ELECTROCHEMISTRY

Thermodynamics has many applications other than expanding gases inside steam
engines. One of the most important areas of applied thermodynamics is
ELECTROCHEMISTRY.

Electrochemistry is an area of chemistry that deals with the inter-conversion of

electrical energy and chemical energy. It is typically investigated through the use of
electrochemical cells, systems that incorporate a redox reaction to produce or utilize electrical
energy.

There are two types of electrochemical cells:

• One type of cell does work by releasing free energy from a spontaneous reaction (∆G
< 0) to produce electricity. A battery houses this type of cell (Voltaic or galvanic cell)
• The other type of cell does work by absorbing free energy from a source of electricity
to drive a nonspontaneous (∆G > 0). (Electrolytic cells).

Redox Reactions and Electrochemical Cells

Electrochemical processes are redox (oxidation-reduction) reactions in which the energy

released by a spontaneous reaction is (converted to electricity in which electricity is used to
drive a nonspontaneous chemical reaction (electrolysis) to redox reactions, electrons are
transferred from one substance to another.

The reaction between zinc metal and sulfur is an example of a redox reaction:
0 0 +2 -2
Zn + S → ZnS
RA OA

GEROA (Gain Electron, Reduction, Oxidizing Agent)

LEORA (Loss Electron, Oxidation, Reducing Agent)

Recall that the numbers above the elements are the oxidation numbers of the elements.
By assigning an oxidation number to each atom, we can see which species was oxidized and
which reduced and, from that, which is the oxidizing agent and which is the reducing agent.
The loss of electrons by an element during oxidation is marked by an increase in the element's
oxidation number. In reduction, there is decrease in oxidation number resulting from a gain of
electrons by an element. In the preceding reaction Zn metal is oxidized and S is reduced. Keep
in mind three key points:

• 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.
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 • Redox reaction can be defined as one in which the oxidation numbers of the species
change.

Rules for Assigning an Oxidation Number (O.N.)

1. The oxidation number of an element in the free or uncombined state is always zero
(including
2. The algebraic sum of the oxidation numbers of all the atoms in the formula of a
compound is zero.
3. The oxidation number of an ion is the same as the charge on the ion.
4. The sum of the oxidation numbers of the atoms in a polyatomic ion must be equal to
the charge on the ion.

Rules for Specific Atoms or Periodic Table Groups

1. Group IA elements are always +1
2. Group Il A are always + 2.
3. Hydrogen is usually +1 except in hydrides.
4. Oxygen is usually -2, except in peroxides
5. Group VII A elements are -1.

GEROA (Gain Electron, Reduction, Oxidizing Agent)

LEORA (Loss Electron, Oxidation, Reducing Agent)

Example:

Use oxidation numbers to decide which of the following are redox reactions. For redox
reaction, identify the species that undergo the reduction and oxidation reaction; and the
oxidizing and reducing agent.
x + 2(-2) = 0; x + 3(-2) = -2;
x =+4 x = +4
+2 -2 +4 -2 +2 -2 +4 -2
1. CaO(s) + CO2 (g) → CaCO3(s) not redox reaction CO3

x + 3(-2) = -1;
+1 +5 -2 x=5
+1 -1 +1 -2 0 0 +5 -2
2. 4KNO3(s) → 2K2O(s) + 2N2(g) + 5O2 (g) redox reaction NO3
OA RA

Balancing Redox Reactions

We balance a redox reaction by making sure that the number of electrons lost by the
reducing agent equals the number of electrons gained by the oxidizing agent. There are two
methods used to balance redox equations: the oxidation number method and the half-reaction

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method — but only the second method will be discussed in this section. The following steps
are used in balancing a redox reaction by the 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 to balance the O atoms and H+ to balance
the H atom.
5. Add electrons (e-) 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.

Example:

1. Balance the equation showing the oxidation of Fe+2 ions to Fe+3 ions by dichromate ions in
an acidic medium. The dichromate ions are reduced to Cr3+ ions.

Step 1) Fe+2 + Cr2O7-2→Fe+3 + Cr+3

Step 2 - 3) Fe+2 →Fe+3

Cr2O7-2→ 2Cr+3

Step 4) Cr2O7-2 + 14H+→ 2Cr+3 + 7H2O

2x + 7(-2) = -2;
x=6
Step 5) Fe+2 →Fe +3
+6 -2
+ e- 6Fe+2
→6Fe+3 + 6e-
+1 -2 +6 -2
6e- + Cr2O7-2 + 14H+→ 2Cr+3 + 7H2O Cr2O7-2
(-2 + 14(+1) = 12) (2(3) + 7(2)(1) + 7(-2) = 6)
(2(6) + 7(-2)+ 14(+1) = 12)

Step 6) 6Fe+2 →6Fe+3 + 6e- Oxidation

6e + Cr2O7 + 14H+→ 2Cr+3 + 7H2O
- -2
Reduction
6Fe+2+ Cr2O7-2 + 14H+→ 6Fe+3 + 2Cr+3 + 7H2O Overall Reaction

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Electrochemical Cells

Electrochemical cell is the experimental apparatus for generating electricity through

the use of a spontaneous redox reaction (∆G < 0). An electrochemical cell is sometimes
referred to as a galvanic cell or voltaic cell, after tile scientists Luigi Galvani and Alessandro
Volta, who constructed early version of this device.
The separation of half-reactions is the essential idea behind a voltaic ceil. The
components of each half-reaction are placed in a separate container, or half-cell, which consist
of one electrode dipping into an electrolyte solution. The two half-cells are joined by the
circuit, which consists of a wire and a salt bridge (the inverted U tube in the figure). In order
to measure the voltage generated by the cell, a voltmeter is inserted in the path of the wire
connecting the electrodes. A switch closes or opens the circuit. The oxidation half-cell (anode
compartment) is shown on the left and the reduction half-cell (cathode compartment) on the
right.

Here are the key points about the Zn/Cu2+ voltaic cell:

1. The oxidation half-cell. The anode compartment consists of a zinc bar (the anode)
immersed in a Zn2+ electrolyte (solution of ZnS04). The zinc bar conducts the released
electrons out of its half-cell.

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 2. The reduction half-cell. The cathode compartment consists of a copper bar (the
cathode) immersed in a Cu2+ electrolyte (solution of CuS04). Copper metal conducts
electrons into its half-cell.
3. Relative charges on the electrodes. The electrode charges are determined by the source
of electrons and the direction of electron flow through the circuit. The electrons flow
left to right through the wire to the cathode. In any voltaic cell, the anode is negative
and the cathode is positive.
4. The purpose of the salt bridge. The oxidation half-cell and the reduction half-cell
originally contain neutral solutions. If the half-cells do not remain neutral, the resulting
charge imbalance would stop cell operation. To avoid this situation and enable the cell
to operate, the two half- cells are joined by a salt ridge, which act as a "liquid wire,"
allowing ions to flow through both compartments and complete the circuit. Therefore,
salt bridge maintains the neutrality of the solutions.

The conventional notation for representing electrochemical cells is the cell diagram
(cell notation). If we assume that the concentrations of Zn2+ and Cu2+ ions are

Zn(s) | Zn2+ (1M) || Cu2+ (1M) | Cu(s)

• The anode is written first, to the left of the double lines, while cathode is on
right.
• The single vertical line represents a phase boundary.
• The double vertical lines denote the salt bridge.
We can write the half- cell reactions as follows:

Anode (oxidation): Zn(s) Zn2+(1M) + 2e- Eᵒox = 0.76V

Cathode (reduction): Cu2+ (1M) + 2e- Cu(s) Eᵒred = 0.34V

Overall: Zn(s) + Cu2+ (1M) Zn2+ (1M) + Cu(s) Eᵒcell= 1.10V

Standard Reduction Potentials

For a reduction reaction at an electrode when all solutes are 1M and all gases are at 1
atm, the voltage is called the standard reduction potential (EO). The larger (more positive)
the EO value, the greater the tendency for the substance to be reduced, and therefore the stronger
its tendency to act as an oxidizing agent (gains electrons more readily). The smaller (more
negative) EO value, the greater the tendency for the substance to be oxidized and act as reducing
agent (loses electrons more readily).

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 Let us consider Cu2+, H+, and Zn2+, three oxidizing agent present in the voltaic cell.
We can rank their relative oxidizing strengths by writing each half-reaction as gain of electrons
(reduction), with its corresponding standard electrode potential:

Cu2+ gains two electrons more readily than I-1+, which gains them more readily than
Zn2+. In terms of strength as an oxidizing agent, therefore, Cu+2> H+ > Zn2+. Therefore Cu2+ is
the strongest oxidizing agents, and Zn is the strongest reducing agent.

Example:

Arrange the following species in order of increasing strength as oxidizing agents under
standard-state conditions: Ce4+, O2, H2O2

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*For all half-reactions the concentration is 1M for dissolved species and the pressure is atm
for gases. These are standard state values.

Please refer to the links for the Table of Standard Reduction Potential

https://chem.libretexts.org/Bookshelves/Ancillary_Materials/Reference/Reference_Tables
/Electrochemistry_Tables/P2%3A_Standard_Reduction_Potentials_by_Value

Calculating the standard emf (Eo) of an Electrochemical Cell

In an electrochemical cell, electric current flows from one electrode to the other (from
anode to cathode) because there is a difference in electrical potential energy between the

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electrodes. The difference in electrical potential between the anode and cathode is measured
by a voltmeter, and the reading (in volts) is called cell voltage. However, two other terms,
electromotive force or emf (E) and cell potential are also used to denote cell voltage. If all
solutes have a concentration of 1 M and all gases have a pressure of 1 atm (standard
conditions), the voltage difference between the two electrodes of the cell is called the
standard emf (EOcell). The standard emf is the sum of the standard oxidation potential and
the standard reduction potential for each half-reaction.

E0cell = E0ox + E0red

We can use the sign of the emf of the cell to predict the spontaneity of redox reaction. Under
standard-state conditions for reactants and products, the redox reaction is spontaneous in the
forward direction if the standard emf of the cell is positive. If it is negative, the reaction is
spontaneous in opposite direction.

Example:

We can calculate the standard emf of the cell using a table of reduction Potentials. As
an example, consider the galvanic cell represented by the following reaction:

Cu(s) + 2Ag+(aq) Cu2+(aq) + Ag(s)

Let’s break this reaction down into its half-reaction.

We can calculate the standard cell emf by adding the oxidation and reduction potentials.

The standard oxidation potential for an anode half-reaction is equal in magnitude, but of
opposite sign to that of the reduction potential for the reverse reaction. For example, [lie
reverse reaction of the copper oxidation is:

reduction
2+ -
Cu (aq) + 2e Cu(s)

You can look up the standard reduction potential for this half-reaction:
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Therefore, the standard oxidation potential for the oxidation of Cu Cu2+ has the opposite of
the standard reduction potential above.

We can also look up the standard reduction potential for silver:

Finally, we can calculate the standard cell emf.

Spontaneity of Redox Reactions

There is a relationship between free energy change and cell emf:

Where,
n = the number of moles of electrons transferred during the redox reaction

F = the Faraday, which is the electrical charge contained in 1 mole of electrons or the amount
of energy required for the flow of one mole of electron.

1F = 96500 C/mol = 96500 J/V.mol

Both n and F are positive quantifies, and we know that ∆G is negative for a spontaneous
process. Therefore, ecell is positive for a spontaneous process.
For reaction in which reactants and products are in their standard states, equation becomes:

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Example:

Predict whether a spontaneous reaction will occur when the following reactants and
products are in their standard states:

Fe2+ + Cr2O72- Fe3+ + Cr3+

6Fe+2 →6Fe+3 + 6e- Oxidation Eᵒox = -0.77V

-
6e + Cr2O7 -2
+ 14H+→ 2Cr+3 + 7H2O Reduction Eᵒred = 1.33V
6Fe+2+ Cr2O7-2 + 14H+→ 6Fe+3 + 2Cr+3 + 7H2O Overall Reaction

Eᵒcell = Eᵒox + Eᵒred = -0.77V + 1.33V = 0.56 V (spontaneous, YES)

n = 6; F = 96500 J/V-mol
∆Gᵒ = -nFEᵒcell = -(6 mol)(96500 J/Vmol)(0.56V) = -324 240 J (spontaneous, YES)

Standard Cell Potential and the Equilibrium Constant

This equation shows that the relationship between standard free energy change and
standard emf is :

Using this relationship, we can relate the standard cell potential to the equilibrium
constant of the redox reaction.

Therefore, from the two equations we obtain

Solving for gives

We can simplify the above equation by

• Substituting the known value of 8.314 J/ mol.K for constant R
• Substituting the known value of 96 500 J/V.mol for constant F
• Substituting the standard temperature of 298 K for T
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 • Multiplying by 2.303 to convert from natural to common (base — 10) logarithms

Example:

Calculate ∆GO and the equilibrium constant at 250C for the reaction

2 Br ¯ (aq) + I2 (s) Br2 (l) + 2I ¯(aq)

2 Br ¯ (aq) Br2 (l) + 2e- Oxidation Eᵒox = -1.07V

2e- + I2 (s) 2I ¯(aq) Reduction Eᵒred= 0.53V

Eᵒcell = Eᵒox + Eᵒred = -1.07 + 0.53 = - 0.54V

n = 2; F = 96500 J/V-mol

∆Gᵒ = -nFEᵒcell = -(2)(96500)(-0.54) = 104220 J (non spontaneous)

0.0591 𝑉
Eᵒcell = log 𝐾
𝑛

0.0591 𝑉
-0.54 V = log 𝐾
2

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 2(−0.54)
= log K
0.0591

log K = -18.274

log K = -18.274
10 10
K = 5.321 x 10-19

The Nernst Equation

We have only focused on redox reactions in which reactants and products are in their standard
states, but standard-state conditions are often difficult, and sometimes impossible to maintain.
Therefore. we need a relationship between cell emf and concentrations of reactants and
products under nonstandard-state conditions.

We encountered a relationship between the free energy change (AG) and the standard free
energy change (∆GO)

where Q is the reaction quotient.

We also know that

and

Substituting for ∆G and ∆GO in the first equation, we find'.

Dividing both sides of the equation by —nF

The above equation is known as the Nernst equation. At 298 K, this equation can be simplified
by substituting R, T, and F into the equation

0.0257
lnQ
n

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or, expressing Equation using the base-10 logarithm of Q

0.05922
logQ
n

At equilibrium, there is no net transfer of electrons, so e = 0 and Q=K, where K is the

equilibrium constant.

Using the Nernst Equation to Predict the Spontaneity of a Redox Reaction

To predict the spontaneity of a redox reaction, we can use the Nernst equation to
calculate the cell emf, e. If the cell emf is positive, the redox reaction is spontaneous.
Conversely, if e is negative, the reaction is not spontaneous.
Example:

Calculate the cell emf and predict whether the following reaction is spontaneous at 25oC.

Zn(s) + 2H+ (1 x 10-4 M) Zn2+ (1.5 M) + H2 (1 atm)

Zn(s) Zn2+ (1.5 M) + 2e- Oxidation Eᵒox = 0.76V

2e- + 2H+ (1 x 10-4 M) H2 (1 atm) Reduction Eᵒred = 0 V

Eᵒcell = Eᵒox + Eᵒred = 0.76 + 0 = 0.76 V

n= 2

1.51
Q = (1 ×10−4)2 = 1.5 x 108

0.05922
logQ
n

0.0592
E = 0.76V - log (1.5 x 108) = 0.518 V
2

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Using the Nernst equation to Calculate Concentration

Recall that the reaction quotient Q equals the concentrations of the product raised to the power
of their stoichiometric coefficients divided by the concentrations of the reactants raised to the
power of their stoichiometric coefficients.

Since Q is in the Nernst equation, if the cell emf is measured and the standard cell emf is
calculated, we can determine the concentration of one of the components if the concentrations
of the other components are known.

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