AmMJa°y1i9i5arm'}    S°me  Studies  on  the  Oxy-pinenes.  209 
Harries's  results  are  strongly  contested  by  E.  Molinari,  E.  Soucini 
and  P.  Fenaroli  in  Annuario  della  Societa  Chimica  di  Milano, 
Berichte,  and  in  other  places,  but  Walter  Frank,  in  his  dissertation 
"  Ueber  Oelensauerozonid  und  seine  Zersetzungsprodukte,"  Ham- 
burg, 19 1 o,  in  comparing  the  two  different  opinions,  comes  to  the 
conclusion  that  the  reason  for  their  ostensibly  contradictory  results 
lies  in  the  strength  of  ozone  used  and  the  method  of  production,  and 
in  his  text-bopk,  "  Treatise  on  General  Industrial  Organic 
Chemistry,"  1913,  Molinari  says  that  "  the  decomposition  of  ozonides 
with  dilute  alkali  or  hot  water  results  in  the  formation  of  acids  and 
in  the  cold  of  aldehydes.  .  . 
In  1908  Harries  gives  an  account  (Ber.,  vol.  41,  1)  of  the  ozoni- 
zation  of  pinene.  He  obtains  two  different  ozonides  in  the  same 
mixture,  viz.,  one  solid  and  one  liquid.  The  solid,  which  amounts  to 
10  to  20  per  cent,  of  the  total,  consists  of  "  small,  elastic  clusters  of 
undefined  crystallinic  form,"  and  this  he  calls  pinene  perozonide. 
He  is  unable  to  get  a  definite  formula  for  it,  and  can  only  say  that 
it  is  nearer  C10H16O4  than  C10H16O3,  and  is  insoluble  in  all  the  usual 
organic  solvents. 
The  oily  ozonide  80  to  90  per  cent,  of  the  yield,  on  the  other  hand, 
has  the  definite  formula  of  C10H16O3.  The  decomposition  products 
he  finds  to  be  peroxide  of  hydrogen,  and  at  ordinary  temperature  the 
intermediary  oxy-pinenes,  i.e.,  aldehydes  and  ketones,  and,  by  heating 
or  by  prolonged  intermolecular  or  auto-oxidation,  pinonic  acid. 
In  1909  W.  J.  Knox  devised  and  patented  an  apparatus  for  the 
production  of  vapors  of  pinene  ozonide.  The  apparatus  consists  of 
a  tank  partly  filled  with  pure  pinene,  over  which  a  current  of  air, 
dried  by  being  drawn  through  chloride  of  calcium,  is  passed,  evapor- 
ating and  carrying  pinene  vapors  along  to  a  mixing  chamber,  where 
it  is  met  by  a  current  of  ozone  generated  by  silent  electrical  discharges 
in  an  ozonizing  tube.  When  the  pinene  vapor  and  the  ozone  meet 
they  form  ozonide  of  pinene,  which  appears  in  the  form  of  a  thick, 
whitish  vapor  or  cloud. 
An  examination  of  this  vapor  by  the  test-papers  ordinarily  used 
for  such  purposes  will  show  that  no  free  ozone  exists,  nor  any  per- 
oxide of  hydrogen,  but  if  the  test-paper  is  moistened  a  peroxide  of 
hydrogen  reaction  will  immediately  take  place. 
If  the  vapor  is  compressed  in  an  ordinary  air  compressor  and 
then  allowed  to  strike  against  a  cold  surface,  such  as  the  bottom  of  a 
glass  beaker,  clusters  of  ill-defined  crystals  can  be  detected  by  a 
