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Chapter 12: Liquids, Solids and Intermolecular Forces
Chemistry 140 Fall 2002 General Chemistry Principles and Modern Applications Petrucci • Harwood • Herring 8th Edition Chapter 12: Liquids, Solids and Intermolecular Forces Philip Dutton University of Windsor, Canada N9B 3P4 Prentice-Hall © 2002
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General Chemistry: Chapter 13
Chemistry 140 Fall 2002 Contents 12-1 Intermolecular Forces and some Properties of Liquids 12-2 Vaporization of Liquids: Vapor Pressure 12-3 Some Properties of Solids 12-4 Phase Diagrams 12-5 Van der Waals Forces 12-6 Hydrogen Bonding 12-7 Chemical Bonds as Intermolecular Forces 12-8 Crystal structures 12-8 Energy Changes in the Formation of Ionic Crystals Focus on Liquid Crystals Prentice-Hall © 2002 General Chemistry: Chapter 13
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12-1 Intermolecular Forces and Some Properties of Liquids
Cohesive Forces Intermolecular forces between like molecules. Adhesive Forces Intermolecular forces between unlike molecules. Surface Tension Energy or work required to increase the surface area of a liquid. Viscosity A liquids resistance to flow Prentice-Hall © 2002 General Chemistry: Chapter 13
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Intermolecular Forces
Prentice-Hall © 2002 General Chemistry: Chapter 13
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Intermolecular Forces
Prentice-Hall © 2002 General Chemistry: Chapter 13
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12-2 Vaporization of Liquids: Vapor Pressure
Chemistry 140 Fall 2002 12-2 Vaporization of Liquids: Vapor Pressure Bonding atomic orbitals are shown in grey. Prentice-Hall © 2002 General Chemistry: Chapter 13
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Enthalpy of Vaporization
ΔHvap = Hvapor – Hliquid = - ΔHcondensation Prentice-Hall © 2002 General Chemistry: Chapter 13
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Boiling Point Mercury manometer Vapor pressure of liquid
Pvap independent of Vliq Pvap independent of Vgas Pvap dependent on T Prentice-Hall © 2002 General Chemistry: Chapter 13
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Vapor Pressure and Boiling Point
(e) (d) (c) (b) (a) Ln P = -A ( ) + B 1 T A = ΔHvap R Prentice-Hall © 2002 General Chemistry: Chapter 13
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Clausius-Clapeyron Equation
Ln P = -A ( ) + B 1 T Ln = ( ) P2 P1 1 T2 T1 ΔHvap R Example 12-1: The vapor pressure is 5.08 kPa at 18.1 °C, the vaporization enthalpy is 41.9 kJ/mol. What is the vapor pressure at 61.1 °C? Example 12-2: A compound has a kPa vapor pressure at °C. At °C it has kPa vapor pressure. What is the molar enthalpy of vaporization in J mol-1 of this compound? Prentice-Hall © 2002 General Chemistry: Chapter 13
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12-3 Some Properties of Solids
Freezing Point Melting Point ΔHfus(H2O) = kJ/mol Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Sublimation ΔHsub = ΔHfus + ΔHvap = -ΔHdeposition Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Chemistry 140 Fall 2002 12-4 Phase Diagrams Iodine OD represents the FUSION CURVE. There is little effect of pressure on melting point. O is the triple point. A unique temperature and pressure at which three states of matter coexist in equilibrium. Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Chemistry 140 Fall 2002 Phase Diagrams Carbon dioxide Triple point is greater than one atmosphere, so we do not form liquid. Sublimation occurs. Liquid present in fire extinguishers (P > 5.1 atm) Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Supercritical Fluids Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Chemistry 140 Fall 2002 Phase Diagram of Water Fusion curve (OD) has a negative slope. Unusual behavior. Ice skating. Polymorphysm, the existence of a solid substance in more than one form. This is common. Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
The Critical Point Prentice-Hall © 2002 General Chemistry: Chapter 13
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Critical Temperatures and Pressures
Prentice-Hall © 2002 General Chemistry: Chapter 13
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3 dimension p-V-T surface
Csonka Gábor © 2008 Általános kémia: 3. fejezet
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Water 3 dimension p-V-T surface
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Van der Waals Constants
The Van der Waals constants can be obtained from the critical data: a = 3pc Vc and b = Vc/3 Csonka Gábor © 2008 Általános kémia: 3. fejezet
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General Chemistry: Chapter 13
12-5 Van der Waals Forces Instantaneous dipoles. Electrons move in an orbital to cause a polarization. Induced dipoles. Electrons move in response to an outside force. Dispersion or London forces. Instaneous dipole – induced dipole attraction. Related to polarizability. Prentice-Hall © 2002 General Chemistry: Chapter 13
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Phenomenon of Induction
Prentice-Hall © 2002 General Chemistry: Chapter 13
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Instantaneous and Induced Dipoles
Prentice-Hall © 2002 General Chemistry: Chapter 13
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London dispersion in hydrocarbons
C5H C15H C18H38
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Dipole Dipole Interactions
Prentice-Hall © 2002 General Chemistry: Chapter 13
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The water molecule (dipole moment)
Dipole moment: = Debye Polarizability: α = x cm3 δ- δ+ General Chemistry: Chapter 13
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General Chemistry: Chapter 13
12-6 Hydrogen Bonding Prentice-Hall © 2002 General Chemistry: Chapter 13
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Hydrogen Bonding in HF(g)
Prentice-Hall © 2002 General Chemistry: Chapter 13
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Hydrogen Bonding in Water
Chemistry 140 Fall 2002 Hydrogen Bonding in Water Solid ice has lower density than liquid water. H-bonding holds the ice in a rigid but open structure. Maximum density of water at 3.98 C. around a molecule in the solid in the liquid Prentice-Hall © 2002 General Chemistry: Chapter 13
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Other examples of H-Bonds
Chemistry 140 Fall 2002 Other examples of H-Bonds Viscosity Units centipoise (cP). Water at 20 C 1 cP. Prentice-Hall © 2002 General Chemistry: Chapter 13
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12-7 Chemical Bonds as Intermolecular Forces
Chemistry 140 Fall 2002 12-7 Chemical Bonds as Intermolecular Forces Network covalent solids. C allotropes: Diamond and Graphite Prentice-Hall © 2002 General Chemistry: Chapter 13
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Other Carbon Allotropes
Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Interionic Forces Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
12-8 Crystal Structures Prentice-Hall © 2002 General Chemistry: Chapter 13
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Unit Cells in the Cubic Crystal System
Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Holes in Crystals Prentice-Hall © 2002 General Chemistry: Chapter 13
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Hexagonal Close Packed (hcp)
Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Coordination Number Prentice-Hall © 2002 General Chemistry: Chapter 13
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Counting Cell Occupancy
Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
X-Ray Diffraction Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
X-Ray Diffraction Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Cesium Chloride Prentice-Hall © 2002 General Chemistry: Chapter 13
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Atomic Radii from Crystal Structures
Chemistry 140 Fall 2002 Atomic Radii from Crystal Structures Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Sodium Chloride Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Holes in Crystals Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Prentice-Hall © 2002 General Chemistry: Chapter 13
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12-9 Energy Changes in the Formation of Ionic Crystals
Prentice-Hall © 2002 General Chemistry: Chapter 13
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General Chemistry: Chapter 13
Chapter 13 Questions 1, 3, 4, 13, 24, 26, 31, 45, 52, 61, 94, 107 Prentice-Hall © 2002 General Chemistry: Chapter 13
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