Advances in Chemical Physics, Volume 2 by K. P. Lawley

By K. P. Lawley

The Advances in Chemical Physics sequence presents the chemical physics and actual chemistry fields with a discussion board for severe, authoritative reviews of advances in each zone of the self-discipline. jam-packed with state-of-the-art learn stated in a cohesive demeanour no longer discovered in other places within the literature, each one quantity of the Advances in Chemical Physics sequence serves because the ideal complement to any complicated graduate type dedicated to the research of chemical physics.


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It was further shown that the solution theory of clathrates can account for this interesting phenomenon. For details the reader is referred to ref. 29. The difference in behavior reported by Von Stackelberg is not thought to be an essential one Whether decomposition of a hydrate containing two solutes by removal (of its vapor through pumping will be a univariant process depends on the number and compositions of the phases formed. I n the system of Fig. 10, for instance, a mixed H,S-propane hydrate will exhibit a constant decomposition pressure on pumping a t - 3°C if it contains HzS and propane in the “azeotropic” ratio of approximately 3 : 1.

D; they show a remarkably good fit to the experimental data. The compositions of the hydrates as calculated along the hydrate line are given in Table VI. The curves were determined from Eqs. 24"-26"; in order to apply these in a numerical calculation one first has to know the values of the following functions a t -3'C: d p , the difference in chemical potential between the "empty" Structure I1 lattice and ice; C p 2 , the Langmuir constant for propane in the larger cavities of Structure I1 ( C p l = 0 for geometrical reasons); C m , C M ~the , Langmuir constants for methane in the two types of cavities of Structure 11.

Numerical Calculations (1) Hydroquinone Clathrates The quantities E and CT are the force constants of the LennardJones interaction p ( R ) of a solute molecule K with an element of the wall of the hydroquinone cage (cf. Eq. 30). It is assumed that for this interaction the frequently-used combining rules for the interaction between two unlike particles hold, CLATHRATE SOLUTIONS E = (E, E & ) ) CT = “geometric mean approximation” ~ ( c T ~ “hard + c Tsphere ~ ) approximation” 29 (40) (41) Here E ~ C , T are ,the force constants for the pure solute K , which can be determined from measurements of its second virial coefficient, and E&, CT&are similar, but as yet unknown, constants characteristic for the B-hydroquinone lattice.

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