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Ebulliometric Determination of Vapour Pressures

Objectives
1. To determine the vapour pressure at various temperatures for a pure substance and to calculate the correlation constants in the vapour pressure equation. 2. Estimation of the latent heat of vaporization for the substance from the vapour pressure data.

Introduction
When the vapor phase of a pure uid is in equilibrium with its liquid phase, the equality of chemical potential, temperature, pressure in both phases leads to the Clausius-Clapeyron equation:

H d ln P = d(1/T ) RZv

(30.1)

Most vapour pressure estimations and correlation equations stem from integration of Equation 30.1. When this is done, an assumption must be made regarding the dependence of the group (Hv /Zv ) on temperature. The simplest approach is to assume that the Hv /Zv is constant and then Equation 30.1 on integration becomes (A being the integration constant:

ln P = A

B T

(30.2)

(where T in in K, and Zv = Zvap Zliq , Z being the compressibility factor). The above equation is called Clausius-Clapeyron equation where, B is given as Hv /RZv (Hv = enthalpy of vaporization). A simple modication of the equation which has been widely used is known as Antoine equation: B (30.3) ln P = A T +C

C = Constant, T = C. As an approximation at low pressures (< 1 atm), if Zv is taken as 1.0, the latent heat of vaporization can be directly obtained from the slope of the plot of ln P vs. 1/T .

Experimental Procedure
1. Accurate data on equilibrium vapor pressures can be determined over a range 100 to 760 mm Hg using a specially designed glass ebulliometer connected to a manifold and pressure control system. The sample of the liquid, or solution whose vapour pressure is to be measured is, charged to ll the bulb of the ebullometer. When the bulb is electrically heated, slugs of vapor bubbles with entrapped liquid rise in the tube (Cottrell Pump) to the ask chamber and are poured on the inner surface of the thermowell where vapour bubbles get disengaged from the liquid. The liquid stream along with the condensed vapor is recirculated till equilibrium is attained. The equilibrium state is indicated by the constancy of both the thermowell temperature and of the vapour condensation drop-rate through the drop-counter. The pressure of the ebulliometer is regulated via a stop-cock, the pressure being recorded by means of an absolute manometer. Electrical heating is regulated in order to minimize superheating and the ebulliometer is adequately insulated in order to minimize heat loss resulting in any subcooling of the liquid. 111

2. Once the pressure in the manifold is xed at any value, the system will on its own adjust to the corresponding equilibrium temperature. Allow at least 20-25 minutes for this, but note the change of temperature with time (not needed to be reported in journal) so that you know when a steady temperature is reached. 3. Once temperature steadies, count the drop rate (per minute) of condensed vapour. 4. This drop rate is proportional to the steady state amount of the substance in the vapor phase (which is, of course, being condensed back into liquid). For vapour-liquid equilibrium the system T remains constant as quality (x) going from 0 to 1. Experimentally low drop rate (< 30/min) correspond to low values of x, while very high droop rates (> 110/min) indicate high value of x. Experimentally both these extremes need to be avoided as these may make the system exist either in the supercooled or superheated region, which will yield an inaccurate equilibrium temperature measurement for a given pressure. At an intermediate drop rate the system is likely to be in the two-phase region with a medium quality. The temperature measured under such a condition will provide a relatively accurate equilibrium value of temperature. 5. Adjust the heat input to the ebulliometer bulb using the rheostat so that you obtain a drop rate in the intermediate range ( 40-90/min). The rheostat is very sensitive; no more than a change by a graduation is recommended at a time. After any such change, wait for system temperature to stabilize and then measure the drop rate. 6. Once you obtain a stable drop-rate in the intermediate range (and a corresponding temperature), change the rheostat reading by half a graduation (either increase or decrease as needed; note that increase in rheostat reading would increase heat input, and hence also the drop rate of condensed vapor), keeping the same pressure, and obtain another drop rate preferably within the same range, and note the stable temperature. Report the average of the two temperatures as the equilibrium temperature corresponding to the pressure of the manifold. 7. Obtain P vs. T data for at least 8 pressures in the range 100-760 mm Hg.

Calculations
1. Plot ln P vs. 1/T . 2. Determine the correlation constants in the vapour pressure equation. 3. If the units of P are changed from mm Hg to atm or Kgf/cm2 , how does the behavior of the curve change? 4. Estimate latent heat of vaporization from the plot in (1). 5. How does the latent heat change with increasing temperature and pressure over a wide range? Under what condition is Hv zero? Why ? 6. The latent heat of vaporization is generally seen to be dependent on properties such as molecular weight and polarity. Explain why these properties are determinant to the enthalpy of vaporization.

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