Silver halides, structure

The formation of the combination of defects may be described as a chemical reaction and thermodynamic equilibrium conditions may be applied. The chemical notations of Kroger-Vink, Schottky, and defect structure elements (DSEs) are used [3, 11]. The chemical reactions have to balance the chemical species, lattice sites, and charges. An unoccupied lattice site is considered to be a chemical species (V) it is quite common that specific crystal structures are only found in the presence of a certain number of vacancies [12]. The Kroger-Vink notation makes use of the chemical element followed by the lattice site of this element as subscript and the charge relative to the ideal undisturbed lattice as superscript. An example is the formation of interstitial metal M ions and metal M ion vacancies, e.g., in silver halides ... 

Despite the fact that not all details of the photographic process are completely understood, the overall mechanism for the production of the latent image is well known. Silver chloride, AgBr, crystallizes with the sodium chloride structure. While Schottky defects are the major structural point defect type present in most crystals with this structure, it is found that the silver halides, including AgBr, favor Frenkel defects (Fig. 2.5). 

At all temperatures above 0°K Schottky, Frenkel, and antisite point defects are present in thermodynamic equilibrium, and it will not be possible to remove them by annealing or other thermal treatments. Unfortunately, it is not possible to predict, from knowledge of crystal structure alone, which defect type will be present in any crystal. However, it is possible to say that rather close-packed compounds, such as those with the NaCl structure, tend to contain Schottky defects. The important exceptions are the silver halides. More open structures, on the other hand, will be more receptive to the presence of Frenkel defects. Semiconductor crystals are more amenable to antisite defects. 

The group of ion-selective electrodes with fixed ion-exchange sites includes systems with various membrane structures. The membranes are either homogeneous (single crystals, pressed pellets, sintered materials) or heterogeneous, set in an inactive skeleton of various polymeric materials. Important electrode materials include silver halides, silver and divalent metal chalcogenides, lanthanum trifluoride and various glassy materials. Here, the latter will be surveyed only briefly, for the sake of completeness. 

Such dyes found early application as sensitizers in photography and many thousands of related structures have been made. Suitable dyes when added to the photographic emulsion extend the sensitivity of the silver halide from the blue and UV region towards the green, red and near IR. The sensitivity of the dyes can be balanced throughout the visible spectrum to give panchromatic emulsions. 

It has been necessary to understand the relationship between molecular fine structure of cyanine dyes and important properties such as colour, dye aggregation, adsorption on silver halide and electrochemical potentials in order to design and prepare sensitizers with optimum performance. For general discussion of these topics and the mechanism of spectral sensitization, the reader is referred to recent surveys on the subject (B-77MI11401, 77HC(30)441). 

Thus increased covalent bonding resulting from Fajans-type phenomena can lower the transition temperatures. For example, the alkali halides (except CsCI, CsBr. and Csl) and the silver halides (except Agl) crystallize in the NaCI structure. The sizes of the cations are comparable Na = M6 pm. Ag = 129 pm, K = 152 pm, yet the melting points of the halides are considerably different (Table 8.6). The greater covalent character of the silver halide bond (resulting from the electron confi J ra-... 

Neutral adducts of silver halides with phosphines have been discussed earlier under Section 54.1.3.1. 1 1 adducts were found to be tetrameric and adopted either a (pseudo)- cubane or chair ( step ) type structure. 

Until recently, only two reports existed for 1 1 adducts of silver halides with amines, namely AgT piperidine57 and Agl-morpholine.381 The first had a tetrameric cubane structure whilst the second was described as a stair polymer adduct. The range has now been extended to include 2-and 3-methylpyridine, quinoline and triethylamine.382 In each case the adduct was obtained by recrystallization of silver(I) iodide from neat base. The colourless crystals were found to lose base readily on exposure to the atmosphere and structural data were collected from crystals mounted in argon-filled capillaries, containing mother liquor. 

Reactions of limited proportions of amine and phosphine Lewis bases with non-molecular copper and silver halides generate crystalline cubanes. Crystallographic determinations of molecular structure have been reported for at least 31 complexes with cf or d10 metal configurations, spanning the following types or homologous series of compounds. Compilations of data occur in references 157, 158 and 167. 

Silver halide precipitates at a rate that depends upon the structure of the alkyl group, tertiary > secondary > primary. Tertiary halides usually react immediately at room temperature, whereas primary halides require heating. That complexes actually are formed between organic halides and silver ion is indicated by an increase in water solubility in the presence of silver ion for those halides that are slow in forming carbocations. 

The thiosulfate ion, S2 O2- "3, is a structural analogue of the sulfate ion where one oxygen atom is replaced by one sulfur atom. The two sulfur atoms of thiosulfate thus are not equivalent. Indeed, the unique chemistry of the thiosulfate ion is dominated by the sulfide-like sulfur atom which is responsible for both the reducing properties and complexing abilities. The ability of thiosulfates to dissolve silver halides through complex formation is the basis for their commercial application in photography (qv). 

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