81

John A. Schreifels
Chemistry 212
Chapter 20-1
Chapter 20
Electrochemistry
82
John A. Schreifels
Chemistry 212
Chapter 20-2
Overview
Half-Reactions
Balancing oxidation reduction in acidic and basic solutions
Voltaic cells
Construction of voltaic cells
Notation for voltaic cells
Electromotive force (EMF)
Standard cell potentials
Equilibrium constants from EMFs
Concentration dependence of EMF
Electrolytic cells
Aqueous electrolysis
Stoichiometry of electrolysis

83
John A. Schreifels
Chemistry 212
Chapter 20-3
Electrochemistry
Electrochemistry - Field of
Chemistry dealing with transfer of
electrons from one species to
another.

E.g. Zn in CuSO
4
(aq).

Electrochemical cell - combination of
two half reactions to produce
electricity from reaction.

E.g. Danielle cell: Zn and Cu
electrodes in salts of these ions.
84
John A. Schreifels
Chemistry 212
Chapter 20-4
Balancing Redox Reactions: Oxidation Number
Method
Determine oxidation # for each atom- both sides of equation.
Determine change in oxidation state for each atom.
Left side: make loss of electrons = gain.
Balance on other side.
Insert coefficients for atoms that don't change oxidation state.
E.g. Balance
FeS(s)+CaC
2
(s)+CaO(s)Fe(s)+CO(g)+CaS(s)
In acidic or basic solution balance as above, then balance
charge with H
+
or OH

on one side and water on other side.

Cancel waters that appear on both sides at end.
E.g. Balance which occurs in acidic solution:

+
2
4 2
CrO Cl CrO ClO
85
John A. Schreifels
Chemistry 212
Chapter 20-5
Balancing: Half-Reaction Method
Write unbalanced half reactions for the oxidation and the
reduction
Balance the number of elements except O and H for each.
Balance O's with H
2
O to the deficient side.
Balance H's with H
+
to the hydrogen deficient side
Acidic: add H
+
Basic: add H
2
O to the deficient side and OH to the other side.
Balance charge by adding e

to the side that needs it.

Multiply each half-reaction by integers to make electrons
cancel.
Add the two half-reactions and simplify.
E.g. Balance:
Acidic: Zn(s) + VO
2+
(aq) Zn
2+
(aq) + V
3+
(aq).
Basic: Ag(s) + HS

(aq) + (aq) Ag
2
S(s) + Cr(OH)
3
(s).
2
4
CrO
86
John A. Schreifels
Chemistry 212
Chapter 20-6
Galvanic (Voltaic) and Electrolytic Cells
Cell reaction Redox reaction involved in
electrochemical cell.
Voltaic (galvanic) cell reaction is spontaneous and
generates electrical current.
Electrolytic non-spontaneous reaction occurs due
to passage of current from external power source.
E.g. charging of batteries.
87
John A. Schreifels
Chemistry 212
Chapter 20-7
Galvanic Cell 2
anode electrode where oxidation occurs.
cathode electrode where reduction occurs.
salt bridge ionic solution connecting two half-
cells (half-reactions) to prevent solutions from
mixing.
E.g. Which is the anode and cathode in the cell
to the right? Write the halfreactions.
Cd(s) + 2Ag
+
(aq) 2Ag(s) + Cd
2+
(aq)
Sign of electrodes (current flows from anode to
cathode):





E.g. determine direction of electron flow for the
reaction for a galvanic cell made from Ni(s) and
Fe(s). The reaction is:

2Fe
3+
(aq) + 3Ni 2Fe(s) + 3Ni
2+
(aq)
Electrode Sign Description
1. Cathode: + cations migrate to it.
cations reduced
2. Anode:

anions migrate to it.
cations made.

88
John A. Schreifels
Chemistry 212
Chapter 20-8
Shorthand Notation for Galvanic Cells
Shorthand way of portraying electrodes in a voltaic
electrochemical cell.
Redox couple-oxidized and reduced forms of same element
when it is involved in electrochemical reaction. Shorthand:
Ox/Red
E.g. Cu
2+
/Cu, Zn
2+
/Zn.
2 couples required for electrochemical reaction.
Shorthand rules:
Anode reaction-left; reduced form first.
Cathode-right; oxidized form first.
Vertical line drawn between different phases including reaction of
gases at metal electrode.
Double vertical drawn where salt bridge separates two half-
reactions.
E.g. draw cell diagram for
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s).
Fe
3+
(aq) + H
2
(g) Fe
2+
(aq) + 2H
+
(aq).
89
John A. Schreifels
Chemistry 212
Chapter 20-9
Electrical Work
Earlier w = PAV
In electrochemistry electrical pressure = potential
difference; w = Eq or charge times the electrical
pressure.
Units: CoulombVolts = Joules (SI Units 1J = 1CV) ;

Also want to relate to # moles.
1 mole e

= 1 Faraday = 1 F
F = qeN = 1.602x10
19
C6.022x10
23
/mol =
9.65x10
4
C/mol e

.
810
John A. Schreifels
Chemistry 212
Chapter 20-10
Cell Potentials for Cell Reactions: Spontaneity of
Redox Reactions
AG vs E:




AG E AG = nFE. Use this to calculate AG for
electrochemical reaction when cell voltage known.

E.g. Determine AG for Zn/Cu cell if E = 1.100V

AG
E
At Equilibrium 0 0
Spontaneous

+
Not spontaneous +


811
John A. Schreifels
Chemistry 212
Chapter 20-11
Standard Reduction Potentials
As with thermodynamic quantities, we list cell potentials at standard state = 1M
at 1 atm and usually 25C.
Cell potential is the sum of half-cell potentials using Hess law.


Half-cell reactions for Daniell cell were




Potential at each electrode initially determined relative to SHE = Standard
hydrogen electrode.
2H
+
(aq)+2e

H
2
(g); [H
+
] = 1M and P
H2
=1atm.
Other reaction run to determine if the SHE reaction proceeds spontaneously in
direction written when connected to other half-cells.
E.g. the cell potential of copper at standard state conditions relative to
SHE(acting as the anode) was 0.340 V; determine the halfcell potential for Zn
Zn
2+
if the potential for the Daniell cell (standard state conditions) was 1.100
V.
Half-cell reactions reported as reductions.
Zn(s) Zn
2+
(aq) + 2e

Anode
Cu
2+
(aq) + 2e

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

o
anode
o
cathode
o
cell
E E E =
812
John A. Schreifels
Chemistry 212
Chapter 20-12
Using Standard Reduction Potentials
Large negative value means oxidation strongly favored; strong reducing
agent.
Large positive value means reduction strongly favored; strong oxidizing
agent.
Relative values in table give an indication that one half-reaction favored over
other. Summing half-cell reactions allow determination of standard cell potential.
Half-cell potential intensive property independent of amount of material we
dont use stoichiometric coefficients for determining standard cell
potentials.
E.g. determine the cell potential of
Br
2
(l) + 2I

(aq) I
2
(l) + 2Br

(aq)
E.g.2 determine the cell potential of
2Ag
+
(aq) + Cu(s) 2Ag(s) + Cu
2+
(aq)
E.g.3 Determine cell potential:
(aq) + Fe(s) Fe
2+
(aq) + Mn
2+
(aq) (balanced?).
when it is operated galvanically. Which is the oxidizing agent? reducing agent?
E.g. 4 Determine if the reaction below is spontaneous in the direction written.
Fe
3+
(aq) + Ag(s) ?

4
MnO
813
John A. Schreifels
Chemistry 212
Chapter 20-13
Spontaneity of Redox Reactions
AG vs E:




AG E AG = nFE. Use this to calculate AG for
electrochemical reaction when cell voltage known.
E.g. Determine AG for Zn/Cu cell if E = 1.100V

AG
E
At Equilibrium 0 0
Spontaneous

+
Not spontaneous +


814
John A. Schreifels
Chemistry 212
Chapter 20-14
Effect of Concentration on Cell EMF: The Nernst
Equation
Recall that AG = AG
o
+ RTlnQ where


or at 25C
which is called Nernst Equation.
E.g. Determine potential of Daniell cell at 25C if
[Zn
2+
] = 0.100 M and [Cu
2+
] = 0.00100 M.


=
b a
n m
] B [ ] A [
] N [ ] M [
Q
Q ln
nF
RT
E E
o
=
Q log
n
0592 . 0
E E
o
=
815
John A. Schreifels
Chemistry 212
Chapter 20-15
Electrochemical Determination of pH
Electrodes can be used to determine acidity of
solution by using hydrogen electrode with another
one e.g. Hg
2
Cl
2
half-cell.


E.g. determine the pH of a solution that develops a
cell potential of 0.280 V (at 25C) given the cell below
Pt(s) | H
2
(g) (1atm) | H
+
(? M) || Pb
2+
(1 M) | Pb(s)
E.g. 2 determine the pH of a solution that develops a
cell potential of 0.200 V (at 25C) given the cell
below (called a concentration cell).
Pt(s)|H
2
(g)(1atm)|H
+
(1.00M)||H
+
(?M)|H
2
(g)(1atm)|Pt(s)
pH . + =
- =
+
0592 0 E'
] log[H 0.0592 ' E E
816
John A. Schreifels
Chemistry 212
Chapter 20-16
Standard Cell Potentials and Equilibrium
Constants
Free energy and equilibrium constant for reaction studied can
be determined from cell voltage.
Cell potential can be determined from AG or from equilibrium
constant.
Recall: AG = nFE = RTlnK.
E.g. Determine free energy and equilibrium constant for reaction
below (unbalanced).
(aq) + Fe(s) Fe
2+
(aq) + Mn
2+
(aq)
E.g.2 Determine cell potential and equilibrium constant of Cl
2
/Br
2

cell.
E.g.3 The following cell has a potential of 0.578 V at 25C;
determine K
sp
.
Ag(s)|AgCl(s)|Cl

(1.0 M)||Ag
+
(1.0 M)|Ag(s).

4
MnO
817
John A. Schreifels
Chemistry 212
Chapter 20-17
Quantitative Aspects of Electrolysis
Current, i, measured units: 1 ampere = 1 coulomb per s (1 A = 1 Cs1).
Time of electrolysis, t (s), also measured.
Total charge, Q, calculated from the product:
Q = i-t
Charge on 1 mol of e:





mol of e in an electrolysis obtained from balanced cell reaction:
E.g. determine # mol of electron involved in the electrolysis of the following:
Ag
+
(aq) + e

Ag(s)
2Cl

(aq) + 2e Cl
2
(g)
Amount deposited given by:

E.g. Determine amount of Cu
2+
electrolyzed from solution at constant current of
6.00 A for period of 1.00 hour.

=
- =
- =
e of mol
C
96500
e
C
10 x 602 . 1
e of mol
e
10 x 02 . 6
e N F
19 23
nF
t i
=
nF
Q
= moles
-
818
John A. Schreifels
Chemistry 212
Chapter 20-18
Electrical Work
Maximum electrical work: AG = w
max
= nFE
n = mol of electrons
F = Faradays constant
E = cell potential
Units Joules
Electrical Power: 1 watt = 1 J/s.
Energy often expressed as kilowatt hr
1 kW*hr = 1000 W*3600 s = 3.6x10
6
J
E.g. determine the maximum work in kW*hr required to produce
1.00 kg of Zn from Zn
2+
in a Daniell cell where the cell potential
is 1.100 V for the production of Zn metal.
Strategy:
Determine n: mol of Zn
2+
times 2.
Calculate work.