Reactants, solid state

Quantitative studies of solid-state organic reactions were performed by Glazman (267. 268). Equal amounts of acetic anhydride and 2-aminothiazole (grain diameter 0.15 mm) were mixed for 20 rain, and the mixture was heated in a glycerol bath at 0.5°C per minute. Heating curves showed that the reaction starts in the solid phase the use of an eutectic composition of organic reactants increases the yields. 

Crystal structure, crystal defects and chemical reactions. Most chemical reactions of interest to materials scientists involve at least one reactant in the solid state examples inelude surfaee oxidation, internal oxidation, the photographie process, electrochemieal reaetions in the solid state. All of these are critieally dependent on crystal defects, point defects in particular, and the thermodynamics of these point defeets, especially in ionic compounds, are far more complex than they are in single-component metals. I have spaee only for a superficial overview. 

The plan of this chapter is first to briefly recall the history of work in solid state chemistry. Following this, the mechanisms that the author proposes control shock-induced solid state chemistry will be considered in terms of shock-induced changes to potential reactants. Enhancements in solid state chemical reactivity are considered in Chap. 7. There are many groups who... 

In solid state chemistry the limited atomic mobility in the solid state controls chemical changes and leads to explicit consideration of the relative location of potential reactants (the configuration) and solid state reactivity as controlled by solid state defects. The same factors dominate shock-induced solid state chemistry. 

Intermetallics also represent an ideal system for study of shock-induced solid state chemical synthesis processes. The materials are technologically important such that a large body of literature on their properties is available. Aluminides are a well known class of intermetallics, and nickel aluminides are of particular interest. Reactants of nickel and aluminum give a mixture with powders of significantly different shock impedances, which should lead to large differential particle velocities at constant pressure. Such localized motion should act to mix the reactants. The mixture also involves a low shock viscosity, deformable material, aluminum, with a harder, high shock viscosity material, nickel, which will not flow as well as the aluminum. 

In solid-state systems it is often advantageous to have some of the electrolyte material mixed in with the reactant. There are two general advantages that result from doing this. One is that the contact area between the electrolyte phase and the electrode phase (the electrochemical interface) is greatly increased. The other is that the presence of the electrolyte material changes the thermal expansion characteristics of the electrode structure so as to be closer to that of the pure electrolyte. By doing so, the stresses that arise as the result of a difference in the expansion coefficients of the two adjacent phases that can use mechanical separation of the interface are reduced. 

The concentrations of reactants are of little significance in the theoretical treatment of the kinetics of solid phase reactions, since this parameter does not usually vary in a manner which is readily related to changes in the quantity of undecomposed reactant remaining. The inhomogeneity inherent in solid state rate processes makes it necessary to consider always both numbers and local spatial distributions of the participants in a chemical change, rather than the total numbers present in the volume of reactant studied. This is in sharp contrast with methods used to analyse rate data for homogeneous reactions in the liquid or gas phases. 

Additional information concerning the mechanisms of solid—solid interactions has been obtained by many diverse experimental approaches, as the following examples testify adsorptive and catalytic properties of the reactant mixture [1,111], reflectance spectroscopy [420], NMR [421], EPR [347], electromotive force determinations [421], tracer experiments [422], and doping effects [423], This list cannot be comprehensive. Electron probe microanalysis has also been used as an analytical (rather than a kinetic) tool [422,424] for the determination of distributions of elements within the reactant mixture. Infrared analyses have been used [425] for the investigation of the solid state reactions between NH3 and S02 at low temperatures in the presence and in the absence of water. 

The slope of the Arrhenius plot has units (temperature) 1 but activation energies are usually expressed as an energy (kJ mol 1), since the measured slope is divided by the gas constant. There is a difficulty, however, in assigning a meaning to the term mole in solid state reactions. In certain reversible reactions, the enthalpy (AH) = E, since E for the reverse reaction is small or approaching zero. Therefore, if an independently measured AH value is available (from DSC or DTA data), and is referred to a mole of reactant, an estimation of the mole of activated complex can be made. 

The reactions of some aromatic metal carboxylates are on the borderline of classification as solid-state processes. While there is no evidence of liquefaction, rates of decomposition in the poorly crystallized or vitreous reactant obey kinetic expressions more characteristic of reactions proceeding in a homogeneous phase. 

The rate of isotopic exchange in the solid state, between cobalt in the cation and in the anion of [60Co(H2O)6] [Co(edta)]2 4 H20, was increased [1144] by irradiation (100 Mrad) of the reactant. It was concluded that exchange occurred via vacancies, rather than through motion of a ring of cobalt atoms, one from a cationic site and the other from a neighbouring anionic site. 

Wydeven [865] concludes that, in the presence of Co304 (6.8%), up to 60% of the reactant NaC103 decomposed in the solid state. During subsequent melting, there was an increase in reaction rate. The catalytic activity of the additive was ascribed to the electron accepting properties of the oxide (Co304 is a p-type semi-conductor). The apparent value of E increased from 120 to 200 kJ mole 1 between a = 0.05 and 0.5. 

Some of the reactions which yield MM0O4 or MW04, referred to in Sect. 4.1.4, are closely related to those discussed here in which a carbonate or higher oxide is used as reactant. For example, the solid state reaction... 

A pellet is pressed of an intimate mixture of finely divided reactants and reaction induced either by arc melting and high-T annealing or by solid-state sintering in an electrical or high-frequency furnace. Isolating the borides from reactive container components can be a problem. The use of boron nitride liners has proved effective. In some cases the protective liner is made of sintered boride containing the same elements as the boride in preparation. 

Traditional solid-state synthesis involves the direct reaction of stoichiometric quantities of pure elements and precursors in the solid state, at relatively high temperatures (ca. 1,000 °C). Briefly, reactants are measured out in a specific ratio, ground together, pressed into a pellet, and heated in order to facilitate interdiffusion and compound formation. The products are often in powdery and multiphase form, and prolonged annealing is necessary in order to manufacture larger crystals and pure end-products. In this manner, thermodynamically stable products under the reaction conditions are obtained, while rational design of desired products is limited, as little, if any, control is possible over the formation of metastable intermediates. ... 

Low-temperature solid-state synthesis is preferred in most cases, where appropriate, for obvious reasons such as energy and cost economy and process safety or for critical concerns regarding the accessibility of compounds that are stable only at low temperatures or non-equilibrium phases, i.e., compounds thermodynamically unstable with respect to the obtained phase (e.g., a ternary instead of binary phase). The use of low-temperature eutectics as solvents for the reactants, hydrothermal growth... 

A + B" reacts to form "C" (Synthesis"), etc. These reactions cover most of those normally found in soUd state chemistry. Once you have mastered these types of reactions, you wUl be able to identify most sohd state reactions in terms of the reactants and products. This is important, especially when you may be trying to form an new composition not well known in solid state science. Addionally, you may wish to form a specific composition by a new method to see if it has superior physical or chemical properties over that same material formed by a different sohd state mechanism or reaction. In many cases, this has been found to be true and this factor has been responsible for several scientific advances in the sohd-state. That is- if you can find a different method for making a material, its properties may prove to be superior to that already known. 

Note that aU of these methods attempt to bypass the dependence of the solid state reaction upon diffusion. But, using a gaseous reactant may not be practical in all cases. And. sometimes it is hard to find a flux which does not interfere with the reaction. A flux is defined as follows ... 

Note that the second loss corresponds to 3.92 mol of water per mol of reactant, whereas the 3rd loss is 1.08 mol. This illustrates a serious problem that can be encountered in dynamic TGA, If the rate of heating is too fiemt and not enough time occurs during programming to achieve true equilibrium between successive solid state reactions, then the loss of water firom one reaction carries over into the next succeeding reaction. 

Thermal solid-state reactions were carried out by keeping a mixture of powdered reactant and reagent at room temperature or elevated temperature, or by mixing with pestle and mortar. In some cases, the solid-state reactions proceed much more efficiently in a water suspension medium or in the presence of a small amount of solvent. Sometimes, a mixture of solid reactant and reagent turns to liquid as the reaction proceeds. All these reactions are called solid-state reactions in this chapter. Solid-state reactions were found to be useful in the study of reaction mechanisms, since it is easy to monitor the reaction by continuous measurement of IR spectra. 

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