1. Intermolecular Forces and
Liquids and Solids
Chapter 11

2. Depends on the intermolecular distance
A phase is a homogeneous part of the system in contact with other parts of the system but separated from them by a well-defined boundary.
2 Phases
Solid phase - ice
Liquid phase - water
Depends on the intermolecular distance

3. Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
41 kJ to vaporize 1 mole of water (inter)
930 kJ to break all O-H bonds in 1 mole of water (intra)
“Measure” of intermolecular force
boiling point
melting point
DHvap
DHfus
DHsub
Generally, intermolecular forces are much weaker than intramolecular forces.
Chemical bonding and physical properties!

4. Intermolecular Forces
Dipole-Dipole Forces
Attractive forces between polar molecules
Orientation of Polar Molecules in a Solid
So higher dipole, larger attractive force.

5. Intermolecular Forces
Ion-Dipole Forces
Attractive forces between an ion and a polar molecule
Ion-Dipole Interaction
Small r, larger F

6. Interaction Between Water and Cations
Hydration(水合)
in solution

7. Intermolecular Forces
Dispersion Forces
分散力(also be called as London Force)
Attractive forces that arise as a result of temporary dipoles induced in atoms or molecules
ion-induced dipole interaction
dipole-induced dipole interaction

8. Dispersion Forces
極化率
The polarizability: the ability to distortion the electron distribution
of a molecular or atoms.
Normally, large amount of electrons or low-density electron
cloud will show higher polarization
Dispersion force is the transition of the dipole-induced attraction
So He or N2 gas/non-polarized maculars can be condensed
in low-temperature.

9. Induced Dipoles Interacting With Each Other
Transition state

10. Intermolecular Forces
Dispersion Forces Continued
Polarizability is the ease with which the electron distribution in the atom or molecule can be distorted.
Polarizability increases with:
greater number of electrons
more diffuse electron cloud
Dispersion forces usually increase with molar mass.
Some dispersion force larger than polarized dipole-dipole force!
e.g. CCl4 (76.5o)shows higher boiling point than CH3F(-78.4o)

11. What type(s) of intermolecular forces exist between each of the following molecules?
HBr
HBr is a polar molecule: dipole-dipole forces. There are also dispersion forces between HBr molecules.
CH4
CH4 is nonpolar: dispersion forces. S O
SO2
SO2 is a polar molecule: dipole-dipole forces. There are also dispersion forces between SO2 molecules.

12. Intermolecular Forces
Hydrogen Bond
The hydrogen bond is a special dipole-dipole interaction between they hydrogen atom in a polar N-H, O-H, or F-H bond and an electronegative O, N, or F atom. A H … B or
A & B are N, O, or F

13. Why is the hydrogen bond considered a “special” dipole-dipole interaction?
Decreasing molar mass
Decreasing boiling point

14. Hydrogen Bond
HCOOH and water

15. The average hydrogen bond is ~ 40KJ/mol.
The strength of hydrogen bond depends on the electronegativity
Of atoms.
e.g. HF shows higher strength than H2O. However, H2O shows
Higher boiling point than HF? Each H2O have 4 H-bond.

16. Strong intermolecular forces
Properties of Liquids
Surface tension is the amount of energy required to stretch or increase the surface of a liquid by a unit area.
Strong intermolecular forces
High surface tension

17. H2O show very strong H-bond, therefore shows higher surface tension than other liquid

18. Polarized molecular and non-polarized molecular

19. Properties of Liquids
Cohesion is the intermolecular attraction between like molecules
Adhesion is an attraction between unlike molecules
Adhesion
Cohesion

20. Strong intermolecular forces
Properties of Liquids
Viscosity is a measure of a fluid’s resistance to flow.
Strong intermolecular forces
High viscosity

21. Similar to H2O, it shows high H-bond
Viscosity
CH2-OH 甘油
Similar to H2O, it shows high H-bond

22. Ice is less dense than water
3-D Structure of Water
Water is a Unique Substance
2 共價鍵
2氫鍵
Maximum Density
4°C
Density of Water
Ice is less dense than water

23. ice
benzene

24. Unit cells in 3 dimensions
A crystalline solid possesses rigid and long-range order. In a crystalline solid, atoms, molecules or ions occupy specific (predictable) positions.
An amorphous solid does not possess a well-defined arrangement and long-range molecular order.
A unit cell is the basic repeating structural unit of a crystalline solid.
lattice
point
At lattice points:
Atoms
Molecules
Ions
Unit Cell
Unit cells in 3 dimensions

25. Seven Basic Unit Cells

26. Three Types of Cubic Unit Cells

27. Arrangement of Identical Spheres in a Simple Cubic Cell

28. Arrangement of Identical Spheres in a Body-Centered Cubic Cell

29. A Corner Atom, a Edge-Centered Atom and a Face-Centered Atom
Shared by 2 unit cells
Shared by 4 unit cells
Shared by 8 unit cells

30. Number of Atoms Per Unit Cell
1 atom/unit cell
2 atoms/unit cell
4 atoms/unit cell
(8 x 1/8 = 1)
(8 x 1/8 + 1 = 2)
(8 x 1/8 + 6 x 1/2 = 4)

31. Relation Between Edge Length and Atomic Radius

32. When silver crystallizes, it forms face-centered cubic cells
When silver crystallizes, it forms face-centered cubic cells. The unit cell edge length is 409 pm. Calculate the density of silver.
d = m V
V = a3
= (409 pm)3 = 6.83 x cm3
4 atoms/unit cell in a face-centered cubic cell
107.9 g
mole Ag x
1 mole Ag
6.022 x 1023 atoms x
m = 4 Ag atoms
= 7.17 x g
d = m V
7.17 x g
6.83 x cm3 =
= 10.5 g/cm3

33. Closest Packing

34. Closest Packing

35. HCP and CCP
AB stacking
ABC stacking

36. X-Ray Diffraction (XRD) X-光繞射光譜

40. Applications: MoS2 crystalline

41. Applications: Graphite oxide

42. XRD

43. The crystal types: Ionic crystals Covalent Crystals Molecular Crystals
Metallic Crystals

44. Types of Crystals Ionic Crystals
Lattice points occupied by cations and anions
Held together by electrostatic attraction
Hard, brittle, high melting point
Poor conductor of heat and electricity
CsCl
ZnS
CaF2

45. EX: KH2PO4

46. NaCl(FCC)

47. Types of Crystals Covalent Crystals Lattice points occupied by atoms
Held together by covalent bonds
Hard, high melting point
Poor conductor of heat and electricity
carbon
atoms
diamond
graphite

48. From graphite to graphene
Slice down to
Atomic layer

49. What is graphene?
Imagine a piece of paper but a million times thinner. This is how thick graphene is.
The thinnest while strongest material in the world!
(0.77 mg/1m2 Graphene, can sustain 4 kg )
Imagine a material more conducting than silver. This is how conductive graphene is.
Image from Nobel committee
From a recently interview with A. K. Geim.

50. Electrical properties of Graphene
Graphene resistivity: 1.0x10-8 Ohm m
Also, it’s current density is > 1.0X108 A/cm
From wikipedia

51. Mechanical properties
Graphene : ~1000 GPa
From wikipedia

52. Thermal conductivity
Graphene : ~5300 W/mK
Movie
From wikipedia

53. Optical properties
Graphene : ~1000 GPa
Science (2008)

54. Carrier mobility in graphene : 1/300 of light speed
Low energy is like a massless 2D Dirac model
Zero band gap semiconductor.
Carrier shows Linear
dispersion around Femi- level.
The electronic behavior
can be described by
QM ‘s Dirac equation.
4. In condense physic :
The unique Massless
Dirac fermions K K’ M
石墨烯
更为奇特之处是它具有独特的电子结构和电学性质.
石墨烯的价带(π 电子)和导带(π*电子)相交于费米能
级处(K 和K′点), 是能隙为零的半导体,
Ballistic transport on submicron to micron distances.
IBM already demonstrated 100 GHz high frequency device.
Dispersion: Dr. Thomas Szkopek, McGill University

55. Energy dispersion

56. Density of state of Graphene

57. Types of Crystals Molecular Crystals
Lattice points occupied by molecules
Held together by intermolecular forces
Soft, low melting point
Poor conductor of heat and electricity
water
benzene

58. EX: S8

59. Cross Section of a Metallic Crystal
Types of Crystals
Metallic Crystals
Lattice points occupied by metal atoms
Held together by metallic bonds
Soft to hard, low to high melting point
Good conductors of heat and electricity
(high density)
Cross Section of a Metallic Crystal
nucleus &
inner shell e-
mobile “sea”
of e-

62. Amorphous solid:
Glass

65. Phase Changes
Greatest
Order
Least

66. The equilibrium vapor pressure is the vapor pressure measured when a dynamic equilibrium exists between condensation and evaporation
H2O (l) H2O (g)
Rate of
condensation
evaporation =
Dynamic Equilibrium

67. Measurement of Vapor Pressure
Before
Evaporation
At Equilibrium

68. Vapor Pressure Versus Temperature
Molar heat of vaporization (DHvap) is the energy required to vaporize 1 mole of a liquid at its boiling point.
ln P = -
DHvap RT
+ C
Clausius-Clapeyron Equation
P = (equilibrium) vapor pressure
T = temperature (K)
R = gas constant (8.314 J/K•mol)
Vapor Pressure Versus Temperature

69. Alternate Forms of the Clausius-Clapeyron Equation
At two temperatures or

70. The boiling point is the temperature at which the (equilibrium) vapor pressure of a liquid is equal to the external pressure.
The normal boiling point is the temperature at which a liquid boils when the external pressure is 1 atm.

71. The critical temperature (Tc) is the temperature above which the gas cannot be made to liquefy, no matter how great the applied pressure.
The critical pressure (Pc) is the minimum pressure that must be applied to bring about liquefaction at the critical temperature.

72. The Critical Phenomenon of SF6
T < Tc
T > Tc
T ~ Tc
T < Tc

73. Solid-Liquid Equilibrium
H2O (s) H2O (l)
The melting point of a solid or the freezing point of a liquid is the temperature at which the solid and liquid phases coexist in equilibrium

74. Molar heat of fusion (DHfus) is the energy required to melt 1 mole of a solid substance at its freezing point.

75. Solid-Gas Equilibrium
H2O (s) H2O (g)
Molar heat of sublimation (DHsub) is the energy required to sublime 1 mole of a solid.
DHsub = DHfus + DHvap
( Hess’s Law)

76. A phase diagram summarizes the conditions at which a substance exists as a solid, liquid, or gas.
Phase Diagram of Water

77. Phase Diagram of Carbon Dioxide
At 1 atm
CO2 (s) CO2 (g)

78. Effect of Increase in Pressure on the Melting Point
of Ice and the Boiling Point of Water

79. CH11 Homework
12.98 Given the phase diagram of carbon shown here, answer these questions: (a) How many triple points are there and what are the phases that can coexist at each triple point? (b) Which has a higher density, graphite or diamond? (c) Synthetic diamond can be made from graphite. Using the phase diagram, how would you go about making diamond?
12.20 Explain the difference in the melting points of these compounds:

80. 12. 80 The vapor pressure of benzene, C6H6, is 40. 1 mmHg at 7. 6°C
12.80 The vapor pressure of benzene, C6H6, is 40.1 mmHg at 7.6°C. What is its vapor pressure at 60.6°C? The molar heat of vaporization of benzene is 31.0 kJ/mol.