Farah Khan

ELECTROCHEMISTRY AND REDOX EQUILIBRIA

INTRODUCTION:
SPECIFICATION POINT: Demonstrate an understanding of the terms oxidation number,
redox, half-reactions and use these to interpret reactions involving electron transfer.
Oxidation is the loss of electrons by an atom, ion or molecule or the increase in oxidation
number of an element.
Reduction is gain of electrons by an atom, ion or molecule or the decrease in oxidation
number of an element.
OXIDATION NUMBER:
Oxidation numbers can be worked out using a series of rules:

The oxidation number of an uncombined element is zero

The oxidation number of the element in a monoatomic ion is the charge on the ion
The sum of oxidation numbers of the atoms in a neutral compound is zero
The sum of the oxidation numbers in a polyatomic ion equals the charge on the ion
All group 1 metals have an oxidation number of +1 in their compounds, all group 2
metals have an oxidation number of+2
HALF-EQUATIONS:
Ionic half equations always have electrons on either the left-hand side or the right-hand
side.
When zinc is added to dilute hydrochloric acid, the hydrogen ions are reduced to hydrogen,
because their oxidation number decreases from +1 to zero. The half-equation is:
2H+ (aq) + 2e- H2(g)
As this is a reduction reaction, the electrons are on the left-hand side of the half-equation.
The zinc atoms are oxidized to zinc ions, because their oxidation number increases from
zero to +2.:
Zn(s) Zn2+ (aq) + 2e-
As this is oxidation, the electrons are on the right-hand side of the equation.
REDOX AS ELECTRON TRANSFER:
When a piece of zinc is placed in a solution of copper (II) sulphate, a reaction takes place in
which the zinc is oxidized to zinc ions and the copper ions are reduced to copper metal.
The two half-equations are:
Zn(s) Zn2+ (aq) + 2e-
Cu2+(aq) + 2e- Cu(s)
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In the reaction shown in the photograph, the

copper ions collide with zinc atoms in the surface of
the metal and remove two electrons from each zinc
atom. However, this reaction can also occur without
the copper ions and the zinc atoms coming into
contact.
The zinc rod is in equilibrium with the solution of
zinc ions:
Zn(s) Zn2+ (aq) + 2e-
The position of equilibrium is to the right-hand side,
so the electrons produced making the zinc rod
negatively charged relative to the solution.
Oxidation takes place at the zinc rode, which is called the anode.
The copper ions are in equilibrium with the copper rod:
Cu2+(aq) + 2e- Cu(s)
The copper rod has given some of its delocalized ions to the copper ions, so the rod
becomes positively charged relative to the solution.
Reduction (of copper ions) takes place at the copper rod, which is called the cathode.
This sets up a potential difference (emf) between two metal rods. A current will flow when
the rods are connected by a wire and the solutions are connected by a salt bridge, which
contains a concentrated solution of an inert electrolyte, such as potassium chloride or
potassium nitrate. The current is carried in that salt bridge by the movement of the ions. The
anions (Cl- or NO3-) moves towards the anode and the cations (K+) move towards the cathode.
The current is carried in the wire by the flow of the electrons from the zinc rode to the copper
rod.
SPECIFICATION POINT: Relate changes in oxidation number to reaction stoichiometry.
REDOX AS CHANGE IN OXIDATION NUMBER:
In any redox reaction the oxidation number of one element in a species increases and that of
another element in another species decreases. The total of two changes in oxidation number
are equal.
WORKED EXAMPLE:
An acidified solution containing dichromate (VI) Cr2O7-2, oxidises iodide ions to iodine. The
dichromate (VI) ions are reduced to Cr3+ ions. Write the overall ionic equation for the
reaction.
Answer:
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Each chromium atom changes in oxidation number from +6 to +3. There are two chromium
atoms per dichromate (VI) ion. So the total change of oxidation number is 6. The oxidation
number of iodine ions changes from -1 to 0, so there must be 6I- on the left-hand side of the
equation. The equation is:
Cr2O7-2 (aq) + 6I- (aq) + 14H+ 2Cr3+ (aq) + 3I2(s) + 7H2O(l)
14H+ ions are needed on the left-hand side to form 7H2O with the oxygen atoms from the
Cr2O7-2 ions and also to make the equation balance for charge (6+ on each side).

SPECIFICATION POINT: Recall the definition of standard electrode potential and standard
hydrogen electrode and understand the need for a reference electrode.
ELECTRODE POTENTIALS:
STANDARD ELECTRODE POTENTIAL:
Standard electrode potential is also called the standard reduction potential, because the
equation is normally written as a reduction half equation with the electrons on the left. By
convention, the standard electrode potential of hydrogen is defined as zero.
The term standard means:

All solutions are at a concentration of 1.0 moldm-3.

All gases are at a pressure of 1.0 atm
The system is at stated temperature, usually 298K (25C)
For zinc, the standard reduction potential for a piece of zinc dipping into a 1.0 moldm-3
solution of zinc ions. It is written either as:
Zn2+ (aq) + 2e- Zn(s) Estandard = -0.76 V
Or as:
Zn2+(aq)/ Zn(s) Estandard = -0.76 V
If the substance is a gas, such as hydrogen or chlorine, the electrode consists of a platinum
plate dipping into 1.0 moldm-3 solution of ions of the element with the gaseous element, at
1.0 atm pressure, bubbling over the surface of the platinum.
If the reduction involves two cations for example, M3+ being reduced to M2+ - the electrode
consists of a platinum rod dipping into a solution containing M 3+ ions and M2+ ions, both at a
concentration of 1.0 moldm-3. An example is the reduction of Fe3+ to Fe2+.

TYPES OF ELECTRODES:
STANDARD HYDROGEN ELECTRODE:
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A standard hydrogen electrode consists of hydrogen gas at 1.0 atm pressure bubbling over a
platinum plate which is dipping into a solution that is 1.0 moldm -3 in H+ ions (such as 1.0
moldm-3 HCl), at a temperature of 298K.
H+ (aq) + e- H2(g) Estandard = 0 V
Or
H+ (aq)/H2 (g), Pt Estandard = 0 V

CALOMEL ELECTRODE:
A standard hydrogen electrode is not easy to use, so a
secondary standard is normally used as the reference
electrode. This is a calomel electrode, which consists of
mercury in contact with a saturated solution of mercury (I)
chloride. This has a reduction potential of +0.27 V.
For a Zn/Zn2+ electrode joined to a calomel electrode:
ECell = E(calomel) - E (Zn2+ / Zn)
Where E (Zn2+ / Zn) is the standard reduction potential of zinc
ions to zinc and ECell = 1.03 V.
E (Zn2+ / Zn) = E(calomel) - ECell = =0.27 1.03 = -0.76 V

GLASS ELECTRODE:
A pH meter utilises a half-cell that is based on the reduction of hydrogen ions:
H+(aq) + e- H2(g)
Which is linked to a reference electrode, such as a calomel electrode.
The potential of H+ / H2 half-cell depends on the concentration of H+ ions. This means that
the voltage produced is a measure of [H+] and therefore of the pH of the solution. The
hydrogen half-cell, which acts as an H+ / H2 system, is called a glass electrode.

SPECIFICATION POINT: set up some simple cells and calculate values of Ecell from standard
electrode potential values and use them to predict the thermodynamic feasibility and extent
of reactions.
Farah Khan

STANDARD ELECTRODE POTENTIAL OF A METAL:

The standard electrode of a metal is measured using the system

The metal is dipping into a 1.0 moldm-3 solution of its ions with a salt bridge to a standard
hydrogen electrode, SHE, or a calomel electrode. The two are connected externally by a high-
resistance voltmeter or a potentiometer, using the apparatus shown at the side, the
voltmeter should read 0.44 V.
ECell = E (standard hydrogen electrode) - E (Fe2+ (aq)/Fe(s)
So the standard electrode potential of iron is:
E (Fe2+ (aq)/Fe(s)) = E (SHE) - ECell = 0 (+0.44) = -0.44
This information can be written as a half-equation:
E (Fe2+ (aq)/Fe(s)) = -0.44
Copper and other metals below hydrogen in the electrochemical series have positive
standard electrode potentials.
STANDARD ELECTRODE POTENTIAL OF A GAS:
If the standard electrode potential of a gas such as chlorine is required, the iron electrode
compartment in the diagram above will be replaced with a platinum plate dipping into a 1.0
moldm-3 solution of sodium chloride, with chlorine gas, at 1.0 atm pressure, bubbling over
the platinum.
Cl2(g) + e- Cl-(aq) E = +1.36 V
STANDARD ELECTRODE POTENTIAL OF AN ION PAIR:
Manganate (VII) is a powerful oxidising agent in acid solution. The half-equation is:
MnO4- (aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l)
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One electrode compartment is made of a piece of platinum dipping into a solution that is
1.00 moldm-3 in MnO4- , H+ and Mn2+ ions. This is connected to a standard hydrogen or
calomel electrode.
SPECIFICATION POINT: Set up some simple cells and calculate values of Ecell from standard
electrode potential values and use them to predict the thermodynamic feasibility and extent
of reactions.
CALCULATION OF Ecell FOR A REACTION:
The standard cell potential, Ecell, can be calculated from standard electrode potential data.
Since these data are normally given as reduction potentials, the two reactants must be
identified. One reactant will be on the left-hand side of one half-equation and the other on
the right-hand side of the second half-equation.
The half-equation with the reactant on the right-hand side must be reversed. This alters the
sign of its E value. If necessary, the two half-equations are multiplied by integers to igve
the same number of electrons in each equation, but this does not alter the E values. The
overall equation is obtained by adding these half-equations together. The E value of the
reversed half-equation is then added to the E value of the unchanged half-equation to give
the value of E cell.
WORKED EXAMPLE:
Use the data below to calculate the value for E cell for the reaction in which the Fe3+ ions
oxidise I- in aqueous solution. Write the overall equation.
Fe3+(aq) + e- Fe2+(aq) E = +0.77V
I2(s) + e- I-(aq) E = +0.54V
Answer:
The reactants are Fe3+ and I-, so the second equation has to be reversed and the sign of its E
value changed.
Both equations have one electron, so no multiplying is needed:
Fe3+(aq) + e- Fe2+(aq) E = +0.77V
I-(aq) I2(s) + e- E = -(+0.54) = -0.54
These two equations and their E values are then added together:
Fe3+(aq) + I-(aq) Fe2+(aq) + I2(s) E cell = +0.77 +(-0.54) = +0.23
This is the safest way to calculate the E of a redox reaction. It also generates an overall
reaction.
There are other methods, but they pose particular difficulties:

The anticlockwise rule works only if the data are presented in increasing numerical
order, with the most negative (least positive) E value on top. Each half-equation
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then occurs in an anticlockwise direction. For example, the direction change for the
combination of the I2/I- and Fe3+/ Fe2+ can be predicted using this rule.
FEASIBILITY OF A REDOX REACTION:
A reaction is thermodynamically spontaneous (feasible) if the value of is positive.
Since the total entropy change is directly proportional to the value of E cell, a redox
reaction that has a positive E cell will be thermodynamically spontaneous. Likewise, if the
cell potential is negative, then the reaction is not thermodynamically spontaneous and the
position of equilibrium will shift to the left.

A redox reaction is thermodynamically spontaneous if the value of

cell potential is positive

Remember:

A positive cell potential means that the reaction is thermodynamically feasible.

A negative cell potential means that the reaction is not thermodynamically feasible.

ACTUALITY OF REACTION:
A reaction may be thermodynamically feasible (E cell positive) but might not take place. The
reasons for this can be kinetic or connected with non-standard conditions.
KINETIC REASONS:
The sign of E cell enables the prediction of whether a reaction is thermodynamically feasible.
However, the thermodynamic feasibility is no guarantee that the reaction will take place in
standard conditions. The reaction may have such a high activation energy that the reaction
would be too slow to observe eat room temperature.

The reactants are kinetically stable with respect to the products if the activation energy of
the reaction is too high

The reactants are thermodynamically stable with respect to the products if

Is negative or if E cell is negative

SPECIFICATION POINT: Demonstrate an understanding that Ecell is directly proportional to

the total entropy change and to lnK for a reaction.
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RELATIONSHIP BETWEEN E , AND K:

The value of total entropy change, , is directly proportional to the standard cell
potential of a reaction. In turn, InK is directly proportional to , where K is the
equilibrium constant for the reaction
This means that positive E results in a positive and hence a value of K greater than
1. The more positive the value of E, the larger is the value of the equilibrium constant.
A negative value of E results in a negative and a value of K that is less than 1.
= n E F

Where n is the number of electrons transferred in the overall equation, and F is the Faraday
constant (96 500Cmol-1)
InK = /R = n E F
Where R is the gas constant with a value of 8.31 J K-1mol-1.
SPECIFICATION POINT: Discuss the use of hydrogen and alcohol fuel cells as energy sources,
including the source of the hydrogen and alcohol, e.g. used in space exploration, in electric
cars.
ELECTRICITY FROM CHEMICAL REACTIONS:
There are three ways in which useful amounts of electricity can be produced from chemical
reactions. Chemical energy is converted directly into electrical energy. The process is not
100% efficient as there are some heat losses.
DISPOSABLE BATTERIES:
Standard AA batteries consist of a zinc anode and a cathode of a carbon rod packed around
with granules of manganese(iv) oxide. The electrolyte is a paste of ammonium chloride. The
zinc loses electrons to form zinc ions. At the cathode, manganese(iv) oxide is reduced to
manganese(iii) compound.
Alkaline batteries are similar, except the electrolyte is sodium hydroxide. Here, the anode
reaction is:
Zn(s) + 2OH-(aq) Zn(OH-)2(S) + 2e-
The cathode reaction is:
2MnO2(s) + 2H2O(l) + 2e- 2MnO(OH-)(s) +
2OH-(aq)
Since the concentration of ions remains constant, the
voltage does not fall until all the zinc has been used, at
which point the battery becomes flat.
Farah Khan

FUEL CELLS:
The principle behind a hydrogen-oxygen fuel cells is that hydrogen gas, in an alkaline solution
of potassium, is oxidised at the anode and oxygen is reduced at the cathode.
The electrodes act both as electrical conductors and as catalysts for the reactions. They are
made from metals such as platinum, nickel or rhodium and must be very porous to allow the
gases to pass through and come into contact with the electrolyte.
The two reduction half-equations are:
4H2O(l) + 2e- H2(g) + 2OH-(aq) E = -0.83 V
O2(g) + H2O(l) + 2e- 2OH-(aq) E = +0.40 V
The overall equation and the cell potential are obtained by reversing the first half-equation
and adding it to the first half-equation. This gives:
H2(g) + O2(g) H2O(g) E cell= +0.40 (-0.83) = +1.23 V
Water is produced as waste product that has been produced by the reaction of the hydrogen
fuel with oxygen.

The statement that there are no emissions (implying no CO2 ) is misleading. The hydrogen
could be produced by electrolysis which means high amounts of energy to produce hydrogen.
This enormous amount of energy is produced by burning fossil fuels and the combustion of
fossil fuels produce CO2 .
Another source of hydrogen is the endothermic reaction of methane with steam in a two-
stage process:
CH4(g) + 2H2O(g) CO2 (g) + 4H2(g)
Methanol is another possibility for a fuel cell. However, methanol itself is made of carbon
monoxide and hydrogen, and the carbon dioxide comes from coal or methane, and the
hydrogen itself has a significant carbon footprint.
Farah Khan

SPECIFICATION POINT: Demonstrate an understanding of the principles of modern

breathalysers based on an ethanol fuel cell and compare this to methods based on the use of
IR and to the reduction of chromium compounds.
BREATHALYSERS:
There are two methods of detecting whether a driver has been drinking alcohol, all of these
methods depend on the equilibrium between ethanol dissolved in the blood and that present
in the air breathed out.

The first method consists of a tube containing potassium dichromate(vi) absorbed into
a silica gel. The driver will blow through the tube and fill a plastic bag attached to the
end of the tube. Ethanol in the breath reduced the dichromate(VI) ions, causing a
colour change from orange to green. The amount of alcohol in the breath and hence
in the bloodstream was measured by the extent of greening. The equation for the
reaction is:
C2H5OH + 2Cr2O72- + 16H+ 2CO2 + 11H2O + 4Cr3+
2 x -2 4 x +6 2 x +4 4 x +3

Infrared analyser- the driver breathes into a box and the infrared absorption in the
fingerprint region of ethanol is measured. This is more accurate than the dichromate
method. Its main drawback is that the peak height does not depend linearly on the
concentration of ethanol

Ethanol fuel cell- this is the most accurate method. A fixed volume of breath is pushed
through a fuel cell. The ethanol in the breath is oxidized at the catalytic anode and
oxygen in the air is reduced at the cathode. The total quantity of electricity produced
depends linearly on the amount of ethanol in the breath sample. The equations for
the reactions are:

C2H5OH + 12OH- 2CO2 + 9H2O + 12e-

O2 + 2H2O + 4e- 4OH-