709

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. HNO
3
(l) H
+
(aq) + NO
3

(aq) b. Na
2
SO
4
(s) 2 Na
+
(aq) + SO
4
2
(aq)

c. Al(NO
3
)
3
(s) Al
3+
(aq) + 3 NO
3

(aq) d. SrBr
2
(s) Sr
2+
(aq) + 2 Br

(aq)

e. KClO
4
(s) K
+
(aq) + ClO
4

(aq) f. NH
4
Br(s) NH
4
+
(aq) + Br

(aq)

g. NH
4
NO
3
(s) NH
4
+
(aq) + NO
3

(aq) h. CuSO
4
(s) Cu
2+
(aq) + SO
4
2
(aq)

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

(aq)

14. Mol Na
2
CO
3
= 0.0700 L
L
CO Na mol 0 . 3
3 2
= 0.21 mol Na
2
CO
3


Na
2
CO
3
(s) 2 Na
+
(aq) + CO
3
2
(aq); mol Na
+
= 2(0.21) = 0.42 mol

Mol NaHCO
3
= 0.0300 L
L
NaHCO mol 0 . 1
3
= 0.030 mol NaHCO
3


NaHCO
3
(s) Na
+
(aq) + HCO
3

(aq); mol Na
+
= 0.030 mol


L 1000 . 0
mol 45 . 0
L 030 . 0 L 0700 . 0
mol 030 . 0 mol 42 . 0
volume total
Na mol total
Na
= = =
+
+
+
+
M = 4.5 M Na
+

710 CHAPTER 17 PROPERTIES OF SOLUTIONS

15. Molality =
g 07 . 62
EG mol 1
kg
g 1000
O H g 0 . 60
EG g 0 . 40
2
= 10.7 mol/kg

Molarity =
g 07 . 62
mol 1
L
cm 1000
cm
g 05 . 1
solution g 0 . 100
EG g 0 . 40
3
3
= 6.77 mol/L

40.0 g EG
g 07 . 62
mol 1
= 0.644 mol EG; 60.0 g H
2
O
g 02 . 18
mol 1
= 3.33 mol H
2
O


644 . 0 33 . 3
644 . 0

EG
+
= = 0.162 = mole fraction ethylene glycol

16. Hydrochloric acid (HCl):

molarity =
g 36.5
HCl mol 1
L
cm 1000
soln cm
soln g 1.19
soln g 100.
HCl g 38
3
3
= 12 mol/L

molality =
g 5 . 36
HCl mol 1
kg
g 1000
solvent g 62
HCl g 38
= 17 mol/kg

38 g HCl
g 5 . 36
mol 1
= 1.0 mol HCl; 62 g H
2
O
g 0 . 18
mol 1
= 3.4 mol H
2
O

mole fraction of HCl =
0 . 1 4 . 3
0 . 1

HCl
+
= = 0.23

Nitric acid (HNO
3
):

g 0 . 63
HNO mol 1
L
cm 1000
soln cm
soln g 42 . 1
soln g . 100
HNO g . 70
3
3
3
3
= 16 mol/L


g 0 . 63
HNO mol 1
kg
g 1000
solvent g . 30
HNO g . 70
3 3
= 37 mol/kg

70. g HNO
3

g 0 . 63
mol 1
= 1.1 mol HNO
3
; 30. g H
2
O
g 0 . 18
mol 1
= 1.7 mol H
2
O


1 . 1 7 . 1
1 . 1

3
HNO
+
= = 0.39



CHAPTER 17 PROPERTIES OF SOLUTIONS 711

Sulfuric acid (H
2
SO
4
):

4 2
4 2
3
3
4 2
SO H g 1 . 98
SO H mol 1
L
cm 1000
soln cm
soln g 84 . 1
soln g . 100
SO H g 95
= 18 mol/L


g 1 . 98
mol 1
kg
g 1000
O H g 5
SO H g 95
2
4 2
= 194 mol/kg ~ 200 mol/kg

95 g H
2
SO
4

g 1 . 98
mol 1
= 0.97 mol H
2
SO
4
; 5 g H
2
O
g 0 . 18
mol 1
= 0.3 mol H
2
O


3 . 0 97 . 0
97 . 0

4 2
SO H
+
= = 0.76

Acetic Acid (CH
3
CO
2
H):

g 05 . 60
mol 1
L
cm 1000
soln cm
soln g 05 . 1
soln g . 100
H CO CH g 99
3
3
2 3
= 17 mol/L


g 05 . 60
mol 1
kg
g 1000
O H g 1
H CO CH g 99
2
2 3
= 1600 mol/kg ~ 2000 mol/kg
99 g CH
3
CO
2
H
g 05 . 60
mol 1
= 1.6 mol CH
3
CO
2
H; 1 g H
2
O
g 0 . 18
mol 1
= 0.06 mol H
2
O


06 . 0 6 . 1
6 . 1

H CO CH
2 3
+
= = 0.96

Ammonia (NH
3
):

g 0 . 17
mol 1
L
cm 1000
cm
g 90 . 0
soln g . 100
NH g 28
3
3
3
= 15 mol/L

g 0 . 17
mol 1
kg
g 1000
O H g 72
NH g 28
2
3
= 23 mol/kg

28 g NH
3

g 0 . 17
mol 1
= 1.6 mol NH
3
; 72 g H
2
O
g 0 . 18
mol 1
= 4.0 mol H
2
O


6 . 1 0 . 4
6 . 1

3
NH
+
= = 0.29

17. 50.0 mL toluene
mL
g 867 . 0
= 43.4 g toluene; 125 mL benzene
mL
g 874 . 0
= 109 g benzene
712 CHAPTER 17 PROPERTIES OF SOLUTIONS

Mass % toluene =
mass total
toluene of mass
100 =
g 109 g 4 . 43
g 4 . 43
+
100 = 28.5%

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

Molality =
toluene g 92.13
toluene mol 1
kg
g 1000
benzene g 09 1
toluene g 43.4
= 4.32 mol/kg

43.4 g toluene
g 13 . 92
mol 1
= 0.471 mol toluene

109 g benzene
benzene g 11 . 78
benzene mol 1
= 1.40 mol benzene; _
toluene
=
40 . 1 471 . 0
471 . 0
+
= 0.252

18. If we have 100.0 mL of wine:

12.5 mL C
2
H
5
OH
mL
g 789 . 0
= 9.86 g C
2
H
5
OH and 87.5 mL H
2
O
mL
g 00 . 1
= 87.5 g H
2
O

Mass % ethanol =
g 86 . 9 g 5 . 87
g 86 . 9
+
100 = 10.1% by mass

Molality =
g 07 . 46
mol 1
O H kg 0875 . 0
OH H C g 86 . 9
2
5 2
= 2.45 mol/kg

19. If we have 1.00 L of solution:

1.37 mol citric acid
mol
g 1 . 192
= 263 g citric acid

1.00 10
3
mL solution
mL
g 10 . 1
= 1.10 10
3
g solution

Mass % of citric acid =
g 10 10 . 1
g 263
3

100 = 23.9%

In 1.00 L of solution, we have 263 g citric acid and (1.10 10
3
263) = 840 g of H
2
O.

Molality =
O H kg 84 . 0
acid citric mol 37 . 1
2
= 1.6 mol/kg

840 g H
2
O
g 0 . 18
mol 1
= 47 mol H
2
O;
37 . 1 47
37 . 1

acid citric
+
= = 0.028
CHAPTER 17 PROPERTIES OF SOLUTIONS 713

20.
ethanol kg 00 . 1
acetone mol 00 . 1
= 1.00 molal; 1.00 10
3
g C
2
H
5
OH
g 07 . 46
mol 1
= 21.7 mol C
2
H
5
OH


acetone
=
7 . 21 00 . 1
00 . 1
+
= 0.0441

1 mol CH
3
COCH
3
H
g 788 . 0
mL 1
COCH CH mol
COCH CH g 08 . 58
3 3
3 3
= 73.7 mL CH
3
COCH
3


1.00 10
3
g ethanol
g 789 . 0
mL 1
= 1270 mL; total volume = 1270 + 73.7 = 1340 mL

Molarity =
L 34 . 1
mol 00 . 1
= 0.746 M

21. Because the density of water is 1.00 g/mL, 100.0 mL of water has a mass of 100. g.

Density =
mL 104
O H g . 100 PO H g 0 . 10
volume
mass
2 4 3
+
= = 1.06 g/mL = 1.06 g/cm
3


Mol H
3
PO
4
= 10.0 g
g 99 . 97
mol 1
= 0.102 mol H
3
PO
4


Mol H
2
O = 100. g
g 02 . 18
mol 1
= 5.55 mol H
2
O

Mole fraction of H
3
PO
4
=
mol ) 55 . 5 102 . 0 (
PO H mol 102 . 0
4 3
+
= 0.0180


O H
2
= 1.0000 0.0180 = 0.9820

Molarity =
soln L 104 . 0
PO H mol 102 . 0
4 3
= 0.981 mol/L

Molality =
solvent kg 100 . 0
PO H mol 102 . 0
4 3
= 1.02 mol/kg

22. a. If we use 100. mL (100. g) of H
2
O, we need:

0.100 kg H
2
O
KCl mol
g 55 . 74
kg
KCl mol 0 . 2
= 14.9 g = 15 g KCl

714 CHAPTER 17 PROPERTIES OF SOLUTIONS

Dissolve 15 g KCl in 100. mL H
2
O 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 H
2
O, the volume would probably be less than 100 mL.
To make sure we have enough solution, lets use 100. mL H
2
O (100. g H
2
O). Let x =
mass of NaCl.
Mass % = 15 =
x
x
+ . 100
100, 1500 + 15x = (100.)x, x = 17.6 g ~ 18 g

Dissolve 18 g NaOH in 100. mL H
2
O to make a 15% NaOH solution by mass.

c. In a fashion similar to part b, lets use 100. mL CH
3
OH. Let x = mass of NaOH.

100. mL CH
3
OH 0.79 g/mL = 79 g CH
3
OH

Mass % = 25 =
x
x
+ 79
100, 25(79) + 25x = (100.)x, x = 26.3 g ~ 26 g

Dissolve 26 g NaOH in 100. mL CH
3
OH.

d. To make sure we have enough solution, lets use 100. mL (100. g) of H
2
O. Let x = mol
C
6
H
12
O
6
.

100. g H
2
O
g 02 . 18
O H mol 1
2
= 5.55 mol H
2
O

6 12 6
O H C
= 0.10 =
55 . 5 + x
x
, (0.10)x + 0.56 = x, x = 0.62 mol C
6
H
12
O
6


0.62 mol C
6
H
12
O
6
180.2 g/mol = 110 g C
6
H
12
O
6

Dissolve 110 g C
6
H
12
O
6
in 100. mL of H
2
O to prepare a solution with
6 12 6
O H C
= 0.10.


Thermodynamics of Solutions and Solubility

23. 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 AH
soln
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, AH
soln
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.
CHAPTER 17 PROPERTIES OF SOLUTIONS 715

24. AH
1
and AH
2
refer to the breaking of intermolecular forces in pure solute

and in pure solvent.
AH
3
refers to the formation of the intermolecular forces in solution between the solute and
solvent. AH
soln
is the sum AH
1
+ AH
2
+ AH
3
.

a. The electrostatic potential diagram illustrates that acetone (CH
3
COCH
3
), 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, AH
1
and AH
2
will be large and positive, while AH
3
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 AH
soln
to be slightly negative. Here AH
3
will be more than
negative enough to overcome the large positive value from the AH
1
and AH
2
terms
combined.

b. These two molecules are named ethanol (CH
3
CH
2
OH) 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 solute-
solvent interactions are somewhat weaker for ethanol-water solutions due to the small
nonpolar part of ethanol (CH
3
CH
2
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, AH
1
and AH
2
are large and positive, while AH
3

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, AH
soln
will be slightly positive because the AH
3
term is not negative enough to overcome the
large, positive AH
1
and AH
2
terms combined.

c. As the electrostatic potential diagrams indicate, both heptane (C
7
H
16
) and hexane (C
6
H
14
)
are nonpolar substances. For a nonpolar solute dissolved in a nonpolar solvent, AH
1
and
AH
2
are small and positive, while the AH
3
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
AH
1
, AH
2
, and AH
3
are all small values, the AH
soln
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, AH
soln
= 0.

d. This combination represents a nonpolar solute in a polar solvent. AH
1
will be small due
to the relative weak London dispersion forces which are broken when the solute (C
7
H
16
)
expands. AH
2
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 AH
3
term will be small because the nonpolar solute and polar solvent do
not interact with each other. The end result is that AH
soln
is a large positive value.


716 CHAPTER 17 PROPERTIES OF SOLUTIONS

25. Although the enthalpy change is endothermic when NaCl dissolves in water, the magnitude
of AH
soln
will be a value close to zero (AH
soln
~ 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 (AS
soln
> 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 AS
soln
furnishes the driving force for NaCl to dissolve in water.



26. 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.

27. Using Hesss law:

NaI(s) Na
+
(g) + I

(g) H = H
LE
= (686 kJ/mol)
Na
+
(g) + I

(g) Na
+
(aq) + I

(aq) H = H
hyd
= 694 kJ/mol

__________________________________________________________________________________________________________

NaI(s) Na
+
(aq) + I

(aq) H
soln
= 8 kJ/mol

H
soln
refers to the heat released or gained when a solute dissolves in a solvent. Here, an
ionic compound dissolves in water.

28. a. CaCl
2
(s) Ca
2+
(g) + 2 Cl

(g) H = H
LE
= (2247 kJ)
Ca
2+
(g) + 2 Cl

(g) Ca
2+
(aq) + 2 Cl

(aq) H = H
hyd

__________________________________________________________________________________________________

CaCl
2
(s) Ca
2+
(aq) + 2 Cl

(aq) H
soln
= 46 kJ

46 kJ = 2247 kJ + H
hyd
, H
hyd
= 2293 kJ

CaI
2
(s) Ca
2+
(g) + 2 I

(g) H = H
LE
= ( 2059 kJ)
Ca
2+
(g) + 2 I

(g) Ca
2+
(aq) + 2 I

(aq) H = H
hyd

____________________________________________________________________________________________________

CaI
2
(s) Ca
2+
(aq) + 2 I

(aq) H
soln
= 104 kJ

104 kJ = 2059 kJ + H
hyd
, H
hyd
= 2163 kJ

b. The enthalpy of hydration for CaCl
2
is more exothermic than for CaI
2
. 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.
CHAPTER 17 PROPERTIES OF SOLUTIONS 717

29. 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 Al
3+
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.

30. a. Mg
2+
; smaller size, higher charge b. Be
2+
; smaller size

c. Fe
3+
; smaller size, higher charge d. F

; smaller size

e. Cl

; smaller size f. SO
4
2
; higher charge

31. 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. NH
3
; similar to water, NH
3
is capable of H-bonding, unlike PH
3
.

b. CH
3
CN; CH
3
CN is polar, while CH
3
CH
3
is nonpolar.

c. CH
3
CO
2
H; CH
3
CO
2
H is capable of H-bonding, unlike the other compound.

32. Water is a polar solvent and dissolves polar solutes and ionic solutes. Carbon tetrachloride
(CCl
4
) 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. KrF
2
, 8 + 2(7) = 22 e

b. SF
2
, 6 + 2(7) = 20 e

nonpolar; soluble in CCl
4






polar; soluble in H
2
O
c. SO
2
, 6 + 2(6) = 18 e

d. CO
2
, 4 + 2(6) = 16 e

+ 1 more



polar; soluble in H
2
O







nonpolar; soluble in CCl
4

e. MgF
2
is an ionic compound so it is soluble in water.





F Kr F
S
F F
O C O
S
O
O
718 CHAPTER 17 PROPERTIES OF SOLUTIONS

f. CH
2
O, 4 + 2(1) + 6 = 12 e

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

polar; soluble in H
2
O nonpolar (like all compounds made up of
only carbon and hydrogen); soluble in CCl
4

33. 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.

34. The main intermolecular forces are:

hexane (C
6
H
14
): London dispersion; chloroform (CHCl
3
): dipole-dipole, London
dispersion; methanol (CH
3
OH): H-bonding; and H
2
O: 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.

35. 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 water-
fearing. 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 O
2
and N
2
, Henrys law works well since these gases do
not react with the water solvent.

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.

36. Henrys law is obeyed most accurately for dilute solutions of gases that do not dissociate in
or react with the solvent. O
2
will bind to hemoglobin in the blood. Because of this reaction in
the solvent, O
2
(g) in blood does not follow Henrys law.

C
H H
O
C C
H
H
H
H
CHAPTER 17 PROPERTIES OF SOLUTIONS 719

37. P
gas
= kC, 0.790 atm = k
L
mol 10 21 . 8
4

, k = 962 L atm/mol

P
gas
= kC, 1.10 atm =
mol
atm L 962
C, C = 1.14 10
3
mol/L

38. 750. mL grape juice
g 07 . 46
OH H C mol 1
mL
OH H C g 79 . 0
juice mL . 100
OH H C mL 12
5 2 5 2 5 2


OH H C mol 2
CO mol 2
5 2
2
= 1.54 mol CO
2
(carry extra significant figure)
1.54 mol CO
2
= total mol CO
2
= mol CO
2
(g) + mol CO
2
(aq) = n
g
+ n
aq



L 10 75
) K 298 (
K mol
atm L 08206 . 0
n
V
RT n
P
3
g
g
CO
2

|
|
.
|

\
|
= = = 326n
g


L 750 . 0
n
mol
atm L 32
kC P
aq
CO
2
= = = (42.7)n
aq



2
CO
P = 326n
g
= (42.7)n
aq
and from above n
aq
= 1.54 n
g
; solving:

326n
g
= 42.7(1.54 n
g
), 369n
g
= 65.8, n
g
= 0.18 mol


2
CO
P = 326(0.18) = 59 atm in gas phase; 59 atm =
mol
atm L 32
C, C = 1.8 mol CO
2
/L in wine

39. 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.


Vapor Pressures of Solution

40. Mol C
3
H
8
O
3
= 164 g
g 09 . 92
mol 1
= 1.78 mol C
3
H
8
O
3


Mol H
2
O = 338 mL
g 02 . 18
mol 1
mL
g 992 . 0
= 18.6 mol H
2
O


o
O H O H soln
2 2
P P = =
mol ) 6 . 18 78 . 1 (
mol 6 . 18
+
54.74 torr = 0.913 54.74 torr = 50.0 torr
720 CHAPTER 17 PROPERTIES OF SOLUTIONS

41.
solution in mol total
solution in OH H C mol
; P P
5 2
OH H C
o
OH H C OH H C soln
5 2 5 2 5 2
= =


53.6 g C
3
H
8
O
3

g 09 . 92
O H C mol 1
3 8 3
= 0.582 mol C
3
H
8
O
3
133.7 g C
2
H
5
OH
g 07 . 46
OH H C mol 1
5 2
= 2.90 mol C
2
H
5
OH; total mol = 0.582 + 2.90 = 3.48 mol
113 torr =
o
OH H C
o
OH H C
5 2 5 2
P , P
mol 3.48
mol 2.90
= 136 torr
42. Compared to H
2
O, solution d (methanol-water) will have the highest vapor pressure since
methanol is more volatile than water (
o
O H
2
P = 23.8 torr at 25C). 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.

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.

43. P = P; 710.0 torr = (760.0 torr), = 0.9342 = mole fraction of methanol

44. P
total
=
total mol 0800 . 0
Cl CH mol 0300 . 0
; P P ; P P
2 2 L
Cl CH
o L
Br CH Cl CH
2 2 2 2 2 2
= = + = 0.375

P
total
= 0.375(133 torr) + (1.000 0.375)(11.4 torr) = 49.9 + 7.13 = 57.0 torr

In the vapor:
torr 0 . 57
torr 9 . 49
P
P

total
Cl CH
V
Cl CH
2 2
2 2
= = = 0.875;
V
Br CH
2 2
= 1.000 0.875 = 0.125
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.

45.
o
B B B
o
B B B
P / P , P P = = = 0.900 atm/0.930 atm = 0.968

0.968 =
mol total
benzene mol
; mol benzene = 78.11 g C
6
H
6

g 11 . 78
mol 1
= 1.000 mol

Let x = mol solute; then:
B
= 0.968 =
x + 1.000
mol 1.000
, 0.968 + (0.968)x = 1.000, x = 0.033 mol
Molar mass =
mol 033 . 0
g 0 . 10
= 303 g/mol ~ 3.0 10
2
g/mol

CHAPTER 17 PROPERTIES OF SOLUTIONS 721

46.
total
V
CS CS
P P
2 2
= = 0.855(263 torr) = 225 torr

torr 375
torr 225
P
P
, P P
o
CS
CS
L
CS
o
CS
L
CS CS
2
2
2 2 2 2
= = = = 0.600

47. a. 25 mL C
5
H
12

15 . 72
mol 1
mL
g 63 . 0
= 0.22 mol C
5
H
12


45 mL C
6
H
14

17 . 86
mol 1
mL
g 66 . 0
= 0.34 mol C
6
H
14
; total mol = 0.22 + 0.34 = 0.56 mol


mol 56 . 0
mol 22 . 0
solution in mol total
solution in pentane mol

L
pen
= = = 0.39,
L
hex
= 1.00 0.39 = 0.61


o
pen
L
pen pen
P P = = 0.39(511 torr) = 2.0 10
2
torr; P
hex
= 0.61(150. torr) = 92 torr

P
total
= P
pen
+ P
hex
= 2.0 10
2
+ 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. For the vapor phase:


torr 290
torr 10 0 . 2
P
P
vapor mol total
vapor in pentane mol

2
total
pen V
pen

= = = = 0.69
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. ; P P , P P
o
ben
L
ben pen
o
tol
L
tol tol
= = for the vapor,
V
A
= P
A
/P
total
. Because the mole fractions of
benzene and toluene are equal in the vapor phase,
ben tol
P P = .

torr 95 ) 00 . 1 ( ) torr 28 ( , P ) 00 . 1 ( P P
L
tol
L
tol
o
ben
L
tol
o
ben
L
ben
o
tol
L
tol
= = =


L
ben
L
tol
L
tol
; 77 . 0 , 95 123 = = = 1.00 0.77 = 0.23

49. P
total
= P
meth
+ P
prop
, 174 torr =
L
meth
L
prop
L
prop
L
meth
000 . 1 ); torr 6 . 44 ( ) torr 303 ( + =
174 = 500 . 0
258
129
, torr 6 . 44 ) 000 . 1 ( 303
L
meth
L
meth
L
meth
= = +
500 . 0 000 . 1
L
prop
= 500 . 0 =




722 CHAPTER 17 PROPERTIES OF SOLUTIONS

50. 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 (CH
3
COCH
3
) 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 (CH
3
CH
2
OH) 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 solute-
solvent interactions are somewhat weaker for ethanol-water solutions due to the
significant nonpolar part of ethanol (CH
3
CH
2
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 (C
7
H
16
) and hexane (C
6
H
14
). 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 (C
7
H
16
) 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).

51. 50.0 g CH
3
COCH
3

g 08 . 58
mol 1
= 0.861 mol acetone
50.0 g CH
3
OH 1 mol/32.04 g = 1.56 mol methanol
644 . 0 000 . 1 ; 356 . 0
56 . 1 861 . 0
861 . 0

L
acetone
L
methanol
L
acetone
= = = =
+

P
total
= P
methanol
+ P
acetone
= 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:

488 . 0 512 . 0 000 . 1 ; 512 . 0
torr 6 . 188
torr 5 . 96
P
P

V
methanol
total
acetone V
acetone
= = = = =
CHAPTER 17 PROPERTIES OF SOLUTIONS 723

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.

52. a. An ideal solution would have a vapor pressure at any mole fraction of H
2
O 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.

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) H
soln
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
O H
2
= 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
O H
2
= 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.

53. 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 H
soln
= 0 for an
ideal solution. H
soln
for methanol-water is not zero. Because H
soln
< 0, this solution
exhibits negative deviation from Raoults law.

54. 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.

55. 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
o
B
P >
o
A
P , B is more volatile than A.)



724 CHAPTER 17 PROPERTIES OF SOLUTIONS

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 (C
6
H
12
O
6
) has
the same colligative properties as a solution of sucrose (C
12
H
22
O
11
) having the same con-
centration.

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.

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 M 0.62
K 295 mol K atm L 0.08206
atm 15
RT

1 - 1 -
= = =

11 22 12
O H C mol
g 30 . 342
L
mol 62 . 0
= 212 g/L ~ 210 g/L
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 K
f

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 AT, 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 =
CO H N g 60.06
CO H N mol 1
kg
g 1000
O H g 150.0
CO H N g 27.0
solvent kg
solute mol
4 2
4 2
2
4 2
= = 3.00 molal


T
b
= K
b
m =
molal
C 51 . 0
3.00 molal = 1.5C

The boiling point is raised from 100.0C to 101.5C (assuming P = 1 atm).

60. T
f
= K
f
m, T
f
= 1.50C =
molal
C 86 . 1
m, m = 0.806 mol/kg

0.200 kg H
2
O
3 8 3
3 8 3
2
3 8 3
O H C mol
O H C g 92.09
O H kg
O H C mol 0.806
= 14.8 g C
3
H
8
O
3


CHAPTER 17 PROPERTIES OF SOLUTIONS 725

61. Molality = m =
g 07 . 62
mol 1
kg
g 1000
O H g 0 . 50
O H C g 0 . 50
2
2 6 2
= 16.1 mol/kg
T
f
= K
f
m = 1.86 C/molal 16.1 molal = 29.9C; T
f
= 0.0C 29.9C = 29.9C
T
b
= K
b
m = 0.51C/molal 16.1 molal = 8.2C; T
b
= 100.0C + 8.2C = 108.2C
62. T = 25.50C 24.59C = 0.91C = K
f
m, m =
molal / C 1 . 9
C 91 . 0
o
o
= 0.10 mol/kg
Mass H
2
O = 0.0100 kg t-butanol
O H mol
O H g 02 . 8 1
butanol - t kg
O H mol 0.10
2
2 2
= 0.018 g H
2
O
63. m =
kg 600 . 0
g 0 . 58
mol 1
g 0 . 24
= 0.690 mol/kg; T
b
= K
b
m = 0.51C kg/mol 0.690 mol/kg = 0.35C
T
b
= 99.725C + 0.35C = 100.08C

64. = MRT, M =
K 298 mol K atm L 08206 . 0
atm 00 . 8
RT

1 1

= = 0.327 mol/L

65. T
b
= 77.85C 76.50C = 1.35C; m =
mol / kg C 03 . 5
C 35 . 1
K
T
o
o
b
b
= = 0.268 mol/kg

Mol biomolecule = 0.0150 kg solvent
solvent kg
n hydrocarbo mol 268 . 0
= 4.02 10
3
mol
From the problem, 2.00 g biomolecule was used, which must contain 4.02 10
3
mol
biomolecule. The molar mass of the biomolecule is:


mol 10 02 . 4
g 00 . 2
3

= 498 g/mol
66. M =
K . 300
mol K
atm L 08206 . 0
torr 760
atm 1
torr 745 . 0
RT

= = 3.98 10
5
mol/L

1.00 L
L
mol 10 98 . 3
5

= 3.98 10
5
mol catalase

Molar mass =
mol 10 98 . 3
g 00 . 10
5

= 2.51 10
5
g/mol
726 CHAPTER 17 PROPERTIES OF SOLUTIONS

67. T
f
= K
f
m, m =
benzene kg
thyroxine mol 10 5.86
mol / kg C 12 . 5
C 300 . 0
K
T
2
f
f

= =
The moles of thyroxine present are:
0.0100 kg benzene
benzene kg
thyroxine mol 10 5.86
2

= 5.86
4
10

mol thyroxine
From the problem, 0.455 g thyroxine was used; this must contain 5.86
4
10

mol thyroxine.
The molar mass of the thyroxine is:

molar mass =
mol 10
g 455 . 0
4
86 . 5

= 776 g/mol

68. m =
mol / kg C 86 . 1
C 0 . 30
K
T
o
o
f
f
= = 16.1 mol C
2
H
6
O
2
/kg

Because the density of water is 1.00 g/cm
3
, the moles of C
2
H
6
O
2
needed are:

15.0 L H
2
O
O H kg
O H C mol 1 . 16
O H L
O H kg 00 . 1
2
2 6 2
2
2
= 242 mol C
2
H
6
O
2

Volume C
2
H
6
O
2
= 242 mol C
2
H
6
O
2

g 11 . 1
cm 1
O H C mol
g 07 . 62
3
2 6 2
= 13,500 cm
3
= 13.5 L
T
b
= K
b
m =
molal
C 51 . 0
o
16.1 molal = 8.2C; T
b
= 100.0C + 8.2C = 108.2C

69. M =
g 10 0 . 9
mol 1
L
g 0 . 1
4

= 1.1 10
5
mol/L; = MRT

At 298 K: =
atm
torr 760
K 298
mol K
atm L 08206 . 0
L
mol 10 1 . 1
5

, = 0.20 torr

Because d = 1.0 g/cm
3
, 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 H
2
O is present, and molality equals molarity to the
correct number of significant figures.

T
f
= K
f
m =
molal
C 86 . 1
o
1.1 10
5
molal = 2.0 10
5
C

70. Osmotic pressure is better for determining the molar mass of large molecules. A temperature
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.

CHAPTER 17 PROPERTIES OF SOLUTIONS 727

71. = MRT = K 298
mol K
atm L 08206 . 0
L
mol 1 . 0
= 2.45 atm ~ 2 atm

= 2 atm
atm
Hg mm 760
~ 2000 mm ~ 2 m

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 H
2
O, then the fluid has a density of 1.0 g/cm
3
. The
density of Hg is 13.6 g/cm
3
.

Height of fluid ~ 2 m 13.6 30 m

72. T
f
= 5.51 - 2.81 = 2.70C;
C/molal 5.12
C 2.70
K
T
o
o
f
f
= = m = 0.527 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).


2 . 128
x
= moles naphthalene and
2 . 178
60 . 1 x
= moles anthracene


) 2 . 178 ( 2 . 128
) 2 . 128 ( ) 2 . 128 ( 60 . 1 ) 2 . 178 (
10 05 . 1 ,
solvent kg 0200 . 0
2 . 178
60 . 1
2 . 128
solvent kg
solute mol 527 . 0
2
x x
x x
+

+
= =



(50.0)x + 205 = 240., (50.0)x = 240. 205, (50.0)x = 35, x = 0.70 g naphthalene

So the mixture is:


g 60 . 1
g 70 . 0
100 = 44% naphthalene by mass and 56% anthracene by mass

73. 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.

Properties of Electrolyte Solutions

74. a. m =
g 44 . 58
mol 1
kg 025 . 0
NaCl g 0 . 5
= 3.4 molal; NaCl(aq) Na
+
(aq) + Cl

(aq), i = 2.0
T
f
= iK
f
m = 2.0 1.86C/molal 3.4 molal = 13C; T
f
= 13C
T
b
= iK
b
m = 2.0 0.51C/molal 3.4 molal = 3.5C; T
b
= 103.5C
728 CHAPTER 17 PROPERTIES OF SOLUTIONS

b. m =
g 01 . 213
mol 1
kg 015 . 0
) NO ( Al g 0 . 2
3 3
= 0.63 mol/kg

Al(NO
3
)
3
(aq) Al
3+
(aq) + 3 NO
3

(aq), i = 4.0
T
f
= iK
f
m = 4.0 1.86C/molal 0.63 molal = 4.7C; T
f
= 4.7C
T
b
= iK
b
m = 4.0 0.51C/molal 0.63 molal = 1.3C; T
b
= 101.3C

75. P = P; 19.6 torr = ) torr 8 . 23 (
O H
2
,
O H
2
= 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, P
soln
= 0.824(71.9 torr) = 59.2 torr.

76. If ideal, NaCl dissociates completely, and i = 2.00. T
f
= iK
f
m; assuming water freezes at
0.00C:

1.28C = 2 1.86 C kg/mol m, m = 0.344 mol NaCl/kg H
2
O

Assume an amount of solution that contains 1.00 kg of water (solvent).

0.344 mol NaCl
mol
g 44 . 58
= 20.1 g NaCl
Mass % NaCl =
g 1 . 20 g 10 00 . 1
g 1 . 20
3
+
100 = 1.97%

77. Na
3
PO
4
(s) 3 Na
+
(aq) + PO
4
3
(aq), i = 4.0; CaBr
2
(s) Ca
2+
(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 Na
3
PO
4
solution; 3.0(0.020 molal) = 0.060 molal
for the CaBr
2
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 Na
3
PO
4
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 C
6
H
12
O
6
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.
CHAPTER 17 PROPERTIES OF SOLUTIONS 729

c. T = K
f
m; the 0.020 m CaBr
2
solution has the largest effective particle concentration, so
it will have the largest freezing point depression (largest T).

78. The solutions of glucose, NaCl and CaCl
2
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 CaCl
2
solution will have the largest effective particle concentration
because it produces three ions per mole of compound.

a. pure water b. CaCl
2

solution c. CaCl
2

solution

d. pure water e. CaCl
2
solution

79. 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:
67 . 1
6
10
dissolved solute of moles
solution in particles of moles
i = = =
80. From Table 17.6, MgSO
4
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 MgSO
4
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 MgSO
4
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.

81. For CaCl
2
: i
molal 091 . 0 /molal C 86 . 1
C 440 . 0
K
T
o
o
f
f

A
= =
m
= 2.6

Percent CaCl
2
ionized =
0 . 1 0 . 3
0 . 1 6 . 2

100 = 80.%; 20.% ion association occurs.

For CsCl: i
molal 091 . 0 /molal C 86 . 1
C 320 . 0
K
T
o
o
f
f

A
= =
m
= 1.9
Percent CsCl ionized =
0 . 1 0 . 2
0 . 1 9 . 1

100 = 90.%; 10% ion association occurs.

The ion association is greater in the CaCl
2
solution.

82. 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
2
O) 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.
730 CHAPTER 17 PROPERTIES OF SOLUTIONS

b. Initially, H
2
O molecules will have a net migration into the solution side. However, the
solute can now migrate into the H
2
O 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.

83. NaCl(s) Na
+
(aq) + Cl

(aq), i = 2.0
= iMRT = 2.0 K 293
mol K
atm L 08206 . 0
L
mol 10 . 0
= 4.8 atm
A pressure greater than 4.8 atm should be applied to ensure purification by reverse osmosis.

84. a. MgCl
2
(s) Mg
2+
(aq) + 2 Cl

(aq), i = 3.0 mol ions/mol solute

T
f
= iK
f
m = 3.0 1.86 C/molal 0.050 molal = 0.28C; T
f
= -0.28C (Assuming water
freezes at 0.00C.)

T
b
= iK
b
m = 3.0 0.51 C/molal 0.050 molal = 0.077C; T
b
= 100.077C (Assuming
water boils at 100.000C.)
b. FeCl
3
(s) Fe
3+
(aq) + 3 Cl

(aq), i = 4.0 mol ions/mol solute

T
f
= iK
f
m = 4.0 1.86 C/molal 0.050 molal = 0.37C; T
f
= 0.37C
T
b
= iK
b
m = 4.0 0.51 C/molal 0.050 molal = 0.10C; T
b
= 100.10C

85. a. MgCl
2
, i (observed) = 2.7
T
f
= iK
f
m = 2.7 1.86 C/molal 0.050 molal = 0.25C; T
f
= 0.25C
T
b
= iK
b
m = 2.7 0.51 C/molal 0.050 molal = 0.069C; T
b
= 100.069C

b. FeCl
3
, i (observed) = 3.4
T
f
= iK
f
m = 3.4 1.86 C/molal 0.050 molal = 0.32C; T
f
= 0.32C
T
b
= iK
b
m = 3.4 0.51C/molal 0.050 molal = 0.087C; T
b
= 100.087C

86. T
f
= iK
f
m, i =
molal 0225 . 0 molal / C 86 . 1
C 110 . 0
K
T
o
o
f
f

=
m
= 2.63 for 0.0225 m CaCl
2


i =
0910 . 0 86 . 1
440 . 0

= 2.60 for 0.0910 m CaCl

2
; i =
278 . 0 86 . 1
330 . 1

= 2.57 for 0.278 m CaCl

2


Note that i is less than the ideal value of 3.0 for CaCl
2
. This is due to ion pairing in solution.

87. t = iMRT, M =
iRT

=
K 298
mol K
atm L 08206 . 0
00 . 2
atm 50 . 2

= 5.11
2
10

mol/L
CHAPTER 17 PROPERTIES OF SOLUTIONS 731

Molar mass of compound =
L
mol 10 11 . 5
L 1000 . 0
g 500 . 0
2

= 97.8 g/mol
88. a. T
C
= 5(T
F
32)/9 = 5(29 32)/9 = 34C

Assuming the solubility of CaCl
2
is temperature independent, the molality of a saturated
CaCl
2
solution is:


O H kg
CaCl mol 71 . 6
CaCl g 98 . 110
CaCl mol 1
kg
g 1000
O H g 0 . 100
CaCl g 5 . 74
2
2
2
2
2
2
=

T
f
= iK
f
m = 3.00 1.86 C kg/mol 6.71 mol/kg = 37.4C

Assuming i = 3.00, a saturated solution of CaCl
2
can lower the freezing point of water to
37.4C. Assuming these conditions, a saturated CaCl
2
solution should melt ice at 34C
(29F).

b. From Exercise 17.86, i ~ 2.6; T
f
= iK
f
m = 2.6 1.86 6.71 = 32C; T
f
= 32C.

Assuming i = 2.6, a saturated CaCl
2
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 parti-
cles 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 SO
4

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.














= nonpolar
hydrocarbon
= detergent
molecule
= SO
4
-
= dirt

732 CHAPTER 17 PROPERTIES OF SOLUTIONS

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. A 92 proof ethanol solution is 46% C
2
H
5
OH by volume. Assuming 100.0 mL of solution:

mol ethanol = 46 mL C
2
H
5
OH
g 07 . 46
OH H C mol 1
mL
g 79 . 0
5 2
= 0.79 mol C
2
H
5
OH
molarity =
L 1000 . 0
mol 79 . 0
= 7.9 M ethanol

94. Mass of H
2
O = 160. mL
mL
g 995 . 0
= 159 g = 0.159 kg

Mol NaDTZ = 0.159 kg
kg
mol 378 . 0
= 0.0601 mol

Molar mass of NaDTZ =
mol 0601 . 0
g 4 . 38
= 639 g/mol

P
soln
=
o
O H O H
2 2
P ; mol H
2
O = 159 g
g 02 . 18
mol 1
= 8.82 mol

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.
O H
2
=
mol 82 . 8 mol 120 . 0
mol 82 . 8
+
= 0.987; P
soln
= 0.987 34.1 torr = 33.7 torr
95. AT = K
f
m, m =
C/molal 86 . 1
C 79 . 2
K
T
o
o
f
= = 1.50 molal

a. AT = K
b
m, AT = 0.51
o
C/molal 1.50 molal = 0.77
o
C, T
b
= 100.77
o
C

CHAPTER 17 PROPERTIES OF SOLUTIONS 733

b.
water
o
water water soln
, P P = =
solute mol O H mol
O H mol
2
2
+


Assuming 1.00 kg of water, we have 1.50 mol solute, and:

mol H
2
O = 1.00 10
3
g H
2
O
O H g 02 . 18
O H mol 1
2
2
= 55.5 mol H
2
O
_
water
=
5 . 55 50 . 1
mol 5 . 55
+
= 0.974; P
soln
= (0.974)(23.76 mm Hg) = 23.1 mm Hg

c. We assumed ideal behavior in solution formation, we assumed the solute was nonvolatile,
and we assumed i = 1 (no ions formed).

96. AT = imK
f
, i =
f
K
T
m
=
mol
kg C 86 . 1
kg 500 . 0
mol 250 . 0
C 79 . 2
o
o

= 3.00

We have three ions in solutions, and we have twice as many anions as cations. Therefore, the
formula of Q is MCl
2
. Assuming 100.00 g of compound:

38.68 g Cl
g 45 . 35
Cl mol 1
= 1.091 mol Cl

mol M = 1.091 mol Cl
Cl mol 2
M mol 1
= 0.5455 mol M

Molar mass of M =
M mol 5455 . 0
M g 32 . 61
= 112.4 g/mol; M is Cd, so Q = CdCl
2
.

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.






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 (AT
f
=
K
f
m).
C O H
O
O H O
C
O H O
C
734 CHAPTER 17 PROPERTIES OF SOLUTIONS

98. Benzoic acid (see Exercise 97) would be more soluble in a basic solution because of the
reaction:
C
6
H
5
CO
2
H + OH

C
6
H
5
CO
2

+ H
2
O
By removing the proton from benzoic acid, an anion forms, and like all anions, the species
becomes more soluble in water.

99. a. NH
4
NO
3
(s) NH
4
+
(aq) + NO
3

(aq) H
soln
= ?

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 NH
4
NO
3
is endothermic (H is positive). Mass of solution = 1.60 +
75.0 = 76.6 g

Heat loss by solution =
g C
J 18 . 4
o
76.6 g (25.00C 23.34C) = 532 J

H
soln
=
3 4
3 4
3 4
NO NH mol
NO NH g 05 . 80
NO NH g 60 . 1
J 532
= 2.66 10
4
J/mol = 26.6 kJ/mol

b. We will use Hesss law to solve for the lattice energy. The lattice energy equation is:

NH
4
+
(g) + NO
3

(g) NH
4
NO
3
(s) H = lattice energy

NH
4
+
(g) + NO
3

(g) NH
4
+
(aq) + NO
3

(aq) H = H
hyd
= 630. kJ/mol
NH
4
+
(aq) + NO
3

(aq) NH
4
NO
3
(s) H = H
soln
= 26.6 kJ/mol

____________________________________________________________________________________________________________

NH
4
+
(g) +

NO
3

(g) NH
4
NO
3
(s) H = H
hyd
H
soln
= 657 kJ/mol

100. a. The average values for each ion are:

300. mg Na
+
, 15.7 mg K
+
, 5.45 mg Ca
2+
, 388 mg Cl

, and 246 mg lactate (C

3
H
5
O
3

)

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 NaC
3
H
5
O
3
.

246 mg C
3
H
5
O
3

3 5 3
3 5 3
O H C mg 07 . 89
O H NaC mg 06 . 112
= 309.5 mg sodium lactate

The only source of Ca
2+
is CaCl
2
-2H
2
O.

5.45 mg Ca
2+

+
-
2
2 2
Ca mg 40.08
O 2H CaCl mg 147.0
= 19.99 or 20.0 mg CaCl
2
-2H
2
O

The only source of K
+
is KCl.

CHAPTER 17 PROPERTIES OF SOLUTIONS 735

15.7 mg K
+

+
K mg 10 . 39
KCl mg 55 . 74
= 29.9 mg KCl

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
+

+
Na mg 99 . 22
NaCl mg 44 . 58
= 601.2 mg NaCl

Now let's check the mass of Cl

added:

20.0 mg CaCl
2
-2H
2
O
O 2H CaCl mg 147.0
Cl mg 70.90
2 2
-

= 9.6 mg Cl

20.0 mg CaCl
2
-2H
2
O = 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 CaCl
2
-2H
2
O, 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:


mg 99 . 22
mmol 1
mL . 100
Na mg 285

+
= 0.124 M;
mg 10 . 39
mmol 1
mL . 100
K mg 1 . 14

+
= 0.00361 M


mg 08 . 40
mmol 1
mL . 100
Ca mg 9 . 4
2

+
= 0.0012 M;
mg 45 . 35
mmol 1
mL . 100
Cl mg 368

= 0.104 M


mg 07 . 89
mmol 1
mL . 100
O H C mg 231
3 5 3

= 0.0259 M (Note: molarity = mol/L = mmol/mL.)

Total = 0.124 + 0.00361 + 0.0012 + 0.104 + 0.0259 = 0.259 M

= MRT =
mol K
atm L 08206 . 0
L
mol 259 . 0
310. K = 6.59 atm

Similarly, at maximum concentrations, the concentration for each ion is:
736 CHAPTER 17 PROPERTIES OF SOLUTIONS

Na
+
: 0.137 M; K
+
: 0.00442 M; Ca
2+
: 0.0015 M; Cl

: 0.115 M; C
3
H
5
O
3

: 0.0293 M

The total concentration of all ions is 0.287 M.

=
mol K
atm L 08206 . 0
L
mol 287 . 0
310. K = 7.30 atm
Osmotic pressure ranges from 6.59 atm to 7.30 atm.
101. .) 150 ( ) 511 ( P P P ; P P ;
P
P
15 . 0
L
hex
L
pen hex pen total
o
pen
L
pen pen
total
pen V
pen
+ + = = = = =

Because
L
pen
L
pen
L
pen total
L
pen
L
hex
361 . 150 .) 150 )( 000 . 1 ( ) 511 ( P : 000 . 1 + + = = =


L
pen
L
pen
L
pen
L
pen
total
pen V
pen
511 ) 361 . 150 ( 15 . 0 ,
361 . 150
) 511 (
15 . 0 ,
P
P
= = = +
+


23 + 54
L
pen
= 511
L
pen
,
L
pen
=
457
23
= 0.050

102. a. Water boils when the vapor pressure equals the pressure above the water. In an open pan,
P
atm
~ 1.0 atm. In a pressure cooker, P
inside
> 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 (T
f
= K
f
m). 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 CO
2
phase diagram (see Figure 16.58), the triple point is above 1 atm, and CO
2
(g)
is the stable phase at 1 atm and room temperature. CO
2
(l) can't exist at normal
atmospheric pressures. Therefore, dry ice sublimes instead of boils. In a fire
extinguisher, P > 1 atm and CO
2
(l) can exist. When CO
2
is released from the fire
extinguisher, CO
2
(g) forms as predicted from the phase diagram.

103. 14.2 mg CO
2

2
CO mg 01 . 44
C mg 01 . 12
= 3.88 mg C; % C =
mg 80 . 4
mg 88 . 3
100 = 80.8% C

1.65 mg H
2
O
O H mg 02 . 18
H mg 016 . 2
2
= 0.185 mg H; % H =
mg 80 . 4
mg 185 . 0
100 = 3.85% H

Mass % O = 100.00 (80.8 + 3.85) = 15.4% O

CHAPTER 17 PROPERTIES OF SOLUTIONS 737

Out of 100.00 g:

80.8 g C
g 01 . 12
mol 1
= 6.73 mol C;
963 . 0
73 . 6
= 6.99 ~ 7

3.85 g H
g 008 . 1
mol 1
= 3.82 mol H;
963 . 0
82 . 3
= 3.97 ~ 4

15.4 g O
g 00 . 16
mol 1
= 0.963 mol O;
963 . 0
963 . 0
= 1.00
Therefore, the empirical formula is C
7
H
4
O.

T
f
= K
f
m, m =
molal / C . 40
C 3 . 22
K
T
o
o
f
f
= = 0.56 molal
Mol anthraquinone = 0.0114 kg camphor
camphor kg
one anthraquin mol 56 . 0
= 6.4 10
3
mol
Molar mass =
mol 10 4 . 6
g 32 . 1
3

= 210 g/mol
The empirical mass of C
7
H
4
O is 7(12) + 4(1) + 16 ~ 104 g/mol. Because the molar mass is
twice the empirical mass, the molecular formula is C
14
H
8
O
2
.

104. Out of 100.00 g, there are:

31.57 g C
g 011 . 12
C mol 1
= 2.628 mol C;
628 . 2
628 . 2
= 1.000

5.30 g H
g 008 . 1
H mol 1
= 5.26 mol H;
628 . 2
26 . 5
= 2.00

63.13 g O
g 999 . 15
O mol 1
= 3.946 mol O;
628 . 2
946 . 3
= 1.502

Empirical formula: C
2
H
4
O
3
; use the freezing-point data to determine the molar mass.

m =
C/molal 1.86
C 5.20
K
T
o
o
f
f
= = 2.80 molal
Mol solute = 0.0250 kg
kg
solute mol 80 . 2
= 0.0700 mol solute
Molar mass =
mol 0700 . 0
g 56 . 10
= 151 g/mol
738 CHAPTER 17 PROPERTIES OF SOLUTIONS

The empirical formula mass of C
2
H
4
O
3
= 76.051 g/mol. Because the molar mass is about
twice the empirical mass, the molecular formula is C
4
H
8
O
6
, 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.

105. a. m =
mol / kg C 12 . 5
C 32 . 1
K
T
o
o
f
f
= = 0.258 mol/kg
Mol unknown = 0.01560 kg
kg
unknown mol 258 . 0
= 4.02 10
3
mol
Molar mass of unknown =
mol 10 02 . 4
g 22 . 1
3

= 303 g/mol

Uncertainty in temperature =
32 . 1
04 . 0
100 = 3%

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 K
f
value, e.g., camphor

106. MX M
+
+ X

K
sp
= [M
+
][X

]; AT = K
f
m, m =
86 . 1
028 . 0
K
T
f
= = 0.015 mol/kg

g 1000
kg 1
kg
mol 015 . 0
250 g = 0.00375 mol total solute particles (carrying extra sig. fig.)

Assume a solution density of 1.0 g/mL so that volume of solution = 250 mL.

[M
+
] =
L 0.25
) (0.00375/2
= 7.5 10
3
M, [X

] =
L 0.25
) (0.00375/2
= 7.5 10
3
M

K
sp
= [M
+
][X

] = (7.5 10
3
)(7.5 10
3
) = 5.6 10
5




CHAPTER 17 PROPERTIES OF SOLUTIONS 739

107. M
3
X
2
(s) 3 M
2+
(aq) + 2 X
3
(aq) K
sp
= [M
2+
]
3
[X
3
]
2


Initial s = solubility (mol/L) 0 0
Equil. 3s 2s

K
sp
= (3s)
3
(2s)
2
= 108s
5
; total ion concentration = 3s + 2s = 5s.

= iMRT, iM = total ion concentration
K 298 mol K atm L 08206 . 0
atm 10 64 . 2
RT

1 1
2

= =
= 1.08 10
3
mol/L
5s = 1.08 10
3
mol/L, s = 2.16 10
4
mol/L

K
sp
= 108s
5
= 108(2.16 10
4
)
5
= 5.08 10
17


108. m =
molal / C 86 . 1
C 426 . 0
K
T
o
o
f
f
= = 0.229 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 C
12
H
22
O
11
= 0.229 mol

Mass NaCl + mass C
12
H
22
O
11
= 20.0 g

2n
NaCl
+
11 22 12
O H C
n = 0.229 and 58.44(n
NaCl
) + ) ( 3 . 342
11 22 12
O H C
n = 20.0

Solving:
11 22 12
O H C
n = 0.0425 mol = 14.5 g and n
NaCl
= 0.0932 mol = 5.45 g

Mass % C
12
H
22
O
11
=
g 0 . 20
g 5 . 14
100 = 72.5 % and 27.5% NaCl by mass

11 22 12
O H C
=
mol 0932 . 0 mol 0425 . 0
mol 0425 . 0
+
= 0.313

109. m =
kg 5000 . 0
g 0 . 100
mol 1
g 100 . 0
= 2.00 10
3
mol/kg ~ 2.00 10
3
mol/L (dilute solution)

T
f
= iK
f
m, 0.0056C = i 1.86 C/molal 2.00 10
3
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

K
a
=
] HA [
] A [ ] H [
+

740 CHAPTER 17 PROPERTIES OF SOLUTIONS

Because the weak acid is 50.% dissociated:

[H
+
] = [A

] = [HA]
o
0.50 = 2.00 10
3
M 0.50 = 1.0 10
3
M

[HA] = [HA]
0
amount HA reacted = 2.00 10
3
M 1.0 10
3
M = 1.0 10
3
M

K
a
=
] HA [
] A [ ] H [
+
=
3
3 3
10 0 . 1
) 10 0 . 1 )( 10 0 . 1 (

= 1.0 10
3


110. T
f
= K
f
m, m =
molal / C 86 . 1
C 40 . 5
K
T
o
o
f
f
= = 2.90 molal


kg 0500 . 0 solvent kg
solute mol 90 . 2 n
= , n = 0.145 mol of ions in solution

Because NaNO
3
and Mg(NO
3
)
2
are strong electrolytes:

n = 2(x mol of NaNO
3
) + 3[y mol Mg(NO
3
)
2
] = 0.145 mol ions

In addition: 6.50 g = x mol NaNO
3 |
.
|

\
|
mol
g 00 . 85
+ y mol Mg(NO
3
)
2 |
.
|

\
|
mol
g 3 . 148


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(NO
3
)
2


Mass of Mg(NO
3
)
2
= 0.016 mol 148.3 g/mol = 2.4 g Mg(NO
3
)
2
, or 37% Mg(NO
3
)
2
by mass

Mass of NaNO
3
= 6.50 g - 2.4 g = 4.1 g NaNO
3
, or 63% NaNO
3
by mass

111. iM
) K 2 . 298 ( mol K atm L 08206 . 0
atm 3950 . 0
RT

1 1
= = = 0.01614 mol/L = total ion concentration

0.01614 mol/L
+ + + +
+ + + = =
Na Mg Cl Cl Na Mg
2 2
2 ; M M M M M M (charge balance)

Combining: 0.01614 =
+ +
+
Na Mg
2
2
3 M M

Let x = mass MgCl
2
and y = mass NaCl; then x + y = 0.5000 g.
CHAPTER 17 PROPERTIES OF SOLUTIONS 741


443 . 58
and
218 . 95
Na Mg
2
y
M
x
M = =
+ +
(Because V = 1.000 L.)

Total ion concentration =
443 . 58
2
218 . 95
3 y x
+ = 0.01614 mol/L
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 MgCl
2
= 0.5000 g 0.14 g = 0.36 g; mass % MgCl
2
=
g 5000 . 0
g 36 . 0
100 = 72%
112. Use the thermodynamic data to calculate the boiling point of the solvent.

At boiling point, G = 0 = H TS, H = TS, T =
1 1
3
mol K J 95 . 95
J/mol 10 90 . 33
S
H

= = 353.3 K
T = K
b
m, (355.4 K 353.3 K) = (2.5 K kg/mol)(m), m =
5 . 2
1 . 2
= 0.84 mol/kg
Mass solvent = 150. mL
g 1000
kg 1
mL
g 879 . 0
= 0.132 kg
Mass solute = 0.132 kg solvent
mol
g 142
solvent kg
solute mol 84 . 0
= 15.7 g = 16 g solute

Challenge Problems

113. From the problem,
L
CCl
L
H C
4 6 6
= = 0.500. We need the pure vapor pressures (P
o
) in order to
calculate the vapor pressure of the solution.

C
6
H
6
(l) C
6
H
6
(g) K
o
H C H C
6 6 6 6
P P = = at 25C

= =
o
) l ( H C , f
o
) g ( H C , f
o
rxn
6 6 6 6
G G G 129.66 kJ/mol 124.50 kJ/mol = 5.16 kJ/mol

G = RT ln K, ln K = = =


) K 298 ( ) mol K J 3145 . 8 (
J/mol 10 16 . 5
RT
G
1 1
3 o
2.08

K =
o
H C
6 6
P = e
2.08
= 0.125 atm
742 CHAPTER 17 PROPERTIES OF SOLUTIONS

For CCl
4
:
o
) l ( CCl , f
o
) g ( CCl , f
o
rxn
4 4
G G G = = 60.59 kJ/mol (65.21 kJ/mol)
= 4.62 kJ/mol

K =
o
CCl
4
P =
|
|
.
|

\
|

|
|
.
|

\
|

=
K 298 mol K J 3145 . 8
J/mol 4620
exp
RT
G
exp
1 1
o
= 0.155 atm

= =
o
H C
L
H C H C
6 6 6 6 6 6
P P 0.500(0.125 atm) = 0.0625 atm;
4
CCl
P = 0.500(0.155 atm)
= 0.0775 atm


1400 . 0
0625 . 0
atm 0775 . 0 atm 0625 . 0
atm 0625 . 0
P
P

total
H C
V
H C
6 6
6 6
= = =
+
= 0.446;
V
CCl
4
= 1.000 0.446
= 0.554

114. Let
L
A
= mole fraction A in solution, so 1.000
L
A
=
L
B
. From the problem,
V
A
= 2
L
A
.


V
A
=
total
A
P
P
=
) torr 0 . 100 )( 000 . 1 ( ) torr 0 . 350 (
) torr 0 . 350 (
L
A
L
A
L
A
+



V
A
= 2
L
A
=
L
A
L
A
L
A
) 0 . 250 ( ,
0 . 100 ) 0 . 250 (
) 0 . 350 (
+
= 75.0,
L
A
= 0.300

The mole fraction of A in solution is 0.300.

115. For the second vapor collected,
V
2 , B
= 0.714 and
V
2 , T
= 0.286. Let
L
2 , B
= mole fraction of
benzene in the second solution and
L
2 , T
= mole fraction of toluene in the second solution.


L
2 , T
L
2 , B
+ = 1.000
V
2 , B
= 0.714 =
T B
B
total
B
P P
P
P
P
+
= =
) torr 0 . 300 )( 000 . 1 ( ) torr 0 . 750 (
) torr 0 . 750 (
L
2 , B
L
2 , B
L
2 , B
+

Solving:
L
2 , B
= 0.500 =
L
2 , T


This second solution came from the vapor collected from the first (initial) solution, so,
V
1 , B
=
V
1 , T
= 0.500. Let
L
1 , B
= mole fraction benzene in the first solution and
L
1 , T
= mole fraction
of toluene in first solution.
L
1 , T
L
1 , B
+ = 1.000.
V
1 , B
= 0.500 =
T B
B
total
B
P P
P
P
P
+
= =
) torr 0 . 300 )( 000 . 1 ( ) torr 0 . 750 (
) torr 0 . 750 (
L
1 , B
L
1 , B
L
1 , B
+

Solving:
L
1 , B
= 0.286; the original solution had _
B
= 0.286 and _
T
= 0.714.
CHAPTER 17 PROPERTIES OF SOLUTIONS 743


116. 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 =
solution liters
solvent moles
; molality =
solvent kg
solvent moles


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/cm
3
. The density of a solution is close to
1.00 g/cm
3
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. AT = K
f
m, m =
f
K
T
=
kg/mol C 1.86
C 0.621
o
o
= 0.334 mol/kg

Assuming 0.334 mol/kg = 0.334 mol/L:

t = MRT = K 298
mol K
atm L 08206 . 0
L
mol 334 . 0
= 8.17 atm
d. m =
b
K
T
=
kg/mol C 0.51
C 2.0
o
o
= 3.92 mol/kg
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.

117. a. Assuming MgCO
3
(s) does not dissociate, the solute concentration in water is:


g 32 . 84
MgCO mol 1
L
g 10 560
L
mg 560
mL
(s) MgCO g 560
3
3
3

= =
= 6.6 10
3
mol MgCO
3
/L

An applied pressure of 8.0 atm will purify water up to a solute concentration of:

M
L
mol 32 . 0
K . 300 mol K atm L 08206 . 0
atm 0 . 8
RT

1 1
= = =

When the concentration of MgCO
3
(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 H
2
O. 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
744 CHAPTER 17 PROPERTIES OF SOLUTIONS

The minimum total volume of water that must be processed is 45 L + 0.96 L = 46 L.

Note: If MgCO
3
does dissociate into Mg
2+
and CO
3
2
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.

118. m =
C/molal 1.86
C 0.406
K
T
o
o
f
= = 0.218 mol/kg
t = 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.

t = 0.218 M 0.08206 L atm K
1
mol
1
298 K = 5.33 atm

119. a. Assuming no ion association between SO
4
2
(aq) and Fe
3+
(aq), then i = 5 for Fe
2
(SO
4
)
3
.

= iMRT = 5 0.0500 mol/L 0.08206 L atm K
1
mol
1
298 K = 6.11 atm

b. Fe
2
(SO
4
)
3
(aq) 2 Fe
3+
(aq) + 3 SO
4
2
(aq)

Under ideal circumstances, 2/5 of calculated above results from Fe
3+
and 3/5 results from
SO
4
2
. The contribution to from SO
4
2
is 3/5 6.11 atm = 3.67 atm. Because SO
4
2
is
assumed unchanged in solution, the SO
4
2
contribution in the actual solution will also be 3.67
atm. The contribution to the actual from the Fe(H
2
O)
6
3+
dissociation reaction is 6.73 3.67
= 3.06 atm.

The initial concentration of Fe(H
2
O)
6
2+
is 2(0.0500) = 0.100 M. The setup for the weak acid
problem is:
Fe(H
2
O)
6
3+
H
+
+ Fe(OH)(H
2
O)
5
2+
K
a
=
] ) O H ( Fe [
] ) O H )( OH ( Fe ][ H [
3
6 2
2
5 2
+
+ +

Initial 0.100 M ~0 0
x mol/L of Fe(H
2
O)
6
3+
reacts to reach equilibrium
Equil. 0.100 x x x

Total ion concentration = iM = = =

) K 298 ( mol K atm L 08206 . 0
atm 06 . 3
RT

1 1
0.125 M
0.125 M = 0.100 x + x + x = 0.100 + x, x = 0.025 M

CHAPTER 17 PROPERTIES OF SOLUTIONS 745


K
a
=
] ) O H ( Fe [
] ) O H )( OH ( Fe ][ H [
3
6 2
2
5 2
+
+ +
=
075 . 0
) 025 . 0 (
) 025 . 0 100 . 0 (
) 025 . 0 (
100 . 0
2 2 2
= =
x
x

= 8.3 10
3


120. Initial moles VCl
4
= 6.6834 g VCl
4
1 mol VCl
4
/192.74 g VCl
4
= 3.4676 10
2
mol VCl
4

Total molality of solute particles = im =
mol / kg C 8 . 29
C 97 . 5
K
T
o
o
f
= , 0.200 mol/kg
Because we have 0.1000 kg CCl
4
, the total moles of solute particles present is:

0.200 mol/kg (0.1000 kg) = 0.0200 mol

2 VCl
4
V
2
Cl
8
K =
2
4
8 2
] VCl [
] Cl V [

Initial 3.4676 10
2
mol 0
2x mol VCl
4
reacts to reach equilibrium
Equil. 3.4676 10
2
2x x

Total moles solute particles = 0.0200 mol = mol VCl
4
+ mol V
2
Cl
8
= 3.4676 10
2
2x + x

0.0200 = 3.4676 10
2
x, x = 0.0147 mol

At equilibrium, we have 0.0147 mol V
2
Cl
8
and 0.0200 - 0.0147 = 0.0053 mol VCl
4
. 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 cm
3
/1.696 g = 62.91 cm
3
= 0.06291 L

The equilibrium concentrations are:

[V
2
Cl
8
] =
L 06291 . 0
mol 0147 . 0
= 0.234 mol/L; [VCl
4
] =
L 06291 . 0
mol 0053 . 0
= 0.084 mol/L

K = = =
2 2
4
8 2
) 084 . 0 (
234 . 0
] VCl [
] Cl V [
33

121. a. = iMRT, iM = = =

K 298 mol K atm L 08206 . 0
atm 83 . 7
RT

1 1
0.320 mol/L
Assuming 1.000 L of solution:

total mol solute particles = mol Na
+
+ mol Cl

+ mol NaCl = 0.320 mol

mass solution = 1000. mL
mL
g 071 . 1
= 1071 g solution

746 CHAPTER 17 PROPERTIES OF SOLUTIONS

mass NaCl in solution = 0.0100 1071 g = 10.7 g NaCl

mol NaCl added to solution = 10.7 g
g 44 . 58
mol 1
= 0.183 mol NaCl
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 =
183 . 0
046 . 0
= 0.25, or 25%
b. T = K
f
m, where K
f
= 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
kg 060 . 1
mol 320 . 0
= 0.562C

Assuming water freezes at 0.000C, then T
f
= 0.562C.

122. For 30.% A by moles in the vapor, 30. =
B A
A
P P
P
+
100:
0.30 =
y x
x
y x
x
) 00 . 1 (

30 . 0 ,


A A
A
B A
A
+ +
=


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
= ;
30 . 0 70 . 0
30 . 0
y x
y
+

B
= 1.00
A
Similarly, if vapor above is 50.% A:
y x
y
y x
y
+

+
= = 00 . 1 ;
B A

If vapor above is 80.% A:
A
= ;
80 . 0 20 . 0
80 . 0
y x
y
+

B
= 1.00
A


CHAPTER 17 PROPERTIES OF SOLUTIONS 747


If the liquid solution is 30.% A by moles,
A
= 0.30.

Thus =
V
A

B A
A
P P
P
+
=
y x
x
y x
x
70 . 0 30 . 0
30 . 0
00 . 1 and
70 . 0 30 . 0
30 . 0
V
B
+

+
=
If solution is 50.% A:
V
A
V
B
V
A
00 . 1 and
+
= =
y x
x

If solution is 80.% A:
V
A
V
B
V
A
00 . 1 and
20 . 0 80 . 0
80 . 0
=
+
=
y x
x


Marathon Problem

123. a. From part a information we can calculate the molar mass of Na
n
A and deduce the
formula.

Mol Na
n
A = mol reducing agent = 0.01526 L
L
mol 02313 . 0
= 3.530 10
4
mol Na
n
A

Molar mass of Na
n
A =
mol 10 530 . 3
g 10 0 . 30
4
3

= 85.0 g/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 EO
2

or
EO
3

, 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 EO
2

, molar mass of E = 62.0 32.0 = 30.0

g/mol. Phosphorus is close, but PO
2

anions are not common. If EO

3

, molar mass of E
= 62.0 48.0 = 14.0. Nitrogen has this molar mass, and NO
3

anions are very common.

Therefore, NO
3

is a possible formula for A

.

Next, we assume Na
2
A and Na
3
A 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 NO
3

= 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 body-
centered 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 = 3 l where l =
cubic edge length.

l =
3
) cm 10 984 . 1 ( 4
3
r 4
8

= = 4.582 10
8
cm

Volume of unit cell = l
3
= (4.582 10
8
)
3
= 9.620 10
23
cm
3

748 CHAPTER 17 PROPERTIES OF SOLUTIONS

Mass of M in a unit cell = 9.620 10
23
cm
3

3
cm
g 243 . 5
= 5.044 10
22
g M
Mol M in a unit cell = 2 atoms
23
10 022 . 6
mol 1

= 3.321 10
24
mol M

Molar mass of M =
M mol 10 321 . 3
M g 10 044 . 5
24
22

= 151.9 g/mol

From the periodic table, M is europium (Eu). Given that the charge of Eu is +3, then the
formula of the salt is Eu(NO
3
)
3
-zH
2
O.

c. Part c data allow determination of the molar mass of Eu(NO
3
)
3
-zH
2
O, from which we can
determine z, the number of waters of hydration.

B = iMRT, iM =
) K 298 ( mol K atm L 08206 . 0
torr 760
atm 1
torr 558
RT

1 1
|
|
.
|

\
|
= = 0.0300 mol/L

The total molarity of solute particles present is 0.0300 M. The solute particles are Eu
3+

and NO
3

ions (the waters of hydration are not solute particles). Because each mole of
Eu(NO
3
)
3
-zH
2
O dissolves to form four ions (Eu
3+
+ 3 NO
3

), the molarity of
Eu(NO
3
)
3
-zH
2
O is 0.0300/4 = 0.00750 M.

Mol Eu(NO
3
)
3
-zH
2
O = 0.01000 L
L
mol 00750 . 0
= 7.50 10
5
mol

Molar mass of Eu(NO
3
)
3
-zH
2
O =
mol 10 50 . 7
g 10 45 . 33
5
3

= 446 g/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(NO
3
)
3
-6H
2
O.