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SURFACTANTS AND
INTERFACIAL PHENOMENA
SURFACTANTS AND
INTERFACIAL PHENOMENA
THIRD EDITION

Milton J. Rosen
Surfactant Research Institute
Brooklyn College
The City University of New York

A JOHN WILEY & SONS, INC., PUBLICATION

Copyright # 2004 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or
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however, may not be available in electronic format.

Library of Congress Cataloging-in-Publication Data is available.

Rosen, Milton J.
Surfactants and interfacial phenomena / Milton J. Rosen. – 3rd ed.
p. cm.
Includes bibliographical references and index.
ISBN 0-471-47818-0
1. Surface active agents. 2. Surface chemistry. I. Title.
TP994.R67 2004
6680 .1–dc22 2004048079

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1
Contents

Preface xiii
1 Characteristic Features of Surfactants 1
A Conditions Under Which Interfacial Phenomena and
Surfactants Become Significant 2
B General Structural Features and Behavior of Surfactants 2
1 General Use of Charge Types 4
2 General Effects of the Nature of the Hydrophobic
Group 5
I Characteristic Features and Uses of Commercially Available
Surfactants 6
I.A Anionics 7
1 Carboxylic Acid Salts 7
2 Sulfonic Acid Salts 8
3 Sulfuric Acid Ester Salts 12
4 Phosphoric and Polyphosphoric Acid Esters 15
5 Fluorinated Anionics 15
I.B Cationics 16
1 Long-Chain Amines and Their Salts 17
2 Acylated Diamines and Polyamines and Their Salts 17
3 Quaternary Ammonium Salts 18
4 Polyoxyethylenated (POE) Long-Chain Amines 19
5 Quaternized POE Long-Chain Amines 19
6 Amine Oxides 19
I.C Nonionics 20
1 POE Alkylphenols, Alkylphenol ‘‘Ethoxylates’’ 20
2 POE Straight-Chain Alcohols, Alcohol
‘‘Ethoxylates’’ 21
3 POE Polyoxypropylene glycols 22
4 POE Mercaptans 22
5 Long-Chain Carboxylic Acid Esters 23
6 Alkanolamine ‘‘Condensates,’’ Alkanolamides 24
7 Tertiary Acetylenic Glycols and Their
‘‘Ethoxylates’’ 24
8 POE Silicones 25
9 N-Alkylpyrrolidones 25

v
vi CONTENTS

10 Alkylpolyglycosides 26
I.D Zwitterionics 26
1 pH-Sensitive Zwitterionics 26
2 pH-Insensitive Zwitterionics 28
I.E Newer Surfactants Based Upon Renewable
Raw Materials 28
1 a-Sulfofatty Acid Methyl Esters (SME) 28
2 Acylated Aminoacids 29
3 N-Acyl L-Glutamates (AG) 29
4 N-Acyl Glycinates 29
5 N-Acyl DL-Alaninates 30
6 Other Acylated Aminoacids 30
7 Nopol Alkoxylates 30
II Environmental Effects of Surfactants 31
II.A Surfactant Biodegradability 31
II.B Surfactant Toxicity To and Bioconcentration in
Marine Organisms 31
III Some Useful Generalizations 32
References 33
Problems 33

2 Adsorption of Surface-Active Agents at Interfaces:

The Electrical Double Layer 34
I The Electrical Double Layer 35
II Adsorption at the Solid–Liquid Interface 38
II.A Mechanisms of Adsorption and Aggregation 39
II.B Adsorption Isotherms 42
1 The Langmuir Adsorption Isotherm 44
II.C Adsorption from Aqueous Solution Onto Adsorbents
with Strongly Charged Sites 47
1 Ionic Surfactants 47
2 Nonionic Surfactants 52
3 pH Change 53
4 Ionic Strength 53
5 Temperature 53
II.D Adsorption from Aqueous Solution Onto Nonpolar,
Hydrophobic Adsorbents 54
II.E Adsorption from Aqueous Solution Onto Polar
Adsorbents without Strongly Charged Sites 56
II.F Effects of Adsorption from Aqueous Solution on the
Surface Properties of the Solid Adsorbent 57
1 Substrates with Strongly Charged Sites 57
2 Nonpolar Adsorbents 58
 CONTENTS vii

II.G Adsorption from Nonaqueous Solution 58

II.H Determination of the Specific Surface Areas of Solids 59
III Adsorption at the Liquid–Gas (L/G) and Liquid–Liquid
(L/L) Interfaces 59
III.A The Gibbs Adsorption Equation 60
III.B Calculation of Surface Concentrations and Area per
Molecule at the Interface By Use of the Gibbs Equation 62
III.C Effectiveness of Adsorption at the L/G and L/L Interfaces 64
III.D The Szyszkowski, Langmuir, and Frumkin Equations 82
III.E Efficiency of Adsorption at the L/G and L/L Interfaces 83
III.F Calculation of Thermodynamic Parameters of
Adsorption at the L/G and L/L Interfaces 87
III.G Adsorption from Mixtures of Two Surfactants 95
References 97
Problems 103

3 Micelle Formation by Surfactants 105

I The Critical Micelle Concentration (CMC) 105
II Micellar Structure and Shape 107
II.A The Packing Parameter 107
II.B Surfactant Structure and Micellar Shape 109
II.C Liquid Crystals 110
III Micellar Aggregation Numbers 113
IV Factors Affecting the Value of the CMC in Aqueous Media 120
IV.A Structure of the Surfactant 121
1 The Hydrophobic Group 121
2 The Hydrophobic Group 138
3 The Counterion in Ionic Surfactants: Degree
of Binding to the Micelle 139
4 Empirical Equations 144
IV.B Electrolyte 144
IV.C Organic Additives 146
1 Class I Materials 146
2 Class II Materials 147
IV.D The Presence of a Second Liquid Phase 148
IV.E Temperature 149
V Micellization in Aqueous Solution and Adsorption
at the Aqueous Solution–Air or Aqueous
Solution–Hydrocarbon Interface 149
V.A. The CMC/C20 ratio 149
VI CMCs in Nonaqueous Media 157
VII Equations for the CMC Based on Theoretical Considerations 157
VIII Thermodynamic Parameters of Micellization 161
viii CONTENTS

IX Mixed Micelle Formation in Mixtures of Two Surfactants 167

References 168
Problems 175

4 Solubilization by Solutions of Surfactants: Micellar Catalysis 178

I Solubilization in Aqueous Media 179
I.A Locus of Solubilization 179
I.B Factors Determining the Extent of Solubilization 181
1 Structure of the Surfactant 182
2 Structure of the Solubilizate 184
3 Effect of Electrolyte 185
4 Effect of Monomeric Organic Additives 185
5 Effect of Polymeric Organic Additives 186
6 Mixed Anionic–Nonionic Micelles 187
7 Effect of Temperature 188
8 Hydrotropy 189
I.C Rate of Solubilization 190
II Solubilization in Nonaqueous Solvents 190
II.A Secondary Solubilization 192
III Some Effects of Solubilization 193
III.A Effect of Solubilization on Micellar Structure 193
III.B Change in the Cloud Points of Aqueous Solutions
of Nonionic Surfactants 193
III.C Reduction of the CMC 197
III.D Miscellaneous Effects of Solubilization 198
IV Micellar Catalysis 198
References 202
Problems 206

5 Reduction of Surface and Interfacial Tension by Surfactants 208

I Efficiency in Surface Tension Reduction 212
II Effectiveness in Surface Tension Reduction 214
II.A The Krafft Point 214
II.B Interfacial Parameter and Chemical Structural Effects 215
III Liquid–Liquid Interfacial Tension Reduction 229
III.A Ultralow Interfacial Tension 230
IV Dynamic Surface Tension Reduction 234
IV.A Dynamic Regions 234
IV.B Apparent Diffusion Coefficients of Surfactants 237
References 238
Problems 242
 CONTENTS ix

6 Wetting and Its Modification by Surfactants 243

I Wetting Equilibria 243
I.A Spreading Wetting 243
1 The Contact Angle 246
2 Measurement of the Contact Angle 247
I.B Adhesional Wetting 249
I.C Immersional Wetting 251
I.D Adsorption and Wetting 253
II Modification of Wetting by Surfactants 255
II.A General Considerations 255
II.B Hard Surface (Equilibrium) Wetting 256
II.C Textile (Nonequilibrium) Wetting 258
II.D Effect of Additives 268
III Synergy in Wetting by Mixtures of Surfactants 269
IV Superspreading (Superwetting) 270
References 273
Problems 275

7 Foaming and Antifoaming by Aqueous Solutions of Surfactants 277

I Theories of Film Elasticity 278
II Factors Determining Foam Persistence 282
II.A Drainage of Liquid in the Lamellae 282
II.B Diffusion of Gas Through the Lamellae 283
II.C Surface Viscosity 284
II.D The Existence and Thickness of the Electrical
Double Layer 284
III The Relation of Surfactant Chemical Structure to Foaming
in Aqueous Solution 285
III.A Efficiency as a Foaming Agent 285
III.B Effectiveness as a Foaming Agent 287
III.C Low-Foaming Surfactants 293
IV Foam-Stabilizing Organic Additives 294
V Antifoaming 297
VI Foaming of Aqueous Dispersions of Finely Divided Solids 298
References 299
Problems 301

8 Emulsification by Surfactants 303

I Macroemulsions 304
I.A Formation 305
I.B Factors Determining Stability 305
x CONTENTS

1 Physical Nature of the Interfacial Film 306

2 Existence of an Electrical or Steric Barrier to
Coalescence on the Dispersed Droplets 308
3 Viscosity of the Continuous Phase 309
4 Size Distribution of Droplets 309
5 Phase Volume Ratio 309
6 Temperature 310
I.C Inversion 311
I.D Multiple Emulsions 313
I.E Theories of Emulsion Type 314
1 Qualitative Theories 314
2 Kinetic Theory of Macroemulsion Type 316
II Microemulsions 317
III Nanoemulsions 319
IV Selection of Surfactants as Emulsifying Agents 320
IV.A The HLB Method 321
IV.B The PIT Method 324
IV.C The HLD Method 326
V Demulsification 327
References 327
Problems 330

9 Dispersion and Aggregation of Solids in Liquid Media

by Surfactants 332
I Interparticle Forces 332
I.A Soft (electrostatic) and van der Waals Forces:
DLVO Theory 332
1 Limitations of the DLVO Theory 338
I.B Steric Forces 339
II Role of the Surfactant in the Dispersion Process 341
II.A Wetting of the Powder 342
II.B Deaggregation or Fragmentation of Particle Clusters 342
II.C Prevention of Reaggregation 342
III Coagulation or Flocculation of Dispersed Solids by Surfactants 343
III.A Neutralization or Reduction of the Potential at the
Stern Layer of the Dispersed Particles 343
III.B Bridging 344
III.C Reversible Flocculation 344
IV The Relation of Surfactant Chemical Structure to
Dispersing Properties 345
IV.A Aqueous Dispersions 345
IV.B Nonaqueous Dispersions 349
 CONTENTS xi

References 350
Problems 351

10 Detergency and Its Modification by Surfactants 353

I Mechanisms of the Cleaning Process 353
I.A Removal of Soil from Substrate 354
1 Removal of Liquid Soil 355
2 Removal of Solid Soil 357
I.B Suspension of the Soil in the Bath and Prevention of
Redeposition 359
1 Solid Particulate Soils: Formation of Electrical and
Steric Barriers; Soil Release Agents 359
2 Liquid Oily Soil 359
I.C Skin Irritation 361
I.D Dry Cleaning 361
II Effect of Water Hardness 362
II.A Builders 363
II.B Lime Soap Dispersing Agents 364
III Fabric Softeners 365
IV The Relation of the Chemical Structure of the Surfactant
to Its Detergency 367
IV.A Effect of Soil and Substrate 367
1 Oily Soil 367
2 Particulate Soil 370
3 Mixed Soil 370
IV.B Effect of the Hydrophobic Group of the Surfactant 371
IV.C Effect of the Hydrophilic Group of the Surfactant 372
IV.D Dry Cleaning 374
References 374
Problems 378

11 Molecular Interactions and Synergism in Mixtures

of Two Surfactants 379
I Evaluation of Molecular Interaction Parameters 380
I.A Notes on the Use of Equations 11.1–11.4 382
II Effect of Chemical Structure and Molecular Environment on
Molecular Interaction Parameters 384
III Conditions for the Existence of Synergism 397
III.A Synergism or Antagonism (Negative Synergism) in
Surface or Interfacial Tension Reduction Efficiency 398
III.B Synergism or Antagonism (Negative Synergism)
in Mixed Micelle Formation in Aqueous Medium 400
xii CONTENTS

III.C Synergism or Antagonism (Negative Synergism) in

Surface or Interfacial Tension Reduction Effectiveness 401
III.D Selection of Surfactants Pairs for
Optimal Interfacial Properties 405
IV The Relation between Synergism in Fundamental Surface
Properties and Synergism in Surfactant Applications 405
References 410
Problems 413

12 Gemini Surfactants 415

I Fundamental Properties 415
II Interaction with Other Surfactant 420
III Performance Properties 423
References 424
Problems 426

Answers to Problems 428

Index 433
Preface

The more than a decade since publication of the second edition has seen
considerable progress in a number of important areas of surfactant chemistry,
necessitating the publication of a third edition. This edition, consequently, contains
a number of areas not included in the previous edition.
These include an entire chapter on ‘‘gemini’’ surfactants (surfactants with two
hydrophilic and two or three hydrophobic groups in the molecule), which have
evoked intense interest, both academic and industrial, because of their unique
properties. Also included are guidelines for the selection of surfactant pairs for
the optimization of surfactant properties and sections on ‘‘green’’ surfactants from
renewable resources, estimation of marine organism toxicity and bioconcentration
of surfactants from their physico-chemical properties, dynamic surface tension
reduction, synergy in wetting and ‘‘superwetting’’ by mixtures of surfactants,
foaming of aqueous dispersions of finely divided solids, and demulsification by
surfactants.
Areas covered in the previous edition have been expanded and upgraded to
reflect new developments. Tables of physico-chemical constants of surfactants,
including critical micelle concentrations, areas/surfactant molecule at interfaces,
and surfactant–surfactant interaction parameters have been greatly increased.
Additional problems have been provided at the ends of the chapters.
I should like to acknowledge and thank a number of colleagues and former
students for their assistance with this edition. I am grateful to Randy Bernhardt and
Gregory Dado of Stepan, Manilal Dahanayake of Rhodia, Paul Berger of Oil Chem
Technologies, Kazayuki Tsubone (now retired) of Kanebo, Richard Thomas of
OMNOVA Solutions, and Michael Cox and Dewey Smith of Sasol for their help in
updating the section on commercially available surfactants. I am indebted to Arno
Cahn for his assistance with the section on detergent ‘‘builders.’’ My former
doctoral student, Qiong Zhou, provided some of the figures.

Great Neck, New York MILTON J. ROSEN

xiii
1 Characteristic Features
of Surfactants

Surfactants are among the most versatile products of the chemical industry,
appearing in such diverse products as the motor oils we use in our automobiles,
the pharmaceuticals we take when we are ill, the detergents we use in cleaning our
laundry and our homes, the drilling muds used in prospecting for petroleum, and the
flotation agents used in benefication of ores. The last decades have seen the
extension of surfactant applications to such high-technology areas as electronic
printing, magnetic recording, biotechnology, micro-electronics, and viral research.
A surfactant (a contraction of the term surface-active agent) is a substance that,
when present at low concentration in a system, has the property of adsorbing onto
the surfaces or interfaces of the system and of altering to a marked degree the
surface or interfacial free energies of those surfaces (or interfaces). The term
interface indicates a boundary between any two immiscible phases; the term
surface denotes an interface where one phase is a gas, usually air.
The interfacial free energy is the minimum amount of work required to create
that interface. The interfacial free energy per unit area is what we measure when we
determine the interfacial tension between two phases. It is the minimum amount of
work required to create unit area of the interface or to expand it by unit area. The
interfacial (or surface) tension is also a measure of the difference in nature of the
two phases meeting at the interface (or surface). The greater the dissimilarity in
their natures, the greater the interfacial (or surface) tension between them.
When we measure the surface tension of a liquid, we are measuring the
interfacial free energy per unit area of the boundary between the liquid and the
air above it. When we expand an interface, therefore, the minimum work required
to create the additional amount of that interface is the product of the interfacial
tension gI and the increase in area of the interface; Wmin ¼ gI 
interfacial area.
A surfactant is therefore a substance that at low concentrations adsorbs at some or
all of the interfaces in the system and significantly changes the amount of work
required to expand those interfaces. Surfactants usually act to reduce interfacial free
energy rather than to increase it, although there are occasions when they are used to
increase it.
The questions that immediately arise are the following: Under what conditions
can surfactants play a significant role in a process? How does one know when to

Surfactants and Interfacial Phenomena, Third Edition. Milton J. Rosen

ISBN 0-471-47818-0 # 2004 John Wiley & Sons, Inc.

1
2 CHARACTERISTIC FEATURES OF SURFACTANTS

expect surfactants to be a significant factor in some system under investigation?

How and why do they work as they do?

A. Conditions Under Which Interfacial Phenomena and

Surfactants Become Significant
The physical, chemical, and electrical properties of matter confined to phase
boundaries are often profoundly different from those of the same matter in bulk.
For many systems, even those containing a number of phases, the fraction of the
total mass that is localized at phase boundaries (interfaces, surfaces) is so small that
the contribution of these ‘‘abnormal’’ properties to the general properties and
behavior of the system is negligible. There are, however, many important circum-
stances under which these ‘‘different’’ properties play a significant, if not a major,
role.
One such circumstance is when the phase boundary area is so large relative to
the volume of the system that a substantial fraction of the total mass of the system is
present at boundaries (e.g., in emulsions, foams, and dispersions of solids). In this
circumstance, surfactants can always be expected to play a major role in the system.
Another such circumstance is when the phenomena occurring at phase bound-
aries are so unusual relative to the expected bulk phase interactions that the entire
behavior of the system is determined by interfacial processes (e.g., heterogeneous
catalysis, corrosion, detergency, or flotation). In this circumstance also surfactants
can play an important role in the process. It is obviously necessary to understand
the causes of this abnormal behavior of matter at the interfaces and the variables
that affect this behavior in order to predict and control the properties of these
systems.

B. General Structural Features and Behavior of Surfactants

The molecules at a surface have higher potential energies than those in the interior.
This is because they interact more strongly with the molecules in the interior of the
substance than they do with the widely spaced gas molecules above it. Work is
therefore required to bring a molecule from the interior to the surface.
Surfactants have a characteristic molecular structure consisting of a structural
group that has very little attraction for the solvent, known as a lyophobic group,
together with a group that has strong attraction for the solvent, called the lyophilic
group. This is known as an amphipathic structure. When a molecule with an
amphipathic structure is dissolved in a solvent, the lyophobic group may distort the
structure of the solvent, increasing the free energy of the system. When that occurs,
the system responds in some fashion in order to minimize contact between the
lyophobic group and the solvent. In the case of a surfactant dissolved in aqueous
medium, the lyophobic (hydrophobic) group distorts the structure of the water (by
breaking hydrogen bonds between the water molecules and by structuring the water
in the vicinity of the hydrophobic group). As a result of this distortion, some of the
 CHARACTERISTIC FEATURES OF SURFACTANTS 3

surfactant molecules are expelled to the interfaces of the system, with their
hydrophobic groups oriented so as to minimize contact with the water molecules.
The surface of the water becomes covered with a single layer of surfactant
molecules with their hydrophobic groups oriented predominantly toward the air.
Since air molecules are essentially nonpolar in nature, as are the hydrophobic
groups, this decrease in the dissimilarity of the two phases contacting each other at
the surface results in a decrease in the surface tension of the water. On the other
hand, the presence of the lyophilic (hydrophilic) group prevents the surfactant from
being expelled completely from the solvent as a separate phase, since that would
require dehydration of the hydrophilic group. The amphipathic structure of
the surfactant therefore causes not only concentration of the surfactant at the
surface and reduction of the surface tension of the water, but also orientation of the
molecule at the surface with its hydrophilic group in the aqueous phase and its
hydrophobic group oriented away from it.
The chemical structures of groupings suitable as the lyophobic and lyophilic
portions of the surfactant molecule vary with the nature of the solvent and the
conditions of use. In a highly polar solvent such as water, the lyophobic group may
be a hydrocarbon or fluorocarbon or siloxane chain of proper length, whereas in a
less polar solvent only some of these may be suitable (e.g., fluorocarbon or siloxane
chains in polypropylene glycol). In a polar solvent such as water, ionic or highly
polar groups may act as lyophilic groups, whereas in a nonpolar solvent such as
heptane they may act as lyophobic groups. As the temperature and use conditions
(e.g., presence of electrolyte or organic additives) vary, modifications in the
structure of the lyophobic and lyophilic groups may become necessary to maintain
surface activity at a suitable level. Thus, for surface activity in a particular system
the surfactant molecule must have a chemical structure that is amphipathic in that
solvent under the conditions of use.
The hydrophobic group is usually a long-chain hydrocarbon residue, and less
often a halogenated or oxygenated hydrocarbon or siloxane chain; the hydrophilic
group is an ionic or highly polar group. Depending on the nature of the hydrophilic
group, surfactants are classified as:

1. Anionic. The surface-active portion of the molecule bears a negative charge,

for example, RCOO Naþ (soap), RC6 H4 SO þ
3 Na (alkylbenzene sulfonate).
2. Cationic. The surface-active portion bears a positive charge, for example,
þ 
RNHþ 
3 Cl (salt of a long-chain amine), RN(CH3 Þ3 Cl (quaternary ammo-
nium chloride).
3. Zwitterionic. Both positive and negative charges may be present in the
surface-active portion, for example, RNþ H2 CH2 COO (long-chain amino
acid), RNþ (CH3 Þ2 CH2 CH2 SO3 (sulfobetaine).
4. Nonionic. The surface-active portion bears no apparent ionic charge, for
example, RCOOCH2 CHOHCH2 OH (monoglyceride of long-chain fatty
acid), RC6 H4 (OC2 H4 Þx OH (polyoxyethylenated alkylphenol), R(OC2 H4 Þx
OH(polyoxyethylenated alcohol).
Exploring the Variety of Random
Documents with Different Content
stages between San Antonio, Texas, and San Diego, California.
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Of all these eight thousand gold-seekers or pioneers, only one
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man of marked personality and far-reaching vision who lived a
generation before his time,” crossed the Sink on his way to San
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Professor Blake, that the arid waste of the Sink, if adequately
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five or six years, he spent much of his time and a large part of his
private means in promoting schemes for the irrigation of this desert
area. His engineer, Ebenezer Hadley of San Diego, made a
preliminary survey of the Sink, and recommended a canal location
practically identical with that which forty years later was adopted. In
1859, upon the initiative of Dr. Wozencraft, the California legislature
asked Congress to cede to the State 3,000,000 acres of arid land,
including the Salton Sink, for irrigation purposes. The bill was
favorably reported by a House committee, but failed to pass. The
Congressmen of that time regarded the reclamation of the Colorado
Desert as a subject for jocular rather than serious treatment, and
most of them were in sympathy with the California humorist, J. Ross
Browne, who said: “I can see no great obstacle to success except
the porous nature of the sand. By removing the sand from the
desert, success would be insured at once.”
With the failure of Dr. Wozencraft’s attempt to bring about the
reclamation of the Colorado Desert, interest in that region gradually
waned. The Butterfield Overland Mail service to the Pacific Coast
was discontinued; a new “Pony Express” line to San Francisco, by
way of Salt Lake City, was established; and before 1865, the
southern route, via Yuma and the Colorado Desert, had been
practically abandoned. Dr. Wozencraft continued talking, to all who
would listen, about his scheme for the irrigation of the Salton Sink;
but most people regarded it as visionary, and nobody seemed
inclined to take it up. Only in 1891, thirty eight years after Professor
Blake first suggested irrigation, and twenty nine years after Dr.
Wozencraft’s bill failed in Congress, was a serious attempt made to
realize the “dream” of turning water into the Salton Sink and creating
a fertile oasis in the heart of the Colorado Desert.

FOOTNOTES:
[1] Rep. of U. S. Geolog. Survey for 1916.
[2] “The Imperial Valley and Salton Sink,” by H. T. Cory,
formerly Chief Engineer of the California Development Co., p. 49;
San Francisco 1915 (embodying paper read Jan. 8, 1913, before
the Amer. Soc. of Civil Engineers and published in its
Transactions as “Paper 1270”).
 THE CREATION OF THE OASIS
In 1891, John C. Beatty, of California, another man who had
imagination and foresight, became interested in the agricultural
possibilities of the Colorado Desert, and formed a corporation under
the name of “The California Irrigation Company” for the purpose of
carrying water into the Salton Sink from the Colorado River. He
engaged as his technical adviser Mr. C. R. Rockwood, who had been
in the employ of the U. S. Reclamation Service, and who was
regarded as “a shrewd and clever man and engineer.”[3] Mr.
Rockwood made a careful survey of the Colorado delta, and found,
as Lieutenant Bergland had found in an earlier survey, that between
the river and the Sink there was a natural obstacle in the shape of a
range of sand hills, which extended southward to the border line of
Mexico. All natural overflows of the river, in prehistoric times, had
been south of this barrier, and Mr. Rockwood thought that it would be
easier and more economical to follow the river’s ancient track than to
put a conduit through these hills on the American side of the
boundary. He proposed, therefore, to take water from the Colorado
at Potholes, twelve miles above Yuma, carry it southward into
Mexico, thence westward around the promontory of sand hills, and
finally northward, across the line again, into southern California. This
plan would involve the digging of a curving canal, forty or fifty miles
in length, through Mexican territory; but it would obviate the
necessity of cutting through the sand hills, and would perhaps
enable the diggers to utilize, on the Mexican side, one of the dry
barrancas, or ancient overflow channels, through which the Colorado
discharged into the Sink in ages past.
 Relief Map of Imperial Valley and Its Environment
Owing to the lack of public confidence in reclamation experiments,
Mr. Beatty and his associates were not able to secure as much
capital as they needed for their enterprise, and when the monetary
panic of 1893 came, they found themselves involved in financial
difficulties from which they could not extricate themselves. In the
latter part of 1893 the California Irrigation Co. went into bankruptcy,
and its maps, records, and engineering data were turned over to Mr.
Rockwood, in satisfaction of a judgment that he obtained in a suit for
his unpaid salary.[4]
 This seemed likely to put an end to the Salton Sink project; but Mr.
Rockwood, whose observations and work in the Colorado delta had
given him unbounded faith in the ultimate success of the scheme,
determined to undertake the promotion of it himself. After several
years of endeavor, he succeeded in forming another organization
which was incorporated in New Jersey, on the 21st of April 1896,
under the title of “The California Development Company.” For two
years or more, this corporation tried to get permission from the
Mexican Government to hold land, acquire rights, and dig an
irrigating canal south of the boundary line; but the Mexican
authorities refused to make any concessions, and it was finally found
necessary to organize a subsidiary Mexican company. This
corporation, which had a nominal capital of $62,000, was wholly
owned and controlled by the California Development Co., but it
operated under a Mexican charter.
As the financial resources of both companies were largely on
paper, it then became necessary to secure real capital for the
prosecution of the work, and this task Mr. Rockwood found extremely
difficult. The proposed reclamation of an arid desert, where the
thermometer went in summer to 120 in the shade, and where only
two or three inches of rain fell in the course of the whole year, did not
strike Eastern capitalists as a very promising venture, and most of
them were disinclined to go into it. At last, however, in 1898, Mr.
Rockwood secured a promise from certain capitalists in New York
that they would advance the necessary funds; but two days before
the papers were to be signed, the American battleship “Maine” was
blown up in the harbor of Havana, and this catastrophe, together
with the war that followed it, put an end to the negotiations.
But the plan for the irrigation of the Salton Sink was not destined
to fail. Among the men with whom Dr. Wozencraft discussed it, in the
early eighties, was George Chaffey, a civil engineer and irrigation
expert of Los Angeles, who had had a good deal of experience in
dealing with water problems, and who had already established
successful irrigation systems in other parts of California.[5] Mr.
Chaffey declined to go into it at Dr. Wozencraft’s solicitation, not
because he was afraid of the engineering difficulties involved, but
because he thought that the torrid climate of the Sink would prevent
colonization of it, even if the colonists were promised plenty of water.
Most men, he reasoned, would be frightened by the prospect of
having to do hard agricultural labor in shade temperatures of 110 to
120, and sun temperatures of perhaps 140 to 150. They simply
would not go to a place where they would be subjected to such heat.
Some years later, however, Mr. Chaffey carried through successfully
an irrigation enterprise in the interior of Australia, where the
temperature in the shade often reached a maximum of 125, but
where, nevertheless, men were able to work without danger or
serious inconvenience. This changed his view of irrigation in the
Colorado Desert; and in 1900, when the California Development Co.
seemed unable to get money enough for its project elsewhere, Mr.
Chaffey offered to finance the undertaking and superintend the work.
His proposals were accepted, and on the 3rd of April 1900, he
became president of the company, and signed a contract by which
he bound himself to construct canals, at a cost of not more than
$150,000, which would carry to the Imperial Valley 400,000 acre-feet
of water per annum.[6]
Mr. Chaffey and his associates modified the plan of Mr. Rockwood
by taking water from the Colorado at Pilot Knob, nearly opposite
Yuma, instead of at Potholes, twelve miles above. Putting in a head-
gate there, they carried their main canal southward across the
Mexican boundary, in a course nearly parallel with the river, until they
reached the barranca, or dry overflow channel, known as the Alamo.
As this ancient watercourse meandered westward in the direction of
the Salton Sink, they were able to clear it out, enlarge it, and utilize
most of it as a part of their irrigation system. Then, at a point about
forty miles west of the Colorado, they carried their canal northward,
across the boundary line again, into southern California. The work
throughout was pushed with great energy, and on the 14th of May,
1901, a little more than a year after Mr. Chaffey assumed direction of
affairs, water was turned in at the Pilot Knob head-gate, and the
irrigation of the Salton Sink became a certainty, if not a fully
accomplished fact.
 As the California Development Co. was a water-selling company
only, and had no proprietary interest in the lands to be irrigated, it
was thought best to form another organization for the promotion of
settlement; and in March 1901 the Imperial Land Company was
incorporated for the purpose of attracting colonists, laying out town
sites, and developing the Sink by bringing its lands into cultivation.
Then Mr. Chaffey and the Land Company began an advertising
campaign for the purpose of interesting the general public in the
scheme; and in order not to frighten settlers and small investors by
using in their advertisements and circulars the ominous words
“desert” and “Sink,” they changed the name of the basin that they
proposed to irrigate and called it “The Imperial Valley.” This title was
evidently alluring, because it attracted small investors in all parts of
the East, and particularly in New England. The Development
Company’s stock was bought, for example, in places as far away
from the Salton Sink as Boston, Concord, Hopedale and Waverley,
Mass.; Barre and Montpelier, Vt.; Portsmouth, N. H.; Elgin, Ill.;
Portland, Oregon; and Toronto, Canada.[7] Settlers soon began to
come in; mutual water companies were organized; and before the
3rd of April 1902, when Mr. Chaffey severed his connection with the
company, four hundred miles of irrigating ditches had been dug, and
water was available for 100,000 acres or more of irrigable land.[8]
About this time, however, the future of the Valley was seriously
imperilled by unfavorable reports concerning its soil. In the early part
of 1902, the Bureau of Soils of the U. S. Agricultural Department
published the results of a survey of the irrigable lands in the
Colorado Desert, and reported that they were so impregnated with
alkali that very few things could be successfully grown on them.
“One hundred and twenty five thousand acres of land” (the
report said) “have already been taken up by prospective
settlers, many of whom talk of planting crops which it will be
absolutely impossible to grow. They must early find that it will
be useless to attempt their growth.... No doubt the best thing
to do is to raise such crops as sugar beet, sorghum, and date
palm (if the climate will permit), that are suited to such alkali
conditions, and abandon as worthless the lands which contain
 too much alkali to grow those crops.” (“Field Operations of the
Bureau of Soils, U. S. Department of Agriculture,” 1901, p.
587.)
This report, which was widely quoted and commented upon, acted
as a serious check to the colonization of the Valley; and if it had
been made two or three years earlier, it might have been fatal to the
whole irrigation project. Fortunately, however, the crops raised by a
few farmers who had already been cultivating this “alkali
impregnated” land proved conclusively that the report of the analysis
of the soil made by the Government experts was unduly pessimistic,
if not wholly erroneous. Almost everything that was tried did grow, in
spite of expert predictions, and the practical experience of men on
the ground gradually revived public confidence in the productiveness
of the irrigated lands. The colonization and development of the
Valley then proceeded with great rapidity. The two thousand settlers
on the ground at the end of 1902 increased to seven thousand in
1903 and to more than ten thousand in 1904. A branch of the
Southern Pacific railroad was built through the Valley from Imperial
Junction to Calexico and Mexicali; town sites were laid out in six or
seven different places; the water system was extended by the
digging of nearly four hundred additional miles of irrigating ditches
and canals; and before the 1st of January 1905, one hundred and
twenty thousand acres of reclaimed land were actually under
cultivation, while two hundred thousand acres more had been
covered by water stock.
 Colorado Delta and Imperial Valley
The observed fertility of the soil completely discredited the reports
of the Government experts, and more than justified the prediction
made by Professor Blake half a century before that when the Sink
should be supplied with water, it would produce “crops of almost any
kind.” Grapes, melons and garden vegetables matured in the Valley
earlier than in any other part of California; barley was a profitable
crop; alfalfa could be cut five or six times a year; and the finest
quality of long-staple Egyptian cotton yielded more than a bale (500
pounds) to the acre. Experiments proved also that the climate and
soil were well adapted to the culture of grapes, grapefruit, oranges,
lemons, olives, figs, dates, pomegranates, apricots, peaches and
pears.
The fear that men would not be willing or able to do hard work in
the hot climate of the valley proved to be wholly groundless. Great
heat is not necessarily weakening or prostrating unless it is
accompanied with great humidity, and the air of the Valley is at all
seasons extremely dry. In a discussion of this subject, Mr. H. T. Cory,
formerly chief engineer of the California Development Co., says:
“The climate of the region, with its long, hot, dry summers,
is peculiarly favorable to agricultural luxuriance. Thus it is that
here the very earliest grapes, fruits and vegetables are
produced for the United States market, with the consequent
advantage of commanding the highest prices. This is notably
true of the Imperial Valley cantaloupe, now famous all over
this country, and of the early grapes, asparagus etc. On
account of the very low humidity and gentle winds which blow
most of the time in hot weather, the sensible temperature—
which is indicated by the wet-bulb thermometer readings and
gives the measure of heat felt by the human body—is much
less than the actual temperature as measured by the dry bulb.
It is conservative to say that a temperature of 110 in Imperial
Valley is not more uncomfortable than 95 in Los Angeles, or
85 in the more humid sections of the Eastern States.
Furthermore the nights are always cool, the low humidity
resulting in rapid and large daily temperature variations.”
Under these favoring conditions of soil and climate, it seemed
almost certain, in 1904, that the Imperial Valley would have a great
and prosperous future; but no forecast in that region is trustworthy
unless it takes into account the irrigating agency, as well as the
climate and the soil. The Colorado River created the Salton Sink,
and made fertile the Imperial Valley; but it could destroy, as well as
create; and in 1904 it showed itself in a new aspect and threatened
the Valley with a terrible calamity.
A Part of the Colorado River Watershed. The Grand Cañon

FOOTNOTES:
[3] Mr. H. T. Cory.
[4] Mr. Cory.
[5] In his “Imperial Valley and Salton Sink,” Mr. H. T. Cory,
formerly chief engineer of the California Development Co., refers
to Mr. Chaffey in the following words:
“The writer takes pleasure in expressing appreciation of the
standing of Mr. George M. Chaffey in irrigation work in the West.
The Ontario Colony he founded in 1883 was selected ten years
later as a model for the irrigation exhibit at the World’s Exposition,
and in his work at Mildura, Australia, he designed, had built in
England, and installed, the first centrifugal pumps on the same
shaft with a total capacity of 320 cubic feet per second lifted 20
feet. He is at present, among other things, head of the
magnificent water system irrigating 10,000 acres of citrus lands
near Whittier, California, including the highest priced agricultural
lands in California ($5,000 per acre). Furthermore he is a man of
affairs, and of large means which he acquired principally in
irrigation enterprises and banking.”
[6] Andrew M. Chaffey.
[7] List of stockholders in Sou. Pac. office, N. Y.
[8] Andrew M. Chaffey.
 THE RUNAWAY RIVER
The most serious problem with which engineers have to deal in
the irrigation of arid land from a turbid river is the getting rid of silt,
and this problem is a particularly difficult one in the Imperial Valley,
owing to the immense amount of sediment that the irrigating water
contains. The Colorado River, until after it passes the Grand Cañon,
is almost everywhere a swift, turbulent stream, with great eroding
capacity. As Mr. E. C. LaRue has said, in a brief but graphic
description of it,
“When the snows melt in the Rocky and Wind River
Mountains, a million cascade brooks unite to form a thousand
torrent creeks; a thousand torrent creeks unite to form half a
hundred rivers beset with cataracts; half a hundred roaring
rivers unite to form the Colorado, which flows, a mad, turbid
stream, into the Gulf of California.” (“Colorado River and Its
Utilization,” a Geological Survey report, Government Printing
Office, Washington 1916.)
Such a river, naturally, dissolves the earth and gnaws the rocks
over which it tears its way, and takes up millions of tons of solid
matter, in the shape of gravel, sand and finely pulverized soil. This
great volume of sediment, when finally dropped, not only tends to
change the river’s course by creating bars at or near its mouth, but
gradually fills up the irrigating ditches and canals and thus lessens
their carrying capacity. A single day’s supply of water for the Imperial
Valley contains silt enough to make a levee twenty feet high, twenty
feet wide, and one mile long. (Imperial Valley Press, July 25 1916). If
this silt is not dredged out, sluiced out, or collected in a settling
basin, it eventually raises the beds of the canals, fills the ditches,
and chokes up the whole irrigation system.
The managers of the California Development Co. had difficulty,
almost from the first, in keeping their waterways open. As more and
more land was brought into cultivation, more and more water was
required, while the silting up of the canals lessened the ability of the
company to meet the constantly increasing demand. There was a
shortage as early as the winter of 1902-3; but the situation did not
become serious until the following year, when the main canal, for a
distance of four miles below the intake, became so silted up that it
could not possibly carry the volume of water that was imperatively
needed. An attempt was made to remedy this state of affairs by
putting in a waste-gate, eight miles below the intake, for the purpose
of sluicing out the channel in time of high water.
“The idea” (as stated by Mr. Cory) “was to divert a large
quantity of water during the flood season, waste it through the
Best waste-gate, and in this way scour out the upper portion
of the canal. At first, the action was as expected, and some
two feet in the bottom were carried away. When, however, the
river reached its maximum height, ... and carried an excessive
silt content, especially of the heavier and sandy type, this
scouring action was entirely overcome, and the bottom of this
stretch was raised approximately one foot higher than during
the previous year.”
This silting up of the main canal, and the consequent reduction of
its carrying capacity, caused great injury to the agricultural interests
of the Valley. Crops in many places perished for lack of water, and
hundreds of farmers put in damage claims, which amounted in the
aggregate to half a million dollars. In the late summer of 1904, it
became evident that radical measures would have to be taken at
once to increase the water supply. As the managers of the company
had neither the financial means nor the requisite machinery for
quickly dredging out the silted part of the canal, they decided, in
September of that year, to cut a new intake from the river at a point
about four miles south of the international boundary. This would
eliminate the choked-up part of the canal, and let water directly into
the part that was unobstructed.
 The Three Headings (or Intakes), in Spring of 1905
If President Heber and Chief Engineer Rockwood had been aware
of the fact that the Colorado was even then preparing to pour its
waters into the Salton Sink, by making one of its semi-millennial
changes of course, they might perhaps have fortified the western
bank instead of cutting through it; but there was little or nothing to
show the extreme instability of the conditions that were then
determining the trend of the river across its delta, and the idea that it
might burst through this intake and again turn the Valley into a fresh-
water lake does not seem to have occurred to anyone. The cutting
was therefore made and the water shortage relieved; but at the cost
of imminent peril to the whole Valley and its twelve thousand
inhabitants.
In view of the tremendous and disastrous consequences of this
measure, it is only fair that Chief Engineer Rockwood should be
allowed to state, with some fullness, his reasons for adopting it, and
for failing to put in a head-gate to control the flow of water through
the channel and thus prevent its enlargement. In an article entitled
“Born of the Desert,” published in the second annual magazine
number of the Calexico Chronicle, in May 1909, he sets forth his
reasons in the following words:
“As soon as the summer flood (1904) dropped, I discovered
that instead of the bottom” (of the canal) “being lower, it was
approximately one foot above that of the year previous.... We
knew that with the dredging tools which we had it would be
impossible to dredge out this four miles of canal in sufficient
time for the uses of the Valley, providing the water in the river
should drop as low as it had the previous year.... We were
then confronted with the proposition of doing one of two
things, either cutting a new heading from the canal to the river
below the silted four-mile section of the canal, or else allowing
the Valley to pass through another winter with an insufficient
water supply. The latter proposition we could not face, for the
reason that the people of the Valley had an absolute right to
demand that water should be furnished them, and it was
questionable in our minds as to whether we would be able to
keep out of bankruptcy if we were to be confronted by another
period of shortage in the coming season of 1904-1905.
“The cutting of the lower intake, after mature deliberation,
and upon the insistence of several of the leading men of the
Valley, was decided upon. We hesitated about making this
cut, not so much because we believed we were incurring
danger of the river’s breaking through, as from the fact that
we had been unable to obtain the consent of the Government
of Mexico to make it, and we believed that we were
jeopardizing our Mexican rights should the cut be made
without the consent of the Government. On a telegraphic
communication, however, from our attorney in the City of
Mexico, to go ahead and make the cut, we did so, under the
presumption that he had obtained the necessary permit from
the Mexican authorities. It was some time after this, in fact
after the cut was made in the river, before we discovered that
he had been unable to obtain the formal permit, but had
simply obtained the promise of certain officials that we would
not be interfered with, providing that plans were at once
submitted for the necessary controlling structures to be
placed in this heading.
“... In cutting from the main canal to the river at this point,
we had to dredge a distance of 3300 feet only, through easy
material to remove, while an attempt to dredge out the main
canal above would have meant the dredging of four miles of
very difficult material. We began the cut the latter end of
September and completed it in about three weeks. As soon
as the cut was decided upon, elaborate plans for a controlling
gate were immediately started, and when completed, early in
November, were immediately forwarded to the City of Mexico
for the approval of the engineers of the Mexican Government,
without whose approval we had no authority or right to
construct the gate. Notwithstanding the insistence of our
attorney in the City of Mexico, and various telegraphic
communications insisting upon this approval being hurried,
we were unable to obtain it until twelve months afterward,
namely, the month of December 1905.
“In the meantime, serious trouble had begun. We have
since been accused of gross negligence and criminal
carelessness in making this cut; but I doubt as to whether
anyone should be accused of negligence, or carelessness, in
failing to foresee what had never happened before. We had
before us at the time the history of the river as shown by the
rod-readings kept at Yuma for a period of twenty seven years.
In the twenty seven years there had been but three winter
floods. In no winter of the twenty seven had there been two
 winter floods. It was not probable, then, that there would be
any winter flood to enlarge the cut made by us, and without
doubt, as it seemed to us, we would be able to close the cut,
before the approach of the summer flood, by the same means
that we had used in closing the cut for three successive years
around the Chaffey gate at the head of the canal.[9] During
this winter of 1905, however, we had more than one winter
flood. The first flood came, I believe, about the first of
February, but did not enlarge the lower intake. On the
contrary, it caused such a silt deposit in the lower intake that I
found it necessary, after the flood had passed, to put the
dredge through in order to deepen the channel sufficiently to
allow water to come into the valley for the use of the people.
This was followed shortly by another heavy flood that did not
erode the banks of the intake, but, on the contrary, the same
as the first, caused a deposit of silt and a necessary dredging.
We were not alarmed by these floods, as it was still very early
in the season. No damage had been done by them, and we
still believed that there would be no difficulty in closing the
intake before the approach of the summer flood, which was
the only one we feared. However, the first two floods were
followed by a third, coming sometime in March, and this was
sufficient notice to us that we were up against a very unusual
season, something unknown in the history of the river as far
back as we were able to reach; and as it was now
approaching the season of the year when we might
reasonably expect the river surface to remain at an elevation
that would allow sufficient water for the uses of the Valley to
be gotten through the upper intake, we decided to close the
lower.” (“Born of the Desert,” by C. R. Rockwood, Calexico
Chronicle, May 1909.)
At the time when the first attempt to close the intake was made,
the cutting was about sixty feet wide. A dam of piles, brush and
sandbags was thrown across it in March 1905, but it had hardly been
completed when another flood came down the Colorado and swept it
away. A second dam of the same kind, built a few weeks later,
shared the same fate. By the middle of June, the river was
discharging 90,000 cubic feet of water per second; the width of the
lower intake had increased from sixty feet to one hundred and sixty;
water was overflowing the banks of the main canal and accumulating
in the deepest part of the Sink; and a new Salton Sea was in process
of formation.

Lower Intake at Time of Southern Pacific Loan

 Such was the state of affairs when Mr. Harriman and the Southern
Pacific Railroad Company first became directly interested in the
problem of river control. Early in 1905, the California Development
Co., finding itself in pecuniary difficulties, applied to Mr. Julius
Kruttschnitt, General Manager of the Southern Pacific, for a loan, on
the alleged ground that the Imperial Valley was furnishing a great
deal of traffic to the railroad, and the irrigation company was
therefore warranted in asking for financial assistance. Mr.
Kruttschnitt, however, declined to consider the application. The
petitioners then addressed the President of the railroad company,
Mr. E. H. Harriman, who, it was thought, might be induced to give the
necessary aid, even though he had no personal interest in the Valley
and no connection whatever with the California Development Co. Mr.
Harriman, as a man of imagination and far-seeing vision, was
naturally in sympathy with the bold attempt to irrigate and reclaim the
arid lands of the Colorado Desert, and when the matter of the loan
was presented to him, he not only gave it immediate consideration,
but ordered an investigation and a report. He finally consented,
against the advice of Mr. Kruttschnitt and other counsellors, to loan
the Development Company $200,000, “to be used in paying off
certain of its floating indebtedness and in completing and perfecting
its canal system.” Inasmuch, however, as the financial management
of the irrigation company had not always been judicious, Mr.
Harriman and the Southern Pacific stipulated that they should have
the right to select three of its directors, one of whom should be
president, and that fifty one per cent of its stock (6300 shares)
should be placed in the hands of a trustee as collateral security for
the loan. This stipulation was agreed to, and on the 20th of June
1905, the Southern Pacific Company, as chief creditor, took
temporary control of the California Development Company by
selecting three of its directors, and by appointing as its president Mr.
Epes Randolph, of Tucson, who was then acting also as president of
the Harriman Lines in Arizona and Mexico.[10]
When Mr. Harriman and the Southern Pacific thus took over the
management of the California Development Company, they had no
intention of assuming its responsibilities, directing its engineering