PHYSICAL CHEMISTRY YEAR 2

LABORATORY REPORT
Experiment No.7
Determination of mean astivity coefficient and
solubility of potassium hydrogen tartrate (KHT) in
aqueous solution at 30C
Date of expt: 15 July 2008
Name: Ameerul Hazeeq Bin Hashim
Matrix No: SEW110001
Lab Patner: Amirol Husaini Bin Azmi
Matrix No: SEW110002
Group: A
Laboratory: Physical chemistry 2nd year
Lecturer: Dr. KHOO SIOW @SIEW KIAN
Date of submission report: 22 October 2012
1
AIM: To determine the mean activity coefficient and solubility of potassium hydrogen
tartarate(KHT).
RESULTS:
Preparation of 250cm
3
0.2moldm
-3
NaCl
No. of mole of NaCl =
1000
MV
=
1000
250 2 . 0
= 0.05 mol
So, mass of NaCl required = 0.05 mol 58.44 gmol
-1
= 2.922 g
Mass of NaCl obtained in the experiment = 2.960g
Preparation series of NaCl solution
Concentration of
NaCl (mol dm
-3
)
Volume of stock solution NaCl
(cm
-3
)
Volume of distilled
water(cm
-3
)
0.0000 0.0 100.0
0.0500 25.0 75.0
0.1000 50.0 50.0
0.1500 75.0 25.0
0.2000 100.0 0.0
Example calculation for preparing 100cm
-3
NaCl solution of concentration 0.0500M from
stock solution NaCl 0.2000M
M
1
V
1
= M
2
V
2
1
2 2
1
M
V M
V
=
2000 . 0
100 0500 . 0
= 25.0 cm
-3
where
M
1
= stock NaCl solution 0.2000M
M
2
= concentration of NaCl
V
1
= Volume of NaCl required
V
2
= Volume solution 100 cm
-3
2
Preparation of NaHT and NaOH
NaHT + NaOH 2Na
+
+ T
2-
+ H
2
O
1 mol NaHT = 1 mol NaOH
No. of mole of NaOH =
1000
MV
= 0.04 mol dm
-3

x 0.25 dm
-3
= 0.01 mol
So, weight of NaOH required = 0.01 mol 40 g mol
-1
= 0.40 g
Weight of NaOH used = 0.3994 g
No. of mole of NaHT= 0.01 mol
1 mol = 190.09g
0.01 mol = 0.76g
The mass of NaHT in the experiment is 0.7611g
Titration of NaOH solution with 25.0cm
3
NaHT. (Standard NaOH)
Temperature of water bath = 30.0C
Titration Burette Reading (0.08 cm
3
)
1 2 3
Final Reading 8.60 19.42 30.18
Initial Reading 18.42 30.18 40.89
Volume of
NaOH used
( cm
3
)
9.82 10.76 10.71
Average volume of NaOH used = (9.82 + 10.76 + 10.71) cm
3
= (10.43 0.02) cm
3
3
Titration of KHT inside NaCl solution with standardize NaOH
Concentration
of NaCl
solution (M)
Titration Burette Reading
( 0.08 cm
3
)
Volume of
NaOH used
(cm
3
)
Average
volume of
NaOH used
(cm
3
)
Final
Reading
Initial
Reading
0.0000 1 30.97 20.78 10.19 10.16
2 27.41 17.28 10.13
0.0500 1 22.20 11.50 10.70 10.76
2 33.02 22.20 10.82
0.1000 1 30.62 19.31 11.08 11.19
2 42.12 30.62 11.31
0.1500 1 31.56 19.21 12.35 12.36
2 7.00 19.37 12.37
0.2000 1 22.58 9.89 12.69 12.58
2 24.87 12.40 12.47
o Calculation for concentration of KHT
Assume c = concentration of KHT in NaCl = solubility of KHT
KHT (c) K
+
+ HT
-
, where [ K ] = [ HT ] = c
From equation ,
KHT + NaOH NaKT + H
2
O
1 mol KHT = 1 mol NaOH
( Assume that electrolyte fully dissociate, and no others equilibrium exist.)

Solubility KHT, c
KHT
NaOH NaOH
V
V M

----------------------------------------(1)
where volume of KHT= volume of solution pipette = 10 cm
3
Ionic strength of solution, I = c+m ------------------------------------------------(2)
where m = concentration of NaCl solution

,
_

+

2
1
2
1
1
2
log 2 ' log
I
AI
s K
s
----------------------------------------------(3)
where A = debye- Huckel constant = 0.5160 at 30C
o Concentration of KTH , s , Ionic strength , I and log Ks for different concentration of
NaCl
Concentration of
NaCl,m (moldm
-3
)
Solubility of KHT,c
(moldm
-3
)
Ionic strength ,I
(moldm
-3
)
Log K
s

0.0000 0.0409 0.0409 -2.950

0.0500 0.0434 0.0934 -2.967
0.1000 0.0451 0.1451 -2.976
0.1500 0.0498 0.1998 -2.924
0.2000 0.0507 0.2507 -2.934
4
From equation 1, 2 and 3, we can calculate the concentration of KHT,s, the ionic strength, I
and the value of Log K
s

o For NaCl 0.0000M

00 . 10
16 . 10 0403 . 0
c
0409 . 0 1
) 0409 . 0 )( 5160 . 0 ( 2
) 0409 . 0 log( 2 ' log
+

s
K
= 0.0409 moldm
-3
= -2.950
I = 0.0000 + 0.0409
= 0.0409 moldm
-3
o For NaCl 0.0500
00 . 10
76 . 10 0403 . 0
c
0934 . 0 1
) 0934 . 0 )( 5160 . 0 ( 2
) 0434 . 0 log( 2 ' log
+

s
K
= 0.0434 moldm
-3
= -2.9666
I = 0.0500 + 0.0434
= 0.0934 moldm
-3
o For NaCl 0.1000
00 . 10
19 . 11 0403 . 0
c
1451 . 0 1
) 1451 . 0 )( 5160 . 0 ( 2
) 0451 . 0 log( 2 ' log
+

s
K
= 0.0451 moldm
-3
= -2.9763
I = 0.1000 + 0.0451
= 0.1451 moldm
-3
o For NaCl 0.1500
00 . 10
36 . 12 0403 . 0
c
1998 . 0 1
) 1998 . 0 )( 5160 . 0 ( 2
) 0498 . 0 log( 2 ' log
+

s
K
= 0.0498 moldm
-3
= -2.9243
I = 0.1500 + 0.0498
= 0.1998 moldm
-3
o For NaCl 0.2000
00 . 10
58 . 12 0403 . 0
c
2507 . 0 1
) 2507 . 0 )( 5160 . 0 ( 2
) 0507 . 0 log( 2 ' log
+

s
K
= 0.0507 moldm
-3
= -2.934
I = 0.2000 + 0.0507
= 0.2507 moldm
-3
5
From the graph, log Ks against I ,
log Ks = log Ks + 2 bI
Slope of graph, -2b = 0.7309
b = -0.36545 mol
-1
dm
3
The intercept at y-axis = log K
s
log K
s
= -2.9241
K
s
= 1.1910 10
-3
mol
2
dm
-6
From the equation
2 2
t
c K
s
and the equation
bI
I
AI
+
+

t
) 1 (
log
2
1
2
1

c
K
S
2
1

1
1
]
1

,
_

+
+
t
2
1
2
1
1
log )
1
(
I
AI
I
b
o For the saturated KHT solution in NaCl of concentration 0.0000 moldm
-3
,
3
2
1
2 2 3
0409 . 0
) 10 1910 . 1 (

moldm
dm mol

1
1
]
1

+
+
0409 . 0 1
) 0409 . 0 )( 5160 . 0 (
8438 . 0 log )
0409 . 0
1
( b
= 0.8438 = 0.3185
o For the saturated KHT solution in NaCl of concentration 0.0500 moldm
-3
,
3
2
1
2 2 3
0434 . 0
) 10 2134 . 1 (

moldm
dm mol

1
1
]
1

+
+
0934 . 0 1
) 0934 . 0 )( 5160 . 0 (
7952 . 0 log )
0934 . 0
1
( b
=0.7952 = 0.2276
o For the saturated KHT solution in NaCl of concentration 0.1000 moldm
-3
,
6
3
2
1
2 2 3
0451 . 0
) 10 2134 . 1 (

moldm
dm mol

1
1
]
1

+
+
1451 . 0 1
) 1451 . 0 )( 5160 . 0 (
7652 . 0 log )
1451 . 0
1
( b
= 0.7652 = 0.1799
o For the saturated KHT solution in NaCl of concentration 0.1500 moldm
-3
,
3
2
1
2 2 3
0498 . 0
) 10 2134 . 1 (

moldm
dm mol

1
1
]
1

+
+
1998 . 0 1
) 1998 . 0 )( 5160 . 0 (
6930 . 0 log )
1998 . 0
1
( b
= 0.6930 = 0.0256
o For the saturated KHT solution in NaCl of concentration 0.2000 moldm
-3
,

3
2
1
2 2 3
0507 . 0
) 10 2134 . 1 (

moldm
dm mol

1
1
]
1

+
+
2507 . 0 1
) 2507 . 0 )( 5160 . 0 (
6807 . 0 log )
2507 . 0
1
( b
= 0.6807 = 0.0204
Concentration of
NaCl, m (moldm
-3
)
Ionic strength,
I = c+m (moldm
-3
)
Activity
coefficient,
t
Parameter b
(mol
-1
dm
3
)
0.0000 0.0431 0.8438 0.3185
0.0500 0.0974 0.7952 0.2276
0.1000 0.1490 0.7652 0.1799
0.1500 0.2000 0.6930 0.0256
0.2000 0.2519 0.6807 0.0204
Average value of b = ( 0.3185 )+( 0.2276 )+( 0.1799 )+( 0.0256 )+( 0.0204 )
5
= 0.1544
KHT (s) K
+
(aq) +HT
-
(aq)
G = G
product
G
reactants
= [G

product
+ RT In(a
k+
+ a
HT
-)] [G

reactant
+ RT In(a
KHT
)]
= G

+ RT In [(a
K+ .
a
HT
-)/a
KHT
]
Since KHT is in solid form, a
KHT
= 1
K
s
= a
K+
. a
HT
-
So, G = G

+ RT In K
s
At equilibrium, G = 0
G

= -RT In K
s
= -(8.314 J K
-1
mol
-1
) x (303 K) x In(1.190 10
-3
mol
2
dm
-6
)
= 16601.75 J/mol
= 16.60175 kJ/mol
Discussion:
7
Based on the experiment results, we found that KHT only slightly soluble in water
compared to NaCl. The solubility constant of potassium hydrogen tartrate depends on some
factors. In this experiment, the variation of activity coefficients of the ionic salt is caused by
the charge of the ionic strength of the electrolytes is the main factor that affect the solubility
constant of potassium hydrogen tartrate.
In the experiment, we found that the solubility of KHT and the ionic strength increase
when the concentration of NaCl increase. The reason is NaCl is a strong electrolit that can
dissociate 100% in the solution.
NaCl Na
+
+ Cl
-
The increasing of the concentration of NaCl causes the Na
+
and Cl
-
ions to increase
and cause the density charge of the solution increase. The polarity of the solution make the
dissociation of KHT become higher. Therefore, the solubility of KHT increase.
The activity coefficient,
t
of KHT increases when the concentration of the solution
decreases. This is because the interaction of ions increasewhen the concentration of solution
increase. It decrease the potential and thus
t
also decrease.According to Debye-Huckel rules,

t
1 when dilution is infinite.
Phenolphthalein was added into the NaCl solution so that we could observe the purple
colour solution (alkali) change to colourless (acid). We stop the titration after we obtaine the
colourless solution because the end- point colour is pale pink. Therefore, we have to stop
immediately after obtaine the colourless solution since we could not achieve the exact end-
point colour.
Some precautions can be carried out during the experiment:
i. While pipetting the KHT solutions in NaCl , a tube containing cotton filter is
placed at the end of the pipette to prevent solid KHT from being drawn into the
pipette.
ii. The standardized pipette must be at the same temperature as the KHT solution
to prevent precipitation of KHT inside the pipette cause the deviation on the value of
volume NaOH used.
Questions:
i. G = H-TS
G = H- (TS + ST)
= H - TS Where T = 0 at constant temperature
G = G + RT In K
s
RT In K
s
= H

- TS

R
S
RT
H
InK
s

is compared with y = mx + c
If a graph In K
s
against 1/T is plot, a linear graph will be obtained,
where gradient =
R
H

and y-intercept =
R
S

Therefore, H

and S

could be determined at constant temperature where R = 8.314 JK

-
1
mol
-1
.
ii. The activity of KHT (solid state) is assumed to be equal 1 in order to compute
G

.
8
Conclusion:
Solubility constant of KHT, K
s
= 1.19 10
-3
mol
2
dm
-6
Reference:
1. Atkins, P.W (1998), Physical chemistry, 7
th
ed. Oxford
9