PERIODIC TRENDS IN PARTIAL MOLAL VOLUMES

OBJECTIVE
To determine the partial molal volume of a solute and a solvent in an aqueous
salt solution.
THEORY
Thermodynamic variables may be regarded as homogeneous functions of
degree n, that is, they are functions having the following property:
( ) ( )
n
1 2 n 1 2 n
f x , x ,... x f x , x ,...x
(1)
Where is an arbitrary constant and the xis are parameters dependent on the
quantity of the components of the system. Extensive properties such as H, S, U,
G, A, and V are homogeneous functions of degree one while intensive properties
such as P, T, and the partial molal quantities are of degree zero.
The total differential of a thermodynamic property F(T,P,n1,, nj) may be
written in terms of its partial derivatives as:
1 j 1 j
j i
j
i
i 1 P,n ,...n T,n ,...n i
T,P,n
F F F
dF dT dP dn
T P n

_ _ _
+ +


, ,
,

1 j 1 j
j
i i
i 1 P,n ,...n T,n ,...n
F F
dF dT dP Fdn
T P

_ _
+ +


, ,
(2)
Where ni is the number of moles of the i
th
component and
i
F is the partial molal
quantity of the property F.
At constant temperature and pressure, equation (2) reduces to:
1 1 2 2 j j
dF Fdn F dn ... Fdn + + + (3)
Eulers theorem for a homogeneous function of degree one at constant T
and P gives the following expressions for F:
1 1 2 2 j j
F Fn F n ... Fn + + + (4)
Differentiation of equation (4) and comparison with equation (3) yields the
Gibbs-Duhem equation, applicable under constant temperature and pressure:
1 1 2 2 j j
n dF n dF ... n dF 0 + + + (5)
Eulers theorem and the Gibbs-Duhem equation may be applied to
solutions. The property of solutions to be studied is its partial molal volume.
Experimentally, the partial molal volume is measured by adding one mole of a
component to a volume of solution so large that the volume effect of the
component will not appreciably alter the concentration of the other components
of the solution. The change in volume due to the component under this condition
is equal to the partial molal volume of that component.
The volume of a two-component solution in the Euler form at a particular
temperature and pressure is:
1 1 2 2
V Vn V n + (constant T, P) (6)
While graphical methods can be used for the evaluation of the partial
molal volumes
1
V and
2
V , the method of slopes which is based on the concept
of apparent molal volumes is convenient for binary systems. In this method the
volume of solution is:
o
1 1 2 2
V V n n + (7)
and
o
1 1
2
2
V V n
n

(8)
where
2

is the apparent molal volume of the solute (component 2), V is the

volume of the solution containing n1 moles of the solvent (component 1), and n2
moles of the solute.
o
1
V is the molar volume of the solvent, at the specified
temperature and pressure.
The quantity
2
V can be obtained from the definition of partial molal
volumes and from equation (7).
1 1
o 2
2 1 1 2 2 2 2
2 2 2
n ,T,P n ,T,P
V
V V n n n
n n n
_ _
1
+ +

]

, ,
(9)
The quantity
1
V can be obtained by equating equations (6) and (7) and
solving for
1
V :
o
1 1 2 2 1 1 2 2
Vn V n V n n + + (10)
( )
o
o 1 1 2 2 2 2 2
1 1 2 2
1 1
V n n V n n
V V V
n n
+
+ (11)
expanding
2
V by equation (9):
1 1
2
o o 2 2 2 2
1 1 2 2 2 1
1 2 1 2
n ,T,P n ,T,P
n n
V V n V
n n n n
_ 1
_ _

1 + +


1
, ,
] ,
(12)
The apparent molal volume
2

, may be expressed in terms of densities,

which are readily measurable. Solving for
2

from equation (10):

( )
o
o 1 1 2 2 1 1 1
2 1 1 2
2 2
Vn V n V n n
V V V
n n
+
+ (13)
Recall that the molar volume (in mL/mol) is simply the ratio of molar mass
and density:
g
M
mL mol
V
g mol
mL
_

_
,

_
,

,
(14)
Replacing molar volumes in equation (13) with densities thru equation
(14):
1 1 1 2 1 1 2
2
2 o 2 o
1 2
2 o
n M M M n M M 1 1
n n
g M 1 1
n
_ _
+ +


, ,
_
+


,
(15)
where M1 is the molar mass of solvent, M2 is the molar mass of solute, is the
density of the solution, o is the density of pure solvent, and g1 is the mass (in
grams) of solvent.
Recall that the molal concentration is defined as the number of moles of
solute per kilogram of solvent:
2 1
1 2
n (mol) g 1000g 1000
m
g (g) 1kg n m
_


,
(16)
Expressing equation (15) in terms of molalities and rearranging:
2
2
o
M 1000 1 1
m
_
+


,
(17)
In 1929, D. O. Masson showed that for solutions of simple electrolytes of
dilute to moderate concentrations, a linear relation exists between
2

and the
square root of molality (
m
). In equation form,
o 2
2 2
d
m
d m
_
+

,
(18)
where
o
2
is obtained by extrapolation of
2

to zero concentration and

2
d
d m
_

,
is
the slope of the plot of
2

versus
m
.
Since
2
d
d m
_

,
is the readily obtainable data, we cannot use equation (9)
and (12) to solve for the partial molal volume unless we express the derivative
2
2
d
dn
_

,
in terms of
2
d
d m
_

,
. For 1000 g of solvent, n2 is equal to m. Hence,
2
2
d
dn
_

,
is equal to
2
d
dm
_

,
. The relation of
2
d
dm
_

,
and
2
d
d m
_

,
is given by:
( )
1
2 2 2 2 2
d d d d d m d 1
m
dm dm dm
d m d m 2 m d m
_
_ _ _




, , ,
,
(19)
Substituting equation (19) to equation (9) and expanding
2

in terms of
equation (18), we obtain an expression for
2
V (recall that for 1000 g of solvent n2
= m):
2 2
2 2 2
o 2 2 2
2 2
d d 1
V m m
dm
2 m d m
d d d m m
m
2 2
d m d m d m
1 _ _
+ +
1
, , ]
1 _ _ _
+ + +
1
, , , ]
o 2
2 2
d 3
V m
2 d m
_
+

,
(20)
Since we assume that there is 1000 g of solvent, the following expression
holds for the number of moles of solvent, n1:
( )
1
1000g 1
1kg n (mol)
1kg M(g/ mol)
_ _

, ,
(21)
We extend the same procedure for
1
V :
2 2 2
o o o 2 2 2
1 1 1 1
1 1
1
2 2
o o 1 2 1 2
1 1
3
2
o 1 2
1
d d d m m m
V V V V
1000
n dm n dm dm
M
Mm d Mm d 1
V V
1000 dm 1000
2 m d m
Mm d
V
2000
d m
_ _ _


, , ,
1 _ _

1
, , ]
_


,
3
2
1 1 2
1
o
M Mm d
V
2000 d m
_

,
(22)
The densities of a series of solutions can be used to calculate
2

from
equation (17). The plot of
2

versus
m
yields
o
2
and
2
d
d m
_

,
.
2
V and
1
V can
then be computed from equations (20) and (22), respectively.
MATERIALS AND APPARATUS
50-mL Weld pycnometer thermometer
analytical balance barometer
(5) 100-mL volumetric flasks (5) 100-mL beakers
deionized water
PROCEDURE
1. Read the barometric pressure and temperature of a wet and dry bulb
thermometer.
2. Clean the pycnometer and rinse thoroughly with deionized water. Oven dry.
3. Prepare of 1.0 M aqueous salt stock solutions of LiCl, NaCl, KCl, KBr, and KI
on 250 mL volumetric flasks by weighing appropriate amount of the salt and
dissolving it in deionized water.
4. For each salt, prepare 100 mL of 0.10 M, 0.20 M, 0.30 M, 0.40 M, and 0.50 M
(or six different concentrations) from the stock 1.0 M solution by serial dilution.
5. Allow the pycnometer to attain thermal equilibrium with the room and weigh on
the analytical balance. Fill up the pycnometer with deionized water and weigh
again.
6. Empty the pycnometer and refill with deionized water and weigh again.
7. Repeat procedure 5 two more times.
8. Empty the pycnometer and rinse thoroughly with the most dilute salt solution
assigned. Weigh the pycnometer filled with the solution.
9. Repeat procedure 7 twice for every salt solution in order of increasing
concentration. Use the mean for the calculations.
SAFETY
1. Potassium chloride: white solid with saline taste; slightly hazardous upon
skin and eye contact or upon ingestion or inhalation, has carcinogenic,
mutagenic, and teratogenic effects; flush eyes with water for 15 minutes upon
eye contact, wash with soap and cold water upon skin contact.
2. Potassium bromide: odorless crystalline solid with strong saline to bitter to
pungent taste; slightly hazardous upon contact with skin, eye, or upon ingestion,
and inhalation, has carcinogenic, mutagenic, and teratogenic effects; flush for at
least 15 minutes upon aye contact, wash with soap and cold water upon skin
contact, irritated skin may be covered with an emollient. (reference 8)
3. Potassium iodide: deliquescent white crystalline solid; slightly hazardous
upon contact with skin, eye, or upon ingestion, and inhalation, has carcinogenic,
mutagenic, and teratogenic effects; flush for at least 15 minutes upon aye
contact, wash with soap and cold water upon skin contact, irritated skin may be
covered with an emollient.
CALCULATIONS AND QUESTIONS
1. Density of air (g/mL)
air
0.001293 B 0.3873E
1 0.00367T 760
1 1

1 1
+
] ]


where T = temperature in C (dry bulb)
B = barometric pressure in mm Hg
E = vapor pressure of water in mm Hg at T
2. Volume of the pycnometer (mL)
pyc water pyc air
pyc
water air
W W
V
+ +

where Wpyc+water = weight of pycnometer filled with water
Wpyc+air = weight of empty pycnometer
water = density of water at temperature T
water = density of air
3. Densities of solutions (g/mL)
pyc soln pyc air pyc air
soln
pyc
W (W V )
V
+ +


where Wpyc+soln = weight of pycnometer filled with solution
4. Molarities of solutions (mol/L)
2
2
sol ' n
g
M
C
V

where g2 = mass of solute

M2 = molar mass of solute
Vsoln = volume of pycnometer
5. Molality of solution (mol/kg)
2
soln
C
m
CM
1000

6. Get the quare root of molality
7. Calculate the apparent molal volume of solute
2

using equation (17) for each

solution.
8. Plot
2

versus
m
. Obtain
2
d
d m
_

,
from the slope and
o
2
from the y-intercept
of the equation of the best-fit quadratic line.
10. Calculate
2
V using equation (20) for all the solutions.
11. Calculate
1
V using equation (21) for all the solutions.
12. Interpret the plot
2

versus
m
. Discuss any trends.
13. Compare your results with values reported in the literature for the same or
similar solutions.
14. Discuss applications of data on partial molar volumes of solution
components.
REFERENCES
1. Daniels,F., et. al., Experimental Physical Chemistry, 7
th
edition. McGraw-Hill
Book Co., New York, 1970.
2. Wirth, H., J. Am. Chem. Soc., 1937, 59, 2549.
3. Shoemaker, D.P., Garland C.W., Experiments in Physical Chemistry: McGraw-
Hill Book Co., 1980.
4. Masson, D.O., Phil. Mag., 1929, 8, 218.