Iheory of Molecular Volumes. 463 



CH 3 CH a 



\ / 



CH 



I 



C 

 S \ 



and 



CH CH 2 



I I 



CH 2 CH 



S 



C 



CH 3 



there is probably very little difference in the configuration, 

 so that the residues 



I 



.1 



and CH 



CH, 

 \ 



would have about the same volume. 



would, however, have a volume larger by 6 



j 



units than the foregoing. 



Thus varying distribution of linkages un- 



qjj accompanied by changes in configuration do not 



affect the volumes. On the other hand, redis- 



qjj tribution of leakages which involve changes in 



| 2 configuration influence the volumes. It is 



probably always true that variations in volumes 



are associated with corresponding changes in the configuration 



and are due to the greater concentration of matter whereby 



the intramolecular forces are more effective. 



The Volume Anomaly. 



This very important constitutive peculiarity is named 

 after the Optical Anomaly. There is nothing, however, to 

 distinguish it from the other constitutive influences which 

 have been noticed — it is doubtless a particular case of the 

 influence of Residual Affinity. 



It may be thus defined : — 



If a side chain of an aromatic compound possess residual 



