EXPERIMENT 4

THE
DETERMINATION
OF PARTIAL MOLAR
ENTHALPY

INTRODUCTION

A partial molar property is a thermodynamic

quantity which indicates how an extensive
property of a solution or mixture varies with
changes in the molar composition of the mixture at
constant temperature and pressure.
Similar to the volume, the enthalpy of a solution
is a function of temperature, pressure and
composition. The partial molar enthalpy of mixing
of a component is the heat change when one
more of that component is added to a large
volume of solution at a specific concentration. The
excess molar enthalpy is identical with the molar
enthalpy change on mixing and therefore is often
termed as the heat of mixing.

INTRODUCTION

The enthalpy of mixing is the enthalpy change

associated with the dissolution of a substance in
a solvent at constant pressure resulting in infinite
dilution. It is most often expressed in kJ/mol at constant
temperature.
A chemical reaction involves the breaking of some
chemical bonds and the formation of the other chemical
bonds. The breaking of bonds requires an input of
energy and the formation of bonds gives off energy, so
that nearly every constant-temperature chemical
reaction is accompanied by energy and enthalpy
changes. If the system gives off heat when a reaction
takes place at constant temperature, the reaction is
called exothermic. If the system absorbs heat at
constant temperature, the reaction is called
endothermic.

INTRODUCTION

In general, the value of a partial molar

property of a constituent in a solution is
not equal to the value for the pure
substance.

OBJECTIVES

To determine the molar

enthalpy of mixing (H) for
the different mixtures of
glycerol and water.
To use the data to estimate the
partial molar enthalpies of
mixing or the two components
in a mixture.

SCHEMATIC
DIAGRAM

Measure out the specified volume of glycerol into the Dewar flask
through a pipet and allow it to equilibrate for two minutes before
recording its constant temperature using a Fischer thermometer.
Add the specified volume of water through a buret them immediately
cover the flask and mix the solution by swirling. Add the specified
volume of water through a buret them immediately cover the flask and
mix the solution by swirling.
For every minute, in three minutes, get the time temperature data and
record the constant temperature obtained.

Rinse and dry the Dewar flask thoroughly before continuing on a new
measurement.
Repeat the last four steps for all the specified mixtures of glycerol and
water.

DATA

Table 1. Composition of Glycerol- Water

Mixtures
No.
mL
mL
Mol
Mol
glycero water glycero water
l
l (n1)
(n2)
1
2
3
4

2.77
13.83
27.67
20.85

67.54
30.69
27.29
11.94

0.038
0.19
0.38
0.29

3.752
1.705
1.516
0.66

5
6
7
8

34.49
38.66
36.76
25.01

8.53
4.17
2.27
0.38

0.47
0.53
0.50
0.34

0.47
0.23
0.126
0.021

CALCULATIONS

Mole fraction of glycerol and

water

Where:
X1=mole fraction of glycerol
X2=mole fraction of water
n1= mole of glycerol
n2= mole of water

CALCULATIONS

Mean heat capacity

: C(water) = 75.3 J/K mol

: C(glycerol) = 207.5 J/K
mol

CALCULATIONS

The molar enthalpy of mixing

Where:
H= Molar Enthalpy
C=Mean heat Capacity
T= Change in temperature

Mole
fraction
of
glycerol
(X1)

Mole
fraction
of water
(X2)

(J/K
mol)

n1

n2

T (K)

0.010032 0.989968

0.038

3.75

0.1

0.100529 0.899471

0.19

1.7

0.9

88.52

79.668

0.202128 0.797872

0.38

1.5

0.9

101.74

91.566

0.305263 0.694737

0.29

0.66

2.3

0.47

0.47

1.5

0.697368 0.302632

0.53

0.23

1.8

167.4921 301.4858

0.793651 0.206349

0.5

0.13

2.3

180.2206 414.5075

0.941828 0.058172

0.34

0.021

0.7

199.8097 139.8668

0.5

0.5

(J/mol)

76.62619 7.662619

115.6558 266.0083
141.4

212.1

CALCULATIONS

If you set the X1 in the general

equation to zero, you can obtain this
formula for H2:

For H1, this is a possible

equation:

CALCULATIONS

H1

H2

7.662619

-562.1942422

7.740267

79.668

-377.3747368

88.52

91.566

-216.8668421

114.4575

266.0083

45.86350272

382.8908

212.1

27.07659574

424.2

301.4858

136.5218669

996.2139

414.5075

306.7355206

2008.767

139.8668

262.8672844

2404.377

CALCULATIONS

Draw a graph of the molar enthalpy of

mixing (H) vs. mol fraction of glycerol
(X1) and determine the value of H1
and H2 for a mixture of 0.45 mol
fraction of water.
y = 259.55x + 73.991
y= 259.55 (0.55) + 73.991

:X1=.55

y= 261.7435 J/mol = H

CALCULATIONS

CALCULATIONS

H vs X1
3000
2500
2000
1500
H

H2
H1
mixing

1000
500
0
0

-500
-1000
X1

DISCUSSIONS

To simplify matters, the volumes for both

glycerol and water had to be cut down to smaller
portions and so we came up with the ones in the
Table 1 since we knew that by doing so, the mole
fractions for both would not be altered. We also
had to make use of pure glycerol which was more
viscous for the later part of the experiment
because we ran out of the less viscous glycerol
and that could be another reason for the
discrepancy in the temperature of each mixture.
The molar enthalpy of mixing at 0.45 mol
fraction of water is 261.7435 J/mol. Its H1
is481.6522 J/mol while its H2 is 1.03352x10-13
J/mol.

CONCLUSION

In this experiment, we learned that the

temperature of glycerol and the temperature of the
solution vary more visibly when the amount of
glycerol is much greater than the amount of water in
a mixture and makes the temperature of solution
higher than that of the glycerol.
This also shows that the mixture of glycerol and
water generally undergoes endothermic process
because of the positive values that we obtained in
our data.
All differences from the expected results can be
accounted to the personal errors that we committed
while performing the experiment when we did not
maintain the consistency of the glycerol that we
used and perhaps while adding the volumes of each
substance into the Dewar flask.