ELECTROCHEMISTRY

PART 1
TUTIYANA MOHAMED
 ELECTROCHEMISTRY
4.1 Electrode potential and electrochemical cells
4.2 Nernst equation
4.3 Electrolysis
 LESSON OUTCOMES
At the end of this lesson, students should be able to :
• Identify redox reaction
• Write half-cell reactions, overall equation and cell
notation/diagram/symbol
• Calculate the cell potential at standard condition and at non standard
condition.
• Calculate the quantitative variable using Faraday’s Law.
 INTRODUCTION
ØElectrochemistry: a study of the inter-conversion electricity and chemical
reactions/energy
ØElectrochemical cell : a cell consisting of electrodes that dip into
electrolytes
ØElectrodes: solid conductors that allows electrons to pass through them.
e.g: platinum, graphite
ØElectrolytes: compounds that conduct electric currents either in the
molten state or aqueous solutions. e.g: ionic compounds
 Oxidation–Reduction Reactions
• Involves two processes:
• Oxidation – loss of electrons from one reactant

Na(s) ⎯→ Na+ + e – Oxidation Half Reaction

• Reduction – gain of electrons from another reactant
Cl2(g) + 2e – ⎯→ 2Cl– Reduction Half Reaction
• Net reaction
2Na(s) + Cl2(g) ⎯→ 2Na+ + 2Cl–
• Oxidation and reduction ALWAYS occur together
• Can't have one without the other
5
 Oxidation-Reduction Reaction
Oxidizing Agent (Reduction)
• Substance that accepts the electrons
• Takes electrons from another substance
• ∴ is itself reduced
• Electron acceptor
• Cl2(g) + 2e – ⎯→ 2 Cl–
Reducing Agent (Oxidation)
• Substance that donates electrons
• Releases electrons to another substance
• ∴ is itself oxidized
• Electron donor
• Na(s) ⎯→ Na+ + e – 6
 Spontaneous Redox Reactions
• When a copper wire is placed in a solution of silver nitrate
• Silver metal spontaneously precipitates
• Copper ion spontaneously forms as evidenced by blue color of solution

7
 Spontaneous Redox Reactions
Redox half reactions:
Anode (Oxidation): Cu(s) ⎯→ Cu2+(aq) + 2e –
Cathode (Reduction): 2Ag+(aq) + 2e – ⎯→ 2Ag(s)
Overall reaction:
Cu(s) + 2Ag+(aq) ⎯→ Cu2+(aq) + 2Ag(s)
Standard Cell Notation:
e-
Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
• Silver metal placed in a solution of AgNO3
• Copper metal placed in solution of Cu(NO3)2
• Each compartment is called a half-cell
8
 Cell Notation
anode Salt Bridge cathode
Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s)
anode oxidation reduction cathode
electrode electrolyte(s) electrolyte(s) electrode

• Single slash (/) or vertical line (|) represents a phase boundary

(solid electrode and solution)
• Double slash (// or ||) represents salt bridge
• There are two phase boundaries, one at each end
• Putting it together
• Write the anode, a slash, then all the soluble ions (separated with a
semicolon, ;) in the oxidation half reaction.
• Insert a double slash for the salt bridge
• Write all the soluble species in the reduction half reaction, a slash, then
the cathode
9
Where there are no conductive metals involved in a process, an inert
electrode is used. C(gr) or Pt(s) are often used. Write the standard
cell notation for the reactions
H2O2(aq) + CO2(g) ⎯→ H2C2O4(aq) + O2(g)
Platinum electrodes (common)
Pt(s)|O2(g)|H2O2(aq); H+(aq)||H2C2O4(aq); H+(aq)|CO2(g)|Pt(s)

Graphite electrodes (less common)

C(gr) |O2(g)|H2O2(aq); H+(aq)||H2C2O4(aq); H+(aq)|CO2(g)|C(gr)
 Half-Cells
• When metal ion collides with • If metal atom on surface of
electrode and gains electrons, electrode loses electrons,
ion becomes reduced becomes oxidized

Left on their own, each individual cell quickly establishes an equilibrium between metal and
ions in solution.
M(s) ⎯→ Mn+(aq) + ne – 11
 Summary of a Galvanic Cell
• Half-cells (compartments containing reactants for each
half-reaction)
• Electrodes provide a site for electron transfer
§ Wire connecting two half-cells conducts
electrons from anode to cathode
§ Flow of ions from salt bridge maintains
electrical neutrality

12
 Electron Flow Between Half-Cells
• At copper end, two electrons are given up
• Cu(s) ⎯→ Cu2+(aq) + 2e –
• Travel across with wire to the silver half-cell
• 2Ag+(aq) + 2e – ⎯→ 2Ag(s)
• What happens to the charge in each half-cell?
§ Each time a copper atom reacts
§ Net charge at copper end
increases by 2
§ Net charge at silver end
decreases by 2
Ø This would violate the principle of electrical neutrality
Ø Cannot have solution with a net charge
Ø We need to balance the charge in order for the electrons to flow
13
 Salt Bridge
Salt bridge
• Needed to complete circuit
• Tube filled with agar saturated with an electrolyte
• Salt composed of ions not involved in cell reaction
• KNO3 and KCl often used
• Enable ions from salt bridge to migrate between half-cells to
neutralize charges in cell compartments
• Anions always migrate toward anode
• Cations always migrate toward cathode

14
 Electrolytic vs Galvanic Cells
• Electrolysis means application of electricity
• Electrolytic means that a particular reaction is not spontaneous
Electrolytic Cell Galvanic Cell
Ø Cathode is negative (reduction) Ø Cathode is positive (reduction)
Ø Anode is positive (oxidation) Ø Anode is negative (oxidation)
Ø Non-spontaneous Ø Spontaneous
Ø Requires a battery Ø Is a battery

• In both galvanic and electrolytic cells, positive ions move to

cathode and negative ions move to anode
§ Attracted there in electrolytic cell by charges on electrodes
§ Diffuse there in galvanic cell to balance developing charges
15
 Cell Potential
• Electrons in different metals have different potential energy
• The potential difference is termed cell potential
• The maximum potential difference across a cell is its electromotive force (e.m.f)
• A cell potential (Ecell): the sum of electrode potentials (E) of the two cells making up
the electrochemical cell.
Unit: volt (V)
• Electrode potential is a measure of the half cell to attract electrons
• The more positive the half cell’s electrode potential, the stronger is its attraction for
electrons E.g: Daniell cell
• The electrode potential of Cu is more positive than Zn since the electrons flowing
from Zn electrode to Cu electrode
 Electrical Potential
• Cell potential
• Competition between two half-cells
• Every half-cell has tendency to gain electrons and proceed as
reduction half-reaction
• Reduction Potential, E
• Relative ease of gaining electrons
• Standard Reduction Potential, E °
• Reduction potential measured under standard conditions

18
 Standard Cell Potential, E °cell
• When two half-cells are connected
• The one with larger (more positive) E °will acquire electrons and undergo
reduction
• The one with lower (less positive) E °will donate electrons and undergo
oxidation
• Determine the standard cell potential, E °cell
• As the difference between E °of one half-cell and E ° of other half-cell
• The more positive E °represents the reduction half reaction and we call it
E °red and the less positive E ° will represent the oxidation half reaction
and is E °ox
• The standard cell potential is E ° cell
E °cell = E °red (reduced) – E °red (oxidized)
19
 Calculating E °cell
• Look at reaction in zinc-copper cell
Zn(s) + Cu2+(aq) ⎯→ Zn2+(aq) + Cu(s)

• Zinc is oxidized
• Copper is reduced
• Half reduction reactions
Zn2+(aq) + 2e – ⎯→ Zn(s)
Cu2+(aq) + 2e – ⎯→ Cu(s)
• Reaction for Cu2+ must have greater
tendency to proceed than Zn2+
as Cu2+ is the one reduced

E °cell = E °Cu2+ – E °Zn2+ 20

 Ex. Galvanic cell of Cu/Cu2+ with
Hydrogen Electrode
Cu2+(aq) + 2e – D Cu(s) (cathode)
H2(g) D 2H+(aq) + 2e – (anode)
Cu2+(aq) + H2(g) D Cu(s) + 2H+(aq) (cell reaction)
E °cell = E °reduced – E °oxidized
E °cell = E °cathode – E °anode
E °cell = E °Cu2+ – E °H+
0.34 V = E °Cu2+ – 0.0 V
E °Cu2+ = 0.34 V

21
 Ex. Galvanic cell of Zn/Zn2+ with
Hydrogen Electrode
• In this case the hydrogen electrode is positive so it is the cathode
Zn(s) D Zn2+(aq) + 2e – (anode)
2H+(aq) + 2e – D H2(g) (cathode)
Zn(s) + 2H+(aq) D Zn2+(aq) + H2(g) (cell reaction)

E ˚cell = E °reduced – E °oxidized

E ˚cell = E °cathode – E °anode
E ˚cell = E °H+ – E °Zn2+
0.76 V = 0.00V – E °Zn2+
E °Zn2+ = –0.76 V
22
 Standard Reduction Potentials (E ˚)
• All tabulated as reduction potentials
• oxidized form + electrons → reduced form
• Can be ions, elements or compounds
• Arranged from top to bottom by decreasing E °
• Positive values of E ° means substance is easily reduced
• The more positive value of E ° indicates reduction is a more likely
reaction

F2(g, 1 atm) + 2e – → 2F–(aq, 1 M) E ° = 2.87 V

• Most easily reduced

23
 Standard Reduction Potentials (E °)
• Low value of E ° (E ° < 0) means substance is easily oxidized
• More negative value of E °(Oxidation) the substance is less likely to
undergo reduction
• Li+ (aq, 1 M) + e – → Li(s) E ° = –3.05 V
• More likely the reverse reaction occurs
• Li(s) → Li+ (aq, 1 M) + e – E ° = +3.05 V
• When reaction reversed, sign of E ° reversed

24
 Using E ˚cell to Calculate E ° of a Half Reaction
2Ag+(aq) + Cu(s) ⎯→ 2Ag(s) + Cu2+(aq)
E °cell = 0.46 V
• Cu(s) undergoes oxidation
E °Cu = + 0.34 V

• Ag+(aq) undergoes reduction

• What is E °for the half-reaction of Ag+ + e – → Ag?
E °cell = E °Ag – E °Cu
+0.46 V = E °Ag – (+0.34 V)
E °Ag = 0.46 V + 0.34 V = +0.80 V 25
Predicting if Reaction is Spontaneous

• Given any redox reaction

• Calculate E °cell for reaction as written
• If E °cell > 0 V (positive), then reaction is spontaneous
• If E °cell < 0 V (negative), then reaction is nonspontaneous. Another
view is that it is spontaneous in the reverse direction.

• Galvanic cell is always spontaneous

• Because it is always set up so E °cell is positive
26
Ex. What spontaneous reaction occurs when Cr and Au are
added to a solution of Au3+ and Cr3+?

Cr3+(aq) + 3e – → Cr(s) E ° = –0.74 V

Au3+(aq) + 3e – → Au(s) E ° = +1.50 V

• Au is more positive so it will be the reduction half reaction

• Cr is least positive so it will be the oxidation half reaction (it
will be reversed below)
Au3+(aq) + 3e – → Au(s)
Cr(s) → Cr3+(aq) + 3e –

Au3+(aq) + Cr(s) → Au(s) + Cr3+(aq)

27
• Use reduction potentials to predict E °cell for the reaction.
Cr3+(aq) + 3e – → Cr(s) E ° = –0.74 V
Au3+(aq) + 3e – → Au(s) E ° = +1.50 V
Overall Reaction = Au3+(aq) + Cr(s) → Au(s) + Cr3+(aq)
• E °cell = E °reduced – E °oxidized
• E °cell = E °Au3+ – E °Cr3+
• E °cell = +1.50 V – (–0.74 V)
• E °cell = +2.24 V (positive V means a spontaneous reaction)

28
Calculating Cell Potentials, E °cell
• Predict the standard cell potential when Mg and Cd are added
to a solution containing Mg2+ and Cd2+ ions.
Cd2+(aq) + 2e – → Cd(s) E ° = –0.40 V
Mg2+(aq) + 2e – → Mg(s) E ° = –2.37 V
• Since Cd2+ has the least negative value, it is reduced and so
Mg is oxidized
• E °cell = E °red – E °ox = –0.40 V – (–2.37 V)
= + 1.97 V
The spontaneous reaction is:
Cd2+(aq) + Mg(s) → Cd(s) + Mg2+(aq)
29
 TUTORIAL
1. Write the standard cell notation for the following electrochemical
cells:
a) Fe(s) + Cd2+(aq) ⎯→ Cd(s) + Fe2+(aq)
b) Al(s) + Au3+(aq) ⎯→ Al3+(aq) + Au(s)
2. Write the overall cell reaction, cell notation and calculate the cell
potential for the galvanic cell employing the following half-
reactions.
Co2+(aq) + 2e – → Co(s) E ° = –0.28 V
Au3+(aq) + 3e – → Au(s) E ° = +1.50 V
 TUTORIAL
3. Determine whether the following reaction is spontaneous as written
6I–(aq) + BrO3–(aq) + 6H+(aq) → 3I2(s) + Br–(aq) + 6H2O
I2(s) + 2e – → 2I–(aq) E °= + 0.54 V
BrO3–(aq) + 6H+(aq) + 6e – → Br–(aq) + 6H2O E ° = + 1.44 V
4. Determine whether or not the following reaction is spontaneous as
written
Au(s) + Al3+(aq) → Au3+(aq) + Al(s)
Al3+(aq) + 3e – → Al(s) E ° = –1.66 V
Au3+(aq) + 3e – → Au(s) E ° = +1.50 V 31
 TUTORIAL
5. A galvanic cell is constructed from the following half cell, Tin and Lead.
Sn4+ (aq) + 2e- → Sn2+ (aq) E ° = 0.13 V
Pb2+ (aq) + 2e- → Pb (s) E ° = -0.13 V
a) Identify anode and cathode.
b) Write the overall cell reaction.
c) Write the cell notation for the reaction.
d) Calculate the standard potential for the cell.
e) Which species is the stronger reducing agent?
f) Predict whether the cell reaction is spontaneous or not.
 Relating E °cell to ΔG °
• Both E °cell to ΔG ° let us predict spontaneity of reaction
• For chemical reaction
• –ΔG ° = maximum work system can do
• In electrical system
• Maximum work = nFE °cell
• Where n = number of moles of electrons transferred
• F = Faraday’s constant = number of Coulombs
of charge equivalent to 1 mole of electrons
• 1 F = 96,500 C
• E °cell = potential of cell in Volts 33
 " coulombs % " joules %
Max Work = (
mol e $$−
) '$
− '$
# mol e & # coulomb &
'' = J

n F Ecell
• Equating the two expressions for maximum work gives
• ΔG = –nFEcell

• If using standard potentials, you can calculate

standard free energy changes
ΔG ° = –nFE °cell
34
 FREE ENERGY
Under standard conditions, (1atm, 25°C, 1M)
∆G° = −nFE°cell
∆G° = RT ln Q
E°cell = -(RT/nF) ln Q
Calculating Cell Potentials, E °cell
Ex. Calculate ΔG ° for the following reaction
• Au3+(aq) + Al(s) → Au(s) + Al3+(aq)
• E °cell = +3.16 V
• Solving
• Std conditions so T = 25oC = 298 K
# 96, 485
96,500 C C & # 1 J &
ΔG  = −(3 mol e − ) %% ( (3.16 V) %%
− (
((
$ 1 mol e ' $ 1C V '

• ΔG ° = –914,820 J/mol = –915 kJ/mol

36
 NERNST EQUATION
∆G = ∆ G0 + RT ln Q

This means −nFE = −nFE0 + RT ln Q

Dividing both sides by −nF, we get the

Nernst equation:
Ecell =E0cell− RT ln Q
nF
§ The term E °cell is used when the system is at standard state and Ecell is
used when the system is not at standard state. Q is the value of the mass action
expression for a given set of concentrations
Using base-10 logarithms, (2.303 log A = ln A)

Ecell = E0cell − 2.303 RT log Q

nF

T = Temperature in K
R = gas constant, 8.314 J/K.mol
F = 96,500 C/mol
n = Number of moles of electrons
Q = [Product]/[Reactant]
Ø At room temperature (298 K):
2.303 RT = 0.0592
F
Ecell = E0cell − 0.0592 log Q
n
 Nernst Equation : Factors affecting the Ecell

• Position of ions in the standard reduction potential

• Concentration of ions in electrolytes
Ø pH due to [H+]
Ø Complex ion
• Temperature of the reaction
• Pressure of the gas when the reaction involves gases
• Factors that affecting the Ecell is represented by Nernst Equation
 Concentration Cells
Definition
an electrolytic cell that is comprised of two half-cells with the same
electrodes, but differing in concentrations.
A concentration cell acts to dilute the more concentrated solution and concentrate
the more dilute solution, creating a voltage as the cell reaches an equilibrium.
From the Nernst Equation,
Ecell = E0cell − 0.0592 log Q
n
Ecell = E0cell − 0.0592 log [Product]
n [Reactant]
The product and reactant are determine from the overall equation and cell notation
•When a voltaic cell using the same substance at both electrodes, E°cell = 0
•Ecell will not be 0 as long as the concentrations are different (Q ≠ 0)
Ex. Calculate the cell potential of an electrochemical cell made of a Cr electrode in a
0.01M Cr(NO3)3 solution and a Sn electrode in a 1.00M SnSO4 solution?

Cr ǀCr3+ (0.01M) ǁ Sn2+ (1.00M) ǀ Sn

E°cell = Ered(reduced) − Ered(oxidised) or E°cell = Ereduction + Eoxidation

= -0.14 − (-0.74) = -0.14 + 0.74
= +0.60V = +0.60V
24
Mol of electron, n = 6
Q = [product]/[reactant] = 0.01M/1.00M = 0.01

Ecell = E0cell − 0.0592 log [Product]

n [Reactant]

Ecell = 0.60 − 0.0592 log (0.01)2

6 (1.00)3

Ecell = 0.60 + 0.0395 = 0.635

= 0.64 V
ELECTROCHEMISTRY
PART 4
TUTIYANA MOHAMED
 ELECTROLYSIS
Ø Electrolysis : a chemical process that uses electricity to cause non
spontaneous redox reaction to occur. The reactions take place in
Electrolytic Cells
Ø Electrolytic cell is made up of two electrodes connected to a battery and
immersed in an electrolyte
Ø Nonspontaneous
Ø Use electrical energy to force nonspontaneous reaction to occur
Anode is still where oxidation occurs
Cathode is still where reduction occurs
Ø Type of reaction that occurs when you recharge batteries
Ø Substance undergoing electrolysis must be molten or in solution so ions can
move freely and conduction can occur
• Molten NaCl cell (801oC)
• Inert electrodes placed into
molten liquid and connected
to source of electricity
• Cathode: Na+(l ) + e – → Na(l )
• Anode: 2Cl–(l ) → Cl2 (g) + 2e –
• Multiply first half-reaction by 2
to balance electrons then add
2Na+(l) + 2e – → 2Na(l )
2Na+(l ) + 2Cl–(l ) → 2Na(l ) + Cl2(g)
• Since nonspontaneous
electrolysis
2Na+(l )+ 2Cl–(l ) ⎯⎯⎯⎯→ 2Na(l ) + Cl2(g)
45
 Atomic View of Oxidation
• Only occurs because reactions take place at surface of
electrode
• Consider molten NaCl electrolytic cell
• When charged anode placed in molten NaCl
• Positive charge attracts Cl– ions
• Positive charge on electrode pulls e– away from Cl– to
form Cl atoms that combine to form Cl2
• Cl2 is neutral so drifts away from charged electrode
• Quickly replaced by other Cl– or anions in solution
• Other negative ions move toward anode causing charge
migration
• Similarly positive ions migrate to cathode
46
 Electrolysis of aqueous NaCl
Ø Aqueous NaCl solution contains Na+, H+ , Cl- and OH- ions.
Ø Carbon electrodes are used in this electrolysis
Ø Cations(Na+, H+) and anion (Cl-,OH-) are competing to discharge at cathode and anode respectively, however only
one cation and one anion can be discharged.
Ø Cation and anion that arrange at the lower position of electrochemical series will be easier to discharged at
electrode. For cation:-
Na+ + e- → Na
2H+ +2e-→H2

Ø H+ ion is discharged at cathode producing H2 gas since its position is lower than Na+ ion.
Ø At pH of 7, the concentration of H+ is too low to consider the reduction to take place. So that, water molecule
undergo reduction to produce H2 gas.
Ø OH- may discharged at anode due to the lower position in electrochemical series but the concentration of OH-
also too low
Ø Therefore chloride ion undergo oxidation to produce Cl2 gas. The two half-cell reactions for the electrolysis of
aqueous NaCl are:-
Ø Reduction= 2H2O +2e- →H2 + 2OH-
Ø Oxidation = 2Cl- → Cl2 +2e-
 Electrolysis of aqueous CuSO4
• Carbon electrodes were used
• Ion present in the solution are Cu2+, H+, SO42- and OH-
• Copper ion is discharged on the cathode
• Water, H2O discharged at anode to form oxygen gas
• BLUE solution of CuSO4 turn to PALE BLUE as the concentration of Cu2+
decreases.
• Reduction at cathode = Cu2+ +2e- → Cu
• Oxidation at anode = 2H2O → O2 + 4H+ + 4e-
 Concentration of Electrolytes
Ø Concentration of solution affects the ion selection to be discharged.
Ø When concentrated solution of NaCl is electrolyzed, Cl2 gas is released
at anode instead of O2.

Reaction at anode= 2Cl- → Cl2 + 2e-

Reaction at cathode= 2H2O +2e- → H2 + 2OH-
• Faraday’s 1st law: the quantity of a substance formed at an electrode is
directly proportional to the quantity of electric charge that has flown in the circuit
• Faraday’s 2nd law: for a given quantity of electric charge, the amount of any
metal formed at the electrode is proportional to its equivalent weight
• Determined that amount of chemical change occurring during electrolysis is
directly proportional to amount of electrical charge passed through cell
• Ampere (A)
• SI unit of electrical current
• Coulomb (C)
• SI unit of charge
• 1 coulomb = 1 ampere × 1 second
• 1C=1A×s
• Faraday (F)
• 1 F = 96,500 C/mol e – 50
• Faraday’s Equation
• q = charge (coulombs, C)
q = It = n F
• I = current (Amperes, A, or C/s)
• t = time (s)
• n = moles of electrons transferred in process
• F = Faraday’s constant (96,500 C/mol)
• Units tell us how these quantities are related
• Calculate moles of substance electrolyzed as

I !t
moles&=&
n !F 51
Calculations Related to Electrolysis
In the electrolysis of a solution containing Ni2+ (aq), metallic Ni(s)
deposits on the cathode. Using a current of 0.150 A for 12.2 min, what
mass of nickel will form?
Faradays
(mole e–)
1"mol"reactant
F n "mol"e −

Mol reactant
Charge (C) (or product)
MM
A×s=C
Mass (g) reactant
Current (or product)
and time 52
 Solution
1. Calculate charge passing through cell in 12.2 min
• Coulombs (C) = current (A) × time (s)
• C = 0.150 A × 12.2 min × 60 s/min
• C = 109.8 C

2. Calculate moles of electrons

–
1 mol e
mol e – = 109.8 C × = 1.14 × 10 -3 mol e –
96,485
96,500 CC
1 mol Ni 58.69 g Ni
Mass = 1.14 ×10 mol e ×
−3 −
−
×
2 mol e 1 mol Ni
= 0.0334 g Ni 53
Example:
An aqueous solution of copper (II) nitrate was electrolysed using a current of 1.5 A
for 60 minutes at 250C and 1 atm. Calculate the mass of copper metal deposited at the
cathode. Molar mass Cu = 63.5 g/mol)

Solution: Half equation at cathode:

Cu2+ (aq) + 2e- → Cu(s)
The amount of electric charged passed through
the solution: Thus,
• 2 F charges formed 1 mol Cu
Q = It
5.6 × 10-2 F charges formed 1 mol × 5.6 × 10-2F
Q = 1.5 × (60 min × 60 s/min) C =5.4×103 C 2F
= 2.8 × 10-2 mol Cu
96 500 C = 1 F
Mass = number of moles × molar mass
5.4×103 C =5.6×10-2 F
= 2.8 × 10-2 mol Cu × 63.5 g/mol = 1.8 g
How long must a current of 0.800 A flow to form 2.50 g of silver metal in
an electroplating experiment? The cathode reaction is
Ag+(aq) + e – → Ag(s)

Faradays
1"mol"reactant (mole e–)
n "mol e − F
Mol reactant
(or product) Charge (C)

MM
A×s=C

Mass (g) reactant Current

(or product) and time
55
 Solution
1. Calculate mole of electrons required

1$mol$Ag 1$mol$e −
mol$e − = 2.500$g$Ag$ × ×
107.9$g$Ag 1$mol$Ag
= 0.02317 mol e–
2. Calculate quantity of charge
96,500
96, C
485&C
0.02317&mol&e × −
= 2236&C
1&mol&e −

3. Calculate time required

Charge*(C) 2236*C 1*A*s 1* min
time = = × × = 46.6min
current*(A) 0.800*A 1*C 60*s 56
 Application of Electrolysis
Electro-refining of Metals
Purifying metals such as Cu
Ø Ultrapure Cu sheets = cathodes
Ø Lower between slabs of impure Cu =
anodes
Ø Aqueous CuSO4 electrolyte solution
Ø 4 weeks for anodes to dissolve and
pure Cu to plate onto cathodes

57
Refining Copper
Refining Copper

58
 Electroplating
E.g: electroplating of chromium
onto iron.
The electrolyte is an aqueous solution
of chromium (lll) chloride.
CrCl3 (aq) → Cr3+ (aq) + 3Cl- (aq)
• Anode: chromium dissolves to form
Cr3+ ions:
Cr (s) → Cr 3+ (aq) + 3e-
• Cathode : chromium gets deposited
onto the surface of the iron object:
Cr 3+ (aq) + 3e- → Cr (s)
 Corrosion of Iron
• Steel mostly iron
• Fe2O3 coating NOT impervious to further corrosion
• Physical stress points leave strain in metal
• More susceptible to corrosion
• Creates anodic and cathodic regions
• Electrochemical process
• Anode region: Fe ⎯→ Fe2+ + 2e –
• Electrons flow through steel to cathode region
• Cathode region: O2 + 2H2O + 4e – ⎯→ 4OH –

60
 Manufacture of Cl2, H2 and NaOH
• By Chlor-alkali process
- Chlorine = used in plastic industry, water treatment
- NaOH = used in making paper, detergent, textiles
• Brine enters the left compartment where chloride ion are oxidized at anode
to produce chlorine gas
• At cathode, electrolysis of H2O will produce H2 gas
• Unreacted sodium ions diffuse through permeable plastic membrane to right
compartment and react with hydroxide ions to form NaOH solution
 Reference
Brady/Jespersen/Hyslop. Chemistry, 7th Edition. John Wiley & Sons
THANK YOU