Date: 18/12/2017

Experiment number: 04
Experiment: Determination of the thermodynamic solubility product of potassium hydrogen
tartrate (KHT) at 35Ċ
THEORY
Potassium hydrogen tartrate is a mono-basic salt with the chemical formula 𝐾 + [OCC-CH(OH)-
CH(OH)-COOH].for simplicity the anion in the compound is denoted by 𝐻𝑇 − .KHT dissociated in
water according to the equation.
𝐾𝐻𝑇 ⇌ 𝐾 + + 𝐻𝑇 − ………………. (1)
By definition the concentration solubility product of KHT is given by
𝐾𝑐 = [𝐾 + ][𝐻𝑇 − ] …………………. (2)
The thermodynamic solubility product of KHT is given by
𝐾𝑇 = 𝑎𝐾+ + 𝑎𝐻𝑇− …………………. (3)
Where, 𝑎𝑥 is the activity of the ionic species X.
If we denote the activity coefficient of ionic species X by 𝛾𝑥 , then we have
𝐾𝑇 = (𝛾𝐾+ [𝐾 + ])(𝛾𝐻𝑇− [𝐻𝑇 − ]) = (𝛾𝐾+ 𝛾𝐻𝑇− )[𝐾 + ][𝐻𝑇 − ]…………………. (4)
However, we know that the mean active coefficient, 𝞬±, of KHT is defined by
𝛾±2 = 𝛾𝐾+ 𝛾𝐻𝑇− ………………… (5a)
Now equation (2), (4) and (5a) gives
𝐾𝑇 = 𝛾±2 𝐾𝑐 ………………….. (5b)
Which, in turn may be written in two forms
𝑙𝑜𝑔10 (𝐾𝑐 ) = −2𝑙𝑜𝑔10 (𝛾𝐾+ ) + 𝑙𝑜𝑔10 (𝐾𝑇 )…………….. (6a)

𝐾𝑇
𝞬± = √ …………………. (6b)
𝐾𝑐

Debye-Hukel extended law gives us the relationship between ionic strength, 𝐼 and the mean
activity coefficient 𝞬±, via,
𝐴|𝑍𝐾+ 𝑍𝐻𝑇− |√𝐼
𝑙𝑜𝑔10 (𝛾 ±) = − ……………. (7)
1+𝛼𝛽√𝐼
Where, A, a and B are constants and 𝑍𝑥 is the charge number of the ionic species X. the ionic
strength 𝐼 is defined by.
1
𝑛
𝐼 = 𝛴𝑖=1 𝐶𝑖 𝑍𝑖2 ………………… (8)
2

Where, 𝐶𝑥 is the molar concentration of ionic species X and the summation runs over all the
ionic species present in the solution.
In an aqueous solution at room temperature (35Ċ) for KHT we have
0.509√𝐼
𝑙𝑜𝑔10 (𝞬±) = − ………. (9)
1+1.25√𝐼
Equation (7) and (9) give
0.509√𝐼
𝑙𝑜𝑔10 𝐾𝑐 = 2 [1+1.25 𝐼] + 𝑙𝑜𝑔10 (𝐾𝑇 )…….. (10)
√

Apparatus and chemicals

100 ml of 0.5 𝑚𝑜𝑙𝑑𝑚−3 𝑁𝑎2 𝑆𝑂4 , A (15 𝑔 𝑁𝑎2 𝑆𝑂4 )
150 ml of 0.04 𝑚𝑜𝑙𝑑𝑚−3 𝑁𝑎𝑂𝐻 solution, B (1 𝑔 𝑁𝑎𝑂𝐻)
Potassium hydrogen tartrate (KHT), (5𝑔)
Phenolphthalein
4, 250 ml-stoppered bottles
5, 250 ml- conical flasks
Burette with stand and porcelain tile
25 ml calibrated pipette

PROCEDURE
A sodium sulphate solution of concentrations 0.1 𝑚𝑜𝑙𝑑𝑚−3 and 0.05 𝑚𝑜𝑙𝑑𝑚−3 was prepared by
pipetting 20.00 𝑐𝑚3 and 10.00 𝑐𝑚3 of 0.5 𝑚𝑜𝑙𝑑𝑚−3 sodium sulphate solution in to two 100 ml
volumetric flasks provided, and filling up to the mark with distilled water. Solutions were labeled
as C and D respectively. A water bath was prepared at room temperature. Four stoppered
bottles and four conical flasks were labeled as 1, 2, 3 and 4. Stoppered bottles were cleaned and
rinsed with little acetone and dried the above mentioned stoppered bottles.
1 𝑔 of KHT was added into each of four stoppered bottles. Next 50 𝑐𝑚3 of distilled water was
added (measured using a measuring cylinder) into bottle 1, similarly 50 𝑐𝑚3 of solution A, B, C
and D into bottles 2, 3 and 4 respectively. Bottles were swirled well and kept in the water bath.
The solution in each bottle was swirled regularly over a period of about 10-15 minutes in order
to permit to reach the equilibrium conditions. If the solid in a bottle was dissolved completely
then added some more KHT until obtain a saturated solution.
10 𝑐𝑚3 of the solution in bottle was filtered into conical flask 1. It was swirled and discard this
filtrate. Continue filtering. The same procedure as described in above steps was used to filter
the solutions in bottle 2, 3 and 4 into appropriate conical flask. (New filter paper was used for
each filter).
10.00 𝑐𝑚3 Of solution in flask 1 was pipetted out in 5th conical flask and titrated with the 𝑁𝑎𝑂𝐻
solution using phenolpthalein as indicator. The titration flask was rinsed and repeat the above
step so that titration results in duplicate.

Results and calculations

Conical flask No: Initial burette Final burette Consumed Average volume/
3
reading / 𝑐𝑚 reading/ 𝑐𝑚3 volume of 𝑐𝑚3
𝑁𝑎𝑂𝐻/ 𝑐𝑚3
0.00 8.00 8.00
① 0.00 7.90 7.90 7.95
0.00 15.00 15.00
② 0.00 14.80 14.80 14.90
0.00 10.60 10.60
③ 0.00 10.60 10.60 10.60
0.00 9.40 9.40
④ 0.00 9.50 9.50 9.45
01.
+ −
𝐾𝐻𝑇(𝒂𝒒) ⇌ 𝐾(𝒂𝒒) + 𝐻𝑇(𝑎𝑞)
−
One mole of sodium hydroxide neutralizes one mole of 𝐻𝑇(𝑎𝑞) ions.

According to 1st titration

Concentration of 𝑁𝑎𝑂𝐻 = 0.04 𝑚𝑜𝑙𝑑𝑚−3
Average volume of consumed 𝑁𝑎𝑂𝐻 = 7.95 𝑐𝑚3
0.04 𝑚𝑜𝑙 3
Consumed moles of 𝑁𝑎𝑂𝐻 = ⨯7.95 𝑐𝑚
1000 𝑐𝑚3
= 3.18⨯10−4 𝑚𝑜𝑙
Moles of 𝐻𝑇 − in 10.00 𝑐𝑚3 = 3.18⨯10−4 𝑚𝑜𝑙
3.18⨯10−4
So, concentration of 𝐻𝑇 − = ⨯1000.00 𝑐𝑚 3
10.00 𝑐𝑚3
= 0.0318 𝑚𝑜𝑙𝑑𝑚−3
𝐾𝑐 = [𝐾 + ][𝐻𝑇 − ]
𝐾𝑐 = [0.0318 𝑚𝑜𝑙𝑑𝑚−3 ] [ 0.0318 𝑚𝑜𝑙𝑑𝑚−3 ]
𝐾𝑐 = 1.011⨯10−3 𝑚𝑜𝑙 2 𝑑𝑚−6

According to 2nd titration

Concentration of 𝑁𝑎𝑂𝐻 = 0.04 𝑚𝑜𝑙𝑑𝑚−3
Average volume of consumed 𝑁𝑎𝑂𝐻 = 14.90 𝑐𝑚3
0.04 𝑚𝑜𝑙
Consumed moles of 𝑁𝑎𝑂𝐻 = ⨯14.90 𝑐𝑚3
1000 𝑐𝑚3
= 5.96⨯10−4 𝑚𝑜𝑙
Moles of 𝐻𝑇 − in 10.00 𝑐𝑚3 = 5.96⨯10−4 𝑚𝑜𝑙
−
5.96⨯10−4
So, concentration of 𝐻𝑇 = ⨯1000.00 𝑐𝑚3
10.00 𝑐𝑚3
= 0.0596 𝑚𝑜𝑙𝑑𝑚−3
𝐾𝑐 = [𝐾 + ][𝐻𝑇 − ]
𝐾𝑐 = [0.0596 𝑚𝑜𝑙𝑑𝑚−3 ] [ 0.0596 𝑚𝑜𝑙𝑑𝑚−3 ]
𝐾𝑐 = 3.552⨯10−3 𝑚𝑜𝑙 2 𝑑𝑚−6
According to 3rd titration
Concentration of 𝑁𝑎𝑂𝐻 = 0.04 𝑚𝑜𝑙𝑑𝑚−3
Average volume of consumed 𝑁𝑎𝑂𝐻 = 10.60 𝑐𝑚3
0.04 𝑚𝑜𝑙 3
Consumed moles of 𝑁𝑎𝑂𝐻 = ⨯10.60 𝑐𝑚
1000 𝑐𝑚3
= 4.24⨯10−4 𝑚𝑜𝑙
Moles of 𝐻𝑇 − in 10.00 𝑐𝑚3 = 5.96⨯10−4 𝑚𝑜𝑙
−
4.24⨯10−4 3
So, concentration of 𝐻𝑇 = ⨯1000.00 𝑐𝑚
10.00 𝑐𝑚3
= 0.0424 𝑚𝑜𝑙𝑑𝑚−3
𝐾𝑐 = [𝐾 + ][𝐻𝑇 − ]
𝐾𝑐 = [0.0424 𝑚𝑜𝑙𝑑𝑚−3 ] [ 0.0424 𝑚𝑜𝑙𝑑𝑚−3 ]
𝐾𝑐 = 1.797⨯10−3 𝑚𝑜𝑙 2 𝑑𝑚−6

According to 4th titration

Concentration of 𝑁𝑎𝑂𝐻 = 0.04 𝑚𝑜𝑙𝑑𝑚−3
Average volume of consumed 𝑁𝑎𝑂𝐻 = 9.45 𝑐𝑚3
0.04 𝑚𝑜𝑙 3
Consumed moles of 𝑁𝑎𝑂𝐻 = ⨯9.45 𝑐𝑚
1000 𝑐𝑚3
= 3.78⨯10−4 𝑚𝑜𝑙
Moles of 𝐻𝑇 − in 10.00 𝑐𝑚3 = 3.78⨯10−4 𝑚𝑜𝑙
−
3.78⨯10−4 3
So, concentration of 𝐻𝑇 = ⨯1000.00 𝑐𝑚
10.00 𝑐𝑚3
= 0.0378 𝑚𝑜𝑙𝑑𝑚−3
𝐾𝑐 = [𝐾 + ][𝐻𝑇 − ]
𝐾𝑐 = [0.0378 𝑚𝑜𝑙𝑑𝑚−3 ] [ 0.0378 𝑚𝑜𝑙𝑑𝑚−3 ]
𝐾𝑐 = 1.428⨯10−3 𝑚𝑜𝑙 2 𝑑𝑚−6

02.
1 𝑛
𝐼= 𝛴𝑖=1 𝐶𝑖 𝑍𝑖2
2
Flask ① (distilled water)

1
𝐼 = ([𝐶𝐾⁺ (𝑍𝐾⁺ )2 ] + [𝐶𝐻𝑇 ¯ (𝑍𝐻𝑇 ¯ )2 ])
2
1
= ([0.0318⨯(+1)²]+[0.0318⨯(-1)²])
2
= 0.0318 𝑚𝑜𝑙𝑑𝑚¯³
Flask ② (0.5 M 𝑁𝑎2 𝑆𝑂4 )

𝑁𝑎2 𝑆𝑂4 ⟶ 2𝑁𝑎+ + 𝑆𝑂4−2

0.5 M …….. ……..
…….. 1.0 M 0.5 M
1
𝐼 = ([𝐶𝑁𝑎⁺ (𝑍𝑁𝑎⁺ )]+[𝐶𝑆𝑂4−2 (𝑍𝑆𝑂4−2 )]+ [𝐶𝐾⁺ (𝑍𝐾⁺ )2 ] + [𝐶𝐻𝑇 ¯ (𝑍𝐻𝑇 ¯ )2 ])
2
1
𝐼 = ([1.0⨯(+1)²]+[0.5⨯(-2)²]+[0.059⨯(+1)²]+[0.059⨯(-1)²])
2

= 1.5596 moldm¯³

Flask ③ (0.1 M 𝑁𝑎2 𝑆𝑂4 )

𝑁𝑎2 𝑆𝑂4 ⟶ 2𝑁𝑎+ + 𝑆𝑂4−2

0.1 M …….. ……..
…….. 0.2 M 0.1 M
1
𝐼 = ([𝐶𝑁𝑎⁺ (𝑍𝑁𝑎⁺ )]+[𝐶𝑆𝑂4−2 (𝑍𝑆𝑂4−2 )]+ [𝐶𝐾⁺ (𝑍𝐾⁺ )2 ] + [𝐶𝐻𝑇 ¯ (𝑍𝐻𝑇 ¯ )2 ])
2
1
𝐼 = ([0.2⨯(+1)²]+[0.1⨯(-2)²]+[0.0424⨯(+1)²]+[0.0424⨯(-1)²])
2

= 0.3424 moldm¯³

Flask ④ (0.05 M 𝑁𝑎2 𝑆𝑂4 )

𝑁𝑎2 𝑆𝑂4 ⟶ 2𝑁𝑎+ + 𝑆𝑂4−2

0.05 M …….. ……..
…….. 0.1 M 0.05 M
1
𝐼 = ([𝐶𝑁𝑎⁺ (𝑍𝑁𝑎⁺ )]+[𝐶𝑆𝑂4−2 (𝑍𝑆𝑂4−2 )]+ [𝐶𝐾⁺ (𝑍𝐾⁺ )2 ] + [𝐶𝐻𝑇 ¯ (𝑍𝐻𝑇 ¯ )2 ])
2
1
𝐼 = ([0.1⨯(+1)²]+[0.05⨯(-2)²]+[0.0378⨯(+1)²]+[0.0378⨯(-1)²])
2

= 0.1878 moldm¯³
03.
0.509√𝐼
[ ]
1 + 1.25√𝐼
For solution① For solution③
0.509√0.0318 0.509√0.3424
[1+1.25 ]= 0.074 [1+1.25 ]= 0.161
√ 0.0318 √0.3424

For solution② For solution④

0.509√1.56 0.509√0.1878
[1+1.25 ]= 0.247 [1+1.25 ]= 0.142
√ 1.56 √0.1878

04.

0.509√𝐼
𝑙𝑜𝑔10 𝐾𝑐 = 2 [ ] + 𝑙𝑜𝑔10 (𝐾𝑇 )
1 + 1.25√𝐼
↓ ↓ ↓ ↓
Y = m x + c

Solution NO: 𝐾𝑐 (mol²dm¯⁶)⨯10¯³ 𝑙𝑜𝑔10 𝐾𝑐 (Y) [

0.509√𝐼
] (x)
1+1.25√𝐼
① 1.011 -2.99 0.074
② 3.552 -2.44 0.247
③ 1.797 -2.74 0.161
④ 1.428 -2.85 0.142
𝑌̅ = -2.75 𝑋̅ = 0.16

According to graph
Intercept (C) = log₁₀ (𝐾𝑇 ) = -3.12
So, 𝐾𝑇 = 7.585⨯10ˉ⁴
05.

𝐼/ 𝑚𝑜𝑙𝑑𝑚¯³ [
0.509√𝐼
] 𝑙𝑜𝑔10 𝐾𝑐 𝐾𝑐 (mol²dm¯⁶)
1+1.25√𝐼
0.01 0.0425 -2.90 1.258⨯10ˉ³
0.03 0.0724 -3.00 1.000⨯10ˉ³
0.1 0.115 -2.87 1.348⨯10ˉ³
0.3 0.167 -2.73 1.862⨯10ˉ³
1.0 0.240 -2.52 3.020⨯10ˉ³

06.

𝐾𝑇 = 𝛾±2 𝐾𝑐

𝐾𝑇
𝞬± = √
𝐾𝑐

Mean activity coefficient (𝞬±) in 𝐼= 0.01 Mean activity coefficient (𝞬±) in 𝐼= 0.1

7.585⨯10¯⁴ 7.585⨯10¯⁴
𝞬± = √ = 0.77 𝞬± = √ = 0.75
1.258⨯10¯³ 1.348⨯10¯³

Mean activity coefficient (𝞬±) in 𝐼= 0.3

Mean activity coefficient (𝞬±) in 𝐼= 0.03

7.585⨯10¯⁴
7.585⨯10¯⁴ 𝞬± = √ = 0.63
𝞬± = √ = 0.87 1.862⨯10¯³
1.000⨯10¯³

Mean activity coefficient (𝞬±) in 𝐼= 1.0

7.585⨯10¯⁴
𝞬± = √ = 0.50
3.020⨯10¯³
 Ionic strength (𝐼) Mean activity coefficient (𝞬±)

0.01 0.77

0.03 0.87

0.10 0.75

0.30 0.63

1.00 0.50

Discussion

The most possible errors that can happen in this experiment are due to human errors. Spilling
part of solution, kind of errors that caused by eye’s inability to read the exact level of liquid in a
graduated cylinder, then it’s a random error. The water bath should be kept at constant
temperature (25Ċ) to minimize the temperature error the water should always be above the
solution level inside the bottle. The bottles should be shaken from time to time distribute the
temperature. It always advisable to discard the first few ml of our sample as it will reduce the
chance of drug adsorption by filter paper., if any.

The 1st 10 ml of the solution is taken to saturate the filter paper. Then the rest of the solution is
allowed to filter through the filter paper.

{𝐶}ᶜ{𝐷}ᵈ
𝐾𝐶 =
{𝐴}ᵃ{𝐵}ᵇ

Where {A}, {B}, {C}, {D} are activity of the chemical species. Activity is one product of
concentration and activity coefficient. 𝐾𝐶 Is determined in a medium of high ionic strength. In
such circumstances the quotient of the activity coefficient is effectively constant. And one
equilibrium constant is taken to be concentration quotient.