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
Prentice-Hall 2002

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

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 2 of 46

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

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 3 of 46

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.
Prentice-Hall 2002 General Chemistry: Chapter 14 Slide 4 of 46

Table 14.1 Some Common Solutions

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 5 of 46

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)

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 6 of 46

10% Ethanol Solution (v/v)

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 7 of 46

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.
Prentice-Hall 2002 General Chemistry: Chapter 14 Slide 8 of 46

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%

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 9 of 46

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)

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 10 of 46

14-3 Intermolecular Forces and the Solution Process

Hb

Hc

Ha

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 11 of 46

Intermolecular Forces in Mixtures

Magnitude of Ha, Hb, and Hc depend on intermolecular forces.

Ideal solution
Forces are similar between all combinations of components.

Hsoln = 0

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 12 of 46

Ideal Solution

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 13 of 46

Non-ideal Solutions
Adhesive forces greater than cohesive forces.

Hsoln < 0

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 14 of 46

Non-ideal Solutions
Adhesive forces are less than cohesive forces. Hsoln > 0

At the limit these solutions are heterogeneous.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 15 of 46

Ionic Solutions

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 16 of 46

Hydration Energy
NaCl(s) Na+(g) + Cl-(g) Na+(g) + xs H2O(l) Na+(aq) Hlattice > 0 Hhydration < 0

Cl-(g) + xs H2O(l) Cl-(aq)

Hhydration < 0

Hsoln > 0 but Gsolution < 0

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 17 of 46

14-4 Solution Formation and Equilibrium

saturated

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 18 of 46

Solubility Curves
Supersaturated Unsaturated

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 19 of 46

14-5 Solubility of Gases

Most gases are less soluble in water as temperature increases. In organic solvents the reverse is often true.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 20 of 46

Henrys Law
Solubility of a gas increases with increasing pressure.
C = Pgas
C k

C = k Pgas

k=

23.54 mL 1.00 atm

= 23.54 ml N2/atm

Pgas =

100 mL

= 4.25 atm

23.54 ml N2/atm
General Chemistry: Chapter 14 Slide 21 of 46

Prentice-Hall 2002

Henrys Law

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 22 of 46

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.

P A = A P A

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 23 of 46

Example 14-6
Predicting vapor pressure of ideal solutions. The vapor pressures of pure benzene and toluene at 25C 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 Pbenzene = (0.500)(96.1 mm Hg) = 47.6 mm Hg Ptoluene = toluene Ptoluene = (0.500)(28.4 mm Hg) = 14.2 mm Hg

Ptotal = Pbenzene + Ptoluene = 61.8 mm Hg

Prentice-Hall 2002 General Chemistry: Chapter 14 Slide 24 of 46

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

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 25 of 46

Liquid-Vapor Equilibrium

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 26 of 46

Fractional Distillation

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 27 of 46

Fractional Distillation

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 28 of 46

Non-ideal behavior

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 29 of 46

14-7 Osmotic Pressure

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 30 of 46

Osmotic Pressure
For dilute solutions of electrolytes:

V = nRT n = RT = M RT V

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 31 of 46

Osmotic Pressure
Hypertonic > 0.92% m/V
crenation

Isotonic Saline 0.92% m/V

Hypotonic > 0.92% m/V

rupture

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 32 of 46

Reverse Osmosis - Desalination

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 33 of 46

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.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 34 of 46

Vapor Pressure Lowering

Tf = -Kf m

Tb = -Kb m

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 35 of 46

Practical Applications

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 36 of 46

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)

Tf = -Kf m = -1.86C m-1 0.0100 m = -0.0186C

Freezing point depression for NaCl is -0.0361C.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 37 of 46

vant Hoff
measured Tf expected Tf 0.0361C 0.0186C

i=

= 1.98

= -i M RT Tf = -i Kf m Tb = -i Kb m

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 38 of 46

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

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 39 of 46

Debye and Hckel

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.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 40 of 46

14-10 Colloidal Mixtures

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 41 of 46

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.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 42 of 46

Dialysis

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 43 of 46

Focus on Chromatography
Stationary Phase silicon gum alumina silica Mobile Phase solvent gas

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 44 of 46

Chromatography

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 45 of 46

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.

Prentice-Hall 2002

General Chemistry: Chapter 14

Slide 46 of 46