Enthalpy & Entropy of Aqueous Borax Solution

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.
3. To become acquainted with the changes in free energy, enthalpy, and entropy and their
relation to the equilibrium constant for a chemical reaction.
Introduction
Borax, most commonly known as sodium borate, sodium tetra borate, or disodium tetra
borate, is an important boron compound, a mineral, and a salt of boric acid. Powdered borax is
white, consisting of soft colorless crystals that dissolve easily in water. Borax is obtained as
tincal, Na
2
B
4
O
5
(OH)
4
.8H
2
O and kernite, Na
2
B
4
O
7
.4H
2
O.
Borax has a wide variety of uses. It is a component of many detergents, cosmetics,
and enamel glazes. It is also used to make buffer solutions in biochemistry, as a fire retardant, as
an anti-fungal compound for fiberglass, as a flux in metallurgy, neutron-capture shields for
radioactive sources, a texturing agent in cooking, and as a precursor for other boron compounds.
Enthalpy is a measure of the total energy of a thermodynamic system. It includes the internal
energy, which is the energy required to create a system, and the amount of energy required to
make room for it by displacing its environment and establishing its volume and pressure.
Enthalpy is a thermodynamic potential. It is a state function and an extensive quantity. The unit
of measurement for enthalpy in the International System of Units (SI) is the joule, but other
historical, conventional units are still in use, such as the British thermal unit and the calorie.
Saturation is the point at which a solution of a substance can dissolve no more of that substance
and additional amounts of it will appear as a separate phase. This point of
maximum concentration, the saturation point, depends on the temperature and pressure of the
solution as well as the chemical nature of the substances involved. This can be used in the
process of re-crystallization to purify a chemical: it is dissolved to the point of saturation in hot
solvent, then as the solvent cools and the solubility decreases, excess solute precipitates.
Impurities, being present in much lower concentration, do not saturate the solvent and so remain
dissolved in the liquid. If a change in conditions (e.g. cooling) means that the concentration is
actually higher than the saturation point, the solution has become supersaturated.
A spontaneous process is the time-evolution of a system in which it releases free
energy (usually as heat) and moves to a lower, more thermodynamically stable energy state. The
sign convention of changes in free energy follows the general convention
for thermodynamic measurements, in which a release of free energy from the system corresponds
to a negative change in free energy, but a positive change for the surroundings.
A spontaneous process is capable of proceeding in a given direction, as written or described,
without needing to be driven by an outside source of energy. The term is used to refer to macro
processes in which entropy increases; such as a smell diffusing in a room, ice melting in
lukewarm water, salt dissolving in water, and iron rusting.
The laws of thermodynamics govern the direction of a spontaneous process, ensuring that if a
sufficiently large number of individual interactions (like atoms colliding) are involved then the
direction will always be in the direction of increased entropy (since entropy increase is
a statistical phenomenon).

The total enthalpy, H, of a system cannot be measured directly. Thus, change in enthalpy, H, is
a more useful quantity than its absolute value. The change H is positive
in endothermic reactions, and negative in heat-releasing exothermic processes. H of a system is
equal to the sum of non-mechanical work done on it and the heat supplied to it.




Theory
Borax dissociates in water to form sodium and borate ions and water. This reaction occurs by the
following chemical equation:
Na
2
B
4
O
7
10H
2
O(s) 2Na
+
(aq) + B
4
O
5
(OH)
4
2
(aq) + 8H
2
O(l)

Free energy change of a chemical process is directly proportional to the equilibrium constant of
the chemical process. This can be deduced by the following equation:
AG = RT ln K = AH TAS

Where R= gas constant T= absolute temperature of reaction in Kelvin , k= equilibrium
constant
Making ln K the subject, we obtain :
Ln K = (-AH/R)(1/T) + (AS/R) (1)
In this form the equation is now linear and 1/T and lnK can be used as (x, y) points on a graph. The slope
of such a graph is related to the change in enthalpy and the change in entropy is related to the y-
intercept:

However; the equilibrium constant used here is the solubility constant. The solubility constant is
used because equilibrium is established in a saturated solution at a specific temperature.
Solubility is highly dependent on temperature.
The solubility constant is obtained by the following equation:
Na
2
B
4
O
7
10H
2
O(s) 2Na
+
(aq) + B
4
O
5
(OH)
4
2
(aq) + 8H
2
O(l)
K
sp
= [Na
+
]
2
[B
4
O
5
(OH)
4
2
]
Since there are two sodium ions produced for each borate ion [B
4
O
5
(OH)
4
2-
] then
[Na
+
] = 2 [B
4
O
5
(OH)
4
2
]
And the K
sp
can be rewritten as: K
sp
= 4[B
4
O
5
(OH)
4
2-
]
3

Hence the k
sp
can be calculated for and used in equation (1) in order to calculate the changes in
entropy and enthalpy of the reaction.
The concentration of borate can easily found by a simple acid-base titration of the borax solution
with HCl. The simplicity of the titration is due to the fact that the borate ion is a weak base. The
endpoint of the titration is signaled by the colour change of bromo cresol green indication
This is the equation of the titration reaction: B
4
O
5
(OH)
4
+ 2H
+

+ 3H
2
O 4B(OH)
3

ln K
sp
=
-AH
RT
TAS
RT
+
ln K
sp
=
-AH
R
AS
R
+
1
T
y = m x + b
experimental procedure will specifically state that you are to make sure there is always some solid borax
remaining in the sample mixture before you remove some of it to analyze. That being the case, the
'concentration' of solid borax can be assumed constant, and the equilibrium expression can be
simplified:
RT ln K
sp =
= AH TAS
A table of free energy values (AG) with the temperatures those values correspond to should be
compiled. This is most conveniently done using equation (A), with values for K
sp
and the temperatures
for which they are valid.
A graph of ln K
sp
vs. 1/T should be made, the slope of which is related to change in enthalpy.
The same graph has a relationship between change in entropy and its y-intercept

The experiment requires that the solubility of borax be found at various temperature values. Samples of
saturated borax solution are collected at no less than 5 different temperatures, four above room
temperature, and one close to or at room temperature. These samples are then warmed (if necessary)
to re-dissolve any precipitated borax, and titrated to the yellow bromocresol green endpoint with
standardized aqueous hydrochloric acid.

.


Chemicals and equipment
Distilled Water
0.500 HCl
30g Borax
Bromo cresol Indicator
Wash Bottle
Burette
Volumetric pipette
Digital analytical Balance
125 ml Erlenmeyer flask
5 Test tubes
Beakers
Water bath
Laboratory Thermometer
Heating Apparatus
Procedure
1) 5 clean test tubes were labeled and 5.00ml of water was transferred into each test tube
with a volumetric pipette.
2) The exact level of the water in the test tube is marked after which it is poured out and the
test tube is dried.
3) Approximately 30g of borax is dissolved in a 100mL beaker in 50mL of distilled water.
4) The mixture is then heated gently to 65
o
C. A little more borax is added to the solution
until excess solid was present and the solution is completely saturated.
5) The solution is allowed to cool to approximately 60
o
C 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 at 60
o
C.
6) The parent solution is then allowed to cool to approximately 50
o
C and yet again exactly
5.00mL of it is poured into test tube #2. The exact temperature of the solution is noted as
well.
7) The process is repeated at temperatures of: 40
o
C, 30
o
C, and 20
o
C. the various cooled
solutions were poured into test tubes #3, #4 and #5 respectively.
8) The contents of test tube #1 were transferred into a clean 125mL Erlenmeyer flask.
Several portions of distilled water was added to the borax solution in order to keep the
solution completely dissolved.
9) Water is added to the crystallized solid remains in the test tube, and is heated gently until
the borax dissolved and then transferred to the flask.
10) 3 drops of Bromo cresol green indicator is added to the flask.
11) A clean 50mL burette is filled with 0.5M HCl solution.
12) A few mL of the acid was drained into an empty beaker and 1 drop of the bromocresol
green was added to the acid in order to verify the colour of the indicator in an acidic
solution.
13) The content of the beaker was titrated to the end point with the HCl solution.
14) Steps 8 through 13 were done to the borax solutions in the other test tubes.







Results
Table of Results
Temperature /
o
C Volume B
4
O
5
(OH)
4
5-
/ml Volume HCl/ml
60 5.0 26.40
50 5.0 12.60
40 5.0 7.2
30 5.0 4.8
20 5.0 3.0

Temp (
o
C) T (Kelvin) 1/T (Kelvin
-1
) [Oxalate] K
sp
In(K
sp
)
60 333 3.003 x 10
-3
1.32 9.20 2.22
50 323 3.096 x 10
-3
0.63 1.000188 0.00
40 313 3.195 x 10
-3
0.36 0.187 -1.68
30 303 3.300 x 10
-3
0.24 0.055 -2.90
20 293 3.413 x 10
-3
0.15 0.0135 -4.31

1) At T = 20
o
C = 273 + 20 = 293K
T
-1
= 293
-1
= 3.413 10
-3
K
-1
2) At T = 30
o
C = 273 + 20 = 303K
T
-1
= 303
-1
= 3.00 10
-3
K
-1

3) At T= 40
o
C =273+20=313K

T
-1
= 313
-1
= 3.195 10
-3
K
-1
4) At T = 50
o
C = 273 + 20 = 323K
T
-1
= 323
-1
= 3.096 10
-3
K
-1

5) At T = 60
o
C = 273 + 20 = 333K
T
-1
= 333
-1
= 3.003 10
-3
K
-1
Calculation
From the equation:
B
4
O
5
(OH)
4
2-

(aq)
+ 2HCl
(aq)
+ 3H
2
O
(l)
----------> 4B(OH)
3 (aq)
+ 2Cl
-

(aq)

1) Vol (HCl) = 26.40ml
1 mol Borate 2 mol HCl
N(Borate) = 0.5 x n(H
+
)
N(H
+
) = [H
+
] x Volume (H
+
) = 0.5 x 26.40/1000
= 0.0132M
Hence
n(Borate) = 0.5 0.0135
= 6.6 x 10
-3
mol
C= n/v
Concentration of borax, [B
4
O
5
(OH)
4
5
] = 6.75 x 10
-3
/0.005
= 1.32M
K
sp
= 4 [Borate]
3
= 4(1.32)
3
= 9.20
Ln (K
sp
) = ln(9.20)
= 2.22
2) Vol (HCl) = 12.60 ml
1 mol Borate 2 mol HCl
N (Borate) = 0.5 x n(H
+
)
N (H
+
) = [H
+
] x Volume (H
+
) = 0.5 x 12.60/1000
= 6.3 x 10
-3
M
Hence
N (Borate) = 0.5 0.0135
= 3.15 x 10
-3
mol
C= n/v
Concentration of borax, [B
4
O
5
(OH)
4
5
] = 3.15 x 10
-3
/0.005
= 0.63M
K
sp
= 4 [Borate]
3
= 4(0.63)
3
= 1.000188
Ln (K
sp
) = ln(1.00)
= 1.88 x 10
-4
3) Vol (HCl) = 7.20 ml
1 mol Borate 2 mol HCl
N (Borate) = 0.5 x n(H
+
)
N (H
+
) = [H
+
] x Volume (H
+
) = 0.5 x 7.20/1000
= 3.6 x 10
-3
M
Hence
N (Borate) = 0.5 3.6 x 10
-3
= 1.8 x 10
-3
mol
C= n/v
Concentration of borax, [ B
4
O
5
(OH)
4
5
] = 6.75 x 10
-3
/0.005
= 0.36M
K
sp
= 4 [Borate]
3
= 4(0.36)
3
= 0.187
Ln (K
sp
) = ln(0.187)
= -1.68

4) Vol (HCl) = 4.80 ml
1 mol Borate 2 mol HCl
N (Borate) = 0.5 x n(H
+
)
N (H
+
) = [H
+
] x Volume (H
+
) = 0.5 x 4.80/1000
= 2.4 x 10
-3
M
Hence
N (Borate) = 0.5 2.4 x 10
-3
M
= 1.2 x 10
-3
mol
C= n/v
Concentration of borax, [ B
4
O
5
(OH)
4
5
] = 1.2 x 10
-3
/0.005
= 0.24M
K
sp
= 4 [Borate]
3
= 4(0.24)
3
= 0.055
Ln (K
sp
) = ln(0.055)
= -2.90
5) Vol (HCl) = 3.00 ml
1 mol Borate 2 mol HCl
N (Borate) = 0.5 x n(H
+
)
N (H
+
) = [H
+
] x Volume (H
+
) = 0.5 x 3.0/1000
= 1.5 x 10
-3
M
Hence
N (Borate) = 0.5 1.5 x 10
-3
= 7.5 x 10
-4
mol
C= n/v
Concentration of borax, [ B
4
O
5
(OH)
4
5
] = 7.5 x 10
-4
/0.005
= 0.15M
K
sp
= 4 [Borate]
3
= 4(0.15)
3
= 0.0135
Ln (K
sp
) = ln(0.0135)
= -4.31

From the graph, the slope is 1.596. But the slope is =

R= 8.314 J/molK
= 8.314 x 1.596 = 13.269 J/molK
If the y-intercept is3.454 then:

= 3.454
= 8.314 x 3.454 = 28.72 J/molK




The two points are:

(3.413 x 10
-3
, -4.31) and (3.003 x 10
-3
,2.22)

-4.31 = -H
o
(3.413 x 10
-3
) + S....... (1)
R R

2.22 = -H
o
(3.003 x 10
-3
) + S... (2)
R R

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

8.314(-4.31) = -H
o
(3.413 x 10
-3
) + S... (1)

y = -1.596x + 3.454
-5
-4
-3
-2
-1
0
1
2
3
0 1 2 3 4 5 6
L
n
(
K
s
p
)

1/T
8.314(2.22) = -H
o
(3.003 x 10
-3
) + S... (2)

(1) (2)

-54.29042= 0.00041 x H
o


H
o
= -132415.66 J/mol

= -132.416 KJ/mol

Substituting H
o
into (1)

-35.83334 = -(3.413 x 10
-3
-132415.66) + S

S = 416.101 J/mol

Discussion
By theory we obtain and enthalpy value of 150kj. We got a little less than that. Indicating that the
substances used in the experiment wasnt pure.
When the borax solution was heated to the specified temperatures, it took only a matter of
seconds to begin recrystallizing. Hence more water was added to the already heated solution and
heated again for a little while to prevent the borax from completely recrystallizing.
Upon the addition of bromo cresol indicator to the borax solution, the colur of the solution within
the Erlenmeyer flask changed from creamy to yellow.
The mixture was then titrated with 0.5M HCl. The endpoint of the titration comes by like a flash.
The colour change was from yellow to bluish green. It was necessary to add the HCl in little
drops. At a temperature of 40
o
C the volume of the titrant required was 7.20ml. After the experiment
was complete and the calculations made, it was deduced that the values of the changes in enthalpy and
entropy of the sytem were: -132.416 KJ/mol and 416.101 J/mol respectively.
Sources of error
Precautions
1. Lab coats, goggles, and disposable gloves were put on throughout the course of the
experiments.
2. We ensured that the glassware were washed with samples of the solution before they
were used
3. We ensured that the experiments were done at the right temperatures required.
4. Readings from the burette were taken from the bottom of the meniscus.
5. The burette was erected upright to ensure accurate reading of the meniscus.
6. The volumetric flask was covered with the stopper immediately it was filled up to its
mark with the solution.
7. Our hands were thoroughly washed before leaving the laboratory.