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8.1

In a 1.0 L vessel at 20C, there will be 17.5 Torr of water vapor. The ideal gas law can be used to calculate the mass of water present:

PV = nRT let m = mass of water

17.5 Torr m (1.0 L) = (0.082 06 L atm K 1 mol1 ) (293 K) 1 1 760 Torr atm 18.02 g mol (17.5 Torr) (1.0 L) (18.02 g mol1 ) m= (760 Torr atm 1 ) (0.082 06 L atm K 1 mol1 ) (293 K) m = 0.017 g

8.3

(a) 99.2C;

(b) 99.7C

8.5

(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 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, which for pressure is P divided by the reference state of 1 atm, so that the quantity inside the ln term is dimensionless.

H vap 58 Torr = + S vap 760 Torr 250.4 K H vap 512 Torr 8.314 J K 1 mol1 ln = + S vap 760 Torr 298.2 K

8.314 J K 1 mol1 ln

SM-198

21.39 J K 1 mol1 = 0.003 994 K 1 H vap + S vap 3.284 J K 1 mol1 = 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 :

18.11 J K 1 mol1 = 0.000 641 H vap H vap = + 28.3 kJ mol1

(b) We can then use H vap to calculate S vap using either of the two equations:

21.39 J K 1 mol1 = 0.003 994 K 1 ( + 28 200 J mol1 ) + S vap S vap = 91.2 J K 1 mol1 3.284 J K 1 mol1 = 0.003 353 K 1 ( + 28 200 J mol1 ) + S vap S vap = 91.3 J K 1 mol1

(d) The boiling point can be calculated using one of several methods. The easiest to use is the one developed in the last chapter:

Gvap = H vap TB S vap = 0 H vap = TB S vap or TB = TB = H vap S vap

H vap P2 = P R 1

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.

SM-199

8.7

(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, which 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 mol1 ln 1 = 8.314 J K 1 mol1 ln

H vap

292.7 K

+ S vap

which give, upon combining terms, 0 J K 1 mol1 = 0.003 416 K 1 H vap + S vap

6.235 J K 1 mol1 = 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 :

+ 6.235 J K 1 mol1 = + 0.000 244 K 1 H vap H vap = + 25.6 kJ mol1

(b) We can then use H vap to calculate S vap using either of the two equations: 0 = 0.003 416 K 1 ( + 25 600 J mol1 ) + S vap

S vap = 87.4 J K 1 mol1 6.235 J K 1 mol1 = 0.003 660 K 1 (+25 600 J mol1 ) + S vap S vap = 87.5 J K 1 mol1

SM-200

ln

H vap P2 = P R 1

1 1 T2 T1

We need to insert the calculated value of the enthalpy of vaporization and one of the known vapor pressure points:

ln 25 600 J mol1 1 1 1 1 1 atm 8.314 J K mol 291.7 K 292.7 K Pat 8.5 C = 1.0 atm or 7.6 102 Torr Pat 8.5 C =

8.9

(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 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 which, for pressure, is P divided by the reference state of 1 atm, so that the quantity inside the ln term is dimensionless.

H vap 35 Torr = + S vap 760 Torr 161.2 K H vap 253 Torr 8.314 J K 1 mol1 ln = + S vap 760 Torr 189.6 K

8.314 J K 1 mol1 ln

25.59 J K 1 mol1 = 0.006 203 K 1 H vap + S vap 9.145 J K 1 mol1 = 0.005 274 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 :

16.45 J K 1 mol1 = 0.000 929 H vap H vap = +17.7 kJ mol1

SM-201

(b) We can then use H vap to calculate S vap using either of the two equations:

25.59 J K 1 mol1 = 0.006 203 K 1 ( +17 700 J mol1 ) + S vap S vap = 84 J K 1 mol1 9.145 J K 1 mol1 = 0.005 274 K 1 ( + 17 700 J mol1 ) + S vap S vap = 84 J K 1 mol1

Notice that the standard Gr is negative, so that the vaporization of arsine is spontaneous, which is as expected; under those conditions arsine is a gas at room temperature. (d) The boiling point can be calculated from one of several methods. The easiest to use is that 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

H vap 1 1 P2 = . P R T2 T1 1

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.

8.11

(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 SM-202

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 which, 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 mol1 ln 1 = 8.314 J K 1 mol1 ln

H vap

315.58 K

+ S vap

14.06 J K 1 mol1 = 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 .

14.06 J K 1 mol1 = 0.000 491 K 1 H vap H vap = + 28.6 kJ mol1

(b) We can then use H vap to calculate S vap using either of the two equations: 0 = 0.003169 K 1 (+ 28 600 J mol1 ) + S vap

S vap = 90.6 J K 1 mol1 14.06 J K 1 mol1 = 0.003 660 K 1 (+ 28 600 J mol1 ) + S vap S vap = 90.6 J K 1 mol1

ln

H vap P2 = P R 1

1 1 T2 T1

We need to insert the calculated value of the enthalpy of vaporization and one of the known vapor pressure points:

ln Pat 25.0 C 1 atm = 28 600 J mol1 1 1 1 1 8.314 J K mol 298.2 K 315.58 K

SM-203

8.13

Table 6.2 contains the enthalpy of vaporization and the boiling point of methanol (at which the vapor pressure = 1 atm). Using this data and the equation

ln

H vap P2 = P R 1

1 1 T2 T1

ln

(a) vapor; (b) liquid; (c) vapor; (d) vapor (a) 2.4 K; (b) about 10 atm; (c) 5.5 K; (d) no (a) At the lower pressure triple point, liquid helium-I and -II are in equilibrium with helium gas; at the higher pressure triple point, liquid helium-I and -II are in equilibrium with solid helium. (b) helium-I

8.21

8.23

H fus dP = dT T V fus

H fus =

dP T V fus dT

V fus

3

(1.20 cm

SM-204

H fus =

dP 1999 bar -1 T V fus = (278.67 K)(0.00120 L mol ) dT 6.08 K = 110 L bar mol-1

-1 -1

S fus = H fus T =

8.25

(b) CCl4

is non-polar, so the best choice is benzene; (c) CH3COOH is polar, so water is the better choice.

8.27

(a) hydrophilic, because NH2 is polar, and has a lone pair and H atoms that can participate in hydrogen bonding to water molecules; hydrophobic, because the CH3 group is not very polar; (c) hydrophobic, because the Br group is not very polar; (d) hydrophilic, because the carboxylic acid group has lone pairs on oxygen and an acidic proton that can participate in hydrogen bonding to water molecules.

8.29

(a) The solubility of O2(g) in water is 1.3 103 mol L1 atm 1. solubility at 50 kPa =

(b) The solubility of CO 2 (g) in water is 2.3 102 mol L1 atm 1 . solubility at 500 Torr =

(c) solubility = 0.10 atm 2.3 102 mol L1 atm 1 = 2.3 103 mol L1 .

8.31

= 4 mg L1 or 4 ppm

SM-205

(b) The solubility of O2 (g) in water is 1.3 103 mol L1 atm 1 which can be converted to parts per million as follows: In 1.00 L (corresponding to 1 kg) of solution there will be

1.3 10 3 mol O 2 1.3 10 3 mol kg 1 atm 1 O 2 32.00 g mol1 O 2 103 mg g 1

(c) P =

0.1 atm = 0.5 atm 0.21

8.33

(a) By Henrys law, the concentration of CO 2 in solution will double. (b) No change in the equilibrium will occur; the partial pressure of CO 2 is unchanged and the concentration is unchanged.

8.35

(a) Because it is exothermic, the enthalpy change must be negative; (b) Li 2SO 4 (s) 2 Li + (aq) + SO 4 2 (aq) + heat; (c) Given that

larger. If the lattice energy were greater, the overall process would be endothermic.

8.37

To answer this question we must first determine the molar enthalpies of solution and multiply this by the number of moles of solid dissolved to get the actual amount of heat released. (a) H hydration = + 3.9

H = 10.0 g NaCl (+3.9 kJ mol1 ) = 0.67 kJ or 6.7 102 J 58.44 g mol1

H = 10.0 g NaBr (0.6 kJ mol1 ) = 0.06 kJ or 6 10 J 1 102.90 g mol

H =

H = 10.0 g NH 4 NO3 (+ 25.7 kJ mol1 ) = +3.21 kJ 80.04 g mol1

8.39

All the enthalpies of solution are positive. Those of the alkali metal chlorides increase as the cation becomes larger and less strongly hydrated by water. All the alkali metal chlorides are soluble in water, but AgCl is not. AgCl has a relatively large positive enthalpy of solution. When dissolving is highly endothermic, the small increase in disorder due to solution formation may not be enough to compensate for the decrease in disorder for the surroundings, and a solution does not form. This is the case for AgCl.

10.0 g NaCl 58.44 g mol1 = = 0.684 m 0.250 kg mass NaOH 40.00 g mol1 = = 0.22 m 0.345 kg

8.41

(a) mNaCl

(b) mNaOH

1.54 g urea 1 60.06 g mol urea = = 0.0498 m 3 1 kg 3 (515 cm ) (1.00 g cm ) 1000 g

(c) murea

8.43

50.0 g K 3 PO 4 1 212.27 g mol K 3 PO 4 = 0.248 m 0.950 kg

(b) The mass of 1.00 L of solution will be 1043 g, which will contain SM-207

52.2 g K 3 PO 4 1 212.27 g mol K 3 PO 4 = 0.246 M 1.00 L

8.45

(a) If xMgCl2 is 0.0175, then there are 0.0175 mol MgCl2 for every 0.9825 mol H 2 O. The mass of water will be 18.02 g mol1 0.9825 mol = 17.70 g or 0.017 70 kg.

2 Cl (0.0175 mol MgCl2 ) MgCl2 = = 1.98 m 0.017 70 kg solvent 7.12 g NaOH 1 40.00 g mol NaOH = = 0.548 m 0.325 kg solvent

mCl

(b) mCl

(c) 1.000 L of 15.00 M HCl(aq) will contain 15.00 mol with a mass of

15.00 36.46 g mol1 = 546.9 g. The density of the 1.000 L of solution

is 1.0745 g cm 3 so the total mass in the solution is 1074.5 g. This leaves 1074.5 g 546.9 g = 527.6 g as water.

15.00 mol HCl = 28.43 m 0.5276 kg solvent

8.47

(a) Molar mass of CaCl 2 6 H 2 O = 219.08 g mol1 , which consists of 110.98 g CaCl2 and 108.10 g of water.

mCaCl2 = x mol CaCl2 6 H 2 O 0.500 kg + x (6 0.018 02 kg H 2 O)

x = number of moles of CaCl2 6 H 2 O needed to prepare a solution of

molality mCaCl2 , in which each mole of CaCl2 6 H 2 O produces 6(0.018 02 kg) of water as solvent (assuming we begin with 0.250 kg H 2 O). For a 0.175 m solution of CaCl2 6 H 2 O, SM-208

0.175 m =

x 0.500 kg + x(6)(0.018 02 kg H 2 O)

x = 0.0875 mol + x(0.0189 mol) x 0.0189 x = 0.0875 mol 0.981 x = 0.0875 mol x = 0.0892 mol CaCl2 6 H 2 O 219.08 g CaCl2 6 H 2 O (0.0892 mol CaCl2 6 H 2 O) = 19.5 g CaCl2 6 H 2 O 1 mol CaCl2 6 H 2 O (b) Molar mass of NiSO 4 6 H 2 O = 262.86 g mol 1 , which consists of 154.77 g NiSO4 and 108.09 g H 2 O.

mNiSO4 = x mol NiSO 4 6 H 2 O 0.500 kg + x (6 0.01802 kg H 2 O)

where x = number of moles of NiSO 4 6H 2 O needed to prepare a solution of molality mNiSO4 , in which each mole of NiSO 4 6 H 2O produces 6(0.018 02 kg) of water as solvent. Assuming we begin with 0.500 kg H 2 O,for a 0.33 m solution of NiSO 4 6 H 2O, 0.33 m = x 0.500 kg + x(6) (0.018 02 kg H 2 O)

x = 0.16 mol + x(0.0357 mol) x 0.0357 x = 0.16 mol 0.964 x = 0.16 mol x = 0.17 mol NiSO 4 6 H 2 O 262.86 g NiSO 4 6 H 2 O (0.17 mol NiSO 4 6 H 2O) = 45 g NiSO 4 6 H 2 O 1 mol NiSO 6 H O 4 2

8.49

(a) P = xsolvent Ppure solvent At 100C, the normal boiling point of water, the vapor pressure of water is 1.00 atm. If the mole fraction of sucrose is 0.100, then the mole fraction of water is 0.900:

P = 0.900 1.000 atm=0.900 atm or 684 Torr

SM-209

(b) First, the molality must be converted to mole fraction. If the molality is 0.100 mol kg 1 , then there will be 0.100 mol sucrose per 1000 g of water. 1000 g nH2O 18.02 g mol1 xH2O = = = 0.998 1000 g nH2O + nsucrose + 0.100 mol 18.02 g mol1 P = 0.998 1.000 atm = 0.998 atm or 758 Torr (a) The vapor pressure of water at 0C is 4.58 Torr. The concentration of the solution must be converted to mole fraction in order to perform the calculation. A solution that is 2.50% ethylene glycol by mass will contain 2.50 g of ethylene glycol per 97.50 g of water. nH2O nH2O + nethylene glycol 97.50 g 18.02 g mol1 = = 0.993 97.50 g 2.50 g + 18.02 g mol1 62.07 g mol1

8.51

xH2O =

P = 0.993 4.58 Torr = 4.55 Torr

(b) The vapor pressure of water is 355.26 Torr at 80C. The concentration given in mol kg 1 must be converted to mole fraction. 1000 g 18.02 g mol1 xH2O = = = 0.9944 1000 g nH2O + nNa + + nOH + 2 0.155 mol 18.02 g mol1 P = 0.9972 355.26 Torr = 354.3 Torr nH2O (c) At 10C , the vapor pressure of water is 9.21 Torr. The concentratioin must be expressed in terms of mole fraction: 100 g 18.02 g mol1 = = 0.982 xH2O = 100 g 5.95 g nH2O + nurea + 18.02 g mol1 60.06 g mol1 P = 0.982 9.21 Torr = 9.04 Torr nH2O The change in the vapor pressure will therefore be 9.21 9.04 = 0.17 Torr SM-210

8.53

(a) From the relationship P = xsolvent Ppure solvent we can calculate the mole fraction of the solvent: 94.8 Torr = xsolvent 100.0 Torr xsolvent = 0.948 The mole fraction of the unknown compound will be 1.000 0.948 = 0.052. (b) The molar mass can be calculated by using the definition of mole fraction for either the solvent or solute. In this case, the math is slightly easier if the definition of mole fraction of the solvent is used: xsolvent = nsolvent nunknown + nsolvent

100 g 78.11 g mol1 0.948 = 100 g 8.05 g + 1 M unknown 78.11 g mol M unknown = 8.05 g = 115 g mol1 100 g 100 g 0.948 1 1 78.11 g mol 78.11 g mol

8.55

Tb = 0.51 K kg mol 1 0.10 mol kg 1 = 0.051 K or 0.051C

The boiling point will be 100.000C + 0.051C = 100.051C. (b) Tb = ikb m For NaCl, i = 2.

Tb = 2 0.51 K kg mol 1 0.22 mol kg 1 = 0.22 K or 0.22C

The boiling point will be 100.00C + 0.22C = 100.22C. (c) Tb = ikb m 0.230 g 1 25.94 g mol Tb = 2 0.51 K kg mol1 = 0.090 K or 0.090C 0.100 kg The boiling point will be 100.000C + 0.090C or 100.090C. SM-211

8.57

(a) Pure water has a vapor pressure of 760.00 Torr at 100C. The mole fraction of the solution can be determined from P = xsolvent Ppure solvent . 751 Torr = xsolvent 760.00 Torr xsolvent = 0.988 The mole fraction needs to be converted to molality:

xsolvent = 0.988 =

Because the absolute amount of solution is not important, we can assume that the total number of moles = 1.00.

0.988 = nH2O nH2O 1.00 mol = 0.988 mol; nsolute = 0.012 mol 0.012 mol = 0.67 mol kg 1 0.988 mol 18.02 g mol1 1000 g kg 1

molality =

Tb = kb m Tb = 0.51 K mol kg 1 0.67 mol kg 1 = 0.34 K or 0.34C Boiling point = 100.00C + 0.34C = 100.34C (b) The procedure is the same as in (a). Pure benzene has a vapor pressure of 760.00 Torr at 80.1C. The mole fraction of the solution can be determined from P = xsolvent Ppure solvent 740 Torr = xsolvent 760.00 Torr xsolvent = 0.974 The mole fraction needs to be converted to molality:

xsolvent = 0.974 = nbenzene nbenzene + nsolute

Because the absolute amount of solution is not important, we can assume that the total number of moles = 1.00:

SM-212

0.974 =

nbenzene 1.00 mol 0.026 mol = 0.34 mol kg 1 1 0.974 mol 78.11 g mol 1000 g kg 1

Knowing the mole fraction, one can calculate Tb : Tb = kb m Tb = 2.53 K kg mol1 0.34 mol kg 1 = 0.86 K or 0.86C Boiling point = 80.1C + 0.86C = 81.0C

8.59

Tb = kb molality 0.31 K = 4.95 K kg mol1 molality 1.05 g M unknown 1 0.31 K = 4.95 K kg mol 0.100 kg 0.100 kg 0.31 K 1.05 g = 1 4.95 K kg mol M unknown M unknown 1.05 g 4.95 K kg mol1 = = 1.7 102 g mol1 0.100 kg 0.31 K

8.61

Tf = 1.86 K kg mol 1 0.10 mol kg 1 = 0.19 K or 0.19C

The freezing point will be 0.000C 0.19C = 0.19C. (b) Tf = ikf m For NaCl, i = 2

Tf = 2 1.86 K kg mol1 0.22 mol kg 1 = 0.82 K or 0.82C

i = 2 for LiF

SM-213

0.120 g 1 25.94 g mol Tf = 2 1.86 K kg mol1 = 0.172 K or 0.172C 0.100 kg The freezing point will be 0.000C 0.172C = 0.172C. Tf = 179.8C 176.9C = 2.9C or 2.9 K Tf = kf m 2.9 K = (39.7 K kg mol1 )m 1.14 g M 2.9 K = (39.7 K kg mol1 ) unknown 0.100 kg 0.100 kg 2.9 K 1.14 g = 1 39.7 K kg mol M unknown M unknown = 1.14 g 39.7 K kg mol1 = 1.6 102 g mol1 0.100 kg 2.9 K

8.63

8.65

(a) First, calculate the molality using the change in boiling point, and then use that value to calculate the change in freezing point. Tb = kb m Tb = 82.0C 80.1C = 1.9C or 1.9 K 1.9 K=2.53 K Kg mol1 molality molality=0.75 mol kg 1 Tf = kf m Tf = 5.12 K kg mol 0.75 mol kg 1

1

Tf = 3.84 K or 3.84C The freezing point will be 5.5C 3.84C = 1.7C (b) Tf = kf m Because the freezing point of water = 0.00C, the freezing point of the solution equals the freezing point depression.

SM-214

(c) Tf = kf m

1.94 K = (1.86 K kg mol1 )m 1.94 K = 1.86 K kg mol1 1.94K = 1.86 K kg mol1 nsolute = 0.209 mol nsolute kg (solvent) nsolute 0.200 kg

8.67

(a) A 1.00% aqueous solution of NaCl will contain 1.00 g of NaCl for 99.0 g of water. To use the freezing point depression equation, we need the molality of the solution: 1.00 g 1 58.44 g mol = 0.173 mol kg 1 molality= 0.0990 kg

Tf = ikf m Tf = i (1.86 K kg mol1 ) (0.173 mol kg 1 ) = 0.593 K i = 1.84

(b) molality of all solute species (undissociated NaCl(aq) plus Na+ (aq) + Cl (aq)) = 1.84 0.173 mol kg 1 = 0.318 mol kg 1 (c) If all the NaCl had dissociated, the total molality in solution would have been 0.346 mol kg 1 , giving an i value equal to 2. If no dissociation had taken place, the molality in solution would have equaled 0.173 mol kg 1. NaCl(aq)

Na + (aq) + Cl (aq)

x x

0.173 mol kg 1 x

0.173 mol kg 1 x + x + x = 0.318 mol kg 1 0.173 mol kg 1 + x = 0.318 mol kg 1 x = 0.145 mol kg 1

% dissociation =

SM-215

8.69

For an electrolyte that dissociates into two ions, the vant Hoff i factor will be 1 plus the degree of dissociation, in this case 0.075. This can be readily seen for the general case MX. Let A = initial concentration of MX (if none is dissociated) and let Y = the concentration of MX that subsequently dissociates: MX(aq) M n + (aq) + X n (aq)

AY

The total concentration of solute species is (A Y) + Y + Y = A + Y The value of i will then be equal to A + Y or 1.075. The freezing point change is then easy to calculate:

Tf = ikf m = 1.075 1.86 K kg mol1 0.10 mol kg 1 = 0.20

Freezing point of the solution will be 0.00C 0.20C = 0.20C. (a) = iRT molarity

= 1 0.082 06 L atm K 1 mol1 293 K 0.010 mol L1 = 0.24 atm or 1.8 102 Torr

8.71

(b) Because HCl is a strong acid, it should dissociate into two ions, H + and Cl , so i = 2.

= 48 atm (c) CaCl2 should dissociate into 3 ions in solution, therefore i = 3.

= 0.72 atm or 5.5 102 Torr

The polypeptide is a nonelectrolye, so i = 1.

8.73

= iRT molarity =

3.74 Torr 760 Torr atm 1 0.40 g M = 1 0.082 06 L atm K 1 mol1 300 K unknown 1.0 L SM-216

M unknown

0.082 06 L atm K 1 mol1 300 K 0.40 g 760 Torr atm 1 = 3.74 Torr 1.0 L = 2.0 103 g mol1

8.75

= iRT molarity =

5.4 Torr 760 Torr atm 1 0.10 g M = 1 0.082 06 L atm K 1 mol1 293 K unknown 0.100 L

M unknown =

0.082 06 L atm K 1 mol1 293 K 0.10 g 760 Torr atm 1 5.4 Torr 0.100 L

8.77

= iRT molarity

= 1 0.082 06 L atm K 1 mol1 293 K 0.050 mol L1 =1.2 atm (b) NaCl dissociates to give 2 ions in solution, so i = 2.

= iRT molarity

= 2 0.082 06 L atm K 1 mol1 293 K 0.0010 mol L1 =0.048 atm or 36 Torr (c) AgCN dissociates in solution to give two ions (Ag + and CN ) , so i = 2.

= iRT molarity

We must assume that the AgCN does not significantly affect either the volume or density of the solution, which is reasonable given the very small amount of it that dissolves.

SM-217

2.3 105 g 1 133.89 g mol 100 g H 2 O 3 3 1 1 g cm H 2 O 1000 cm L = 8.3 105 atm

8.79

=n

RT m RT = V M V

mRT VC (0.166 g) (0.082 06 L atm K 1 mol1 ) (293 K) = 2.5 105 g mol1 M= 1.2 Torr (0.010 L) 1 760 Torr atm M=

8.81

(a) To determine the vapor pressure of the solution, we need to know the mole fraction of each component. xbenzene = 1.50 mol = 0.75 1.50 mol + 0.50 mol

xtoluene = 1 xbenzene = 0.25 Ptotal = (0.75 94.6 Torr) + (0.25 29.1 Torr) = 78.2 Torr The vapor phase composition will be given by xbenzene in vapor phase = Pbenzene 0.75 94.6 Torr = = 0.91 Ptotal 78.2 Torr

xtoluene in vapor phase = 1 0.91 = 0.09 The vapor is richer in the more volatile benzene, as expected. (b) The procedure is the same as in (a) but the number of moles of each component must be calculated first:

nbenzene = ntoluene 15.0 g = 0.192 78.11 g mol1 65.3 g = = 0.709 92.14 g mol1

SM-218

xbenzene =

xtoluene = 1 xbenzene = 0.787 Ptotal = (0.213 94.6 Torr) + (0.787 29.1 Torr) = 43.0 Torr The vapor phase composition will be given by xbenzene in vapor phase = Pbenzene 0.213 94.6 Torr = = 0.469 Ptotal 43.0 Torr

8.83

To calculate this quantity, we must first find the mole fraction of each that will be present in the mixture. This value is obtained from the relationship Ptotal = [ x1,1-dichloroethane Ppure 1,1-dichloroethane ] +[x1,1-dichlorotetrafluoroethane Ppure 1,1-dichlorotetrafluoroethane ] 157 Torr = [ x1,1-dichloroethane 228 Torr] + [ x1,1-dichlorotetrafluoroethane 79 Torr] 157 Torr = [ x1,1-dichloroethane 228 Torr] + [(1 x1,1-dichloroethane ) 79 Torr] 157 Torr = 79 Torr + [( x1,1-dichloroethane 228 Torr) ( x1,1-dichloroethane 79 Torr)] 78 Torr = x1,1-dichloroethane 149 Torr x1,1-dichloroethane = 0.52 x1,1-dichlorotetrafluoroethane = 1 0.52 = 0.48 To calculate the number of grams of 1,1-dichloroethane, we use the definition of mole fraction. Mathematically, it is simpler to use the

x1,1-dichlorotetrafluoroethane definition:

n1,1-dichlorotetrafluoroethane = x1,1-dichlorotetrafluoroethane

100.0 g = 0.5851 mol 170.92 g mol1 0.5851 mol = = 0.48 m 0.5851 mol + 98.95 g mol1

m 0.5851 mol = 0.48 0.5851 mol + 1 98.95 g mol m 0.5851 mol (0.48 0.5851 mol) = 0.48 1 98.95 g mol 0.3042 mol = 0.004 851 mol g 1 m m = 63 g SM-219

8.85

Raoults Law applies to the vapor pressure of the mixture, so positive deviation means that the vapor pressure is higher than expected for an ideal solution. Negative deviation means that the vapor pressure is lower than expected for an ideal solution. Negative deviation will occur when the interactions between the different molecules are somewhat stronger than the interactions between molecules of the same kind (a) For methanol and ethanol, we expect the types of intermolecular attractions in the mixture to be similar to those in the component liquids, so that an ideal solution is predicted. (b) For HF and H 2 O , the possibility of intermolecular hydrogen bonding between water and HF would suggest that negative deviation would be observed, which is the case. HF and H 2 O form an azeotrope that boils at 111C , a temperature higher than the boiling point of either HF (19.4C) or water. (c) Because hexane is nonpolar and water is polar with hydrogen bonding, we would expect a mixture of these two to exhibit positive deviation (the interactions between the different molecules would be weaker than the intermolecular forces between like molecules). Hexane and water do form an azeotrope that boils at 61.6C, a temperature below the boiling point of either hexane or water.

8.87

* = ( 0.65 )(122.7 Torr ) = 80 Torr Pmethanol = xmethanol Pmethanol * = ( 0.35 )( 58.9 Torr ) = 21 Torr Pethanol = xethanol Pethanol

from the ideal gas law we know that n P, therefore: nmethanol Pmethanol 80 Torr xmethanol = = = = 0.79 nmethanol + nethanol Pmethanol + Pethanol 80 Torr + 21 Torr and xethanol = nethanol Pethanol 21 Torr = = = 0.21 nmethanol + nethanol Pmethanol + Pethanol 80 Torr + 21 Torr

8.89

(a) stronger;

(b) low; (c) high; (d) weaker; (e) weak, low; (f) SM-220

8.91

(a, b) Viscosity and surface tension decrease with increasing temperature; at high temperatures the molecules readily move away from their neighbors because of increased kinetic energy. (c) Evaporation rate and vapor pressure increase with increasing temperature because the kinetic energy of the molecules increase with temperature, and the molecules are more likely to escape into the gas phase.

8.93

If the external pressure is lowered, water boils at a lower temperature. The boiling temperature is the temperature at which the vapor pressure equals the external pressure. Vapor pressure increases with temperature. If the external pressure is reduced, the vapor pressure of the water will reach that value at a lower temperature; thus, lowering the external pressure lowers the boiling temperature.

8.95

(a) No. Solid helium will melt before converting to a gas at 5 K. phase change to monoclinic sulfur at 96C . form observed.

(b)

Yes. Raising the temperature of rhombic sulfur at 1 atm will result in a (c) Rhombic sulfur is the (d) At 100C and 1 atm, the monoclinic form is more

stable. (e) No. The phase diagram shows no area where solid diamond and gaseous carbon are adjacent.

25.0 Torr 100 = 78.5%; 31.83 Torr

8.97

(a)

is only 23.76 Torr, so some of the water vapor in the air would condense as dew or fog.

8.99

(a) At 30C, the vapor pressure of pure water = 31.83 Torr. According to Raoults law, P = xsolvent Ppure . To calculate the xsolvent: 0.50 m NaCl gives 0.50 moles Na+ and 0.50 moles Cl per kg solvent. The number of moles of solvent is 1000 kg 18.02 g mol1 = 55.49 mol. The total number of moles = 0.50 mol + 0.50 mol + 55.49 mol = 56.49 mol. SM-221

55.49 mol = 0.9823 56.49 mol P = xsolvent Ppure = 0.9823 31.83 Torr = 31.26 Torr xsolvent = (b) At 100C, Ppure = 760 Torr : P = xsolvent Ppure = 0.9823 760 Torr = 747 Torr At 0C,Ppure = 4.58 Torr; P = xsolvent Ppure = 0.9823 4.58 Torr=4.50 Torr

8.101 T = 77.19C 76.54C = 0.65 0.65 K

msolute M Tb = ikb m = ikb solute kg solvent

M solute =

= 76 g mol1

8.103 T = kf m, m =

or

T = kf

M solute =

(a) If masssolute appears greater, Msolute appears greater than actual molar mass, as masssolute occurs in the numerator above. Also, the T measured will be smaller because less solute will actually be dissolved. This has the same effect as increasing the apparent Msolute. (b) Because the true masssolvent = d V , if dsolvent is less than 1.00 g cm 3 , then the true masssolvent will be less than the assumed mass. Msolute is inversely proportional to masssolvent, so an artificially high masssolvent will lead to an artificially low Msolute. SM-222

(c) If true freezing point is higher than the recorded freezing point, true

T < assumed T , or assumed T > true T , and M solute appears less

than actual M solute , as T occurs in the denominator. (d) If not all solute dissolved, the true masssolute < assumed masssolute or assumed masssolute > true masssolute, and Msolute appears greater than the actual Msolute, as masssolute occurs in the numerator.

8.105 The water Coleridge referred to was seawater. The boards shrank due to

osmosis (a net movement of water from the cells of the wood to the saline water). You cant drink seawater: osmosis would cause a net flow of water from the cells of the body to the saline-enriched surround solution and the cells would die.

8.107 When a drop of aqueous solution containing Ca(HCO3)2 seeps through a

cave ceiling, it encounters a situation where the partial pressure of CO2 is reduced and the reaction Ca(HCO3)2(aq) CaCO2(s) + CO2(g) + H2O(l) occurs. The concentration of CO2 decreases as the CO2 escapes as a gas, with CaCO3 precipitating and forming a column that extends downward from the ceiling to form a stalacite. Stalagmite formation is similar, except the drops fall to the floor and the precipitate grows upward.

8.109 (a) The 5.22 cm or 52.2 mm rise for an aqueous solution must be

converted to Torr or mmHg in order to be expressed into consistent units. 52.2 mm 0.998 g cm 3 = 3.83 mmHg or 3.83 Torr 13.6 g cm 3

The molar mass can be calculated using the osmotic pressure equation:

= iRT molarity

Assume that the protein is a nonelectrolyte with i = 1 and that the amount of protein added does not significantly affect the volume of the solution.

SM-223

0.010 g M protein 3.83 Torr = 1 1 = 1 0.082 06 L atm K mol 293 K 0.010 L 760 Torr atm 1 1 0.082 06 L atm K 1 mol1 293 K 0.010 g 760 Torr atm 1 0.010 L 3.83 Torr

M protein =

(b) The freezing point can be calculated using the relationship Tf = ikf m Tf = ikf m 0.010 g 3 1 4.8 10 g mol = 1 1.86 K kg mol1 10 mL 1.00 g mL1 1000 g kg 1 = 3.9 104 K or 3.9 104 C The freezing point will be 0.00C 3.9 104C = 3.9 104C. (c) The freezing point change is so small that it cannot be measured accurately, so osmotic pressure would be the preferred method for measuring the molecular weight.

8.111 (a) The vapor pressure data can be used to obtain the concentration of the

solution in terms of mole fraction, which in turn can be converted to molarity and used to calculate the osmotic pressure. Because 80.1C is the boiling point of benzene, the vapor pressure of pure benzene at that temperature will be 760 Torr.

Psolution = xsolvent Ppure solvent

740 Torr = xsolvent 760 Torr xsolvent = 0.974 The mole fraction of solute is, therefore, 1 0.974 = 0.026 . This means that there will be 0.026 moles of solute and 0.974 moles of benzene. From this we can calculate the molarity: SM-224

molarity =

0.026 mol = 0.30 mol L1 1 0.974 mol benzene 78.11 g mol benzene 0.88 g mL1 1000 mL L1

(b) As in (a), the freezing point will be used to calculate the molality of the solution, which will be converted to molarity for the osmotic pressure calculation.

Tf = 5.5C 5.4C = 0.1C or 0.1 K Tf = i kf m 0.1 K = 1 5.12 K kg mol1 molality molality = 0.02 mol kg 1 A 0.02 mol kg 1 solution will contain 0.02 mol of solute and 1 kg of solvent. The volume of the solvent will be 1000 g 0.88 g mL1 = 1.1 103 mL or 1.1 L. The molar concentration will thus be

0.02 mol = 0.02 M. 1.1 L

(c) The height of the rise of the solution is inversely proportional to the density of that solution. Mercury with a density of 13.6 g cm 3 would produce a rise of 0.5 atm 760 mmHg atm 1 or 380 mmHg. For the benzene solution with a density of 0.88 g cm 3 , we would obtain 0.5 atm 760 mm 13.6 g cm 3 = 6 103 mm or 6 m 3 1 atm 0.88 g cm

naa 0.95 kg

SM-225

naa =

(1.86 K kg mol )

-1

(1.72 K )( 0.95 kg )

= 0.878 mol

Experimentally, the molar mass of acetic acid is, therefore: 50 g = 56.9 g mol-1 0.878 mol This experimental molar mass of acetic acid is less than the known molecular mass of the acid (60.0 g mol-1 ) indicating that the acid is dissociating in solution giving an i > 1.

(b) As in part (a) the experimental molar mass is first found: naa T f = 2.32 K = i k f m = ( 5.12 K kg mol-1 ) 0.95 kg where naa are the moles of acetic acid in solution.

Assuming i = 1: naa =

( 5.12 K kg mol )

-1

( 2.32 K )( 0.95 kg )

= 0.430 mol

Experimentally, the molar mass of acetic acid is, therefore: 50 g = 116 g mol-1 0.43 mol This experimental molar mass of acetic acid is significantlyhigher than the known molecular mass of the acid (60.0 g mol-1 ) indicating that the acid is dissociating in solution giving an i < 1. A van't Hoff factor less than 1 indicates that acetic acid is not completely dissolved in the benzene, or acetic acid molecules are agregating together in solution.

8.115 (a) The data in Appendix 2A can be used to calculate the change in

CH 3OH(l) CH 3OH(g)

H vap = H f (CH 3OH, g) H f (CH 3OH, l) = ( 200.66 kJ mol1 ) (238.86 kJ mol1 ) = 38.20 kJ mol1 S vap = S m (CH 3OH(g)) S m (CH 3OH(l)) = 239.81 J K 1 mol1 126.8 J K 1 mol1 = 113.0 J K 1 mol1

SM-226

G vap = RT ln P , where P is the vapor pressure of the solvent. Because G vap = H vap T S vap , this is the relationship to use to determine the

temperature dependence of ln P:

H vap T S vap = RT ln P

To create an equation specific to methanol, we can plug in the actual values of R, H vap , and S vap :

ln P = =

38 200 J mol1 1 113.0 J K 1 mol1 + 8.314 J K 1 mol1 T 8.314 J K 1 mol1 4595 K + 13.59 T

1 . This should result in a T

(b) The relationship to plot is ln P versus straight line whose slope is H vap R

S vap R

. The

pressure must be given in atm for this relationship, because atm is the standard state condition. (c) Because we have already determined the equation, it is easiest to calculate the vapor by inserting the value of 0.0C or 273.2 K :

ln P = 4595 K 4595 K + 13.59 = + 13.59 = 16.82 + 13.59 = 3.23 T 273.2 K

P = 0.040 atm or 30 Torr (d) As in (c) we can use the equation to find the point where the vapor pressure of methanol = 1 atm.

ln P = ln 1 = 0 = 4595 K + 13.59 T

T = 338.1 K

SM-227

8.117 The plot of the data is shown below. On this plot, the slope =

H vap R

S vap R

. Vapor pressure (Torr) V.P. (atm) 3.2 68 240 672 0.0042 0.089 0.316 0.884 ln P

y = 3358.714 x + 12.247

(b)

H vap R

= 3359

(c) S vap R = 12.25

(d) The normal boiling point will be the temperature at which the vapor pressure = 1 atm or at which the ln 1 = 0. This will occur when T 1 = 0.0036 or T = 2.7 102 K. This is most easily done by using an equation derived from H vap and S vap :

H vap 1 S vap + R T R 15 Torr 28 000 J mol1 1 100 J K 1 mol1 = + ln 760 Torr 8.314 J K 1 mol1 T 8.314 J K 1 mol1 ln P = T = 2.1 102 K

82.1

32.2 SM-228

C3H8 C4H10

96.8 152

The critical temperatures increase with increasing mass, showing the influence of the stronger London forces.

8.121 (a) If sufficient chloroform and acetone are available, the pressures in the

flasks will be the equilibrium vapor pressures at that temperature. We can calculate these amounts using the ideal gas equation:

195 Torr (1.00 L) = 1 760 Torr atm mchloroform 1 1 (0.08206 L atm K mol )(298 K) 1 119.37 g mol chloroform

mchloroform = 1.25 g

225 Torr (1.00 L) = 1 760 Torr atm macetone 1 1 (0.08206 L atm K mol )(298 K) 1 58.08 g mol acetone

macetone = 0.703 g In both cases, sufficient compound is available to achieve the vapor pressure; flask A will have a pressure of 195 Torr and flask B will have a pressure of 222 Torr. (b) When the stopcock is opened, some chloroform will move into flask B and acetone will move into flask A to restore the equilibrium vapor pressure. Additionally, however, some acetone vapor will dissolve in the liquid chloroform and vice versa. Ultimately the system will reach an equilibrium state in which the compositions of the liquid phases in both flasks are the same and the gas phase composition is uniform. The gas phase and liquid phase compositions will be established by Raoults law. It is conceptually most convenient for this calculation to start by putting all the material into one liquid phase. Such a solution would have the following composition: SM-229

acetone

35.0 g 58.08 g mol1 acetone = 35.0 g 35.0 g + 1 58.08 g mol acetone 119.37 g mol 1 chloroform 35.0 g 119.37 g mol 1 chloroform = or 1 acetone 35.0 g 35.0 g + 58.08 g mol1 acetone 119.37 g mol1 chloroform = 0.33

This gives the composition of the liquid phase. The composition of the gas phase will be determined from the pressures of the gases: Pacetone = acetone, liquid Pacetone = (0.67)(222 Torr) = 149 Torr Pchloroform = chloroform, liquid Pchloroform = (0.33)(195 Torr) = 64 Torr Pacetone Pacetone + Pchloroform

149 Torr = 0.70 149 Torr + 64 Torr chloroform, gas = 1 acetone, gas = 0.30

The gas phase composition will, therefore, be slightly richer in acetone than in chloroform. The total pressure in the flask will be 213 Torr. (c) The solution shows negative deviation from Raoults law. This means that the molecules of acetone and chloroform attract each other slightly more than molecules of the same kind. Under such circumstances, the vapor pressure is lower than expected from the ideal calculation. This will give rise to a high-boiling azeotrope. The gas phase composition will also be slightly different from that calculated from the ideal state, but whether acetone or chloroform would be richer in the gas phase depends on which side of the azeotrope the composition lies. Because we are not given the composition of the azeotrope, we cannot state which way the values will vary.

8.123 (a) The vapor pressure above the sucrose solution will be lower than the

vapor pressure of the pure solvent. This results in an imbalance in the SM-230

system that causes pure ethanol to condense into the sucrose solution. As this happens, the sucrose solution becomes more dilute and its vapor pressure would approach that of pure ethanol if there were sufficient pure ethanol. In this case, however, the process will stop once all the pure ethanol has transferred to the solution. This will result in a solution that has 1 2 the original concentration, or 7.5 m. (b) The vapor pressure of this solution will be given by P = ethanol Pethanol = ethanol 60 Torr We need to convert the molality of the solution to mole fraction. A 7.5 m solution will contain 7.5 mol sucrose for 1.0 kg solvent. The molar mass of ethanol is 46.07 g mol1 , so 1.0 kg represents 22 mol of ethanol. The mole fraction of ethanol will be given by

ethanol =

8.125 The vapor pressure is more sensitive if H vap is small. The fact that

H vap is small indicates that it takes little energy to volatilize the sample,

which means that the intermolecular forces are weaker. Hence we expect the vapor pressure to be more dramatically affected by small changes in temperature.

8.127 (a) = iRT molarity

-1

-1

0.500 L

X = 13 800 g mol = molar mass of the polymer (b) The molecular mass of CH3CHCH2 is 42.08 g mol-1. Dividing the molar mass of the polymer by the molar mass of the

SM-231

monomer, 13800 g mol-1 / 42.08 g mol-1 = 328 , indicates that there are approximately 328 monomers in the average polymer. (c) ( 308 pm monomer -1 ) (328 monomers) = 101000 pm or 101 nm

8.129 The initial information tells us that the detector is more responsive to A

than to B. Under these conditions, the response is 5.44 cm 2 0.52 mgA = 11 cm 2 mg 1 A whereas the response for B is 8.72 cm 2 2.30 mg = 3.79 cm 2 mg 1 B. The detector is thus 11 cm 2 mg 1 3.79 cm 2 mg 1 = 2.9 times more sensitive for A than B. Because the conditions are different for determining the unknown amount of A present, we cannot use the area ratios directly to determine the quantity of A. Instead, we use the standard B as a reference. (X = mg A) 3.52 cm 2 7.58 cm 2 = 2.9 X 2.00 mg (B) 3.52 cm 2 2.00 mg 2.9 7.58 cm 2 X = 0.32 mg A X=

8.131 = iRT molarity Assuming i = 1

7.7 atm = ( 0.0821 L atm K -1 mol-1 ) ( 310 K ) ( M ) M = 0.303 mol L-1 If 0.500 L of solution is needed:

-1

8.133 First, calculate the weight % of acetic acid in a solution with xacetic acid =

0.15:

SM-232

If you have 1 mol total of a solution with xacetic acid = 0.15 and xH2O = 0.85, you would have 0.15 mol of acetic acid (60.053 g mol-1 ) in 0.85 mol of H 2O (18.015 g mol-1 ). The weight % of acetic acid in such a solution is:

( 0.15 mol ) (60.053 g mol-1 ) = 9.01 g of acetic acid ( 0.85 mol ) (18.015 g mol-1 ) = 15.3 g of H 2 O

9.01 g (100% ) = 37.0% acetic acid by weight 9.01 g + 15.3 g If a solution with xacetic acid = 0.15 is 37.0% acetic acid by weight, 30 g of such a solution will contain:

11.1 g = 0.185 mol of acetic acid 60.053 g mol-1 given that acetic acid is a monoprotic acid which will react in a 1:1 fashion with NaOH, 0.185 mol of NaOH will completely react with 0.185 mol of acetic acid. The volume of a 0.010 M solution of NaOH needed to completely consume the acetic acid 0.185 mol is: = 18.5 L 0.010 mol L-1

(0.262)(100 g) = 26.2 g O 1.638 mol O (0.0710)(100 g) = 7.10 g H 7.044 mol H (0.0760)(100 g) = 7.60 g N 0.5424 mol N Dividing by 0.5424 mol and rounding to the nearest whole number we find the C:O:H:N ratio to be 9:3:13:1, giving an empirical formula of C9 H13O3 N

(b) Molar mass may be found using the freezing point depression:

SM-233

T f = i k f m, assuming i = 1: 0.64 g -1 X g mol 0.50 K = ( 5.12 K kg mol-1 ) 0.0360 kg X = 182 g mol-1 The molar mass of the compound will be an integral multiple of the molar mass of the empirical formula: n((9 12.011 g mol-1 ) + (3 16.00 g mol-1 ) + (13 1.0079 g mol-1 ) + (14.01 g mol-1 )) = 182 g mol-1 n =1 Therefore, the molecular formula is C9*n H13*n O3*n N n = C9 H13 O3 N

8.137 The non-polar chains of both the surfactant and pentanol will interact to

form a hydrophobic region with the heads of the two molecules pointing away from this region towards the aqueous solution. To prevent the heads of the shorter pentanol molecules from winding up in the hydrophobic region, the layered structure might be comprised of a water region, a surfactant layer (heads pointing toward the water) a pentanol layer (with tails pointing toward the hydrophobic tails of the surfactant) and back to an aqueous region.

SM-234

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