Potentiometric

TITRATION
Titration curves
 What does a titration
curve look like for an
acid/base titration?

Typical pH titration

14
12
10
8
pH

6
4
2
0
0 5 10 15 20
mL of HBr
 OverTitration
REDOX
Titrations

Ecell
Equivalence Point

0.05916V [ Ared ]
EA  EA  Nernst Equation for A
o
log
nA [ Aox ]
0.05916V [ Bred ] Nernst Equation for B
EB  EB 
o
log
nB [ Box ]
Since at equilibrium, [Ared] = [Box] and [Bred] = [Aox] we massage the two
general equations to yield:

n A E Ao  nB EBo
Eeq 
n A  nB
Equivalence Point

n A E  nB E o o
Eeq  A B
n A  nB
Note: This expression only works for simple REDOX TITRATIONS:

Simple redox titrations:

Only Aox, Box, Ared, Bred are involved in the reaction …
Just like Acid/Base Titrations
There are four significant regions,
 The Start (awal)
 The Buffer Region/ daerah sebelum TE
 The equivalence Point (titik Ekuivalen, TE)
 Overtitration (setelah TE)

Let’s Use our simple example:

 Fe2+ + Ce4+  Fe3+ + Ce3+
Our simple example

Let’s Use our simple example:

 Fe2+ + Ce4+  Fe3+ + Ce3+

Titrate 50 mL of 0.05 M Fe2+ with 0.10 M Ce4+

0% Titration
Unlike acid/base titrations, we can’t find this point
exactly.

 While some Fe3+ must be present, we can only

guess what the concentration is.

 No Ce4+ or Ce3+ present, so we don’t have a

complete reaction
0% Titration
2
0.05916V [ Fe ]
EFe  EFe 
o
log
nA [ Fe3 ]
0.05916V 0.05
EFe  0.771V  log
1 0
NO … some of the iron is oxidized by air to give some
EFe   Fe3+ … how much ? We generally estimate that less
Than one in 1000 are oxidized.
0.05916V 0.05
EFe  0.771V  log
1 5 x10 5
 0.771V  0.177V  0.594V vs. SHE
“Buffer Region”
Fe2+ + Ce4+  Fe3+ + Ce3+
10 ml of Ce4+ is added
Goes to completion … Excess Fe2+ pushes
equilibrium to the right.

Thus E is not dependent on Ce3+/Ce4+, but only

on Iron.
“Buffer Region”
2
0.05916V [ Fe ]
EFe  EFe 
o
log 3
nA [ Fe ]
2
0.05916V 2.5 10
EFe  0.771V  log 2
1 1.7 10

EFe  0.771V  0.010  0.761V

Closer look at the “buffer”
region

Ratio Fe2+/Fe3+ E
9 0.715
4 0.735
1.5 0.761
1 0.771
0.25 0.807
0.11 0.829
Equivalence Point
 From Before
 Eeq = 1.24 V

What volume?
25 ml Ce4+
Excess Ce4+ (post titration)
 Fe2+ + Ce4+  Fe3+ + Ce3+

 The predominate change is that Ce4+ is being added and diluted

into a solution of Ce3+.

 All Fe2+ has been converted to Fe3+ and no longer figures into the
calculations

 We just need to keep track of the amounts of Ce3+ and Ce4+ as

well as the VOLUME of the system.
Excess Ce4+ (post titration)

 At 30.0 mL Ce4+ Vt = 30.0 mL+ 50.0 mL

3
0.05916V [Ce ]
ECe  ECe 
o
log
n [Ce 4 ]
3
0.05916V [Ce ]
ECe  1.70  log
1 [Ce 4 ]
Excess Ce4+ (post titration)

 Fe2+ + Ce4+  Fe3+ + Ce3+

Ce3+/Ce4+

3
[Ce ]  ?
4
[Ce ]  ?
Excess Ce4+ (post titration)

3
0.05916V [Ce ]
ECe  1.70  log 4
1 [Ce ]
2
0.05916V 3.1x10
ECe  1.70  log 3
1 6.2 x10
ECe  1.70  0.041  1.66V vs. SHE