CHEMICAL AND BIOMOLECULAR ENGINEERING LAB

CH2801

Partial Molar Volume

Location: N1.2 B4-16

Name: _______________________________________

Matric Number: _______________________________________

Group: _______________________________________

Date of experiment: _______________________________________

Objectives:
1. To study partial molar properties of components in a mixture.
2. To determine partial molar volumes of ethanol-water solutions.

Theory:
A. 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 ( M i ). Partial molar properties such as partial molar volume Vi , 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 property Mt of the mixture and is defined as follows:
t
M i = (∂M /∂ni)T, P, nj(j≠i) (1)

t
M i 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 volume Vi , partial
molar enthalpy H i , and partial molar Gibbs energy Gi , are defined as:

t
Vi = (∂V /∂ni)T,P,nj(j≠i) (2)

t
H i = (∂H /∂ni)T,P,nj(j≠i) (3)

t
Gi = µi = (∂G /∂ni)T,P,nj(j≠i) (4)

Partial molar Gibbs energy Gi is also known as chemical potential of component i, µi in a mixture.
Partial molar properties are important properties and used extensively in the analysis of processes
and process equipment in chemical engineering. For example, for phase equilibrium involving
vapour-liquid equilibrium, the criteria require that
V L
Gi = Gi (for all i =1 to k components) (5)

at constant T & P.

B. Partial Molar Volume

Partial molar volume of a component (say component i) 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

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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
instance, the change in partial molar Gibbs energy with pressure at constant temperature is equal to
partial molar volume as follows.

From basic laws,

d Gi = - S i dT + Vi dP

(∂ Gi /∂P)T = Vi (6)

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, γi according to the following equation:

ln γi = (1/RT) ∫ PPref ( Vi - Vi ) dP (7)

where Vi is the molar volume of pure i measured at the same T and P as the mixture.

C. Method for Determining Partial Molar Volumes

For the determination of partial molar volumes, the graphical method based on apparent molar
volume φ described by Lewis and Randall1 may be applied.

Considering a binary mixture consisting of two components 1 and 2, the total volume of the mixture
is related to their respective partial molar volumes, V1 and V 2 as follows:

Vt = n1 V1 + n2 V 2 (8)

where n1 and n2 are moles of components 1 and 2 in the mixture respectively, and
t
V1 = (∂V /∂n1)T, P, n2 (9)

t
V 2 = (∂V /∂n2)T, P, n1 (10)

If the mixture consists of a solvent (liquid water as component 1) and a solute (ethanol as
component 2) and let V1o 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) φ as:

Vt = n1 V1o + n2 φ (11)

The solute apparent volume may therefore be defined as follows:

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φ = (Vt - n1 V1o ) / n2 (12)

From experimentally measured density ρ (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,

Vt = (n1 W1 + n2 W2) / ρ (13)

However, it is convenient to base on l000g (1 kg) of pure water with a density of ρ1 (g/ml) at the T
and P of measurement in a solution of total volume Vt. Hence

n1 V1o = 1000 / ρ1 (14)

and

Vt = (1000 + n2 W2) / ρ (15)

Equation (12) can be rewritten as,

φ = (1 / ρ) {W2 - (1000 / n2 ) [(ρ - ρ1) / ρ1 ] } (16)

By the definition of partial molar volumes according to Eqs. (9) and (10) and the total volume by
Eqs. (8) and (11),
t
V 2 = (∂V /∂n2)T, P, n1 = φ + n2 (∂φ/∂n2)T, P, n1 (17)

t o 2
V1 = (V - n2 V 2 ) / n1 = V1 - [(n2 /n1) (∂φ/∂n2) T, P, n1] (18)

The apparent solute volumes φ can be determined according to Eq. (16) from density measurements
of pure solvent ρ1 and solution mixture ρ at the same T and P at different n2. The plot of φ versus n2
will allow the evaluation of slopes (∂φ/∂n2) at different n2. V1 and V 2 can then be determined from
the above Eqs. (17) and (18).

Materials and Methods

A. Materials and Apparatus

Materials used include ultrapure water, absolute ethanol and acetone. Acetone is used for the
cleaning and drying of density measuring cell. A densiW\PHWHU shown in Figure 1 is
used for density measurements. Burettes, pipettes and glass-stoppered bottles or conical flasks
are used IRU solution preparation.

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Figure 1: Density meter
Experimental Procedures
The general procedures for using the density meter involves a cleaning step followed by a
measuring step. If there is more than 1 sample to be measured, the cleaning step should be
done in between measuring samples.
At the end of the experiment, a cleaning step is to be done before switching off the
equipment.
Note: For partial molar volume experiment, 2 sets of data is to be done at either 20°C, 30°C
or 40°C. Each temperature condition is counted as 1 set. Students are free to choose the
temperatures they want to measure.
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. Care should be taken to prevent
evaporation of the volatile component(s). A total of 25ml for each solution is required for
density measurements.
(The molecular weights of water and ethanol are 18.015 and 46.070 in g/mol respectively)

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General procedure
1) Cleaning step
2) Measuring step
Cleaning step
1) Prepare a syringe with around 2ml of acetone.
2) Click the “Dry” button. Wash the measuring cell by injecting the acetone and moving the
plunger of the syringe in & out. Flush out the acetone with the syringe.
3) Connect the drying tube to the inlet of the measuring cell. Press the green play button to
dry the cell for 60 seconds. If the cell is not completely dry, you can press the green play
button to repeat the drying process.
4) Press the “Home” button
Measuring step
1) Click “Measure”. Check that your desired temperature settings is correct (20°C, 30°C or
40°C). Temperature can be set at this step. Press the green play button.
2) Inject around 2ml to 3 ml of sample into the measuring cell. Do not remove the syringe.
From the live view camera, make sure there is no air bubbles in the measuring cell. If there
are air bubbles, repeat step 2 again. Press the green play button to start measuring the density
of your sample.
NOTE: The measuring cell should be free of air bubbles for accurate density measurements
3) You will hear a beep sound when the measurement is done. Record your results shown on
the screen. Flush out the remaining sample from measuring cell with syringe then press “ok”.
4) Tap “ok” then connect drying tube to dry measuring cell.
5) Press “Home” button
6) Before measuring your next sample, perform the cleaning step.
End of experiment
At the end of your experiment, please do a cleaning step before you leave the lab.

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References
1. Smith, J.M., and Van Ness, H. C., 'Introduction to Chemical Thermodynamics', Sixth Edition.
In SI Units, McGraw Hill (2001).

2. S. I. Sandler, “Chemical and Engineering Thermodynamics”, 2nd Edition, Wiley, (2001).

3. Daniels, F., et al. 'Experimental Physical Chemistry' 7th Edition. McGraw Hill (1970).

4. Shoemaker, D. P., and Garland, C.W., 'Experiments in Physical Chemistry', 7th Edition.
McGraw Hill (2002).

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 LOG SHEET

Name: Group: Date:

Results and discussion

Tabulation and Calculations

1. Tabulate your results under the following headings in Table 1:

Table 1: Density measurements for water-ethanol mixture (T = 20/30/40 oC, P = 1 atm)

Density of ultrapure water: ρ1 = (g/ml)
Density of absolute ethanol: ρ2 = (g/ml)

Sample Ethanol Density n1 n2 φ φ/dn2)

(dφ V1 V2
no. (Vol %) ρ (ml/g) (mol) (mol) (ml/mol) (ml/mol) (ml/mol)

2. Plot φ versus n2 using the determined density values of the mixture according to Eq.
(16). Determine (dφ/dn2) from the slopes and also calculate V1 and V 2 .

3. Plot also the calculate values of V1 and V 2 versus n2 and draw a smooth curve for each
of the two partial molar volumes. Discuss the results in relation to Gibbs-Duhem
equation:
∑ xi d Vi = 0 at constant T and P.

4. Discuss qualitatively the effects of temperature and pressure on partial molar volumes.