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AN INTRODUCTION TO

ELECTRODE
POTENTIALS

KNOCKHARDY PUBLISHING
2008
SPECIFICATIONS
ELECTRODE POTENTIALS
INTRODUCTION
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ELECTRODE POTENTIALS

CONTENTS
Types of half cells
Cell potential
The standard hydrogen electrode
Measuring electrode potentials
The electrochemical series
Combining half cells
Cell diagrams
Uses of E values
ELECTRODE POTENTIALS

Before you start it would be helpful to

Recall the definitions of oxidation and reduction


Be able to balance simple ionic equations
Have a knowledge of simple circuitry
TYPES OF HALF CELL
These are systems involving oxidation or reduction

METALS IN CONTACT WITH SOLUTIONS OF THEIR IONS

Reaction Cu2+(aq) + 2e Cu(s)


Electrode copper
Solution Cu2+(aq) (1M) - 1M copper sulphate solution
Potential + 0.34V

Reaction Zn2+(aq) + 2e Zn(s)


Electrode zinc
Solution Zn2+(aq) (1M) - 1M zinc sulphate solution
Potential - 0.76V
TYPES OF HALF CELL
These are systems involving oxidation or reduction

GASES IN CONTACT WITH SOLUTIONS OF THEIR IONS

Reaction 2H+(aq) + 2e H2(g)


Electrode platinum
Solution H+(aq) (1M) - 1M HCl or 0.5M H2SO4
Gas hydrogen at 100 kPa (1atm) pressure
Potential 0.00V

Reaction Cl2(aq) + 2e 2Cl(g)


Electrode platinum
Solution Cl(aq) (1M) - 1M sodium chloride
Gas chorine at 100 kPa (1atm) pressure
Potential + 1.36V
TYPES OF HALF CELL
These are systems involving oxidation or reduction

SOLUTIONS OF IONS IN TWO DIFFERENT OXIDATION STATES

Reaction Fe3+(aq) + e Fe2+(aq)


Electrode platinum
Solution Fe3+(aq) (1M) and Fe2+(aq) (1M)
Potential + 0.77 V
TYPES OF HALF CELL
These are systems involving oxidation or reduction

SOLUTIONS OF IONS IN TWO DIFFERENT OXIDATION STATES

Reaction Fe3+(aq) + e Fe2+(aq)


Electrode platinum
Solution Fe3+(aq) (1M) and Fe2+(aq) (1M)
Potential + 0.77 V

SOLUTIONS OF OXIDISING AGENTS IN ACID SOLUTION

Reaction MnO4 + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l)


Electrode platinum
Solution MnO4(aq) (1M) and Mn2+(aq) (1M) and H+(aq)
Potential + 1.52 V
CELL POTENTIAL
Each electrode / electrolyte combination has its own
half-reaction which sets up a potential difference

The value is
affected by ... TEMPERATURE
PRESSURE OF ANY GASES
SOLUTION CONCENTRATION

Measurement it is impossible to measure the potential of a single electrode

BUT... you can measure the potential difference between two electrodes
it is measured relative to a reference cell under standard conditions

The ultimate reference is the STANDARD HYDROGEN ELECTRODE.


However, as it is difficult to set up, secondary standards are used.
THE STANDARD HYDROGEN ELECTRODE

The ultimate reference is the STANDARD HYDROGEN ELECTRODE. However as it is


difficult to set up secondary standards are used.

HYDROGEN GAS AT
298K (25C) 100 kPa PRESSURE

SOLUTION OF 1M H+(aq) PLATINUM


ELECTRODE
e.g. 1M HCl or 0.5M H2SO4

The standard hydrogen electrode is assigned an E value of 0.00V.


MEASUREMENT OF E VALUES

SALT BRIDGE

HYDROGEN (100 kPa)

ZINC PLATINUM ELECTRODE

HYDROCHLORIC
ZINC SULPHATE (1M) ACID (1M)

In the diagram the standard hydrogen electrode is shown coupled up to a zinc half
cell. The voltmeter reading gives the standard electrode potential of the zinc cell.

conditions temperature 298K


solution conc. 1 Molar (1 mol dm-3) with respect to ions
gases 100 kPa pressure

salt bridge filled with saturated potassium chloride solution


it enables the circuit to be completed
THE ELECTROCHEMICAL SERIES
E / V
F2(g) + 2e 2F(aq) +2.87
MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l) +1.52
Cl2(g) + 2e 2Cl(aq) +1.36
Cr2O72-(aq) + I4H+(aq) + 6e 2Cr3+(aq) + 7H2O(l) +1.33
Br2(l) + 2e 2Br(aq) +1.07
REACTION MORE
Ag+(aq) + e Ag(s) +0.80 LIKELY TO WORK
Fe3+(aq) + e Fe2+(aq) +0.77
SPECIES ON LEFT
O2(g) + 2H+(aq) + 2e H2O2(aq) +0.68 ARE MORE POWERFUL
I2(s) + 2e2I(aq) +0.54 OXIDATION AGENTS

Cu+(aq) + eCu(s) +0.52


Cu2+(aq) + 2eCu(s) +0.34
Cu2+(aq) + eCu+(aq) +0.15
2H+(aq) + 2e H2(g) 0.00
Sn2+(aq) + 2eSn(s) -0.14
Fe2+(aq) + 2e Fe(s) -0.44
Zn2+ (aq) + 2e Zn(s) -0.76

Layout If species are arranged in order of their standard electrode potentials you
get a series that shows how good each substance is at gaining electrons.
All equations are written as reduction processes ... i.e. gaining electrons
A species with a higher E value oxidise (reverses) one with a lower value
THE ELECTROCHEMICAL SERIES
E / V
F2(g) + 2e 2F(aq) +2.87
MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l) +1.52
Cl2(g) + 2e 2Cl(aq) +1.36 AN EQUATION
Cr2O72-(aq) + I4H+(aq) + 6e 2Cr3+(aq) + 7H2O(l) +1.33 WITH A
HIGHER E
Br2(l) + 2e 2Br(aq) +1.07
VALUE WILL
Ag+(aq) + e Ag(s) +0.80 REVERSE AN
Fe3+(aq) + e Fe2+(aq) +0.77 EQUATION
O2(g) + 2H+(aq) + 2e H2O2(aq) +0.68 WITH A LOWER
I2(s) + 2e2I(aq) +0.54
VALUE

Cu+(aq) + eCu(s) +0.52


Cu2+(aq) + 2eCu(s) +0.34
Cu2+(aq) + eCu+(aq) +0.15
2H+(aq) + 2e H2(g) 0.00
Sn2+(aq) + 2eSn(s) -0.14
Fe2+(aq) + 2e Fe(s) -0.44
Zn2+ (aq) + 2e Zn(s) -0.76

Application Chlorine is a more powerful oxidising agent - it has a higher E


Chlorine will get its electrons by reversing the iodine equation
Cl2(g) + 2e > 2Cl(aq) and 2I(aq) > I2(s) + 2e
Overall equation is Cl2(g) + 2I(aq) > I2(s) + 2Cl(aq)
SECONDARY STANDARDS

Why? The standard hydrogen electrode (SHE) is difficult to set up


it is easier to choose a more convenient secondary standard
the secondary standard has been calibrated against the SHE

Calomel the calomel electrode contains Hg2Cl2


it has a standard electrode potential of +0.27V
is used as the LH electrode to determine the potential of an unknown
to get the value of the other cell ADD 0.27V to the measured cell potential
ELECTROCHEMICAL CELLS

CELLS electrochemical cells contain two electrodes


each electrode / electrolyte combination has its own half-reaction
the electrons produced by one half reaction are available for the other
oxidation occurs at the anode
reduction occurs at the cathode.

ANODE Zn(s) > Zn2+(aq) + 2eOXIDATION

CATHODE Cu2+(aq) + 2e > Cu(s) REDUCTION

The resulting cell has a potential difference (voltage) called the cell
potential which depends on the difference between the two potentials

It is affected by ... current


temperature
pressure of any gases
solution concentrations
A TYPICAL COMBINATION OF HALF CELLS

1.10V

ZINC
_ + COPPER
ZINC
SULPHATE (1M) COPPER
SULPHATE (1M)
E = - 0.76V E = + 0.34V

zinc is more reactive - it dissolves to give ions Zn(s) > Zn2+(aq) + 2e


the electrons produced go round the external circuit to the copper electrode

electrons are picked up by copper ions Cu2+(aq) + 2e > Cu(s)


As a result, copper is deposited

overall reaction Zn(s) + Cu2+(aq) > Zn2+(aq) + Cu(s)


CELL DIAGRAMS
These give a diagrammatic representation of what is happening in a cell.
Place the cell with the more positive E value on the RHS of the diagram.
Cu2+(aq) + 2e Cu(s) E = + 0.34V put on the RHS
Zn2+(aq) + 2e Zn(s) E = - 0.76V put on the LHS

Zn Zn2+ Cu2+ Cu
CELL DIAGRAMS
These give a diagrammatic representation of what is happening in a cell.
Place the cell with the more positive E value on the RHS of the diagram.
Cu2+(aq) + 2e Cu(s) E = + 0.34V put on the RHS
Zn2+(aq) + 2e Zn(s) E = - 0.76V put on the LHS

_ Zn Zn2+ Cu2+ Cu
+
ZINC IS IN CONTACT THE SOLUTIONS A SOLUTION OF
WITH A SOLUTION ARE JOINED VIA A COPPER IONS IN
OF ZINC IONS SALT BRIDGE TO CONTACT WITH COPPER
CELL DIAGRAMS
These give a diagrammatic representation of what is happening in a cell.
Place the cell with the more positive E value on the RHS of the diagram.
Cu2+(aq) + 2e Cu(s) E = + 0.34V put on the RHS
Zn2+(aq) + 2e Zn(s) E = - 0.76V put on the LHS

_ Zn Zn2+ Cu2+ Cu
+

Draw as shown the cell reaction goes from left to right

the zinc metal dissolves Zn(s) > Zn2+(aq) + 2e OXIDATION


copper is deposited Cu2+(aq) + 2e > Cu(s) REDUCTION
oxidation takes place at the anode
reduction at the cathode
CELL DIAGRAMS
These give a diagrammatic representation of what is happening in a cell.
Place the cell with the more positive E value on the RHS of the diagram.
Cu2+(aq) + 2e Cu(s) E = + 0.34V put on the RHS
Zn2+(aq) + 2e Zn(s) E = - 0.76V put on the LHS

_ Zn Zn2+ Cu2+ Cu
+

V
Draw as shown the electrons go round the external circuit from left to right

electrons are released when zinc turns into zinc ions


the electrons produced go round the external circuit to the copper
electrons are picked up by copper ions and copper is deposited
CELL DIAGRAMS
These give a diagrammatic representation of what is happening in a cell.
Place the cell with the more positive E value on the RHS of the diagram.
Cu2+(aq) + 2e Cu(s) E = + 0.34V put on the RHS
Zn2+(aq) + 2e Zn(s) E = - 0.76V put on the LHS

_ Zn Zn2+ Cu2+ Cu
+

Draw as shown the cell voltage is E(RHS) - E(LHS) - it must be positive

cell voltage = +0.34V - (-0.76V) = +1.10V


USE OF Eo VALUES - WILL IT WORK?
E values Can be used to predict the feasibility of redox and cell reactions

In theory ANY REDOX REACTION WITH A POSITIVE E VALUE WILL WORK

In practice, it proceeds if the E value of the reaction is greater than + 0.40V

An equation with a more positive E value reverse a less positive one


USE OF Eo VALUES - WILL IT WORK?
An equation with a more positive E value reverse a less positive one

What happens if an Sn(s) / Sn2+(aq) and a Cu(s) / Cu2+(aq) cell are connected?

Write out the equations Cu2+(aq) + 2e Cu(s) ; E = +0.34V


Sn2+(aq) + 2e Sn(s) ; E = -0.14V
USE OF Eo VALUES - WILL IT WORK?
An equation with a more positive E value reverse a less positive one

What happens if an Sn(s) / Sn2+(aq) and a Cu(s) / Cu2+(aq) cell are connected?

Write out the equations Cu2+(aq) + 2e Cu(s) ; E = +0.34V


Sn2+(aq) + 2e Sn(s) ; E = -0.14V

the half reaction with the more positive E value is more likely to work
it gets the electrons by reversing the half reaction with the lower E value

therefore Cu2+(aq) > Cu(s) and


Sn(s) > Sn2+(aq)
USE OF Eo VALUES - WILL IT WORK?
An equation with a more positive E value reverse a less positive one

What happens if an Sn(s) / Sn2+(aq) and a Cu(s) / Cu2+(aq) cell are connected?

Write out the equations Cu2+(aq) + 2e Cu(s) ; E = +0.34V


Sn2+(aq) + 2e Sn(s) ; E = -0.14V

the half reaction with the more positive E value is more likely to work
it gets the electrons by reversing the half reaction with the lower E value

therefore Cu2+(aq) > Cu(s) and


Sn(s) > Sn2+(aq)

the overall reaction is Cu2+(aq) + Sn(s) > Sn2+(aq) + Cu(s)

the cell voltage is the difference in E values... (+0.34) - (-0.14) = + 0.48V


USE OF Eo VALUES - WILL IT WORK?
An equation with a more positive E value reverse a less positive one

Will this reaction be spontaneous? Sn(s) + Cu2+(aq) > Sn2+(aq) + Cu(s)

Write out the appropriate equations Cu2+(aq) + 2e Cu(s) ; E = +0.34V


as reductions with their E values Sn2+(aq) + 2e Sn(s) ; E = - 0.14V

The reaction which takes place will involve the more positive one reversing the other
i.e. Cu2+(aq) > Cu(s) and Sn(s) > Sn2+(aq)

The cell voltage will be the difference


in E values and will be positive... (+0.34) - (- 0.14) = + 0.48V

If this is the equation you want then it will be spontaneous


If it is the opposite equation (going the other way) it will not be spontaneous
USE OF Eo VALUES - WILL IT WORK?
An equation with a more positive E value reverse a less positive one

Will this reaction be spontaneous? Sn(s) + Cu2+(aq) > Sn2+(aq) + Cu(s)

Split equation into two half equations Cu2+(aq) + 2e > Cu(s)


Sn(s) > Sn2+(aq) + 2e

Find the electrode potentials Cu2+(aq) + 2e Cu(s) ; E = +0.34V


and the usual equations Sn2+(aq) + 2e Sn(s) ; E = - 0.14V

Reverse one equation and its sign Sn(s) > Sn2+(aq) + 2e ; E = +0.14V

Combine the two half equations Sn(s) + Cu2+(aq) > Sn2+(aq) + Cu(s)

Add the two numerical values (+0.34V) + (+ 0.14V) = +0.48V


If the value is positive the reaction will be spontaneous
REVISION CHECK
What should you be able to do?

Recall the different types of half cells


Recall the structure of the standard hydrogen electrode
Recall the methods used to calculate standard electrode electrode potentials
Write balanced full and half equations representing electrochemical processes
Know that a reaction can be spontaneous if it has a positive E value
Calculate if a reaction is feasible by finding its E value

CAN YOU DO ALL OF THESE? YES NO


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AN INTRODUCTION TO

ELECTRODE
POTENTIALS
THE
END

2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING