Problems

4, 6, 8, 11, 15
Fundamentals of
Analytical Chemistry
Chapter 19
Applications of Standard
Electrode Potentials

Calculations of Equilibrium Calculation of Equilibrium

Constants Constants

From thermodynamics, we know that at 0.05916
We know E = E O log Q
equilibrium, G = 0 n

Also, G = -nFE At equilibrium 0 = E O
0.05916
log K
n

Since both n and F are greater than zero, it
0.05916
means that at equilibrium, E = 0 Re arranging; E O = log K
n
nE O
= log K

Q = mass action quotient 0.05916
nE O

At equilibrium (by definition) Q = K K = 10 0.05916

Calculation of Equilibrium Calculation of Standard Cell

Constants Potentials

Standard cell potentials can be calculated

EO is a standard cell potential for many cells involving slightly soluble

NOT a cell potential metal salts

NOT a cell potential under non-
non-standard
In these cases, the electrochemical process
conditions involved the reduction of the metal ion

If we can calculate the underlying ion
concentration, we can calculate the standard
cell potential

Must know Ksp

1
 AgCl(s) + e-  Ag(s) + Cl-(aq) AgCl(s) + e-  Ag(s) + Cl-(aq)

Driving reaction is the reduction of Ag
For AgCl  Ag+ + Cl-

Ag+ + e-  Ag
Ksp = 1.8 x 10-10

Note that there is no change in the oxidation state
This IS NOT the same as the reaction!!!
of chlorine
Ag+ rather than Ag as the product

Under standard conditions, all species are at
NO electron exchange
unit activity.
If Ksp = [Ag+] * [Cl-] and by definition [Cl-] = 1

AgCl and Ag are under standard conditions when
Ksp = [Ag+]
there is some present

Cl- is at unit activity when the concentration is such
that the activity is 1 (assume Cl = 1)

AgCl(s) + e-  Ag(s) + Cl-(aq) Calculation of Ksp values

From the Nernst equation for the reduction
of silver

E = EO (0.05916/n) log (1/Ksp)

E = 0.799 (0.05916/1) log (1/1.8 x 10-10)

E = 0.223

But since these conditions came from the
standard conditions for the above reaction,
EO = 0.223V

Consider AgBr(s)  Ag+ + Br-

Not normally considered an electrochemical
process

K is a state function

Independent of the path used to derive the value

If we can write the reaction as a redox
process, we can calculate EO, and from that
we can calculate K

Calculation of Ksp values Potentiometric Titrations

For AgBr(s)  Ag+ + Br-
For a potentiometric titration curve, we plot
AgBr(s) + e-  Ag + Br- EO = 0.073 volume of titrant (x-
(x-axis) vs cell potential
Ag  Ag+ + e- EO = 0.799 (y
(y--axis) vs. the SHE
EOcell = EOcathode EOanode
We can measure the cell potential for either
EOcell = 0.073 0.799 = -0.726 the cathode and anode

During a titration reaction, the overall cell
potential is zero
log K = n EOcell / 0.05916 = (1)(-
(1)(-0.726) / 0.05916

Cathodic cell potential has to equal the anodic
K = 5.3 x 10-13 cell potential

2
 Potentiometric Titration

We must also determine the reaction!
Consider the titration of 50.0 mL of 0.050 M
Sn2+ with 0.020 M MnO4- in 1M H2SO4
What is the reaction?
Potentiometric Titration

Two things we MUST remember

We have to have an oxidation and a reduction
reaction combined for our overall reaction

The REACTANTS are MnO4- and Sn2+

One of the reactants MUST be listed as a
product in the reduction reactions

When we reverse that reaction, we get redox and
the proper reactants.
2MnO4- + 16H+ + 5Sn2+  5Sn4+ + 2Mn2+ + 8H2O
Potentiometric Titration

At the equivalence point
n E O + na EaO

E1 = c c
2 nc + na

This equation will work ONLY if

No pH dependance OR

pH = 0

Will not work with non 1:1 stoichiometry between the
oxidized and reduced forms in the reaction

Cr2O72- + 14H+ + 6e-  2Cr3+ + 7H2O
Potentiometric Titration

For permanganate, the only viable
reaction for titration is reduction to Mn2+

MnO4- + 8H+ + 5e-  Mn2+ + 4H2O

For tin, there are a couple of reactions

Sn2+ + 2e-  Sn

Sn4+ + 2e-  Sn2+

What is the reaction?
Potentiometric Titration

At every point except one along the
titration curve, we will have enough
information to calculate the cell potential
from either the titrant or analyte

Before the equivalence point, the analyte is in
excess

After the equivalence point, the titrant is in
excess
Potentiometric Titration

Consider the titration of 50.0 mL of 0.050 M
Sn2+ with 0.020 M MnO4- (assume [H+] = 1M)

Before the equivalence point

Sn2+ is in excess

reaction Sn4+ + 2e-  Sn2+

Note that the reaction is shown as a reduction for
purposes of calculation using the Nernst equation.

After the equivalence point

MnO4- is in excess

reaction MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
3
 50.0 mL of 0.050 M Sn2+ with 50.0 mL of 0.050 M Sn2+ with
0.020 M MnO4- ([H+] = 1M) 0.020 M MnO4- ([H+] = 1M)
After 10.00 mL of titrant is added: After 50.00 mL of titrant is added:
2MnO4- + 5Sn2+  5Sn4+ + 2Mn2+ 2MnO4- + 5Sn2+  5Sn4+ + 2Mn2+
I 0.20 2.50 0 0 I 1.00 2.50 0 0
-0.20 -0.50 +0.50 +0.20 -1.00 -2.50 +2.50 +1.00
F ~0 2.00 0.50 0.20 F ~0 ~0 2.50 1.00
Using Sn4+ + 2e-  Sn2+ Equivalence Point
E = 0.154 (0.05916/2) * log[(2.00/60)/(0.50/60)] E = [(5*1.51) + (2*0.154)] / (5+2)
E = 0.136 V E = 1.12 V

50.0 mL of 0.050 M Sn2+ with

0.020 M MnO4- ([H+] = 1M)
After 70.00 mL of titrant is added:
2MnO4- + 5Sn2+  5Sn4+ + 2Mn2+
I 1.40 2.50 0 0
-1.00 -2.50 +2.50 +1.00
F 0.40 ~0 2.50 1.00
Using MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
E = 1.51 (0.05916/5) * log [(1.00*120) / (0.40/120)(18)
E = 1.51 V