# CHAPTER 8

PHYSICAL EQUILIBRIA

8.2

The volume of the supply room (neglecting any contents of the room) is
3.0 m × 2.0 m × 2.0 m = 12 m3 or 12 m3 × 1000 L ⋅ m −3 = 12 000 L. The
ideal gas law can be used to calculate the mass of mercury present:

PV = nRT
let m = mass of mercury

0.227 Pa
(12 000 L)

5
−1 ⎟
⎝ 1.01325 × 10 Pa ⋅ atm ⎠

m
=⎜
(0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol −1 )(298 K)
−1 ⎟
⎝ 200.59 g ⋅ mol ⎠
(0.227 Pa)(12 000 L)(200.59 g ⋅ mol−1 )
(1.0135 × 105 Pa ⋅ atm −1 )(0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K)
m = 0.22 g
m=

8.4

8.6

(a) The quantities of ∆H °vap and ∆S °vap can be calculated using the
relationship
ln P = −

∆H °vap 1 ∆S °vap
⋅ +
R
T
R

Because we have two temperatures with corresponding vapor pressures,
we can set up two equations with two unknowns and solve for
∆H °vap and ∆S ° vap . If the equation is used as is, P must be expressed in

atm, which is the standard reference state. Remember that the value used

208

for P is really activity that, for pressure, is P divided by the reference state
of 1 atm so that the quantity inside the ln term is dimensionless.
∆H °vap
67 Torr
=−
+ ∆S °vap
760 Torr
273.2 K
∆H °vap
222 Torr
=−
+ ∆S °vap
8.314 J ⋅ K −1 ⋅ mol−1 × ln
760 Torr
298.2 K
8.314 J ⋅ K −1 ⋅ mol−1 × ln

which give, upon combining terms,
−20.19 J ⋅ K −1 ⋅ mol−1 = −0.003 660 K −1 × ∆H °vap + ∆S °vap
−10.23 J ⋅ K −1 ⋅ mol−1 = −0.003 353 K −1 × ∆H °vap + ∆S ° vap
Subtracting one equation from the other will eliminate the ∆S °vap term and
allow us to solve for
∆H °vap :
−9.96 J ⋅ K −1 ⋅ mol−1 = −0.000 307 × ∆H °vap
∆H °vap = +32.4 kJ ⋅ mol−1

(b) We can then use ∆H °vap to calculate ∆S °vap using either of the two
equations:
−20.19 J ⋅ K −1 ⋅ mol−1 = −0.003 660 K −1 × (+32 400 J ⋅ mol−1 ) + ∆S °vap
∆S °vap = 98.4 J ⋅ K −1 ⋅ mol−1
−10.23 J ⋅ K −1 ⋅ mol−1 = −0.003 353 K −1 × (+32 400 J ⋅ mol−1 ) + ∆S ° vap
∆S °vap = 98.4 J ⋅ K −1 ⋅ mol−1
(c) The ∆G ° vap is calculated using ∆G°r = ∆H °r − T ∆S °r

∆G°r = +32.4 kJ ⋅ mol−1 − (298 K)(98.4 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 )
∆G°r = +3.08 kJ ⋅ mol−1
(d) The boiling point can be calculated using one of several methods. The
easiest to use is the method developed in the last chapter:
∆G°vap = ∆H °vap − TB ∆S ° vap = 0
∆H °vap = TB ∆S °vap or TB =

∆H °vap
∆S °vap

209

32.4 kJ ⋅ mol−1 × 1000 J ⋅ kJ −1
TB =
= 329 K or 56°C
98.4 J ⋅ K −1 ⋅ mol−1
Alternatively, we could use the relationship ln

∆H °vap
P2
=−
P1
R

⎡1
1⎤
⎢ − ⎥.
⎣ T2 T1 ⎦

Here, we would substitute, in one of the known vapor pressure points, the
value of the enthalpy of vaporization and the condition that P = 1 atm at
the normal boiling point.
8.8

(a) The quantities ∆H °vap and ∆S ° vap can be calculated using the
relationship ln P = −

∆H °vap 1 ∆S °vap
⋅ +
R
T
R

Because we have two temperatures with corresponding vapor pressures
(we know that the vapor pressure = 1 atm at the boiling point), we can set
up two equations with two unknowns and solve for ∆H °vap and ∆S ° vap . If
the equation is used as is, P must be expressed in atm, which is the
standard reference state. Remember that the value used for P is really
activity that, for pressure, is P divided by the reference state of 1 atm so
that the quantity inside the ln term is dimensionless.
8.314 J ⋅ K −1 ⋅ mol−1 × ln 1 = −
8.314 J ⋅ K −1 ⋅ mol−1 × ln

∆H °vap
326.1 K

+ ∆S °vap

∆H °vap
96 Torr
=−
+ ∆S °vap
760 Torr
273.2 K

which give, upon combining terms,
0 J ⋅ K −1 ⋅ mol−1 = −0.003 067 K −1 × ∆H °vap + ∆S °vap
−17.2 J ⋅ K −1 ⋅ mol−1 = −0.003 660 K −1 × ∆H °vap + ∆S °vap
Subtracting one equation from the other will eliminate the ∆S °vap term and
allow us to solve for ∆H °vap :
+17.2 J ⋅ K −1 ⋅ mol−1 = +0.000 593 K −1 × ∆H °vap
∆H °vap = +29.0 kJ ⋅ mol−1

210

1 K ⎦ Pat 35° C = 0.40 K ∆H °vap 485 Torr =− + ∆S °vap 8.2 J ⋅ K −1 ⋅ mol−1 = −0.9 J ⋅ K −1 ⋅ mol−1 −17. for pressure. 211 .2 K 8. we can set up two equations with two unknowns and solve for ∆H °vap and ∆S ° vap .10 =− 29 000 J ⋅ mol−1 8.314 J ⋅ K −1 ⋅ mol−1 (a) The quantities ∆H °vap and ∆S ° vap can be calculated using the relationship ln P = − ∆H °vap 1 ∆S °vap ⋅ + R T R Because we have two temperatures with corresponding vapor pressures.314 J ⋅ K −1 ⋅ mol−1 × ln which give.314 J ⋅ K −1 ⋅ mol−1 × ln 760 Torr 273.003 660 K −1 × (+29 000 J ⋅ mol−1 ) + ∆S °vap ∆S °vap = 88.8 × 102 Torr ln 8. is P divided by the reference state of 1 atm so that the quantity inside the ln term is dimensionless. which is the standard reference state. P must be expressed in atm. upon combining terms.(b) We can then use ∆H °vap to calculate ∆S °vap using either of the two equations: 0 = −0. If the equation is used as is.9 J ⋅ K −1 ⋅ mol−1 (c) The vapor pressure at another temperature is calculated using ln ∆H °vap P2 =− P1 R ⎡1 1⎤ ⎢ − ⎥ ⎣ T2 T1 ⎦ We need to insert the calculated value of the enthalpy of vaporization and one of the known vapor pressure points: Pat 35° C ⎡ 1 1 ⎤ − ⎢ ⎥ 1 atm ⎣ 308 K 326.63 atm or 4. ∆H °vap 155 Torr =− + ∆S °vap 760 Torr 250.003 066 K −1 × (+29 000 J ⋅ mol−1 ) + ∆S °vap ∆S °vap = 88. Remember that the value used for P is really activity that.

000 334 K −1 × ∆H °vap ∆H °vap = +28.003 660 K −1 × ∆H °vap + ∆S °vap Subtracting one equation from the other will eliminate the ∆S °vap term and allow us to solve for ∆H °vap : −9. the value 212 .734 J ⋅ K −1 ⋅ mol−1 = −0.−13.00 × 102 J ⋅ K −1 ⋅ mol−1 (c) The ∆G ° vap is calculated using ∆G°r = ∆H °r − T ∆S °r ∆G°r = +28.734 J ⋅ K −1 ⋅ mol−1 = −0. so the vaporization of ClO2 is spontaneous as expected.4 kJ ⋅ mol−1 − (298 K)(100 J ⋅ K −1 ⋅ mol−1 )/(1000 J ⋅ kJ −1 ) ∆G°r = −1.49 J ⋅ K −1 ⋅ mol−1 = −0. The easiest to use is the one developed in the last chapter: ∆G°vap = ∆H °vap − TB ∆S ° vap = 0 ∆H °vap = TB ∆S °vap or TB = TB = ∆H °vap ∆S °vap 28.4 kJ ⋅ mol−1 × 1000 J ⋅ kJ −1 = 284 K or 11°C 100 J ⋅ K −1 ⋅ mol−1 Alternatively. in one of the known pressure points. (d) The boiling point can be calculated using one of several methods.22 J ⋅ K −1 ⋅ mol−1 = −0. under those conditions it is a gas at room temperature. we could use the relationship ln ∆H °vap ⎡ 1 P2 1⎤ =− ⎢ − ⎥. P1 R ⎣ T2 T1 ⎦ Here.4 kJ ⋅ mol−1 Notice that the standard ∆G°r is negative. we would substitute.003 994 K −1 × (+28 400 J ⋅ mol−1 ) + ∆S °vap ∆S °vap = 1.22 J ⋅ K −1 ⋅ mol−1 = −0.003 660 K −1 × (+28 400 J ⋅ mol−1 ) + ∆S °vap ∆S °vap = 1.4 kJ ⋅ mol−1 (b) We can then use ∆H °vap to calculate ∆S °vap using either of the two equations: −13.00 × 102 J ⋅ K −1 ⋅ mol−1 −3.003 994 K −1 × ∆H °vap + ∆S °vap −3.

Remember that the value used for P is really activity that.314 J ⋅ K −1 ⋅ mol−1 × ln ∆H °vap 311. 8.8 kJ ⋅ mol−1 (b) We can then use ∆H °vap to calculate ∆S °vap using either of the two equations: 213 .6 K + ∆S °vap ∆H °vap 13 Torr =− + ∆S °vap 760 Torr 227. for pressure. 0 J ⋅ K −1 ⋅ mol−1 = −0.004 387 1 K −1 × ∆H °vap + ∆S °vap Subtracting one equation from the other will eliminate the ∆S °vap term and allow us to solve for ∆H °vap : +33.94 K which give. If the equation is used as is. P must be expressed in atm. which is the standard reference state.003209 K −1 × ∆H °vap + ∆S °vap −33. upon combining terms. 8.of the enthalpy of vaporization and the condition that P = 1 atm at the normal boiling point.001178 K −1 × ∆H °vap ∆H °vap = +28. is P divided by the reference state of 1 atm so that the quantity inside the ln term is dimensionless.9 J ⋅ K −1 ⋅ mol−1 = −0.9 J ⋅ K −1 ⋅ mol−1 = +0. we can set up two equations with two unknowns and solve for ∆H °vap and ∆S °vap .314 J ⋅ K −1 ⋅ mol−1 × ln 1 = − 8.12 (a) The quantities ∆H °vap and ∆S ° vap can be calculated using the relationship ln P = − ∆H °vap 1 ∆S °vap ⋅ + R T R Because we have two temperatures with corresponding vapor pressures (we know that the vapor pressure = 1 atm at the boiling point).

4 J ⋅ K −1 ⋅ mol−1 −33.41 atm or 3.314 J ⋅ K −1 ⋅ mol−1 (a) solid.7 K ⎦ P215 K = 0.4 J ⋅ K −1 ⋅ mol−1 (c) The vapor pressure at another temperature is calculated using ln ∆H °vap P2 =− P1 R ⎡1 1⎤ ⎢ − ⎥ ⎣ T2 T1 ⎦ We need to insert the calculated value of the enthalpy of vaporization and one of the known vapor pressure points: Pat 15. and vapor (triple point) 8.003 209 K −1 × (+28 800 J ⋅ mol−1 ) + ∆S °vap ∆S °vap = 92.6 K ⎦ Pat 25.26 atm or 2. (c) liquid. 214 .0°C = 0.2 K 311. they appear to be so because the rate of conversion is very slow.314 J ⋅ K ⋅ mol ⎣ 288.14 =− Table 6.2 contains the enthalpy of vaporization and the boiling point of ammonia (at which the vapor pressure = 1 atm).0° C ⎤ 28 800 J ⋅ mol−1 ⎡ 1 1 − ⎥ −1 −1 ⎢ 1 atm 8.0 × 102 Torr ln 8. (b) approximately 3600 K. liquid. (d) equilibrium between solid.18 (a) close to 105 atm.9 J ⋅ K −1 ⋅ mol−1 = −0.0 = −0. We say that diamonds are kinetically inert.1 × 102 Torr ln 8.004 387 1 K −1 × (+28 800 J ⋅ mol−1 ) + ∆S °vap ∆S °vap = 92. (b) vapor. (d) The phase diagram indicates that diamonds are not thermodynamically stable (see Chapter 6) under normal conditions. Using this data and the equation ln ∆H °vap P2 =− P1 R P215 K ⎡1 1⎤ ⎢ − ⎥ ⎣ T2 T1 ⎦ ⎡ 1 ⎤ 1 − ⎢ ⎥ 1 ⎣ 215 K 239. (c) approximately 105 atm.16 =− 23 400 J ⋅ mol−1 8.

7oC Temperature (b) The cooling curve for a sample of this material will resemble this sketch (not to scale): Vapor Temp. (b) The diamond/graphite interface line has a positive slope. hence diamond is less dense than liquid carbon. Decreasing Temperature 177 Liquid Temp. we are given the relationship: dP ∆H fus = dT T ⋅ ∆V Therefore. The order is graphite < diamond < liquid.24 In the previous problem.8. substituting in the values given in the problem: 317 × 105 Pa 2290 J ⋅ mol −1 = 1.6oC 177oC 83. hence diamond is denser than graphite.Liquid 1 atm Pressure Solid Liquid 200 Torr Liquid .5217 cm3⋅mol−1. 8.4 K ⋅ ∆V Solving for ∆V we find ∆V = −5. Decreasing Condensation Freezing 83. Converting to a per gram quantity: 215 .7 Solid Temp. The diamond/liquid line has a negative slope.7 K 235.22 (a) Solid . Decreasing Time 8.20 (a) graphite ⎯⎯ → diamond ⎯⎯ → liquid.Gas Gas 38.217 × 10−7 m3⋅mol−1 or −0.

26 (a) water. as well as the symmetry or asymmetry of the molecule in which it is found).1 g ⋅ cm -3 0.60 × 10−3 cm3 ⋅ g −1 −1 200. London forces would predominate and Cl would be hydrophobic. and dipole-dipole interactions. hydrogen bonding. (b) hydrophobic.07353 cm 3 .07093 cm 3 giving a density for the solid: 1g = 14.5217 cm3 ⋅ mol−1 = .9 × 10−4 mol ⋅ L−1 ⋅ atm −1 × 28.1).7 × 10−4 mol ⋅ L−1 ⋅ atm −1 .6 g ⋅ mol Given the density of liquid mercury. Otherwise. solubility 216 .30 (a) The solubility of air in water is 7.0 atm × 7.2.97 g ⋅ mol−1 × 103 mg ⋅ g −1 = 23 mg ⋅ L−1 (b) The solubility of He is 3.07093 cm3 8. nonpolar. (c) tetrachloromethane 8.97 g ⋅ mol−1 (see Table 5. (c) hydrophilic. 8.9 × 10−4 mol ⋅ L−1 ⋅ atm −1 and the molar mass of air (average) = 28.60 × 10 −3 cm3 = 0. hydrogen bonding. solubility = kH × P solubility (g ⋅ L−1 ) = 1.28 (a) hydrophilic.−0.2. the volume of one gram of liquid mercury is 1g =0. (d) Cl could be hydrophilic because of possible dipole-dipole interactions (depending on the electronegativity of the atom to which the Cl atom is bonded. (b) water.07353 cm3 -3 13.60 g ⋅ cm The volume of 1 g of solid mercury under the conditions given is then: 0.

8 × 10−4 mol ⋅ L−1 ⋅ atm −1 × 10. The factor by which the concentration will increase cannot be predicted.37 mg 8.8 × 10−4 mol ⋅ L−1 ⋅ atm −1 )(10. more CO2(g) will be forced into solution under pressure (Henry’s law). which can be converted to volume using the ideal gas expression: volume of plasma = 0. addition of heat increases the speed and 217 .34 CO2(g) ⎯⎯ → CO2(aq) + heat (exothermic reaction) (a) If the pressure of CO2 is increased.00 L) (0.0 atm × 3. the heat added will favor the escape of CO2 from solution—the reverse process is exothermic. We then use the solution component of the blood volume to determine the total number of moles present.00 L S = kH × P = 5.48 mg ⋅ L−1 (c) solubility (g ⋅ L−1 ) = 25 kPa × 3. (b) If the temperature is raised. because the amount of CO2 present above the solution is unknown.00 g ⋅ mol−1 × 103 mg ⋅ g −1 = 1.(g ⋅ L−1 ) = 1.7 × 10−4 mol ⋅ L−1 ⋅ atm −1 × 4. the concentration of CO2 in solution will decrease.00 atm nN2 = S × 2. Further.325 kPa ⋅ atm × 103 mg ⋅ g −1 = 0.32 This answer can be calculated from the solubility data. which will give an answer in mol ⋅ L−1 .40 L × 8. The concentration of CO2 in solution will thus increase.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(310 K) 1 atm = 0.0 atm)(0. as is the amount of water. however.00 g ⋅ mol−1 −1 101.45)(6.7 × 10−4 mol ⋅ L−1 ⋅ atm −1 × 4.45 × 6.7 L PV = nRT or V = nRT P VN2 = (5.

(b) NH4NO3(s) + heat U NH 4 + (aq) + NO3− (aq).36 (a) endothermically: a positive enthalpy of solution means enthalpy is absorbed by the system during the dissolution process.38 The molar enthalpies of solution are given in Table 8.1 K or + 24.energy of the CO2 molecules.1°C (c) enthalpy of solution of KNO 3 = +34. the endothermic values of solution enthalpy result from systems with lattice enthalpies greater than their enthalpies of hydration. Therefore.26 K or −8.18 J ⋅ K −1 ⋅ g −1 )(100. (c) Given that ∆H L + ∆H hydration = ∆H of solution.0 g) = +24. allowing more of them to break out into the gas phase.13 g ⋅ mol MgBr2 ∆T = − (4.2 kJ ⋅ mol−1 10.18 J ⋅ K −1 ⋅ g −1 )(100.6. 8.0 g) (b) enthalpy of solution of MgBr2 = −185.5 kJ ⋅ mol−1 218 .55 g ⋅ mol KCl ∆T = − = −5. The change in temperature will be given by dividing the heat released by the specific heat capacity of the solution. 8. we expect that for NH4NO3 the lattice enthalpy will be greater than the enthalpy of hydration.9 kJ ⋅ mol −1 10.0 g KCl × (+17 200 J ⋅ mol−1 ) −1 74.18 J ⋅ K −1 ⋅ g −1 )(100.11 g ⋅ mol KNO3 ∆T = − (4.26°C (d) enthalpy of solution of NaOH = −44.52°C (4.0 g MgBr2 × (−185 600 J ⋅ mol−1 ) −1 184. Multiplying these numbers by the number of moles of solid dissolved will give the amount of heat released.6 kJ ⋅ mol −1 10. (a) enthalpy of solution of KCl = +17.0 g KNO3 × (+34 900 J ⋅ mol−1 ) −1 101.0 g) = −8.52 K or −5.

11 m 0. ∆H soln = ∆H L + ∆H hyd . so ∆Hsol would be expected to decrease.11 g ⋅ mol KOH ⎠ ⎝ = = 3.9 g HCl and 961. and ∆Hsol generally does decrease on proceeding down the group of halides. indicating a reluctance to dissolve.00 kg of solution will contain 38.6.0 g) = +26. The decrease in ∆HL outweighs the increase in ∆Hhyd. as the data partly indicate. has an unusually high ∆HL. NaI.07 g ⋅ mol−1 ⎠ ⎝ (b) = 0. NaCl.9 kJ ⋅ mol−1 . NaF.1 g H2O. The exception to the trend.3).9611 kg 219 . It is difficult to say precisely why ionic size has a slightly greater effect on ∆HL than on ∆Hhyd.0 g NaOH × (−44 500 J ⋅ mol−1 ) −1 40.10. +3.0750 kg ⎛ mass ethylene glycol ⎞ ⎜ ⎟ 62.9 kJ ⋅ mol−1 .46 g ⋅ mol HCl ⎠ = 1. NaBr.26 m 0. but ∆Hhyd increases (becomes less negative. ∆HL decreases (see Table 6.9 g HCl ⎜ ⎟ −1 ⎝ 36. ⎛ ⎞ 38. We are effectively taking the difference of two large quantities (recall ∆Hhyd is negative).42 (a) mKOH ⎛ ⎞ 13. and that difference cannot be precisely related to ionic size.44 m 1. −0. 8. − 7.00 g ⋅ mol NaOH ∆T = − (4.5. 1.5 kg mass ethylene glycol = 41 g (c) 1.40 The data for the heats of solution are (in kJ ⋅ mol−1 ) NaF.6 K or + 26.72 g KOH ⎜ ⎟ −1 56. Table 8. As the size of the anion increases.18 J ⋅ K −1 ⋅ g −1 )(100.8).6°C 8.

000 L of 12. The mass of water will be 18.01765 kg.7475 kg solvent 8.36 g ⋅ mol Ba(OH) 2 ⎠ ⎝ = = 0.0205.25 g Ba(OH) 2 ⎟ ⎜ ⎟⎜ −1 1 mol Ba(OH) 2 ⎠ ⎝ 171.183 kg solvent (c) 1.197 mol acetone ⎛ 1 kg ⎞ (0.65 g or 0.100 g H 2SO4 = 8.9795 mol = 17.00% CsCl will contain 100.9 g.9519 g ⋅ cm −3 .00 M NH3(aq) will contain 12. This leaves 951.02 g ⋅ mol−1 ) ⎜ ⎟ ⎝ 1000 g ⎠ 8.9795 mol H2O.46 = 14. mOH− ⎛ 3 Cl− ⎞ ⎜ ⎟ (0.03 g ⋅ mol−1 = 204.29 g ⋅ mol sucrose ⎠ (a) ⎝ = 0.8. then there are 0.5 g as water. so the total mass in the solution is 951.765 mol H2O.0 g CsCl and 900.4 g = 747.235 mol of acetone for 0.00 mol with a mass of 12.0650 m 0.00 × 17.000 L of solution is 0.590 m 0.05 m 0.0205 mol FeCl3 ) FeCl3 ⎠ ⎝ = = 3. ⎛ ⎞ 100.01765 kg solvent (b) mCl− ⎞ ⎛ 2 mol OH − ⎞ ⎛ 9. 12. 0.765 mol H 2 O)(18.02 g ⋅ mol−1 × 0.0 g H2O.9000 kg (c) The solution contains 0.612 kg (b) 1 kg of 10.4 g.07 g ⋅ cm −3 × 0.36 g ⋅ mol CsCl ⎠ = 0.48 m 0.37 g H 2SO 4 1g 220 .63 g sucrose ⎜ ⎟ −1 342.6600 m 0.00 mol NH3 = 16.0205 mol FeCl3 for every 0.0 g CsCl ⎜ ⎟ −1 ⎝ 168.3 m (a) If xFeCl3 is 0. The density of the 1.48 (a) X × 1.44 ⎛ ⎞ 13.9 g − 204.

81 × 55. If the mole fraction of fructose in solutions is 0.07 g ⋅ mol−1 = 0. P = xsolvent × Ppure solvent P = 0.11. so molality = 0.000 − 0.26 Torr = 338 Torr (b) At 25°C.950. xH2O = nH2O nH2O + nurea 1000 g 18.0 g of H2SO4 and 90.950 × 355.2 mL X = (b) 100 g of solution contains 10.02 g ⋅ mol−1 P = 0. 10.0 g equals 0. P = xsolvent × Ppure solvent P = 0.76 Torr.37 g H 2 SO 4 0.9982 1000 g + 0.102 mol = 1.0 g of water. then the mole fraction of the solvent water will be 1.10 mol 18.0 g ÷ 98.0900 kg (c) 250 mL × 1.07 g ⋅ cm −3 × 0. the vapor pressure of water is 23.0900 kg of solvent.50 (a) The vapor pressure of water at 80°C is 355. If the mole fraction of glucose is 0.02 g ⋅ mol−1 = = 0. A 0.050 = 0.100 g H 2 SO 4 ⋅ (g solution) −1 = 26. 90.72 Torr 8.8.07 g ⋅ cm −3 × 1g = 78.81.050.102 mol H2SO4.13 mol ⋅ kg −1 0.76 Torr = 23. then the mole fraction of the solvent will be 0.52 (a) The vapor pressure of pure water at 40°C is 55.100 g H 2 SO 4 1.9982 × 23.10 m solution will contain 0.10 mol urea per 1000 g H2O. The molality of the urea solution must be converted to mole fraction.34 Torr = 45 Torr 221 .34 Torr.26 Torr.8 g H 2 SO 4 8.

58 Torr = 4.58 Torr at 0°C.008 g 0.025 mol + (3 × 0.58 Torr 8.31 g ⋅ mol 62. Assume that the Fe(NO3)3 undergoes complete dissociation is solution: Fe(NO3 )3 (s) ⎯⎯ → Fe3+ (aq) + 3 NO3− (aq) The concentration must be converted from molality to mole fraction: xH2O = nH2O nH2O + nFe3+ + nNO − 3 = 1000 g 18.5 Torr (c) The vapor pressure of pure water is 4.00 Torr 222 .54 Torr.02 g ⋅ mol−1 ≈ 1.00 × 17.00 P = 1.02 g ⋅ mol−1 = ⎛ ⎞ 100 g 0. we will assume it dissociates completely into Mg+2 and F− ions: MgF2 (s) ⎯⎯ → Mg 2 + (aq) + 2 F− (aq) Note that the F− ion concentration will be 2 × that of the Mg2+ concentration: xH2O = nH2O nH2O + nMg2 + + nF− 100 g 18.54 (a) From the relationship P = xsolvent × Ppure solvent we can calculate the mole fraction of the solvent.∆P = 55. (b) The vapor pressure of pure water at 20°C is 17.02 g ⋅ mol 62.025 mol) 18.008 g + + ⎜2× −1 ⎟ −1 −1 18.34 Torr − 45 Torr = 10 Torr.31 g ⋅ mol ⎠ ⎝ ≈ 1.00 Torr: 740 Torr = xsolvent × 760.02 g ⋅ mol−1 1000 g + 0.00 P = 1. the vapor pressure of any liquid will be 760.00 × 4. making use of the fact that at its normal boiling point. When MgF2 dissolves.54 Torr = 17.

974 = 0. i = 3 ⎛ ⎞ 0.15 g + −1 M unknown 46.974 ⎥ ⎢ ⎝ 46.51 K ⋅ kg ⋅ mol −1 × 0. the math is slightly easier if the definition of mole fraction of the solvent is used: xsolvent = nsolvent nunknown + nsolvent 100 g 46.974 = 100 g 9.15 K or 0.xsolvent = 0.00°C + 0. (b) ∆Tb = ikb m For Li2CO3.72 g ⎜ −1 ⎟ 73.100 kg The boiling point will be 100.34°C. 223 .07 g ⋅ mol ⎠ ⎢ ⎥ ⎣ ⎦ (a) ∆Tb = ikb m For CaCl2.15°C = 100.026.07 g ⋅ mol M unknown = 8.34°C The boiling point will be 100.7% solution of urea will contain 1.7 g of urea per 98. (b) The molar mass can be calculated using the definition of mole fraction for either the solvent or the solute.00°C + 0. In this case.89 g ⋅ mol ⎠ ∆Tb = 3 × 0.51 K ⋅ kg ⋅ mol −1 × ⎝ = 0. A 1. i = 1.15 g = 158 g ⋅ mol−1 ⎡⎛ ⎤ ⎞ 100 g ⎢⎜ ⎥ ⎛ −1 ⎟ ⎞ 100 g ⎢⎝ 46.3 g of water.34°C = 100.07 g ⋅ mol ⎠ ⎥−⎜ ⎟ − 1 0.000 − 0.22 mol ⋅ kg −1 = 0. (c) ∆Tb = ikb m Because urea is a nonelectrolyte.34 K or 0.974 The mole fraction of the unknown compound will be 1.56 9. i = 3 ∆Tb = 3 × 0.15°C 0.07 g ⋅ mol−1 0.15°C.

86 K ⋅ kg ⋅ mol−1 × molality molality = 0.0983 kg The boiling point will be 100.12 K ⋅ kg ⋅ mol−1 × molality molality = 0.29 K or 0.7°C boiling point = 80.481°C or 0.559 mol ⋅ kg −1 ∆Tb = kb m = 0. the freezing point of the solution is also the ∆Tf .7 K or 1.559 mol ⋅ kg −1 = 0.68 mol ⋅ kg −1 = 1.1°C + 1.15°C 0.29°C boiling point = 100.04 K = 1.29°C (b) ∆Tf = kf m ∆Tf = 5.06 g ⋅ mol ⎠ ∆Tb = 0.15 K or 0. 8.5 K = 5.58 (a) The molality of the solution can be calculated.5°C or 3. this value can.53 K ⋅ kg ⋅ mol−1 × 0.51 K ⋅ kg ⋅ mol −1 × ⎝ = 0. 1.00°C + 0.68 mol ⋅ kg −1 ∆Tb = kb m = 2. knowing the freezing point.15°C or 100.7°C = 81.5 K 3. be used to calculate the boiling point.5°C − 2.29°C = 100.⎛ ⎞ 1. in turn.0°C = 3. ∆Tf = kf m Because the solvent is water with a normal freezing point of 0˚C.7 g ⎜ −1 ⎟ 60.15°C.8°C 8.481 K ∆Tb = kb × molality 224 .51 K ⋅ kg ⋅ mol−1 × 0.60 ∆Tb = 0.00°C + 0.

001 54 g ⎞ ⎜ ⎟ 73.7 g ⎜ ⎟ 60.481 K 2.25 g = −1 M unknown 2.150 kg 0. 8.54 K or 0.2°C = − 1.481 K (a) ∆Tf = ikf m For CaCl2. (c) ∆Tf = ikf m Because urea is a nonelectrolyte.89 g × mol−1 ⎠ ⎝ −1 ∆Tf = 3 × 1.2°C. i = 3 ∆Tf = 3 × 1.00°C − 0.481 K = 2.3 g of water.0 g ⋅ mol−1 0. i = 3 ⎛ 0.62 2.16 × 10−3 °C.150 kg × 0.481 K = 2.7 g of urea per 98.00°C − 1.64 ∆Tf = kf m 225 .06 g ⋅ mol−1 ⎠ ⎝ −1 ∆Tf = 1.00°C − 1.0983 kg The freezing point will be 0.79 K ⋅ kg ⋅ mol−1 × molality ⎛ 2.100 kg = 1.86 K ⋅ kg ⋅ mol × = 0.86 K ⋅ kg ⋅ mol × 0. (b) ∆Tf = ikf m For Li2CO3.22 mol ⋅ kg −1 = 1.54°C.16 × 10−3°C The boiling point will be 0.79 K ⋅ kg ⋅ mol M unknown = 8.150 kg × 0.16 × 10−3 K or 1.79 K ⋅ kg ⋅ mol × 0. i = 1 A 1.7% solution of urea will contain 1.54°C 0.79 K ⋅ kg ⋅ mol−1 = 87.2°C The freezing point will be 0. ⎛ ⎞ 1.54°C or − 0.2 K or 1.25 g × 2.0.25 g ⎞ ⎜ ⎟ M unknown ⎠ ⎝ −1 0.16 × 10−3°C = − 1.86 K ⋅ kg ⋅ mol−1 × 0.

7°C The freezing point will be 5.12°C − 1.0500 kg × 1.12 K ⋅ kg ⋅ mol−1 × 0.32 g = −1 M unknown 7.454 K 1. nsolute = 0. Psolvent = xsolvent × Ppure solvent 740 Torr = xsolvent × 760 Torr (Remember that the vapor pressure of a liquid at its boiling point is 760 Torr by definition. 226 = 0.27 K ⋅ kg ⋅ mol−1 = 132 g ⋅ mol−1 0.026 molality of solute = 0.454 K (a) We use the vapor pressure to calculate the mole fraction of benzene and then convert this quantity to molality.11 g ⋅ mol ⎞ ⎜ ⎟ 1000 g ⋅ kg −1 ⎝ ⎠ −1 ∆Tf = kf m = 5. we can assume that the total number of moles = 1.34 mol ⋅ kg −1 .34 mol ⋅ kg −1 = 1.27 K ⋅ kg ⋅ mol−1 ) m ⎛ 1.1.974.) xsolvent = 0.974 mol × 78.974 = nsolvent n = solvent nsolvent + nsolute 1 nsolvent = 0.7°C = 3.4°C .66 1.32 g ⎞ ⎜ ⎟ M unknown ⎠ −1 ⎝ 1. which in turn is used to calculate the freezing point depression.974 Because the absolute amount of solvent is not important here. xsolvent = 0.026 mol ⎛ 0.27 K ⋅ kg ⋅ mol ) 0.27 K ⋅ kg ⋅ mol M unknown = 8.454 K = (7.0500 kg 0.0500 kg × 1.454 K = (7.32 g × 7.

To use the freezing point depression equation. ⎛ ⎞ 1.02 K = 1.86 K ⋅ kg ⋅ mol−1 )(0.59 mol ∆Tf = kf m ∆Tf = 1.200 kg nCO( NH2 )2 = 2.168 mol ⋅ kg −1 . giving an i value equal to 2. the total molality in solution would have been 0.86 K ⋅ kg ⋅ mol−1 × nCO( NH2 )2 kg solvent = 1.0839 mol ⋅ kg −1 − x Mg 2+ (aq) + SO 4 2− (aq) x x 227 .192 K i = 1.86 K ⋅ kg ⋅ mol−1 × ⎝ 1.68 (a) A 1.(b) ∆Tf = kf m 4. MgSO4 (aq) U 0.0 g of water.00 g of MgSO4 for 99. we need the molality of the solution.0839 mol ⋅ kg −1 = 0.37 g ⋅ mol ⎠ molality = ⎝ = 0.0839 mol ⋅ kg −1 ) = 0.9 × 10−5 °C (c) freezing point ≈ 0.0 kg = 1.0 × 10 g ⋅ mol ⎠ = 1.0839 mol ⋅ kg −1 .103 mol ⋅ kg −1 (c) If all the MgSO4 had dissociated.02 K = 1.0°C 8. the molality in solution would have equaled 0. If no dissociation had taken place.00 g ⎜ −1 ⎟ 120.23 (b) molality of all solute species (undissociated MgSO4(aq) plus Mg2+(aq) + SO 4 2 − (aq)) = 1.0839 mol ⋅ kg −1 0.9 × 10−5 K or 1.00% aqueous solution of MgSO4 will contain 1.23 × 0.0990 kg ∆Tf = ikf m ∆Tf = i (1.86 K ⋅ kg ⋅ mol −1 × molality 4.0 g ⎜ 5 −1 ⎟ 1.86 K ⋅ kg ⋅ mol−1 × nprotein kg solvent ⎛ ⎞ 1.86 K ⋅ kg ⋅ mol−1 × nCO( NH2 )2 1.

019 mol ⋅ kg −1 × 100 = 23% 0. (a) KCl is an ionic compound that dissociates into 2 ions.248 mol ⋅ kg −1 .1% 0. so i = 2.3 atm (b) urea.86 K ⋅ kg ⋅ mol −1 × 0.0.72 0.124 mol ⋅ kg −1 − x U H + (aq) + CCl3 COO − (aq) x x 0. giving an i value equal to 2.423 K = i × 1.124 mol ⋅ kg −1 i = 1.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 323 K × 0.019 mol ⋅ kg −1 % dissociation = 8.227 mol ⋅ kg −1 x = 0.103 mol ⋅ kg −1 x = 0. 228 . CCl3 COOH(aq) 0.124 mol ⋅ kg −1 + x = 0.124 mol ⋅ kg −1 = 0.124 mol ⋅ kg −1 First. CO(NH2)2 is a nonelectrolyte.83 × 0.103 mol ⋅ kg −1 × 100 = 83.103 mol ⋅ kg −1 0.103 mol ⋅ kg −1 % ionization = 8.124 mol ⋅ kg −1 − x + x + x = 0.10 mol ⋅ L−1 = 5. the total molality in solution would have been 0. If no dissociation had taken place.0839 mol ⋅ kg −1 + x = 0.0839 mol ⋅ kg −1 First calculate the van’t Hoff i factor: ∆Tf = ikf m 0.227 mol ⋅ kg −1 0.124 mol ⋅ kg −1 . calculate the osmotic pressure of each solution from Π = iRT × molarity .70 0.227 mol ⋅ kg −1 If all the CCl3COOH(aq) had dissociated. so i = 1. the molality in solution would have equaled 0. Π = 2 × 0.0839 mol ⋅ kg −1 − x + x + x = 0.83 The molality of all solute species (undissociated CCl3COOH(aq) plus CCl3 COO − (aq) + H + (aq)) = 1.

9 atm (c) K2SO4 is an ionic solid that dissolves in solution to produce 3 ions.10 g ⎞ ⎜ ⎟ M unknown ⎠ ⎝ × 298 K × 0.76 We assume the polymer to be a nonelectrolyte. so i = 3.74 Insulin is a nonelectrolyte.0 × 103 g ⋅ mol−1 8.30 mol ⋅ L−1 = 24 atm Solution (c) has the highest osmotic pressure. 8.200 L 229 . Π = 3 × 0.30 Torr = 1 × 0.50 g ⎞ ⎜ ⎟ M unknown ⎠ ⎝ × 293 K × 0. Π = iRT × molarity Π = 2.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 760 Torr ⋅ atm −1 ⎛ 0. so i = 1.582 Torr = 1 × 0. so i = 1.30 Torr × 0.60 mol ⋅ L−1 = 15.30 Torr × 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 −1 760 Torr ⋅ atm ⎛ 0. Π = iRT × molarity Π = 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 = 2.200 L M unknown 0.200 L × 293 K × 0.Π = 1 × 0.10 g × 760 Torr ⋅ atm −1 2.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 323 K × 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 323 K × 0.200 L = 4.

082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 293 K × 3.16 g ⋅ mol ⎠ and Π = iRTM = (1)(0.8 × 104 g ⋅ mol−1 8.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 293 K × = 0.80 5% glucose = 5.200 L = 7.28 mol ⋅ L−1 ⎟ ⎜ −3 ⎟ ⎜ 2 −1 ⎟ ⎝ 1. 230 .200 L 0. i = 3.072 atm (b) CaCl2 is an ionic compound that will dissolve in solution to give 3 ions.0 × 10−3 mol ⋅ L−1 = 0.M unknown 0.0 g glucose 1.582 Torr × 0. we need to know the mole fraction of each component.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(310 K)(0.28 mol ⋅ L−1 ) = 7.50 g × 760 Torr ⋅ atm −1 × 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 293 K × 0.0 g glucose ⎞ ⎛ 1 mL ⎞ ⎛ 1 mol glucose ⎞ Then ⎜ = 0.0 × 10 mL ⎠ ⎝ 10 L ⎠ ⎝ 180.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 293 K × 2. Π = iRT × molarity = 1 × 0.0 × 102 g solution assume the solution density ≈ 1 g ⋅ mL−1 ⎛ 5.72 atm 8.0 × 10−3 mol ⋅ L−1 = 0.582 Torr × 0. Π = iRT × molarity = 3 × 0.82 (a) To determine the vapor pressure of the solution.1 atm 8. so i = 1.14 atm (c) K2SO4 is an ionic compound that will dissolve into 3 ions in solution.78 (a) Assume that C6H12O6 is a nonelectrolyte. so i =3. Π = iRT × molarity = 3 × 0.010 mol ⋅ L−1 = 0.

494 × 151 Torr) + (0.506 × 98 Torr) = 124 Torr The vapor phase composition will be given by xhexane in vapor phase = Phexane 0.18 g ⋅ mol−1 10.602 = 0.37 = 0.84 We are given the following information: Pbutanone.28 × 151 Torr = = 0.) Ptotal = 135 Torr 231 .63 The vapor is richer in the more volatile cyclohexane. as expected.W.37 113 Torr Ptotal xcyclohexane in vapor phrase = 1 − 0.72 × 98 Torr) = 113 Torr The vapor phase composition will be given by xhexane in vapor phase = Phexane 0.398 8.107 g ⋅ mol−1 M.602 124 Torr Ptotal xcyclohexane in vapor phase = 1 − 0. Torr at 25o C.119 mol xcyclohexane = 1 − xhexane = 0.119 84.25 mol = 0. pure = 100.16 g ⋅ mol−1 nhexane = 0.116 mol + 0.65 mol xcyclohexane = 1 − xhexane = 0. 350. pure = 222 Torr at 25o C (58.0 g = 0.494 0.28 × 151 Torr) + (0. (b) The procedure is the same as in (a) but the number of moles of each component must be calculated first: 10.116 86.0 g ncyclohexane = = 0.506 xhexane = Ptotal = (0.) Ppropanone.72 xhexane = Ptotal = (0.080 g ⋅ mol−1 M.0g (72.116 mol = 0.W.25 mol + 0.28 0.0.494 × 151 Torr = = 0.

we would expect a positive deviation. pure + Ppropanone.81 mol − 4. pure + total Ppropanone.and Raoult's Law states: Ptotal = X butanone Pbutanone.85 mol = 1. pure ntotal ntotal = given ntot al = nbutanone + npropanone we can write: Ptot = nbutanone n − nbutanone Pbutanone. Negative deviation means that the vapor pressure is lower than expected for an ideal solution.8539 mol ⋅ 222 Torr ) 135 Torr − 222 Torr = 6. Benzene and formic acid form an azeotrope that boils 232 . pure ) − ( nbutanone ⋅ Ppropanone. which is observed. pure ) Ptotal − Ppropanone.8539 mol ⋅ 100. pure ntotal ntotal Rearranging to solve for ntotal:’ ntotal = = (n butanone ⋅ Pbutanone. npropanone = ntotal − nbutanone = 6.81 mol Therefore. Negative deviation will occur when the interactions between the different molecules are somewhat stronger than the interactions between molecules of the same kind. which is higher than the boiling point of either HBr (−67°C) or water. HBr and H2O form an azeotrope that boils at 126 ° C. Torr ) − ( 4.080 g ⋅ mol−1 = 113 g 8. the possibility of intermolecular hydrogen bonding between water and HBr would suggest that negative deviation would be observed. pure ( 4. (b) Because formic acid is a very polar molecule with hydrogen bonding and benzene is nonpolar.95 mol ⋅ 58. so a positive deviation means that the vapor pressure is higher than expected for an ideal solution. (a) For HBr and H2O. pure npropanone nbutanone Pbutanone. which is the case.95 mol and masspropanone = 1. pure + X propanone Ppropanone.86 Raoult’s Law applies to the vapor pressure of the mixture.

which is well below the boiling point of either benzene (80. 233 . 1.603 atm = 0.389 ⋅ 1.611 (b) The gas-phase mole fraction is given by: PA = X A. gas = 0. the less volatile component.397 atm Ptot = PA + PB = 0. component A.00 atm Raoult's Law states: Ptot = X A PA.389 = 0. (c) Because cyclohexane and cyclopentane are both nonpolar hydrocarbons of similar size and with similar intermolecular forces.650 atm.55 atm. Solving for X A : XA = Ptot − PB .55 atm = 0.397 atm = 0. The gas phase. pure To solve for the mole fractions of A and B we use: X A + X B = 1. on the other hand.00 atm X B.at 71° C .650 atm and X B = 1 − X A = 1 − 0. but will slowly gain more of component B as the boiling process proceeds.603. the liquid becomes enriched in component B. as the boiling proceeds.397 1. pure = 1. pure = 0.397 atm = 1.00 atm and X A. pure = 1. pure . pure PA. pure + X B PB . and therefore: X B = 1 − X A .603 atm + 0.611 ⋅ 0. PB . 8. and Ptotal = 1. pure − PB .88 (a) Given: PA. pure = 0. gas = 0. liquid PB.650 atm = 0.603 atm PB = X B.00 atm (c) Qualitatively. pure = 0.1° C) or formic acid (101° C) . liquid PA.389 1.55 atm − 0. starts out highly enriched in the more volatile component.650 atm = 0. pure + (1 − X A ) PB . we would expect them to form an ideal solution.00 atm − 0. Substituting into the equation above we obtain: Ptot = X A PA.

but additional liquid evaporates. the water will begin to boil. Sublimation is complete upon further pressure decrease: the system now contains the vapor alone.96 (a) In a sense.98 Partial pressure of H 2 O = 64% × 39. but pressure changes have only a small and usually negligible effect on vapor pressure. which is determined only by the temperature.92 (a) Vapor pressure increases due to the increased kinetic energy of the molecules at higher temperatures. (b) At 50° C . (c) No effect on the vapor pressure. which allows for greater London forces. Adding air above the liquid could increase the external pressure on the liquid.100 Boiling point elevation and freezing point depression both arise because dissolving a solute in a solvent increases the entropy of the solvent. therefore. nothing (the air mass simply warms up and the percent humidity is reduced). 8. 8. (d) Very little effect. For the vapor pressure curve.76 Torr. 8. Hydrogen bonding should occur for both molecules. the lines 234 .8. The vapor pressure of water at 50° C is greater than 5 Torr (between 55 and 150 Torr).90 H2O2 has a greater molar mass than H2O.90 Torr = 26 Torr 100% The vapor pressure of H2O at 25° C is 23. Decreased pressure brings it to the ice/vapor boundary. 8. (b) No effect on the vapor pressure as such. 8. when the solid sublimes. the system exists at the ice/liquid boundary. fog or dew will form. which is determined only by the temperature. water begins in the liquid phase. As the pressure is lowered to 5 Torr. thereby decreasing its free energy.94 (a) At 0° C and 2 atm. but the rate of evaporation increases. (b) It condenses to fog or freezes to frost.

This is explained in detail in section 8.102 (a) ∆Tf = 1.34).17.0 g) = M solute = (kg solvent) (∆Tf ) (0. 235 . 8. so the molecular formula is C6 H 4 Cl2 .0 4.3°C ⎛ msolute ⎞ ⎜ ⎟ M solute ⎠ ⎝ ∆Tf = ik f m = ik f kg solvent ik f msolute (1) (5.5 × 102 g ⋅ mol−1 (b) The empirical formula mass = 73. so the boiling point is higher in the presence of a solute (see Fig.64 3.60 0.representing the free energies of the liquid solution and the vapor intersect at a higher temperature than for the pure solvent.12 K ⋅ kg ⋅ mol−1 ) (10.33b).02 H 7.5°C = − 4.91 9. the experimental formula mass is roughly double this value.04 O 26. so the freezing point is lower in the presence of the solute (see Fig.4 g ⋅ mol−1 . 8.10 7.542 1 The empirical formula is C9 H13 O3 N (formula mass ~ 183 g ⋅ mol−1 ).20°C − 5.99 g ⋅ mol−1 8. (c) molar mass = 146. the lines representing the free energies of the liquid and solid phases of the solvent intersect at a lower temperature than for the pure solvent.542 for N) C 59.0800 kg) (4. Similarly for freezing point depression.04 13.2 1.3°C) = 1.0 N 7.104 (a) The elemental analysis yields the following: ratio to smallest moles element % by mass mol in 100 g (0. 8.

or 2 × 691 Torr = 1. If the volume is halved at constant temperature. so its pressure should follow the ideal gas law.38 × 103 Torr + 58.89 g Li 2 CO3 Π = iRT × molarity = 3 × 0.036 kg)(0.208 mol ⋅ L−1 73. Molar mass of epinephrine =183.108 (a) Given d = 1. Some of the ethanol will condense to return the ethanol(l) U ethanol(g) reaction to the equilibrium point. (b) The total pressure will be the sum of the pressures due to the ethanol vapor and to the air.50°C) = 1.54 g = 15.64 g) M solute = = (kg solvent) (∆Tf ) (0.12 K ⋅ kg ⋅ mol−1 ) (0.9 Torr is due to ethanol vapor.44 × 103 Torr. The total pressure will then be 1. ∴ 1.106 (a) The partial pressure remains the same.4 g ⋅ L−1 100 mL solution 15.4 g ⋅ L−1 × 1 mol Li 2 CO3 = 0.00 g ⋅ mL−1 .208 mol ⋅ L−1 = 14.20 g ⋅ mol−1 .9 Torr = 691 Torr will be due to the air. C9H13O3N.00 g ⋅ cm −3 = 1. The air will not condense.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 273 K × 0. If the total pressure initially is 750 Torr and 58.(b) and (c) ⎛ masssolute ⎞ ⎜ ⎟ M solute ⎠ ⎝ ∆Tf = ik f m = ik f kg solvent ik f masssolute (1)(5. 8. the 750 Torr – 58.8 × 102 g ⋅ mol−1 The molecular formula is the same as the empirical formula. then the pressure due to the air will be doubled. 8.0 atm (b) Psolution = xsolvent × Ppure solvent 751 Torr = xsolvent × 760 Torr 236 .38 × 103 Torr.9 Torr = 1.

012 mol = 0. CO(NH 2 ) 2 .0 mol ⋅ kg −1 −1 kb 0.02 g H 2 O 1. (c) Pressure must be applied to the more concentrated solution. assume i = 1.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 374 K × 2.xsolvent = 0.00 g 1000 mL × × = 2. to equilibrate the water flow. Assume that the volume of solution equals the volume of H 2 O.0 mol ⋅ kg −1 × 1 kg 1.012 Consider a solution of 0.51 K ⋅ kg ⋅ mol Given that d solution = d water = 1. 237 .0 mol ⋅ L−1 1000 g 1. will become more dilute with the passage of H 2 O molecules through the membrane.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 373 K × 0.0178 L Assuming that i = 1. Π = 1 × 0. so i = 1).988 = 0. then molality = ∆Tb 1K = = 2.8 mL = 0.988 xsolute = 1 − 0.67 mol ⋅ L−1 0.00 g ⋅ cm −3 = 1.110 (a) Because the osmotic pressure is calculated from Π = iRT × molarity (both compounds are nonelectrolytes. (b) The more concentrated solution. we have 2.00 g H 2 O = 17.67 mol ⋅ L−1 = 21 atm (c) ∆T = ikb × molality.988 mol H 2 O. CO(NH 2 ) 2 . CO(NH 2 ) 2 . Then V = 0. which in this case is the solution of urea.0 mol ⋅ L−1 = 61 atm 8.00 mL 1.0178 L molarity of solution = 0.988 mol H 2 O × 18.00 L Then Π = iRT × molarity = 1 × 0.00 g ⋅ mL−1 .00 mL H 2 O × 1. the solution with the higher concentration will have the higher osmotic pressure.00 mol H 2 O 1.012 mol solute in 0.

155 g g = 15300 mol -5 1.80665 ) (1000 ) (1000 )( 0. Because ∆G °vap = ∆H ° vap − T ∆S ° vap .5 cm ) ) ( 298 K ) 100 cm 2 m = 1.010 L ) = 1.112 As illustrated in example 8.31447 g cm3 L cm m kg m 2 s 2 K mol )( cm3 1 kg 1000 g ) ( 32.0°C. we start with the expression that ∆G °vap = − RT ln P.02 × 10−3 M ) ( 0. = 0.2 K or 80. C6 H 6 (l) U C6 H 6 (g) ∆H °vap = 30. this is the relationship to use to determine the temperature dependence of ln P: ∆H °vap − T ∆S ° vap = − RT ln P This equation can be rearranged to give: 238 .73 atm 8.02 × 10−3 M The moles of protein in the solution is then: nprotein = (1.02 × 10−5 mol and the molar mass is: M.8. the molar mass is determined by first finding the concentration of the prepared solution: RTc = gdh.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 298 K × 0.114 (a) The data in Table 6. To derive the general equation. where P is the vapor pressure of the solvent.2 can be used to obtain the heat of vaporization and boiling point of benzene.02 × 10 mol 8.038 mol ⋅ L−1 = 0.8 KJ ⋅ mol−1 The boiling point is 353.M. therefore. and. at which the vapor pressure = 1 atm.(d) Π = iRT × ∆M (where ∆M is the difference in molar concentration between the two solutions): Π = 1 × 0.79 ) ( = m s2 (8. c = gdh RT ( 9.

70 × 103 K + 10.∆H °vap ln P = − R × 1 ∆S °vap + T R Because we do not have enough data to calculate ∆S °vap from the table or appendix.655 = − 3. T (c) The solution will boil when the vapor pressure equals the external pressure. This equation is obtained by subtracting one specific point from another as shown: ∆H °vap ln P2 = − R × 1 ∆S °vap + T2 R ∆H °vap 1 ∆S °vap ⎤ ⎡ − ⎢ln P1 = − × + ⎥ R T1 R ⎦ ⎣ ln ∆H °vap P2 =− P1 R ⎡ 1 1⎤ − ⎥ ⎢ T1 ⎦ ⎣ T2 Because we know ∆H °vap and one point.70 × 103 K + 10. Simply substitute the numbers once the equation has been derived: ln P = − 3. we can use the alternate form of the equation.70 × 103 K + 10.314 J ⋅ K −1 ⋅ mol−1 ln P = − ⎡1 1 ⎤ ⎢ T − 353.5 T ln 0.5 T T = 339 K or 66°C 239 . which relates the vapor pressure at two points to the corresponding temperatures.5 T (b) The appropriate quantities to plot to get a straight line are ln P versus 1 .2 K ⎥ ⎣ ⎦ 3. we can introduce those values: ln 30 800 J ⋅ mol−1 P =− 1 8.

26 Torr.9 = − 4.116 The equation to give vapor pressure as a function of temperature is ln P = − ∆H °vap R × 1 ∆S °vap + T R 57 814 J ⋅ mol−1 124 J ⋅ mol −1 1 ln P = − × + 8.314 J ⋅ K −1 ⋅ mol−1 ln P = − 6954 K + 14.3 J ⋅ K −1 ⋅ mol −1 = S °m (benzene.3 J ⋅ K −1 ⋅ mol −1 S °m (benzene. g) − S °m (benzene.314 J ⋅ K −1 ⋅ mol−1 = 87.5 ∆S °vap = 10. g) − 173.5 × 8.008 23 atm or 6. = 10.3 J ⋅ K −1 ⋅ mol−1 Because ∆S ° vap = S °m (benzene.5 is equal to ∆S °vap R ∆S °vap R .26 Torr The pressure needs to be reduced to 6. g) = 260. l) we can now calculate the standard molar entropy of benzene(g) 87. 8.(d) The equation of the line is written in such a form that the constant 10. we need to reduce the external pressure on the sample to its vapor pressure at that temperature.314 J ⋅ K −1 ⋅ mol −1 T 8. the problem becomes simply a matter of calculating the vapor pressure at 80°C : ln P = − 6954 K + 14.6 J ⋅ K −1 mol −1 8.80 353 K P = 0. Thus.9 T In order for the substance to boil.118 The critical pressures and temperatures of the compounds are as follows: 240 .

8 Methyl amine.7 41.9 40.00 L) = ⎜ ⎟ ⎜ −1 ⎟ −1 ⎝ 760 Torr ⋅ atm ⎠ ⎝ 74. (b) mdiethyl ether ⎛ ⎞ ⎛ ⎞ 535 Torr (1. CF4 −45.297 g Because there are 1. Either methane or tetrafluoromethane would be suitable for this application. then the pressure will be due to the vapor pressure of diethyl ether at that temperature. the vapor pressure will be achieved. ammonia would not be suitable because one could not access the supercritical state due to the pressure limitation. Given the rating of the autoclave. mdiethyl ether ⎛ ⎞ ⎛ ⎞ 57 Torr (1. we must have conditions in excess of the critical temperature and pressure. If there is insufficient diethyl ether present. We can calculate the amount of diethyl ether necessary to achieve the vapor pressure from the ideal gas equation. CH 4 −82.13 g 241 . CH 3 NH 2 156. 8.4 In order to access the supercritical fluid state. using the vapor pressure as the pressure of the gas. so the answer to (a) is 57 Torr.Compound TC (°C) PC (atm) Methane.2 Ammonia.12 g ⋅ mol diethyl ether ⎠ mdiethyl ether (0.50 g of diethyl ether.00 L) = ⎜ ⎟ ⎜ −1 ⎟ −1 ⎝ 760 Torr ⋅ atm ⎠ ⎝ 74. then it will all convert to gas and the pressure will be determined from the ideal gas law. NH3 132.5 Tetrafluoromethane. Methylamine would not be suitable for a room temperature extraction because its TC is too high.120 (a) If there is enough diethyl ether present.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 ) (228 K) mdiethyl ether = 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 ) (298 K) = 2.12 g ⋅ mol diethyl ether ⎠ (0.1 45.5 112.

The vapor pressure is lower over the more concentrated solution so ethanol will condense on that side of the apparatus.772 8. there will be a 242 .50 = 0.12 g ⋅ mol diethyl ether ⎠ (0.50 = ␹ pentane. ethanol. the liquid ether in flask A will continue to vaporize and will do so until all the ether has condensed in flask B. liquid = 0. (d) If flask B is cooled by liquid nitrogen. This volume will accommodate twice as much diethyl ether or 2 × 0. liquid P°pentane + (1 − ␹ pentane.50 = ␹ pentane. its temperature will approach −196°C. The pressure will be ⎛ ⎞ 1.495 atm or 376 Torr (c) The system is at the same temperature as in (a) but the volume is now doubled.594 g.122 0.00 L) = ⎜ ⎟ −1 ⎝ 74.In this case.228. liquid ) (512 Torr ) (␹ pentane. The volatile component. As the ether condenses in flask B.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 ) (298 K) P = 0. there is not enough diethyl ether to achieve equilibrium so all of the ether will vaporize.297 g = 0. The vapor pressure of ether at that temperature is negligible and the ether will solidify in flask B. ␹ hexane. will transfer from one solution to the other until the vapor pressures (and therefore concentrations) are equal. liquid = 0. or 57 Torr. liquid P°pentane ␹ pentane. liquid ) (151 Torr) ␹ pentane. There is still sufficient diethyl ether for this to occur so that the pressure will again be equal to the vapor pressure of diethyl ether. 8. As this takes place. gas = 0.124 (a) The vapor pressures over the two solutions are different.50 g diethyl ether ( P ) (1. At the end of this. liquid P°hexane (␹ pentane. liquid P°pentane ␹ pentane. liquid ) (512 Torr) + (1 − ␹ pentane. liquid ) P°hexane ␹ pentane. there will be no ether left in flask A and the pressure in the apparatus will be 0. liquid P°pentane + ␹ hexane.

9955) (60 Torr) ≅ 60 Torr. The mole fraction of sucrose for the solution will be 0.0 g of solution there will be 0.73 g ⎜ −1 ⎟ ⎝ 342. corresponding to 17 g sucrose and a total solution mass of 1017 g.07 g ⋅ mol ⎠ ⎝ 342. For the 0.15 m solution.29 g ⋅ mol ⎠ = ⎞ ⎛ 14.29 g ⋅ mol ⎠ Solving this equation gives x = 7.098 m solution of sucrose.0045.27 g of ethanol. In order to calculate the vapor pressure. This can be expressed mathematically by the following relationship: ⎛ ⎞ 0. for the 0.75 − x g ⎞ ⎛ 0. The concentrations will be made equal by transferring some ethanol from one solution to the other. At equilibrium. A 0. there will be 0.0045 = 0.050 mol sucrose for 1000 g ethanol. In 15.29 g ⋅ mol ⎠ ⎞ ⎛ 14.3 g. Similarly. In 15.73 g +⎜ ⎜ −1 ⎟ −1 ⎟ ⎝ 46. the concentrations must be equal.75 g ethanol.0 g of solution there will be 0.29 g ⋅ mol ⎠ ⎛ ⎞ 0.27 + x g ⎞ ⎛ 0. (b) The vapor pressure will be determined by the concentration of the solution (the solutions in both sides of the apparatus will have the same concentration) once the system reaches equilibrium. 243 . This corresponds to 51 g of sucrose for a total solution mass of 1051 g. there will be 0.25 g sucrose and 14.25 g ⎜ −1 ⎟ ⎝ 342.050 m solution.15 mol sucrose (342.07 g ⋅ mol ⎠ ⎝ 342. we need to know the concentration in terms of mole fractions.0045 mole fraction corresponds to a 0. and the mole fraction of ethanol will be 1 – 0.9955.29 g ⋅ mol−1 ) for 1000 g ethanol (46. The vapor pressure will be P = ␹ ethanol P°ethanol = (0.25 g +⎜ ⎜ −1 ⎟ −1 ⎟ ⎝ 46.73 g sucrose and 14.07 g ⋅ mol−1 ).net transfer of ethanol from the less concentrated side to the more concentrated side of the apparatus.

76 Torr ) = 23. nH 2O = (100 mL ) (1. 8.00133 mol = ( 0. then the molar mass of a monomer is 53.100 L ) ( 0.0133 M (1)( 0.1 % upon addition of the polymer.55 mol = 0.75 Torr X H2O = PH2O (d) Measuring the change in osmotic pressure proves to be a better method in this case.7 g g M.M.55 mol + 0.126 (a) The polymer concentration is given by: c= Π iRT = 0. Because compound (a) has two carboxylic acid units (COOH).128 Compound (a).9998 )( 23.00 mLg ) 18.0133 M )( 0.8. so the more polar compound of (a) and (b) should be attracted more strongly to the stationary phase and should remain on the column longer.08206 KL atm mol )( 298 K ) The moles of polymer in solution are: npolymer = ( 0. npolymer = ( 0.325 atm = 0. it will be more polar and will have the greater value of k.01328 mol L ) = 0.06 g/mol ) = 135 monomers .02 g mol = 5.00133 mol.9998 and 5.00664 mol and the molar mass of the polymer is: 47. The osmotic pressure developed by the resulting polymer solution is readily measured while the change in partial pressure of H2O(g) changes by less than 0. The stationary phase is more polar than the liquid phase. pure in 100 mL.55 mol and.06 g/mol and the average number of monomers in a polymer is: ( 7180g/mol ) / ( 53. 244 . 5.500 L ) = 0. = = 7180 mol 0. (c) The pressure of H2O(g) above the mixture is given by: PH2O = X H 2O ⋅ PH2O. Therefore.00664 mol (b) If a monomer in the polymer is −CH2CH(CN)−.

8 g S ⎞ ⎜ M ⎟ Sx −1 ⎜ ⎟ 0.575 kg ⎟ ⎜ ⎟ ⎝ ⎠ M S x = 257 g ⋅ mol−1 The molecular formula for the sulfur compound is: Freezing-point depression = k f × molality 257 g Sx ⋅ mol−1 =8 32. Octane would have the lowest vapor pressure as it is the most massive of the three options.06 g S ⋅ mol−1 Therefore.8.322 ⎞ M 0.0 K ⋅ mol ⋅ kg ) ⎜ 0.2 K × ⎜ ⎟ ⎝ 0.0 K ⋅ mol−1 ⋅ kg −1 molality 1 mol ⋅ kg The molecular weight of the Sx is found using: Freezing-point depression = k f × molality ⎛ 14.7 = ( 7.130 We can use the initial data to calculate an experimental freezing-point depression constant for naphthalene: Freezing-point depression = k f × molality kf = Freezing-point depression 7.134 (a) The molar mass of L-carnitine is found as in problem 8.130 above: Π = iRT × molarity g ⎛ 0. 8.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 × 305. the molecular formula is S8 .501 atm = 1 × 0. One would expect that neopentane would have the highest vapor pressure as the molecules are rigid and unable to “flex” to increase favorable intermolecular interactions.132 All three molecules possess the same weak London forces holding them in the condensed phase.100 kg ⎠ M = 161 g ⋅ mol−1 (b) The empirical formula is found first using the observed composition of the compound: Assuming 100 g of compound: 245 .0 K = = 7. 8.

343 mol 12.9994 g ⋅ mol−1 C: (7) (15) (1) (3) (the whole numbers on the right were obtained by dividing the number of moles of each element by the moles of N present. therefore.011 g ⋅ mol−1 9.52.620 mol 14. which matches the molecular mass determined using the osmotic pressure above indicating that C7H15O3N is the molecular formula for L-carnitine.00794 g ⋅ mol−1 8.38 g H: = 9.861 mol 15.69 g N: = 0. 8. (c) CsBr would be more soluble.31 mol 1.) The empirical formula is. which gives this molecule some polar character. 246 . (b) KI would be more soluble as it is less polar than KCl.2 g mol−1.01 g ⋅ mol−1 29.136 (a) CH3OH will be more soluble as it has a polar –OH group. C7H15O3N.78 g O: = 1. CH4 is completely nonpolar. The molecular mass of this formula is 161. again because CsBr is less polar than highly polar LiBr.16 g = 4. a highly polar molecule.