SM Chapter 17

CHAPTER 17
PROPERTIES OF SOLUTIONS
Solution Composition
12.
Mass percent: the percent by mass of the solute in the solution.

Mole fraction: the ratio of the number of moles of a given component to the total number of
moles of solution.
Molarity: the number of moles of solute per liter of solution.
Molality: the number of moles of solute per kilogram of solvent.
Volume is temperature-dependent, whereas mass and the number of moles are not. Only
molarity has a volume term, so only molarity is temperature-dependent.
13.
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.
g. NH4NO3(s) NH4+(aq) + NO3(aq)
h. CuSO4(s) Cu2+(aq) + SO42(aq)
i.
14.
NH4Br(s) NH4+(aq) + Br(aq)
NaOH(s) Na+(aq) + OH(aq)
Mol Na2CO3 = 0.0700 L
3.0 mol Na 2 CO 3
= 0.21 mol Na2CO3
L
Na2CO3(s) 2 Na+(aq) + CO32(aq); mol Na+ = 2(0.21) = 0.42 mol

Mol NaHCO3 = 0.0300 L
1.0 mol NaHCO3

= 0.030 mol NaHCO3
L
NaHCO3(s) Na+(aq) + HCO3(aq); mol Na+ = 0.030 mol

M Na
totalmol Na
0.42 mol 0.030 mol 0.45 mol
= 4.5 M Na+
totalvolume
0.0700 L 0.030 L
0.1000 L
709
710
15.
CHAPTER 17
If we have 1.00 L of solution:

1.37 mol citric acid
192.1 g
= 263 g citric acid
mol
1.00 103 mL solution

Mass % of citric acid =
1.10 g
= 1.10 103 g solution
mL
263 g
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.
Molality =
1.37 mol citric acid

= 1.6 mol/kg
0.84 kg H 2 O
840 g H2O
16.
1.37
1 mol
= 47 mol H2O; citric acid
= 0.028
47 1.37
18.0 g
a. If we use 100. mL (100. g) of H2O, we need:

0.100 kg H2O
2.0 mol KCl

74.55 g
= 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 dont know the density of the solution, we cant 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 would probably be less than 100 mL.
To make sure we have enough solution, lets 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, lets use 100. mL CH3OH. Let x = mass of NaOH.
100. mL CH3OH 0.79 g/mL = 79 g CH3OH
Mass % = 25 =
x
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, lets use 100. mL (100. g) of H2O. Let x = mol
C6H12O6.
CHAPTER 17
100. g H2O
711
1 mol H 2 O
= 5.55 mol H2O
18.02 g
x
, (0.10)x + 0.56 = x, x = 0.62 mol C6H12O6
x 5.55
C6H12O6 = 0.10 =
0.62 mol C6H12O6 180.2 g/mol = 110 g C6H12O6

Dissolve 110 g C6H12O6 in 100. mL of H2O to prepare a solution with C6H12O6 = 0.10.
17.
Molality =
40.0 g EG
1000 g 1 mol EG
= 10.7 mol/kg
60.0 g H 2 O
kg
62.07 g
Molarity =
40.0 g EG
1.05 g 1000 cm3
1 mol
= 6.77 mol/L
3
100.0 g solution
L
62.07 g
cm
40.0 g EG
EG
18.
1 mol
1 mol
= 0.644 mol EG; 60.0 g H2O
= 3.33 mol H2O
18.02 g
62.07 g
0.644
= 0.162 = mole fraction ethylene glycol
3.33 0.644
1.00 mol acetone

1 mol
= 1.00 molal; 1.00 103 g C2H5OH
= 21.7 mol C2H5OH
1.00 kg ethanol
46.07 g
acetone =
1.00
= 0.0441
1.00 21.7
1 mol CH3COCH3
58.08 g CH 3COCH 3
1 mL
= 73.7 mL CH3COCH3
mol CH 3COCH 3
0.788 g
1.00 103 g ethanol
Molarity =
19.
1 mL
= 1270 mL; total volume = 1270 + 73.7 = 1340 mL
0.789 g
1.00 mol
= 0.746 M
1.34 L
50.0 mL toluene
0.867 g
0.874 g
= 43.4 g toluene; 125 mL benzene
= 109 g benzene
mL
mL
Mass % toluene =
mass of toluene
43.4 g
100 =
100 = 28.5%
totalmass
43.4 g 109 g
712
20.
CHAPTER 17
Molarity =
43.4 g toluene 1000 mL

1 mol toluene
= 2.69 mol/L
175 mL soln
L
92.13g toluene
Molality =
43.4 g toluene 1000 g

1 mol toluene
= 4.32 mol/kg
109 g benzene
kg
92.13g toluene
43.4 g toluene
1 mol
= 0.471 mol toluene
92.13 g
109 g benzene
1 mol benzene
0.471
= 1.40 mol benzene; toluene =
= 0.252
78.11 g benzene
0.471 1.40
Hydrochloric acid (HCl):

molarity =
38 g HCl
1.19 g soln 1000 cm3 1 mol HCl
= 12 mol/L
100.g soln
L
36.5 g
cm3 soln
molality =
38 g HCl
1000 g 1 mol HCl
= 17 mol/kg
62 g solvent
kg
36.5 g
1 mol
1 mol
= 1.0 mol HCl; 62 g H2O
= 3.4 mol H2O
36.5 g
18.0 g
1.0
mole fraction of HCl = HCl
= 0.23
3.4 1.0
38 g HCl
Nitric acid (HNO3):

70. g HNO3 1.42 g soln 1000 cm3 1 mol HNO3
= 16 mol/L
100. g soln
L
63.0 g
cm3 soln
70. g HNO3
1000 g 1 mol HNO3
= 37 mol/kg
30. g solvent
kg
63.0 g
70. g HNO3
HNO3
1 mol
1 mol
= 1.1 mol HNO3; 30. g H2O
= 1.7 mol H2O
63.0 g
18.0 g
1.1
= 0.39
1.7 1.1
Sulfuric acid (H2SO4):

95 g H 2SO 4 1.84 g soln 1000 cm3
1 mol H 2SO 4
= 18 mol/L
3
100. g soln
L
98.1 g H 2SO 4
cm soln
CHAPTER 17
95 g H 2SO 4 1000 g 1 mol
= 194 mol/kg 200 mol/kg

5 g H 2O
kg
98.1 g
95 g H2SO4
H 2SO4
1 mol
1 mol
= 0.97 mol H2SO4; 5 g H2O
= 0.3 mol H2O
18.0 g
98.1 g
0.97
= 0.76
0.97 0.3
Acetic Acid (CH3CO2H):

99 g CH 3CO 2 H 1.05 g soln 1000 cm3
1 mol
= 17 mol/L
3
100. g soln
L
60.05 g
cm soln
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
CH3CO2 H
1.6
= 0.96
1.6 0.06
Ammonia (NH3):
28 g NH3
0.90 g 1000 cm3
1 mol
= 15 mol/L
3
100. g soln
L
17.0 g
cm
28 g NH3
1000 g 1 mol
= 23 mol/kg
72 g H 2 O
kg
17.0 g
28 g NH3
NH3
21.
1 mol
1 mol
= 1.6 mol NH3; 72 g H2O
= 4.0 mol H2O
17.0 g
18.0 g
1.6
= 0.29
4.0 1.6
Because the density of water is 1.00 g/mL, 100.0 mL of water has a mass of 100. g.
Density =
10.0 g H 3 PO4 100. g H 2 O

mass
= 1.06 g/mL = 1.06 g/cm3

volume
104 mL
Mol H3PO4 = 10.0 g
1 mol
= 0.102 mol H3PO4
97.99 g
713
714
CHAPTER 17
Mol H2O = 100. g
1 mol
= 5.55 mol H2O
18.02 g
Mole fraction of H3PO4 =
0.102 mol H 3 PO4

= 0.0180
(0.102 5.55) mol
H 2O = 1.0000 0.0180 = 0.9820
22.
Molarity =
0.102 mol H 3 PO4

= 0.981 mol/L
0.104 L soln
Molality =
0.102 mol H 3 PO4

= 1.02 mol/kg
0.100 kg solvent
If we have 100.0 mL of wine:

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

23.
Although the enthalpy change is endothermic when NaCl dissolves in water, the magnitude
of Hsoln will be a value close to zero (Hsoln 0). This is typical for soluble ionic
compounds. So energy is not the reason why ionic solids like NaCl are so soluble in water.
The answer lies in natures tendency toward the higher probability of the mixed state;
solutions form due to an increase in entropy (Ssoln 0). In the mixed state, the Na+ and Cl
ions have access to a larger volume and therefore have more positions available to them.
When a solution forms, positional probability increases, which translates into an increase in
entropy. The positive Ssoln furnishes the driving force for NaCl to dissolve in water.
24.
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
CHAPTER 17
715
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.
25.
Like dissolves like refers to the nature of the intermolecular forces. Polar solutes and ionic
solutes dissolve in polar solvents because the types of intermolecular forces present in solute
and solvent are similar. When they dissolve, the strengths of the intermolecular forces in
solution are about the same as in pure solute and pure solvent. The same is true for nonpolar
solutes in nonpolar solvents. The strengths of the intermolecular forces (London dispersion
forces) are about the same in solution as in pure solute and pure solvent. In all cases of like
dissolves like, the magnitude of Hsoln is either a small positive number (endothermic) or a
small negative number (exothermic), with a value close to zero. For polar solutes in nonpolar
solvents and vice versa, Hsoln is a very large, unfavorable value (very endothermic). Because
the energetics are so unfavorable, polar solutes do not dissolve in nonpolar solvents, and vice
versa.
26.
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 17.4 on nonideal solutions, acetone-water solutions exhibit
negative deviations from Raoults 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
Hbond with itself. Because acetone and water show negative deviations from Raoults
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 Raoults law. Both substances can hydrogen
bond in the pure state, and they can continue this in solution. However, the solutesolvent 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 Raoults 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
716
CHAPTER 17
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 (C 7H16)
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.
27.
Both Al(OH)3 and NaOH are ionic compounds. Because 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.
28.
a.
CaCl2(s) Ca2+(g) + 2 Cl(g)

Ca2+(g) + 2 Cl(g) Ca2+(aq) + 2 Cl(aq)
H = HLE = (2247 kJ)

H = Hhyd
__________________________________________________________________________________________________
CaCl2(s) Ca2+(aq) + 2 Cl(aq)
Hsoln = 46 kJ
46 kJ = 2247 kJ + Hhyd, Hhyd = 2293 kJ

CaI2(s) Ca2+(g) + 2 I(g)
Ca2+(g) + 2 I(g) Ca2+(aq) + 2 I(aq)
H = HLE = ( 2059 kJ)

H = Hhyd
____________________________________________________________________________________________________
CaI2(s) Ca2+(aq) + 2 I(aq)
Hsoln = 104 kJ
104 kJ = 2059 kJ + Hhyd, Hhyd = 2163 kJ

b. The enthalpy of hydration for CaCl2 is more exothermic than for CaI2. Any differences
must be due to differences in hydrations between Cl and I. Thus the chloride ion is more
strongly hydrated than the iodide ion.
29.
Using Hesss law:

NaI(s) Na+(g) + I(g)
Na+(g) + I(g) Na+(aq) + I(aq)
H = HLE = (686 kJ/mol)

H = Hhyd = 694 kJ/mol
__________________________________________________________________________________________________________
NaI(s) Na+(aq) + I(aq)
Hsoln = 8 kJ/mol
Hsoln refers to the heat released or gained when a solute dissolves in a solvent. Here, an
ionic compound dissolves in water.
CHAPTER 17
30.
717
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
Kr
nonpolar; soluble in CCl4

c. SO2, 6 + 2(6) = 18 e
S
polar; soluble in H2O

d. CO2, 4 + 2(6) = 16 e
+ 1 more
nonpolar; soluble in CCl4
e. MgF2 is an ionic compound so it is soluble in water.

f.
CH2O, 4 + 2(1) + 6 = 12 e
O
H
C

31.
H
C
C
H
g. C2H4, 2(4) + 4(1) = 12 e
nonpolar (like all compounds made up of

only carbon and hydrogen); soluble in CCl4
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; similar to water, 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.
32.
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
718
CHAPTER 17
33.
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.
34.
Henrys law is obeyed most accurately for dilute solutions of gases that do not dissociate in
or react with the solvent. O2 will bind to hemoglobin in the blood. Because of this reaction in
the solvent, O2(g) in blood does not follow Henrys law.
35.
Pgas = kC, 0.790 atm = k
36.
8.21 104 mol

, k = 962 L atm/mol
L
Pgas = kC, 1.10 atm =
962 L atm
C, C = 1.14 103 mol/L
mol
750. mL grape juice
12 mL C 2 H 5OH 0.79 g C 2 H 5OH 1 mol C 2 H 5OH
100. mL juice
mL
46.07 g
2 mol CO 2
= 1.54 mol CO2 (carry extra significant figure)
2 mol C 2 H 5OH
1.54 mol CO2 = total mol CO2 = mol CO2(g) + mol CO2(aq) = ng + naq
PCO2
0.08206L atm
(298 K )
n g
n g RT
mol K
= 326ng
3
V
75 10 L
PCO2 kC
n aq
32 L atm
= (42.7)naq
mol
0.750 L
PCO2 = 326ng = (42.7)naq and from above naq = 1.54 ng; solving:
326ng = 42.7(1.54 ng), 369ng = 65.8, ng = 0.18 mol
PCO2 = 326(0.18) = 59 atm in gas phase; 59 atm =

37.
32 L atm
C, C = 1.8 mol CO2/L in wine
mol
Structure effects refer to solute and solvent having similar polarities in order for solution
formation to occur. Hydrophobic solutes are mostly nonpolar substances that are waterfearing. Hydrophilic solutes are mostly polar or ionic substances that are water-loving.
Pressure has little effect on the solubilities of solids or liquids; it does significantly affect the
solubility of a gas. Henrys law states that the amount of a gas dissolved in a solution is
directly proportional to the pressure of the gas above the solution (C = kP). The equation for
Henrys law works best for dilute solutions of gases that do not dissociate in or react with the
solvent. HCl(g) does not follow Henrys law because it dissociates into H+(aq) and Cl(aq) in
solution (HCl is a strong acid). For O2 and N2, Henrys law works well since these gases do
not react with the water solvent.
CHAPTER 17
719
An increase in temperature can either increase or decrease the solubility of a solid solute in
water. It is true that a solute dissolves more rapidly with an increase in temperature, but the
amount of solid solute that dissolves to form a saturated solution can either decrease or
increase with temperature. The temperature effect is difficult to predict for solid solutes.
However, the temperature effect for gas solutes is easier to predict because the solubility of a
gas typically decreases with increasing temperature.
38.
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.
39.
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.
Vapor Pressures of Solution

40.
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 25C). Both solution b (glucosewater) 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.
Solution d (methanol-water) will have the highest total vapor pressure. 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 temperature.
41.
P = P; 710.0 torr = (760.0 torr), = 0.9342 = mole fraction of methanol
42.
Mol C3H8O3 = 164 g
Mol H2O = 338 mL
Psoln H 2O PHo 2O =
1 mol
= 1.78 mol C3H8O3
92.09 g
0.992 g 1 mol
= 18.6 mol H2O

mL
18.02 g
18.6 mol
54.74 torr = 0.913 54.74 torr = 50.0 torr
(1.78 18.6) mol
720
43.
CHAPTER 17
Psoln C2 H5OH PCo2 H5OH ; C2 H5OH
53.6 g C3H8O3
mol C 2 H 5OH in solution

totalmol in solution
1 mol C3 H 8O3
= 0.582 mol C3H8O3
92.09 g
1 mol C 2 H 5OH
= 2.90 mol C2H5OH; total mol = 0.582 + 2.90 = 3.48 mol
46.07 g
2.90 mol
PCo2 H5OH , PCo2 H5OH = 136 torr
113 torr =
3.48 mol
133.7 g C2H5OH
44.
V
PCS2 CS
P = 0.855(263 torr) = 225 torr
2 total
L
L
PCS2 CS
P o , CS
2 CS2
2
45.
PCS2
o
PCS
2
225 torr
= 0.600
375 torr
Ptotal = Pmeth + Pprop, 174 torr = Lmeth (303 torr) Lprop (44.6 torr); Lprop 1.000 Lmeth
174 = 303 Lmeth (1.000 Lmeth )44.6 torr,
129
Lmeth 0.500
258
Lprop 1.000 0.500 0.500

46.
o
o
Ptol LtolPtol
, Ppen Lben Pben
; for the vapor, VA = PA/Ptotal. Because the mole fractions of
benzene and toluene are equal in the vapor phase, Ptol Pben .
o
o
o
LtolPtol
LbenPben
(1.00 Ltol )Pben
, Ltol (28 torr) (1.00 Ltol ) 95 torr
123 Ltol 95, Ltol 0.77; Lben = 1.00 0.77 = 0.23
47.
a. 25 mL C5H12
45 mL C6H14
Lpen
0.63 g 1 mol
= 0.22 mol C5H12

mL
72.15
0.66 g 1 mol
= 0.34 mol C6H14; total mol = 0.22 + 0.34 = 0.56 mol

mL
86.17
mol pentanein solution 0.22 mol
= 0.39, Lhex = 1.00 0.39 = 0.61

totalmol in solution
0.56 mol
o
Ppen Lpen Ppen
= 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
CHAPTER 17
721
b. From Chapter 5 on gases, the partial pressure of a gas is proportional to the number of
moles of gas present. For the vapor phase:
Vpen
P
mol pentanein vapor
2.0 102 torr
= 0.69
pen
totalmol vapor
Ptotal
290 torr
Note: In the Solutions Guide, we added V or L to the mole fraction symbol to emphasize
which value we are solving. If the L or V is omitted, then the liquid phase is assumed.
48.
Ptotal = PCH2Cl2 PCH2Br2 ; P L P o ; CH

2 Cl2
0.0300 mol CH 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
V
In the vapor: CH
2 Cl2
PCH2Cl2
Ptotal
49.9 torr
V
= 0.875; CH
= 1.000 0.875 = 0.125
2 Br2
57.0 torr
Note: In the Solutions Guide we added V or L to the mole fraction symbol to emphasize
which value we are solving. If the L or V is omitted, then the liquid phase is assumed.
49.
PB B PBo , B PB / PBo = 0.900 atm/0.930 atm = 0.968
0.968 =
mol benzene
1 mol
; mol benzene = 78.11 g C6H6
= 1.000 mol
78.11 g
totalmol
Let x = mol solute; then: B = 0.968 =

Molar mass =
1.000 mol
, 0.968 + (0.968)x = 1.000, x = 0.033 mol
1.000 x
10.0 g
= 303 g/mol 3.0 102 g/mol
0.033 mol
50.
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.
51.
No, the solution is not ideal. For an ideal solution, the strengths of intermolecular forces in
the solution are the same as in pure solute and pure solvent. This results in Hsoln = 0 for an
ideal solution. Hsoln for methanol-water is not zero. Because Hsoln < 0, this solution
exhibits negative deviation from Raoults law.
722
52.
CHAPTER 17
The first diagram shows positive deviation from Raoult's law. This occurs when the solutesolvent 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 17.4 on nonideal solutions, acetone-water solutions exhibit negative deviations
from Raoults 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 Hbond with itself. So the
middle diagram illustrating negative deviations from Raoults 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 Raoults law. Both substances can hydrogen
bond in the pure state, and they can continue this in solution. However, the solutesolvent interactions are somewhat weaker for ethanol-water solutions due to the
significant nonpolar part of ethanol (CH3CH2 is the nonpolar part of ethanol). This
nonpolar part of ethanol slightly weakens the intermolecular forces in solution. So the
first diagram illustrating positive deviations from Raoults 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 CH 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 Raoults 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 Raoults law (the first diagram).
53.
Solutions of A and B have vapor pressures less than ideal (see Figure 17.11 of the text), so
this plot shows negative deviations from Raults 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 B = 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 B = 0.6 will have a higher boiling point than
either pure A or pure B. (Note that because PBo > PAo , B is more volatile than A.)
54.
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 torr 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.
CHAPTER 17
723
b. From the data, the vapor pressures of the various solutions are greater than if the
solutions behaved ideally (positive deviation from Raoults 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) Hsoln values.
c. The interactions between propanol and water molecules are weaker than between the pure
substances because the solutions exhibit a positive deviation from Raoults law.
d. At 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
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.
55.
50.0 g CH3COCH3
1 mol
= 0.861 mol acetone
58.08 g
50.0 g CH3OH 1 mol/32.04 g = 1.56 mol methanol

L
acetone
0.861
L
0.356; Lmethanol 1.000 acetone
0.644
0.861 1.56
Ptotal = Pmethanol + Pacetone = 0.644(143 torr) + 0.356(271 torr) = 92.1 torr + 96.5 torr
= 188.6 torr
Because partial pressures are proportional to the moles of gas present, in the vapor phase:
V
acetone
Pacetone
96.5 torr
0.512; 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 Raoults law. This occurs when the solute-solvent interactions are stronger than in pure
solute and pure solvent.
Colligative Properties
56.
Colligative properties are properties of a solution that depend only on the number, not the
identity, of the solute particles. A solution of some concentration of glucose (C6H12O6) has
the same colligative properties as a solution of sucrose (C12H22O11) having the same concentration.
A substance freezes when the vapor pressure of the liquid and solid are identical to each
other. Adding a solute to a substance lowers the vapor pressure of the liquid. A lower
temperature is needed to reach the point where the vapor pressures of the solution and solid
are identical. Hence the freezing point is depressed when a solution forms.
724
CHAPTER 17
A substance boils when the vapor pressure of the liquid equals the external pressure. Because
a solute lowers the vapor pressure of the liquid, a higher temperature is needed to reach the
point where the vapor pressure of the liquid equals the external pressure. Hence the boiling
point is elevated when a solution forms.
57.
= MRT, M
15 atm
0.62 M
RT
0.08206L atm K -1 mol-1 295 K
0.62 mol
342.30 g
= 212 g/L 210 g/L

L
mol C12 H 22O11
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.
58.
This is true if the solute will dissolve in camphor. Camphor has the largest K b 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 is the measurement,
and the more precise is the calculated molar mass. However, if the solute wont dissolve in
camphor, then camphor is no good, and another solvent must be chosen that will dissolve the
solute.
59.
Molality = m =
50.0 g C 2 H 6 O 2 1000 g
1 mol
= 16.1 mol/kg
50.0 g H 2 O
kg
62.07 g
Tf = Kfm = 1.86 C/molal 16.1 molal = 29.9C; Tf = 0.0C 29.9C = 29.9C

Tb = Kbm = 0.51C/molal 16.1 molal = 8.2C; Tb = 100.0C + 8.2C = 108.2C
60.
T = 25.50C 24.59C = 0.91C = Kfm, m =
Mass H2O = 0.0100 kg t-butanol
61.
Molality = m =
Tb = Kbm =
0.91 o C
= 0.10 mol/kg
9.1 o C / molal
0.10 mol H 2 O 18.02 g H 2 O
kg t - butanol
mol H 2 O
= 0.018 g H2O
1 mol N 2 H 4 CO
mol solute 27.0 g N 2 H 4 CO 1000 g
= 3.00 molal
kg solvent
150.0g H 2 O
kg
60.06g N 2 H 4 CO
0.51 C
3.00 molal = 1.5C
molal
The boiling point is raised from 100.0C to 101.5C (assuming P = 1 atm).

62.
Tf = Kfm, Tf = 1.50C =
1.86 C
m, m = 0.806 mol/kg
molal
CHAPTER 17
0.200 kg H2O
63.
725
0.806 mol C3H8O3

92.09g C3 H8O3
kg H 2 O
mol C3H8O3
Tb = 77.85C 76.50C = 1.35C; m =
Mol biomolecule = 0.0150 kg solvent
= 14.8 g C3H8O3
Tb
1.35 o C
= 0.268 mol/kg
Kb
5.03 o C kg / mol
0.268 mol hydrocarbon

= 4.02 103 mol
kg solvent
From the problem, 2.00 g biomolecule was used, which must contain 4.02 103 mol
biomolecule. The molar mass of the biomolecule is:
2.00 g
= 498 g/mol
4.02 103 mol
64.
m=
Tf
30.0o C
= 16.1 mol C2H6O2/kg
Kf
1.86 o C kg / mol
Because the density of water is 1.00 g/cm3, the moles of C2H6O2 needed are:
15.0 L H2O
1.00 kg H 2 O 16.1 mol C 2 H 6 O 2
= 242 mol C2H6O2

L H 2O
kg H 2 O
Volume C2H6O2 = 242 mol C2H6O2

Tb = Kbm =
62.07 g
1 cm3
= 13,500 cm3 = 13.5 L
mol C 2 H 6 O 2 1.11 g
0.51 o C
16.1 molal = 8.2C; Tb = 100.0C + 8.2C = 108.2C
molal
1 mol
58.0 g
= 0.690 mol/kg; Tb = Kbm = 0.51C kg/mol 0.690 mol/kg = 0.35C
0.600 kg
24.0 g
65.
m=
Tb = 99.725C + 0.35C = 100.08C
8.00 atm
= 0.327 mol/L
RT
0.08206L atm K 1 mol1 298 K
66.
= MRT, M =
67.
5.86 102 mol thyroxine

Tf
0.300C
Tf = Kfm, m =
Kf
5.12 C kg / mol
kg benzene
The moles of thyroxine present are:

0.0100 kg benzene
5.86 102 mol thyroxine

kg benzene
= 5.86 104 mol thyroxine
726
CHAPTER 17
From the problem, 0.455 g thyroxine was used; this must contain 5.86 104 mol thyroxine.
The molar mass of the thyroxine is:
molar mass =
68.
5.86 104 mol
= 776 g/mol
1 atm
0.745 torr
760 torr
M=
= 3.98 105 mol/L
0.08206L atm
RT
300. K
K mol
1.00 L
3.98 105 mol

= 3.98 105 mol catalase
L
Molar mass =
69.
0.455 g
M=
10.00 g
= 2.51 105 g/mol
5
3.98 10 mol
1.0 g
1 mol
= 1.1 105 mol/L; = MRT

4
L
9.0 10 g
At 298 K: =
1.1 105 mol 0.08206L atm

760 torr
, = 0.20 torr
298 K
L
K mol
atm
Because d = 1.0 g/cm3, 1.0 L of solution has a mass of 1.0 kg. Because only 1.0 g of protein
is present per liter solution, 1.0 kg of H2O is present, and molality equals molarity to the
correct number of significant figures.
Tf = Kfm =
1.86 o C
1.1 105 molal = 2.0 105 C
molal
70.
Osmotic pressure is better for determining the molar mass of large molecules. A temperature
change of 10-5C 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.
71.
With addition of salt or sugar, the osmotic pressure inside the fruit cells (and bacteria) is less
than outside the cell. Water will leave the cells, which will dehydrate any bacteria present,
causing them to die.
72.
Tf = 5.51 2.81 = 2.70C; m
Tf
2.70o C
= 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).
CHAPTER 17
727
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
73.
= MRT =
0.1 mol 0.08206L atm
298 K = 2.45 atm 2 atm

L
K mol
= 2 atm
760 mm Hg
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
Properties of Electrolyte Solutions

74.
75.
The solutions of glucose, 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
d. pure water
e. CaCl2 solution
c. CaCl2 solution
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
728
CHAPTER 17
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 = P; as the solute concentration decreases, the solvents vapor pressure increases
because increases. Therefore, the 0.020 m HF solution will have the highest vapor
pressure because it has the smallest effective particle concentration.
c. T = Kfm; the 0.020 m CaBr2 solution has the largest effective particle concentration, so
it will have the largest freezing point depression (largest T).
76.
a. As discussed in Figure 17.16 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 (H 2O) 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.
77.
NaCl(s) Na+(aq) + Cl(aq), i = 2.0

= iMRT = 2.0
0.10 mol 0.08206L atm
293 K = 4.8 atm

L
K mol
A pressure greater than 4.8 atm should be applied to ensure purification by reverse osmosis.
78.
If ideal, NaCl dissociates completely, and i = 2.00. Tf = iKfm; assuming water freezes at
0.00C:
1.28C = 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
= 20.1 g NaCl
mol
20.1 g
Mass % NaCl =
100 = 1.97%
1.00 103 g 20.1 g
0.344 mol NaCl
CHAPTER 17
79.
729
P = P; 19.6 torr = H 2O (23.8 torr) , H 2O = 0.824; solute = 1.000 - 0.824 = 0.176

0.176 is the mole fraction of all the solute particles present. Because NaCl dissolves to
produce two ions in solution (Na+ and Cl), 0.176 is the mole fraction of Na+ and Cl ions
present. The mole fraction of NaCl is 1/2 (0.176) = 0.0880 = NaCl .
At 45C, Psoln = 0.824(71.9 torr) = 59.2 torr.
80.
a. m =
5.0 g NaCl
1 mol
= 3.4 molal; NaCl(aq) Na+(aq) + Cl(aq), i = 2.0

0.025 kg
58.44 g
Tf = iKfm = 2.0 1.86C/molal 3.4 molal = 13C; Tf = 13C

Tb = iKbm = 2.0 0.51C/molal 3.4 molal = 3.5C; Tb = 103.5C
b.
m=
2.0 g Al( NO3 )3

1 mol
= 0.63 mol/kg
0.015 kg
213.01 g
Al(NO3)3(aq) Al3+(aq) + 3 NO3(aq), i = 4.0

Tf = iKfm = 4.0 1.86C/molal 0.63 molal = 4.7C; Tf = 4.7C
81.
For CaCl2: i
Tf
0.440o C
= 2.6
K f m 1.86 o C/molal 0.091molal
Percent CaCl2 ionized =

For CsCl: i
2.6 1.0
100 = 80.%; 20.% ion association occurs.
3.0 1.0
Tf
0.320o C
= 1.9
K f m 1.86 o C/molal 0.091molal
Percent CsCl ionized =
1.9 1.0
100 = 90.%; 10% ion association occurs.
2.0 1.0
The ion association is greater in the CaCl2 solution.

82.
a. MgCl2(s) Mg2+(aq) + 2 Cl(aq), i = 3.0 mol ions/mol solute

Tf = iKfm = 3.0 1.86 C/molal 0.050 molal = 0.28C; Tf = -0.28C (Assuming water
freezes at 0.00C.)
Tb = iKbm = 3.0 0.51 C/molal 0.050 molal = 0.077C; Tb = 100.077C (Assuming
water boils at 100.000C.)
730
CHAPTER 17
b. FeCl3(s) Fe3+(aq) + 3 Cl(aq), i = 4.0 mol ions/mol solute

Tf = iKfm = 4.0 1.86 C/molal 0.050 molal = 0.37C; Tf = 0.37C
Tb = iKbm = 4.0 0.51 C/molal 0.050 molal = 0.10C; Tb = 100.10C
83.
a. MgCl2, i (observed) = 2.7

Tb = iKbm = 2.7 0.51 C/molal 0.050 molal = 0.069C; Tb = 100.069C
b. FeCl3, i (observed) = 3.4
84.
From Table 17.6, 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 solution 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 vant Hoff factor very close to the
expected i value.
85.
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 vant Hoff factor is:
i
86.
moles of particlesin solution

moles of solute dissolved
Tf = iKfm, i =
i=
10
1.67
6
Tf
0.110o C
= 2.63 for 0.0225 m CaCl2
K f m 1.86 o C / molal 0.0225 molal
1.330
0.440
= 2.60 for 0.0910 m CaCl2; i =
= 2.57 for 0.278 m CaCl2
1.86 0.0910
1.86 0.278
Note that i is less than the ideal value of 3.0 for CaCl2. This is due to ion pairing in solution.
87.
= iMRT, M =
2.50 atm
=
= 5.11 102 mol/L
0
.
08206
L
atm
iRT
2.00
298 K
K mol
Molar mass of compound =
0.500 g
= 97.8 g/mol
5.11 10 2 mol
0.1000 L
L
CHAPTER 17
88.
731
a. TC = 5(TF 32)/9 = 5(29 32)/9 = 34C

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
Tf = iKfm = 3.00 1.86 C kg/mol 6.71 mol/kg = 37.4C
Assuming i = 3.00, a saturated solution of CaCl2 can lower the freezing point of water to
37.4C. Assuming these conditions, a saturated CaCl2 solution should melt ice at 34C
(29F).
b. From Exercise 17.86, i 2.6; Tf = iKfm = 2.6 1.86 6.71 = 32C; Tf = 32C.
Assuming i = 2.6, a saturated CaCl2 solution will not melt ice at 34C (29F).
Additional Exercises
89.
Both solutions and colloids have suspended particles in some medium. The major difference
between the two is the size of the particles. A colloid is a suspension of relatively large particles compared to a solution. Because of this, colloids will scatter light, whereas solutions
will not. The scattering of light by a colloidal suspension is called the Tyndall effect.
90.
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.
= detergent
molecule
= SO 4= nonpolar
hydrocarbon
= dirt
732
CHAPTER 17
91.
Coagulation is the destruction of a colloid by the aggregation of many suspended particles to

form a large particle that settles out of solution.
92.
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.
93.
14.2 mg CO2
3.88 mg
12.01 mg C
= 3.88 mg C; % C =
100 = 80.8% C
44.01 mg CO 2
4.80 mg
1.65 mg H2O
0.185 mg
2.016 mg H
= 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:
80.8 g C
1 mol
6.73
= 6.73 mol C;
= 6.99 7
12.01 g
0.963
3.85 g H
1 mol
3.82
= 3.82 mol H;
= 3.97 4
1.008 g
0.963
15.4 g O
1 mol
0.963
= 0.963 mol O;
= 1.00
16.00 g
0.963
Therefore, the empirical formula is C7H4O.

Tf = Kfm, m =
Tf
22.3 o C
= 0.56 molal
Kf
40. o C / molal
Mol anthraquinone = 0.0114 kg camphor
Molar mass =
0.56 mol anthraquinone

= 6.4 103 mol
kg camphor
1.32 g
= 210 g/mol
6.4 103 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.
CHAPTER 17
94.
733
Benzoic acid (see Exercise 101) 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.
95.
M3X2(s)
Initial s = solubility (mol/L)

Equil.
3 M2+(aq) +
0
3s
2 X3(aq)
Ksp = [M2+]3[X3 ]2
0
2s
Ksp = (3s)3(2s)2 = 108s5; total ion concentration = 3s + 2s = 5s.

= iMRT, iM = total ion concentration
2.64 102 atm
RT 0.08206L atm K 1 mol1 298 K
= 1.08 103 mol/L
5s = 1.08 10 mol/L, s = 2.16 10 mol/L

Ksp = 108s5 = 108(2.16 104)5 = 5.08 1017
96.
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
temperature. The higher the cooking temperature, the faster is the cooking time.
b. Salt dissolves in water, forming a solution with a melting point lower than that of pure
water (Tf = Kfm). This happens in water on the surface of ice. If it is not too cold, the
ice melts. This won't work if the ambient temperature is lower than the depressed
freezing point of the salt solution.
c. When water freezes from a solution, it freezes as pure water, leaving behind a more
concentrated salt solution.
d. On the CO2 phase diagram (see Figure 16.58), the triple point is above 1 atm, and 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.
97.
iM
0.3950 atm
= 0.01614 mol/L = total ion concentration

RT 0.08206L atm K 1 mol1 (298.2 K)
0.01614 mol/L M Mg 2 M Na M Cl ; M Cl 2M Mg 2 M Na (charge balance)

Combining: 0.01614 = 3 M Mg 2 2M Na
734
CHAPTER 17
Let x = mass MgCl2 and y = mass NaCl; then x + y = 0.5000 g.
M Mg 2
x
y
and M Na
(Because V = 1.000 L.)
95.218
58.443
Total ion concentration =
3x
2y
= 0.01614 mol/L
95.218 58.443
Rearranging: 3x + (3.2585)y = 1.537

Solving by simultaneous equations:
3x + (3.2585)y = 1.537
3(x +
y) = 3(0.5000)
___________________________________________
(0.2585)y = 0.037,
y = 0.14 g NaCl
Mass MgCl2 = 0.5000 g 0.14 g = 0.36 g; mass % MgCl2 =
98.
T = imKf, i =
0.36 g
100 = 72%
0.5000 g
T
2.79o C
=
= 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:
38.68 g Cl
1 mol Cl
= 1.091 mol Cl
35.45 g
mol M = 1.091 mol Cl

Molar mass of M =
1 mol M
= 0.5455 mol M
2 mol Cl
61.32 g M
= 112.4 g/mol; M is Cd, so Q = CdCl2.
0.5455 mol M
1 mol
100.0 g
= 2.00 103 mol/kg 2.00 103 mol/L (dilute solution)
0.5000 kg
0.100 g
99.
m=
Tf = iKfm, 0.0056C = i 1.86 C/molal 2.00 103 molal, i = 1.5

If i = 1.0, percent dissociation = 0%, and if i = 2.0, percent dissociation = 100%. Because i =
1.5, the weak acid is 50.% dissociated.
HA H+ + A
Ka =
[H ][A ]
[HA]
CHAPTER 17
735
Because the weak acid is 50.% dissociated:

[H+] = [A] = [HA]o 0.50 = 2.00 103 M 0.50 = 1.0 103 M
[HA] = [HA]0 amount HA reacted = 2.00 103 M 1.0 103 M = 1.0 103 M
Ka =
100.
[H ][A ]
(1.0 103 )(1.0 103 )
=
= 1.0 103
3
[HA]
1.0 10
Mass of H2O = 160. mL
0.995 g
= 159 g = 0.159 kg
mL
Mol NaDTZ = 0.159 kg
0.378 mol
= 0.0601 mol
kg
Molar mass of NaDTZ =
38.4 g
= 639 g/mol
0.0601mol
Psoln = H 2O PHo 2O ; mol H2O = 159 g
1 mol
= 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.
H 2O =
8.82 mol
= 0.987; Psoln = 0.987 34.1 torr = 33.7 torr
0.120 mol 8.82 mol
101.
O
C
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
C
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 5.12C (Tf =
Kf m).
736
102.
CHAPTER 17
Out of 100.00 g, there are:

31.57 g C
5.30 g H
1 mol C
= 2.628 mol C;
12.011g
1 mol H
= 5.26 mol H;
1.008 g
63.13 g O
1 mol O
= 3.946 mol O;
15.999 g
2.628
= 1.000
2.628
5.26
= 2.00
2.628
3.946
= 1.502
2.628
Empirical formula: C2H4O3; use the freezing-point data to determine the molar mass.
m=
Tf
5.20o C
= 2.80 molal
Kf
1.86 o C/molal
Mol solute = 0.0250 kg
Molar mass =
2.80 mol solute

= 0.0700 mol solute
kg
10.56 g
= 151 g/mol
0.0700 mol
The empirical formula mass of C2H4O3 = 76.051 g/mol. Because the molar mass is about
twice the empirical mass, the molecular formula is C4H8O6, which has a molar mass of
152.101 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 atomic masses.
103.
A 92 proof ethanol solution is 46% C2H5OH by volume. Assuming 100.0 mL of solution:

mol ethanol = 46 mL C2H5OH
molarity =
104.
0.79 g 1 mol C 2 H 5 OH
= 0.79 mol C2H5OH

mL
46.07 g
0.79 mol
= 7.9 M ethanol
0.1000 L
Tf = Kfm, m =
Tf
5.40o C
= 2.90 molal
Kf
1.86 o C / molal
2.90 mol solute

n
, n = 0.145 mol of ions in solution

kg solvent
0.0500 kg
Because NaNO3 and Mg(NO3)2 are strong electrolytes:
n = 2(x mol of NaNO3) + 3[y mol Mg(NO3)2] = 0.145 mol ions
CHAPTER 17
737
85.00 g
148.3 g
In addition: 6.50 g = x mol NaNO3
+ y mol Mg(NO3)2
mol
mol
We have two equations: 2x + 3y = 0.145 and (85.00)x + (148.3)y = 6.50
Solving by simultaneous equations:
(85.00)x (127.5)y = 6.16
(85.00)x + (148.3)y = 6.50
______________________
(20.8)y = 0.34,
y = 0.016 mol Mg(NO3)2
Mass of Mg(NO3)2 = 0.016 mol 148.3 g/mol = 2.4 g Mg(NO3)2, or 37% Mg(NO3)2 by mass
Mass of NaNO3 = 6.50 g - 2.4 g = 4.1 g NaNO3, or 63% NaNO3 by mass
105.
a. NH4NO3(s) NH4+(aq) + NO3(aq) Hsoln = ?

Heat gain by dissolution process = heat loss by solution; We will keep all quantities
positive in order to avoid sign errors. Because the temperature of the water decreased,
the dissolution of NH4NO3 is endothermic (H is positive). Mass of solution = 1.60 +
75.0 = 76.6 g
Heat loss by solution =
Hsoln =
4.18 J
76.6 g (25.00C 23.34C) = 532 J
o
Cg
80.05 g NH 4 NO3
532 J
= 2.66 104 J/mol = 26.6 kJ/mol

1.60 g NH 4 NO3
mol NH 4 NO3
b. We will use Hesss law to solve for the lattice energy. The lattice energy equation is:
NH4+(g) + NO3(g) NH4NO3(s)
H = lattice energy
NH4+(g) + NO3(g) NH4+(aq) + NO3(aq) H = Hhyd = 630. kJ/mol

NH4+(aq) + NO3(aq) NH4NO3(s)
H = Hsoln = 26.6 kJ/mol
____________________________________________________________________________________________________________
NH4+(g) + NO3(g) NH4NO3(s)

106.
H = Hhyd Hsoln = 657 kJ/mol
Use the thermodynamic data to calculate the boiling point of the solvent.
At boiling point, G = 0 = H TS, H = TS, T =
H
33.90 103 J/mol
= 353.3 K
S
95.95 J K 1 mol1
T = Kbm, (355.4 K 353.3 K) = (2.5 K kg/mol)(m), m =

Mass solvent = 150. mL
0.879 g
1 kg
= 0.132 kg
mL
1000 g
2 .1
= 0.84 mol/kg
2 .5
738
CHAPTER 17
Mass solute = 0.132 kg solvent
107.
Vpen 0.15
Ppen
Ptotal
0.84 mol solute 142 g
= 15.7 g = 16 g solute
kg solvent
mol
o
; Ppen Lpen Ppen
; Ptotal Ppen Phex Lpen (511) Lhex (150.)
Because Lhex 1.000 Lpen : Ptotal Lpen (511) (1.000 Lpen )(150.) 150. 361 Lpen
Vpen
Ppen
Ptotal
, 0.15
Lpen (511)
150.
361 Lpen
23 + 54 Lpen = 511 Lpen , Lpen =

108.
, 0.15(150. 361 Lpen ) 511 Lpen
23
= 0.050
457
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.
246 mg C3H5O3
112.06 mg NaC3 H 5O3

89.07 mg C3 H 5O3
= 309.5 mg sodium lactate
The only source of Ca2+ is CaCl22H2O.

5.45 mg Ca2+
147.0 mg CaCl 2 2H2 O

= 19.99 or 20.0 mg CaCl22H2O
40.08 mg Ca 2
The only source of K+ is KCl.

15.7 mg K+
74.55 mg KCl
= 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.
236.5 mg Na+
58.44 mg NaCl
= 601.2 mg NaCl
22.99 mg Na
CHAPTER 17
739
Now let's check the mass of Cl added:

20.0 mg CaCl22H2O
70.90 mg Cl
= 9.6 mg Cl
147.0 mg CaCl 2 2H2 O
20.0 mg CaCl22H2O = 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 CaCl22H2O, 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
368 mg Cl
4.9 mg Ca 2
1 mmol
1 mmol
= 0.0012 M;
= 0.104 M
100. mL
100. mL
35.45 mg
40.08 mg
231 mg C3 H 5O3
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

= MRT =
0.259 mol 0.08206L atm
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 0.08206L atm
310. K = 7.30 atm

L
K mol
Osmotic pressure ranges from 6.59 atm to 7.30 atm.
740
109.
CHAPTER 17
T = Kfm, m =
T
2.79o C
= 1.50 molal
Kf
1.86 o C/molal
a. T = Kbm, T = 0.51oC/molal 1.50 molal = 0.77oC, Tb = 100.77oC

b.
o
Psoln water Pwater
, water =
mol H 2 O
mol H 2 O mol solute
Assuming 1.00 kg of water, we have 1.50 mol solute, and:

mol H2O = 1.00 103 g H2O
water =
1 mol H 2 O
= 55.5 mol H2O
18.02 g H 2 O
55.5 mol
= 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).
110.
MX M+ + X Ksp = [M+][X]; T = Kfm, m =
T 0.028
= 0.015 mol/kg
Kf
1.86
0.015 mol
1 kg
250 g = 0.00375 mol total solute particles (carrying extra sig. fig.)
kg
1000 g
Assume a solution density of 1.0 g/mL so that volume of solution = 250 mL.
[M+] =
(0.00375/2)
(0.00375/2)
= 7.5 103 M, [X] =
= 7.5 103 M
0.25 L
0.25 L
Ksp = [M+][X] = (7.5 103)(7.5 103) = 5.6 105

111.
a. m =
Tf
1.32o C
= 0.258 mol/kg
Kf
5.12 o C kg / mol
0.258 mol unknown

= 4.02 103 mol
kg
1.22 g
Molar mass of unknown =
= 303 g/mol
4.02 103 mol
0.04
Uncertainty in temperature =
100 = 3%
1.32
Mol unknown = 0.01560 kg
A 3% uncertainty in 303 g/mol = 9 g/mol.

So molar mass = 303 9 g/mol.
CHAPTER 17
741
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
112.
m=
Tf
0.426o C
= 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 + nC12H 22O11 = 0.229 and 58.44(nNaCl) + 342.3(nC12H 22O11 ) = 20.0
Solving: nC12H 22O11 = 0.0425 mol = 14.5 g and nNaCl = 0.0932 mol = 5.45 g
Mass % C12H22O11 =
C12H 22O11 =
14.5 g
100 = 72.5 % and 27.5% NaCl by mass
20.0 g
0.0425 mol
= 0.313
0.0425 mol 0.0932 mol
Challenge Problems
113.
a. Assuming no ion association between SO42(aq) and Fe3+(aq), then i = 5 for Fe2(SO4)3.
= iMRT = 5 0.0500 mol/L 0.08206 L atm K1 mol1 298 K = 6.11 atm
b. Fe2(SO4)3(aq) 2 Fe3+(aq) + 3 SO42 (aq)
Under ideal circumstances, 2/5 of calculated above results from Fe3+ and 3/5 results from
SO42. The contribution to from SO42 is 3/5 6.11 atm = 3.67 atm. Because SO42 is
assumed unchanged in solution, the SO42 contribution in the actual solution will also be 3.67
atm. The contribution to the actual from the Fe(H2O)63+ dissociation reaction is 6.73 3.67
= 3.06 atm.
The initial concentration of Fe(H2O)62+ is 2(0.0500) = 0.100 M. The setup for the weak acid
problem is:
742
CHAPTER 17
Fe(H2O)63+
H+
Fe(OH)(H2O)52+
Ka =
[H ][Fe(OH)(H 2 O)52 ]
[Fe(H 2 O) 36 ]
Initial 0.100 M
~0
0
3+
x mol/L of Fe(H2O)6 reacts to reach equilibrium
Equil. 0.100 x
x
x
Total ion concentration = iM
3.06 atm
0.125 M
RT 0.08206L atm K 1 mol1 (298 K)
0.125 M = 0.100 x + x + x = 0.100 + x, x = 0.025 M

Ka =
114.
[H ][Fe(OH)(H 2 O)52 ]
x2
(0.025) 2
(0.025) 2
=
= 8.3 103
0.100 x
(0.100 0.025)
0.075
[Fe(H 2 O) 36 ]
Initial moles VCl4 = 6.6834 g VCl4 1 mol VCl4/192.74 g VCl4 = 3.4676 102 mol VCl4
Total molality of solute particles = im =
T
5.97o C
, 0.200 mol/kg
Kf
29.8 o C kg / mol
Because we have 0.1000 kg CCl4, the total moles of solute particles present is:
0.200 mol/kg (0.1000 kg) = 0.0200 mol
2 VCl4
Initial
Equil.
V2Cl8
3.4676 102 mol

0
2x mol VCl4 reacts to reach equilibrium
3.4676 102 2x
x
K=
[V2 Cl 8 ]
[VCl 4 ]2
Total moles solute particles = 0.0200 mol = mol VCl4 + mol V2Cl8 = 3.4676 102 2x + x
0.0200 = 3.4676 102 x, x = 0.0147 mol
At equilibrium, we have 0.0147 mol V2Cl8 and 0.0200 - 0.0147 = 0.0053 mol VCl4. To
determine the equilibrium constant, we need the total volume of solution in order to calculate
equilibrium concentrations. The total mass of solution is 100.0 g + 6.6834 g = 106.7 g.
Total volume = 106.7 g 1 cm3/1.696 g = 62.91 cm3 = 0.06291 L
The equilibrium concentrations are:
[V2Cl8] =
0.0147 mol
0.0053 mol
= 0.234 mol/L; [VCl4] =
= 0.084 mol/L
0.06291L
0.06291L
[V2 Cl 8 ]
0.234
33
2
[VCl 4 ]
(0.084) 2
CHAPTER 17
115.
a. Assuming MgCO3(s) does not dissociate, the solute concentration in water is:
560 g MgCO 3 (s)
560 mg 560 103 g 1 mol MgCO 3
mL
L
L
84.32 g
= 6.6 103 mol MgCO3/L
An applied pressure of 8.0 atm will purify water up to a solute concentration of:
M
8.0 atm
0.32 mol
1
1
RT 0.08206L 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:
6.6 103 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 1.3 102 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.
116.
Let LA = mole fraction A in solution, so 1.000 LA = LB . From the problem, VA = 2 LA .

VA =
PA
LA (350.0 torr)
= L
Ptotal
A (350.0 torr) (1.000 LA )(100.0 torr)
VA = 2 LA =
(350.0) LA
, (250.0) LA = 75.0, LA = 0.300
(250.0) LA 100.0
The mole fraction of A in solution is 0.300.

117.
a. = iMRT, iM
7.83 atm
0.320 mol/L
RT 0.08206L atm K 1 mol1 298 K
Assuming 1.000 L of solution:

total mol solute particles = mol Na+ + mol Cl + mol NaCl = 0.320 mol
743
744
CHAPTER 17
mass solution = 1000. mL
1.071g
= 1071 g solution
mL
mass NaCl in solution = 0.0100 1071 g = 10.7 g NaCl

mol NaCl added to solution = 10.7 g
1 mol
= 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
Fraction of ion pairs =
0.046
= 0.25, or 25%
0.183
b. T = 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
T = 1.86 C kg/mol
0.320 mol
= 0.562C
1.060 kg
Assuming water freezes at 0.000C, then Tf = 0.562C.

118.
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.
b. Molarity =
moles solvent
moles solvent
; 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.
c. T = Kf m, m =
T
0.621o C
=
= 0.334 mol/kg
Kf
1.86 o C kg/mol
CHAPTER 17
745
Assuming 0.334 mol/kg = 0.334 mol/L:

= MRT =
d. m =
0.334 mol 0.08206L atm
298 K = 8.17 atm

L
K mol
T
2.0o C
=
= 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.
119.
L
From the problem, CL 6 H6 CCl
= 0.500. We need the pure vapor pressures (Po) in order to
4
calculate the vapor pressure of the solution.
C6H6(l)
C6H6(g)
K PC6H6 PCo6H6 at 25C
G orxn G of , C6H6 (g ) G of , C6H6 (l) 129.66 kJ/mol 124.50 kJ/mol = 5.16 kJ/mol
G = RT ln K, ln K
G o
5.16 103 J/mol
2.08
RT
(8.3145 J K 1 mol1 ) (298 K)
K = PCo6 H 6 = e2.08 = 0.125 atm

For CCl4: G orxn G of , CCl4 (g ) G of , CCl4 (l) = 60.59 kJ/mol (65.21 kJ/mol)
= 4.62 kJ/mol
G o
4620 J/mol
o
exp
exp
K = PCCl
=
1
4
8.3145 J K mol 298 K = 0.155 atm
RT
PC6H6 CL 6H6 PCo6H6 0.500(0.125 atm) = 0.0625 atm; PCCl4 = 0.500(0.155 atm)
= 0.0775 atm
CV6 H 6
PC6 H 6
Ptotal
0.0625 atm
0.0625 atm 0.0775 atm
0.0625
0.1400
V
= 0.446; CCl
= 1.000 0.446
4
= 0.554
120.
For 30.% A by moles in the vapor, 30. =
0.30 =
PA
100:
PA PB
Ax
Ax
, 0.30
Ax By
A x (1.00 A ) y
746
CHAPTER 17
A x = 0.30(A x) + 0.30 y 0.30(A y), A x (0.30)A x + (0.30)A y = 0.30 y

A(x 0.30 x + 0.30 y) = 0.30 y, A =
0.30 y
; B = 1.00 A
0.70 x 0.30 y
Similarly, if vapor above is 50.% A: A

If vapor above is 80.% A: A =
y
y
; B 1.00
x y
x y
0.80 y
; B = 1.00 A
0.20 x 0.80 y
If the liquid solution is 30.% A by moles, A = 0.30.

Thus VA
121.
PA
0.30 x
0.30 x
and VB 1.00
=
0.30 x 0.70 y
PA PB
0.30 x 0.70 y
If solution is 50.% A: VA
x
x y
If solution is 80.% A: VA
0.80 x
and VB 1.00 VA
0.80 x 0.20 y
and VB 1.00 VA
For the second vapor collected, VB, 2 = 0.714 and TV, 2 = 0.286. Let LB, 2 = mole fraction of
benzene in the second solution and TL, 2 = mole fraction of toluene in the second solution.
LB, 2 TL, 2 = 1.000

VB, 2 = 0.714 =
LB, 2 (750.0 torr)

PB
PB
= L
Ptotal
PB PT
B, 2 (750.0 torr) (1.000 LB, 2 )(300.0 torr)
Solving: LB, 2 = 0.500 = TL, 2

This second solution came from the vapor collected from the first (initial) solution, so, VB, 1 =
TV, 1 = 0.500. Let LB, 1 = mole fraction benzene in the first solution and TL, 1 = mole fraction
of toluene in first solution. LB, 1 TL, 1 = 1.000.
VB, 1 = 0.500 =
LB, 1 (750.0 torr)

PB
PB
= L
Ptotal
PB PT
B, 1 (750.0 torr) (1.000 LB, 1 )(300.0 torr)
Solving: LB, 1 = 0.286; the original solution had B = 0.286 and T = 0.714.
CHAPTER 17
122.
m=
747
T
0.406o C
= 0.218 mol/kg
Kf
1.86 o C/molal
= 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 complete dissociation of NaCl, 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.
= 0.218 M 0.08206 L atm K1 mol1 298 K = 5.33 atm
Marathon Problem
123.
a. From part a information we can calculate the molar mass of NanA and deduce the
formula.
Mol NanA = mol reducing agent = 0.01526 L
Molar mass of NanA =
0.02313mol
= 3.530 104 mol NanA
L
30.0 103 g
= 85.0 g/mol
3.530 104 mol
To deduce the formula, we will assume various charges and numbers of oxygens present
in the oxyanion, and then use the periodic table to see if an element fits the molar mass
data. Assuming n = 1 so that the formula is NaA. The molar mass of the oxyanion A- is
85.0 23.0 = 62.0 g/mol. The oxyanion part of the formula could be EO or EO2 or
EO3, where E is some element. If EO, then the molar mass of E is 62.0 16.0 = 46.0
g/mol; no element has this molar mass. If EO2, molar mass of E = 62.0 32.0 = 30.0
g/mol. Phosphorus is close, but PO2 anions are not common. If EO3, molar mass of E
= 62.0 48.0 = 14.0. Nitrogen has this molar mass, and NO3 anions are very common.
Therefore, NO3 is a possible formula for A.
Next, we assume Na2A and Na3A formulas and go through the same procedure as above.
In all cases, no element in the periodic table fits the data. Therefore, we assume the
oxyanion is NO3 = A.
b. The crystal data in part b allow determination of the metal M in the formula. See
Exercise 16.47 for a review of relationships in body-centered cubic cells. In a bodycentered cubic unit cell and there are two atoms per unit cell, and the body diagonal of
the cubic cell is related to the radius of the metal by the equation 4r = l 3 where l =
cubic edge length.
l=
4r
3
4(1.984 108 cm)

3
= 4.582 108 cm
748
CHAPTER 17
Volume of unit cell = l3 = (4.582 108)3 = 9.620 1023 cm3

Mass of M in a unit cell = 9.620 1023 cm3
Mol M in a unit cell = 2 atoms
Molar mass of M =
5.243 g
= 5.044 1022 g M
cm3
1 mol
= 3.321 1024 mol M
23
6.022 10
5.044 1022 g M
= 151.9 g/mol
3.321 10 24 mol M
From the periodic table, M is europium (Eu). Given that the charge of Eu is +3, then the
formula of the salt is Eu(NO3)3zH2O.
c. Part c data allow determination of the molar mass of Eu(NO3)3zH2O, from which we can
determine z, the number of waters of hydration.
1 atm
558 torr
760 torr
= iMRT, iM =
= 0.0300 mol/L
RT
0.08206L atm K 1 mol1 (298 K )
The total molarity of solute particles present is 0.0300 M. The solute particles are Eu3+
and NO3 ions (the waters of hydration are not solute particles). Because each mole of
Eu(NO3)3zH2O dissolves to form four ions (Eu3+ + 3 NO3), the molarity of
Eu(NO3)3zH2O is 0.0300/4 = 0.00750 M.
Mol Eu(NO3)3zH2O = 0.01000 L
Molar mass of Eu(NO3)3zH2O =
0.00750mol
= 7.50 105 mol
L
33.45 103 g
= 446 g/mol
7.50 105 mol
446 g/mol = 152.0 + 3(62.0) + z(18.0), z(18.0) = 108, z = 6.00

The formula for the strong electrolyte is Eu(NO3)36H2O.

SM Chapter 17

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CHAPTER 17

Mass percent: the percent by mass of the solute in the solution.

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)

g. NH4NO3(s) NH4+(aq) + NO3(aq)

h. CuSO4(s) Cu2+(aq) + SO42(aq)

NH4Br(s) NH4+(aq) + Br(aq)

NaOH(s) Na+(aq) + OH(aq)

Mol Na2CO3 = 0.0700 L

Na2CO3(s) 2 Na+(aq) + CO32(aq); mol Na+ = 2(0.21) = 0.42 mol

1.0 mol NaHCO3

NaHCO3(s) Na+(aq) + HCO3(aq); mol Na+ = 0.030 mol

If we have 1.00 L of solution:

1.00 103 mL solution

1.37 mol citric acid

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

2.0 mol KCl

Dissolve 26 g NaOH in 100. mL CH3OH.

0.62 mol C6H12O6 180.2 g/mol = 110 g C6H12O6

1.00 mol acetone

1.00 103 g ethanol

43.4 g toluene 1000 mL

43.4 g toluene 1000 g

Hydrochloric acid (HCl):

Nitric acid (HNO3):

Sulfuric acid (H2SO4):

95 g H 2SO 4 1000 g 1 mol

= 194 mol/kg 200 mol/kg

Acetic Acid (CH3CO2H):

= 1600 mol/kg 2000 mol/kg

10.0 g H 3 PO4 100. g H 2 O

= 1.06 g/mL = 1.06 g/cm3

Mol H3PO4 = 10.0 g

Mol H2O = 100. g

Mole fraction of H3PO4 =

0.102 mol H 3 PO4

H 2O = 1.0000 0.0180 = 0.9820

0.102 mol H 3 PO4

0.102 mol H 3 PO4

If we have 100.0 mL of wine:

Thermodynamics of Solutions and Solubility

CaCl2(s) Ca2+(g) + 2 Cl(g)

H = HLE = (2247 kJ)

CaCl2(s) Ca2+(aq) + 2 Cl(aq)

46 kJ = 2247 kJ + Hhyd, Hhyd = 2293 kJ

H = HLE = ( 2059 kJ)

CaI2(s) Ca2+(aq) + 2 I(aq)

104 kJ = 2059 kJ + Hhyd, Hhyd = 2163 kJ

Using Hesss law:

H = HLE = (686 kJ/mol)

NaI(s) Na+(aq) + I(aq)

nonpolar; soluble in CCl4

polar; soluble in H2O

polar; soluble in H2O

nonpolar; soluble in CCl4

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

polar; soluble in H2O

g. C2H4, 2(4) + 4(1) = 12 e

nonpolar (like all compounds made up of

a. Mg2+; smaller size, higher charge