Chem 1B Dr.

White 77  

Experiment  9  –  Polyprotic  Acid  Titration  Curves  

   
Objectives   Acid  Dissociation  Constants  
 To   learn   the   difference   between   titration   For   diprotic   acids,   titration   curves   allow   you   to  
curves   involving   a   monoprotic   acid   and   a   calculate  the  Ka1  and  Ka2  of  the  acid.  
diprotic  acid    
 To  determine  the  concentration  of  an  unknown   At   the   beginning   of   a   titration,   the   added   base   is  
acid  using  a  titration  curve  for  a  diprotic  acid   converting  the  diprotic  acid  H2A  into  its  conjugate  base  
 To   determine   the   Ka’s   of   an   unknown   acid   HA-­‐.   At   half   of   the   volume   of   base   needed   to   reach   the  
using  a  titration  curve  for  a  diprotic  acid   first  equivalence  point,  there  is  a  special  data  point.  At  
  this   point,   only   half   of   the   diprotic   acid   H2A   has   been  
Introduction   converted   into   its   conjugate   base   HA-­‐,   so   the   amounts  
of   acid   and   conjugate   base   must   be   equal.   The   Ka1  
Other   than   by   strength   and   concentration,   another   way  
expression  for  the  acid  H2A  is  given  by  
of   classifying   acids   involves   the   number   of   H+   ions   an  
 
acid   can   donate.   A   monoprotic   acid   will   ionize   and  
donate   one   mole   of   H+   for   every   one   mole   of   acid   [H O+ ][HA − ]  
K a1 = 3
molecules   (e.g.,   HCl   or   HNO2).   A   diprotic   acid   will   [H 2 A]
produce   two   moles   of   H+   (e.g.   H2SO4),   a   triprotic   acid        
three  moles  of  H+  (e.g.  H3PO4),  etc.   If   the   concentrations   of   H2A   and   HA-­‐   are   equal   at   the  
  half-­‐first   equivalence   point,   then   the   Ka1   must   equal   the  
Shown   below   is   a   sample   titration   curve   for   a   diprotic   hydronium   € ion  concentration  
acid.  Note  the  two  equivalence  points.    
      Ka1    =      [H3O+]  
 
By  taking  the  negative  logarithm  of  the  equation  
 
    pKa1    =    pH    
 
therefore,  the  pH  at  the  half-­‐first  equivalence  point  in  a  
titration  equals  the  pKa1  of  the  acid.  
 
When   the   first   equivalence   point   has   been   reached,   all  
of   the   acid   H2A   has   been   converted   into   HA-­‐.   Past   this  
point   the   added   base   is   converting   the   weak   acid   HA-­‐  
into  its  conjugate  base  A2-­‐.  At  half  of  the  volume  of  base  
needed  to  reach  the  second  equivalence  point,  there  is  
a   special   data   point.   At   this   point,   only   half   of   the   HA-­‐  
  has   been   converted   into   its   conjugate   base   A2-­‐,   so   the  
  amounts   of   HA-­‐   and   A2-­‐   must   be   equal.   The   Ka2  
The   first   equivalence   point   represents   the   point   of   the   expression  for  the  acid  H2A  is  given  by  
titration   where   the   first   hydrogen   ion   from   the   initial    
amount  of  acid  has  been  neutralized  by  the  added  base.     [H O+ ][A 2− ]  
  K a2 = 3
H2A    +    OH-­‐    →    H2O    +    HA-­‐   [HA − ]
   
Therefore,   at   the   first   equivalence   point:   1   mole   of   If   the   concentrations   of   HA-­‐   and   A2-­‐   are   equal   at   the  
acid  has  reacted  with  1  mole  of  base.   half-­‐second  equivalence  point,  then  the  Ka2  must  equal  
€
the  hydronium   ion  concentration  
 
The   second   equivalence   point   represents   the   point   of    
the   titration   where   the   both   hydrogen   ions   from   the       Ka2    =      [H3O+]  
initial   amount   of   acid   have   been   neutralized   by   the    
added  base.     By  taking  the  negative  logarithm  of  the  equation  
   
H2A    +    2OH-­‐    →    2H2O    +    A2-­‐       pKa2    =    pH    
   
Therefore,  at  the  second  equivalence  point:  1  mole  of   therefore,   the   pH   at   the   half-­‐second   equivalence   point  
acid  has  reacted  with  2  mole  of  base.   in  a  titration  equals  the  pKa2  of  the  acid.  
78   Chem 1B Dr. White

  checking   your   calculation.   The   concentration   of   the  

Acid  Concentration   unknown   acid   based   on   the   first   equivalence   point  
To   determine   the   concentration   of   an   acid   or   base   should   be   the   same   as   the   concentration   of   the   acid  
during   a   titration,   we   will   focus   on   the   equivalence   based   on   the   second   (or   third)   equivalence   point   as  
points.   At   the   first   equivalence   point   for   a   diprotic   acid,   long  as  you  used  the  correct  acid  to  base  molar  ratio.  
you   have   added   enough   base   to   remove   the   first    
hydrogen   ion   from   every   molecule   of   acid;   therefore,    
the  molar  ratio  of  acid  to  base  is  one-­‐to-­‐one  at  the  first   Procedure  
equivalence  point.   See   Procedure   for   Experiment   8.     Follow   the   same  
  procedure   except   use   10.00   mL   of   the   unknown  
H2A    +    OH-­‐    →    H2O    +    HA-­‐   acid  instead  of  5.00  mL.  
  Note:    There  will  be  2  peaks  in  the  derivative  curve.    
Notice   that   this   relationship   is   in   terms   of   moles,   not   You  will  used  both  of  these  peaks  to  determine  the  two  
concentration.   Therefore,   at   the   first   equivalence   equivalence  points  and  thus  the  two  pKa  values.
point:  1  mole  of  acid  has  reacted  with  1  mole  of  base  
 
Using   the   first   equivalence   point,   the   concentration   of  
the   base   used   in   the   titration,   and   the   volume   of   base  
needed   to   reach   the   first   equivalence   point,   we   can  
determine   the   number   of   moles   of   base   needed   up   to  
this   point   in   the   titration.   At   the   first   equivalence   point,  
the   number   of   moles   of   base   needed   must   be   equal   to  
the   number   of   moles   of   acid   in   the   titration   sample.  
Dividing  the  number  of  moles  of  acid  by  the  volume  of  
acid   used   in   the   titration,   we   can   determine   the  
concentration  of  the  acid  unknown.  
 
At  the  second  equivalence  point  for  a  diprotic  acid,  you  
have   added   enough   base   to   remove   both   the   first   and  
the   second   hydrogen   ions   from   the   acid.   The   molar  
ratio  of  acid  to  base  at  this  point  is  not  one-­‐to-­‐one,  but  
is  rather  one-­‐to-­‐two.    
 
H2A    +    2OH-­‐    →    2H2O    +    A2-­‐  
 
Therefore,  at  the  second  equivalence  point:  1  mole  of  
acid  has  reacted  with  2  moles  of  base  
 
Using   the   second   equivalence   point,   the   concentration  
of  the  base  used  in  the  titration,  and  the  volume  of  base  
needed   to   reach   the   second   equivalence   point,   we   can  
determine   the   number   of   moles   of   base   needed   up   to  
this   point   in   the   titration.   At   the   second   equivalence  
point,   the   number   of   moles   of   base   needed   must   be  
twice   the   number   of   moles   of   acid   in   the   titration  
sample.   Dividing   the   number   of   moles   of   acid   by   the  
volume  of  acid  used  in  the  titration,  we  can  determine  
the  concentration  of  the  acid  unknown.  
 
By   choosing   either   of   the   equivalence   points   and   the  
corresponding   molar   ratio   of   acid   to   base   at   that  
equivalence  point,  you  can  determine  number  of  moles  
of   base   needed   and   therefore,   the   number   of   moles   of  
acid   in   the   sample.   From   there,   you   can   calculate   the  
concentration  of  the  unknown  polyprotic  acid.  
 
A   polyprotic   acid   also   provides   a   way   of   double-­‐
 Chem 1B Dr. White 79  

Name:                               Lab  Day/Time:    ____________________                  

Experiment  9:  Titration  Curve  for  a  Diprotic  Acid  

Data  and  Results  
 
Unknown  Diprotic  Acid-­Strong  Base  Titration  

Acid:   UNKNOWN  #:         Molarity:              UNKNOWN   _________  

Base:               Molarity:          

•   Using  your  titration  and  derivative  curves,  fill  in  the  following  data  table.  
(a)  The  exact  pH  of  the  solution  at  the  1st  equivalence  point    
(b)  The  exact  pH  of  the  solution  at  the  2nd  equivalence  point    
(c)  The  volume  required  to  reach  the  1st  equivalence  point    
(d)  The  volume  required  to  reach  the  2nd  equivalence  point    
(e)  pKa,1  for  this  acid    
(f)  The  Ka,1  for  this  acid    
(g)  pKa,2  for  this  acid    
(h)  The  Ka,2  for  this  acid    
(i)  The  molarity  of  the  acid  calculated  using  the  1st    
equivalence  point  
(j)  The  molarity  of  the  acid  calculated  using  the  2nd    
equivalence  point  
 

(f)  Show  your  calculation  for  Ka,  1   (h)  Show  your  calculation  for  Ka,  2  
 
 
 
 
 
 
 
 
 
(i)  Show  your  calculation  for  molarity  using  the  1st  e.p.   (j)  Show  your  calculation  for  molarity  using  the  2nd  e.p.  
 
 
 
 
 
 
 
 
 
 
 
•   Attach  your  titration  curve  and  derivative  plot  to  the  end  of  the  report.  
80   Chem 1B Dr. White

On  your  printed  Logger  Pro  graph,  label  the  following  points:  

 
(a) The  point  on  the  titration  curve  when  the  solution  contains  only  the  diprotic  acid  H2X  
 
(b) The  point  on  the  titration  curve  when  the  solution  contains  equal  amounts  of  H2X  and  HX-­‐  
 
(c) The  point  on  the  titration  curve  when  the  solution  contains  only  HX-­‐  
 
(d) The  point  on  the  titration  curve  when  the  solution  contains  equal  amounts  of  HX-­‐  and  X2-­‐  
   
(e) The  point  on  the  titration  curve  when  the  solution  contains  only  X2-­‐  
 

•   From  the  calculated  molarity,  Ka1,  and  Ka2  values  for  your  unknown  diprotic  acid  H2A,  determine  the  concentrations  in  
the  original  unknown  solution  of  H2A,  HA-­‐,  A2-­‐,  and  H3O+.