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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 .16 104 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 250.1103[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 8.1103 J mol-1 S mvaporization = 91.1103 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 349.1103 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 8.110 3 J mol-1 37.39) At 298.84 103 [Pa] P8.5 kJ mol1 P G 8.269 10539 Pa Ptp 2.314 J K mol Ptp 0.1 kJ mol1 8.314 J mol1 K 1 298. G G f H 2O.1103 J mol-1 1 1 ln 1.6 kJ mol-1 and G f (H2O.5 kJ mol1 ln 3.1103 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 mol1 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.

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