Chapter 14

Solutions and Their Behavior

Chapter 14 Solutions and Their Behavior

INSTRUCTOR'S NOTES We generally cover all the topics in this chapter (except for Section 14.4) in 2-3 lectures. Students are able to deal with straightforward problems and discuss solution phenomena with little difficulty. SUGGESTED DEMONSTRATIONS 1. The Solution Process Several demonstrations in Volume 1 of Chemical Demonstrations by Shakhashiri are suitable. Suggestions include Chemical Cold Packs, Crystallization from Supersaturated Solutions of Sodium Acetate, Chemical Hot Packs, and Endothermic Reactions of Hydrated Barium Chloride and Ammonium Salts. A demonstration of Henry's Law, Effect of Temperature and Pressure on the Solubility of Gases in Liquids, is contained in Volume 3 of the Chemical Demonstrations series. Also in Volume 3 are: Getting Colder: Freezing-Point Depression, Getting Hotter: Boiling Point Elevation by Nonvolatile Solutes, Osmosis Through the Membrane of an Egg, and Osmotic Pressure of a Sugar Solution. Several of the photos in the chapter represent demonstrations we do in class. For example, Figure 14.1 shows the difference between molality and molarity, and Figure 14.5, showing the preferential solubility of iodine in CCl4, is easy to do. One of our favorites is the frozen solution in Figure 14.13. We place an indicator in water and then allow the solution to freeze slowly in the freezer of a lab refrigerator. The result clearly shows that the solute concentrates in the solution and that the solid is pure solvent. 2. Additional demonstrations Mundell, D. W. Heat of Solution and Colligative Properties: An Illustration of Enthalpy and Entropy, Journal of Chemical Education 1990, 67, 426. Levy, J. B.; Hornack, F. M.; Levy, M. A. Simple Determination of Henry's Law Constant for Carbon Dioxide, Journal of Chemical Education 1987, 64, 260.

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Chapter 14

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Solutions to Study Questions

14.1 False. Colligative properties depend only on the number of solute particles per solvent molecule and not on the identity of the solute. 14.2 Raoults law (change in vapor pressure) Boiling point elevation Freezing point depression Osmotic pressure 14.3 Psolv = XsolvPsolv T bp = K bpmsolute T fp = K fpmsolute = cRT

molality: amount of solute per kilogram of solvent molarity: amount of solute per liter of solution

14.4 14.5

temperature, pressure, and the intermolecular forces between the gas and water molecules When the solids dissolve in water, CaCl2 produces three ions per mole of solute while NaCl produces only two moles of ions per mole of solute. The solution with a higher concentration of ions (particles) will have a lower freezing point.

14.6

The solution inside the cucumber has a higher solvent concentration than the concentrated salt solution. The solvent molecules flow out of the cucumber, and the cucumber shrivels.

14.7

Solubility is the concentration of solute in equilibrium with undissolved solute in a saturated solution. Add a known quantity of NaCl to 100 mL of water, making sure that enough NaCl is added so that some of the salt does not dissolve. Filter the solution and weight the undissolved salt. The difference between the original mass and the undissolved salt is the solubility of NaCl per 100 mL of water.

14.8

Using KF as an example: KF(s) K+(g) + F(g) K+(g) + F(g) K+(aq) + F (aq) KF(s) K+(aq) + F (aq) H = lattice energy H = enthalpy of solvation of the ions H = heat of solution

14.9

At the particulate level, Na+ and Cl ions are still leaving the solid state and entering solution. Concurrently, solid NaCl is forming from Na+ and Cl ions in solution.

14.10

Make a solution from a known quantity of solute (with unknown molar mass) and solvent. Measure the freezing point depression of the solution and use this to calculate the molality of the solution. From this determine the amount of solute (mol) in the solution. The ratio of the mass and amount of solute gives the molar mass.

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Chapter 14

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14.11

Two or more nonpolar liquids (such as octane, C8H18, and carbon tetrachloride, CCl 4) frequently are miscible, just as are two or more polar liquids (such as water, H2O, and ethanol, C2H5OH).

14.12

(a) ionic solid, soluble in water (b) polar, soluble in water (c) nonpolar, soluble in benzene (d) ionic solid, soluble in water (e) nonpolar, soluble in benzene

14.13

In a true solution, no settling of the solute is observed and the solute particles are ions or relatively small molecules. In a suspension, solute particles are visible and gradually settle to the bottom of the container. A colloidal dispersion is a state intermediate between a solution and a suspension.

14.14

A sol is a dispersion of a solid substance in a fluid medium (milk of magnesia) and a gel is a dispersion that has a structure that prevents it from being mobile (cheese).

14.15

The nonpolar oil molecules interact with the nonpolar hydrocarbon tails of the soap molecules, leaving the polar heads of the soap to interact with surrounding water molecules. The oil and water then mix. If the oily material on a piece of clothing or a dish also contains some dirt particles, the dirt can now be washed away.

14.16

1 mol C4 H 6O 4 = 0.0217 mol C H 6O 4 4 118.1 g 1 cm3 1.00 g 1 mol H2O 500. mL = 27.7 mol H2O 1 mL 1 cm3 18.02 g amount of solute 0.0217 mol C4 H 6O4 M = = = 0.0434 M volume of solution 0.500 L amount of solute 0.0217 mol C4 H 6O 4 10 3 g m= = = 0.0434 m kg of solvent 500. g 1 kg 0.0217 mol X acid = = 0.000781 0.0217 mol + 27.7 mol 2.56 g Weight % = 100% = 0.509% 2.56 g + 500. g 2.56 g 1 mol = 0.296 mol C H 16O 10 152.2 g 0.785 g 1 mol 425 mL C2 H 5OH = 7.24 mol C H 5OH 2 1 mL 46.07 g amount of solute 0.296 mol C H16O 10 M = = = 0.696 M volume of solution 0.425 L C2H 5OH amount of solute 0.296 mol C10H 16O 1 mL 10 3 g m= = = 0.886 m kg of solvent 425 mL C2H 5OH 0.785 g 1 kg 45.0 g C10H 16O

14.17

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0.296 mol = 0.0392 0.296 mol + 7.24 mol 45.0 g Weight % = 100% = 11.9% 0.785 g 45.0 g + 425 mL 1 mL X camphor = 14.18 Compound NaI C 2H5OH C 12H22O11 Molality 0.15 1.1 0.15 Weight percent 2.2 5.0 4.9 Mole fraction 0.0027 0.020 0.0027

NaI: 0.15 mol NaI dissolved in 1.0 kg H2O 150. g 1 mol 0.15 mol = 23 g NaI 1.0 10 3 g = 56 mol H2O 1 mol 18.0 g 23 g Weight % = 100% = 2.2% 23 g + 1.0 10 3 g 0.15 mol X NaI = = 0.0027 0.15 mol + 56 mol C 2H5OH: 5.0 g C2H5OH dissolved in 95.0 g H2O 1 mol 1 mol 5.0 g = 0.11 mol C2H 5OH 95.0 g = 5.27 mol H2O 46.1 g 18.02 g amount of solute 0.11 mol C2 H 5OH m= = = 1.1 m kg of solvent 0.0950 kg H2O 0.11 mol X C H OH = = 0.020 0.11 mol + 5.27 mol
2 5

C 12H22O11: 0.15 mol C12H22O11 dissolved in 1.0 kg H2O 342 g 0.15 mol = 51.3 g C12H 22O11 1 mol 51.3 g Weight % = 100% = 4.9% 51.3 g + 1.0 10 3 g 0.15 mol XC H O = = 0.0027 0.15 mol + 56 mol
12 22 11

1.0 10 3 g

1 mol = 56 mol H2O 18.0 g

14.19

Compound KNO3 CH3CO2H HOC2H4OH

Molality 1.10 0.0183 3.54

Weight percent 10.0 0.110 18.0

Mole fraction 0.0194 3.30 10 4 0.0599

KNO3: 10.0 g KNO3 dissolved in 90.0 g H2O 1 mol 1 mol 10.0 g = 0.0989 mol KNO3 90.0 g = 4.99 mol H2O 101.1 g 18.02 g amount of solute 0.0989 mol KNO3 m= = = 1.10 m kg of solvent 0.0900 kg H2O

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Chapter 14

Solutions and Their Behavior

X KNO =
3

0.0989 mol = 0.0194 0.0989 mol + 4.99 mol

CH3CO2H: 0.0183 mol CH3CO2H dissolved in 1.00 kg H2O 60.05 g 1 mol 0.0183 mol = 1.10 g CH3CO2 H 1.00 10 3 g = 55.5 mol H2O 1 mol 18.02 g 1.10 g Weight % = 100% = 0.110% 1.10 g + 1.00 10 3 g 0.0183 mol X CH CO H = = 3.30 10 4 0.0183 mol + 55.5 mol
3 2

HOCH2CH2OH: 18.0 g HOCH2CH2OH dissolved in 82.0 g H2O 1 mol 1 mol 18.0 g = 0.290 mol HOCH2CH 2OH 82.0 g = 4.55 mol H2O 62.07 g 18.02 g amount of solute 0.290 mol HOCH2CH 2OH m= = = 3.54 m kg of solvent 0.0820 kg H2O 0.290 mol X HOCH CH OH = = 0.0599 0.290 mol + 4.55 mol
2 2

14.20

0.200 mol Na2CO3 106.0 g 125 g H 2O = 2.65 g Na2CO3 1 kg H2O 1 mol Na 2CO3 103 g/1 kg 0.200 mol Na2CO3 X Na CO = = 0.00359 3 1 mol H2O 0.200 mol Na 2CO3 + 10 g 18.02 g
2 3

14.21

0.0512 mol NaNO3 85.00 g 500. g H2O = 2.18 g NaNO3 1 kg H 2O 1 mol NaNO 3 10 3 g/1 kg 0.0512 mol NaNO 3 X NaNO = = 9.22 10 4 3 1 mol H2O 0.0512 mol NaNO 3 + 10 g 18.02 g
3

14.22

x mol C3H 5 (OH) 3 1 mol H2O x mol C3 H 5 (OH) 3 + 425 g 18.02 g 92.1 g 2.4 mol C3 H 5(OH) 3 = 220 g C3H 5 (OH) 3 1 mol 2.4 mol C3H 5 (OH) 3 m= = 5.7 m 0.425 kg H2O 0.093 = 0.125 =

x = 2.4 mol C3H 5 (OH) 3

14.23

x mol HOCH2CH2OH x = 7.57 mol HOCH2CH2OH 1 mol x mol HOCH2CH2OH + 955 g H 2O 18.02 g 62.07 g 7.57 mol HOCH2CH 2OH = 470. g HOCH2CH2OH 1 mol HOCH2CH2OH 7.57 mol HOCH2CH2OH m= = 7.93 m 0.955 kg H2O

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14.24

1000 mL 1.18 g = 1180 g solution 1L mL 12.0 mol HCl 36.46 g Mass of HCl = 1 L = 438 g HCl 1L 1 mol HCl Mass of H 2O = 1180 g 438 g = 742 g H2O 12.0 mol HCl m= = 16.2 m 0.742 kg H2O 438 g HCl (b) Weight % = 100% = 37.1% 1180 g solution (a) Mass of solution = 1 L 95.0 g H2SO4 1 mol = 0.969 mol H2SO4 98.08 g 0.969 mol H2SO4 m= = 194 m 0.0050 kg H 2O 1 cm3 1 mL 1L 100.0 g solution 3 = 0.0543 L solution 3 1.84 g 1 cm 10 mL 0.969 mol H2SO4 M = = 17.8 M 0.0543 L solution 0.18g Li+ 1 mol 10 3 g = 2.6 10 6 m 1 10 6 g H 2O 6.941 g 1 kg 1 ppm = 1 g solute/106 g solvent, so 1 ppb = 1 g solute/109 g solvent 28 g Ag 1 mol Ag 1000 g (a) = 2.6 10 7 m 9 108 g 1 kg 1 10 g H 2O 1 10 9 g H 2O 1L (b) 1.0 10 2 g Ag = 3.6 10 6 L H 2O 28 g Ag 1000 g (b) C 6H6 and CCl4 (c) H2O and CH 3CO2H both are nonpolar molecules both are polar molecules

14.25

14.26

14.27

14.28

14.29

Acetone is a polar molecule, so the strong dipoledipole interactions between acetone and water molecules lead to a high solubility of acetone in water.

14.30

LiCl(s) LiCl(aq) Hsoln = Hf [LiCl(aq)] Hf [LiCl(s)] = 445.6 kJ/mol (408.6 kJ/mol) = 37.0 kJ/mol The enthalpy of solution of LiCl is exothermic while that of NaCl is endothermic (+3.9 kJ/mol).

14.31

NaClO4(s) NaClO4(aq) Hsoln = Hf [NaClO4(aq)] Hf [NaClO4(s)] = 369.5 kJ/mol (382.9 kJ/mol) = 13.4 kJ/mol

14.32

(c) Raise the temperature of the solution and add some NaCl

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14.33

As temperature increases the solubility of Li2SO4 decreases; additional solid should appear in the beaker. As temperature increases the solubility of LiCl increases; additional solid should dissolve.

14.34

(a) LiCl (b) Mg(NO3)2 (c) NiCl 2

Lithium ions are smaller than cesium ions Magnesium has a larger positive charge (+2) than sodium (+1) Nickel has a larger positive charge (+2) than rubidium (+1) and it is a smaller ion

14.35

Mg2+ is most strongly hydrated because of its small size and large positive charge. Cs+ is least strongly hydrated because of its large size and smaller positive charge.

14.36

1.66 10 6 M 40 mm Hg = 7 10 5 M mm Hg 7 10 5 mol O 2 32 g = 0.002 g O2 /L 1L 1 mol SO = k HPO =

2 2

14.37

Since the solubility of a gas generally decreases with increasing temperature, (a) 8.80 10 7 M/mm Hg is the only reasonable choice because it is less than the value of the constant at 25 C.

14.38

PCO =
2

SCO kH

0.0506 M = 1130 mm Hg (1.49 atm) 4.48 10 5 M/mm Hg

14.39

PH2 = Ptotal PH2 O = 760.0 mm Hg 23.8 mm Hg = 736.2 mm Hg 1.07 10 6 M SH = 736.2 mm Hg = 7.88 10 4 M mm Hg

2

7.88 10 4 mol H2 1L 2.016 g = 1.59 10 6 g/mL 1L 1000 mL 1 mol H2 14.40 35.0 g XHO
2

PH O
2 2

1 mol = 0.564 mol HOCH2CH 2OH 62.07 g 27.75 mol = = 0.980 27.75 mol + 0.564 mol = X H OP H O
2 2

500.0 g

1 mol = 27.75 mol H2O 18.02 g

PH O = (0.980)(35.7 mm Hg) = 35.0 mm Hg 14.41 9.00 g XHO

2

PH O
2 2

1 mol = 0.150 mol (NH2) 2 CO 60.06 g 0.555 mol = = 0.787 0.555 mol + 0.150 mol = X H OP H O
2 2

10.0 mL

1.00 g 1 mol = 0.555 mol H2O 1mL 18.02 g

PH O = (0.787)(22.4 mm Hg) = 17.6 mm Hg

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14.42

PH O 457 mm Hg 1 mol = = 0.869 2.00 10 3 g = 111 mol H2O P H O 525.8 mm Hg 18.02 g 111 mol H2O X H O = 0.869 = 111 mol H2O + x mol HOCH2CH2OH x = 16.7 mol HOCH2CH 2OH 62.07 g 16.7 mol HOCH2CH2OH = 1040 g HOCH2CH2OH 1 mol XHO =
2 2 2 2

14.43

105 g X CCl PCCl

4

1 mol 1mol = 0.414 mol I2 325 g = 2.11 mol CCl4 253.8 g 153.8 g 2.11 mol = = 0.836 2.11 mol + 0.414 mol = X CCl PCCl = (0.836)(531 mm Hg) = 444 mm Hg
4 4

14.44

0.200 mol solute T bp = (2.53 C/m) = 4.05 C 0.125 kg benzene T bp = 80.10 C + 4.05 C = 84.15 C 15.0 g 1 mol urea 60.06 g 0.500 kg H2O

14.45

murea =

= 0.500 m

T bp = (0.5121 C/m)(0.500 m) = 0.256 C T bp = 100.00 C + 0.256 C = 100.26 C 0.515 g 14.46 mC H =

12 10

1 mol C12 H10 154.2 g = 0.223 m 0.0150 kg CHCl3

T bp = (3.63 C/m)(0.223 m) = 0.808 C T bp = 61.70 C + 0.808 C = 62.51 C 0.755 g 14.47 mcaffeine = 1 mol caffeine 194.2 g = 0.0407 m 0.0956 kg benzene

T bp = (2.53 C/m)(0.0407 m) = 0.103 C T bp = 80.10 C + 0.103 C = 80.20 C 14.48 T bp = 80.51 C 80.10 C = 0.41 C Tbp 0.41 C mC H = = = 0.16 m K bp 2.53 C/m
14 10

0.16 mol C14 H10 178 g 0.0500 kg benzene = 1.4 g C H 10 14 1kg benzene 1 mol C14 H 10

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14.49

T bp = 104.4 C 100.0 C = 4.4 C Tbp 4.4 C msolute = = = 8.6 m K bp 0.5121 C/m 8.6 mol C3 H 5(OH) 3 0.735 kg H2O = 6.3 mol C H 5 (OH) 3 3 1 kg H 2O 92.1 g 6.3 mol C3 H 5(OH) 3 = 580 g C3 H 5 (OH) 3 1 mol 6.3 mol C3H 5 (OH) 3 X glycerol = = 0.13 1 mol H2O 6.3 mol C3H 5 (OH) 3 + 735 g 18.02 g

14.50

(a) methanol =

Tfp 16.0 C = = 8.60 m K fp 1.86 C/m

(b) 8.60mol C2 H 5OH

46.07 g = 396 g C2 H 5OH 1 mol 396 g C2 H 5OH Weight % = 100% = 28.4% 396 g C2 H 5OH + 1.00 10 3 g H 2O Tfp 15.0 C = = 8.06 m K fp 1.86 C/m

14.51

msolute =

8.06 mol HOCH2CH 2OH 62.07 g 5.0 kg H2O = 2500 g HOCH2CH 2OH 1 kg H 2O 1 mol 15.0 g 14.52 msucrose = 1 mol sucrose 342.3 g = 0.195 m 0.225 kg H2O

T fp = (1.86 C/m)(0.195 m) = 0.362 C T fp = 0.362 C 14.53 11 g C2H5OH 1mol = 0.24 mol C2H5OH 46.1 g mC H OH =
2 5

0.24 mol C2H 5OH = 2.7 m 0.089 kg H2O

T fp = (1.86 C/m)(2.7 m) = 5.0 C T fp = 5.0 C 14.54 The solution will begin freeze if it is chilled to 20 C.

T bp = 80.26 C 80.10 C = 0.16 C Tbp 0.16 C msolute = = = 0.063 m K bp 2.53 C/m 0.063 mol solute 0.01112 kg benzene = 7.0 10 4 mol solute 1 kg benzene 0.255 g = 360 g/mol 7.0 10 4 mol 360 g/mol = 2 The molecular formula is (C10H8Fe)2 or C 20H16Fe2 184 g/mol

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14.55

T bp = 62.22 C 61.70 C = 0.52 C Tbp 0.52 C mBHA = = = 0.14 m K bp 3.63 C/m 0.14 mol BHA 0.0250 kg CHCl = 0.0035 mol BHA 3 1 kg CHCl3 0.640 g BHA = 180 g/mol 0.0035 mol BHA

14.56

= 61.82 C 61.70 C = 0.12 C T bp 0.12 C mbenzyl acetate = = = 0.033 m K bp 3.63 C/m

bp

0.033 mol benzyl acetate 0.0250 kg CHCl = 8.3 10 4 mol benzyl acetate 3 1 kg CHCl3 0.125 g benzyl acetate = 150 g/mol 8.3 10 4 mol benzyl acetate 14.57 T bp = 80.34 C 80.10 C = 0.24 C Tbp 0.24 C manthracene = = = 0.095 m K bp 2.53 C/m 0.095 mol anthracene 0.0300 kg benzene = 0.0028 mol anthracene 1 kg benzene 0.500 g anthracene = 180 g/mol 0.0028 mol anthracene 180 g/mol = 2 The molecular formula is (C7H5)2 or C 14H10 89 g/mol 14.58 msolute = Tfp 0.040 C = = 0.022 m K fp 1.86 C/m

0.022mol solute 0.0500 kg H2O = 0.0011 mol solute 1 kg H 2O 0.180 g solute = 170 g/mol 0.0011 mol solute 14.59 msolute = Tfp 0.197 C = = 0.106 m K fp 1.86 C/m

0.106 mol aluminon 0.0500 kg H2O = 0.00530 mol aluminon 1 kg H 2O 2.50 g aluminon = 472 g/mol 0.00530 mol aluminon

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Chapter 14

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14.60

T fp = 69.40 C 70.03 C = 0.63 C Tfp 0.63 C mnaphthalene = = = 0.079 m K fp 8.00 C/m 0.079 mol naphthalene 0.0100 kg biphenyl = 7.9 10 4 mol naphthalene 1 kg biphenyl 0.100g naphthalene = 130 g/mol 7.9 10 4 mol naphthalene

14.61

mphenylcarbinol =

Tfp 0.36 C = = 0.19 m K fp 1.86 C/m

0.19 mol phenylcarbinol 0.0250 kg H2O = 0.048 mol phenylcarbinol 1 kg H 2O 0.52 g phenylcarbinol = 110 g/mol 0.048 mol phenylcarbinol 52.5 g 14.62 mLiF = 1 mol LiF 25.94 g = 6.61 m 0.306kg H 2O

T fp = (1.86 C/m)(6.61 m)(2) = 24.6 C T fp = 24.6 C 14.63 mNaCl = tfp 10. C = = 2.9 m K fp i (1.86 C/m)(1.85)

2.9mol NaCl 58.5 g 3.0 kg H2O = 510 g NaCl 1 kg H 2O 1 mol 14.64 solute (a) sugar (b) NaCl (c) CaCl 2 (d) Na2SO4 solution concentration 0.1 m 0.1 m 0.08 m 0.04 m particle concentration (0.1 1) = 0.1 m (0.1 2) = 0.2 m (0.08 3) = 0.24 m (0.04 3) = 0.12 m

Freezing point decreases as the particle concentration increases: 0.1 m sugar > 0.04 m Na2SO4 > 0.1 m NaCl > 0.08 m CaCl 2

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14.65

solute (a) ethylene glycol (b) K2SO4 (c) MgCl 2 (d) KBr

solution concentration 0.20 m 0.12 m 0.10 m 0.12 m

particle concentration (0.20 1) = 0.20 m (0.12 3) = 0.36 m (0.10 3) = 0.30 m (0.12 2) = 0.24 m

Freezing point decreases as the particle concentration increases: 0.20 m ethylene glycol > 0.12 m KBr > 0.10 m MgCl2 > 0.12 m K2SO4 14.66 3.00g C 9H 11NO 2
9

1 mol = 0.0182 mol C9H 11NO 2 165.2 g

11NO2

mC H
9

11NO 2

0.0182 mol C9H 11NO 2 = 0.187 m 0.09700kg H 2O

(a) Tfp = K fp m C H

= (1.86 C/m)(0.187 m) = 0.348 C

T fp = 0.348 C (b) Tbp = K bp m C H

9

11NO2

= (0.5121 C/m)(0.187 m) = 0.0959 C

T fp = 100.0959 C 0.0182 mol (c) = cRT = (0.082057 L atm/K mol)(298 K) = 4.58 atm 0.09700 L The osmotic pressure is large and can be measured with the least experimental error. 14.67 Concentration of ions in solution = (0.16 M)(1.9) = 0.30 M = cRT = (0.30 mol/L)(0.082057 L atm/K mol)(310. K) = 7.7 atm 1 atm 3.1 mm Hg 760 mm Hg(1.00 L) V n= = = 1.7 10 4 mol bovine insulin RT (0.082057 L atm/K mol)(298 K) 1.00 g = 6.0 10 3 g/mol 4 1.7 10 mol Concentration of ions in solution = (0.0120 M)(1.94) = 0.0233 M = cRT = (0.0233 mol/L)(0.08257 L atm/K mol)(273 K) = 0.522 atm 14.70 (a) BaCl 2(aq) + Na2SO4(aq) BaSO 4(s) + 2 NaCl(aq) (b) Initially the BaSO4 particles form a colloidal suspension. (c) Over time the particles of BaSO 4(s) grow and precipitate. 14.71 diameter = 1.0 10 2 nm, radius = 50. nm (a) V = 4/3 r3 = 4/3 (50. nm)3 = 5.2 10 5 nm 3 A = 4 r2 = 4 (50. nm)2 = 3.1 10 4 nm 2

14.68

14.69

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3

107 nm 1 sphere 15 (b) 1.0 cm = 1.9 10 spheres 5.2 10 5 nm3 1 cm

3

1.9 10

15

3.1 10 4 nm2 1 m 2 spheres 9 = 60. m 1 sphere 10 nm

2

14.72

Li2SO4 should have the more exothermic heat of hydration because the lithium ion is smaller than the cesium ion.

14.73

(a) The 0.10 m Na2SO4 solution has a higher particle concentration (0.30 m) so it should have the higher boiling point. (b) The 0.30 m NH4NO3 solution has a lower particle concentration (0.60 m) so it should have the higher water vapor pressure.

14.74

solute (a) HOCH2CH2OH (b) sugar (c) KBr (d) Na2SO4

solution concentration 0.35 m 0.50 m 0.20 m 0.20 m

particle concentration (0.35 1) = 0.35 m (0.50 1) = 0.50 m (0.20 2) = 0.40 m (0.20 3) = 0.60 m

(i) Vapor pressure increases as the particle concentration decreases: 0.20 m Na2SO4 < 0.50 m sugar < 0.20 m KBr < 0.35 m HOCH2CH2OH (ii) Boiling point increases as the particle concentration increases: 0.35 m HOCH2CH2OH < 0.20 m KBr < 0.50 m sugar < 0.20 m Na2SO4 14.75 1130 g NaCl 100% = 13.5% 1130 g NaCl + 7250 g H2O 1 mol 1 mol (b) 1130g NaCl = 19.3 mol NaCl 7250 g H 2O = 402 mol H2O 58.44 g 18.02 g 19.3 mol NaCl X NaCl = = 0.0459 19.3 mol NaCl + 402 mol H2O 19.3 mol NaCl (c) mNaCl = = 2.67 m 7.25 kg H2O (a) Weight % = 53.0 g DMG (a) X DMG (b) mDMG
2 5

14.76

1 mol 1 mol = 0.457 mol DMG 525 g C2H 5OH = 11.4 mol C H 5OH 2 116.1 g 46.07 g 0.457 mol DMG = = 0.0385 0.457 mol DMG + 11.4 mol C2H 5OH 0.457 mol DMG = = 0.870 m 0.525kg C2 H 5OH
2 5 2 5

(c) PC H OH = X C H OH P C H OH = (1 0.0386)(760 mm Hg) = 731 mm Hg

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(d) Tbp = K bp mC H OH = (1.22 C/m)(0.870 m) = 1.06 C

2 5

T bp = 78.4 C + 1.06 C = 79.5 C 14.77 40.00 g 1 mol = 428 g NaOH 1 10 3 g H 2O = 55.5 mol H2O 1 mol 18.02 g 1 cm3 1 mL 1L (428 g + 1000 g) = 1.07 L solution 1.33 g 1 cm3 10 3 mL 10.7 mol NaOH (a) X NaOH = = 0.162 10.7 mol NaOH + 55.5 mol H2O 428 g NaOH (b) Weight % = 100% = 30.0% 428 g NaOH + 1000 g H 2O 10.7 mol NaOH (c) MNaOH = = 9.97 M 1.07 L solution 10.7 mol NaOH 14.8 mol NH 3 17.03 g = 252 g NH 3 1 mol 1000 mL solution 0.90 g = 9.0 10 2 g = 0.90 kg 1 mL 1 mol 650 g H2O = 36 mol H2O 18.0 g

14.78

9.0 10 2 g solution 252 g NH3 = 650 g H2O 14.8 mol NH3 = 23 m 0.65 kg 14.8 mol NH3 X NH = = 0.29 14.8 mol NH 3 + 36 mol H2O 252 g NH 3 Weight % = 100% = 28% 9.0 10 2 g solution m=
3

14.79

1 mol Ca(NO3 ) 2 164.1 g mCa(NO ) = = 0.016 m 0.75 kg H 2O 0.016 mol Ca(NO3) 2 3 mol ions mions = = 0.049 m 1kg H 2O 1 mol Ca(NO 3 ) 2 2.00 g
3 2

14.80

Na2SO4(s) 2 Na +(aq) + SO 42(aq) 0.100 mol ions 0.125 kg H2O = 0.0125 mol ions 1 kg H 2O 1 mol Na 2SO4 142.0 g 0.0125 mol ions 3 mol ions 1 mol Na 2SO4 solute (i) HOCH2CH2OH (ii) CaCl 2 (iii) KBr (iv) Na2SO4

= 0.592 g Na 2SO4

14.81

solution concentration 0.20 m 0.10 m 0.12 m 0.12 m

particle concentration (0.20 1) = 0.20 m (0.10 3) = 0.30 m (0.12 2) = 0.24 m (0.12 3) = 0.36 m

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(a) 0.12 m Na2SO4 (b) 0.12 m Na2SO4 (c) 0.20 m HOCH2CH2OH 14.82

Boiling point increases as the particle concentration increases Freezing point decreases as the particle concentration increases Vapor pressure increases as particle concentration decreases

(a) 0.20 m KBr (higher particle concentration, 0.40 m) (b) 0.10 m Na2CO3 (higher particle concentration, 0.30 m) 39.1 g 1mol NaCl 58.44 g = 6.69 m 0.100 kg H2O

14.83

mNaCl =

T bp = K bpmNaCl i = (0.5121 C/m)(6.69 m)(1.85) = 6.34 C T bp = 100.00 C + 6.34 C = 106.34 C 35.0 g 14.84 mCaCl =
2

1mol CaCl2 111.0 g = 2.10 m 0.150 kg H2O

2

Tfp = K fp m CaCl i = (1.86 C/m)(2.10 m)(2.7) = 10.6 C T fp = 10.6 C 14.85 T bp = 61.82 C 61.70 C = 0.12 C Tbp 0.12 C msolute = = = 0.033 m K bp 3.63 C/m 0.033 mol solute 0.0250 kg CHCl = 8.3 10 4 mol solute 3 1 kg CHCl3 0.135 g solute = 160 g/mol 8.3 10 4 mol solute 160 g/mol = 2 The molecular formula is (C5H6O)2 or C 10H12O2 82 g/mol 14.86 T fp = 61.93 C 61.70 C = 0.23 C Tbp 0.23 C msolute = = = 0.063 m K bp 3.63 C/m 0.063mol hexachlorophene 0.0250 kg CHCl = 0.0016 mol hexachlorophene 3 1 kg CHCl3 0.640 g hexachlorophene = 4.0 10 2 g/mol 0.0016 mol hexachlorophene 14.87 At 80 C 1092 g NH4CHO2 will dissolve in 200 g of water (546 g/100 g). At 0 C only 204 g NH4CHO2 will dissolve in 200 g of water (102 g/100 g). 1092 g 204 g = 888 g NH4CHO2 precipitates at 0 C 14.88 SN2 = (8.42 10 7 M/mm Hg)(585 mm Hg) = 4.93 10 4 mol/L

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14.89

15.5 mm Hg 0.55 = 8.53 mm Hg PH O 8.53 mm Hg XHO = = = 0.550 X C H (OH) = 1 0.550 = 0.450 P H O 15.5 mm Hg 18.02 g 92.09 g 0.550 mol H2O = 9.91 g H2O 0.450 mol C3 H 5(OH) 3 = 41.4 g C3H 5 (OH) 3 1 mol 1 mol 41.4g C3 H 5 (OH) 3 Weight % = 100% = 80.7% 41.4 g C3 H 5 (OH) 3 + 9.91 g H2O
2 2 3 5 3 2

14.90

1 atm 3.8 mm Hg 760 mm Hg (a) cstarch = = = 2.0 10 4 mol/L RT (0.082057 L atm/K mol)(298 K) 10.0 g/L = 4.9 10 4 g/mol 0.00020 mol/L (b) Tfp = K fp msolute = (1.86 C/m)(2.0 10 4 m) = 3 . 8 10 4 C The very small change in the freezing point would make it very difficult to determine the molar mass of starch using freezing-point depression.

14.91

5 g CH3CO2H
3 2

1 mol 1 mol = 0.08 mol CH3CO2 H 95 g H 2O = 5.3 mol H2O 60.0 g 18.0 g 0.08 mol CH3CO2 H X CH CO H = = 0.016 0.08 mol CH3CO2 H + 5.8 mol H2O 0.08 mol CH3CO 2H mCH CO H = = 0.9 m 0.095kg H2O 5 10 3 mg CH3CO 2H = 0.05 mg/L = 0.05 ppm 1 mL 1L 100 g solution 3 1g 10 mL
3 2

Calculating molarity requires knowing the total volume of the solution. Without knowing the density of the acetic acid solution it is impossible to calculate the molarity of the solution. 14.92 Benzene solution: T fp = 3.37 C 5.50 C = 2.13 C Tbp 2.13 C msolute = = = 0.416 m K bp 5.12 C/m 0.416mol acetic acid 0.100 kg benzene= 0.0416 mol acetic acid 1 kg benzene 5.00 g acetic acid = 120. g/mol 0.0416 mol acetic acid

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Aqueous solution: T fp = 1.49 C Tbp 1.49 C msolute = = = 0.801 m K bp 1.86 C/m 0.801mol acetic acid 0.100 kg H2O = 0.0801 mol acetic acid 1 kg H 2O 5.00 g acetic acid = 62.4 g/mol 0.0801 mol acetic acid The actual molar mass of acetic acid is 60.05 g/mol. The aqueous solution calculated molar mass is slightly higher, suggesting that the i value for acetic acid is slightly greater than 1 (the acid is weakly ionized in solution). This is consistent with acetic acid being a weak acid in aqueous solution. The benzene solution calculated molar mass is twice the actual molar mass, suggesting that the acetic acid molecules form dimers in benzene. O CH3 H C
O C H3C O H O

14.93

mHOCH CH OH =
2 2

Tfp K fp
2 2

15.0 C = 8.06 m 1.86 C/m

Tbp = K bp m HOCH CH OH = (+0.5121 C/m)(8.06 m) = 4.13 C Tbp = 100.00 C + 4.13 C = 104.13 C 14.94 The acetic acid only reacts with the calcium carbonate shell, not with the egg membrane. When the egg is placed in water, it swells because the concentration of solute is higher inside the egg than outside. There is therefore a net flow of water into the egg. The situation is opposite when the egg is placed in corn syrup. Water passes out of the egg from a solution of low solute concentration to one of relatively higher concentration. 14.95 All of the alcohols contain a polar OH group that can interact with polar water molecules. The smaller alcohols are miscible with water because of this polar group. However, with an increase in the size of the hydrocarbon group, the organic group (the nonpolar part of the molecule) has become a larger fraction of the molecule, and properties associated with nonpolarity begin to dominate. 14.96 The CC and CH bonds in hydrocarbons being nonpolar would tend to make such dispersions hydrophobic. The CO and OH bonds in starch present opportunities for hydrogen bonding with water, and hence such dispersions are expected to be hydrophilic.

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14.97 14.98

As lattice energy becomes more negative, solubility increases. Li2SO4(s) Li 2SO4(aq) Hsoln = Hf [Li2SO4(aq)] Hf [Li2SO4(s)] = 1464.4 kJ/mol (1436.4 kJ/mol) = 28.0 kJ/mol K2SO4(s) K2SO4(aq) Hsoln = Hf [K2SO4(aq)] Hf [K2SO4(s)] = 1414.0 kJ/mol (1437.7 kJ/mol) = 23.7 kJ/mol The enthalpy of solution for Li2SO4 is exothermic, and that for K2SO4 is endothermic LiCl(s) LiCl(aq) Hsoln = Hf [LiCl(aq)] Hf [LiCl(s)] = 445.6 kJ/mol (408.6 kJ/mol) = 37.0 kJ/mol KCl(s) KCl(aq) Hsoln = Hf [KCl(aq)] Hf [KCl(s)] = 419.5 kJ/mol (436.7 kJ/mol) = 17.2 kJ/mol Again, the lithium salt has an exothermic enthalpy of solution and the potassium salt enthalpy of solution is endothermic.

14.99

The density of water is 0.997 g/cm3, so 1000. mL of water will have a mass of 997 g. 997 g H2O 1 mol = 55.3 M 1L 18.02 g 55.3 mol H2O = 55.5 m 0.997 kg 1.0 mol = 0.33 1.0mol + 2.0 mol Xbenzene = 2.0mol = 0.67 2.0 mol + 1.0 mol

14.100 liquid: Xtoluene =

Ptotal = Ptoluene + Pbenzene = XtoluenePtoluene + XbenzenePbenzene Ptotal = (0.33)(22 mm Hg) + (0.67)(75 mm Hg) = 7.3 mm Hg + 50. mm Hg = 57 mm Hg P 7.3 mm Hg P 50. mm Hg vapor Xtoluene = toluene = = 0.13 Xbenzene = benzene = = 0.87 P toluene 57 mm Hg P benzene 57 mm Hg 14.101 50.0 mL C2H 5OH 0.785 g 1 mol = 0.852 mol C2H 5OH 1 mL 46.07 g 1.00 g 1 mol 50.0 mL H 2O = 2.77 mol H2O 1 mL 18.02 g 0.852 mol X C H OH = = 0.235 0.852 + 2.77
2 5

Ptotal = PC2 H5 OH + PH2 O = XC2 H5 OHPC2 H5 OH + (1 XC2 H5 OH)PH2 O Ptotal = (0.235)(43.6 mm Hg) + (1 0.235)(17.5 mm Hg) = 23.6 mm Hg 1 mol C13 H 21ClN 2O2 273g m= = 0.075 m 0.0980kg H 2O Tfp 0.237 C i = = = 1.7 K fp m (1.86 C/m)(0.075 m) 2.0 g There are approximately 2 moles of ions in solution per mole of compound.
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14.102

Chapter 14

Solutions and Their Behavior

14.103 (a) mmaltose =

Tfp K fp

0.229 C = 0.123 m 1.86 C/m

0.123mol maltose 0.09600 kg H2O = 0.0118 mol maltose 1 kg H 2O 4.00 g maltose = 338 g/mol 0.0118 mol maltose 1 mL (b) 100.00 g solution = 98.62 mL 1.014 g 4.00 g cmaltose = 1 mol 338 g = 0.120 mol/L 0.09862 L

at 25 C : = cRT = (0.120 mol/L)(0.082057 L atm/K mol)(298 K) = 2.93 atm 14.104 (a) Assume a mass of 1 10 6 g seawater 1 mol Cl 1.95 10 4 g = 550. mol Cl 35.45 g 1 mol Na+ 1.08 10 4 g = 470. mol Na + 22.99 g 1 mol 2+ Mg2+ 1.29 10 3 g = 53.1. mol Mg 24.31 g 1 mol 2 SO42 9.05 10 2 g = 9.42 mol SO 4 96.06 g 1 mol Ca2+ 4.12 10 2 g = 10.3 mol Ca2+ 40.08 g 1 mol K+ 3.80 10 2 g = 9.72 mol K+ 39.10 g 1 mol Br 67 g = 0.84 mol Br 79.90 g 1103 mol ions mions = = 1.103 m 1 10 3 kg H 2O Tfp = K fp m ions = (1.86 C/m)(1.103 m) = 2.05 C 1.103 mol ions (b) = cRT = (0.082057 L atm/K mol)(298 K) = 27.0 atm 1L A pressure greater than 27.0 atm is required to purify seawater by reverse osmosis. 14.105 (a) The 10 m tree is equal to a column of water 104 mm tall. The equivalent column of mercury would be 1.0 mm Hg 104 mm Hg = 735 mm Hg 13.6 mm H2O 1 atm 735 mm Hg 760 mm Hg c= = = 0.0402 M RT (0.082057 L atm/K mol)(293 K) (b) Assuming the density of sap is 1.0 g/mL, the mass of 1 L of sap is 103 g (0.0402 mol/L)(342.3 g/mol) Weight % = 100% = 1.38% 1.0 10 3 g/L T fp = 2.05 C

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1 mol H2SO4 98.08g 14.106 (a) m = = 0.208 m 0.09800kg H 2O Tfp 0.796 C i = = = 2.06 K fp m (1.86 C/m)(0.208 m) 2.00 g (b) H+ + HSO4 14.107 m= Tfp 1.28 C = = 0.344 m K fp i (1.86 C/m)(2)

0.344mol KX 0.100 kg H2O = 0.0344 mol KX 1 kg H 2O 4.00 g KX = 116 g/mol 0.344mol KX 116 g/mol 39 g/mol = 77 g/mol The halide ion is probably Br

14.108 (a) Assume 100.0 g compound 1 mol B 1 mol F 22.1 g = 2.04 mol B 77.9 g = 4.10 mol F 10.81 g 19.00 g 4.10 mol F 2 mol F = The empirical formula is BF2 2.04 mol B 1 mol B PC H 94.16 mm Hg 1 mol XCH = = = 0.9885 10.0 g C6H 6 = 0.128 mol C6H 6 P C H 95.26 mm Hg 78.11 g
6 6 6 6 6 6

0.9885 =

0.128 mol C6 H 6 0.128 mol C6 H 6 + x mol solute x = 0.00150 mol solute 0.146 g solute = 97.6 g/mol 0.00150 mol solute 97.6 g/mol = 2 The molecular formula is (BF2 ) 2 or B2 F4 48.81 g/mol F F B F B F All bond angles are 120; the boron atom is sp2 hybridized

(b)

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14.109 Compound contains 73.94% C, 8.27% H, and 17.79% Cr 1 mol 1 mol 73.94 g C = 6.156 mol C 8.27 g H = 8.20 mol H 12.011 g 1.008 g 1 mol 17.79 g Cr = 0.3421 mol Cr 51.996 g 6.156 mol C 18 mol C 8.20 mol H 24 mol H = = The empirical formula is C18 H 24Cr 0.3421mol Cr 1 mol Cr 0.3421mol Cr 1 mol Cr 1 atm 3.17 mm Hg 760 mm Hg(0.100 L) V n= = = 1.70 10 5 mol RT (0.082057 L atm/K mol)(298.2 K) 5.00 10 3g compound = 293 g/mol 1.70 10 5 mol The empirical formula weight is 292.4 g/mol, so the molecular formula is also C18H24Cr 14.110 (a) Additional NiCl2 can be dissolved. (b) Disturbing the solution in some way will lead to precipitation. 14.111 (a) CCl 4. Yes, both I2 and CCl4 are nonpolar molecules. (b) Hexane is a nonpolar molecule so it will be more soluble in CCl4 than in H2O. 14.112 The rate at which molecules of gas enter the solution equals the rate at which they leave the solution to return to the gas phase. 14.113 10.0 g of ethylene glycol contains more moles of solute, so it has a greater influence on the vapor pressure. 14.114 (a) Boiling point elevation is the consequence of the decrease in solvent vapor pressure, owing to the dissolution of solute. (b) The ionic solute 0.10 m NH4NO3 14.115 (a) The membrane surrounding the egg white (b) The egg would shrink. (c) [NaCl] = 1.0 M; [KNO3] = 0.88 M The KNO3 solution has a higher solvent concentration, so solvent will flow from the KNO3 solution to the NaCl solution. 14.116 See the sidebar on CD-ROM Screen 14.11.

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