Chem 150

1
st
Semester,
2012-2013
Classification of Electrolytes
1. Based on conductivity
i. Strong electrolyte
ii. Weak electrolyte

2. Based on structure
i. True electrolyte
ii. Potential electrolyte


HCl(g) + H
2
O(l) H
3
O
+
(aq) + Cl
-
(aq)

NaCl(s) + H
2
O(l) Na
+
(aq) + Cl
-
(aq)

CH
3
COOH + H
2
O(l) H
3
O
+
(aq) + CH
3
COO
-
(aq)
Review of Theories
1. Arrhenius Theory of Dissociation
Electrolytes ionize such that the total positive charge is
equal to the total negative charge
The extent of ionization depends on the concentration of
the electrolyte.
2. Debye-Huckel Theory of
Interionic Attraction
An ionic sphere surrounds a
dissolved ion in solution
Ionic Strength
The thermodynamic properties of electrolyte solutions depend on:
valence of ions in solution (charge)
concentration
temperature
dielectric constant of medium (solvent)

At constant T and solvent, only the first two factors affect the
properties of a solution. The effect of these quantities are
reflected in the ionic strength of the solution.

=
i
2
i i
z C
2
1

=
i
2
i i
z C
2
1
| |
C
2
C 2
) 1 ( C ) 1 ( C
2
1
2 2
= =
+ =
For a 1-1 electrolyte,
C
+
= C
-
= C
z
+
= z
-
= 1, C
+
z
+
= C
-
z
-

For a 2-1 electrolyte,
C
+
= C, C
-
= 2C
z
+
= 2, z
-
= 1
| |
C 3
2
C 6
) 1 ( C 2 ) 2 ( C
2
1
2 2
= =
+ =
Type of Electrolyte Example Ionic Strength
1-1 NaCl C
2-1, 1-2 Ba(NO
3
)
2
, Na
2
SO
4
3C
3-1, 1-3 Al(NO
3
)
3
, Na
3
PO
4
6C
2-2 MgSO
4
4C
Compare the of 0.1M solutions of NaCl, HCl, SrCl
2
, AlCl
3
,
ZnSO
4
and Fe
2
(SO
4
)
3
.

0.1 M NaCl = 0.1 M
0.1 M HCl = 0.1 M
0.1 M SrCl
2
= 0.3 M

0.1 M AlCl
3
= 0.6 M

0.1 M ZnSO
4
= 0.4 M

0.1 M Fe
2
(SO
4
)
3
= 1.5 M

=
i
2
i i
z C
2
1
A solution is 0.5 M in MgSO
4
, 0.1 M in AlCl
3
and 0.2 M in
(NH
4
)
2
SO
4
. What is the total ionic strength?

=
i
2
i i
z C
2
1
| |
+ + + + + +
+ + + + =
Cl Cl NH NH Al Al SO SO Mg Mg
z C z C z C z C z C
2
1
4 4
3 3 2
4
2
4
2 2
| |
2 2 2 2 2
) 1 )( 3 M 1 . 0 ( ) 1 )( M 4 . 0 ( ) 3 )( M 1 . 0 ( ) 2 )( M 2 . 0 M 5 . 0 ( ) 2 )( M 5 . 0 (
2
1
+ + + + + =
M 2 . 3 =
The vant Hoff factor, i, of an electrolyte solution can be
determined given the ionic strength of the solution. The
equation that relates these two quantities is called Debye-
Huckel equation.

) z z 375 . 0 1 ( i v =
+
Using the Debye-Huckel equation, calculate the values of i for
0.0005 M HCl and La(NO
3
)
3
.
For 0.0005 M HCl:
( ) ( )( ) | | M 0005 . 0 1 M 0005 . 0 ) 1 ( M 0005 . 0
2
1
2
2
= + =
) M 0005 . 0 ) 1 )( 1 ( 375 . 0 1 ( 2 i =
983 . 1 i =
For 0.0005 La(NO
3
)
3
M , i = 3.734
ELECTROLYSIS
Electrolysis is a process in which a non-spontaneous reaction is
driven by the application of electric energy.


Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) E
cell
= 1.103 V

G = -n FE

If this cell is connected to an external source of electricity, the
reaction will proceed in which direction?



Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) E
cell
= 1.103 V

Cu(s) + Zn
2+
(aq) Cu
2+
(aq) + Zn(s) E
cell
= -1.103 V

In predicting electrolysis reactions, consider the state of the
substances, whether the electrodes are inert or active and
whether there is overpotential (for O
2
).

A. Molten state with inert electrodes
Only one reduction and one oxidation are possible.
E.g. electrolysis of NaCl with platinum electrodes
Reduction: 2Na
+
+ 2e

2Na(l)
Oxidation: 2Cl

Cl
2
(g) + 2e

B. Aqueous state with inert electrodes
Reduction:
2Na
+
+ 2e

2Na(l) E = -2.71 V
2H
2
O(l) + 2e

H
2
(g) + 2 OH

(aq) E = -0.83 V
Oxidation:
2Cl

Cl
2
(g) + 2e

-E = -(1.36 V)
2H
2
O(l) O
2
(g) + 4H
+
+ 4e

-E = -(1.23 V)

There are two possibilities:
(1) 2Cl

+ 2H
2
O(l) Cl
2
(g) + H
2
(g) + 2 OH

(aq) E
cell
= -2.19V
(2) 2H
2
O(l) 2 H
2
(g) + O
2
(g) E
cell
= -2.06 V
HOMEWORK

In the electrolysis of AgNO
3
(aq), what are the expected
electrolysis products if the anode is silver metal and the
cathode is platinum?
1. The mass of an element produced at
an electrode is proportional to the
quantity of electricity Q passing
through the liquid.
Q = It

2. The mass of an element liberated at an
electrode is proportional to the
equivalent weight of the element.

Faradays constant (F) = 96490 C/e


Faradays Law of Electrolysis
Review of Equivalents
The definition of equivalents depends on the type of substance
(and reaction) being considered acid/base, salt,
reductant/oxidant

In the case of reductant or oxidant, equivalents refers to the
number of e

involved in its oxidation or reduction.

The advantage of using equivalents is that a conversion factor
from moles ion to moles e

is no longer needed.

Equivalent weight is the molar weight of a substance divided by
its equivalents.
To illustrate, suppose the same current was used to electrolyze
H
2
(g), Ag(s) and Cu(s) in a solution of dilute sulfuric acid, a
solution of AgNO
3
and a solution of CuSO
4
.

The following reactions were involved:
2H
+
(aq) + 2e

H
2
(g) [H
+
(aq) + e

H
2
(g)]
Ag
+
+ e

Ag(s)
Cu
2+
+ 2e

Cu(s) [ Cu
2+
+ e

Cu(s)]

For the same amount of electricity,
mol H
2
(g) = 1 mol Ag(s) = Cu(s)
1 eq H
2
(g) = 1 eq Ag(s) = 1 eq Cu(s)
SAMPLE PROBLEM
A constant direct current flows through an iodine coulometer for
a period of 2 hours. At the end of this time is found that the
coulometer contains 0.0020 equivalent of liberated I
2
. What was
the current passing through the coulometer?
SAMPLE PROBLEM
A constant direct current flows through an iodine coulometer for
a period of 2 hours. At the end of this time is found that the
coulometer contains 0.0020 equivalent of liberated I
2
. What was
the current passing through the coulometer?
The reaction involved is:
2I

(aq) I
2
(g) + 2e

SAMPLE PROBLEM
A constant direct current flows through an iodine coulometer for
a period of 2 hours. At the end of this time is found that the
coulometer contains 0.0020 equivalent of liberated I
2
. What was
the current passing through the coulometer?
The reaction involved is:
2I

(aq) I
2
(g) + 2e


A 0268 . 0 or
s
C
0268 . 0
hr
s 3600
hr 2
e
C 96490
e 0020 . 0
t
Q
I =
|
.
|

\
|
|
.
|

\
|
= =

SAMPLE PROBLEM
What was the mass of the liberated I
2
?
SAMPLE PROBLEM
What was the mass of the liberated I
2
?
( )
2
2
2 2
2
2
2
2
2
2
2
I g 2538 . 0
hr 1
s 3600
hr 2
I mol 1
I g 8 . 253
e mol 2
I mol 1
C 96490
e mol
s
C
0268 . 0 I g
I g 2538 . 0
I mol 1
I g 8 . 253
I eq 2
I mol 1
eq 0020 . 0 I g
=
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
=
=
|
|
.
|

\
|
|
|
.
|

\
|
=

HOMEWORK
Electrolysis of molten KBr generates bromine gas, which can be
used in industrial bromination processes. How long will it take to
convert a 500.00 kg batch of phenol to monobromophenol using
a current of 20 000A?