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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
6
19.4
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 zi2
= -97.7 mV
Electrochemical cells
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:
Cathode reaction:
Hg2Cl2(s) + 2e- 2Hg(l) + 2Cl-(aq) E1/2 = 0.27 V
Anode reaction:
H2(g) 2H+(aq) + 2e- E1/2 = 0.0 V
Cell reaction:
Hg2Cl2(s) + H2(g) 2Hg(l) + 2H+(aq) + 2Cl-(aq)Cath
18
Measurement of pH (cont.)
Hg2Cl2(s) + H2(g) 2Hg(l) + 2H+(aq) + 2Cl-(aq)
What if we let [H+] vary?
Q H Cl
2 2
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.
22
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 Ka 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.
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
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
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
Good luck
43