Department of Mining, Metallurgical and Materials Engineering

MatE 104 Experiment Guide

Partial Molar Volume Measurement

THEORY

Most thermodynamic variables fall into two types. Those representing extensive properties of a
phase are proportional to the amount of the phase under consideration. Those representing
intensive properties are independent of the amount of the phase. Variables of both types may be
regarded as examples of homogeneous functions of degree l, that is, functions having the
property
f (kn1 ,...kni ,...) = k f (n1 ,..., ni ,...) Equation 4- 1

Where ni represents for our purposes the number of moles of component i in a phase.

Extensive variables are functions of degree one and intensive variables are functions of degree
zero.

Among variables important in thermodynamics are partial molar quantities, defined by the
equation
Q
Qi =
ni p ,T ,n j i
Equation 4- 2

Q may be any of the extensive quantities already mentioned. For a phase of one component,
partial molar quantities are identical with so-called molar quantities, Q = Q n .

A property of great usefulness possessed by partial molar quantities derives from Eulers
theorem for homogeneous functions, which states that, for a homogeneous function
f (n1 ,...ni ,...) of degree l,
f f f
n1 + n2 + ! + ni + ! = lf Equation 4- 3
n1 n2 ni

Applied to an extensive thermodynamic variable Q , for which l = 1 , we see that

n1Q1 + n2Q2 + ! + ni Qi + ! = Q Equation 4- 4

For the important special case of constant pressure and temperature,

n1 dQ1 + ! + ni dQi + ! = 0 at constant p and T Equation 4- 5

This equation tells us that changes in partial molar quantities (resulting of necessity from
changes in the ni) are not all independent. For a binary solution, one can write
dQ 2 X
= 1 Equation 4- 6
dQ1 X2

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 Department of Mining, Metallurgical and Materials Engineering
MatE 104 Experiment Guide
Partial Molar Volume Measurement

ni
where the Xi are mole fractions, X i = . In application to free energy this equation is
ni
commonly known as the Gibbs-Duhem equation.

We are concerned in this experiment with the partial molar volume Vi , which may be thought
of as the increase in the volume of an infinite amount of solution (or an amount so large that
insignificant concentration change will result) when 1 mole of component i is added. This is by
no means necessarily equal to the volume of 1 mole of pure i.

Partial molar volumes, and in particular their deviations from the values expected for ideal
solutions, are of considerable interest in connection with the theory of solutions. As applied to
binary mixtures of liquid components, where they are related to heats of mixing and deviations
from Raoults law.

We see from Equation 4-4 that the total volume of an amount of solution containing 1 kg of
water and m mole of solute is given by
V = n1V1 + n2V2 = 55.51V1 + mV2 Equation 4- 7
0
where the subscripts 1 and 2 refer to solvent and solute, respectively. Let V1 be the molar
volume of pure water equivalent to 18.016/0.997044 = 18.069 cm3/mol at 25C. Then we define
the apparent molar volume of the solute by the equation:
1 1
=
n2
( ) (
V n1V1 0 = V 55.51V1 0
m
) Equation 4- 8

1 1000 W W0
= MW *
Equation 4- 9
d m W0 We

where d = density of the solution in g/cm3

MW = the solute molecular weight in grams
W = weight of pycnometer filled to mark with solution
W0 = weight of pycnometer filled to mark with pure water
We = weight of empty pycnometer

Now, by the definition of partial molar volumes and by use of Equations 4-7 and 4-8,
V d
V2 = = + n2 = +m Equation 4- 10
n2 n1 ,T , p n2 dm

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 Department of Mining, Metallurgical and Materials Engineering
MatE 104 Experiment Guide
Partial Molar Volume Measurement

Also
1 0 2 0 m 2 d
V1 = n1V1 n2
= V1
n1 n2 55.51 dm Equation 4- 11

We might proceed by plotting versus m, drawing a smooth curve through the points, and
constructing tangents to the curve at the desired concentrations in order to measure the slopes.
However, for solutions of simple electrolytes, it has been found that many apparent molar
quantities such as vary linearly with m even up to moderate concentrations. This behavior
is in agreement with the prediction of the Debye-Hckel theory for dilute solutions. Since
d d d m 1 d
= =
dm d m dm 2 md m Equation 4- 12

we obtain from Equations 4-10 and 4-11

m d m d 3 m d
V2 = + = + =0 +
2 md m 2 d m 2 d m Equation 4- 13

m m d
V1 = V1 0
Equation 4- 14
55.51 2 d m

where 0 = apparent molar volume extrapolated to zero concentration

V1 0 = 18.069 cm3/mol
Now one can plot versus m and determine the best straight line through the points. From
d
the slope and the value of 0 , both V1 and V2 can be obtained.
d m

MATERIALS AND EQUIPMENT

Pycnometer Analytical Balance Aspirator Acetone/Methanol

Thermometer Volumetric flasks Reagent-grade NaCl Lint-free wipes
Water Bath Pipette Distilled water

Some points regarding the Pycnometer:

1. The pycnometer should be thoroughly dried before use.
2. The filling of a weld-type pycnometer must be carried out with great care.
3. The temperature of the laboratory must be below the temperature at which the
determination is to be made.

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 Department of Mining, Metallurgical and Materials Engineering
MatE 104 Experiment Guide
Partial Molar Volume Measurement

4. As the pycnometer cools to room temperature, the liquid column in the capillary will
descend. Be careful not to heat the pycnometer with your hands since this will force
liquid out of the capillary.

PROCEDURE

A. Preparation of Solutions
1. Prepare 200 mL of 1.5 M, 0.75 M, 0.375 M, 0.1875 M and 0.09375 M NaCl solutions by
successive volumetric dilutions; and
2. Put necessary labels.
B. Calibration of the Pycnometer
1. Obtain a pycnometer and rinse it with distilled water. Use an aspirator and dry by
suction. Use a few rinses of acetone/methanol to expedite drying.
2. Weigh the pycnometer until a weight difference of 0.01 gram is obtained
3. Fill the pycnometer with distilled water and seat the capillary stopper firmly.
4. Wipe off excess liquid around the joint and immerse in a water bath just below the cap
of the pycnometer. The water bath must be maintained at a constant temperature (must
be noted).
5. Allow the pycnometer to reach equilibrium with the water bath (approximately three
minutes). Remove from the bath and wipe off excess liquid from the capillary tip, being
careful not to draw additional liquid out of the capillary.
6. Measure the weight and record.
7. Make three replicates.

C. Experimentation Proper
1. Starting with the 1.5 M NaCl solution, rinse the calibrated pycnometer with some of the
new sample and discard before filling.
2. Fill the pycnometer with the corresponding solution. Follow the same procedures as in
the calibration with water.
3. Make three replicates for each of the concentrations of NaCl solution.

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 Department of Mining, Metallurgical and Materials Engineering
MatE 104 Experiment Guide
Partial Molar Volume Measurement

TREATMENT OF RESULTS

1. Calculate the density d of each solution using the obtained data and the calibrated
volume of the pycnometer.
2. Calculate molality m of each solution:

1
m= Equation 4- 15
d M2
_
M 1000

where d = density of the solution (g/cm3)

M = molarity of the solution (mol/L)
M 2 = molecular weight of the solute (g/mol)
3. Calculate (apparent molar volume).
d
4. Plot versus m and determine the best-fit line. Calculate the slope and
d m
extrapolate to zero concentration 0 (use statistical methods to solve accurately).
5. For each molarity of solution, calculate the partial molar volume of NaCl, V2 .
6. Calculate the partial molar volume of H2O, V1 .
7. Present in tabular form the derived values for M, m, d, V1 and V2 .
8. What is the effect of increasing concentration of NaCl on the partial molar volume of
NaCl and H2O? Explain your answer.
9. Looking at the graph of versus m , how accurate would you say your
determinations were for solution densities?
10. Discuss major sources of errors in the experiment and how these can be eliminated.

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