Chap 18: Electrochemistry

1 18
Chapter 18. Electrochemistry Chapter 18. Electrochemistry
Redox rxns involve exchange of e

Consider as the sum of two elementary half rxns:

Zn (s) + Cu
2+
(aq) Zn
2+
(aq) + Cu (s)
Cu
2+
is reduced: oxidation # reduced from +2 to 0
Zn is oxidized: oxidation # increased from 0 to +2
Zn provides e

= reducing agent
Cu
2+
accepts e

= oxidizing agent
review redox rxns
Zn (s) Zn
2+
(aq) + 2 e

oxidation
Cu
2+
(aq) + 2 e

Cu (s) reduction
In solution, e

transfer occurs directly, but in an electrochemical cell, we

physically separate the half rxns and make use of the transferred e

.
Cu
2+
(aq) + 2 e

Cu (s) Zn (s) Zn
2+
(aq) + 2 e

Zn Cu
Zn
2+
Cu
2+
SO
4
2
2e

2e

SO
4
2
e

+
anode
(-)
oxidation
cathode
(+)
reduction
salt
bridge
shorthand: Zn(s) Zn
2+
(aq) Cu
2+
(aq) Cu(s)
Converts chemical energy
to electrical energy
Electrochemical (Galvanic) Cell Electrochemical (Galvanic) Cell
Electrical potential is the driving force that pushes e

through a wire.
It is measured with a voltmeter in units of Volts (V).
Potential is related to energy through the relationship:
1 J = 1 C 1 V (C, Coulomb, is a unit of electrical charge)
Each Galvanic cell has an associated cell potential, E.
E is a measure of the tendency of the rxn to proceed:
E > 0; rxn proceeds spontaneously in forward direction
E < 0; rxn proceeds spontaneously in reverse direction
magnitude of E measure the strength of the tendency
E
0
is cell potential under standard conditions:
solid/liquids in pure form
solutions at 1.0 M concentration
gases at 1.0 atm
T = 25 C.
Cell Potential Cell Potential
Cell potential, E, and free energy, DG, are both quantitative
measures of the tendency of a rxn to occur (spontaneity).
They can be related through the expression:
DG = nFE or
n = # moles of e

transferred in the rxn

F = 96,485 J/Vmol (Faraday constant)
Example:
Zn(s) Zn
2+
(aq) Cu
2+
(aq) Cu(s) E
0
= 1.10 V
DG
0
= nFE
0
(standard conditions)
DG
0
= nFE
0
= (2 mol)(96,485 J/Vmol)(1.10 V) = 212 kJ
Note: rxn spontaneous if
E > 0
DG < 0
Relating Cell Potential to Free Energy Relating Cell Potential to Free Energy
instead of tabulating E
0
for every possible rxn, we would like to
define standard half-cell potentials such that:
Zn (s) Zn
2+
(aq) + 2 e

E
0
= x
Cu
2+
(aq) + 2 e

Cu (s) E
0
= y
Zn (s) + Cu
2+
(aq) Zn
2+
(aq) + Cu (s) E
0
cell
= x + y
However, only potential differences are meaningful, so we must
measure half-cell potentials relative to an arbitrary sea level
half-reaction whose half-cell potential will be defined as E
0
= 0.
Arbitrarily choose the standard hydrogen electrode (S.H.E.)
2 H
+
(aq, 1 M) + 2 e

H
2
(g, 1 atm) E
0
0
Note: rxn better represented as 2 H
3
O
+
(aq) + 2 e

H
2
(g) + 2 H
2
O (l)
Standard (half-cell) Reduction Potentials Standard (half-cell) Reduction Potentials
Zn (s) Zn
2+
(aq) + 2 e

2 H
+
(aq) + 2 e

H
2
(g)
To measure the potential for the half-rxn: Zn (s) Zn
2+
(aq) + 2 e

set up the following experiment

Zn
Zn
2+
(1 M)
e

+
anode cathode
salt
bridge
E
0
cell
= 0.76 V
H
3
O
+
(1 M)
H
2
(1 atm)
inert Pt
electrode
voltmeter
Measuring a Standard 1/2-cell Potential Measuring a Standard 1/2-cell Potential
Chap 18: Electrochemistry
2 18
Reduction half-reaction E
0
(V)
Cl
2
(g) + 2 e

2 Cl

(aq) 1.36
Br
2
(g) + 2 e

2 Br

(aq) 1.09
Ag
+
(aq) + e

Ag (s) 0.80
Cu
2+
(aq) + 2 e

Cu (s) 0.34
2 H
+
(aq) + 2 e

H
2
(g) 0
Sn
2+
(aq) + 2 e

Sn (s) 0.14
Zn
2+
(aq) + 2 e

Zn (s) 0.76
Al
3+
(aq) + 3 e

Al (s) 1.66
Reactants higher on the list are stronger oxidizing agents
In a redox rxn, the half-rxn higher on the list will go spontaneously in
the forward direction
Reversing direction of a half-rxn switches the sign of E
0
Changing stoichiometric coefficients does not change E
0
Tabulated Standard Reduction Potentials Tabulated Standard Reduction Potentials

E = E
0
-
RT
nF
lnQ Nernst equation
Deviation from standard conditions changes driving force for rxn:
where Q is the rxn quotient
at 25 C the Nernst equation can be written

E = E
0
-
0.0592
n
log
10
Q
Non-standard Conditions: Non-standard Conditions: Nernst Nernst Equation Equation
Zn
2+
(aq) + 2 e

Zn (s) Cu (s) Cu
2+
(aq) + 2 e

Drive electrical current through cell to make

rxn run in non-spontaneous direction.
Converts electrical energy to chemical energy
Zn Cu
Zn
2+
Cu
2+
SO
4
2
2e

2e

SO
4
2
e

+
anode
oxidation
cathode
reduction
salt
bridge
power
supply
+
Electrolysis Electrolysis
Pb (s) + HSO
4

(aq) PbSO
4
(s) + H
+
(aq) + 2 e

PbO
2
(s) + HSO
4

(aq) + 3 H
+
(aq) + 2 e

PbSO
4
(s) + 2 H
2
O (l)
Rechargeable lead storage battery (car battery)
Pb PbO
2 HSO
4
HSO
4

+
anode cathode
salt
bridge
H
+
H
+
Anode:
Cathode:
Rechargeable because product, PbSO
4
(s) coats both electrodes.
Recharge by supplying electrical energy and forcing rxn to run backwards.
2 V
Batteries Batteries
Reactants are not contained in a sealed cell.
Instead, the reactants are continuously supplied to the cell.
Clean, compact source of electrical energy.
Widely considered to be the power supply of choice for the future!
OH

C electrodes
+ catalysts
Anode

Cathode
+
H
2
(g)
O
2
(g)
H
2
O(l)
H
2
O(l)
Anode: 2 H
2
+ 4 OH

4 H
2
O + 4 e

Cathode: O
2
+ 4 H
2
O + 4 e

4 OH

2 H
2
+ O
2
2 H
2
O
Fuel Cells Fuel Cells
Net rxn is the same as burning hydrogen.
Why is it better to use a fuel cell?
Stoichiometry of electrolysis
# moles of product related to # moles of e

passed through cell

by stoichiometric coefficients
total charge (C) = current (A) time (s) = I t
moles of e

= total charge / F = (total charge) / (96,485 C/mol)

therefore, moles of e

= I t / F
Electron Counting in Electrolysis Electron Counting in Electrolysis