ELECTROCHEMISTRY

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Lecture 1
Electrochemistry: deals with the interconversion of electrical energy and chemical energy.
Electrical processes are redox reactions in which the energy released by a spontaneous reaction is converted to
electricity or in which electricity is used to drive a non-spontaneous reaction.

Electrochemical cells that are spontaneous are known as voltaic or galvanic cells.

Voltaic Cells
• The energy released in a spontaneous redox reaction may be used to perform electrical work. Voltaic, or galvanic
cells, are devices in which electron transfer occurs via an external circuit. Voltaic cells utilise spontaneous
chemical reactions.
Oxidation Numbers and Balancing Redox Equations
• Chemical reactions in which the oxidation state of more than one substance changes (in opposite directions) are
called oxidation-reduction reactions (redox reactions).

Recall:
• Oxidation involves loss of electrons (OIL). Reduction involves gain of electrons (RIG}.
• Consider the spontaneous reaction that occurs when Zn is added to HCI.
• The oxidation numbers of Zn and H+ have changed.
• The oxidation number of Zn has increased from Oto +2
Therefore, Zn is oxidised to Zn2+ •, while H1+ is reduced to H2
.

• The oxidation number of H1+ has decreased from +1 to 0. H+1 causes Zn to be oxidised.

Thus, H1+ is the oxidising agent, or oxidant. Zn causes H1+ to be reduced. Thus, Zn is the reducing agent, or reductant.
 Note that the reducing agent is oxidised and the oxidising agent is reduced.
• Recall the law of conservation of mass: The amount of each element present at the beginning of the reaction must be
present at the end.
• Conservation of charge state that electrons are not lost in a chemical reaction.
• Some redox equations may be easily balanced by inspection.

However, for many redox reactions we need to look carefully at the transfer of electrons.
Half-Reactions
•Half-reactions are a convenient way of separating oxidation and reduction reactions.

•Consider the reaction:

Sn2+ (aq) + 2Fe3+ (aq)
,.,
Sn4+ (aq) + 2Fe2+ (aq)

• The oxidation half-reaction is:

Sn2+(aq) Sn4+ (aq) +2e- . Note that electrons are a product here.
• The reduction half-reaction is: Fe3+ (aq) + e- Fe2+ (aq). Note that electrons are a reactant here.

For the reduction half-reaction the number of electrons are less than that for the oxidation half-reaction, therefore the
reduction half-reaction must be x2 to balance for the number of electrons that is found for the oxidation half-reaction.
2Fe3+ (aq) + 2e- 2Fe2+ (aq)
• Also note that the number of electrons on each half-reaction are equal and on opposite sides of the arrow.
Balancing Equations by the Method of Half-Reactions
Consider the titration of an acidic solution of Na2C2O4 (sodium oxalate, colourless) with KMnO4 (deep purple).
MnO4- is reduced to Mn2+ (pale pink-colourless), while the C 2 O 4- is oxidised to CO2. The equivalence point is indicated by the
presence of a pale pink colour.

If more KMnO4 is added, the solution turns purple due to the presence of excess KMnO4.
What is the balanced chemical equation for this reaction? We can determine this using the Method of Half-Reactions:
Write down the two incomplete half reactions.
MnO4- (aq) Mn2+ (aq) and C 2 O 4 2- (aq) CO2(g)
Balance each half-reactions.

• First, balance elements other than H and 0. 2

MnO4- (aq) Mn2+ (aq)

C 2 O 4 2- (aq) 2CO2(g)

• Then balance O by adding water(/).

MnO4- (aq) Mn2+ (aq) + 4H2O (l)
Next balance for H by adding H+
MnO4- (aq) + 8H+ Mn2+ (aq) + 4H2O (l)
Finish balancing by adding electrons 2

C 2 O 4 2- (aq) +2e 2CO2(g)

MnO4- (aq) + 8H+ +5e Mn2+ (aq) + 4H2O (l)
For the permanganate half-reaction, note that there is a charge of 7+ on the left and 2+ on the right. Therefore, 5 electrons
Multiply each half-reaction to make the number of electrons equal in each half-reaction.

To balance the 5 electrons for permanganate and 2 electrons for oxalate, we need 10 electrons for both

Multiplying MnO4- haf-reaction by 2

and C 2 O 4 2- by 5 gives:

10e- + 16H1+(aq) + 2MnO4- (aq) 2Mn+2 (aq) + 8H20(/)

5C2O4- (aq) - 1 0C O2(g) + 10e-

Adding the oxidation and reduction half-reactions results in:

16H+(aq) + 2MnO4- (aq) + 5C2O 42- (aq) 2Mn+ (aq) + 8H2O(I) + 10CO2(g)
The equation is now balanced!

Note that all of the electrons have cancelled out!

Balancing Equations for Reactions Occurring in Basic Solution
The same method as above is used, but OH- is added to neutralise" the H+ us ed. The equation must again be simplified by
cancelling like terms on both sides of the equation.

1.Electrode Process
A Molecular View of the Electrode Process
"Rules" of voltaic cells:
• At the anode electrons are products.
• Oxidation occurs at the anode.
• At the cathode electrons are reagents.
• Reduction occurs at the cathode.
• The flow of electrons from anode to cathode requires an external wire.
• The transfer of ions through a salt bridge maintains overall charge balance for the two compartments.

Passage of electricity through a chemical solution promotes reaction in the vicinity of the electrodes and is referred to as
electrolysis.
If on the other hand reaction are chosen so that it involves a loss of electrons (oxidation) and a gain of electrons (reduction)
and the arrangement is such that electrons are transferred from one reaction vessel to the other via a metallic conductor then
such an arrangement is found to serve as a source of electrical energy. This is known as electrochemical and galvanic cell.
Worked Example I

The following sketch of a galvanic cell is based on the Self assessment question 1.

Salt Bridge

Zn Cu

Zn++ 50 4 2- cu++ s0 4·2

(i) The Zn rod/plate dipping into a solution of Zn2+is called a Zn half cell or
Zn electrode. Similarly the Cu/Cu•2 is referred to as the Cu half cell.

(ii) The solutions are connected indirectly through a salt bridge e.g. KCI or
NH4NQ3 in a U-tube. If the solutions were allowed direct contact, energy of
the reaction would be liberated as heat.

Zn+ Cuz+ Zn2+ + Cu + heat

no measurement of electrical energy.

(iii) The voltmeter (V) indicates the cell voltage or the electrometotiveforce
(e.m.f.) produced by the two halfcells combined.

(iv) Reaction at the electrodes:

At the LHE
Zn (f r om electrode) -+ zn2+ + 2e- ( oxidation)

At the RHE
cuz+ ( f r o m solution)+ ze- -+ Cu ( redution)
Self assessment question 2

Sketch a galvanic cell involving the reactions ZnSO4 and standard hydrogen electrode (where H2(g) at 1 atm is
passed over platinum electrode in contact with 1M HCl/ solution. Explain how it works. Why is a salt bridge
needed?
Lecture 2

Half Cell voltage (Standard Electrode Potentials)

Since the cell voltage arises through the combined action of the two half-cells, the contribution from each is referred to as the half-cell voltage or electrode potential. An element dipping into a 1M solution of its ions is called a standard half-cell or
electrode and the voltage associated with the latter is known as the standard half cell voltage or electrode potential.

Electrode potentials cannot be measured directly. However, they may be determined with reference to a standard hydrogen gas electrode (i.e. pure hydrogen gas at 1 atm pressure in contact with 1 M hydrogen ions and at a temperature of 298.15 K)
which is arbitrarily fixed at zero potential. Consequently, in any cell which contains the hydrogen electrode, the entire measured voltage is attributed to the half reaction at the other electrode.

Standard State Conditions.

Solution is 1 M or more precisely the activities (ideal concentrations) of solutes and

gases equal 1. Therefore 1 M solution refers to an ideal solution. The gas pressure is equal to 1 atm and the temperature is usually 298.15 K or 25 °c.

Cell emf under Standard Conditions

• The flow of electrons from anode to cathode is spontaneous.
What is the "driving force"?
Electrons flow from anode to cathode because the cathode has a lower electrical potential energy than the anode.
• Potential difference is the difference in electrical potential.
• The potential difference is measured in volts.
• One volt (V) is the potential difference required to impart one joule (J) of energy to a charge of one coulomb (C):

1V = 1 J.c-1

• Electromotive force (emf) is the force required to push electrons through the external circuit.
• Cell potential: Eceu is the emf of a cell.
• This is known as the cell voltage.
• Eceuis> 0 for a spontaneous reaction -
• For 1 M solutions or 1 bar pressure for gases at 25°C (standard conditions), the standard emf (standard cell potential) is called E°ceu-
• For example, for the reaction:

Zn(s) + Cu•2 (aq) - Zn•2 (aq) + Cu(s)

• E0 cell = + 1.10 V
NOTE:
(i) When the Zn/Zn2+is coupled to the standard hydrogen electrode (SHE)
the electrons flow from the former to the latter: i.e.
Zn -+ zn 2+ + 2e- ( Zn 2+ + 2e- - Zn)
2H+ + 2e- -+ H2u,) ( 2H+ + 2e- ...+ H 2 )
But with a Cu/Cu2+system the electrons flow in the opposite direction:
i.e.

Cu 2+ + ze- -+ Cu ( cu2+ + ze- +-+Cu)

thus the electrode potential must have opposite signs.

(ii) A standard half-cell will have negative voltage if the electrons flow from
the metal (containing the electrode or half-cell) through the wire to the
H2 electrode (anode is where oxidation takes place, therefore
electrons flow from anode to cathode).

(iii) A negative voltage indicates a tendency of an electrode to give up

electrons. Thus when two half-cells are coupled to form an
electrochemical cell, the half-cell with the more negative exhibits a
stronger tendency to give up electrons whilst the electrode with the less
negative voltage will take up electrons.

(iv) When the half-cell reaction is written as a reduction process the voltage
associated with it is called the reductionpotential.

(v} The complete cell voltage is given by the expression:

Egel! = E HE - EfHE
or Egell= EgathDde - E nDde
Where £' ce11 values represent reduction potential (in the arrangement of
an electrochemical cell, the half-cell with the most negative value is put
on the LHS)
In the case of a voltaic cell consisting of Zn/Zn2+ (1 M) and Cu/Cu2+
arranged as shown in the diagram and for which the values are
zn2+ + ze- ~ Zn, ED = -0.76V
Cu 2+ + ze- +-+ Cu, ED= +0.34 V
The complete cell voltage is given by:
Eget!= E HE - EfHE Egell =
0.34 - (-0.76)
Egell = 1.10V
(vi} A table of E°ce11 values (i.e. standard reduction potentials) gives the
half-cell voltages in order of decreasing negative values. That is
 positive denotes a decreasing tendency to give up electrons (refer to
tables in the text book and tutorials).
This is also referred to as the electromotive series from which one can
predict whether an element will oxidize or reduce. Standard electrode
potentials are useful in detennining the strength of oxidizing and
reducing agents under standard-state conditions.

2. Significance of E°cell values

The sign of E°cell may be used to predict whether a given chemical reaction
resulting from the combination of any two half-cells will occur spoteneous/y or
not. It can be shown from thermodynamics that if E°ce11 is positive the reaction
will occur spontaneously.

Worked Example 2
Given 2 standard electrodes: viz:
Zn 2+ + 2e- H Zn E0= -0.76V
Ag ++ e- H Ag ; E = o.aov
0

(i) Arrange the electrodes to form a cell according to conversion.

(ii) Write the electrode reactions.
(iii) Write the overall cell reaction
(iv) Calculate the cell voltage
(v) State whether the rxn will occur spontaneously as written.
(vi) Denote the polarity of the electrodes in the diagram in (i).

Solution:

e
Zn 1zn 2 +(1 M )11Ag +(1 M )1Ag
®

Salt bridge
(i)

(ii) At LHE : zn2+ + 2e- H Zn (oxidation)

RHE : Ag+ + e- H Ag (reduction)

(iii) Zn ze- + Zn2+

_ ,2.A.:"g+""' ._+---2"""e'--- ..:...2.,.A..>,lg;l'---- - - Balance to "cancel" electrons.
Zn+ 2Ag+ 2Ag + Zn+2
(iv} E°ce/1 = E°RHE - E°LHE
= 0.8 - (-0.76)
= 1.56V

{v) E°ce11 is +ve. Therefore reaction will occur as denoted in (iii).

(vi) Zn electrode is -ve (anode where oxidation occurs)

Cu electrode is +ve.
NOTE: The electrode potential is an intensive property. This means that its value is
independent of the amount of species in the reaction. Thus, the electrode potential for
the half reaction

2Cu 2+(aq) + 4e- 2Cu(s)

Is the same as for

Cu2+(aq) + ze- Cu(s)

The emf corresponds to the free energy change per faraday, so that all emfs are on
the same basis. Therefore the emfs are subtracted/added directly. Only the
coefficients of equations may change to "cancel out electrons.

Strengths of Oxidising and Reducing Agents

Consider a table of standard reduction potentials.

• We can use this table to determine the relative strengths of reducing (and
oxidising) agents.
• The more positive the E° red, the stronger the oxidising agent (written in the
table as a reactant).
• The more negative the P red, the stronger the reducing agent (written as a
product in the table).
• We can use this to predict if one reactant can spontaneously oxidise another.
• Any substance on the right will reduce any substance higher than it on the left
- E0 cell > 0

Self assessment question 3

State whether the following are TRUE or FALSE

• W e can use this table to predict if one reactant can spontaneously reduce
another.

• F2 can oxidise H 2 or Liand Ni 2 +can oxidise Al(s).

• Li can reduce F2.

Thermodynamics of cells

Electrical work is performed when a reaction takes place in a galvanic cell. Since this
is reversible work at constant temperature and pressure, it is therefore the free
energy change. i.e.

Δ.G = -n F E

or under standard conditions

Δ..G0= - n FE 0 cell

where Δ.G0=free energy change

n =number of moles of electroons transferred between electrodes.

F = Faraday constant (96 500 C /moz-1)

E = cell emf(volts)

E(volts) x F(coulumbs) = EF volt- coulomb

= EF joules
Units for Δ.G is joules.

NOTE: a +ve cell emf therefore corresponds to a spontaneous cell reaction and
hence to a -ve free energy change.

e.g. calculate Δ.G0 for the reaction:

Zn(s) + 2Ag+(aq) → Zn2+( aq) + 2Ag(s)

Note the details in the earlier example

Δ.G0 = - n FE 0cell
=-2 x 96500C x 1.56V
= -3.01 X 105 J
Reaction is spontaneous because ΔG0 is - ve.
SELF ASSESSMENT QUESTION
Consider the reaction of nickel with silver ion:

Ni(s) + 2Ag+(aq) → Ni2 (aq) + 2Ag(s)

Predict whether the reaction is spontaneous or not?

Calculate the work done by the Ni-Ag cell

Lecture3

NERNST EQUATION

Dependence of e.m.f. on concentration

The e.m.f. of a cell depends on the concentration of ion and on gas pressures. We
can relate cell e.m.fs for various concentrations of ions and various gas pressures to
standard electrode potentials by means of the Nernst equation.
The free-energy change, Δ G, is related to the standard free-energy change,.e.G0, by
the equation:
ΔG = t:..G0 + RT In Q..............................(1)

Here Q is the thermodynamic reaction quotient. We can apply this equation to a

galvanic cell: Since l:J.G = -nFEcell and ll G 0 = - nFE 0 cell , we can write the above
equation (1) in the form:

-nF Ecell =- n FE 0
cell + RT ln Q ... ... ... ... ... ... (1.1)

or
Ecell = E0 cell - RT /nF ln Q ... ... ... ... ... ... (1.2)

This is the Nernst equation which relates the cell emf (Eceu) to its standard emf (E0 ce11)
and the reaction quotient , Q.

NOTE: R=8.314J/mol.K; F=96 500C/mol; n = number of electrons ; T = absolute

temp (K); In x = 2.303 log x

therefore at 25°C or 298K

The Nernst eqn. can be used to calculate the cell emf for non-standard
conditions.
 Worked Example 3:

W hat is the emf of the following cell at 298 K?

Zn{s}I zn2•(1.oox10 ·5 M Cu2+ (0.100M1Cu(s}

Given: Zn 2+( aq ) + 2e- Zn (s), E0 = -0.76V

Cu 2+( aq) + 2e- H Zn (s), £ 0
= +0.34V
(RTln 10)/F = 0.0591V

LHE: Zn (s) H Zn2+(aq ) + 2e-, £ 0

=+0.76V
RHE : c ui+( aq) + 2e- H Cu(s). E0 =+ 0,34V
Overall: Zn (s) + c ui+( aq) H Zn2+( aq) + Cu(s) £ 0= 1.10V
n=2

[Zn2+] 1.0 X 1 0- 5 -4
Q= [Cu 2+]= o.1 = 1.00x10

o o.os911 Q
now Ecell = Ecel-
l -- n og

=1.10 - 0.0591
2
log 1.0 X 10- 4

Equilibrium Constant (K)

Δ .G = Δ G0+RTIn Q refer to equation (1)

At equilibrium Δ G = 0
W hen the galvanic cell reaction has reached equilibrium. Ece11 = 0

Therefore O = Δ .G0 +RTlnQ

At equilibrium conditions, the quotient Q is denoted by K: Q =;i,K, equilibrium

constant.

Therefore, we can write;

Δ .G 0 =-RT InK =-nFE°cen at equilibrium

or In K = nFE 0ceul RT

or Log K = nF E 0cen/2.303RT
We can now also calculate the equilibrium constant for a galvanic cell reaction,
given the appropriate information.
Concentration Cells
•A concentration cell is one whose emf is generated solely because of a
concentration difference.

Worked Example 4:

Consider a cell with two compartments, each with a Ni(s) electrode but with different

concentrations of Ni 2+ (aq).

• One cell has [Ni2+ 1 = 1.0 M and the other has [Ni 2+ ] = 0.001 M.
• The standard cell potential is zero - since both half-reaction are the same.

• But this cell is operating under non-standard conditions!

• The driving force is the difference in Ni2+concentrations.

• Anode (dilute Ni 2+ ): Ni(s) → Ni2+(aq) + 2e

• Cathode (concentrated Ni2+): Ni2+(aq) + 2 e → Ni(s)
• Using the Nernst equation we can calculate a cell potential of +0.0888 V for this
concentration cell.

SELF ASSESSMENT QUESTIONS

1.Calculate the standard Gibbs free energy change, .G0, in J/mol at 25°C for the following reaction from standard
electrode potentials.

4Sn4+ + 2Cr 3Sn 2+ + 2Cr3+

Lecture 4

Quantitative Aspects of Electrolysis

,. We want to know how much2material we obtain with electrolysis.
Consider the reduction of Cu to Cu.

Cu+2 ( aq} + 2e- →Cu(s).

•2 mol of electrons will plate 1 mol of Cu.
• The charge of one mol of electrons is 96,500 C (1 F).
A Coulomb is the amount of charge passing a point in one second when the current is one Ampere.
•The amount of Cu can be calculated from the current(/) and time (t) required to plate.
Q =It

Electrolytic Cells
An electrolytic cell is an electrochemical cell in which an electric current drives a
nonspontaneuos reaction. The process of producing a chemical change in an electrolytic cell is called electrolysis.

Electrolysis
When electrodes connected to the poles of a battery that are placed in a solution of an acid, base or a salt, the positive (+)
and negative (-) ions each migrate towards the electrode which is of opposite sign to their own, and become discharged when
they come into contact with the electrodes. This process is called electrolys;s and the acids, bases and salts are called
electrolytes. The positive ions travel to the cathode and are called cations. The negative ions travel to the anode and are
called anions.
When the ions are discharged at the electrodes they always go into other reactions, either with each other, with the electrode,
with the water or with substances in solution. These reactions are called secondary reactions. A great variety of products
can thus be obtained by electrolytic process.
Electrolysis of Molten Salts
Figure: shows a simple electrolytic cell. Wires from a battery from a battery are connected to electrodes that dip into molten sodium
chloride (NaCl melts at 801°C). At the electrode connected to the negative pole of the battery, globules of sodium metal form; chloride
gas evolves from the other electrode. The half-reactions are:

As we noted earlier, the anode is the electrode at which oxidation occurs,

and the cathode is the electrode at which reduction occurs (these
--
Cl'
definitions hold for electrolytic cells as well as for voltaic cells). Thus during
the electrolysis of molten NaCl, the reduction of Na• to Na occurs at the
cathode, and the oxidation of er to Cl2 occurs at the anode (note the labeling
of electrodes in figure below).
Electrolys1s of NaCl solutions
V\/hen you electrolyse an aqueous solution of NaCl, the possible species involved in half-reactions are Na+, er and H20. The
possible cathode half-reactions are: 2cr - → Cl2 (g) + 2e

(note cathode and anode are inert e.g. platinum electrode). The possible half-reactions at the anode are:

Electrode potentials depend on concentrations (refer to Nernst equation). When the solution is concentrated in er, Cl2 is
the product. At the anode; but in dilute solution, 02 is the product.
In very dilute solutions the half-reactions are:
Therefore
Cu 2+( a q ) + 2e- H Cues)

at anode

Stoichiometry of electrolysis

Faraday showed that the amounts of substances released at the electrodes during
electrolysis are related to the total charge that has flowed in the electric circuit.

Faraday's Laws

(1) The quantity of a substance liberated at an electrode is directly

proportional to the quantity of electric charge that has flowed in the circuit.
(2) For a given quantity of electric charge, the amount of any metal that is
deposited is proportional to its atomic mass divided by the charge on the
ion.

Quantity of electricity is measured in coulombs(C).

A current which delivers 1C/s has a magnitude of ampere (1A).
Hence quantity of electricity
q = i xt
where i is thecurrent and t is time in seconds
e.g. quantity of electricity involved when a current of 2A flows for
3mins is q = i xt
= 2 x 3 x 60 C = 360 C.

Standard amount of substance is the mole and the corresponding quantity of

electricity is the Faraday, F = 96 500 coulombs. This is the electrical charge
on one mole of electrons.
Na+ + e- → Na
1 mole of e- produces 1 mole of Na atoms.
1 mole of e- has a charge of 1F = 96 500 C/mol

so the quantity of charge is a measure of the quantity of substance produced.

Therefore: n= _g
zF
Where q is the number of coulombs of electricity flowing, n is the number of
moles of chemical substance either oxidized or reduced, and z is the charge
per ion.
 e.g. (i) What mass of Ag will be deposited at the cathode when a current of
0.5A flows 10.0 mins through a solution of AgNO3? ( A g = 107.9 g.mol).

Ag+ + e- Ag(s)
=
q Ix t =0.5 x 10 x 60C
q
ZF = n(mole Ag)

(ii) What current would have flowed for 1 hour through a cell containing silver
nitrate if 2.158g of silver had been deposited? What mass of zinc would be
deposited if the same current were passed through zinc chloride solution?
(1F = 96500 C/mol, Ag =107.99/mol, Zn= 65.4g/mol)
To deposite 1 mole Ag+ i.e. 107.9 requires 96500C

This last method can be used for cells connected in series (any number of
cells).

"' - - - _._ -- .._ - ,,: ,...,_ - ,. ..

 SELF ASSESSMENT QUESTIONS
1. In the industrial production of aluminium, aluminium oxide, Al2O3, is electrolysed
at 100 °C. Assume that the cathode reaction is
Al3+ + 3e- Al

How many coulombs of electricity are required to produce 5.12 kg of

aluminium?

2. A steady current of 1.5A passed through an electrolytic cell containing AgNO3

until 1.45g of silver were deposited at the cathode.
(i) How long did the current flow?
(ii) What mass of zinc would be deposited if the same quantity of
electricity passed through cell containing ZnSO4?

Further Reading:
, . Marten J. ten Hoor, ' Redox Balancing without Puzzling," J. Chem. Educ., Vol. 74, 1997, 1376-1368.

2. P. J. Moran and E. Gileadi. "Alleviating the Common Confusion Caused by Polarity in Electrochemlstry," J. Chem. Educ.,
Vol. 66, 1989, 912 .

3. Ron Delorenzo. "Electrochemical Errors," J. Chem. Educ., Vol. 62, 1985, 424-425.