KWAME NKRUMAH UNIVERSITY OF SCIENCE

AND TECHNOLOGY

COLLEGE OF ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING

TITLE: ENTHALPY AND ENTROPY OF AN

AQUEOUS BORAX SOLUTION
NAME:

KWAKYI KOFI BOSOMPEM

COURSE:

BSC. CHEMICAL ENGINEERING

YEAR:

SECOND YEAR

EXPERIMENT NO. : P.1.2.2.

I.D. NO:

9664813

DEMONSTRATOR:

J. Y. GYESI

DATE:

4TH FEBRUARY, 2015

Aims and Objectives

1. To measure the enthalpy (H) and entropy (S) of an aqueous

solution of borax (sodium tetraborate decahydrate) from the
temperature dependence of the equilibrium constant for the
dissolution reaction of borax in water.
2. To study a system of an aqueous solution of borax.

SAFETY PRECAUTIONS
3. Safety glasses and aprons must be worn at all times in the lab.
4. Dilute solutions of acid, other chemicals and experimental apparatus
should be handled with care since spillage and breakages can cause
injuries.
5. When using volumetric pipettes, always use a pipette bulb, never
pipette by mouth.

INTRODUCTION/THEORY
The changes in free energy (G), enthalpy (H), and entropy (S), are
related to the equilibrium constant (K) for a chemical reaction at
temperature (T) by the equation below:
(1)G= -RT lnK = H - TS
Where R is the universal Gas Constant and equals 8.314 J/molK. Equation
(1) can be rearranged to eliminate G and solve for the natural log of K in
terms of H, S and T:
(2)lnK = (-H/R) (1/T) + (S/R)
Equation (2) can be compared to the point slope of a line (y = mx + b) so
that lnK versus 1/T should result in a straight line with slope being equal
to (-H/R) and the y-axis intercept (S/R).
The solubility of salt is dependent on the temperature of the solution.
When equilibrium is established in a saturated solution at a specific
temperature, the rate of formation of ions in a solution is equal to the rate
of deposition of the solid. The equilibrium constant for the dissociation of
the solid in a solvent is called the solubility product constant (Ksp). It is
equal to the product of the concentration of ions in solution. Since the
concentration of ions can change with temperature, the equilibrium
constant for the reaction is temperature dependent. Sodium tetraborate
decahydrate (borax) dissociates in water to form sodium and borate ions
and water.
(3)Na2B4O7.10H2O(s) 2Na(aq) + B4O5(OH)42-(aq) + 8H2O(l)

The equilibrium constant for the expression is:

(4)Ksp = [Na+]2 [B4O5(OH)42-]
Note that there are two sodium ions produced for each borate ion in the
reaction. Therefore, the concentration of sodium ion is twice the
concentration of borate ion.
(5)[Na+] = 2[B4O5(OH)42-]
And the equilibrium can now be re-written as total borate ion
concentration by substituting the equations from (5) into (4):
(6) Ksp = 4[B4O5(OH)42-]3+
Thus the equilibrium constant for the reaction can be determined if the
total borate ion concentration is known. Since borate ions are bases, their
concentration can be determined by a simple acid-base titration requiring
two moles of H+ ions for each mole of orate ion:
(7) B4O5(OH)42- + 2H+ + 3H2O 4B(OH)3
If a set saturated borax solutions are formed at various temperatures and
titrated to determine borate ion concentration, the data can be used to
compute Ksp values at each temperature and a plot of ln(Ksp) versus 1/T
can then be used to provide sufficient information which will allow
calculation of H and S.

EXPERIMENTAL APPARATUS AND CHEMICAL

Erlenmeyer flask
Test tubes
Burette
Pipette
Laboratory thermometer
Burner
Beaker
Digital analytical balance

PROCEDURE

5 clean test tubes were labelled and 5.00ml of water was

transferred into each test tube with a volumetric pipette.

The exact level of the liquid in the test tube was carefully marked
after which the liquid was discarded and the test tube dried.

Approximately 30g of borax was dissolved in 50mL of distilled water

in a beaker.

The mixture was then heated gently to 65C and a little more borax
was added to the solution until excess solid was present and the
solution was completely saturated.

The solution was allowed to cool to approximately 60C and was

poured into the test tube #1 until the level of the solution reached
the exact 5.00mL mark on the test tube. The exact temperature of
the solution was noted.

The solution was allowed to cool to approximately 50C and exactly

5.00mL of it was poured into test tube #2. The exact temperature of
the solution temperature was noted.

The steps were repeated and the solution was cooled to

approximately 40C, 30C and 20C in the tubes #3, #4 and #5
respectively.

The contents of test tube #1 were transferred into a clean 125mL

Erlenmeyer flask and the test tube was rinsed with several portions
of distilled water, adding the rinse to the flask.

Water was added to the crystallized solid remains in the test tube,
and was heated gently until the borax dissolved and then
transferred to the flask.

2 to 3 drops of bromocresol green indicator was added to the flask.

A clean 50mL burette was filled with 0.5M HCl solution.

A few mL of the acid was drained into an empty beaker and 1 drop
of the bromocresol green was added to the acid.

The content of the beaker was titrated o the end point with the HCl
solution.

The steps were repeated and the contents of each remaining test
tube were titrated.

OBSERVATIONS
It was observed that not all the borax dissolved wen approximately 30g
was dissolved in 50ml of distilled water at room temperature.
Also the color of bromocresol green when added to the flask containing
the borax solution turned blue.

A pale yellow color was observed at the end point with the HCl solution.

TABLE OF RESULTS
Temperature /oC

Volume
B4O5(OH)45-/ml

Volume HCl/ml

60

5.0

15.40

50

5.0

14.80

40

5.0

8.60

30

5.0

5.60

20

5.0

4.30

CALCULATIONS
Temp (oC)

T (Kelvin)

60
50
40
30
20

333
323
313
303
293

1/T
(Kelvin-1)
0.003003
0.003096
0.003195
0.0033
0.003413

[Oxalate]

Ksp

In(Ksp)

0.77
0.74
0.43
0.28
0.215

1.826
1.621
0.318
0.088
0.0398

0.60213
0.48304
-1.1457
-2.4304
-3.22389

1) At T = 60oC = 273 + 60 = 333K

T-1 = 333-1 = 3.003 10-3 K-1
From reaction equation: B4O5(OH)42 (aq) + 2HCl(aq) + 3H2O(l) 4B(OH)3(aq) + 2Cl (aq)
n(borate) =1
n(H+)
2
n(borate) = 0.5 n(H+)
n(H+) =

[H+] volume of H+

=
=

0.5 15.40
7.7mol

Hence n(borate)

= 7.7 0.5
= 3.85mol

C= n/v
Concentration of borax, C ((B4O5(OH)45) = 3.85/5
= 0.77M
Ksp = 4 [borate] 3
= 4 (0.77)3
= 1.826
InKsp = 0.6022
2) At T = 50oC = 273 + 50 = 323K
T-1 = 333-1 = 3.096 10-3 K-1
n(borate) = 0.5 n(H+)
n(H+) =
=
=

[H+] volume of H+
0.5 14.80
7.4mol

Hence n(borate)

= 7.4 0.5
= 3.70mol

C= n/v
Concentration of borax, C ((B4O5(OH)45) = 3.70/5
= 0.74M
Ksp = 4 [borate] 3
= 4 (0.74)3
= 1.671
InKsp = 0.4830
3) At T = 40oC = 273 + 40 = 313K
T-1 = 333-1 = 3.195 10-3 K-1
n(borate) = 0.5 n(H+)
n(H+) =
=
=

[H+] volume of H+
0.5 8.60
4.3mol

Hence n(borate)

= 4.3 0.5

= 2.15mol
C= n/v
Concentration of borax, C ((B4O5(OH)45) = 2.15/5
= 0.43M
Ksp = 4 [borate] 3
= 4 (0.43)3
= 0.318
InKsp = -1.1457
4) At T = 30oC = 273 + 40 = 303K
T-1 = 303-1 = 3.300 10-3 K-1
n(borate) = 0.5 n(H+)
n(H+) =
=
=

[H+] volume of H+
0.5 5.60
2.8mol

Hence n(borate)

= 2.8 0.5
= 1.4mol

C= n/v
Concentration of borax, C ((B4O5(OH)45) = 1.4/5
= 0.28M
Ksp = 4 [borate] 3
= 4 (0.28)3
= 0.088
InKsp = -2.4304
5) At T = 20oC = 273 + 20 = 293K
T-1 = 293-1 = 3.413 10-3 K-1
n(borate) = 0.5 n(H+)
n(H+) =
=
=

[H+] volume of H+
0.5 4.30
2.15mol

Hence n(borate)

= 2.15 0.5
= 1.075mol

C= n/v
Concentration of borax, C ((B4O5(OH)45) = 1.075/5
= 0.215M

Ksp = 4 [borate] 3
= 4 (0.215)3
= 0.0398
InKsp = -3.2239

Graph of lnKsp versus 1/T

Graph of lnKsp and 1/T

1
0.5
0
-0.5
lnKsp

0
(lnKsp, 1/T)

-1

Linear ((lnKsp, 1/T))

-1.5
-2
-2.5
-3
-3.5
1/T

Slope of the line

From graph,
Gradient

= Y2 Y1
X2 X1
=
=

-0.5- (-3)
.
0.003104 0.003308
-12254.90

But from equation (2), slope = -Ho = 12254.90

R
-H = 12254.90 R
R = 8.314J/molK
Ho = 8.314 -12254.90
= 101887.25 KJ/molK

3. The two points are:

(0.003104, -0.5) and (0.003308, -3)
Substituting into equation (2)
-0.5 = -Ho (0.003104) + S
R
R
-3 = -Ho (0.003308) + S
R
R

(1)
(2)

But R = 8.314 J/mol and multiplying both sides by the value of R

8.314(-0.5) = -Ho (0.003104) + S
(1)
8.314(-3) = -Ho (0.003308) + S

(2)

(1) (2)
20.785 = 0.000204Ho

Ho

= 101887.25 J/mol
= 101887.25 KJ/mol

Substituting

Ho into (1)

-4.157 = -(0.003104 101887.25) + S

S = -4.157 + 316.26
S = 312.10 J/mol

4. The value of the enthalpy of the dissociation of borax solution from the experiment
conducted was 101.887KJ/mol. Comparing this value to the literature value (110
KJ/mol), it can be noticed that the value has deviated to some extent. This deviation
can be attributed to certain factors:
a) Temperature reading.

b) Titer value obtained as a result of poor volume reading as a result of parallax.

c) The nature of the borax solution (it solidifies quickly).
d) Some of the solution clanged to the stirrer which was used as a result not all the
5.00ml borax solution was used in the titration.
e) Recording the amount of acid used for titrating at very low temperatures was
impossible due to the room temperature which was higher.
5. From the experiment conducted and the values obtained, it is realized that as the
temperature increased, there was an increase in solubility as indicated by the Ksp
values and their corresponding temperatures.
On the other hand, when the temperature was decreasing, the borax solution was
observed to be solidifying indicating also that a decrease in temperature reduces the
solubility

6. The positive value of Ho obtained signifies an endothermic reaction. It was observed

during the course of the experiment that beaker was cold to touch until heating and
when left standing when the borax was dissolved in water, the system caked and
became cold implying an endothermic process taking place.

7. From the calculated value, the entropy of the system is positive. This is so because the
entropy of the borax (initial state) is lower than the borax solution (final state). In the
reaction, the reactants and products are of the same phase but the number of moles of
the products is greater than the number of moles of the reactants which leads to an
increase in entropy (positive).

DISCUSSION
For a series of borax containing samples taken at different temperatures, the
concentration of borate ions will be determined. The borate ions react with a
monoprotic acid HCL in a 1:2 ratio:
B4O5 (OH)42-(aq) +2 HCl(aq) + 3 H2O(l) 4 B (OH)3 (aq) + 2Cl-(aq)
The experiment requires that the solubility of borax be found at various temperatures.
The solubility of the borate ion depends on temperature such that it increases as
temperature increases. When equilibrium is established in the saturated solution at a
specific temperature, the rate of formation of borate ions is equal to the rate of
deposition of the borax. The equilibrium constant for the dissolution of a solid in a

solvent is called the solubility product constant (Ksp) which is equal to the product of
the concentration of the ions in solution.
Heat is applied to the borate ion in the conical flask so as to allow the full reaction of
the borate ions and the HCl in solution.
Recording the amount of acid used for titrating at very low temperatures was
impossible due to the room temperature which was higher.
It was observed during the course of the experiment that beaker was cold to touch
until heating and when left standing when the borax was dissolved in water, the
system caked and became cold implying an exothermic process taking place.
EXPERIMENTAL PRECAUTION
1. The volumetric pipette was never used with heated solutions.
2. The exact level of the liquid on the test tube to ensure accuracy.
3. It was ensured that the solid borax was not transferred from the beaker to the test tube.
CONCLUSION
From the experiment conducted and the values obtained, it is realized that as the temperature
increased, there was an increase in solubility as indicated by the Ksp values and their
corresponding temperatures.
On the other hand, when the temperature was decreasing, the borax solution was observed to
be solidifying indicating also that a decrease in temperature reduces the solubility. In effect,
there is a linear relationship between temperature and solubility.
The positive value of Ho obtained signifies an endothermic reaction.
Bromocresol green as an indicator turn yellow in an acidic region of 3.6-5.2. The color of the
solution changed to light yellow indicating the end point of the reaction. This shows that the
indicator was suitable for the experiment.
REFFERENCES
1. Chemistry the central science 7th edition by Brown Lemay Bursten (Page 5978)