CHE 401 : ANALYTICAL CHEMISTRY

MODULE
6
OXIDATION – REDUCTION REACTIONS AND
TITRATIONS

INTRODUCTION
This module discuss the methods used in oxidation reaction reactions. It is important to learn to
balance the oxidation reduction reactions and the principle of the process. At the end of the module,
the students are expected to understand the calculations involved in this method, be familiar with
electrochemical cell and acquire techniques in laboratory experiments involving electrochemistry.

INTENDED LEARNING OUTCOMES

At the end of the module, the following learning outcomes are expected to be acquired by the
students:
1. Understand the concepts and principles of oxidation reduction reactions.
2. Execute calculation techniques used in oxidation reduction reactions.
3. Acquire skills in laboratory technique required to perform and plan chemical analysis and
systematically collect and interpret data obtained in quantitative analytical process.

CONTENT OVERVIEW
Indicative contents included the following topics:
1. Characterizing oxidation reduction reactions
2. Oxidation reduction titration
3. Electrochemical Cells

END OF THE MODULE TEST

The following are the assessment provided to evaluate students level of understanding after the
discussion of the modules:

Coursework (100 points )

Solving problems involving oxidation reduction reactions.

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Table of Contents

MODULE 6. OXIDATION REDUCTION REACTIONS AND TITRATIONS ................... 3

6.1 CHARACTERIZING OXIDATION/REDUCTION REACTIONS ......................... 3

6.1.1 Oxidation Reduction Reactions .................................................................................... 3

6.1.2 Three categories in the General Methods of REDOX Analysis: ................................. 4

6.1.3 Indicators for REDOX Reactions ................................................................................ 5

6.1.4 Comparing Redox Reactions to Acid/Base Reactions ................................................ 6

6.2 OXIDATION- REDUCTION TITRATIONS ............................................................. 7

6.2.1 Permanganimetric Titration ........................................................................................ 7

6.2.2 Titrations Involving Iodine ....................................................................................... 8

6.2.3 Oxidation/Reduction Reactions in Electrochemical Cells......................................... 10

6.3 ELECTROCHEMICAL CELLS ................................................................................ 12

6.3.1 Cathodes and Anodes ................................................................................................. 12

6.3.2 Types of Electrochemical Cells ................................................................................. 13

6.3.3 Representing Cells Schematically .............................................................................. 13

6.3.4 Currents in Electrochemical Cells .............................................................................. 14

6.3.5 Electrode Potentials .................................................................................................... 15

6.4 END OF MODULE TEST ........................................................................................... 16

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MODULE 6. OXIDATION REDUCTION REACTIONS AND TITRATIONS

An oxidation-reduction (REDOX) reaction is a type of chemical reaction that involves a transfer

of electrons between two species. An oxidation-reduction reaction is any chemical reaction in
which the oxidation number of a molecule, atom, or ion changes by gaining or losing an electron.

6.1 CHARACTERIZING OXIDATION/REDUCTION REACTIONS

There are two types of reactions in aqueous solutions:

1. Methatesis or Double Decompositon – ( Precipitation/Neutralization )

2. Oxidation-Reduction ( Change in oxidation state )

Gaining of electron – reduced → GEROA

Losing an electrons – oxidized → LEORA

6.1.1 Oxidation Reduction Reactions

In an oxidation/reduction reaction, electrons are transferred from one reactant to another.
An example is the oxidation of iron(II) ions by cerium(IV) ions. The reaction is described by the
equation
𝐶𝑒 4+ + 𝐹𝑒 2+ ⇌ 𝐶𝑒 3+ + 𝐹𝑒 3+ (6.1)
1e + Ce+4 → Ce+3 O.A.
Fe+2 → Fe+3 + 1e R.A.

In this reaction, an electron is transferred from Fe 2+ to Ce4+ to form Ce3+ and Fe3+ ions. A
substance that has strong affinity for electrons, such as, Ce 4+, is called an oxidizing agent, or an
oxidant. A reducing agent, or reductant, is a species, such as Fe 2+, that easily donates electrons to
another species. To describe the chemical behavior represented by equation 9-1, we say that Fe2+
is oxidized by Ce4+ similarly Ce4+ is reduced by Fe2+.

We can split any oxidation/reduction equation into two half-reactions that show which
species gains electrons and which loses them. For example, Equation 9-1 is the sum of the two
half-reactions
𝐶𝑒 4+ + 𝑒 − ⇌ 𝐶𝑒 3+ (𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐶𝑒 4+)
𝐹𝑒 2+ ⇌ 𝐹𝑒 3+ + 𝑒 − (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐹𝑒 2+)

The rules for balancing half-reactions (see Feature 18-1) as the same as those for other
reaction types; that is, the number of atoms of each element as well as the net charge on each side
of the equation must be the same. Thus, for the oxidation of Fe 2+ by 𝑀𝑛𝑂4−, the half-reactions are
𝑀𝑛𝑂4− + 5𝑒 − + 8𝐻 + ⇌ 𝑀𝑛2+ + 4𝐻2 𝑂

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5𝐹𝑒 2+ ⇌ 5𝐹𝑒 3+ + 5𝑒 −

In the first half-reaction, the net charge on the left side is (-1-5+8) = +2, which is the same
as the charge on the right. Note also that we have the second half-reaction by 5 so that the number
of electrons lost by Fe2+ equals the number gained by 𝑀𝑛𝑂4− . We can then write a balanced net-
ionic equation of the overall reaction by adding the two-half reactions
𝑀𝑛𝑂4− + 5𝐹𝑒 2+ + 8𝐻 + ⇌ 𝑀𝑛2+ + 5𝐹𝑒 3+ + 4𝐻2 𝑂

REDOX reaction may be used as basis for a volumetric analysis if:

1. There is only one reaction under the given condition
2. This reaction goes essentially to completion at the equivalence point
3. Suitable indicator ( or other means ) is available to locate the endpoint

6.1.2 Three categories in the General Methods of REDOX Analysis:

1. A solution of a substance that is readily oxidized is titrated by a standard solution of strong

oxidizing agent ( SOA)
Most widely used strong oxidizing agent
a. Mn04- in acidic solution
b. Cr2O72- I acid solution
c. Ce+4 in acid solution
d. I2 in I- solution
e. MnO4- in basic solution

In titration of reducing agents by a strong oxidizing agent, it is necessary to pre-

treat the sample before the titrations to insure that all the sought substances is reduced o its
lower oxidation state and to insure that no reducing get other that the sought material is in
solution.
2Fe+3 + Zn → 2Fe+2 + Zn+2

After reduction, metallic Zn is removed from the solution then titrated by a standard
solution of KMn04

MnO4- + 5Fe+2 + 8H+ → Mn+2 + 5Fe+3 + 4H2O

2. If the sample is a strong oxidizing agent, it is necessary to pre-treat the sample before the
titrations to insure that all the sought substances is reduced to its lower oxidation state and
to insure that no reducing get other that the sought material is in the solution.

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A. Ferrous salt solution

B. Arsenious acid

3. An indirect method is frequently used for analyses of oxidizing agents. The sample is
treated with a solution of KI, and the liberated iodine is titrated by a solution of Na 2S2O3
which reacts rapidly and quantitatively with I2.
I2 + S2O3-2 → 2I- + S4O6-2

Three standard reagents

1. KMnO4 – strong OA
2. H3AsO3 – strong OA
3. Na2S2O3 – specific reagent for I2

6.1.3 Indicators for REDOX Reactions

The indicators must be the substance that is oxidized or reduced at or near the equivalence
point of the titration. For titrating a reducing agent indicator must be substance that is more difficult
to oxidize than the sample.

Two most widely used indicators

1. Dipheylamine sulfonic acid (normally used a the soluble barium or sodium salt)→
strong R for Cr2O72=
2. Ferrous complex of orthophenanthroline (Ferroin)

More common specific REDOX Indicators

1. Color of the permangate ion
a. When reduced the Mn04- gives (in acid solution ) the colorless Mn+2
b. The colored endpoint appears with the first drop of MnO4- in excess after the
entire sample is oxidized.
2. Starch indicator for I2
- Colloidal suspension of starch will, in presence of I-give an intense blue color
with free I2

3. Spot test indicator

- Made as the equivalence point is approached
- Done by withdrawing a drop of solution after each addition of reagent and testing
this drop for the constituent that is being oxidized or reduced.

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4. Potentiometric endpoint
- “voltage difference”

6.1.4 Comparing Redox Reactions to Acid/Base Reactions

Oxidation/Reduction reactions can be viewed in a way that is analogous to the Bronsted-

Lowry concept of acid/base reactions. Both involve the transfer of one or more charged particles
from a donor to an acceptor- the particles being electrons in oxidation/reduction and protons in
neutralization. When an acid donates a proton, it becomes a conjugate base that is capable of
accepting a proton. By analogy, when a reducing agent donates an electron, it becomes an
oxidizing agent that can then accept an electron. This product could be called a conjugate oxidant,
but that terminology is seldom, if ever, used. With this idea in mind we can write a generalized
equation for a redox reaction as

𝐴𝑟𝑒𝑑 + 𝐵𝑜𝑥 ⇌ 𝐴𝑜𝑥 + 𝐵𝑟𝑒𝑑 (6.2)

Here, Box, the oxidized form of species B, accepts electrons from Ared to form the new
reductant, Bred. At the same time, reductant Ared, having given up electrons, becomes oxidizing
agent, Aox. If we know from chemical evidence that the equilibrium in equation 9-2 lies to the
right, we can state that Box is a better electron acceptor (stronger oxidant) that A ox. Furthermore,
Ared is a more effective electron donor (better reductant) than Bred.

Example 6.1
The following reactions are spontaneous and thus proceed to the right, as written

2𝐻 + + 𝐶𝑑(𝑠) ⇌ 𝐻2 + 𝐶𝑑 2+
2𝐴𝑔+ + 𝐻2 (𝑔) ⇌ 2𝐴𝑔(𝑠) + 2𝐻 +
𝐶𝑑 2+ + 𝑍𝑛(𝑠) ⇌ 𝐶𝑑(𝑠) + 𝑍𝑛2+

What can we deduce regarding the strength of H+,Ag+,Cd2+, and Zn2+ as electron acceptors
(or oxidizing agent)?
The second reaction establishes that Ag+ is a more effective electron acceptor than H+; the
first equation demonstrates that H+ is more effective than Cd2+. Finally, the third equation shows
that Cd2+ is more effective than Zn2+, Thus the order of oxidizing strength is Ag+>H+>Cd2+>Zn2+.

Table 6.1 Common Oxidizing and Reducing Agents

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OXIDIZING AGENTS REDUCING AGENTS

Bromine Carbon
Chlorine Carbon Monoxide
Concentrated Sulfuric Acid Hydrogen
Nitric Acid Hydrogen Sulfide
Oxygen Metals
Potassium Manganate(VII) Potassium Iodide
Potassium Dichromate(VI) Sulfur Dioxide
Hydrogen Peroxide Ammonia

6.2 OXIDATION- REDUCTION TITRATIONS

6.2.1 Permanganimetric Titration

Manganese can exist in several oxidation states; the most stable are 7, 6, 4, 3, and 2.
The 1 and 5 oxidation states exist, but are too unstable to be of analytical interest.

The most widely used group of permanganimetric titrations is based on the reduction
of MnO4- to Mn2+ in acid solution.

MnO4 − + 8H+ + 5e− → Mn2+4H2 O E0 = +1.5 volts

Potassium permanganate, KMnO4, is a very powerful oxidizing agent that may be used
to determine many substances by direct or indirect titration. The reactions from which these
determinations are based and have been well studied and most of the determinations are highly
accurate. The particular advantage of KMnO4 is that it serves as its own indicator owing to the
intense purple of the permanganate ion; one drop in excess colors the solution a definite pink
and this is taken as the end point in titration.

These are, however, some disadvantages of KMnO4 as an oxidizing agent. From

thermodynamic considerations, permanganate solutions are inherently unstable because
KMnO4, Is capable of oxidizing water spontaneously.

4MnO4 − + 2H2 O+ → 4MnO2 + 3O2 + 4OH −

Fortunately the rate of this reaction is very slow if proper precautions are taken in the
original preparation of the solution. The reaction had been observed to be catalyzed by heat,
light, acids, bases, Mn2+, salts, and especially by MnO2. Even with precaution, permanganate

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solutions decompose with time and therefore should be standardized again at frequent
intervals.

Example 6.2
A standardized 4 M solution of KMnO4 is titrated against a 100 ml sample of an
unknown analyte containing Fe2+. A student conducts the redox titration and reaches the
endpoint after adding 25 ml of the titrant. What is the concentration of the analyte?

2+
1L 4 mol KMnO4 5 mol Fe2+
mol Fe = 25 ml KMnO4 × × × = 0.5 mol Fe2+
1000 ml 1L 1 mol KMnO4
0.5 mol Fe2+
concentration of analyte = = 5M
0.100 L

6.2.2 Titrations Involving Iodine

Solid elemental iodine, I2, is only slightly soluble in water. Its solubility is enhanced by the
presence of sodium of potassium iodide because of the formation of the triiodide ion:
I2 + I− → I3−

A large number of analytical methods have been developed involving iodine-iodide ion
equilibrium. For convenience in writing and balancing chemical equations, iodine dissolved in
water will simply be written as I2. The standard potential for half-reaction is
I2 + 2e− → 2I− E0 = +0.535 V

Two major classification of redox methods involving the use of this half-reaction are as
follows:..

1. Iodimetric method or Direct method – a solution of iodine serves as standard

oxidizing agent.

2. Iodometric method or Indirect method – free iodine (I2) is formed through a reaction
of excess iodine ion with some oxidizing agent.

The prevalence of redox methods involving iodine may be further attributed to the
availability of a sensitive indicator, starch; dispersed starch forms an intense blue complex
with iodine. Water and iodide are also involved in the complex, which is really a hydrated
colloidal particle with iodide and iodine absorbed upon it. The blue color is readily
reversible and may be used as a sensitive indicator for traces of iodine in solution.

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I− + I2 + starchcolorless → (starch, I −, I2 )blue

Since the blue color is destroyed by alkalis, titration to a starch end point should be
made below pH 8. In general, agents that coagulate colloids or hinder adsorption of iodine
decrease the sensitivity of the test. Heat, alcohol, and concentrated solutions of strong
electrolytes are to be avoided, if possible.

1. Direct Titration with Iodine (Iodimetry)

Since iodine is only a weak oxidizing agent, its application as a titrant is quite
limited. Nevertheless, several substances are commonly determined by titration with a
standard iodine solution. Some of these titration reactions are as follows:
I2 + Sn2+ → Sn4+ + 2I −
I2 + H2 S → S 0 + 2I − + 2H +
I2 + SO3 2− + H2 O → SO4 2− + 2I− + 2H+
I2 + 2S2 O3 2− → S4 O6 2− + 2I−

2. Indirect Titration with Iodine (Iodometry)

Iodometric methods are very important in determining substances with oxidizing

properties. The general scheme is as follows:
Aox + I −(excess) → Ared + I2 (6.3)
I2 + 2S2 O3 2− → S4 O6 2− + 2I − (6.4)

The iodine formed in equation 1 is equivalent to the amount of Aox in the sample.
The iodide (added as potassium or sodium) is in large excess and is not a standard solution.
The iodine formed is titrated with standard Na 2S2O3 and the iodine and the tetrathionate
ions are formed. The starch indicator is added when the last tinge of yellow (due to excess
iodine) disappears which should be near the equivalence point. If the starch is added too
soon, that is, while iodine concentration is still high, iodine is absorbed onto the starch,
making the end point very slow and hard to detect. The end point is taken when the blue
starch-iodine complex disappears.

The following reactions can be determined by the indirect iodine titration:

Cr2 O7 2− + 6I − + 14H3 O+ → 2Cr 3+ + 3I2 + 21H2 O

Cl2 + 2I− → 2Cl− + I2

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IO3 − + 5I − + 6H+ → 3I2 + 3H2 O

2Cu2+ + 4I − → 2CuIs + I2

6.2.3 Oxidation/Reduction Reactions in Electrochemical Cells

Many oxidation-reduction reactions can be carried out in either of two ways that are
physically quite different. In one, the reaction is performed by bringing the oxidant and the
reluctant into direct contact in a suitable container. In the second, the reaction is carried out in an
electrochemical cell in which the reactants do not come in direct contact with one another. A
marvelous example of direct contact is the famous “silver tree” experiment, in which a piece of
copper is immersed in a silver nitrate solution (figure 9-1). Silver ions migrate to the metal are
reduced:
𝐴𝑔+ + 𝑒 − ⇌ 𝐴𝑔(𝑠)

At the same time, an equivalent quantity of copper is oxidized:

𝐶𝑢(𝑠) ⇌ 𝐶𝑢2+ + 2𝑒 −

By multiplying the silver half-reaction by two and adding the reactions, we obtain a net ionic
equation for the overall process
2𝐴𝑔+ + 𝐶𝑢(𝑠) ⇌ 2𝐴𝑔(𝑠) + 𝐶𝑢2+ (6.5)

The equilibrium-constant expression for the reaction shown in 6.6 is

[𝐶𝑢2+ ]
𝐾𝑒𝑞 = [𝐴𝑔2+ ] = 4.1 × 1015 (6.6)

Fig. 6.1. Silver-tree Experiment

A unique aspect of oxidation/reduction reactions is that the transfer of electrons- and thus
an identical net reaction can often be brought about in an electrochemical cell, in which the
oxidizing agent and the reducing agent are physically separated from one another. Figure 6.1a
shows such an arrangement. Note that a salt bridge isolates the reactants. But maintains electrical
contact between the two halves of the cell. When a voltmeter of high internal resistance is

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connected as shown or the electrodes are not connected externally, the cell is said to be open circuit
and delivers the full cell potential. When the circuit is open , no net reactions occurs on the cell,
although we will show that the cell has the potential difference, or voltage, between the two
electrodes at any instant. This voltage is a measure of the tendency of the cell reaction to proceed
toward equilibrium.

In figure 6.1 b, the cell is connected so that electrons can pass through a low resistance external
circuit. The potential energy of the cell is now converted to electrical energy to light a lamp, run a
motor, or does some other type of electrical work. In the cell in Figure 9-2b, metallic copper is
oxidized at the left hand electrode, silver ions are reduced at the right-hand electrode, and electrons
flow through the external circuit to the silver electrode. As the reaction goes on, the cell potential,
initially 0.412 V when the circuit is open, decreases continuously and approaches zero as the
overall reaction approaches equilibrium. When the cell is at equilibrium, both cell half-reactions
occur at the same time, and the cell voltage is zero. A cell with zero voltage does not perform
work, as anyone who has found a “dead” battery in a flashlight or in a laptop computer can attest.

When zero voltage is reached in the cell figure 6.1b, the concentration of Cu(II) and Ag(I) ions
will have values that satisfy the equilibrium-constant expression shown in Equation 6.6 At this
point, no further net flow of electrons will occur. It is important to recognize that the overall
reaction and its position of equilibrium are totally independent of the way the reaction is carried
out, whether it is by direct reaction in a solution or by indirect reaction in an electrochemical cell.

A standard solution (or a standard titrant) is a reagent of known concentration that is used to carry
out a titrimetric analysis. A titration is performed by slowly adding a standard solution from a buret
or other liquid-dispensing device to a solution of the analyte until the reaction between the two is
judged complete. The volume or mass of reagent needed to complete the titration is determined
from the difference between the initial and final readings.

It is sometimes necessary to add an excess of the standard titrant and then determine the excess
amount by back-titration with a second standard titrant. For example, the amount of phosphate in
a sample can be determined by adding a measured excess of standard silver nitrate to a solution of
the sample, which leads to the formation of insoluble silver phosphate:

Ag+ + PO43- à Ag3PO4(s)

The excess silver nitrate is then back-titrated with a standard solution of potassium thiocyanate:

Ag+ + SCN- à AgSCN(s)

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Here, the amount of silver nitrate is chemically equivalent to the amount of phosphate ion plus the
amount of thiocyanate used for the back-titration.

6.3 ELECTROCHEMICAL CELLS

Electrochemical cells consist of two conductors called electrodes, each of which is

immersed in an electrolyte solution. In most of the cell that will be of interest to us, the solution
surrounding the two electrodes are different and must be separated to avoid direct reaction between
the reactants. The most common way of avoiding mixing is to insert salt bridge such as shown in
Figure, between the solution. Conduction of electricity from one electrolyte solution to the other
then occurs by migration of potassium ions in the bridge in one direction and chloride ions in the
other. However, direct contact between copper metal and silver ions is prevented.

Fig 6.2. (a) A galvanic cell at open circuit; (b) a galvanic cell doing work; (c) an electrolytic cell

6.3.1 Cathodes and Anodes

The cathode in an electrochemical cell is the electrode at which reduction occurs. The
anode is the electrode at which oxidation takes place.

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Examples of cathodic reactions include:

𝐴𝑔+ + 𝑒 − ↔ 𝐴𝑔(𝑠)
𝐹𝑒 3++𝑒 − ↔ 𝐹𝑒 2+
𝑁𝑂3− + 10𝐻 + +8𝑒 − ↔ 𝑁𝐻4+ + 𝐻2 𝑂

We can force a desired reaction to occur by applying a suitable potential to an electrode

made of an unreactive material such as platinum. Note that the reaction of NO3- in the third reaction
reveals that anions can migrate to a cathode and be reduced.
Typical anodic reaction include
𝐶𝑢(𝑠) ↔ 𝐶𝑢2+ + 2𝑒 −
2𝐶𝑙 ↔ 𝐶𝑙2 (𝑔) + 2𝑒 −
𝐹𝑒 3+ ↔ 𝐹𝑒 2+ + 𝑒 −

The first reaction requires a copper anode, but the other two can be carried out at the surface
of an inert platinum electrode.

6.3.2 Types of Electrochemical Cells

Electrochemical cells are either galvanic or electrolytic. They can also be classified as
reversible or irreversible.

Galvanic, or voltaic, cells store electrical energy. Batteries are usually made from several
such cells connected in series to produce higher voltages than a single cell can produce. The
reaction at the two electrodes in such cells tends to proceed spontaneous and produce a flow of
electrons from the anode to the cathode via an external conductor. An electrolytic cell, in contrast
to a voltaic cell, requires an external source of electrical energy for operation. The cell just
considered can be operated electrolytically by connecting the positive terminal of an external
voltage source with a potential somewhat greater than 0.412V to the silver electrode and the
negative terminal of the source to the copper electrode.

6.3.3 Representing Cells Schematically

Chemists frequently use a shorthand notation to describe electrochemical cells. The cell in
figure 9-2a for example, is described by
Cu|Cu2+(0.0200 M)||Ag+(0.0200 M)|Ag

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By convention, a single vertical line indicates a phase boundary, or interface, at which a

potential develops. For example, the first vertical line in this schematic indicates that a potential
develops at the phase boundary between the copper electrode and the copper sulfate solution. The
double vertical line represents two phase boundaries, one at each end of the salt bridge. A liquid-
junction potential develops at each of these interfaces. The junction potential results from
differences in the rates at which the ions in the cell compartments and the salt bridge migrate across
the interfaces. A liquid-junction potential can amount to as much as several hundredths of a volt
but can be negligibly small if the electrolyte in the salt bridge has an anion and a cation that migrate
at nearly the same rate. A saturated solution of potassium chloride, KCI, is the electrolyte that is
most widely used: it can reduce the junction potential to a few millivolts or less. For our purposes,
we will neglect the contribution of liquid-junction potentials to the total potential of the cell. There
are also several examples of cells that are without liquid junction and therefore do not require a
salt bridge.
An alternative way of writing the cell shown in Figure 9-2a is
Cu|CuSO4(0.0200 M)||AgNO3(0.0200 M)|Ag (9-5)
Here, the compounds used to prepare the cell are indicated rather than the active
participants in the cell half-reactions.

6.3.4 Currents in Electrochemical Cells

Figure9-3 shows the movement of various charge carriers in a galvanic cell during
discharge. The electrodes are connected with a wire so that the spontaneous cell reaction occurs.
Charge is transported through such an electrochemical cell by three mechanisms:
1. Electrons carry the charge within the electrodes as well as the external conductor. Notice
that by convention, current, which is normally indicated by the symbol __ , is opposite in
direction to electron flow.
2. Anions and cations are the charge carriers within the cell. At the left-hand electrode, copper
is oxidized to copper ions, giving up electrons to the electrode. As shown in Figure18-3,
the copper ions formed move away from the copper electrode into the bulk of solution,
while anions, such as sulfate and hydrogen sulfate ions, migrate toward the copper anode.
Within the salt bridge, chloride ions migrate toward and into the copper compartment, and
potassium ions move in the opposite direction. In the right-hand compartment, silver ions
move toward the silver electrode, where they are reduced to silver metal, and the nitrate
ions move away from the electrode into the bulk of solution.
3. The ionic conduction of the solution is coupled to the electronic conduction in the
electrodes by the reduction reaction at the cathode and the oxidation reaction at the anode.

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Fig. 6.3. Movement of charge in a galvanic cell

6.3.5 Electrode Potentials

The potential difference that develops between the electrodes of the cell is a measure of the
tendency for the reaction

2 Ag+ + Cu(s) ⇄ 2 Ag(s) + Cu2+

to proceed from a non-equilibrium state to the condition of equilibrium. The cell potential Ecell is
related to the free energy of the reaction △G by

△ 𝐺 = −𝑛𝐹𝐸𝑐𝑒𝑙𝑙 (6.7)

where n is the number of electrons transferred in the reaction, and F is Faraday’s constant. If the
reactants and products are in their standard states, the resulting cell potential is called standard
cell potential. The standard state of a substance is a reference state that allows us to obtain relative
values of such thermodynamic quantities as free energy, activity, enthalpy, and entropy. All
substances are assigned unit activity in their standard state. This quantity is related to the standard
free energy change for the reaction and thus to the equilibrium constant by

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△ 𝐺 0 = −𝑛𝐹𝐸0 𝑐𝑒𝑙𝑙 = −𝑅𝑇𝑙𝑛𝐾𝑒𝑞 (6.8)

where R is the gas constant, and T is the absolute temperature.

6.4 End of Module Test

1. Write balanced net-ionic equations for the following reactions. Supply H+ and/or H2O, as
needed, to obtain balance.
a. MnO4 2− + VO2+ → Mn2+ + V(OH)4 +
b. Cr2 O7 2− + U 4+ → Cr 3+ + UO2 2+
c. IO3 − + I− → I2 −
d. HPO3 2− + MnO4 − + OH− → PO4 3− + MnO4 −
+
e. V2+ + V(OH)4 → VO2+

2. Consider the following oxidation/ reduction reactions:

AgBr(s) + V2+ → Ag(s) + V 3+ + Br −
Tl3+ + 2Fe(CN)6 4− → Tl+ + 2Fe(CN)6 3−
2V3+ + Zn(s) → 2V2+ + Zn2+
Fe(CN)6 3− + Ag(s) + Br − → Fe(CN)6 4− + AgBr(s)
S2 O8 2− + Tl+ → 2SO4 2− + Tl3+
a. Write each net process in terms of two balanced half-reactions.
b. Express each half-reaction as a reduction.
c. Arrange the half-reactions in part (b) in order of decreasing effectiveness as
electron acceptors.

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