CAPE UNIT ONE MODULE 2 TOPIC: REDOX EQUILIBRIA

Syllabus objectives:

6.1 Define the terms standard electrode potential and standard cell potential

6.2 Describe the standard hydrogen electrode

6.3 Describe methods used to measure the standard electrode potentials of:

- Metals or non-metals in contact with their ions in aqueous solutions

- Ions of the same element in different oxidation states

6.4 Calculate standard cell potentials from standard electrode potentials of two half cells

6.5 Use standard electrode potentials of cells:

- To determine the direction of electron flow

- To determine the feasibility of a reaction

6.6 Predict how the value of an electrode potential varies with concentration (apply Le Chatelier’s principle)

6.7 Apply the principles of redox processes to batteries and fuel cells

• Standard electrode potential, Eө is the potential of a half-cell relative to a standard hydrogen half-cell

under standard conditions of 25°C, 1 atm pressure and 1M concentration.

• Standard cell potential is the overall e.m.f. of a cell and can be calculated from the standard electrode

potentials of the half-cells.

Electron Flow in Daniell Cell

Because of the difference in reduction potential, there will be
a flow of electrons from Zn to Cu. Zn is a stronger reducing
agent than Cu so it is more easily oxidized (loses electrons)
when in contact with a solution of its ions. Therefore, Cu is
able to gain electrons from Zn and is the oxidizing agent in
this set up.

The Zn rod dissolves away and the

concentration of Zn2+ ions rises.
This excess Zn2+ ions is reduced by
SO42- ions moving out from salt
bridge.
Movement of
Similarly, the reduction in Cu2+ ions +ve charge
on the right side is replaced with
Na+ ions from the salt bridge.
What will happen if an external
power source such as a battery is
connected?

Standard Hydrogen
Electrode (SHE)

- To measure std electrode

potential, the half-cell is
connected to SHE.
SHE:
Consists of platinised Pt electrode
immersed in a 1M solution of H + ions.
H2 gas is adsorbed on the Pt and an
equilibrium is established between the
adsorbed layer of H 2 gas and H+ ions
• Assigned 0.000 V
• Can be anode or cathode
• Pt is inert and platinised in order to
increase surface area so equilibrium
reached more quickly

Standard Conditions:
1 atm for gases, 1.0M for solutions, 25 oC for all (298 K)
 Standard Electrode Potentials in Aqueous Solution at 25ƒ C
as measured using SHE

How can we determine which substance is being oxidized and which

is being reduced? The MORE POSITIVE the electrode
potential value gets …. the stronger the oxidizing agent

 Elements that have the most positive reduction potentials are easily reduced.

 Elements that have the least positive reduction potentials are easily oxidized.

 The table can also be used to tell the strength of various oxidizing and reducing agents.

 It can also be used as an activity series.

Metals having less positive reduction potentials are more active and will replace metals with more positive

potentials.

Calculation of overall standard cell potential

Cell Diagram Convention
Notation - overall cell reaction denoted by cell diagram
– Phase boundary denoted by single vertical line (|)
– Liquid junction, aqueous solution boundary denoted by comma (,)
– Interface with no junction potential double vertical line (||) i.e. Salt bridge
r.a.(more –ve Eƒ value)// o.a.(more +ve Eƒ value)
(oxidation ) (reduction)
Flow of e-

1. Write r.h.s. as reduction

2. Write l.h.s. as oxidation
3. Then r.h.s. minus l.h.s.
The stronger r.a. placed on l.h.s. (i.e. more -ve Eө value)
hence oxidation on l.h.s.
and flow of electrons from left to right.
DO NOT CHANGE SIGN!

Calculating Standard Cell Potential

IMPORTANT: Write both equations AS IS from the table in the

reduction form with their voltages. DO NOT CHANGE SIGN!

Example: Calculate E0 for the cell shown in the Figure below:

Cu2+ + 2e-  Cu(s) Eo = 0.337 V

Zn2+ + 2e-  Zn(s) Eo = -0.763 V

o
ECell  ERe
o
d  EOx
o e- V

Zn e-
i.e. r.h.s – l.h.s. -ve
Cu
electrode +ve electrode

Zn/Zn2+//Cu2+/Cu
Zn 2+ Cu2+
Zn + Cu2+  Zn2+ + Cu NO3-
NO3-

Eo = (0.337) – (-0.763) = +1.10 V

 Remember:
In terms of electrode charge

Electrolytic cell Anode (+) Cathode (-)

(electrolysis) (anions) (cations)

Galvanic (Daniell cell) Anode (-) Cathode (+)

(oxidation occurs, (reduction occurs)
e- flow from here)
N.B. For BOTH AN OX RED CAT

• (ƒ) means standard conditions: 1atm, 1M, 25C.

• Negative Eo implies non-spontaneous
• Positive Eo implies spontaneous (would be a good battery!).

Example: Using the table of standard reduction potentials,

predict whether 1 M HNO3 will dissolve gold metal to form a 1 M
Au3+ solution.
Au3+ + 3e-  Au(s) Eo = 1.50 V
NO3- +4H3O+ + 3e-  NO(g) + 6H2O(l) Eo = 0.96 V

To dissolve Au, it should be as Au3+

NO3- +4H3O+ + Au  Au3+ + NO(g) + 6H2O(l) Eo = ?? V

Au/Au3+//NO3-,H3O+/NO, H2O

o
ECell  0.96  1.50  0.54V

Answer: NO!

Dependence of Cell Potential on Concentration

For voltaic cells at non-standard conditions
– Le Chatelier’s principle can be applied.
An increase in the concentration of a reactant will favor the forward
reaction and the cell potential E, will increase.
The converse is also true!
Example: For the cell reaction:
2Al + 3Mn2+ → 2Al3+ + 3Mn
Predict whether Ecell is larger or smaller than E °cell for the following
cases:
(a) [Al3+ ] = 2.0 M, [Mn2+ ] = 1.0 M
(b) [Al3+ ] = 1.0 M, [Mn2+] = 3.0 M (a): Ecell < E°cell
(b): Ecell > E°cell
 Concentration Cells

We can construct a cell where both

compartments contain the same
components BUT at different
concentrations.

Ag+ + e-  Ag at 1M concentration
25ƒC

Solid silver will be deposited on the right electrode, thus

lowering the concentration of Ag+ in the right compartment.
(standard conditions)

In the left compartment (concentration Ag + lowered) the silver

electrode dissolves [producing Ag + ions] to raise the
concentration of Ag+ in solution.

Example : Determine Eocell and Ecell based on the following

half-reactions:
VO2 + + 2H+
+ e- → VO2+ + H2O E° = 1.00 V
2+ -
Zn + 2e → Zn E° = -0.76V

o
ECell  ECathode
o
 E Anode
o

= 1.00 – (-0.76) = 1.76 V

0.1M [Zn2+]: Ecell > Eƒcell

2VO2+ + 4H+ + Zn → 2VO2+ + 2H2O + Zn2+

How a Fuel Cell Works

A simplified description of a H2-02 Proton Exchange Membrane
(PEM) Fuel cell will illustrate, in general, how a fuel cell works.
The fuel cell consists of a negative electrode (the anode), a positive
electrode (the cathode), and an electrolyte. Fuel gas (in this case pure
hydrogen) is transported through the anode towards the anode-electrolyte
interface where the following (simplified) oxidation reaction occurs: Fuel Cells
e.g. Proton Exchange Membrane Cell
H2(g) = 2H+ + 2e-
The liberated electrons migrate out of the anode and through the external
circuit where work is performed, then finally, into the cathode.
On the other hand, the positive hydrogen ions (H+) migrate across the
electrolyte, towards the cathode, where they ultimately react with oxygen
gas and electrons to form water according to:
2H+ + ½ 02 (g) + 2e- = H20
The overall fuel cell reaction then is simply:
H2 + ½02 = H20