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Department of Chemistry

Revision Aid

Electrochemistry

Department of Chemistry Revision Aid Electrochemistry Electrochemistry Electrochemistry is the basis of all chemistry. It
Department of Chemistry Revision Aid Electrochemistry Electrochemistry Electrochemistry is the basis of all chemistry. It

Electrochemistry

Electrochemistry is the basis of all chemistry. It simply studies the movement of electrons.

95% of all chemistry involves the flow of electrons!

By measuring electrical potential differences we can determine thermodynamic properties.

By measuring current fluxes we can determine kinetic parameters.

Some Uses of Electrochemistry

Batteries

Chemical synthesis

Extraction of metals

Corrosion

Solar cells

Metal plating and polishing

Water purification

Sensors

LCD and photochromic devices

Life!

Physical Constants

Name

Common

Value

Symbol

Avogadro constant Boltzmann constant Elementary charge Faraday constant Gas constant Mass of an electron Planck constant Speed of light Vacuum permittivity

N

A

6.0221

x 10 23

mol -1

 

k

1.3807

x 10 -23

J K -1

e

1.6022

x 10 -19

C

F

9.6485

x 10 4

C mol -1

 

R

8.3145

J K -1

mol -1

 

m

e

9.1094

x 10 -31

kg

h

6.6261

x 10 -34

J s

c

2.9979

x 10 8

m s -1

 

ε

o

8.8542

x 10 -12

C 2

J -1

m -1

Learn more about the Chemistry Department:-

Contact Details

Department of Chemistry University of Leicester University Road Leicester LE1 7RH UK

Tel: 0116 252 2100 Fax: 0116 252 3789 E-mail: chemistry@le.ac.uk Web: http://www.le.ac.uk/chemistry/

What is the role of the electrode?

Let us look at a simple solution phase reaction

A + B C + D

Reduction:

A + e C

Oxidation:

B D + e

OILRIG – Oxidation Involves Loss Reduction Involves Gain

Homogeneous Reaction

3 Dimensional reaction

Reaction occurs without producing “useful” work

■ Reaction occurs without producing “useful” work Heterogeneous Reaction ■ 2 Dimensional reaction (only

Heterogeneous Reaction

2 Dimensional reaction (only occurs at the electrode surface)

Useful work extracted

occurs at the electrode surface) ■ Useful work extracted The energy of the two systems that

The energy of the two systems that are joined will tend to equilibrium. The only way that this can occur is via a chemical reaction.

e.g. if one beaker contains an Fe 3+ solution and the other an Fe 2+ solution, electrons will flow until [Fe 3+ ] = [Fe 2+ ] in both solutions.

Nomenclature of Cells

 

1) Cell can be represented as a cell diagram. Each phase boundary is drawn as a line. ( || = a salt bridge). We need a salt bridge for ions to flow and neutralise the charge in the two half-cells.

Example

The spontaneous reaction occurs from left to right

1)

1)

Oxidation occurs at the Left hand electrode (LHE) – (negative polarity)

Reduction occurs at the Right hand electrode (RHE) – (positive polarity)

 

2) ALL ELECTRODE REACTIONS SHOULD BE WRITTEN AS REDUCTION REACTIONS

2) Cu 2+ + 2e Cu Zn 2+ + 2e Zn

E o = 0.34 V E o = -0.76 V

3) Cell e.m.f

E cell = E RHE - E LHE

3) E cell = E RHE - E LHE = 0.34 – (-0.76) = 1.10V

 

4) Since E cell is positive

4) The e.m.f. of a spontaneous reaction is positive

Spontaneous reaction is Zn + CuSO 4 Cu + ZnSO 4

Standard Electrode Potentials

The potential of a single electrode process cannot be measured. The potential must always be measured with respect to another half-cell. Hence we define a standard reference electrode. The internationally recognised primary reference is the Standard Hydrogen Electrode (SHE)

Pt | H 2 (p=1atm) | H + (c=1 mol dm -3 ) ||

Pt | H 2 (p=1atm) | H + (c=1 mol dm - 3 ) || Assumed

Assumed to have a potential of 0.0V This is difficult to use and miniaturise. Therefore other reversible electrodes are used and their potentials are referenced back to SHE.

Other Reference Electrodes

Saturated Calomel Electrode (SCE)

Pt|Hg|Hg 2 Cl 2 |KCl (sat.) ||

E o = 0.242 V vs. SHE

2 Cl 2 |KCl (sat.) || E o = 0.242 V vs. SHE Silver/Silver Chloride Ag|AgCl|KCl
2 Cl 2 |KCl (sat.) || E o = 0.242 V vs. SHE Silver/Silver Chloride Ag|AgCl|KCl

Silver/Silver Chloride Ag|AgCl|KCl (sat.)|| E o = 0.197 V vs. SHE

Standard Electrochemical Reduction Potentials Hence lithium metal is a strong reducing agent and fluorine gas
Standard Electrochemical Reduction
Potentials
Hence lithium metal is a strong reducing agent
and fluorine gas is a strong oxidising agent

Balancing Redox Equations

Write a balanced equation for the oxidation of aluminium with sodium perchlorate and determine whether the reaction is thermodynamically viable.

We are looking at the oxidation of aluminium so LHE is

Al 3+ (aq) + 3e- Al(s)

-1.66 V

and the reduction of perchlorate

ClO 4 - (aq) + H 2 O(l) + 2e - ClO 3 - (aq) + 2OH - (aq)

+0.17 V

Balanced equation involves 6e -

3ClO 4 - (aq) + 3H 2 O(l) + 2Al 3ClO 3 - (aq) + 6 OH - (aq) + 2Al 3+

E cell = E RHE - E LHE = 0.17 – (-1.66) = 1.83V

Since the cell potential is positive the reaction is spontaneous ie aluminium is oxidised by perchlorate ions.

Thermodynamic Properties of Reversible Cells

Relationship between Cell E.M.F. and Gibbs Energy Change

One mole of electrons carries 96484 Coulombs of charge. This is called the Faraday Constant (F). Thus for a process involving n electrons where the resulting cell potential is E Volts then the electrical energy of the cell is nFE J/mol If the cell acts reversibly then the electrical energy is equivalent to the decrease in Gibbs Energy of the cell.

G = -nFE

For a spontaneous change G is –ve therefore E is +ve

Example Pb | PbSO 4 | H 2 SO 4 | PbSO 4 | PbO 2

Anodic reaction:

PbSO 4 + 2e Pb + SO 4 2-

 

E o = -0.41V

Cathodic reaction:

PbO 2 + SO 4 2- + 4H +

PbSO 4 + 2H 2 O

E o = 1.68 V

E cell = E c –E a = 1.68 – (-0.41) = 2.09V

G = -nFE = -2 x 96484 x 2.09 = -403 kJ mol -1

(This looks like a large amount of energy but because of the large weight of Pb the energy density is low - enough to power a 60W bulb for 3 hours!)

pH

pH is defined by the negative logarithm of the hydrogen ion activity:

pH = -log 10 [H + ]

where [H + ] = concentration of the hydrogen ion Pure water has a low conductivity and is only slightly ionised into hydronium ions and hydroxide ions:

2H 2 O H 3 O + + OH -

The concentration of H + and OH - ions, which are equal, are 1x 10 -7 ions per litre. The equilibrium constant for the dissociation of water, K w , is

K w = [H + ][OH - ] = 1 x 10 -14 at 25 o C

by taking logs of both side we get:

-log 10 [H + ]+ -log 10 [OH - ] = 14

Using the standard abbreviation p for {-log 10 } we get:

pH + pOH = 14

This equation sets the pH scale to 0-14, which gives a convenient way to express 14 orders of magnitude

of [H + ]. Any solution with pH>7 contains excess hydroxyl ions and is alkaline; those with pH<7 are acidic, containing excess hydrogen ions.

pH scale

contains excess hydroxyl ions and is alkaline; those with pH<7 are acidic, containing excess hydrogen ions.

pKa

For acids that do not fully dissociate (weak acids)

e.g. acetic acid, it is useful to know the extent to which the acid dissociates.

e.g CH 3 COOH + H 2 O

to which the acid dissociates. e.g CH 3 COOH + H 2 O CH 3 COO

CH 3 COO - + H 3 O +

We can define an acidity constant Ka as

K a = [H 3 O + ] [CH 3 COO - ]

[CH 3 COOH]

pK a = -log 10 K a

The smaller the value of pK a the stronger the acid

Ionization Constants of Organic Acids

Ionization Constants of Organic Acids