This reaction is in acidic medium since there are H+ ions present.

To make the
ELECTROCHEMISTRY reaction in basic medium, just add same amount of OH- to that of H+. The reaction
will then look like
Electrochemistry is the branch of chemistry that deal with the interconversion of
electrical energy and chemical energy. Electrochemical processes are redox 6𝐹𝑒 2+ + 7𝐻2 𝑂 + 𝐶𝑟2 𝑂72− → 6𝐹𝑒 3+ + 2𝐶𝑟 3+ + 14 𝑂𝐻 −
reaction in which the energy released by spontaneous reaction is converted to
electricity, or in which electrical energy Is used to cause a nonspontaneous reaction ACTIVITY
to occur. 1. Write a balanced ionic equation to represent the oxidation of iodide ion
𝐼− by permanganate ion 𝑀𝑛𝑂4− in basic solution to yield molecular
BALANCING REDOX REACTION iodine 𝐼2 and manganese (IV) oxide 𝑀𝑛𝑂2 .
Brief Mnemonic Guide

OIL RIG oxidation is losing (electron) reduction is gaining (electron)

LEORA GEROA losing electron, oxidation, reducing agent

gaining election, reduction, oxidizing agent

In order to balance redox reactions, we should be able to recognize which species

undergo reduction or oxidation process. For example, for the reaction

𝐹𝑒 2+ + 𝐶𝑟2 𝑂72− → 𝐹𝑒 3+ + 𝐶𝑟 3+

We will notice that the oxidation number of iron increases from (2+) to (3+), thus
iron underwent an oxidation process. Consequently, this means that chromate ion
underwent reduction process to chromium (III) ion. We can write these two half-
reactions as

𝐹𝑒 2+ → 𝐹𝑒 3+ oxidation 2. Write the balanced equation 𝐹𝑒 2+ + 𝑀𝑛𝑂4− → 𝐹𝑒 3+ + 𝑀𝑛2+

𝐶𝑟2 𝑂72− → 𝐶𝑟 3+ reduction

Balance each half-reaction for the number and type of atoms and charges. Add H2O
to balance O atoms and H+ to balance H atoms. To balance charges, add electrons.
The resulting balanced half-reactions are shown as below.

𝐹𝑒 2+ → 𝐹𝑒 3+ + 𝑒 − oxidation

6𝑒 − + 14𝐻+ + 𝐶𝑟2 𝑂72− → 2𝐶𝑟 3+ + 7𝐻2 𝑂 reduction

Finally, add the two half-reactions together. The electrons must cancel out in the
final equation, so you may multiply a factor to any of the two equations.

The balanced equation is written as

6 𝐹𝑒 2+ + 14 𝐻+ + 𝐶𝑟2 𝑂72− → 6 𝐹𝑒 3+ + 2 𝐶𝑟 3+ + 7𝐻2 𝑂

CRUZ | Chemistry for Engineers
3. Write the balanced equation 𝑆𝑛 + 𝑁𝑂3− → 𝑆𝑛𝑂2 + 𝑁𝑂2
4. Write the balanced equation 𝑍𝑛 + 𝑁𝑂3− → 𝑍𝑛2+ + 𝑁𝐻4+
VOLTAIC CELL
An electrochemical cell is a system consisting of electrodes that dip into an
electrolyte and in which a chemical reaction either uses or generates an electric
current.
A voltaic, or galvanic, cell is an electrochemical cell in which a spontaneous reaction
generates an electric current. An electrolytic cell is an electrochemical cell in which
an electric current drives an otherwise nonspontaneous reaction.
CONSTRUCTION OF VOLTAIC CELLS
A voltaic cell consists of two half-cells that are electrically connected. Each half-cell
is the portion of an electrochemical cell in which a half-reaction takes place. The
electrode at which oxidation occurs is called the anode. The other electrode at which
the reduction occurs is called the cathode. The two half-cells are connected by a salt
bridge. A salt bridge is a tube on an electrolyte in a gel that is connected to the two
half-cells of a voltaic cell; the salt bridge allows the flow of ions but prevents the
mixing of the different solutions that would allow direct reaction of the cell
reactants.
Brief Mnemonic Guide
OXAN REDCAT oxidation-anode; reduction cathode
The image shown above has the half-cell reactions
𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 − oxidation (anode)
𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 reduction (cathode)
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CRUZ | Chemistry for Engineers
The sum of the two half-reactions is

𝑍𝑛 + 𝐶𝑢2+ → 𝑍𝑛2+ + 𝐶𝑢 ACTIVITY

1. A voltaic cell is constructed from a half-cell in which a cadmium rod dips
The net reaction that occurs in the voltaic cell is called the cell reaction.
into a solution of cadmium nitrate, Cd(NO3)2, and another half-cell in
which a silver rod dips into a solution of silver nitrate, AgNO 3. The two
half-cells are connected by a salt bridge. Silver ion is reduced during
operation of the voltaic cell. Draw a sketch of the cell. Label the anode
and cathode, showing the corresponding half-reactions at these
electrodes. Indicate the electron flow in the external circuit (with a
lightbulb), the signs of the electrodes, and the direction of cation
migration in the half-cells.

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CRUZ | Chemistry for Engineers
2. A voltaic cell consists of a silver–silver ion half-cell and a nickel–nickel(II) 3. 3𝐹𝑒 2+ + 2𝐴𝑙 → 3𝐹𝑒 + 2𝐴𝑙 3+
ion half-cell. Silver ion is reduced during operation of the cell. Sketch the
cell, labeling the anode and cathode and indicating the corresponding
electrode reactions. Show the direction of electron flow in the external
circuit and the direction of cation movement in the half-cells.

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CRUZ | Chemistry for Engineers
NOTATION FOR VOLTAIC CELLS b. 𝑍𝑛(𝑠) | 𝑍𝑛2+ (𝑎𝑞) || 𝐹𝑒 3+ (𝑎𝑞), 𝐹𝑒 2+ (𝑎𝑞) | 𝑃𝑡

There is a shorthand way of designating particular voltaic cells. The cell described
earlier consisting of zinc metal-zinc ion half-cell and copper metal-copper ion half-
cell is written as

𝑍𝑛(𝑠) | 𝑍𝑛2+ (𝑎𝑞) || 𝐶𝑢2+ (𝑎𝑞) | 𝐶𝑢(𝑠)

In this notation, the anode is always written on the left; the cathode is written on the c. 𝐶𝑑(𝑠) | 𝐶𝑑2+ (𝑎𝑞) || 𝐻+ (𝑎𝑞) | 𝐻2 (𝑔) | 𝑃𝑡
right. The two electrodes are electrically connected by a salt bridge, denoted by two
vertical bars. The single vertical bar, however, says that there is a phase boundary
between the solid terminal and the electrolyte solution. A comma can be used to
separate ions present in the same solution.

When the half-reaction involves a gas, an inert material such as platinum serves as
a terminal and as an electrode surface on which the half-reaction occurs. For To fully specify a voltaic cell, it is necessary to give the concentrations of solution or
example, the cathode half-reaction ions and the pressure of gases. In the cell notation, these are written within
parenthesis for each species. For example,
2𝐻 + + 2𝑒 − ⇌ 𝐻2
𝑍𝑛(𝑠) | 𝑍𝑛2+ (1.0𝑀) || 𝐻+ (1.0𝑀) |𝐻2 (1.0 𝑎𝑡𝑚) | 𝑃𝑡
The notation for the hydrogen electrode as cathode is

𝐻+ (𝑎𝑞) | 𝐻2 (𝑔) | 𝑃𝑡 STANDARD CELL POTENTIALS AND STANDARD ELECTRODE

POTENTIAL
To write this as an anode, simply reverse the notation
A cell potential is a measure of the driving force of the cell reaction. This reaction
𝑃𝑡 | 𝐻2 (𝑔) | 𝐻+ (𝑎𝑞) occurs in the cell as separate half-reactions: and oxidation half-reaction and a
reduction half-reaction. The cell potential is the sum of the contributions of oxidation
ACTIVITY potential and reduction potential, that is
1. Write the notation for a cell in which the electrode reactions are
a. 2𝐻+ + 2𝑒 − → 𝐻2 𝐸𝑐𝑒𝑙𝑙 = oxidation potential + reduction potential

A reduction potential is a measure of the tendency for an oxidized species to gain

b. 𝑍𝑛 → 𝑍𝑛 2+
+ 2𝑒 − electrons in the reduction half-reaction. The oxidation potential is the negative of
the reduction potential on the other hand.
𝑜
2. Write the cell reaction for the voltaic cell By convention, the standard emf of the cell 𝐸𝑐𝑒𝑙𝑙 is given by
a. 𝑇𝑙 (𝑠) | 𝑇𝑙 + (𝑎𝑞) || 𝑆𝑛2+ (𝑎𝑞) | 𝑆𝑛(𝑠)
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒

where both 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 and 𝑬𝒐𝒂𝒏𝒐𝒅𝒆 are the standard reduction potentials of the
electrodes.

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CRUZ | Chemistry for Engineers
Consider the zinc-copper cell

𝑍𝑛(𝑠)|𝑍𝑛2+ (𝑎𝑞)||𝐶𝑢2+ (𝑎𝑞)|𝐶𝑢(𝑠)

The half-reactions are

𝑍𝑛(𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 − 𝑎𝑛𝑜𝑑𝑒

𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) 𝑐𝑎𝑡ℎ𝑜𝑑𝑒

The emf of the cell is

𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜 𝑜
= 𝐸𝐶𝑢2+/𝐶𝑢 − 𝐸𝑍𝑛 2+ /𝑍𝑛

= 0.34 𝑉 − (−0.76𝑉)
= 1.10 𝑉

Table 19.1 lists standard reduction potentials for several half-cell reactions. The
SHE has an E° value of 0.00 V. Below the SHE the negative standard reduction
potentials increase, and above it the positive standard reduction potentials
increase. It is important to know the following points about the table in calculations:

1. The E° values apply to the half-cell reactions as read in the forward (left to
right) direction.
2. The more positive E° is, the greater the tendency for the substance to be
reduced.
3. Under standard-state conditions, any species on the left of a given half-cell
reaction will react spontaneously with a species that appears on the right
of any half-cell reaction located below it in Table 19.1. This principle is
sometimes called the diagonal rule.
4. Changing the stoichiometric coefficients of a half-cell reaction does not
affect the value of E° because electrode potentials are intensive
properties.
5. The sign of E° changes but its magnitude remains the same when we
reverse a reaction.
6. The positive E°cell means that the reaction is galvanic cell / the reaction is
spontaneous.

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CRUZ | Chemistry for Engineers
ACTIVITY e. 𝐹𝑒 2+ + 𝐶𝑟2 𝑂72− → 𝐹𝑒 3+ + 𝐶𝑟 3+
𝑜
1. Determine the 𝐸𝑐𝑒𝑙𝑙 of the following reactions
a. 𝐶𝑑(𝑠) | 𝐶𝑑2+ (𝑎𝑞) || 𝐻+ (𝑎𝑞) | 𝐻2 (𝑔) | 𝑃𝑡

f. 𝐹𝑒 2+ + 𝑀𝑛𝑂4− → 𝐹𝑒 3+ + 𝑀𝑛2+

b. 𝑍𝑛(𝑠) | 𝑍𝑛2+ (𝑎𝑞) || 𝐹𝑒 3+ (𝑎𝑞), 𝐹𝑒 2+ (𝑎𝑞) | 𝑃𝑡

2. A galvanic cell consists of a Mg electrode in a 1.0 M Mg(NO 3)2 solution

and a Ag electrode in a 1.0 M AgNO3 solution. Calculate the standard
emf of this cell at 25°C.
c. 𝐻𝑔22+ (𝑎𝑞) + 𝐻2 (𝑔) ⇌ 2𝐻𝑔(𝑙) + 2𝐻+ (𝑎𝑞)

3. 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
d. 3𝐹𝑒 2+ + 2𝐴𝑙 → 3𝐹𝑒 + 2𝐴𝑙 3+ standard states.

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CRUZ | Chemistry for Engineers
4. Can Sn reduce Zn2+(aq) under standard-state conditions? Therefore, the total charge can now be expressed as nF, where n is the number of
moles of electrons exchanged between the reducing agent and the oxidizing agent
in the overall redox equation.

The measured emf (Ecell) is the maximum voltage the cell can achieve. It is given by
the electrical work done (wele) divided by the total charge; that is,

−𝑤𝑒𝑙𝑒 −𝑤𝑒𝑙𝑒
𝐸𝑐𝑒𝑙𝑙 = = 𝑜𝑟
𝑡𝑜𝑡𝑎𝑙 𝑐ℎ𝑎𝑟𝑔𝑒 𝑛𝐹
5. What is the standard emf of a galvanic cell made of a Cd electrode in a
1.0 M Cd(NO3)2 solution and a Cr electrode in a 1.0 M Cr(NO3)3 solution
𝑤𝑒𝑙𝑒 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
at 25°C?
The negative sign indicates that the electrical work is done by the system (galvanic
cell) on the surroundings

In previous chapters, free energy is defined as the energy available to do work.

Specifically, the change in free energy Δ𝐺 represents the maximum amount of
useful work that can be obtained in a reaction:

Δ𝐺 = 𝑤𝑚𝑎𝑥 = 𝑤𝑒𝑙𝑒
THERMODYNAMICS OF REDOX REACTIONS
Therefore,
Work is needed to move electrons in a wire. An electric charge moves from a point
at high electrical potential (high electrical pressure) to a point at low electric Δ𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
potential (low electrical pressure). The work needed to move an electric charge
through a conductor depends on the total charge moved and the potential At standard conditions
difference. Potential difference is the difference in electric potential (electrical
𝑜
pressure) between two points. This is measured in volts. The electrical work Δ𝐺 𝑜 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
expended in moving a charge through a conductor is
For the reaction to be spontaneous, 𝐸𝑐𝑒𝑙𝑙 must be positive.
electrical work = charge × potential difference
𝑜
Now, 𝐸𝑐𝑒𝑙𝑙 can be related to the equilibrium constant 𝐾 of a redox reaction given by
Corresponding SI units for the terms in this equation is the equation

Joules = coulombs × volts Δ𝐺 𝑜 = −𝑅𝑇 ln 𝐾

The total charge is determined by the number of electrons that pass through the Combining the Δ𝐺 𝑜 expressions, we obtain
cell, so we have
𝑜
−𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑅𝑇 ln 𝐾
− −
total charge = # of e × charge of one e
𝑜
Solving for 𝐸𝑐𝑒𝑙𝑙
In general, it is more convenient to express the total charge in molar quantities. The
Faraday constant, F, is the magnitude of charge on one mole of electrons; it equals 𝑜 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = ln 𝐾
96485 C/mol e-. The faraday is a unit of charge equal to 96485 C. 𝑛𝐹

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CRUZ | Chemistry for Engineers
When 𝑇 = 298 𝐾, the previous expression can be simplified as b. 𝐹𝑒 2+ (𝑎𝑞) + 2𝐴𝑔(𝑠) ⇌ 𝐹𝑒(𝑠) + 2𝐴𝑔+ (𝑎𝑞)

𝐽
(8.314 ) (298 𝐾)
𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝑚𝑜𝑙𝐾 ln 𝐾 𝑜𝑟 𝑠𝑖𝑚𝑝𝑙𝑦
𝐽
𝑛 (96500 )
𝑉𝑚𝑜𝑙

𝑜 0.0257 𝑉
𝐸𝑐𝑒𝑙𝑙 = ln 𝐾 𝑜𝑟
𝑛

𝑜 0.0592 𝑉
𝐸𝑐𝑒𝑙𝑙 = log 𝐾
𝑛

c. 𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) ⇌ 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)

ACTIVITY
1. Calculate the equilibrium constant for the following reaction at 25°C.
a. 𝑆𝑛(𝑠) + 2𝐶𝑢2+ (𝑎𝑞) ⇌ 𝑆𝑛2+ (𝑎𝑞) + 2𝐶𝑢+ (𝑎𝑞)

d. 𝐹𝑒(𝑠) + 𝑆𝑛4+ (𝑎𝑞) ⇌ 𝐹𝑒 2+ (𝑎𝑞) + 𝑆𝑛2+ (𝑎𝑞)

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CRUZ | Chemistry for Engineers
2. Calculate the standard free-energy change for the following reaction at d. 𝑆𝑛2+ (𝑎𝑞) + 2𝐻𝑔2+ (𝑎𝑞) → 𝑆𝑛4+ (𝑎𝑞) + 𝐻𝑔22+ (𝑎𝑞)
25°C:
a. 2𝐴𝑢(𝑠) + 3𝐶𝑎2+ (1.0 𝑀) → 2𝐴𝑢3+ (1.0 𝑀) + 3𝐶𝑎(𝑠)

b. 2𝐴𝑙 3+ (𝑎𝑞) + 3𝑀𝑔(𝑠) ⇌ 2𝐴𝑙(𝑠) + 3𝑀𝑔2+ THE EFFECT OF CONCEN TRATION ON CELL EMF
Recall that the free-energy change, Δ𝐺 , is related to the standard free-energy
change, Δ𝐺 𝑜 , by the following equation:

Δ𝐺 = Δ𝐺 𝑜 + 𝑅𝑇 ln 𝑄

Here Q is the thermodynamic reaction quotient. The reaction quotient has the form
of the equilibrium constant, except that the concentrations and gas pressures are
those that exist in a reaction mixture at a given instant. You can apply this equation
to a voltaic cell. In that case, the concentrations and gas pressures are those that
𝑜
exist in the cell at an instant. If you substitute Δ𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 and Δ𝐺 𝑜 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙
into this equation, you obtain
𝑜
c. 𝑍𝑛(𝑠) + 2𝐴𝑔 + (𝑎𝑞) → 𝑍𝑛2+ + 2𝐴𝑔(𝑠) −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 + 𝑅𝑇 ln 𝑄

Rearranging in terms of cell potential, this results to the Nernst Equation, an

equation relating the cell potential to its standard cell potential and the reaction
quotient.

𝑜 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln 𝑄
𝑛𝐹

𝑜 2.303𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log 𝑄
𝑛𝐹

At 298 K,

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CRUZ | Chemistry for Engineers
𝑜 0.0592 2. Consider the galvanic cell shown below. In a certain experiment, the emf
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log 𝑄
𝑛 of the cell is found to be 0.54 V at 25°C. Suppose that [𝑍𝑛2+ ] = 2.5 𝑀
and 𝑃𝐻2 = 1.0 𝑎𝑡𝑚, what is the pH of the solution?
The Nernst equation enables us to calculate E as a function of reactant and product 𝑍𝑛(𝑠) + 2𝐻+ (? 𝑀) → 𝑍𝑛2+ (2.5 𝑀) + 𝐻2 (1.0 𝑎𝑡𝑚)
concentrations in a redox reaction. For example, for the Daniell cell

𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠)

The Nernst equation for this cell at 25°C can be written as

0.0257 𝑉 [𝑍𝑛2+ ]
𝐸 = 1.10 𝑉 − ln
2 [𝐶𝑢2+ ]

ACTIVITY
1. Predict whether the following reaction would proceed spontaneously at
298 K
a. 𝐶𝑜(𝑠) + 𝐹𝑒 2+ (𝑎𝑞) → 𝐶𝑜2+ (𝑎𝑞) + 𝐹𝑒(𝑠) given that [𝐶𝑜2+ ] =
0.25 𝑀 and [𝐹𝑒 2+ ] = 0.94 𝑀

3. What is the emf of a galvanic cell consisting of a Cd 2+/Cd half-cell and a

Pt/H+/H2 half-cell if [𝐶𝑑2+ ] = 0.20 𝑀 , [𝐻+ ] = 0.16 𝑀 , and 𝑃𝐻2 =
0.80 𝑎𝑡𝑚?

b. 𝐶𝑑(𝑠) + 𝐹𝑒 2+ (𝑎𝑞) → 𝐶𝑑2+ (𝑎𝑞) + 𝐹𝑒(𝑠) given that [𝐹𝑒 2+ ] =

0.60 𝑀 and [𝐶𝑑2+ ] = 0.010 𝑀

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4. Consider the cell diagram
𝑀𝑔(𝑠)|𝑀𝑔𝑆𝑂4 (0.40 𝑀)||𝑁𝑖𝑆𝑂4 (0.60 𝑀)|𝑁𝑖(𝑠)
Calculate the cell voltage at 25°C. How does the cell voltage change
when:
a. [𝑀𝑔2+ ] is decreased by a factor of 4
b. [𝑁𝑖 2+ ] is decreased by a factor of 3

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