Electrochemistry

•is one of the most important interfaces between

chemistry and everyday life, e.g. when you start your car,
turn on your calculator, use your smartphone, use your
laptop etc, you are applying electrochemistry
(electrochemical/redox rxions). An electrochemical/
redox rxion is one that involves complete transfer of e-s
from one reactant to another.
•is the study of interchange of chemical and electrical
energy using electrochemical(redox)rxions.
•involves generation of an electric current from a
spontaneous redox rxion and also
•use of a current to produce a non-spontaneous redox
rxion
 1. Electrochemical/Redox
Reactions: Balancing Redox Equations:
• A redox rxion occurring in an aqueous soln
comprises two half-rxions:
- an oxidation half-rxion and
- a reduction half-rxion.
e.g. for the unbalanced redox equation,
Ce4+(aq) + Sn2+(aq) → Ce3+(aq) + Sn4+(aq)
the reduction and oxidation half-rxions are:
Reduction half-rxion: Ce4+(aq) → Ce3+(aq)
Oxidation half-rxion: Sn2+(aq) → Sn4+(aq)
 Half-Rxion Method for Balancing
Redox Rxions in Aqueous Solns
In acidic solution:
• Write separate equations for oxidation and reduction
half-rxions.
• For each half-rxion,
a. balance all elements except hydrogen and oxygen.
b. then balance oxygen by adding H2O.
c. then balance hydrogen by adding H+.
d. then balance charge by adding e-s.
• If need be, multiply one or both balanced half-rxions by a
number so as to equalize no. of e-s transferred in the two half-
rxions.
• Add the half-rxions RHSs and LHSs respectively, and cancel
identical species.
• Check that the elements and charges are balanced.
 Example
Balance the equation for the following rxion in an
acidic soln:
MnO4ˉ(aq) + Fe2+(aq) Acid Fe3+(aq) + Mn2+(aq)
1. Identify and write equations for oxidation and
reduction half-rxions involved.
MnO4ˉ → Mn2+ this is the reduction half-rxion
+7 -2 (each O) +2 - Mn(VII) is reduced to Mn(II)
Fe2+ → Fe3+ this is the oxidation half-rxion
+2 +3 - iron(II) is oxidised to iron(III)
 Example Cont’d
2. Balance each half-rxion starting with all other
elements, then oxygen and then hydrogen:
Reduction half-rxion:
MnO4ˉ (aq) → Mn2+(aq)
a. Mn is balanced.
b. balance oxygen by adding 4H2O to the right
side of the equation:
MnO4ˉ (aq) → Mn2+(aq) + 4H2O(l)
c. balance hydrogen by adding 8H+ to the left side:
8H+(aq) + MnO4ˉ(aq) → Mn2+(aq) + 4H2O(l)
 Example Cont’d
• All elements have been balanced. Now balance the
charge using e-s. (We have the following overall charges
for reactants and products in the reduction half-rxion)
8H+(aq)+ MnO4ˉ(aq) → Mn2+(aq) + 4H2O(l)
8+ + -1 2+ + 0
7+ 2+
• equalize the charges by adding 5 e-s to the left side:
5eˉ + 8H+(aq) + MnO4ˉ(aq) → Mn+(aq) + 4H2O(l)
-5 + 8+ + -1 2+ + 0
2+ 2+
 Example Cont’d
• Both elements and charges are now balanced, so
this is now a balanced reduction half-rxion.
Oxidation half-rxion: Fe2+(aq) → Fe3+(aq)
the elements are balanced, we balance the charge:
Fe2+(aq) → Fe3+(aq)
2+ 3+
• One e- is needed on the right side to give a net 2+
charge on both sides:
Fe2+(aq) → Fe3+(aq) + e-
2+ 2+
 Example Cont’d
3. Equalize e- transfer in the two half-rxions. Since the
reduction half-rxion involves a transfer of 5 e-s and the
oxidation half-rxion involves a transfer of only 1 e-, the
oxidation half-rxion is multiplied by 5:
5Fe2+(aq) → 5Fe3+(aq) + 5e-
4. Add the half-rxions’ LHSs and RHSs respectively:
5e-+5Fe2+(aq)+MnO4ˉ(aq)+8H+(aq)→
5Fe3+(aq)+Mn2+(aq)+ 4H2O(l) + 5e-
Note: e-s cancel to give the final balanced equation:
5Fe2+(aq)+MnO4ˉ(aq)+8H+(aq)→5Fe3+(aq)+Mn2+(aq)+4H2O(l)
5. Check that elements and charges are balanced.
Elements balance: 5Fe,1Mn,4O,8H → 5Fe, 1Mn, 4O, 8H
Charges balance:5(2+)+(1-+8(1+)=17+→5(3+)+(2+)+0=17+
The equation is balanced.
 Half-Rxion Method for Balancing
Equations for Redox Rxions Occurring
in Basic Soln Procedure
a. Use the half-rxion method for acidic solns to obtain
the final balanced equation as if H+ ions were present.
b. To both sides of the equation obtained above, add
no. of OH- ions equal to no. of H+ ions.
(eliminate H+ by forming H2O.)
c. Form H2O on the side containing both H+ and OH-
ions, and eliminate the no. of H2O molecules that
appear on both sides of the equation.
d. Check that elements and charges are balanced.
 Example
• Aqueous CN- solution is used to extract silver under
basic conditions as follows:
Ag(s) + CN-(aq) + O2(g) Base Ag(CN)2-(aq)
Balance this equation using the half-rxion method.
Solution
• 1st balance the equation like in acidic soln.
Balance the oxidation half-rxion:
CN-(aq) + Ag(s) → Ag(CN)2-(aq)
• Balance all elements apart from hydrogen and oxygen:
2CN-(aq) + Ag(s) → Ag(CN)2-(aq)
• Balance charge:
2CN-(aq) + Ag(s) → Ag(CN)2-(aq) + e-
 Example Cont’d
• Balance the reduction half-rxion:
O2(g) →
• Balance oxygen:
O2(g) → 2H2O(l)
• Balance hydrogen:
O2(g) + 4H+(aq) → 2H2O(l)
• Balance charge:
4e- + O2(g) + 4H+(aq) → 2H2O(l)
• Multiply the balanced oxidation half-rxion by 4:
8CN-(aq) + 4Ag(s) → 4Ag(CN)2-(aq) + 4e-
• Add the half-rxions, and cancel identical species:
8CN-(aq) + 4Ag(s) → 4Ag(CN)2-(aq) + 4e-
4e- + O2(g) + 4H+(aq) → 2H2O(l)
8CN-(aq)+ 4Ag(s)+ O2(g) + 4H+(aq) → 4Ag(CN)2-(aq) + 2H2O(l)
 Worked Example Cont’d
2. 2nd Now add OH- ions to both sides of the balanced
equation to eliminate H+ ions.
8CN-(aq)+ 4Ag(s)+ O2(g)+ 4H+(aq)+ 4OH-(aq)→ 4Ag(CN)2-(aq)+ 2H2O(l) + 4OH-(aq)
4H2O

3. Eliminate as many H2O molecules as possible:

8CN-(aq)+ 4Ag(s)+ O2(g)+ 2H2O(l) → 4Ag(CN)2-(aq)+ 4OH-(aq)
4. Check that elements and charges are balanced.
• Elements balance: 8C, 8N, 4Ag, 4O, 4H → 8C, 8N, 4Ag, 4O, 4H
• Charges balance: 8(1-) + 0 + 0 + 0 = 8- → 4(1-) + 4(1-) = 8-
Equation is balanced
2. Electrochemical Cells (Galvanic Cells)
-a device in which chemical energy from a spontaneous
redox rxion is changed to electrical energy that can be
used to do work
How to use a redox rxion to generate a current:
consider the redox rxion:
8H+(aq)+ MnO4-(aq)+ 5Fe2+(aq) → Mn2+(aq)+ 5Fe3+(aq)+ 4H2O(l)
• Fe2+ is oxidized; MnO4- is reduced; e-s are transferred
from Fe2+(reducing agent) to MnO4- (oxidizing agent).
• Broken down into oxidation and reduction half-rxions:
Reduction: 8H+ + MnO4- + 5e- → Mn2+ + 4H2O
Oxidation: 5(Fe2+ → Fe3+ + e-)
• oxidation rxion must occur 5X for each time the
reduction rxion occurs. The balanced overall reaction is
the sum of these two half-rxions.
 Galvanic Cells Cont’d
When MnO4 and Fe are present in the same soln, e-s
- 2+

are transferred directly when reactants collide.

No useful work is obtained from chemical energy
involved in the rxion because it’s released as heat.
This Energy is harnessed by separating the oxidizing
agent from the reducing agent and forcing e- transfer
to occur through a wire.
Current produced in the wire by e- flow can then be
used to do useful work.
However, when apparatus is set up as below, e-s should
flow through the wire from Fe2+ to MnO4-, but, no
flow of e-s is observed. Why?
Because current flows for an instant, then stops due to
charge build-ups in the two parts.
 Galvanic Cells Cont’d

If e-s flowed from the right to the left part in the

apparatus as shown, the left part (receiving e-s) would
become (-) charged, and the right part (losing e-s)
would become (+) charged.
Creating a charge separation requires a large amount
of energy. Thus sustained e- flow cannot occur under
these conditions.
 Galvanic Cells Cont’d
This problem is overcome by connecting the solns
through a salt bridge (a U-tube filled with an
electrolyte which completes the circuit by balancing
the charges in each unit) or a porous disk (a semi-
permeable membrane that allows ions to flow back and
forth without extensive mixing of the two solns), so
that ions can flow to keep net charge in each unit zero.
(see fig below).
 Galvanic Cells Cont’d
The rxion in an electrochemical cell occurs at the
interface between the electrode and the soln where
e- transfer occurs. The electrode portion in which
oxidation occurs is called anode; the electrode
portion in which reduction occurs is called cathode
(see fig below).
 Galvanic Cells Cont’d
Cell Potential
In a galvanic cell, the oxididing agent in the cathode unit pulls e-s
through a wire from the reducing agent in the anode unit. This
“pull,” or driving force, on the e-s is called cell potential (Ecell), or
electromotive force (emf) of the cell.
Unit of electrical potential is the volt (V), which is defined as:
1V = 1J/1C.
Cell potential is measured using a voltmeter, which works by
drawing a current through a known resistance. When current
flows through a wire, frictional heating occurs. This wastes
some of the energy of the cell. Thus, voltmeter measured
potential is less than maximum cell potential.
Maximum cell potential is obtained if voltage is measured when no
current is flowing (zero current) using a potentiometer, so
there’s no energy wasted.
 Galvanic Cells Cont’d
Voltage on the potentiometer is adjusted until no
current flows in the cell circuit. Thus, cell potential =
voltage set on the potentiometer but with opposite
sign. The value obtained is maximum cell potential,
since no energy is wasted on heating the wire.
(Digital voltmeters that draw only a
negligible amount of current (see
Fig.) are now available and are more
convenient to use. Thus, they have
replaced potentiometers in the
modern laboratory).
 3. Standard Reduction Potential
A galvanic cell rxion is always a redox rxion that can be
broken down into two half-rxions, each with a potential.
When a cell is constructed from a given pair of half-rxns,
cell potential is the sum of half-cell potentials.
 Standard Reduction Potentials Cont’d
e.g. in fig(a) above, the cell rxion is:
Zn(s) + 2H+(aq) → Zn2++ H2(g)
the anode is Zn metal electrode with Zn2+and SO42- ions in
aqueous solution;
the anode rxion is the oxidation half-rxion:
Zn → Zn2+ + 2e-
Zinc metal, to produce Zn2+ ions that go into soln, gives
up e-s, which flow through the wire.
Assumption: all cell components are in their standard
states, i.e. the soln in anode unit at 1M Zn2+ conc, and 1
atm pressure.
The cathode rxion is the reduction half-rxion:
2H+ + 2e- → H2
the cathode is a Pt electrode in contact with 1M H+ ions
and H gas at 1atm. This is the standard hydrogen
electrode, and is shown in Fig.(b) above.
 Standard Reduction Potentials Cont’d
Total cell potential = 0.76 V as measured on digital
voltmeter.
If we arbitrarily assign the rxion 2H+ + 2e- → H2
where [H+] = 1M and PH2 = 1atm, a potential = 0.00 V,
then the rxion Zn → Zn2+ + 2e-
will have a potential = 0.76V because
E°cell = E°H →H + E°Zn→Zn NB: the superscript ° indicates
+
2
2+

that standard conditions

0.76V = 0V + 0.76V have been used.
By setting standard potential for the half-rxion
2H+ + 2e- → H2 equal to zero,
values of all other half-rxions have been assigned.
 Standard Reduction Potentials Cont’d
For example, measured potential for the cell shown in the
Fig. below is 1.10V. The cell reaction is:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
 Standard Reduction Potentials Cont’d
• Cell rxion divided into the half-rxions:
Anode: Zn → Zn2+ + 2e-
Cathode: Cu2+ + 2e- → Cu
• Then E°cell = E°Zn→Zn + E°Cu →Cu
2+ 2+

• E°Zn→Zn = 0.76V, thus, E°Cu →Cu = 0.34V because

2+ 2+

1.10V = 0.76V + 0.34V

• All half-rxion potentials are based on the
assignment of 0.00V to the process 2H+ + 2e- → H2
under standard conditions.
 Standard Reduction Potentials Cont’d
Essential characteristics of half-cell potentials
• By convention, all half-rxion potentials are
reduction potentials i.e. potentials for reduction
processes.
e.g. 2H+ + 2e- → H2
Cu2+ + 2e- → Cu
Zn2+ + 2e- → Zn
• E° values of reduction half-rxions with all solutes at
1M and all gases at 1atm are called standard
reduction potentials.
 Standard Reduction Potentials Cont’d
To combine two reduction half-rxions to get a balanced
overall redox rxion:
1. One of the reduction half-rxions is reversed.
The half-rxion with largest (+) potential remains a
reduction rxion, the other half-rxion is reversed to
become an oxidation rxion.
Net cell potential is now the difference between the
reduction half-rxion and the oxidation half-rxion.
E°cell = E°(cathode) - E°(anode)
2. no. of e-s lost = no. of e-s gained, so, multiply the half-
rxions by integers so as to balance the charge and thus
the equation but, the value of E° is not changed because
standard reduction potential is an intensive property
Standard Reduction Potentials Cont’d
E.g.: for a galvanic cell based on the redox rxion
Fe3+(aq) + Cu(s) → Cu2+(aq) + Fe2+(aq)
• Half-rxions in this cell are:
Fe3+ + e- → Fe2+ E° = 0.77V (1)
Cu2+ + 2e- → Cu E° = 0.34 V (2)
• These are all reduction rxions. To balance the cell
rxion and calculate standard cell potential, rxion
(2) is reversed because it has smallest reduction
potential:
Cu → Cu2+ + 2e- - E° = - 0.34V
 Worked Example Cont’d
Each Cu atom yields 2 e-s but each Fe3+ ion accepts
only 1 e-, thus rxion (1) is multiplied by 2 as follows:
2Fe3+ + 2e- → 2Fe2+ E° = 0.77V
NB: E° is not changed.
A balanced overall cell rxion = sum of modified half-
rxions:
2Fe3+ + 2e- → 2Fe2+ E(cathode) = 0.77V
Cu → Cu2+ + 2e- -E(anode) = -0.34 V
Cell rxion: Cu(s) + 2Fe3+(aq) → Cu2+(aq) + 2Fe2+(aq)
E°cell = E°(cathode) - E°(anode)
= 0.77V - 0.34V = 0.43V
 Standard Reduction Potentials at 25°C (298 K) for
Some Common Half-Reactions
• Half-Reaction %° (V) Half-Reaction %° (V)
• F2 + 2e- → 2F- 2.87 O2 + 2H2O + 4e- → 4OH- 0.40
• Ag2+ + e- → Ag+ 1.99 Cu2+ + 2e- → Cu 0.34
• Co3- + e- → Co2- 1.82 Hg2Cl2 + 2e- → 2Hg + 2Cl- 0.27
• H2O2 + 2H2 + 2e- → 2H2O 1.78 AgCl + e- → Ag + Cl- 0.22
• Ce4+ + e- → Ce3+ 1.70 SO42-+4H++2e-→H2SO3+H2O0.20
• PbO2+4H++SO42-+2e-→PbSO4+2H2O 1.69 Cu2+ + e- → Cu+ 0.16
• MnO4- + 4H+ + 3e- → MnO2 + 2H2O 1.68 2H+ + 2e- → H2 0.00
• 2e- + 2H+ + IO4- → IO3- + H2O 1.60 Fe3+ + 3e- → Fe -0.036
• MnO4- + 8H+ + 5e- → Mn2+ + 4H2O 1.51 Pb2+ + 2e- → Pb -0.13
• Au3+ + 3e- → Au 1.50 Sn2+ + 2e- → Sn -0.14
• PbO2 + 4H+ + 2e- → Pb2+ + 2H2O 1.46 Ni2+ + 2e- → Ni -0.23
• Cl2 + 2e- → 2Cl- 1.36 PbSO4 + 2e- → Pb + SO42- -0.35
• Cr2O72- + 14H+ + 6e- → 2Cr3+ + 7H2O 1.33 Cd2+ + 2e- → Cd -0.40
• O2 + 4H+ + 4e- → 2H2O 1.23 Fe + 2e → Fe
2+ - -0.44
• MnO2 + 4H+ + 2e- → Mn2+ + 2H2O 1.21 Cr3+ + e- → Cr2+ -0.50
• IO3- + 6H+ + 5e- → ½ I2 + 3H2O 1.20 Cr3+ + 3e- → Cr -0.73
• Br2 + 2e- → 2Br- 1.09 Zn2+ + 2e- → Zn -0.76
• VO2+ + 2H+ + e- → VO2+ + H2O 1.00 2H2O + 2e- → H2 + 2OH- -0.83
• AuCl4- + 3e- → Au + 4Cl- 0.99 Mn2+ + 2e- → Mn -1.18
• NO3- + 4H+ + 3e- → NO + 2H2O 0.96 Al3+ + 3e- → Al -1.66
• ClO2 + e- → ClO2- 0.954 H2 + 2e- → 2H- -2.23
• 2Hg2+ + 2e- → Hg22+ 0.91 Mg2+ + 2e- → Mg -2.37
• Ag+ + e- → Ag 0.80 La3+ + 3e- → La -2.37
• Hg22+ + 2e- → 2Hg 0.80 Na+ + e- → Na -2.71
• Fe3+ + e- → Fe2+ 0.77 Ca2+ + 2e- → Ca -2.76
• O2 + 2H+ + 2e- → H2O2 0.68 Ba2+ + 2e- → Ba -2.90
• MnO4- + e- → MnO42- 0.56 K + + e- → K -2.92
• I2 + 2e- → 2I- 0.54 Li+ + e- → Li -3.05
• Cu+ + e- → Cu 0.52
 Electrochemical Cells Line Notation
Anode components are listed Left; Cathode components Right,
separated by double vertical lines (= salt bridge or porous
disk)
e.g. Mg(s)│Mg2+(aq)║Al3+(aq) │Al(s)
Phase difference (boundary) is shown by a single vertical line
between solid Mg metal and Mg2+ in aqueous soln and
between solid Al and Al3+ in aqueous soln.
The anode electrode is listed outer far left; the cathode
electrode outer far right.
For a cell whose components involved in a redox rxion are ALL
ions, a nonreacting (inert) conductor, e.g. Platinum, is used
because dissolved ions can not be an electrode.
e.g.
Pt(s)│ClO3-(aq), ClO4-(aq), H+(aq) ║H+(aq), MnO4-(aq), Mn2+(aq)│Pt(s)
 Electrochemical Cells Cont’d
How to describe a galvanic cell fully, given its half- rxions
To fully describe a galvanic cell, indicate:
(1)cell potential (2) cell rxion (3) cell setup (4) e- flow
e.g. A galvanic cell is based on the following half-rxions:
Fe2+ + 2e- → Fe E° = -0.44 V
MnO4- + 5e- + 8H+ → Mn2+ + 4H2O E° = 1.51 V
1. Cell potential: one of these rxns must run in reverse.
HINT: A cell runs spontaneously in the direction that
produces (+) cell potential. Thus, the half-rxion
involving iron is reversed, since it leads to a (+) cell
potential:
Fe → Fe2+ + 2e- -E° = 0.44 V Anode rxion
MnO4-+5e-+8H+→Mn2++4H2O E° = 1.51V Cathode rxion
E°cell = E°(cathode)- E°(anode) = 1.51V + 0.44V = 1.95V
 Electrochemical Cells Cont’d
2. Balanced cell rxion:
5(Fe → Fe2+ + 2e-)
2(MnO4- + 5e- + 8H+ → Mn2+ + 4H2O)
2MnO4-(aq)+ 5Fe(s)+ 16H+(aq)→5Fe2+(aq)+ 2Mn2+(aq)+ 8H2O(l)
3. Cell setup: Physical
4. e- flow: In the left
partition, the half-rxion
that takes place at this
electrode
Fe → Fe2+ + 2e-
is an oxidation rxion, so
this partition is the
anode. The electrode is
pure Fe metal.
 Electrochemical Cells Cont’d
In the right partition, the half-rxion that occurs
MnO4- + 5e- + 8H+ → Mn2+ + 4H2O
is a reduction rxion, so this partition is the cathode.
Neither MnO4- nor Mn2+ ions can be electrodes, so, a
nonreacting conductor, Pt, is used. To determine
direction of e- flow: In the left partition, Fe oxidation
half-rxion:
Fe → Fe2+ + 2e- releases e-s.
• In the right partition the MnO4- reduction half-rxion:
MnO4- + 5e- + 8H+ → Mn2+ + 4H2O consumes e-s.
• Thus e-s flow from Fe to MnO4- i.e. from the anode to
the cathode. Thus, the line notation for this cell is:
Fe(s)│Fe2+(aq) ║MnO4-(aq), Mn2+(aq)│Pt(s)
4. Cell Potential, Electrical Work & Free Energy
(Relationship between Thermodynamics & Electrochemistry)
Work done when e-s are transferred through a wire
depends on a thermodynamic driving force behind the
e-s, the emf, which is the potential difference (V)
between two points in a circuit. REM: 1 volt = 1 joule of
work done/1 coulomb of charge transferred. Thus, emf
= potential difference (V) = work(J)/charge (C)
Therefore, 1 joule of work is done when 1 coulomb of
charge is transferred between two points in a circuit
that differ by a potential of 1 volt.
From a system point of view, work done by the system
carries a minus sign because energy is expended, but,
when a cell produces current, cell potential is (+), thus,
cell potential, E, and work, w, carry opposite signs:
E = -w/q thus, -w = qE
and maximum work in a cell is obtained when cell
potential is maximum: -wmax = qEmax or wmax = -qEmax
 Cell Potential, Electrical Work & Free
Energy Cont’d
• To obtain electrical work, current must flow. When
current flows, some energy is lost through frictional
heating, and wmax cannot be obtained. In any real,
spontaneous process some energy is always wasted i.e.
actual work done is always less than maximum possible.
Though we can never achieve wmax from a galvanic cell,
we can measure Emax.
Current flow is negligible when cell potential is
measured using a potentiometer or an efficient digital
voltmeter. No current flow means no energy wasted,
hence, measured potential is maximum.
Cell Potential, Electrical Work & Free Energy
• We can’t realize wmax from a cell rxion, but the
value for work done, is still needed to evaluate
efficiency of a cell. Example: A galvanic cell has
Emax = 2.50V. In an expt, 1.33 moles of e-s were
passed through this cell at average Eactual=2.10V.
Actual work done is: w = -qEactual
Eactual=potential difference at which a current of
2.10V = 2.10J/C was flowing.
q = charge transferred in Coulombs.
• Charge on 1 mole of e-s=constant= one faraday
(F) = 96,485C = charge per mole of e-s.
 Cell Potential, Electrical Work & Free Energy
Thus q = no. of moles of e-s x charge per mole of e-s
q = nF = 1.33 mol e- x 96,485 C/mol e-
Therefore, for the above expt, actual work done is:
w = -qE = -nFE
= -(1.33mole- x 96,485C/mole-)(2.10J/C)
= -2.69 x 105 J
For maximum work, wmax, maximum cell potential,
Emax, is used: wmax= -qEmax
= -(1.33mol e- x 96,485C/mol e-)(2.50J/C)
= -3.21 x 105 J
Note: Work is never the maximum possible if any
current is flowing.
Thus, in its actual operation, efficiency of this cell is:
(w/wmax)x100%=(-2.69x105J/-3.21x105J)x100%
= 83.8%
 Cell Potential, Electrical Work & Free Energy
Relation Between Cell Potential and Free Energy
In a process that is at constant temp & pressure, change in
free energy equals maximum work obtainable from that
process: wmax= ΔG
For a galvanic cell: wmax = -qEmax = ΔG
q = nF, thus ΔG = -qEmax = -nFEmax
NB: any potential hereafter given is maximum potential
Thus ΔG = -nFE. For standard conditions: ΔG° = -nFE°
Thus, Emax α the free energy difference between reactants
and products in a cell.
This relationship
(1)gives experimental means to obtain ΔG for a rxion,
(2) confirms that a galvanic cell will run in the direction that
gives a (+) value for Ecell. NB: A positive Ecell value relates
to a negative ΔG value, the condition for spontaneity.
 Cell Potential, Electrical Work & Free Energy
Dependence of Cell Potential on Concentration
• So far we’ve discussed cells under std conditions i.e.
1M conc, 1atm pressure and 298K. What happens to
Ecell when conc changes? Under std conditions, the
cell with the rxion
Cu(s) + 2Ce4+(aq) → Cu2+(aq) + 2Ce3+(aq)
has Ecell = 1.36V.
What will Ecell be if [Ce4+] is greater than 1.0M?
• Qualitative answer in terms of Le Châtelier’s principle.
• Increase in conc. of Ce4+ favours the forward rxion.
This increases the driving force on the e-s, thus Cell
potential increases.
• Increase in conc. of a product (Cu2+ or Ce3+) opposes
the forward rxion. This decreases Cell potential.
Cell Potential, Electrical Work & Free Energy
Effects of Concentration on Ecell
• For the cell rxion
2Al(s) + 3Mn2+(aq) → 2Al3+(aq) + 3Mn(s) E°cell = 0.48V
predict whether Ecell is larger or smaller than E°cell for
the following cases.
a. [Al3+] = 2.0M, [Mn2+] = 1.0M
b. [Al3+] = 1.0M, [Mn2+] = 3.0M
• Solution
a. A product concentration has been raised above 1.0M.
This will oppose the cell rxion and causes Ecell to be less
than E°cell (Ecell < 0.48 V).
b. A reactant conc. has been increased above 1.0M,
thus Ecell will be greater than E°cell (E°cell > 0.48 V).
Cell Potential, Electrical Work & Free Energy
Concentration Cells
are galvanic cells in which both units (anode and
cathode) have the same components but at different
concs because Ecell depends on conc, e.g. in a cell in
which both partitions contain aqueous AgNO3, but at
different concs, what will be the Ecell and the direction of
e- flow?
The reduction half-rxion occurring in both partitions of
this cell is:
Ag+ + e- → Ag E° = 0.80V.
If the cell had 1M Ag+ in both partitions,
E°cell = 0.80V - 0.80V = 0V.
But, in this cell, concs of Ag+ in the two partitions are 1M
and 0.1M. Because concs of Ag+ are unequal, half-cell
potentials will not be the same, and the cell will exhibit a
(+) voltage. In which direction will e-s flow in this cell?
 Cell Potential, Electrical Work & Free Energy
Nature equalizes the concs of Ag+ in the two partitions
by transferring e-s from the 0.1M Ag+ partition to the
1M Ag+ partition. This e- transfer produces more Ag+ in
the left partition and consumes Ag+ (to form Ag) in the
right partition.
Difference in conc is the only factor that produces
Ecell and voltages are typically small.
The Nernst Equation
Dependence of Ecell on conc is a result of dependence of
free energy on concentration.
Rem: equation ΔG = ΔG° + RT ln(Q), where Q = rxion
quotient used to calculate effect of conc. on ΔG.
Since ΔG = -nFE and ΔG° = -nFE°
the equation becomes -nFE = -nFE° + RT ln(Q)
 Cell Potential, Electrical Work & Free Energy
Dividing each side of the equation by (-nF) gives
E = E° - RT ln(Q)
nF
i.e. relationship between Ecell and concs of cell
components, and is called Nernst equation.
At 25°C, Nernst equation becomes:
E = E° - 0.0591 log(Q)
n
This relationship is used to calculate Ecell of a cell in which
some or all components are not in their standard states.
e.g. for a galvanic cell based on the rxion below,
2Al(s) + 3Mn2+(aq) → 2Al3+(aq) + 3Mn(s), E°cell=0.48V.
If [Mn2+] = 0.50M and [Al3+] = 1.50M, Ecell @ 25°C for
this cell can be calculated using Nernst equation as
follows: Ecell = E°cell - (0.0591/n) log(Q)
 Cell Potential, Electrical Work & Free Energy
Note: E°cell = 0.48V and
Q = [Al3+]2/[Mn2+]3 = [(1.50)]2/[0.50]3 = 18
From the oxidation and reduction half-rxions:
Oxidation: 2Al → 2Al3+ + 6e-
Reduction: 3Mn2+ + 6e- → 3Mn we deduce n = 6
Thus Ecell = 0.48 - (0.0591/6) log(18)
= 0.48 - (0.0591/6)(1.26)= 0.48-0.01=0.47V
Note: Ecell is slightly less due to non-std concs used. The
cell will spontaneously discharge until it reaches
equilibrium, at which point: Q = K (equilibrium
constant) and Ecell = 0
A “dead” battery is one in which the cell rxion has
reached equilibrium, and there is no longer any
chemical driving force to push e-s through the wire, i.e.
at equilibrium, components in the two cell partitions
have the same free energy, and ΔG = 0 . The cell no
 Cell Potential, Electrical Work & Free Energy Cont’d
Ion-Selective Electrodes
Because Ecell is sensitive to concs of reactants and
products involved in the cell rxion, measured potentials
can be used to determine conc of an ion. An
instrument that measures concentration using
potential is a pH meter.
A pH meter has three main components: a standard
electrode of known potential, a special glass electrode
that changes potential with conc of H+ ions in the soln
into which it is dipped, and a potentiometer that
measures potential between electrodes. The
potentiometer reading is automatically converted
electronically to a pH reading of the soln being tested.
The glass electrode contains a reference soln of dil. HCl
in contact with a thin glass membrane.
 Cell Potential, Electrical Work & Free Energy
Electrical potential of the glass electrode depends on the
difference in [H+] between the reference soln and the
soln into which the electrode is dipped.
Thus electrical potential varies with pH of the soln being
tested. Electrodes that are sensitive to the conc of a
particular ion are called ion-selective electrodes, e.g.
glass electrode for pH measurement.
Calculation of Equilibrium Constants for Redox Rxions
For a cell at equilibrium, Ecell = 0 and Q = K
Applying these conditions to the Nernst equation at 25°C
E = E°- 0.0591/n log(Q)
0 = E°- 0.0591/n log(K)
log(K) = nE°/0.0591 @ 25°C.
 Batteries & Fuel Cells
A battery is a group of galvanic cells connected in series,
where potentials of individual cells add up to give total
battery potential.
Most Common types of Batteries
Lead Storage Battery:
can function for several yrs under temp extremes (-1.1°C -
48.9°C).
Pb is the anode, and Pb coated with PbO2 is the cathode.
Both electrodes dip into an electrolyte soln of H2SO4.
Electrode rxions are:
Anode rxion: Pb + HSO4- → PbSO4 + H+ + 2e-
Cathode rxion: PbO2+HSO4-+3H++2e- → PbSO4+2H2O
Cell rxion: Pb(s)+PbO2(s)+2H+(aq)+2HSO4-(aq)
→2PbSO4(s)+2H2O(l)
 Batteries & Fuel Cells
A typical vehicle lead storage battery has six cells
connected in series. Each cell produces 2V, to give
total battery potential of 12V. H2SO4 is consumed as
battery discharges. This reduces the electrolyte
density from its initial value of about 1.28 g/cm3 in
fully charged battery. Thus, battery condition can be
monitored by measuring density of H2SO4 soln. Solid
PbSO4 formed in the cell rxion during discharge
adheres to the surface of the electrodes. Battery is
recharged by forcing current through it in the
opposite direction to reverse the cell rxion. A car’s
battery is continuously charged by an alternator
driven by vehicle engine.
 Batteries & Fuel Cells
Dry cell battery is the most common.
An acid dry cell battery contains a Zn inner case that acts
as the anode and a C rod in contact with a moist paste of
solid MnO2, solid NH4Cl, and C that acts as the cathode.
Half-rxns are complex but can be approximated as
follows:
Anode rxion: Zn → Zn2+ + 2e-
Cathode rxion: 2NH4++2MnO2+2e- → Mn2O3+2NH3+H2O
This cell produces a potential of about 1.5V.
In an alkaline dry cell battery, solid NH4Cl is replaced
with KOH or NaOH. Hence, half-rxions are as follows:
Anode rxion: Zn + 2OH- → ZnO + H2O + 2e-
Cathode rxion: 2MnO2 + H2O + 2e- → Mn2O3 + 2OH-
Alkaline dry cells last longer mainly because the Zn anode
corrodes less rapidly under basic conditions than under
acidic conditions.
 Batteries & Fuel Cells
A silver cell has a Zn anode and a cathode that uses
Ag2O as oxidizing agent in a basic environment.
Mercury cells, often used in calculators, have a Zn
anode and a cathode involving HgO as the oxidizing
agent in a basic medium.
The nickel–cadmium battery, an especially important
type of battery, in which electrode rxions are:
Anode rxion: Cd + 2OH- → Cd(OH)2 + 2e-
Cathode rxion: NiO2 + 2H2O + 2e- → Ni(OH)2 + 2OH-
As in the lead storage battery, products adhere to the
electrodes. Therefore, a Ni–Cd battery can be
recharged an indefinite number of times.
 Batteries & Fuel Cells
Lithium-ion batteries involve migration of Li+ ions from
cathode to anode, where they intercalate when the battery
is charging. Simultaneously, charge-balancing e-s travel to
the anode through the external circuit in the charger. On
discharge, the opposite process occurs.
The cathode of early lithium-ion batteries contained LiCoO2
and a lithium-intercalated carbon (LiC6) anode. More
recently, transition metals e.g. Ni and Mn are now included
in the cathode in addition to Co. Mixed-metal cathodes
have greater charge capacity and power output and
shorter recharge times.
Lithium-ion batteries are used in a wide variety of
applications, including cell phones, laptops, power tools,
and even in electric cars and motorcycles.
 Batteries & Fuel Cells
A fuel cell is a galvanic cell for which the reactants are
continuously supplied.
Ordinarily, energy from an exothermic rxion, e.g.
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g) + energy
is used as heat to warm homes and to run machines. But,
in a fuel cell that uses this rxion, this energy is used to
produce an electric current. e-s flow from reducing
agent, CH4, to oxidizing agent, O2, through a conductor.
For a fuel cell that uses the rxion:
2H2(g) + O2(g) → 2H2O(l)
the half- rxions are:
Anode rxion: 2H2 + 4OH- → 4H2O + 4e-
Cathode rxion: 4e- + O2 + 2H2O → 4OH-
A cell of this type (weighing about 226.8kg) is used in
space vehicles. Cars powered by fuel cells are now
being tested on the streets, e.g. Uganda busses.
 Corrosion
Corrosion is the spontaneous oxidation of metal.
Metals corrode because they oxidize easily. Metals used
for structural and decorative steel have standard
reduction potentials less (+) than that of oxygen gas
except gold.
When a half- rxion of any of these metals is reversed (to
show oxidation of the metal) and combined with the
reduction half-rxion for oxygen, the result is a (+) E° value.
Thus, oxidation of most metals by oxygen is spontaneous.
Despite the large difference in reduction potentials
between oxygen and most metals, corrosion does not
prevent use of metals in air, because most metals
develop a thin oxide coating, which protects their
internal atoms against further oxidation.
 Corrosion
• e.g. Al, with a -1.7 V reduction potential, should be
easily oxidized by O2. Going by the thermodynamics of
the rxion, an Al airplane could dissolve in a rainstorm,
but due to formation of a thin, adherent Al2O3 layer,
further corrosion is stopped. Potential of the “passive,”
oxide-coated Al is -0.6V, a value that causes it to
behave like a noble metal, i.e. copper, gold, silver,
platinum, which are relatively difficult to oxidize
• Iron also forms a protective oxide coating, but it fails to
shield against further corrosion because, when steel is
exposed to oxygen in moist air, the oxide that forms
scales off and exposes new metal surfaces to further
corrosion.
• Gold, with a positive standard reduction potential of
1.50V, much larger than that for oxygen (1.23V), does
not corrode in air.
 Corrosion
The corrosion mechanism
Corrosion of iron is not a direct oxidation process, but an
electrochemical rxion as shown here below:

Steel has a non-uniform surface because it’s chemical

composition is not 100% homogeneous. Non-uniformities
cause areas where iron is more easily oxidized (anodic
regions) and areas where it is less easily oxidized
(cathodic regions). In anodic regions each iron atom gives
up 2 e-s to form the Fe2+ ions: Fe → Fe2+ + 2e-
 Corrosion of Iron
• The e-s released flow through steel, as they do through
the wire of a galvanic cell, to a cathodic region, where
they react with oxygen:
O2 + 2H2O + 4e- → 4OH-
• Fe2+ ions formed in anodic regions travel to cathodic
regions through moisture on the surface of steel, just as
ions travel through a salt bridge in a galvanic cell. In
cathodic regions Fe2+ ions react with oxygen to form
rust, i.e. hydrated iron(III) oxide of variable
compositions as follows:
4Fe2+(aq)+O2(g)+(4 + n)H2O(l)→2Fe2O3∙nH2O(s)+8H+(aq)
Moisture acts as a salt bridge between anodic and
cathodic regions.
 Prevention of Corrosion
Primary protection against corrosion is by painting or metal
plating, to shield the metal from oxygen and moisture.
Cr and Sn are often used to plate steel because they oxidize to
form a durable, effective oxide coating. Zn, is used to coat steel
in a process called galvanizing, forms a mixed oxide–carbonate
coating. Since Zn is a more active (has a more (+) std reduction
potential) than iron,
Fe → Fe2+ + 2e- -E° = 0.44V
Zn → Zn2+ + 2e- -E° = 0.76V
any oxidation that occurs dissolves Zn rather than Fe.
Alloying is also used to prevent corrosion. Stainless steel
contains Cr and Ni, both of which form oxide coatings that
change steel’s reduction potential to one that is characteristic
of noble metals
Cathodic protection is a method used to protect steel in buried
fuel tanks and pipelines and Ships’ hulls.
 Electrolysis
• A galvanic cell produces current when a redox rxion
proceeds spontaneously.
• An electrolytic cell, uses electrical energy to force a
chemical rxion to produce a chemical change.
Electrolysis involves forcing a current through a cell
to produce a chemical change for which cell
potential is negative, i.e. electrical work causes a
nonspontaneous chemical rxion to occur.
• Practical Importance of Electrolysis; e.g. charging
of a battery, aluminium metal production, chrome
plating of an object, copper purification.
 Electrolysis Cont’d
Difference between a galvanic cell and an
electrolytic cell

- + - +

Galvanic Cell Electrolytic Cell

 Electrolysis Cont’d
• In the galvanic cell (a) which runs spontaneously to
produce 1.10V, the half-rxions are:,
Anode rxion: Zn → Zn2+ + 2e-
Cathode rxion: Cu2+ + 2e- → Cu
• In the electrolytic cell(b), an external power source
forces e-s through the cell in the opposite direction to
that in (a). This requires external potential greater than
1.10V, which must be applied in opposition to the
normal cell potential.
• Note: since e- flow is opposite in the two cases,
the anode and cathode are reversed btwn (a) and (b).
ion-flow through the salt-bridge is opposite in the two
cells.
 Electrolysis Cont’d
• Stoichiometry of electrolytic processes
• If we want to determine the mass of Cu that is plated
out when a current of 10.0 A, [1A = 1 C / 1 sec] is
passed for 30.0 minutes through a soln containing
Cu2+. [Plating means depositing a neutral metal on
the electrode by reducing metal ions that are in soln].
In this case, each Cu2+ ion requires two e-s to become
an atom of Cu metal:
Cu2+(aq) + 2e- → Cu(s)
• This is the reduction rxion occurring at the cathode of
the electrolytic cell.
• Steps needed to solve this problem:
• current & time 1 qty of charge in coulombs 2 moles of e-s 3 moles of copper 4 grams of copper
 Electrolysis Cont’d
1. Total coulombs of charge passed into the Cu2+ soln at the
cathode:
Coulombs = amps x seconds = C/s x s
= 10.0 C/ s x 30.0 min x 60.0 s/min
= 1.80 x 104 C
2. No. of moles of e-s required to carry 1.80 x 104 coulombs of
charge (recall: 1 mole of e-s carries a charge of 1 F, i.e., 96,485C):
1.80 x 104 C x 1 mol e-/ 96,485C = 1.87 x 10-1 mol e-
i.e. 0.187 mole of e-s flowed into the Cu2+ soln.
3. Each Cu2+ ion requires 2 e-s to become a Cu atom. Thus 1
mole of e-s produces ½ mole of Cu metal:
1.87x10-1mol e-x 1molCu/2 mol e- =9.35x10-2mol Cu
4. We now know no. of moles of copper metal plated onto the
cathode, and we can calculate the mass of copper formed:
9.35x10-2 mol Cu x 63.546g/mol Cu=5.94g Cu
 Electrolysis Cont’d
Electrolysis of Water
H and O react spontaneously to form water and the accompanying
decrease in free energy can be used to run a fuel cell to produce
electricity. The reverse nonspontaneous process can be forced by
electrolysis:
Anode rxion: 2H2O → O2 + 4H+ + 4e- -E° = -1.23V
Cathode rxion: 4H2O + 4e- → 2H2 + 4OH- E° = -0.83V
Net reaction: 6H2O → 2H2 + O2 + 4(H+ + OH-) E° = -2.06V
4H2O
or 2H2O → 2H2 + O2
Note that these potentials assume an anode unit with 1M H+ and
a cathode unit with 1M OH-. In pure water, where [H+] = [OH-] =
10-7 M, the potential for the overall process is -1.23 V.
In practice, however, if platinum electrodes connected to a 6V
battery are dipped into pure water, no reaction is observed
because pure water contains so few ions that only a negligible
current can flow. However, addition of even a small amount of a
soluble salt causes an immediate evolution of bubbles of
hydrogen and oxygen.
 Electrolysis Cont’d
Electrolysis of Mixtures of Ions
• If a solution in an electrolytic cell contains Cu2+, Ag+, and Zn2+ ions and
if voltage is initially very low but is gradually increased, in which order
will the metals be plated out onto the cathode?
• To answer this question, refer to standard reduction potentials of
these ions:
Ag+ + e- → Ag E° = 0.80 V
Cu2+ + 2e- → Cu E° = 0.34 V
Zn2+ + 2e- → Zn E° = -0.76 V
Note: the more (+) the E° value, the more the rxion proceeds in the
direction indicated. Of the three rxions, reduction of Ag+ occurs most
easily, and the order of oxidizing ability is Ag+ > Cu2+ > Zn2+. This
means silver will plate out first as potential is increased, followed by
copper, and finally zinc.
 Electrolysis Cont’d
• Relative Oxidizing Abilities
An acidic solution contains the ions Ce4+, VO2+, and Fe3+.
Using E° values listed in the Reduction Potentials Table,
give the order of oxidizing ability of these species, and
predict which one will be reduced at the cathode of an
electrolytic cell at the lowest voltage.
• Solution
The half-reactions and E° values are
Ce4+ + e- → Ce3+ E° = 1.70 V
VO2+ + 2H+ + e- → VO2+ + H2O E° = 1.00 V
Fe3+ + e- → Fe2+ E° = 0.77 V
• Order of oxidizing ability is therefore Ce4+ . VO2+ . Fe3+
• The Ce4+ ion will be reduced at the lowest voltage in an
electrolytic cell.
 Electrolysis Cont’d
Caution: in electrolysis of aqueous NaCl, E° values can’t be used
to predict the products because, of the major species in the soln
(Na+, Cl2, and H2O), only Cl2 and H2O can be readily oxidized. The
half-rxions (written as oxidization processes) are
2Cl- → Cl2 + 2e- -E° = -1.36 V
2H2O → O2 + 4H+ + 4e- -E° = -1.23 V
Since water has a more (+) potential, O2 should be produced at
the anode because it is easier (thermodynamically) to oxidize
H2O than Cl2, but this does not happen. As voltage is increased in
the cell, the Cl- ion is the first to be oxidized. A much higher
potential than expected is required to oxidize water. The voltage
required in excess of the expected value (the overvoltage) is
much greater for the production of O2 than for Cl2. This is why
chlorine is produced first.
Overvoltage is caused by difficulties in transferring e-s from the
species in soln to atoms on the electrode across the
electrode–soln interface. Because of this, E° values must be
used cautiously in predicting the actual order of oxidation or
ELECTROCHEMISTRY

•THE END