Standard electrode

potentials
Electricity from chemical change
 Electromotive force (e.m.f.) – the ‘push’ that a
cell is able to provide to a current flowing through
it (volts)
 Standard electrode potentials (SEP) – the
potential difference of a half-cell relative to the
standard hydrogen electrode
 Zn(s)  Zn2+(aq) + 2e- oxidation
Cu2+(aq) + 2e-  Cu(s) reduction

The electrochemical cell

The reaction releases energy A high-resistance voltmeter is used

The zinc electrode decreases in so that negligible current flows,
(lost as heat) if the process is
mass but the copper electrode and therefore the maximum
carried out in a single
increases potential difference is being
reaction vessel.
measured.
Half-cell notation

These should be
DOTTED lines
Ecell is directly proportional
to the total entropy change
in a reaction.
Reverse this
one!

Calculating the e.m.f.

 Reverse the least positive value
 Zn  Zn2+ + 2e Eº = -0.76V
 Cu2+ + 2e  Cu Eº = +0.34V
 Overall reaction: Cu2+ + Zn2+  Cu + Zn
 Ecell= +0.34 – (-0.76) = 1.10V For a reaction to be feasible, the
Ecell value must be positive. Once
the value reaches about +0.6V,
the reaction is very likely to
progress.

REMEMBER: The e.m.f. is independent of the number of electrons being transferred

(so don’t change the value when balancing equations!)
http://ibchem.com/IB/ibnotes/full/red_htm/19.1.htm
 The standard hydrogen electrode
 Reference half-cell
 Used to measure other electrode
potentials
 Consists of hydrogen gas at 1atm
pressure and 298K bubbling through an
inert platinum electrode in 1.00 mol
dm-3 H+(aq) ions.

2H+(aq, 1.00 mol dm-3) + 2e- H2(298K, 1atm) Eº = 0.00V

 Measuring standard electrode
potentials

Electrons
flow towards
the positive
electrode
The stronger reducing agent with the
more negative Ecell is on the RHS of the
equation.

The stronger oxidising agent

with the more positive Ecell is
on the LHS of the equation.
Conditions and conventions
 All solutions have unit activity (1.00 mol dm-3)
 All measurements are made at 1atm pressure
 All measurements are made at 298K
 If Eºcell > +0.6V reaction should go to completion
 If 0 < Eºcell < +0.6V PRODUCTS predominate
 If -0.6V < Eºcell < 0 REACTANTS predominate
 If Eºcell < -0.6V no reaction

The reaction is not affected by the

quantity of materials in the reacting
mixture
Limitations
A reaction with a positive Eºcell may not actually
take place – gives no indication of reaction rate
 The reaction conditions may be very different
from standard conditions
 SEPs apply to aqueous equilibria, but there are
many reactions that take place that are not in
aqueous solutions