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Shivam Mishra
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Phase Equilibria 733 We have defined jz = (8G/8n) , , (Equation 23.3), so udn = dG. Now recall (Equation 22.13) that G=U-TS+PV dG =dU -TdS+ Pav dn _ dU > pap dst pa gs epebt dS = + pdV—Fdn For this system, since dU = dV =0, ec) hy a8, =—Tan, a8, = —Ftdn, Then If molecules are flowing into compartment 1, then dn, is positive and j1, > j1, (since transfer ‘occurs from the system with higher chemical potential to the system with lower chemical potential). Then both terms in the expression above are positive and dS... > 0. If molecules are flowing into compartment 2, then dm, is negative and 1, < jz,, making both terms negative and dS... > 0. If dn, is 0 (no transfer occurs), then the two compartments are in equilibrium with respect to material flow, and dS,,,.., = 0. 23-20. Determine the value of dT /d P for water at its normal boiling point of 373.15 K given that the molar enthalpy of vaporization is 40.65 kJ-mol"', and the densities of the liquid and vapor are 0.9584 g-L~! and 0.6010 g-mL"", respectively. Estimate the boiling point of water at 2 atm. st find VS — << a 1 1 ai (carve dm? 958.4 gdm = 29.96 dm’- mol" ) (sors g-mol"') Now use Equation 23.10 to write aT TAY dP ow __ [ G73.15 K)(29.96 dm’ mol!) 83147 - 40 650 J-mol 0.08206 dm’-atm. =27.9K-atm' 734 Chapter 23, To estimate the boiling point of water at 2 atm, we can find the change in temperature which accompanies a change in pressure of I atm (since we know the boiling point of water at 1 atm). That is AT = (27.9 K-atm”")(1 atm) = 27.9 K. Therefore, the boiling point of water at 2 atm is about 127.9°C. 23-21. The orthobaric densities of liquid and gaseous ethyl acetate are 0.826 g-mL! and 0.00319 g-mL-', respectively, at its normal boiling point (77.11°C), The rate of change of ‘vapor pressure with temperature is 23.0 torr-K~! at the normal boiling point. Estimate the molar enthalpy of vaporization of ethyl acetate at its normal boiling point. First find VV: vev aoe SER) (t8.102¢-mor) 0.00319 g-mL~" 0.826 g-mL* V = 27510 cm’-mol"! = 75.10 dm*- mol Now use Equation 23.10 to write = — (ae AH =TA¥ (Fe = (850.26 K)(27.51 dm?-mol“")(23.0 torr-K™) ( Soe 760 torr, 0.08206 L-atm. = 29.5 kJ-mol™ 23-22. The vapor pressure of mercury from 400°C to 1300°C can be expressed by 7060.7 K In(P ftorr) = ——"* + 17.85 T ‘The density of the vapor at its normal boiling point is 3.82 g-’ and that of the liquid is 12.7 g-mL“'. Estimate the molar enthalpy of vaporization of mercury at its normal boiling point. If we express P using the above equation, we find that aP _ , (1080.2 ar Tt At the boiling point and one atmosphere of pressure, ap 7060.7 K aT (29.88 KY 13.52 torr-K~" aT = 760 torr) [ We find A,,,V by subtracting V' from V*: 1 4 3.82g-dm™~ 12700 g-dm= Ago ¥ = 52.49 dm*-mol™ ) (200.59 g-mol~) 762 Chapter 24 Substitute this result into the equations for V, and V, given in Problem 24-10 with M, = 18.02 and M, = 92.09 to get the following result 80r Glycerol sor 40h V/mL+ mol! 24-13. Just before Example 24-2, we showed that if one component of a binary solution obeys Raoult’s law over the entire composition range, the other component does also. Now show that if Hy = Hy + RT Inx, fOr X, ay S Xz x, if Py > and that y, 1 (Ps > P;), then the right side is always positive because 0 < x, <1 and 0 < x, <1 and Jy > Xp If R < 1 (P] < P*), then the right side is always negative. This result simply says that the mole fraction of a given component in the vapor phase will be sr than that of the other component if it is more volatile. Tetrachloromethane and trichloroethylene form essentially an ideal solution at 40°C at all trations. Given that the vapor pressure of tetrachloromethane and trichloroethylene at 40°C 214 torr and 138 torr, respectively, plot the pressure-composition diagram for this system (see jem 24-17). ey 214 torr — x,(76 torr) P= Py Py (214 torr)(138 torr) “ 138 torr + y,(76 torr) 220 180] 0.0 0.2 0.4 0.6 0.8 1.0 Mole fraction The vapor pressures of tetrachloromethane (1) and trichloroethylene (2) between 76.8°C and ;2°C can be expressed empirically by the formulas 2790.78 In(Py tom) = 15.8401 — =F

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