Chapter 4:

Thermodynamics of Electrochemical Systems

1. Gibbs free energy defining the spontaneous direction of
chemical reactions
2. Chemical potential, the Gibbs equation and equilibria
3. Activity of ions
4. Electrode standard potentials
5. The Nernst equation
6. Pourbaix diagrams, region of aqueous electrochemistry and
corrosion
7. Concentration cells
8. Alloy plating
9. Heat of electrochemical reactions
10. Electrodes of the second kind
11. Reference electrodes
12. Liquid Junction potentials

4-1
Chapter 4: Thermodynamics of Electrochemical Systems

Thermodynamics is the study of equilibria states. Thus, it provides us information on

systems which do not carry current. Thermo applies also to pseudo-steady states, i.e.,
systems whose response time is faster (shorter) than the imposed change (perturbation),
and therefore if the reaction is fast, thermo will still apply. However, electrochemical
systems are often characterized by sluggish electrode kinetics and slow diffusion, hence;
one should apply themodynamic analysis with care to such systems, since it can be
misleading. Accordingly, thermo indicates that we cannot plate zinc out of acidic solutions,
the lead acid battery cannot exist, and that we cannot plate InSb, GaAs and other
compounds from aqueous solutions – all of which are wrong.

Nonetheless, thermo provides the ‘base line’ – i.e., the ideal or the basis from which we
start to analyze our system. This relates primarily to the standard potential, direction of
spontaneous reactions, energy content in chemicals, etc.

We focus our discussion on electrochemical systems, i.e., systems involving ionic species
in contact with electrodes.

Energy Expressions used in thermo:

 G = Gibbs Free energy

 A = Helmholtz free energy

We can determine the change in Gibbs Free energy of a system undergoing a reaction
readily from thermodynamic measurable and tabulated values:

G  H  T S [4-1]

Where H is the change in the enthalpy (~ heat content) of the system, and S, the change
in its entropy. The latter term is typically quite small at ambient temperatures.

We shall also see that G is directly linked to the standard potential of the electrode reaction, E:

G  nFE [4-2]

Where n is the number of electrons transferred in the electrode reaction, and F is Faraday’s
constant.

The Gibbs free energy can be viewed (imprecisely) as the chemical energy stored in a
system. Hence a change in the Gibbs free energy will tell us if the system will react
spontaneously (negative G for the reaction).
Criterion for Spontaneity:

AG provides a criterion for determining the spontaneous direction a chemical reaction

will take.
4-2
The change in free energy for any process is either negative or remains constant, at
constant temperature and pressure, for any closed system. The change in G provides
the clue whether a reaction will spontaneously proceed in a particular direction. This is
why G is also called the thermodynamic or chemical potential. It is analogous as far as
equilibrium and changes are concerned to potential energy in mechanical systems.

Note:

1. G determines the possibility and direction of change in a chemical system - not

its rate.

2. Never try to propose a process in which G increases.

3. G and direction of the chemical reaction can change with the temperature.
(Why do we often heat systems where G is already negative?)

4. Will reaction "1" proceed more readily than reaction "2" if G1 < G2 both
being negative.
[define "readily" faster (no) or to a further extent (yes)].

5. In electrochemical systems G = -nFE, hence we can drive any reaction to any

extent by externally applying the appropriate voltage.
Gibbs Equation and the Chemical Potential
Gibbs free energy is a function of the temperature, pressure and chemical composition of
the system:
G  G T , P, ni  [4-3]

A complete differential becomes,

 G   G   G 
dG    dT    dP     dni [4-4]
 T  P ,ni  P T ,ni  ni T , P ,n j

Gibbs defined the chemical potential of species i, i,

 G   A 
i      [4-5]
 ni T , P ,n j  ni T ,V ,n j

We can now re-write the Gibbs equation 4-4,

dG   SdT  VdP   i dni [4-6]

4-3
Reversible Work

dW=dG const. T,P at equilibrium, no work  dG=0

The chemical potential provides the criterion for phase equilibrium:

For two phases  and , in contact, in which species can transfer from one to the other,

at equilibrium:

  i  i
For all species, including charged
species.

Also: T = T
P = P

Activity

We cannot measure directly the chemical potential and also its mathematical behavior is
inconvenient (goes to negative infinity when a species is absent), hence we want to
account for it in terms of another parameter, the activity.

Availability of a species in solution for a chemical reaction is equal to its concentration

only in the absence of any intermolecular forces In any non-ideal solution such forces will
exist between the -solvent and the solute molecules. In the case of ionic solutions, in
particular those of strong electrolytes, strong long range coulombic forces also exist
between the ions. Therefore, in all these practical solutions we must replace the
concentration with an "effective concentration" which we will designate as the activity, a.
Hence for the reaction
A B  C  D

aC aD CC CD
K 
aA aB C A CB
Also, when the ionic solution is extremely dilute the activity approach the concentration:

ai ~ Ci as C 0

We would like to speak about the absolute activity of a species i, ai (dimensionless)

irrespective of the concentration units used. We will say that the absolute activity is equal
to the concentration times an activity coefficient.
ai =fi Ci

4-4
Since we have two major concentration systems:
m - molability [gr moles solute/1000 gr solvent]
or
c - molarity [gr moles solute/liter solution]

We must define two systems of activity coefficients:

ai = imi or ai = fiCi
We relate the activity to the chemical potential:

i  RT ln ai (absolute activity according to Gugenheim)

i  i0  RT ln ai (activity defined by Lewis and Randall)
Mean Properties
While conceptually we may discuss the activity of an ionic species, in reality, we are
always faced with a solution containing multiple species (as required by electroneutrality).
Since the activity of an ion is strongly affected by its neighboring ions, we must therefore
discuss (and measure) the activity of an ion in combination with the other constituents of
the solution. We do this by defining the mean properties of the neutral combination:

a /     /  m / 
Calculating the activity
Consider the salt: BaCl2 Ba++ + 2Cl-

Or in a general form: A+B-  +A + -B

Define: = + + -

 
1
  
Mean molality m /   m  
Mean activity a /     /  m / 
a   a /  

Activity:

Determining the activity coefficients:

a. Use tabulated values (hard to find, but available)

b. Use the Debye-Huckel limiting law: log   /   0.51 z  z I

1
Where I is the ionic strength of the solution, given by: I 
2 i
zi2Ci

4-5
Example:

Determine the activity of 0.1 m H2SO4 given that +/- = 0.265

(Always assume complete dissociation, even if you know
H2SO4 2H+ + SO4-2 [as the case here is] this to be incorrect. The activity
coefficient takes care of this ‘wrong’ assumption)
+ =2; - = 1

= + + - = 2 + 1=3

 
1 1
  
m /   m      0.1(22 *11 ) 3
 0.1587

a /     / m /   0.265*0.1587

a   a /     0.1587 *0.265  7.4 *105

 3

4-6
Standard Electrode Potentials
Measured vs. Normal Hydrogen Electrode.
In Practice, we use secondary ‘reference electrodes’
Expresses the relative tendency of an electrode to give up or accept electrons
and change its oxidation state.
Conventionally written as reduction potentials for the half-cell reaction:

M1z+ + ne-  M1(z-n)+ G1=(H1-TS1)=- nFE01  E01=-G1/nF

or:
Cu++ +2e-  Cu0 (cupric ion being reduced to metallic copper) E0=0.34 V
E0 =‘Standard’ Electrode potentials; refers to potential of electrode in contact
with unit activity solution (a Mn+ =1)
Related definitions for: Equilibrium potentials, Galvani potentials, Open
circuit potential (OCP), EMF:

Because of the need for a charge balance we must have an accompanying

oxidation reaction which provides the electrons. E.g.:

M2  M2n+ + ne-

4-7
Standard electrode potentials:
Active (anodic)
Li+ +e Li0 -3.045 V H+ +e 1/2H2 0V

K+ +e K0 -2.935 HgO +H2O +2e Hg+2OH- 0.098

Ca2+ +2e Ca0 -2.866 Cu++ +e Cu+ 0.153

Na+ +e Na0 -2.714 AgCl + e Ag+Cl- 0.2224

Mg++ +2e Mg0 -2.363 HgCl2 + 2e 2Hg+2Cl- 0.2676

Al+3 +3e Al0 -1.662 Cu++ +2e Cu0 0.337

Ti++ +2e Ti0 -1.628 Fe(CN)6-3 +e  Fe(CN)6-4 0.36

Zn(OH)2 +2e
-1.245 I2 +2e  2I- 0.536
Zn0+2OH-
Mn++ +2e Mn0 -1.180 O2 +2H+ +2e  H2O2 0.682

2H2O +2e H2+2OH- -0.822 Fe+3 +e  Fe+2 0.771

Zn++ +2e Zn0 -0.764 Ag+ +e Cu0 0.9

Cr3+ + 3 e  Cr –0.744 Br2 +2e 2Br- 1.065

Fe++ +2e Fe0 -0.441 O2 +4H+ +4e 2H2O 1.229

Cd++ +2e Cd0 -0.403 Cl2 +2e 2Cl- 1.358

PbO2 +4H+ + e Pb+2 +
Ni++ +2e Ni0 -0.250 1.455
2H2O
Sn++ +2e Sn0 -0.136 Ce+4 +e  Ce+3 1.61

Pb++ +2e Pb0 -0.126 Au+ + e  Au0 1.692

H+ +e 1/2H2 0 F2 +2e 2F- 1.87

Nobel (Cathodic)

4-8
These are half cell potentials. Obviously, for a process we require two half
cells: one with anodic reaction, the other with cathodic (why?)
For example consider the Zn/Cu cell

e- - + e-
LOAD

Zn Cu Battery or Fuel-Cell

A spontaneous chemical
-- reaction is used to produce
SO4
electrical energy
M+
Zn++ Cu++

Anodic Oxidation: Cathodic Reduction:

Zn Zn++ + 2e Cu++ + 2e Cu

Assume:
Cu+++2eCu0 E0 = 0.34 V
Zn+++2eZn0 E0 = -0.76 V
We must reverse one of the reactions (Why?). Note also, that when we add
the standard potentials we get -0.42 and hence G will be positive. This
indicates impossible reaction. We will pick the half cell reaction with the
lower standard potential and reverse it:
Now we can sum
Cathode: ++
Cu +2eCu 0 0
E = 0.34 V up the reactions
and the standard
Anode: Zn0 Zn+++2e - E0 = +0.76 V potentials:
_________________________ ___________
Cu++ + Zn0Cu0 + Zn++ V = + 1.1 V  G =-nFE0 < 0

We note that the cell voltage is: VCell = E0Anoder - E0Cathode

4-9
 Materials that are active (very negative) tend to get easily oxidized. This will
reverse the cathodic reaction and yield a positive E0 corresponding to negative
(spontaneous) G. They are suitable to be anodes in batteries.
The other electrode reaction in the battery during discharge will be cathodic
reduction. However, here we have a problem, since we do not want the proton
to be reduced to hydrogen gas, which will tend to explode the battery.
Possible materials are those that inhibit hydrogen evolution kinetically – Zinc,
and lead, or mercury, or Cd. Alternatively, if we want to e.g., use Li, we must
use non-aqueous (a-protic) solvents.

Note: Battery applications - Cathodes Li = -3 V

Zn = - 0.l76
Pb= - 0.126

The highest voltage: Li-F Battery: 1.87 V – (-3.045 V) = 4.91 V

Leclanche Cell (Zn-Carbon)

Anode: Zn(s) → Zn2+(aq) + 2 e-

Cathode: 2MnO2(s) + 2 H+(aq) + 2 e- → Mn2O3(s) + H2O(l)
[ Mn+4  Mn+3 + e ]
We find for Mn:
i. Mn++ + 2 e Mn –1.185
ii. Mn3+ + 3e Mn2+ 1.5415
iii. MnO2 + 4 H+ + 2 e Mn2+ + 2 H2O 1.224
iv. MnO4– + e  MnO42– 0.558
v. MnO4– + 4 H+ + 3 e  MnO2 + 2 H2O 1.679
vi. MnO4– + 8 H+ + 5 e  Mn2+ + 4 H2O 1.507
vii. MnO4– + 2 H2O + 3 e  MnO2 + 4 OH– 0.595
viii. MnO42– + 2 H2O + 2 e  MnO2 + 4 OH– 0.60
ix. Mn(OH)2 + 2 e  Mn + 2 OH– –1.56
4-10
 x. Mn(OH)3 + e  Mn(OH)2 + OH– 0.15
xi. Mn2O3 + 6 H+ + 2e  2 Mn2+ + 3 H2O 1.485

2 iii. 2MnO2 + 8 H+ + 4 e  2Mn2+ + 4 H2O G=-4F(1.224)

xi. 2 Mn2+ + 3 H2O Mn2O3 + 6 H+ +2 e G=-2F(-1.485)
___________________________________ _____
2MnO2 + 8 H+ + 4 e+. 2 Mn2+ + 3 H2O  G= F(-4x1.224+2x1.485)
2Mn2+ + 4 H2O + Mn2O3 + 6 H+ +2 e
When considering energetics we never add voltages. We add and subtract
energies or G. When n is identical in the two reactions, we may add and
subtract voltages, since G=-nFE. However when adding half cell reactions
with different n we must add or subtract G.
Combining identical terms:
Cathode: 2MnO2 + 2 H+ + 2 e  Mn2O3 + H2O
G= F(-4x1.224+2x1.485) =F(-1.926)
Switching back to voltage:
E=G/nF= 1.926/2=0.963 V
Combining with the Zinc reaction:
Zn2+(aq) + 2 e- → Zn(s) E = -0.764 V
Reversing the zinc reaction:
Anode: Zn(s) → Zn2+(aq) + 2 e- E= + 0.764
Summing the anode and cathode reactions we get:
Zn(s) + 2MnO2 + 2 H+  Mn2O3 + H2O+ Zn2+(aq)
E= 0.963+0.764= 1.727 V (in reality we have V~ 1.5 V)
This difference is mainly due to the fact that the proton comes from
ammonia:
NH4+(aq) → H+(aq) + NH3(aq) E= ?

4-11
Review Problems – Thermo – Standard Potentials -
1. Given that E0Au, Au+ = +1.68 Volt and E0Au, Au+3 = 1.42 V, evaluate E0Au+, Au3+ = ?

Check your answer against the data for the standard potential of this reaction provided
in the class meeting. (Note: The tables are correct!)
2. In order to alleviate the energy shortage, it is suggested to use the salinity difference
between Lake Erie (0.01 M NaCl) and the ocean (0.5 M NaCl) to obtain electrical
energy employing a concentration cell without transference. Do you consider this
scheme promising? Support your arguments by calculating the maximum voltage
obtainable.

3. A piece of copper is placed into 1 liter of a 0.5 molal solution of CuSO4. Assuming that
all activity coefficients are unity, determine the composition of the solution after
equilibrium has been reached.

E0Cu, Cu++ = +0.34 Volt E0Cu, Cu+ = +0.52V

(Note the implication for anodes hanging inside a plating bath)

4. State the overall, as well as the half cell reactions corresponding to the combustion of
propyl alcohol to CO2 and H2O in a fuel cell which employs an acid aqueous (H2SO4)
electrolyte.

5. Estimate the minimum voltage required to pass current through the cell:

Pt / H2SO4 (0.1 M, aq.), CuSO4 (0.5M) / Cu

Assume: aCu++ = 0.5 aH+ = 0.1

6. Does the thermodynamic decomposition potential of aqueous solutions of KOH, and

of H2SO4 depend on the concentration of the base or the acid respectively? Back your
statement by calculations. Are your arguments entirely correct? If not, why not?

7. Estimate the standard potentials of the following fuel-cell schemes:

a) H2/HC1 (aq.) C12
b) Na/NaOH (aq.)/O2
c) Zn / Zn (OH)2 (aq.) / O2
d) CH3OH / O2

4-12
Solutions to Sample Problems:

Problem 1:
E10 Au+ + e- → Au0 ΔG10
E20 Au3+ + 3e- → Au0 ΔG20
E30 Au3+ + 2e- → Au+ ΔG30

-n3FE30 = - n2FE20 – (- n1FE10)

E30 = 3/2E20 - 1/2E10 = 3/2*1.42V – 1/2*1.68V = 1.29V

03-04 CRC Values:

E10 = 1.692V, E20 = 1.498V, new calculated E30 = 1.401V

Problem 2:
Na | Na+(0.01M) || Na+(0.5M) | Na

ΔE = Ec + Ea = E0 – 0.059 log (1/0.5) + (- E0 – 0.059 log (0.01))

ΔE = - 0.059 log (0.01/0.5) = 0.1V

This is a rather low maximum voltage and will only get worse with overpotentials. Even
with large stacks this will not produce a lot of energy.

Problem 3:
Cu++ + 2e  Cu E0 = +0.340 V [1]
Cu+1 + e  Cu E0 = +0.520 V [2]

The copper metal is in equilibrium with both cuprous and cupric species. Therefore, E
must be the same for both reactions:

0.059 a
E1  E10  log Cu ,metal  0.34  0.059 log[Cu  ]1/ 2
2 aCu  2

0.059 a
E2  E20  log Cu , metal  0.52  0.059 log[Cu  ]
1 aCu 1
At equilibrium E1=E2

0.34  0.059 log[Cu  ]1/ 2  0.52  0.059 log[Cu  ]

4-13
 [Cu  ]1/ 2
0.059 log  0.18
[Cu  ]

Assume: [Cu++] = 0.5 m (Excess concentration (1 liter) of Cu++ is present. Small

equilibrium related changes won’t affect it significantly).

[0.5]1/ 2

 1.13  103
[Cu ]

[Cu  ]  6.313  104 m

Problem 4:
Overall: C3H8O + 9/2 O2 → 3 CO2 + 4 H2O

Anode: C3H8O + 5 H2O → 3 CO2 + 18 H+ + 18 e-

Cathode: 9/2 O2 + 18 H+ + 18 e- → 9 H2O

Problem 5:

Pt / H2SO4 (0.1 M, aq.), CuSO4 (0.5M) / Cu

Here, the anodic reaction (on the left) is water decomposition with oxygen evolution, and
the cathodic reaction should be copper deposition. Rigorously, the cell diagram should be
presented as:

Pt / O2 / H2SO4 (0.1 M, aq.), CuSO4 (0.5M) / Cu

And the electrode reactions are:

0.059
(+) H2O  2H+ ½ O2 + 2e E40 = -1.23 V E4  1.23  log[ H  ]2 [4]
2

(Assuming that all the gasses are at unit partial pressures)

0.059
(-) Cu++ + 2e  Cu E20 = +0.340 V E2  0.34  log[Cu  ] [2]
2
The cell voltage at equilibrium (no current) for the couple [4] and [2] is:

RT [ H  ]2 (8.31)(298) [0.1]2
V  E2  E4  ETotal 0  log  0.89  log  0.841 V
nF [Cu  ] (2)(96, 491) [0.5]

4-14
The negative sign indicates that the reaction is not spontaneous and copper ions will not be
reduced spontaneously to metallic copper in acidic solution, decomposing water.

Thus, the voltage required to hold the cell at zero current is (-) 0.84 V. The negative
sign here just indicates the polarity or direction of the applied voltage. If we hold the cell at
a larger (absolute voltage, or a larger negative value), the reaction will proceed at a larger
current, i.e., we will have enhanced copper deposition and water decomposition into
protons and evolving oxygen. If the applied voltage will be smaller (smaller absolute
value, or a smaller negative value), reactions [4] and [2] as written will reverse, and we
will have copper dissolution (provided that we have metallic copper) and oxygen gas
consumption.

Problem 6:
Individual electrode potentials change relative to concentration of the base or the acid, but
the decomposition potential does not.

In acid:

Cathode: 4 H+ + 4 e- → 2 H2 Ec = 0 – 0.059/4 log (1/ [H+]4)

Anode: 2 H2O → 4 H+ + O2 + 4 e- Ea = -1.23 – 0.059/4 log ([H+]4)

E = Ec + Ea = -1.23V – 0.059/4 log ([H+]4/[H+]4) = - 1.23V, independent of [H+] or [OH-]

Decomposition potential will change if activities are not constant.

Problem 7:
Anode Cathode Total
(a) H2 → 2 H + 2 e-
+ -
0V Cl2 + 2 e → 2 Cl -
1.358V 1.358V
(b) 4 Na → 4 Na+ + 4 e- 2.71V O2 + 2 H2O + 4 e- → 4 OH- 0.401V 3.111V
(c) 2 Zn → 2 Zn2+ + 4 e- 0.762V O2 + 2 H2O + 4 e- → 4 OH- 0.401V 1.163V

Problem 8:
There is a potential difference because the activities of the two electrodes are different.
There are several reasons why the activities may be different, including interaction with Pt,
but those reasons are not important here.
Ag+ + e- → Aga
Agb → Ag+ + e-
E = Ea + Ec = EAg0 – 0.059 log (aAga / aAg+) + [- EAg0 – 0.059 log (aAg+ / aAgb)]
0.01V = -0.059 log (aAga / aAgb)
aAga / aAgb = 10e(-0.01/0.059) = 0.677

4-15
Corrosion implications:
All very negative material ‘love’ to give electrons (are readily oxidized). All
very positive materials tend to be reduced (accept electrons). This is why we
find in nature the alkali metals only as cations, and all ‘active’ metals are
found as oxides. On the other hand, noble metals such as gold or platinum
might be found in nature in the reduce form, as e.g., gold metallic nuggets (if
we are lucky to find them). We will never find active metal as a reduced (non
oxidized) species.
By the same token, we never want to have an active element in its reduced
form (e.g., Li, zinc, or even iron) in contact with a ‘noble’ species in its
oxidized form. The active metal will readily give its electrons to the noble
material.
This is why we never want to store CuSO4 solution in zinc or iron container.
We will have the reaction:
Zn + Cu++  Zn++ + Cu
which will have a Positive E (or negative G), indicating a spontaneous
reaction.
Dissimilar metal corrosion
The Cementation reaction
Fe + Cu++  Fe++ + Cu E0>0
Copper (in the form of carbonates, sulfates, etc.) is dug from the ground and
leached with sulfuric acid, producing impure copper sulfate. Iron scrap is then
thrown into the bath, causing the reaction above. The copper ‘mud’
precipitates, with codeposits of irom. Gold. Silver..
The copper ‘mud’ is then used as anode in a copper refining cell.

4-16
Nernst equation:
Correcting for activities different from unity:

 A A   B B   CC   D D
RT aCC  aDD RT CC C  CDD (assuming i=1)
EE  0
ln ~E 
0
ln
nF aAA  aBB nF CAA  CBB
For the half cell reaction:
 M n   ne  M
RT aM RT areduced RT aright
E  E0  ln   E 0  ln   E0  ln 
nF aM n  nF aoxidized nF aleft

At 25 C = 298 K:
RT
 0.02565 V
F
RT
ln X  0.02565ln X  2.30.02565log X  0.059 l o g X
F
0.02565 aM 0.059 aM
E  E0  ln   E 0  log  
n aM n  n aM n 
Also,
aelement =1
ln a   ln a
1
ln   ln X
X
a
ln a  ln b  ln
b
RT aM RT 1 RT RT
E  E0  ln   E 0  ln   E 0  ln aM n   E 0  ln aM n 
n aM n  n aM n  n n

4-17
4-46
Cells with Varying Concentrations

A. Identical Species V 

Cu | CuSO4 (a1) || CuSO4 (a2) | Cu

Cu++(a1) +2e Cu0 E(a1)

Cu++(a2) +2e Cu0 E(a2) Cu Cu
Reverse the more negative:
Cu0 Cu++(a1) +2e - E(a1)
Add up: CuSO4 CuSO4
++ ++
Cu (a2)  Cu (a1) a1 a2

0
a1 < a2
E(a1) = E -(RT/nF)ln(1/a1)
E(a2) = E0-(RT/nF)ln(1/a2)
- E(a1) = -E0+(RT/nF)ln(1/a1)
Add up potentials (G):
E=-E(a1)+ E(a2) = -E0+(RT/nF)ln(1/a1)+ E0-(RT/nF)ln(1/a2)
E = (RT/nF)ln(a2/a1) >0 [Spontaneous]
a1 = anode (dissolves)
a2= cathode (plates)

4-18
4-50
Cells with Varying Concentrations

B. Non- Identical Species

Cu | Zn | ZnSO4 (a=0.2) || CuSO4 (a=0.5) | Cu | Cu

ECell=?
V 
Cu++(a=0.5) +2e Cu0 E(Cu)
Zn++(a=0.5) +2e Zn0 E(Zn)
Reverse the more negative:
Zn0 Zn++(a=0.2) +2e -E(Zn)
Add up: Zn Cu
Cu++(a=0.5) + Zn0 
 Cu0 + Zn++(a=0.2)
ZnSO4 CuSO4
RT aCu0
ECu E 
0
Cu ln a=0.2 a=0.5
2 F aCu 
RT aZn0
EZn  EZn
0
 ln
2 F aZn 
RT aZn0
 EZn   EZn
0
 ln
2 F aZn 
RT aCu0 RT aZn0
ECell  ECu    EZn   ECu
0
 EZn
0
 ln  ln
2 F aCu  2 F aZn 

ECell   ECu    ECu 

RT aZn0 aCu  RT aCu  
0
 EZn
0
ln 0
 EZn
0
 ln
2 F aZn  aCu0 2 F aZn 
0.059 0.5
ECell   0.34  [ 0.784]  lo g  1.115  0.03* 0.398  1.127V
2 0.2

4-51 4-19
Determine now the concentrations upon short circuit:
Ecell = 0 V

ECell  0   ECu  RT aCu  

0
 EZn
0
ln 
2 F aZn  
0.059 a  a 
  0.34  [ 0.784]  l o g Cu  1.115  0.03* l o g Cu
2 aZn   aZn  
aCu 
 1037
aZn  

Since azn cannot be significantly larger than 1, very few atoms of cupric ions
remain in solution
Industrial application: Copper displacement by iron scrap.

4-51 b 4-20
E-pH diagrams (Pourbaix diagrams)

Water may be electrolytically decomposed (= ‘electrolyzed’) according to:

Cathodic reduction: 4 H+ + 4 e  2 H2 E01 = 0 V

Anodic Oxidation: 2 H2O  O2 + 4H+ + 4e E02 = 1.23 V

Overall: 2 H2O  H2 + O2 E0 = E01 - E02 = -1.23 V

The negative standard potential tells us that the reaction is not spontaneous (positive G).
Acidic medium has been assumed at pH=0, however a similar reaction can be written for
neutral or basic environment, remembering that under neutral conditions we have both H+
and OH- species, and in base environment we only have OH- and water.

In base environment (pH= 14) we have:

Cathodic reduction: 4 H2O + 4 e  2H2 + 4 OH- E01 = - 0.826 V

Anodic Oxidation: 4 OH-  O2 + 2H2O + 4 e E02 = + 0.404 V

Overall: 2 H2O  H2 + O2 E0 = E01 - E02 = -1.23 V

Obviously, both reactions exhibit the same overall standard potential (- 1.23 V), and it
should be so, because the overall reaction is the same, and does not involve the pH.

It is instructive to write the potential for each of the electrode reactions separately. We will
assume, here, arbitrarily for this illustration) that we are in acidic environment (pH=0).

Cathodic reduction: 4 H+ + 4 e  2 H2 E01 = 0 V

RT ap r oducts
EE  0
log 
nF areac tan ts
0.059 pH 0.059
EH 2  0  log 4 2   log aH4  pH2  0.059log aH   pH 2
4 aH  4
Since: pH   log aH 

EH2  0.059 pH log pH 2

Assuming that the partial pressure of hydrogen is 1 (pH2=1),

EH 2  0.059 pH

We can show, similarly, for the oxygen:

4-21
 EO2  1.23  0.059 pH
The overall reaction, EH2 – E O2

EH2  EO2  1.23

The same as before. Clearly, from Nernst Eq., only reactions that exhibit explicitly either
H+ or OH – will show a dependence of E on the pH.

We now will plot a diagram of the dependence of each of the electrode reactions on the
pH:

O2 Liberated

2 H 2O  O2  4 H   4e
EO2  1.23  0.059 pH
Water is stable

2 H   2e  H 2
H2 Liberated
EH 2  0.059 pH

4-22
4-23
4-24
4-25
4-26
4-27
 E  S S can be either negative or
   positive, but it is a small number
 T  P nF
under ambient temperatures

4-28
4-29
4-30
Examples: Heat Effects in Cells
1. Determine the difference in the potential of the oxidation of ammonia to nitrogen when it is
conducted at a pressure of 100 at. Vs. that at 1 at.

Solution:
1. 2NH3(g) + 1.5O2(g)  N2(g) + 3H2O(g)
# of electrons transferred (n) = 6
# of moles of gas changed by reaction (ΔN) = Nproducts - Nreactants = (1+3)-(2+1.5) =
+0.5

------------------------------------------------------------------------------------
2. Determine the maximum energy that can be obtained from a hydrogen/oxygen fuel cell run at
25C vs. burning the hydrogen in direct combustion at 1000˚C followed by heat engine with
heatrejection at 25˚C.

Solution:
2. (A) Fuel Cell at 25˚C

(B) Direct combustion at 1000˚C followed by heat engine with heat rejection at
25˚C

Ratio

3. Determine the heat absorbed or released during the discharge of a lead acid battery.

4-31
Solution:

3.

(Heat absorbed)
------------------------------------------

4-32
4-33
4-34
4-35
Liquid Junction Potential (LJP)

 A small (few mV) potential that typically exists over regions of electrolyte with
varying concentrations.

 The origin of liquid Junction potential is in diffusion and electrostatics, and it is

present in cells without current passage (equilibrium), hence it lies in the border
region between thermo and transport.

 The liquid junction potential is a function of the electrolyte type and the
structure of the region of varying concentrations; hence it is typically a constant
value for a given system.

 The determination of the LJP is complicated since it requires detailed

knowledge of the concentration profile in the junction region

 LJP is always present when using reference electrodes, since those involve a
concentration gradient across a salt bridge.

 LJP is of little importance to engineers. Areas where it is important are:

o The determination of accurate absolute equilibrium potentials
o Biological systems (e.g., cell membranes) that are characterized by a
small potential.

Consider a two compartment cell, separated V 

by a diaphragm.

One compartment contains copper sulfate;

the other water.

Clearly, Cupric and sulfate ions will diffuse

From the right compartment to the left one.

However their properties are different:

Cu Cu

CuCu= 54 D ~ 5*10-6 _ Cu++

+
SO4SO4= 80 D ~ 7.4*10-6 SO4--

Water CuSO4

4-66 4-36
As a consequence of the different diffusivity, the Sulfate ion will diffuse faster that the
cupric ion. Since the the sulfate is negatively charged, the left compartment will build-up a
negative charge, the right one will become positive.

The different charge gives rise to a potential. The potential will now slow down the fast
moving sulfate ion and will enhance (electrostatically) the transport of the slow moving
copper. , This potential difference which causes both ions to continue diffusing at the same
speed is the LJP.

The preferred salt in salt bridges for reference electrodes is KCl. The reason being is that

K ~Cl
Hence both ions diffuse at about the same rate, minimizing the LJP.

4-67 4-37