Glass-dissolution reaction

For the purposes of this review, the key concept embedded in equation (1) is the chemical affinity term, which is expressed as 1 — Q/K. The chemical affinity of a system is related to the free energy of the reaction and is a measure of the degree of departure from equilibrium (i.e.,/(AG) = 1 — Q/K). The form of the chemical affinity term indicates that as the concentrations of dissolved elements build up in solution, the system approaches saturation in a rate-limiting solid and the overall dissolution reaction slows down, and, at equilibrium, the rate would be zero. In the case of glass dissolution, there are many circumstances, which are reviewed below, where the rate behaviour does not comply with these expectations. 

The other predominant reaction of water with glass is dissolution. This typically occurs with basic solutions. Glass dissolution reactions result in the release of metal ions and other inorganic materials [2] (see Figure 3). 

Therefore the setup where the dissolution reaction is followed by potentiometric measurements of the pertinent H -concentration within the galvanic cell (glass electrode solution salt bridge reference electrode) is an optimal system for solubility measurements. This method is called potentiometric method of solubility measiuements ( Potentio in Table 1.1). An example of such measurements could be tiiat of solubility of metal oxides at temperatures up to 300°C performed in ORNL using simultaneously sampling method and the hydrogen-electrode concentration cell (HECC). The details of such measurements and experimental setup can be found in Chapter 3 in this Book. 

Potassium siUcates are manufactured in a manner similar to sodium siUcates by the reaction of K CO and sand. However, crystalline products are not manufactured and the glass is suppHed as a flake. A 3.90 mole ratio potassium siUcate flake glass dissolves readily in water at ca 88°C without pressure by incremental addition of glass to water. The exothermic heat of dissolution causes the temperature of the solution to rise to the boiling point. Lithium sihcate solutions are usually prepared by dissolving siUca gel in a LiOH solution or mixing colloidal siUca with LiOH. 

The results of determination of the form of presence of As, Se, Nb, Mo, Ni, Cu in different solid compounds ai e given. The application of RII LEL for the study of stmctural transformations in chalkogenid glasses is shown. The X-ray spectral determination of crystal water, the possibility of studying of dissolution-crystallization processes and kinetics of some chemical reactions ai e discussed. 

On cooling (NH4)2S5 crystallizes as yellow to orange-yellow needles which melt at 95 °C in a sealed glass tube but decompose in air [reverse reaction at Eq. (17)] and on dissolution in water. (Et4N)2Ss is obtained by reaction of Et4NCl with Na2S5 in ethanol [33]. 

Ring-opening polymerization was used to synthesize PTMC. The polymerization was carried out in evacuated and sealed glass ampoules with stannous octoate as a catalyst. The schematic reaction equations are shown in Schemes 8.7 and 8.8. The reaction time for aU homo- and copolymerizations were three days and the reaction temperature at 130 2°C. The obtained polymers were purified by dissolution in chloroform and precipitation in isopropanol. The precipitated polymers were collected, and washed with fresh isopropanol, and dried under reduced pressure at room temperamre until constant weight. 

While the cuprous cyanide solution is warmed gently (to 60°-70°) on the water bath, a solution of p-tolyldiazonium chloride is prepared as follows Heat 20 g. of p-toluidine with a mixture of 50 g. of concentrated hydrochloric acid and 150 c.c. of water until dissolution is complete. Immerse the solution in ice-water and stir vigorously with a glass rod so that the toluidine hydrochloride separates as far as possible in a microcrystalline form. Then cool the mixture in ice and diazotise with a solution of 16 g. of sodium nitrite in 80 c.c. of water, added until the nitrous acid test with potassium iodide-starch paper persists. The diazonium chloride solution so obtained is poured during the course of about ten minutes into the warm cuprous cyanide solution, which is meanwhile shaken frequently. After the diazo-solution has been added the reaction mixture is heated under an air condenser on the water bath fox a further quarter of an hour, and then the toluic nitrile is separated by distillation with steam (fume chamber, HCN ). The nitrile (which passes over as a yellowish oil) is extracted from the distillate with ether, the p-cresol produced as a by-product is removed by shaking the ethereal extract twice with 2 A-sodium hydroxide solution, the ether is evaporated,... 

Qualitatively, the dipole-dipole interactions between the macro-molecular chains and the halide salt compensate for the lattice energy of the halide crystal and tend to decrease the interactions existing in the glass between the oxide macroanions. This decrease is probably the reason for the significant drop in the glass transition temperature resulting from the addition of a halide salt (Reggiani et al, 1978). Furthermore this type of reaction is consistent with the fact that dissolution of a halide salt in a vitreous solvent requires the existence of ionic bonds provided by a network modifier. 

Diffusion is ubiquitous in nature whenever there is heterogeneity, there is diffusion. In liquid and gas, flow or convection is often present, which might be the dominant means of mass transfer. However, inside solid phases (minerals and glass), diffusion is the only way of mass transfer. Diffusion often plays a major role in solid-state reactions, but in the presence of a fluid dissolution and recrystallization may dominate. 

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