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157 (Questions on ConceptsQ9.1 Show using the differential form of G that if ln mixing i ii G nRT x x =∆ ∑ then0 , mixing mixing HV =∆=∆ .

12 ,, lnln and0lnln0 mixing i iimixingmixing i iiPmixingmixingT n nmixing mixing mixing i i i ii i G nRT x xGS nR x xT GV P H G T S nRT x x T nR x x ⎜= − = ∆ + ∆ = ∆⎜⎜⎜ ⎜ ∂⎜⎜= = ∆⎜⎜ ∆∂⎜⎜ ∂⎜⎜− = − = ∆⎜⎜∆∂= ∆ ⎜ ⎜⎜ ∑ ∑∑∑ (Q9.2 For a pure substance, the liquid and gaseous phases can only coexist for a singlevalue of the pressure at a given temperature. Is this also the case for an ideal solution of two volatile liquids?No, an ideal solution of two volatile liquids can exist over a range of pressures that arelimited by the pressure for which only a trace of liquid remains, and .the pressure forwhich only a trace of gas remains (Q9.3 Fractional distillation of a binary liquid mixture leaves behind a liquid consistingof both components in which the composition does not change as the liquid is boiled off.Is this behavior characteristic of a maximum or a minimum boiling point azeotrope?This behavior is characteristic of a maximum-boiling azeotrope. After initially giving off the more volatile component, the liquid remaining tends to the composition of themaximum boiling point at intermediate composition. After the more volatile componenthas boiled .away, the azeotrope evaporates at constant composition (Q9.4 Why is the magnitude of the boiling point elevation less than that of the freezingpoint depression?The boiling point elevation is less than the freezing point depression because thechemical potential of the vapor is a much more steeply decreasing function of temperature than the solid, as seen in Figure 9.11a. This is due to the relation d µ –= SdT at constant P

Henry’s law definesthe appropriate standard state for the solute at a low solute concentration. Because the magnitude of 158the slope of the µ gas curve is greater than that of the µ solid .5 = solutionbecause in this limit the solute has only a weak effect on the solvent.curve T b moves up less than the T m .11a). Is there a natural standard state for the solution for which x solvent = x solute Raoult's law defines the appropriate standard state of the solvent in a dilute?0.neither standard state adequately describes the standard state for x solvent = x solute .and the fact that the molar entropy of a vapor is much larger than that of asolid. However.moves down (Q9.5 The natural standard state for the solvent in an ideal dilute solution is the Roualt'slaw standard state. and the standard state for the solute in an ideal dilute solution is theHenry's law standard state. When the µ liquid curve is displaced down by the addition of the solute. the intersection of the µ liquid curve with the µ solid curve and the µ gas curvedertermine the shift in the freezing and boiling temperatures.9. (see Fig.

it is seen that a decrease in P leads to adecrease in T b . Moles per kilogram is thus amore useful concentration unit than moles per . independent of temperature and . Qualitatively. changes as T or P are varied because the thermal expansioncoefficient and the isothermal compressibility are not zero.6 Is a whale likely to get the bends when it dives deep into the ocean andresurfaces? Answer this question by considering the likelihood of a diver getting thebends if he or she dives and resurfaces on one lung full of air as opposed to breathing airfor a long time at the deepest point of the dive. By looking at the liquid-vapor coexistence curves. will result in saturated blood for the diver.4.The volume.Inthis case. the dependence of boilingpoint on pressure can be traced.4 .The whale is unlikely to get the bends on one lungful of air. For thisreason.7 The statement “The boiling point of a typical liquid mixture can be reduced byapproximately 100ºC if the pressure is reduced from 760 to 20 Torr” is found in Section9.phase diagram such as that of Figure9. the diver is more susceptible to getting the bends .8 Explain why chemists doing quantitative work using liquid solutions prefer toexpress concentration in terms of molality rather than molarity.9 Explain the usefulness of a tie line on a P-Z .11 (b) shows the P T phase diagram of a pure substance (and a correspondingsolution).than the whale (Q9. however. What figure(s) in Chapter 8 can you identify to support this statement in a qualitativesense?Figure 9. There is not enough N 2 present in a single lungful to yield a saturated solution of N 2 in the blood. (Q9. but neither has a firm physical . Breathing airfor a long time at depth.The molality of a solution is the preferred unit because it is independent of P and T Akilogram of a substance is a conserved quantity. however.0.basis (Q9. pressure. either standard state can be used.liter. which changes with thethermodynamic state (Q9.5 = .

4 . thusreducing the mass of toluene in the beaker by 2.272180 Torr + 82.2 A volume of 5. Assuming that the air emergingfrom the beaker .38 g.116 bar5. This statistical likelihood of being near the interface doesn't depend on the identity of the solute – only the number insolution.1 Torr.450.only on the number of speciesin solution Problems P9. and not onthe identity of the molecule.25118 total benzene benzene cyclohexene cyclohexene PxPxP = × − + × =+ = (P9. Calculate the vapor pressure of a solution for which x benzene .distances (Q9.10 Explain why colligative properties depend only on the concentration. The vaporpressure of pure A is 180 Torr and that of pure B is 82.3 ( An ideal solution is formed by mixing liquids A and B at 298 K. Specifically.25 = () ** Torr10.1 ( At 303 K.The tie line allows the compositions of the liquid and vapor phases to be 159 determinedgeometrically for a given total composition and pressure. Therefore.08314 L barK298 K78.45082. which lowers itsvapor pressure.38 g0.450 0.50 L 1 nRT PV = =× × × P9. colligative properties (ideally) depend .is saturated with toluene. If the mole fraction of A inthe vapor ?is 0.25122 Torr121 Torr 0.50 L of air is bubbled through liquid toluene at 298 K.1 Torr180 Torr0. what is the mole fraction of A in the solution () () **** Torr= 0. determine the vapor pressure of toluene at thistemperature 1-1mol2.1 ABAABAA y P xP P P y − +× −= =× (P9. the ratio of molesin liquid and vapor phase is inversely proportional to the ratio of tie line .The origin of the colligative properties is the dilution of the solvent.assumingideal behavior 0. This is the case because solute molecules at the surface of the liquidaffects the relative rates of evaporation and condensation.11 gmol= 0. the vapor pressure of benzene is 118 Torr and that of cyclohexane is122 Torr.

0.Using this information.650 = . At a total pressure of 0..900 bar y A and 0. calculate the vapor pressure of pure A and of pure B .A and B form an ideal solution.450 = x A .