﻿Velocity 
  of 
  Molecular 
  and 
  Chemical 
  Reactions. 
  539 
  

  

  used 
  by 
  Noyes 
  and 
  Whitney 
  is 
  -i- 
  =C 
  (to 
  — 
  t) 
  (they 
  take 
  the 
  

  

  surface 
  to 
  remain 
  constant) 
  ; 
  Bruner 
  and 
  Tolloczko 
  use 
  my 
  

   equation 
  CXrito^t) 
  ; 
  the 
  equation 
  used 
  by 
  Nernst 
  and 
  

  

  Branner 
  is 
  y 
  ='-^X(fo—t), 
  where 
  ^ 
  are 
  also 
  constants, 
  i, 
  e. 
  

  

  the 
  equation 
  o£ 
  the 
  above 
  authors 
  is 
  identical 
  with 
  the 
  first 
  

   (less 
  accurate 
  one) 
  of 
  mine. 
  As 
  my 
  papers 
  were 
  published 
  

   also 
  in 
  the 
  very 
  same 
  Zeitsch. 
  filr. 
  phys. 
  Cliem. 
  in 
  which 
  these 
  

   and 
  other 
  authors 
  * 
  later 
  published 
  their 
  papers, 
  I 
  must 
  

   clearly 
  uphold 
  here 
  my 
  priority 
  rights, 
  since 
  all 
  these 
  authors 
  

   do 
  is 
  to 
  give 
  their 
  own 
  interpretation 
  to 
  my 
  constant. 
  All 
  

   the 
  more 
  so, 
  since 
  Nernst 
  and 
  E. 
  Brunner, 
  L. 
  Bruner 
  and 
  

   Tolloczko, 
  give 
  us 
  in 
  an 
  arbitrary 
  manner 
  (with 
  their 
  methods, 
  

   see 
  §2) 
  for 
  a 
  part 
  of 
  the 
  curve 
  what 
  was 
  established 
  by 
  me 
  

   before, 
  on 
  careful 
  experiments, 
  for 
  the 
  whole 
  curve 
  ; 
  my 
  

   reactions 
  were 
  photographed 
  and 
  carried 
  out 
  by 
  methods 
  of 
  

   infinitely 
  greater 
  accuracy 
  and 
  reliability 
  than 
  theirs. 
  

  

  In 
  my 
  general 
  equation 
  the 
  assumption 
  was 
  made 
  that 
  the 
  

   volume 
  remains 
  the 
  same 
  during 
  the 
  whole 
  time 
  of 
  the 
  reaction. 
  

   Mr. 
  Drucker 
  also 
  investigated 
  the 
  effect 
  of 
  the 
  volume 
  upon 
  

   the 
  speed 
  of 
  solution 
  of 
  solids, 
  and 
  found 
  that 
  the 
  speed 
  is 
  

   indirectly 
  proportional 
  to 
  the 
  volume 
  of 
  the 
  liquid. 
  I 
  wish 
  

   to 
  add 
  that, 
  from 
  the 
  standpoint 
  of 
  my 
  general 
  equation, 
  this 
  

   is, 
  at 
  a 
  constant 
  surface 
  of 
  the 
  solid, 
  a 
  self-understood, 
  un- 
  

   avoidable 
  necessity. 
  Because, 
  as 
  the 
  reaction 
  goes 
  on 
  at 
  the 
  

   surface 
  of 
  the 
  solicl 
  in 
  contact 
  ivith 
  the 
  liquid, 
  the 
  amount 
  of 
  

   substance 
  going 
  into 
  solution 
  is, 
  at 
  a 
  constant 
  surface, 
  at 
  the 
  

   time 
  T 
  only 
  dependent 
  upon 
  the 
  concentration 
  of 
  the 
  solution, 
  

   and 
  this 
  amount 
  is 
  according 
  to 
  our 
  conception 
  subsequently 
  

   distributed 
  by 
  the 
  stirrer, 
  through 
  the 
  whole 
  volume 
  of 
  the 
  

   liquid. 
  If 
  the 
  volume 
  is, 
  for 
  example, 
  twice 
  as 
  large, 
  the 
  

   increase 
  in 
  its 
  concentration 
  must 
  be 
  twice 
  as 
  slow, 
  i. 
  e. 
  the 
  

   speed 
  of 
  solution, 
  as 
  measured 
  from 
  the 
  concentrations 
  of 
  the 
  

   solution^ 
  will 
  be 
  twice 
  as 
  small. 
  This 
  naturally 
  applies 
  to 
  all 
  

   molecular 
  reactions^ 
  of 
  which 
  solution 
  of 
  solids 
  forms 
  only 
  one 
  

   particular 
  case. 
  But 
  I 
  wish 
  clearly 
  to 
  point 
  out, 
  that 
  this 
  

   dependence 
  wpon 
  the 
  volume 
  is 
  only 
  an 
  apparent 
  one, 
  for 
  the 
  

   reason 
  that 
  we 
  are 
  able 
  only 
  to 
  measure 
  the 
  concentrations 
  

   of 
  the 
  solution. 
  The 
  time 
  reaction 
  takes 
  place 
  only 
  at 
  the 
  

   surface 
  of 
  the 
  solid, 
  and 
  here 
  the 
  phenomenon 
  of 
  solution 
  is 
  

   indejyendent 
  of 
  the 
  volume 
  oi 
  the 
  rest 
  of 
  the 
  solution. 
  Only 
  

   the 
  surface 
  of 
  contact 
  and 
  the 
  concentration 
  of 
  the 
  solution 
  

   in 
  contact 
  with 
  the 
  solid 
  are 
  the 
  working 
  factors 
  and 
  come 
  

   into 
  consideration 
  here. 
  

  

  * 
  See 
  Karl 
  Druker 
  {Zeitsch. 
  fiir 
  phys. 
  Chem. 
  1901, 
  p. 
  173, 
  and 
  p. 
  693), 
  

   who 
  wrongly 
  attributes 
  my 
  equation 
  to 
  Noyes 
  & 
  Whitney. 
  

  

  2 
  2 
  

  

  