CHEM 131: CHEMISTRY FOR ENGINEERS

ELECTROCHEMISTRY
Prepared by: Engr. Karla Jane N. Puracan

Electrochemistry is the study of the interconversion of electrical and chemical energy. This conversion takes
place in an electrochemical cell:
• voltaic cell where a spontaneous reaction generates electricity
• electrolytic cell wherein electricity is used to bring about a non-spontaneous reaction

A spontaneous reaction by definition is a reaction that occurs without the intervention of the outside. It occurs
naturally under certain conditions. On the other hand, a non-spontaneous reaction will not take place unless it is
driven by the continual input of energy from an external source.
VOLTAIC CELLS

In spontaneous oxidation-reduction reactions, electrons are transferred and energy is released.

This energy released can be used to do work if the electrons are made to flow through an external device. This
can be achieved through a set-up called a voltaic or galvanic cell.

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Galvanic cells or voltaic cells are electrochemical cells in which spontaneous oxidation-reduction reactions
produce electrical energy. The cell directs the transfer of electrons in an external pathway instead of directly
between the reactants. The reactants, the oxidizing and reducing agents, force the electrons to travel through a
wire. It uses the oxidation and reduction occurring at two terminals to change chemical potential energy into
electric potential energy.

Components of the Voltaic Cell

1. electrodes
In this type of cell, two solid metals called electrodes are connected by an external circuit where the electrons
will be made to flow.
A. anode - the electrode at which oxidation occurs ; where electrons are lost
B. cathode - the electrode at which reduction occurs; where electrons are gained
The electrons lost at the anode will pass through the external circuit and will be accepted at the cathode.
The type of the electrode used in the cell can be:
• participative electrode/reactive electrode - the material used as an electrode participate in the reaction and
will gradually disappear as the reaction progresses
• inert electrode - the material used as an electrode is a conducting material, such as platinum or graphite, that
does not gain or lose mass during the reaction but serves as a surface at which electrons are transferred.
2. Half-cell
The half-cell is a single electrode, generally a metal, immersed in a container filled with an electrolyte solution,
and having a specific potential for a given combination of electrode and electrolyte.
The electrolyte solution is a solution that generally contains ions, atoms or molecules that have lost or gained
electrons, and is electrically conducive.
3. Salt bridge
A salt bridge is an inverted U shaped glass tube plugged with glass wool at each end and filled with a weak
electrolyte solution that does not take part in the electrode reactions. A salt bridge is used as a connection
between the oxidation and reduction half-cells. Its purpose is to prevent the buildup of ions on one side of the
cell and balances the charge.

How Do the Electrons Flow through a Cell?

1. The electrons are produced in the anode by the oxidation half-reaction. The anode “pumps” the electrons
into the external circuit.
2. The electrons generated at the anode move through the external circuit to the cathode connected to a
voltmeter.
3. The electrons are consumed at the cathode where the reduction half-reaction happens.
4. As the half-reactions proceed, positive ions tend to build up around the anode and the cathode becomes
deficient in positive ions. To maintain electrical neutrality, cations must move toward the cathode and anions
must move toward the anode. This movement of ions occurs through the salt bridge.

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Cell Diagrams Notation
The reaction in a voltaic cell may be represented using a cell diagram where we place the anode on the left and
cathode on the right. “ | ” represents the boundary between the two phases and “ || ” represents the salt bridge.
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
Sample Problems:
1. The oxidation - reduction reaction
Cr2O72−(a q) + 14H +(a q) + 6I −(a q) → 2Cr 3+(a q) + 3I2(s) + 7H2O(l )
is spontaneous. A solution containing K2CrO7 and H2SO4 is poured into one beaker, and a solution of KI is
poured into another. A salt bridge is used to join the beakers. A metallic conductor that will not react with either
solution (such as platinum foil) is suspended in each solution, and the two conductors are connected with wires
through a voltmeter or some other device to detect an electric current. The resultant voltaic cell generates an
electric current.
A. Draw a sketch of the cell and indicate the reaction occurring at the anode and at the cathode the
reaction occurring at the cathode, the direction of the electron migration, the direction of the ion
migration, and the signs of the electrodes.
B. Write an abbreviated notation for the cell.
2. Two half reactions in a voltaic cell are
Z n(s) → Z n 2+(a q) + 2e −
ClO3−(a q) + 6H +(a q) + 6e − → Cl −(a q) + 3H2O(l )
A. Indicate which reaction occurs a the anode and which at the cathode.
B. Which electrode is consumed in the cell reaction?
C. Which electrode is positive?
D. Write an abbreviated notation for the cell.

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CELL POTENTIAL UNDER STANDARD CONDITIONS (STANDARD VOLTAGE)
The driving force behind the spontaneous reaction in a voltaic cell is measured by the cell voltage. This cell
voltage is the potential difference between the two electrodes which caused the electrons to flow from the
anode to the cathode. The flow of electrons in the cell can be likened to the flow of water in a waterfall flowing
from a point of high potential energy to that of low potential energy. Electrons flow from the electron rich anode
to the electron poor cathode.
Physically, the cell voltage is a measure of how strongly can one electrode attract electrons over the other which
leads to the current flow.

The cell voltage between two electrodes is measure in volts. One volt (V) is the potential difference to impart 1 J
of energy to a charge of 1 C.
J
1V = 1 recall that 1e − = 1.60x10−19C
C
It is otherwise called the cell potential and is denoted Ecell. Because it provides the driving force that pushes
electrons through the external circuit, we also call it the electromotive(“causing electron motion”) force, or emf.
Because Ecell is measured in volts, it is commonly called the voltage of the cell.

Since the reaction in a voltaic cell is spontaneous, its cell voltage is positive.
The cell voltage is:
• an intensive property so it does not depend on the number of electrons passing through the cell
• dependent on two factors : (a) nature of the redox reaction
(b)concentration of the species involved

Standard Voltage
The cell voltage of voltaic cells operated at 25°C under standard conditions is referred to as the standard
voltage, E°. Recall that standard conditions means that the concentration of the reactants and products in
solution is 1M and the pressure for gaseous reactants and products is 1 atm.

Standard Reduction/Oxidation Voltage

The standard cell voltage depends on the particular cathode and anode half cells where the two half-reactions,
reduction and oxidation, take place. The half-cell where oxidation occurs is assigned a standard oxidation
voltage, E°ox and the half-cell where reduction occurs is assigned a standard reduction voltage, E°red. The
standard voltage for the overall cell reaction, E°, is the sum of these two quantities.

E° = E°red + E°ox

How were the assigned standard oxidation and reduction voltages determined?

Standard Hydrogen Electrode

There is no way to measure the standard voltage for a half-reaction, only E° can be measured directly. To obtain
values for E°red and E°ox , a standard voltage is assigned to a certain reference half reaction. This reference half
reaction is the reduction of H+(aq) to H2(g) under standard conditions, which is assigned a standard reduction
voltage of 0V:
2H +(a q,1M ) + 2e − → H2(g,1a t m) ∘
Ered = 0V

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The electrode designed to produce this half-reaction is called a standard hydrogen electrode(SHE). An SHE
consists of a platinum wire connected to a piece of platinum foil covered with finely divided platinum that serves
as an inert surface for the reaction. The SHE allows platinum to be in contact with both 1M H+(aq) and a stream
of hydrogen gas at 1 atm. The SHE can operate as either the anode or the cathode of the cell, depending on the
nature of the other electrode.

The standard half-cell voltages are ordinarily obtained from a list of standard potentials such as

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Rules for Using Standard Reduction Voltages:
1. Read the half-reactions as written
2. The more positive the reduction voltage, the greater the tendency is for the substance to be reduced( and
therefore the better oxidizing agent)
It is important to note that for each half-cell in a voltaic cell, the standard reduction voltage provides a measure
of the tendency for the reduction to occur. The more positive the value of E°red, the greater the tendency for
reduction under standard conditions. In any voltaic cell operating under standard conditions, the E°red value for
the reaction at the cathode is more positive than the E°red value for the reaction at the anode. Thus, electrons
flow spontaneously through the external circuit from the electrode with the more negative value of E°red to the
electrode with the more positive value of E°red.
3. The half-cell reactions are reversible. If you need to reverse, you must change the sign of E°.
4. If you change the stoichiometric coefficients, E°cell remains the same.

In general, for voltaic cell voltages:

1. The calculated cell voltage is always a positive quantity for a reaction taking place in a voltaic cell.
2. The quantities of E°, E°red, and E°ox are independent of how the equation for the cell reaction is written. You
never multiply the voltage by the coefficients of the balanced equation.

How do we determine whether a given redox reaction is spontaneous?

If the calculated voltage for a redox reaction is a positive quantity, the reaction will be spontaneous. If
the calculated voltage is negative, the reaction is not spontaneous.

Sample Problems.
1. For a Zn-Cu2+ voltaic cell, we have
Z n(s) + Cu 2+(a q,1M ) → Z n 2+(a q,1M ) + Cu(s) E ∘ = 1.10V
Calculate the Ered for Cu2+ to Cu.
anode : Z n(s) → Z n 2+(a q,1M ) + 2e − ∘
Eox = 0.76V
cathode : Cu 2+(a q,1M ) + 2e − → Cu(s) ∘
Ered =?
∘ ∘ ∘
Ecell = Ered + Eox
∘
1.10V = Ered + 0.76V
∘
Ered = 0.34V (this standard reduction voltage agrees with that listed on the table)
2. The standard cell voltage is 1.46 V for a voltaic cell based on the following half-reactions:
In +(a q) → In 3+(a q) + 2e −
Br2(l ) + 2e − → 2Br −(a q)
Using the table of values, calculate the Ered for the reduction of In3+ to In.
anode : In +(a q) → In 3+(a q) + 2e − ∘
Eox =?
reduction : Br2(l ) + 2e − → 2Br −(a q) ∘
Ered = 1.06V
∘ ∘ ∘
Ecell = Ered + Eox
∘
1.46V = 1.06V + Eox
∘
Eox = 0.4V In +(a q) → In 3+(a q) + 2e − ∘
Eox = 0.4V
In 3+(a q) + 2e − → In +(a q) ∘
Eox = − 0.4V

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3. Use the table to calculate the standard cell voltage for the voltaic cell based on the reaction
Cr2O72−(a q) + 14H +(a q) + 6I −(a q) → 2Cr 3+(a q) + 3I2(s) + 7H2O(l) ∘
Ecell =?
anode : 6I −(a q) → 3I2(s) + 6e − ∘
Eox = − 0.54V
cathode : Cr2O72−(a q) + 14H +(a q) + 6e − → 2Cr 3+(a q) + 7H2O(l) ∘
Ered = 1.33V
∘ ∘ ∘
Ecell = Ered + Eox
∘
Ecell = 1.33V − 0.54V
∘
Ecell = 0.79V (a voltaic cell must have a positive voltage)
4. Use the table to calculate the standard cell voltage for a cell that employs the overall cell reaction
2Al(s) + 3I2(s) → 2Al 3+(a q) + 6I −(a q) ∘
Ecell =?
anode : 2Al(s) → 2Al 3+(a q) + 6e − ∘
Eox = 1.66V
cathode : 3I2(s) + 6e − → 6I −(a q) ∘
Ered = 0.54V
∘ ∘ ∘
Ecell = Ered + Eox
∘
Ecell = 1.66V + 0.54V
∘
Ecell = 2.2V (a voltaic cell must have a positive voltage)
5. A voltaic cell is based on the two standard half-reactions
Cd 2+(a q) + 2e − → Cd(s)
Sn 2+(a q) + 2e − → Sn(s)
Determine (a) which half-reaction occurs at the cathode and which occurs at the anode
(b) the standard cell voltage
(c) the overall cell reaction
Cd (a q) + 2e − → Cd(s)
2+ ∘
Ered = − 0.403V
Sn 2+(a q) + 2e − → Sn(s) ∘
Ered = − 0.136V
Since the standard voltage for the reduction of Sn2+(aq) to Sn(s) is more positive, it will take place at the
cathode and the oxidation of Cd(s) to Cd2+(aq) will take place at the anode.
anode : Cd(s) → Cd 2+(a q) + 2e − ∘
Eox = 0.403V
cathode : Sn 2+(a q) + 2e − → Sn(s) ∘
Ered = − 0.136V
∘ ∘ ∘
Ecell = Ered + Eox
∘
Ecell = − 0.136V + 0.403V
∘
Ecell = 0.267V (a voltaic cell must have a positive voltage)
Cd(s) + Sn 2+(a q) → Cd 2+(a q) + Sn(s) ∘
Ecell = 0.267V
6. A voltaic cell is based on a Co2+ | Co half-cell and an AgCl | Ag half-cell.
(a) What half-reaction occurs at the anode?
(b) what is the standard cell voltage?
(c) What is the overall cell reaction?
Co 2+(a q) + 2e − → Co(s) ∘
Ered = − 0.277V
A gCl(s) + e − → A g(s) + Cl −(a q) ∘
Ered = 0.222V
anode : Co(s) → Co 2+(a q) + 2e − ∘
Eox = 0.277V
cathode : A gCl(s) + e − → A g(s) + Cl −(a q) ∘
Ered = 0.222V

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 ∘ ∘ ∘
Ecell = Ered + Eox
∘
Ecell = 0.222V + 0.277V
∘
Ecell = 0.499V (a voltaic cell must have a positive voltage)
2A gCl(s) + Co(s) → 2A g(s) + 2Cl −(a q) + Co 2+(a q) ∘
Ecell = 0.499V
7. At standard conditions, will the reaction below occur?
Ni(s) + Z n 2+ → Ni 2+(a q) + Z n(s)

Practice Problems:
1. Write the half-reactions occurring at the anode and the cathode for the following reactions in a voltaic cell
and calculate the standard cell voltage.
a. Pb(s) + 2A g +(a q) → Pb 2+(a q) + 2A g(s)
b. MnO2(aq) + 4H +(a q) + 2I −(a q) → Mn 2+(a q) + 2H2O(l ) + I2(s)
c. Al | Al 3+(a q,1M ) | | Cu 2+(a q,1M ) | Cu
2. Write the cell notation for (a) and (b) in #1.
3. Is the reaction below spontaneous? Prove your answer by showing equations.
I2(s) + 2Br −(a q) → 2I −(a q) + Br2(l )
4. To obtain Mn2+ using Cl- as a reducing agent, should you use MnO2 or MnO4-?

CELL POTENTIAL UNDER NONSTANDARD CONDITIONS

We have learned how to calculate the voltage of cell under standard conditions. We recall that when we say
“standard” voltage, we mean voltage when gases are at 1 atm pressure and species in aqueous solutions are at
a concentration of 1M. However in reality, when a cell is discharged, standard conditions are not maintained as
the reactants are consumed in the process and the products are generated.

So what happens to the cell voltage when the concentration is not 1M?
When a voltaic cell operates supplying electrical energy, the concentration of the reactants decreases and that
of the products increases. The cell voltage drops until Ecell = 0V, at which point the cell is already dead. When
Ecell = 0V , the redox reaction taking place within the cell is at equilibrium, and there is no driving force to
produce a voltage.
How does the concentration of the reactants and products affect the cell voltage?
The cell voltage is directly proportional to the concentration of the reactant and inversely proportional to the
concentration of the product.

• The voltage will increase if

(a) the concentration of the reactant is increased
(b) the concentration of the product is decreased

• The voltage will decrease if

(a) the concentration of the reactant is decreased
(b) the concentration of the product is increased

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NERNST EQUATION
Walther Nernst, a German chemist who established many of the theoretical foundations of electrochemistry,
proposed the relationship between the cell voltage and concentration using the formula
0.0257V
E = E∘ − l nQ
n
where E = cell voltage, V
E°= standard voltage
n = number of moles of electrons exchanged in the reaction
Q = reaction quotient
The Reaction Quotient (Q)
The reaction quotient (Q) measures the relative amounts of products and reactants present during a reaction at
a particular point in time. The reaction quotient aids in figuring out which direction a reaction is likely to proceed,
given either the pressures or the concentrations of the reactants and the products.]
For a given reaction
a A + bB → cC + d D
Q is given by
[C ]c[D]d
Q=
[A]a[B]b
This equation only shows components in the gaseous or aqueous states. Gases enter Q as their partial
pressures in the atmosphere. Species in aqueous solutions enter as their molar concentrations. Pure liquids and
solids do not appear in the expression since their concentrations do not change.
[C ]c(D)d
a A(s) + bB(a q) → cC(a q) + d D(g) Q=
[B]b
How does Q relate to the cell voltage?
Q Concentration ln Q E vs E°

Q>1 Products > reactants positive E < E°

Q<1 Products < reactants Negative E > E°

Q=1 Standard conditions 0 E = E°

Sample Problems:
1. Consider a voltaic cell in which the following reaction occurs:
O2(g) + 4H +(a q) + 4Br −(a q) → 2H2O(l ) + 2Br2(l )
Calculate the cell voltage when O2 is at 1.0 atm pressure and [H +] = [Br −] = 0.10M
(a) break the equation into two half-reactions to solve for n
O2(g) + 4H +(a q) + 4e − → 2H2O(l ) ∘
Ered = + 1.229V
4Br −(a q) → 2Br2(l ) + 4e − ∘
Eox = − 1.077V
(b) solve E ∘
E ∘ = Eox
∘ ∘
+ Ered
E ∘ = 1.229V − 1.077V
E ∘ = 0.152V

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 (c) solve E using Nernst equation
0.0257V
E = E∘ − l nQ
n
0.0257V 1
E = E∘ − ln
n (PO2 )[H ]4[Br −]4
+

0.0257V 1
E = 0.152V − ln
4 (1.0a t m)[0.10M ]4[0.1M ]4

E = 0.035V
2. Consider a voltaic cell in which the following reaction takes place:
2H2O2(a q) + 6H +(a q) + 2Au(s) → 2Au 3+(a q) + 6H2O(l )
Calculate the cell voltage when [Au 3+] = 0.250M; [H +] = 1.25M; [H2O2 ] = 1.50M
(a) break the reaction into two half-reactions to solve n
H2O2(a q) + 2H +(a q) + 2e − → 2H2O(l ) ∘
Ered = + 1.763V
Au(s) → Au 3+(a q) + 3e − ∘
Eox = − 1.498V
(b) solve E ∘
E ∘ = Eox
∘ ∘
+ Ered
E ∘ = − 1.498V + 1.763V
E ∘ = 0.265V
(c) solve E using Nernst equation
0.0257V [Au 3+]2
E = E∘ − ln + 6
n [H ] [H2O2 ]3

0.0257V [0.25M ]2
E = 0.265V − ln
6 [1.25M ]6[1.50M ]3
E = 0.288V
3. Consider a voltaic cell in which the following reaction takes place:
3O2(g) + 4NO(g) + 2H2O(l ) → 4NO3−(a q) + 4H +(a q)
Calculate the cell voltage under the following conditions:
[NO3−] = 0.750M; PNO = 0.993a t m, PO2 = 0.515a t m; pH = 2.85
(a) break the reaction into two half-reactions to solve n
O2(g) + 4H +(a q) + 4e − → 2H2O(l ) ∘
Ered = + 1.229V
NO(g) + 2H2O(l ) → NO3−(a q) + 4H +(a q) + 3e − ∘
Eox = − 0.964V
(b) solve E ∘
E ∘ = Eox
∘ ∘
+ Ered
E ∘ = − 0.964V + 1.229V
E ∘ = 0.265V
(c) solve [H +]
pH = − log[H +]
[H +] = 10−pH

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 [H +] = 10−2.85
[H +] = 1.41x10−3 M
(d) solve E using Nernst equation
0.0257V [H +]4[NO3−]4
∘
E =E − ln
n (O2 )6(NO)4

0.0257V [1.41x10−3 M ]4[0.75M ]4

E = 0.265V − ln
12 (0.515a t m)3(0.993a t m)4

E = 0.319V
4. Consider a voltaic cell in which the reaction is
Z n(s) + 2H +(a q) → Z n 2+(a q) + H2(g)
It is found that the voltage is 0.560V when [Z n 2+] = 1.0M; PH 2 = 1.0a t m. What must be the
concentration of H + in the H2 − H + half cell?
(a) break the reaction into two half-reactions to solve n
Z n(s) → Z n 2+(a q) + 2e − ∘
Eox = + 0.762V
2H +(a q) + 2e − → H2(g) ∘
Ered = 0.00V
(b) solve E ∘
E ∘ = Eox
∘ ∘
+ Ered
E ∘ = 0.762V + 0.00V
E ∘ = 0.762V
(c) solve [H +] using Nernst equation
0.0257V (H2 )[Z n 2+]
E = E∘ − ln
n [H +]2

0.0257V (1.0a t m)[1.0M ]

0.560V = 0.762V − ln
2 [H +]2

1 0.762V − 0.560V
ln =
[H ]
+ 2 0.0257V
2

1
ln = 15.72
[H +]2

1
= e 15.72
[H +]2

[H +] = 3.716x10−4 M
5. Find the concentration of [H +] in the given cell notation.
Z n(s) | Z n 2+(a q,1.0M ) | | H +(a q, M ) | H2(g,1.0a t m) | Pt E = 0.40V
(a) break the reaction into two half-reactions to solve n
Z n(s) → Z n 2+(a q) + 2e − ∘
Eox = + 0.762V
2H +(a q) + 2e − → H2(g) ∘
Ered = 0.00V

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 (b) solve E ∘
E ∘ = Eox
∘ ∘
+ Ered
E ∘ = 0.762V + 0.00V
E ∘ = 0.762V
(c) solve [H +] using Nernst equation
0.0257V (H2 )[Z n 2+]
E = E∘ − ln
n [H +]2

0.0257V (1.0a t m)[1.0M ]4

0.40V = 0.762V − ln
2 [H +]2

1 0.762V − 0.40V
ln =
[H +]2 0.0257V
2

1
ln = 28.17
[H +]2

1
= e 28.17
[H +]2

[H +] = 7.63x10−7 M

6. Consider a voltaic cell in which the reaction is

S(s) + 2H +(a q) + 2A g(s) + 2Br −(a q) → 2A gBr (s) + H2 S(a q)
At what pH is the voltage zero if all the other species are at standard conditions?
(a) break the reaction into two half-reactions to solve n
S(s) + 2H +(a q) + 2e − → H2 S(a q) ∘
Ered = + 0.144V
A g(s) + Br −(a q) → A gBr (s) + e − ∘
Eox = − 0.073V
(b) solve E ∘
E ∘ = Eox
∘ ∘
+ Ered
E ∘ = − − 0.073V + 0.144V
E ∘ = 0.071V
(c) solve [H +] using Nernst equation
0.0257V ([H S ]
E = E∘ − ln + 2 2 − 2
n [H ] [Br ]

0.0257V ([1.0M ]
0.00V = 0.071V − ln + 2
2 [H ] [1.0M ]2

1 0.071V
ln =
[H +]2 0.0257V
2

1
ln = 5.53
[H +]2

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 1
= e 5.53
[H +]2

[H +] = 0.063M
pH = − log[H +]
pH = − log[0.063]
pH = 1.20

Practice Problems:
1. Consider the reaction:
MnO2(s) + 4H +(a q) + 2Br −(a q) → Mn 2+(a q) + Br2(l ) + 2H2O(l )
At what pH is the voltage zero if all the other species are at standard concentrations?
2. Find the concentration of [H +] in the given cell notation.
A g(s) | Br −(a q,3.73M ) | | H +(a q, M ) | H2(g,1.0a t m) | Pt E = − 0.03V
3. Consider the reaction at 25∘C
2NO3−(a q) + 8H +(a q) + 3Cu(s) → 3Cu 2+(a q) + 2NO(g) + 4H2O(l )
(a) is the reaction spontaneous?
(b) is the reaction spontaneous at pH=3.00 with all the other ionic species at 0.100M and gases at 1.00 atm?
(c) is the reaction spontaneous at pH=6.00 with all the other ionic species at 0.100M and gases at 1.00 atm?
(d) at what pH is the reaction at equilibrium with all other ionic species at 0.100M and gases at 1.00 atm?
4. Find the concentration of [H +] in the given cell notation.
A g(s) | Br −(a q,3.73M ) | | H +(a q, M ) | H2(g,1.0a t m) | Pt E = − 0.03V

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