Abstract:

The objective of this experiment is to determine the degree of dissociation, and the
thermodynamic equilibrium constant, K for acetic acid, CH3COOH at 25oC. To prepared
the acetic acid solutions, the pipettes and the volumetric flasks are required. Firstly, fill
deionized water into the volumetric flasks containing 0.1M of acetic acid up to the calibration
mark to prepare solutions of CH3COOH with molarities 0.05, 0.01, 0.005, 0.001, 0.0005 and
0.0001M. Now we have six acetic acid solutions available for measuring the conductivity at
different concentrations. Then, calibrated the digital conductivity meter with conductivity
probe throughly with deionized water. After thoroughly rinsing the conductivity probe with
deionized water, fixed it in the clamp, so that its height can be adjusted by loosening and
fastening the screw of the crossed bosshead at the stand. Started with the solution of the
lowest concentration 0.0001M and following the order up to concentrated acetic acid, the
value of

was measured. The experimental value of dissociation constant of acetic acid Ka is

1.8197x10-3 and the experimental value of molar conductivity of acetic acid is 125
Scm2mol-1. Meanwhile the degree of dissociations, , at concentrations 0.05M, 0.01M,
0.005M, 0.001M, 0.0005M and 0.0001M is 0.077, 0.176, 0.240, 0.720, 0.480 and 0.800. We
succeed to obtain the objective of this experiment.

Introduction:
Kohlrauschs law describing the effect of dilution on the molar conductivity of strong
electrolytes, Kohlrauschs law of independent ion migration and the DebyeHckel limiting
law (both in general and simplified forms) and explain their importance. The conductivity
meter actually measures a solutions resistance but displays its conductivity. Explain how a
set of conductivity standard solutions can be used to calibrate the conductivity meter and how
the meter can then calculate conductivity, ,values (your explanation should include the
concept of a cell constant). Then define equivalent conductance, , as:

Eq1
Here, v is the number of equivalent ions per molecule, is the fractional dissociation, U is the
ionic mobility of the charged species and c is the concentration of the electrolyte in mol/L.
Using this formula will yield having unit -1m2mol-1 (or S-1 m2mol-1). For strong
electrolytes

is unity and is roughly constant at all concentrations. It will however

approach a finite value at infinite dilution, . Onsager showed that for strong electrolytes in
dilute solution as:

Eq2

Thus, the conduvtance at infinite dilution of solutions of strong electrolytes may be

detremined from measurements of conductance at varying concentration. The y-intercept of a
graph of versus will yield this value. For weak electrolytes, the fraction dissociated is
not unity but is given by the ration of equivalent conductance to the conductance at the
infinite dilution, assuming that ion mobilities are independent of concentration

Eq3

Now present the expression for the equilibrium constant, c with c expressed as a molarity:

Eq4

The equilibrium constant for the dissociation of acetic acid obtained using this equation will
differ from , the true thermodynamic value, because the activity coeffeicient, , are left out
of the numerator and because of the assumptions made when calculating using equation 3.
2
Since K = c is a good approximation, it follows that:

log

log

According to the Debye-Huckel Theory, the mean activity coefficient at low and moderate
ionic concentration is given by:

Eq6

The ionic strength is defined by the expression:

Eq7

Where is the molality of the th ionic species in moles per kilogram of solvent,
is the charge on ion and the sum is taken over all ionic species in the solution. In equation
6, for dilute solutions at 25oC, A= 0.509kg1/2mol-1/2 and the quantity B is nearly unity for
many electrolytes. In addition, it is valid to approximate molality by molarity(mol/L). For the
very dilute solutions of acetic acid used in the experiment, the I=c is very small and equation 6
is well approximated by:

log

log

Hence, if Kc has been determined at many dilute concentrations, a plot of log Kc versus
will give a straight line. Extrapolation to c=0 (the y-intercept) can be made to yield log Ka
from which Ka can be easily calculated.

Procedure:
1.
2.
3.
4.
5.
6.
7.
8.

Cleaned burette with 0.1M CH3COOH solution.

Drained out required volume of 0.1M CH3COOH into six volumetric flasks.
Added deionized water to the calibration mark for each volumetric flask to prepared
molarities of 0.05M, 0.01M, 0.005M, 0.001M, 0.0005M and 0.0001M.
Calibrated the digital conductivity meter with conductivity standard of 84S cm-1
at 25oC.
Rinsed stirring bar with 50mL deionized water and put it in the 50mL beaker with
deionized water and placed the magnetic stirrer.
Immersed probe 5cm in the solution and switch on the magnetic stirrer.
Record the electric conductivity
Repeated step 5 to 7 with diluted CH3COOH. Begin with the lowest molarity to the
higher molarity of CH3COOH.

Results:
Data sheet experiment 5:
Concentration (M)
0.05
0.01
0.005
0.001
0.0005
0.0001

Electrolytic conductivity of HAc () at

25oC (S cm-1)
480
220
150
90
30
10

Electrolytic conductivity of deionized water (DIwater) at 25oC = 1.9S cm-1

Calculation and discussion:

The value of (S cm2 mol-1) for CH3COOH solutions is:
i)

C = 0.0001M
= 10 S cm-1

ii) C = 0.0005M
= 30 S cm-1

5
5

iii) C = 0.001M
= 90S cm-1

iv) C = 0.005M
= 150 S cm-1

5
5

5
5

v) C = 0.01M
= 220S cm-1

vi) C = 0.05M
= 480 S cm-1

5
5

 (S cm2 mol-1)

1/ (S-1 cm-2 mol)

C (mol cm-3)

100.0
60.0
90.0
30.0
22.0
9.6

0.010
0.016
0.011
0.033
0.045
0.104

0.01x10-5
0.05x10-5
0.10x10-5
0.50x10-5
1.00x10-5
5.00x10-5

(S cm-1 mol)
1.00x10-5
3.00x10-5
9.00x10-5
15.0x10-5
22.0x10-5
48.0x10-5

From this experiment, we obtained the values of by using the formula molar conductivity,
which is 100, 60, 90, 30, 22 and 9.6 Scm2mol-1. Through this, we also can calculate the
values of 1/ which is 0.010, 0.016, 0.011, 0.033, 0.045 and 0.104 S-1cm-2mol. Meanwhile the
values of c that we obtained are 1.00x10-5, 3.00x10-5, 9.00x10-5, 15.0x10-5, 22.0x10-5,
48.0x10-5. From this resulted, we can plotted graph 1/ versus c, the graph used to
determine the value of by extrapolation to zero concentration. The equation c = 1/
implies that, if 1/ is plotted against c, then the intercept at c=0 will be 1/ .
Value of 1/ = 0.008 S-1cm-2mol

= = 125 Scm2mol-1
Then, we can calculate the value of Kc from the slope of the graph by using formula:

This equation represents Y = C + MX:

Y = 1/

C = 1/

M=

From the graph slope, we find that value of M written as:

5 5

X = c

Substitute in:
M=
585.71x105 =
]

585.71

5 5

S-1cm-1

According to the standard data of molar ionic conductivity, the theoretical value of molar
conductivity in the limit of zero concentration of acetic acid:

5
5

From calculation, the experimental value of is 125 Scm2mol-1 (from Kohlrauschs law).
|

5
5

The major systematics error in this experiment is not rinsed the electrode with deionized
water properly before use. This cause the contaminant in the smaple to be tested and lead to
higher percentage error which is 67.99% and have low accuracy between experimental and
theoretical results. On the other hand, calculation of degree of dissociation () of CH3COOH
at the concentrations of 0.05M, 0.01M, 0.005M, 0.001M, 0.0005M and 0.0001M is:
At 0.05M(5.00x10-5molcm-3)

= 9.6

= /
= 9.6 / 125
= 0.077

At 0.01M(1.00x10-5molcm-3)

= 22.0

= /
= 22.0 / 125
= 0.176

At 0.005M(0.50x10-5molcm-3)

= 22.0

= /
= 30.0 / 125
= 0.240

At 0.001M(0.10x10-5molcm-3)

= 22.0

= /
= 90.0 / 125
= 0.720

At 0.0005M(0.05x10-5molcm-3)

= 22.0

= /
= 60.0 / 125
= 0.480

At 0.0001M(0.01x10-5molcm-3)

= 22.0

= /
= 100.0 / 125
= 0.800

Degree of dissociation, is inversely proportional to concentration of given electrolyte, thus

as the concentration decreases, the degree of dissociation increases. As the concentration C
approaches to zero or dilution approaches to infinity, the degree of dissociation, reaches to
unity that is maximum value of that. This generalization is called as Ostwald dilution law.
According to Physical Chemistry (8th edition), thetheoretical value of dissociation constant of
acetic acid (Ka) is 1.4 x 10-5M. From calculation, the experimental value of Ka is:
log

log

log

log
5

log
log

The molar conductivity is found to vary according to the concentration. One reason for this
variation is that the number of ions in the solution might not be proportional to the
concentration of the electrolyte. For instance, the concentration of ions in a solutionof a weak
acid depends on the concentration of the acid in acomplicated way, and doubling the
concentration of the acid added does not double the number of ions. Secondly, because ions
interact strongly with one another, the conductivity of a solution is not exactly proportional to
the number of ions present.

Conclusion:
In conclusion, we conclude that the experimental value of dissociation constant of
acetic acid Ka is 1.8197x10-3 and the experimental value of molar conductivity of acetic acid
is 125 Scm2mol-1. Meanwhile the degree of dissociations, , at concentrations 0.05M,
0.01M, 0.005M, 0.001M, 0.0005M and 0.0001M is 0.077, 0.176, 0.240, 0.720, 0.480 and
0.800. We succeed to obtain the objective of this experiment.