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Electrochemistry
1
Copyright (c) 2011 by Michael A. Janusa, PhD. All rights reserved.
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+
2
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
: Fe( s ) Fe ( aq ) 2e
ox________________________
2 2
Fe( s ) Cu ( aq ) Fe ( aq ) Cu( s ) 3
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 (s) Cu ( aq )
________________________ 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). 4
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).
5
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
6
volt
meter
Figure : or light
Voltaic cell
consisting oxidation reduction
of cadmium
and silver
electrodes. KCl
Cd(NO3)2 AgNO3
10
Figure : Two electrodes are connected by
an external circuit.
ox red
NO3-
NO3-
Cl- Cl- K+ K+ Cu(NO3)2
12
–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.
13
36.2.1 Electrochemical Cell Notation
14
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 )
15
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
16
Notation for Cells
17
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) 18
- 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
19
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
20
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.
21
Electromotive Force
22
Electromotive Force
23
Standard Cell emf’s and Standard
Electrode Potentials
24
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. E A (s) A+ + 1e- E = -x V
ox
25
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 ) 2e Eo = 0.76V (changed sign from table)
2
red : Cu ( aq ) 2e 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) 26
All are reductions;
reducing agent Flip and change sign
for oxidation
oxidized
H: reference electrode
Cu Cu2+
Ag+ Ag spon
Slide 26
Slide 33
oxidizing agent 27
Ebbing, D. D.; Gammon, S. D. General Chemistr
8th ed., Houghton Mifflin, New York, NY, 2005.
Standard Cell emf’s and Standard
Electrode Potentials
28
Standard Cell emf’s and Standard
Electrode Potentials
– Thus, the electrode potential for the half-reaction
30
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.
Slide 27
32
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
33
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
Cd (aq ) 2e Cd(s ); E 0.40 V o
Reducing agent
Ag (aq ) 1e Ag(s ); E 0.80 V o
Oxidizing agent
Ag+ higher E therefore expect to be reduced (ox agent) and
Cd (s) oxidized (red agent) in spon rxn.
34
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
ox : Cd ( s ) Cd ( aq ) 2e ; E 0.40 V
o
red : Ag ( aq ) 1e Ag ( s ); E 0.80 V o
35
Calculating Cell emf’s from Standard
Potentials
– Now we can add the two half-reactions to obtain the
overall cell reaction and cell emf.
red : 2 Ag ( aq ) 2e 2 Ag ( s ); E 0.80 V
o
e-
- +
Cd Ag
Cd2+ 1M Ag+ 1M
ox red
anode cathode
37
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
Al (aq ) 3e Al(s ); E 1.66 V
o
2
Fe (aq ) 2e Fe(s ); E 0.41 V
o
38
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
39
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
40
A Problem To Consider
– Now we add the reactions to get the overall cell
reaction and cell emf.
3
2 Al(s ) 2 Al (aq ) 6e ; E 1.66 V
o
2
3Fe (aq ) 6e 3Fe(s ); E 0.41 V
o
HW 49
code: seven 41
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
2.303RT
o
Ecell log K
nF
42
Equilibrium Constants from emf’s
0.0592
o
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 43
• Previously we determined the standard emf for the
following cell is 1.10 V Slide 26 .
Zn ( s ) | Zn 2 (1M ) || Cu 2 (1M ) | Cu ( s )
2 2
Zn(s ) Cu (aq ) Zn (aq ) Cu(s ) o
Ecell 1.10V
45
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:
46
36.6 Nernst Equation
• The Nernst equation is an equation
relating the cell emf to its standard emf
and the reaction quotient.
2.303RT
Ecell Ecell
o
log Q
nF
0.0592
Ecell o
Ecell log Q at 25oC
n
47
Dependence of emf on Concentration
0.0592
Ecell o
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.
49
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 50
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.
51
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 ) Eo = 0.80V
Cu 2 ( 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
52
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
53
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
H+
Calculate Eocell
ox red
Ag | AgCl (sat’d, Ksp = 1.82 x 10-10), NaCl (0.0200 M) || HBr (0.0200 M) | H2 (0.800 atm) | Pt
Given: Ag+ + 1e- Ag Eo = 0.799V
2H+ + 2e- H2 Eo = 0.000V
ox: 2(Ag Ag+ + 1e- ) Eo = -0.799V
2H+ + 2e- H2 Eo = 0.000V
red: ____________________________________
2Ag + 2H+ 2Ag+ + H2 Eo = -0.799V
?
Ksp =
= [AgCl]
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.
58
Stoichiometry of Electrolysis
59
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 ) 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)
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
61
Figure : A
hydrogen
electrode.
Slide 16