Glafkides Photographic Chemistry Vol 1 Compressed PDF

PIERRE GLAFKIDES
Chemical Engineer of the Institute of Chemistry of Paris
PHOTOGRAPHIC
CHEMISTRY
VOLUME ONE
Translated from the French by

KEITH M . HORNSBY, F.R.P.S.
With a Foreword by
L. P. CLERC, HoN. F.R .P.S.
FOUNTAIN PRESS · LONDON

Volume One
of the English language edition first published 1958
Translated into English in two volumes from the second French edition
(published 1957) with the authorization of the
Publications Photographiques et Cinematographiques Paul Monte!, Paris
Printed in Great Britain by

J. W . Arrowsmith Ltd., Bristol
CONTENTS
(Figures in brackets refer to page numbers) Page
FOREWORD by L. P. Clerc, Hon. F .R.P.s. Xlll
Part One
THE FORMATION AND DEVELOPMENT OF THE

PHOTOGRAPHIC IMAGE
Chapter I
NATURE OF LIGHT 3
§1 The wave-like character of light (3) §2 Structure of light (4) §3 The
photon (5) §4 The electromagnetic wave (6) §5 Theory of the annihilation
of photons (7) §6 Emission of radiation by matter (7) §7 The action of radia-
tion on atoms (9) §8 Photoelectric effect (9) §9 Absorption of light by
molecules (9)
Chapter II
PHOTOCHEMISTRY 11
§10 Basic laws (11) §11 Photochemical dissociation (14) §12 Organic photo-
chemical reactions (14) §13 Inorganic photochemical reactions (15) §14
Phototropy (16) §15 Fluorescence and phosphorescence (17)
Chapter III
THEORY OF THE LATENT IMAGE 20
§16 The silver bromide crystal (20) §17 Adsorptions on the surface of
crystals (22) §18 Absorption spectra and photoconductivity (22) §19
Alkali halides (23) §20 Defects of the crystal lattice (24) §21 Sensitivity
specks (25) §22 Process of latent image formation according to the Gurney-
Mott theory (26) §23 Positive holes (28) §24 Mitchell's theory (28) §25
Stasiw and Teltow's theory (29) §26 Constitution of the latent image (30)
§27 Internal latent image (31) §28 Printing out (32) §29 Effects of low
temperatures (33) §30 Effect of high pressure (33) §31 Intensification of
the latent image (34)
Chapter IV
REDOX POTENTIAL 39
§32 The pH (39) §33 Measuring the pH (41) §33A Oxidation and reduction
(42) §34 Electrode potential (43) §35 Redox potential (44)
v
VI CONTENTS
Chapter V Page
THEORY OF DEVELOPMENT 48
§36 Development centres and redox potential (48) §37 Adsorption of de-
veloper and development theory (49) §38 Structure of the developed grain
(51) §39 Influence of pH on the development potential (52) §40 Influence of
the sulphite (53) §41 Modification of the potential barrier (55) §42 Induc-
tion period (56)
Chapter VI
THE DEVELOPING SOLUTIONS 60
§43 Composition of the developing solution (60) §44 Water used for de-
velopers (61) §45 Hard waters (62) §46 Developer alkalis (62) §47 Sulphite
(63) §48 Developers preparation (64) §49 Energy of a developer (64) §50
Negative developers with a single developing agent (66) §51 Diaminophenol
developers (68) §52 Superadditivity of developers (68) §53 Metol-hydro-
quinone developers (70) §54 Pryo-metol developer (71) §55 Phenidone
developer (71) §56 Combined developers (72) §57 Developer for doubling
speed (73) §58 Compensating developers (73) §59 Tropical developers (74)
§60 Bromide paper developers (76) §61 Developers for contrasty emulsions
(76) §62 Developers for motion-picture positives (77) §63 Caustic developers
for maximum contrast (77) §64 Chloride paper developers (78) §65 De-
velopers for warm tones with chlorobromide or chloride emulsions (79) §66
Special developers for warm-tone lantern plates (80) §67 Inorganic develop-
ers (82) §68 Metal-organic complexes (82) §69 Reversible developers. De-
velopment with vanadium salts (84) §70 Special developers (85) §71
Physical development (86)
Chapter VII
FINE-GRAIN DEVELOPERS 89
§72 What is 'grain' in a photographic image? (89) §73 Effect of the developer
on grain (93) §74 Borax developers (95) §75 Pyro, p-aminophenol, and pheni-
done developers (96) §76 Plain metol developers (97) §77 Simple pyrocate-
chin developer (97) §78 Thiocyanate developer (97) §79 p-phenylenedia-
mine developers (98) §80 Developers using combined p-phenylenediamine
(99) §81 o-phenylenediamine developers (99) §82 Atomal developer (99)
§83 Miscellaneous fine-grain developers (100)
Chapter VIII
USE OF DEVELOPING SOLUTIONS 101
§84 Methods of development (101) §85 Development time (102) §86 De-
velopment temperature (102) §87 Agitation (103) §88 Equipment materials
(103) §89 Sulphide fog (104) §90 Aerial oxidation of developers (105) §91
Exhaustion of developing solutions (105) §92 Continuous development (106)
§93 Faults due to development (108) §94 Development accelerators (108) §95
Ultra-rapid development (109)
CONTENTS Vll
Chapter IX Page
THE DEVELOPING AGENTS 112
§96 The developing functions of cyclic compounds ( 112) §97 H ydroquinone
(113) §98 Hydroquinone derivative developers (114) §99 Pyrocatechin (115)
§100 Pyrogallol (116) §101 Naphthols (117) §102 Hydroxyanthracenes (117)
§103 Influence of aldehyde, carboxyl and ketone groups (117) §104 Proper-
ties of aminophenols (118) §105 Preparation of the aminophenols (119)
§106 Aminonaphthols (120) §107 Metol or p-methylaminophenol (122)
§108 Glycin or p-hydroxyphenylglycin (123) §109 Preparation of N-substi-
ted aminophenols (Metol and others) (123) §110 Simple diamines (124)
§111 Substituted diamines (125) §112 Diaminophenols (125) §113 Prepara-
tion of diaminophenols (126) §114 Polyamines (127) §115 The Heterocyclic
bases (127) §116 Phenidone (128) §117 Combined developers (128) §118
Aliphatic developers (129)
Chapter X
DEVELOPER ANALYSIS 132
. §119 Importance of analysis (132) §120 Selective extraction of hydroquinone
and metol from developers (132) §121 Non-selective extraction of metol and
hydroquinone (134) §122 Estimation of hydroquinone in the separated
extract (134) §123 Estimation of metol in separate extract (135) §124 Esti-
mation of metol and hydroquinone in a single extract (136) §125 Simul-
taneous spectrophotometric determination of metol and hydroquinone (137)
§126 Estimation of other developers (137) §127 Estimation of sulphite (138)
§128 Estimation of carbonate (138) §129 Estimation of borates (139) §130
Measurement of developer pH (139) §131 Estimation of various constituents
(140) §132 Bromide estimation (140) §133 Iodide estimation (141) §134
Estimation of impurities (142) §135 Analytical reactions of developing
agents (142) §135b Chromatographic analysis (143) §136 A.S.A. standards
of purity for developing agents (143) §137 A.S.A. standards of purity for
photographic chemicals (145)
Chapter XI
FIXING, WASHING AND DRYING 148
§138 Stop baths (148) §139 Hardening stop baths (148) §140 Control of
stop baths (149) §141 Formalin hardeners (150) §142 Silver halide solvents
(150) §143 Fixing with thiosulphate (152) §144 Acid fixers (153) §145 Hard-
ening fixers (154) §146 The fixing operation (155) §147 Rapid fixing (156)
§148 Simultaneous development and fixation (157) §149 Stabilizing images
by fixing (158) §150 Washing (159) §151 Control of the wash water (160)
§152 Control of the washed image (161) §153 Elimination of hypo by oxida-
tion (162) §154 Fixing bath analysis (162) §155 Recovery of silver from
hypo baths (163) §156 Drying (165) §157 Reticulation (167) §158 Glazing
and drying prints (168) §159 Analytical examination of image marks (169)
Vlll CONTENTS
Chapter XII Page

REVERSAL 171
§160 Reversal, reduction and intensification (171) §161 First development
(171) §162 Reversal baths (173) §163 Clearing the reversed image (174)
§164 Second exposure (175) §165 Reversal without re-exposure (175) §166
Second development (175) §167 Single bath reversal (176) §168 Reversal
identity photographs (176) §169 Reduction (176) §170 Cutting reducers
(177) §171 Potassium ferricyanide cutting reducers (178) §172 Proportional
reduction (180) §173 Superproportional reduction (181) §174 Special re-
ducers (183) §175 Mercuric chloride intensification (183) §176 Mercuric
iodide intensification (184) §177 Indophenol intensification (185) §178
Ferrocyanide intensification (185) §179 Physical intensification (186) §180
Chromium intensification (186) §181 Quinone intensification (187) §182
Intensification by dyeing (187)
Chapter XIII
TONING 189
§184 Sulphiding after bleaching (189) §185 Sulphiding images bleached
with metal salts (190) §186 Sulphiding with sulphur complexes (191) §187
Toning by direct sulphiding (192) §188 Selenium toning (193) §189 Col-
loidal silver toning (194) §190 Gold toning (195) §191 Gold-toning baths
(195) §192 Gold-toning baths with solvent (196) §193 Gold-toning of
sulphided images (197) §194 Toning-fixing (198) §195 Platinum toning
(199)
Chapter XIV
SENSITOMETRIC LAWS 200
§196 Exposure (200) §197 Opacity (200) §198 Density (201) §199 Charac-
teristic curve (203) §200 Contrast (203) §201 Effect of developing time on
contrast (205) §202 Equations of the characteristic curve (206) §203 Shape of
the characteristic curve (207) §204 Variation of contrast along the character-
istic curve (209) §205 Exposure latitude (209) §206 Solarization (210) §207
Reciprocity failure (212) §208 Threshold of effective illumination (213)
§209 Schwartzchild coefficient (214) §210 Intermittency effect (214) §211
Reversal effects (215) §212 Herschel effect (216) §213 Becquerel effect (216)
§214 Photochemical reversal (217) §215 Sabattier effect (217) §216 Weigert
effect (217) §217 Emulsion fog (218) §218 Other causes of fog (219)
Chapter XV
SENSITOMETRY 221
§220 Exposing instruments-sensitometers (222) §221 Photometric absorb-
ing wedges (223) §222 Density measurements (225) §223 Photoelectric
densitometers (226) §224 Null-reading photoelectric densitometers (227)
CONTENTS IX
Page
§225 Reflection densitometers (228) §226 Development (229) §227 Measure-
ment of sensitivity (231) §228 Measurement of sensitivity by the threshold
method (232) §229 Measurements of sensitivity by the inertia method (234)
§230 Fixed gradient methods (235) §231 ASA system (235) §232 Notes on
the choice of a criterion of sensitivity (237) §233 Resolving power (238)
§234 Diffusion (Irradiation) (239) §235 Granularity (240) §236 Graininess
.
(242) §237 Influence of contrast on the resolving power (243)
Chapter XVI
PHOTOGRAPHIC REPRODUCTION 246
§238 The negative (246) §239 Duplicate negatives (246) §240 Reversal
(248) §241 Transparent positive copies (249) §242 Photographic papers
(250) §243 Gradation of papers (252) §244 Reproduction of extreme den-
sities (254) §245 Industrial papers (255) §246 Variable contrast papers (255)
§247 General properties of sound (256) §248 Principle of sound recording
(257) §249 Emulsions for sound recording (260) §250 Development of
sound recordings (261) §251 Sound tracks on colour films (263)
X CONTENTS
Part two
PHOTOGRAPHIC EMULSIONS
Chapter XVII Page

GELATIN 269
§252 Colloidal properties of proteins (269) §253 Isoelectric point (270) §253b
Gelatin solvents (271) §254 Viscosity of aqueous gelatin solutions (271) §255
Surface tension (271) §256 Swelling of gelatin (271) §257 Gelatin gels (272)
§258 The amino acids (274) §259 The peptides (275) §260 The proteins
(276) §261 Hydrolysis of gelatin (277) §262 Molecular weight of gelatin
(279) §263 Structure of gelatin (279) §264 Conversion of the collagen to
gelatin (280) §265 Photographic gelatin (280) §266 Ripening retarders (281)
§267 Measurement of the retarding power (283) §268 Gelatin sulphur sensi-
tizers (284) §269 Estimation of sulphur sensitizers (285) §270 Desensitizers
and contrast modifiers (286) §271 Ripening accelerators (287) §272 Alde-
hydes (287) §273 Sugars and carbohydrates (288) §274 Fog inhibitors (288)
§275 Gelatin examination (289) §276 Inorganic compounds in gelatin (289)
§277 Raw materials (291) §278 Liming (292) §279 Neutralization (292)
§280 Cooking (293) §281 Acid process gelatin (293) §282 De-activation of
gelatin (294) §283 Demineralization of gelatin (295)
Chapter XVIII
GENERAL PRINCIPLES OF EMULSION PREPARATION 298
§284 Formation of photosensitive silver halides (298) §285 Silver bromide
without protective colloid (299) §286 Mechanism of precipitation (299) §287
Precipitation methods (301) §288 Working conditions (304) §289 Physical
ripening (305) §290 Retarders and accelerators of physical ripening (307)
§291 Distribution of grains after physical ripening (307) §292 Setting and
washing (309) §293 Treatment of emulsions without washing (311) §294
After-ripening (311) §295 Sensitivity specks (313) §296 Choice of gelatin
(313) §297 Sulphur sensitizers (315) §298 Various organic sensitizers (316)
§299 Inorganic sulphur sensitizers (317) §300 Influence of metallic salts (318)
§301 Gold sensitizing (319) §302 Role of silver iodide (320) §303 Lead and
thallium emulsions (321) §304 Ultrasonic action (322) §305 Commercial
emulsion manufacture (322) §306 Powdered emulsions (323) §307 Manu-
facture of silver nitrate (323) §308 Analysis of sensitive materials (324)
Chapter XIX
NEGATIVE EMULSIONS 327
§310 Neutral emulsions (327) §311 Double-jet neutral emulsions (329) §312
Acid emulsions (330) §313 Borax emulsions (330) §314 Ammonia emulsions
(331) §315 Completely ammoniacal emulsions (332) §316 Semi-ammoniacal
emulsions (334) §317 Emulsion mixtures (335)
CONTENTS XI
Chapter XX Page
SLOW EMULSIONS 337
§319 Fast neutral diapositive emulsions (337) §320 Ammoniacal positive
emulsions (338) §321 Bromide emulsions for high-speed papers (339) §322
Bromide emulsions for printing papers (339) §323 Agfa Brovira bromide
paper emulsions (340) §324 Methods of preparation of silver chlorobromide
emulsions (342) §325 Chlorobromide emulsions by normal precipitation
(type A) (344) §326 Reverse precipitation chlorobromide emulsion (type B)
(347) §327 Chlorobromide emulsions with part of the chloride precipitated
separately later (type C) (348) §328 Chlorobromide emulsion with separate
precipitations of bromide and chloride (type D) (350) §329 Silver chloride
emulsion types (350) §330 Chloride emulsion formulas (351) §331 Chloride
emulsions, unwashed, with cadmium (353) §332 Chloride emulsions with
cobalticyanide (355) §333 Direct positive emulsions (autopositive) (355)
§334 Print-out emulsions (citrate papers) (356) §334b Other silver salts
(358) §335 General properties of collodion emulsions (359) §336 Wet
collodion (359) §336b Eggert and Kleinschrod process (360) §336c Dry
collodion (360) §337 Celloidin emulsions (361) §338 Polyvinyl alcohol
emulsions (363) §339 Polyvinylpyrrolidones (364) §340 Sensitized cellulose
(364) §341 Sensitized cellulose acetate (364) §342 General properties of
Lippmann emulsions (365) §343 Preparation of Lippmann emulsions (365)
Chapter XXI
STABILIZING AND FINISHING PHOTOGRAPHIC
EMULSIONS 369
§344 Law of mass action (369) §345 Variations in the concentration of silver
and bromide ions (370) §346 Measurement of the silver ion concentration
(370) §347 Effect of silver ion concentration (372) §348 Low temperature
storage (374) §349 Organic antifoggants (374) §350 lndolizines (378) §351
Use of antifoggants (379) §352 Finals (380) §353 Antiseptics (381) §354
Matting agents (381) §355 Hardeners (382) §356 Wetting agents (383) §357
Antifrothing agents (384) §358 Viscosity of emulsions (385) §359 Emulsion
coating (386) §360 Emulsion drying (388) '
Chapter XXII
ULTRA-VIOLET PHOTOGRAPHY 391
§361 Ultra-violet sources (391) §362 Absorption (392) §363 Spectrographs
(393) §364 Ultra-violet sensitive layers (393) §365 Schumann method (394)
§366 Superficial fluorescent layer method (395) §367 Actinometric paper
(396) §368 Applications (397)
Chapter XXIII
X-RAY AND CHARGED PARTICLE PHOTOGRAPHY 399
§369 X-ray sources (399) §370 Photographic action of X-rays (399) §371
X-ray sensitive layers (401) §372 Fluorescent intensifying screens (404)
§373 Copies of radiographs (404) §374 Applications (405) §375 Gamma
Xll CONTENTS
Page
radiography (406) §376 Contamination of emulsion packages by atmospheric
radioactive substances (406) §377 General observations on the photographic
action of electrons (406) §378 Electron emulsions (407) §379 Autoradio-
graphy (408) §380 Photographic action of charged particles (408) §381
Nuclear emulsions (409) §382 Development of nuclear emulsions (412)
§383 Measurement and differentiation of nuclear tracks (414)
Chapter XXIV
PHOTOSENSITIVE SYSTEMS & SPECIAL TECHNIQUES 419
§384 Photosensitive systems (419) §385 Insoluble systems (419) §386
Mercury salts (420) §387 Insoluble lead salts (420) §387b Phosphotungstic
acids (421) §388 Endothermic compounds (421) §389 Soluble systems (421)
§390 Iron salts (422) §391 Iron organic complexes (422) §392 Iron-organic
system (424) §393 Iron-silver system (sepia paper) (424) §394 Iron-mercury
system (425) §395 Iron-platinum system (Platinum process) (425) §396 Iron-
gold system (426) §397 Iron-ferricyanide systems (427) §398 Ferroprussiate
paper (428) §399 Sensitizing formulas (428) §400 Other photosensitive
systems (429) §401 Photoceramics (430) §402 Preparation of ferric oxalates
and citrates (430) §403 Sensitive layers adsorbed on glass (431) §404 Sensi-
tized anodized aluminium (432) §405 Photographic tracing on sheet metal
(433) §406 Reversal transfer (434) §407 Polaroid-Land process (435) §408
Xerography (436) §408b Electrofax (437) §408c Berchtold process (437)
§408d Thermofax (438) §409 Ferrography (438) §410 Photosensitive glass
(438)
Chapter XXV
PHOTOGRAPHIC BASE MATERIALS 441
§411 Constitution of cellulose (441) §412 Paper (442) §413 Sizing (444) §414
Baryta coating (445) §415 Waterproof paper (448) §416 Tests on papers
(448) §417 Cellulose esters (449) §418 Cellulose acetates (449) §419 Pre-
paration of cellulose acetate in homogeneous medium (450) §420 Prepara-
tion of cellulose acetate in suspension (heterogeneous medium) (451) §421
Cellulose raw material (452) §422 Cellulose acetopropionate and acetobuty-
rate (453) §423 Other cellulose organic esters (454) §424 Cellulose nitrate
(455) §425 Plasticizers (456) §426 Dopes for film casting (457) §427 Sol-
vents (458) §428 Film-base casting (460) §429 Deformation of films (461)
§430 Burning and decomposition of films (463) §431 Gelatin removal (463)
§432 Analysis of cellulose esters (464) §433 Cellophane (464) §434 Polyethy-
lene terephthalate films (465) §435 Constitution and manufacture of poly-
ethylene tereph thalate (465) §436 Other film bases (467) §437 The substratum
(467) §438 Halation (469) §439 Anti-halo layers for photographic films (470)
§440 Anti-halo layers for cine films (471) §441 Anti-halo backing for plates
(472) §442 Antistatic layers (473) §443 Anti-abrasion layer (474) §444 Strip-
ping layers (474) §445 Two-colour backing paper (475) §446 Film splicing
(475) §447 Film cleaning (475) §447b Protective lacquers (476) §448
Mountants (477) §448b Stripping negatives (478)
INDEX 483
FOREWORD
TO THE FIRST FRENCH EDITION
MR. P. GLAFKIDE S, who was kind enough to ask me for a Foreword
has certainly done useful work in writing this book on Photographic
Chemistry. All the books on this subject, published in the French lan-
guage, are at least thirty years old, and therefore very largely out of
date; some, indeed, were already out-dated on publication!
The author, who has worked in a photographic research laboratory
in the United States is highly qualified to undertake this important
task, which embraces a very vast field, several aspects of which were,
in France, covered only by fragmentary and widely dispersed writings.
Precise directions are given for the preparation of several types of
emulsion; the chapter devoted to colour sensitizers is treated as ex-
tensively as anyone could desire, and the theory of the latent image
and development include the most recent information.
This book will not only be of great value to chemists in the photo-
graphic industries, but will also enable enterprising photographers-
both professional and amateur-to acquaint themselves, at no great
effort, with the rudiments of chemistry necessary for an intelligent
practice of their profession or hobby. The great number of references
will enable the reader to refer to original sources should he wish to
give further study to a particular subject.
It is my very sincere wish that this useful book may enjoy all the
success which it deserves.
L . P. CLERC
FOREWORD
TO THE SECOND FRENCH EDITION
IN THE FOREWORD to the first edition of this volume which I had pride
in writing at M. Glafkides request, I had the pleasure of affirming the
excellence of this work. In the last few years considerable progress
has been made in this field, and it is therefore pleasing that the author
has prepared a new revised edition, always fully documented. If any
fault can be found in this work it is that of being too complete, dealing
with many matters alien to chemistry, but which are admirably treated.
I hope that this second edition will be at least as successful as the first.
L. P. CLERC
xiii
PART ONE
The Formation and Development of the

Photographic Image
CHAPTER I
NATURE OF LIGHT
1. The Wave-like Character ofLight
1.-Light is propagated in a vibratory movement or waves.
This pronouncement, formulated by Huyghens in the seventeenth century,
was revived by Young at the beginning of the nineteenth century, then
developed successively by Fresnel and Maxwell. The latter, referring par-
ticularly to the idea of a transversal wave, considered it as an electromagnetic
disturbance. It was thus possible to explain the effects of diffraction, inter-
ference and polarization.
According to the electromagnetic theory, a light-wave is represented at

each point of its motion by a plane set at right angles to its direction of travel,
and in this plane two vectors are present--one being electric and the other
magnetic-which oscillate in mutually perpendicular directions. In other
words, a radiation could be defined as a periodical variation in space of com-
bined electric and magnetic fields.
Fig. 1.
If we represent (Fig. 1) the resultant elementary wave by an oscillation

AMBNC proceeding in the direction XY, the length ,\of this wave will be
shown by the distance AC.
The speed of travel c, or distance covered in one second, is constant :
300,000 km per second.
During one second, a light ray performs a number of complete oscillations
(AMBNC) equal to v = cf ,\
B 3
PHOTOGRAPHIC CHEMISTRY
v is the frequency of the wave. It is higher as the .\ is smaller. Since v

oscillations take one second, a single oscillation will take a time or period
equal toT= 1Jv seconds.
The wave-length .\ is characterized by the colour (also its frequency v to
which it is related). Wavelengths are measured by taking as units the micron
p, (or thousandth of a millimetre), the millimicron mp, (or millionth of a
millimetre) and the Angstrom unit A (or ten-millionth of a millimetre). One
mp, is therefore equal to 10 A.
2. The range of elect1'omagnetic waves is continuous from the radio waves

measured in thousands of metres, to the y rays of radium, which are lower
than one-thousandth of an A as follows:
Radio waves from several tens of kilometres to
1 millimetre
Infra-red (or heat radiations) from 1,000p, to ·74p,
Visible spectrum from 740 mp, to 400 mp,
Ultra-violet from 400 mp, to 10 mp,
Undefined rays from 100 A to 20 A
Soft X-rays about 12 A
Hard X-rays about 0·05 A
y rays of radium about 0·001 A
The visible spectrum occupies no more than a very limited band in the
range of radiations. It is situated in the centre of the spectrum produced by
the optical systems, between the ultra-violet and the infra-red, and is sub-
divided into a certain number of colours, or rather groups of monochromatic
light, as follows :
Violet 395 to 435 mp, Yellow 570 to 595 mp,
Blue 435 to 500 mp, Orange 595 to 625 mp,
Green 500 to 570 mp, Red 625 to 740 mp,
All radiations carry energy. This energy can be discerned by the human
eye within narrow limits; over a greater range by means of a photographic
plate, a photoelectric cell, a thermopile, a bolometer (resistance variation of
a metallic strip) or a Crooke's radiometer. It is thus possible to observe a flux
of energy of 10- 9 to 10- 15 watt.
2. Structure of Light
1. According to the theory of the wave system, a sine wave emitted by a light
source should lose itself in space through progressive dispersal. But this does
not occur, since--even after having travelled for a considerable distance-a
ray of light is capable of producing photochemical and photoelectrical
effects which necessitate a certain amount of energy.
Light is made up of units which cannot be sub-divided. We already know
the discontinuity of matter, which is made up of complete and independent
fragments such as molecules, atoms and electrons. That light should display
NATURE OF LIGHT 5
an equally discontinuous nature should cause no surprise, and this hypothesis,
formerly propounded by Newton, was later revived with success by Ein-
stein.
Yet a ray can travel around an obstacle, as proved by the effects of diffrac-
tion and interferences-a property which is absent in a projectile, which would
be completely deviated from its course.
The undulatory character of light being an unquestionable, though unex-
plained, fact, it became necessary to devise a logical explanation. This was
accomplished by the ingenious association of the two theories-corpuscular
and undulatory-a point which had in fact, been considered by Newton
himself.
2. The wave mechanism, developed by L. de Broglie and Schrodinger, is
based upon Planck's quantum theory, perfected by Bohr.
This theory suggests that corpuscular movements occur according to an
unbroken sequence of entire values, or quanta. In other words, all action
proceeds in abrupt and independent steps.
Since light is of a vibratory nature, it is not divisible infinitely. Each com-
plete oscillation (Fig. 1) corresponds to a fixed amount of energy h, equal to
6·55 X 10-27 erg/second. <Il his Planck's constant.
If v is the frequency of the radiation under consideration (number of
cycles per second) the smallest quantity of isolated energy which it is possible
to bring into play is hv. hv is a quantum of energy or photon.
It will consequently be seen that the higher the frequency-i.e., the shortel'
the wave-length-the higher will be the amount of energy conveyed by the
radiation. Thus X-rays are stronger than ultra-violet rays, which in turn are
stronger than the blue and green radiations, and these latter are in turn more
energetic than the red or infra-red radiations.
By considering each single vibration h, or quantum, as a corpuscle, the
conclusion is reached that light is formed of units of energy, or photons, associ-
ated in a wave movement.
3. The Photon
The photon is an electically neutral particle, with an extremely small mass.
It can only acquire energy by reason of its very high speed.
The quantum theory, applied to the electromagnetic fields, had suggested
zero mass for the photon, in order to comply with Maxwell's equations. But
the calculations of undulatory action, on the other hand, demand that there
should be some mass, however small. If the mass of the electron is m =
0·9 X 10-25 grammes, that of the photon flo would be in the region of 10-45
to 10- 65• It follows, therefore, that the velocity of light is a maximum velocity
which the photon never reaches, and that the relativity phenomena do not
depend on light.
When studying the electron, it will be observed that it displays a spin, or
rotary movement on its own axis, accompanied by a magnetic effect.
Spin is measured in units hf21T. The spin of an electron is rated at lf2(hf21T);
in other words, the electron has a spin of l f2.
6 PHOTOGRAPHIC CHEMISTRY
Photons are also subject to spin, but in this case the figure is 1. Now since
spin is the result of three straight line components, a photon may thus pass
through different states according to the value of these components. One of
these may be positive, negative or neutral, i.e., equal to +hf2TT, 0, or -hj2TT.
If the component is positive, then perpendicular electric and magnetic fields
are formed, which accompany the photon. The area formed by the directions
of these two fields is animated by a rotary movement towards the left, around
the third axis, viz., that of propagation. The angular speed of rotation is
2TTv. This pattern corresponds with that of Maxwell's representation given
in paragraph 1. It is similar when the component of the spin, according to the
axis of propagation, is negative, except that the plane of the electromagnetic
fields revolves to the right. The wave is described as having a left or right
circular polarization. The combination of a right circular wave with a left
circular wave produces a straight or elliptical polarized wave, according to
the equivalence of the two elementary waves, or to the predominance of one
of them.
In the case of a neutral-spin component, the photon is accompanied solely
by an electrical wave, travelling in the same direction.
A photon with a spin of 1 therefore conforms very well with the result of
Maxwell's equations on electromagnetic waves. However, there are other
types of equation, bringing in a photon with a spin of 0, which is still unknown.
It may even be considered that photons with a spin of 1 or 0 are the result
of the fusion of two corpuscles with a spin of 1/2, whose respective spins add
up or can~el out. Those two hypothetical corpuscles, the ergon and the anti-
ergon, have been the object of many suppositions, and it has been felt that
they should be associated in the same manner as electrons and positrons.
Indeed, a photon with an energy exceeding a million electron-volts is capable
of materializing in the form of a positron and an electron when it passes
through an atom. Conversely, it is possible to de-materialize a positron-
electron combination in the shape of two photons of half a million electron-
volts each. This is the reversible conversion of light to matter.
The associations of photons follow the Bose-Einstein statistical law, by
which the same state may apply to any number of corpuscles. Electrons, on
the other hand, follow the Fermi-Dirac statistical law, in which a single
corpuscle is present in one particular ~tate, to the exclusion of all other cor-
puscles. This latter principle, formulated by Pauli, states that two electrons
cannot follow exactly the same orbit.
In short, light consists of corpuscles of energy, or photons, which carry an
anisotropic electromagnetic wave.
4. The electromagnetic wave

Actually, the wave itself, which characterizes the vibratory condition of the photon,
does not carry any energy. The wave has no physical existence. It is a function of
probability, of fixed frequency, which defines the position of the corpuscle in time. In
other words, the photon is guided by a wave of probability.
The wave-function .p(x, y, z, t) of the photon, called the field, is based upon a func-
tion of Lagrange, with sixteen components,<•! but in this case a linear operative term H
NATURE OF LIGHT 7
(called 'Hamiltonian and Hermitian') is brought in. The evolution of the wave-function
.p, in time, is then written as follows:
h d!f
- - =H!fo
27Ti dt
Since there are sixteen components, sixteen simultaneous partial differential
equations are obtained. .P is thus a complex quantity formed by rP~> .P 2 , f 3 , etc. By
substituting other quantities of a particular character, for the sixteen original com-
ponents, it is possible to represent the potentials and the fields of the orthodox
electromagnetic theory.
Let us now consider a number n of photons in all the possible states of energy.
Their evolution in space accords with a distribution function R which presumes that
at the instant t there are n corpuscles in state 1, n 2 corpuscles in state 2, etc.; i.e., as
shown by [R(n, n 2 • • • t)) 2 • This function of distribution progresses according to the
same type of equation as that given for .p, but in this case the operative factors H
influence the variable n. The quantum theory, when applied to electromagnetic
x,
fields, gives the electromagnetic quantities (which depend on space y, z and time t)
to these operative factors H which act upon n .
5. Theory of the annihilation of photons

L. de Broglie developed a theory whereby the photons can 'exist' in a particular state
of annihilation (represented by a wave-function f( 0)) which renders them unobserv-
able. In order to disappear in this manner, the photons must give up their energy and
their movement quantity to such material elements as electrons, and this is what
happens in the case of any photon absorbed by matter. Conversely, under the influence
of electric charges, the electromagnetic field which was cancelled reappears and the
photon becomes observable again.
Space, known as vacuum, would thus be the repository of an immense and constant
number of annihilated photons, whose field, of course, is nil.
But photons may be unobservable without being annihilated, e.g., photons ex-
changed by two n eighbouring electrons.
The theory of annihilation provides an explanation for the existence of an electro-
static field between two electrons, as well as the creation by the latter of an electro-
magnetic field and the emission of radiations by matter.
In order to introduce the function of the annihilated state f( 0) in undulatory action,
it is necessary to agree that propagation occurs, not in a four-dimensional space
(x, y, z, t), but in a five-dimensional space (x 0 , x, y, z, t) in which x 0 is beyond our
perception. The components of the function !f of the normal state of · the photon
depend on x 0 by the factor eik,x, which, when introduced into the equation, produces
the following for the non-disintegrated states:
!fen = frn(x,y, z, t)eik,x,

where a, -r = 1, 2, 3, 4.
6. Emission of radiation by matter

Let us consider an atom in a state of repose (or stationary). Each electron
travels around the smallest orbit it can adopt, provided that the length of its
trajectory is an exact number of times the length of the associated wave. In
this stable condition of minimum energy the atom does not emit any radiation.
If, for any reason, an electron 'jumps' from the minimum orbit to an orbit
of higher degree, with an absorption of a 'finite quantity' of energy, the atom
is then in an activated state, similar to that of a tightened spring ready to be

released. The potential energy of the atom is increased.
It may happen that the spring will be released, i.e., that the activated
electron will revert either to its original orbit, or to an intermediary orbit,
with a decrease of its activation. The surplus energy which the electron has
acquired is then naturally released in the form of radiation.
Since the smallest particle of theoretical energy ish (1 oscillation), and that
the energy of a photon is hv, the frequency is equal to the quotient of lost
energy E by h: v = Efh, since one must have hv = E.
When the energy released is sufficiently low, the luminous emission occurs
near the visible spectrum. This emission is the result of the activation of the
surrounding levels only, which are more readily affected. This is what happens
with the average incandescent substances.
One particular method of activation of atoms consists in bombarding them
in high vacuum by cathode rays (which are themselves formed by streams of
electrons of various speeds). When it has been de-activated, an activated
element (or anticathode) emits a very high-frequency radiation, viz., X-rays.
It is observed that the spectrum of these X-rays varies with, and characterizes,
each element. This spectrum is formed of groups of lines corresponding with
the various levels of energy of the electrons, which may thus be located and
studied. It is then possible, by means of X-rays, to determine the electronic
structure of the elements.
The energy lost by an electron En - Em is approximately related to the
characteristics of the latter by the formula
En 21T2me4
h n 2 h3
in which m is the mass of the electron, e its charge, h is Planck's constant

and n is an integral positive number. En fh is called the spectral term. The
division in two of the hydrogen emission lines led Sommerfeld to a more
complete formula, which was then generalized by Rydberg, viz.:
in which rx is the 'fine structure constant', n and k integral numbers, and t:l a
characteristic quantity for each element.
In fact, a line of light emitted by a body consists of more than two lines in
close proximity. By taking as a basis the properties of spin, Dirac made the
spectral term depend from three quantum numbers, n, l, and j. In order that
an emission should occur at a certain frequency, it is necessary that the
probability of transition of the electron from one state to another should not
be nil.
In the case of radioactive bodies the y-radiation (or very high-frequency
photons j is due to the effect on the nucleus caused by the departure of helions
(nuclei of helium). The corpuscles constituting the heavy nucleus of the radio-
NATURE OF LIGHT 9
active body are distributed over the energy levels, as are the planetary elec-
trons. Any departure of a helion produces a redistribution of energy levels
with a rearrangement accompanied by an emissicn of photons.
7. The action of radiation on atoms

A photon which meets an atom may, by electromagnetic action, disturb the
movement and the state of an electron. If the energy of this photon does not
correspond with any state of excitation in the atom, it is emitted again in
another direction, i.e., scattering takes place. The scattering is the more pro-
nounced as the frequency is higher.
If the energy of the photon corresponds with an excitation level in the
atom, the photon disappears after having given out its energy. This is called
absorption. The frequency of the absorbed photon corresponds with that of
the photons which can be emitted.
A disturbed electron may transfer to a more distant orbit if the energy of
the photon agrees with that of the level considered (resonance). The greater
the difference of energies, the lesser will be the probability of detachment.
The excited electrons can, however, resume their original orbit, or succes-
sive intermediary orbits, until the original orbit is reached, while emitting
each time a weaker radiation, i.e., a radiation of longer wavelength.
In the action of X-rays upon atoms, the wavelength of the absorbed
photons is constant and characteristic for each level of electrons (X-rays
spectra).
8. Photoelectric effect
When the photons bring about the complete extraction of an extra-orbital
electron, the latter escapes from the atom, thus creating an electric current.
This is the photoelectric effect. The photons disappear in giving out their
energy.
hv =exciting energy+kinetic energy taken away by the electron.
The energy required for the extraction corresponds with the ionizing energy
of the atom, which amounts, for instance, to 4·3 electron-volts for potassium.
In this manner, a luminous ray will produce from a thin film of alkaline
metal (potassium or caesium) placed at the bottom of a bulb filled with an
inert gas under low pressure, a number of electrons proportionate to the
number of photons received, i.e., proportionate to the intensity of the light.
The weak electric current obtained is amplified before use.
It may happen that the energy of the photons does not agree with the states
of excitation of the electrons in the atom. If the frequency of the incident
radiation is high (X- andy-rays) it is possible to have a scattering of photons
as well as an ejection of electrons. This is the Compton effect.
9. Absorption of light by molecules

Any light which penetrates through a substance emerges minus a certain
number of photons of given wavelengths. A selective absorption occurs. This
absorption is constant and characteristic of the substance considered. If the
absorbed radiations are situated outside the visible spectrum, the substance
appears colourless to the human eye. If certain radiations are absorbed, it
appears coloured by transmitted or reflected rays. Finally, if most of the
visible radiations are absorbed, the substance looks black or dark in appear-
ance.
The absorption which occurs in the areas between the ultra-violet and
infra-red depends on the molecular constitution, and molecules are the source
of three kinds of movement (i.e., of variations of energy), viz.:
(a) Rotary movement of the molecules themselves around an axis perpen-
dicular to the main coordinating axis of the atoms.
(b) Vibratory movement of the nuclei.
(c) Movement of the electrons, especially the outer orbital electrons.
Each one of these movements causes an absorption of photons. The very
long wavelengths of infra-red (10 to 100 p) usually correspond with the mole-
cular rotations, and those from 1 to 10 p to the vibratory movements. How-
ever, certain vibrations may cause thin lines of absorption in the ultra-violet
(see para. 11). But the radiations near the visible part of the spectrum (infra-
red to ultra-violet) correspond with an electronic state of the molecule, which
is shown by a system of absorption bands.
This electronic condition depends not only on the nature and number of
atoms present in the molecule, but also on the relative distances of their
nuclei and their position. It depends therefore on the orbits described by the
outer orbital electrons of the associated system, and on their various states
of energy. In order that absorption may occur, resonance must be present
between the vibratory condition of the incident photons and that of the elec-
tronic system of the molecule.
1. The term 'erg' is used to d escribe the work accomplished by a force of 1 dyne
acting through 1 centimetre in the same direction as the force. A dyne is the unit
of force which, applied to a mass of 1 gramme, imparts to it a velocity of 1 centi-
m etre per second. F = m y. 1 kilogramme-metre = approximately 10 " ergs, and
1 watt = 10 7 erg/seconds .
2. de Broglie L., M ecanique Odulatoire du Photon et Theorie Quantitique des Champs.
(Gauthier Villars, P aris, 1949.)
Chapter II
PHOTOCHEMISTRY
Photochemistry is the study of chemical reactions brought about by light.
The photochemical action consists of two main phases, viz.:
(a) The reception of luminous energy; and
(b) The actual chemical process.
Depending on whether a single substance is involved, or of a system com-

prising several substances together, it is possible to obtain either a decomposi-
tion of the compound into its elements (photolysis), or a combination of several
substances into a single one (photosynthesis).
10. Basic laws

1. Grotthus-Draper's absorption law. A radiation cannot bring about a
chemical action unless it is absorbed by a body (or a system of bodies). Other-
wise it is impossible for any transmission of luminous energy to take place.
It may be appropriate to note that the radiations which constitute the
colour of a body are precisely those which are not absorbed, and they conse-
quently have no effect upon it. On the other hand, the complementary
radiations of this colour are absorbed and are capable of action. For instance,
a green substance will reflect green, but absorb the blue and red, and can
be decomposed only by these two colours.
However, absorbed radiation does not necessarily act upon the substance
which receives it. It must, in addition, satisfy several other conditions.
2. Energizing law. In order to act efficiently, a luminous radiation must
possess an amount of energy at least equal to that required by the chemical
process.
It is known that the radiations are more energetic as their wavelengths are
shorter (or that their frequency v is the higher), the energy carried by a photon
being expressed by the formula
he
E = hv = - (c = velocity of light)
.\
in which his Planck's constant equal to 6·55 X 10-27 erg.

One gram-photon (containing N photons, i.e., 603 X 10- 21 photons, of which
the total energy is U = Nhc fA. ergs.) corresponds to one gram-molecule
B* 11
containing N molecules (para. 838). By converting to equivalent calories,

the calorific energy of a gram-photon is obtained by the formula
28,420,000
U= calories
Amp
The following table gives an idea of the energy of the various radiations:
Radiations Calories
Ultra-violet 200mf-l 142,500
250m# 114,000
" 284m# 100,000
" 300m# 95,000
Violet" 400mf-l 71,250
Blue-green SOOmf-l 57,000
Green 568mf-l 50,000
Orange 600mf-l 47,500
Red 700mf-l 40,700
Infra-red 800mf-l 35,600
3. Law of photochemical equivalence (or Einstein's Law). For each absorbed

photon there is a corresponding decomposed or synthesized molecule.
It is understood that the active photon complies with the foregoing law of
energy.
Yet it is found in practice that the number of active photons absorbed in a
chemical process seldom agrees with the number of molecules formed or
decomposed. If one calls the ratio of the number of molecules decomposed
to the number of photons absorbed, quantum ratio p.
no. decomposed molecules

p= no. absorbed photons
then a quantum yield is obtained which varies considerably within extensive

limits (between ·1 and 1000 and over). A few reactions only have a theoretical
yield of unity.
However, this contradiction does not bring any doubt to the validity of
Einstein's Law, and the reason for the experimental variations is simple:
(a) When the chemical action demands an addition of external energy
(endothermic reaction)-and this is the case with the silver halides- then p is
equal to 1 at the most. Usually it is less, as in the photochemical decomposition
of hydrochloric gas <1 l since this process is reversible
ZHCl ~ H2 + Cl2
In order to decompose ammonia NH 3 into nitrogen and hydrogen by
means of ultra-violet rays, 4 photons are required for each molecule (p = ·25).
Depending on the wavelength, it is possible to cause a variation in the
PHOTOCHEMISTRY 13
photochemical balance, either in one direction or in the other. The following
is a typical reversible reaction:
Maleic acid ~fumaric acid<2 l
in which, with the ultra-violet,\= 313 mfl, there is 44 % of maleic acid and
56 % of fumaric acid, while with a shorter wave-length (..\ = 200 mtt) the
maleic acid re-forms with 75 % of maleic acid and 25 % of fumaric acid. In
the first instance, the quantum yield amounts to ·03 (30 photons) while it
rises to ·1 (10 photons) for the reverse process (re-formation of maleic
acid).
A similar process can be observed in the formation of sulphuryl chloride
S0 2 Cl 2 from sulphur dioxide and chlorine, viz.:
S0 2Cl 2 ~ S0 2 + Cl 2
Sulphuryl Sulp hur Chlorine
Chloride dioxide
(b) When the absorbed radiations first result in an activation of the mole-
cule, the activated molecule will then react upon a second neutral molecule,
to give products of decomposition, according to the following pattern: <3 l
AB +hv = [AB]
[AB]+AB =2A+2B I
The quantum yield is then in the neighbourhood of 2. An example of this

is the decomposition of nitrogen peroxide N0 2 into nitric oxide NO and
oxygen by the action of ultra-violet light (260 to 360 mtt), as follows:
2N02 + hv-+ 2NO + 0 2
When ..\ = 400 mtt the yield p drops to ·75, and decreases to nil in the
visible spectrum.
(c) When the reaction is purely exothermic (with production of heat) the
quantum yield becomes very high. In this case it is only necessary for the
light to initiate the reaction for the latter to continue of its own accord by
means of its own self-produced heat, in a chain of reactions.
A classical example is the combination of chlorine with hydrogen (in the
presence of a trace of water vapour) under the influence of light. p may reach
up to 100,000 (it varies with the pressure in, and size of, the vessel), and a
whole range of similar combinations may be noted:
CO + Cl 2 = COC1 2 'hith p = 1000
Carbon Chlorine Phosgen e
monoxide
2CH4 + Cl 2 = 2CH 3 Cl +H 2 with p = 10,000

Methane Chlorine M ethyl H ydrogen
Chloride
as well as the combinations of chlorine with a number of organic substances,

such as alcohol, ether, acetic acid, benzene, toluene, etc. With the latter,
p = 30.
In order to take place, a photochemical reaction sometimes demands the

presence of a sensitizer, e.g., the action of hydrogen on benzene< 4 >and the
photochemical reactions of propane< 5 >are catalyzed by mercury. The photo-
decomposition of oxalic acid is sentiti:ted by uranyl ions. Here, a transfer of
electrons occurs, from the excited uranyl ions to the oxalate ions. Other reac-
tions are sensitized by zinc oxide.
The intensity of the light is sometimes an important factor to consider.
Thus a 10-kW electric discharge lasting from ·1 to 3 minutes will produce
different substances from those obtained with radiations of moderate inten-
sity. <6 >
11. Photochemical dissociation

The photochemical decomposition of a molecule is shown by its absorption spectrum.
A spectrum will thus consist of two adjacent parts, viz., a broken spectrum formed of
fine absorption lines which correspond with a vibration of the nuclei of the atoms
within the molecule; and a continuous spectrum whose absorption varies continuously.
The vibratory movements are such that the atoms oscillate around their point of
balance and escape as soon as the vibratory energy exceeds a certain value. The mole-
cule then dissociates.
Thus the spectrum of a substance displays, on the one side, some narrow bands of
absorption which, although clearly separated at first, finally unite in one continuous
spectrum. The region in which these two forms of spectrum separate is called the
limit of convergence. Now, the power to decompose substances is present only in radiations
which form part of a continuous spectrum; and if the temperature is increased, the bands
nearest to the continuous spectrum will merge with the latter, and the radiations
belonging to these bands, formerly inert, become active.
This effect, discovered by Victor Henri, is called 'predissociation'. Many examples
exist, e.g., photolysis of acetaldehyde (effective A< 315 mJL); of benzaldehyde (effec-
tive A < 250 mJL); of carbon disulphide CS 2 (two limits of convergence in ultra-
violet); of sulphur dioxide SO 2 (also two limits corresponding with two regions of
absorption); of nitrogen peroxide N0 2 (A < 400 mJL and A < 245), etc., etc.
The narrow bands of absorption correspond with a vibration of atoms or groups of
atoms which cancel out at the limit of convergence, in the case of active radiations.
The molecules are then in a state of predissociation or electronic excitation, without
any true dissociation, due to the absorption of photons.
12. Organic photochemical reactions
All known types of organic reaction may be subject to the influence of light,
and some of these are noted below :
Decomposition: Acetone, <7 >acetamide, <8 >methyl formate, <9 >mercaptans. <10 >
At 253 ·7 mfl a quantum will decompose 1·7 molecules of mercaptan. Roten-
one<11> is also susceptible to photochemical decomposition.
Hydrolysis: Carbon tetrachloride into hydrochloric acid and carbon di-
oxide; <12 >mono- and dichloracetic acids into glycolic and glyoxylic acids ; <13 >
cyclohexanone into caproic acid. <14 >
Oxidation: When under the influence of light, and in the presence of
oxygen, alcohols, phenols, ketones, aldehydes and acids will oxidize. Some of
the di- and triarylmethanes will convert to peroxides, and this effect is
particularly marked in the case of 9-phenylxanthane. <15 > Many catalyzed
photo-oxidations have been used in the preparation of organic compounds. <16 >
PHOTOCHEMISTRY 15
Addition reactions occur with halides, ammonia, aniline, etc., and in the
latter case anilides are obtained.
Isomerizations and polymerizations: o-nitrobenzaldehyde, when dissolved
in benzene or ether, will be converted to o-nitrosobenzoic acid. o-nitro-
benzylideneacetophenone forms indigo: <17 >
There may be changes of form, such as with dibenzoylethylene and di-

benzostyrol. Carvone is converted to carvocamphor.
Acetylene polymerizes into benzene<18 > (the same applies to its derivates).
Stilbene dimerizes into distilbene. Anthracene, phenylacetaldehyde, cinn-
amylidenemalonic acid, cx-naphtoquinone, etc. also produce dimers.
Methyl acrylate and methacrylate will polymerize in the presence of ben-
zoin or diacetyl, acting as catalysts. In this way it is possible to obtain reliefs
for printing purposes. <19 >
Under the influence of ultra-violet rays, on the other hand, many polymers
undergo a marked degree of depolymerization. It is thus possible to observe
a decrease in the viscosity of solutions of cellulose nitrate and acetate, <20l or
of methyl-cellulose. <20 > Any radiation of a .\ lower than 340 mfl will degrade
most fibres, while between 340 and 400 mfl the action must often be activated
by atmospheric humidity and oxygen, or by traces of metals.
13. Inorganic photochemical reactions

The allotropic modification of certain elements by the action of light are
commonplace operations in inorganic chemistry. White phosphorus will
change to red phosphorus, yellow arsenic to grey arsenic, yellow antimony to
black antimony, and red selenium to black selenium. The final product is
always the more stable. The hydrogen and sulphur derivates of all these
substances are also light sensitive. The photolysis of hydrazoic acid and of the
alkaline nitrides has also been studied. <22 J This is a chain reaction, the inter-
mediate substance being activated nitrogen.
Most of the metallic salts are photo-sensitive. Sulphides in suspension in
water may undergo a slow oxidation, while a blue colouring has been ob-
tained with ammonium molybdate or sodium tungstate+ HCl.
The point which distinguishes the behaviour of the salt substances from
that of the above-mentioned compounds is essentially their ionic character.
Whereas, in gaseous systems, molecules alone would come into play, here we
have only to consider the movement of the valency electrons, since the
metallic salts-crystallized or in aqueous solution-dissociate into ions.
Among the photochemical decompositions, the most noticeable are those
of the following elements-iron, chromium, manganese, cobalt, uranium,
copper, mercury, and especially silver. The reaction is often reversible.
Examples:
Ferric Ferrous Chlorine

Chloride Chloride
2AgCl ~ 2Ag + Cl 2
Silver Silver Chlorine
Chloride
If the chlorine is absorbed as and when it is formed, only the photolytic

reaction occurs (decomposition).
The sensitivity to light of iran salts has given rise to several applications
which we shall examine later, and the same applies to chromium salts.
In common with the ferric salts, the manganic (Mn+++) and cobaltic
(Co+++) salts revert, under the action of light, to the state of manganous
(Mn++) and cobaltous (Co++) salts, by each acquiring one valency electron.
Cuprous chloride CuCl assumes a violet-brown colouring, while cupric
chloride CuC1 2 , dissolved in alcohol, is reduced to cuprous chloride. Simi-
larly, salts of uranium, lead and thallium are sensitive to the action of light.
Among the salts of mercury, mercurous nitrate HgN0 3 , basic mercurous
tartrate, basic mercurous oxalate and especially mercury-ammonium oxalate,
display interesting reactions.
Eder' s reaction. A mixture of mercuric chloride HgC1 2 and ammonium
oxalate in an unsaturated solution will decompose rapidly into insoluble
mercurous chloride HgCI (calomel) which precipitates. This very sensitive
reaction may serve as a photometer. The action would be as follows:<23 >
C 2 0 4-+Hg++ ~ 2C0 2 +Hg+

Hg++C 20 4----+ Hg+C 2 0 4-
Hg+Hg++ ~ Hg 2++
Eder's reaction is sensitized by plane-molecule cyanines and erythrosine

This sensitizing appears to operate by means of a transfer of energy. <24 >
14. Phototropy
Certain organic substances, when subjected to the influence of light, will change colour
and, when placed in darkness again, will revert to their original colour. This is a
reversible change of colour which is called phototropy.
Phototropic compounds are relatively numerous. An exposure of 1 minute to a
50-watt lamp at a distance of 2 inches is generally sufficient for a change of colour to
take place, the phototropic substance being dissolved in water, alcohol or acetone, or
also in the crystalline state. Sometimes the new colour remains for several days, in
the dark, before disappearing, but in most cases the reversion to the original state is
rapid. We append a list below of a few of the many phototropic compounds:
Benzaldehyde-phenylhydrazone<25 >-colourless, becomes scarlet-as well as many
other phenylhydrazones. <31 >
Quinoquinoline hydrochloride< 2 •>-yellow crystals become green.
cx-Naphthylamino-camphor< 2 7 >-colourless (chloroform solution), becomes green.
Tetrabenzoylethylene< 2 8 >-colourless, becomes yellow.
Triphenylfulgide-yellow, becomes brown, and other fulgides are affected.< 2 •>
PHOTOCHEMISTRY 17
Diacetylamino-p-2-stilbene-o-2-sulphonic acid, a light yellow powder, becomes
red.< 30 >
Derivates of salicydene-amine: salicydene-o-anisidine, /1-naphthylamine-salicydene,
salicydene-aniline, m-phenylenediamine-disalicydene.
Naphthylosazones: anisyl-<X-naphthyl-osazone, piperyl-<X-naphthylosazone.
Acetanilide-p-disulphoxide.
Certain dyes.< 32 >
The phototropic fulgides, for instance, have a general constitution represented by
the following formula:
The carbazones, such as cinnamaldehyde-phenylsemicarbazone, when subjected

for several hours to diffused light, produce an invisible latent change which, after a
return to darkness followed by a second exposure to light, will give a visible yellow
colour. This is the effect called inverse phototropy.<••>
Phototropy is attributed to the reversible displacement of electrons, corresponding
with several mesomeric forms of a same substance. The coloured state is an inter-
mediate state resulting from the superimposition of several extreme structures. One
of the mesomeric forms may predominate, as in substances which are already coloured
(/1-tetrachloro-<X-cetonaphthalene, fulgides, Schiff's bases). This is an electrotropic
effect.< 34 >
A particular case of phototropy on plates has been observed by J. Sivadjian<••> in
the following manner:
Photographic plates, after being fogged, developed, fixed, washed, bleached in a
1% solution of mercuric chloride, then rinsed, are sensitized in ·5% potassium iodide.
Yellow layers of mercury iodide are obtained. After rinsing and drying, the plates are
exposed to light and the coating assumes a purplish-black tone, but becomes colourless
again in darkness. This process is accelerated by washing. It can provide images
suitable for copying.
Cupric bromide and cupric chloride, when damped with water, become dark green.
They decolourise in darkness-in a few hours at an ordinary temperature, and
instantly at 75 °C.<•••> This change is accelerated by the Be and Cl- ions.
Phototropy of 4-(p-dimethylamine-benzene-azo )-phenylmercuric acetate: see Jl. Am.
Chem. Soc., 1955, 77, ·p . 5011.
15. Fluorescence and phosphorescence

A fluorescent substance, when subjected to the action of radiation of a certain
wavelength (ultra-violet, for instance) will convert these incident rays into
other emitted and visible radiations of a greater wavelength.
This is because the molecule M, having absorbed a quantum hv, passes
through an unstable activated state M', then deactivates when reverting to its
stable condition, while emitting a quantum hv' of a lower frequency. This
lowering of the frequency is explained by the fact that activated molecules
are in continuous rotation. Deactivation stops the movement of the molecule,
then causes the expulsion of a photon with less energy than that of the
absorbed photon.
The length of time between activation and deactivation varies from one
hundred-millionth to a thousandth of a second (uranyl salts) according to the
nature of the substance. The yield varies also: the ratio between emitted and
absorbed photons comes near to unity for diluted fluorescein . The light
emitted by a fluorescent body may be compared, according to J. Perrin, with
a 'discontinuous sum of minute identical sparks'.
2. In the effect of phosphorescence, the irradiated substance retains its
luminosity for a comparatively long time (often for several hours). This
property is due to the presence of what are known as phosphorogenic sub-
stances, particularly sulphides. The presence of impurities such as copper,
manganese, calcium, rare earths, etc. is essential to maintain the instability of
the crystalline structures thus deformed.
A molecule, activated by an absorbed photon, will produce an unstable
molecule when deactivated at a slightly lower level. This molecule, by reason
of thermal agitation, will receive a little energy, which will enable it to revert
to the activated state by returning to its original level of activation. The same
cycle is repeated until the gap between the level of activation and that to
which it drops becomes too wide to be closed.
1. Emschwiller: L'Action Chimique de la Lumiere: la Photolyse. (Centre de Docu-

mentation Chimique, Paris.)
2. Henri Victor: L es Progres Recents de la Photochirnie, p.3 . (Centre de Documen-
tation Chimique, Paris.)
3. Henri Victor: Zoe. cit., p. 2.
4. Forbes G . S. and Cline J. E.: Jl. Amer. Chern. Soc., 1941, 1713-1716.
5. Darwent B. de B. and Steacie E. W. R.: Jl. Chern. Physics, 1942, 563-571.
6. Norrish R. G . W.: Zeits. Elektrochem., 1952, 705-712.
7. Jl . Amer. Chern. Soc., 1944, 974-977 and 1940, 2052-2069.
8. Jl. Arner. Chern. Soc., 1941, 2000-2002.
9. Jl. Arner. Chern. Soc., 1941, 1521-1525.
10. Trans. Faraday Soc., 1942, 81-82.
11. Jl. Arner. Chern. Soc ., 1941, 1717-1918.
12. Liebig Ann., 1911, 382, 222.
13. Z eits. f. phys. Chern., 1913, 371.
14. Ber., 46, 3077.
15. Schonberg A. and Mustafa A.: Jl. Chern. Soc., 1945, 657-660.
16. Schenck G. 0.: Angew. Chernie, 1952, 12-13.
17. Engler and Dorant: Ber., 1895,28,2497.
18. Dunicz B. L.: Jl. Arner. Chern. Soc., 1941, 2461-72.
19. Lawton T. S. and Nason R.N.: Ind. Eng. Chern ., 1944, 1128-30.
20. Spitze, Mooradian, Hartegan and Hansen: Jl. Amer. Chern. Soc., 1941,1576-80
21. Gates and I. C. I.: B.P. 566, 795 (1943).
22. Bonnemay M.: Jl. Chim. Phys., April 1944, 56-81.
23. Cartledge: Jl. Arner. Chern. Soc., 1941, 906-12.
24. Kornfeld G.: Sc. Ind. Phot., 1952, 378.
25 . Biltz: Liebig Annalen, 1899, 303, 170.
26. Marckwald: Zeits. Phys. Chern., 1898, 30, 143 .
27. Singh:Jl. Ind. Chern. Soc., 1924,1, 45.
28. Halban and Geisel: Zeits. Phys. Chern., 1920, 96, 233.
29. Stobbe: Liebig Annalen, 1907,359, 1.
PHOTOCHEMISTRY 19
30. Stobbe and Malisson: Ber., 1913, 46, 1227.
31. See various numbers of Atti Academia Lincei (1925-1935).
32. Stearns: Jl. Opt. Soc. Amer., 1947, 32, 282.
33. Heilbron, Hudson and Huish: Jl. Chem. Soc., 1923, 123, 2273.
34. Gheorgiu C. V.: Bull. Ec. Polyt. Jassy, June 1947, 141.
35. Sivadjian J.: Comptes R endus Ac. Sc. Paris, 1949, 1296-97 and 1951, p.1956-58.
35a. Hecht H. and Muller G.: Zeits. Phys. Chem., 1954, 202, 403--423.
Chapter III
THEORY OF THE LATENT IMAGE

In order to obtain a photographic image, it is necessary to expose a sensitive
emulsion<I> to light. Inside this 'emulsion' a change occurs, invisible yet fac-
tual, which bears the name of latent image. It is given this name because a
visible image is obtained from it when a substance known as a developer is
caused to act upon the latent image, in the operation of development. The
sensitive medium on a photographic plate is a heterogeneous mixture formed
of a dispersion of very fine crystals of silver bromide AgBr in gelatin. It may
contain a certain proportion of silver iodide.
16. The silver bromide crystal

Silver bromide cyrstallizes in a cubic pattern, like the halides of alkaline
metals (NaCl, KBr, etc.). <2 >
The cubic system, which is the simplest form of the seven systems of
crystallization, is characterized by three axes of symmetry which are all per-
pendicular to one another. The arrangement of the atoms, called the pattern
or cry~tallattice, takes place on the upper surfaces of the cubes. The outer
appearance of the crystal may vary, according to the nature of the substance
and the way in which it was obtained, by a truncation of the angles (dihedral
angles) or of the summits (trihedral angles). Thus the silver bromide appears
in the form of hexagonal or triangular tablets (Fig. 2) and cubes or short
needles with rounded ends. The former are obtained by precipitation in a
neutral medium, and the latter in an ammoniacal medium.
FrG. 3. Crystal lattice of silver hal-

lides. The silver ions ( •) and halides
(o) alternate on the top of the cubes.
The effect is shown here in diagram,
FIG. 2. Silver bromide crystals whereas in reality the ion spheres are
(neutral emulsion). closer.
20
The crystal lattice constitutes the true structure of the cr tal. It is formed
by an assembly of ions situated at equal distances in the three directions,
following a regular pattern. The entire assembly resembles a pile of cannon-
balls.
The Ag+ and Br- (or Cl-) ions are situated alternately at the intersection of
the lines of a cubic lattice according to the diagram in Fig. 3. The lattice is
'face-centred', since each silver ion is connected with six halide ions, and
vice versa. The distance between the centres of two identical atoms, or mesh,
is 5·774 A for AgBr, and 5·55 A for AgCl. The halide ions are larger than
the silver ions. (2a)
The crystals of photographic emulsions correspond mostly with cross-
sections made along the octahedral sides, i.e., at right angles to the diagonals
of the cube.
As for silver iodide, in the cold state it has a hexagonal shape, of the ZnO
type. However, Oshino and Miyaka noted that silver iodide may have crystals
of two shapes according to temperature, <3 > especially a cubic rx shape, of the
blende ZnS type, which is stable up to 137°C, and hexagonal f3 shape, of the
wurtzite type, stable from 137° to 146°C. Using a pressure of 3,500 Kg,
Jacobson obtained inward faced cubes.
The study of crystals. When studying the photochemical effects which take
place inside the silver halides, it is possible to use either large crystals or
strips cut out of fused halide. In the latter case, the strips (obtained by saw-
ing) must be heated above melting-point for forty-eight hours, then allowed
to cool slowly for twelve hours. <4 > The best procedure is to work in an
atmosphere of pure nitrogen. <5 > It is also possible to prepare strips of 10-4 or
10-3 centimetres thickness by crushing fused salt between two strips of
quartz. <6 > Another method consists in sublimating some silver on a sheet of
glass and to expose it afterwards to bromine or chlorine vapour. Considering,
however, that the igneous fusion produces crystalline structures which differ
from those produced at an ordinary temperature, Tamura and Tukihosi
obtain polycrystalline layers by precipitation on a sintered glass partition
separating the two reagent solutions of 0·5N silver nitrate and potassium
bromide. <7 >
Mixed crystals. The various silver halides will crystallize readily together.
Mixed crystals are produced by fusion as well as by precipitation, and the size
of the mesh is, of course, related to their composition. The variations in struc-
ture may be revealed by X-ray diffraction, by examining the reflection spectra
and by measuring the birefringence and the specific gravity. (?a) Silver
bromide and chloride produce mixed crystals in all proportions, but an intro-
duction of silver iodide causes a disturbance of the crystalline structure. With
any quantity up to 4 % of Agl, in relation to AgBr, and 11 ·5% in relation to
AgCl, it is possible to obtain inward-faced cubic crystals. (This is the most
usual case in practice.) With a very high content of silver iodide, mixed
crystals belong to the hexagonal group, while with medium contents there is
a mixture of both types of crystal. Silver iodide produces local deformations
(since the ions r- are larger), and moves the absorption spectrum towards
22. PHOTOGRAPHIC CHEMISTRY
the longer wavelengths. This displacement relates to the presence of cubic,

and not hexagonal, Agl. (The limit of absorption of the latter is, on the con-
trary, of a,\ lower than that of silver bromide.)
17. Adsorptions on the surface of crystals

The crystals of silver bromide or chloride emulsions are prepared by
precipitatiol(_Jp the presence of a protective colloid-i.e., gelatin-and an
excess of ala!fli halide. The latter is solvent of silver salts and forms several
complex negative ions such as (Br 2 Ag)-, (Br 3 Ag)--, etc., adsorbed on the
surface of the cry,:tals, particularly on the surface defects.
Enlarging upon Helmoltz's conceptions of the double layers of parallel ions
and of opposite symbols, and also on Gouy's, which considered the outer
layer as a diffused ionic atmosphere, Stern showed< 8 >that there are indeed
two successive layers, but that the inside layer is attached rigidly to the
crystal, while the outer is diffused. The crystal of silver bromide has thus
two inter-faces, <9 >i.e., crystal to adhesive layer, and adhesive layer to diffused
layer.
According to Bourne and Loening, <10 >the OH ions are also adsorbed by the
silver salt precipitate. This adsorption increases with the pH, and at pH 9·5
there would be an OH group for five ion sites on the surface.
Finally, gelatin should not be forgotten. Its ions are charged negatively,
and it is readily adsorbed. The gelatin covering which encloses the crystal
may be seen under an electron microscope, <n> and photolysis under the action
of electrons shows a transparent covering containing the liberated silver and
possibly formed by a silver-gelatin complex.
Strictly speaking, apart from unproved and hazardous suppositions, we do
not know the exact, yet extremely important, mechanism by means of which
gelatin contributes to the formation of the latent image.
18. Absorption spectra and photoconductivity

The spectral regions of photographic sensitivity belonging to the silver halide
crystals correspond with their absorption bands. Now, the absorption spectrum
of a crystal depends on the nature of its constituent parts and consequently
on the d~formations of the electronic orbits occasioned by the mutual reactions
of the adjacent elements. The deformations are the more pronounced as the
atoms are the larger; thus the halides of alkaline metals-which are lighter-
have two absorption bands in the ultra-violet, while the silver halides have
their bands in the near ultra-violet, violet and blue. The limits of these bands,
moreover, are the less abrupt as their wavelengths are the higher. One of De
Boer's formulae< 12 >enables the frequency of these main absorption bands to
be calculated.
The movement of the electrons within the halide crystals is evidenced by
means of photoconductivity, and the latter is specific for a given spectral
absorption band.
In any photo-sensitive crystal a potential difference occurs when it is sub-
jected to unilateral lighting. The process has been studied on cuprous oxide
by Dember, <13 > then on silver halides, particularly by Kotlyarewski. <14 > An
electrode (formed by the sublimation of silver on the crystal), which is illumin-
ated by a light of given .\, will assume a positive charge (normal effect) or
negative charge (reverse effect~. On silver chloride the effect is normal at
room temperature with its maximum at 340 mf.-t. The reverse occurs on silver
bromide with its maximum at 320 mfl. At - ·18°, the effect is seven times more
pronounced. On strips of 1 to 10 fl thickness, Barschevski <15 > obtained the
following maximum effects :
AgBr-313 mft
AgCl-365 mfl
Agl-365 and 420 mfl
On AgBr which has already been exposed to light the maximum reaches
575 mft.
The photoconductivity of silver bromide is considerably accentuated by
the addition of cadmium or lead bromide.
Photoconductivity in emulsions. West and Carro!l! 16 l have measured photoconduc-
tivity, not, in this case, within isolated crystals, but directly within t he photographic
emulsion. A piece of film was placed between two electrodes subjected to a difference
of potential. Under the influence of light, the resistance of the system decreases and
the current in the circuit increases. The incident luminous energy is measured by
means of a thermopile. Miller and Hamm< 17 l made a similar study by using an electro-
m eter and an oscilloscope. They observed that the current continues to increase after
exposure to light has ceased, the maximum being reached two seconds later. This
effect may be due to an electrolytic current resulting from a re-arrangement of the
ions in the double layer enclosing every crystal, in the vicinity of the specks of the
latent image.
19. Alkali halides

The alkali halides (sodium chloride, potassium bromide, etc.) are sensitive to light.
This can be explained by the fact that the photo-sensitive element is not a metal ion but
a halide ion.
The crystals of alkaline halides become coloured when exposed to ultra-violet,
X- and y-rays; likewise when exposed to electrons, and when heated in metal vapour.
When exposed to light, these crystals show several absorption bands (in addition to
the main ones) which result from defects in the crystal lattice, particularly the follow-
ing: <' ")
(a) F band, resulting from defects in the lattice, with an excess of metal ions.
(b) M band, resulting from a surplus of electrons.
(c) V band, resulting from positive holes (absence of halogen).
(d) Various bands resulting from impurities.
The F and M bands will form readily by exposure to X-rays (about 10 8 rontgen
per sq. em.). After a further exposure-to light, in this case-additional bands; called
R bands, are formed, as well as infra-red N bands situated beyond the M band.<' 9 l
An excess of metal ions in an unusual position will form F centres, and the radiations
absorbed in this band will discolour the crystal, although only partially. Some of the
F centres will return to an F ' state, of which the corresponding absorption band is
weaker and of longer wavelength.< 20 l
The alkali halides may be sensitized by the corresponding hydride. When coloured
by X-rays, the alkali halides emit an ultra-violet and visible fluorescence, and the
effect is intensified when the temperature of the crystal is increased from that of liquid
air to that of ordinary air.( 21 l A blue fluorescence may be obtained by exposing mineral
salt to X-rays, in liquid nitrogen; and by a slow heating process an ultra-violet
phosphorescence will be produced.( 22 )
Potassium chloride, crushed with 2·28 % of silver chloride, becomes phosphor-
escent (12 seconds). (23 l If it contains metallic thallium it is photoelectric, with a
maximum at 550 mfL.( 23 b)
20. Defects of the crystal lattice

The photochemical sensitivity of a crystal of silver bromide (and generally of
any photosensitive crystal) depends on the imperfection of the crystal lattice.
Lohle, Stasiw and Teltow, and Pohl have shown that light has no effect upon
a perfect crystal.
But before looking for local imperfections, it must be pointed out that the
crystal lattice shows a certain structural deformation. In the ionic crystals it is,
as we have seen, the ions and not the atoms which are the constituent units.
Thus silver appears with one electron less, i.e., in the state of an ion Ag+,
and bromine in the state of an ion Br-, having appropriated the ion lost by
the silver atom. The nuclei of the atoms are surrounded by their clouds of
electrons, which revolve in their respective orbits.
It so happens that a closer grouping of the nuclei will produce, by reciprocal
action, a deformation of the electron orbits. This deformation depends on the
nature, hence on the size, of the elements present. It is more pronounced in
the silver halides than in the alkaline halides, whose ionic feature is more per-
fect. The deformed ions produce crystalline structures of weak coordination.
Since it is the halide ion which is attacked by the photon, it will become more
sensitive as its electronic orbits are more deformed, and for this reason,
silver-which produces a greater degree of deformation than alkali metals-
will produce salts which are more photo-sensitive than those produced by
alkali halides.
Let us now examine the local defects. A crystal may be considered as an
imperfect grouping of more perfect polyhedric blocks. The joins form areas
of dislocation which are sometimes in a spiral, with cracked meshes, holes,
and badly fitting ions. This dislocation is assisted by the gelatin, which exerts
a considerable amount of physical tension (as revealed by examination under
a polarizing microscope). Also, an addition of iodide to th"e bromide will
increase the mesh in an irregular manner, with a confusion of the ions. The
same result could be obtained by adding thallium salts. The resulting internal
tension assists the movement of the electrons and ions, as in such phenomena
as phosphorescence, in which impurities play a similar part.
The diffraction patterns of silver chloride, in fused crystalline blocks,
show diffused patches and streaks attributed to a displacement of the rows
of atoms parallel to the axis of the elementary mesh. The process of irradia-
tion will cause photolytic silver to collect at the defective points of the
lattice. <24 >
The degree of perfection of a crystal is measured by a comparison between
its true density and its theoretical density, calculated from the mass and
volume of matter (Straumanis, Phys. Rev., 1953, t.92, p. 1155). Its mesh is
measured by X-ray diffraction. Corrections are carried out by Nelson and
Riley's extrapolation technique, and Wilson's for X-ray refraction. <26 >
Two kinds of defects are usually present together in crystals of silver brom-
ide and chloride, i.e., Frenkel and Schottky defects.
Frenkel defects. These are formed by interstitial Ag+ ions and an equal
number of locations devoid of cations (Ag0 ). The anion network remains
intact. The study of the effects of conductivity reveals that an abrupt increase
in the specific heat of the crystal of AgBr conduces to the formation of these
defects. <25 > The number of interstitial Ag+ ions increases with the tempera-
ture.
Schottky defect~. Schottky's defects consist of shallow vacant sites of Br-
and Ag+ ions, in equal quantity. The equality of the vacant sites is confirmed
by studies with radioactive ions carried out by Kolthoff and O'Brien, <26 >
followed by Langer. <27 > The existence of Schottky's defects has been verified
by taking measurements of the expansion of crystals (H. Kanzaki). <25 >
The defects in the network of a crystal of AgBr are called traps. Berg even
accepts the existence of shallow secondary traps which act as an intermediate
image, the electrons captured by these traps being reduced by thermal
agitation and the silver ions dispersed. In addition, Seitz calculated that the
number of defective atoms in relation to the number of normal atoms is
r = e-•kT, in which E = 0·36 electron-volt.
21. Sensitivity specks
The physical defects in the crystal lattice form during the first phase in the
preparation of a photographic emulsion (precipitation and physical ripening).
But in the second phase, digestion or chemical ripening-they can bring
about the production of sensitivity specks. These specks are on the surface,
and they occur especially along the lines of dislocation.
The existence of sensitivity specks was suspected in 1897 by Abbeg, but it
was not until 1921 that their presence was demonstrated by Svedberg and
Anderson. <28 > Their size is, of course, too small to initiate development.
Each grain has its own distribution of centres, and it is on this assumption
that Webb based his calculations on the probabilities of distribution of the
centres within an emulsion. This is in opposition to Silberstein and Trivelli,
who assumed in their calculations that same-sized grains have the same
sensitivity. <30)
The question now arises as to the composition of the sensitivity specks. They
may be formed either by silver<31 > derived from a reduction process, or by
silver sulphide originating from the sulphur introduced by the gelatin. Mitchell
and Meiklyar, on the other hand, have accepted the fact that chemical
ripening produces stable aggregates of a few shallow F centres. F centres,
whose existence has been proved by Anastasevitch and Frenkel, <32 > are
formed by the appropriation of electrons by sites devoid of halides, while
thermal diffusion will produce large aggregates of from 3 to 10 F centres,
which form sensitivity specks.
At all events, it is extremely difficult to study crystals free from any im-
purity, for one always finds traces of Ag 2 0, Zn, Cu, AI, Fe, Si, etc.
But let us return to the sulphide sensitivity specks. To them is rightly attri-
buted the largest part in the sensitivity of a photographic emulsion. How do
they operate? The X-ray diffraction patterns of silver bromide crystals con-
taining Ag 2 S produce wider lines than with pure silver bromide, which
indicates a deformation of the crystallites. <33 > The bivalent ions--, confronted
by the vacant bromide ion site Br ~ changes to a monovalent sulphur ion by
losing an electron and forming an F centre (as the electron occupies the
positive hole):
s- -+ Br ~--+ s- a+F
It has been possible, thanks to the researches of Stasiw and Teltow<34 > on
the formation of absorption bands in fused crystals of combined AgBr and
Ag 2 S, to identify some complexes, the main type of which is
[S- G Br+]
0
formed by the coupling of a monovalent interstitial ion of sulphide S- with
a vacant bromide site.
The chemical sensitivity specks will act only at low intensities. Berg has
estimated that it is possible to have up to 10 molecules of silver sulphide for
every centre. <35 >
22. Process of latent image formation according to the Gurney-

Mott theory
The relation between the movement of electrons released by light, and the
formation of the latent image, has been prompted by the effects of photo-
conductivity in crystals of silver halides-effects which were made known by
Arrhenius (1887). This induced Dauvillier (in 1920), then Fajans and von
Beckeroth, and also Sheppard and Trivelli, to present the first hypotheses on
the process of the formation of the latent image. <36 > But it was not until 1938
that Gurney and Mott<37 > were able to produce a consistent theory, which has
since become standard.
According to Gurney and Mott, the latent image forms in three phases:
(a) Primary photochemical effect. A quantum of luminous energy hv (or
photon), penetrating into a silver bromide crystal, reacts-at the outer
energizing level-upon a bromide ion Br-, simultaneously yielding its energy
to the latter. This energy enables the bromide ion to expel its supplementary
electron in order to revert to the state of free bromine Br (with seven sur-
rounding electrons, instead of eight for the Br- ion). The reaction may be
written thus (e signifying one electron):
Since the decomposition of silver bromide is a reversible effect, it is neces-

sary-in order to prevent the bromine from re-combining-to fix the latter.
This fixing of a halide is effected by water and, with better effect, by the
gelatin which acts as a binder for the crystals. Gelatin is a bromine
acceptor.
(b) Electronic current. The electron expelled by the bromide ion is, at the
outset, at a higher energy level than that of the surrounding orbit of the
(missing) valency electron of the corresponding silver ion Ag+ (since the
valency electron of silver is at 0 level, while that of bromine is at N level, of
lower degree and therefore of higher energy).
The electron, then, will jump to 0 level. But in the assembly of Ag+ ions
formed by the crystal, the many 0 levels of these ions, being empty, form a
wide band in which the electron can travel freely before dropping to a slightly
lower level. <38 > This conductivity band 0 corresponds with the F absorption
band.
In fact, the second phase in the formation of a latent image resolves itself
in the migration of electrons through a crystal lattice. This migration is
facilitated when the ions adjacent to this lattice do not display any reciprocally
abrupt potential differences, since the atoms are very close together; this in
opposition to the effect produced in purely ionic crystalline structures, such
as those of potassium bromide or sodium chloride, in which the potentials
are more marked.
What becomes of the electrons in motion? They eventually meet, encounter
a luwer energy level, than that which they are in, and are trapped by it.
Now, this lower energy level is a sensitivity speck (Ag+Ag 2S). The elec-
trons will accumulate in this centre and, naturally, form negative electric
fields .
(c) Ionic current Ag+. This is the third and last phase of the latent image
speck formation.
The electric field-increasing in size through the arrival of new electrons-
attracts the (positive) silver ions Ag+, and this migration of Ag+ ions consti-
tutes an ionic current, which, in fact, can be studied, as done by Tubandt, by
external application of artificial electric fields.
But the ions do not travel as fast as the electrons, and do not always succeed
in discharging the negative field soon enough, in which case the latter may
oppose the arrival of new electrons. The formation of the image is thus
retarded.
The ions Ag+, in turn, capture the electrons assembled around the sensi-
tivity centres, by giving out atoms of metallic silver fixed on the same centres,
i.e., Ag++ e = Ag. They then constitute'-when in sufficient number---the
latent image centres. These specks are separated from one another and are
each formed by a certain number of silver atoms.
The Ag+ ions, attracted by the field created by the assembled electrons,
are detached under the influence of thermal agitation, more readily as they are
less firmly attached. Those which depart first are the ones which are situated
on the irregularities of the lattice (distorted parts or breaks). This is why we
have previously insisted upon the necessity for having crystals of AgBr as
imperfect as possible, especially if the photographic emulsion is to be fast.
23. Positive holes

Atoms of bromine are formed from the loss of photoelectrons by the Br-
ions. These bromine atoms have no action upon the latent image at low inten-
sities. But an electron may attach itself to a bromine atom, to produce a Br-
ion, which enables another bromine atom to undergo the same reaction, and
so forth, in the manner of a cascade. Everything occurs as if the Br moved
irregularly through the lattice, as far as the interface, where it combines
slowly with the gelatin. It is possible, in conformity with de Boer's hypo-
thesis, to liken the bromine atoms to a mobile 'positive hole'. The same pro-
cess is to be found again in other crystalline systems studied by Wagner, such
as NiO and Cu 2 0. The mobility of the Br- ions is very low, a fact which
Zimens observed after having exchanged Br for the radioactive bromine 82
and comparing its speed with that of radioactive silver 106, whose mobility
is high.
When a halogen acceptor is added to the emulsion, the photoconductivity .
is doubled. To do this West used ,8-naphthyl semicarbazide hydrochloride or
the ,8-naphthothiazole sernicarbazone. (3 9 )
24. Mitchell's theory
As stated above, the crystal lattice contains some Frenkel defects (inter-
stitial Ag+ ions) as well as some Schottky defects (vacant sites of bromine
and silver ions). The vacant sites of anions form positive holes Br ~ ,
which should not be mistaken for bromine atoms.
The electrons which are produced in the course of the primary photo-
chemical phase are, according to Mitchell's original theory< 40 > captured by
these mobile vacant sites of bromine ions Br ~ , and produce F centres.
Anastasevitch and Frenkel <41 > had already stressed the function of these
centres formed by an electron in a positive hole. F centres exist also in the
alkali halides, where they result in coloured centres characterized by the
corresponding absorption band.
An F centre may also be considered as an electron surrounded by six
potential silver atoms. Several F centres will unite in aggregates, which are
comparatively stable when formed in the neighbourhood of a sensitivity
speck such as an ion s-G · But when these F aggregates reach a critical size
they produce-with their surrounding silver ions-metallic silver, which is a
constituent of the latent image.
It will thus be seen that, in this theory, there is no migration of ions Ag+,
but a redistribution of the metallic silver, after exposure, by reason of the move-
ment of the F centres. In addition, a photon, instead of acting upon a Br-ion
can act upon an existing F centre. The latter will release its electron, which
is captured by other F centres, and the association F +e can in turn attract
interstitial ions. No release of bromine is required, as in the orthodox theory.
i\1itchell's second theory. Mitchell later< 41 a) revized his conception of the
formation of the latent image, which may be summarized as follows:
(a) Liberation of electrons with a simultaneous formation of an equal
number of positive holes by the photons. Or action of the excitation waves
upon the Br- ions occupying the indentures and other imperfections of the
crystal; since these superficial Br- ions surrounded by only a small number
of Ag+ ions, are at a lower potential, which always requires less energy to
eject the electrons.
(b) If there are positive holes, these are appropriated first by the ions Be
occupying the indentures, with a formation of rapidly-absorbed bromine
atoms. In addition to the binder, the chemical sensitizer acts as an acceptor of
halide.
(c) The electrons set free are raised to the energy level of the conduction
band (or to levels lower than the locations of sensitivity specks with a lower
potential). The electrons are appropriated by sensitivity specks together with
the surface Ag+ ions situated at the defective parts of the crystal, or emanating
from the surroundings of the missing bromine ions, and give rise to isolated
and mobile silver atoms.
(d) Formation of latent sub-image consisting of dispersed pairs of silver
atoms, less mobile than the isolated atoms, by a concentration of the latter
at the sensitivity specks.
(e) Formation of a stable latent image consisting of the specks of at least
four silver atoms, by a grouping of the pairs of the neutral silver atoms of the
sub-image, in positively charged aggregates-a charge which is balanced by
the superficial Br- ions. The stable specks are more active for the catalysis of
development than the unstable specks.
The latent image is produced in the regions of tension where the sensitizers
are located, mostly in the centre of the crystal, in the case of hexagonal tablets
prepared in a neutral medium; also at the junctions of the elementary crystals
which constitute the structure of the cubes, when the precipitation of the
silver bromide is effected in an ammoniacal medium.
25. Stasiw and Teltow's theory

We saw in para. 21 that a sulphide ions- G joins with a vacant Br0 site to
form a complex [S- G Br[j]. The sign G indicates here an interstitial posi-
tion, and the sign O a vacancy.
Now, the above complex is a trap. It is capable of capturing a photoelectron
to give a negative-charged unstable complex,
which, in turn, can attract an interstitial silver Ag0+ ion and become<42l:
neutral Ag0+[S- G Br0 ]
possessing an absorption band at 560 m,u. This complex is very mobile. It

may assemble in aggregates which, in turn, may disperse to produce free
colloidal silver (several thousand atoms).
In the process proposed by Stasiw, the specks of atomic silver are thus
formed in the immediate vicinity of a sensitivity speck, itself resulting from a
sulphide ion and the neighbouring vacant site of a bromide ion. At low
temperatures, it is even possible to observe the following primary effect:
[Ag0 + S-aJ + hv--+ [Ag+ Sa] +r
[Ag0+ Sa] --+ Ag+ + Sa
the subsequent reaction occurring as described above.
A more recent study by Seifert and Stasiw< 42•l showed that the complex
[S-a Ag0 +] absorbs at 436 mfl. On the other hand, the centres formed by the
electrons appropriated by the vacant bromine ions sites absorb radiations of
480 to 490 mfl, but the complex [S- G Br ~ ] shows an absorption band at 630
mfl. By an appropriation of electrons, it forms a line at 720 m,u, correspond-
ing with the larger aggregates. In silver chloride, the mobility of the inter-
stitial silver ions is greater than in silver bromide, but the low concentration of
these ions will only allow a lower degree of conductivity.
26. Constitution of the latent image

It was formerly believed that, under the influence of light, bromide would
convert to a silver sub-bromide Ag 2Br or Ag 3Br, alone reducible by the
developer. Some authors even claimed to have succeeded in chemically
preparing these sub-bromides and sub-chlorides in an isolated state. Nowa-
days, the existence of these compounds is refuted, since they are merely a
mixture of a normal silver salt and colloidal ~ilver.
What, then, constitutes the latent image? Solely metallic silver. This can
be proved by a study of the patterns produced by an electron beam acting
upon a coating of ~ilver bromide. The pattern of the latter will soon be con-
verted to the pattern of free silver. <43 l
The appropriation of Ag+ ions takes place in the [110] orientation of the
irregular features of the lattice. C43al
The average proportion of metallic silver forming the latent image is about
1 atom for 10 million silver bromide molecules.
The formation of a latent image in a crystal produces a modification of the
absorption spectrum of the latter. Whereas the normal absorption band,
covering ultra-violet, stops at about 400 mfl, a second band appears in the
visible portion and the infra-red, with its maximum at 690 mfl. Hilsch and
Pohl, <4 4 l who carried out these experiments, used the letter F for this charac-
teristic band. It corresponds with the upper energizing level of the silver
ions in the crystal lattice.
The latent image has a discontinuous structure, being formed of points scattered
in the emulsion coating. As a result, the density of the image is governed by the
number of spechs distributed on the grains which can be developed completely.
The number of these grains will therefore increase with the amount of light.
By computing the number of latent image specks produced by a given
number of quanta (or photons), then taking a microscopic count of the actual
number of these specks which has been produced, it is found that the quan-
tum yield (or ratio of the number of released silver atoms to that of the
quanta absorbed) approaches 1. With gelatino-bromide it is 0·92 to 0·96.
The quantum yield of photolysis in vacuum is shown by the formula
cf> = Q(1 - e-ka) in which Q is the superficial efficiency, k the coefficient of
absorption, and a a parameter equal to 0·5 1-l for AgBr and 0·24 1-l for AgCl,
at an average t (see Luckey, G. W., Jl. Chern. Physics, May 1955, pp. 882-
890).
The grain becomes developable when a critical condition is achieved. Little
information is available on the nature of this critical condition:<45 > it may
depend on the size of the silver grain, its structure, or the properties of its
interface with the halide.
Sub-specks. According to Burton,<••> the latent image utilizes the specks which can
be developed, but there also exists some incomplete specks< 47 >which form a sub-latent
image. These grains, whose specks have not yet reached an optimum size, may respond
to development in the course of a second and very low intensity exposure. The larger
of the incomplete specks tend to increase in size, while the smaller ones shrink.
When a latent image is kept in darkness, the sub-specks increase in size, the elec-
trons necessary for this growth being supplied by thermal agitation. This is the basis
for the intensification of a latent image by time.
In Webb's opinion<••>the sub-image centres are formed of two silver atoms, while
the normal centres contain eight. They do not occur in any great numbers except at
high luminous intensities, since they form in a shorter time than that required for
exposure. On the other hand, development is slower when the exposure is at high
intensity (Cabannes-Hoftmann effect).
Huggins's hypothesis. Huggins<••> propounded a hypothesis according to which the
latent image is constituted, not by silver, but by silver bromide which has changed
from its normal B1 structure (of the sodium chloride type) to B3 (of the zinc sulphide
type) (Jl. Chern. Phys., 1943, 412). The B3 structure, stabilized by photoelectrons and
possibly also by Ag+ ions, is the structure of silver iodide. It would contain positive
and negative potential holes, and the former would be possible positions for photo-
electrons.
Junghanns and Staude, who tested this hypothesis by determining the specific
masses of the crystals before and after irradiation, did not observe any expansion.< 50 >
27. Internal latent image

The suggestion of an internal latent image, touched upon by Kogelmann in
1894, was not considered seriously until1931 by Luppo-Cramer. Belliot, in
admitting its existence, made a distinction between the surface latent image-
which can be eliminated with a solution of chromic acid- and the internal
latent image, inside the crystal, which is not attacked by oxidizing agents.
Various authors have even separated a 'sub-surface' image, thicker than the
surface layer, and soluble in a more concentrated solution of chromic acid.
Thus, starting from the outside, the following will appear:
surface specks;
intermediate specks (at ten reticular distances);
deep specks (clearly separated).
The internal image which, according to Hautot and Falla, is sensitive to
yellow and red, is formed at high intensities when electrons are produced in
great numbers. As the latent image grows, so the electron levels become
deeper. In order to produce deep specks it is necessary for the exposure to
be 1,000 to 100,000 times longer (according to the emulsions) than the time
required to obtain surface specks. The internal latent image forms after the•
external image. The opposite occurs in the case of X-rays, <51 l and the process
is examined by using the radioactive tracer method. <52 l .
The internal latent image is of the same constitution as the external image.
When over-exposure occurs, that part of the image which constitutes the
over-exposure will move to the surface in colloidal form. The internal image
is the cause of the second solarization maximum. The reciprocity failure at
high intensities is smaller, and vice versa.
In Hautot's view< 53 l the formatory mechanism of the internal latent image
is identical with that of Gurney and Mott, while the forrnatory mechanism of
the external latent image follows the pattern outlined by Mitchell. The
· aptitude of an emulsion to produce an internal image depends on the degree
of physical ripening.
Methods of treatment. The intermediate (sub-surface) specks will resist a
0·2% solution of chromic acid for about 2l minutes, while the deep specks
are resistant to 5 % chromic acid for 3 mins. It is thus possible to dissolve the
surface specks without touching the others. It is also possible to eliminat~
the external latent image by means of ammonium persulphate.
In order to develop the surface image alone, use a ferrous oxalate or glycin
developer without sulphite. <54 l After an oxidizing treatment, the internal
image can be developed (para. 70).
To develop the internal image< 55 l use a metol-hydroquinone developer
containing a solvent, in this case 0·6 to 1·8 % of hypo. Another developer •
frequently used contains paraphenylene-diamine+6 % of sulphite+O·ll%
of caustic soda; development time, 2 minutes. It is also possible to develop
by means of a physical developer.
To dissolve a surface layer of the grains, use a solution containing 1·6 % of
hypo and 0·1 % of sulphite. Time: from 30 seconds to 4 minutes.
28. Printing out

The decomposition of an insoluble silver salt is lirr.ited by the reverse action,
when the vapour pressure of the gas (chlorine or bromine) reaches a certain
value for a given temperature.
In the case of a latent image, the bromine set free in the primary photo-
graphic reaction is in very minute quantity, since there is only one molecule
affected in ten million. The gelatin is capable of absorbing this bromine, and
the photochemical process may proceed in the same direction.
But the decomposition of silver chloride by light is a more vigorous process
than with bromide. The number of molecules affected is very great, and as a
result a relatively dense deposit of metallic silver is formed, as well as a fair
amount of chlorine which the gelatin can no longer hold. Indeed, the system
is self-sensitized by the liberated silver. <56 l
It is therefore necessary to add a chlorine acceptor to the gelatino-chloride.
The most common are silver nitrate, sodium nitrite and acetone-semi-
carbazone.
The visible image is formed by violet-coloured colloidal silver, distributed
within the remaining gelatino-chloride.
29. Effects of low temperatures

Above -20°C ( -4°F) the radiation absorbed is completely used for photo-
lysis (quantum yield is about 1). Between -zooc and -150°C ( -228°F),
only a fraction of the luminous energy is absorbed. The free electrons can
move, while the interstitial ions are immobilized. Below -150°C a large
proportion of the energy is liberated as a green fluorescence, by a recombina-
tion of the electrons with the bromine atoms. <57 >
The loss of speed (about ten to forty times) is most apparent in the surface
image. <58 > It is more pronounced in fine-grain emulsions and in those
ripened with sulphur sensitizers, thus proving that a loss of energy occurs in
the chemical sensitivity specks.
30. Eff~ct of high pressure

High pressure (1,000 to 2,000 kg/cm2) bearing upon photographic emulsions
will produce two simultaneous variations of sensitivity, i.e., a decrease in the
external sensitivity, and an increase in the internal sensitivity. <59 > In this de-
sensitization, two processes are present, i.e., reversible desensitizing and
irreversible desensitizing, <60 > which represents only 10 to 15 % of the total loss
of sensitivity.
Desensitizing appears to be due to a retarding of the ionic conductivity of
the crystals, and the effect is at its maximum at high inten~ities with short
exposures. The larger grains are those most affected by pressure, and a
smaller amount of gelatin will increase the effect. Amongst the manufactured
emulsions, the make which, up to now, has been the most sensitive to pressure
is 'Radio Crystallix' film. (61)
The speed of compression, and pressure after exposure have no effect.
The wavelength, however, has a considerable influence, i.e., the desensitizing
is more pronounced in the violet than in the green.
As far as internal sensitizing is concerned, this is probably due to dis-
locations of the crystals, with formation of internal traps. <62 >
Finally, we would note that Eggert and Zund <63 > have obtained pressures
ranging up to 10,000 kgjcm2, using a steel-ball system.
Friction. Friction on the surface of a sensitized coating produces fog due to
heat, accompanied by desensitizing due to pressure. The fog is usually
sufficient to render the coating useless for practical purposes; hence the value
of anti-abrasion supercoatings.
Furthermore, it is often observed that films show accidental foldings, called
'creases', in the shape of small crescents. When unexposed film is developed,
they appear as black marks on a transparent ground, while after exposure
they are light against a grey ground. As well as an emission of heat, the gelatin
is probably removed from some crystals, which, thus become spontaneously
developable.
31. Intensification of the latent image

There are several methods <64 > for intensifying an underexposed latent image
-methods which consist in converting the sub-specks into developable
specks. This intensification-commonly called latensification-is an auxiliary
operation which takes place after exposure and before development. It should
not be confused with hypersensitizing (which is an operation performed
before exposure), nor with normal intensification which takes place on the
developed image. The various processes of latent image intensification are
usually critical operations to perform in practice, since the results obtained
will vary, not only with the type of emulsion, but also between two identical
operations on the same emulsion.
(a) Second-exposure method. After exposure, the sensitive surface is sub-
jected to a uniform additional exposure of low intensity and long duration.
If this exposure is at high intensity, it will merely increase the number of
sub-specks. The intensification is more effective if the emulsion is previously
subjected to the Herschel effect. <65 > It is nil with X-rays.
The second exposure method is used in the processing of cinematograph
films, and in this case an exposure of some 15 minutes must be given at a
sufficient intensity to develop a density of 0·05. The sensitivity at the toe of
the curve is multiplied by 3. <66 > Sometimes it is necessary to go up to a fog
density of 0·2. When making a record of oscilloscope images, an exposure of
20 minutes is given at a distance of 2·4 metres from a 10-watt lamp in a
safelight fitted with a No. 3 Wratten filter, and lined with a sheet of white
paper. <67 > It is possible for the developed image to be intensified further
chemically. Second-exposure has also been used for colour films, such as
Ektrachrome.
(b) Mercury-vapour method. This is carried out in a closed vessel, at
an absolutely constant temperature and humidity. The latent image continues
to intensify after leaving for a time, and the cycle may be repeated several
times. The latensification can be explained by the condensation of the mer-
cury on the smallest specks, coupled with some adsorption on the silver
sulphide.
The intensification of the latent image by mercury vapour is, however, less
effective than hypersensitizing (before exposure) by the same medium. <68 >
Furthermore, it is very irregular, and the operation is tedious. Operating
conditions: t = 20°C (68°F); humidity = SO % R.H. duration of process =
6 to 24 hours.
(c) Organic acid method. The acids used are, for instance, formic, acetic
and propionic acid (vapours, or solutions in carbon tetrachloride or ben-
zene). <69 > After the evaporation of the acid absorbed by the emulsion the effect
remains for one or two weeks. When latensifying, traces of moisture must be
present, but immersion in an aqueous solution of acid will desensitize. How-
ever, it is possible to use an aqueous solution of oxalic acid. <70 > The gain in
speed is from 100 % to 300%. Sheppard, Vanselow and Quirk explain this
method of latensification by the hypothesis that the Ag+ ions situated on the
THEORY OF THE LATENT IMAGE 3S
surface of the grains are moved, due to the neutralization, by the acid, of the
amine or imide groups of the gelatin.
(d) Sulphur dioxide method. The intensification of the latent image by an
atmosphere of sulphur dioxide, at SO % humidity, was shown in 1943 by
Simmons. <71 > The duration of the process is from 2 to 24 hours, for a three-
to five-times increase in sensitivity and a fog density increase of 0·2 to 0·4.
The contrast decreases, which the experimenters compensate by developing
twice as long- then praising latensification for the increased speed thus
obtained.
A container of liquid sulphur dioxide may be used or a solution of bisul-
phite or metabisulphite may be acidified. Example:
Sodium bisulphite liq. 40 cc

Water so cc
Acetic acid 10 cc
It is possible, however, to latensify by immersion in a solution of sulphur

dioxide (at 1 or lt % ). The speed is doubled.
With bilttlphite, the procedure is the same. For example, immerse the ex-
posed negative for S minutes in the following solution:
Potassium metabisulphite 3g
Sodium sulphite, anhydrous 1g
Water 100 cc
Rinse for one minute before developing.

The latent image may also be intensified by sulphite and hypo in 2% solu-
tion. A few minutes' treatment is sufficient, but if prolonged too far, would
produce a reversal of the image. (72)
(e) Oxidation method. This method calls for the use of such media as
hydrogen peroxide, ozone and sodium perborate, which activate the Ag+ ions
in t~e neighbourhood of the specks.
Hydrogen peroxide was used by Liippo-Cramer in 191S (for a complete
exposition, see Wightman, Trivelli and Sheppard). <73 > Immersion: S minutes
in a one-volume solution, before development.
With an atmosphere of oxygen containing 4% of ozone<74 > a 90-minute
treatment is necessary, followed by a further one of 24 hours in a normal
atmosphere. The increase of speed with a rapid emulsion is only 30 %,
whereas it is 90% with an X-ray emulsion. It has, however, been possible to
obtain an increase of 100% in a rapid emulsion by using air with only
1 millionth part of ozone.
The simplest method is to immerse the exposed negative for 60 seconds
in a 0·2% solution of sodium perborate, and develop without washing; the
speed is doubled. The increase is greater if a 1% solution is used, with anti-
foggant added (0·1S % of bromide or 0·0()3% of benzotriazole). The treat-
ment time must then be reduced to S seconds. <75 > The efficiency of the latensi-
fication decreases when development is prolonged.
c
(f) Ammonia and amines method. In this case the Ag+ ions are liberated
as complex (NH 3 )Ag+ ions and lose their ammonia (or other basic radical)
after precipitation on the specks. This method is seldom used. With ammonia
gas it is possible to double the sensitivity of a negative emulsion.
(g) Gold method. The exposed material is immersed for 5 minutes at 20°C
in the following solution (76 >:
Heat until boiling just starts:
0·1% solution of potassium chloroaurate 40 cc
Potassium thiocyanate 0·5 g
then add
Potassium bromide 0·6g
Water to make 1000 cc
Wash for 20 minutes before developing. The sensitivity is increased two
or three times.
It would appear that the sensitivity specks containing silver react with the
aurous thiocyanate and that metallic gold forms a deposit there. The latter
no doubt enables the development to be initiated more easily.
1. This is actually a suspension, viz., a dispersal of a solid, and not of a liquid.

2. Solids will usually crystallize in one of three forms: atomic, ionic or molecular.
Sulphur and diamond produce atomic crystals, in which the atoms are retained
by powerful covalent forces. Salts produce ionic crystals, in which the atoms (in
the state of ions) are kept together by electrovalent bonds. Organic substances
will form molecular crystals, and in this case, the atoms are retained in less rigid
groups by weak cohesive forces, known as Van der Waals' forces.
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75. Vanselow W., Quirk R. F. and Lerrmaker J. A.: Phot. Soc. Amer. Jl., 1948,
675-680.
76. James T. H., VanselowW. and Quirk R. F . : Phot. Soc. Amer. Jl., 1948,349-353.
Chapter IV
REDOX POTENTIAL
Development consists in converting the latent image into a visible image, but
before explaining its mechanism it is essential to give a few brief notes on
the meaning of pH and redox potential, which affect it closely.
32. The pH
We know (para. 845) that water H(OH) is formed by two ions H+ and
(OH)-.
On the other hand, a base results from the union of a positive ion, such as
Na+, with the negative ion (OH)- , while an acid, on the contrary, is formed
by a negative radical Cl-, for example, with the positive ion H+ (para. 844).
All these expositions call for a knowledge of the nature of ions, which it is
advisable to master before pursuing the matter further (para. 841 ).
By reacting an acid AH with a base B(OH), a salt AB and water H(OH) or
(H20) will be produced according to the following equation:
AH+B(OH) = AB+H(OH)
Acid Base Salt Water
But acids, bases and salts in solution will dissociate into ions.
AH~A-+H+ B(OH) ~ B++ (OH)- AB ~A-+B+
The former reaction may then be written:
Acid Base Salt Water
If we now eliminate the similar terms, there remains:

H++(OH)- = H(OH)
This means that the neutralizing of an acid by a base is no more than a
reaction between the ions H+ and (OH)- with a forming of water and a
neutralizing of the electric charges. It seems obvious that the number of
H+ and (OH)- ions which combine depends on the degree of dissociation of
the complete molecules AH and B(OH) into their ions, i.e., the degree of
ionization.
As the acid and the base are the ~tronger, so they ionize the more fully. Sul-
phuric acid will ionize almost completely in dilute aqueous solution: This is
39
a strong acid. Acetic acid, on the contrary, ionizes but slightly, and is a weak
acid.
Since the operation is carried out in an aqueous solution, it is necessary to
take into account the ionization of the water itself:
H(OH) ~H+ +(OH)-
If we call [H+J+[(OH)-J the number of ions H+ and (OH)-, and if we

call [H 20J the total number of molecules of water, then the following
equation ensues:
LH+JX l(OH)- J
- - -- -- - KHo
[HzO] - '
The number of dissociated molecules of water being small, the total quan-
tity of water shows no practical variation, so that the following formula will
result:
~is a characteristic constant of the ionic dissociation of water, equal to

10-14 at 25°C and 0·6 x 10-14 at 18°C.
The concentrations of H+ and (OH)- being naturally equal, it suffices here
to know one of them, viz., that of ions H +, which is the square root of K 0 ,
t.e.:
[H+J = yK0 = 10- 7 as an average.
A concentration in hydrogen ions equal to 10- 7 is characteristic of a neutral

solution (pure water). If the concentration in ions H + is higher than 10-7 , then
an acid is present, but if it is lower than 10- 7 , a base is present. (In this case
(OH) ions predominate.)
For greater convenience, the logarithm of the reciprocal of the [H+J con-
centration is used, and the value thus obtained is called the pH, thus:
1
pH = log10 - -
[H+]
For a neutral medium in which [H+] = 10- 7 , the pH is 7. For an increasingly
acid medium, the pH drops from 7 to 0. For a basic (or alkaline) medium, the
pH rises from 7 to over 14.
In short, the pH is a measure of acidity or alkalinity of a medium. (ll It is
very important to know this, since the properties of compounds vary con-
siderably in this connection-solubility, speed of reaction, stability, redox
potential, all depend on the pH. In every chemical process, it has to be
specified in the same manner as temperature.
Buffer solutions. Buffer solutions contain either a mixture of a weak acid with a salt
of a strong base and this acid (e.g., acetic acid plus sodium acetate), or a mixture of a
weak base with a salt of a strong acid and this base (e.g., ammonia and ammonium
chloride).
REDOX POTENTIAL 41
The pH of a buffer solution depends on the relative proportion of its active con-
stituents.
The pH of a buffer solution is independent of the concentration.
Buffer solutions which are used as standards for comparison are as follows:
KCl + HCl for pHs varying from 1 to 2·2.

Potassium acid phthalate + HCl for pHs varying from 2·2 to 3 ·8.
Potassium acid phthalate + NaOH for pHs varying from 4 to 6 ·2.
KH 2PO, + NaOH for pHs varying from 5 ·8 to 8.
H 3B0 3 +KCl + NaOH for pHs varying from 7·8 to 10.
33. Measuring the pH

1. Electrometric method. In order to determine the concentration of hydrogen ions
accurately, the 'electrometric method' is commonly used, and consists in measuring
the potential of a hydrogen electrode immersed in the liquid under examination. A
comparison is made with a known reference electrode, which is connected with the
former by a solution of potassium chloride serving as an electrolyte. The hydrogen
electrode consists of a platinum plate surrounded with hydrogen which is continu-
ously bubbled past it. The reference electrode is a standard calomel electrode of
known e.m.f.
If E is the e.m.f. of the cell formed by the hydrogen electrode-calomel electrode
(measured by means of a potentiometer)-then the pH is expressed by the formula
pH = E -a/ b, in which a and b are two constants depending on the temperature and
the connecting electrolyte. If the latter is potassium chloride at a concentration of
1 molecule per litre (74·5 g pl) at 20°C, then a = 0·2835, and b = 0·0581.
The hydrogen electrode requires complicated equipment and precise handling. In
everyday practice, a glass electrode is used.
The glass electrode is based upon the following principle :
Two solutions, each with a different pH, will-when separated by a thin glass
partition-produce a potential difference in relation to a standard (calomel) electrode.
Electrode I Sol. A I Glass I Sol. B I Standard electrode. The potential E is
given by E = A(pHA -pHB) + E 0 , in which A and E 0 are constants of the electrode
depending on the nature of the glass; A varies also with the temperature.
The glass electrode is a very thin blown glass bulb and must possess a compara-
tively low electric resistance, so that a galvanometer with a sensitivity of 10-'A will be
adequate for measuring. The orthodox type contains a liquid of known potential, but
some people prefer a glass electrode metallized on the inside.
A glass electrode has the disadvantage of being prone to attack by very alkaline
solutions (e.g. caustic developers).
The normal pH-meters fall into two categories: (a) the direct-reading type, con-
sisting of an amplifier and millivoltmeter, which is simple to use, and (b) the null
reading type, in which the e.m.f. is measured without the system supplying any
current. Accuracy up to 0·01 pH unit. Finally, the supply of current can be taken
from the mains or from a battery.
2. Colorimetric method. The colorimetric method for determining the pH does
not call for any expensive equipment, but it is much less accurate than the electro-
metric method. It is based upon the use of colour indicators.
In order to ascertain the pH of the solution under examination, a diluted solution
is added, of an indicator whose colour changes with the pH (the concentration of this
solution must be a known quantity, e.g., from 0·02 to 1 %). The colour obtained is
compared with that of a solution of known pH (standards which are obtainable com-
mercially in the form of ready-to-use liquids).
The full list of coloured indicators is very long, but a few only are sufficient to test
over the whole pH range.
Indicator pH Range Indicator pH Range

Methyl violet I 0·2 to 1 ·8 Phenol red 6·8 to 8 ·4
Thymol blue 1·2 to 2 ·8 Cresol red 7·2 to 8·8
m-Dinitrophenol 2·2 to 3·8 Thymol blue 8·0 to 9·6
Bromophenol blue 3·0 to 4·6 Phenolphtalein 8·6 to 10 ·2
Bromoscresol green 4 ·0 to 5·6 Alizarine yellow GG 10 ·2 to 11·8
Chlorophenol red 5·2 to 6 ·8 Tropeoline 0 11·2to12·8
Bromothymol blue 6 ·0 to 7·6
There exist some mixed indicators, known as 'universal', which give a large number
of colours over a very extensive pH range. They are also to be found in the form of
very convenient indicator papers for rapid, though approximate, measurements.
33a. Oxidation and reduction

The process of oxidation and reduction consists of a transfer of valency
electrons. It has nothing to do with oxygen itself.
When a positive ion loses a surrounding electron, it increases in valency; it
is said to oxidize. For instance, a ferrous ion Fe++ is bivalent; it is derived
from an atom of iron Fe, with the loss of two electrons. If it loses a third
electron, it becomes still more positive by changing to a trivalent ferric
ion Fe+++. The ferrous ion has been oxidized into a ferric ion according to
the reaction :
Fe++- e --* Fe+++
Conversely, a ferric ion may be reduced to a ferrous one by appropriating

an external electron. The valency decreases from 3 to 2 by increasing the
number of the surrounding electrons, i.e., Fe++++e--* Fe++.
In the same manner, cuprous salts Cu+ will be 'oxidized' to cupric salts
Cu++, stannous salts Sn++ to stannic salts Sn+++, mercurous salts Hg+ to
mercuric salts Hg++; or conversely, the cupric, stannic and mercuric salts
will be reduced to cuprous, stannous and mercurous salts.
If, instead of starting from an ion, one starts from an electrically neutral
metallic atom, the latter may be 'oxidized' by losing an electron. It passes to
the state of a positive ion: thus metallic silver will be oxidized to an Ag+ ion.
Ag-e -*Ag+
and the ion Ag+, on the other hand, may be reduced to metallic silver Ag by
appropriating an electron: Ag++e -> Ag.
Any substance capable of appropriating electrons is an oxidizing agent and
any substance capable of supplying electrons is a reducing agent.
The oxidizing agent itself will be reduced while it oxidizes another sub-
stance, and the reducing agent itself will be oxidized while it reduces the
other substance. This is why oxidation and reduction are two closely con-
nected processes, since when there is oxidation on the one hand, there is
certainly reduction on the other and vice versa. For example, potassium
permanganate KMn04 is mixed with ferrous chloride, according to the
procedure described in para. 848. We shall now write this in a different
manner, -viz.:
REDOX POTENTIAL 43
The permanganate contains the permanganic anion (Mn04)-, in which Mn
is heptavalent (secondary valency): Mn7+. But the latter lacks five electrons
to produce the ion Mn++ (main valency), according to the formula Mn 7++
Se-+ Mn++.
The permanganate, therefore- capable as it is of absorbing 5 electrons-
is a strong oxidizing agent. These 5 electrons are supplied by a reducing
agent, i.e. the ferrous chloride FeC1 2 , of which the ion Fe++ will oxidize to a
ferric ion F+++, thus:
Mn7+ + 5Fe++ -+ Mn++ + 5Fe+++
The permanganate (oxidizing agent) is reduced to manganese chloride, and

the ferrous chloride (reducer) is oxidized to ferric chloride.
34. Electrode potential

Let us immerse a strip of metal, such as a silver electrode, for instance, into
an aqueous solution of one of its salts.
The metal may give off ions to the solution, while itself assuming a negative
charge. A difference of potential is established between this solution and the metal.
This potential is due to the electrons released by the positive ions which have
passed into the liquid and those remaining in the metal.
The pressure P of the metallic electrode ions, to become a solution, is the
solution potential of the metal.
If p denotes the pressure on the electrode (osmotic pressure) of the ions
already contained in the saline solution-in this case, silver ions Ag+-three
situations may arise, viz.:
(a) P = p. There is an even balance and nothing occurs.
(b) P > p. The electrode gives off Ag+ ions and is brought to a negative
potential in relation to the solution.
(c) P < p. The ions Ag+ of the solution pass to the electrode, which is
brought to a positive potential.
The electric field, which is formed immediately, balances the difference of

pressure, and the movement of the ions stops. But if the metallic electrode is
connected with a second and non-attackable electrode immersed in the same
liquid, then the current of ions will continue.
The potential of a metallic electrode immersed in one of its salts is given by
the formula:
RT P
E = - log-
nF p
in which T is the absolute temperature (273+e), R the gas constant

(83·155 x l0 4'), n the valency of the ions, Fa Faraday equal to 96·490 cou-
lombs, and log-natural logarithms.
The osmotic pressure p of the ions is proportionate to their concentration c.
c*
For Ag+ ions, this is represented by [Ag+]. Since p = K[Ag+J and since
n = 1 for silver, the above formula becomes:
RT P
E =Flog K[Ag+]
which may be written:

RT P RT
E = -log-+-log [Ag+]
F K F
The expression RT/F log PJK is constant and is designated by E 0 •
The silver electrode potential thus becomes :
RT
E = Eo+-log[Ag+]
F
in which E 0 is the potential of a silver electrode immersed in a solution con-
taining one gram-ion of silver per 1000 cc, i.e., [Ag+J = 1.
E 0 is the normal potential of the metal. For silver, it is +0·86 V the normal
potential of hydrogen being 0.
All calculations made, the formula resolves itself as follows :
EAg = 0·86 + 0·06 log1o [Ag+] volt
and generally speaking:
0·06
E = Eo+ -log [X] volt
n
As a standard electrode for comparison, a standard hydrogen electrode is

used (strip of platinum covered with platinum black surrounded with hydro-
gen gas), or alternatively a calomel electrode formed by the following chain:
mercury I calomel HgCl I normal solution of potassium chloride.
The mercury is connected with the conductor by a platinum wire, and a
syphon enables contact to be established with the silver solution. Since the
potential of this electrode is 0·283 in relation to that of hydrogen, the true
value of the potential of the measured silver electrode is E = E 0 +0·283 Vat
25°.
35. Redox potential

1. Let us revert to the example of permanganate, <2 l which oxidizes the solu-
tion of a ferrous salt. We have seen (para. 33a) that:
Instead of making up the solutions in the usual manner, let us place them in two
concentric containers M and F (Fig. 4). M contains the permanganate solution, and
F-made of porous material-contains the solution of ferrous salt. A platinum electrode
REDOX POTENTIAL 45
is immersed in each of these solutions, and if the two electrodes M and F are con-
nected, a current will be observed flowing from M to F. At the same time, the bivalent
iron Fe++ is oxidized into trivalent iron Fe+++ by a loss of electrons, while the per-
manganate is reduced to the state of manganous salt Mn++ by the appropriation of
electrons. These migrating electrons start from the ferrous solution, travel along the
conducting wire from F towards M (in the reverse direction from the conventional
current) and disperse in the manganic solution.
FIG. 4.
The migration of these electrons can readily be explained if one notes that in F and
M we have two electrodes necessarily possessing their own potentials in relation to
their respective solutions, according to our remarks in the previous paragraph. In
order to produce a current from M towards F, it is necessary for electrode M to
possess a greater potential than that of electrode F, so that EM- EF > 0.
Since these potentials depend on the power of emission or absorption of electrons
in the reducing and oxidizing solutions, in which the electrodes are immersed, the
potentials EM and EF must represent respectively the redox potentials of permangan-
ate and ferrous salt.
If the concentrations of permanganate, ferrous salt and resulting ferric salt are
indicated by the expressions [Mn0 4 - ] , [Fe++] and [Fe+++], the following will be
produced by applying the general formula previously established:
0·06
E =Eo + -log [X]
n
For permanganate EMnO, = 1·45 + 0·06/ 5 log [MnO,-]

For the ferrous-ferric mixture:
[Fe+++)
E = 0· 7 + 0·06 log volt
Fe [Fe++]
In short, the oxidizing and reducing powers of a substance are measured by

its redox potential. Knowing the concentration in gram-molecules of this
substance per 1000 cc, and the normal potential or the proportionate potential
to a normal solution (1 valency gramfl) it is possible to calculate the redox
potential by means of the above formula.
The normal potential is measured once and for all in relation to a standard
electrode, i.e., a hydrogen electrode.
It should be remembered, however, that the redox potential depends on the

pH. For every value of the latter there is a corresponding and different value
of the redox potential <3 l:
For instance, with pH= 0, the following potentials occur<4 l:
(Mn0 4 ) - : 1·45 V permanganates
Fe+++jFe++ : 0·70 V . ferric salts
FerricyanidesfFerrocyanides 0·70 V
IJI- : 0·65 V iodine
ClfCl- : 1·30 V chlorine
8 20 8 : 2 V persulphates
Cr6+fCr3+ : 1 V dichromates
V 5 +fV4+ : 1 V vanadates
V4+fV3+ : 0·4 V vanadium
Ce4+fCe3+ : 1·45 V cenum
H 2S0 3(at pH= 1) : 0·50 V sulphurous acid
It will thus be seen that permanganates, chlorine, persulphates and cerium

salts Ce4+ are very strong oxidizing agents.
At pH = 0 potassium permanganate has a potential of 1·45 V while at
pH : 4·5 it drops to 1·10 V and at pH : 10 it is only 0·72 V. With vanadates,
the difference is still more striking, for at pH : 0, E = 1 V; while at pH : 8,
E is nil. Iodine, on the contrary, does not alter with acidity.
2. Ag+ ions have a comparatively high normal redox potential, viz.,
0·8 V. Ag+ is reduced to metallic Ag by appropriating an electron according
to the pattern Ag++e ~Ag, in which Ag+ is an oxidizing agent.
As we saw in para. 34, the relative potential to a given [Ag+] concentration
is calculated by the formula EAg = 0·80 V+ 0·06 log [Ag+], which means
that the solution oxidizes more strongly as more Ag+ ions are present. It is
much less when the silver salt is insoluble, because then log[ Ag+] becomes
negative. Example:
Silver chloride, insoluble in hydrochloric acid medium, produces only
10-10 ions; log 10- 10 is 10; the expression 0·06 V log[Ag+] becomes equal to
0·06 Vx ( -10) = -0 ·60 V to subtract from 0·80 V leaving only 0·20 V.
3. The redox potential is measured by means of a platinum wire immersed

in the liquid under examination, in an atmosphere of nitrogen. The cell is
connected with a calomel electrode by means of a right-angle tube filled with
gelose saturated with potassium chloride. A potentiometer shows the potential
of the platinum electrode at a given temperature and pH.
The colorimetric r'nethod is quicker, though often subject to error. In this
case, indicator dyes are used (safranines, sulphonated indigoes, methylene
blue, indo-phenols, etc.) which change colour in a certain range of the redox
potential. (They lose their colour in a reducing medium.) Some indicator
systems show two ranges of change, e.g., a mixture of starch paste, iodine
and colourless potassium iodide (at an acid or neutral pH) becomes blue at
0·65 V and loses colour again at 0·9 V. As a general rule, it is advisable to
REDOX POTENTIAL 4-7
check the accuracy in the colour change of an indicator, for a given substance
and under given conditions, by the potentiometric method.
1. Note.-The pH of pure water, fixed at 7, is theoretical. Distilled water is acid

(pH = 5·5). Double-distilled water is less so, with a· pH of 6 ·2.
2. Charlot G.: Annales de Chimie Analytique. Importance of theoretical knowledge
in analytical chemistry.
3. The redox potential is linked to the pH b y the expression Ea = -0·06 pH-
0·03 log P, in which Pis the hydrogen pressure in equilibrium with the solution.
-logP is designated by the symbol rH. In practice, the following occurs in
measurements:
b
EH = a- -rH
2
+ b.pH
in which a and b are constants. Oxidizing systems have an rH higher than 27.
Chapter V
THEORY OF DEVELOPMENT
36. Development centres and redox potential
1. As we have already seen, the latent image is formed of microscopic
aggregates of metallic silver dispersed on the surface of the silver bromide
crystal.
Development consists in reducing the grains of silver bromide to metallic silver
which forms the visible image. But only the grains affected by light, that is,
the grains having centres are reduced. This means firstly that the visible image
obtained is discontinuous, for it is formed of individual points, separate or in
groups depending on whether the light was weak or strong; therefore a grain
begins to be blackened around the centres in successive concentric spheres
until the grain is completely reduced (Fig. 5). The gelatino-bromide layer is
then at its normal limit of blackening and its maximum contrast or 'y-infinity';
it is then composed of completely reduced grains, and grains which are un-
affected, with no intermediate state. The initial amount of silver in the
development centres is increased about ten billion times.
FrG. 5.
Development is carried out by immersing the exposed sensitive layer in a

bath (developer) containing a reducing agent for a certain time. Study of redox
potentials teaches that a reducing substance is one which has a much lower
potential than the compound to be reduced. The reducer parts with electrons
which are received by the oxidizing agent; in these conditions, the reducer
becomes oxidized and the oxidizing agent is reduced. The oxidizing agent is
in this case the Ag+ ion which is converted to metallic silver, by acquiring an
electron according to the scheme:
Reducer+Ag+ = Ag++e+ oxidized reducer
Ag
48
2. It was explained in para. 35 that for a reaction to take place between an
oxidizing agent and a reducer, the potential of the oxidizing agent must be
greater than that of the reducer. In this case the oxidizing agent is the Ag+ ion
and the reducer is the developing agent: there must therefore be a positive
potential difference between EAg and Ered
LlE = EAg - Ered
But the redox potential of silver is a function of the concentration of Ag+
following the formula
RT
EAg = Eo+-logAg+
F
As the silver ion concentration is reduced by the presence of bromide ions,
whose usual concentration is 0·01 gram-ion, EAg is, at the most, 0·202 V at
l8°C.
Reinders (ll has shown that for development to take place it is insufficient
for the developer to have a lower potential than the silver; there must be a
substantial minimum which varies with the exposure. This potential differ-
ence must be about 0·07 V for the high exposures and 0·1 V for the low ones.
If an average value of 0·08 V is chosen, then the maximum potential of a
reducing agent, for development to take place must be 0·12 V, for 0·08 V =
0·202 V -Ered
Therefore Ered < 0·12 V.
The potential (or activity) of development therefore diminishes as the oxida-
tion potential increases. <2 >
In other words, any substance with a redox potential below 0·120 V can
develop a photographic image. Abribat<3 l has successfully tried a wide range
of products: sugars, leuco bases, haemoglobin, anaerobic bacteria cultures,
old Burgundy wines made alkaline, etc.
3. The developing power of a developer towards a silver halide is not only
dependent on its reducing power, but also on the potential of the halide, and
consequently on the composition of the latter: silver chloride is more easily
reduced than silver bromide<ab) whilst the iodide is very difficult to reduce.
Similarly, of the bromides which contain a proportion of iodide, those with
the highest content need a more powerful developer.
The size and structure of the grain also have an effect. In general, fine-grain
emulsions can be developed at a higher redox potential (that is, a weaker
developer) than fast coarse-grain emulsions.
As a general rule, it can be considered that the silver halides can be re-
duced even without exposure; but the rate of reduction is slow. The centres
formed on exposure accelerate the phenomenon considerably.
37. Adsorption of developer and development theory

1. In practice, reduction only takes place around the development centres,
for the silver bromide crystal is surrounded by a potential barrier which can
only be breached in the neighbourhood of the centres. <4 l Each surface silver
ion is surrounded by only 5 Br ions instead of 6 ; to saturate its affinity it
adsorbs a Br- from the potassium bromide. The layer of Br- protecting the
Ag+ is itself surrounded by a layer of K + ions.
Sheppard and Meyer< 5 l in 1920 put forward the hypothesis that the
developing agent is first adsorbed by the silver bromide. James and Vanselovv< 6 l
have recently confirmed this chromatographically, and have shown that the
developing agent is found in the ionized state.
Luppo-Cramer, however, stated in 1924 that the induction period of a
hydroquinone developer is shortened by the presence of its oxidation products.
Frotzsher, then Luther< 7 l considered that these products were essential to
the triggering-off of development. Staude<8 l stated more precisely that they
behave as intermediates for the adsorption of the reducing agent. Further
experiments of Staude and Brauer< 9 l have just confirmed this: without the
presence of quinone, the hydroquinone is not adsorbed, and will not develop, and
furthermore the quinone itself, oxidation product, is only adsorbed by exposed
silver; the quantity increasing with the txposun received.
Rabinovitch (lOl has shown also that the reduction of the adsorbed developer
takes place at the silver-bromide boundary, and that the metal resulting from
the reaction in turn adsorbs further developer. According to the same worker,
all metals in a finely divided state, whose crystal lattice is cubic (silver, gold,
platinum, copper) bring about catalytic oxidation of the developer.
It might be, however, an interface catalysis at the crystal-centre-developer
point of contact.
Sheppard, applying James' hypothesis<11 l has disputed Rabinovitch's the-
ory according to which the adsorption takes place on the centres only. He
thought that this takes place more on the silver ions surrounding the silver
metal of the latent image. Holes form around the centres: migration of silver
atoms on one hand (uncovering fresh silver bromide surfaces to the developer)
and passage of bromide ions on the other. Harker and Sheppard have put
forward the hypothesis that the migration of freshly formed silver atoms on
the surface of the metal, before they are incorporated in the lattice results in
the formation of filaments.
For a developer to develop, it is not sufficient that it should have a suitable
redox potential; it is also essential that both the developer and its oxidation
product should be adsorbed by the development centres of the latent image. (12.)
2. Electrolytic theory. According to the Gurney-Mott theory, extended to
development by Webb and Evans, there is a potential difference between the
interior and exterior of the silver bromide grain. Normally, the electrons can-
not cross the' barrier formed of Br- (themselves surrounded by K.+ ions).
However, the silver specks of the latent image break it down, like an electrode
buried in the grain. The reducer (developer) then gives electrons to the Ag
metal and the potential of the speck rises.
The interstitial silver ions of the lattice are displaced by thermal agitation,
and are attracted towards the speck to form new layers at the interface,
Ag++e = Ag. Having no room, the silver metal is pushed out (into the
gelatin) as spongy filaments. The crystal becomes more deformed as develop-
ment proceeds, which further accelerates the production of silver ions capable
of being neutralized by the electrons.
Berg does not bring in the interstitial silver ions: the growing specks leave
empty places where positive holes collect. The Br- ions can then reach the
surface to pass into solution.
Jaenicke, Kruger and Hauffe<13 > combine the role of electrode played by
the specks with the theory of Wagner and Traud (1936) following which the
oxidation of the developer and the reduction of the silver ions are two pheno-
mena which take place at different places.
38. Structure of the developed grain

1. The electron microscope shows that during development, filaments of
metallic silver are pushed out of the crystal, the grain being finally made up
of a mass of irregular metallic threads, similar to masses of seaweed (Fig. Sa).
The length of each filament is greater than the diameter of the crystal. On
the other hand, the distance of projection depends on the rigidity of the
gelatin. The developed grain therefore appears as a spongy, filamentary mass.
When the grains are very small, as in Lippmann emulsions (0·04 f-l diameter)
a single filament, longer but thinner than the grain is formed.
Hydroquinone produces thick filaments; metol and amidol give fine fila-
ments. Physical development, contrary to chemical development, results in
compact grains, or crystalline plates. When physical development takes place
before fixing, however, ribbons are formed, 0·1 f-l wide and several f-llong.
FIG. Sa.
If the reducing power of a chemical developer decreases, there is a transi-

tion of the grain structure from filamentary to plate; <14 > for example, by
developing for twenty-eight hours in a solution containing ferrous sulphate,
ferric nitrate and sodium citrate. According to Levenson and Tabor, in the
beginning the silver tends to form a thin plate structure; this is during the
induction period. Then, as the rate of growth increases, the silver tends to
reform into filaments. The silver of the plates must therefore be quite mobile
to be re-used for the production of these filaments.
2. In the previous paragraph it was shown that these are several processes
by which the 'tangled seaweed' structure of the developed grain can be
explained. Thus for James and Kornfeld <16 > the filaments are due to the migra-
tion of the silver from the point of its production at the Ag- AgBr-developer
interface along the surface of the already reduced metal. Levenson and Tabor
considered that it takes place along the fissures and other crystal defects, and
insist that it is from the labile mass of silver and not from the AgBr itself,
which is caused by the great mobility of the Ag+ ions along the filament. On
the other hand we have seen that following the Gurney-Mott electrolytic
theory the developer provides the specks with electrons which produce a
negative electric field, to which the interstitial ions are rapidly attracted,
producing a pressure which pushes the silver out of the grain. For Keith and
Mitchell <16 > the electric negative charges are concentrated at the extremities
of the specks where they are neutralized by the Ag+ ions.
We would note that the formation of fine filaments of silver was studied
.in 1932 by Kohlschiitter. (17) Then, at the conclusion of the electrolysis
studies of Samartsev and Vagramyan, <18 > Gorbunova and Dankov stated that
the growth of the crystal takes place on one face. <19 > The laws of the crystalliza-
tion of fine filaments was then studied by Gorbunova and Zhukova, <20 >
Boisson<21 > and Vuille< 21 b> who noted that the silver polygonal figures in
AgBr crystals, caused by the arrival of Ag+ ions, grow up along the inter-
section of the crystal surface and the (111] or (100] orientations.
3. Electron microscope studies of the structure of silver bromide grains have been
made successively by the following workers who have reported their operating tech-
nique: Von Ardenne,( 22 l Hall and Schoen,(•s> Kuster,( 24 > Selme,( 25 > Hamm and
Comer.(••> The emulsion, dissolved in warm water, is generally deposited on an
extremely thin colloidon film forming the carrier. This film can be obtained by placing
a drop of 1-2% nitro-cellulose solution (in amyl acetate) on a sheet of water; it is
removed on a thin disc of perforated platinum or on a fine metal gauze. After putting
it in position the apparatus is exhausted. The images are photographed on electron-
sensitive plates or on normal plates if an intermediate fluorescent screen is used. The
actual enlargement of the apparatus, assisted by an enlargement of the negative gives
a final magnification of 25,000 to 10,000 diameters. Only very thin crystals can be
examined due to the low penetrating power of the electrons: 10-50 mf' layer thickness
for a resolution of 5 mfL.
To separate the gelatin from the crystals in order to study the latter under the
microscope, the emulsion can be hydrolysed with an enzyme. The suspension is then
centrifuged and washed before being placed on the carrier.(••>
The structure of unexposed grains cannot be recorded directly as they are sensitive
to electrons. They must be strongly overexposed to bring about complete photolysis:
dark aggregates can be seen formed on the surface of the grain, at certain well-defined
spots, probably the sensitivity centres or the fissures, whilst the droplets of silver form
a halo around the grain. The double moulding technique used by Hamm and Comer(••>
enables the action of the electrons on the crystal to be avoided. A better method is to
protect the crystals by a carbon deposit which can be obtained either by sublima-
tion(26b> or action of effluvia in benzene vapours.( 26c>
39. Influence of pH on the development potential

As the redox potential of a solution is a function of its pH, it is obvious that
the development potential (or activity) of a developer increases with the pH, that
is with the alkalinity. The development potential becomes higher as the redox
potential drops, and also, this diminishes with the pH following the equation
RT [Ox] RT
Ered = Eo + - l o g e - - + - loge[l-I+]
nF [Red] nF
in which [Ox] represents the concentration of the oxidized form of the
developer, [Red] that of the normal form, [H+] the concentration of hydrogen
ions. All calculations made with the preceding formula become
0·058 [Ox]
Ered = Eo+ --logw- - - 0·058 pH
n [Red]
If the curve of the change in redox potential is plotted against pH, it is seen
that the development of an image is only possible, with the reservation of
adsorption, above a certain pH value (which varies with the developing
agent) from which the redox potential has a value less than 0 ·120 V.
Some substances, which are oxidizing agents in acid solution become
reducers (and hence developers) in strongly alkaline or even neutral solution;
this is the case with hydrogen peroxide, a powerful oxidizing agent at pH 0
withE equal to 0·88 V falling to 0 ·1 Vat a pH of 11 (very alkaline). We have
already shown similar cases of change of potential as a function of the acidity:
the vanadates for example give E = 0 ·5 Vat pH 4 and 0·1 Vat pH 7 (neu-
tral).
When the developing agent is neither acid nor basic the pH has only a
slight influence on the development potential; this is the case with ferrous
oxalate which shows no appreciable variation between pH 4 and 9.
It is therefore evident that for consistent development the pH must be kept
constant.
Now the decomposition of silver bromide by the reducing agent produces
both metallic silver making up the image and hydrobromic acid resulting
from the liberation of the bromide ions, which tends to reduce the pH of the
solution. It is therefore necessary to neutralize the acid as it is produced by
a buffering agent: this is why a large excess of alkali which maintains the pH
constant is added to a developer.
The chemical constitution of the alkali is of relatively slight importance in
itself as long as it can fulfil its two roles :
1. Produce the required pH of the solution;
2. Neutralize the resulting hydrobromic acid and maintain the pH constant
by its buffering action.
40. Influence of the sulphite

Consider the redox potential formula of a developer at fixed pH
0·058 [Ox]
Ered = Eo+ --logw - -
n [Red]
0·058 [Ox]
where --logw-- is a negative term.
n [Red]
The ratio [Ox ]/[Red] must be very small in the case where E 0 is greater
than 0·12 V; thus log [Ox ]/[Red], sufficiently great, subtracted from E 0
brings ERed to less than 0·12 V, anyway.
By eliminating the oxidized form of the developer as it is formed, the ratio
of the concentrations [OX]/[Red] can be kept sufficiently low for ERed to
remain substantially constant below 0·12 V, even with substances apparently
possessing a high redox potential. Pouradier and Abribat< 27 l have shown that
the reduction of silver bromide by a ferrous salt produces ferric ions (oxidized
form) which are eliminated by converting them to a ferri-hydrofluoric com-
plex, (FeF 6)- - -, by adding sodium fluoride. Otherwise, the normal potential
of the system Fe++f Fe+++ being 0·75 V, the ferrous solution would not
develop.
The sodium sulphite which is added to a developer in order to preserve it,
by preventing atmospheric oxidation also brings about, during development,
the elimination of the oxidized form of the reducing agent by converting it
to the sulphonate.
If, for example, the developing agent is hydroquinone with the empirical
formula C 6H 4(0H) 2 the sequence of reactions is as follows: <28 >
The hydroquinone is first ionized to quinone ion (C 6 H 40 2) - - and hydrogen
ions H +
hydroquinone quinone ion h ydrogen

lOllS
and the quinone ion gives 2 electrons to 2 silver ions which become 2 atoms
of silver metal, and is itself converted to quinone
quinone silver silver quinone

ion ions metal
The hydrogen ions combine with the bromide wns to produce hydro-
bromic acid.
2H++2Br- = 2HBr.
The quinone combines with sodium sulphitt to form the mono and di-
sulphonates of quinone.
Thus the oxidized form of the developer disappears and the ratio [Ox]/
[Red] drops. The redox potential is consequently lowered, having the remit
of increasing the development potential.
In the presence of aerial O:Jt.;ygen, colourless hydroquinone monosulphonate
and sodium sulphate are formed by the action of sulphite on hydroquinone:
h yd roquinone sodium oxygen sodium hydroquinone sodium sodium

sulphite monosulphonate sulphate hydroxide
In the absence of sulphite, strongly coloured brown oxidation products

are formed. <29 l
The sulphite also prevents autoxidation of the developing agent. There are,
however, other inhibiting substances which are more effective such as
cysteine, thioglycolic acid and especially ascorbic acid. <30 >
Action of sulphite on emulsion speed. The sulphite increases the speed of
emulsions more effectively if they are incompletely developed. The effect is
marked with double-charged developers such as hydroguinone, especially if
the oxidation products are accelerators. It is less with single-charge developers
(metol).
This action of sulphite appears to be due to the solution of the surface layer
of the grains, exposing the development centres and probably forming
argentisulphites. Thiosulphate produces a similar effect at a much lower con-
centration.
Sulphite is therefore a solvent. A 50-g.p.L. solution dissolves 0·9 g of silver
bromide and 2 ·1 g of chloride.
To sum up, the addition of sodium sulphite to a developing solution has the
purposes:
(1) To preserve the developer by inhibiting autoxidation and slowing down
aerial oxidation.
(2) To stabilize the reduction of the silver salt by removing the oxidation
product as it is formed, as the sulphonate.
(3) To act as a solvent (see para. 43/5).
Solvents of silver halides, like sulphites, bromides, thiocyanates, thio-
sulphates or ammonia, when added to developers, produce silver complexes
which, in turn, result in physical development (see para. 71), which is slower
than chemical development. (30b)
41. Modification of the potential barrier .

We have already seen that the silver bromide crystal is surrounded by a
double barrier of Br- ions and K + ions. The height of this potential barrier can
be increased or reduced with retarders or accelerators.
1. Soluble bromide. A small quantity of potassium bromide is normally
added to a new developer to avoid chemical fog produced by a violent reduc-
tion of silver bromide even without exposure. Development is also slowed
down by the addition or formation of soluble bromide resulting from the
reduction of silver bromide. A used developer necessarily contains a large
amount of bromide and cannot therefore develop normally even though it
still contains a high proportion of developing agent. The emulsion speed is
therefore greatly reduced.
The action of soluble bromide in development is due to the raising of the
potential barrier following the mass action of Br- ions. This barrier protects
the unexposed parts of the crystal but at the same time lengthens the induc-
tion period.
Soluble bromide has no influence on developers with a zero charge.
2. Devtlopment accelerators. The opposite effect to the addition of potas-
sium bromide-the reduction, cancellation or reversal of the potential
barrier-can be achieved by adding certain strongly electroactive compounds,

especially cationic surface active agents of the ammonium quaternary type,
in the concentration of 0·05 %· In this way development is greatly accelera-
ted-the period of induction being considerably reduced.
The most interesting among the cationic surface active agents are lauryl-
pyridinium chloride (or sulphate) used by Lottermoser and Steudel in 1938, <31 >
laurylpyridinium p-toluene-sulplumate, {3-pheny lethy l-rx -picolinium bromide.
Laury! pyridinium sulphate Cetyl trimethylammonium bromide

(Repellat T 59) (33) (Cetavlon) (34)
Dimethyl-benzyl-laury l am m onium chloride

(Zepyrol) (35)
Tests have been made with ammonium derivatives having the structure: <32 )
[CH 3 -(CH 2) - N
n
= RR'R"]+X-.
It is probable that the developer oxidation products, which, for the smooth
progress of development, must, as we have seen, have been adsorbed on to the
development centres, act by reducing the potential barrier. It is the same
with the weakly-charged developers, which, associated with other developers,
facilitate development and reduce the induction period: this is the pheno-
menon of superadditivity (which will be examined in the following
chapter).
Finally it should be noted that certain dyes (safranines, pinacyanols, etc.)
act as development accelerators. They are used in some ultra rapid developer
formulas. (See following chapter.)
42. Induction period

The intitial phase of development, the period which precedes the start of
development, is called the induction. It is logically the result of the existence
of the negative potential barrier which surround each silver bromide crystal.
The charges which accumulate there are not neutralized and the barrier is
broken down, in a greater or less time, denoting the induction period.
James<36 l has shown that the induction period increases with the charge of
the developer: a developer with a charge of 2 has more difficulty in
overcoming the potential barrier than a developer with a charge of 1.
Development as a whole takes much longer as the developer has a stronger
electric charge, or alternatively a high valency.
Charge (or valency) 0: diaminodurene, substituted p-phenylene-diamines,
etc.
Charge (or valency) 1: metol, p-aminophenol, dimethyl-p-aminophenol,
p-aminocarvacrol, pyrocatechin.
Charge (or valency) 2: hydroquinone, glycine, ascorbic acid, ferrous
oxalate, etc.
Charge (or valency) 3: sodium hydroquinone-monosulphonate.
The added bromine ions which raise the barrier have less effect when the
developer has a low charge.
Burton stated that the apparent induction period is longer for the deep
silver bromide crystals than for the surface crystals, the difference can be
30 sees. In addition it is possible that the small centres are less effective for
an equal surface than the large silver specks making up the latent image.
The induction period increases with the dilution. However, it is nil with
the zero charge reducers even when very dilute. It decreases with the exposure
and the bromide concentration as well as with fast colour sensitive emulsions;
the dyes reduce the potential barrier.
The addition of quinone to hydroquinone in the absence of sulphite
accelerates development (acceleration due to the decomposition products of
quinone in alkaline solution). With less rapid emulsions and medium contrast
it has been stated that lower curved part of the development curve disappears
with increase of contrast at the beginning of reduction.
The sulphite, which destroys the oxidation products of the developing
agent, prevents the preceding phenomenon from taking place, and conse-
quently lengthens the toe of the characteristic curve.
The addition of bromide to an unbromided developer, during development,
changes the rate but not the maximum density except where the addition
is excessive. In the latter case, a variation in the number of developed grains
occurs, due to the increase in the induction period of the grains which have
not, at that moment, been affected.
James has also given evidence of the influence of the charge of the developer
on the speed: the densities corresponding to the low exposures are higher
with the reducing ions which have a single charge, and still greater with the
zero charge ions. Thus at y = 0·65 the following H and D speeds are ob-
tained: zero charge 65, single charge 32, double charge 2.
On the other hand, a reduction of the potential barrier with the benefit of an
increase in speed by adding a safranine or pinacyanol dye, or even with thallous
ions, is only effective with the double-charge developers (hydroquinone).
Some action is produced by preliminary immersion in a 0·01 M solution of
lead acetate. However, better results are obtained with a 0·001 M solution of
a dodecylpyridinium salt. (3 7 )
The effect of the developer charge is mainly apparent for the low exposures.
It becomes negligible with large exposures.
For a mathematical study of the kinetics of development, see Bagdassarian's

work.<38 >
1. Reinders W.: Jl. Phys. Chem., 1934, 38, 783.

2. Some American writers use the opposite sign for the redox potential: the reducing
activity then increases with the latter.
3. Abribat M.: Sci. et Ind. Phot., 1944, 15, 204.
3b. Stated by A. & L. Lumiere in 1911: Bull. Soc. Fr. Phot., 1911, 168-171.
4. Schwarz and Urbach: Sci. et Ind. Phot., 3, 298-5, 36; Evans and Hanson: Sci. et
Ind. Phot., 8, 329 and 361.
5. Sheppard and Meyer: J.A.C.S., 1920, 689.
6. James T. H. and Vanselow W.: J.A.C.S., 1952, 2374-2377.
7. Luther: Sci. et Ind. Phot., 8, 247(11).
8. Staude H.: Sci. et Ind. Phot., 10, 336.
9. Staude H. and Brauer E.: Comm. to the 'Bunsen Gesellschaft (Photochemie),'
Lindau, May 1952.
10. Rabinovitch A.: IX Gong. Int. Phot., 1935, 327.
11. J.C.S., 1943, 338.
12. Cf. Rzymkowski J.: Sci. et Ind. Phot., 1950, 125 and 1951, 1.
Rzymkowski found that titanous chloride does not develop despite its con-
siderable reducing power, as it is not adsorbed, whereas potassium titano-oxalate,
which is an adsorbable complex, is a developer. Abribat and Pouradier found, on
the contrary, that a developer can only develop very slowly when its molecules
are too big and diffuse slowly; ex. ferrous pyrophosphate.
13. Jaenicke W., Kruger A. and Hauffe K.: Zeits. Phys. Chem., 1951, 161.
14. Levenson G. I. P. and Tabor J . H.: Sci. et Ind. Phot., 1952,295.
15. Berry C. R.:Jl. Opt. Soc.Amer., 1950,615.
16. Keith H. D. and Mitchell J. W.: Phil. Mag., 1953, 877.
17. Kohlschtitter: Zeits. Elektrochem., 1932, 213 and 345.
18. Samartsev: Doklady, 1935, 2, 478; Vagramyan: Doklady, 1939, 22, 243.
19. Gorbunova K. M. and Dankov: Doklady, 1945, 48, 15.
20. Gorbunova K. M. and Zhukova A. L.: Zh. Fiziki. Kimii, 1949, 603-615.
21. Boissonas C. G.: C.R., 1950, 1270-1280. Summary in Sci. et Ind. Phot., 1950,
269; 1951, 351.
21 b. Vuille R.: Helv. Chim. Acta, 1954, 37, 2264-2271.
22. Von Ardenne M. : Zeits. Angew. Phot., 1940, 14-20.
23. Hall C. E. and Schoen A. L.: Jl. Opt. Soc. Amer., 1941, 281-285.
24. Kuster A.: Zeits. Wiss. Phot., 1949, 191-200.
25. Selme P.: Sci. et Ind. Phot., 1951, 361.
26. Hamm F. A. H. and Comer J. J,: Jl. Appl. Physics., 1953, 1495 .
26b. Bradley: Sc. Ind. Phot., 1954, 319.
26c. Konig: Z eits. Phys., 1951,491.
27. Pouradier J. and Abribat M.: Sci. et Ind. Phot., 1944, 206.
28. This classical scheme is the most convenient. In fact, the study of the absorption
spectra always shows that there is greater reactivity due to the release of the1r
electrons. The displacement of the absorption band is less for the non-developing
tsomers.
29. The preserving action of sulphite on the developing agent is mutual.
30. Lu Valle}. E. and WeissbergerA.:J.A.C.S., 1947, 1821; Summ. in Sci. etind.
Phot., 1948, 108.
30b. James T. H. and Vanselow W.: Phot. Sci. Techn., 1955, 2, 135-143.
31. Lottermoser and Steudel: Koll. Zeits., 1938, 319.
32. Abribat M.: Sci. et Ind. Phot., 1952, 234.
33. Produit Chimiques de laMer Rouge (Mulhouse) Bohme: Fettchemie (Chemnitz).
34. Imp. Chern. Ind., London.
35. I. G. Farben (Ludwigshafen).
36. James T. H.: Jl. Franklin Inst., 1945, 83.
37. James T. H. and Vanselow W.: Sc. Ind. Phot., 10 (2), 271.
38. Bagdassariane C.: Acta Physicochim. (U.S.S.R.), 1945, 20, 441-458. Summary in
Sci. et Ind. Phot., 1946, 87-90.
Chapter VI
THE DEVELOPING SOLUTIONS

43. Composition of the developing solution
The developing solution, as we have seen, is a solution of adsorbable develop-
ing agents having a redox potential less than 120mV. This potential can in
fact be negative, between zero and -200mV for example: as the potential
becomes lower, so the activity of the developer increases.
In practice the developing solution generally contains:
1. An organic reducing agtnt which is the essential constituent of the bath.
Its function is to convert the silver ions Ag+ of the silver bromide crystals
into silver metal, by supplying the necessary electrons.
The number of reducing, or developing agents, is extremely great, and
their chemical constitution will be studied in a following chapter. The most
widely used are hydroquinone and metol, but p-aminophenol, diamino-
phenol, glycin, pyrogallol, p-phenylenediamine are also useful.
The concentration of developing agent is of the order of 5 g per litre.
2. An alkali, whose purpose is to maintain the reduction potential at a
sufficiently low value by working at a high pH (that is, alkaline) for we know
that the redox potential is decreased as the pH is increased. In addition, the
pH must be kept constant, and by using excess alkali, the hydrobromic acid
liberated during the development reaction is neutralized.
Generally, sodium carbonate and borax are used; less frequently, caustic
soda.
The pH depends on the nature of the alkali.
3. A preservative: sulphite which also has the function of controlling
development. The sulphite is an essential constituent of the bath. The amount
used can vary from 25 to 100 g per litre. If the quantity is reduced to 2 g per
litre the oxidation products of the developing agent are not completely
neutralized and tan the gelatin in proportion to the image density. In the third
part formulas for these tanning developers will be given.
4. An anti-Jogging retarder: potassium bromide. Quantity: 0·3-2 g per litre.
During development the concentration is however increased, the bromide
being provided by reduction of the silver salt to such an extent that the quan-
tity added to the new bath becomes negligible compared with the consider-
able quantity resulting from prolonged use of the solution: the slowing down
of development becomes greater and greater. At the same time, a reduction
in sensitivity of the emulsion occurs and the contrast is increased.
60
Organic anti-foggants used in stabilizing emulsions can be used to replace
potassium bromide. Those currently used are 6-nitrobenziminazole nitrate
and benzotriazol. Concentration 0·25-0·5 g per litre. They are necessary for
development at high temperatures.
5. A silver bromide solvent. The one most frequently used is the sulphite
itself which has this action. It can be used up to 100 g per litre. But it is also
possible to add in low concentration potassium thiocyanate KCNS; sodium
thiosulphate or even ammonia. A high solvent action encourages the formation
of fine grains of silver.
p-phenylenediamine is at the same time a developer and a solvent (less than
ammonia). This property is attributable to its oxidation products.
6. A calcium sequestering agent. This is optional, most frequently it is
omitted.
7. A . wetting agent, also optional.
44. Water used for developers

Tap water or drinking-water is not chemically pure: it contains among other
things calcium bicarbonate and sulphate, chlorides, iron oxide, silica, carbon
dioxide, and dissolved oxygen. Also traces of hypochlorite are added to sterilize
it. The degree of acidity varies according to the source.
The calcium in the water is precipitated in a newly prepared developer and
makes it turbid. Calcium carbonate and sulphite which are deposited on
standing as whitish mud, are not very inconvenient: the solution can be
decanted and filtered. But the smears of calcium and other products which
may appear after drying from drops adhering to the washed films, are com-
posed of these materials.
Silica can be formed in acid-fixing baths as fine colloidal particles which
stick to the gelatin and spoil the surface after glazing.
Dissolved oxygen is the most awkward constituent present as it leads to
premature oxidation of the developer.
Unusual impurities: these are hydrogen sulphide, rust from defective pipes,
and copper from water stills. These are very objectionable.
Ordinary drinking water must not contain more than 60 mg of chloride per
litre. It contains 5-30 mg of sulphuric acid as sulphates. It:s content of organic
matter must be less than 2 mg (expressed as oxygen) or less than 40 mg of
actual material; with a higher concentration, the water under consideration
is suspect.
The presence of ammonia (and of nitrite) is an unfavourable indication.
The water has probably been fouled by animal materials.
Water are classed by degrees of hardness (1 degree being 10 p.p.m. calcium
carbonate). This depends on the behaviour of a sample towards a standard
soap solution and the persistence of the lather. Ordinary drinking-water has
a hardness of less than 30°. Water of 60° hardness or above is not suitable
for any purpose.
For developers it is preferable to use boiled water. Boiling expels the dis-
solved gases and precipitates part of the calcium as carbonate. Distilled water
is not necessary. In the absence of boiled water, ordinary tap water can be
used without harmful effects.
45. Hard Waters
Hard water produces deposits of calcium carbonate in developers and sensttlve
layers. With borax developers, calcium sulphite is formed (lower pH). Henn and
Crabtree have pointed out that 0·3 g per litre CaC1 2 in a normal developer produce
this effect, 0·07 g per litre in a borax developer and 1·7 g p er litre in a caustic bath.
The calcium salts can be eliminated by precipitation (this does not remove the
calcium from the gelatin) or they can be sequestered by forming innocuous complex
ions with citric or tartaric acid (5-10% ).
This effect is dependent upon the pH. It is better to use sodium hexametaphosphate
(NaPO 3 ) 6 , pyrophosphate or tetraphosphate Na 6 P 4 0 13 • These compounds are hydro-
lyzed in warm water to the orthophosphates and lose their sequestering power. Of
the three compounds, only the tetraphosphate has no effect on the pH of the bath,
and is therefore preferable to the other two; in addition to which, it is stable in the
solid state. For carbonate and borax developers, about 2 g per litre is used, and about
0·5 g for acid developers. Under tropical conditions, hydrolysis is prevented by the
addition of 2-4 times the weight of sodium citrate (Jl. Soc. Mot. Pict. Eng., 1944, 426).
Sodium hexametaphosphate in a 1% solution has a pH of 7 ·2; it is known under the
name of Calgon.
The crystalline pyrophosphate has the formula Na4P 20 7 • 10 H 20. Its pH in 1%
solution is 9 ·8.
Tripolyphosphate (Giltex 0) has the formula Na 5P 3 0 10 • pH = 9·8.
A simple method for obtaining calcium-free water is to soften it by passing through
one or more ion exchangers in special apparatus filled with permutit or, better, with
certain synthetic resins. With permutit the calcium is replaced by sodium, and the
exchanger is regenerated with a solution of sodium chloride. With the synthetic resins
the metal and acid radicals are substituted by Hand OH, that is with water. Regenera-
tion is then carried out with soda and hydrochloric acid.
46. Developer alkalis

We have said that the energy of a developer increases with its alkalinity. In
order of increasing alkalinity we have: borax, sodium metaborate, sodium
carbonate, caustic soda.
Borax is sodium tetraborate Na 2 B40 7 • 10 H 2 0. Slightly soluble cold, it
should be powdered before dissolving.
Metaborate (Kodalk) is obtained by fusing borax with caustic soda. Its pH
is greater than that of borax. It is very soluble in water.
Borax or metaborate are frequently used together with boric acid H 3 B0 3
to give a buffer, which however is not very effective.
Concentration
2% 4% 6% 8%
Borax pH 9·4 pH 9·6
Meta borate ph 10·4 pH 10·6 pH 10·7 pH 10·8
Boric acid pH 4·5 pH 3·9
Sodium carbonate. Sodium carbonate Na 2C0 3 is generally used in the
anhydrous form or as the monohydrate Na 2C0 3 H 20. The ordinary crystal-
line form Na 2C0 3 10 H 20 effloresces rapidly in air, and its use is not
advised.
100 g of anhydrous sodium carbonate is equivalent of 117 g of the mono-
hydrate and 275 g of the decahydrate.
Caustic soda NaOH is a very strong alkali which is used in high contrast
developers. It is dangerous to handle as it attacks the skin and gelatin. It is
preferably used in granular form. Caustic soda is deliquescent, and in air is
quickly converted to carbonate; it must therefore be kept in well-stoppered
bottles:
Trisodium phosphate Na 3P0 4 12 H:P· This compound, not frequently used,

owes its alkalinity to its ready decomposition, in solution, into disodium
phosphate and caustic soda.
Potassium salts. The potassium alkalis, although having similar chemical
properties to the sodium compounds, alter the developing properties of the
solution. (I) The K + ions are photographically more active than the Na+ ions,
particularly towards the internal latent image of the silver bromide grains.
The emulsion sensitivity is increased. The simultaneous presence of K+ and
Na+ ions increases the efficiency of anti-fogging compounds.
Potassium carbonate K 2CO 3 is available as a deliquescent anhydrous pow-
der. Its molecular weight is 148 compared with 106 for sodium carbonate
and therefore chemically 130 grams of potassium carbonate must be used in
place of 100 grams of sodium salt. However, as it is photographically more
active, 80 grams of potassium carbonate are sufficient to replace 100 grams
of anhydrous sodium carbonate.
Caustic potash KOH has the same uses as caustic soda. It also has the same
physical properties. 100 g of anhydrous sodium carbonate corresponds photo-
graphically to 10·4 g of caustic soda and 14·5 g of caustic potash.
47. Sulphite
Anhydrous sodium sulphite with the formula Na 2S0 3 is stable when dry. It
has a higher purity than the crystalline sulphite Na 2 S0 37H 20 which is
efflorescent and readily oxidized to sulphate.
100 g of anhydrous sulphite is equivalent to 200 g of crystals.
Sulphite solutions of less than 20 % concentration are rapidly oxidized. The
oxidation is retarded in the presence of another reducing agent by a reciprocal
anti-oxidation action.
Instead of sulphite, potassium metabisulphite K 2S 20 5 can be used by first
adding a caustic alkali which converts it into neutral sulphite. Bisulphite
NaHS0 3 as the commercial 32 % lye can also be used. 100 cc of bisulphite
exert the same action as 47·5 g of potassium metabisulphite. Do not use
sodium metabisulphite which is not so pure, and less stable than the potas-
sium salt.
100 g anhydrous sodium sulphite are equivalent to: 200 cc sodium bisul-
phite lye+32 g caustic soda or 95 g potassium metabisulphite+32 g
caustic soda (or 79 cc 30% lye).
64 PHOTOGRAPHI C CHEMISTRY
Conversely 100 cc of bisulphite can be replaced by 50 g of sulphite and

10·5 cc (19·3 g) sulphuric acid dissolved in 65 cc of water.
Solubility of anhydrous sodium sulphite in a litre of water: 210 gat 10°C,
280 g at 20°C, 380 g at 30°C.
We would finally note that acetone added to a sulphite solution of hydro-
quinone with no alkali present forms the compound [2(NaHS0 3)2(CH 3-
CO-CH3)] and the sodium salt of hydroquinone C 6Hi0Na) 2 : the latter
behaves as a developer in alkaline solution.
48. Developers preparation
Developers are prepared in units of 1, 2, 5 litres or more.
Dissolving. Use a flask three-quarters full of tepid boiled water (50°C). Add
successively the following products in the order given: metol, sulphite,
hydroquinone, carbonate, bromide.
Make sure that each item is completely dissolved before adding the next one.
After each addition shake the flask.
Add each item gently, sprinkling it with the aid of a sheet of clean paper.
To finish preparation: Make up to the required volume using cold water.
Stir and leave for several hours. Check that the volume is correct and if
necessary filter through paper which should be pleated and placed in a funnel
the same size as the paper. 500 cc or 1,000 cc bottles should be completely
filled with the solution and carefully stoppered.
If the developer is poured directly into a tank, cover with a floating lid.
Aerial oxidation fog: even when not used a developer when exposed to the
air becomes oxidized by the oxygen in the air. It is particularly the hydro-
quinone which is affected. At the same time sodium sulphate is formed
together with caustic soda and tanning organic compounds. Each reduction of
sulphite in a developer, whether accidental or not, encourages the oxidation
of the developing agent by loss of protective power. A bottle of partly used
developer becomes more and more brown as it is oxidized and gives off an
unpleasant smell.
Packed developers: ready prepared photographic products are commercially
available for the preparation of developing and fixing baths. Even when these
products are already weighted and mixed, great care is necessary when using
them. In general they are packed in temporary paper or card containers and
unless they are to be used at once it is advisable to transfer the contents to
bottles.
Packed developers for 250 cc quantities are often marketed in glass tubes;
these glass tubes have a separating division; one side is filled with metol and
hydroquinone, the other with carbonate, sulphite and bromide. The metol
hydroquinone mixture is fir1't dissolved in water, then the remainder of the
packet.
49. Energy of a developer
An energetic reducer develops all parts of the image rapidly, both shadows
and highlights: the resulting contrast is necessary low and the image appears
greyish. Diaminophenol and metol have this action.
A less energetic reducer first develops the parts of the image which have
had the greatest exposure; the contrast then becomes great. This happens with
hydroquinone.
Dilution of the developer slows down development, promotes the develop-
ment of the less exposed areas, and reduces the contrast.
The addition of bromide slows down development, but on the contrary,
prevents the development of underexposed areas (reduction of sensitivity)
and increases the contrast.
Instead of measuring the redox potential, developing agents are often
classified by their ability to withstand the retarding influence of a given quan-
tity of potassium bromide. The greater the reducing power, the less the loss
of density caused by the addition of bromide, and conversely. The following
table reproduces the Nietz-Tschibissoff series <2 > in which the reducing power
of hydroquinone is taken as 1. The higher the number, the higher the reduc-
mg power.
Ferrous oxalate 0·3
p-phenylenediamine HCl (without alkali) 0·3
p-phenylenediamine HCl (with alkali) 0·4
Methyl-p-phenylenediamine (without alkali) 0·7
Phenylhydrazine <1
Hydroquinone 1
2-hydroxhydroquinone >1
Glycin 1·6
Hydroxylamine 2·0
Toluhydroquinone 2·2
Methyl-p-phenylenediamine (with alkali) 3·5
Benzy1-p-aminophenol <5
Dimethyl-p-phenylenediamine HCl 5
p-hydroxydiphenylamine <6
p-aminophenol 6
Chlorohydroquinone 6-7
p-amino- o-cresol 7
Dibromohydroquinone 8
p-amino-m-cresol 9
Dimethyl-p-aminophenol (sulphate) 10
Dichlorohydroquinone 11
Pyrogallol 16
Metol 20
Bromohydroquinone 21
p-methylamino-o-cresol 23
2 : 4-diaminophenol (with alkali) 30--40
Thiourea 50
It is easy to state, after this table, that the introduction of CH 3 into the
nucleus of hydroquinone doubles the reducing power in the resulting tolu-
hydroquinone. A methyl group substituting an amino hydrogen atom of
p-phenylenediamine (methyl-p-phenylenediamine) increases the reducing

power from 0·4 to 3·5-almost nine times greater; two methyl groups give
dimethyl-p-phenylenediamine and the index of reducing power increases
from 3·5 to 5. The introduction of halogens increases the developing
energy hydroquinone = 1, chlorohydroquinone = 6, bromohydroquinone
= 21.
Influence of temperature. Raising the temperature increases the developing
potential (by a corresponding decrease in redox potential). The apparent
sensitivity of an exposed emulsion is doubled if the temperature is increased,
for example, from 15°C to 33°C.
50. Negative developers with a single developing agent

Developing solutions containing only one developing agent are less
frequently used than solutions containing a mixture of two developing
agents. They giv~, however, excellent results each having its own particular
characteristics.
1. Metol. Metol (Elon, Genol, etc.) is found as fine white crystals which are
insoluble in concentrated sulphite solutions: this is why it must be dissolved
first. Metol has a high reduction potential which rapidly brings up the low
exposure regions, that is the shadows, whilst it generally gives low contrast
when it is used alone.
The impurities frequently present in metol can produce dermatitis. To cure
this, it is recommended to soak the hands for more than an hour in hot water.
Water to 1000 cc
Metol 15 g
Sodium sulphite anh. 75 g
Potassium carbonate 50 g
Potassium bromide 1g
Immediately before use take one part of this solution and one or two parts
of water. Development time at 18°C, 4--6 minutes. The image appears
quickly, after about 4--10 seconds.
2. Pyrogallol. Pyrogallol i~ found as colourless needles which are very
soluble and oxidize very rapidly in solution (which becomes brown). It can
also stain the gelatin and the fingers. Pyrogallol baths can only be used once.
Stock solutions are therefore prepared with bisulphite or metabisulphite and
a little bromide. Just before use they are mixed with a solution of sulphite
and a solution of sodium carbonate. If the stock solutions are concentrated
they are diluted with a large quantity of water. The developer obtained in this
way changes rapidly. In preparing the concentrated stock solution of pyro-
gallol the latter must not be added until the metabisulphite has dissolved.
The following formula (D1) gives vigorous developers whose energy is not
reduced by dilution. The image appears slowly but the gamma can reach a
high value if the time is extended. A yellowish residual organic stain image
is formed at the same time as the silver image.
THE DEVELOPI N G SOLUTIONS 67
A. Water to 1000 cc
Sodium metabisulphite 10 g
Pyragallol 60 g
B. Water to 1000 cc
C. Water to 1000 cc
Sodium carbonate anh. 7S g
For development take:
Tank: 1 part of A, Band C+ll parts of water; (12 minutes at 18°C).
Dish: 1 part A, B and C+ 7 parts of water; (6 minutes at 18°C).
In this formula sodium metabisulphite can be advantageously replaced by
the more stable potassium salt.
3. Jlyrocatechin
A. Water to soo cc
Sodium sulphite anh. 3S g
Pyrocatechin 12 g
B. Water to soo cc
For use take 1 part of each solution.
4. Glycin. Glycin (Kodurol) is found as small mica-like plates slightly
soluble in the absence of alkali or sulphite. Glycin must therefore be dissolved
after the sulphite. Glycin gives developers which are very resistant to oxida-
tion and suitable for prolonged use in a dish. A large quantity of stock
solution can therefore be prepared. The more the developer is diluted, the
softer the results. Glycin baths are very sensitive to potassium bromide and
to temperature. Furthermore, when they contain too much sulphite there is a
risk of producing dichroic fog. Potassium carbonate gives a more powerful
developer than sodium carbonate.
KL Agfa
Water to 1000 1000 1000 cc
Sodium sulphite anh. 3 100 12S g
Glycin 3 40 so g
Sodium carbonate anh. 6 80
Potassium carbonate so 2SO g
Dilution Undiluted +3 parts +4 parts
water water
Development time at 18°C 1S-2S 8-10 S-10 mins.
S. p-Aminophenol. p-aminophenol is a readily oxidized compound which
needs an adequate amount of sulphite. The developers must be kept in well-
stoppered bottles. The hydrochloride is more soluble than the free base, but
as it is precipitated by alkalis there is no point in using it. The caustic alkalis
form very soluble phenates which can be kept in concentrated solution: for 100 g
of p-aminophenol, 21 g of caustic soda, 36 g of caustic potash or 6·4 g of
D
lithium hydroxide (rarely used) are needed for this. The p-aminophenol
developers are sensitive to potassium bromide.
A B C D
Water to 1000 1000 1000 1000 cc
Sodium sulphite anh. 70 100 7S so g
p-aminophenol base 8 10 10 8g
Sodium carbonate anh. 60 so - g
Potassium carbonate so g
Caustic soda 2·1 - g
Lithium hydroxide 4 - g
The formula A develops in 3-6 minutes. Formulas Band Care more active.
If the concentration of C is doubled, a bath is obtained which develops in
oue minute.
51. Diaminophenol developers

Some developing agents have a sufficiently low redox potential in neutral or
acid solutions to be able to develop without the addition of alkali. The
presence of sodium sulphite is sufficient to bring about reduction.
For this, it is necessary that the developing agent molecule should contain
at least one and preferably two, amino groups, as with diaminophenol.
Diaminophenol (or amidol) is used as the hydrochloride, found as a colour-
less or blue-grey crystalline powder which is very soluble. It is a very powerful
reducer which can develop in neutral or acid solution. Diaminophenol acts mainly
at the bottom of the emulsion layer.
In alkaline solution it is rapidly oxidized. Stock solutions can be prepared
with bisulphite and before use are neutralized by adding a solution of carbon-
ate. The following formulas are generally preferable.
Neutral (Sodium sulphite anhydrous 100 g
Formula Diaminophenol 20 g
Water to 1000 cc
This solution keeps in full, well-corked bottles. For use, take one part of
solution to three parts of water. The image appears in about 12 seconds and
development is continued for 4-6 minutes. In cases of overexposure add up to
20% of a 10% solution of potassium bromide.
Sodium bisulphite 2S cc
Acid Sodium sulphite 20 g
Formula Diaminophenol Sg
( Potassium bromide 2g
Water to 1000 cc
This bisulphite bath keeps better than the previous one.
52. Superadditivity of developers

Two developers are said to be superadditive when used together, if the
sum of their simultaneous action is greater than the sum of their actions
considered separately. The phenomenon of superadditivity is mainly
apparent with short development times. The most common example is
that of the metol-hydroquinone system.
This phenomenon was first noticed by Luppo-Cramer. Reinders and
Beukers have observed that metol serves to shorten the induction period of
development by lowering the potential barrier surrounding each grain of
silver bromide. The hydroquinone takes no part until this has happened.
T. H. James<3 > has put forward the hypothesis that superadditivity is
only possible if the two developing agents have different electrical charges
(or free valencies). That with the low charge (like metol) reduces the
potential barrier and starts off development. It is not until then that the
developer with the higher charge (hydroquinone) can take part in the
reduction.
Thus many developers, with a charge of 1 or 0, can be used with hydro-
quinone (charge 2) or better with sodium-hydroquinone-monosulphonate:
these are metol, hydroxylamine, diaminodurene, and Phenidone. The two
latter show stronger superadditivity than metol. R. W. Henn <4 > has made
many tests with various substituted p-aminophenols.
Levenson's theory. The preceding conception in which metol alone acts
first has been criticized by G. I. P. Levenson. <5 > According to him, the
hydroquinone takes part in the reduction from the beginning of development,
its action being catalyzed by the metol, confirmed by the fact that hydro-
quinone can only develop if it is adsorbed via an oxidation product (see
Theory of development). The hydroquinone regenerates the metol by reducing
its oxidation product, p-methyl-quinone-imine. This action is furthermore
dependent on the conversion of the two oxidation products (of metol and
hydro quinone) to the sulphonates, by the sulphite. Thus a change in the
structure of hydroquinone such as the inclusion of a CH 3 groups tends to
slow down the sulphonation of its oxidized form and reduces the super-
additivity. Similarly, a change in the structure of metol, which, on the con-
trary, accelerates the sulphonation of the oxidized form also reduces the super-
additivity. I
To sum up, a mixture of developers is superadditive when one of them can
readily reduce the oxidized form of the other, and when the sulphite reacts less
rapidly on the former than on the latter.
Axford and Kendall have shown that at a pH of 8·2, hydroquinone is in-
active but regenerates phenidone from its coloured oxidation products.
In the case of metol, Levenson has shown that it dissociates differently
depending on the pH:<s>
Cation OH-C 6H 4-HN 2 • CH 3+ charge +1
Metol Hybrid O-C 6H 4-NH 2 • CH 3 charge 0
{ Fr~e base OH-C 6H 4-NH. CH 3 charge 0
Amon O--C 6 H 4-NH. CH 3 • charge -1
The cation is formed from pH 8·3 but towards pH 10-4 there will be an
equivalent of anions and free base plus hybrid.
53. Metol-hydroquinone developers

Metol-hydroquinone developers are used more frequently than others because
of their versatility given by the phenomenon of superadditivity. The formula
variations are infinite; however, experience has shown that it is better not
to deviate too far from certain proportions if maximum sensitivity, average
contrast, little fog, acceptable grain and good keeping qualities are required.
Universal metol-hydroquinone formula
The following formula is the most suitable one for the majority of emul-
sions-negative or positive. It produces optimum speed without excessive
contrast or very coarse grain.
Water to 1000 cc
Metol 2g
Hydroquinone 5g
Sodium carbonate anh. 25 g
Development time at 18°C: 5 minutes for average contrast, 10 minutes for
underexposed images. To reduce the contrast, dilute with an equal part of
water. Increasing the metol with a corresponding reduction of hydroquinone
also reduces contrast.
Among the other formulas we would mention D 72 which is in current
use, and MQ.80 which used to be used for rack development of films.
D72 MQ.80
Water to 1000 1000 cc
Metol 3 2g
Sodium sulphite anh. 45 18·75 g
Hydroquinone 12 0·5 g
Sodium carbonate anh. 62·5 12·5 g
Potassium bromide 2 0·75 g
D 72 is used diluted with an equal part of water. Development time, 5
minutes in a tank and 4 minutes in a dish. The sensitivity obtained is less
than that given by the preceding formula and the grain is coarser.
Formulas for under-exposed images
P.G. D 82
Metol 1·75 14g
Sodium sulphite anh. 45 52·5 g
Hydroquinone 4·35 14g
Sodium carbonate anh. 22 - g
Potassium bromide 0·9 9g
Caustic soda 9g
Alcohol (methylated spirit) 48 cc
Development time at 18°C 12 mins. 4-5 mins.
D 82 keeps for only a few days in stoppered bottles and for only two hours
in a dish.
54. Pyro-metol developer

The pyro-metol developer whose preparation is quite complicated, can be
used for negative development. It is used to obtain maximum sensitivity.
The D 7 formula is typical:
A. Water to 1000 cc
Metol 7·5 g
Sodium metabisulphite 7·5 g
Pyrogallol 30 g
B. Water to 1000 cc
C. Water to 1000 cc
This developer can be used two or three weeks.
For use take:
Dish: 1 part A, 1 part B, 1 part C and 8 parts water. Develop 7-9 mins.
Tank: 1 part A, 1 part B, 1 part C and 13 parts water. Develop 9-12 mins.
To maintain the volume of solution add 1 part of 1, 1 part of B, 1 part of C
and 4 parts of water.
55. Phenidone developer

Ilford's Phenidone is a new developing agent disclosed by Kendall which can
be used together with hydroquinone. It produces even greater superadditivity
than metol. Used alone, on the other hand, it gives very low contrast.
Phenidone, which is 1-phenyl-3-pyrazolidone has a zero charge at low pH
and a charge of 1 at a higher pH. It initiates development so rapidly that
the induction period is practically nil. <7 > It appears to form a positively
charged intermediate oxidation product which helps to reduce still further
the potential barrier and facilitates the adsorption of the developing agent
ions which are negatively charged.
Axford and Kendall <8 > have shown that the maximum development rate is
reached when the developer contains 7% of Phenidone compared with
hydroquinone. This rate is SO% faster than that of the metol-hydroquinone
combination (which reaches its maximum rate with 28 % metol), the two
measurements being made at pH 10·4. Unfortunately, Phenidone tends to
produce fog with high-speed emulsions. This disadvantage can be overcome
by adding 0·15 g of benzotriazole per litre of developer.
The advantage of Phenidone over metol appears to be, apart from its greater
development rate, a greater consistency of sensitivity and a high activity at
relatively low pH values The latter property enables high contrasts to be
obtained with X-ray materials in a less alkaline bath than is customary for
metol hydroquinone, and even an equivalent effect to that of a hydroquinone

caustic bath.
In the preparation of Phenidone-hydroquinone solutions the hydroquinone
must be dissolved before the Phenidone, which is previously mixed with 2·5
times its weight of potassium metabisulphite. Phenidone does not appear to
produce dermatitis like metol.
Universal formula ID 62< 9 >
Water to 1000 cc
Hydroquinone 12 g
Phenidone 0·5 g
Sodium carbonate 60 g
Potassium bromide 2
Benzotriazole 0·2 g
For development, add water in the following proportions:
Emulsion Developer Water Development time
at 20°C
Chloride paper 1 + 1 45-60 sees.
Bromide paper 1 + 3 1!-2 mins.
Films (dish) 1 + 3 2-4 mins.
Films (tank) 1 + 7 4--8 mins.
56. Combined developers

Metol can develop over-exposed images without alkali. If it is combined
chemically with hydroquinone its activity is increased and the resulting
product, Metoquinone (Lumiere) develops normally in neutral solution.
Water to 1000 cc
Metoquinone 10 g
Metol has also been combined with chlorohydroquinone (Chloranol) and
p-phenylenediamine with hydroquinone (Hydramine). These compounds are
not used any more but Meritol (Johnson's) is made and is a combination of
p-phenylenediamine and pyrocatechin. Meritol is used for fine-grain develop-
ment<10' but the caustic soda formula (two bath) has been recommended for
under-exposed negatives:
A. Water to 1000 cc
Meritol 8g
B. Water to 1000 cc
Caustic soda 6·3 g
For development treat for 3 minutes in A, then for 3 minutes in B. To
reduce the contrast dilute A. IU
57. Developer for doubling speed

According to Renwick (1920) then Stauffer, Smith and Trivelli, certain
hydrazine derivatives can make the under-exposed grains of an emulsion
developable by a contagious effect. Miller, Henn and Crabtree<11 l use a hydra-
zine derivative together with an anti-foggant in a developer such as D 19
having a high sulphite and bromide concentration.
A. Water to 1000 cc
Metol 2g
Sodium sulphite anhydrous 100 g
H ydroquinone 9g
Potassium carbonate so g
Potassium bromide Sg
B. Water to 30 cc
Nitrobenziminazol nitrate or benzotriazole
2: 1000 20 cc
H ydrazine hydrochloride 1·6 cc
Add B to A immediately before use as the developer does not keep for more
than a day.
The amount of hydrazine hydrochloride must be increased with the sul-
phite. Optimum pH 9·5. Semicarbazide hydrochloride also produces the
same effect.
The peculiarity of this developer is that it only shows the maximum effect
when the fog density is an high as 0·4-0·6, which would be inadmissible with
a normal developer. A grainy image is produced.
M. Tajima <12 > has disclosed D 72 diluted with an equal volume of water
together with 14 mg of nitrobenziminazole and 3 g of a hydrazine salt.
The increase of sensitivity, although definite, has frequently been exagger-
ated by some writers. This 'contagious' development appears to be due to the
formation of a semi-quinone which diffuses towards the other grains. This
quinone becomes a hydroxyhydroquinone, the sulphite acting as a catalyst. <12b l
I
58. Compensating developers

The so-called compensating developers are used for the development of
images which normally have a long density scale, a scale which they reduce
by accelerating the appearance of the shadows and slowing down that of the
highlights. A metol-hydroquinone developer with a high proportion of metol
in slightly alkaline solution is used for this:
Water to 1000 cc
Metol 3g
Hydroquinone 1g
Borax 10 g
Development time: 12-20 mins. at 20°C.
A plain metol bath, slightly alkaline and containing a solvent, primarily

alters the intermediate gradations:
Water to 1000 cc
Metol r
5g
Borax 10 g
Hypo 2g
Another method to reduce the density range is to develop in a tanning
developer with a low concentration of sulphite; this produces, at the same time
as the silver image, a residual coloured organic image which particularly
intensifies the lower densities. This residual image is produced by the
oxidation products of the developer which are deposited in the absence of
sulphite. The very unstable bath must be made up as two solutions:
A. Water to 1000 cc
Potassium metabisulphite 12 g
Pyrocatechin 80 g
B. Water to 1000 cc
Caustic soda 35 g
For use take:
A 10 cc
B 10 cc
Water 200 cc
For under-exposure increase the quantity of caustic solution.
For over-exposure add 1 cc of 5 % potassium bromide.
A Windisch formula uses :

A. Water to 1000 cc
Sodium sulphite anh. 5g
Pyrocatechin 16 g
B. Water to 1000 cc
Caustic soda 100 g
For use take:
A 5 cc
B 2-3 cc
Water 200 cc
Development time: 18-24 mins.
59. Tropical developers

There are several methods for developing at relatively high temperatures
without producing reticulation of the gelatin.
1. Pre-hardening.
2. Hardening development.
3. Addition of sodium sulphate to a normal developer to prevent the
gelatin from swelling.
Hardening developer. Diaminophenol can be used together with chrome
alum:
Water to 1000 cc
Diaminophenol 5g
Chrome alum (5 % solution) 100 cc
In the case of very high temperatures a developer containing formaldehy de
or glyoxal can be used together with an anti-foggant (see ultra rapid develop-
ment, para. 95).
Sodium sulphate developers: the addition of sodium sulphate to a developer
enables development to be carried out up to 35°C without inconvenience
owing to the reduced swelling of the sensitive layer. The necessary quantity
of sodium sulphate depends on the temperature at which it is to be used.
Average quantities for metol-hydroquinone developers of the D.72 (diluted
with an equal part of water) and D 76 types:
50 g up to 26°C
Sodium sulphate anh. 100 g up to 32°C
( 150 g up to 36°C
In spite of the considerable increase in temperature, development time is

only slightly reduced: at 32°C the reduction is only 30 % .
Special developers containing sodium sulphate
Agfa 55 DK.15
Metol 15 6g
Sodium sulphite anh. 75 90 g
, sulphate anh. 50 45 g
,, metaborates 22·5 g
Development time 8- 10 mins. 3t rnins. at
at 30°C 30°C
6 rnins. at
25°C
10 mins. at
18°C
A reduction in the metaborate to 5 gin DK15 reduces the contrast.
Equivalents of the various forms of sodium sulphate
Sodium sulphate anh. Na 2 S04 100 g
, , heptahydrate Na 2 S047H 20 190 g
, , decahydrate Na 2S04 10H 20 260 g
(Glauber's salt)
o•
The Agfa formulary for photomechanical emulsions recommends the
addition to the developer of 10-20 g of sodium nitrite to maintain the clarity
of negatives above 25°C.
60. Bromide paper developers

Developers for positive emulsions are generally contrasty developers. They
give strong blacks and develop rapidly. It is true that positive emulsions are
fine grained which enables them to be readily reduced by the developer. The
fog must be practically nil but this is due more to the emulsion layer than to
the developer.
Any well-balanced developer can be used to develop positive images. If it is
too dilute, good blacks cannot be obtained, and if it contains too much brom-
ide the image will appear slowly.
The universal metol-hydroquinone developer given in para. 53 can be used
to develop bromide papers. Development time 2-3 minutes at 18°C. The
proportion of hydroquinone can, however, be increased while the metol is
reduced in order to give a rapid increase in contrast. It must not be forgotten
that development of positive images is generally taken to gamma infinity;
therefore development is complete. The contrast, therefore, depends on the
nature of the paper rather than on the time of development.
D 72 Kodak Agfa
Metol 3 2g
Hydroquinone 12 6g
Sodium carbonate anh. 67 ·5 52g
Potassium bromide 2 2g
Dilution for papers add 3 parts add 1 part
water water
Development time 1 t-2 mins. at 2 nuns. at
21 °C 18°C
Lantern slides add 1 part
water
1-2 mins.
at 21 oc
61. Developers for contrasty emulsions

D 11 for
D 154 for Infra-red high contrast
documents plates, lantern
microfilms plates
Water to 1000 1000 1000 cc
Metol 1·25 2·25 1g
Sodium sulphite anh. 22·5 72 75 g
Hydroquinone 6 8·75 9g
Sodium carbonate anh. 30 48 25 g
Potassium bromide 0·5 4 Sg
Development time undiluted 2-3 mins. 6--7 mins. St mins.
at 18°C at 18°C at 21°C
1-1! mins.
at 21°C
Soft-working developer for photo-mechanical emulsions (Agfa)
Water to 1000 cc
Metol 1g
Hydroquinone 6g
Potassium metabisulphite 1·5 g
Citric acid 0·5 g
Develop 4-6 mins. at 18°C.
62. Developers for motion-picture positives

D 16 [2] Levenson<13 >
Water 1000 1000 1000 cc
Metol 0·3 0·7 0·7 g
Sodium sulphite anh. 38 50 40 g
Hydroquinone 6 7 4g
Sodium carbonate anh. 19 40 20 g
Potassium bromide ·9 2 1g
Potassium metabisulphite 1·5 - g
Citric acid 0·7 - g
To replenish the D 16 formula: metol 0·3 g, sulphite 38 g, hydroquinone
9 g, carbonate 38 g, bromide 0·7 g, metabisulphite 1·5 g.
For titles and variable area sound-recording negatives, use formula 2. For
variable-density tracks whose gamma is low, develop in soft negative
developers.
63. Caustic developers for maximum contrast

The high alkalinity of caustic soda or potash developers gives them a very
high energy which is shown as a rapid increase in the high densities. Caustic
developers, generally using hydroquinone, utilize this property for the
development of very high-contrast images with strong blacks such as positives
for photomechanical processes (process-type emulsions).
Caustic developers have the disadvantage that they attack the gelatin and
the skin; also their action must not be carried on for longer than necessary.
Furthermore they do not keep well.
D 8 Kodak Agfa 1 Agfa 2
Water to 1000 500 500 cc
Sodium sulphite anh. 90 - g
Potassium metabisulphite 5 12·5 g
Hydroquinone 45 5 12·5 g
Caustic soda 37·5 - g
Potassium bromide 30 1 12·5 g
B. Water to 500 500 cc
Caustic potash 25 25 g
Water to dilute 500 - cc
Development time at l8°C 2 mins. 3-5 mins. 2-3 mins.
Wash carefully before fixing to avoid smears and dichroic fog. Fix in a
hardening fixer.
64. Chloride paper developers

Chloride (gaslight) papers are made with two emulsion types: black tone and
bluish tone. The emulsions giving black tones are generally coated on ivory
cream bases, whilst the bluish-tone ones are coated on white base. The black-
tone papers can easily give bluish tones by incorporating certain anti-foggants
in the developer. Conversely, warm black tones can be obtained on bluish
materials by modifying the developer.
Chloride papers develop very quickly, the image being completely formed
at once, the density then increasing: this enables exposure errors to be cor-
rected-a property of great use to printers of amateur negatives. This effect
depends upon the quality of the emulsion.
Chloride papers tend to become yellowish particularly when kept for a long
time. The manufacturers incorporate anti-yellowing agents to overcome this
fault; these compounds can also be added to the developer. Nevertheless, it
is recommended that development of chloride papers should not be continued
longer than necessary. For the same reason the developer should not contain
an excess of sulphite which dissolves the silver chloride (subsequently
reduced by the developer to yellow colloidal silver).
Generally, the following developer formulas can be used for the develop-
ment of both black and bluish chloride papers:
Universal M.Q. developer (para. 53): development time 60- 90 sees. at
l8°C.
Formula D 72 (para. 53): one part stock solution to two parts of water.
Development time: 45-60 sees. at 21 °C.
Phenidone formula (para. 55): one part stock solution and one part water.
Development time 45-60 sees. at 20°C.
Special chloride paper formula:
Water to 1000 cc
Metol 2g
Hydroquinone 5g
Potassium bromide 0·5 g
Development time: 90 sees. at l8°C.
To obtain bluish tones from papers normally giving black tones, one of the
following compounds should be added: benzotriazole or 6-nitrobenziminazole
nitrate. Concentration 0·1-0·25 g per litre. The best procedure is to add 25 cc
per litre of a 1 % aqueous-alcoholic solution of benzotriazole. Many other
compounds have a similar effect-methylbenzoxazoles, azimidobenzenes,
azimidonaphthalenes, methylnaphthothiazoles, quinine salts, formalcystine
(1 : 1000). Salts of 5-halogen-2-aminopyridine and the 3 : 5-disubstituted
compounds also produce bluish images. (14 >
To overcome yellowing add 15 cc of a 1 % aqueous solution of Antiflavog per
litre of developer. (15 > This is a diphenyliodonium compound.
Development of warm black images on blue-black papers. The bluish tone
does not appear in the presence of a high concentration of bromide. As the
latter retards development, it is desirable to accelerate it by raising the
temperature.
Water to 1000 cc
Metol 0·8 g
Hydroquinone 4g
Development time 2!--3 mins. at 23-24°C. Compared with a normal
developer, the contrast is increased, and the sensitivity reduced slightly.
65. Developers for warm tones with chlorobromide or chloride

emulsions
The development of warm tones on papers and lantern plates made with
silver chlorobrornide or chloride is primarily dependant on the fineness of
grain of these emulsions and upon their bromide/chloride ratio.
For a given emulsion, the tone becomes warmer, that is more red, as the
developer is diluted, contains more bromide, and as development is reduced.
This implies that for a given colour, a given contrast is produced, and there-
fore the emulsion contrast must be selected to suit. On the other hand, to
compensate for the loss of sensitivity, the print must be overexposed, especially
when development is shortened. As a general rule close control of the results
is difficult.
Warm black formula D 166
Water to 1000 cc
Metol 1·15 g
Hydroquinone 8·5 g
Dilute with 3 parts of water.
Development time: 3 mins. at 18°C for chlorobromide papers.
Formula for brown tone (Agfa Portriga type emulsions):

Water to 1000 cc
Hydroquinone 24g
Development time: 4-7 mins. at l8°C.
Formula for sepia and red-brown tones with glycin: D.l59.
This bath, which gives attractive warm tones, must be used with a harder
emulsion than that used with D 166, to compensate for the apparent reduc-
tion in contrast:
Water to 1000 cc
Hydroquinone 7g
Glycin 4g
Sodium carbonate anh. 26g
Potassium bromide lg
Development times: red tones 2! mins.; brown tones 6 mins.
66. Special developers for warm-tone lantern plates

1. Standard bromide formula:
Water to 1000 cc
Hydroquinone 12 g
Dilute wth an equal part of water.
Examples of relative exposure and development times:
Exposure Development Colour obtained
24 sees. 3 mins. red
20 , 4 red-brown
16 , 5 , brown
12 , 6 , sepia
4 , 10 , warm black
2. Ferrocyanide developer: often gives brighter colours. First prepare:
Water 1000 cc
Potassium ferrocyanide 30 g
Hydroquinone 10 g
Caustic potash 50 g
and add, to a litre of developer, the following quantities of 10% potassium bromide:
Amount of bromide Colour obtained Developing time
100 cc Purplish brown 10-15 mins.
180 cc Purple 20-30 mins.
200 cc Carmine 30-40 mins.
3. For green tones develop 2-3 minutes in:
Water to 1000 cc
Potassium ferrocyanide 30 g
Hydroquinone 4g
Sodium carbonate anh. 1S g
The colour becomes yellowish if 3S% of aS g per litre hypo solution is added.
4. Bright colours can be obtained by mixing metal with tartaric acid and hypo. A
red image is obtained by developing for 6-8 mins. in the following solution:
Water to 1000 cc
Metol 2·S g
Hypo 2·S g
Tartaric acid 0·7S g
If the amount of tartaric acid is increased, together with the developing time, the
colour passes through purplish red to violet, then to blue. With 4 g of the acid and a
development time greater than 20 minutes, a blue image is developed. On the other
hand, with only 0·2S g tartaric acid the image colour shifts towards the orange.
S. The addition of ammonia or ammonium salts to a hydroquinone bath accelerates
the formation of red tones without a great reduction in contrast:
A. Water to 1000 cc
Sodium sulphite anh. 6S g
Hydroquinone 14 g
Potassium bromide 10 g
B. Water to 1000 cc
Ammonia S.G. 0·920 32 g
Ammonium bromide 6g
Mix 1 part A with 1 part Band develop 3 mins. at 18°C.
6. Thiocarbamide (thiourea) produces warm tones following the method which has
been given by Mees. Three baths are prepared : A-metol 10, hydroquinone S, sul-
phite anh. SO, carbonate anh. 36, water 2,000.
B-ammonium carbonate SO, ammonium bromide SO, water SOO.
C-thiocarbamide 3, ammonium bromide 1, water 400.
The solutions A, B and C are mixed in the following proportions: brown tones,
14 : 18 : 1; blue-grey tones, 12 : 3 : 1; warm black tones, 10 : S : 1. The warm tones
are obtained with long exposures and the contrast must be kept constant for each tone.
The order of the colours is successively: yellow, purple, blue-grey and black.
Carreil has used thiourea for physical development (Phot. Jl., 1947, p. 1S7) after
iodide conversion. The stock solutions are as follows: silver nitrate + excess sulphite
+hypo; M.Q. developer; thiocarbamide + ammonium bromide. Depending on the
exposure and development time, blue, blue-black, purple-black, brown, purple, red-
brown and warm black tones are produced.
It should be remembered that the colours and development times shown for all
these warm tone formulas are given only as examples. The results are greatly depen-
dent on the emulsion type.
The exact colour of lantern images is only seen after drying.
7. Warm tone developer using reductone. Willmanns and Schneider have claimed< 18 >
that organic compounds containing the grouping OH. CH = C. OH -have develop-
ing properties and that they give brown or red images. Stewart<'') has used glycore-
ductone, isolated by Euler and Martius,< 18> and prepared in the following way:
20 g of anhydrous sodium carbonate (or 22·5 g of the monohydrate) is dissolved

with SO g glucose in 300 cc of warm water. The solution is heated to 91-93 °C for
two-and-a-half minutes and then cooled rapidly. A second solution of 45 g of anhy-
drous sulphite, 12 g of hydroquinone and 4 g of potassium bromide in 400 cc of water
is prepared. The two solutions are mixed and made up to a litre. This solution
develops warm tones in about five minutes at 18°C.
67. Inorganic developers

1. A number of inorganic substances are capable of developing photographic
images. They are not used in practice but can be of use in certain cases where organic
developers are not available and also for laboratory research.
Gaseous hydrogen in the presence of colloidal palladium, <19 > hydrazine NH 2-NH 2 ,
hydroxylamine<••> NH 2-0H, hydrogen peroxide in an alkaline solution, and all salts
which can pass from a lower to a higher valency, are reducers of silver halides. In the
latter case the degree of reduction is limited by the reversible reaction and develop-
ment ceases when an equilibrium is reached, for example with copper chloride
Cu++Ag+ ~ Cu++ + Ag
For development to take place normally, it is necessary to displace the equilibrium
of the reaction by removing the higher valency ions completely as they are produced.
This can be done by converting them into complex ions: thus a ferrous ion reduces
a silver salt and itself is oxidized to the ferric state:
Fe+++ Ag+ ~ Fe++++Ag
The ferric ions are sequestered by the addition of sodium fluoride (NaF) which con-
verts them into a ferrifluoride ion (FeF .)--- in which the ferric ion is not reactive.
2. Sodium hydrosulphite
Sodium hydrosulphite, Na.s.o. or more exactly Na . 0-S-0-0-S-0. Na
is an energetic reducer. It has, however, the disadvantage that its solutions are un-
stable and the vapour is suffocating. Lumiere and Seyewetz have prepared a relatively
stable dry mixture:
Sodium hydrosulphite anh. 100 g
Sodium bisulphite anh. 165 g
Potassium bromide, dry 35 g
To prepare the developer, 120 g of this powder is dissolved in a litre of water. This
developer has a strong d esensitizing action (200 times) which p ermits the use of a
deep yellow light during development. With some emulsions a high fog level is
produced.
68. Metal-organic complexes

Polybasic organic acids have the general formula R(CO.OH)n, where R is
an organic radical and CO.OH is the carboxylic acid radical. Among the
bivalent acids the simplest of the series are oxalic acid CO.OH-CO.OH,
malonic acid CO.OH-CH 2-CO.OH. Of the tribasic acids, citric acid
CO.OH-CH 2-C.OH(CO.OH)- CH 2-CO.OH is the most common.
With polyvalent metals, such as iron, titanium, vanadium molybdenum,
uranium, etc., these acids form complex anions which correspond to each
valence, and in which the characteristics of the metal are completely masked.
The general discussion of complexes will be deferred but the ions of interest
in this connection are those with the constitution [(R(C0 2)n)x Myy- where
M is a metallic atom and the integers x andy depend upon the valency of the
metal and the number of acid radicals in the ion, whilst the basicity of the
complex ion is represented by the usual symbol-, the number of such elec-
trons being shown by z.
Thus iron, bivalent in the ferrous state Fe++ and trivalent in the ferric
state Fe+++, forms with the oxalate ion (CO.O-CO.O)-- or (C 2 0 4) - -,
ferro-oxalic [(C 2 0 4) 2 Fe]-- andferri-oxalic [(C 2 0 4 hFe]--- ions respectively.
With bases, ferro-oxalates and ferri-oxalates are formed.
The ferro-oxalic ion, being derived from the ferrous ion, is a reducing agent.
It reduces silver ions, and is itself oxidized to the ferri-oxalic ion:
[(C 20 4 ) 2Fe]- -+(C 20 4)--+Ag+ = Ag+[(C 20 4) 3 Fe]-- -
terro-oxatic ion oxalic ion silver silver ferri-oxalic ion
ion metal
Sodium or potassium ferro-oxalates are therefore developers, whilst the

corresponding ferri-oxalates are oxidizing agents. Similar behaviour is found
with ferro-malonate (CH 2 = C 2 0 4hFe K 2 and ferro-citrates; the titano-
oxalates whose valency changes from 3 to 4, and the uranium derivatives
having valency changes from 4 to 6.
Many other complex substances studied by Rzymkowski show developing
properties, particularly cuprammonium oxalate, tartrate and citrate(21 > and
complexes of iron Fe++ and titanium Ti+++ with nitrilotriacetic acid and
ethylenediamine-tetracetic acid. (22 > The cuprammonium compounds can be
obtained by mixing an ammoniacal solution of cuprous chloride with a
solution of neutral potassium tartrate, oxalate or citrate. The iron and titan-
ium complexes are produced by mixing the corresponding acid or its sodium
salt with an ammoniacal solution of ferrous or titanous sulphate. The most
interesting complexes are those from the tetrasodium salt of ethylenediamine-
tetracetic acid, with the formula:
NaO.CO.CH , CH,.CO.ONa
"" N-CH -CH -N/
2 2
NaO.CO.CH , / "" CH,.CO.ONa

better known by the names Trilon B or F, Celon E, Versene and Seques-
trene.
Titanium oxalate developer. This developer has the property of depositing,
in proportion to the silver image, titanium oxide TiO 2 which can be used as a
mordant for dyes. It is prepared by mixing the two following solutions: (23 >
Potassium oxalate 3% 550 cc
Titanium trichloride comml. soln. 50 cc
Ferrous oxalate developer. To prepare a ferrous oxalate developer, a f errous salt is
mixed with an excess of potassium oxalate in distilled water. As it does not keep, it
must be prepared just before use. To prepare the developer, 3 parts of a 330 g per litre
solution of potassium oxalate is mixed with one part of a 330 g per litre solution of
ferrous sulphate and 20 drops of 10% potassium bromide solution should be added
to each 100 cc of mixed solution. To accelerate d evelopment, 3 drops of 5% hypo is
added to 100 cc of developer.
When the ferrous sulphate and potassium oxalate are mixed a precipitate of ferrous
oxalate is formed, but this is redissolved in excess potassium oxalate (which gives a
ferro-oxalic complex).
Aerial oxidation results in the precipitation of basic ferric salt. This disadvantage
can be overcome by replacing the ferrous sulphate with ferrous lactate (Rzymkowski):
7 g of ferrous lactate in 100 cc of 25% potassium oxalate. The resulting red solution
is neutral.< 24 l
A more stable bath is obtained using sodium glycolate :<2 •l 3 parts of 300 g per litre
potassium oxalate, 1 ·5 parts of 350 g per litre sodium glycolate and 1 part of 350 g
per litre ferrous sulphate.
The three ingredients can be mixed in the dry state, after each has been powdered
separately and dried at 100°C under reduced pressure. The yellow powder obtained
by mixing 91 parts of ferrous sulphate, 244 parts of neutral potassium oxalate and
15 5 parts of sodium glycolate, dissolves readily in water at a strength of 250 g per litre.
After development, the plate is treated in a hydrochloric acid stop bath, rinsed in
distilled water, and fixed in a bath containing 1% calgon to avoid precipitating calcium
oxalate in the gelatin.
T . H. James has studied dilute ferrous oxalate developers in a basic solution.< 26 l
69. Reversible developers. Development with vanadium salts

Normal developers are irreversible reducing systems. The study of super-
additivity, however, has shown that, with some developer combinations, one
is immediately regenerated from its oxidized form by the other. Some organic
derivatives such as those from anthraquinone-,8-sulphonic acid can be re-
generated by electrolytic reduction.
The most suitable compounds for experiments on reversible systems are
metallic ones. In 1894 A. and L. Lumiere<27) foresaw the use of vanadium
salts Va++ as developers, Liesegang<28 > the use of chromium, zinc and molyb-
denum salts. The first systematic study of the electrolytic regeneration of
vanadium salts was carried out by Rutter in 1906. <29 > Much later, Fuchs <30 >
used an electrolytically reduced chrome alum solution, and Kellner and
Bennevitz<31 > developed with nascent hydrogen liberated at a cathode.
Rzymkowski <32 > has finally disclosed since 1935 a series of photographic
developers prepared electrolytically, by stressing the reversibility of metallic
complexes such as potassium ferro-oxalate and titano-oxalate.
For a reversible system to be used as a developer bath, oxidized and re-
duced forms must be soluble, and the redox potential must be sufficiently
low.
Vanadium developer. The complete reversible system represented by
V++-e ~ V+++ has recently been studied by Roman< 33 > and used in prac-
tice. Bivalent vanadium bromide develops a positive emulsion very quickly;
the resulting oxidation products are electrolytically regenerated at a lead
cathode, following the scheme:
vo++++ZH++e-+ v++++H 2 0
v++++e -+ v++
The developer must be kept in a high-pressure nitrogen atmosphere. A
cell enables the intensity of regeneration to be controlled. Fortmiller and
James <34 > have shown that the development velocity depends mainly on the
concentration of vanadous ions.
Rasch and Crabtree<35 > have used a developer made from a solution of
vanadic anhydride in dilute sulphuric acid, in the presence of oxalic acid,
which is electrolytically reduced to the vanadous salt. A specially constructed
machine enables 1000 metres of 35-mm positive film to be developed in
only 1 litre of solution, the liberated bromide being partially eliminated
by diffusion into the cathode section of the cell. The image is developed in
20 sees. at l5°C and the sensitivity is doubled. The tendency to fog can be
avoided by including some potassium iodide. The high acidity of the bath
makes hardened emulsions necessary. Tests on negative emulsions have not,
so far, been satisfactory.
70. Special developers

1. Deep-acting developers. The most effective are acid diaminophenol
(amidol) (para. 51) and p-phenylenediamine developers. The addition of
safranine favours depth development (Namias 1924).
2. Solutions for developing the surface latent image
Ferrous oxalate developer: <36 >
A. 25 % neutral potassium oxalate
Water to 300 cc
B. Ferrous sulphate cryst. 25 g
( Citric acid 1g
For use, mix equal parts of A and B and develop for 5 minutes at 18°C.
Sulphite-free glycin solution:<37 >
Water to 1000 cc
Glycin 30 g
Sodium carbonate anh. 44·4g
Develop 5 minutes at 18°C.
Isoascorbic acid developer: <38 >
Water to 1000 cc
Metol 2·5 g
Isoascorbic acid 10 g
Sodium metaborate 35 g
3. Solutions for developing the internal latent image.
The internal latent image of silver bromide crystals can be developed by
adding 1-4% hypo to a normal organic developer.
Hautot and Sauvenier's formula:
Water to 1000 cc
Metol 1·5 g
Hydroquinone 6g
Hypo crystals lOg
The following bath has also been used:
A. Water to 800 cc
Pyrocatechin 50 g
Sodium metabisulphite 52 g
Potassium bromide lOOg
Potassium iodide 6g
B. Water to 200 cc
Caustic soda 50 g
Develop for 3 minutes at l8°C.
71. Physical development

Physical development is the production of a visible image by depositing
metallic silver on the development centres, from a solution containing a
soluble silver salt and a reducing agent.
In normal chemical development it is the silver bromide crystals containing
the development centres which are reduced, but here in contrast, the sensi-
tive silver salt takes no part in the development process; the only reaction is
between the developing solution and the development centres. Consequently,
the first step can be to remove the silver halide, allowing development to be
carried out in white light.
The developing solution consists of a solution of a silver salt-silver
nitrate, or preferably silver sodium sulphite-and a reducing agent. The
reducing agent is normally an ordinary developing agent such as hydro-
quinone, metol, p-aminophenol or p-phenylenediamine.
Even in the absence of a sensitive layer, the silver salt is reduced very
slowly to produce colloidal silver. In the presence of the particles of metallic
silver which constitute the latent image, however, the reduction takes place
much more rapidly, depositing silver from the solution on the development
nuclei to produce very fine silver grains which soon give a visible image
which increases in density.
With such a fine-grain image, a much greater resolving power can be
achieved by physical development. On the other hand, there is a loss of
speed which necessitates an increase of 2-4 times in exposure. The images
are flat and frequently foggy. Furthermore, development is very slow, often
taking several hours.
1. Development before fixation. It is necessary to reduce the soluble silver
salt in the solution but not the insoluble halide. This can be done merely by
raising the redox potential of any kind of developer to a value not exceeding
120 m V, by reducing the pH (that is by acidifying the solution). At this
potential the soluble silver salts are still reducible. An acidified developer is
therefore used (pyrogallol, sulphite and acetic acid, for example) to which is
added 10 % of a 10 % silver nitrate solution, or silver sodium sulphite.
The following solutions are prepared:
A. {Distilled water 60 cc
B. {Distilled water 20 cc
Silver nitrate 3 ·2 g
Pour B into A with stirring. Then add 70 cc water followed by 32 g hypo.
This solution of silver sodium sulphite will keep. Just before use, 800 cc of
water containing 3 ·3 g diaminophenol (ami dol) is added.
2. Development after fixation. The plate is first fixed in 6 % hypo. Mter
washing, it is developed in a mixture of the following solutions, a suitable
ratio being 1 part of A to 5 parts of B.
A. Distilled water 1000 cc
10% silver nitrate 75 g
B. Water 1000 cc
p-phenylenediamine 20 g
Other developing agents can be used together with the silver sodium sul-
phite solution (solution A).
If the silver nitrate is replaced by mercuric nitrate, a solution of mercury
sodium sulphite is formed, which gives a mercury image similar to the silver
image. The mercury developer is more stable, but less active than the silver
developer.
3. Quinhydrone physical developer. This developer disclosed by Rzym-
kowski <39> is a powerful intensifier.
A. Distilled water to 100 cc
Citric acid 12 g
B. Alcohol 90 % to 100 cc
p-benzoquinone 2g
C. Distilled water to 100 cc
Hydroquinone 2g
D. Distilled water to 100 cc
Silver nitrate 10 g
Mix in the order A : 3 cc; B : 7·5 cc; C : 7·5 cc; D : 4·5 cc and make up
to 100 cc with distilled water.
4.'Development after iodizing. To prevent reduction of the silver halide,
it cari be converted to silver iodide by bathing for a few minutes in 1% potas-
sium iodide containing 2·5 % anhydrous sulphite. After rinsing, develop for
30-40 minutes.
1. Lous-Labetoulle L. : Sci. Ind. Phot., 1946, 65; Sauvenier H . : Sci. Ind. Phot.,
1951 , 41; Gauvin : C.R., 1953,807-809.
2. White D . R. and Weber J. R. in Henney and Dudley Handbook of Photography
(McGraw-Hill, New York).
3. James T. H.: R.P.S. Cent. Conf., London, 1953.
4. Henn R. W.: Phot. Soc. Arner.Jl., 1953,131-136.
5. Levenson G . I. P.: Sci. Ind. Phot., 20(11), 213; Int . Cong. Pure and Appl. Chern.,
1947, 533-539; Phot. Jl., 1949, 13-20; 1952, 109-110.
6. Levenson G. I. P. :Jl. Phot. Sci., 1953, 117-122; Sci. Ind. Phot., 1953, 465-467.
7. James T . H.: Phot. Soc. Arner.Jl., 1953,156 and Vanselow W.: Phot. Sci. and
Tech., 1954, 77-80; Sci. Ind. Phot., 1954,439.
8. Axford A. S. and Kendall}. D . : R.P.S . Cent. Conj., London 1953 .
9. Kendall J.D.: Brit.Jl. Phot., 1954, 8.
10. See following chapter.
11. Phot. Soc. Arner. Jl., 1946, 586 and 692.
12. T ajima M. : Sci. Ind. Phot., 1952, 472.
12b. Lu Valle J. E.: Phot. Engng., 1954, 5, 273-275.
13. Levenson G. I. P.: Sci. Ind. Phot., 1949, 55.
14. French Pot. 830,935.
15. Made by Dr. Sager and Grassier at Heidelberg, Germany (see para. 349k).
16. U.S.P. 2,122, 599.
17. Stewart 0. ].: Phot. Soc. Arner. Jl., 1952, 80-81.
18. Euler and Martius: Ann. Chern., 505, 83.
19. Rzymkowski : F.P. 873, 028 .
20. As hydrochloride.
21. Rzymkowski }.: Sci. Ind. Phot., 1954, 385-388.
22. Rzyrnkowski ] . : Sci. Ind. Phot., 1952, 21 and 362.
23. Rzymkowski J.: Arhiv. K erniju 1948, 26-45; Sci. Ind. Phot., 1950, 139.
24. Rzymkowski J.: Phot. Korr., 1951, 22; Gen. Pat. appl., 112,941 (1942).
25 . G.P. 286,727 (1914) and 286,775 (1915) . Glycolic acid has the formula
CH 2 0H . COOH containing both acid and alcohol groups.
26. James T . H.: J.A.C.S ., 1945, 1908-1911; Sci. Ind. Phot., 16(11), 220, 17(11), 233.
See also Amman-Brass: Sci. Ind. Phot., 8, 347.
27. Lumiere A. and L. : Bull. Soc. Fr. Phot., 1894, 108-110.
28. Liesegang : Phot. Archiv., 1895, 282.
29. Rutter R. G.: Die kataly tischen eigenschaften des Vanadins; Inaugural disser-
tation, Leipzig, 1906.
30. Fuchs: Phot. Ind., 1930, 927 ; Sci. Ind. Phot., 1930,417.
31. Kellner and Bennevitz: Z eit. Wiss. Phot., 1935, 212-233; Sci. Ind. Phot., 1935,
120.
32. Rzymkowski }.: G .P. 691,913 (1935) ; Phot. Ind., 1937, 453; F.P. 846,968 and
847,179 (1938) ; Phot. Korr., 1943, 1; Sci. Ind. Phot., 1950, 139 ; Phot. Korr,
1951 , 22-25; Sci. Ind. Phot.,1951, 326-330, 1953, 43 .
33 . Roman P.: Sci. Ind. Phot., 1952, 417-426 .
34. Fortmiller L. J. and James T . H.: R .P.S. Cent. Conf., London, 1953 .
35. Rasch A. A. and Crabtree J . 1. , S ci. Ind. Phot., 1954, 201 and 399.
36. Hautot and Sauvenier: S ci. Ind. Phot., 1952, 169.
37. Stevens: Phot. Jl., 1942, 42; Sci. Ind. Phot., 1944, 275 . Hautot and Sauvenier:
Sci. Ind. Phot., 1952, 169.
38. James, Vanselow and Quirk: Phot. Soc. Arner.Jl., 1953,170-172.
39. G.P. 711,286 (1936); Sci. Ind. Phot., 1950,44.
Chapter VII
FINE-GRAIN DEVELOPERS
72. What is 'grain' in a photographic image?
Everyone knows that the photographic image is made up of a dispersion of
silver particles in a thin layer of gelatin. The average diameter of these par-
ticles in negatives is l-3,u; and depending whether there are many or few, the
image appears dark or light. The image is therefore discontinuous like a more
or less coarse mosaic.
It is obviously always beneficial to have images whose grain appears as
fine as possible. Now it is best to see how and to what extent fine grain is
possible, without upsetting the other important aspects. It is also advisable
to correct certain false preconceived ideas which are widely held, but whose
correctness has not been established.
A negative emulsion has coarser grain as it is made faster. An emulsion of
extreme sensitivity and very fine grain cannot be obtained. The individual grain
diameter is not however the only factor, and we will see the part that the
other ones play.
The commonly used methods of determining graininess are by judging
either a photomicrograph of the negative or, more frequently, an enlarged
print. Now it is very easy to be deceived by one or other of these methods.
By enlarging parts of each step of sensitometer strips on a coarse-grain fast
emulsion and a slow fine-grain one, using a microscope (Fig. 6a) the differ-
ence of average grain size is readily seen. However, the most striking point is
that the grains, at first not numerous in the clear parts of the negative (corres-
ponding to the shadows of the subject) multiply as the density increases, and
aggregate to form large black veins leaving big empty spaces (half-tones of the
subject). The texture of this mottling is finer with medium speed emulsions.
In the dense areas of the negative (which are the subject highlights), the
grains are so numerous that they cover the major part of the surface of each
zone examined, but they leave empty spaces between them, which contract in
the very high densities. These empty spaces form holes which are smaller as
the emulsion grain is finer.
Let us make a positive print, which as far as practical results are concerned
is the final product:
The clear parts of the negative, containing the dispersed black grains give,
on printing, the shadows of the positive (Fig. 6b). The black grains become
white patches which, as the negative density increases, become bigger, to give
89
FIG. 6A. Photomicrographs of developed areas of increasing density on two emulsions, one
coarse-grained, the other fine-grained . Enlargement, SSOX.
.. r •
. -
.. . .·
FIG. 6B. Positive prints corresponding to the two negative wedges (enlarged to 850 diameters}
of Fig. 6A. The light negative areas with isolated silver grains naturally give dark positive
areas whilst the dark negative areas give the clear areas in the print, whose 'grains' are in fact
the spaces between the silver grains of the corresponding negative images.
mottled areas in the positive half tones. Finally, in the highlights of the print
(printed from the high negative densities) black dots are found which corres-
pond to the spaces between the grain clumps of the negative.
Now, where is the grain most obvious, in the enlargement? Not obvious in the
highlights, it becomes more apparent as the density increases, with a maxi-
mum in the middle densities. Beyond there, the black patches on a white
background are replaced by white patches on a black background, which
become smaller and less noticeable.
We can therefore draw the following primary conclusions:
1. The grain which we see on a positive print is not the grain of the nega-
tive emulsion, but the image of the holes left between the grain aggregates,
these holes being considerably larger than the grains themselves.
2. In the shadows of the print, white patches are seen which correspond
to the grain aggregates and not the individual grains.
3. The half-tones are formed of large mottled black and white areas whose
pattern is more likely to be finer as the initial grain size is smaller. However,
the individual small size of the grains of the negative is not enough to ensure
apparent fine grain in the print; a regular topographical dispersion of the
grains in the gelatin during the manufacture of the material is essential. This
is not easy, as the precipitated crystals generally form chain aggregates. It is
these chains which lead to the formation of the large veins of reduced silver
seen with the microscope. By varying the conditions under which a single
emulsion was prepared, the writer obtained different dispersions, with the
same average grain diameter. This shows that the dispersed state of the
crystals affects the final apparent graininess on the print.
4. Comparison of a fine- and a coarse-grain emulsion is only of value at
equal densities. The mottled structure of the areas of different density can
lead to errors of judgment.
5. This leads to the printing of positives which has an influence on grain.
The masses and spaces of the negative image are not sharply defined. Their
density decreases at the borders. This results in a variation in their apparent
diameter by diffusion depending on the exposure given during printing, in
turn depending on the general density of the negative. This effect can be
estimated from the examples in Fig. 6c.
(a) For dense negative areas giving the light areas in the print, the grain
increases with printing exposure.
(b) For light negative areas giving the shadows in the print, the grain
decreases with printing exposure.
(c) For the middle negative densities giving the half tones, the grain is at
a maximum with the optimum exposure. It is reduced by underexposure
(enlargement of the whites) and by overexposure (enlargement of the
shadows).
In consequence, therefore, of the printing factors, that is on the choice of
subject, we are obliged to use the dense or clear negative areas and under-
expose or overexpose, print of different apparent graininess will be obtained
in which chance plays a considerable part.
73. Effect of the developer on grain
Of the various factors which, as we shall see, affect the grain of the photo-
graphic image, we will study first the developer and the development pro-
cedure.
The effect of the developer is great, but it is not always enough to counter-
balance the effect of initially coarse grain, of a bad crystalline dispersion or
unfavourable printing conditions.
(i) Print with increasing density of a dense negative area. The sensation of graininess increases
with increasing exposure.
(ii) Print with increasing density of a medium density negative area. The graininess is at a
maximum in the area of optimum exposure (in the centre).
FIG. 6c. Effect of exposure during the printing of a positive on the

'apparent grain' of the image. The n egative was enlarged 300X.
A fine-grain developer cannot restore the loss of definition caused by a

coarse-grain emulsion. We would add, furthermore, that the effectiveness of
M.Q.-borax, and metol-sulphite developers has been greatly overrated, and
contrary to the general belief, they are not at all suitable for certain types of
ammoniacal emulsions. In general, care must be taken before generalizing
on the good results which can be obtained with some negative materials.
What is the mechanism which produces finer developed grain than that
produced by normal development.
Fine-grain developers generally contain a solvent for silver bromide: this
solvent can be excess sulphite, potassium thic,cyanate, or the developing agent
itself, e.g. p-phenylenediamine. It is unlikely that the solvent works by
simply breaking the bromide crystal into small pieces as was thought at one
time. The silver grains are as we know, spongy clusters of filaments which are
extruded during the reduction process carried out by the developing agent,
a process which is affected by a large number of factors such as the adsorption
of the developing agent onto the halide crystal. The shape, the size and the
constitution of the developed grains are in the first place dependent on the
nature of the developing agents, which is shown in Fig. 6d.
94 PHOTOGRAPHIC C HEMISTRY
By reducing the alkalinity, the energy of the developer is reduced, develop-

ment takes place more slowly and the mass of filaments thus formed is more
fragile In the presence of a solvent, which during this time etches the crystal
surface, the latter can become detached from the parent mass to form separate
grains, often with their own side branches.
Simultaneously, the crystals undergo physical development, by deposition
of silver around the centres, due to soluble silver complexes formed by the
solvent (see end of para. 40). Unfortunately, the importance of that physical
process has not yet been estimated.
FrG. 6o. Action of different developers

on the grains of the same emulsion
(after Trivelli)
H : hydroquinone ;
HG: metol-hydroquinone;
D: diominophenol;
P: paraphenylene-diamine.
There are two types of fine-grain developer:

(a) Pseudo fine-grain developers of the M.Q. borax or metol-sulphite types,
whose effectiveness is questionable. In the most favourable cases they only
produce a slight reduction in grain. On the other hand the loss in sensitivity
is nil or negligible. The solvent action is of slight importance, it results only
from the long immersion in the developer.
(b) True fine-grain developers: principally those containing thiocyanate or
p-phenylenediamine. They have a strong solvent action towards the silver
bromide, which has the result of reducing the emulsion sensitivity, neces-
sitating an increase in exposure of 50- 100 %.
Before passing to the description of the different baths used, we note that
the development gamma varies between 0·6 and 0·8. Many workers prefer
the higher value. In fact, the choice depends on the contrast of the subject
photographed. A flat subject is preferably developed to y0·8 and a harshly lit
subject to 0·65. The shape of the characteristic curve also intervenes, and can
completely falsify tone values. We will return to this important point in the
chapter on sensitometry.
Fine-grain images are warmer toned and more transparent than coarse-
grain ones. Their visual contrast is frequently lower than their true contrast.
This must be taken into account when judging their results.
74. Borax developers
M.Q. borax developers are widely used for the development of amateur and
cine negatives. The development time is long and the contrast is low. As
amateur films are generally treated alike whatever their make, considerable
differences between them are found: emulsions with a high gelatin ratio or
ammoniacal types usually give flat results if the time is adjusted for a make of
neutral emulsion.
D 76 type formula
Working Replenishment
solution solution
Metol 2 3g
Hydroquinone 5 7·5 g
Borax 2 20 g
Development time at 18°C: films 8-16 minutes in dish, 10-20 minutes in

tank. Cine films: 10-25 minutes in tank. These times are for y = 0·8; for
y = 0·65 reduce times to 60%. At 24°C andy= 0·8 reduce to 65%.
Development time is doubled after treating 0·25 m 2 of film that is 7·5 m
of 35 mm film. Also, replenisher can be added gradually to maintain the level
of the solution, but it is not recommended to add more than 1f5th of the initial
volume; it is better to change the bath.
The activity of D 76 in a tank increases the first day, then drops rapidly.
Levenson (I) has shown that the increase in activity is due to the oxidation of
some hydro quinone which liberates caustic soda from the sulphite; thus the
hydroquinone is used up.
Development with D 76 is more rapid if the borax is replaced by sodium
metaborate (DK 76). The development times for various quantities of alkali
are as follows :
Quantity per litre Borax Metaborate
2g 20 mins. 10 rnins.
10 g 15 rnins. 7! mins.
20 g 10 rnins. 5 mins.
Buffered borax developer formula D 76d. The addition of boric acid to a
D 76 developer increases its resistance to pH variations (buffer effect). Also
it produces lower gammas. This bath has mainly been used for the develop-
ment of cine and sound recording negatives (variable density) which only need
a low gamma.
Water to 1000 cc
Metol 2g
Hydroquinone 5g
Borax 8g
Boric acid crystals 8g
With a new bath add 0·25 g potassium bromide.
Development time 10-15 mins. at 18°C.
75. Pyro, p-aminophenol, and Phenidone developers

Pyro developer. <2 l If the hydroquinone in D 76 is replaced by pyrogallol, and
the borax is increased to maintain the pH at 7 ·6, a developer is obtained which
not only gives the same graininess as D 76, but higher contrast due to the
formation of a secondary organic image, from the oxidation of pyrogallol,
which intensifies the main image. The sensitivity appears higher than with
D 76.
Water to 1000 cc
Metol 2g
Pyro 2g
Borax 6g
Development time 15 mins. at 20°C for Super XX film.
p-Aminophenol developer I.D 44

Water to 1000 cc
Metol 4g
p-Amino phenol hydrochloride 5g
Glucose 20g
Sodium .hexametaphosphate lg
Salicylic acid 0·5 g
Exposures must be doubled.
Phenidone developer. Axford and Kendal have proposed<3 l the following

phenidone developer for relatively fine grain:
Replenisher
Working
Continuous Intermittent
solution
Water to 1000 1000 1000 cc
Sodium sulphite anh. 100 100 100 g
Hydroquinone 5 8 6·5 g
Phenidone 0·2 0·24 0·22g
Borax 3 9 4g
Boric acid 3 ·5 1 0·25g
Potassium bromide 1 -g
Continuous regeneration requires 365 cc per square metre of film. Note
the small amount of Phenidone in the formula, sufficient to promote
superadditivity, because hydroquinone regenerates Phenidone from its oxidation
product.
76. Plain metol developers

These simple formula developers contain a single developing agent. The
results which they give vary with various emulsions; also the published
information on the fineness of grain must be taken with reserve.
Metol formula D 23. Metol, in simple sulphite solutions has little tendency
to fog, which at a pH of 7 ·6 enables development to be carried out up to
30°C.
Water to 1000 cc
Metol 7·5 g
Development time at 20°C, about 25 rnins.
Metol formula D 25. The preceding bath is acidified with metabisulphite,

and its activity is reduced. It therefore develops more slowly and is said to
give finer grain than D 76, but with only 50% of the emulsion speed. <4 >
Water to 1000 cc
Metol 7·5 g
Potassium metabisulphite 15 g
Average development time 22 rnins. at 25°C.
77. Simple pyrocatechin developer

Burki and Jenny<5 > have stated that ammonium sulphate added to a pyro-
catechin developer gives warm-toned colloidal silver. They have prepared
a fine-grain developer by adding a phosphate buffer to keep the pH between
9·7 and 10. The sensitivity is reduced by 50%.
Water to 1000 cc
Sodium sulphite cryst. 15 g
Pyrocatechin 3g
Disodium phosphate cryst. 2g
Trisodium phosphate cryst. 14 g
Ammonium sulphate 14 g
78. Thiocyanate developer

This developer gives quite fine grain, intermediate between that given by
D 76 and that from p-phenylenediarnine. The loss of sensitivity is_40 % .
Working
DK 20 formula solution Replenisher
Metol 5 7·5 g
Sodium metaborate 2 20 g
Potassium thiocyanate 1 5g
Potassium bromide 0·5 1g
Development time 15-25 mins. at 18°C in dish or 12-20 mins. in tank.
79. p-phenylenediamine developers

p-Pheny lenediamine developers< 6 > give very fine grain. They have the dis-
advantages of being slow and toxic; they must therefore be handled with
great care. They stain the skin brown. Loss of sensitivity is 50 % .
p-Phenylenediamine alone
Water to 1000 cc
p-Phenylenediamine (base) lOg
Sodium sulphite anh. so g
Development time: average 25 mins.
p-Phenylenediamine-glycin, preferable to the above.
Water to 1000 cc
p-Phenylenediamine (base) 10 g
Glycin 8g
Development time: 12-20 mins. depending on the initial emulsion grain.
Developers with better solubility and reduced toxicity are obtained by
substituting one of the amino hydrogens with a sulphone group of the types
-S0 2NH 2,-S0 2NHR, -NH-S0 2R (F.P. 866,339-1941).
A satisfactory compound of this type is N-(3-methyl-sulphonamidoethyl-
4-aminoaniline NH 2-C 6H 4-NH-CH 2-CH 2-NH-S0 2-CH 3 • It can
be used in the following bath:
Water to 1000 cc
Sulphonamido-p-diamine Sg
Unfortunately, these compounds are not available commercially, except
for some colour motion picture films.
p-Phenylenediamine-metol formulas
Super Micros T.P.1
p-Phenylenediamine (base) 5 15 g
Metol 10 8g
Hydroquinone 0·5 g
Trisodium phosphate 5 Sg
Potassium bromide 1 0·5 g
Development time at 18°C 6-9 mins. 10-12 mins.
Loss of sensitivity 60 % 50 %
80. Developers using combined p-phenylenediamine
We have already seen (para. 56) that developing agents can be reacted
together to give combined developers such as, for example, metol and hydro-
quinone and p-phenylenediamine and hydroquinone. The compound of
p-phenylenediamine and pyrocatechin gives a fine-grain developing agent,
Johnson's Meritol.
Water to 1000 cc
Meritol 16 g
Developing time: 13-24 rnins. at 18°C.
Loss of sensitivity 50 % .
Used with metol the grain is less fine, but the loss of sensitivity is only
25 % .
Water to 1000 cc
Meritol 13 ·5 g
Metol 2·5 g
Once used, the solutions do not keep.
Taylor<7 l was able to prepare compounds of p-phenylenediamine with
diglycocoll derivatives, which in alkaline sulphite solutions are fine-grain
developers. For example, p-phenylenediglycocoll obtained by condensing
p-phenylenediamine with monochloracetic acid.
81. o-Phenylenediamine developers

Windisch compounded a developer using o-phenylenediarnine and metol
which gave images with grain intermediate between p-phenylenediamine and
D 76. The W 665 formulas are given below:
W665 W665N
o-Phenylenediamine (base) 11 ·6 7g
Metol 11·6 11g
Hydroquinone 1g
Potassium metabisulphite 10 7g
Development time at 18°C 12- 18 mins. 12-15 rnins.
Loss of sensitivity-50 %
82. Atomal developer

The Agfa 'Atomal' fine-grain developer uses hydroxyethyl-o-aminophenol. <8 l
A. {Warm water 800 cc
H ydroxyethyl-o-arninophenol 6g
Pyrocatechin 10 g
Hydroquinone 4g
E
B. {Sulphite anh. 100 g

Sodium metaphosphate 1g
Add B to solution A and make up to 1 litre.
83. Miscellaneous fine-grain developers

A series of fine-grain developers comprises certain basic heterocyclic com-
pounds such as 6-amino-1 : 2 : 3 : 4-tetrahydroquinaldine.
By combining a pyridine nucleus with chlorohydroquinones a developing agent
is obtained <9 > which can be used for the preparation of fine-grain developers.
Negative substituents in the molecule help in this. For example, from
2 : 3-dichlorhydroquinone, hydroquinone-pyridine chloride is obtained which
can be used in a concentration of 7 g per litre together with 60 g anhydrous
sulphite and 15 g anhydrous carbonate. With positive substituents (methyl),
on the contrary, very vigorous developing agents are obtained, for example
2 : 3-dimethylhydroquinone-pyridine, which can be used in normal
developers.
1. Levenson G. I. P.: Brit. Kin., 1948, 37-49; Sci. Ind. Phot., 1948, 211.
2. Smethurst P. C.: Brit. Jl. Phot., 1951, 410; Sci. Ind. Phot., 1951, 418.
3. Kendall J.D.: Brit. Jl. Phot., 1954, 81; Axford A. and Kendall J.D.: Brit. Jl.
Phot., 1954, 138-140.
4. Henn and Crabtree: Phot. Soc. Amer. Jl., 1944, 727.
5. Burki and Jenny: Camera, 1943, 55.
6. For a study of phenylenediamine development see: Fortmiller L. J. and James
T. H.: Phot. Soc. Amer. Jl., 1951, 102; Sci. Ind. Phot., 1952, 100.
7. Taylor G .: B.P. 481,681 (1936).
8. F.P. 636,478 and add. 35,793 (1928).
9. Kumetat K.: Zeits. Wiss. Phot., 1948, 113-119; Sci. Ind. Phot., 1949,96.
Chapter VIII
USE OF DEVELOPING SOLUTIONS

84. Methods of development
The simplest and oldest development method is to immerse the exposed
sensitive material in a quantity of developer sufficient to cover it completely.
The surface of the material can be either horizontal or vertical. In the former
case the operation is carried out in a dish, and in the latter, a tank. The stag-
nant accumulation of development by-products in a tank where a large volume
of liquid remains stationary is greater than in a dish. This is why tank
development generally takes longer.
When the liquid is circulated, or the material agitated, the development
time can be greatly reduced. This takes place in the development of motion
picture materials in a continuously running machine; here, the film, guided
by rollers passes successively through the development, fixing and washing
tanks.
It is, however, sometimes necessary to perform all these operations-
development, fixing and washing-in the same vessel without disturbing the
material. This takes place, for example, in some radar ultra-rapid processing
units. (ll The vessel in this case is very small and is equipped with a pump to
change the baths rapidly.
Another method which is becoming widely used is spray development. The
developer is applied as flat conical jets from nozzles. <2 >Oxidation is obviously
accelerated, but as the volume of the bath is small it is frequently renewed.
The system is more economic if the pH of the bath is ~ 9.
Katz and Esthimer<3 > have speeded up development up to three times by
applying a turbulent liquid to the development surface, that is, a rapidly
circulated liquid.
Application of a viscous developer is used in the treatment of optical sound
tracks in some colour processes. The developer is thickened with carboxy-
methylcellulose or with methylcellulose. If the picture area is treated in the
same way, one would imagine that the bromide liberated in the high densities
would soon prevent the small quantity of developer from functioning.
According to Rudkin, this disadvantage can be overcome by adding colloidal
silica or kieselguhr. <4 >
Finally, it is possible to develop with a sponge which is kept moving over the
image to avoid uneven treatment. This method is often used for processing
large bromide prints.
101
85. Development time

The development time is influenced by many factors: emulsion type,
developer formula, dilution and working method, required gamma, tempera-
ture and agitation.
Negative development takes a long time with fine-grain developers-10 to
20 minutes. With ordinary developers the time is 5 to 10 minutes. Motion
picture positive is developed in 3 to 4 minutes.
The contrast increases with development time until a limit is reached depen-
dent on the emulsion type and the developer composition.
Fine-grain emulsions develop much more quickly than coarse-grain high-
speed ones. The speed of development also depends on the crystalline form
of the silver bromide and the gelatin ratio of the photographic layer.
As a general rule in continuous professional work the development time must
be periodically modified to compensate for the changes in contrast due to varia-
tions in the composition of the bath, changes which can reach or even
exceed ± 10 % of the required gamma.
86. Development temperature

Temperature influence is represented by an Arrhenius equation which has
been studied by James. (<tb > The normal development temperature is 18- 20°C,
but it is possible that development must be carried out at temperatures lower
or higher than this. In this case the normal time must consequently be in-
creased or decreased. Inadequate temperature control of the bath always
results in irregular development.
Below l8°C the activity of hydroquinone decreases much more rapidly than
that of metol, which, in effect, varies the composition of an M.Q. developer
towards a less contrasty bath. The reverse takes place at temperatures above
18°C.
Generally, the developnunt time should be doubled or halved for a difference
of 8°C less or more. As an example, here are the relative times for three differ-
ent developers :
D76 D 72, 1 : 1 Dll
13°C 17 mins. 8! mins. 6 mins.
15·Soc 13 6! 5
18°C 10 " 5 " 4 "
21 °C 7!
" 4 " "
3!
24°C 6 " " "
3 2!
" " "
We have already seen that in the presence of sodium sulphate, which
prevents the gelatin from swelling, the development time at 24°C is practically
the same as at 18°C. It is the same with an unhardened film developed at
l8°C and the same film pre-hardened and developed at 24°C. Above 24°C
the time must be reduced:
Temp. 27°C 29°C
Take 85 % 70 % 60% 50% 25 % of the nor-
mal time
To develop at low temperatures without too great an increase in time, <5 >
5-15 % urea can be added to swell the gelatin and speed up development by
25 %. The oxidation of the developer is accelerated, giving warmer tone
images.
87. Agitation
Developer agitation is an important operation which has a consider-
able influence on the image characteristics. The rapid elimination of by-
products can bring about a considerable reduction in the time taken to
complete the image; this takes place by development with a turbulent
liquid.
Agitation by intermittent jets of gas< 6 > at a pressure of 0·35 kgfcm2 is
preferable to mechanical agitation or simple circulation. Changes in the
developer are negligible if nitrogen is used.
The development of low densities is governed chiefly by the reaction speed
of the developer, but that of high densities depends on the diffusion of
the developer in the emulsion layer. This is important in case of short
developing times. The use of hydroquinone prepared with radioactive carbon
C 14 permits the phenomenon to be observed. (Sc)
88. Equipment materials

Development is carried out in dishes or tanks made from materials inert to the
developer. Pyrex glass and porcelain are suitable only for small apparatus. Enamelled
iron<•bJ is often used for dishes, and stoneware for tanks; the former is readily chipped,
whilst the latter is very heavy and awkward. Stainless steel and plastic materials are
best.
Stainless steel must not contain more than 0 ·08% carbon otherwise an iron carbide
is formed during welding which leads to corrosion.<•> Welding is preferably done
electrically in an inert atmosphere with a jet of cooling water on the opposite side.
The sheets must be annealed and polished. Treatment with nitric acid diluted with
2·5 parts of water for 30 minutes at 50-60°C removes the superficial impurities (this
operation must be carried out where there is adequate ventilation and gloves must be
used).
Muehler and Crabtree have given the following test for molybdenum stainless steel,
the only resistant one: put a drop of concentrated nitric acid onto a clean area of the
vessel or sheet, then a drop of concentrated hydrochloric acid. L eave for 30 seconds.
Transfer the reacted drops to a porcelain crucible with a micropipette. Add 10 drops
of distilled water then 4 drops of 10% potassium thiocyanate. Stir, then add 5 drops
of stannous chloride solution (dissolve 6·5 g stannous chloride in 5 cc hot hydro-
chloric acid then make up to 25 cc with water). If an orange-red coloration is produced
the steel is molybdenum stainless type 316, but if only pale green then the steel is
type 304 without molybdenum.
D eveloping tanks are often made from polyvinyl chloride which can be hot-air
welded. At one time ebonite was used, but chlorinated rubber is better. T eflon (poly-
tetrafiuoroethylene), which has very high chemical resistance can also be used. In the
absence of other materials, wood can be used, but if possible it should be impregnated
with paraffin wax, bitumen or bakelite, or it will be necessary to sterilize it periodically
with a toxic solution of 1 : 1000 pentachlorophenol.
The developing apparatus fittings (pump, pipes, taps) should be stainless steel,
lead, ebonite or P.V.C.
Non-metallic equipment can be cleaned with the corrosive solution of dichromate in

sulphuric acid:
Water 1000 cc
Potassium dichromate 80 g
Sulphuric acid cone. 50 g
Dissolve the dichromate in warm water. Cool, then slowly, and with stirring, add the
acid to the solution. Warning : n ever pour water into the sulphuric acid: this can splash
acid into the air.
After cleaning retain the chromic acid solution, and wash with plenty of water.
M etallic apparatus is cleaned with damp pads and fine chalk or pumice powders
or even household cleaners. Remove rust marks with 10% nitric acid or sodium
nitrate.
The bath is contaminated during development with foreign matter brought in by
the films and by the air, and with particles of gelatin, colloidal silver and insoluble
calcium salts. The sludge which is produced necessitates careful filtration of the
circulated bath, using clean filters. The sludge is deposited on the inside of tanks and
in the pipes. Periodic cleaning in 1% hydrochloric acid for 3-4 hours is advisable .<•>
Neutralization with 2% soda and washing follows.
89. Sulphide fog

Water frequently contains sulphur-producing bacteria which attack the sulphite
of a developer left in a deep tank. They form sodium sulphide which results in
a yellow fog of silver sulphide. Mter a few films have been developed, this fog
disappears due to exhaustion of the sulphide.
Hypo-contaminated clips can also produce this fog.
Bacterial reduction (proteus vulgaris) of sulphite (or hypo) of used develo-
pers was noted by Dundon and Crabtree. <9 l It produces a slight grey
deposit or dichroic fog with a metallic lustre on the gelatin surface of films.
This deposit is not firmly fixed; it can be removed with a pad damped with
alcohol, or by immersing in a 10 % solution of ammonium thiosulphate con-
taining 0·5 % acetic acid, or failing that, in an acid-hardening fixer. It con-
sists of silver sulphide Ag 2 S covered with metallic silver. It can be reproduced
artificially by adding 0·2-10 mg per litre of sodium sulphide to the bath. Its
natural occurrence is encouraged by the presence of particles of gelatin (rich
in sulphur compounds such as cysteine), red antimony sulphide rubber, or
atmospheric hydrogen sulphide.
The sulphide fog can be avoided by adding to the bath 30 cc per litre of 1%
cadmium chloride.
To neutralize the sulphide, add 0·1 g per litre lead acetate dissolved in a
little water. The resulting precipitate is allowed to settle.
To prevent the action of sulphide bacteria Henn and Crabtree <10 l re-
commend resorcinol (0·1-0·5 %) and pentachlorophenol (0·005- 0·01 %)
(poisonous). Rogers (ll) proposed derivatives of 3 : 6-diaminoacridine:
acriflavine, proflavine and dyestuff 914 (I. C. I.) in a concentration of 1·25 mg
per litre.
Whatever method of elimination is used, cleaning the tanks with warm
water containing 5% trisodium phosphate is recommended.
90. Aerial oxidation of developers
Aerial oxidation of developers takes place spontaneously without use. During
development, the two oxidation processes-aerial and by silver bromide
-take place concurrently. In aerial oxidation it is primarily the hydro-
quinone which is affected, the products being hydroquinone-mono-
sulphonate, sodium sulphate, sodium hydroxide and various brown tanning
substances (5 %).
The amount of sodium sulphate which is produced can be used to determine
the degree of aerial oxidation, as this substance is not produced during oxida-
tion by silver bromide. One molecule of oxygen, 0 2 , forms one molecule of
sodium sulphate Na 2S04 from sodium sulphite Na 2S0 3 , the other half of the
oxygen being used in the formation of a molecule of sodium hydroxide. The
sodium sulphate is estimated by adding barium nitrate, and weighing the
barium sulphate BaS04 , which is precipitated.
In developing machines, aerial oxidation is encouraged by circulating
pumps, filtration systems, film perforations and by air forced in for agitation.
Oxidized baths give much lower gammas.
Aerial oxidation fog is accelerated by copper in concentrations of 2 mg per
litre (except with the non-alkaline D 76). The action of the copper can be
neutralized with 0·1 % phenosafranine and sequestering agents: Versene,
Sequestrene, Trilon B or F.
Keeping properties of developers. Developers keep for 24 hours in dishes,
15-30 days in tanks, and 3-6 months in well-stoppered bottles.
Tank Stoppered bottle
D72 15 days 3 months
D76 30 days 6 months
DK20 30 days 6 months
D 11 30 days 6 months
Caustic soda developers do not keep.
91. Exhaustion of developing solutions

Take, for example, a metol-hydroquinone solution contaimng sulphite, car-
bonate and 1% potassium bromide. The reduced silver bromide liberates an
equivalent quantity of soluble bromide, whilst the silver is deposited in the
gelatin layer. The silver iodide produces soluble iodide. The developing agents
are used up in proportion to the amount offilm developed. To reduce 1 g of silver
bromide, 0·36 g of hydroquinone or 0·8 g of metol are needed and they
decompose 0·55 g sulphite, forming monosulphonates and small quantities of
disulphonates. The halide dissolved by the sulphite is reduced to colloidal
silver which coagulates to muddy materials removed by filtration.
The progressive destruction of the developing substance leads to a reduc-
tion of image contrast; the accumulation of bromide slows down develop-
ment although, after a certain limit is reached, the iodide in solution is taken
up by the sensitive layer. (l2l
106 PHOTOGRAPHIC CHEMIST RY
With an unreplenished developer the necessary development time increases

in proportion to the exhaustion. After an area of 0·5 m 2 has been developed
the time is doubled with an M.Q. carbonate bath. It is doubled after only
0·25 m 2 in D 76 which is spent after 0·37 m 2. It is the same with the thio-
cyanate containing DK 20.
In the case of papers, D 72, diluted with an equal volume of water can
develop 1·5 m2.
92. Continuous development

In the development of film on continuous machines the composition of the
developer must be kept constant for months on end. Let us see what happens
during the treatment of 35 rom film.
When the developed film leaves the developer, it takes with it a certain
amount of developer (observed to be in the region of 30 ccfmetre) which is
completely lost. In the same film 0·05 g of metallic silver per metre (5 g/100 m)
is produced, and a corresponding quantity of soluble bromide is left in the
solution. The proportions of metol and hydroquinone which are used up have
already been given. Knowing the quantity of film developed in an hour
(1800 metres for example) it is easy to calculate the approximate weights of
materials involved.
Consequently, on one hand the concentration of active constituents is
reduced, whilst the concentration of unwanted by-products is increased.
Hydroquinone, metol and sulphite are used up, whilst bromide, sulphonates
and sodium sulphate are produced, and the pH is altered by the liberation of
hydrobromic acid and sodium hydroxide.
Use is made of the carry-over of solution in regenerating the bath by
maintaining the solution level with a new solution of special composition
(replenisher).
If, after an hour, for example, a quantity h of hydroquinone is used in each
litre (by oxidation by silver bromide and by the air) and if the volume of
liquid lost is L, a similar volume L of new solution containing Vh + L(H - h )g
of hydroquinone must be added. Vis the total volume of developer and H the
initial hydroquinone concentration per litre. Similarly with the other con-
stituents, metol and sulphite. Taking a smaller unit of time, more accurate
amounts can be calculated.
Calculations are more complicated in the case of the by-products formed
in the same bath. The solution is continually enriched with more and more
unwanted substances. The loss of the volume L of developer in each unit of
time removes a certain amount, but as this is again diluted with the bulk of
the liquid, the quantity removed is less than the quantity produced.
Suppose that sg hydroquinone-sulphonate are produced per litre per hour.
At the end of the hour L litres of old developer are removed and replaced by
L litres of a new developer. After this operation there are s(V - L)/(L)g of sul-
phonate per litre. (V- L )/V is the proportion of solution kept after each
operation. If we represent it by r, the amount of substance remaining after
the first replenisher addition is sr. After the second hour, there is s+sr g of
sulphonate of which it remains (s+sr) x r = sr+sr2 • And after the nth opera-
tion, we shall have sr+ sr2 +sr3 • •• srn, which can be written: s(r+r2 +r3 ••• rn)
Actually the variation does not take place each hour, but continuously at each
instant dt. One can therefore apply the Evans formula <13 l
X = k- (k- a)e-Lt/V
where x represents the concentration (per litre) of the substance under

consideration at timet (minutes) a is the initial concentration of the substance
in the bath, k the concentration of substance formed at each moment,
assumed to be dissolved in the volume L (per minute) and e is the Naperian
logarithm base.
There then comes a time when the concentration of the unwanted sub-
stance formed is so high that the amount disposed of in the volume L of the
solution carried over equals the amount formed. At this moment the bath is in
equilibrium; the unwanted material is removed as quickly as it is formed. The
function x represented by the Evans formula is an exponential function which
consequently tends towards a limit which is precisely this equilibrium. But
there are several different equilibriums for each of the substances concerned.
Take, for example, the example of soluble bromide given by Evans.
The initial concentration in the developer is I g per litre therefore a = I.
Let L = 10 litresjminute, and the total volume of liquid, V = 40,000 litres,
feeding several machines. If a total of 300 metres of film per minute is devel-
oped under these conditions an average of 15 g of silver and 15 g of sodium
bromide are produced per minute.
As!= 10Lwehavek= 15J10= 1·5gofbromide. Theequationbecomes
w t
x = 1·5- (1·5 -l)e-<o,ooo t = 1·5-0·5e-<.ooo
At t = oo it is seen that x = 1·5 g: at the equilibrium the bromide con-
centration is, in fact, constant. To reach a concentration of 1·4 g per litre
(starting with the initial concentration in a fresh bath) the time necessary is
given by substitution in the preceding formula:
2·3V (k- a)
t = - - log10 - - -
L (k- x)
giving t = 9,200 minutes, or about six days. The new bath is, then, almost
at the equilibrium for bromide after six days' continuous use.
The calculation which has just been made for the bromide can be applied
to all of the bath constituents. In each case an equilibrium is reached.
The study of continuous development must be completed by:
1. Analytical estimation of the substances present at various determined
times.
2. The measurement and adjustment of pH.
3. The development of sensitometric strips.
4. The working out of suitable different replenishers for when the machine
is in use or idle (surface oxidation only in this case).
E•
108 PHOTOGRAPHIC CHEM ISTRY
93. Faults due to development

Certain faults of developed images are due to improper development conditions.
Patches : uneven development due to poor circulation of the bath. They are particu-
larly prevalent when the development is short in an energetic bath.
Clear parallel lines going in the opposite direction to the film movement (streamers)
or downwards if it is in a static vertical position : due to by-products streaming from
high density areas which slow down development in the adjoining area.
Development too slow: spent developer, temperature too low or an accidental excess
of bromide.
Development too fast: developer too concentrated or too warm.
Fog: over-development, developer too warm or lacking bromide (assuming that it
is not emulsion or light fog), accidental presence of an organic fogging agent provided,
for example, by red rubber or a nearby chemical store.
Yellow fog: bath, or sensitive material, sulphide contaminated-chloride paper
defective or developed too long.
Pressure marks: from slides or rollers; irregular circulation of by-products.
Clear circular spots. Air bells on the surface of the sensitive material at the time of
immersion. They are also caused by the perforations, circulating pumps and air
agitation jets.
Dust can be stuck to the dry film or may come from a badly filtered bath.
Oil marks from the mechanism of the machine.
Reticulation: developer too warm or caustic, followed by a cold rinse.
Certain faults are due to the emulsion: absorbent spots due to static electricity
(effluvia), grey mottle on papers, white points with dark centres or black points with
halos, due to dust falling on paper during baryta treatment or on the emulsion during
coating.
94. Development accelerators

There are six ways to increase the development rate of a particular emulsion.
The first three depend on the same principle-the increase of developer
energy. <14 >
1. Concentration of the developer (to an optimum value).
2. Increase of alkalinity.
3. Raising the temperature.
4. Swelling the gelatin by adding urea to the bath (para. 86).
5. Reduction of the potential barrier surrounding the silver bromide grain
by including a cationic surface active agent< 15 >such as laurylpyridinium chloride
in a concentration of 0·1 g per litre. The maximum density is also increased.
The access of developer ions is increased due to the reduction in negative
surface charge by this product. <16 >
6. Addition (or pre-treatment) of 0·1 g per litre of a dye such as neutral red,
safranine, methylene blue, methyl violet, janus green, pinakryptol yellow, <17 >
3 : 3'-diethyl-oxa- and thia-carbocyanine chlorides, etc. This can at the same
time produce fog and colour desensitizing or sensitizing.
, According to James, the dye acts as a surface active agent to reduce the
potential barrier. Levenson <18 > on the contrary, has put forward the idea that
their action is more like that of a developing agent analogous to metol in
superadditive developers, based on the fact that the leuco derivatives of the
dyes are powerful developers.
95. Ultra-rapid development
We have just seen that the rate of development is dependent un the concen-
tration of developer, on the pH, on the temperature and on the presence of
accelerators. It also depends to a great extent on the rate of agitation, that is,
on the rapid renewal of the liquid.
In caustic solutions at high temperatures, development is particularly
rapid. Under these conditions it is advisable to add an antifoggant, and also
formalin or glyoxal if the emulsion has not been previously hardened.
The following formula is widely used:
Water to 1000 cc
Alcohol 100 cc
Ethylene glycol 100 cc
Metol 15 g
H ydroquinone 15 g
Caustic soda 15 g
This bath can be used concentrated, or diluted with 500 cc of 10 % ethy-
lene glycol. Thus diluted it develops in 4 seconds at 60°C. <19 > It is advisable
to add 0·5 g of benzotriazole as an antifoggant.
Fix in 10 % hypo containing 50 cc bisulphite, heated to 60°C. Do not add
alum as it decomposes at this temperature.
The above formula can also be used without the addition of glycol. The
latter is a hygroscopic compound and enables the material to be dried after
rapid fixing and washing without crystallization of the substances still present
in the film.
If the emulsion is not hardened, add 5-10 % formalin.
Another bath which develops in 30 sees. at 40°C contains:
Water to 1000 cc
Metol 27 g
Hydroquinone 27 g
Caustic soda 40 g
Benzotriazole 1g
Formalin 35 cc
Pyrocatechin formula:
Water to 1000 cc
A Pyrocatechin 100 g
( Sodium sulphite anh.
100 g
Water 1000 cc
B Caustic soda 60 g
( Potassium bromide
100 g
C Formalin 200 cc
Omit the formalin with hardened emulsions.

Development time: 40 sees. at 30°C. A few seconds at 60°C.
Phenosafranine formula:
Water to 1000 cc
A Sodium sulphite anh. 25 g
H
{ ydroquinone 50 g
Phenosafranine 1 : 5000 25 cc
Water to 1000 cc
B Caustic soda 300 g
( Potassium bromide lOg
Treat for 5 seconds in A, then 1 second in B.
According to Crabtree and Russel, a well hardened emulsion can be devel-

oped in 1 second at 65°C in D 8 developer (hydroquinone-caustic-excess
bromide). Jaenicke also disclosed a sensitive layer impregnated with hydro-
quinone, dried and exposed, which gives an image in 1 second by simply
treating in strong alkali.
Development is stopped by immersing in a stop bath heated to 50°C con-
taining a buffering agent like sodium acetate. If the emulsion is lightly coated,
fixing can be omitted.
To develop with maximum speed, the solution must be rapidly streamed
down as a thin layer, on the surface of the sensitive material. Equipment to
do this has been made. <2o>
1. Blackner, Brown and Kunz: Jl. Frankl. Inst., 1946, 203-216; S ci. Ind. Phot.,
1947, 21. Katzen and Ganes: Phot. Engng., 1951, 195-202.
2. lves C. E .: Phot. Engng., 1951, 116-126; Levenson G. I. P.: Brit. Kin., 1949,
65-81; Sci. Ind. Phot., 1949, 252.
3. Katz L . and Esthimer W . F .: Jl. Soc. Mot. Pet. Tel. Eng., 1953, 105-129.
4. Rudkin L. C .: Brit. Kin., 1954, 18; S ci. Ind. Phot., 1954, 456.
4b. James T . H. : Phot. Sci. Techn ., 1955, 81- 90.
5. Dersch F., Phot. Soc. Amer. Jl., 1945, 467; Varden L. and Krause, Phot. Age,
1949, 20.
6. Smibert ]. A. and O'Bern M., R.P.S. Cent. Conj., London 1953; and Sci. Ind.
Phot., 1953,410.
6b. Galvanized iron is readily attacked and should never be used.
6c. Lu Valle, Dunnington and Margnetti : Phot. Engng., 1955,6,42-49.
7. Muehler L. E . and Crabtree J. I.: Phot. Soc. Amer. Jl. , 1953, 92-104.
8. Unless the tank or the piping are in a metal which is attacked by weak acids.
9. Dundon and Crabtree: Sci. Ind. Phot., 1925, 25.
10. H enn R. W . and Crabtree J . I. : Phot. Soc. Amer. Jl., 1947, 752-758 .
11. Rogers T. H.: Jl. Chern. Ind. Soc., 1940, 34.
12. SeeJl. Soc. Mot . Pict. Tel. Eng., F eb . 1943.
13. Evans R. M.: Jl. Soc. Mot. Pict. T el. Eng., 1938, 31, 278 .
14. A reduction of sulphite also increases the development rate.
15. See chapter on theory of development.
16. James T. H.: Sci. Ind. Phot., 1951,416. Fortmiller and James : Phot. Soc. Amer.
Jl., 1952, 76-80.
17. Rzymkowski J.: Sci. Ind. Phot., 1951,98.
18. Levenson G . I. P.: XIth Int. Cong. Pure and Appl. Chem. , 1947, 533.
19. Blackner, Brown and Kunz: Jl. Frankl. Inst., 1946, 203-212.
20. Tuttle C. M., Brown and Tuttle N. R.: Phot. Engng., 1952, 65.
Chapter IX
THE DEVELOPING AGENTS

96. The developing functions of cyclic compounds
A compound is a reducer with respect to exposed silver bromide when its
redox potential is lower than 120 m V at a predetermined pH, and when it
can be adsorbed to the crystal surface.
Whilst the chemical constitution of the reducer is unimportant in itself
when the preceding condition is fulfilled, it is nevertheless true that these
conditions are essentially dependent on the constitution. (I) To be of practical
use, a developing agent must, in other respects, have certain characteristics
which simplify its use: solubility, keeping qualities, absence of stain, reason-
able power at a moderate pH, non-toxicity, simplicity of preparation to be
economical, etc. No developing agent possesses all of these properties
together.
Developing agents having an aliphatic (non-cyclic) structure are known,
but have no place in current use. Only a few aromatic (or cyclic) uevelopers
are made on a large scale and made available to photographers.
Organic compounds capable of developing fall into two groups, the
hydroxy compounds and the amines; they can be hydroxy and amino at the
same time= aminophenols.
In all cases, at least two functional groups, hydroxyl or amino, must be pres-
ent; in other words, the nucleus must contain two -OH gr oups, two -NH 2
groups or one -OH group and one -NH2 group.
OH and NH 2 are, by convention, termed developing functions.
In addition, for the developing functions to be active, they must be present
in the ortho or para positions relative to each other.
Thus o-dihydroxybenzene and p-dihydroxybenzene (also known as pyro-
catechin and hydroquinone) are developers, whilst m-dihydroxybenzene
(resorcinol) although a reducer, does not develop, or only with great difficulty.
OOH
OH
0 OH
OH
o-dihydroxybenzene p-dihydroxybenzene m-dihydroxybenzene
(pyrocatechin) (hydroquinone) (resorcinol)
112
The same is true of m-aminophenol and m-phenylenediamine.
The reason for this anomaly lies in the fact that the meta compounds are
more prone to exist in the keto form, with one of the phenolic hydrogen atoms
migrating to an adjacent nuclear methine group, C. OH becoming C : 0.
This molecular rearrangement is most pronounced in phloroglucinol
C 6H 3{0H) 3 in which the three hydroxyl groups are all meta to each other.
If the migration of the hydrogen atoms is prevented by nuclear substituents,
the meta compounds have developing properties. When the nuclear carbon
atoms adjacent to the hydroxyl groups carry methyl, CH 3 , substituents, the
hydroxyl groups retain their hydrogen atoms ; mesoresorcinol is a developer.
OH
c~oc~
OH
CH3
resorcinol mesoresorcinol
(non-developer) (d eveloper)
The mechanism of reduction by the di- and tri-hydroxybenzenes is, there-

fore, essentially a transformation from the phenolic to the quinonoid state in
which the phenolic function C-OH becomes a cyclic ketone function C = 0
with liberation of hydrogen ions :
H ydroquinone quinone ion H ydrogene ion
It has already been shown how quinone combines with the sulphite present
in the developer to form a sulphonate. <2 >
We have said that resorcinol develops only slightly-if at all. In fact, it can
be made to develop very slowly. James and Levenson<3 > used a solution con-
taining 11 g resorcinol and 28 g caustic potash per litre, for 4 hours at 25°C
in an atmosphere devoid of oxygen. A yellow residual image was formed at
the same time.
HYDROXYBENZENES
97. Hydroquinone
Hydroquinone, C 6HiOH) 2 (p-dihydroxybenzene) was disclosed as a devel-
oper by Abney in 1880. It occurs in needle-shaped orthorhombic prisms,
melting point 169°C. It is more readily dissolved in hot than cold water, and
is soluble in alcohol and ether.
It is identified by sulphomolybdic acid; 80 cc of 15 % ammonium molyb-
date and 20 cc of 30 % sulphuric acid give a dark blue coloration when boiled
with hydroquinone. Pyrocatechin and the phenolic acids are first removed by
precipitation with 10% lead acetate.
Preparation. Quinone, prepared by oxidizing aniline, is reduced to hydro-

quinone with sulphur dioxide.
C 6H 40 2 +S0 2 +H 20 --+ C 6 HiOH) 2 + H 2S04
One part of aniline is dissolved in 8 parts of dilute sulphuric acid and 3
parts of sodium dichromate are added in small portions. After the solution
clears, the temperature is raised to 35°C and the quinone is extracted with
ether, and purified by steam distillation. The yellow crystals which are
obtained are treated with sulphur dioxide in alkaline solution. The resulting
hydroquinone is extracted with ether. It is purified by dissolving in water,
decolorizing with activated carbon, and crystallizing after a short treatment
with sulphur dioxide. Other reducing agents can be used- bisulphite< 4 l or
ferrous sulphate, <5 l or the reaction can be carried out under reduced pres-
sure. <6 l Following another procedure <7 l the reduction is stopped when the
pH is between 5 and 9; the reaction is finished after adding a primary amine
which precipitates the hydroquinone produced.
Hydroquinone can be prepared by the following scheme: 16 ·g aniline are poured
into a flask containing 400 cc water and 80 g sulphuric acid cooled in iced water.
About 40 g of finely ground dichromate is slowly added until the green precipitate
formed is redissolved. The resulting solution is poured into a vessel containing 200 cc
of ether; after shaking and standing 30 minutes, the ether layer is separated, and the
ether is evaporated off. Quinone crystals are left. These crystals are dissolved in a
little water on the water-bath, and an excess of saturated sulphur dioxide solution
(about 150 cc) is added. The quinone is reduced to hydroquinone. Heating is con-
tinued in an evaporating basin until the water is removed and the hydroquinone
crystallizes. The product is recrystallized from boiling water (20 g to 100 cc). By
cooling to 10°C, 17 g of the purified product is deposited. The remaining 3 g can be
recovered from the mother liquor by evaporation.
Aniline can be oxidized with manganese dioxide and sulphuric acid. The quinone
is then reduced with iron powder. Using the method of von Bramer and Zabrisbie
of the Tennessee Eastman Corp., the yield of purification is increased by steam
distilling rather than crystallizing.< 8 >
Instead of starting with aniline, benzene C 6H 6 can be oxidized by electro-
lysis in an acid medium. <9 l To reduce quinone to hydroquinone, Kikuchi and
Masago<10 l used as catholyte 300 cc of 2% H 2 S04 containing 5 g of quinone
and 0·5 g ammonium vanadate (catalyst) and as anolyte, 30 cc of 2 % H 2S04 •
Lead electrodes. Temp. 50°C; D.C. 3Afdm2 at 6-7·5V; time 3 hours.
Also, by treating p-bromophenol with an alkali between 75 and 150°C,
hydroquinone is produced. (Ul
Br. C 6H 40H + KOH--+ C 6 H 4(0H) 2 +'KBr
Fasciati <12 l treated p-dichlorophenol with oleum, then with soda lye in the
presence of copper.
98. Hydroquinone derivative developers

2-Chlorohydroquinone (Adurol) which occurs as colourless needles or tablets
M.Pt. W3°C. It is soluble in water and alcohol. ClC 6H 3(0Hh
Schering's bromohydroquinone and 2 : 3-dichlorohydroquinone.
The halogens generally increase the energy of the developer when substi-
tuted in the nucleus, especially bromine.
Toluhydroquinone CH 3C 6H 3(0H) 2 and xylohydroquinone (CH 3) 2 • C 6H 2
(OH) 2 are the hydroquinones derived from toluene and m-xylene.
1 : 2 : 5-Trihydroxybenzene is a developer, although phloroglucinol (the
1 : 3 : 5 compound) does not develop, its hydroxyl groups are in the meta
position to each other.
Nitro groups, being oxidizing groups, completely neutralize the developing
properties of hydroquinone when they are introduced into the nucleus.
The following alkyl and acylamino derivatives of hydroquinone were dis-
. closed as developers in 1936 by L. Schinzel <13 >: 2 : 5-dimethyl and 2 : 5-di-
ethylhydroquinone; 2 : 5-diphenoxyhydroquinone, 2 : 5-di-p-phenetyl-
hydroquinone, 2 : 5-dibenzoylaminohydroquinone, 2 : 5-diacetaminohydro-
quinone, 2 : 5-diphenyl-3 : 6-dibenzylhydroquinone.
Hydroquinone-pyridine derivatives: Buchta, Barnett, then Diels succeeded
in replacing the chlorine of chlorhydroquinone with pyridine. It now seems
preferable to react quinone and pyridine in the presence of acetic acid. <14 >
By adding HCl, yellow needles are obtained, M.Pt. 225°C.
The hydroquinone-pyridine derivatives are more soluble than hydro-
quinone (for they form hydrochlorides), often produce less fog and are not so
prone to aerial oxidation.
To prepare a developing solution, 7 g of this product are used with 30 g
sulphite and 70 g carbonate (per litre).
The energy is increased by introducing positive substituents into the
hydroquinone nucleus, e.g. 2 : 3-dimethylhydroquinone-pyridine which yields
very energetic developers (K. Kumetat): <15 >
Water to 1000 cc
2 : 3-dimethylhydroquinone-pyridine 7g
Sodium sulphite, anhydrous 60 g
Potassium carbonate cryst. 35 g
99. Pyrocatechin
Pyrocatechin, used by Eder and Toth in 1880 is an o-dihydroxybenzene
isomeric with hydroquinone. It crystallizes in orthorhombic prismatic
needles which melt at 104°C, and is readily soluble in water, alcohol and
ether.
Pyrocatechin is prepared by reacting caustic soda with a-chlorophenol in
an autoclave at 300°C.
o-chlorophenol caustic soda sodium water sodium

o-diphenate chloride
Copper salts are catalysts in this reaction. The sodium salt is reacted with
sulphuric acid to liberate the pyrocatechin, which is extracted with ether
(removed by distillation at reduced pressure).
Pyrocatechin is also obtained by fusing a-dichlorobenzene with caustic

potash and also by heating guaiacol <16 > with hydrochloric acid in an autoclave
at 140°C.
Adrenalin: hormone derived from pyrocatechin, l-adrenalin with the for-
mula C 6H 3(0Hh. CH(OH)-CH 2 • NH. CH 3 , is a developer. J. Rzym-
kowski <17 > used the following bath: adrenalin 4 g, caustic soda 4 g, potassium
bromide 1 g, water to 1000 cc.
100. Pyrogallol
Pyrogallol was disclosed by Regnault and Archer in 1851; it is a 1 : 2 : 3-tri-
hydroxybenzene (diphenol) with the formula:
OH
c) OH
OH
It is in the form of colourless needles melting between 131·5 and 132·5°C,

soluble in water, alcohol and ether. In alkaline solution it rapidly absorbs
oxygen from the air, and turns brown. When poured into lime wash, a charac-
teristic red colour is produced.
Pyrogallol is formed by the action of caustic potash solution on dibromo-
salicylic acid, but in practice it is prepared by thermal decomposition of gallic
acid.
Gallic acid Pyrogallol Carbon

dioxide
Gallic acid, the monocarboxylic acid corresponding to pyrogallol is itself

obtained from the tannin of gall nuts. The crushed gall nuts are extracted
with a mixture of 5 parts ether, 0·6 parts alcohol and 0·2 parts water. After
24 hours, the liquid is drawn off and separates into two layers. The lower
layer, yellow and syrupy is extracted with ether, and the extract is evaporated
under reduced pressure. The yellowish white powder which remains is com-
posed of tannin. The tannin solution together with a dilute acid is heated to
70-80°C for 24 hours. The tannin is hydrolyzed to gallic acid which is deposi-
ted from the filtered solution. It is purified by decolorizing with animal
charcoal and recrystallizing from alcohol. The hydrolysis can also take place
by means of 'penicillium glaucum' or 'aspergillus niger', both of which
contain a diastase, tannase, which attaches the elements of a molecule of water
to the tannin.
To convert the gallic acid to pyrogallol, it is heated to 200°C together with
two parts of water. The carbon dioxide is released at intervals. The resulting
solution is decolorized with animal charcoal then, after concentration, is left
to crystallize. The gallic acid can also be distilled with powdered pumice-
stone in a current of carbon dioxide which carries away the resulting
pyrogallol.
The esters of pyrogallol are developers. These include !-methyl and
1-ethyl-pyrogallols disclosed by Schuster<18 >and Stockelbach's<19 >1-tert-butyl
and diethyl-pyrogallols.
A further trihydroxy-benzene, methylated directly in the nucleus was dis-
dosed by Schinzel<20 >-2 : 4 : 6-trimethyl-1 : 2 : 3-trihydroxybenzene.
101. Naphthols
Many naphthols have been used successfully as photographic developers:
1 : 4-Dihydroxynaphthalene C10H 6{0H) 2 , 1 : 5-dihydroxynaphthalene,
1 : 5-dihydroxynaphthalene-6-sulphonic acid (Andresen 1889), <21 > 4-meth-
oxy-1-naphthol OH. C10H 6 • OCH 3 and 4-ethoxy-1-naphthol, <22 >2-phenyl
-1 : 4-dihydroxynaphthalene C 6H 5 • C 10H 5{0H) 2 (Schinzel1936).
102. Hydroxyanthracenes
Schinzel <23 >has also desclosed the following compounds as developers:
1 : 2-dihydroxyanthracene
1 : 4-dihydroxyanthracene
1 : 2-dihyroxyanthracene moilomethyl ester
1 : 4~dihydroxyanthracene monomethyl ester
103. Influence of aldehyde, carboxyl and ketone groups

The introduction of an aldehyde group -CH = 0 into the benzene ring of
the developer has no appreciable influence on the developing power; thus
protocatechuic aldehyde C 6 H 3{0H) 2CHO, a hydroquinone derivative, is a
normal developer.
The carboxyl grou.'> -COOH, characteristic of organic acids, has a more
pronounced influence. If the carboxyl group is directly substituted in the
nucleus in the para position, developing power disappears. Thus gallic acid,
a pyrogallol derivative, does not develop, nor does the pyrocatechin deriva-
tive, protocatechuic acid C 6H 3(0H) 2 • COOH. This is explained by the
assumption that the carboxyl group and the hydroxyl group, in the para
positions to each other, are transformed into anhydride groups in the pres-
ence of alkalis. This results in the loss of a developing function -OH, that
remaining in the ortho position being insufficient. By esterifying the carboxyl
group this conversion to the anhydride is prevented, and consequently the
developing power is not lost; thus ethyl gallate develops whilst gallic acid does
not:
OH OH
O O
OH OH
CO.OC2H5 OH CO.OH OH
Ethyl gallate Gallic acid
(develops) (does not develop)
If the acid group, instead of being directly substituted in the nucleus is

separated by an acyclic chain the developing properties are retained. This is
the case with caffeic acid, a pyrocatechin derivative.
OH
O
OH
CH=CH-CO.OH
Caffeic acid
(develops)
The ketone group -CO- has no appreciable effect on the developing

power. Thus 1 : 4-dihydroxy-3-acetophenone (OH) 2 • C 6H 3-CO-CH 3 ,
1 : 2 : 3-trihydroxy-5-acetophenone and 1 : 2 : 3-trihydroxy-5-benzophen-
one (OHh. C 6 H 2-CO-C 6 H 5 , are developers.
On the other hand, this property disappears in trihydroxybenzophenone if
the phenyl radical, C 6 H 5 , contains a hydroxyl group, for this produces an
anhydride conversion effect which destroys one of the OH developing func-
tions.
AMINOPHENOLS
104. Properties
The arninophenols are compounds which contain both an amino -NH 2
group and a hydroxyl -OH group. They only have developing properties
when the -NH 2 and -OH groups are ortho or para to each other. The
m-aminophenols <24 l generally do not develop. It is, furthermore, necessary
that the hydroxyl group is not blocked by an alkyl radical -OR.
The simplest members of the series are: o-aminophenol (hydrochloride)
melt3ng point of base 170°C, soluble in water; p-aminophenol, <25 l hydro-
chloride or oxalate, whose base melts at 183°C, crystallizes in prisms, soluble
in water, soluble with difficulty in alcohol and ether, also called p-amido-
phenol.
o-aminophenol p-aminophenol p-aminocresol
p-Amino-o-cresol or 5-amino-2-hydroxy-toluenc as the sulphate is also a

developer. It is the p-aminophenol of toluene. The introduction of a methyl
-CH 3 or ethyl -C 2 H 5 into the ortho nuclear position relative to the
hydroxyl, increases the developing power. Also known are 2-amino-3-
hydroxy-toluene and 2-hydroxy-3-arnino-1 : 4-dimethylbenzene. <26 l
Sulphonic acid groups on the other hand reduce the developing power; thus
p-aminophenol-3-sulphonic acid HS0 3 • ClH 3 • (OH) 2 is a much weaker
developer than the parent compound.
The effect of introducing a carboxylic acid group is not as great; o-amino-
salicylic acid NH 2 • C 6 N 3(COOH). (OH) is a good developer. Similarly with
p-aminosalicylic acid (Hauff's Neol) which crystallizes in sublimable needles,
soluble with difficulty in cold water.
If an alcohol group - CH 2 0H is substituted in the 2- position of the nucleus
instead of carboxyl, Edinol, o-hydroxymethyl-p-aminophenol hydrochloride<27l
is obtained, a compound readily soluble in water but only slightly in alcohol.
By substituting a phenylamine (anilino) group -C 6H 4 NH 2 in the 3-posi-
tion of p-aminophenol, diaminohydroxy-diphenyl<28 > (OH)(NH 2) . C 6H 3-
- C 6H 4 NH 2 is formed, known as Diphenal and related to benzidine. It occurs
as long velvety needles melting at 148°C, almost insoluble in cold water, but
soluble in alcohol.
2-Hydroxy-3-aminobenzylamine (OH)(NH 2)C 6H 3CH 2- NH 2 is another
type of aminophenol disclosed by Einthorn. <29 >
The diphenyl nucleus C 6H 5-C 6H 5 is capable of providing a large number
of developing agents, many of which were used by Trumbull <30 > (1934), these
are the:
p-hydroxyphenyltoluidines OH. C 6H 4-C 6 H 3 (CH 3)(NH 2)
p-hydroxyphenylanisidines OH. C 6H 4- C 6 H 3 (0CH 3 )(NH 2 )
p-hydroxyphenylphenetidines OH. C 6H 4-C 6 H 3(0C 2H 5)(NH 2)
R. W. Henn <31 > disclosed that the introduction of a phenyl group in a

p-aminophenol reduces the activity by half, whilst with o-aminophenol the
activity is considerably increased.
The replacement of the hydroxyl group -OH by a mercapto group -SH
destroys the developing properties.
105. Preparation of the aminophenols

The aminophenols are prepared in three different ways:
1. Action of ammonia on dihydroxybenzenes under pressure in an auto-
clave:
Hydroquinone therefore yields p-aminophenol. The ammonia can be re-

placed by ammonium chloride.
2. Action of ammonia on a chlorophenol in the presence of copper sul-
phate, <32 > in an autoclave at 140°C.
The chlorophenols are produced by the controlled reaction of chlorine on

phenols.
3. Reduction of nitrophenols to aminophenols:
Many methods of reduction can be used:

With tin and hydrochloric acid; with thiosulphuric acid<33 l H 2 S 20 3 ; with
powdered zinc and sodium bisulphite <34 ) at 50-50°C; with aluminium
amalgam in dilute alcoholic suspension at the boil (the filtrate being subse-
quently treated with CO 2); with stannous chloride SnC1 2 which gives the
chlorostannates of the aminophenols which are insoluble in hydrochloric
acid, and from which the tin is removed by precipitation with hydrogen sul-
phide. Nitrophenols can also be reduced electrolytically<35 l in an alkaline
solution using a nickel cathode, or by reduction of nitrophenol vapour with
hydrogen using pumice stone impregnated with reduced copper as a catalyst,
at a temperature of 265°C. <36 l
The nitrophenol corresponding to the aminophenol can be obtained by
nitration of phenol; one part of phenol is treated with a cooled mixture of
two parts of nitric acid and four parts of water. The oil which separates as
the top layer is washed and then steam distilled. Only the o-nitrophenol
passes over, the para compound is in the residue from which it is extracted
with boiling water. The lower the temperature of nitration the more of the
para isomer is formed.
o-Nitrophenol can also be prepared by heating a mixture of 25 parts phenol,
25 parts ethyl nitrate, C 2H 5 • N0 3 , 80 parts of water and 160 parts of sul-
phuric acid at 150°C. After 5 hours the upper layer is removed and distilled.
Other methods of preparing p-nitrophenol are: boiling p-nitraniline with
concentrated caustic soda; heating p-nitrochlorobenzene N0 2 • C 6H 4 • Cl
with sodium carbonate. The product is purified by dissolving in boiling water,
neutralizing with carbonate, evaporating, and recrystallizing from hot con-
centrated hydrochloric acid. M.Pt. 114°C.
Hydroxyalkylaminophenols. The hydroxyalkylaminophenols such as Edinol,
hydroxymethyl-p-aminophenol hydrochloride, are prepared like the simple
p-aminophenols by introducing a chloroalkyl group such as -CH 2Cl by
means of formaldehyde. For example, p-nitrophenol reacts with formalde-
hyde, H. CHO, in the presence of hydrochloric acid to give chloromethyl-
p-nitro phenol
OH. C 6H 4 • N0 2 + HCHO + HCl -7 OH. C 6H 3(CH 2Cl)(N0 2) +H 2 0
The chloromethyl compound is hydrolyzed by water to hydroxymethyl-
p-nitrophenol OH. C 6H 3(CH 2 0H)(N0 2).
The latter is converted to hydroxymethyl p-aminophenol by the methods
already given, for example, with tin and hydrochloric acid.
106. Aminonaphthols
The naphthols, as do the phenols, give aminonaphthol developing agents.
It is in all cases essential that the two developing functions are located in the
same ring of the naphthalene nucleus.
They are generally used as sulphonates in order to increase their solubility;
the activity of the parent aminonaphthol is but slightly diminished by the
introduction of the sulpho groups. Aminonaphthols are not commercially
available.
Eikonogen is the sodium salt of 1-amino-2-naphthol-6-sulphonic acid <37 }
and crystallizes with 2! molecules of water. It occurs in the form of rhombo-
hedral plates and loses its water of crystallization at 110°C. It is more soluble
in warm than cold water, but is very slightly soluble in alcohol and ether. In
acid solutions the free sulphonic acid precipitates.
Diogen is similar to the previous compound but differs by having a second
free sulphonic acid group in the 3-position; it is therefore 1-amino-2-naph-
thol-3-sulpho-6-sodium sulphonate. Diogen crystallizes in colourless needles,
slightly soluble in cold water, but readily soluble in alkaline sodium sulphite
solutions. Other known derivatives include 4-amino-1-hydroxy-3-naphthoic
acid (Hauff) 3-amino-2-naphthol-7-sulphonic acid (Andresen), etc.
The preparation of the aminonaphthols is similar to the aminophenols;
methylamine can be reacted with 1" : 2-dihydroxynaphthalene under pres-
sure. Another method is to react sodamide with a naphthol sulphonic acid
Eikonogen Diogen
The more common method is to reduce the corresponding azo derivative.

Thus, diazotized aniline C 6H 5N = NCl is coupled with Schaeffer's acid or
FJ-naphthol-6-sulphonic acid to form benzene-azo-FJ-naphthol-6-sulphonic
acid. The latter is reduced with stannous chloride to give 1-amino-2-naph-
thol-6-sulphonic acid or Eikonogen, by losing a molecule of aniline
C 6 H 5N = N-C10H 5(0H)(S0 3 H) 2H 2 +
-+ C 10H 5(NH 2)(0H)(S0 3 H) +
C 6H 5 NH 2
If the same procedure is followed using FJ-naphthol-3 : 6-disulphonic acid,
1-amino-2-naphthol-3 : 6-disulphonic acid is produced, whose sodium salt is
Diogen.
N-SUBSTITUTED AMINOPHENOLS
So far only the simple aminophenols having the amino group intact have
been considered. It is possible, though, to replace one of the hydrogen atoms
of this group with an alkyl radical, an alkyl carboxylic or sulphonic acid, a
phenyl radical, etc. Although any substitution of the hydroxyl group destroys
the developing power, <38 > substitution in the amino group on the contrary,
increases this power.
The simplest of the series of N-substituted aminophenols are the methyl-
p-aminophenols.
107. Metol or p-methylaminophenol

Disclosed by Hauff, <39 >p-methylaminophenol (sulphate) has the structure:
it is known under the trade names Metol, Genol, Elon, Planetol, etc.
It occurs as a white powder, of needle or prismatic crystals, and decom-
poses on heating. Metol is readily soluble in water, but only with difficulty
in alcohol and ether. The free base is slightly soluble in cold water and very
soluble in alcohol and ether, M.Pt. 87°C.
Also used are p-dimethylaminophenol OH. C 6 H 4N(CH 3) 2 oxalate,
p-benzylaminophenol OH. C 6 H 4NH. CH 2C 6 H 5 hydrochloride, and o-
methylaminophenol hydrochloride.
Ortol consisted of a mixture of o-methylaminophenol and hydroquinone.
Dimethyl-o-aminophenol, corresponding to pyrogallol, was perhaps the
essential constituent of Pyrophane prepared by condensing pyrogallol with
dimethylamine NH(CH 3) 2. It developed without alkali.
From toluene, C 6H 5 CH 3, many interesting developers are derived.
6-methylamino-3-hydroxytoluenel
2-methylamino-3-hydroxytoluene CH 3NH. C 6 H 3(CH 3)(0H)
3-methylamino-2-hydroxytoluene
The methyl group can be replaced by an alcohol or acid group, giving for
example, 3-methylamino-2-hydroxybenzoic acid CH 3 . NH. C 6 H 3(COOH)
(OH) derived from salicylic acid.
The aminophenol nucleus can be halogenated; by doing so in this case the
4- or 5-chloro-2-methylaminophenol (Hauff) <40 > and the 4 : 6-dichloro-
2-methylaminophenol (Schneider and Williams)< 41 >are obtained.
It can also be substituted by an alkoxy group R-0-, as in 5-methoxy-
2-methylaminophenol <42> CH 30. C 6 H 3(0H)(NH. CH 3).
Reddelein and Muller< 43 > used developers in which the alkyl substituent
of the amino group is further substituted by an alcoholic hydroxyl -OH
group:
p-hydroxyethyl-am~nophenol } OH. C H . NH. C H OH

o-hydroxyethyl-ammophenol 2 4 6
4
3-methyl-4-hydroxethylaminophenol OH. C 2H 4 • NH. C 6Hs(OH)(CH 3)

2-chloro-4-hydroxyethylaminophenol OH. C 2H 4 • NH. C 6H 3(0H)(Cl)
The most interesting are the p-hydroxyethylaminophenol, almost as power-

ful as metol, but less easily oxidized and more soluble, and o-hy droxy-
ethylaminophenol, a fine-grain developer known by the name Atomal (Agfa),
and prepared by reacting ethylene oxide with o-aminophenol.
Diphenylamine gives the following derivatives:
4-Hydroxydiphenylamine OH. C 6 H 4 • NH. C 6H 5 (Hauff 1891) and
4: 4-dihydroxydiphenylamine OH. C 6H 4 • NH. C 6H 4 • OH (Schering 1907).
108. Glycin or p-hydroxyphenylglycin, OH. C 6H 4 • NH. CH 2 COOH p-

aminophenol derivative in which an amino hydrogen atom has been replaced
by the alkyl radical of glycolic acid HO. CH 2 • COOH, acid-alcohol. Glycin
disclosed by Bogisch in 1891, is in the form of mica-like plates and is decom-
posed on heating. It is slightly soluble in water and alcohol, but dissolves in
alkaline sulphite solutions (forming the sodium salt of the acid radical). It is
a slow but powerful developer, very resistant to aerial oxidation and producing
no fog.
By replacing the carboxylic acid group of glycin with sulphonic acid
-S0 3H, Eurekine was obtained with the formula OH. C 6H 4 • NH.
CH 2 S0 3H, and was used as the sodium salt. This compound is ready soluble
in cold water and warm alcohol, crystallizes in long needles and decomposes
on heating.
The substitution of a phenyl group in the amino group diminishes the
developing energy, but if the phenyl group contains a -NH 2 or - OH group
the energy is restored and surpasses that of the parent substance. This is the
reason why the following are active developers :
p-dihydroxydiphenylamine OH . C 6H 4 • NH. C 6H 4 • OH
p-aminohydroxydiphenylamine OH. C 6H 4 • NH. C 6H 4 • NH 2
With the aminonaphthols the following developers are obtained:
4-methylamino-1-naphthol-6-sulphonic acid, 1 -amino-4-hydroxy-2-naphthoic
acid (Hauff 1891), 3- or 4-phenyl-amino-1-naphthol C 6 H 5 NH. C10H 6 0H
(Trumbull 1934), <44 > 4-acetamino-1 : 2-dihydroxynaphthalene CH 3 • CO.
NH. C10H 5 (0H) 2 , 2 acetamino-3-chloro-1 : 4-dihydroxynaphthalene, 2: 8-di-
acetamino-1 : 4-dihydroxynaphthalene (Schinzel 1939). <45 >
109. Preparation of N-substituted aminophenols (Metol and others)

The N-substituted aminophenols can be obtained by reacting an alkylamine
R. NH 2 or R 2NH with a dihydroxybenzene at 200°C under pressure; thus
metol is prepared by reacting methylamine CH 3NH 2 on hydroquinone. <46 >
C 6H 4(0H) 2 + CH NH
3 2 -* OH. C 6H 4 • NH. CH 3 +H 2 0
At the Eastman Kodak plant at Rochester, a 40 % aqueous solution of
methylamine is reacted with hydroquinone for 4 hours in an autoclave at
170- 180°C in the presence of sodium bisulphite. Caustic soda is then added
to give the sodium salt. By treating with hydrochloric acid, crude metol is
obtained. By redissolving in a basic medium, the base can be recrystallized.
It is then converted to the sulphate. <46b )
Similarly dimethylamine (CH 3 ) 2NH, and mono- and diethylamine can be
reacted with the o- or p-dihydroxybenzenes.
Metol can also be prepared by methylation of p-aminophenol OH. C 6 H 4 •

NH 2 by means of methyl sulphate. The quantity of the latter must not exceed
the theoretical amount otherwise some dimethyl derivative will be formed.
The p-arninophenol sulphate which is formed at the same time, is separated
by acidifying the solution with a little acetic acid and then precipitating with
benzaldehyde, the metol remaining in solution. The solution is then concen-
trated to give needle crystals which are then recrystallized.
The derivatives of p-hydroxyphenylglycin are prepared by fusing chloracetic
or bromacetic acid with the corresponding aminophenol, in the presence of
an alkali. By thermal decomposition (145°C) in solvents such as ketonesC 47 >or
a mixture of cyclohexane and chlorobenzene (Agfa)C 48 >metol base, which is
then converted to the sulphate, is produced industrially.
DIAMINES
110. Simple diamines
o- and p-dinitrobenzene C 6 HiN0 2) 2 give, on reduction, the two diarnines,
o-phenylenediamine and p-phenylenediamine, both of which have developing
properties.
a-phenylenediamine p-phenylenediamine
In practice, p-phenylenediamine is mostly used, as the hydrochloride.

This is readily soluble in water, but slightly soluble in alcohol. The
phenylenediamines are strong bases. They are oxidized to quinonoid
compounds.
Preparation: the phenylenediarnines are prepared by reduction of nitro-
benzeneC49> or nitranilinecso) N0 2 • C 6H 4 • NH 2 •
The latter are obtained by nitration of acetanilide C 6H 5NH. CO. CH 3 ,
in sulphuric acid solution for the para derivative, or in acetic acid for the ortho
compound. The separation of the three nitranilines o-, m-, and p- is carried
out by fractional neutralization in the order o-, m-, then para.
The toluylene diamines CH 3C 6H 3(NH 2) 2 derivatives of toluene C 6H 5CH 3
are obtained in a similar way.
A different procedure is to treat p-chloronitrobenzene with ammonia
in alcoholic solution, the product being readily reduced to p-phenylene-
diamine.
In the naphthalene series, three diarnines were disclosed by Andresen
(1889): 1 : 2-naphthalenediamine, 2 : 3-naphthalenediamine and 1 : 4-naphtha-
lenediamine sulphonated in the 6- or 7- position.
111. Substituted diamines
The alkyl derivatives of the p-phenylenediamines are good developers especi-
ally the unsymmetrical N-dimethyl and N-diethyl-p-phenylenediamines
R 2 N. C 6H 4NH 2 , also called dimethyl and diethylarninoanilines. Colour
development is based on the use of these compounds. They are prepared by
reducing the p-nitroso or p-nitrodialkylanilines. <51 l The alkylanilines which
.are to be nitrated or nitrosated are themselves prepared by alkylation of
.aniline with an alkyl chloride, such as methyl chloride, or an alkyl sulphate,
Dr by reacting aniline hydrochloride with an alcohol.
The splitting of dialkylaminoazobenzenes R 2 N. C 6 H 4 N = NC 6 H 4NR 2 also
produces dialkylarninoanilines.
The number of substituted p-phenylenediarnines which possess developing
properties is very great; the methyl, dimethyl, ethyl, diethyl, butyl, 2-methyl-N-
diethyl derivatives were used by Hauff<52 l in 1891. Fischer<53 l disclosed the
dipropyl and 3-methyl-N-diethyl derivatives, and Kodak, <54 l diethylamino-p-
phenylenediamine, 3-bromo-p-phenylenediamine and supplementary alkoxy
substituents as in 2-amino-5-diethylaminophenetole C 2H 50. C 6H 3(NH 2)
N(C 2H 5) 2 • Mention must also be made of the p-phenylenediarnines with acid
substituents in one of the NH 2 groups: 4-amino-N-methylarninobenzene-w-
sulphonic acid; 4-arnino-N-benzylarninobenzene-4' -sulphonic acid; <55 l and
4-aminobenzene-iminodiacetic acid <56 l NH 2 • C 6H 4 N: (CH 2COOH) 2 •
The alkylarninoanilines with the structure NH 2 • C 6H 4 • NHRY where Y
is a sulphone derivative such as -S0 2 NH 2 , -S0 2NHR or -NH-S0 2 • R
are more soluble than the ordinary alkyl derivatives and are more suitable for
fine-grain development.
Such is N-,B-methylsulphonamidoethyl-4-aminoaniline<57 l
These sulphone compounds are prepared by reacting a primary amine

with an alkyl sulphonyl chloride or a chlorosulphonic ester. F.P. 1,080,501
discloses the use of sulphobenzoic anhydrides.
If the benzene nucleus of a substituted p-phenylene diamine is replaced by
a naphthalene nucleus, the alkyl-naphthylenediamines are produced, the sim-
plest of which, disclosed by Hauff< 58 l ass. diethyl (or dimethy l)-1 : 4-naphthy-
lenediamine (C 2H 5hN. C10H 6NH 2 , monomethyl-1 : 4-naphthylenediarnine,
etc.
DIAMINOPHENOLS
112. Diaminophenols
These are used as the hydrochloride (Arnidol). <59 l Diarninophenol can be con-
sidered as the o-hydroxy compound of m-phenylenediamine (non-developer).
It is an energetic developer but is rather unstable. It is preserved by adding
boric, lactic or glycolic acid.
HO NH2
N~
HO
m-phenylene diaminophenol diaminore3orcinol
diamine
diaminocresol
By introducing a second -OH group in the diaminophenol nucleus,

diaminoresorcinol is obtained in which the OH and NH 2 groups are each in
the meta position to each other (non-developing position) but which together
give a powerful developer. Diaminocresol< 60 > OH. C 6 H 2(CH 3 )(NH 2) 2 has
also been used.
Diaminophenol hydrochloride is found as colourless needles which de-
compose on heating. It is very soluble in water, slightly soluble in alcohol. It
has already been seen that diaminophenol is used without alkali.
Among the other diaminophenols disclosed by various authors, are the
following: 4-hydroxyethylamino-2-aminophenol OH. CH 2CH 2NH. C 6H 3
(NH 2)( 0 H), 2-hydroxyethylamino-4-aminophenol and 4-hydroxyethylamino-
2-acetaminophenol (Reddelein and Muller); <61 > 5-dimethylamino-2-methyl-
aminophenol (CH 3hN. C 6H 3(CH 3 NH)(OH), 4-amino-6-methyl-2-methyl-
aminophenol and 6-amino-4-methyl-2-methylaminophenol (Schneider and
Wilmanus). <62 >
The following derivatives of diphenylamine <63 > C 6 H 5 • NH . C 6H 5 have
been suggested: 4-hydroxyphenyl-4-toluidine OH. C 6H 4 • NH. C 6H 4 • CH 3 ,
4-hydroxyphenylanisidine and phenetidine OH. C 6H 4 • NH. C 6 H 4 • OR, 4-
amino-4-hydroxydiphenylamine-2-sulphonic acid (S0 3H )(NH 2)C 6H 3 • NH .
C 6H 4 • OH and 4-hydroxy-4-dimethylamino-diphenylamine.
113. Preparation of diaminophenols

The aminophenols are prepared by reducing the corresponding dinitro-
phenols. To do this, a mixture of red phosphorus and iodine in aqueous
suspension can be used <64 > or tin and hydrochloric acid:
1 : 2 : 4-dinitrophenol is reduced by four times its weight of tin and twelve
parts of hydrochloric acid giving the stannic chloride double salt, from which
the base can be separated by treatment with soda.
A third method is the elctrolytic reduction of one part of m-nitraniline
N0 2 • C 6H 4 • NH 2 or m-dinitrobenzene C 6H 4 • (N0 2) 2 in 7 parts of concen-
trated sulphuric acid.
The base crystallizes in needles M.Pt. 78-80°C, and is converted to the
hydrochloride.
Diaminoresorcinol is prepared by reducing dinitroresorcinol (NO 2) 2
C 6 H 2(0H) 2 with tin in hydrochloric acid. The nitro derivative itself is
obtained by treating a 10 % ethereal solution of resorcinol with nitrous fumes.
In the naphthalene series, the most common members are: 1 : 2-diamino-
8-naphthol-3 : 6-disulphonic acid (Andresen 1889), 2 : 8-diamino-1-naphthol-
3: 6-disulphonic acid, 2 : 8-diamino-1-naphthol-3: 5-disulphonic acid, and
2 : 8-diamino-1-naphthol-5-sulphonic acid. <65 l
114. Polyamines 1 :2 : 4-Triaminobenzene is a developer, and also sym-

metrical triaminophenol hydrochloride known as Reducine.
From diphenylamine, C 6H 5 • NH. C 6H 5 , the following are obtained:
2 : 4-diaminodiphenylamine (NH 2) 2C 6H 3 • NH . C 6H 5 and 2 : 4 : 4' -triamino-
diphenylamine (NH 2) 2 • C 6 H 3 • NH. C 6H 4 NH 2•
HETEROCYCLIC BASES
115. The Heterocyclic bases< 66 l are capable of providing a large number of
developing agents. Their practical use is always limited by their price, which
is considerably more than the simpler benzene derivatives, with no compen-
sating advantages. The following compounds have been suggested:
o- and p-dihydroxyquinolines (Lumiere and Seyewetz 1892).
o-hydroxyalkylhydroquinolines (Lembach and Schleicher 1895). <67 l
dihydroxytetrahydroquinoline (A.G.F.A. 1896). <68 l
o-hydroxyalkylhydroquinolines (A.G.F.A. 1896).
o-diaminoquinoline (Lumiere and Seyewetz 1892). <69 l
8-methoxy-6-amino-1 : 2 : 3 : 4-tetrahydroquinoline (I.G.F. 1938).
6-amino-1 : 2 : 3 : 4-tetrahydroquinoline (I.F.F. 1938).
8-methoxy-6-amino-1 : 2: 3 : 4-tetrahydroquinaldine (I.G.F. 1938).
4-hydroxy-N-phenylpyrrole (Reed 1933). <70l
4-hydroxy-N-phenyltetrahydropyrrole (Reed 1933).
4-amino-N-phenylpiperidine (Fischer 1914). <71 l
4-amino-N-phenylpiperazine (Fischer 1914).
1-phenyl-3-methyl-4-amino-5-pyrazolone (I.G.F. 1937). <72 l
1-phenyl-2 : 3-dimethyl-4-sulphamino-5-pyrazolone (Scheitlin 1909). <73 l
2 : 6-dihydroxy-4 : 5-diamino-pyrimidine (I. G .F. 1938). <74 l
6-hydroxy-2 : 4 : 5-triamino-pyrimidine (I.G.F. 1938).
2 : 4 : 5 : 6-tetraminopyrimidine (I.G.F. 1938).
6-amino-2 : 4 : 5-trihydroxypyrimidine (I.G.F. 1938).
5-aminodihydro-2-methylindole (I.G.F. 1938).
3-amino-4-oxo-2-iminotetrahydrothiophene (I.G.F. 1937). <75 l
6-amino benzothiazoline (I.G.F. 1938).
amino and hydroxymorpholines (Reed 1933). <76 l
00:: OH NH2
8-hydroxy-1 : 2 : 3 : 4-
tetrahydroquinoline
p-hydroxy-N -phenyl
piperidine
H2 ~
HOG-(}
H2 H2
p-amino-N-phenyl p-hydroxy-N-phenyl
m orpho line piperazine
8-Hydroxy-1 :2:3: 4-tetrahydroquinoline is known as Tetra-Q (Dillon

and Searle: U.S.P. 2,596,978) (1940). 6-Amino-1 :2:3 : 4-tetrahydro-
aldine gives fine-grain images.
116. Phenidone
Phenidone is 1-phenyl-3-pyrazolidone
H2C-C=O
I I
H2C, .,NH
N
I
C&Hs
which was synthesized in 1890. <77 > It was not proposed as a developer until
1940, by Kendall, and was used after a new and simpler method of prepara-
tion had been worked out: reaction of a hydrazine compound RNH-NH 2
R2 R•
X=C"
3
R 'co.OR4
with an ester or an acrylic nitrile, in the presence of an alkaline catalyst. (?7b)
Phenidone occurs as colourless crystals slightly soluble in cold water but
very soluble in solutions which are not neutral. By oxidation in alkaline solu-
tion, inactive 1-phenyl-3-pyrazolone is produced. <78 >
Phenidone can be used with hydroquinone. Maximum rate of development
is obtained using 7 % of phenidone with respect to the hydroquinone. Fog is
produced with high-speed emulsions, but can be avoided by including an
antifoggant (e.g. 0·15 g per litre benzotriazole).
117. Combined developers

A developing agent with an acid function (polyhydroxybenzene) is able to
combine chemically with a developing agent containing a basic function,
arninophenol or p-phenylenediarnine to produce a neutral substance which
will develop without alkali. The hydroxyl function is neutralized by the
amino group. The principal combinations which are used in practice are:
Metoquinone: combination of metol and hydroquinone. White powder
slightly soluble in cold water, soluble in alcohol.
Chloranol: combination of metol and chlorhydroquinone. More soluble
than metoquinone~ Resistant to aerial oxidation, keeps well in sulphite
solution.
Hydramine: equimolecular combination of p-phenylenediamine and hydro-
quinone. Was found as pellets more soluble in warm than cold water, soluble
in alcohol.
A commercial product is available which is a combination of p-phenylene-
diamine and pyrocatechin-Meritol-and is used as a fine-grain developer.
The solubility of these compounds is notably greater in alkaline solutions.
118. Aliphatic developers

The developing agents of the aliphatic (non-cyclic) type are mainly derived
from the aldols and the hydroxyacids.
The aldehydes are reducers. They can be used as their bisulphite compounds
for development in alkaline solution.
The sugars, polyhydric alcohols with an aldehyde or ketone group also
develop in alkaline solution. M. Abribat< 79 > successfully used glucose, man-
nose, arbinose, xylose, lactose, galactose, and dihydroxyacetone at a pH varying
from 6 to 11. Thus with glucose (previously heated in alkali with the air
excluded) the redox potential at pH 7 ·2 is -200mV and -420 m Vat pH 11.
The aldols and hydroxy acids having an ethylene linkage are energetic
developers; Reducton disclosed by von Euler<80 > had the formula
HO . CH = C. OH-CH : 0
It is an aldehyde and ethylene-dihydric alcohol and is used with carbonate
and sulphite.
The hydroxyacids HO-R-CO. OH give, when a molecule of water is
removed, inner esters called lactones in which the hydroxy and carboxyl
groups are linked by an atom of oxygen forming, therefore, a closed ring. Now
the ethylenic lactones, derivatives of the hydroxy acids with a double bond are
powerful developers. Examples :
Lactone of hydroxytetronic acid (Michiel)<81 > and the lactone of ascorbic
acid, isomer of vitamin C.
OI-IOH OH OH OH OH
I I I I I I
CH2-C=C-C=O CH2-CH-CH-C=C- C=O
L-o___j L-o___J
Lactone of hydroxy- Lactone of ascorbic acid
tetronic acid
The developing and reducing properties are due to the presence of the two
hydroxyl groups situated on each side of a double bond, and to the presence
of the lactonic chain which some authors consider as a heterocyclic

nucleus.
Another interesting developing agent is ethyl aminoacetoacetate<82 >
NH 2 • CH 2 • CO. CH 2 • CO. OC 2 H 5 •
Ascorbic acid developers see T. H. James' paper: Jl. Am. Chem. Soc., Jan.
1944, p. 91.
1. According to M. Abribat the exceptions to the redox potential rule are explained
only by too low a solubility, or rather, by too low a concentration of developing
agent around the grains.
2. The hydroxylamine sulphonic acids have been advocated as development regu-
lators and solarization preventers. F.P. 600,532.
3. Phot. Soc. Amer. Jl., Feb. 1944, 136-137.
4. U.R.S.S. 32,493 (1933).
5. U.S.P. 2,006,324 (1935).
6. U.S.P. 1,998,177 (1934).
7. U.S.P. 1,908,817 (1933).
8. Ind. and Eng. Chem., 1952, 1730-1735.
9. B.P. 450,572 (1934); Bull. Soc. Fr. Chim., 1923, 449-459.
10. Jl. Soc. Sci. Phot.,Japan, Aug. 1951,11-16 and Sci. Ind. Phot., 1952,191.
11. U.S.P. 1,934,632.
12. Fasciati A.: Thesis, Zurich 1945, 55 pages.
13. Das Lichtbild, Aus. 12-XI-1935, p. 173, and B.P. 498,869.
14. Buchta: Ber., 1937, 70, 2339.
15. Kumetat K.: Zeits. Wiss. Phot., Oct. 1948, 113-119.
16. Guaiacol is pyrocatechol-monomethyl-ether OH. C 6H 4 • OCH 3 •
17. Rzymkowski J.: Die Pharmazie, Aug., 1948, 346-349.
18. U.S.P. 2,017,295 (1933).
19. U.S.P. 2,037,742 (1934).
20. B.P. 498,869.
21. B.P. 5,207.
22. Homolka, 1914.
23. Canadian P. 380,587 (1939).
24. 2 : 4 : 6-trimethyl-m-aminophenol, however, was disclosed by Homolka, in 1914,
as a developer.
25. Disclosed by Andresen in 1888.
26. Hauff: B. P. 15,434 (1891).
27. Schering: F.B. 382, 367 (1907).
28. B.P. 20,690 (1891).
29. G.P. 167,572 (1905).
30. U.S.P. 1,969,243.
31. Henn R. W.: Phot. Soc. Amer. Jl., Nov. 1953, 149.
32. Diepolder: Ber., 1904, 42, 2,920-F.B. 397,524 (1908).
33. Goldberg: Oesterrichen Chem. Ztg., 1900, 3, 470.
34. Sidgwick and Callow: J.C.S., 1924, 125, 522.
35. Auwers and Eisenlohr: Ann., 1909, 369, 223.
36. Brown and Carrick: J.A.C.S., 1919, 41, 434.
37. Disclosed by Meldola in 1881.
38. Phenylhydrazine C 6Hs. NH. NH 2 and phenylhydroxylamine C 6 H 5 • NH. OH
although possessing no phenolic function are developers.
39. B.P. 15,434 (1891) .
40. B.P. 27,931 (1896).
41. U.S.P. 2,060,594 (1936).
42. Schneider and Williams: U.S.P. 2,060,595 (1936).
43. U.S.P. 1,758,892 and 1,799,568 (1930 and 1931).
44. See also Harger: J.A .C.S., 1919, 41, 270.
45 . U.S.P. 1,969,243.
46. B.P. 498,869 and U.S.P. 2,286,796.
46b. Chern. Engng., 1953, 276-279.
47. Norman S.: U.S.P. 2,101,750 (1935).
48. B .I .O.S. Report, 773, H.M. Stationery Office, London.
49. Rinne and Zincke: Ber., 1874, 7, 869. Mignonac: Bull. Soc. Fr. Chim., 1910(4),
7, 154. Martin: Organic Syntheses, 1939, 29, 70.
50. Hofmann: Proc. Roy. Soc., 1863, 12, 639. Brown and Carrick : J.A.C.S., 1919,
41,436.
51. Wurster: Ber., 1879, 12, 522-528. Meyer: Ber., 1903,36,2978.
52. B.P. 15,434.
53. U.S.P. 1,102,028 (1914).
54. F.P. 804,472 (1936).
55. I.G.F.: B.P. 460,580 (1937).
56. Taylor: B.P. 481,581 (1938).
57. Kodak-Pathe: F.P. 866,339 (1941).
58. B.P. 15,434 (1891).
59. Andresen: G.P. 60,174 (1891).
60. Hauff: G.P. 74,842 (1892).
61. U .S.P. 1,853,455 (1932).
62. U.S.P. 2,060,596 (1936).
63. Trumbull: U.S.P. 1,969,243 (1934) and Schering: F .P. 444,639 (1911).
64. Hemilian: Ber., 1875, 8, 768.
65. B.P. 21,595.
66. Discussed at the beginning of part 4 concerning the sensitizing dyes.
67. G.P. 89,181.
68. B.P.
69. B.P. 479,446.
70. U.S.P. 1,937,844.
71. U .S.P. 1,102,028.
72. B.P. 459,665.
73. U .S.P. 930,091.
74. B.P. 479,446.
75. B.P. 459,665.
76. U.S.P. 1,937,844.
77. Sci. etJl. Phot., 1953, 146.
77b. F.P. 1,064,875 (Brit. prior. 17 Oct. 1951)-Duffin and Kendall : XXVII Congres
Intern. Chim. Ind., Bruxelles, 1954-55.
78. Axford and Kendall: R.P.S. Cent. Conf., London 1953 and Sci. et Ind. Phot.,
1953, 467.
79. Abribat M.: Sci. et Ind. Phot., 1944, 7-8.
80. Von Euler: Ann., 1933, 505, 78.
81. Maurer and Zopf: Phot. Ind., 1935, 33-90. Michie!: Ber., 1933,66, 1291; B er.,
1934, 67, 1239.
82. I.G.F.: U.S.P. 2,163,781 (1937).
F
Chapter X
DEVELOPER ANALYSIS
119. Importance of analysis
The properties of a developer depend on the relative concentrations of its
constituents. We know that these proportions are continually changing during
the useful life of the developer, not only during development, but also when
not in use, due to aerial oxidation.
Constant estimation of all the compounds in the developer is necessary to
maintain constant activity when continuous machines are used. The analyses
are first necessary to determine the constitution of the developer, then to
control the smooth running of the process, and detect accidental changes.
The frequency of analysis is obviously dependent on the amount of work
done in the bath. Those used for continuous negative development must be
analysed every day. The bromide should even be estimated every four hours
in the case of positive films which pass through in large quantities. Finally,
the pH must be measured frequently-every two hours for example.
It should be emphasized that developer analysis requires extreme care;
and if the results are required as quickly as possible, the operations must be
suitably organized with adequate apparatus and personnel. Otherwise the
figures have no real value, for they will not correspond to the present condition
of the developer.
Some methods enable a rough estimation of the state of the bath to be
made quickly, but the results obtained are not accurate. These are principally
the methylene blue test and the ferricyanide test.
Methylene blue test. 20 cc of a 1 : 15,000 solution of methylene blue in a test tube
are shaken with 3 cc of developer. Normally, a fresh developer will declorize the dye
in about 3 minutes, a used developer in 15-20 minutes, and two hours or more if the
bath is exhausted.
Ferricyanide test (1). A standard ferricyanide solution is added to a 5 cc sample of
developer diluted with 10 cc water. The test sample turns yellow, then orange and
finally red-brown after a few minutes. The addition is stopped at the orange tint :
4 mols. of ferricyanide is equivalent to 1 mol. of metol or hydroquinone. The orange
tint is generally very difficult to differentiate, which takes away all the accuracy of the
test.
120. Selective extraction of hydroquinone and metol from developers

As metol-hydroquinone developers are the most widely used, these two
developing agents are the ones most frequently estimated.
132
The estimation of developing agents includes a preliminary stage: the extraction
of the pure substance. The direct titration of a used developer does not distin-
guish between the oxidized and the non-oxidized product. To estimate, for
example, quinone in the presence of hydroquinone, a special technique based
on the formation of hydroquinone-a-dithiosulphuric acid must be used, dis-
closed by Rzymkowski, which can be removed with an ion exchanger, Wofa-
tito, M.<2 >
The extraction of the organic developing agents contained in a developer
can be carried out with an organic solvent which has no action on the corres-
ponding quinones. At the same time, the hydroquinone and metol must be
separated. This is made possible by the fact that metol remains in aqueous
solution if the pH is far removed from 8, which enables the hydroquinone to be
extracted first, in acid solution, then the metol, after neutralizing.
Atkinson and Shaner's method.( 3 ) AS cc sample is put into the extraction apparatus
(made up of a dropping funnel attached to a U -tube whose end is bent down again,
and which has a restricting capillary tube at its lower bend). A few drops of 0 ·04%
thymol blue in aqueous alcohol is added, followed by hydrochloric acid, until the
solution is red (pH 2). Then sodium chloride is added until a slight excess remains,
in order to reduce the solubility of the hydroquinone. The funnel tap is opened, and
pure ether is run through at such a rate that the developer is not carried through the
tube. After 100 cc of ether has passed into the receiver, water is poured into the funnel
to recover the remaining solvent. The ether extract is transferred to a SOO cc flask of
thick glass containing 200 cc hot water and 1 cc of concentrated hydrochloric acid;
the ether is removed by evacuating. The acid aqueous solution obtained in this way
is used for estimating the hydroquinone.
A second sample of developer is taken and sufficient hydrochloric acid is added to
adjust the pH to 8 (beginning of yellow colour of thymol blue). The metol and hydro-
quinone are then extracted as above, and the aqueous solution of the two developers is
titrated.
In the absence of the special extraction apparatus, an ordinary separating funnel can
be used, using a small portion of the ether for the first extract, running off the aqueous
layer into another funnel and again extracting with a fresh portion of ether. Three
operations are necessary for total extraction. The ether extracts are combined. In this
case it is advisable to use larger samples of the developer.
Stott's method.(') 2S cc of developer is put into a 1SO cc separating funnel, and a
few drops of thymol blue is added. 2S cc of SO% sulphuric acid is added until the
solution turns red, and 1 cc extra is added. The solution is then shaken vigorously
with SO cc of ethyl acetate and left. The aqueous layer is transferred to a second funnel
and the operation is repeated. The two extracts are combined, and contain the hydro-
quinone, whilst the aqueous layer is retained to extract the metol. The sulphur dioxide
in the ethyl acetate resulting from the acidification of the sulphite is neutralized by
shaking with 2S cc of a solution containing 100 g per litre anhydrous sulphite, 10 g
boric acid and 1 g caustic potash. The aqueous layer which separates is discarded,
and the ethyl acetate extract is analysed.
The aqueous layer which still contains the m etol is in turn poured into a separating
funnel, thymol blue added, followed by 2N caustic until a blue colour is obtained
(pH > 9 ·6). Three successive extractions are made with 2S, 1S and 10 cc of ethyl
acetate. The three extracts are combined and are then ready for metol estimation.
Stott's operating method has been slightly modified by Levenson( 5 l to reduce the
causes of errors: thymol blue is replaced by phenolphthalein and in the metol extrac-
tion, after neutralizing with caustic to a pink colour, it is decolorized again with sod-
jum bicarbonate, following a suggestion by Gloyns.
121. Non-selective extraction of metol and hydroquinone

Non-selective extraction has the advantage of enabling both developers to be
estimated in the same extract. As the solvent used is insoluble in salt-contain-
ing solutions, but soluble in pure water, it is unnecessary to evaporate after
extraction.
Baumbach's method. <6 l 25 cc of developer is put into a 250 cc separating
funnel, and neutralized with hydrochloric acid until yellow to thymol blue.
15 g of potassium bromide and 25 cc of methyl acetate are then added and the
mixture is shaken for 3 minutes. After leaving for at least 3 minutes the aque-
ous layer is run off and again extracted with 25 cc of methyl acetate. The
aqueous layer is then discarded and the two acetate extracts are mixed. The
organic solution is dried by being passed several times through layers of
drying agent, then 150 cc water is added and the solution is titrated.
Shaner and Sparks method. <7 > Instead of extracting with ordinary separating
funnels, the Atkinson and Shaner extractor is used, whilst the more readily
obtained methyl ethyl ketone (M.E.K.) is used as the solvent. The course of
the operation is similar to Baumbach's: 10 cc of developer is put into the
extractor with 0·5 cc of 0·04 % thymol blue and enough 50 % sulphuric acid
to turn the indicator yellow. The solution is saturated with powdered potas-
sium bromide, and 50 cc of M.E.K. is run through and collected at the exit
tube in a graduated vessel.
Brunner, Means and Zappert's method. (B) Baumbach's method has been
modified as follows : 25 cc of developer is placed in a separating funnel. Two
drops of thymol blue is added, then 50 % sulphuric acid until the solution is
yellow (pH 8-8·5). 12 g potassium bromide and 25 cc isopropyl acetate are
then added, and the funnel is shaken for 3 minutes, and the separated aqueous
phase is run off into a 50 cc beaker (the solvent must fill the tube in the tap).
The solvent is then run into a dry beaker, and the aqueous layer is returned
to the funnel and again extracted with 25 cc isopropyl acetate (which has been
used to rinse the beaker). The first solvent extract is transferred successively
into three dry beakers, then into a fourth 400 cc one. The empty beakers are
rinsed with the second extract, which is finally added to the first.
122. Estimation of hydroquinone in the separated extract

There are two methods of estimating the hydroquinone extracted from a
developer: by titration with iodine or with eerie salts.
The iodometric method is to oxidize the hydroquinone with iodine solution
in the presence of bicarbonate and starch solution which turns blue with
excess iodine. The blue coloration must persist for one minute. It is more
accurate to add excess iodine and back titrate with standard thiosulphate in
the presence of an acetic acid--sodium acetate buffer. The blue colour is less
persistent if the developer extract contains less than 0·02 M.
Bogdanof's procedure. <9 l Twenty cc 2M sodium acetate solution, 0·6 cc
4 M acetic acid and then the developer extract are added to 25 cc standardized
iodine solution. Mter adding 1 cc of starch solution, the excess iodine is
back-titrated with thiosulphate. If the hydroquinone is extracted from 25 cc
of developer with treatment of the ether extract with 50 cc 2 M sulphuric
acid, the final aqueous solution is made up to 200 cc, neutralized to methyl
orange and 25 cc is taken for titration.
Atkinson and Shaner's procedure. The hydroquinone extract obtained by
one of the methods already described is titrated with 0·01 M iodine in the
presence of starch until there is a blue colour. The sulphur dioxide is neutral-
ized in this way, but the hydroquinone does not react in acid solution. One
hundred cc of a buffer containing 3% disodium phosphate and 1%sodium
metaborate (pH 7 ·5) is added. The solution is then titrated with 0·01 N
iodine until a persistent blue colour is obtained, or excess iodine is added and
back-titrated with standardized thiosulphate.
Cerium colorimetric estimation. Sasai and Mizusawa. (SbJ After extracting the
metol and hydroquinone at pH 8·4, sulphuric acid and diphenylamine are
added, and the solution is titrated with 0·05 N eerie sulphate until a blue-
violet colour is obtained. A second extraction at pH 2 only removes the hydro-
quinone. Formalin is added to prevent the S0 2 from reacting, and the titra-
tion is carried out as above. The solvent used is ethyl acetate.
Cerium potentiometric estimation of hydroquinone. The estimation of hydro-
quinone with eerie sulphate (oxidizing agent) using potentiometric control was
disclosed in 1935 by Furman and Valas, then recommended by Bogdanof:
the developer extract in aqueous acid solution (50 cc of M H 2 S04 to 25 cc
developer) is freed from ether, and a further 150 cc of acid is added before
titrating with a eerie sulphate solution.
The course of the reaction is followed with a pH meter fitted with a
platinum or glass electrode and a calomel helf cell. The curve of the potential
against the number of cc of reagent is plotted, whose inflection point shows
the neutralization point. Agitation must be vigorous during the whole opera-
tion.
Stott's potentiometric method. Ten cc of the ethyl acetate hydroquinone
extract prepared by the same writer's method (para. 120) is slowly added to
200 cc water acidified with 2 cc of 50 % sulphuric acid. The mixture is
vigorously shaken to dissolve the solvent, then the electrodes are introduced
and titration is carried out with 0·01 N eerie sulphate. This is prepared from
a 0·1 N stock solution (in dilute H 2 S04) diluted before use with water con-
taining 5 cc of 50 % H 2S04 per litre. Temperature control is unnecessary,
especially if comparison is made with a known amount of pure dried hydro-
quinone. The weighting per litre of the hydroquinone is given by 0·22 X
volume in cc of eerie solution, or more accurately H = 0·22 (x - 0·05)
(Levenson).
123. Estimation of metol in separate extract

The metol is estimated in the same way as the hydroquinone, with iodine or
eerie sulphate.
For iodometric estimation the amount of the product should be less than
0·02 M so that the end point will be clearly visible. The acid extract solution
is neutralized to methyl orange before titrating. If p-aminophenol is also

present, this is estimated at the same time.
Atkinson and Shaner estimate the metol + hydroquinone mixture obtained
from 5 cc of developer neutralized to pH 8 with thymol blue (yellow colour).
Knowing the weight of hydroquinone from a prior test, the metol can easily
be calculated.
Stott's potentiometric method. The extract of the metol in ethyl acetate (para.
120) is poured into a 50 cc burette whose tip is immersed in a beaker filled
with 400 cc water acidified with 4 cc of 50 % sulphuric acid. Twenty-five cc
of the solution is slowly run in with stirring. When dissolved, it is titrated
with eerie sulphate, as for hydroquinone. The amount of metol in g per litre
is given by 0·069 X n cc of eerie solution. Levenson, using 20 cc of extract
removed with a pipette, obtained the weight of metol from the following ex-
pression, where K is an error coefficient and H is the weight of hydroquinone
M = 0·088 n K -0·003 H
124. Estimation of metol and hydroquinone in a single extract

Baumbach's method (see para. 121) enables both the metol and the hydro-
quinone to be estimated in an extract containing the two compounds: the
metol base is first titrated with a strong acid potentiometrically, then the sum
of metol + hydroquinone with iodine.
The extract containing the developing agents, obtained by the method
already given, is mixed with three volumes of water and one part of methyl
acetate or isopropanol to reduce the polarity of the liquid (the inflection of the
curve is less distinct, but still visible). The metol is then titrated with 0·1 M
hydrochloric acid, despite the presence of the hydroquinone, after intro-
ducing the platinum and calomel or glass and calomel electrodes.
A buffer solution of 10 % disodium phosphate is then added until the pH
has reached 6·5 to 7, followed by 1 cc of starch solution before titrating with
0·1 N iodine. The metol and hydroquinone are converted to methylquinone-
imide and quinone. In this way the weight of metol + hydroquinone is ob-
tained. By difference, the quantity of hydroquinone is known.
Shaner and Sparks' procedure. The extract of metol-hydroquinone obtained
from 10cc of developer using methyl-ethyl-ketone (para. 121) is poured into
10 cc water. Sufficient methanol is added to make the ketone miscible, then
the electrodes are immersed. The metol is titrated with 0·1 M hydrochloric
acid. The amount of metol in g per litre is obtained by dividing the product
of volume of HCl X strength X molecular weight of metol (172] by the volume
of the sample.
The metol + hydroquinone sum is then determined, after adding enough
disodium phosphate to raise the pH to 8, and 1 cc of starch solution, with
0·1 M iodine. If n is the volume in cc of the iodine solution, eits I 2 content,
v the volume of the test, M the weight of metol per litre, the concentration of
hydroquinone in g per litre is:
55(n Bfv) -2M
Accuracy: metol 3- 5 % , hydroquinone 1·5-4% .
Brunner, Means and Zappert's procedure. The metol + hydroquinone extract
in isopropyl acetate (see para. 121) is mixed with 100 cc water and 50 cc
methanol. Potentiometric titration with 0·05 M hydrochloric acid is then
carried out with glass and calomel electrodes. The inflection point is given
by the pH v volume of HCl curve. The weight of metol is
M = 6·88 ve
where v is the volume of the hydrochloric acid and () its strength.
Five cc of a mixture of equal volumes of water and H 2S04 is then added,
and two drops of an 0 ·025 M solution of ferroin (ferrous complex of o-phen-
anthroline). The solution is titrated with 0·1 N eerie sulphate with mechanical
agitation until the pink colour turns to a yellow-green which persists for 30
seconds. The weight of hydroquinone in g per litre is given by:
H = 2·2[V'0'- c~~)]
To obtain a sharper inflection point in the potentiometric titration curve,
Idelson (JO ) replaced the water by acetic acid as a solvent for the metol and the
acid (which is sulphuric or perchloric), as normally weak bases behave as
strong bases in acetic acid. The disadvantage of this method, is that a precipi-
tate is formed during the second titration with eerie sulphate.
125. Simultaneous spectrophotometric determination of metol and

hydroquinone
Rees and Anderson <n >have worked out an interesting method of simultaneous
spectrophotometric analysis of metol and hydroquinone, based on the fact
that the absorption spectra of the two developers have characteristic ultra-
violet absorptions if the dilution is great enough. Good results are obtained
with 1 cc of developer in 100 cc of a pH 5 sodium acetate buffer solution.
Both pH and temperature must be carefully adjusted.
Metol: Absorption maximum at 270 mp,.
Hydroquinone: Absorption maximum at 290 mp, +slight absorption due
to metol.
Accuracy: in the order of a few mg. per litre.
126. Estimation of other developers

p-Aminophenol, glycin, amidol and p-phenylenediamine are estimated in the
same way as metol. Pyrogallol is treated like hydroquinone.
Colorimetric determination of p-aminophenol. The amount of p-aminophenol
can be determined colorimetrically by converting it to a dye with one of the
two following methods used by Ballard: <12 >
(a) Diazotization with sodium nitrate, then coupling with resorcinol.
(b) Reaction with dimethylaminobenzaldehyde. If metol is also present,
the determination must be made with a spectrophotometer to separate the
two coloured constituents_
Glycin estimation. The glycin is converted to nitrosamine with nitrous acid,

following the method of Brune, Rieyer and Schultze. <13 > Pour 50 cc of
developer into a solution of 20 cc water and 5 g barium chloride BaC1 2 • 2H 20
to first precipitate the sulphite and carbonate. Filter through sintered glass,
wash three times with 15 cc boiling water, and after cooling, add 2 cc"'of
hydrochloric acid diluted with 2 cc water. Then titrate with a known solution
of sodium nitrite with stirring. To find the end-point of the reaction put a
drop of liquid onto a porcelain plate with a drop of starch iodide solution and
continue until a permanent blue colour is obtained. 2·42 mg of glycin is c~n
verted by 1 mg of nitrite.
Estimation of pyrogallol. Pyrogallol is extracted with ether or other solvent,
from the acidified developer, like hydroquinone. If the latter is also present,
the extract is redissolved in water, acidified with acetic acid, and the pyro-
gallol is precipitated with lead acetate, filtered, dried and weighed. 1 g of the
insoluble lead salt is equivalent to 0·333 g of pyrogallol.
Estimation of Phenidone. Oxidize with iodine in acid solution.
Estimation of dialky-p-phenylenediamines: see para. 562.
127. Estimation of sulphite

The sulphite is estimated with iodine in acid solution (to prevent developer
oxidation). Run the developer from a burette into a flask containing 20 cc of
0·5 M iodine solution and 5 cc concentrated hydrochloric acid, until de-
colorizing is almost complete. Add 2 cc starch and continue titrating to a faint
blue.
Bune, Reiyer and Schulze<15 > take 20 cc of developer and dilute to 100 cc.
A 10 cc sample is poured into a solution of 5 g crystalline barium chloride in
5 cc water. The precipitate is collected on a sintered glass filter, and is washed
four times with 15 cc boiling water. The filter is then placed over a 600 cc
beaker and 20 cc 0·1 N iodine and 5 cc HCl with 5 cc water is put in the filter.
After 3 minutes, 300 cc water is poured through the filter. The SO 2 reacts
with iodine which is back-titrated with thiosulphate. One cc of iodine solution
is equivalent to 6·3 mg sulphite.
Another technique is to precipitate the sulphite and carbonate with barium
chloride, then to convert the sulphite to sulphate with hydrogen peroxide. The
carbonate is decomposed on the water-bath with a known quantity of methyl
red. If borate is present, add minnitol and follow the reaction with the
potentiometer. (Pope, C. I.: J.S.M.P. T.E. 1955, 64, 420).
Bisulphite. Bisulphite reacts with iodine in the same way as sulphite. The
sulphitejbisulphite ratio is determined empirically by pH comparison of the
test developer with that of a developer prepared according to the analytical
results.
128. Estimation of carbonate

The carbonate in a developer is estimated by liberating carbon dioxide with
an acid in a stream of air, passing through a chromosulphuric solution to
remove S0 2 , before absorbing with soda-lime, which often produces errors.
It is generally preferable to titrate potentiometrically using a pH meter fitted
with a calomel reference electrode and a platinum electrode, or if this is not
available, a glass electrode. The second inflection point gives the end point of
the reaction, the first corresponding to the formation of bicarbonate.
The procedure is as follows: (lSl 10 cc of developer, diluted with 100 cc
water is titrated with 0·1 N HCl with the electrodes in position. Agitation
must be violent as dissolved oxygen affects the result. The weighting per litre
of carbonate is given by 1·06 n, n being the volume in cc of hydrochloric acid
solution.
Another method is to titrate in the presence of a coloured indicator made
up of 0·1 g methyl orange and 0·25 g indigo carmine in 100 cc water. The
green alkaline solution becomes grey at the neutral point, and then violet in
acid solution.
129. Estimation of borates

As borate estimation is rather tedious it is often preferable to determine only
the pH. The estimation is made in the following way:C17 > One hundred cc of
developer at pH 8 is extracted three times with 50 cc ether to remove the
developing agents. The aqueous phase is then acidified with a few cc of HCl
to eliminate the CO 2 and SO 2 • The remaining traces of sulphite are oxidized
with hydrogen peroxide. The solution is neutralized to bromocresol green
(Blue at pH 5·2) with caustic soda, 50 cc glycerin is added, and then it is
titrated with NflO caustic soda in the presence of phenolphthalein. When the
pink colour is obtained, its permanence is checked by adding more glycerin
and heating. One cc of soda solution corresponds to 0·00618 g of H 3B0 3 •
The borate ion can be detected by the red coloration of curcuma paper in
acid solution, or by the green colour of a flame test on the dry extract mixed
with alcohol and sulphuric acid.
The presence of boric acid and borates cannot be directly distinguished.
An approximate idea can be obtained by pH comparison of the test developer
made up according to the analysis.
130. Measurement of developer pH

The knowledge of the pH of the developerC18 > is of interest for the control of
its activity, although it is less important than the knowledge of the alkali con-
tent. It has only the advantage of being obtained by rapid measurement.
Colorimetric determination is only approximate; a glass electrode potentio-
metric instrument is required. If this is not of a special type, a correction
must be used above pH 9·5, due to the presence of sodium ions. The relative
values are, however, generally adequate.
To standardize the instrument, it is advisable to use a buffer with the same
sodium ion concentration as the developer to avoid errors due to the influence
of sodium ions. For example (Levenson) : sodium carbonate anh. 5 g, sodium
bicarbonate 5 g, sodium chloride 58·5 g water to 1 litre. The pH of this
solution is 9·3. The calomel reference electrode can advantageously be re-
placed by a more accurate one having the constitution Ag/AgClfKCl (N/ 10)
F*
The relationship between pH value, carbonate concentration and gamma

is :<19)
pH 10·38 10·14 10·12 10·11 10·10 10·08 10·10
Car b. 68·0 38·7 37·0 35·8 22·4 18 ·0 18·0
y 2·86 2·82 2·77 2·75 2·72 2·70 2·70
It is seen that slight variations in pH correspond to considerable differences
in carbonate, and that the corresponding variations in y are moderate.
131. Estimation of various constituents

Sodium sulphate. In a used developer, 10-20 % of the sulphite is converted to
sulphate, mainly by aerial oxidation. If more than 5 % is found in a fresh
developer, it is probably due to its deliberate addition to reduce the swelling
of the gelatin.
To estimate the sodium sulphate, it is precipitated with barium chloride
after acidifying the developer with HCl to decompose the sulphite and
carbonate, which would otherwise also precipitate. The resulting barium
sulphate will coagulate after boiling for one minute. It is then filtered, washed,
dried and weighed in a tared Gooch crucible.
Potassium thiocyanate. To estimate the thiocyanate, put 25 cc developer,
180 cc distilled water and 60 cc sulphuric acid in a 400 cc beaker. Insert a
silver and a calomel electrode and titrate potentiometrically (with a pH
meter), using N /10 silver nitrate, which first precipitates the halides.
Orthophosphates give a yellow precipitate of ammonium phosphomolyb-
date<20> with an acidified developer, after prior precipitation of the iodides,
bromides and chlorides with silver nitrate.
Sodium citrate. The sodium citrate in certain developers is precipitated with
barium chloride at the same time as the sulphite, sulphate and carbonate. The
washed precipitate is redissolved in an acid to separate the insoluble sulphate.
The resulting solution is boiled to eliminate CO 2 and SO 2 and the citric acid
is re-precipitated with a barium salt.
Other substances. A developer may contain alcohol, formalin (detected after
distillation), ammonia, a desensitizing dye, a wetting agent, a sequestering
agent such as hexametaphosphate, tetraphosphate, pyrophosphate, or ethy-
lenediamine-tetraacetic acid. For the detection and estimation of these com-
pounds, refer to general analytical works.
132. Bromide estimation

Two principal methods are used with many vanatwns: oxidation of the
bromide or precipitation with silver nitrate. The former is little used for
developer analysis, but could be adopted.
(a) Kapur, Verma and Khoshla<21 >oxidize the bromide with a mixture of
chromic and nitric acids. The liberated bromine is collected in carbon tetra-
chloride, then potassium iodide is added. The liberated iodine is titrated with
thiosulphate.
(b) Lane<22 l liberates the bromine by adding chlorine water in the presence
of sulphuric acid, and estimates it colorimetrically with a photoelectric
instrument.
(c) Farkas and Lewin<23 l treat the solution with hypochlorite at a pH
between 9 and 9·4. Hypobromite is formed which is reduced by a basic
solution of phenol, and the excess hypochlorite is estimated.
(d) Atkinson and Shaner<24 l precipitate the bromide with silver nitrate in
nitric solution, and in the presence of metanil yellow and a known excess of
bromide.
(e) Baumbach <25 l titrates the bromide potentiometrically with silver
nitrate in acid solution with a silver and a calomel electrode. The addition of
barium nitrate or alum gives better agreement between the inflection and
equivalence points.
(f) Laitinen, Jennings and Parks<26 l titrate with silver nitrate using a
turning platinum electrode (current measurement).
Atkinson and Shaner's method. 15 cc concentrated nitric acid, 4 cc of 0·2% metanil
yellow and 10 cc of 10% potassium bromide (to ensure an adequate bromide concen-
tration) are added to 100 cc developer in a 300-cc flask. This is titrated with a 1.427%
silver nitrate solution. The colour is blue at the beginning, and red at the end of the
titration. The bromide concentration in g per litre is given by n -100/10, where n is
the volume in cc of silver nitrate required.
Potentiometric method. Evans, Hanson and Glasoe( 27 > have disclosed a potentio-
metric method in which the sulphur dioxide is first eliminated by boiling in acid
solution, before adding sodium acetate.
When a mixture of silver iodide, bromide and chloride is precipitated the inflection
points of the e.m.f.-vol. AgNO 3 curve do not correspond exactly with the points of
chemical neutralization. Better agreement is obtained when barium nitrate or alum is
added. However, in current practice the accuracy is adequate without this addition.
25 cc of positive developer (or 100 cc negative developer) are mixed with 75 cc
distilled water, 0·5 cc bromocresol green and sufficient concentrated sulphuric acid
to tum the solution yellow, plus a further 0·5 cc, and finally 100 cc distilled water.
The silver and calomel electrodes are immersed in the solution together with a
mechanical stirrer. Silver nitrate solution is then added drop by drop, but at a fairly
fast rate until the potentiometer indicates 70 m V, then more slowly, waiting after
each addition until equilibrium is reached. At about 120 mV the titration is complete,
and it is unnecessary to draw the curve. Titration time 10 minutes. Maximum error
3%.
The silver electrode is prepared by electrolytic deposition of silver on a platinum
wire, from an argenticyanide solution. ·
133. Iodide estimation

The iodide, precipitated as silver iodide with silver nitrate, is oxidized with
chlorine. It is converted to iodate which is estimated polarographically by the
technique of Evans, Hanson and Glasoe. <28 l Another equally laborious method
of Levenson's, is to first eliminate the reducing agents, then extract the iodine
with cyclohexane and estimate it calorimetrically. <29 l
The procedures of these two methods are so lengthy that we refer the reader
to the original papers.
134. Estimation of impurities

Traces of copper in a hydroquinone developer can produce aerial fog. It is
therefore advisable to estimate this metal. Evans, Hanson and Glasoe have
determined it polarographically in the presence of 2 % of a 60 % solution of
ethylenediamine which doubles the amplitude of the curve. Levenson used a
colorimetric method. <31 > The developer is shaken with a solution of zinc
diethyldithiocarbamate in butyl acetate. The copper salt collects in the solvent
layer, which it colours brown.
Lambert used the catalytic autoxidation of resorcinol by copper: <32 > the
green coloration of autoxidized resorcinol solutions increases linearly in
density with the copper content.
Sulphide can be rapidly estimated with the polargraph, following the in-
structions of Evans, Glasoe, and Hanson. <30 >
135. Analytical reactions of developing agents

The developing agents, as received, or extracted from a developer, can be
identified by the characteristic reactions in the following table.
1. Ultra-violet examination
Fluorescence
Substance In sulphite Powder
solution
Hydroquinone Very light red-violet light violet
Pyrocatechin weak violet none
p-Aminophenol HCl none weak violet
Glycin violet weak whitish
Ami dol none weak whitish
p-Phenylenediamine violet none
Dimethyl-p-phenylenediamine blue none
2. Ferric chloride FeCl 3 gives the following reactions :

Hydroquinone Brown colour
Pyrocatechin Dark green colour
Pyrogallol Blue colour changing to brown
p-Aminophenol HCl Brown precipitate
Metal Red-brown colour-slow
Metoquinone Brown colour then ·precipitate
Glycin Red-brown colour turning green and violet
Diaminoresorcinol Violet colour turning brown.
Ami dol Blood-red colour
Eikonogen Reddish-brown colour
3. Potassium ferricyanide K 3 Fe(CN) 6 also gives characteristic reactions.

Pyrogallol Dark red colour
p-Phenylenediamine Green-brown colour turning brown with
dark green precipitate
p-Aminophenol Brown precipitate
Metal Yellowish red colour
Glycin Yellow colour
Ami dol Red colour turning brown
4. With nitric acid
Hydroquinone Dark red colour becoming yellow
Pyrocatechin Reddish-yellow colour
Py.rogallol Dark red colour
p-Aminophenol Yellow colour
Metol Dark red colour
Metoquinone Yellow colour
Glycin Reddish yellow coldur
5. The alkali carbonates colour amidol-sulphite solutions blue, and those
of diaminoresorcinol, yellow-brown. With caustic alkalis the same solutions
turn bordeaux red and blue respectively. With alkaline solution Eikonogen
gives a golden yellow colour.
6. Plauman <33 > has given the following system for the identification of a
commercial developing agent.
Seven different tests are made on a 5 % solution of the unknown, each taking
50 cc (see table, p. 144).
1. Addition of a few drops of 20% carbonate.
2. One or two drops of 5 % ammonium vanadate.
3. A few drops of 5% caustic potash.
4. Addition of 10 % ferricyanide, then a few drops of 20 % carbonate.
5. Addition of 10 % ferricyanide alone.
6. Addition of 10 % ferrous sulphate.
7. Addition of 2 % ferric chloride.
We would add a characteristic reaction of metol: a drop of its ether solu-
tion is put on filter paper followed by a drop of 16 % hypochlorite. A definite
bright blue-green colour is produced.
13Sb. Chromatographic analysis

Sasai, Mizusawa and Otoka<33b) have worked out a system for identifying
developers by chromatography on paper. The developer, deposited on the
latter is treated with a mixture of water, acetic acid and n-butyl alcohol (or
ethyl acetate). The diffusion times are respectively 5-8 hours and 3!--5 hours.
After drying, the paper is sprayed with a 2 % ammoniacal solution of silver
nitrate. The migration distance distinguishes the developers.
A similar technique was used by Mariani and Martinelli. <33c) A 35 X 35 em
sheet of paper is wrapped around a cylinder, and 3 mm3 of a 1 % aqueous
solution of the developing agent is placed at the beginning. After drying at
45°C the paper is damped with solvent from a spray and again dried.
The best solvent is made up of 15 % water, 80 % n-butyl alcohol and 5 %
acetic acid. The patches are then treated with NflO ammoniacal silver nitrate
which makes them grey, black or grey-violet.
136. A.S.A. standards of purity for developing agents

Metal: must dissolve completely in cold water to the extent of 4 g per 100 cc with
5 drops 10% H 2 S04 • One gramme of product must dissolve completely in 3 cc con-
centrated HCI. The fraction soluble in absolute alcohol or ether must not exceed
IDENTIFICATION TABLE FOR DEVELOPING AGENTS t
Test 4
Insoluble in Test 1 Test 2 Test 3 Ferricyanide Check test
Carbonate Am. vanadate Potash and carbonate
Hydroquinone - Yellow-+ No change Yellow-+ Golden yellow Test 7-deep

brown brown -+brown green
Pyrogallol - Yellow-+ Blue Yellow-+ Brown Test 6-Biue

..,
::z::
brown brown Add 1-+
blue-violet ,.,
0
0
C)
Pyrocatechin - No change Violet Green-brown Green-+ Test 6-Green :>;)
green- Add 1-+ ..,>

brown red-violet ::z::
.....
0
p-aminophenol Ether No change Blue-green Violet Decolorized - 0
HCI ::z::
~
s:::
.....
Ami dol Ether Blue Red Yellow-brown - Test 5-Red
,.,
Ul
:>;)
Metol
f Alcohol Yellow-brown Olive green Yellow-brown Yellow-brown Test 7-Weak red ><:
l_Ether -+violet -+deep red-
brown
p-phenylene- f Alcohol No change Brilliant No change Green Test 7-Deep

diamine H Cl l_Ether green -+ green
olive green
Glycin Water - - - - -
0·04% . Must give sulphate reaction. Ash .;;0 ·1 %. Volatile matter .;;0 ·3%. Iron
.;;2·5%. Amount of p-aminophenol .;;2.5%.
Characteristic reactions: purple colour in less than 5 minutes by adding 0·2% mer-
curic acetate to 0·1% metol. Immediate colour when 1 cc of 2% caustic soda is added
to 50 cc 2% metol.
Absence of dimethyl-p-phenylene diamine (toxic to the skin): Dissolve 2 g metol in
10 cc water. Filter into a 100-cc separating funnel. Add 10 cc 40% caustic soda and
10 cc ether. Shake. Separate the aqueous layer. Rinse with 10 cc water without shak-
ing. Run off the water. Add 10 cc 10% (by volume) H 2SO., shake and run off the
acid. Divide the ether solution equally between two tubes with ground stoppers.
Shake one of the tubes for one minute-no pink colour must form. Add 2 cc 10%
nitrite to the second and shake. There must be no brown colour or precipitate.
Hydroquinone: M.Pt. 170-174°C. 5 g must dissolve cold in 100 cc distilled water,
95% alcohol or ether. Ash .;;0·075%. Iron .;;0·001 %. Negative result with lead
acetate test for resorcinol.
Chlorhydroquinone: M.Pt. 103-106°C with softening at 90-95 °C. Ash .;;0·1 °,
Iron .;;0·005%. Chlorine 24·1-25·1 %.
Pyrocatechin: colour-white to pink. M.Pt. 101-104°C . Ash .;;0·1 %. Iron
.;;0·001 %. Intense green colour on adding FeCI 3 to the hydrochloric acid solution.
Pyrogallol: white to blue-grey crystalline powder. M.Pt. 130-133°C. Ash .;;0 ·02%.
Iron .;;0·001 %.
p-aminophenol hydrochloride: the free base, precipitated by sulphite, washed and
dried for one hour at 70°C must melt between 185 and 190°C. 5 g of p-aminophenol
hydrochloride must dissolve completely in 100 cc cold water. Ether-soluble fraction
maximum 0 ·04%. Cl24-25%. Ash .;;0·5%. Volatile matter .;;0·5%. Iron .;;0·005%.
Glycin. M.Pt. (with decomposition) 220°C. 1 g must dissolve completely in 10 cc
of hydrochloric acid diluted with 10 cc water, or in 10 cc 10% caustic (slight opal-
escence). The fraction soluble in cold water or in acetic acid must not exceed 0·04% .
Ash ,;; 1%. Volatile fraction .;; 0 ·5%. Iron .;; 0 ·005%. By adding Fe Cl 3 to hydrochloric
acid solution: red-brown colour turning grey-green and violet.
Diaminophenol (hydrochloride). White or blue-grey cryst. powder. 5 g must dissolve
in 100 cc cold water with no residue, in 30 minutes. When 5 cc of 10% sodium car-
bonate is added to this solution there must be no smell of ammonia. Cl 35·5-36·5%.
Ash .;; 1%. Volatile matter at 85-95 °C .;;0 ·5%. Iron .;;0·001 %. Byadding4 cc of 10%
nitrite in 100 cc of 1% solution of the product a deep red colour is produced. By
adding one drop of a solution containing 1% of the compound and 10% sulphite to
potassium carbonate, a bluish colour is produced.
p-phenylenediamine (base). 1 g must dissolve completely in 100 cc cold water or
20 cc absolute alcohol. Ash .;; 0 ·1%. Iron .;; 0 ·005%. Add 5 cc of 3% acetic acid to 1 cc
of 1% solution; heat to 45 °C and add 1 drop of a saturated aqueous solution of aniline
. and a few crystals of ammonium persulphate: blue-green colour in 5 seconds.
p-phenylenediamine (hydrochloride). Sg must dissolve completely in 100 cc cold
water. Fraction soluble in absolute alcohol .;;0·08%; in ether .;;0·04%; Cl39·5-41 % .
Ash .;;0·1 %. Volatile matter .;;0·5%. Iron .;;0·005%. FeCl 3 added to hydrochloric
solution -+ green colour turning brown.
137. A.S.A. standards of purity for photographic chemicals(3•l

Sodium sulphite anhydrous: sulphite content ;-. 96%. Carbonate .;;0·15%. Hypo
cryst. .;;0·1 % . Precipitation by ammonia .;;0 ·5%. Heavy metals (Ph) .;; 0·002%.
Iron .;;0·005%. Reducing agents-see carbonate.
Potassium metabisulphite: K 2 S 20 5 ;-.90%. Hypo .;;0·1 %. Insoluble in ammonia
.;;0·5%. Heavy metals 0 ·005%. Iron .;;0·005%.
Sodium carbonate: Na 2C0 3 ;-.98%. Caustic soda .;;0·5%. Bicarbonate .;;0·17%.
Lead .;;0·001 %. Iron .;;0·001 %. Presence of reducing agents: one gramme of car-
bonate is dissolved in 20 cc distilled water, and 10 cc of ammoniacal silver nitrate
(prepared from 10% AgN0 3 and ammonia) is added. After 2 minutes, the solution
must be neither turbid nor more coloured than a blank test. This test is also used for
sulphite and metasulphite.
Borax: content 99-103% (efflorescence). No effervescence with HCl. Pb .:;;0·001 %.
Fe .:;; 0·03 . Presence of reducing agents-see carbonate.
Metaborate: Na 2B 2 0 4 8H 20 ;,.98 ·5%. Acidity HB0 3 .:;;1 %. Free NaOH .:;;0·2%.
Ca .:;; 0 ·01 %. Pb .:;;0·001 % . Fe .:;;0·003%.
Caustic soda: Na 2 C0 3 .:;;2·5%. NaCl .:;;0·5%. Heavy metals 0 ·001 %. Fe .:;;0·003%.
Potassium bromide: KBr ;,.99%. NaCl .:;;0·3%. H .O .:;;0·3%. Neutrality: a solu-
tion of 1 g in 50 cc water must not colour phenolphthalein, but the addition of one
drop of N/10 caustic soda must give a pink colour. Presence of iodide: dissolve 1 g
KBr in 10 cc water and add 1 cc 10% H 2 So 4 , 0·5 cc FeCl 3 , then 1 cc chloroform or
carbon tetrachloride: the solvent layer must not be coloured. Absence of oxidizing
agents : 1 g in 10 cc water + 0 ·5 g KI + 1 cc chloroform: no colour in chloroform.
Na 2 S .:;;0·0005. Ammonia precipitate .:;; 0·75 %. Heavy metals 0·0005 % . Iron
0·0005 % .
1. Strauss P. : Foto. Kino. Technik., 1949, 30-31; Sci. et Ind. Phot., 1949, 179.
2. Brauer, E. and Staude H.: Zeits. Wiss. Phot., 1953, 16-19.
3. Atkinson, R. B. and Shaner V. C.: Jl. Soc. Mot. Pict. Tel. Eng., 1940, 485-523;
Sci. et Ind. Phot., 1940, 190-194.
4. Stott, J. G.: Jl. Soc. Mot. Pict. Tel. Eng., 1942, 37-54; Sci. et Ind. Phot., 1946,
155-58. .
5. Levenson G. I. P.: Phot.Jl., 1947, 18-24; Sci. et Ind. Phot., 1947,168-169.
6. Baumbach H. L. : Jl. Soc ~ Mot. Pict. Tel. Eng., 1946, 403-407; Sci. et Ind. Phot.,
1947, 110-112.
7. Shaner and Sparks:Jl. Soc. Mot. Pict. Tel. Eng., 1946, 409-413; Sci. et Ind. Phot.,
1947, 112-113.
8. Brunner, Means and Zappert : Jl. Soc . Mot. Pict. Tel. Eng., 1949, 25-35; Sci. et
Ind. Phot., 1949, 420.
9. Bogdanof S.: Kino. Photo. Chim . Prom., 1939, 50-54; Sci. et Ind. Phot., 1940,
189-190.
9b. Sasai and Mizusawa : Jl. Soc. Sci. Phot. Japan, 1954, 17, 60-64; Sci. et Ind. Phot.,
1955,26,476-477.
10. ldelson M.: Jl. Soc. Mot. Pict. Tel. Eng., 1950, 492-493; Sci. et Ind. Phot.,
1950, 381. Crowell, Gausman and Baumbach: Jl. Soc. Mot. Pict. Tel. Eng.,
1951, 411-415; Sci. et Ind. Phot., 1952, 151.
11. Rees and Anderson: Jl. Soc. Mot. Pict. Tel. Eng., 1949, 268-284; Sci. et Ind.
Phot., 1949, 459.
12. Ballard: Analyst., 1950, 430-436; Sci. et Ind. Phot., 1951, 137.
13. Brune, Rieyer and Schulze: Zeits. Wiss. Phot., 1952, 118-122; Sci. et Ind. Phot.,
1952, 441.
14. Atkinson and Shaner: Zoe. cit.
14b. Axford A. J.: Brit. Jl. Phot., Feb. 1956,88-89, or Sci. Ind. Phot., 1956, 198.
15. Brune, Rieyer and Schulze: Zoe. cit.
16. Stott: Zoe. cit.
17. Atkinson and Shaner: Zoe. cit.
18. See chapter IV on redox potential.
19. Stott: Zoe. cit.
20. With ammonium molybdate in nitric solution with warming.
21. Kapur, Verma and Khosla: Ind. Eng. Chem., Anal. Ed., 1942, 157; Sci. et Ind.
Phot., 1944, Nos. 9-12.
22. Lanes: Ind. Eng. Chem., Anal. Ed., 1942, 149; Sci. et Ind. Phot., 1944, Nos. 9-12.
23. Farkas and Lewin: Anal. Chem., Sept. 1947.
24. Atkinson and Shaner : Zoe. cit.
25. Crowell, Luke and Baumbach : Jl. Soc. Mot. Pict. Tel. Eng., 1945, 472-480; S ci.
et Ind. Phot., 1945, 283.
26. Laitinen, Jennings and Parks: Ind. Eng. Chem., Anal. Ed., 1946, 355.
27. Evans, Hanson and Glascoe : Sci. et Ind. Phot., 16(2), 36.
28. Evans, Hanson and Glascoe: Ind. Eng. Chem., Anal. Ed., 1942, 314-316; S ci. et
Ind. Phot., 1944, 304-305.
29. Levenson: Jl. Soc. Chem. Ind. , 1947, 198-200; Sci. et Ind. Phot., 1948, 96-98.
30. Evans, Hanson and Glascoe: Jl. Soc. Mot. Pict. T el. Eng., 1943, 88-96.
31. Levenson: Analyst, 1948, 31-33; Sci. et Ind. Phot., 1948, 254.
32. Lambert, R. H. : Anal. Chem., 1952, 868-879; Sci. et Ind. Phot. , 1952, 367.
33. Plauman H.: Phot. Ind., 1931,34,341.
33b. Sasai, Mizusawa and Otoka : Jl. Soc. Sci. Phot. Japan, 1954, 50-53; Sci. et Ind.
Ind. Phot., 1955, 26, 44.
33c. Mariani and Martinelli: Sci. et Ind. Phot., 1956, 27, 1-4.
34. Standards Z 38.8.125, 1948 to Z 38.8.134, 1948 (Sci. et Ind. Phot., 1949, 427).
35. Z 38.8.225, 1948 to Z 38.8.232, 1948 and Z 38.8.200, 1949 to Z 38.8.206, 1949
(Sci. et Ind. Phot., 1949, 465).
Chapter XI
FIXING, WASHING AND DRYING

138. Stop baths
The stop bath, which follows development, quickly checks the action of the
developer on the sensitive layer by neutralizing the alkali. The rapid lowering
of the pH which results, increases the redox potential, and consequently
reduces the energy of the developer.
The acid retarders which are added to a developer to slow down develop-
ment, are not more than diluted stop bath constituents which lower the pH.
The developed image is immersed for 10-20 seconds in the following
solution, then rinsed and fixed:
Water 1000 cc
Acetic acid 40 cc
For papers, the acetic acid can be reduced to 15 cc.
In the absence of acetic acid, sodium bisulphite lye can be used at a concen-
tration of 50-100 cc per litre, or the equivalent of sodium or potassium meta-
bisulphite (25-50 g). Monosodium citrate can also be used at a concentration
of 5-10 % .
To prevent the gelatin from swelling, sodium sulphate can be added to the
acetic acid solution, for example:
Sodium aulphate anh. 45 g
SB.5a Acetic acid 20 cc
( Water to 1 litre
Treatment time: 3 mins. Temperature up to 26°C. Sufficient for twenty-
five films.
139. Hardening stop baths

Hardening stop baths for negative emulsions are generally chrome alum
solutions:
Chrome alum 30 g
SB. 3 {Water to 1 litre
Treatment time: 3-5 mins.
Sodium sulphate anh. 60 g (or cryst.
140 g)
SB.4
{ Chrome alum 30 g
Water to 1 litre
148
The activity of this bath falls rapidly. It must be renewed when it becomes
yellow-green in colour or if it becomes covered with scum.
Chrome alum is the double sulphate of chromium and potassium
Cr 2(SOJ 3 • K 2 S04 • 24H 20. It crystallizes in regular violet octahedral
crystals. It is isomorphous with ordinary alum Al 2(S04)a. K 2 S04 • 24H 20
which is also a gelatin hardener.
Chrome alum gives the violet Cr(H 20) 6+++ ions, which, when acidified
slowly, become the green Cr(H 2 0h(OH)++ and ordinary alum gives com-
plex hydrated ions such as Al(H 20) 6+++, Al(H 20hOH+, Al(H 20MOH) 2+,
Al(H 20) 3(0H)a+, which are the gelatin hardening functions.
With the carboxyl groups of the gelatin molecule, these ions form co-
ordination compounds. These compounds are broken down in the presence
of citrate or tartrate ions, with a greater tendency to form co-ordination com-
pounds which destroy the hardening properties of the bath. Baumbach and
Gausman put forward the hypothesis that water molecules, being polar, attach
themselves to groups which are also polar; now the number of ionic groups is
reduced by co-ordination with the aluminium complex ions. The swelling of
the gelatin is therefore reduced. The necessity of having a large number of
positively charged Cr ions and a large number of negatively charged gelatin
carboxyl groups impose two opposing conditions which reduce the pH range
in which hardening is possible. In fact, the chromium ions lose their positive
charge when the pH exceeds 4·7.
In 1934, Spiers showed that the chromium atoms are linked to the poly-
peptide chains by a carboxyl and an amino group. At moderate acidity the
polypeptide chain is coiled up, and this favours the formation of intermediate
bridging, therefore hardening. (ll ·
140. Control of stop baths

Stop baths will keep indefinitely in corked bottles. In a tank the average life is a
month. In dishes the life is much shorter-three days for acetic acid baths, and one
day for chrome alum ones. They have the following exhaustion properties : Acetic
acid baths-55 dm 2 , weak acetic acid-100 dm2 of paper, SB.5a-150 dm 2, SB.3-
32 dm 2 , SB.4-32 dm 2 •
The SB.5a is generally better for amateur work.
The condition of a stop bath can be calculated with reference to the volume of
carry-over and the amount of acid added, using Hentzberger and Henn's equation,<•!
but in practice an empirical method is used. Henn and Crabtree<•! recommend the
addition of 11 cc of 10% acetic acid for each spool removed. For a 120-1. tank, 51.
glacial acetic acid must be added after treating 5,000 spools. The bath is discarded
after treatment of 35,000 spools.
Measurement of pH is a simple way of controlling the activity of stop baths. Without
a meter, indicator dyes can be used. The pH should be about 4 for a fresh bath, always
below 4·7 when it contains chrome alum, and can go up to 5 during use (5 ·5 for
prints). The following indicators are recommended:< 4 l
Bromocresol green (for acetic acid negative baths). Yellow when the bath is fresh,
green when in good condition during use, and blue when it is not acid enough.
Bromocresol purple (for prints). Yellow when the bath is new, orange when the bath
is still in good condition and purple when there is too little acid present.
Risso-Dominguez<•> suggested Congo red and alizarin red S.

Congo red : blue at pH 3, red at pH 5.
Arlizarin redS: yellow at pH 3 ·7 and pink at pH 5 ·2.
A paper impregnated with Congo red appears black or colourless in red light
depending on whether or not the bath is sufficiently acid.
141. Formalin hardeners

Formalin <6 l is a very active gelatin hardener. It can be l!sed either as a harden-
ing fore-bath before development to harden the gelatin thoroughly, or after
development, or after washing.
Hardening forebath (before development):
SH.5 -Sodium carbonate anh. lOg
Sodium sulphate anh. 50 g
Benzotriazole (0·5% alcoholic soln.) 40 cc
Water to 1 litre
Add 5 cc formalin just before use.
The benzotriazole is an antifoggant and can be replaced by 6-nitro-
benziminazole nitrate. <7 l The quantity must be doubled for development at
42°C.
The films are left in this bath for 10 mins. and are then rinsed for 30 sees.
The development times then become:
at 24°C (75·2°F)-same time as for 18°C. (64·4°F).
29°C (84·2°F)-time reduced to 70%
32°C (89·6°F)-time reduced to 60%
35°C (95°F)-time reducedto 50%
43°C (109°F)-time reduced to 25%.
Bath for hardening after development: 5% formalin solution, preferably
containing 40 cc 0·5% benzotriazole-treatment time 1 min. This method is
not widely used but has sometimes been recommended for photomechanical
emulsions.
Bath for hardening after washing. For papers which are insufficiently hard
because they are too new, dip in a 5 % formalin solution for 2 mins. then wash
for 3 mins.
Films which are to be intensified or reduced are hardened for 3 mins. in:
SH.1 Formalin 10 cc
( 1litre
Water to
Wash for 5 mins. It is sometimes advisable to fix again in a fresh acid bath
and wash thoroughly.
142. Silver halide solvents

The removal of the unaffected silver bromide remaining after development is
called fixation. This operation makes the photographic layer transparent and
permanent and prevents subsequent darkening.
The silver halide is made soluble by converting it to a complex double salt
of silver and alkali metal which can be eliminated by washing with water.
The silver halides (chloride, bromide and iodide) are soluble in solutions
of several substances, mostly inorganic, amongst which are the following:
Sodium thiosulphate (see next paragraph).
Ammonia NH4 0H, is a solvent for silver chloride. The soluble chloride of a
complex silver-ammonium ion is formed. By evaporating, the solution slowly
loses ammonia, and octahedral crystals of silver chloride are deposited. A 4 %
ammonia solution dissolves silver chloride in 2-5 mins.; it has less effect on
solver bromide, and none on silver iodide. Ammonia can be replaced by
neutral ammonium carbonate.
Potassium Bromide KBr. In a concentrated solution it dissolves silver
chloride and bromide, but works slowly with iodide. As it attacks gelatin
strongly, it can only be used in the presence of a hardening agent:
Water 1000 cc
Potash alum 10 g
Fixing time: 12 mins.
With silver bromide, a soluble double bromide of silver and potassium
AgBr . KBr is formed.
Potassium iodide KI. In a concentrated solution it dissolves silver chloride,
bromide and iodide: chloride and iodide rapidly-four times more quickly
than bromide. The gelatin swells and breaks up without a hardener; in all
these cases the image when wet appears in relief. The following formula can
be used:
A Water 1000 cc
Potassium iodide 200 g
B Water 1000 cc
Potash alum 100 g
Acetic acid 3 cc
Take 5 parts of A to 1 part of B. Fixing time: 5-10 minutes for silver iodide.
After several days the bath becomes brown due to the liberation of iodine;
it then stains the gelatin.
Potassium thiocyanate KCNS. It only dissolves silver bromide and chloride
well, with the formation of a double silver and potassium thiocyanate:
AgBr
Silver
+ 2KCNS =
Potassium
AgCNS . KCNS
Silver potassium
+ KBr
Potassium
bromide thiocyanate thiocyanate bromide
Thiocyanate can only be used in relatively weak solutions:

Water 1000 cc
Potassium thiocyanate 50 g
Potash alum 10 g
Fixing time 2-5 mins., followed by a rinse in a fresh bath before washing,
to avoid precipitation of the double salt in the gelatin.
Potassium cyanide and potassium ferrocyanide are also solvents for silver
halides. The former is very effective but it is too poisonous for practical use.
It forms double cyanides AgCN. KCN, and reticulates and disaggregates the
gelatin.
Magnesium chloride MgC1 2 , sodium sulphite Na 2 S0 3 , thiourea CS(NH 2h,
and thiosinamine (or allyl thiourea) NH 2- CS-NH. CH 2-CH = CH 2 , are
only effective with silver chloride.
Magnesium chloride and thiourea attack the gelatin. In the presence of
silver nitrate, thiourea gives an insoluble precipitate which remains in the
gelatin layer.
Thiosinamine is easier to use. A slightly acidified 1 % solution dissolves silver
chloride in 5 mins.
143. Fixing with thiosulphate

The fixing agent which is almost always used in current practice is sodium
thiosulphate or 'hypo' Na 2S 2 0 3 • 5Hp. It is effective with all the silver
halides, and attacks neither the gelatin nor the silver image.
Silver bromide reacts with hypo to give the argentothiosulphates following
the reaction:
+ +
x Na 2 S 20 3 y AgBr -+ Ag y (S 20 3)x< 2x-y)(-) y Br- 2x Na+ +
The thiosulphate ions, adsorbed by the surface of the grains, form the com-
plex salt Na[Ag(S 20 3)] which, with an excess of thiosulphate, becomes
water-soluble Na 3[Ag(S 20 3) 2 ]. The existence of numerous other compounds
has been proved (see para. 149). What is certain, is the formation of insoluble
argentothiosulphates when silver ions are in excess.
The fixing of a sensitive layer takes place by double diffusion: the hypo
towards the silver bromide grains and, in the opposite direction, the argento-
thiosulphate towards the liquid. Agitation speeds up this process. If the
material is placed in stagnant fixer, sensitive surface down, diffusion is
assisted by the tendency of the heavy complex salts to fall. If the gelatin is
swollen, the increased thickness counteracts in practice the speeding up of
diffusion. (B )
Sodium thiosulphate crystallizes in transparent clinorhombic prisms which have· a
bitter taste and are very soluble in water. Dissolving the crystals lowers the tempera-
ture. The crystalline salt melts at 48 oc (118 ·4 °F) and is dehydrated to the anhydrous
salt N a 2 S 2 0 3 of which 0 ·64 g is equivalent to 1 g of crystals.
Hypo is prepared by boiling a solution of sodium sulphite with sulphur following
the reaction :
Na.SOa + 1/2S. = Na.s.o.
Sodium sulphite Sulphur Sodium thiosulphate
The raction mixture is filtered, evaporated and crystallized.
It is also prepared by the action of sulphur dioxide, S0 2 , on calcium sulphide CaS;
this gives calcium thiosulphate which is treated with sodium carbonate to give the
sodium salt.
Hypo is formed when an excess of flowers of sulphur is boiled in a solution of
caustic soda. After filtering it is treated with sulphur dioxide until colourless, and
crystallized after evaporation.
It is also obtained by fusing 100 parts of crystalline carbonate with 30 parts of
powdered sulphur. The sulphite formed is extracted with water and boiled with a
further quantity of sulphur, filtered and crystallized.
Finally a 20% hypo solution can be obtained by the action of sodium amalgam on
bisulphite (F.P. 825,226, 1937).
Density of solutions of hypo crystals at 19°C
2% 1·010 12% 1·063 22% 1·120 32% 1·180
4% 1·021 14% 1·075 24% 1·132 34% 1·192
6% 1·031 16% 1·086 26% 1·144 36% 1·204
8% 1·042 18% 1·097 28% 1·155 38% 1·217
10% 1·052 20% 1·108 30% 1 ·167 40% 1·229
144. Acid fixers

The alkali of the developer, carried over in the photographic layers, can de-
compose the soluble argentothiosulphate, giving rise to stains. Furthermore,
the developing agents from the developer will be oxidized in the fixing bath
to coloured compounds.
Acids on the other hand decompose hypo to sulphur and sulphur dioxide.
Hydrogen sulphide and sodium trithionate Na 2S 3 0 6 are then formed. The
action of S on SO 2 in addition produces pentathionic acids
5S + 5 S02 + 2 H20 = 2 H2Ss0s
The decomposition of fixing baths can be prevented by adding sodium
bisulphite or metabisulphite and a little sulphite. In this way the hypo is buf-
fered against both acids and alkalis. The bisulphite neutralizes the developer
alkali, giving sulphite, whilst the sulphite is converted to bisulphite by acids,
before the hypo is decomposed.
If the hypo is oxidized to tetrathionate and the sulphite to sulphate with
iodine, the trithionate remains, which by boiling with barium chloride is
decomposed to sulphuric acid (as BaS04), sulphur and S0 2; this is a method
of estimating the trithionate. <9 >
H2Sa0s ~ H2S04 + S + S0 2
In a neutralized solution, the sulphite splits the pentathionate, contained
in a hypo solution, into trithionate and hypo:
Na 2S 50 6 + 2 Na 2S0 3 ~ Na 2 S 3 0 6 + 2 Na S 0
2 2 3
pentathionate sulphite trithionate h ypo
By estimating the trithionate form~d, the amount of pentathionate can be

found.
An acid fixing bath is made up as follows:
Water to 1000 cc
Hypo cryst. 250 to 300 g
Bisulphite lye (S.G. 1·35) 50 cc
Sodium sulphite 10 g
Fixing time: 5-10 mins.
154 PHOTO G RAPHIC CHEMISTRY
The neutral sulphite is frequently wrongly omitted. With 350 g per litre
hypo, the bisulphite must be increased to 70 cc. In addition the latter can
be replaced by 25- 30 g metabisulphite.
250 g of crystalline hypo can be replaced by 159 g of anhydrous hypo.
The above bath can fix 60 dm 2 per litre without a stop bath, and 90 dm 2
with an intermediate stop bath. It will keep for 3 months in a stoppered
bottle, one month in a tank, and a week in a dish.
Fixing rate. The speed of fixing is greatest at a concentration of 30 % . It
increases with the temperature-2·3 times for 10°C (18°F).
145. Hardening fixers

The fixing bath can also be made to harden, by incorporating potash alum or
chrome alum.
For the alum to retain its hardening properties, the pH of the bath must
not exceed 6·3 for potash alum or 4·7 for chrome alum. On the other hand,
the pH must not be less than 3·7 for below this the hypo will decompose.
Also, to stabilize the pH of the bath by a buffer effect neutral sulphite is used
at a maximum concentration of 20 g per litre. The acidity is provided by
sodium bisulphite NaHS0 3 or bisulphate NaHS0 4 in the case of chrome alum,
and by acetic or boric acid or sodium bisulphate in the case of potash alum.
Potash alum hardening fixers. The quantity of alum used is 10- 50 g per litre.
Above this, the emulsion becomes opalescent. As a buffer, sodium acetate
CH 3COONa is used. The latter, furthermore, together with boric acid retards
the formation of sludge in the bath. In the presence of an acetate buffer, the
amount of sodium bisulphate can be much higher without risk of decom-
posing the hypo.
The following formula studied by Woolsey and Pankhurst give good
results <10 > and will keep for 3 months.
Cine
Nega- Nega- Posi- Posi- X-ray
tives tives tives tives
water to 1000 cc 1000 cc 1000 cc 1000 cc 1000 cc

Hypo cryst. 240 g 350 g 240 g 350 g 250 g
Sodium sulphite anh. 15 g 8g 15 g 15 g 15 g
Sodium acetate - 15 g - 15 g 15 g
Boric acid 7·5 g 10 g - 10 g 10 g
Sodium bisulphate - 15 g - 15 g 15 g
p otash alum 15 g 10 g 15 g 30 g 30 g
A cetic acid 18 cc - 18 cc - -
The hypo is dissolved first at 50°C (122°F), then in succession the sulphite,
the acetate and the boric acid. The bisulphate and alum are dissolved separ-
ately at 50°C and this solution is poured into the former with stirring. The
total volume is then made to 1 litre. In the formulas containing acetic acid,
this is added after the sulphite; the boric acid and alum and then dissolved.
For the preparation of dry powders to be dissolved as required, anhydrous
hypo is used with sulphite, sodium acetate and boric acid. The alum and
sodium bisulphate are contained in a separate packet.
During use, the pH of the hardening bath is increased, and its hardening
power decreases: when the pH increases from about 4·5 to 7, the fixing time
is trebled.
Chrome alum hardening fixers. These baths harden gelatin very well, the
melting point being much higher than with potash alum. The hardening
power, however, is much more sensitive to pH variations. Sodium acetate
reduces this power. Furthermore, as there is no tendency for a sludge to form,
the boric acid is unnecessary. Chrome alum baths do not keep as well as
those with ordinary alum (one week).
Chrome alum formulas:
A B c
Water to 1000 cc 1000 cc 1000 cc
Hypo cryst. 250 g 340 g 250 g
Sulphite anh. 15 g 17 g 15 g
Sod. bisulphate 15 g
Bisulphite lye 100 cc
Chrome alum 15 g 30 g lOg
Sulphuric acid 2 cc
The chrome alum is dissolved separately in 250 cc water and added to the
solution of the other items with stirring. The bath B is suitable for machine
development. After treatment 500ft. of film, 10 litres of new solution are
added to 140 litres of old bath and so on. The formula C can be prepared in
a powder form; the chrome alum is kept separate and the crystalline hypo
is replaced by anhydrous.
The temperature of hardening fixers must not exceed 21 oc (70°F).
146. The fixing operation

1. When a photographic emulsion is immersed in a fixing bath, it becomes
transparent in a few rnins. and all milkiness disappears. At this point about
5 % of the silver bromide still remains in the gelatin. To reduce this to less
than 0·25 % treatment must be continued for at least as long again as the time
taken to clear. In practice the fixing time is rather more than double this
(clearing time X 2).
The speed of solution of the silver bromide is dependent on many factors:
thickness and grain size; amount of halide in the layer; concentration of silver
iodide, which slows down fixing; temperature, <12 > agitation, exhaustion of the
bath, to say nothing of the initial hypo content of the bath which has been
shown to vary from 20-35 %, with an optimum at 30 % -
In cold weather, fixing can be accelerated by adding ammonium chloride
NH4Cl; by double decomposition this gives ammonium thiosulphate which
is more active but much less stable than the sodium salt.
2. Exhaustion of the bath. When the clearing time becomes more than twice
that of the new bath the solution is considered to be exhausted. A drop of the
bath applied to paper and exposed to light becomes brown when the fixer is
exhausted. A fixed print, washed for one hour and treated in 0·2 % mono-
sulphide, must be free from fog.
A litre of solution can fix about 10 sq. ft. of negative and 20 sq. ft. of paper.
Chrome alum solutions are exhausted before potash alum, especially when no
stop-bath is used.
Acidity control. The acidity limits differ for each type of fixing bath. The upper pH
limit is 6·3 in the case of potash alum and 4·7 for chrome alum.
A turbid potash alum fixer must be discarded. Neutralization can be retarded by
adding one-third of the normal amount of acetic acid (diluted). This can only be
repeated three times.
Chrome alum fixers cannot be re-acidified.
The pH of the solutions can be controlled electrometrically, or failing that, with dye
indicators. RzymkowskiP 3 > proposed using fluorescent indicators such as pyranine,
which becomes yellow with green fluorescence above pH 7. Concentration: 20 cc of
<H% dye per litre of the bath. The fluorescence can be brought about using an
immersed blue phosphorescent tube (Permaphan of Auergesellschaft, Berlin). In the
dark, an intense fluorescence can be seen around the tube when the bath becomes
alkaline.
147. Rapid fixing

Fixing can be accelerated, especially in cold weather, by adding 50 g per
litre ammonium chloride to the bath. However, better results are obtained by
replacing the hypo with ammonium thiosulphate (Hoechst rapid fixing salts).
The fixing time with ammonium thiosulphate is reduced by 75 %. With
alum, the hardening is retained over a wider pH range. The only disadvantage
is a possible reduction of the image if the grain is fine. At 15%, however, this
attack is negligible.
Allnut's formula<14 l (Hardening bath):
Water to 1000 cc
Ammonium thiosulphate cryst. 200 g
Sulphite anh. 15 g
Acetic acid 15 cc
Boric acid 7·5 g
Alum (potash) 2·5 g
One way of manufacturing anhydrous ammonium thiosulphate<15 l is to
react ammonium sulphite with sulphur in ammonia at 50°C in the presence
Qf a trace of ammonium sulphide. The filtered liquid is then evaporated in a
current of ammonia gas.
A sodium and ammonium double thiosulphate has been described <16 l as being
more soluble and more active than ordinary hypo.
Finally, Barnes has proposed amidine and guanidine thiosulphates.
Acceleration with active cations. The negative potential barrier surrounding
each silver bromide grain can be reduced with a substance capable of provid-
ing positively charged ions: ammonium chloride works in this way, but good
results are also obtained with ethylenediamine and quaternary ammonium
compounds such as those of pyridine and piperidine (para. 41) <17 ) at a concen-
tration of 40 g per litre. The fixing time is reduced by 50 % ·
Extra rapid fixing. Fixing can be accelerated by making the fixer alkaline
or by raising the temperature of a hypo, or better still, ammonium thiosul-
phate (15-30 %) bath, to 50-60°C (122-140°F). An increase of 10°C (18°F)
increases the speed 2·3 times. The addition of thiocyanate can treble it. The
maximum rate of fixing is, however, obtained using potassium cyanide which
can fix a photograph in 1 second. Because cyanide is so poisonous, it is prefer-
able to use 50 % ammonium thiocyanate at a temperature below 54°C
(129°F). The fixing time then varies from 2-15 seconds. To avoid disinte-
gration of the gelatin, 35 cc per litre of formalin is added. The plate can also be
printed immediately after clearing, preferably by projection. Emulsions which
are to be fixed rapidly must, of course, be hardened beforehand.
148. Simultaneous development and fixation

The baths used for this purpose can be criticized for their irregular action
and instability as well as for the loss of sensitivity which they cause. For the
most part, these disadvantages can be overcome by adding a buffer whose
purpose is to keep the pH constant. Alburger used sodium aluminate; Keller
Maetzig and Moglich, <18 ) sodium zincate or plumbite. For example, with the
solution: water 1000, caustic soda 25, alum 40, sulphite 50, glycin 10, metol
10, bromide 7, hypo 100, development and fixation take place simultaneously
at 30°C (86°F), a negative in 2t minutes (y = 0·6) and a positive in 1 min-
ute (pH 11·8).
The equilibrium between development and fixing depends on the emul-
sion, and is valid only for one type. The amount of fixer added must be adjusted
in each case. The figures given can be used as a basis for experiments.
Keelan <19 ) has given the following formulas derived from those of Alburger:
I No. 212 No. 365 No. 315 No. 348
Water to 1000 cc 1000 cc 1000 cc 1000 cc

Metol 1·5 g 1·9 g 10 g 33·5 g
Sulphite anh. 25 g 33 g 50 g 50 g
H ydroquinone 13·5 g 17·1 g 40 g 15 g
Alum (potash) 5g 20 g 20 g 20 g
Caustic soda 9g 16 g 35 g 30 g
Hypo 30 g 60 g 110 g 50 g
Benzotriazole 1g 1g - -
6-Nitrobenziminazole (0· 5 %) - - 20 cc 20 cc
Potassium bromide 3·35 g - - -
Gluconic acid 0·1 g - - -
pH 11·2 11·3 11·55 11·35
Formula 212 for slow contact papers: 2-3 mins. (20 sq. ft.) .
+
Formula 365 for fast bromide papers: 3 mins. 40 sees. in hypo.
Formula 315 for negative emulsions of the Aero XX type: 3 mins . at 24°C
(75°F). Fog = 0·3, y = 1·3.
Formula 348 for emulsions of the Super XX type: 10 mins. at 20°C
(68°F) in a machine. Fog = 0·3, y = 1·7.
Another simpler formula has been published for giving satisfactory
results: <20 l
Water to 1000 cc
Sulphite anh. 30 g
Hydroquinone 15 g
Caustic soda 12·5 g
Hypo 50 g
Development-fixing time, 2 mins. at 20°C (68°F) for Aero-XX with
supplementary fixing, or 6 mins. in the single bath. The low densities have
finer grain.
With all of these solutions, if the y drops, the fixer must be reduced, or the
developer and alkali increased. As they usually contain caustic soda their life
is short. Colloidal silver rapidly forms a mud from which the solution must
be decanted.
149. Stabilizing images by fixing

Stabilization of images by simple fixing, not followed by washing is due to the con-
version of the residual halides to colourless silver complexes which are not light
sensitive. Stabilization enables photographic negatives and prints to be obtained very
quickly in all cases where a saving of time is essential.
Even in 1893 Bogish stabilized images with thiourea, but thiocyanates, thiosulphates
and organic compounds R-SH such as thiosalicylic acid can also be used.
Stabilization with thiosulphates of sodium or magnesium. Those of ammonium or
the amines give less stable results.
The thiosulphates have the advantage over the other stabilizers that they can be
eliminated by washing. Basset and Lemon< 21 >have isolated four stable complex salts:
5Na .s.o •. Ag.s.o • . 4H .o
}very soluble
3Na.s.o •. Ag.s.o •. 4H.o
Na.s.o •. Ag.s.o •. 2H.o slightly soluble
Na.s.o • . 3Ag.s.o •. 2H.o insoluble
For jilms< 22 > the best stabilizer is 30% hypo containing 5% bisulphite. After treat-
ment, rinse for 10 seconds in pure water, or better, in a solution of sodium metaborate
to avoid superficial crystallization. To stabilize quickly, work at a high temperature,
38°C (100 °F) for example. Wipe off surplus water and dry.
For papers, develop 4-10 sees. in dilute D72 at 38 °C (100 °F), stop development by
immersing for 4-10 sees. in 5% acetic acid and stabilize 4-10 sees . at 38 °C in 30%
(or less) hypo, containing 4·5 % bisulphite and 1·5 % anhydrous sulphite. Press between
blotting paper.< 23J
An excess of stabilizer eventually results in subsequent fading, whereas insufficient
amount results in darkening. A short rinse improves keeping.
Prints always become discoloured, although they remain legible for several years.
Stabilizing with thiourea. Thiourea stabilizers are neutral, for in alkaline solution
silver sulphide is produced. According to Levinos and Burners' method<"'> the
exposed layer is developed in amidol at pH 7 (stabilized against oxidation with
0·1% carboxymethylcellulose), and films are stopped in 3% chrome alum, papers in
3% bisulphite, for 3 mins. Stabilize films in 3% thiourea and 2% glycerin. For papers,
halve the amount of thiourea and omit glycerin. Blot well but do not wash (unless
followed by fixing and a thorough wash).
Thiourea stabilized images kept in a hot damp atmosphere become stained in the
highlights due to decomposition of the complex. They fade if the bath is too concen-
trated. Separate stored sheets with sheets of cellophane. A litre of solution is sufficient
for 13 sq. ft. of sensitive material.
Other stabilizers have been used more or less successfully: ammonium thiocyanate,
allylthiourea, thiosemicarbazide, sulphonates, RSH derivatives such as thioglycolic
Qr thiosalicylic acid, monothiohydroquinone, etc.
150. Washing
Unless the image is stabilized as in the preceding paragraph, or is only kept
for a short time, the silver complexes remaining in the gelatin are likely to
decompose into yellow-brown silver sulphide and sulphuric acid. The free
thiosulphate decomposes to hydrogen sulphide, sulphur and sulphur
dioxide which attack the silver image and sulphide it at the same time. This
is why all traces of fixer must be carefully eliminated by washing for a long
period.
Perfect keeping is only achieved by complete washing. In this operation, the
soluble salts are eliminated from the gelatin by osmosis, the osmotic pressure
being in the order of 15 kgfcm2 • Washing is much more efficient and rapid if
fresh water is constantly brought to the surface so that the concentration
difference is always the maximum (mechanical or air agitation). <24hl
The washing time depends on the thickness of the layer and the method of
washing; usually it is 15-30 mins. for cine films and 30 mins. to 2 hours for
still materials. For washing by changing the water at intervals, at least 2litres
per sq. foot must be used (for 5 mins.) changing the water six times. This
method is economical.
Washing becomes faster as the temperature is raised (2·3 times for a
10°C (18°F) rise). It is more difficult when the fixer is exhausted, that is, con-
taining a high concentration of silver complexes.
Crabtree, Eaton and Muehler have shown that washing in ammonia water
(pH alkaline) is a better eliminator for the thiosulphates and argentothio-
sulphates retained by the gelatin than plain water. Perhaps the co-ordination
compound formed between the gelatin and the argentothiosulphate ion
(AgS 20 3)- is ruptured. Concentration of ammonia 70 ccfl.
The ease of washing also depends on the composition of the fixer and its
pH. Thus with an alum fixer, elimination is not complete until the pH of the
fixer is equal to or greater than 4·9. Washing is more efficient if the layer is
first hardened in alum, then fixed.
Crabtree and Eaton have investigated washing with sea water. <25 > The
hypo is expelled from the gelatin more easily as the sea water tends to shrink
rather than swell the gelatin. Five minutes wash in sea water is adequate but
a final wash in soft water is necessary.
Washing in a closed circuit with ion exchangers. Gregor and Sherman have
perfected a method of washing with a small amount of water, which is purified
in a closed circuit, using ion exchangers. For the cation they used a phenol-
formaldehyde resin, and for the anion, an aniline-formaldehyde resin, or
guanidine or quaternary base-formaldehyde.
Dowex 50 (Dow Chern. Co.) is useful for the cations and lonac A 300
(Amer. Cyanamide Co.) for the anion. A column 45 em high and 2·5 em
in diameter passes 5-10 cc per minute. The cation exchanger is acidified
with HCl. The liberated thiosulphuric acid is split to S0 9 and S, which
produces AgS; the excess is taken up by the anion exchanger. The pro-
duction of pure water is avoided by adding urea which is not absorbed by
the resins.
Wetting agents. The inclusion of a wetting agent in the final wash avoids the
formation of large drops on drying, and helps glazing. On the other hand,
they encourage the formation of froth especially with hard water. Commercial
wetting agents (see para. 356) are sold in concentrated solutions. For use, first
prepare a 10% solution, 5 cc of which is used per litre of wash water. The
immersion time should be about 2 mins.
Wetting agents facilitate the removal of excess water and prevent the for-
mation of air bubbles when prints are squeegeed onto glazing plates.
Organic deposits in washing tanks. Running water brings about the formation
of organic deposits which accumulate on the washing tank walls. They are
removed by periodic brushing and rinsing. If this is not done, particles may
be detached and stick to the emulsion surface. Deep tanks can be washed with
hypochlorite solution diluted with six volumes of water.
Calcium and silica mud is formed in addition to the organic deposit, and this
frequently marks the gelatin surface. It must be removed with damp cotton
wool.
151. Control of the wash water

This generally consists of checking for the presence of hypo in either the water in
the wash tanks, or in the drops collected from the emulsion.
Electrometric control
This is based upon the conductivity difference between the fresh water and the
water containing salts.< 27 > To avoid electrode polarization, alternating current is
preferably used. A neon lamp serves as an indicator.
Chemical control of hypo elimination

(a) Permanganate test. A few drops of water from the washed material are added to
a drop of the following reagent:
Water 1000 cc
Potassium permanganate 1g
The pink colour must remain. If the liquid becomes greenish there is hypo in the
wash water. The permanganate is reduced to manganage and the hypo is oxidized to
tetrathionate.
(b) Iodine test. Starch paper, made blue with a weak iodine + Kl solution is de-
colorized by a few drops of water containing hypo; the iodine is reduced to sodium
iodide whilst the hypo is oxidized to tetrathionate.
2Na,s,o. +I, = 2Nai + Na.s,o.
By using known solutions, the hypo content of the wash water can be found; com-
parison is made with standard hypo solutions.
The following methods are more sensitive:
(c) Decolorization of starch-iodine blue in the presence of sodium nitride following
Jelley and Clark.< 2 8>
(d) Colorimetric estimation with silver nitrate used by Lumiere and Seyewetz, then
by Hackl (see following paragraph).
(e) Mercuric chloride test disclosed by Crabtree and Ross ;<• 9 > a mercury chloro-
sulphide HgC1 2 • 2HgS is formed and 0 ·5 mg per litre hypo can be detected, which is
one-twentieth of the limit with permanganate.
The silver nitrate method is sensitive to 1 mg per litre and the nitride test to 6 mg
per litre.
152. Control of the washed image

The fact that the wash water contains only a trace of hypo does not necessarily mean
that the image will be stable, but only as Crabtree said, that there is no point in pro-
longing the washing. It is therefore necessary to check if any fixer remains in the
washed photographic layer. In this case it is the material itself which is treated with
the reagent, using one of the following methods:
(a) Iodine test.< 30 > An N /10 iodine solution is prepared by dissolving 12·7 g iodine
and 30 g potassium iodide in water to make one litre. Twenty-five cc of this solution is
then diluted to 1000 cc. Five drops of the dilute solution are put on the four corners
and the back of a 6 in. print. Washing is insufficient if the stain disappears quickly.
The discoloration indicates at least 4 mg hypo per sq. ft.
(b) Mercuric chloride test:< 31 > The reagent is a solution of 2·5% potassium bromide
and 2·5% mercuric chloride (poison). A piece of film 1 in. square is folded and placed
in a test tube ! in. diameter. Increasing amounts of hypo (1 : 20,000 to 1 : 1000
solns.) are introduced into seven other similar tubes: 0, 0·005, 0 ·01, 0·02, 0·04, 0·1
and 0·2 mg hypo (calculated anhydrous), and 10 cc of reagent is added to the tube
containing the film and to each of the control tubes. After leaving for 15 mins., the
turbidity is observed which is due to a precipitate of mercuric chlorosulphide, show-
ing the presence of hypo.
(c) Silver nitrate test applicable to papers :<••> The test piece is first treated for
3 mins. in 1% silver nitrate containing 0·5% sulphuric acid (by volume) and 2%
acetic acid, then for 3 mins. in 5% sodium chloride, and finally in a fixing solution of
5% hypo and 2% sulphite. It is then washed and dried. The density of the silver
sulphide stain is measured, showing the amount of residual hypo.
For films, the method has been modified as follows:<••> a drop of a solution con-
taining 0 ·75% silver nitrate and 3% acetic acid is placed on the image face of the film.
After two minutes the excess is removed and the resulting stain is compared with a
colour scale printed on acetate sheet. The palest stain corresponds to the washing
necessary for films which are to be stored for reference.
(d) Selenium test, recommended by Henn and Crabtree, (Ssb) already known in
fixing-bath analysis (para. 154). It has the advantage not to react with the baryta
coating and to produce well-defined spots. Make a paste with 10 g black selenium
and 100 g sulphite in a little water at 90°C. Add 125 cc water, then dilute to 1/20. A
selenosulphate solution is obtained which contains 0·2% Se. A mixture of selenium
toner and hypo can also be used.
153. Elimination of hypo by oxidation

The best way of eliminating the residual hypo in a photographic layer is by
treating with alkaline hydrogen peroxide. After washing, treat for 6 mins. at
18°C (65°F) in the following bath, mixed just before use:
Water 500 cc
{ Hydrogen peroxide 10 vol. 125 cc
HE.1 {Ammonia S.G. ·920 14·5 cc
{ Water 85·5 cc
Water to 1000 cc
This solution does not keep and must not be placed in stoppered bottles as gas
is evolved which may cause breakage.
Wash 10 mins. after treatment.
Area treated: 5 sq. ft. per litre.
With 300 cc 10 vol. peroxide 8·5 sq. ft. can be treated (HE. 2 bath).
Use of these baths may cause either a slight change in the image colour, a
slight yellowing of the whites or softening of the gelatin causing prints to
stick when glazed hot. The colour change can be avoided by adding 1 g
bromide, and the yellowing is destroyed by 2 mins. treatment in 1% acetic
acid or 2 % sulphite followed by washing. The same treatment will harden
the softened gelatin, but where sticking occurs, bathe in 50 % alcohol.
The hypo can also be destroyed by oxidation with 1 % potassium or ammon-
ium persulphate in the presence of a trisodium citrate buffer. Unfortunately
thionates are produced which can quickly sulphide a silver image.
154. Fixing bath analysis

Silver. To estimate the silver content of the fixing bath, it is precipitated as
sulphide. A 50 cc sample is diluted to 100 cc and heated to 50°C. Thirty cc of
20 % sodium sulphide are added and after half an hour at 70- 80°C (158°-
1760F) the precipitate coagulates. It is filtered off and dissolved in 25 cc
boiling concentrated nitric acid. The solution is diluted and treated with
hydrochloric acid, the precipitated silver chloride is filtered, washed, dried
and weighed.
The nitric acid solution of the silver can also be titrated with ammonium
thiocyanate in the presence of ferric sulphate.
Another method of estimating the silver content, due to M. Abribat<34) is
to treat the exhausted fixer with sodium selenosulphate or selenotrithionate
in the presence of gelatin. A colloidal suspension of the corresponding silver
salt is produced and the amount can be determined colorimetrically, the
density being proportional to the amount of silver present. Ten cc of 0·15 %
reagent containing 0·4 % gelatin are added to 0·5 cc of fixer and two drops of
soda lye; the colour is then compared with a standard.
Hypo. The sulphite must first be converted to a compound which does not
react with iodide. To do this, 2 cc of fixer is treated with 2 cc of formalin in
200 cc of iced water. The solution is then acidified with a little acetic acid and
FIXING WASHING, AND DRYING 163
titrated with decinormal iodine using a starch indicator. The process is
repeated without the formalin treatment which gives the total hypo + sulphite
content. The sulphite concentration is obtained by subtraction of the hypo
figure (Atkinson and Shaner).
The alum (chrome or potassium) is estimated gravimetrically by precipi-
tation with ammonia, and after washing the precipitate with a warm solution
of ammonium nitrate, it is ignited to Al 20 3 or Cr 20 3 •
The total acidity is obtained by titrating with soda using a bromocresol
green or bromothymol blue indicator.
Boric acid is estimated after precipitation of the alum with ammonia, and
the hypo and sulphite with mercuric chloride. The solution is filtered and
boiled to remove the acetic acid. Excess sulphuric acid is added to neutralize
to bromocresol green, and finally the titration is made with sodium carbonate
in the presence of glycerin.
Sodium acetate. Fifty cc of fixer is precipitated with mercuric chloride, and
the absence of sulphite is confirmed by testing with iodine and starch. Fifteen
cc phosphoric acid is then added and the solution is distilled. The acetic acid
is distilled over and is titrated in the usual way with a phenolphthalein indi-
cator. (Atkinson and Shaner, Zoe. cit.)
Bromide. The fixer, treated with ammonia to eliminate the alum, is boiled,
filtered and precipitated with mercuric or lead chloride. After further boiling
and filtering, the solution is acidified with nitric acid and excess silver nitrate
is added and back-titrated with ammonium thiocyanate in the presence of a
ferric salt.
Ammonium salts. The fixer is made alkaline with soda and distilled and the
ammonia vapour is absorbed in boric acid. The resulting borate is then
titrated with HCl using a methyl orange indicator.
Sulphates. After precipitating the alum with ammonia and neutralizing,
the sulphate, thiosulphate and sulphite are precipitated with a lead salt.
Knowing the hypo and sulphite content, the sulphate concentration can be
calculated.
Polarographic method. Shaner and Sparks have worked out a method of
estimating alums, sulphite and silver polarographically. <35 l The alum must
first be separated from the fixer by precipitating with ammonia.
155. Recovery of silver from hypo baths

There are several methods of recovering the silver from spent fixing baths
(containing about 5 g per litre). However, a fixing bath, evaporated to one quar-
ter of its volume will deposit almost pure hypo on cooling. All the argentothio-
sulphate remains in the mother liquor. This can then be treated to recover
the metal.
1. Precipitation with zinc. Zinc displaces silver from its salts forming the
corresponding zinc salt and precipitating the metallic silver slowly. The fixing
bath is left to evaporate in a shallow vat, and is then treated with zinc foil
(0·2 sq. ft. per litre). A considerable black deposit forms on the zinc and some
sulphur is precipitated. The metallic deposit is brushed off every day. After
G
about two weeks the operation is complete. <36 l It is also possible to neutralize
the old bath, re-acidify it with 2·5 cc H 2 S04 per litre, and precipitate the
silver with 200 g granulated zinc (per litre) contained in a cloth bag.
The precipitate, composed of silver and sulphur is collected, washed and
dried. It can be fused in the presence of sodium carbonate, or the silver can
be dissolved in nitric acid.
2. Precipitation with guanidine compounds. <37 l The silver from the fixing
bath can be precipitated by guanidine anthranilate or ethyl-xanthate. The
bath treated in this way can be mixed with a fresh bath after addition of alkali
to raise the pH to 10. One g of the guanidine salt is used for each litre of
fixer.
Guanidine is a strong base related to urea CO : (NH 2) 2 in which the oxygen
is replaced by an NH group giving C(NH) : (NH 2) 2 • It is formed when
ammonium thiocyanate NH4CNS is heated to 180°C.
Hydroxylamine hydrochloride also precipitates silver in caustic soda solution.
3. Precipitation with sodium sulphide. This is the most commonly used
method. The bath is first neutralized with sodium carbonate when the alum,
if present, is precipitated.
A 20 % solution of sodium sulphide Na 2S is then added until no further
precipitate forms. As an excess of the reagent must be avoided, small addi-
tions are made to test quantities of the supernatent liquid. The precipitate is
silver sulphide.
Mter decanting and filtering, the precipitate is dried. It contains 750-800 g
silver per kg.
To recover the metal <38 l the silver sulphide is mixed with the same weight
of potassium nitrate KNO 3 • The mixture is placed in a crucible and heated
to 200°C then ignited. The mass becomes incandescent. The sulphide is
reduced to silver and potassium sulphate and nitric oxide is liberated.
Ag 2 S + 2KN0 3 = Ag 2 +K 2 S04 + 2NO
Before it solidifies, the mass is poured into water where it dissolves. The
precipitate, of crude silver, is washed by decantation.
By fusing the crude metal with a small quantity of borax, silver of 97- 99 %
assay is obtained.
Another method is to roast the sulphide in air and then to heat this product
to white heat with sodium and potassium carbonates.
4. Precipitation with hydrosulphite. The pH of the fixer is adjusted to 8
with carbonate, and hydrosulphite is added. A yellowish deposit is produced
which is complete after 24 hours. A copper wire dipped in the solution
should not be silvered (lack of reagent) nor should it be blackened (excess of
reagent).
5. Electrolytic recovery of the silver from fixing baths enables the solutions
to be re-used. It has the disadvantage, however, that elaborate equipment is
required and there must be close control of the operation.
The recovered bath must be made up and re-acidified before re-use. It
must not be used for fixing papers as yellow staining may result.
One system is to pass an electrie current through a vat filled with the old
filtered fixer. A series of stainless steel cathodes and graphite anodes are
immersed in the bath which must be vigorously agitated. The silver is, of
course, deposited on the cathodes. A voltage of 0·3-0·5 is used. Agitation is
necessary to avoid low Ag+ ion concentration near the cathode.
A high current density is generally used in large installations. <39 > On the
contrary, small units give the best results when working at 1-2 rnA per dm2
only. They present the great advantage not to need any agitation. In the
Doffin 'Purhypo' process, <40 >the cathode is a stainless steel grid and the anode
is a carbon rod (F.P. 813,483).
The fixer may become coloured during regeneration. This coloration
occurs at the anode and is due to the presence of developing agents. It is slight
when low current densities are used and when the solution contains hi-
sulphite. <41 >
Rasch and Crabtree<41b) recommend moderate current densities without
agitation: with an acid sodium thiosulphite solution containing 8 g sulphite
and 0·5 g silver per litre, the current density must be 0·01 to 0·02 Afdm2 ;
with ammonium thiosulphate c.d. = 0·02 to 0·04 Afdm2 • Sulphite prevents
chain reactions and sulphide formation. The latter is also prevented by the
small quantity of gelatin deposited on the cathode.
In all cases of electrolytic recovery rigorous control must be exercised over
the solution concentration, the pH, the agitation and the temperature.
6. Electrolysis with no external electric source. The external electrical source
can be dispensed with by using a stainless-steel electrode and a zinc electrode,
joined externally via a rheostat and a milliammeter. <42 > The zinc electrode is
wrapped in cloth or in cellulose paste. With an immersed area 16 X 22 em,
0·5 A can be delivered over 48 hours, but 12 rnA per dm2 is enough. Twenty-
two g of zinc are used for 10 g silver. Most of the silver is deposited on the
stainless-steel cathode from which it is separated by slight flexing.
Recovery of the iodide: precipitation with thallous sulphate<43 >gives thallous
iodide. The bromide precipitates after the iodide. This operation has no
practical importance.
156. Drying
Mter removing the surface water by mechanical or pneumatic means, the
developed, fixed and washed photographic element is dried in a current of
filtered air. The quantity of water retained by the gelatin is between 5 and
20 g per sq. foot, depending on the thickness of the layer and the nature of
the gelatin. Generally 1000 feet of negative film absorb 1000 g of water;
positive film, with its thinner coating, only one half of this.
With photographic papers the water absorbed by the base must be taken
into account as it greatly retards drying.
The temperature used for drying is between 24° and 28°C (75° and 82·5°F).
Drying is stopped when the water content is again about 15 % , otherwise the
gelatin becomes brittle.
With a relative humidity of 60-75 % , film drying takes 15-40 mins. for
negatives and 8-20 mins. for positive. Drying must be preceded by either
air-squeegeeing (sucking or blowing) or by mechanical wiping with cotton
wool. A cine negative film still contains over a litre of water per 1000 feet after
the surface water has been removed; a positive film contains about 450 cc per
1000 feet. The speed of drying depends on the thickness of the layer (therefore
on hardening) and the rate of air circulation and the relative humidity.
Drying which is too rapid can result in curled edges and water-drop marks.
Where necessary, a rapid drying process can be used for a plate by immers-
ing it in 80 % alcohol for three minutes, draining and drying in a stream of
warm a1r.
Another expedient is to treat the plate in a concentrated solution of potas-
sium carbonate-1000 g per litre-and after draining, to wipe and polish the
surface of the gelatin. A negative treated in this way will not be permanent.
At the first opportunity it should be washed and dried normally.
Deformations. The dry photographic image can suffer from two sorts of
deformation: those due to the contraction or expansion of a flexible support,
and those due to internal stressing of the gelatin during the drying of the
unexposed or processed emulsion. The stresses become greater as the thick-
ness of the layer increases.
If drying is too rapid, the presence of drops of water results in areas of
lower density. Hardening reduces these deformations, for the gelatin swells
less; on the other hand, where the marks are present, they cannot be removed
whereas with an unhardened emulsion there is always the possibility of
restoring the gelatin to its original condition by immersing in water, then in
alcohol.
These marks are inconvenient in photogrammetry. To avoid them to some
degree, the unexposed emulsion is soaked in water for half an hour, washed
with alcohol and dried. The drying must be slow and in damp air.
The errors due to deformation of the gelatin are of the order of 1-4,u .
Shrinkage of motion-picture base amounts 0·0(H)·2%.<44l
Effect of drying on density. R. Pinoir has shown< 44 > that the temperature
and relative humidity of the drying air have a considerable effect on density
by altering the physical state of the gelatin.
Raising the temperature and the relative humidity increase the density,
although these two factors work in different directions, the one opposing the
other, and this affects the drying rate. For example a density of 3·08 obtained
at 30°C 75% R.H. falls to 2·35 at zzoc and 35% R.H.-a difference of 0·73.
The effect is greatest with the large grains. It is less pronounced with har-
dened layers. It necessitates rigorous control of all factors when drying sensito-
metric strips, and even films.
The effect of drying upon density is explained by Silberstein's theory of the
rotation of the grains, and also by the theory of compression of the grains
which have a filamentary rather than a solid structure.
Rapid drying. Great progress has been made in this operation in the last
few years and it is due to the necessity for projection immediately after taking
of radar and television film images, to say nothing of the many other appli-
cations. Extra rapid treatment is mainly given to special films which have
thin, hardened emulsions.
We have already seen that by raising the temperature to SO or 60°C (122 or
H0°F), developing and fixing can be carried out in a few seconds. <45 l Thus
Tuttle and Brown<46 l carried out the complete cycle in 4 sees. (development
0·8 sec., fixing 1·7 sec., washing 0·3 sec. and drying 1·2 sec.). At a temperature
of 60°C (H0°F) with a liquid flow of SO cc per sec. and avoiding fixing, they
even cut the time down to 0·34 sec. A film treated in this way can be kept for
a week if tightly wound. After this time, it must be well washed.
When using 70 mm radiographic film, the total time can be one minute
without inconvenience, giving 1S sec. for each stage ; temperature S0°C
(122°F).
Rapid drying can be achieved in four different ways:
(a) On a heated drum: 2 sec. for a film moving at 5 ft.fmin. (lves and
Kunz). Disadvantage: poor conductivity of the cellulose support.
(b) Hot-air blast at 60 ft. fsec. and a temperature between SO and 90°C
(122 and 194°F). Miller< 47 l made a device for this, having 256 jets on the
front and 128 on the rear of the film, with a total air flow of 2·3 m 3/min.
At 60 ft. Jsec. it takes 8 sees. to dry Plus-X film to 10 % humidity at 93°C
(200°F), 12 sees. at 6S°C (1S0°F) and 18 sees. at S2°C (12S°F). There is an
optimum air flow at each speed.
The physical properties of a film dried in this way are excellent.
The slowness of normal drying is due to the presence of a stagnant layer of
saturated air between the gelatin and the atmosphere. This can only be dis-
turbed by violent turbulation-not to be confused with simple agitation-
using an apparatus similar to Miller's.
Katz<48 l has thought of another method of turbulent drying in which the
film is wound on a 3S em diameter drum, heated internally with a 3 kW
heater to compensate for the cooling produced by rapid evaporation. A 3 h.p.
fan blows air onto the moving film at a rate of 0·42S m 3 fmin. and a pressure
of 0·3S kgfcm2 • Five kg of water per hour is evaporated in this way at 48°C
(118°F).
(c) Drying with organic solvents. This interesting method, due to Davies
and Soper<49 l enables films of a limited area-radiographs for example-to
be dried rapidly, taking a minute at the most.
The blotted film is immersed in a solution of 2S % diacetone alcohol in
petroleum ether (inflammable), and is gently agitated. The diacetone removes
the water from the swollen gelatin and falls to the bottom of the vessel, as a
layer which is not miscible with petroleum ether.
157. Reticulation
Reticulation is an irregularity of the surface of a gelatin layer, produced by a
rapid change of temperature when the material is passed from one solution to
another, for example, warm fixer after a cold wash. It is due to the gelatin
being distended parallel to the support, only the surface being able to move. (so)
Reticulation can be produced artificially by treatment in dilute acid or in a

concentrated solution of potassium bromide or iodide. Smethurst< 51 l obtained
the same result by tanning superficially in a 5 % acetone solution of chromic
acid or an alcoholic solution of formaldehyde, or swelling in phosphoric acid,
or, best, in an alcohol solution of gaseous formaldehyde.
The internal tension does not occur if drying is carried out at a temperature
above the melting point of the gelatin, that is, without turning the layer to a
jelly.
158. Glazing and drying prints

Positive paper prints can be given a high gloss by being in intimate contact
with a polished surface during drying. This surface can be a sheet of glass, a
chromed cylinder or a chromed sheet. The gloss of the print surface depends
on the gloss of the glazing surface.
Cold glazing. The washed print is applied wet to a very clean sheet of glass
previously damped with a wetting agent (sulphonated lauryl alcohol, ox-gall,
etc.) or a sulphoricinate. The dry paper comes away by itself. This process
gives the best results, but it is slow.
Hot wet glazing. This is carried out with special glazing apparatus-convex
sheets or rotating cylinders heated to 75°C (167°F). The prints are kept in
perfect contact with a stretched cloth which must be removed and washed
periodically. The gelatin must be well hardened or it will melt and stick to the
metal. Excess hardness due to old material or too much hardener during
emulsion preparation produces unglazed spots. If the paper is freshly coated
(less than two weeks) the gelatin may melt. It is advisable to damp the washed
prints with a wetting agent before putting them on the hot plate to ensure
uniform application. Faults in the baryta coating can result in unglazed
areas.
Dry glazing. Hot dry glazing of photographic prints is much more rapid
than wet glazing. Although the gloss is not as good, it is used for commercial
work such as the production of postcards.
Dry glazing is only possible if the gelatin contains 10-15% moisture and
if the temperature is above 80°C (176°F). The best results are obtained
between 110 and tzooc (230 and 248°F). The critical optimum temperature
depends on the gelatin and its moisture content. If it is too wet, the gelatin
sticks, and if too dry, no gloss results. If the cylinder is too hot, yellowing
results. Undoubtedly, there are many other unknown factors involved, for
dry glazing is generally a source of 'inexplicable' troubles. Calcium deposits
can also reduce the brilliance. Also, contrary to the general belief, a cylinder
which is too clean can cause prints to stick. Any use of wetting agents, soaps,
or organic solvents on the gelatin, before glazing, is undesirable.
Drying on the glazer. A print placed in the glazer, gelatin to the blanket, will
be dried without glazing. Matt surface papers and document papers can be
treated in this way. Gelatin which is too soft or freshly coated, will stick to the
cloth making it necessary to pull the print off. If the paper paste has not an
even structure the dry print will roll up or be deformed irregularly.
159. Analytical examination of image marks
Henn<••J has worked out a method of determining the nature of stains and spots acci-
dentally present on photographic images. The test is carried out on a piece of scrap.
Two drops of solvent are placed on the stain. After dissolving, a drop of the solution
is transferred to a glass or porcelain plate to be treated with the identifying reagent.
Calcium. Solvent: 40% acetic acid. Neutralize with AmOH. Precipitate with 4%
sodium oxalate. Or dissolve the mark in warm HCl. Add 2 drops 10% AmOH then
1 drop of 0·1% Alizarin S. A blue colour is produced with Ca, with crystals visible
under the microscope.
Aluminium. Solvent: 40% acetic acid or 10% (soda+ sodium sulphate). Add 1
drop of alcoholic solution of morin (then 1 drop of acetic acid if the soda solvent was
used): coloration-brown to yellow-green. The lake obtained fluoresces in U .V.
radiation or in sunlight filtered with a Wratten 35 filter.
Chromium. Solvent: dilute HCl. Add 1 drop of bromine water. The chromic ion
produced is neutralized with soda and the excess bromine with phenol, and 1% alco-
holic diphenylcarbazide is added with 2N H 2S04 : a blue-violet colour is produced.
Iron. Yellow stains soluble in 5% potassium oxalate containing 5% HCl.
Blue stains-decolorized with soda.
The hydrochloric acid solution gives a blue precipitate with potassium ferrocyanide.
Silver. Yellow or brownish stains, frequently dichroic, soluble in ferricyanide +
hypo. A nitric acid solution of the stain gives a precipitate with hydrochloric acid.
Also reacts with p-dimethylamino-benzilidene-rhodanine.
1. Pouradier, Roman, Venet, Chateau and Accary: Bull. Soc., 1952, 928-937.
Plant D. A.: Jl. Soc. Leather. Tr. Chem., 1952, 351-357.
2. Herzberger and Henn: Sci. et Ind. Phot., 18(2), 337.
3. Henn R. W. and Crabtree J. I.: P.S.A. Jl., 1951, 13-18.
4. Henn R. W. and Crabtree J. 1.: P.S.A.Jl., 1953, 140-145.
5. Risso-Dominguez C. J.: P.S.A. Jl., 1951, 58-60.
6. Formalin is a 40 or 35% solution of the gas formaldehyde H. CHO in water. It
has an acrid smell. It polymerizes to trihydroxymethylene (H. CH0) 3 which
precipitates as white flakes; this is decomposed to the simple aldehyde by heating.
7. 1 g 6-nitrobenziminazole is dissolved in 200 cc water already containing 1 g caustic
soda.
8. Chateau and Pouradier: Sci. et Ind. Phot., 1953, 129; Baines H . : Jl. Phot. Sci.,
1955, 175-179.
9. Gruenthal E.: P.S.A. Jl., 1951, 95 (from a Berlin thesis).
10. Woolsey D. P . and Pankhurst A., Phot. Jl., 1952, 82, 12.
11. Silver bromide dissolves rapidly at first, then more and more slowly, following
an exponential curve.
12. As far as possible, all photographic solutions should be at the same temperature,
otherwise reticulation of the gelatin may occur when going from a cold to a warm
solution or vice-versa.
13. Rzymkowski J.: Sci. et Ind. Phot., 1952, 245.
14. Alnutt D. B.: Jl. Soc. Mot. Pict. Eng., 1943, 300
15. Malinckrodt Chern. Wks.: U.S.P. 2,586,559 (1952).
16. U.S.P. 2,475,616.
17. Abribat M. and Pouradier J.: Sci. et Ind. Phot., 1953,473--475.
18. Sci. et Ind. Phot., Feb. 1948, 68.
19. Keelan S.: Phot. Eng., 1953, 157-161.
20. Clarke R. G., Milner C. E. and Gomez-Ibanez J.: Phot. Eng., 1953, 331.
21. Sci. et Ind. Phot., 5, 52.
22. Russel H . D., Yackel C. and Bruce J. S.: P.S.A. Jl., 1950, 59-62; Sci. et Ind.
Phot., 1950, 456.
23 . Machines for paper stabilization-see Sci. et Ind. Phot., 1949, 216 and 1952, 398
(Phot. Eng., 1951, 136).
24. Levinos S. and BurnerW. C. : Phot. Eng., 1951, 148; Sci. et Ind. Phot., 1953,65.
24b. Golwasser S. R. : Jl. Soc. Mot. Pict. Tel. Eng., 1955, 64, 248.
25. Eaton and Crabtree: Jl. Soc. Mot. Pict. Tel. Eng., 1943, 380.
26. Gregor H. P. and Sherman N. N.: Jl. Soc. Mot. Pict. Tel. Eng., 1949, 183-192;
Sci. et Ind. Phot., 1949, 461.
27. Hickman and Spencer: Sci. et Ind. Phot.,(IJ 3R, 109 and SR, 5.
28. Jelley and Clarke: Sci. et Ind. Phot., 1(2), 57 and 253.
29. Crabtree and Ross: Sci. et Ind. Phot., 1(2), 215.
30. Cary E. and Wheeler H. H. (U.S. Dept. of Agriculture), Amer. Phot., 1942.,
1942, 16-18.
31. This method was disclosed by Gibson and Weber (Sci. et Ind. Phot., 10, 120) and
was used by the A.S.A.: PH .4-8-1953 (Sci. et Ind. Phot., 1954, 441).
32. Crabtree J. 1., Eaton G . T. and Muehler L. E. : Jl. Franklin Inst., 1943, 351-360.
33. Henn R. W . and Crabtree J . I.: Phot. Sci. and Tech., 1954, 83 and Sci. et Ind.
Phot., 1954, 441.
53b. Henn R. W. and Crabtree J. 1.: Phot. Sci. Tech., 1955 , 111-113.
34. F .P. 825,306 (1936).
35. Shaner V. C. and Sparks M.R.: Jl. Soc. Mot. Pict. Tel. Eng., 1945, 20-32 and
Sci. et Ind. Phot., Nos. 9-10.
36. Sedlaczek disclosed the use of metallic powders in the presence of sulphocarbonic
acid derivatives (G.P. 713,056).
37. U.S.P. 2,221,163.
38. Stratter: Chim. e Industrie (Milano), 1941,23, 213.
39. Hickman: Sci. et Ind. Phot., 2(2), 462.
40. Sharpe C. J.: Sci. et Ind. Phot., 1952, 185; see also Doffin H. G.: Sci. et Ind.
Phot., 10(2), 182.
41. Sharpe C. J.: Brit. Jl. Phot., 1954, 140.
41b. Rasch A. and Crabtree J. I.: Phot. Sci. Tech., 1955, 2, 15-33.
42. Heiberg K.: ActaRadiol., 1950, 215-224; Sci. etind. Phot., 1951,133.
43 . Kieser K.: Phot. Ind., 1940,38, 96; Welliver: Sc. et Ind. Phot., 1956,27,144-145.
44. Pinoir R. : Sci. Ind. Phot., Nov. 1943.
45. Crabtree J. 1.: P .S.A.Jl., 1949, 130-136; Sci. et Ind. Phot., 1949,216. lves and
Kunz.: Jl. Sci. Instrum., 1951, 318; Sci. et Ind. Phot., 1952,21.
46. Tuttle C. M. and Brown F. M.: Jl. Soc. Mot. Pict. Tel. Eng., 1950, 144-160;
Sci. et Ind. Phot., 1950, 223; Phot. Eng., 1952,65-77.
47. Miller F. D.: Jl. Soc. Mot. Pict. Tel. Eng., 1953, 85-104; Sci. et Ind. Phot., 1953,
288.
48. Katz L.: Jl. Soc. Mot. Pict. Tel. Eng., 1951, 264-279; Sci. et Ind. Phot., 1951, 309.
49. Davies I. and Soper A. K.: Brit. Jl. Phot., 1950, 268; Sci. et Ind. Phot., 1950,
295.
50. See work by Sheppard and Elliot: Ind. Eng. Chem., 1918, 727.
51. Smethurst P. C.: Brit. Jl. Phot., 1949, 371-374.
52. Henn R. W.: P.S.A.Jl., quoted in Sci. et Ind. Phot., 1951,299.
Chapter XII
REVERSAL
160. Reversal, reduction and intensification
The name reversal is given to the sequence of operations which enables a
positive image to be obtained in the same layer which has recorded the nega-
tive image. The principle is quite simple:
Mter developing the negative image, the silver of which it is composed is
dissolved in a reducer (or reversal bath). The residual silver bromide is ex-
posed and developed to give the corresponding positive. In the areas where
the negative was dense (subject highlights) there is no residual silver salt to be
blackened and the final image is transparent; on the contrary, in the areas
where the negative was clear (subject shadows), the whole of the silver salt
is left to be blackened and the image is dense.
To reverse a negative to a positive, two conditions must be complied with:
(a) The thickness of the sensitive layer must be reduced so that the maximum
density of the negative corresponding to the subject highlights is equal to the
total density which can be given by this layer: the light parts of the subject
are in this way reproduced in the positive by transparent areas and the whites
are pure. On the other hand, the maximum black must be high enough to
enable the subject shadows to be reproduced by sufficiently high densities.
In practice, the absolute maximum black is slightly greater than the useful
maximum density ; we shall see why later.
(b) The negative image must be developed to a higher contrast than that
of a normal photograph, in fact to a contrast at least equal to that which is
required in the positive image.
161. First development

The negative image can be developed in any type of developer.
It is, however, preferable to use a developer containing a silver bromide
solvent: ammonia, hypo, thiocyanate, or p-phenylenediamine.
The object of this addition is to dissolve a certain amount of the silver
bromide of the sensitive layer slowly and progressively as development pro-
' ceeds. The layer contains more silver salt than is necessary to give the maxi-
mum useful density: the solvent reduces this concentration of sensitive salt
by the required amount, for once the maximum contrast is reached any
continuation of development merely dissolves the excess silver bromide. In
this way the maximum black can be increased or reduced to a certain extent
to correct exposure errors.
171
The most widely used developers contain metol and hydroquinone to-
gether with potassium thiocyanate: 2 g of metol, 8 g of hydroquinone and 5 g
of potassium thiocyanate are the optimum concentrations.
The effect of thiocyanate and bromide are shown in the following tables
based on the work of Verkinderen: (t)
y Dmax. D min.
Thiocyanate
0 1·6 3·15 0·3
0·2% 1·6 3·0 0·1
0·5% 1·6 2·5 0·0
0·7% 1·4 1·9 0·0
Bromide
0·2% 1·3 1·9 0·0
0·5% 1·6 2·5 0·0
1% 1·6 2·6 0·0
A development time should be chosen so that a D max. of about 2·4 is
obtained. When a coarse-grain emulsion is used it develops slowly. A caustic
developer such as D 8 containing a solvent is therefore used. <2 > A formalin+
benzotriazole pre-hardener is recommended.
The following thiocyanate formula <3 > also gives good results:
Water to 1000 cc
Metol 1g
Hydroquinone 8g
Potassium thiocyanate 9g
Hydroquinone-hypo developer:
Water to 1000 cc
Hydroquinone 10 g
Caustic potash Sg
Hypo crystals 2g
Metol-hydroquinone-ammonia developer:
Water to 1000 cc
Metol 4g
Hydroquinone 2g
Ammonia S.G. 0·920 8 cc
REVERSAL 173
p-Phenylenediamine caustic developer:
Water to 1000 cc
· p-Phenylenediamine hydrochloride 10 g
Caustic soda 10 g
Mter development the negative image is rinsed for 1 or 2 minutes, or is
treated in a stop-bath for 30-60 seconds then washed for 2 minutes.
Hardening the gelatin in a bath such as the following is sometimes recom-
mended:
Water to 1000 cc
- 40% Formalin 25 cc
Caustic soda 1·5 g
Sodium sulphate anh. 150 g
Harden for 2 minutes then wash 2-3 minutes.
162. Reversal baths

The reversal operation consists of dissolving the silver which makes up the
negative image. To do this a reducing solution <4 > of the permanganate, di-
chromate, or cerium sulphate type is used.
(a) Permanganate reversing bath. Potassium permanganate, KMn04 , in a
sulphuric acid solution oxidizes the silver, converting it to silver sulphate
Ag 2S04 , whilst the permanganate itself is reduced to manganese sulphate
MnS04
2 KMn04 + 8H 2S04 + 5Ag 2 = 5Ag 2S04 + K 2S04 + 2MnS04 + 8H 20
Furthermore, a small amount of permanganate is reduced by the gelatin to
manganese dioxide which gives the image a brown colour.
2KMn04 +H 2 S04 = 2Mn0 2 +K 2 S04 + 30 + H 2 0
In practice, the bath has the following composition:
Water to 1000 cc
Potassium permanganate 3g
Sulphuric acid S.G. 1·87 10 cc
Treatment time: 4 minutes. Wash: 2-5 minutes.
The permanganate bath reduces the dense parts of the image more rapidly
than the light areas; the rate of reaction is higher at the bottom of the layer
than at the surface.
Potassium permanganate< 5 > is in the well-known form of violet crystals.
Dilute solutions are bluish pink. The crystals must not be allowed to come
in contact with sulphuric acid which decomposes them violently. Perman-
ganate is readily reduced by sulphurous acid, hypo, ferrous sulphate,
organic substances, etc.
174- PHOTOGRAPHIC CHEMISTRY
(b) Dichromate reversing bath. Potassium dichromate K 2Cr 20 7 is a vigor-

ous oxidizing agent. In sulphuric solutions it converts silver to the soluble
silver sulphate. At the same time the dichromate is reduced to chromium
sulphate Cr 2 (S0 4) 3 and potassium sulphate K 2S04 :
K 2Cr 20 7 + 5H 2S04 + 2Ag = Ag 2S04 + Cr 2(S04)a+ K 2S04 + 0 2 + SH:.O

The gelatin reduces a very small amount of dichromate forming the green-
ish chromium oxide Cr 2 0 3 which must be removed
The dichromate solution is composed of:

Water to 1000 cc
Potassium dichromate 5-8 g
Sulphuric acid S.G. 1·87 10 cc
Reversal time: 2-3 minutes. Wash: 2-5 minutes.
Like permanganate, dichromate reacts mainly deep in the layer on the
dense parts of the image.
Potassium dichromate is in the form of orange-red triclinic crystals.
(c) Cerium sulphate reversing solution. Yellow cerium sulphate Ce 2(S04) 3
in weak sulphuric acid oxidizes the image to silver sulphate and is itself
reduced to colourless cerous sulphate, CeS04 •
+
Ce+++ e = Ce++
Ag -e = Ag+
The eerie ion takes an electron from the atom of silver metal and is con-
verted to the cerous ion whilst the Ag loses this electron to become the ion
Ag+.
The bath is made up of:
Water to 1000 cc
Ceric sulphate 10 g
Sulphuric acid 4-cc
which can be diluted if desired.
Ceric sulphate dissolves very readily in water. An excess of water without
sulphuric acid precipitates a basic sulphate.
The eerie bath acts uniformly on the silver image. It has the disadvantage
of being more costly than the previous solutions.
163. Clearing the reversed image

When the gelatin layer is removed from the reversal bath, it is stained with a
precipitate of brown manganese dioxide or greenish chromium oxide.
A solution containing 25-50 cc per litre of sodium bishulphite lye is used to
decolorize the layer. <6 > The image is treated in this solution for two minutes,
REVERSAL 175
then washed for three minutes. The oxides are converted to the soluble man-
ganese or chromium sulphates.
The bisulphite (or sulphite) has the property of partially restoring the sensi-
tivity of the emulsion which is destroyed by the oxidizing agent.
164. Second exposure

After the negative image has been dissolved in the reversal bath, the residual
silver bromide is re-exposed to light so that it, in turn, can be developed.
An exposure of one to three minutes at 18 in. from a 100-W lamp is
usually enough for cine films.
Second exposure method. Instead of fogging the reversed film completely,
the amount of light is regulated according to the density of the residual
sensitive salt. If the film is overexposed, the amount of residual bromide is
small, and it is therefore strongly exposed; if the film is underexposed, there
is a much greater amount of residual bromide and, in this case, the intensity
of the light is reduced so that the positive image will not be too dense. The
intensity of the lamp is varied automatically: an infra-red beam passes through
the reversed film and is modulated according to the latter's density; it is
received by a thermocouple which adjusts the exposure via a relay. The infra-
red radiation has no effect on the silver bromide. Each scene on a roll there-
fore receives a suitable exposure so that exposure errors are corrected.
This second exposure control, originated by Capstaff, is based on the
following observation: in the strongly exposed negative areas the large grains
of silver bromide-the most sensitive-are exposed and developed. None
remain in the residual bromide. In the underexposed negative images, on the
contrary, the large fast grains are only slightly affected, and a large propor-
tion remain in the residual halide. If the intensity of the second exposure is
adjusted so that only grains of a certain sensitivity (or size) are affected, it is
obvious that low negative exposure areas will be affected more than high
negative exposures.
A variation of the second exposure technique (Fred-Jeannot) is to re-
expose the film with a weak even light, equal to that necessary for an under-
exposed image. After development, the film receives a third exposure controlled
by the density of the image, so that an underexposed image receives no
appreciable further exposure, whilst an overexposed image receives a strong
supplementary exposure.
165. Reversal without re-exposure

Second exposure can be avoided by treating in a solution of a Jogging agent<7 >
such as a hydrazine or a semicarbazide, for example, 10 g per litre of
semicarbazide hydrochloride.
The fogging agent can be added directly to the second developer.
166. Second development

Second development can be carried out in any developing solution which will
result in complete or controlled reduction of the residual halide in 4 or 5

minutes. Metol-hydroquinone developers are suitable, for example:
A B
Metol 1 3g
Hydroquinone 5 3g
Sodium carbonate anh. 25 25 g
Potassium bromide 1 2g
The contrast of the positive image can be reduced by shortening the
developing time or by using a less active solution.
After this operation the film is rinsed, fixed-preferably in a hardening
bath-and then washed and dried.
167. Single bath reversal

The exposed film is developed in a developer-fixer (see para. 148). It is then re-ex-
posed on both sides and development is finished in the same solution. It is then
washed and dried.
For example, Miller<•> used the following procedure with Super Panchro Press:
Developer D 19 + 5 g caustic soda and 25 g hypo. Develop 15 minutes at 20°C,
expose for 10 seconds, redevelop and wash.
A reversed image is superimposed on the normal one; it is more contrasty but this
is therefore partly counteracted. This method demands exact exposure.
168. Reversal identity photographs

A widespread method of producing identity photographs rapidly, uses reversal of
waterproof card material, coated with a reversal type negative emulsion. The sequence
of operations is as follows: exposure 1/10th second-1st development in M.Q.
developer 90 seconds at 18°C-rinse 17 seconds-reversal 45 seconds-wash 17
seconds-second exposure 45 seconds-wash 17 seconds-dry 45 seconds.
169. Reduction
Reduction is the name given to the process of lowering the density of a photo-
graph. If reduction is carried out to finality, the image is dissolved away and
disappears completely; this is exactly what happens with reversal baths.
The reduction of the density of overexposed or overdeveloped images is
not widely used in current practice except in photomechanical processes, as
it often leads to uneven results. <9 > On the other hand, the complete removal
of silver images by means of reducers is essential for colour photography as
we shall see in the part III: reduction is then called bleaching.
Reducers are normally divided into three classes according to their action
on the image: cutting, proportional and superproportional.
Cutting and proportional reducers lower the resolving power as this is
highest in the upper part of the image-the part which is affected. Super-
proportional reducers improve resolving power in the low densities and lower
it in the mid-densities. (lO)
Reduction can be carried out by local application, or after applying a
protective layer. To do this, natural latex in ammoniacal solution can be
REVERSAL 177
applied with a brush; this coagulates in air. The protective layer is finally
removed by rubbing with carbon tetrachloride.
Harmonizing. This is the reduction of only the high densities of a negative,
to make them more transparent. Instead of direct partial reduction of the
image, it is preferable to first bleach it completely, for example in cupric
chloride, then, after fully exposing the bleached negative, re-develop it in a
slow-acting developer so that development is stopped before the high densities
are completely blackened. Slow developers such as diluted glycin, D.76, and
p-phenylenediamine, are suitable for this sort of work although any other
developer either diluted or acidified could also be used.
170. Cutting reducers

The effect on the image takes place at the surface of the layer. As the reduc-
tion of density is uniform without changing the contrast, they can be used for
overexposed or fogged images.
The image silver is always dissolved by means of an oxidizing agent; this
removes an electron from the silver metal and converts it to a silver ion:
Ag-e-+- Ag+
As we have already pointed out in the chapter on oxidation and reduction,
an oxidizing agent is a substance which acquires electrons as it tends to pass
to a lower valency. The electron removed from the silver therefore converts
it to a more electronegative reduced form.
The silver ion readily reacts with a negative ion present in the solution to
give either a silver halide or a soluble silver salt.
(a) Bromine water, chlorine water and iodine water can all be used to oxidize
the image, converting it respectively to silver bromide, chloride or iodide
which can then be dissolved in hypo. With iodine water the following bath
can be used:
Water to 1000 cc
Iodine Sg
in which the potassium iodide behaves as a solvent for the iodine whose
solubility in pure water is low.
(b) Cupric chloride reducers:
Most salts in which the metal ion can reduce its valency can be used as
oxidizing agents, the most common being the cupric and ferric salts. Thus
+
with cupric salts the valency changes from 2 to 1: Cu++ e = Cu+ and the
cupric salt is converted to the insoluble cuprous salt.
Water to 1000 cc
Cupric chloride 30 g
Hydrochloric acid 3 cc
The image is bleached and, if carried out completely, gives silver chloride
which can be dissolved in hypo.
If the cupric chloride is replaced by cupric bromide CuBr 2 , the silver

image is converted to silver bromide and insoluble cuprous bromide which is
treated in the same way.
Copper sulphate formula. The cupric bromide can be replaced by a mixture
of cupric sulphate (CuS04 • 5H 2 0) and potassium bromide which acts in the
same way. The oxidized silver is converted to silver sulphate which is preci-
pitated by the alkali bromide as insoluble silver bromide.
Water 1000 cc
Copper sulphate cryst. 40g
Acetic acid 0·5 cc
The silver bromide is then dissolved in hypo. With copper sulphate and
sodium or potassium chloride a silver chloride image will be obtained.
Single-bath sopper reducer. The cupric salt and the hypo can be used in
the same bath in the following way: the cupric salt is converted to a cupram-
monium complex salt which is not precipitated by hypo, as the copper ion is
in the form of a complex ion. To prepare it, it is only necessary to add
ammonia to a 5 % cupric chloride solution until the precipitate of copper
hydroxide is just redissolved (with no excess). A 20% hypo solution is also
prepared. Just before use, take cuprammonium solution 50 cc, hypo solution
500 cc, water 450 cc. If the cupric solution is used alone, a silver chloride
image will be obtained which can be redeveloped.
171. Potassium ferricyanide cutting reducers

Potassium ferricyanide K 3[Fe(CN) 6 ] is a complex salt in which the iron atom
is in the complex ion [Fe(CN) 6 ] - - - and consequently can be mixed with
hypo without mutual action.
The iron in the ferricyanide ion is trivalent: six negative valencies of the
6(CN)- ions are partially neutralized by three positive valencies of the Fe+++
ion; three negative valencies of the total complex ion therefore remain.
If the Fe+++ ion is provided with an electron, it is naturally reduced to the
ferrous Fe++ ion: Fe++++ e -+Fe++.
As the Fe++ ion has only two positive valencies against the 6(CN)- of the
iron cyanide ion, the resulting valence of this ion becomes 6(-) - 2( +) =
4(-), giving [Fe(CN) 6 ] - - - - which is the ferrocyanide ion.
Thus potassium ferricyanide is an oxidizing agent which is itself reduced to
potassium ferrocyanide by a reduction in the valency of the iron ion. The
electron is provided by the oxidized compound which, in this case, is silver
which passes, as we have already seen, from the metallic state to the ionic:
Ag = Ag+ + e. The change from the ferricyanide to the ferrocyanide xs
summed up as follows:
[Fe+++(CN)- 6 ] - - - + e = [Fe++(CN)- 6 ] - - - -
The silver image oxidized by ferricyanide is converted to silver ferro cyanide
which is insoluble in water but soluble in the usual silver halide solvents. <12 >
REVERSAL 179
Ferricyanide solutions are decomposed by light, gtvmg K 2[Fe(CNhJ.
H 1p. <13 > For this reason they should not only be kept in darkness but should
only be used in dim light.
Bleaching is accelerated by having the solution slightly alkaline. It is
dependent also on the size of the silver grains and the thickness of the gelatin
layer.
Farmer's reducer is made up of a mixture ofjerricyanide and hypo. It is un-
stable and must be prepared just before use. The presence of an alkali
increases its stability.
A. { Water 1000 cc
Hypo 100 g
B. {Water 200 cc
Ferricyanide 20 g
Take A 100 cc, B 20 cc, water 200 cc.
This mixture produces a density reduction which in 5 minutes is equivalent
to a speed reduction of 2·5 times. After 25 minutes treatment the drop in
speed is about ten times.
To accelerate the action add 2 cc ammonia. If the water is not added,
reduction takes place four times as quickly.
The photograph must be carefully washed, as reduction continues at a low
rate during washing until the oxidizing agent is completely eliminated.
For continuous use, the above solution is too unstable. It is therefore
preferable to use two solutions : first, the oxidizing agent, then the hypo
solvent. For this the following bleach formula is used:
Water 1000 cc
Ferricyanide 50 g
Ammonia 5 cc
The image is completely bleached in 2 minutes. It dissolves rapidly in 10 %
hypo.
Ferricyanide-bromide reducer. The bleached image is made up of silver
bromide.
Water 1000 cc
Ferricyanide 20 g
The following formula, which was used for the complete bleaching of
certain colour films is stablized with disodium phosphate Na 2 HP04 and
sodium bisulphate NaHS04 which give a stable pH of 6·2. The image is
bleached in 6 minutes at 20°C (68°F):
Water to 1000 cc
Ferricyanide 100 g
Sodium bisulphate 35 g
Disodium phosphate 40g
Ferricyanide-iodid~ reducer: used to bleach the image to silver iodide (treat-

ment time 2-5 minutes):
Water 1000 cc
Ferricyanide 20 g
172. Proportional reduction

(a) Ferric sulphate reacts evenly throughout the image. This results in a
drop in contrast as well as a general reduction of density.
The silver is oxidized to soluble silver sulphate whilst the ferric sulphate
FelS04)a is changed to ferrous sulphate FeSO,. It is not necessary to use a
fixing solution.
The stable ferric potassium or ferric ammonium alums are generally used
in place offerric sulphate; they are double salts: Fe 2(S04h. K 2S04 • 24H 20
Water to 1000 cc
Ferric alum 15 g
Sulphuric acid 10 cc
Ferric chloride FeCl 3 can also be used as a reducer in a 1 % solution. It is,
however, preferable to use the Belitzki mixture which can be used in the
presence of hypo.
(b) Iron-hypo reducer (modified Belitzki formula):
Water to 1000 cc
Ferric chloride cryst. 25 g
Potassium citrate 75 g
Citric acid 20g
Hypo 200g
+
The ferric chloride, the potassium citrate sulphite, the citric acid and the
hypo are each dissolved separately in water. The citrate is added to the ferric
chloride, then the citric acid and finally the hypo.
A potassium ferri-citrate is formed-a complex similar to potassium ferri-
oxalate (which will be studied in the second part), and which, furthermore,
can be used as follows :
Water to 1000 cc
Potassium ferri-oxalate 50 g
Oxalic acid 40g
Hypo 100-200 g
As with the cuprammonium complex, the metal is sequestered in the ferri-
citric and ferri-oxalic complexes; this is why hypo does not precipitate it,
and can be present in the same solution.
For removing the silver from colour prints on paper, a bleach-fix solution
containing the ferric salt of ethylenediamine-tetraacetic acid is used; this is a
REVERSAL 181
complex which has the same function as the ferri-citrate in Belitski's reducer
(para. 555).
(c) Cerium sulphate reducer. The formula is the same as that of the reversing
bath. It must be diluted since slower action is desired. As with the ferric
sulphate reducer, fixing in hypo is unnecessary.
(d) Dichromate reducer. Same formula (more diluted) as the reversal bath.
Clear in sulphite or bisulphite.
Another reducer includes dichromate and potassium bisulphate. This
enables it to be packaged in the solid state: potassium dichromate 250 g +
potassium bisulphate 625 g. Dissolve 9 g of the mixture in 1 litre of water.
For slower action, dilute with an equal volume of water.
(e) Permanganate reducer:
Water to 1000 cc
A. {Potassium permanganate 4g
B. {Water
Sulphuric acid
1000 cc
2 cc
Just before use take : A, 3cc; B, 3 cc; water, 100 cc.
Rinse and clear in 1 % bisulphite.
Contrary to the usual statements in the literature, the dichromate and
particularly permanganate reducers are not proportional, but slightly super-
proportional, and because of this should be included in the following group.
Permanganate only appears to behave as a cutting reducer in acetic solutions.
(/) Conversion to chloride in the presence of permanganate or dichromate.
The silver image can be converted to chloride with permanganate in hydro-
chloric acid solution-KMn04+4HCl+Ag -+ AgCl+MnCl 2 +KCl+H 2 0
using a bath containing 1 % permanganate and 2·5 % hydrochloric acid. The
same result is obtained with dichromate and hydrochloric acid, or dichromate,
sulphuric acid and an alkali halide such as potassium bromide. In the latter
case a silver bromide image is produced.
(g) Ammonium thiosulphate reducer. Ammonium thiosulphate attacks the
silver image-especially in acid solution and at high temperature. As its action
is slow, the dichroic fog and stains of Ag and Ag 2S are removed before the
image is affected. (14)
Use the following solution:
Ammonium thiosulphate 15% +citric acid 1·5-3 % ·
With 3% acid the bath may precipitate sulphur after two days.
For a contrast reduction of 20%, Super XX emulsion must be treated for
10-15 minutes.
173. Superproportional reduction

The action takes place mainly in the dense silver deposits: the shadows are
affected before the clear areas which produces, apart from a reduction of
contrast, a distortion of the characteristic curve: in other words, the high
densities are flatter than the low or medium ones.
(a) Ammonium persulphate reducer. Ammonium persulphate-{NH4) 2 S 110 8

-a salt of persulphuric acid OH-S0 20-0-S0 2-0H is a vigorous
oxidizing agent. It is obtained by electrolysis of a saturated solution of
ammonium sulphate (NH4)zS04 in sulphuric acid. The oxygen produced at
the anode removes two atoms of hydrogen from two atoms of the ammonium
bisulphate which is formed, and these are joined via the two oxygens of the
two OH groups attacked in this way:
502 -ONH4
1 ••••
O!lj~
+ 0 =
,
o+i~
....
so2 -0NH4
2 molecules of ammonium Ammonium persulphate
bisulphate
Conversely the ammonium persulphate decomposes readily to ammonium

sulphate and sulphuric acid in the presence of a substance which can be oxi-
dized, such as silver. Soluble silver sulphate is produced, and removed in the
solution. The decomposition of the persulphate appears to be due to catalysis;
this is why the reduction takes place in the presence of the greater silver
deposit in the dense rather than the light image areas. Furthermore, oxidation
of the image takes place more rapidly as more silver sulphate is formed, which
is in the more opaque areas. In fact, the addition of small amounts of an alkali
halide (sodium chloride for example) slows down image attack by precipi-
tation of the silver salt.
The reducing solution has the following composition:
Water to 1000 cc
Ammonium persulphate 25 g
Sulphuric acid, concentrated 1 cc
The reduced photograph is treated in 10 % sulphite solution to arrest
oxidation, and is then thoroughly washed.
(b) Quinone reducer. Quinone, C 6H 4 0 2 and sodium quinone sulphonate
C 6H 30 2 • S0 3 Na are related to hydroquinone C 6H 4(0H) 2 , and are oxidizing
agents which, in sulphuric acid solution, reduce photographic images: the
resulting Ag+ ion is dissolved as silver sulphate.
Like persulphate, permanganate and dichromate, quinone reacts more
strongly in the dense image areas where more silver sulphate is produced.
For reduction use:
Water to 1000 cc
Quinone Sg
Sulphuric acid 20 cc
Before washing, stop the oxidation in 10 % sodium sulphite or 20% hi-
sulphite.
REVERSAL 183
Quinone is a cyclic diketone prepared by oxidizing aniline with potassium
dichromate in sulphuric acid solution
CH=CH
/ \
O=C C::.O
\ /
CH=CH
Quinone
It crystallizes in golden yellow needles whose odour is somewhat like

iodine; melting point l10°C, very soluble in water, alcohol and ether. It is
reduced to hydroquinone-the corresponding diphenol. In time its solutions
become brown together with the formation of a precipitate of quinhydrone
OH-C 6 H 4-0-0-C 6 H 4-0H.
174. Special reducers

(a) Iodine thiourea reducer. This reducer which replaces the very poisonous iodine-
cyanide reducer, was disclosed by Greenhall in 1926. <16> It is prepared by pouring an
aqueous solution of thiourea into an alcoholic solution of iodine. This can advan-
tageously be replaced by a solution of iodine in potassium iodide<' •> : 6 g potassium
iodide in 10 cc water and 10 g iodine. Make up to 100 cc with isopropanol. Add two
parts of 10% thiourea just before use. Fix in 30% hypo without intermediate rinsing.
(b) Thiourea reducer to remove dichroic fog: thiourea 12 g, citric acid 12 g, water
1000 cc.
Before using a reducer containing thiourea it is advisable to harden the gelatin with
formalin.
(c) Iodine water reducer for local application to the fogged borders of old paper:
potassium iodide 5 g (or bromide 15 g), iodine 2 g, water 100 cc. Then clear in an
acid fixer.
INTENSIFICATION
Intensification of photographic images, which enables the contrast to be con-
siderably increased, must only be carried out using methods which give
stable images. Furthermore, for even intensification, prior hardening of the
gelatin layer should be avoided. Before intensifying, it is advisable to soak the
negative in water for 10 to 20 minutes to swell the gelatin.
175. Mercuric chloride intensification

Mercuric chloride, HgC1 2 , oxidizes the silver of the image, and is itself con-
verted to the insoluble mercurous chloride HgCl:
+
Hg++ e = Hg+
{Ag - e = Ag+
The silver is converted to chloride so that the bleached image is finally
made up of a mixture of mercurous chloride and silver chloride.
To produce a black image again it is sufficient to develop the photograph;
the mercury and silver chlorides are reduced to metallic mercury and silver.
The original image is accompanied by an equivalent quantity of mercury.
The blackening methods which use ammonia or potassium argentocyanide<17 l

instead of a developer should be avoided as the resulting images are unstable
(with ammonia, a mercurosoammonium chloride is formed). Blackening with
10 % sulphite is also of little interest as it results in a minimum intensification.
If necessary the bleacheg image can be sulphided in 2-10 g per litre sodium
sulphide.
Before bleaching with mercury it is necessary to carefully remove any trace
of hypo which would produce yellow stains of mercury sulphide HgS. The
mercury bath is made up of:
Water 1000 cc
Mercuric chloride 20g
( Sodium chloride 10 g
(or potassium bromide 20 g)
which can be diluted as desired; or of:
Water 1000 cc
Mercuric chloride 20 g
( Hydrochloric acid 3 cc
The water used for washing for the first few changes after bleaching should
be acidified with hydrochloric acid (1 %) to prevent mercury salts from be-
coming attached to the gelatin, which would make the image unstable.
It must never be forgotten that mercuric chloride (corrosive sublimate) is
a dangerous poison which must be handled with great care. It must be com-
pletely removed by prolonged washing. Its solutions are decomposed by
light; it is more stable in the presence of hydrochloric acid, or an alkali
halide.
176. Mercuric iodide intensification

Mercuric iodide Hgl 2 is a red powder, slightly soluble in water, which is
produced when a solution of potassium iodide is added to a solution of a
mercuric salt:
+
HgCl 2KI = Hgl 2 2KC1 +
Mercuric iodide is soluble in potassium iodide (forming potassium mercury
iodide), in hypo, and in sodium sulphite. Only the last solution is stable and
can be used as an intensifier.
The negative is treated in:
Water 1000 cc
Mercuric iodide 10 g
Sulphite, anhydrous 100 g
in which it is intensified gradually.
Another bath can be prepared by adding to 300 cc of water, alternately
and little by little, 100 cc of 2 % mercuric chloride and 25 cc of 10 % potas-
sium iodide until the red precipitate is dissolved. It is made up with 40 cc of
10% hypo.
REVERSAL 185
The mercuric iodide Hgl 2 is reduced to mercurous iodide Hgl, whilst the
silver is converted to silver iodide Agl. The mercurous iodide is in turn
reduced by the sulphite to mercury and mercuric iodide, The latter is re-
dissolved in the sulphite (as a complex) and the sequence of reactions starts
again. The final image is made up of yellowish silver iodide and metallic
mercury.
To prevent the mercury from being oxidized by prolonged contact with
the silver iodide, the latter is developed, after washing, in a developer; stable
metallic silver and mercury remain.
177. Indophenol intensification

This method depends on the property of a colour developer to develop an organic dye
image together with the silver image. The mechanism of this reaction will be con-
sidered in the third part.
At the moment it is sufficient to note that the silver image, bleached and redeveloped
is accompanied by a second organic image in situ with the silver image; the latter can
again be bleached and redeveloped a second time and so on. With each operation the
contrast is considerably increased. If such an image is to be used as a negative, its
colour must be borne in mind when printing, to obtain the maximum contrast.
A blue-violet image is obtained with the following developer, which is used on a
negative which has been bleached to silver chloride or bromide.
N : N-dimethyl-p-phenylenediamine 6g
A Sodium sulphite anh. 10 g
{ Sodium carbonate anh. 7g
Water 1000 cc
ex-naphthol 14·5 g
B { Caustic soda 8g
Water 1000 cc
Take: A 100 cc
B 33 cc
Water 200 cc
Printing is preferably carried out on an orthochromatic positive emulsion.
178. Ferrocyanide intensification

Ferrocyanide toning (which we will study in para. 569) results in a great increase
in contrast. It can be used for positive images. Toning with uranium ferrocyanide in
particular enables high-density sepia photographs to be obtained. For negatives, lead
intensification is preferable.
Lead ferrocyanide is white. By treating with sodium sulphide, brown-black images
which are greatly intensified are obtained. Toning is carried out in the following
solution after washing the negative in distilled water.
Distilled water 500 cc
Potassium ferricyanide 40g
Lead nitrate (or acetate) 40g
Acetic acid 5 cc
It is washed first with distilled water, then with tap water before sulphiding.
The negative must be absolutely free from fog.
179. Physical intensification

Physical intensification with silver is similar to physical development; silver
nitrate is reduced by a developing agent in the presence of the particles of
silver in the image. The silver from the decomposed silver nitrate is deposited
on the image silver, increasing its density.
The solution therefore contains silver nitrate, a developing agent (hydro-
quinone, pyrogallol, etc.) and an acid inhibitor of spontaneous reduction
(citric acid). For example:
{ Silver nitrate 5g
Pyrogallol 3g
(
Citric acid 5g
With thick emulsions, dichroic fog is produced, and intensification is very
slow.
Physical intensification with mercury is similar to that with silver. A solu-
tion of the double sulphite of sodium and mercury is used together with a
reducing agent.
Formula IN.S using silver:
{Water 1000 cc
A.
Silver nitrate 60 g
{Water 1000 cc
B. Sulphite anh. 60 g
{Water 1000 cc
c. Hypo 105 g
D.
rate<
Metol
3000 cc
24g
Sulphite anh. 15 g
Slowly add one part of B to one part of A. The resulting white precipitate
is dissolved by adding one part of C. After leaving for several minutes, add
three parts of D with stirring. The mixed solution keeps for only 30 minutes.
Fix the negative in 30% hypo and wash thoroughly.
180. Chromium intensification

This frequently recommended intensifier results in only a slight increase. It
is a mixture of dichromate and hydrochloric acid, and forms a deposit of silver
chloride by oxidation of the metal to Ag+ and precipitation with the ion Cl-,
together with chromic oxide (the amount of which increases as the acidity of
the bath is reduced). Example of formula:
Water 1000 cc
Potassium dichromate lOg
( Hydrochloric acid 7 cc
REVERSAL 187
The bleached image is washed and redeveloped in daylight. Rinse, fix 5 min-
utes and again wash. The bleached image can also be treated with sulphide.
The addition of 5 g of bromide slightly increases the degree of intensi-
fication.
The following dry mixture can be prepared:
Potassium bisulphate 62 g
( Sodium chloride so g
When required, dissolve 14 g of the mixture in a litre of water.
181. Quinone intensification

This process can be carried out with a mixture of quinone and potassium
bromide. It was developed by Hickman and Hecker who used quinone and
hydroquinone-thiosulphuric acid. Muehler and Crabtree<18 l made a more
complete study. The silver is converted to a salt of hydroquinone-thio-
sulphuric acid, which has a dark colour, in the presence of an oxidizing agent.
Other coloured compounds are also produced. The disadvantages of the
process are that the image is not completely stable (being destroyed by acid
fixers), and that intensification does not take place in the presence of more
than 25 p.p.m. chlorides in the water.
r·t" (chlo,ide-f,ee) to 1000 cc
A. Sulphuric acid cone. 30 cc
(Wat" to 1000 cc
B. Potassium metabisulphite 4g
Hydroquinone 15 g
1000 cc
c. {Water
Hypo 22·5 g
Four g of a wetting agent may be added to B. Take one part of A, add two
parts of B with stirring, then two parts of C, and finally, still stirring, one
part of A. The mixture will keep for a maximum of 3 hours. Treat negatives
one at a time for 10 minutes at 20°C (68°F). Wash 20 minutes and dry.
182. Intensification by dyeing

The image is first converted to copper thiocyanate or other mordant, then
dyed (see para. 580).
1. Verkinderen H.: Brit. Kin., 1948, 37-45.

2. Miller H. A., Russel H. D. and Crabtree J.: P.S.A.Jl., 1949,382.
3. Dufaycolour.
4. There is another reversal process in which part of the gelatin layer corresponding
to the image is dissolved. (See Chapter XXXII.)
5. Potassium permanganate is obtained by alkaline electrolysis of the manganate
K 2Mn04 , which is prepared by calcining a mixture of manganese dioxide MnO 2
and potassium nitrate KNO 1 , or of natural pyrolusite and caustic potash.
6. Or sulphite (in the case of dichromate).

7. Ville J. G. and Kodak: U.S.P. 2,150,704 (1937).
8. Miller H . A.: P.S.A. Jl., 1948, 103 and Sci. et Ind. Phot., 1948, 216.
9. To avoid unevenness, it is advisable to swell the gelatin in weak alkali before
reducing.
10. Perrin F. H . and Altman J. H.:Jl. Opt. Soc. Amer., 1952,462-467.
11. Wakefield G. C . : Proc. Engr. Monthly, 1951, 206-208.
12. The exhaustion of ferricyanide bleach baths is controlled by adding a ferric salt
to a sample of the solution. The amount of the resulting Prussian blue is deter-
mined calorimetrically.
13. Lal B. B. and Singhal C. P.: Current Sci., 1944, 78-79.
14. Henn R. W., Crabtree J. I. and Russell H. D.: P.S.A.Jl., 1951, 110-113.
15. Greenhall T. H.: Sci. et Ind. Phot., 6R(1), 168.
16. Willcock R . B. : Sci. et Ind. Phot., 1950, 459.
17. Potassium argentocyanide is prepared by mixing equal volumes of 4·5% silver
nitrate (in distilled water) and 3% potassium cyanide (poison). The argenta-
cyanide gives the maximum contrast with mercuric chloride.
18. Muehler L . E., and Crabtree J. I.: P.S.A. Jl. , 1945, 9; Sci. et Ind. Phot., 1945 ,
222.
Chapter XIII
TONING
~
Toning is a process for altering the colour of positive prints. Bromide papers
only give black images, and it is sometimes desirable to tone them sepia; the
sulphide method is generally used for this. Toning is unnecessary for chloro-
bromide papers and lantern plates, as these can be directly developed in
warm tones. On the other hand, 'print-out' papers, whose colour is not .
pleasant, must be toned; gold toning is usually used for this, but the precious
metals of the platinum group can also be used.
The methods for producing coloured images by ferrocyanide toning will be
considered in Part Ill. They are of more interest for colour reproduction.
The colour of an image can be changed by bleaching to chloride in a per-
manganate or dichromate bath (para. 172 (f)) then redeveloping, in, for
example, a solution containing 0·75 % pyrocatechin and 6 % sodium car-
bonate, followed by clearing in acid hypo.
SULPHIDE TONING
Sulphide toning can be carried out in two different ways:
1. By bleaching to silver halide followed by darkening with sodium
sulphide.
2. By direct convertion of the silver image to silver sulphide.
The image colour tends to become more yellow as the silver image grain
size becomes finer.
--- Sulphiding after bleaching
/ 184.
This is the process which is generally used.
The image is first bleached in a ferricyanide-bromide bath:
Water 1000 cc
Potassium ferricyanide 30 g
This forms an image of silver bromide and soluble potassium ferrocyanide :
the silver, oxidized by the ferricyanide to Ag+, is precipitated by the bromide,
whilst the ferricyanide is reduced to ferrocyanide.
189
After washing thoroughly, the bleached print is treated in a solution of

sodium sulphide<1 > Na 2S; this results in a change of cations between the
+
bromide and the sulphide: 2AgBr Na 2S -+ Ag 2S 2NaBr.+
The following sulphiding bath is preferable:
Saturated alum solution 1000 cc
Saturated sodium sulphide solution 5 cc
By diluting, warmer tones are produced. Higher concentrations of sulphide
produce colder results.
The sodium sulphide can be replaced by ammonium sulphide (NH4hS ,
barium hydrosulphide BaHS, the alkali sulphoxyphosphates or, best of all,
thiourea.
Thiourea NH 2-CS-NH 2, which is a silver bromide solvent, is used in
alkaline solution. The tone becomes colder as the pH is raised (coagulation of
sulphide particles). A normal bath is composed of:
Thiourea 2g
Water to 1000 cc
The carbonate can be replaced by caustic soda at a concentration of 0·4%,
and the thiourea doubled: maroon tones.
185. Sulphiding images bleached with metal salts

(a) Sulphiding mercury-bleached images. By introducing mercury into the
bleached image, pleasing tones from warm sepia to gravure black can be
obtained. To do this, the following bleach is used:
A. Potassium ferricyanide 30 g
Water 266 cc
B. Mercuric chloride 4g
Water 150 cc
Colour Gravure Warm Warm
black black Sepia sepia
Solution A 10 10 10 10
B 30 10 5 0
"
Water 160 160 120 120
Wash, rinse three times in 1% hydrochloric acid to remove the mercuric
chloride (very poisonous) which would be retained by the gelatin, again wash
in water, then tone in:
Sodium sulphide 9g
{ Water 100 cc
( Water 800 cc
TONING 191
(b) Sulphiding a copper-bleached image. When the image is bleached in
cupric chloride or bromide, the insoluble cuprous chloride or bromide is
formed at the same time as the silver halide. Part of the former is removed
by oxidation during washing; the remainder stays in the image. On sul-
phiding, a mixture of copper and silver sulphides is formed which has a
slightly different colour from pure silver sulphide. This method cannot be
used on paper as the paper retains some copper salts, which produce a general
stain on toning.
(c) Sulphiding chromium images. The best bleach is dichromate-hydro-
chloric acid, which gives a deposit of silver chloride and chromium oxide
(para. 172 {f)). 6Ag+K 2Cr 20 7 +8HC1--+ 6AgCl+Cr 20 3 + 2KC1+4H 20
which on toning is converted to silver sulphide Ag 2S and chromium sulphide
Cr 2 S 3 •
The bleach has the following composition:
Water 1000 cc
When thiourea is used for toning, warmer tones than with a ferricyanide-
bromide bleach are obtained by replacing the latter with a ferricyanide-
dichromate-bromide bleach such as:
Potassium dichromate 22g
Potassium ferricyanide 30 g
Water 1000 cc
(d) Sulphiding ferrocyanide images. <3 > Various sepia tints can be obtained
by sulphiding images converted to the ferrocyanides of copper, uranium,
molybdenum, titanium, cadmium, etc. A mixture of silver sulphide on the
sulphide of the other metal is obtained. The original silver image must be
underdeveloped as toning and sulphiding produces considerable intensifi-
cation.
186. Sulphiding with sulphur complexes

A bleached print treated in:
Sodium thioantimoniate 10 g
Ammonia 1 cc
Water 1000 cc
has a much warmer sepia colour with an orange tinge, than when sodium
sulphide is used, due to a deposit of antimony sulphide mixed with the silver
sulphide.
Sodium thioantimoniate, or the double sulphide of sodium and antimony
Na 3SbS4 • 9H 20, is commonly called Schlippe's salt, and crystallizes as
yellow tetrahedral crystals, covered with a brown layer of antimony penta-
sulphide Sb 2S 5 •
The thioantimoniate can be replaced by a thiomolybdate, a thioarsenate or a

thiostannate. The image is yellowish with the thioarsenate and reddish with
the thiostannate.
The alkalinity of the bath is important in determining the colour of the
image. With thiostannate the following shades are obtained:
Sodium thiostannate 10 g
Warm Potassium bromide 160 g
tones { Sodium carbonate anh. 3g
Water 850 cc
Sepia tones: add 100 cc 10% carbonate.
Cold tones: add 200 cc 10% carbonate.
The double sulphides, together with sodium sulphide, give intermediate
colours, becoming a deeper brown as the proportion of sodium sulphide is
increased. With equal quantities of thioantimoniate and sulphide, warm
brown tones are obtained.
Other combinations can be produced by treating the copper-, chromium-,
or ferrocyanide-toned images with the double sulphides.
187. Toning by direct sulphiding

The direct sulphiding of a silver image is achieved with a hypo-alum solution, with
colloidal sulphide or with sodium bisulphide. Only the first method is in current use.
(a) Hypo-alum toning. A photograph treated in a hot solution of hypo and ordinary
alum is slowly sulphided to give a sepia image.
The hypo reacts with the alum (potassium aluminium sulphate): on one hand,
aluminium thiosulphate Al 2 (SO 2 0 3) 3 is formed, which hydrolyses to aluminium sul-
phate Al.(S0 4) 3 and hydrogen sulphide H 28 is formed, and on the other, a precipitate
of sulphur and alumina Al 2 0 8 with the evolution of sulphur dioxide SO 2 • The hypo
is, furthermore, decomposed by the hydrogen sulphide to sodium bisulphite, sodium
hydrosulphide and sulphur, whilst the combined action of sulphur dioxide and hydro-
gen sulphide produces pentathionic acid H 28 50 6 • At the boil, the main products are a
precipitate of sulphur and alumina accompanied by sulphur dioxide. The various
reactions can be summed up as follows:
3Na.s.o. + Al,(S0,) 8 = 38+ 3S0 2 +Al 20 8 +3Na 2 SO,
3Na.s,o. + Al,(SO,). = Al,(S.Oa)a+3Na.so,
Al.(S,Oa)s+3H.O = AI.(S0,) 8 +3H,S
Na,S.Os+H,S = NaHS0 8 +NaHS+S
SH 2S+SS0 1 = H,S 60 6 +5S+ 4H,O
The sulphiding of the silver image is therefore due to nascent sulphur together
with hydrogen sulphide.
The hypo alum solution is practically an argentithiosulphate in the presence of
excess sodium chloride. It is prepared as follows:
To the solution
Cold water 700 cc
{ Hypo 120 g
add
Hot water (70°C or 158°F) 180 cc
{ Alum 30 g
TONING 193
Then pour in slowly with vigorous stirring:
Cold water 18 cc
Silver nitrate 1g
{
Sodium chloride 1g
including the white precipitate of silver chloride which is formed; make up to 1
litre.
For toning, heat the bath to 50°C (122°F) and put the previously wetted print in,
and leave for 15-30 mins. After toning, first rinse in warm water, then wash in running
water.
At 20°C (68 °F) toning takes 6-8 hours.
(b) Toning with colloidal sulphur. An image treated in a colloidal sulphur solution
for 20-30 mins. then given a prolonged wash (1-2 hours) is toned warm sepia.
The same result is obtained by treating a print impregnated with hypo in 1%
hydrochloric acid for at least 30 mins. The nascent colloidal sulphur formed by the
action of the acid on the hypo reacts directly with the image silver
Na.s.os + 2HCl = 2NaCl + S +so.+ H.o
Colloidal sulphur is obtained from hypo solution treated with an acid in the presence
of a protective colloid:
Water 1000 cc
Hypo 150 g
25% Dextrine 500 cc
(c) Toning with sodium bisulphide. Sodium bisulphide Na 2S 2 is prepared by fusing
a molecule of sulphur with a molecule of sodium sulphide i.e. 32 g sulphur with 78 g
sulphide. It is also obtained by adding 200 cc of hydrogen peroxide<'> to 800 cc 5%
sodium sulphide: the sulphide is converted to bisulphide and caustic soda.
A photograph is toned sepia in 30 mins. in a 2% bisulphide solution. The whites
are slightly stained with a sulphur deposit.
(d) Liver of sulphur toning. Liver of sulphur is a crude potassium pentasulphide
obtained by heating equal parts of sulphur and potassium carbonate S + K 2 CO 8 • It
is in the form of a reddish brown mass, smelling of hydrogen sulphide.
When it is dissolved in water, colloidal sulphur is formed which can tone photo-
graphic images.
To tone, treat the previously hardened photograph in a solution of 50 cc of 20%
liver of sulphur in a litre of water at 35-40°C (95-104°F) for a few minutes.
(e) Toning with ammonium polysulphide. Ammonium polysulphide is prepared
by dissolving sulphur in ammonium sulphide (NH4) 2 S; about 10 g per 100 cc is
enough.
The toning solution is prepared by diluting 10-15 cc of the polysulphide stock
solution to one litre with water. The speed of toning can be increased by warming
to 35-40°C.
188. Selenium toning

A silver image from a chlorobromide material immersed in an alkali selenide
becomes reddish, probably due to a deposit of selenium on the black metal.
The best results are obtained with underdeveloped images.
Good selenium toning is obtained by using sodium thioselenate Na 2Se 20 3
obtained by the action of a large excess of hypo on sodium selenosulphate.
The latter is obtained by dissolving selenium in a boiling solution of sodium
sulphite. The toning bath contains about 1 g per litre selenium. It is accelerated
by ammonium chloride.
The T.55 formula has the following composition:
Selenium cryst. 6g
Ammonium chloride 190 g
Water to 1000 cc
For use, dilute with five parts of water. Toning time 3-10 mins. Wash 15
mms.
The selenium can be used combined with sodium sulphide as the selena-
sulphide: 5 g selenium and 135 g sulphide in 200 cc hot water; the solution is
stabilized by adding a few cc of sodium bisulphite. For use, dilute with twenty
parts of water. A ferricyanide-bleached image is toned to a colder colour in
this bath than in monosulphide alone.
PRECIOUS METALS TONING

189. Colloidal silver toning
A silver image, bleached to chloride with cupric chloride can be redeveloped
with a reducing agent. Depending on the nature of the latter, the size of the
resulting particles will vary giving a wide range of tints.
The image is first bleached in the bath recommended by Formstecher:
Cupric chloride 30 g
Hydrochloric acid 3cc
Ammonium persulphate 10 g
Water 1000 cc
The washed image, formed of silver chloride, 1s exposed to light and
reduced with one of the three following solutions.
Stannous chloride 10 g
A. Hydrochloric acid 1 cc
(
Water 100 cc
Hydrazine sulphate 10 g
B. {Water 500 cc
Sodium nitrite 10 g
c. {Water 500 cc
The stannous chloride gives colours from yellow to red. If the print has been
washed after exposure, the colour is purplish brown.
The hydrazine sulphate gives blue tones, provided the image has been
washed after exposure.
The sodium nitrite gives red-violet tints.
Only chloride emulsions give the best results: with chlorobrornide emul-
sions it is preferable to use hydrazine sulphate.
TONING 195
190. Gold toning
Aqua regia< 5 l readily dissolves gold. By slow evaporation yellow crystals of
chloroauric acid AuCl 3 • HCl. 3H 2 0 are deposited, a combination of auric
chloride and hydrochloric acid. By heating, the acid is eliminated giving the
chloride AuC1 3 •
Chloroauric acid combines with alkalis to give the chloroaurates, crystalline
soluble double salts, in which the complex ion is unstable. The most common
are the sodium (yellow crystals) and potassium (orange prisms) chloroaurates
AuCl 3 • NaCl. 2H 2 0 and AuC1 3 • KCl. 3H 2 0.
Auric chloride is decomposed by the silver of the photographic image,
giving silver chloride and metallic gold.
Actually, the image is not completely attacked; the majority of the silver
remains unchanged.
In addition, the size of the particles of gold deposited depends on the pH of
the bath. This means that the colour of the image is a function of the acidity
or alkalinity, as well as the dilution and toning time. In this way, a wide range
of colours, bluish and violet to red, can be produced.
The blue tones result from a coagulated form whilst the red tones are
produced by a very dispersed state of the gold.
Neutral and slightly alkaline solutions give blue tones.
Acid baths, without solvent give pinkish tones.
Gold toning is used with citrate or collodion print-out papers, whose colour
is unpleasant. Printing is prolonged to give a higher density than that re-
quired, as the image is reduced later. The print is washed to remove the
soluble salts, and is then toned in a fresh bath. After toning, the print is care-
fully washed to remove all traces of gold salts (which would give a yellow
stain with hypo). Fixing is carried out in 10-20% hypo, which is completely
removed by a third long wash.
This toning method is used less and less, but is of interest.
191. Gold-toning baths

Gold-toning baths are generally neutral, slightly alkaline or slightly acid. A
solution which is too alkaline decomposes the gold salt to the oxide, which
redissolves in excess alkali; too much acid removes the half-tones.
The gold chloride can either be the neutral chloride AuC1 3 , chloroauric
acid or a chloroaurate. In the case of chloroauric acid, it is best to neutralize
the hydrochloric acid molecule with chalk.
(a) Neutral baths. These are prepared from a solution of gold chloride
containing an insoluble carbonate (calcium, barium, magnesium) to neutralize
the acidity.
Example:
Gold chloride lg
Calcium carbonate 20g
Water to 1000 cc
H
The addition of a few drops of sodium chloride solution to the bath pro-
duces a silver complex which is converted to adsorbed colloidal silver chloride
which reduces the action of the auric ions. This slowing down is even more
marked with the alkali bromides. The colour of the resulting images tends to
sep1a.
With potassium iodide distinctly red shades result.
The reverse effect occurs when the gold salt is included in the emulsion
(self-toning paper). In this case the halides accelerate toning and produce
bluer tones.
(b) Alkaline baths. Sodium carbonate, borax, sodium phosphate, etc. are
used:
Gold chloride 1g
Sodium carbonate 5g
Water 1000 cc
or
Gold chloride 1g
Borax 20 g
Water 1000 cc
(c) Weakly acid baths. Sodium acetate, benzoate, etc. are used, frequently
together with borax or sodium tungstate. Example:
Chloride 1g
Sodium acetate 10 g
Water 1000 cc
to which 10 g borax or sodium tungstate may be added.
192. Gold-toning baths with solvent

(a) Thiocyanate baths. Ammonium thiocyanate NH4CNS is a silver halide
solvent. Using a solution containing 10-20 g per litre with 2 g per litre gold
chloride, bluish-black, sepia or purple tones are produced according to the
dilution.
With 5 g per litre thiocyanate and 0·25 g per litre neutral gold chloride,
blue-blacks are produced. By adding 0·5-1·5 g potassium iodide, the image
is toned more to violet and red. The toning time is controlled in each
case.
The following formula gives purple tones after 5-10 mins.:
Ammonium thiocyanate 12g
A {Water 500 cc
Gold chloride 1g
B {Water 500 cc
Just before use take 10 cc of A, 10 cc of Band 100 cc water.
Neutral thiocyanate baths, however, have a tendency to deposit. They are
much more stable in the presence of an acid such as tartaric, and can tone the
TONING 197
depths of the image; which is not true of the other baths. The best formula
is Namias':
Ammonium thiocyanate 25 g
Tartaric acid 2g
Sodium chloride 5g
Gold chloride, 1% sol. 25 cc
Water to 1000 cc
tones violet-black in 20 mins.
This bath enables print-out papers to be toned after fixing. It can also be
used with chlorobromide prints.
(b) Thiourea baths. We have seen that thiourea is a good silver chloride
solvent, with which it forms complexes. In high concentrations, it also attacks
gelatin. To obtain bluish tones, the following bath can be used:
Thiourea 3g
f (
Citric acid
Distilled water
2g
1000 cc
l( Gold chloride
Sodium chloride
Distilled water
1g
25 g
1000 cc
The sodium chloride moderates the action of the thiourea.
Thiourea baths lose their activity more quickly than acid thiocyanate ones.
193. Gold-toning of sulphided images

Silver sulphide images obtained by one of the methods already described can
be gold toned.
Red tones are obtained with a bath containing 0·4 g of thiocyanate and
0·2 g gold per litre. Blood red tones are obtained with the yellowish images,
preferably obtained with polysulphides, when treated in the above thiourea
bath. With sepia sulphide images the tone becomes red-violet.
{Ammonium thiocyanate 20 g
A
Water 1000 cc
{ Gold chloride 2g
B
Water 1000 cc
Purple-black Brown Red
A 100 25 16
B 100 25 16
Water 1000 1000 1000
The images should be overexposed and developed in a diluted developer.
Nelson toner. Excellent brown tones can be obtained with a single toning-
sulphiding bath. The sulphiding is produced by the colloidal sulphur resulting
from the decomposition of hypo with alum, and whose bleaching action is
retarded by silver bromide. The bath is made alkaline and gold chloride is
added. The practical method is as follows: boil 450 g hypo and 56 g alum in
4 litres of water. Mter cooling, the solution is made alkaline with 56 g tri-
sodium phosphate, then the reaction product of 8 g of bromide dissolved in
30 cc water with 4 g silver nitrate in 30 cc water (silver bromide) is added.
Finally, just before use, 7·5 cc gold chloride per litre of liquid is added.
Toning temperature 32-45° C (90-113 °F). Rinse and fix for 5 mins.
The Kodak formula uses: A. Warm water 41., hypo 960 g, ammonium
persulphate 120 g (added after the hypo is dissolved; if the solution becomes
milky, warm until it is clear). B. Cold water 65 cc, silver nitrate 5 g, then
sodium chloride 5 g. C. Water 250 cc, gold chloride 1 g. Just before use,
add 125 cc C to B with rapid stirring, then pour the mixture into A. Tone
at 43°C (110° F), agitating the prints. Rinse and fix for 5 mins.
194. Toning-fixing
The toning-fixing bath simplifies the operation of gold toning. It contains both
gold chloride and hypo. The washed print is simultaneously toned and fixed in the
same bath.
With gold chloride, hypo gives a double thiosulphate of gold and sodium. This is
decomposed by the silver of the image, producing metallic gold, which is deposited,
and sodium argentithiosulphate which dissolves.
The usual additions to toning-fixing baths are : lead salts, a pH stabilizer such as
sodium acetate, alum, and optionally, a reducer-solvent such as ammonium thio-
cyanate. Alkalis such as carbonates, borates, phosphates, etc., can also be included.
The lead salts activate the reaction. They are themselves toning agents (PbS forma-
tion) and can be used without gold.
Toning-fixer formulas:
Hypo 200 g
Lead nitrate 8g
( Gold chloride 1g
Water 1000 cc
Hypo 200 g
Alum 10 g
Citric acid 1g
Lead acetate 1g
( Gold chloride 0·6 g
Water 1000 cc
240g
=onium thiocyanate 24g
Nitric acid 6 cc
Lead acetate 6g
( Gold chloride 0·3 g
Water 1000 cc
Hypo 200 g
Ammonium thiocyanate 2g
Alum 10 g
Lead acetate Sg
Sodium acetate 10 g
Gold chloride 10 g
Water 1000 ce
TONING 199
195. Platinum toning
Platinum toning gives black images. Platinous chloride PtCl 2 is used, which in the
presence of an alkali chloride gives a chloroplatinite such as PtCl 2 • 2KCl.
The silver of the photographic image displaces the platinum from these compounds:
this is precipitated as the metal, whilst the silver is converted to the insoluble halide :
PtCl 2 + 2Ag = Pt + 2AgCl
The reaction only takes place in acid solution: inorganic acids or acetic or lactic
acids can be used. The preferred platinum salt is potassium chloroplatinite. These
baths keep well, and can be used almost until they are exhausted. After toning at
least 25% of the silver is unaffected.
Example of formula:
Potassium chloroplatinite 0·5 g
Phosphoric acid 10 cc
Water 1000 cc
The chlorides of the metals of the platinum group: iridium, ruthenium, rhodium,
osmium and palladium have the same reactions. Palladium chloride PdCl 2 • 2H 2 0
tones sepia.
1. Sodium monosulphide crystallizes with 9 mols. water : Na 2 S . 9H 2 0 . It is a white

compound, unstable in the air, forming caustic soda, hypo and polysulphide.
The solution only keeps at a concentration above 20% . It must be used away from
sensitive materials in a ventilated room. It is caustic; avoid contact with the skin.
2. Henney and Dudley: Handbook of Photography (McGraw-Hill. New York).
3. For ferrocyanide toning, see para. 569.
4. Generally an oxidizing agent.
5. Aqua regia: mixture of 1-2 vols. nitric acid with 4 vols. hydrochloric acid; the
reaction of the two acids produces chlorine, nitrogen dioxide N O., and nitrosyl-
chloride NOCl.
Chapter XIV
SENSITOMETRIC LAWS
DEFINITIONS
Each amount of light can produce, on a sufficiently sensitive photographic

emulsion, a fixed degree of darkening through the action of the developer. U>
The knowledge of this amount of light, or illumination is the first require-
ment in the study of the relation between the action of radiant energy and the
photographic image.
196. Exposure
This is the product of the luminous intensity by the time of exposure
E=lt
The unit of luminous intensity is the candle-metre or lux which is the
illumination produced by a source of one new candle (or 'candela') at a dis-
tance of one metre. The unit of duration, or time, is the second so that the
exposure It is measured in candle-metre-seconds. The characteristics of stan-
dard sources will be studied at the beginning of the third part, and for the
moment we will ignore the spectral composition of the source, supposing
that uniform white light is used.
If the light beam strikes the layer obliquely, the intensity is diminished
E =Eo cosoc
where oc is the angle between the light beam and the normal to the layer.
197. Opacity
The black silver deposit produced by an exposure E will reduce the intensity
of an incident light beam F 0 to a transmitted intensity F.
The relationship between the two intensities F 0 and F is termed the
opacity:
Fo
0=-
F
The opacity is the reciprocal of the transparency: the lower the intensity
of the transmitted beam, the greater the opacity: for example, an opacity of
200
10 corresponds to a transparency of 1/10 and an opacity of 100 to a trans-
parency of 1/100.
198. Density
Density is the logarithm of the opacity
D = log10 0
The following table shows the relationship between transparency, opacity
and density.
Transmission Opacity Density
1/10,000th 10,000 4
1/1,000th 1,000 3
1/300th 300 2·5
1/100th 100 2
1/SOth so 1·7
1/20th 20 1·3
1/10th 10 1
1/Sth 5 0 ·7
1/3rd 3 0 ·5
1/2 2 0·3
If a is the thickness of the sensitive layer <2 l and kits coefficient of luminous
absorption, the effective exposure at the depth xis Ex = E,- kx which enables
the total density to be derived from the relation
1Ja
DE = - f(Ee-k:!')dx
a o
The density can be expressed by an infinite number of different values
depending on the measurement method. In practice it is measured by specular
or diffuse light. With specular light one has
D _ normal incident flux
1 10
li - og normal transmitted flux
It is very difficult to measure specular density unless the measuring beam
is perfectly collimated.
In diffuse light (by an opal glass for example) the density value is lower than
the preceding value.
D = lo diffuse incident flux
i\.. g10 normal transmitted flux
The relationship Q = D11 /D* is the Callier coefficient about 1·5 (1·25 for
fine-grain images and 1·8 for coarse-grain images). As the variations of this
coefficient are not well defined the Renwick and Bloch formula is preferred
log10 Di\.. =a .log10 Dn +b
in which a and b are coefficients constant for the same opal glass and the
same emulsion. L. P. Clerc gives the following figures for a particular
example
log10 D il-. = 1·045 log10 D 11 - 0· 286
The effective density D<f> which corresponds to contact printing where the
transmitted light is immediately received by the positive emulsion behind
the negative. In this case it is the total transmitted light, specular and diffuse,
which is effective
normal incident flux
D </> = I og10
total transmitted flux
The effective density is related to the diffuse density by the formula
D Pq, = kDil-.
where p is about 1.
If the incident light is, however, diffused, the density is measured with
respect to this diffuse light
D·'· _ diffuse incident flux
1 10
'I' - og total transmitted flux
and the four densities are mutually related by the formula
+
DrjJ = D<f> Dil-. - D 11
where D 11 > D r~- > D<f>
In projection printing, the incident and transmitted beams will be parallel
if the negative is non-diffusing and if scattering of the light can be avoided. In
fact, the effective density in this case is intermediate between D 11 and Dr~-.
This also holds for motion picture 'optical' printing.
The density value also depends on the image colour; it is at the maximum
with the most strongly absorbed light, that is when it is measured with light
of a complementary colour.
Reflection density. The reflection density of an image on paper is obtained
by measuring the intensity of the normal diffuse beam, when the incident
light is projected at an angle of 45°. This density is defined as the relationship
between the light reflected from a pure white and the light reflected by the
sample
normal reflected light from pure white
D = 1og10
R normal reflected light from sample
The pure white rarely reflects more than 80 % of the incident light, and
this is the reason why the ratio of incident to reflected light is not used. The
densest blacks reflect about 4-6% of the light. This reduces the luminosity
range of photographic papers.
When the paper texture is pronounced, the density varies regularly as the
sample is rotated about its perpendicular axis.
The densities obtained on matt paper are appreciably lower than those on
glossy paper. The luminosity range of the latter appears greater but the
elimination of unwanted reflections by using polarized light eliminates this
difference. All papers then appear to have the same maximum density, as the
reflected light is not diluted with specular reflections.
CHARACTERISTIC CURVE
199. If a series of increasing exposures is given to a photographic emulsion,
each different exposure gives, after development, an image, or silver deposit,
represented by a specific darkening (Fig. 7).
By measuring the density of each step and drawing a graph with the den-
sities on the ordinate and the log exposures on the abscissa the characteristic
curve<3 > of the emulsion is obtained (Fig. 8). It comprises an underexposed
region AB (toe), a straight line region BC which is the normal exposure region,
an overexposure region CD (shoulder) and a solarization region DE where
the densities again decrease. The part A0A represents the period of photo-
chemical induction, A being the first visible point or threshold.
200. Contrast
The gradient of the characteristic curve is measured at each point by the
tangent at this point (Fig. 9); we have
mn
tan ex=-
pn
Now mn = Dm and pn = log10 En -log10 EP
D
therefore tan ex=
log10 En - log10 EP
where Dm = tan IX (log10 En - log 10 EP).
It is obvious that the value of tan IX, low at A, increases up to B, remains
constant from B to C, then decreases from C to D until it is zero, then be-
comes negative from D to E.
When IX = 45°, tan IX = 1.
The tangent to the characteristic curve measures the contrast y (gamma).
This varies along the curve; if only the straight line portion is considered, the
preceding equation becomes
D = y (log10 E -log10 i)
in which i is an emulsion constant, which represents the exposure corres-
ponding to the point of intersection of the produced straight line with the
abscissa. This is customarily (but wrongly) called the inertia.
Photographic reproduction is said to be correct when the contrast is unity.
Negatives are developed to a much lower y (0·65-0·8) to take advantage of
the increased exposure scale. The positive copies are therefore developed to a
y greater than 1 to restore the true rendering following the equation:
y positive image = y negative image X y positive development
H*
FIG. 9.
FIG. 10.
FIG. 7. Scale of increasing densities.
For example: to obtain a motion picture positive image with a contrast of
1·4 starting with a negative with a contrast of 0·7, the positive must be
developed toy= 2 as 1·4 = 0·7 x 2.
201. Effect of developing time on contrast

As soon as an image appears during development, it has a very low contrast.
This increases as development proceeds (Fig. 10) until a limiting value is
reached-gamma infinity Yeo· With negative emulsions Yeo is about 1-1·6
whilst it can be as high as 4 for positive emulsions.
As we have already seen, gamma infinity corresponds to the complete
blackening of all exposed grains; the different densities are therefore com-
posed of completely developed crystals with none in an intermediate con-
dition, and differ from each other only in the number of these grains. In
Part II, the relationship between y eo and the emulsion type will be shown.
The straight-line portions of the various curves of the same emulsion
coincide at the point i if the developer contains no alkali bromide. This
condition can never be satisfied in practice for a soluble bromide is formed
during development at the same point as the image, and similarly, bromide is
added to the developer to reduce fog. The intersection of the straight lines
takes place below the abscissa (and sometimes above also), which results in an
increase of the whole image as development is prolonged.
If an excess of alkali bromide is added or formed, a regression of inertia
occurs; the point i is displaced towards the greater exposures whilst the point
of intersection of the straight lines is pushed still further below the exposure
axis. At the same time, the contrast increases.
o.---r---~~~--~
2.1---_;1---:::;;;~"'
.,.,
.... -··
~~--- .. ~ ........
-~jL~~-
------· --·
------·
2
---
3 4
FIG. 11.
Variation in density as function of development time.
Time of development. If D eo is the highest density for a given exposure, t the

development time to obtain density D with the same exposure (Fig. 11 ), t 0
the time taken for the image to appear, r a coefficient depending on the
developer type and e the naperian log base, Sheppard's formula gives the
value of D:
D = Doo (l- e-(n,l)
This formula can be compared with Watkins' empirical law:

D00 t
log = Ko log -
Doo- D to
where K 0 is the development velocity constant. After simplifying, it becomes:
t 1
- = 2Ko
to
where t = t 0 C for the production of a normal contrast. C is the 'Watkins
Factor' for the particular developer.
The contrast obtained as a function of the development time t, is given by
the exponential equation of Mees and Sheppard:( 4 l
y = y 00 (1 - ekt) and D = Doo(1 - ekt)
k, which is dependent on both emulsion and developer, has a value of 0·3-0·5,
being higher for slow emulsions.
Influence of temperature. Both density and contrast increase with tempera-
ture. For equal contrast, the development timet as a function of the tempera-
ture (} is calculated from the formula
t = KeAII
where lOA =log Cr, Cr depending on the developer. Thus hydroquinone
has a coefficient double that of metol; the effect, in an M.Q. developer of an
increase in temperature is greater on the hydroquinone than on the metol;
the hydroquinone becomes more active than metol. Conversely, at low
temperatures, it is primarily the latter which is effective.
202. Equations of the characteristic curve

The characteristic curve of an emulsion results from the properties of the various
grains. If v is the number of centres per crystal, the number of grains made develop-
able by an exposure E is:
X= a(1- e-V)
where a is the total number of grains per em•. A grain becomes developable only after
a definite exposure; the nature of the developer is not generally important, except
for hydroxylamine and glycin which develop the heavier exposures. If E is the effective
coefficient of absorption, a the average projected area of a grain and n the number of
quanta incident per unit area, it is found that the grains a require at least an effective
quanta to become developable by an illumination of n quanta. Only a small proportion
Ea of this area is effective in the formation of this latent image By letting y be a variable,
a function of the illumination such that y = Ean, there is an inflexion point, and for a
number of effective quanta per grain of 2:
D y2(3 +y)
Dm (1 +y) 3
On Trivelli's supposition that the distribution of grains follows an exponential
c urve, and putting ll = D/Dm, we have :
2 ( arc. cos y1- /))
y =-=-COS 60° - -1
v1- a 3
The coefficient of effective absorption E is related to y and n by the equation
log E = 16293 -log (,\u) +logy -logE
where E is the exposure in ergs/em•.
Toraldo di Francia represents the characteristic curve by the general equation
n 1 logc-n 2 log(C-c) =n 8 logE+k
in which c /C- c = kE (Boll. Ass. Ott. !tal., Jan. 1944, p . 75).
2
If Eo is the exposure on the front of the emulsion and EP the exposure at the rear,.
log E 0 /EP is proportional to the thickness of the emulsion. Webb has shown that for
slow emulsions where this logarithm is greater than 2, the relative gradient y/D m is
fixed almost entirely by the absorbing power, whilst for rapid emulsions with a
relatively low slope, the form of the curve is also dependent on the distribution of light
between the grains. In other words, the influence of absorption on the curve shape
decreases as the initial value of y/D m decreases.
Additivity law. Let lA be the intensity of a coloured light A necessary to increase
by d a density D obtained with this light A, and In the intensity of light B necessary
to increase by d the same density D obtained with light B, and let IM be the equivalent
intensity obtained by mixing lights A and B. Putting aiM = alA and hiM = fJin,
where a+{J = 1; we have
and for n coloured lights
"'niM = 1
L In
E . Katz (Thesis, Utrecht, July 1941, p. 57) found an equation of the form
~ - -1-st·~
IA tz-tl t, IA(t)
B B
Van Kreveld's law, put into general terms by Webb is a satisfactory approximation
to this function: If two exposures IA and In, of two radiation bands A and B, each give
in t the same density D, this will also be obtained by a mixture of A and B such that the·
exposure is ociA +(1- :x)In.
SHAPE OF THE CHARACTERISTIC CURVE

203. The characteristic curve of a normal emulsion is generally S-shaJJed
with a straight part between the two regions of underexposure and over-
exposure. The photographic reproduction becomes more exact when the toe
is reduced to the benefit of the central straight part: these emulsions are
found in the sensitive elements for colour photography and for photo-
mechanical reproduction (orthophotic emulsions).
There are, on the other hand, anorthophotic emulsions which have no-
straight-line portion or which have two.
In the first case the concave toe is very long, only a tangent at the inflexion
point marking the transition to the overexposure region (Fig. 12). The image
obtained cannot be a precise reproduction of the subject.
The curves having more than one distinct straight line are obtained with
emulsions with grains of different sizes (and therefore sensitivities): these
emulsions obtained by precipitation in steps, by mixture or by superimposition of
two layers of different sensitivities (being themselves mixtures) are currently
used in the manufacture of plates and films to increase the exposure latitude.
D D
Log. E
FIG. 12 FIG. 13
Anorthophotic emulsion with no Anorthophotic emulsion with two
straight line. straight-line portions.
Each group of straight lines in the family of curves converges at a different

point on or below the log E axis (Fig. 13), but frequently the lower part of
the curve has no definite slope; this is a simple arc which joins the straight
line higher up. These are called long-toe emulsions. Although approved
commercially, these emulsions are inferior to the straight-line emulsions
from the viewpoints of accurate reproduction and subsequent ease of printing.
The characteristic curve, instead of having a regularly increasing slope as
above, can on the contrary, be composed of several straight portions with
crossing gradients (Fig. 14) due to the non-correspondence of the constituent
emulsions (bad blending for example).
6 minutes
D f..
""0 _,0
""II
3
4
3
minutes
minutes
0 1 3 4
FIG. 14 FIG. 15
Anorthophotic emulsion with Derivative curves of a
decreasing gradient. positive emulsion.
204. Variation of contrast along the characteristic curve
The image contrast increases along the curve up to the start of the straight-line
part after which it decreases to zero at the beginning of solarization; but the
change in slope is not constant along the curve. Starting at the threshold, the
increase is at first slow, then it increases progressively up to the straight line
when it remains constant; it changes again if there is a break in the curve,
then drops after a sharp turn at the beginning of the shoulder. This is shown
in the derivative curves corresponding to the characteristic curves in which
the ordinates are dD /d log E (Fig. 15).
205. Exposure latitude

The latitude is the brightness range which can be accommodated by a sensitive
layer.
A good negative emulsion has a characteristic curve similar to that shown
in Fig. 16; the straight-line portion covers a brightness range of 1 : 132. This
range is sufficient to accommodate most subjects, but the latitude is in fact
much greater, for the brightness range between A and Dis 1 : 2,400. With a
subject having a brightness range of 1 : 100 the total exposure latitude is
24-12 times for overexposure and 12 times for underexposure. It is obvious
that the greater the brightness range of the subject, the lower the exposure
latitude; the exposure time must be estimated more accurately.
The measurements of the extreme brightness values of a subject are there-
fore very useful; they can be made more or less accurately with various photo-
electric photometers which are directed successively on the shadows and high-
lights of the subject. On the other hand the parts which are to be accentuated
must be chosen in order to eliminate the extremes which would falsify the
calculations: areas of snow, reflections from the sea, dazzling sky, useless
shadows, etc., unless the interesting details are situated in the luminosity
extremes, when the exposure is reduced or increased accordingly.
D 128
64 D
32
2 16
8
-I 0 1
Log. E
FIG. 16. FIG. 17.
The normal brightness range-that is the range covered by the straight
line-is reduced somewhat as development proceeds and contrast increases.
Always, and this should be carefully noted, it is the difference between the
extreme densities which reproduces a fixed exposure range; if development is
continued to y = 1, the opacity range obtained will be equal to the exposure
range, and consequently, when printing the positive, the negative gives an
equal exposure range which the paper cannot accommodate. If, on the con-
trary, the y is below 1, an extended luminosity scale will be translated into
an opacity range which is much lower, as if it were compressed. The negative
therefore has a reduced luminosity range; printing of positive copies will be
simplified.
If ~E is the log brightness range of the subject, and o the density range
which reproduces this brightness range, then
o=~Exy
Compared with negative materials, photographic papers have but a slight
exposure latitude. This explains why the negative must not have too great a
brightness range. The greatest range is accepted by positive emulsions of
low contrast (soft papers) as a low y corresponds to a high ~E.
Photographic papers have the following average characteristics:
Paper Brightness range
Soft 30
Normal 20
Hard 10
206. Solarization
Solarization is a reversal phenomenon which is produced after a certain ex-
posure when the density decreases instead of increasing (E = 10,000-
20,000 threshold value).
Referring to the characteristic curve of Fig. 17, it is seen that after the
point C there is a more and more accentuated drop in the rate of density
increase as a function of exposure. The contrast drops until it is zero at D
whilst the density is relatively constant for a considerable exposure range.
The overexposure region CD, with its characteristic slowing down of the
density increase, is already related to the solarization phenomenon which it
precedes.
Reversal by solarization takes place in the region DEM of the curve; the
density falls as exposure is increased and the resulting image is a direct
positive. The length of the part DM depends on the emulsion; most fre-
quently it does not reach the exposure axis and leaves a considerable uniform
residual density.
With some sensitive layers, a second reversal MN occurs, the density rising
again. Some authorities state that there are several successive alternating
cycles, of decreasing amplitude.
The relationship between solarization and the overexposure region gives
rise to the supposition that the development centres are destroyed; that is,
two opposite reactions both produced by light: after a certain exposure the
destruction process completely predominates over the production of develop-
ment centres.
The destruction can only take place on the centres already produced. It is
admitted that the number of atoms of silver constituting a development
centre is diminished below the developability level by reconversion to silver
bromide by the halogen diffusing from the interior of the crystal towards the
surface.
Solarization is enhanced by the presence of iodide ions I-, whose concen-
tration must be at an optimum, as well as by bromide ions Br- (Chloride
ions Cl- , have no effect). Conversely, silver ions Ag+, retard the phenomenon.
Solarization is also favoured by bromine acceptors, 1% sodium nitrite, acetone-
semicarbazone or phenol. <5 >
Low temperatures ( -160°C) prevent solarization. A static pressure, on
the contrary, accelerates reversal: <6 > 100 kgfcm2 for papers and 400 kgfcm2
for films.
Chemicals such as sodium arsenite or stannous chloride which can form a
latent image in the absence of light, also produce reversal by solarization.
Similarly, hydrogen peroxide and ozone can be used. <7 >
The preparation of a solarized emulsion for the production of direct
positives consists in producing a uniform latent image corresponding to the
critical exposure. This can be produced by light, or can be chemical fog
-controlled action of an arsenite for example. The sensitivity of such a
material is lower than that of a chloride paper. Maurer and Yule have
noted that certain emulsions, easily solarized, produce positives with a
very long low intensity second exposure< 8 > following a relatively short first
exposure.
The effect of gelatins with a high reducing power (producing internal fog
and an unstable emulsion) is also important in the second reversal following
solarization. In this case it assists a photoreduction process.
It should finally be noted that colour sensitization of direct positive emul-
sions requires higher concentrations of sensitizer than normal. In addition,
desensitizers like fuchsine sensitize them to long wavelengths without altering
the general sensitivity.
The rehalogenization theory which was outlined above was proposed by
Luppo-Cramer in 1905, then supported by Webb and Berg (see Webb and
Evans: J.O.S.A., 1940, p. 445). It is generally accepted today. Other theories
propose the interference of coagulated silver which loses its catalytic properties
(Eggert, Arens, Noddack, Meidinger, von Ardenne); the coagulation of the
gelatin around the grain (Luther); the reduction of contact between the brom-
ide and silver metal by the liberated bromine (Kuhn and Erdos); and finally,
more recently (1948), the blocking theory when the surface silver which
develops quickly blocks the grain and isolates it from the developer (Hautot
and Debot). The latter theory appears to have been abandoned by the first
of its proposers.
LAWS OF PHOTOGRAPHIC ACTION

207. Reciprocity failure
Plot the characteristic curves of an emulsion first at constant intensity and
varying time, then at constant time and varying intensity, in each case having
the luminous energies of the two series corresponding to each other.
E = l ctv = lvtc
The two curves obtained are different. If low intensities are used, the vari-
able time curve will be less contrasty than the variable intensity curve; but if
a high intensity is used, then the variable intensity curve will have a lower
gamma than the variable time one. It can be further stated that whatever the
intensity used, the variable time curve has practically the same gamma, whilst
the variable intensity curve has an appreciably higher gamma at low inten-
sities.
Bunsen and Roscoe stated that the photographic action P is proportional
to the product of the intensity of the light and the duration of the exposure:
P =It. It is seen that this law is incorrect except for very active radiation:
y-, X-, oc-, {J- and cathode rays.
Log I
-3 - -s -4 -:s -2 -1 o 1 2
FIG. 18.
Graphical representation of reciprocity failure having the log I values on

the abscissa and on the ordinate the log It values which give a constant den-
sity at each intensity value (Fig. 18). The exposure times are on the parallel
lines which cut the resulting curve diagonally.
It can be stated that the exposure It, necessary to give a certain given den-
sity, is at a minimum for an average optimum intensity I 0 (maximum effi-
ciency); with low and high intensities a greater exposure is needed to produce
the same density.
At 0°C the minimum of the curve is still visible; at 50°C and with high
intensities log It tends to decrease, whilst at -75°C it tends to increase.
The inclusion of silver iodide in an emulsion produces a shift of the
reciprocity curve without changing its shape. <9 >
FIG. 19.
Characteristic surface of an
Agfa negative emulsion ob-
tained by Arens and Eggert
having log 1 and log t hori-
zontally and D vertically.
The horizontal region of the
front corner , represents the
"inertia zone" limited by
the threshold of effective
exposure (black line) : in the
upper part the gradient of
solarization followed by a
further upward curve of the
surface will be noted.
To calculate the reciprocity failure with the characteristic curves, these

are sometimes represented in three dimensions which correspond respectively
to the log intensities, the log exposure times and the densities (vertically).
This results in what are known as 'characteristic surfaces' or rather volumes.
The characteristic surfaces are more difficult to interpret than ordinary
characteristic curves without considerable experience. They can be replaced
with flat representations (Fig. 20).
-7r--n~~nr~~n-~~~~~~~
cit
~6~-i~rf~M\~\-~~~~~r-~~~~
5~,_~~~~~~~.,~~~-4
4~-r--~~~~~~~~~~~+-~
3~-r--r-~~~~~~~~~-+--4
2~-r--r--r~~~~~~~~~~
-s -4 -3 -2 -1
FIG. 20.
Flat representation of the characteristic surface of a negative.
208. Threshold of effective illumination

At low light levels, no impression is made on the sensztzve layer below a
critical level of illumination whatever the time of exposure. This is the true
inertia value: the threshold of effective illumination.
214
There is no reciprocity failure with exposure times less than 4 X 10- 5 sees.
according to Berg's calculations, confirmed by Alentsev. <10 > However, at high
intensity levels with exposures of 1 JLSec. on a panchromatic emulsion, Milne
found failure with red light, but not with blue light. <11 >
Reciprocity failure is explained by the delays which can occur during the
concentration of the silver ions Ag+ around the sensitivity specks. These
become saturated with electrons and the electron transfer is retarded. Accord-
ing to Mott, the small centres lose their electrons which recombine with
bromine atoms.
At low intensities, thermal decomposition prevents the sub-latent image
from increasing by capturing electrons.
Emulsions for Raman effect. The emulsions for the study of the Raman
effect must be very sensitive to low intensities of illumination at exposure
times as long as 20 hours. Grain sufficiently fine to give a resolving power of
20 linesjmm. Development gamma: 1·5.
209. Schwartzchild coefficient

Schwartzchild has stated that the photographic effect P can be expressed
with a satisfactory approximation by the formula
p = JtP
where pis a variable term about 0·85. It is given by Renwicks formula
yt
p=---;-
yt
where y 1 and Y; are the contrast factors of the curves obtained with intensity
scale and time scale exposures. p, which possess a minimum at average bright-
ness, is lower for slow emulsions and moreover varies with the wavelength.
Kron's formula, on the other hand, represents experimental observations:
P =It X 10-aw with w = j1 +(log :J 2
The coefficients a and I 0 depend on the emulsion. a is in general about 0·2.

For low illuminations the relation is reduced to that of Schwartzchild where
p = 1/1+a and, for high intensities, to the Bunsen-Roscoe formula.
The Schwartzchild conception is no longer accepted for medium intensities.
210. Intermittency effect

The effect produced by an intermittent exposure is, for equal energies, lower
than the effect produced by a continuous exposure; the characteristic curve
obtained with intermittent exposures has lower densities especially at the
lower It values (Fig. 21).
Intermittency has no effect once the frequency of interruption reaches a
critical level which depends on the nature of the emulsion. This critical
frequency increases with the square root of intensity and drops with the
total exposure time. <12 > This phenomenon is attributed to the fact that the
dark periods, becoming very small, become comparable with the intervals
which separate the individual quanta affecting each grain.
The critical frequency is proportional to the relationship: time of flash/
+
time of flash darkness; and is not dependent on the emulsion and the
development. <13 >
With very active radiation, such as X-rays, a single quantum can make a
silver bromide grain developable; interruption of the exposure then has no
effect whatever the frequency.
log. E
FIG. 21. A: continuous exposure. B: intermittent exposure.
To explain the photographic action of intermittent exposures in the case

of moderate intensities two opposing factors must be considered: the forma-
tion of the latent image and its subsequent destruction. The latent image
can lose electrons to form silver ions Ag+ which again become dispersed
interstitially in the crystal lattice. This regression of the latent image can
continue even during the start of the following exposure and is accelerated
by raising the temperature and increasing the dark period. <14 >
REVERSAL EFFECTS
211.
A photographic image can be reversed, that is, destroyed, by a second expo-
sure of long duration when the first exposure was made by the most vigorous
photochemical action. This can be with X-, y- or corpuscular rays (Villard
effect), or even with visible radiation of extremely high intensity and short
duration (Clay den effect). In practice, the sensitive layer is first fogged uni-
formly by one of the methods mentioned, then the fogged emulsion is again
exposed at a low intensity for a sufficiently long time. The first exposure
produces a strong latent image, but in the interior of the grain. Silver bromide
solvents which favour development of the internal latent image must be
avoided as they destroy the reversal effect. E. Weyde<15 > stated that the Clay-
den effect can be applied to printing out of coarse-grain emulsions; Agfa
'Registrier papier L' has a silver bromothiocyanate emulsion containing
halogen acceptors.
212. Herschel effect
A latent image can also be reversed by a second exposure to red or infra-red
light. The sensitive layer is first fogged uniformly to its maximum density
with blue-violet light, then re-exposed at a wavelength greater than 600 rnp.
behind a positive, preferably at low intensity for a long time. Mter develop-
ment, a positive is obtained. Similarly, an ordinary latent image loses con-
trast when exposed to these radiations for a short time. If red light is used, an
intermittent exposure enhances the destructive effect; on the other hand, an
intermittent exposure has little effect when infra-red light is used.
The reversal effect caused by red and infra-red light depends for its effec-
tiveness on the nature of the emulsion, on the total exposure and on the inten-
sity of the first exposure. Low densities are especially affected when obtained
with low intensity blue light. <16 > Bromide ions and oxidizing metallic ions
such as Fe+++ and Cu++ favour the Herschel effect.
The influence of humidity on the Herschel effect is considerable and explains
the difference obtained by many workers. <17 > This influence varies with each
emulsion and cannot be generalized.
Certain oxidizing agents have a favourable effect, especially quinone-
0·05 %-together with an equal quantity of potassium bromide or iodide, or
0·05 % potassium dichromate + 0·5 % manganese sulphate. (lS) The bathed
plate is dried without rinsing, exposed to uniform blue light then to red light.
Sensitization with perborate has also been studied. <19 >
Emulsions ripened in the presence of sulphur sensitizers are more prone to
the Herschel effect whilst those treated with gold are inert. <20 >
By applying the general theory of Gurney and Mott, and after the work of
Hautot and Falla it appears that the Herschel effect is due to the absorption
of red light by the metallic silver development centres. The spectral region of
this absorption is at about 700 mi-L-exactly where the F -band of the alkali
halides is found, which as we know, appears after irradiation with ultra-violet.
Debot has shown that the affected centres lose their electrons which pass into
the conduction levels whilst the Ag+ ions formed, activated by thermal
agitation, migrate towards the interior, or vice-versa. The internal image is
intensified by recombination of the Ag+ ions with electrons re-forming
metallic silver Ag. The total mass of the latter therefore remains constant,
but is found dispersed in smaller centres. In the solarization region, the effect
is sometimes additive, sometimes subtractive. If the latent image is strong,
the photo-electrons can return to the silver ions, or be captured by an F -centre
where silver ions are found (case of overexposure).
213. Becquerel effect

Contrary to the reversal effects, it is possible to strengthen or induce the
printing-out of an image by a second uniform exposure to green or orange
light (itself inert). The photolytic silver, produced by the first exposure
renders the emulsion orthochromatic. Chloride print-out papers bearing an
image have been strengthened in this way, whilst a print-out image can be
formed in a silver gelatino-bromide emulsion which has previously been
exposed to X-rays.
214. Photochemical reversal

A uniformly fogged sensitive layer impregnated with a dilute solution of de-
sensitizer (such as safranine) and potassium bromide, and dried, will be reversed
by a second exposure under an image, due to the proportional destruction of
the latent fog. Good results are obtained with fine-grain lantern plates and
1 : 5,000 solutions of safranine or Pinakryptol Green containing 1% potas-
sium bromide.
The active radiations are those which are obsorbed by the dye except for
a shift of 50 mp, towards the longer wavelengths. See the notes below. <21 l
215. Sabattier effect

Reversal takes place when the material is uniformly exposed (or bathed in a
solution of sodium arsenite) after the image development has started.
The lines separating the dark and light areas in the first image and which
have been affected by the uniform exposure form, after reversal and complete
development, clear lines having a 'piped' appearance (application: in spectro-
graphy and sensitometry with absorbing wedges, to accentuate the difference
between dark and light areas).
To Stevens and Norrish <22 l the Sabattier effect seemed to be due to the
desensitization of the silver bromide by the silver developed during first
development (even very short). The desensitizing effect is, in fact, destroyed
when the metallic silver is removed in a bleaching solution.
The Sabattier effect is very pronounced with very low contrast emulsions.
According to Arens, <23 l these emulsions have only an internal latent image
after first exposure. By developing, the superficial sensitivity specks of the
unexposed grains are reinforced. The second uniform exposure produces, on
the latter grains, an external image, whilst the electrons freed in the pre-
exposed grains go to the internal centres. In normal emulsions there is, from
the start, a balance between the surface sub-centres and the internal centres
of the grains with no surface centres.
The second exposure can be replaced by a solution of hydrogen peroxide
or sodium arsenite, or merely by simply adding a fogging agent to the first
developer: hydrazine or hydroxylamine salts, thiourea, etc. The image
appears first as a negative, then becomes positive under the action of the
fogging agent.
ACTION OF POLARIZED LIGHT

216. Weigert effect
Polariz ed light, diffused by the turbid emulsion, acts anisotropically in two
directions at right angles. If Ox is the direction of the incident beam and Oy
that of its perpendicular electric component, the corresponding absorption
coefficients Llx and Lly will not be equal.
A photographic emulsion exposed to polarized light gives, if the crystals

are sufficiently fine, oriented silver grains which produce a dichroic effect. <24 1
This dichroism is most readily seen with Lippmann emulsions after
development, as well as with print-out emulsions whose particles are about
35 m11- in diameter. This dichroism increases as a function of the exposure
time up to a saturation value. If there has been a preliminary exposure to
non-polarized light, the dichroism has a sharply defined maximum corres-
ponding to an optimum degree of pre-exposure. In every way the appearance
of this phenomenon varies with the emulsion type as well as the development
method used.
Photodichroism is also produced in single crystals of alkali halides (and also
in silver halides), previously exposed until the F-band of absorption
appears, <25 > the band due to an excess of metal ions in irregular positions in
the lattice. By exposing to plane polarized light, the crystals fade and become
dichroic.
The Weigert effect on dyes has been studied by Nikitine. <26 > The dye
molecules diffuse the light anisotropically, this enables them to be destroyed
irregularly, by polarization, in two different directions thereby producing
dichroism.
FOG
Fog, general or partial, is a more or less intense blackening which can be
due to the nature of the emulsion, to development, to aerial oxidation or to
agemg.
217. Emulsion fog

This is caused by the presence of silver bromide grains which are spontan-
eously developable without light action. Over-ripening, excess washing during
the preparation, addition of sulphur sensitizers or certain metallic salts, the
presence of gelatin degradation products, colour sensitizers, are among the
causes of fog.
Fog is measured by its density. Almost absent in positives, it can be tolera-
ted up to 0·2 for negatives. <27 > In current measuring technique the fog value
is deducted from the other densities. This method leads to incorrect results,
for the fog decreases with density, and becomes negligible at high densities.
In fact the reduction of relatively large amounts of silver bromide results in
the local formation of equivalent quantities of soluble bromide which helps
to prevent the development of fog in the dense areas of the photograph.
Uniform fog obtained by pre-exposure leads to an increase in sensitivity.
By post-exposure, it is a method of latensification (see para. 31 ). The maxi-
mum density increase is obtained when the image is at the beginning of the
straight line of the curve. The increase in sensitivity is due to the fact that
the fogging exposure, if taken just to the threshold, leads to the formation of
development centres which are very small but sufficient to initiate the rapid
increase to larger grains. The sensitization by fogging is used in astronomy
for the study of nebulae which are barely visible.
218. Other causes of fog

Development fog is sometimes produced by the developer or desensitizer,
by chemical formation of spontaneously developable grains. Hydrogen
peroxide, formalin and some resins have a similar action.
Aerial oxidation fog is caused by contact with atmospheric oxygen when
the emulsion is removed from the developer. It is said to be an effect of
luminescence. Oxidation fog is produced by hydroquinone alone and by
metol, glycin and p-aminophenol in the presence of traces of copper salts or
by the influence of certain sensitizers.
Age fog is produced when the emulsion is stored for too long. It is produced
more rapidly with colour sensitized plates than ordinary ones. Age fog
depends on the sensitivity of the emulsion, that is on the presence of sensi-
tivity centres in an unstable state which become spontaneously developable.
Hypersensitized emulsions will only keep for a very short time. The storage
of emulsion is an important matter which will be examined in the second
part (para. 347).
Physical fog is caused by unwanted images which are produced by reflec-
tion of the light on the surfaces of the lens. If there are n surfaces, the total
number of unwanted images, y, is
n(n -1)
y=
2
For example, in a lens with four separate glasses y = 28. These images
have the effect of reducing contrast by increasing the clear areas and reducing
the dense ones.
1. This blackening is due to the liberation of a certain amount of silver by the

developer. For a given mass of metal per unit area, it can vary with the size of the
particles which itself depends on the emulsion type, the nature of the developer
and the time of development. That is, the covering power of the silver can take
a wide variety of values depending on the more or less spongy structure of the
grains. An average value is 1 g of metal per m 2 for a density of 1.
2. The sensitive layers have a thickness in the order of 30 p.. Some have 6-10 p.. This
means, if the grains have an average diameter of 1 p., a number of crystal layers
between 6 and 30.
3. It is often of interest to plot non-logarithmic curves or again with the densities
on the ordinate and the exposure (non-log) on the abcissa, by limiting it to the
threshold and underexposure region. In this way, the point of limiting effect is
shown on the curve. If there is no photochemical inertia, the y is at a maximum
at the origin. If there is inertia the slope is nil at the beginning.
4. During the induction period, y = y 00 (1- e-k<t-tol). If the point is below D = 0
D = D oo -(D 00 + D 0)e-kt.
5. Loening E. E.: Bristol Phot. Conf., 1950, 126-148.
6. Oyama Y.:Jl. Soc. Sci. Phot.Japan, 1947,115-120.
7. A 0·2-0 ·5 mol./1. solution of hydrogen peroxide, for example.

8. Maurer R. F. and Yule J, A. C.: J.O.S.A., 1952, 402-408.
9. Fujisawa S. and Misuki E.: Sci. Ind. Phot., 1953, 302-308.
10. Alentsev M. H.: Jl. Exp. Theor. Phys. (U.S.S .R.), Jan. 1947, 75-78 and Sci. et
Ind. Phot., 11, 174.
11. Milne G. G . : Thesis, Univ., Rochester, 1952, 30 pages.
12. Webb J. H.: J.O.S.A ., 1933, 23, 157. Kartuzanskii: Sc. Ind. Phot., 1956, 27,
20-22.
13. Kartuzhanskii A. L. and Meiklyar P. V.: Jl. Eksper. Teor. Fiziki, 1951, 598-609
and Sci. Ind. Phot., 1953, 351-352.
14. Blair J. M.: J.O.S.A., 1942, 32, 332.
15. Zeits. Wiss. Phot., April 1953, 45-57.
16. Trivelli, Leszynski and Hall, cited by Clerc in 'Structure et proprietes des couches
photographiques', Zoe. cit., p. 106, 1st edition, Paris.
17. Vanselow, Quirk and James: P.S.A.Jl., 1953,66-69.
18. Kaempf: Zeits. Wiss. Phot., Dec. 1950, 165-173, also Hautot and Sauvenier: Sci.
Ind. Phot., 1949, 287.
19. Fortmiller, James, Quirk and Vanselow:J.O.S.A., 1950,487-496.
20. Sasai A.: R.P.S . Cent. Conj., London 1953; Bull. Soc. Sci. Phot. Japan, 1952,
19-30.
21. Luppo-Cramer: Zeits. Wiss. Phot., May 1928, 282-287; Sci. Ind. Phot., 1928,
114. Mauz E.: Zeits. Wiss. Phot., Feb. 1929, 289-294. Carroll and Kretchmas:
Jl. Res. Bur. Stand., 1933, 449-464; Sci. Ind. Phot., 1933, 223. Cohen-Solal:
Sci. Ind. Phot., 1952, 388.
22. Stevens and Norrish: Sci. Ind. Phot., 1938, 9, 331.
23. Arens H., Zeits. Wiss. Phot., July 1949, 44-50; Oct. 1949, 172-181; Dec. 1951,
125-134; April1953, 48-52.
24. Narath and Wasserroth: Colloque Sci. Phot., Paris 1951, 38-46 and R.P.S. Cent.
Conj., London 1953.
25. Nikitine S.: Compt. Rend. Ac. Sc., Paris 1941, 32-34.
26. Nikitine S.: Ann. Phys., 1941, 284-348.
27. The fog of new commercial negative emulsions should not exceed 0·08. That of
positive emulsions should be almost nil.
Chapter XV
SENSITOMETRY
219. To obtain the characteristic curve of a photographic emulsion, 1t ts
exposed to a known light source; the sensitive layer receives a series of ex-
posures of either varying time or varying intensity. Mter developing the
'wedge', the resulting densities are measured with a photometer (or densito-
meter), and the characteristic curve is plotted, as shown in the previous
chapter.
We know that the slope of the curve (Fig. 22) is the contrast factor y:
a D
y = tancx = - = ----
b logE -logi
or D = y(logE -logi)
As y increases with development time, up to y00 , several identical sensito-
meter strips must be exposed, which are developed for increasing times.
0
a
1
b
Log. E
0 -1 E 0
FIG. 22.
The choice of the light source is of great importance, for the different sources
each emit light of different spectral compositions. The results obtained by
exposing a plate to two different light sources cannot be compared directly.
The sources corresponding to practical use are: daylight, normal or over-
run incandescent lamps, arc lamps, flashbulbs and U.V. sources.
In sensitometric work it is usual to use electric light, suitably filtered to give
the desired spectral composition. The sensitometric sources used in the past
were the Hefner amyl acetate lamp, the paraffin lamp and the acetylene
burner.
221
The tests should in every way be related to practical working conditions

or the results will have only a limited significance; thus a material intended
for use in artificial light should not be tested in daylight conditions and vice-
versa.
220. Exposing instruments-sensitometers

The exposure of sensitive layers to obtain sensitometric wedges can be made
in two different ways:
(a) by varying the exposure time: single or intermittent exposure;
(b) by varying the intensity of the light.
The first method is relatively simple to carry out, but does not correspond
to practical use where the time is constant and the light intensity varies. Also
intermittent exposure introduces a further cause of error.
(a) Time-scale sensitometers. The simplest type consists of a shutter which
uniformly uncovers the plate being exposed. The best types have an auto-
matic mechanism for moving the shutter. A shutter having a series of vertical
apertures of different lengths can also be used.
FIG. 23.
More frequently a sector disc is used, where openings subtend an increasing

angle at the centre following a geometrical progression. By turning the disc
in front of a sensitive layer, this is uncovered for time t. If the time for a
complete revolution is r, for an angle rt. one has: t 1 = rt.r/360 and for n revo-
lutions t n = nrt.r /360.
With a big disc having large apertures, only one revolution need be made:
such is the Jones sensitometer in which the ten exposure times increase in a
geometrical progression with a factor of 2.
To increase the exposure range, two revolving discs must be used.
The Eastman liB motion picture sensitometer(!) has a rotating drum whose
surface is cut in a series of parallel apertures of different lengths increasing
in y2 steps. The light passes through these apertures via a stationary mirror
fixed inside the drum, the film being held outside. (Fig. 23.)
(b) Intensity scale sensitometers. Intensity scale sensitometers with constant
exposure time, consist in principle of a means of modifying the intensity of
the light source to be used for the exposure.
The variation of the light can be produced by a diaphragm or by absorption.
The Roulleau and Lafouasse instrument(2 > for example, has a series of
thirty-eight circular diaphragms. The image of the lamp is projected onto the
SENSITOMETRY 223
plate with a simple lens. The plate must therefore be moved thirty-eight times
mechanically.
A diaphragm with slotted apertures avoids zonal aberrations. It is also
possible to use metallic grills or even the penumbra of a shadow. <3 ) Another
system forms, using a cylindrical lens, the image of a series of stepped
parallel apertures. <4 )
The light absorption can be effected with a polarization apparatus such as
Tardy's< 5 ) where four Glazebrook prisms replace the nicol prisms. Thirty-
two v2 intensities are obtained.
The most practical sensitometers are those with absorbing wedges or prefer-
ably step-wedges. They have been criticized for lack of neutrality towards the
various wavelengths, and for their lack of precision. This however is quite
adequate for routine work.
The simplest method is to place a wedge over the material under test and
expose it to the selected light source.
A sensitometer similar to the D.I.N. instrument (standard in Germany)
and using a step wedge is also very convenient (Fig. 24); the tungsten filament
lamp is placed in front of a matt black surface, a filter cell, having one or two
layers of filtering liquid, allows light of the required spectral quality to be
used. The sensitive layer is 1 m from the lamp and is behind a wedge having
thirty steps from zero to density 3. The exposure time (in this case 1/20th sec.)
is given by a falling plate with a fixed opening. The guillotine shutter can be
replaced by the more accurate pendulum type. The standard Japanese
sensitometer N.S.G.<Sb) is of this type, with an exposure time of 1/SOth sec.
and the light source is a 500-W lamp operating at 2848° K behind a Davis-
Gibson filter. The D .I.N. sensitometer is primarily used to measure the
threshold sensitivity. (5c)
FIG. 24. FIG. 25.

221. Photometric absorbing wedges
(a) Photometric (or neutral density) wedges are used to progressively absorb the
incident light. A wedge can be made from several superimposed layers as in Fig. 25.
If Io is the intensity of the incident light, € the transmission coefficient of the single
layer, and n the numbers of layers, the intensity of the transmitted light is, for the
first layer l1 = lo. € and for n layers In = 10 • En. The intensity of the transmitted
light decreases exponentially with n, that is, with the thickness of the absorbing layer.
Fig. 25 shows a step wedge in which the densities of the simple layers are added.
In the case of a continuous wedge, the density is a function of the distance 1 along the
wedge, following the formula
D = Kl
where K is the wedge constant. If the unit chosen is the centimetre, for l = 1 em,
D = K; therefore K is the value by which the density increases per centimetre. Fig.
224 PHOTOGRAPHIC CHEMI S TRY
26 shows the variation in transmitted light as a function of l, for a constant of 0 ·4. The
value of K can be established by measuring the densities at two points land l + x (em)
and dividing the density difference by x.
To examine negative emulsions, wedges with a constant of0·25 and sometimes 0·5 are
used ; for bromide papers wedges with a constant of 0 ·25, and for studying halation, 0 ·7 5.
When the wedge is made by casting, it can have irregularities in thickness or in pig-
ment concentration; lines of equal density across the wedge are then found by making
a large number of measurements.
100
c.,;n K:0.4
4 5 6
Distonc.e :r 1cm
~~00----5~50----~·0----6~5~0--~70~0---7~50
FIG. 26. FIG. 27. Neutral glasses
Neutral density wedges are never absolutely neutral; their absorption varies to some
extent with the wavelength; this is why precise measurements necessitate a certain
correction dependent on the characteristics of the wedge and the light source used.
For each gelatin wedge, K can vary, for example, from 0·189 to 0 ·203 passing from
600 to 440 mp.. The constant can similarly be doubled from 480 to 230 mp.. So-called
neutral glasses also have irregular transmission spectra (Fig. 27).
(b) Gelatin wedges are made by preparing a mould from two inclined pieces of glass
separated at one end by a spacer 1 mm thick, and pouring in a 20 % solution of
coloured gelatin. The lower glass is covered with a very thin layer of albumen to facilitate
removal of the dry wedge. The wedge is then mounted between two thin pieces of
glass, preferably together with a compensating wedge of colourless gelatin.
The gelatin is usually coloured with reduced silver< 6 l (in a developing solution) or
with graphite. Indian ink (or carbon black) together with dyes has also been used.
Neutral glass wedges are bound up with an identical compensating wedge of clear
glass.
Step wedges can be made more accurately than continuous ones as the individual
steps can be retouched with an abrasive reducer to obtain the exact density. Two
methods are used to make these wedges: the photographic method by successive
exposure and development of a photomechanical emulsion, or by casting a suspension
of silver in gelatin, using a machined bronze mould which has been waxed (Sci. et
Ind. Phot., July 1951, p. 254). Finally the availability of circular wedges should be
noted.
(c) Preparation of characteristic curves using continuous wedges. The characteristic
curve of an emulsion can be obtained automatically with a continuous wedge.
The emulsion under test is exposed under a wedge so that the minimum exposure
given at the dense end of the wedge is known, for example 0·01 c.m.s. (log E = '2).
After development the emulsion has a series of densities corresponding to the grada-
tions in the wedge. The original wedge and the wedge on the material under test are
then superimposed at right angles. A print is then made from this combination with
an exposure such that the densities above 3 for example give no image. After develop-
ment, the paper will have two diagonally placed areas in black and white separated by
a line following the characteristic curve of the emulsion being tested. Along this line
the sum of the densities of the two crossed wedges D N + Dw is constant; now D w =
SENSITOMETRY 225
Kl where DN = C - Kl. If the limiting density for printing the system is chosen to
be 3 then C = 3. In addition, it is known that the exposure of the negative varies
inversely with the density of the wedge, that is Kl = log E.
Wedges with a constant of 0·4, 8-10 em square are generally used. For cine films,
a normal 3 ·5 em wedge is first used, then for the print on paper, a wedge with a high
constant l or l = 3 ·5. The curves obtained in this way are flattened, their ordinates
having a value 2 ·5 times greater than their abcissae.
222. Density measurements

The densities of the different steps of a sensitometer strip can be measured
with specular or diffuse light. The first method, which is more accurate, is
used with materials intended for projection, enlargement, photometry or
spectroscopy; the second corresponds to contact printing.
The instruments used for measuring photographic densities are called
photometers or densitometers. When small areas are to be measured, micro-
densitometers are used.
Whatever the instrument, it must contain a light source, photosensitive
receiver (which can be the eye) and a measuring device. The density to be
measured is placed between the source and the receiver; some type of dia-
phragm limits the measured area. <6h>
(a) Visual densitomers. The best-known type is the classic Bunsen photo-
meter in which the brightness of two sources is balanced by varying the dis-
tance, until the areas of equal brilliance are obtained. The Fergusson photo-
meter is based on the same principle. These are cumbersome instruments.
The Martens polarizing photometer<7 > is inaccurate for high densities.
The light can also be reduced with a sector disc (Jones' instrument). <8 >
Two revolving adjacent discs were used by Lob and Vodar.
A circular wedge is used to match the two fields in the Capstaff-Purdy
densitometer. <9 >
The simplest method of varying the intensity of the light is to use absorbing
wedges. This is a very convenient method. For measurements of the highest
precision the spectral absorption of the wedge must be determined. The most
common instrument is the Fabry and Buisson microdensitometer(l0 > which
is a modification of the Hartmann apparatus; the eye sees two adjacent fields
provided by the measuring area and the modifying wedge. As the images are
formed on the pupil rather than the retina of the eye, graininess is not appar-
ent. The Martin microphotometer is based on the same principle.
The Goldberg densograph enables the characteristic curve to be drawn
directly; the sensitometric print and the wedge are placed at right angles to
each other and are examined by two light sources. The two beams are
simultaneously examined with a photometric cube. For each density of the
sensitometric print, the wedge, mounted on a movable carriage with a pen,
is moved to achieve balance of the two beams. Knowing the densities of the
wedge, and hence those of the sensitometric print, a graph is obtained. <11 >
The Bull and Cartwright integrating sphere measures the effective density
De/> directly. (12 >
Danjon's microdensitometer uses the disappearance of diffraction fringes,

produced by polarization.
In Meggers and Foote's instrument, the brightness of the lamp filament is
varied.
(b) Thermoelectric densitometers. The receiving device is a thermopile or
thermocouple, a bismuth-silver couple for example, and is connected directly
to a galvanometer or to an amplifier (Lyot). The method has the advantage
of stability and speed. The optical system must be completely achromatic
and the apparatus must be well insulated.
The best-known instruments are those of Moll, made by Kipp and Zonen
at Delft, of Harrison and of Albrecht and Dorneich. They are recording instru-
ments.<13>
223. Photoelectric densitometers

Various types of photocell are used as receiving devices.<14 l
Barrier cells are very easy to use. The current produced by the light is measured
with a galvanometer. However, the current is not proportional to the incident light,
making individual calibration necessary. Over long periods of use the cell is liable to
fatigue and the current drops.
Photoemissive cells are more accurate than the barrier type but even so the current
is not exactly proportional to the incident light. The current is generally amplified,
before measurement, by what are generally called electron multipliers.
Each cell has its individual characteristics, and this makes it almost impossible to
obtain two identical ones.
A sheet of photographic paper moving at a definite distance past the galvanometer
beam can record the deflections reflected by the mirror. The accuracy drops at high
densities which has led to the construction of log scale galvanometers.
Among the principal barrier type photoelectric densitometers should be mentioned
the Baker instrument (Jl. Scient. Instr., Oct. 1947, p. 275) and the Evans Electro-
selenium (EEL) Densitometer made at Harlow, Essex.
The Kruger and Moeller, Koch, Lambert and Challonge< 15 l instruments are recording
types using photoemissive cells.
Among recent densitometers are the following:
The Ansco-Sweet Densitometer (Sci. et Ind. Phot. (2), 16, p . 261 and 18, p . 165 and
J.O.S.A., 1947, p.432) in which the cell sensitivity is a logarithm of the applied
voltage.
The Baldwin Densitometer, a direct reading instrument made at Dartford, Kent.
The Frayne and Crane Integrating Sphere Densitometer (Electrical Research Co.)
which measures the effective density. (J.S.M.P.E., 1940, 184-199 and Sci. et Ind.
Phot., 1940, 248).
The Streiffert (Kodak) Densitometer: the light passing through an integrating sphere
is measured by two cells to give Du and D* (J.S.M.P.E., 1947, 506-522 and Sci. et
Ind. Phot., 1948, 119).
Linse A. G. (Berlin) Densitometer designed for use on a rewind table. A portion of
the light beam forms an enlarged image of the illuminated part of the film, on opal
glass. (Sci. et Ind. Phot., 1950, 291.)
Grabke Densitometer for cine film has an optical system, an amplifier and a paper
recording system (Bild und Ton, 1952, 6-11 and Sci. et Ind. Phot., 1952, 265).
The Altmann (Kodak) Densitometer whose optical system gives an extremely small
illuminated area (J.O.S.A., 1951, 560 and Sci. et Ind. Phot., 1951, 217).
The Pinoir and Baby Instrument (Kodak), adapted from the Sannie recording
microdensitometer, produces a pen-drawn curve (Sci. et Ind. Phot., 1951, 88).
SENSITOMETRY 227
224. Null-reading photoelectric densitometers
As with the visual instruments, two fields are compared with the cell, but successively;
two light beams, one via the sample and the other via a known wedge are balanced.
The measurement consists of returning the galvanometer to zero each time.
Many methods have been used to produce the two beams simultaneously: revolving
discs partly cut away, moving total reflection prisms, nicol prisms, etc.
A simpler method is to superimpose the wedge and the sample. The light passing
through the system is reduced or increased by moving the wedge in such a way that
the current is constant. Rosenberg's instrument is of this type.
Other instruments use two cells, connected in series and illuminated by the same
source. The galvanometer is adjusted to zero, and the sample is placed in front of one
of the cells; the needle is then brought back to zero by moving a corresponding wedge.
The movement of the wedge gives the density following the formula D = Kl.
In the Boutry microdensitometer, (l•) the light beam is divided in two, one beam passes
through the sample adjusting wedge system, whilst the other passes through a constant
comparison density. By moving the wedge a certain amount, the measuring beam is
balanced with the comparison beam. The light received by the cell is therefore con-
stant. A revolving toothed disc, placed in front of the cell, enables the two beams to
be received successively. Because of the simplicity of its principle the instrument is
accurate. E. Vassy has converted it to a recording instrument by mechanically in-
creasing the movement of the wedge and recording the trace on graph paper (made
by Kodak-Pathe).
The Agfa sensitograph is a development of the Goldberg densograph, having two
cells in opposition and a mechanism for automatically drawing the curve. (F.P.
753,809 (1933), Sci. et Ind. Phot., 1934, 77.)
In the Eckelmann and Schmidt densitometer, the image of a slit is first projected onto
the sample, then onto a screen on which it is enlarged. Two cells in opposition are
used. (Kinotechnik, 1941, 5-8 and Sci. et Ind. Phot., 1941, 115.)
Wernick's sound-track densitometer has two cells in opposition (Kinotechnik, 1940,
31-33 and Sci. et Ind. Phot., 1940, 247).
Hall's microdensimeter uses a logarithmic potentiometer (Jl. Sci. Instr., 1949, 365
and Sci. et Ind. Phot., 1950, 51).
Pinoir's densitometer (Kodak-Pathe). The e.m.f. generated by the cell is cancelled
out with an equal e.m.f. to give a constant reading (Sci. et Ind. Phot., 1951, 321).
Goble automatic densitometer has an optical system with two cells, using a circular
comparison wedge, an amplifier and a mechanical system. (Jl. Sci. Instr., 1953,
110-113 and Sci. et Ind. Phot., 1953, 279.)
Equal-density curve recorder: two bridged cells receive two beams transmitted by the
sample and a reference density respectively. The light source is the spot of a cathode
ray oscilloscope. A reading oscilloscope synchronized with the first records the in-
tensity difference of the two circuits (Fowler, Johnson and Billings, J.O.S.A., 1953,
69).
New Kodak densitometer. This very accurate instrument has an optical system with
two b eams, one for comparison, an amplifier and a galvanometer whose deviation
corresponds to the log of the current intensity. (K. G. Macleish: J.S.M.P.E., 1953,
696-708.)
Special densitometers. Some densitometers have been modified for restricted pur-
poses. Among these are:
The Dietert and Schucht projection comparison densitometer for spectrographic
analysis (J.O .S.A., 1941,54-57 and Sci. et Ind. Phot., 1941, 116).
The apparatus described by Kirchgessner and made by Bausch and Lomb is also
intended for spectrography (Rev. Sci. Instr., 1951, 289-292 and Sci. et Ind. Phot.,
1951, 373).
Taylor's direct-reading microdensitometer for X-ray diffra ction patterns (Jl. Sci.
Instr., 1951, 200-205) is a variation of Dobson's apparatus (Sci. et Ind. Phot., 3R,
1923, 182).
Also for X-ray diffraction patterns is the Brentano recording microphotometer. The
galvanometer spot is received on a photographic plate (R.P.S. Centenary Conf.,
London 1953, and Sci. et Ind. Phot., 1954, 16).
Densitometer for radiographs by Bruch, Lochet and Valentin is derived from
Boutry's constant light apparatus (Jl. Physique, 1950,41, and Sci. et Ind. Phot., 1950,
16).
Photographic densitometers. In this class of densitometer the sensitometer print is
placed in contact with a wedge and the combination is illuminated. The wedge pro-
duces a graduated illumination of the sample. A print made through this combination
has a higher band as the density of the sample decreases. The automatic printing of
characteristic curves using crossed wedges is no more than a system of photographic
densitometry.
For the densitometry of small samples (3 mm) Abribat< ' 7 l made a microdensito-
meter on this principle. The print, instead of being made by contact is made by
enlargement and the wedge is placed in front of the recording plate. Knowing the
wedge constant, the corresponding densities can be determined from the height of
the printed curve. Graininess caused by the small size of the sample is removed by
vibrating the wedge-plate combination vertically.
225. Reflection densitometers

Used for paper sensitometry.
The reflection density increases more rapidly than the transmission density
as the light beam has to pass through the silver image twice. It is consequently
limited, depending on the type of base, to a density of about 1· 6- 1· 8 for glossy
papers.
Among the visual densitometers, that of L. P. Clerc<18 > based on the prin-
ciple of the Fabry and Buisson photometer, should be mentioned.
There are relatively simple paper densitometers: <19 > the incident light, after
passing through a wedge, is reflected by the paper at 45° and received by a
cell. The wedge is moved until the galvanometer returns to its original
position (white paper density).
The 'Evans Electro Selenium' and Baldwin photoelectric densitometers,
already mentioned among the transmission densitometers, are also available
as reflection instruments. The former use a barrier cell and the latter a photo-
emissive cell.
Another apparatus was described by Nitka and Stammers (I.C.I.) (R.P.S.
Cent. Conf., London 1953).
The DuPont model should also be mentioned. It is a modification by Huber
and Rakuo of the Frayne and Crane densitometer (J.O.S .A., 1949, 873-876).
Paper surface. The surface of the paper has a great influence on the measure-
ment of reflection densities. The diffusion depends on the grain size, the
refractive index of the gelatin and above all on the physical structure of the
layer. The diffusion is measured with a goniophotometer (that of Hilger for
example) and it can be easily seen that the density varies considerably with the
angle of incidence, particularly with matt papers. The density is at a maximum
in a direction between the incident beam and the normal (Nitka and Stam-
mers); to receive the reflected light under the best conditions the receiver
SENSITOMETRY 229
must be in the maximum density position. The angle of the beam must not
exceed 10°.
The goniometer measurements are more critical with glossy than with matt
papers. E. Seve has estimated the brilliance by comparing the elliptical
reflection spots, the paper being held on a drum and illuminated by a point
source arc. The length of each spot is measured parallel to the source in the
incident plane and parallel to this plane. (Sci. et Ind. Phot., 1953, 461).
Two papers, one glossy, the other matt, but otherwise identical, will give
totally different figures when their densities are read. They must be considered
as equivalent, taking this difference into account in the evaluation (fixed for
each type of emulsion). For example, with the same normal contrast emulsion,
but different surfaces, the following figures could be obtained:
Dmax . y
Glossy surface 1·65 2
Matt surface 1·2 1·6
Semi-matt surfaces give intermediate figures.
The characteristic curves of photographic papers are therefore only
directly comparable with one type of manufacture. If not, use must be made
of relative coefficients.
In current practice it is often considered enough to compare visually two
sensitometer step wedges, obtained on different papers. In this way the sur-
face effects are of little importance in judging, which primarily depends on
the range between extreme densities.
226. Development
(a) A complete sensitometric test must include several sensitometric wedges
which are developed for increasing times until y oo is reached. The contrast,
that is the slope, of each curve increases with development time.
The type and strength of the developer has a more or less pronounced
effect on the numerical value of the densities. Precise comparisons necessitate
standardization of the developer solution; unfortunately, a standard developer
rarely conforms to all the conditions of practical use, and it is therefore usual
to work with a normal working solution, which is after all quite logical.
Among normal developers there are M.Q., p-aminophenol, amidol-
carbonate, metoquinone (5 g per litre with 30 g sulphite and 30 g carbonate)
and pyro (6 g per litre with 15 g sulphite and 11 g carbonate).
Each developer reacts differently with a given sensitive layer; the speed of
y increase, the threshold and fog density obtained with different baths are
never the same. Furthermore, even with the same bath it is impossible to
obtain absolutely identical results because of the action of phenomena such
as diffusion which is impossible to control.
When must exposed sensitometer strips be developed? In principle, they
should be kept for six hours to let the immediate latent image regression
following exposure take place. In practice the laboratories, because of the
time involved, develop the strips immediately after exposure.
(b) Agitation. The speed of development depends, in addition to the nor-

mal reaction rate, on the rate of diffusion in the gelatin layer of the new devel-
oper and of the by-products from the reduction of silver bromide.
The nature of the gelatin, its hardness and also its age influence the
swelling properties of the layer and consequently the diffusion of the reac-
tion products, and the inequalities in the thickness of the layer must also be
taken into account.
On one hand, the more concentrated the developer the more superficial its
action. The surface effect can be accentuated by the addition of certain sub-
stances to the developer, a method which has been used for processing colour
films. Conversely the addition of silver halide solvents favours development
in the interior due to the formation of silver complexes on the surface.
Amidol in acid solution is also known to have a similar action as sodium hi-
sulphite is retained at the surface by the gelatin; with the pH being higher in
the interior of the emulsion than at the surface, the reducer is more energetic
in the interior of the layer (the redox potential drops with pH increase).
The nature of the image is another source of irregularity. The presence of
high density areas close to lower density areas can produce an irregular
diffusion of bromide, iodide and other by-products towards the low density;
the by-products have a local retarding action which results in areas or trails
of low density around the high densities. <20 > The effect of this can be great in
the case of sound records; these irregularities can be produced in opposite
directions depending on whether the dense area precedes or follows the light
area in the passage of the film through the developing machine.
It is therefore apparent that agitation of the developing solution can have a
pronounced effect on the density values and consequently the quality and
sharpness of the image; this is troublesome, considering the difficulty of con-
trolling the agitation and reproducing it accurately.
Development in a vertical position gives better results than horizontal
development in a dish as the formation of stationary waves is avoided. It is
always better to agitate irregularly rather than in a regular manner as the
movement of the developer alone is insufficient.
To some extent the diffusion irregularities can be reduced by passing a flat
brush across the surface during development. The development of sensito-
meter tests by shaking in a thermos flask is more convenient. There is in fact
no perfect system of agitation especially as it is frequently preferable to use
the exact conditions of practical use for the development of sensitometer
tests, however bad these may be. In general, each laboratory has its own
particular device for agitation in the development of sensitometric tests, and
the variety of these devices is infinite. It will be sufficient to note those used
in certain important laboratories. <20 b l
(c) Eberhard effect: <21 l The local variations in concentration of developer
and development by-products produce, in small areas where high and low
densities are adjacent, two lines of separation which can greatly affect the
Image.
The effect is even more pronounced when a large number of different
SENSITOMETRY 231
intensities are present in a restricted area. This is the case in stellar spectra
whose images contain many density variations per millimetre.
The dense areas contain exhausted developer whilst the light areas still
contain active developer. This results in a double flow of developer; the
exhausted developer moves towards the clear portion whilst the active
developer flows to the dense region. This results on one hand in a density
increase in the heavy area at the boundary and on the other, a decrease in the
light area at the boundary. The effect is noticed up to 1·5 mm away from the
edge; it is diminished by prolonging development when the y approaches
Yeo· It is evident that this effect becomes greater as the image considered
becomes smaller. The normal density does not appear in the centre of the
area until its diameter is at least twice the size of the border formed.
(d) Kostinsky effect. <22 l This is produced on two very small images which
are close together such as spectrum lines or double stars; the distance be-
tween the two developed images is greater than the distance between the
exposed areas. The effect is explained by the diffusion of developer exhaustion
products to the clear separating areas, the formation of lateral high densities
and the outward displacement of the dense parts of the images.
MEASUREMENT OF SENSITIVITY
227. Two emulsions, A and B, are exposed under identical conditions: if,
after development to y co , A gives a greater silver deposit than B, it is said that
for a fixed exposure, A is more sensitive (or faster) than B.
Consider, however, the curves of the two emulsions A and B shown in
Fig. 28; they cross at the point C. To produce a density D, an exposure a1
must be given to A, which is less than the exposure b1 which must be given
to B: A is therefore faster than B. The same result is achieved if the thresholds
b, a2
Log . E
FIG. 28.
sA and sn, or the 'inertia points' iA and in, of the two emulsions are com-
pared. But if a minimum density D 2 is to be obtained, which is greater than
the density at C, then emulsion B needs the lower exposure, b 2 < a 2 ; B,
therefore, is faster than A. This happens in stellar spectrophotography where
a minimum density of 0·6 is required for the detection and measurement of

weak emission lines.
Determination of the exposure for the production of a complex image
requires knowledge of the contrast achieved on development. Generally the
maximum y obtainable without excessive fog is 80 % of the y co ·
In astronomy the following definition of sensitivity is used: a quantity
inversely proportional to the exposure necessary to produce a density of 0·6
when development is to 80% y 00 , the plate being 1 metre from a source
equivalent to 1 candle.
In practice, the speed of sensitive layers is measured with reference to the
threshold or inertia. Whatever criterion is used, a complete knowledge of the
spectral distribution of the source used is essential.
It is, in fact, difficult to estimate the speed of an emulsion without con-
sidering its specific use, for to have any real significance the sensitometric
test must be made under the same conditions. As the sensitivity is dependent
on a combination of the properties shown by the characteristic curve it is
misleading to indicate it by a single figure. As a general rule, it is best to know
the threshold and the inertia point.
Intrinsic sensitivity. To become developable a grain must absorb a certain
number of effective quanta r. This number is the same for all the grains of an
emulsion. If, of N grains, k become developable with an exposure E, the
form of the curve representing k/N as a function of log E is a characteristic
of the number of quanta r.
Silberstein defined the intrinsic sensitivity E as the probability that the
grain will absorb a number of effective quanta to be made developable after
having received a certain exposure related to r. The coefficient of effective
absorption determines E; it is lower than the coefficient of absorption of silver
halide. E increases as the grains become larger; it can be altered by chemical
sensitizers.
Theoretical limit of sensitivity. Bruscagnioli has determined the theoretical
limit of sensitivity with the formula
hvP2
It ~ 4 · 10 4 --
7TGW7J
where G is the smallest brightness difference which can be recorded, w the
thermodynamic equivalent of the light in lumen-watts, TJ is the coefficient of
utilization of the light by the sensitive layer, P the resolving power (in lines/
em), his Planck's constant 6·57 x 10- 34 W. sec.
w = 4·6 X 10-3 TJ = 0·4 G = 2·10- 2 p = 103
228. Measurement of sensitivity by the threshold method

The threshold is the point where the least exposure can give a density which
can just be seen in the sensitive layer. It can readily be determined with a
photometric wedge which has been standardized for exposures (metre-
candles).
SENSITOMETRY 233
As the threshold is visually rather vague, it is preferable to use a density of
0·1 above fog which can be measured precisely.
The speed of photographic materials is frequently determined by the
threshold method. The figure thus obtained gives no idea of the behaviour of
the rest of the curve; it is concerned only with the underexposure region.
(a) Scheiner System. A time-scale sensitometric exposure is given using a
sector wheel. The light source is a paraffin burner. The speed is given in
0
Sch., after threshold measurement. The yellow light benefits panchromatic
emulsions. This method is not used any more except for advertising. In this
case, the figures given are very conventional; 33 o representing an ultra-rapid
emulsion.
(b) DIN System. Standard German system, it is similar to the preceding
one. The lowest exposure capable of giving a density 0·1 above fog is meas-
ured using the apparatus shown in Fig. 24. The step wedge has thirty steps
from 0 to 3 (interval of 0·1 ). The exposure time is standardized at 1/20th sec.
with a luminous flux of 40 lux of daylight quality.
After development in an M.Q. bath of fixed composition, the negative is
examined under a neutral grey filter and the step corresponding to a density
0·1 above fog is found. If, for example, this is the step corresponding to a
wedge density of 1·8 the speed is 18/ 10 DIN. As the scale is logarithmic, the
speed is doubled every 3° as with the Scheiner system.
In practice the DIN system can be used for comparative threshold meas-
urements. In this case the spectral composition of the source, the exposure
time, the bath and method of development are all adjusted to give conditions
as close as possible to those under which the material will be used.
Instead of giving the threshold sensitivities in terms of the wedge density,
we prefer to give them in exposure values, as these are simpler and more
informative. Thus 23° DIN corresponds to an actual threshold exposure of
0·01 c.m.s. (the density of the wedge is 2·3-giving an opacity of 200 and
the exposure transmitted
40
;O~·OS = 0·01). The figures obtained in this
way have the advantage of being proportional.
Neo-DIN System. In the new DIN system, development is carried out in
an agitated thermos flask for 4 mins. at 20°C in:
Metol 2g
Hydroquinone 4g
Sodium ~ulphite anh. so g
Water to 1 litre
GOST system. In this Russian system, the GOST unit is the unit of
sensitivity of an emulsion corresponding to a density 0·2 above fog using an
exposure of 1 c.m.s. The sensitivity is the reciprocal of the exposure. Develop-
ment is at 20°C with a liquid flow of 10-15 cmjsec. Sensitometer of the DIN
type with a wedge of twenty-one steps with a 0·15 interval and exposure time
of 1/20 sec.
(c) Eder-Hechtsystem. The sensitive layer is exposed under a 9 X 12 em wedge
with a constant of about 0·4. A scale in 2-mm squares enables the densities
to be located. The threshold is given by the last mark visible after develop-
ment.
Although speed determination in Eder-Hecht degrees requires magnesium
light in the fixed working conditions, comparative measurements with various
sources are possible, and even preferable.
The relative sensitivity corresponds to the figures marked on the wedge
and a table is provided by the manufacturer (Herlango, of Vienna). They are,
however, easy to calculate if the wedge constant is known. The Eder-Hecht
wedge, together with its mounting, is an extremely simple and convenient
instrument for everyday measurements. It is only used for laboratory tests.
229. Measurements of sensitivity by the inertia method

The inertia method of speed measurement was conceived by Hurter and
Driffield. The speed of an emulsion in H and D units is obtained from the
characteristic curve in the following way:
The exposure corresponding to the intersection i of the straight line with
the exposure axis (Fig. 29); the value obtained is conventionally called the
inertia. The sensitivity is proportional to the reciprocal of the inertia and is
given by the expression S = 34/i H and D units, the exposures are given in
candle-metre-seconds (c.m.s.). The expression S = 10/i is also used, giving
appreciably lower figures.
0
Log. E
FIG. 29.
S can be easily determined in c.m.s. units, the sensitivity being greater as i

becomes smaller. This enables the threshold and inertia to be obtained at
the same time in figures which are directly comparable without the use of
arbitrary units.
For the intersection of the produced straight lines of the different curves of
a sensitometric test, to meet at the same point, no bromide is added to the
developer. Theoretically the speed value is therefore independent of the
development time.
SENSITOMETRY 235
This is not so in practice where the developer contains increasing quan-
tities of bromide. Fig. 30 shows the variations in speed as a function of
development time using the inertia method (10/i) compared with the Jones
and Russel (10 ji1) method using a slope of 0·2 (explained later). It is seen
that the speed increases rapidly at first, until a maximum is reached, after
which it falls slightly.
230. Fixed gradient methods

Instead of using the inertia, the point corresponding to the minimum useful
gradient is measured, which Jones and Russel found to be 0·2 in the threshold
region (Fig. 29).
The exposure A where the slope is 0·2 is used to determine the speed.
The expression S1R = 10ji1 can also be used.
(b) The sensitivity determined by an old standard of the Aeronautique
Franyaise is the point where the slopes of 0-2 and 0·4 intersect, the curved toe
being likened to a parabola.
(c) Labussiere proposed to use the point where the gradient is 0·5 (Fig. 29).
Knowing the exposure corresponding to iL the speed value is given by
10
SL =-:-
lL
(d) Lapeyre system. A subject with a brightness range of 1· 5 is used. The

exposure corresponding to a slope of 0-8 gives the sensitivity.
231. ASA system

A system similar to the preceding one was established by Jones by statistical
observations, and was approved by the 'American Standards Committee' for
the calculation of ASA units (1939).
The subject has a brightness range of 1·5, a point A on the lower part of
the curve is found such that the slope YA at this point is 0·3 of the average
1400
v G1J -
1200
1000 '(
/
D
800
.....
600 J r"ii'D.lO
Tf.--
~
400 I
200
0 5 10 15 20 25 a
FIG. 30. FIG. 31.

r*
gradient M measured from the point A. This average gradient is the chord
between points A and B of the curve (Fig. 31 ). YA and M have values corres-
ponding to the tangents of the angles ex. and {J. The average gradient M has a
value of 0· 7 for films for normal negatives and 0·6 for miniature films.
The exposure corresponding to point A gives the ASA speed:<23 > 1/EA-
The number found is preceded by the figure 0.
To find point A, two transparent rules are used, having on one a line with
a slope of 0·6 for example, and on the other, a line with a slope 3/ 10 of this,
i.e. 0·18. A brightness range of 1·5 covered by the line whose slope is 0·6 is
found and the slope at the point of intersection A is checked to be 0·18. The
Jones and Russell desensitometer<24 > gives the point A by examination of two
fixed areas of the test wedge without using graphical methods.
Conditioning of samples: atmosphere maintained at 20 °C±S o and R.H. 55 ± 5%.

Sensitometer type: non-intermittent intensity scale.
Exposure time: between 1/20 and 1/80th sec. The exposure of one step must not
be greater than twice that of the preceding step.
Light source of 2,360°K together with a Davis-Gibson filter (see Light Sources,
Part IV).
Development. Wait 2 hours after exposure. Develop at 20 °C (68 °F) for 4 minutes
m
Metol 2g
Hydroquinone 4g
Distilled water (air free) to 1 litre
Apparatus: thermos flask 22 em long and internal diameter 4 em, three-quarters
full. The test is attached by rubber bands to a strip of glass 20 x 3 ·5 em which is fixed
to the bung.
Agitation: the flask must be agitated in a vertical plane through an angle of about
45 ° above and below the horizontal the cycle taking 1 sec. At the same time it must
be turned on itself every 5 seconds.
Fixing: after development, in
Sodium thiosulphate 250 g
Sodium bisulphite 25 g
Water to 1 litre
Miniature sizes: develop in the following developer for 8 minutes at 20°C.

M~ 2g
Hydroquinone 4g
Borax 4g
Distilled water (air free) to 1 litre
If the average slope is below 0·50, increase the developing time until this value is
obtained.
Density is measured by diffuse light.
SENSITOMETRY 237
BSI system (British Standards Institute). This system was originally
based on the exposure necessary to obtain a density 0·1 above fog as in the
DIN system. It appeared preferable later to adopt the same point for esti-
mation of sensitivity as the ASA method, but with a logarithmic scale: the
sensitivity is increased by v2
for an increase of 1°' for example:
Exposure 0·01 0·0064 0·005 0·0032 0·0025

logE 2 3·8 3·7 3·5 3·4
ASA speed 0100 0160 0200 0320 0400
ASA index 25 40 50 80 100
BSI index 25° 27° 28° 30° 31°
232. Notes on the choice of a criterion of sensitivity

The great number of methods proposed for the measurement of the sensitivity
of a photographic emulsion demonstrates the insatiable character of this
objective. It is impossible to express in one figure a physico-chemical system
which is controlled by many laws. In a sensitive layer, the practical value of
the sensitivity is dependent on the shape of the characteristic curve, on the
contrast, the rate of development and the colour sensitivity. Also, the com-
parison of two emulsions with different properties is meaningless. Two emul-
sions do not have the same y in the same development time; their optimum
usable y are rarely the same; the shapes of their characteristic curves are
certainly different and each has its individual reaction to various light sources.
It has already been stressed that there are two types of negative emulsion
commercially available: those whose characteristic curve has a long straight
line and a relatively short toe, and those with a long curved toe. Only the
emulsions with a straight characteristic give correct reproduction. The existence
of curves with long toe regions merely denotes a manufacturing expedient
(mixture with a fast coarse-grain emulsion, sensitization with gold, etc.)
which in use gives the illusion of high sensitivity, for the emulsion always
gives in this way a vague image of some sort. It is a great error to think that
this type of emulsion with indefinite contrast can help in the artistic rendering
of subjects by complete falsification of their tone values.
With a correct emulsion with a straight line the best way to illustrate its
sensitivity is to measure at a given contrast (0·8 for example) the inertia point:
Hand D method, and the position of a density 0·1 above fog (DIN method)
together.
In the case of long-toe emulsions, the DIN method gives information about
the first usable point but tells nothing of the rest of the curve. There remain
the specified gradient methods. The slope of 0·2 is too close to the threshold.
But the ASA system was created to help with this type of emulsion. It can
always be criticized for its useless complexity giving an illusion of precision.
In fact, an equally good practical estimate can be obtained much more easily,
from the exposure corresponding to the point on the curve which has a gradient
of0·3.
RESOLVING POWER AND GRANULARITY
233. Resolving power

The resolving power of a sensitive layer, is measured by the minimum dis-
tance separating the images of two luminous points.
With the images of two parallel lines separated by a distance d equal to
their width, the resolving power r is given by
1000
r
2d
where d is in fl- · r also represents the number of lines per millimetre which can
be separated. The resolution is much higher if the clear areas are small,
relative to the opaque areas of the grid, but r increases ten times more slowly
if the ratio-width of clear area/width of opaque area-does not decrease.
Finally, the figures obtained depend to some extent on the methods used for
printing and examination.
The objects generally used for the measurement of resolving power are the Fou-
cault targets. These are formed of alternate clear and dark lines of the same width.
The complete charts contain a series of these targets of decreasing size grouped in
four different directions, vertical, horizontal and two diagonal. The chart is preferably
used as a transparency, being illuminated diffusely from behind.!25 l Many photo-
graphs are taken with different exposure times, each series being developed with
increasing times. The results are examined with a lens or microscope to find out which
lines are only just separated. Another method sometimes used is to find the first patch
in which directional lines are visible and to note the number of lines corresponding
to it.
The resolving power depends on the object contrast. It also depends on the lens.
The resolution of the optical system must be better than that of the layer tested; it is
an increasing function of the aperture up to a maximum; it diminishes with the wave-
length.!••)
Communication No. 533 from the Bureau of Standards of the 20th March, 1953,
gives recommendations for the determination of the resolving power of photographic
lenses using printed targets.
Perrin and Hoadley have worked out a special apochromatic objective for measuring
the resolving power of sensitive layers, made from two fluorite convergent elements
on either side of a divergent element made from Bausch and Lomb S.K.16 glass. It
is called 1381.! 27 l The following are some results obtained with it:
Ord. Fuess
Emulsion Lens Lens 1381
Super XX 50 95
Panatomic-X 65 105
Tri-X 40 70
Duplicating negative 80 105
Cine positive 60 105
High-contrast positive 105 170
Duplicating positive 135 170
Sound recording 1357 55 100
Microfile 170 180
SENSITOMETRY 239
234. Diffusion (Irradiation)
The light striking an emulsion is laterally diffused by the minute crystals of
silver bromide, reflected many times between the different faces and irradiated
in every way, which results in a general spreading of the image: <28 > this usually
happens with turbid media.
The diameter of the image increases with the amount of light received, or
more exactly with the logarithm of the exposure:
d = do+ flogE
where do and rare constants. r, also called 'astrogamma' is a measure of the

turbidity of the emulsion. If two measurements of d: d1 and d 2 with E1 and
E 2 , one has
d1 = do+ flogE1
d2 = do+ flogE2
and d2 - dt = r (log E2 - log Et)
d2- dt
therefore r = - - ---
log E2 - log E1
Goldberg gives the following average values of r for different emulsions:

Grainless emulsions 0 fL
Positive emulsions (lantern) 7 fL
Process emulsions 11 fL
Rapid emulsions 18 fL
Bromide papers 48 fL
The diffusion brings together neighbouring images (spectrum line, double
stars) the effect becoming more apparent in underexposed images than with
overexposed ones where the Kostinsky effect also comes into play.
If an emulsion is partly covered by a mask with a straight edge in intimate
contact, and the remainder exposed to increasing intensities, it is found
that irradiation takes place under the mask, starting at its edge and pene-
trating progressively with the exposure. The shading-off thus formed follows
the laws of the penetration of light into an absorbing medium. The charac-
teristic curve in this region of diffusion measured with a microdensitometer as
a function of the distance in fL from the edge, isS-shaped. <2 9 > If 4> is the slope
of this curve and K the coefficient of absorption of the emulsion, then
4> = yJK. 4> is a characteristic of the sharpness of the image. <30 >
The diffusion of the incident light by the silver halide crystals is the same
for all visible A, for grains up to 1 fL but for larger grains it is greater in the
red. <31 >
An important factor in the spreading of light by an emulsion, with a drop
in its resolving power, is the thickness of the layer. An image at the bottom
of the layer is less sharp than one at the surface. This is why U.V. radiation,
which does not penetrate far into the layer gives images which are better
resolved. A current method of limiting the penetration of light into a sensitive

layer, and therefore obtaining a higher resolving power, is to stain the layer.
Kowaliski <32 > got good results with quinoline yellow and naphthol orange.
With a cine positive emulsion which can resolve 100 lines/mm in the depth
of the emulsion and 115 lines jmm at the surface, he obtained, after staining
in a 0·1% solution of quinoline yellow, 135 lines in the interior and 150 lines
at the surface. Naphthol orange enabled 170 lines to be recorded. The sensi-
tivity is reduced considerably at the same time: 10-25 times for the dyes
mentioned above.
235. Granularity
Since diffusion is produced by the granularity of the emulsion, the resolving
power must increase as the grain becomes finer. If an image of an illuminated
slit is photographed, the negative has an area of apparently uniform density
between two clear regions. When examined with a micro densitometer, the
deposit in fact shows appreciable variations in density (Fig. 32); the hori-
. zontal line AB represents the average density; the relationship between the
FIG. 32.
total area bounded by the undulations between D and E and the length of DE
is the mean density 11 of the variations; the quotient of the length DE
divided by the number of intersections of the curve by AB represents the
average apparent size of the grain g. The distance HG = h from the point H
to the geometrical limit separating the two areas can be used to determine the
turbidity. <33 >
The local fluctuations of density of an unexposed or uniformly exposed
(and developed) layer, determine the lowest value of the densities difference
detected by this layer, and which in sound recording is called 'noise'. Useful
densities must be higher. <33 bl
The measurement of granularity is made using objective methods in which
psychophysical sensations take no part. Generally it is carried out by the
methods of Van Kreveld, Goetz and Gould or Selwyn. In each case the
statistical frequency of the density fluctuations over a uniform area is approxi-
mately determined by the Gaussian function of probable distribution. <34 >
For Van Kreveld the granularity constant is GK = (Ta1 -Ta 2 ) average
where T a1 and T a 2 are the transparencies of two adjacent areas of equal
surface.
SENSITOMETRY 241
Goetz and Gould basing it on the distribution equation
2
- -- = J xe- (x/G')'dx
G'y';- o
where G ' represents the distribution, fixed the granularity constant by
G = G ' /1000 and constructed an apparatus enabling this constant to be
measured. <35 ) If at is the mean quadratic variation of the relative transparency
fluctuations, then G = at v'Z and G ' = 1000 at v'2.
Let the area a of the examining light beam be considered. If ad is the mean
quadratic variation of the density fluctuations as a function of area a, n the
number of silver grains covered by the spot, and !X. the average projected area
of these grains on the spot, Nuttings equation, verified by Romer<36 ) gives the
relation
D = -log10[1- ~r
Selwyn uses, for the measurement of granularity, G = adv'a where ad is
the mean quadratic variation in the density fluctuation. Granularity therefore
increases with the area of the examining spot. <36b) lngarden and Min-
kusinski <3 7 ) have verified, by probability calculations, that there is a value for
a for which a minimum is, however, attained.
What is the relationship between granularity and contrast? Selwyn has shown
that the mean fluctuations around the density are of the order of 0-6G/v'a;
that is, that the measured density D* is
D* = D ± 0·6Gjv a
but as D = y (log E) - b, it becomes
D* = y(log E)- b ± 0·6G/v a-
The error on the evaluation of the exposure is
logE* -logE = ± 0·6(G/y)/va
The practical granularity G is measured by
G = G - logy
Debot <3 8 ) has found, taking G = log (at y'a)
G G
Pan negative emulsion 2·44 2-65
Fine-grain pan. neg. emulsion 2·28 2-43
Cine positive 2·35 2-17
An electronic granularometer<39 ) enables the quadratic mean of the relative
transparency variations to be measured continually with the negative moving,
to integrate the average value of this transparency, to calculate the deviations,
then the square of these, the mean of the squares and finally the relationship
at= a(~T) / T
Another means of measuring the granularity was suggested by Thread-
gold, then by Kuster and Eggert: it consists of determining the ratio of the
specular and diffuse densities, the latter having a value of 0-5
K = 100logD 11 /D*
Stricker< 40 l found that at increasing gamma in a metol developer:
'Y = 0 -34 0 -48 0-62 0-76 0-92
K = 18 23 26 28 28
236. Graininess
If the fluctuations of the transparency constitute the granularity, the visual
sensation of a heterogeneous photographic layer is a psychophysical pheno-
menon which is usually called graininess.
Graininess can be measured by the distance at which the unevenness due to
grain in an enlargement disappears. For Selwyn it is a function of the granu-
larity of the negative and the contrast of the printing paper: 'Yp. G. The
optical system of the enlarger must also be considered as this can influence
the appearance of the enlarged image.
Jones and Higgins< 41 l who have made many statistical observations on this
subject, have come to the conclusion that the retinal cones send nervous
impulses to the brain which depend on the sharp variations in excitation, and
that consequently the examination area for the measurement of granularity
should correspond to the dimensions of the retinal cones.
If ~x corresponds to the distance between area elements (the images of
which are formed on the cones contiguous with the fovea), ~x becomes equal
to the diameter of these cones multiplied by the amplification coefficient of the
retina with regard to the sample, therefore equal to the diameter of the spot
of the microdensitometer (10 fL, for instance). The differences ~D of the
densities between neighbouring elementary areas (called 'syzygetic' densities)
produce the graininess feeling.
80
0 2 3 0 1 2 3
FIG. 33 . FrG. 34.
SENSITOMETRY 243
t:J.D j!:J.x is the 'illumination gradient', while S!:J.D is the measure of granu-
larity. <41b> The value of S!:J.D is obtained with the aid of a microdensitometer
having two contiguous spots, which renders possible several hundred
readings, thus permitting to trace the distribution curve. The graininess can
be determined directly by means of the Jones and Higgins apparatus,
assuming that a fovea cone has a 1· 5 fL diameter, and that the focal length
of the eye lens is 17 ·5 mm. If H represents the graininess, M the amplification
corresponding to the threshold of perception, and cp the critical diameter of
the exploring area relative to a fovea cone, we have
H = 1000/M and cp = 0·175 H
The mean granularity S!:J.D* measures the threshold of graininess (with cp for
the spot diameter); then it can be possible to obtain the curve 'log S!:J.D*
function of D'.
Reduction of graininess. The graininess of an image can be reduced by using
one of the following methods: (42)
Shifting the focus.
Interposing a silk or screen.
Vibration.
Successive printing with several identical negatives.
Chemical diffusion. Strauss<43 > reduced the graininess by converting the
silver to silver bromide, then to silver sulphide in a sulphide-hypo bath (1 %
sulphide, 0·1-10 % hypo).
0 5 10 15 20 tn~r.
FIG. 35.
Improvement of resolution. The resolution can only be improved by com-

bining, in the same print, the effects of several identical negatives, as has
been shown in the experiments of Stevens. <44 > This process is only of use if
perforations permit perfect registration and if each image is of low contrast.
Nothing is gained by superimposing more than four images because of the
difficulty of locating them. Application in astronomy. <45 >
237. Influence of contrast on the resolving power

The resolving power depends on the subject contrast and upon the density
of the photographic image. Thus the curve in Fig. 33 shows the variation in
244 PHOTOGRAPHIC CHEM I ST RY
resolving power as a function of the image density for a brightness range of

1-000 and 8 minutes development; in this example, the resolution increases
with density up to 1·3, then decreases to become very low at 3·5 .
The resolution increases with the brightness range of the subject up to a
limiting value. In Fig. 34 the variations in brightness are shown. On the
contrary, it decreases with development time (Fig. 35).
1. Another instrument uses, for automatic control, a metronome which lights and then
extinguishes an electric lamp (Reeves 'Sensitester').
3. Roulleau and Lafouasse: Sci. et Ind. Phot., 1954, 25, 389-392. The latter model
is made by Desgranges and Huot, Paris.
3. King E. S.: Annals Harvard Observ., 1899, 59, No. 2.
4. Miller 0 ., Sci. et Ind. Phot., 1932,3,81-87.
5. Tardy H. : IXth Int. Cong. Phot., Paris, 1935, 641.
5b. Sci. et Ind. Phot., 6(2), 264 and 1953, 24, 349.
5c. E. R. Davies used an instrument with a step wedge having intervals of 0·2 up to
4·3 (Phot. Jl ., 1944, 1885). For the sensitometry of variable density sound tracks,
the grey scale is produced on a film running in contact with the film wedge over a
supporting drum. The image of a slit is projected on the two films giving an
exposure time of 1/25,000 sec.
6. Goldberg E.: Sci. et Ind. Phot., 1925, SM, 64 and 69.
6b. For a comparative study of the various types of densitometer, see Weaver,
J.O.S .A., 1950, 524-536.
7. Martens F. F.: Ver. deutsch. phys. Ges. , 1899, 1, 204; Arch. Wiss. Phot., 1900, 2,
184.
8. Jones L. A.:J.S.M.P.E., 1931, XVII, 536; Sci. Ind. Phot., 1923,92.
9. Capstaff J. G. and Purdy R. A.: Trans. S.M.P.E., 1927, 11, 607.
10. N---, Sci. et Ind. Phot., 1923, 1. A recent modification of this instrument was
shown by Gaultier du Marache and Duffiers: Sci. et Ind. Phot., 1952, 359.
11. Lobel L. and Dubois M.: Manuel de S ensitometrie (P. Monte!, Paris) .
12. Bull A. J. and Cartwright H. M.: Sci. et Ind. Phot., 1924, 36.
13. Moll W. H. J .: Sci. et Ind. Phot., 1921, 105; 1930,89. Thomson K. B.: Sci. et.
Ind. Phot., 1935, 398. Harrison G. R.: J .O .S.A., 7, 999; 10, 157; Sci. et Ind.
Phot., 1924, 34; 1925, 80. Albrecht and Dorneich: Phys. Zeits., 26, 514; Sci. et
Ind. Phot., 1925, 181.
14. Vassy E . : La mesure des densities photographiques. (Centre de perfectionnement
technique. Presses Documentaires, Paris.)
15. Chalonge D and Lambert P.: Sci. et Ind. Phot., 1925, 94; 1927, 6; 1932, 94.
16. Boutry A.: Sci. et Ind. Phot., 1934, 41. See also the new E. R. Davies apparatus
(Phot.Jl. , 1944, 185 and Sci. et Ind. Phot., 1945, 77.)
17. Abribat M.: Sci. et Ind. Phot., 1931, 321.
18. Clerc L. P.: Sci. et Ind. Phot., March 1925,28.
19. Davies E. R.: Phot. Jl., 1932, 118. A new model is semi-automatic. Tuttle made a
completely automatic densitometer (see Sci. et Ind. Phot. (2), 7, 309).
20. Another effect noticed by J. Dufay (Compt. R end. Ac. Sc. Paris, 1932, 1898) and
studied, among others, by L. Falla (Sci. et Ind. Phot., 1949, 449) is the variation
of the characteristic curve as a function of the size of the luminous spot used for
exposure; when this is less than 60 !-', areas of different width do not have the
same density. There is a proximity effect during development giving a higher
density to the broader bands.
20b. Bates, Berley and Kowalak (Ansco): Phot. Eng., 1951, 182-191; Sci. et Ind. Phot.,
1953, 112.
SENSITOMETRY 245
21. Walenkow N.: Sci. et Ind. Phot., 1930, 51; Junkes J.: Sci. et Ind. Phot., 1938,
16 and 133.
22. Junkes J.: Sci. Ind. Phot., 1938, 16; Ross: Sci. et Ind. Phot., 1921, 89.
23. With exposure meters, an exposure index is used equal to a quarter of the ASA
speed. A panchromatic negative emulsion will have an index of 100 to daylight
and 65 to tungsten.
24. Jones and Russel: Sci. et Ind. Phot., 1935, 325; 1939, 303. The Kodak gradient
Meter is a variation of Nelson's apparatus for reading the speed directly from the
curve: it is a transparent disc having, at a distance of 1 ·5 from the centre, a
perpendicular to an arc graduated in slopes.
25. Perrin F. H. and Altman J. H .: Sci. et Ind. Phot., 1951, 375.
26. Perrin F. H. and Altman J. H. :J.O.S.A., 1951, 1038-1047; Study of target types,
Sci. et Ind. Phot., 1952, 266; J.O.S.A., 1953, 780-790; Sci. et Ind. Phot., 1954,
57.
27. J.O.S.A., 1948, 1040-1053.
28. When the grains are very fine, they also result in diffusion caused by diffraction.
29. Ross F. E.: Astrophys. Jl., 1920, 201. Sandvik 0.: Sci. et Ind. Phot., 1928, 8M,
18 and 27.
30. Clerc L. P.: Structure et properties des couches photographiques, p. 148 (Ed. de Ia
Revue Optique, Paris).
31. Breido I. I. and Pruss P . K.: Doklady Ak. Nauk. (U.S.S.R.), 1952, 893-896.
32. Thesis: Zurich 1944.
33. Kreveld A. V.: Phot. Jl., 1934, 590; Sci. et Ind. Phot., 1935, 53 and 271. Kreveld
A. V.: (Photoelectric apparatus) Sci. et Ind. Phot., 1936, 206 and 243. Rauden-
busch H.: (C-R oscillograph), Physik. Zeits., 1941, 208-212.
33b. Clark Jones R. (Polaroid Corp.): Phot. Sc. Techn., May 1955, 56-65.
34. According to Jones and Higgins, this distribution of the fluctuations IS not
Gaussian.
35. J.S.M.P.E., 1942, 375.
36. Romer W .: Sci. et Ind. Phot., 1953, 312.
36b. The granularity also depends on the shape of the illuminated spot-circular or
slit.
37. lngarden R. S. and Minkusinski J. G.: Sci. et Ind. Phot., 1953, 280.
38. Debot R.: Sci. et Ind. Phot., 1953, 408.
39. Sci. et Ind. Phot., 1952, 148; 1956, 217-222.
40. Stricker K.: Helv. Chim. Acta., 1948, 1487-1496.
41. Jones L.A. and Higgins G. C.:J.O.S.A., 1951, 41-52; Sci. et Ind. Phot., 1951,
178; J .O.S.A., 1951, 192-200; Sci. et Ind. Phot., 1951, 260.
42. Hickman: Sci. et Ind. Phot. (1), 6A, 117.
43. Strauss, Sci. et Ind. Phot., (2), 11, 185.
44. Stevens G . W. W.: Phot. Jl., 1947, 74-80; Sci. et Ind. Phot., 1947, 303-305.
45. Blair and Stanton: Amer. Phot., 1939, 361. Lyot: Sci. et Ind. Phot. (2), 3, 107 and
14, 185.
Chapter XVI
PHOTOGRAPHIC REPRODUCTION
PRODUCTION OF THE IMAGE
238. The negative

Very sensitive emulsions with great exposure latitude are used to make
negatives. These emulsions are from 100 to 10,000 times as fast as positive
paper emulsions and 40 times as fast as cine positive emulsions.
Negatives are developed to a y between 0·6 and 0·8.
Fog density. A freshly made negative material should not have a fog den-
sity exceeding 0·08. If the emulsion is old the fog may exceed 0·2 (except
in the presence of a strong antifoggant). Above 0·2, irregular emulsion fog
can alter the low densities of the negative image.
FIG. 36. FIG. 37.
In general, intensification and reduction of negatives should be avoided. If

such treatment appears necessary, it is always essential to choose the type of
bath which will produce the desired effect; Figs. 36 and 37 show the effect on
the characteristic curve of reducers and intensifiers.
239. Duplicate negatives

Duplicate negatives are made in two stages: (a) printing a special positive;
(b) printing the duplicate negative from this positive.
Printing the positive. The positive emulsion must have very fine grain and a
characteristic curve with a long straight line with the toe as short as possible.
It must have a high contrast with a relatively high maximum density (but
246
PHOTOGRAPHIC REPRODUCTIO N 247
little exposure latitude), depending on the brightness range present in the
original negative (Fig. 38). A yellow dye can be incorporated in the emulsion
to reduce irradiation, whilst the flaws in the base are reduced by colouring it
blue or violet (lavender hue).
• B OJ
0
t
l11 c. re a'jinq light
FIG. 38. Preparation of a duplicate negative.
As the original negative is developed to a YN = 0·65, the print onto positive

material is developed to y = 1· 7.
The image MN is printed only on the straight line in order to avoid distor-
tion. It therefore follows that the print must be overexposed to such an extent
that a dense image with no clear parts is obtained. A positive developer is
used. If the y is 1· 7 and the negative y 0·65 then the positive image will have
a y product:
YN X yp = 1·1
Printing the duplicate negative. The duplicate negative emulsion is also slow
with very fine grain and a long straight line, but it is less contrasty and the
maximum density is lower than the positive.
The dupe negative is developed in M.Q.-Borax to a yn = 0·59. The final
y of the dupe negative is the product of the 3y, negative, positive and dupli-
cate, YN X Yp X yn = 0·65 X 1·7 x 0·59 = 0·65. In fact, the product Yp X yn =
1· 7 X 0 ·60 = 1· 02, the contrast of the original is practically unchanged.
To obtain the image on the straight line, the duplicate negative, like the
positive, is slightly overexposed. It therefore differs visually from the original
as it is more dense, having no clear areas. In addition, it may appear flatter
than the original if the image is slightly coloured, due to the finer grain.
It is possible to vary the y of the three images, provided that the final y is
between 0·6, and 0·8. Thus positive films can be used for duplicating with a y
of only 1·25 and negative films for a y of 0·65, borax developers being used in
each case. The original must have, to compensate for the lower contrast, a
higher y-0·8 if the duplicate is to have a y of 0·65.
After washing, the films are carefully cleaned with a pad of soft chamois
soaked in carbon tetrachloride.
240. Reversal
As we have seen in a previous chapter, the reversal of a negative to a positive
can be accomplished in three ways: simple reversal; using a solvent ; and con-
trolled re-exposure.
In each case, the contrast of the reversed image is equal to the contrast of
the negative image, which must therefore be developed to a high y (1·4 for
films). Actually the reversed image appears slightly less contrasty than the
negative, as it is composed of the finer grains (left behind as they are less
sensitive); it is known that for an equal mass of silver, fine grains are more
transparent than coarse ones.
With simple reversal the silver bromide remaining after negative develop-
ment and bleaching is blackened. As the thickness of the layer is constant,
overexposure of the negative produces a positive which is too light and under-
exposure gives a dense positive (Fig. 39); in the former case detail is lacking
FrG. 39. Simple reversal.
in the highlights, whilst in the latter case the shadows suffer. It can be seen in
the first two curves the highlights are recorded on the straight line, the clear
parts of the reversed positive having correct rendering whilst the dense
shadows are on the distorted part of the curve.
When the negative is developed in a solvent developer, a thicker emulsion
can be used, the excess halide being eliminated by prolonging development
after reaching y cc · If the negative image is overexposed there is sufficient lati-
tude, however, to record the whole density scale.
Contrary to the general belief, reversal with solvent does not increase the
speed of the layer at all, but only permits overexposure by using thicker
emulsions.
It is the same with controlled second exposure. The emulsion layer is also
thick. If the exposure is normal, that is making best use of the emulsion speed,
the excess silver bromide is neutralized by using a low intensity for the second
exposure; the larger grains only are affected and the blackening is therefore
restricted, the remaining halide being eliminated by fixing; thus the result of
PHOTOGRAP H I C REPRODUCTION 249
normal reversal is achieved. If the negative is overexposed, the major part of
the halide is removed by first development and bleaching. There is then a
relatively small amount of halide left, and most of this must be used to form
the image. In this case a stronger second exposure is given than for the nor-
mal exposure (Fig. 40).
ITl
FIG. 40. Reversal with a solvent or b y controlled second exposure.
241. Transparent positive copies

Emulsions for transparent positives have characteristic curves which are
generally similar to those of negative emulsions, but their exposure latitude
is greatly reduced. In compensation, the y ., and maximum density are high.
Positive emulsions for transparencies are slow and fine grained.
These positive materials are printed by contact or projection. In the former
case the effective density has a value close to the diffuse density. In projection
printing, the effective density of the negative approaches the specular density.
The image itself is diffusing, more so as its grain becomes coarser. A coarse-
grain negative produces a much greater difference between contact and pro-
jection printing than a fine-grain one.
Cine positive films are developed to a gamma of 1·8-2·6 so that with a
negative developed for example to YN = 0·7 a positive image, with a contrast
YN XyP = 0-7 x 2 = 1·4 minimum, is obtained. A tolerance of 0·05 is per-
missible. When fine-grain positive stock is used the prints are more trans-
parent and to obtain a sufficiently contrasty projected image, the diffuse light
control y<1 l must be increased to 2·5.
Important note: It must never be forgotten that the characteristics of an
emulsion do not only vary from one batch to another, but also during storage,
which makes frequent tests necessary .
Sixteen-millimetre prints. Prints on 16 mm film from 35 mm originals are

made with an optical printer in which stray light is reduced to a minimum. <2 >
The contrast factor inherent in optical printing must be considered, when
determining the development.
Positive emulsions for reproduction. These emulsions can be divided into
two categories: those for document copying and those for the graphic arts.
For the reproduction of documents both ortho and pan microfilms are in
current use. The microfilm emulsions are generally rapid chlorobromide with
extremely fine grain. Bromide types are available but the grain is much
coarser. They are made relatively fast by colour sensitizing (in the yellow-
orange for ortho). They is from 3-3·5. There are films for 16 mm reproduc-
tions and positive sheet-films for preparing tracings. The tracing emulsions
are also available on translucent waterproof paper; their contrast is very high.
For the graphic arts fairly fast emulsions with contrasts varying from 1·6-
2·5 are used for half-tone work. Slow fine-grain chlorobromide emulsions
with high contrast are used only for line work.
242. Photographic papers

Photographic papers have slow emulsions-bromide, chlorobromide or
chloride.
Bromide papers are used primarily for reproductions in large sizes and in-
dustrial work. Chlorobromide papers give warm tone images and because of
this are used for portraits. The principal use of chloride papers is for printing
amateur snapshots.
The gelatin used for glossy papers is well hardened so that they can be
hot-glazed.
The emulsion layer is relatively thin and development is to y "" to obtain the
maximum black.
The exposure latitude of photographic papers is very small, the more so
with more contrasty emulsions; the positive image almost always includes
the extremes of the negative.
The support. The paper base is made in two thicknesses: paper and card-
two colours: white and ivory (or chamois or cream)-three surfaces: glossy,
semi-matt and matt and four physical forms: smooth, grained, silk and velvet.
The paper is deformed by wetting and drying. This is to be expected and
results in a shrinkage of less than 0· 5 o/o. Drying on a heated drum on the
contrary stretches the paper to a greater extent. This deformation is aniso-
tropic, that is different in the two directions. It is noticeable mainly with
machine drying where the expansion is greater in the transverse direction.
The anisotropy is accentuated further by hot glazing. The variations continue
for several days following drying.
White base is always slightly tinted pink blue or yellow. This can easily be
seen by rolling the paper into a cylinder and observing the inside. Primarily
this tinting is to mask the greyish colour of the gelatin. Ivory papers are some-
times dyed in the mass and sometimes stained superficially.
Sensitivity. Bromide papers are relatively sensitive, about one-hundredth
that of a fast negative material. Orthochromatic chlorobromide papers are
only half as fast as bromide; unsensitized they are five to ten times slower.
The chloride papers (gaslight) are much slower: generally about one-hun-
dredth the speed of a bromide emulsion. They are therefore printed with
powerful lamps. In H and D units the following comparative figures can be
quoted (in order of speed):
Non-sensitized ultra-rapid negative emulsion 1000
Medium-speed half-tone emulsion 120
Ortho microfilm 60
Process emulsion 18
Normal bromide paper 10
Ortho chlorobromide paper 3-5
Unsensitized chlorobromide paper 1- 2
Chloride paper 0·1
The speed (or sensitivity) of a photographic paper depends on the ease
with which the maximum usable black is obtained, which for glossy papers can
be fixed at 1·5, and 1·15 for matt papers. If two different papers require 8 and
4 seconds to give the maximum black, the second is twice as fast as the first.
After the Lilienthal Gesellschaft, the speed has been fixed by the formula
10,000
8 = --
E
where E is the exposure necessary to give a density of 0·8.
With the ASA standard, which uses the same formula, the density used is
determined by a point above the toe such that the slope at this point is ten
times as high as that at a lower point which is found experimentally. This
controversial method will be discussed later.
Maximum black. We have said that the maximum usable black of a glossy
paper is 1·5 and that of a matt paper 1·15. However, the maximum obtainable
black can reach 1·65-1·7 for a bromide paper and 1·75- 1·85 for a chloride
paper. It depends mainly on the structure of the silver grains and upon the
thickness of the layer. The absolute density of a matt paper generally reaches
1·3; those of semi-matt papers have intermediate values.
A paper poor in silver or having only enough to give grey images easily
appears to have a low contrast due to the absence of real blacks. If the paper
is made with the minimum of silver, slight differences in layer thickness
result in a visible irregularity on development.
Shape of the characteristic curve. Photographic papers have an S-shaped
characteristic curve (Fig. 41 ), very similar to those of negative emulsions.
Generally there is a central straight line region which is sharply defined and
predominant. The length of the toe and its curvature vary from one type to
another and even from one batch to another of the same type because of the
presence of a long tail to the toe. Of the many thousands of photographic
papers examined by the author there were but two with a badly defined
252 PHOTO G R A PHIC CHEMISTRY
straight line. From all this evidence, and contrary to the opinion unfortun-
ately widespread, the straight line of a paper emulsion is a definite character-
istic and even the principal criterion.
FIG. 41. Normal glossy paper.
243. Gradation of papers

Following the classical conception, the gradation of a paper is determined by
the usable extent of luminosities recorded between two points on the charac-
teristic curve situated on the toe and shoulder of the curve corresponding to
slopes of 0·2. The lower the brightness range, the more vigorous (in prin-
ciple) the images obtained. It is true that a normal bromide emulsion can
accommodate a range of 1·1-1·2, a soft emulsion 1·2-1 ·5 and a hard emulsion
0·8- 0·5.
In the ASA system worked out by Jones and Nelson, <3 ) two points P and Q
are taken which are on the toe and upper part respectively such that the
slope of the chord joining them (tan PQ) has a value equal to ten times that
of the lower tangent passing through P: tan PQ = 10 tan P.
The distance Pq where q is the foot of the perpendicular dropped from Q
to the horizontal through P, measures the gradation. Qq is the usable density
range.
The tangent PQ can be found by the method of W. Swift< 4 ) which uses the
pivoting of two solid rules, or with Morisson's apparatus. <5 )
The determination of gradation using the special gradient methods which
have just been described (Chapter XV) has two serious drawbacks: it is not at
all reproducible, and does not represent the actual character of the paper. It is
not reproducible as it is practically impossible to determine accurately the posi-
tion of the point where the gradient is as low as 0·1 or 0·2 of an emulsion< 6 )
whose toe (that is the low density region) varies greatly with slight experi-
mental errors and storage conditions. A simple calculation shows, further-
more, that the thickness of a pencil line in the drawing of the curve is enough
to change the gradation. Anyone familiar with the practice of emulsion
making knows to what extent they are unpredictable and elusive.
Even if the determination of gradient, by finding low slopes on the toe of
the curve, were not subject to errors, it can be asserted that the figure found
is not representative of the character of the paper studied. The author has
prepared soft, normal and hard positive emulsions which have, however, the
same extreme brightness range and therefore, apparently the same gradation.
We have already said that most paper emulsions have a characteristic
curve whose straight line is well defined. It is therefore the contrast or slope
of the central part which should be known to determine the classification. This
does not lessen the desirability of finding whether the shape and length of the
toe harmonizes with they. The toe of a paper emulsion can vary greatly from
batch to batch (of the same type), from day to day and from one processing to
another; whilst the contrast of the majority of the curve remains relatively
stable.
The Deutsche Lilienthal Gesellschaft has proposed that the average
gradient should be the y of the chord joining the points where the density is
0 ·3 and 1·55 (or 1·3 for papers other than glossy), and the usable range is the
distance between the points corresponding to densities of 0·03 and 1·55 (or
1·3).
Apparent contrasts of different paper grades (read on the same densitometer):
Soft Normal Vigorous Hard Extra hard
Glossy bromide 1·5 2 3 4 5
Matt bromide 1·2 1·6 2·5 3·2 4
Glossy chloride 2 3 4 5·5 7
ASA standard for photographic papers (No. 38, 2nd March 1947). The
sample is conditioned at zoo ±soc and R.H. 50 ± 5% and exposed in a non-
intermittent intensity scale sensitometer for 4-8 sees. A tungsten filament
lamp with a colour temperature of 2850 ± 15° K is used.
The exposed paper is developed after 2 hours in the following developer, diluted
before use with two parts of water.
Water at 50°C (122°F) 500 cc
Metol 3·1 g
Hydroquinone 12 g
Sodium carbonate monohydrate 67 ·5 g
Cold water to 1 litre
Temperature: 20 ± 0·5 °C (68°F).
Agitation: 2-litre dish, rocked in four directions, fifteen times in 2 minutes.
Development time: 90 sees.
Acid stop bath: 1 minute in
Acetic acid 28% 45 cc
Water to 1litre
Fixing: 10 mins. at 20°C (68°F) in
Hypo 480 g
Water to 2litres
to which is added the hardener:

Water 160 cc
Acetic acid 28 % 96 cc
Potash alum 30 g
Washing: 15 mins. at 20 ± 5°C.
Drying: below 40°C (104°F).
Density measurement in diffuse light. For special surfaces, two readings are taken,
the second after rotation of the sample through 90 ° on the measurement axis. The
average is used.
Curve: Determine P and Q such that the slope of the tangent at Pis 1/10 that of
the chord PQ
10 4
S=-
EQ
The Standard Z.38 has been modified in certain respects in ASA Standard
PH 2.2. 1953. The point a where the density is 0-02 is found, then a trans-
parent sheet carrying oblique parallel lines is used. That on the right being
the tangent to the toe, and that on the left, the tangent at the shoulder d. The
difference log Ed - log Ea measures the log brightness range (scale index).
Dd- D a is the usable density range (density scale). The useful black Dd is
the maximum evaluated density. Log Ed is the shadow exposure index.
The slope of the oblique lines on the calculator is bar gamma y.
Remarks. (1) The base density 0-02 is much too low to be indicative of the
main character of the curve. (2) The reason for the development time of
90 sees. for all papers is not clear.
244. Reproduction of extreme densities

The extreme density range of a negative is usually greater than the brightness range
of the paper. It is sometimes desirable either to reduce the density range of the nega-
tive whilst maintaining the contrast of the details, or to reduce the gamma of the paper
to match it with the negative.
Reduction of the extreme density range of a negative: this reduction can be effected
by two different methods: the first uses unsharp masks using the technique ofYule;< 8 >
the second, which is quicker, is an application of the Herschel effect. The technique
described by Miss M. Johnson<•> is as follows: the negative is first printed by contact,
using a short exposure to white light. A transparent film is then inserted between the
negative and the paper, and a second exposure of long duration to red light is made.
The extreme densities of the negative are thus reduced to such a degree that they can
be accommodated on the paper. Source of red light: 4 photofioods + 3 Wratten 40
filters to each (ventilated and protected by glass sheets).
The Herschel effect is more pronounced with a desensitized paper. The white
source then used is two photofioods, and the exposure 3-9 seconds. The filters for the
red light are then Wratten 25 and the second exposure is 30 sees.
Reduction of contrast of papers using the Sterry effect. The Sterry process consists in
softening a paper image by treatment, after exposure, with 1% dichromate, for 1
minute. The paper is then rinsed for 20 sees. and developed. For chloride papers, the
dichromate concentration is reduced to 0·2%.
The exposure time is adjusted so that the low density details are recorded. The di-
chromate concentration and treatment time are governed in practice by the difference
between the contrast of the negative and of the paper. An empirical rule! 10 l is to deter-
mine the optimum times for the shadows and highlights and to obtain the quotient.
The number found, v, is the number of cc of 5% dichromate to be diluted in volume
V. 1 ·5 V then gives the treatment time in seconds.
'High-key' images. High-key images, having most of the subject in light tones, some-
times with dark patches, are generally used for portraits. The simplest method is
obviously to photograph a light subject with no strong contrast. Negative and positive
are both developed soft. If there are unwanted high densities, the printing time is
reduced. A second method is to bleach the positive image in a tanning dichromate
bleach which hardens the gelatin in the dense areas. By redeveloping in a dilute amidol
developer only the light areas redevelop normally.
245. Industrial papers

Industrial papers are used for document reproduction. There are several types.
Generally they have matt surfaces and the emulsion is balanced with the support in
such a way that they do not roll up after drying on a hot drum.
Document paper: bromide emulsion on thin paper (90 gramme-no baryta). Sensi-
tivity equal to or less than that of glossy bromide papers. Use: enlargements from
microfilms. The same type is made coated on both sides. Some of these papers have
chlorobromide emulsions.
Rapid document paper : orthochromatic bromide or chlorobromide emulsion on
baryta paper. Ten times as fast as ordinary document paper. High contrast. Use:
direct photography of documents on Photostat type machines with lens and reversing
pnsm.
Cardiographic paper: ordinary bromide emulsion on glossy paper slit into laterally
perforated bands.
R ecording paper: very fast emulsion of negative type, coated on thin non-baryta
paper. Use: recording machines with luminous spot.
Reflex paper: extra hard orthochromatic chloride emulsion with very short threshold,
coated on a non-baryta coated thin base. It can be handled in weak electric light or
very weak daylight.
Use: reflex document copying. The emulsion is placed in close contact with the
document and exposed through the base using a yellow filter. By r apid development in
30-60 sees. a negative is obtained. After drying, the negative can be printed on the
same paper by normal contact to give a positive.
As the foot of the curve is very short the first exposure through the emulsion pro-
duces no latent image or fog, but a sub-latent image. The light reflected by the white
areas of the document again acts on the emulsion; it augments the action of the
incident light to producing a developable latent image, which is very dense as the
emulsion is very contrasty (y : 7).
Autopositive paper: solarized contrasty orthochromatic chloride emulsion on a thin
non-baryta treated base. Use: direct positives by normal or reflex printing. Sensitivity
equal to that of diazo paper.
246. Variable contrast papers

(a) llford 'Multigrade' paper. This paper whose principle was disclosed by K. Fischer
in 1912 was perfected by F. Renwick in 1940. It consists of a mixture of two emulsions,
one with high contrast sensitized to green, the other not colour sensitive and soft.
D epending on the predominance of green or violet light, one emulsion or the other is
affected which results in a more or less contrasty final image . A range of coloured
filters is used in printing. (Phot. Jl., 1940, 266.)
Filter Exposure Contrast
Without filter 1- sec. very soft
Light yellow i sec. soft
Normal yellow 1 sec. normal
Dark yellow 1! sec. hard
(b) Defender 'Varigam' paper has a chlorobromide emulsion sensitized with a
sensitizer such as 1 : 1-diethylpseudocyanine at a concentration below the optimum.
This emulsion is washed to remove the excess dye. Potter and Hagaman stated that
the dye is adsorbed solely by the larger grains (U.S.P. 2,280,300). By printing with
green light, only the sensitized grains are affected which, and owing to their size give
a soft image, whilst with violet light the non-sensitized grains are affected giving a
contrast 50% higher. Ten filters passing from blue to yellow are used in printing.
(c) Kemart fluorescent paper. This paper has a fluorescent support and is intended
for photomechanical reproduction. It is exposed to an auxiliary ultra-violet source
which increases the contrast by excitation of the fluorescent compound.
In the numerous patents concerned with fluorescent substances( 11 l are: acids derived
from amino substituted 4 : 4-diaminostilbene; derivatives of 7 -aminomethyl-coumar-
one; derivatives of 2-styrylbenzimidazole, etc.
Document reproduction on fluorescent paper. This method, which will be returned to,
later, in connexion with colour reproduction, enables the maximum contrast to be
obtained in ordinary photography of documents. The latter are made on fluorescent
paper. Retouching is carried out on the fluorescent layer. The drawing is lit with a
mixture of ordinary and ultra-violet light, whilst a U.V. filter is placed over the lens.
The areas activated by the ultra-violet become more brilliant, which increases the
luminosity scale and therefore the subject contrast.
SOUND RECORDING
247. General properties of sound
Sound is a vibration phenomena defined (in simple cases) by a sinusoidal
movement.
x = a sin ( wt + cf>)
in which x is the elongation, a the amplitude, w the pulsation and t the time.
The period T, or time necessary to complete one vibration is 27T/w and the
frequency, number of vibrations per second F = wj21T.
The intensity is measured by the product of the square of the amplitude a
by the square of the pulsation w
The ratio of two intensities I 1 /I 0 is therefore equal to a12 /a 02 •

In practice, two intensities are compared following a log scale where
log I 1 /I 0 is given in bels (or 10 log I 1 /I 0 decibels). In using the ratio of power
in watts one has: 10 log wl;w0watts.
Harmonics. When the vibratory movement produces several sinusoidal
vibrations whose frequencies are successive multiples of the fundamental fre-
quency, the results are called harmonics. The shape of the wave depends on
the amplitude and phase of each harmonic. A periodic function having higher
order harmonics of quite high amplitude has breaks in the wave representing
it.
Properties of a sound. A sound has the properties: pitch, intensity and
quality or timbre.
Frequency produces the pitch of a note. A low note has a low frequency
and a high note a high frequency. The lowest audible notes have a frequency
of about 16, but the musical scale does not begin until E 0 = 40. The upper
limit for very high notes is about 16,000, but varies with the age of the
observer.
To have a clear impression of a note, a minimum duration of one-tenth of
a second is necessary; this corresponds to 5 cycles for A 3 = 435 and C4 = 512
and 10 cycles for C 5 = 1024.
Intensity. The intensity of a note, as we have seen, is a function of the square
of the amplitude. The aural sensation is not directly proportional to the
intensity; it varies with the log of the excitation. Below a certain threshold no
sound is audible. The aural response curve plotted against the log intensity
is S-shaped like the photographic characteristic curve.
The voice in average conversation has a strength of 40 decibels. The ear
can detect a difference of 2 dB.
Timbre. The timbre or quality of a note is due to the presence of a certain
number of harmonics of various amplitude superimposed on the fundamental
note; their vibration shape has only a secondary influence. For example, the
flute produces notes almost free from harmonics; stringed instruments have
five or six, whilst brass instruments mainly emit higher harmonics.
248. Principle of sound recording

As sounds are periodic vibratory movements, they can be recorded by photo-
graphic sensitive layers.
The sound is received by a microphone and converted to electrical vibra-
tions. These, in turn, modulate a light beam projected onto a moving film.
The sound is recorded on a track 2·5 mm wide.
There are two systems of recording the change in intensity on the sensitive
layer: (a) by varying the width of a continuous line of even density giving a
saw-tooth effect and (b) by varying the density of a continuous band (Fig. 42a).
In each case the result is the same: a periodic modulation of the total light
passed through the sound track. This is brought about by projecting the
image of a very narrow slit onto the recording film by an optical system. The
slit is illuminated by the modulated light.
A. Variable density recording. In this system, the light is varied by means
of a light-valve, a Kerr cell or a glow lamp.
The light-valve consists, in principle, of two flat metallic ribbons placed
between the poles of an electromagnet. A modulated current passing through
the ribbons alters the separation between them and in consequence, the
height of a light beam projected by a fixed source (Western Electric
System).
258 PHOTOGRAPHIC CHEMI S TRY
The Kerr cell is dependent on the electromagnetic properties of light. A

light beam is polarized by passing through a nicol prism, then cut out by a
second nicol prism at 90° to the first. Between the two prisms is a small cell
filled with nitrobenzene containing two electrodes whose purpose is to pro-
duce a varying electrostatic field due to the potential difference between the
electrodes resulting from the amplified modulations of the microphone cur-
rent. The field variations in the nitrobenzene produce corresponding rota-
tions, more or less pronounced, of the polarization plane which alters the
intensity of the beam transmitted by the second polarizer. (Toblis-Klangfilm
System.)
A B
FIG. 42a.
Sound tracks: A. Variable area.
B. Variable density.
The Kerr cell can be advantageously replaced by a thin crystalline layer

cut perpendicularly to the geometrical axis, from a crystal of monopotassium
phosphate, and placed between two transparent electrodes. With changes in
the potential, the layer becomes birefringent and transmits more or less
polarized light (Pockels photoelectric effect). (llb )
The glow-lamp produces a variation in light intensity directly, with varia-
tions in the current received. The luminous discharge takes place in a rarified
gas between a red-hot anode of platinum coated with the oxide of an alkaline
earth, and a nickel cathode. The lamp is placed in a quartz tube.
B. Variable area (variable width) recording. The amplified microphone cur-
rent is received by a mirror galvanometer. This reflects a constant intensity
light beam onto the recording film deflecting the beam in proportion to the
modulating current (RCA system) .
The light modulation can also be carried out, however, with a ribbon valve
at 90°. An anamorphic optical system enables the very small ribbon move-
ments to be amplified (Western Electric). <12 >
There are several types of variable area track (Fig. 42b ).
(a) Unilateral track
(b) Bilateral symmetrical tracks
(c) Opposed tracks (push-pull) } Cl=A
(d) Double unilateral track
(e) Opposed tracks Class B
(a) (b) (c) (d) (e)

FIG. 42b. Different types of variable area sound track negatives.
Opposed type Ac tracks are composed of two separate 'out of phase' parts.
They give the best recording for original tracks (for subsequent re-recording
on the final negative) by eliminating even harmonics and reducing back-
ground noise. The opposed tracks of type b, one of which records the nega-
tive half-wave and the other the positive, have, on the other hand, a high
distortion factor.
The double unilaterals track (Ad), which gives excellent results, has the
advantage that it is less sensitive to misalignment of the recording apparatus.
It is obtained by optically doubling the track image, the ribbon movement
being halved.
C. Magnetic recording. Magnetic sound recording has displaced direct
photographic recording for the production of originals. The principle of this
method is well known: a plastic tape having a layer of iron oxide is passed
through a varying magnetic field which affects it permanently. By the reverse
process, passing the tape between the poles of an electromagnet produces a
modulated current.
The tape is made of cellulose triacetate coated with a layer of ferric oxide
Fe 20 3 whose particle size is less than 1/L, or polyvinyl chloride containing
the oxide. <12b >
Reproduction. One method of applying sound to cine films is to stick a
magnetic tape or coat with a magnetic layer within a narrow band. Stereo-
phonic films have four magnetic sound tracks, on each side of the perfora-
tions.
A second method is to re-record the sound photographically on an inter-
mediate negative film. J. G. Frayne (Bell Tel. Co.) has shown that two
parallel narrow optical tracks, recorded on a normal 2·5 mm width, are
sufficient to produce a stereophonic effect. <12c) The two tracks are separated
by an 0·1 mm interval.
For editing, a film carrying both positive photographic (by re-recording)
and a stuck-on or coated magnetic track can be used. <13 > Some machines use
K
an oscilloscope so that the effect of the magnetic track can be seen, and this
enables the photographic track to be dispensed with. <14 > Others enable cutting
to be performed without visual aid by moving a magnetic head over the
stationary drum. (15)
Photographic sound recording is made on a separate special negative film.
Mter development, the sound track is printed in the appropriate area of the
positive film (which carries both picture and sound). These are developed at
the same time in the same operation.
The sound is reproduced by illuminating a narrow slit whose image is
projected onto the moving positive film. The periodic light variations pro-
duced by the sound track are received by a photoelectric cell placed on the
other side of the film, and converted to an electrical impulse, which is ampli-
fied and fed to the loudspeaker.
Photoelectric cells containing low-pressure gas (such as argon) are much
more sensitive than the completely exhausted ones. The former produce, for
example, 100 p.A per lumen whilst the latter give only 20. The wavelength of
optimum sensitivity is at about 700 mp. in the deep red; it can be increased
to 840 mp. (near infra-red) for caesium-silver oxide cells, whilst antimony-
caesium SbCs 3 cells have a maximum response at 460 mp. in the blue. <16 >
249. Emulsions for sound recording

A sound recording must be capable of linear reproduction, that is, without
distortion, from 40 to 10,000 c.p.s. at a level of 50-60 db.
As the negative film travels at a speed of 456 mmjsec. (length of twenty-
four frames), a single cycle of a low note, 120 for example, will cover on the
sound track, a distance of 3·8 mm whilst the length of one cycle of a very
high note of a frequency of 8,000 occupies only 0·057 mm.
It is therefore evident that for recording high frequencies, a much higher
resolving power is required than for low frequencies.
Also, the sharpness of the recording depends on the loss of density by
diffusion (irradiation). This is why the negative emulsion must have regular
and very fine grain (0·5 p.). A dye of the complementary colour to the sensi-
tivity can be used to limit the penetration and irradiation of the light in the
depth of the emulsion.
Halation, which is particularly troublesome, is avoided by including a thin
layer coloured yellow, red or blue, depending on the colour sensitivity, be-
tween the emulsion and the base. Anti-halation layers on the opposite side of
the base are less effective.
The speed of the negative material varies with the recording system, but is
generally higher than cine positive stock. With a movement of 456 mmjsec.
and a slit width of 10-20 p., ultra short exposures of 1/20,000 to 1/50,000 sec.
are used at intensities about 100,000 candle-metres. An inertia value of about
0·2 is therefore necessary.
In order to avoid distortion in the reproduction, it is furthermore necessary
that the image is produced only on the straight part of the characteristic
curve.
Because of this, the negative emulsion must have a well-defined straight
line with a very short toe. Furthermore, it must be capable of giving suffi-
ciently high densities as we shall see later.
For variable area recording, contrasty emulsions are used, whilst for variable
density recording, a contrast five times lower is enough.
We note finally that the negative emulsion should have as little fog as
possible. However, this is less important than for the positive film. The latter
is also used for the picture; it is advantageous to have a long straight line with
little irradiation.
To give examples we would quote film characteristics:
Kodak 1372 for variable area recording. Sufficiently slow to dispense with
the U.V. filter. Sensitivity limit: 460 mtt. Resolution: 150 linesfmm. High
contrast: y 3- 3·5 reached in 4 mins. in D 16. It is usually developed toy 2·4-
2·8. Grey base, density 0·12.
Kodak 1373 for variable density recording. Maximum contrast 0·5. Slow
development (6 mins.) for easy control of y which normally varies between
0·35 and 0-45. Resolving power in borax developer: 90 linesfmm.
DuPont films. The old film for positive copies of sound tracks, No. 225,
printed in ultra-violet light, the y obtained being 1·55 (2·3 in white light).
The new film No. 232 enables copies to be made in white light at a y of 1·6,
from negatives of y = 0-85, destined primarily for ultra-violet light.
For variable density recording No. 236 is preferably used, developed to
y 0·65 (measured with a lib sensitometer control), the unmodulated density
being 0·52. Copied in white light it has more latitude in print density than
the old type 226 which was printed by ultra-violet.
Sound tracks are developed in the same baths used for negative and positive
picture images.
250. Development of sound recordings

The development of sound recordings differs with the system (variable area
or density) used.
Whatever system is used, the operations are carefully controlled with
sensitometric tests. All sensitometric methods are good if used with dis-
cretion. Sound recording is always carried out with varying intensity (of high
value) and fixed time (very short): these conditions are not produced with
normal sensitometers. <17 > By careful comparison of the values given by the
sensitometer and on the actual recording, coefficients relating them can
readily be found, which are adequate for production work.
Variable area recordings. The negative film is developed in an energetic
developer to a y of 2·4-2·8. The recording light is adjusted to give a track
density of about 1·5, the fog being below 0·06. For push-pull tracks, the
recommended density is sometimes higher.
The positive copy is printed so that the part protected by the opaque track
remains quite clear, whilst the unprotected region has a density of about
1-35- 1·5. As we know, the positive carrying both picture and sound is
developed to a y of 2-2·6.
262 pHOTOGRAPHIC CHEMISTRY
The difference in transparency between the dense and clear areas is even
greater, and consequently leads to better reproduction, if the clear areas are
free from fog. The benefit obtained by increasing the density of the opaque
area is much less than the reverse operation of increasing the transparency
of the clear area.
To reduce the background noise which masks the low intensities, the
'RCA High Fidelity' system uses a central track, dense in the negative and
clear in the positive, with a double row of saw teeth. This track, very narrow
in the silent parts, widens when modulated. Thus imperfections in the clear
areas have a diminished effect on the reproduction.
Variable density recording. As the modulation is due to variations in the
density of the sound track, it is necessary that:
1. The complete density range recorded is on the straight line so that there
is no distortion. <lS>
2. The effective contrast (with reference to the sensitivity of the photocell)
of the picture-sound positive is 1 : YN X Yp = 1.
All effective y greater or less than 1 lead to distortion.
A variable density sound record consists of a double set of variations
higher and lower than an average density of zero level (Fig. 43). This average
density corresponds to silence.
..,
. ..'
'' ~
' '
Log. E
FIG. 43.
Now it can be stated that the background noise is reduced if, during the
silent periods, the cell received less light, that is, if the average positive
average density is higher (conversely, if the negative track is less dense). As a
limit is set by the length of the straight line, the Western Electric 'Noiseless'
system can vary the average density automatically depending on the intensity
of the sound reproduced. In the silent periods the positive density is maxi-
mum; it is reduced during modulation for the high intensities; thus the high
density peaks are still found on the straight line below the limiting point B.
A sensitometer strip is developed at the same time as the negative in a fine-
grain developer. Now depending on the modulation system used, the inter-
pretation of the control must be varied. The light-valve modulates on a time-
scale whilst the Kerr cell varies the intensity. In the former case the gamma
does not change whatever the intensity used, and is therefore comparable
PHOTOGRAPHI C REPRODUCTION 263
with the sensitometer control. In the case of intensity variation, the gamma is
lower for high intensities, that is, the sensitometer gives values which are
apparently much higher. Call YN the negative gamma as a function of the
openings of the light-valve, YsN the gamma of the negative sensitometer strip,
Ysc the positive copy of the negative sensitometer strip and YsP the gamma of
a positive strip developed at the same time as the positive film.
We know, furthermore, that the ratio of the effective gamma in the optical
system of the soundhead and the photometric gamma in diffused light is
about 1· 3. Taking this value in the example equation we have :
effective y = 1 = YN X Ysc X 1·3
but YN = a . YSN and YSC = b . YSP
a and b being the coefficients which show firstly the ratio of the sensitometric
and actual negative measurements, and secondly the relationship between
the sensitometric measurements and the positive copy. a is determined once
and is constant, whilst b must be checked daily. <19 > Therefore we have
effective y = YSN X YSP X 1·3 X a X b
If the negative is developed to YsN = 0·4 and the positive to YsP = 2·10
we get
YSN X YSP = 0·84
Knowing that a x b = 0·91, we have effectively
YSN X YSP X 1·3 X a X b = 1.
The average density of the negative is 0·6-0·7, and that of the positive
0·5-0·7 depending on the amplitude recorded.
The glow-lamp produces much smaller exposure variations than the light-
valve or the Kerr cell. In this case, for maximum volume, the negative is
developed to a much higher y whilst the density is reduced to 0·35.
Development and printing. The control of temperature and composition of
the developing solution have a great influence on the constancy of sound track
development. Furthermore, inefficient agitation can produce distortion due
to the local accumulation of by-products in the region separating the clear
and dense areas. (20)
Microdensitometer measurements enable these defects to be detected. <21 >
When prints are made, the shrinkage of the negative (which is not con-
stant), must be considered, whilst the shrinkage of the unexposed positive
depends on the time it has been stored. Shrinkage can vary between 0 and
1% and the slip of the negative over the unexposed positive can result in
more or less pronounced distortions.
The effect of shrinkage can be overcome by using non-slip printers in
which the films only touch each other at the exposure point.
Loss in volume due to shrinkage amounts to 1 dB for a difference in length
of 0·1 % . The other principal losses are: increase of printing speed from 24 to
48 frames /sec. loses 2 dB; increase of the aperture of the optical system, up
to 3·5 dB; increase of the height of the exposure aperture, up to 6 dB.
251. Sound tracks on colour films
When the colour print is made with the three subtractive colours and an addi-
tional silver key image as in the Technicolor process, the development of the
sound track presents no special difficulties; the film has a silver bromide
emulsion: the sound track and, if desired, a grey silver image, are printed
and developed together. The three colour images are then printed by imbibi-
tion. Another method used in the three-colour Supercinecolor process is to
tone only the picture area without affecting the silver image of the sound track.
In the case of films whose sound track is also coloured the problem is more
difficult to solve; the photocells used in soundheads have their maximum
sensitivity in the extreme red or near infra-red (caesium cells). Now most
colouring materials are transparent in these spectral regions; it follows that a
coloured sound track has no effective absorption on the light beam which it
should modulate.
The difficulty can be overcome by using a blue sensitive photocell (antimony-
caesium) and a red (or more exactly, magenta+ yellow) sound track. These
cells however are not generally used. '
Another simple solution is to use, for the cyan, an iron ferrocyanide image.
This is an inorganic pigment, and unlike the organic colouring materials,
has a strong absorption in the red and infra-red. The sound is therefore
printed in the layer used for printing the red record negative, and after
development, both are toned cyan. The contrast and the maximum and
average densities are controlled with a spectrophotometer in such a way that
the toned positive sound track has the same characteristics towards the photo-
cell of a silver track. The considerable increase in contrast due to iron toning
must be considered and the picture-sound record is developed to a gamma
two or three times lower, depending on the toning bath. The gamma of the
sound negative, and the light used for printing the copy, are adjusted and
controlled as a function of the selective absorption of the cyan image com-
pared with a silver track. Iron toning is generally used in two-colour pro-
cesses. <22 > It can also be used for three-colour work as it gives excellent colour
rendering, although transmitting part of the orange. However, if the sound-
head uses a lead sulphide cell, sensitive between 1 and 3 1-L as in some 16 mm
projectors, iron toning is unsuitable.
Sound tracks on colour-developed films. When the colour images are obtained
by colour forming development, the sound track is composed of silver and
dyes. It is usual to remove the silver of the image in a reducer. Now, in the
track area, the metal should not be removed.
There are four methods for keeping the sound records on colour films:
(a) After bleaching with ferricyanide and superficially drying with an air
squeegee, the sound track is redeveloped locally, using a narrow roller which
applies a vigorous developer rendered viscous (1000 centipoises) by addition
of a thickening agent, such as hydroxymethylcellulose, hydroxyethylcellulose,
carboxymethylcellulose or a vinylmaleic resin.
The developer can be a hydrosulphite solution (para. 67) or the following:
metol20 g, hydroquinone 20 g, sulphite anh. 40 g, water to 1000 cc. Lauryl-
pyridinium sulphate 1 g (accelerator) and formalin 20 cc (hardener) can be
added. An Ansco formula contains 3 g hypo. If the developer is too viscous,
it does not penetrate into the layer quickly enough.
Colour films have a yellow filter made of colloidal silver. It is redeveloped
with the sound image and produces a yellowish uniform stain which causes
a loss of sound volume of only 2 dB. However, it is possible to eliminate it
in a very dilute bleach.
The above method has been used with Eastman and Ansco films.
(b) The silver of the sound track is not attacked: the picture area is locally
bleached with a viscous 10% ferricyanide bath, preferably containing a
wetting agent such as Nekal BX (5/1000). The jelly is applied to the film, by
means of a roller or through a narrow slit, then removed by an oblique
scraper. Agfa and Gevaert.
(c) The sound track silver is converted to silver sulphide, after bleaching (Du
Pont), with: sodium sulphide cryst. 63 g, carboxymethylcellulose 20 g, dis-
tilled water 100 cc. This method enables the low contrast of the sound record
to be increased when the amount of silver in the film layers is too small.
(d) The sound track is protected with a local layer of varnish, applied after
development, or an adhesive tape. Not used in practice.
By restricting diffusion, the sound track is located in the two upper layers
of the film, but it is possible to print it in all three layers. <23 > For variable area
recordings, density must exceed 2·4, whilst variable density recordings need
much less silver; in that case the upper layers are sufficient.
The dyes which are present in the sound track have no influence upon the
sound qualities.
1. Streiffert J. G.: J.S.M.P.T.E., 1947, 506-522.

2. Tutchings A.: Brit. Kin., 1951, 132-139.
3. Sci. et Ind. Phot. (2), 16, 84.
4. Swift W.: Phot. Jl., 1946, 71; Sci. et Ind. Phot., 1946, 339.
4. Morisson C. A.: J. Frank. Inst., 1947, 55-61; Sci. et Ind. Phot., 1947, 102-104.
6. The 1 : 10 tangent ratio is much too low; it should be at least 1 : 3.
8. Sci. et Ind. Phot. (2), 16, 170.
9. J .O.S.A., 1951, 748-751.
10. Marmet: Phot. Techn. Sc. Wirtsch., 1950. 80.
11. See a long list of patents in the advertising pages of Sci. et Ind. Phot., March
1953. An liford F.P. 1,074,579 recommends 4-methyl-1 ·3-diphenylpyrazoline.
11b. Dressler and Chesnes: J.S.M.P.T.E., March 1953, 205-216.
12. Frayne J. G.: J.S.M.P.T.E., 1948, 501-520; Sci. et Ind. Phot., 1949, 113.
Browder L. B.: J .S.M.P.T.E., 1948, 521-533; Sci. et Ind. Phot., 1949, 113.
12b. Lovichi and D eriaud : Onde. Elect., March 1954, 241. Kojima: Konishiroku R ev.,
Sept. 1953, 133-150 (in Japanese). See also Mitt. Forschungslabo Agfa, L ever-
kusen, 1955, 1, 289-325 (Springer-Verlag).
12c. Frayne: J.S.M.P.T .E., 1955, 303-308.
13. Frayne and Livadary: J.S.M.P.T.E., 1952, 389-397.
14. Miller R. C. : J.S.M.P.T.E., 1953, 304.
15. Hicks W. R . :J.S .M.P.T.E., 1953,324-332.
16. Sommer A.: Proc. Phys. Soc., 1943,55, 145.
17. The Eastman lib time scale sensitomer is still often used for this purpose. For
a theoretical study, see Lovichi, Sensitometrie des films sonores, Paris.
18. For a graphical method of controlling the positive parameters, see Lobel and
Dubois, Manuel de Sensitometrie, p. 199. Paul Montel, Paris.
19. With sensitometers such as the Eastman lib the gamma given is 1·75 times the
actual gamma by exposing for a very short time, and measured in diffuse light.
20. Sewell G. : Jl. Br. Kin. Soc., 1940, 84.
21. The distortion can be measured by recording a high frequency modulated by a
low frequency. The variations in the average transparency show the distortion .
22. F.P. 697,095 (1930)-B.P. 360,819 (1930).
23. Evans and Finkle: J.S.M.P.T.E., 1951, 131-139.
PART TWO
Photographic Emulsions
Chapter XVII
GELATIN
252. Colloidal properties of proteins
Gelatin is a protein which plays an important part in photographic emulsions
where its chemical and physical properties are utilized.
As with most of the proteins, gelatin is a colloid, so we will begin with a
brief general revue of the colloidal state.
Compounds are usually divided into the crystalloids and colloids: the first
gives true solutions in which the molecules are completely dispersed, whilst
the second give pseudo solutions in which the smallest fragments are much
larger than those of ordinary molecules.
Colloidal solutions are intermediate between true solutions and suspensions
of finely divided material in a liquid. It is true to say that there is no well-
defined border between solutions and suspensions; only the size of the
smallest particles varies resulting in the formation of a solution for the very
small ones (simple molecules), a pseudo solution for the medium ones (thirty
times as big as the simple molecules), and a coarse suspension for the big ones
(insoluble aggregates).
Normal centrifuging cannot separate suspended particles smaller than
0·04 p.. whilst molecules vary in size from 0·001 to 0·0001 p... Ultra-centrifuging
at a 100,000 r.p.m. enables the protein molecules from 0·02 to 0·003 p.. to be
isolated. The colloidal particles can be detected with the ultra-microscope
down to 0·003 p... Beyond that the electron microscope must be used.
These particles are subject to 'Brownian movement' which is a continuous
and random vibration with a molecular origin. The vibration is greater as the
viscosity of the liquid is lower, and consequently as the temperature is higher.
All translatory movement is accompanied by a rotatory movement: whilst the
amplitude of the translatory movement is inversely proportional to the dia-
meter of the particle, the speed of rotation is inversely proportional to the
cube of the diameter.
Many substances are known which exist in the colloidal state: inorganic
substances such as silica, ferric hydroxide, colloidal silver, or organic com-
pounds such as gum arabic, starch, cellulose or albumen. The organic colloids
owe their state to a greater or lesser degree of polymerization; in other words
they occur as associations of more simple molecules. This results in their
molecular weight in this complex state being very high: 70,000 for egg al-
bumen and 300,000 for starch, for example, whilst the molecular weight of
hydrogen is 2 and alcohol is 46.
269
Polymerization is therefore an essential factor in the colloidal state of

organic substances; it explains the size of their complex molecules which are
in fact 'complexes of complexes'. The simple particles of the colloid, or
micelles formed when these polymers are treated with intermicelliary liquid
are made up of two parts: one part is physically inactive and the other plays
the part of the contact layer. Colloidal micelles are found in living tissues in
various proportions giving therefore biocolloidal micelles. The increasing
complexity of the proteins is demonstrated by the fact that their molecular
weights are exact multiples, frequently in geometric progression of the
molecular weight of a simpler protein. Thus crystalline albumen has a mole-
cular weight of 34,500, that of egg albumen is twice as great whilst blood
albumen is three times as great.
253. Isoelectric point

The proteins are amphoteric substances, that is they have both acid and basic
functions and can form either protein salts with acids or proteinates with bases.
Their behaviour depends upon pH. Albumen for example behaves as an
acid at a high pH or as a base at a low pH. The equilibrium point of the two
phases is termed the isoelectric point. It generally corresponds to a hydrogen
ion concentration given at a pH of 4·8.
The micelles are electrically charged. When subjected to an electric cur-
rent (cataphoresis), they migrate towards one of the poles depending on the
pH. Thus in an acid solution (low pH) gelatin migrates towards the cathode
(-)whilst in alkaline solution it moves towards the anode ( +). The neutral
point of the electrical properties of the colloid is exactly at the isoelectric
point, at a pH of 4· 7 to 5 for lime gelatins. The micelles do not then respond
to an electric current.
pH
H OH
(HC1> 4 3 2 1 0 1 2 3 4 (KOH)
FIG. 44. The titration curve of gelatin.
The titration curve has the shape shown in Fig. 44: the pH is on the ordin-
ate and the amount of acid (hydrochloric for example) and base (caustic
potash) on the abscissa, on either side of the ordinate axis. The pH is deter-
mined electrometrically after each addition of reagent.
GELATIN 271
Calf-skin gelatin prepared by the lime method has an isoelectric point from
4·7 to 5·2. Obtained by acid treatment (acetic) it has an isoelectric point
between 7 and 9. With pigskin treated with acid, the i.p. is at 8·2. The higher
isoelectric point of the gelatins obtained by the second process is due to the
treatment time being stopped relatively early (20 hours); if the treatment
time is prolonged the i.p. drops to the limit of 4·8.
PHYSICAL PROPERTIES OF GELATIN

253b. Gelatin solvents
The normal solvent for gelatin is warm water. It can, however, be dissolved
cold either in concentrated solutions of urea, thiourea, potassium thiocyanate,
bromide or iodide, or in organic acids such as acetic, benzoylacetic, salicylic
or phthalic. 3N benzene sulphonic acid dissolves gelatin cold without altering
it.
254. Viscosity of aqueous gelatin solutions

Due to its complex chemical structure which is easily changed, the internal
structure of a gelatin solution becomes more and more rigid on standing;
this has the result that the solution does not have a constant viscosity as this
increases with time. Agitation on the other hand reduces it.
The increase in viscosity is essentially dependent on the temperature : it is
more pronounced at low temperatures when it soon becomes evident. It is
important to note that at about 35°C the variations are very small.
If the pH of a gelatin solution is varied, the viscosity is lowest at the iso-
electric point, at least when the solution is freshly prepared (max. 10 hours).
A solution kept for 25 hours at 52°C shows at the end of this time a sharp
viscosity maximum at about pH 7·6.
In acid solution at high temperature (50°C) the viscosity drops consider-
ably on standing for several hours until it is 40% of its original value (after
24 hours). At the isoelectric point the variations on standing are, on the contrary,
very small, almost negligible. They remain unimportant up to pH 8 (alkaline);
beyond this they become appreciable again.
255. Surface tension

The surface tension of gelatin solutions is lowest at the isoelectric point.
There are two maxima in acid and basic media respectively.
At a low temperature (l6°C) and with solutions of at least 0·5 % there is a
temporary flocculation of the gelatin after the isoelectric point which is
shown by a sharp increase in the surface tension. <I l
Surface active agents readily reduce the surface tension of gelatin solutions.
256. Swelling of gelatin

As with the other properties of gelatin, swelling in water is at a minimum at
the isoelectric point. In very acid media the swelling is particularly rapid
with a maximum at about pH 2·5, especially in the presence of hydrochloric

acid.
The amount of water absorbed increases with the temperature. Further-
more, it is higher with a ready prepared jelly than with dry gelatin, and when
the concentration of gelatin is low; a 5% jelly absorbs twice as much water
as a 50% jelly (compared with the weight of dry gelatin). We will return to
this when emulsion washing is considered.
In the case of dry gelatin films immersed in water at moderate temperatures,
the stretching due to swelling is preceded by a contraction which is greater as
the layer is thinner. A layer 10 1-L thick can in this way contract 20% when left
in water for an hour, before it assumes its original dimensions after 2 hours
and stretches 40 % after 2t hours.
The degree of swelling depends on the temperature at which the film was
dried: with slow drying it swells normally, but with hot drying it swells then
contracts. (2 > It also varies with the dampness of the atmosphere; a high
humidity weakens the intermolecular links.
All gelatin swells to an equilibrium with the liquid in which it is treated;
the absorption of water is due to the difference between the internal and
external osmotic pressures. (3 > The gelatin therefore swells more as the internal
pressure is greater; this internal osmotic pressure increases with the formation
of a gelatin salt which can dissociate into ions due to a strongly acid pH
(maximum between 2·5 and 2·7); the diffusion of the water from the exterior
towards the interior again restores the equilibrium. When the acid is in great
excess, reducing the pH further, the exterior pressure increases faster than
the internal pressure and swelling is reduced.
By similar mechanism the addition of alkali brings about an increase in
internal pressure and the resulting swelling due to the formation of a gelatin-
ate, until the pH reaches a value of 10. An excess of alkali again decreases the
amount of water absorbed.
The swelling of gelatin can be reduced by adding a neutral salt (sodium
chloride for example): this gives an increase of external osmotic pressure at
the same time as a possible reduction of the internal pressure, by reducing
the ionization coefficient of the gelatin salt. Sodium sulphate has a stronger
action than any of the other sodium salts; this property is used in high
temperature development.
257. Gelatin gels

The gelatin gels are distinguished for their hardness and their melting point;
the gelatins which are used for their preparation are usually classed as hard or
soft gelatins. The 'hard' types are made up of relatively unaltered materials
whilst in the 'soft' types the original substance has been attacked and hydro-
lyzed more strongly thus producing degradation products.
Solutions of hard gelatin therefore appear to contain substances of high
molecular weight, making up the gel, which gives them their mechanical
strength and their great affinity for foreign materials. This is not, however,
GELATIN 273
4>
the opinion of G. Stainsby< who maintains that the jelly strength is inde-
pendent of the molecular weight. In fact the stiffness does not increase after
a certain molecular weight is reached.
Gelatin gels are made up of two phases; one, solid, formed of a lattice of
joined micelles; the other liquid, which lubricates the lattice and keeps it soft
due to its osmotic pressure.
The lattice which has an oriented structure is made up of stacked simple
chains. When a gelatin solution is cooled, the least soluble isoelectric part
precipitates first, forming the skeleton of the lattice (organized period) by
lateral linking of chains.
The liquid phase is made up of the degradation products of gelatin and by
the calcium gelatinate which is always present in commercial gelatins. Con-
trary to the solid phase which has a large number of chains joined by cross
links (gel form), the liquid phase (sol form), is essentially made up of single
chains. From 35°C all the gelatin is converted into a sol. The intermediate
systems at various temperatures below 35°C can be detected by variations in
rotatory power which increases with the appearance of the gel form
T < 15°C gel form: (cxn) = 313°
T > 35°C sol form: (cxn) = 141°
It has been assumed that when a jelly is liquified, the amide groups
-CO-NH- (which are in the keto form) take up the enolic form -C =N -.
I
OH
A gelatin, precipitated with ammonium sulphate from its neutralized sodium
solution, does not give jellies.
High frequency treated gelatin will not gel. Substances such as urea and
guanidine also prevent gelling.
Melting point. This is the point of total conversion from the gel to the sol
form by rapid depolymerization, that is by rupture of the lateral links joining
the various strata.
The melting point is naturally higher with gelatins which are only slightly
hydrolyzed; it indicates the purest gelatins although it gives no indication of
their chemical composition, nor is it an adequate criterion of their photo-
graphic quality. It is generally about 32°C at 6% with solidifying temperature
around zzoc at the same concentration.
The melting point is highest at the isoelectric point (4·7-5). We have seen
that the swelling is, on the contrary, lowest at this same point; conversely
there is a melting point minimum (falling suddenly) corresponding to the
maximum swelling at pH 2·7. A second weak maximum occurs at about pH 2.
We would finally note that between the isoelectric point and pH 8 (slightly
alkaline) the melting point varies only slightly; this is an important matter in
the use of commercial gelatin.
The melting point is reduced by adding potassium salts, <5 > and in order of
increasing effectiveness (Hofmeister series) are: sulphate < chloride <
bromide < nitrate < iodide < thiocyanate.
The melting point is raised by adding to the gelatin solution small quantities
of aluminium salts (as alum) or chromium salts (chrome alum). At the same
time the viscosity increases but only when the solutions are relatively concen-
trated.
The Al and Cr salts produce complex hydrated ions which form co-ordina-
tion complexes with the gelatin. The reaction is slow (several days). When the
carboxyl groups are esterified, the metal cannot form a complex which only
seems to take place at a single point in each chain. At the isoelectric point the
links are intramolecular as the chains are coiled up (para. 139).
CHEMICAL CONSTITUTION OF GELATIN

The amino acids are the basis of the proteins, especially gelatin. These
simple groups are joined in long polypeptide chains which themselves polymer-
ize to form the simple proteins. At a higher degree of polymerization, frequently
together with other groups, the natural complex proteins are obtained.
258. The amino acids

The amino acids< 6 > are compounds which possess two functions: the amino
function -NH 2 and the acid -CO.OH. As the amino function is basic
the amino acids are amphoteric compounds, both basic and acid.
The simplest member of the series is glycocol or glycine or aminoethanoic
acid NH 2 -CH 2 - CO.OH which crystallizes in clinorhombic prisms,
melting point 236°C.
In the role of acid, glycocol can give metallic salts such as silver glyco-
collate NH 2 - CH 2 - CO.OAg, and in the role of base, salts of glycocol with
other acids, for example glycocol sulphate.
Among the other members of the series those usually encountered are
alanine CH 3 -CH.(NH 2)-CO.OH (a derivative of propionic acid
CH 3 -CH 2 -CO.OH), leucine CH 3 - (CH 2) 3 -CH.(NH 2)-CO.OH,
isoleucine, serine OH.CH 2 -CH(NH 2)-CO.OH or amino-gly ceric acid,
valine, etc.
The molecule can have an acid group and two amino groups such as lysine
and arginine or, on the other hand, two acid groups and one amino group, for
example aspartic acid OH.CO-CH(NH 2)-CH 2 -CO.OH and glutamic
acid OH.CO-CH(NH 2)-(CH 2) 2 -CO.OH.
An amino acid containing a cyclic nucleus generally has a constitution
similar to that of phenyl-alanine C 6H 5 -CH 2 -CH(NH 2 )-CO.OH.
Tyrosine is the corresponding phenol: OH.C 6H 4 -CH 2 -CH(NH 2) -
CO.OH.
If the nucleus is heterocyclic we have tryptophane, histidine, proline and
oxyproline.
Finally there are sulphur derivatives such as cystine with the formula
OH.CO-CH(NH 2)-CH 2-S-S-CH 2 -CH(NH 2)-CO.OH
GELATIN 275
Properties
The amino acids are crystalline solids which are generally soluble in water but in-
soluble in ether and the benzene hydrocarbons. They decompose when melted.
When distilled dry in the presence of baryta, they are split into an amine and carbon
dioxide. Dehydrated, 2 mols. combine together to form a diketopiperazine or double
cyclic amide. When suspended in acetyl chloride and in the presence of phosphorus
pentachloride, they give the hydrochlorides of the corresponding acid chlorides.
RCH-(CO . Cl)-NH, . HCI.
Preparation : the simple amino acids can be prepared by reacting ammonia m
alcoholic solution on the corresponding chloracid, for example:
Cl. CH 2-CO.OH + 2NH 3 = NH 2 • CH 2-CO.OH + NH Cl 4
chloracetic acid ammonia glycocol ammonium
chloride
They are also obtained by the action of ammonium cyanide on the aldehydes and
ketones, by reduction of the nitro or nitroso acids with aluminium amalgam in ether,
or reduction of the cyano acids. Other methods consist of attaching NH 3 to ethylene
acids, oxidation of amino ketones, etc.
Usually the amino acids are prepared by the hydrolysis of animal or vegetable
proteins: gelatin, albumen, gluten, etc. Thus gelatin treated with boiling dilute
sulphuric acid gives, on neutralizing with calcium carbonate and evaporation of the
filtered liquid, crystalline glycocol. Similar treatment decomposes gluten to glutamic
acid, leucine and tyrosine.
259. The peptides

The peptides are polyamides produced by the union of 2 or more ammo acid
molecules following the general scheme:
R R'
I I
NH 2-CH-CO.OH + NH 2-CH-CO.OH -+
amino- amino-
acid acid
R R1
I I
NH 2-CH-CO.NH-CH-CO.OH + H .O
p eptide water
The group CO . NH, which is the amide function, is repeated each time a new
molecule is added to the peptide chain. This always has the basic and acidic charac-
teristics due to the terminal NH • and CO.OH groups.
The peptides are usually soluble in water, acids and alkalis, insoluble in alcohol,
decomposed above 200°C. When treated with hydrochloric acid they are hydrolyzed
with the regeneration of the amino acids which make them up.
Synthesis (a) The union of two or more molecules of amino acids is a dehydration
reaction: NH 2 and CO.OH are condensed to CO.NH with the elimination of a
molecule of water. This dehydration can be carried out with phosphorus pentoxide
P 2 0 5 or by heating to a high temperature. In nature the peptides are produced by
means of the diastases acting on the amino-acids.
(b) The ex-halogenated acid chlorides react with the ex-amino acids to give ex-halogena-
ted amino acids, which by the action of ammonia are converted to dipeptides. A di-
peptide which is in turn reacted with an ex-halogenated acid chloride, then with
ammonia, produces a tripeptide, and so on. Examples: chloracetyl chloride reacts
with glycocol following the scheme:
ClCH 2-CO.Cl + NH.-CH.-CO.OH =
= Cl.CH 2- CO.NH- CH 2-CO.OH + HCI.
By the action of ammonia the <X-halogenated amino acids produced gives glycocol
dipeptide
Cl.CH 2-CO.NH-CH.-CO.OH + 2NH 3 -+
-+ NH.-CH.-CO.NH-CH.-CO.OH + NH,Cl
Similarly bromo-isocaproylglycinic acid chloride C 4 H.-CH.Br-CO.NH-
-CH 2-CO.Cl is converted to bromoisocaproylglycyl-glycine C,H.-CH.Br-
-CO.NH-CH,-CO.NH-CH,-CO.OH which treated with ammonia gives
leucylglycylglycine C 4 H 9-CH.NH .-CO.NH-CH .-CO.NH-CH 2-CO.OH.
(c) The methyl ester of a simple peptide is first prepared such as diglycylglycine
ester NH 2-CH .-CO.NH-CH .-CO.NH-CH 2-CO.CH 3 •
On heating, this polymerizes to pentaglycylglycinic ester NH 2-CH 2-CO
(NH.CH 2 .CO),NH-CH 2-CO.CH 3 •
(d) Glutamic acid OH.CO-CH(NH 2 )-CH,-CH,-CO.OH reacts with the
azolactone of acetamino-cinnamic acid C 6H 6-CH = C(NH.CO.CH 3)-CO.OH
in the presence of acetone and caustic soda: acetamino-cinnamoyl-glutamic acid is
formed
CH 3-CO.NH-C-CO.NH-CH-CO.OH
II I
C 6 H 5-CH CH 2-CH,-CO.OH
which can be reduced in the presence of a catalyst (palladium) to N-acetylphenyl-
alanylglutamic acid.
The peptides are the polymers of the <X or 2-amino acids. They have the general
formula NH 2-CH(R')-CO.NH-CH(R2)-CO.NH- . . . . CH(R")-CO.OH.
It is interesting to compare with these the polyamide resins obtained from the acids
with an amino group with the seven to eighteen positions such as 10-aminodecanoic
NH 2-(CH 2).-CO.OH :
-NH-(CH .) n-CO.NH-(CH .) n-CO.NH-(CH .) n-CO-
and with the polyamide resins similar to nylon obtained by condensing a diacid
(adipic acid) and a diamine (hexamethylene-diamine) in m-cresol.
-NH-(CH .) n-NH.CO-(CH .) n-CO.NH-(CH ,) n-NH-
260. The proteins

The proteins are nitrogenous compounds which are produced from the complex
polymerization of the peptides. We have seen that the latter are polyamides in long
chains whose terminal groups are amino and acid respectively.
The nature of the amino-acids from which the peptides are formed is very varied,
and this gives an infinite number of combinations.
The proteins are made of a very large number of oriented or coiled peptide chains
which are frequently linked together by secondary valencies linking certain -CO- of
one chain to the -NH- of another chain. Such complex systems result in col-
loidal micelles. The degree of polymerization, that is the length of the chains and their
number, influence the properties of the proteins; these are also dependent on the
number of cross-links and their stability. X-ray examination enables the structure of
the reseau to be deduced as with silk fibres.
The proteins are divided into two main groups: the holoproteins essentially made
up of amino-acids for example, the albumens, globulins and protamines; the hetero-
proteins resulting from the union of peptides with other groups such as nucleoproteins,
glycoproteins, phosphoproteins. Natural proteins are, however, usually mixtures of
various types.
The proteins are also classified as linear proteins and globular proteins (globulines).
GELATIN 277
The linear proteins have the simple or multiple chain structure molecule; they are
either soluble in water at various temperatures such as gelatin, fibrinogene and sericine,
or insoluble due to the presence of extra links as in the case of ossein (or collagen), silk
fibroine, and keratine (with sulphur links - S-S- ).
The globular proteins are made up of linked cyclic or globular nuclei. These globules
frequently show no aggregation force because of the absence of negative groups on
their surface, as with albumen and haemoglobin. They have, on the contrary, a tendency
to aggregate with casein and the phosphoproteins, due to the presence of superficial
positive and negative groups.
The globulines can be represented by structural formulae similar to the following
in which the characteristic nucleus of diketopiperazine is found:
CO-NH
I \
RCH CHR
\ N-C.OH
I \N -
\N- C.OH
I \N-C.OH
I
RCH
I \CHR I
RCH
\CHR
\ I \ I
CO-NH CO-NH
261. Hydrolysis of gelatin

When proteins are treated with an acid, a base or a diastase, they are hydro-
lized giving the amino-acids from which they are made. If a controlled action
is carried out, only partial degradation occurs with the formation of peptides
with lower and lower molecular weight.
In practice, hydrolysis is carried out with boiling hydrochloric acid, warm
baryta or lime water or with bacterial, fungous, or pancreatic diastases at
55°C and a pH of 6·5-7 (for gelatin). In the case of progressive hydrolysis,
the reaction is carried out with the reagents sufficiently diluted or at a suffi-
ciently low temperature to enable the different stages to be readily controlled.
The viscosity gradually drops at a fixed pH and concentration as the depolari-
zation or degradation progresses.
The amino acids are then separated chromatographically with a column or
on paper, identified with special reactions and estimated colorimetrically. <7 >
The choice of solvent is very important: Clayton and Strong used a mixture
of 75 volumes of methyl ethyl ketone, 25 volumes propionic acid and 30
volumes of water. <8 > The separation can also be carried out with an ion
exchanger after preparing the dinitrophenyl derivative following the tech-
nique of Schroeder, Kay, Le Geth Honnen and Green. <9 > Turner and
Schmerzler identified the terminal groups of the peptides chromatographically
after treatment with acetic anhydride and pyridine. <10 > For the colour reac-
tions Muting<11 > recommends the use of sodium-1 : 2-naphthoquinone-4-
sulphonate which, on filter paper, gives characteristic colorations with

25 amino acids.
High-voltage electrophoresis (10,000 V) is another method for separating
amino-acids. <11 bJ
The hydrolysis and separation of the amino acids of gelatin is, however, a
very critical task, and even now we have only an approximate idea of the
proportion of the various elements, the figures varying somewhat between
the different workers. The following list shows the approximate proportions
of the amino acids compared to the lowest values found by Neuman (Arch .
of Biochem., 1949, 24, 289).
A verage value Neuman

Glycocol 26 % 26 %
Proline 15 % 15 %
Hydroxyproline 14% 14·1 %
Glutamic acid 8% 10·2%
Aspartic acid 4·5 % 5·5 %
Alanine 6·5 % 8·7 %
Phenylanaline 1·8 % 2·2 %
Argenine 6·5 % 8·6 %
Lysine 4·5 % 4·1 %
Oxylysine 0·8 % 1%
Serine 2·5 % 3·2 %
Leucine 2·3 % 3·2%
Valine 1·8 % 2·5 %
Threonine 1·8% 1·9%
Histidine 0·8% 0·6 %
Tyrosine 1·1 % 0·5 %
Methionine 0·8% 0·6 %
We can easily see that the major part of gelatin is made up of glycocol
NH 2 -CH 2 - CO.OH and proline or hydroxyproline.
HO-CH-CH 2
I I
CH2 CH-COOH
'NH/
proline h ydroxyproline
By electrochemical reduction of gelatin, piperazines are formed <12 > which

according to Koperina and Gavrilov provide the diketopiperazine rings.
High frequency sound has a destructive action with the liberation of ammonia
and aldehydes. <13 > At the same time the viscosity drops and the gelling
property disappears. It is principally the protein nucleus which is ruptured.
GELATIN 279
262. Molecular weight of gelatin
Commercial gelatin is a mixture of many gelatins of varying molecular weight
from 15,000 to 250,000. The distribution of these component gelatins is
obviously dependent on the origin of the raw materials and the treatment
which they have received. The least degraded commercial gelatins have a
relatively high molecular weight, the average being about 55,000.
Fractionation of a mixture of gelatins by fractional dissolution is unsatis-
factory; it is better to work by gradual precipitation for which a dispersing
agent such as urea can be used. Some compounds like sodium cetyl sulphate
can form addition complexes which are easier to separate. Another method
is to precipitate the gelatin with alcohol (coacervation). <14 > The addition of
alcohol brings about separation into two layers; the lower one containing a
large amount of high molecular weight material which is refractionated.
Measurement of molecular weight. This can be done by one of the five
following methods.
(a) Estimation of the terminal groups chromatographically after reacting
with fluorodinitrobenzene and hydrolysis (see Court: Biochem. Jl., 1954,
58, 70).
(b) Ultra centrifuging: mainly applicable to degraded gelatins.
(c) Determination of osmotic pressure. The gelatin is first dissolved in a
salt solution, in a solution of urea or in anhydrous m-cresol (see: Pouradier
and Venet:Jl. Chim. Phys., 1950,47, 11).
(d) Surface tension differences using surface active agents (see: Guastalla:
Cahiers de Physique, 1943, 13, 5).
(e) Diffusion of light (see: Signer and Mosimann: Helv. Chim. Acta.,
1941, 24, 1058).
263. Structure of gelatin

Thin, dry gelatin films have a two-dimensional crystalline structure which
gives them anisotropic characteristics. <1 5 > The plane of the axes is perpen-
dicular to the plane of the gelatin layer and is the direction of maximum
elasticity.
X-ray study of the structure of gelatin shows that the peptides chains are
made up of 288 amino-acid groups 0·29 mft apart giving a total chain length
of 83·5 mft. <16 > Huggins has suggested that the links are arranged in a zig-zag
pattern with a gly cocol molecule every third group, a proline or hydroxyproline
molecule, the remainder being divided between the other amino-acids:
CH2 CH-OH
/ ~
CH2 ~CH2 CH2 CH2
l I I I
N-CH CH 2 NH N-CH
CO
/ ' /
CO-NH
, / ,
CO CH-CO
/
CO-
'
R '
Each gelatin molecular chain is, furthermore, turned-back on itself when it

is at the isoelectric point. It opens up away, from the isoelectric point. The
measurements of optical rotation<18 > have confirmed this mechanism below
36°C. It should be noted, however, that other polypeptides, natural and syn-
thetic, also have the folded and open forms. The infra-red spectra of gelatin,
however, are sufficiently varied <19 > to suggest a particular degree of folding
which is also found in the parent collagen.
Recent work by Huggins<20 > has shown that the polypeptide chain of
collagen is rolled in a spiral: each 2·86 mfL spiral having ten groups of three
radicals in the order
R R'R" . R R' R"
where R" represents proline, hydroxyproline, aspartic acid or glutamic acid;
R R' representing glycocol and another amino acid. Furthermore, the CO
and NH groups produce, by linking -CO ... NH-, 8-membered cyclic
rings.
264. Conversion of the collagen to gelatin

Gelatin results from conversion of the collagen which makes up the cellular
material of the skin and bones (ossein). It is extracted by hydrolyzing the
collagen, either with alkali (liming), with acid, with a liquefying agent such as
potassium thiocyanate, urea, or with pepsin digestion. It is always finished
with cooking, which by hydration separates the gelatin formed during
hydrolysis.
Gelatin is formed by rupture of the amide cross linkages which cyclise at the
same time. Furthermore, some groups are destroyed first by alkali, for ex-
ample those of guanidine and arginine. These groups-cx-amino, imidazol,
carboxyl, guanidine- can be evaluated by a technique of Kenchington and
Ward.<20 b>
Collagen is formed by several constituents and several phases. The
fibres are minute rigid rods 1·1 mfL diameter (5 to 7 mfL for other observers),
290 mfL long and having a molecular weight of 300,000 (20°C); they are called
tropocollagen. From collagen, 10 to 15 % of a crystallized protein existing in
all living tissues-the procollagen-can be extracted. The substance of the
fibres, which remains, is collastromin. <21 >
Collagen is water repellent but after treatment becomes capable of absorb-
ing 35 % of its weight of water by hydrogen links.
The structure of gelatin is therefore determined by the method of hydrolysis
(in the case of lime process). It is here that the variations in the isoelectric
point occur.
265. Photographic gelatin

Gelatin, as we have seen, is made up of a complex mixture of many simple
gelatins of different molecular weights, together with degradation products
and various animal impurities. These secondary compounds have, from the
GELATIN 281
photographic point of view, as much importance as the structure of the gelatin
itself for they have considerable influence on the properties of the resulting
emulsions.
The properties of a photographic gelatin depend not only on the treatment
received during manufacture but also on the type and origin of the starting
materials: the breed and age of the animals which provide the skin or the
bones, their food, the parts used, all influence the final chemical constitution.
It is therefore understandable that the preparation of two absolutely identical
batches of gelatin is practically impossible.
It is difficult to classify photographic gelatins as they have so many properties.
The physical characteristics, especially the viscosity, play an important role,
but are not adequate criteria for use. An arbitrary classification based on the
redox potential<22 ) can be made but this method although useful cannot give
a full picture of the state of the gelatin.
The following groups of substances contained by gelatin are of interest to
the photographic chemist.
(a) Ripening retarders.
(b) Sulphur sensitizers.
(c) Desensitizers, contrast modifiers.
(d) Ripening accelerators.
(e) Aldehydes.
(f) Sugars and carbohydrates.
(g) Fog inhibitors.
(h) Inorganic impurities.
Protein impurities are very numerous as the skin and bones are usually
accompanied by flesh, nerve fibres, tendons, cartileges and blood. The
impurities are, however, not well known as usually only traces are present.
Finally, the possible presence of bacteria should be noted. <22b)
266. Ripening retarders

In some gelatins there are substances which retard the ripening of photo-
graphic emulsions to a greater or less degree, that is, they prevent the growth
of the halide grains on heating. The retarding power of egg albumen and lead
salts has been known for some time, but it was Steigmann who first drew
attention to the retarding power of gelatin, and disclosed a list of artificial
retarders. <23 )
Among the natural retarders in order of increasing activity are: histidine,
arginine, methionine, cystine, cysteine and glutathion. Cystine, which is
present in gelatin to the extent of 0·1- 0 ·2%, is about thirty times as active as
methionine and 100 times as active as histidine. The cystine comes from
keratine or the interfibrous protein. The amount of methionine is from 0 · 8-1 % ;
it can be recognized after stirring its acid solution (pH 3·2- 5·5) with silver
chloride; <24 ) the filtrate which has dissolved a little halide reacts with Feigl's
reagent. <25 ) In basic solution, the silver chloride is dissolved by other amino
acids.
Artificial retarders. Nucleic acid contains no sulphur, its sodium salt is

marketed as Inhibitor SN by P.A.C. Chemicals. Egg albumen is also used. <26 >
Among the other compounds which have retarding properties are thio-
glycollic acid, 2-mercaptobenziminazole, 2-mt;!rcaptobenzthiazole, ethyl thio-
carbamate, benzotriazole, the indazoles, phenyliodium salts, etc.
/,CH
# '\
N NH NH 2
I I I Histidine
CH=C -CH 2 -CH-CO.OH
Arginine
Methionine
Cystine
Cysteine
Glutathion
Cadmium and thorium salts, and to a less extent, lithium and lead salts are
also ripening retarders.
Lime process hide gelatins are usually rich in retarders, but not acid process
gelatins. Bone gelatins are poor in them. The retarders can be eliminated in
several ways as we shall see when gelatin manufacture is considered. Gelatins
rich in ripening retarders are particularly necessary for the preparation of
contrasty positive emulsions, especially chloride ones.
GELATIN 283
The retarders in gelatin originate from certain collagen polypeptides which
are hydrolyzed by liming, these polypeptides being mainly present in the
hides. Part of the inhibiting power is also due to imino groups as in proline
and arginine.
To explain the retarding mechanism, the hypothesis has been put forward
that the silver bromide is attached to gelatin via the imino groups and the
peripheral Ag ions. Crystal growth is therefore retarded. It is also thought
that the action of the imino groups is due to the presence of labile hydrogen.
This action varies with the pH. Compounds having no imino group also form
silver complexes similarly on the crystal surface which, by diminishing the Ag+
concentration, slow down ripening. These compounds can be broken down
by sulphur sensitizers.
The retarders can bring about desensitization of emulsions. Thus cystine,
in the presence of a sensitizer, loses sulphur to give the desensitizer cysteine,
and H 2 S, producing fog.
267. Measurement of the retarding power

A photographic emulsion, precipitated and ripened, becomes more and more
opalescent (as a function of the time and temperature) due to the growth of its
crystals. With the same time and temperature, an inert gelatin enables the
emulsion to ripen more rapidly than a retarding gelatin. Measurement of the
turbidity of the test emulsion indicates the modifying power of the gelatin
under test compared with the standard gelatin (Steigmann's method).
The test emulsion is often made with silver chloride as with the Amman-
Brass method. <27 > It is preferable to work also with silver bromide emulsions
which do not always react towards retarders in the same way as chloride.
The following formula given by Amman-Brass uses cadmium chloride to give a
more obvious minimum to the curves.
Stock { Distilled water to 1000 cc
soln. Sodium chloride 35 g
Cadmium chloride CdCI 2 2H 2 0 12 g
Soln. 1 { Distilled water 120-x cc
at n oc Gelatin xg
. Stock soln. 10 cc
Soln. 2 17 g per litre soln. of silver nitrate 20 cc
at 77°C
Eight different emulsions are prepared with the amount of gelatin x, varying from
0·75 to 15 g. Pour solution 2 (silver) into solution 1 (salts) rapidly and ripen for 32
minutes. The emulsions contain respectively 0·5, 1, 2, 3, 4, 6, 8 and 10% of gelatin.
5 cc samples taken at equal intervals are poured into 145 cc cold water and the
turbidity of the resulting liquid is measured. <2 8> Then the curves of turbidity as a func-
tion of the gelatin concentration are drawn, each curve corresponding to one ripening time.
This gives a turbidity solid formed by a group of curves which shows the characteristics
of the gelatin.
A variation has been disclosed by Evva :<••> to a solution of 5 g of gelatin in 25 cc
water add 10 cc of a solution of (NaCI 10 g + CdCI 2 • 2H 2 0 3 ·5 g + H 2 S04 (normal)
125 cc, water to 1000 cc) then 10 cc of 17 g per litre silver nitrate. Ripen for 1, 2, 4 and
8 minutes at 75°C and take 1 cc of each and dilute to 200 cc.
Inert gelatins give curves with horizontal straight lines, almost parallel and des-
cending slightly but the interpretation is complicated in the case of active gelatins as
sulphur sensitizers and contrast modifiers interfere, also due to protective action which
gives families of curves of complex shape. The sensitizers lead to the formation of
characteristic depressions marking a minimum of turbidity compared with an optimum
concentration. The minimum is even more accentuated when there is little retarder.
Gelatins rich in retarders and with an average sensitizer content give a family of
undulating curves which drop suddenly at high concentration to a minimum; others,
very active but poor in retarders give a family of well-spaced lines marked by a mini-
mum whose location differs with the ripening time. Finally, another system of classi-
fication uses the turbidity measured as a function of the ripening time, each curve
corresponding to a different gelatin concentration.
To get an even more complete picture of the characteristics of a gelatin it is neces-
sary to work not only with the gelatin as supplied but with the gelatin washed, and
filtered through active charcoal or magnesium silicate.(3°) The latter especially only
eliminates the true protein retarders which enables a decision to be made as to whether
the modifying action of the tested gelatin is due to a pseudo retarder such as
thiazolidine or the polythionates. A slowing down of ripening followed by speeding
up often indicates the presence of a thiosulphate.
The presence of protein retarders shown by the turbidity test with gelatino-silver
chloride must be confirmed with a silver sulphite test described below.
If this test is negative when the turbidity test is positive the presence of ripening
accelerators is indicated.( 3 'l
Silver sulphite retarder test. This test can be carried out by heating a 10% gelatin
solution with 20 % of 0·4% sulphurous acid and 20 % ammoniacal silver nitrate. It is
easier to prepare the following reagent:
17 g per litre silver nitrate soln. 30 cc
Sodium sulphite anh. 2g
Water to 150 cc
Add 2 cc of the fresh reagent to 10 cc of 10% gelatin solution. Heat the tube for
5 mins. in boiling water. Cool rapidly and note the blackening rate of the liquid
(reduced colloidal silver). In the absence of activators, the retarders prevent the solu-
tion from blackening too rapidly.
268. Gelatin sulphur sensitizers

By examining the lime liquors produced in the manufacture of gelatin,
Sheppard was able to isolate an active substance, allyl isothiocyanate, a com-
pound contained in mustc>.rd oil. This compound was undoubtedly a degrada-
tion product of more complex molecules.
It is certain that the natural active substances in gelatin are sulphur com-
pounds and that their concentration is higher with shorter liming. When
lime attacks collagen the main products are methionine, cysteine and cystine,
all of which, as we have seen, are retarders: methionine CH 3 -S-CH 2-
-CH(NH2)-COOH; cystine COOH-(NH 2)CH- CH 2-S-S-CH 2-
-CH(NH2)-COOH; cysteine SH-CH 2-CH(NH 2)-COOH.
It is believed that the group R-SH is characteristic of sensitizers whilst the
group R-S-S-R' desensitizes. This is the case with cystine, which de-
sensitizes emulsions and retards ripening. However, cysteine also desensitizes,
and even, in some cases, appears to be the cause of desensitizing by cystine,
of which it is a half.
GELATIN 285
We can also detect, in an active gelatin, active sulphur and labile sulphur,
the latter being sulphur which will combine readily with silver to give silver
sulphide. The presence of labile sulphur is not in itself a sufficient guide to
the sensitizing activity, as the retarders and fogging agents can also contain
appreciable amounts. Furthermore, the thiosulphates and the polythionates,
which some workers say are the best sensitizers, contain no labile sulphur.
Sulphur content. A photographic gelatin poor in sulphur contains at least
4 mg per kilo whilst a sulphur rich gelatin can contain 30- 75 mg per kilo.
What are the sulphur compounds, contained in gelatin, which are actually
active? This is a very controversial question. For instance, there is a trend to
favour the thiosulphates and the thionates preferred by Steigmann. Wood has
shown, with his chromatographic work<32 > that the sensitizer is an inorganic
anion which is soluble in water, or which can be converted to the soluble form
by heating in alkaline medium. Wood was able to confirm this work by
electrophoresis of gelatin extracts<33 l and concluded that the active sulphur
compounds are the thiosulphates and the tetrathionates.
Na 2S20 3 Na S 0
2 4 6
Sodium t hiosulphate Sodium tetrathionate
The thiosulphates and thionates originate in the cystine (and consequently

keratine and the mucoproteins) hydrolyzed by bases, and in the compounds
used for depilation of the skin. One could think together with Linderstrom,
Lang and Jacobsen that the thiazolidine rings in the animal proteins may be
opened by hydrolysis to give mercaptans RSH, which are then converted.
Gelatins of German origin have been reputed to be artificially activated
with sodium and ammonium thiosulphate, and even with ammonium poly-
sulphide (although the latter is not a sensitizer, but a fogging agent). The
amount of crystalline thiosulphate added to an inert gelatin is 40 to 300 mg
per kilo. Another method which has been disclosed is to heat the gelatin
solution with colloidal sulphur. <3 4 >
We would add that it is possible that the addition of thiosulphate to an
inert gelatin before emulsion preparation can give interesting results, but the
addition to a high-speed emulsion, during preparation, on the contrary
generally produces desensitizing and results in fog. The addition of thio-
sulphates can only give a speed increase with certain slow emulsions.
269. Estimation of sulphur sensitizers

The low molecular weight amino-acids are soluble in a saturated solution of
sodium or ammonium thiosulphate. The thiosulphates and trithionates can
be separated by absorption on magnesium silicate.
Feigl's reaction. The estimation of the active sulphur with Feigl's reagent is
carried out in a graduated test tube with a bent capillary tube. Ten cc of 10%
gelatin solution is put in it with 2 cc of 1% borax and 5 cc Feigl's reagent
with the formula
N /10 iodine 100 cc
Sodium nitride 2g
The tube is filled with water and is closed with the cork fitted with the
capillary tube. The whole is upended in the water-bath at 65°C. Nitrogen is
evolved. After heating for one hour the volume of gas is measured, 0·5 cc
corresponding to one Feigl unit, and standards are made using known
amounts of thiosulphate.
The Feigl reaction is sensitive to pH. Furthermore, it cannot be used with
gelatins containing hydrogen peroxide. <37 >
Thiosulphate test. <37 > 0·1 g thionine is dissolved in 50 cc ethylene glycol.
One cc of this stock solution is diluted to 100 cc with distilled water. One cc
of the dilute solution is added to 3 cc of the solution to be tested (filtered
through activated carbon and concentrated). 0·4 cc 5N sulphuric acid is
added and the tube is heated in boiling water for 8 mins. and cooled in running
water for 20 mins. If the thiosulphate content is very low the solution turns
from violet to blue. With a higher concentration than 1/40,000 gjmol. it is
decolorized. Amounts of thiocarbamide fifty times greater than this also
decolorize the solution, but without first turning it blue.
Ammoniacal silver nitrate reaction. <38 > When a gelatin solution is heated
with ammoniacal silver nitrate, it turns brown. The intensity of the colour
enables the active sulphur content to be estimated. Fifty cc of 6% ammoniacal
silver nitrate is added to 50 cc of 2% gelatin at 40°C in 15 sees. with stirring.
The density of the mixture is measured over 100 hours and Dis plotted against
time. Ripening retarders slow down the darkening during the first 50 hours,
but the density is independent of the gelatin concentration up to 30 hours.
Potentiometric titration with silver nitrate. A silver electrode is used to-
gether with a calomel electrode. The curve potential/nitrate volume is drawn.
Active gelatins give an inflection point.
Estimation of labile sulphur. 'Labile sulphur' is that which combines directly
with silver. It is difficult to assess the importance of this test if the natural
sensitizers are thiosulphates and thionates whose sulphur is not labile, and
contrary to the work of many writers, Feigl's test does not give the labile
sulphur content of gelatin.
Vogel's reaction has been used to estimate the labile sulphur (formation of
lead sulphide with lead acetate in caustic solution), and another method is to
convert it to hydrogen sulphide by heating the gelatin with alkali, removing
the H 2 S in a current of nitrogen. <39 > The latter method has been used by
Sheppard and Hudson <40 > in particular, the hydrogen sulphide being esti-
mated colorimetrically with methylene blue.
Abribat< 41 > has worked out a simpler method, which is to digest the gelatin
solution with a known quantity of ammoniacal silver nitrate (as with the
method already given) and to back titrate the excess silver nitrate with a sul-
phur solution of thiourea or allylthiourea. The end point is determined
potentiometrically with a silver sulphide electrode, or with an opacimeter.
270. Desensitizers and contrast modifiers

Some compounds found in the liming liquors have the property of desensi-
tizing negative emulsions and increasing the contrast of positive ones
GELATIN 287
depending on the speed. <42 > They are also found in acid process hide gelatins
from which they can be extracted with saturated sodium sulphate solution.
A characteristic type of contrast controlling compound is thiazolidine-
4-carboxylic acid, which can result from the action of an aldehyde on cysteine.
/s,
CH 2 CH- R
I I
CH-NH
I
.CO.OH
Cysteine Aldehyde Thiazolidine-4
carboxylic acid
However, the retarders are themselves desensitizers.

Steigmann <43 > prepared the following derivatives, which are also fogging
agents:
(a) Seventy cc of 1 : 1000 solution of the sodium salt of cystine+ 30 cc
1 : 1000 glyoxal (pH 9) are heated to 90°C and the pH of the solution is then
adjusted to 4·5 by adding acetic acid.
Fifty to 100 cc of this solution per kg gelatin increases the contrast of silver
chloride emulsions and fogs emulsions containing gold salts.
(b) 0·6 g glucosamine hydrochloride and 0·2 g cysteine hydrochloride in
20 cc water (pH 12). Boil until the solution turns brown. Adjust to pH 4-5
with acetic acid, dilute to 40 cc, and 1 g active charcoal and filter. Use 10- 25 cc
per kg gelatin. The contrast modifying substances give a characteristic reac-
tion with palladium chloride.
271. Ripening accelerators

We have just seen that the aldehydes react with cysteine or cystine, giving
thiazolidines which can produce fog. Ripening accelerators can be present in
gelatin, and are also fogging agents. Their presence is indicated by an un-
usual susceptibility to traces of thiosulphate, giving a loss in speed together
with fog. As an artificial accelerator, the copper salt of pseudothiohydantoin is
very active. <44 >
Silver halide solvents: thiourea, thiocyanates, thiosulphates are ripening
accelerators.
A long list of ripening accelerators for polyvinyl alcohol emulsions has been
established by Oh-Yama and Futaki (para. 338).
272. Aldehydes
Photographic gelatin contains 3-15 g per kg of aldehydes. The aldehydes
result from the degradation of the mucopolysaccharides. The main aldehyde
seems to be similar to reductone CHOH = C. OH-CHO, <45 > which is itself
decomposed to formaldehyde and glycolaldehyde or a derivative (in acid pro~

cess, the formation of the latter negligible). Besides, the presence of an IX-acid
ketone, such as pyruvic acid, has been observed. ·
The gelatin aldehydes may be fixed to the chain by a labile link.
The mucopolysaccharides which provide the aldehydes are decomposed on
liming or by an enzyme, hyaluronidase, to proteins, amino sugars and glycur-
onic acid. Steigmann <4 6 l has shown the presence of hydroxymethyl-furfur-
aldehyde which is produced from the latter, themselves formed by bacterial
action on hyaluronic and chondroitine-sulphuric acids contained in the skin,
cartilage and certain bones.
Detection of the aldehydes. It is carried out with 2-thiobarbituric acid or
1 : 3 : 5-triphenyl-tetrazolium chloride.
Dissolve 1 g 2-thiobarbituric acid in 180 cc glacial acetic acid. Heat until
a slight yellow colour appears. <47 l Leave and add 20 cc water. For the test,
take 1 g powdered gelatin and 5 cc of reagent. Allow to swell for 15 mins. and
heat for 30 mins. in boiling water. A coloration from yellow-brown to red is
produced. The solution can be diluted to 20 cc, centrifuged, and the trans-
parency measured. <48 l It is compared with the colour given by a solution of
freshly distilled furfural in 10% acetic acid.
The colour formed by the action of 2-thiobarbituric acid on gelatin has five
absorption bands at 390, 455, 495, 535 and 555 mfL.
Triphenyltetrazolium chloride reagent. Dissolve 0·25 % in 0·4 % caustic
soda. <48 hl Take 5 cc for 0·5 g gelatin: a red colour is observed after one hour
at 20°C, if aldehydes are present.
The aldehydes can also be detected by Schift's test with fuchsine (water
500 cc, basic fuchsine 0·1 g, potassium metabisulphite 2 g, N hydrochloric
acid 8 cc, hydrosulphite 0 ·2 g): 0·5 g dry gelatin for 5 cc reagent-becomes
red after two hours, purple with pigskin gelatin.
For paper chromatography, with iodine treatment, see (48c).
273. Sugars and carbohydrates

Collagen contains more sugars and various carbohydrates than gelatin-
about 1%. These sugars are present as impurities and may cause the colour
of gelatin. They can be estimated colorimetrically after heating to 180°C in
acetic acid, or by reacting with orcinol. <49 l
Acid process gelatins contain more sugars and carbohydrates than lime
process ones.
Fats. Gelatin can contain several decigrams of fats per kilo. Extraction with
petroleum ether is ineffective, as part of the fat is present as calcium soaps.
The best method of extraction is that of Abribat. <49 b l This is to saponify the
fats and to liberate the corresponding acids. These are then removed by
adsorption on calcined alumina.
274. Fog inhibitors

Kameyana <50 l prepared gelatin extracts, starting with a wide variety of hides,
which had a pronounced anti-fogging action. He was able to concentrate the
GELATIN 289
active material, but could neither isolate nor identify it. However, it appeared
to be a nitrogenous substance, probably containing sulphur. The gelatins
which were richest in this material were obtained from calves and small
animals. A prolonged, but not excessive, liming increases the inhibiting
power, but it is reduced by washing and destroyed by excess acid. Treatment
with washing waters increases it. The active substance is stable between
pH 4· 7 and 6·8. It is completely absorbed by active charcoal in acid medium.
275. Gelatin examination

The gelatin to be studied is first treated with sodium sulphate to remove the
active agents: 100 g powdered gelatin is added to 300 cc of saturated sodium
sulphate at 55°C. After digesting for 20 mins., the solution is decanted, and
the gelatin is put into a press; the extract obtained is mixed with the decanted
solution. Two g magnesium silicate is added (if the gelatin is a lime process
one) and the extract is filtered. The following tests are then made:
(a) Add 3 cc palladous chloride reagent< 52> to 5 cc of the extract. Heat the tube for
5 mins. in boiling water, then add 2 cc 5N ammonia. These reactions can take place:
Dark brown precipitate (PdS): presence of thiosulphates and polythionates.
Pale yellow coloration: presence of cysteine and thiazolidines.
Slight brown coloration on prolonged heating after adding ammonia: presence of
thiazolidines only.
(b) Add 3 cc fuchsine reagent< 53> to 5 cc of the extract, then 2 cc of cold saturated
mercuric bromide solution:
Violet precipitate after more than two hours: traces of thiosulphates.
Purple to blue-violet coloration without mercuric bromide : presence of thiols, if
the solution is again decolorized with palladous chloride.
Silver nitrate-methylene blue test:< 54 >

Gelatin-10% soln. at 40°C 5 cc
Ammonia- ·880 + 3 vol. water 0·5 cc
Silver nitrate N/10 (17 g/1) 1 cc
Methylene blue 1 : 5,000 1 cc
Expose the solution to sunlight for 5-10 mins.
No decoloration: Inert gelatin containing 1/10 5-1/10 6 thiosulphate.
Decoloration: Inert gelatin.
Decoloration and formation of brown colloidal silver: active gelatin.
Ammoniacal silver nitrate test. The gelatin solution is heated for 30 mins. in the
boiling water bath after adding silver nitrate containing enough ammonia to redissolve
the precipitate.
Strong reduction of nitrate: gelatin has a tendency to fog.
Weak reduction of nitrate: contrasty gelatin.
276. Inorganic compounds in gelatin

Estimation of chlorides. The chlorides can be estimated by three principal methods:
(a) Burning, and estimating the Cl in the ash.
(b) Hydrolysis with hot concentrated nitric acid then precipitation with silver
nitrate (gravimetrically, nephelometrically or back-titration of excess silver).
(c) Precipitation with silver nitrate, then hydrolysis of the gelatin. <••> AgCl is dis-
solved in ammonia and titrated with a standard solution of thiourea.
290 PHOTOGRAPHIC CHEMI STRY
T est for nitrates.< ••) First prepare the following reagent: 1 g carbazol and 1·4 g
dimethylglyoxime in 100 cc hot isopropyl alcohol. Add 0 ·2 cc of reagent to a solution
of 3 cc concentrated hydrochloric acid and 0 ·5 cc of guanidine carbonate or arginine
hydrochloride, then five drops of the solution of gelatin to be tested. Heat for 20 mins.
in boiling water. Traces of nitrates are shown by a pale blue colour.
Conversely, the presence of arginine and guanidine can be checked the same
way.
Estimation of sulphur dioxide. The presence of sulphur dioxide, SO 2 , in gelatin
retards or prevents an ammoniacal solution of argentisulphite containing excess hypo
from turning brown. To 100 cc of 15% hypo add 20 cc of 10% ammoniacal silver
nitrate. Take 2 · 5 cc of this solution and add to 10 cc of 1 5% gelatin. Heat for 30
mins. in boiling water and observe for brown coloration.
To estimate the SO 2 , one of the three following methods can be used :
(a) Distillation of the SO 2 in the presence of chloroform, in a current of CO 2 • The
SO 2 is collected for an hour in water, and is estimated with iodine, permanganate or
excess hydrogen peroxide.< " l
(b) Put 75 cc water, 25 g gelatin and 25 cc dilute H 2 S04 in a flask with a long neck
with a right-angle bend and an opening in the bulb for steam. Connect the flask to a
conical flask via a condenser. Put 20 cc of water in the conical flask and steam distil
until 100 cc of distillate has been collected. Titrate with N / 20 caustic using methyl
orange.<••)
(c) Heath 15 g gelatin in 150 cc water with 2·5 cc phosphoric acid.The air is ex-
pelled with CO 2 • 100 cc of distillate is collected in a flask containing 12 ·5 cc N /20
iodine. Concentrate to 32 cc after adding 2 ·5 cc hydrochloric acid. The solution is
then filtered, brought to the boil and 5 cc N /5 barium chloride is added. The barium
sulphate is determined by the usual method.
Estimation of iron. Iron can be detected by coloration of p-phenylenediamine and
hydrogen peroxide in strongly acid solution.<' 9 l The same reaction in ammoniacal
solution indicates copper.
A colorimetric method is to treat the gelatin, previously dried at 110°C, with con-
centrated sulphuric acid and 30 % hydrogen peroxide. After the organic material is
decomposed it is taken up in hydrogen peroxide and excess potassium thiocyanate is
added. The colour is compared with that from a standard solution of ferric sul-
phate.<••)
Estimation of zinc, lead and copper. Zinc gives a red coloration with dithiazone (or
dimethylthiocarbazone) in chloroform solution which enables a colorimetric estimation
to be made with gelatin ash. Burning must not be carried out above 450 °C, and also,
if other metals are present they must be converted to complexes by extracting in the
presence of thiosulphate.<••l
A more accurate and simpler method of estimating zinc, copper and lead in gelatin
is to use a polarograph as worked out by Michel and Maron.<6 3 l Twenty-five g of
gelatin is ashed at 450°C, and the residue is dissolved in 5 cc of 6N . HCI. Distilled
water is added and the pH is b rought back to 2·5-3 (thymol blue indicator) with 4N
caustic potash. The solution is made up to SO cc and analysed for copper, lead and
zinc with the polarograph.
The method given by the British Standards Institute< ••) involves the precipitation
of the metals with ferrous sulphide. The lead is estimated colorimetrically as the sul-
phide; the zinc by precipitation with 8-hydroxyquinoline and copper as the diethyl-
dithiocarbamate or the pyridine complex.
Estimation of Ca, Ba, Al, M g and Ag in the ash is done by normal analytical m ethods .
The arsenic can be detected by spotting on mercuric bromide paper, developed in
potassium iodide. Its estimation is important for food gelatins.
GELATIN 291
MANUFACTURE OF PHOTOGRAPHIC GELATIN
277. Raw materials

Photographic gelatins are prepared from calf skin or bones. They have
different properties depending on the raw materials used in their manu-
facture.
To obtain pure, well-defined and consistent batches of gelatin selected parts
of skin and bone completely free from adhering flesh must always be used.
For obvious reasons these conditions are not always complied with and to
some extent, therefore, commercial gelatins are variable. This leads to diffi-
culties in preparing photographic emulsions of definite properties.
Hides. The hides used for preparing photographic gelatins are calf hides.
Kid, rabbit, dog, shark, whale and other skins have also been used or tried.
Usually the waste from the tanneries are used as raw materials; these are not
the best parts as they include the head, ears, hooves and certain parts of the
stomach. The cartilage must be removed as this is converted to chondrine, a
substance similar to gelatin but having an intense fogging action, and which
brings about the rapid coagulation of the latter with chrome alum.
The hair is removed from the tannery scraps with sodium sulphide
and chalk. This must be removed by washing, preferably slightly acid,
together with the sodium chloride used as a preservative by the slaughter-
house.
If the hides are fresh, it is better to remove the hair after pre-liming in
6° Be. milk of lime for a few days, followed by washing.
The selection of skins is still a purely empirical operation.
Bones. The bones come either from the slaughter-houses (red bones) or
ready prepared, and in large quantities from South America and India. The
Indian bones which are naturally cleaned and bleached are preferred. Another
source is the scraps from button manufacturers. Ten to twelve parts of bone
are needed for one part of gelatin.
Bones are mainly composed of ossein and tricalcium phosphate: 18%
ossein- more from calf head bones- and 71 % inorganic matter plus 8%
water. The inorganic matter is made up as follows:
Tricalcium phosphate 85 %
Calcium carbonate 10%
Magnesium phosphate 1·5 %
Calcium fluoride 0·3 %
Calcium chloride 0·2%
Other compounds 3%
The sorted bones are first crushed, degreased with trichlorethylene, sifted
to remove the tendons and scrubbed with water. They are then acidified in
3-6° Be. hydrochloric acid (for 2-3 weeks or more at 10-15°C) which dissolves
the tricalcium and monocalcium phosphates. The gradual demineralizing is
followed visually by examination of the texture of the material.
L
Acidification with sulphurous acid has the advantage of attacking the

ossein less.
The bones in which the ossein remains are washed in running water for
liming.
278. Liming
The washed skins and ossein are treated with milk of lime which hydrolyzes
the collagen and solubilizes the other materials, fats, albumens, mucoids,
elastine. The action of the lime is due not only to its alkalinity but also to the
activity of the Ca ions.
The skins are plunged into 4-8° Be. milk of lime for two days, then rinsed
in hatched for 3-8 weeks, at a temperature of 3- 12°C.
The bones are limed in vats in milk of lime, 0·8- 2° Be., which is frequently
renewed. At the end of the treatment it is reduced to 0·5° Be. The liming
time varies with the temperature and the concentration; it varies from 1-3
months.
The end of liming is judged by touch. A knife should readily pass through
ossein. A more precise method is to estimate the tyrosin, which is completely
extracted in the waters.
Liming is the most important stage in the manufacture of gelatin. It deter-
mines the structure of the gelatin. High temperatures must be avoided (maxi-
mum 12°C) as must too long a duration which can cause degradation which
produces fogging agents.
Pure gelatins for slow emulsions are preferably obtained at very low tempera-
tures (3- 5°C) and for a relatively short time, 2-4 weeks. Active gelatins for
fast emulsions are obtained between 5 and 12°C for 5-8 weeks depending on
the temperature. An optimum time must not, however, be exceeded as
beyond it there is a loss of sensitivity.
Samples must be removed at regular intervals and converted to gelatin
under fixed conditions.
Reduced liming. Preliminary scalding, by swelling the collagen and re-
moving certain cohesive forces or apolar links (called Vander Waals' forces),
enables liming to be shortened.
Another method used by Kind and Potnis< 66 l is to treat the collagen first
in a solution of 0·1 M calcium chloride for 14 hours. After 4 hours washing,
6 days liming is enough with 3° Be. milk of lime.
The yield decreases when the concentration of CaC1 2 is increased beyond
1·25 M.
279. Neutralization
The limed collagen is washed in running water and then treated in an acid
bath to neutralize and dissolve all the lime (to pH S-7). It ends with a final
wash in pure water.
The acid used can be hydrochloric, phosphoric or sulphurous. Concentration:
1- 2 % , average time 12-24 hours. The neutralization must be neither in-
complete nor exceeded.
GELATIN 293
280. Cooking
Only the cooking shows the chemical effect of liming. At its best it can be
considered as a physico-chemical hydration action.
Cooking must be carried out at a relatively low temperature to avoid
degradation by hydrolysis (rupture of the normal chains).
The mass is broken up and heated in water with agitation. The operation
is repeated four or five times giving extracts whose quality drops with succes-
sive extractions. Only the first three extracts are suitable for photographic
use. These extracts can be mixed but it is better to group them separately.
When the temperature of cooking is very low, only the readily hydrated,
slightly polymerized fractions are attacked which gives low melting point
gelatins.
1st extract at 60- 70°C 3 hrs. gelatin cone. 8%
Photographic 2nd , , 70- 80°C 3-i hrs.
gelatin ( 3rd , 80- 85°C 4 hrs.
4th ,, 85- 90°C 5 hrs.
Glue { 5th , 90-1 00°C (optional).
The pH is kept between 5 and 6 for the complete duration of cooking. Con-
centration is not necessary except for the glue which is evaporated at reduced
pressure. Similarly only the last extracts are clarified (by forming a precipitate
which carries down the impurities using albumen or aluminium sulphite and
lime salts).
Some manufacturers add, before or after cooking, a small quantity of

sulphurous acid as a preservative (15 1. of saturated solution for 500 kg
gelatin).
Filtration on a cellulose bed keeps back the ossein residues and the coag u-
lated substances, also traces of fat. The cellulose paste is regenerated by boil-
ing in an alkaline solution.
Gelification. The gelatin solution is set on an endless belt made of stainless
steel and dried on metal grids or cotton nets until a maximum moisture
content of 15% is reached. The jelly can also be noodled before drying.
Photographic gelatin is generally sold in small flakes produced when the
sheets are broken up, more rarely as a powder.
Many runs are mixed by the manufacturer to make batches of several tons.
281. Acid process gelatin

The hydrolysis of the collagen can be carried out just as well by acid treatment
as by basic treatment. Acid treatment has the great advantage of being much
faster. However, the properties of the gelatins produced in this way differ
greatly from those produced by liming, as they contain a large number of
intact amide groups. Furthermore, the free or liberated proteins are not dis-
solved and remain in the mass. The isoelectric point of acid processed gelatins
is at a pH between 7 and 9 instead of 5. With pigskin which is usually treated
this way the i.p. can reach 8·2. We have already noted that by greatly pro-
longing the acid treatment the i.p. can be reduced to 4·8.
Acid treatment of hides is carried out in 3% hydrochloric acid for 24 hours.
The excess acid is eliminated by washing and the gelatin is extracted by
cooking at a pH of about 4.
282. De-activation of gelatin

Gelatin is de-activated to make it inert from the photographic point of view,
that is, to eliminate or destroy the sulphur compounds, the retarders, and the
desensitizers or fogging agents. Many methods have been disclosed to do this.
The choice of the raw material is also important: gelatin prepared from hard
bones, with extended liming is naturally more inert than hide gelatin.
A. De-activation by prolonged washing, eliminates part of the sulphur
sensitizers and a small proportion of retarders. The action of washing is more
effective if the water is made slightly ammoniacal. Irregular results.
B. Treatment with active charcoal at a pH of 4--4·5, or better, with a mixture
of carbon and kieselguhr (Steigmann).
The sulphur sensitizers are eliminated together with the cysteine and the
thiazolidines; but the retarders still remain.
C. Treatment with inorganic absorbers, such as tricalcium phosphate
(retarders) or magnesium silicate (retarders and proteins). Activated alumina
removes the arsenic. (67 >
D. Extraction with sodium sulphate in a saturated solution or 10% sodium
chloride, of powdered gelatin. The retarding proteins dissolve. They can be
extracted, following Steigmann's process, by precipitation with 5 % zirconyl
basic sulphate (Zircotan N- Rohm and Haas). The precipitate is then
ground up in 1% soda solution which dissolves it.
E. Treatment with ion exchangers (cations plus anions). The gelatin is de-
mineralized and at the same time loses its retarders and some of the sensi-
tizers.
F. Oxidation treatment with hydrogen peroxide. (68 > It has also been pro-
posed to use calcium hypochlorite, bromine water( 69 > and sodium peroxide.
The excess oxidizing agent is destroyed with SO 2 . The after ripening of the
emulsion and the appearance of fog are retarded but not suppressed. The
writer has observed that, contrary to certain indications in the literature,
fogging substances are not destroyed by hydrogen peroxide.
G. De-activation with powdered metals, (70 > such as Ni, Co, Ph, Pt.
H . De-activation with silver salts. (7l) Silver nitrate is added to the gelatin
before emulsification to 'block' the sensitizers. The amount of silver nitrate
necessary is equal to ten times the weight of sulphur present in the gelatin.
Yellowish colloidal silver sulphide is formed. Amman-Brass has modified
the process using a silver chloride thread 0·07 mm in diameter. The tangled
mass of threads is kept for 30 mins. in the gelatin solution. The retarders are
not affected.
The mass of AgCl thread is obtained by the action of chlorine water on
silver thread.
GELATIN 295
283. Demineralization of gelatin
We have seen that gelatin solution can be demineralized by treatment with
an ion exchanger: Permutit or synthetic resins. <72 >
The calcium is substituted by sodium in the first case. All the cations are
replaced by hydrogen in the second.
The calcium can also be dissolved and eliminated by a 12-hour wash in
water containing carbon dioxide.
Cooling a 0·5 % gelatin solution to 15° flocculates the isoelectric fraction.
Mter centrifuging, calcium gelatinate remains in solution. The isoelectric
gelatin obtained in this way contains less than 0·026% ash.
1. Grignard R.: Quelques propri tes de Ia gelatine isoelectrique.

2. Bradbury and Martin: Sci. et Ind. Phot., 23(2), 108; Jopling D. W.: Research,
April1953, 29s-31s.
3. Meunier L.: La gelatine (Centre de Documentation Chimique, Paris).
4. Stainsby J.:Jl. Polym. Sci., Jan. 1954,325-335.
5. Meunier L.: loc. cit.
6. It takes place on the a-amino-acids in which the fractional groups are attached to
the same carbon atom.
7. Cramer F.: Paper Chromatography (Macmillan, 1954). Martin A.: Endeavour,
1947, 21. Bri.iggermann J and Drepper K.: Naturwiss., 1952, 301. See also Nature,
1950, 999; Anal. Chern., 1950, 1561. For the fractionation of protein mixtures:
Nitschmann H.: Chimia, 1953, 191-198. For the titration of sulphydryl groups:
Kolthoff, Stricks and Morren: Anal. Chern., 1954, 366-372; H erbert and Denson:
Anal. Chern., 1954, 440.
8. Clayton R. A. and Strong F . M.: Anal. Chern., 1954,1362.
9. J.A.C.S., 1954, 3556-3564.
10. Turner R. A. and Schmerzler G.: J.A.C.S., 1954, 949. See also Schlogl and
Wawersich: Naturwiss., 1954, 38.
11. Muting D.: Naturwiss., 1952, 303. See also: Oreskis and Saifer: Anal. Chern.,
May 1955, 27, 854-856. Ziselius: Angew-Chem., May 1955, 67, 245- 257.
11b. Werner G. and Westphal: Angew. Chern., May 1955, 67, 251- 256. Gross D.:
Nature, July 1955, 176, 72-73.
12. Koperina A. V. and Gavrilov N. I.: Zh. Obsh. Khimii, Sept. 1950, 1651-1654.
13. Khenokh M.A. and Lapinskaya E. M.: Dok. Ak. Nauk. S.S.S.R., Oct. 1951,
921- 924.
14. Pouradier J. and Abribat M.: Sci. et Ind. Phot., 1949, 444. B. Jurgensons used
acetone to titrate gelatin, using slight turbidity as the end point, Biochem. Z eits.,
1942, 325-334.
15, Szalay L. and Grasselly G.: Magyar Chern. Folyoirat, 1950, 325-327.
16. Astbury: Jl. Int. Soc. Leather. Tr. Chemists, 1940, 69.
17. Huggins M. L.: J. Chern. Phys., 1940, 598.
18. Robinson C. and Bott M . J .: Nature, 1951, 325.
19. Ambrose J. and Elliott A.: Proc. Roy. Soc., 1951, 206- 219.
20. Huggins M. L.: J.A.C.S., 1954, 4045 .
20b Kenchington and Ward: Biochem. Jl., 1954, 58, 202-207.
20c. Boedtker and Doty: J.A.C.S., 1955, 77, 248.
21. Orekhovich V. N., Tustanovskii A. A. and Plotnikova N . E.: Dokl. Ak. Nauk.
S.S.S.R., 1948, 837-839. Tustanovskii and others: Dokl. Ak. Nauk. S.S.S.R..
July 1954. 121-124.
296 PHOTOGRAPHIC CHE M ISTRY
22. Bicychin, Sehlik, Kovarik and Halamek: Sci. et Ind. Phot., 1954, 407. These
workers were prompted by the work of Kikuchi and Fejii (Sci. et Ind. Phot., 21,
100) and determined the redox potential using an auxiliary ferricyanide-ferro-
cyanide system. The gelatins for negative emulsions have potentials varying from
160-200 m V; those for chlorobromide emulsions from 173-200 m V and for
chloride emulsions, 144-200 mV.
22b. Steigmann, A . : Jl . Soc. Chern. Ind., 1944, 288 .
Skorodunov, L . N . : Kino. Photo. Khem. Prom., 1939,47; Sci. et Ind. Phot., 1946,
138.
23. Steigmann A.: Camera (Lucern), March and April 1926; Koll. Zeits., 1927,
400-402.
24. Steigmann A.: Jl. Soc. Chern. Ind., 1944, 316 ; Sci. et Ind. Phot., 1946, 166.
25 . 2-3 g sodium nitride in 100 cc N/10 iodine.
26. Egg albumen is a globuline whose different types include myosine, musculin,
globuline-fibrine, vitelline, edestine, etc.
27. Ammann-Brass H. : Sci. et Ind. Phot., 1948,401 and Dec. 1949.
28. Koseki Y.: Sci. et Ind. Phot., 1952, 444-after Jl. Soc. Sci. Phot. Japan, 1951 ,
50-55-described the mounting of a cell turbidity meter for this purpose.
29. Evva F . : Magyar Kem. Folyo., 1952, 43--48 or Sci. et Ind. Phot. , 1952, 36.
30. Steigmann A.: Sci. et Ind. Phot., 1949, 284.
31. Steigmann A.: Jl. Soc. Chern. Ind., 1942, 67.
32. Wood H . W.: Sci. et Ind. Phot., 1952, 209 .
33. Wood H . W . : Jl. Phot. Sci., 1954, 154-159.
34. F.P. 645,104 and 645,471 (1927).
35 . Steigmann A. : Sci. et Ind. Phot., 1949, 318. Evva F . : Magyar Kern. Folyo, 1952,
43--48 or Sci. et Ind. Phot., Sept. 1952, 369.
36. Bycichin A., Halamek C., Lacnak J. and Nemek B.: Prehled Photo Filmove Tech.,
1951, 103-105 .
37. Steigmann A.: Jl. Soc . Chern. Ind., 1946, 233-234.
38. Tamura M ., Sasai A. and Kubota K.: Jl. Soc. S ci. Phot. Japan ., May 1953 , 109-
113 and Sci. et Ind. Phot., 1954,214.
38b. Umano and Nakamura: Jl. Soc. Sci. Phot. Japan, Nov. 1954, 17, 54-59.
39. Maxwell, Bischoff and Blatherwick: Jl. Biol. Chern. Soc., 1927, 51.
40. Sheppard S. E. and Hudson J . H .: Ind. Eng. Chern. (Anal. Ed.), Jan. 1930, 73 .
41. Abribat M. : Sci. et Ind. Phot., Jan. 1941, 1-7.
42. Steigmann A. : Phot. Ind., 1934, 1352-1354; 1936, 198-200.
43. Steigmann A.: Sci. et Ind. Phot., 1951, 441.
44. Steigmann A. : Sci. et Ind. Phot., 1947, 142.
45. Landucci J . M.: Bull. Soc. Chim. Fr., 1954, 120-127; 1955, 857-865 . Pouradier J .
and Venet Mlle. : Sci. et Ind. Phot., 1952, 303.
46. Steigmann A.: Jl. Soc . Chern. Ind., 1943, 206.
47. Steigmann A. : Sci. et Ind. Phot., 1951,441.
48. Evva F.: Magyar Kern. Folyo., 1952, 43--48 and Sci. et Ind. Phot., 1952, 369.
48b. Steyman A. : Sci. et Ind. Phot., 1956, 27, 46--48 and 226.
48c. Wood H . W. : Nature, 1955, 1084.
49. Blake J . N. and Plaster F. H.: Jl. Soc. Leather Tr. Chern., 1950, 177-186.
49b. Abribat M .: Sci. et Ind. Phot., 1943, 1--4.
50. Kameyana N.: R.P.S. Cent. Conf., London 1953 and Sci. et Ind. Phot., 1954, 332.
51. Steigmann A.: Sci. et Ind. Phot., 1951,441.
52. Palladous chloride reagent: 1 g palladous chloride in 50 cc distilled water con-
taining 20 cc 5N HCl, then water to 200 cc. Dilute ten times with N HCl just
before use.
53. Fuchsine reagent: 475 cc water, 22 cc concentrated H 2 S0 4 , 2 cc of 3% alcoholic
basic fuchsine. The solution must be colourless. Just before use add 2 volumes of
5% formalin to 8 vol. of the fuchsine solution.
GELATIN 297
54. Steigmann A. :Jl. Sci. Chem. Ind., 1942, 162-164 and Sci. et Ind. Phot., 1949, 270.
55. Pouradier J. and Chateau H.: Sci. et Ind. Phot., 1951, 164.
56. Steigmann A.: Jl. Soc. Chem. Ind., 1946, 233.
57. Tschirch: Chem. Zeitg., 1941, 193-196.
58. Francis A. C. and Pilgrim A. J.: Analyst, March 1944, 90.
59. Steigmann A.: Foods, 1946, 105.
60. Pelz J. and Solnicka J.: Sci. et Ind. Phot., 1942,445.
61. Bycichin, Halamek and Hlavacek: Sci. et Ind. Phot., 1951, 185. Erdey, Rady and
Kaplar: Magyar Kem. Folyo., 1953, 151-154.
62. Hilbard P. L.: Ind. Eng. Chem., 1937, 127. Fisher and Leopoldi: Zeits. Anal.
Chem., 1934, 385; 1937, 241. Maron: Sci. et Ind. Phot., Oct. 1951.
63. Michel G . and Maron N.: Sci. et Ind. Phot., 1951, 350 and Anal. Chim. Acta,
1950, 542-550.
64. Brit. St. Methods for Testing Gelatin, 1944, No. 757.
65. Steigmann A. : Foods, 1946, 105.
66. Kind F. A. and Potnis 0. V.: Jl. Sci. Ind. Res. India, 1954, 55-59.
67. B.P. 625,200 (1947).
68. B.P. 245,456 (1925) and Fuch E.: Phot. Ind., 1933, 558.
69. Four cc bromine water for 100 cc 2% gelatin. The sensitivity increases with the
quantity of bromine then decreases. The fog increases then decreases before
S decreases. (S. Kikuchi: Jl. Soc. Phot. Japan, 1944, 111.)
70. Kodak: F.P. 966,006 (U.S. Priory 1946).
71. Amman-Brass H.: Gong. Int. Chim. Ind. Brussels, 1954; Sci. et Ind. Phot., 1954,
491.
72. Kodak: F.P. 861,783 (1941).
Chapter XVIII
GENERAL PRINCIPLES OF EMULSION

PREPARATION
284. Formation of photosensitive silver halides
The crystals of silver bromide, AgBr, are formed by the action of silver nitrate
AgN0 3 on an alkali bromide- potassium or ammonium bromide-in a
gelatinous solution. Whilst the Br- and Ag+ ions precipitate together, an
equivalent amount of soluble alkali nitrate is formed.
AgN0 3 + KBr --+ AgBr + KN0 3
Silver Po tass ium S ilver Potassium
nitrate bromide bromide nitrate
Silver chloride is similarly precipitated when silver nitrate is reacted with

sodium or ammonium chloride.
As a general rule, the silver nitrate solution is poured into the solution of
gelatin and bromide (which may include a small proportion of potassium
iodide). To prepare silver chloride, either the silver nitrate solution is added
to the alkali chloride, or the chloride may be added to the silver.
Whatever the method, an excess of alkali halide must be used.
The quantities of the reactants are readily calculated from their molecular
weight:
AgN0 3 : 170 AgBr: 180 AgCl: 143·5 Agi : 235
Ag: 108 KBr: 119 NaCl: 58·5 KI: 166
AmBr: 98 AmCl: 53·5
This shows, for example, that 170 g of silver nitrate, contammg 108 g
silver, requires 119 g of potassium bromide to give 180 g of silver bromide.
One g of silver nitrate corresponds to 0·7 g KBr, 0·5 8 g AmBr and 0·98 g
of KI. It gives, respectively 1·1 g AgBr, 1·38 g Agi and 0·63 gAg.
In practice, 1 g KI replaces 0· 7 g KBr or 0·6 g AmBr. The function of the
iodide is to modify the emulsion's characteristics, particularly by increasing
the sensitivity. The amount necessary rarely exceeds 5% for negative emul-
sions. It is much less than this for positive ones.
The silver halides crystallize in the cubic system. They are found as hexa-
gonal tablets, often reduced to triangles (Fig. 2), or as cubes with rounded
peaks (Fig. 45). The tablets are formed by precipitation in neutral or acid
solution, the cubes with ammonia.
298
285. Silver bromide without protective colloid
Tablet crystals of silver bromide with no protective colloid can be obtained by evapora-
ting an ammoniacal solution of silver bromide. These crystals are relatively large-
10 to 40 f.L and can be used for studying the action of IightY!
Gelatin-free plates can also be obtained by sedimentation on a layer of rubber from
a suspension of silver bromide.<•! The images obtained by developing such plates are
grey, weak and of low contrast. By adding 0 ·1% gelatin to the suspension, the reduced
silver assumes the normal black colour. The influence of the gelatin is very definite.
Another method is to grind up silver bromide containing 0 ·001 % Ag 2 S and up to
5% Agl, fused at 430°C, in an atmosphere of 95 % nitrogen and 5% oxygen. The
resulting product can then be dispersed in gelatin.Pl
Loening<•l has studied the behaviour of silver bromide sols.
FIG. 45. Silver bromide crystals (ammoniacal emulsion); compare with Fig. 2.
286. Mechanism of precipitation

The precipitation of the silver halide is the most important stage in the prepara-
tion of an emulsion. On it depends the future behaviour. It is also the most
critical process to operate, for it is most subject to a large number of factors
which are difficult to control.
According to classical theories, a mixture of alkali iodide, bromide and
chloride is first supposed to give a precipitate of silver iodide, then of bromide
and lastly of silver chloride, because the iodide is the least soluble of the three
halides:
Silver iodide: 10- 8 mol. per litre (0·0025 mg).
Silver bromide: 5 X 10- 7 mol. per litre (0·9 mg). Gledhill and Malan <5 !
found the solubility to be one-fifth of this.
Silver chloride: 10- 5 mol. per litre (1·5 mg). Davies and Jones< 5 b! found
the solubility 1-334 x 10- 5 mol. per litre at 25°C and
the solubility product 1·765 x 10- 10.
The silver halides are, however, much more soluble in the alkali halides,
present in great excess at the beginning of precipitation, which changes the data
of the problem, for complex salts are formed whose constitution is dependent
on the concentration of soluble halide. These complexes are of the form
[AgnBrm]<-Hm- n>, for example [AgBr 3 ]-- and [AgBr 5 ]----. Chateau and
Pouradier<6 >have verified that in the presence of a mixture of supersaturated
halide silver salts, the mixed crystals are precipitated from the start. However,
the first crystals contain most of the iodide and are of the hexagonal type. The
following, with a lower iodide content are cubic. The first ones take part in
the formation of the later ones, and are changed, perhaps bringing about
dislocations in the crystal lattices.
The formation of mixed crystals is favoured by a low concentration of
soluble halides. It is inhibited by the presence of neutral salts with polyvalent
ions such as Al+++. Chateau (Gb) has deduced certain rules for the operation of
silver analyses, for which mixed crystals are a source of error: stop the titration
before the first end point; boiling and cooling before finishing the operation.
By using the radioactive isotope Aglll, Jonte and Martin <7 >were able to
study more closely the complex solutions of silver chloride. They were led to
the conclusion that there are non-ionized AgCl molecules in solution. It had
already been shown that several types of centre are formed in the same opera-
tion, and that they are not all equally effective in bringing about crystalliza-
tion. As the most active centres are rapidly used, the crystallization rate is
changed. Loveland and Trivelli said that fractions of particular dimensions
correspond to particular types of centre, controlled by the Laplace-Gauss
law, which explains the anomalies in the grain size distribution curves.
The unstable state of the Ag+ and Br- ions during the supersaturation
period means that the equilibrium will easily be disturbed by external
factors, particularly variations in temperature, degree of agitation and type of
agitation. It should also be understood that the slightest change in concen-
tration during the course of precipitation has repercussions on the emulsion
characteristics.
Kolthoff has put forward the hypothesis that the first crystals which are
formed are spongy, and that having a large contact area they redissolve giving
rise to smaller compact homogeneous crystals.
In fact, the faces having a rapid rate of growth, in the circumstances the
[100] faces of the octahedral AgBr crystals, disappear to the benefit of the
[111] faces which grow more slowly. If growth takes place primarily in two
dimensions, tablets which are hexagonal, or may appear triangular, are
formed.
The silver halides crystallize in the cubic system with offset faces, that is,
in octahedra. The faces of the cube contain both the Ag+ and X- ions, whilst
the octahedron faces only have one or the other. <8 >The former, which are less
strongly charged, grow more slowly than the latter, which attract ions with
opposite charge strongly. The growth of the crystals depends on the concen-
tration of silver ions; it becomes more rapid as the silver ion concentration
falls. This is explained by the fact that at low Ag+ concentrations the silver
complexes are readily dissociated, and consequently provide a regular source
of Ag+ ions.
Precipitation in ammoniacal medium. The emulsions known as ammoniacal
are prepared by adding a solution of ammoniacal silver nitrate to a gelatin
solution of alkali bromide.
The ammoniacal silver nitrate is obtained by pouring ammonia into a silver
nitrate solution; a brown silver hydroxide is formed first, which readily re-
dissolves by adding just enough excess ammonia. Argentoammonium com-
plex ions are formed: [Ag(NH 3) 2]+ and [Ag(NH 3)s]+.
These ammonium complexes reduce the potential barrier which surrounds
each precipitation centre and each crystal. They therefore bring about a more
intimate contact between the Ag+ and Br- ions. Crystal growth therefore takes
place in a more regular way, in three dimensions. This results in the grains
having the form of cubes with rounded peaks and with similar dimensions,
. which has the effect of giving high contrast emulsions.
Adsorption of gelatin. A thin layer of gelatin is adsorbed to the surface of
the silver halide crystals. During crystal growth, this envelope is enlarged
like a growing cellular bag.
The gelatin layer surrounding each grain is only attached by a few active
groups, the majority of the hydrophilic groups (- CO.OH and -NH 2)
remaining in contact with the liquid. It is not very probable that there are
two layers of gelatin joined by their hydrophobic groups.
The adsorbed gelatin cannot be removed by washing. For 1 g of silver
bromide, 1-3 g is found, <9 l the layer thickness being in the order of 28 A. If
the surface gelatin is removed with hypobromite<10 l the residual gelatin can
be recovered, after dissolving the bromide in hypo, by concentration. Davis
in this way found 0·5 microgram of gelatin per gram of silver salt.
287. Precipitation methods

A precipitate of silver iodide, bromide or chloride formed in a solution of the
corresponding alkali halide adsorbs the excess negative ions I-, Br- or Cl-, to
form an equilibrium electric system with the positive metal ion. For example,
with silver chloride, precipitated in potassium chloride, a system will be
formed represented by
AgCl. Cl- i K+
An ionizable dye, such as fluorescein, added to this medium, will retain its
original yellow colour, for the negative fluorescein ion will remain free . This
continues until the precipitation of silver chloride by silver nitrate is complete.
But as soon as an excess of silver nitrate is p~esent, the silver chloride does
not adsorb the Cl- ions, but the positive Ag+, to give AgCl . Ag+ which
carries with it the negative organic ion: Ag. Cl. Ag+ ! fluorescein-.
The colour of the dye changes immediately; from yellow it becomes pink,
indicating the completion of precipitation.
Similar phenomena are observed when silver bromide is precipitated in
the presence of eosin, or silver iodide in the presence of eosin or fluorescein.
Conversely, a silver solution can be titrated with potassium bromide in the

presence of Rhodamine 6G as indicator. <n>
The adsorption of halide ions (- ) by the resulting precipitate becomes
stronger as the concentration of soluble halide is increased. The result of this
is that the higher this concentration, the more compact the precipitate due to
a very rough texture.
It is, in fact, easy to show that the globule of silver bromide, precipitated
in contact with a drop of silver nitrate in a gelatinous solution of ammonium
bromide (in excess) breaks up with more difficulty as the bromide solution
becomes more concentrated. A very dilute solution, on the contrary, gives a
precipitate which disperses easily with simple agitation into a homogeneous
milky suspension.
We have made the following tests: to 3% gelatin solutions kept at 38°C
(100°F) we added, respectively, increasing amounts of ammonium bromide,
then to each test solution, one drop of normal silver nitrate solution, and we
noted the ease with which the resulting silver bromide globule was dispersed:
1 g NH 4 Br Rapid dispersion.
100 cc of 3% gelating solution 1·8 g , Fairly rapid dispersion.
to which the ammonium 2 ·8 g , Dispersion by agitating.
bromide was added, fol- 3 ·7 g , Flocculation when agitation stopped.
lowed by one drop of ( 4 ·6 g , Vigorous continuous agitation.
silver nitrate. 7 ·4 g , Flocculation despite agitation.
The same experiment was tried with 1% gelatin solution, giving the following
results:
O·S g NH.Br Flocculent ppt. dispersing rapidly.
1 ·0 g " Less rapid dispersion than in the first
experiment, accelerated by agi-
1 % gelatin solution to which
ammonium bromide, then r
one drop of silver nitrate \ 1 ·8 g
tation.
Compact ppt. only dispersed with
vigorous agitation .
is added.
2·8 g Compact ppt. dispersed with ex-
l
3·7 g
tremely vigorous agitation.
Total dispersion difficult.
A high gelatin concentration therefore favours dispersion by forming floccular
globules. With 1% gelatin, the emulsion becomes difficult to prepare.
A high temperature also favours dispersion. With 1% gelatin containing 1%
ammonium bromide, a very compact precipitate of silver bromide is formed at 25 °C,
which only breaks up with agitation, whereas at 50°C the precipitate is light, and dis-
perses without agitation.
On the other hand, the product which is precipitated and dispersed at a low tempera-
ture is more transparent, indicating finer grain.
The addition of potassium iodide to the bromide solution increases the compactness
of the precipitate.
Ammonia, on the other hand, considerably facilitates its dispersion, by forming a
very loose-textured precipitate, the Br- ions adsorbed by the AgBr being neutralized
and displaced. Thus with 1% gelatin and 3 ·7 g bromide a flocculent precipitate is
obtained without ammonia, but this disperses immediately in the presence of the
latter. The speed of dispersion increases with the amount of ammonia.
The speed of dispersion of the silver bromide precipitate also increases with the
dilution of the silver nitrate solution.
Conclusions
(a) The precipitation of the silver bromide must be carried out at high
temperatures when a neutral solution is used, and at a moderate temperature
in ammoniacal solution, the temperature being lower as the ammonia concen-
tration is raised.
(b) The precipitation temperature must be higher as the gelatin concen-
tration is reduced and the iodide concentration is raised.
(c) Neutral precipitation in dilute gelatin, or with concentrated solutions
requires more vigorous agitation.
(d) Neutral emulsions can be prepared at relatively low temperatures
without forming a 'curd' by adding the alkali bromide at the same time
through separate jets, so that there is always a slight excess of bromide, as
constant as possible, which should never exceed a given limited value.
(e) The topographical distribution of the grains depends on the precipitation
conditions, that is, on the dispersion difficulties. This is an important con-
sideration in the case of fine-grain emulsions (see para. 72). .
In practice, photographic emulsions are prepared in neutral (or acid)
solution, and in ammoniacal (or semi-ammoniacal) medium. There are many
intermediate varieties, depending on whether the whole or part of the grains
are precipitated in neutral or ammoniacal medium, then ripened in neutral or
ammoniacal medium.
Type A
1. Neutral emulsions. These are prepared at about 70°C (158°F). They are
more stable than ammoniacal emulsions and have coarser grain and lower
contrast.
2. Acid emulsions. These are prepared as neutral emulsions, but in the
presence of a small quantity of inorganic or organic acid. In the case of silver
chloride, the soluble halide is frequently poured into the nitrate-gelatin
solution.
3. Borax emulsions. These emulsions are prepared in neutral medium,
borax being added finally to bring the pH to 8.
4. 'Double-jet' neutral emulsions can be precipitated at temperatures as low
as 45°C (113°F) using two simultaneous streams of bromide and nitrate, the
former always being a little ahead of the latter.
5. Mixed emulsions. Precipitation is carried out in neutral or acid solution,
but ammonia is added before ripening.
Type B
6. Ammonia emulsions. Precipitated at 65-70°C (149-158°F) in a gelatin-
bromide solution containing a certain amount of ammonia. With high alkali
concentrations the temperature can be reduced to 45-55°C (113-131 °F).
7. Partly ammoniacal emulsions. The first part of the silver is added in the
neutral condition (one-third or one-half for example). The remainder is
added in the 'converted' form. The temperature can be higher at the be-
gmnmg.
8. Completely ammoniacal emulsions. All the silver nitrate is converted to
the ammoniacal salt. Temperature 45°C (l13°F). This is the most common
method.
9. Acid-ammoniacal emulsions. The ammoniacal silver nitrate is added to a
gelatin-bromide which is acidified with a small amount of an organic (tartaric,
citric, lactic, etc.) or inorganic (nitric, perchloric, etc.) acid. The first crystal-
lization centres, formed in acid solution, are different from the normal
ammoniacal ones, and this influences the final characteristics.
288. Working conditions

Precipitation is the most important operation in the preparation of an emul-
sion. Its future is decided at this moment. That is why the physicochemical
medium and the working conditions must be examined carefully.
Little is known about the initial state of the crystallization centres, but it is
certain that for reproducibility the same operating conditions must be
observed each time.
Grain size. The grains formed during precipitation are finer as the addition
is made more quickly, as the concentrations of nitrate and bromide are re-
duced, as the gelatin concentration is increased (to a certain limit) and as
the temperature is reduced. In other words, the grains are fine when the
reaction between the consituents is least violent; if the precipitation time
must be short, it is only to prevent the first formed crystals from ripening
while the others are being formed.
The sensitivity of the emulsion is a function of the size of the grains. The
contrast depends on their fineness and their uniformity.
Precipitation time. We have seen that the grain size, and hence the emulsion
characteristics are dependent on the concentrations of the reactants taking
part. ~ow if a volume A of nitrate is poured into volume B of gelatin-
bromide, it is obvious that the first drop of silver nitrate reaches a medium
of high gelatin and bromide concentration, whereas the last drop enters a
solution diluted by the same nitrate solution. Therefore the first drop pro-
duces finer grains than the last, the mass passing through all the intermediate
SIZeS.
The ionic state of the solution varies gradually with the disappearance of
the soluble bromide during the reaction. Furthermore, the majority of the
potassium iodide is precipitated at the beginning. It follows that the later
parts of the precipitate are formed in the presence of pre-existing grains,
whilst the first ones are in a fresh solution.
The gelatin concentration can also be reduced to one-half-from 5% to
2!% for example-whilst the soluble bromide concentration falls from 18%
to 1·8 %.
It can therefore be seen that a system involving such variable factors will
be difficult to control, and even impossible to reproduce twice in an absolute
way.
GENERAL PRINCIPLES OF EM U LSION PREPARATION 305
Negative emulsions, however, whose exposure latitude must be as great
as possible, must have a wide range of grain sizes (and therefore of different
sensitivities): to this effect, stepped precipitation can be used, by adding the
silver solution in several separate fractions, separated by periods of time. The
first grains grow by ripening, whilst those from a later addition remain small
having less time to ripen.
For the preparation of identical successive batches of emulsion, average
values are expected. In fact, stepped precipitation introduce new factors
causing dissimilarity, in addition to those of simple precipitation: the frac-
tions which are successively precipitated are each produced in a different
medium, which results in the formation of grains which are characterized,
not only by their size differences, but also by structural differences due to
changes in the colloidal and ionic condition of the solution.
It is preferable to substitute a mixture of several emulsions of the same
type, with different, but well-defined grain sizes and structure, for stepped
precipitation. The preparation of each emulsion is then carried out by fairly
rapid mixing of the two reagents with vigorous agitation, enabling the maxi-
mum homogeneity and constancy of results to be obtained. We have also
used a second method, which is to divide the gelatin between the bromide
and the sil-'fer solution in equal concentrations: thus during the whole precipi-
tation time, the gelatin concentration remains constant. If a double jet method
is used to introduce the bromide and silver into a pure gelatin solution a
medium of constant ionic composition can thereby be obtained. The tempera-
ture must be kept constant, and it is advisable to bring all solutions, in-
cluding the silver nitrate, to a definite precipitation temperature, and take
into account the heat produced by the reaction itself.
289. Physical ripening

This operation has the object of increasing the size of the silver halide grains,
and consequently their sensitivity. The precipitated emulsion is kept at a
fixed temperature, between 45° and 70°C in the presence of excess soluble
bromide. During the whole of the ripening operation, the emulsion is constantly
and regularly stirred.
The sensitivity increases with prolonged heating of the emulsion : the crys-
tals formed by precipitation increase in size, the larger ones increasing at the
expense of the smaller, under the influence of slight supersaturation. Finally
the smallest grains disappear because of their greater solubility in the excess
silver bromide solvent.
The phenomenon is accelerated in the presence of ammonia which is a
silver halide solvent. This ammonia can be used as ammoniacal silver nitrate,
or can merely be added before or after precipitation.
Ripening is essentially dependent on the solubility of the silver bromide
in the bromide solution due to the formation of a complex. In neutral emul-
sions this solubility increases with the Br- concentration, but in ammoniacal
emulsions it increases at first, then decreases when an optimum value has
been exceeded.
According to Lyalikov's measurements<12 l the velocity of growth V of a

crystal, for a radius r and a ripening time t is related to the concentration c
of the silver bromide in solution and the solubility Sr, by the equation
(C- Sr)
Vrt = A- - -
. r
where A is a coefficient of proportionality equal to the coefficient of diffusion.

The rate of growth is a linear function of 1/r 2 • For short ripening times the
function is somewhat hyperbolic.
The rate increases with temperature:
H
logVr = F--
T
where T is the absolute temperature and F and H are constants.
The number of grains n after time t, compared with the number of grains n 0
initially present is given by Lambert and Sheppard's equation, verified by
Lyalikov: <13 > n = n 0 /1 + kn 0t where k is the constant of crystallization rate.
What is the mechanism of crystal growth? Two are assumed:
(a) Progressive growth of crystals at the expense of the finest (Ostwald
ripening).
(b) Joining of several crystals by coagulation.
Progressive growth takes place in low concentrations of gelatin and silver
halide as well as in the presence of inert gelatins. <14 >
Dimensions of ripened grains. The size of the grains increases with time,
temperature, concentration of soluble halide, concentration of ammonia (if
any), the dilution of the gelatin and the rate of agitation.
The increase in size of the grains is shown by an increase in the turbidity of
the emulsion. With negative emulsions the diameter easily reaches 3 p., but
there is, in actual fact, a wide range of smaller diameters. For slow emulsions
the average diameter is 0-6 p., 'process' emulsions 0·3 p. and positive emul-
sions, 0·1 p..
The sensitivity of an emulsion increases with the time of physical ripening,
but only up to a certain limit.
Contrast. Coarse-grain emulsions are less contrasty than fine-grain ones.
Those having a wide range of grain size have an average contrast, resulting
from the contrasts of the different groups of grains. Separation of an emulsion
into two layers by sedimentation gave Renwick the following significant figures:
Relative Fog
sensitivity Contrast density
Initial emulsion 100 1-14 0·14
Coarse grains 170 1·10 0·22
Fine grains 25 1·76 0·10
To obtain a high-contrast emulsion it is consequently necessary to preci-
pitate the grains so that they are as nearly as possible of the same size, and to
avoid long ripening. Commercial process emulsions for line work, which
need very high contrast, have, even so, a fair range of grain size whose relative
areas are 10 : 1. This ratio goes to 100 : 1 for negative emulsions.
290. Retarders and accelerators of physical ripening

Crystal growth during ripening is, as we have seen, inhibited by gelatin.
This contains a greater or less quantity of natural retarders; also the ripening
rate is in inverse proportion to the amount of gelatin present.
Gelatins rich in retarders are generally obtained from hides. Gelatins poor
in retarders are obtained from bones or by deactivation (inert gelatins).
Artificial retarders. The introduction of egg albumen can, to some extent,
make up for the lack of retarders in gelatin. Cystine which is sometimes re-
commended is only effective in fairly high concentrations and also desensi-
tizes. It is better to use imidazoles, thiazoles or thiolactic acid; for example, a
concentration of 0·2- 2% of the weight of dry gelatin of 4-thiazolidone (Steig-
mann). Excellent results can also be obtained with dithiopyrimidine and
dithioquinazoline. <15 >
Cadmium ions Cd++ retard the ripening of silver chloride, onto which it
is adsorbed. Their effect drops with the pH. Cadmium salts are often used
in the preparation of contrasty chloride and chlorobromide emulsions.
Ripening accelerators. Sulphur sensitizers generally accelerate crystal
growth. The turbidity diagrams established to determine the retarding power
of gelatin have inflection points due to disturbances introduced by natural
sensitizers which are present. However, a gelatin rich in labile sulphur does
not necessarily bring about grain growth by coagulation. <16 >
Ohyama and Futoki have studied several very active accelerators: <17 >
1- thio - 2- ethyl-]: 2- dihydrobenzoxazole, rhodanine, sym- N: N - dioctadecyl-
thiourea, N-octadecyl-N-allylthiourea and N -octadecylrhodanine.
291. Distribution of grains after physical ripening

The distribution of grains in an emulsion is shown by a frequency curve (Fig. 46). The
dimensions in 1-' are plotted on the abscissa and the frequency per 1000 grains on the
ordinate.
The frequency curve can be represented by the equation
Y = yoe-k<z-ctlz
in which y is the frequency p er 1000 g rains, y 0 the maximum ordinate value, IX the
abscissa value corresponding to this maximum, Z the average diameter of the group
of grains considered, k is a constant and e is the Naperian logarithm base. The values
of y 0, k and IX for three emulsions are shown in the table below:
Millions mg of Per- Pro- Area in Constants of the

of Ag centage Dia- jected frequency
Emulsion grains Halide Ag meter area Volume Mass in JL'ofthe equation
in p..3 10- 12 g largest
per per Halide JL in p,2 grains
cm2 cm2 in dry Yo k 0(
emulsion
Process 668 1-37 33·6 0·844 0·560 0·317 2·05 1·6 340 8·95 0 ·55
Rapid 940 1·30 32·5 0 ·799 0 ·502 0·213 1·38 6 ·2 277 4·27 0 ·53
Extra-fast 478 1·47 33 ·7 1-67 2·198 0·476 3·08 12·6 {200 2·78 0 ·76
30 6·45 2·05
The evaluation of emulsion grain sizes is made with photomicrographic enlarge-

ments of these emulsions which have been previously diluted to a known extent in a
larger quantity of gelatin solution, then coated in very thin layers.< 18 l To simplify
measurements specially graduated rulers which directly show linear measurements
and area in p. • can be used. Loveland used three different graduations for triangular
grains, hexagonal grains and substantially circular ones: he measured respectively the
height of the triangle, the distance between opposite sides of the hexagon (average
value when the hexagon is irregular) and the diameter of the circle.
.: .. \B
,
''
'
''
'
''
''
''
''
''
'
''
''
'•,
',,,..
2.,.
2 ,....
FIG. 46. Frequency curves of silver bromide grains.
Sheppard and Trivelli have shown that the grains resulting from the collision of
ions and particles follow a probability law whic4 is also effective with their initial
distribution. Loveland and Trivelli1 20 l established the general equation y = cf• where
y is a characteristic of the distribution of grains by dimensions such as the total num-
ber of grains, the average diameter or the dispersion around this average diameter;
f is a variable ripening factor (for example, the concentration of soluble bromide) :
a and c are two parameters.
Another m ethod of representation is to express the area of the grains logarithmically,
and use its function Z, called the normal frequency function, in place of the frequency
itself:
1
z = --e-x2 /2. dx
y27T
In practice the cumulative frequencies are plotted on a graph of the logarithmic
probabilities. A distribution like that of the function of the cumulative frequencies
will be a straight line on a graph of probabilities and can be expressed by:
y = Anxnexp[- k(Logex- 1Xn)2] dx

where y is the frequency, x is a property of the size, A, k and IX are constants and n is a
whole number.
This equation has the same form as the Gauss one:
f(x) = fm exp[- C2(x- xm)2]
where f(x) is the nwnber of grains with an area between
x and x + dx
fm = f(xm) being the maximwn ordinate and C 2 is a positive constant. A modification
suggested by Loveland and used by Kapteyn represents the phenomenon more
exactly by replacing x by log x in the Gauss formula:
f(x) = fm exp[- C2 log2(x/xm)]
where the preceding Loveland and Trivelli formula is again found.
Silberstein, however, prefers the empirical equation:
log [(f(x)/fm] = - k(x- Xm)2f(x- q)!
where q is a constant, k a positive constant, x m and f constants which define the maxi-
mum of the curve.<•'> For example, if Xm = 0 ·65 fl- 2 , then q = 0 ·261 fl- 2 , x = 0·082 fl-2
and fm = 760 for a total of 3,830 grains measured.
Kottler,< 22 > referring to recent work of Pearson and Fisher, has made many critic-
isms of calculations based upon the Gauss error function as well as Kapteyn's trans-
formation. Kottler substituted algebraic for graphical analysis< 23 > by introducing the
principle of the minimum square, ex• = ~ '6 2/s 2 where '6 is the individual error, and
s the average quadratic error). The time of growth is related to a parameter a and the
rate of growth to a parameter b.
292. Setting and washing

Dry gelatin is added to the precipitated and ripened emulsion, and dissolves
after 15 minutes. The liquid is then rapidly cooled and set in vessels placed
in a refrigerator at 5-6°C (41-43°F), so that it is turned into agel. The amount
of gelatin added must be such that the concentration of gelatin in the emulsion
before cooling is 7-10% (of the total amount of water, the evaporated water
being replaced). A minimum of 7 % is necessary so that during washing the
gel will not swell and absorb too much water. If, for example, the gelatin
concentration after precipitation is 3 % for a volume of water equal to 900 cc,
that is 27 g, 6% or 54 g of gelatin must be added to bring this concentration
up to 9% .
The setting time depends on the volume of the emulsion. Small quantities
can be coated on trays at a thickness of 0·5-1 em which enables them to be
thoroughly set in less than 2 hours. <24 > It is, however, preferable to keep the
set emulsion in a refrigerator for 12 hours.
The solid block of emulsion is shredded into noodles 3 or 4 mm diameter
in a press, or with a knife if setting has been carried out in a dish. For small
quantities muslin or a net can be used.
The shredded emulsion is then washed in running water. The purpose of
washing is to remove all the soluble salts, particularly the excess bromide and
the alkali nitrate which is formed during the reaction. The time of this opera-
tion depends on the concentration and nature of the gelatin, the thickness of
the shreds, the total volume, the agitation, <25 > the hardness of the water
(120 mg CaO average), the rate of flow and mainly the temperature. Hard
water, a low rate of flow and a low temperature lead to slow washing. Gener-
ally this varies from 3 to 6 hours.
Washing is limited on one hand by the softening, swelling and water

absorption of the shredded mass, and on the other by the risk of fog in over-
washed emulsions. The elimination of the soluble salts must be controlled by
analysis (Nessler's reaction) and measurement of the Br- ion concentration or
by measurement of the resistivity of the water. The purity of the water used
must also be checked. In experimental work a circuit of distilled water is
sometimes used but as it tends to swell the noodles too much, 200 mg of
anhydrous sodium sulphate is added per litre.
It is important to know the quantity of water absorbed by the emulsion
shreds: the emulsion is weighed before and after washing; it is, however,
difficult to obtain constant results because of the large number of influencing
factors.
This increase in weight due to absorption of washing water is measured
after draining for 30 mins. to 2 hours or even after blotting.
The emulsion noodles swell in water, this action being more rapid as the
noodles are made smaller. They also swell more as the water temperature
becomes higher. Furthermore, in the presence of ammonia, weak gels absorb
more water than concentrated ones. Ammonium bromide also increases
swelling; its action is stronger than that of potassium bromide.
The bromide is removed twice as quickly as the ammonia. This is checked
with a few cc of liquid in which a few pieces of the noodles have been crushed
by adding a few drops of Nessler's reagent (potassium mercury iodide), which
gives a brown precipitate in the presence of ammonia. Riegler's reagent of
p-nitrodiazobenzene hydrochloride can also be used; this turns red. The tests
are of course carried out after filtering the sample liquid.
A current method of controlling wash-water is by its electrical resistivity.
G. G. Blake has disclosed a special system in which a variable resistance is
connected in parallel with the condenser of an electrical oscillator. <26 >
Washing technique. In practice two different methods are used:
(a) Washing in racks in stagnant water, which is renewed every 15 or
30 minutes, with periodic stirring of the noodles.
(b) Washing in running water in a tank or in a trough similar to that used
for making paper paste.
Contrary to what might be thought, the old method of washing in racks is
the quickest and most efficient, and a smaller number of noodles are broken
by agitation.
The washing time is 3-4 hours for slow emulsions and S-6 hours for fast
ones.
The water temperature should not exceed l2°C (54°F) or the noodles may
swell and form a mass from which the soluble salts cannot be removed.
The water should have the lowest possible calcium content. Calcium salts
make the gelatin opaque and the resulting coatings are matt and grainy. Town
water containing 120 mg CaO produce a definite matt surface. This is quite a
serious disadvantage which can only be overcome by purifying the water with
a permutit or resin ion exchanger. The effect of these should, however, be
very carefully checked, for with improperly treated organic resins an intense
fog can be produced in the emulsion. A more costly method of purification
is to add 2 g per litre of sodium hexametaphosphate to the wash water; this
sequesters the calcium and magnesium (the use of Sequestrene or ethylene-
diamine tetraacetate is even more expensive). Finally, small batches of
emulsion can be washed with distilled water obtained from a thermo-com-
pression apparatus; 200 mg per litre of anhydrous sodium sulphate should be
added to this water (or 484 mg of Na 2S04 • 10H 20).
The wash water almost always contains organic substances which have not
been properly identified. These organic substances vary in type and quantity
depending on the source (spring, river, well, and according to the seasonal
variation in rain and drought). They can cause 'inexplicable' variations, by
their action on the sensitivity and other properties of the emulsions.
293. Treatment of emulsions without washing

Three methods can be used to separate the ripened silver halide crystals (or
at least, the majority of them) from the gelatin:
(a) Centrifuging.
(b) Sedimentation of grains precipitated in the presence of very little
gelatin and ripened without the addition of further protective colloid. The
grains, freed from their salts can then be redispersed in fresh gelatin. This
method has been used commercially, but large AgBr grains from which the
liquid can be readily decanted are necessary.
(c) Coagulation with sodium sulphate. An equal quantity of an 80- 90%
solution of sodium sulphate decahydrate is added to the emulsion. The
coagulum is washed, then redispersed in water to which gelatin solution has
been added. This method is the most interesting of the three.
We would note here the washing of an emulsion by dialysis through a mem-
brane (parchment or cellophane). This enables the soluble salts to be removed
from the warm liquid emulsion. This process can be used with polyvinyl
alcohol emulsions. (27l
294. After-ripening
The digestion of an emulsion after washing, or chemical ripening, has the
object of forming sensitivity specks on the surface of the silver halide crystals,
whose effect is to increase their sensitivity.
After-ripening has no direct effect on the size of the grains except for possible
coagulation.
The after-ripening temperature depends on the emulsion type: it is about
45°-50°C for ammoniacal emulsions, but may go up to 65°C for neutral
emulsions.
After-ripening time. The chemical ripening of an emulsion during digestion
is more rapid as the temperature is raised. For extreme speed ammoniacal
negative emulsions, it is about one to one-and-a-half hours at 50°C.
The general sensitivity of an emulsion increases with the after-ripening
time. It increases to an optimum value after which it starts to drop. The appear-
ance and increase of fog follows the increase in speed but in a different way. The
fog starts to be appreciable around the point of optimum sensitivity; this is

why after-ripening is stopped when the fog becomes appreciable (but acceptable),
say 0·06 for a negative emulsion.
An emulsion which is not digested up to the optimum point will continue
to ripen slowly when cold, unless this action is stopped by the addition of a
powerful antifoggant.
To follow the progress of after-ripening and to be able to stop the process
at the required time, it is necessary to remove samples at equal intervals, coat
them rapidly on glass or paper and expose and develop them wet, so that the
sensitivity and fog can be known.
After-ripening principally increases the sensitivity of emulsions which have
had little first ripening. The gamma is, at the same time higher, and the grain
finer. As an example, the sensitivity and gamma obtained with an ammoniacal
emulsion at varying first and after-ripening times are shown below. The
corresponding fog values are also included.
Time of After-ripening After-ripening Mter-ripening

first ripening 30 mins. 60 mins. 90 mins.
s 19·5
= s = 26 s= 26
0 y= 2·1 y= 2·85 y= 3
F= 0 ·02 F = 0·04 F= 0·1
S =72 8=71 s=57

10 mins. y= 2·1 y= 2·45 y=2-4
F= 0 ·03 F = 0·05 F= 0·25
s = 107 s= 98 s = 75
20 mins. y= 2·3 y = 2·2 y= 2·1
F = 0 ·04 F= 0·13 F = 0-4
From this table we see that:

(a) For the same after-ripening time, the sensitivity increases regularly
with the first ripening time.
(b) For the same first ripening time, the sensitivity does not necessarily
increase with second ripening time, but reaches an optimum, then drops.
(c) The highest contrast is obtained with a short first ripening followed by a
long after-ripening.
(d) For a short after-ripening, the fog only increases slightly with first
ripening, but with extended after-ripening, the fog increases considerably.
' (e) Whatever the first ripening time, the fog increases quickly when the
optimum after-ripening is exceeded.
(f) For a practically useful emulsion, either the first ripening must be
brief, followed by fairly long digestion (fine grain, low sensitivity, low fog
and high contrast) or a fairly long first ripening must be followed by a
relatively short digestion (fairly coarse grain, high sensitivity, low fog,
moderate contrast).
Influence of ammonia. The addition of a small quantity of ammonia before
after-ripening accelerates the rate of chemical ripening. In addition, the fog
also increases rapidly, and the ammonia must be neutralized at the end of the
operation. This ripening method is not widely used in practice.
Many organic bases have been proposed in place of ammonia: anilines,
morpholine, piperazine hydrate, N:N-dihydroxyethylpiperazine, N-
hydroxyethyl piperidine, and especially pyridine.
Influence of antifoggants. They are strong ripening retarders, and can even
prevent ripening completely.
295. Sensitivity specks

The increase of sensitivity by chemical ripening is due to the formation of
specks on the surface of the halide crystals.
The sensitivity specks consist of either silver sulphide or metallic silver.
The sulphur compounds contained in gelatin are indisputably the source
of these specks. It is, however, difficult to understand the mechanism of their
action. Does the silver sulphide produced remain finally in this form? Some
workers, notably Chibissov and his collaborators(28 > think not. They grant
that if the sulphur compounds effectively accelerate the after-ripening by the
formation of adsorption compounds, it is the autocatalytic reduction of silver
salts to silver which brings about the increase in sensitivity.
Whilst it is true that one can produce silver specks during digestion, using
for example, stannous chloride SnC1 2 (5-100 mg per kg of AgN0 3), (29 > it is
certain that the active compounds in gelatin have a greater influence on the
sensitivity of an emulsion. Silver sulphide in either a simple or complex form
must react with surface sensitivity specks which are already present. We have
seen in para. 25 how the study of the formation of the latent image leads us
to consider the specks as complex structures formed by the association of a
sulphide ion and a positive hole.
Such a conception is entirely in accordance with observations based on the
practice of emulsion preparation, the most important of which is: all the
characteristics of an emulsion are defined, in a latent form, at the moment of
precipitation, particularly if this is carried out in the presence of an active
gelatin. The later operations of first and second ripening only result in the
development of these characteristics-not their creation.
296. Choice of gelatin

The choice of gelatin depends on the type of emulsion which is required.
Furthermore, each phase in the preparation- precipitation, ripening, after-
ripening-must be suited to a particular type of gelatin.
Active gelatins. These are suitable for the precipitation of negative emul-
sions. Some workers use them to sensitize afterwards. Experience, however,
has shown that this does not give the best results, for these active gelatins
only produce their optimum effect at the moment of precipitation.
The sensitivity of an extreme speed emulsion is not proportional to the

amount of sulphur sensitizer; quite a small percentage of active gelatin (10%
of the total) is enough to ensure the speed. Any increase in this amount of
gelatin only results in an increase of fog.
Added gelatins. This term applies to gelatins added after precipitation, but
before after-ripening (second and third gelatins). These gelatins need not be
rich in sensitizers, but rather should have a very low fogging tendency. They
must retain the latent sensitivity of precipitation, that is, they must not
neutralize the precipitation gelatin. They must, furthermore, have another
extremely important quality: not to accelerate after-ripening. There are gelatins
whose optimum ripening time is zero. These are bad gelatins (at least for the
chosen emulsion type). To obtain a good high-speed negative emulsion, the
sensitivity and density of the blacks should be very low at the beginning of
after-ripening: they increase very gradually, and only reach their maxima at
the optimum digestion time, before fog becomes objectionable.
Inert gelatins. These gelatins (mainly from bones) have been de-activated
by various processes (which have already been enumerated). Some workers
use them together with artificial sensitizers. Other gelatins are said to be inert
to gold: these are ones which do not produce emulsion fog in the presence of
gold salts.
Retarding gelatins. These are generally made from calf skins. Emulsions
prepared from such gelatins are contrasty; when sufficiently active, the
emulsions are of the 'process' or 'contrasty' bromide positive types. As they
are free from degradation products and sensitizers, they are suitable for the
preparation of silver chloride emulsions. The presence of contrast bodies can
intensify the power of these gelatins.
Gelatin content. The gelatin concentration of an emulsion must be such that
it can be coated and set easily on glass, film or paper. The measurement of the
viscosity is therefore a very important measurement. The amount of gelatin
must be balanced with the amount of water. The emulsion can, however,
have a high or low concentration of silver halides. An emulsion containing
little gelatin compared with the silver will develop more rapidly, and the y oo
will be reached more quickly.
The variations of this limiting development time as a function of R =
gelatin/silver are represented by the curve in Fig. 47. From R = 2, the time
necessary to reach y 00 remains practically constant.
The contrast given by a photographic layer is not the same for each wave-
length; but near y 00 the differences become negligible; so that for an identical
gamma throughout the spectrum with the same sensitive layer, development to
y 00 must be rapidly reached. Under these conditions it is necessary to use
an emulsion with a low gelatin content, and this is practiced with reseau
colour films.
Gelatin tests. There are many chemical and physical tests which have
already been dealt with which can give useful information on the behaviour
of the gelatin. However, experience has shown that the best test is still that of
preparing a given emulsion and carefully determining all the sensitometric
characteristics. It must, however, be borne in mind that the physical and
chemical ripening times can be slightly changed without prejudice to the
results; several different preparations are therefore sometimes made, and it is
advantageous to plot the characteristic curves of the samples removed during
digestion and coated on glass or paper.
V'"
/
,/
I' r
R.Geta1ln
Silve•
0 0,5 1.5 2 2.5

FIG. 47.
CHEMICAL SENSITIZERS
297. Sulphur sensitizers
Gelatin introduces sulphur sensitizers into the emulsion, which bring about
the formation of specks during digestion to considerably increase the light
sensitivity. What are these natural sensitizers? We have seen that opinions are
divided. For some, the gelatin sensitizers are thiosulphates and thionates,
whilst for others they are organic substances of relatively high molecular weight,
linked perhaps to the gelatin. Despite the work of the upholders of the thio-
sulphates, it is the second hypothesis which at the moment, and until absolute
proof to the contrary is obtained, appears the most likely. None of the known
artificial sulphur sensitizers behave like an active gelatin. Also, it has been
wrongly thought for some time that the activity of gelatin is due to allyl iso-
thiocyanate, a compound in mustard oil and discovered by Sheppard in the
liming water. What is true, is that collagen which is limed for too long a time
loses its sulphur compounds, but only the degradation products are found,
particularly methionine ( 1% ), cystine, cysteine, polythionates and thio-
sulphates:
Methionine: CH 3 -S-CH 2 -CH 2 -(CH-NH 2)-CO. OH

Cystine: OH. CO(NH 2) : CH-CH 2-S- S-CH 2 -CH:
(NH 2 )CO. OH
Cysteine: OH. CO(NH 2 ) : CH-CH 2 -SH
The active sulphur, estimated by Feigl's reaction, and the labile sulphur
by the sulphiding of silver, can only give results of meagre practical value.
The only effective test is to study the behaviour in an emulsion. In addition we
know that the turbidity curves obtained from physical ripening show inflec-
tion points, each of which corresponds to an active substance of gelatin;
however, the shape of an inflection zone given by a naturally active gelatin
.differs greatly from that due to an artificial sensitizer.
Among the artificial organic sulphur sensitizers which have been proposed
and tried with greater or less success are the following:
Allylthiourea (or thiosinamine) NH,-CS-NH-CH,-CH = CH 2 and its

.derivatives such as allylbenzylthiourea, diethylthiourea and allylpiperidylthiourea.
Allylthiourea generally produces intense fog, and is not usable in practice. Concen-
tration 0 ·1-1 mg per gram of AgBr. The latter quantity can produce image reversal
by chemical solarization.
Thiourea NH 2-CS-NH 2 also produces fog. It has, however, been tried by many
workers <30 l even using the compound with the radioactive isotope 8 3 6 • Thiourea is
most active at pH 8.
Thiosemicarbaz ide NH 2-CS-NH-NH 2 • This is produced by boiling a solution
.of hydrazine and ammonium thiocyanate. Concentration 0 ·01-0 ·1 mg per gram of
AgBr. Murobushi, Kawaguchi and Ashikowa used aldehyde-thiosemicarbazones which
.are ripening retarders at the same time.<3 2 l
1-thio-2-ethyl-1 :2-dihydrobenzoxazole is also a retarder. <33 l
Benzothiazole methyl sulphide is only effective with rapid emulsions (concentration
20 mg per litre of emulsion).
Aminothiazole base (in 5 : 1000 aqueous alcoholic solution) increases the sensitivity
.of fast emulsions but produces fog. ·
Allylpseudothiohydantoin hydrochloride (5 : 1000 alcoholic solution) . Twenty mg
per litre of emulsion fogs silver bromide emulsions but increases the sensitivity and
·Contrast of chloride ones.
Thiolactic acid. One hundred mg per litre increases the sensitivity and contrast of
.chloride emulsions. It desensitizes and increases the contrast of process emulsions and
.desensitizes fast emulsions.
Ergothioneine hydrochloride only increases the contrast of chloride emulsions.
Thiodiphenylamine (or phenothiazine) increases the contrast of process emulsions
but desensitizes.
Thiochrome (vitamin B.1) at a concentration of0·05 mg per litre of emulsion appears
to increase speed when added before after-ripeningY'l
Phenyl-P:P-dimercaptovinylacetone.
Sulphomalic acids.
Dithiolactic and dithioacetic acids.
Potassium dithiocyanate (0·015 mg per g AgBr) .
Guanidine thiocyanate.
The thiocyanates generally activate sulphur sensitizers and are anti-retarders.
298. Various organic sensitizers

Gelatin hydroly sis products studied by Bycichin and Vlach, appear to have no
practical value .
Phenylalanine
Slight increase in sensitivity together Tyrosine
with considerable fog.
{ Glutamic acid
Goose haemoglobin
Alanine
Proline
Hydroxyproline
Aspartic acid
Arginine
Glycocol
Reduction of sensitivity and fog retarded
Leucine
Albumen
Globulin
Cholesterin
Lecithin
Blood serum
Reduction of sensitivity with prevention Cystine
of fog.
A gelatin hydrolysis product, however, had increased sensitivity, the fog not in-
creasing until the end of after-ripening.
Betaine and lecithine reduce sensitivity and fog.<" 5 l
Creatine and arginine have been proposed for increasing the sensitivity of sensitized
cellulose films< 36 l in 1 g per litre baths.
Rivanol is the lactate of 2-ethoxy-6 : 9-diaminoacridine. It has a sensitizing action
on some emulsions with a slight increase in contrast. It can be used as a 4 : 1000
solution. Using 1·2 mg per gram AgBr it can increase the speed of slow emulsions by
one half. It has the disadvantage of staining the emulsion yellow.
Esculin can increase the sensitivity of moderate-speed emulsions when about 1 mg
per gram AgBr is added. The fog rises by 0 ·03 with no change in contrast.
299. Inorganic sulphur sensitizers

Among the inorganic sulphur sensitizers, the most widely used are the sodium
or ammonium thiosulphates. We have already seen that these compounds are
considered by some workers to be the active substances in gelatin, together
with the polythionates (which behave like the thiosulphates).
It is, in fact, necessary to discriminate between the action of thiosulphates
added to the emulsion (at the end of preparation) and added to the gelatin
before precipitation. The best results are obtained when the thiosulphate is
added to the gelatin in amounts of a few mg. per kg. When added to a completed
emulsion, positive results are only obtained with certain slow emulsions;
the speed of a slow emulsion, for example, has been increased 2·6 times by
adding 1 mg. hypo per gram of AgBr, the fog rising from 0-02 to 0·06. With
fast emulsions, however, the speed generally drops, accompanied by an
increase in fog. This also occurs when thiosulphate or polythionate is added
before precipitation in too high a concentration.
Lorenz, (37 l who studied the action of many sulphur compounds, has stated
that the trithionate Na 2S 30 6 liberates sulphur most easily. In acid solution
(pH 3-5) it is 2·5 times more active than thiosulphate. Its activity drops to
half in neutral or basic solution. Some commercial sulphiding preparations
behave like the polythionates, in particular like the pentathionate Na 2S 5 0 6 •
As far as sodium thiosulphate Na 2S 20 3 is concerned, its sensitizing is
probably due to only one of the two sulphur atoms. It first forms several
argentothiosulphates but not all of these dissociate spontaneously. (SSJ At low
Ag+ concentrations, and in acid media, secondary reactions can take place,
which interfere with the activity of the product.
Sodium sulphide Na 2 S. Added to the emulsion it produces fog and an in-
tense yellowing. It sometimes produces a sensitizing action if added to certain
gelatins in concentrations below 1 mg per kg.
Colloidal sulphur has been disclosed in F.P. 645,104 and 645,471 (1927) to
activate gelatin by heating together. A small fraction of the resulting product
is added to the precipitation gelatin.
300. Influence of metallic salts

Metallic salts have very diverse actions on photographic emulsions.
Magnesium as the chloride or bromide. Favours a slight increase in sensi-
tivity with reduction of fog when added before after-ripening.
Ferrous and mercurous salts- slight increase in sensitivity with the formation
of fog.
Ferric and mercuric salts-reduction of sensitivity and increase of fog.
Nickel reduces sensitivity, and sometimes increases contrast a little. No
increase of fog. Nickel and cobalt are ripening accelerators.
Lithium reduces sensitivity and increases fog.
Lead and thallium reduce sensitivity and increase fog. Thallium was dis-
closed by Schwarz in 1926. Mueller<39 > stated in 1935 that lead and thallium
salts added in a concentration of 0·04 molecules per cent of the silver halide
increase the sensitivity of gold-sensitized X-ray emulsions by 50-100 % . The
addition is preferably made before precipitation. In the presence of vacant
silver ion sites in the halide crystals, a complex [Pb++Ag0 ] is produced,
which increases the electrical conductivity. <40 >
Rhodium has a very powerful action on silver chloride emulsions. It results
in a strong reduction in sensitivity accompanied by an important increase in
contrast (see silver chloride emulsions).
Cadmium is a retarder of physical ripening. Its action with chloride emul-
sions results in an increase in contrast. The addition of cadmium salts is made
before precipitation.
Copper salts reduce emulsion sensitivity. They are used in some slow pro-
cess bromide emulsions to increase the contrast by adding before digestion.
Copper salts can increase the speed of chloride emulsions when accompanied
by organic acids (e.g. citric). <41 >
Heavy anions. Certain insoluble silver salts with heavy anions such as
tunstate, molybdate, vanadate, have been proposed for increasing emulsion
sensitivity. To do this, the corresponding alkali metal salt is added to the
solution of alkali halide.
The thiocyanates, added before precipitation or during digestion have also
been disclosed for increasing emulsion sensitivity. <42 >
It is advisable to make reservations as to the efficiency of these products.
It can even happen in some cases that there is a complete loss of sensitivity
and fog results.
301. Gold sensitizing
Gold increases emulsion sens1t1v1ty considerably when added as complex
aurous thiocyanate (or aurothiocyanate).
In 1925 Kropp£ envisaged the possibility of sensitizing an emulsion with
gold chloride AuCl 3 . <43 l Then Carroll and Hubbard tried colloidal gold in
1928, Kantelwitz traces of gold salt in the presence of mercuric salts <44 l and
Schmieschek, basic gold salts. <45 l
It was Koslowsky <46 l who first had the idea in 1936 of using gold as the
aurothiocyanate NH4Au(CNS) 2 , inspired by the fact that gold toning is
more effective in the presence of an alkali thiocyanate. The process was at
first kept secret and used exclusively for Agfa emulsions. Patents were later
applied for by many other workers: Keller, <47 l Waller, Collins and Dodd, <4 Sl
Balsiefen. <49 l
According to the generally accepted hypothesis, the aurothiocyanate acts
by substituting the silver specks with metallic gold. In fact, when the emulsion
has not been chemically ripened the effect is practically nil. Faelens<49bl however,
has recently shown that silver bromide without binder can be immediately
sensitized with gold, without a ripening stage. This implies that the decompo-
sition of the aurothiocyanate is catalyzed by the silver bromide itself, and not
by the silver in the specks, or more exactly, as Steigmann confirms, by the
halide ions. <49c ) The experimenters have omitted to specify the size of the
crystals used in their tests. Now in practice, it is the large grains which
react most favourably to gold sensitizing.
Instead of adding the gold thiocyanate to the emulsion, the latter can be
immersed in the solution for a few minutes. In this way the sensitivity and
the development rate are increased (James). <50 l The gold is deposited auto-
catalytically; it reaches a thickness of 20- 80 mt--t after 64 hours immersion. It
is resistant to oxidizing agents unlike the silver specks.
Despite its apparent simplicity, gold sensitizing is an operation which is
very difficult to carry out conveniently. It is frequently deceptive: for if the
simple addition of a suitable amount of a gold salt raises the sensitivity three
times, the fog, and even more the instability, increase to such an extent that
the emulsion becomes useless after being kept for a few days.
There are two important factors which influence gold sensitization: the
choice of gelatin and the presence of a powerful antijoggant.
Among the most effective antifoggants are the azaindolizines (see para. 350).
Gold sensitizing technique. Some workers have shown an increase in sensi-
tivity when using gold chloride or sodium chloroaurate. We have been unable
to produce any useful effect from these products. Sodium gold thiosulphate
reduces the sensitivity and increases fog. Only the aurothiocyanate has been
shown effective.
To prepare ammonium aurothiocyanate add a 1·3 g per litre solution of am-
monium thiocyanate to an equal volume of a 2 g per litre solution of gold
chloride AuCl 3 , just before use. For example, 40 mg AuCl 3 corresponding to
20 cc of solution, and 20 cc of ammonium thiocyanate solution. Steigmann used
6 cc of 1% HAuCl4 • 3H 20 in 50 cc of 1% ammonium thiocyanate. The

B.I.O.S. report on German industry gives 1-5 cc of solution with 40 % Au in
1·5 litre of 1% ammonium thiocyanate, and 6·2 cc of this mixture is used
for 50 g silver nitrate.
If the aurothiocyanate is added to a completed emulsion, 30-40 mg AuCla:
is necessary to produce a speed increase of 3X.
If the aurothiocyanate is added before after-ripening, the amount should
should be at most one-third of this, as chemical ripening is greatly accelerated
with rapid increase in fog.
Gold sensitizing reduces the slope of the main part of the characteristic
curve and lengthens the toe. It is mainly effective with the large grains,
which are also the most sensitive.
For gold sensitizing to be effective, the parent emulsion must have a very
low fog level.
Influence of gelatin on gold sensitizing. The great disadvantage of gold
sensitizing is the fog. This originates with the reducing substances present in
the gelatin, and particularly the aldehydes. Furthermore, desensitizers in the
gelatin prevent aurothiocyanate sensitizing as they form a more stable com-
plex with the gold; these include glutathion, cysteine and the 4-carboxy-
thiazolidines. Traces of metals like copper and tin can also have an inhibiting
action from 1 part in 100,000 of dry gelatin.
The choice of gelatin is therefore important. It is, however, very difficult
to find gelatins free from reducing substances, for these are not removed with
active carbon. In fact, according to work by Landucci and Durante( 50u) a cer-
tain content of reductones is necessary for effective sensitizing, by enhancing
the prior formation of silver specks.
Steigmenn (51 > considers that sulphur sensitizers are useless when an emul-
sion is treated with gold unless the iodide content is less than 4 % and the
excess bromide during precipitation is small, in which case small quantities
of sulphur compounds and retarders are necessary. The same writer classifies
gelatins as ultra-inert, inert and gold-sensitive. The ultra-inert gelatins which
contain neither sensitizer nor retarder are the most suitable. Gelatins termed
inert to gold also give good results. They contain small amounts of sulphur
sensitizers and retarders. The 'gold-sensitive' gelatins are those which give fog.
To make the gelatin tests Steigmann preferred a neutral unwashed chloride
emulsion ripened in the presence of SO 2 and sensitized with aurothio-
cyanate. (52 > The emulsion is stabilized with 2-mercaptobenzoxazole usmg
25 parts to 100,000 of dry gelatin.
Effect of thallium and lead salts: see para. 303 and 371.
Platinum and palladium: their salts sensitize, but less effectively than
gold. (52b> The study of these elements showed the inhibiting action of
gelatin on sensitization by noble metals. Polyvinyl-alcohol is without action.
302. Role of silver iodide

The purpose of adding potassium iodide to the alkali halide is to precipitate
a small amount of silver iodide together with the bromide.
The silver iodide itself is not very sensitive to light, but in moderate
proportions, up to 6% , it increases, on the contrary, the sensitivity of
silver bromide by deforming the crystal lattice, the meshes of the two halides
being different. Its presence confers the following characteristics on an.
emulsion.
(a) Extended under exposure region therefore a less uniform curve.
(b) Larger grains. The protection given by gelatin against crystal growth
becomes less effective in the presence of a little Agi.
(c) The sensitivity increases with the Agi content to an optimum value. A
fast negative emulsion will contain about 3% iodide whilst a slow emulsion
may only contain 0·5 %. The optimum concentration varies with the emul-
sion type and the gelatin.
(d) After-ripening cannot be carried on as long with iodide present. With
0·5 % Agi digestion is difficult.
(e) The tendency to solarize increases with the iodide content.
(f) Gold sensitizing is facilitated.
The presence of silver iodide in an emulsion therefore has both advantages
and disadvantages. The advantages are greater sensitivity with extended
digestion and better colour sensitivity. The disadvantages are mainly a
characteristic curve which is distorted at each end, and coarser grain.
At higher iodide concentrations than those generally used, the latent
image is mainly internal, although close to the surface. <53 ) It is located on
the interfaces of the distinct silver bromide and iodide lattices in the same
gram.
FIG, 48.
303. Lead and thallium emulsions

The introduction of lead or thallium bromide into an emulsion changes its
principal characteristics:
(a) The grains become spherical in shape, more so as the proportion of lead
or thallium is increased.
(b) The sensitivity is reduced, but digestion fog is also lowered and the
Images are purer.
(c) The contrast is increased.

(d) The emulsion is more easily solarized.
Emulsions made entirely of lead or thallium halides can be prepared. They
have the characteristic curves shown in Fig. 48 -very contrasty and readily
solarized.
To precipitate lead or thallium bromide, the corresponding nitrates are
used as the soluble salts . In other respects the method is the same as for an
ordinary emulsion, but the temperature is lower-35 °C according to
Thom, (54 > who studied thallium bromide. The incorporation of thallous
bromide in a silver iodide emulsion increases the sensitivity one hundredfold;
the maximum is in the green. (55 >
Thallium salts, added to ammoniacal, gold sensitized emulsions in quan-
tities from 0·4 to 0·7 mg per g of silver have only a negligible influence.
304. Ultrasonic action

Following the communications of Claus( 57 l in 1933 affirming the power of
ultrasonic vibrations in dispersing silver halides in gelatin, and the memoirs
of other workers, the experiments of Protas (58 l in 1940, then of Peronnet and
Biquard (59 > in 1947 had shown that ultrasonics have no specific action on
photographic emulsions. The only things which can happen are on one hand,
the rupture of certain cyclic links in the gelatin molecule, and on the other,
the formation of a latent image by local pressure. (SO) More recently, Herold,
Jones and Knighton (SOb l have, however, successfully used ultrasonic vibrations
to increase the sensitivity of emulsions. Their apparatus consisted of a cooled
perspex cylinder immersed in oil to transfer the vibration. Under the tank of
oil is a barium titanate vibrating element. Energy SW jcm 2 at a frequency of
800,000 c.p.s.
305. Commercial emulsion manufacture

Photographic emulsions are commercially manufactured in 20-250 litre vessels
depending on the importance of the undertaking. These tanks are made of stainless
steel or enamel. They are generally jacketed for steam heating and fitted with a
m echanical stirrer. The enamel ones are of the usual double-wall type in a tipping
holder. A more highly developed system which can be heated or cooled at will is
fitted with a tight lid enabling work to be done in white light.
The emulsion is either cooled in the precipitation vessel, or is first poured into
20-litre vessels which are placed in vats of cold water. In some works it is put into
large flat enamel dishes cooled by water circulating at 2 °C.
If the emulsion is in pots it is set by leaving for several hours in a refrigerated room.
Neutral emulsions must not be placed in rooms which have had ammoniacal types in
them, for there is risk of fog or yellowing.
The set emulsion is shredded in a press by forcing it through a grid with sharp
edges.
Washing is carried out with water cooled to 10-12°C by the methods already given
in the chapter devoted to this operation. For a 500-litre washing tank, the water flow
is generally about 30 litre per minute.
After draining for two hours, the emulsion is remelted either in small lots in stainless
steel 20-litre pots or in 300-litre tanks of stainless steel or enamelled iron, heated in
the water-bath. Samples are removed every 10-15 minutes for sensitometric tests. The
after-ripening temperature must be rigorously controlled, and it is advisable to use a
thermostat.
After digestion, the emulsion is cooled rapidly to about 35 °C when the finals are
added before taking the emulsion to be coated. It can also be kept in a refrigerator
until it is used. The final product should be filtered under pressure through a cellulose
paste. Some manufacturers merely filter through a cloth bag which retains the large
particles and the froth. A storage tank kept at 32°C permits the air bubbles to rise to
the surface; it is preferable to use a baffled receptacle which retains the bubbles more
effectively and prevents them from being carried to the coating head.
Continuous preparation. Emulsions can be precipitated continuously. A series of
pumps introduce carefully controlled quantities of solutions of gelatin+ bromide and
silver nitrate at constant temperature into a small vessel. After remaining for a short
time, the emulsion is circulated through a spiral which is of sufficient length for
ripening, then falls into another receptacle where a SO% gelatin solution is added
before setting.
Another experimental system was described by Oshima and Ken-Ichi Ariga' "'l in
which the emulsion is ripened in the precipitation vessel from which it is drawn before
adding gelatin. The volume is kept constant at 1000 cc whilst 30 cc per minute of 10%
silver nitrate and 10 cc of a solution of 5% gelatin, 23% KBr and 0·9% KI are added,
and at the same time 40 cc of emulsion per minute is drawn off, to which is added
10 cc of 53% gelatin.
306. Powdered emulsions

The preparation of powdered photographic emulsions was suggested by Kennet in
1876. They are in fact obtained by desiccation, the product having the appearance of
semolina, which keeps indefinitely and can be readily redispersed in water.
The precipitated, washed and remelted emulsion is only partly ripened; it is then
broken up through a nickel gauze, the droplets being received in a slightly volatile
non-alcoholic liquid. The emulsion (in its proper sense) is then dehydrated at a
temperature sufficient to finish the after-ripening. The dry product still contains 15 %
water.
Slow chloride emulsions are also prepared, which can be manipulated in weak
white light, which are used for prints of sheet-metal templates, prints on anodized
aluminium or varnished zinc for placards, etc. The aqueous solution is sprayed on,
over an isolating varnish, at a pressure of about 3 Kg.
307. Manufacture of silver nitrate

The silver nitrate used for the manufacture of photographic emulsions must be
extremely pure and its preparation must be carefully supervised.
The crude 98-99% silver is first dissolved in nitric acid. By electrolysis of the result-
ing solution, silver with an assay better than 99·9% is obtained. This is redissolved in
nitric acid S.G. 1·4. This is boiled until crystallization starts and then poured into
receptacles, when 60-70% of the silver nitrate crystallizes overnight. The mother
liquors provide a second crop of crystals, frequently of lower purity when the metal
has been insufficiently refined. After rinsing in a centrifuge, the crystals are dried, or
preferably recrystallized from distilled water. (62 )
The silver is dissolved in batteries of double-walled tanks of 309 or 310 steel placed
in cascades until the concentration reaches 65 % . By evaporation, this is increased to
85%. The nitrous vapours which are evolved are oxidized to nitric acid and are
absorbed in water.
In the preparation of silver nitrate, rinsing the crystals with alcohol must be avoided
as the latter produces the explosive silver isocyanate.
M
308. Analysis of sensitive materials

The estimation of the silver and the halides in photographic emulsions is
usually made after dissolving the silver halide in a solvent.
(a) Dissolving in N /10 potassium cyanide. Mter separation of the metals,
the halides are titrated electrometrically in the presence of ammonium nitrate
following Clark's method.< 64 l Wagner and Pelz< 65 l passed a current of C0 2
then H 2 S through the cyanide solution; Ag 2S precipitates leaving in solution
the halides, which are titrated potentiometrically. The method of estimation
using cyanide is not recommended as it is dangerous and complicated.
(b) Dissolving in sodium thiosulphate free from halides. Thirty cc of 25 %
solution for 1 dm 2 of emulsion. The wash waters are added to the hypo
solution. Eight cc of 10% Na 2 S is then added and the solution brought to
the boil; the precipitate of silver sulphide coagulates. Mter filtering hot and
washing the precipitate with hot water, the silver sulphide is decomposed
with hot nitric acid which converts it to silver nitrate; distilled water and a
ferric alum indicator are then added before titrating with ammonium thio-
cyanate. <66 l The filtrate contains the halides. Sixteen cc of 5N sulphuric acid
is added and the solution is left for the SO 2 to be given off. Then 1 cc of
N / 10 KI is added followed by N /5 permanganate until a bluish colour is
produced. The halides are then titrated potentiometrically using N / 10 silver
nitrate and a silver electrode. <67 l The amount of iodide previously added is
naturally subtracted from the amount found by titration.
(c) Attack by a caustic alkali according to the method of Tellez-Plasen-
cia: <68 l this produces alkali halides which can be titrated directly, whilst the
precipitated silver hydroxide is recovered and converted to nitrate for
volumetric or potentiometric estimation.
Estimation of metallic silver. In addition to the usual methods of estimating
metallic silver after dissolving in nitric acid, the following can be used:
(a) Colorimetric estimation of silver using 2-thio-5-keto-4-carbethoxy-3-
dihydropyrimidine, in the presence of a buffer of nitric acid and sodium
acetate giving a pH of 2. (69)
(b) Colorimetric estimation of silver using insoluble tetramethylthionine
mercury iodide which liberates a dye in proportion to the amount of Ag
ions. <70 l
(c) Action of iodine on the silver, and electrometric estimation of the
excess iodine with standard sodium arsenite solution. The silver iodide formed
is dissolved in potassium iodide and the liberated hydriodic acid is neutralized
with sodium bicarbonate. Accurary 0·005 mg to ± 1 o/o. The electrode used is
a Foulk and Bawden polarized electrode. <71 l
(d) Formation of radioactive cobalt ferrocyanide on the silver and measure-
ment of the radioactivity with a Geiger counter (Baenziger). <72 l
(d) Conversion of the silver to the iodide with radioactive iodine P 31
according to the method of Ballard, Stevens and Zuehlke. <73 l To do this, a
mixture of potassium ferricyanide and radioactive potassium iodide is used.
1. Frieser H.: Zeits. Wiss. Phot., 1940, 67-80. Yano T.: Jl. Soc. Chem. Ind. Japan,
1940,44B.
2. Ollendorf and Rhodius: Sci. et Ind. Phot., 6(2), 245.
3. Stasiw 0. and Teltow J.: Sci. et Ind. Phot., 1948, 449.
4. Loening E. E.: Sci. et Ind. Phot., 1951, 455-457 and 1953, 437-451.
5. Gledhill and Malan found 10-• mol. per litre at 25 °C. Solubility product 5 ·08 x
10- 13 (Trans. Farad. Soc., 1953, 166).
5b. Davies C. W. and Jones A. L.: Trans. Farad. Soc., 1955, 51, 812-867.
6. Chateau H. and Pouradier J.: Colloque de phot. scient. Paris 1951; Sci. et Ind.
Phot., 1954, 3. See also: Jl. Chim. Phys., 1955, 133-140; Sci. et Ind. Phot., 1955,
240-242.
6b. Chateau H.: These Conserv. Nat. Arts et Metiers, Paris, Feb. 1955, Sci. et Ind.
Phot., 1955, 405.
7. Jonte J. H. and Martin D . S. Jr. :J.A.C.S., 1952,2052.
8. Abribat M . : Chimie Physique des couches sensibles, p. 76, Presses Universitaires,
Paris.
9. Pouradier J. and Roman J. : Sci. et Ind. Phot., 1952, 4.
10. Davis P.: R.P.S. Cent. Conference, London, 1953.
11. Estimations are made with soluble halide concentrations varying from 0·1 N-
0·001 N. The principle is applicable to many other elements.
12. Lyalikov K. S.: Compt. Rend. Ac. Sc. (U.S.S.R.), 1946, 425.
13. Lyalikov K. S.: Probl. Kinetiki i Kataliza, 1949, 7, 174-202.
14. Amman-Brass H.: Sci. et Ind. Phot., 1952, 249.
15. Murobushi K. and Ashikawa E.: Jl. Chem. Soc. Japan, 1949, 12.
16. Evva F. and Sziman 0.: Magyar Kemia Folyo., April1953, 97; Sci. et Ind. Phot.,
1953, 308.
17. Ohyama Y: R.P.S. Cent. Conj., London, 1953. Ohyama Y. and Futoki K.: Jl.
Soc. Sci. Phot.Japan, 1953, 39-47; Sci. et Ind. Phot., 1954,356.
18. Given by L.P.Clerc: 'Structure et proprietes des couches photographiques', p. 16.
Editions de la Revue d'Optique, Paris 1939.
19. See Slade and Higson: Phot.Jl., 1919,59, 260-265; 1920,60,140-145.
20. Loveland and Trivelli: Jl. Phys. Chem., 1947, 1004.
21. Silberstein L.: J.O.S.A., 1943, 33, 35.
22. Kottler F.: Jl. Franklin Inst., 1950, 339-356; Sci. et Ind. Phot., 1951, 49.
23 . Kottler F.: Jl. Franklin Inst., 1951,499-514, 617-641; Sci. et Ind. Phot., 1951,
370.
24. They can be floated on iced water.
25. The water jet, directed tangentially into the vessel, provides the agitation.
26. Blake G. G.: Chem. Ind., 1946, 28. The Philips Philoscope, a combination of a
bridge and a 1000-cycle oscillator, enables the wash water conductivity to be
measured.
27. Umano S. and Nakano Y.: Jl. Soc. Sci. Phot. Japan, 1952, 63-68, 69-76; Sci. et
Ind. Phot., 1952, 468.
28. Chibissov K. V., Titov A. A. and Mikhailova A. A.: C.R. Acad. Sci. (U.S.S.R.),
1946, 709; 1951, 319 and 1952, 547. See also: Sci. et Ind. Phot., 1952, 308.
29. Use of stannous salts: B. H. Carroll and Kodak, F.P. 1,008,788 (1949)-Chibissov
used hydrazine sulphate which lowers the sensitivity despite being a reducer.
30. Collins R. B. and Dickinson H. 0.: Sci. et Ind. Phot., 1952, 92.
31. Suzuki S. and Toriu T.: Jl. Soc. Sci. Phot. Japan, 1952, 9-26 ; Sci. et Ind. Phot.,
1953, 276.
32. Murobushi, Kawaguchi and Ashikawa: Jl. Chem. Soc. Japan, 1953, 373.
33. Ohyama, Y.: R.P.S. Cent. Conf. London, 1953.
34. Geuda, Matsuoka and Iwamoto : Bull. Inst. Phys. Chem. Tokyo, 1942, 884-889;
35. Bycichin and Vlach: Sci. et Ind. Phot., 1948, 263.
36. Evelgard E. R. E.: Swedish P. 100,681.

37. Lorenz R.: Sci. et Ind. Phot., 1953, 338.
38. Chateau H. and Pouradier J.: Sci. et Ind. Phot., 1954, 305.
39. Mueller F. W. H.: R .P.S. Cent. Conf., London 1953; Sci. et Ind. Phot., 1953, 494.
40. Teltow: Sci. et Ind. Phot., 20, 375.
41. Asai I.: Jl. Soc. Chim. Ind. Japan, 1939, 98B.
42. Kodak : F.P. 868,562 (1941).
43. Kroppf F.: Sci. et Ind. Phot., 1925, 197; Meyer K.: Sci. et Ind. Phot., 1952, 393.
44. G.P. 618,354 (1934).
45. G.P. 692,828.
46. Koslowsky R.: Z eits. Wiss. Phot., Aug. 1951, 65-72; Sci. et Ind. Phot., 1951,454.
47. G.P. Applic. 114,185 (Feb. 1943).
48. U.S.P. 2,399,083 (1946).
49. U.S.P. 2,540,085-6.
49b. Faelens P.: Sci. et Ind. Phot., 1956, 47.
49c. Steigmann A.: Sci. et Ind. Phot., 1955, 289-304.
SO. James T. H.:Jl. Colloid. Sc., 1948, 447-455; Sci. et Ind. Phot., 1949,52.
SOb. Landucci and Durante : Sci. et Ind. Phot., 1956, 11- 13.
51. SteigmannA.: Brit. Jl. Phot., 1951, 378; Sci. et Ind. Phot., 1951,433.
52. Steigmann A.: Sci. et Ind. Phot., 1952, 256-262 and 354.
52b. Faelens P.: Sci. et Ind. Phot., 1956, 121.
53. Hautot A and Sauvenier H.: Sci. et Ind. Phot., 1952, 169.
54. Thorn J. A.: Sci. et Ind. Phot., 1946, 193-204; see also Harper and Ritchie:
Trans. Faraday Soc., 1950, 641.
55. Luppo-Cramer: Phot. Korr., 1939, 137. For the preparation of these emulsions,
see Sci. et Ind. Phot., 8(2), 297.
56. Polster A.: Phot. Korr. 1955, 124-133; S ci. et Ind. Phot., 1956, 13.
57. F.P. 752,847 (1933) and Zeits. Techn. Phys., Feb. 1934, 74-79.
58. Protas I. R.: Kino. Phot. Chem. Prom., 1940, 39-41.
59. Peronnet J. and Biquard P.: Sci. et Ind. Phot., 1947, 161.
60. Bennet G. S.: Jl. Acoust. Soc. Amer., 1953, 1149.
60b. Herold, Jones and Knighton:Jl. Acoust. Soc. Amer., 1955,27, 9-12; Sci. et Ind.
Phot., 1955, 213.
61. Sci. et Ind. Phot., 1952, 41.
62. White D . R. and Rose C. E. : FIAT Final Report, No. 356, H.M. Stat. Office,
London.
63. Chem. Engng., 1952, 217-220.
64. Clark W.: Jl. Chem . Soc., 1926, 749-775; Sci. et Ind. Phot., 1926, 131.
65. Wagner G. and Pelz A.: Osterr. Chem. Ztg., 1951, 209-212; Sci. et Ind. Phot.,
1952, 323.
66. Kieser K.: Phot. Ind., 1943, 39.
67. Kheinmann A. S.: Kino. Foto. Khim. Prom., 1940, 53-56; Sci. et Ind. Phot.,
1948, 370.
68. Tellez-Plasencia H.: Sci. et Ind. Phot., 1943, 101-103.
69. Yoe and Overholser: Ind. Eng. Chem. (Anal. Ed.), 1942, 148.
70. Bouilloux G.: Bull. Soc., 1940, 184.
71. Lambert R. H. and Walker R. D.: Ind. Eng. Chem. (Anal. Ed.), 1941, 846.
72. Baenziger: Jl. Chem. Phys., 1948, 1175.
73 . Ballard E. A., Stevens G. W. W. and Zuehlke C. W.: P.S.A. Jl., 1951, 27-32.
Chapter XIX
NEGATIVE EMULSIONS
309. The preparation of photographic emulsions, and especially negative
emulsions, is a critical process whose results depend, as we shall see, on many
factors: quality and careful choice of gelatin, purity of the chemicals, prepara-
tion equipment, working method, etc.
The reproducibility of an emulsion is not always perfect, especially when
it is necessary to use different batches of gelatin. Furthermore, the large-scale
application of formulas worked out on an experimental scale, due to the
differences in volume brings about variations, so that it is necessary to adjust
all the conditions again to produce the same characteristics.
There is, therefore, no exact preparation formula for photographic emul-
sions, as the results always vary with the worker, his apparatus and the quality
of the working materials; some factors, such as the agitation and the tempera-
ture of the liquids, can have a great influence if insufficiently well controlled.
Above all, it must be remembered that because a gelatin is termed 'photo-
graphic' it is not necessarily suitable for an emulsion formula without giving
chancy results.
This is why the following emulsion formulas are given purely as illustra-
tions, which can be used as a basis for the preparation of particular emulsions.
All the formulas given here have produced excellent results for their origina-
tors, but used in a slightly different way, with other gelatins, they may not
always give satisfactory results: the different working factors must be ad-
justed until the desired characteristics are obtained.
In this, and the following chapter, the preparation of the emulsions them-
selves will be described, whilst in another chapter the finishing and stabiliza-
tion of emulsions before coating on their supports will be studied.
310. Neutral emulsions

The greatest danger in the preparation of neutral emulsions is the formation
of spontaneously developable aggregates of grains appearing as black spots
(grit) frequently visible to the naked eye. These spots are reduced in size and
number when the following factors are changed during precipitation: dilution
of the silver solution, reduction of the proportion of iodide, adjusting the
pH to as nearly neutral as possible, raising the temperature, increasing the
agitation.
327
The following formula, in our opinion, is the one which is best from all
points of view. The amounts of gelatin and silver nitrate are adjusted to give a
suitable viscosity and silver bromide content, two factors which must be
borne in mind in the composition of an emulsion for commercial use.
A Gelatin 3·5 g
70°C { Potassium bromide 31 g
Potassium iodide 10% 8 cc
{ Silver nitrate 37·5 g
Dry gelatin 55 g
Pour B into A with stirring, the time being variable between 30 seconds
and 5 minutes. Ripen for 60 minutes at 70°C. Add the dry gelatin. Continue
ripening for 30 minutes. Cool, set and wash 5 hours. Drain the noodles for
1 hour.
Add 20 g gelatin dissolved in 80 cc water, then 2 cc of 1% magnesium
bromide and digest for 2 hours at 55°C. If the noodles have absorbed too
much water, add only dry gelatin (2 hours before digestion to allow time for
it to swell).
The gelatin concentration has the following values at various stages:
Beginning of precipitation 3·2%
End of precipitation 0·75%
End of ripening 13%
During digestion 11%
Silver iodide content 2·1%
Excess of soluble bromide 20%
For more marked ripening, this excess can be increased to 40% using 36 g instead
of 31 g.
Amount of silver bromide per litre of emulsion 60 g
Amount of silver per litre of emulsion 34 ·5 g
Ratio R: gelatin/silver 2-4
Only the starting gelatin should be rich in sensitizers.

Quick precipitation gives higher contrast. Short ripening gives finer grain,
balanced by lower sensitivity.
Digestion can be continued until fog starts, without exceeding 0·05. The
emulsion is then stabilized with an antifoggant.
If the water in A in this formula is doubled, and that in B reduced, the
sensitivity drops; if the iodide is increased the sensitivity may also drop.
Carroll and Hubbard's formula:
A Ammonium bromide 42·7 g
{ Potassium iodide 2·3 g
Gelatin 20 g
B { Silver nitrate 60 g
c Dry gelatin 80 g
Pour B into A in 3-9 mins. at 65-70°C. Ripen for 30-60 minutes. Add the
gelatin C and continue ripening for 20-30 minutes with stirring. Cool, set,
wash and digest at 65°C until fog appears.
Initial gelatin content 5·7%
Gelatin content after precipitation 2·5 %
Gelatin content after ripening 12·5 %
Gelatin content during digestion 8-10%
Silver iodide content 4%
R = gelatin/silver 2·6
Extra-rapid Agfa 'Night film' formula {from F.I.A.T. Final Report No. 355,
Aug. 1945. H.M. Stationery Office, London).
A Potassium bromide 8g
{ Potassium iodide 0·5 g
Gelatin 1g
B {
Silver nitrate 9g
c Dry gelatin 25 g
D Potassium thiocyanate 0·03 g
( Silver nitrate 1% sol. sufficient for the precipi-
tate to remain dissolved.
Temperature 65-70°C. Pour half of B into A in one minute, then add the
second half in 29 minutes.
Add the gelatin C and ripen for a further 15-20 minutes with stirring.
Cool, set and wash. Digest in the presence of D for 60 minutes at 50°C.
311. Double-jet neutral emulsions

To prepare these emulsions, the bromide and silver solutions are added from
separate jets into a gelatin solution. The bromide must be adjusted so that
it is ahead of the silver by a constant amount. If a drop in the gelatin concen-
tration during precipitation is to be avoided, the colloid is added to the three
solutions and a uniform temperature is maintained. Example of formula:
A { Distilled water 400 cc
Gelatin 12 g
Ammonium bromide 61·5 g
B
{ Potassium iodide 3g
Gelatin 9g

C Gelatin 9g
( Silver nitrate 90 g
D Gelatin 60 g
Temperature 45-70°C.
Ripen for one hour at 65-70°C, add gelatin D, continue heating for a fur-
ther 15- 20 minutes, cool, set and wash the emulsion. Digest between 55
and 65°C after adding 36 g gelatin.
Concentration of gelatin during precipitation 3%
Concentration of gelatin on setting 9%
Excess soluble bromide 23 ·5%
The gelatin concentrations and the times can be modified according to the
gelatins used.
312. Acid emulsions

Emulsions precipitated in acid solution are generally slow emulsions. The acid
used is most frequently sulphuric acid, but it is possible to work at a higher
pH using citric acid (or other organic acid) or even monosodium citrate.
Two cc of sulphuric acid S.G. 1·18 in solution A of the formula in para. 310
reduces the speed but increases the contrast. The sensitivity increases with
the precipitation temperature (70°C) but the optimum gamma is obtained
at 55°C. There is an optimum amount of acid beyond which no increase in
gamma is obtained.
313. Borax emulsions

Borax emulsions are actually neutral emulsions which are made alkaline to
pH 8 during ripening. Steigmann's formula is:
ristilled
Gelatin
water 110 cc
4g
A
Potassium iodide 0·4g
{ Distilled water 90 cc
B
Silver nitrate 7g
c Silver nitrate 4g
{Distilled water 20cc
D
Silver nitrate 4g
E Dry gelatin 24g
{Water 15 cc
F
Borax 1·5 g
NEGATIVE EM U LSIONS 331
The bromide solution is used at 70°C and the silver solutions at 65-70°C.
To achieve stepped precipitation, 20 cc of B is added in 15 seconds, then the
remainder of B in 20 minutes with moderate agitation. Ripen for a further
5 minutes then add C in 1 minute. Ripen for 10 minutes. Finally, add D, the
gelatin E and the borax solution F. Ripen the whole for 20 minutes maintain-
ing the temperature at 70°C throughout. Set, wash, drain and digest at 65°C
in the usual way. During digestion an equal amount of borax can again be
added.
Initial gelatin concentration 3 ·6%
After first precipitation (B) 2%
After second precipitation (C) 1·8%
After third precipitation (D) 1·66%
Concentration for digestion 11·4%
Excess of soluble bromide 6·7%
314. Ammonia emulsions

To prepare ammonia emulsions, a certain amount of ammonia is added to
the gelatin-halide solution whereas with ammoniacal emulsions, the silver is
converted to the ammonia complex. Ammonia emulsions of high sensitivity
can be prepared with suitable gelatins free from sulphur dioxide. Formula
example:
Gelatin 6g
A Ammonium bromide 19 g
( Potassium iodide 0·7 g
Ammonia (S.G. 0·91) 4cc
B {
Silver nitrate 20 g
c { Distilled water
Silver nitrate
70 cc
10 g
D Dry gelatin 35 g
Temperature: 42- 70°C depending on the retarding power of the gelatin.
Pour B into A in 1-5 minutes. Ripen 10-60 minutes. Add C in 30 seconds
then gelatin D and continue heating for at least 15 minutes. Cool, set, wash.
Digest at 50°C after adding 9 g of gelatin which is allowed to swell in the
noodles.
Gelatin concentrations:
At the beginning of precipitation 3·6%
At the end of first precipitation 2%
At the end of ripening 11 %
During digestion 9-10%
Excess of soluble bromide 11·7%
In any formula it is essential to vary only one factor at a time to obtain the
optimum required result. Here, besides the temperature, the ripening times,
the initial gelatin content and the iodide content, the amount of ammonia can
be varied. Some users of this type of formula prefer to precipitate with a
gelatin of moderate activity, then add the gelatin rich in sensitizers just before
digestion.
A variation is to precipitate part of the bromide in neutral solution, then
add the ammonia and continue precipitation.
315. Completely ammoniacal emulsions

These emulsions are precipitated using ammoniacal silver nitrate which is
simply prepared by adding concentrated ammonia to the silver nitrate
solution until the first formed black precipitate of silver hydr_oxide is just re-
dissolved. The ammoniacal silver nitrate solution is formed of argento-
ammonium complexes whose composition varies with time. The ammoniacal
silver nitrate solution ages: It must therefore be used with the minimum delay
if reproducible results are to be obtained. Chibissov and his co-workers have
shown that with an old solution, silver nitride is formed in the emulsion; (I >
to overcome this disadvantage they disclosed crystalline ammoniacal silver
nitrate. (2 >
Formula for fine-grain emulsion:
A
ristilled wate>c
Potassium bromide
200 cc
63 g.
45°C Potassium iodide 10% 20 cc
Active gelatin 25 g
B { Distilled water 480 cc
35°C Silver nitrate 75 g
c f Distilled water 120 cc
45°C l Gelatin (low activity) 65 g
Add B to A in 5 minutes. Ripen 20 minutes at 45 °C. Add gelatin C. Wait
10 minutes then cool, set and wash. Mter draining, swell 40 g of dry gelatin
in the noodles and digest for about 60 minutes at 50°C.
At the beginning of precipitation 11-3 %
End of precipitation 3·6 %
End of ripening 11 %
During digestion about 10%
Silver iodide concentration 2 ·7%
Excess soluble bromide 23·5 %
R = gelatin/silver 2 ·3
Amount of silver bromide per litre of emulsion: about 75 g.
It is evident that by reducing the initial quantity of gelatin in this formula,
the speed is increased due to larger grains. Furthermore, part of the silver
nitrate need not be added until after 30 minutes ripening in order to extend
the gradati<>n of the emulsion. In this way ultra-rapid emulsions are obtained
with suitable gelatins.
Contrast formula:< 3 >
Gelatin 40 g
A
{ Ammonium bromide 18·4 g
Potassium iodide 0·6 g
Distilled water so cc
B Silver nitrate 14g
( Ammonia Q.S.
. (Distilled water 30 cc
C Silver nitrate 7g
Ammonia Q.S.
D Silver nitrate 7g
( Ammonia Q.S.
Solution temperatures: A, 45°C; B, C and D, 20°C. Add B to A with
moderate agitation. Ripen 5 minutes at 45°C. Then add C, wait 5 minutes
and add I). Ripen for a further 20 minutes. The set and washed emulsion is
digested for 60-90 minutes at 50°C. The after-ripening must be shorter if
the physical ripening is curtailed, that is, with .finer grain. For example:
Ripening Optimum Relative
time digestion time sensitivity Contrast Fog
10 m.ins. 65 mins. 25 3·2 0-01
30 mins. 90 mins. 240 2 0·02
Initial gelatin concentration 17%
Concentration after precipitation 11·4%
Excess soluble bromide 17·2%
R =gelatin/silver: 2·3.
Nelson-Kieser formula:
· Gelatin 40 g
A Ammonium bromide 20 g
( Potassium iodide · 0·7 g
Disodium phosphate 1g
B Silver nitrate 14·8 g
( Ammonia Q.S.
C Silver nitrate 14·8 g
( Ammonia Q.S.
Temperature of solution A: 45°C. Add B to A in 30 seconds. Ripen 45

minutes at 45°C. Add C and ripen for a further 15 minutes. Cool, set and
wash. Digest at 45-50°C, adding dry gelatin if desired.
Gelatin concentration after precipitation 8·5%
(after adding 2% of gelatin during digestion).
Start in acid solution. If a small quantity of inorganic or organic acid is
added to the bromide solution in an ammoniacal formula the formation of
spontaneously developable grains, which may be produced with some
gelatins, is prevented. The sensitivity is reduced however. Amount of acid :
2 g citric acid per 100 g silver nitrate.
316. Semi-ammoniacal emulsions

In this type of emulsion, part of the silver is first added as the normal nitrate.
After a certain ripening time, the remaining silver is added as the ammoniacal
solution, and ripening is continued for the full time. This procedure enables
fairly fast contrasty emulsions for photomechanical work to be obtained.
Example:
A
{ Potassium iodide 2g
Gelatin 50 g
c Silver nitrate
( Ammonia
50 g
Q.S.
D { Gelatin 50 g
Solution temperatures: A, 60°C; B, 55°C; C, 33°C; D, 45°C. Pour B into
A in 2 minutes. Drop the temperature to 45°C in 3 minutes, add the ammon-
iacal silver nitrate solution C in one minute, then ripen 10 minutes at 45°C.
Add gelatin D, stir 5 minutes, set and wash. Add 50 g dry gelatin to the
draining noodles, allow to swell for 2 hours, then digest for about 60 minutes
at 50°C.
Gelatin concentrations :
Initial 25%
After 1st precipitation 10%
After 2nd precipitation 6%
After ripening 10·7%
During digestion, about 10%
Excess soluble bromide 17·4%
The temperature of the neutral precipitation stage can be reduced to 45°C
if desired, and the ripening time shortened or lengthened, depending on the
retarding power of the gelatin used.
Simultaneous precipitation semi-ammoniacal emulsions. The two silver
solutions-neutral and ammoniacal-are not added separately as in the
preceding formula, but simultaneously. The following is a Steigmann third-
ammoniacal formula:
Gelatin lOg
( Potassium iodide 0·8 g
Sodium sulphate anh. 4g
c Silver nitrate
( Ammonia
10 g
Q.S.
D Dry gelatin 40 g
The two solutions, B and C are preferably used at 58°C. They are added
simultaneously, with moderate agitation, B in 2 minutes and C in 1 minute.
After 14 minutes ripening the dry gelatin is added, and heating is continued
for 20 minutes before cooling. The washed emulsion is digested at 50-65°C.
The introduction of sodium sulphate into the precipitation solution has,
according to the author of the formula, the effect of increasing the contrast
greatly. The action of sodium sulphate has only been claimed for this emul-
sion exclusively.
Initial 4 ·16%
After precipitation 2·17%
After ripening 10·8%
Excess soluble bromide 8·8 %
(without adding gelatin for digestion).
317. Emulsion mixtures

The gradation of an emulsion, that is, the exposure latitude, is improved by
stepped precipitation. It is increased even more by mixing a slow emulsion
with an ultra-fast one. To do this properly, it is essential that the speed and
contrast of the slow emulsion are such that the curve joins perfectly onto that
of the fast emulsion which it should continue in the high exposure region. As
the contrast of the slow emulsion is reduced by mixing, it must be harder
than the fast emulsion, the result should be a characteristic curve which is as
straight as possible. In the opposite case, the curve has a definite junction
point. A perfect mixture is very critical to prepare, for it is also necessary to
consider the colour sensitization which can alter the contrasts of the two
constituents unequally, and destroy the balance of the curves. The effect of
the colour sensitizer must therefore be considered when the characteristics
of the parent slow emulsion are established.
These phenomena become more complex when three emulsions of different
sensitivity are blended. In principle, extremely long curves can be obtained
by combining a large number of emulsions, by integrating, in series, their
characteristic properties, the resulting curve then appearing as a more or less
uniform chain.
Superimposed emulsions. Many commercial materials are made up of two
superimposed emulsions, the first layer next to the base being slower than
the rapid outer layer. The joining of the two characteristic curves presents
the same difficulties as with blends. Usually the curve has a flat portion.
Note. All the amounts of bromide, iodide and silver nitrate given are assumed
to be those of the theoretically dry compounds. In practice, the percentage
of water which they contain must be added, and this is determined by drying
samples in an oven at 120°C. Commercial gelatin generally contains 15 %
water; the quantities given can be left as they are.
1. Chibissov K. V., Titov A. A. and Mikailova A. A.: Doklady Akad. Nauk .

U.S.S.R., 1950, 453.
2. Sov. Pat. 72,274 (1948).
3. Steigmann.
Chapter XX
SLOW EMULSIONS
318. Slow emulsions, for transparencies and papers, are notable for their
fine grain, generally high contrast and absence of fog. Those to be used for
transparencies must be rich in silver so that high densities can be readily
obtained. Paper emulsions are necessarily weak and used in thin layers, for
the image density-and therefore contrast-is doubled by reflection.
Slow emulsions generally have a low iodide concentration and a high
gelatin content.
The choice of gelatin is of extreme importance, it affects the cleanness, the
sensitivity, and above all, the contrast. Gelatins for bromide emulsions are
fairly rich in sensitizers and retarders; they generally give solutions of low
viscosity. Gelatins for chloride emulsions are inert, but rich in sensitizers;
they are also harder.
Only a practical test can show if a gelatin is suitable for a particular formula.
This test must not only be made for the determination of sensitometric
values, but also the keeping properties.
The properties of a gelatin depend on the nature of the raw materials used
in its manufacture. Only the manufacturer can know this: the user is almost
always in complete ignorance of the relationship existing between the photo-
graphic characteristics of an emulsion and the treatment which the gelatin
has received.
Starting with a standard formula, it is possible, however, to prepare emul-
sions with varying sensitivity and contrast, by bringing into play the different
operational factors : concentration of gelatin, precipitation temperature, pH
of precipitation, time of ripening, and addition of various substances.
SILVER BROMIDE EMULSIONS

319. Fast neutral diapositive emulsions
We have shown, in the previous chapter, that a neutral negative formula can
be used for process work. This formula, suitably modified, will give an excel-
lent, and relatively fast, positive emulsion. Example:
A Distilled water 100 cc
Gelatin 10 g
337
B Distilled water 350 cc

Silver nitrate 37·5 g
C Dry gelatin 50 g
Precipitation temperature: 70°C. Pour B into A in one minute. Add the
dry gelatin and continue to heat for 15 minutes, after dropping the tempera-
ture to 45°C if only moderate ripening is required. Set, wash and after-ripen
for 60 mins. at 55°C after adding 20 g gelatin in 80 cc water and 2 cc of 1%
potassium bromide.
To avoid any ripening, the dry gelatin C can be dissolved in 120 cc water.
The speed and contrast of the emulsion is dependent on the grain size.
320. Ammoniacal positive emulsions

Good positive emulsions can be obtained by modifying the fine-grain ammonia-
cal emulsion given in the previous chapter, or the contrast formula. The
sensitivity decreases and the gamma increases as the ripening is reduced. A
high initial gelatin concentration slows down ripening. In addition, the iodide
concentration can be reduced to half. In the contrast formula, the silver
nitrate solution can be added rapidly in one stage.
When the physical ripening must be reduced as much as possible, a quan-
tity of sulphuric acid sufficient to neutralize all, or a great part of, the am-
monia, must be added immediately after precipitation.
The contrast can be increased if the bromide solution is acidified before
precipitation with a little sulphuric or citric acid: for example, 3 cc of concen-
trated sulphuric acid for 100 g silver nitrate.
The contrast can also be increased by first adding a small proportion of the
silver nitrate unconverted (semi-ammoniacal type), for example:
Moderate speed contrasty formula:
Gelatin 83 g
Sulphuric acid 1 : 6 vfv 0·7 cc
Silver nitrate 7g
c Distilled water 230 cc
Silver nitrate 50 g
Ammonia Q.S.
Temperatures: A and B, 45°C; C, 35 °C. Pour B then C, rapidly into A.
Ripening 10 mins. at 45°C. After washing, after-ripen for about 50 mins. at
50°C.
It is very important to after-ripen diapositive emulsions until they have
reached their maximum contrast. Sometimes this operation is carried out in
the presence of cadmium or copper chloride (in the proportion of 0·3 parts
SLOW EM U LSIONS 339
per 1,000 of silver nitrate) which reduces the speed, and increases the con-
trast slightly. After-ripening in acid solution also reduces speed.
Hard positive emulsions, such as those used in the graphic arts, cine
positives and microfilms are made more and more in chlorobromide types,
which will be studied later.
321. Bromide emulsions for high-speed papers

Photographic papers with high speed are used for direct document reproduc-
tion. Fast bromide emulsions with high contrast and giving a good black
image are needed.
Neutral emulsion:
Gelatin 5g
C Distilled water 75 cc
Gelatin 37·5 g
Solutions at 70°C. Pour B into A quickly. Wait 2 mins. and add the gelatin.
Ripen for a further 5 minutes and set. Wash, and after-ripen 50- 60 mins. in
the presence of 2 cc of 1% potassium bromide. Sensitize to green.
Semi-ammoniacal formula:
Gelatin 160 g
Sulphuric acid, 10% sol. 2 cc
Silver nitrate 10 g
Silver nitrate 60 g
Ammonia Q.S.
Temperatures: A, 45°C; B and C, 38°C. Pour B into A in one minute, and
add C in 30 sees. Ripen 10 mins. at 45°C. Set, wash. Mter-ripen 45 minutes,
after adding 55 g of gelatin and 200 cc water. Stop after-ripening by adding an
antifoggant (see emulsion finishing) and green sensitize.
322. Bromide emulsions for printing papers

These emulsion formulas are similar in principle to the preceding ones.
Ripening is reduced to a minimum and sufficient 8- 10% gelatin is added to
the washed product to give a final emulsion containing the equivalent of 20 g
silver nitrate per litre. The following proportions can be used as a starting
point (ammoniacal type).
Gelatin 230 g
Silver nitrate 100 cc
Ammonia Q.S.
Precipitation temperature: 40°C. Precipitation time 30 sees. to 10 mins.
depending on the gradation required; the faster the precipitation, the more
vigorous the emulsion. The emulsion is set immediately after precipitation.
Ripening can be quickly stopped by adding a dilute acid which neutralizes
the ammonia.
After washing, 1000-1800 cc of 9% gelatin is added to the melted emulsion.
Mter-ripening at 50°C increases the sensitivity, and often alters the contrast.
The addition of 10-50 mg of cupric chloride during after-ripening gives a
reduced speed, often balanced by an increase in contrast. The addition of an
acid, sulphuric or citric for example, also reduces the speed.
It is not, however, always necessary to after-ripen a paper positive emul-
sion. The emulsion can simply be stablized by adding an antifoggant: 3 g of
potassium bromide or 1 g of benzotriazole. Changes· in the characteristics can
nevertheless be produced with citric acid (1 g) and also by a supplementary
addition of potassium iodide which iodizes the grain surface.
It goes without saying, that the basic formula can be varied: increase or
decrease of the iodide concentration; addition of citric acid to the salts; using
part of the silver unconverted, etc. The way in which the emulsion is modi-
fied and the magnitude depends mainly on the gelatins used.
323. Agfa Brovira bromide paper emulsions

The F.I.A.T. Final Report No. 355<1 > from the investigation teams in Ger-
many gives a number of formulas for Agfa Brovira papers of different grada-
tions, which are reproduced below. The most interesting is the 'extra hard'
formula which several firms have tried to reproduce with disappointing
results.
The extra hard emulsion has three special features: firstly, it is not the
silver nitrate which is poured into the bromide, but the ammoniacal bromide
which is poured into the gelatin-silver nitrate solution. Secondly, the contrast
is obtained by adding rhodium chloride to the silver nitrate, and this is ex-
tremely active in very small quantities; it results in a simultaneous reduction
of speed. Thirdly, the washed emulsion has a long after-ripening in the pres-
ence of potassium iodide and citric acid to acquire its characteristics. We
would add that for this type of emulsion special gelatins are needed which are
rich in sensitizers and retarders, gelatins which have been produced by the
Cie Rousselot among others.
SLOW EMULSIONS 341
When such formulas as these are used, an intense yellowing is frequently
produced due to traces of ammonia in the air and which contaminate the
gelatin solution containing silver nitrate. This yellowing is easily avoided by
adding to the gelatin 20% of its weight of citric or tartaric acid.
More serious is the question of the rhodium chloride. This is extremely
unstable in solution. It is better to use the double chloride of rhodium and
ammonium which is dissolved just before use in 5% sodium chloride. 0-4 mg
is sufficient, when added to a litre of an emulsion containing 26 g silver
nitrate, to raise they to 5. Unfortunately this high contrast is not maintained
in the conditions prescribed by the formula. After three months it drops, and
the extra hard emulsion becomes an emulsion which is only vigorous. This is
undoubtedly due to the instability of the rhodium centres on the silver brom-
ide crystal. This is not the case with silver chloride which, with this metal,
forms much more stable compounds.
The sensitivity is proportional to the quantity of ammonia. It increases
also, as we know, with the ripening time and temperature with a correspond-
ing decrease in contrast.
For matt emulsions add 11 g starch per litre.
The Brovira emulsions are prepared, with the exception of the extra hard,
by adding 2 to 1 then 3 to (1 +2). The silver nitrate solution 4 is then added
and the remainder in the order given. For the extra hard emulsion, 4 is first
added to 1, following by 3 then 2.
Solution temperatures:
1. Extra hard and special: 45°C; hard, normal: 48°C; soft: 40°C.
4. Extra hard: 45°C; 25°C for the others.
SILVER CHLOROBROMIDE EMULSIONS

324. Methods of preparation
Chlorobromide emulsions are prepared by the action of silver nitrate on a
mixture of alkali chloride and bromide in a gelatin solution, and in a slightly
acid medium.
It takes 58·5 g of sodium chloride NaCl to completely precipitate 170 g of
silver nitrate, forming 143·5 g of silver chloride. The equivalent quantity of
potassium bromide is 119 g. One mole of sodium chloride can be replaced
by one mole of ammonium chloride (53·5 g) or one mole of cadmium chloride
(147·1 g).
The sensitivity of a chlorobromide emulsion increases with the proportion of
bromide, and with the size of the grains, for the same gelatin and a definite
preparation type. In parallel with this, the image colour is less warm as the
bromide increases.
Compared with pure bromide emulsions, chlorobromide ones are slow,
contrasty and very fine grained. Their sensitivity, however, can be very
greatly increased by colour sensitizing, as their inherent sensitivity barely
reaches the blue. This enables emulsions to be prepared which are, at the
w
+
N
BROVIRA FORMULAS FOR GELATINO BROMIDE PAPER
Extra hard Hard Normal · Special Soft
JGelatin 500 g 500 g 500 g 500 g 4000 g

1
\_Water 201 201 201 25 1 161
(Potassium bromide 750 g 750 g 750 g 750 g 3060 g "0

I Sodium chloride - - - 100 g - :t
2 ~ Potassium iodide 10% 0
l
Ammonia
Water
100 cc
1000 cc
2 ·5 cc
100 cc
-
-
300 cc
-
-
100 cc
200 cc
-
1250 g
260 cc
25 % Am Br
t-l
0
Cl
~
= 21 >
"0
:t
f Sodium chloride 25 % 180 cc 180 cc 100 cc - - .....
3 ()
\_Rhodium chloride 1 : 10,000 18 cc 6·5 cc 1-2 cc - -
()
:t
(Silver nitrate 1 kg 1 kg 1 kg 1 kg 5 kg t%1
JWater
Ammonia -
31 61
11
61
11
61
Add in 10 sec.
so 1
-
~
.....
r:.n
4 t-l
I then AmOH ~
><
I 800 cc
l Ammonium nitrate 10% - - - - 1125 cc
sf Gelatin 2500 g 2500 g 2500 g 2500 g 3750 g

\_Water - - - - 121
Ripen 30 mins. at 30 mins. at 30 mins. at 30 mins. at

45 oc 45 °C 45 °C 45 °C
Brovia Formulas for Gelatino Bromide Paper-continued.
Then add: Extra hard Hard Normal Special Soft
(Sulphuric acid S.G. 1·18 1200 cc 1500 cc 1570 cc 1575 cc

6~ Citric acid 40% 60 cc - - 300 cc
l Citric acid 50% - 250 cc 300 cc
I Wash the emulsion, remelt and add:

Water
Gelatin
-
700 g
-
1000g
-
850 g
-
1000 g
60 l
9000 g
00
1:"'
0
7
l Potassium iodide 0 ·65%
Potassium bromide 25 %
Sodium chloride 25 %
300 cc
10 cc
-
250 cc
10 cc
-
250 cc
10 cc
25 cc
250 cc
40 cc
-
-
-
-
~
tT.I
:s:
l Cupric chloride 1% Cu - - 3 cc - - c=
1:"'
00
.....
Ripen 75 mins. at 55 mins. at 50-60 mins. at 60 mins. at 60 mins. at 0
48°C 48°C sooc 48 °C 75 °C z
00
then add:
8 Citric acid 50% 40 cc so cc 55 cc 50 cc 275 cc
Before coating add, per litre:

(Chrome alum 10% 4 cc 4 cc 4 cc 4 cc 4 cc
J
Formalin 30% 7 cc 7 cc 7 cc 7 cc 7cc
9
l
Potassium m etabisulphite 10%
Citric acid 50%
Cupric chloride 1%
2·5 cc
4 cc
1 cc
3 cc
4 cc
2·5 cc
2·5 cc
4 cc
2·5 cc
2·5 cc
4 cc
2·5 cc
4 cc
LSaponin 3% 50 cc 50 cc 50 cc 50 cc 50 cc
w
4>--
w
344- PHOTOGRAPHIC CHEMISTRY
same time, very fine grained, of high contrast and relatively high sensitivity,
and which are used for photomechanical work, microfilms and also for cine
positive films.
Very high contrast chlorobromide emulsions are prepared with cadmium
chloride. Minute amounts of the double chloride of rhodium and ammonium
also produce a great increase in contrast. Potassium iodide added after precipi-
tation has a slight effect in the same direction. But always, the highest contrast
is obtained when the percentage of chloride is increased with a very short
ripening (to the detriment of the sensitivity). Finally, acidification of the
finished emulsion can also increase the contrast.
Extra fine grain emulsions rich in silver give very warm tone images. They
are also the slowest. They are obtained either with a very short or low
temperature ripening step or with gelatin containing a high proportion of
retarders. The addition of 200 mgflitre of hydrazine hydrochloride has been
disclosed by Trivelli and Smith as a means of obtaining the warmest tones.
Some chlorobromide emulsions are not washed. Although their preparation
is apparently simple, in practice it is difficult to obtain adequate sensitivity,
and their stability is inferior to washed emulsions. Furthermore; suitable
gelatins are less common.
Precipitation methods. In practice there are at least eight different precipi-
tation methods used for preparing chlorobromide emulsions, which can be
divided into four groups:
A. Normal precipitation
1. Silver into salts.
2. Double jet of silver and salts.
3. Two consecutive precipitations silver into salts.
B. Reverse precipitation
4. Salts into silver.
C. Part of the chloride precipitated separately at the end
5. Normal precipitation, then addition of chloride followed by more
silver.
6. Normal precipitation, then excess silver, precipitated by more chlor-
ide (second precipitation reversed).
D. Separate precipitation of bromide and chloride
7. Precipitation of bromide by the silver, then chloride by the silver
(two normal precipitations).
8. Precipitation of bromide by excess silver, then precipitation of the
latter by the chloride (second precipitation reversed).
325. Chlorobromide emulsions by normal precipitation (type A)

The gelatin-halide solution is generally acidified with citric, sulphuric or
hydrochloric acid. The silver nitrate solution can be neutral or acid (citric
or nitric acid). The precipitation temperature varies from 40-70°C.
SLOW EMULSIONS 345
1. Wall's formula for warm tones:
Ammonium bromide 20g
Sodium chloride 10 g
Citric acid 50 g
Gelatin 70 g
Silver nitrate 50 g
Citric acid 50 g
Heat solution A to 70°C and add to it, with stirring, solution B, cold. Ripen
for at least 10 minutes. If the emulsion is washed, add, after digestion, 40 g
gelatin and 2 g sodium chloride.
lb. Steigmann's formula:< 2 >
Sodium chloride 4·2 g
Cadmium chloride 1g
Gd~n 12g
Sulphuric acid 5% 15 cc
B Distilled water · 120 cc
Silver nitrate 12 g
If the gelatin is poor in retarders, add finally 1-3 cc of 2% egg albumen.
More retarders must be present if contrast is required. A soft emulsion must
contain very little.
Precipitation temperature: 40°C.
Pour B into A with stirring, then add 42 g gelatin. For a normal emulsion,
then add 1 cc albumen solution; 8 cc for a contrasty emulsion. Ripen 15 mins,
at 40°C. 7·5% gelatin solution is then added as follows:
Contrasty emulsion 150 g
Normal emulsion 200 g
Soft emulsion 250 g
then the following solutions of 0·1 % formolcystine and 1 : 2000 ammonium
thiosulphate are added:
Formal- Ammonium
cystine thiosulphate
Contrasty emulsion 6 cc 6 cc
Normal emulsion 3 cc
Soft emulsion
A second ripening is then given: 20 mins. for a contrasty emulsion, 30 mins.
for a normal emulsion and 50 mins. for a soft emulsion. Coat without washing.
Formolcystine is prepared as follows:
Dissolve 1 g of cystine in the minimum of 5% caustic soda at 90°C. Add
0·5 cc formalin and boil for 5 mins. The yellow-brown liquid is made up to
llitre. It will keep in the dark.
2. Double-jet emulsion for brown tones: <3 l

Gelatin Sg
Citric acid 0·5 g
Silver nitrate Sg
5% Gelatin sol. Sg
D Gelatin 4g
Temperature of solutions: 45°C.
First add a few drops of the salt solution B to the stirred gelatin solution A,
then simultaneously, from two separate jets add B and C in the ratio of 2 cc
of B to 5 cc C (each 10 sees. for example). Ripen 10 mins. at 45°C, then cool
and set in a refrigerator, cut up and wash for one hour. The shredded emul-
sion is then melted at 42°C, gelatin D added together with 2 cc phenol
solution (see para. 205) and then 0·1 g sodium chloride.
Concentration after precipitation 8%
Concentration after re-melting 10-11 %
Amount of silver bromide in the chlorobromide : 36 % .
Quantity of chlorobromide per litre of emulsion: about SO g.
2b. Rapid warm tone double-jet emulsion: <4 l
The gelatin used for precipitation should preferably contain more retarders
than the gelatin added later.
A Distilled water 300cc
Sodium chloride 9g
Cadmium chloride 0·9 g
Gelatin 15 g
Silver nitrate 24g
First pour a few cc of A into the mixing crock, then add A and B simul-
taneously with agitation, taking care that an excess of A is always present.
Add 54 g gelatin which dissolves in about 15 mins., the 3 cc of 5% sulphuric
acid. Ripenfor 1 hour between 70 and 75 °C or between 60 and 65°C if 9 cc
of 1 : 2000 ammonium thiosulphate has been added:
The above formula should give very high contrast. For contrasty, normal
and soft emulsions, use the following proportions:
SLOW EMULSIONS 347
Contrasty Normal Soft
A Distilled water 300 cc 300 cc 360 cc
Sodium chloride 6g 4·5 g 3g
Potassium bromide 8·4 g 10·5 g 15 g
Gelatin 15 g 15 g 24 g
B Distilled water 450 g 450 g 450 g
Silver nitrate 24 g 24 g 24 g
Precipitation temperature 50°C 55°C 55°C
Dissolve second gelatin at 55°C 60°C 60°C
For the normal emulsion, the second gelatin must contain less retarders
and more sensitizers.
For the soft emulsion the amount of retarders must be still less and the
sulphuric acid omitted.
3. Rapid chlorobromide emulsion using two consecutive precipitations: <5 >
65°C Sodium chloride 1·5 g
Gelatin 9g
20°C Silver nitrate 6g
Sulphuric acid 5% 5-11 cc
D Distilled water 120 cc
Add B to A in one minute. Ripen 10 mins. at 65°C; add solution C, then D.
Continue to ripen for 20 mins. Add 39 g gelatin and ripen again for 30-60
mins. Add 120 cc of 8% gelatin and cool. Coat without washing.
For emulsion choose a gelatin which contains little retarders, but rich in
so2 or bisulphite, which favour ripening.
Concentration for second ripening 9·4%
Quantity of silver chlorobromide per litre of emulsion: about 22 g.
326. Reverse precipitation chlorobromide emulsion (Type B)

4. 'Brovira Braun' extra hard type formula:
Gelatin 10 g
Citric acid 40% 4 cc
B Silver nitrate 10 g
Lead nitrate 1% 10 cc
Sodium chloride 25 % 20 cc
Ammonium bromide 25 % 11 cc
Rhodium ammonium chloride 1 : 10,000
in 25 % NaCl 0-2 cc
Gelatin 40 g
Potassium iodide 0-65 % 2 cc
E Potassium iodide 0-65 % 4 cc
All solutions, except E, at 60°C. The sodium chloride and ammonium
bromide solutions contain 25 g in 100 cc water.
Add the silver B to A in 15 sees. with stirring. Wait 30 sees. Add C in
15 sees. Ripen 40 mins. at 60°C. Then pour in the gelatin D and continue
ripening for a further 60 mins. Finally add the iodide E, cool and set.
The original emulsion is unwashed. It gives, when developed, a yellow fog.
Much better results have been obtained, by the author, with a washed ernul-
swn:
Precipitation Ripening Rel.
temperature time Variable Gamma Speed Tone
mms.
60°C 40+60 3·7 17 warm black
60°C 40+ 0 6·4 13 warm
45°C 40+ 0 8·5 5 very warm
60°C 40+60 Double 2·2 25 black
lead
50°C 0+ 0 No 4·7 14 warm
rhodium
These figures were obtained on paper. The addition of 1 g per litre semi-
carbazide hydrochloride or hydrazine sulphate gives warmer tones. Adding
20 mg per litre of gold chloride as the aurothiocyanate doubles the speed.
Increasing the proportion of bromide gives a more sensitive emulsion, but the
image is colder (owing to the larger grains).
327. Chlorobromide emulsions with part of the chloride precipitated

separately later (Type C)
5. Final chloride precipitated normally. In this type of emulsion, a mixture of
alkali bromide and chloride is precipitated by the silver in acid solution. After
a certain ripening time, the remaining chloride is added, then this is precipi-
tated by a second acidified silver nitrate solution. Washing follows, then
SLOW EMULSIONS 349
after-ripening at 50°C for 30 mins. with the addition of a gelatin solution.
Emulsions obtained in this way generally keep badly and have only a slightly
warm tone.
6. Chlorobromide emulsions with second chloride precipitation reversed. These
emulsions give very warm tone images of good quality, but their sensitivity
is relatively low, necessitating colour sensitization, and they must be stabilized
with antifoggants and also anti-yellowing agents. A typical example for the
'Portriga' type of paper is:
Gelatin 62 g
Sodium chloride 4g
Monosodium citrate 6g
Silver nitrate 50 g
C Sodium chloride 19·5 g
D Gelatin 165 g
Precipitation temperature: 40-45°C. The silver solution B is first added to
A. Mter 10 minutes the chloride C is added very quickly. The emulsion is
ripened for 30 minutes at 45°C and then the gelatin solution Dis added, and
ripening is continued for a further 30 minutes. Wash and after-ripen 0-60
minutes at 50°C.
The purpose of the chloride in solution A is to increase contrast. It must
therefore be reduced in the case of a softer emulsion. The monosodium citrate
buffers the solution at a moderately low pH to avoid the formation of develop-
ment centres. The sensitivity increases with the proportion of bromide whilst
the tone becomes colder. The addition of 2·5 g citric acid to the finished
emulsion increases the contrast and reduces the sensitivity. Increasing the
amount of iodide in solution D increases the sensitivity to the detriment of
the warm tone.
6b. Extra hard unwashed chlorobromide emulsion:<6 l
A Water (ordinary) 4000 cc
60°C Gelatin (inert) 400 g
Cadmium chloride 40 g
Egg albumen 2% 60 cc
Colour sensitizer 0·5 % 120 cc
c Water (ordinary) 11,000 cc

60°C Sodium chloride 180 g
E Distilled water 3000 cc
21 °C Silver nitrate 200g
F Water (ordinary) 3000 cc
50°C Sodium chloride 100 g
Gelatin (inert) 400 g
Cadmium chloride 10 g
Add B to A rapidly. Bring to 60°C and ripen 10 mins. Add C then the silver
D in 3 mins. Continue ripening for 20 mins. and add 1350 g of dry inert
gelatin; stir for 10 mins., then reduce the temperature to 49°C. Add the silver
E then the mixture F and finally 250 cc 2% egg albumen. In the case of a
very inert gelatin add 100- 200 cc hypo (0·5 g per litre). Add antifoggant and
if desired, gelatin solution.
328. Chlorobromide emulsion with separate precipitations of bromide

and chloride (Type D)
7. Into a solution of an alkali halide and gelatin, pour, first, a solution of silver nitrate
which precipitates the silver bromide. After ripening, add a chloride solution and
precipitate with a second silver nitrate solution. Gelatin is then added, and the
emulsion is again ripened for a suitable time before being set, washed and digested
at 50 °C.
The emulsion prepared in this way has relatively coarse grain. It has, however, a
high contrast (y = 3 for diapositives).
8. Separate reversed chloride precipitation formula (Brovira-weich Braun type):
A. Distilled water 700 cc
60°C Gelatin 100 g
Ammonium bromide 30 g
Citric acid 15 g
B. Distilled water 1000 cc
60 °C Silver nitrate 100 g
D. Water 1000 cc
55 °C Sodium chloride 30 g
E. Water 2000 cc
60°C Gelatin 400 g
Pour B into A in 10 sees. Stir 20 sees. and add D. Ripen 40 mins. at 60 °C. Add E
and raise the temperature to 68 °C in 10 mins. Stir 25 mins. and cool. Can be washed
or unwashed.
SILVER CHLORIDE EMULSIONS

329. Silver chloride emulsion types
Chloride emulsions are used to make 'gaslight' papers for printing amateur
negatives. They are available in extra hard grades which enable prints to be
made from very thin negatives.
SLOW EMULSIONS 351
Chloride papers generally give warm black or bluish-black images. The
bluish-black tones are readily obtained by adding certain compounds which
will be described in the next chapter. Warm black materials are more difficult
to obtain commercially as the most effective antifoggants generally favour
blue tones, and those which keep the warm tone are less effective stabilizers.
For the image colour to be sufficiently black, relatively coarse grain is
necessary which necessitates some ripening. If the grain is very fine the image
is definitely warm, and at the same time, the sensitivity is low.
Ivory and chamois chloride papers necessarily have warm tone emulsions.
There are many ways of precipitating chloride emulsions:
(a) The simplest is to pour the silver into an acid solution of gelatin and
soluble chloride.
(b) The soluble chloride is added to the silver solution (reverse precipi-
tation).
(c) Some silver is added to a small part of the halide, then the rest of the
latter followed by the second silver addition.
(d) The silver is added in excess to a part of the chloride (normal precipi-
tation). The rest of the chloride is then added to the excess silver (reverse
precipitation).
Reversed precipitation generally results in high contrast. Contrast can also
be increased by using cadmium chloride or a trace of rhodium ammonium
chloride.
The addition of a small amount of bromide to the soluble chloride reduces
the contrast and increases the sensitivity.
Gelatins for chloride emulsions are those with high viscosity, poor in
sensitizers but rich in retarders. The presence of SO 2 reduces the contrast.
Furthermore, they must not contain hydrolysis products which can form
soluble silver complex compounds, and therefore promote the production of
yellow fog. (See para. 349 F and K.)
Some emulsions are unwashed.
The principal difficulties in the preparation of commercial chloride emul-
sions are to obtain high contrast and to make them keep. They often need
large amounts of stabilizer.
330. Chloride emulsion formulas

Normal precipitation:
Gelatin 200 g
Silver nitrate 100 g
C Gelatin 80 g
Precipitation temperature: 60-65°C.
B is poured jnto A, quickly and with moderate agitation for high contrast,
and slowly with vigorous agitation for low contrast. The emulsion is ripened
at 65 °C for 20-60 mins. It is then set and washed for 3 hours in running water,
drained and melted at 40°C; the gelatin C is then added with 1 g sodium
chloride.
The above proportions can be altered-the gelatin concentration-the
dilution of solution B (which produces a softer emulsion with increased
dilution)-and by introducing a little potassium iodide after ripening.
Agfa 'Lupex' type formulas
Extra hard Normal Soft
(Gelatin 8001
7001 6751
I Water 15000 L6ooc 30500 20500
I Hydrolyzed albumen 1soo 1 1500 1500
1 ~ Citric acid 27Sj - ~45 o c - ~63 °C
I Sodium chloride
I Potassium bromide 25 %
-
-
soo I soo
13
I
l Sulphuric acid S.G. 1 ·18 - 100J 23J
j Silver nitrate 1000\.._ 55 oc 1000\.._ 45 oc 1000 \.._ 58 0C

2
\.._Water 2000f 16000 J 10000J
Pour 2 into 1 in 20 mins. in 50 mins.

Add
(Sodium chloride 5651
j Water 8soo 1
I
3
I Rhodium chloride 2·5 mg lss oc
l 5 N hydrochloric acid
35
in 40
mtns.
(Gelatin 38001 4000 3675

4l Water 1000 ~75 o c Heat 25 mins. 14000
Potassium iodide 0·65 % 230J at 60°C 200
Add KI sol. 200
Ripen 15 mins. at 10 mins. at 55 mins. at

70 °C 60°C 63°C
cool to 60°C
Add:
5 Potassium iodide 0 ·65% 400 200 250
Ripen 10 mins. at 10 mins. at 10 mins. at

60°C 60 °C 63°C
Add:
6-Mercaptobenzothiazole so 30 so
1 % in alcohol
Set, wash 2 hrs. and add per litre

SLOW EMULSIONS 353
Agfa 'Lupex' type formulas-continued
Extra hard Normal Soft

I
rGelatin 2·S 2 ·S 2·S
Chrome alum 8 11 11
Formalin 30% I 3 3 3
7 ~ Citric acid SO% 1 1 1
I Hydrochloric acid N
Mercaptobenzothiazole 1%
1
3
-
3 I
-
3
lSaponin 3% so so I so
For matt emulsions: 8-25 g rice starch.
Hydrolyzed albumen: Add 120 g egg albumen to 7litres water at 35°C.
Bring up to 70°C and add 170 cc N/10 sulphuric acid. Heat 3 hours at 90°C
and filter through paper. A similar product has been prepared by treating egg
albumen with 23° Be. hydrochloric acid at room temperature.
Practice has shown that hydrolyzed albumen is not indispensable if the
gelatin is suitable.
The rhodium chloride is preferably replaced by rhodium ammonium
chloride RhC1 6(NH4 )a. H 20 very freshly dissolved in sodium chloride solu-
tion. It is extremely effective in increasing contrast, even in very small
amounts. Its presence in the normal emulsion is not necessary as the y of 4
is adequate.
The emulsions made to the above formulas do not keep well unless a great
quantity of antifoggant is included, e.g. benzotriazole. The image colour is
therefore bluish.
Reflex copying papers. These papers, which are used for reflex document
reproduction, that is exposure to yellow light through the support (the emul-
sion being in contact with the document) have a very slow orthochromatic
emulsion. The emulsion must be very contrasty and have a very small toe to
the characteristic curve. The light which passes through the paper the first
time to reach the document, is insufficient to produce developable fog. But
on the return, after reflection by the document, its effect augments that of
the incident light and a developable image results. The extra hard Lupex-type
emulsion is very suitable for this type of work, provided that the silver/
gelatin+water ratio is increased, and the emulsion is sensitized. The reduc-
tion of sensitivity necessary for working in diffuse light is obtained by an
increase in the amount of rhodium chloride, and reduced ripening.
331. Chloride emulsions, unwashed, with cadmium (Steigmann)< 7 >

Contrast formula:
Gelatin 9g

Silver nitrate 15 g
Solution temperature: 60°C.
Pour B rapidly into A, ripen 20 mins., add 54 g of gelatin which dissolves
after 15 mins., add 150 cc water at 60°C and again ripen for 30 mins. at
70-80°C. Coat without washing.
Initial gelatin concentration 2·1%
Concentration at second ripening 9%
Amount of silver chloride per litre of emulsion: 18 g.
Normal formula: Work as above replacing only solution A by:

Sodium chloride 7 ·5 g
Gelatin 6g
Soft formula: Reduce greatly the quantity of cadmium chloride or even omit
it completely:
Silver nitrate 15 g
Pour B into A with stirring. Ripen 20 mins., add 54 g of gelatin, 15 mins.
after add 180 cc of water and continue with a second ripening for 30 mins.
between 70 and 75 °C. Coat without washing.
High contrast formula:
Hydrochloric acid 31 % 3 cc
Gelatin 12 g
Silver nitrate 3g
SLOW EMULSIONS 355
Silver nitrate 12 g
Precipitation temperature: 60"C.
First pour B into A with stirring. Ripen 10 mins. then, after adding C, pour
in D. Again ripen for 10 mins., add 48 g of gelatin and if desired 7·2 cc of a
2% albumen solution. The gelatin is dissolved after 10 mins. After adding
120 cc of water at 60°C the emulsion is ripened a third time for 30 mins. at
70-80°C. It is coated unwashed.
Initial gelatin concentration 2·8%
Concentration after precipitation 2·1 %
Concentration for third ripening 8 ·7%
Quantity of silver chloride per litre of the emulsion: about 17 g.
332. Chloride emulsions with cobalticyanide

According to J. H. Christensen it is possible to increase the contrast of chloride
emulsions by incorporating alkali cobalticyanides.< 8 l Amount: less than 1 g per litre
of emulsion.
To prepare the cobalticyanide, dissolve 30 g of cobalt carbonate CoC03 in acetic
acid. Filter, concentrate, then pour into a warm solution of 120 g of potassium cyanide
(poison) in 400 cc of water. Then oxidize by bubbling air through. Concentrate and
crystallize.
The following formula has been given as an example:
A. Silver nitrate 100 g
Distilled water to 300 cc
B. Ammonium chloride 35 g
Zinc acetate 8g
Acetic acid 0·3 cc
Distilled water to 300 cc
c. G elatin 10 g
Acetic acid 0 ·3 cc
Water to 100 cc
Pour into the gelatin C 13 cc of A and 15 cc of B then continue using double jets,
the chloride always being in excess. Time 1-2 mins. Ripen 60-80 mins. at 48 °C . Add
the cobalticyanide and continue ripening for a further 30 mins. Washing optional.
333. Direct positive emulsions (autopositive)

Papers for development of direct positives have very slow emulsions-as slow
as diazo papers. They are used for reflex document copying.
Autopositive emulsions are orthochromatic; printing is by yellow light.
They are artificially fogged up to the solarization region. They can be fogged
by light or by a fogging agent (hydrazine, sulphur compounds, controlled
action of an arsenite, etc.).
Although autopositive emulsions can be bromide emulsions <9 l they gener-
ally use silver chloride. Bayer and Cauer <10 ) recommend the addition of 10%
silver bromide and traces of colloidal silver for the spontaneous development
of the halide grains.
N
Kendall and Hille <11 >have used photochemical reversal (para. 214) in the
preparation of autopositive emulsions: a desensitizer is added to the silver
chloride emulsion (0·1 to 2 g per 100 g of AgCl). For example, a chloride
emulsion prepared from 100 g of silver nitrate has 17 mg of a desensitizer
containing at least one N0 2 group added to it; it is then fogged by exposure
to white light until a density of 1·2 is obtained.
Among the desensitizers which can be used are the following:
2-(o-nitrostyryl)-3-ethylbenzothiazolium iodide.
2-( o-p-dinitrostyryl)-3-ethylbenzothiazolium iodide.
2-( o-p-dinitrostyryl) benzthiazole.
2-(p-nitrostyryl)-quinoline methyl-p-toluene sulphonate 3 : 3 dimethyl-2-(p-nitro-
stytyl)-indolene methiodide.
6-nitro-benzo-1 : 2 : 3-triazole.
5-(o-nitrobenzylidene)-3-ethyl rhodanine.
Another method of obtaining autopositive emulsions, disclosed by Fallesen,
Spence and Stauffer <12 > is to produce only an internal latent image by the
action of light. On development in a surface fogging developer only the un-
exposed grains are developed.
Clayden effect. High intensity illumination of short duration-produces
positive images on silver bromothiocyanate emulsions containing a halogen
acceptor (Registrier Papier L Agfa).
Positive images on silver iodide. In 1839, Lassaigne noted that silver chloride,
blackened to light, faded to the latter when treated by potassium iodide. Ren-
wick<12b> made the operation easier by adding sulphite and thiosulphate to
the iodide.
Instead of chloride, a bromide lantern plate is fogged to diffuse light for
a few seconds, in order to obtain a moderate latent image. Then it is im-
mersed 10 mins. in a bath containing: water 1000 cc, potassium iodide 10 g,
sulphite 10 g, thiosulphate 30 g. The plate is washed 30 mins. and dried;
it can be kept only a few days. After exposure, it is developed 5 mins. to
a positive in water 500 cc, amidol 5 g, sulphite anh. 50 g, to which is
added, just before use, 500 cc of a 10% sodium carbonate solution. Fix in
30 % hypo at 30-40°C (86- 104°F) because silver iodide is not readily soluble
cold.
Li.ippo-Cramer<12c> succeeded in colour sensitizing these iodized plates,
with erythrosin, rhodamine B, and even with phenosofranine and pina-
kryptol yellow which are known as desensitizers.
The initial sensitivity of the silver bromide does not affect in the sensi-
tivity of the iodized plate.
334. Print-out emulsions (citrate papers)

Print-out emulsions consist of silver chloride to which a halogen acceptor,
silver nitrate or citrate, has been added.
Formerly, print-out papers were simply prepared by first impregnating the
surface of the paper with sodium chloride, then treating this with a solution
of silver nitrate which left a deposit of silver chloride with an excess of silver ;
SLOW EMULSIONS 357
this was the 'salted paper' which could not be kept more than three days. A
paper with better keeping properties could be made by replacing the sodium
chloride by a mixture of sodium chloride and citrate in equal parts. Chloride
albumen paper, which was used later, also had the disadvantage of not keeping;
it was substituted by the gelatino-chloro-citrate paper and with collodio-
silver chloride. The following is a formula of a gelatino-citrate type of
emulsion:
A {
Gelatin 132 g
{ Silver nitrate 100 g
Water 330 cc
B Sodium chloride 27 g
( Sodium citrate 27 g
Pour A into B with stirring at a temperature of at least 45°C. Three g of
salicylic acid dissolved in 12 cc of warm water, 0·4 g of chrome alum and a
surface tension reducer are then added.
Alternative formula using Seignette salt (potassium sodium tartrate):

A fWater 500 cc
50°C l Gelatin 115g
{ ~;::acid
3
B ~~ ;c
50°C Ammonium chloride 5g
Seignette salt 6g
C f Distilled water 200 cc
18°C l Silver nitrate 50 g
Pour A into B then C into A+ B. Ripen 1 hour at 50°C and add 60 cc
alcohol.
Lead nitrate formula . The inclusion of lead nitrate produces more violet
images.
A Water 2200 cc
Gelatin 215 g
B Water 150 cc
Potassium citrate 27 g
Silver nitrate 50 g
Lead nitrate 5g
D Water 170 cc
Citric acid 22 g
Sodium chloride 5g
Add in the order B, C, D to A.
Extra-fast formula of Dybvig and Thomson, <12c> for the detection of ioniz-
ing particles: citric acid and excess silver nitrate are added to a ripened
ammoniacal coarse-grained bromide emulsion. The speed obtained with such
emulsions is twenty to a hundred times higher than with ordinary print-out
papers.
{~~:::ium bromide ~~ ;c
1
A
50°C Potassium iodide 1g
Gelatin 10 g
( Ammonia (28%) 59 cc
C {Water 300 cc
Gelatin 70 g
Water 90 cc
D Citric acid 30 g
( Ammonia (28%) 30 cc
E ( Distilled water 50 cc
\Silver nitrate 9·6 g
B is poured into A in 20 mins. Gelatin C is added and the emulsion is set
and washed. Then D and E are added to the melted emulsion. Higher silver
content results in greater speed.
Self-toning citrate papers. Self-toning paper is prepared by incorporating a
gold salt in the emulsion-chloride or thiocyanate-corresponding to 2·5 g
commercial AuCl 3 per 100 g silver nitrate. The gold salt is preferably added
to the gelatin before precipitation.
Treatment of citrate papers. After exposure, citrate papers are fixed for 10
mins. in 10% hypo. The image colour is generally an unattractive yellow,
which must be toned with gold, or failing that, fixed in a lead toning fixer.
Wash 15 mins.
Citrate papers keep badly. The back of the paper sometimes turns yellow.
The sheets must be interleaved with straw paper which alone seems to
guarantee fairly good stability.
Grassman has studied the sensitization of print-out emulsions with pyrimi-
dine and imidazole derivatives. <13 >
334b. Other silver salts

A great number of insoluble silver salts can give photosensitive emulsions. The most
interesting have been studied by Umano and Nakamura:< 13b) these are the silver
orthophosphate, pyrophosphate and thiocyanate.
Silver orthophosphate. Solution A: cryst. disodium phosphate 4 ·8 g and gelatin
1·2 g in 100 cc water. Solution B: silver nitrate 6 g in 60 cc distilled water. Pour A
into Bin 10 mins. at 40 °C., dialyze in distilled water for 60 mins. Add 10·8 g gelatin
dissolved in 40 cc water. Coat on glass plates. After-ripening produces fog. Develop
in D 72 diluted with 40 volumes water. The images are violet-red. Maximum
sensitidty: 480 mfl; limit 561 mfl.
SLOW EM U L S IONS 359
Silver pyrophosphate. Same preparation. Limit of sensitivity, 440 mf'.
Silver thiocyanate. Solution A: potassium thiocyanate 1·8 g and gelatin 1·2 g in
50 cc water. Solution B: silver nitrate 3 gin 100 cc distilled water. Solution C: 10 ·8 g
gelatin in 40 cc water. Limit of sensitivity at 382 miL with a maximum at 340 mf'.
Silver bromothiocyanate is used in autopositive emulsions, sensit ive to Clayden
effect (para. 211).
Silv er nitride AgN 3 • These emulsions have been prepared by R . Z emp. (' 3' >
COLLODION EMULSIONS
335. General properties
Collodion emulsions consist of dispersions of silver halides- iodide, bromide
or chloride-in nitrocellulose. They are notable for their fine grain which
confers a high resolving power (AgCl-1000 lines/mm).
Collodion is a solution of nitrocellulose in a mixture of equal parts of
alcohol and ether. In the presence of water, and after evaporation, it forms a
more or less permeable layer. To prepare an emulsion of a silver salt in
collodion, one can either proceed directly, as for gelatin emulsions, or the
collodion can first be coated onto glass, and then sensitized by bathing. The
formation of the silver precipitate in the colloid is possible because the
halides are generally soluble in alcohol.
Celloidin papers are silver collodio-chloride papers, generally made self-
toning by incorporating a gold salt. They are still used today, although on a
small scale. Coating collodio-chloride emulsions on paper necessitates a
special coating machine with horizontal drying and a solvent recovery
unit.
336. Wet collodion

Wet collodion was very much used at one time. A paper in 1880 was certain
that this was the most practical and cheapest photographic process. It is
still used today for the preparation of graticules and in photomechanical
work.(14 >
The plates are cleaned in dichromate-sulphuric acid solution, rubbed with
a pad containing tincture of iodine, dusted with talc and cleaned with a
brush. The collodion coated on such plates can be readily removed. If, on
the contrary, the coating is to remain on the glass, then the plate is first
coated with a thin layer of albumen, made from an egg-white beaten with
20 cc water and made up to 200 cc.
Collodion coating is carried out with a solution such as:
Alcohol (95 %) 200 cc
Ether 300 cc
Guncotton 5g
Ammonium iodide 3g
Cadmium iodide 3g
Ammonium bromide 1g
The salts are ground in a mortar with several 20 cc portions of alcohol,

which are added to the guncotton in a large flask. The ether is added.
When dissolved, it is left several days to clarify the collodion, which is
decanted.
The plates are sensitized in:
Silver nitrate 80 g
Boric acid (optional) 0·2 g
and after draining are exposed wet in a slide protected with blotting paper to
absorb the excess silver nitrate. The exposure is very long.
The image can be developed physically, using the excess silver nitrate
present in the layer. A solution of 50 g per litre ferrous sulphate acidified
with 10 g tartaric (or acetic) acid and containing 30 cc alcohol develops
rapidly. The plate is then washed. The image can be physically intensified.
Fixing: in hypo.
336b. Eggert and Kleinschrod process

Prepare the following solutions in the order given:
A Silver nitrate 8g
Water at 70°C 3 cc
Alcohol 99%, tepid 240 cc
Collodion, 4% 150 cc
B Zinc bromide, dry 5-6 g
Alcohol99% 80 cc
Collodion 4% 150 cc
Pour A into B slowly, taking one hour. Precipitate everything with distilled
water; wash on the filter with distilled water, then with alcohol. Dissolve in
200 cc of an equal part mixture of alcohol and ether containing 0·5 g zinc
bromide. Coat on glass plates, and preferably expose and develop before
drying. Develop 5 mins. in a glycin developer and fix in hypo.
336c. Dry collodion

Collodion plates gradually lose their permeability when they are dried.
This can be overcome by treatment in tanin which keeps the collodion porous
and is dissolved on development.
The sensitized plates are washed to remove the excess silver nitrate, then
immersed in:
Water 100 cc
Tanin 4g
The drained and dried plates keep well, but they are three to five times
slower than wet collodion.
SLOW EMULSIONS 361
337. Celloidin emulsions
Celloidin emulsions consist of silver chloride dispersed in dry collodion. They
are print-out materials. Here are several preparation formulas:
Formula 1 ( (Alcohol 95 % 200 cc
(Mathet) Strontium chloride 2g
A Lithium chloride 1g
Nitrocellulose 12 g
Ether 200 cc
Distilled water 8 cc dis-
B { Silver nitrate (powdered) 14 g solve
( Alcohol90% 50 ccwarm
Pour A into B slowly, and with vigorous agitation. Add 50 cc of ether, 6 cc
glycerin and filter.
Formula 2 A Nitrocellulose 40 g
(Wall) Alcohol95 % 900 cc
Ether 1000 cc
B Citric acid 3·4 g
Lithium chloride 3·4 g
Strontium chloride 6·8 g
Alcohol 40 cc
c Silver nitrate 15 g
Water 40 cc
Glycerin 4 cc
Alcohol90% 60 cc
Formula 3 A Collodion 4% 500 g
(Trumm) B Alcohol 50 cc
Strontium chloride 10% 3 cc
Lithium chloride 10% 1 cc
c Silver nitrate solution 1 : 1 24 cc
Alcohol 50 cc
D Citric acid 25 % 60 cc
Alcohol 25 cc
E Castor oil 1 cc
Alcohol 25 cc
Glycerin 2·5 cc
Magnesium chloride (MgC1 2 • 6H 20) 1 g
{ Alcohol 90% 100 cc
Formula 4 A
{ Ether 100 cc
Nitrocellulose 3g
The magnesium chloride is dissolved in the warm alcohol. This is cooled
before adding the ether. The mixture is shaken frequently to dissolve the
362 PHOTOGRAPHIC CH E MI ST RY
nitrocellulose. The mass does not thicken until it has been left for twelve
days. The silver nitrate solution is similarly prepared:
Silver nitrate powdered 4g
{ Distilled water, warm 4 cc
B { Alcohol90 % 100 cc
{ Ether 100 cc
Nitrocellulose 3g
Mix the A and B collodions and agitate vigorously; a very fine precipitate
of silver chloride is formed and a large excess of silver nitrate remains. The
following is added to the emulsion:
Water 0·5 cc
{ Citric acid 0·5 cc
c 4 cc
{ Alcohol 90 %
Ammonia 20% 1 drop
Formula 5 Lithium chloride anh. 5g

(Goldberg) A Distilled water 20 cc
( Alcohol 70 cc
Silver nitrate 24 g
( Alcohol 60 cc
Citric acid 12 g
c r Alcohol 50 cc
l Ether 50 cc
Fourteen cc of each solution is added to three separate 100-cc portions of
2% collodion, and the three collodions thus obtained are then mixed.
Formula 6, for matt paper:

(Trumm) A Collodion 4% 500 g
{Calcium chloride anh. 1·5 g
B
(
Alcohol
Ether
50 cc
30 cc
c Silver nitrate solution 1 : 1 30 cc
Alcohol 60 cc
D Tartaric acid 0·4 g
Citric acid 6g
Alcohol 95 cc
E Glycerin 4 cc
Water 8 cc
Ammonia 25 % 4cc
Alcohol 30 cc
To make the emulsion matt, add 10 cc of an alcoholic 10% solution of
dewaxed gum lac.
SLOW EMULSIONS 363
Gold, as chloride or thiocyanate can be added to all the emulsions given,
in the proportion of 1- 3 g of chloride per 100 g silver nitrate.
Treatment of celloidin paper. Mter exposure to daylight or mercury-vapour
lamp, until a higher density than required is obtained, the paper is washed
for 3 mins., then fixed for 10-15 mins. in 10% hypo. The image colour be-
comes colder as fixing is prolonged. Wash for one hour, drain and dry. For
reddish tones, bathe the exposed paper for 5-10 mins. in 10% sodium chlor-
ide. Wash for 1 min. then fix. The tone becomes colder with longer treatment
in the saline solution.
338. Polyvinyl alcohol emulsions

Polyvinyl alcohol is the polymer of the hypothetical vinyl alcohol CH 2 =
CH . OH. It is prepared by saponification of polyvinyl acetate which
g1ves:
-CH 2 -CH(OH)-CH 2 -CH(OH)-CH 2 - CH(OH)-CH 2 -CH(OH)-
Low polymer polyvinyl alcohol is soluble in cold water. Higher polymers

are only soluble in warm water; on cooling, they form gels. Polyvinyl alcohol
is known in France under the name Rhodoviol: type H.S. 100 dissolves cold,
H.S. 10 dissolves at 60°C. Sodium carbonate, sodium sulphate, borax (1 %),
resorcinol, IX- naphthol <1 5 > convert the solutions to gels. Other coagulating
agents are the polyphenols, <16 > the o-hydroxybenzoketones, di-2-hydroxy-
3-naphthoylbenzidine, etc.
Polyvinyl alcohol can be used to prepare slow or artificially activated
emulsions. It is not miscible with gelatin. The adsorption of polyvinyl
alcohol by silver bromide has been studied by Sheppard, O'Brien and
Beyer. <17 >
Polyvinyl alcohol has a retarding action on ripening which is much greater
than that of gelatin. (18)
Polyvinyl acetal can be used as a protective colloid for emulsions. It is
prepared by reacting an aldehyde with polyvinyl alcohol. <19 > The proportion
of hydroxyl groups must be 50- 60% for the layer to be sufficiently permeable.
Example of preparation : a solution of 100 parts of polyvinyl alcohol in 2000
parts of water is mixed with SO parts of hydrochloric acid and 25 parts of
propionaldehyde. The acetal which separates is washed with water at 60°C.
To increase the solubility of the acetal, and enable silver halide to be
precipitated, it is recommended that an organic solvent, such as alcohol,
acetone or cellosolve, should be added. It is also possible to precipitate the
emulsion in another colloid, then add the acetal. Among the dispersion
colloids are: the copolymer of maleic anhydride and vinyl acetate and water-
soluble ethanolamine-cellulose acetate. The latter is prepared by reacting
p-toluene-sulphonyl chloride on cellulose acetate in the presence of
pyridine, then ethanolamine. Precipitation can also be carried out in a
solution of polyacrylamides. <20 >
N*
339. Polyvinylpyrrolidones
N-vinyl-2-pyrrolidone, which is obtained from acetylene with a high pressure
reaction, will polymerize to give water-soluble colloids, the polyvinyl-
pyrrolidones: <21 >
The British Oxygen Co. Ltd. makes polyvinylpyrrolidones with molecular

weights from 40,000 to 100,000 which behave like gelatin. <22 > In the U.S.A.,
the Gen. Aniline Corp. produces them at the Calvert city plant.
340. Sensitized cellulose

Cellophane is immersed for five minutes in an M/2 silver nitrate solution,
then for 15 minutes in normal potassium bromide. The cellophane is then
washed in running water and dried (Eggert and Kleinschrod). G. Sjostedt has
disclosed the following commercial process: the cellulose foil is impregnated
successively with M /5 potassium iodide for 2 mins., M/5 to M /2 silver nitrate
for 1 min., then M potassium bromide containing M/2 citric acid for 1-15
mins. The contrast increases linearly with the silver nitrate concentration.
The sensitivity can be increased by immersing in a solution of ethylenediamine
or arginine. <23 >
Stachowiak<23h> sensitizes by 30 sees. immersion in a 5·6 % iodide solution,
then 30 sees. in a 16·9% silver nitrate solution, and finally in a bath containing
19% potassium bromide, and 2·5% nitric acid, at 28-30°C. Resulting gamma
1·2 to 1·5. With 8·5 % silver nitrate and a bath containing 24% bromide +
3% nitric acid, and without any iodide, gamma is higher: 2·2.
341. Sensitized cellulose acetate

Kleinschrod and Eggert have sensitized hydrolyzed cellulose acetate in the
following way: <24 > a solution of 9·8 g of silver nitrate in 20 cc water with
20 cc acetone is poured, in 20 mins. at 45°C into:
Cellulose acetate, strongly hydrolyzed llg
Acetone at 70°C 50 cc
{ Water at 70°C 50 cc
( Potassium bromide 7·15 g
{Acetone 40 % 30 cc
The emulsion is precipitated in distilled water, washed, dried and re-
dissolved in 250 cc 40% acetone before coating. An M.Q. developer is used.
J. Seiberlich <25 > has disclosed a method of sensitizing any permeable support,
SLOW EMULSIONS 365
by impregnating with an alcoholic solution of silver nitrate, then exposing
to the vapour of an organic bromide such as ethyl bromide.
LIPPMANN EMULSIONS
342. General properties

Lippmann emulsions, also called 'grainless emulsions', are formed of crystals
of silver bromide which are so fine that they can be seen only with an electron
microscope. The diameter of these crystals is between 10 and 50 mp,. Lipp-
man emulsions are used for interference photography for the production of
monochromatic filters (see: para. 493).
To obtain such fine-grain emulsions, the use of gelatin with strong retarding
power is necessary, or artificial retarders can be added. Precipitation must be
carried out with very dilute reagents and at the lowest possible temperature to
avoid ripening. The concentration of silver bromide in the final emulsion is
only 8-10 g per litre.
The chloride emulsions are more sensitive than the bromide ones. They are
also less transparent. By ripening, the bromide emulsions become more
sensitive than the chloride ones by rapid growth of the grains. The addition
of colour sensitizers prevents the enlargement of the grains; the sensitivity to
blue is decreased but that to the green or red is increased. In the presence
of a bromine acceptor such as a bisulphite, the increase in sensitivity is
accentuated, except when the dye itself is an acceptor, such as Pinaftavol.
Liippo-Cramer<26 > has stated that a grainless emulsion containing 3% iodide
is less sensitive than a pure bromide emulsion. The iodide emulsion sensi-
tivity increases on ripening faster than the bromide one, but after 3 hours it
passes through a maximum and decreases after 4 hours. The bromide emul-
sion continues, on the contrary, to become faster.
343. Preparation of Lippmann emulsions

Formula 1 (old type). Mix the two following solutions at a temperature
below 40°C:
ri,tilled
wate< 100 cc
A Potassium bromide 1·5 g
Gelatin 5g
B
Gelatin 6g
Silver nitrate 2g
A is poured into B with moderate agitation. Colour sensitizers are added
and the emulsion is coated onto plates in a very thin layer. As soon as the
emulsion is set, the plates are dipped for a few seconds in alcohol, then
washed for 30 mins. They are then dried (keeping time: 6 months).
Plates prepared in this way are not sensitive enough to be used as they are.
They must be hypersensitized in the following solution for 1 minute:
Acetic acid 0·5 cc
Drained and dried, they can be used a few hours later. They can be kept
for several days. The initial sensitivity is increased fifty times.
Formula 2 (classic type). The method is the same as that for a normal
emulsion. The gelatin must contain sensitizers and be very rich in retarders.
Gelatin 8g
Potassium iodide 0-02g
B {Gelatin 8g
Silver nitrate 2g
( Ammonia Q.S.
Temperature: 34°C. Pour A into B very quickly with stirring. Immediately
add 10 cc of 10% sulphuric acid whilst cooling. The emulsion is washed and
remelted at 50°C.
Formula 3 (chlorobromide type):

A Gelatin 40 g
Citric acid 40 % 4cc
Sodium chloride 25 % 18 cc
Ammonium bromide 25 % 16 cc
D Gelatin 20 g
Potassium iodide 0·65 % 18 cc
Precipitation temperature 36°C. Pour B into A, then, very quickly, C into
A+B. Add D molten. Cool immediately. Wash 3 hours. Melt and colour
sensitize before coating.
Double-Jet formula (Crawford): <27 l

Gelatin 12 g
A { Distilled water 80 cc
SLOW EMULSIONS 367
B { Distilled water 10 cc
Silver nitrate 10 cc
c{ Distilled water 0·375 g
Temperature: 37°C.
Pour B into C, two drops per sec. Add 3 cc 2 % chrome alum and 2 cc of a
0·1% sensitizing dye solution (in alcohol). The emulsion is coated on plates,
washed and dried. To have perfectly smooth layers it is recommended to
mould the emulsion by pouring it upon the horizontal plate (previously
treated with a non-adhesion agent such as chloromethylsilane) then covering
with sheet of glass held at a small distance by three pieces of steel wire or
any other system. After 30 mins., the covering glass is removed with the
emulsion adhering to it.
The graininess can be measured by the ratio of the intensities of blue light/
red light diffused by the emulsion layer (3·3 to 3·7 with a 2,900°K lamp and
llford filters violet 621 and red 608).
Resolving power: 5,000 linesjmrn.
More bromide in the formula gives coarser grains.
Bromination of colloidal silver. (28 > A dry gelatin layer containing colloidal
silver, treated in a solution of cupric bromide, washed and dried, is sensitized
in silver nitrate solution.
1. London. H.M. Stationery Office, 1945.

2. IX Int. Cong. Phot., Paris 1935.
3. Author's formula.
4. Steigmann.
5. Steigmann.
6. Steigmann A.: Brit.Jl. Phot., 1946, 140; Sci. et Ind. Phot., 1946, 138.
7. IX Int. Cong. Phot., Paris 1935.
8 F.P. 971,858 (1950).
9. Nishimura, Furuya and Kono: Jl. Soc. Sci. Phot. Japan, 1951, 17-27; Sci. et Ind.
Phot., 1952, 262, give the following emulsion: A =water 150, gelatin 10, potas-
sium bromide 8·8, potassium iodide 0 ·65, potassium chloride 0 ·4; B =water 35,
silver nitrate 15, ammonia Q.S.; C = water 125, potassium bromide 8, gelatin 20.
10. F.P. 993,337.
11. Kodak-Pathe: F.P. 989,400 (1951).
12. Kodak-Pathe: F.P. 983,013; 1,001,730; 1,001,739.
12b. Renwick: Brit. Jl. Phot., 1920, Nos. 3142 and 3143.
12c. Luppo-Cramer: VI Congres Int. de Photogr., 1925.
12d. Dybvig H. T. and Thomson T. R. : Phot. Eng., April 1954, 127-132. The image
can be intensified by heating, the citrate acting as a physical developer; or by
post-illumination to long wavelength radiation (Becquerel effect).
13. Grassman H . : Z eits. Wiss. Phot., March 1951, 233-252.
13b. Umano S. and Nakamura N.: Jl. Soc. Sci. Phot. Japan, May 1954, 59-65.
13c. Zemp R.: These, Zurich and Zeits. Naturforsch, 1953, 389-395.
14. Chassang C.: La technique moderne du proctde au collodion humide. Paris, Gauthier-
Villars . Ed. 1936.
15. Kodak-Pathe: F.P. 961,819 and U .S.P. 2,311,058.
16. Kodak-Patht> ' F .P. 868,564 and 869,973.

17. Jl. Colloid. Sci., 1946, 213.
18. Fujii : Sci. Ind. Phot., 1953, 106 and 273.
18b. Ohyama and Futaki: Sci. Ind. Phot., 1956, 41-46.
19. Kodak-Pathe: F.P. 961,835 (1949).
20. Kodak-Pathe: F .P. 1,055,759.
21. Reppe W.: monograph of 72 pp. Verlag. Chemie, G.m.b.H. Weinheim/Bergstr.,
1954.
22. Ind. Chem ., March 1953, 122.
23 . Sci. Ind. Phot., (2)11, 17, 171 and 241.
23b. Stachowiack: Bild und Ton, Oct. 1955, 271-273.
24. Zeit. Wiss. Phot., Jan. 1941, 165.
25. G .P. 660,164 (1934).
26. Li.ippo-Cramer: Zeit. Wiss . Phot., Sept. 1931, 201.
27. Jenny L. : Sci. Ind. Phot., 1951,336.
Crawford B. H.: Jl. Sc. Instrum., Sept. 1954, 333-335.
28. Leroy M. N.: Dipl. Et. Sup., 1929, Paris.
Chapter XXI
STABILIZING AND FINISHING

PHOTOGRAPHIC EMULSIONS
BROMIDE AND SILVER ION CONCENTRATION
344. Law of mass action

Consider a reversible equation of the type
A2+B2 ~ 2AB
For each temperature there is a fixed state of equilibrium. If (A 2), (B 2 ) and
(AB) represent the molecular concentrations of the reactants in equilibrium
we have the relation (A 2 ) x (B 2)/(ABh = KAB·
KAB is the dissociation constant of the compound AB. Its reciprocal is the
constant of formation.
When an electrolyte is dissolved in water it dissociates into its mobile
constituents, or ions. For example, with silver nitrate:
AgNOa ~ Ag+ + NOa-
The metallic cation Ag+ and the acid anion N0 3 - are in equilibrium with
the non-dissociated salt.
In the case of a very sparingly soluble salt such as silver bromide, the
dissociation is very slight. We have nevertheless the ionic reaction
AgBr ~ Ag+ + Br-
and by applying the law of mass action to the ions we have
(Ag+) x (Br-)
(AgBr) = KAgBr
But the solution is saturated with AgBr which is present in great excess.
The concentration (AgBr) therefore remains practically constant. This results
in the relation
(Ag+) x (Br-) = Ct
where Ct, which has a constant value, is the product of the concentrations of
the ions Ag+ and Br-, and is called the solubility product.
369
345. Variations in the concentration of silver and bromide ions

Let us now consider an emulsion containing pure silver bromide: this is
partially dissociated into its ions. The addition of an excess of Br- ions as
potassium bromide brings about a reduction in the concentration of Ag+
ions, as the solubility product remains constant. Conversely an excess of Ag+
ions as silver nitrate diminishes the concentration of Br- ions.
At temperature t, the concentration of silver ions has a fixed value repre-
sented by the ordinate rna of the curve in Fig. 49, and equal to Ct. By assum-
ing that the bromide is completely dissociated at very great dilutions, and
representing the number of added KBr molecules by b, (b-x) gram-ions of
new Br- are formed, x being the number of molecules of AgBr re-precipi-
tated. We have, therefore, [(Ag+)-x] [(Br- )+ b-x] = Ct. By replacing
(Ag+) and (Br-) by .,/Ct we have x2 -(b+2yCt)x+ byCt = 0, a simple
quadratic equation.
~
0
u
c:
.!!
+
<
d
---m~ KBr
FIG. 49.
Referring again to Fig. 49, the reduction in the concentration of Ag+ ions
by adding bromide is represented by the portion ad of the curve. The addition
of silver sulphate, on the contrary, reduces the concentration of Br- ions,
(Ag+) increases along the part ah.
The silver ion concentration is shown by variations in the e.m.f. of the
system.
346. Measurement of the silver ion concentration

The silver ion concentration of an emulsion is measured by immersing a silver
electrode in the liquid mass, and measuring the potential compared with a
reference electrode.
First, the potential difference is determined between a silver electrode in a
solution of known silver ion concentration and a standard hydrogen electrode
(para. 34), at a fixed temperature. As the potential of the hydrogen electrode
is, by definition, zero, the potential e 0 of the known solution is:
RT RT EO- EN
EO = EN +- log (Ao+) where- = ---
F F log(Ao+)
STABILIZING, FINISHING PHOTOGRAPHIC EMULSIONS 371
By repeating the operation with the test emulsion:
RT EO- EN
EO = EN + -log(A+) OrE= EN+ log(A+)
F log(Ao+)
and as
E- 0·80
EN = 0·80, log (A+) = log (Ao+)
EO- 0·80
If, instead of using a hydrogen electrode, a bridge<1 > is made between the
emulsion on one side and the known silver solution on the other, with two
silver electrodes, the relation
RT (Ao+)
e = EO- E = - log - -
F (A+)
is obtained where e is the measured e.m.f., Eo the potential of the known
solution and E the potential of the unknown solution, in this case, the emul-
sion (para. 34).
In practice, the known solution is a suspension of silver bromide containing
an excess of either silver ions (using silver sulphate) or bromide ions (using
potassium bromide). The e.m.f.'s are measured by the usual electrometric
methods.
The curve in Fig. SO shows the amounts of bromide and silver sulphate
which must be added to give different Ag+ concentrations in 175 cc of emul-
sion containing 0·04 gram-mols. of silver bromide (7·52 g); it is seen that the
neutral point is at about log (Ag+) = - 6·5, but as the emulsion already con-
tains soluble bromide, an excess of the silver salt must be added.
The number of equivalents of KBr or t(Ag 2S04 ) which must be added to
1000 mols. AgBr, to give a given Ag+ concentration (and therefore a corres-
ponding Br- concentration), are as follows:
(Ag+) Gm-equivalents
per 1000 AgBr
Low concentrations
0·65 X 10- 9 15 KBr
0·7 X 10- 9 12·25 ,
0·77 X 10- 9 11·25 ,
0-9 x 10- 9 5-25 ,
1 X 10- 9 3·5 ,
0·7 x 10- 8 0·35 ,
Neutral point
"' 1 X 10- 8 0·25 i(Ag 2 S0 4 )
1 X 10- 7 1·5 ,
1 x 10- 6 3·5 ,
1 x to-s 6-75 ,
High concentrations
Schleussner's method. The reference solution is an M/1000 solution of silver brom-
ide obtained by adding 20 cc of M/10 potassium bromide to 10 cc of M/10 silver
nitrate+ 970 cc distilled water, which is kept in the dark. Two spirals of silver wire
protected by glass tubes are used as the electrodes. One is used for comparison whilst
the other is dipped in the emulsion.
The electrodes are connected to a sensitive millivoltmeter, the measure-
ments being made in red light. When both electrodes are immersed in the
reference solution, the potential must be zero; if not the electrodes are cleaned,
first in 10% caustic (10 mins.) then in 1% cyanide (5 mins.) and finally in
dilute nitric acid until bubbles are produced, before washing in distilled water.
A table shows the relation between the e.m.f. in m V, the concentration of
bromide in 0·0001 gjmol jlitre. Temperature corrections are also included.
E = k log (C1/C2) where k = 0 ·1985 (273 + ttC
and C1 and C 2 are the bromide ion concentrations (Phot. Ind., Feb. 1941,
115).
FIG. 50.
EMULSION STABILIZING
347. Effect of silver ion concentration
The sensitivity of a photographic emulsion increases with the concentration
of silver ions: there is an increase of redox potential, that is, an increase of
oxidizing power. We have also seen (para. 35) that this potential varies with
the pH (degree of acidity or alkalinity of the medium).
Together with the sensitivity, the fogging tendency of the emulsion in-
creases: the Ag+ and Br- ions of the silver bromide crystals give, in the
presence of traces of moisture, silver hydroxide Ag+ /(OH)- and hydrobromic
acid Br-jH+. The silver hydroxide is also reduced by gelatin, or other reduc-
ing agents, to metallic silver according to the reaction:
Ag+j(OH)- + (H+ +e-)~ Ag + H+j(OH)-
Silver Hydrogen Si:ver Water
H ydroxide
When the specks of silver form a sufficiently large group, they make up
centres of spontaneous development which produce fog. The dry emulsion
when left, continues, in short, the after-ripening at a slower rate, which can,
however, become appreciable when the silver ion concentration exceeds a
certain value.
To retard this formation of age fog and to improve keeping it is neces-
sary to maintain the Ag+ concentration within well-defined limits. This is
STABILIZING, FINISHING PHOTOGRAPHIC EM U LSIONS 373
achieved by adding a certain amount of Br- ions as potassium bromide,
whose effect, as we saw in the preceding paragraph, is to reduce the Ag+
concentration below the fog region. In all cases careful measurements must
be made.
If an excess of Br- is added to reduce the concentration of Ag+ and ensure
long stability, the sensitivity is also reduced. Sensitivity and stability are two
opposing factors and a compromise must be reached.
Slow emulsions are more easily stabilized than fast ones; this is explained
by the fact that large quantities of soluble bromide may be added without
inconvenience. Thus bromide papers will keep well for three or four years
whilst negative materials deteriorate much more quickly.
A shelf life of 6-12 months can only be assured for a negative emulsion if
the Ag+ concentration does not exceed 0·5 x 10- 8, which corresponds to an
addition of 2·5 KBr per 1000 AgBr. This Ag+ concentration must not fall
below 0·8 x 10- 9 (10 KBr per 1000 AgBr) or the sensitivity will drop con-
siderably.
The potassium bromide can be advantageously replaced by magnesium
bromide with which both the bromide and magnesium ions are effective.
Two to 4 cc of a 1% solution can be added, before after-ripening, to a litre
of negative emulsion.
The nature of the emulsion influences the stability greatly: the degree of
degradation and activity of the gelatin are the main factors. Furthermore,
ammoniacal emulsions are less stable than neutral ones. Ammoniacal emulsions
after-ripened at low temperatures are more stable than those digested at a
high temperature.
The most important external influences which must be considered are
temperature and humidity: they can bring about rapid changes in sensitive
layers, by favouring the mechanism given above.
The loss of sensitivity on storage of photographic layers appears to be due
to an oxidation reaction, especially by atmospheric oxygen. On the contrary,
the increase of superficial fog is inhibited by oxygen. <2 > In both cases the
changes are accelerated by humidity and temperature. Internal fog is attri-
buted to thermal agitation in the interior of the crystal.
To study the keeping properties of dry emulsions they are artificially
aged by being left in an oven at 40-50°C. The results obtained are not
absolutely identical with those of natural ageing, but very useful information
is obtained.
Desiccated films. To ensure good keeping. a sensitive layer must be care-
fully dried. The desiccants which are generally used are calcium chloride,
preferably absorbed on active carbon, and silica gel. Anhydrous calcium
sulphate, activated alumina, crumpled paper, cotton, rice and tea leaves are
also desiccants but less effective.
Before unrolling desiccated films, they must be rehumidified by leaving
for 48 hours in a room at a suitable relative humidity. Unless this precaution
is taken, static discharge sparks are liable to occur on unrolling, which affect
the film.
348. Low temperature storage

Sensitive materials, particularly high-speed and colour ones, can be satis-
factorily stored at low temperatures. Even for short-term storage it is in-
advisable to exceed 25°C (77°F). It is recommended that films be kept at
15°C (59°F) if stored for 6 months and at 10°C (50°F) for 12 months.
A very low temperature of about - 15°C (5°F) ensures even greater stability,
provided that the films are put into sealed containers. For use in tropical condi-
tions solid carbon dioxide ( -70°C) can be used advantageously.
The wrappings of refrigerated films must not be removed before warming
up to normal temperature or condensation of atmospheric water may occur
on the material.
After manufacture, films are conditioned in an atmosphere of 40- 60 %
R.H., and the water content of the emulsion does not exceed 15 % . Refrigera-
tion and hermetic sealing does not result in internal frosting unless the
water content reaches 34%. (S)
349. Organic antifoggants

A large number of organic compounds have strong antifogging properties.
Some of them stabilize emulsions much more effectively than the bromides.
When added to chloride emulsions the antifoggants produce bluish colours,
with the exception of certain mercapto derivatives.
As a general rule, the solubility of the silver salt of an antifoggant must be
lower than that of silver bromide, (4 > which results in a reduction of the Ag+
concentration around the crystal.
A. Cyclic amines. Diphenylamine C 6 H 5 -NH-C 6H 5 (in a concentration
of 1 mol. per 100 mols. AgBr) and certain benzidine derivatives having at
least two NH 2 groups. ( S)
B. Iminazoles. The best known of these compounds is 6-nitrobenzimin-
azole. (G) It occurs as pink needles M.Pt. 207°C. It gives a nitrate which is
used in practice (M.Pt. 215-225°C with decomposition). Solubility in 50 %
alcohol : 0·5 % ; in 10% caustic soda: 1% . Concentration: 10-30 mg per litre
of emulsion.
The benziminazoles are prepared from the o-phenylenediamines and the
iminoethers. (?) p-nitrobenziminazole can be prepared merely by boiling
nitro-a-phenylenediamine with formic acid.
Mercaptobenziminazole is a very active stabilizer(S) and an antioxidant. It
is prepared by condensing thiourea with pyrocatechin.
OH HN NH
O OH
+
HN
~
,.C-SH ---+
O 'c-SH
N~
However, 2-thio-4-methyl-5-acetyliminazole is better.

STABILIZING, FINISHING PHOTOGRAPHIC EM ULS IONS 375
O
~oNH'cH N~
~N
N~ NIV
\
p-nitrobenziminazole benzotriazole p-nitro-pseudo azimidobenzene
SH-C-N-C6 H5
0
CoH5 -C-NH
C-CH 3 II I II I
~ N .~N N N
N 'Nr 'N~
/\
C~
4
S0 .CH
3
5-phenyltetrazole 1-phenyl-5-mercaptotetrazole
2-methylbenzthiazole methyl
sulphate
~00'c-oR' HC/N~CH SH-C/N~-SH

II I u I
~ HC,C~N HC,~N
N
H I
c~
oxybenzoxazole pyrimidine 4-methyl-2: 6-dimercaptopyrimidine
HC-~ 0 H2 c-s
II I H2C/ H2 'c I I
CH -C C-NH2 I I CO.OH-HC CH-R
3 '
N~ H2C C H2 ' NH"
'N/
I
C&Hs
2-amino-4-methylthiazol phenyl-morpholine 4-carboxythiazolidine
The thioiminazoles reduce the sensitivity considerably, with the exception

of 3-allyl-2-dimethyl-2-thiohydantoine.
C. Triazoles. The benzotriazoles are widely used in the manufacture of
photographic emulsions, as well as for development antifoggants. Ordinary
benzotriazole is in the form of white needles melting at 93-97°C. One g of the
pure compound will dissolve completely in 100 cc water or 100 cc absolute
alcohol. It is better to use it in aqueous alcohol. Concentration: 10-20 mg per
litre of emulsion.
Benzotriazole is estimated argentometrically in caustic solution. Bromide
and iodide are detected, according to the A.S.A. standard, by adding to 5 cc
of 1% aqueous solution: 1 cc of concentrated sulphuric acid then 5 cc of a
solution of 1·5% eerie sulphate and 1·5 % sulphuric acid. When the mixture
is shaken with 1 cc chloroform, the latter must not be coloured.
5-methylbenzotriazole is a white crystalline powder melting at 80-84°C.
p-nitro-!f-azimidobenzene is a benzotriazole.
The benzotriazoles are prepared by the action of nitrous acid on the ortho-
diamines (see N oelting, B er. , 20, 3001).
D. Tetrazoles. The tetrazoles, to which attention was drawn by Steig-
mann, have a 5-atom nucleus. The phenyltetrazole derivatives having an
active mercapto or imino group are effective stabilizers for neutral emulsions.
Murobushi, Ichifugi and Ashikawa <9 > have given the following, used at a
concentration of 10-4 mol. per molecule of silver nitrate.
1-phenyl-5-mercaptotetrazole (strong ripening retarder).
5-phenyltetrazole.
5-( m-nitrophenyl)-tetrazole.
E. Thiazoles. The derivatives of 2-methylbenzthiazole are antifoggants,
including the methiodide (or ethyl-p-toluenesulphonate) of 2-methyl-
benzthiazole added in a concentration of 20- 80 mg per litre of emulsion. <10 >
Suzuki and Toriu <11 > have studied 2-amino-4-methylthiazole and 2-diethyl-
amino-4-methylthiazole.
Kashida, Yokota and Hai <12 > have prepared a 2-aminothiazole-5' : 4' : 5 :
6-quinoline which stabilizes neutral and ammoniacal emulsions. To prepare
this substance, dissolve 4·6 g of 6-aminoquinoline in 61 g of glacial acetic
acid cooled in ice and salt. Add 18 g of potassium thiocyanate dissolved in
90 g acetic acid, then, drop by drop, 5 ·4 g bromine dissolved in 45 g of acetic
acid. After 12 hours, the solution is concentrated in vacuo, water is added
and the solution neutralized with sodium carbonate. The product is re-
crystallized from methanol (Yield 4·8 g).
Kashida <12b> has also disclosed 2-thio-4-methyl and 2-thione-3-benzyl-4-
methylthiazole and 2-benzylidenehydrazino-4-oxat'hiazoles.
F. Mercaptobenzthiazoles. Mercaptobenzthiazole is sometimes used as an
antifoggant, especially in silver chloride black tone emulsions at a concen-
tration of 20- 30 mg per litre of emulsion, and in bromide emulsions, before
washing, using 1- 3 g per kg of dry gelatin. It is, however, a weak antifoggant
and it is better to use 2-methylmercaptobenzthiazole. Against yellow fog,
200 mg of mercapto derivative is necessary per kg of gelatin.
Mercaptobenzthiazole exists in two tautomeric forms:
O S~C-SH ~ os~C=S
N~ NH
The N-ethyl and N-benzyl derivatives have a better stabilizing action than
the simple compounds. <13 > The benzyl derivative is slightly soluble and gives
bluish toned images with silver chloride.
For the preparation of mercaptobenzthiazole, see the patents listed. <14 >
G. Oxazoles. The oxazoles are considered superior to the corresponding
thiazoles as stabilizers as they reduce the emulsion sensitivity less. They are
used at a concentration of 20- 30 mg per litre.
Mariani and Martinelli have, in a recent paper, <15 > disclosed 2-hydroxy-
benzoxaz ole and 2-hydroxy-6-nitrobenzoxazole as very efficient stabilizers.
The mercaptobenzoxazoles correspond to the mercaptobenzthiazoles. With
them, chloride emulsions retain their black tone. Concentration: 20-30 mg
per litre.
The antifogging properties of the thiazoles and the oxazoles is again found
in indoline derivatives such as 1-methyl-dimethylindoline dimethylsulphate.
H. Thiosemicarbazides. Thiosemicarbazide with the formula NH 2-CS-
-NH -NH 2 , prepared from hydrazine sulphate and potassium thiocyanate,
is an antifoggant. The aldehyde-semicarbazones are, however, more active. <16 >
I. Pyrimidines. Pyrimidine derivatives are strongly adsorbed onto the sur-
face of the grains, which to some extent explains their strong antifogging action.
Kikuch and Sakaguchi <17 > have measured the normal free energy to form the
silver salt, and the solubility product of fifty-five pyrimidine derivatives.
Pyrimidine has a 6-atom nucleus having two nitrogen atoms in the 1 : 3
(meta) positions. Koseki and Fukawa (IS) have prepared and studied the
photographic properties of thirty-three derivatives.
The best antifoggants are the following:
2 -mercapto-4-methylpyrimidine.
2-mercapto-4-methyl-6-hydroxypyrimidine.
2-mercapto-5-methyl-6-hydroxypyrimidine.
2-mercapto-3-allyl-4-methyl-6-hydroxypyrimidine.
2-mercapto-4 : 6-diaminopyrimidine.
2 : 6-dihydroxy-4 : 5-diaminopyrimidine.
4-methyl-2: 6-dimercaptopyrimidine.
The amount of any of these compounds which is required is at least 3-6
mg per litre of bromide emulsion. Kendall had already disclosed the 2-mer-
capto-4-hydroxy and 2-amino-4-hydroxypyrimidines. <19 >
The halogenated hydroxypyrimidines have been claimed by Knott, <20 > for
example the 5-chloro- or bromo-2: 6-dihydroxypyrimidine. Amount: 10-20 mg
per litre of emulsion. Thioderivatives of 2 : 6-dihydroxypyrimidine were dis-
disclosed by Sheppard and Vanselow. <21 >
]. Thiazolidines. The 4-carboxythiazolidines which are, as we know, con-
trast modifiers (para. 270) can, depending on the example, be fog producers
or antifoggants. The derivatives of penicillin are thiazolidines: <22 > the penicil-
loic, penicillic and penaldic acids and penilolaldehyde. They are all retarders
of chemical ripening. Penicillamine is a fogging agent. Tajima and Kawa-
guchi <23 > have prepared 2-styryl-4-carboxythiazolidines which are weak
sensitizers or desensitizers with maximum activity in acid medium.
K. Iodonium derivatives have been disclosed by Steigmann. <24 > They are
primarily very effective anti-yellowing agents. The Antifiavog of 'Felix Sager
and Dr Grossler' (Heidelburg, Germany) is diphenyliodonium nitrate and is
used in amounts from 100-200 mg per litre of chloride emulsion. To prepare
it<25 > dichlorophenyliodide C 6 H 5 IC1 2 is converted to iodosobenzene, C 6H 5 IO,
then to iodoxybenzene C 6 H 5 l0 2 . This, treated with silver oxide, then with
sodium nitrate, gives diphenyliodonium nitrate. By combining the latter
with benzotriazole in the presence of ammonia, an addition compound,
Antipanog, is formed which is an anti-yellowing agent and an antifoggant,
used at a concentration of 40- 150 mg per litre of emulsion.
Kashida has recommended, as a particularly active antifoggant, 4-(2' :
4'-diiodophenoxy) quinaldinic acid. (12b>
L. Thiobarbituric acids. The thiobarbituric acids, related to the pyrimi-

dines, have an antifogging action in a concentration of 10- 5 to 10- 6 compared
with the amount of AgN0 3 • Among the most active we would mention
phenyl-thiobarbituric acid, 2-hydroxylidine-thiobarbituric acid and 3-
methoxy-4-hydroxybenzylidine-thiobarbituric acid. <26 >
M. Benzene-sulphinic acids. The benzene-sulphinic acids are prepared by
treating benzene with aluminium chloride, first in a current of hydrogen
chloride, then a current of sulphur dioxide at a temperature below l0°C. At a
concentration of 3-5 g per litre they have an antifoggant action with some
emulsions. They are used as antioxidants in photographic emulsions.
N. Alkaloids. Especially the hydrochlorides of quinine and quinidine at a
concentration of 1 mol. per 100 AgBr. Sheppard and Vanselow have disclosed
morpho line derivatives such as phenyl-morpholine. Concentration: 20-400
mg per litre. Other very effective antifoggants are 2'-aminothiazole-5: 6: 5'
6' -hydrocinchonidine and its derivatives. 2-picolic acid is also active.
0. Thioanilides such as thioacetanilide. <27 > These compounds are strong
desensitizers.
P. Saccharin and pyrazoline derivatives. <28 >
Q. Brominated fatty acids and acetylene dicarboxylic acids as their soluble
salts.
R. Protein degradation products: cysteine<29 > and histidine< 30 > hydrochlor-
ides.
S. Allylaminothiodiazole hydrosulphide and 2 : 6-dimercapto-4-keto-3 :
5-diphenylpenthiophene. <31 >
350. Indolizines
The most remarkable of all the photographic emulsion stabilizers are the
aza-indolizines discovered in 1935 by Birr. <32 > They were kept secret for many
years, and enable gold sensitizers to be used which, as we know, produce
considerable storage fog.
Indolizine is produced by reacting picoline (or methyl pyridine) with
bromacetaldehyde, following the scheme of Tschitschibabin:
. CH~
--+
O ~cH
Indolizine
CH
STABILIZING, FINISHING PHOTOGRAPHIC EM UL SIONS 379
An azaindolizine is obtained when the starting compound is IX-hydrazino-
pyridine. It is reacted with nitrous or formic acid (Markwald and Rudzik): <33 >
C
c~N,
l N 2 : 3~di azaindoli zi ne
NH·NH 'r\¢ N, ~
C
~/ 2
CH
~2
cx-hydrazinopyridine
With formic acid, a diazaindolizine is produced, and with nitrous acid, a

triazaindolizine.
It is possible to obtain more complex derivatives by the action of an amino-
triazole on an acetoacetic ester, by Bulow and Mitarbeiter's method: <34 >
CO, CH
acetoacetic ester 3-amino-l :2:4-triazole

- H2C~
I
7
cH;c~~r.. c~N/
N" I~
I 2N
5-methyl-7-oxy-2 : 3 :4-triazaindolizine
(enol form)
5-methyl-7-oxy-2: 3: 4-triazaindolizine is a powerful stabilizer. It is used

in 1% aqueous solution.
There is also 4-hydroxy-5-ethyl-6-methyl-2 : 3 : 7-triazaindolizine. <34b>
With a tetrazole, a 1 : 2 : 3 : 4-tetrazaindolizine is formed. The indolizines
can, however, have very varied constitutions and it is easy to see that the
number of these derivatives is very great.
In general, a 3-amino-1 : 2 : 4-triazole is condensed with ethyl ethoxy-
malonate to produce a 6-carbethoxy-5-hy droxy-2 : 3 : 4-triaz aindolizine. Cat
and Van Dormael <35 > reacted other amines of cyclammonium bases such as
2-aminobenziminazole, 4-phenyl-2-aminoiminazole, 4 : 5-diphenyl-2-amino-
iminazole, etc. with acetoacetic esters, malonic nitriles, and cyanacetic esters.
These esters have two reactive groups such as keto, nitrile, aldehyde or ester,
in the fJ position.
Birr and Walther<36 l have recently shown that the 1 : 3 : 4-triazaindolizines
are formed in fact with the nitrogen atoms in the 2 : 3 : 4-positions; position 1
being that which immediately follows the middle nitrogen adjacent to the two
nuclei.
351. Use of antifoggants

Antifoggants are either added to the emulsion or to the developer. Added to
the emulsion, they confer stability, therefore long storage life. The concen-
tration used in this case is in the order of 20 mg per litre of negative emulsion,
although this amount can vary widely according to the type of emulsion, the
degree of after-ripening, the purity of the gelatin and the nature of the anti-
foggant. It can be as high as 300 mg per litre with chloride emulsions contain-
ing 20 g silver nitrate per litre. The optimum amount can only be found
empirically.
The simplest method of use is to add the antifoggant (in aqueous, alcoholic
or aqueous-alcoholic solution) after digestion at the same time as the other
'finals'. It is also possible, and frequently advantageous, to add a small amount
before digestion in place of the bromide, to slow down chemical ripening and
prevent the production of a high fog level. In some chloride emulsion for-
mulas, it is even added before washing, but this does not dispense with a final
addition.
The actual effectiveness of an antifoggant can only be shown by experiments
with the coated and dried emulsion kept over long periods at normal tempera-
tures. A rough idea of its action can be obtained by prolonged digestion for
several hours, then by an oven test on the dry emulsion (10-60 hours at 40°C
(104°F) in a dry atmosphere). No absolute value should be given to the results
obtained, as time and temperature do not have equivalent effects.
Bluish tones are generally produced by the addition of antifoggants to
chloride emulsions. The antifoggants include nitrobenziminazole, benzo-
triazole, methylbenzthiazole, quinine hydrochloride and ethylbromacetate.
If the bluish tones are undesirable, certain mercapto derivatives can be used
to avoid the effect.
Addition to the developer. The antifoggant can be added to the developer
in a concentration of about 200 mg per litre. Too great an amount can bring
about a reduction of sensitivity. The addition of benzotriazole to developers
for chloride emulsions can produce bluish tones.
EMULSION FINISHING
352. Finals
Before an after-ripened emulsion is coated on its support, certain compounds
must be added to it to produce certain photographic characteristics, to ensure
good storage and to facilitate coating. These are:
1. Water to adjust the coating weight.
2. An antifoggant-necessary.
3. A pH buffer-optional: citric acid, mono- or disodium citrate, etc.
Sheppard (ash) disclosed diethylbarbituric, malic, malonic, diethylsuccinic
acids, etc. as buffers.
4. A sensitizing dye-optional: for colour sensitizing.
6. A removable filter dye-optional-such as tartrazine, using 30 cc of a ·
2 % solution per litre of emulsion, to limit light penetration; or a permanent
pink dye for warm tone papers.
6. An antioxidant-optional-such as sodium benzene-sulphinate or pyro-
catechin (colour emulsions).
7. An antiseptic-optional.
8. A matting agent-optional.
9. A hardener-necessary.
10. A wetting agent- necessary.
11. Alcohol to reduce viscosity-optional.
12. A plasticiser---optional- 1 : 1000 glycerin.
13. In the case of chloride emulsions, a contrast stabilizer. Developed chloride
images lose contrast when dried hot. This phenomenon is due to the aggrega-
tion of silver particles with an increase in reflecting power.
Traces of various compounds can be used to prevent this loss of contrast:
mercaptans, compounds with imino groups (in basic medium), potassium
iodide, selenosulphate, selenites, tellurites, mercuric nitrate, chloroauric acid,
chloroplatinic acid, etc. (See Schwartz: Ind. Eng. Chem., Anal. Ed., 1940,
369.)
353. Antiseptics
The antiseptics suitable for use in emulsions are phenol, thymol, methyl
p-hydroxy-benzoate and p-chloro-m-cresol.
Methyl p-hydroxybenz oate (Solbrol, Nipagine T) can be used at a concen-
tration of 0·2-1 % of the weight of dry emulsion. It is first dissolved in alcohol.
When phenol is added to emulsions made with some poor gelatins, in quan-
tities greatly in excess of those required for antiseptic purposes, it serves as
an excellent antifoggant: 4 g of phenol in 8 cc alcohol and 10 cc water for a
litre of emulsion containing 60 g AgBr.
There are many other strong antiseptics but their action towards photo-
graphic emulsions is not well known.
Sodium orthophenylphenate: four times as active as thymol or methyl
p-hydroxybenzoate.
Sodium pentachlorophenate (Xylophene, Santobrite).
p-chlorometaxylenol. <37 ) One part to 1000 dry gelatin. Soluble in water to
0·5 %.
Cationic surface active agents such as lauryl-dimethylbenzyl-ammonium
(Zephiran) can be used as antiseptics even at 1 : 20,000. These compounds
appear to arrest the growth of bacteria rather than kill them.
354. Matting agents

Matt emulsions are obtained by simply adding starch prepared as follows :
Rice starch 100 g
Cold water 150 cc
Make into a paste, add 180 cc water at 55°C then filter.
The amount for 1 litre of emulsion is 40 cc. Reduce to one-half or one-third
for semi-matt materials. Films are generally only made matt on the back.
Matt surfaces are also obtained by precipitating ethyl cellulose or cellulose
acetate in the emulsion. <3 8)
Colloidal silica is replacing starch. Kaolin gives rough surfaces.
355. Hardeners
The gelatin of negative emulsions is hardened with chrome alum. The amount
of chrome alum is 1% of the weight of gelatin. It is used as a freshly made 5%
solution which is added slowly with sitrring to avoid any coagulation. In paper
emulsions, from 1·6-2% of the weight of gelatin is used.
Compounds of zirconium and other tetravalent metals of group 4 of the
periodic table have been disclosed for replacing chrome alum. <39 >
For hardening the gelatin of paper emulsions, formalin or formaldehyde is
widely used as well as chrome alum (which has the advantage of increasing
the viscosity. The addition of enough formalin completely hardens the gelatin,
but after a period of at least 15 days, enabling it to be glazed with no risk of
melting. If too little formalin is used the gelatin melts and sticks to the plate
or the blanket; if too much is used, the paper, as it ages, leaves unglazed spots
on glazing. The amount which is necessary depends on the nature of the
gelatin and on its initial physical state.
Commercial solutions, said to be 40 %, have a density of 1·090 at 15°C.
They contain 360- 380 g H.CHO per litre. To avoid polymerization to para-
formaldehyde, 10- 15 % methanol is frequently added. <40 > Dilute solutions
polymerize less readily. Formalin is estimated colorimetrically using Schiff's
fuchsine reagent. <41 >
Concentration of formalin for paper emulsions: 16-24 cc of solution diluted
with four parts of water for 100 g gelatin, that is, 3·2-4·8 cc of concentrated
40% solution to 100 g gelatin. If the initial concentration is 30% the calcu-
lation must be adjusted.
Many organic hardeners have been proposed to replace formalin which has
the disadvantage of accelerating emulsion fog to the detriment of good keeping,
and it also has a choking odour.
Glyoxal, the dialdehyde of glycol, CHO-CHO, is sometimes used. <42 > Its
commercial 30 % solution contains polymers, 5% glyoxylic acid, 2 % acetic
acid, 0-03 % formalin and 0-18 % of inorganic matter. D = 1-25, pH = 3·5-
4·5. Glyoxal has no odour. From the photographic viewpoint, it can produce
fog in rapid negative emulsions and a loss of contrast in paper emulsions.
Amount for positive bromide emulsions: 8 cc of 30 % concentrated solution
for 100 g gelatin, in addition to chrome alum. ·
Dihydroxymethylurea (Finish EN- Sandoz; Ureol AC- Ciba) at a con-
centration of 4 g per 100 g gelatin hardens but reduces contrast.
The dihydroxyketones at a concentration of 0·5- 5 g per 100 g gelatin, <43 >
including fructose and p-hydroxybenzoylcarbinol. Also halogenated
ketones : dichloroacetone.
White< 44 > has disclosed the use of halogenated derivatives of the aldehyde
acids such as dibromo-butenaloic acid, at a concentration of 0·5-5 g per 100 g
gelatin. It is also called mucobromic acid COOH-CBr = CBr-CHO, and
is obtained by Simonis' method. <45 > If the pH of the emulsion is above 7, use
the corresponding sodium salt.
Variations in the melting point during storage can be prevented, according
to Sheppard and Houck<46 > by adding a hardening accelerator, such as resor-
cinol, phloroglucinol, cresol, thymol, etc. Concentration: 0·2% of the weight
of gelatin.
Hydroxyaldehydes up to the pentoses, such as arabinose. <4 7 >
Aminoaldehydes<48 > like piperidinoacetaldehyde hydrochloride or diethy-
aminoacetaldehyde at a concentration of at least 0·5 g per 100 g gelatin.
The condensation products of the dialkylamines with formalin are also
gelatin hardeners. (49)
Worwell and Kaye have put forward the hypothesis that the hardener com-
bines (at the isoelectric point) with the amino groups of the lysine derivatives.
In acid solution attachment is via the glutamic acid groups. <50 >
356. Wetting agents

Gelatin is a compound which is made hydrophilic by its -CO . NH- and
amino groups; it is made hydrophobic by its -CH 2 - groups. A gelatin
layer, coated and dried has its hydrophobic groups outermost. This prevents
wetting with water, although organic solvents readily make contact. This is
the reason why a photographic emulsion coated onto a gelatin treated base cannot
stick perfectly without the use of a wetting agent.
Surface tension. The wetting agents, also called surface active agents, have
the property of lowering the surface tension of liquids.
This tension is the force, in dynes per em necessary to break the contact
between a platinum ring touching the liquid (Lecomte Du Nouy tensiometer).
It can also be measured by the Wilhelmy method which is to partially immerse
a sheet in the gelatin solution or emulsion. Surface tension supports the sheet.
It is enough, to balance the resulting couple, to find the force exerted on the
sheet by the liquid. The Dognon-Abribat tensiometer is suitable for this
measurement. Perfect wetting of the sheet is assured by making the surface
matt. The emulsion temperature must be kept constant with a thermostat.
A surface-active agent is a compound in which one part of the molecule is
hydrophilic and the other is lipophilic. The hydrophilic part is made up of a
polyalcohol, a sulphate or a sulphone group, the lipophilic group is a hydro-
carbon chain. If, for example, the lipophilic chain of an oleic compound is
always oriented out of the water (weak hydrophilic force) the attachment of
polyethylene oxide chains makes this substance hydrophilic and literally
draws the oleic chain into the water.
The surface-active agents are divided into three groups :
(a) Anionic wetting agents: that is, when only the anion is active, for
example, the sulphonated, sulphated or carboxylated fatty alcohols. The salt-
forming groups are, respectively, - S0 3 Na, - OS0 3 Na or - CO. ONa.
(b) Cationic wetting agents or ammonium quaternary salts in which the
fatty radical 1s positively charged. Example, hexadecyltrimethylammonium
bromide:
(R-N = (CHa)a]+Br-
1
(c) Non-ionic wetting agents. These are the saponins, the hydroxyethyl
fatty substances (Peregal 0, Cemulsols) and phenolic side chain compounds.
Only the anionic and cationic compounds are used in practice as emulsion
additives for coating. The cationic compounds are used in development to
reduce the induction period.
An important condition of the use of a wetting agent is its chemical inertness
towards the emulsion. Sensitometric and storage tests must precede its experi-
mental use. Fog can be produced by impurities in the product.
Saponin is the most widely used wetting agent for emulsion coating al-
though it has only moderate surface active power. (50b J It is a natural product
of uncertain chemical constitution, and its activity varies with its source,
which must be carefully controlled. The sources are still quillaya bark, horse-
chestnuts and soapwort root. Saponin is used in a concentration of 5- 10 cc
of a 5% solution per litre of emulsion.
Alkyl sulphates with the general formula R. CH 2 -0. S0 3 • Na are im-
properly called sulphonated fatty alcohols. The fatty portion contains 8-15
carbon atoms. The most common are sodium capryl-, undecenyl-, and lauryl
sulphates CH 3 - (CH 2) 10 - CH 2 -0-S0 3 Na. Teepol is a mixture of secon-
dary alkyl sulphates of caprylic to stearic alcohols at a concentration of 21 % .
All of these compounds must be in the pure state, otherwise storage fog
will be produced.
The surface tension of water is reduced from 70 to 45 dynes by adding
20 mg of the dry product per litre.
The succinic sulpho-esters are very active, especially those from 1-methyl-
4-ethyl-hexanol. C51 l They are obtained by reacting ethyl maleate with sodium
bisulphite. Another interesting succinic derivative is sodium pentadecylene-
succinate with the formula
Condensation products of succinic anhydride with tertiary amines includ-

ing a group which can react with carboxyl bases has also been disclosed C52 l
for example, tetradecylene succinic anhydride and diethylethanolamine.
Two other surface active agents suitable for use in emulsions are:
Nekal EX-sodium isobutylnaphthalene-sulphonate.
Igepal C -condensation product of a dodecylphenol with ethylene oxide.
Concentration 8 cc of 4 % solution per litre.
Superimposed emulsions. Better adhesion between superimposed emulsion
layers is achieved if the two wetting agents are of different types, e.g. a succinic
derivative and Nekal BX, Saponin and Igepal, Igepal and Nekal, etc.
357. Antifrothing agents

Wetting agents have the disadvantage that they encourage frothing, which is
a great nuisance during coating. It is often necessary to stand the finished
emulsion before running into the coating trough. The addition of certain
alcohols can rapidly disperse froth: butyl, amyl, benzyl alcohols or better,
2-ethylhexyl alcohol (2-ethylhexanol of the Carbide and Carbon Chemical
Co.) and 3:5: 5-trimethylhexyl alcohol (Nonanol-I.C.I.).
These compounds are also, like the amyl alcohols, energetic surface active
agents. They can therefore bring about a pronounced reduction in surface
tension if too high a concentration is used and if another layer is coated on
top this operation would be made more difficult. The amyl alcohols have a
very choking smell.
Another variety of anti-frothing compounds includes glycerin and glycol
esters such as glyceryl monolaurate or propylene glycol monolaurate.
358. Viscosity of emulsions

It is important to know the viscosity of emulsions as it controls the thickness
of the layer. It depends on the gelatin concentration, the natural viscosity of
the gelatin and the amount of hardener added (especially chrome alum). It can
be reduced by adding water or alcohol.
The viscosity of an emulsion increases with the time which the emulsion is
left in the coating machine, due to the progressive hardening action of the
hardeners. It is important to bear this in mind.
The viscosity drops as the temperature rises but this reduction is not propor-
tional. The viscosity drops violently around the setting point but as the
temperature increases the variation becomes of less and less importance. If
the emulsion sets at 27°C (81 °F) the drop in viscosity is almost insignificant
around 40°C (104°F). It is, on the contrary, very definite between 32 and
36°C (90- 97°F). The progress of this phenomenon can be respresented by
a hyperbolic curve.
According to Bogomolov, the setting temperature is given by tgel = 22·8 +0·137] 39

where 7J•• is the viscosity in centipoises at 39°C. The viscosity is related to the tempera-
ture t by the relation 1) = By't -tgel where B is a characteristic constant of the
emulsion. Shor<••> has shown that the curves log 1) = f(t) are in fact formed of two
straight lines which cut at about 35°C. If the viscosity at 40° is known, then:
at t < 35°C: 7)t = 7)40 x 10 exp (0·40- O·lt) with d7J = - 0·0257)
dt
at t > 35°C: 7Jt = 7)40 x 10 exp (0·75 - 0·02t) with d7J = - 0·05 1)
dt
Viscosity measurement. The viscosity is due to internal resistance which opposes the
flow of a liquid, that is, a displacement of its molecule3 relative to each other. It is
therefore a negative force. The unit is the poise; it is the opposite of a force of 1
dyne.
If the rate of flow of an emulsion or a simple solution of gelatin down a capillary
tube maintained at constant temperature by circulating warm water is measured, the
coefficient of viscosity is given by the formula 1rr 4 pT/8lV where Vis the volume which
flows out, T the time to flow, p the flow pressure, r the radius of the tube and 1 its
length. The specific viscosity is given by comparison with that of water which is fixed
at 100. To do this, viscometers similar to the Baume one is used. The French
A.F.N.O.R. apparatus consists of a cylinder of thick brass whose conical base is drilled
with a calibrated hole. The cylinder is first plunged into hot water at the same
temperature as the emulsion, drained and filled to the brim with emulsion whilst the
hole is stopped up. An outer rim enables the apparatus to be filled to the brim. The
emulsion is allowed to run out and the time in seconds is noted whilst a small thermo-
meter is put into the liquid to determine its exact temperature. The opening in the
instrument is chosen to give a flow time in the order of 90 seconds.
A more rapid method of measuring the viscosity, is to rotate a cylinder in the liquid
and measure the opposing force. This is the principle of the Couette-Sheppard appara-
tus. Another very convenient instrument is the Brookfield Synchro-Lectric Viscometer
(made by Brookfield Engineering Laboratories at Sloughton, Mass., U.S.A.) which is
made up of a small electric motor having a cylindrical rotor attached: the speed of the
motor is reduced more as the opposition due to the viscosity is greater. The scale is
graduated in centipoises.
High-frequency impulse viscometer. This apparatus, based on the principle of
magnetostriction, includes a generator of high-frequency current which elongates
(about 0 ·5 !-') a thin sheet. When this is plunged into a liquid the oscillations are
damped and their average amplitude decreases with increasing viscosity. The measure-
ment is therefore very rapid and is carried out with the minimum inconvenience, for
all that has to be done is to immene a stem in the liquid t o be m ~ asured, and read off
the viscosity on a dial. The simplicity of this method is only equalled by the complex-
ity of the apparatus required: in addition to the generator, an amplifier and an inte-
grating circuit. The high-frequency impulse viscometer was perfected by Rich and
Roth (Hartford, Conn., U.S.A.) and the Bendix Aviation Corp. (Cincinnati, Ohio,
U.S.A.).
359. Emulsion coating

The emulsion is coated onto paper or film either by dipping, or with a roller.
In the dipping process the base passes under an ebonite roller into a trough
of emulsion, removing a certain amount. In the second process, it is an auxili-
ary roller which dips in the reservoir, and by turning deposits emulsion on
the base. The roller does not touch the support. Its diameter and speed of
rotation determines the amount of emulsion carried up. The triangular space
formed between the roller and the support is filled with emulsion; it is the
'bead' which must be kept full .
Roller coating is more difficult to perform correctly than dip coating; if the
roller diameter, its speed of rotation, the speed at which the base is moving,
the emulsion viscosity and surface tension are not correctly adjusted, parallel
line marks in the direction of travel will result.
Many other coating systems have been tried: doctoring with a knife kept
a short distance away or with a 'blade' of compressed air, scraping with a
rotating shaft around which is wound a spiral of very fine wire, spraying with
a spray gun, etc.
During the whole coating operation, the emulsion must be kept at constant
temperature; this is fixed between 32 and 38°C (90- 97°F) depending on the
emulsion viscosity and the required setting speed. The emulsion viscosity
must be higher when the dipping method is used. It is, however, difficult
to maintain the temperature constant throughout the length of the trough, so
an excess of liquid is fed into the trough so that it overflows. Furthermore,
care must be taken that the cold air from the setting chamber does not flow
down into the emulsion trough.
The thickness of the coating is fixed by the viscosity of the emulsion at a
given temperature and by the machine speed. The more viscous the emulsion
and the higher the machine speed, the thicker the coating.
The layer evens out by running back vertically. After receiving the liquid
emulsion, the film (or paper) is drawn up vertically for a height of 3-6
feet.
Setting. The films are cooled in a chamber fed with cold air at l5°C. The
temperature must be neither too low nor too high, for setting can only take
place after a fixed period of time. Papers are set either in a long chamber or
by passing them over a metallic drum cooled internally.
Supercoating. The set emulsion receives, preferably by dipping, a thin sur-
face protective gelatin layer. This very critical operation is termed super-
coating. The gelatin solution is made up of:
Water 800cc
Inert gelatin 22g
Alcohol 200 cc
5% alum 0·8 cc
5% Saponin 5 cc
Too high a percentage of alcohol brings about the formation of coagulation
streaks.
For the best supercoating, the temperature of the coated paper or film must
be balanced with that of the gelatin solution. If the emulsion is too cold, the
layer does not adhere (streaks) and if it is too warm there is a risk of remelting
it. The temperature of the supercoating solution is kept at about 27°C. After
supercoating the emulsion is again cooled.
Thick bromide paper for postcards, which is dry-glazed, is not generally
supercoated.
Coating speed: 18-45 feet per minute depending on the type of machine and the
length and efficiency of the drying chamber. Most frequently it is about 18 feet. Some
document papers, which do not need a uniform coating, are coated at high speed.
Transport of the base. The base is driven at the end of the coating machine with a
felt blanket fitted with a suction system. Irregular running on one side or the other
leads to the formation of creases and stops the machine.
Width of the base. The three standard widths of paper and film are 43, 48 and 54
inches but there are many other smaller widths.
Plate coating. Emulsion is coated on plates with a weir having the shape of a tray.
This tray is fitted, on the side where the liquid is introduced, with an inclined plate
which is hinged and ends with a sheet of celluloid. The celluloid rests very lightly on
the glass plates moving by underneath it, and the emulsion flows down it. The glass
plates positioned by guides of variable width, are moved by rollers, one group of
which is cooled with water. The amount of emulsion coated is determined by the flow
from the tube which carries the liquid.
Another form of weir is made up by a roller dipped into a dish which feeds an
inclined plate via a scraper.
0
360. Emulsion drying

After coating with emulsion, photographic films and papers are dried for
several hours in drying chambers 80-100 yards long. The support is arranged
in festoons 6-12 feet high supported by sticks 15 in. apart. The sticks are
supported by two chains which advance slowly. Thus the festoons starting
from one end of the drying chamber are dry by the time they reach the other
end and can then be rolled up.
The sticks have the disadvantage that they leave marks. They can be re-
placed by hollow cylinders.
The drying chamber can be in a straight line or horse-shoe shaped. The air
temperature is at a maximum in the middle. For the first quarter is must be
25- 30°C (77- 86°F); in the second and third quarters 30- 40°C (86-104°F)
and 20-25°C (68-77°F) in the remainder. Drying which is too fierce crinkles
the edges of the paper and makes its manipulation and reeling very difficult,
and this is why the relative humidity must be constantly controlled. Good
drying depends above all on careful distribution of the air: the air led out of
one section and readmitted in another, saturated with moisture, can obviously
have no useful effect.
The air brought into the drying chamber should be filtered, preferably
over ferrous hydroxide then over paper, then washed with water at 10-15°C
(50-59°F) before being reheated. In some works the air is merely passed
through an oiled filter. For correct drying, more than 100,000 cubic feet of
air per hour must be used for each machine.
Machine with rapid drying (Agfa) for thin layers. These machines are used
for the manufacture of multilayer colour films. The film after receiving the
emulsion by dipping, is immediately dried with air at 35°C without inter-
mediate setting. The path of the film consists of a vertical run of 6·5 feet, then
a horizontal one of 46 feet. A large 16 ft. drum enables the film to be brought
back. Speed: 10- 13 feet. Drying time: 10 minutes. Thickness of dry layer:
10 fL·
The same operation with a normal machine requires a drying chamber
160 feet long at a speed of 26 feet per minute and uses 40,000 cubic feet of air
per hour at 35°C and 30 % R.H.
Continuous running machine. The coated film is set in a vertical chamber,
then passes into a drying room through which it moves continuously in a
zig-zag guided by upper and lower rollers. The upper rollers guide the film
by its two non-coated edges whilst the lower rollers with lateral flanges keep
it vertical and compensate for stretching and shrinkage. The drying chamber
is divided into sections through which the temperature increases then de-
creases. The rollers are mounted on ball bearings. A viscometer is permanently
installed in the emulsion trough.
Photoelectric control of the liquid emulsion layer. The thickness of the layer
of liquid coated on the film can be immediately measured with a system of a
light source, a filter which only transmits infra-red, a photo-cell and a galvano-
meter (with a scale or a recorder).
The thickness is checked in this way at several points across the width of
the band. With a lateral sweep using a mobile infra-red source, the thickness
can be measured everywhere.
Shrinkage. An emulsion test coated on a thin film of oxidized aluminium
is dried. The shrinkage of the dry emulsion is measured by the contraction of
the metal foil. It is stated that the shrinkage passes through a maximum at the
isoelectric point. The shrinkage corresponds to the crinkling of film or paper
bands in the coating machines.
Difficulties of emulsion coating. Coating is a very critical operation and it is
rare that it can be carried out without incident owing to the fact that it is
necessary to work in almost complete darkness. A coating of a constant thick-
ness, without bubbles, streaks or dust, is very difficult to obtain. The problem
becomes still more complex when it is necessary to superimpose several layers
for colour work.
1. Concentration bridge. A chain of two silver nitrate solutions of different concen-

trations, and in which two silver electrodes Ag 1 and Ag 2 are immersed, following
the plan Ag 1 !(AgN0 8 ) 1 j: (AgN0 3 ) 2 !Ag 2 • If (AgN0 3 ) 2 is more concentrated than
(AgN0 3) \ and if Ag 1 is joined to Ag 2 by a metallic conductor the electrochemi-
cal system produced has an e.m.f. which will tend to circulate the current from
Ag 2 towards Ag\ the more concentrated solution <2 > loses ions to the correspond-
ing electrode-Ag-1-+e- = Ag. The electrons necessary for this movement come
via the conductor, in the opposite direction to the arbitrary current, from the
electrode Ag 1 in the weaker solution; here, it is the metal which tends to dis-
solve in the solution to form ions, -Ag = Ag++e-. The Ag+ ion enriches the
solution(') whilst the electron e-, travelling to Ag 2 discharges the ions in solu-
tion. <2 > The observed e.m.f. is composed of two terms E 1 and "• corresponding to
the potential differences which occur between each electrode and the solution in
which it is immersed.
2. Smith T. D.: R.P.S. Cent. Conj., London 1953 and Sci. et Ind. Phot., 1953, 403-
405.
3. Calhoun J. M.: P.S.A. Jl., 1952, 86-89.
4. Kikuchi S. and Sakagushi Y.: Jl. Soc. Sci. Phot. Japan, May 1951, 126-131; Sci.
et Ind. Phot., 1952, 178.
5. Sheppard and Vanselow: Ger. Pat. 707,785.
6. WulffP.: U.S.P. 1,697,930 and Trivelli and Jensen:Jl. Frank. Inst., 1930,287.
7. King and Acheson: J.C.S., 1949, 1396-1400.
8. Steigmann A.: Jl. Soc. Chern. Ind., 1943, 42. Bicychin and Vlach: Sci. et Ind.
Phot., 1947, 333. Oyama: Bull. Inst. Phys. Chern. Res. Tokyo, 1942, 364-374;
1943, 483-489; 1944, 23-20; Sci. et Ind. Phot., 1950, SO.
9. Bull. Soc. Sci. Phot. Japan, Dec. 1953, 14-25 (in English); Sci. et Ind. Phot.,
1955, 172.
10. Brooker and Staud (Kodak): F.P. 851,912 (1938), U.S.P. 2,131,038.
11. Suzuki and Toriu: Jl. Soc. Sci. Phot. Japan, Nov. 1952, 9-26; Sci. et Ind. Phot.,
1952, 276.
12. Kashida, Yokota and Hai: Jl. Pharrn. Soc. Japan, 1951, 553 ; Sci. et Ind. Phot.,
1952, 432.
12b. Kashida : Jl. Soc. Sci. Phot.Japan, Aug.1953, 16,1-32 (in Japanese).
13. Oyama: Bull. Soc. Sci. Phot. Japan, in Sci. et Ind. Phot., 1952, 178.
14. B.P. 283,679 (1926); B.P. 283,661 (1926); F.P. 716,836 (1931).
15. Mariani and Martinelli: Sci. et Ind. Phot., 1955, 1-3.
16. Murobushi, Kawaguchi and Ashikawa: Jl. Chem. Soc. Japan, 1953, 373 (in
Japanese).
17. Kikuchi and Sakaguchi: Colloque Sc. Phot., Paris 1951, 248-260.
18. Koseki and Fukawa: Jl. Soc. Phot. Japan, March 1951, 95, 102 and 103-108 ;
19. Kendall J. D.: F.P. 847,881 and 828,343.
20. Knott E. B. and Kodak: F.P. 968,637 (1946); Brit. prior. 1941.
21. Sheppard S. E. and Vanselow W .: F.P. 916,255 (1945).
22. Koseki and Ishida: Bull. Soc. Sci. Phot. Japan, Aug. 1951, 17-23.
23. Tajima and Kawaguchi: Jl. Soc. Sci. Phot. Japan, Nov. 1949, 1-14; Sci. et Ind.
Phot., 1951, 253.
24. Steigmann: Sci. et Ind. Phot., 8(2), 65.
25. B.I.O.S. Trip 2133, Report V, 1946, 2 pp. H.M. Stationery Office, London and
Sci. et Ind. Phot. 1951, 186. B.P. 477,628.
26. Murobushi, lchifugi and Ashikawa: Jl. Chem. Soc. Japan, 1953, 539-542 (in
Japanese).
27. Sheppard S. E.: Sci. et Ind. Phot., 1930,378.
28. Sheppard and Wightman (Kodak): F.P. 690,646 and 690,647.
29. Trivelli and Jensen: Jl. Franklin Inst., 1930, 287.
30. Wulff P.: U.S.P. 1,696,830.
31. Fuchs: Phot. Ind., 1932, 834 and 864.
32. Birr E. J.: Zeits. Wiss. Phot., July 1952, 2-27.
33. Ber., 1903, 1111.
34. Ber. (1909), 2208, 2487, 3555, 4429, 4638 and (1910), 375 and 1973.
34b. Kuwahara and Aoki: Konishiroku Rev., March 1955, 1-10 (in Japanese).
35. de Cat and Van Dormael: Bull. Soc. Chim. Belge, Dec. 1950, 573-587 and
April1951, 69-75.
36. Bir and Walther: Ber., 1953, 1401-1403; Sci. et Ind. Phot., 1954, 159.
36b. F.P. 825,975.
37. Monsanto.
38. I.G.F.: B.P. 510,090 (1938).
39. Kodak-Pathe: F.P. 864,501 (1941).
40. Homer H. W.: Jl. Soc. Chem. Ind., 1941, 213-218.
41. SegalL. : Anal. Chem., 1951, 1499.
42. I.G.F.: G.P. 538,713 .
43. I.G.F.: F.P. 823,500 (1937).
44. Kodak-Pathe: F.P. 826,942 (1938).
45. Ber., 1899, 2084.
46. Sheppard and Houck: F.P. 827,125 (1938).
47. Kodak-Pathe: F.P. 795,451 (1935).
48. I.G.F. : F.P. 871,377 (1941).
49. Brintzinger and Hesse: Kolloid. Zeits., 1948, 156-166.
50. Worwell and Kaye : Nature, 1944, 525.
SOb. For the measurement of surface and interfacial tensions of the saponins, see
Ruyssen: Rec. Trav. Chim. Pays-Bas., 1946, 580.
51. Caryl C. R.: Ind. Eng. Chem., 1941, 731-737.
52. I.G.F.: F.P. 892,548 (1943) .
53. Shor M. I.: Zh. Prikl. Khimii, 1951, 847-852.
ULTRA-VIOLET PHOTOGRAPHY
GENERAL CHARACTERISTICS OF THE
ULTRA-VIOLET SPECTRUM
The existence of ultra-violet radiations, forecast by Herschel in 1800, was

established by Ritter, Inglefield and Wollaston immediately after the dis-
covery of the infra-red.
At about 415 mJL the violet darkens considerably and at 396 mJL colour
becomes greyish and hardly visible. In practice the ultra-violet spectrum
extends from 400 to 13 ffiJL.
361. Ultra-violet sources

Natural sources. The ultra-violet region of the solar and stellar spectra is
limited by the atmosphere in which we live. The short wavelength ultra-
violet produces ozone when it reacts with oxygen and axone absorbs these
radiations strongly. Ten miles above the earth is a layer containing sufficient
ozone to absorb all the ultra-violet below 290 mJL. The transmitted solar
radiations contain only 5 % of ultra-violet rays.
Artificial sources. A study of black body radiation shows that the emission
of ultra-violet rays increases with the temperature: the arc lamp is much
richer in these radiations than the incandescent lamp whose emission is
negligible. The limit of the arc spectrum, which is more extensive than the
sun after absorption, is a little beyond 300 mJL. The strongest emission band
is at about 290 mJL. It can be accentuated by incorporating metallic salts in
the arc carbons.
The light given by the oxy-hydrogen flame on chalk or magnesia gives no
radiations beyond 300 mJL and the intensity drops sharply beyond about
350mJL.
Heated metals, necessarily at a fairly low temperature, emit little ultra-
violet.
Magnesium light is much richer: its limit of emission is at 280 mJL.
Metallic vapours give lines of much shorter wavelength : iron at 237 mp.,
zinc at 202 mJL and aluminium at 185 mp.. It is the same with spark spectra.
Sparks formed in water are used as sources in spectro-photometric measure-
ments. An iron rod covered with Eder's alloy (Cd Fe Ph) gives an almost
continuous spectrum from 481 to 231 mP- together with many lines as far as
202mJL.
391
By discharge in rarefied hydrogen, 103 mJ-t can be reached. The mercury-

vapour lamp is very rich in ultra-violet lines up to 200 mJ-t, the spectrum has
about forty strong lines, one of the most intense of which is at 365 mJ-t.
Beyond this limit, the quartz bulb absorbs the majority of the radiations.
The emissive power of the mercury lamp is increased by operating under
pressure: up to 40 atm. in air and more than 100 atm. if the lamp is water
cooled.
A high-voltage discharge through an acetylene flame gives a continuous
spectrum which extends considerably further into the ultra-violet than that of
the usual light sources.
362. Absorption
The absorption of the ultra-violet by various substances varies greatly. The
following are transparent to the near ultra-violet (300-400 mJ-t): mica, cellu-
loid, Canada Balsam, glycerin, acetone, etc.
Transparent to the middle ultra-violet (200-300 mft): fused quartz, rock
salt, fluorite, alum, gypsum, sugar, water, alcohol, liquid ammonia.
The absorption limit obviously depends on the thickness.
Window-glass transmits to 310 mp. Its transmission curve varies with the
time of exposure to light.
Ordinary glass n = 1· 51 transmits down to 295 mJ-t.

Light flint n = 1· 57 transmits down to 305 mJ-t.
Dense flint n = 1·69 transmits down to 335 mJ-t.
Helioglass transmits down to 280 mJ-t.

Crystal quartz is more transparent than fuzed quartz. Its transmission limit
is 185 mJ-t.
The middle ultra-violet is readily absorbed by the air as far as 200 mJ-t.
The radiations below 305 mJ-t are detrimental to living cells. As to the eye,
the cornea is opaque to rays below 295 mJ-t and the crystalline lens to those
below 350 mJ-t.
Ultra-violet transmitting filters. Glass coloured with nickel oxide is trans-
parent to ultra-violet and opaque to the visible spectrum. Similarly with the
following glasses (309 to 400 mft with a maximum at 360 mJ-t)
Corning Ultra Violet 586
Chance No. 14
Schott U.G.l, U.G.2, U.G.4.
Also used are:
Silvered quartz (transmission to 320 mJ-t).
Wratten 18A (gelatin filter).
Solution of p-nitrosodimethylaniline (200-370 mJ-t). (See para. 469.)
Absorbing filters. In para. 466 the composition of many ultra-violet absorb-
ing filters will be given. To these add the following solution:
Cerium ammonium nitrate 1 : 1000 acidified with sulphuric acid: trans-
mits radiations above 375 mp,. Ten times as concentrated, it only transmits
above 460 mp,.
363. Spectrographs
Prism spectrographs are used exclusively for the study of the ultra-violet down
to 125 mp,. Below 125 mp, they are replaced by metal grating instruments.
Flint prisms are used for spectra between 400 and 360 mp,.
Quartz is used between 400 and 180 mp,.
To reach 125 mp, fluorite (CuF 2) prisms must be used and work carried
out in a vacuum.
Schott Uviol prisms can be used down to 253 mp,.
With quartz, a special prism must be used because of the birefringence and
rotatory power. Two 30° half prisms, one from a laevorotatory and the other
from a dextrorotatory crystal are used, cut in such a way that the refraction
pattern is perpendicular to the optical axis, and stuck together with a trace
of water or glycerin (Cornu prism). The use of the apparatus requires great
care due to the invisible radiation. When the collimating lens is achromatic
(quartz-fluorite) the collimator is adjusted with radiation which is easy to
standardize. The sensitive layer is placed obliquely to the axis of the con-
vergent lens and takes the shape of a caustic curve. The apparatus is then
adjusted approximately using a fluorescent screen, for example, uranium
glass or a gelatin layer 0-15 mm thick containing 1 : 1000 aesculine and
2·5 : 1000 uranine. Successive negatives are made to standardize. The Fery
apparatus has no lenses, but a curved face prism, and gives a spectrum from
670 to 215 mp, with a length of 21 em.
ULTRA-VIOLET SENSITIVE LAYERS

364. The maximum absolute sensitivity of silver bromide is at about 350 mf.'
in the ultra-violet. The sensitivity then decreases rapidly to 300 mp, because
of absorption by the gelatin, and at 240 mp, is practically nil.
We shall see in the fourth part of this work that the sensitization by dyes
is possible only if there is a certain gap between the spectral absorptions of
the emulsion and the dye. As the photographic emulsion absorbs the majority
of the ultra-violet, the absorption maximum of the dye must be displaced
towards the longer wavelengths; this is the case with the simple oxacyanines
which sensitize silver chloride but not silver bromide. It can therefore be
understood that there can be no sensitizing substances for the ultra-violet, at
least in the limits of spectral sensitivity, by a process similar to that of colour
sensitization.
There are actually two principal methods of preparing ultra-violet sensitive
emulsions, with many variations:
The Schumann method.
The fluorescent layer method.
365. Schumann method

The method invented by Schumann in 1894 is to prepare a fine-grain emul-
sion containing only a small proportion of gelatin. The absorption of radia-
tions by the colloid is in this way reduced to a minimum. With ordinary
emulsions only the surface layer is affected.
The preparation method is as follows:
A suspension of silver bromide is made in very dilute gelatin. After some
time the liquid, coated on plates, deposits the silver bromide which takes down
with it a very small amount of gelatin; the excess liquid is removed leaving a
very thin layer of silver bromide with a small amount of colloid.
Hopfield and Appleyard process. The emulsion is coated upon gelatin-
coated plates. Unexposed commercial plates, fixed in hypo and alum, washed
for 8- 10 hours in running water then in distilled water before drying in a
dust-free place are used.
Each plate is placed on a piece of plate-glass 1 em smaller each way than
the plate, resting on a perfectly level glass table and each supported by two
perfectly cylindrical glass rods 8 mm diameter. A sheet of thin paper the size
of the plate glass can be placed between the latter and the plate.
Using a pipette, a layer of molten emulsion 2-3 mm thick is poured onto
each plate and allowed to remain for three hours. To remove the excess liquid,
one edge of the plate can be run along a vertical glass tube whilst the other
edge is slightly raised. Care must be taken not to disturb the layer deposited
on the plate. This is then dried in a horizontal position.
The emulsion is prepared as follows:
In the waterbath at 60°C is:
Gelatin 7·5 g
( Potassium bromide 15 g
into which is slowly poured (in red light):

{ Silver nitrate 18·75 g
with constant agitation. The vessel containing the emulsion is corked and
kept at 50°C for 30 mins. for ripening.
After decanting, the emulsion is set, noodled and washed for three hours at
10-12°C. After draining and remelting, the emulsion is ready for coating.
More rapid, but softer plates are obtained by ripening for a much longer
time-at 60°C. The sensitivity is increased fifteen times, the fog not becoming
important until after three days.
These plates enable wavelengths down to 50 mJL to be recorded. They
keep for a maximum of two months.
Instead of using a support covered only with gelatin, plates which have not
been fixed can be used. In this way a very extended spectral sensitivity can be
obtained.
If films are used, they must be kept flat during preparation.
There are now new plates commercially available-Eastman Kodak SWR
-having a very low gelatin content, and which are very sensitive (as fast as
fluorescent layer plates). These plates have been studied by Schoen and
Hodge (J.O.S.A., 1950, 23-28).
Duclaux and Jeantet Process. Commercial plates are placed horizontally in
the bottom of a dish of dilute sulphuric acid (100 cc of acid S.G. 1·84 per
litre). After four hours immersion at an average temperature of 25°C (a little
higher at the beginning, a little lower at the end) they are carefully removed
and immersed in a dish of water through which running water passes so
slowly that the liquid is not disturbed. After 30 mins. the plates are
dried; as the remaining emulsion layer is very thin, drying takes only a few
minutes.
This layer, poor in gelatin, is very fragile and must be covered with a thin
layer of collodion before development. By immersing the plate in water before
the collodion is dry, it is possibl~ to develop the plate normally.
The plates giving the best results are fine-grain cold tone lantern plates.
At A = 184 they are ten times more sensitive than ordinary Schumann plates
and two hundred times more sensitive than before the acid treatment.
366. Superficial fluorescent layer method

This method, also due to Duclaux and Jeantet, consists in applying to the sur-
face of an ordinary plate, a very thin layer of a fluorescent substance which,
excited by ultra-violet radiations, emits radiations of longer wavelengths in
the blue-violet which expose the emulsion.
The selected substances must have a blue or violet fluorescence, and must
be soluble in a solvent which does not swell gelatin. Good results have been
obtained with a solution of aesculine in glycerin. It is, however, better to apply
a few drops of machine oil using a wad of cotton. The fluorescence is due to
the presence of hydrocarbons such as phenanthrene, anthracene, etc.
Before development the plate is washed with ether, then with alcohol. Other
solvents can be used.
Fluorescent layers which are thinner and more effective are obtained by
using a solution of the oil in a volatile solvent-alcohol or petrol.
The sensitivity of ordinary or orthochromatic plates treated in this way is
double that of the sulphuric acid treated ones. With a water-prism spectro-
graph, sixty iron lines between 199·5 mf.L and 187·6 mf.L can be recorded
with an exposure of a fraction of a second. Three minutes exposure enables
151lines to be recorded in the same spectral interval.
Lyman was, in this way, able to photograph the ultra-violet down to 58 mf.L.
Many other substances have been suggested to replace machine oil:
Vaseline oil in petroleum ether (Beach).
Clear paraffin oil (Nujol type).
Salicylic acid in alcohol (1 %) (Thovert).
Fluorene-2·5 % in ethyl acetate.
o*
396 PHOTOGRAPHI C CHEM I S TRY
Before use, 4 % of a saturated alcoholic solution of bleached shellac can be

added. Fluorene, with the structure
is a compound with a violet fluorescence. It melts at 113°C. It is found in

coal-tar fractions taken off between 270° and 300°C. B.Pt. 295°C. Fluorene
can be replaced by the following:
2 % Carbaz ol.
2 % Ethy l carbaz ol.
2% Naphthylamine sulphonic acids.
Carbazol or dibenzopyrrole has the formula
M.Pt. 238°C, B.Pt. 351 oc, contained in crude anthracene from which it can
be extracted as the potassium salt by fusion with potash: N-ethyl carbazol
melts at 68°C.
Among the naphthylamine sulphonic acids are: 1-naphthylamine-4-sul-
phonic acid. Obtained by treating 1-naphthylamine with an excess of sul-
phuric acid at 130°C.
2-naphthylamine-1-sulphonic acid.
2-naphthylamine-6-sulphonic acid.
2-naphthylamine-6 : 8-disulphonic acid (4% ).
We would also add 2-naphthol-6 : 8-disulphonic acid-4 %. It is best to
use these compounds in a slightly alkaline solution.
Dihydrocollidine carboxy lic ester in a volatile solvent. It is removed with
acetone.
Eastman 103a-O plates are provided with a resinous fluorescent layer 10 1-L
thick. The maximum fluorescence is at 315 mJ.L. After exposure, the layer is
removed with hexane. No information is given on reciprocity failure between
15 sees. and 7 mins. , nor on the intermittency effect. <1 >
367. Actinometric paper

Apart from the silver salt emulsions, there is a host of organic and inorganic
compounds which are sensitive to ultra-violet rays .These compounds are dis-
cussed in the chapters concerned with inorganic photosensitive systems and
with the photochemical formation and destruction of organic compounds.
They have only a limited application in the practical recording of the ultra-
violet. We would mention, however, an actinometric paper sensitive to the far
ultra-violet based on the formation of a triphenylmethane dyestuff which has
previously been converted to the cyanide compound. Light liberates -CN
groups. The following formula is a variation of that of J. Lifschitz (1919) by
Chalkley (J.O.S.A., 1952, 387).
Filter paper is impregnated with:
4 : 4' : 4"-triaminotriphenylacetonitrile 0·1 g
r(
Acetonitrile 10 cc
Toluene 10 cc
~ (Crystolite 1g
l
Toluene (warm) 10 cc
,8-(p-tert. butylphenoxy)-ethyl alcohol 5·8 g
Toluene to 80 cc
(Crystolite is a Rohm and Haas methacrylate.)
The white paper becomes pink in sunlight. It is sensitive between 230 and
326 mp,.
When the dyestuff contains hydrophilic groups, the solvent may be water.
The preparations of such substances: ethyl green, xylene blue VS and xylene
blue AS cyanides have been described (J.A.C.S., 1955, 1848).
APPLICATIONS
368. The scientific applications of ultra-violet photography are numerous:
spectrography and spectral analysis, metallurgy, biology, botany, astronomy,
etc.
When a subject is photographed through a filter of a solution of p-nitroso-
dimethylaniline (transmission 370-200 mp,) or a solution of cobalt sulphate or
Hofmann violet (380-300 mp,) it is stated that on the image, the shadows dis-
appear.
The differences of reflection or transmission of ultra-violet by different
substances enables interesting photographic effects to be obtained.
White zinc oxide appears absolutely black.
Polished silver also appears black.
White flowers 'phlox' which absorb ultra-violet give an almost black image.
Photography of the full moon with ultra-violet shows a black deposit around
the Aristarchus crater which is not found in ordinary photographs.
Photomicrography in ultra-violet light enables evidence to be obtained of the
structure of objects whose details cannot otherwise be seen.
The resolving power of a microscope objective, that is, the property of
showing fine detail, varies with the aperture and the wavelength. If o is the
smallest distance between two points which can be seen and separated, we
have the relation
.\
0=-
2b
where b is the objective aperture given by the formula b = n sin <X, n being
the refractive index of the medium in which the objective is working and <X is
the angle between the optical axis and the extreme ray passing through the
objective.
To increase the resolving power the aperture can be made very large, or
the shortest possible wavelength can be used. As there is a limit to the aper-
ture, the second solution must be adopted. Ultra-violet light is used, as near
monochromatic as possible.
The objective is of fused quartz and is corrected for spherical aberration.
The slides are of quartz. The immersion liquid must be transparent to the
radiation used-e.g. water+glycerin. With the naked eye, a fluorescent
image is used.
The light source may be a mercury lamp whose light is filtered as has been
shown already, or a spark in air or better, in water. Instead of filtering, the
radiations can be separated with a special spectrograph.
In addition to a characteristic differentiation of the object details by their
opacity differences, there is therefore an increase in the resolving power of
the apparatus. But there is also an increase in the resolving power of the
emulsion due to the limitation of penetration of the rays into the layer when
there is less diffusion. Between 436 and 365 mp, there is a difference in re-
solving power of 1·5 to 2.<2 > The measurements can be made with a resolving
power meter like Burmistrov's<3 > with an achromatic quartz-fluorite objective,
a wet collodion graticule on quartz and a filtered mercury arc. The appli-
cations of the process are in fact very numerous in all branches of science and
industry especially in anatomy, biology, botany, textiles and metallography.
1. Lee and Weissler: J.O.S.A., 1953, 512.

2. Breido: Zh. tekhn. Fiziki, 1952, 508-514.
3. Sci. Ind. Phot., 8(2), 204.
Chapter XXIII
X-RAY AND CHARGED PARTICLE

PHOTOGRAPHY
ACTION OF X-RAYS ON PHOTOGRAPHIC EMULSIONS
369. X-ray sources

X-rays are produced by bombardment of an anticathode in a vacuum with a
high-speed electron stream.
A practical X-ray source consists of a bulb which is evacuated to a high
vacuum, inside which are heated a tungsten filament to emit electrons, kept
at a negative potential (cathode), a positive electrode (anode), and between the
two, a metallic obstacle or anticathode. The speed of the electrons emitted by
the filament is higher as the voltage between the latter and the anode is in-
creased.
The electrons directed towards the anode are intercepted by the anti-
cathode. They strike the metallic atoms of the latter violently, and the result-
ing disturbance produces an emission of electromagnetic waves called X-rays.
Positive particles of matter are simultaneously produced, and are directed to-
wards the cathode.
X-rays are of the same nature as light waves, but have a much higher
frequency. Their wavelengths vary from 12 A for 'soft' rays, to 0·05 A for
the 'hard' rays. Beyond this are they rays of radium with a wavelength 100
times smaller.
The nature of the X-ray beam emitted by a tube is dependent on the metal
of the anticathode: each electronic shell of an atom (see para. 840) produces an
identical emission of characteristic .\ (indicated by the letters K, L, M, etc.).
In other words, each element, due to its differently constituted electron system
has its particular X -ray spectrum. The rays are therefore divided according to
the atomic number of the element, the square root of the frequency being a
function of these atomic numbers, of the form: v = A(1r - B)2 •
To obtain the X-ray spectral images, that is, to analyse them, diffraction
gratings with very fine spacing made of natural crystals are used.
370. Photographic action of X-rays

X-rays, which are much more energetic than light rays, have a powerful
action on photographic layers when absorbed by them. (1)
399
. liberated Ag
If rp indicates t h e rat1o , the following yields are
quanta absorbed
obtained: <2 >
A (A) 4,356 4,047 3,658 1·54 1·09 0·63 0-24
rp 0-96 0-92 0-93 148 210 363 920
violet ultra-violet Hard X-rays
A single X-ray quantum will make a silver bromide grain developable. It
follows that sensitivity specks do not take part in latent image formation, and
that desensitizers (towards visible radiations) are inactive relative to very
short wavelengths.
The radiation is more effective as the wavelength is shorter: thus a
quantum of 0-06 A makes 10 silver bromide grains developable, whilst a
1·3 A quantum will only put one grain in this state. <3 > 10 8 quanta per cm2
of 1·3 A radiations are needed to produce a density of 1·5.
The reciprocity law is directly applicable to X-rays, because of the indepen-
dence of these radiations towards the centres of attraction of the sensitive
crystals. It is the same with the intermittency effect whose influence is nil.
Unlike visible radiation, the effect of X-rays on a photographic layer is to
first produce an internal latent image before producing an external (surface)
latent image. The characteristic curve is only a straight line at high densities.
The X-ray latent image can be destroyed by low intensity visible radiation:
this phenomenon is known as the Villard effect.
Influence of wavelength. The minimum wavelength of the radiation dimini-
shes, as we know, as the voltage applied to the tube is increased.
E.M.F. (kV) 0·08 1 12 120 220
A (A) 140 12 1 0·1 0·05
This is given by the formula A0 = 12,340/Ekv·
Now, silver bromide has two absorption minima, at 0·48 and 0·92 A due
to the K discontinuities of silver and bromine. Because of this it is neces-
sary to work at A = < 0·48 to avoid fluctuations due to wavelength. Radia-
tions with A greater than 0·48 are arrested by silver foil.
X-rays are selectively absorbed by the radiographed object and any varia-
tion in A affects the contrast of the dense parts of the image. The clear areas,
on the other hand, are affected by penumbra variations.
The emission spectrum of the tube has a continuous background, with
bands characteristic of the anticathode metal, generally copper (E = 26-40kV)
or tungsten (200-250 kV). The intensity of the spectrum is proportional to
the atomic number Z of the metal and to the square of the voltage.
X-rays are stopped by lead. On the contrary, they readily pass through
the metals with low atomic numbers, particularly beryllium, which at a thick-
ness of O·Smm transmits 56% of 2·5 A radiation; aluminium only transmits
27% for a thickness of 0·025 mm.
Part of the radiation absorbed by an obstacle is re-emitted as secondary
radiation, of longer wavelength, which is generally undesirable. The
secondary radiation of an aluminium filter is, however, less troublesome; it is
readily absorbed by black paper.
Granularity increases as the wavelength decreases, but below 0-12 A the
variations are small. <4 > At high powers there is a diffusion effect of photo-
electrons around the initial grain.
X-ray sensitometry. A rotating lead disc is used with cut-out sectors,
giving, for example, 5 exposure times per revolution, the shortest being 1/ 10th
sec. The test plate is positioned 30-50 em from the exit opening of the tube.
The results obtained are not always comparable as the coefficient of efficiency
of the emitting tube varies with the time (overheating, release of occluded
gas etc.) Furthermore, there is no simple relationship between the ionisation
energy and the effective photographic energy due to variations in the spectral
composition, the energy of a quantum being inversely proportional to the
wavelength.
A commoncriterion of sensitivity is often given by the abscissa value corres-
ponding to a density of 0-05 above fog.
With a 200 kV tube, the emission is filtered by a steel plate 19 mm thick.
Distance from exit: 90 em. Exposures from 5 seconds to 20 minutes.
Contrast. This depends on the tube voltage and on the development time.
The contrast decreases with the voltage and naturally increases with the
development time. To reduce contrast, expose more and develop less.
Metallic screens. These are thin metal foils stuck to card. They are used
in industrial radiography. The most common metal is lead with 6% anti-
mony, but gold, platinum and bismuth are also effective. Their action is due
to emission of electrons. There must be perfect contact between screen and
film. Intensification: 3. Application to microanalysis.
Antidiffusion grids. A grid of thin layers of lead absorbs the diffused rays
(as well as a fraction of the direct rays), and in this way increases contrast.
Antidiffusion grids are used in medical radiography at high voltages (150 kV)
to reduce the exposure time to a third. <6 >
371. X-ray sensitive layers

It has already been stated that the quantum efficiency of the photochemical
action of X-rays on silver gelatinobromide is very high, always on condition
that these rays are absorbed by the sensitive crystals. Now the majority of the
rays pass through the photographic layer and produce no effect. Only
a small fraction of the incident radiation is absorbed ( 1%) to lead to the formation
of development centres. This is explained by the fact that the image is formed
in the interior of the grains.
The absorption yield can be increased by using an emulsion very rich in
silver bromide and coating a thick layer of it. As the thickness of the layer
prevents convenient development and fixation, it is preferable to coat the
base on both sides with a normal thickness.
The resulting improvement is not great. To increase the action of the
X-rays, the following expedient is used: each emulsion layer is supercoated
with a fluorescent layer. <7 > Excitation of this layer results in the emission of
visible light-blue or violet-which affects the silver salt normally.
The fluorescent substance can be placed under the emulsion layer in the
form of a finely divided white pigment, as with Kryptoscreen radiographic
paper.
The intensifying screen reduces the image sharpness, but considerably
increases the sensitivity.
Emulsion preparation. Radiographic emulsions must be sufficiently con-
trasty, completely fog-free and made of hardened gelatin. They must be
developable in urgent cases, at any temperature. The silver content of a
double coated radiographic emulsion without screen can reach 3·6 g per
sq. ft. A sensitive layer for screen radiography contains up to 1·2 g of silver
per sq. ft. An ordinary negative film contains only 0·65 g of silver.
Radiographic emulsions have a high iodide content. They have little
gelatin. The grain is quite coarse and has a maximum of 3 p,. The thickness
of each coating is about 25-30 p,; it is reduced by half for emulsions used
with a screen (that is, relatively insensitive to X-rays but very sensitive to
ordinary light).
Some photographic emulsions studied by Sauvenier< 8 > gave the following
characteristics by exposure to X-rays:
The contrast drops with precipitation time up to 25 seconds then increases
to 2 minutes precipitation. The differences are small if ripening is curtailed.
The contrast drops with the ripening time (50%).
The sensitivity increases with the precipitation time and with the ripening
time (with exceptions).
Digestion (chemical ripening) time generally has little effect on X-ray
emulsions. Only the weak surface image, which can form, is intensified by
high voltage radiation. <9 >
Emulsions precipitated in the presence of 0·04 mol. per cent (relative to
AgBr) of a lead salt are 50-100 % more sensitive to X-rays. This phenomenon,
noted by Schwartz in 1926 for thallium, was verified for lead by Mueller in
1935. <10> An excess of lead results in desensitisation.
Gold thiocyanate as potassium aurothiocyanate increases the sensitivity of
X-ray emulsions. This sensitivity is further increased by incorporating a lead
halide during precipitation. The increase is SX for 1·07 A radiation and
lOX for 0·011 A.
Lead ions assist the formation of vacant silver ion sites<11 > and of the com-
plex system (Pb++ Ag0 ) which serves as an internal trap, whilst the aurous
ion adsorbed on the surface serves as a surface trap.
'Screenless' formula (after F .I.A.T. Final Report, No. 355).<1 2 >
A (Water 300 cc
T: 45-50 ° C~ Potassium bromide 100 g
l Gelatin 12 g
(Water 500 cc
~ Silver nitrate 100 g
lAmmonia Q.S.
c Gelatin 25 g
D Gelatin 30 g
Pour half of A into B in one minute. After 15 minutes, add the remainder of B in
15 minutes. Add C. After the gelatin has dissolved, cool, set, wash and digest at 50°C.
For coating: with D add glyoxal, chrome alum and saponin.
'Screen' formula
A
50°C
II Water
Potassium bromide
Potassium iodide
480 cc
150 g
1·5 g
l Gelatin 30 g
B !Water 900 cc
27°C ~ Silver nitrate 150 g
l Ammonia 25% Q.S.
c Gelatin 150 g
D Gelatin 120 g
Pour 400 cc of B into A in one minute. Ripen 7 minutes at 50°C and add the
remainder of B in 7 minutes, ripen for 15 minutes more and add C. After the gelatin
has melted, cool, set, wash and melt at 52°C. Add D and digest for 60-90 minutes.
To perfect a radiographic emulsion, the various factors which can modify the
characteristics must be varied successively : choice of gelatin, AgBr/gelatin ratio,
iodide content, precipitation rate, ripening time. Washing can be replaced by sodium
sulphate precipitation.
The slow, relatively fine-grained 'screenless' emulsions are generally more contrasty
than the fast coarse-grain ones. The characteristic curves of the slow emulsions have a
toe extending to D 1·7 instead of 1·1 for the fast emulsions. The characteristics of an
X-ray emulsion depend not only on the nature of the emulsion, but on its thickness,
that is, the amount of silver per unit surface area. Rapid films are rich in silver. A
dental X-ray film must be adequately exposed in one second at 55 kV and 8 rnA.
The properties of emulsions for use with fluorescent screens are similar to those for
ordinary photography.
Development. A developer for X-ray films must be very active, but with a
high bromide content to give high contrast without fog. Examples:
Typical Ilford
formula ID-19
Water to 1000 cc 1000 cc
Metol 5g Z-Z5 g
Sodium sulphite anh. 60 g 72-5 g
Hydroquinone 7-5 g 8·75 g
Sodium carbonate anh. 4Zg 50 g
Potassium bromide 4·5 g 4g
An increase in hydroquinone at the expense of the metol gives high con-

trast but lower sensitivity.
With ID 19, the development times at various temperatures are 16° C
(61° F): 6-8 minutes. zoo C (68° F): 4-5 minutes. Z4°C (75° F): Z! to
3}- minutes. For dental films the time is 5-8 minutes at zoo C and 4-10
minutes depending on type for industrial films.
372. Fluorescent intensifying screens

Fluorescent screens permit a considerable reduction in exposure. They
improve contrast but reduce resolving power. This becomes lower as intensi-
fication is greater.
Fluorescent screens are usually used in pairs: a thin front layer and a thicker
rear one. There are three main types: calcium tungstate screens, zinc sul-
phide screens and lead and barium sulphate screens.
Grain size has very little effect on image sharpness, for the grains are
divided into clumps, and it is the size and topography of these clumps which
determines the sharpness. Their size varies from 20 to 100 11-· <13 >
Calcium tungstate Ca W0 4 screens exist in various types depending on the size of the
crystals (2-20 !-') and the layer thickness. The brightness of a tungstate screen in-
creases with the energy of the radiation, that is at short wavelengths. In fact, the losses
are very great below 80 kV.< 14 l
Zinc sulphide screens. Zinc sulphide, in 10-15 !-' crystals, is activated by traces of
silver or cadmium sulphide. Traces of nickel prevent fluorescence. The crystals are
large as grinding reduces their fluorescent power. The zinc sulphide screens are
brighter than the tungstate ones when .\ < 0·11 A which corresponds to a voltage
lower than 70 kV.< 15 > Their efficiency, unlike the tungstate screens, does not vary
with the penetrating power. They are known by the name 'Fluorazure'.
Lead and barium sulphate screens of Renwick and Tasker. The substance is precipi-
tated in the active state. Optimum content 5 or 20% PbS0 4 • The grains are about 1 1-'·
These screens are mainly used for industrial radiography, and for high-voltage medical
work. Dampness can result in parasitic fluorescence.
Emission wavelengths. Tungstate, 350-560 ml-'; zinc sulphide, 390-550 mf'; lead
sulphate, 300-450 mf'.
Intensifying factor. Tungstate, 10-30 at 40-90 kV; zinc sulphide, 40 at 40-90 kV.
At 200 kV the intensifying factor for tungstate screens passes to 400.
Contrast. Without screen, 2·1; tungstate, 3 ·1; sulphide, 3 ·2; sulphate, 2·7.
The second (rear) screen always has double the amount of fluorescent substance of
the front screen.
Other intensifying screens: with zinc, or zinc+ beryllium silicate, borate or german-
ate.
373. Copies of radiographs

Radiographs have a large density range, often greater than 3, which cannot
be reproduced by photographic papers which at best only give a density of
1·8 (chloride papers).
To retain local contrast whilst reducing the general contrast, it is necessary
to utilize masks. Yule<17 > has disclosed the use of unsharp masks for this
purpose.
The working method is as follows: <18 >
(a) First print a mask of the clear areas on process film and under-develop
it so that the original densities of 0·1 and 0·7 are reproduced by densities of
0·7 and 0·1. By registering the original with this mask, a uniform density of
0-8 should be obtained.
(b) The highlight mask obtained in this way is mounted 12 mm from the
original using a piece of plate glass, and registering the two. The image
faces of the two films are outermost, and with the original against opal glass,
place an unexposed film against the mask. Expose and develop moderately
to produce the unsharp mask.
(c) Print a negative of the original + unsharp mask onto film.
(d) Print a positive of the negative (c) on paper.
Copies of medical radiographs by solarization on X-ray film with a single
layer with a supplementary exposure (30-60 seconds in ordinary light) and
development in the presence of an antifoggant. <19
374. Applications
Medical radiography by very penetrating X-rays. The voltage used for
medical radiography is generally between 40 and 90 kV. More penetrating
radiation emitted at 150 kV enables the dose received to be reduced as
well as the exposure time, at the same time as ensuring better quality
images.
Radiocinematography without a screen can be carried out at 10 f.p.s. With
a fluorescent screen 50 f.p.s. can be reached easily.
Polychromatic transposition. Donovan <21 > has proposed making three radio-
graphic negatives using three radiations of different penetrating power,
obtained respectively at 45 kV for soft tissues, 90 kV for bones and an inter-
mediate voltage. Each negative is differently colour developed: magenta,
cyan and yellow. By superimposing the three, a colour transposition of the
radiograph is obtained which can differentiate certain particular elements.
A transposition in only two colours can also be used.
Industrial radiography. Radiography of thick steel objects requires high
voltage generators-ZOO to 2,000 kV. An antimony-lead screen (6% Sb)
must be used to absorb the less penetrating radiation. The thickness of this
screen varies from 2·5 to 5% of the thickness of the steel object.
For industrial radiography with a 22 MeV Betatron see Miller and
Steeley. <22 >
Radiomicrography is primarily used for biological work. The micro-
radiographic technique, conceived in 1913 by Gaby was perfected by Dauvil-
lier, Lamarque, then Barclay. It needs point opening generator tubes.
Mitchell <23 > used a tube for diffraction taking 5-10 rnA at 5-20 kV with a glu-
cinium opening. A molybdenum anticathode enabled a very narrow wave-
band to be obtained. The sensitive layer is a Lippman plate twice coated, at
40 em from the exit. Another apparatus described by Legrand and Salmon <24 >
uses K ex radiation from chromium of >. 2·28 A. In this case the sensitive
plate is 5 em from the tube exit. Exposure time: one minute. A small exit
with a 1 mm2 focal patch is made by Machlett, but Ely<25 > has disclosed a
system with a rotating anode giving a focal patch of only 0·3 mm2• We would
finally mention a 4-mirror X-ray microscope made by Kirkpatrick and
Pattee, based on the reflecting power of glass and metals for X-rays at a narrow
angle of incidence: this system enables abberations to be reduced, and reaches
a high separating power. (26)
375. Gamma radiography

Gamma rays, emitted by radium, affect photographic films in the same way
as X-rays. The resulting images, however, lack sharpness, contrast is often low
and exposures are too long. The radium is mounted in a copper capsule 4 mm
thick. The sensitive material is placed between the lead foils which serve as
intensifying screens. The rear screen is 0· 75 mm thick, whilst the thickness
of the front one depends on the thickness of the steel to be photographed: <27 >
for 12·7 mm steel the screen is 0-75 mm and for 76 mm of steel, 0·45 mm.
Radon is more effective than radium. Radon is an inert gas resulting from
the disintegration of radium. It emits high intensity y rays. Their lower
penetration increases contrast. On fine grain emulsions it is possible to obtain
images of better quality than those from 200 kV X-rays. <28 >
Use of radioactive isotopes can advantageously replace radium and even
X-rays for radiography. The principal ones are lanthanum 140, cobalt 60,
tantalum 182, iridium 192, cesium 137 and thalium 170. Application in in-
dustrial radiography: lanthanum, <29 > tantalum, cobalt<30 > and cesium <31 > for
steel; iridium for light alloys. <32 > The emission of thalium is comparable in
action with 80 kV X-rays. <33 >
The life of these elements is often short. Their half-life periods are:
iridium 74 days, tantalum 97 days, thalium 129 days, cobalt 5·3 years,
cesium 37 years (radium 1,580 years).
376. Contamination of emulsion packages by atmospheric radio-

active substances
Some accidental fogging of X-rays film has been due to the radioactivity of
the card used for packing. The latter appears to have been made radioactive
by contamination of the water or straw used in its manufacture by atomic
experiments.
The contamination can take place over great distances, as it has been
possible to detect radioactive matter (emitting electrons or ,8-particles) in
the atmosphere of the Paris area, and particularly in rain water. <34 >
To detect and measure the radioactivity of cardboard it is necessary to
work with about a dozen kilos. The ash is taken up in hydrochloric acid at
70° C: the radioactive matter is present in the filtrate. It is precipitated with
barium sulphate. <35 > The elements of the radium and uranium group emit-
ting ,8-particles can be identified in this way: one of them is only emitted by
their disintegration products.
This emission of ,8-particles produces black spots on radiographic emulsions.
Production of ex-particles also occurs, which can affect nuclear emulsions.
PHOTOGRAPHIC ACTION OF ELECTRONS

377. General observations
Electrons affect photographic materials. According to their energy (which
depends on the speed with which they are directed) their action approaches
either that of visible light or of X-rays.
An electron transfers its energy to silver bromide more easily as its energy
is reduced. The ratio between the number of grains developed and the aver-
age number of electrons received, is a function of this energy expressed in
keV. <36 > An emulsion will therefore be less sensitive to high energy electrons
(emitted at very high voltage). The result of this is that ionization is greatest
towards the end of the trajectory of each electron, and that the grains at the
beginning of the path acquire only a sub-image. <37 > However, even though
it loses only a fraction of its energy (about 25 keV) an electron can make
several grains in its path developable although a quantum of light can only
liberate a single electron.
The highly penetrating electrons diffuse laterally which reduces the resolv-
ing power (2 f.L at 10 kV and 17 f.L at 50 kV).
When emitted at a very low voltage, 5 V for example, electrons have no
effective action on gelatin emulsions, they will affect silver bromide free from
protective colloid. Meier has recorded them on Schumann plates (used for
ultra-violet photography). Above 50 V gelatin plates begin to be affected.
At low voltages the photographic action of electrons follows the sensito-
metric laws of visible light. Below several kilovolts the results obtained are
similar to those given by X-rays. Some electron microscopes work at 220-
300 kV but from 20 kV the impact produces a flourescent emission. In this
case a filter of aluminium foil 1 f.L thick is used 15 em from the sensitive
surface, placed inside a Faraday cylinder. A thin aluminium deposit, or
even cellophane, can also be used as intensifying screens at high velocities
(factor 1·5).
The images produced by electrons can be made visible immediately with
fluorescent screens. This occurs on oscilloscope and radar screens. It is often
convenient to photograph these fluorescent screens. The best screens for
photographic reproduction are zinc sulphide ones (blue fluorescence) and
zinc and cadmium sulphide (yellow-green fluorescence) activated by silver.
For the shortest exposures the wavelength of the emission maximum of the
screen should correspond to the sensitivity maximum of the emulsion.
Kopp and Mollenstedt's electron micrographic technique <39 > uses an inter-
mediate fluorescent screen. This consists of a layer of zinc oxide obtained by
vacuum evaporation.
378. Electron emulsions

Emulsions for electron work should be rich in silver bromide. For this, Von
Ardenne disclosed Schumann type UV plates, others used process plates.
The sensitivity increases as the grain becomes coarser, for to become develop-
able, the large grains need less ionization than small ones. On the other hand,
the resolving power drops with layer thickness, so it is necessary to limit this,
even though a thick layer records the trajectories more completely.
The contrast should not be too high except for slightly absorbent samples,
otherwise very hard images are obtained.
Koseki, Karigome and Tajima studied the behaviour of a neutral iodo-
bromide emulsion. <40 > They found an increase in sensitivity with chemical
ripening. The contrast increases with the silver concentration at high voltages
(40 kV) whilst it drops at low voltages (20 kV) at the same time as sensitivity.
The specific sensitivity of the grains towards electrons emitted below 80 kV
was increased by Berriman by colour sensitiz ing, although there is no direct
relationship between optical sensitization and the action of electrons: the
effect is undoubtedly due to a modification of the surface condition of the
grains. The increase in sensitivity enables the grain size to be reduced to
0·2 p. (NT 2a plates). Development 30-40 minutes in D 19 developer.
379. Autoradiography
Autoradiography is the recording of the electron rays from a histological
section impregnated with a differentially absorbed radioactive isotope. This
technique was used in 1924 by Lacassagne and Lattes. In 1947, Pelc had the
idea of stripping the dry emulsion from its support and applying it to the speci-
men after damping with water. Such an emulsion must be rich in silver, and
have very fine grain, but must be coated in a thin layer of 4-12 p. on an under-
lying gelatin layer of 10 p., which is attached to the glass with a hydrophobic
substratum. The section is placed on a microscope slide coated with hardened
gelatin, then the whole is immersed in water. A small strip of emulsion is
floated face down over the specimen and slide. After 3 minutes the latter is
raised and together with the film is drained and dried. <41 l
For standardization, emulsions for autoradiography are 'exposed' to
gelatin coated plates containing a radioactive element (iodine 131, phosphorus
32 or sulphur 35) acting as a source of radiation. The resolving power is
determined using grids activated with iodine 131, obtained by iodizing a
photographic image. <42 l The power of the action of these plates is expressed
in microcuries. !43)
Development: in a low-alkali developer to avoid diffusion of the dyes in
the specimen. In addition it is necessary to check that these dyes do not
desensitize the emulsion.
The number of electrons emitted by the radioactive isotope, whatever it is,
determines the density, which should be at least about 0·5.
Ageno< 44 l has suggested placing a fluorescent film between the emulsion
and the radioactive specimen to amplify the effect: the fluorescent substance
may be tetraphenylbutadiene (D x 2), zinc sulphide (D x 3) or calcium
tungstate (D x 6).
A uranium intensified photographic image can give a copy after several
months contact with a sensitive layer. Rosenblum obtained a better result
in only 30 minutes by incorporating traces of plutonium nitrate in the
intensifier. <45 l
CHARGED PARTICLES
380. Photographic action or"charged particles

The photographic emulsion is sensitive to the action of charged particles:
light ions such as electrons, protons, deuterons, tritons, helions (1X-rays), or
heavy, like the fission products or uranium in addition to the neutrons and
mesons.
Very diverse sources can be used: protons from a cyclotron, <X-rays
from polonium, neutrons emitted by paraffin surrounding glucinium and
radium.
The charged particles act on photographic emulsions by ionization: the
energy absorbed by the silver bromide is proportional to the ionizing power.
Particles with a single charge have the least ionizing power.
The energy of the ionizing particles is denoted in millions of electron-
volts, whilst that of the visible photons by only 2 to 3 electron-volts. The
probability P that a silver bromide grain will become developable is given by
the equation< 46 >
P = c{1 - exp [- b (dE/dR)ll2]}
in which E is the energy in MeV, R the length of the track in f.L, and band c
are parameters. These last are the same for various particles but change with
the emulsion.
When a particle strikes a sensitive layer it activates the movements of the
constituent atoms, particularly C, N and 0 (perhaps producing transitory
substructures). In imparting some of its energy to the emulsion, the
particle liberates a certain number of electrons whose velocity is a function
of its own, and which act on the silver bromide crystals. Some electrons
are raised to the conduction band due to the collisions produced in the
crystals. The primary effect of the charged particle lasts less than 10-13
seconds.
381. Nuclear emulsions

Emulsions for the recording of charged particles, called nuclear emulsions,
have a very high concentration of silver bromide (80%), fine grain (0·1 to
0·5 f.L), and are coated in very thick layers-50, 100, 200,400, 700, 1,200 and
even 2,000 microns.
Ordinary emulsions, such as diapositive ones, are but slightly sensitive to
moderate energy protons, but they can be used, should the occasion arise,
for the study of high energy protons and for mesons.
To prepare a nuclear emulsion, concentrated reagents must be used which
are poured simultaneously, and very slowly into a gelatin solution which
dilutes the liquid streams sufficiently for the grain to be very fine. Further-
more, to avoid any ripening, no excess of soluble bromide is added, and pre-
cipitation is carried out at a relatively low temperature in the presence of an
inactive gelatin.
Many writers have worked out nuclear emulsion formulas. The prepara-
tion of the principle ones is given below, but it should not be forgotten that a
formula which will succeed for one person can give deceptive results to
another. The nature of the gelatin, the personal stirring and a host of other
uncontrollable factors intervene.
Demer'sformulas. The first 'double-jet' formula gives a concentrated emulsion with

a grain size of 1 f'· Prepare :
Gelatin 6% 75 cc
Silver nitrate 60 % 30 cc
Potassium bromide 42% 30 ·5 cc
(equivalent solution).
The nitrate and bromide solutions are poured slowly and simultaneously into the
gelatin solutions, with vigorous agitation, over a period of 30 minutes at 40°C. The
bromide solution should be 0 ·5 to 1 cc ahead of the nitrate solution. The emulsion is
then set, washed, remelted and coated. It is insensitive to ordinary light. Twenty-five
cc of the water in the gelatin solution can be replaced by 25 cc alcohol after the gelatin
has been dissolved.
To improve reproducibility Demers used equipment in which the nitrate and brom-
ide we:re introduced by two syringes, or, preferably, two stainless steel pumps for
nylon extrusion.< 47 l The piston determining the flow of bromide can be adjusted with
a rack and pinion.
Formula 2:
A. Solution containing 600 g AgNO 3 per 1,000 cc.
B. Solution containing 420 g KBr per 1,000 cc.
C. Solution of 15 g gelatin in 167 cc water with 83 cc alcohol. Temperature:
40-50 °C.
After adding 1 ·3 cc of B to C, add 100 cc of A and 100 cc of B simultaneously in
3 minutes. The initial stirring speed of 240 r .p .m . is increased to 550 r .p.m. Set at
0--2°C, wash for one hour at this temperature, and melt for coating. Sensitize before
use by bathing in 6% triethanolamine for one minute, or better, add 12 ·5 cc tri-
ethanolamine to 1,000 cc emulsion.
Formula 3. Prepare the following solutions:<• 8 l
A. 600 g AgNO 3 per litre (D = 1 ·482) .
B. 420 g KBr per litre (D = 1 ·228).
C. 225 g gelatin in 1,500 cc water, and add 500 cc 90% alcohol.
Precipitation temperature: 48 °C.
One cc of bromide solution is first added to the gelatin solution. A pump must add
1,911 cc of A and another, simultaneously, 1,950 cc B. The excess ofB is kept constant
at 2%. The flow, first slow, is speeded up and the jets drop below the liquid level. If
drops of A and B reach the stirrer, a spontaneously developable precipitate of silver
bromide is formed.
The emulsion is cooled in water at 12-15 °C, then set in a refrigerator at 0-5°C,
shredded and washed for 2--4 hours below 5 °C. Before coating, digest at 50°C and add
precisely 40 ·5 cc triethanolamine. Finally 1·5 g thymol dissolved in 300 cc alcohol.
Thick emulsion layers must be dried very slowly to avoid cracking (2 days for 300 f').
Grain diameter 0 ·08 f'· After development, 0·1 to 0·2 f' in the weak tracks and up to
0 ·4 f' in the dense ones.
Halg and Jenny formulas:< 49 l
A
J Distilled water 70 cc
\..Gelatin 6·5 g
B J Distilled water
Potassium bromide
I Cadmium chloride cryst. 10%
23 cc
14 g
5 cc
lPotassium iodide 10% 2 cc
f
c \.. Distilled water 30 cc
Silver nitrate 18 g
Temperature 50°C.
Pour B and C simultaneously into A taking 28 minutes for B and 27 minutes for C
with constant stirring. Ripen 4S minutes at S0°C. Set, wash 16 hours then digest at
3S°C. Make up to 1SO cc and add 9 cc of the solution: distilled water 78 cc, chrome
alum 2 g, 96% alcohol 60 cc, 10% potassium bromide 0·7S cc, glycerin 42 cc. Also
add S cc of 0 ·2% wetting agent and finally a sensitizing dye like acridine orange (1 cc
of 0·2% solution). Coat 1S-30 cc of emulsion per 9 x 12 em plate. Dry at 34°C. Layer
thickness: S0-1 00 p..
Alternative formula( 60 l for better recording of oc-particles. Select a gelatin rich in
retarders and sensitizers.
(Distilled water 60 cc
A ~ Gelatin 3 ·6 g
l Nitrobenziminazole 0 ·2% 1 cc
B J Distilled water
Potassium bromide
I Potassium iodide
30 cc
14·8 g
0·6 g
l Cadmium bromide (hydrated) 0·7 g
c Jl. Distilled water

Silver nitrate
30 cc
20 g
Temperature: 37°C.
Add three drops of B to A, then simultaneously B and C at the rate of two drops
per second, dropping to one drop every three seconds. Total time 30 minutes. Agi-
tation is increased towards the end. Add 6 cc of 0 ·91 ammonia, wait S minutes (which
trebles the speed), then neutralize with 4·S g citric acid. Add 1 g gelatin, allow 12
minutes to dissolve, then set. Wash 1S hours. Melt at 28°C, make up to 200 cc and
add 2 % alum, 2 cc; glycerin diluted with 2 volumes water 6 cc and S cc of a 0 ·04%
alcoholic solution of the 'Ciba' sensitizing dye with the formula
For a 400 p. coating, SO cc of emulsion is used on a S x 8 em plate. Set one hour.

Dry two days. AgBr concentration: 84% . Grain diameter: O·S p..
Markockiformula:( >I)
A J Distilled water 100 cc
60°C l. Gelatin 8g
B J Distilled water to
Potassium bromide
20°C I Potassium iodide
SO cc
19 g
0·4 g
l Cadmium nitrate cryst. 1g
C J Distilled water SO cc
20°C l_Silver nitrate 22 ·S g
Add S cc of B to A, then S cc C, and continue alternately. Ripen SO minutes at
60°C, set, wash 8 hours, melt and add: distilled waterS cc, alcohol S cc, 2% alum
2 cc, 1% potassium bromide 1 cc.
A comparative study of the various formulas has been made by Ctier and Simon. ( 5 2 l
Sensitizers. Some dyes sensitize nuclear emulsions. These are: erythrosin,

eosine, rose Bengal, methyl violet, acridine orange and more complex ones
of the type given above. Sensitization to protons by Pinak.ryptol yellow has
been contested by several workers.
Triethanolamine increases sensitivity slightly. Diphenylamine has a
similar action, particularly towards a-particles. Such sensitizers generally
contain NH 2 or OH groups. Jenny has tried many compounds including
dehydrothiotoluidine-sulphonic acid and pyrrol derivatives. The auxo-
chromic groups which cede electrons are the most effective.
Weak latent images from protons can be latensified by immersing for
1-5 minutes in 0·01% hydrogen peroxide (Demers).
Borate emulsions. The boron nucleus is readily disintegrated by a slow
neutron with the emission of an a-particle (whose track in an emulsion is 7 t-t)·
Impregnation of an emulsion with a borate therefore sensitizes to neutrons.
Lithium borate is preferably used. This is prepared <53 > by neutralizing 225 g
boric acid dissolved in 700 cc water with 51 g of lithium carbonate. The
carbon dioxide is expelled by boiling. The solution is filtered and made up
to a litre giving a 15% solution. It contains 39 mg of boron and 10 mg
lithium per cc. 3% glycerin and 0·004% of a wetting agent are added, and
8 cc of solution per dm 2 is applied to the emulsion. After standing for 16
hours in a damp atmosphere the plates are drained and dried.
Commercial nuclear plates are generally for one or several particle types.
They differ between themselves by the emulsion type, the grain size, the
sensitivity or the thickness. They may be impregnated with various salts:
borates, glucinium, bismuth, or uranyl salts.
The most sensitive plates are used to record proton and meson tracks,
those with medium sensitivity for a-particles, which are readily distinguished
from the finer proton tracks. The slow plates enable the heavy fission particles
to be studied.
Each emulsion has a safety limit for the registration of various particles.
For example, for the NT2a plate these limits are: <54 > electrons 50 kV, protons
100 MeV, deutons 200 MeV, a:> 400 MeV, mesons 10 MeV.
Emulsions without support. Nuclear emulsions 150-300 f1- thick can be
supplied without supports, enabling a large number to be stacked for record-
ing cosmic rays. <55 > For example, 50-600 f1- layers separated by silk paper
were exposed to these radiations at an altitude of 10,000 M. <56 > Registration
marks are made with X-rays. Then each layer is applied to a subbed plate
after immersion in glycerin and water. To avoid frilling the substratum can
be made up of a first layer of sodium silicate (3% solution) which is dried,
followed by 5% alum-hardened gelatin, which is not dried before the damp
emulsion is applied.
382. Development of nuclear emulsions

Exposed nuclear emulsions must be developed as soon as possible because of
latent image regression. The fading is greatly increased by heat: 5 hours at
50° C will destroy the image. It is even more pronounced as the grain is
finer, when the plate is old and when the particles have a low velocity. Acid
pH and moisture favour fading. <58 >
The latent image regression is due to recombination of the silver nuclei,
which are internal, with bromine after ejection of electrons. This electron
ejection is partly due to aerial oxidation in the presence of moisture, and
partly to thermal agitation. (59>
Fading of tracks is avoided at low temperatures, by keeping in an atmos-
sphere of nitrogen or by impregnation, before exposure, with sodium nitrate,
(5 minutes in a 10% solution). <60 >
The first developers used for nuclear emulsions were M.Q. ones, with a
high sulphite content to develop the internal image: metol 2 g, anhydrous
sulphite 75 g, hydroquinone 8 g, anhydrous sodium carbonate 85 g, potas-
sium bromide 5 g, water to 1000 cc or D.19 containing 2, 100, 9, 50 and 5 g
of the same compounds.
The use of very thick layers requires a considerable modification of the
development technique, started by Dilworth, Occhialini and Payne, by im-
mersing the plate in cold developer, and allowing the temperature to rise
slowly. <GOb>
Amidol development (61) (62)

Water to 1000 cc 1000 cc
Sodium sulphite anh. 18 g 7·5 g
Ami dol 4·5 g 3g
Sodium bisulphite lye 14 cc
Boric acid 35 g
The exposed plate is immersed in distilled water at soc for 2 hours, then
for 2 hours in the developer at soc with frequent agitation. <63 > It is then
drained and warmed up to 21-33°C. Mter a suitable time, which may be up
to 50 minutes, the temperature is again reduced to 5°C in 10 minutes. The
plate is immersed in a stop bath of 0·5 % acetic acid, fixed in 40% hypo
containing 0· 7% ammonium chloride and washed at 5°C. A little colloidal
silver may be formed. This is removed with 0-08% ferricyanide followed by
rapid fixing. A final clearing bath of 3% ammonium acetate, 1% citric acid
and 1% thiourea followed by washing is also recommended together with
impregnation with a plasticizer such as hexylene glycol, carbowax or Ansco
Flexoglass. <64 > The sequence of operations for a 600 f:1- layer in bath 61 can
be summed up as follows: impregnation with water at 5°C-150 minutes,
impregnation with developer at 5°C- 150 minutes, 'dry' development at
23°C- 180 minutes, cooling to 9°C - 5 minutes, stop bath-150 minutes,
fixing at 5°C- 75 minutes, washing at 5°C-30 hours, clearing at 5°C-24
hours, plasticizing at 5°C-1 hour, drying at 21 °C-5 days.
Metal developers. Some workers prefer metol developers to amidol ones,
for example: (A) water to 1000 cc, metol 3 g, anhydrous sulphite 12·5 g;
(B) water to 1000 cc, anhydrous sodium carbonate 50 g, bicarbonate 50 g.
Mix equal volumes of A and B, cool to zoe and immerse the plate for 1-10
hours according to thickness. Re-heat to 21 °C in 10 minutes and keep at
this temperature for 30 minutes or more.
Metol can be used with borax;< 65 > (A) water to 1000 cc, metol 3 g, anhy-
drous sulphite 12·S g; (B) water to 1000 cc, borax 40 g. Mix equal parts of
A and B. For a 200 p, layer immerse the plate in the developer < soc for
120- 1SO minutes. Allow it to warm to 19°C in 1S minutes, then immerse in
another portion of developer at 19° C, and leave for 60 minutes. Rinse and
place in a 0-S% acetic acid stop bath for 7S minutes at 19° C. Rinse and fix
in a hardening fixer for 26 hours, then in 3 non-hardening baths for 26, 36
and 40 hours respectively. Wash 72 hours.
Caustic developers. Demers disclosed the use of D8 (para 63) diluted with
an equal volume of water, <66 > then a chlorhydroquinone developer. Water
to 1000 cc, anhydrous sulphite 30 g, pure chlorhydroquinone 4S g, caustic
potash 32-S g and potassium bromide 8 g. Just before use dilute with 6
parts of water. Development time 7! hours at 0·2° C for an emulsion 300 p,
thick. Stop 1S minutes, fix 2-S hours.
Fixing of nuclear emulsions is generally carried out in 40 % hypo. It is
extremely slow: 3 weeks for a 1,200 p, layer.< 67 > Slow rocking of the fixing
dish reduces the time to half. By using a sintered glass support, the fixer can
have access to both sides of the emulsion (Occhialini and Rechenmann).
Ammonium thiosulphate at socan only be used for layers less than 600 p,
as it reduces the developed image.
To reduce distortion it is best to replace the fixer progressively with sodium
sulphate, which is then diluted.
Background fog, which often appears on the plates can be eliminated by
Libermann and Barschall's method: the unexposed plate is immersed in a
developer for a longer time than normal, washed, then treated in O·S %
sulphuric acid and 0-07 % permanganate for 30 minutes. The plate is
then washed, cleared in 10% bisulphite, re-washed and dried. It can then
be used to record the fission of uranium 23S, for example, by exposure to
neutrons.
Another method is to apply the Herschel effect< 6 7 h> using a SOO watt infra-
red lamp with a Wratten 88 filter.
Parasite tracks due to cosmic rays. These can be removed by a method
disclosed by Weiner and Yagoda, and used by Albouy, in which the plates
are placed in a damp atmosphere for several hours. <68 > Mitilsch, Matiasek
and K arlik< 6 9 > have stated that the action of the water is actually due to
the chlorine which it contains: with water containing 12 mg chlorine per litre,
removal is achieved in its vapour after S hours at 60° C.
383. Measurement and differentiation of nuclear tracks

Each particle results in the appearance, in the developed emulsion, of a
track made of a certain number of grains, the number being greater as the
particle velocity is lower. By dividing each track into sections of a few p,,
the silver grains can be counted. If the grains cannot be enumerated then all
sections of the trace separated by a break are counted, and similarly, when
the emulsion is thick, only the breaks are seen. Sometimes the aggregated
grains can be separated by swelling the gelatin. <70 >
An accurate microscope enables measurements to be made ± 111-, on
condition that humidity variations in the ambient air are avoided, for be-
tween 55 % and 80% the thickness can increase 25 % . <71l Mechanical
instruments have been invented for the examination of the plates; <72 > some
of them include a photomultiplier tube. <73 l In this way, after measuring the
number, the course and the diffusion, the velocity, mass and charge of the
particles can be evaluated. <7 4 l
Differentiation. The latent tracks of particles with different ionizing power
are more or less readily developed, enabling them to be separated by varying
the pH of the developer. Stevens<75 l used a bisulphite-amidol solution with
a mixture of two buffer solutions of di- and tri-sodium phosphate and sul-
phite. The most alkaline developer only develops the tracks of the least
ionizing particles, whereas the most acid solution only develops the fission
tracks. A plate impregnated with 2% chromic acid before exposure, dried
and impregnated with thorium acetate, gives, under the action of neutrons,
only the fission tracks, by preventing the formation of proton tracks.
The proton tracks are finer than the oc-particle tracks: a plate impregnated
with thorium nitrate and kept wet for 50 minutes gives, after washing and
development, a large number of oc-tracks which are chemically intensified
(Powel, Occhialini, Livesey and Chilton).
Uranyl ions prevent neutron tracks from forming, which enables plates to
be bombarded by these particles in the presence of a uranyl salt, or a uranate
in dilute acetic solution.
With 1-4% of uranyl ions, the proton paths disappear and those of
X-rays are weakened (broken). The tracks of fission particles are still quite
sharp.
Oxidizing agents like chromic acid, by dissolving the surface and sub-
surface image, remove oc-particle tracks.
Finally, the penetrating power of each group of particles can be measured
by interposition of aluminium foil in steps.
Cosmic rays are made up of a mixture of y-rays, mesons, electrons, positrons
and protons of high energy, which act on the emulsion by liberating electrons.
In 24 hours a surface 1 cm2 is traversed by about 840 cosmic particles at sea
level. <76 l An X-ray emulsion has its fog increased by 0·05 in a year. A nuclear
plate exposed for several days on a mountain top leaves tracks longer than
10 mm and stars with 12-15 points. Impregnated with borate, it is suitable
for the recording of slow mesions, which themselves bring about the disinte-
gration of atomic nuclei. Electron plates are readily affected by cosmic rays.
The very high energy particles disintegrate the silver and bromine nuclei in
the emulsion, producing patterns. <77 l
Blackening laws. Kinoshito has established the following relation for oc-
particles and a single layer material:
D = Dm(l- e-CN)
where N is the number of IX- particles per unit area of the plate during time t,
and C is a probability constant.
In the case of thick emulsions, C decreases at high densities, and in some
cases, increases to a maximum value, then decreases. Sheppard, Wilkins,
Wightman and Wolfe have suggested the two equations :
D = 1·57DM(l- eGfGM) and G = GM(l- e-kNJGM)
where G is the number of accessible grains in the emulsion and k the average
number of grains per track.
Special techniques. Some studies require the immersion of the emitting
substance in the emulsion. The support generally consists of wires< 78 > or
capillary tubes <79 > buried in the sensitive layer.
Russell effect. Metals with a bare surface can affect photographic layers in
the absence of light. This can take place at short distances even through
paper, cellophane or aluminium. It is practically nil in vacuo or in hydro-
gen, <80 > more intense in oxygen. Zinc, magnesium and cadmium are the most
active metals (24 hours at 0·1 mm). Aluminium, nickel, tin, antimony,
chromium, and magnesium take several days. Copper, tin and mercury-
almost inactive-give active alloys.
The photographic action of metals has been attributed to radiation emitted
by the metal under the influence of cosmic rays, with the formation of hydro-
gen peroxide whose effect is added to that of the radiation. Another explana-
tion attributes the generation of particles to the oxidation of the metal only.
A third theory proposes that the photographic effect is solely due to the hydro-
gen peroxide formed during the oxidation of the metal, <81 > with no radiation
intervention. The last explanation seems the most likely.
1. The unit of X-ray energy is the rontgen r, which can produce a charge of one
electrostatic unit in a centimetre cube of air at ooc and 760 mm. The micro-
rontgen is one-millionth of a rontgen.
2. Eggert and Noddack: Zeits. Physik, 1923, 299-314.
3. Hoerlin H.: J.O.S.A. and Sci. et Ind. Phot., 1949, 363.
4. Herz R. H . : Phot. Jl., 1949, 89-96.
5. Saulnier A.: Compt. Rend. Ac. Sc., Paris 1946, 876.
6. Seemann H. E. and Splettstosser H. R.: Radiology, 1954, 575-583.
7. This fluorescent layer can be separate from the photographic film; a coated glass
plate which is placed on the sensitive layer just before exposure.
8. Sauvenier H. : Sci. et Ind. Phot., 1948, 1.
9. Miyauchi A .: Symposium of Phot. Sensitivity, Hakone, 1953; Sci. et Ind. Phot.,
1954, 238.
10. Mueller F. W. H. : R.P.S. Cent. Conf., London 1953. Hoerlin H. and Mueller
F. W . H.: J.O.S.A., 1950, 246-251.
11. Tetlow: Sci. et Ind. Phot., 1949, 375 .
12. August 1945, H.M. Stationery Office, London.
13. Schober H. and Klett C. : Rontgen Blatter, 1953, 214-228.
14. Coltman J. W., etc.: Jl. App. Phys., 1947, 530-544.
15 . Destriau G.: Compt . Rend. Ac. Sc., Paris 1943, 571.
16. Destriau G.: Compt. R end. Ac. Sc., Paris 1943, 571.
17. Yule J. A. C.: Sci. et Ind. Phot., 16,170.
18. Medical Radial. and Phot., 1951, 121-125; Sci. et Ind. Phot., 1952, 195.
19. Illingworth, Bertoluzzi and Pietra: Jl. Radial. Electrol., 1951, 621-624.
20. Wachsmann, Brever and Buckheim: Fortschr. Geb. Rontgenstr., 1952, 147-157.
21. Donovan G. E.: Lancet, 1951,832.
22. Miller N.C. and Steeley J.D.: Non-dest. Testing, Dec. 1953, 35-40.
23. Mitchell G. A.:Jl. Phot. Sci., Aug. 1954,113-118.
24. Legrand C. and Salmon J.: Jl. Rech. C.N.R.S., Paris 1954, 298-304.
25. Ely R. V.:Jl. Phot. Sci., Aug.1954, 119-124.
26. Cosslett V. E.:Jl. Phot. Sci., Aug. 1954,125-130.
27. Johns H. E. and Garrett C.: Canad. Jl. Res., 1948, 292-305.
28. Dawson}. H. T.: Jl. Sci. Instr., July 1946, 138.
29. Tenney G. H.: Non-dest. Testing, Spring 1954, 4-10.
30. Dutli, Tenney and Withrow: Non-dest. Testing, Winter 1949/50, 9-11 and 25.
31. Dutli and Taylor: Non-dest. Testing, April1954, 35-38.
32. Morisson A.: Non-dest. Testing, Summer 1951, 26-28. Wolf R. V. and Wolf
K. P. W.: Non-dest. Testing, Feb. 1954, 26-29.
33. Untermyer S., Spadding F. H., etc.: Nucleonics, 1954, 35.
34. Abribat M. and Pouradier}.: Compt. Rend. Ac. Sc., Paris 1953, 1233.
35. Pouradier, Venet and Chateau: Ass. Tech. Ind. Papet., 1953, No. 2, 34; Sci. et
Ind. Phot., 1953, 277.
36. Okrent D. and Solomov A. K.: Phys. Rev., 1951,826-833.
37. Digby, Firth and Hercock: Jl. Phot. Sci., Dec. 1953, 194-208. Grenishin S . G.:
Zh. Tekhn. Fiziki, Jan. 1952, 33-39; Sci. et Ind. Phot., 1953, 277.
38. Hopkinson R. G.: Phot.Jl., Dec. 1946.
39. Kopp, C. and Mollenstedt G.: Optik, 1947, 283-300; Sci. et Ind. Phot., 1948, 145.
40. Koseki, Karigome and Tajima: Jl. Soc. Sci. Phot. Japan, Nov. 1954, 31-36;
41. Berriman, Herz and Stevens: Brit. Jl. Radial., 1950, 472-477; Sci. et Ind. Phot.,
1950,441.
42. Lumerton L. F. and Harriss E. B.: Jl. Phot. Sci., Aug. 1954, 135-144; see also
43. Curie: Quantity of radioactive isotope subject to 3 ·7 X 1010 disintegrations per
second.
44. Ageno M.: Nuouo Cimiento, 1955, 266.
45. Rosenblum S.: Compt. Rend. Ac. Sc., Paris 1950, 1766.
46. Blau M.: Phys. Rev., 1949, 279-282.
47. Demers P.: Science, 1949, 380; Compt. Rend. Ac. Sc., Paris 1950,616.
48. Demers P.: Compt. Rend. Ac. Sc., Paris 1953, 1228; Canad. Jl. Phys., 1954,
538-554.
49. Halg W. and Jenny L.: Helv. Chim. Acta., 19-4-8, 131-136.
SO. Jenny L.: Bristol Phot. Conj., 1950, 259-264.
51. Markocki W.: Wiadonmosci Chemiczne, 1952, 2-27; Sci. et Ind. Phot., Dec. 1952.
52. Cuer P. and Simon F.: R.P.S. Cent. Conf., London 1953.
53. Kaplan N. and Yagoda H.: Rev. Sc. Instr., 1952, 155-161.
54. Herz R. H.: Phys. Rev., 1949,478-485.
55. Demers P.: Canad. Jl. Res., 1950, 628-655.
56. Powell C. F.: Phil. Mag., 1953, 219.
57. Kayas G.: Jl. Phys., 1953, 621.
58. Faraggi and Albouy: Compt. Rend. Ac. Sc., Paris 1948, 717; 1949, 68.
59. Breiser A.: Phys. Rev., Oct. 1950, 112.
60. Winand L. and Falla L.: Bull. Soc. R. Sci. Liege, 1940, 185.
60b. For the use of D.19 developer see: Blau and Felice: Phys. Rev., 1948, 1198.
Wilson and Vanselow: Phys. Rev., 1949, 1144.
61. Dilworth, Occhialini and Vermaesen: Bristol Phot. Conf., 1950, 297-309.
62. Dainton, Gattiker and Lock: Sci. et Ind. Phot., 1951, 264.
63. Herz H.}.: Jl. Sci. Instr., 1952, 60.
64. Stiller, Shapiro and O'Dell : Rev. Sci. Instr., 1954, 340-348.
65 . Dhit K. R.: Sci. et Ind. Phot., 1954, 1.
66. Demers P.: Sci. et Ind. Phot., 1952, 1.
67. Longchamps}. P. and Braun H.: Jl. Phys., 1954, 139A-144A.
67b. Goldstein A. M. and Sherman C . H .: Rev. Sci. Instr., 1952, 267-271.
68. Albouy G.: Colloque Sci. Phot., Paris 1951, 361.
69. Mitilsch T., Matiasek C. and Karlik B.: Nature, 1955, 35 .
70. Pniewski }. :Acta. Phys. Polon., 1953, 230.
71. McAllister: Proc. Phys. Soc., 1951, 91.
72 . Masket A. V. and Williams L. B.: Rev. Sci. Instr., Feb. 1951, 113.
73. Van Rossum L.: Compt. Rend. Ac. Sc., Paris 1953, 2234.
74. Fowler P. H. and Perkins D. H.: Bristol Phot. Conf., 1950, 340-345. Kayas G.:
Compt. Rend. Ac. Sc., Paris 1954, 2153. Hoans T. F . : Compt. Rend. Ac. Sc.,
Paris 1954, 1790. Mabboux C. and Morellet D.: Nuovo. Cimiento, 1954, 405.
75. Stevens G. W. W.: Sci. et Ind. Phot., 1948, 468; Bristol Phot. Conf., 1950, 310-
316; Sci. et Ind. Phot., 1951, 346.
76. Herz R. H.: Phot.Jl., 1951,134.
77. Nature, 1949, 47 and 82.
78. Silver E. G. and Wamek R. W.: Rev. Sci. Instr., 1954, 1119.
79. Reinhez M. and Vanderhage G . : Nuovo Cimiento, 1954, 243.
80. Reboul J. A. : Jl. Phys., Feb.1940, 57.
81. Roikh I. L.: Dokl. Ak. Nauk. S.S.S.R., 1954, 1117.
Chapter XXIV
PHOTOSENSITIVE SYSTEMS AND

SPECIAL TECHNIQUES
384. Photosensitive systems
The salts of silver are not the only ones which are light sensitive. Those of
various other metals, have, in various degrees, the ability to react under the
action of luminous energy, the phenomenon generally taking place by a redox
effect.
We have already mentioned the preparation of photographic emulsions
using salts of lead and thallium. The mercury complex es comprise another
interesting group. Lead, thallium and the mercury complexes form insolub.e
halides and organic salts : their systems are analogous to those of silver halide
emulsions.
The salts of iron and cobalt on the other hand form soluble photosensitive
systems, even in the absence of protective colloid. Their sensitivity is effective
when they are in the complex state.
There are two other categories of photochemical reaction which we shall
study in later chapters: these are the insolubilization of dichromated colloids
and the photochemical destruction of dyes.
The photosensitive systems apart from the silver salts, the dichromated
colloids and the dyes have not at the moment a great practical importance;
however, their theoretical study is not without a certain interest.
INSOLUBLE SYSTEMS
385. The best known insoluble systems are the silver halide emulsions.
Note first that these can be obtained in the absence of any protective colloid:<1 l
pure silver bromide plates can be obtained by sedimentation on a layer of rub-
ber; in this way phenomena which would be masked by gelatin can be
studied (para 285). We know also that daguerreotypes were plates of polished
silver which were treated with the vapour of iodine, bromine, or chlorine:
the silver halide formed on the surface of the plate was, after exposure, able
to attract mercury vapour in all the exposed areas (amalgam formation).
The action of light on the halogenized plates can be demonstrated by im-
mersing two such plates (chlorine treated for example) in an electrolyte and
joining them with a conducting wire: a current passes through the wire when
one plate is illuminated, leaving the other in darkness.
p 419
386. Mercury salts

Many mercury salts show a definite photosensitivity:<2 >
Mercurous nitrate, HgN0 3 • H 20, which is only soluble in acid solutions
(nitric) is converted to a basic salt after three minutes exposure to diffuse
light. The image cannot be seen; it must be developed in a solution of ferrous
sulphate and tartaric acid which only reduces the basic salt to metallic
mercury. The residual mercurous nitrate is stabilized by conversion to mer-
curous chloride with an alkali chloride solution.
Basic mercurous tartrate is also very sensitive. It can give an image develop-
able in ferrous tartrate as above, or a print-out image. The image is stabilized
by substituting platinum for the mercury, by treating with a solution of
platinic chloride in tartaric acid.
Masic mercurous tartrate is prepared by saturating a solution of tartaric
acid with mercurous carbonate.
Basic mercurous oxalate which is formed when mercurous carbonate is
boiled in a solution of a neutral acetate, gives, like the tartrate, both direct
and developable images. A mercurous oxalate paper requires, for develop-
ment, an exposure of about fifteen minutes. Ferrous tartrate is used for
development and sodium chloride for fixing. The image can also be developed
physically by heating at 100° C: this phenomenon is reversible, the image
returning to its original state after a few days. <2b>
Mercury-ammonium oxalate. This is the most interesting compound of the
series. Mercuric chloride, treated with excess sodium carbonate gives a pre-
cipitate of mercuric carbonate. This is washed and heated with a solution of
ammonium oxalate; by double decomposition this gives mercury ammonium
oxalate.
Mercury ammonium oxalate<3 > can be dispersed in gelatin as an 'emulsion'.
Several seconds exposure in sunlight and development in alkaline sulphite
gives black mercury images. Hypo fixes slowly in concentrated solution,
or thiocyanate can be used.
387. Insoluble lead salts

Besides the lead halides which have already been described, many salts have
been claimed by various experimenters for the preparation of sensitive
materials:
Sheppard and Vanselow< 4 > disclosed organic salts such as the oxalate,
malonate, succinate or thioacetate dispersed in gelatin.
Lead arsenite despersed in gelatin can be developed by heat. <5 > Lead
oxides and sodium arsenite ground together in a mortar give a mixture which
darkens rapidly in light.
Lead xanthogenate gives a latent image which is developable with ferrous
sulphate after treating with silver nitrate (Philips).
Gelatino-lead nitride emulsions have been studied by Moskovitch (Phot.
Abst., Dec. 1940, 215). They are less sensitive than gelatino-silver nitride
ones.
PHOTOSENSITIVE SYSTEMS AND SPECIAL TECHNIQUES 421
Other metals used. Zinc and cadmium sulphides for printing out, in presence
of moisture (Zeits. Phys. Chemie., Jan. 1956, 146-159).
387b. Phosphotungstic acids

Simple and mixed tungstic acids, and most particularly silicotungstic and
phosphotungstic acids are reducible by light. A study of these compounds
by L. Chalkley (J.O.S.A., 1954, 699-702) has shown that the phosphotungstic
acid of the No. 12 series of Keggin (Proc. Roy. Soc., 1934, 144, 75), colourless
and water soluble, changes to phosphotungstous acid, water and spirit soluble.
The reaction favoured by organic substances:
H 3 PW12 0 40 ---* H 4 PW12 0 40
Phosphotungstous acid, which forms the image can reduce iron, silver or
gold salts (silver and gold precipitate). Treated by amines, the two acids
become insoluble but keep their original colours. Phosphotungstic acid can
be combined to the leuco-derivatives of triphenylmethane basic dyestuffs, to
give insoluble and colourless salts. These salts, when exposed to radiations
les~ than 440 mt-t, give the corresponding black phosphotungstites which
are altered by air into coloured phosphotungstates. The remaining leuco-
base must be removed with benzene.
388. Endothermic compounds

Certain endothermic compounds (that is compounds whose formation in-
volves the absorption of heat and which are therefore unstable) can decom-
pose violently, in a very explosive way under the influence of an intense ex-
posure. These photosensitive endothermic compounds have been studied
principally by Eggert, Arens and Berchtold; (Sb> the principal ones are:
nitrogen iodide, silver nitride, the mercury nitrides, lead nitride, silver oxalate,
silver acetylide, silver imide Ag2NH.
Nitrogen iodide can be prepared on paper. It needs an exposure of 18
watt/second (300 watt/second for silver nitride) to give a positive image.
This is stabilized in a solution of silver nitrate. Nitrogen iodide is only sensi-
tive to visible radiations.
SOLUBLE SYSTEMS
389. The most common soluble photosensitive salts are those of iron,
cobalt, manganese, uranium, lead and, of course, silver.
Soluble lead acetate gives homogenoeus layers which are sensitized with
thioacetamide, a compound which readily parts with sulphur. Staib and
Hickman added hexaminocobalt chloride and stabilized with acetic acid. <6 >
The ammonia from the hexamine is liberated by light, and accelerates the
reaction of the lead with the thioacetamide.
Lead acetate only, in gelatin, gives a brown image on exposure to light;
this can be intensified with silver nitrate.
Silver nitrate darkens in light. <7 > Its decomposition is accelerated by organic
compounds capable of accepting the group (NO a)-, or which reduce it (glucose,
tartaric acid etc.). If the reducer is too vigorous there is the risk that the paper
will darken without exposure.
The following mixture can be used:
Silver nitrate 8g
Citric acid 16 g
By exposure to sunlight, brown-violet or red-brown images are obtained
which can be washed and preferably fixed in dilute hypo.
Although the darkening of silver nitrate was known since its discovery by
the Arabs in the eighth century, it was not attributed to light until the begin-
ning of the eighteenth century.
390. Iron salts

The ferric salts, especially the chloride, are sensitive to the action of light.
Ferric chloride is reduced to ferrous chloride and chlorine. The reaction
is reversible and stops at a state of equilibrium
2FeCla ~ 2FeC1 2 + Cl 2
if the chlorine formed is not taken by a halogen acceptor.

Ferric chloride dissolved in a mixture of alcohol and ether is reduced by
blue and ultra-violet radiations. The same thing happens with cupric
chloride. We have already seen, at the beginning of this book, a similar
reaction with mercuric chloride, which is also seen with mercuric iodide in
hypo solution.
391. Iron organic complexes

With organic polybasic acids iron forms complexes of the formula (FeY A naY
in which y is the valency of iron, a the valency of the organic acid and x that
of the resulting complex ion: the relation x = an - y must apply, n being the
number of molecules of acid. For example:
With bivalent oxalic acid COOH -COOH and trivalent ferric iron, the ferri-
oxalate ion is obtained [Fe+++ (C 2 0 4 )-- a]---, which is negative and trivalent,
the three negative valencies being the difference between the three positive
valencies of iron and the six negative valencies of oxalic acid. The ferrous
ion Fe++ gives the ferro-oxalate ion [Fe++ (C 20 4) 2 - - ] - - in the same way.
These groupings have already been considered in connexion with ferrous
oxalate developers and the change from the ferrous to the ferric state by oxida-
tion and vice versa (para 33b ).
The ferrous ion Fe++ on oxidation passes to valency 3 by losing an electron
to give Fe+++. On the contrary, by gaining an electron the ferric ion Fe+++
passes to valency 2 giving Fe++ which automatically brings about a re-
arrangement in the complex structure.
It will be recalled that in the complex ions the simple metallic ion (such as
Fe+++) is disguised although it takes part in oxidation-reduction reactions:
the ordinary analytical reactions do not indicate its presence without previous
decomposition (which may be easy or difficult): thus the ferri-oxalate ion
has not the characteristics of iron.
However, each complex ion dissociates into its constituent elements
following the equilibrium reaction
(MmY+. Ana-)~ mMY+ + nAa-
which is interpreted by the law of mass action by the relation
(M¥+)m X (Aa-)n
----- = k
(MmY+. Ana-)
The smaller the value of k, the more stable the complex: k is the instability
coefficient of the complex ion; it is dependent on the pH.
A large number of metals form complex oxalates in the same way as iron:
chromium, manganese, cobalt, copper platinum, iridium, titanium, vanadium,
uranium, etc. Chromium for example gives the blue chromioxalate with the
formula
Ka[Cr(C204)a]
and another red compound with a slightly different constitution
K[Cr(C204)2]. ZH20
In the same way as oxalic acid, the other organic acids like tartaric acid and
citric acid give complex salts with these metals. A large number of these
oxalic, tartaric and citric compounds, particularly the iron ones, are sensitive
to light.
The most sensitive salts are the oxalates, then the tartrates. The citrates
are the most stable of them.
The sensitivity appears greater if, instead of using the pure salt, a mixture
of ferric chloride and an excess of the corresponding acid is used.
Under the action of light, the ferric ion of the complex group loses a valency
and becomes a ferrous ion: the ferrioxalates, ferritartrate and ferricitrate
became the ferrooxalates, ferrotartrates and ferrocitrates, which are all
reducers.
It becomes evident that if these ferrous compounds are in the presence of
compounds which are reducible, then they reduce the latter and show their
presence. For example, ferric ammonium tartrate (NH4 ) 3 [Fe(C4 H 4 0 6)a]-
prepared by dissolving ferric hydroxide Fe(OH)a in tartaric acid, saturating
with ammonia and evaporating after filtration- is converted, in the solid
state as well as in solution, into ferrous ammonium tartrate which can reduce
silver nitrate and Fehling's solution.
The reducing power of organic ferric and cobaltic salts has been used in
practice in the following systems: iron-silver, iron-mercury, iron-platinum,
iron-gold, iron-ferricyanide, cobalt-ferricyanide, which will be dealt with
briefly. We would finally mention the light sensitivity of iron carbonyl, a

compound of iron and carbon monoxide which provides images which can be
toned.
APPLICATIONS OF ORGANIC COMPLEX SALTS
392. Iron-organic system

This system is used in the ferrogallate process.
A ferric salt, exposed to light under a negative, gives a positive image of
the corresponding ferrous salt. This image is rendered visible by treatment
with gallic acid which combines with the ferrous salt to give a black compound
similar to iron ink.
Ferrogallate paper is preferably prepared with the following mixture:
Ferric sulphate 3g
{Water 40 cc
Tartaric acid 5g
({
( Water 40 cc
\ {Gum arabic 6g
{
t Water 80 cc
Ferric chloride 7·5 cc
The sensitized paper is dried and must be kept away from moisture other-
wise it deteriorates very rapidly.
After exposure, the image is developed in
Gallic acid 0·2% 100 cc
Oxalic acid 0·1% 5 cc
Rinse, fix in 2% hypo and wash.
Kogel <8 > disclosed a paper sensitizing formula using ferric salts in the
presence of (/..-naphthoquinone sulphonic acid and a mordant. The ferrous salt
formed in the photochemical reduction forms a coloured compound with the
naphthoquinone.
Gay used a mixture of ferric salt and starch paste and developed the image
in potassium iodide.
393. Iron-silver system (sepia paper).

A paper sensitized with a solution of ferrioxalate, tartrate or citrate containing
silver nitrate, and exposed to light, gives an image by reduction of the silver
salt, in the presence of moisture, by the process already described. The
excess ferric complex is removed by washing.
The following two formulas can be used on gelatin <9 > or gum coated paper:
Ferric ammonium citrate-green <10 > 80 g 200 g
Silver nitrate 12 g 66 g
Citric acid 15 g 66 g
Water 1000 cc 1000 cc
The silver nitrate is dissolved separately in part of the water.
The image is developed in water, washed, fixed in 2% hypo and again
washed. It can be toned.
Ferric oxalate with silver nitrate in the presence of mercury salt catalysts
has also been used. <11 >
The ferric salt used alone gives a latent image which can be developed in
ammoniacal silver nitrate, then fixed.
The old 'iron paper' was made by sensitizing paper with a mixture such as:
Water 100 cc.
Ferric nitrate 5g
Silver nitrate 5g
Tartaric acid 25 g
394. Iron-mercury system

The reducible substance in this case is a mercurous salt, preferably the
oxalate. The paper is sensitized, for example, with a solution of ferric oxalate
and mercurous oxalate in the presence of gum arabic. In this case, after a long
exposure to light (15-60 mins) insoluble ferrous oxalate is formed which can
only react in a 5% potassium oxalate solution in which it is soluble (forma-
tion of ferro-oxalate). It is therefore better to use simple ferric ferrioxalate
and then develop in water.
The deep brown image, washed with oxalic acid, then with water, can be
fixed in 10% ammonium chloride which converts the residual mercurous
oxalate to mercurous chloride.
395. Iron-platinum system (Platinum process)

The principle of this once widely used system, which has the advantage of
giving permanent prints of a good black colour, is similar to the preceding
ones:
(a) an organic ferric salt (the oxalate) is reduced by exposure to light to
the ferrous salt.
(b) the ferrous salt formed in turn reduces potassium chloroplatinite
K 2 [PtCI4 ] or Pt Cl 2 • 2KC1, which gives metallic platinum by the reaction:
6FeC 20 4 + 3Pt Cl 2 = 3Pt + 2FeCI 3 + 2Fe 2(C 20 4) 3
Ferrous Platinous Platinum Ferric Ferric
oxalate chloride chloride oxalate
The chloroplatinite is used, as platinous chloride is insoluble.

A mixture of chloroplatinite and ferric oxalate, coated on paper and exposed
to light, gives a grey-violet image which must be developed as the ferrous
oxalate produced is insoluble and cannot reduce the chloroplatinite. To dis-
solve the ferrous oxalate it must be converted to a ferro-oxalate by bathing
the exposed paper in a solution of neutral potassium oxalate. By replacing
the ferric oxalate in the sensitizing solution with an alkali ferri-oxalate, the
reducing ferro-oxalate is obtained directly and only water treatment is neces-
sary. The solutions must be slightly acid (by adding an organic acid) to
prevent the formation of basic iron salts which would make the paper yellow.
The sensitizing mixture must contain substantially equal quantities of
chloroplatinite and ferric oxalate.
Operating procedure
Gelatin coated paper is sensitized with the solution
Potassium chloroplatinite 10% 250 cc
Ferric oxalate 30 % 100 cc
Potassium chlorate saturated soln. 100 cc
Oxalic acid 10% 10 cc
For less contrasty images omit the chlorate and increase the ferric solution.
Printing is continued until a light brown image, full of detail is obtained.
It is then developed in:
Water 1000 cc
zoo C Neutral potassium oxalate
( Tartaric acid
350 g
100 g
This solution is suitable for sepia images. For black tones replace it with
Potassium oxalate 70 g
Oxalic acid 3g
Disodium phosphate 10 g
Water 1000 cc
Wash, fix in 1-2% hydrochloric acid, again wash and dry.
For sepia tones replace part of the platinum with iridium and size the paper
with arrowroot.
The platinum process is not used due to the high price of this metal. In
addition, the sensitized paper does not keep well, the reduction of the ferric
salt to the ferrous taking place in the dark with the least trace of moisture.
396. Iron-gold system

Results similar to those of the platinum process are obtained by replacing the
chloroplatinite by sodium chloroaurate (double chloride of sodium and gold)
Na [AuC1 4 ] . 2H 2 0. This is reduced to metallic gold by the photolytic ferrous
salt. The images are always warm toned.
Printing takes much longer than for the platinum process. Tranchant
formula for brown-black tones :
Water 80 cc
{Sodium chloroaurate 10 g
Water 50 g
{Ferric oxalate 50 g
[ Water 50cc
Potassium chlorate 50 g
( Tartaric acid 50 g
Red-violet to red-brown tones are obtained by adding 10-40 cc of a satura•
ted solution of stannous chloride SnCl 2 •
The image which appears by printing is developed in a bath of potassium
oxalate and fixed in hydrochloric acid. If stannous chloride has been used,
it is necessary to wash again and fix a second time in 5% acetic acid.
397. Iron-ferricyanide systems

Ferrous and ferric salts, treated respectively with an alkali cyanide give
precipitates of ferrous and ferric cyanides Fe(CN) 2 and Fe(CNh which re-
dissolve in excess cyanide to give two complexes-the ferrocyanide and
ferricyanide, such as K 4 [Fe(CN) 6 ] and K 3[Fe(CN) 6 ], and in which the
bivalent and trivalent iron exists in the complex ions [Fe(CN) 6 ] - - - - and
[Fe(CN) 6 ] - - -.
The change from one to the other of these complexes is easy to bring about
as we have already explained: the resulting valency of the complex ion is
equal to that of the negative radical (CN) 6 less the valency of the metal ion,
which in this case is 2 for ferrous iron and 3 for ferric iron. This makes the
ferrocyanide ion corresponding to ferrous iron, tetravalent; whilst the ferri-
cyanide ion corresponding to ferric iron is trivalent. When the iron ion Fe++
of the ferro complex changes to valency 3 by losing an electron to form Fe+++
the ferro ion is converted to the trivalent ferri ion
Ferrocyanide io n electron Ferricyanide ion
Conversely, if the ferric ion of the ferricyanide receives an electron, it

passes to the ferrous state which brings about the change of the ferri ion to
ferrocyanide.
The ferrocyanide ion is a reducer and in this capacity becomes oxidized to
ferricyanide. The ferricyanide ion on the other hand is an oxidizing agent
which during oxidation becomes reduced to the ferro state. We know in
fact, that a reducer is a compound capable of giving electrons easily whilst an
oxidizing agent is a compound with an affinity for electrons in the same way
that a dehydrating agent is one with an affinity for water.
The ferro and ferricyanide ions give salts, the ferrocyanides and the ferri-
cyanides. The alkali salts are soluble; the others generally insoluble, coloured,
and decomposed by alkalis. Ferrous salts form a bluish-white precipitate
with the ferrocyanides, which is ferrous ferrocyanide; ferric salts give an
intense blue precipitate of ferric ferrocyanide, or Prussian blue
4FeC1 3 + 3K 4 [Fe(CN) 6] = Fe4 [Fe(CN) 6 Ja + 12 KCl

Ferric Potassium Ferric Potassium
chloride ferrocyanide ferro cyanide chloride
Potassium ferricyanide does not precipitate pure ferric salts. With ferrous
salts it gives an insoluble blue ferrous ferricyanide (Turnbull's blue).
At one time potassium ferrocyanide was prepared by heating nitrogenous
organic compounds with potassium carbonate and iron residues, but it is now
p*
prepared from the by-products of coal-gas. Ferricyanide is obtained from

the ferrocyanide by electrolytic or chlorine oxidation.
Potassium ferrocyanide occurs as yellow crystals, containing 3H 20, which
are very soluble in water. The ferricyanide crystallizes in red prisms which
are very soluble in water. Its solutions are unstable to light.
398. Ferroprussiate paper

Aferric salt, exposed to light, is reduced to a ferrous salt. The negative ferrous
image treated with a potassium ferricyanide solution is coloured blue due to
the formation of a precipitate of ferrous ferricyanide (Turnbull's blue). If,
on the contrary it is treated with a solution of potassium ferrocyanide, the
unchanged ferric salt reacts to form a blue precipitate of ferric ferrocyanide
(Prussian blue) whilst the ferrous image produces a bluish-white precipitate
which is superimposed on the other and reduces the positive image (cyanotype
paper).
If a mixture of a ferric salt and potassium ferricyanide were exposed to light
to give a negative blue image of ferrous ferricyanide directly, it would be too
unstable and would react spontaneously. The ferric salt must be stabilized
by incorporating it as an organic complex: ferric ammonium or potassium
citrate or oxalate. In fact, the sensitizing mixture is made up of a ferric
organic complex and potassium ferricyanide which is coated on paper.
The ferrioxalate for example, is reduced by light to the ferrooxalate, losing
a molecule of oxalic acid which is decomposed to CO 2 •
[Fe(COO. COO)a] --- + e- --* [Fe(COO. C00) 2] - - + 2C0 2
Ferrioxalate ion F errooxalate ion
But the ferrooxalate is a reducer: it can locally convert the ferricyanide to

ferrocyanide and precipitate with the latter as ferric ferrocyanide (Prussian
blue). This is not all: potassium ferricyanide is itself light sensitive. Exposed
to light it is reduced to ferrocyanide which reacts with ferric salts to form
ferric ferrocyanide.
The photosensitivity of the ferrioxalates is related to their photoconduc-
tivity. Suzuki has worked on this. {llb)
The importance of the stability of the ferrous complex is in each case made
evident by the fact that the ferrotartrate produced by photochemical decom-
position of ferric potassium tartrate does not, contrary to published infor-
mation, give a blue precipitate, but simply a soluble violet complex. This .
is because the ferrotartrate is much more stable than the ferrooxalate or the
ferrocitrate.
399. Sensitizing formulas

Paper sensitized with ferric potassium oxalate is faster than the ferricitrate
paper but it does not keep as long. In each case gelatin sized paper must be
completely free from reducing substances which would quickly fog the sensi-
tive layer. It must be thoroughly dried at a temperature below 55°C and
keeps for 3 months.
Ferric potassium oxalate formulas< 12 l
Author's formula
Ferric potassium oxalate 12% 240 cc
AOxalic acid 20% so cc
pH - 1 { ( Ammonium tartrate 35 %. 30 cc
B Potassium ferricyanide 10% 70 cc
Tomoda's formula (12bJ
Water 80-260 cc
Ferric ammonium oxalate 12 g
Oxalic acid 0·5 g
Neutral potassium oxalate 0·75 g
Ammonium dichromate 0·2 g
Dextrin 0·75 g
Pot~ssium ferricyanide 2g
Ferric ammonium citrate formulas:
pH < 2·3 {Ferric ammonium citrate (green) 25 % 100 cc
Potassium ferricyanide 12% 100 cc
Ferric ammonium citrate (Brown) 20% 100 cc
pH > 2·3 Potassium ferricyanide 16% 100 cc
( Ammonia 1-4 cc
The addition of small quantities of dichromate increases the contrast.
Triethanolamine ( 1 cc) increases the sensitivity and reduces the contrast.
Prints are fixed merely by washing which dissolves the excess sensitizer.
The final wash is acidified slightly with hydrochloric acid, to prevent decom-
position of the ferroprussiate into iron oxide.
Modification of ferroprussiate colours. The material is first treated in weak
alkali such as 1% sodium carbonate, which decomposes the ferric ferro-
cyanide to ferric hydroxide and soluble alkali ferrocyanide: the blue colour
is destroyed leaving only a faint pink image.
The decolorized paper is washed and treated in a solution of tanin <13 l
which reacts with the iron hydrooxide to give a highly coloured image, similar
to ordinary ink. The colour of the image depends on the variety of tanin:
with gallic acid, or gall-nut tanin, the image is black.
with oak tanin the image is violet.
with catechu tanin the image is brown. A little boric acid is added to
this bath.
400. Other photosensitive systems

Systems similar to the iron-ferricyanide ones can be obtained, on one hand
by replacing the potassium ferricyanide by potassium cobalticyanide
K 3[Co(CN) 6 ], and on the other, by replacing the ferri-organic complex by an
analogous cobalt or copper compound: thus one can use cobaltic ammonium
oxalate (NH 3)a. [Co(C 20 4) 3 ] obtained by electrolytic oxidation of cobaltic
oxalate in ammonia, or cupric ammonium (or potassium) citrate. Photo-

chemically produced cobalt ferrocyanide, and complexes of Cr and Mn have
been used in ceramics to obtain glazed colours.
Manganic salts like the ferric, cobaltic and cupric ones are reduced by
light to the lower valency manganous ones. Most of the inorganic man-
ganic salts are unstable, and it is therefore better to use the organic salts:
oxalate, tartrate, citrate, lactate, etc. They are obtained by treating potassium
permanganate with an excess of organic acid. Manganic tartrate, coated on
gelatinated paper, becomes discoloured by light, giving a positive image
which can oxidize o-toluidine hydrochloride: the image becomes blue-green.
401. Photoceramics
It is possible to impregnate porous pottery with a light sensitive mixture.
Mter exposure under a negative, it is sufficient to wash and fire . The com-
pound which forms the image is destroyed by the heat but leaves in its place
a metallic oxide. It is then glazed.
The ferroprussiate solution can be used, but the iron oxide produced is
soluble in porcelain glazing compounds. Jorgensen (lab l recommends the
following formula:
Potassium cobalticyanide 3g
Hot water 8 cc
Glycerin lg
after cooling to below 40°C add:
Ammonium colbaltioxalate 6g
Ferric citrate 0·5 g
Citric acid 0·3 g
Use immediately.
Using cobalt, chromium and manganese, multicolour effects can be
obtained.
402. Preparation of ferric oxalates and citrates

1. Ferric oxalate Fe 2 (C 20 4) 3 • Ferric hydroxide, precipitated from a solution of the
chloride or sulphate with ammonia, is washed and then dissolved in a hot solution of
oxalic acid (the hydroxide being in excess). The solution of ferric oxalate is filtered
and concentrated by evaporation to a syrupy liquid which precipitates oily droplets
on the addition of alcohol. Solid ferric oxalate is obtained as brown granules. Its solu-
tions must be kept in the dark.
2. Ferric potassium oxalate K 3 [Fe(C 20 4) 3] . A mixture of concentrated solutions of
ferric chloride and neutral potassium oxalate, when slowly cooled, deposits green
crystals of ferric potassium oxalate which can be washed and recrystallized. It is also
obtained by mixing ferric and potassium oxalates.
3. Normal ferric citrate. This compound does not seem to exist_<l•l
4. Ferric ammonium citrates. Citric acid,
COOH-CH 2-C(OH) . CH • . COOH
I
COOH
treated with ferric hydrate forms a complex cation:
[Fe 3 (C 8H 50 7) ,(OH) ,(H ,0) ,] +
which can give salts like the chloroplatinate or the citrate. The latter is obtained in
the presence of excess acid and crystallizes with 18H 20.
[Fes(C.H 5 0 7),(0H).(H .O).] s CaHs0 7 • 18H.O
To prepare it, freshly precipitated ferric hydroxide is dissolved in 3N citric acid
at 50°C, then evaporated at this temperature until a surface skin forms. The citrate
is precipitated with 95 % alcohol, dried at 50°C and redissolved in water and crystal-
lized at a moderate temperature. Red-brown scales are obtained.
5. Ammonia converts this complex citrate to brown ferric ammonium citrate which
is believed to be the citrate of the complex ion:
[Fe(C 6H 4 • FeO . 0 7) 2 (NH 4) 2 (H 2 0) 2]+
A solution of the complex ferric citrate is mixed with a slight excess of ammonia
and concentrated on the water bath below 50°C, when it deposits a brown ferric
ammonium citrate with 15H 2 0. This compound is heated for an hour at 90-100°C to
give another brown citrate containing 6H 20 as deep red scales. By further prolonged
heating the remaining 6H 2 0 are removed. The complex ion begins to decompose at
l20°C.
The brown ferric citrates appear to form colloidal solutions in water, which do not
exist until the pH is 2·3.
Commercially, the brown ferric citrate is prepared by treating 41 parts of ferric
hydroxide (containing 11 % Fe 2 0 3) with 10 parts of citric acid and 6 parts of ammonia
(20% NH 3) .
6. Green iron citrates. The addition of citric acid or an alkali citrate to brown ferric
citrates converts them to green ferric citrates, such as green ferric ammonium citrate
from which the brown salt can be obtained again by treating with ammonia.
The green salts come from ferricitric acid with the formula H 3 [Fe 2 (C 6H 5 0 7) s
which is prepared by dissolving ferric hydroxide in cold citric acid and evaporating
at a low temperature until yellow-brown scales are obtained. By replacing the 3H of
the acid with ammonia or potash in the appropriate quantities the green ferric ammon-
ium (or potassium) citrates are obtained. The same result is obtained by mixing the
theoretical quantities of citric acid, ferric hydroxide and ammonia or potash. The
solution is then concentrated on the water-bath at a low temperature until the deli-
quescent green scales are produced. A mixture of ferric chloride and alkali citrate
deposits the same compound after evaporation. The green citrates always have an
acid reaction. ·
Commercially ·this material is prepared from 25 parts of ferric hydroxide (11%
Fe 2 0 3), 10 parts of citric acid and 5 parts of ammonia (20% NH 3).
The green citrate contains 14-15 % Fe whilst the brown citrate contains 21·7-
22 ·4 % .
SPECIAL TECHNIQUES
403. Sensitive layers adsorbed on glass
Grebenesikow has shown that water attacks glass to form superficially a very
thin film of colloidal silica having a very high absorptive power. Burmistrow
(Phot. Jour., April 1936) made use of this property to prepare glass plates
with a sensitized surface, without using organic colloids. The photosensitive
compound can be silver nitrate, silver nitrate precipitated with an already
adsorbed halide, or colloidal silver chlorinated with CuC1 2 after adsorption.
Physical development in a solution of silver nitrate and hydroquinone is used.

1% ferric chloride attacks the glass to produce a silica layer ten times as
thick as that from pure water. However, the thickness varies with the glass
and the action is increased by heating.
A glass plate can be suitably sensitized by successive treatments in nitric
acid, tincture of iodine and dilute ammonia followed by bathing in 10%
silver nitrate, washing and drying. It gives an image with 30 minutes exposure
at 3 feet from a 15A arc, then 15 minutes physical development before fixing
in 25 % hypo.
The layer thickness varies from 5 to 20 mJL. Resolving power - 2·5 x
that of a Lippmann emulsion separating two lines 0·25 JL apart.
Application-graticule preparation. The surface must be protected with a
varnish or well hardened by heating to 350°C and polishing.
It should be added that the success of the method given above is very
critical: the image is often too weak or too fragile. Leiztner reports having had
only failures, C15 l but Loening and Farnell, Cl 5 b ) obtained satisfactory results
with precipitated silica.
404. Sensitized anodized aluminium

Aluminium, covered with a thin superficial layer of alumina by electro-
lytic oxidation (anodizing), can hold in its pores without a protective colloid,
various photosensitive mixtures: precipitated silver salts, soluble silver and
iron salts, ferricyanide etc., which have already been dealt with earlier. C16 l
The alumina layer, exposed under a negative, or by optical projection can
then be developed and fixed without difficulty depending on the nature of
the sensitizer used. The resulting image, silver or otherwise, is stable and
resistant to shock.
The images can be coloured by dyeing the oxide layer using the usual
resist methods.
Sheet or foil aluminium without an oxide layer can be coated with a ferric
sensitizer in a resin f17 l dissolved in an organic solvent and printed.
For anodizing, Kirilov and Kheinman<18 l used the following technique:
aluminium sheets containing at least 99·4% AI are polished, and degreased
in a hydrocarbon containing alcohol, then in a solution containing disodium
orthophosphate 46 g, caustic soda 8 g and soldium silicate 28 g per litre for
2- 3 minutes at 50°-60°C. They are then oxidized by electrolysis in 10%
sulphuric acid at 30°C. The aluminium plates form the anode ( +) whilst
the cathode ( - ) is lead. Current density 1·5 Afdm2 • The voltage (6--18 V)
is adjusted so that the alumina layer formed is suitable after 30--40 minutes.
If the acid concentration is increased or the temperature is raised, the oxide
is attacked and the layer is thinner. A greater dilution makes the oxide
brittle and porous. The thickness increases noticeably with the duration of
electrolysis; if, for example, it is 15 JL after 45 minutes it will be 25 JL at 60
minutes.
The aluminium can also be oxidized in oxalic or chromic acid. In the
latter case, the solution generally contains 50--100 g per litre chromic acid, 0·1 g
sodium chloride and 0·4 g sulphuric acid. Voltage 10-40 V, temperature
30-40°C, current density 0·1S-0·6 Ajdm2 (at 40 V), time about 30 minutes
At higher temperatures the oxide film becomes powdery.
Sensitizing. The oxidized aluminium plate is sensitized by immersing
alternately in solutions of 10% potassium bromide, then silver nitrate.
Kirilov and Kheinman did this 39 times before filling up 1/3 of the volume
of the alumina pores. Fog due to spontaneously formed silver specks is over-
come by treating for S minutes in a solution containing SO g of ferricyanide
and SO g potassium bromide per litre. After washing, drying and exposing
for 1-2 seconds at 20 em from a SOO W lamp, development is carried out in a
solution containing S g amidol, 2S g anhydrous sulphite, 1-10 g of potassium
bromide and 4 g 40% lactic acid (anti-oxidant). The image is yellow-brown-
or sometimes black. Owing to the low contrast, intensification is necessary.
Diazo sensitization can be used but reproducible results are difficult to
obtain.
Sensitization in the oxide pores requires care. Furthermore it gives plates
which do not keep well and are slow.
Pure aluminium plates, suitably oxidized can have a mirror surface. They
can then receive a layer of photographic emulsion---:.:hloride or bromide.
These plates, when treated like photographic papers give beautiful images
on a metallic base which look like Daguerrotypes. Another available type has
a white under-layer for the production of dials or industrial plates.
An unhardened emulsion freshly coated on anodized aluminium, then
developed in a tanning developer can be used for photomechanical work to
repel greasy inks after hot water development. Printing must be prolonged
to expose the gelatin in contact with the metal.
Another technique used by the writer is to coat the sensitizing emulsion
on dyed anodized aluminium (black, blue or other colour). After develop-
ment, the image, is attacked by a hydrogen peroxide bath (see para 596)
which leaves a cavity where the silver was. The washed print is then im-
mersed for a few seconds in a bleaching solution-hypochlorite for example-
which destroys the dye staining the base wherever there is a cavity, in propor-
tion to the thickness of the residual gelatin.
Among the dyes which can dye anodized aluminium are: nigrosine (J and
JB), Niagara direct blue, Pontamine fast turquoise blue 8 GL, naphthol
green B, naphthalene green V, quinoline yellow, polar yellow, azorubine,
neolan red, etc. Dyeing time 30-60 minutes in a 1-S g per litre solution con-
taining 1 cc acetic acid, and at a temperature of 80-92°C. Finishing in a
mordant of S g per litre nickel acetate at 9S°C is often carried out for 1S
minutes. Immersion in boiling water for 30 minutes improves the fastness
of the dye.
405. Photographic tracing on sheet metal

Tracings on sheet metal for fabrication or for the preparation of templets are
frequently made photographically (by contact or projection), after sensitiza-
tion of the previously varnished sheet. The sensitive layer can be either an
emulsion applied with a spray-gun or an emulsion already coated on a tem-

porary paper support and transferred to the sheet.
(a) Coating method. The washed and dried metal is coated with a resin
layer rich in plasticizer, then two other layers with decreasing plasticizer
content but containing a white pigment. The photographic emulsion, in small
pieces kept at 7°C (45°F) or in powder (which is dissolved in water), is heated
to 37°C (99°F) and sprayed with compressed air. After drying at 35 °C (95°F),
the sensitized sheets are exposed under negatives and developed in large
tanks.
(b) Transfer process. The metal surface is first covered with two layers of
white varnish. The varnish is dried and made tacky by swelling, then the
paper carrying the emulsion is applied with a roller or with an automatic
machine. The support is stripped off dry and the image is printed onto the
transferred emulsion and then developed in an M.Q. developer.
The transfer paper can be prepared by coating a layer of beeswax (dis-
solved in trichlorethylene) on the base, then an emulsion and finally a nitro-
cullulose layer containing a rubber ester (as an adhesive layer). High contrast
process emulsions are used (B.P. 559,843).
(c) Copying. The original drawing must be dimensionally stable. It can be
drawn in reverse on plate glass or vinyl sheet covered with a white opaque
varnish. To avoid drawing in reverse, it can be reflex printed from an original,
the right way round on a sheet of white aluminium. The copy is made on
plate glass for large sizes or on gummed paper.
It is possible to make the copy with a phosphorescent layer which is ex-
cited by X-rays before being placed in contact with the drawing and the
~ensitive material. The degreased aluminium plate is coated successively
with a clear lacquer, a black lacquer, then a phosphorescent paint on which
the drawing is made after matting with special glasspaper. Excitation is by
X-rays from a 200-kV 20 rnA source for two minutes. The phosphorescent
image is then placed in contact with the sensitized surface for 3 minutes, or
reflex printed.
406. Reversal transfer

Reversal transfer is a process in which silver bromide diffuses from a photo-
graphic layer into another gelatin layer containing development centres of
colloidal silver, in the presence of a solvent. If the solvent contains a develop-
ing agent a new image is formed at the same time in the transfer layer by
physical development brought about by the development centres. (lBb>
The emulsion layer and the transfer layer can be superimposed on the
·same base or can be on two separate sheets. In the former case (Gevaert
Diaversal), the base is first coated with a layer of hardened gelatin containing
a suspension of colloidal silver, then a coating of fast unhardened emulsion.
Mter exposure and negative development, the paper, still containing the
developer, is immersed without agitation in a solvent bath. The residual silver
bromide is dissolved and diffuses into the lower layer, where it is reduced
imagewise. The upper emulsion layer is then removed in hot water. A brown-
ish image remains. Resolving power, 10 lines per mm. (A. Rott's process,
F.P. 873,507 and Add. cert. 53,404, 53,502, 53,513, 53,515.)
Agfa Copyrapid paper is the result of E. Weyde's work carried out at the
same time as Rott's, and consists of a system using two separate papers, one
negative carrying a silver bromide emulsion, and the other a positive paper
carrying a gelatin layer containing development centres.
As the negative is exposed via the base for reflex copying, the emulsion
must be very contrasty, with a very short toe to the characteristic curve.
Orthochromatic chloride reflex papers are very suitable for reversal transfer
although they contain more silver halide than necessary. The Copyrapid
negative emulsion is very thin (which makes it cheaper).
The paper is exposed in a reflex printer emulsion towards the document.
It is then placed face to face with the positive paper and inserted into a
developing machine. This consists, in principle, of two rollers which press
the moistened sheets together. Development is complete in a few seconds
with a concentrated caustic soda developer containing a solvent for silver
halides. When transfer is complete, it is only necessary to part the papers if
only limited keeping is necessary. Otherwise, it is better to wash before
drying. The image is yellow-brown on a white ground when washed, or
yellow when not washed.
The development centres of the positive transfer paper are generally of
colloidal silver, silver sulphide, gold, etc. A faint image can be obtained
merely by using fixed out, washed and dried photographic paper.
407. Polaroid-Land process

This process for obtaining a negative and a positive simultaneously is used
mainly in the U.S.A. to obtain a 'picture in a minute'. It is controversial
whether Rott or the Agfa laboratories have priority over Land for the image
transfer idea. Whatever it is, the Land process deserves mention because of
the orginality with which it is applied, and the quality of the results. This is
the principle:
A paper support, which is the final positive, is unrolled in the camera and
brought into contact by two rollers with the exposed negative material. A
viscous developer contained in a pod attached to the paper is spread between
the two materials when the pod is burst passing through the rollers. The
resulting sandwich pack is withdrawn from the camera through a slit fitted
with a knife. The two supports must each be opaque. One minute after being
brought into contact the positive is complete.
The viscous developer contains hydroquinone, caustic soda, sodium sul-
phate and hypo, or a developer such as benzylsulphonylhydrazine (Wood-
ward); its viscosity is increased with a soluble cellulose compound. Develop-
ment is very rapid, and at the same time the undeveloped silver bromide is
dissolved by the hypo to diffuse into the positive layer where it is reduced to
form a brown or black positive image.
For the process to be possible, development must be more rapid than the
formation of the transferable complex. Furthermore, it is essential that the
complex is only reduced in contact with the positive material. The positive
negative ratio depends on the ratio of the rates of complex formation and
development. The yield is at an optimum when the two are in equilibrium.
Furthermore for the precipitation of the silver from the argentothiosul-
phate to take place before the solution is saturated with silver, metallic, or
preferably sulphide or selenide ions must be present, producing develop-
ment centres of silver sulphide or selenide. The concentration of these ions
must not exceed 10- 10 or the positive will have low density and contrast, and
will not be black. The difficulty is overcome by dispersing a slightly soluble
sulphide on the surface of the positive material.
The positive image can be stabilized with a viscous solution containing
acetic acid and a zinc salt: colourless sulphide ions are formed(F.P. 1,105,617).
An antioxidant, such as ascorbic acid+ethyl tartrate is added to the stabilizer.
Obtaining several prints. A print uses only 14% of the silver present in
the layer. If the negative, put in contact with a second positive, is developed
again, there is no image. But A. J. Sievers noted that when the solvent (hypo)
is reduced to an optimum value, three more copies can be obtained. Theo-
retically, the maximum number is seven. <18 cl
408. Xerography
Xerography is the local destruction by light of an electrostatic charge on a
metal plate coated with a semiconductor. The image is made visible with a
powder which is then transferred to paper by electrostatic discharge.
Selenyi disclosed in 1935 <19 l the principle of this method, and the idea was
taken up again by Carlson in 1938. The process acquired by the Haloid
Company was perfected by Schaffert and Oughton at the Battelle Memorial
Institute. <20 >
One starts with an aluminium sheet covered with selenium whose dark
resistance is 1015 Q em and 1010 Q em in the light. The selenium is deposited
by vacuum sublimation. Theoretically it can be replaced by sulphur or anthra-
cene. The plate is charged (or sensitized) by passing, 1 em from its surface, a
stretched metal wire at an E.M.F. of 4000 to 7000 V. The semi-conductor is
charged by the Couronne effect, the metal being earthed. The electrostatic
charge acquired in this way is unchanged for seven hours and then starts to
discharge slowly in the dark.
By exposing to light behind a photographic lens, the selenium becomes con-
ductive where it has been exposed. It locally conducts its superficial charge
to the metal support. The discharge continues slowly after exposure but the
image contrast is not appreciably reduced. The visible radiation can be
replaced by X-rays. In this case the exposure is 1-7 times shorter than with a
fine-grain X-ray film without a screen. Resolving power in visible radiations:
10 lines /mm.
Development. The surface of the plate is covered with a resinous powder
(diam. 0·1-20 f.L) containing crystalline grains about 300 fL diameter. These
PHOTOSENSITIVE SYSTEMS AND SPECIAL TECH N IQUES 437
grains can be of tartaric acid or ammonium chloride, if the plate is positively
charged. The resin is negatively charged by friction. (The resin powder,
however, can be charged by direct electrical means, giving better half tones.)
Thus the negatively charged resinous powder is attracted to the positively
charged image and makes it visible. The exposed plate is placed at the bottom
of a dish containing the powder mixture, and is moved about until a satis-
factory contrast is obtained.
Metcalfe<20 b> develops with a liquid (petrol, turpentine, carbon tetra-
chloride) containing a dispersed pigment. Time: 1 to 10 seconds.
Transfer. This only consists in applying to the image a negatively charged
sheet of paper and pressing the combination between two metal plates and
heating to melt the resin and attach it to its new support.
The selenium-covered plate can be used again after wiping the surface
with powdered sodium chloride.
In this way a photographic print can be obtained two minutes after expo-
sure.
Reversal. When a pigment is blown between the exposed plate and a parallel
electrode charged to 300 V, a reversed image is obtained. (Rayford: Phot.
Engng., 1955, 173- 182.)
408b. E1ectrofax. This process, similar to Xerography, was worked out by
Young and Greig of the R.C.A. Corp.<20c>A layer of zinc oxide ZnO (0·25-
0·35 fL diam), dispersed in a resin, is coated on baryta paper. The sheet is
negatively charged with a high tension charge. When exposed to light,
ZnO becomes a conductor; the charges are dissipated in the exposed
areas. To develop the image, a positively charged pigment is used, which
adheres to the non-exposed regions. Then the resin is softened by heat,
making the pigment stick. Minimum voltage between the exposed and
unexposed areas: 150 V. In practice, the sensitized sheet is charged to
300-600 V, by passing it under a wire at 3-7 kV, the sheet being placed on a
metal plate connected to the earth. Efficient A: 320 to 420 mfL. Zinc oxide
can be rendered colour-sensitive with a dye such as rose Bengal, eosin,
fluorescein, acridine orange, methylene blue. Sensitivity is influenced by
moisture; however, it is sufficient to make photographic enlargements.
408c. Berchtold process. Whilst, in Xerography and Electrofax, the resi-
dual charge of a photoconductor is used, here this is the photoconductor
which emits a current under the action of light. <20d> A selenium or thallium
sulphide photoelectric layer, covered by a transparent electrode, is coated on a
special plate having unidirectional conductivity exclusively perpendicular
to the plane of the plate. This is obtained by sawing a block of parallel
varnished metal wires, cemented together. Under the plate, is placed a sheet
of paper sensitive to electric current, such as diazo paper, the pH of which
can vary by electrolysis (or a system reacting to redox phenomena). The back
of the paper must lay on a counter-electrode made of graphite containing
rubber. Twenty-two volts are applied to the entire block, during exposure
which must be intermittent. Time : 60 sees. with 600 lux.
408d. Thermofax (Minnesota Mnfg. Co.). A translucent sheet of paper is

covered with a substance which blackens when heated, then with a white
pigment, the layers containing a spirit-soluble resin. Under the action of
intense infra-red rays, the sensitive layer darkens locally (blue-black image
on yellow background). Application: document reproduction.
409. Ferrography
Ferrography is the magnetic recording of an image on tape, after analyzing
with a cathode iconoscope of the type used in television cameras, then copying
on a cylindrical steel sleeve. A magnetic powder is sprayed onto the cylinder and
adheres in proportion to the intensity of the field and makes the image
visible; the image can then be transferred onto paper as in xerography. A
print is thus obtained with a 48lines per em pattern in about a minute. For
further details, see the works of Atkinson and Ellis. (21 l
The transcription can also be made direct from the iconoscope to the steel
cylinder or from the magnetic tape onto a machine for printing a half-tone
image point by point.
410. Photosensitive glass

Glass capable of producing an image by exposure to light was perfected by
the Corning Glass Works following the work of Dalton, Stookey and Armi-
stead. Dalton (22 l was the first to notice that copper ruby glasses are more
quickly coloured when exposed to U.V. radiation before firing. He then
disclosed that an image could be formed of metallic particles after exposure
and firing.
The photosensitive glasses must contain a photosensitive metal such as
silver, gold, copper or cerium. After 10 minutes exposure to an arc lamp, the
glass is heated to 650°C to obtain an image through the glass. A glass studied
before 1943(23 > had the composition: Si0 2 - 100; Na 2C0 3 - 37; AlP 3 -
3-3; BaC0 3 - 15; NaN0 3 - 6; cryolite- 10; Ce0 2 - 0 ·05; Au -
0·014; and gave a blue to red image depending on the exposure time, before
firing for 30 minutes at 550°C, depending on whether the coagulation is
superficial or deep in the glass. A point source favours the production of a
deep image. (24 l
The region of spectral sensitivity is between 300 and 370 mEL for copper or
silver glasses. (25 l It is below 254 mEL for gold glasses, but the addition of
cerium raises the limit to 350 mfL.
The glasses must be free from lead, but more than 5% of an alkali oxide is
necessary. Borates and phosphates give spontaneous colouring on firing .
Baryta is beneficial to gold sensitizing. Traces of tin and bismuth increase
sensitivity but reduce contrast. Cerium compounds act by absorbing the
active radiations.
Latent image: this is formed by the electrons given out by the photosensitive
ions which are kept in an active metastable state by the traps made by the
faults in the glass lattice, or by the metallic ions. During firing, the metallic
ions acquire electrons to become atoms, which aggregate to produce metallic
particles. A brief heating destroys the latent image by thermal agitation.
Opal glasses. The metallic silver particles produced by exposure to light
can bring about, during firing, the crystallization of non-metallic particles
which finally give a milky image on a clear ground. Some opalized glasses are
more quickly attacked by hydrofluoric acid than the untreated glass.
Transparent glasses. Transparent glasses with a coloured image can be of
two types: gold glasses giving blue, purple or ruby images and gold+ palla-
dium for sepia images, used mainly in stained glass.
Transferring a silver image to glass. Stookey<26 > disclosed a process for trans-
ferring a photographic image onto glass in which the procedure is as follows:
the silver image in gelatin is applied to the glass surface and covered with a
special paste of ferric sulphate (25 %) and yellow ochre (75 %) in a liquid
binder (oil or water). Drying is followed by baking at 450°C for 30 minutes.
A latent silver image is then formed on the glass surface. To make it visible,
the glass must be heated in a reducing atmosphere (mixture of hydrogen and
nitrogen) for an hour between 450 and 500°C, which transforms the silver
ions to metal. The ferric sulphate oxidizes the silver whilst the ochre prevents
the deformation of the image during the decomposition of the gelatin.
1. Goetz A. and Inn E. C. Y. made a photosensitive system [silver oxide adsorbed

onto zinc oxide or titanium oxide] dispersed in a concentration of 20 mg per
sq. ft. Black to yellowish images are produced depending on the state of sub-
division. (Rev. Mod. Physics., 1948, 131-142.)
2. Namias: Bull. Soc. Fr. Phot., 1895, 117. The photosensitivity of the mercury salts
was studied by Bergmann in 1779.
2b. Van der Meulen and Countryman studied a similar preparation of mercurous
oxalate dispersed in gelatin and developed by heating to 120°C, after exposure.
Fierce heating produces an explosion of the mercurous oxalate. Maximum
sensitivity between 230 and 320 mf.'. (Phot. Eng., 1953, 104-112.)
3. Mercury oxalate can also be converted to an amino complex and introduced into
the gelatin. It is sensitized by metals like silver, gold, thallium, etc. and by eosin.
Images by development or by printing out can be obtained in this way. I.G.F. :
G.P. 470,611 and 619.
4. F .P . 728,099.
5. Reissaus: G.P. 540,888. Weyland Cramer: J.O.S.A., 1949, 889.
6. F .P. 730,043, 730,876.
6b. Arens and Eggert: Sci. Ind. Phot., 2, 381. Eggert J. : Bristol Phot. Conj., 1950,
94-98. Eggert J.: Sci. Ind. Phot., 1953, 377-385. Berchtold]. and Eggert J.:
Naturwiss., 1953, 55. Berchtold J.: Thesis No. 2376, Phot. Inst. ETH, Zurich,
60 pages.
7. Except when it is extremely pure and dry.
8. F.P. 665,491 (1928).
9. F .P. 874,014 (1942).
10. For the preparation of organic ferric salts, see para. 402.
11. G.P. 261,342 (1910), 366,068 (1922).
11b. Suzuki 8.: R.P.S. Phot. Conj., London 1953.
12. For the preparation of organic ferric salts, see para. 402.
12b. Tomoda Y. : Jl. Soc. Phot. Japan, May 1951, 161.
13. The tanins are glucosides, combinations of glucose and gallic acid derivatives.
13b. Jorgensen C. V. : K em. Maanedsblad, 1939, 201; Nordiske Kemikermode, 1939,

254.
14. Belloni: Gaz. Chim. !tal., 50, II, 190 and 210.
15. Phot. Engng., 1950, 7-15.
15b. Phot. Jl., 1952, 187-194.
16. Mason R. B.: U.S.P. 2,115,342 (1932).
17. Philips: F.P. 864,723.
18. Zh. Prikl. Khimii, 1951,4019-4025.
18b. Stevens and Norrish: (Sci. et Ind. Phot., 9(2), 334) had noted, in 1938, that the
images of an emulsion layer can diffuse in a gelatin layer, in close contact. Frln. E .
Weyde made the same observation with a baryta coated paper.
18c. Sievers A. J.: Phot. Sci. and Techn ., May 1955, 75.
19. Selenyi P.: Zeitz. Techn . Phys., 1935, 607.
20. Schaffert R. M. and Oughton C. D.: J.O .S.A., 1948, 991-998. McMaster R. C . :
Non Destr. Testing, 1951, 8-25 .
20b. Metcalfe K. A.: Jl . Sci. lnstrum ., 1955, 74.
20c. Young C. J . and Greig H . G . : R.C.A. Review, 1954, 469-484.
20d. Berchtold J.: Sci. et Ind. Phot., 1955, 465-471.
21. Atkinson R. B. and Ellis S. G.: Jl. Frank. lnst., 1951, 373-381.
22. U.S.P. 2,326,012 and 2,422,472.
23. B.P. 597,089 (1943).
24. Stookey S. D.: P .S.A. Jl., 1948, 399.
25. Stookey S.D.: Ind. and Eng. Chem., 1949, 856-861.
26. Stookey S. D. : Ind. and Eng. Chem., 1954, 174-176.
Chapter XXV
PHOTOGRAPHIC BASE MATERIALS

PHOTOGRAPHIC PAPER
411. Constitution of cellulose

Cellulose is the essential constituent of all vegetable material. It is found in
many varieties, and in various degrees of purity. It is almost pure in cotton,
and in wood is mixed with lignine, proteins, resins, waxes and inorganic
matter.
In practice cellulose is divided into three types, designated by ()(, {3 and y:
()(-cellulose: insoluble in 18% soda, constitutes 98·5-99% of cotton.
{3-cellulose: soluble in 18% soda, but is reprecipitated by adding acid.
y-cellulose: soluble in 18% soda and is not reprecipitated on acidifying.
The {3 andy varieties are termed hemicelluloses. Photographic paper should
contain less than 4% of them.
Cellulose is a derivative of glucose, a pentahydroxyaldehyde, in the form of
its anhydride
CHPH-CHOH-CHOH-CHOH- CHOH-CHO
Glucose
CHPH-CH-CHOH-CHOH-CHOH-CHOH
I 0 I
Glucosic anhydride
Glucosic anhydride, or 1)(-glucopyranone is represented schematically by a

hexagon, one of whose peaks is occupied by an oxygen atom. Two or more
molecules of 1)(-glucopyranone unite in a chain via the oxygen to give a cello-
biose, a cellotriose, cellotetrose, cellohexose, etc.
OH~
H COHO H OH ~OHQ
ORQH + H Fl OH -+ OeO HH
H H H OH + H20
OHH H Q HH
H H 0 H H H
OH H OH OH
0 OH
a-glucopyranone Cellobiose
Cellulose is a very long chain of glucopyranic nuclei, on the cellobiose

model, the number of these nuclei being 100 to 200.
441
442 PHOT OG RAPHIC C H EM I S TRY
~H
0~
CH OH H OH VC
OHO
H OH
H H 1:1 0 HHI:i
-0 H
H O H H
H H
l:t
·
0-
H OH CH;!OH
0 H OH CHt'H
0
Cellulose
The X-ray diffraction spectra show that cellulose is in the crystalline state,
the simple crystals, or crystallites, having dimensions and shapes which vary
with the nature of the fibre. Furthermore, the chains which make up the
crystallites are themselves made up of groups of smaller chains, each con-
taining four glucosic nuclei.
Lignine, which impregnates the cellulose in wood appears to be a polymer
of benzofurfurane, formed from a ketol by migration of an H and cyclization
with loss of water. Pectin is formed by the union of many substances: pen-
toses, hexoses, galaturonic acid, acetic acid, methanol.
Lignine
Cellulose is hydrolyzed by acids into simpler degradation products, the

final product being glucose. Controlled hydrolysis produces intermediate
products. With sulphuric acid and acetic anhydride the principal product is
octaacetylcellobiose.
When cellulose is pure, as in cotton, its treatment is simple but when it is
associated with lignine in wood, it is necessary to solubilize the latter. Use is
made of the relative inertness of cellulose to sodium bisulphite and chlorine:
the lignine combines with the bisulphite giving soluble sulphonates. With
chlorine, chloroderivatives are formed which can be solubilized with soda.
The soda also dissolves resins, waxes, fats and proteins.
412. Paper
Paper is made up of a tangle of cellulose fibres . Many starting materials are
normally used in its manufacture: rags and textile clippings, wood, straw,
esparto, cane, etc.
For photographic use, however, paper must have certain properties which
can only be achieved by judicious choice of materials, and manufacturing
processes. The water, which is used in very great amounts (1000-2000 litres
per kilo of rags, and 200-450 litres per kilo of of bisulphite paste) must be
very pure and non radioactive.
For photographic paper, the principal sources of cellulose are a mixture of
rag pulp or cotton with bisulphite wood pulp.
Rag pulp. The rags should be cotton or linen exclusively, but sometimes
hemp is included. Cotton has fibres which stretch relatively little in water,
and whose chemical resistance is relatively high. Linen, with its tangled
fibres, ensures great mechanical stability.
The sorted and cleaned rags are washed with an alkali: caustic soda or a
mixture of chalk and sodium carbonate. They are bleached with chlorine
whose excess is neutralized with an antichlor such as sodium sulphite.
The carefully washed fibres are then separated and chopped in a Dutch
beating trough equipped with a drum of blades (Fig. 51).
FIG. 51. Treating the paper pulp. Photo: Eastman-Kodak, Rochester, U.S.A.
Bisulphite pulp.' This is usually obtained from fir and spruce. It must be
stirred hot, and under pressure, with calcium bisulphite in the presence of
excess sulphur dioxide. The bark is then removed and the wood reduced to
chips and treated in large washing vats lined with acid-resistant bricks. The
sulphonated lignine dissolves. At the same time, aldehyde groups are pro-
duced from the side chains. To prevent their liberation with darkening of
the mass by polymerization the bisulphite must be maintained in excess. <1 >
The wood is then washed and bleached with chlorine or hypochlorite (hot
in the second case). Brick-lined concrete beaters in which the pulp is circu-
lated around baffles are used. The process is completed with thorough wash-
ing, after an alkali bath if chlorine has been used.
The pulp if incompletely cooked, then processed, gives waterproof
papers.
The yield is 45% of the weight of the dry wood whilst rag pulp gives
70-90%.
Other methods. The soda process is applicable to all woods, but it is more
expensive than the bisulphite process as 20-30% of reagent is required.
Papers obtained from birch, aspen and chestnut are slightly absorbent. They
must be bleached.
Straw, rye, esparto and bamboo treated with soda, or chlorine and soda
alternatively give fibres with interesting properties: those from straw are
waterproof, translucent and stiff, from esparto they are bulky and absorbent,
whilst bamboo produces tough porous papers.
The treatment of papers with soda obtained from sodium sulphate and lime
produces sodium sulphide which is ruinous for photographic papers. Further-
more, the bleaching of these high-coloured pulps, called 'kraft', reduces their
principal qualities, namely great strength and flexibility.
Finally we would note that half the world's paper consumption, particu-
larly newsprints, is obtained by mechanical breaking down of wood.
413. Sizing
To make the paper resistant, binders and fillers must be added to the cellulose
pulp.
The binder is made up of several of the following materials: gelatin, casein,
colophony, melamine, starch.
Colophony, which is the commonest binder is generally accompanied by
aluminium sulphate which lowers the pH to 4·5. The source of the colophony
can influence its photographic behaviour. Red or brown stains must not be
produced when the paper is treated with diazonium compounds after several
hours. To make the resin inert it should be treated with nitrous acid or a
nitrate.
· To produce very resistant papers it is advisable to size with 3% melamine<lb)
even together with colophony and aluminiumsulphate. Paraformaldehyde is
added to the melamine, which is first dissolved in water containing hydro-
chloric acid, and ripened for 24-48 hours. It is incompatible with casein.
A method of analyzing the sizing substances has been perfected by Seve. <2 >
Extracts are made with boiling acidified alcohol (colophony), acidified water
(gelatin), ammoniacal water (casein) and boiling acetic acid (melamine).
Filler. This is generally kaolin.
Dyes. These beling to the indanthrene group: indanthrene (or solanthrene)
blue and brilliant pink or sirius pink K.L., to tint whites; and indanthrene
orange or Hansa yellow G. I. for cream and ivory.
Testing the absence of iron and copper. The paper pulp, added to potassium
ferrocyanide must not give bluish or reddish stains. Iron content: less than
0·1 mg per kilo.
414. Baryta coating

The paper, and the emulsion which later covers it, are separated by a layer of
gelatin containing a suspension of barium sulphate (BaS04) in extremely fine
particles (0·5-11-L)· The barium sulphate increases the reflecting power of
the paper, and gives it a perfectly white surface covering all the faults. The
baryta solution is often tinted.
The barium sulphate is obtained by precipitating barium chloride with
sodium sulphate at 55°C. The dilution of the reagents, the temperature and
the agitation determine the fineness of the precipitate, and hence the degree
of mattness of the paper. Precipitation in the presence of glycerin gives a
very fine precipitate. This becomes more difficult to wash as the particles
decrease in size. The water content is reduced to 30-50%.
FIG. 52. Reeling up the Baryta coated paper. Photo: Eastman-Kodak, Rochester, U.S.A .
Baryta coating is carried out by applying the mixture with brushes, which
spread it over the paper which goes past them around a large drum. The wet
paper is led into a tunnel where it is arranged in long festoons which move
slowly. Linear speed: 90 to 150 feet per minute.
The paper is dried with a current of warm filtered air during its passage
through the tunnel, (which can accommodate 3000- 6000 feet) and after
rehumidifying to 18°C is reeled up (Fig. 52).
The operation can be repeated several times depending on the gloss
required.
Trumm
Baryta formulas Agfa Schoeller
Gloss Matt
I
'
Baryta paste (water % ) 120 kg SO% 50 kg 50 % 180 kg 30% 100 kg 44%
Baryta powder - 5 kg - -
Water 20 I 25 I 30 I 70 I
Glycerin 0 ·61 0 ·3 I 61 1·25 I
Water
I
30 I I 15 I 75 I ?
G elatin 4 ·5 kg 1 ·5 kg 18 kg 5 kg
Water 1I 1I 170 I -
Chrome alum 10% 1·5 I 1I 61 1·5 I
Formalin 30 % - - 100 cc +
Milk 2·5 I - 41 -
Alcohol 21 21 - -
Citric acid 10% 1I 0 ·21 - -
Dye solution 5% 0 ·1 I 0 ·15 I + +
Saponin 5% + + + +
Coarse-grain baryta is suitable for matt surfaces. Note that the percentage
in the paste indicates water and not barium sulphate. The milk is an anti-
frothing agent; it must be boiled. Citric acid is only used when the pH must
be reduced.
The purity of the water must be carefully controlled. If necessary, it must
be filtered over active carbon, then distilled. The gelatin must be photo-
graphically inert. Its selection is important.
Method of preparation. The white baryta paste is mixed in a Werner mill
with the water, glycerin and dye for 20 minutes at 30 r.p.m. The gelatin
solution (filtered through cloth at a pressure of 1 kg) is then added, and
mixing is continued for 15 minutes more. The mud is filtered through stain-
less steel gauze using a brush, then the remaining solutions are added.
Number of baryta layers. Matt surfaces 1, half matt 2, glossy 3 or 4. Weight
of BaS04 per m 2 per layer : 10-11 g.
Calendering. The coated paper is tteated at 80°C in a 5- or 7-roller calender
at a pressure of 3 tons (Fig. 53). Glossy surfaces three times, semi-matt twice
and matt surfaces, once or not at all. Wait one month, to let the baryta layer
harden, before coating the emulsion. (Fig. 54).
FIG. 53. Calendering the photographic paper.
FIG. 54. Coating the emulsion.

Photos: Eastman-Kodak, Rochester, U.S.A.
415. Waterproof paper

Waterproof paper is used for continuous printing of aerial photographs, reversal
identity photographs and the production of transparent photographic scales.
Cellulose, vinyl or acrylic lacquer can be used, if surface application with a solvent
is used. It is, however, possible to make the paper waterproof by incorporating the
compound in the pulp: melamine, vinyl acetate emulsion, vinyl copolymer, or prefer-
ably vinyl chloride emulsion plasticized with butadiene nitrile (Geon or Breon). These
emulsions can also be applied superficially. Some of them need curing at 120°C to
fuse the resin particles; others are film-forming when cold.
In all cases the lacquered paper must be coated with a substratum, otherwise the
emulsion would not adhere. This substratum can be a resin emulsion mixed with
gelatin. For example, for an acrylic lacquer, an acrylic emulsion with gelatin and
chrome alum can be used.'"l If necessary, several subbing layers can be used with
increasing proportions of gelatin.
The paper can even be waterproofed by exposure to vapour of tetra ethyl or methyl
silicate, followed by water treatment.<•l This fixes silicon atoms on the lateral chains.
Transparent waterproof photographic paper. Both sides of a long-fibre paper
(90 gm/m 2 ) are coated with a nitrocellulose lacquer such as: Nitrocellulose 20, ethanol
15, butanol 10, acetone 20, ethyl acetate 27, tricresyl phosphate 4 and castor oil 4.
Amount-100 g per m 2 • The emulsion surface is subbed with: gelatin 2, water 2,
acetic acid 10, methanol 76, amyl alcohol 10. Anti-halo: 5% gelatin coloured with.
acid fuchsine (60 cc/m 2).< 5 l '
416. Tests on papers

All papers, baryta coated or otherwise, which are to be used for photographic pur-
poses must be subjected to many control tests-chemical, mechanical, optical and
photographic.
Ash content (fillers) Homogeneity (holes)
Weight of size Resistance to breaking, wet and dry
Weight of baryta Stretching with wetting (two directions)
Humidity Resistance to tearing, wet and dry
Degree of water absorption on wetting Resistance to wear (rubbing).
Presence of iron, copper, etc. Crumpling
Presence of oxidizing or reducing agents Pliability
pH Bursting
Grease and other spots Swelling in water
Occluded air content Shrinkage on slow drying (two direc-
Dust (organic, mineral and metallic) tions) and rapid drying (two direc-
Moulds tions)
Sticking marks in rolls Flatness after drying (deformation)
Weight per sq. metre Resistance to photographic baths and
Density flatness
Thickness Formation of blisters
Microscopic examination of cross-sec- Uniformity of baryta coating (brushing
tion streaks)
Length and orientation of fibres Colour and whiteness (colorimetric
measurement)< •l
Gloss and grain (in all directions)
T ests with photographic emulsion-check:
Absence of white spots with centres (desensitizing dust) .
Absence of black dots with craters (dye which is a red light sensitizer).
Variations in speed and contrast compared with a standard paper..
Fog, after 30 days at 40 °C in dry oven, compared with standard paper.
Weight of paper. Ordinary photographic paper is supplied in two thicknesses: Paper
(properly named) 135-150 g/m 2 and card, 230-250 g/m 2 •
Document papers are generally 80 g but they can be lighter or heavier.
CELLULOSE ESTER FILMS
417. Cellulose esters

Cellulose, which, as we have seen, is an oxidation polymer of glucosic
anhydride, contains three hydroxyl groups per unit in its molecule: two OH
· · are directly attached to the pyranic nucleus and a third via a -CH 2 - . These
three OH groups therefore have not the same activity. The action of acids
esterifies the alcohol groups to give, according to conditions, cellulose mono-,
di-, and tri- esters, whose chemical properties differ. Frequently, it is simpler
to obtain the tri-ester first and then hydrolyze back.
Cellulose combines with most known acids, giving a very large number of
possible esters. The most interesting, as a photographic base is the triacetate,
which has replaced the dangerous nitrate.
The structure of cellulose derivatives is studied with X-rays, and ultra-
violet and infra-red radiation. In this way the hydroxyl, aldehyde, ketone and
acid groups which may be present can be identified and enumerated. <7 > The
X-ray diffraction spectra show the degree of crystallinity. If the ester has been
prepared in a homogeneous medium (in a solvent) it no longer has the fibrous
structure of cellulose. On the contrary, when a non-solvent diluent is used,
the resulting product retains the structure of the original material, which
imparts beneficial mechanical properties. The size of a main link is 10·3 A,
but the distance between two parallel chains depends on the number of
attached groups. In the presence of a solvent, the ester first dissolves these-
it is said to gelatinize-which brings about the separation of the chains
following the attachment of a solvent molecule on an acyl group (by a hexose
group). The parallel chains then become mobile relative to each other; they
can then disperse if excess solvent is added.
418. Cellulose acetates

Cellulose which is completely esterified with acetic acid is the triacetate which
contains 62·5% of acid combined in the form CH 3 • CO. 0. R. Ordinary
non-inflammable base is intermediate between diacetate and triacetate, and
is obtained by partial hydrolysis of triacetate. Triacetate is superior to it in
mechanical strength, and it alone is used for professional positive cine film.
When correctly prepared, it is less deformed by processing than diacetate
or nitrate.
Distinguishing. Acetate safety base can be distinguished from nitrate base
by its ultra-violet fluorescence. Another method is to place a piece of film in
trichlorethylene. The heavier nitrate (D 1· 52) sinks whilst the lighter acetate
(D 1·25) floats.
There are three main methods of preparing the cellulose acetates:

(a) Acetylation in homogeneous medium by acetic anhydride in acetic acid,
in the presence of a catalyst such as sulphuric acid. Pre-treatment is necessary
to swell the fibres (acetic acid + sulphuric acid).
(b) Acetylation in suspension in a diluent (heterogeneous medium), in the
presence of a catalyst- sulphuric acid or zinc chloride. Pre-treatment is also
necessary.
(c) Acetylation with acetyl chloride in pyridine, or, preferably, dioxane. <Bl
Acetylation in suspension, in which the cellulose fibrous structure is
retained, is preferable for film base.
Separation of the acetates. An acetone solution of cellulose acetate will
throw down the most acetylated fractions when water is added; when
ethylene chloride or dichloroethane is added, the less acetylated portions
come out. (Rb)
Physical properties. The density of the cellulose acetates increases with
the degree of acetylation from 1·2 to 1·35. Refractive index, 1·5. Resist-
ance to heat 175- 200°C. Decomposes at 250°C. It does not continue to
burn.
The acetates will disperse in certain saline solutions such as zinc chloride
and calcium bromide or thiocyanate.
The addition of 10- 30% alcohol to solvents increases the solution rate.
The number of possible solvents decreases as the acetyl content increases.
Methylene
Acetic acid Acetone Ethyl chloride
content acetate + 20 % alcohol
51 % soluble sl. soluble soluble
54 % soluble mod. soluble soluble
56 % soluble soluble soluble
58 % soluble soluble soluble
59 % sl. soluble sl. soluble soluble
62 ·5% insoluble insoluble soluble
Methyl formate and concentrated acetic acid dissolve all the acetates from
50 to 62·5 % .
Viscosity. The viscosity of cellulose acetate solutions depends on the
molecular weight, the degree of esterification, the solvent and the moisture
content. This reduces the viscosity.
419. Preparation of cellulose acetate in homogeneous medium

Pre-treatment. The cellulose is treated in the following bath:
Acetic acid 4kg
Sulphuric acid 0·020 kg
Cotton 1 kg
for half an hour between 30 and 40°C. It is left for another hour between
25 and 30°C, drained, washed and dried.
Acetylation. The hydrocellulose is acetylated at 40°C in:
Acetic acid 80 parts
Acetic anhydride 100 parts
( Zinc chloride
20 parts
or at 70°C in:
{ Sulphuric acid S.G. 1·82 25 parts
which can be used for 125 parts of hydrocellulose. An acetate with 60%
acetyl content is obtained.
In all cases the anhydride must be kept in excess. The reaction is carried
out slowly, with cooling to avoid any rise in temperature. The operation is
complete when all the cellulose is dissolved. It must then be stopped so that
the product is not gellified.
Hydrolysis. Five to 10% of water is added to the drained triacetate to de-
compose the anhydride. Precipitation of the acetate is avoided by adding this
water as dilute acetic acid. The mass is left for 12 hours.
The hydrolysis proper is carried out with more or less dilute sulphuric acid
-70% for example, at a constant temperature, generally above the ambient.
The more dilute the acid, the less hydrolysis: the degree of hydrolysis can
therefore be regulated at will. With concentrated acid, de-esterification can-
not be continued below 30% acetyl. With more dilute acid acting for a longer
time it can be carried down to 20% ; the product then becomes water-soluble,
and is precipitated by alcohol or acetone. At 13 % acetyl, the product de-
composes and regenerates insoluble cellulose.
The hydrolyzed acetate is precipitated with water. The viscosity of the
mass is first reduced by adding dilute acetic acid, followed by a large volume
of water. The acetate precipitates. It is washed with water to recover the acid,
and sometimes it is treated with a,lcohol. The acetate, washed as pulp, is
dried.
420. Preparation of cellulose acetate in suspension (heterogeneous

medium)
Pre-treatment. The cellulose, dried to 3-6% moisture, is introduced into the
stainless-steel pre-treatment vessel. Thirty-five parts acetic acid to 100 parts
of cellulose is added, and the mass is stirred for one or two hours.
The swelling of the cellulose can be accelerated by adding some sulphuric
or phosphoric acid. The acetic acid is then partly displaced with carbon
tetrachloride (Eastman-Kodak).
Acetylation. This is catalyzed by sulphuric acid. The chloride has the dis-
advantage of gelling the resulting ester.
The cellulose, in a second vessel (of bronze- 95 % Cu and 5% Sn) is
mixed with 300 parts of acetic anhydride, 400 parts of methylene chloride
Q
and 1 part of 98 % acid to 100 parts cellulose. The reagent mixture is added
in fractions. For a cellulose containing 3% water these will be:
Acetic anhydride 1/2 1/4
1/4)
CH 2 Cl 2 2/3 1/6 1/6 of the total
Sulphuric acid 1/4 1/4 1/2
Each addition is made after the temperature has dropped; a water jacket
may be used to assist this. A reflux condenser returns the methylene chloride.
After 4---6 hours all fibres have disappeared, indicating the end of the process.
The temperature is kept at 45°C until the required viscosity is obtained. (Sc >
The diluent could theoretically be benzene, toluene, xylene, trichlor-
ethylene, carbon tetrachloride, pyridine, etc.
Triacetate. The triacetate thus obtained must be washed and dried. To
avoid hydrolysis, the sulphuric groups present must be displaced by acetyl
groups. Sindl used ethyl acetate for this as it does not dissolve triacetate. (Sd>
Fifty-eight to 59% acetate. The triacetate is partially hydrolyzed. Eighty to
100 parts of water mixed with 65 parts of sulphuric acid is added to the mass.
The temperature is raised to 55-60°C. When the acetyl content has dropped
to 59 %, the acetate is pumped from the hydrolysis vessel and is neutralized
with sodium acetate. The operation takes 6 hours at 53-58°C. To obtain an
acetyl content of 58 % the product must dissolve completely in a mixture of
equal weights of methylene chloride and acetone. To achieve this the hydro-
lysis is continued for a further 20 minutes. For 56 % acetate, the testing sol-
vent is 9 parts of acetone and one part of ethanol.
When hydrolysis is judged to be complete, the temperature is raised to
80°C for a short time to remove the methylene chloride. The acetate is then
precipitated. If a low viscosity is required, water is added, with stirring. For
photographic acetate, 600-700 parts of 6% acetic acid is added, stirring only
for the first minute. After precipitation, stirring is continued for a further
10 minutes.
The precipitate is broken up and the suspension is drained on a moving
perforated band for 1 hour. The acetate is carried to a mixer where it is
ground with 10% of its weight of 30-35% acetic acid. The new suspension
is pumped onto a second perforated band where it is drained and washed
with eleven successive jets of acetic acid of decreasing concentration, and
finally with a jet of water. Each wash water is used in the previous treatment.
The resulting mass is centrifuged, which still leaves 150% of water. It is
dried at 60-70°C and at 10-20 mm pressure until its moisture content is
0·5-3 %. Drying time: 6 hours.
Construction materials: acetylation and precipitation-bronze. Other
stages, stainless steel, except the blower, piping and drier, which are alumin-
mm.
421. Cellulose raw material

The starting materials for the manufacture of cellulose esters are cotton linters
and wood pulp.
Cotton linters is the short down on the cotton seed left after the main
stripping. Manufacturing scraps are added to it. The fibres are first beaten to
remove the husk and earth, and are then degreased with trichlorethylene.
They are then purified by cooking for several hours in autoclaves containing
3% sodium carbonate, which removes the waxes and pectic materials (the
same result can be obtained with 3% caustic at normal pressure). The mass
is then successively washed, bleached, acidified, re-washed, dried and carded.
Nor more than 0·3 % ash and 0·2% fats must remain in the linters, which
must contain 98·5 % ot-cellulose and have a moisture content of 1% .
Wood jmlp. Wood pulp obtained from fir or beech by the bisulphite or the
alkali process must be as pure as possible. It is quite difficult to reach 96%
ot-cellulose. The pulp generally contains < 1% ash, < 0·5% waxes and fats ,
< 2 % pentosanes. Pulp sheets 1- 2 mm thick must be shredded before
esterification.
Purification of cellulose is absolutely essential for the preparation of cellulose
nitrate. Crude cellulose containing lignine, fats and waxes can ignite spontan-
eously when nitrated.
422. Cellulose acetopropionate and acetobutyrate

Propionic CH 3 - CH 2-CO. OH, butyric CH 3 - CH 2-CH 2 -CO. OH and
isobutyric (CH 3 ) 2 : CH-CO. OH acids esterify cellulose to form plastic
materials similar to the acetates. The general method of preparation is to react
a mixture of the corresponding acids and anhydrides on hydrocellulose in the
presence of a catalyst. Another standard method uses the acid chloride in the
presence of the corresponding magnesium salt: mix, for example, 162 parts
of regenerated cellulose with 198 parts of magnesium butyrate, dry, and add
213 parts of butyryl chloride and 25 parts of butyric anhydride. The mass
thickens rapidly and the temperature rises. It is diluted with nitrobenzene,
then poured into water, which precipitates the cellulose butyrate. For various
other methods, see <9 >.
The acetobutyrates and to a less extent, the acetopropionates are preferred to
these simple esters, as they give films which are very resistant to deformation
by heat and moisture. <9b> They are prepared as follows:
Action of propionic or butyric anhydride on partially hydrolyzed cellulose
acetate.
Action of a mixture of propionic or butyric acid and anhydride on cellulose
previously heated for 4 hours at 45°C in acetic acid. <10 >
Action of a mixture of acetic and propionic (or butyric) anhydrides on pre-
treated cellulose. The reaction can be catalyzed with monochloracetic acid
and magnesium perchlorate.
Action of propionic or butyric acid on partially hydrolyzed cellulose acetate
in the presence of monochloracetic anhydride.
Action of propionyl or butyryl chloride on partially hydrolyzed cellulose
acetate in pyridine.
Action of propionyl or butyryl chloride and acetic anhydride on cellulose
in the presence of a tertiary organic base.
Action of a mixture of acetyl chloride, acetic anhydride and magnesium

propionate or butyrate on regenerated cellulose.
See also the following patents <11 > and a study of the preparation and proper-
ties of the acetobutyrate by Sato, Lodai, and Kodama. <12 >
Finally, here is the method used in Germany for the preparation of cellulose
acetobutyrate.
The cellulose is pre-treated with acetic acid as above. Esterification 1s
carried out in the mixture:
Acetobutyric anhydride 300 parts
Methylene chloride 350 parts
Sulphuric acid 98 % 1 part
Esterification time: 7-10 hours. Temperature the same as for acetylation.
The final product contains 16-18% butyric acid and 43-44 % acetic acid.
Acetic acid, dehydrated at a high temperature and low pressure in the
presence of triphenyl phosphate gives a product CH 2CO called ketene, which
with butyric acid gives an acetobutyric anhydride C 3 H 7 • CO-O-CO. CH 3 •
The acetobutyrates and acetopropionates are soluble in acetone, ethyl
acetate, butyl acetate, ethyl lactate, methyl glycol acetate, diacetone, alcohol,
dioxane, methylene chloride, propylene chloride + 10% alcohol, etc.
423. Other cellulose organic esters

Cellulose esters other than the acetate, acetopropionate and acetobutyrate are
not used for the manufacture of films. Some of them, however, have been
tried for the formation of auxiliary layers:
Cellulose formate, less stable than the acetate.
The esters of fatty acids such as cellulose palmitate, obtained by the action
of the corresponding acid chlorides.
Cellulose phthalate. Phthalic anhydride combines with cellulose in the
presence of pyridine to give a triphthalate whose sodium salts are soluble.
The cellulose ethers result from the union of alkyl radicals to the cellulose
nucleus via an oxygen atom, following the scheme Cellulose-O-R. The
radical is generally methyl, ethyl, or benzyl. They are prepared by reacting
the alkyl sulphate or iodide on alkali cellulose, hot, and in the presence of
excess caustic soda.
The most important ethers are methyl cellulose, ethyl cellulose and benzyl
cellulose. Methyl cellulose with 13-18% -OCH 3 is soluble in cold water.
Carboxymethyl cellulose, or sodium cellulose glycollate, Cellulose-O-
-CH2-CO. ONa, is produced by the action of monochloracetic acid on
alkali cellulose. It is water soluble, giving very viscous solutions, and is used
as a thickener.
Alkali cellulose is obtained by heating cellulose with 35% caustic soda. The
drained mass is dissolved in water from which it is precipitated with sulphuric
or acetic acid after filtration. The hydrocellulose is redissolved in soda lye:
8% NaOH and 8% cellulose (see para. 433: Cellophane).
424. Cellulose nitrate
Cellulose nitrate is little used today except for roll- and sheet-film base, and
even in this role it has been largely replaced by acetate. Cellulose nitrate film
has excellent mechanical properties and its price is much lower than acetate,
qualities which have justified its choice despite its inflammability.
Cellulose, treated with fuming nitric acid in the presence of sulphuric acid,
is converted to the nitrate, but the nitrogen content varies with the operating
conditions. In general it increases with the acid concentration.
Its solubility depends on the degree of nitration:
Nitrogen Alcohol Acetone Ethyl Amyl
content + ether acetate acetate
9·5 % ins. mod. sol. mod. sol. mod. sol.
10·5 % sl. sol. sol. sol. sol.
11·5 % sol. sol. sol. sol.
12·5 % mod. sol. sol. sol. sol.
12·9% gelat. sol. sol. sol.
13·5 % InS. sol. sol. sol.
Complete nitration corresponds to 14·14% nitrogen. This requires nitric

acid whose concentration is greater than 85 %. For the usual lower degrees,
Lunge and Bebie give the following nitration mixtures:
Nitrogen Nitric Sulphuric
content acid acid Water
9·31 39·78 36 ·72 23 ·50
9·76 40·30 37 ·20 22·50
10 ·93 41·31 38 ·43 20 ·26
11 ·59 42·15 38·95 18 ·90
12 ·05 42 ·73 39·45 17·82
12 ·31 43·25 40·14 16 ·61
12 ·58 43 ·85 40·66 15-49
12·76 44·45 41·03 14 ·52
13 ·21 46·01 42·61 11·38
13 ·65 49·07 45·31 5·62
The viscosity of cellulose nitrate solutions depends not on the degree of

nitration, but on the nitration temperature. The viscosity falls as this tempera-
ture rises. It also depends of course on the solvent. The alcohol-ether ratio is
a characteristic for a certain nitrocellulose to obtain the minimum viscosity.
More alcohol can be added as the nitrogen content falls. The moisture content
must be borne in mind as it affects the viscosity of solutions.
The cellulose nitrates in current use contain 11- 12·5 % nitrogen (optimum
11·5-12%). Their viscosities vary from 0·5 to 200 seconds (ball method).
The low viscosity grades give thick even films most readily, whilst the viscous
varieties give stronger films.
Manufacture. Cellulose nitrate is made from wood pulp, or preferably, cotton linters,
purified by methods already given. This purification with hot alkali is essential, or the
mass may ignite when nitrated due to the formation of unstable nitroderivatives.
456 PHOTOGR APHIC C HEMISTRY
Nitration can be performed with the usual nitro sulphuric mixtures given above ,
or by a variation such as the following (which gives a product very soluble in alcohol-
ether): nitric acid 23 ·7 % sulphuric acid 61 ·71 % , water 14 ·6%. Nitrating time : 30
minutes maximum. Twenty-eight kg of acids are required to give 1 kg nitrate.
It is, however, better to nitrate in the presence of nitrogen peroxide N 2 0 4 (B. Pt.
21 ·6°C) which retains the fibrous structure of the cellulose. To avoid degrading the
cellulose, the peroxide is dissolved in the nitric acid. The nitrogen content depends
on the percentage of peroxide: with 30 % , a content of 13 ·7 % N is obtained. A nitro-
sulphuric mixture containing the peroxide can also be used, for example, nitric acid
22, sulphuric acid 57, nitrogen peroxide 2, water 19. Nitrating time: 45 minutes at
30°C.
Cellulose nitrates with a high nitrogen content are also prepared with acetonitric
and phosphonitric acid mixtures.
The nitration acid mixtures must always be cooled before use. The nitro cotton is
then drained (but not completely) and washed for several days in a large amount of
water. To stabilize it, it is boiled in 0·5 % sulphuric or hydrochloric acid for two days .
After washing and pulping, it must be bleached in 1% hypochlorite or chlorine water,
n eutralized with bisulphite, again thoroughly washed, and then drained. To de-
hydrate the mass, it is squeezed in a press. By imbibing 95 % alcohol, and again pressing,
the water is removed; this can be repeated. Cellulose nitrate must not be dried.
Together with camphor, it gives celluloid.
425. Plasticizers
A plasticizer is a substance which can soften a polymer by jellifying it. It is
located between the side members of the molecular chains (and particularly
the ester groups) which enables the chains to shift by sliding over each other.
Plasticizers are generally high boiling solvents (low vapour pressure). They
must be resistant to heat and light, be colourless, insoluble and not hydrolyz-
able.
By combining a solvent, having keto and ester groups, with a heavy nucleus
it is possible to obtain these qualities. Thus with phthalic acid C 6HiCO. OHh
and fatty alcohols, phthalic esters are obtained which are excellent plasticizers:
Ethyl phthalate C 6 H 4 (CO. OC 2 H 5 ) 2
Butyl phthalate C 6 HiCO. OC 4H 9) 2
Isoamyl phthalate C 6HiCO . OC 5 H 11) 2
Octyl phthalate C 6HiCO. OC 8Hu) 2
Ethyl phthlate, which boils at 298·5°C can advantageously be replaced by
the less volatile higher homologues. The amount added to cellulose acetate
should not exceed 10% .
Another group of placitizers in current use are the phosphates: triphenyl
phosphate (C 6H 5) 3P0 4 (M.Pt. 48·8°C) and m-tricresylphosphate (C 6H 4
CH 3 )a P04 (B.Pt. 420°C). Up to 25 % can be used in an acetate. The jellifying
properties of tricresylphosphate are attributed to the flexible pyramid shape
of its molecule.
Among the other plasticizers the most interesting are:
Tartrates- butyl (B.Pt. 300°C) and especially amyl (B.Pt. 400°C). Miscible
in all proportions with cellulose esters.
Glycerin esters: triacetin (or glycerin triacetate) and the tripropionate and
tributyrate. They have the disadvantage that they hydrolyze. More stable
products are obtained by combining diacetin with phthalic acid, or glycerin
with abietic acid derivatives. The tribenzoate is also a good plasticizer (M.Pt.
71°C).
Sulphamides, such as monoethyl-p-toluene sulphamide CH 3 • C 6H 4 • S0 2 •
NH. C 2 H 5 or Elastol (M.Pt. 63°C). They have been criticized for producing
brittle films.
The esters of fatty acids are not volatile, but the length of their chains
reduces their jellifying power. They can only be used as additives. Butyl
oleate (B.Pt. 357-370°C) with benzyl alcohol, butyl stearate (M.Pt. 18-20°C)
mixed with phthalates or tartrates, amyl borate, etc.
Cellulose acetopropionates and acetobutyrates are placticized like the
acetates. The following have also been recommended, however: octyl
phthalate, tributyl phosphate, cyclohexyl adipate, p-toluene sulphamide,
camphor, tetrahydrofurfuryl furoate, glycol furoate, <14 > furfuryloxyacetic
esters, U 5 l alkyl acetamides, <16 > glycol dilactates, <17 > glycolic esters of 3 : 4 :
5-trimethylbenzoic acid, <18 > the ester-amides <19 l and triethanolamine esters. <20 >
Plasticizers for cellulose nitrate. The best and most common plasticizer for
cellulose nitrate is camphor. <21 > Good results are also obtained with butyl
phthalate (up to 50%), ethylene glycol phthalate (cellosolve phthalate) (B.Pt.
345°C), butylene glycol phthalate (B.Pt. 370°C), ethylacetanilide C 6 H 5 .
N(C 2H 5 ) CO. CH 3 , a camphor substitute called Manno! (M.Pt. 54°C,
B.Pt. 258°C), hydroxynaphthalide-2 : 3 (Mittel P.H.), symmetrical di-
ethyldiphenylurea (C 6H 5 )(C 2 H 5)N-CO-N(C 6H 5 )(C 2H 5), (Mollit I)
(M.Pt. 72°C, B.Pt. 325°C).
The action of many plasticizers on various cellulose esters has been studied
in detail by many writers, to whom reference should be made. <22 >
426. Dopes for film casting

The dopes for film making are prepared by dissolving the cellulose ester and
the plasticizer in a volatile solvent which preferably contains a heavier solvent
to avoid reticulation during drying.
Cellulose triacetate-58% and over. Eighty-five parts of acetate are plasti-
cized, for example, with 15 parts of a mixture of triphenyl phosphate and
diethyl phthalate, in a solvent made up of methylene chloride 85, chloroform 10,
amyl alcohol 5, or a mixture of methylene chloride and butanol or ethanol,
or methylene chloride, acetone and methanol. A suitable mixture contains:
methylene chloride 90, methanol 3, n-butanol 7. <22 hl
A non-solvent (e.g. amyl alcohol) produces a gel which improves the initial
rigidity.
Acetate-56% and less. The solvent is generally acetone; anhydrous ethanol
and toluene can be added, for example: acetone 85, alcohol 10 and toluene 5.
Plasticizers: triphenyl phosphate and ethyl (or other) phthalate. Seventy-
seven parts of solvent to 20 of acetate and 3 of plasticizer are required.
458 PHOTOGRAPHIC CH E MISTRY
A formula attributed to Schleussner contains acetate 25, acetone 100,

triphenyl phosphate 3, tricresyl phosphate 0-1, phthalic ester 0·2, p-toluene
sulphamide 2.
The volatile solvent can be partly or completely replaced by methyl or
ethyl formate or acetate. Unlike the nitrate, cellulose acetate is insoluble in
amyl acetate.
Cellulose acetobutyrate. In acetone solution. The same plasticizers as ace-
tate, or those already given.
Cellulose nitrate. The solvent is acetone or anhydrous methanol. Example:
cellulose nitrate 18, camphor 4, butyl phthalate 0·5, acetone 77·5 .
Another formula includes: cellulose nitrate 25, camphor 3·8, tricresyl
phosphate 0-05, phthalic ester 0-1, butanol2·5, ethanol 13·5.
Amyl or butyl acetate can be added to the solvent. It is also well known that
cellulose nitrate forms a dope with an alcohol-ether mixture.
The dopes are prepared in mixers, filtered by pumping through cotton,
and degassed by standing. Slight heating speeds up the ascent of the bub-
bles. <22 cJ It is then led to the reservoirs of the coating machines.
427. Solvents
As stated above, the main solvent for 58% triacetate is methylene chloride
CH 2 Cl 2 • It is a very volatile non-inflammable liquid, but it is toxic. Its use
necessitates well-sealed machinery and good ventilation. Compared with
ether and acetone, the evaporation times are: ether 1, methylene chloride 1·8,
acetone 2·1.
Boiling points of cellulose ester solvents (A = acetate, N = nitrate, E = ethyl cellu-
lose, B =benzyl cellulose).<23 >
oc oc
Methyl formate (A, N) 32 Epichlorhydrin (A) 117
Ether (N + alcohol) 34-35 n-butanol 114-118
Methylene chloride (A + alcohol) 40-42 Isobutyl acetate (N) 116
Ethyl formate 54 Acetic acid (A, N) 118
Acetone (A, N) (acetobutyrate) 55-56 Glycol diethyl ether (N) 121
Methyl acetate (A, N) (E with Ethyl butyrate (N) 122
solvents) 56-62 Amyl formate (N) 123
Chloroform (A) 61 n-butyl acetate (N, E) 121-127
Methanol (N, E) 64-65 Mesityl oxide (A, N) 129
Ethyl acetate (N) (A + alcohol) Methyl cellosolve (ethylene gly-
(acetobutyrate) 74-77 col monomethyl ether) (A,
Ethanol (E) (B + benzene) 78 N) 115-130
Methyl ethyl ketone (A, N) 79 Isoamyl alcohol (E) 132
Isopropanol 82 Cellosolve (ethylene glycol
Isopropyl acetate (N) 84-93 monoethyl ether) (N) 126-138
n-propyl acetate (N) 97-101 Isoamyl acetate (N) (E +
n-propanol 96-98 alcohol) 138
Dioxane (A) (N +alcohol) (aceta- Methyl cellosolve acetate (A, N) 138-145
butyrate) 101 n-propyl ketone (butyrone)(A,
I so butanol 104-107 N) 144
Toluene (E) 109-110 Cellosolve acetate (N) 149-160
Trichloroethane (A) 110-115 Cyclohexanone (A, N) 150-165
oc
Diacetone alcohol (A, N) 150-165 Ethylene glycol monoacetate
Cyclohexanol (B) 155-170 (A, N) 178-195
Ethyl lactate (A, N) 155-163 Ethyl acetylglycolate (A, N) 181-195
Furfurol (A, N) 160-165 Carbitol (diethylene glycol
Methylcyclohexanone (A, N) 165-171 monoethyl ether) (N) 180-200
Isoamyl butyrate (N) 179 Benzyl alcohol (A, N, E) 204--208
Cyclohexyl acetate (A, N) 170- 180 Ethyl benzoate (A, N) 212- 215
Furfuryl alcohol (N) 177 Diethylene glycol (N) 244
T etrahydrofurfuryl alcohol (N) 177 Diacetin and triacetin (A) 258-259
Ethylene glycol diacetate (A, N) 186-190 Butyl tartrate (A, N) 298
Butyl lactate (N) (acetate Butyl tartrate (A, N) 325
diluent) 170-195 Amyl tartrate (A, N) 400
It should be remembered that the use of solvents requires stringent pre-
cautions against their toxicity and inflammability. In general, solvents should be
regarded as dangerous, for either long or short periods. The chlorinated
compounds are the most toxic, together with the benzene hydrocarbons,
methanol, the formates, dioxane and mesityl oxide.
The inflammability is determined by the flash point. The solvents having a
boiling point below ll5°C can form explosive mixtures at room temperature.
The chlorinated compounds are practically non-inflammable, but at high
temperatures the poisonous phosgene can be produced.
The highly inflammable liquids can be ignited by static discharge, produced
for example, by the friction of the product in a casting tube. For this reason
all vessels must be earthed.
Measurement of the viscosity of dopes. The viscosity of dopes is generally
measured by the time taken for a steel ball to fall between two marks in a
vertical glass tube. The viscosity in poises is given by the equation
v = K(D -d)t
where Dis the density of the ball (7·65 for steel), dis the density of the vis-
cous liquid, t the falling time in seconds and K the constant of the instrument.
Glycerin can be used as the standard liquid.
The dimensions of the apparatus are:
Distance
Tube Distance Tube to upper Ball
diam. length mark diam.
U .S.A. 1 in. 10 in. 14 in. 2 in. 5/16 in.

(25-4 mm) (254 mm) (355·6mm) (50·8 mm} (7·93 mm)
Brit. Eng. St. Ass. 32mm 150mm 260 mm 55 mm lin.
(3·16 mm)
1 .
nm.
(1·58 mm)
The viscosity can also be measured by the other methods given in para.
358.
Q*
428. Film-base casting

Film base is prepared by spreading the dope on a polished moving metal
surface. The metal surface can be either a drum or an endless belt. The dope
is poured through a hopper of variable height in a layer of constant thickness,
which on steady drying gives a thin transparent film.
Drums with a diameter of 12 to 20 feet (Fig. 55) revolve continuously at
about two revolutions per hour, giving an output of about 90 feet of film, 4 to
FIG. 55 . M anufacture of film base by casting on t o m etal drums.

(Photograph: Eastman-Kodak, Rochester, U.S.A.)
5 feet wide. Smaller 6-foot drums are also used for casting triacetate from
methylene chloride. The drum surface is silvered, and perfectly polished.
The film is removed from the heated drum before it is completely dry, by a
system of other rollers which completes the removal of solvent.
Casting is a very critical operation which requires precise control of the
operating conditions. The viscosity of the dope must be kept constant, the
drying temperature and speed of rotation, uniform, and the air must be
thoroughly filtered. If the solvent is removed too rapidly, a surface skin may
form, which reticulates. The presence of water can result in the film bloom-
ing. The rate of evaporation of each solvent depends on its vapour pressure
and the working temperature.
Endless band machines are used more in Europe. They consist of a nickel
or copper band supported by two drums. These bands are about 4 ft. 9 in.
wide and 75-100 feet long. The dope is generally spread over about 48 in.
and trimmed to 42 in. Speed: 150- 300 feet per hour. The electrolytic copper
bands are 0·03 inches thick and are silver soldered, smoothed and undergo
many tests. Nickel bands 0·02 inches thick are to be preferred. The machine
carrying the band must permit its thermal expansion. The surface of the
bands must be repolished every two or three years owing to pitting by cor-
rosiOn.
Copper belts have a layer of gelatin applied to them for acetate casting or
hydrolyzed cellulose acetate for nitrate. Nickel ones are not protected. The
drying tunnel is at 40°C and the first drum at 35°C. The film is dried com-
pletely at 60-70°C after removal from the band. It can be subbed whilst it
still contains 5- 8% of solvent. The drying rate depends more on the tempera-
ture of the air than on its velocity. When highly inflammable solvents are
used, it is advisable to reduce the oxygen content of the air to below 8% by
introducing nitrogen into the drying air.
In all cases, the solvent vapour content must be lower than that corres-
ponding to the lower explosive limit or higher than that corresponding to the
higher explosive limit. A mixture of inflammable gas with air will not burn
if it is too poor or too rich.
The solvent is recovered either by absorption with active carbon, or by con-
densation (cooling to below l0°C). It is then purified. Active carbon is
regenerated with live steam.
Static electricity is eliminated either with electrical apparatus using the
corona effect (Chapman, Skimex, Calorit, Corona, Simco, etc.) or by IX-ray
bombardment using polonium (United States Radium Corp.). The half life
of this metal is 136 days.
Setting method. A cellulose ester, dissolved only in an active solvent above
a certain temperature will set when it is cooled. It can then be stripped and
dried on both sides. For example, cellulose acetate, triphenyl phosphate,
propylene chloride and isopropyl alcohol; the solution is coated at 60°C and
cooled to l0°C. The set film still containing 20% solvent is separated and
dried. <24 >
Coagulation method. The dope is coagulated in a hot damp atmosphere.
Sizes of film base. Width 41- 54 inches. Thickness: roll-film ·003 in., cine
film ·005 in., sheet film ·008 in.
429. Deformation of films

Cellulose esters absorb 2-3 % of water.
They expand, then contract on drying with unequal shrinkage in the two
perpendicular directions. Drying stresses, by orienting the linear molecules,
shrink the film in this direction by releasing the mechanical tension.
462 PHOTOGRAPHIC CH E MISTRY
Hysteresis phenomena affect re-wetting. Furthermore, the emulsion swells

eight times more than the base. The size variations by wetting are reversible.
Those due to loss of solvents and release of mechanical stresses are not.
The shrinkage of a film must not exceed 1% after 10 days at 40°C, 50-SS%
R.H. This shrinkage is increasing by ageing, but it may be irregular, depend-
ing on variations of temperature and humidity. It should be less than 0·3%.
The new triacetate films only shrink 0·15 % in length and 0·2% in width
after two years at 25 °C and 50 % R.H. For photogrammetry, however, aceta-
butyrate films are preferred as their shrinkage is only 0·04% . Shrinkage on
keeping for one year is 0·01 % . The difference between the length and width
shrinkage is less than 0·01 %. Swelling is 7·10- 5 per degree Centigrade and
8·10- 5 per hygrometric degree.
The longitudinal and lateral shrinkage by processing and the expansion on
moistening and heating of several commercial films was measured by Fordyce,
Calhoun and Moyer. <2 4c J
Per cent Per cent expansion for an

shrinkage increase of
after I
processing 10% RH II 5·5 °C
I
long. lat. long. lat. long. lat.
I
Negative
I
(B. and W, and colour) 0 ·06 0 ·07 0 ·07 0 ·08 0 ·03 0 ·035
Positive
(B and W, and sound) 0 ·05 0·05 0 ·05 0 ·06 0·03 0 ·035
Eastman colour prints 0·07 0·08 0·06 0·07 0 ·03 0·035
Kodachrome 16 mm
(acetopropionate) 0·09 0 ·10 0 ·08 0·10 0 ·035 0·04
For printing on continuous printers, the pitch of the perforations must be

+ 0·5 %, - 0·2% of that of the positive raw stock.
All films are distorted by being wound on spools. The difference in these
deformations in the two directions is, after four months:
0·01 % emulsion in.
0·05 % emulsion out.
Drying with alcohol increases shrinkage. It is least with isopropyl alcohol,
but age shrinkage increases.
Mechanical tests on films. The mechanical tests show the following proper-
ties.
Breaking strength per mm 2 (about 12 kg).
Stretch to breaking (45 %).
Number of folds (80 for nitrate).
The figures are relative to nitrate which has the best mechanical strength.
The resistance of triacetate approaches nitrate, but diacetate can only be
folded forty times at the most.
To these main tests, others for hardness, elasticity, perforation, tearing
from a started cut, resistance of perforations, and the effect of high and very
low temperatures can be added. Note the softening and decomposition
temperatures (80°C and 130°C for nitrate).
The best-known apparatus for determining these physical characteristics
is made by Louis Schopper (Leipzig).
Degradation by light. Ultra-violet radiation depolymerizes cellulose, cellu-
lose nitrate, cellulose acetate, and other esters like acetobutyrate with dis-
colouring and reduction of mechanical strength. The chains are ruptured
with a reduction in molecular weight. Depolymerization is accelerated by
oxygen.
430. Burning and decomposition of films

The cellulose esters are not perfectly stable systems. For many reasons they are sub-
ject to changes. Also the storage of films, particularly developed ones, necessitates
certain precautions.
Of all the esters the nitrate is the least stable. The ease with which it is decomposed
and ignited is well known. It readily gives off nitrous fumes which attack the gelatin
in the presence of moisture. A freshly made nitrate film will not decompose after
20 days in an oven at sooc,<••> but if it is old, nitrogen peroxide is evolved after 3 days.
If it is impregnated with hypo it will ignite at 80°C after one or two days-a danger of
incomplete washing of nitrate films.
It is usual to distinguish between the ignition temperature at which combustible gas
is evolved, and the temperature of spontaneous combustion. The test can be carried out
either in an oven, in a test-tube slowly heated in an oil bath, or in a current of air
whose temperature is raised.<••> With the latter method, the ignition and spontaneous
combustion figures following are obtained:
Celluloid, 141 and 141 oc (instead of 130 and 180°C}.
Cellulose acetate, 305 and 475 °C .
The stability of an ester is also determined by the loss of weight after at least 48
hours in an oven at 105°C: <10% for nitrate.
Films which are to be kept for a long time must be examined periodically. An official
method is to heat a 6-mm diameter sample from the leader, weighing 7 mg in a tube
in an oven at 134°C.< 27 >The stopper of the tube is fitted with a piece of alizarin red
paper. The acid vapours decolorize the paper to a height of 3 mm.
Decolorizing time Film can be kept
10-30 mins. 6 months
30-60 mins. 1 year
>60 mins. Repeat test after 2 years
If decoloration is very rapid, another print must be made immediately.
Nitrate films should be kept in a cooled, well-ventilated place at 2-4°C and 50%
R.H., and in non-metallic containers.
Acetate films can be kept at 18°C without harm.
431. Gelatin removal

This is used for recovery of film base, and three main methods are used.
(a) Immersion in a solution of caustic soda. This method is unsuitable for hardened
gelatin. It has the disadvantage of hydrolyzing the base, and with cellulose nitrate,
there is the danger of spontaneous ignition of the recovered base.
(b) Immersion in a solution of sodium hypochlorite. Effective even with hardened
gelatin. Stripping takes place in a few minutes.
(c) Treatment with a protein attacking enzyme. In work on the action of Rhozyme
P 11, Gansel<••> found that the activity was quadrupled by raising the pH from 5 to
8, and doubled from 40 to 50 °C. He also tried Serizyme and Takamine.
Denitration of films : Nitrate film scraps, dissolved and cast in sheets, are denitrated
by treating for an hour in a solution of magnesium acid sulphide, in the presence of
an ammonium salt. The role of the latter is to avoid precipitation of magnesia. After
washing and drying sheets of regenerated cellulose, which still contains 0 · 5% nitrogen,
are obtained.
432. Analysis of cellulose esters

The determination of the combined acid in cellulose esters is carried out either by
alkaline saponification or by acid hydrolysis. The estimation can be carried out on the
solid ester, but it is better if the ester is in solution. <30 >
(a) Saponification with hot caustic, and estimation of the excess alkali with HCl
(Eberstadt's method). The ester is first heated at 50-60 °C for 30 minutes in 75 %
alcohol. It is then heated for 15 minutes with 0·5 N caustic, then, after 48 hours
titrate with 0 ·5 N HCl. Wait several hours for the end of the reaction.<31 >Values too
high.
(b) Koevenagel and Koenig heat the ester for 90 minutes in alcohol, then agitate
for 2~8 hours with cold 0·5 N NaOH. Back titrate with H 2 S0 4 •
(c) Saponify with alcoholic caustic, 24 hours, at 25-30°C. Back-titrate with an
acid. This method can be used for all esters.
(d) Saponification of the ester dissolved in acetone (Barnett's method).
(e) Saponification of the ester dissolved in pyridine (Battegay and Peuche).
(f) Hydrolysis with 50 % sulphuric acid followed by distillation of the organic
acid in vacuo, after adding sodium phosphate (Hess), or by steam distillation (Ost and
Katayama). The distillate is titrated with soda or back-titrated with H 2 SO•.
(g) Separation as methyl esters by treating with sodium methoxide in the presence
of excess p-toluene sulphonic acid which acts as a catalyst. The volatile products are
distilled into an alkali. <32 >
Determination of the nitrogen content of cellulose nitrate.
If the nitrocellulose is free from plasticizer it can be decomposed with mercury in
concentrated sulphuric acid. Nitric oxide is evolved and its volume is measured:
2HNO s + 3H 2 S0 4 + 3Hg -7 2NO + 3HgS0 + 4H 4 2 0
The Schultz-Teeman method uses ferrous chloride in hydrochloric acid. The reac-
tion takes place in a flask connected to a graduated tube filled with caustic soda, which
absorbs the carbon dioxide.
2HNO a + 3FeC1 3 + 3HC1 -7 NO + 3FeC1 + 2H

3 2 0
Extraction and determination of plasticizers in cellulose acetate. This is done in a

microsoxhlet with 0·5 g of material.< 33 >
433. Cellophane
Cellophane is a transparent, hygrometric and extensible material made of
regenerated cellulose. It can be used as a temporary support for carbon images,
and as a sensitized silver salt layer (see para. 340) and for diazo processes.
Cellophane contains 15 % plasticizer, mainly glycerin. Its surfaces can be
coated with an impermeable layer. It is made by coagulating viscose with
dilute sulphuric acid.
N ON -CELLULOSE FILMS
434. Polyethylene terephthalate films
Polyethylene terephthalate, studied by Whinfield and Dickson in 1940, is a
new plastic substance with remarkable properties. Known by the names
Dacron and Mylar (Du Pont), Terylene (I.C.I.) and Tergal (France), it
can give film bases which are much more resistant than cellulose bases.
These new bases are specially manufactured by Du Pont under the name
Cronar.
Polyethylene terephthalate is a high polymer with a molecular weight as
high as 15,000. Its density is 1·4 and it softens between 220 and 240°C and
melts at 260°C. It can be welded and is three times as reistant to heat as
cellulose triacetate. Furthermore, at low temperatures it loses none of its
qualities.
A polyethylene terephthalate film is dimensionally very stable as it contains
no plasticizer. The water take-up at 25°C and 65 % R.H. is 0·:4%. The ex-
pansion produced by 1% R.H. is 0-001 mm per metre against 0-004 for
acetate. Expansion per oc is 0-036 mm against 0 -041. !33b >
The tensile strength is particularly high: 1,330 kg per cm2 against 880 for
triacetate. Resistance to tearing is double that of other plastics. Impact strength
is 75 kg/cm2 against 3 for acetate. Abrasion resistance: 100, polyamides 150,
other films 5- 25. Resistance to alternate flexing is equal to Nylon. In short, the
life of the film is trebled compared with other cellulose films. Because of this
exceptional resistance the thickness can be easily reduced by 25 % enabling
the amount on a spool to be increased.
The resistance to light is equal, but not better than that of other films. How-
ever, the harmful radiations are between 300 and 360 mi-L and can be absorbed
by a sheet of glass. Transmission limit: 315 mf-L.
Terephthalate is not very inflammable. It burns only slowly releasing
burning droplets which extinguish themselves.
Chemical properties. Terephthalate is not readily hydrolyzed, except by hot
concentrated alkali. Oxidizing and reducing agents have little effect. It is not
affected by acids. Organic solvents have no effect, except phenols and chloro-
phenols.
435. Constitution and manufacture of polyethylene terephthalate

Terephthalic acid is an aromatic para diacid corresponding to phthalic acid,
which is the equivalent ortho acid. It is produced by aerial oxidation, in liquid
medium of p-xylene, from petroleum refineries, at 130-140°C in the presence
of a cobalt salt as catalyst. The accompanying o- and m-xylene and the ethyl-
benzene are previously removed by crystallization, distillation, then re-
crystallization or sulphonation.
The terephthalic acid is first esterified to methyl terephthalate which is
purified. This is then heated with excess ethylene glycol in the presence of a
catalyst-zinc borate or litharge (PbO). (aac) In this reaction, a mixture of
CO.OH
OCO.OH ~ 02 ~H
v _ v+H20
CH 3 CO.OH
Phthalic acid p-xylene Terephthalic acid
hydroxyethyl terephthalate and low molecular weight polymers is formed.

The excess ethylene glycol is eliminated by vacuum distillation whilst the
condensation gives long polymer chains of 40-55 units.
CH,O.CO OcO.OCH, • 2 OH.CH,-CH,PH

Methyl terephthalate Ethylene glycol
-
OH.cH;CH,O. CO 0 CO OCH2·CH.OH + 2 CH,OH
Hydroxyethyl terephthalate
Low polymer (y = 1-4)
High polymer (u = 4Q-55)

Polyethylene terephthalate
Manufacture of terephthalate film. The molten mass of plastic is coated by

extrusion, without the use of solvents, onto a polished surface. If the film is
stretched in two perpendicular directions its physical characteristics are
modified with an increase of mechanical resistance. To retain this modified
condition, it is necessary to heat the base to about its softening point resulting
in a reorientation of the recrystallized macromolecules. The same treatment
on a filament changes its properties from those of linen to those of silk.
The thickness of the resulting terephthalate films varies from 6 to 200 1-'
(·0003-·01 inches).
436. Other film bases

A large number of other plastic materials can be used to prepare film bases, or trans-
parent or translucent sheets. These supports, however, lack mechanical resistance or
elasticity, although they could be coated. The principal ones are:
Polyvinyl chloride and its co-polymers with polyvinyl acetate. The films are obtained
by extrusion.
Polyvinylidene chloride or Saran.
Methyacrylate resins (Perspex) and stearyl methacrylate (Rohm and Haas).
Polystyrene in transparent plates: the films are brittle.
Polyamides: Nylon, Rilsan.
Polyurethanes: Perlon.
Rubber hydrochloride (Pliofilm).
Polyethylene (soft and translucent).
Trijluorochlorethylene (Kel-F).
Tetrafluoroethylene (Teflon).
The use of these bases involves emulsion adhesion difficulties, particularly with the
fluoro derivatives.
AUXILIARY LAYERS
437. The substratum
The photographic emulsion will not adhere directly to cellulose nitrate or
acetate supports.
Before coating the emulsion, the cellulose film is covered with a very thin
layer of a substratum which facilitates the mutual adhesion of the two materials.
Subbing consists in principle of introducing a small amount of gelatin into
the base surface, swollen by alcohol. Koslow and Podgorodetzki have shown
that gelatin applied in aqueous solution to a nitrocellulose film previously
immersed in alcohol, adheres perfectly. Adhesion can also be achieved by
superficial saponification with 25% caustic soda at 50-65°C for a few seconds.
In practice gelatin is used as a weak solution in alcohol containing acetic
acid and a little water. The acetic acid enables the gelatin to be dissolved in
the alcohol, which is essential. The water content is also critical; if there is
too much water the base does not swell, and the gelatin does not stick, but if
there is not enough, the gelatin precipitates and no longer sticks.
Cellulose nitrate. A thin layer of substratum is applied from the following
solution:
Gelatin 1·2 g
Acetic acid 2g
Water 5 cc
Methanol 99·5% 92 cc
The gelatin is first dissolved in a mixture of the water and acetic acid by
heating on the water-bath after soaking for several hours. The methanol is
then added little by little. If the emulsion does not adhere well, reduce the
water; if a white deposit is formed, increase it.
Cellulose acetate below 56%. There are several ways of subbing ordinary
cellulose acetate.
(a) It is first coated with a thin layer of nitrate, which may contain a little
acetate, followed by a substratum for nitrate as above.
(b) Gelatin-nitrocellulose substratum.
Gelatin 1g
Acetic acid 2g
Water 4 cc
Nitrocellulose 1g
Acetone 60 cc
Methanol 32 cc
(c) Gelatin-chrome alum substratum< > 34
Gelatin 0·6 g
Chrome alum 0·06 g
Water 4 cc
Acetic acid 2g
Ethanol 12 cc
Methanol 34 cc
Acetone 48 cc
(d) Add 5 cc methylene chloride to the above recipe.
(e) Acetic acid as a gelatin solvent has the great disadvantage that it is
difficult to remove by evaporation. Any remaining after drying may change
the pH of the emulsion and alter its characteristics. The same is true of
salicylic and phthalic acids: being non-volatile, they diffuse into the emulsion.
Nadeau<35 > solved the problem by using ,8-keto acids, which decompose
with moderate heating into the ketone, which has no effect on the emulsion,
and carbon dioxide. Thus benzoylacetic, methylacetoacetic and trimethyl-
acetoacetic acids decompose respectively into acetophenone, methyl ethyl
ketone and pinacolone:
+ C0
C 6H 5 -CO-CH 2 -CO. OH-+ C 6H 5 -CO-CH 3 2
Benzoylacetic acid Acetophenone
CH -CO-CH(CH )-CO. OH-+ CH -CO-C H + C0
3 3 3 2 5 2
Methylacetoacetic acid Methyl-ethyl ketone
(CH ! C-CO-CH -CO. OH-+ (CH h ) C-CO-CH + C0
3) 3 2 3 3 2
·Trimethylacetoacetic acid Pinacolone
The acetate film is subbed, for example, with the following solution:
Gelatin 1g
Benzoylacetic acid 2g
Water 4g
Methanol 99·5% 28 g
Acetone 65 g
to which 0·1 g chrome alum may be added. The film is then quickly heated
to 82-135°C to decompose the acid. Nadeau and Stark add chromium chlor-
ide or nitrate to the organic solutions (acetic or otherwise) to increase ad-
hesion. <36 >
Cellulose triacetate, propionate and butyrate. It is difficult to sub these
esters. Several coats a few microns thick of the same ester, more and more
hydrolyzed, until a normal adhesion layer is obtained can be applied. The
last coat is treated with an ordinary substratum. For triacetate the gelatin
can be dissolved in formic acid and chloral hydrate, and add to this solution
a mixture of methylene chloride, glycol chlorhydrin and ethanol. <37 >
Superficial hydrolysis of the film before subbing has also been suggested.
Vinyl chloride. Dimitriev<38 > subbed Astralon film by first coating a solution
of 1% perspex in dichlorethylene, then a gelatin-celluloid solution: gelatin
1·8 g, water 3-75 cc, and after dissolving acetic acid 1 cc, methanol 10 cc;
add a solution of 2 g celluloid in 70 cc methanol and 70 cc acetone.
Some patents propose the use of a mixture of gelatin and polyvinyl acetate,
in a layer 2·5 p, thick, then a layer of gelatin, <39 > or a mixture of gelatin and
incompletely esterified polyvinyl acetate. <40 >
Another substratum for vinyl chloride, and for polystyrene, is to coat two
layers of a methacrylate. <41 >
Methacrylate (Perspex) with a low carboxyl group content has greater
adhesive power when it is recovered with a methacrylate with more carboxyl
groups. Fillins <42 > recommends an acrylic emulsion mixed with a gelatin
solution in one or more progressive layers.
Nylon: solution of gelatin in a phenol. <43 > For example: gelatin, water,
m-cresol and formalin in methanol.
Glass plates. The glass is washed in soda and rinsed, before subbing with an
aqueous solution of gelatin and chrome alum, using a wad of cotton or flannel.
Gelatin 0·5 g
Water 100 cc
Chrome alum 10% 1 cc
Optionally 10% of 2 % alcoholic thymol can be added.
Aluminium. Aluminium sheets are subbed by superficial electrolytic oxida-
tion (para. 404) or chemical attack by an acid: phosphoric, molybdic, or
fluosilicic in the presence of ammonium nitrate. <4 4 > Similar treatment can be
used for zinc.
438. Halation
Halation is light-scattering produced by reflection of light rays from the rear
face of the base. It only occurs beyond a certain exposure intensity: the image
of the brightest parts of the subject is more or less spread, and bounded at
some distance by a halo whose outer limit diffuses towards neighbouring
areas.
470 PHOTOGRAP H I C C H E MISTRY
To determine the exposure limit at which halation is produced, Mauge's

method is used. The sensitive layer is placed behind a 12 em wedge with a
constant of 0·5 to 0·6; between the wedge and the sensitive layer is a mask
with a 1 mm slit down the centre. The layer is exposed to light so that
solarization is almost reached on the clear part of the wedge. The developed
material shows an image of the slit which becomes wider at high exposures
(irradiation); after a certain point the image is bordered by two other parallel
bands due to halation, which become bigger and bigger, finally joining to
produce a greatly spread patch.
With an unprotected layer, halation appears at an exposure of about eighty
times the threshold. With a layer having an absorbing backing halation does
not appear until exposures above 3,000 times the threshold are given.
Determination of halation with a screen. Von Kujawa, then Watter( 44h ) have
proposed the determination of halation objectively using a uni-directional
screen together with a sensitometric wedge. The characteristic curves with
and without the screen are compared. If the sensitive layer shows no halation,
the clear lines corresponding to the opaque parts of the screen are quite trans-
parent. In the opposite case, halation has the effect of increasing the density
obtained under the screen. It is stronger as the distance between the two
characteristic curves decreases.
A wedge with a constant of 0·3, or a DIN wedge is used, half of which is
covered by a 20 line per em screen. The wedge- screen-sensitive layer
pack is exposed to a point source, then, after development, the curves are
drawn in the region of D = 1. For colour films, a colour densitometer is used
to determine the halation for each layer. If the halation value is given by the
antilog of the distance between the two curves, the Agfacolor figures are:
Without With
anti-halo anti-halo
Yellow 34 1620
Magenta 4 331
Cyan 3·5 89
Halation is avoided by using bases having a coloured backing or inter-
mediate layer which can be decolorized or eliminated.
439. Anti-halo layers for photographic films

Photographic films always have a backing layer of coloured gelatin. This acts
not only as an anti-halo layer, but also prevents the film from curling.
The dye used in the rear gelatin layer must be readily decolorized by the
developer alkali or sulphite. It is generally an acid dye.
For ortho films it is generally pink, and for pan films, blue, green or yellow-
brown.
Matt backing is obtained by incorporating starch previously pasted with
warm water.
Pink anti-halo. Water 1000 cc, gelatin 110 g, 10% acid fuchsine 60 cc, 5%
chrome alum 18 cc, 5% saponin 4 cc, alcohol30 cc. Coat at 36°C. ·
Green anti-halo. Instead of fuchsine use 100 cc of 5% sulpho green. Mter
development, sulpho green leaves an insoluble greenish residue in the gelatin,
which in acid solution may re-form the dye. It is therefore preferable to use
other dyes including: methyl green (2 g per litre) whose colour is bluish, or
Helvetia or acid green. For blue, Hoechst New Blue, and for violet, Benzyl
violet 4B. <45 >
Acid green is prepared in the following way: 1. Formation of dimethoxy-
triphenylmethane by dropwise addition of cold sulphuric acid to a mixture
of anisole and benzaldehyde in concentrated acetic acid. 2. Oxidation to
dimethoxytriphenyl-carbinol with Pb0 2 in acetic acid. 3. Drying at l10°C
with benzoic acid, and the action of 6-chloro-3-amino benzoic acid. The dye
is extracted with water, and purified by dissolving in NaOH and precipitating
with HCI.
A yellow dye, flavaniline S is decolorized by alkalis. It can be prepared by
heating one part of acetanilide, two parts of aniline hydrochloride and two
parts of zinc chloride to 230-250°C. Boil in water to separate the zinc chlor-
ide. The residue is dissolved in a dilute acid, filtered, and the dye is precipi-
tated with sodium chloride. It is then sulphonated with fuming sulphuric
acid. Flavaniline S is sulphonated IX-p-aminolepidine. (Rowe Index 803).
Azamethine dyes which are decolorized by alkalis are obtained by con-
densing equimolecular parts of aromatic or heterocyclic aldehydes with
substituted amines, then combining with organic acids containing at least
one salt-forming -OH or -CO . OH group. <46 >
Sheppard and Houck< 47 > have disclosed dyes of the murexide type of which
the most common is the ammonium salt of purpuric acid. These dyes are
decolorized in acid fixers with a pH of 4 by tautomeric transformation to the
keto derivative which then hydrolyzes.
By condensing pyrazolones, rhodanines, oxindoles, etc. with 1 : 3-diketones
in a solvent, decolorizable oxa-oxythrimethine dyes are obtained. <48 >
Yellow-brown anti-halo. Permanganate is reduced by organic materials to
the brown dioxide. A yellow-brown anti-halo layer which is very effective is
readily obtained by adding an alkaline permanganate solution to a warm
gelatin solution <48b> containing an organic reducer (glucose or tartaric acid).
It is best to noodle and wash the mass, and add further gelatin before
coating.
440. Anti-halo layers for cine films

Cine films have no gelatin backing. The coloured anti-halo layer is applied as
a backing varnish soluble in the developer or in a solvent which does not
affect the base, or as an underlying layer.
The backing varnish is grey-violet, blue-grey or black. The interlayer can
be made of brown or black silver dispersed in a colloid. It is only used for
reversal films.
The backing varnish must be soluble in the developer, but not in plain
w_ater, and must be sufficiently resistant in a thin layer. It is applied from a
solution in an organic solvent. A suitable varnish can be made from de-waxed
or hard shellac in alcohol, polyvinyl phthalate in butyl acetate, <49 > a poly-
acrylic acid or a polystyrene-maleic acid. (49b>
Agfa anti-halo backing varnishes which are non-decolorizable were made
of gelatin in an organic solvent:
Grey Blue
Gelatin 660 g 660 g
Water 1·32 I 1·321
Phthalic anhydride (10% in metl,lanol) 1·25 I 1·25 I
Methanol 721 771
Acetone 111 111
Baryta white 51
Lacquer black extra 80 g 9 ·3 g
Flavazines E + G L extra cone. 57 g
Rhodamine Ponceau GG extra 1·6 g
Aniline blue BB 13·4 g
The dyes are previously dissolved in alcohol.
A colorizable backing varnish is based on a co-polymer of maleic anhydride
and vinyl ester (Povimal BA).
Nitrate Acetate
Povimal BA 487 g 609 g
Isopropyl alcohol 50 I
Isobutyl alcohol 50 I 25 I
Methyl phthalate 80 cc 100 cc
Ethanol 75 I
Acid green (para. 438) 324 g 405 g
It takes two hours for the resin to dissolve at 65°C.
Anti-halo dyes are produced by coupling a phenolic resin with a diazonium
compound, the resin having in the para position to the hydroxyl a replaceable
H which can couple with the azo group. <50 > The same resins can be combined
to give indophenol blues. <51 >
Dyed base. The anti-halo backing varnish of negative and miniature cine
films is often replaced by dyeing the whole base grey, blue-grey or violet-
grey.
Reversal films. The backing layer of a reversal film may be a varnish which
is developer-soluble or is decolorized in the oxidizing reversal bath. When an
under-layer forms the anti-halo layer the colouring matter is usually colloidal
silver, thickness 2 f-1-·
The brown colloidal silver is obtained by reducing a gelatinous solution of
silver nitrate with amidol then setting and washing. Black colloidal silver is
produced by reducing silver hydroxide, formed by pouring silver nitrate into
a caustic solution of dextrine, with hydroquinone. After adding gelatin, the
mass is washed. It can also be prepared by developing a fogged photographic
emulsion.
441. Anti-halo backing for plates

A plate-backing must be readily soluble in the developer, and must not prev-
ent the plates from being cut. Furthermore, it must be readily applied to the
plates and must not dirty the developer. These various requirements rule out
gelatin, dextrine, cellulose derivatives and other colloidal substances.
Ordinary and ortho plates are backed with an alcoholic solution of rosolic
acid (orange red). Rosolic acid is a trihydroxytriphenyl carbinol.
The addition of a green dye, very soluble in alcohol and non-crystallizing
such as naphthalene green, to rosolic acid, enables very dark, almost black,
layers to be obtained, which are suitable for panchromatic plates.
The backing is brighter and more resistant to rubbing if 0·5% ammonia is
added.
442. Antistatic layers

The greatest source of chance troubles in the manufacture of photographic
layers is the formation of discharges of static electricity.
The coated film is charged by rubbing, and is the parting of two layers or
a strip on an insulating roller which produces flashes.
The polarization of a film is made up of the residual charges resulting from
the influence of an electric field. This polarization can be measured on the
two sides of a film independently of any temporary charge, with an electro-
static voltmeter. <Sib)
The potential resulting from reeling an acetate film at a speed of 90 feet per
minute under a mechanical tension of 1 kg reaches 4-5 kV. The polarization
potential is below this value, but sparks are produced when the polarization
charges accumulate on the successive layers of a roll of film.
The flashes are mainly produced during slitting, inspection and reeling.
Manual inspection should be avoided as it causes a large number of these dis-
charges.
Precautions are generally taken during the manipulation of films: humidifi-
cation of the air, earthing the machines, rubber rollers made conducting by
incorporating graphite, brushing a film with 'angel's hair' in aluminium joined
to earth. These precautions are not very effective; they are not always carried
out, and furthermore, the discharged film can be immediately recharged and
produce flashes in the camera or on rapid unwinding before development.
Static discharge is not produced in ionized air. Unfortunately neither the
electrically produced corona effect, nor ionization by IX-rays from polonium,
or with a flame, can be used with films due to the danger of fog and the diffi-
culties of the systems.
The only practical way of avoiding flashing is to use an antistatic base, that
is, one which is difficult to charge.
One objectionable process is to keep moisture in the emulsion, with glycerin
or a hygroscopic salt like lithium chloride. A more interesting method is the
application to both sides of the film of a quaternary ammonium salt like tri-
methyloctadecylammonium methyl sulphate in an organic solvent, <52 > or
sodium ethyl phosphate dispersed in cellulose-di-n-butylamine sulphate. <52b>
Superficial hydrolysis of the base with alkali has been disclosed by Stinch-
field. <53 > It is preferable, however, to apply a surface film of a different type.
For example, benzyl cellulose, ethyl cellulose or cellulose nitroacetate on
nitrate, or for acetate, polymerized carboxylic acids< 54 ) such as polyacrylic

acids, cellulose carbamates, <55 ) abietic esters, <56 ) zein (maize casein), <57 ) etc.
Acrylic antistatic layer. This is based on a mixture of 60% polymethyl
methacrylate (CH 2 = CH-CO. OCH 3 ) 0 and 40% polyacrylonitrile
(CH 2 = CH-CN)m, partially saponified until it has adequate solubility.< 58 )
The resulting resin, called Meniviskol, is dissolved in four hours at the boil:
methanol 19·31., water 41., N caustic potash in methanol 6·671., Meniviskol
1·33 kg. For use take 23·71. of this stock solution and 2111. of methanol.
Cellulose acetomaleate antistatic layers. <59 ) The starting material is a 44-45%
acetyl cellulose acetate (Serikose) prepared by hydrolysis of triacetate with
sulphuric acid. To maintain a high molecular weight for the acetate, the
acetylation temperature must be kept relatively low, maximum 50°C (cf.
para. 420). The hydrolyzed acetate is treated for 3 hours at 100-105°C in the
following mixture: maleic anhydride 23 kg, citric acid 8 kg, triacetin 10 kg,
cellulose acetate 17 kg. After cooling, the product is precipitated with water,
washed and dried.
One kg of this resin is dissolved in 15 1. of distilled water and 25 1. toluene
below 75°C, then a further 140 1. toluene and 45 1. distilled water is added.
The resin is then partially saponified by adding 2· 5 1. of N /2 caustic soda.
The solution is decanted after 16 hours, and filtered before being applied to
the base.
443. Anti-abrasion layer

The photographic emulsion, coated on paper or film is generally re-coated
with a thin layer of gelatin a few microns thick.
Films are coated, after the emulsion is applied, with:
Water 11
Gelatin 30 g
27°C Alum, 5% 10 cc
( Saponin 5% 5 cc
Alcohol 280 cc
444. Stripping layers

Some photographic layers are coated on temporary supports, so that they
can be transferred after development, to permanent supports, for example,
in photogravure.
The temporary support is generally paper, but may be acetate sheet. The
paper is first coated with a layer of nitrocellulose< 60 ) which is subbed. Above
this, a gelatin or gum arabic adhesive layer is coated, containing a little gly-
cerin. The permanent support consists of a relatively thick layer of nitro-
cellulose. This is subbed and coated with emulsion. Mter development the
emulsion can be detached from its temporary paper support by prolonged
immersion in water.
Another system is to coat the paper first with gum dammar, which is water-
proof, then with emulsion, and finally with nitrocellulose (which is the final
support). This nitrocellulose layer is itself coated with a thermoplastic
resin, <61 > vinyl acetate, for example. By hot pressure against a metal plate, the
resin sticks, enabling the paper to be removed.
A temporary triacetate support, covered with 20 fL of nitrocellulose, then
with the emulsion, enables dry stripping to be carried out, after surface
lacquering.
445. Two-colour backing paper

The two-colour backing paper for roll-film is lacquered on the green-, red-,
grey- or yellow-coloured side.
The figures and instructions are first printed: in a dark colour with a gum-
arabic base ink containing solanthrene blue or carbon black, or in a light colour
with a gum-arabic ink containing very fine titanium white. A kilo of ink con-
taining 180 g of blue pigment (previously ground with a little glycerin) can
print 10,000 m of 6·5 em wide paper.
The printed face is then protected on the same machine with a layer of
lacquer: nitrocellulose in acetone and butyl acetate, zein (maize casein) in
alcohol, polystyrene plasticized with octyl phthalate in trichlorethylene, etc.
Lacquered backing paper must be tested for inertness towards the emulsion
by an oven test. The printed figures must not be transferred onto the emul-
sion, and the increase in fog must be practically nil, compared with a similarly
treated blank without the backing paper. It should be noted that excessive
activity can result from poor quality paper pulp.
446. Film splicing

Cellulose nitrate films are readily spliced with a solution of celluloid in a mix-
ture of acetone and amyl or butyl acetate. The emulsion must be scraped off
first.
Acetate films of 56% acetyl and below need a solution of acetate in a mixture
of acetone and ethyl acetate. Other solvents are methyl ethyl ketone (B.Pt.
79°C), cellosolve (B.Pt. 115- 130°C) and cellosolve acetate (B.Pt. 138-145°C).
For triacetate films (56 % and over) a mixture of methylene chloride and
alcohol must be used. Add a little toluene if necessary.
Splicing acetate films without cement. Herzig<63 > has described a welding
process of joining end to end, without scraping or overlapping. The necessary
apparatus has a nichrome band heating element of 16 W fern. The films to be
joined are pressed against the band with a pressure of 14 kgfcm2 • A mica
sheet insulates them from the teflon pressure plate. It is advisable to moisten
the ends of triacetate with plasticizer to compensate for evaporation.
Splicing terephthalate (Cronar)films is done with an adhesive Mylar ribbon,
without scraping. The joint resists 1000 projections. <6 4 >
447. Film cleaning

Carbon tetrachloride, which is normally used for cleaning developed films< 65 >
can be advantageously replaced by Freon 113, which is a fluorinated hydro-
carbon with the formula C. ClF2 - C. Cl2F. It is volatile, non-flam and
almost non-toxic. As a powerful organic grease-solvent, it can cause irritation

to the hands if used without gloves.
The film can be protected at the same time as it is cleaned by adding 0·1%
beeswax or cetyl alcohol to the solvent. A recommended mixture includes
0 ·03% Carnauba wax, 0·025 % beeswax and 0·075 % ethyl cellulose.
447b. Protective lacquers
The purpose of using protective lacquers on prints is to protect them against
abrasion and chemical action.
The old recipes are all based on natural resins, which have the disadvan-
tages of being either brittle or soft and sticky: dammar 10 g, benzine 50cc,
carbon tetrachloride 50 cc; or sandarac 100 g, castor oil 1 g, alcoho to
1000 cc (with the optional addition of 50 g benzoin). For hot lacquering:
sandarac 55 g, bleached shellac 83 g, castor oil 20 g, turpentine 10 cc, alcioho
to 1000 cc. For an opalescent layer: sandarac 103 g, mastic 23 g, ether 1000
cc, benzine 25-750 cc depending on the opalescence desired (very in-
flammable lacquer).
For retouching: clear colophony 230 g, dammar 100 g, mastic 23 g, lavender
oil 1 g, turpentine 1000-2000 cc-or sandarac 113 g, lavender oil 85 cc,
alcohol 800 cc (matt the dry layer by rubbing, after powdering with pulver-
ized colophony if desired).
The synthetic resin industry now offers a wide range of products from which
excellent varnishes can be made: transparent phenolic resins which are
alcohol soluble, coumarone, glycerophthalic, maleic and acrylic resins, etc. For
example, Alresate 177 dissolved in toluene or solvent naphtha gives a tough
film whose properties can be modified with a plasticizer (para. 425). The
coumarone resins are soluble in benzene and carbon tetrachloride, sometimes
in acetone; the methacrylates in acetone, ethyl acetate and benzene; poly-
styrene in all chlorinated solvents; polyvinyl acetate in alcohol, ethyl acetate
and the chloro solvents; polyvinyl acetals in alcohol, acetone, ethyl acetate and
benzene; polyvinyl chloride in dichlorethylene; chlorinated rubber in ethyl
acetate, benzene and dichlorethylene; the alkyd resins, simple or modified,
in acetone.
Resins which are too soft should be avoided as they give tacky layers: this
happens with polyvinyl acetate, which is preferably replaced by a polyvinyl
acetate-chloride copolymer.
The cellulose esters can give lacquers with interesting properties: nitro-
cellulose, cellulose acetate and benzyl cellulose in particular. Nitro-cellulose is
compatible with co pal gum (Manilla) in methanol, butanol and cellosolve;
with Kauri gum in methanol, butanol and butyl acetate, with dammar and
mastic in butyl acetate and solvent naphtha. It is also compatible with
phenolic resins like the Albertols, some maleic resins (Synresols) and the
pentaerythrole esters. The solution may contain a plasticizer (such as castor
oil). Plasticized benzyl cellulose gives flexible glossy films; it is soluble in a
mixture of 90 parts toluene and 10 alcohol.
The following formula (66) contains a vinyl copolymer. To avoid yellowing,
PHOTOGRAPHIC BA S E MATERIALS 477
an ultra-violet stabilizer has been added: 2 : 2'-dihydroxybenzophenone
with triethanolamine. The plasticizer is tricresyl phosphate. In this case,
nitrocellulose is included to enhance adhesion.
Cellulose nitrate ('half-second' viscosity) 1
Vinylite VYGC (40 % solution in butyl
acetate) 6·3
Tricresyl phosphate 2
Butyl acetate 6
Butyl alcohol 1
Ethyl acetate 1
Ethanol 1
Toluene 15
Triethanolamine 1·6
2 : 2'-dihydroxybenzophenone 0·1
Microcrystalline wax (not specified) 0·3
Vinylite VYGC is manufactured by Union Carbide and Carbon Co.
Geon (or Breon) 652 emulsion (Goodrich Chemical Co.), made from poly-
vinyl chloride and butadiene-nitrile rubber, gives transparent, glossy, supple
films by simple application, but they are not sufficiently resistant to rubbing.
Fungicide for tropical countries. t67 > Treat negatives for archives in 0·5- 1%
zinc fluosilicate solution for 3 minutes and dry. Zinc fluosilicate is very poison-
ous and contact with the skin must be avoided. Avoid direct handling of
treated negatives by a very clear warning. The method is not applicable to
papers because of yellowing.
448. Mountants
To stick paper to plate glass or metal plates, use the following mixture:
Gelatin 60 g
Syrup (sugar) 60 g
Glycerin 60 g
Chrome alum 1g
Water to 1000 cc
The alum is dissolved separately in a little cold water. Amount used:
40-50 cc per sq. ft. The liquid sets after about 24 hours and cannot be re-
melted.
Cold soft adhesives
A B c D
Hercolyn (methyl dihydro abietate) t68 > 42 40 40 38
Hydrogenated colophony 50 50
Rubber 10
Ordinary colophony 52
Ethyl cellulose 8 8
Dammar 50
Chlorinated rubber 12
Microcrystalline wax 10
The Hercolyn and hydrogenated colophony are heated to 140-160°C. The

ethyl cellulose is added slowly with stirring.
Hot adhesive. An acetate film 0 -06 mm thick covered with a hot adhesive
substance is commercially available (Kodak).
A recommended plastic mixture includes Hercolyn 42p, Staybelit No. 10
SOp, ethylcellulose 8p, and microcrystalline wax 5-20p. Staybelit is an
hydrogenated colophony. (68>
448b. Stripping negatives

To transfer a film image to glass, the image is first stuck onto a subbed plate
with liquid 10 % gelatin containing 2% formalin under pressure. After
drying for 24 hours, the backing is removed in 40% caustic soda at 50°C, or
better, in sodium hypochlorite. Rinse, blot, then dissolve the base in acetone,
ethyl acetate or methyl cellosolve. Rather than stick the negative directly
onto the glass, the image can merely be protected by applying several layers
of rubber (in benzene solution). By sticking a sheet of paper under, double
transfer can be effected.
Sterry process. A negative on film or glass can be stripped in the following
way: immerse the negative in potassium carbonate 40 g, 40 % formalin 25 cc,
glycerin 20 g, water to 1000 cc for 30 minutes. Drain and dry. Cut around
the border to the base 2 mm from the edge. Immerse the negative, treated
thus, in 5% hydrochloric acid, which results in the formation of bubbles of
carbon dioxide. Apply under water to the image side a sheet of moistened
sulphided paper. Remove the pack and squeegee out the air bubbles and
gently strip off the paper at an angle, carrying with it the image layer. Trans-
fer to a second paper immersed in a dish full of water. Remove excess liquid
with a roller and strip off the first paper. The image can then be re-transferred
to a glass plate coated with a warm 3% gelatin solution.
Hydrofluoric acid process (for negatives on glass). Cut all round the image
and 3 mm from the edge. Place the plate on three levelling screws, and pour
onto it a solution of: alcohol 25 cc, water 1 cc, glycerin 1 cc (stock solution)
+ 6-30 drops of hydrofluoric acid (just before use). Spread the liquid with a
piece of paper. After a minute, test an edge to make sure the gelatin is free,
then pass a waxed wire (stretched on a bow) between the image layer and the
glass. Pour on some stock solution (without acid) and then apply a sheet of
waxed paper under light pressure. Remove the paper plus image from the
original glass, and transfer the image to a gelatin-coated plate. A second
transfer enables the image to be reversed.
A variation is to immerse the plate for 8 hours at 12 oc in a solution at pH 8
containing 1·2% acetic acid, 1·64% sodium acetate and 0·2% hydrofluoric
acid. <69 >
Hydrofluoric acid is dangerous to handle. It is sometimes replaced with
4% sodium fluoride mixed with half its volume of formalin. Transfer is
carried out in water.
Strengthening the image layer by applying a layer of gelatin or collodion
(plunged into water before drying to make it permeable) is advised.
Transfer onto talc-powdered glass enables the image layer to be detached
finally.
Stripping collodion negatives. Strengthen with a layer of rubber, then
collodion. Cut round 5 mm from the edge. Apply moist paper with a roller.
Detach the paper + image layer, starting at an angle, and helping with the
point of a knife. Transfer to another moist paper then onto gelatin or gum-
coated glass.
1. Michel-J affard R.: La fabrication des pates a papier, Bull. Inst. Chimie de Paris,
Jan. 1938, 6.
1b. Melamine is a triaminotriazine of the urea family, formed from 3 [ = N -C(NH 2 )
= groups joined in a six-membered ring. It reacts with formalin to give first
a methylolamine = N -C(NH. CH 2 0H) =
2. SeveR.: Resume Trav. Lab. Kodak, Jan.1955, 251; Sci. et Ind. Phot., 1955,145.
3. Kodak-Pathe: F.P. 970,208 (1950).
4. Jallander 1.: Nature, 1948, 300.
5. B.I.O.S. Trip No. 2133, Report II, 29th April 1947. H.M. Stationery Office,
London.
6. Knipe G. F. G. and Reid J. B.: Proc. Roy. Soc., 1943, 81, described a double
monochromator with cells isolating the X, Y and Z regions of the C.I.E. colori-
metric system, which is intended for the control of almost white papers.
7. Rowen]. W., Hunt C. M. and Plyler E. K.: Jl. Res. Bur. of Standards, 1947,
133-140.
8. Popov R. V.: S.R. Acad. Sci. U.R.S.S., 1945, 325.
8b. Pakshver A. B. and Kopolnikova G. P. : Zh. Prikl. Khimii, 1951, 1052.
8c. Process of the I. G. Dormagen works (Germany). Final Report No. 262, London,
H .M. Stationery Office.
8d. F .P. 755,981 (1933), 809,867 (1935).
9. B.P. 161,564 and 167,143 (1921)-U.S.P. 1,425,580/1 (1920), F.P. 672,220 (1929)
and 820,270 (1937).
9b. Kodak: F.P. 834,554 (1938); Ind. Eng. Chem., 1949, 695-701.
10. Kodak: U.S.P. 2,208,569 (1937).
11. F.P. 653,742 and Add. 35,278 (1928); U.S.P. 2,097,954 (1934); 2,113,304/5
(1935). Fordyce C and coil.: Ind. Eng. Chem., 1936, 1310.
12. Sato H., Godai R. and Kodama H.: Konishiroku Rev., 1953, 1-32 (in Japanese).
13. U.S.P. 2,093,462.
14. U.S.P. 2,186,631/2 (1939).
15. U.S.P. 2,196,746/49/51 (1938).
16. U.S.P. 2,211,327 (1939).
17. U.S.P. 2,231,729 (1939).
18. U .S.P. 2,234,706 (1940).
19. U.S.P. 2,253,064 (1938).
20. U.S.P. 2,253,065 (1938).
21. Camphor is a cyclic ketone derived from borneol. Natural camphor is extracted
from taurus camphora from Japan and China. Synthetic camphor obtained from
turpentine whose hydrochloride is converted to bornyl acetate then borneol, is
more frequently used. The latter is oxidized to camphor.
22. Maim C. J., Fordyce C. R. and Tanner H. A.: Ind. Eng. Chem., 1940, 1052;
1942,430. GloorW. E. and Gilbert C. B.: Ind. Eng. Chem., 1941,597.
22b. Kodak: U.S.P. 2,336,310 (1941) and F.P. 1,078,989 (U.S. prior. 1951).
22c. Carver E. K. and Kodak: U.S.P. 2,168,972 (1937).
23. The solubilities of the acetates given here refer to compounds having an acetyl
content of 56 % at most. The triacetates which are more completely esterified are
more difficult to dissolve.
24. Kodak-Pathe: F .P . 865,189.
24b. Kodak-Pathe: F.P. 838,071.
24c. Calhoun M . : Photogram. Eng., 1947, 163. Fordyce C. R. , Calhoun]. M. and
Moyer E. E.,J.S.M.P.T.E., 1955,62-66.
25 . Sasai A.: Jl. Soc . Phot. Japan , 1951, 109.
26. Setchkin N. P.: Jl. Res. Bur. Stand., 1949, 591-608.
27. Hutchinson, Ellis and Ashmore : Sci. et Ind. Phot., 1948, 435 .
28. Filter paper impregnated with 0 ·1% alizarin red containing 2% ammonia, dried
and heated for 10 minutes in an oven to eliminate the ammonia.
29. Gansel E . : P .S .A. Jl., 1952, 82.
30. Genung L. B.: Anal. Chem., 1950, 401.
31. Genung and Mallatt : Ind. Eng. Chem., Anal. ed. , 1941, 369.
32. Cramer, G ardner and Purves: Ind. Eng. Chem., Anal. ed., 1943, 319.
33 . Whitnack G. C. and St. Clair G anz : Anal. Chem., 1952, 1060.
33b. White D. R . and coll.:J.M.S.M.P.T.E., 1955,674-678.
33c. Du Pont: F .P . 1,084,387 and 1,086,433 (1955) disclose the Li, Na and Ca
hydrides and the organic salts of Col, Mg and Zn.
34. A Schleussner formula uses : stock solution-gelatin 54 g, water 54 cc, acetic
acid SO g, methanol 700 cc. To sub acetate take stock solution 140 cc, methanol
240 cc, acetone 700 cc. When this formula was tried a white deposit was produced
on the film.
35 . U .S.P. 2,066,850.
36. B.P. 545,905.
37. Recono K. Ges. Stock and Co.: F.P. 894,789 (1943).
38. Dimitriev V. K.: Poligraf Proizvodstvo, 1951, 1214.
39. N adeau G. F . and Eastman-Kodak: U.S.P. 2,169,004 (1938) .
40. N adeau G . F. and Stark C . B.: F .P . 943,135 or 945,135 (1945).
41. liford: B.P. 573,917.
42. Fillins and Kodak-Pathe : F.P. 970,208 (1951) .
43. Middleton E. B., Queen D. McM. and Hall J, R. (DuPont): U.S.P . 2,341,877
(1940), B.P. 552,085 (1941).
44. Cartwright, H aigh and Smith : B.P. 545,942 and 548,716 (1940/41) .
44b. Von Kujawa: Sci. et Ind. Phot., 2(2), 411. Watter 0. (Agfa) : Bild und ton, 1954,
7, 326; 1955,8, 8; Sci. et Ind. Phot., 1955, 133 .
45. These dyes are not commercial ones. Their Rowe Colour Index Nos. are:
Helvetia Green No. 660, Hoechst New Blue No. 708 (dimethyl-diphenyl-diamino-
sulphofuchsone) , Benzyl violet 4B No. 697 (dibenzyl-diethyl-dimethyltriamino-
triphenyl-carbinol disulphonate).
46. Gavaert: F.P. 894,181.
47. F .P. 827,126.
48. Gaspar B.: F .P. 854,975 (1939).
48b. The dioxide can also be precipitated in dextrine, before adding gelatine solution.
49 . F .P. 852,992.
49b. F .P . 886,651.
SO. Collins R. B.: B.P. 545,529.
51. Collins R. B.: B.P. 546,631.
51 b. Tyler, Webb and York (Kodak): Jl. App. Phys. , 1955, 61-68. An electrostatic
charge detector is sold by Ste. AOIP, Paris.
52. I.G.F . : F .P . 894,097 (1942).
52b. Kodak: F.P. 1,089,923 (U.S. prior. 1950).
53. U .S.P. 1,683 ,315 (1926).
54. I.G.F.: G.P. 604,456 (1932); Kodak: F.P. 1,084,777 (1954) .
55. DuPont: U.S.P. 1,703,470 (1927).
-56. Kodak: U.S.P. 1,687,041/2 (1927).
57. Kodak: U.S.P. 2,338,664 (1940).
58. (Agfa formula): B.I.O.S. Final Report, 1355, 1945, London, H.M. Stationery
Office.
59. (Agfa formula): B.I.O.S. Final Report, 1355.
60. Nadeau G . F. : U .S.P. 2,143,791.
61. Hart and Lee: B.P. 566,832 (1943).
62. Kodak-Pathe : F.P. 977,567 (1942).
63. Herzig L.A.: J.S.M.P.T.E., 1953, 181-188.
64. Holm W. R. : J.S.M.P.T.E., 1955,5.
65. Also isopropyl alcohol.
66. Ranger H. 0.: P.S.A. Jl., 1953, 23-27.
67. N.*: Bull. Trop. Kodak Labo., 1951, 10.
68. Hercules Powder Co. (U.S.A.).
69. Dahanayaka C.: Nuovo Cimiento, 1955,1251.
INDEX
Accelerators, development, 108 Antipanog, 377
ripening, 287, 307 Antiseptics, 381
Acetyl cellulose, h ydrolyzed, sensitiza- Antistatic layers, 473
tion, 364 Arginine, 281
Acid-alcohols-developers, 128 ASA system for negative materials, 235
Acriflavine, anti-sulphide agent, 104 -system for papers, 253
Adhesives, 477 Ascorbic acid developers, 129
Adrenaline, developer, 115 Aspartic acid, 274
Adsorption of d eveloping agent, 49 Atomal, 99, 123
- to the crystal surface, 21 Aurothiocyanates, preparation, 320
After-ripening, 311 Autoradiography, 407
Agitation, of developer, 102, 229 Aza-indolizines, 378
Air bells, 108
Alanine, 274
Albumen, egg, 307 Baryta coating, 445
Aldehydes of gelatin, 288 Bas-relief effect (contour), 435
- alcohols, developers, 128 Bases, heterocyclic, developing agents,
Alkalis for developers, 62 127
-cellulose, 455 Becquerel (effect), 216
Alkali halides, 23 Benzene sulphinates, 377
Alkyl sulphate wetting agents, 384 Benzotriazole, 375
Aluminium, oxidized, 431 Benzoylacetic acid, 468
Alums, estimation, 163 Berchtold process, 437
- chrome, 148 Binding, 443
- chrome, in emulsions, 382 Bisulphite, 63
-potassium (ordinary), 148 -analysis, 138
Aminoacetic acid ethyl ester, developing - for latensification, 34
agent, 129 Blocking theory, 211
Amino acids, 273 Borates, analysis, 139
Aminonaphthols, 121 Borax, 62
Aminophenols, developing agents, 117 Boric acid in fixers, analysis, 163
- analysis, 137 Bose-Einstein statistical law, 7
Aminotetrahydroquinaldine, 100 Brilliance of paper, 228
Ammoniacal salts, estimation m fixers, Bromothiocyanate emulsions, 215
163 Bromide, action of, 55
Ammoniacal fixers, 150 - analysis in developers, 140
Analysis of emulsions, 324 - - i n fixers, 163
- of cellulose esters, 464 -fixing bath, 150
-of developers, 132 -silver, without colloid, 299
-spectrophotometric (developers), 137 Brownian movement, 269
Antiabrasion layers, 474 B.S.I. system, 236
Antifiavog, 79, 377
Antifoggants (use of), 379
-organic, 374 Cadmium, effect of salts, 318
Anti-frothing agents, 385 Calendering, 446
Antihalation layers for cine film, 470, 471 Callier coefficient, 201
-for plates, 472 Carbazones, phototropes, 17
R 483
484 INDEX
Carbonate, estimation, 138 Copper, effect of salts, 318

- potassium, 62 - in developers, 104
-sodium, 62 Copyrapid, 435
Carboxymethylcellulose, 455 Cronar, 464
Carboxythiazolidines, anti-foggant, 377 Crystals, characteristics, 21
Caustic potash, 63 -mixed, 21
Celloidine, 360 Cupricitrate, ammonium, 430
Cellophane, 464 Curve frequency, 307
Cellulose, acetates, 449 . - characteristic, 203
- acetobutyrate, 452 - characteristic, equation, 205
- acetopropionate, 452 - characteristic, shape, 207
- constitution, 441 Cyanide fixer, 151
- esters, analysis, 463 Cyanotype, 427
-ethers, 455 Cysteine, 281, 315
-nitrate, 455 Cystine, 281
-phthalate, 455
- preparation, 450 D.23, 97
-raw materials, 452 D .25, 97
- sensitized, 364 D .76, 94
- triacetate, 451 D acron, 464
Celon E, 104 D ammar, 475
Cemulsols, 384 Decomposition, photochemical, 15
Centres, F , 23, 25 Defect in development, 108
- of sensitivity, 25 - Frenkel, 24
Charge of developer, 57 - of the crystal lattice, 23
Chloranol, 72, 128 -Schottky, 24
Chloride, silver, 20 Deformation of developed layer, 165
Chlorobromide emulsions, developers, 79 - of film, 461
Chlorohydroquinone, 100, 114 D ensitometers , 225
Chromatography of developers, 143 - reflection, 227
Clayden effect, 215 Density, 200
Coating, 475 - effective, 202
Cobalticyanide, potassium, 430 - extreme (reduction of), 254
Cobaltioxalate, ammonium, 430 - measurement, 225
Collagen, 280 - reflection, 202
Collastromine, 280 -variable, recording, 257, 262
Collodion, see Emulsion. D ensographe, 225
- for films, 457 Depolymerization, photochemical, 15
-dry, 360 D esensitizer, contrast modifiers, 287
-wet, 358 Developer:
- viscosity, 459 -analysis, 132
Compensating developers, 73 - borox, 94
Compton effect, 9 - caustic, 76
Concentration of silver ions, measure- - cine positive, 76
ment, 370 - for chlorobromide emulsions, 79
- of silver and bromide ions, 369 - composition, 60
Contagious effect, 73 - compensating, 73
Contrast, 203 - contrast, 76
- as a function of grain, 306 -energy, 65
-developers, caustic, 76 - exhaustion, 1OS
- developers, for emulsions, 76 -fine grain, 94 to 100
- modifiers, 287 - inorganic, 81
- variable (papers), 255 - internal image, 86
Control of washed images, 160 -for nuclear emulsions, 413
Cooking, gelatin, 293 - paraphenylenediamine, 98
INDEX 485
Developer-contd . Eberhard effect, 230

- physical, 86 Eder's reaction, 16
- preparation, 63 Eder-Hecht, 234
- reversible, 84 Edinol, 118
-storage, 105 Effect, Becquerel, 216
- surface, 85 - Clayden, 215
- tropical, 74 - Eberhard, 230
- ultra rapid, 109 -Herschel, 216
- warm black tone, 79 -intermittency, 215
- warm tone, 79 - Kostinsky, 230
Developing agents, identification - photoelectric, 9
characteristics, 112, 141 - Pockets, 257
-chromatography, 143 -Raman (Emulsions for), 214
- combined, 72, 128 -reversal, 215
Developing functions, 11 2, 11 7 - Russel, 41 5
D evelopment accelerators, 55 - Sabattier, 217
- centres, 48 - Sterry, 254
-continuous, 105 - Villard, 215
- and fixing, 157 - Weigert, 217
- physical, 86 Einstein's Law, 12
- theory of, 49 Electricity, static, 461
- ultra-rapid, 109 Electrolytic theory of development, 50
Dialkylanilines, 124 Electrofax, 437
Diamines developing agents, 124 Electromagnetic waves, 7
-substituted, 124 Electrode potential, 42
Diaminodurene, d eveloping agent, 68 Electrons (action of), 406
Diaminophenol develop ers, 125 Elon, see Metol
- formulas, 68 Emission of rays, 8
- hardening, d evelopers, 74 Emulsion fog, 218
- preparation, 126 Emulsions, acid, 329
Diaversal, 435 - ammonia, 331
Diethyl-p-phen ylen ediamine, 124 - ammoniacal, 332
Differentiation of traces, 414 - analysis, 324
Diffusion, 238 - auto-positive, 355
Diglycocolle, combined d eveloping - bromide, for ordinary papers, 339
agents, 99 - bromide, for rapid papers, 339
Dihydroxyketone hardeners, 382 - bromothiocyanate, 216
Dihydroxymethylurea, hard ener, 382 - Brovira, 340
Dimethyl-hydroquinone-pyridine, 115 - cadmium, 353
Dimethyl-p-phenylene-diamines, 124 - celloidine, 360
DIN, system, 233 - chloride, 350
Diogen, 121 - chlorobromide, 343 to 350
Diphenol, 118 -citrate, 357
D iphenylamine, anti-foggant, 374 -coating, 386
Diphenyliodonium, 377 - cobalticyanide, 355
Dissociation, photochemical, 13 -collodion, 358
Distribution of grains, 293 - double coated, 335
Dithiopyrimidine, retarder, 307 - 'double jet', 329
Dithioquinazoline, retarder, 307 - drying, 387
Document paper, 254 - for electrons, 407
Dodecylpyridium, 56, 57 -industrial manufacture, 321
Drying processed material, 165 - Lippmann, 365
Duclaux and Jeantot process, 374 - Lupex, 352
Duplicate negatives, 246 - mixtures, 335
Duration of development, 102 - negative, 327
R•
486 INDEX
Emulsions, acid-contd. Fog-contd.

- neutral, 327 -sulphide, 104
-nuclear, development, 412 - with age, 219
- polyvinyl alcohol, 363 -yellow, 108
- positive, ammoniacal, 338 Fogging agents, 217
-positive, neutral, 337 Formalin hardener, 382
- powdered, 323 Frenkel defects, 24
- preparation, 298 Friction, 33
-print-out, 356 Fuchine, acid, for anti-halo, 470
-semi-ammoniacal, 334 Fulgides, phototropic, 1 7
- setting, 309 Fungicide, 476
-slow, 337
-sound recording, 260
-types, 302
- viscosity, 385 Gallic acid, 116
Endothermic compounds, 421 Galvanometer, ribbon, 257
Energy of radiations, 11 Gamma, 203
- of developers, 65 - infinity, 203
Esculine, 316 Gamma radiography, 405
Ethylene-diamine tetraacetic acid, 82 Gels of gelatin, 272
Eurekine, 123 Gelatin, 386
Exhaustion of developers, 105 Gelatin active, 313
Exposure, 200 - choice of, 313
-auxiliary, 33 -concentration, 313
- constitution, 278
- deactivation, 293
F-centres, 23, 25 - demineralization, 294
Fat in gelatin, 288 - hydrolysis, 277
Fermi-Dirac law, 7 -inert, 313
Ferricitrates, 430 - manufacture, 291
Ferricyanide, potassium, 427 - mineral content, 290
Ferrioxalates, 427 - molecular weight, 278
Ferrocitrates, 82 - photographic, 280
Ferrogallate process, 423 - practical examination, 289
Ferrograph, 438 -reducers, 288
Ferromalonates, 82 - retarders, 313
Ferro-oxalates, 82, 427 - solvents for, 270
Filaments of the developed grain, 51 - structure, 279
Film base, 467 -surface tension of solutions, 271
Film-base casting, 459 - swelling, 271
Film cleaning, 475 - viscosity of solution, 271
Films, physical tests, 462 Glazing, 167
Finishing of emulsions, 381 Globulines, 277
Fixers, acid, 152 Glucopyranone, 441
-analysis, 161 Glutamic acid, 274
- hardening, 153 Glutathion, 281
Fixing, 154 Glycin, 123
-rapid, 156 -developing solutions, 67
-theory, 151 -estimation, 137
Fluorescence, 17 Glycocolate developers, 84
Fluorescent layers for U.V., 395 Glyoxal, hardener, 382
Fluorescent reinforcing screens, 403 Gold intensification, 36
Fog: aerial oxidation, 63, 218 - sensitization, 318
- inhibitors, 289 Goldberg densograph, 225
- physical, 219 G.O.S .T. system, 234
INDEX 487
Grain, structure of developed, 51 Internal latent image, 31

- distribution, 307 Iodide, estimation in developers, 141
- fine, developers, 89 -fixer, 150
- size, 354, 306 -silver, 21
Graininess, 240 Iodonium, derivative antifoggants, 377
Granulation, 242 Ionizing particles, action of, 409
Grotthus-Draper law, 11 Iron, organic complexes, 422
Gurney & Mott theory, 26 -effect of salts, 317
- photosensitive salts, 421
Isoelectric point, 270
Isoleucine, 274
H . & D. system, 234
Isomerization, photochemical, 15
Halo, 469
Isothiocyanate, allyl, 283
Halides alkali, 23
Isotopes, radioactive, 405
- silver, 298
Hardener, 382
Jones & Russel system, 235
-baths, 149
Harmonization, 165
Kemart, 255
Helmoltz, 409
Kerr cell, 257
Herschel, effect, 216
Kodalk, 62
Hexametaphosphate, 61
Kostinsky effect, 230
High key, 254
Kron (formula), 214
Histidine, 274, 281
Hopfield and Appleyard process, 393
Lacquer, protective, 475
Hydramine, 72, 128
Lactate, ferrous, 84
Hydrogen peroxide for latensification, 34
Land process, 435
Hydroquinone, 113
Lapeyre system, 235
-estimation, 132 et seq.
Latensification, 33
-pyridine, 100, 115
Latent image, constitution, 30
Hydroxyanthracene, developers, 117
- formation, 26
p-Hydroxybenzoic acid, methyl ester,
-internal, 31
381
- internal developers for, 86
Hydroxylamine, developers, 68
-measurement of density, 36
Hydroxyproline, 274
Latitude of exposure, 209
Hydroxytetrahydroquinoline, 127
Laurylpyridinium chloride, 55
Hydroxytetronic acid, 129
Laurylsulphate, 384
Lead emulsions, 321
-influence of salts, 318
Iconogen, 121 -photosensitive salts, 420, 421
Identity photographs, 176 Leucine, 274
Igepal C, 384 Light, properties, 3
Impurities in developers, 141 -polarized action of, 217
Indicators, pH, 41 Light-value, 257
Induction period, 57 Lignine, 442
Inflammability of films, 463 Liming, 292
Inhibitor S.N., 282 Lithium, influence of salts, 317
Intensification of latent image, 33 Low temperatures, 32
Intensifiers: chromium, 187 Lysine, 274
-dye, 187
- ferrocyanide, 185 Magnetic recording, 259
-indophenol, 185 Magnesium, chloride fixer, 1 51
- mercuric chloride, 183 - effect of salts, 317
-mercuric iodide, 184 Manganese, photosensitive salts, 430
-physical, 185 Mass-action, Law of, 369
Intermittency, 215 Material for processing equipment, 103
488 INDEX
Matt finish, 381 Oxidation, aerial, 63, 104

Mauge's method, 470 - Photochemical, 15
Melamine, 444
Mercaptobenziminazole, 375
Mercaptobenzothiazole, 376 Palladium sensitization, 320
Mercaptobenzoxazole, 377 Paper, actinometric, 396
M ercury iodide phototropic, 17 - albumerized, 357
- effect of salts, 317 - base, 442
- latensifier, 34 -bromide, developers for, 75
- photosensitive salts, 419 - celloidine, 360
Meritol, 72, 99, 128 - chloride, developers for, 78
Mesoresorcinol, 113 - citrate, 357
Metaborate, 62 - dirty, 357
Methacrylates, 467 - ferroprussiate, 425 to 430
Methionine, 281, 315 - industrial, 254
Methyl-7-hydroxy-2 .3 .4.-triaza- -iron, 424
indolizine, 379 - photographic, 249
Methyl green, 470 -photographic, curves, 251
Metal, 122 - photographic, gradation of, 251
- estimation 132 et seq·. - photographic, sensitivity, 250
- fine grain formulae, 97 - platinum, 424
- formulae, 66 -self toning, 358
- -hydroquinone, 69, 70 -sepia, 423
- preparation, 123 - testing, 327
- -pyrogallol, 71 - translucent, 448
Metoquinone, 72, 128 - variable contrast, 255
Microscope, electron, 53 Paraminophenol, 118, 119
Mitchell's theory, 28 -developers, 67
Mucobromic acid, 382 - estimation, 13 7
Mucochloric acid, 382 - fine grain developers, 96
Mucopolysaccharides, 264 Pauli's principle, 7
Multigrade, 255 Penicillin derivatives, antifoggants, 377
Mylar, 464 Pentachlorometaxylenol, 381
Pentachlorophenate, sodium, 381
a-Naphthol developers, 116 Pentachlorophenol, anti-sulphide, 104
Nekal BX, 384 Peptides, 274
Neo-DIN system, 233 Perborate latensification, 34
Nickel, effect of salts, 31 7 Peregal 0, 384
Nitriloacetic acid, 82 Period of induction, 57
Nitrobenziminazol, 374 pH, 39
Nitrosodimethylaniline, 396 -effect on development, 53
Noel,118 - measurement, 3
Nuclear emulsions, 409 - measurement in developers, 139
Nuclear trace differentiation, 414 Phenidone, 68
Nucleic acid, 282 - chloride paper developers, 78
Nylon, substratum for, 469 - developers, 71
- estimation, 138
Opacity, 200 - fine grain developers, 97
Orthophenylenediamine, 124 -preparation, 128
- in developers, 99 Phenols, antiseptics, 381
Orthophenylphenate, sodium, 381 Phenylalanine, 274
Ortol, 122 p-phenylenediamine, 124
Oxalate, ferrous, developer, 84 - developers, 98
- ferric, 430 - sulphonamido, 98
Oxazole, antifoggant, 377 Phenylhydrazones, phototropes, 17.
INDEX 489
Phenylmorpholine, 377 Pyrogallol, 116

Phenyl-3-pyrazolidone, 128 - develop ers, 67
Phosphates, estimation, 140 -estimation , 138
- silver, 358 - fine grain developers, 96
- trisodium, 62 - -metol, 71
Phosphorescence, 17 Pyrophosphate, 61
Phosphotungstic acid, 420 - silver, 358
Photochemistry, 11, 13, 15
Photoconductivity of crystals, 22 Quantum theory, 4
- of emulsions, 22 -yield, 12
Photoelectric effect, 9 Quinhydrone physical developer, 87
Photometers, photoelectric, 226 Quinone, 377
- null reading, 226 Quinone in d evelopment, 55
- photographic, 227
- thermoelectric, 226 Radiation energies, 11
- visual, 225 Radiocinematography, 404
Photomicrography by U.V., 397 Radiography, industrial, 405
Photons, 5 - medical, 404
- annihilation, 7 - with gamma rays, 405
- -gramme; 7 Radiomicrography, 405
Photosensitive glass, 438 Rag, 443
Phototropy, 16 - bisulphite, 443
Physical development, 86 Raman, effect emulsions, 214
Planck's constant, 5 Rapid d rying, 167
Plasticizers, 456 Reciprocity effect, 211
Platinum, paper, 424 - law, 211
- sensitization, 320 Redox potential, 44, 46
Pockels effect, 257 Reducine, 126
Polyamides, 467 Reducer Belitzki's, 179
Polyethylene, 467 - ammoniumthiosulphate, 181
Polyethylene terephthalate, 465, 466 - bromine, 177
Polymerization, photochemical, 15 - eerie sulphate, 181
Polyvinyl alcohol, 363 - chlorine, 177
Polyvinyl, chloride, 467 - cupric chloride, 177
Polyvinylpyrrolidones, 364 - cupric sulphate, 177
Positive developers, cine, 76 - cutting, 176
Positive holes, 28 - dichromate, 181
Post-exposure, 33 - Farmer's, 178
Potential barrier, 55 - ferric sulphate, 179
Precipitation duration, 304 - with ferricyanide, 177
- mechanism, 299 -iodine, 177-183
- methods, 301 -iodine-thiourea, 183
Pressure effects, 33 - permanganate, 181
Printing, 249 - proportional, 179
Print-out, 32 - superproportional, 182
Procollagen, 280 -thiourea, 183
Proflavine, anti-sulphide agent; 104 Reduction, 129
Proline, 274 Reduction of extreme densities, 254
Proteins, 263, 269 Reductone of gelatin, 288
Purity: ASA standards, 143 Reflex copying, emulsions, 353
Pyrimidine anti-foggants, 377 - p apers, 25 5
Pryocatechin, 115 Reh alogenation theory, 211
- compensating developers, 74 Removal of gelatin, 463
- developers, 67 Renwick's formula, 214
- fine grain develop ers, 97 Repol, 384
490 INDEX
Resins for resists, 475 Sodium acetate in fixers, analysis of, 163
Resolving power, 237 Sodium hydroxide, 62
Resorcinol, 112 SOF, degrees, 236
-anti-sulphide agent, 104 Solarization, 210
Retarding power measurement, 282 Solvents, 458
Reticulation, 167 Sound: recording, 256
Reversal, 171 , 247 -general properties, 255
-bath, 173 Sound track developing, 261
-clearing after, 174 Spectral bands, 23
- effect, 21 5 Spin, 5
- photochemical, 217 Spots, white, 108
- second exposure, 174 -black, 108
-single solution, 176 Stabilization of emulsions, 369, 371
- -transfer, 434 -of image by fixing, 158
Rhodium, effect of salts, 318 Stasiw and Tetlow's theory, 29
Ripening, accelerators, 287 Sterry effect, 254
- physical, 305 Stop baths, 148
Ripening retarders, 281, 307 -control of, 149
Rivanol, 316 -hardening, 148
Rubber hydrochloride, 467 Storage at low temperatures, 374
Russel, effect, 415 - of developers, 105
Streamers, 108
Sub-image, 31
Sabatties effect, 217 Substratum, 46 7
Safranine, accelerators, 57 Succinic ester wetting agents, 384
Sandarac, 475 Sugars in gelatin, 288
Saponin, 384 Sulphate: barium, 445
Saran, 467 -in fixers, 153
Scheiner system, 233 - sodium, estimation, 139
Schottky defects, 24 -sodium, in developers, 104
Schumann method, 393 Sulphide fog, 104
Schwarzschild coefficient, 214 Sulphide sensitizers, 283, 315
Sedimentation of emulsions, 310 -estimation, 285
Semicarbazide, 73 - inorganic, 317
Sensitivity specks, 25 Sulphite: chemical properties, 63
- intrinsic, 232 -estimation, 138
- measurement, 230 - effect on development, 54
Sensitization with gold, 318 -effect on speed, 55
Sensitometer strips: development, 228 Sulpho green, 470
Sensitometers, 221 Sulphonates in developers, 55
Sensitometry, 221 Sulphur: active, 284
Sequestering agents, 61, 104 - colloidal as sensitizer, 317
Serine, 274 - labile, 284
Shrinkage of layers, 389 Sulphur dioxide latensification, 34
Silica, emulsions on, 431 Superadditivity, 68
Silver estimation in developer, 324 Surface active accelerators, 55
- electrode potential, 44 Surface tension , 383
-electrolytic recovery, 164
- nitrate, manufacture, 323
- oxide, photosensitive, 419 Teflon, 467
-recovery from fixing baths, 163 Temperature : low, 32
Silver nitrate manufacture, 323 - of development, 102
-photosensitive solution, 421 - effect on development, 66
Silver thiocyanate emulsions, 358 Templet making, 434
Skin, 291 Terephthalic acid, 465
INDEX 491
Tergal, 464 Triaminophenol, 126

Terylene, 464 Trilon, 104
Tetrafluoroethylene, 467 Triphenyltetrazolium, 288
Tetraphosphate, 61 Tripolyphosphate, 62
Tetra-Q, 128 Trithionate sensitizer, 317
Tetrathionate sensitizer, 284 Tropical developers, 74
Tetrazols, 375 Tropocollagen, 280
Thallium, accelerator, 57 Tryptophane, 274
- effect of salts, 318 Tungstates, in emulsions, 318
- emulsions, 321 Turnbull's blue, 427
Thermofax process, 438 Two colour wrapping paper, 474
Thiazol, antifoggants, 375 Tyrosine, 274
Thiazolidine, antifoggants, 377 Ultracentrifuge, 269
- 4-carboxylic acid, 287 Ultrasonic action on gelatin, 278
Thiazolidone, retarder, 307 Ultra-violet absorption, 392
Thioanilide, antifoggant, 378 - application, 396
Thiobarbituric acid, 288 - sensitive layers, 393
- antifoggant, 377 - sources, 391
Thiocarbamide, warm tones with, 81 - spectrography, 392
Thiocyanates: estimation, 140
- in developers, 97 Valine, 274
-in emulsions, 318 Vanadium developers, 84
-as fixer, 151 Variable area recording, 257 to 261
Thioglycolic acid, 282 Varigam, 255
Thiosemicarbazide antifoggants, 284, 317 Versene, 104
Thiosinamine fixers, 151 Villard effect, 215
Thiosulphate sensitizer, 284, 317 Vinyl chloride base, 469
Thiosulphate, ammonium, 156 Viscosity of dope, 459
-double salt of sodium and ammonium, - of emulsions, 385
157
-elimination, 161
-estimation, 156 Warm black developers, 79
-sodium, 152 Warm tones, 79, 80
Thiourea : fixer, 151 Washing processed material, 159
-stabilizer, 158 - emulsions, 309
Threshold, 233 Water control for washing, 160
-of illumination, 213 -for developers, 61
Thymol, antiseptic, 381 Watkins factor, 205
Titano-oxalates, 82 Wedges, 223
Toluylenediamines, 124 Weigert effect, 217
Toning: colloidal silver, 193 Wetting agents, 160, 383
- -fixing, 197
-gold, 195
-gold (Nelson), 197 Xerography, 436
-gold-thiocyanate, 196 X-rays, photographic action, 399
- gold, thiourea, 197 - sensitive layers, 401
- gold, after sulphur toning, 197 - sources, 399
- platinum, 198
- selenium, 193
- sulphide, 2 bath, 189 to 191 Yellowing of photographic papers, 79
- sulphide, hypo alum, 191
- sulphide with sulphur, 192
- sulphide with polysulphide, 193 Zein, 474
Transmission, 200 Zinc, photosensitive salts, 419
Triaminobenzene, 126 Zirconium, hardeners, 382
VOLUME TWO
The second volume of Photographic Chemistry dealing

largely with colour photography is to be published late in
1959. Comprehensive sections cover in detail:
Spectrosensitometry
Colour photography and cinematography
Separation negatives for colour reproduction
Control and correction of colour images
Colour development
Production of coloured images after development
Photographic images by modifying gelatin and other
colloids
Photographic processes involving the dyeing of gelatin
Photochemical destruction and formation of dyes
Colour sensitization
Intermediates used in the preparation of sensitizing dyes
Cyanines
Carbocyanines
Hemicyanines
Infra-red sensitization. The polycarbocyanines
Colour sensitizing technique and theory
D esensitization
The Atoms
Fundamental chemical principles
Constitution and properties of organic compounds
R eserve your copy now
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PIERRE GLAFKIDES

Chemical Engineer of the Institute of Chemistry of Paris

Translated from the French by

FOUNTAIN PRESS · LONDON

Printed in Great Britain by

FOREWORD by L. P. Clerc, Hon. F .R.P.s. Xlll

THE FORMATION AND DEVELOPMENT OF THE

Chapter XII Page

Chapter XVII Page

The Formation and Development of the

According to the electromagnetic theory, a light-wave is represented at

If we represent (Fig. 1) the resultant elementary wave by an oscillation

v is the frequency of the wave. It is higher as the .\ is smaller. Since v

2. The range of elect1'omagnetic waves is continuous from the radio waves

4. The electromagnetic wave

5. Theory of the annihilation of photons

!fen = frn(x,y, z, t)eik,x,

6. Emission of radiation by matter

is then in an activated state, similar to that of a tightened spring ready to be

in which m is the mass of the electron, e its charge, h is Planck's constant

7. The action of radiation on atoms

9. Absorption of light by molecules

Depending on whether a single substance is involved, or of a system com-

10. Basic laws

in which his Planck's constant equal to 6·55 X 10-27 erg.

containing N molecules (para. 838). By converting to equivalent calories,

3. Law of photochemical equivalence (or Einstein's Law). For each absorbed

no. decomposed molecules

then a quantum yield is obtained which varies considerably within extensive

The quantum yield is then in the neighbourhood of 2. An example of this

2CH4 + Cl 2 = 2CH 3 Cl +H 2 with p = 10,000

as well as the combinations of chlorine with a number of organic substances,

In order to take place, a photochemical reaction sometimes demands the

11. Photochemical dissociation

There may be changes of form, such as with dibenzoylethylene and di-

13. Inorganic photochemical reactions

Ferric Ferrous Chlorine

If the chlorine is absorbed as and when it is formed, only the photolytic

C 2 0 4-+Hg++ ~ 2C0 2 +Hg+

Eder's reaction is sensitized by plane-molecule cyanines and erythrosine

The carbazones, such as cinnamaldehyde-phenylsemicarbazone, when subjected

15. Fluorescence and phosphorescence

1. Emschwiller: L'Action Chimique de la Lumiere: la Photolyse. (Centre de Docu-

THEORY OF THE LATENT IMAGE

16. The silver bromide crystal

FrG. 3. Crystal lattice of silver hal-

the longer wavelengths. This displacement relates to the presence of cubic,

17. Adsorptions on the surface of crystals

18. Absorption spectra and photoconductivity

19. Alkali halides

20. Defects of the crystal lattice

22. Process of latent image formation according to the Gurney-

Since the decomposition of silver bromide is a reversible effect, it is neces-

23. Positive holes

25. Stasiw and Teltow's theory