CHAPTER 13

SOLUTIONS AND THEIR PHYSICAL PROPERTIES

PRACTICE EXAMPLES
1A To determine mass percent, we need both the mass of ethanol and the mass of solution. From
volume percent, we know that 100.0 mL of solution contains 20.0 mL pure ethanol. The
density of pure ethanol is 0.789 g/mL. We now can determine the mass of solute (ethanol)
and solution. We perform the calculation in one step.
0.789 g
20.0 mL ethanol 
mass percent ethanol = 1 mL ethanol  100%  16.2% ethanol by mass
0.977 g
100.0 mL soln 
1 mL soln

1B In each case, we use the definition of the concentration unit, making sure that the numerator
and denominator are converted to the correct units.
(a) We first determine the mass in grams of the solute and of the solution.
0.793 g
mass CH 3OH = 11.3 mL CH 3OH  = 8.96 g CH 3OH
1 mL
0.980 g
mass soln = 75.0 mL soln  = 73.5 g soln
1 mL
1 mol H 2 O
amount of H 2 O =  73.5 g soln  8.96 g CH 3OH  
18.02 g H 2 O
amount of H 2 O = 3.58 mol H 2O
1 mol CH 3OH
amount of CH 3OH = 8.96 g CH 3OH  = 0.280 mol CH 3OH
32.04 g CH 3OH
H 2 O mole amount of H 2 O in moles 3.58 mol H 2 O
= = = 0.927
fraction amount of soln in moles 3.58 mol H 2 O + 0.280 mol CH 3OH

amount of CH 3OH in moles 0.280 mol CH 3OH

(b) CH 3OH = =  3.73 M
volume of soln in L 1L
75.0 mL soln 
1000 mL
mass of H 2 O  7.35  8.96  64.5 g H 2 O
amount of CH 3OH in moles 0.280 mol CH 3OH
(c) molality of CH 3OH = =  4.34 m
mass of H 2 O in kg 1 kg
64.5 g H 2 O 
1000 g

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2A First we need to find the amount of each component in solution. Let us consider a 100.00-g
sample of solution, in which there are 16.00 g glycerol and 84.00 g water.
The shorthand notation for glycerol, HOCH 2CH(OH)CH 2OH, is C3 H 5  OH 3
1 mol C3 H 5  OH 3
amount of glycerol = 16.00 g C3 H 5  OH 3  = 0.1737 mol C3H 5  OH 3
92.10 g C3H 5  OH 3
1 mol H 2 O
amount of water = 84.00 g H 2 O  = 4.661 mol H 2 O
18.02 g H 2 O

nC3H5  OH  0.1737 mol C3H 5  OH 3

mole fraction of C3 H 5  OH 3 = 3
=
n[C3H5 (OH)3 + H 2O] 0.1737 mol C3 H 5  OH 3 + 4.661 mol H 2 O
mole fraction of C3 H5  OH 3 = 0.03593

2B First we need the amount of sucrose in solution. We use a 100.00-g sample of solution, in
which there are 10.00 g sucrose and 90.00 g water.
1 mol C12 H 22 O11
amount C12 H 22 O11 = 10.00 g C12 H 22 O11  = 0.02921 mol C12 H 22 O11
342.30 g C12 H 22 O11
(a) Molarity is amount of solute in moles per liter of solution. Convert the 100.00 g of
solution to L with density as a conversion factor.
0.02921 mol C12 H 22 O11 1.040 g soln 1000 mL
C12 H 22 O11 molarity =   = 0.3038 M
1000. g soln 1 mL 1L
(b) Molality is amount of solute in moles per kilogram of solvent.
Convert 90.00 g of solvent to kg.
0.02921 mol C12 H 22 O11 1000 g
C12 H 22 O11 molality =  = 0.3246 m
90.00 g H 2 O 1 kg
(c) Mole fraction is the moles of solute per moles of solution. First compute the moles in
90.00 g H 2 O .
1 mol H 2 O
n H 2 O = 90.00 g  = 4.994 mol H 2 O
18.02 g H 2 O
0.02921 mol C12 H 22 O11
mole fraction C12 H 22 O11 = = 0.005815
0.02921 mol C12 H 22 O11 + 4.994 mol H 2 O

3A Water is a highly polar compound. In fact, water molecules bond to each other through
hydrogen bonds, which are unusually strong dipole–dipole interactions. Thus, water should
mix well with other polar, hydrogen bonding compounds. (a) Toluene is nonpolar and should
not be very soluble in water. (c) Benzaldehyde can form hydrogen bonds to water through its
O atom. However, most of the molecule is nonpolar and, as a result, it has limited solubility
in water. (b) Oxalic acid is polar and can form hydrogen bonds. Of these three compounds,
oxalic acid should be the most readily soluble in water. Actual solubilities (w/w%) are:
toluene (0.067%)  benzaldehyde (0.28%)  oxalic acid (14%).

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3B Both I 2 and CCl 4 are nonpolar molecules. It does not take much energy to break the
attractions among I 2 molecules, or among CCl 4 molecules. Also, there is not a strong
I 2  CCl4 attraction created when a solution forms. Thus, I 2 should dissolve well in CCl 4 by
simple mixing. H 2 O is extensively hydrogen bonded with strong intermolecular forces that
are difficult to break, but there is not a strong I 2  H 2 O attraction created when a solution
forms. Thus, we expect I 2 to dissolve poorly in water. Actual solubilities are:
2.603 g I 2 /100 g CCl 4 and 0.033 g I 2 /100 g H 2 O .

4A The two suggestions are quoted first, followed by the means for achieving each one.
(1) Dissolve the 95 g NH 4 Cl in just enough water to produce a saturated solution
(55 g NH 4 Cl / 100 g H 2 O) at 60 C .
100 g H 2 O
mass of water needed = 95 g NH 4 Cl  = 173 g H 2 O
55 g NH 4 Cl
The mass of NH 4 Cl in the saturated solution at 20 C will be smaller.
37 g NH 4 Cl
mass NH 4 Cl dissolved = 173 g H 2 O  = 64 g NH 4 Cl dissolved
100 g H 2 O
crystallized mass NH 4 Cl = 95 g NH 4 Cl total  64 g NH 4 Cl dissolved at 20 C
= 31 g NH 4 Cl crystallized

(2) Lower the final temperature to 0º C, rather than 20º C. From Figure 13-8, at 0º C, the
solubility of NH4Cl is 28.5 g NH4Cl/100 g H2O. From this (and knowing that there are
173 g H2O present in the solution) we calculate the mass of NH4Cl dissolved at this
lower temperature.
28.5 g NH 4 Cl
mass dissolved NH 4Cl = 173 g H 2 O  = 49.3 g NH 4Cl dissolved
100 g H 2 O
The mass of NH 4 Cl recrystallized is 95 g  49.3 g = 46 g
 46 g 
yield =   100% = 48%
 95 g 

4B Percent yield for the recrystallization can be defined as:

mass crystallized
% yield =  100%
mass dissolved  40C 
mass dissolved  at 40C   mass dissolved  at 20C 
% yield =  100%
mass dissolved  at 40C 
Figure 13-8 solubilities per 100 g H2O are followed by percent yield calculations.
Solubility of KClO 4 : 4.84 g at 40o C and 3.0 g at 20o C
4.84 g  3.0 g
Percent yield of KClO 4 = ×100% = 38% KClO 4
4.84 g

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Solubility of KNO3: 60.7 g at 40o C and 32.3 g at 20o C

60.7 g  32.3 g
Percent Yield of KNO3 = ×100% = 47% KNO3
60.7 g
Solubility of K 2SO 4 : 15.1 g at 40o C and 11.9 g at 20o C
15.1 g  11.9 g
Percent yield of K 2SO 4 = ×100% = 21% K 2SO 4
15.1 g
Ranked in order of decreasing percent yield we have:
KNO3  47%   KClO 4  38%   K 2SO 4  21% 

5A From Example 13-5, we know that the Henry's law constant for O2 dissolved in water is
k = 2.18  103 M atm1 . Consequently,
1 mol O 2
5.00  103 g 
32.00 g O 2
C 0.100 L
Pgas = = = 0.717 atm O 2 pressure
k 2.18  103 M atm 1
5B We note the relationship between gas partial pressure over a liquid and its dissolved
concentration is given by Henry’s Law: C = kH P, where C is the concentration (given in
dimensionless “volume parts” unit, akin to ppm), kH is the Henry’s Law constant, and P is the
partial pressure of CO, which is given by:  P CO  PCO Ptotal . Assuming a CO partial pressure
of 1.0 (100% at 1 atm), the kH value is 0.0354 mL·mL-1·atm-1.

First, since the concentration of CO is 0.0100 mol CO/1.000 L of H2O, we have to find the
volume of CO at 273 K and 1.0 atm. That is,

nRT  0.0100 mol   0.08206 L  atm  mol  K   273 K 

1 1

V=   0.224 L
P 1.0 atm
Therefore, the concentration of CO may be expressed as follows:
0.224 L CO
v/v concentration of CO =  0.224 L/L or 0.224 mL/mL
1.000 L H 2 O
C 0.224 mL  mL1
PCO = = = 6.328 atm
k 0.0354 mL  mL1  atm 1

6A Raoult's law enables us to determine the vapor pressure of each component.

Phex =  hex P hex = 0.750  149.1 mmHg = 112 mmHg
Ppen =  pen P pen = 0.250  508.5 mmHg = 127 mmHg.
We use Dalton's law to determine the total vapor pressure:
Ptotal = Phex + Ppen = 112 mmHg +127 mmHg = 239 mmHg

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6B The masses of solution components need to be converted to amounts in moles through the use
of molar masses. Let us choose as our amount precisely 1.0000 mole of C 6 H 6 = 78.11 g C 6 H 6
and an equal mass of toluene.
1 mol C7 H 8
amount of toluene = 78.11 g C7 H 8  = 0.8477 mol C7 H 8
92.14 g C7 H 8
0.8477 mol C7 H 8
mole fraction toluene =  tol = = 0.4588
0.8477 mol C7 H 8 +1.0000 mol C6 H 6
toluene vapor pressure =  tol P tol = 0.4588  28.4 mmHg = 13.0 mmHg
b g
benzene vapor pressure =  benz P benz = 1.0000  0.4588  95.1 mmHg = 51.5 mmHg.
total vapor pressure = 13.0 mmHg + 51.5 mmHg = 64.5 mmHg

7A The vapor pressure composition of each component is that component's partial pressure
divided by the total pressure. Again, we note that the vapor is richer in the more volatile
component.
P 112 mmHg hexane P 127 mmHg pentane
yhexane = hexane = = 0.469 ypentane = pentane = = 0.531 or
Ptotal 239 mmHg total Ptotal 239 mmHg total
simply 1.000  0.469 = 0.531

7B The vapor pressure composition of each component is that component's partial pressure divided by
the total pressure. Again we note that the vapor is richer in the more volatile component.
P 13.0 mmHg toluene P 51.5 mmHg benzene
yt = toluene = = 0.202 yb = benzene = = 0.798
Ptotal 64.5 mmHg total Ptotal 64.5 mmHg total
or simply 1.000-0.202 = 0.798

8A We use the osmotic pressure equation, converting the mass of solute to amount in moles, the
temperature to Kelvin, and the solution volume to liters.
FG
. g C12 H 22 O11 
150
1 mol C12 H 22 O11 IJ
 0.08206
L atm
 298 K

nRT

H 342.3 g C12 H 22 O11 K mol K
 0.857 atm
V 1L
125 mL 
1000 mL
8B We use the osmotic pressure equation to determine the molarity of the solution.
n  0.015 atm
= = 1 1
= 6.1104 M
V RT 0.08206 L atm mol K  298 K

Now, we can calculate the mass of urea.

6.1  104 mol urea 60.06 g CO  NH 2 2
urea mass = 0.225 L   = 8.24  103 g
1 L soln 1 mol CO  NH 2  2

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9A We could substitute directly into the equation for molar mass derived in Example 13-9, but let
us rather think our way through each step of the process. First, we find the concentration of
n
the solution, by rearranging  = RT . We need to convert the osmotic pressure to
V
atmospheres.
1 atm
8.73 mmHg 
n  760 mmHg
   4.70 104 M
V RT L atm
0.08206  298 K
mol K
Next we determine the amount in moles of dissolved solute.
1L 4.70  104 mol solute
amount of solute = 100.0 mL   = 4.70  105 mol solute
1000 mL 1 L solution
We use the mass of solute, 4.04 g
 M= = 8.60 104 g/mol
4.04 g, to determine the molar mass. 
4.70  10 mol
5

9B We use the osmotic pressure equation along with the molarity of the solution.
1 mol
2.12 g 
n 6.86  104 g 0.08206 L atm
  RT    (310.2)K  0.0105 atm = 7.97 mmHg
V 1L mol K
75.00 mL 
1000 mL

10A (a) The freezing point depression constant for water is K f = 1.86  C m1 .
T f 0.227 C
molality = = = 0.122 m
 K f 1.86 C m 1

(b) We will use the definition of molality to determine the number of moles of riboflavin
in 0.833 g of dissolved riboflavin.
1 kg solvent 0.122 mol solute
amount of riboflavin = 18.1 g solvent H 2 O  
1000 g 1 kg solvent
amount of riboflavin = 2.21  103 mol riboflavin
0.833 g riboflavin
molar mass = = 377 g/mol
2.21103 mol
(c) We use the method of Chapter 3 to find riboflavin's empirical formula, starting with a
100.00-g sample.

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Chapter 13: Solutions and Their Physical Properties

1 mol C
54.25 g C  = 4.517 mol C 1.063  = 4.249 mol C
12.01 g C
1 mol H
5.36 g H  = 5.32 mol H 1.063  = 5.00 mol H
1.008 g H
1 mol O
25.51 g O  = 1.594 mol O 1.063  = 1.500 mol O
16.00 g O
1 mol N
14.89 g N  = 1.063 mol N  1.063  = 1.000 mol N
14.01 g N
If we multiply each of these amounts by 4 (because 4.249 is almost equal to 4 41 ), the
empirical formula is found to be C17 H 20O 6 N 4 with a molar mass of 376 g/mol. The
molecular formula is C17 H 20O 6 N 4 .

10B The boiling point of pure water at 760.0 mmHg is 100.000 C. For higher pressures, the
boiling point occurs at a higher temperature; for lower pressures, a lower boiling point is
observed. The boiling point elevation for the urea solution is calculated as follows.
Tb = Kb  m = 0.512  Cm1  0.205m = 0.105  C
b g
We would expect this urea solution to boil at 100.00 + 0.105 = 100.105  C under 760.0
mmHg atmospheric pressure. Since it boils at a lower temperature, the atmospheric pressure
must be lower than 760.0 mmHg.

11A We assume a van't Hoff factor of i = 3.00 and convert the temperature to Kelvin, 298 K.
3.00 mol ions 0.0530 mol MgCl2 L atm
 = iMRT =   0.08206  298 K = 3.89 atm
1 mol MgCl2 1 L soln mol K

11B We first determine the molality of the solution, and assume a van't Hoff factor of i = 2.00.
Tf 0.100 C
m= = = 0.0269 m  0.0269 M
 K f  i 1.86  Cm 1  2.00
0.0269 mmol HCl 1 mL conc soln
volume of HCl  aq  = 250.0 mL final soln  
1 mL soln 12.0 mmol HCl
volume of HCl  aq  = 0.560 mL conc soln

INTEGRATIVE EXAMPLE
A. We determine the mass of each component in the water-rich phase.
92.50 g H 2 O
mass H 2O  32.8 g phase   30.3 g H 2 O
100.00 g phase
mass phenol = 32.8 g phase – 30.3 g H2O = 2.5 g phenol
Then we determine the mass of each component in the other phase.
mass phenol = 50.0 g – 2.5 g = 47.5 g phenol mass H2O = 50.0 g – 30.3 g = 19.7 g H2O

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 Chapter 13: Solutions and Their Physical Properties

19.7 g H 2 O
% H 2O   100%  29.3% H 2 O
19.7 g H 2 O  47.5 g phenol
Above 66.8 C phenol and water are completely miscible. Consequently, for temperatures
above 66.8 C, the mixture will be a homogeneous solution consisting of 50.0 g of H2O and
50.0 g of phenol. To calculate the mole fraction of phenol in the mixture, we must first
determine the number of moles of each component.

1 mol H 2 O
number of moles of H2O = 50.0 g H2O × = 2.775 mol H2O
18.016 g H 2 O
1 mol phenol
number of moles of H2O = 50.0 g phenol × = 0.531 mol phenol
94.11 g phenol
0.531 mol phenol
Thus χphenol(mol fraction) = = 0.161
2.775 mol phenol + 0.531 mol H 2 O

PA  PA
B. (a) Rearrange Raoult’s law (Equation 13.3) to the form  xB . The mass of H2O
PA
absorbed by D1 is proportional to PA°; the mass of H2O absorbed by D2 is proportional
to PA. Hence,

11.7458 11.5057
 xB  0.0204 . XA = 0.9796,
11.7458

PA = 0.9796  23.76 mmHg = 23.28 mmHg.

The observed vapor pressure lowering = 23.76 mmHg  23.28 mmHg = 0.48 mmHg.

(b) Calculate xB for a 1.00 m solution. xB = 0.0177; xA = 0.9823. Calculate PA using

Raoult’s law. PA = 23.34 mmHg. The expected vapor pressure lowering = (23.76 
23.34) mmHg = 0.42 mmHg.

EXERCISES
Homogeneous and Heterogeneous Mixtures

1. bg bg
NH 2 OH s should be the most soluble in water. Both C6 H 6 l and C10 H 8 s arebg
composed of essentially nonpolar molecules, which are barely (if at all) soluble in water.
bg bg
Both NH 2 OH s and CaCO 3 s should be able to interact with water molecules. But
bg
CaCO 3 s contains ions of high charge, and thus it dissolves with great difficulty because
of the high lattice energy. (Recall the solubility rules of Chapter 5: most carbonates are
insoluble in water.)

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Chapter 13: Solutions and Their Physical Properties

3. (b) Salicyl alcohol probably is moderately soluble in both benzene and water. The reason
for this assertion is that salicyl alcohol contains a benzene ring, which would make it
soluble in benzene, and also can use its  OH groups to hydrogen bond to water
molecules. On the other hand, (c) diphenyl contains only nonpolar benzene rings; it should
be soluble in benzene but not in water. (a) para-dichlorobenzene contains a benzene ring,
making it soluble in benzene, and two polar CCl bonds, which oppose each other,
producing a nonpolar—and thus water-insoluble—molecule. (d) Hydroxyacetic acid is a
very polar molecule with many opportunities for hydrogen bonding. Its polar nature would
make it insoluble in benzene, while the prospective hydrogen bonding will enhance
aqueous solubility.

5. (c) Formic acid and (f) propylene glycol are soluble in water. They both can form hydrogen
bonds with water, and they both have small nonpolar portions. (b) Benzoic acid and (d) 1-
Butanol are only slightly soluble in water. Although they both can form hydrogen bonds with
water, both molecules contain reasonably large nonpolar portions, which will not interact
strongly with water. (a) Iodoform and (e) chlorobenzene are insoluble in water. Although both
molecules have polar groups, their influence is too small to enable the molecules to disrupt
the hydrogen bonds in water and form a homogeneous liquid mixture.

7. We expect small, highly charged ions to form crystals with large lattice energies, which
tends to decrease their solubility in water. Based on this information, we would expect
MgF2 to be insoluble and KF to be soluble. It is also probable that CaF2 is insoluble due to
its high lattice energy, but that NaF, with smaller lattice energy, is soluble. Of all of the
fluorides listed, KF is probably the most water soluble. The actual solubilities at 25  C are:
0.00020 M CaF2 < 0.0021 M MgF2 < 0.95 M NaF < 16 M KF.

Percent Concentration

116 g NaBr
9. % NaBr =  100% = 53.7% = 53.7 g NaBr /100 g solution
116 g NaBr +100 g H 2 O

1000 g NaCl 100.00 g soln 75.0 mL soln 1 L soln

11. soln. volume = 725 kg NaCl    
1 kg NaCl 3.87 g NaCl 76.9 g soln 1000 mL soln
= 1.83  104 L sol'n

13. For water, the mass in grams and the volume in mL are about equal; the density of water is
close to 1.0 g/mL. For ethanol, on the other hand, the density is about 0.8 g/mL. As long as
the final solution volume after mixing is close to the sum of the volumes for the two pure
liquids, the percent by volume of ethanol will have to be larger than its percent by mass.
This would not necessarily be true of other ethanol solutions. It would only be true in those
cases where the density of the other component is greater than the density of ethanol.

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 Chapter 13: Solutions and Their Physical Properties

1.01 g vinegar 6.02 g HC2 H3 O2

15. mass HC2 H 3 O 2 = 355 mL vinegar   = 21.6 g HC2 H3 O 2
1 mL 100.00 g vinegar
46.1 mg SO 24 
17. 46.1 ppm = (Assumes density of water ~1.00 g mL-1)
1 L solution
2- 46.1 mg SO 24 1 g SO 24  1 mol SO 24
[SO4 ] =  2
 2
= 4.80  10-4 M
1 L solution 1000 mg SO 4 96.06 g SO 4

Molarity

19.
1 mol CH3 OH
6.00 g CH 3 OH 
32.04 g CH 3 OH
molarity =  1.85 M = [CH 3 OH]
1 mL 1L
100.00 g soln  
0.988 g 1000 mL

21. The solution of Example 13-1 is 1.71 M C 2 H 5OH , or 1.71 mmol C 2 H 5OH in each mL of
solution.
0.235 mmol C 2 H 5OH 1 mL conc. soln
volume conc. soln = 825 mL  
1 mL soln 1.71 mmol C2 H 5OH
= 113 mL conc. soln

23. The easiest way to work with ppm is to think of it in terms of mg of a substance in a kg of
solvent. The molarity of CO2 is calculated as follows:

280 mg CO 2 1 g CO 2 1 mol CO 2 1027 kg H 2 O

molarity of CO 2    
1 kg H 2 O 1000 mg CO 2 44.0 g CO 2 1000 L H 2 O
 0.00654 M

Molality
25.
1 mol C6 H 4 Cl2
2.65 g C6 H 4 Cl2 
147.0 g C6 H 4 Cl2
molality =  0.410 m
0.879 g 1 kg
50.0 mL  
1 mL 1000 g

27. The mass of solvent in kg multiplied by the molality gives the amount in moles of the solute.
FG
mass I 2 = 725.0 mL CS2 
1.261 g

1 kg IJ

0.236 mol I 2 253.8 g I 2

H 1 mL 1000 g K 1 kg CS2 1 mol I 2
= 54.8 g I 2

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Chapter 13: Solutions and Their Physical Properties

29. 1 mol H 3 PO 4
34.0 g H 3 PO 4 
98.00 g H 3 PO 4
H 3 PO 4 molarity =  4.19 M
1 mL 1L
100.0 g soln  
1.209 g 1000 mL
1 mol H 3 PO 4
34.0 g H 3 PO 4 
98.00 g H 3 PO 4
H 3 PO 4 molality =  5.26 m
1 kg
66.0 g solvent 
1000 g

Mole Fraction, Mole Percent

31. The total number of moles = 1.28 mol C7 H16 + 2.92 mol C8 H18 + 2.64 mol C9 H 20 = 6.84 moles
1.28 mol C7 H16
(a)  C7 H16 = = 0.187  b   100% = 18.7 mol% C7 H16
(b)
6.84 moles total
2.92 mol C8 H18
 C8H18 = = 0.427  100% = 42.7 mol% C8 H18
6.84 moles total
2.64 mol C9 H 20
 C9 H20 = = 0.386  100% = 38.6 mol% C9 H 20
6.84 moles total
or 1.00-0.187-0.427 = 0.386 or 100-18.7-42.7 = 38.6 %

33. (a) The amount of solvent is found after the solute's mass is subtracted from the total mass
of the solution.
solvent   1000 mL 1.006 g   180.2 g C6 H12 O 6  
amount =   1 L soln  1 L     0.112 mol C6 H12 O6  
 1 mL   1 mol C6 H12 O 6  
1 mol H 2 O
= 1006 g solution  20.2 g C6 H12 O 6   = 54.7 mol H 2 O
18.02 g H 2 O
0.112 mol C6 H12 O6
 solute = = 0.00204
0.112 mol C6 H12 O6 + 54.7 mol H 2 O
(b) First we must determine the mass and the number of moles of ethanol. The number of
moles of solvent is calculated after the ethanol's mass is subtracted from the solution's
mass. Use a 100.00-mL sample of solution for computation. This 100 mL sample would
contain 3.20 mL of C2H5OH. We calculate the mass of ethanol first, followed by the
number of moles:
0.789 g
mass C2 H5OH  3.20 mL C 2 H 5 OH  = 2.52 g C 2 H 5 OH
1 mL C2 H 5 OH
1 mol C 2 H 5 OH
moles C 2 H 5 OH = 2.52 g C 2 H 5 OH  = 0.0547 mol C 2 H 5 OH
46.07 g C2 H 5 OH

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 0.993 g  
mass of H 2 O =  100.0 mL soln    2.52 g C 2 H 5 OH   96.8 g H 2 O
 1 mL  
1 mol H 2 O
amount of H 2 O = 96.8 g H 2 O  = 5.37 mol H 2 O
18.02 g H 2 O
0.0547 mol C 2 H 5 OH
 solute = = 0.0101
0.0547 mol C 2 H 5OH + 5.37 mol H 2 O

35. The amount of water present in 1 kg is

1 mol H 2 O
nwater = 1000 g H 2 O  = 55.49 mol H 2 O . Now, solve the following expression
18.02 g H 2 O
for n gly , the amount of glycerol. 4.85% = 0.0485 mole fraction.
ngly
 gly = 0.0485 = ngly = 0.0485 ngly + 2.69
ngly + 55.49
2.69
= = 2.83 mol glycerol
ngly
b
1.0000  0.0485 g
92.09 g C 3 H 8O 3 1 mL
volume glycerol = 2.83 mol C 3 H 8O 3   = 207 mL glycerol
1 mol C 3 H 8O 3 1.26 g
37. We assume that density of water is 1.000 g/mL, so 1.000 mL of water has a mass of 1.000 g.
First, determine the number of moles of Pb, and then the number of moles of water:
15  g Pb 1g 1 mol Pb
mol Pb =  6   7.24  108 mol
1.000 g H 2 O 10  g 207.19 g Pb
6.022  1023 atoms
# Pb atoms = 7.24  108 mol Pb   4.36 1016 atoms
1 mol Pb
1 mol H 2 O
mol H 2 O  1.000 g H 2 O   0.05556 mol
18.0 g H 2 O
7.24  108
 Pb   1.303  106
0.05556  7.24  108

Solubility Equilibrium

39. At 40  C the solubility of NH 4 Cl is 46.3 g per 100 g of H 2 O . To determine molality, we

calculate amount in moles of the solute and the solvent mass in kg.
1 mol NH 4 Cl
46.3 g 
53.49 g NH 4 Cl
molarity =  8.66 m
1 kg
100 g H 2 O 
1000 g

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Chapter 13: Solutions and Their Physical Properties

41. (a) The concentration for KClO4 in this mixture is calculated first.
mass solute 20.0 g KClO 4
= 100 g H 2 O  = 4.00 g KClO 4
100 g H 2 O 500.0 g water
At 40  C a saturated KClO 4 solution has a concentration of about 4.6 g KClO 4
dissolved in 100 g water. Thus, the solution is unsaturated.

(b) The mass of KClO 4 that must be added is the difference between the mass now present
in the mixture and the mass that is dissolved in 500 g H 2 O to produce a saturated
solution.
FG
mass to be added = 500.0 g H 2 O 
4.6 g KClO 4 IJ
 20.0 g KClO 4 = 3.0 g KClO 4
H 100 g H 2 O K
Solubility of Gases
43. We first determine the number of moles of O 2 that have dissolved.
PV 1.00 atm  0.02831 L
moles of O2 = = 1 1
= 1.16 103 mol O2
RT 0.08206 L atm mol K  298 K
1.16  103 mol O 2
O2 = = 1.16  103 M
1.00 L soln
The oxygen concentration now is computed at the higher pressure.
1.16  103 M
O2 =  3.86 atm O 2 = 4.48  103 M
1 atm O 2
0.02 g CH 4
45. mass of CH 4 = 1.00  103 kg H 2 O   20 atm = 4  102 g CH 4 (natural gas)
1 kg H 2 O  atm

47. b g
We use the STP molar volume 22.414 L = 22,414 mL to determine the molarity of Ar
under 1 atmosphere of pressure and then use Henry's law.
33.7 mL Ar 1 mol Ar

C 1 L soln 22,414 mL at STP 0.00150 M
k Ar = = =
PAr 1 atm pressure atm
In the atmosphere, the partial pressure of argon is PAr = 0.00934 atm. (Recall that pressure
fractions equal volume fractions for ideal gases.) We now compute the concentration of argon
in aqueous solution.
0.00150 M
C = kAr PAr =  0.00934 atm = 1.40  105 M Ar
atm

49. Because of the low density of molecules in the gaseous state, the solution volume remains
essentially constant as a gas dissolves in a liquid. Changes in concentrations in the solution
result from changes in the number of dissolved gas molecules (recall Figure 13-11). This
number is directly proportional to the mass of dissolved gas.

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 Chapter 13: Solutions and Their Physical Properties

Raoult's Law and Liquid–Vapor Equilibrium

51. First we determine the number of moles of each component, its mole fraction in the solution,
the partial pressure due to that component above the solution, and finally the total pressure.
1 mol C 6 H 6
amount benzene = nb = 35.8 g C 6 H 6  = 0.458 mol C 6 H 6
78.11 g C 6 H 6
1 mol C 7 H 8
amount toluene = nt = 56.7 g C 7 H 8  = 0.615 mol C 7 H 8
92.14 g C 7 H 8
0.458 mol C6 H 6 0.615 mol C7 H8
b = = 0.427 t = = 0.573
 0.458 + 0.615 total moles  0.458 + 0.615 total moles
Pb = 0.427  95.1 mmHg = 40.6 mmHg Pt = 0.573  28.4 mmHg = 16.3 mmHg
total pressure = 40.6 mmHg +16.3 mmHg = 56.9 mmHg

53. We need to determine the mole fraction of water in this solution.

1 mol C6 H12 O6
nglucose = 165 g C6 H12 O6  = 0.916 mol C6 H12 O6
180.2 g C6 H12 O6
1 mol H 2 O 38.0 mol H 2 O
nwater = 685 g H 2 O  = 38.0 mol H 2 O  water = = 0.976
18.02 g H 2 O  38.0 + 0.916  total moles
Psol'n =  water Pwater = 0.976  23.8 mmHg = 23.2 mmHg
*

55. We consider a sample of 100.0 g of the solution and determine the number of moles of each
component in this sample. From this information and the given vapor pressures, we determine
the vapor pressure of each component. Note that styrene, C6H5C=CH2, is represented by the
simplified molecular formula C8H8 in this problem.
1 mol C8 H8
amount of styrene = ns = 38 g styrene  = 0.37 mol C8 H8
104 g C8 H8
1 mol C8 H10
amount of ethylbenzene = ne = 62 g ethylbenzene  = 0.58 mol C8 H10
106 g C8 H10
ns 0.37 mol styrene
s = = = 0.39; Ps = 0.39  134 mmHg = 52 mmHg for C8 H 8
ns + ne  0.37 + 0.58  total moles
ne 0.58 mol ethylbenzene
e = = = 0.61; Pe = 0.61  182 mmHg = 111 mmHg for C8 H10
ns + ne  0.37 + 0.58  total moles
Then the mole fraction in the vapor can be determined.
Pe 111 mmHg
ye = = = 0.68 ys = 1.00  0.68 = 0.32
Pe + Ps 111+ 52  mmHg

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57. The total vapor pressure above the solution at its normal boiling point is 760 mm Hg.
The vapor pressure due to toluene is given by the following equation.
Ptoluene = toluene . Ptoluene = 0.700  533 mm Hg = 373 mm Hg. Next, the vapor pressure due
to benzene is determined, followed by the vapor pressure for pure benzene.
Pbenzene = Ptotal  Ptoluene = 760 mm Hg - 373 mm Hg = 387 mm Hg = benzene . Pbenzene
387 mm Hg = 0.300  Pbenzene and hence, Pbenzene = 1.29  103 mm Hg

Osmotic Pressure
59. We first compute the concentration of the solution. Then, assuming that the solution volume is the
same as that of the solvent (0.2500 L), we determine the amount of solute dissolved, and finally the
molar mass.
1 atm
1.67 mmHg 
n  760 mmHg
= = = 8.98  105 M
V RT 0.08206 L atm mol K 1  298.2 K
1

5
solute = 0.2500 L  8.98  10 mol = 2.25  105 mol M =
0.72 g
= 3.2  104 g/mol
amount 1L 5
2.25  10 mol

61. Both the flowers and the cucumber contain ionic solutions (plant sap), but both of these
solutions are less concentrated than the salt solution. Thus, the solution in the plant
material moves across the semipermeable membrane in an attempt to dilute the salt
solution, leaving behind wilted flowers and shriveled pickles (wilted/shriveled plants have
less water in their tissues).
63. We first determine the molarity of the solution. Let's work the problem out with three
significant figures.
n  1.00 atm
= = = 0.0446 M
V RT 0.08206 L atm mol1 K 1  273 K
1L
volume = 1 mol  = 22.4 L solution  22.4 L solvent
0.0446 mol solute
We have assumed that the solution is so dilute that its volume closely approximates the
volume of the solvent constituting it. Note that this volume corresponds to the STP molar
volume of an ideal gas. The osmotic pressure equation also resembles the ideal gas equation.

65. First we determine the concentration of the solution from the osmotic pressure, then the
amount of solute dissolved, and finally the molar mass of that solute.
0.88 mmHg 1 atm
 = 5.1 mm soln   = 4.3 104 atm
13.6 mm soln 760 mmHg
n  4.3  104 atm
= = 1 1
= 1.8  105 M
V RT 0.08206 L atm mol K  298 K

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 Chapter 13: Solutions and Their Physical Properties

1L
amount solute = 100.0 mL   1.8  105 M = 1.8  106 mol solute
1000 mL
0.50 g
molar mass = = 2.8 105 g/mol
1.8  106 mol
67. The reverse osmosis process requires a pressure equal to or slightly greater than the osmotic
pressure of the solution. We assume that this solution has a density of 1.00 g/mL. First, we
determine the molar concentration of ions in the solution.
1 mol NaCl 2 mol ions
2.5 g NaCl  
58.4 g NaCl 1 mol NaCl
[ions]=  0.86 M
1 mL soln 1 L soln
100.0 mL soln  
1.00 g 1000 mL
n mol
 = RT = 0.86  0.08206 L atm mol1 K 1   25 + 273.2  K = 21 atm
V L

Freezing-Point Depression and Boiling-Point Elevation

69. First we compute the molality of the benzene solution, then the number of moles of solute
dissolved, and finally the molar mass of the unknown compound.
T f 4.92C  5.53C
m= = = 0.12 m
K f 5.12 C/m
0.12 mol solute
amount solute = 0.07522 kg benzene  = 9.0  103 mol solute
1 kg benzene
1.10 g unknown compound
molecular weight = = 1.2 102 g/mol
9.0  103 mol
71. (a) First we determine the molality of the solution, then the value of the freezing-point
depression constant.
1 mol C6 H6
1.00 g C6 H6 
78.11 g C6 H6 Tf 3.3C  6.5C
m=  0.160 m Kf    20.C / m
1 kg m 0.160 m
80.00 g solvent 
1000 g
(b) For benzene, Kf = 5.12  Cm1 . Cyclohexane is the better solvent for freezing-point
depression determinations of molar mass, because a less concentrated solution will still
give a substantial freezing-point depression. For the same concentration, cyclohexane
solutions will show a freezing-point depression approximately four times that of
benzene. Also, one should steer clear of benzene because it is a known carcinogen.

73. Here we determine the molality of the solution, then the number of moles of solute present,
and the molar mass of the solute to start things off. Then we determine the compound's
empirical formula, and combine this with the molar mass to determine the molecular formula.
Tf 1.37  C  5.53  C
m= = = 0.813 m
 Kf 5.12  C / m

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Chapter 13: Solutions and Their Physical Properties

FG
amount = 50.0 mL C 6 H 6 
0.879 g

1 kg

IJ
0.813 mol solute
= 3.57  102 mol
H 1 mL 1000 g K
1 kg C 6 H 6
6.45 g
molecular weight = = 181 g/mol
3.57  102 mol
Now, calculate the empirical formula from the provided mass percents for C, H, N, and O.
1 mol C
42.9 g C  = 3.57 mol C 1.19  3.00 mol C
12.01 g C
1 mol H
2.4 g H  = 2.4 mol H 1.19  2.0 mol H
1.01 g H
1 mol N
16.7 g N  = 1.19 mol N 1.19  1.00 mol N
14.01 g N
1 mol O
38.1 g O  = 2.38 mol O 1.19  2.00 mol O
16.00 g O
The empirical formula is C3 H 2 NO 2 , with a formula mass of 84.0 g/mol. This is one-half the
experimentally determined molar mass. Thus, the molecular formula is C6 H 4 N 2 O 4 .

75. We determine the molality of the benzene solution first, then the molar mass of the solute.
Tf 1.183 C
m= = = 0.231 m
 K f 5.12 C/m
0.231 mol solute
amount solute = 0.04456 kg benzene  = 0.0103 mol solute
1 kg benzene
0.867 g thiophene
molar mass = = 84.2 g/mol
0.0103 mol thiophene
Next, we determine the empirical formula from the masses of the combustion products.
1 mol CO 2 1 mol C
amount C = 4.913 g CO 2   = 0.1116 mol C  0.02791  4.000 mol C
44.010 g CO 2 1 mol CO 2
1 mol H 2 O 2 mol H
amount H = 1.005 g H 2 O   = 0.1116 mol H  0.02791  4.000 mol H
18.015 g H 2 O 1 mol H 2 O
1 mol SO 2 1 mol S
amount S = 1.788 g SO 2   = 0.02791 mol S  0.02791  1.000 mol S
64.065 g SO 2 1 mol SO 2
A reasonable empirical formula is C 4 H 4S , which has an empirical mass of 84.1 g/mol. Since this is the
same as the experimentally determined molar mass, the molecular formula of thiophene is C 4 H 4S .

77. The boiling point must go up by 2 °C, so Tb = 2 C. We know that Kb = 0.512 C/m for water. We
assume that the mass of a liter of water is 1.000 kg and the van't Hoff factor for NaCl is i = 2. We
first determine the molality of the saltwater solution and then the mass of solute needed.
Tb 2o C
m=  =2m
i Kb 2.00  0.512 o C/m

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 Chapter 13: Solutions and Their Physical Properties

1 kg H 2 O 2 mol NaCl 58.4 g NaCl

solute mass = 1.00 L H2O    = 120 g NaCl
1 L H2 O 1 kg H 2 O 1 mol NaCl
This is at least ten times the amount of salt one would typically add to a liter of water for
cooking purposes!

79. Assume that 1 L of ocean water has a mass of 1 kg.

Tf   K f  m
1.94  C   1.86  C  m 1   m
m  1.04

Strong Electrolytes, Weak Electrolytes, and Nonelectrolytes

81. The freezing-point depression is given by Tf = iKf m . Since Kf = 1.86 C / m for water,
Tf = i 0.186 C for this group of 0.10 m solutions.
(a) Tf = –0.186° C. Urea is a nonelectrolyte, and i = 1.
(b) Tf = –0.372° C. NH4NO3 is a strong electrolyte, composed of two ions per formula
unit; i = 2 .
(c) Tf = –0.372° C. HCl is a strong electrolyte, composed of two ions per formula unit;
i = 2.

(d) Tf = –0.558° C. CaCl2 is a strong electrolyte, composed of three ions per formula unit;
i = 3.

(e) Tf = –0.372° C. MgSO4 is a strong electrolyte, composed of two ions per formula unit;
i = 2.

(f) Tf = –0.186° C. Ethanol is a nonelectrolyte; i = 1.

(g) Tf < –0.186° C. HC2H3O2 is a weak electrolyte; i is somewhat larger than 1.

83. The combination of NH 3 (aq) with HC2 H 3O 2 (aq), results in the formation of
NH 4 C2 H 3O 2 (aq), which is a solution of the ions NH4+ and CH3COO-.
b g b g b g +
b g
NH 3 aq + HC 2 H 3O 2 aq  NH 4 C 2 H 3O 2 aq  NH 4 aq + C 2 H 3O 2 aq

b g
This solution of ions or strong electrolytes conducts a current very well.

85. The answer is (d). The other options describe (a) a gas dissolved in water, (b) a gas which
when dissolved in water fully dissociates and is a strong electrolyte, and (c) a non-electrolytic
molecule in water.

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INTEGRATIVE AND ADVANCED EXERCISES

88. The molarity of the original solution is computed first.

1 mol KOH
109.2 g KOH 
56.010 g KOH
KOH molarity   1.950 M
1 L soln
A 1.950 M solution is more concentrated than a 0.250 m solution. Thus, we must dilute the
original solution. First we determine the mass of water produced in the final solution, and
the mass of water present in the original solution, and finally the mass of water we must
add.
1.950 mol KOH 1 kg H 2 O
mass H 2 O in final soln  0.1000 L orig. soln    0.780 kg H 2 O
1 L soln 0.250 mol KOH
1.09 g
mass original solution  100.0 mL   109 g original solution
1 mL

1L 109.2 g KOH
mass KOH  100.0 mL    10.92 g KOH
1000 mL 1 L soln
original mass of water  109 g soln - 10.92 g KOH  98 g H 2 O
mass added H 2 O  780.g H 2 O - 98 g H 2 O  682 g H 2 O

92. First determine the molality of the solution with the desired freezing point and compare it
to the molality of the supplied solution to determine if ethanol or water needs to be added.
 Tf –2.0 C
m    1.1 m (desired)
– Kf –1.86 C/m
1000 mL 0.9767 g
mass solution  2.50 L    2.44  103 g solution
1L 1 mL
13.8 g C2 H 5OH
mass solute  2.44  103 g soln   337 g C2 H 5OH
100.0 g soln
1 kg
mass H 2O  (2.44  103 g - 337 g C2 H 5OH)   2.10 kg H 2 O
1000 g
1 mol C2 H5OH
337 g C2 H 5OH 
46.07 g C2 H 5OH
m  3.48 m (available)
2.10 kg H 2 O

Thus we need to dilute the solution with water. We must find the mass of water needed in the
final solution, then the mass of water that must be added.
1 mol C2 H 5OH 1 kg H 2 O
final mass of water  337 g C 2 H 5OH    6.6 kg H 2 O
46.07 g C 2 H 5OH 1.1 mol C 2 H 5OH
mass H 2 O needed  6.6 kg total - 2.10 kg already present  4.5 kg H 2O

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 Chapter 13: Solutions and Their Physical Properties

95. First we determine the molality of the benzene solution, and then the number of moles of
solute in the sample.

Tf 5.072 C  5.533 C

molality    0.0900 m
 Kf  5.12 C/m

0.879 g 1 kg 0.0900 mol solute

amount of solute  50.00 mL     0.00396 mol solute
1 mL 1000 g 1 kg solvent

We use this amount to determine the amount of each acid in the solute, with the added data of
the molar masses of stearic acid, C18H36O2, 284.5 g/mol, and palmitic acid, C18H36O2,
256.4 g/mol. We let x represent the amount in moles of palmitic acid.

1.115 g sample  (0.00396  x) mol  284.5 g/mol  x mol  256.4 g/mol

 1.127  284.5 x  256.4 x  1.127  28.1 x
1.127  1.115
x  0.00043 mol palmitic acid
28.1
0.00396  0.00043  0.00353 mol stearic acid

mass palmitic acid = 0.00043 mol × 256.4 g/mol = 0.11 g palmitic acid

0.11 g palmitic acid

% palmitic acid  100%  1101 % palmitic acid (about 10%)
1.115 g sample

97. We first determine the amount in moles of each substance.

1 mol CO(NH 2 ) 2
amount CO(NH 2 ) 2  0.515 g CO(NH 2 ) 2   0.00858 mol CO(NH 2 ) 2
60.06 g CO(NH 2 ) 2

1 mol H 2 O
amount H 2 O with urea  92.5 g H 2 O   5.13 mol H 2 O
18.015 g H 2 O

1 mol C12 H 22 O11

amount C12 H 22 O11  2.50 g C12 H 22 O11   0.00730 mol C12 H 22 O11
342.3 g C12 H 22 O11

1 mol H 2 O
amount H 2 O with sucrose  85.0 g H 2O   4.72 mol H 2 O
18.015 g H 2 O

The vapor pressure of water will be the same above both solutions when their mole fractions
are equal. We assume that the amount of water present as water vapor is negligible. The total

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Chapter 13: Solutions and Their Physical Properties

amount of water in the two solutions is (4.72 + 5.13 =) 9.85 mol H2O. We let nwater designate
the amount of water in the urea solution. The amount of water in the sucrose solution is then
9.85 mole – nwater. Note that we can compute the mole fraction of solute for comparison,
since when the two solute mole fractions are equal, the mole fractions of solvent will also be
equal (  solvent  1.0000   solute ) .

0.00857 mol urea 0.00730 mol sucrose

  urea   sucrose 
0.00858 mol urea  n water 0.00730 mol sucrose  (9.85  n water )

We “cross multiply’’ to begin the solution for n water .

0.00857 (0.00730  9.85  n water )  0.00730 (0.00858  n water )

0.0845  0.0000626
0.0845  0.00857 n water  0.0000626  0.00730 n water n water   5.32 mol
0.00730  0.00857

We check the answer by substitution into the mole fraction equation.

0.00857 mol urea 0.00730 mol sucrose

 0.00161   urea  sucrose  0.00161 
0.00857 mol  5.324 0.00730 mol  (9.85  5.324)mol

The mole fraction of water in each solution is (1.00000 – 0.00161 =) 0.99839, or 99.839 mol%

100.
(a) Surface area of a particle = 4r2 = 4(3.1416)(1x10-7m)2 = 1.26x10-13 m2/particle. We
need to find the number of particles present (not atoms!)

4 r 3 4 (110-7 m)3
particle volume    4.19  1021 m3
3 3

19.3 g (100cm)3
particle mass  density  volume  3 3
 4.19  1021 m3  8.09 1014 g/particle
cm (1m)

mass of Au 1.00 103g Au

number of Au particles    1.24 1010 particles
particle mass 8.09 1014 g/particle

total surface area  (1.26 10-13 m 2 /particle)(1.24 1010 particles)  1.56  103 m 2

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 Chapter 13: Solutions and Their Physical Properties

(b) For 1.00 mg Au the volume of Au is: (1.00 mg)(1 g/1000 mg)/(19.3 g/cm3) = 5.18 × 10-5
cm3

Volume of a cube is L3, where L is the edge length, so

L = 3 5.18 10-5 cm3 = 3.73 10-2 cm

area = 6×L2 = 6×(3.73×10-2 cm)2 × (1m/100cm)2 = 8.34×10-7 m2

105. We determine the volumes of O2 and N2 that dissolve under the appropriate partial
pressures of 0.2095 atm O2 and 0.7808 atm N2, and at a temperature of 25 °C, with both
gas volumes measured at 1.00 atm and 25 °C. Note that the percent by volume and the
percent by partial pressures of the atmosphere are numerically the same.

28.31 mL O 2 mL O 2
O 2 volume  0.2095 atm   5.931
1 atm  L soln L solution
14.34 mL N 2 mL N 2
N 2 volume  0.7808 atm   11.20
1 atm  L soln L solution
mL N 2
11.20
volume % N 2  L solution  100%  65.38% N 2 by volume
mL N 2 mL O 2
11.20  5.931
L solution L solution
volume % O 2  100.00%  65.38%  34.62% O 2 by volume

107. First we determine the mass of CuSO4 in the original solution at 70 °C.

32.0 g CuSO 4
335 g sample   107.2 g CuSO 4
100.0 g soln

We let x represent the mass of CuSO4 removed from the solution when the
CuSO45H2O recrystallizes. Then the mass of H2O present in the recrystallized
product is determined.

1 mol CuSO 4 5 mol H 2 O 18.02 g H 2 O

mass H 2 O  x g CuSO 4     0.565 x g H 2 O
159.6 g CuSO 4 1 mol CuSO 4 1 mol H 2 O

Now we determine the value of x by using the concentration of the saturated solution at
0 °C.

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Chapter 13: Solutions and Their Physical Properties

12.5 g CuSO 4 (107.2  x) g CuSO 4


100.0 g soln (335  x  0.565 x) g soln

1.072  104  100.0 x  4.19  103  19.6 x (100.0  19.6) x  1.072  104  4.19  103

6.53  103
x  81 g CuSO 4
80.4

1.000 g CuSO 4  0.565 g H 2 O

mass CuSO 4  5H 2 O  81 g CuSO 4   1.3  102 g CuSO 4  5H 2 O
1.000 g CuSO 4

109.
445 106 mol N 2 28.0 g N 2 g
mass of N 2 =   0.0125
L of seawater 1 mol L
Partial pressure can be determined from Henry’s Law:
C  kH P
445 106 M   0.61103 M  atm 1  P
445 106 M
P  0.73 atm
0.61 103 M  atm 1

111. First, determine what molality of ethylene glycol is needed to cause a 10.0 °C freezing-point
depression:
Tf  K f  m
10  C   1.86  C  m 1   m
m  5.376 m

Then, determine the num\ber of moles of ethylene glycol, which can be used to determine the
volume, using the density of ethylene glycol given.

5.376 mol C2 H 6 O 2 1 kg H 2 O 20.0 L H 2 O

mol C2 H 6 O 2 =    107.53 mol C2 H 6 O 2 /sample
1 kg H 2 O 1 L H 2O sample
62.09 g C2 H 6 O 2 1 mL
Vol C2 H 6 O 2 = 107.53 mol C2 H 6 O 2    5961 mL = 5.96 L
1 mol C2 H 6 O 2 1.12 g C2 H 6 O 2

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FEATURE PROBLEMS

114. (a) A solution with  HCl = 0.50 begins to boil at about18 C . At that temperature, the
composition of the vapor is about  HCl = 0.63 , reading directly across the tie line at
18° C. The vapor has  HCl  0.50 .
(b) The composition of HCl(aq) changes as the solution boils in an open container because
the vapor has a different composition than does the liquid. Thus, the component with
the lower boiling point is depleted as the solution boils. The boiling point of the
remaining solution must change as the vapor escapes due to changing composition.

(c) The azeotrope occurs at the maximum of the curve: at  HCl = 0.12 and a boiling
temperature of 110  C .

(d) We first determine the amount of HCl in the sample.

1L 1.006 mol NaOH 1 mol HCl

amount HCl = 30.32 mL NaOH   
1000 mL 1L 1 mol NaOH
amount HCl = 0.03050 mol HCl
The mass of water is the difference between the mass of solution and that of HCl.
FG 1.099 gIJ FG 36.46 g HCl IJ
H
mass H 2 O = 5.00 mL soln 
1 mL K H
 0.03050 mol HCl 
1 mol HCl K
= 4.38 g

Now we determine the amount of H 2 O and then the mole fraction of HCl.
1 mol H 2 O
amount H 2 O = 4.38 g H 2 O  = 0.243 mol H 2 O
18.02 g H 2 O
0.03050 mol HCl
 HCl = = 0.112
0.03050 mol HCl + 0.243 mol H 2 O

115. (a) At 20  C , the solubility of NaCl is 35.9 g NaCl / 100 g H 2 O . We determine the mole
fraction of H 2 O in this solution
1 mol H 2 O
amount H 2 O = 100 g H 2O  = 5.549 mol H 2O
18.02 g H 2 O
1 mol NaCl
amount NaCl = 35.9 g NaCl   0.614 mol NaCl
58.44 g NaCl
5.549 mol H 2 O
 water = = 0.9004
0.614 mol NaCl + 5.549 mol H 2 O
The approximate relative humidity then will be 90% (90.04%), because the water vapor
pressure above the NaCl saturated solution will be 90.04% of the vapor pressure of pure
water at 20 C .

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Chapter 13: Solutions and Their Physical Properties

(b) CaCl 2  6 H 2 O deliquesces if the relative humidity is over 32%. Thus, CaCl 2  6 H 2 O
will deliquesce (i.e., it will absorb water from the atmosphere).

(c) If the substance in the bottom of the desiccator has high water solubility, its saturated
solution will have a low  water , which in turn will produce a low relative humidity.
Thus, a relative humidity lower than 32% is needed to keep CaCl 2  6 H 2 O dry.

116. (a) We first compute the molality of a 0.92% mass/volume solution, assuming the
solution's density is about 1.00 g/mL, meaning that 100.0 mL solution has a mass of
100.0 g.
1 mol NaCl
0.92 g NaCl 
58.44 g NaCl
molality =  0.16 m
1 kg solvent
(100.0 g soln  0.92 g NaCl) 
1000 g
Then we compute the freezing-point depression of this solution.
 2.0 mol ions 1.86 C
Tf = iK f m =   0.16 m = 0.60  C
mol NaCl m
The van't Hoff factor of NaCl most likely is not equal to 2.0, but a bit less and thus the
two definitions are in fair agreement.

(b) We calculate the amount of each solute, assume 1.00 L of solution has a mass of
1000 g, and subtract the mass of all solutes to determine the mass of solvent.
1 mol NaCl 2 mol ions
amount NaCl ions = 3.5 g NaCl   = 0.12 mol ions
58.44 g NaCl 1 mol NaCl
1 mol KCl 2 mol ions
amount KCl ions = 1.5 g   = 0.040 mol ions
74.55 g KCl 1 mol KCl
1 mol Na 3 C6 H 5 O7 4 mol ions
amount Na 3 C6 H 5 O7 ions = 2.9 g  
258.07 g Na 3 C6 H 5 O7 1 mol Na 3 C6 H 5 O7
amount Na 3 C6 H 5 O7 ions = 0.045 mol ions
1 mol C6 H12 O6
amount C6 H12 O6 = 20.0 g C6 H12 O6  = 0.111 mol C6 H12O 6
180.2 g C6 H12 O6
solvent mass = 1000.0 g   3.5 g +1.5 g + 2.9 g + 20.0 g  = 972.1 g H 2 O
solvent mass = 0.9721 kg H 2 O

solution molality =
 0.120 + 0.040 + 0.045 + 0.111 mol = 0.325 m
0.9721 kg H 2 O
Tf =  K f m = 1.86 C/m  0.325 m = 0.60 C


This again is close to the defined freezing point of 0.52  C , with the error most likely
arising from the van't Hoff factors not being integral. We can conclude, therefore, that
the solution is isotonic.

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SELF-ASSESSMENT EXERCISES
120. The answer is (b), because molality is moles solute/kg solvent. Assuming a volume of 1 L, at
a concentration of 0.010 m, the mass of the water (~1 kg) is nearly the same as the volume of
the solution (1 L).

121. The answer is (d), because the other choices either don’t form a solution because they are
immiscible or the solute-solvent interactions are stronger than intramolecular interactions for
either of the pure solute or solvent, making the solutions non-ideal.

122. The answer is (a). As partial pressure of the gas increases, Henry’s law shows that the
concentration of the gas in the liquid increases.

123. The answer is (d), because the total ionic molality of the MgCl2 is 3×0.008 = 0.024.

124. The answer is (c), because nothing in the information provided suggests that the
concentrations of the two volatile species are the same.

125. The mass of NH4Cl is: 1.12 mol NH4Cl × (53.45 g/mol) = 59.86 g.
Solubility is 59.86 g NH4Cl / 150.0 g H2O = 0.40, or 40 g/100 g.
Based on Figure 13-8, the concentration limit of NH4Cl is 42 g per 100 g of H2O. Since the
amount of NH4Cl is below the solubility limit, no crystals will form.

0.92 g NaCl 1 mol NaCl 1 mol Na  1000 mL

 

126. (a)  Na       0.16 M Na 
100 mL H 2 O 58.45 g NaCl 1 mol NaCl 1L
1 mol NaCl 2 mol ions
(b) total molarity of ions  0.16 M Na     0.32 M
1 mol Na  1 mol NaCl
(c)   MRT   0.32 M   0.08206 L  atm  K 1   310 K   8.1 atm
(d) Determine the solution molality first, then determine freezing-point depression.
0.32 mol ions 1 L solution
molality H 2 O    0.3184 m
1 L solution 1.005 kg solution
Tf   1.86 o C / m   0.3184 m   0.60 o C

127. (a)
62.0 g C3 H8O3 1.159 g sol'n 1000 mL sol'n 1 mol C3 H8O3
 C3 H 8 O 3     
100 g sol 'n 1 mL sol'n 1 L sol'n 92.11 g C3H8O3
 7.80 M C3 H8O3
(b)
38.0 g H 2 O 1.159 g sol'n 1000 mL sol'n 1 mol H 2 O
 H 2O    
100 g sol ' n 1 mL sol'n 1 L sol'n 18.02 g H 2O
 24.4 M H 2 O

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Chapter 13: Solutions and Their Physical Properties

(c)
38.0 g H 2 O 1000 g solvent 1 mol H 2 O
 H 2O   
62.0 g C3 H8O3 1kg solvent 18.02 g H 2 O
 34.0 m H 2 O

(d) We can determine the moles of C3H8O3 and H2O from the above calculations.
moles of H2O = 2.11 mol.
moles of C3H8O3 = 0.673 mol.

0.673 mol C3 H8O3

xC3H8O3   0.242
0.673 mol C3 H8O3  2.11 mol H 2 O
2.11 mol H 2 O
(e) mol% H 2 O  100  75.8%
0.673 mol C3 H8O3  2.11 mol H 2 O

128. (1) Solution with lowest conductivity: (b) 0.15 m C12H22O11, because it is a non-electrolyte.
(2) Lowest boiling point: (d) 0.05 m NaCl, because the molality of the solute is the smallest,
making boiling-point elevation the smallest value.
(3) Highest vapor pressure of water: (d), for the same reason as above.
(4) Lowest freezing point: (a), because the molality of the solute is the highest (2×0.10 m).

129. The answer is (c). It shows solvation of individual ions by oriented water molecules.

130. The answer is (b), because the charge in all species is the same (+1 or -1), but F– is the
smallest.

131. The magnitude of ΔHlattice is larger than the sum of the ΔHhydration of the individual ions. Since
the test tube turns cold, dissolution of NH4Cl is endothermic, which means that the final
energy of the system, the hydration of the individual ions, is less than the initial energy of the
system, which is the lattice energy of the solid.

132. The answer is (a). Lowering temperature increases solubility.

133. The answer is (b), because the HCl dissociates completely in water to give cations and anions,
which are then solvated with water (and are none-volatile).

134. The answer is (a). Use Raoult’s law to determine the mole fraction:
PC H  x C H  PC* H
6 14 6 14 6 14

600 mm Hg = xsolute  760 mm Hg

xC H  0.789
6 14

xsolute  1  0.789  0.211

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135. The answer is (e).

  MRT
   0.312 M   0.08206 L  atm  K 1   348 K   8.91 atm
1.0135 barr
P(barr) = 8.91 atm   9.03 barr
1 atm

136. The answer is (c).

18.0 g H 2 O
10.5 mol H 2 O   189 g H 2 O
1 mol H 2 O
23.4
mass%  100  11.0%
189  23.4

337