Silver bromide

Silver bromide (AgBr), a soft, pale-yellow, water-insoluble salt well known (along
with other silver halides) for its unusual sensitivity to light. This property has allowed
silver halides to become the basis of modern photographic materials. AgBr is widely
used in photographic films and is believed by some to have been used for making the
Shroud of Turin. The salt can be found naturally as the mineral bromargyrite
(bromyrite).

Silver bromide

Names

Other names

bromargyrite
bromyrite
silver(I) bromide

Identifiers

CAS Number ▪ 7785-23-1

3D model (JSmol) ▪ Interactive image

ChemSpider ▪ 59584

ECHA InfoCard 100.029.160

UNII ▪ NHQ37BJZ2Z

CompTox ▪ DTXSID4064844
Dashboard (EPA)

InChI

SMILES

Properties

Chemical formula AgBr

Molar mass 187.77 g/mol

Appearance Pale yellow solid

photosensitive

Density 6.473 g/cm3, solid

Melting point 432 °C (810 °F; 705 K)

Boiling point 1,502 °C (2,736 °F;

1,775 K) (decomposes)

Solubility in water 0.140 mg/L (20 °C)

Solubility product 5.4 × 10 −13

(Ksp)

Solubility insoluble in alcohol, most

acids
sparingly soluble
in ammonia
soluble in alkali cyanide
solutions

Band gap 2.5 eV

Electron mobility 4000 cm2/(V·s)

 Magnetic −59.7·10−6 cm3/mol
susceptibility (χ)

Refractive index (nD) 2.253

Thermochemistry

Heat capacity (C) 270 J/(kg·K)

Std molar 107 J·mol−1·K−1

entropy (So298)

Std enthalpy of −100 kJ·mol−1

formation (ΔfH⦵298)

Related compounds

Other anions Silver(I) fluoride

Silver chloride
Silver iodide

Other cations Copper(I) bromide

Mercury(I) bromide

Except where otherwise noted, data are given for

materials in their standard state (at 25 °C [77 °F],
100 kPa).

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Infobox references

Preparation
Although the compound can be found in mineral form, AgBr is typically prepared by
the reaction of silver nitrate with an alkali bromide, typically potassium bromide:
AgNO3(aq) + KBr(aq) → AgBr(s)+ KNO3(aq)

Although less convenient, the salt can also be prepared directly from its elements.

Modern preparation of a simple, light-sensitive surface involves forming an emulsion

of silver halide crystals in a gelatine, which is then coated onto a film or other support.
The crystals are formed by precipitation in a controlled environment to produce
small, uniform crystals (typically < 1 μm in diameter and containing ~1012 Ag atoms)
called grains.
Reactions
Silver bromide reacts readily with liquid ammonia to generate a variety of ammine
complexes, like Ag(NH
3)

2Br and Ag(NH

3)

2Br−

2. In general:

AgBr + m NH3 + (n - 1) Br−

→ Ag(NH
3)

mBr1-n

Silver bromide reacts with triphenylphosphine to give a tris(triphenylphosphine)

product:

Physical properties
Crystal structure
AgF, AgCl, and AgBr all have face-centered cubic (fcc) rock-salt (NaCl) lattice structure
with the following lattice parameters:
Unit cell structure

Silver halide lattice properties

Compound Crystal Structure Lattice, a /Å

AgF fcc rock-salt, NaCl 4.936

AgCl, Chlorargyrite fcc rock-salt, NaCl 5.5491

AgBr, Bromargyrite fcc rock-salt, NaCl 5.7745

 face-centered cubic rock-salt structure

The larger halide ions are arranged in a cubic close-packing, while the smaller silver
ions fill the octahedral gaps between them, giving a 6-coordinate structure where a
silver ion Ag+ is surrounded by 6 Br− ions, and vice versa. The coordination geometry
for AgBr in the NaCl structure is unexpected for Ag(I) which typically forms linear,
trigonal (3-coordinated Ag) or tetrahedral (4-coordinated Ag) complexes.
Unlike the other silver halides, iodargyrite (AgI) contains a hexagonal zincite lattice
structure.

Solubility
The silver halides have a wide range of solubilities. The solubility of AgF is about 6 ×
107 times that of AgI. These differences are attributed to the relative solvation
enthalpies of the halide ions; the enthalpy of solvation of fluoride is anomalously
large.
Silver halide solubilities

Compound Solubility (g / 100 g H2O)

AgF 172

AgCl 0.00019

AgBr 0.000014

AgI 0.000003

Photosensitivity
Although photographic processes have been in development since the mid-1800s,
there were no suitable theoretical explanations until 1938 with the publication of a
paper by R.W. Gurney and N.F. Mott. This paper triggered a large amount of research
in fields of solid-state chemistry and physics, as well more specifically in silver halide
photosensitivity phenomena.
Further research into this mechanism revealed that the photographic properties of
silver halides (in particular AgBr) were a result of deviations from an ideal crystal
structure. Factors such as crystal growth, impurities, and surface defects all affect
concentrations of point ionic defects and electronic traps, which affect the sensitivity
to light and allow for the formation of a latent image.
Frenkel defects and quadropolar deformation

The major defect in silver halides is the Frenkel defect, where silver ions are located
interstitially (Agi+) in high concentration with their corresponding negatively charged
silver-ion vacancies (Agv−). What is unique about AgBr Frenkel pairs is that the
interstitial Agi+ are exceptionally mobile, and that its concentration in the layer below
the grain surface (called the space-charge layer) far exceeds that of the intrinsic
bulk. The formation energy of the Frenkel pair is low at 1.16 eV, and the migration
activation energy is unusually low at 0.05 eV (compare to NaCl: 2.18 eV for the
formation of a Schottky pair and 0.75 eV for cationic migration). These low energies
result in large defect concentrations, which can reach near 1% near the melting point.
The low activation energy in silver bromide can be attributed the silver ions’ high
quadrupolar polarizability; that is, it can easily deform from a sphere into an ellipsoid.
This property, a result of the d9 electronic configuration of the silver ion, facilitates
migration in both the silver ion and in silver-ion vacancies, thus giving the unusually
low migration energy (for Agv−: 0.29–0.33 eV, compared to 0.65 eV for NaCl).
Studies have demonstrated that the defect concentrations are strongly affected (up to
several powers of 10) by crystal size. Most defects, such as interstitial silver ion
concentration and surface kinks, are inversely proportional to crystal size, although
vacancy defects are directly proportional. This phenomenon is attributed to changes
in the surface chemistry equilibrium, and thus affects each defect concentration
differently.
Impurity concentrations can be controlled by crystal growth or direct addition of
impurities to the crystal solutions. Although impurities in the silver bromide lattice
are necessary to encourage Frenkel defect formation, studies by Hamilton have shown
that above a specific concentration of impurities, the numbers of defects of interstitial
silver ions and positive kinks reduce sharply by several orders of magnitude. After
this point, only silver-ion vacancy defects, which actually increase by several orders of
magnitude, are prominent.
Electron traps and hole traps

When light is incident on the silver halide grain surface, a photoelectron is generated
when a halide loses its electron to the conduction band:
X− + hν → X + e−

After the electron is released, it will combine with an interstitial Agi+ to create a silver
metal atom Agi0:
e− + Agi+ → Agi0

Through the defects in the crystal, the electron is able to reduce its energy and
become trapped in the atom. The extent of grain boundaries and defects in the crystal
affect the lifetime of the photoelectron, where crystals with a large concentration of
defects will trap an electron much faster than a purer crystal.
When a photoelectron is mobilized, a photohole h• is also formed, which also needs to
be neutralized. The lifetime of a photohole, however, does not correlate with that of a
photoelectron. This detail suggests a different trapping mechanism; Malinowski
suggests that the hole traps may be related to defects as a result of impurities. Once
trapped, the holes attract mobile, negatively charged defects in the lattice: the
interstitial silver vacancy Agv−:
h• + Agv− ⇌ h.Agv

The formation of the h.Agv lowers its energy sufficiently to stabilize the complex and
reduce the probability of ejection of the hole back into the valance band (the
equilibrium constant for hole-complex in the interior of the crystal is estimated at
10−4.
Additional investigations on electron- and hole-trapping demonstrated that impurities
also can be a significant trapping system. Consequently, interstitial silver ions may not
be reduced. Therefore, these traps are actually loss mechanisms, and are considered
trapping inefficiencies. For example, atmospheric oxygen can interact with
photoelectrons to form an O2− species, which can interact with a hole to reverse the
complex and undergo recombination. Metal ion impurities such as copper(I), iron(II),
and cadmium(II) have demonstrated hole-trapping in silver bromide.
Crystal surface chemistry;

Once the hole-complexes are formed, they diffuse to the surface of the grain as a result
of the formed concentration gradient. Studies demonstrated that the lifetimes of holes
near the surface of the grain are much longer than those in the bulk, and that these
holes are in equilibrium with adsorbed bromine. The net effect is an equilibrium push
at the surface to form more holes. Therefore, as the hole-complexes reach the surface,
they disassociate:
h.Agv− → h• + Agv− → Br → FRACTION Br2

By this reaction equilibrium, the hole-complexes are constantly consumed at the

surface, which acts as a sink, until removed from the crystal. This mechanism provides
the counterpart to the reduction of the interstitial Agi+ to Agi0, giving an overall
equation of:
AgBr → Ag + FRACTION Br2
Latent image formation and photography

Now that some of the theory has been presented, the actual mechanism of the
photographic process can be discussed. To summarize, as a photographic film is
subjected to an image, photons incident on the grain produce electrons which interact
to yield silver metal. More photons hitting a particular grain will produce a larger
concentration of silver atoms, containing between 5 and 50 silver atoms (out of
~1012 atoms), depending on the sensitivity of the emulsion. The film now has a
concentration gradient of silver atom specks based upon varying intensity light across
its area, producing an invisible "latent image".
While this process is occurring, bromine atoms are being produced at the surface of
the crystal. To collect the bromine, a layer on top of the emulsion, called a sensitizer,
acts as a bromine acceptor.
During film development the latent image is intensified by addition of a chemical,
typically hydroquinone, that selectivity reduces those grains which contain atoms of
silver. The process, which is sensitive to temperature and concentration, will
completely reduce grains to silver metal, intensifying the latent image on the order of
1010 to 1011. This step demonstrates the advantage and superiority of silver halides
over other systems: the latent image, which takes only milliseconds to form and is
invisible, is sufficient to produce a full image from it.
After development, the film is "fixed," during which the remaining silver salts are
removed to prevent further reduction, leaving the "negative" image on the film. The
agent used is sodium thiosulfate, and reacts according to the following equation:
AgX(s) + 2 Na2S2O3(aq) → Na3[Ag(S2O3)2](aq) + NaX(aq)

An indefinite number of positive prints can be generated from the negative by passing
light through it and undertaking the same steps outlined above.
Semiconductor properties
As silver bromide is heated within 100 °C of its melting point, an Arrhenius plot of the
ionic conductivity shows the value increasing and "upward-turning." Other physical
properties such as elastic moduli, specific heat, and the electronic energy gap also
increase, suggesting the crystal is approaching instability. This behavior, typical of a
semi-conductor, is attributed to a temperature-dependence of Frenkel defect
formation, and, when normalized against the concentration of Frenkel defects, the
Arrhenius plot linearizes.

References
1. Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company.
p. A23. ISBN 978-0-618-94690-7.
2. Greenwood, N.N., Earnshaw, A. (1984). Chemistry of the Elements. New York: Permagon
Press. pp. 1185–87. ISBN 978-0-08-022057-4.
3. Hamilton, J.F. (1974). "Physical Properties of Silver Halide Microcrystals". Photographic
Science and Engineering. 18 (5): 493–500.
4. Leden, I., Persson, G.; Persson; Sjöberg; Dam; Sjöberg; Toft (1961). "The Solubility of
Silver Chloride and Silver Bromide in Aqueous Ammonia and the Formation of Mixed
Silver-Ammonia-Halide Complexes". Acta Chem. Scand. 15: 607–614.
doi:10.3891/acta.chem.scand.15-0607.
5. Engelhardt, LM; Healy, PC; Patrick, VA; White, AH (1987). "Lewis-Base Adducts of Group-
11 Metal(I) Compounds. XXX. 3:1 Complexes of Triphenylphosphine With Silver(I)
Halides". Aust. J. Chem. 40 (11): 1873–1880. doi:10.1071/CH9871873.
6. Glaus, S. & Calzaferri, G. (2003). "The band structures of the silver halides AgF, AgCl, and
AgBr: A comparative study". Photochem. Photobiol. Sci. 2 (4): 398–401.
doi:10.1039/b211678b.
7. Lide, David R. (ed). (2005)Handbook of Chemistry and Physics, 86th Edition, The
Chemical Rubber Publishing Co., Cleveland.
8. Gurney, R. W.; Mott, N. F. (1938). "The theory of the photolysis of silver bromide and the
photographic latent image". Proc. Roy. Soc. A164 (917): 151–167.
Bibcode:1938RSPSA.164..151G. doi:10.1098/rspa.1938.0011.
9. Slifkin, L. M. (1989). "The Physics of Lattice Defects in Silver Halides". Crystal Lattice
Defects and Amorphous Materials. 18: 81–96.
10. Malinowski, J. (1968). "The Role of Holes in the Photographic Process". The Journal of
Photographic Science. 16 (2): 57–62.