EQUILBRIUM CONSTANT AND KSP

SUMMARY OF THERMODYNAMIC, EQUILIBRIUM

AND ELECTROCHEMICAL RELATIONSHIPS.
3
CALCULATING CELL EMF’S FROM STANDARD
POTENTIALS
– How would we write and draw the cell we just did in
short notation?

Cd(s ) | Cd 2 (1M ) || Ag  (1M ) | Ag(s )

e-

- +
Cd Ag

Cd2+ 1M Ag+ 1M
ox red
anode cathode
4
A PROBLEM TO CONSIDER
• Calculate the standard emf, Eocell, for the
following cell
3
at 25°C. 2 
Al ( s ) | Al (1M ) || Fe (1M ) | Fe ( s )
ox red
– The reduction half-reactions and standard
potentials are (given)
3  o
Al (aq )  3e  Al(s ); E  1.66 V
2  o
Fe (aq )  2e  Fe(s ); E  0.41 V
5
A PROBLEM TO CONSIDER
Given
Al 3 (aq )  3e   Al(s ); Eo  1.66 V
Fe 2 (aq )  2e   Fe(s ); Eo  0.41 V
3 2
Al ( s ) | Al (1M ) || Fe (1M ) | Fe ( s )
– You reverse the first half-reaction and its half-cell
potential to obtain

ox : Al ( s )  Al 3 ( aq )  3e  ; E o  1.66 V
red : Fe 2  ( aq )  2e   Fe ( s ); E o  0.41 V
6
A PROBLEM TO CONSIDER
3 2
Al ( s ) | Al (1M ) || Fe (1M ) | Fe ( s )
3 
2X ox : Al ( s )  Al ( aq )  3e ; E  1.66 V
o

2 
3X red : Fe ( aq )  2e  Fe ( s ); E  0.41 V o

– To obtain the overall reaction we must balance the

electrons.
3  o
2 Al(s )  2 Al (aq )  6e ; E  1.66 V
2  o
3Fe (aq )  6e  3Fe(s ); E  0.41 V
note: no multiply by factor to E
7
A PROBLEM TO CONSIDER
– Now we add the reactions to get the overall cell reaction and cell
emf.

2 Al(s )  2 Al 3 (aq )  6e  ; Eo  1.66 V

2  o
3Fe (aq )  6e  3Fe(s ); E  0.41 V
Spon - +V obtained for std cell
2 Al(s )  3Fe 2 (aq )  2 Al (aq )  3Fe(s ); E  1.25 V
3 o

reducing oxidizing
agent agent
8
EQUILIBRIUM CONSTANT, K, AND EOCELL

• Some of the most important results from

electrochemistry are the relationships among E°cell,
Gibbs free energy, and equilibrium constant.
– The measurement of cell emf’s gives you
yet another way of calculating equilibrium
constants. Combining several equations
we obtain
o 2.303RT
Ecell  log K
nF
9
EQUILIBRIUM CONSTANTS FROM EMF’S
– Substituting values for the constants R and F at
25oC gives the equation
o 0.0592
Ecell  log K (value in volts at 25 oC)
n
0.0592 combination of constants including temp at
298 K
n = number of electrons transferred in balanced eq.
K is equil constant or setup for calc - prod/reactants
example aA +bB cC + dD [C]c[D]d
[A]a[B]b
• Previously we determined the standard emf for 10

the following cell is 1.10 V .

Zn ( s ) | Zn 2  (1M ) || Cu 2  (1M ) | Cu ( s )
2 2
Zn(s )  Cu (aq ) Zn (aq )  Cu(s ) o
Ecell  1.10V

Calculate the equilibrium constant Kc for the reaction

0.0592
E o
cell  log K
n
– Note that n=2. Substituting into the equation
relating Eocell and K gives
0.0592
1.10 V  log K
2
11
A PROBLEM TO CONSIDER
– Solving for log Kc, you find
(1.10)(2)
log K   37.2
0.0592
– Now take the antilog of both sides:

K c  anti log(37.2)  10 37.2

 1.6  10 37

– The number of significant figures in the answer

equals the number of decimal places in 37.2 (one).
Thus 37
K c  2  10
 DEPENDENCE OF EMF ON CONCENTRATION
12

• Recall that everything we have done so far has been with a

standard cell.
• If an electrode is a measure of the extent to which
concentration in a half cell differs from an equil value; then
concentration will affect equil and vary electrode potential.
• Electrode potential is dependent on concentration. Further
from equil, greater potential (higher voltage).
• Remember E for table is for standard conditions. If
concentrations are not std concentrations, then the cell
potential must be corrected.
• Basically, the potential for non std cell will be equal to the
std cell potential with a correcting factor for nonstd
concentrations. The basic equation is as follows:
13
NERNST EQUATION

• The Nernst equation is an equation relating the cell emf

to its standard emf and the reaction quotient.
2.303RT
Ecell  E o
cell  log Q
nF

o 0.0592
Ecell  Ecell  log Q at 25oC
n
14
DEPENDENCE OF EMF ON CONCENTRATION

o 0.0592
Ecell  Ecell  log Q
n
• Basically, second half of equation is correcting
factor for not being std conc. If at std conc (1M
each), Q=1 and log 1 = 0. Could use even at
• std and get correct answer.
What is the emf, Ecell, of the following cell at 25°C?
2 5 2
Zn ( s ) | Zn (1.0  10 M ) || Cu (0.100 M ) | Cu ( s )
note: not std cell
 Zn ( s ) | Zn 2  (1.0  10 5 M ) || Cu 2  (0.100 M ) | Cu ( s )
15
Given:
Zn 2  ( aq )  2e   Zn ( s ) Eo = -0.76V
2 
Cu ( aq )  2e  Cu ( s ) Eo = 0.34V

– The two half-reactions are

2 
ox : Zn ( s )  Zn ( aq )  2e Eo = 0.76V (changed sign from table)
2 
red : Cu ( aq )  2e  Cu ( s ) Eo = 0.34V

– The cell reaction is

Zn(s )  Cu 2 (aq ) Zn 2 (aq )  Cu(s ) Eocell = 1.10V

for std cell but not a std cell

 2 2
Zn(s )  Cu (aq ) Zn (aq )  Cu(s ) Eocell = 1.10V

0.0592
Ecell  E o
cell  log Q
n
2
0.0592 [ Zn ]
Ecell  E o
cell  log 2
n [Cu ]
5
0.0592 1.0  10
Ecell  1.10 V  log
2 0.100
Ecell  1.10 V  ( 0.12)  1.22 V
voltaic, spon
17 ELECTROLYTIC CELLS

• An electrolytic cell is an electrochemical

cell in which an electric current drives an
otherwise nonspontaneous reaction.
– The process of producing a chemical change in an
electrolytic cell is called electrolysis.
– Many important substances, such as aluminum
metal and chlorine gas are produced commercially
by electrolysis.
 example : Calculate Ecell
 2 2
18
Ag ( s ) | Ag (1.00  10 M ) || Cu (1.50 M ) | Cu ( s )
Given: ox   red
Ag ( aq )  1e  Ag ( s ) E = 0.80V
o

2 
Cu ( aq )  2e  Cu ( s ) Eo = 0.34V
– The two half-reactions are
 
ox : [ Ag ( s )  Ag ( aq )  1e ]2 Eo = -0.80V (changed sign from table)
2 
red : Cu ( aq )  2e  Cu ( s ) Eo = 0.34V

2 Ag ( s )  Cu 2  ( aq ) 2 Ag  ( aq )  Cu ( s ) Eocell = -0.46V

for std cell but not a std cell

continue
2 Ag ( s )  Cu 2  ( aq ) 2 Ag  ( aq )  Cu ( s ) Eocell = -0.46V
0.0592
Ecell  E o
cell  log Q
n
 2
0.0592 [ Ag ]
Ecell  E o
cell  log 2
n [Cu ]
2 2
0.0592 (1.00  10 )
Ecell  0.46 V  log
2 1.50
E cell  0.46 V  ( 0.124V )  0.34 V
electrolytic, nonspon
Calculate Eocell What if source of H+ is HCl? SA, problem works the same.
Pt | U4+ (0.200M), UO22+ (0.0150M), H+ (0.0300M) || Fe3+ (0.0250M), Fe2+ (0.0100M) | Pt
ox red
Given: Fe3+ + 1e-  Fe2+ Eo = 0.771V
UO22+ + 4H+ + 2e-  U4+ + 2H2O Eo = 0.334V

Red: 2( Fe3+ + 1e-  Fe2+ ) Eo = 0.771V

Ox: U4+ + 2H2O  UO22+ + 4H+ + 2e- Eo = -0.334V
______________________________________________
2Fe3+ + U4+ + 2H2O  UO22+ + 4H+ + 2Fe2+ Eo = 0.437V
Calculate Eocell What if source of H+ is HCN, weak acid?
Pt | U4+ (0.200M), UO22+ (0.0150M), HCN (0.0300M, Ka = 6.2 x 10-10) || Fe3+ (0.0250M), Fe2+ (0.0100M) | Pt

HCN (aq) + H2O (l) H3O+ (aq) + CN- (aq)

[HCN] [H3O+] [CN-]
Initial, [ ]o 0.0300 0 0
Change, D[ ] -x +x +x

Equilibrium, [ ]eq 0.0300 - x x x

H+
Calculate Eocell
ox red
Ag | AgCl (sat’d, Ksp = 1.82 x 10 ), NaCl (0.0200 M) || HBr (0.0200 M) | H2 (0.800 atm) | Pt
-10

Given: Ag+ + 1e-  Ag Eo = 0.799V

2H+ + 2e-  H2 Eo = 0.000V
ox: 2(Ag  Ag+ + 1e- ) Eo = -0.799V
2H+ + 2e-  H2
red: ____________________________________
Eo = 0.000V
2Ag + 2H+  2Ag+ + H2 Eo = -0.799V
?

NaCl (s)  Na+ (aq) + Cl- (aq)

0.0200 M 0.0200 M
AgCl (s) Ag+ (aq) + Cl- (aq)
[Ag+] [Cl-]
Initial, [ ]o 0 0.0200
Change, D[ ] +s +s
Equilibrium, [ ]eq s 0.0200 + s
 AgCl (s) Ag+ (aq) + Cl- (aq)
[Ag+] [Cl-]
Initial, [ ]o 0 0.0200
Change, D[ ] +s +s
Equilibrium, [ ]eq s 0.0200 + s

Ksp =

= [AgCl]
24
STOICHIOMETRY OF ELECTROLYSIS
• What is new in this type of stoichiometric problem is the
measurement of numbers of electrons.

You do not weigh them as you do substances.

Rather, you measure the quantity of electric
charge that has passed through a circuit.
To determine this we must know the current
and the length of time it has been flowing.
25
STOICHIOMETRY OF ELECTROLYSIS
Electric current is measured in amperes.
An ampere (A) is the base SI unit of current
equivalent to 1 coulomb/second. 1 A = 1 C/s

The quantity of electric charge passing through

a circuit in a given amount of time is given by

Electric charge(coul) = electric current (A or coul/sec)  time lapse(sec)

note: A = C/s
26
A PROBLEM
When anTO CONSIDER
aqueous solution of potassium
iodide is electrolyzed using platinum
electrodes, the
 half-reactions
 are
ox : 2 I ( aq )  I 2 ( s )  2e
red : 2 H 2 O (l )  2e   H 2 ( g )  2OH  ( aq )
How many grams of iodine are produced when a
current of 8.52 mA flows through the cell for 10.0 min?
Electric charge(coul) = electric current (A or coul/sec)  time lapse(sec)

When the current flows for 6.00 x 102 s (10.0 min),

the amount of charge is
3
charge  (8.52  10 C / s )  (6.00  10 s )  5.11 C 2

96,500 C = charge of 1 mole e-

A=C/s
27
A PROBLEM TO CONSIDER
2 I  ( aq )  I 2 ( s )  2e 
Note that two moles of electrons are equivalent to
one mole of I2. Hence,
1 mol e  1 mol I 2 254 g I 2
5.11 C      6 .73  10 3
g I2
9.65 10 C 2 mol e
4
1 mol I 2

HW 50
code: nernst
28
FIGURE : A
HYDROGEN
ELECTRODE
.

Slide 16

Ebbing, D. D.; Gammon, S. D. General

Chemistry, 8th ed., Houghton Mifflin, New
York, NY, 2005.