Chapter 13

Practice Exercises

13.1 CH2S = kHPH2S

 0.11 mol H 2S   34.08g H 2S  –1
PH2S = 1.0 atm CH2S =    1 mol H S  = 3.7 g L
 L  2 
3.7 g L–1 H2S = kH (1.0 atm HsS)
kH = 3.7 g L–1
Hydrogen sulfide is more soluble in water than nitrogen and oxygen. Hydrogen sulfide reacts with the
water to form hydronium ions and HS–.

13.2 With one atmosphere of air, the concentrations of the gases in the water depends on the partial pressures of
the gases.
 0.00430 g O 2  159 mm Hg 
Oxygen: CO2 =    = 0.899 mg O2/ 100 mL
 100 mL H 2 O   760 mm Hg 
g O2 in 125 g of water = 0.899 mg O2/ 100 mL x 125 mL = 1.12 g

 0.00190 g N 2   593 mm Hg 
Nitrogen CN2 =    = 1.48 mg N2/ 100 mL
 100 mL H 2 O   760 mm Hg 

g N2 in 125 mL of water = 1.48 mg N2/ 100 mL x 125 mL = 1.85 g

13.3 A 10% w/w solution of sucrose will need 10 grams of sucrose for each 100 g of solution. For a solution
with 45.0 g of sucrose:
45.0 g sucrose
10% solution =
x g solution
x = 450 g solution
g water = 450 g solution – 45.0 g sucrose
g water = 405 g water
 1 cm3 
mL water = (405 g water)   = 405.7 mL water
 0.9982 g 
 

13.4 The total mass of the solution is to be 25.0 g. If the solution is to be 1.00 % (w/w) NaBr, then the mass of
NaBr will be: 25.0 g × 1.00 g NaBr/100 g solution = 0.250 g NaBr. We therefore need 0.250 g of NaBr
and (25.0 – 0.250) = 24.75 g H2O. The volume of water that is needed is: 24.75 g/0.988 g/mL = 25.0 mL
H2O.

13.5 An HCl solution that is 37 % (w/w) has 37 grams of HCl for every 1.0 × 102 grams of solution.
 1.0 × 102 g solution 
g solution = (7.5 g HCl)   = 2.0 × 101 g solution
 37 g HCl 
 
13.6 We need to know the number of moles of Na2SO4 and the number of kg of water.
44.00 g Na2SO4 ÷ 142.0 g/mol = 0.3099 mol Na2SO4
250 g H2O × 1 kg/1000 g = 0.250 kg H2O

The molality is thus given by:

m = 0.3099 mol/0.25 kg = 1.239 mol Na2SO4/kg H2O = 1.239 m

Molarity is moles solute per liters of solution. The moles of solute is the same for molarity and molality but
the volume of solution would be larger than the kilograms of solvent so M < m.

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 0.050 mol CH3OH   32.0 g CH3OH 

13.7 g CH3OH for 0.050 m = 0.200 kg   
 kg H 2 O  1 mol CH3OH 
= 0.320 g

 0.100 mol CH3OH   32.0 g CH3OH 

g CH3OH for 0.100 m = 0.200 kg   
 kg H 2 O  1 mol CH3OH 
= 0.640 g

 0.150 mol CH3OH   32.0 g CH3OH 

g CH3OH for 0.150 m = 0.200 kg   
 kg H 2 O  1 mol CH3OH 
= 0.960 g
 0.200 mol CH3OH   32.0 g CH3OH 
g CH3OH for 0.200 m = 0.200 kg   
 kg H 2 O  1 mol CH3OH 
= 1.28 g

 0.250 mol CH3OH   32.0 g CH3OH 

g CH3OH for 0.250 m = (0.200 kg H2O)   
 kg H 2 O  1 mol CH3OH 
= 1.60 g CH3OH

13.8 First we need to find the number of grams of Fe(NO3)3 for each kg of solvent.
 241.86 g Fe ( NO3 ) 
0.853 m Fe(NO3)3 = 0.853 mol Fe(NO3)3  3  = 206.3 g Fe(NO )
3 3
 1 mol Fe ( NO3 ) 
 3 
Then we need to find how the ratio of the moles of Fe(NO3)3 to the mass of the solution:
0.853 mol Fe ( NO3 )3
ratio = = 7.072 × 10–4 mol Fe(NO3)3 / g solution
1000 g H 2 O + 206.3 g Fe ( NO3 )3
 1 g solvent 
(a) g solution = (0.0200 mol Fe(NO3)3)   = 28.3 g solution
 7.07 ×10−4 mol Fe ( NO3 ) 
 3

 1mol Fe ( NO3 )   1 g solvent 

(b) g sol'n = (0.0500 mol Fe3+)  3   = 70.7 g sol'n
 1 mol Fe3+   7.07 ×10−4 mol Fe ( NO3 ) 
   3

 1mol Fe ( NO3 )   1 g solvent 

3   = 1.41 g sol'n
(c) g sol'n = (0.00300 mol NO3–) 
 3 mol NO −   7.07 ×10−4 mol Fe ( NO ) 
 3  3 3
13.9 If a solution is 52% NaOH, then it has 52 g of NaOH for each 100 g of solution. The mass of water is 48 g
of water for 52 g of NaOH. To calculate the molality of the solution, we need to find the moles of NaOH
for each kilogram of water.
 52 g NaOH   1 mol NaOH   1000 g H 2 O 
m=     = 27 mol NaOH/kg H2O = 27 m NaOH
 48 g H 2 O   40.0 g NaOH   1 kg H 2 O 

13.10 If a solution is 37.0% (w/w) HCl, then 37.0% of the mass of any sample of such a solution is HCl and
(100.0 – 37.0) = 63.0% of the mass is water. In order to determine the molality of the solution, we can
conveniently choose 100.0 g of the solution as a starting point. Then 37.0 g of this solution are HCl and
63.0 g are H2O. For molality, we need to know the number of moles of HCl and the mass in kg of the
solvent:
37.0 g HCl ÷ 36.46 g/mol = 1.01 mol HCl
63.0 g H2O × 1 kg/1000 g = 0.0630 kg H2O

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molality = mol HCl/kg H2O = 1.01 mol/0.0630 kg = 16.1 m

13.11 40.0 % HBr means 40 g of HBr per 100 g of solution. Since molarity is defined as moles of solute per liter
of solution we need to determine the volume of solution. The density of the solution allows us to determine
the volume of the solution

40 g HBr 1mol HBr 1.38 g 1000mL

x x x = 6.82 M
100 g solution 80.91g mL L

13.12 First determine the number of moles of Al(NO3)3 dissolved in the liter of water.
 1 mol Al ( NO3 ) 
mol Al(NO3)3 = (1.00 g Al(NO3)3)  3  = 0.00469 mol Al(NO3)3
 212.996 g Al ( NO3 ) 
 3
Next find the mass of the water:
 1000 mL H 2 O  0.9982 g H 2 O 
g H2O = (1.00 L H2O)    = 998.2 g H2O
 1 L H 2 O  1 mL H 2 O 
To find the molarity of the solution, first we need to find the mass of the solution, and then the volume of
the solution:
g solution = 998.2 g H2O + 1.00 g Al(NO3)3 = 999.2 g solution
 1 mL solution   1 L solution 
L solution = (999.2 solution)    = 1.0003 L
 0.9989 g solution   1000 mL solution 
0.00469 mol Al ( NO3 )3
M of solution = = 0.00469 M Al(NO3)3
1.0003 L solution
The molality of the solution can also be determined
0.00469 mol Al ( NO3 )3
m of solution = = 0.00470 m Al(NO3)3
0.9982 kg H 2 O

13.13 First determine the number of moles of each component of the solution:
For C16H22O4, 20.0 g/278 g/mol = 0.0719 mol
For C5H12, 50.0 g/72.2 g/mol = 0.692 mol
The mole fraction of solvent is:
0.692 mol/(0.692 mol + 0.0719 mol) = 0.906
Using Raoult's Law, we next find the vapor pressure to expect for the solution, which arises only from the
solvent (since the solute is known to be nonvolatile):

Psolvent = χsolvent × P°solvent = 0.906 × 541 torr = 4.90 x 102 torr

13.14 Pacetone = χacetone × P°acetone

 1 mol acetone 
mol acetone = (156 g acetone)   = 2.690 mol acetone
 58.0 mol acetone 
Do not round your answers until the end. The moles of stearic acid is small compared to the moles of
acetone and rounding error may give you too high of a mass of stearic acid.
 2.690 mol acetone 
155 torr =   x 162 torr
 2.690 mol acetone + x mol stearic acid 
 2.690 mol acetone 
0.957 =  
 2.690 mol acetone + x mol stearic acid 
2.574 mol acetone + 0.957x mol stearic acid = 2.690 mol acetone
0.957x mol stearic acid = 0.116
x mol stearic acid = 0.121 mol stearic acid

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Finally solve to find the number of grams of stearic acid

 284.5 g stearic acid 
g stearic acid = (0.121 mol stearic acid)   = 34.5 g stearic acid
 1 mol stearic acid 
13.15 Pcyclohexane = χcyclohexane × P°cyclohexane = 0.750 × 66.9 torr = 50.2 torr
Ptoluene = χtoluene × P°toluene = 0.250 × 21.1 torr = 5.28 torr
Ptotal = Pcyclohexane + Ptoluene = 33.5 torr + 10.6 torr = 55.4 torr

13.16 First we need to find the moles of the cyclohexane and the moles of toluene.
 1 mol cyclohexane 
mol cylcohexane: = (122 g cyclohexane)   = 1.450 mol cyclohexane
 84.15 g cyclohexane 
 1 mol toluene 
mol toluene = (122 g toluene)   = 1.324 mol toluene
 92.14 g toluene 
Now, find the χcyclohexane and the χtoluene
1.450 mol cyclohexane
χcyclohexane = = 0.523
1.450 mol cyclohexane + 1.324 mol toluene
χtoluene =1 – χcyclohexane = 1 – 0.523 = 0.477
Pcyclohexane = χcyclohexane × P°cyclohexane = 0.523 × 66.9 torr = 35.0 torr
Ptoluene = χtoluene × P°toluene = 0.477 × 21.1 torr = 10.1 torr
Ptotal = Pcyclohexane + Ptoluene = 35.0 torr + 10.1 torr = 45.1 torr

13.17 First convert 0F to 0C. 235 0F = 112.78 0C and 240 0F = 115.56 0C

The corresponding boiling point elevations are then 12.78 0C and 15.56 0C respectively.
The molality of the two solutions is given as:
m =12.78 0C/ 0.51 0C m-1 = 25.06 m
m = 15.56 0C/0/51 0C m-1 = 30.51 m

The solution that boils at 235 0F has the following mass percent of sugar:

25.06mol C12H22O11 342 g 8.57 g C12H22O11

x =
1000 g H2O mol C12H22O11 g H2O

Total grams of the solution = 8.57 g C12H22O11 + 1.00 g H2O = 9.57 g

8.57 g
Percent sugar = x100 = 89.5%
9.57 g
For the solution that boils at 240 0F

30.51mol C12H22O11 342 g 10.43 g C12H22O11

x =
1000 g H2O mol C12H22O11 g H2O

10.43 g
Percent sugar = x100 = 91.2%
11.43 g

The mass percent range for the solutions is 89.5 % to 91.2 %

13.18 ∆Tb = Kb × m = 0.51 °C m–1× x m = 2.36 °C

x m = 4.627 m
To find the number of grams of glucose, first we need to find the number of moles of glucose.

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mol glucose = (m solution)(kg solvent)

mol glucose = (4.627 m)(0.255 kg H2O) = 1.18 mol glucose
 180.9 g glucose 
g glucose = (1.18 mol glucose)   = 213 g glucose
 1 mol glucose 
13.19 It is first necessary to obtain the values of the freezing point of pure benzene and the value of Kf for
benzene from Table 13.4 of the text. We proceed to determine the number of moles of solute that are
present and that have caused this depression in the freezing point: ∆T = Kfm
∴ m = ∆T/Kf = (5.45 °C – 4.13 °C)/(5.07 °C kg mol–1) = 0.260 m
Next, use this molality to determine the number of moles of solute that must be present:
0.260 mol solute/kg solvent × 0.0850 kg solvent = 0.0221 mol solute
Last, determine the formula mass of the solute:
3.46 g/0.0221 mol = 157 g mol-1

13.20 To find the molar mass of the substance, first, we need to find the molality of the solution from the freezing
point depression, and then using the 5.0% (wt/wt) amount, determine the moles of the solute.
∆T 80.2 o C − 77.3 o C
m= = = 0.420 m
Kf 6.9 o C m −1
Assume there is 100 g of solution:
5 g unknown substance
5.0% (wt/wt) =
5 g unknown substance + 95 g naphthalene
We have 95 g of naphthalene, or 0.095 kg naphthalene and 5 g of the unknown.
Using the equation for molality, we can determine the number of moles of the unknown
mol unknown = (m solution)(kg solvent) = (0.420 m)(0.095 kg naphthalene) = 0.0399 mol unknown
5.0 g unknown
molar mass = = 125 g mol–1
0.0399 mol unknown

13.21 Use the equation Π = MRT:

 1 mol protein 
( 5 g protein )  
M=  235, 000 g protein  = 2.13 × 10–4 M solution
0.1000 L solution
R = 0.0821 L atm/K mol
T = 4.0 + 273.2 = 277.2 K
Π = (2.13 × 10–4 M solution)(0.0821 L atm/K mol)(277.2 K) = 4.84 × 10–3 atm
 760 mm Hg 
mm Hg = 4.84 × 10–3 atm   = 3.68 mm Hg
 1 atm 
 13.6 mm H 2 O 
mm H2O = 3.68 mm Hg   = 50.0 mm H2O
 1 mm Hg 

13.22 We can use the equation Π = MRT:

Π = (0.0115 M)(0.0821 L atm/K mol)(310 K)
Π = 0.293 atm
Π = 0.293 atm x 760 torr atm-1 = 222 torr

To determine the boiling and freezing temperatures of the solution we can assume that the molality is equal
to the molarity. At low concentrations the two values are nearly identical.

Tf = 0 0C –m Kf = -0.0115 m x 1.86 0C m-1 = -0.021 0C

Tbp = 100 0C + m Kbp = 100 + 0.0115 m x 0.51 0C m-1 = 100.006 0C

Note that significant figures rules were not used for the boiling point answer.

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13.23 Π = MRT
 10 mm H 2 O   1.00 g mL−1   1 atm 
Π = 6.45 cm water    
−1   760 mm Hg 
= 6.24 × 10–3 atm
 1 cm H 2 O   13.6 g mL   
R = 0.0821 L atm / mol K
T = 277 K

M=
Π
=
(
6.24 × 10−3 atm )
= 2.74 × 10–4 mol L–1
RT ( 0.0821 L atm/mol K )( 277 K )
mol protein = (2.74 × 10–3 mol L–1)(0.1000 L) = 2.74 × 10–5 mol
0.1372 g protein
molar mass = = 5.00 x 103 g mol–1
2.74 × 10−5 mol protein

13.24 We can use the equation Π = MRT, remembering to convert pressure to atm:
 1 atm 
atm = (25.0 torr)   = 0.0329 atm
 760 torr 
Π = 0.0329 atm = M × (0.0821 L atm/K mol)(298 K)
M = 1.34 × 10–3 mol L–1
mol = 1.34 × 10–3 mol L–1 × 0.100 L = 1.34 × 10–4 mol
72.4 × 10−3 g
formula mass = = 5.38 × 102 g mol–1
−4
1.34 × 10 mol

13.25 For the solution as if the solute were 100% dissociated:

∆T = (1.86 °C m–1)(2 × 0.237 m) = 0.882 °C and the freezing point should be –0.882 °C.
For the solution as if the solute were 0% dissociated:
∆T = (1.86 °C m–1)(1 × 0.237 m) = 0.441 °C and the freezing point should be –0.441 °C.

13.26 Use the freezing point depression equation:

∆T = Kfm
Remember that there are two moles of ions for each mole of MgSO4.
Kf water = 1.86 °C m–1
(a) For 0.1 m MgSO4 m = 0.2 m
∆T = (1.86 °C m–1)(0.2 m) = 0.372 °C thus, Tf = − 0.372 oC

(b) For 0.01 m MgSO4 m = 0.02 m

–1
∆T = (1.86 °C m )(0.02 m) = 0.0372 °C thus, Tf = − 0.0372 °C

(c) For 0.001 m MgSO4 m = 0.002 m

∆T = (1.86 °C m–1)(0.002 m) = 0.00372 °C thus, Tf = − 0.00372 °C

The first freezing point depression could be measured using a laboratory thermometer that can measure
1 °C increments.

Review Questions

13.1 This event, diagrammed in Figure 13.1, is due to the tendency for all systems to proceed spontaneously
towards a state with a higher degree of randomness (disorder).

13.2 First, the tendency towards randomness drives the solution process, and second, the new forces of attraction
between solute and solvent molecules drive the process. Thus the relative degree of solute–solute, solvent–
solvent and solute–solvent interactions will determine if a solute is soluble in a solvent.

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13.3 Since water and methanol both have OH groups, there can be hydrogen bonding between a water molecule
and a methanol molecule. This allows any proportion of methyl alcohol in water to be nearly as stable as
either separate water samples or separate methyl alcohol samples.

13.4 Water molecules are tightly linked to one another by hydrogen bonding. In hexane, however, which is a
nonpolar organic substance, we have only weak London forces of attraction. This means that hexane as a
solute in water offers no advantage in attraction to individual water molecules, and the solvent is therefore
not disrupted to allow the solute to dissolve.

13.5 The dipole moments of water molecules can be oriented so as to stabilize both the dissolved cation and the
dissolved anion.

13.6 There is no solvating force provided by carbon tetrachloride that can overcome and offset the very strong
ion–ion forces of the solid KCl sample.

13.7 Since the enthalpy of solution is positive, the process is endothermic. The system thus requires heat for the
dissolving process, and the heat flow should cause the temperature to decrease as the solute dissolves.

13.8 The lattice energy is numerically larger since that step is endothermic, that is it requires energy to separate
the particles.

13.9 The Al3+ ion, having the greater positive charge, should have the larger hydration energy.

13.10 When a gas dissolves in a liquid, there is no endothermic step analogous to the lattice energy of a solid.
The only enthalpy change is the one associated with hydration, and this is always negative.

13.11 There is a greater attraction between water and acetone molecules in the resulting solution than there is
among acetone molecules in the starting pure solute or water molecules in the starting pure solvent.

13.12 The disruption of ethyl alcohol and the disruption of hexane together cost more energy than is gained on
formation of the solution. This is because the two liquids are not alike; ethyl alcohol is a polar substance
with hydrogen bonding, whereas hexane is a nonpolar liquid having only London forces.

13.13 If the solution becomes cool, it is an endothermic process and the ∆Hsoln is positive. This is because the
solution is absorbing heat from the surroundings. The solubility is likely to increase with increasing
temperature because heat is required for the reaction to proceed, so increasing the temperature increases the
amount of heat available.

13.14 The fact that the ∆Hsoln value for the formation of a mixture of A and B is zero, implies that the relative
strengths of A–A, B–B, and A–B intermolecular attractions are similar.

13.15 We can estimate from Figure 13.10 that the solubility of NH4NO3 in 100 g of H2O is 550 g at 75 °C and
165 g at 15 °C. The amount of solid that will crystallize is the difference between these two solubilities,
namely 550 – 165= 385 g in 100 g of solvent. However, we have 125 g of solvent.

385 g NH 4 NO3
x 125 g solvent = 481 g NH 4 NO3 will separate out of the solution.
100 g solvent

13.16 Oxygen solubility increases as the temperature decreases. The larger fish will need more oxygen and will
be found in the colder areas of lake bottoms.

13.17 Henry's Law is the statement, applied to the dissolving of a gas in a solvent, that at a given temperature, the
concentration (Cg) of the gas in a solution is directly proportional to the partial pressure (Pg) of the gas on
the solution, where k in the following equation is the constant of proportionality: Cg = k × Pg. As

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discussed in the text, an alternate statement expresses the relationship of concentration at one pressure P1 to
the concentration that would exist at some new pressure P2: C1/P1 = C2/P2

13.18 The atmospheric pressure on a mountain is less than the atmospheric pressure at sea level. From Henry's
Law, as the partial pressure of oxygen decreases, the concentration of the oxygen also decreases.
Therefore, there is less oxygen to sustain life in mountain streams.

13.19 Ammonia is more soluble in water than nitrogen because ammonia is able to hydrogen bond with solvent
molecules, whereas nitrogen cannot. Nitrogen is a nonpolar molecular substance, whereas ammonia is a
polar substance capable of hydrogen bonding. Also, ammonia reacts with water to form nonvolatile ions:
NH3(g) + H2O(l)
NH4+(aq) + OH–(aq)

Hydrogen chloride would have a high solubility in water because it ionizes in water:
HCl(g) + H2O(l)
H3O+(aq) + Cl–(aq)

13.20 When the cap is removed from a bottle of carbonated beverage, the liquid fizzes because CO2 is being
released from the liquid. When the cap is on, the CO2 fills the space above the liquid until equilibrium is
established between the gas and the liquid. After the cap is removed, the equilibrium is disrupted and more
of the gas leaves the solution. This is the fizzing.

13.21 (a) mole fraction = moles component/total number of moles

(b) mole percent = mole fraction × 100%
(c) molality = moles solute/kg solvent
(d) percent by mass = (mass component/total mass) × 100%

The maximum value for mole fraction is 1, and the maximum value for mole percent and percent by mass
is 100 %.

13.22 Molality is independent of temperature. Molarity decreases with increasing temperature because the
volume of the solvent increases with increasing temperature.

13.23 The molarity will be greater than 1.0. Since the density of the solution is greater than one, the mass of the
solution in kg will be greater than its volume in liters.

13.24 A colligative property of a solution is one that depends only on the molal concentration of the solute
particles, and not on the identity of the solute.

13.25 A solution is ideal if the sum of the partial pressures of the components of the solution equals the observed
vapor pressure of the solution, i.e., if the solution obeys Raoult's Law. Also, it should be true that the heat
of solution is nearly zero.

13.26 A positive deviation indicates that the vapor pressure of the real solution is greater than expected if the
solution behaved ideally. Positive deviations result when mixtures with weaker intermolecular forces of
attraction between the two substances as compared to the intermolecular forces of the pure substances are
formed.

13.27 When a solute is dissolved in a solvent, the vapor pressure is lowered. As a result, the boiling point is
increased to a temperature where the vapor pressure is high enough to once again allow boiling to occur.
This affect also reduces the triple point and the entire solid-liquid equilibrium curve on a phase diagram
shifts to lower temperatures. The net result is a lowering of the freezing point.

13.28 These are semipermeable because only certain substances are able to pass through the membrane. A
nonpermeable material would allow nothing to pass through.

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13.29 An osmotic membrane allows only solvent to pass, whereas a dialyzing membrane allows solvated ions of a
certain minimum size to pass as well as solvent molecules. A dialyzing membrane prevents the passage of
only certain solute particles, usually those of large size, such as colloid particles.

13.30 The side of the membrane less concentrated in solute will be more concentrated in solvent. Therefore, the
escaping tendency of the solvent will be greater than on the side of the membrane less concentrated in
solute. The solvent will shift through the membrane from the side less concentrated in solute to the side
more concentrated in solute.

13.31 The solution that loses solvent into the other solution is the one with the lower molarity.

13.32 In each case, the osmotic pressure Π is given by the equation: Π = M × R × T. Since we do not know
either the density of the solution or the volume of the solution, we cannot convert values for % by mass into
molarities. However, we do know that glucose, having the smaller molecular mass, has the higher
molarity, and we conclude that it will have the larger osmotic pressure.

13.33 By the "association of solute particles" we mean that some particles are attracted to others, or that solvent
does not perfectly insulate solute particles from attachment to one another. This is another way of saying
that there is less than 100% dissociation or dissolution of solute in such a solution.

Colligative properties depend on the number of particles in solution. If association of solute occurs, this
decreases the number of independent particles in solution. Therefore, the freezing point will not be lowered
as much as expected, and the boiling point and osmotic pressure will not increase as much as expected.

13.34 If a cell is placed in a solution, the concentration of salts in the solution will affect the cell. If the solution
is hypertonic, the concentration of salts is higher than the concentration of salts in the cell. If the solution is
hypotonic, then the concentration of salts is lower than the concentration of salts in the cell.

13.35 Ionic compounds dissociate in solution. The dissociation results in an increase in the number of particles in
the solution, i.e., one NaCl “molecule” will dissociate creating two ions; Na+ and Cl–. Colligative
properties depend upon the concentration of particles so any compound that dissociates into multiple
particles will have pronounced effects on colligative properties.

13.36 The van't Hoff factor is the ratio of the value for a colligative property as actually measured to that value of
the colligative property that is expected in the complete absence of any solute dissociation. A van't Hoff
factor of one is expected for all nondissociating molecular solutes. A van’t Hoff factor greater than one
indicates a dissociation of the solute. A van’t Hoff factor less than one indicates association of the solute.
If the van’t Hoff factor is 0.5, then this indicates the formation of dimers.

13.37 The solute that dissolves to produce the greater number of ions, Na2CO3, gives the solution with the larger
boiling point elevation and, thus, the higher boiling point.

13.38 (a) suspension

(b) solution or a suspension. It depends on the type of apple juice
(c) solution
(d) solution
(e) suspension. The oils from the lemon are not soluble on water.
(f) suspension

The laser can be used to test light scattering by the liquid.

13.39 Sodium stearate is a soap and will stabilize a water in oil emulsion. The hydrophilic head (carboxylate
group) of the molecule attaches to water and the hydrophobic tail (non-polar section) of the molecule
attaches to the oil molecules.

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13.40 A colloidal particle of BaSO4 in solution has a charged surface due to the adsorption of excess positive or
negative ions on its surface as it grows. This ionic atmosphere has a defined volume. Consider a colloidal
particle that has an excess of Ba2+ ions adsorbed on its surface. The colloidal particle will be repelled by
other positively charged colloidal particles when they come within each others ionic boundary. The
addition of an electrolyte, such as an acid or salt, to this solution decreases the volume of the ionic
boundary. The negative ions of the electrolyte will attach to a positively charged colloidal particle reducing
its overall charge. As a result, colloidal particles can come closer together and thus form larger aggregates.
Also, heating the solution can be used to increase the kinetic energy of the particles allowing them to
collide with enough energy to overcome repulsion and thus increasing particle size.
13.41 A micelle is a cluster of surfactant molecules dispersed in a colloidal suspension. Micelles form due to the
structure of surfactant molecules. They have a hydrophilic head and a hydrophobic tail. Surfactant
molecules aggregate in a manner that will minimize contact between the hydrophobic end with water
molecules. This results in a spherical structure.

Review Problems

13.42 This is to be very much like that shown in Figure 13.5:

The lattice energy is defined as: K+(g) + Cl–(g)
KCl(s) ∆H° = –715 kJ mol–1

(a) KCl(s)
K+(g) + Cl–(g), ∆H° = +715 kJ mol–1

(b) K+(g) + Cl–(g)
K+(aq) + Cl–(aq), ∆H° = –686 kJ mol–1
KCl(s)
K+(aq) + Cl–(aq), ∆H° = +29 kJ mol–1

13.43 ∆Hsoln = ∆Hlattice energy + ∆Hhydration

∆Hlattice energy = ∆Hsoln – ∆Hhydration
∆Hlattice energy = –56 kJ mol–1 – (–894 kJ mol–1) = 838 kJ mol–1

C1 C 2
13.44 =
P1 P2

C2 =
C1 × P2
=
( )
0.025 g L−1 × (1.4 atm )
= 0.035 g/L.
P1 (1.0 atm )
13.45 We can compare the solubility that is actually observed with the predicted solubility based on Henry's Law.
If the actual and the predicted solubilities are the same, we conclude that the gas obeys Henry's Law. We
proceed as in Review Problem 12.40:
C1 C 2
=
P1 P2

C2 =
C1 × P2
=
( )
0.018 g L−1 × ( 620 torr )
= 0.015 g/L.
P1 ( 740 torr )
The calculated value of C2 is the same as the observed value, and we conclude that over this pressure range,
nitrogen does obey Henry's Law.

C1 C 2
13.46 =
P1 P2

C2 =
C1 × P2
=
( )
0.015 g L−1 × ( 2.0 atm )
= 0.030 g L–1
P1 (1.0 atm )
13.47 Cgas = kH × Pgas

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 Chapter 13

CO2 = 0.0039 g O2/100 mL solution PO2 = 1.0 atm

3.9 ×10−5 g mL–1
kH = = 3.9 × 10– 5 g mL–1 atm–1
1.0 atm

13.48 One liter of solution has a mass of:

 1000 mL solution  1.07 g solution 
g solution = 1 L solution    = 1,070 g
 1 L solution  1 mL solution 

According to the given molarity, it contains 3.000 mol NaCl. This has a mass of:
 58.45 g NaCl 
g NaCl = 3.000 mol NaCl   = 175.4 g NaCl
 1 mol NaCl 

Thus, the mass of water in 1 L solution must be:

1,070 g – 175.4 g = 895 g water

 3.000 mol NaCl 

m=   = 3.35 m
 0.895 kg solvent 

13.49 Since the density of the solution is 1.00 g mL–1, the molarity and molality are the same
 0.158 mol CH3O 2 H  1 L soln   1 mL soln 
molality of the acetic acid solution =    
 1 L soln   1000 mL soln   1.00 g soln 
 1000 g soln 
×  = 0.158 m
 1 kg soln 

13.50 27.5 g glucose ÷ 180.16 g/mol = 0.153 mol glucose

molality = 0.153 mol glucose/1.00 kg solvent = 0.153 m
mole fraction = moles glucose/total moles
moles glucose = 0.153
 1 mole H 2 O 
moles H2O = (1.00 × 103 g H2O)   = 55.5 mol H2O
 18.01 g H 2 O 
0.153
χglucose = = 2.75 × 10–3
55.5 + 0.153
27.5 g glucose
mass % = × 100% = 2.68%
1000 g H 2 O + 27.5 g glucose

 1 mol NaCl 
13.51 mol of NaCl = 11.5 g NaCl   = 0.197 mol NaCl
 58.44 g NaCl 
molality = 0.197 mol NaCl/1.00 kg H2O = 0.197 molal
mass % = 11.5/1011.5 g × 100% = 1.14%

mole % =
( mol NaCl ) × 100%
( total mol )
moles NaCl = 0.197 moles

mole % =
( 0.197 mol NaCl ) × 100% = 0.354%
( 55.5 mol H 2 O + 0.197 mol NaCl )

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 Chapter 13

Since the density of water is 1.00 g/mL, the volume of 1 kg is 1 L. Thus, the molarity is: 0.197 mol/1.00 L
= 0.197 M. A solvent must have a density close to 1 g/mL for this to happen. Also, the volume of the
solvent must not change appreciably on addition of the solute.

13.52 We need to know the mole amounts of both components of the mixture. It is convenient to work from an
amount of solution that contains 1.35 mol of ethyl alcohol and, therefore, 1.00 kg of solvent. Convert the
number of moles into mass amounts as follows:
For CH3CH2OH:
g ethanol  1.35 mol ethanol   46.08 g ethanol   1 kg water 
=    = 62.2 g ethanol/1000 g water
g solution  1 kg water   1 mol ethanol   1000 g water 
Mass % ethanol = (mass ethanol/(total solution mass) × 100%
Mass % ethanol = (62.2 g ethanol/(1,000 g water + 62.2 g ethanol) × 100%
= 5.86%

13.53 If we have 100.0 g of the solution, then 19.5 g is NaCl and the remainder, 80.5 g, is water. We need to
know the number of moles of NaCl and the number of kg of water:
 1 mol NaCl 
mol NaCl = (19.5 g NaCl)   = 0.334 mol NaCl;
 58.44 g NaCl 
 1 kg H 2 O  –2
kg H2O = (80.5 g)   = 8.05 × 10 kg H2O.
 1000 g H O
2 
0.334 mol NaCl
Molality = = 4.14 m NaCl.
8.05 ×10−2 kg H 2 O

13.54 If we assume 100 g of solution we have 6.85 g NH3 and 93.15 g H2O.
 1 mole NH3 
mol NH3 = (6.85 g NH3)   = 0.402 mol NH3
 17.03 g NH3 
 1 kg 
kg H2O = (93.15 g H2O)   = 0.09315 kg H2O
 1000 g 
0.402 moles NH3
m= = 4.32 m
0.09315 kg H 2 O
 1 mole H 2 O 
mol H2O = (93.15 g H2O)   = 5.169 mol H2O
 18.0 g H 2 O 
0.402 mol NH3
mole percent = × 100% = 7.22%
( 0.402 mol NH3 + 5.169 mol H 2 O )
13.55 Assume 1 mole total.
 60.10 g 
g C3H8O = 0.250 mol   = 15.02 g C3H8O
 1 mol 
mol H2O = 0.750 mol
 18.0 g H 2 O 
g H2O = (0.750 mol H2O)   = 13.5 g H2O
 1 mol H 2 O 
15.02 g
C3H8O mass % = × 100% = 52.7%
13.5 g + 15.02 g

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 Chapter 13

0.250 mol
Molality = = 18.5 m
 1 kg 
(13.5 g ) 
 1000 g 

13.56 If we choose, for convenience, an amount of solution that contains 1 kg of solvent, then it also contains
0.363 moles of NaNO3. The number of moles of solvent is:
 1 mole H 2 O 
mol H2O = (1000 g)   = 55.6 mol H2O
 18.02 g H 2 O 
Now, convert the number of moles to a number of grams: for NaNO3, 0.363 mol × 85.0 g/mol = 30.9 g; for
H2O, 1000 g was assumed and the percent (w/w) values are:
% NaNO3 = 30.9 g/1030.9 g × 100% = 3.00%
% H2O = 1000 g/1030.9 g × 100 = 97.0%

To determine the molar concentration of NaNO3 assume 1 kg of solvent which would then contain 0.363
mole of NaNO3 or 30.9 g NaNO3. The total mass of the solution would be 1000 g + 30.9 g = 1031 g of
solution. Now, the ratio of moles of solute to grams of solution is 0.363 mol NaNO3/1031 g solution.
From this calculate the molarity of the solution
 0.363 mol NaNO3   1.0185 g soln  1000 mL soln 
M of solution =     = 0.359 M NaNO3
 1031 g solution   1 mL soln  1 L soln 
0.363 mol NaNO3
χNaNO3 = = 6.49 × 10–3
55.6 mol H 2 O + 0.363 mol NaNO3

13.57 (a) If the sample is 1.89 mol% H2SO4, then an amount of the solution that contains 1.89 mol of H2SO4
also contains (100 – 1.89) = 98.11 mol water. We can calculate the molality if we know the
number of moles of H2SO4 and the number of kg of solvent. The latter is determined as follows:
kg H2O = 98.11 mol H2O × 18.02 g/mol × 1 kg/1000 g = 1.768 kg H2O.
 1.89 mol H 2SO 4 
Molality =   = 1.07 m H2SO4.
 1.768 kg H 2 O 
(b) The mass of H2SO4 in the above sample is: 1.89 mol × 98.1 g/mol = 185 g H2SO4. The total mass
of the solution is then equal to [185 g + (1.768 × 103 g)] = 1.953 × 103 g, and the % (w/w) values
are: for H2SO4,
185 g H 2SO 4
Mass % H2SO4 = × 100 = 9.47%;
1953 g total mass
for H2O,
1768 g H 2 O
Mass % water = × 100 = 90.53%.
1953 g total mass
(c) If we have on hand 100 mL (0.100 L) of this solution, it will have a mass that can be determined
using its known density:
 1.0645 g solution 
mass solution = (100.0 mL)   = 106.4 g of solution.
 1 mL solution 
Since this solution has 9.49% (w/w) H2SO4, the mass of H2SO4 in 0.100 L of the solution is:
Mass H2SO4 = 106.4 g × 0.0949 = 10.1 g H2SO4.
The number of moles of H2SO4 is thus:
 1 mol H 2SO 4 
mol H2SO4 = (10.1 g H2SO4)   = 0.103 mol H2SO4.
 98.1 g H 2SO 4 
The molarity is the number of moles of H2SO4 divided by the volume of solution:
 0.103 mol H 2SO4 
Molarity =   = 1.03 M H2SO4.
 0.100 L solution 

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 Chapter 13

13.58 Psolution = P°solvent × χsolvent

We need to determine χsolvent:

 1 mol 
mol glucose = (55.0 g)   = 0.305 mol glucose
 180.2 g 
 1 mol H 2 O 
mol H2O = (125 g H2O)   = 6.94 mol H2O
 18.02 g H 2 O 

The total number of moles is thus: 6.94 mol + 0.305 mol = 7.25 mol and the mole fraction of the solvent is:
 6.94 mol solvent 
χsolvent =   = 0.958. Therefore,
 7.25 mol solution 
Psolution = 23.8 torr × 0.958 = 22.8 torr.

13.59 In 100 g of the mixture we have the following mole amounts:

65.0 g H2O ÷ 18.02 g/mol = 3.61 mol H2O
35 g C2H6O2 ÷ 62.07 g/mol = 0.564 mol ethylene glycol
3.61 mol H 2 O
χH2O = = 0.865
3.61 mol H 2 O + 0.564 mol ethylene glycol
Psolution = P°solvent × χsolvent = 17.5 torr × 0.865 = 15.1 torr

13.60 Pbenzene = χbenzene × P°benzene

Ptoluene = χtoluene × P°toluene
PTot = Pbenzene + PToluene
 1 mol 
mol benzene = (35.0 g)   = 0.448 mol benzene
 78.11 g 
 1 mol 
mol toluene = (65.0 g)   = 0.705 mol toluene
 92.14 g 
0.448
χbenzene = = 0.389
0.448 + 0.705
0.705
χtoluene = = 0.611
0.448 + 0.705
Pbenzene = (0.389)(93.4 torr)= 36.3 torr
Ptoluene = (0.611)(26.9 torr)= 16.4 torr
PTotal = 36.3 torr + 16.4 torr = 52.7 torr

13.61 Assume 50 g of each substance:

 1 mol pentane 
mol pentane = (50 g pentane)   = 0.693 mol
 72.15 g pentane 
 1 mol heptane 
mol heptane = (50 g heptane)   = 0.499 mol heptane
 100.21 g heptane 
0.693
χpentane = = 0.581
0.693 + 0.499
0.499
χheptane = = 0.419
0.693 + 0.499
Ppentane = χpentane × P°pentane = 0.581 × 422 torr = 245 torr

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 Chapter 13

Pheptane = χheptane × P°heptane = 0.419 × 36 torr = 15.1 torr

PTotal = Ppentane + Pheptane = (245 + 15.1) torr = 260 torr

13.62 The following relationships are to be established: PTotal = 84 torr = (P°benzene × χbenzene) + (P°toluene × χtoluene).
The relationship between the two mole fractions is: χbenzene = 1 – χtoluene, since the sum of the two mole
fractions is one. Substituting this expression for χbenzene into the first equation gives:
84 torr = [P°benzene × (1 – χToluene)] + [P°Toluene × χToluene],
84 torr = [180 torr × (1 – χToluene)] + [60 torr × χToluene].
Solving for χToluene we get: 120 × χToluene = 96,
χToluene = 0.80 and χbenzene = 0.20. The mole % values are to be 80 mol% toluene and 20 mol% benzene.

13.63 χCH3OH= P/P° = 145 torr/164 torr = 0.884

 1 mol CH3OH 
mol CH3OH = (115 g)   = 3.59 mol CH3OH
 32.0 g CH3OH 
3.59 mol CH 3OH
0.884 =
3.59 mol CH3OH + x mol C3 H5 ( OH )3
3.59 mol CH3OH
3.59 mol CH3OH + x mol C3H5(OH)3 =
0.884

x=
( 3.59 mol ) – 3.59 mol = 0.471 mol
0.884
 92.1 g 
g C3H5(OH)3 = (0.471 mol)   = 43.4 g C3H5(OH)3
 1 mol 

P 511 torr
13.64 (a) χsolvent= = = 0.971
P
526 torr
χsolute = 1 – χsolvent = 0.029
1 mol
(b) We know 0.971 = x = 2.99 × 10–2 moles
1 mol + x mol
8.3 g
(c) molar mass = = 278 g/mol
2.99 ×10−2 mol

13.65 Psolvent = χsolvent × P°solvent

336.0 torr = χsolvent × 400.0 torr
χsolvent = 0.8400
χsolute = 1 – 0.8400 = 0.1600
The number of moles of solvent is: 33.25 g ÷ 109.0 g/mol = 0.3050 mol and the following expression for
mole fraction of solvent can be solved to determine the number of moles of solute
We know 0.8400 = 0.3050 mol/(0.3050 mol + x), x = 5.81 × 10–2 moles
Molar mass = 18.26 g/5.81 × 10–2 mol = 314.3 g/mol

13.66 ∆Tf = Kfm

m = ∆Tf/Kf = 3.00 °C/1.86 °C kg/mol = 1.61 mol/kg
 1 kg 
kg = (175 g)   = 0.175 kg
 1000 g 

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 Chapter 13

 1.61 mol 
mol =   (0.175 kg) = 0.282 mol
 1 kg 
 342.3 g 
g = (0.282 mol)   = 96.4 g
 1 mol 

13.67 ∆Tb = Kbm

 5 oC 
Tc = (270 °F – 32 °F)   = 132 °C
 9 oC 
 
(132 °C – 100 °C) = (0.51 °C kg/mol) × m
m = 63 m
 
 
χsucrose =   = 0.53
63 mol sucrose
 1 mol H 2 O  
 1000 g water   + 63 mol sucrose 
 
  18.01 g H 2 O  

13.68 ∆Tb = Kbm

∆Tb = 81.7 °C – 80.2 °C = 1.5 °C
m= ∆Tb/Kb = 1.5 °C/2.53 °C kg/mol = 0.593 mol/kg
mol solute = (0.593 mol/kg)(0.100 kg) = 0.0593 mol
molar mass = (14 g)/0.0593 mol = 240 g/mol

13.69 ∆T = (5.45 – 3.45) = 2.00 °C = Kf × m = 5.07 °C kg mol–1 × m

m = 0.394 mol solute/kg solvent
0.394 mol/kg benzene × 0.200 kg benzene = 0.0788 mol solute and the molecular mass is: 12.00 g/0.0788
mol = 152 g/mol

13.70 ∆Tf = Kfm

m = ∆Tf/Kf = 0.337 °C/5.07 °C kg/mol = 0.0665 mol/kg
 0.0665 mol 
mol =   (0.5 kg) = 0.0332 mol
 1 kg 
4.26 g
molar mass = = 128.3 g/mol
0.0332 mol
The empirical formula has a mass of 64.1 g/mol. So the molecular formula is C8H4N2.

13.71 (a) For convenience we choose to work with 100 g of the compound, and then to convert the mass
amounts of each element found in this compound into mole amounts:
for C, 42.86 g ÷ 12.01 g/mol = 3.569 mol C
for H, 2.40 g ÷ 1.01 g/mol = 2.38 mol H
for N, 16.67 g ÷ 14.01 g/mol = 1.190 mol N
for O, 38.07 g ÷ 16.00 g/mol = 2.379 mol O
The relative mole amounts that represent the empirical formula are determined by dividing the
above mole amounts each by the smallest mole amount:
for C: 3.569 mol ÷ 1.190 mol = 2.999
for H: 2.37 mol ÷ 1.190 mol = 1.99
for N: 1.190 mol ÷ 1.190 mol = 1.000
for O: 2.379 mol ÷ 1.190 mol = 1.999
and the empirical formula is C3H2NO2.
(b) ∆Tb = 1.84 °C = Kb × m = 2.53 °C kg mol–1 × m
m = 0.727 mol solute/kg benzene.

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 Chapter 13

The number of moles of solute is: 0.727 mol/kg benzene × 0.045 kg benzene = 0.0327 mol, and
the formula mass is: 5.5g/0.0327 mol = 168 g/mol. Since the mass of the empirical unit is 84, the
molecular formula must be twice the empirical formula, namely C6H4N2O4.

13.72 (a) If the equation is correct, the units on both sides of the equation should be g/mol. The units on the
right side of this equation are:

(g) × (L atm mol−1 K −1 ) × (K)

= g/mol
L × atm
which is correct.

(b) Π = MRT = (n/V)RT, n = ΠV/RT

This means that we can calculate the number of moles of solute in one L of solution, as follows:

( 0.021 torr ) (1 atm 760 torr ) (1.0 L )

n= = 1.1 × 10−6 mol
( 0.0821 L atm mol−1 K −1 ) ( 298 K )
The molecular mass is the mass in 1 L divided by the number of moles in 1 L:
2.0 g/1.1 × 10–6 mol = 1.8 × 106 g/mol

13.73 Π = MRT = (n/V)RT, n = ΠV/RT

 1 atm 
( 3.74 torr )   (1 L )
n=  760 torr  = 2.00 × 10−4 mol
 Latm 
 0.0821 mol K  ( 300 K )
 
0.400 g
molar mass = = 2.00 × 103 g/mol
−4
2.00 × 10 mol

13.74 The equation for the vapor pressure is:

Psolution = P°H2O × χH2O
Where P°H2O is 17.5 torr. To calculate the vapor pressure we need to find the mole fraction of water first.
χH2O = moles H2O/(moles H2O + moles NaCl)
Calculate the moles of NaCl in 21.5 g
 1 mol NaCl 
mol NaCl = ( 21.5 g NaCl )   = 0.368 moles NaCl
 58.44 g NaCl 
When NaCl dissolves in water, Na+ and Cl– are formed. So, for every mole of NaCl that dissolves, two
moles of ions are formed. For this solution, the number of moles of ions is 0.736.
The number of moles of solvent (water) is:
 1 mol H 2 O 
mol H 2 O = (100 g H 2 O )   = 5.55 moles H 2 O
 18.02 g H 2 O 
Calculate the mole fraction as
( moles H 2 O ) 5.55 mol
χ H2O = = = 0.883
(moles H 2 O + moles NaCl) (5.55 mol + 0.736 mol)
The vapor pressure is then Psolution = P°H2O × χH2O = 17.5 torr × 0.883 = 15.5 torr

P 38.7 torr
13.75 χH2O = = = 0.917
o 42.2 torr
P

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 Chapter 13

 1 g   1 mol 
mol H 2 O = (175 mL)    = 9.71 mol
 1 mL   18.02 g 
9.71 mol
0.917 =
9.71 mol + x mol
X = 0.883 mole
Since the van't Hoff factor for AlCl3 is 4, we need:
0.883 mol/4 = 0.221 mol AlCl3
 133.3 g 
g AlCl3 = (0.221 mol)   = 29.4 g AlCl3
 1 mol 

13.76 Assume 100 mL of solution, that is, 2.0 g NaCl and 0.100 L of solution:
Π = MRT
 1 mol NaCl 
(2.0 g NaCl)  
M =  58.45 g NaCl  = 0.34 M
0.100 L
For every NaCl there are two ions produces so M = 0.68 M
 760 torr  4
∏ = (0.68 M)(0.0821 L atm/mol K)(298 K)   = 1.3 × 10 torr
 1 atm 
13.77 Π = MRT For each ion, multiply the concentration by 24.47 L atm/mol

Ion Molality (mol/L) Π (atm)

Cl– 0.566 13.9
Na+ 0.486 11.9
Mg2+ 0.055 1.35
SO42– 0.029 0.710
Ca2+ 0.011 0.269
K+ 0.011 0.269
HCO3– 0.002 0.0489

Adding these together we get Π = 28.4 atm. Thus, a pressure greater than 28.4 atm is needed to desalinate
seawater by reverse osmosis.

13.78 CaCl2
Ca2+ + 2Cl–; van’t Hoff factor, i = 3

∆Tf = i × Kf × m = (3)(1.86 °C m–1)(0.24 m) = 1.3 °C
The freezing point is –1.3 °C.

13.79 If we assume that mercury(I) nitrate has the formula HgNO3, we predict a freezing point of –0.37 °C,
∆Tf = i × Kf × m = 2 × 1.86 °C/m × 0.10, m = 0.37 °C.
However, the observed freezing point depression is lower than this. So, assume that the correct formula of
the compound is Hg2(NO3)2 where the mercury ion is dimeric and divalent, i.e., Hg22+.

Assuming that the person who prepared the solution thought it was HgNO3 when they calculated the
molality, the concentration of the solution based on the correct formula for the compound would be
recalculated correctly as 0.050 m since the true formula mass is twice that assumed, and
∆Tf = i × Kf × m = 3 × 1.86 °C/m × 0.050 m = 0.28 °C.
Therefore, the dissociation produces three ions and the equation is:
Hg2(NO3)2
Hg22+ + 2NO3–

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13.80 Any electrolyte such as NiSO4, that dissociated to give 2 ions, if fully dissociated should have a van't Hoff
factor of 2.

13.81 MgSO4
Mg2+ + SO42–, the van’t Hoff factor is expected to be two.

13.82 ∆Tf = i × Kf × m

i = ∆Tf/Kf × m = 0.415°C/(1.86 °C m–1)(0.118 m) = 1.89

13.83 To solve this problem, we need to assume the density of the solution is 1 g/mL. From problem 13.82 we
know that most of the LiCl has dissociated. As a result, the affect of the dissociated ions will increase the
osmotic pressure.
Π = MRT
If we consider the dissociation
Π = iMRT
Π = (1.89)(0.118 mol L–1)(0.0821 L atm/mol K)(283 K)(760 torr/1atm) = 3.94 × 103 torr

Additional Exercises

13.84 The partial pressure of N2 in air is:

PN2 = 1.00 atm(78 mol%) = 0.78 atm
Therefore, according to Henry’s Law, the amount of N2 dissolved per liter of blood at 1.00 atm is:
(1 L)(0.015 g/L)(0.78/1.00) = 0.012 g N2
0.012 g N2 (1 mol N2/28.0 g N2) = 0.00043 mol N2
The amount of N2 dissolved per liter of blood at 4.00 atm would be four times that, or: 0.0017 mol N2

The amount of nitrogen released per liter of blood upon quickly surfacing is the difference between the
two, or (0.0017 mol – 0.00043 mol) = 0.0013 mol N2. The volume of that gas at 1.00 atm and 37 °C would
be given by the ideal gas law:
PV = nRT
V = nRT/P
V = (0.0013 mol N2)(0.0821 L·atm/mol·K)[(273+37) K]/1 atm
V = 0.033 L = 33 mL N2 per liter of blood

13.85 Let A = CCl4 and B = unknown

PTot = PA + PB
PTot = χAPA° + χBPB°
We also know that χA + χB = 1
So, PTot = (1 – χB)PA° + χBPB°

PTot – PA° = χB(PB° – PA°)

P − PAo   137 torr − 143 torr 

χB =  Tot = = 0.103
 Po − P o   85 torr − 143 torr 
 B A 

χA = 0.897

mol CCl4
χCCl4 = , rearranging, we get
mol CCl4 + mol unknown

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 
moles unknown = mol CCl4  1 − 1
 χCCl 
 4 

 1 mol CCl4 
mol CCl4 = (400 g CCl4)   = 2.60 mol CCl4
 153.8 g CCl4 

mol unknown = 2.60 mol CCl4  1 

− 1 = 0.299 mol unknown
 0.897 

43.3 g
molar mass = = 145 g / mol
0.299 moles

13.86 Π = MRT = (0.0100 mol/L)(0.0821 L atm K–1 mol–1)(298 K) = 0.245 atm

0.245 atm × 760 torr/atm = 186 torr.

13.87 (a) Since –40.0°F is equal to –40.0°C, the following expression applies: ∆T = Kfm, so
40 °C = (1.86 °C kg mol–1) × m, m = 40/1.86 mol/kg = 21.5 molal
Therefore, 21.5 moles must be added to 1 kg of water.
 62.1 g   1.00 mL  3
(b) mL = (21.5 moles)    = 1.2 × 10 mL
 1 mol   1.11 g 
(c) There are 946 mL in one quart. Thus, for 1 qt of water we are to have 946 mL, and the required
number of quarts of ethylene glycol is:

 1.2 × 103 mL C H O   1 g H O   946 mL H O   1 qt C H O

qt C2 H 6 O 2
 2 6 2  2 2 2 6 2 
1 qt H 2 O  1000 g H 2 O   1 mL H 2 O   1 qt H 2 O   946 mL C2 H 6 O 2 
    
 
= 1.2 qt C2H6O2
The proper ratio of ethylene glycol to water is 1.2 qt to 1 qt.

13.88 (a) The height difference is proportional to the osmotic pressure, therefore ∏ may be calculated by
converting the height difference to the height of a mercury column in mm, which is equal to the
pressure in torr (1 mm Hg = 1 torr):
hHg = hsolution × (dsolution/dHg) = (12.6 mm) × (1.00 g/mL/13.6 g/mL) = 0.926 mm Hg
P = 0.926 torr

(b) ∏ = MRT
 1atm 
(0.926 torr)  
M = ∏/RT =  760 torr  = 4.98 × 10–5 M
 L atm 
 0.0821 mol K  (298 K)
 
(c) Since this is a dilute solution and the solute does not dissociate, we can assume that the molarity
and molality are equivalent. So,
∆Tf = kfm = (1.86 °C m–1)(4.98 × 10–5 m)
= 9.26 × 10–5 °C
Freezing point will be –9.26 × 10–5 °C

(d) The magnitude of the temperature change is too small to measure.

13.89 (a) Since the molarity of the solution is 4.613 mol/L, then one L of this solution contains:

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4.613 mol × 46.07 g/mol = 212.5 g C2H5OH.

The mass of the total 1 L of solution is:
1000 mL × 0.9677 g/mL = 967.7 g.
The mass of water is thus 967.7 g – 212.5 g = 755.2 g H2O, and the molality is:
4.613 mol C2H5OH/0.7552 kg H2O = 6.108 m.
(b) % (w/w) C2H5OH = (212.5 g/967.7 g) × 100% = 21.96%

13.90 (a) ∆Tb = kbm = (0.51 °C m–1)(1.25 m)

= 0.64 °C
∆Tb = 100 °C + 0.64°C = 100.64 °C
(b) ∆Tb = ikbm = (4)(0.51 °C m–1)(1.25 m)
= 2.55 °C
∆Tb = 100 °C + 2.55°C = 102.55 °C
(c) i = 0.229 °C/0.51 °C = 0.449

13.91 Colligative properties are based on the number of particles in solution. In each of the two cases we are told
to assume complete dissociation. Thus, one formula unit of AlCl3 contributes 4 ions and one formula unit
of Na2SO4contributes 3 ions to the solution.

The total molality, mT, of the solution is the sum of the molalities of the two salts.
mT = m1(AlCl3) + m2(Na2SO4)
The molality of AlCl3 is 4/7 of mT and the molality of Na2SO4 is 3/7 of mT.

∆Tf = i × Kf × mT

o
C
2.65 o C = 7 x 1.86 x mT
molal
mT = 0.2035 m

Since the total molality is small we can assume that molarity and molality are approximately the same
value.

4
M(AlCl3) = x 0.2035 m = 0.116 M
7

3
M(Na2SO4) = x 0.2035 m = 0.0872 M
7

Multi-Concept Problems

13.92 From the boiling point elevation we can determine the total molality of the solution.

∆Tf = i × Kf × mT

0
C
4.6 o C = 5 x 0.51 x mT
molal

mT = 1.804 m

The molality of the KCl solution is:

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 Chapter 13

2
x 1.804 m = 0.7216 m
5

The molality of the Fe(NO3)2 is:

3
x 1.804 m = 1.0824 m
5

From the titration we can determine the molarity of the iron(II) nitrate.

6Fe2+ + Cr2O72- + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O

2-
0.220 mmol Cr2 O 7 6 mmol Fe 2+
36.3 mL x x = 47.916 mmol Fe 2+
mL mmol Cr2 O72-

Or 47.916 x 10-3 mol Fe2+

We can determine the volume of solvent from the calculated molality of the iron(II) solution and the
solution’s density.

First, we need to determine the mass of solvent containing 4.7916 x 10-2 mol of iron salt.

1 kg solvent
x 0.04792 mol = 4.427 x 10−2 kg solvent
1.0824 mol Fe(NO3 ) 2

Or 44.27 g of solvent

179.857 g
Mass of Fe(NO3 ) 2 = 0.04792 mol x = 8.62 g
mol Fe(NO3 ) 2

Mass of solution = 8.62 g Fe(NO3)2 + 44.27 g H2O = 52.89 g

1 mL
Volume of solution = 52.89 g x = 51.25 mL
1.032 g

47.916 mmol Fe(NO3 ) 2

M{Fe(NO3)2} = = 0.93 M
51.25 mL

The molarity of the KCl solution would be:

0.7216 mol KCl 1

M{KCl} = x 4.427 x 10−2 kg solvent x = 0.62 M
kg solvent 5.125 x 10−2 L

13.93 Osmotic pressure is given by Π = iMRT

Since this is a mixture, the molarity, M, is the sum of the individual solutes in solution. BaSO4 will
precipitate out of solution. Therefore, we need to determine how much Ba2+ and SO42− will be removed
from the solution.

Before reaction:

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mmol Ba2+ = 25.00 mL x 0.200 M = 5 mmol

mmol NO3− = 2 x 5 mmol = 10 mmol
mmol SO42− = 14.00 mL x 0.250 M = 3.5 mmol
mmol K+ = 2 x 3.5 mmol = 7 mmol

SO42− is the limiting reagent.

After reaction we have:

1.5 mmol of Ba2+

10 mmol of NO3−
7 mmol of K+

1.5 mmol + 10 mmol + 7 mmol

iM = = 0.474 M
39.00 mL

Π = 0.474 M x 0.0821 L atm K-1 mol-1 x 298 K = 11.6 atm

11.6 atm x 760 torr atm-1 = 8.82 x 103 torr

13.94 There are two isomers of C2H6O, ethanol, and dimethyl ether.

Shown below are the abbreviated structural forms of the two isomers.

(a) Both are expected to be liquids at 25 oC. Ethanol possesses a dipole moment, 1.68 Debye, it can
hydrogen bond with itself, and has significant London forces. Dimethyl ether has a dipole, 1.30 Debye,
and possesses significant London forces.
(b) Both should be soluble in water since they are both polar and can interact with polar water molecules.
Also, ethanol will hydrogen bond with water. Neither should be significantly soluble in non-polar
pentane.
(c) Ethanol will form hydrogen bonds due the presence of the OH group and unshared electrons on the
oxygen atom. Dimethyl ether cannot hydrogen bond as it does not have a hydrogen attached to the
oxygen atom.
(d) Both are non-electrolytes since they do not significantly ionize in water. The hydrogen on the OH
group is not an ionizable hydrogen.

13.95 The reaction is given below.

3Sn2+ + Cr2O72- + 14H+ → 3Sn4+ + 2Cr3+ + 7H2O

0.650 mol Sn 2+
0.155 L x = 0.1008mol Sn 2 +
L

1 mol Cr2 O72 − mol Cr2 O72 −

0.1008 mol Sn 2 + x = 0.223 xV
3 mol Sn 2 + L

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 Chapter 13

V = 0.151 L or 151 mL required

To determine the osmotic pressure we first need to determine the molarity of the resulting solution.

0.1008 mol Sn 2 +
M(Sn 2 + ) = = 0.329 M
(0.155 L + 0.151 L)

0.1008 mol Sn 2 + 1 mol Cr2 O72 −

M(Cr2 O72− ) = x = 0.110 M
(0.155 L + 0.151 L) 3 mol Sn 2 +

Using these molarities and the number of particles created for each solution when the reaction is complete,
we can determine the osmotic pressure. Be sure to include the spectator ions when determining the value of
“i.”

Π = iMRT

 2−
mol Cr2 O7 mol Sn 2 +  −1 −1
Π =  4 x 0.110 + 3 x 0.329  x 0.0821 L atm K mol x 298 K
 L L 

Π = 34.9 atm Π = 34.9 atm x 760 torr atm-1 = 2.65 x 104 torr

In this solution to the problem a value of i = 4 was used for the dichromate since 2 moles of Cr3+ are
produced by the reaction. Alternately, you could determine the molar concentration of the Cr3+ and then use
the molar concentration of the dichromate to determine the molar concentration of the K+ ions.

13.96 (a) The formula masses are Na2Cr2O7·2H2O: 298 g/mol, C3H8O: 60.1 g/mol, and C3H6O: 58.1 g/mol.
 1 mol C3 H8 O   1 mol Na 2 Cr2 O7 • 2H 2 O 
g Na 2 Cr2 O7 • 2H 2 O = (21.4 g C3 H8 O)   
 60.1 g C3 H8 O   3 mol C3 H8 O 
 298 g Na 2 Cr2 O7 • 2H 2 O 
×  = 35.4 g Na 2 Cr2 O7 • 2H 2 O
 1 mol Na 2 Cr2 O7 • 2H 2 O 
(b) The theoretical yield is:
 1 mol C3 H8 O  3 mol C3 H 6 O  58.1 g C3 H 6 O 
g C3H6O = (21.4 g C3H8O)     = 20.7 g C3H8O
 60.1 g C3 H8 O  3 mol C3 H8 O  1 mol C3 H 6 O 
The percent yield is therefore: 12.4/20.7 × 100% = 59.9%

(c) First, we determine the number of grams of C, H, and O that are found in the products, and then
the % by mass of C, H, and O that were present in the sample that was analyzed by combustion,
i.e. the by–product:

 12.011 g C 
g C = (22.368 × 10–3 g CO2)  –3
 = 6.1046 × 10 g C
 44.010 g CO 2 
and the % C is: (6.1046 × 10–3 g/8.654 × 10–3 g) × 100% = 70.54% C

 2.0159 g H 
g H = (10.655 × 10–3 g H2O)  –3
 = 1.1923 × 10 g H
 18.015 g H O
2 
and the % H is: (1.1923 × 10–3 g H/8.654 × 10–3 g) × 100% = 13.78% H

For O, the mass is the total mass minus that of C and H in the sample that was analyzed:

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 Chapter 13

8.654 × 10–3 g total – (6.1046 × 10–3 g C + 1.1923 × 10–3 g H) = 1.357 × 10–3 g O

and the % O is: (1.357 × 10–3 g)/(8.654 × 10–3 g) × 100% = 15.68% O.
Alternatively, we could have determined the amount of oxygen by using the mass % values,
realizing that the sum of the mass percent values should be 100.
Next, we convert these mass amounts for C, H, and O into mole amounts by dividing the amount
of each element by the atomic mass of each element:
For C, 6.1046 × 10–3 g C ÷ 12.011 g/mol = 0.50825 × 10–3 mol C
For H, 1.1923 × 10–3 g H ÷ 1.0079 g/mol = 1.1829 × 10–3 mol H
For O, 1.357 × 10–3 g O ÷ 16.00 g/mol = 0.08481 × 10–3 mol O
Lastly, these are converted to relative mole amounts by dividing each of the above mole amounts
by the smallest of the three (We can ignore the 10–3 term since it is common to all three
components):
For C, 0.50825 mol/0.08481 mol = 5.993
For H, 1.1829 mol/0.08481 mol = 13.95
For O, 0.08481 mol/0.08481 mol = 1.000
and the empirical formula is given by this ratio of relative mole amounts, namely C6H14O.

(d) ∆Tf = Kfm, (5.45 °C – 4.87 °C) = (5.07 °C/m) × m, m = 0.11 molal, and there are 0.11 moles of
solute dissolved in each kg of solvent. Thus, the number of moles of solute that have been used
here is:
0.11 mol/kg × 0.1150 kg = 1.3 × 10–2 mol solute.
The formula mass is thus: 1.338 g/0.013 mol = 102 g/mol. Since the empirical formula has this
same mass, we conclude that the molecular formula is the same as the empirical formula, i.e.
C6H14O.

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