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Intermolecular Forces: Liquids, Solids, and Phase Changes Chapter 12 12-1

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Page 1: Handout CHM102 Chapter 12

Intermolecular Forces: Liquids, Solids, and Phase Changes

Chapter 12

12-1

Page 2: Handout CHM102 Chapter 12

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.

12-2

• 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?

Page 3: Handout CHM102 Chapter 12

Chapter Outlines

• Physical States and Phase Changes

• Quantitative Aspects of Phase Changes

• Types of Intermolecular Forces

12-3

• Properties of the Liquid State

• The Uniqueness of Water

• The Solid State: Structure, Properties, and Bonding

Page 4: Handout CHM102 Chapter 12

Phases of Matter

• A physically distinctive form of matter is called a phase.

• The properties of each phase are determined by thebalance between the potential and kinetic energyof the particles.

12-4

• Potential energy in the form of intermolecular forcestends to draw the molecules together. Why?

• Kinetic energy associated with the random motion ofthe molecules tends to disperse them.

Page 5: Handout CHM102 Chapter 12

Potential energy vs. Kinetic energy

Properties

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

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

Kinetic Molecular View of the Three States

12-5

Liquid Attractive forces are stronger because particles are touching.

A liquid can flow and change shape, but has a fixed volume.

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

A solid has a fixed shape and volume.

Page 6: Handout CHM102 Chapter 12

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

12-6

• 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

6

Page 7: Handout CHM102 Chapter 12

Types of Phase Changes and their Enthalpies

melting vaporizingendothermic

sublimation

• As temperature increases, the average KE does too, so the fastermoving particles overcome attractions more easily.

• As temperature decreases, particles slow, so attractions can pull them together.

12-7

solid liquid gas

freezing condensing

endothermic

exothermic

deposition

Page 8: Handout CHM102 Chapter 12

Two familiar Phase Changes

12-8

Page 9: Handout CHM102 Chapter 12

Heats of Vaporization and Fusion for several common substances

12-9

Page 10: Handout CHM102 Chapter 12

Phase Changes and their Enthalpy Changes

12-10

Page 11: Handout CHM102 Chapter 12

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

Liquid water coolsLiquid water freezes

Gaseous water condenses

Solid water cools

Gaseous water cools

12-11

Page 12: Handout CHM102 Chapter 12

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

Heat Involved in Phase Changes

q = (amount) x (heat capacity) x ΔT

12-12

q = (amount)(ΔH of phase change)

• During a phase change, heat flow occurs at constant temperature, as the average distance between particles changes.

Page 13: Handout CHM102 Chapter 12

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.

12-13

Page 14: Handout CHM102 Chapter 12

SOLUTION: There are 3 stages involved in this process:1) heating of the liquid to its boiling point2) the phase change from liquid to gas3) heating the gas to the final temperature

mol H2O = 24.3 g H2O x1 mol H2O

18.02 g H2O= 1.35 mol H2O

For Stage 1:q1 = n x Cwater(l) x ΔT

= (1.35 mol)(75.4 J/mol·°C)(100. - 85.0°C) = 1527 J = 1.53 kJ

12-14

= 1527 J = 1.53 kJ

For Stage 2:q2 = n(ΔH°vap) = (1.35 mol)(40.7 kJ/mol) = 54.9 kJ

qtotal = q1 + q2 + q3= 1.53 + 54.9 + 0.760 kJ = 57.2 kJ

For Stage 3:q3 = n x Cwater(g) x ΔT

= (1.35 mol)(33.1 J/mol·°C)(117 – 100.°C) = 759.6 J = 0.760 kJ

Page 15: Handout CHM102 Chapter 12

Liquid-Gas Equilibrium

12-15

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

Page 16: Handout CHM102 Chapter 12

12-16

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.

Page 17: Handout CHM102 Chapter 12

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

12-17

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

higher T higher P

weaker forces higher P

Page 18: Handout CHM102 Chapter 12

The effect of temperature on the distribution of molecular speeds

12-18

Page 19: Handout CHM102 Chapter 12

Vapor Pressure as a function of Temperature and Intermolecular Forces

• Vapor pressure increases astemperature increases.

• Vapor pressure decreases as

12-19

• Vapor pressure decreases asthe strength of the intermolecularforces increases.

Page 20: Handout CHM102 Chapter 12

The Clausius-Clapeyron Equation

CTR

HP +Δ⎟⎟

⎜⎜

⎛ 1- = ln vap

This equation relates vapor pressure to temperature.

12-20

⎟⎟⎠

⎞⎜⎜⎝

⎛ −Δ

12

vap

1

2 11- = ln

TTR

H

P

P

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

Page 21: Handout CHM102 Chapter 12

Linear plots of the relationship between vapor pressure and temperature

CTR

HP +Δ⎟⎟

⎜⎜

⎛ 1- = ln vap

12-21

RHvap-Δslope =

Page 22: Handout CHM102 Chapter 12

Problem 12.2 Applying the Clausius-Clapeyron Equation

SOLUTION:

PROBLEM: The vapor pressure of ethanol is 115 torr at 34.9°C. If ΔHvap of ethanol is 40.5 kJ/mol, calculate the temperature (in °C) when the vapor pressure is 760 torr.

P2P1

ln = - ΔHvap

R1T2

1T1

12-22

T1 = 34.9°C + 273.15 = 308.0 K

ln760 torr115 torr

=- 40.5 x103 J/mol

8.314 J/mol·K1T2

1308.0 K

T2 = 350.00 K

= 350.00 K– 273.15

= 76.85°C

R T2 T1

Page 23: Handout CHM102 Chapter 12

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.

12-23

As the external pressure on a liquid increases, the boiling point increases.

standard atmospheric pressure or 760 torr.

Real world examples:

Page 24: Handout CHM102 Chapter 12

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.

12-24

A typical phase diagram. The dotted green line gives the anomalousbehavior of water. The Clausius–Clapeyron relation can be used to find therelationship between pressure and temperature along phase boundaries.

gas phases become equal.

At the triple point, all three phases are in equilibrium.

Page 25: Handout CHM102 Chapter 12

Phase Diagram for CO2

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

12-25

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

liquid.

Page 26: Handout CHM102 Chapter 12

Phase Diagram for H2O

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

12-26

liquid. Water expands on freezing.

Page 27: Handout CHM102 Chapter 12

Types of Intermolecular Forces

Intermolecular forces are relatively weak compared to

Intermolecular forces arise from the attraction between molecules with partial charges, or between ions and molecules.

12-27

Intermolecular forces are relatively weak compared to bonding forces because they involve smaller charges that are farther apart.

Page 28: Handout CHM102 Chapter 12

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

12-28

Page 29: Handout CHM102 Chapter 12

Comparison of Bonding (intramolecular) and Nonbonding (Intermolecular) Forces ……cont’d

12-29

Page 30: Handout CHM102 Chapter 12

Polar molecules and dipole-dipole forces

Dipole–dipole forces arise when permanent dipoles align themselves with the positive end of one dipole directed toward the negative ends of neighboring dipoles.

12-30

Page 31: Handout CHM102 Chapter 12

Dipole moment and Boiling point

12-31

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.

Page 32: Handout CHM102 Chapter 12

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.

12-32

the N, O, or F atom of another molecule.

Page 33: Handout CHM102 Chapter 12

Hydrogen bonding and Boiling point

12-33

Page 34: Handout CHM102 Chapter 12

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)

12-34

SOLUTION:

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

Page 35: Handout CHM102 Chapter 12

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

12-35

(c) can form H bonds at two sites:

Page 36: Handout CHM102 Chapter 12

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

12-36

- For a polar molecule, the field enhances the existing dipole moment.

Polarizability: the ease with which a particle’s electron cloud can be distorted.

Page 37: Handout CHM102 Chapter 12

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.

12-37

Polarizability decreases across a period because of increasing Zeff.

Cations are smaller than their parent atoms and less polarizable; anions show the opposite trend.

Page 38: Handout CHM102 Chapter 12

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.

12-38

• 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.

molecules result in a temporary dipole.

Page 39: Handout CHM102 Chapter 12

Dispersion Forces among Nonpolar Particles

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

12-39

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.

Page 40: Handout CHM102 Chapter 12

Molar mass and trends in boiling point

Dispersion forces are stronger for larger, more polarizable particles.

Polarizability depends on the

12-40

Polarizability depends on the number of electrons, which correlates closely with molar mass.

Page 41: Handout CHM102 Chapter 12

Molecular shape, intermolecular contact, and boiling point

There are more points at which dispersion forces act.

There are fewer points

12-41

There are fewer points at which dispersion forces act.

Page 42: Handout CHM102 Chapter 12

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

12-42

(d) Hexane (CH3CH2CH2CH2CH2CH3) or 2,2-dimethylbutane

Page 43: Handout CHM102 Chapter 12

SOLUTION:

(a) MgCl2 consists of Mg2+ and Cl- ions held together by ionic bonding forces; PCl3 consists of polar molecules, so intermolecular dipole-dipole 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

12-43

(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.

Page 44: Handout CHM102 Chapter 12

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

12-44

CH3CH2OH has a higher boiling point than CH3OH.

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

Page 45: Handout CHM102 Chapter 12

(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.

12-45

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.

Page 46: Handout CHM102 Chapter 12

Surface Tension:

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

Properties of the Liquid State

12-46

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.

Page 47: Handout CHM102 Chapter 12

Substance FormulaSurface Tension

(J/m2) at 200C Major Force(s)

Diethyl ether

Ethanol

Dipole-dipole; dispersion

H bonding

1.7x10-2

2.3x10-2

CH3CH2OCH2CH3

CH3CH2OH

Surface Tension and Forces Between Particles

12-47

Ethanol

Butanol

Water

Mercury

H bonding

H bonding; dispersion

H bonding

Metallic bonding

2.3x10

2.5x10-2

7.3x10-2

48x10-2

CH3CH2OH

CH3CH2CH2CH2OH

H2O

Hg

Page 48: Handout CHM102 Chapter 12

Capillary Action:

12-48

A. Water displays a concave meniscus.

B. Mercury displays a convex meniscus.

Page 49: Handout CHM102 Chapter 12

H-bonding ability of Water:

hydrogen bond donor

hydrogen bond acceptor

Properties of Water

12-49

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

1. Solvent Properties of Water

Page 50: Handout CHM102 Chapter 12

The hexagonal structure of ice

2. Unusual density of solid water

12-50

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

3. Thermal Properties of water

4. Surface Properties

Page 51: Handout CHM102 Chapter 12

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

12-51

Amorphous solids lack orderly arrangement and have poorly defined shapes.

Page 52: Handout CHM102 Chapter 12

12-52Some crystalline solids

Page 53: Handout CHM102 Chapter 12

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.

12-53

Page 54: Handout CHM102 Chapter 12

7 Unit Cells

Cubica = b = call 90°

a

b

c

Tetragonala = c < ball 90°

a

b

c

Orthorhombica ≠ b ≠ call 90°

a

b

c

Monoclinica ≠ b ≠ c

2 faces 90°

a b

c

12-54

all 90° all 90° all 90°

Hexagonala = c < b

2 faces 90°1 face 120°

c

a

b

Rhombohedrala = b = cno 90°

ab

c

Triclinica ≠ b ≠ cno 90°

a

b

c

54

Page 55: Handout CHM102 Chapter 12

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,

12-55

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

55

Tro: Chemistry: A Molecular Approach, 2/e

Page 56: Handout CHM102 Chapter 12

Simple Cubic Unit Cell

Expanded view.

Space-filling view.

12-56

Atoms/unit cell = (⅛ x 8) = 1

⅛ atom at 8 corners

Coordination number = 6

Space-filling view.

Page 57: Handout CHM102 Chapter 12

Body-centered cubic unit cell

12-57

⅛ atom at 8 corners

1 atom at center

Atoms/unit cell = (⅛ x 8) + 1 = 2

Coordination number = 8

Page 58: Handout CHM102 Chapter 12

The face-centered cubic cell.

12-58

Atoms/unit cell = (⅛ x 8) + (½ x 6) = 4

⅛ atom at 8 corners

½ atom at 6 faces

Coordination number = 12

Page 59: Handout CHM102 Chapter 12

12-5959

Page 60: Handout CHM102 Chapter 12

Packing spheres to obtain three cubic and hexagonal cells

large diamond space

2nd layer directly over 1st

12-60

simple cubic(52% packing efficiency)

body-centered cubic(68% packing efficiency)

2nd layer over diamond spaces in 1st

3rd layer over diamond spaces in 2nd

Page 61: Handout CHM102 Chapter 12

12-61

Page 62: Handout CHM102 Chapter 12

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 = πr3.)43

12-62

Page 63: Handout CHM102 Chapter 12

SOLUTION:

Volume/mole of Ba metal = 1density

x M 1 cm3

3.62 g Ba= x

137.3 g Ba1 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

12-63

= 37.9 cm3/mol Ba x 0.68 = 26 cm3/mol Ba atoms

= 4.3 x 10-23 cm3/Ba atom

Volume of Ba atom = 26 cm3

1 mol Ba atomsx

1 mol Ba atoms6.022x1023 Ba atoms

Page 64: Handout CHM102 Chapter 12

Volume of Ba atom = πr343

r =4π√ 3V3

√3 3(4.3x10-23cm3)

4 x 3.14=

= 2.2 x 10-8 cm

12-64

Page 65: Handout CHM102 Chapter 12

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

12-65

Page 66: Handout CHM102 Chapter 12

Diffraction of x-rays by crystal planes

Tools of the Laboratory

12-66

Page 67: Handout CHM102 Chapter 12

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

12-67

Page 68: Handout CHM102 Chapter 12

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?

12-68

Page 69: Handout CHM102 Chapter 12

SOLUTION:

Using the Pythagorean theorem to find C, the diagonal of the cell’s face:

C = A2 + B2√ The unit cell is a cube, so A = B, Therefore

12-69

C = 2A2√ = 2(361.5 pm)2√ = 511.2 pm

C = 4r, so r =511.2 pm

4= 127.8 pm

Page 70: Handout CHM102 Chapter 12

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.

12-70

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.

Page 71: Handout CHM102 Chapter 12

Characteristics of the Major Types of Crystalline Solids

Type Particle(s) Interparticle Forces

Physical Properties Examples [mp, °C]

Atomic Atoms Dispersion Soft, very low mp, poor thermal and electrical conductors

Group 8A(18)(Ne [-249) to Rn [-71])

Molecular Molecules Dispersion, Fairly soft, low to Nonpolar*

12-71

Molecular Molecules Dispersion, dipole-dipole, H bonds

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

NonpolarO2 [-219], C4H10 [-138]Cl2 [-101], C6H14 [-95]P4 [44.1]PolarSO2 [-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).

Page 72: Handout CHM102 Chapter 12

Characteristics of the Major Types of Crystalline Solids

Type Particle(s) Interparticle Forces

Physical Properties Examples [mp, °C]

Ionic Positive and negative ions

Ion-ion attraction Hard and brittle, high mp, good thermal and electrical conductors when molten

NaCl [801]CaF2 [1423]MgO [2852]

Metallic Atoms Metallic bond Soft to hard, low to very Na [97.8]

12-72

Metallic 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]

Network covalent

Atoms Covalent bond Very hard, very high mp, usually poor thermal and electrical conductors

SiO2 (quartz) [1610]C (diamond) [~3550]

Page 73: Handout CHM102 Chapter 12

Rock Salt Structures:

• Coordination number = 6

• Cl─ ions in a face-centered cubic arrangement– ⅛ of each corner Cl─ inside the unit cell

– ½ of each face Cl─ inside the unit cell

• Na+ in holes between Cl─

– octahedral holes

Structures of Some Ionic Solids

12-73

– octahedral holes– 1 in center of unit cell

– 1 whole particle in every octahedral hole

– ¼ of each edge Na+ inside the unit cell

• Na:Cl = (¼ x 12) + 1: (⅛ x 8) + (½ x 6)

=4:4

• Therefore, the formula is NaCl

73

Page 74: Handout CHM102 Chapter 12

Zinc Blende Structures

• Coordination number = 4

• S2─ ions in a face-centered cubic arrangement– ⅛ of each corner S2─ inside the unit cell

– ½ of each face S2─ inside the unit cell

• Each Zn2+ in holes between S2

12-74

• Each Zn2+ in holes between S2─

– tetrahedral holes– 1 whole particle in ½ the holes

• Zn:S = (4 x 1) : (⅛ x 8) + (½ x 6)

= 4:4 = 1:1

• Therefore the formula is ZnS

74

Page 75: Handout CHM102 Chapter 12

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

Structures of Some Network Covalent Solids

12-75

– due to the strong covalent bonds holding the atoms in position

– used as abrasives

• Electrical insulator

• Thermal conductor– best known

• Chemically very nonreactive

75

sp3 hybridzed C atoms, each of which is bonded with tetraheral geometry to four other carbons

Page 76: Handout CHM102 Chapter 12

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

12-76

• bond length = 142 pm

– sp2

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

76

Page 77: Handout CHM102 Chapter 12

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

12-77

the sheets together, they can slide past each other• glide planes

– lubricants

• Electrical conductor– parallel to sheets

• Thermal insulator

• Chemically very nonreactive

77

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

Page 78: Handout CHM102 Chapter 12

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

12-7878

sp2 hybridzed C atoms, each of which is bonded to three other carbons

each atom sp2-hybridzed and bonded to three other atoms.

Page 79: Handout CHM102 Chapter 12

• 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.

Structure of Graphene

12-79

• 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.

Page 80: Handout CHM102 Chapter 12

Quartz• SiO2 in pure form

– impurities add color

• 3-dimensional array of Si covalently bonded to 4 O– tetrahedral

12-80

– tetrahedral

• Melts at ~1600 °C• Very hard

80

Tro: Chemistry: A Molecular Approach, 2/e

Page 81: Handout CHM102 Chapter 12

Metallic Bonding

• Metal atoms release their valence electrons

• Metal cation “islands” fixed in a “sea” of mobile electrons

+ + + + + + + + +

12-81

e-

e-e-

e-

e-

e-

e-

e-

e-

e-

e-

e-

e-

e-

e-

e-

+ + + + + + + + +

+ + + + + + + + +

+ + + + + + + + +

81

Page 82: Handout CHM102 Chapter 12

Crystal structures of metals

12-82

A. Copper adopts cubic closest packing.

B. Magnesium adopts hexagonal closest packing.

Page 83: Handout CHM102 Chapter 12

The band of molecular orbitals in lithium metal

12-83

Page 84: Handout CHM102 Chapter 12

Electrical conductivity in a conductor, semiconductor, and insulator

12-84

conductor semiconductor insulator

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

Page 85: Handout CHM102 Chapter 12

n- and p-Type SemiconductorsAn n-type semiconductor is produced when a crystal is “doped” with another substance with more valence electrons

The energy levels of

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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

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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

The energy levels of

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

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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 EOS

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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 semi-conductor, such as Si doped with Al, in contact with an n-type semiconductor, such as Si doped with P

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The p-type semiconductor in the solar cell must be very thin—about 1 × 10–4 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

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EOS

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p-n junction

The p-n junction

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