Spontaneity of redox reactions

-Any reaction that can occur in a voltaic cell to produce a positive

e.m.f must be spontaneous.

Eo=E
o
red
(reduction process) E
o
red
(oxidation process)

We can now make a general statement about the spontaneity of a
reaction and its associated emf, E: a positive value of E indicates a
spontaneous process and a negative value of E indicates a
nonspontaneous one.

So E indicates non standard condition
E
o
indicates stand condition
Gibbs free energy, G is a measure of the spontaneity of a
process that occur at the contant pressure and temperature

When a reaction takes place in a voltaic cell, it performs
work.
We can think of this electrical work as the work produced
by electrical charges in motion.
The total work done = cell voltage x the number of moles of
electrons (n) transferred between electrodes x the electric
charge per mole of electrons (1 Faraday = 96 485
coulombs per mole)
w
elec
= E
cell
x n x F


The maximum electrical work can expressed by the
following equation:

W
max
= W
electrical
= nF x E
cell

where work is defined as positive into the system and
negative by the system.

Since the free energy is the maximum amount of work that
can be extracted from a system, one can write:

G = nF x Ecell

where G is Gibbs free energy.




A positive cell potential gives a negative change in
Gibbs free energy. That mean when E is positive G is
negative and the reaction is spontaneous.

This is consistent with the cell production of an electric
current flowing from the cathode to the anode through the
external circuit(e flow from anode to cathode). If the current
is driven in the opposite direction by imposing an external
potential, then work is done on the cell to drive electrolysis.
The relation between the equilibrium constant, K, and the Gibbs free
energy for an electrochemical cell is expressed as follows:
G = RT ln(K
eq
)
= nF x E
cell

Rearranging to express the relation between standard potential and
equilibrium constant yields




where R is the gas constant (8.3145Jmol
-1
K
-1
), T is the Kelvin
temperature, n the no. of moles of electrons involved in the
reaction and F the Faraday constant

Nernst Equations
Example:
Calculate the values of G
o
and K
eq
at 25
o
C for the reaction
Cu(s) + 2Ag
+
(aq) Cu
2+
(aq) + 2Ag(s)
Given E
o
cell
= 0.460V (see following slide)
Solution:
G
o
= -n x F x E
o
cell
= -2 mole e x 96 485 C/mol e x 0.460V
= -8.88 x 10
4
J

E
o
cell
=

ln K
eq
= =
K
eq
= 4 x 10
15
0.025693V
n
Ln K
eq
2 x 0.460V
0.025693V
35.8
Spontanity
Will copper metal displace silver ion from aqueous solution? That is, does
this reaction occur spontaneously from left to right given E
o
Ag+/Ag
= 0.800
and E
o
Cu2+/Cu
= 0.340?
Cu(s) + 2Ag
+
(aq) Cu
2+
(aq) + 2Ag(s)
Solution:
Reduction: 2Ag
+
(aq) + 2e 2Ag(s) E
o
= 0.800V
Oxidation Cu(s) Cu
2+
(aq) + 2e E
o
= 0.340V

E
o
cell
= E
o
(reduction) E
o
(oxidation)
= 0.800V 0.340V
= 0.460V
E
o
cell
is positive, the forward direction should be the direction of
spontaneous change. Copper metal should displace silver ions from
solution.
To determine if a redox reaction is spontaneous, you
should compute the voltage of the reaction.
If the voltage is positive, the reaction is spontaneous
If the voltage is negative, the reaction is not spontaneous
Example: Is the reaction below spontaneous?
Cu(s) + 2Fe
3+
(aq) --> Cu
2+
(aq) + 2Fe
2+
(aq)

Solution: To determine spontaneity, we need to determine
the voltage. Break the reaction up into two half reactions and
check the voltages of each
Cu(s) --> Cu2+ + 2e- E
ox
= -0.339 V
Fe
3+
(aq) +e - -> Fe
2+
(aq) E
red
= +0.769 V

The cell voltage is thus E
cell
= E
red
- E
ox

= 0.769 (-0.339)
= +0. V.
Since E is positive, the reaction is spontaneous.

Activity : Predicting spontaneity

For the following reactions:
1) Write the total and net ionic reactions.
2) Identify the substance that is oxidized and reduced and the oxidizing and
reducing agent.
3) Using a table of reduction half reactions from the internet or a text book,
determine if the reaction is spontaneous.

Reactions

1) 2Au (s) + 3 Cu(NO
3
)
2
(aq) 2 Au(NO
3
)
3
(aq) + 3 Cu (s)
2) Mg (s) + 2 HCl (aq) MgCl
2
(aq) + H
2
(g)
3) Cl
2
(g) + 2 NaBr (aq) 2 NaCl (aq) + Br
2
(l)
4) 2 KF (aq) + I
2
(s) 2 KI (aq) + F
2
(g)
5) CaBr
2
(aq) + Sn (s) SnBr
2
(aq) + Ca(s)
6) Pb(NO
3
)
2
(aq) + Li (s) LiNO
3
(aq) + Pb (s)
7) 2 Al (s) + 3 Pb(CH
3
COO)
2
(aq) 2 Al (CH
3
COO)
3
(aq) + 3 Pb (s)
8) Cu (s) + CoCl
2
(aq) CuCl
2
(aq) + Co (s)
Exercise:
1. Calculate the values of G
o
and K
eq
at 25
o
C for the
reaction that follows
3Mg(s) + 2Al
3+
(1M) 3Mg
2+
(1M) + 2Al(s)

2. Determine K
eq
for the reaction of silver metal with nitric
acid. The silver is oxidized to Ag
+
(aq) and nitrate ion is
reduced to NO(g).
Criteria for spontaneous change in redox reactions
1. If E
cell
is positive, the reaction in the forward
direction (from left to right) is spontaneous.
2. If E
cell
is negative, the reaction in the forward
direction is nonspontaneous.
3. If E
cell
= 0, the system is at equilibrium.
4. When a cell reaction is reversed, E
cell
and G
change signs.
The effect of concentration on cell
EMF (The Nernst Equation)
Effect of concentration on cell EMF
A voltaic cell is discharged, the reactant of the reaction are consumed
and products are generated, so the concentration of these substances
changes.

The emf progressively drops until E=0, at which point we said the cell
is dead.

At the point the [ ] of the reactant and products cease to change; they
are at equilibrium.

The emf generated under nonstandard condition can be calculated by
using the Nernst equation.
The standard potential of an electrochemical cell
requires standard conditions for all of the reactants.

When reactant concentrations differ from standard
conditions, the cell potential will deviate from the
standard potential.

In the 20th century German chemist Nernst proposed a
mathematical model to determine the effect of reactant
concentration on electrochemical cell potential.
In the late 19th century, Gibbs had formulated a theory to
predict whether a chemical reaction is spontaneous
based on the free energy
G = G + RTx ln(Q)

Here G is change in Gibbs free energy, T is absolute
temperature, R is the gas constant and Q is reaction
quotient.
Gibbs' key contribution was to formalize the understanding
of the effect of reactant concentration on spontaneity.

Based on Gibbs' work, Nernst extended the theory to include the
contribution from electric potential on charged species. The
change in Gibbs free energy for an electrochemical cell can be related
to the cell potential. Thus, Gibbs' theory becomes

nFE = nFE RT ln(Q)

Here n is the number of electrons/mole product, F is the Faraday
constant (coulombs/mole), and E is cell potential.
Finally, Nernst divided through by the amount of charge transferred to
arrive at a new equation which now bears his name:

E = E (RT/nF)ln(Q)
E = E (2.303RT/nF)logQ

Assuming standard conditions (T = 25 C) and R = 8.3145 J/(Kmol),
the equation above can be expressed on base 10 log.
At T=298K the quantity 2.303RT/nF equals 0.0592V, so equation
simplifiers to:
E = E (0.0592/n) log Q



Example:
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)

In This Case n=2 (two electrons are transferred from Zn to
Cu+2) and the standard emf is +1.10V. Thus, at 298K the
Nernst equation gives
E= 1.10V 0.0592V/2 log [Zn
2+
]/[Cu
2+
]

Pure solids are excluded from the expression for Q
The equation show that the emf increase as [Cu
2+
] increase
and as [Zn
2+
] decrease.
For example, when [Cu
2+
] is 5.0M and [Zn
2+
] is 0.050M, we
have
E= 1.10V 0.0592V/2 log( 0.05/5.0) = 1.16V

In general, if the concentrations of reactants increase
relative to those of products, the cell reaction becomes more
spontaneous and the emf increase. Conversely, if the
concentrations of products increase relative to reactants, the
emf decrease.

As voltaic cell operates, reactants are converted into
products, which increase the value of Q and causes the emf
to decrease.
Concentration cells

A concentration cell is an electrochemical cell where the two
electrodes are the same material, the electrolytes on the two half-cells
involve the same ions, but the electrolyte concentration differs between
the two half-cells.

For example an electrochemical cell, where two copper electrodes are
submerged in two copper(II) sulphate solutions, whose concentrations
are 0.05M and 2.0M, connected through a salt bridge. This type of cell
will generate a potential that can be predicted by the Nernst equation.
Both electrodes undergo the same chemistry (although the reaction
proceeds in reverse at the cathode)
Cu
2+
(aq) + 2 e Cu(s)

Cu
2+
(aq) + 2e Cu(s)

Le Chateliers principle indicates that the reaction is more
favorable to reduction as the concentration of Cu
2+
ions
increases. Reduction will take place in the cell's
compartment where concentration is higher and oxidation
will occur on the more dilute side.
The following cell diagram describes the cell mentioned
above:
Cu(s) | Cu
2+
(0.05 M) || Cu
2+
(2.0 M) | Cu(s)
Where the half cell reactions for oxidation and reduction
are:
Oxidation: Cu(s) Cu
2+
(0.05 M) + 2 e
Reduction: Cu
2+
(2.0 M) + 2 e Cu(s)
Overall reaction: Cu
2+
(2.0 M) Cu
2+
(0.05 M)