Vapour Pressure Osmometry

Objective
Determination of molecular weight of given salt using vapour pressure osmotry.

Introduction

Salt is very essential for the sustenance of the human body which can endure for long periods
without food but without water and salt, the living cells would die from dehydration and other
than that it has its applications in the food industry as preservative being a very safe and
inexpensive desiccant.
Similar kind of compounds need to be used for calibration and molecular
weight determination . Otherwise there could be considerable deviation in the actual and
experimental values to the way they differ in their interaction with the solvent (water in our
case). Therefore, NaCl has been used for calibration to find out the molecular weight of the salt
KCl.

THEORY

Determination of number average molecular weight depends on basic equations of dilute

solution chemistry and physical chemistry. In a dilute solution, the vapour pressure of a
solvent is given by basic Raoult’s Law:

P1=P10 *X1
P1 = partial pressure of solvent in solution
P10 = vapor pressure of pure solvent
X1 = mole fraction of solvent

So, vapour pressure of any solution is lower than vapour pressure of its pure solvent. If one
places the drop of solution along with that of pure solvent in the vapour environment of pure
solvent, then condensation will occur on the solution drop because its vapour pressure will be
less than that of the solvent. Condensation will lead to relative increase in temperature of the
solution drop with respect to the pure solvent drop. Increased temperature in turn changes
resistance and hence, generates a potential difference. This potential difference is recorded
until equilibrium is reached.

The basic relation for molecular mass determination equals:

m
sample
n M
sample = sample
m m

n = Number of sample molecules

m = Mass of sample and solvent respectively

M = Molecular mass of the sample

For a molecular mass less than 500 g/mol the measurement value is proportional to the
number of moles. The change in vapour pressure is proportional to the number of species
present in the solution, which is measured in terms of osmol units. Hence the this is very
similar to the osmolality determination. A sample is measured where concentration and
molecular mass are known (c in mol/kg). The slope of the graph of measurement value v/s
concentration is c a l i b with kg/mol.
K = MV
calibration
c

Unknown molecular mass of the sample can be determined by a known concentration. The
slope of the curve of measured value gives Kmeasurement

The molecular weight of unknown sample is determined with:

M (molg )= Kcalibration / Kmeasurement

Methodology
Vapour pressure osmometer K-7000 is designed to exactly measure the number average
molecular weight of polymers. This measurement is based on the principle that chemical
potential of a solvent is altered in presence of a non-volatile substance. In dilute solution this
phenomenon depends only on the number of particles dissolved. Therefore change in chemical
potential is measured in terms of change of osmotic pressure and average molecular weight is
determined. Figure 1 gives the internal view of the instrument.
Apparatus
Vapour pressure osmometer, volumetric flasks, pipette

Chemicals
NaCl (AR Grade), Millipore water, KCl

PROCEDURE
1. Prepare samples of different concentration for which molecular weight is to be
determined
2. Check whether thermistors are working or not

3. Fill 25% of beaker with pure solvent along with the wick.
4. Insert the thermistor assembly inside the beaker and place it in an equipment chamber
and tighten to avoid leakage which will disturb the stabilization.
5. Place all the syringes inside the syringe ports. Fill two syringes with pure solvent and
place them back to the syringe holders to attain the temperature of head.
 6. Set the temperature according to your requirement but within a limit given in an
O O
equipment manual for different solvents. Selectable cell temperature 20 C -130 C.
7. After temperature setting, place GAIN value to maximum (256).Then let it stabilize.
Selectable gain settings are 1,2,4,8,16,32,64,128,256
8. Before starting the experiment adjust the Wheatstone bridge signal value to zero with the
help of AUTOZERO function. After that add a drop of one of the solution prepared on
one thermistor. If the signal value is showing OVERLOAD then adjust the gain
accordingly to get signal value. In this way note down the signal and gain value for every
solution.

RESULTS
Table1: Calibration data for standard solute (NaCl)

Concentration of NaCl Average Signal

Gain Signal (mv) Signal/Gain
(mole/lt) (mv)

0.3 16
8
0.4 8
4
8
0.5
4
4
0.6 2

From the Table, a calibration graph and calibration factor may be generated.

Fig.1: Calibration graph for NaCl

 For NaCl sample, the relationship between the mol concentration and the osmol concentration may
be obtained by referring to the standard manuals (Table-2)

Table2: Osmolality data of NaCl (From Manual)

Osmo lality NaCl Mo lality

(osmol/kg solvent) (mol/ kg)
0.1 0.0527
0.2 0.10665
0.3 0.16155
0.4 0.2169
0.5 0.2725
0.6 0.32785
0.7 0.38375
0.75 0.41195
1.2 0.66255
1.8 0.9916

Fig.2: Concentration vs Os molality (NaCl)

 Table3: Data for unknown sample (KCl)

Concentration salt Average Signal

Gain Signal (mV) Signal/Gain
(g/kg) (mV)

256
2
128
64
3
32
256
4
128
256
5
128

Fig.3: Measurement graph of KCl

Method of calculating the molecular weight of

sample From Figure 3,
Kmeasurement = .............. mv.Kg/g
 Molecular weight of KCl = Kcalibration/ Kmeasurement = ..............g/Osmol.
This weight is then converted into molar weight depending on the interaction of KCl with
water .

Discussions and Conclusion

The reasons for deviation of experimental form actual (if any) should be analyzed and reasons
may be given( improper contact between thermistor tip and drop, drop size etc.)

Reading material
Vapor pressure osmometry as a means of determining polymer molecular weight, I.J
Goldfab, A.C. Meeks, May 1996