Recap on Electrochemistry

Excerpts taken from Chemistry: the Nature of Atoms, Author Silberberg.

 Assigning Oxidation Numbers
Oxidation
number, also
called oxidation
state, the total
number of
electrons that an
atom either gains
or loses in order to
form a chemical
bond with another
atom
 Assigning Oxidation Numbers

Rule 1. The oxidation number of an element in its free (uncombined) state is

zero — for example, Al(s) or Zn(s).

This is also true for elements found in nature as diatomic (two-atom)

elements such as I2, Cl2, F2, Br2, N2, H2, O2, and for sulfur found as S8.

Rule 2. Group 1 metals are always +1.

Rule 3. Group 2 metals are always +2.

 Assigning Oxidation Numbers

• Oxidation number, Ne
also called oxidation
state, the total number
of electrons that an
atom either gains or
loses in order to form a
chemical bond with
another atom

Symbols and periodic table locations of some monatomic ions

11Na: [10Ne] 3s1

17Cl: [10Ne] 3s2 3p5

 Assigning Oxidation Numbers

Rule 4. Fluorine is always -1. Chlorine, bromine, and iodine usually have an
oxidation number of -1, unless they’re in combination with oxygen
or fluorine.

Rule 5. Oxygen almost always has an oxidation number of -2, except in

peroxides such as H2O2 (when it is -1) and in OF2 (when it is +2).

Rule 6. The oxidation state of hydrogen in a compound is usually +1. If the

hydrogen is part of a binary metal hydride (compound of hydrogen
and some metal), then the oxidation state of hydrogen is -1.
 Assigning Oxidation Numbers

Rule 7. The sum of the oxidation numbers of all the atoms in a compound is
zero.

Determine the oxidation number of the underlined element.

CuO KMnO4 MnO2

𝑥 + −2 = 0 1 + 𝑥 + 4 −2 = 0 𝑥 + 2 −2 = 0

𝑥 = +2 𝑥 = +7 𝑥 = +4
 Assigning Oxidation Numbers

Rule 8. The sum of the oxidation numbers of all the atoms in a polyatomic
ion is the charge of the ion.

Determine the oxidation number of the underlined element.

-2 ‒ 2‒
SO4 MnO4 Cr2O7
𝑥 + 4 −2 = −2 𝑥 + 4 −2 = −1 2𝑥 + 7 −2 = −2

𝑥 = +6 𝑥 = +7 2𝑥 = +12

𝑥 = +6
 Learning Check

What is the oxidation number of the underlined element?

PbO2 PbO Pb

𝑥 + 2 −2 = 0 𝑥 + −2 = 0 𝑥 =0

𝑥 = +4 𝑥 = +2 Oxidation number is zero in

elemental state.

• The oxidation number determines how many electrons can be transferred

between compounds.
 Learning Check

What is the oxidation number of the underlined element?

Al2O3 Li2O CrO2

𝑥 = +3 𝑥 = +1 𝑥 + 2(−2) = +4
𝑥 = +4

• The oxidation number determines how many electrons can be transferred

between compounds.
 Fundamentals of Electrochemistry
Redox reaction involves transfer of electrons from one species to another.

0 +2 -2 +2 0 OIL RIG
Fe + CuSO4 → FeSO4 + Cu
oxidation
LEO GER
reduction

Oxidation – Loss of electrons; increase in oxidation number

Reduction – Gain of electrons; decrease in oxidation number

Reducing Agent: Fe
• the reactant that loses electrons (is oxidized)

Oxidizing agent: CuSO4

• the reactant that gains electrons (is reduced)
Your Acronyms
 Fundamentals of Electrochemistry

Redox reaction involves transfer of electrons from one species to another.

0 +2 +3 0 Balancing Redox reactions
Al + Cu2+ → Al3+ + Cu
Step 1. Write 'skeleton' half-equations
oxidation
reduction Step 2. Balance each half equation
'atomically' in this order.
• atoms other than H and O
oxidation Al → Al3+ + 3e– × 2 • O atoms by adding H2O with the
appropriate coefficient
reduction 3× 2e– + Cu2+ → Cu • H atoms by adding H+ with the
appropriate coefficient
2Al + 3Cu2+ → 2Al3+ + 3Cu Step 3. Balance each half equation
Reducing Oxidizing 'electrically’.
Agent Agent
Step 4. Add the two half-reactions together
and simplify if necessary
 Fundamentals of Electrochemistry
Balance the following reaction in acidic medium:
Balancing Redox reactions
MnO4‒ + I‒ → I2 + MnO2
OA RA Step 1. Write 'skeleton' half-equations

reduction 2 3e‒ + 4H+ + MnO4‒ → MnO2 + 2H2O Step 2. Balance each half equation 'atomically' in
this order.
oxidation 3 2 I‒ → I2 + 2e‒ • atoms other than H and O
8H+ + 2MnO4‒ + 6I‒ → 2MnO2 + 4H2O + 3I 2 • O atoms by adding H2O with the
appropriate coefficient
• H atoms by adding H+ with the
Balance above reaction in basic medium: appropriate coefficient

Step 3. Balance each half equation 'electrically’.

8OH‒ + 8H+ + 2MnO4‒ + 6I‒ → 2MnO2 + 4H2O + 3I2 + 8OH‒
Step 4. Add the two half-reactions together and
+ 8H2O simplify if necessary

4H2O + 2MnO4‒ + 6I‒ → 2MnO2 + 3I2 + 8OH‒ Step 5. Change from an acidic to a basic medium
by adding OH‒ to both sides of the net equation;
combine H+ and OH– to form H2O and simplify.
Drill 1: Balancing Redox Equations
Instructions: Submit your answers in the submission portal in Elearn. For students whose
surnames begin with the letters A-M, Please answer items (a) & ( c), students whose
surnames start with N-Z, answer items (b) and (d).
Redox Reactions and
Electrochemistry

• Electrochemistry is a branch of
chemistry that deals with the flow of
electricity by chemical reactions

• An electrochemical cell is a device

that can generate electrical energy
from the chemical reactions
occurring in it, or use the electrical
energy supplied to it to facilitate
chemical reactions in it.
 Two Types of Electrochemical Cells
1. Galvanic Cell or Voltaic Cell - is an electrochemical cell that uses a chemical reaction
to produce electrical energy.

• spontaneous chemical reactions

• e.g. battery

Zn + Cu2+ → Cu + Zn2+ E° = + 1.10 V

 Two Types of Electrochemical Cells

2.Electrolytic Cell - uses electrical energy to force a chemical reaction to happen that
would not otherwise occur

• Requires electric current to drive a non-spontaneous reaction

• (DC power source)

Zn2+ + Cu → Zn + Cu2+ E° = - 1.10 V

An electrochemical cell can be either voltaic or electrolytic. In an
electrochemical cell, oxidation occurs at the anode and reduction at
the cathode.

Red Cat An Ox
Reduction at Oxidation at the
the Cathode Anode
 Parts of the voltaic or galvanic cell
Anode – is the electrode where oxidation occurs
• After a period of time, the anode may appear to become smaller as it falls into solution.

Cathode – is the electrode where reduction occurs

• After a period, it may appear larger, due to ions from solution plating onto it.

Salt bridge – is the chamber of electrolytes necessary to complete the circuit in a voltaic cell.
• a device used to maintain electrical neutrality

External circuit – is used to conduct the flow of electrons between the electrodes of the voltaic cell and
usually includes a load.

Load – is the part of the circuit which utilizes the flow of electrons to perform some function.

Electron Flow - always from anode to cathode (through the wire)

 Zn + Cu2+ → Cu + Zn2+ E° = + 1.10 V
Voltaic Cell
Anode -oxidation Cathode -reduction
takes place takes place

e- e- e- e-

e-
e-
- e- +
e-

e- Cu2+ + 2e– Cu
Zn Zn2+ + 2e- e-
e- Electrons
Electrons
needed
released
here by here for
oxidation reduction

ZnSO4 solution CuSO4 solution

Electrons flow from the anode (- electrode) to the cathode (+ electrode) through the wire in a voltaic cell.
 Cell Diagram
The cell diagram (or cell notation) is a shorthand notation to represent the redox reactions
of an electrical cell.
Zn + Cu2+ →Cu + Zn2+ E° = + 1.10 V

anode │ anode solution cathode solution │ cathode

Zn (s)│ Zn2+ (aq) Cu2+ (aq) │Cu (s)

anode salt bridge cathode

Convention: e-
V

• Double vertical line - represents the salt bridge e-

Zn Cu
• Single vertical line | - is used to separate different states of
matter on the same side, and a comma is used to separate
Zn2+ Cu2+
like states of matter on the same side. NO3–
NO3–
 Cell Potential
Cell potential or Electromotive force (EMF):
• is the measure of the potential difference e-
V

between two half cells in an electrochemical cell e-

Zn Cu

work or electrical potential energy J

𝐸𝑐𝑒𝑙𝑙 = = = 𝑉
unit of charge moved C Zn2+
NO3–
Cu2+
NO3–

• The potential difference is measured in units of volts.

• One volt (V) is the potential difference necessary to generate a charge of 1

coulomb (C) from 1 joule (J) of energy.
 Standard cell potential (E°cell)

Standard cell potential (E°cell) - is the potential difference between the cathode and anode.

𝐸°𝑐𝑒𝑙𝑙 =
𝐸° 𝑟𝑒𝑑 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸° 𝑟𝑒𝑑 𝑎𝑛𝑜𝑑𝑒

e-
where: V

e-

• 𝐸°𝑐𝑒𝑙𝑙 - the overall cell potential at standard conditions (1 M, 1 atm, Zn Cu

and 298 K)

• 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 - the standard reduction potential for the reduction half

Zn2+ Cu2+
reaction occurring at the cathode NO3–
NO3–

• 𝐸°𝑎𝑛𝑜𝑑𝑒 - the standard reduction potential for the oxidation half

reaction occurring at the anode
 Standard reduction potential (E°)

• The standard reduction potential is defined relative to a standard hydrogen electrode

(SHE) reference electrode, which is arbitrarily given a potential of 0.00 volts.

Standard Hydrogen Electrode (S.H.E)

2H+ (aq, 1 M) + 2e– → H2 (g, 1 atm) E°1/2(SHE) = 0 V

Standard thermodynamic conditions:

• Temperature: 25 °𝐶
• 𝑃𝐻2 = 1 𝑎𝑡𝑚
• [𝐻+] = 1 𝑀
 Standard reduction potential (E°)
• The standard electrode potential is a relative
quantity in the sense that it is the potential of an
Standard Potentials for Selected
electrochemical cell in which the reference electrode Reduction Half-Reactions at 25 °C
(left-hand electrode) is the standard hydrogen
electrode, whose potential has been assigned the
value of 0.000 V.

• The standard electrode potential for a half-reaction

refers exclusively to a reduction reaction.

Zn+2 + 2e– → Zn 𝐸° = −0.76 𝑉

• A positive electrode potential indicates that the

half-reaction in question is spontaneous with
respect to SHE.
 Standard reduction potential (E°)
Standard Potentials for Selected
Reduction Half-Reactions at 25 °C
• Reduction potential -
measures the tendency
of a molecule to be
reduced by taking up new
electrons

Oxidizing power Reducing power

increases increases

• The more positive the reduction potential means the stronger the oxidizing agent, and the more readily it
can accept electrons.
o F2 is the strongest oxidizing agent

• The more negative the reduction potential, the stronger the reducing agent, and the more readily it can
give up electrons.
o Li is the strongest reducing agent
 Standard reduction potential (E°)

• If in constructing an electrochemical cell, you need to write

the reaction as an oxidation instead of a reduction, the sign Standard Potentials for Selected
of the half cell potential changes. Reduction Half-Reactions at 25 °C

Zn+2 + 2e– → Zn 𝐸° = −0.76 𝑉

Zn → Zn+2 + 2e– 𝐸° = +0.76 𝑉

• The standard electrode potential is independent of the

number of moles of reactant and product shown in the
balanced half reaction. Electrode potentials are intensive
variables.

Zn+2 + 2e– → Zn 𝐸° = −0.76 𝑉

2Zn+2 + 4e– → 2Zn 𝐸° = −0.76 𝑉

The electrode potential for the above reaction is still -0.76 V

though it is multiplied by a coefficient of 2.
 Standard cell potential (E°cell)

What is the standard cell potential, E°cell of the reaction:

Zn + Cu2+ ⮀ Cu + Zn2+
Standard Potentials for Selected
Reduction Half-Reactions at 25 °C
𝐸°𝑐𝑒𝑙𝑙 =
𝐸° 𝑟𝑒𝑑 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸° 𝑟𝑒𝑑 𝑎𝑛𝑜𝑑𝑒

cathode Cu2+ (aq) + e– → Cu (s) 𝐸° = + 0.34 𝑉

anode Zn2+ (aq) + 2e– → Zn(s) 𝐸° = − 0.76 𝑉

𝐸° 𝑐𝑒𝑙𝑙 = 0.34 𝑉 – (−0.76 𝑉)

𝐸°𝑐𝑒𝑙𝑙 = + 1.10 𝑉
 Standard cell potential (E°cell)

What is the standard cell potential, E°cell of the reaction: Standard Potentials for Selected
Reduction Half-Reactions at 25 °C
Zn + Cu2+ ⮀ Cu + Zn2+
Note that the standard cell potential can also be written as a
sum rather than a difference:

𝐸°𝑐𝑒𝑙𝑙 =
𝐸° 𝑟𝑒𝑑 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 + 𝐸° 𝑜𝑥 𝑎𝑛𝑜𝑑𝑒

cathode Cu2+ (aq) + e– → Cu (s) 𝐸° = + 0.34 𝑉

anode Zn(s) → Zn2+ (aq) + 2e–
𝐸° 𝑐𝑒𝑙𝑙 = 0.34 𝑉 + 0.76 𝑉
𝐸°𝑐𝑒𝑙𝑙 = + 1.10 𝑉
𝐸° = + 0.76 𝑉
Note that the standard cell potential can also be
written as a sum rather than a difference where
we have switched our strategy from taking the
difference between two reduction potentials
(which are traditionally what one finds in
reference tables) to taking the sum of the
oxidation potential and the reduction potential
(which are the reactions that actually occur).
Use whichever you find simpler.
Drill 2: Standard Potentials
For the cell: Ni | Ni2+ Cu2+ | Cu
a. write the overall balanced redox equation
b. calculate the standard cell potential
Ni | Ni2+ Cu2+ | Cu
 Non-standard state cell potentials

• The Nernst equation allows the cell potential to be determined other than the
standard conditions of 1 M, 1 atmosphere, and 25 °C.
• The effects of different temperatures and concentrations may be tracked in terms of
the Gibbs free energy change, ΔG. Merging electrochemistry with thermodynamics
generates the formula:
where:
Δ𝐺 = −𝑛𝐹𝐸 n = no. of moles of electrons
F = Faraday's constant (96,485 C/mole e–)
E = potential difference
Under standard conditions:

Δ𝐺° = −𝑛𝐹𝐸°
 Non-standard state cell potentials
From thermodynamics, the Gibbs energy change under non-standard conditions can be related to the
Gibbs energy change under standard equations via:

∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝑄

Substituting ΔG = −nFE and ΔG° = −nFE°, we have:

−𝑛𝐹𝐸 = −𝑛𝐹𝐸° + 𝑅𝑇 ln 𝑄

Divide both sides by −nF to obtain the Nernst equation:

where:
𝐸𝑐𝑒𝑙𝑙 = cell potential at non-standard state conditions
𝑅𝑇 𝐸° 𝑐𝑒𝑙𝑙 = standard state cell potential
𝐸 = 𝐸° − 𝑙𝑛𝑄 𝑅 = ideal gas constant (8.31 J/mole K)
𝑛𝐹
𝑇 = absolute temperature (in Kelvin scale)
𝑄 = reaction quotient for the reaction: aA + bB → cC + dD, is

𝐷𝑑 𝐶𝑐
𝑄 =
𝐴𝑎 𝐵𝑏
 Non-standard state cell potentials
𝑅𝑇
𝐸 = 𝐸° − 𝑙𝑛𝑄
𝑛𝐹

The Nernst equation is more commonly written in base-10 log form (ln =
𝑛𝑎𝑡𝑢𝑟𝑎𝑙 𝑙𝑜𝑔𝑎𝑟𝑖𝑡ℎ𝑚 = 2.303 log ).

2.303𝑅𝑇
𝐸 = 𝐸° − 𝑙𝑜𝑔𝑄
𝑛𝐹

2.303𝑅𝑇
At standard temperature (𝑇 = 298 𝐾): = 0.0592
𝐹

0.0592
𝐸 = 𝐸° − 𝑙𝑜𝑔𝑄 Nernst equation
𝑛
 Non-standard state cell potentials
At equilibrium, the reaction quotient 𝑄 = 𝐾𝑒𝑞 𝐸 = 0
0.0592
0 = 𝐸° − 𝑙𝑜𝑔𝐾𝑒𝑞
𝑛
This can be rearranged into:

0.0592
𝐸° = 𝑙𝑜𝑔 𝐾𝑒𝑞
𝑛
or aA + bB → cC + dD
𝑛𝐸°
log 𝐾𝑒𝑞 =
0.0592 𝐷𝑑 𝐶 𝑐
𝐾𝑒𝑞 =
Keq is proportional to the standard potential of the reaction. 𝐴𝑎 𝐵 𝑏

K > 1, E° > 0 : reaction favours formation of the products.

K < 1, E° < 0 : reaction favours formation of the reactants. Le Chatelier’s Principle
Drill 3
1. For the cell: Ag|Ag+ (0.1544 M) H+ (0.0794 M) │ O2 (1.12 atm) | Pt
anode cathode
a. Calculate the theoretical cell potential and identify whether the cell, as written, is galvanic or
electrolytic.

b. Calculate the free energy change, ∆G

Ag+ + 1e– → Ag E° = +0.80 V

O2 (g) + 4H+ + 4e– → 2H2O (l) E° = +1.23 V

𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 – 𝐸°𝑎𝑛𝑜𝑑𝑒

𝐸°𝑐𝑒𝑙𝑙 = 1.23 𝑉 – 0.80 𝑉

𝑬°𝒄𝒆𝒍𝒍 = 𝟎. 𝟒𝟑 𝑽
Drill 3
3.