Lecture 4

Learning objectives

 Determine the standard reduction potentials

and use them to calculate the emf of a cell
and hence the spontaneity of the reaction.
Electrochemistry
Electrochemistry – is the branch of chemistry that deals with the
interconversion of electrical energy and chemical energy.
-- Is the science of the chemistry associated with the flow of
electricity.

Electrochemical process – are spontaneous or non-spontaneous

redox reactions.
 Spontaneous reactions (of electrochemical processes) – the energy
released by chemical reactions are converted to electricity.
 Electrolysis – where electricity is used to drive a non-spontaneous
redox reactions.
Electrochemistry
1. Certain chemical reaction can create
electricity.
Electrochemistry
2. Electricity can make certain chemical reactions happen
that wouldn't happen otherwise.

O H
Redox reactions

 are reactions in which electrons are transferred from one substance

to another.
 Describe all chemical reactions in which there is a net change in
atomic charge
 Oxidation- reduction reaction

 It is class of reactions that includes

Formation of compounds from its elements

All combustions reactions
Reactions that generate electricity
Reaction that produce cellular energy.
Redox reactions

Three Key Points

• Redox reaction can be defined as one in which the oxidation
numbers of the species change.
• Oxidation (electron loss) always accompanies reduction
(electron gain). The oxidizing agent is reduced, and the
reducing agent is oxidized.
• The total number of electrons gained by the atoms/ ions of the
oxidizing agent always equals the total number lost by the
atoms/ions of the reducing agent.
Redox reactions

Terminologies
 The key idea is the movement of electrons from one reactant to
another.
 Oxidation is the loss of electrons
 Reduction is the gain of electrons
 Oxidizing agent is the electron acceptor, species doing oxidizing
 Reducing agent is the species doing the reducing.
 Redox reactions
Rules for Assigning an Oxidation Number (O.N.)

 Oxidation numbers of elements in the free or uncombined state are

always zero.

 The algebraic sum of the oxidation numbers of all the atoms in the
formula of a compound is zero.

 The oxidation number of an ion is the same as the charge on the ion.

 The sum of the oxidation numbers of the atoms in a polyatomic ion

must be equal to the charge on the ion.
 Redox reactions
Rules for Specific Atoms or Periodic Table Groups

 Group IA elements are always +1

 Group Il A are always + 2.
 Hydrogen is usually +1 except in hydrides.
 Oxygen is usually -2, except in peroxides
 Group VII A elements are -1.
Redox reactions
Example:
0 0 + -

H2 + F2 2 HF

H2 F2
- Oxidized - Reduced
- Reducing agent - Oxidizing agent
Redox illustrations
Determine the oxidation number of each elements in these
compounds:
1. CaO (s)
2. KNO3 (s)
3. CaCO3 (s)

2 -2 1 5 -2 2 4 -2

CaO (s) KNO3 (s) CaCO3 (s)

1+ N + (-2x3)=0 2+ C + (-2x3)=0
N= 5 C= 4
Redox illustrations

Identify the reducing and oxidizing agent

0 0 +1 -1
2H2 + 02 H2O2

H2 is being oxidized, lose electron, reducing agent

O2 is reduced, gain electron, oxidizing agent
Balancing Redox Reactions

 Half-reaction method
1. Write the unbalanced equation for the reaction in ionic form.
2. Separate the equation into two half-reactions.
3. Balance each half-reaction for number and type of atoms and charges.
Balance the atoms other than O and H in each half-reaction separately.
4. For reactions in an acidic medium, add H2O and for basic medium, add OH-
to balance the O atoms and H+ to balance the H atom.
5. Add electrons on one side of each half-reaction to balance the charges. If
necessary, equalize the number of electrons in the two half-reactions by
multiplying one or both half-reactions by appropriate coefficients,
6. Add the two half-reactions and balance the final equation by inspection.
The electrons on both sides must cancel.
7. Verify that the equation contains the same type and numbers of atoms and
the same charges on both sides of the equation.
Balancing Redox Reactions

Use half reaction method to balance the

equation
Balancing Redox Reactions
Balancing Redox Reactions
Balancing Redox Reactions
Balancing Redox Reactions
Balancing Redox Reactions

Oxidation Number Method

1. Assign oxidation numbers to all elements in the reaction
2. From the changes in O.N., identify the oxidized and
reduced species
3. Compute the number of electrons lost in the oxidation and
gained in the reduction from the O.N. changes
4. Multiply one or both of these numbers by appropriate
factors to make the electrons lost equal the electrons
gained, and use the factors as balancing coefficients
5. Complete the balancing by inspection, adding states of
matter
Balancing Redox Reactions
Use oxidation number method to balance the equation:

0 1 6 -2 3 6 -2 0
Al(s) + H2SO4 (aq) Al2(SO4)3 (aq) + H2 (g)
Step 1: Assign oxidation number to all elements
Step 2: Identify oxidized and reduced species
(Al – oxidized , H2SO4- reduced)
Step 3: compute the e lost and e gained
(in oxidation: 3 e were lost from Al)
(in reduction: 1 e were gained by H)
Step 4: Multiply by factors to make e lost equal to electron gained, and use
the factors as coefficients
(Al lost 3e, so the 1e gained by H should be multiplied by 3. Put 3
coefficient H2SO4 and H2
Step 5. Complete the balancing by inspection
Electrochemical Cells
 Galvanic Cell – also called as Voltaic cells
– an apparatus that generates electricity using a
spontaneous chemical reaction
 Luigi Galvani and Alessandro Volta built the first versions of the
galvanic cell.
Anode – is the Cathode – is the
electrode at electrode at
which oxidation which reduction
occurs(lose e-) occurs (gain e-)

Zn and Cu
(Electrode)

Figure 2: Daniel cell

Galvanic Cells
 1. Daniel Cell – a galvanic cell where the spontaneous chemical reaction of the
oxidation of Zn to Zn2+ and the reduction of Cu2+ to Cu.
Zn electrode (anode): Zn(s)  Zn2+(aq) + 2e-
Cu electrode (cathode): Cu2+(aq) + 2e-  Cu(s)
Zn(s) + CuSO4(aq)Cu(s) + ZnSO4(aq)

 Salt bridge
– contains an inert electrolyte solution of KCL or NH4NO3
-is a conducting medium through which the cations and anions can move from
one electron compartment to the other.

The electrons flow eternally from the anode through the wire to the cathode. In
the solution, the cations (Zn2+, Cu2+, and K+) move towards the cathode, while the anions
(SO42- and Cl-) move toward the anode. The difference in electrical potential between
the electrodes creates an electric current.
 Galvanic Cells
2. Battery – is a galvanic cell, or a series of galvanic cells, that can be used
as a source of direct electric current at a constant voltage. It is self-
contained and requires no auxiliary components such as salt bridges.

Kinds of Battery
 Dry Cell Battery or Leclanché cell (Zinc-Carbon) – used in flashlights and
transistor radios
 Anode: Zinc can
 Cathode: Graphite
 Middle: Manganese dioxide and electrolyte paste of ZnCl2 and NH4Cl
 Anode: Zn(s) Zn2+(aq) +2e-
 Cathode 2NH4+(aq) + 2MnO2(s) + 2e- Mn2O3(s) + 2NH3(aq)+ H2O(l)
 Overall:
Zn(s)+2NH4(aq)+2MnO2(s)Zn2+(aq)+2NH3(aq)+H2O(l)+Mn2O3(s)

Figure 2: Leclanché cell

Galvanic Cells

Other Types of Battery

 Carbon-Zinc
 Alkaline (by Lewis Urry of Eveready in 1949)
 NiCd (Nickel-Cadmium) - rechargeable
 NiMH (Nickel-metal hydride) - rechargeable
 Li-ion Figure 3: Li-ion Battery
◦ Cathode: Li compound
◦ Anode: graphite
◦ LCO or LiCoO2 (Lithium-Cobalt oxide)
Anode (oxidation) : Li(s) Li+ + e-
Cathode (reduction) : Li+ + CoO2 + e- LiCoO2(s)
Li(s) + CoO2 LiCoO2(s)
Galvanic Cells
Other Types of Battery
 Li-ion
◦ LiFeS2 (Lithium Iron disulphide)
◦ LTC or LiSOCL2 (Lithium thionyl chloride) – used in horizontal drilling or fracking
◦ Li-M or LiMnO2 (Lithium-Manganese dioxide) – used in meter sensing, medical
devices, sensors and cameras.
◦ LiFeSO4 or LFP
◦ LiMnFePO4 or LMFP
◦ LiNiCoAlO2 or NCA
◦ LTO (Lithium-Titanate) or Li2TiO3 or Li4Ti5O12
◦ LiNiMnCoO2 (NMC, NCM, CNM,CMN, MNC, MCN)
The standard working voltage for AA batteries are: non-rechargeable =1.5V,
rechargeable=1.2V. Li-ion batteries can deliver 3V and higher. The US DOT and
Federal Aviation Administration restrict bulk shipments of primary Li-ion batteries on
passenger flights.
 Galvanic Cells
Other Types of Battery
Figure 4: Mercury Battery
 Mercury Battery – used in medicine and electronic industries.
Anode: Zn(Hg) + 2OH-(aq)  ZnO(s) + H2O(l) + 2e-
Cathode: HgO(s) + H2O(l) + 2e-  Hg(l) + 2OH-(aq)
Overall: Zn(Hg) + HgO(s)  ZnO(s) + Hg(l)

 Lead-acid battery – used in automobiles; rechargeable

Anode: Pb(s) + SO42-(aq)  PbSO4(s) + 2e-
Figure 5: Lead-acid
Battery Cathode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e-  PbSO4(s) + 2H2o(l)
Overall:Pb(s)+PbO2(s)+ 4H+(aq) + 2SO42-(aq) 2PbSO4(s)+2H2O(l)
Galvanic Cells
Other Types of Battery
 Fuel Cells – requires a continuous supply of reactants to keep
functioning.
Anode: 2H2(g) + 4OH-(aq)  4H2O(l) + 4e-
Cathode: O2(g) + 2H2O(l) + 4e-  4OH-(aq)
Overall: 2H2(g) + O2(g)  2H2O(l)

Figure 6: Fuel Cell

Electrode Potentials and Cell EMF
 Electromotive force or emf (E) – is the voltage across the electrodes of a
galvanic cell or by varying magnetic fields.

 It is also referred as cell voltage or cell potential. It is dependent on the

nature of electrons, concentrations and temperature.

 Cell diagram – is the conventional notation for representing galvanic

cells.
Anode Cathode
Cell diagram of a Daniel cell: Zn(s) l Zn2+(1M) ll Cu2+(1M) l Cu(s)

*The single vertical lines represent a phase boundary while the double vertical
line represents the salt bridge.
 Electrode Potentials and Cell EMF
 Standard Reduction Potential –
denoted with (°), is the voltage associated with a
reduction reaction at an electrode when all solutes are 1M and all gases are
at 1atm.

Table 1: Standard Reduction Potentials at 25°C

Sample problems

Example 1: Compute for the E°cell for a Daniel cell under steady-
state conditions and at 25°C:
Zn electrode (anode): Zn(s)  Zn2+(1M) + 2e-
Cu electrode (cathode): Cu2+(1M) + 2e-  Cu(s)
Zn(s)+CuSO4 (1M) ZnSO4(1M) + Cu(s)

E°cell = E°cathode – E°anode

= E°Cu2+/Cu – E°Zn2+/Zn
= 0.34 V – (-0.76 V)
= 1.10 V
Sample problems

Example 2: Compute for the E°cell under steady-state conditions and at 25°C
for:
Zn(s) l Zn2+(1M) ll H+ (1M) l H2(1atm) l Pt(s)

Anode (oxidation): Zn(s)  Zn2+(1M) +2e-

Cathode (reduction): 2H+(1M) + 2e-  H2(1atm) _______________
Zn(s)+ 2H+(1M)  Zn2+(1M) + H2(1atm)

E°cell = E°cathode – E°anode

= E°H+/H2 – E°Zn2+/Zn
= 0 V – (-0.76 V)
= 0.76 V
Sample problems

 Example 3: Compute for the E°cell under steady-state conditions and at

25°C for:
Pt(s) l H2(1atm) l H+(1M) ll Cu2+(1M) l Cu(s)

Anode (oxidation): H2(1atm) 2H+(1M) + 2e-

Cathode (reduction): Cu2+ (1M) +2e-  Cu(s)___________
Overall: H2(1atm) + Cu2+(1M)  2H+(1M) + Cu(s)

E°cell = E°cathode – E°anode

= E°Cu2+/Cu - E°H+/H2
= 0.34 V – 0 V
= 0.34 V
Gibbs Energy and Spontaneity of Reactions

Gibb’s Free Energy (G) – formulated by Joshia Willard Gibbs, is an

equation used to predict the spontaneity of reactions.
- is the amount of useful work that can be obtained in a reaction

Electrical energy – is the product of the emf of the cell and the
total electrical charge that passes through the cell.

 Electrical energy = coulombs * volts = joules

 Total charge = number of e- * charge of 1e-
Gibbs Energy and Spontaneity of Reactions

Faraday’s constant (F)– is the charge of 1 mole of electrons;

 1F = 6.022 E23 e-/mol e- * 1.602 E-19 C/e = 9.647 E4 C/mol
Total charge = nF
 1 Faraday (F) = (6.022 E23 e-/mol e-) * (1.602 E-19 C/e-) = 9.647 E4
C/mol e-

Ecell = maximum voltage the cell can achieve

Wmax = electrical work done
𝑤𝑚𝑎𝑥 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
Gibbs Energy and Spontaneity of Reactions

ΔG = change in free energy. When T=298K,

∆𝐺 = 𝑤𝑚𝑎𝑥 𝐽
(8.314 )(298𝐾)
∆𝐺 = − 𝑛𝐹𝐸𝑐𝑒𝑙𝑙 𝐸°𝑐𝑒𝑙𝑙 = 𝐾 ∗ 𝑚𝑜𝑙 𝑙𝑛𝐾
∆𝐺° = − 𝑛𝐹𝐸°𝑐𝑒𝑙𝑙 𝐽
𝑛(96500 )
∆𝐺° = − 𝑅𝑇 𝑙𝑛𝐾 𝑉 ∗ 𝑚𝑜𝑙
Solving for 𝐸°𝑐𝑒𝑙𝑙 , 0.0257 𝑉
− 𝑛𝐹𝐸°𝑐𝑒𝑙𝑙 = − 𝑅𝑇 𝑙𝑛𝐾 𝐸°𝑐𝑒𝑙𝑙 = 𝑙𝑛𝐾
𝑛
𝑅𝑇 0.0592 𝑉
𝐸°𝑐𝑒𝑙𝑙 = 𝑙𝑛𝐾 𝐸°𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔𝐾
𝑛𝐹 𝑛

K = equilibrium constant
Gibbs Energy and Spontaneity of Reactions

Under Standard Steady-State Conditions

∆𝑮° K 𝑬°𝒄𝒆𝒍𝒍 Reaction
Negative >1 Positive Favors formation of products.
0 =1 0 Reactants and products are equally
favored.
Positive <1 Negative Favors formation of reactants.
Sample problem
1. Calculate the equilibrium constant for the following reaction at 25°C:
Fe2+(aq) + 2Ag(s) Fe(s) + 2Ag+(aq)

Anode (oxidation): 2Ag(s)  2Ag+(aq) +2e-

0.0257 𝑉
Cathode (reduction): Fe2+(aq) +2e-  Fe(s) 𝐸°𝑐𝑒𝑙𝑙 = 𝑙𝑛𝐾
𝑛

E°cell = E°cathode – E°anode

𝑛𝐸°𝑐𝑒𝑙𝑙
= E°Fe2+/Fe - E°Ag+/Ag 𝑙𝑛𝐾 =
0.0257 𝑉
= - 0.44 V – (0.80 V) 2 −1.24𝑉
E°cell = -1.24 V 𝑙𝑛𝐾 = = −96.4981
0.0257 𝑉
𝐾 = 𝑒 −96.4981

𝑲 = 𝟏. 𝟐𝟑 ∗ 𝟏𝟎−𝟒𝟐
Sample problem

2. Calculate ΔG for the following reaction at 25°C.

2Al3+(aq) + 3Mg(s) 2Al(s) + 3Mg2+(aq)

Anode (oxidation): 3Mg(s)  3Mg2+(aq) + 6e-

Cathode (reduction): 2Al3+(aq) + 6e-  2Al(s)

E°cell = E°cathode – E°anode

= E°Al3+/Al - E°Mg2+/Mg
= - 1.66 V – (-2.37 V)
E°cell = 0.71 V

∆𝐺° = − 𝑛𝐹𝐸°𝑐𝑒𝑙𝑙
𝑘𝐽
∆𝐺° = −(6)(96.5 )(0.71)
𝑉 ∗ 𝑚𝑜𝑙
∆𝑮° = 𝟒. 𝟏𝟏 ∗ 𝟏𝟎𝟐 𝒌𝑱
Nernst Equation
Nernst Equation – is a formula by Walther Nerst that relates the
electromotive force of an electrochemical cell to the
concentrations of the species in the solution.
Consider a redox reaction of the type
aA + bB  cC + dD
From equation: ∆𝐺 = ∆𝐺° + 𝑅𝑇 𝑙𝑛𝑄
Where:
 ∆𝐺 = 𝐺𝑖𝑏𝑏𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
 ∆𝐺° = 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐺𝑖𝑏𝑏𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
𝐽
 𝑅 = 𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑎𝑙 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑖𝑛 𝑚𝑜𝑙∗𝐾
 𝑇 = 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑖𝑛 𝐾
 𝑄 = 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑞𝑢𝑜𝑡𝑖𝑒𝑛𝑡 [𝐶]𝑐 [𝐷]𝑑
 𝐹 = 𝐹𝑎𝑟𝑎𝑑𝑎𝑦 ′ 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑄=
[𝐴]𝑎 [𝐵]𝑏
Nernst Equation
Since ∆𝐺 = −𝑛𝐹𝐸 and ∆𝐺° = −𝑛𝐹𝐸° + 𝑅𝑇 𝑙𝑛𝑄,
−𝑛𝐹𝐸 = −𝑛𝐹𝐸° + 𝑅𝑇 𝑙𝑛𝑄
𝑅𝑇
The Nernst equation is: 𝐸 = 𝐸° − ln 𝑄
𝑛𝐹

0.0257
𝐸 = 𝐸° − ln 𝑄
𝑛

0.0592
𝐸 = 𝐸° − log 𝑄
𝑛
 Electrons flow from the anode to the cathode resulting in reactant
consumption (decrease in concentration) and product formation.
 When Q increases, E decreases.
 When the cell reached equilibrium, there is no net transfer of
electrons so E = 0 and Q = K where K is the equilibrium constant.
Sample problem
Problem 1: Predict whether the following reaction would proceed spontaneously as
written at 298K:
Co(s) + Fe2+(aq)  Co2+(aq) + Fe(s)
given that [Co2+] = 0.5M and [Fe2+] = 0.68M.

Anode (oxidation): Co(s)  Co2+(aq) + 2e-

Cathode (reduction): Fe2+(aq) + 2e-  Fe(s)

0.0257
E°cell = E°cathode – E°anode 𝐸 = 𝐸° − ln 𝑄
𝑛
= E°Fe2+/Fe - E°Co2+/Co 0.0257 𝑉 [𝐶𝑜 2+ ]
𝐸 = −0.16 𝑉 − ln
= - 0.44 V – (-0.28 V) 2 [𝐹𝑒 2+ ]
E°cell = - 0.16 V 0.0257 𝑉 [0.15]
𝐸 = −0.16 𝑉 − ln
2 [0.68]

𝐸 = −0.16 𝑉 + 0.019 V = −𝟎. 𝟏𝟒𝟏 𝑽

Thus, the reaction is not spontaneous in the direction written.

Sample problem
Problem 2: What is the ratio of [Co2+] to [Fe2+] in the previous
problem (Problem 1) to make it spontaneous?
0.0257
𝐸 = 𝐸° − ln 𝑄
𝑛

0.0257 𝑉 [𝐶𝑜2+ ]
𝐸 = −0.16 𝑉 − ln
2 [𝐹𝑒 2+ ]
[𝐶𝑜2+ ]
ln 2+ = −12.5
[𝐹𝑒 ]

[𝐶𝑜2+ ]
2+ = 𝑒 −12.5
[𝐹𝑒 ]

[𝑪𝒐𝟐+ ]
𝟐+
= 𝟒 ∗ 𝟏𝟎−𝟔
[𝑭𝒆 ]
Concentration Cells
Concentration cells – a galvanic cell from two half-cells composed of the
same material but differing in ion concentrations.

Zn(s) l Zn2+(0.10M) ll Zn2+(1.0M) l Zn(s)

Anode (oxidation): Zn(s)  Zn2+(0.10M) + 2e-

Cathode (reduction): Zn2+(1.0M) + 2e-  Zn(s)_____________
Zn2+(1.0M)  Zn2+(0.10M)

0.0257 𝑉 [𝑍𝑛2+ ]𝑙𝑜𝑤

𝐸 = 𝐸° − ln
2 [𝑍𝑛2+ ]ℎ𝑖𝑔ℎ

0.0257 𝑉 0.10
𝐸 =0− ln
2 1.0

𝑬 = 𝟎. 𝟎𝟐𝟗𝟔 𝑽
Electrolysis
Electrolysis – is the process of using electrical energy to cause a
nonspontaneous reaction to occur in an electrolytic cell.

 Electrolysis of Molten Sodium Chloride (Downs cell) – major

source of pure Na and Cl2.
Anode (oxidation): 2Cl-(l)  Cl2(g) + 2e-
Cathode (reduction: 2Na+(l) + 2e-  2Na(l)________
Overall: 2Na+(l) + 2Cl-(l) 2Na(l) + Cl2(g)
Electrolysis

Electrolysis of Water
Anode (oxidation): 2H2O(l)  O2(g) + 4H+(aq) + 4e-
Cathode (reduction): 4[ H+(aq) + e-  0.5 H2(g)]____________
Overall: 2H2O(l)  2H2(g) + O2(g)

ΔG = 474.4 kJ/mol
Faraday’s Laws of Electrolysis
 First Law: The amount of chemical reaction which occurs at
any electrode during electrolysis by a current is directly
proportional to the quantity of electricity passed though the
electrolyte.
 Second Law: The amounts of different substances liberated by
the same quantity of electricity passing through the
electrolytic solution are proportional to their chemical
equivalent and weights (Atomic Mass of Metal ÷ Number of
electrons required to reduce the cation.)
𝑄 = 𝐼𝑡
where Q = charge in Coulombs
I = current in ampere
t = time in seconds
Sample problem
A solution of CuSO4 is electrolysed for 10mins with a current of
1.5A. What is the mass of copper deposited at the cathode?

Solution: t = 10mins = 600s; I = 1.5A

𝑄 = 𝐼𝑡 = 1.5 𝐴 ∗ 600𝑠 = 900 𝐶
According to the reaction: Cu2+(l) + 2e- = Cu, we require
2F or 2 96487C to deposit 1 mol or 63g of Cu. Thus,
the mass of Cu deposited at the cathode is
63 𝑔
∗900 𝐶
= 𝑚𝑜𝑙
96487 𝐶 = 0.2938 𝑔.
2∗
𝑚𝑜𝑙