ABSTRACT

The objective of this experiment is to study the relationship of the solubility product constant
(Ksp) to the change of Gibbs free energy (G) from the solution process of barium nitrate.
There are two parts in this experiment where part 1 the Ksp value was calculate based on
the room temperature. The value for Ksp calculated is 1.4292. Hence, in part 2 is the
calculation based on the function of temperature that vary to the Ksp value. So the value of
Ksp was calculated is 0.1822.
INTRODUCTION
Le Chateliers principle said when a chemical system at equilibrium is disturbed, it retains
equilibrium by undergoing a net reaction that reduces the effect of disturbance (Silberberg:
principles of general chemistry). Standard thermodynamic functions of reaction is know how
to use thermodynamic data to find H, S, G when a system of constant composition
undergoes changes in temperature and pressure, (ira N,levine: physical chemistry 3th
edition). So here, in order to know standard state we must know how to calculates the
change in H,S, and G for a process that start with separated reactant, each in a specified
state at temperature T, called its standard state.
So for the barium nitrate the solubility product constant is defined by Ksp. When barium
nitrate in pure water so the value of molar solubility = 2S, which is its for one barium nitrate
complex there are 2 nitrate ions. So, the Ksp value can be written as:
Ksp = (S) (2S)
2
= 4S
3
When the salt was dissolved in the solution that have an additional source of nitrate ion
example 0.5 M HNO3, so there is two source of nitrate ions come from. Hence the equation
of Ksp written as:
Ksp = (s) (2s + 0.5)
2

So the solubility of product constant is related to the Gibbs free energy:
ln Ksp = -G/RT
this equation is valid for the very dilute solution since G = H TS. Besided, it also can
calculate as ln Ksp = (-H/RT) + (S/R). there also a way to calculated it by using the
plotted graph ln Ksp versus 1/T so the general equation is : ln Ksp = (-H/RT) + C.



APPARATUS/MATERIALS
- Barium nitrate Ba(NO
3
)
2

- 0.5 M nitric acid HNO
3

- 50 mL clear glass volumetric pipette
- 10 mL clear glass volumetric pipette
- Thermometer
- 100 mL, 250 mL, 500 mL
- Stop watch
- Hot plate
- Glass rod
- Label
PROCEDURE
Part A (i)
1. A clean, dry 250 mL beaker was weighed to 0.01 g.
2. 5 g of solid Ba(NO
3
)
2
was placed in the beaker and was weighed to 0.01 g.
3. 50.0 mL off deionized water was added with volumetric pipette.
4. Solution was stirred about 10 minutes.
5. The temperature of the solution was measured, and the saturated solution was
decanted as much as possible into waste water container.
6. The beaker and the contents was heat on the hot plate.
7. The solution was evaporated to dryness about 5 minutes. The heating rate was
reduced as evaporation near to completed.
8. The beaker and the contents were let to cool at room temperature, and then the
beaker and the contents was weighed to 0.01 g.
Part A (ii)
1. The procedure in Part A (i) was repeated except substitute the 50.0 mL deionised
water with 50.0 mL of 0.5 M HNO
3
and was evaporated the contents in the fume
hood.
Part B
1. Eight dry, clean 100 mL beakers was label and weighed to 0.0 g.
2. 40 g of solid Ba(NO
3
)
2
was placed into 500 mL beaker and was weighed to 0.0 g.
3. 200 mL of deionized water was added with volumetric pipettes.
4. The solution with stirring was heat on hot plate until the temperature of the solution is
about 70C.
5. As soon as the solution was cooled to 45 C, it was quickly decanted about 10 mL of
the solution into one of the pre-weighed 100 mL beakers, the temperature was
recorded.
6. The temperature of the solution was monitoring continuously.
7. When the temperature was cooled to 40 C, another 10 mL of solution was decanted
into a second pre- weighed 100 mL beaker. The step was repeated when the
solutions cooled to 35, 30, 25, 20, 15, and 10C.
8. The last temperature was attained by placed the solution into ice bath. Each of the
solution in 100 mL beakers was allowed to come to room temperature and was
weighed to 0.01g.
9. Each of decant solution was heat on hot plate and was evaporated to dryness.
10. The heating rate was reduced as evaporation near completion to avoid splattering.
11. The beakers were allowed to cool at room temperature and each beaker and the
remaining residue was weighed to 0.01 g.

DATA AND RESULT
Results for Part A:

Part
Temperature of the
solution (
0
C)
Mass of the empty beaker
(g)
Mass of beaker + dry Ba(NO
3
)
2

(g)
A (i) 28.80 90.21 90.54
A (ii) 28.80 101.46 103.68

Results for Part B:
Temperature of
the solution (
0
C)
Mass of the empty
beaker (g)
Mass of beaker +
saturated solution (g)
Mass of beaker +
dry Ba(NO
3
)
2
(g)
45 47.19 57.62 48.70
40 59.43 70.39 61.07
35 56.22 67.02 57.85
30 47.34 58.22 48.35
25 52.53 63.23 53.81
20 57.27 68.07 58.51
15 48.31 58.98 49.18
10 59.85 70.38 60.87

Process data:
Part A:

Part Temperature of the solution (
0
C) Mass of dry Ba(NO
3
)
2
(g)
A (i) 28.80 0.33
A (ii) 28.80 2.22

Part B:

Temperature of the solution
(
0
C)
Mass of H
2
O
(g)
Mass of dry Ba(NO
3
)
2

(g)
45 10.43 1.51
40 10.96 1.64
35 10.80 1.63
30 10.88 1.01
25 10.70 1.28
20 10.80 1.24
15 10.67 0.87
10 10.53 1.02











CALCULATION
1. Calculate the K
sp
and K
sp
for Part A (i) and (ii), respectively.
Part A (i):
Molar solubility, M = initial mass Ba(NO
3
)
2
mass Ba(NO
3
)
2

(0.050 L) (molar mass Ba(NO
3
)
2
)
= (5.0 g) 0.33 g
(0.050 L) (261.37 g/mol)
= 0.3573
K
sp
= (M) (2M)
2

= 4M
3

= 4(0.3573)
= 1.4292
Part A (ii):
Molar solubility, M = initial mass Ba(NO
3
)
2
mass Ba(NO
3
)
2

(0.050 L) (molar mass Ba(NO
3
)
2
)
= (5.0 g) 2.22 g
(0.050 L) (261.37 g/mol)
= 0.2127
K
sp
= (M) (2M + 0.5)
2

= (0.2127) [(2)( 0.2127) + 0.5]
2

= 0.1822




2. Calculate the values of K
sp
at 8 different temperatures.

Molal solubility, m = [mass Ba(NO
3
)
2
] (1000 g/kg)
[molar mass Ba(NO
3
)
2
] (mass H
2
O)

K
sp
= 4m
3


T (
0
C) m K
sp

45 m = (1.51 g) (1000 g/kg)
(261.37 g/mol) (10.43 g)
= 0.5539
K
sp
= 4m
3

= (0.5539)
3

= 0.6798
40 m = (1.64 g) (1000 g/kg)
(261.37 g/mol) (10.96 g)
= 0.5725
K
sp
= 4m
3

= (0.5725)
3
= 0.7506
35 m = (1.63 g) (1000 g/kg)
(261.37 g/mol) (10.80 g)
= 0.5774
K
sp
= 4m
3

= (0.5774)
3

= 0.7700
30 m = (1.01 g) (1000 g/kg)
(261.37 g/mol) (10.88 g)
= 0.3552
K
sp
= 4m
3

= (0.3552)
3

= 0.1793
25 m = (1.28g) (1000 g/kg)
(261.37 g/mol) (10.70g)
= 0.4577
K
sp
= 4m
3

= (0.4577)
3

= 0.3835
20 m = (1.24 g) (1000 g/kg)
(261.37 g/mol) (10.80 g)
= 0.4393
K
sp
= 4m
3

= (0.4393)
3

= 0.3391
15 m = (0.87 g) (1000 g/kg)
(261.37 g/mol) (10.67 g)
= 0.3120
K
sp
= 4m
3

= (0.3120)
3

= 0.1215
10 m = (1.02 g) (1000 g/kg)
(261.37 g/mol) (10.53 g)
= 0.3706
K
sp
= 4m
3

= (0.3706)
3

= 0.2036

3. Calculate and tabulate the values of In K
sp
and 1/T.

K
sp
In K
sp
T (K) 1/T (K
-1
)
0.6798 -0.39 318 3.14 x 10
-3

0.7506 -0.29 313 3.19 x 10
-3

0.7700 -0.26 308 3.25 x 10
-3

0.1793 -1.72 303 3.30 x 10
-3

0.3835 -0.96 298 3.36 x 10
-3

0.3391 -1.08 293 3.41 x 10
-3

0.1215 -2.11 288 3.47 x 10
-3

0.2036 -1.59 283 3.53 x 10
-3



4. Sketch a plot of In K
sp
versus 1/T. from the slope and intercept, calculate H and S,
respectively for the solution process.


From the graph;
Slope = -0.1012
Intercept = -9.5321
y = -0.1012x - 9.5321
R = 0.0309
-12
-10
-8
-6
-4
-2
0
0 2 4 6 8 10
l
n

K
s
p

1/T
ln Ksp
Linear (ln Ksp)
H = - slope x R
= - (-0.1012) (8.3145 J K
-1
mol
-1
)
= 0.8414 J mol
-1


S= intercept x R
= (-9.5321) ((8.3145 J K
-1
mol
-1
)
= -79.255 J mol
-1
K
-1


5. Calculate G for the solubility of Ba(NO
3
)
2
at 25
0
C. H and S are constant with
variation of temperature.

G = H - TS
= (0.8414 J mol
-1
) (298 K) (-79.255 J mol
-1
K
-1
)
= 23 618.8 J mol
-1

6. Calculate the G
theory
from the standard data for the above solution process.

In K
sp
= H + S
RT R
= 0.8414 J mol
-1
+ -79.255 J mol
-1
K
-1

(8.3145 J K
-1
mol
-1
) (298 K) 298 K
= -0.2656

G
theory
= -In K
sp
(RT)
= - (-0.2656) (8.3145 J K
-1
mol
-1
) (298 K)
= 658.083 J mol
-1

DISCUSSION
In this experiment, there are two parts which are Part A (i and ii) and Part B. Based on
Calculation 1 above, the value of K
sp
for Part A (i) and (ii) are different that are 1.4292 and
0.1822. Both of these values should be same since K
sp
does not affected by the same
temperature of the solutions. However, the values of K
sp
for both solutions are not equal
even their temperatures are same (28.8
0
C). This condition occurred due to the errors either
personal or instrument errors. One of the sources of personal errors is lacking of skills while
handling the apparatus. Others, dry Ba(NO
3
)
2
and beaker may not be cooled enough before
they are weighed.
Calculation 2 above shows the values of K
sp
at 8 different temperatures for Part B. The table
shows K
sp
changes as temperature changes.
The slope and intercept can be obtained from a plot of In K
sp
versus 1/T as shown on from
the graph plotted. H and S can be calculated by using these equations:
H = -(slope)(R) and S = (intercept)(R)
The value of H is 0.8414 J mol
-1
. It is a positive value and it shows that this reaction is
endothermic. The heat of the surrounding is absorbed by the system. However, it does not
agree with Le Chateliers Principle. This principle states that, decreasing temperature of the
system will favor the exothermic reaction whereby the system released heat to the
surrounding thus produce negative value of H.
The entropy change for the solution process, S is in negative value that is 79.255 J mol
-1

K
-1
. It means the reaction in this experiment is less disorder or more ordered.
G
experiment
that calculated in Calculation 5 is 23 618.8 J mol
-1
is different with G
theory
that
calculated in Calculation 6 above; 658.083 J mol
-1
. The positive values of both G show that
the process that occurred in this experiment is non-spontaneous since H is more than 0
and S is less than zero.
There might be some errors in this experiment. There are splattering occur while heating the
decanted solution thus it effect the mass of the Ba(NO
3
)
2
which might reduce the real mass
of it. The beaker and its content may not cooled enough after they are heated on the hot
plate. The heat that come from the beaker or content may affect the actual mass of Ba(NO
3
)
2

too. This will give the incorrect values for K
sp
then it affected the values of H, S and G.


QUESTION
1. What is the value of K
sp
for Ag
2
SO
4
if 5.4g is soluble in 1 L of water?
Molar solubility, M = mass Ag
2
SO
4

(1 L) (molar mass Ag
2
SO
4
)

= 5.4 g
(1L)(311.87 g/mol)
= 0.0173
K
sp
= 4M
3

= 4(0.0173)
3

= 2.076 X 10
-5

2. The molar solubility of Pb(IO
3
)
2
at 26 C is 4.0 X 10
-5
. Determine the K
sp
of lead (II)
iodate
K
sp
= 4M
3

= 4(4.0 X 10
-5
)
3

= 2.56X10
-13

3. Balance the chemical equations and predict the spontaneity of a reaction for the
following 4 cases. Explain your answer.
Case 1 and case 4
CH
4
+ 2O
2
CO
2
+ 2H
2
O
CO
2
+ 2H
2
O CH
4
+ 2O
2

: Spontaneous process which is it is a reversible process in case 1 there is
increase in randomness or increase in disorder. Hence, the case 4 it is non-
spontaneous because it less disorder.
Case 2 and case 3
H2O (s) H2O(l)
: The process change the states form solid to liquid make particles more
randomness and it is spontaneous process.
H2O (g) H2O (l)
: it is non-spontaneous process where it become less disorder.



CONCLUSION
As the conclusion the value for ksp obtained in the part I and part (ii) is not same. From the
result we get its not agree with the Le Chateliers Principle.

REFERENCES
1. Standard Thermodynamic Functions of Reaction, (page 141- 164).Levin, Ira N.
(1988). Physical Chemistry. Third edition. Singapore: McGraw Hill.(ISBN 0-07-
100563-3).
2. Reaction Condition and the Equilibrium state: Le Chateliers Principle, (page 573-
580).Martin S. Silberberg. (2010). Principles Of General Chemistry. Second edition.
New York: McGraw- Hill. (ISBN 978- 0- 07- 017263- 0).
3. Entropy, (page328- 350).Yunus A.Cengel, Michael A.Boles (2011). Thermodynamics
an engineering approach. Seventh edition.New York: McGraw- Hill. (ISBN 978- 007-
131111-3).
4. Energy and Equilibrium, (page 123- 162).D.Eisenberg, D. Crothers (1979). Physical
Chemistry with applications to the life Sciences. Philippines: Benjamin. (ISBN 0-
8053-2402-x).