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OBJECTIVE

To determine the molar conductivity at infinite dilution (0) of sodium chloride, hydrochloric acid,
sodium acetate, and acetic acid at 250c.

INTRODUCTION
Electrolytes are substances which dissolve in water to produce solutions which conduct electrical current.
Such substances produce ions when dissolve in water, and the ions carry the current through solution.
Nonelectrolytes are the substances whose aqueous solution do not contain ions and hence do not conduct
electrical current. Electrolytes are classified as either strong electrolytes or weak electrolytes. Strong
electrolytes when dissolved in water ionize completely to produce ions. For example, when NaCl is
dissolved in water:
NaCl (s) Na+ (aq) + Cl- (aq)
There are no dissolved NaCl molecule present in the solution. Solutions of strong electrolytes are good
conductor of electricity because they contain a relatively high concentration of ions.
Strong Electrolytes
The electrolytic conductivity (K) (S cm-1) of a solution increases with concentration. However, quantity K
is not a suitable quantity for comparing the conductivities of different solutions. If a solution of one
electrolyte is much more concentrated than another, it may have a higher conductivity simply because it
contains more ions. Instead, molar conductivity ( ) (S cm -1) should be adopted for comparison. It is
defined as (K/concentration). Quantity decreases as the concentration increases. Onsager showed
theoretically for strong electrolytes in dilute solution that the effect of ionic attraction reduces the molar
conductivity as in Eq. (1)
= 0 - Kc

(1)

Quantities c and 0 denote concentration of the electrolyte of the molar conductivity at in finite dilution.
Below concentrations of about 0.1 M, a plot of against c result in a straight line. The intersection of
this line with the ordinate is the 0. The 0 values are found to be additive. Kohlrausch assumed that in
such a system the molar conductivity at infinite dilution is simply the sum of the independent contribution
of the ions.

Consider a strong electrolytes that yields ions A and B solution:


ApBq pAz+ + qBzKohlrauschs law of independent migration of ions proposed:
0 = p0+ + q0-

(2)

For a 1-1 electrolyte A+B0 = 0+ + 0-

(3)

Quantity 0 denotes molar ionic conductivity at infinite dilution. (S cm2 mol-1). This equation has been
written for infinite dilution since it only under such conditions, when ion-ion interactions are at a
minimum that the law strictly holds. It is the applicable to both strong and weak electrolytes.

CHEMICALS
1) 0.1 M sodium chloride, NaCl
2) 0.1 M hydrochloric acid, HCl
3) 0.1 M sodium acetate, NaAc

APPARATUS
1)
2)
3)
4)
5)
6)

Digital conductivity meter (1)


100 mL volumetric flask (18)
50 mL burette (3)
100 mL beaker (9)
Magnetic stirrer with stirring bar (1)
Conductivity probe holder (1)

PROCEDURES
1) A clean burette was filled with 0.1 M NaCl solution.
2) The required volume of 0.1 M NaCl was drained out into each volumetric flask and top up with
DI water to prepared the following molarities, 0.05, 0.01, 0.005, 0.001, 0.0005 and 0.0001 M.
3) The digital conductivity meter was calibrated with conductivity standard of 1413 S cm -1 or 12.88
mS cm-1 at 250c.

4)
5)
6)
7)

Stirring bar and conductivity probe was rinsed by using DI water.


The beaker was filled with 50 mL deionized water and stirring bar was placed in.
The beaker was placed on the magnetic stirrer.
The probe was immersed to a depth approximately 5 cm in the solution. Probe was support with

probe holder.
8) The magnetic stirrer was switch on and the electrolytic conductivity (K) of the DI water at 250c
was recorded.
9) Steps 4-8 were repeated with the diluted NaCl. The NaCl solution was begin with the lowest
concentration first.
10) Steps 1-9 by using HCl and NaAc solutions.
11) All electrolytic conductivity measurements was measured at 25 0c. If the K values of the solutions
are comparable to the DI water, quantities of K was corrected as (K-Kwater).

RESULTS AND DISCUSSIONS


1) Tabulate the results.

Refer to the appendix

2) Determine the (S cm2 mol-1) for each of the strong electrolyte solutions, then plot versus c
(unit of c in mol cm-3). You may include all the three plots (NaCl, HCl, NaAc) 0n the same graph
paper.

NaCl
Concentration = 0.0001 M
(S cm2 mol-1) =

K
c

2 3

mol 1000 L ( 10 ) m
0.0001

3
3
L
1m
cm

= 509 S cm2 mol-1


Concentration = 0.0005 M
(S cm2 mol-1) =

50.9 x 10 S cm

K
c

103.9 x 106 S cm1


2 3

mol 1000 L ( 10 ) m
0.0005

L
1 m3
cm3

= 207.8 S cm2 mol-1


Concentration = 0.001 M
(S cm2 mol-1) =

K
c

2 3

2 3

168.1 x 106 S cm1


mol 1000 L ( 10 ) m
0.001

L
1m3
cm 3

= 168.1 S cm2 mol-1


Concentration = 0.005 M
2

-1

(S cm mol ) =

K
c

635.0 x 106 S cm1


mol 1000 L ( 10 ) m
0.005

L
1 m3
cm 3

= 127 S cm2 mol-1


Concentration = 0.01 M
(S cm2 mol-1) =

K
c

1232 x 10 S cm

2 3

mol 1000 L ( 10 ) m
0.01

3
3
L
1m
cm

= 123.2 S cm2 mol-1

Concentration = 0.05 M
(S cm2 mol-1) =

K
c

5.71 x 103 S cm1


2 3

mol 1000 L ( 10 ) m
0.05

L
1 m3
cm3

= 114.2 S cm2 mol-1

HCl
Concentration = 0.0001 M
(S cm2 mol-1) =

K
c

2 3

2 3

199.5 x 10 S cm

mol 1000 L ( 10 ) m
0.0001

3
3
L
1m
cm

= 1995 S cm2 mol-1


Concentration = 0.0005 M
(S cm2 mol-1) =

K
c

215.0 x 10 S cm

mol 1000 L ( 10 ) m
0.0005

3
3
L
1m
cm

= 430 S cm2 mol-1


Concentration = 0.001 M

(S cm2 mol-1) =

K
c

2 3

2 3

423.0 x 10 S cm

mol 1000 L ( 10 ) m
0.001

3
3
L
1m
cm

= 423 S cm2 mol-1


Concentration = 0.005 M
(S cm2 mol-1) =

K
c

2.09 x 10 S cm

mol 1000 L ( 10 ) m
0.005

3
3
L
1m
cm

= 418 S cm2 mol-1


Concentration = 0.01 M
(S cm2 mol-1) =

K
c

4.12 x 103 S cm1

= 412 S cm2 mol-1

Concentration = 0.05 M
(S cm2 mol-1) =

2 3

mol 1000 L ( 10 ) m
0.01

L
1 m3
cm3

K
c

19.73 x 103 S cm1


2 3

mol 1000 L ( 10 ) m
0.05

L
1 m3
cm3

= 394.6 S cm2 mol-1

NaAc
Concentration = 0.0001 M
(S cm2 mol-1) =

K
c

2 3

2 3

37.1 x 106 S cm1


mol 1000 L ( 10 ) m
0.0001

L
1m3
cm3

= 371 S cm2 mol-1


Concentration = 0.0005 M
(S cm2 mol-1) =

K
c

72.2 x 106 S cm1


mol 1000 L ( 10 ) m
0.0005

L
1 m3
cm3

= 144.4 S cm2 mol-1


Concentration = 0.001 M
(S cm2 mol-1) =

K
c

2 3

2 3

128.1 x 106 S cm1


mol 1000 L ( 10 ) m
0.001

L
1m3
cm 3

= 128 S cm2 mol-1


Concentration = 0.005 M
(S cm2 mol-1) =

K
c

461.0 x 106 S cm1


mol 1000 L ( 10 ) m
0.005

L
1 m3
cm 3

= 92.2 S cm2 mol-1


Concentration = 0.01 M
2

-1

(S cm mol ) =

K
c

2 3

2 3

857.0 x 10 S cm

mol 1000 L ( 10 ) m
0.01

3
3
L
1m
cm

= 85.7 S cm2 mol-1

Concentration = 0.05 M
(S cm2 mol-1) =

K
c

4.24 x 103 S cm1


mol 1000 L ( 10 ) m
0.05

L
1 m3
cm3

= 84.8 S cm2 mol-1

Table of versus c

c (mol L-1)

c (mol cm-3)

0.0001
0.0005
0.001
0.005
0.01
0.05

3.1623 x 10-4
7.0712 x 10-4
1.0000 x 10-3
2.2361 x 10-3
3.1623 x 10-3
7.0712 x 10-3

NaCl
509
207.8
168.1
127
123.2
114.2

(S cm2 mol-1)
HCl
1995
430
423
418
412
394.6

NaAc
371
144.4
128
92.2
85.7
84.8

Graph of versus c
Refer to the appendix

3) From the linear regressions, determine the value of 0 for each of the solution.

From the graph:


0 (NaCl) = 230 S cm2 mol-1
0 (HCl) = 475 S cm2 mol-1
0 (NaAc) = 100 S cm2 mol-1

The value of slope for the graph of versus c are negative. The value of 0 for each
solution were determined by extended the straight line to the 0.0 M concentration.

4) Report the standard errors in the 0.

The equivalent conductivity of weak electrolytes increases steeply at very low concentrations
(see the above graph) and hence their limiting values ( o) cannot be determined by
extrapolating the c to zero concentration.

Molar conductivities of weak electrolytes, mo can be easily calculated with the help of
Kohlrausch's law.

5) From the 0 value, determine the value of 0 for acetic acid (HAc).

0 (NaCl) = 230 S cm2 mol-1


0 (HCl) = 475 S cm2 mol-1
0 (NaAc) = 100 S cm2 mol-1

0CH3COOH = 0CH3COO- + 0H+


0CH3COONa = 0CH3COO- + 0Na+
0HCl = 0H+ + 0Cl0NaCl = 0Na+ + 0ClTherefore:
0CH3COOH = 0CH3COONa + 0HCl - 0NaCl
= (100 + 475 230) S cm2 mol-1
= 345 S cm2 mol-1

6) Using the table of molar ionic conductivities of electrolyte at in finite dilution in aqueous solution
at 250c find the 0 of NaCl, HCl, NaAc and HAc.

Cations
H+
Li+
Na+
K+
Mg2+

+0 /S cm2mol-1
349.6
38.69
50.11
73.50
106.12

anions
OHClBrISO42-

-0 /S cm2mol-1
199.1
76.34
78.4
76.8
159.6

Ca2+
Ba2+

119.00
127.28

NO3CH3COO-

71.4
40.9

HCl
0HCl = 0H+ + 0Cl= 349.6 + 76.34
= 425.94 S cm2 mol-1

NaCl
0NaCl = 0Na+ + 0Cl= 50.11 + 76.34
= 126.45 S cm2 mol-1

NaAc
0CH3COONa = 0CH3COO- + 0Na+
= 40.9 + 50.11
= 91.01 S cm2 mol-1

HAc
0CH3COOH = 0CH3COO- + 0H+
= 40.9 + 349.6
= 390.5 S cm2 mol-1

7) Compare 0,exp with the 0,theory determined from the standard data. Describe possible sources for
systematic errors and degree of their importance.

,exp , theory
, theory

% error (NaCl) =

230126.45
126.45

x 100

x 100

= 81.89%

,exp , theory
, theory

% error (HCl) =

475425.94
425.94

x 100

x 100

= 11.51%

% error (NaAc) =

,exp , theory
, theory

10091.01
91.01

x 100

x 100

= 9.88%

Possible factor that affect the errors:

Interionic attractions: depends on solute-solute interactions.


Solvation of ions: depends on solute-solvent interactions.
Viscosity solvent: depends upon solvent-solvent interactions.
Concentration of solution: Higher concentration of solution less is conduction. If
weak electrolyte, ionization is less & if strong

electrolyte.
Temperature: Electrolytic conduction increase with increase in temp.

CONCLUSION
From the experiment, the value of 0 at 250c for NaCl is 230 S cm2 mol-1, for HCl is 475 S cm2 mol-1, for
NaAc is 100 S cm2 mol-1 and for HAc is 345 S cm2 mol-1.

REFERENCES
1) http://www.adichemistry.com/physical/electrochemistry/kohlrausch/kohlrausch-law.html
2) http://en.wikipedia.org/wiki/Conductivity_%28electrolytic%29
3) http://www.jesuitnola.org/upload/clark/labs/PerError.htm

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