18 IONIC EQUILIBRIA IN ANALYTICAL CHEMISTRY

II-6. IMPORTANCE OF EQUILIBRIUM CALCULATIONS

Complex mixtures, in which a whole series of chemical

reactions can occur, are frequently encountered. In such mix-

tures the final composition is quite different from that of the

initially prepared mixture. A detailed knowledge of the com-

position of such mixtures is essential for the understanding of

their chemistry. Short of actually measuring the amount of

each and every species present, the only way to obtain this

knowledge is from a consideration of the appropriate equilibria.

In planning analytical procedures, questions of the following

sort can be answered by information obtained through equilib-

rium calculations: (a) Will a substance precipitate (or sepa-

rate in another manner such as by solvent extraction or ion

exchange) from solution, and if so, to what extent? Will other

substances separate under the same conditions? If so, can we

alter conditions by using complexing agents or controlling the

acidity of the solution, to obtain a selective separation?

(b) What are the characteristics of reactions that are of prac-

tical use in methods of determination? Do they proceed to a

sufficient extent? What are the nature and extent of any side

reactions? In titrimetry, what are the criteria for the selec-

tion of suitable indicators?

In trying to interpret the physical, chemical, or biological

properties of solutions, it is equally essential to know their de-

tailed composition since each species that is present makes a

unique contribution to these properties.

The determination of equilibrium constants is naturally of

utmost importance for the solution of problems of the type out-

lined above. In addition, the equilibrium constant (and AF)

provides a means of characterizing a chemical reaction and is

useful in theoretical considerations. A study of equilibrium

constant values provides a basis for evaluation of the influence

on chemical reactions of the many factors related to chemical

structure. In this connection, AH as well as AF, is of

importance.

The orientation of this book is largely based on the assump-

tion that all appropriate equilibrium constant values are avail-

able for use in the calculations described. Descriptions of the

means of the accurate determination of equilibrium constants

is beyond the scope of this book. However, the essential fea-

tures of such determinations are implicit in the expressions de-

rived in the text. That is, instead of having the concentration

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