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  Hamor 
  and 
  Gill 
  — 
  New 
  Synthesis 
  of 
  Phosgenite. 
  

  

  Art. 
  XXVIII. 
  — 
  A 
  New 
  Synthesis 
  of 
  Phosgenite; 
  by 
  

   W. 
  A. 
  Hamor 
  and 
  H. 
  E. 
  Gill. 
  

  

  Phosgenite, 
  the 
  chlorcarbonate 
  of 
  lead, 
  PbC0 
  3 
  .PbCl 
  2 
  , 
  

   which 
  occurs 
  in 
  Scotland, 
  Sardinia, 
  and 
  Upper 
  Silesia, 
  

   has 
  heretofore 
  been 
  synthesized 
  by 
  two 
  procedures. 
  C. 
  

   Friedel 
  and 
  E. 
  Sarasin 
  1 
  heated 
  lead 
  chloride, 
  lead 
  car- 
  

   bonate, 
  and 
  water 
  together 
  in 
  a 
  sealed 
  tube 
  to 
  180° 
  C, 
  

   and 
  effected 
  the 
  synthesis 
  ; 
  and 
  another 
  preparation 
  was 
  

   that 
  of 
  A. 
  de 
  Schulten, 
  2 
  who 
  allowed 
  a 
  filtered 
  solution 
  of 
  

   lead 
  chloride 
  to 
  stand 
  in 
  a 
  large 
  flask 
  while 
  a 
  current 
  of 
  

   carbon 
  dioxide 
  passed 
  slowly 
  through 
  the 
  space 
  above. 
  

  

  A 
  third, 
  and 
  very 
  logical 
  method, 
  occurred 
  to 
  us 
  as 
  

   worthy 
  of 
  trial. 
  This 
  consisted 
  in 
  heating 
  lead 
  hydrox- 
  

   ide 
  and 
  phosgene 
  under 
  pressure 
  in 
  a 
  sealed 
  tube, 
  to 
  

   effect 
  the 
  linkage 
  of 
  the 
  lead 
  hydroxide 
  with 
  phosgene, 
  

   accompanied 
  by 
  the 
  liberation 
  of 
  two 
  molecules 
  of 
  water. 
  

   "With 
  this 
  object 
  in 
  view, 
  a 
  series 
  of 
  experiments 
  were 
  

   carried 
  out 
  using 
  anhydrous 
  lead 
  hydroxide 
  and 
  phos- 
  

   gene, 
  3 
  the 
  phosgene 
  being 
  in 
  excess. 
  The 
  experiments 
  

   were 
  repeated 
  many 
  times, 
  varying 
  both 
  the 
  temperature 
  

   (95°, 
  120°, 
  150°, 
  175°, 
  200°, 
  and 
  250° 
  C.) 
  and 
  the 
  period 
  of 
  

   heating 
  (1 
  to 
  4 
  hrs.). 
  

  

  The 
  best 
  results 
  were 
  observed 
  at 
  a 
  temperature 
  of 
  

   175° 
  C, 
  falling 
  off 
  entirely 
  at 
  250° 
  C. 
  Atthe 
  interme- 
  

   diate 
  temperatures 
  slight 
  yields 
  were 
  obtained, 
  but 
  the 
  

   crystal 
  formation 
  was 
  very 
  ununiform. 
  The 
  resulting 
  

   material 
  in 
  each 
  experiment 
  was 
  freed 
  from 
  phosgene 
  

   and 
  any 
  lead 
  hydroxide 
  that 
  remained 
  and 
  was 
  then 
  sub- 
  

   mitted 
  to 
  a 
  thorough 
  examination. 
  The 
  crystals 
  obtained 
  

   at 
  175° 
  C. 
  were 
  quite 
  small, 
  but 
  well-formed, 
  faintly 
  

   yellow 
  in 
  color, 
  and 
  soluble 
  in 
  dilute 
  nitric 
  acid. 
  These 
  

   crystals 
  gave 
  positive 
  chemical 
  tests, 
  responding 
  to 
  tests 
  

   for 
  chloride 
  and 
  carbonate 
  radicals, 
  and 
  fusing 
  to 
  a 
  glob- 
  

   ule 
  of 
  lead 
  covered 
  with 
  a 
  white 
  coating 
  of 
  lead 
  chloride 
  

   when 
  heated 
  upon 
  charcoal: 
  the 
  crystals 
  were 
  unques- 
  

   tionably 
  identified, 
  both 
  chemically 
  and 
  crystallographi- 
  

   cally, 
  as 
  phosgenite. 
  

  

  Mellon 
  Institute 
  of 
  Industrial 
  Research, 
  

   Pittsburgh, 
  Pa., 
  April 
  24, 
  1919. 
  

  

  1 
  Bull. 
  Soc. 
  Min., 
  4, 
  175, 
  1881. 
  

  

  2 
  Idem, 
  20, 
  194, 
  1897. 
  

  

  3 
  The 
  phosgene 
  used 
  was 
  obtained 
  from 
  the 
  Edgewood 
  Arsenal, 
  Baltimore, 
  

   Md. 
  

  

  