General Chemistry
Principles and Modern Applications
Petrucci • Harwood • Herring
8th Edition
Chapter 14: Solutions and Their
Physical Properties
Philip Dutton
University of Windsor, Canada
N9B 3P4
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Contents
14-1
14-2
14-3
14-4
14-5
14-6
14-7
Types of Solutions: Some Terminology
Solution Concentration
Intermolecular Forces and the Solution Process
Solution Formation and Equilibrium
Solubilities of Gases
Vapor Pressure of Solutions
Osmotic Pressure
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Contents
14-8
Freezing-Point Depression and Boiling-Point Elevation
of Nonelectrolyte solutions.
14-9 Solutions of Electrolytes
14-10 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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Table 14.1 Some Common Solutions
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14-2 Solution Concentration.
• Mass percent.
• Volume percent.
• Mass/volume percent.
(m/m)
(v/v)
(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
ppb: parts per billion
ppt: parts per trillion
(g/g, mg/L)
(ng/g, g/L)
(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) =
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Mass of solvent (in kilograms)
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14-3 Intermolecular Forces and the
Solution Process
ΔHc
ΔHb
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.
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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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14-4 Solution Formation and Equilibrium
saturated
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Solubility Curves
Supersaturated
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Unsaturated
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14-5 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
with increasing pressure.
k=
Pgas =
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C
=
Pgas
C
k
=
23.54 mL
1.00 atm
C = k Pgas
= 23.54 ml N2/atm
100 mL
= 4.25 atm
23.54 ml N2/atm
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Henry’s Law
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14-6 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 14-6
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 14-7
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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14-7 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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14-8 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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14-9 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
i=
measured ΔTf
expected ΔTf
=
0.0361°C
= 1.98
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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14-10 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 14 Questions
Develop problem solving skills and base your strategy not
on solutions to specific problems but on understanding.
Choose a variety of problems from the text as examples.
Practice good techniques and get coaching from people who
have been here before.
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