Electrochemistry

1
Copyright (c) 2011 by Michael A. Janusa, PhD. All rights reserved.
 Redox Reactions

• Examples of Redox Reactions:

Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s);
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)

Cu(s) + 2AgNO3(aq)  CuSO4(aq) + 2Ag(s);

Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s)

MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) 

Mn2+(aq) + 5Fe3+(aq) + 4H2O
 Balancing Redox Equations
• Review of Terms:
– Oxidation–reduction (redox) reaction – involves a
transfer of electrons from the reducing agent to the
oxidizing agent
– Oxidation – loss of electrons
– Reduction – gain of electrons
– Reducing agent – electron donor
– Oxidizing agent – electron acceptor
 Balancing Redox Equations

• Half–Reactions Method:
• The overall reaction is split into two half–
reactions, one involving oxidation and one
reduction.
8H+ + MnO4 + 5Fe2+  Mn2+ + 5Fe3+ + 4H2O

Reduction: 8H+ + MnO4 + 5e  Mn2+ + 4H2O

Oxidation: 5Fe2+  5Fe3+ + 5e
 Balancing Redox Equations

• The Half–Reaction Method for Balancing Equations

for Oxidation–Reduction Reactions Occurring in
Acidic Solution
1. Write separate equations for the oxidation and
reduction half–reactions.
2. For each half–reaction:
A. Balance all the elements except H and O.
B. Balance O using H2O.
C. Balance H using H+.
D. Balance the charge using electrons.
 Balancing Redox Equations:
The Half-Reaction Method

1. Write separate equations for oxidation and

reduction half–reactions.
2. For each half–reaction:
Balance all the elements except H and O.
Balance O using H2O.
Balance H using H+.
Balance the charge using electrons.
3. If necessary, multiply one or both balanced half–
reactions by an integer to make the number of
electrons in both half–reactions equal.
4. Add half–reactions and cancel identical species.
 Balancing Redox Equations

Example:

Cr2O72-(aq) + HSO3-(aq)  Cr3+(aq) + HSO4-(aq)

• How can we balance this equation?

• First Steps:
 Separate into half-reactions.
 Balance elements except H and O.
 Balancing Redox Equation:
The Half-Reaction Method

• Cr2O72-(aq)  2Cr3+(aq)  
• HSO3-(aq)  HSO4-(aq)

• How many electrons are needed to balance the

charge in each half-reaction?
 Balancing Redox Equation:
The Half-Reaction Method

• Adding electrons:
• 6e- + Cr2O72-(aq)  2Cr3+(aq) 
• HSO3-(aq)  HSO4-(aq) + 2e-

• How can we balance the oxygen atoms?

 Balancing Redox Equation:
The Half-Reaction Method

• 6e- + Cr2O72-(aq)  Cr3+(aq) + 7H2O 

• H2O + SO32-(aq)  + SO42-(aq) + 2e-

• How can we balance the hydrogen atoms?

 Balancing Redox Equation:
The Half-Reaction Method

• This reaction occurs in an acidic solution.

• 14H+ + 6e- + Cr2O72-  2Cr3+ + 7H2O 
• H2O + HSO3-  HSO4- + 2e- + 2H+

• How can we balance the electrons?

 Balancing Redox Equation:
The Half-Reaction Method

• 14H+ + 6e- + Cr2O72-  2Cr3+ + 7H2O

• 3[H2O + HSO3-  HSO42- + 2e- + 2H+]

• The final balanced equation:

Cr2O72- + 3HSO3- + 8H+  2Cr3+ + 3HSO4- + 4H2O

 Sample Exercises

Balance the following redox reactions in acidic

solution.

1) Br–(aq) + MnO4–(aq)  Br2(l) + Mn2+(aq)

2) Cr2O72-(aq) + H2O2(aq)  Cr3+(aq) + H2O(l) + O2(g)

Br–(aq) + MnO4–(aq)  Br2(l) + Mn2+(aq)

14
Cr2O72-(aq) + H2O2(aq)  Cr3+(aq) + H2O(l) + O2(g)

15
 The Half–Reaction Method for Balancing
Redox Equations in Basic Solution

1. Use the half–reaction method as specified for acidic

solutions to obtain the final balanced equation as if
H+ ions were present.
2. To both sides of the equation, add a number of OH–
ions that is equal to the number of H+ ions present.
(You want to eliminate H+ by turning is into H2O)
3. Form H2O on the side containing both H+ and OH–
ions, and eliminate the number of H2O molecules
that appear on both sides of the equation.
4. Check that elements and charges are balanced.
 Sample Exercises

• Balance the following redox reactions in

basic solution:

• Br2(aq) + OH-(aq)  BrO3-(aq) + Br-(aq) +

H2O;

• Cr(OH)4-(aq) + OH-(aq)  CrO42-(aq) + H2O;

Br2(aq) + OH-(aq)  BrO3-(aq) + Br-(aq) + H2O

18
Cr(OH)4-(aq) + OH-(aq)  CrO42-(aq) + H2O

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 36.1 Oxidation-Reduction Reactions
• Back in general chemistry I and the beginning
of this semester we covered the half-
reaction method for balancing oxidation-
reduction reactions.
– Oxidation-reduction reactions always involve a
transfer of electrons from one species to
another.
– oxidation - lose electron - higher ox state
Fe2+  Fe3+ + 1e-
– reduction - gain electrons - lower ox state
Fe3+ + 1e-  Fe2+

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 Oxidation-Reduction Reactions
– An oxidizing agent is a species that oxidizes
another species; it is itself reduced.
– A reducing agent is a species that reduces
another species; it is itself oxidized.
Loss of 2 e-1 oxidation
reducing agent
2 2
Fe( s )  Cu ( aq )  Fe ( aq )  Cu( s )
oxidizing agent
Gain of 2 e-1 reduction

2 
red : Cu ( aq )  2e  Cu ( s )
2 
ox________________________
: Fe( s )  Fe ( aq )  2 e
2 2
Fe( s )  Cu ( aq )  Fe ( aq )  Cu( s ) 21
 Oxidation-Reduction Reactions
• In this chapter we will show how a cell is constructed to
physically separate an oxidation-reduction reaction
into two half-reactions.
 
red : ( Ag ( aq )  1e  Ag ( s ) ) 2
e- 2 
Ag(s) Cu Cu2+ ox : Cu  Cu ( aq )
________________________
(s)  2 e
AgNO3(aq) Cu  Cu2+ Ag+ Ag
Cu ( s )  2 Ag  ( aq )  Cu 2 ( aq )  2 Ag ( s )
ox red

electrochemical cell
– The force with which electrons travel from the
oxidation half-reaction to the reduction half-
reaction is measured as voltage (actually
produces electricity). 22
 Electrochemistry
• An electrochemical cell is a system consisting of
electrodes that dip into an electrolyte in which a
chemical reaction either uses or generates an electric
current.
– A voltaic, or galvanic, cell is an electrochemical
cell in which a spontaneous reaction generates
an electric current (+V, rxn occurs on own).
– An electrolytic cell is an electrochemical cell in
which an electric current drives an otherwise
nonspontaneous reaction (-V, rxn does not occur
on own, need outside source).

23
 36.2 Voltaic Cells
• A voltaic cell consists of two half-cells that
are electrically connected.
– Each half-cell is a portion of the electrochemical
cell in which a half-reaction takes place. No
reaction between species involved just a transfer
of electrons.
– A simple half-cell can be made from a metal strip
dipped into a solution of its metal ion.
– For example, the silver-silver ion half cell consists
consists of a silver strip dipped into a solution of a
silver salt.
electrode
Cu Ag

AgNO3
24
 volt
meter
Figure : or light
Voltaic cell
consisting oxidation reduction
of cadmium
and silver
electrodes. KCl

Cd(NO3)2 AgNO3

Ebbing, D. D.; Gammon, S. D. General 25

Chemistry, 8th ed., Houghton Mifflin, New
York, NY, 2005.
 Voltaic Cells
– In a voltaic cell, two half-cells are connected in such a
way that electrons flow from one metal electrode to
the other through an external circuit.
– This cell has Ag reduced and Cd oxidized.
– Cathode red: [Ag+ + 1e-  Ag (s)] 2 (must happen twice)
– Anode ox: Cd (s)  Cd2+ + 2 e-
– overall: 2Ag+ + Cd (s)  2 Ag (s) + Cd2+

is the net reaction that occurs in the voltaic cell; it is

called the cell reaction
– Note that electrons are given up at the anode (-)
and thus flow from it to the cathode (+) where
reduction occurs.
26
 Voltaic Cells
• As long as there is an external circuit, electrons
can flow through it from one electrode to the other.
– Because cadmium has a greater tendency to
lose electrons than silver, cadmium atoms in the
cadmium electrode lose electrons to form
cadmium ions.
– The electrons flow through the external circuit to
the silver electrode where silver ions gain the
electrons to become silver metal.
– The anode (oxidation) in a voltaic cell has a negative
sign because electrons flow from it.
The cathode (reduction) in a voltaic cell has a positive
sign
27
 Voltaic Cells
• The two half-cells must also be
connected internally to allow ions to flow
between them and complete the circuit.
– Without this internal connection (salt bridge), too
much positive charge builds up in the cadmium
half-cell (and too much negative charge in the
silver half-cell) causing the reaction to stop (must
have counter ion to balance charges). KCl salt
bridge is present for this purpose.

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 Figure : Two electrodes are connected by
an external circuit.

ox red

NO3-
NO3-
Cl- Cl- K+ K+ Cu(NO3)2

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

Chemistry, 8th ed., Houghton Mifflin, New 29
York, NY, 2005.
 Voltaic Cells

• A salt bridge is a tube of an electrolyte in a gel that

is connected to the two half-cells of a cell.
– The salt bridge allows the flow of ions but
prevents the mixing of the different solutions
that would allow direct reaction of the cell
reactants.
– completes circuit
– keeps electrostatic neutral

30
–The voltage produced is from the potential
difference between the two metals at any instant. It
is a measure of the tendency of the cell reaction to
proceed toward equilibrium.
–Equil is driving force of reaction. As reaction
proceeds, potential difference decreases
continuously and approaches zero as equil is
approached.
–Not infinite amount of electricity. When reach equil
have 0V. The conc . of species has effect on equil
and the amount of voltage. Further away from equil,
the higher the potential difference.

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 36.2.1 Electrochemical Cell Notation

• It is convenient to have a shorthand way of

designating particular cells.
– The cell consisting of the cadmium-cadmium ion
half-cell and the silver-silver ion half-cell, is written
2 
Cd ( s ) | Cd ( aq ) || Ag ( aq ) | Ag ( s )
anode cathode
(ox) salt bridge red
– The anode (oxidation half-cell) is written on the left. The cathode (reduction
half-cell) is written on the right.
– Double line indicates salt bridge is present but not always present; both half
reactions can be in same container.

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 2 2
Zn(s ) | Zn (aq ) || Cu (aq ) | Cu(s )
salt bridge
anode cathode
– The cell terminals are at the extreme ends in the cell notation
(electrode metal).

– A single vertical bar indicates a phase boundary, such as between

a solid terminal and the electrode solution (states usually omitted).

red : Cu 2  ( aq )  2e   Cu ( s )
2 
ox : Zn  Zn ( aq
____________________
(s) )  2 e
Zn ( s )  Cu 2  ( aq )  Cu ( s )  Zn 2  ( aq )

33
 Notation for Cells
• When the half-reaction involves a gas, an inert
material such as platinum or carbon serves as a
terminal and the electrode surface on which the
reaction occurs.
– Example is the hydrogen electrode; hydrogen
bubbles over a platinum plate immersed in an
acidic solution.
– The cathode half-reaction is
 
2H (aq )  2e  H 2 ( g )
Slide 59

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 Notation for Cells

– The notation for the hydrogen electrode,

written as a cathode, is

anode || 
H (aq ) | H 2 ( g ) | Pt Sometimes written as
SHE (1atm, 1M)

– To write such an electrode as an anode,

you simply reverse the notation; want
terminal as extreme end.
Pt | H 2 ( g ) | H (aq ) ||
 cathode

35
 Notation for Cells
• To fully specify a cell, it is necessary to give the
concentrations of solutions and the pressure of
gases.
– In the cell notation, these are written in
parentheses. For example,
2 
Zn | Zn (1 .0 M ) || H (1 .0 M ) | H 2 (1 .0 atm ) | Pt
e-
- +

Zn Pt
ox: Zn  Zn2+ +2e- Eo
H2 1atm red: 2H+ +2e-  H2 Eo
Zn2+ 1M H+ 1M
ox red
2H+ + Zn  Zn2+ + H2 Eocell
anode cathode
note: spectator ions are not usually present in short notation.
This is an example of a standard cell: 1M, 1atm, 25oC (298K) 36
 - e- +

Cd Pt
H2 1atm
Cd2+ 1M H+ 1M
ox red
anode cathode
• Draw cell and write the overall cell reaction for
the given cell
2 
Cd ( s ) | Cd (1 .0 M ) || H (1 .0 M ) | H 2 (1 .0 atm ) | Pt
– The half-cell reactions are
2 
anode ox: Cd(s )  Cd (aq )  2e Eo
 
cath red: 2H (aq )  2e  H 2 ( g ) Eo

 2
Cd(s )  2H (aq )  Cd (aq )  H 2 ( g ) Eocell

37
 Electromotive Force
• Potential difference, Ecell, is the
difference in electric potential (electrical
pressure) between two points.
– You measure this quantity in volts.
– The volt, V, is the SI unit of potential
difference equivalent to 1 joule of energy
per coulomb of charge.

1 volt  1 J
C
38
 Electromotive Force
• The Faraday constant, F, is the magnitude
of charge on one mole of electrons; it equals
96,500 coulombs (9.65 x 104 C).
1 F = 96,500 C = charge of 1 mole e-
– In moving 1 mol of electrons through a circuit, the
numerical value of the work done by a cell is the
product of the Faraday constant (F) times the
potential difference between the electrodes.

work(J)   F(coulombs )  volts(J/ coulomb )

work done by the system

39
 Electromotive Force

– In the normal operation of a voltaic cell, the potential

difference (voltage) across the electrodes is less
than the maximum possible voltage of the cell.

– The actual flow of electrons reduces the electrical

pressure; therefore, slightly lower voltage obtained.

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 Electromotive Force

• electromotive force (emf) of the cell,

or Ecell - the maximum potential
difference between the electrodes of a
cell.
– It can be measured by an electronic digital
voltmeter.

41
 Standard Cell emf’s and Standard
Electrode Potentials

• A cell emf is a measure of the driving

force of the cell reaction.
– The reaction at the anode has a definite oxidation
potential, while the reaction at the cathode has a
definite reduction potential.
– Thus, the overall cell emf is a combination of these
two potentials.

Ecell = reduction potential, Ered + oxidation potential, Eox

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 Standard Cell emf’s and Standard
Electrode Potentials
– A reduction potential, Ered, is a measure
of the tendency to gain electrons in the
reduction half-reaction.
Ered A+ + 1e-  A (s) E=xV
– You can look at the oxidation half-reaction as the
reverse of a corresponding reduction reaction.
– The oxidation potential, Eox, for an
oxidation half-reaction is the negative of
the reduction potential for the reverse
reaction. Eox A (s)  A+ + 1e- E = -x V

43
 36.3 Standard Electrode Potentials Slide 44
• By convention, the Table of Standard (1M, 1atm,
25oC) Electrode Potentials are tabulated as Slide 28
reduction potentials (all).
Slide 27
– Consider the zinc-copper cell described earlier,
calculate the Eocell.
2 2
Zn ( s ) | Zn (1M ) || Cu (1M ) | Cu ( s )
– The two half-reactions are
2 
ox : Zn ( s )  Zn ( aq )  2 e Eo = 0.76V (changed sign from table)

red : Cu 2
( aq )  2 e 
 Cu ( s ) Eo = 0.34V
_________________________________________
Zn + Cu2+ --> Zn2+ + Cu Eocell = 1.10 V voltaic, spon
This voltage for standard cell: 1M otherwise need to correct from std conc of 1M.
Note table is electrode potentials for standard (superscript o: 1M, 1atm, 298K) 44
 All are reductions;
reducing agent Flip and change sign
for oxidation
oxidized

Std: 1M, 1atm, 25oC

reduced

H: reference electrode

Cu  Cu2+
Ag+  Ag spon
Slide 26

Slide 33
oxidizing agent 45
Ebbing, D. D.; Gammon, S. D. General Chemistr
8th ed., Houghton Mifflin, New York, NY, 2005.
 Standard Cell emf’s and Standard
Electrode Potentials

– The electrode potential is an intensive

property whose value is independent of
the amount of species in the reaction.

46
 Standard Cell emf’s and Standard
Electrode Potentials
– Thus, the electrode potential for the half-reaction

Cu 2 (aq )  2e   Cu(s ) Eo = 0.34V

is the same as for

2Cu 2 (aq )  4e   2Cu(s ) Eo = 0.34V

Recall: K flip 1/K

n factor Kn
H flip -H
n factor nH
 flip -
47
n factor E
36.3.1 Standard Cell Electrode Potentials
• The standard emf (theoretical potential),
E°cell, is the emf of a cell operating under
standard conditions of concentration (1 M),
pressure (1 atm), and temperature (25°C).
– Note that individual electrode potentials require that
we choose a reference electrode.
– arbitrarily assign this reference electrode a potential
of zero and obtain the potentials of the other
electrodes by measuring the emf’s. These are
relative values not absolute.

48
Tabulating Standard Electrode Potentials
– By convention, the reference chosen for comparing electrode
potentials is the standard hydrogen electrode (SHE).
– Standard electrode potentials are measured relative to this
hydrogen reference as the anode.
– For example, when measure the emf of a cell composed of a zinc
electrode connected to a hydrogen electrode, you obtain 0.76
V with hydrogen being cathode and zinc as anode for the spon
rxn. By definition, we want the comparison of hydrogen to other
species to be hydrogen as anode and the other species as
cathode; Since hydrogen is given zero value all voltage measured
is given to zinc but we must change sign for reduction value of
zinc as defined in table.

– Since zinc acts as the anode (oxidation) in this spon cell, its
reduction potential is listed as –0.76 V. This means that zinc has
a potential that is 0.76 less than hydrogen (relative not abs)
49
36.4 Predicting the Spontaneous Direction
of a Redox Reaction
• Standard electrode potentials are useful in determining the
strengths of oxidizing and reducing agents under standard-
state conditions.

– the strongest oxidizing agents (species undergoes

reduction) in a table of standard electrode potentials are the
species corresponding to the half-reactions with the largest
(most positive) Eo values. (For example F2(g) highest E in the
table and strongest ox agent in the table -- prefers to be
reduced compared to any other species in table. Will always
be reduced in spon rxn. with any of species in table.)
– Bottom line: Larger Eo, stronger oxidizing agent, more tendency
to undergo reduction with other species.
Slide 27

50
 Strengths of Oxidizing and Reducing
Agents
– Consequently, the strongest reducing agents
(species undergoes oxidation) in a table of standard
electrode potentials are the species corresponding to
the half-reactions with the smallest (most negative)
Eo values. (for example, Li smallest E in the table;
therefore, Li (s) strongest red agent in the table [note:
must flip for oxidation] -- prefers to be oxidized
compared to any other species in table. Will always
be oxidized in spon rxn. with any of species in table.)
– Bottom line: Smaller Eo, stronger reducing agent, more
tendency to undergo oxidation with other species.

Slide 27
51
 Calculating Cell emf’s from Standard
Potentials
• What would be the spon rxn between Cd and
Ag? Calculate Eocell for spon rxn at 25oC and 1
M (std cell)
– Consider a cell constructed of the following two
half-reactions (given from table)
2  o
Cd (aq )  2e  Cd(s ); E  0.40 V
Reducing agent
  o
Ag (aq )  1e  Ag(s ); E  0.80 V
Oxidizing agent
Ag+ higher E therefore expect to be reduced (ox agent) and
Cd (s) oxidized (red agent) in spon rxn.
52
 Calculating Cell emf’s from Standard
Potentials
– Therefore, you reverse the half-reaction and
change the sign of the half-cell potential of
cadmium.
2  o
ox : Cd ( s )  Cd ( aq )  2e ; E  0.40 V
  o
red : Ag ( aq )  1e  Ag ( s ); E  0.80 V
– We must double the silver half-reaction so that when
the reactions are added, the electrons cancel.

– This does not affect the half-cell potentials, which do

not depend on the amount of substance.

53
 Calculating Cell emf’s from Standard
Potentials
– Now we can add the two half-reactions to obtain the overall cell reaction and cell emf.

– note: positive voltage meaning spon reaction for standard cell. If not std cell must correct and will discuss later.

2  o
ox : Cd ( s )  Cd ( aq )  2 e ; E  0.40 V
  o
red : 2 Ag ( aq )  2 e  2 Ag ( s ); E  0.80 V

Cd(s )  2 Ag  (aq )  Cd 2 (aq )  2 Ag (s ); Eocell  1.20 V

54
 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
55
 A Problem To Consider
• Calculate the standard emf, Eocell, for the
following cell at 25°C.
3 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

56
 A Problem To Consider
Given
Al 3 (aq )  3e   Al(s ); E o  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 )  2 e   Fe ( s ); E o   0.41 V
57
 A Problem To Consider
3 2
Al ( s ) | Al (1M ) || Fe (1M ) | Fe ( s )
3  o
2X ox : Al ( s )  Al ( aq )  3e ; E  1.66 V
2  o
3X red : Fe ( aq )  2 e  Fe ( s ); E   0.41 V
– To obtain the overall reaction we must balance the electrons.

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

3Fe 2 (aq )  6e   3Fe (s ); E o  0.41 V
note: no multiply by factor to E

58
 A Problem To Consider

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

2  o
3Fe (aq )  6e  3Fe (s ); E  0.41 V

2 Al(s )  3Fe 2 (aq )  2 Al 3 (aq )  3Fe(s ); Eo  1.25 V

reducing oxidizing
agent agent

HW 49
code: seven 59
 36.5 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
60
 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 61
• Previously we determined the standard emf for the
following cell is 1.10 V Slide 26 .
2 2
Zn ( s ) | Zn (1M ) || Cu (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

o 0.0592
E 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
62
 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:
37.2 37
K c  anti log( 37.2)  10  1.6  10
– The number of significant figures in the answer
equals the number of decimal places in 37.2 (one).
Thus 37
K c  2  10

63
 Dependence of emf on Concentration
• 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:

64
 36.6 Nernst Equation
• The Nernst equation is an equation
relating the cell emf to its standard emf
and the reaction quotient.
o 2.303RT
Ecell  Ecell  log Q
nF

o 0.0592
Ecell  Ecell  log Q at 25oC
n

65
 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
66
 Zn ( s ) | Zn 2  (1.0  10 5 M ) || Cu 2  ( 0.100 M ) | Cu ( s )
Given: 2 
Zn ( aq )  2 e  Zn ( s ) Eo = -0.76V
2 
Cu ( aq )  2 e  Cu ( s ) Eo = 0.34V

– The two half-reactions are

2 
ox : Zn ( s )  Zn ( aq )  2 e 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

67
 2 2
Zn(s )  Cu (aq ) Zn (aq )  Cu(s ) Eocell = 1.10V

o 0.0592
Ecell  E cell  log Q
n
2
o 0.0592 [ Zn ]
Ecell  E cell  log 2
n [Cu ]
5
0.0592 1.0  10
Ecell  1.10 V  log
2 0.100
E cell  1.10 V  ( 0.12)  1.22 V
voltaic, spon 68
 36.7 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.

69
example : Calculate Ecell
 2 2
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

Cu 2  ( aq )  2 e   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  Eo = 0.34V
red : Cu ( aq )  2e  Cu ( s )
2 Ag ( s )  Cu 2  ( aq ) 2 A g  ( aq )  Cu ( s ) Eocell = -0.46V

for std cell but not a std cell

70
continue
2 Ag ( s )  Cu 2  ( aq ) 2 A g  ( aq )  Cu ( s ) Eocell = -0.46V

o 0.0592
Ecell  E cell  log Q
n
 2
o 0.0592 [ Ag ]
Ecell  E 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
71
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
 36.8 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.

73
 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

74
 A Problem To Consider
When an 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 )  2 e   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 2
charge  (8.52  10 C / s )  ( 6.00  10 s )  5 .11 C
96,500 C = charge of 1 mole e-
A=C/s
75
 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  4
    6. 73  10 3
g I2
9.65 10 C 2 mol e 1 mol I 2

76
Figure : A
hydrogen
electrode.

Slide 16

Ebbing, D. D.; Gammon, S. D. General 77

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