Chapter 11 PDF

Changes of State
• A change of state or phase transition is a

change of a substance from one state to
another.
States of Matter:
Liquids and Solids gas
boiling condensation
sublimation liquid condensation or
deposition
melting freezing
solid
Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 11–3
States of Matter Vapor Pressure
• States of matter: gases, liquids, and solids. • The vapor pressure of a liquid depends on its
– Gases are compressible fluids. Their molecules are temperature.)
widely separated. – As the temperature increases, the kinetic energy of the
– Liquids are relatively incompressible fluids. Their molecular motion becomes greater, and vapor pressure
molecules are more tightly packed. increases.
– Solids are nearly incompressible and rigid. Their – Liquids and solids with relatively high vapor pressures at
molecules or ions are in close contact and do not move. normal temperatures are said to be volatile.
•The temperature at which the vapor pressure of a liquid equals the
pressure exerted on the liquid is called the boiling point.
–The normal boiling point is the boiling point at 1 atm.
Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 11–2 Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 11–4
1
Figure 11.7: Variation of vapor pressure with temperature.
Heat of Phase Transition
• To melt a pure substance at its melting point

requires an extra boost of energy to overcome
lattice energies.
– The heat needed to melt 1 mol of a pure substance is
called the heat of fusion and denoted ∆Hfus.
– For ice, the heat of fusion is 6.01 kJ/mol.
H2O(s) →H2O(l); ∆Hfus = 6.01kJ

Freezing Point Heat of Phase Transition
• The temperature at which a pure liquid changes – The heat needed to boil 1 mol of a pure substance is called
to a crystalline solid, or freezes, is called the the heat of vaporization and denoted ∆Hvap.
freezing point. – For ice, the heat of vaporization is 40.66 kJ/mol.

• The melting point is identical to the freezing
H2O(l) →H2O(g); ∆Hvap = 40.66kJ
point and is defined as the temperature at
which a solid becomes a liquid.
– Unlike boiling points, melting points are affected
significantly by only large pressure changes.
2
A Problem to Consider Phase Diagrams
• The heat of vaporization of ammonia is 23.4 • Curve AB, dividing the solid region from the
kJ/mol. How much heat is required to vaporize liquid region, represents the conditions under
1.00 kg of ammonia? which the solid and liquid are in equilibrium.
– First, we must determine the number of moles of
ammonia in 1.00 kg (1000 g).
B .C
pressure
solid liquid
1mol NH3
1.00×103 g NH3 × = 58.8mol NH3
17.0g NH3
–Then we can determine the heat required for vaporization. .A gas
58.8mol NH3 ×23.4kJ/mol =1.38×103 kJ D

temperature
Phase Diagrams Phase Diagrams

• A phase diagram is a graphical way to summarize the three areas
representing each state of the substance under which the • Usually, the melting point is only slightly
different states of a substance (solid, liquid and gas) are stable. The
affected by pressure. For this reason, the
curves separating each area represent the boundaries of
phase changes. melting point curve, AB, is nearly vertical.
B .C B .C
pressure
pressure
solid liquid solid liquid
D
.A gas .A gas
D
temperature temperature
3
• Curve AC, which divides the liquid region • The temperature above which the liquid state
from the gaseous region, represents the of a substance no longer exists regardless of
boiling points of the liquid for various pressure is called the critical temperature.
pressures.
B .C B .C
pressure
pressure
.A gas .A gas
D D Tcrit
• The curves intersect at A, the triple point, • The vapor pressure at the critical temperature
which is the temperature and pressure where is called the critical pressure. Note that
three phases of a substance exist in curve AC ends at the critical point, C.
equilibrium.
B .C Pcrit B .C
pressure
pressure
.A gas .A gas
D D Tcrit
4
Phase diagram for water (not to scale). Dipole-Dipole Forces
• Polar molecules can attract one another through dipole-dipole
forces.
– The dipole-dipole force is an attractive intermolecular
force resulting from the tendency of polar molecules to
align themselves positive end to negative end.
δ+ H Cl δ− δ+ H Cl δ−
shows the alignment of polar molecules.
Intermolecular Forces; Explaining

London Forces
Liquid Properties
• Many of the physical properties of liquids (and certain solids) • London forces are the weak attractive forces resulting from
can be explained in terms of intermolecular forces, the instantaneous dipoles that occur due to the distortion of the
forces of attraction between molecules. electron cloud surrounding a molecule.
Three types of forces are known to exist between neutral London forces increase with molecular weight. The larger a molecule, the
molecules. more easily it can be distorted to give an instantaneous dipole.
1. Dipole-dipole forces All covalent molecules exhibit some London force.
2. London (or dispersion) forces •In summary, intermolecular forces play a large role in many of the
3. Hydrogen bonding physical properties of liquids and gases. These include:
•The term van der Waals forces is a general term including dipole- vapor pressure
dipole and London forces.
boiling point
Van der Waals forces are the weak attractive forces in a large number of
substances.
surface tension
Hydrogen bonding occurs in substances containing hydrogen atoms bonded to viscosity
certain very electronegativePresentation
Copyright © Houghton Mifflin Company.All rights reserved. atoms. of Lecture Outlines, 11–18 Copyright © Houghton Mifflin Company.All rights reserved. Presentation of Lecture Outlines, 11–20
5
Van der Waals Forces and the
Hydrogen Bonding
Properties of Liquids
• The vapor pressure of a liquid depends on • Molecules exhibiting hydrogen bonding have abnormally high
boiling points compared to molecules with similar van der
intermolecular forces. When the intermolecular forces Waals forces.
in a liquid are strong, you expect the vapor pressure to
be low. O O
As intermolecular forces increase, vapor pressures
decrease.
H H H H
•Surface tension increases with increasing intermolecular forces.
Surface tension is the energy needed to reduce the surface area of a O O
liquid.
To increase surface area, it is necessary to pull molecules apart
H H H H
against the intermolecular forces of attraction.
Hydrogen Bonding Solid State

•Viscosity increases with increasing intermolecular forces because • A solid is a nearly incompressible state of matter with
increasing these forces increases the resistance to flow. a well-defined shape. The units making up the solid
• Hydrogen bonding is a force that exists between a hydrogen are in close contact and in fixed positions.
atom covalently bonded to a very electronegative atom, X, and – Solids are characterized by the type of force holding the
a lone pair of electrons on a very electronegative atom, Y. structural units together.
– To exhibit hydrogen bonding, one of the following three structures must – In some cases, these forces are intermolecular, but in
be present. others they are chemical bonds (metallic, ionic, or
covalent).
•From this point of view, there are four types of solids.
:
H N H O H F Molecular (Van der Waals forces)

Metallic (Metallic bond)
– Only N, O, and F are electronegative enough to
Ionic (Ionic bond)
leave the hydrogen nucleus exposed.
Covalent (Covalent bond)
6
Types of Solids Physical Properties
• A molecular solid is a solid that consists of atoms or
molecules held together by intermolecular forces. • Many physical properties of a solid can be
– Many solids are of this type. attributed to its structure.
– Examples include solid neon, solid water (ice), and solid
carbon dioxide (dry ice). • Melting Point and Structure
– For a solid to melt, the forces holding the structural units
together must be overcome.
• A metallic solid is a solid that consists of positive cores of – For a molecular solid, these are weak intermolecular
atoms held together by a surrounding “sea” of electrons attractions.
(metallic bonding).
• In this kind of bonding, positively charged atomic cores are – Thus, molecular solids tend to have low melting points
surrounded by delocalized electrons. (below 300oC).
– Examples include iron, copper, and silver. For ionic solids and covalent network solids to melt, chemical
bonds must be broken.
For that reason, their melting points are relatively high.
Types of Solids Physical Properties
• An ionic solid is a solid that consists of cations and • Many physical properties of a solid can be attributed to its
anions held together by electrical attraction of opposite structure.
charges (ionic bond). • Hardness and Structure
– Examples include cesium chloride, sodium – Hardness depends on how easily structural units can be moved
chloride, and zinc sulfide (but ZnS has relative to one another.
considerable covalent character). – Molecular solids with weak intermolecular attractions are rather
soft compared with ionic compounds, where forces are much
•A covalent network solid is a solid that consists of atoms held stronger.
together in large networks or chains by covalent bonds.
Covalent network solids are quite hard because of the rigidity of the
Examples include carbon, in its forms as diamond or graphite , covalent network structure.
asbestos, and silicon carbide.
Diamond and silicon carbide (SiC), three-dimensional covalent
network solids, are among the hardest substances known.
7
Physical Properties Crystal Lattices
• Many physical properties of a solid can be attributed to its • A crystal lattice is the geometric arrangement
structure.
of lattice points in a crystal.
• Electrical Conductivity and Structure
– A unit cell is the smallest boxlike unit from which
– Molecular and ionic solids are generally considered you can construct a crystal by stacking the units in
nonconductors. three dimensions. There are seven basic shapes
– Ionic compounds conduct in their molten state, as ions are possible for unit cells, which give rise to seven
then free to move. crystal systems used to classify crystals.
– Metals are all considered conductors. These seven systems can have more than one
Of the covalent network solids, only graphite conducts electricity. possible crystal lattice.
This is due to the delocalization of the resonant p electrons in A “primitive” lattice has lattice points only at the corners
graphite’s sp2 hybridization. of each cell.
Crystalline Solids; Crystal Lattices

Crystal Defects
and Unit Cells
• Solids can be crystalline or amorphous.
• There are principally two kinds of defects that
– A crystalline solid is composed of one or more crystals; occur in crystalline substances.
each crystal has a well-defined, ordered structure in three
dimensions.
Examples include sodium chloride and sucrose. – Chemical impurities, such as in rubies, where the
– An amorphous solid has a disordered structure. It lacks crystal is mainly aluminum oxide with an occasional Al3+
the well-defined arrangement of basic units found in a ion replaced with Cr3+, which gives a red color.
crystal. – Defects in the formation of the lattice. Crystal planes
Glass is an amorphous solid. may be misaligned, or sites in the crystal lattice may
remain vacant.
8
Calculations Involving Unit
Operational Skills
Cell Dimensions
• X-ray diffraction is a method for determining the
structure and dimensions of a unit cell in a crystalline • Calculating the heat required for a phase
compound. change of a given mass of substance.
• Calculating vapor pressures and heats of
– Once the dimensions and structure are known, the volume
vaporization.
and mass of a single atom in the crystal can be calculated.
• Relating the conditions for the liquification of
– The determination of the mass of a single atom gave us
one of the first accurate determinations of Avogadro’s
a gas to the critical temperature.
number. • Identifying intermolecular forces.
• Determining relative vapor pressure on the
basis of intermolecular attraction.
• Identifying types of solids.
Determination of Crystal Lattice by

Operational Skills
X-Ray Diffraction
• When x-rays are reflected from the • Determining the relative melting points
planes of a crystal, they show a based on types of solids.
diffraction pattern that can be recorded • Determining the number of atoms per
on photographic film. unit cell.
– Analysis of these diffraction patterns allows the • Calculating atomic mass from unit-cell
determination of the positions of the atoms in the dimension and density.
unit cell of the solid. • Calculating unit-cell dimensions from
– Figures 11.48 and 11.49 illustrate how the unit-cell type and density.
diffraction of the x-rays occurs.

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Changes of State

• A change of state or phase transition is a

States of Matter Vapor Pressure

–The normal boiling point is the boiling point at 1 atm.

• To melt a pure substance at its melting point

– For ice, the heat of fusion is 6.01 kJ/mol.

H2O(s) →H2O(l); ∆Hfus = 6.01kJ

Freezing Point Heat of Phase Transition

freezing point. – For ice, the heat of vaporization is 40.66 kJ/mol.

58.8mol NH3 ×23.4kJ/mol =1.38×103 kJ D

Phase Diagrams Phase Diagrams

Phase Diagrams Phase Diagrams

Intermolecular Forces; Explaining

Hydrogen Bonding Solid State

H N H O H F Molecular (Van der Waals forces)

Types of Solids Physical Properties

Crystalline Solids; Crystal Lattices

Determination of Crystal Lattice by

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