General Chemistry: Solutions and Their Physical Properties

GENERAL CHEMISTRY
Principles and Modern Applications TENTH EDITION
PETRUCCI HERRING MADURA BISSONNETTE
Solutions and Their

Physical Properties 13
Slide 1 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.
Solutions and Their Physical
Properties CONTENTS
13-1 Types of Solutions: Some

Terminology
13-2 Solution Concentration
13-3 Intermolecular Forces and the
Solution Process
13-4 Solubility of Gases
13-5 Vapor Pressures of Solutions
13-6 Osmotic Pressure
13-7 Freezing-Point Depression

and Boiling-Point Elevation of
Nonelectrolyte Solutions
13-8 Solutions of Electrolytes
13-9 Colloidal Mixtures

13-1 Types of Solution: Some Terminology
Solutions are homogeneous mixtures and are uniform throughout.

Solvent.
Determines the state of matter in which the solution exists.
Is the largest component.
Solutes
Other solution components said to be dissolved in the solution.

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)
Parts per Million, Parts per Billion, and Parts per Trillion
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.

Mole Fraction and Mole Percent
Amount of component i (in moles)

i =
Total amount of all components (in moles)
1 + 2 + 3 + …n = 1
Mole % i = i  100%

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)

13-3 Intermolecular Forces and the Solution Process
FIGURE 13-2
Enthalpy diagram for solution formation
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
FIGURE 13-3
Intermolecular forces in a solution
FIGURE 13-4
Two components of a nearly ideal solution

If adhesive forces greater
than cohesive forces.
ΔHsoln < 0
FIGURE 13-5
Intermolecular force between unlike molecules leading to a nonideal solution

If adhesive forces are
less than cohesive
forces.
ΔHsoln > 0
At the limit these

solutions are
heterogeneous.

Formation of Ionic Solutions
FIGURE 13-6
An ionic crystal dissolving in water
Enthalpies involved in the solution process:
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 (~ 5 kcal/mol) but ΔGsolution < 0

13-4 Solution Formation and Equilibrium
FIGURE 13-7
Formation of a saturated solution
Supersaturated Unsaturated
FIGURE 13-8
Aqueous solubility of several salts as a
function of temperature

FIGURE 13-9
Recrystallization of KNO3
13-5 Solubility of Gases
Effect of Temperature
Most gases are less

soluble in water as
temperature increases.
In organic solvents the
reverse is often true.
Figure 13-10
Effect of temperature on the
solubilities of gases

Effect of Pressure
William Henry found that the solubility of a gas

increases with increasing pressure.
C = kPgas
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

FIGURE 13-11
Effect of pressure on the solubility of a gas

* Henry’s law fails for gases at high
pressures; it also fails if the gas
ionizes in water or reacts with water.

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 = AP°
A

Liquid-Vapor Equilibrium: Ideal Solutions
FIGURE 13-12
Liquid-vapor equilibrium for benzene-toluene mixtures at 25°C
Fractional Distillation
FIGURE 13-13
Liquid-vapor equilibrium for benzene-toluene mixtures at 1 atm
cooling
H2O
FIGURE 13-14 Fractional distillation is used in

Fractional distillation many industrial processes.

Liquid-Vapor Equilibrium: Nonideal Solutions
FIGURE 13-15
A minimum boiling-point azeotrope
13-7 Osmotic Pressure
FIGURE 13-16
Observing the direction of flow of water vapor
FIGURE 13-17
Osmosis

Osmotic Pressure
For dilute solutions of electrolytes:
πV = nRT
n
π= RT = MRT
V

Practical Applications
FIGURE 13-8
Desalination of saltwater by reverse osmosis
Hypertonic Isotonic Saline Hypotonic
> 0.92% m/V 0.92% m/V < 0.92% m/V
water flows out of water flows into
the cells causing the cells causing
crenation rupture

13-8 Freezing-Point Depression and Boiling Point
Elevation of Nonelectrolyte Solutions
A Colligative property.
Depends on the number of particles present.
Vapor pressure is lowered when a solute is present.

This results in boiling point elevation.
Freezing point is also effected and is lowered.

ΔTf = -Kf  m
ΔTb = Kb  m
FIGURE 13-19
Vapor-pressure lowering by a nonvolatile solute

ΔTf = -Kf  m ΔTb = Kb  m

Practical Applications

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.

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

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

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.
The magnitudes of colligative properties are reduced.

FIGURE 13-20
Interionic attractions in aqueous solution

13-10 Colloidal Mixtures
FIGURE 13-21
The Tyndall effect
Particles of 1-1000 nm size.
Nanoparticles of various
shapes: rods, discs, spheres.
Particles can remain suspended
indefinitely.
Milk is colloidal.
Increasing ionic strength can

cause precipitation.
FIGURE 13-22
Surface of SiO2 article in colloidal silica

Fe2O3 colloid Al2(SO4)3 Fe2O3 precipitate
FIGURE 13-23
Coagulation of colloidal iron oxide

FIGURE 13-24
The principles of dialysis


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GENERAL CHEMISTRY

Principles and Modern Applications TENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Solutions and Their

13-1 Types of Solutions: Some

13-6 Osmotic Pressure

13-7 Freezing-Point Depression

Slide 2 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Solutions are homogeneous mixtures and are uniform throughout.

Slide 3 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Mass Percent (m/m)

Isotonic saline is prepared by dissolving

Very low solute concentrations are expressed as:

ppm: parts per million (g/g, mg/L)

note that 1.0 L  1.0 g/mL = 1000 g

Slide 6 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Amount of component i (in moles)

Slide 7 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Amount of solute (in moles)

Amount of solute (in moles)

Slide 8 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Magnitude of ΔHa, ΔHb, and ΔHc

Slide 14 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 15 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

At the limit these

Slide 16 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

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 (~ 5 kcal/mol) but ΔGsolution < 0

Slide 19 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 21 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Most gases are less

Slide 23 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

William Henry found that the solubility of a gas

Slide 24 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 25 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 26 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 28 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

FIGURE 13-14 Fractional distillation is used in

Slide 33 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 36 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

For dilute solutions of electrolytes:

Slide 37 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 39 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Vapor pressure is lowered when a solute is present.

Slide 41 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 42 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 43 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 45 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

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

ΔTf = -Kf  m = -1.86°C m-1  0.0100 m = -

Slide 46 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

measured ΔTf 0.0361°C

Slide 47 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 48 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

The magnitudes of colligative properties are reduced.

Slide 49 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 50 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Increasing ionic strength can

Slide 53 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 54 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.

Slide 55 of 46 General Chemistry: Chapter 13 Copyright © 2011 Pearson Canada Inc.