CHAPTER 5

electrochemistry

DTC 1043 Physical & Organic Chemistry

Saidatul Radhiah Ghazali
FTK (Kimia) UCTATI
1.0 ELECTROCHEMISTRY
DEFINATION OF ELECTROCHEMISTRY
 Electrochemical reaction : chemical reaction that involves the
flow of electrons.

Redox : Oxidation-reduction reaction.

Is a reaction in which electrons are transferred between
species or in which atoms change oxidation number.

Oxidation : is the half reaction when the oxidation

number increase (or there is loss of electrons).

Reduction : is the half reaction when the oxidation

number decrease ( or there is gain of electrons)
 Reducing agent : substance that losses electrons (or decreased in oxidation
number).
 Oxidizing agent : substance that gains electrons ( or increased in oxidation
number).

Example :
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
Can be divided into separate oxidation and reduction
half-reaction.
Zn(s)  Zn2+ + 2e- Oxidation
2H+(aq) + 2e-  H2(g) Reduction

Zn(s) is the reducing agent.

H+(aq) is the oxidizing agent.
1.1 OXIDATION-REDUCTION REACTIONS
– An oxidizing agent is a species that oxidizes another
species; it is itself reduced.
– A reducing agent is a species that reduces another
species; it is itself oxidized.

Loss of 2 e-1 oxidation

reducing agent
+2 +2
𝐹 𝑒 +𝐶𝑢
(𝑠) (𝑎𝑞) →𝐹𝑒 (𝑎𝑞 ) +𝐶 𝑢( 𝑠)
oxidizing agent
Gain of 2 e-1 reduction

+2 −
𝑟𝑒𝑑: 𝐶𝑢 +2𝑒 → 𝐶𝑢(𝑠)
(𝑎𝑞)
+2 −
𝑜𝑥 : 𝐹 𝑒(𝑠) → 𝐹 𝑒 (𝑎𝑞 ) +2 𝑒
_______________________
+2 +2 4
𝐹 𝑒 (𝑠) + 𝐶 𝑢 _
(𝑎𝑞) →𝐹𝑒 (𝑎𝑞 ) +𝐶 𝑢( 𝑠)
1.2 OXIDATION NUMBER :
THE ACTUAL CHARGE OF THE ATOM IF IT EXISTS AS
A MONATOMIC ION.
Oxidation Number Rules :
 Elements : Oxidation number = 0.

 Monatomic ions : Oxidation number in a monatomic ion equals the charge on

the ion.
 Oxygen : Oxidation number = -2 in most of its compound.

 Hydrogen : Oxidation number in most of its compound = +1.

Oxidation number = -1 in binary compounds with a metal.

 Halogens : Oxidation number = -1.

 Compounds and ions : The sum of the oxidation numbers of the atoms in a
compound is zero. The sum of the oxidation numbers of the atoms in a
polyatomic ion equals the charge on the ion.
Exercise :
Divide into half reaction for the following :
2 Na(s) + Cl2(g)  2 NaCl(s)
Balancing Oxidation-Reduction Equation (Acidic Solution)
1. Assign oxidation numbers to each atom.
2. Split into two half-reactions.
3. Complete and balance each half-reaction.
a) Balance all atoms except O and H.
b) Balance O atoms by adding H2O to one side of the
equation.
c) Balance H atoms by adding H+ ions to one side of the
equation.
d) Balance electric charge by adding electrons, e- to the more
positive side
4. Combine the two half-reactions to obtain the final
balanced oxidation-reduction.(Electrons can’t appear in
the final equation).

Additional steps for balancing basic reaction.

5. Note the number of H+ ions in the equation. Add this

number of OH- ions to both sides of the equation.
6. Simplify the equation by noting that H+ react with OH- ions
to give H2O.
Example :
Balancing redox reaction (acidic solution):
Zn(s) + NO3-(aq)  Zn2+(aq) + NH4+(aq)

Answer :
Assign oxidation number to each atom :
Zn(s) + NO3-(aq)  Zn2+(aq) + NH4+(aq)
0 +5 +2 -3
Split into half-reactions :
Zn(s)  Zn2+(aq)
NO3-(aq)  NH4+(aq)
Balance the half-reactions : No O or H atom , ignore step 3 (b)
Zn(s)  Zn2+(aq) + 2e- & 3(c), but add electron to follow
step 3(d).
  For the other half-reaction :

NO3-(aq) + 10H+(aq) + 8 e-  NH4+(aq) + 3H2O(l)

N is balanced, but not for O or H, add three H2O to balance for
O, add ten H+ ions to balance for H and add eight electron to
balance for the charge. Check that charge and different kinds of
atom are balanced.

 Combine the half reaction :

4Zn(s)  4 Zn2+(aq) + 8 e-
NO3-(aq) + 10H+(aq) + 8e-  NH4+(aq) + 3H2O(l)
_____________________________________________
4Zn(s) + 10H+(aq) + NO3-(aq)  4Zn2+(aq) + NH4+(aq)
+ 3H2O(l)
____________________________________________

To ensure that no electron appears, the first half-reaction is

multiplied by a factor of 4.
 1.3 ELECTROCHEMICAL CELL
 is a system consisting of electrodes that dip into an electrolyte and in
which a chemical reaction either uses or generate electric current.
 Two types of electrochemical cell :

- Voltaic or Galvanic cell.

- Electrolytic cell.

1) Voltaic or Galvanic Cell

A voltaic or galvanic cell is an electrochemical cell in which a
spontaneous reaction generates an electric current.
 Salt bridge – is a tube of an
electrolyte in a gel that is connected to
the half-cells of a voltaic cell; allows
the flow of ions but prevents the
mixing of the different solutions (to
balance electrical charge).

Anode – negative terminal (oxidation).

Cathode – positive terminal (reduction).
Electrons flow from the anode to the cathode.
• Cation : positive ion, flow toward the cathode.
• Anion : negative ion, flow toward the anion.
EXAMPLE :
TWO HALF-CELL REACTIONS:
Zn(s)  Zn2+(aq) + 2e- (OXIDATION HALF REACTION)
Cu2+ (aq) + 2e-  Cu(s) (REDUCTION HALF REACTION)
__________________________
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s) (CELL REACTION)

1.3 1 Galvanic cell/ Voltanoic cell

Notation for galvanic cells

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

Zn(s) | Zn2+ (aq) anode

|| salt bridge
Cu2+(aq) | Cu(s) cathode
For hydrogen electrode, where platinum serves as the terminal and
involves hydrogen gas :

2H+(aq) + 2e-  H2(g)

As a cathode : H+(aq) | H2(g)| Pt
As an anode : Pt | H2(g) | H+(aq)
1.3.2 Cell Potential
 Electromotive force (emf) of the cell or Ecell is the maximum
potential difference (electrical pressure) between the
electrodes of a voltaic cell. It is measured in volt : 1 V = 1 J/s
 Standard emf (Eo) is the emf of a voltaic cell at standard
condition :
1) Solutions are at 1M.
2) Gas pressures are at 1 atm.
3) Temperat
ure normally taken at 25oC.
Example :
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g) Eo = 0.76 V

Zn(s)  Zn2+(aq) + 2e- Eo oxidation = 0.76 V

2 H+(aq) + 2e-  H2(g) Eo reduction = 0.00
V
_________________________________________________
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g) Eo = 0.76 + 0.00
= 0.76 V
_________________________________________________
Positive E : means spontaneous reaction.
Oxidation-reduction reactions that have a positive overall cell potential
are spontanoeous.
Example :
2 Ag+(aq) + Cu(s)  2Ag(s) + Cu2+(aq)

2Ag+(aq) + 2e-  2Ag(s) Eo = 0.80 V

Cu(s)  Cu2+(aq) + 2e- Eo = -0.34 V
______________________________________
2Ag+(aq) + Cu(s)  2Ag(s) + Cu2+(aq) Eo = 0.46 V
______________________________________
The overall reaction is spontaneous.
1.3.3 Strength of Oxidizing & Reducing Agents
 A reduction half-reaction

Oxidized species + ne-  reduced species

Reduced species  oxidized species + ne-
 The strongest oxidizing agents : are the oxidized species
with the largest Eo, i.e. Fluorine.
 The strongest reducing agents : are the reduced species
with the most negative Eo, i.e. K
Example :
1) Order the following oxidizing agents by increasing strength under
standard state condition :
Cl2(g), H2O2(aq), Fe3+(aq)

Answer :
Fe3+(aq) + e-  Fe2+(aq) 0.77 V
Cl2(g) + e-  2Cl-(aq) 1.36 V
H2O2(aq) + 2H+(aq) + 2e-  2H2O(l) 1.78 V

Order : Fe3+(aq), Cl2(g), H2O2(aq)

2. Order the following reducing agents by increasing strength under standard
state condition :
H2(g), Al(s), Cu(s)

Al(s)  Al3+ (aq) + 3e- 1.66V

H2(g)  2H+(aq) + 2e- 0.00V
Cu(s)  Cu2+ + 2e- 0.34V
Order : Cu(s), H2(g), Al(s)
1.3.4 The Nernst Equation

For a Daniel Cell :

Zn | Zn2+ (1.0M) || Cu2+ (1.0M) | Cu Eo = 1.10 V

When this cell is used to do work :

a) Zinc electrode becomes lighter.
b) Copper electrode becomes heavier.
c) Concentration of Zn2+ ions at the anode increases and
the concentration of Cu2+ at the cathode decreases.
d) Negative ions flow from the salt bridge toward the
anode.
e) Positive ions flow from the salt bridge toward the
cathode.

So as the time goes by : the cell potential becomes smaller.

Nernst Equation can be used to determine the new cell
potential :
RT
o
E=E − lnQ c
nF

E = the cell potential at time t.

Eo = the cell potential at standard condition.
R = ideal gas constant in units of joules/mole.K, 8.314
J/mol.K.
T = temperature in K.
n = number of moles of electrons transferred.
Qc = the reaction quotient at time t.
F = charge on a mole of electrons, 96500 C/mol.
• After simplication at T = 25oC :

0.0592
0
𝐸=𝐸 − log❑𝑄
( values
𝑐
in volts at 25oC)
𝑛
• For a Daniel Cell :

Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s) Eo = 1.10

Zn(s)  Zn2+(aq) + 2e- E = 0.76
Cu2+(aq) + 2e-  Cu(s) E = 0.34

n=2
Qc = conc of (product/ reactant) = [Zn2+]/[Cu2+]
Example :
Calculate the potential at 25oC for the following cell :
Cu | Cu2+ (0.024M) || Ag+ (0.0048M) | Ag

Chemical equation :
Cu(s) + 2Ag+(aq)  Cu2+ (aq) + 2Ag(s)

Oxidation : Cu  Cu2+ + 2e- Eo oxidation = - 0.3402 V

Reduction : 2Ag+ + 2e-  2Ag Eo reduction = 0.7996 V
Eo = 0.4594V

E = Eo - 0.0592/2 x log ([Cu2+] / [Ag+]2)

=0.4594 - 0.0592/2 x log (0.024 / 0.00482)
= 0.4387 V.
1.3.5 Nernst Equation to Measure Equilibrium
Constant, Kc

At equilibrium E = 0, Qc=Kc

0RT
0=E − log K c
nF
nF Eo =RT ln K c

K C =exp (
nF E o
RT )
Example :
Calculate the equilibrium constant at 25oC for the reaction
between zinc metal and acid :
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)

Solution :
Zn  Zn2+ + 2e- Eo oxi = - 0.7628V
2H+ + 2e-  H2 Eo red = 0.0000V
Zn + 2H+  Zn2+ + H2 Eo = 0.7628V

Kc = exp (nFEo/RT)
= exp (2 x 96500 x 0.7628 / (8.314 x 298))
= 6.3 x 1025
1.4 DETERMINATION OF PH
Consider this cell :
Zn | Zn2+ (1M) || H+(test solution) | H2 (1atm)

The cell reaction is :

Zn(s) + 2H (test solution)  Zn2+ (1 M) + H2 (1 atm)
Qc = [Zn2+] PH2 / [H+]2 = 1/[H+]2

Substituting into Nernst equation :

0 0.0592
E ¿E − log Q c
n
= 0.76 - 0.0592 / 2 x log (1/ [H+]2)
= 0.76 + 0.0592 x log [H+]
= 0.76 - 0.0592 x pH
pH = (0.76 - E) / 0.0592 valid only for the above reaction
Note : pH = - log [H+]
 1.5 ELECTROLYSIS
 Electrolytic cell : is an electrochemical cell in which an electric
current drives an otherwise nonspontaneous reaction.
 Using electric current to produce chemical reaction : electrolysis.
 Using chemical reaction to produce electric current : galvanic cell.
1.5.1 ELECTROLYTIC CELL
Anode – positive (oxidation)
Cathode – negative (reduction), since the anode attracts anions
from the solution.
 Cation : positively charged ion.
 Anion : negatively charged ion.
Example :
Electrolysis of molten sodium chloride ( T > 801oC) :
Cathode (-) : 2Na+(l) + 2e-  2Na(l) -2.70 V
Anode (+) : Cl-(l)  Cl2(g) + 2 e- -1.36 V

2 NaCl(l)  Cl2(g) + 2Na(l) -4.07 V

 At least 4.07 V is required to drive the reaction.

Anode
 oxidation reaction.
 -ve electrode (galvanic cell).
 +ve electrode (electrolysis).
 e- moves from electrode.
 anion move towards
electrode.
Cathode
 reduction reaction.
 +ve electrode (galvanic cell).
 -ve electrode(electrolysis).
 e- moves toward electrode.
 cation moves toward
electrode.
1.5.2 ELECTROLYSIS OF SULFURIC ACID SOLUTION

 Strong acid : completely ionizes into H+ & SO42-.

 Species involved : H+, SO42-, H2O.

 At the cathode, possible reduction half reaction :

2 H+(aq) + 2 e-  H2(g) Eo= 0.00 V

2 H2O(l) + 2e-  H2(g) + 2OH-(aq) Eo= - 0.83 V

 At the anode, possible oxidation half reaction:

2 SO42-(aq)  S2O82-(aq) + 2e- Eo= -2.050 V

2 H2O(l)  O2(g) + 4H+(aq) + 4e- Eo= -1.229 V
 Half reaction which has bigger value of Eo is preferred (more
spontaneous).
 So at the anode, the reduction of H+ is preferred.
 At the cathode, the decomposition of H2O is preferred.

 The overall cell reaction is :

(2x) 2H+(aq) + 2e-  H2(g) Eo= 0.000 V

2H2O(l)  O2(g) + 4H+(aq) + 4e- Eo= -1.229 V
2H2O(l)  2 H2(g) + O2(g) Eo = -1.229 V
 1.5.3 ELECTROLYSIS OF DILUTE SODIUM
CHLORIDE SOLUTION
• Species involved in half reactions are : Na+, Cl- & H 2O.
• Possible cathode half reactions are :

Na+(aq) + e-  Na(s) Eo = -2.71 V

2H2O(l) + 2e-  H2(g) + 2OH-(aq) Eo = -0.83 V

The second half reaction is more spontaneous, so H 2 gas

evolved at the cathode.

• Possible anode half reactions are :

2Cl-(aq) Cl2(g) + 2e- Eo = -1.36 V

2H2O(l)  O2(g) + 4H+(aq) + 4e- Eo = -1.23 V

The second half reaction is more spontaneous, so at standard

condition H2O is reduced.
• The overall reaction at standard condition is :
(2x) 2H2O(l) + 2e-  H2(g) + 2OH-(aq) Eo = -0.83 V
2H2O(l)  O2(g) + 4H+(aq) + 4e- Eo = -1.23 V

6H2O(l)  2H2(g) + 4OH-(aq) + 4H+(aq) + O2(g)

or 2H2O(l)  2H2(g) + O2(g) Eo = - 2.06 V

After sometimes, the Cl- concentration increases after sometimes.

Therefore, the oxidation potential of Cl - increases until Cl- is oxidized
in preference to H2O. The product changes from O2 to Cl2.
2H2O(l) + 2e-  H2(g) + 2OH-(aq)
2Cl-(aq)  Cl2(g) + 2e-

2H2O(l) + 2Cl-(aq)  H2(g) + Cl2(g) + 2OH-(aq)

1.6 FARADAY’S LAW
• Consider : Na+ + e-  Na(l)
• When 1 mole of electrons reacts with sodium ions, one faraday of
charge passes through the circuit.

1 Faraday = 96500 C/mol e- : charge in 1 mole of electrons.

Q=Ixt
Q = Electric charge (Coulombs)
I = Electric current (Ampere or C/s)
t = Time lapse (second)
• Faraday's Law : mass produced in an electrolysis is proportional to I x t.
Or
mIxt
m = It

Where
 = electrochemistry equivalence
= MW / (nF)

MW = molecular weight
n = number of charges / mol electron i.e 96500 C/ e.
F = Faraday (equivalent to the mol of electron
participates in half reaction).
(H2) = 1.044 x 10-5 g/C
(Ag) = 1.118 x 10-3 g/C
(Cu) = 3.290 x 10-4 g/C
Example :
When an aqueous solution of potassium iodide is electrolyzed
using platinum electrodes, the half reactions are
2I(aq) I2(aq) + 2e-
2H2O(l) + 2e-  H2(g) + 2OH-(aq)
How many grams of iodine produced when a current of 8.52 mA
flows through the cell for 10.0 minutes.

Solution :
Amount of charge, Q = I x t
= 8.52 x 10-3 C/s x 600 s = 5.11 C

Grams of Iodine produced :

1 mol e
−
1 mol I 2 254 gram I 2 −3
= 5.11 C × × −
× =6.73 ×1 0 gram I 2
96500 C 2 mol e mol I 2
Example :
When an aqueous solution of copper (II) sulfate, CuSO 4. Is
electrolyzed, copper metal is deposited.
Cu2+(aq) + 2e-  Cu(s)
If a constant current was passed for 5 hours and 404 mg copper
was deposited, what was the current.

Solution :
Charge required to deposit 404 mg of copper is :
−
= 0.404 gram Cu × 1 mol Cu 2 mol e 96500 C
× × −
=1226 C
63.6 gramCu 1mol Cu mol e
Current required to produce that amount of copper is :
Current = charge/time
= 1226 C / 18000 s = 6.81 x 10-2 A.
EXERCISES
1. A voltaic cell is constructed from half- cells in which cadmium rod dips
into a solution of cadmium nitrate, Cd(NO3)2 & silver rod dips in silver
nitrate, AgNO3. Draw a sketch of the cell.

2. Find the standard potential for the following :

Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
Is the reaction is spontaneous or not?
(Ans : Eo = 1.10 V)

3. Show that copper does not dissolve in typical strong acid such as HCl.

4. What is the emf of the following voltaic cell at 25oC?

Zn(s) Zn2+ (1 x 10-5 M)Cu2+ (0.1M)Cu(s)
5. In an electrolytic cell, copper is used as the cathode and
graphite as the anode. Both electrodes are dipped into
CuCl2 aquoeus solution. Determine the overall reaction
and the minimum potential to carry out the reaction.

6. In an electrolysis, Zn is oxidized and Cu(II) ion is

reduced. Current of 0.780 A flows through the circuit for
25 minutes.
a) How many moles of electron transferred in the circuit?
b) How many moles of Zn dissolved in the solution?
c) How many grams of Cu produced?
(Ans : 0.0121 mol e-, 6.062 x 10-3 mol Zn, 0.3845 g Cu)