MOLECULAR VOLUME 

 II. A Closing of the Partial Ring. 



i 

 i 



CH 2 - CH 2 - CH 2 - CI + Na 



679 



Complete 

 Hings. 



CH 2 - CH 2 - CH 2 - CI + Na 



CH, 



CH 2 — CHc 



CH 2 — CH 2 — CH; 



Hexamethylene. 



L 12- 



CH 2 



CH = CH - CH 



M.V. C 6 H 12 116-3 



6 x CH 2 = 6 x 22*2 = 133*2 

 A — 16-9 

 This large difference is an expression of the difference in struc- 

 ture between Hexamethylene and Hexane or Hexylene, C 6 Hj 



III. The Formation of Benzene from Hexamethylene. 



CH 2 - CH 2 - CH 2 CH = CH - - CH 



- 6H 2 = 



CH 2 — CH 2 

 M.V. of Benzene C 6 H 6 96-0 



V. C 6 H 12 - V6H = 116-3 -6x3-2 = 97-1 = C 6 H 6 

 or Hexane CeH 12 139*93 



Hexylene C 6 Hi 2 132-4 ^ ^3 

 Dipropargyl C 6 H 6 139*93 -4x7-5 



= l 39'9 — 3°'° = k>9'9 

 A = 109*9 — 96 = — 13-9 or 14*0 approx. 



In this case again we notice a large contraction for ring 

 structure. 



IV. Substitutions in the Benzene Ring. 



(i) Nitrobenzene C H 5 NO 2 



CH CH 



S \ * V 



Volume 

 Anomaly, 



CH 



I 

 CH 



\ / 

 CH 



CH 



CH CH 



CH 



+ HNO3 



CH 



% / 

 CH 



CH - N0 3 



+ etc. 



C 6 H 6 V. 96-0 C 6 H 5 N0 2 V. i22-i 



Vol. of 2N0 2 is 64-0 N0 2 = 32-0 



V. C e H 5 N0 2 = V. (C 6 H 6 - H + N0 2 ) 

 = 96 — 3*2 + 32*0 = 124*8 

 A between calculated and observed results 

 124-8 — i22*i = — 2-7 



This small difference expresses the effect of an interaction 

 between the unsaturated — N0 2 group and the nucleus. This 

 44 



