Solvent free Chemistry 2 Chemical Examples

At the same time, chemical research is far from dormant. Even a cursory inspection of the current chemical literature will reveal that there is considerable activity being devoted to green chemistry. For example, the use of ionic liquids as solvents and the development of solvent free systems are not only reducing the need for the traditional... 

In many cases the product S is itself a free radical (S ), or a hyper-reduced metal ion, which in turn reacts in one-electron gain or loss processes. It is not surprising, then, that radiation-chemical methods are widely used in the study of electron-transfer processes. Of particular value is the technique of pulse radiolysis which permits reactions to be studied on timescales ranging from seconds down to picoseconds, so that even the most reaetive speeies ean be studied. It is this technique and its applications that form the subject matter of this chapter which begins with an outline of the radiation chemistry of water and other solvents. Next there is a historical view of pulse radiolysis, some of the landmark discoveries are discussed, followed by a description of the principal features of a pulse radiolysis facility and the various methods of detecting and measuring transient speeies. The chapter ends with some examples of data capture and analysis, and methods of sample preparation. 

A simple classification scheme of solids is given in Fig. 7.1. In order to differentiate between the types of solids, we have to consider the Gibbs phase rule, which is discussed in any physical chemistry textbook. The basic question is whether the solid substance consists of only one chemical entity (component) or more than one. Usually the component is one molecular unit, with only covalent bonded atoms. However, a component can also consist of more constituents if their concentration cannot be varied independently. An example of this is a salt. The hydrochloride salt of a base must be regarded as a one-component system as long as the acid and the base are present in a stoichiometric ratio. A deficiency of hydrochloric acid results in a mixture of the salt and the free base, which behave as two completely different substances (i.e. two different systems). Polymorphic forms, the glassy state, or the melt of the base (or the salt) are considered as different phases within such a system (a phase is defined as the portion of a system that itself is homogeneous in composition but physically distinguishable from other phases). When the base (or salt) is dissolved in a solvent, a new system is obtained this is also tme when a solvent is part of the crystal lattice, as in the case of a solvate. Thus, each solvate represents a different multicomponent system of a compound, whereas, polymorphic forms are different phases. The variables in the solvate are the kind of solvate (hydrate. 

In certain contexts, the calculation of free energy differences is difficult to access computationally. Examples would include problems in which a large amount of solvent would need to be displaced in a chemical association, one in which a large conformational change occurs, or one in which a complex chemical intermediate is present. In these cases, one of which is described below in the context of acid-base chemistry, the method can often be readily combined with a hypothetical free energy cycle[46], with individual legs that are each readily evaluated computationally. 

---