Silver halide

A silver halide is one of the compounds formed between silver and one of the halogens — silver bromide (AgBr), chloride (AgCl), iodide (AgI), and two forms of silver fluorides. As a group, they are often referred to as the silver halides, and are often given the pseudo-chemical notation AgX. Although most silver halides involve silver atoms with oxidation states of +1 (Ag⁺), silver halides in which the silver atoms have oxidation states of +2 (Ag²⁺) are known, of which silver(II) fluoride is the only known stable one.

In photography, "silver halide" precludes silver fluoride.

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Applications

Light sensitivity

Silver halides are used in photographic film and photographic paper where silver halide crystals in gelatin are coated on to a film base, glass or paper substrate. The gelatin is a vital part of the emulsion as the protective colloid of appropriate physical and chemical properties. Gelatin may also contain trace elements (such as sulfur) which increase the light sensitivity of the emulsion, although modern practice uses gelatin without such components. When absorbed by an AgX crystal, photons cause electrons to be promoted to a conduction band (de-localized electron orbital with higher energy than a valence band) which can be attracted by a sensitivity speck, which is a shallow electron trap, which may be a crystalline defect or a cluster of silver sulfide, gold, other trace elements (dopant), or combination thereof, and then combined with an interstitial silver ion to form silver metal speck. Silver bromide and silver chloride may be used separately or combined, depending on the sensitivity and tonal qualities desired in the product. Silver iodide is always combined with silver bromide or silver chloride, except in the case of daguerreotype production where a daguerreotype (one of the oldest photographic processes) is developed with pure red light instead of mercury vapors (a method known as the Bequerelle method, named for the inventor who discovered the phenomenon).

Silver halides are also used to make some corrective lenses darken when exposed to ultraviolet light (see photochromism).

When a silver halide crystal is exposed to light, a sensitivity speck on the surface of the crystal is turned into a small speck of metallic silver (these comprise the invisible or latent image). If the speck of silver contains approximately four or more atoms, it is rendered developable - meaning that it can undergo development which turns the entire crystal into metallic silver. Areas of the emulsion receiving larger amounts of light (reflected from a subject being photographed, for example) undergo the greatest development and therefore results in the highest optical density.

Chemistry

Silver halides, except for silver fluoride, are extremely insoluble in water. Silver nitrate can be used to precipitate halides; this application is useful in quantitative analysis of halides. The precipitation of silver halides via silver nitrate is also useful for abstracting halide leaving groups.

However, close attention is necessary for other compounds in the test solution. Some compounds can considerably increase or decrease the solubility of AgX. Examples of compounds that increase the solubility include: cyanide, thiocyanate, thiosulfate, thiourea, amines, ammonia, sulfite, thioether, crown ether. Examples of compounds that reduces the solubility include many organic thiols and nitrogen compounds that do not posses solubilizing group other than mercapto group or the nitrogen site, such as mercaptooxazoles, mercaptotetrazoles, especially 1-phenyl-5-mercaptotetrazole, benzimidazoles, especially 2-mercaptobenzimidazole, benzotriazole, and these compounds further substituted by hydrophobic groups. Compounds such as thiocyanate and thiosulfate enhance solubility when they are present in a sufficiently large quantity, due to formation of highly soluble complex ions, but they also significantly depress solubility when present in a very small quantity, due to formation of sparingly soluble complex ions.

References