Electrochemical Cell

– an experimental apparatus for generating

electricity through the use of a spontaneous
redox reaction
– also referred to as galvanic or voltaic cell

A typical electrochemical cell looks like: (see

next slide)

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 Electrochemical Cell

Daniell Cell

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Electrochemical 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)

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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)

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Electrochemical Cell
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

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Electrochemical Cell
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
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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).
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 Electrochemical Cell
Example
For the cell diagram:
Zn(s) | Zn2+(1 M) || H+(1 M) | H2(1 atm) | Pt(s)
(a) Write the anode reaction.
(b) Write the cathode reaction.
(c) What is the overall reaction?

Answers
Anode (oxidation): 𝑍𝑛 𝑠 → 𝑍𝑛2+ 1 𝑀 + 2𝑒 −
Cathode (reduction): 2𝐻 + 1 𝑀 + 2𝑒 − → 𝐻2 (1 𝑎𝑡𝑚)
Overall: 𝑍𝑛 𝑠 + 2𝐻 + 1 𝑀 → 𝑍𝑛2+ 1 𝑀 + 𝐻2 (1 𝑎𝑡𝑚)

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 Electrochemical Cell
 A cell consisting of a zinc electrode and a
hydrogen electrode

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Electrochemical Cell
Example
For the cell diagram:
Pt(s) | H2(1 atm) | H+(1 M) || Cu2+(1 M) | Cu(s)
(a) Write the anode reaction.
(b) Write the cathode reaction.
(c) What is the overall reaction?

Answers
Anode (oxidation): 𝐻2 1 𝑎𝑡𝑚 → 2𝐻 + 1 𝑀 + 2𝑒 −
Cathode (reduction): 𝐶𝑢2+ 1 𝑀 + 2𝑒 − → 𝐶𝑢 𝑠
Overall: 𝐻2 1 𝑎𝑡𝑚 + 𝐶𝑢2+ 1 𝑀 → 2𝐻 + 1 𝑀 + 𝐶𝑢 𝑠

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Electrochemical Cell
 A cell consisting of a copper electrode and a
hydrogen electrode

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Electrochemical Cell
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.
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Electrochemical Cell
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.
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 Electrochemical Cell
 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.

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Electrochemical Cell
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

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Electrochemical Cell
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.

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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

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Standard Electrode (Reduction)
Potentials at 25°C (Refer to the next slides)
Acidic Solution

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Standard Electrode (Reduction) Potentials at 25°C

Acidic Solution

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 Standard Electrode (Reduction) Potentials at 25°C

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Electrochemical Cell
Standard emf of the cell, E°cell
– is composed of a contribution from the anode and a
contribution from the cathode
Three alternative equations:
𝐸°𝑐𝑒𝑙𝑙 = 𝐸°(𝑟𝑖𝑔ℎ𝑡) − 𝐸°(𝑙𝑒𝑓𝑡)
𝐸°𝑐𝑒𝑙𝑙 = 𝐸°(𝑐𝑎𝑡ℎ𝑜𝑑𝑒) − 𝐸°(𝑎𝑛𝑜𝑑𝑒)
𝐸°𝑐𝑒𝑙𝑙 = 𝐸°(𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 ℎ𝑎𝑙𝑓−𝑐𝑒𝑙𝑙) − 𝐸°(𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 ℎ𝑎𝑙𝑓−𝑐𝑒𝑙𝑙)
where
𝐸°(𝑐𝑎𝑡ℎ𝑜𝑑𝑒) 𝑎𝑛𝑑 𝐸°(𝑎𝑛𝑜𝑑𝑒) = standard reduction potentials
of the electrodes
Note: the values of E° can be found in the SRP table
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Electrochemical Cell
For the cell described in the previous example,
Zn(s) | Zn2+(1.00M) || H+(1.00M) | H2(1.00atm) | Pt(s)

The E° is:

𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝐻 + /𝐻2 − 𝐸°𝑍𝑛2+ /𝑍𝑛

0.76 𝑉 = 0 − 𝐸°𝑍𝑛2+ /𝑍𝑛
𝐸°𝑍𝑛2+ /𝑍𝑛 = −0.76 𝑉

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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
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 Electrochemical Cell
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
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Diagonal Rule
Example
 𝑪𝒖𝟐+ 𝟏𝑴 + 𝟐𝒆− → 𝑪𝒖 𝒔 𝑬° = 𝟎. 𝟑𝟒𝑽
 𝒁𝒏𝟐+ 𝟏𝑴 + 𝟐𝒆− → 𝒁𝒏(𝒔) 𝑬° = −𝟎. 𝟕𝟔𝑽

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

is 𝐶𝑢2+ and the substance on the right in the second
half-cell reaction is Zn. Zn spontaneously reduces
𝐶𝑢2+ to form 𝑍𝑛2+ and Cu.
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Sample Problem
Predict what will happen if molecular bromine (𝐵𝑟2 ) is
added to a solution containing 𝑁𝑎𝐶𝑙 and 𝑁𝑎𝐼 at 25°𝐶.
Assume all species are in their standard states.

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Solution
From the table, the standard reduction potentials are
𝐶𝑙2 1 𝑎𝑡𝑚 + 2𝑒 − → 2𝐶𝑙 − 1 𝑀 𝐸 𝑜 = 1.36 𝑉
𝐵𝑟2(𝑙) + 2𝑒 − → 2𝐵𝑟 − 1 𝑀 𝐸 𝑜 = 1.07 𝑉
𝐼2(𝑠) + 2𝑒 − → 2𝐼 − 1 𝑀 𝐸 𝑜 = 0.53 𝑉
Applying diagonal rule:
𝐵𝑟2 will oxidize 𝐼 − but not 𝐶𝑙 −
Oxidation: 2𝐼 − 1 𝑀 → 𝐼2(𝑠) + 2𝑒 −
Reduction: 𝐵𝑟2(𝑙) + 2𝑒 − → 2𝐵𝑟 − (1 𝑀)
Overall: 2𝐼 − 1 𝑀 + 𝐵𝑟2 𝑙 → 𝐼2 𝑠 + 2𝐵𝑟 − (1 𝑀)
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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:
𝐴𝑔+ 1.0 𝑀 + 𝑒 − → 𝐴𝑔(𝑠) Eo = 0.80 V
𝑀𝑔2+ 1.0 𝑀 + 2𝑒 − → 𝑀𝑔 𝑠 Eo = −2.37 V
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Solution cont’d.
Applying the diagonal rule, we see that Ag+ will oxidize
Mg:
Anode (oxidation): 𝑀𝑔 𝑠 → 𝑀𝑔2+ 1.0 𝑀 + 2𝑒 −
Cathode (reduction): 2𝐴𝑔+ 1.0 𝑀 + 2𝑒 − → 2𝐴𝑔 𝑠
Overall:
𝑀𝑔 𝑠 + 2𝐴𝑔+ 1.0 𝑀 → 𝑀𝑔2+ 1.0 𝑀 + 2𝐴𝑔 𝑠

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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
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜 𝑜
= 𝐸𝐴𝑔 + /𝐴𝑔 − 𝐸𝑀𝑔2+ /𝑀𝑔

= 0.80 𝑉 − −2.37 𝑉
= 3.17 𝑉
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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 𝐸𝑐𝑒𝑙𝑙𝑜
of this
voltaic cell?

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Solution
Anode (Oxidation):
𝑍𝑛 𝑠 → 𝑍𝑛2+
𝑎𝑞 + 2𝑒 − 𝐸 𝑜 = −0.76 𝑉
Cathode (Reduction):
𝐶𝑙2 𝑔 + 2𝑒 − → 2𝐶𝑙 −𝑎𝑞 𝐸 𝑜 = +1.36 𝑉
Overall: 𝑍𝑛 𝑠 + 𝐶𝑙2 𝑔 → 𝑍𝑛2+
𝑎𝑞 + 2𝐶𝑙 −
𝑎𝑞

𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 reduction half−cell − 𝐸 𝑜 oxidation half−cell
= 1.36 𝑉 − −0.76 𝑉
= 2.12 𝑉

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Electrochemical Cell
 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
𝑆𝑐 𝑠 | 𝑆𝑐 3+
𝑎𝑞 || 𝐴𝑔 𝑎𝑞 | 𝐴𝑔
+
𝑠
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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

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Relation between Gibb’s Free Energy and

Electrode Potential

General form of the equation:

Δ𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
during standard-state conditions:
𝑜
Δ𝐺° = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 → (1)
from thermodynamics:
Δ𝐺 𝑜 = −𝑅𝑇ln(𝐾) → (2)

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Combining equations 1 and 2

𝑜
−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑅𝑇 ln 𝐾
Solving for 𝑬𝒐𝒄𝒆𝒍𝒍
𝑜 −𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = ln(𝐾)
−𝑛𝐹
𝑜 8.314 𝐽/𝐾 ∙ 𝑚𝑜𝑙 25 + 273 𝐾
𝐸𝑐𝑒𝑙𝑙 = ln 𝐾
𝑛 96,500 𝐽/𝑉 ∙ 𝑚𝑜𝑙
𝑜 0.0257 𝑉
𝐸𝑐𝑒𝑙𝑙 = ln(𝐾)
𝑛

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 Relationships among E°, K, and ∆G°

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 Thermodynamics of Redox Reactions

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

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Thermodynamics of Redox Reactions

Sample Problem
Calculate the equilibrium constant, K, for the following
redox reaction at 25°C:
2+
𝑆𝑛𝑠 + 2𝐶𝑢(𝑎𝑞) 2+
⇌ 𝑆𝑛(𝑎𝑞) + 2𝐶𝑢+𝑎𝑞

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Solution
Two half-cell reactions:
Anode (oxidation)
𝑆𝑛 𝑠 → 𝑆𝑛2+
𝑎𝑞 + 2𝑒 − 𝐸 𝑜 = −0.14 𝑉
Cathode (reduction)
2𝐶𝑢2+
𝑎𝑞 + 2𝑒 −
→ 2𝐶𝑢 +
(𝑎𝑞) 𝐸 𝑜
= +0.15 𝑉
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜 𝑜
= 𝐸𝐶𝑢 2+ /𝐶𝑢+ − 𝐸𝑆𝑛2+ /𝑆𝑛

= 0.15 𝑉 − −0.14 𝑉
= 0.29 𝑉
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𝑛𝐸 𝑜
ln 𝐾 =
0.0257 𝑉
In the overall reaction, 𝑛 = 2.
Therefore,
2 0.29 𝑉
ln 𝐾 = = 22.6
0.0257 𝑉
𝐾 = 𝑒 22.6 = 7 × 109

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Sample Problem
Calculate the standard free energy
change for the following redox reaction at
25°C:
2+ 3+
2𝐴𝑢(𝑠) + 3𝐶𝑎 𝑎𝑞 → 2𝐴𝑢 𝑎𝑞 + 3𝐶𝑎(𝑠)

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Solution
Two half-cell reactions:
Anode (oxidation):
2𝐴𝑢 𝑠 → 2𝐴𝑢3+ 1.0 𝑀 + 6𝑒 − 𝐸 𝑜 = +1.50 𝑉
Cathode (reduction):
3𝐶𝑎2+ 1.0 𝑀 + 6𝑒 − → 3𝐶𝑎 𝑠 𝐸 𝑜 = −2.87 𝑉
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜 𝑜
= 𝐸𝐶𝑎 2+ /𝐶𝑎 − 𝐸𝐴𝑢3+ /𝐴𝑢

= −2.87 𝑉 − 1.50 𝑉
= −4.37 𝑉
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Solution cont’d.
Δ𝐺 𝑜 = −𝑛𝐹𝐸 𝑜 ; 𝑛 = 6
Δ𝐺 𝑜 = −(6)(96,500 𝐽/𝑉 ∙ 𝑚𝑜𝑙)(−4.37 𝑉)
= 2.53 × 106 𝐽/𝑚𝑜𝑙
= 2.53 × 103 𝑘𝐽/𝑚𝑜𝑙
Note: The large positive value of Δ𝐺 𝑜 means the
reaction favors the reactants at equilibrium.
*𝐸 𝑜 for the galvanic cell is negative

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Thermodynamics of Redox Reactions

Practice Exercise
Use electrode potential data to determine
Δ𝐺 𝑜 for the reaction
2𝐴𝑙 𝑠 + 3𝐵𝑟2 𝑙 → 2𝐴𝑙3+ 𝑎𝑞,1𝑀 + 6𝐵𝑟 −
𝑎𝑞,1𝑀
Δ𝐺 𝑜 = ?

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The 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 redox reaction

𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
𝑜 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln(𝑄)
𝑛𝐹
 where R = gas constant (8.314 J/K.mol)
T = absolute temperature of the reaction
Q = reaction quotient
𝑜 8.314 𝐽/𝐾∙𝑚𝑜𝑙 25°𝐶+273𝐾
 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln(𝑄)
𝑛 96,500 𝐽/𝑉∙𝑚𝑜𝑙
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where
𝐶 𝐶 𝐷 𝑑
𝑄= 𝑎 𝑏
𝐴 𝐵
Therefore:
𝑜 0.0257 𝑉 𝐶𝑐𝐷𝑑
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln famously known as the
𝑛 𝐴𝑎𝐵𝑏
NERNST EQUATION

Example
Write a Nernst equation that represents the redox
reaction:
2+ 2+
𝑍𝑛(𝑠) + 𝐶𝑢(𝑎𝑞) → 𝑍𝑛(𝑎𝑞) + 𝐶𝑢(𝑠)
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 Nernst Equation for the cell at 25°C

0.0257 𝑉 𝑍𝑛2+
 𝐸𝑐𝑒𝑙𝑙 = 1.10 𝑉 − ln
2 𝐶𝑢2+

Note:
Since 𝐶𝑢(𝑠) 𝑎𝑛𝑑 𝑍𝑛(𝑠) are both solids, they do not
appear in the equilibrium constant.

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Sample Problem
Predict whether the following reaction would proceed
spontaneously as written at 298 K:
2+ 2+
𝐶𝑜(𝑠) + 𝐹𝑒(𝑎𝑞) → 𝐶𝑜(𝑎𝑞) + 𝐹𝑒(𝑠)
Given that
[Co2+] = 0.15 M and
[Fe2+] = 0.68 M

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Solution
The half-cell reactions are:
Anode (oxidation): 𝐶𝑜 𝑠 → 𝐶𝑜 2+
𝑎𝑞 + 2𝑒 −

Cathode (reduction): 𝐹𝑒 2+
𝑎𝑞 + 2𝑒 −
→ 𝐹𝑒 𝑠

𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜 𝑜
= 𝐸𝐹𝑒 2+ /𝐹𝑒 − 𝐸𝐶𝑜2+ /𝐶𝑜

= −0.44 𝑉 − −0.28 𝑉
= −0.16 𝑉
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The Effect of Cell Concentration on Cell emf

Solution cont’d.
0.0257 𝑉
𝐸= 𝐸𝑜 − ln(𝑄)
𝑛
0.0257 𝑉 𝐶𝑜2+
= 𝐸𝑜 − ln 2+
𝑛 𝐹𝑒
0.0257 𝑉 0.15
= −0.16 𝑉 − ln
2 0.68
= −0.16 𝑉 + 0.019 𝑉
= −0.14 𝑉
Because E is negative, the reaction is not spontaneous in
the direction written.

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The Effect of Cell Concentration on Cell emf

Sample Problem
Consider the electrochemical cell shown below:
𝑍𝑛 𝑠 + 2𝐻 + ? 𝑀 → 𝑍𝑛2+ 1.0𝑀 + 𝐻2(1.0 𝑎𝑡𝑚)
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.

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The Effect of Cell Concentration on Cell emf

Solution
0.0257 𝑉
𝐸= 𝐸𝑜 − ln 𝑄
𝑛
0.0257 𝑉 𝑍𝑛2+ 𝑃𝐻2
𝐸 = 𝐸𝑜 − ln
𝑛 𝐻+ 2
0.0257 𝑉 1.0 1.0
0.54 𝑉 = 0.76 𝑉 − ln
2 𝐻+ 2
0.0257 𝑉 1
−0.22 𝑉 = − ln + 2
2 𝐻
Note: If gases are involved in the cell reaction, their
concentrations should be expressed in atm.

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Solution cont’d.
1
17.1 = ln + 2
𝐻
17.1
1
𝑒 = +2
𝐻
1
𝐻+ = = 2 × 10 −4 𝑀
3 × 107

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The Effect of Cell Concentration on Cell emf

Practice Exercise
Will the following redox reaction occur
spontaneously at 25°C, given that
[Fe2+] = 0.60 M and
[Cd2+] = 0.010 M?

𝐶𝑑 𝑠 + 𝐹𝑒 2+
𝑎𝑞 → 𝐶𝑑 2+
𝑎𝑞 + 𝐹𝑒 𝑠

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The Effect of Cell Concentration on Cell emf

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 PH2 = 0.80 atm?

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