Electrochemistry

Electrochemical Cell
 An electrochemical cell is a device or a

mechanism that can either generate
electrical energy from a chemical
reaction or utilize electrical energy to
produce a chemical reaction.
Chemistry
Electrochemical Cell cont’d.
 Galvanic or Voltaic cell

 an electrochemical cell in which a spontaneous
chemical reaction produces electricity

 Electrolytic cell
 an electrochemical cell in which a nonspontaneous
reaction is carried out by electrolysis

 Electrolysis
 a process in which electrical energy is used to
cause a nonspontaneous chemical reaction to

occur
09/28/2020 Chemistry
Daniell Cell
Anode
– the electrode at which oxidation occurs
Cathode
– the electrode at which reduction occurs
Considering the above electrochemical cell as
example, the redox reaction taking place is:
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
The anodic reaction (OHR) occurs at the zinc

electrode: Zn(s) → Zn2+(aq) + 2e-
The cathodic reaction (RHR) occurs at the

copper electrode: Cu2+(aq) + 2e- → Cu(s)
salt bridge
– an inverted U-tube containing an inert electrolyte
solution whose ions will not react with the other ions
in solution or with the electrodes
cell voltage
– difference in electrical potential between the anode
and cathode, in volts
– also known as electromotive force (emf) or cell
potential
The voltage of a cell depends on:

1. nature of the electrodes and ions
2. concentrations of the ions
3. temperature at which the cell is operated
Cell diagram
– the conventional notation for representing
electrochemical cells
– short hand way of interpreting the actual
electrochemical cell
For
 the redox reaction:
Zn(s) + Cu2+(aq)Zn2+(aq) + Cu(s)
The cell diagram is:
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
phase boundary salt bridge phase boundary
Convention: Anode is written first, to the left of the

double line (salt bridge) while cathode is written last,
immediately after the double line (salt bridge).
Example

For the cell diagram:
Zn(s) | Zn2+(1M) || H+(1M) | H2(1atm) | Pt(s)
(a) Write the anode reaction.
(b) Write the cathode reaction.
(c) What is the overall reaction?
Answers
Anode (oxidation):
Cathode (reduction):
Overall:
 A cell consisting of a zinc electrode and a

hydrogen electrode
Example

For the cell diagram:
Pt(s) | H2(1atm) | H+(1M) || Cu2+(1M) | Cu(s)
(a) Write the anode reaction.
(b) Write the cathode reaction.
(c) What is the overall reaction?
Answers
Anode (oxidation):
Overall:
 A cell consisting of a copper electrode and a

hydrogen electrode
Standard Electrode Potentials

The voltage of a cell can be related directly to the
redox reactions, but how?
Just as the overall cell reaction can be obtained by
taking the sum of the two (2) half-cell reactions, the
cell emf can also be treated as the sum of the
electrode potentials.
Note: It is impossible to measure the potential of just

a single electrode.
Hydrogen Electrode
– an arbitrary electrode set at zero which is used as a
reference
Example:
Hydrogen gas is bubbled through a hydrochloric acid
solution at 25°C, the platinum electrode has two (2)
functions:
(1) It provides a surface on which the dissociation of
hydrogen molecules can take place: H2 → 2H+ + 2e-
(2) It serves as an electrical conductor to the external
circuit.
 A hydrogen electrode operating

under standard-state conditions.
Hydrogen gas at 1 atm is bubbled
through a 1 M HCl solution. The
platinum electrode is part of the
hydrogen electrode.
Under standard-state conditions (that is, when

pressure of H2 is 1 atm and (HCl = 1.00M), the
potential for the reduction of H+ at 25°C is taken to be
exactly ZERO:
2H+(1M) + 2e- → H2(1 atm) E° = 0.00 V
The superscript “°” stands for

STANDARD STATE CONDITIONS
Standard Reduction Potential, E°

– Eo is read as “E knot”
– this is the voltage associated with a reduction
reaction at an electrode when all solutes are 1 M and all
gases are at 1 atm
Note:
The Eo of a hydrogen electrode = 0.00 V
A hydrogen electrode is more commonly known as
“S H E” or Standard Hydrogen Electrode.
Standard Electrode (Reduction) Potential (SRP) Table

– is a table showing the relationship of the species
reduced to the corresponding energy in volts, taking
note that the temperature should always be 25°C
Standard Electrode (Reduction)
Potentials at 25°C (Refer to the next slides)
Acidic Solution
Standard Electrode (Reduction) Potentials at 25°C
Acidic Solution
Standard Electrode (Reduction) Potentials at 25°C
Standard
 emf of the cell, E°cell
– is composed of a contribution from the anode and a
contribution from the cathode
Three alternative equations:
where
= standard reduction potentials of the electrodes
Note: the values of E° can be found in the SRP table
For
 the cell described in the previous example,
Zn(s) | Zn2+(1.00M) || H+(1.00M) | H2(1.00atm) | Pt(s)
The E° is:
Important Notes for determining the E° of a cell
1. The more positive (+) the E°, the greater the
tendency for the substance to be reduced.
Example:
F2(1atm) + 2e- → 2F1-(1M) E° = 2.87 V
Therefore, it is the STRONGEST oxidizing agent
2. The more negative (-) the E°, the greater the
tendency for the substance to be oxidized
Example:
Li+(1M) + e- → Li(s) E° = –3.05 V
Therefore, it is the WEAKEST oxidizing agent
3. Trends in the SRP table

(a) oxidizing agents increase in strength from
bottom to top
(b) reducing agents increase in strength from top
to bottom
4. Changing the stoichiometric coefficients of a half-cell
reaction DOES NOT affect the value of E° because
electrode potentials are intensive/intrinsic properties
Example: I2(s) + 2e- → 2I1-(1M) E° = 0.53 V
2I2(s) + 4e- → 4I-(1M) E° = still 0.53 V

Diagonal Rule
Example
 The substance on the left of the first half-cell

reaction is and the substance on the right in the
second half-cell reaction is Zn. Zn spontaneously
reduces to form and Cu.
Sample
 Problem
Predict what will happen if molecular bromine () is
added to a solution containing and at . Assume all
species are in their standard states.
Solution

From the table, the standard reduction potentials are
Applying diagonal rule:

will oxidize but not
Oxidation:
Reduction:
Overall:
Sample
 Problem
A galvanic cell consists of a magnesium (Mg)
electrode in a 1.0 M Mg(NO3)2 solution and a silver (Ag)
electrode in a 1.0 M AgNO3 solution. Calculate the
standard emf of this electrochemical cell at 25°C.
Solution
From the table, the standard reduction potentials are:
Solution
 cont’d.
Applying the diagonal rule, we see that Ag + will oxidize
Mg:
Anode (oxidation):
Overall:
Solution
 cont’d.
Note:
In order to balance the overall equation, we
multiplied the reduction of Ag+ by 2.
Eo is not affected by this procedure.
emf of the cell
Sample
 Problem
A new battery system currently under study for
possible use in electric vehicles is the zinc-chlorine
battery.
The overall reaction producing electricity in this cell is
Zn (s) + Cl2 (g) ZnCl2 (aq). What is of this voltaic cell?
Solution

Anode (Oxidation):
Cathode (Reduction):
Overall:
 Practice Exercises
1. What is the standard potential of an
electrochemical cell made of a cadmium (Cd)
electrode in a 1.0M Cd(NO3)2 solution and a
chromium (Cr) electrode in a 1.0M Cr(NO3)3
solution?
2. Write the overall equation for the redox
reaction that occurs in the voltaic cell
| || |
Thermodynamics of Redox Reactions
electrical energy = volts x coulombs
= V x C = Joules
total charge = number of e- x charge of one e-
total charge = n x F
where:
F = Faraday’s constant (the electrical charge contained in 1
mole of electrons)
1F = 96,500 (96,485) coulombs (C)
1J = 1C x 1V
1F = 96,500 (96,485) J/V-mol
Relation
 between Gibb’s Free Energy and
Electrode Potential
 Gibbs Free Energy or Free Energy
(G)
 the energy available to do useful work
 General form of the equation
During
 standard-state conditions
(1)
From thermodynamics
(2)
 Equilibrium constant (K)
 a number equal to the ratio of the equilibrium
concentrations of products to the equilibrium

concentrations of reactants, each raised to the
power of its stoichiometric coefficient
Combining
 equations 1 and 2
Solving for
 Relationships among E°, K, and ∆G°
Table showing the relationship of ΔG°, K, and E°cell
Sample
 Problem
Calculate the equilibrium constant, K, for the following
redox reaction at 25°C:
Solution

Two half-cell reactions:
Anode (oxidation)
Cathode (reduction)

In the overall reaction, .
Therefore,
Sample
 Problem
Calculate the standard free energy
change for the following redox reaction at
25°C:
Solution

Two half-cell reactions:
Anode (oxidation):
Solution
 cont’d.
Note: The large positive value of means the reaction

favors the reactants at equilibrium.
* for the galvanic cell is negative
Practice
 Exercise
Use electrode potential data to determine
for the reaction
Effect of Cell Concentration on Cell emf
–
 If the cell concentration is not 1.00 M, we have to consider
another way of solving the Ecell
Consider a reaction
 where R = gas constant (8.314 J/K.mol)

T = absolute temperature of the reaction
Q = reaction quotient
Effect of Cell Concentration on Cell Emf
 where
Therefore:
famously known as the

Example NERNST EQUATION
Write a Nernst equation that represents the redox
reaction:
 Nernst Equation for the cell at 25°C
Note:
Since are both solids, they do not appear in the
equilibrium constant.
Sample
 Problem
Predict whether the following reaction would proceed
spontaneously as written at 298 K.
Given that
[Co2+] = 0.15 M and
[Fe2+] = 0.68 M
Solution

The half-cell reactions are:
Anode (oxidation):
Solution
 cont’d.
Because E is negative, the reaction is not spontaneous in

the direction written.
Sample
 Problem
Consider the electrochemical cell shown below:
In a certain experiment, the emf of the cell is found to

be 0.54 V at 25°C. Suppose that [Zn2+] = 1.0 M and
the partial pressure of H2 is 1.0 atm, calculate the molar
concentration of H+ if the standard emf of the cell is
0.76 V.
Solution

Note: If gases are involved in the cell reaction, their

concentrations should be expressed in atm.
Solution
 cont’d.
Practice
 Exercise
Will the following redox reaction occur
spontaneously at 25°C, given that
[Fe2+] = 0.60 M and
[Cd2+] = 0.010 M?
Practice
 Exercise
What is the emf of a cell consisting of a
Cd2+/Cd half-cell and a Pt/H+/H2 half-cell if
[Cd2+] = 0.20 M, [H+] = 0.16 M and the
= 0.80 atm?

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Electrochemistry

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Electrochemical Cell

 An electrochemical cell is a device or a

 Galvanic or Voltaic cell

chemical reaction produces electricity

reaction is carried out by electrolysis

cause a nonspontaneous chemical reaction to

The anodic reaction (OHR) occurs at the zinc

The cathodic reaction (RHR) occurs at the

The voltage of a cell depends on:

phase boundary salt bridge phase boundary

Convention: Anode is written first, to the left of the

 A cell consisting of a zinc electrode and a

 A cell consisting of a copper electrode and a

Standard Electrode Potentials

Note: It is impossible to measure the potential of just

 A hydrogen electrode operating

Under standard-state conditions (that is, when

2H+(1M) + 2e- → H2(1 atm) E° = 0.00 V

The superscript “°” stands for

Standard Reduction Potential, E°

Standard Electrode (Reduction) Potential (SRP) Table

3. Trends in the SRP table

 The substance on the left of the first half-cell

Applying diagonal rule:

 General form of the equation

concentrations of products to the equilibrium

Table showing the relationship of ΔG°, K, and E°cell

Note: The large positive value of means the reaction

 where R = gas constant (8.314 J/K.mol)

famously known as the

 Nernst Equation for the cell at 25°C

Because E is negative, the reaction is not spontaneous in

In a certain experiment, the emf of the cell is found to

Note: If gases are involved in the cell reaction, their

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