Electrochemistry 110811014016 Phpapp01

Electrochemistry
Chapter 19
Electron Transfer Reactions

Electron transfer reactions are oxidation-reduction or
redox reactions.
Results in the generation of an electric current (electricity)
or be caused by imposing an electric current.
Therefore, this field of chemistry is often called
ELECTROCHEMISTRY.
Electrochemical processes are oxidation-reduction

reactions in which:
the energy released by a spontaneous reaction is

converted to electricity or
electrical energy is used to cause a nonspontaneous

reaction to occur
0
2+ 2-
2Mg (s) + O2 (g)

2Mg
O2 + 4e-
2MgO (s)
2Mg2+ + 4e-
Oxidation half-reaction (lose e-)
2O2-
Reduction half-reaction (gain e-)

19.1
Terminology for Redox Reactions

OXIDATION
OXIDATIONloss
loss of
of electron(s)
electron(s) by
by aa species;
species;
increase
increase in
in oxidation
oxidation number;
number; increase
increase in
in oxygen.
oxygen.
REDUCTION
REDUCTIONgain
gain of
of electron(s);
electron(s); decrease
decrease in
in
oxidation
oxidation number;
number; decrease
decrease in
in oxygen;
oxygen; increase
increase
in
in hydrogen.
hydrogen.
OXIDIZING
OXIDIZING AGENT
AGENTelectron
electron acceptor;
acceptor; species
species is
is
reduced.
reduced. (an
(an agent
agent facilitates
facilitates something;
something; ex.
ex.
Travel
Travel agents
agents dont
dont travel,
travel, they
they facilitate
facilitate travel)
travel)
REDUCING
REDUCING AGENT
AGENTelectron
electron donor;
donor; species
species is
is
oxidized.
oxidized.
You cant have one without the other!

Reduction (gaining electrons) cant happen without an
oxidation to provide the electrons.
You cant have 2 oxidations or 2 reductions in the same
equation. Reduction has to occur at the cost of oxidation
LEO the lion says GER!

o
s
e
GER!
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Another way to remember
OIL RIG
x s o
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s
d
e
a
t
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e s a
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Review of Oxidation numbers

The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.
1. Free elements (uncombined state) have an oxidation
number of zero.
Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.
Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually 2. In H2O2
and O22- it is 1.
4.4
4. The oxidation number of hydrogen is +1 except when

it is bonded to metals in binary compounds. In these
cases, its oxidation number is 1.
5. Group IA metals are +1, IIA metals are +2 and fluorine is
always 1.
6. The sum of the oxidation numbers of all the atoms in
a molecule or ion is equal to the charge on the
molecule or ion.
HCO3Oxidation numbers of all

the atoms in HCO3- ?
O = -2
H = +1
3x(-2) + 1 + ? = -1
C = +4
4.4
Balancing Redox Equations

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?
1. Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72-
Fe3+ + Cr3+
2. Separate the equation into two half-reactions.

+2
Oxidation:
Reduction:
Fe2+
+6
Cr2O72-
+3
Fe3+
+3
Cr3+
3. Balance the atoms other than O and H in each half-reaction.

Cr2O72-
2Cr3+
19.1

4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O722Cr3+ + 7H2O
14H+ + Cr2O722Cr3+ + 7H2O
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+
6e- + 14H+ + Cr2O72-
Fe3+ + 1e2Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two halfreactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+
6Fe3+ + 6e6e- + 14H+ + Cr2O72-
2Cr3+ + 7H2O
19.1

7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel. You should also cancel like species.
Oxidation:
6Fe2+
Reduction: 6e- + 14H+ + Cr2O7214H+ + Cr2O72- + 6Fe2+
6Fe3+ + 6e2Cr3+ + 7H2O
6Fe3+ + 2Cr3+ + 7H2O
8. Verify that the number of atoms and the charges are balanced.
14x1 2 + 6x2 = 24 = 6x3 + 2x3
9. For reactions in basic solutions, add OH- to both sides of the
equation for every H+ that appears in the final equation. You
should combine H+ and OH- to make H2O.
19.1
CHEMICAL CHANGE --->

ELECTRIC CURRENT
To obtain a useful current,
we separate the oxidizing
and reducing agents so that
electron transfer occurs thru
an external wire.
wire
wire
Zn
Zn
electrons
electrons
2+
Zn
Zn2+ions
ions
Cu
Cu
salt
salt
bridge
bridge
2+
Cu
Cu2+ions
ions
This is accomplished in a GALVANIC or

VOLTAIC cell. http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/galvan5.swf
A group of such cells is called a battery.
Galvanic Cells
anode
oxidation
cathode
reduction
spontaneous
redox reaction
19.2
Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
cell voltage
electromotive force (emf)
cell potential
Cell Diagram
Zn (s) + Cu2+ (aq)
Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode
cathode
19.2
Standard Electrode Potentials
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation):
Zn (s)
Cathode (reduction): 2e- + 2H+ (1 M)

Zn (s) + 2H+ (1 M)
Zn2+ (1 M) + 2eH2 (1 atm)

Zn2+ + H2 (1 atm)
19.3

Standard reduction potential (E0) is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.
Reduction Reaction
2e- + 2H+ (1 M)
H2 (1 atm)
E0 = 0 V
Standard hydrogen electrode (SHE)
19.3
E0 is for the reaction as

written
The more positive E0 the

greater the tendency for the
substance to be reduced
The half-cell reactions are

reversible
The sign of E0 changes

when the reaction is
reversed
Changing the stoichiometric

coefficients of a half-cell
reaction does not change
the value of E0
19.3

0
Standard emf (Ecell
)
0
0
0
Ecell
= Ecathode
+ Eanode
If the reaction is
backwards, be sure to
flip the sign!
Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)
0
0
+2
Ecell
= EH0+/H 2+ EZn
/Zn
Zn2+ (1 M) + 2e-
Zn E0 = -0.76 V
So Eo Zn/Zn +2= + 0.76 V
0
Ecell
= 0 + 0.76 V = 0.76 V
19.3

0
Ecell
= 0.34 V
0
0
0
Ecell
= Ecathode
+ Eanode
0 = E0
Ecell
Cu
2+
/Cu
+EH
/H+
2
0 2+
0.34 = ECu
/Cu + - 0
0 2+
ECu
/Cu = 0.34 V
Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation):
H2 (1 atm)
Cathode (reduction): 2e- + Cu2+ (1 M)

H2 (1 atm) + Cu2+ (1 M)
2H+ (1 M) + 2eCu (s)
Cu (s) + 2H+ (1 M)
19.3
What is the standard emf of an electrochemical cell made

of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?
Cd2+ (aq) + 2e-
Cd (s) E0 = -0.40 V
Cr3+ (aq) + 3e-
Cr (s)
Anode (oxidation):
Cd is the stronger oxidizer
E0 = -0.74 V
Cr3+ (1 M) + 3e- x 2
Cr (s)
Cathode (reduction): 2e- + Cd2+ (1 M)

2Cr (s) + 3Cd2+ (1 M)
Cd will oxidize Cr
Cd (s)
x3
3Cd (s) + 2Cr3+ (1 M)
0
0
0
Ecell
= Ecathode
+ Eanode
0
Ecell
= -0.40 + (+0.74)
0
Ecell
= 0.34 V
19.3
Spontaneity of Redox Reactions

G = -nFEcell
G =
0
-nFE 0
cell
n = number of moles of electrons in reaction

J
F = 96,500
= 96,500 C/mol
V mol
0
G0 = -RT ln K = -nFEcell
(8.314 J/Kmol)(298 K)
RT
0 =
ln K =
ln K
Ecell
nF
n (96,500 J/Vmol)
0
Ecell
=
0
Ecell
0.0257 V
ln K
n
0.0592 V
log K
=
n
19.4
Spontaneity of Redox Reactions
19.4
What is the equilibrium constant for the following reaction

at 250C? Fe2+ (aq) + 2Ag (s)
Fe (s) + 2Ag+ (aq)
0.0257 V
ln K
Ecell =
n
0
Oxidation:
2Ag
Reduction: 2e- + Fe2+

E0 = EFe0 2+/Fe + EAg0 /Ag
2Ag+ + 2eFe
n=2
E0 = -0.44 + -0.80
E0 = -1.24 V
0
Ecell
xn
-1.24 V x 2
= exp
K = exp
0.0257 V
0.0257 V
K = 1.23 x 10-42
19.4
The Effect of Concentration on Cell Emf

G = G0 + RT ln Q
G = -nFE
G0 = -nFE 0
-nFE = -nFE0 + RT ln Q
Nernst equation
E = E0 -
RT
ln Q
nF
At 298
E = E0 -
0.0257 V
ln Q
n
E = E0 -
0.0592 V
log Q
n
19.5
Will the following reaction occur spontaneously at 250C if

[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s)
Fe (s) + Cd2+ (aq)
Oxidation:
Cd
Cd2+ + 2e-
Reduction: 2e- + Fe2+

E0 = EFe0 2+/Fe + ECd0 /Cd
E0 = -0.44 + -(-0.40)
E0 = -0.04 V
2Fe
n=2
2+
0.0257 V
ln Q
n
0.010
0.0257 V
ln
E = -0.04 V 2
0.60
E = E0 -
E = 0.013
E>0
Spontaneous
19.5
Charging a Battery
When you charge a battery, you are
forcing the electrons backwards (from
the + to the -). To do this, you will
need a higher voltage backwards than
forwards. This is why the ammeter in
your car often goes slightly higher
while your battery is charging, and then
returns to normal.
In your car, the battery charger is
called an alternator. If you have a
dead battery, it could be the
battery needs to be replaced OR
the alternator is not charging the
battery properly.
Batteries
Dry cell
Leclanch cell
Zn (s)
Anode:
Cathode:
2NH+4 (aq) + 2MnO2 (s) + 2e-
Zn (s) + 2NH4 (aq) + 2MnO2 (s)
Zn2+ (aq) + 2eMn2O3 (s) + 2NH3 (aq) + H2O (l)
Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

19.6
Batteries
Mercury Battery
Anode:
Cathode:
Zn(Hg) + 2OH- (aq)

HgO (s) + H2O (l) + 2eZn(Hg) + HgO (s)
ZnO (s) + H2O (l) + 2eHg (l) + 2OH- (aq)

ZnO (s) + Hg (l)
19.6
Batteries
Lead storage
battery
Anode:
Cathode:
Pb (s) + SO42- (aq)
PbSO4 (s) + 2e-
PbO2 (s) + 4H+ (aq) + SO42- (aq) + 2e-
Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-4 (aq)
PbSO4 (s) + 2H2O (l)
2PbSO4 (s) + 2H2O (l)

19.6
Batteries
Solid State Lithium Battery
19.6
Batteries
A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning
Anode:
Cathode:
2H2 (g) + 4OH- (aq)

O2 (g) + 2H2O (l) + 4e2H2 (g) + O2 (g)
4H2O (l) + 4e4OH- (aq)

2H2O (l)
19.6
Corrosion
19.7
Cathodic Protection of an Iron Storage Tank
19.7
Electrolysis is the process in which electrical energy is used

to cause a nonspontaneous chemical reaction to occur.
19.8
Electrolysis of Water
19.8
Chemistry In Action: Dental Filling Discomfort
2+
Hg2 /Ag2Hg3 0.85 V

2+
Sn /Ag3Sn -0.05 V
2+
Sn /Ag3Sn -0.05 V
Electrolysis and Mass Changes
charge (Coulombs) = current (Amperes) x time (sec)

1 mole e- = 96,500 C = 1 Faraday
19.8
How much Ca will be produced in an electrolytic cell of

molten CaCl2 if a current of 0.452 A is passed through the
cell for 1.5 hours?
Anode:
Cathode:
2Cl- (l)
Ca2+ (l) + 2eCa2+ (l) + 2Cl- (l)
Cl2 (g) + 2eCa (s)

Ca (s) + Cl2 (g)
2 mole e- = 1 mole Ca
C
s 1 mol e- 1 mol Ca
mol Ca = 0.452
x 1.5 hr x 3600 x
x
s
hr 96,500 C 2 mol e= 0.0126 mol Ca
= 0.50 g Ca
19.8

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Electrochemistry

Electron Transfer Reactions

Electrochemical processes are oxidation-reduction

the energy released by a spontaneous reaction is

electrical energy is used to cause a nonspontaneous

2Mg (s) + O2 (g)

Oxidation half-reaction (lose e-)

Reduction half-reaction (gain e-)

Terminology for Redox Reactions

You cant have one without the other!

LEO the lion says GER!

Another way to remember

Review of Oxidation numbers

Na, Be, K, Pb, H2, O2, P4 = 0

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

4. The oxidation number of hydrogen is +1 except when

HCO3Oxidation numbers of all

Balancing Redox Equations

2. Separate the equation into two half-reactions.

3. Balance the atoms other than O and H in each half-reaction.

Balancing Redox Equations

Fe3+ + 1e2Cr3+ + 7H2O

Balancing Redox Equations

Reduction: 6e- + 14H+ + Cr2O7214H+ + Cr2O72- + 6Fe2+

6Fe3+ + 6e2Cr3+ + 7H2O

6Fe3+ + 2Cr3+ + 7H2O

CHEMICAL CHANGE --->

This is accomplished in a GALVANIC or

Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M & [Zn2+] = 1 M

Standard Electrode Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Cathode (reduction): 2e- + 2H+ (1 M)

Zn2+ (1 M) + 2eH2 (1 atm)

Standard Electrode Potentials

Standard hydrogen electrode (SHE)

E0 is for the reaction as

The more positive E0 the

The half-cell reactions are

The sign of E0 changes

Changing the stoichiometric

Standard Electrode Potentials

Standard Electrode Potentials

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Cathode (reduction): 2e- + Cu2+ (1 M)

2H+ (1 M) + 2eCu (s)

What is the standard emf of an electrochemical cell made

Cr3+ (aq) + 3e-

Cd is the stronger oxidizer

Cathode (reduction): 2e- + Cd2+ (1 M)

3Cd (s) + 2Cr3+ (1 M)

Spontaneity of Redox Reactions

n = number of moles of electrons in reaction

Spontaneity of Redox Reactions

What is the equilibrium constant for the following reaction

Reduction: 2e- + Fe2+

The Effect of Concentration on Cell Emf

Will the following reaction occur spontaneously at 250C if

Reduction: 2e- + Fe2+