General Chemistry

Principles and Modern Applications

Petrucci • Harwood • Herring
8th Edition

Chapter 13: Solutions and Their

Physical Properties

Khurshid Ayub
King Faisal University

Prentice-Hall © 2002
https://sites.google.com/site/engchem142/
 Contents

13-1 Types of Solutions: Some Terminology

13-2 Solution Concentration
13-3 Intermolecular Forces and the Solution Process
13-4 Solution Formation and Equilibrium
13-5 Solubilities of Gases
13-6 Vapor Pressure of Solutions
13-7 Osmotic Pressure

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 Contents

13-8 Freezing-Point Depression and Boiling-Point Elevation

of Nonelectrolyte solutions.
13-9 Solutions of Electrolytes
13-10 Colloidal Mixtures
Focus on Chromatography

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 13-1 Types of Solution:
Some Terminology
• Solutions are homogeneous mixtures.
– Uniform throughout.
• Solvent.
– Determines the state of matter in which the solution
exists.
– Is the largest component.
• Solute.
– Other solution components said to be dissolved in the
solution.

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General Chemistry: Chapter 13
 Table 14.1 Some Common Solutions

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 13-2 Solution Concentration.

• Mass percent. (m/m)

• Volume percent. (v/v)
• Mass/volume percent. (m/v)

• Isotonic saline is prepared by dissolving 0.9 g

of NaCl in 100 mL of water and is said to be:
0.9% NaCl (mass/volume)

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 10% Ethanol Solution (v/v)

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 ppm, ppb and ppt

• Very low solute concentrations are expressed as:

ppm: parts per million (g/g, mg/L)

ppb: parts per billion (ng/g, g/L)
ppt: parts per trillion (pg/g, ng/L)

note that 1.0 L  1.0 g/mL = 1000 g

ppm, ppb, and ppt are properly m/m or v/v.

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 Mole Fraction and Mole Percent

Amount of component i (in moles)

=
Total amount of all components (in
moles)

1 + 2 + 3 + …n = 1

Mole % i = i  100%

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 Molarity and Molality

Amount of solute (in moles)

Molarity (M) =
Volume of solution (in liters)

Amount of solute (in moles)

Molality (m) =
Mass of solvent (in kilograms)

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 13-3 Intermolecular Forces and the
Solution Process

ΔHb ΔHc

ΔHa

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 Intermolecular Forces in Mixtures

• Magnitude of ΔHa, ΔHb, and

ΔHc depend on intermolecular
forces.

• Ideal solution
– Forces are similar between all
combinations of components.
ΔHsoln = 0

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 Ideal Solution

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 Non-ideal Solutions

• Adhesive forces greater

than cohesive forces.

ΔHsoln < 0

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 Non-ideal Solutions

• Adhesive forces are less than

cohesive forces.

ΔHsoln > 0

• At the limit these solutions

are heterogeneous.

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 Ionic Solutions

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 Hydration Energy

NaCl(s) → Na+(g) + Cl-(g) ΔHlattice > 0

Na+(g) + xs H2O(l) → Na+(aq) ΔHhydration < 0

Cl-(g) + xs H2O(l) → Cl-(aq) ΔHhydration < 0

ΔHsoln > 0 but ΔGsolution < 0

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13-4 Solution Formation and Equilibrium

saturated

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 Solubility Curves

Supersaturated Unsaturated

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 13-5 Solubility of Gases

• Most gases are less soluble

in water as temperature
increases.
• In organic solvents the
reverse is often true.

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 Henry’s Law

• Solubility of a gas increases

C = k Pgas
with increasing pressure.

C 23.54 mL = 23.54 ml N2/atm

k= =
Pgas 1.00 atm

C 100 mL
Pgas = = = 4.25 atm
k 23.54 ml N2/atm

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 Henry’s Law

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 13-6 Vapor Pressures of Solutions

• Roault, 1880s.
– Dissolved solute lowers vapor pressure of solvent.
– The partial pressure exerted by solvent vapor above an
ideal solution is the product of the mole fraction of
solvent in the solution and the vapor pressure of the
pure solvent at a given temperature.

PA = A P°A

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Example 13-6
Predicting vapor pressure of ideal solutions.
The vapor pressures of pure benzene and toluene at 25°C are
95.1 and 28.4 mm Hg, respectively. A solution is prepared in
which the mole fractions of benzene and toluene are both
0.500. What are the partial pressures of the benzene and
toluene above this solution? What is the total vapor pressure?

Balanced Chemical Equation:

Pbenzene = benzene P°benzene = (0.500)(96.1 mm Hg) = 47.6 mm Hg

Ptoluene = toluene P°toluene = (0.500)(28.4 mm Hg) = 14.2 mm Hg

Ptotal = Pbenzene + Ptoluene = 61.8 mm Hg

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Example 13-7
Calculating the Composition of Vapor in Equilibrium with a
Liquid Solution.
What is the composition of the vapor in equilibrium with the
benzene-toluene solution?
Partial pressure and mole fraction:

benzene = Pbenzene/Ptotal = 47.6 mm Hg/61.89 mm Hg = 0.770

toluene = Ptoluene/Ptotal = 14.2 mm Hg/61.89 mm Hg = 0.230

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 Liquid-Vapor Equilibrium

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 Fractional Distillation

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 Fractional Distillation

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 Non-ideal behavior

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 13-7 Osmotic Pressure

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 Osmotic Pressure

For dilute solutions of electrolytes:

πV = nRT

n
π= RT = M RT
V

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 Osmotic Pressure

Hypertonic > 0.92% m/V

crenation

Isotonic Saline 0.92% m/V

Hypotonic > 0.92% m/V

rupture

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 Reverse Osmosis - Desalination

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 13-8 Freezing-Point Depression and
Boiling Point Elevation of Nonelectrolyte
Solutions

• Vapor pressure is lowered when a solute is present.

– This results in boiling point elevation.
– Freezing point is also effected and is lowered.
• Colligative properties.
– Depends on the number of particles present.

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 Vapor Pressure Lowering

ΔTf = -Kf  m

ΔTb = -Kb  m

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 Practical Applications

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 13-9 Solutions of Electrolytes
• Svante Arrhenius
– Nobel Prize 1903.
– Ions form when electrolytes dissolve in solution.
– Explained anomalous colligative properties

Compare 0.0100 m aqueous urea to 0.0100 m NaCl (aq)

ΔTf = -Kf  m = -1.86°C m-1  0.0100 m = -0.0186°C

Freezing point depression for NaCl is -0.0361°C.

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 van’t Hoff

measured ΔTf 0.0361°C

i= = = 1.98
expected ΔTf 0.0186°C

π = -i  M  RT

ΔTf = -i  Kf  m

ΔTb = -i  Kb  m

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 Interionic Interactions
• Arrhenius theory does not correctly predict the
conductivity of concentrated electrolytes.

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 Debye and Hückel

• 1923
– Ions in solution do not
behave independently.
– Each ion is surrounded
by others of opposite
charge.
– Ion mobility is reduced
by the drag of the ionic
atmosphere.

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 13-10 Colloidal Mixtures

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 Colloids

• Particles of 1-1000 nm size.

– Nanoparticles of various
shapes: rods, discs, spheres.
– Particles can remain
suspended indefinitly.
• Milk is colloidal.
• Increasing ionic strength
can cause precipitation.

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 Dialysis

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 Focus on Chromatography

Stationary Phase
silicon gum
alumina
silica
Mobile Phase
solvent
gas

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 Chromatography

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 Chapter 13 Questions

Develop problem solving skills and base your strategy not

on solutions to specific problems but on understanding.

9, 11, 13, 23,

27, 15, 51, 43,
57, 62, 69, 71
73, 79, 83, 85, 86
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