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
(energies in parenthesis)
13-4
 “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 solvent-

solvent 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

 Gas-Gas
 Gas-Solid
 Solid-Solid

13-9
 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 Predicting relative solubilities of substances

PROBLEM: 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

Non-polar gas solubility in

water is directly related to
QuickTime™ and a
Photo - JPEG decompressor
are needed to see this picture.
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) solution + heat Hmix < 0

13-18
 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.

H2O
M+ (g) [or X- (g)] M+ (aq) [or X- (aq)] Hhydr of the ion < 0
(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

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

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

13-22
 Table 13.4 Trends in Ionic Heats of Hydration

ion ionic radius (pm) Hhydr (kJ/mol)

Group 1A
Li+ 76 -510
Na+ 102 -410
K+ 138 -336
Rb+ 152 -315
Cs+ 167 -282
Group 2A
Mg2+ 72 -1903
Ca2+ 100 -1591
Sr2+ 118 -1424
Ba2+ 135 -1317
Group 7A
F- 133 -431
Cl- 181 -313
Br- 196 -284
I- 220 -247
13-23
 Enthalpy Diagrams for Dissolving Three
Different Ionic Compounds in Water

NaCl NH4NO3

Figure 13.6 NaOH

13-24
 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! In this case, dissolution is

entropy-driven!

Figure 13.7
13-26
 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

solute (undissolved) solute (dissolved)

Figure 13.8
13-28
 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 saturated solution

13-34
 The effect of pressure on gas solubility

gas volume is reduced;

pressure (concentration!)
increases; more collisions
Figure 13.12 occur with liquid surface
13-35
 Henry’s 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.

Implications for scuba diving!

kH = Henry’s law constant
for a gas; units of mol/L.atm

13-36
 SAMPLE PROBLEM 13.2 Using Henry’s Law to calculate gas solubility

PROBLEM: 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
Henry’s law constant for CO2 dissolved in water is 3.3 x 10-2
mol/L.atm at 25 oC.
PLAN: Knowing kH and Pgas, we can substitute into the Henry’s Law
equation.

SOLUTION: 0.1 mol / L

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

13-37
 Table 13.5 Concentration Definitions

concentration term ratio

amount (mol) of solute

molarity (M)
volume (L) of solution

amount (mol) of solute

molality (m)
mass (kg) of solvent

mass of solute
parts by mass
mass of solution

volume of solute
parts by volume
volume of solution

mole fraction amount (mol) of solute

amount (mol) of solute + amount (mol) of solvent

13-38
 SAMPLE PROBLEM 13.3 Calculating molality

PROBLEM: 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: mole CaCl2
32.0 g CaCl2 x = 0.288 mole CaCl2
110.98 g CaCl2

0.288 mole CaCl2

molality = = 1.06 m CaCl2
kg
271 g H2O x
103 g

13-39
 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: (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.

13-42
 SAMPLE PROBLEM 13.4 (continued)

g
SOLUTION: (a) 40.5 mg Ca x
103 mg
x 106 = 1.16 x 104 ppm Ca
3.5 g

(b) 11.5 L alcohol

0.750 L chianti x = 0.0862 L alcohol
100. L chianti

mole
(c) moles isopropyl alcohol = 142 g x = 2.36 mol C3H7OH
60.09 g
mole
moles water = 58.0 g x = 3.22 mol H2O
18.02 g

2.36 mol C3H7OH 3.22 mol H2O

2.36 mol C3H7OH + 3.22 mol H2O 2.36 mol C3H7OH + 3.22 mol H2O

= 0.423 C3H7OH = 0.577 H2O

13-43
 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

mol H2O2
30.0 g H2O2 x
34.02 g H2O2
molality = = 12.6 m H2O2
kg H2O
70.0 g H2O x
103 g
13-44
 SAMPLE PROBLEM 13.5 (continued)

(b) mol H2O

70.0 g H2O x = 3.88 mol H2O
18.02 g H2O

0.882 mol H2O2

= 0.185 =  of H2O2
0.882 mol H2O2 + 3.88 mol H2O

(c) mL
100.0 g solution x = 90.1 mL solution
1.11 g

0.882 mol H2O2

= 9.79 M H2O2
90.1 mL solution x L
103 mL

13-45
 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
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Copyright © The McGraw-Hill Companies, Inc.

Permission required for reproduction or display.

strong non-electrolyte

Figure 13.14 weak

13-47
 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

Raoult’s 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 Using Raoult’s Law to find the vapor pressure
lowering

PROBLEM: 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.
PLAN: Find the mol fraction, , of glycerol in solution and multiply by the
vapor pressure of water.

SOLUTION:
1.26 g C3H8O3 mol C3H8O3
10.0 mL C3H8O3 x x = 0.137 mol C3H8O3
mL C3H8O3 92.09 g C3H8O3
0.988 g H2O mol H2O
500.0 mL H2O x x = 27.4 mol H2O
mL H2O 18.02 g H2O
 = 0.00498
P = 0.137 mol C3H8O3
x 92.5 torr = 0.461 torr
0.137 mol C3H8O3 + 27.4 mol H2O

13-50
 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

boiling melting
solvent point (oC)* Kb (oC/m) point (oC) Kf (oC/m)

acetic acid 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 30.
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

water 100.0 0.512 0.0 1.86

*at 1 atm.

13-55
 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?
PLAN: 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
16.1 mol C2H6O2
= 3.62 m C2H6O2
4.450 kg H2O

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 FP = -6.73 oC

13-56
 Osmotic Pressure

 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)

13-57
 The development of osmotic pressure
osmotic
pressure
applied
pressure
needed to
prevent
volume
pure solution increase;
solvent
equal to
the
osmotic
semipermeable pressure
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  M

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?
PLAN: 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
(0.0821 L . atm/mol . K)(278.15 K)
2.08 x 10-4 mol L
x 1.50 mL x = 3.12 x 10-7 mol
L 103 mL
# mol = g/M
g 1
21.5 mg x x = 6.89 x 104 g/mol
103 mg 3.12 x 10-7 mol
13-62
 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

Gasoline 38 oC
The process of
Kerosene 150 oC
fractional
distillation Heating oil 260 oC
Lubricating oil 315 oC - 370 oC

Crude oil vapors

from heater

Steam
Figure 13.18 Residue (asphalt, tar)
13-64
 Colligative Properties of Electrolyte Solutions

Must consider the full dissociation into ions!

van’t 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)

 water purification

13-68
 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