Revised 01/05 CHEMISTRY 232

Partial Molar Volumes

The purpose of this experiment is the determination of the partial molal volume
of water and of salt in a series of NaCl - H
2
O solutions of known weight-percent
composition.

DISCUSSION:

If the solution contains n
A
moles of A and n
B
moles of B, then

n
V
=
V
A
n , T P,
A
B
(1)

In principle, it is possible to measure the increase in volume (V) on adding an
infinitesimal amount (n) at constant pressure and temperature, to a large amount of
mixture of known composition.

constant) P (T,
V
n
+ V
n
= V
B
B A
(2)

V
A
and V
B
may be evaluated by density measurements on the solutions. We define a
quantity called the apparent molal volume

n
V n
- V
=
B
0
A A
V
(3)

V = volume of solution containing n
A
moles of A and n
B
moles of B.

o
A
V = volume of 1 mole of pure A (solvent) at given T and P.

Rearranging:
(4)
V n
+
n
= V
0
A A
V
B

Differentiate (4) with respect to n
B

n
n
+ =
n
V
=
V
B
V
n
P, T,
B
V
B
n
T, P,
B
A A
(5)


CHEMISTRY 231 Partial Molar Volumes Page 2
Rearranging (2) -
n
V
n
- V
=
V
A
B
B
A
(6)
Combining (4), (5) and (6)

n
n
-
n
-
V
n
+
n
n
1
=
V
B
V
n
P, T,
2
B V
B
0
A
A
V
B
A
A
A
(7)

Let the molecular weights of A & B be M
A
& M
B
respectively, and let be the
experimental density of the solution.

M n
+
M n
= V
B B A A
(8)

Substitute (8) into (3) -

V
n
-
M n
+
M n
n
1
=
0
A
A
B B A A
B
V
(9)

If we use the molal scale, then


A A B B
M / 1000 n and m n = =

where A is the solvent.

Thus

V
M
1000
-
M m
+ 1000
m
1
=
0
A
A
B B
B
V
(10)

but M
A
/V
A
= = density of pure A at constant T, P.
0
A

M
+ ) - (

m
1000
=
B 0
A 0
A
B
V
(11)








CHEMISTRY 231 Partial Molar Volumes Page 3
PROCEDURE:
WASTE DISPOSAL
all solutions Sink with lots of water.

Each pycnometer should be clean and dry. Make sure all flasks and stoppers are
labelled and that the same stopper is used with a flask throughout the experiment.
Each dry air-filled flask is weighed.

Each flask is then filled with deionized water. The flask is then placed in the
constant temperature bath and let equilibrate for at least five minutes. The flask is
then removed, dried carefully and the stopper inserted. The flask is now reweighed.

A similar procedure is then followed using sodium chloride solutions instead of
deionized water.

Prepare NaCl solutions of ~2%, 7%, 10%, 14% and 20%. (One for each
pycnometer).

To determine the weight of the flask itself, a correction must be made for the
mass of air.

Look up the handbook value for the density of air at the room temperature and
barometric pressure in question, then calculate the mass of air in 25 mL. Subtract
this weight from the weight of the air-filled flask to give the weight of the empty
flask.


PROCESSING OF DATA:

From your data, and the C.R.C. density of water, calculate the exact volume of
each flask.

Then a density can be obtained for each salt solution. Knowing the EXACT
amount of NaCl used to prepare each NaCl solution, we can calculate the molality of
each solution.

From these values we can use equation (11) to calculate
v
.

CHEMISTRY 231 Partial Molar Volumes Page 4
If we plot
v
versus molality we do not get a very good straight line.

However,

m
2
1
=
m
m

m m 2
1
=
m
m

m
=
m
=
n
2 1 -
2 1
2 1
v
P , T , n
2 1
2 1
2 1
v v
P , T , n
B
v
P , T , n
A
A A

(12)

Now if we plot
v
versus m
1/2
, a much straighter line is obtained.

Plot the graph, draw the best-fitting straight line, and from the slope and
equations 5 and 12, calculate the partial molal volume of NaCl at three different
concentrations. Compare these to the molar volume of NaCl.