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 Electrode Solution Potential

Cu2+(aq) + 2e copper Cu2+(aq) (1M) + 0.34V

Cu(s) - 1M copper sulphate solution

Reaction Electrode Solution Potential

Zn2+(aq) + 2e zinc Zn2+(aq) (1M) - 0.76V

Zn(s) - 1M zinc sulphate solution

TYPES OF HALF CELL

These are systems involving oxidation or reduction

GASES IN CONTACT WITH SOLUTIONS OF THEIR IONS

Reaction Electrode Solution Gas Potential

2H+(aq) + 2e platinum H+(aq) (1M) 0.00V

H2(g)

- 1M HCl or 0.5M H2SO4

hydrogen at 100 kPa (1atm) pressure

Reaction Electrode Solution Gas

Cl2(aq) + 2e platinum Cl(aq) (1M)

2Cl(g)

- 1M sodium chloride

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 Electrode Solution Potential

Fe3+(aq) + e platinum + 0.77 V

Fe2+(aq)

Fe3+(aq) (1M) and Fe2+(aq) (1M)

TYPES OF HALF CELL

These are systems involving oxidation or reduction

SOLUTIONS OF IONS IN TWO DIFFERENT OXIDATION STATES

Reaction Electrode Solution Potential

Fe3+(aq) + e platinum + 0.77 V

Fe2+(aq)

Fe3+(aq) (1M) and Fe2+(aq) (1M)

SOLUTIONS OF OXIDISING AGENTS IN ACID SOLUTION

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

Solution
Potential

MnO4(aq) (1M) and

+ 1.52 V

Mn2+(aq) (1M) and H+(aq)

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 BUT...

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

298K (25C)

HYDROGEN GAS AT 100 kPa PRESSURE

SOLUTION OF 1M H+(aq) e.g. 1M HCl or 0.5M H2SO4

PLATINUM ELECTRODE

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

MEASUREMENT OF E VALUES

SALT BRIDGE HYDROGEN (100 kPa) ZINC ZINC SULPHATE (1M) PLATINUM ELECTRODE HYDROCHLORIC 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 solution conc. gases

298K 1 Molar (1 mol dm-3) with respect to ions 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 MnO4(aq) + 8H+(aq) + 5e Cl2(g) + 2e Cr2O72-(aq) + I4H+(aq) + 6e Br2(l) + 2e Ag+(aq) + e Fe3+(aq) + e Fe2+(aq) O2(g) + 2H+(aq) + 2e H2O2(aq) +0.54 Cu(s) Cu(s) Cu+(aq) 0.00 Sn(s) -0.44 Zn(s) -0.76 -0.14 +0.52 +0.34 +0.15 I2(s) + 2e2I(aq) Cu+(aq) + e Cu2+(aq) + 2e Cu2+(aq) + e 2H+(aq) + 2eH2(g) Sn2+(aq) + 2e Fe2+(aq) + 2e Fe(s) Zn2+ (aq) + 2e 2F(aq) Mn2+(aq) + 4H2O(l) 2Cl(aq) 2Cr3+(aq) + 7H2O(l) 2Br(aq) Ag(s) +0.77 +0.68 +2.87 +1.52 +1.36 +1.33 +1.07 +0.80
REACTION MORE LIKELY TO WORK SPECIES ON LEFT ARE MORE POWERFUL OXIDATION AGENTS

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 MnO4(aq) + 8H+(aq) + 5e Cl2(g) + 2e Cr2O72-(aq) + I4H+(aq) + 6e Br2(l) + 2e Ag+(aq) + e Fe3+(aq) + e Fe2+(aq) O2(g) + 2H+(aq) + 2e H2O2(aq) +0.54 Cu(s) Cu(s) Cu+(aq) 0.00 Sn(s) -0.44 Zn(s) -0.76 -0.14 +0.52 +0.34 +0.15 I2(s) + 2e2I(aq) Cu+(aq) + e Cu2+(aq) + 2e Cu2+(aq) + e 2H+(aq) + 2eH2(g) Sn2+(aq) + 2e Fe2+(aq) + 2e Fe(s) Zn2+ (aq) + 2e 2F(aq) Mn2+(aq) + 4H2O(l) 2Cl(aq) 2Cr3+(aq) + 7H2O(l) 2Br(aq) Ag(s) +0.77 +0.68 +2.87 +1.52 +1.36 +1.33 +1.07 +0.80

AN EQUATION WITH A HIGHER E VALUE WILL REVERSE AN EQUATION WITH A LOWER VALUE

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 > Overall equation is 2Cl(aq) Cl2(g) + and 2I(aq) 2I(aq) > I2(s) + 2e > 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 CATHODE Zn(s) > Zn2+(aq) + 2e Cu2+(aq) + 2e > Cu(s) OXIDATION 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 ZINC SULPHATE (1M) E = - 0.76V

+
COPPER

COPPER SULPHATE (1M) 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 As a result, copper is deposited overall reaction Cu2+(aq) + 2e > Cu(s)

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 Zn2+(aq) + 2e Cu(s) Zn(s) E = + 0.34V E = - 0.76V put on the RHS 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 Zn2+(aq) + 2e Cu(s) Zn(s) E = + 0.34V E = - 0.76V put on the RHS put on the LHS

Zn

Zn2+

Cu2+

Cu

+
A SOLUTION OF COPPER IONS IN CONTACT WITH COPPER

ZINC IS IN CONTACT WITH A SOLUTION OF ZINC IONS

THE SOLUTIONS ARE JOINED VIA A SALT BRIDGE TO

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 Zn2+(aq) + 2e Cu(s) Zn(s) E = + 0.34V E = - 0.76V put on the RHS put on the LHS

Zn

Zn2+

Cu2+

Cu

Draw as shown the cell reaction goes from left to right

the zinc metal dissolves copper is deposited reduction at the cathode Zn(s) > Zn2+(aq) + 2e Cu2+(aq) + 2e > Cu(s) OXIDATION REDUCTION

oxidation takes place at the anode

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 Zn2+(aq) + 2e Cu(s) Zn(s) E = + 0.34V E = - 0.76V put on the RHS put on the LHS

Zn

Zn2+ V

Cu2+

Cu

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 Zn2+(aq) + 2e Cu(s) Zn(s) E = + 0.34V E = - 0.76V put on the RHS put on the LHS

Zn

Zn2+ V

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)

Sn(s) > Sn2+(aq)

and

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)

Sn(s) > Sn2+(aq)

and

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? Write out the appropriate equations Sn(s) + Cu2+(aq) > Sn2+(aq) + Cu(s) 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? Split equation into two half equations Sn(s) + Cu2+(aq) > Sn2+(aq) + Cu(s) Cu2+(aq) + 2e > Cu(s)

Sn(s)

> Sn2+(aq)

+ 2e

Find the electrode potentials and the usual equations Reverse one equation and its sign

Cu2+(aq) + 2e Sn2+(aq) + 2e

Cu(s) ; Sn(s) ;

E = +0.34V E = - 0.14V

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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WELL DONE!
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AN INTRODUCTION TO

ELECTRODE POTENTIALS
THE END

2009 JONATHAN HOPTON & KNOCKHARDY PUBLISHING