I.

ABSTRACT

The focus of this experiment is the determination of the partial molar volume of ethanol-water
system. This experiment also emphasized the demonstration on how to use the pycnometer for
measuring density and specific gravity, which was then further explained in the procedures part of
this report. These density and specific gravity measurements were then used to determine the
partial molar volume of the considered ethanol-water system at different concentrations. By the end
of the data gathering, the results were then interpreted and the group was able to present that the
molar volume of pure ethanol is 58.801 cm3/mol and that of distilled water is 18.073 cm3/mol.
II.

INTRODUCTION

The volumes of the components of a solution are not additive in general. First of all, considering a
mixture of water and ethanol, the molecules experience different intermolecular forces than in the
pure substances in the solution. That is, the intermolecular forces between a water molecule and an
ethanol molecule, is different from the intermolecular forces between two water molecules, or
between two ethanol molecules. Secondly, water and ethanol molecules have different sizes and
shapes, and, consequently, the molecules in pure water, or in pure ethanol, are going to fit together
differently, than the molecules in a solution of ethanol and water. These two factors: differences in
molecular sizes and shapes and differences in intermolecular forces, compared to the pure
substances, cause the molecules to pack together differently in the mixture than in the pure liquids,
and result in the non-additivity of the volumes.
A quantitative treatment of this behavior requires the introduction of the partial molar volume.
Consider a solution at constant pressure and temperature prepared by mixing n1, n2ni moles of
substances 1, 2, i. The total volume of the unmixed pure substances is:
V*= n1Vm,1* + n2Vm,2* + niVm,i*
Where Vm,i* is the molar volume of pure substance i. After the pure substances are mixed to form
the solution, the total volume of the solution is:
V = n1V1 + n2V2 + niV
In equations (1) and (2), V is not necessarily equal to V*. In equation (2), the quantity Viis the molar
volume of the ith substance in the solution, and is called the partial molar volume of substance i. For
the reasons mentioned above, Vi is not necessarily equal to Vm,i*. That is, the volume occupied by
one mole of i in solution is different from the volume occupied by one mole of pure i.
The partial molar volume of a substance is an intensive property. That is, it depends on the
composition of the solution, but not on the amount of solution. Another way of saying this is that Vi
depends on the mole fractions and not on the number of moles. The total volume, on the other
hand is an extensive property. The partial molar volume of a substance is the molar volume of the
substance in a solution at a particular composition.
The value of V(m) is obtained for several values of m. The slope of V(m) plotted versus m is the first
derivative. The slope at any point on the curve is obtained by drawing a line tangent to the curve at
the point of interest. The slope of the curve at that point is the slope of the tangent line, and is equal
to the partial molar volume of the solute, V2. The graph above shows that, generally, the slope and,
hence, the partial molar volume varies with concentration.

III.

METHODOLOGY

LIST OF CHEMICALS AND APPARATUS

Ethanol
Distilled water
Acetone (for drying)
25 ml pycnometer
This apparatus is used for measuring the density of a solution using a
reference liquid, such as water. This would identify the specific gravity
of the solution which was then used to determine the partial molar
volumes. The total volume of the mixture could also be computed
afterwards.

Erlenmeyer flasks
Since ethanol is volatile the Erlenmeyer flasks were needed
to be covered with parafilm paper to prevent ethanol from
evaporating in the surrounding. Each flasks were labeled
according to the % volume of ethanol content.

Analytical balance
Thermometer/barometer
25 ml graduated cylinder

Water bath

It is important that the temperature is the same

throughout the measurement of densities of the samples.
Thus, water bath is essential in this experiment. Flaks had
to be put in water bath within 3-5 minutes to ensure that
they had the right temperature.

A. PREPARATIONS OF LIQUID MIXTURES

1. 7 clean empty labeled erlenmeyer flasks covered with parafilm paper were weighed in an
analytical balance.
Each flask was labeled according to its % vol. ethanol content. (0, 17, 33,50, 67, 83 and
100%)
2. Each flasks contained 30ml samples of solutions of ethanol and water. The mass of each
component were determined by using this procedure:
i.
Put approximate volume of water into flask
(mass of flask + water)
ii.
Put the ethanol
(mass of flask + water + ethanol)
iii.
Data were recorded in the data blanks
3. After the mass determinations, actual mole fraction of each solutions prepared were
calculated.
4. These solutions were put in a thermostated bath for atleast 3 minutes before measuring
their densities.
5. The temperature of the bath was recorded afterwards.

B. MEASURING THE MASS OF THE REFERENCE LIQUID USING A PYCNOMETER

1. A clean and dry pycnometer was weighed.
2. It had been filled with water and mass was also measured. This set to be the Mass
reference.
3. Upon using the pycnometer, it had to be clean using technical acetone.
C. DENSITY MEASUREMENTS
1. The procedure outlined in part B was also performed for other samples prepared in part
A as well as for the pure alcohol sample.
2. Data were recorded
3. Densities of each mixture was then calculated.
4. Ideal molar volume of each prepared solution(Vm*) was then determined using the
density of pure ethanol and water.
5. Actual volume and actual molar volume (Vm) of each prepared solution could also be
calculated by using the density values of each solution.
D. PARTIAL MOLAR VOLUME CALCULATION

1. The graph of molar volume (Vm) vs. Mole Fraction of ethanol using the data could now
be plotted.
2. Using the tangent method, the partial molar volume of water and ethanol for each
concentration was then determined.
These values had to be compared with the molar volumes of the pure compounds and conclusions
could now be drawn from these comparisons.

IV.

RESULTS AND DISCUSSIONS:

Table 2.1: Preparation of Liquid Solutions

Approx Appr
mass of
Approx
Volume ox
empy
flask + A
Vethanol ,
%
of Vwater
flask (mo), (mA*)
mL
Ethanol , mL
g
100
0
30
93.4693
93.4693
83
5
25
92.7797
97.0732
67
10
20
95.0010
104.3756
50
15
15
95.1046
109.6534
33
20
10
93.8422
113.2388
17
25
5
88.6713
113.1670
Temperature of water bath:

300K

Density of distilled water:

0.996513 g/cm3

flask + A
mA* m0 mB*-mA*
+B (mB*)
mA, g
mB, g
,g

nA

nB

117.133
116.2086
119.5494
120.8670
120.6230
116.5632

0
0.23853
0.52081
0.80827
1.07759
1.36087

0.5144
0.4160
0.3299
0.2438
0.1605
0.0738

0
4.2935
9.3746
14.5488
19.3966
24.4957

23.6637
19.1354
15.1738
11.2136
7.3842
3.3962

molar volume of distilled water: 18.0730 cm3/mol

Table 2.2: Density Determinations
Approx
Volume
X
%
of B
Ethanol

XA(1-XB)

Mavg
(g/mol)

Mass
of mass
pycnometer, pycnometer
g
+ liquid

Mass
of Density
liquid, g
mix g/cm3

100
83
67
50
33
17
0

0
0.3644
0.6122
0.7683
0.8703
0.9485
1

46.0000
35.7958
28.8575
24.4880
21.6303
19.4409
18.0000

13.6428
13.6500
13.6505
13.6467
13.6561
13.6385
13.627

20.1022
21.8830
22.6088
24.2544
24.4746
25.0965
25.6073

1
0.6356
0.3878
0.2317
0.1297
0.0515
0

33.7450
35.5330
36.2593
37.9011
38.1307
38.7350
39.2343

0.7823
0.8516
0.8798
0.9439
0.9524
0.9766
0.9965

Molar volume, like the term implies, is the volume occupied by 1 mole of a substance or mixture of
substances at a particular temperatur and pressure. Distilled water, for instance has a molar volume
of 18.0630 cm3/mol at 300K. Just like density, which is the ratio of mass to volume, and specific
gravity which is the ratio of a subtances density to that of a reference substance, molar volume is an
intensive property. Its value is constant for a specific substance or mixture at certain temperature
and pressure. This means that the molar volume of 20 mL of distilled water is the same even if the
volume is increased to 30 or 40, and so on.
4

Partial molar volume, in contrast to molar volume, is an intensive property. The partial molar volume
of a substance in a mixture, say substance A, is the change in volume per mole of A added to a large
volume of the mixture. As an illustration, imagine a huge volume of pure water at 25C. When a
further 1 mol H2O is added, the volume increases by 18 cm3 so it can be reported that 18 cm3 / mol
is the molar volume of pure water. However, when 1 mol H2O is added to a huge volume of pure
ethanol, the volume increases by only 14 cm3. The reason for the differen (Atkins & de Paula, 2010)t
increase in volume is that the volume occupied by a given number of water molecules depends on
the identity of the molecules that surround them. In the latter case there is so much ethanol present
that each H2O molecule is surrounded by ethanol molecules. The network of hydrogen bonds that
normally hold H2O molecules at certain distances from each other in pure water does not form. The
packing of the molecules in the mixture results in the H2O molecules increasing the volume by only
14 cm3. The quantity 14 cm3 /mol is the partial molar volume of water in pure ethanol.
In this experiment, the effect of increasing the molar concentration of ethanol in a 30 mL waterethanol mixture to the its partial molar volume and eventually to the molar volume of the entire
mixture was illustrated. The molar volume of the seven solutions with varying molar concentration
of ethanol was obtained in three different methods:

; this was considered as the experimental value of molar volume.

Vm*=(XB*VmB) + (XA*VmA) ; this was considered the theoretical value of the molar volume
Vm was obained by tangent method.

In the first method, Mave is the molar mass of the mixture which was obtained by using the mole
fraction of the components. Component B is the ethanol and component A is water. Mave was then
divided to the density, , of the corresponding mixture. The derivation was as follow:

For the second method, the partial molar volume of each component was obtained by multiplying
the mole fraction to the literature value of substances molar value at a particular temperature.
For each method it can be predicted, base from the formula, that as the molar concentration of
ethanol increases, the molar volume of the mixture increases also. This is true provided that all other
conditions such as the components total volume of the mixture, temperature, and volume are held
constant.
Table 2. 3: Determination of Molar Volume of Solutions
Approx
Volume VM*
VM
Vmix
%
of (cm3/mol) (cm3/mol) cm3/mol
Ethanol

%difference

100
83
67

0.0024
4.4659
3.1827

58.8010
43.9547
33.8599

58.8024
42.0346
32.7991

0.0014
1.9201
1.0608

50
33
17
0

27.5026
23.3448
20.1594
18.0630

25.9444
22.7106
19.9060
18.0630

1.5582
0.6343
0.2534
0.0000

5.8308
2.7544
1.2649
0.0001

Temperature of water bath, oC:

Density of pure ethanol,
g/cm3:
Density of distilled water, g/cm

27
0.783336

0.996513
3

Molar Volume of pure ethanol, cm /mol:

58.801

Molar Volume of distilled water, cm3/mol:

18.073

In the tangent method shown below, a value of XB was chosen. In this case 0.2317. A tangent line
was then drawn from it. From the tangent line, partial molar volume of B and partial molar volume
of A was determined. Those values were used to calculate for the molar volume of the mixture
containing XB mole fraction ethanol, using the following computation:

% difference = 3.44%
It was observed that the theoretical value of Vm is greater than the experimental and by tangent
method, but with only a small % difference. This is can be accounted to the fact that while the
theoretical value is just an estimate based on the amount of components molecules, the partial
molar volumes of the components of a mixture vary with composition because the environment of
each type of molecule changes as the composition changes from pure water to pure ethanol. It is
this changing molecular environment, and the consequential modification of the forces acting
between molecules, that results in the variation of the thermodynamic properties of a mixture as its
composition is changed.

Molar Volume vs Molar Fraction of B

70.00
60.00

Partial molar
volume of B at
XB: 55 g/cm3

50.00
40.00

Vm
30.00

Power (Vm)

20.00

Partial molar
volume of A at

10.00

XB
0.00
0.00000.10000.20000.30000.40000.50000.60000.70000.80000.90001.00001.1000

Figure 2.1. Tangent Method in Determining Molar Volumes

TANGENT-INTERCEPT METHOD
X
Y
Approx
Volume %
of Ethanol

VM*
(cm3/mol)

XB

Vmix
cm3/mol

Partial
Volume of
Water

Partial
Volume of
Ethanol

100
83
67
50
33
17
0

58.801
43.95466561
33.85990039
27.50261845
23.34482912
20.15939554
18.063

1
0.635565
0.387768
0.231715
0.129654
0.05146
0

0.00140
1.92011
1.06078
1.55819
0.63427
0.25340
0.00001

0.00000
15.37605
17.87447
17.38092
18.01378
18.06324
18.06300

58.80100
57.32060
56.36307
54.33851
54.23938
53.87242
58.80100

Approx Volume %
of Ethanol
100

Y
X=1
VM*
Vmix
XB
(cm3/mol)
cm3/mol
58.8010 1.0000 0.0014 0.0014

Molar
Volume
Using
TangentIntercept
Method
58.80100
42.03456
31.26951
25.94456
22.71056
19.90599
18.06300

Values Y, given the following X of Tangent Line

X=0.6356 X=0.3878 X=0.2317 X=0.1297 X=0.0515

1.4804

2.4379

4.4625

4.5616

4.9286
7

83
67
50
33
17
0

43.9547

0.6356

1.9201

33.8599

0.3878

1.0608

27.5026

0.2317

1.5582

23.3448

0.1297

0.6343

20.1594

0.0515

0.2534

18.0630

0.0000

0.0000

3.1326
3.0176
3.7867
4.2898
4.6752
4.9288

1.9201

1.6182

3.0848

2.9171

3.1323

2.2191

1.0608

2.1480

1.7990

1.9110

2.4074

0.7098

1.5581

1.0948

1.1418

2.5305

0.4802

1.1722

0.6343

0.6388

2.6249

0.3043

0.8766

0.2814

0.2534

2.6870

0.1885

0.6821

0.0492

-0.0002

6.00000

5.00000

4.00000

Vmix cm3/mol
tangent at X=0.635565

3.00000

tangent at X=0.38777
tangent at X=0.23175
tangent at X= 0.129654
2.00000

tangent at X=0.05146
Poly. (Vmix cm3/mol)

1.00000

0.00000
0

0.1

0.2

0.3

0.4

y = -3.4127x3 - 1.7351x2 + 5.1345x + 0.0402

0.5
0.6
0.7
0.8
0.9
1

1.1

-1.00000

Figure 2.2 Difference in Molar Volume vs Mole Fraction of Ethanol: Tangent-Intercept Method of
Finding the Partial Molar Volume

70.00000

60.00000

50.00000

40.00000
Ethanol
Water

30.00000

20.00000

10.00000

0.00000
0

0.2

0.4

0.6

0.8

1.2

Figure 2.3. Partial Molar Volume of Ethanol and Water

As mentioned earlier, that while the value of molar volume is constant no matter what the volume
of a given substance or mixture is, all other conditions must remain constant as well such as
temperature. Molar volume will already be different once these conditions changed. When the
temperature is increased, molecules occupy a bigger volume but the number of moles remain the
same. This would make the value of molar volume increase as well, but for liquids which have strong
intermolecular forces of attraction such as water, this change would not be as big as compared to
ethanol which evaporates easily.
For ideal solutions,those that are formed from components that have very similar structures and
hence similar forces of attraction operating among molecules, very similar forces of attraction lead
to minimal expansion or contraction in the volume of the mixture formed from the components.
Thus we can expect the partial molar volume to be equal to the molar volume of each component.
However, there are no two compounds which are exactly alike, at some point there will always be a
deviation so in reality, the only time that partial molar volume is equal to the molar volume is then
the solution is made up of pure substance.
V.

SAMPLE CALCULATIONS

A. PREPARATION OF LIQUID SOLUTIONS:

dH2O = 0.996573
Molar Volume of distilled water:
mH2O = 28.4724 g
10

VH2O =

VH2O = 28.5720 g/cm3

Vm1H2O =

Vm1H2O = 18.0630 cm3/mol

Comparing it with literature value of VmH2O = 18.0730 cm3/mol
B. DENSITY DETERMINATIONS (USING 83% ETOH):
XB =

= 0.6356

XA =

= 0.3644

mixture =

x H2O @ 27C

Mavg= XbMb + XaMa

= (0.6356) (46) + (0.6344) (18)

x 0.996573

mixture = 0.8156 g/cm3

Mavg = 35.7968 g/mol

C. MOLAR VOLUME OF SOLUTIONS (USING 83% ETOH)
Vm(exp) =

= 42.0348

Vm*(theo) = XBVmB* + XAVmA*

= (0.6356) (58.8010) + (0.6344) (18.0630)
Vm*(theo) = 45.9561 cm3/mol

VI.

SUMMARY AND CONCLUSION

The preparation of liquid solutions provided insight on the process to determine the molar
volume of distilled water, with a very slight difference to the literature value of the molar density of
distilled water. The calculations used in the lectures were used, and it enabled us to understand
more the concept of the topic because we were able to apply it to actual experiments. The
experiment could have been easier to perform if more apparatus were available for each group. The
experiment also showed the direct proportionality of the amount of a substance to its mole fraction
in a solution. We were able to determine the molar volume of solution, wherein ethanol was used in
different volume percentages. Overall the experiment helped us to gain more knowledge in molar
volumes, and varying densities, however more accurate results could have been achieved had there
been more apparatus available, so more time could have been saved.
VII.

REFERENCES:

(n.d.). Retrieved on October 2014, from

http://www.chemistry.mtu.edu/~kmsmith/PChem/Experiments/3511/MolVol/MolVol.pdf
11

(n.d.). Retrieved on October 2014, from

http://www2.stetson.edu/~wgrubbs/datadriven/fchen/bartender/partialmolarvolumechen.
html
Atkins, P., & de Paula, J. (2010). Physical Chemistry. New York, NY: W.H. Freeman and Company.
Epstein, L. (1986). Laboratory Manual for Chemistry.
Nicol, M. F., Russell, A. A., & Siebert, E. D. (1973). Experimental Studies for General Chemistry.

12