Irrationality factor

When electrolyte solutions are involved, however, the osmotic effects such as freezing point lowering, osmotic pressure increase, and rise in boiling point are much greater than corresponds to the total electrolyte concentration. Accordingly, van t Hoff introduced the irrationality factor i (van t Hoff factor) by which the particular osmotic effect could be divided to yield a number which satisfied the equation of state (i is always greater than 1). The van t Hoff factor is purely empirical and does not account for the anomalous behavior of strong electrolyte solutions. 

Not only was it possible to explain, by the new theory, the anomalous osmotic behavior of strong electrolytes, but intensive quantitative studies indicated clearly the existence of a simple relationship between the irrationality factor i and the degree of electrolytic dissociation a. In a solution of a uni-univalent electrolyte of concentration c, the sum of concentrations of all particles evidently exceeds c. This summation is equal to (1 — a)c -f 2ac = c(l -1- a). From the definition of irrationality factor. 

Let us assume for purposes of this paper that we can know the composition of a gas from some suitable measurement. It is then possible, in principle, to calculate pertinent properties such as heating value, relative density, compressibility factor. Unfortunately, as often happens in practice, these supposedly unambiguous calculations become clouded by accepted procedirres, misconceptions, misguided regulations. The discussion in this paper attempts to dispel the misconceptions and to clarify the accepted procedures. As for the regulations, it is only possible to wish that they would not always choose the path of maximum irrationality and to try to perform the calculations in the least offensive (technically) marmer possible. The calculations described in this paper reflect those suggested in GPA Standard 2172-85. However, this paper contains considerable amplification and discussion of the techniques. 

---