Liquids and solids

They are similar to each other

Different than gases. x They are incompressible. x Their density doesnt change much with temperature. x These similarities are due to the molecules staying close together in solids and liquids and far apart in gases x What holds them close together?
x

Intermolecular forces
Inside molecules (intramolecular) the atoms are bonded to each other. x Intermolecular refers to the forces between the molecules. x Holds the molecules together in the condensed states.
x

Strong covalent bonding ionic bonding x Weak Dipole dipole London dispersion forces x During phase changes the molecules stay intact. x Energy used to overcome forces.
x

Intermolecular forces

Dipole - Dipole
Remember where the polar definition came from? x Molecules line up in the presence of a electric field. The opposite ends of the dipole can attract each other so the molecules stay close together. x 1% as strong as covalent bonds x Weaker with greater distance. x Small role in gases.
x

+
-

+
-

Hydrogen Bonding
Especially strong dipole-dipole forces when H is attached to F, O, or N x These three because They have high electronegativity. They are small enough to get close. x Effects boiling point.
x

100 H2O HF NH3 -100 CH4 PH3 SiH4 200 H2S HCl

Boiling Points
H2Te SbH3 HI SnH4

0C

H2Se AsH3 HBr GeH4

Water
+ +

Each water molecule can make up to four H-bonds

London Dispersion Forces

Non - polar molecules also exert forces on each other. x Otherwise, no solids or liquids. x Electrons are not evenly distributed at every instant in time. x Have an instantaneous dipole. x Induces a dipole in the atom next to it. x Induced dipole- induced dipole interaction.
x

Example
+
H

+
H H

London Dispersion Forces

Weak, short lived. x Lasts longer at low temperature. x Eventually long enough to make liquids. x More electrons, more polarizable. x Bigger molecules, higher melting and boiling points. x Weaker than other forces.
x

Van der Waals forces

London dispersion forces and Dipole interactions x Order of increasing strength LDF Dipole H-bond Real bonds
x

Liquids
Many of the properties due to internal attraction of atoms. Beading Surface tension Capillary action Viscosity x Stronger intermolecular forces cause each of these to increase.
x

Surface tension
x

Molecules at the the top are only pulled inside. x Molecules in the middle are attracted in all directions. Minimizes surface area.

Capillary Action
Liquids spontaneously rise in a narrow tube. x Intermolecular forces are cohesive, connecting like things. x Adhesive forces connect to something else. x Glass is polar. It attracts water molecules.
x

Beading
x

If a polar substance is placed on a nonpolar surface. There are cohesive, But no adhesive forces.

Viscosity
How much a liquid resists flowing. x Large forces, more viscous. x Large molecules can get tangled up. x Cyclohexane has a lower viscosity than hexane. x Because it is a circle- more compact.
x

How much of these?

Stronger forces, bigger effect. Hydrogen bonding H next to O,N, or F Dipole-dipole Polar molecules LDF All molecules x In that order
x

Model of a Liquid
Cant see molecules so picture them asx In motion but attracted to each other x With regions arranged like solids but with higher disorder. with fewer holes than a gas. Highly dynamic, regions changing between types.
x

Phases
x

The phase of a substance is determined by three things. The temperature. The pressure. The strength of intermolecular forces.

Solids
Two major types. x Amorphous- those with much disorder in their structure. x Crystalline- have a regular arrangement of components in their structure.
x

Crystals
Lattice- a three dimensional grid that describes the locations of the pieces in a crystalline solid. x Unit Cell-The smallest repeating unit in of the lattice. x Three common types.
x

Cubic

Body-Centered Cubic

Face-Centered Cubic

The book drones on about

Using diffraction patterns to identify crystal structures. x Talks about metals and the closest packing model. x It is interesting, but trivial. x We need to focus on metallic bonding. x Why do metal atoms stay together? x How their bonding affects their properties.
x

There are many amorphous solids. x Like glass. x We tend to focus on crystalline solids. x two types. Ionic solids have ions at the lattice points. Molecular solids have molecules. x Sugar vs. Salt.
x

Solids

Metallic Bonds
How atoms are held together in the solid. x Metals hold onto their valence electrons very weakly. x Think of them as positive ions floating in a sea of electrons.
x

Sea of Electrons
Electrons are free to move through the solid. x Metals conduct electricity.
x

+ + + + + + + + + + +

Metals are Malleable

Hammered into shape (bend). x Ductile - drawn into wires. x Because of mobile valence electrons
x

Malleable

+ + + + + + + + + + +

Malleable
x

Electrons allow atoms to slide by but still be attracted.

+ + + + + + + + + + + +

Metallic bonding
3p 3s 2p 2s 1s Magnesium Atoms Empty Molecular Orbitals Filled Molecular Orbitals

The 1s, 2s, and 2p electrons are close to nucleus, so they are not able to move around. Empty Molecular 3p Orbitals Filled Molecular Orbitals 3s 2p 2s 1s Magnesium Atoms

The 3s and 3p orbitals overlap and form molecular orbitals. 3p 3s 2p 2s 1s Magnesium Atoms Empty Molecular Orbitals Filled Molecular Orbitals

Electrons in these energy levels can travel freely throughout the crystal. Empty Molecular 3p Orbitals Filled Molecular Orbitals 3s 2p 2s 1s Magnesium Atoms

This makes metals conductors Malleable because the bonds are flexible.

3p 3s 2p 2s 1s

Empty Molecular Orbitals Filled Molecular Orbitals

Magnesium Atoms

Carbon- A Special Atomic Solid

There are three types of solid carbon. x Amorphous- soot - uninteresting. x Diamond- hardest natural substance on earth, insulates both heat and electricity. x Graphite- slippery, conducts electricity. x How the atoms in these network solids are connected explains why.
x

Diamond- each Carbon is sp hybridized, connected to four other carbons.

3

Carbon atoms are locked into tetrahedral shape. x Strong bonds give the huge molecule its hardness.
x

Why is it an insulator?
All the electrons need to be shared in the covalent bonds Cant move around

Graphite is different.
Each carbon is connected to three other carbons and sp2 hybridized. x The molecule is flat with 120 angles in fused 6 member rings. x The bonds extend above and below the plane.
x

Electrons are free to move throughout these delocalized orbitals. x Conducts electricity x The layers slide by each other. x Lubricant
x

This bond overlap forms a huge bonding network.

Molecular solids.
Molecules occupy the corners of the lattices. x Different molecules have different forces between them. x These forces depend on the size of the molecule. x They also depend on the strength and nature of dipole moments.
x

Those without dipoles.

Most are gases at 25C. x The only forces are London Dispersion Forces. x These depend on number of electrons. x Large molecules (such as I2 ) can be solids even without dipoles. (LDF)
x

Dipole-dipole forces are generally stronger than L.D.F. x Hydrogen bonding is stronger than Dipole-dipole forces. x No matter how strong the intermolecular force, it is always much, much weaker than the forces in bonds. x Stronger forces lead to higher melting and freezing points.
x

Those with dipoles.

Water is special
x

Each molecule has two polar O-H bonds.

+ H H +

Water is special
Each molecule has two polar O-H bonds. +x Each molecule has two lone H pair on its oxygen.
x

H +

Water is special
Each molecule has two polar O-H bonds. +x Each molecule has two lone H pair on its oxygen. O x Each oxygen can interact with H 2 hydrogen atoms. +
x

Water is special
+ H O H + H O H +
+

+ H O H +

This gives water an especially high melting and boiling point.

The extremes in dipole-dipole forcesatoms are actually held together by opposite charges. x Huge melting and boiling points. x Atoms are locked in lattice so hard and brittle. x Every electron is accounted for so they are poor conductors-good insulators. x Until melted or dissolved.
x

Ionic Solids

Phase Changes

Vaporization - change from liquid to gas at boiling point. Evaporation - change from liquid to gas below boiling point Heat (or Enthalpy) of Vaporization ( Hvap )- the energy required to vaporize 1 mol at 1 atm.

Vapor Pressure

Vaporization is an endothermic process - it requires heat. x Energy is required to overcome intermolecular forces. x Responsible for cool beaches. x Why we sweat.
x

Condensation
Change from gas to liquid. x Achieves a dynamic equilibrium with vaporization in a closed system. x What is a closed system? x A closed system means matter cant go in or out. x Put a cork in it. x What the heck is a dynamic equilibrium?
x

Dynamic equilibrium
 When

first sealed the molecules gradually escape the surface of the liquid

Dynamic equilibrium
 When

first sealed the molecules gradually escape the surface of the liquid  As the molecules build up above the liquid some condense back to a liquid.

Dynamic equilibrium
 As

time goes by the rate of vaporization remains constant  but the rate of condensation increases because there are more molecules to condense.  Equilibrium is reached when

Dynamic equilibrium
Rate of Vaporization = Rate of Condensation
x

Molecules are constantly changing phase Dynamic The total amount of liquid and vapor remains constant Equilibrium

Vapor pressure
The pressure above the liquid at equilibrium. x Liquids with high vapor pressures evaporate easily. x They are called volatile. x Decreases with increasing intermolecular forces. Bigger molecules (bigger LDF) More polar molecules (dipole-dipole)
x

Vapor pressure
Increases with increasing temperature. x Easily measured in a barometer.
x

Vacuum A barometer will hold a column of mercury 760 mm high at one atm

Patm = 760 torr

Dish of Hg

Vacuum A barometer will hold a column of mercury 760 mm high at one atm. If we inject a volatile liquid in the barometer it will rise to the top of the mercury.

Patm = 760 torr

Dish of Hg

Patm = 760 torr

Dish of Hg

Water A barometer will hold a column of mercury 760 mm high at one atm. If we inject a volatile liquid in the barometer it will rise to the top of the mercury. There it will vaporize and push the column of mercury down.

Water Vapor x

736 mm Hg
x x x

The mercury is pushed down by the vapor pressure. Patm = PHg + Pvap Patm - PHg = Pvap 760 - 736 = 24 torr

Dish of Hg

Temperature Effect
# of molecules
T1

Energy needed to overcome intermolecular forces

Kinetic energy

At higher temperature more molecules have enough energy - higher vapor pressure.

# of molecules

T1

Energy needed to overcome intermolecular forces

T2

Kinetic energy

Mathematical relationship
vap PT1 ln vap = PT 2

vap 1 H - R T2T1

ln is the natural logarithm ln = Log base e e = Eulers number an irrational number like x Hvap is the heat of vaporization in J/mol
x

Mathematical relationship
vap PT1 ln vap = PT 2

vap 1 H - R T2T1

R = 8.3145 J/K mol. x Surprisingly this is the graph of a straight line. x If you graph ln P vs 1/T
x

Mathematical relationship
vap PT1 ln vap = PT 2

vap 1 H - R T2T1

The vapor pressure of water is 23.8 torr at 25C. The heat of vaporization of water is 43.9 kJ/mol. Calculate the vapor pressure at 50C x At what temperature would it have a vapor pressure of 760 torr?
x

Changes of state
The graph of temperature versus heat applied is called a heating curve. x The temperature a solid turns to a liquid is the melting point. x The energy required to accomplish this change is called the Heat (or Enthalpy) of Fusion Hfus
x

Heating Curve for Water

140 120 100 80 60 40 20 0 -20 -40 0

Steam Water and Steam

Water Ice10 Water and Ice 90

190 730 740

Heating Curve for Water

140 120 100 80 60 40 20 0 -20 -40 0

1/ Slope is Heat Capacity

Heat of Vaporization Heat of 90 Fusion

10

190

730

740

Melting Point
Melting point is determined by the vapor pressure of the solid and the liquid. x At the melting point the vapor pressure of the solid = vapor pressure of the liquid
x

Water Vapor Vapor Solid Water

Liquid Water

If the vapor pressure of the solid is higher than that of the liquid the solid will release molecules to achieve equilibrium.

Water Vapor Vapor Solid Water

Liquid Water

While the molecules of condense to a liquid. Water Vapor Vapor Solid Water

Liquid Water

This can only happen if the temperature is above the freezing point since solid is turning to liquid. Water Vapor Vapor Solid Water

Liquid Water

If the vapor pressure of the liquid is higher than that of the solid, the liquid will release molecules to achieve equilibrium.

Water Vapor Vapor Solid Water

Liquid Water

While the molecules condense to a solid. Water Vapor Vapor Solid Water

Liquid Water

The temperature must be below the freezing point since the liquid is turning to a solid. Water Vapor Vapor Solid Water

Liquid Water

If the vapor pressure of the solid and liquid are equal, the solid and liquid are vaporizing and condensing at the same rate. The Melting point.

Water Vapor Vapor Solid Water

Liquid Water

Boiling Point
Reached when the vapor pressure equals the external pressure. x Normal boiling point is the boiling point at 1 atm pressure. x Superheating - Heating above the boiling point. x Supercooling - Cooling below the freezing point.
x

Phase Diagrams.
x

A plot of temperature versus pressure for a closed system, with lines to indicate where there is a phase change.

Pressure

Solid C

D
Liquid C B

D D

1 Atm B

A
Gas

Temperature

Pressure

Solid

Liquid

Critical Point

Triple Point Gas

Temperature

Pressure

This is the phase diagram for water. x The density of liquid water is higher than Solid solid water.
x

Liquid

Gas

Temperature

x x

This is the phase diagram for CO2 The solid is more dense than the liquid The solid sublimes at 1 atm.
Solid Liquid

Pressure

1 Atm
Gas

Temperature