CHAPTER 7

Electrochemical Equilibrium
• Electrochemical reactions involve the transfer of electrons
• We recognize the importance of electrochemical equilibria in
galvanic cells for example; which can produce electric
current.
• Battery technology relies on this knowledge where it is
possible to convert Gibbs energy change into useful form of
work
• On the other hand, we also have electrolytic cells which
consume electric power to induce a chemical reaction
• This is used in the industries such as in the process
1
electroplating and electro-refining (Aluminum production)
• The measurement of electromotive force
of an electrochemical cell at various
temperature makes it possible to obtain the
thermodynamic properties
• i.e. E = f(temp)
• The chemical potential () of the
electrolytes, for instance, can be calculated
based on these measurements

2
 Equilibria Involving Potential Differences

• When a small charge dQ moves through an electric potential

, the work done on the charge is given by
dw (joule) =  (volt or Joule/coulomb).dQ (coulomb)
• If ions (that carry electric charge) with charge number of zi
are transferred, the differential charge dQ can be related to the
differential amount of mol dni by :
dQ(coul.) = zi .F(coul./mol).dni (mol)
• Where F is the Faraday Constant which is equal to the
avogadro’s number x charge of proton (or electron) :
F = Na.e = (6.0221367x1023 / mol) x (1.60217733x10-19 C )
3
F = 96485.309 C/mol
• So when we consider a multiphase system with phases at
different potential the electrical work term is of the form:
w =  zi F i ni
• where i is the potential of the phase containing species i
• When we want to relate this to the thermodynamic
equation, however, it should be noted that i is not a
natural variable of Gibbs Energy, Hence it is necessary to
make the necessary transformation :
G’ = G -  zi F i ni
Substituting G =  i ni gives G’ =  (i - ziFi) ni
or G’ =  i‘.ni where i‘ = i - zi F  i
4
Based on this, the differential of the transformed Gibbs
Energy :
dG’ = dG -  ziFi dni -  zi F ni di
Substituting dG = - SdT + VdP + idni
we then have :
dG’ = - SdT + VdP + idni -  ziFi dni -  zi F ni di
OR
dG’ = - SdT + VdP + (i -  ziFi ) dni -  zi F ni di
and as before we have : i‘ = i - zi F i then
dG’ = - SdT + VdP + i‘dni -  zi F ni dI
 dG  
and consistently for chemical potential :     i
 dni  T , P ,nj ,i 5
Equation for an electrochemical cell
• Electrochemical cell can be classified as a galvanic cell in
which chemical reaction occur spontaneously. The Gibbs
(free) energy of this reaction is harnessed to generate useful
work (recall: it produces potential differences in Volt)
• On the other hand we can also have electrochemical cell that
work in reverse, in which, chemical reaction is caused/
induced by an externally applied potential differences
• (i) Cathode is the electrode in which reduction occurs; in a
galvanic cell this electrode is positive since electrons are
flowing into it and reacting to form a reduced species
• (ii) Anode is the electrode in which an oxidation reaction
occurs; (it is negative in a galvanic cell)
6
Galvanic Cell :
At cathode : A + e-  A- (reduction, electron is supplied)
At Anode : A  A+ + e- (oxidation, electron is released)

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Swiss German University
• As the potential difference is
increased, a point will be
reached that no current is
flowing
• This is the equilibrium
potential that is of primary
concerned in this chapter
• This is a thermodynamic
measurement as the direction of
the current through the cell can
be changed by an infinitesimal
change in the applied voltage
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8
Chemistry
A wide variety of galvanic cell can be constructed :
Cells without liquid junctions :
Pt(s)H2(g)HCl(m)AgCl(s)Ag(s)
The vertical lines represent the phase
boundary
• In the figure on the side: H2(g) a
non-metal is passed over a platinum
electrode (oxidized to H+), on the
other side Ag+ is reduced to Ag(s)
while the Cl- is released to the solution
9
 Cells with liquid junctions :

Zn(s)Zn2+(m1) Cu2+(m2)Cu(s)
Zn(s)Zn2+(m1) Zn2+(m2)Zn(s)
In the above example Zn is oxidized
into Zn2+ while Cu2+ is reduced to
Cu(s)
•  represent a junction between two
liquids
•   represent a salt bridge
Note: for a galvanic typically made up of potassium
cell there is a chloride or ammonium chloride in
convention to draw which the anion and cations have
oxidation on the left nearly equal mobility
while reduction on • salt bridge prevents mixing/reaction
right 10
To obtain the relationship between electromotive force (E)
and the chemical potential or activities of reactants &
products consider the following cell without liquid junction :
PtLH2(g)HCl(m)AgCl(s)Ag(s)PtR
Note: m indicates molality of the species and we assume
international convention in which the left side is oxidation
and the right side is reduction
So the reactions are :
2AgCl(s) + 2e-(PtR)  2Ag(s) + 2Cl-(aq) (reduction)
H2(g)  2H+(aq) + 2e-(PtL) (oxidation)

11
The sum of these two electrode reactions is :
H2(g) + 2AgCl(s) + 2e-(PtR)  2H+(aq) + 2Ag(s) + 2Cl-(aq) + 2e-(PtL)

alternatively this can also be written (shorter version) :

H2(g) + 2AgCl(s) + 2e-(PtR)  2HCl(aq) + 2Ag(s) + 2e-(PtL)
Consider the cell in the figure
beside; in which the electrodes are
not connected electrically (open
circuit)
Under this condition, when the
system is at equilibrium the
relationship
i i = 0 must be satisfied 12
Such that for :
H2(g) + 2AgCl(s) + 2e-(PtR)  2HCl(aq) + 2Ag(s) + 2e-(PtL)
We have ( for i i = 0) :
2(HCl,aq) + 2(Ag,s) + 2(e-,PtL)
- (H2,g) - 2(AgCl,s) - 2(e-,PtR) = 0
From before we have : i = ’+ ziFi
and for electrically neutral species zi = 0 such that i = ’
only for electrons: (e-,PtL) = ’(e-,PtL) – FL and
(e-,PtR) = ’(e-,PtR) – FR
But for electrons at equilibrium we have : ’(e-,PtL) = ’(e-,PtR)
So the ’ term can cancel out ; Therefore we have in summary :

13
2(HCl,aq) + 2(Ag,s) – 2FL
- (H2,g) - 2(AgCl,s) + 2FR = 0
But we also know that change in chemical potential :
2(HCl,aq) + 2(Ag,s) - (H2,g) - 2(AgCl,s) = rG
Therefore : rG = 2F(L-R) = -2F (R-L) = -2FE
Hence : rG = = -2FE note that the ‘2’ is coming from ‘i’
where E = R - L which is the electromotive force which can
be measured using a potentiometer

14
The relationship rG = -2FE can actually be generalized
to any electrochemical reaction in which it can be written as

 r G    e FE
• Where e is the absolute value of the stoichiometric
number of the electron in the electrochemical reaction (or
simply the number of electron being transferred during the
redox reaction)
• Since we are dealing with Gibbs energy change, then we
know if the right hand electrode has more potential than
the left hand electrode, the value of the electromotive force
(E) of the cell is positive
• This will give a negative value of rG which means that the
electrochemical reaction is spontaneous 15
If the schematic diagram of the cell is reversed
(i.e. the electrochemical reaction is reversed),
the sign of E and therefore the sign of rG
would also be reversed
The reversed reaction then should have rG
which is positive and this means that the reverse
reaction is not a spontaneous reaction

16
Relation between E and the equilibrium constant (K)
• Since the value of E can be obtained under equilibrium
condition, then we can somehow relate it to the value of K
• Recall from the previous chapter we have rGo = -RT ln K
• but before we also have rG = -|e|FE or equivalently for
standard state we have rGo = -|e|FEo (note we will see how
Eo is determined in later discussion)
• Hence we have : |e|FEo = RT ln K such that :
RT   FE o

ln K or K  exp  F = 96485.309 C/mol
e
E 
o

e F  RT 
 

17
Example : Three different galvanic cells have standard
electromotive forces (Eo) of 0.01 V, 0.1 V and 1.0 V at
25C. Calculate K for each reaction assuming |e| = 1 for
these reactions
  e FE o 
Ans. : K  exp  So by entering the values, we get :
 RT 
 
 (96485 Coul mol )(0.01V ) 
K  exp   1.476
 (8.3145 mol .K )(298.15 K ) 
J

(Note that equivalent unit for Volt is Joule/coulomb)

similarly we have K = 49.0 for Eo = 0.1 V,
K = 8.02x1016 for Eo = 1 V
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 RECALL FROM CHAPTER FOR (USE TABLE C2 or C3

Calculate enthalpy, Entropy and Gibbs Energy. Also, if

spontaneous calculate how much energy is available for work.
Zn + Cu2+  Zn2+ + Cu
fHo (kJ) 0 64.77 -153.89 0 Ho = -218.66
So (J/K) 41.63 -99.6 -112.1 33.15 So = -21.0
Therefore: G = H - TS = -218.66x103 - 298x(-21.0)
= - 212.402 kJ/mol < 0 ; spontaneous
While -TS is equal to qsurr : heat transferred to surrounding
G if negative signifies the amount of energy that is available
for work (our purposes) hence also called Gibbs Free Energy

19
Furthermore, knowing that rGo = -|e|FEo if we have data
on the variation of Gibbs energy as a function of Temp
than we can also obtain the expressions for S and H
recall that S = -(G/T) then we have So = |e|F( Eo/ T)
moreover, G = H - TS or H = G + TS, thus
Ho = -|e|FEo + |e|FT( Eo/ T)
So, if we know the variation of Eo as a function of
temperature then we can calculate the above entities.

20
Example : the electrochemical reaction Pt|H2(g)|HCl(aq)|
AgCl(s)|Ag(s) has Eo (Volt) as a function of temperature
(in celcius) as follow (0 to 90Celcius) :
Eo= 0.23659 - 4.8564x10-4 T - 3.4205x10-6 T2 + 5.869x10-9 T3
calculate Go, So, Ho for this reaction at 25C
(i) for Go we simply need to calculate Eo by substituting
the value of T, and then calculate rGo = -|e|FEo
so Eo = 0.22240 V (at 298K), hence :
rGo = - (1) x (96485 Coul/mol) x (0.22240 Volt)
= - 21.458 kJ/mol

21
(ii) So = |e|F( Eo/ T) =
1 x (96485 Coul/mol) x [-4.8564x10-4 - 2(3.4205x10-6)T +
3(5.869 x 10-9) T2] Volt = -62.297 J/mol.K (at 298K)

(iii) H = G + TS
= -21.458 kJ/mol+ (298.15K)(-62.297x10-3 kJ/mol.K)
= -40.032 kj/mol (at 298K)

22
Standard Electrode Potential (standard reduction
potential, Eo)
For both research and industrial purposes, the value of
standard electrode potential (Eo) for many substances
are tabulated
For this purpose, we need to define the reference
electrode against which all of the other
substances/electrodes are measured
In this case, the standard
measurement is measured
against a hydrogen electrode in
which H2(g) is oxidized to H+
(aq).
23
Hence, the measurement is done against the oxidation of
H2(gas) at the anode i.e. ½ H2(g)  H+(aq) + e-
To facilitate the measurement, a convention was adopted
such that the standard electrode potential of the hydrogen
(H2(g) at 1 atm on Pt electrode) is arbitrarily assigned
the value zero:
H+(aq) + e-  ½H2(g) Eo = 0.0000 V
(Note that it is written in terms of reduction reaction)
for example: for the measurement of Eo for the reduction
of Ag+(aq) + e-  Ag(s) we have :
AgCl(s) + e-  Cl-(aq) + Ag(s) Eo = 0.2224 V
Hence Eo is called the standard reduction potential 24
Hence, we can also see the Eo or standard electrode
potential is the measured tendency of an electrode reaction to
occur in the direction of reduction
A brief listing of standard electrode potentials (25°C) can be
seen in table 7.2 (p.240)
Note that fluorine, for instance, electrode has the most positive
electrode potential ½F2(g) + e-  F- - Eo = +2.87 V
if we connect this to the expression : rGo = -|e|FEo and since
we expect, if G < 0, then we know this reaction is spontaneous
Furthermore, as the value is also the highest among other
listed electrode potential for other substances

25
The fluorine electrode has the highest tendency to pull
electrons from the other electrode such that it will undergo
reduction
On the other hand, Li is at the bottom of the list i.e. it has the
lowest Eo, in fact it has negative value of Eo
For such electrodes, the highest tendency is not to undergo
reduction (or to pull electrons from the other electrode), but
rather they have a higher tendency to give up/donate electron
i.e. to undergo oxidation reaction
Similarly, we can see it from the point of view Go = -|e|FEo
such that Gibbs energy change is positive for the reduction of
Li, therefore, we know that it is the reverse
reaction/oxidation that should occur spontaneously (Note:
against H2(g) on Pt electrode) 26
Earlier we discussed the electromotive force of a cell is given
by E = R - L
Based on this we can express the standard electromotive force
for a cell as : Eo = ERo - ELo
Eo = Ereduction – Eoxidation
Hence based on this we can :
(i) Calculate the standard electrode potential of any cell
involving any substances that are available on the list (table
7.2)
(ii) Moreover, we can also determine which electrode will act
as anode and cathode when the cell delivers current
(iii) We can also evaluate equilibrium constant K based on the
relation ln K = |e| FEo/(RT) ; [also rG]
27
Example: Calculate Eo for : Pt|H2(g)|HCl(aq)|Cl2(g)|Pt
Ans.: Write the relevant half reaction (reduction) i.e.
(1) Cl2 + 2e-  2Cl-(aq) Eo = 1.3604 V (EoR)
(2) H2(g) + 2e-  2H+(aq) Eo = 0.0000 V (EoL)
Note: The two reactions must have the same number of
electron (donated = accepted), if not multiplied one of them
to have the same electron. The value of Eo is not affected by
this multiplication
Then Eocell = EoR - EoL = 1.3604 - 0.0000 = 1.3604 Volt
Hence the full reaction can be written as :
H2(g) + Cl2(aq)  2H+(aq) + 2Cl-(aq) (i.e. HCl(ai)) Eo = 1.3604 V
NOTE: Eo = Ereduction – Eoxidation
28
If necessary we can calculate Go from Go = -|e|
FEo
Go = -(2)x(96458 coul)(1.3604 J/coul) = -262.44
kJ/mol
i.e. volt

we can also calculate equilibrium constant K :

  e FE o   2 x(96485coul ) x (1.3604 J )
K  exp   exp  coul   9.78 x1045
RT   (8.3145 J  298.15 K  
   mol . K 

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29
Chemistry
Swiss German University

If we need to evaluate E not at standard state (eg. not at

P=1 bar)
a ( HCl ) 2 RT
K hence from E  E 
o
ln K
 PH 2  Cl 2 
P e F
 o  o
 P  P 

 
RT   a ( HCl ) 2 
EE 
o
ln 
 e F   PH 2  PCl 2  
 P o 
P o
   

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30
Chemistry
Activity of Electrolytes
• When we deal with activity coefficient, it is customary to use
concentration in molal unit (rather than mole fraction or
molarity)
• molality (m) is the amount in mole of the electrolyte in 1 kg
of solvent such that the unit would be mol/kg
• One of the advantage with working with molality is that the
unit is not affected by temperature (unlike molarities for
example)
• the activity of a solute on the m scale is defined by :

 i mi Where mo is the standard value of

ai  o
m the molality ( 1 mol/kg solvent)
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31
Chemistry
 For this relationship, for very low concentration (m  0)
lim  i  1
mi  0

 i mi
Such that for very dilute solution the activity ai a i 
mo
Would simplify to ai = mi/mo (note that mo is simply 1 molal)
At very low concentration the distribution of ions in the
solution can be considered to be completely random and the
ions are too far apart to exert any interaction among
themselves, thus the i is unity
At higher concentration, the attraction and repulsion become
more important. Hence the  is reduced from unity (<1)
32
Swiss German University

END SLIDES…

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33
Chemistry
Swiss German University

Fuel Cell
A fuel cell is a type of battery which is continuously supplied
with oxidant and reductant so that the redox reactions that
generate electricity can occur indefinitely
Some of the currently designed fuel cell can work at the lower
range temperature (25-100C), mid range temperature (100-
500C), high temperature (500 to 1000C) and very high
temperature (above 1000C)
at very low temperature, the use of generally expensive catalyst
is necessary. While at high temperature, the challenge is in the
choice of material that can withstand the temperature as well as
the energy required to maintain the high temperature

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34
Chemistry
Swiss German University

Determination of pH
• In many cases in practice, chemists needs to deal with
the concentration of hydrogen ions (H+) which could range
from 10-1 M to 10-14 M
• Back in 1909, a chemist named Sorenson adopted
exponential notation for [H+]. He defined pH as the
negative exponent of 10 that gives the H+ concentration
i.e. [H+] = 10-pH
• Today, pH is defined to be as close as possible to the
negative base 10 logarithm of hydrogen ion (H+) activity :
pH = -log (aH+)_

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35
Chemistry
Swiss German University

• The pH may be measured with a hydrogen electrode

connected with a calomel electrode through a salt bridge :
Pt | H2(PH2) | H+(aH+)   Cl- | Hg2Cl2 | Hg
• The electromotive force of this cell may be considered to
be made up of three contributions :
 a  
E  0.2802  0.0591 log H 1   E
  PH 2 P o  2  liquid junction **
• The contribution of the calomel electrode is 0.2802 V,
while the Eliquid junction can be assumed to be 0.00 V
• the number 0.0591 is coming from RT/nF but still
multiplied by conversion factor from ln to log (base 10),
recall originally the middle term is : RT  a  
ln  H 1 
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nF  
 P 
PH 2
o
2

36
Chemistry
Swiss German University

• Furthermore, to make the situation more simple we can

use PH2 = 1 bar such that the partial pressure contribution
is reduced to 1
• So after the simplification the equation (**) is :
E – 0.2802 = -0.0591 log aH+
• and since pH is defined as –log (aH+) then

E  0.2802
pH 
E – 0.2802 = 0.0591 log aH+ or 0.0591

• Currently, the use of H2 in the measurement of pH is

avoided. The use of glass electrode is typically used in
practice in most laboratories

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Chemistry
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The basic process is shown

in the figure beside which is
a hydrogen-oxygen fuel cell
with solid electrolyte
The membrane is
impermeable to reactant
gases but not to H+ ions
The (ion exchange)
membrane is also acting as
the electrolyte
For low temp operation, the
membrane is covered with
finely divided Pt catalyst
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Chemistry
Swiss German University

The half cell reactions are :

½O2(g) + 2H+ + 2e-  H2O(l) Eo = 1.2288 V
2H+ + 2e-  H2(g) Eo = 0 V (reversed)
H2(g) + ½O2(g)  H2O(l) Eo = 1.2288 V

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39
Chemistry
Swiss German University

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40
Chemistry