﻿the 
  Unit-Stere 
  Theory. 
  

  

  63 
  

  

  aliphatic 
  series, 
  additive 
  volume 
  relations 
  will 
  be 
  considered 
  

   at 
  the 
  melting-point 
  and 
  at 
  the 
  boiling-point. 
  It 
  is 
  natural 
  

   to 
  suppose 
  that 
  some 
  constitutive 
  effect 
  is 
  noticeable, 
  as 
  

   appears 
  to 
  be 
  the 
  case 
  when 
  other 
  physical 
  properties 
  are 
  

   taken 
  into 
  consideration. 
  Although 
  there 
  is 
  a 
  contraction 
  in 
  

   both 
  the 
  defines 
  and 
  the 
  acetylenes 
  at 
  the 
  melting-point, 
  

   apparently 
  due 
  to 
  unsaturation, 
  none 
  is 
  found 
  when 
  the 
  

   molecular 
  volumes 
  of 
  the 
  simpler 
  homologues 
  of 
  the 
  unsatu- 
  

   rated 
  series 
  are 
  considered 
  at 
  the 
  boiling-point. 
  Yery 
  much 
  

   more 
  experimental 
  work 
  will 
  have 
  to 
  be 
  done 
  before 
  it 
  is 
  

   possible 
  to 
  draw 
  any 
  very 
  general 
  conclusions, 
  and 
  under 
  as 
  

   great 
  a 
  variety 
  of 
  physical 
  conditions 
  as 
  possible. 
  Only 
  the 
  

   barest 
  outlines 
  of 
  the 
  theory 
  can 
  be 
  presented 
  under 
  the 
  

   circumstances, 
  and 
  it 
  is 
  possible 
  that 
  it 
  will 
  have 
  to 
  be 
  modi- 
  

   fied 
  in 
  certain 
  of 
  its 
  details 
  in 
  the 
  light 
  of 
  fuller 
  knowledge, 
  

   and 
  with 
  much 
  more 
  extended 
  experimental 
  material 
  than 
  is 
  

   available 
  at 
  present. 
  

  

  (a) 
  The 
  Olefines, 
  C 
  jr 
  E 
  2 
  J 
  = 
  |. 
  (Krafffc, 
  Ber. 
  1886, 
  xvi. 
  p. 
  3018.) 
  

  

  Table 
  I. 
  

   Table 
  of 
  Volumes 
  of 
  the 
  Olefines 
  at 
  the 
  M.P. 
  

  

  

  

  

  

  

  M.P. 
  

  

  

  No, 
  

  

  define, 
  C 
  rt 
  H.2n 
  {—]■ 
  

  

  W. 
  

  

  V. 
  

  

  A. 
  

  

  B.P. 
  

  

  (15 
  mm.) 
  

  

  WS 
  

   -2-50. 
  

  

  1. 
  

  

  Dodecylene, 
  C 
  12 
  H 
  24 
  |=| 
  ... 
  

  

  72 
  

  

  211-2 
  

  

  35-7 
  

  

  •656 
  

  

  211-4 
  

  

  2. 
  

  

  Tetradecylene, 
  C 
  14 
  H 
  2S 
  | 
  = 
  | 
  ... 
  

  

  84 
  

  

  246-9 
  

  

  36-0 
  

  

  •652 
  

  

  247-03 
  

  

  3. 
  

  

  Hexadecylene, 
  16 
  H 
  32 
  [=] 
  ... 
  

  

  96 
  

  

  282-9 
  

  

  35-7 
  

  

  •647 
  

  

  282-7 
  

  

  4. 
  

  

  Octadecylene, 
  18 
  H 
  3G 
  |=| 
  ... 
  

  

  108 
  

  

  318-6 
  

  

  

  •644 
  

  

  318-3 
  

  

  Mean 
  val 
  

  

  ae 
  

  

  

  35-8 
  

   12x2-9 
  

  

  8 
  

  

  

  The 
  value 
  of 
  S 
  used 
  in 
  the 
  calculation 
  of 
  the 
  molecular 
  

   volume 
  is 
  2*970 
  — 
  a 
  number 
  which 
  is 
  justified 
  by 
  the 
  very 
  

   close 
  approximation 
  of 
  the 
  calculated 
  to 
  the 
  observed 
  values. 
  

  

  The 
  contraction 
  for 
  unsaturation 
  is 
  2*50 
  at 
  the 
  melting- 
  

   point 
  in 
  the 
  above 
  cases. 
  

  

  In 
  order 
  to 
  obtain 
  a 
  more 
  extended 
  view, 
  it 
  is, 
  however, 
  

   necessary 
  to 
  study 
  the 
  liquid 
  volumes 
  of 
  the 
  olefines 
  above 
  the 
  

   melting-point. 
  For 
  this 
  reason, 
  calculations 
  similar 
  to 
  those 
  

   followed 
  for 
  the 
  saturated 
  paraffin 
  series 
  are 
  here 
  worked 
  out. 
  

  

  