SCHOOL OF CHEMICAL & BIOMEDICAL ENGINEERING

CHEMICAL & BIOMOLECULAR ENGINEERING

CH2801: CHEMICAL/ BIOMOLECULAR ENGINEERING LABORATORY

2A

Year 2: C7 Partial Molar Volume

( Water-Ethanol System)

Name: Muhammad Ilyas Hassan

Matriculation Number: U1322800G
Group: 9
Date of Experiment: 9th Sept 2014

1.

Aim
The objective of the experiment is to study partial
molar properties of components in the mixture by
determining partial molar volumes of ethanol-water
solutions.

2.

Abstract
Mixing substances together are currently a heavy part
of our lives. We depend on mixtures all the time as they
are part of our daily lives; our food, drinks, petrol,
industries, research, etc. Partial molar properties are
intensive thermodynamic properties of substances that
constitutes a mixture. These thermodynamic properties
are important in studies that involves mixtures as it
determines the contribution of a component to the
respective properties of a mixture, requiring it as basis
for our equation balances (energy, mass, momentum,
etc) . Partial molar properties include partial molar
volumes, partial molar enthalpies, partial molar Gibbs
energy, etc which are all independent of the total
amount of mixture but are dependent on
thermodynamic conditions, usually temperature and
pressure, depending on the property. In this study, we
are focusing into partial molar volumes to help us
familiarise ourselves with the concept of partial molar
properties.

3.

Principles
Just like any other chemical process/experiment, we
have to understand the theoretical concept and
methodology behind the experiment.
3.1 Partial Molar Volume
Partial molar volume of a component (component I for
example) may be considered to be the change in total
volume of a mixture when 1 mole of pure i is added to
an infinite amount of a mixture (or an amount so large
that insignificant concentration change will result).
Partial molar volumes are of considerable interest as
there are often used in connection with other partial
molar quantities. For example, the change in partial
molar Gibbs energy with pressure at constant
temperature is equal to partial molar volume as
follows.
From basic laws,
dGi = -Si dT + Vi dP

Making Vi the subject,

(Gi /P)T = Vi

Moreover, the difference between partial molar volume

of a component in a mixture Vi and its molar volume of

pure substance under the same T and P is related to its

measure of deviation from ideal solution behaviour or
activity coefficient, i according to the following
equation:
P
lni =(1/RT) Pref (Vi -Vi )dP

where Vi is the molar volume of pure i measured at the

same T and P as the mixture.

3.2 Derivation of Partial Molar Volumes

There are several methids to determine partial molar
volumes. In this study, we will use the most common
method, the graphical method based on apparent
molar volume described by Lewis and Randall to find
the partial molar volumes of absolute ethanol and
ultrapure water in a water-ethanol binary system. The
apparent molar volume is graphed based on small
increments in concentration of a substance to another
substance which constitutes majority of the binary
mixture.
Considering a binary mixture consisting of two
components, component 1 being ultrapure water and 2
being absolute ethanol, the total volume of the mixture
is related to their respective partial molar volumes, V1
and V2 as follows:
t
V =n1V1 +n2V2

(Eq. 1)

where n1 and n2 are moles of components 1 and 2 in

the mixture respectively, and
dVt *
) T, P, n2
V1 = (
d n1

(Eq. 2)

dVt
)
V2 = (
d n 2 T, P, n1

(Eq. 3)

If the mixture consists of a solvent (liquid water as

component 1) and a solute (ethanol as component 2)
o
and let V1 be the molar volume of pure water in
ml/mole at the same T and P as the mixture, the total

volume is related to apparent molar volume of solute

(component 2) as:
t
o
V =n1 V1 +n2

(Eq. 4)

The solute apparent volume may therefore be defined

as follows:
t
o
=(V - n1 V1 )/n2

(Eq. 5)

From experimentally measured density (g/ml) of the

mixture at T and P, the total volume of the mixture can
be related to the molecular weights of the components
W1 and W2 in (g/mol) as follows,
t
V =(n1 W1 + n2 W2)/

(Eq. 6)

However, it is convenient to base on l000g (1 kg) of

pure water with a density of 1 (g/ml) at the T and P of
t
measurement in a solution of total volume V . Hence
o
n1 V1 = 1000 / 1

(Eq. 7)

and
t
V =(1000 + n2 W2)/

(Eq. 8)

Eq. 5 can be rewritten as,

= (1/){W2 - (1000/n2 )[(-1)/1 ]} (Eq. 9)
By the definition of partial molar volumes according to
Eqs. (2) and (3) and the total volume by Eqs. (1) and
(4),
t
V2 = (d V /d n2)T, P, n1 = + n2 (d / d n2)T, P, n1
(Eq 10)
t
o
2
V1 = (V -n2 V2)/n1 = V1 - [(n2 /n1)(d / d
n2)T,P,n1] (Eq 11)

The apparent solute volumes can be determined

according to Eq. (9) from density measurements of
pure solvent 1 and solution mixture at the same T
and P at different n2. The plot of versus n2 will allow
the evaluation of slopes (d /d n2) at different n2. V1
and V2 can then be determined from the above Eqs.
(10) and (11).
(The molecular weights of water and ethanol are
18.015 and 46.070 in g/mol respectively)

4.

Reagents, Equipment and Apparatus

The 3 main reagents in this experiment are ultrapure
water, absolute ethanol and acetone. Ultrapure water
and absolute ethanol are reagents that are involved in
the binary mixture in which involves their partial molar
volume calculations while acetone is used for the
cleaning and drying of density measuring cell.
The main equipment used is a DMA 5000 densitometer
for density measurements of the mixtures and pure
reagents.
Other apparatus includes common labaratory
equipments including burettes, pipettes and conical
flasks are used of solution preparation.

Figure 1: Image of the DMA5000

5.

Procedure
The experiment is fairly a straight-forward one with 3
main parts; preparation of solutions, measurement of
mixture densities, and calculations for results. A brief
outline of the procedure is listed below.
(a) Preparation of water-ethanol solutions
Solutions of ethanol in water containing 0, 5, 10, 15,
20, 30 and 40 volume % are prepared. The volumes of
ethanol and water are measured out accurately into
glass-stoppered bottle or conical flasks using burettes
or pipettes at room temperature. A total of 25ml for
each solution is required for density measurements.
(b) Density determination
The density of each solution is measured accurately at
o
o
a preset temperature of 20 C or 30 C using the
DMA5000 densitometer as follows:
1. Turn on the DMA5000 using the power switch and wait
for green light for an indication that the machine is
ready for use.
2. Check that the density cell has already been thoroughly
cleaned to remove all foreign substances and dried.
Cleaning and drying procedure:

(i) Fill the measuring cell with ultrapure water

using a syringe with Luer tip and attach it to the
filling nozzle. Move the plunger of the syringe in
and out several times to facilitate cleaning.
Remove the cleaning water.
1 (ii) Repeat the above cleaning process with pure
acetone.
(iii) Remove the acetone and attach the air hose
to the filling nozzle. Turn on the air pump for about
1 minute. Turn off the air pump and remove the air
hose from the filling nozzle.
Cleaning and drying of the measuring cell after each
measurement is necessary if samples with different
chemical composition are to be used.
3. Density measurements for ultrapure water (0%
ethanol) and absolute ethanol at the preset
o
o
temperature of 20 C and 30 C:
(i) Activate the required method using the
Method soft key.
(ii) Select Density 20 or Density 30 at a preset
o
o
temperature of 20 C or 30 C respectively.
(iii) Take a sample of about 2.5 ml from the bottle
of ultrapure water provided using a syringe and
ensure that there are no air bubbles in the sample.
(iv) Inject the sample through the filling nozzle
into the measuring cell of the DMA 5000.
(v) Observe and ensure that there are no gas
bubbles in the measuring cell and excess solution
emerges from the outlet hose connected to the
waste bottle.
(vi) If gas bubbles are observed in the cell, repeat
steps (iii) to (v).
(vii) After ensuring that there are no air bubbles
in the cell, press Start for density measurement.
Density reading will appears on the screen after

the system has equilibrated.

(viii) When Condition: Predetermined appears on
the screen, a density reading of 5-decimal places
will show.
(ix) Press Continue for density measurement for
the duplicate sample.
(x) If the density check for the duplicate samples
are OK, press Print to print out a copy of the
result.
(xi) Repeat the procedure for density
measurement for samples of absolute ethanol.
4. Density measurements for the water-ethanol solutions:
Repeat the above procedure for density measurements
for the prepared samples of water-ethanol solutions
with different compositions. It is advisable to carry out
the measurement according to the order from low to
high ethanol concentration.

(PRECAUTIONS: 1. Cleaning and drying of the

measuring cell after each measurement is necessary. 2.
Samples for density measurements must be
homogeneous and free of gas bubbles.)

6.

Results and Calculations

6.1 Density Measurements

Temperature at 20
: 20
: 1 atm

Temperature
Pressure
Ultrapure Water
Run

Density (g/mL)

0.99816

0.99817

0.99818

Average

0.99817

Table 1 : Density of ultrapure water at 20

Absolute Ethanol
Run

Density (g/mL)

0.78931

0.78935

0.78937

Average

0.78934

Table 2 : Density of absolute ethanol at 20

Binary Mixture
Ethanol (Vol%)

Run

Density (g/mL)

0.99109

0.99114

10

15

20

30

40

0.99119

Average

0.99114

0.98477

0.98484

0.98484

Average

0.98482

0.97908

0.97910

0.97906

Average

0.97908

0.97360

0.97364

0.97364

Average

0.97363

0.96200

0.96197

0.96297

Average

0.96199

0.94725

0.94745

0.94743

Average

0.94736

Table 3 : Density of Mixture at 20

Temperature at 30

Temperature
Pressure

: 30
: 1 atm

Ultraoure Water
Run

Density (g/mL)

0.99562

0.99557

0.99555

Average

0.99558

Table 4 : Density of ultrapure water at 30

Absolute ethanol
Run

Density (g/mL)

0.78086

0.78086

0.78086

Average

0.78086

Table 5 : Density of absolute ethanol at 30

Binary Mixture
Ethanol (Vol%)

Run

Density (g/mL)

0.98774

0.98714

0.98525

Average

0.98671

0.98204

0.98195

0.98190

Average

0.98196

0.97578

0.97560

0.97550

Average

0.97563

0.96863

0.96843

0.96833

Average

0.96846

0.95602

0.95598

0.95596

Average

0.95599

0.93948

0.93917

0.93903

Average

0.93923

10

15

20

30

40

Table 6 : Density of Mixture at 30

6.2 Tabulated results from sample calculation

Tabulated Results for 20oC
Sampl
e no.

Ethan
ol (Vol
%)

Density

0.9911

(mL/g)

n1
(mol)

n2
(mol)

55.5

0.90

(mL/mol
)
54.34

(d /
dn2)
-0.406

V 1

V 2

(mL/mol
)

(mL/mol
)

18.054

53.976

41

10

0.9848
15

55.5
1

1.91

53.90

-0.345

18.070

53.243

15

0.9790
82

55.5
1

3.03

53.50

-0.278

18.094

52.659

20

0.9736
29

55.5
1

4.29

53.20

-0.202

18.115

52.335

30

0.9619
99

55.5
1

7.36

53.01

-0.017

18.065

52.882

40

0.9473
60

55.5
1

11.4
4

53.32

0.229

17.509

55.941

Table 7: Tabulated Results for calculations at 20oC

Tabulated Results for 30oC

V 1

V 2

(mL/mol
)

(mL/mol
)

-0.785

18.106

56.066

54.28

-0.659

18.137

53.035

3.00

54.06

-0.520

18.179

52.494

55.5
1

4.26

54.18

-0.364

18.214

52.629

0.9559
9

55.5
1

7.30

53.89

0.015

18.081

53.998

0.9392
3

55.5
1

11.3
5

54.36

0.520

16.889

60.258

Sampl
e no.

Ethan
ol (Vol
%)

Densit
y
(mL/g)

n1
(mol)

n2
(mol)

0.9867
1

55.5
1

0.90

56.77

10

0.9819
6

55.5
1

1.89

15

0.9756
3

55.5
1

20

0.9684
6

30

40

(mL/mol
)

(d /
dn2)

Table 8: Tabulated Results for calculations at 30oC

6.3 Sample Calculations and Derivations

Sample Calculations for Ethanol = 5 vol% at T = 20C
and P = 1atm:
1 = 0.99817g/ml ; 2 = 0.78936g/ml ; average =
0.99114g/ml
1000
w1

n1 =

1000
1

Vt = (
=(

1000
18.015

= 55.51 mol

/ volume of water used ) x 25ml

1000
/ 23.75ml ) x 25ml
0.99817

= 1054.56 ml
n2 = (

x Vt 1000 ) / W2

= ( 0.99114g/ml x 1045.56ml 1000g ) / 46.070 g/mol

= 0.90 mol
=

{ W2 (

1000
n2

)(

}=

1
0.99114

{ 46.070

1000
0.991140.99817
(
)}
0.90
0.99817
= 54.34 ml/mol

NOTE: After attaining the values of for all concentration

levels, the graphs of vs n2 as seen in Fig 2 below can be
plotted for both temperatures.
V 1

=(

1000
d *
n2
1000
) ( 2 )(
) =(
)(
1 n1
d n2
0.998167 x 55.51
n1

0.902
)(-0.406) = 18.054 ml/mol
55.51
V 2

+ n2 (

d
) = 54.34 + 0.90(-0.406) = 53.976
d n2

ml/mol
*

d
d n2

is determined from the slope of the graph in Fig 2

below by differentiation of the function at the various points.

The partial molar volume graphs can then be plotted
against n2 after attaining the various respective partial
molar volumes for the two substances, to give a clearer
relation of partial molar volumes of water with
temperature and amount of solute as seen in Fig 3
below.

6.3 Graphs of various relationships plotted

The figures below shows the graphs of absolute molar
volumes and partial molar volmues against n2 , the
amount of solute.

Graph of Apparent Molar Volume of Solute, (mL/mol) against n2 (mol)

58
57
56
55
Apparent Molar Volume of Solute , (mL/mol) 54
53
52
51
0 5 10 15
n2(mol)
T=20

T=30

Figure 2: Graphs of apparent molar volumes of solute at

both temperatures

Graph of V1 and V2 against n2 for Temperature = 20C and 30C

70
60
50
40
V1/V2 30
20
10
0
0

10

12

14

n2 / mol
V1 @ T=20

V2 @ T=20

V1 @ T=30

V2 @ T=30

Figure 3: Graphs of partial molar volumes against

amount of solute at both temperatures
7.

Discussion
7.1 Results in relation to Gibbs-Duhem equation
The Gibbs Duhem equation is defined as: x1dVi = 0
at constant T and P. Based on the linearity of graphs of
V1 and V2 against n2 as seen in Fig.3, it is generally a
flat straight line that is parallel to the x axis. This
therefore implies that Vi does not change regardless of
n2, making it a constant despite the amount of
substance in the mixture. Therefore dV i is always 0,
satisfying the Gibbs - Duhem equation. However, by
observation of the results of graphs above, the general
shape of the graphs of Vi at 30 oC are slightly curved
especially so for the V2 graph. This indicates that it is
the experiment was not perfect, mainly due to some
possible sources of error for the study. Otherwise, it can
be observed that the Gibbs Duhem equation has been
satisfied.
7.2 Effects of temperature & pressure on partial
molar volumes
Although insignificant, it can be observed in Fig. 3 that

the partial molar volumes increases as temperature

increases. This is the case for BOTH substances of the
mixture, thus backing up the assumption that it holds
true for all partial molar volumes of all substances in
general. This is due to the fact of more energy is
supplied to the molecules and hence they are able to
vibrate more at higher temperature, as a results of this
more vigorous vibration, the volume occupied by the
molecules increases as temperature increases.
However, this study is not conclusive enough to fully
back up the hypothesis. The changes to the partial
molar volumes are minimal for both substances in this
study. This is due to both substances being in liquid
state, thus enabling us to treat it as good as
incompressible with the minimal changes in density
and partial molar volumes.
On the other hand, the effect of pressure on partial
molar volumes cannot be determined for this
experiment or study. The independent variable is only
the temperature while assuming constant pressure,
thus making it inconclusive to indicate the effects of
pressure on partial molar volumes. However, it can be
assumed that pressure has an effect on the partial
molar volumes as increasing pressure results in
increasing forces on the molecules, thus affecting the
apparent and partial molar volumes of the substances.
This is because the partial molar volumes are
dependent on the amount of moles of ultrapure water
and ethanol, as can be seen in the sample calculations.
However, since amount of moles increases with
increasing pressure at constant total volume,
calculated partial molar volumes of individual
component will decrease with increasing pressure. The
effects of pressure on partial molar volumes are small
and negligible in this experiment as the mixture is in
the liquid phase and can be assumed to be
incompressible. However, the effects of pressure on
partial molar volumes of gaseous mixtures will be
significant.
7.3 Possible sources of error & recommendations

Like any experiment, this study is based on an

experiment that is not perfect and has a tendency to
produce experimental results that deviate from true
values. Below are the possible sources of error for the
deviations.
1. Basis/assumptions used for calculations
In the study, when deriving the partial molar volumes,
we used the mass of solvent to be fixed at 1000g for
convenience purposes when in actual fact, we are
actually changing the number of moles/mass of solvent
used, when we prepare the solutions, total volume of
mixture is fixed at 25ml. Therefore, we are already
assuming that the partial molar volume of substances
does not change based on total amount of mixture but
the fraction of substances used. Therefore, it is
possible that errors may occur as we did not fix the
mass of the solvent during the experiment, but fixed
the volume of mixture instead. A recommendation
would be to test this assumption so that our results
have a stronger foundation.
In addition, it was assumed in the calculations that the
apparent molar volume of the ultrapure water remains
unchanged for the simplicity of calculations. This thus,
is a possible source of error, basing calculations on
assumptions.

2. Evaporation of volatile substances

The absolute ethanol used in the study is relatively a
volatile liquid. Therefore, when preparing the solutions
and measuring their mixture densities, ethanol might
have vaporise, thus affecting the mole fraction of the
substances in the mixture. This would thus affect the
measurements of densities of the mixture, thus
affecting the whole result of the experiment especially
since the slope of the graphs are sensitive to the
changes in apparent molar volumes. A suggestion

would be to put a lid over the beakers containing the

solutions before measuring the density of the mixture
should it take a while to use the densitometer. Another
way to avoid this situation would be to measure the
density immediately after preparing the solutions, thus
minimising the error of vaporisation.
3. Factors affecting density measurements
air bubbles
Possible errors may arise when measuring the
densitites of the mixtures/solutions. Especially so for
the densitometer. The machine is used consecutively
for all the solutions which are at different concetration
levels of ethanol thus emphasising on the importance
of cleaning process of the cell. Slight impurities of
previously used solutions could render changes in
concentration levels of the intended mixture which
density is to be measured. This would thus affect the
readings of the densities, thus causing a chain of effect
in the error made to the calculations. Also, one main
concern and disadvantage of the pump of the
densitometer and injection of solutions are the
possible air bubbles. Air has a much lower density than
any liquid, thus this would affect the readings
significantly. One recommendation would be to use a
different approach of measuring densities alongside
this method. Additional measurement of densities of
same solutions using the pycnometer[1], for example,
can reduce error of air bubbles and thus improve
accuracy of results.
4. Techniques to prepare solutions
Techniques due to human error when measuring the
solutions using common apparatus might cause results
to deviate slightly from true values. Measurement of
volumes using a burette for example might incur
parallex errors, thus affecting exact or true
concentration levels of mixtures which densities are to
be measured subsequently. A strong suggestion would
be to increase the number of samples of solutions of
the same concentration level in which the

measurement of densities is taken from. This would

substantially reduce the possibility of human error
affecting the results, thus improving accuracy of
experimental values.
5. Fluctuating and non uniform temperatures
Possibility of fluctuating temperatures may also incur
error of partial molar volumes. Although changes in
partial molar volumes are not significant in this case
with changes of temperature as seen in the results,
maintaining a constant temperature is difficult and
time is needed to reach a steady stead for energy
balance. Also, it is possible that temperature across
the sample is not uniform, thus possibly affecting
experimental values of the densities. However, the
deviations may be negligible as densitometers are
usually
efficient
in
maintaining
solutions
at
temperatures.

9.

Conclusion
In conclusion, the twofold aim of the study has been
met to a large extent. The study has given a better
understanding of partial molar properties, such as its
intrinsic property as shown by the graphs in Figure 3
above. In addition to that, in the study, we were able
to determine the partial molar volumes of both the
substances in the mixture using a the simple, fast and
effective approach by Lewis & Randall in yielding fast
and positive results of partial molar volumes. From the
study, it can also be concluded that the temperature of
the mixture affects the partial molar volumes of its
constituents. However, other methods and studies also
have to be done to support this study due to the
various possible sources of error and assumptions used
as a basis of the calculation and derivations of the
partial molar volumes of both ultrapure water and
absolute ethanol. Also, from the study, we cannot
determine the relationship of partial molar volumes
with
thermodynamic
parameters
other
than
temperature, like pressure for example, as only
temperature and concentration levels of solute are
variables.

10.

References

[1] Measurement of Partial Molar Volumes , Retrieved 18

Sept,
2014
from
http://infohost.nmt.edu/~jaltig/PartVol.pdf
[2] Partial Molar Properties definitions , Retrived 18 Sept,
2014,
from
http://www.le.ac.uk/chemistry/thermodynamics/pdfs/3
000/Topic2585.pdf
[3]

Molecular theory of partial molar volume and its

applications to biomolecular systems , Retrived 18
Sept,
2014,
from
http://www.icmp.lviv.ua/journal/zbirnyk.51/004/art04.
pdf

11.

Appendix

11.1 Partial Molar Properties

When a mixture is formed from mixing several pure
components, the thermodynamic properties of individual
component in the mixture are generally expressed in terms
of partial molar properties (Mi ). Partial molar properties such
as partial molar volumeVi , partial molar
enthalpy H i , partial molar Gibbs energy Gi , are intensive
properties based on unit mole and are independent of the
total amount of the mixture. Partial molar property M i is a
measure of a contribution of a component to the total
t
property M of the mixture and is defined as follows:
t
Mi = (M /ni)T, P, nj(j=i) (1)
t
Mi measures the change in total property M with change in
ni when T, P and composition of all other components except
component i are kept constant. Like wise, partial molar
volumeVi , partial molar enthalpy Hi , and partial molar Gibbs
energyGi , are defined as:
t
t
Vi = (V /ni)T,P,nj(j=i)Hi = (H /ni)T,P,nj(j=i)Gi = i =
t
(G /ni)T,P,nj(j=i)
Partial molar properties are important properties and used
extensively in the analysis of processes and process
equipment in chemical engineering.

11.2 Pycnometer

[1]

The pycnometer is first calibrated against Water. The

pycnometer is cleaned, dried and weighed empty. Then it is
filled with Water. Using the density of Water at the measuring
temperature and the mass of the Water required to fill the
pycnometer, the volume of the pycnometer can be
calculated. The pycnometer is then filled with the solution
whose density is to be determined and weighed. This mass,
along with the calibration volume, gives us the desired
density measurement.

Figure 4: An image of the pycnometer[1]