Electrochemistry

Outline (2 lectures, 1 tutorial)

 Reactions at electrodes
 Half equations
 Electrode Potentials
 Electrolytic and Galvanic cells
 Cell emf
 The Standard Hydrogen Electrode (SHE)
 Standard Electrode Potential, SEP (E0)
 Outline

 The Nernst Equation

 Relationship between Eo, Gibb’s Free Energy (G) and
equilibrium Constants (K).
 Measurement of pH.
 Electrochemistry

 Is the interchange between electricity and materials

that may involve charge (electron) or ion transfer.
 Electron Transfer reactions (Redox)

 The exchange of charge in reactions is not always easy to

see, so the concept of oxidation number was devised.
 Example
2 Mg(s) + O2(g) → MgO(s)
 Mg is oxidized:
2 Mg(s) → 2 Mg2+(aq) + 4e-
 O2 is reduced:
O2(g) + 4e- → 2O2-(aq)
Oxidation : loss of electrons
Reduction: Gain in electrons
OIL RIG
Oxidation Is Loss Reduction Is Gain
 Electrochemistry

 Observations:
Redox Reaction
- a spontaneous reaction occurs (ΔG is –ve) & will continue until it reaches
equilibrium.
- Gradually a grayish white deposit forms on the copper
- The solution becomes pale blue as hydrated Cu2+ ions enter the solution.
- Cu0(s) → Cu2+(aq) and Ag+(aq) → Ag0(s)
- Overall reaction : Cu(s) + Ag+(aq) → Cu2+(aq) + Ag(s)
 Redox Reaction (Electron Transfer)

 Half equations

 Oxidation
Cu0(s) → Cu2+(aq)+ 2e-

 Reduction
Ag+(aq) + e- → Ag0(s)
 Electrochemistry

 It would be useful to be able to convert this chemical

energy to electrical energy instead of heat energy.

 This is done by an electrochemical cell.

 An Electrochemical Cell - is a device used to convert

chemical energy (produced in a redox reaction) into
electrical energy.
 Galvanic or Voltaic Cell

 Electrochemical Cells are also known as Galvanic or

Voltaic Cells.

 Named after Luigi Galvani( 1737-1798) an Italian

anatomist who discovered that electricity can cause the
contraction of muscles.

 Also called voltaic cells after another Italian scientist

Alessandro Volta (1745-1827), the inventor of the battery.

 Galvanic cell is one in which the energy released in a

spontaneous redox reaction is used to perform electrical
work (drive e-s through an external circuit).
 Example of an Early Galvanic Cell –
.

Daniell Cell (Porous Pot)

Galvanic cells are formed when we separate the
sites where oxidation and reduction in a
spontaneous reaction occur.
Higher electrode potential
How does the Daniell Cell work?

- the copper strip attracts electrons from the zinc strip.

- these electrons pass through the wires of our external circuit.

- As the copper electrode receives electrons, free positive ions in the solution arrive
to equalize the charges.

- Positive Cu2+ are attracted to the charged copper electrode where they receive two
electrons and become neutral and deposit on the electrode in metallic form.

- The use of a porous barrier allows SO42- to move from right to left (to balance e-
flow in circuit) but prevents the Cu2+ and Zn2+ from moving between electrodes.

-For each copper atom that is deposited on the copper electrode, a zinc atom goes
into solution, giving up two electrons to the zinc electrode.
 Electromotive Force (emf)

 The electromotive force is the maximum

potential difference between two electrodes of a
galvanic or voltaic cell. (the energy converted into
electrical energy when unit charge passes through
the source)

 It measures the pulling tendency of the two

electrodes.

 That is the tendency to acquire (i.e. gain) or release

(loss) electrons.
 Daniell Cell

 The maximum potential between Zn and Cu of the Daniell cell

has been measured to be 1.10 V, but this is not observed in
practice.
 Factors that affect the measured potential in a cell (e.g. Daniell Cell)?

1. Porosity of the pot

2. Cleanliness of the electrodes
3. Electrical Resistance of the Measuring Device

 Minimize
 Make pot as porous as possible without allowing solutions to mix
 Electrodes clean
 High Resistance Voltmeter
 Internal Resistance {there is build up of charges inside pot }
 Liquid Junction Potential (LJP) {difference in ion mobility}
 Liquid Junction Potential (LJP)

 The liquid junction, porous pot, is also a source of “lost” potential

 Why is this?

 Build-up of charge results from the difference in mobility of the

ions as they move across the wall of the porous pot to neutralize
the charge.

 Potential difference exists between the inner & outer surfaces of

the wall of the porous pot .

 This potential that results is called a LIQUID JUNCTION

POTENTIAL
 How do we overcome the liquid junction potential?

 We need to provide a good conducting path

 Use a salt bridge with ions of similar mobilities to reduce the

effect of liquid junction potentials (i.e. potentials which arise
because of the difference in mobilities of the ions).

 Once these precautions are taken the emf of the cell depends
solely on the concentrations of the solutions & the metals used
as the electrodes.
 Or No electrical
current could be
Salt Bridge produced by the
cell

 For a galvanic cell to work, the solution in both half cells

must remain electrically neutral (charge must be
balance).
 Therefore ions must be permitted to enter and leave the
solutions.
 Salt Bridge: a tube filled with an electrolyte
solution(viscous), such as KNO3 or KCl and fitted with a
porous plug at each end or simply a strip of filter paper
soaked in saturated KNO3.
 Function:
- Maintains electrolytic contact (w/o mixing solutions)
- Completes the circuit
- Reduces liquid junction potential (LJP)
 Daniell Cell – Salt Bridge
Cu2+ a better Galvanic or Voltaic Cell
oxidizing agent
than Zn2+
 Electrochemical Cell

 Each half-cell has a characteristic voltage.

 Different choices of substances for each half-cell give

different potential differences.

 Each reaction is undergoing an equilibrium reaction

between different oxidation states of the ions—when
equilibrium is reached the cell cannot provide
further voltage.
 The spontaneous reaction that drives the Daniell cell is:
Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
 Galvanic or Voltaic Cell

0.46V

Oxidation Reduction
Ag

- Ag+ has a greater tendency to pull electrons than Cu2+

- Ag+ is a better oxidizing agent than Cu2+
The spontaneous reaction: Cu + 2Ag+ → Cu2+ + Ag
 Electrolytic Cell

 An electrochemical cells which uses energy from other

source (e.g. DC) to induce redox reactions and in which
electrical energy converts into chemical energy.
 Electrolytic vs Galvanic Cell

 NOTE: It is the nature of the chemical change and

not the electrical charge that determines whether we
label an electrode as cathode or anode.

Electrolytic Cell Galvanic Cell

Cathode is negative (reduction) Cathode is positive (reduction)

Anode is positive (oxidation) Anode is negative (oxidation)

 Electrode (Cell) Potential

 What is potential (E)?

 Potential is the amount of work required to bring one
unit of charge from infinity to a fixed distance in space.

 Electrode Potential or Cell Potential (emf or

electromotive force) : is the difference in
potential between two half-reactions or electrodes.
 i.e. Ecell = ΔE= Ecathode– Eanode = Eoxidation + Ereduction

 Ecell is expressed in Volts.

 Potential is a relative quantity and a standard state needs

to be defined.
 Electrode Potential & Half Cells

 Each electrode, i.e. the ion & its neutral atom

 Contributes a characteristic potential to the overall cell potential

 Independent of the other electrode in the pair

 Cu | Cu2+ half cell has a characteristic potential

Zn | Zn2+ half cell has a characteristic potential
Ag | Ag+ half cell has a characteristic potential

 To assign a potential to each half cell one must assign an

electrode as a “standard electrode” & measure each
electrode relative to this standard electrode.
 Standard Hydrogen Electrode (SHE)

 The standard to which all electrodes

are compared is the Standard
Hydrogen Electrode

 Its characteristic potential is ZERO

at ALL temperatures

 Potentials measured against the SHE

The SHE is represented as: are called Reduction Potentials and
Pt(s) | H2(g) | H+(aq) are represented by Eo in Volts

H2+ 2e- → 2H+

E0 = 0.0Volts
Standard Electrode Potentials

 Standard potentials are

measured with the test
electrode on the right hand
side
 The measured potential is +ve
if the electrode has a greater
tendency to pull electrons
than the H2 electrode (SHE)
and –ve if it has a lower
tendency
 Reduction Potentials
 Cu2+ + 2e-  Cu Eθ = + 0.34V
 Zn2+ + 2e-  Zn Eθ = - 0.76V
 Ag+ + e-  Ag Eθ = + 0.80V
 Pb2+ + 2e- Pb Eθ = - 0.13V
 Pb4+ + 2e- Pb2+ Eθ = + 1.67V

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 The standard-state cell potentials for some
common half-reactions More –ve E 0

Half-Reaction Eored/V Species at the top

 K+ + e- ↔ K -2.924 of the series are
 Ba2+ + 2 e- ↔ Ba -2.90 more readily
 Ca2+ + 2 e- ↔ Ca -2.76 oxidized
 Na+ + e- ↔ Na -2.7109
Zn2+ is oxidized

Increasing reducing strength

 Mg2+ + 2 e- ↔ Mg -2.375
 H2 + 2 e- ↔ 2 H- -2.23 when paired with
 Al3+ + 3 e- ↔ Al -1.706 the hydrogen
 Mn2+ + 2 e- ↔ Mn -1.04
 Zn2+ + 2 e- ↔ Zn -0.7628
electrode
 Cr3+ + 3 e- ↔ Cr -0.74
 S + 2 e- ↔ S2- -0.5082
 CO2 + 2 H+ + 2 e- ↔ H2C2O4 -0.49
 Cr3+ + e- ↔ Cr2+ -0.41
 Fe2+ + 2 e- ↔ Fe -0.409
 Co2+ + 2 e- ↔ Co -0.28
 Ni2+ + 2 e- ↔ Ni -0.23
 Sn2+ + 2 e- ↔ Sn -0.1364
E°Cell
 Pb2+ + 2 e- ↔ Pb -0.1263 1.Measured against SHE
 Fe3+ + 3 e- ↔ Fe -0.036 2.Concentration 1 Molar
 2H+ + 2 e- ↔H2 0.0000
3.Pressure 1 atmosphere
4.Temperature 25°C
 The standard-state cell potentials for some
common half-reactions Copper is
reduced when
paired with
 S4O62- + 2 e- ↔ 2S2O3 2- 0.0895 hydrogen
 Sn4+ + 2 e- ↔ Sn2+ 0.15
 Cu2+ + e- ↔ Cu+ 0.158
 Cu2+ + 2 e- ↔ Cu 0.3402

Increasing reducing strength

O2 + 2 H2O + 4 e- ↔ 4 OH- 0.401
Increasing oxidizing strength


 Cu+ + e- ↔ Cu 0.522
 I3- + 2 e- ↔ 3 I- 0.5338
 MnO4- + 2 H2O + 3 e- ↔ MnO2 + 4OH- 0.588
 O2 + 2 H+ + 2 e- ↔ H2O2 0.682
 Fe3+ + e- ↔ Fe2+ 0.770
 Hg22+ + 2 e- ↔ Hg 0.7961
 Ag+ + e- ↔ Ag 0.7996
 Hg2+ + 2 e- ↔ Hg 0.851
 H2O2 + 2 e- ↔ 2 OH- 0.88
 HNO3 + 3 H+ + 3 e- ↔ NO + 2 H2O 0.96
 Br2(aq) + 2 e- ↔ 2 Br- 1.0872
 IO3- + 12 H+ + 10 e- ↔ I2 + 6 H2O 1.19
 CrO42- + 8 H+ + 3 e- ↔ Cr3+ + 4 H2O 1.195 More
+ve E0
*The more positive the Eo value for a half-reaction, the greater the More easily
tendency for that reaction to occur as written. reduced
 Standard Cell Notation for Galvanic Cell

 A s a matter of convenience chemists have devised a

shorthand way of representing a galvanic cell.
 For example the copper-silver cell is represented as follows.
Salt bridge

Cu(s) Cu2+(aq) Ag+(aq) Ag(s)

Phase
boundary

 By convention anode half cell is specified on left

 Exercise : Write the anode and cathode half reactions for the
following galvanic cell. Al(s) Al3+(aq)+ 3e-
Al(s) Al3+(aq) Pb2+(aq) Pb(s)
Pb2+(aq) + 2e- Pb(s)
 Daniell Cell - Cell Notation

 Daniell Cell can be written as

Zn(s) | ZnSO4(aq) || CuSO4(aq) | Cu(s) or

Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu(s)

 Cell Potential - Calculating E0 of Cells

 To calculate voltages for any two electrochemical cell we

can do the following:
Daniell Cell:

Zn(s) | Zn2+ (aq) || Cu2+ (aq) | Cu(s)

 a) Locate the two half cells reactions in the table of

standard reduction potentials.

1. Cu2+ (aq) + 2e-  Cu(s) E0 = + 0.34V

2. Zn2+ (aq) + 2e-  Zn(s) E0 = - 0.76V
 Cell Potential - Calculating E0 of Cells

b) The half reaction that has the higher reduction

potential will reduce and can be written as you find it in
the table.

1. Cu2+ + 2e-  Cu Eθ = + 0.34V

c) The half reaction that has the lower reduction

potential must be reversed and written as an
oxidation. (The sign of the Eo value of the lower half
reaction is changed ).
 Reverse Eqn. 2
 Zn  Zn2+ + 2e- Eθ = + 0.76V
 Cell Potential - Calculating E0 of Cells

d) The two half reactions are balanced for the number

of electrons exchanged but the value of each Eo
remains unchanged.
Cu2+ + 2e-  Cu Eθ = + 0.34V

Zn  Zn2+ + 2e- Eθ = + 0.76V

 E0oxi= - E0red
 Cell Potential - Calculating E0 of Cells

g) The two half reactions are then added together and

so are the Eo values. ( This value will always be
positive for an electrochemical cell).
 Cu2+ + 2e-  Cu E0 = + 0.34V
 Zn  Zn2+ + 2e- E0 = + 0.76V
Overall eqn. Cu2+ + Zn  Zn2+ + Cu

 Overall Ecell0= E0oxi + E0red= 0.34 +0.76 = 1.10V

 When E0 is +ve the reaction is spontaneous

(thermodynamically favourable) in the direction written.
 Cell Potential -Exercise

 Determine the cell potential for a galvanic cell based on

the redox reaction.
 Cu(s) + Fe3+ (aq)  Cu2+ (aq) + Fe2+ (aq)

 Fe3+ (aq) + e- Fe2+ (aq) Eº = 0.77 V

 Cu2+ (aq)+2e- Cu(s) Eº = 0.34 V

 2Fe3+ (aq) + 2e- 2Fe2+ (aq) Eº = 0.77 V

 Cu(s) Cu2+ (aq)+2e- Eº = -0.34 V

Overall eqn. Cu(s) + 2Fe3+ (aq)  Cu2+ (aq) + 2Fe2+ (aq)

 Ecello = E0xi + Ered =0.43V

 Free Energy and Electrode Potentials

 The cell potential of a voltaic cell is a measure of the

maximum amount of energy per unit charge which is
available to do work when charge is transferred through
an external circuit.

 This maximum work is equal to the change in Gibbs free

energy, ΔG, in the reaction.
Maximum work = ΔG = -nFE°cell
 n= number of electrons transferred per mole of reactant
(after balancing)
 F = Faraday’s constant (96485 Cmol-1)
 E°cell= standard cell potential
 Free Energy and Electrode Potentials

 Consider the historic Daniell cell in which zinc and

copper were used as electrodes.
Cathode (Reduction) Half-Rxn Standard Potential E° (volts)
Zn2+(aq) + 2e- → Zn(s) -0.76

Cu2+(aq) + 2e- → Cu(s) +0.34

 E°cell = 1.1 Volts

 n= 2 electrons are transferred per mole of reactant.
 ΔG = -nFE°cell = -2 x 96,485 Cmol-1 x 1.10 JC-1 = -212 kJ
 Voltage is defined as the work done per unit charge.
 (1V = 1JC-1)
 Gibb's Free Energy

 The Gibb's free energy DG is the negative value of maximum

electric work,
 DG = - W
= - q DE
 W = maximum electric work is the product of charge q in Coulomb
(C), and the potential DE in Volt (= J/C)
 A redox reaction equation represents definite amounts of reactants
in the formation of also definite amounts of products.
 The number (n) of electrons in such a reaction equation, is related
to the amount of charge transferred when the reaction is completed.
 Since each mole of electron has a charge of 96485 C (known as the
Faraday's constant, F),
 q=nF
 and, DG = - n F DE
 At standard conditions,
 DG° = - n F DE°
 DG0& E0 - Spontaneity

 DG0 = -n F E0

 When E0 is +ve, DG0is -ve = reaction is spontaneous

 When E0 is -ve, DG0 is +ve = reaction is not spontaneous

 Nernst Equation

 As a voltaic cell is discharged, its emf falls until E = 0, at

which point we say that the cell is dead.

 Studies show that the emf depends on the concentrations of

the reactants and products in the cell reaction.

 Increasing the [reactants] will increase the cell emf.

 Increasing the [products] will decrease the cell emf.

 The emf generated under nonstandard conditions can be

calculated by using an equation first derived by Walther
Hermann Nernst (1864 - 1941).
 Nernst Equation

 The dependence of the cell emf on concentration can be

obtained from the dependence of the ΔG on concentration.
 Recall:
 ΔGat any stage of rxn = ΔGo + RT ln Qrxn ….……. ….eqn. 1
where R = Universal gas constant, T = temperature
and for a generalized equation of the form:
cC + bB+….. mM+ nN+……

At equilibrium, Ecell = 0 hence DG = 0 and Qrxn corresponds to Keq.

 Activity- effective
Activity concentration of
species.

 Some of the species that take part in these electrode

reactions are pure solid compounds and pure liquid
compounds. In dilute aqueous solutions, water can be
treated as a pure liquid.
 For pure solid compounds or pure liquid compounds,
activities are constant and their values are considered to
be unity. i.e. a= 1
 The activities of gases are usually taken as their partial
pressures and the activities (ai) of solutes such as ions are
the product of the molar concentration and the activity
coefficient of each chemical species :
ai = γ[i]i ≈ [i]
 Nernst Equation

 Substituting ΔG = -nFEcell into eqn. 1 gives:

-nFEcell = -nFEocell + RT ln Q

 Solving this equation for E gives the Nernst equation:

 The equation is usually written in term of common logarithms:

 Nernst Equation

 At 298 K the quantity

2.303RT / F = 0.0592 V,

- so at 298 K a simplified form of the Nernst equation is:

 Non-standard Conditions

 The SEP values refer to standard conditions i.e. 1 Molar concentrations at

25ºC and atmospheric pressure.
 If these conditions change then so does the electrode potential.
 For example, according to standard electrode potentials, MnO2 will not
react spontaneously with HCl, however this is the standard preparation of
chlorine in the laboratory.
 MnO2(s) + 4H+(aq) + 2e- Mn2+ + 2H2O(l) Eº = 1.23 V
 Cl2(g) + 2e- 2Cl-(aq) Eº = 1.36V
 Predicting spontaneity, E = Ered + Eox = 1.23 +(- 1.36 ) Eocell = - 0.13V
 Negative value therefore no reaction!!
 In the lab preparation the MnO2 is heated with the concentrated HCl - these
are not standard conditions, the temperature >>25ºC and [HCl] >>1 mol
dm-3.
 Under these new conditions the reaction becomes spontaneous and
proceeds at a comfortable rate to collect the chlorine gas produced.
 MnO2(s) + 4H+(aq) + 2Cl-(aq) Mn2+ (aq) + 2H2O(l) + Cl2(g)
 Worked Example

 Calculate the emf of the following cell at 25°C;

Sn(s)|Sn2+(0.025 M)||Ag+(2.0 M)|Ag(s)
 Sn2+(aq) +2e- Sn(s) -0.14V
 Ag+ +e- Ag(s) 0.80V
 2Ag+ + Sn(s) Sn2+ + 2Ag(s)
 E°cell = E°oxi + E°red = 0.80 V + 0.14 V = 0.94 V

•
 Nernst Equation

 If we have a Cu2+/Cu electrode in one half & the SHE in

the other
Pt(s) | H2(g) | H+(aq) || Cu2+(aq) | Cu(s) E0 = + 0.34V

Cu2+ + 2e-  Cu E0 = + 0.34 V

2H+ + 2e-  H2 E0 = 0.00 V

(E0xi + Ered) Cu2+(aq) + H2(g) Cu(s) + 2H+(aq) E0 = + 0.34 V

 Q = [aH+]2 [aCu]/[aH2][aCu2+]
 Q = [1.00]2 [1]/[1.0][1.00] = 1

45
 Nernst Equation - pH

 When H+ concentration is NOT 1.00 M but everything remains the same.

 log10Q, for pH measurements, can be expressed in terms of the

hydrogen ion activity by :-log10aH+ which is the pH of a solution and the
equation becomes:

 The measured potential is related to the activity/ concentration of H+ and

E0 of the cell

 pH can be measured electrically

 E.g. pH meter

46
 Nernst Equation - pH

Take for example:

 MnO4- + 5e- + 8H+ ↔ Mn2+ + 4H2O E0 = 1.51V

 Here the potential depends not only on the

concentrations of the manganese species but also
on the pH of the solution.

8
 Applications

 Widespread applications of electrochemistry.

 In the industry important chemical : liquid
bleach(NaOCl) and lye (NaOH) are manufactured by
electrochemical reactions.
 Batteries (galvanic cells) which produce electrical energy
by means of chemical reactions are used to power toys,
flashlights, calculators, laptop computers, cellphones,
clocks, watches, remote controllers etc. (Dry Cells)
 Wet cells : lead acid batteries in some cars.
 Fuel Cells e.g. hydrogen fuel cell

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