V

Physical Chemistry

MOLECULAR WEIGHT DETERMINATION I. Victor Meyer's method A liquid which can be readily vaporized is made to displace an equivalent amount of air. By using a known weight of liquid it is possible to calculate an approximate molecular weight for the compound from your knowledge of the molar volume of gases. Even when care is taken, poor results are frequently obtained in this experiment. Requirements Victor Meyer apparatus. Hempel gas burette. Hofmann bottle. Sample of liquid such as dichloromethane, chloroform, carbon tetrachloride. Set up the apparatus shown in Fig. 16. Weigh accurately a Hofmann bottle, first empty and then containing a sample of liquid (roughly 0'15 g). Add water to the Hempel burette until the water is at a definite mark (Vo) near the top of the graduated tube and level with the water in the other tube. Close the top tap on the Hempel burette. With the rubber stopper removed from the Victor Meyer apparatus, heat the water in the outer jacket so that it boils steadily without much loss from the side vent. Find out if temperature equilibrium has been reached by inserting the rubber stopper and opening the top tap on the Hempel burette. After an immediate movement downwards there should be no change in the water level in the graduated tube. Equalize accurately the water levels in the Hempel burette and record the volume reading. This is the initial volume (VI)' Now remove the rubber stopper from the Victor Meyer apparatus and bring the water levels in the Hempel burette back to their original setting (Vo) .. This procedure allows for changes caused by inserting the rubber stopper. Working quickly, loosen the stopper of the Hofmann bottle, drop it into the Victor Meyer apparatus and replace the rubber stopper. Check that the top tap of the Hempel burette is open. The liquid should vaporize, displacing air into the graduated tube. Run water out of the Hempel burette so that the water remains approximately level in the two tubes. When no further change can be seen, equalize accurately the water levels and close the top' tap. Check the water levels after allowing the Hempel burette to cool to room temperature, and record the final volume (V2)' Record also room temperature and the barometric pressure. Determine the vapour pressure
93

VictorMeyer apparatus---

Hempel gasburette----I

Fig. 16. The Victor Meyer weight determination.

apparatus

for

molecular

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PHYSICAL CHEMISTRY

of water at the recorded room temperature Table 7.

Table 7
Room temperature

from

To calculate the molecular weight of the compound, the volume of air collected must be adjusted to standard conditions: volume of air at S.T.P. = volume of air collected (V2 ~ VI)
X

Aqueous vapour pressure (torr)

917 1046 1191 13'54 1536 1739 1966 2218 2499 2810 31'55

actual air pressure Standard Pressure

Standard Temperature X ----------~~---room temperature The actual pressure of the air is given by (barometric pressure - water vapour pressure). The molecular weight is the weight of compound that would displace 22'4 litres of air at S.T.P.

2.

Gaseous effusion method Place two pieces of sticky paper on the barrel of the gas syringe to indicate clearly two marks about 70 ml apart. Now connect the syringe to the effusion tube while the piston is drawn out. Clamp

The kinetic theory of gases suggests that at a fixed temperature gases have different average molecular velocities which are related to their different molecular weights. The relationship can be studied by determining the time taken for gas samples to diffuse in identical conditions. 100 ml gas-tight syringes are very suitable for this experiment. They are used ungreased and care is necessary to avoid damage by abrasive dirt: wash in clean soapy water, rinse well in pure water and ethanol and allow to dry at room temperature. Requirements 100 ml gas syringe. Effusion tube. Three-way stop-tap. Stop-clock. Dry samples of gases. The effusion. tube consists of a short length of glass tube sealed at one end, except for a pin-hole, with a disc of aluminium foil (Fig. I7a). The open end of the tube is fitted with a piece of plastic tube for attachment to the gas syringe. To make an effusion tube, cut with a cork borer a disc of thin aluminium foil and stick it to the glass tube by means of an expoxy-resin such as 'Araldite'. A suitable pin-hole is readily made by pricking the foil with an ordinary pin.

- 100 ml gas syringe

Plastic tube

Fig. 17a. Gas syringe for gaseous effusion.

the syringe upright and release the piston so that air is forced out by the weight of the piston alone. Note the time taken for the piston to travel between your two marks. If the pin-hole is satisfactory the time should be between one and two minutes. To repeat the experiment with other gases, the syringe is disconnected from the effusion tube