Chapter 12

Intermolecular Forces: Liquids, Solids, and Phase Changes

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Objectives
Our goal in this chapter to learn about the interplay of forces that give rise to the three states of matter and their changes.

Seek to Answer Many Questions : Why does ice float on liquid water? Why is diamond, one form of carbon, so hard that it can scratch glass, whereas graphite, another form of carbon, is soft enough to use in pencils?
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Chapter Outlines
Physical States and Phase Changes Quantitative Aspects of Phase Changes Types of Intermolecular Forces Properties of the Liquid State The Uniqueness of Water The Solid State: Structure, Properties, and Bonding

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Phases of Matter
A physically distinctive form of matter is called a phase. The properties of each phase are determined by the balance between the potential and kinetic energy of the particles. Potential energy in the form of intermolecular forces tends to draw the molecules together. Why? Kinetic energy associated with the random motion of the molecules tends to disperse them.

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Kinetic Molecular View of the Three States

Potential energy vs. Kinetic energy Gas

Potential energy (energy of attraction) is small relative to kinetic energy.

Properties
Particles are far apart. A gas has no fixed shape or volume.

Liquid Attractive forces are stronger A liquid can flow and

because particles are touching. change shape, but has a fixed volume. A solid has a fixed shape and volume.

Solid

Attractions dominate the motion. Particles are fixed in place relative to each other.

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Why are molecules attracted to each other?

intermolecular attractions are due to attractive forces between opposite charges
+ ion to - ion + end of polar molecule to - end of polar molecule
H-bonding especially strong

even nonpolar molecules will have temporary charges

larger the charge = stronger attraction longer the distance = weaker attraction however, these attractive forces are small relative to the bonding forces between atoms
generally smaller charges generally over much larger distances

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Types of Phase Changes and their Enthalpies

As temperature increases, the average KE does too, so the faster moving particles overcome attractions more easily. As temperature decreases, particles slow, so attractions can pull them together. sublimation melting endothermic vaporizing

solid

liquid

gas

freezing

condensing deposition

exothermic

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Two familiar Phase Changes

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Heats of Vaporization and Fusion for several common substances

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Phase Changes and their Enthalpy Changes

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Heat Involved in Phase Changes

A cooling curve for the conversion of gaseous water to ice Consider: 2.5 mol of gaseous water in a closed container Gaseous Gaseous water water condenses cools Liquid Solid water water freezes cools

Liquid water cools

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Heat Involved in Phase Changes Within a phase, heat flow is accompanied by a change in
temperature, since the average Ek of the particles changes.

q = (amount) x (heat capacity) x T

During a phase change, heat flow occurs at constant

temperature, as the average distance between particles changes.

q = (amount)(H of phase change)

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Problem 12.1

Finding the Heat of a Phase Change Depicted by Molecular Scenes

PROBLEM: The scenes below represent a phase change of water. Find the heat (in kJ) released or absorbed when 24.3 g of H2O undergoes this change.

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SOLUTION: There are 3 stages involved in this process: 1) heating of the liquid to its boiling point 2) the phase change from liquid to gas 3) heating the gas to the final temperature 1 mol H2O = 1.35 mol H2O mol H2O = 24.3 g H2O x 18.02 g H2O For Stage 1: q1 = n x Cwater(l) x T = (1.35 mol)(75.4 J/molC)(100. - 85.0C) = 1527 J = 1.53 kJ For Stage 2: q2 = n(Hvap) = (1.35 mol)(40.7 kJ/mol) = 54.9 kJ For Stage 3: q3 = n x Cwater(g) x T = (1.35 mol)(33.1 J/molC)(117 100.C) = 759.6 J = 0.760 kJ qtotal = q1 + q2 + q3 = 1.53 + 54.9 + 0.760 kJ = 57.2 kJ

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Liquid-Gas Equilibrium

In a closed flask, the system reaches a state of dynamic equilibrium, where molecules are leaving and entering the liquid at the same rate.

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The vapor pressure is the pressure exerted by the vapor on the liquid. The pressure increases until equilibrium is reached; at equilibrium the pressure is constant.

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Factors affecting Vapor Pressure

As temperature increases, the fraction of molecules with enough energy to enter the vapor phase increases, and the vapor pressure increases. higher T higher P

The weaker the intermolecular forces, the more easily particles enter the vapor phase, and the higher the vapor pressure. weaker forces higher P

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The effect of temperature on the distribution of molecular speeds

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Vapor Pressure as a function of Temperature and Intermolecular Forces

Vapor pressure increases as temperature increases. Vapor pressure decreases as the strength of the intermolecular forces increases.

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The Clausius-Clapeyron Equation

This equation relates vapor pressure to temperature.

1 H +C ln P = R T
vap

The two-point form is used when the vapor pressures at two different temperatures are known.

P2 - Hvap 1 1 ln = P R T T 2 1 1

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Linear plots of the relationship between vapor pressure and temperature

1 H +C ln P = R T
vap

slope =

- H R

vap

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Problem 12.2

Applying the Clausius-Clapeyron Equation

PROBLEM: The vapor pressure of ethanol is 115 torr at 34.9C. If Hvap of ethanol is 40.5 kJ/mol, calculate the temperature (in C) when the vapor pressure is 760 torr. SOLUTION: ln P2 P1 = - Hvap R 1 1 T2 T1

T1 = 34.9C + 273.15 = 308.0 K 760 torr ln 115 torr - 40.5 x103 J/mol = 8.314 J/molK 1 1 T2 308.0 K

T2 = 350.00 K = 350.00 K 273.15 = 76.85C

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Vapor Pressure and Boiling Point

The boiling point of a liquid is the temperature at which the vapor pressure equals the external pressure. The normal boiling point of a substance is observed at standard atmospheric pressure or 760 torr. As the external pressure on a liquid increases, the boiling point increases.

Real world examples:

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What is Phase Diagram ?

A phase diagram is a graphical representation of the temperature and pressure conditions under which a substance exists as a solid, liquid, gas, or some combination of these in equilibrium.

At the critical point, the densities of the liquid and gas phases become equal.

At the triple point, all three phases are in equilibrium. A typical phase diagram. The dotted green line gives the anomalous behavior of water. The ClausiusClapeyron relation can be used to find the relationship between pressure and temperature along phase boundaries.

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Phase Diagram for CO2

The solid-liquid line has positive slope, because the solid is denser than the liquid.

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The critical temperature, Tc, is the highest temperature at which a liquid and vapor can coexist in equilibrium as physically distinct states of matter

Phase Diagram for H2O

The solid-liquid line has negative slope, because the solid is less dense than the liquid. Water expands on freezing.

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Types of Intermolecular Forces

Intermolecular forces arise from the attraction between molecules with partial charges, or between ions and molecules. Intermolecular forces are relatively weak compared to bonding forces because they involve smaller charges that are farther apart.

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Comparison of Bonding (intramolecular) and Nonbonding (Intermolecular) Forces

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Comparison of Bonding (intramolecular) and Nonbonding (Intermolecular) Forces contd

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Polar molecules and dipole-dipole forces Dipoledipole forces arise when permanent dipoles align themselves with the positive end of one dipole directed toward the negative ends of neighboring dipoles.

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Dipole moment and Boiling point

For compounds of similar molar mass, the greater the molecular dipole moment, the greater the dipole-dipole forces, so the more energy it takes to separate the molecules, thus the boiling point is higher.

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The Hydrogen Bond

Hydrogen bonding is possible for molecules that have a hydrogen atom covalently bonded to a small, highly electronegative atom with lone electron pairs, specifically N, O, or F. An intermolecular hydrogen bond is the attraction between the H atom of one molecule and a lone pair of the N, O, or F atom of another molecule.

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Hydrogen bonding and Boiling point

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Problem 12.3 Drawing Hydrogen Bonds Between Molecules of a Substance

PROBLEM: Which of the following substances exhibits H bonding? For any that do, draw the H bonds between two of its molecules. (a) C2H6 (b) CH3OH (c)

SOLUTION: (a) C2H6 has no N, O, or F, so no H-bonds can form.

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(b) CH3OH contains a covalent bond between O and H. It can form H bonds between its molecules:

(c)

can form H bonds at two sites:

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Polarizability and Induced Dipoles

A nearby electric field can induce a distortion in the electron cloud of an atom, ion, or molecule. - For a nonpolar molecule, this induces a temporary dipole moment. - For a polar molecule, the field enhances the existing dipole moment. Polarizability: the ease with which a particles electron cloud can be distorted.

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Trends in Polarizability
Smaller particles are less polarizable than larger ones because their electrons are held more tightly. Polarizability increases down a group because atomic size increases and larger electron clouds distort more easily. Polarizability decreases across a period because of increasing Zeff. Cations are smaller than their parent atoms and less polarizable; anions show the opposite trend.

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Dispersion (London) Forces

Dispersion (or London) forces arises when an instantaneous dipole in one particle induces a dipole in another, resulting in an attraction between them. Fluctuations in the electron distribution in atoms and molecules result in a temporary dipole. Dispersion forces exist between all particles (atoms, ions, molecules), increasing the energy of attraction in all matter. Dispersion forces are stronger for more polarizable particles.
Larger particles experience stronger dispersion forces than smaller ones.

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Dispersion Forces among Nonpolar Particles

A. When atoms are far apart they do not influence one other.

B. When atoms are close together, the instantaneous dipole in one atom induces a dipole in the other.

C. The process occurs throughout the sample.

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Molar mass and trends in boiling point

Dispersion forces are stronger for larger, more polarizable particles. Polarizability depends on the number of electrons, which correlates closely with molar mass.

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Molecular shape, intermolecular contact, and boiling point

There are more points at which dispersion forces act.

There are fewer points at which dispersion forces act.

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Problem 12.4

Predicting the Types of Intermolecular Forces

PROBLEM: For each pair of substances, identify the key bonding and/or intermolecular force(s), and predict which one of the pair has the higher boiling point: (a) MgCl2 or PCl3 (b) CH3NH2 or CH3F (c) CH3OH or CH3CH2OH (d) Hexane (CH3CH2CH2CH2CH2CH3) or 2,2-dimethylbutane

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SOLUTION: (a) MgCl2 consists of Mg2+ and Cl- ions held together by ionic bonding forces; PCl3 consists of polar molecules, so intermolecular dipoledipole forces are present. The ionic bonding forces in MgCl2 are stronger than the dipole-dipole forces in PCl3.. MgCl2 has a higher boiling point than PCl3. (b) CH3NH2 and CH3F both consist of polar molecules of about the same molar mass. CH3NH2 has covalent N-H bonds, so it can form H bonds between its molecules. CH3F contains a C-F bond but no H-F bond, so dipole-dipole forces occur but not H bonds.

CH3NH2 has a higher boiling point than CH3F.

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(c) CH3OH and CH3CH2OH are both polar molecules and both contain a covalent O-H bond. Both can therefore form H bonds.

CH3CH2OH has a larger molar mass than CH3OH and its dispersion forces are therefore stronger.

CH3CH2OH has a higher boiling point than CH3OH.

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(d) Hexane and 2,2-dimethylbutane are both nonpolar molecules and therefore experience dispersion forces as their only intermolecular force. They have equal molar masses but different molecular shapes.

Cylindrical hexane molecules make more intermolecular contact than the more compact 2,2-dimethylbutane molecules. Hexane has a higher boiling point than 2,2-dimethylbutane.

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Properties of the Liquid State

Surface Tension:
A surface molecule experiences a net attraction downward. This causes a liquid surface to have the smallest area possible.

An interior molecule is attracted by others on all sides.

Surface tension is the energy required to increase the surface area of a liquid. The stronger the forces between the particles the higher the surface tension.

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Surface Tension and Forces Between Particles

Surface Tension Substance Formula
(J/m2) at 200C

Major Force(s)

Diethyl ether CH3CH2OCH2CH3 Ethanol Butanol Water Mercury CH3CH2OH CH3CH2CH2CH2OH H2O Hg

1.7x10-2 2.3x10-2 2.5x10-2 7.3x10-2 48x10-2

Dipole-dipole; dispersion H bonding H bonding; dispersion H bonding Metallic bonding

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Capillary Action:

A. Water displays a concave meniscus.

B. Mercury displays a convex meniscus.

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Properties of Water
H-bonding ability of Water:
hydrogen bond donor

hydrogen bond acceptor

Each H2O molecule can form four H bonds to other molecules, resulting in a tetrahedral arrangement.

1. Solvent Properties of Water

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2. Unusual density of solid water The hexagonal structure of ice

Ice has an open structure due to H bonding. Ice is therefore less dense than liquid water.

3. Thermal Properties of water

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4. Surface Properties

Solids: Properties and structure

Solids are divided into two categories: Crystalline solids have well defined shapes due to the orderly arrangement of their particles. Amorphous solids lack orderly arrangement and have poorly defined shapes.

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Some crystalline solids

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The Crystal Lattice and the Unit Cell The arrangement of the particles in a crystalline solid is called the crystal lattice. The smallest unit that shows the pattern of arrangement for all the particles is called the unit cell.

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7 Unit Cells
c c b a Cubic a=b=c all 90 c c b a Hexagonal a=c<b 2 faces 90 1 face 120 b a Rhombohedral a=b=c no 90 a Triclinic abc no 90 a Tetragonal a=c<b all 90 a Orthorhombic abc all 90 b c b a b c

Monoclinic abc 2 faces 90 c b

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Unit Cells
The number of other particles each particle is in contact with is called its coordination number
for ions, it is the number of oppositely charged ions an ion is in contact with

Higher coordination number means more interaction, therefore stronger attractive forces holding the crystal together The packing efficiency is the percentage of volume in the unit cell occupied by particles
the higher the coordination number, the more efficiently the particles are packing together
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12-55 Tro: Chemistry: A Molecular Approach, 2/e

Simple Cubic Unit Cell

Expanded view. Space-filling view.

atom at 8
corners

Coordination number = 6

Atoms/unit cell = ( x 8) = 1

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Body-centered cubic unit cell

atom at 8 corners 1 atom at center Atoms/unit cell = ( x 8) + 1 = 2 Coordination number = 8

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The face-centered cubic cell.

atom at 8 corners atom at 6 faces

Coordination number = 12

Atoms/unit cell = ( x 8) + ( x 6) = 4

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59

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Packing spheres to obtain three cubic and hexagonal cells

2nd layer directly over 1st

large diamond space simple cubic (52% packing efficiency) 3rd layer over diamond spaces in 2nd

2nd layer over diamond spaces in 1st

body-centered cubic (68% packing efficiency)

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12-61

Problem 12.5

Determining Atomic Radius

PROBLEM: Barium is the largest nonradioactive alkaline earth metal. It has a body-centered cubic unit cell and a density of 3.62 g/cm3. What is the atomic radius of barium? (Volume of a sphere = 4 r3.)
3

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SOLUTION:
3 1 1 cm 137.3 g Ba Volume/mole of Ba metal = xM = x density 3.62 g Ba 1 mol Ba

= 37.9 cm3/mol Ba Volume/mole of Ba atoms = cm3/mol Ba x packing efficiency = 37.9 cm3/mol Ba x 0.68 = 26 cm3/mol Ba atoms 1 mol Ba atoms 26 cm3 x Volume of Ba atom = 6.022x1023 Ba atoms 1 mol Ba atoms = 4.3 x 10-23 cm3/Ba atom

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Volume of Ba atom =

4 r3 3

r=

3V 4

3(4.3x10-23cm3) 4 x 3.14

= 2.2 x 10-8 cm

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Edge length and atomic (ionic) radius in the three cubic unit cells

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Tools of the Laboratory

Diffraction of x-rays by crystal planes

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Formation of an x-ray diffraction pattern of the protein hemoglobin

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Problem 12.6

Determining Atomic Radius from the Unit Cell

PROBLEM: Copper adopts cubic closest packing, and the edge length of the unit cell is 361.5 pm. What is the atomic radius of copper?

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SOLUTION: Using the Pythagorean theorem to find C, the diagonal of the cells face: C =

A2 + B2

The unit cell is a cube, so A = B, Therefore C =

2A2

2(361.5 pm)2

= 511.2 pm

C = 4r, so r =

511.2 pm 4

= 127.8 pm

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Types of Crystalline Solids

Atomic solids consist of individual atoms held together only by dispersion forces. Molecular solids consist of individual molecules held together by various combinations of intermolecular forces. Ionic solids consist of a regular array of cations and anions. Metallic solids have exhibit an organized crystal structure. Network Covalent solids consist of atoms covalently bonded together in a three-dimensional network.

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Characteristics of the Major Types of Crystalline Solids

Type
Atomic

Particle(s)
Atoms

Interparticle Forces
Dispersion

Physical Properties
Soft, very low mp, poor thermal and electrical conductors

Examples [mp, C]
Group 8A(18) (Ne [-249) to Rn [-71])

Molecular Molecules

Dispersion, dipole-dipole, H bonds

Fairly soft, low to moderate mp, poor thermal and electrical conductors

Nonpolar* O2 [-219], C4H10 [-138] Cl2 [-101], C6H14 [-95] P4 [44.1] Polar SO2 [-73], CHCl3 [-64] HNO3 [-42], H2O [0.0] CH3COOH [17]

*Nonpolar

molecular solids are arranged in order of increasing molar mass. Note the correlation with increasing melting point (mp).

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Characteristics of the Major Types of Crystalline Solids Type

Ionic

Particle(s)

Interparticle Forces

Physical Properties

Examples [mp, C]

Positive and Ion-ion attraction Hard and brittle, high mp, NaCl [801] negative ions good thermal and CaF2 [1423] electrical conductors MgO [2852] when molten Atoms Metallic bond Soft to hard, low to very high mp, excellent thermal and electrical conductors, malleable and ductile Na [97.8] Zn [420] Fe [1535]

Metallic

Network covalent

Atoms

Covalent bond

Very hard, very high mp, SiO2 (quartz) [1610] usually poor thermal and C (diamond) [~3550] electrical conductors

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Structures of Some Ionic Solids

Rock Salt Structures: Coordination number = 6 Cl ions in a face-centered cubic arrangement
of each corner Cl inside the unit cell of each face Cl inside the unit cell

Na+ in holes between Cl

octahedral holes 1 in center of unit cell 1 whole particle in every octahedral hole of each edge Na+ inside the unit cell

Na:Cl = ( x 12) + 1: ( x 8) + ( x 6) =4:4 Therefore, the formula is NaCl

73

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Zinc Blende Structures

Coordination number = 4 S2 ions in a face-centered cubic arrangement
of each corner S2 inside the unit cell of each face S2 inside the unit cell

Each Zn2+ in holes between S2

tetrahedral holes 1 whole particle in the holes

Zn:S = (4 x 1) : ( x 8) + ( x 6) = 4:4 = 1:1 Therefore the formula is ZnS

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Structures of Some Network Covalent Solids

Properties of Diamond
Very high melting point, ~3800 C
need to overcome some covalent bonds

Very rigid
due to the directionality of the covalent bonds

Very hard
due to the strong covalent bonds holding the atoms in position used as abrasives sp3 hybridzed C atoms,

Electrical insulator Thermal conductor

best known

each of which is bonded with tetraheral geometry to four other carbons

Chemically very nonreactive

75

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The Graphite Structure: a 2-Dimensional Network

In graphite, the carbon atoms in a sheet are covalently bonded together
forming six-member flat rings fused together
similar to benzene bond length = 142 pm

sp2

The sheets are then stacked and held together by dispersion forces
sheets are 341 pm apart

76

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Properties of Graphite
Hexagonal crystals High melting point, ~3800 C
need to overcome some covalent bonding

Slippery feel
because there are only dispersion forces holding the sheets together, they can slide past each other
glide planes

lubricants

Electrical conductor
parallel to sheets

Thermal insulator Chemically very nonreactive

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sp2 hybridzed C atoms, each of which is bonded with trogonal planar geometry to three other carbons
77

Structure of Fullerene
The third crystalline allotrope of carbon is called fullerene. It consists of spherical C60 molecules with extraordinary shape of a soccer ball. The C60 molecule has 12 pentagonal and 20 hexagonal faces, with each atom sp2-hybridzed and bonded to three other atoms. sp2 hybridzed C atoms, each of which is bonded to three other carbons

78

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Structure of Graphene
Graphene is a one-atom-thick planar sheet of sp2-bondec carbon atoms that are densely packed in a honeycomb crystal lattice Graphite itself consists of many graphene sheets stacked together. The carbon-carbon bond length in graphene is approximately 0.142 nm.

Properties:
Graphene is as the strongest material ever measured, some 200 times stronger than structural steel.

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Quartz
SiO2 in pure form
impurities add color

3-dimensional array of Si covalently bonded to 4 O

tetrahedral

Melts at ~1600 C Very hard

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Metallic Bonding
Metal atoms release their valence electrons Metal cation islands fixed in a sea of mobile electrons
+ e+ e+ + + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + + ee+ + +

81

12-81

Crystal structures of metals

A. Copper adopts cubic closest packing.

B. Magnesium adopts hexagonal closest packing.

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The band of molecular orbitals in lithium metal

12-83

Electrical conductivity in a conductor, semiconductor, and insulator

conductor

semiconductor

insulator

The conducting properties of a substance are determined by the energy gap between the valence and conduction bands of MOs.

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n- and p-Type Semiconductors

An n-type semiconductor is produced when a crystal is doped with another substance with more valence electrons

The energy levels of these donor atoms lie quite close to the conduction band and the extra electron(s) are lost to the conduction band
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Crystal structures and band representations of doped semiconductors

Pure silicon has an energy gap between its valence and conduction bands. Its conductivity is low at room temperature.

Doping silicon with phosphorus adds additional valence e-. These enter the conductance band, bridging the energy gap and increasing conductivity.

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n- and p-Type Semiconductors

A p-type semiconductor is produced when a crystal is doped with another substance with less valence electrons

The energy levels of these acceptor atoms lie quite close to the valence band and electrons are easily promoted from the valence band into the acceptor level
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EOS

Doping silicon with gallium removes electrons from the valence band and introduces positive ions. Si electrons can migrate to the empty orbitals, increasing conductivity.

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The Photovoltaic Cell

A photovoltaic cell, or solar cell, is a semiconductor device that converts light to electricity The cell consists of a thin layer of p-type semiconductor, such as Si doped with Al, in contact with an n-type semiconductor, such as Si doped with P The p-type semiconductor in the solar cell must be very thinabout 1 104 cm to reduce the tendency for conduction electrons produced by sunlight to be captured by positive holes and immobilized in covalent bonds.

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An Example Cell

EOS

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The p-n junction

p-n junction

Placing a p-type semiconductor adjacent to an n-type creates a p-n junction. Electrons flow freely in the n-to-p direction.

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