Lecture20Ch161April13

Hs and rhs match that gives a1 1 a2 a3 2b2 2 3b3

Info iconThis preview shows page 1. Sign up to view the full content.

View Full Document Right Arrow Icon
This is the end of the preview. Sign up to access the rest of the document.

Unformatted text preview: er all substitutions: p = kT + B2 (T ) 2 + B3 (T ) 1 3 ...... Z12 B2 (T ) = b2 = 2 B3 (T ) = 4b2 ( 2!V ) ( Z 2b3 = 1 V Z3 3V 2 ( 2 ) 3Z 2 Z1 + 2Z12 ( ) 3( Z 2 Z12 )) 2 This expression looks very different from what we saw before. How comes? Now lest us calculate, e.g. second term above: Z1 = Z2 = Z3 = dr = V 1 U2 e e kT U3 kT drdr2 drdr2 dr 3 U (r12 ) U (r ) kT 1 1 B2 (T ) == Z2 Z12 = 2V 2V ( ) e kT 1 dr1dr2 1 2 e 1 dr Virial Expansion: A general Consideration For third virial coefficient we get after a considerable effort: B3 (T ) = 1 3V f12 f 23 f31dr1dr2 dr3 Using this GCPF formalism Mayer was able to prove the remarkable general theorem: Virial expansion can be expressed in terms of cluster integrals or stars B2 = f12 B3 = f12 f23 +.... f13 Extrapolation to high density: the van der Waals Equation Now we consider the property of the intermolecular potential which consists of weak attr...
View Full Document

This note was uploaded on 05/04/2010 for the course CHEM 161 taught by Professor Shaklovich during the Spring '10 term at Harvard.

Ask a homework question - tutors are online