Chapter 13

Properties of Mixtures: Solutions

13-1

Properties of Mixtures: Solutions

13.1 Types of solutions: Intermolecular forces and
predicting solubility
13.2 Energy changes in the solution process
13.3 Solubility as an equilibrium process
13.4 Quantitative ways of expressing concentration
13.5 Colligative properties of solutions

13-2

13-3

The major
types of
intermolecular
forces in
solutions
(from Chapter 12)

Figure 13.1
13-4

(energies in parenthesis)

LIKE DISSOLVES LIKE

Substances with similar types of
intermolecular forces dissolve in each other.
When a solute dissolves in a solvent, solute-solute interactions and solventsolvent interactions are partly replaced with solute-solvent interactions.
The new forces created between solute and solvent must be comparable in
strength to the forces destroyed within the solute and the solvent.

13-5

A major factor that determines

whether a solution forms:
The relative strengths of the intermolecular forces within and
between solute and solvent molecules

13-6

Some Definitions
Solvent: the most abundant component of a given solution
Solute: component dissolved in the solvent
Solubility (S): the maximum amount of solute that dissolves in a
fixed quantity of solvent at a given temperature (in the presence
of excess solute)

Dilute and concentrated solutions: qualitative terms

13-7

Hydration
shells
around an
aqueous ion

Formation of ion-dipole
forces when a salt dissolves
in water

Figure 13.2
13-8

Liquid Solutions

Liquid-Liquid
Gas-Liquid

Gas and Solid Solutions

13-9

Gas-Gas
Gas-Solid
Solid-Solid

hexane =
CH3(CH2)4CH3

Competition
between
H-bonding
and dispersion
forces

13-10

Molecular Basis for the Solubility of CH3OH in H2O

H-bonding: CH3OH can serve as a donor and acceptor

(maximum number of three H-bonds / molecule)
Figure 13.3
13-11

SAMPLE PROBLEM 13.1

PROBLEM:

Predicting relative solubilities of substances

Predict which solvent will dissolve more of the given solute:

(a) Sodium chloride in methanol (CH3OH) or in propanol (CH3CH2CH2OH)

(b) Ethylene glycol (HOCH2CH2OH) in hexane (CH3CH2CH2CH2CH2CH3)
or in water.
(c) Diethyl ether (CH3CH2OCH2CH3) in water or in ethanol (CH3CH2OH)
PLAN:

Consider the intermolecular forces that exist between solute

molecules and consider whether the new solvent-solute interactions
can substitute for them.

SOLUTION:
(a) NaCl is ionic and forms ion-dipoles with the OH groups of both
methanol and propanol. However, propanol is subject to greater
dispersion forces (more CH bonds than methanol).
(b) Hexane has no dipoles to interact with the OH groups of ethylene glycol.
Water can H-bond to ethylene glycol.
(c) Diethyl ether can interact through dipole and dispersion forces. Ethanol
can provide both while water can only H-bond.
13-12

Structure-Function Correlations: A Soap

Soap: the salt form of a long-chain fatty acid; is amphipathic

in character (has polar and non-polar components)
Figure B13.1
13-13

The mode of
action of the
antibiotic,
Gramicidin A

Destroys the Na+/K+ ion

concentration gradients
in the cell

Figure B13.2
13-14

Gas-Liquid Solutions

QuickTime and a
Photo - JPEG decompressor
are needed to see this picture.

Non-polar gas solubility in

water is directly related to
the boiling point of the gas.

important to
aquatic life

13-15

Gas-gas solutions: All gases are infinitely soluble in one another.

Gas-solid solutions: The gas molecules occupy the spaces
between the closely packed particles of the solid.
Solid-solid solutions: alloys (substitutional or interstitial)

13-16

The arrangement of atoms in two types of alloys

Figure 13.4
13-17

Heats of solution and solution cycles

Dissolution of a solid: breaking down the process into three steps

1. Solute particles separate from each other - endothermic

solute (aggregated) + heat

solute (separated)

Hsolute > 0

2. Solvent particles separate from each other - endothermic

solvent (aggregated) + heat

solvent (separated)

Hsolvent > 0

3. Separate solute and solvent particles mix - exothermic

solute (separated) + solvent (separated)

13-18

solution + heat

Hmix < 0

Calculating the heat of solution, Hsoln

The total enthalpy change that occurs when a solution forms by
dissolving a solute into a solvent.

Hsoln = Hsolute + Hsolvent + Hmix

A thermochemical solution cycle

13-19

Solution cycles and the enthalpy components of the heat of solution

Figure 13.5
13-20

Heats of Hydration
The solvation of ions by water is always exothermic.

M+ (g) [or X- (g)]

H2 O

Hhydr of the ion < 0

M+ (aq) [or X- (aq)]

(for 1 mole of gaseous ions)

Hhydr is related to the charge density of the ion, that is,

both coulombic charge and ion size are important.
Lattice energy is the H involved in the
formation of an ionic solid from its gaseous ions.
M+ (g) + X- (g)

MX(s)

Hlattice is always (-)

Thus, Hsoln = -Hlattice + Hhydr

13-21

Heats of Hydration and Ionic Character

13-22

For a given size, greater charge leads to a more (-) Hhydr

For a given charge, smaller size leads to a more (-) Hhydr

Table 13.4
ion

Trends in Ionic Heats of Hydration

Hhydr (kJ/mol)

ionic radius (pm)

Group 1A
Li+
Na+
K+
Rb+
Cs+

76
102
138
152
167

-510
-410
-336
-315
-282

72
100
118
135

-1903
-1591
-1424
-1317

133
181
196
220

-431
-313
-284
-247

Group 2A
Mg2+
Ca2+
Sr2+
Ba2+
Group 7A

13-23

FClBrI-

Enthalpy Diagrams for Dissolving Three

Different Ionic Compounds in Water

NaCl

Figure 13.6
13-24

NH4NO3

NaOH

Entropy Considerations
The natural tendency of most systems is to become more
disordered; entropy increases.
Entropy always favors the formation of solutions.
Dissolution: involves a change in enthalpy and a change in
entropy.

13-25

Enthalpy diagrams for dissolving NaCl and octane in hexane

NaCl in insoluble in hexane!

Figure 13.7
13-26

In this case, dissolution is

entropy-driven!

More Definitions
When excess undissolved solute is in equilibrium with
the dissolved solute: a saturated solution
An unsaturated solution: more solute can be dissolved,
ultimately producing a saturated solution
A supersaturated solution: a solution that contains more
than the equilibrium amount of dissolved solute

13-27

Equilibrium in a saturated solution

Figure 13.8
13-28

solute (undissolved)

solute (dissolved)

Sodium acetate crystallizing from a supersaturated solution

nucleation

a saturated solution
results

Figure 13.9
13-29

Solubility and Temperature

Most solids are more soluble at higher temperatures.
The sign of the heat of solution, however, does not predict reliably the effect
of temperature on solubility; e.g., NaOH and NH4NO3 have
Hsoln of opposite signs, yet their solubility in H2O increases
with temperature.

13-30

The relation
between
solubility and
temperature
for several
ionic
compounds

Figure 13.10
13-31

Gas Solubility in Water: Temperature Effects

For all gases, Hsolute = 0, Hhydr < 0; thus, Hsoln < 0
solute(g) + water(l)

saturated solution(aq) + heat

Implications: gas solubility in water decreases with

increasing temperature

13-32

Thermal
Pollution

Leads to O2
deprivation in aquatic
systems

Figure 13.11
13-33

Pressure Effects on Solubility

Essentially zero for solids and liquids, but substantial for gases!
gas + solvent

13-34

saturated solution

The effect of pressure on gas solubility

Figure 13.12
13-35

gas volume is reduced;

pressure (concentration!)
increases; more collisions
occur with liquid surface

Henrys Law
A quantitative relationship
between gas solubility and
pressure

Sgas = kH x Pgas
The solubility of a gas
(Sgas) is directly
proportional to the
partial pressure of the
gas (Pgas) above the
solution.

kH = Henrys law constant

Implications for scuba diving!

for a gas; units of mol/L.atm

13-36

SAMPLE PROBLEM 13.2

PROBLEM:

Using Henrys Law to calculate gas solubility

The partial pressure of carbon dioxide gas inside a bottle of

cola is 4 atm at 25 oC. What is the solubility of CO2? The
Henrys law constant for CO2 dissolved in water is 3.3 x 10-2

PLAN:

mol/L.atm at 25 oC.
Knowing kH and Pgas, we can substitute into the Henrys Law
equation.

SOLUTION:

SCO = (3.3 x 10-2 mol/L.atm)(4 atm) =

2

13-37

0.1 mol / L

Table 13.5

Concentration Definitions

concentration term
molarity (M)

molality (m)

parts by mass
parts by volume
mole fraction

ratio
amount (mol) of solute
volume (L) of solution
amount (mol) of solute
mass (kg) of solvent
mass of solute
mass of solution
volume of solute
volume of solution
amount (mol) of solute
amount (mol) of solute + amount (mol) of solvent

13-38

SAMPLE PROBLEM 13.3

PROBLEM:

Calculating molality

What is the molality of a solution prepared by dissolving 32.0 g

of CaCl2 in 271 g of water?

PLAN: Convert grams of CaCl2 into moles and grams of water to kg. Then
substitute into the equation for molality.
SOLUTION:

molality =

32.0 g CaCl2 x

110.98 g CaCl2

0.288 mole CaCl2

271 g H2O x

13-39

mole CaCl2

kg

= 0.288 mole CaCl2

= 1.06 m CaCl2

103 g

The Sex Attractant of the Gypsy Moth

Potent at Extremely Low Concentrations!

100-300 molecules/mL air

100 parts per quadrillion by volume!
Practical Implications: a strategy used to target and
trap specific insects (Japanese beetles)
Figure 13.13
13-40

Other Expressions of Concentration

mass percent (% w/w) = mass solute / mass of solution x 100
(related to parts per million (ppm) or parts per billion (ppb))
volume percent (% (v/v) = volume solute / volume of solution x 100
% (w/v) = solute mass / solution volume x 100
mole percent (mol%) = mole fraction x 100

13-41

SAMPLE PROBLEM 13.4

Expressing concentration in parts by mass,

parts by volume, and mole fraction

PROBLEM: (a) Find the concentration of calcium (in ppm) in a 3.50 g pill that
contains 40.5 mg of Ca.
(b) The label on a 0.750 liter bottle of Italian chianti indicates
11.5% alcohol by volume. How many liters of alcohol
does the wine contain?
(c) A sample of rubbing alcohol contains 142 g of isopropyl
alcohol (C3H7OH) and 58.0 g of water. What are the
mole fractions of alcohol and water?
PLAN:

13-42

(a) Convert mg to g of Ca, find the ratio of g Ca to g pill, and multiply

by 106.
(b) Knowing the % alcohol and the total volume, the volume of
alcohol can be calculated.
(c) Convert g of solute and solvent to moles, and find the ratios of
each part to the total.

SAMPLE PROBLEM 13.4

SOLUTION:

(a)

(continued)

40.5 mg Ca x

g
103 mg

3.5 g
(b)

(c)

0.750 L chianti x

11.5 L alcohol
100. L chianti

moles isopropyl alcohol = 142 g x

moles water = 58.0 g x

2.36 mol C3H7OH

2.36 mol C3H7OH + 3.22 mol H2O
= 0.423

13-43

C3H7OH

mole
18.02 g

x 106

= 1.16 x 104 ppm Ca

= 0.0862 L alcohol

mole
60.09 g

= 2.36 mol C3H7OH

= 3.22 mol H2O

3.22 mol H2O

2.36 mol C3H7OH + 3.22 mol H2O

= 0.577

H2O

SAMPLE PROBLEM 13.5

Converting concentration units

PROBLEM: Hydrogen peroxide is a powerful oxidizing agent used in

concentrated solution in rocket fuels and in dilute solution as a
hair bleach. An aqueous solution of H2O2 is 30.0% by mass
and has a density of 1.11 g/mL. Calculate its:
(a) molality
(b) mole fraction
(c) molarity
PLAN: (a) To find the mass of solvent, assume the % is per 100 g of solution.
Take the difference in the mass of the solute and solution to
determine the mass of solvent.
(b) Convert g of solute and solvent to moles before finding .
(c) Use the density to find the volume of the solution.
SOLUTION:

(a)

g of H2O = 100. g solution - 30.0 g H2O2 = 70.0 g H2O

30.0 g H2O2 x

molality =
70.0 g H2O x
13-44

mol H2O2
34.02 g H2O2
kg H2O
103 g

= 12.6 m H2O2

SAMPLE PROBLEM 13.5

(b)

70.0 g H2O

(continued)
mol H2O

18.02 g H2O

0.882 mol H2O2

= 3.88 mol H2O

= 0.185 = of H2O2

0.882 mol H2O2 + 3.88 mol H2O

(c)

100.0 g solution x

mL
1.11 g

= 90.1 mL solution

0.882 mol H2O2

90.1 mL solution x

13-45

= 9.79 M H2O2

103 mL

Colligative Properties
Physical properties of solutions dictated by the number of
solute particles present. Their chemical structures are
not factors in determining these properties!

vapor pressure lowering

boiling point elevation
freezing point depression
osmotic pressure

13-46

Three types of electrolytes

Copyright The McGraw-Hill Companies, Inc.
Permission required for reproduction or display.

Copyright The McGraw-Hill Companies, Inc.

Permission required for reproduction or display.
Copyright The McGraw-Hill Companies, Inc.
Permission required for reproduction or display.

non-electrolyte

strong
Figure 13.14
13-47

weak

Vapor Pressure Lowering

The vapor pressure of a solution of a nonvolatile nonelectrolyte
is always lower than the vapor pressure of the pure solvent.

An entropy argument!
Figure 13.15
13-48

Quantitative Treatment of VP Lowering

Raoults Law (vapor pressure of a solvent above a solution, Psolvent)
Psolvent = solvent x Posolvent
where Posolvent = vapor pressure of the pure solvent
How does the amount of solute affect the magnitude of the VP lowering?
( substitute 1- solute for solvent in the above equation and rearrange)
Posolvent - Psolvent = P = solute x Posolvent
(change in VP is proportional to the mole fraction of solute)

13-49

SAMPLE PROBLEM 13.6

PROBLEM:

PLAN:

Using Raoults Law to find the vapor pressure

lowering

Calculate the vapor pressure lowering, P, when 10.0 mL of

glycerol (C3H8O3) is added to 500. mL of water at 50. oC. At this
temperature, the vapor pressure of pure water is 92.5 torr and its
density is 0.988 g/mL. The density of glycerol is 1.26 g/mL.

Find the mol fraction, , of glycerol in solution and multiply by the

vapor pressure of water.

SOLUTION:
10.0 mL C3H8O3 x
500.0 mL H2O x
P =

1.26 g C3H8O3

mL C3H8O3
0.988 g H2O
mL H2O

mol C3H8O3
mol H2O
18.02 g H2O

0.137 mol C3H8O3

0.137 mol C3H8O3 + 27.4 mol H2O

13-50

= 0.137 mol C3H8O3

92.09 g C3H8O3

= 27.4 mol H2O

= 0.00498
x

92.5 torr

= 0.461 torr

Boiling Point Elevation

A solution boils at a higher temperature than the pure solvent.

This effect is explained by differences between the VP of

the solution and VP of the pure solvent at a given temperature.

13-51

Superimposed phase diagrams of solvent and solution

aqueous solution:
dashed lines
pure water:
solid lines

Figure 13.16
13-52

Quantitative Treatment of BP Elevation

The magnitude of the effect is proportional to solute concentration.

Tb = Kbm
(m = solution molality, Kb = molal BP elevation constant, Tb = BP elevation)
Tb = Tb (solution) - Tb (solvent)

13-53

Quantitative Treatment of FP Depression

The magnitude of the effect is proportional to solute concentration.
Tf = Kfm
(m = solution molality, Kf = molal FP depression constant, Tf = FP depression)
Tf = Tf (solvent) - Tf (solution)

13-54

Table 13.6

Molal Boiling Point Elevation and Freezing Point

Depression Constants of Several Solvents
melting
point (oC)

boiling
point (oC)*

Kb (oC/m)

117.9

3.07

16.6

3.90

benzene

80.1

2.53

5.5

4.90

carbon disulfide

46.2

2.34

-111.5

3.83

carbon tetrachloride

76.5

5.03

-23

chloroform

61.7

3.63

-63.5

4.70

diethyl ether

34.5

2.02

-116.2

1.79

ethanol

78.5

1.22

-117.3

1.99

100.0

0.512

0.0

1.86

solvent
acetic acid

water
*at 1 atm.
13-55

Kf (oC/m)

30.

SAMPLE PROBLEM 13.7

Determining the boiling point elevation and

freezing point depression of a solution

PROBLEM: You add 1.00 kg of ethylene glycol antifreeze (C2H6O2) to your car
radiator, which contains 4450 g of water. What are the boiling and
freezing points of the resulting solution?
Find the number of mols of ethylene glycol and m of the solution;
multiply by the boiling or freezing point constant; add or subtract,
respectively, the changes from the boiling point and freezing point
of water.
SOLUTION:
mol C2H6O2
1.00 x 103 g C2H6O2 x
= 16.1 mol C2H6O2
62.07 g C2H6O2
PLAN:

16.1 mol C2H6O2

4.450 kg H2O

= 3.62 m C2H6O2

Tb = 0.512 oC/m x 3.62 m = 1.85 oC

Tf = 1.86 oC/m x 3.62 m

BP = 101.85 oC
13-56

FP = -6.73 oC

Osmotic Pressure

13-57

Applies only to aqueous solutions!

Two solutions of different concentrations are separated by

a semi-permeable membrane (allows water but not
solute to pass through)

The development of osmotic pressure

osmotic
pressure

pure
solvent

applied
pressure
needed to
prevent
volume
increase;
equal to
the
osmotic
pressure

solution

semipermeable
membrane

13-58

Figure 13.17

Quantitative Treatment of Osmotic Pressure ()

OP is proportional to the number of solute particles in a given
volume of solution (to M).
nsolute/Vsoln

or

The constant of proportionality = RT, so = M x R x T

T is the Kelvin temperature

13-59

Underlying Principle of Colligative Properties

Each property stems from an inability of solute particles to
cross between two phases.

13-60

Determination of Solute Molar Mass by Exploiting Colligative Properties

In principle, any colligative property can be used, but OP gives the
most accurate results (better dynamic range).

13-61

SAMPLE PROBLEM 13.8

Determining molar mass from osmotic pressure

PROBLEM: Biochemists have discovered more than 400 mutant varieties of

hemoglobin (Hb), the blood protein that carries oxygen
throughout the body. A physician studying a form of Hb
associated with a fatal disease first finds its molar mass (M).
She dissolves 21.5 mg of the protein in water at 5.0 oC to make
1.50 mL of solution and measures an osmotic pressure of 3.61
torr. What is the molar mass of this Hb mutant?
We know as well as R and T. Convert to atm and T to Kelvin.
Use the equation to find the molarity M and then the amount and
volume of the sample to calculate M.
atm

SOLUTION:
3.61 torr x
M=
=
760 torr
RT
= 2.08 x 10-4 M
PLAN:

# mol = g/M

(0.0821 L . atm/mol . K)(278.15 K)

L
2.08 x 10-4 mol
= 3.12 x 10-7 mol
x
1.50
mL
x
L
103 mL
21.5 mg

13-62

g
103 mg

1
3.12 x 10-7 mol

= 6.89 x 104 g/mol

Fractional Distillation of Volatile

Nonelectrolytes
The presence of each volatile component
lowers the vapor pressure of the other.
partial pressure = mole fraction x vapor pressure of pure gas
For vapor: mole fraction = partial pressure / total pressure
(thus, the vapor has a higher mole fraction of the more volatile
solution component)

13-63

Gasoline vapors
Condenser
Gas

The process
of fractional
distillation

Gasoline 38 oC
Kerosene 150 oC
Heating oil 260 oC
Lubricating oil 315 oC - 370 oC

Crude oil vapors

from heater
Steam
Figure 13.18
13-64

Residue (asphalt, tar)

Colligative Properties of Electrolyte Solutions

Must consider the full dissociation into ions!
vant Hoff factor (i) = measured value for electrolyte solution
expected value for nonelectrolyte solution
This factor is multiplied into the appropriate equations; for example,
= i (MRT).
For ideal behavior, i = mol particles in solution / mol dissolved solute
But solutions are not ideal; for example, for BP elevation of NaCl
solutions, i = 1.9, not 2!
Data suggest that the ions are not behaving
as independent particles!
13-65

Non-ideal
behavior of
electrolyte
solutions
Observed values of i are less
than the predicted (expected)
values.

Figure 13.19
13-66

An ionic
atmosphere
model for
non-ideal
behavior of
electrolyte
solutions
ionic atmospheres
Concept of effective
concentration

Figure 13.20
13-67

Some Practical Applications

ion-exchange (water softeners)

13-68

water purification

Ion exchange
for removal of
hard-water
cations

Use of ion-exchange
resins

Figure B13.4
13-69

Reverse osmosis for the removal of ions

Desalination Process
Figure B13.5
13-70

End of Assigned Material

13-71

Light scattering and the Tyndall effect

Figure 13.21
13-72

Photo by C.A.Bailey, CalPoly SLO (Myanmar)

A Cottrell precipitator for removing particulates from

industrial smokestack gases

13-73

Figure 13.22

The steps in a typical municipal water treatment plant

Figure B13.3
13-74