CHM271

CHAPTER 4
ELECTROCHEMISTRY
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 CHAPTER 4 : ELECTROCHEMISTRY
4.1 Types of electrochemical cell (Galvanic & Electrolytic)
4.2 Half-reactions and electrodes
4.2.1 Redox reaction
4.2.2 Calculation of standard cell potential, E°cell by using Standard Reduction Potential (SRP) table
4.2.3 Symbolic representation of a cell (Cell Notation)
4.2.4 Predicting spontaneity of redox reactions
4.2.5 The Nernst equation
4.2.6 Concentration cells
4.2.7 Factors affecting the redox potential
4.3 Electrolysis
4.3.1 Factors affecting electrolysis and Electrochemical series
4.3.2 Faraday’s law and quantitative aspects of electrolysis
4.3.3 Applications of electrolysis
 INTRODUCTION

ELECTROCHEMISTRY
A study of the inter-conversion electrical & chemical energy.

ELECTROCHEMICAL CELL
A cell consisting of electrodes that dip into electrolyte.
• 2 types : Galvanic & Electrolytic cell

REDOX REACTION
A chemical reaction which oxidation and reduction occur simultaneously.
• Oxidation at anode & Reduction at cathode

OIL = Oxidization is Loss (of e-)

RIG = Reduction is Gain (of e-)
 INTRODUCTION

HALF-CELL REACTIONS
The reaction occurs at anode & cathode.
• Combination of the two (2) half-cells gives an overall redox reactions

ELECTRODE
Represented by the anode and cathode of the cell

SALT BRIDGE
A U-shape tube which contains a gel permeated with a solution of inert
electrolyte such as KCl whoses ions will not react with other ions in
solution or with the electrodes.
TYPE OF ELECTROCHEMICAL CELL
 GALVANIC CELL
• Also known as Voltaic Cell
• A cell which a chemical reaction (redox) generates an
electric current spontaneously.
• Ecell > 0 for a spontaneous reaction.
• Anode is negative, cathode is postive
Once even one electron flows from the
ANODE the CATHODE, the charges in
each beaker would not be balanced and
the flow of electrons would stop.

Therefore, we use a salt bridge, usually

a U-shaped tube that contains a salt
solution, to keep the charges balanced.
❖Cations move toward the CATHODE.
❖Anions move toward the ANODE.
Voltaic cell based on zinc-copper reaction.

Oxidation half-reaction Reduction half-reaction

Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)

Overall (cell) reaction

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
 VOLTAIC CELLS

Voltaic Cell Voltage (V)

Common alkaline flashlight battery 1.5

Lead-acid car battery (6 cells = 12 V) 2.0

Calculator battery (mercury) 1.3

Lithium-ion laptop battery 3.7

Electric eel (~5000 cells in 6-ft eel = 750 V) 0.15

Nerve of giant squid (across cell membrane) 0.070

 ELECTROMOTIVE FORCE (EMF)
DEFINITION
The potential difference between the anode and cathode in a cell.
• Also called the Cell Potential, and is designated E°cell
• Measured in volts (V)
• E°cell at standard conditions
Concentration of electrolyte = 1.0 M
T = 25°C
P = 1 atm
E° cell = Eº (cathode) − Eº (anode)
@
Ecell = Eº (oxidation) + Eº (reduction)
 STANDARD REDUCTION POTENTIALS (SRP)
IMPORTANCE
• Identify the cathode & anode
• Determination of Ecell

More positive Eº
• Reduction (cathode)
• More easily electron is added
• More easily reduced
• Better oxidizing agent

More negative Eº
• Oxidation (anode)
• More easily electron is lost
• More easily oxidized
• Better reducing agent
 STANDARD HYDROGEN ELECTRODE

• As a reference to SRP values

• By definition, the reduction potential for hydrogen is 0 V
2 H+ (aq, 1M) + 2 e− → H2 (g, 1 atm)
 CELL POTENTIALS
EXAMPLE
Determine the cell potential, Ecell of a voltaic cell that uses
Zn/Zn2+ and Cu/Cu2+ half cell reactions.
Given Eored Zn/Zn2+ = -0.76V and Eored Cu/Cu2+= +0.34V

SOLUTION
E°cell = Eº (cathode) − Eº (anode)
= +0.34V- (-0.76V )
= 1.10 V
@
E°cell = Eº (oxidation) + Eº (reduction)
= +0.34V- (-0.76V )
= 1.10 V
 CELL NOTATION / CELL DIAGRAM
components of anode components of cathodecompartment
compartment (oxidation half-cell) (reduction half-cell)

Electrode Phase of Phase of Phase of Phase of Electrode

lower higher higher lower
oxidation oxidation oxidation oxidation
state state state state
Example 1 Anode : Zn(s) →Zn2+(aq) + 2e-
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s) Cathode : Cu2+(aq) + 2e- → Cu (s)

Example 2
- + 4- 2+
graphite | I (aq) | I2 (s) ║H (aq), MnO (aq) | Mn (aq) | graphite

Electrode Anode : 2I-(aq)→ I2 (s) + 2e-

graphite(inert) Cathode : MnO4-(aq)+ 8H+(aq)+ 5e- → Mn2+(aq) + 4H2O
 SPONTANEOUS OR NOT?

Spontaneity of the reactions involved in Voltaic Cell can be predicted directly

by the sign of calculated Ecell.

SPONTANEOUS
Ecell > 0
ΔG < 0

NONSPONTANEOUS
Ecell < 0
ΔG >0
 FREE ENERGY, ΔG

• ΔG for a REDOX reaction can be found by using the equation

ΔG = - nFEcell
where
n = number of moles of electrons transferred.
F = Faraday’s constant (96,500 C/mol)

• Under standard conditions, (1atm, 25°C, 1M)

ΔG° = - nFE°cell
ΔG° = RT ln Q
E°cell = -(RT/nF) ln Q
 FACTORS AFFECTING THE Ecell

1. Position of ions in the standard reduction potential.

2. Concentration of ions in electrolytes.
3. Temperature of the reaction.
4. Pressure of the gas when the reaction involves gases.

Factors that affecting the Ecell is represented by

NERNST EQUATION
 NERNST EQUATION

ΔG = ΔG° - RT lnQ
- nFEcell = - nFE°cell - RT lnQ where
T =Temperature (Kelvin)
RT
Ecell = E°cell - lnQ R = Gas Constant (8.314 J/mol K)
nF n = Moles of electrons transferred
F = Faraday’s Constant (96500 C/mol)
@
Q = [Product]x × P
[Reactant]y
2.303RT
Ecell = E°cell - log Q x & y is the stoichiometry number
nF P is pressure of gas (if any)

T = 25°C, P = 1atm 0.0592 V

Ecell = E°cell - log Q
n
EXAMPLE
In a test of a new reference electrode, a chemist constructs a voltaic cell
consisting of a Zn/Zn2+(0.010 M) half-cell and an H2/H+(2.5 M) half-cell at
0.30 atm. Determine Ecell at 298 K.
Given Eored Zn/Zn2+ = -0.76V and Eored H2/H+ = 0.00V

SOLUTION
Anode: Zn→ Zn2+ + 2e- E° = - 0.76 V

Cathode: 2H+ + 2e- → H2 E° = 0.00 V

Overall Zn + 2H+ → Zn2+ + H2
 SOLUTION (cont.)
E°cell = Eº (cathode) − Eº (anode)
= 0 V - (-0.76V )
= 0.76 V

Ecell 0.0592
= E°cell − n log Q

0.0592 [Zn2+]
= 0.76 − log ( + 2 × P)
2 [H ]

0.0592 [0.01]
= 0.76 − log ( × 0.3)
2 [2.5]2

= 0.76 − (- 0.10) V
= 0.86 V
 CONCENTRATION CELL
DEFINITION
An electrochemical cell with identical half-cells with different ion
concentration.

Applying Nernst Equation at T = 25°C, P = 1atm

0.0592 [Mn+]dilute
Ecell = E°cell - log
n [Mn+]conc.
EXAMPLE
Determine 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 1M SnSO4solution.

Cr I Cr3+ (0.01M) II Sn2+ (1.00M) I Sn

SOLUTION
Anode: (Cr → Cr3+ + 3e-) × 2 E° = - 0.74 V
2Cr → 2Cr3+ + 6e-

Cathode: (Sn2+ + 2e- → Sn) × 3 E° = - 0.14 V

3Sn2+ + 6e- → 3Sn
Overall 2Cr + 3Sn2+ → 2Cr3+ + 3Sn
 SOLUTION
E°cell = Eº (cathode) − Eº (anode)
= - 0.14V - (-0.74V )
= 0.60 V

Ecell 0.0592
= E°cell − log Q
n

0.0592 [Cr3+]2
= 0.60 − log
6 [Sn2+]3

0.0592 [0.01]2
= 0.60 − log
6 [1.00]3

= 0.60 − (- 0.04) V
= 0.64 V
 FACTORS AFFECTING THE REDOX POTENTIAL
1. Concentration of Ions (Electrolytes)
• Cell potential decreases as the concentration of ion in the cell decreases.

2. Temperature
• According to Nernst Equation, cell potential is temperature dependent.
• Ecell decreases with increasing temperature

RT
Ecell = E°cell + lnQ
nF
@

2.303RT
Ecell = E°cell + log Q
nF
 ELECTROLYSIS
DEFINITION
A process of dissociation or decomposition of electrolyte to produce
elements using an electric current to force a chemical reaction

• Reaction take place in electrolytic cell

• Opposite mechanism compared to
voltaic cell
• Electrons flow from anode to
cathode through external circuit.
• Steps involved :
1. Ion movement towards
electrodes
2. Ion discharged at electrodes.
 ELECTROLYTIC CELL

• Cations (+) move toward the CATHODE (-).

• Anions (-) move toward the ANODE (+).
• Commonly used electrode : Inert electrodes (Pt / graphite)
• Electrolytes : molten salts / aqueous solution of salts
 FACTORS AFFECTING ELECTROLYSIS

FACTORS AFFECTING
ELECTROLYSIS

Position of ions in Concentration of

Types of electrodes
electrochemical series electrolytes
Inert Particular ion with
higher concentration
will be selectively
discharged

Active

Lower position will be selectively discharged

 ELECTROLYSIS OF MOLTEN NaCl
• Major source of pure sodium metal & chlorine
• Molten NaCl consists of Na+ and Cl- ions

Anode (+) Cathode (-)

Cl- Na+
Electrode : Inert (Pt)

Half equation
Anode (Oxidation) 2Cl- → Cl2 + 2e-
Cathode (Reduction) Na+ → Na + e-
Overall reaction 2Cl- + 2Na+ → Cl2 + 2Na
 ELECTROLYSIS OF NaCl Solution (diluted)
• Aqueous NaCl solution consists of Na+, H+, Cl- and OH- ions

Electrode : Inert (Pt)

Anode (+) Cathode (-)
Cl- and OH- Na+ and H+
OH- is less stable than Cl- H+ is less stable than Na+
OH- is selectively discharged H+ is selectively discharged
4OH- → 2H2O + O2 + 4e- 4H+ + 4e- → 2H2
Overall reaction : 2H2O → O2 + 2H2
 ELECTROLYSIS OF NaCl Solution (conc.)
Reference video : https://www.youtube.com/watch?v=1FDzt5VP50c

[H+] & [OH-]

too low

Electrode : Inert (Pt)

Anode (+) Cathode (-)
Cl- and OH- Na+ and H+
[Cl-] >>> [OH-] H+ is less stable than Na+
Cl- is selectively discharged H+ is selectively discharged
[H+] too low, consider H2O itself
2Cl- → Cl2 + 2e- 2H2O + 2e- → H2 + 2OH-
Overall reaction : 2Cl- + 2H2O → Cl2 + H2 + 2OH-
 ELECTROLYSIS OF CuSO4 Solution
• Aqueous CuSO4 solution consists of Cu2+, H+, SO42- and OH- ions

[H+] & [OH-]

too low

Electrode : Inert (Carbon)

Anode (+) Cathode (-)
SO42- and OH- Cu2+ and H+
OH- is less stable than SO42- Cu2+ is less stable than H+
OH- is selectively discharged c2+ is selectively discharged
2H2O → O2 + 4H+ + 4e- 2Cu2+ + 4e- → 2Cu
BLUE → PALE BLUE
Overall reaction : 2H2O + 2Cu2+→ O2 + 4H+ + 2Cu
 TYPES OF ELECTRODES
2 types of electrode:
Inert Active

Metals do involve in
Electrode does not
reaction if the
take part in the
solution is made of
reaction
same element

Electrolysis of
carbon (graphite), CuSO4 solution
platinum using copper
electrode
 ELECTROLYSIS OF CuSO4 Solution
• Aqueous CuSO4 solution consists of Cu2+, H+, SO42- and OH- ions

[H+] & [OH-]

too low

Inert Electrode (Carbon)

Anode (+) Cathode (-)
SO42- and OH- Cu2+ and H+
OH- is less stable than SO42- Cu2+ is less stable than H+
OH- is selectively discharged c2+ is selectively discharged
2H2O → O2 + 4H+ + 4e- 2Cu2+ + 4e- → 2Cu
BLUE → PALE BLUE
Overall reaction : 2H2O + 2Cu2+→ O2 + 4H+ + 2Cu
 ELECTROLYSIS OF CuSO4 Solution
• Aqueous CuSO4 solution consists of Cu2+, H+, SO42- and OH- ions

Active Electrode
(Copper)
Anode (+) Cathode (-)
Cu2+ Cu2+
2Cu→ Cu2+ + 2e- 2Cu2+ + 2e- → Cu
 ELECTROLYSIS OF NaCl Solution (conc.)
Concentration affects the ion selection to be discharged as well
regardless the positions of ions in electrochemical series.

[H+] & [OH-]

too low

Electrode : Inert (Pt)

Anode (+) Cathode (-)
Cl- and OH- Na+ and H+
[Cl-] >>> [OH-] H+ is less stable than Na+
Cl- is selectively discharged H+ is selectively discharged
[H+] too low, consider H2O itself
2Cl- → Cl2 + 2e- 2H2O + 2e- → H2 + 2OH-
Overall reaction : 2Cl- + 2H2O → Cl2 + H2 + 2OH-
 FARADAY’s LAW
1st Law
The quantity of a substance formed at an electrode is directly
proportional to the quantity of electric charge that has flowed in the circuit
2nd Law
For a given quantity of electric charge, the amount of any metal formed
at the electrode is proportional to its equivalent weight.
• The quantity of electric charge is given by:

where
Q= It Q =electric charge in coulombs (C)
I = current in amperes (A) ; 1A = 1 J/C

ne-= Q/F t = time in seconds (s)

ne- = mol of electrons transferred (mol)
F = Faraday’s Constant (96500 C/mol)
 CALCULATING ON PLATING

Reference Video : https://www.youtube.com/watch?v=m5wV6R7RKg0

 SUMMARY : CALCULATING ON PLATING

mol gram @ L
Mol of substance mass = mol × molar mass Mass/volume
oxidized/reduced Molar volume at STP = 22.4 L/mol of substance
oxidized / reduced
Half
reactions

n e- = ? n X
C
Mol of electrons ne- = Q/F
Charge , Q
transferred F = 96500 C/mol
mol
Q= It
Current, I Time, t
A s
EXAMPLE
Determine the mass of Ca that will be produced in an electrolytic cell of
molten CaCl2 if a current of 0.452 A is passed through the cell for 1.5 hours.

SOLUTION
Cathode (Reduction) : Ca2+ + 2e- → Ca
Q = It ne- = Q/F
= 0.452 C/s × 5400 s = 2, 440.8 C / 96500 C/mol
= 2, 440.8 C = 0.0253 mol of electrons

nCa = ½ ne- mCa = nCa ×molar mass

= ½ × 0.0253 mol = 0.0126 mol × 40 g/mol
= 0.0126 mol of Ca = 0.504 g
EXAMPLE
A silver-plated spoon typically contains about 2.00 g of Ag. If 12.0 h are
required to achieve the desired thickness of the Ag coating, determine the
average current per spoon that must flow during the electroplating process.

SOLUTION
Cathode (Reduction) : Ag+ + e- → Ag
mAg = nAg × molar mass ne- = Q/F
nAg = mAg ÷ molar mass Q = ne- × F
= 2.00 g ÷ 107.87 g/mol = 0.0185 mol × 96500 C/mol
= 0.0185 mol of Ag = 17891.19 C

nAg = ne- Q = It
= 0.0185 mol of electrons I = Q/t
= 17891.19 C / 43,200s
= 0.4141 C/s @ 0.4141 A
 APPLICATION OF ELECTROLYSIS
1. Electro-refining
• purification of a metal by electrolysis
2. Electroplating
• the coating of one metal on the surface of another metal by
electrolysis.
• The coating process can protect metals from corrosion
APPLICATION OF ELECTROLYSIS : ELECTRO-REFINING
PURIFICATION OF COPPER Anode:
Cu → Cu2+ + 2e
• In anode, the Cu from the electrode are
ionized to form Cu2+
• Anode becomes thinner as the reaction
continues
Cathode
Cu2+ → Cu + 2e
In cathode, the Cu2+ are discharged to
Impurities form Cu and then deposit on the surface of
less reactive than copper the cathode.
(e.g. Au, Ag, Pt) will collect • Impurities in the copper do not dissolve,
below the anode, while more and instead fall off the anode as anode
reactive impurities (e. g. Zn) sludge.
will dissolve in the solution • At the cathode, the copper ions are
as aqueous ions. deposited as pure copper metal.
APPLICATION OF ELECTROLYSIS : ELECTROPLATING

ELECTROPLATING OF CHROMIUM ONTO IRON

anode cathode

Cr (s) iron object

Cr3+ (aq)

Electrolyte :aqueous solution of chromium (lll) chloride.

CrCl3 (aq) → Cr3+ (aq) + 3Cl- (aq)

At the chromium anode,

the chromium dissolves to form Cr3+ ions:
 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 is 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
COMPARISON : VOLTAIC Vs ELECTROLYTIC CELL

Spontaneity Electrode
Cell Type ΔG E°cell Name Process Sign
Voltaic <0 >0 Anode Oxidation -
>0 <0 Cathode Reduction +
Electrolytic <0 >0 Anode Oxidation +
>0 <0 Cathode Reduction -