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Electrochemistry
Electrochemistry
Electrochemistry
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)
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
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
I Batteries I Extraction of metals I Solar cells I Water purification I LCD and photochromic devices
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.
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
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
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.
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+
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