Properties of Solutions: Solution Review

CHAPTER 11
PROPERTIES OF SOLUTIONS
Solution Review
1 mol C3 H 7 OH
585 g C3 H 7 OH ×
60.09 g C3 H 7 OH
13. = 9.74 M
1.00 L
0.100 mol 134.00 g

14. 0.250 L × × = 3.35 g Na2C2O4
L mol
0.040 mol HCl 1L

15. 1.00 L × = 0.040 mol HCl; 0.040 mol HCl × = 0.16 L
L 0.25 mol HCl
= 160 mL
1 mol CaCl 2 1L 1000 mL

16. 1.28 g CaCl2 × × × = 19.9 mL
110.98 g CaCl 2 0.580 mol CaCl 2 L
3.0 mol Na 2 CO 3
17. Mol Na2CO3 = 0.0700 L × = 0.21 mol Na2CO3
L
Na2CO3(s) → 2 Na+(aq) + CO32−(aq); mol Na+ = 2(0.21) = 0.42 mol
1.0 mol NaHCO 3
Mol NaHCO3 = 0.0300 L × = 0.030 mol NaHCO3
L
NaHCO3(s) → Na+(aq) + HCO3−(aq); mol Na+ = 0.030 mol
total mol Na + 0.42 mol + 0.030 mol 0.45 mol

M Na + = = = = 4.5 M Na+
total volume 0.0700 L + 0.030 L 0.1000 L
18. a. HNO3(l) → H+(aq) + NO3−(aq) b. Na2SO4(s) → 2 Na+(aq) + SO42−(aq)
c. Al(NO3)3(s) → Al3+(aq) + 3 NO3−(aq) d. SrBr2(s) → Sr2+(aq) + 2 Br−(aq)
e. KClO4(s) → K+(aq) + ClO4−(aq) f. NH4Br(s) → NH4+(aq) + Br−(aq)
g. NH4NO3(s) → NH4+(aq) + NO3−(aq) h. CuSO4(s) → Cu2+(aq) + SO42−(aq)
i. NaOH(s) → Na+(aq) + OH−(aq)
408
CHAPTER 11 PROPERTIES OF SOLUTIONS 409
Questions
19. As the temperature increases, the gas molecules will have a greater average kinetic energy. A
greater fraction of the gas molecules in solution will have a kinetic energy greater than the
attractive forces between the gas molecules and the solvent molecules. More gas molecules
are able to escape to the vapor phase, and the solubility of the gas decreases.
20. Henry’s law is obeyed most accurately for dilute solutions of gases that do not dissociate in
or react with the solvent. NH3 is a weak base and reacts with water by the following reaction:
NH3(aq) + H2O(l) → NH4+(aq) + OH−(aq)
O2 will bind to hemoglobin in the blood. Due to these reactions in the solvent, NH3(g) in
water and O2(g) in blood do not follow Henry’s law.
21. Because the solute is volatile, both the water and solute will transfer back and forth between
the two beakers. The volume in each beaker will become constant when the concentrations of
solute in the beakers are equal to each other. Because the solute is less volatile than water,
one would expect there to be a larger net transfer of water molecules into the right beaker
than the net transfer of solute molecules into the left beaker. This results in a larger solution
volume in the right beaker when equilibrium is reached, i.e., when the solute concentration is
identical in each beaker.
22. Solutions of A and B have vapor pressures less than ideal (see Figure 11.14 of the text), so
this plot shows negative deviations from Raoult’s law. Negative deviations occur when the
intermolecular forces are stronger in solution than in pure solvent and solute. This results in
an exothermic enthalpy of solution. The only statement that is false is e. A substance boils
when the vapor pressure equals the external pressure. Because χB = 0.6 has a lower vapor
pressure at the temperature of the plot than either pure A or pure B, one would expect this
solution to require the highest temperature in order for the vapor pressure to reach the
external pressure. Therefore, the solution with χB = 0.6 will have a higher boiling point than
either pure A or pure B. (Note that because P°B > P°A, B is more volatile than A, and B will
have a lower boiling point temperature than A).
23. No, the solution is not ideal. For an ideal solution, the strengths of intermolecular forces in
solution are the same as in pure solute and pure solvent. This results in ΔHsoln = 0 for an ideal
solution. ΔHsoln for methanol-water is not zero. Because ΔHsoln < 0 (heat is released), this
solution shows a negative deviation from Raoult’s law.
24. The micelles form so that the ionic ends of the detergent molecules, the SO4− ends, are
exposed to the polar water molecules on the outside, whereas the nonpolar hydrocarbon
chains from the detergent molecules are hidden from the water by pointing toward the inside
of the micelle. Dirt, which is basically nonpolar, is stabilized in the nonpolar interior of the
micelle and is washed away. See the illustration on the following page.
410 CHAPTER 11 PROPERTIES OF SOLUTIONS
= detergent
molecule
= SO 4-
= nonpolar
hydrocarbon
= dirt
25. Normality is the number of equivalents per liter of solution. For an acid or a base, an
equivalent is the mass of acid or base that can furnish 1 mole of protons (if an acid) or accept
1 mole of protons (if a base). A proton is an H+ ion. Molarity is defined as the moles of solute
per liter of solution. When the number of equivalents equals the number of moles of solute,
then normality = molarity. This is true for acids which only have one acidic proton in them
and for bases that accept only one proton per formula unit. Examples of acids where
equivalents = moles solute are HCl, HNO3, HF, and HC2H3O2. Examples of bases where
equivalents = moles solute are NaOH, KOH, and NH3. When equivalents ≠ moles solute,
then normality ≠ molarity. This is true for acids that donate more than one proton (H2SO4,
H3PO4, H2CO3, etc.) and for bases that react with more than one proton per formula unit
[Ca(OH)2, Ba(OH)2, Sr(OH)2, etc.].
26. It is true that the sodium chloride lattice must be broken in order to dissolve in water, but a lot
of energy is released when the water molecules hydrate the Na+ and Cl− ions. These two
processes have relatively large values for the amount of energy associated with them, but they
are opposite in sign. The end result is they basically cancel each other out resulting in a ∆Hsoln
≈ 0. So energy is not the reason why ionic solids like NaCl are so soluble in water. The
answer lies in nature’s tendency toward the higher probability of the mixed state. Processes,
in general, are favored that result in an increase in disorder because the disordered state is the
easiest (most probable) state to achieve. The tendency of processes to increase disorder will
be discussed in Chapter 17 when entropy, S, is introduced.
27. Only statement b is true. A substance freezes when the vapor pressure of the liquid and solid
are the same. When a solute is added to water, the vapor pressure of the solution at 0°C is less
than the vapor pressure of the solid, and the net result is for any ice present to convert to
liquid in order to try to equalize the vapor pressures (which never can occur at 0°C). A lower
temperature is needed to equalize the vapor pressure of water and ice, hence, the freezing
point is depressed.
For statement a, the vapor pressure of a solution is directly related to the mole fraction of
solvent (not solute) by Raoult’s law. For statement c, colligative properties depend on the
number of solute particles present and not on the identity of the solute. For statement d, the
boiling point of water is increased because the sugar solute decreases the vapor pressure of
the water; a higher temperature is required for the vapor pressure of the solution to equal the
external pressure so boiling can occur.
28. This is true if the solute will dissolve in camphor. Camphor has the largest Kb and Kf
constants. This means that camphor shows the largest change in boiling point and melting
point as a solute is added. The larger the change in ∆T, the more precise the measurement and
the more precise the calculated molar mass. However, if the solute won’t dissolve in
camphor, then camphor is no good and another solvent must be chosen which will dissolve
the solute.
29. Adding a solute to a solvent increases the boiling point and decreases the freezing point of the
solvent. Thus the solvent is a liquid over a wider range of temperatures when a solute is
dissolved.
30. Table sugar (C12H22O11) and urea [(NH2)2CO] are nonelectrolytes in water, i.e., they stay
together when dissolved in water. CaCl2 is a strong electrolyte which breaks up into three
ions when dissolved in water. A 1 molal solution of CaCl2 has an effective particle
concentration of 3 molal (assuming complete dissociation). If the three solutions have equal
molal concentrations, the CaCl2 solution will have many more particles present and will have
a lower freezing point; it will be more effective at melting ice on roads.
31. Colligative properties are ones that only depend on the number of solute particles present and
not on the identity of the solute. So if the boiling points of the two aqueous solutions are the
same, then the two solutions have the same moles of proteins present. Other colligative
properties that will be the same between the two solutions are vapor pressure, boiling point,
and osmotic pressure. This assumes that molarity = molality for the solutions, which is a
reasonable assumption for dilute solutions.
32. In dialysis, the blood is passed through cellophane tube which acts as a semipermeable
membrane. The tube is surrounded by a dialyzing solution which has the same ion and small
particle concentrations as healthy blood. As the patient’s blood passes through the cellophane
tube, waste products in the blood move from the patient’s blood into the dialyzing solution,
which cleanses the blood.
33. Isotonic solutions are those which have identical osmotic pressures. Crenation and hemolysis
refer to phenomena that occur when red blood cells are bathed in solutions having a mismatch
in osmotic pressures inside and outside the cell. When red blood cells are in a solution having
a higher osmotic pressure than that of the cells, the cells shrivel as there is a net transfer of
water out of the cells. This is called crenation. Hemolysis occurs when the red blood cells are
bathed in a solution having lower osmotic pressure than that inside the cell. Here, the cells
rupture as there is a net transfer of water to into the red blood cells.
34. Ion pairing is a phenomenon that occurs in solution when oppositely charged ions aggregate
and behave as a single particle. For example, when NaCl is dissolved in water, one would
expect sodium chloride to exist as separate hydrated Na+ ions and Cl− ions. A few ions,
however, stay together as NaCl and behave as just one particle. Ion pairing increases in a
solution as the ion concentration increases (as the molality increases).
Exercises
Solution Composition
2.5 mol NaCl 58.44 g

35. 0.0075 kg × × = 11g NaCl
kg mol NaCl
mass of NaCl 11 g
Mass % = × 100 = × 100 = 1.9%
mass of solution 500. + 75
1 mol 0.025 mol

36. 5.0 g C6H12O6•H2O × = 0.025 mol; molarity = = 0.25 mol/L
198.17 g 0.1000 L
0.025 mol C 6 H 12 O 6 • H 2 O
Molality = = 0.25 mol/kg
1.01 g 1 kg
100.0 mL × ×
mL 1000 g
37. Because the density of water is 1.00 g/mL, 100.0 mL of water has a mass of 100. g.
mass 10.0 g H 3 PO 4 + 100. g H 2 O
Density = = = 1.06 g/mL = 1.06 g/cm3
volume 104 mL
1 mol
Mol H3PO4 = 10.0 g × = 0.102 mol H3PO4
97.99 g
1 mol
Mol H2O = 100. g × = 5.55 mol H2O
18.02 g
0.102 mol H 3 PO 4
Mole fraction of H3PO4 = = 0.0180
(0.102 + 5.55) mol
χ H 2O = 1.000 – 0.0180 = 0.9820
0.102 mol H 3 PO 4
Molarity = = 0.981 mol/L
0.104 L
0.102 mol H 3 PO 4
0.100 kg
40.0 g C 2 H 6 O 2 1000 g 1 mol C 2 H 6 O 2

38. Molality = × × = 10.7 mol/kg
60.0 g H 2 O kg 62.07 g
40.0 g C 2 H 6 O 2 1.05 g 1000 cm 3 1 mol C 2 H 6 O 2
Molarity = × 3
× × = 6.77 mol/L
100.0 g solution cm L 62.07 g
1 mol 1 mol
40.0 g C2H6O2 × = 0.644 mol C2H6O2; 60.0 g H2O × = 3.33 mol H2O
62.07 g 18.02 g
0.644
χ EG = = 0.162 = mole fraction ethylene glycol (C2H6O2)
3.33 + 0.644
39. Hydrochloric acid (HCl):
38 g HCl 1.19 g soln 1000 cm 3 1 mol HCl

molarity = × × × = 12 mol/L
100. g soln cm 3 soln L 36.5 g
38 g HCl 1000 g 1 mol HCl
molality = × × = 17 mol/kg
62 g solvent kg 36.5 g
1 mol 1 mol
38 g HCl × = 1.0 mol HCl; 62 g H2O × = 3.4 mol H2O
36.5 g 18.0 g
1.0
mole fraction of HCl = χ HCl = = 0.23
3.4 + 1.0
Nitric acid (HNO3):
70. g HNO 3 1.42 g soln 1000 cm 3 1 mol HNO 3

× × × = 16 mol/L
100. g soln cm 3 soln L 63.0 g
70. g HNO 3 1000 g 1 mol HNO 3
× × = 37 mol/kg
30. g solvent kg 63.0 g
1 mol 1 mol
70. g HNO3 × = 1.1 mol HNO3; 30. g H2O × = 1.7 mol H2O
63.0 g 18.0 g
1.1
χ HNO3 = = 0.39
1.7 + 1.1
Sulfuric acid (H2SO4):
95 g H 2SO 4 1.84 g soln 1000 cm 3 1 mol H 2SO 4

× 3
× × = 18 mol/L
100. g soln cm soln L 98.1 g H 2SO 4
95 g H 2SO 4 1000 g 1 mol
× × = 194 mol/kg ≈ 200 mol/kg
5 g H 2O kg 98.1 g
1 mol 1 mol
95 g H2SO4 × = 0.97 mol H2SO4; 5 g H2O × = 0.3 mol H2O
98.1 g 18.0 g
0.97
χ H 2SO 4 = = 0.76
0.97 + 0.3
Acetic acid (CH3CO2H):
99 g CH 3CO 2 H 1.05 g soln 1000 cm 3 1 mol

× 3
× × = 17 mol/L
100. g soln cm soln L 60.05 g
99 g CH 3CO 2 H 1000 g 1 mol

× × = 1600 mol/kg ≈ 2000 mol/kg
1 g H 2O kg 60.05 g
1 mol 1 mol
99 g CH3CO2H × = 1.6 mol CH3CO2H; 1 g H2O × = 0.06 mol H2O
60.05 g 18.0 g
1.6
χ CH 3CO 2 H = = 0.96
1.6 + 0.06
Ammonia (NH3):
28 g NH 3 0.90 g 1000 cm 3 1 mol

× 3
× × = 15 mol/L
100. g soln cm L 17.0 g
28 g NH 3 1000 g 1 mol
× × = 23 mol/kg
72 g H 2 O kg 17.0 g
1 mol 1 mol
28 g NH3 × = 1.6 mol NH3; 72 g H2O × = 4.0 mol H2O
17.0 g 18.0 g
1.6
χ NH 3 = = 0.29
4.0 + 1.6
40. a. If we use 100. mL (100. g) of H2O, we need:

2.0 mol KCl 74.55 g
0.100 kg H2O × × = 14.9 g = 15 g KCl
kg mol KCl
Dissolve 15 g KCl in 100. mL H2O to prepare a 2.0 m KCl solution. This will give us
slightly more than 100 mL, but this will be the easiest way to make the solution. Because
we don’t know the density of the solution, we can’t calculate the molarity and use a
volumetric flask to make exactly 100 mL of solution.
b. If we took 15 g NaOH and 85 g H2O, the volume probably would be less than 100 mL.
To make sure we have enough solution, let’s use 100. mL H2O (100. g H2O). Let x =
mass of NaCl.
x
Mass % = 15 = × 100, 1500 + 15x = (100.)x, x = 17.6 g ≈ 18 g
100. + x
Dissolve 18 g NaOH in 100. mL H2O to make a 15% NaOH solution by mass.
c. In a fashion similar to part b, let’s use 100. mL CH3OH. Let x = mass of NaOH.
0.79 g
100. mL CH3OH × = 79 g CH3OH
mL
x
Mass % = 25 = × 100, 25(79) + 25x = (100.)x, x = 26.3 g ≈ 26 g
79 + x
Dissolve 26 g NaOH in 100. mL CH3OH.
d. To make sure we have enough solution, let’s use 100. mL (100. g) of H2O. Let x = mol
C6H12O6.
1 mol H 2 O
100. g H2O × = 5.55 mol H2O
18.02 g
x
χ C6 H12O 6 = 0.10 = , (0.10)x + 0.56 = x, x = 0.62 mol C6H12O6
x + 5.55
180.2 g
0.62 mol C6H12O6 × = 110 g C6H12O6
mol
Dissolve 110 g C6H12O6 in 100. mL of H2O to prepare a solution with χ C6 H12O 6 = 0.10.
0.63 g 0.63 g 1 mol

41. 25 mL C5H12 × = 16 g C5H12; 25 mL × × = 0.22 mol C5H12
mL mL 72.15 g
0.66 g 0.66 g 1 mol
45 mL C6H14 × = 30. g C6H14; 45 mL × × = 0.34 mol C6H14
mL mL 86.17 g
mass pentane 16 g
Mass % pentane = × 100 = × 100 = 35%
total mass 16 g + 30. g
mol pentane 0.22 mol
χpentane = = = 0.39
total mol 0.22 mol + 0.34 mol
mol pentane 0.22 mol
Molality = = = 7.3 mol/kg
kg hexane 0.030 kg
mol pentane 0.22 mol 1000 mL
Molarity = = × = 3.1 mol/L
L solution 25 mL + 45 mL 1L
0.867 g 0.874 g
42. 50.0 mL toluene × = 43.4 g toluene; 125 mL benzene × = 109 g benzene
mL mL
mass of toluene 43.4 g
Mass % toluene = × 100 = × 100 = 28.5%
total mass 43.4 g + 109 g
43.4 g toluene 1000 mL 1 mol toluene
Molarity = × × = 2.69 mol/L
175 mL soln L 92.13 g toluene
43.4 g toluene 1000 g 1 mol toluene
Molality = × × = 4.32 mol/kg
109 g benzene kg 92.13 g toluene
1 mol
43.4 g toluene × = 0.471 mol toluene
92.13 g
1 mol benzene 0.471
109 g benzene × = 1.40 mol benzene; χtoluene = = 0.252
78.11 g benzene 0.471 + 1.40
43. If we have 100.0 mL of wine:

0.789 g 1.00 g
12.5 mL C2H5OH × = 9.86 g C2H5OH and 87.5 mL H2O × = 87.5 g H2O
mL mL
9.86 g
Mass % ethanol = × 100 = 10.1% by mass
87.5 g + 9.86 g
9.86 g C 2 H 5 OH 1 mol
Molality = × = 2.45 mol/kg
0.0875 kg H 2 O 46.07 g
1.00 mol acetone 1 mol

44. = 1.00 molal; 1.00 × 103 g C2H5OH × = 21.7 mol C2H5OH
1.00 kg ethanol 46.07 g
1.00
χacetone = = 0.0441
1.00 + 21.7
58.08 g CH 3COCH 3 1 mL
1 mol CH3COCH3 × × = 73.7 mL CH3COCH3
mol CH 3COCH 3 0.788 g
1 mL
1.00 × 103 g ethanol × = 1270 mL; total volume = 1270 + 73.7 = 1340 mL
0.789 g
1.00 mol
Molarity = = 0.746 M
1.34 L
45. If we have 1.00 L of solution:

192.12 g
1.37 mol citric acid × = 263 g citric acid (H3C6H5O7)
mol
1.10 g
1.00 × 103 mL solution × = 1.10 × 103 g solution
mL
263 g
Mass % of citric acid = × 100 = 23.9%
1.10 × 103 g
In 1.00 L of solution, we have 263 g citric acid and (1.10 × 103 − 263) = 840 g of H2O.
1.37 mol citric acid
0.84 kg H 2 O
1 mol 1.37
840 g H2O × = 47 mol H2O; χ citric acid = = 0.028
18.02 g 47 + 1.37
Because citric acid is a triprotic acid, the number of protons citric acid can provide is three
times the molarity. Therefore, normality = 3 × molarity:
normality = 3 × 1.37 M = 4.11 N
46. When expressing concentration in terms of normality, equivalents per liter are determined.
For acid-base reactions, equivalents are equal to the moles of H+ an acid can donate or the
moles of H+ a base can accept. For monoprotic acids like HCl, the equivalents of H+
furnished equals the moles of acid present. Diprotic acids like H2SO4 furnish two equivalents
of H+ per mole of acid, whereas triprotic acids like H3PO4 furnish three equivalents of H+ per
mole of acid. For the bases in this problem, the equivalents of H+ accepted equals the number
of OH− anions present in the formula (H+ + OH− → H2O). Finally, the equivalent mass of
a substance is the mass of acid or base that can furnish or accept 1 mole of protons (H+ ions).
0.250 mol HCl 1 equivalent 0.250 equivalents

a. Normality = × =
L mol HCl L
Equivalent mass = molar mass of HCl = 36.46 g
0.105 mol H 2 SO 4 2 equivalents 0.210 equivalents
b. Normality = × =
L mol H 2 SO 4 L
Equivalent mass = 1/2(molar mass of H2SO4) = 1/2(98.09) = 49.05 g
5.3 × 10 −2 mol H 3 PO 4 3 equivalents 0.16 equivalents

c. Normality = × =
L mol H 3 PO 4 L
Equivalent mass = 1/3(molar mass of H3PO4) = 1/3(97.09) = 32.66 g
0.134 mol NaOH 1 equivalent 0.134 equivalents
d. Normality = × =
L mol NaOH L
Equivalent mass = molar mass of NaOH = 40.00 g
0.00521 mol Ca (OH) 2 2 equivalents 0.0104 equivalents
e. Normality = × =
L mol Ca (OH) 2 L
Equivalent mass = 1/2[molar mass of Ca (OH) 2 ] = 1/2(74.10) = 37.05 g
Energetics of Solutions and Solubility
47. Using Hess’s law:
NaI(s) → Na+(g) + I−(g) ΔH = −ΔHLE = −(−686 kJ/mol)

Na (g) + I−(g) → Na+(aq) + I−(aq)
+
ΔH = ΔHhyd = −694 kJ/mol
NaI(s) → Na+(aq) + I−(aq) ΔHsoln = −8 kJ/mol
ΔHsoln refers to the heat released or gained when a solute dissolves in a solvent. Here, an
ionic compound dissolves in water.
48. a. CaCl2(s) → Ca2+(g) + 2 Cl−(g) ΔH = −ΔHLE = −(−2247 kJ)

Ca2+(g) + 2 Cl−(g) → Ca2+(aq) + 2 Cl−(aq) ΔH = ΔHhyd
CaCl2(s) → Ca2+(aq) + 2 Cl−(aq) ΔHsoln = –46 kJ
−46 kJ = 2247 kJ + ΔHhyd, ΔHhyd −2293 kJ
CaI2(s) → Ca2+(g) + 2 I−(g) ΔH = −ΔHLE = −(−2059 kJ)

Ca (g) + 2 I−(g) → Ca2+(aq) + 2 I−(aq)
2+
ΔH = ΔHhyd
CaI2(s) → Ca2+(aq) + 2 I−(aq) ΔHsoln = −104 kJ
−104 kJ = 2059 kJ + ΔHhyd, ΔHhyd = –2163 kJ

b. The enthalpy of hydration for CaCl2 is more exothermic than for CaI2. Any differences
must be due to differences in hydration between Cl− and I−. Thus the smaller chloride ion
is more strongly hydrated than the iodide ion.
49. Both Al(OH)3 and NaOH are ionic compounds. Since the lattice energy is proportional to the
charge of the ions, the lattice energy of aluminum hydroxide is greater than that of sodium
hydroxide. The attraction of water molecules for Al3+ and OH− cannot overcome the larger
lattice energy, and Al(OH)3 is insoluble. For NaOH, the favorable hydration energy is large
enough to overcome the smaller lattice energy, and NaOH is soluble.
50. The dissolving of an ionic solute in water can be thought of as taking place in two steps. The
first step, called the lattice-energy term, refers to breaking apart the ionic compound into
gaseous ions. This step, as indicated in the problem, requires a lot of energy and is
unfavorable. The second step, called the hydration-energy term, refers to the energy released
when the separated gaseous ions are stabilized as water molecules surround the ions. Because
the interactions between water molecules and ions are strong, a lot of energy is released when
ions are hydrated. Thus the dissolution process for ionic compounds can be thought of as
consisting of an unfavorable and a favorable energy term. These two processes basically
cancel each other out, so when ionic solids dissolve in water, the heat released or gained is
minimal, and the temperature change is minimal.
51. Water is a polar solvent and dissolves polar solutes and ionic solutes. Carbon tetrachloride
(CCl4) is a nonpolar solvent and dissolves nonpolar solutes (like dissolves like). To predict
the polarity of the following molecules, draw the correct Lewis structure and then determine
if the individual bond dipoles cancel or not. If the bond dipoles are arranged in such a manner
that they cancel each other out, then the molecule is nonpolar. If the bond dipoles do not
cancel each other out, then the molecule is polar.
a. KrF2, 8 + 2(7) = 22 e− b. SF2, 6 + 2(7) = 20 e−

S
F Kr F
F F
nonpolar; soluble in CCl4 polar; soluble in H2O
c. SO2, 6 + 2(6) = 18 e− d. CO2, 4 + 2(6) = 16 e−
S + 1 more
O C O
O O
polar; soluble in H2O nonpolar; soluble in CCl4
e. MgF2 is an ionic compound so it is soluble in water.

f. CH2O, 4 + 2(1) + 6 = 12 e− g. C2H4, 2(4) + 4(1) = 12 e−

O
H H
C C C
H H
H H
polar; soluble in H2O nonpolar (like all compounds made up of

only carbon and hydrogen); soluble in CCl4
52. Water is a polar solvent and dissolves polar solutes and ionic solutes. Hexane (C6H14) is a
nonpolar solvent and dissolves nonpolar solutes (like dissolves like).
a. Water; Cu(NO3)2 is an ionic compound.
b. C6H14; CS2 is a nonpolar molecule. c. Water; CH3OH is polar.
d. C6H14; the long nonpolar hydrocarbon chain favors a nonpolar solvent (the molecule
is mostly nonpolar).
e. Water; HCl is polar. f. C6H14; C6H6 is nonpolar.
53. Water exhibits H-bonding in the pure state and is classified as a polar solvent. Water will
dissolve other polar solutes and ionic solutes.
a. NH3; NH3 is capable of H-bonding, unlike PH3.
b. CH3CN; CH3CN is polar, while CH3CH3 is nonpolar.
c. CH3CO2H; CH3CO2H is capable of H-bonding, unlike the other compound.
54. For ionic compounds, as the charge of the ions increases and/or the size of the ions decreases,
the attraction to water (hydration) increases.
a. Mg2+; smaller size, higher charge b. Be2+; smaller size
c. Fe3+; smaller size, higher charge d. F−; smaller size
e. Cl−; smaller size f. SO42−; higher charge
55. As the length of the hydrocarbon chain increases, the solubility decreases. The ‒OH end of
the alcohols can hydrogen-bond with water. The hydrocarbon chain, however, is basically
nonpolar and interacts poorly with water. As the hydrocarbon chain gets longer, a greater
portion of the molecule cannot interact with the water molecules, and the solubility decreases;
i.e., the effect of the ‒OH group decreases as the alcohols get larger.
56. The main intermolecular forces are:
hexane (C6H14): London dispersion; chloroform (CHCl3): dipole-dipole, London

dispersion; methanol (CH3OH): H-bonding; and H2O: H-bonding (two places)
There is a gradual change in the nature of the intermolecular forces (weaker to stronger).
Each preceding solvent is miscible in its predecessor because there is not a great change in
the strengths of the intermolecular forces from one solvent to the next.
8.21 × 10 −4 mol
57. C = kP, = k × 0.790 atm, k = 1.04 × 10 −3 mol/L•atm
L
1.04 × 10 −4 mol
C = kP, C = × 1.10 atm = 1.14 × 10 −3 mol/L
L atm
1.3 × 10 −3 mol 1 atm

58. C = kP = × 120 torr × = 2.1 × 10−4 mol/L
L atm 760 torr
Vapor Pressures of Solutions
moles of C 2 H 5 OH
59. Psoln = χ C 2 H 5OH PCo2 H 5OH ; χ C 2 H 5OH =
total moles in solution
1 mol C 3 H 8 O 3
53.6 g C3H8O3 × = 0.582 mol C3H8O3
92.09 g
1 mol C 2 H 5 OH
133.7 g C2H5OH × = 2.90 mol C2H5OH
46.07 g
Total mol = 0.582 + 2.90 = 3.48 mol
2.90 mol
113 torr = × PCo2 H5OH , PCo2 H5OH = 136 torr
3.48 mol
60. P = χP°, 19.6 torr = χ(23.8 torr), χ = 0.824 = mole fraction of water
P = 0.824(71.9 torr) = 59.2 torr = vapor pressure at 45oC for glucose solution
When equal moles of NaCl is substituted for glucose, we must consider that NaCl breaks up
into two ions in solution. So the moles of solute particles will be double for the NaCl solution
as compared to the glucose solution (assuming complete dissociation of NaCl). If we have
100.0 moles of the glucose solution, χ = 0.824 determines that we have 82.4 moles of H2O
and 17.6 moles of glucose. The moles of solute particles if 17.6 moles of NaCl is substituted
for the glucose will be 2(17.6) = 35.2 mol.
moles of H 2 O 82.4
χ= = = 0.701; P = 0.701(71.9 torr) = 50.4 torr
total moles in solution 35.2 + 82.4
As expected the NaCl solution with more solute particles has the lower vapor pressure.
61. The normal boiling point of a substance is the boiling point at 1 atm pressure. So for this
problem, P° = 760. torr at 34.5°C (the normal boiling point of diethyl ether).
P = χP°; 698 torr = χ(760. torr), χ = 0.918 = mole fraction of diethyl ether
62. PB = χ B PBo , χ B = PB / PBo = 0.900 atm/0.930 atm = 0.968
mol benzene 1 mol

0.968 = ; mol benzene = 78.11 g C6H6 × = 1.000 mol
total mol 78.11 g
1.000 mol
Let x = mol solute, then: χB = 0.968 = , 0.968 + (0.968)x = 1.000, x = 0.033 mol
1.000 + x
10.0 g
Molar mass = = 303 g/mol ≈ 3.0 × 102 g/mol
0.033 mol
0.63 g 1 mol
63. a. 25 mL C5H12 × × = 0.22 mol C5H12
mL 72.15 g
0.66 g 1 mol
45 mL C6H14 × × = 0.34 mol C6H14; total mol = 0.22 + 0.34 = 0.56 mol
mL 86.17 g
mol pentane in solution 0.22 mol
χ pen
L
= = = 0.39, χ Lhex = 1.00 – 0.39 = 0.61
total mol in solution 0.56 mol
Ppen = χ Lpen Ppen

o
= 0.39(511 torr) = 2.0 × 102 torr; Phex = 0.61(150. torr) = 92 torr
Ptotal = Ppen + Phex = 2.0 × 102 + 92 = 292 torr = 290 torr
b. From Chapter 5 on gases, the partial pressure of a gas is proportional to the number of
moles of gas present (at constant volume and temperature). For the vapor phase:
mol pentane in vapor Ppen 2.0 × 10 2 torr
χ Vpen = = = = 0.69
total mol vapor Ptotal 290 torr
Note: In the Solutions Guide, we added V or L superscripts to the mole fraction symbol to
emphasize for which value we are solving. If the L or V is omitted, then the liquid phase is
assumed.
0.0300 mol CH 2 Cl 2
64. Ptotal = PCH 2Cl 2 + PCH 2 Br2 ; P = χ L P o ; χ CH
L
2 Cl 2
= = 0.375
0.0800 mol total
Ptotal = 0.375(133 torr) + (1.000 − 0.375)(11.4 torr) = 49.9 + 7.13 = 57.0 torr
PCH 2Cl 2 49.9 torr
In the vapor: χ CH
V
2 Cl 2
= = = 0.875; χ CH
V
2 Br2
= 1.000 – 0.875 = 0.125
Ptotal 57.0 torr
assumed.
65. Ptotal = Pmeth + Pprop, 174 torr = χ Lmeth (303 torr ) + χ prop
L
(44.6 torr ); χ Lprop = 1.000 − χ Lmeth
129
174 = 303χ Lmeth + (1.000 − χ Lmeth )44.6 torr, = χ Lmeth = 0.500
258
χ Lprop = 1.000 − 0.500 = 0.500
66. Ptol = χ Ltol Ptol

o
, Ppen = χ Lben Pben
o
; for the vapor, χ VA = PA/Ptotal. Because the mole fractions of
benzene and toluene are equal in the vapor phase, Ptol = Pben .
χ Ltol Ptol
o
= χ Lben Pben
o
= (1.00 − χ Ltol )Pben
o
, χ Ltol (28 torr ) = (1.00 − χ Ltol ) 95 torr
123 χ Ltol = 95, χ Ltol = 0.77; χ Lben = 1.00 – 0.77 = 0.23
67. Compared to H2O, solution d (methanol-water) will have the highest vapor pressure since
methanol is more volatile than water (PHo 2O = 23.8 torr at 25°C). Both solution b (glucose-
water) and solution c (NaCl-water) will have a lower vapor pressure than water by Raoult's
law. NaCl dissolves to give Na+ ions and Cl− ions; glucose is a nonelectrolyte. Because there
are more solute particles in solution c, the vapor pressure of solution c will be the lowest.
68. Solution d (methanol-water); methanol is more volatile than water, which will increase the
total vapor pressure to a value greater than the vapor pressure of pure water at this tempera-
ture.
69. The first diagram shows positive deviation from Raoult's law. This occurs when the solute-
solvent interactions are weaker than the interactions in pure solvent and pure solute. The
second diagram illustrates negative deviation from Raoult's law. This occurs when the
solute-solvent interactions are stronger than the interactions in pure solvent and pure solute.
The third diagram illustrates an ideal solution with no deviation from Raoult's law. This
occurs when the solute-solvent interactions are about equal to the pure solvent and pure
solute interactions.
a. These two molecules are named acetone (CH3COCH3) and water. As discussed in
section 11.4 on nonideal solutions, acetone-water solutions exhibit negative deviations
from Raoult’s law. Acetone and water have the ability to hydrogen bond with each other,
which gives the solution stronger intermolecular forces as compared to the pure states of
both solute and solvent. In the pure state, acetone cannot H−bond with itself. So the
middle diagram illustrating negative deviations from Raoult’s law is the correct choice
for acetone-water solutions.
b. These two molecules are named ethanol (CH3CH2OH) and water. Ethanol-water
solutions show positive deviations from Raoult’s law. Both substances can hydrogen
bond in the pure state, and they can continue this in solution. However, the solute-
solvent interactions are somewhat weaker for ethanol-water solutions due to the
significant nonpolar part of ethanol (CH3−CH2 is the nonpolar part of ethanol). This
nonpolar part of ethanol weakens the intermolecular forces in solution. So the first
diagram illustrating positive deviations from Raoult’s law is the correct choice for
ethanol-water solutions.
c. These two molecules are named heptane (C7H16) and hexane (C6H14). Heptane and
hexane are very similar nonpolar substances; both are composed entirely of nonpolar
C−C bonds and relatively nonpolar C−H bonds, and both have a similar size and shape.
Solutions of heptane and hexane should be ideal. So the third diagram illustrating no
deviation from Raoult’s law is the correct choice for heptane-hexane solutions.
d. These two molecules are named heptane (C7H16) and water. The interactions between the
nonpolar heptane molecules and the polar water molecules will certainly be weaker in
solution as compared to the pure solvent and pure solute interactions. This results in
positive deviations from Raoult’s law (the first diagram).
70. a. An ideal solution would have a vapor pressure at any mole fraction of H2O between that
of pure propanol and pure water (between 74.0 and 71.9 torr). The vapor pressures of the
various solutions are not between these limits, so water and propanol do not form ideal
solutions.
b. From the data, the vapor pressures of the various solutions are greater than if the
solutions behaved ideally (positive deviation from Raoult’s law). This occurs when the
intermolecular forces in solution are weaker than the intermolecular forces in pure
solvent and pure solute. This gives rise to endothermic (positive) ΔHsoln values.
c. The interactions between propanol and water molecules are weaker than between the pure
substances because the solutions exhibit a positive deviation from Raoult’s law.
d. At χ H 2O = 0.54, the vapor pressure is highest as compared to the other solutions. Because
a solution boils when the vapor pressure of the solution equals the external pressure, the
χ H 2O = 0.54 solution should have the lowest normal boiling point; this solution will have
a vapor pressure equal to 1 atm at a lower temperature as compared to the other solutions.
Colligative Properties
mol solute 27.0 g N 2 H 4 CO 1000 g 1 mol N 2 H 4 CO

71. Molality = m = = × × = 3.00 molal
kg solvent 150.0 g H 2 O kg 60.06 g N 2 H 4 CO
0.51 °C
ΔTb = Kbm = × 3.00 molal = 1.5°C
molal
The boiling point is raised from 100.0 to 101.5°C (assuming P = 1 atm).
ΔTb 1.35°C
72. ΔTb = 77.85°C − 76.50°C = 1.35°C; m = = = 0.268 mol/kg
K b 5.03 °C kg / mol
0.268 mol hydrocarbon
Mol biomolecule = 0.0150 kg solvent × = 4.02 × 10 −3 mol
kg solvent
From the problem, 2.00 g biomolecule was used that must contain 4.02 × 10 −3 mol
biomolecule. The molar mass of the biomolecule is:
2.00 g
= 498 g/mol
4.02 × 10 −3 mol
1.86 °C
73. ΔTf = Kfm, ΔTf = 1.50°C = × m, m = 0.806 mol/kg
molal
0.806 mol C 3 H 8 O 3 92.09 g C 3 H 8 O 3
0.200 kg H2O × × = 14.8 g C3H8O3
kg H 2 O mol C 3 H 8 O 3
0.91 °C
74. ΔTf = 25.50°C − 24.59°C = 0.91°C = Kfm, m = = 0.10 mol/kg
9.1 °C / molal
0.10 mol H 2 O 18.02 g H 2 O
Mass H2O = 0.0100 kg t-butanol × × = 0.018 g H2O
kg t - butanol mol H 2 O
50.0 g C 2 H 6 O 2 1000 g 1 mol

75. Molality = m = × × = 16.1 mol/kg
50.0 g H 2 O kg 62.07 g
ΔTf = Kfm = 1.86°C/molal × 16.1 molal = 29.9°C; Tf = 0.0°C − 29.9°C = –29.9°C
ΔTb = Kbm = 0.51°C/molal × 16.1 molal = 8.2°C; Tb = 100.0°C + 8.2°C = 108.2°C
∆Tf 25.0 °C
76. m= = = 13.4 mol C2H6O2/kg
Kf 1.86 °C kg / mol
Because the density of water is 1.00 g/cm3, the moles of C2H6O2 needed are:
1.00 kg H 2 O 13.4 mol C 2 H 6 O 2
15.0 L H2O × × = 201 mol C2H6O2
L H 2O kg H 2 O
62.07 g 1 cm 3
Volume C2H6O2 = 201 mol C2H6O2 × × = 11,200 cm3 = 11.2 L
mol C 2 H 6 O 2 1.11 g
0.51 °C
ΔTb = Kbm = × 13.4 molal = 6.8°C; Tb = 100.0°C + 6.8°C = 106.8°C
molal
∆Tf 2.63o C 6.6 × 10 −2 mol reserpine

77. ΔTf = Kfm, m = = =
Kf 40. o C kg/mol kg solvent
The moles of reserpine present is:
6.6 × 10 −2 mol reserpine

0.0250 kg solvent × = 1.7 × 10−3 mol reserpine
kg solvent
From the problem, 1.00 g reserpine was used, which must contain 1.7 × 10−3 mol reserpine.
The molar mass of reserpine is:
1.00 g
= 590 g/mol (610 g/mol if no rounding of numbers)
1.7 × 10 −3 mol
∆Tb 0.55o C
78. m = = = 0.32 mol/kg
Kb 1.71 o C kg/mol
0.32 mol hydrocarbon

Mol hydrocarbon = 0.095 kg solvent × = 0.030 mol hydrocarbon
kg solvent
From the problem, 3.75 g hydrocarbon was used, which must contain 0.030 mol hydrocarbon.
The molar mass of the hydrocarbon is:
3.75 g
= 130 g/mol (120 g/mol if no rounding of numbers)
0.030 mol
1.0 g protein 1 mol

79. a. M = × = 1.1 × 10 −5 mol/L; π = MRT
L 9.0 × 10 g
4
1.1 × 10 −5 mol 0.08206 L atm 760 torr

At 298 K: π = × × 298 K × , π = 0.20 torr
L K mol atm
Because d = 1.0 g/cm3, 1.0 L solution has a mass of 1.0 kg. Because only 1.0 g of protein
is present per liter of solution, 1.0 kg of H2O is present to the correct number of signifi-
cant figures, and molality equals molarity.
1.86 °C
ΔTf = Kfm = × 1.1 × 10 −5 molal = 2.0 × 10 −5 °C
molal
b. Osmotic pressure is better for determining the molar mass of large molecules. A tem-
perature change of 10 −5 °C is very difficult to measure. A change in height of a column
of mercury by 0.2 mm (0.2 torr) is not as hard to measure precisely.
ΔT 0.406 o C
80. m= = = 0.218 mol/kg
Kf 1.86 o C/molal
π = MRT, where M = mol/L; we must assume that molarity = molality so that we can
calculate the osmotic pressure. This is a reasonable assumption for dilute solutions when 1.00
kg of water ≈ 1.00 L of solution. Assuming NaCl exists as Na+ and Cl– ions in solution, a
0.218 m solution corresponds to 6.37 g NaCl dissolved in 1.00 kg of water. The volume of
solution may be a little larger than 1.00 L but not by much (to three sig. figs.). The
assumption that molarity = molality will be good here.
π = (0.218 M)(0.08206 L atm/K • mol)(298 K) = 5.33 atm
1 atm
0.745 torr ×
π 760 torr
81. M= = = 3.98 × 10−5 mol/L
RT 0.08206 L atm
× 300. K
K mol
3.98 × 10 −5 mol
1.00 L × = 3.98 × 10−5 mol catalase
L
10.00 g
Molar mass = = 2.51 × 105 g/mol
3.98 × 10 −5 mol
1 atm 0.08206 L atm

82. π = MRT, π = 18.6 torr × =M× × 298 K, M = 1.00 × 10−3 mol/L
760 torr K mol
1.00 × 10 −3 mol protein
Mol protein = 0.0020 L × = 2.0 × 10−6 mol protein
L
0.15 g
2.0 × 10 −6 mol
π 15 atm
83. π = MRT, M = = = 0.62 M
RT 0.08206 L atm
× 295 K
K mol
0.62 mol 342.30 g
× = 212 g/L ≈ 210 g/L
L mol C12 H 22 O11
Dissolve 210 g of sucrose in some water and dilute to 1.0 L in a volumetric flask. To get 0.62
±0.01 mol/L, we need 212 ±3 g sucrose.
π 15 atm
84. M= = = 0.62 M solute particles
RT 0.08206 L atm
× 295 K
K mol
This represents the total molarity of the solute particles. NaCl is a soluble ionic compound
that breaks up into two ions, Na+ and Cl−. Therefore, the concentration of NaCl needed is
0.62/2 = 0.31 M; this NaCl concentration will produce a 0.62 M solute particle solution
assuming complete dissociation.
0.31 mol NaCl 58.44 g NaCl
1.0 L × × = 18.1 ≈ 18 g NaCl
L mol NaCl
Dissolve 18 g of NaCl in some water and dilute to 1.0 L in a volumetric flask. To get 0.31
±0.01 mol/L, we need 18.1 g ±0.6 g NaCl in 1.00 L solution.
Properties of Electrolyte Solutions

85. Na3PO4(s) → 3 Na+(aq) + PO43−(aq), i = 4.0; CaBr2(s) → Ca2+(aq) + 2 Br−(aq), i = 3.0
KCl(s) → K+(aq) + Cl−(aq), i = 2.0
The effective particle concentrations of the solutions are (assuming complete dissociation):
4.0(0.010 molal) = 0.040 molal for the Na3PO4 solution; 3.0(0.020 molal) = 0.060 molal
for the CaBr2 solution; 2.0(0.020 molal) = 0.040 molal for the KCl solution; slightly
greater than 0.020 molal for the HF solution because HF only partially dissociates in
water (it is a weak acid).
a. The 0.010 m Na3PO4 solution and the 0.020 m KCl solution both have effective particle
concentrations of 0.040 m (assuming complete dissociation), so both of these solutions
should have the same boiling point as the 0.040 m C6H12O6 solution (a nonelectrolyte).
b. P = χP°; as the solute concentration decreases, the solvent’s vapor pressure increases
because χ increases. Therefore, the 0.020 m HF solution will have the highest vapor
pressure because it has the smallest effective particle concentration.
c. ΔT = Kfm; the 0.020 m CaBr2 solution has the largest effective particle concentration, so
it will have the largest freezing point depression (largest ΔT).
86. The solutions of C12H22O11, NaCl, and CaCl2 will all have lower freezing points, higher
boiling points, and higher osmotic pressures than pure water. The solution with the largest
particle concentration will have the lowest freezing point, the highest boiling point, and the
highest osmotic pressure. The CaCl2 solution will have the largest effective particle
concentration because it produces three ions per mole of compound.
a. pure water b. CaCl2 solution c. CaCl2 solution
d. pure water e. CaCl2 solution
5.0 g NaCl 1 mol

87. a. m = × = 3.4 molal; NaCl(aq) → Na+(aq) + Cl−(aq), i = 2.0
0.025 kg 58.44 g
ΔTf = iKfm = 2.0 × 1.86°C/molal × 3.4 molal = 13°C; Tf = −13°C
ΔTb = iKbm = 2.0 × 0.51°C/molal × 3.4 molal = 3.5°C; Tb = 103.5°C
2.0 g Al( NO 3 ) 3 1 mol

b. m= × = 0.63 mol/kg
0.015 kg 213.01 g
Al(NO3)3(aq) → Al3+(aq) + 3 NO3−(aq), i = 4.0
ΔTf = iKfm = 4.0 × 1.86°C/molal × 0.63 molal = 4.7°C; Tf = −4.7°C
88. NaCl(s) → Na+(aq) + Cl−(aq), i = 2.0

0.10 mol 0.08206 L atm
π = iMRT = 2.0 × × × 293 K = 4.8 atm
L K mol
A pressure greater than 4.8 atm should be applied to ensure purification by reverse osmosis.
89. There are six cations and six anions in the illustration which indicates six solute formula units
initially. There are a total of 10 solute particles in solution (a combined ion pair counts as
one solute particle). So the value for the van’t Hoff factor is:
moles of particles in solution 10
i = = = 1.67
moles of solute dissolved 6
90. From Table 11.6, MgSO4 has an observed i value of 1.3 while the observed i value for NaCl
is 1.9. Both salts have an expected i value of 2. The expected i value for a salt is determined
by assuming 100% of the salt breaks up into separate cations and anions. The MgSO4 solu-
tion is furthest from the expected i value because it forms the most combined ion pairs in
solution. So the figure on the left with the most combined ion pairs represents the MgSO4
solution. The figure on the right represents the NaCl solution. When NaCl is in solution, it
has very few combined ion pairs and, hence, has a van’t Hoff factor very close to the
expected i value.
91. a. MgCl2(s) → Mg2+(aq) + 2 Cl−(aq), i = 3.0 mol ions/mol solute
ΔTf = iKfm = 3.0 × 1.86 °C/molal × 0.050 molal = 0.28°C
Assuming water freezes at 0.00°C, the freezing point would be –0.28°C.
ΔTb = iKbm = 3.0 × 0.51 °C/molal × 0.050 molal = 0.077°C; Tb = 100.077°C (Assuming
water boils at 100.000°C.)
b. FeCl3(s) → Fe3+(aq) + 3 Cl−(aq), i = 4.0 mol ions/mol solute
ΔTf = iKfm = 4.0 × 1.86 °C/molal × 0.050 molal = 0.37°C; Tf = −0.37°C
ΔTb = iKbm = 4.0 × 0.51 °C/molal × 0.050 molal = 0.10°C; Tb = 100.10°C
92. a. MgCl2, i (observed) = 2.7
ΔTf = iKfm = 2.7 × 1.86 °C/molal × 0.050 molal = 0.25°C; Tf = −0.25°C
ΔTb = iKbm = 2.7 × 0.51 °C/molal × 0.050 molal = 0.069°C; Tb = 100.069°C
b. FeCl3, i (observed) = 3.4
ΔTf = iKfm = 3.4 × 1.86 °C/molal × 0.050 molal = 0.32°C; Tf = –0.32°C
∆Tf 0.110 C
93. ΔTf = iKfm, i = = = 2.63 for 0.0225 m CaCl2
Kf m 1.86 C / molal × 0.0225 molal
0.440 1.330
i= = 2.60 for 0.0910 m CaCl2; i = = 2.57 for 0.278 m CaCl2
1.86 × 0.0910 1.86 × 0.278
iave = (2.63 + 2.60 + 2.57)/3 = 2.60
Note that i is less than the ideal value of 3.0 for CaCl2. This is due to ion pairing in solution.
Also note that as molality increases, i decreases. More ion pairing appears to occur as the
solute concentration increases.
∆Tf 0.440 o C
94. For CaCl2: i = = = 2.6
K f m 1.86 o C/molal × 0.091 molal
2.6 − 1.0
Percent CaCl2 ionized = × 100 = 80.%; 20.% ion association occurs.
3.0 − 1.0
∆Tf 0.320 o C
For CsCl: i = = = 1.9
K f m 1.86 o C/molal × 0.091 molal
1.9 − 1.0
Percent CsCl ionized = × 100 = 90.%; 10% ion association occurs.
2.0 − 1.0
The ion association is greater in the CaCl2 solution.
95. a. TC = 5(TF − 32)/9 = 5(−29 − 32)/9 = −34°C

Assuming the solubility of CaCl2 is temperature independent, the molality of a saturated
CaCl2 solution is:
74.5 g CaCl 2 1000 g 1 mol CaCl 2 6.71 mol CaCl 2
× × =
100.0 g H 2 O kg 110.98 g CaCl 2 kg H 2 O
ΔTf = iKfm = 3.00 × 1.86 °C kg/mol × 6.71 mol/kg = 37.4°C
Assuming i = 3.00, a saturated solution of CaCl2 can lower the freezing point of water to
−37.4°C. Assuming these conditions, a saturated CaCl2 solution should melt ice at −34°C
(−29°F).
b. From Exercise 93, i ≈ 2.6; ΔTf = iKfm = 2.6 × 1.86 × 6.71 = 32°C; Tf = −32°C.
Assuming i = 2.6, a saturated CaCl2 solution will not melt ice at −34°C (−29°F).
π 2.50 atm
96. π = iMRT, M = = = 5.11 × 10 −2 mol/L
iRT 0 . 08206 L atm
2.00 × × 298 K
K mol
0.500 g
Molar mass of compound = = 97.8 g/mol
5.11 × 10 − 2 mol
0.1000 L ×
L
Additional Exercises
97. Benzoic acid is capable of hydrogen-bonding, but a significant part of benzoic acid is the
nonpolar benzene ring. In benzene, a hydrogen-bonded dimer forms.
O O H O
C O H C C
O H O
The dimer is relatively nonpolar and thus more soluble in benzene than in water. Because
benzoic acid forms dimers in benzene, the effective solute particle concentration will be less
than 1.0 molal. Therefore, the freezing-point depression would be less than 5.12°C (∆Tf =
Kf m).
98. Benzoic acid (see Exercise 97) would be more soluble in a basic solution because of the
reaction:
C6H5CO2H + OH− → C6H5CO2− + H2O
By removing the proton from benzoic acid, an anion forms, and like all anions, the species
becomes more soluble in water.
99. The main factor for stabilization seems to be electrostatic repulsion. The center of a colloid
particle is surrounded by a layer of same charged ions, with oppositely charged ions forming
another charged layer on the outside. Overall, there are equal numbers of charged and
oppositely charged ions, so the colloidal particles are electrically neutral. However, since the
outer layers are the same charge, the particles repel each other and do not easily aggregate for
precipitation to occur.
Heating increases the velocities of the colloidal particles. This causes the particles to collide
with enough energy to break the ion barriers, allowing the colloids to aggregate and
eventually precipitate out. Adding an electrolyte neutralizes the adsorbed ion layers, which
allows colloidal particles to aggregate and then precipitate out.
100. Water is a polar solvent because the H2O molecule exhibits a dipole moment, that is, H2O is
a molecule which has a partial negative charged end and a partial positive charged end. The
electrostatic potential diagram for H2O illustrates this with colors. The partial negative end of
the dipole moment is the red end and the partial positive end is around the blue end.
Because water is a polar solvent, it will dissolve other polar covalent compounds. The
electrostatic potential diagram for NH3 illustrates that NH3 has a dipole moment (the red end
is the partial negative end and the light blue end is the partial positive end). Because NH3 has
a dipole moment (is polar), it will be soluble in water. However, the electrostatic potential
diagram for CH4 doesn’t have one specific negative (red) end and has four blue regions
arranged symmetrically about the molecule. CH4 does not have a dipole moment (is nonpolar)
and will not be soluble in water.
101. Na3PO4(s) → 3 Na+(aq) + PO43−(aq); if the solution is ideal, i = 4.0
ΔTf = iKfm = 4.0 × 1.86 °C kg/mol × 0.25 mol/kg = 1.9°C
If ideal, the solution would have a freezing point of −1.9°C. Since the freezing point is only
−1.6°C, the solution is not ideal and there is some ion pairing in solution.
12 mL C 2 H 5 OH 0.79 g C 2 H 5 OH 1 mol C 2 H 5 OH
102. 750. mL grape juice × × ×
100. mL juice mL 46.07 g
2 mol CO 2
× = 1.54 mol CO2 (carry extra significant figure)
2 mol C 2 H 5 OH
1.54 mol CO2 = total mol CO2 = mol CO2(g) + mol CO2(aq) = ng + naq
 0.08206 L atm 
n g   (298 K )
PCO 2 =
n g RT
=  mol K  = 326ng
V 75 × 10 −3 L
n aq
C 0.750 L
PCO 2 = = = (43.0)naq
k 3.1 × 10 − 2 mol
L atm
PCO 2 = 326ng = (43.0)naq, and from above, naq = 1.54 − ng; solving:
326ng = 43.0(1.54 − ng), 369ng = 66.2, ng = 0.18 mol
PCO 2 = 326(0.18) = 59 atm in gas phase

3.1 × 10 −2 mol 1.8 mol CO 2
C = kPCO 2 = × 59 atm = (in wine)
L atm L
103. a. Water boils when the vapor pressure equals the pressure above the water. In an open pan,
Patm ≈ 1.0 atm. In a pressure cooker, Pinside > 1.0 atm, and water boils at a higher temper-
ature. The higher the cooking temperature, the faster is the cooking time.
b. When water freezes from a solution, it freezes as pure water, leaving behind a more
concentrated salt solution. Therefore, the melt of frozen sea ice is pure water.
c. In the CO2 phase diagram in Chapter 10, the triple point is above 1 atm, so CO2(g) is the
stable phase at 1 atm and room temperature. CO2(l) can't exist at normal atmospheric
pressures. Therefore, dry ice sublimes instead of boils. In a fire extinguisher, P > 1 atm,
and CO2(l) can exist. When CO2 is released from the fire extinguisher, CO2(g) forms, as
predicted from the phase diagram.
104. A 92 proof ethanol solution is 46% C2H5OH by volume. Assuming 100.0 mL of solution:
0.79 g 1 mol C 2 H 5 OH
mol ethanol = 46 mL C2H5OH × × = 0.79 mol C2H5OH
mL 46.07 g
0.79 mol
molarity = = 7.9 M ethanol
0.1000 L
105. Because partial pressures are proportional to the moles of gas present, then:
χ CS
V
2
= PCS2 /Ptotal
PCS2 = χ CS
V
P = 0.855(263 torr) = 225 torr
2 total
PCS2 225 torr

PCS2 = χ CS
L
P o , χ CS
2 CS2
L
2
= o
= = 0.600
PCS 375 torr
2
106. ∆H1 and ∆H2 refer to the breaking of intermolecular forces in pure solute and in pure solvent.
∆H3 refers to the formation of the intermolecular forces in solution between the solute and
solvent. ∆Hsoln is the sum ∆H1 + ∆H2 + ∆H3.
a. The electrostatic potential diagram illustrates that acetone (CH3COCH3), like water, is a
polar substance (each has a red end indicating the partial negative end of the dipole
moment and a blue end indicating the partial positive end). For a polar solute in a polar
solvent, ∆H1 and ∆H2 will be large and positive, while ∆H3 will be a large negative value.
As discussed in section 11.4 on nonideal solutions, acetone-water solutions exhibit
negative deviations from Raoult’s law. Acetone and water have the ability to hydrogen
bond with each other, which gives the solution stronger intermolecular forces as
compared to the pure states of both solute and solvent. In the pure state, acetone cannot
H−bond with itself. Because acetone and water show negative deviations from Raoult’s
law, one would expect ∆Hsoln to be slightly negative. Here ∆H3 will be more than
negative enough to overcome the large positive value from the ∆H1 and ∆H2 terms
combined.
b. These two molecules are named ethanol (CH3CH2OH) and water. Ethanol-water
solutions show positive deviations from Raoult’s law. Both substances can hydrogen
bond in the pure state, and they can continue this in solution. However, the solute-
solvent interactions are somewhat weaker for ethanol-water solutions due to the small
nonpolar part of ethanol (CH3CH2 is the nonpolar part of ethanol). This nonpolar part of
ethanol slightly weakens the intermolecular forces in solution. So as in part a, when a
polar solute and polar solvent are present, ∆H1 and ∆H2 are large and positive, while ∆H3
is large and negative. For positive deviations from Raoult’s law, the interactions in
solution are weaker than the interactions in pure solute and pure solvent. Here, ∆Hsoln
will be slightly positive because the ∆H3 term is not negative enough to overcome the
large, positive ∆H1 and ∆H2 terms combined.
c. As the electrostatic potential diagrams indicate, both heptane (C7H16) and hexane (C6H14)
are nonpolar substances. For a nonpolar solute dissolved in a nonpolar solvent, ∆H1 and
∆H2 are small and positive, while the ∆H3 term is small and negative. These three terms
have small values due to the relatively weak London dispersion forces that are broken
and formed for solutions consisting of a nonpolar solute in a nonpolar solvent. Because
∆H1, ∆H2, and ∆H3 are all small values, the ∆Hsoln value will be small. Here, heptane and
hexane would form an ideal solution because the relative strengths of the London
dispersion forces are about equal in pure solute and pure solvent as compared to those LD
forces in solution. For ideal solutions, ∆Hsoln = 0.
d. This combination represents a nonpolar solute in a polar solvent. ∆H1 will be small due
to the relative weak London dispersion forces which are broken when the solute (C7H16)
expands. ∆H2 will be large and positive because of the relatively strong hydrogen
bonding interactions that must be broken when the polar solvent (water) is expanded.
And finally, the ∆H3 term will be small because the nonpolar solute and polar solvent do
not interact with each other. The end result is that ∆Hsoln is a large positive value.
1 mol
107. 50.0 g CH3COCH3 × = 0.861 mol acetone
58.08 g
1 mol
50.0 g CH3OH × = 1.56 mol methanol
32.04 g
0.861
χ acetone
L
= = 0.356; χ Lmethanol = 1.000 − χ acetone
L
= 0.644
0.861 + 1.56
Ptotal = Pmethanol + Pacetone = 0.644(143 torr) + 0.356(271 torr) = 92.1 + 96.5 = 188.6 torr
Because partial pressures are proportional to the moles of gas present, in the vapor phase:
Pacetone 96.5 torr
χ acetone
V
= = = 0.512; χ Vmethanol = 1.000 − 0.512 = 0.488
Ptotal 188.6 torr
The actual vapor pressure of the solution (161 torr) is less than the calculated pressure
assuming ideal behavior (188.6 torr). Therefore, the solution exhibits negative deviations
from Raoult’s law. This occurs when the solute-solvent interactions are stronger than in pure
solute and pure solvent.
0.1 mol 0.08206 L atm

108. π = MRT = × × 298 K = 2.45 atm ≈ 2 atm
L K mol
760 mm Hg
π = 2 atm × ≈ 2000 mm ≈ 2 m
atm
The osmotic pressure would support a mercury column of approximately 2 m. The height of
a fluid column in a tree will be higher because Hg is more dense than the fluid in a tree. If we
assume the fluid in a tree is mostly H2O, then the fluid has a density of 1.0 g/cm3. The
density of Hg is 13.6 g/cm3.
Height of fluid ≈ 2 m × 13.6 ≈ 30 m
∆Tf 0.300 °C 5.86 × 10 −2 mol thyroxine

109. ΔTf = Kfm, m = = =
Kf 5.12 °C kg/mol kg benzene
The moles of thyroxine present are:
5.86 × 10 −2 mol thyroxine

0.0100 kg benzene × = 5.86 × 10 −4 mol thyroxine
kg benzene
From the problem, 0.455 g thyroxine was used; this must contain 5.86 × 10 −4 mol thyroxine.
The molar mass of the thyroxine is:
0.455 g
molar mass = = 776 g/mol
5.86 × 10 − 4 mol
π 8.00 atm
110. π = MRT, M = = = 0.327 mol/L
RT 0.08206 L atm/K • mol × 298 K
111. Out of 100.00 g, there are:

1 mol C 2.629
31.57 g C × = 2.629 mol C; = 1.000
12.01 g 2.629
1 mol H 5.26
5.30 g H × = 5.26 mol H; = 2.00
1.008 g 2.629
1 mol O 3.946
63.13 g O × = 3.946 mol O; = 1.501
16.00 g 2.629
Empirical formula: C2H4O3; use the freezing-point data to determine the molar mass.
∆Tf 5.20 °C
m= = = 2.80 molal
Kf 1.86 °C/molal
2.80 mol solute
Mol solute = 0.0250 kg × = 0.0700 mol solute
kg
10.56 g
Molar mass = = 151 g/mol
0.0700 mol
The empirical formula mass of C2H4O3 = 76.05 g/mol. Because the molar mass is about twice
the empirical mass, the molecular formula is C4H8O6, which has a molar mass of 152.10
g/mol.
Note: We use the experimental molar mass to determine the molecular formula. Knowing
this, we calculate the molar mass precisely from the molecular formula using the atomic
masses in the periodic table.
112. a. As discussed in Figure 11.19 of the text, the water would migrate from left to right (to the
side with the solution). Initially, the level of liquid in the left arm would go down, and the
level in the right arm would go up. At some point the rate of solvent (H2O) transfer will
be the same in both directions, and the levels of the liquids in the two arms will stabilize.
The height difference between the two arms is a measure of the osmotic pressure of the
solution.
b. Initially, H2O molecules will have a net migration into the solution side. However, the
solute can now migrate into the H2O side. Because solute and solvent transfer are both
possible, the levels of the liquids will be equal once the rates of solute and solvent
transfer are equal in both directions. At this point the concentration of solute will be equal
in both chambers, and the levels of liquid will be equal.
113. If ideal, NaCl dissociates completely, and i = 2.00. ΔTf = iKfm; assuming water freezes at
0.00°C:
1.28°C = 2 × 1.86°C kg/mol × m, m = 0.344 mol NaCl/kg H2O
Assume an amount of solution that contains 1.00 kg of water (solvent).
58.44 g
0.344 mol NaCl × = 20.1 g NaCl
mol
20.1 g
Mass % NaCl = × 100 = 1.97%
1.00 × 103 g + 20.1 g
114. The pair of compounds which have similar strength intermolecular forces will behave most
ideally. This will be the pair of compounds which have the most similar structures.
a. CH3(CH2)6CH3 and CH3(CH2)5CH3 have similar nonpolar structures so this pair will
behave most ideally. CH3-O-CH3 will have significantly weaker intermolecular forces
than H2O which exhibits extensive hydrogen bonding.
b. CH3OH and CH3CH2OH have the most similar structures and will behave most ideally.
HF, with its ability to hydrogen bond, will have significantly stronger intermolecular
forces than CH3F which cannot hydrogen bond.
ΔT 2.79 o C
115. ∆T = Kfm, m = = = 1.50 molal
Kf 1.86 o C/molal
a. ∆T = Kbm, ∆T = (0.51°C/molal)(1.50 molal) = 0.77°C, Tb = 100.77°C

mol H 2 O
b. Psoln = χ water Pwater
o
, χ water =
mol H 2 O + mol solute
Assuming 1.00 kg of water, we have 1.50 mol solute, and:
1 mol H 2 O
mol H2O = 1.00 × 103 g H2O × = 55.5 mol H2O
18.02 g H 2 O
55.5 mol
χwater = = 0.974; Psoln = (0.974)(23.76 mm Hg) = 23.1 mm Hg
1.50 + 55.5
c. We assumed ideal behavior in solution formation, we assumed the solute was nonvolatile,
and we assumed i = 1 (no ions formed).
2.0 mol A
116. χ LA = = 0.40, χ LB = 1.00 – 0.40 = 0.60; Ptotal = PA + PB; P = χ L P o
5.0 mol total
Ptotal = 240. torr = 0.40(150 torr) + 0.60( PBo ), PBo = 3.0 × 102 torr
0.995 g
117. Mass of H2O = 160. mL × = 159 g = 0.159 kg
mL
0.378 mol
Mol NaDTZ = 0.159 kg × = 0.0601 mol
kg
38.4 g
Molar mass of NaDTZ = = 639 g/mol
0.0601 mol
1 mol
Psoln = χ H 2O PHo 2O ; mol H2O = 159 g × = 8.82 mol
18.02 g
Sodium diatrizoate is a salt because there is a metal (sodium) in the compound. From the
short-hand notation for sodium diatrizoate, NaDTZ, we can assume this salt breaks up into
Na+ and DTZ− ions. So the moles of solute particles are 2(0.0601) = 0.120 mol solute
particles.
8.82 mol
χ H 2O = = 0.987; Psoln = 0.987 × 34.1 torr = 33.7 torr
0.120 mol + 8.82 mol
ChemWork Problems
mass CsCl 52.3 g
118. Mass % CsCl = × 100 = × 100 = 46.6%
total mass 52.3 g + 60.0. g
1 mol
Mol CsCl = 52.3 g × = 0.311 mol CsCl
168.4 g
1 mol
Mol H2O = 60.0 g × = 3.33 mol H2O
18.02 g
mol CsCl 0.311 mol CsCl
Molarity = = = 4.91 mol/L
L solution 0.0633 L
mol CsCl 0.311 mol CsCl
Molality = = = 5.18 mol/kg
kg solvent 0.0600 kg
mol CsCl 0.331 mol
Mole fraction = χCsCl = = = 0.0904
total mol 0.331 mol + 3.33 mol
119. Using Hess’s law:
NaCl(s) → Na+(g) + Cl−(g) ΔH = −ΔHLE = −(−786 kJ/mol)

Na+(g) + Cl−(g) → Na+(aq) + Cl−(aq) ΔH = ΔHhyd = −783 kJ/mol
NaCl(s) → Na+(aq) + Cl−(aq) ΔHsoln = 3 kJ/mol
ΔHsoln refers to the heat released or gained when a solute dissolves in a solvent. Here, an
ionic compound dissolves in water.
120. Water exhibits H-bonding in the pure state and is classified as a polar solvent. Water will
dissolve other polar solutes and ionic solutes.
a. NH3; NH3 is more polar CH3NH3. The CH3 group, like all hydrocarbon groups, is a
nonpolar group.
b. CH3CN; CH3CN is more polar than CH3OCH3 due to the 2 nonpolar CH3 groups in
CH3OCH3.
c. CH3CH2OH; CH3CH2OH is polar while CH3CH2CH3 is nonpolar.
d. CH3OH; CH3OH is more polar than CH3CH2OH.
e. (CH3)3CCH2OH; (CH3)3CCH2OH has a slightly smaller nonpolar part than

CH3(CH2)6OH. Neither compound would be expected to be very soluble in water.
f. CH3CO2H; CH3CO2H is capable of H-bonding, unlike the other compound.
121. The normal boiling point of a substance is the boiling point at 1 atm pressure. So for this
problem, P° = 760. torr at 64.7°C (the normal boiling point of methanol).
P = χP°; 556 torr = χ(760. torr), χ = 0.732 = mole fraction of methanol
1.000 mol CH 3 OH
122. Ptotal = PCH 3OH + PCH 3CH 2CH 2OH ; P = χ L P o ; χ CH
L
3OH
= = 0.239
4.18 mol total
Ptotal = 0.239(303 torr) + (1.000 − 0.239)(44.6 torr) = 72.4 + 33.9 = 106.3 torr
PCH 3OH 72.4 torr
In the vapor: χ CH
V
3 OH
= = = 0.681
Ptotal 106.3 torr
χ CH
V
3CH 2 CH 2 OH
= 1.000 – 0.681 = 0.319
assumed.
mol solute 35.0 g solute 1000 g 1 mol solute

123. Molality = m = = × × = 1.01 molal
kg solvent 600.0 g H 2 O kg 58.0 g solute
0.51 °C
ΔTb = Kbm = × 1.01 molal = 0.52°C; 99.725 oC + 0.52 oC = 100.25 oC
molal
The boiling point is raised from 99.725 oC to 100.25°C.
1 atm 0.08206 L atm

124. π = MRT, π = 0.56 torr × =M× × 298 K, M = 3.0 × 10−5 mol/L
760 torr K mol
3.0 × 10 −5 mol protein
Mol protein = 0.00025 L × = 7.5 × 10−9 mol protein
L
4.7 × 10 −5 g
7.5 × 10 −9 mol
ΔTf 5.23 o C
125. m= = = 2.81 molal
Kf 1.86 o C/molal
2.81 mol solute n
= , n = 0.141 mol of ions in solution
kg solvent 0.0500 kg
Since NaNO3 and Mg(NO3)2 are strong electrolytes:
0.141 mol ions = 2(x mol of NaNO3) + 3[y mol of Mg(NO3)2]
85.00 g 148.3 g
In addition: 6.50 g = x mol NaNO3 × + y mol of Mg(NO3)2 ×
mol mol
We have two equations: 2x + 3y = 0.141 and 85.00 x + 148.3 y = 6.50
Solving by simultaneous equations:
−85.00 x – 127.5 y = −5.99

85.00 x + 148.3 y = 6.50
20.8 y = 0.51, y = 0.025 mol Mg(NO3)2
148.3 g
Mass of Mg(NO3)2 = 0.025 mol × = 3.7 g Mg(NO3)2
mol
Mass of NaNO3 = 6.50 g – 3.7 g = 2.8 g NaNO3
2.8 g
Mass % NaNO3 = × 100 = 43% NaNO3 and 57% Mg(NO3)2 by mass
6.50 g
Challenge Problems
126. For the second vapor collected, χ VB, 2 = 0.714 and χ TV, 2 = 0.286. Let χ BL , 2 = mole fraction of
benzene in the second solution and χ TL, 2 = mole fraction of toluene in the second solution.
χ LB, 2 + χ TL, 2 = 1.000
PB PB χ LB, 2 (750.0 torr )

χ VB, 2 = 0.714 = = = L
Ptotal PB + PT χ B, 2 (750.0 torr ) + (1.000 − χ BL , 2 )(300.0 torr )
Solving: χ LB, 2 = 0.500 = χ TL, 2
This second solution came from the vapor collected from the first (initial) solution, so, χ BV, 1 =
χ TV, 1 = 0.500. Let χ BL , 1 = mole fraction benzene in the first solution and χ TL, 1 = mole fraction
of toluene in first solution. χ BL , 1 + χ TL, 1 = 1.000.
PB PB χ BL , 1 (750.0 torr )
χ BV, 1 = 0.500 = = = L
Ptotal PB + PT χ B, 1 (750.0 torr ) + (1.000 − χ BL , 1 )(300.0 torr )
Solving: χ BL , 1 = 0.286; the original solution had χB = 0.286 and χT = 0.714.
PA
127. For 30.% A by moles in the vapor, 30. = × 100:
PA + PB
χAx χAx
0.30 = , 0.30 =
χAx + χBy χ A x + (1.00 − χ A ) y
χA x = 0.30(χA x) + 0.30 y – 0.30(χA y), χA x – (0.30)χA x + (0.30)χA y = 0.30 y
0.30 y
χA(x – 0.30 x + 0.30 y) = 0.30 y, χA = ; χB = 1.00 – χA
0.70 x + 0.30 y
y y
Similarly, if vapor above is 50.% A: χ A = ; χ B = 1.00 −
x+ y x+ y
0.80 y
If vapor above is 80.% A: χA = ; χB = 1.00 − χA
0.20 x + 0.80 y
If the liquid solution is 30.% A by moles, χA = 0.30.

PA 0.30 x 0.30 x
Thus χ VA = = and χ VB = 1.00 −
PA + PB 0.30 x + 0.70 y 0.30 x + 0.70 y
x
If solution is 50.% A: χ VA = and χ VB = 1.00 − χ VA
x+ y
0.80 x
If solution is 80.% A: χ VA = and χ VB = 1.00 − χ VA
0.80 x + 0.20 y
128. a. Freezing-point depression is determined using molality for the concentration units,
whereas molarity units are used to determine osmotic pressure. We need to assume that
the molality of the solution equals the molarity of the solution.
moles solvent moles solvent
b. Molarity = ; molality =
liters solution kg solvent
When the liters of solution equal the kilograms of solvent present for a solution, then
molarity equals molality. This occurs for an aqueous solution when the density of the
solution is equal to the density of water, 1.00 g/cm3. The density of a solution is close to
1.00 g/cm3 when not a lot of solute is dissolved in solution. Therefore, molarity and
molality values are close to each other only for dilute solutions.
ΔT 0.621o C
c. ∆T = Kf m, m = = = 0.334 mol/kg
Kf 1.86 o C kg/mol
Assuming 0.334 mol/kg = 0.334 mol/L:
0.334 mol 0.08206 L atm
π = MRT = × × 298 K = 8.17 atm
L K mol
ΔT 2.0 o C
d. m = = = 3.92 mol/kg
Kb 0.51 o C kg/mol
This solution is much more concentrated than the isotonic solution in part c. Here, water
will leave the plant cells in order to try to equilibrate the ion concentration both inside
and outside the cell. Because there is such a large concentration discrepancy, all the
water will leave the plant cells, causing them to shrivel and die.
ΔTf 0.426 o C
129. m= = = 0.229 molal
Kf 1.86 o C / molal
Assuming a solution density = 1.00 g/mL, then 1.00 L contains 0.229 mol solute.
NaCl → Na+ + Cl− i = 2; so: 2(mol NaCl) + mol C12H22O11 = 0.229 mol
Mass NaCl + mass C12H22O11 = 20.0 g
2nNaCl + nC12 H 22O11 = 0.229 and 58.44(nNaCl) + 342.3(nC12 H 22O11 ) = 20.0
Solving: nC12 H 22O11 = 0.0425 mol = 14.5 g and nNaCl = 0.0932 mol = 5.45 g
Mass % C12H22O11 = (14.5 g/20.0 g) × 100 = 72.5 % and 27.5% NaCl by mass
0.0425 mol
χ C12 H 22O11 = = 0.313
0.0425 mol + 0.0932 mol
π 7.83 atm
130. a. π = iMRT, iM = = = 0.320 mol/L
RT 0.08206 L atm/K • mol × 298 K
Assuming 1.000 L of solution:
total mol solute particles = mol Na+ + mol Cl− + mol NaCl = 0.320 mol
1.071 g
mass solution = 1000. mL × = 1071 g solution
mL
mass NaCl in solution = 0.0100 × 1071 g = 10.7 g NaCl
1 mol
mol NaCl added to solution = 10.7 g × = 0.183 mol NaCl
58.44 g
Some of this NaCl dissociates into Na+ and Cl− (two moles of ions per mole of NaCl),
and some remains undissociated. Let x = mol undissociated NaCl = mol ion pairs.
Mol solute particles = 0.320 mol = 2(0.183 − x) + x
0.320 = 0.366 − x, x = 0.046 mol ion pairs

0.046
Fraction of ion pairs = = 0.25, or 25%
0.183
b. ΔT = Kfm, where Kf = 1.86 °C kg/mol; from part a, 1.000 L of solution contains 0.320
mol of solute particles. To calculate the molality of the solution, we need the kilograms
of solvent present in 1.000 L of solution.
Mass of 1.000 L solution = 1071 g; mass of NaCl = 10.7 g
Mass of solvent in 1.000 L solution = 1071 g − 10.7 g = 1060. g

0.320 mol
ΔT = 1.86 °C kg/mol × = 0.562°C
1.060 kg
Assuming water freezes at 0.000°C, then Tf = −0.562°C.
Ppen
131. χ Vpen = 0.15 = ; Ppen = χ Lpen Ppen
o
; Ptotal = Ppen + Phex = χ Lpen (511) + χ Lhex (150.)
Ptotal
Because χ hex
L
= 1.000 − χ Lpen : Ptotal = χ pen
L
(511) + (1.000 − χ pen
L
)(150.) = 150. + 361χ pen
L
Ppen χ Lpen (511)

χ Vpen = , 0.15 = , 0.15(150. + 361 χ pen
L
) = 511 χ Lpen
Ptotal 150. + 361 χ Lpen
23
23 + 54 χ Lpen = 511 χ Lpen , χ Lpen = = 0.050
457
ΔTf 1.32 o C
132. a. m = = = 0.258 mol/kg
Kf 5.12 o C kg/mol
0.258 mol unknown

Mol unknown = 0.01560 kg × = 4.02 × 10−3 mol
kg
1.22 g
Molar mass of unknown = = 303 g/mol
4.02 × 10 −3 mol
0.04
Uncertainty in temperature = × 100 = 3%
1.32
A 3% uncertainty in 303 g/mol = 9 g/mol.
So molar mass = 303 ±9 g/mol.
b. No, codeine could not be eliminated since its molar mass is in the possible range
including the uncertainty.
c. We would like the uncertainty to be ±1 g/mol. We need the freezing-point depression to

be about 10 times what it was in this problem. Two possibilities are:
(1) make the solution 10 times more concentrated (may be solubility problem)
(2) use a solvent with a larger Kf value, e.g., camphor
ΔTf 2.70 o C
133. ΔTf = 5.51 − 2.81 = 2.70°C; m = = = 0.527 molal
Kf 5.12 o C/molal
Let x = mass of naphthalene (molar mass = 128.2 g/mol). Then 1.60 − x = mass of
anthracene (molar mass = 178.2 g/mol).
x 1.60 − x
= moles naphthalene and = moles anthracene
128.2 178.2
x 1.60 − x
+
0.527 mol solute
= 128.2 178.2 , 1.05 × 10 − 2 = (178.2) x + 1.60(128.2) − (128.2) x
kg solvent 0.0200 kg solvent 128.2(178.2)
(50.0)x + 205 = 240., (50.0)x = 240. − 205, (50.0)x = 35, x = 0.70 g naphthalene
So the mixture is:

0.70 g
× 100 = 44% naphthalene by mass and 56% anthracene by mass
1.60 g
π 0.3950 atm
134. iM = = = 0.01614 mol/L = total ion concentration
RT 0.08206 L atm
× 298.2 K
K mol
0.01614 mol/L = M Mg 2+ + M Na + + M Cl − ; M Cl − = 2M Mg 2 + + M Na + (charge balance)
Combining: 0.01614 = 3M Mg 2 + + 2M Na +
Let x = mass MgCl2 and y = mass NaCl; then x + y = 0.5000 g.

x y
M Mg 2 + = and M Na + = (Because V = 1.000 L.)
95.21 58.44
3x 2y
Total ion concentration = + = 0.01614 mol/L
95.21 58.44
Rearranging: 3x + (3.258)y = 1.537
Solving by simultaneous equations:
3x + (3.258)y = 1.537
–3(x + y) = –3(0.5000)
(0.258)y = 0.037, y = 0.14 g NaCl
0.36 g
Mass MgCl2 = 0.5000 g − 0.14 g = 0.36 g; mass % MgCl2 = × 100 = 72%
0.5000 g
135. HCO2H → H+ + HCO2−; only 4.2% of HCO2H ionizes. The amount of H+ or HCO2−
produced is 0.042 × 0.10 M = 0.0042 M.
The amount of HCO2H remaining in solution after ionization is 0.10 M − 0.0042 M = 0.10 M.
The total molarity of species present = M HCO 2 H + M H + + M HCO −

2
= 0.10 + 0.0042 + 0.0042 = 0.11 M
Assuming 0.11 M = 0.11 molal, and assuming ample significant figures in the freezing point
and boiling point of water at P = 1 atm:
ΔT = Kfm = 1.86°C/molal × 0.11 molal = 0.20°C; freezing point = –0.20°C
ΔT = Kbm = 0.51°C/molal × 0.11 molal = 0.056°C; boiling point = 100.056°C
136. Let χ LA = mole fraction A in solution, so 1.000 − χ LA = χ LB . From the problem, χ VA = 2 χ LA .

PA χ LA (350.0 torr )
χ VA = = L
Ptotal χ A (350.0 torr ) + (1.000 − χ LA )(100.0 torr )
(350.0)χ LA
χ VA = 2 χ LA = , (250.0)χ LA = 75.0, χ LA = 0.300
(250.0)χ LA + 100.0
The mole fraction of A in solution is 0.300.
137. a. Assuming MgCO3(s) does not dissociate, the solute concentration in water is:
560 μg MgCO 3 (s) 560 mg 560 × 10 −3 g 1 mol MgCO 3

= = ×
mL L L 84.32 g
= 6.6 × 10−3 mol MgCO3/L
An applied pressure of 8.0 atm will purify water up to a solute concentration of:
π 8.0 atm 0.32 mol

M = = =
RT 0.08206 L atm/K mol × 300. K L
When the concentration of MgCO3(s) reaches 0.32 mol/L, the reverse osmosis unit can
no longer purify the water. Let V = volume (L) of water remaining after purifying 45 L
of H2O. When V + 45 L of water has been processed, the moles of solute particles will
equal:
6.6 × 10−3 mol/L × (45 L + V) = 0.32 mol/L × V
Solving: 0.30 = (0.32 − 0.0066) × V, V = 0.96 L
The minimum total volume of water that must be processed is 45 L + 0.96 L = 46 L.
Note: If MgCO3 does dissociate into Mg2+ and CO32− ions, then the solute concentration
increases to 1.3 × 10−2 M, and at least 47 L of water must be processed.
b. No; a reverse osmosis system that applies 8.0 atm can only purify water with a solute
concentration of less than 0.32 mol/L. Salt water has a solute concentration of 2(0.60 M)
= 1.2 mol/L ions. The solute concentration of salt water is much too high for this reverse
osmosis unit to work.
138. a. The average values for each ion are:
300. mg Na+, 15.7 mg K+, 5.45 mg Ca2+, 388 mg Cl−, and 246 mg lactate (C3H5O3−)
Note: Because we can precisely weigh to ±0.1 mg on an analytical balance, we'll carry
extra significant figures and calculate results to ±0.1 mg.
The only source of lactate is NaC3H5O3.

112.06 mg NaC3 H 5 O 3
246 mg C3H5O3− × −
= 309.5 mg sodium lactate
89.07 mg C 3 H 5 O 3
The only source of Ca2+ is CaCl2•2H2O.

147.0 mg CaCl 2 • 2H 2 O
5.45 mg Ca2+ × = 19.99 or 20.0 mg CaCl2•2H2O
40.08 mg Ca 2+
The only source of K+ is KCl.
74.55 mg KCl
15.7 mg K+ × = 29.9 mg KCl
39.10 mg K +
From what we have used already, let's calculate the mass of Na+ added.
309.5 mg sodium lactate − 246.0 mg lactate = 63.5 mg Na+
Thus we need to add an additional 236.5 mg Na+ to get the desired 300. mg.
58.44 mg NaCl
236.5 mg Na+ × = 601.2 mg NaCl
22.99 mg Na +
Now let's check the mass of Cl− added:
70.90 mg Cl −
20.0 mg CaCl2•2H2O × = 9.6 mg Cl−
147.0 mg CaCl 2 • 2H 2 O
20.0 mg CaCl2•2H2O = 9.6 mg Cl−

29.9 mg KCl − 15.7 mg K+ = 14.2 mg Cl−
601.2 mg NaCl − 236.5 mg Na+ = 364.7 mg Cl−
Total Cl− = 388.5 mg Cl−
This is the quantity of Cl− we want (the average amount of Cl−).
An analytical balance can weigh to the nearest 0.1 mg. We would use 309.5 mg sodium
lactate, 20.0 mg CaCl2•2H2O, 29.9 mg KCl, and 601.2 mg NaCl.
b. To get the range of osmotic pressure, we need to calculate the molar concentration of
each ion at its minimum and maximum values. At minimum concentrations, we have:
285 mg Na + 1 mmol 14.1 mg K + 1 mmol
× = 0.124 M; × = 0.00361 M
100. mL 22.99 mg 100. mL 39.10 mg
4.9 mg Ca 2+ 1 mmol 368 mg Cl − 1 mmol
× = 0.0012 M; × = 0.104 M
100. mL 40.08 mg 100. mL 35.45 mg
−
231 mg C 3 H 5 O 3 1 mmol
× = 0.0259 M (Note: molarity = mol/L = mmol/mL.)
100. mL 89.07 mg
Total = 0.124 + 0.00361 + 0.0012 + 0.104 + 0.0259 = 0.259 M
0.259 mol 0.08206 L atm
π = MRT = × × 310. K = 6.59 atm
L K mol
Similarly, at maximum concentrations, the concentration for each ion is:
Na+: 0.137 M; K+: 0.00442 M; Ca2+: 0.0015 M; Cl−: 0.115 M; C3H5O3−: 0.0293 M
The total concentration of all ions is 0.287 M.

0.287 mol 0.08206 L atm
π= × × 310. K = 7.30 atm
L K mol
Osmotic pressure ranges from 6.59 atm to 7.30 atm.
Integrative Problems
139. a. NH4NO3(s) → NH4+(aq) + NO3−(aq) ΔHsoln = ?
Heat gain by dissolution process = heat loss by solution; we will keep all quantities posi-
tive in order to avoid sign errors. Because the temperature of the water decreased, the
dissolution of NH4NO3 is endothermic (ΔH is positive). Mass of solution = 1.60 + 75.0
= 76.6 g.
4.18 J
Heat loss by solution = × 76.6 g × (25.00°C − 23.34°C) = 532 J
°C g
532 J 80.05 g NH 4 NO 3
ΔHsoln = × = 2.66 × 104 J/mol = 26.6 kJ/mol
1.60 g NH 4 NO 3 mol NH 4 NO 3
b. We will use Hess’s law to solve for the lattice energy. The lattice-energy equation is:
NH4+(g) + NO3−(g) → NH4NO3(s) ΔH = lattice energy
NH4+(g) + NO3−(g) → NH4+(aq) + NO3−(aq) ΔH = ΔHhyd = –630. kJ/mol

NH4+(aq) + NO3−(aq) → NH4NO3(s) ΔH = –ΔHsoln = –26.6 kJ/mol
NH4+(g) + NO3−(g) → NH4NO3(s) ΔH = ΔHhyd – ΔHsoln
ΔH = –657 kJ/mol
1L 10 dL 1.0 mg C 4 H 7 N 3 O 1g 1 mol C 4 H 7 N 3 O
140. 10.0 mL blood × × × × ×
1000 mL 1L 1 dL blood 1000 mg 113.13 g
= 8.8 × 10 −7 mol C4H7N3O
1.025 g
Mass of blood = 10.0 mL × = 10.3 g
mL
8.8 × 10 −7 mol
Molality = = 8.5 × 10 −5 mol/kg
0.0103 kg
8.8 × 10 −7 mol
π = MRT, M = = 8.8 × 10 −5 mol/L
0.0100 L
0.08206 L atm
π = 8.8 × 10 −5 mol/L × × 298 K = 2.2 × 10 −3 atm
K mol
ΔT 2.79 o C
141. ∆T = imKf, i = = = 3.00
mK f 0.250 mol 1.86 o C kg
×
0.500 kg mol
We have three ions in solutions, and we have twice as many anions as cations. Therefore, the
formula of Q is MCl2. Assuming 100.00 g of compound:
1 mol Cl
38.68 g Cl × = 1.091 mol Cl
35.45 g
1 mol M
mol M = 1.091 mol Cl × = 0.5455 mol M
2 mol Cl
61.32 g M
Molar mass of M = = 112.4 g/mol; M is Cd, so Q = CdCl2.
0.5455 mol M
12.01 mg C 3.88 mg
142. 14.2 mg CO2 × = 3.88 mg C; % C = × 100 = 80.8% C
44.01 mg CO 2 4.80 mg
2.016 mg H 0.185 mg
1.65 mg H2O × = 0.185 mg H; % H = × 100 = 3.85% H
18.02 mg H 2 O 4.80 mg
Mass % O = 100.00 − (80.8 + 3.85) = 15.4% O
Out of 100.00 g:
1 mol 6.73
80.8 g C × = 6.73 mol C; = 6.99 ≈ 7
12.01 g 0.963
1 mol 3.82
3.85 g H × = 3.82 mol H; = 3.97 ≈ 4
1.008 g 0.963
1 mol 0.963
15.4 g O × = 0.963 mol O; = 1.00
16.00 g 0.963
Therefore, the empirical formula is C7H4O.
ΔTf 22.3 o C
ΔTf = Kfm, m = = = 0.56 molal
Kf 40. o C / molal
0.56 mol anthraquinone
Mol anthraquinone = 0.0114 kg camphor × = 6.4 × 10−3 mol
kg camphor
1.32 g
Molar mass = = 210 g/mol
6.4 × 10 −3 mol
The empirical mass of C7H4O is 7(12) + 4(1) + 16 ≈ 104 g/mol. Because the molar mass is
twice the empirical mass, the molecular formula is C14H8O2.

Properties of Solutions: Solution Review

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CHAPTER 11

0.100 mol 134.00 g

0.040 mol HCl 1L

1 mol CaCl 2 1L 1000 mL

total mol Na + 0.42 mol + 0.030 mol 0.45 mol

18. a. HNO3(l) → H+(aq) + NO3−(aq) b. Na2SO4(s) → 2 Na+(aq) + SO42−(aq)

c. Al(NO3)3(s) → Al3+(aq) + 3 NO3−(aq) d. SrBr2(s) → Sr2+(aq) + 2 Br−(aq)

e. KClO4(s) → K+(aq) + ClO4−(aq) f. NH4Br(s) → NH4+(aq) + Br−(aq)

g. NH4NO3(s) → NH4+(aq) + NO3−(aq) h. CuSO4(s) → Cu2+(aq) + SO42−(aq)

i. NaOH(s) → Na+(aq) + OH−(aq)

NH3(aq) + H2O(l) → NH4+(aq) + OH−(aq)

2.5 mol NaCl 58.44 g

1 mol 0.025 mol

χ H 2O = 1.000 – 0.0180 = 0.9820

40.0 g C 2 H 6 O 2 1000 g 1 mol C 2 H 6 O 2

39. Hydrochloric acid (HCl):

38 g HCl 1.19 g soln 1000 cm 3 1 mol HCl

70. g HNO 3 1.42 g soln 1000 cm 3 1 mol HNO 3

95 g H 2SO 4 1.84 g soln 1000 cm 3 1 mol H 2SO 4

99 g CH 3CO 2 H 1.05 g soln 1000 cm 3 1 mol

99 g CH 3CO 2 H 1000 g 1 mol

28 g NH 3 0.90 g 1000 cm 3 1 mol

40. a. If we use 100. mL (100. g) of H2O, we need:

0.63 g 0.63 g 1 mol

43. If we have 100.0 mL of wine:

1.00 mol acetone 1 mol

45. If we have 1.00 L of solution:

normality = 3 × 1.37 M = 4.11 N

0.250 mol HCl 1 equivalent 0.250 equivalents

5.3 × 10 −2 mol H 3 PO 4 3 equivalents 0.16 equivalents

Equivalent mass = 1/2[molar mass of Ca (OH) 2 ] = 1/2(74.10) = 37.05 g

Energetics of Solutions and Solubility

47. Using Hess’s law:

NaI(s) → Na+(g) + I−(g) ΔH = −ΔHLE = −(−686 kJ/mol)

48. a. CaCl2(s) → Ca2+(g) + 2 Cl−(g) ΔH = −ΔHLE = −(−2247 kJ)

−46 kJ = 2247 kJ + ΔHhyd, ΔHhyd −2293 kJ

CaI2(s) → Ca2+(g) + 2 I−(g) ΔH = −ΔHLE = −(−2059 kJ)

−104 kJ = 2059 kJ + ΔHhyd, ΔHhyd = –2163 kJ

a. KrF2, 8 + 2(7) = 22 e− b. SF2, 6 + 2(7) = 20 e−

nonpolar; soluble in CCl4 polar; soluble in H2O

c. SO2, 6 + 2(6) = 18 e− d. CO2, 4 + 2(6) = 16 e−

polar; soluble in H2O nonpolar; soluble in CCl4

e. MgF2 is an ionic compound so it is soluble in water.

f. CH2O, 4 + 2(1) + 6 = 12 e− g. C2H4, 2(4) + 4(1) = 12 e−

polar; soluble in H2O nonpolar (like all compounds made up of

a. Water; Cu(NO3)2 is an ionic compound.

b. C6H14; CS2 is a nonpolar molecule. c. Water; CH3OH is polar.

e. Water; HCl is polar. f. C6H14; C6H6 is nonpolar.

a. NH3; NH3 is capable of H-bonding, unlike PH3.

b. CH3CN; CH3CN is polar, while CH3CH3 is nonpolar.

c. CH3CO2H; CH3CO2H is capable of H-bonding, unlike the other compound.

a. Mg2+; smaller size, higher charge b. Be2+; smaller size

c. Fe3+; smaller size, higher charge d. F−; smaller size

e. Cl−; smaller size f. SO42−; higher charge

56. The main intermolecular forces are:

hexane (C6H14): London dispersion; chloroform (CHCl3): dipole-dipole, London

1.3 × 10 −3 mol 1 atm

Vapor Pressures of Solutions

62. PB = χ B PBo , χ B = PB / PBo = 0.900 atm/0.930 atm = 0.968