Department of Chemistry

Physical Constants
Name Common Value Symbol NA k e F R me h c 6.0221 1.3807 1.6022 9.6485 8.3145 9.1094 6.6261 2.9979 8.8542 x 1023 mol-1 x 10-23 J K-1 x 10-19 C x 104 C mol-1 J K-1 mol-1 x 10-31 kg x 10-34 J s x 108 m s-1 x 10-12 C2 J-1 m-1

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. The spontaneous reaction occurs from left to right

Revision Aid

Electrochemistry

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

Example
1)

Oxidation occurs at the Left hand electrode (LHE) (negative polarity) Reduction occurs at the Right hand electrode (RHE) (positive polarity)

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/

2) ALL ELECTRODE REACTIONS SHOULD BE WRITTEN AS REDUCTION REACTIONS 3) Cell e.m.f Ecell = ERHE - ELHE

2) Cu2+ + 2e Cu Zn2+ + 2e Zn

Eo = 0.34 V Eo = -0.76 V

3) Ecell = ERHE - ELHE = 0.34 (-0.76) = 1.10V 4) Since Ecell is positive Spontaneous reaction is Zn + CuSO4 Cu + ZnSO4

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

What is the role of the electrode?

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 | H2(p=1atm) | H+ (c=1 mol dm-3) || 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.

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

Let us look at a simple solution phase reaction A+BC+D Reduction: A+eC Oxidation: BD+e OILRIG Oxidation Involves Loss Reduction Involves Gain Homogeneous Reaction I 3 Dimensional reaction I Reaction occurs without producing useful work Heterogeneous Reaction I 2 Dimensional reaction (only occurs at the electrode surface) I Useful work extracted

Other Reference Electrodes

Saturated Calomel Electrode (SCE) Pt|Hg|Hg2Cl2|KCl (sat.) || Eo = 0.242 V vs. SHE

I Batteries I Extraction of metals I Solar cells I Water purification I LCD and photochromic devices

I Chemical synthesis I Corrosion I Metal plating and polishing I Sensors I Life!

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 Fe3+ solution and the other an Fe2+ solution, electrons will flow until [Fe3+] = [Fe2+] in both solutions.

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

Standard Electrochemical Reduction Potentials

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
Al3+(aq) + 3e- Al(s) -1.66 V

pH
pH is defined by the negative logarithm of the hydrogen ion activity: pH = -log10 [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 O H O+ + OH2 3

pH scale

and the reduction of perchlorate

ClO4-(aq) + H2O(l) + 2e- ClO3-(aq) + 2OH- (aq) +0.17 V

Balanced equation involves 6e3ClO4-(aq) + 3H2O(l) + 2Al 3ClO3-(aq) + 6 OH-(aq) + 2Al3+

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, Kw, is K = [H+][OH-] = 1 x 10-14 at 25 oC
w

by taking logs of both side we get: -log [H+]+ -log [OH-] = 14

10 10

Ecell = ERHE - ELHE = 0.17 (-1.66) = 1.83V

Using the standard abbreviation p for {-log10} 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.

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 | PbSO4 | H2SO4 | PbSO4 | PbO2 Anodic reaction: PbSO4 + 2e Pb + SO42Eo = -0.41V

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 CH3COOH + H2O CH3COO- + H3O+

Ionization Constants of Organic Acids

We can define an acidity constant Ka as

Ka = [H3O+] [CH3COO-]
[CH3COOH]
pKa = -log10Ka

Cathodic reaction: PbO2 + SO42- + 4H+ PbSO4 + 2H2O Eo = 1.68 V Ecell = Ec Ea = 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!)

Hence lithium metal is a strong reducing agent and fluorine gas is a strong oxidising agent

The smaller the value of pKa the stronger the acid