Electrochemistry
Galvanic cells
Electrochemical cells fall into
one of two basic types
Galvanic cells convert chemical
energy into electrical energy
(batteries)
Electrolytic cells convert
electrical energy into chemical
energy.
2
Here we put a
piece of zinc
metal into a Cu2+
ion solution. A
reaction occurs
where we get
Zn2+ ions and
solid copper
deposited on the
zinc surface.
3
Redox reaction
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)
Half-reactions
To clarify the redox process, we often break a redox
reaction down into two separate steps (half-reactions).
In one half-reaction, a chemical loses electrons (is
oxidized)
Half-reactions
The sum of these half-reactions
must give us the overall reaction
of interest.
Zn (s) Zn2+ (aq) + 2 eCu2+ (aq) + 2 e- Cu (s)
Zn (s) + Cu2+ (aq) + 2 e- Zn2+ (aq) + 2 e- + Cu (s)
Half-reactions
Why do we call them half-reactions?
Each half-reaction is written so we can see what is
happening to the electrons in the overall reaction.
In reality a half reaction CANNOT occur by itself to
any great extent.
The lost electrons in the oxidation half-reaction
MUST go somewhere.
The gained electrons in the reduction half-reaction
MUST come from somewhere.
Two half-reactions ALWAYS work together to give
an overall reaction that can occur to a great extent.
9
Half-reactions
M (s)
oxidation
reduction
M n (aq) ne -
10
12
The halfreactions
to take place in
separate
containers
(called half-cells).
Since a half-reaction cannot take place by itself we
need to connect the half-cells together. It turns out
that we must make a circuit (two connections!) for
the entire galvanic cell to work.
13
Oxidation occurs
at the copper
electrode, which
we give the
special name
ANODE
Since the anode collects the electrons that are
lost, it has a negative charge and positive copper
ions leave the anode!
Electrons move
from the
ANODE
to the silver
electrode through
the wire
Reduction occurs
at the silver
electrode, which
we give the special
name
CATHODE
Since the cathode collects the positive silver ions
so they can gain the electrons, the cathode has a
positive charge!
18
Overall, negative
charges (electrons and
negative ions) are
moving clockwise
Overall, positive
charges (positive ions
and electron holes)
are moving
counterclockwise
19
Note # of emust
balance!
24
Problem
Write the shorthand notation for a
galvanic cell that uses the reaction
Fe (s) + Sn2+ (aq) Fe2+ (aq) + Sn (s)
30
Problem
Write a balanced equation for the overall
cell reaction and give a brief description
of the galvanic cell represented by
Pb (s) | Pb2+ (aq) || Br2 (l) | Br- (aq) | Pt (s)
Potential
The difference in the free energy for the
electrons in the anode and the cathode is
somewhat like the slope from the top to
the bottom of the hill.
If the hill is steep, the ball experiences
more of the force of gravity than it does
on a gentle hill.
33
Potential
The equivalent of the force of gravity to
the difference in the free energy of
electrons in different atoms is called the
electromotive force (emf)
also known as the cell potential (E)
or the cell voltage (V).
Like a ball on a steep hill, electrons are
under a greater force to transfer from the
anode to the cathode when the cell
potential has a larger magnitude.
34
Potential
Because there is a free energy difference for
an electron in the anode as compared to the
same electron in the cathode, the electron
must lose free energy during the trip, just like
a ball loses potential energy (as motion!) as
it rolls down the hill.
The free energy change is negative and so
the movement of the electrons is a
spontaneous process!
35
Potential
The free energy change is negative
and so the movement of the electrons
is a spontaneous process!
Potential
We can get energy out of a ball
(with its certain mass) rolling down
a slope (the experienced gravity),
We can get energy out of an
electron (with electrical charge)
that rolls down the slope that is
the potential difference of electron
free energy between the two
electrodes.
37
Potential
In terms of units, we can define
one Joule as the energy
we get from a
charge of one Coulomb
multiplied by the
potential of one volt.
1 J = 1 CV (one Coulomb-volt)
38
Potential
A Coulomb is a very large unit of
charge!
The charge on one electron is
1.60 x 10-19 C, so
one Coulomb is the charge of
about
6 billion billion electrons!
39
Potential
It is generally easier to talk about the charge
of one mole of electrons, which we give
the special name of
Faraday Constant or faraday (F)
1 faraday = 6.022 x 1023 mol-1 e- x 1.60 x 10-19 C
40
Potential
We can measure the potential between two
electrodes with a voltmeter, which should
give a positive reading when the positive
terminal of the voltmeter is connected to
the positive electrode (the cathode),
and
the negative terminal is connected to the
negative electrode (the anode).
When the voltmeter gives a positive
potential, we have identified the direction
of spontaneous change!
41
42
45
E (red),cathode = - E (red),anode
48
E (red),cathode = E H /H = 0 V
+
51
H2 (g, 1 bar)
2 H+ (aq, 1 molL-1) + 2 eReversing a reaction
changes the sign of the
potential. For the S.H.E.
E (red),anode = - E (red),cathode
= - E H+/H = 0 V
2
52
53
56
Zn (s) Zn (aq) + 2 e
E (ox) = 0.763 V
2+
57
Zn (aq) + 2 e Zn (s)
E (red) = -0.763 V
2+
60
E cell = 1.563 V
62
Why?
63
Potential
Recall the potential is
like the slope
of a hill.
64
Problem
The standard cell potential for the following
galvanic cell is 0.78 V
Al (s) | Al3+ (aq) || Cr2+ (aq) | Cr (s)
The standard electrode potential for the Al
electrode is -1.676 V. Calculate the
standard electrode potential for the Cr
E
electrode. E E
cell
(red),cathode
(red),anode
Problem
Use the data from Table 20.1 to determine
the Ecell for the redox reaction in which
Fe2+ (aq) is oxidized to Fe3+ (aq) by MnO4(aq) in acidic solution. Also provide the
overall reaction.
Answer: Ecell = 0.74 V
5 Fe2+ (aq) + MnO4- (aq) + 8 H+ (aq)
5 Fe3+ (aq) + Mn2+ (aq) + 4 H2O (l)
66
G = H - TS
at standard conditions, or
G = H TS
at non-standard conditions.
67
G -Ecell
or
G = welec = -nFEcell
73
G = welec = -nFEcell
= -(mol)(Cmol-1)(V)
= CV = J
Yes! The units match
those for work.
74
Problem
Use the given electrode potential data to
determine G for the reaction
2 Al (s) + 3 Br2 (l)
2 Al3+ (aq, 1 M) + 6 Br- (aq, 1 M)
Al3+ (aq) + 3 e- Al (s)
EAl
3+/Al
= -1.676 V
75
Problem
The hydrogen-oxygen fuel cell is a galvanic cell
with a reaction
2 H2 (g) + O2 (g) 2 H2O (l)
Using the given data calculate Ecell for this
reaction:
Gf (H2O) = -237.1 kJmol-1
Gf (H2) = 0.00 kJmol-1
Gf (O2) = 0.00 kJmol-1
Answer: Since G is -474.2 kJ and the rxn
involves 4 mol of e-, then Ecell is 1.229 V .
76
G < 0
WHICH MEANS E cell > 0
MUST HAVE
Problem
When sodium metal is added to seawater,
which has [Mg2+] = 0.0512 M, no
magnesium metal is obtained. According
to the data below, should this reaction
occur? What reaction does occur?
Na+ (aq) + 1 e- Na (s)
ENa+/Na = -2.713 V
EMg2+/Mg = -2.356 V
78
Problem answer
For the reaction
2 Na (s) + Mg2+ (aq) 2 Na+ (aq) + Mg (s)
E cell = 0.357 V and the reaction should be
spontaneous. However, the reaction of sodium with
water is
2 Na (s) + 2 H2O (l) 2 Na+ (aq) + H2 (g) + 2 OH- (aq)
and has E cell = 1.885 V and this reaction should also
be spontaneous.
Since this reaction is more spontaneous (higher
E cell) sodium preferentially reacts with water and not
magnesium ions!
79
Problem
Without using the data for a detailed
calculation, explain why Sn2+ solutions
must be protected from oxygen. One way
to protect them is to add metallic (solid)
tin.
Sn4+ (aq) + 2 e- Sn2+ (aq)
ESn2+/ Sn = -0.137 V
EO2/H2O = 1.229 V
80
Problem answer
For both possible reactions the
reduction of oxygen is the cathode
half-cell reaction.
Since E cell = E (red),cathode - E (red),anode, then
the anode half-cell reaction that is
more negative will give the higher
(more spontaneous) E cell reaction that
will preferentially occur.
81
E (red),cathode = E H /H = 0 V
+
(0 V) - E (red),anode > 0
E (red),anode < 0
84
E (red),cathode = E NO3-/NO
= +0.956 V
87
G = -RT ln Keq
and
G = -nFE cell
90
BE CAREFUL!
This form ONLY applies
at 298.15 K!
93
Everything is connected!
Problem
Should the reaction of solid Al with Cu2+
ions go to completion at 25 C if Ecell for
the reaction is 2.016 V?
2 Al (s) + 3 Cu2+ (1 M) 3 Cu (s) + 2 Al3+ (1 M)
Problem
Should the reaction of solid Sn with Pb 2+
ions go to completion at 25 C?
Pb2+ (aq) + 2 e- Pb (s)
EPb
2+/Pb
= -0.125 V
ESn
2+/Sn
= -0.137 V
G = G + RT ln Qeq
and
G = -nFEcell
99
or
Ecell = E cell - (RT/nF) ln Qeq
100
104
Ecell = E cell
(0.0592 V/n) log Qeq
It makes the most sense to
memorize the Nernst
Equation and substitute
rather than remembering this
form for one temperature!
106
Problem
Calculate Ecell for the for the following
galvanic cells at 298.15 K. Will the
reactions be spontaneous?
Al (s) | Al3+ (0.36 M)
|| Sn4+ (0.086 M), Sn2+ (0.54 M) | Pt(s)
Pt(s) | Cl2 (1 atm) | Cl- (1.0 M)
|| Pb2+ (0.050 M), H+ (0.10 M) | PbO2(s)
107
Problem data
Sn4+ (aq) + 2 e- Sn2+ (aq)
E Sn4+/Sn2+ = 0.154 V
Al3+ (aq) + 3 e- Al (s)
E Al3+/Al = -1.676 V
PbO2 (s) + 4 H+ (aq) + 2 e- Pb2+ (aq) + 2 H2O (l)
E PbO2/Pb2+ = 1.455 V
Cl2 (g) + 2 e- 2 Cl- (aq)
E Cl2/Cl- = 1.358 V
108
Problem answer
3 Sn4+ (0.086 M) + 2 Al (s)
3 Sn2+ (0.54 M) + 2 Al3+ (0.36 M)
E cell = 1.830 V and Ecell = 1.815 V
PbO2 (s) + 4 H+ (0.10 M) + Cl2 (1 atm)
Pb2+ (0.050 M) + 2 H2O (l) + 2 Cl- (1.0 M)
E cell = 0.097 V and Ecell = 0.017 V
Since both Ecell values are positive, both reactions
will be spontaneous at the given conditions.
109
Problem
For what ratio of [Sn2+] / [Pb2+] will
the given cell reaction NOT be
spontaneous in either direction?
Sn (s) | Sn2+ (aq) || Pb2+ (aq) | Pb (s)
Pb2+ (aq) + 2 e- Pb (s)
EPb
2+/Pb
= -0.125 V
ESn
2+/Sn
= -0.137 V
110
Problem answer
The reaction is NOT spontaneous in
either direction ONLY at equilibrium,
where Ecell = 0.
Since for this cell Ecell = 0.012 V the
equilibrium occurs when
Qeq = [Sn2+] / [Pb2+] = Keq = 2.5
(see slide 96)
111
Concentration cells
We know if we mix two solutions of the
same chemical but with different
concentrations, then the final solution
will have a single uniform
concentration.
The mixing is a
spontaneous process!
112
Concentration cells
We can set up the mixing process
as an electrochemical cell!
The different concentrations in the
two half-cells
will lead to a
non-zero Ecell
113
Concentration cells
We can set up the mixing process
as an electrochemical cell!
The different concentrations in the
two half-cells
will lead to a
Ecell
different from
E cell
114
Net reaction: 2 H+ (1 M) 2 H+ (x M)
E cell
will ALWAYS
be zero for a
concentration
cell
115
E cell
will ALWAYS
be zero for a
concentration
cell
118
Since
Q = [Ag+] / [Ag+]
and
Ecell = E cell
(0.0592 V/n) log Qeq
and n = 1
119
120
came from a
saturated AgI solution, then
[Ag+] = [I-] = 9.04 x 10-9 M
and Ksp = [Ag+] [I-]
-9
-9
Ksp = (9.04 x 10 ) (9.04 x 10 )
Ksp = 8.3 x 10
-17
121
Problem
If Ksp = 1.8 x 10-10 for silver chloride then
what would be Ecell for
Ag (s) | Ag+ (satd AgCl) || Ag+ (0.100 M) | Ag (s)
122
Problem
Calculate the Ksp for lead iodide with the
given concentration cell information
Pb (s) | Pb2+ (satd PbI2) || Pb2+ (0.100 M) | Pb (s)
Ecell = 0.0567 V
Answer: Ksp = 7.1 x 10-9
123
Cathode is ve!
Reduction!
Anode is +ve!
Oxidation!
127
Overpotentials
The electrolytic cell has electron transfers
occurring at the surface of the electrodes. If
solutions are involved then there is generally a
good contact to the electrode.
However, if gases are contacting the electrode
the contact is problematic.
As the contact to the electrode gets worse we
often need to apply an overpotential (extra
Eoverpotential) to make up for this problem.
131
Overpotentials
Competing reactions
If we set up an electrolytic cell expecting
Competing reactions
Competing reactions
Often, but not always, when we do
electrolysis in aqueous solutions we
get the competing reactions
2 H2O (l) + 2e- H2 (g) + 2 OH- (aq)
at the cathode and
2 H2O (l) O2 (g) + 4 H+ (aq) + 4 eat the anode.
135
Competing reactions
When we do electrolysis in aqueous solution
we must identify which of the two possible
reduction reactions is more spontaneous
when forced and
we must identify which of the two possible
oxidation reactions is more spontaneous
when forced.
See pages 850-851 and Example Problem 2011 in the text for more info on this
very important topic
136
Non-standard conditions
Industrially we try to maximize product
with minimum energy and money input.
This often means that we do electrolysis
on cells at non-standard conditions,
which means
Ecell E cell
137
Electrodes
Platinum is an inert electrode that only
provides a surface for the true reactants to
transfer electrons.
An active electrode is an actual reactant
in the half-cell reaction.
Using a different electrode on one side
of the electrolytic cell might change the
half-cell reaction on that side!
138
139
Problem
How many kilograms of aluminum can be
produced in 8.00 h by passing a constant
current of 1.00 x 105 A for an electrolytic cell
with the following half reaction at the
cathode?
Al3+ + 3 e- Al
Molar mass of Al is 26.9815 gmol-1
Answer: 268 kg
144
Problem
A layer of silver is electroplated (an
electrolytic process) on a coffee server
using a constant current of 0.100 A. How
much time is required to deposit 3.00 g of
silver?
Molar mass of silver is 107.868 gmol-1
145