Silver bromide (AgBr) structure, properties and uses

2019
Egbert Haynes

The silver bromide it is an inorganic salt whose chemical formula is AgBr. Its solid consists of cations Ag+ and Br anions- in a 1: 1 ratio, attracted by electrostatic forces or ionic bonds. It can be seen as if metallic silver had given one of its valence electrons to molecular bromine.

Its nature resembles its "brothers" silver chloride and iodide. All three salts are insoluble in water, have similar colors, and are also sensitive to light; that is, they undergo photochemical reactions. This property has been used in obtaining photographs, as a result of the reduction of Ag ions+ to metallic silver.

Silver bromide ions. Source: Claudio Pistilli [CC BY-SA 4.0 (https://creativecommons.org/licenses/by-sa/4.0)]

The image above shows an ion pair Ag+Br-, in which the white and brown spheres correspond to Ag ions+ and Br-, respectively. Here they represent the ionic bond as Ag-Br, but it is necessary to indicate that there is no such covalent bond between both ions.

It may seem contradictory that silver is the one that contributes the black color to photographs without color. This is because the AgBr reacts with light, generating a latent image; which, then, is intensified by increasing the reduction of silver.

Article index

  • 1 Structure of silver bromide
    • 1.1 Crystal defects
  • 2 Synthesis
  • 3 Properties
    • 3.1 Appearance
    • 3.2 Molecular mass
    • 3.3 Density
    • 3.4 Melting point
    • 3.5 Boiling point
    • 3.6 Solubility in water
    • 3.7 Refractive index
    • 3.8 Heat capacity
    • 3.9 Sensitivity to light
  • 4 Uses
  • 5 References

Structure of silver bromide

Crystal structure of silver bromide. Source: Benjah-bmm27 via Wikipedia.

Above is the lattice or crystal structure of silver bromide. Here is a more faithful representation of the difference in size between the ionic radii of Ag+ and Br-. Br anions-, more voluminous, they leave interstices where the Ag cations are located+, which is surrounded by six Br- (and vice versa).

This structure is characteristic of a cubic crystalline system, specifically of the rock salt type; the same, for example, as for sodium chloride, NaCl. In fact, the image facilitates this by arranging a perfect cubic boundary.

At first glance it can be seen that there is a certain difference in size between the ions. This, and perhaps the electronic characteristics of the Ag+ (and the possible effect of some impurities), leads to AgBr crystals showing defects; that is, places where the ordering sequence of ions in space is "broken".

Crystal defects

These defects consist of voids left by absent or displaced ions. For example, between six anions Br- normally the cation Ag should be+; but instead, there may be a void due to the silver having moved into another gap (Frenkel defect).

Although they affect the crystal lattice, they favor the reactions of silver with light; and the larger the crystals or their cluster (size of grains), the greater the number of defects, and therefore, it will be more sensitive to light. Likewise, impurities influence the structure and this property, especially those that can be reduced with electrons..

As a consequence of the latter, large AgBr crystals require less exposure to light to reduce them; that is, they are more desirable for photographic purposes.

Synthesis

In the laboratory, silver bromide can be synthesized by mixing an aqueous solution of silver nitrate, AgNO3, with the salt of sodium bromide, NaBr. The first salt contributes the silver, and the second the bromide. What follows is a double displacement or metathesis reaction that can be represented by the chemical equation below:

AgNO3(aq) + NaBr (s) => NaNO3(aq) + AgBr (s)

Note that the sodium nitrate salt, NaNO3, it is soluble in water, while AgBr precipitates as a solid with a faint yellow color. Subsequently the solid is washed and subjected to vacuum drying. In addition to NaBr, KBr could also be used as a source of bromide anions.

On the other hand, AgBr can naturally be obtained through its mineral bromirite and its due purification processes..

Properties

Appearance

Clay-like, whitish-yellow solid.

Molecular mass

187.77 g / mol.

Density

6.473 g / mL.

Melting point

432 ° C.

Boiling point

1502 ° C.

Water solubility

0.140 g / mL at 20 ° C.

Refractive index

2,253.

Heat capacity

270 J / Kg K.

Sensitivity to light

It was said in the previous section that there are defects in AgBr crystals that promote the sensitivity of this salt to light, since they trap the electrons formed; and thus, in theory, they are prevented from reacting with other species in the environment, such as oxygen in the air.

The electron is released from the Br reaction- with a photon:

Br- + hv => 1 / 2Brtwo + and-

Note that Br is producedtwo, which will stain the solid red if it is not removed. Released electrons reduce Ag cations+, in its interstices, to metallic silver (sometimes represented as Ag0):

Ag+ + and- => Ag

Having then the net equation:

AgBr => Ag + 1 / 2Brtwo

When the "first layers" of metallic silver form on the surface, it is said that there is a latent image, still invisible to the human eye. This image becomes millions of times more visible if another chemical species (such as hydroquinone and phenidone, in the development process) increases the reduction of the AgBr crystals to metallic silver.

Applications

Black and white photograph of pocket watch. Source: Pexels.

Silver bromide is the most widely used of all its halides in the field of photographic film development. AgBr is applied on said films, made with cellulose acetate, suspended in a gelatin (photographic emulsion), and in the presence of 4- (methylamino) phenol sulfate (Metol) or phenidone, and hydroquinone.

With all these reagents, the latent image can be brought to life; finish and accelerate the transformation of ionic to metallic silver. But, if you do not proceed with certain care and experience, all the silver on the surface will oxidize, and the contrast between the black and white colors will end..

That is why the stop, fixation and wash dipping steps of photographic films are vital..

There are artists who play with these processes in such a way that they create shades of gray, which enrich the beauty of the image and their own legacy; and they do all this, sometimes perhaps without suspecting it, thanks to chemical reactions, whose theoretical basis can become a bit complex, and to a light-sensitive AgBr that marks a starting point.

References

  1. Wikipedia. (2019). Silver bromide. Recovered from: en.wikipedia.org
  2. Michael W. Davidson. (2015, November 13). Polarized Light Digital Image Gallery: Silver Bromide. Olympus. Recovered from: micro.magnet.fsu.edu
  3. Crystran Ltd. (2012). Silver bromide (AgBr). Recovered from: crystran.co.uk
  4. Lothar Duenkel, Juergen Eichler, Gerhard Ackermann, and Claudia Schneeweiss. (June 29, 2004). Self-made silver-bromide-based emulsions for users in holography: manufacturing, processing, and application, Proc. SPIE 5290, Practical Holography XVIII: Materials and Applications; doi: 10.1117 / 12.525035; https://doi.org/10.1117/12.525035
  5. Alan G. Shape. (1993). Inorganic chemistry. (Second edition.). Editorial Reverté.
  6. Carlos Güido and Ma Eugenia Bautista. (2018). Introduction to photographic chemistry. Recovered from: fotografia.ceduc.com.mx
  7. García D. Bello. (January 9, 2014). Chemistry, photography and Chema Madoz. Recovered from: dimethylsulfuro.es

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