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Slide 50

The End of Chem1051 Classes!


Now, Review Classes
Practice lots of examples, a few each day, do not
try and study all of 1051 in a couple of days, it will
not work!
Read the questions! And recognise what the asker
wants!
Get help if you need it; Resource Room,
Tutors/TAs, Tutorial, Me (e-mail: fkerton@mun.ca)
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arrange an appointment or just try and find me.
Slide 49
2 more examples.
Gold can be plated out of a solution containing
Au
3+
. What mass of gold (in grams) will be plated
by the flow of 5.5 A of current for 25 minutes?
Silver can be plated out of a solution containing
Ag
+
. How much time (in minutes) would it take to
plate 12 g of silver using a current of 3.0 A?
Slide 48
Problem Calculating quantities in electrolysis
PROBLEM: A technician is plating a faucet (tap) with 0.86 g of Cr from an
electrolytic bath containing aqueous Cr
2
(SO
4
)
3
. If 12.5 min is
allowed for the plating, what current is needed?
PLAN:
SOLUTION:
mol of e
-
transferred
divide by M
9.65x10
4
C/mol e
-
3mol e
-
/mol Cr
divide by time
mass of Cr needed
mol of Cr needed
charge (C)
current (A)
Cr
3+
(aq) + 3e
-
Cr(s)
0.86g (mol Cr) (3 mol e
-
)
(52.00 gCr) (mol Cr)
= 0.050 mol e
-
0.050 mol e
-
(9.65x10
4
C/mol e
-
) = 4.8x10
3
C
4.8x10
3
C
12.5 min
(min)
(60s)
= 6.4C/s = 6.4 A
Slide 47
Quantitative Aspects of Electrolysis
1 mol e
-
= 96485 C Charge (C) = current (C/s) x time (s)
Mass of product?
C/sC mol e- mol product g product
MASS (g)
of substance
oxidized or
reduced
MASS (g)
of substance
oxidized or
reduced
AMOUNT (MOL)
of electrons
transferred
AMOUNT (MOL)
of electrons
transferred
AMOUNT (MOL)
of substance
oxidized or
reduced
AMOUNT (MOL)
of substance
oxidized or
reduced
CHARGE (C)
CHARGE (C)
CURRENT (A)
CURRENT (A)
balanced
half-reaction
Faraday
constant
(C/mol e
-
)
M(g/mol)
time(s)
Slide 46
Problem Making qualitative predictions
Predict the half-reaction occurring at the anode and
the cathode for electrolysis of each of the following:
A mixture of molten AlBr
3
and MgBr
2
An aqueous solution of LiI
Slide 45
continued
E
0
= -0.42V 2H
2
O(l) + 2e
-
H
2
(g) + 2OH
-
(aq)
E
0
= -0.80V (b) Ag
+
(aq) + e
-
Ag(s)
Ag
+
is the cation of an inactive metal and therefore will be reduced to Ag
at the cathode.
Ag
+
(aq) + e
-
Ag(s)
The N in NO
3
-
is already in its most oxidized form so water will have to be
oxidized to produce O
2
at the anode.
2H
2
O(l) O
2
(g) + 4H
+
(aq) + 4e
-
Mg is an active metal and its cation cannot be reduced in the presence of
water. So as in (a) water is reduced and H
2
(g) is produced at the cathode.
The S in SO
4
2-
is in its highest oxidation state; therefore water must be
oxidized and O
2
(g) will be produced at the anode.
E
0
= -2.37V (c) Mg
2+
(aq) + 2e
-
Mg(s)
Slide 44
Problem Predicting half- and overall reactions in
electrolysis
PROBLEM: What products form during electrolysis of aqueous solution of the
following salts: (a) KBr; (b) AgNO
3
; (c) MgSO
4
?
SOLUTION:
PLAN: Compare the potentials of the reacting ions with those of water,
remembering to consider the 0.4 to 0.6V overvoltage.
The reduction half-reaction with the less negative potential, and the oxidation half-
reaction with the less positive potential will occur at their respective electrodes.
E
0
= -2.93V (a) K
+
(aq) + e
-
K(s)
E
0
= -0.42V 2H
2
O(l) + 2e
-
H
2
(g) + 2OH
-
(aq)
The overvoltage would make the water reduction -0.82 to -1.02 but the
reduction of K
+
is still a higher potential so H
2
(g) is produced at the cathode.
The overvoltage would give the water half-cell more potential than
the Br
-
, so the Br
-
will be oxidized. Br
2
(g) forms at the anode.
E
0
= 1.07V 2Br
-
(aq) Br
2
(g) + 2e
-
2H
2
O(l) O
2
(g) + 4H
+
(aq) + 4e
-
E
0
= 0.82V
Slide 43
Complications in Electrolytic Cells
Overpotential.(1)
Competing reactions.(2)
Non-standard states.(3)
Nature of electrodes.(4)
Slide 42
Comparison of Voltaic and Electrolytic Cells
Cell Type G E
cell
Electrode
Name Process Sign
Voltaic
Voltaic
Electrolytic
Electrolytic
< 0
< 0
> 0
> 0
> 0
> 0
< 0
< 0
Anode
Anode
Cathode
Cathode
Oxidation
Oxidation
Reduction
Reduction
-
-
+
+
Slide 41
The tin-copper reaction as the basis of a voltaic (galvanic) and an
electrolytic cell.
Oxidation half-reaction
Sn(s) Sn
2+
(aq) + 2e
-
Reduction half-reaction
Cu
2+
(aq) + 2e
-
Cu(s)
Oxidation half-reaction
Cu(s) Cu
2+
(aq) + 2e
-
Reduction half-reaction
Sn
2+
(aq) + 2e
-
Sn(s)
Overall (cell) reaction
Sn(s) + Cu
2+
(aq) Sn
2+
(aq) + Cu(s)
Overall (cell) reaction
Sn(s) + Cu
2+
(aq) Sn
2+
(aq) + Cu(s)
voltaic cell electrolytic cell
Slide 40
20-7 Electrolysis: Causing
Non-spontaneous Reactions to Occur
Galvanic Cell: also known as voltaic
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) E
o
cell
= 1.103 V
Electrolytic Cell:
Zn
2+
(aq) + Cu(s) Zn(s) + Cu
2+
(aq) E
o
cell
= -1.103 V
Batteries and Corrosion (Sections 20-5 and 20-6) omitted
Slide 39
Example 20-10
E
cell
= E
cell
- log
n
0.0592 V
[Ag
+
]
0.10 M soln
[Ag
+
]
satd AgI
E
cell
= E
cell
- log
n
0.0592 V
0.100
x
0.417 =0 - (log x log 0.100)
1
0.0592 V
0.417
log 0.100-
0.0592
log x = = -1 7.04 = -8.04
x = 10
-8.04
= 9.1 x 10
-9
K
sp
= x
2
= 8.3 x 10
-17
Slide 38
Example 20-10
Using a Voltaic Cell to Determine K
sp
of a Slightly
Soluble Solute.
With the data given for the reaction on the previous slide,
calculate K
sp
for AgI.
AgI(s) Ag
+
(aq) + I
-
(aq)
Let [Ag+] in a saturated Ag
+
solution be x:
Ag
+
(0.100 M) Ag
+
(satd M)
E
cell
= E
cell
- log Q =
n
0.0592 V
E
cell
- log
n
0.0592 V
[Ag
+
]
0.10 M soln
[Ag
+
]
satd AgI
Slide 37
Measurement of K
sp
Ag
+
(0.100 M) Ag
+
(satd M)
Ag|Ag
+
(satd AgI)||Ag
+
(0.10 M)|Ag(s)
Ag
+
(0.100 M) + e
-
Ag(s)
Ag(s) Ag+(satd) + e
-
Slide 36
PROBLEM: A concentration cell consists of two Ag/Ag
+
half-cells. In
half-cell A, electrode A dips into 0.0100M AgNO
3
; in half-cell
B, electrode B dips into 4.0x10
-4
M AgNO
3
. What is the cell
potential at 298 K? Which electrode has a positive charge?
PLAN: E
0
cell
will be zero since the half-cell potentials are equal. E
cell
is calculated from the Nernst equation with half-cell A (higher
[Ag
+
]) having Ag
+
being reduced and plating out, and in half-
cell B Ag(s) will be oxidized to Ag
+
.
SOLUTION: Ag
+
(aq, 0.010M) half-cell A Ag
+
(aq, 4.0x10
-4
M) half-cell B
E
cell
= E
0
cell
-
0.0592V
1
log
[Ag
+
]
dilute
[Ag
+
]
concentrated
E
cell
= 0 V - 0.0592 log 4.0x10
-2
= 0.0828V
Half-cell A is the cathode and has the positive electrode.
Slide 35
Concentration Cells
E
cell
= E
cell
- log
n
0.0592 V x
2
1
2
E
cell
= 0 - log
2
0.0592 V x
2
1
E
cell
= - 0.0592 V log x
E
cell
= (0.0592 V) pH
2 H
+
(1 M) 2 H
+
(x M) E
cell
= E
cell
- log Q
n
0.0592 V
Slide 34
Concentration Cells
Two half cells with identical electrodes
but different ion concentrations.
2 H
+
(1 M) 2 H
+
(x M)
Pt|H
2
(1 atm)|H
+
(x M)||H
+
(1.0 M)|H
2
(1 atm)|Pt(s)
2 H
+
(1 M) + 2 e
-
H
2
(g, 1 atm)
H
2
(g, 1 atm) 2 H
+
(x M) + 2 e
-
Slide 33
Problem Predicting spontaneous reactions for
non-standard conditions
Will the cell reaction proceed spontaneously as
written for the following cell?
Sn(s)|Sn
2+
(0.50 M)||Pb
2+
(0.0010 M)|Pb(s)
Slide 32
PROBLEM: In a test of a new reference electrode, a chemist constructs a
voltaic cell consisting of a Zn/Zn
2+
half-cell and an H
2
/H
+
half-cell under the
following conditions:
PLAN:
SOLUTION:
[Zn
2+
] = 0.010M [H
+
] = 2.5M P = 0.30atm
H
2
Calculate E
cell
at 298 K.
Find E
0
cell
and Q in order to use the Nernst equation.
Determining E
0
cell
:
E
0
= 0.00V 2H
+
(aq) + 2e
-
H
2
(g)
E
0
= -0.76V Zn
2+
(aq) + 2e
-
Zn(s)
Zn(s) Zn
2+
(aq) + 2e
-
E
0
= +0.76V
Q =
P x [Zn
2+
]
H
2
[H
+
]
2
Q = 4.8x10
-4
Q =
(0.30)(0.010)
(2.5)
2
E
cell
= E
0
cell
-
0.0592V
n
log Q
E
cell
= 0.76 - (0.0592/2)log(4.8x10
-4
) = 0.86V
Slide 31
Example 20-8
E
cell
= E
cell
- log Q
n
0.0592 V
Pt|Fe
2+
(0.10 M),Fe
3+
(0.20 M)||Ag
+
(1.0 M)|Ag(s)
E
cell
= E
cell
- log
n
0.0592 V [Fe
3+
]
[Fe
2+
] [Ag
+
]
Fe
2+
(aq) + Ag
+
(aq) Fe
3+
(aq) + Ag (s)
E
cell
= 0.029 V 0.018 V = 0.011 V
Slide 30
Example 20-8
Pt|Fe
2+
(0.10 M),Fe
3+
(0.20 M)||Ag
+
(1.0 M)|Ag(s)
Applying the Nernst Equation for Determining E
cell
.
What is the value of E
cell
for the voltaic cell pictured
below and diagrammed as follows?
Slide 29
20-4 E
cell
as a Function of Concentration
G = G + RT ln Q
-nFE
cell
= -nFE
cell
+ RT ln Q
E
cell
= E
cell
- ln Q
nF
RT
Convert to log
10
and calculate constants
E
cell
= E
cell
- log Q
n
0.0592 V
The Nernst Equation:
Slide 28
Summary of Important Thermodynamic, Equilibrium
and Electrochemistry Relationships
Slide 27
Problem Relating K
eq
to E
o
cell
for a redox reaction
PLAN:
SOLUTION:
PROBLEM: Lead can displace silver from solution:
As a consequence, silver is a valuable by-product in the industrial extraction
of lead from its ore. Calculate K and G
0
at 298 K for this reaction.
Pb(s) + 2Ag
+
(aq) Pb
2+
(aq) + 2Ag(s)
Break the reaction into half-reactions, find the E
0
for each half-reaction
and then the E
0
cell
.
E
0
= -0.13V
E
0
= 0.80V
2X
E
0
= 0.13V
E
0
= 0.80V
E
0
cell
= 0.93V
Ag
+
(aq) + e
-
Ag(s)
Pb
2+
(aq) + 2e
-
Pb(s)
Ag
+
(aq) + e
-
Ag(s)
Pb(s) Pb
2+
(aq) + 2e
-
E
0
cell
= ln K
eq
0.025693V
n
lnK = K = 2.75x10
31
n x E
0
cell
0.025693V
(2)(0.93V)
0.025693V
=
G
0
= -nFE
0
cell
= -(2)(96.5kJ/mol*V)(0.93V)
G
0
= -1.8x10
2
kJ
Slide 26
Relationship Between E
cell
and K
eq
G = -RT ln K
eq
= -nFE
cell
E
cell
=
nF
RT
ln K
eq
Slide 25
Relative Reactivities (Activities) of Metals
1. Metals that can displace H from acid
2. Metals that cannot displace H from acid
3. Metals that can displace H from water
4. Metals that can displace other metals from
solution
Slide 24
The Behavior of Metals Toward Acids
M(s) M
2+
(aq) + 2 e
-
E = -E
M
2+
/M
2 H
+
(aq) + 2 e
-
H
2
(g) E
H
+
/H2
= 0 V
2 H
+
(aq) + M(s) H
2
(g) + M
2+
(aq)
E
cell
= E
H
+
/H2
- E
M
2+
/M
= 0 -E
M
2+
/M
= -E
M
2+
/M
When E
M
2+
/M
< 0, E
cell
> 0. Therefore G < 0.
Metals with negative reduction potentials react with acids
All metals below hydrogen in table of E
o
should displace H
2
(g)
from acidic solutions (Pb through Li)
Slide 23
Problem Making qualitative predictions
Peroxodisulfate salts such as Na
2
S
2
O
8
are good
oxidizing agents used in bleaching. Dichromates
such as K
2
Cr
2
O
7
have been used as laboratory
oxidizing agents. Which is the better oxidizing
agent in acidic solution under standard conditions,
Cr
2
O
7
2-
or S
2
O
8
2-
?
Slide 22
Problem Applying the criterion for spontaneous
change in a redox reaction
PROBLEM: (a) Combine the following three half-reactions into three balanced
equations (A, B, and C) for spontaneous reactions, and
calculate E
0
cell
for each.
PLAN:
(b) Rank the relative strengths of the oxidizing and reducing agents:
E
0
= 0.96V (1) NO
3
-
(aq) + 4H
+
(aq) + 3e
-
NO(g) + 2H
2
O(l)
E
0
= -0.23V (2) N
2
(g) + 5H
+
(aq) + 4e
-
N
2
H
5
+
(aq)
E
0
= 1.23V (3) MnO
2
(s) +4H
+
(aq) + 2e
-
Mn
2+
(aq) + 2H
2
O(l)
Put the equations together in varying combinations so as to produce
(+) E
0
cell
for the combination. Since the reactions are written as
reductions, remember that as you reverse one reaction for an
oxidation, reverse the sign of E
0
. Balance the number of electrons
gained and lost without changing the E
0
.
In ranking the strengths, compare the combinations in terms of E
0
cell
.
Slide 21
Spontaneous Change
G < 0 for spontaneous change.
Therefore:
E
cell
> 0, (E
cell
+ve)
Reaction proceeds spontaneously as written.
E
cell
= 0
Reaction is at equilibrium.
E
cell
< 0, (E
cell
-ve)
Reaction proceeds in the reverse direction spontaneously.
Slide 20
Combining Half Reactions
Fe
3+
(aq) + 3e
-
Fe(s) E
Fe
3+
/Fe
= ?
Fe
2+
(aq) + 2e
-
Fe(s) E
Fe
2+
/Fe
= -0.440 V
Fe
3+
(aq) + 3e
-
Fe
2+
(aq) E
Fe
3+
/Fe
2+ = 0.771 V
Fe
3+
(aq) + 3e
-
Fe(s)
G = +0.880 J
G = -0.771 J
G = +0.109 V E
Fe
3+
/Fe
= +0.331 V
G = +0.109 V = -nFE
E
Fe
3+
/Fe
= +0.109 V /(-3F) = -0.0363 V
Slide 19
20-3 E
cell
, G, and K
eq
Cells do electrical work.
Moving electric charge.
Faraday constant, F = 96,485 C mol
-1

elec
= nFE
G = -nFE
G = -nFE
Slide 18
Problem Determining E
o
from an E
o
cell
measurement
PROBLEM: A voltaic cell houses the reaction between aqueous bromine
and zinc metal:
PLAN:
SOLUTION:
Br
2
(aq) + Zn(s) Zn
2+
(aq) + 2Br
-
(aq) E
0
cell
= 1.83V
Calculate E
0
bromine
given E
0
zinc
= -0.76V
The reaction is spontaneous as written since the E
0
cell
is (+).
Zinc is being oxidized and is the anode. Therefore the
E
0
bromine
can be found using E
0
cell
= E
0
cathode
- E
0
anode
.
anode: Zn(s) Zn
2+
(aq) + 2e
-
E = +0.76
E
0
Zn
as Zn
2+
(aq) + 2e
-
Zn(s) is -0.76V
E
0
cell
= E
0
cathode
- E
0
anode
= 1.83 = E
0
bromine
- (-0.76)
E
0
bromine
= 1.83 - 0.76 = +1.07 V
Slide 17
Problem Calculating E
o
cell
for a reaction
A new battery system currently under study for possible use in
electric vehicles is the zinc-chlorine battery. The overall reaction
producing electricity in this cell is Zn(s) + Cl
2
(g) ZnCl
2
(aq).
What is E
o
cell
of this voltaic cell?
Slide 16
Standard Reduction Potentials
Slide 15
Measuring Standard Reduction Potential
cathode cathode anode anode
Slide 14
Standard Cell Potential
Pt|H
2
(g, 1 bar)|H
+
(a = 1) || Cu
2+
(1 M)|Cu(s) E
cell
= 0.340 V
E
cell
= E
right
- E
left
E
cell
= E
Cu
2+
/Cu
- E
H
+
/H2
0.340 V = E
Cu
2+
/Cu
- 0 V
E
Cu
2+
/Cu
= +0.340 V
H
2
(g, 1 atm) + Cu
2+
(1 M) H
+
(1 M) + Cu(s) E
cell
= 0.340 V
Slide 13
Reduction Couples
Cu
2+
(1M) + 2 e
-
Cu(s) E
Cu
2+
/Cu
= ?
Pt|H
2
(g, 1 bar)|H
+
(a = 1) || Cu
2+
(1 M)|Cu(s) E
cell
= 0.340 V
Standard cell potential: the potential difference of a
cell formed from two standard electrodes.
E
cell
= E(right)
cathode
- E(left)
anode
cathode anode
Slide 12
Standard Electrode Potential, E
E defined by international agreement.
The tendency for a reduction process to occur at
an electrode.
All ionic species present at a=1 (approximately 1 M).
All gases are at 1 bar (approximately 1 atm).
Where no metallic substance is indicated, the potential is
established on an inert metallic electrode (ex. Pt).
Slide 11
Standard Hydrogen Electrode
2 H
+
(a = 1) + 2 e
-
H
2
(g, 1 bar) E = 0 V
Pt|H
2
(g, 1 bar)|H
+
(a = 1)
Slide 10
20-2 Standard Electrode Potentials
Cell voltages, the potential differences between
electrodes, are among the most precise scientific
measurements.
The potential of an individual electrode is difficult to
establish.
Arbitrary zero is chosen.
The Standard Hydrogen Electrode (SHE)
Slide 9
Problem - Representing a Redox Reaction by
Means of a Cell Diagram
PROBLEM: Diagram, show balanced equations, and write the notation for a
voltaic cell that consists of one half-cell with a Cr bar in a Cr(NO
3
)
3
solution, another half-cell with an Ag bar in an AgNO
3
solution, and
a KNO
3
salt bridge. Measurement indicates that the Cr electrode is
negative relative to the Ag electrode.
PLAN:
SOLUTION:
Identify the oxidation and reduction reactions and write each half-
reaction. Associate the (-)(Cr) pole with the anode (oxidation) and
the (+) pole with the cathode (reduction).
Voltmeter
Oxidation half-reaction
Cr(s) Cr
3+
(aq) + 3e
-
Reduction half-reaction
Ag
+
(aq) + e
-
Ag(s)
Overall (cell) reaction
Cr(s) + 3Ag
+
(aq) Cr
3+
(aq) + 3Ag(s)
Cr
Cr
3+
Ag
Ag
+
K
+
NO
3
-
salt bridge
e
-
Cr(s) | Cr
3+
(aq) || Ag
+
(aq) | Ag(s)
Slide 8
A voltaic (galvanic) cell based on the zinc-copper reaction.
Oxidation half-reaction
Zn(s) Zn
2+
(aq) + 2e
-
Reduction half-reaction
Cu
2+
(aq) + 2e
-
Cu(s)
Overall (cell) reaction
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
Slide 7
Terminology
Galvanic cells.
Produce electricity as a result of spontaneous
reactions, e.g. Cells on slides 4 & 6
Electrolytic cells.
Non-spontaneous chemical change driven by
electricity.
Couple, M|M
n+
A pair of species related by a change in number of e
-
.
Slide 6
Terminology
E
cell
= 1.103 V
Slide 5
Terminology
Electromotive force, E
cell
.
The cell voltage or cell potential.
Cell diagram.
Shows the components of the cell in a symbolic way.
Anode (where oxidation occurs) on the left.
Cathode (where reduction occurs) on the right.
Boundary between phases shown by |.
Boundary between half cells
(usually a salt bridge) shown by ||.
Slide 4
An Electrochemical Cell
Slide 3
An Electrochemical Half-Cell
Anode
Cathode
Slide 2
Electrode Potentials and Their Measurement
Cu(s) + 2Ag
+
(aq)
Cu
2+
(aq) + 2 Ag(s)
Cu(s) + Zn
2+
(aq)
No reaction
General Chemistry
Principles and Modern Applications
Petrucci Harwood Herring Madura
9
th
Edition
Chapter 20: Electrochemistry
Fran Kerton
Memorial University of Newfoundland,
St. Johns, Canada
A1B 3X7