Miles Eckles April 22, 2011

Chemistry 101 Ch 11 (cont’d)

Intermolecular forces, Liquids and Solids (cont’d)

Types of Intermolecular Forces

 Ion-dipole forces

o Important in solutions

 Dipole-dipole forces

 London dispersion forces

 Hydrogen-bonding forces

o The latter three are sometimes known as van der Waals forces, and are limited

to interactions between neutral molecules.

Ion-dipole Forces

 Force which exists between an ion and the partial charge on the end of a polar

molecule. Positive ions are attracted to negative end of dipole, and negative ions are

attracted to positive end of dipole.

  The magnitude of the attraction increases as either the charge of the ion or magnitude

of the dipole moment increases.

o Especially important for ionic substances dissolved in polar liquids.

Dipole-Dipole Forces

 Forces between neutral polar molecules, when the positive end of one molecule is near

the negative end of another.

- + - +

 Dipole-dipole forces are only effective over very short distances, and they are generally

weaker than ion-dipole forces.

 For molecules of approximately equal mass and size, the strengths of intermolecular

attractions increase with increasing polarity

London Dispersion Forces

 London forces are attractive forces due to instantaneous dipole moments in molecules

(which can be different from the average dipole).

electrostatic
attraction

e- e-
+2 +2

e- e-
 He He

 Significant in nonpolar molecules.

 These forces are significantly only over short distances.

 Polarizability—ease with which charge distribution can be distorted by an external

electric field.

 Dispersion forces tend to increase with increasing molecular size or weight.

 Dispersion forces operate between all molecules, whether polar or nonpolar. Often

dispersion forces contribute more to intermolecular forces in polar molecules than

dipole-dipole forces.

Hydrogen Bonding

 A special type of intermolecular attraction that exists between the hydrogen atom in a

polar bond (esp. H-F, H-O, or H-N bond) and an unshared electron pair on a nearby

electronegative ion or atom (usually an F, O, or N atom on another molecule)

 Energies on the order of 4-25 kJ/mol, so generally stronger than dispersion forces or

dipole-dipole forces.

 Play important roles in biological systems (enzymes, DNA duplexes)

 H-bonding elevates boiling point (why water boils at 100 ˚C even though only MW =

18.0 amu) and makes ice less dense than liquid water.

Liquid Viscosity

 Viscosity—the resistance of a liquid to flow. The greater the viscosity, the slower the

flow.
 o Ex. maple syrup is more viscous than beer

 Viscosity is related to the ease with which individual molecules of the liquid move w/rt

one another (thus, the attractive forces between molecules).

 Viscosity decreases with increasing temperature because at higher temperatures the

greater average kinetic energy of the molecules more easily overcomes the attractive

forces between molecules.

Surface Tension

 Surface tension—the amount of energy required to increase the surface area of a liquid

by a unit amount

o water has a high surface tension of 7.29 x 10-2 J/m2, due in large part to H—

bonding

 Intermolecular forces that bind similar molecules together are known as cohesive

forces.

 Adhesive forces—intermolecular forces that bind a substance to a surface

 Capillary action—the rise of liquids up a narrow tube. The adhesive forces between the

wall of the tube and liquid to increase surface area of liquid is countered by surface

tension which tends to reduce area, pulling liquid up the tube.

Phase Changes

 Phase changes are transformations of matter from one phase to another.

 Endothermic processes include:

o Solid →liquid (melting)

o Solid →gas (sublimation)

 o Liquid →gas (vaporization)

Energy Changes Accompanying Phase Changes

 Heat of fusion (ΔHfus) is the enthalpy change associated with melting a solid.

 Heat of vaporization (ΔHvap) is the enthalpy associated with vaporizing a liquid.

 ΔHfus is less than ΔHvap because less energy is needed to get molecules to move across

one another than to separate them.

 Since melting, vaporization, and sublimation are all endothermic, their reverse

processes (freezing, condensation, and deposition) are all exothermic processes.

Heating Curve for H2O

Critical Temperature and Pressure

 Critical temperature is the highest temperature at which a substance can exist as a

liquid, while critical pressure is the highest pressure at which a substance can exist as a

liquid. Above these points, the substance exists as a supercritical fluid.

Vapor Pressure
  Vapor pressure of a liquid measures the tendency of a liquid to evaporate. The vapor

pressure is the partial pressure of the vapor when it is in dynamic equilibrium with the

liquid.

 At equilibrium, the rate of transfer of molecules from the liquid to the vapor equals the

rate of transfer from the vapor to the liquid.

Volatility

 The higher the vapor pressure of a liquid, the more volatile it is.

 Vapor pressure increases non-linearly with temperature.

 A liquid boils when its vapor pressure equals the external pressure acting on the surface

of the liquid. At 1 atm pressure this called the normal boiling point.

Phase Diagrams

 The equilibria between solid, liquid, and gas phases of a substance as a function of

temperature and pressure are displayed on a phase diagram. Equilibria between any

two phases are indicated by a line.

Generalized Phase Diagram

Critical point

melting
vaporization
freezing
condensation
 sublimation

deposition

Highlights of Phase Diagram

 Line TC represents vapor-pressure curve between liquid and gas phases. At B, the

critical point, liquid and gas phases become indistinguishable from one another.

 Line TA represents variation in vapor pressure of solid as it sublimes

 Line TF represents change in melting point with pressure. Usually slopes to the right.

The melting point (or freezing point) at 1 atm. Is the normal melting point.

The Triple Point

 Point T in the phase diagram is known as the triple point. At this temperature and

pressure, all three phases of matter are in equilibrium. Any other point on the curves

represents a two phase equilibrium, and any other point represents matter of only a

single phase.

Structures of Solids

 A crystalline solid is a solid whose atoms, ions, or molecules are ordered in well-defined

arrangements (e.g., quartz rock, diamond)

 An amorphous solid is a solid whose particles have no orderly structure (e.g., rubber and

glass)
Unit Cells

 Unit cell—the smallest part of a crystal that can, by simple displacement, reproduce the

three-dimensional structure of the crystal. The unit cell contains all the essential

features of the crystalline solid.

 Crystal lattice—the three dimensional structures of a crystal; the points in the lattice

represent positions in structure where there are identical environments.

 Simple cubic cell is also known as a primitive cubic cell

Fractions of an Atom That Occupies a Unit Cell

Position in Unit Cell Fraction of Unit Cell

Center 1

Face 1/2

Edge 1/4

Corner 1/8
Crystal Structure of NaCl

 NaCl has a face-centered cubic lattice structure. Determine the net number of Na + and

Cl- in each unit cell.

Na+: (1/4 Na+ per edge)(12 edges) = 3 Na+

(1 Na+ per center)(1 center) = 1 Na+
Cl-: (1/8 Cl- per corner)(8 corners) = 1 Cl-
(1/2 Cl- per face)(6 faces) = 3 Cl-
Thus, 4 Na+ and 4 Cl-

Density Problem

LiF has same geometric arrangement as NaCl. Unit cell is 4.02 Å on an edge. What is the density

of LiF in g/cm3?

Mass = 4 (6.94 amu) + 4 (19.0 amu) = 103.8 amu

(1 g)
103.8 amu = 1.72 x 10-22 g
23
(6.02 x 10 amu)

(10-8cm)3
Volume = (4.02 Å)3 = 6.50 x 10-23 cm3
(1 Å)3

1.72 x 10-22 g
Density = = 2.65 g/cm3
-23 3
6.50 x 10 cm

Close Packing of Spheres

 Many solids have closed-packed structure in which spherical particles are arranged so as

to leave the minimal amount of empty space.

 Two closely related forms of close packing are cubic close packing and hexagonal close

packing. In each, the sphere has a coordination number of 12.

Bonding in Solids

 Molecular solids consist of atoms or molecules held together by intermolecular forces

(dipole-dipole, dispersion forces, and hydrogen bonds). Because these forces are weak,

molecular solids are soft and have low melting points.

o Ex: Ar, methane, sucrose, dry ice

Covalent Network Solids

 Covalent network solids consist of atoms held together in large networks or chains by

covalent bonds, which are much stronger than intermolecular forces. These solids are

harder and have higher melting points.

o Ex: diamond, graphite, quartz, silicon carbide (SiC), boron nitride (BN)

 Ionic solids are hard and brittle and have hard melting points.

o Ex: NaCl, ZnS, CaF2

 Metallic solids consist of metal cations held together by a “sea” of electrons, and exhibit

a wide range of properties, but they are good conductors of heat and electricity.