UP204: Assignment No. 2 Due: February 11, 2014 1.

A gas can coexist with a droplet of radius r of its own liquid if the pressure of the gas is Pr (T ). The purpose of this problem is to calculate the dependence of Pr (T ) on r. The Gibbs potential of the system consisting of the gas and the liquid droplet can be written as Gtot = M2 g2 + M1 g1 + 4Sr2 , where M1 and M2 are the masses of the droplet and the vapor, respectively, g1 and g2 are the respective Gibbs potentials per unit mass in the innite volume limit, and S is the coecient of surface tension. Use the extremization condition on G for equilibrium to obtain the relation g2 g1 = 2S , r

where is the liquid density. Dierentiate with respect to pressure at constant temperature, and using the ideal gas law for the vapor whose density is much smaller than , obtain the relation Pr (T ) = P (T ) exp[2Sm/(kB T r)], where m is the mass of a gas molecule. 2. A substance whose state is specied by P , V , T can exist in two distinct phases. At a given temperature T , the two phases can coexist if the pressure is P (T ). The following information is known about the two phases. At the temperature and pressure where they can coexist in equilibrium, (a) there is no dierence in the specic volumes of the two phases. (b) there is no dierence in the specic entropies of the two phases. (c) the specic heat cp and the volume expansion coecient are dierent for the two phases. Using this information, nd dP (T )/dT as a function of T . 3. The vapour pressure p (in millimeters of mercury) of solid ammonia is given by ln p = 23.03 3754/T (T is the absolute temperature) and that of liquid ammonia is given by ln p = 19.49 3063/T . Use this information to answer the following questions. (a) What is the temperature of the triple point of ammonia? (b) What are the latent heats of sublimation and vaporization of ammonia at the triple point? (c) What is the latent heat of melting of ammonia at the triple point? 1

4. One mole of a monatomic ideal gas is in a cylinder with a movable piston on the other side of which is a pressure reservoir with Pr = 1 atm. How much heat must be added to the gas to increase its volume from 20 to 50 liters? Also calculate the heat required for the same process assuming that the gas obeys the van der Waals equation of state with parameters appropriate for argon (a = 0.132 Pa.m6 , b = 30.2 106 m3 ). 5. Two moles of a van der Waals uid are maintained at a temperature T = 0.95Tc in a volume of 200 cm3 . Find the mole number and volume of each phase. Use the van der Waals parameters of oxygen (a = 0.138 Pa.m6 , b = 32.6 106 m3 ). 6. Let Vl (T ) and Vg (T ) be the molar volumes of the coexisting liquid and gas phases of a van der Waals uid at a temperature T < Tc . Show that [Vg (T ) Vl (T )] |t| for |t| 0 where t (T Tc )/Tc .