Equilibrium Electrochemistry

Dr. Neil V. Rees

School of Chemical Engineering
[email protected]

Introduction to Electrochemistry
21-25 October 2013
 Equilibrium electrochemistry

• Principle of batteries
– E.g. Daniell Cell
• Half-cell reactions
– Anode (-)
Zn2+(aq) + 2e→ Zn(s)
– Cathode (+)
Cu2+(aq) + 2e→ Cu(s)
– Overall cell reaction
Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
2
 Electrical Potential

• The electrical potential of an object (in Volts) is

defined as the work needed (in Joules) to bring
up a charge of one Coulomb from an infinite
distance to the object.
• As “non-expansion” work, electrical potential
can be related to Gibbs Free Energy.
• How can we measure?
 Electrical Potential
• “Thought” experiment
• Is the cat positively or negatively charged?

+ = ?
5
The cat may be either positively or negatively
charged.

How can we
tell?
If we bring up a test probe, (with a unit positive
charge of one Coulomb), from an infinite distance
to the pussycat.

• We can measure the

amount of work
needed to do this
• This is the electrical
potential, , of the
cat.
 + +

+
+
+

+
+
+
More
+ +
WORK Positive
+
+

If the cat is positively charged then the work to

move the probe will be positive and the cat is said to
bear a positive electrical potential.
 - -

-
-
- +

- -
-
- More
WORK Negative
- -

Conversely, if the cat is negatively charged, then the

work of transfer is negative and energy is released.
The cat is said to bear a negative electrical potential.
 Electric Potential
• Replace the cat with a wire Pt wire

immersed in an electrolyte…
• The metal wire and solution
M Fe2+
will have their own X-
Fe3+

(generally different) electric H2O

potentials S

– M and S
– why are M and S different?

10
The wire be either a source or a sink of electrons.
Thus at equilibrium there will be a charge separation and
hence a potential difference between the metal and the
solution, i.e. there is an electrode potential between the
metal and the solution
The potential difference is given by
M -  S
Pt wire

M Fe2+
Fe3+
X-
H2O

S
 Electrode Potentials
Platinum wire At the metal-solution interface an
equilibrium is set up:-

Fe3+(aq) + e-(metal) Fe2+(aq)

2+
Fe This leads to a potential drop
between metal and solution
Fe3+
X-
 Initial
Solution Metal
e-

Energy Fermi le
vel
(of electron)
Filled
Fe3+ Conduction
Band

Final
Solution Metal

Original position
of Fermi le
vel

3+ 2+
Fe Fe Filled
Original position of Conduction
solution energyvels
le Band

NB: A negligible amount of charge is exchanged

Hence [Fe2+] and [Fe3+] are essentially unchanged from

their initial values
How can we describe the equilibrium?
Consider the following gas phase reaction

A(g) B(g)

The simplest way of keeping track of this system is to note that

at equilibrium the reactants and products must have identical
chemical potentials so that,

mA = mB (1.4)

14
e can define a new quantity, the electrochemical potent

mA, of a species A

mA = mA + zAFf

where zA is the charge on the molecule A.

At equilibrium,

Total electrochemical total electrochemical

= potential of products
potential of reactants

Electrochemical potential, , comprises chemical potential

and electrical potential
=

18
Platinum wire
Electrode Potentials

Fe3+(aq) + e-(metal) Fe2+(aq)

2+
Fe

Fe3+ + =
X-

¿ ¿
𝐹 ( 𝜙 𝑠 − 𝜙 𝑀 )❑= 𝜇 𝐹𝑒 3 +¿
+ 𝜇 𝐹𝑒2+ ¿ ¿
+𝜇 − ¿
𝑒

But we recall from solution thermodynamics:

𝜇 𝐹𝑒 3+ ¿
= 𝜇 𝐹𝑒 ¿ ¿
+ 𝑅𝑇𝑙𝑛 ¿ ¿

𝐹 ( 𝜙 𝑠 − 𝜙 𝑀 )❑= ¿
𝐹 ( 𝜙 𝑠 − 𝜙 𝑀 )❑= ¿
1
( 𝜙𝑠 − 𝜙𝑀 )❑ = 𝐹 ¿
measured a constant

0 𝑅𝑇
𝐸 𝑒𝑞 = 𝐸 − 𝑙𝑛 ¿¿
Nernst Equation
𝐹

R = universal gas constant (8.314 J K -1 mol-1)

T = absolute temperature (measure in K)
F = Faraday constant (96487 C mol-1)
20
 The Nernst Equation

• The equilibrium potential (Eeq) is not always the

same as E0
• The 2 are related by the Nernst equation

• where F is the Faraday constant (96485 Cmol-1)

• [Ox] & [Red] are concentrations (more
correctly, activities) of oxidised and reduced
species respectively
21
 Nernst equation
• Assumes a dynamic equilibrium at the
electrode species, i.e. the electron transfer
kinetics are fast

• What if the kinetics are slow?

– Need to account for the kinetics via electron
transfer theory

22
 Implications
• The Nernst equation just derived implies 2 different modes of
experiment:
(1) Where an electrode dips into a solution so that a potential
develops in accordance with the Nernst equation. This
“equilibrium electrochemistry” gives simple access to
thermodynamic data
(2) Where a potential is applied between electrode and
solution, forcing the concentrations of solution species to
adjust in order to conform to the Nernst equation. This
requires current to flow and electrolysis to occur and is the
basis of “dynamic electrochemistry”

23
 The Nernst equation and some other
electrode/solution interfaces

H2 Platinised
Pt electrode

The hydrogen electrode

HCl (aq)
 The chlorine electrode

Cl2 Platinin
um

A chlorine electrode

KCl
The silver/silver chloride electrode
Ag wire

Coat of porous
AgCl

Cl- (aq)

A silver/silver chloride electrode

AgCl(s) + e-(m) Ag(m) + Cl-(aq)

 Concentrations or activities ?
An ion, A, has a chemical potential

mA = mA0 + RTln aA
where aA is the activity of species A, instead of

mA = mA0 + RTln [A]

for an ideal solution
 Activities: Reminder
• Activity = effective concentration
• Reflects real (i.e. non-ideal solutions) of
electrolytes
• Concentrations should only strictly be used for
electrolyte at infinite dilution
• Related to concentration by activity coefficient,
±, which has values between 0 and 1

𝑎 ( 𝐴 ) =𝛾 ± [ 𝐴 ]
32
Activity coefficients: working them out
• For concentrations <10-3 M
– Debye-Huckel Limiting Law

, A = -0.509 for aqueous

I is the ionic strength, given by

33
 Activity coefficients
• For concentrations between 10-3 and 0.1M use
the Extended Deby-Huckel Limiting Law
• For more concentrated solutions use
Robinson-Stokes Equations

• For more details on these see, for example,

P.W. Atkins, Physical Chemistry, OUP.

34
Some Examples

37
 Example 1

• Answer

38
39
Example 2

40
41
 Measurement of electrode potentials:
the need for a reference electrode.
(a) (b)
0.368

? A B A

Two possible electrochemical measurements.

(a) A sure-to-fail attempt to measure the electrode potential using a single
electrode/electrolyte interface.
(b) A successful two electrode system employing a reference electrode.
It is impossible to measure an absolute value for the potential
drop at a single electrode solution interface.

∆f= (fMetal A - fS) - (fMetal A - fS) = fMetal A - fMetal B

One electrode (e.g. B) must act as a reference
electrode
0.368 Reference electrode | Solution | Test
electrode

Where the vertical line (|) notates a

B A boundary
between two separate phases.

The measured potential of the cell is

given by
measured potential= (test-s) - (reference-
s)

Suppose the reference electrode

operates in
such a way that the quantity (reference-s)
is kept constant.
Only changes in test-s can be measured
Then measured potential= (test-s) + a
constant
Requirements for a Reference Electrode
• The reference electrode (RE) must:
• Have reduced and oxidised species in constant
concentrations
• Involve a rapidly-established equilibrium (i.e. fast electrode
kinetics)
• Not have a current passed through it
• Be chosen to avoid interference with desired cell reaction
• Examples….
– Standard hydrogen electrode (SHE)
– Saturated Calomel electrode (SCE)
– Ag/AgCl electrode

45
 Example: The standard hydrogen electrode (SHE)

0.770

The standard hydrogen

electrode employed to measure the
Salt potential of the Fe2+/Fe3+ couple.
bridge
H2
Pt wire

2+
Fe
Platinised
Pt electr
ode
3+
Fe

HCI
 The standard hydrogen electrode (SHE)

• Has fixed composition: [HCl] = 1.18M for a(H+) = 1.00

• Has no current passed through it (use of digital voltmeter,

DVM), and

• Has fast electrode kinetics (Pt black)

 H
The way platinum black catalyses the
H+/H2 equilibrium is by providing
Pt - H
H+ (aq) ‘adsorption sites’ for the hydrogen
+ Slow reaction atoms, H˙, formed as intermediates.
-
e (metal)
The adsorption sites permit chemical
bonding of the atoms with the
1
H (g) electrode surface so stabilising the
2 2
Fast reaction intermediate and hence speeding up
the electrode
Reaction co-ordinate
kinetics.
 0.770

Salt
bridge
H2
Pt wire

Fe2+
Platinised
Pt electr
ode

Fe3+

HCI
 0.770

Salt
bridge
H2
Pt wire

2+
Fe
Platinised
Pt electr
ode
3+
Fe

HCI
 Cell Notation
0.337

Salt
bridge
H2
Cu wire

Platinised
platinum
2+
Cu

HCI

Pt | H2(g) (P=1 atm) | H+(aq) (a=1) || Cu2+(aq) (a=1) | Cu

where the symbol || denotes the salt bridge.

The single vertical lines, |, denotes boundaries between two
separate phases.

The SEP of the 0Cu/Cu2+ couple is given by,

ECu/Cu2+ = Cu - Pt
In addition:
half reactions are always written as reductions by convention
Such tables are valuable since they allow us to
predict the potential of any cell from any pair of
half cells. For example the cell,

Cu | Cu2+(aq) (a=1) || Zn2+ (aq) (a=1) | Zn

has a potential of
0
Ecell = Zn - Cu
KCl (aq)
Cu Salt bridge Zn
Which is equivalent to
0 0 0
Ecell = EZn/Zn2+ -ECu/Cu2+
Cu2+ Zn2+
This therefore is the formal reaction for the cell

Cd | Cd2+(aq) (aCd2+) || Pb2+ (aq) (aPb2+) | Pb

but is opposite of that we deduced earlier for the cell

Pb | Pb2+(aq) (aPb2+) || Cd2+ (aq) (aCd2+) | Cd

Example 3

76
77
-
-

78
…..just one caveat

79
 Water

Oxide layer
MgO prevents reaction
of Mg + H2O
Magnesium
 Summary
• Equilibrium electrochemistry is a useful means
of obtaining thermodynamic data (G = nFE)
• Nernst equation predicts equilibrium potential
– activity vs concentration
• Reference electrodes
• Conventions – cell reactions etc
• Thermodynamics vs kinetics

82
 Suggested Reading
• Electrode Potentials, RG Compton & GHW Sanders, OCP
#41, OUP. 1996
• Electrochemistry, CH Hamann, A Hamnett, W Vielstich
• Understanding voltammetry (& Problems book) RG
Compton & CE Banks

For heroes:
• Electrochemical Methods: Fundamentals &
Applications, AJ Bard & LR Faulkner.
• Analytical & Physical Electrochemistry, HH Girault
83