Chapter 8

Part 3
Electrochemical cells
(Review electrochemistry in CHM 102)
1
 Outline
Part 1
Introduction and terminology
Daniell cells
Types of electrodes
Standard electrode potential
Thermodynamics of electrochemical cells
Part 2
Nernst equation
Types of electrochemical cells
Applications of emf measurements
Read Sections 8.6, 8.7 and 8.8 on your own.
2
 Nernst equation
and equilibrium constant
Recall that the Gibbs energy of reaction is
related to composition:
rG = rG + RTlnQ
where Q is reaction quotient = ianproducts/ i an reactants

Since rG = -zFE and rG0 = -zFE0

Hence:

E = E - (RT/zF)lnQ (Nernst Equation)

E is the emf when all reactants and products are at their
standard states [a products = 1 and a reactants = 1]
This will give a value of Q = 1 and ln(Q) = 0
Hence E = E at standard state. 3
 Continued

Or: E = E 2.303 (RT/zF)logQ

Nernst Equation indicates a plot of F(E-
Eo)/RT vs. logQ will give straight line
having:
Slope = -(2.303/z)
Intercept = 0
At 25C:
RT/F = 0.0257 V
Hence, Nernst equation becomes:
E = E - (0.0257/z)lnQ
Or E = E - (0.0591/z)logQ
4
 Continued
At equilibrium, by definition no work can be done
E=0
Concentrations are fixed by the equilibrium constant (K)
K=Q
Recall Nernst Equation: E = E - (RT/zF)lnQ
In this case: E = 0, so
E = (RT/zF)lnK
Rearranging,
lnK = E/ (RT/zF) = zFE/ RT
or
K = exp(zFE/ RT)
This means standard cell potentials can be used to
determine equilibrium constants 5
 Spontaneity of Redox Reactions
0
DG0 = -RT ln K= -zFEcell

19.4
6
 Example 8.4 (modified)
Use Nernst equation and DHLL to calculate the
emf for the cell
CoCoCl2 (0.10 m) NiCl2 (1.0 m) Ni
Solution:
Write the cell reaction and apply Nernst Equation and DHLL: logi= -0.509 x zi

Anode: Co2+ (0.1 m) + 2Cl- (0.2 m)+ 2e Co (s) + 2Cl-(aq)(0.2m) Eo = -0.280;

I = 0.3; Co2+ = 0.076
Cathode : Ni2+ (1.0 m) + 2Cl- (2.0 m)+ 2e Ni (s) + 2Cl-(aq)(2.0 m) Eo = -0.257;
I = 3.0; Ni2+ = 0.000297
Over all reaction : Ni2+ (1.0 m)+ Co + Ni (s) + Co2+ (0.1 m) Eo = 0.023

E= E - (RT/zF)lnQ; z= 2 E= E - (RT/zF)ln(aCo2+ )/(aNi2+)

E= 0.023 - 0.0129 ln [(0.1) (Co2+ ) /(1.0)(Ni2+)]

E= 0.023 - 0.0129 ln [7.6 x 10-3/2.97 x10-4]
7
= -0.0188 V
 Nernst potential
Consider two different concentration of the
same electrolyte are separated by
permeable membrane to both ions. After
some times, the concentration will be equal
on both sides. (Figure 8.7 a)
If the membrane was replaced by
semipermeable one that allows the passage
of K+ ions only. (Figure 8.7 b)
Given that the concentration in the left is
greater than on the right (C1 >C2).
K+ ions will pass from left to right for certain
time and will stop.
This is due a potential build up across the
membrane.
More positive ions on the right than on the left.
8
 Continued
This potential difference between the two sides (R -
L) is called Nernst potential ().
The work associated with this process:
we = zF = Ge (z is charge on permeable ion)
This potential can be related to concentration using
the concentration dependence of Gibbs free energy:
Gc = Gco + RTlnc,
The change in Gibbs free energy across the membrane
due to concentration gradient is (GcR-GcL);
Gc = RTlnCR/CL;
9
 Continued
The total free energy change across the
membrane is:
GTot = Gc + Ge
At equilibrium:
GTot = 0
Hence:
RTlnCR/CL + zF = 0
Thus the Nernst potential is given by:
= R - L = (RT/zF) lnCL/CR
Solve example 8.5
10
 = (RT/zF) lnC1/C2
By convention, we take the ratio of concentration of ions
outside the cell to the concentration of ions inside the cell.
Hence, = inside - outside
= inside - outside = (RT/zF) lnCoustside/Cinside =

= -97.7 mV

The potential inside the cell is lower than the

potential outside the cell. 11
 Types of electrochemical cells

Electrochemical cells

Chemical cell Concentration cell

Without transference(1) With transference(2) Solution Amalgam (6) Gas(7)

electrodes are involved (2) Redox cells (3) Without transference (4) With transference (5)

12
 Examples
Chemical cells: net chemical change
1- Pt, H2(1 Bar)HCl( 1m)AgClAg (without transference)
2- Zn |Zn2+|Cu2+ Cu (with transference)
3- Pt, H2(1 Bar)H+, Fe2+, Fe3+Pt (Redox)
Concentration cells: the driving force is dilution
process:
4- Pt, H2(g)HCl(m1)Cl-(aq)Ag-AgCl(s)|HCl(m2)|H2,Pt
5- Pt, H2 |H+(m1)||H+(m2)| H2, Pt
6- Na in Hg at c1|Na in Hg at c2
7- Pt, H2 (P1)|H+| H2(P2), Pt 13
 Concentration cell
Refers to a cell in which the cathode and anode
compartment differ in only in concentration of the
substances. All other parameters are the same.
For the cell
Pt, H2(1 Bar) HCl(m1)HCl(m2)H2(1 Bar), Pt
Anode: H+ (m1)+ e H2 Eo = 0
Cathode: H+ (m2)+ e H2 Eo = 0
Overall reaction: cathode anode
H+ (m2) H+ (m1)
For this cell, z =1, then: E = Eo RT/Flna1/a2; Since Eo = 0,
hence:
E = (RT/F)ln(a2/a1) 14
 Example 8.8:

Calculate the emf for the following cell at 25 0C:

Pt, H2(1 Bar)HCl(0.2) HCl(3.0) H2(1 Bar), Pt
Solution:
Cell reaction: H+ (3 m) H+ (0.2 m)
E = (RT/F)ln(aH+(3m)/aH+(0.2m))
= [8.314 x 298/96484][ln([H+]cath/ ([H+]anode) + ln(+cath /-anode)]
ln+cath = - 0.51(3)1/2 = 0.13; ln+anode = - 0.51(0.2)1/2 = 0.59
= (8.314 x 298/96484)(ln3/0.2 + ln0.13/0.59)
= 0.0256(2.71 + (-1.51)) = 0.03 V
15
 Redox cells
Refers to a cell in which the redox couple are in solution.
The electrode acts as catalyst to facilitate the reduction
process.
Pt, H2(1 Bar) HCl( 1m) Fe+2,Fe+3Pt
Overall rxn:
Fe+3 + H2H+ (1 m) + Fe+2
Assuming activity = concentration,
E = E0 -(RT/F)ln[Fe+2][H+] /[Fe+3]
Since [H+] = 1, then
E = E0 -(RT/F)ln[Fe+2] /[Fe+3]
16
 Applications of emf
pH determination (pH meter)
Determination of activity coefficients
Determination of equilibrium constants
Quantitative analysis (potentiometric
titration).

17
 Measurement of pH
1- pH meters using hydrogen electrode.
Consider the following cell:
Pt|H2( 1bar)|HCl(aq)|| KCl (0.1m)|Hg2Cl2|Hg
Specific reactions:
Cathodereaction:
Hg2Cl2(s)+2e 2Hg(l)+2Cl(aq)E1/2=0.27V

Anodereaction:
H2(g)2H+(aq)+2e E1/2=0.0V

Cellreaction:
Hg2Cl2(s)+H2(g) 2Hg(l)+2H+(aq)+2Cl(aq)Cath
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 Measurement of pH (cont.)
Hg2Cl2(s)+H2(g) 2Hg(l)+2H+(aq)+2Cl(aq)

Whatifwelet[H+]vary?
Q H Cl
2 2

Ecell=Ecell(0.0591/2)log(Q)
Assumeactivity=concentration:
E
=E (0.0591/2)(2log[H+]+2log[Cl])
cell cell
Constant(Why??
Ecell=Ecell(0.0591)(log[H+]+log[Cl])
Saturatedsoln
Ecell=Constant+(0.0591)pH
EcellisdirectlyproportionaltopH.
However,hydrogenelectrodeisnotconvenienttouse. 19
 2- Ion selective electrodes
pH meters using ion selective electrodes:
Respond to the presence of a specific ion. pH
probes are sensitive to H3O+.
For glass electrode, the pH is proportional to emf.
From calibration using known pH, the instrument
can directly convert E to pH.

20
 Determination of Activity Coefficients
We need to measure for HCl.
Construct the following cell which, hopefully will give
values for from E measurements:
Pt, H2 (1 bar) HCl (m)(aq) AgCl(s) Ag
Cell reaction:
H2 + AgCl Ag + H+ + Cl- (z =1)
[Note: AgCl + e = Ag + Cl- Eo = 0.22233 V]

G = Go + RT ln a+. a-

Or: E = Eo - (RT/F)ln a+. a-

21
 Activity Coefficients (contd)
E = Eo RT/F ln m2 RT/F ln + -
Rearrange to get:

E + 2RT/F ln m = Eo 2RT/F ln

Plot left side vs. m, a straight line should be

obtained with intercept is Eo .

This is because as m 0 , 1.
Since Eo is constant, can be
determined at any m.
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 Generalization
In general, to determine for any soluble
substance MN, construct the following cell:
M(s)MN (m)(aq) insoluble salt of N with X metal [XN(s)]X
Then the following equation can be derived:
E + 2RT/F ln m = Eo 2RT/F ln
Hence, can be determined at any concentration
from E measurement. (see next slide)

23
Mean activity coefficient for some strong electrolytes at
different concentration at 298 K

24
 Equilibrium constant

a- Equilibrium constant for weak acid or weak base

Consider weak acid HA:
onstruct the following cell:
Pt, H2 (1 bar) HA (m1), NaA(m2), NaCl(m3) AgCl(s) Ag
ver all reaction:
H2 + AgCl Ag + H+ + Cl-
Use Nernst equation:
E = Eo RT/F ln mH+mCl- RT/F ln +- --------------1
Ka = (mH+mCl-/mHA) ( + - / HA)-----------------2
Substitute for mH+ from equation 2 into equation 1 to get Equation 48.

Plot of the LHS versus Ionic strength will yield K a from the intercept (figure 8.10)
25
 How to get the equilibrium concentration of
each species?
mCl- = m3, the molality of NaCl
mHA = m1 mH+
mA- = m2 + mH+
mH+ can be obtained from the approximate equilibrium constant
value as follows:
Neglect mH+ from above equations.
Substitute the initial values of mHA = m1 and mA- = m2 in equation 48.
Obtain approximate value of Ka.
Evaluate mH+ from:

Calculate new equilibrium values for mHA and mA- and then substitute in
equation 48 to get new value for Ka.
Reiterate the above procedure, until the results diverge.
26
The first term of RHS of equation
8.48 is proportional to ionic
strength.
The ionic strength can be
calculate from m2 and m3. (the
contribution of H+ from HA is
neglected)
A plot of the LHS of equation 48 vs I,
should yield a straight line.

At I = 0, all = 1 and hence the first

term on the RHS of equation 8.48 = 0

Hence the intercept is = -ln.

27
 Example
The LHS of equation 8.48 was measured at
two ionic strengths for a cell containing acetic
acid at 25.0 oC:
LHS I (mol/Kg)
-7.30 0.10
-25.80 0.20
Calculate the thermodynamic equilibrium
constant ()of acetic acid at this temperature.

28
 Solution
We need to evaluate the intercept of equation 48
Equation 48 can be written as:
LHS = aI - b
where b = ln Koa
Hence from the data, two equations can be formulated:
-7.30 = 0.1a - b ----(1)
-25.80 = 0.2a - b (2)
Solve for b by elimination as follows:
multiply equation 1 by -2 to get equation 3.
Add equation 2 and equation 3 to get:
-11.20 = b
Hence: ln Koa = -11.2;
Or Koa = 1.34 and 10-5
29
b- Determination of the Solubility Product constant

The following cell can be used to obtain Ksp for AgCl

Pt|Cl2(g)I 1 bar) HCl (aq)AgCl (s) Ag(s)
Anode reduction half reaction:
Cl- Cl 2 + e Eo1 = 1.357
Cathode reduction half reaction:
AgCl(s) + e Ag(s) + Cl- Eo2 = 0.2222v
Cell reaction:
AgCl (s) Ag (s) + 1/2Cl2 (g)
But AgCl (s) in equilibrium with Ag+ and Cl-, hence:
Ag+ + Cl- Ag (s) + 1/2Cl2 (g) --------(1)
From Nernst equation:
E = E + (RT/F) ln a a
30
o
 Continued
Equation 1 can be obtained from the following half
reactions:
1/2Cl2 + e Cl- Eo2 = 1.35827 V (2)
Ag+ + e Ag (s) Eo3 = 0.7996 V -----(3)
Subtract equation 2 from equation 3 to get equation
1.
Nernst equation for equation 1 is:
Ecell = Eocell + (RT/F) ln aAg+ aCl-
where Eocell = Eo3 Eo2 = -0.5587
Then you measure Ecell in the lab.
31
Since AgCl (s) Ag+ + Cl-
Then: Kosp = aAg+ aCl-
Nernst equation becomes:
E = (Eo2 Eo3 ) + (RT/F) ln Kosp
Example
The measured value of E for the cell:
Pt|Cl2(g)I 1 bar) HCl (aq)AgCl (s) Ag(s)
is -1.140 V. Calculate Kosp for AgCl
Solution:
Substitute values in Nernst equation:
-1.140 = (0.7996 1.35827) + 0.0256 ln Kosp
ln Kosp = -22.71, Hence
32
Ko
= 1.37 x 10 -10
Ksp values for some salts

33
In general, to determine Ksp for any salt MB
Construct the following cell:
Pt|BHB (aq)MB (s) M(s)
Over all reaction:
M+ + B- MB(s) M (s) + B

ln Ksp = [E ((Eo2 Eo1 )]/ 0.0256

Half reactions:
Cathode: M+ + e M (s) Eo2
Anode: B + e B- Eo1

34
 Potentiometric titration
A technique that employs the effect of titrant on the
concentration of ions in the Analyte solution that results in
changing the emf according to Nernst equation.
You plot cell potential vs. volume of titrant added

35
 Continued
It is used in all types of volumetric analysis:
1- acid base titration
2- Precipitation titration
3- complex formation titration
4- redox titration
It is used best when it is not easy or impossible to
detect the end point by ordinary visual methods i.e:
a. For highly colored or turbid solutions.
b. For very dilute solutions 10-3 to 10-6 M.
c. When there is no available indicator

36
 Derivation of titration curve
Use Nernst equation to relate E to Eo and concentration:
E = = E - (RT/nF)lnQ
For precipitation reactions:
- The indicator electrode for a precipitation titration is frequently the metal from which
the reacting cation was derived.
- Theoretical curves for a potentiometric titration are readily derived
- Initially we use the half reaction for the reduction of the salt:
MX(s) + e M(s) + X- (EMX )
To calculate E at the start of the titration use
E = EMX - 0.0591 log [X ]
Then E can be calculated from reduction of half reaction of the reduction of the metal ion:
the following equation: M+ + e M(s)
E = EM - 0.0591 log 1/ [M+]
As the titrant concentration increases, E increases.
until a point where all [Cl-] is consumed completely,
Hence, any added M+ will stay in solution, and E will increase sharply at the end point
Then it levels of to give typical titration curve
37
Potentiometric titration curves

38
 Methods of obtaining the end point
1- Graphical: for the plot of E vs volume (V)
2- First derivative: calculate E and V and then plot
E/V vs. V. The volume at which E/V is maximum
is the end point.
3- Second derivative:
a- obtain the difference between two successive
E/V [(E/V)2 - [(E/V)1] and then divide by V.
This will give the second derivative (2E/V2).
b- Plot this value vs. V. The intercept with x-axis is
the end point (see next slide). 39
Manipulation of titration curve to
determine the end point

40
 Application of potentiometric titration in
a) Neutralization reactions: glass / calomel electrode
for determination of pH
b) Precipitation reactions: Membrane electrodes for
the determination of the halogens using silver
nitrate reagent
c) Complex formation titration: metal and membrane
electrodes for determination of many cations
(mixture of Bi3+, Cd2+ and Ca2+, using EDTA)
d) Redox titration: platinum electrode For
example for reaction of Fe3+/ Fe2+, with
Ce4+/Ce3+ 41
 Revision of chapter 8
Sections 8.1-8.5
Calculation involving standard electrode potential, cell
notation and cell reaction
Calculation of the thermodynamic parameters of Redox
reactions from cell potential and temperature
dependence.
Calculation involving Nernst equation
Calculation involving Nernst potential
Types of electrochemical cells
Application: pH, activity coefficient, Equilibrium
constants measurements (Ka and Ksp), and
potentiometric titration 42
 Announcement
Suggested problems:
1, 3, 6, 8, 11, 12, 20, 32, 34

Homework 4: Consult ilearn for deadline

Ist exam includes chapters 7 and 8. consult syllabus

Good luck

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