Physical Chemistry II Chem 402 Spring 2012

Chapter 8 (4, 6, 11, 23, 28, 34, 39)

P8.4) Use the vapor pressures for PbS given in the following table to estimate the temperature
and pressure of the triple point and also the enthalpies of fusion, vaporization, and sublimation.

Phase T (°C) P (Torr)
Solid 1048 40.0
Solid 1108 100.
Liquid 1221 400.
Liquid 1281 760.
To estimate H msublimation , use the vapor pressures of the solid phase

P2 H sublimation  1 1 
ln    
P1 R  T2 T1 
P  100 Torr 
R ln 2 8.314 J mol-1 K -1  ln  
H msublimation 
P1
  400 Torr 
1 1 1 1
   1048 + 273.15 K  1108 + 273.15 K
 T1 T2 
= 231.7 kJ mol-1

To estimate H mvaporization , use the vapor pressures of the liquid phase

P2  760 
R ln 8.314 J mol-1 K -1  ln  
H mvaporization 
P1
  400 
1 1 1

1
  
 T1 T2  1221 + 273.15 1281 + 273.15
H mvaporization  206.5 kJ mol-1
H mfusion  H msublimation  H mvaporization
 231.7 kJ mol-1  206.5 kJ mol-1
 25.2 [kJ mol-1 ]

Tliquid . Pliquid .ref  1494 K 1 1  232 103 J mol-1 207 103 J mol-1    Ttp  232  207  103 J mol-1  1381 K 1494 K  100.ref T  1 1  H msublimation H mvaporization      R ln Psolid .ref T    232  103 J mol-1  1 1  Ptp  100. Torr    7.ref  R ln Pliquid .ref T   Pliquid  H mvaporization  1 1 ln  P        liquid .ref R   Tsolid . Torr    8. Torr  exp      8. the solid and liquid have the same vapor pressure.ref  T H msublimation  H msublimation  Tsolid .ref Tliquid .16 104 K -1 Ttp  1398 [K] The pressure at the triple point can be obtained from either the equation for vapor pressure of the solid or the solid phases.ref T  H msublimation  1 1     ln Psolid .ref  1381 K .314 J mol-1 K -1  ln    400.ref  for Psolid .ref  400 Torr Tsolid .ref  R  Tliquid .ref T  H mvaporization  1 1      ln Pliquid .ref exp  m      R  Tsolid .ref  R  Tsolid .  H sublimation  1 1  Psolid T   Psolid . At the triple point.6) A P–T phase diagram for potassium is shown below .  P  H msublimation  1 1 ln  solid P        solid .ref R   Tliquid .ref  100 Torr .314 J mol K  1381 K 1398 K   -1 -1 Ptp  128 [Torr] P8.

P8.11) Use the vapor pressures for C2N2 given in the following table to estimate the temperature and pressure of the triple point and also the enthalpies of fusion. and sublimation. for a given temperature. Phase T (°C) P (Torr) Solid –62. Does fcc potassium float on or sink in liquid potassium? Explain your answer. The slope of the vapor–liquid coexistence line is always positive because the vapor pressure increases rather than decreases with increasing temperature. The vapor phase is found at much lower pressures and higher temperatures. Therefore the fcc phase is more dense b) Indicate the range of P and T in the phase diagram for which fcc and liquid potassium are in equilibrium.a) Which phase has the higher density. The fcc phase will sink in the liquid because the slope of the two phase liquid–solid coexistence line is positive. vaporization. the phase with the higher density will be found at higher pressure. fcc and liquid potassium are in equilibrium on the liquid–solid coexistence line existing upward from the triple point.0 . c) Extend P and T on this diagram and indicate where you might expect to find the vapor phase. Explain how you chose the slope of your liquid–vapor coexistence line. According to LeChatelier’s principle. the fcc or the bcc phase? Explain your answer.7 40.

Ttp  240. Torr  exp       403 [Torr]  8.6745 103 ln  A 1   23.ref  221.9  103 J mol-1  221.9 103 J mol-1    Ttp  32. Torr   1  0.2 K Pliquid .0 760.Solid –51. Liquid –33.07 104 [Pa] .23) Calculate the vapor pressure of ethanol droplets of radius 1. to calculate the triple point temperature.58   10. P T  A  2 3.314 J mol-1 K -1  ln    400.4 K 240.6 103 J mol-1 26. Use the tabulated value of the density and the surface tension at 298 K from Appendix B for this problem. Torr   + 8.ref  240.0 400. Torr 1 1  32. Torr Tliquid .00416 K -1 .6  26.6 103 J mol-1  1 1  Ptp  100.3. (Hint: You need to calculate the vapor pressure of ethanol at this temperature.ref  100.) We first calculate the vapor pressure of ethanol at 298 K using Table 8.8 100.314 J mol K  221. Liquid –21.702 K P  5.4 K 240.4 K Psolid .2 K  100.8345 Pa T  A  3 335  46. take Tsolid .3 K   -1 -1 P8.00  10–8 m at 335 K in equilibrium with ethanol vapor.ref  400. K Ttp  32.

07 104  Pa M P   P  P0  -3 789.00 10-8 m Pinside  Pvapor  P  5.97 10-3 N m -1 P   = 4.44 106  5. 2 2  21.39 10 6 Pa = 4.4 9.807 249.096 P0  5.934 238.105 272.3 6.314 J mol K  335 K -1 -1 P  1. T (K) P (atm) T (K) P (atm) 227.25).8 1. We next calculate the pressure difference across the interface using Equation 8. 46.9 2.07 10-3 kg mol-1   4.07 10 4 Pa + 4.56 104 [Pa] P8.173 260.483 327.585 283.388 316.29.28) Use the vapor pressures of Cl2(l) given in the following table to calculate the enthalpy of vaporization using a graphical method or a least squares fitting routine.5 12.2083 10-2  P0  RT 8.0 3.676 .39 106 Pa r 1.6 15.15 4.6 0.7 0.3 kg m ln     = 9.566 305.44 10 6 Pa We calculate the increase in the vapor pressure using Equation (8.982 294.

The vapor pressure of the solid is 270. Pa at 232 K and 1092 Pa at 250.34) Carbon tetrachloride melts at 250.1103[J mol-1 ]  1 1      340 K 290 K  . a) Pf H mvaporization  1 1  ln     Pi R  T f Ti  P R ln f Pi H mvaporization    1 1     T f Ti  74518 Pa 8. Calculate the normal boiling point and Smvaporization at the boiling point. d.32 kJ mol-1.A least squares fit of ln P versus 1/T gives the result H mvaporization = 20. K. Calculate the triple point pressure and temperature. K and 74. c. Calculate H mvaporization and H msublimation . b. a. The vapor pressure of the liquid is 10.518 Pa at 340. K. Calculate H mfusion . P8.314 J mol-1K -1  ln H mvaporization   10539 Pa = 32.539 Pa at 290. K.

314 J mol-1K -1  ln H msublimation   270 Pa = 37.5 K . [K] -1  32. c) Pf H mvaporization  1 1 ln     Pi R  T f Ti  H mvaporization Tf   H mvaporization P  R  ln f   RTi Pi  At the normal boiling point. P = 101325 Pa.1  103 J mol-1 = 5.314 J mol K  340 K -1 -1 74518 Pa  H mvaporization 32. 32.314 J mol K   -1  ln   8.1103 J mol-1 S mvaporization   = 91.1103 J mol-1 101325 Pa  8. Pf H msublimation  1 1  ln     Pi R  T f Ti  P R ln f Pi H msublimation    1 1     T f Ti  1092 Pa 8.4  103 J mol-1 – 32.3  103 [J mol-1].8 [J mol-1K -1 ] Tvaporization 349.1103 J mol-1 Tb .normal   350.4 103[J mol-1 ]  1 1      250 K 232 K  b) H mfusion  H msublimation  H mvaporization = 37.

K -1 -1  Ptp H mvaporization  1 1  ln     Pi R  Ttp Ti  Ptp 32. g   G f  H 2O.4 103 J mol-1   264 K  10539 Pa 270 Pa 37.1 kJ mol-1.3112  264 K 290.g) = ─228. d) From Example Problem 8.2.l)= ─237. K  -1 -1 10539 Pa 8.110 3 J mol-1  37.39) At 298.84  103 [Pa] P8.5 kJ mol1 P G 8.269 10539 Pa Ptp  2.314 J K mol Ptp  0.1 kJ mol1  8.314 J mol1 K 1  298. G  G f  H 2O.1103 J mol-1  1 1  ln      1.6 kJ mol-1 and G f (H2O.5 kJ mol1 ln    3.1103 J mol-1  +   8.15 K.24 103 [Pa] . Calculate the vapor pressure of water at this temperature.314 J K mol  232 K  5 -1 -1 8. l   228. G f (H2O.15 K P  3.429 P RT 8.314 J K mol  290.6 kJ mol1  237. Ttp   H vaporization m  H msublimation   P liquid P solid H msublimation H mvaporization  R  ln i  ln i     P P RTi solid RTi liquid  Ttp   32.4 103 J mol-1   ln  ln   5 10 Pa 10 Pa 8.314 J K -1 mol-1    32.