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MSE 260, Solution Set 4.

One component phase equilibrium

1. Calculate the approximate pressure required to distill mercury at 100C. Data: lnpHg(l) = -7611/T - 0.795lnT + 17.168 atm.

2. CaF2 can exist in two solid forms, and . Using the vapor pressure - temperature relationships for CaF2(), CaF2() and liquid CaF2 calculate: (a) The temperatures and pressures of the triple points for the equilibria : CaF2()-CaF2()CaF2(v) and CaF2()-CaF2(l)-CaF2(v) (b) The normal boiling point of CaF2 (c) The molar latent heat of the transformation CaF2()CaF2() (d) The molar latent heat of melting of CaF2() Data: lnpCaF2() = -54350/T - 4.525lnT + 56.57 atm. lnpCaF2() = -53780/T -4.525lnT + 56.08 atm. lnpCaF2(l) = -50200/T - 4.525lnT + 53.96 atm

7. Below the triple point (-56.2C) the vapor pressure of solid CO2 is: lnp(s) = -3116/T + 16.01 atm. The molar latent heat of melting of CO2 is 8330 joules. Calculate the vapor pressure exerted by liquid CO2 at 25C and explain why solid CO2 is referred to as "dry ice". Ignore any heat capacity terms.

4. One mole of SiCl4 vapor is contained at 1 atm pressure and 350K in a rigid container of fixed volume. The temperature of the container and its contents is cooled to 280 K. (a) At what temperature does condensation of the SiCl4 vapor begin? (b) What fraction of the vapor has condensed when the temperature is 280 K ? lnp(l)SiCl = -3620/T + 10.96 atm. 4

As the vapor is cooled at constant volume the pressure will drop (PV=nRT); at some temperature the pressure will reach a value equal to the vapor pressure of the liquid. At that temperature the liquid will start to condense and the pressure of the vapor must satisfy BOTH PV=nRT and th lnp(l) equation. As the system continues to be cooled the pressure of the vapor must continue to drop, therefore the number of moles of vapor will decrease and the amount of liquid will increase. (a) When condensation first begins: Pressure of the vapor must obey PV=nRT and lnp(l)SiCl = -3620/T + 10.96 atm. 4 When condensation first begins the vapor still contains 1 mole of SiCl4 Therefore P(vap) = nRT/V = (1 mol) (0.082)T/V. Need V: from the data in the problem at 350K, 1mole of vapor has P = 1atm: V = 1(0.082)(350)/1 = 28.7L P(vap) = (1 mol)(0.082 L.atm.mol-1K-1)T/28.7L lnp(l)SiCl = -3620/T + 10.96 atm. 4 (equation 1) (equation 2)

Equate (1) and (2) and solve for T: T = 328.4K. (and p = 0.939 atm) (b) Fraction of condensed vapor at 280K. At 280K: lnp(l)SiCl = -3620/280 + 10.96 atm; p(l)SiCl = 0.14 atm. 4 4 How many moles of vapor? Use PV = nRT. n = (0.14)(28.7)/(0.082)(280) = 0.175 mol vapor. Therefore have (1-0.15) = 0.825 mol liquid. 82.5% of the SiCl4 has condensed. See below for approximate path of the system

Prob 4. Path followed by system.

P atm

solid liquid

0.94 0.14 vapor

328.4 280