Chapter 7
Solutions of Electrolytes
7-2
Molar conductivity
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Outline
Resistance, conductance and
conductivity
Molar Conductivity of strong and weak
electrolytes
Arrhenius theory and Ostwald dilution
law
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7.2 Conductivity and its measurement
Conductivity: Is the ability of a solution
to conduct electric current.
It is measured using conductivity meter:
1- Determine the resistance (R) of the
solution between two flat or cylindrical
electrodes separated by a fixed distance.
2- An alternating voltage is used in order
to avoid electrolysis. Typical frequencies
used are in the range 13 kHz.
3- The resistance is measured by a
conductivity meter.
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Conductance and conductivity
Conductance, G, is the inverse of electrical resistance
G = 1/R ---------1
Units ohm-1, -1, or mhos
SI unit: Siemens (S): 1 S = 1 -1= 1 C/(Vs); from Ohm law
Conductance is inversely proportional to the length between
electrodes (L) and directly proportional to the area of the
electrodes (A):
G = A/L ---------2
is the proportionality constant and is called conductivity (S/cm)
L = length (cm)
A = area (cm2)
Define the cell constant (K) = L/A, then:
(S/cm) = G K --------------------3
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Example
The conductivity of 0.1 M solution of weak acid is
5.3x 10-4 Scm-1. the cell constant (K = L/A) was 0.1
cm-1. Calculate The observed conductance (G) and
resistance of the solution.
(S/cm) = G(S) K (cm-1)
G = /K
= 5.3x 10-4 Scm-1 / 0.1 cm-1
G = 5.3x 10-3 S
G = 1/R or R = 1/G = 189 or 189 V s/C
I = V/R
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Molar conductivity
Introduce the Molar conductivity, m,(Scm2
mol-1) where:
m = 1000 /c -------------4
where c is in mol/dm3 (1 dm3 = 1L)
Variation of m with concentration:
m is function of:
1- the number of ions in solution
2- interaction between ions
Two behaviors are observed:
Strong electrolyte weak dependence
Weak electrolyte - strong dependence
We need theories to explain these
behaviors.
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Manipulation of the experimental data
For weak electrolyte, it
was found the plot 1/ m
vs cm will give a straight
line.
For strong electrolyte, it
was found that the plot of
m vs C1/2 will give straight
line.
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Two theories were introduced
Arrhenius and Ostwald theory: Proposed the
presence of ions is solution. They derived the
Ostwald dilution law. This theory explained the
observed behavior of the dependence of molar
conductivity on concentration for o weak
electrolytes.
Debye- Hckel theory: Based on the presence of
ionic atmosphere.
Derived Onsager- Hckel-Debye equation, which
accounted for the observed behavior of the
dependence of molar conductivity on concentration
for strong electrolytes.
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Variation of Molar Conductivity
Weak Electrolytes (Arrhenius Theory)
Not fully ionized in solution
For weak Brnsted acids and bases (e.g., acetic acid,
ammonia)
HA(aq) + H2O(l) A-(aq) + H3O+(aq) (1)
aH O a A
Ka 3
(2)
a HA
Let the activity concentration
[ H O ][ A ] (3)
Ka 3
[ HA]
Conductivity depends on degree of ionization, ,
(degree of deprotonation for weak acids)
[H3O+] = c; [A-] = c; [HA] = c- c = (1- )c
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Linearization
Substitute these value in equation 3:
2 2 2
c c
Ka
1 c 1
Solving for using the quadratic formula
K a 4c
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1 1
2c K a
The acid is fully deprotonated at infinite
dilution m m
The molar conductivity, m, becomes
m = m
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Ostwalds Dilution Law
Ka
2c Ka c 1 c
or
1
1 K a 1
Re arranging
1 c or
1
1
c
Ka Ka
Lm
But , ;
Lm
o
substitute
L
for
m
c
L o
L o
L mc
m
1 m
1
Lm Ka K a Lom
DividingbyLom ,
1 1 L mc
o Ostwalds Dilution Law
Lm Lm K a Lom
2
If you plot 1/ Lm vs. Lmc, a straight is obtained.
The y-intercept [at infinite dilution (c = 0)] is 1/Lm
The slope is 1/Kam2, hence the acid dissociation constant (Ka) can be
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obtained from the slope and intercept.
Example
The conductivity of 0.100 M solution of weak acid is 5.30x 10-4 Scm-1. the
cell constant (K = l/A) was 0.100 cm-1. Calculate:
1- The observed conductance (G)
G = /K
= 5.3x 10-4 Scm-1 / 0.100 cm-1
= 5.30x 10-3 S
2- The molar conductivity(Lm)
m = 1000 /c = 0.530/0.100 = 5.30 S cm2mol-1
3- The acid dissociation constant (Ka) (Lm for acetic acid = 390.55 S
cm2mol-1)
m = m ; = 5.30/390.55 = 0.0136
2 c2 2c
Ka
1 c 1 = (0.0136)2 x 0.100/0.986
Ka = 1.87x 10-5
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Testing the hypothesis
and i Vant Hoff factor
Degree of ionization can be obtained independently
from Vant Hoff factor of osmotic pressure.
The osmotic pressure for electrolytes is given by:
= iMRT
where i is the vant Hoff factor.
For NaCl, i = 2, for MgCl2 , i = 3
For weak electrolytes i is different than the
number of ions. It is determined experimentally.
Once we know i, we can calculate :
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Continued
Assume upon complete dissociation of one
molecule, it gives ions.
MA M+ + A-
Thus for molecules having degree of
dissociation :
MA M+ + A-
The number of ions produced =
and number of intact molecules is (1- ).
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Continued
The total number of particles produced by one
molecule is:
i = (1- ) +
Hence: = i-1/ -1
Values of obtained from osmotic pressure
measurements for weak electrolyte, agree very well
with those obtained from conductivity measurement
( =Lm/Lm).
They dont agree with those obtained for strong
electrolyte.
Hence Arrhenius theory is satisfactory when applied
to weak electrolytes.
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Example
The observed osmotic pressure of 0.100 M acetic
acid solution is 2.48 atm at 298 K.
a- Calculate the degree of dissociation ()
= iMRT;
i = 2.48/ (0.100x0.0821x 298) = 1.0136
= i-1/ -1 = 1.0136-1/2-1 = 0.0136
b- Compare its value with that obtained from
conductivity measurements (Slide 12)
= m/Lm = 5.30/390.55 = 0.0136;
hence they are the same.
Arrhenius theory is valid.
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Announcements
Suggested questions: 5, 7, 8 and 9
Good luck
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