Announcements

Homework 27 and Homework 27 answers will be available on Blackboard after lecture. Quiz IX next time. Exam V will be returned at the end of lecture. Your course-to-date percentage will be available on Blackboard under the heading 3rd% after lecture.

Recap
The forces of attraction that give liquids and solids their fixed volumes are called intermolecular forces. Intermolecular forces are forces of attraction between molecules or between molecules and ions. There are four types of intermolecular forces, also known as van der Waals forces:
Ion-dipole forces Dipole-dipole forces Hydrogen bonds London dispersion forces

The relative strengths of the intermolecular forces: Ion-dipole > H-bond > dipole-dipole > London dispersion A substances boiling point is a measure of the strength of its intermolecular forces.

London Dispersion Forces

London dispersion forces are the attractive forces between nonpolar molecules.
CO2 or Br2

All atoms and molecules exhibit London dispersion forces. Because they arise from induced dipoles, London dispersion forces are the weakest intermolecular forces.

London Dispersion Force Strength

The relative strength of the London dispersion force depends on the polarizability of the molecule. Polarizability is the ease with which a molecules electron cloud is distorted by a nearby electric field. The greater the polarizability, the greater the London dispersion force strength. Polarizability correlates with molar mass. London dispersion force polarizability molar mass

Rank Br2, F2, and I2 according to increasing London dispersion force strength. a. b. c. d. I2 < F2 < Br2 I2 < Br2 < F2 F2 < I2 < Br2 F2 < Br2 < I2
I2 < F 2 < B r2

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I2 < B r2 < F 2

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< I2 < B r2

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< B r2 < I2 F 2

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F 2

Ranking of Intermolecular Forces

The relative strengths of the intermolecular forces: Ion-dipole > H-bond > dipole-dipole > London dispersion A substances boiling point is a measure of the strength of its intermolecular forces. Formula O2 HCl NH3 Intermolecular Force Boiling Point (oC) London -183 Dipole-dipole -85 H-bond -33

As intermolecular force strength increases, boiling point increases. This same trend is observed in melting points.

Rank the following compounds according to increasing boiling point: CO2, H2O, and SO2.
a. b. c. d. CO2 < SO2 < H2O SO2 < H2O < CO2 H2O < CO2 < SO2 CO2 < H2O < SO2
H 2O < SO 2 < C O 2

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C O 2 <

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<

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SO 2 < C O 2 < H 2O

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SO 2

H 2O

<

H 2O

S O 2

<

C O 2

Liquids, Solids, and Phase Changes

Viscosity
Viscosity is a measure of a liquids resistance to flow.

Van der Waals force strength: glycerol > water > ethanol > benzene > pentane Viscosity van der Waals force strength Viscosity particle size

Types of Solids
At their broadest level, solids can be classified as either crystalline or amorphous. Crystalline solids are those whose atoms, ions, or molecules have an ordered arrangement
extending over a long range. E.g., iron, table salt, ice, and diamond.

Amorphous solids are those whose constituent parts are randomly arranged and have no longrange order.
Rubber

Types of Crystalline Solids

Crystalline solids can be subclassified as:
Metallic Ionic Molecular Covalent network

The different subtypes of crystalline solids have different forces of attraction between the particles. Because they have different forces of attraction, different subtypes of crystalline solids have different physical properties.

Metallic Solids
Metallic solids are the simplest examples of crystalline solids because their constituent particles are atoms, which can be approximated as spheres. How can spheres be packed together in an ordered arrangement that extends over a long range? There are four typically observed results:
Simple cubic packing Body-centered cubic packing Hexagonal closest packing Cubic closest packing

Unit Cells
Because these crystalline solids exhibit long-range order, it isnt necessary to know what the extended solid looks like. Knowing the arrangement of the fundamental unit that is repeated to compose the overall solid is enough. The unit cell is the fundamental repeating unit that makes up the overall solid. There are three cubic unit cells:
Primitive cubic Body-centered cubic Face-centered cubic

Primitive and Body-Centered Cubic Unit Cells

Face-Centered Cubic Unit Cells

Metallic Solids Summary

There are two important variables that describe each packing type:
Number of nearest neighbors (aka coordination number): the number of other atoms adjacent to any particular atom. Packing efficiency: the percentage of unit cell volume occupied by atoms. Number of Nearest Neighbors 6 8 12 12 Packing Efficiency 52% 68% 74% 74% Number of Metals with Packing Type 1 16 21 18

Packing Type Simple cubic Body-centered cubic Hexagonal closest Cubic closest

Unit Cell Primitive cubic Body-centered cubic Face-centered cubic

Conclusion: Particles pack together in solids as closely as possible, maximizing their interparticle attractions.

What Bonding in Metallic Solids Isnt

Metallic bonds cant be ionic. Metals can readily lose electrons to satisfy the octet rule, but they cant gain enough electrons to do so.
Na+ is possible. Na7- is not.

Metallic bonds cant be localized or metals wouldnt be malleable (capable of being beaten into shapes). At the atomic level, being beaten into new shapes means moving atoms around, distorting the packing arrangement. If metallic bonds were localized, distorting the packing arrangement would amount to breaking bonds, which requires an enormous amount of energy.

What Bonding in Metallic Solids Is

Metallic bonds involve delocalized sharing of electrons. Molecular orbital theory is best at describing delocalized sharing of electrons. Increasing the number of interacting atoms increases the number of MOs. As the number of MOs increases, the energy differences between the MOs decreaes.

(Conduction band)

(Valence band)

Conductors, Insulators, and Semiconductors

In conductors such as metals, the conduction and valence bands overlap. In insulators, the gap between the valence and conduction bands is too great to be spanned. In semiconductors, the gap between the valence and conduction bands is small enough that it can be spanned by reasonably sized electric potentials.

Ionic Solids
Like metallic solids, the particles that compose ionic solids can be approximated as spheres. Unlike metallic solids, the particles that compose ionic solids (cations and anions) have charges and different sizes. Because of their charges, the nearest neighbors of each cation will be anions, and vice versa.

Sodium Chloride Unit Cell

Bonding and Properties Ionic Solids

Ionic solids have high melting points because melting somewhat overcomes the very strong ionic bonds. Ionic solids are electrical nonconductors because the ions are essentially fixed in place. Ionic solids are hard because distorting the solid requires moving ionsovercoming the ionic bonds. Ionic solids are brittle because when ions are moved, strong repulsions result.

Molecular Solids
Molecular solids are held together by van der Waals forces. Because van der Waals forces are typically weaker than metallic or ionic bonds, molecular solids tend to be soft, easily deformed, and possessed of low melting points. Because there are no charged species and the attractions are between molecules, molecular solids are typically nonconductors.

Ice Lattice Structure

Solid water is held together by hydrogen bonds. The hydrogen bonds cause water to have a hexagonal symmetry because a hexagonal arrangement maximizes the hydrogen bonding attractions.

Covalent Network Solids

Covalent network solids are held together by covalent bonds. Since covalent bonds are strong and localized, covalent network solids tend to be hard, high melting, electrical nonconductors.

Graphite and Diamond Lattice Structures

Summary of Crystalline Solids and Their Properties

What interparticle forces maintain solid krypton?

a. b. c. d. e. f. g. Ion-ion forces Ion-dipole forces Hydrogen bonds Dipole-dipole forces London dispersion forces Metallic bonds Covalent bonds

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Io n -i o n fo Io r n c -d e s ip o le fo H rc y d e ro s g e D n ip b o o le n -d d s ip L o o n le d fo o n rc d e is p e r s io n ..

M e ta lli c b o C n o d v s a le n tb o n d s

Phase Changes
Phase changes, or changes of state, are changes in the physical form of a substance that leave its chemical identity intact.
E.g., boiling water converts liquid water into gaseous water.

The names of the various phase changes:

Fusion (melting): solid to liquid Freezing: liquid to solid Vaporization: liquid to gas Condensation: gas to liquid Sublimation: solid to gas Deposition: gas to solid

Enthalpy, Entropy, & Phase Changes

Energetics of Phase Changes

How much heat is required to convert 1.00 mol of H2O at -25.0 to 125.0 oC? 1. Heat ice from -25.0 oC to 0.0 oC. q1 = nCH2O(s)T q1 = (1.00 mol)(0.03657 kJ/moloC)(0.0 25.0 oC) = 0.914 kJ 2. Melt ice at 0.0 oC. q2 = nHfusion = (1.00 mol)(6.01 kJ/mol) = 6.01 kJ 3. Heat liquid water from 0.0 oC to 100.0 oC. q3 = nCH2O(l)T q3 = (1.00 mol)(0.0754 kJ/moloC)(100.0 0.0 oC) = 7.54 kJ 4. Boil water at 100.0 oC. q4 = nHvap = (1.00 mol)(40.67 kJ/mol) = 40.67 kJ 5. Heat steam from 100.0 oC to 125.0 oC. q5 = nCH2O(g)T q5 = (1.00 mol)(0.0331 kJ/moloC)(125.0 100.0 oC) = 0.828 kJ qtotal = q1 + q2 + q3 + q4 + q5 = 55.96 kJ

Heating Curve for 1 mol of H2O

Molecular-Level Interpretation of H2O Heating Curve

Temperature changes when heating or cooling within a phase. Ergo, particle kinetic energy (molecular speed) is changing. Temperature is constant during a phase change. Thus, potential energy (intermolecular force) is changing.

Evaporation
Why will a glass of water left out on a table eventually evaporate completely, without being heated? At a given temperature, the molecules in the water have a distribution of speeds, some of which are great enough to allow the molecules to escape the liquid phase.

Evaporation and Vapor Pressure

Vapor Pressure
Vapor pressure (Pvap) is the pressure exerted by a vapor over its liquid. What factors affect vapor pressure?

Vapor pressure T Vapor pressure 1/van der Waals force strength

Clausius-Clapeyron Equation
The relationship between vapor pressure and temperature is given by the Clausius-Clapeyron equation: lnPvap = -(Hvap/R)(1/T) + C The Clausisus-Clapeyron equation has the form of a straight line. y = mx + b

Clausius-Clapeyron Equation Example

When data is scarce, a two-point version of the Clausius-Clapeyron equation may be used: ln(P2/P1) = -(Hvap/R)(1/T2 1/T1)

ln(P2/P1) = -(Hvap/R)(1/T2 1/T1) Butane lighters typically contain a mixture of liquid and vapor. At 25 oC the vapor pressure of butane is 2.3 atm. What is the pressure in the container at 150 oC? (The Hvap of butane is 24.3 kJ/mol.)

a. b. c. d.

2.90 atm 6.66 atm 18.1 atm 41.6 atm

2 .9 0 a tm

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6 .6 6 a tm

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1 8 .1 a tm

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4 1 .6 a tm

Vapor Pressure and Boiling Point

The boiling point is the temperature at which the vapor pressure equals the external pressure. The normal boiling point is the temperature at which the vapor pressure equals an external pressure of 1 atm.

Summary
Viscosity van der Waals force strength; viscosity particle size Most metallic solids exhibit hexagonal closest or cubic closest packing because doing so packs the atoms as closely together as possible, maximizing interparticle attractions. Metallic bonds involve delocalized sharing of electrons, which is best described as bands of MOs. Ionic solids pack similarly to metals, except that the particles that compose ionic solids (cations and anions) have charges and different sizes. Molecular solids are held together by van der Waals forces. Covalent network solids are held together by covalent bonds. Phase changes, or changes of state, are changes in the physical form of a substance that leave its chemical identity intact. Vapor pressure is the pressure exerted by a vapor over its liquid. The relationship between vapor pressure and temperature is given by the Clausius-Clapeyron equation: lnPvap = -(Hvap/R)(1/T) + C