EXPERIMENT 5: EXCESS MOLAR VOLUMES OF LIQUID MIXTURES

INTRODUCTION

Excess volume, V E , is the difference between the volume observed when species are mixed
and the volume of an ideal solution i.e.

m A  mB mA mB
V E  Vobs  V A  VB or VE   
 A B

where V obs = volume of mixture observed, m A , m B = mass of liquid A and B, respectively, 

= density of mixture, A, B = density of liquid A and B, respectively. It is often convenient
expressing V E , in units of volume per mole and hence the term excess molar volume, V mE .
Mathematically,

VE
VmE  cm3 mol-1
n A  nB

where n A , n B = moles of liquid A and B, respectively.

V mE can take both positive and negative values depending on several factors such as
temperature, segment-segment interactions, chain length, etc. For ideal solutions, V mE = 0. In
a real (non-ideal) solution of solvents A and B, negative deviation ( V mE < 0) is observed if, for
instance, attractions between unlike molecules are greater than those between like molecules
i.e. attractive interactions A−B > A−A and/or B−B. Molecules tend to associate in this case
e.g. a mixture of chloroform with acetone due to possible hydrogen bonding. If, however, the
attraction between unlike molecules is less than that of like molecules (i.e. A−B < A−A and/or
B−B), positive deviation is observed e.g. a mixture of methanol and carbon tetrachloride in
which hydrogen bonding is destroyed due to mixing.

SUGGESTED BACKGROUND READING

Atkins, P.W., Physical Chemistry, 6th ed., 7th ed., Oxford University Press, Oxford, 1998/9
(Chapter 7)
Atkins, P.W., & Julio de Paula, Physical Chemistry, 8th ed., Oxford University Press,
Oxford, 2006 (Chapter 5)

EXPERIMENTAL

You will be provided with any two of the following solvents: water, methanol, ethanol,
propanol, isopropanol, butanol, isobutanol, cyclohexanone, cyclohexanol, cyclohexane,
pentane, hexane, etc.
Before coming to the lab, you are required to:
(a) find out from the technicians/demonstrators which pair of solvents you will be using,
and;
(b) then make of calculations of amounts by weight of solvents required to make mixtures
such that the mole fractions (i.e. XA and XB) of the solvents in each mixture are
approximately as indicated the table below. Note that you may need literature density
values of the pure solvents to do these calculations. It is advised that the total weight
should be in the range 15 – 20 g for 10 cm3 density bottles so that you have enough
sample volume for density measurement of each mixture. An example of mole
fractions required is given in the table 5.1. Please note that the table is simply a guide
and so the amounts required may differ considerably depending on the mixture used.

Table 5.1
Mixture 1 2 3 4 5 6 7 8 9 10
XA 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5
XB 0.95 0.9 0.85 0.8 0.75 0.7 0.65 0.6 0.55 0.5
Mixture 11 12 13 14 15 16 17 18 19
XA 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95
XB 0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05

Prepare the mixtures by weight (weights must be made to 4 decimal places).

Calibrate the volume(s) of density bottle(s) using distilled water (see results table 5.2).

Measure the densities of the pure solvents and the mixtures using the density bottle(s) and
enter the results in the table similar to the one given below. The density bottle has to be
cleaned using acetone and dried before each measurement.

TREATMENT OF EXPERIMENTAL DATA AND DISCUSSION

1. Do the measured densities of the pure solvents compare well with the literature values?

2. Make a table Solvent A / g, Solvent B / g, moles A, moles B, Mole fraction A, Mixture

density/ gcm-3 and V mE / cm3mol-1.

3. Plot V mE versus mole fraction of A.

4. Comment on the interactions between the two solvents.

NAME:
Student number: Date:

EXPERIMENT 5: EXCESS MOLAR VOLUMES OF LIQUID MIXTURES

Name of solvent A:.................................... Name of solvent B:....................................

1. Calibration of the density bottle

Room temperature =....................... Density of water =.....................

Table 5.1

Run wt. bottle wt. bottle + water wt. water vol. bottle
1
2
3
4
5
6
Mean volume:

Table 15.3: Example of treatment of data

No wt. A (g) nA wt. B nB XA mmixture / gcm-3 VmE / cm3mol-1
. (g) (g)
Appendix: Proposed masses of water and ethanol to prepare 15 g different mixtures of
varying mole fractions (Note: Weigh the masses using an analytical balance, i.e. 4 decimal
places).

Mixture Mass Mass

No. H2O(g) EtOH(g)
1 0 15
2 0.2 14.8
3 0.4 14.6
4 0.6 14.4
5 1 14
6 1.4 13.6
7 1.6 13.4
8 2 13
9 2.5 12.5
10 3 12
11 3.5 11.5
12 4 11
13 4.5 10.5
14 5 10
15 6 9
16 7 8
17 8 7
18 9 6
19 10 5
20 11 4
21 12 3
22 13 2
23 14 1
24 15 0