Experiment

Title: The effect of ionic strength on the equilibrium constant

Purpose
The aim of this experiment is to neutralize potassium hydrogen phthalate (KHP) with NaOH at
different ionic strengths and hence evaluate the effect of the ionic strength on K a

Theory
The acid dissociation constant Ka of a monopronic acid, HA, is represented by the reaction:

H . A
HA H +
+ A where Ka = = Ka H
+
. A
-
HA

Where i is the activity coefficient of species i ( HA is assumed to be unity) and Ka is the

apparent acid dissociation constant. The Debye- Huckel theory gives the activity coefficient i of
species I as :

Log I = - (0.05091 Zi2 I )(1+ I ) for a 1:1 electrolyte in aqueous medium at 25 degrees
Celsius where I = v icizi2 where ci is the concentration of species i in solution , v i is the
stoichiometric coefficient of species i and z i is the charge on species i. KHP is a salt hence is assumed
to dissociate completely in solution: KHP K +(aq) + HP-(aq) .

The anion HP- is a weak acid and it is partially dissociate in solution to for : HP -(aq) H+(aq) + P-
2
(aq)

Experimental

Preparation
A 0.05M KHP solution was prepared in 250 ml. A 0.05M Sodium borate solution was prepared in
100ml. A 0.001M KHP solution was careful prepared by dilution in 250 ml and 0.01M Sodium
hydroxide solution was prepared into 100ml.

Procedure
The pH meter was calibrated. A 0.001M KHP solution was transferred into a 250 ml beaker. A 50ml of
distilled water was added to the titration vessel and was stirred gently with a magnetic stirrer bar.
About 0.5ml Sodium Hydroxide solution was added from the burette. The actual burette reading was
recorded in two decimals. The pH reading was recorded was recorded after it was allowed to have
sufficient time for the system to equilibrate. That procedure was repeated until the volume of the
base added was about 10 ml.

The amount of Sodium Chloride was calculated, required to achieve the ionic strength that was
assigned in the group in a solution that contains 50ml of 0.001M KHP and 50ml distilled water.
The calculated results were shown to the supervisor and then those amounts were quantitatively
added to the titration vessel. Titration was done as above.

Calculations and results

1. KHP, C = 0.001M
KHP = K+ + HP-
[k+] = [HP-]
1 1
I= vicizi2 = [(0.05)(+1)2+(0.05)(-1)2] = 0.05
2 2
1+ ( 0.05)
(0.05091 Z 2i I )
Log = = = -9.3 10
3
i
(1+ I ) (0.05091) ( +1 )2 (1 )2 ( 0.05)

I = 0.9788

NaOH, c = 0.01m. Hence [Na+] = [OH-] = 0.01M

NaOH = Na+ + OH-

1 1
I= vicizi2 = [(0.01)(+1)2+(0.01)(-1)2] = 0.01
2 2

2
1+ ( 0.01)
(0.05091 Z i I )
Log = = = -4.6 10-3
)2 (1 )2 (0.01)
i
(1+ I ) (0.05091) ( +1

I = 0.9894

Na2B4O7 [0.05] = 2Na++ 4B3++702-

[Na+] = 0.1, [B3+] =0.2 and [O2-] = 0.35

1 1
I= vicizi2 = [(0.1)(+1)2+(0.2)(+3)2+(0.35)(-2)2] = 1.65
2 2
2


(0.05091 Z 2i I ) 2 (1.65)
Log i = = = -1.03
(1+ I )
1+ (1.65)
2 2
(0.05091) ( +1 ) (+3 )

I = 0.093

NaCl[0.001] =Na++ Cl-.[Na+] =[Cl-]= 0.001

 1 1
I= vicizi2 = [(0.001)(+1)2+(0.001)(-1)2] = 0.01
2 2

2
1+ ( 0.001)
(0.05091 Z i I )
Log = = = - 1.710-3
i
(1+ I ) (0.05091) ( +1 )2 (1 )2 (0.001)

I = 0.9964

(II)KHP pH = 4.50

10PH 104.50
[H+] = = [H+] = = 3.2310-5
0.9788
NaOH pH = 12

10PH 1012
[H+] = = [H+] = = 1.0110-12
0,9894
Na2B4O7 pH = 12.7

10PH 1012.7
[H+] = = [H+] = = 2.1510-12
0,093

10PH 107
pH = 7 NaCl [H+] = = [H+] = = 1.0010-7
0,9964

Volume of pH of Solution pH of Solution pH of Solution pH of Solution

NaOH (ml) (KHP) (0.25M NaCl) (0.5M NaCl) (0.08M NaCl)
0.00 3.58 3.05 2.98 3.64
0.50 3.28 3.36 3.21 3.77
1.00 3.37 3.63 3.43 3.91
1.50 3.58 3.89 3.64 4.12
2.00 3.80 4.14 3.95 4.31
2.50 4.01 4.44 4.18 4.60
3.00 4.27 4.61 4.46 4.78
3.50 4.41 4.98 4.73 5.05
4.00 4.70 5.34 5.10 5.40
4.50 5.01 5.96 5.71 5.77
5.00 5.47 7.78 7.16 6.73
5.50 5.96 9.12 9.01 9.03
6.00 7.28 9.36 9.29 9.36
6.50 8.84 9.60 9.52 9.58
7.00 9.19 9.72 9.69 9.70
7.50 9.39 9.80 9.77 9.81
8.00 9.61 9.89 9.88 9.90
8.50 9.65 9.94 9.93 10.02
9.00 9.74 9.98 9.97 10.05
9.50 9.78 10.07 10.00 10.10
10.00 9.89 10.09 10.07 10.13

DISCUSSION:
The graphs for which the values were calculated then plotted onto the graphs, its observed that the
graphs for the plot of [H+].V versus V have a similar shape with the values that are similar (close) to
each-other, and I also observed that if we were to plot a graph using all the values that weve
calculated we would obtain a curve whereby the observed shape is sort of a zig-zag, with the values
alternating in a range close to each other but descending or ascending in small values.

Then for the plot of pKa versus ( I )/(1 + I ) for the KHP solution, the graph holds a structure which
is of different form than the graphs in question since it denotes/records different values, however
the thing which makes it unordinary is that it contains a loop which is formed by a reduce in pKa of
the solution which causes the graph to have a drastic descent in the solutions pKa. Then for the
values of I which are recorded for the KHP solution are relatively close if not the same for all the
values of the different volumes of base added to the solution.

Hence for the plot of KHP having a irregular structure is due to the change in the Ka of the solutions
at the different volumes of the base added to the solution, however the loop could be caused by an
over titration of the base to the solution, or the mixing of the solution wasnt done efficiently in the
previous titration, or the current one, hence when the readings were taken they contained a large
difference in pKa solution.
The assumption that the plot of [H+].V versus V will cause formation of a zig-zag structure if all the
values were to be strung together was risen by the observing of the values which were recorded, as
seen above, however this is an assumption, and hence its concluded by the fact that there isnt a
large difference between the solutions values, and even though they arent the same they are within
a certain range.

Then for the plot of pKa versus ( I )/(1 + I ) the unordinary structure of the graph can be caused by
the values of I recorded for the solution being relatively close, and these values alternate from being
greater or less than the expected value, then the loop can be accounted for by a probable error
which had occurred in the reading of solutions values or an experimental error which occurred
during the procedure of the experiment.

The experimental methods that were used, to my observing, there isnt anything which can be
altered or changed. Even though there are errors which can be easily observed, there arent any
drastic changes which can be seen that change the experiments outcome. Never the less, my
observations and conclusions could be caused by a lack of understanding from me, but the theory
was used as a guide for the conduction of the procedure and the values obtained are normal for
the values which were needed.

Conclusion

However, the purpose was reached due to use of calibrated and advanced pH meter. In this
experiment, we observed that pH is the very powerful method of analysis to measure the pH
parameters of a different solution and same solutions under different ionic strength. The pH meter is
based on giving large pH values of base but less than 14 and gives acidic values less than 7 and
neutral 7. As the [H+] multiplied by V then versus v the graph decreases and there were some zigzag
form in the beginning and in the end but the in the middle was continuously decreasing.

References
1. G.J Price (1998), Thermodynamics of Chemical Process, Oxford University Press, Great Britain.

2. Green. John and Damy.Sandru, (2001), Chemical for International Baccalaureate, Second edition,
IBID press, Australia.

3. P.W.Atkins and Julio de Paula, (2000), The elements of Physical Chemistry, Oxford University Press,
Great Britain.
4. P.W.Atkins and Julio de Paula, (2006), Physical Chemistry, Oxford University Press, Great Britain.