Anderson - MCHS States of Matter AP Chem.

Unit 03
Page 1

States of Matter
Unit Overview
Unit 4: Chapter 10 Gases
Chapter 11 Solids, Liquids and Intermolecular forces
Unit 4: States of Matter

Chapter 10) Gases (1.5 wk)
- Gas Laws (Charles, Boyles, Combined, Ideal). Charles and Boyles
Law lab. Stoichiometry with Gases, Daltons Law of Partial Pressure.
Real Gas Laws, Kinetic Theory.
Chapter 10 Test

Chapter 11) Liquids and Solids (1.5 wk)
- Clausius-Clapeyron Equation, phase diagrams. Solid structural types
(Ionic, molecular covalent, network covalent, metallic), Intermolecular
Forces (dipole, hydrogen bonding, dispersion or London forces).
structures (simple cubic, face-centered cubic,body-centered cubic).
Chapter 11 Test

Related Labs:
Determining the Molar Volume of a Gas (AP requirement Determination
of the Molar Volume of a Gas) (Vonderbrink)
Determination of the Molar Mass of Gases and Volatile Liquids (AP
requirement #3 Determination of the Molar Mass by Vapor Density)(
Vonderbrink)
Liquid Chromatography (AP requirement #18 Separation by
Chromatography)( Vonderbrink)
The Structure of Crystals (Slowinski)



UNIT 03 EXAM AP FORMAT STATES OF MATTER
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 2


Unit Objectives
Chapter 10 Gases
AP10-1,2-01 Describe the general characteristics of gases and compared to other states of
matter, and list the ways in which gases are distinct
AP10-1,2-02 Define atmosphere, torr, and pascal, the most important units in which
pressure is expressed. Also describe how a barometer and a manometer
work.
AP10-3,4,5-01 Describe how a gas responds to changes in pressure, volume, temperature and
quantity of gas.
AP10-3,4,5-02 Use the ideal gas equation to solve for one variable (P,V, n, or T), given the
other three variables of information from which they can be determined
AP10-3,4,5-03 Use the gas laws, including the combined gas law to calculate how one
variable of a gas (P,V,n,or T) responds to changes in one or more of the other
variables.
AP10-3,4,5-04 Calculate the molar mass of a gas, given the gas density under specified
conditions of temperature and pressure. Also calculate gas density under
stated conditions, knowing the molar mass.
AP10-6-01 Calculate the partial pressure of any gas in a mixture, given the composition of
that mixture.
AP10-6-02 Calculate the mole fraction of a gas mixture, given its partial pressure and
total pressure of the system.
AP10-7,8-01 Describe how the distribution of speeds and the average speed of gas
molecules changes with temperature.
AP10-7,8-02 Describe how the relative rates of effusion and diffusion of two gases depend
on their molar masses. (Graham's Law)
AP10-7,8-03 Use the principles of the Kinetic Molecular Theory of gases to explain the
nature of gas pressure and temperature at the molecular level.
AP10-9-01 Explain the origin of deviations shown by real gases from the ideal gas
relationship.
AP10-9-02 Cite the general conditions of P and T under which real gases most closely
approximate ideal gas behavior.
AP10-9-03 Explain the origins of the correction terms to P and V that appears in the van
der Waals equation.
Anderson - MCHS States of Matter AP Chem. Unit 03
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Unit Objectives

Chapter 11 Intermolecular forces, Liquids & Solids
AP11-1-01 Employ the kinetic-molecular model to explain the differences in motion of
particles in gases, liquids and solids and how these relate to their states.
AP11-1-02 Describe the various types of intermolecular attractive forces, and state the
kinds of intermolecular forces expected for a substance given its molecular
structure.
AP11-3,4,5-01 Explain the meaning of the terms viscosity, surface tension, critical
temperature, and critical pressure, and account for the variations in these
properties in terms of intermolecular forces and temperature.

AP11-3,4,5-02
Explain the way in which the vapor pressure of a substance changes with
intermolecular forces and temperature.
AP11-3,4,5-03 Describe the relationship between the pressure on the surface of a liquid and
the boiling point of the liquid.
AP11-3,4,5-04 Given the needed heat capacities and enthalpies for phase changes, calculate
the heat absorbed or evolved when a qiven quantity of a substance changes
from one condition of another.
AP11-6-01 Draw a phase diagram of a substance given appropriate data, and use a phase
diagram to predict which phases are present at any given temperature and
pressure.
AP11-7,8-01 Distinguish between crystalline and amorphous solids.
AP11-7,8-02 Determine the net contents in a cubic unit cell, given a drawing or verbal
description of the cell. Use this information, together with the atomic weights
of the atoms in the cell and the cell dimensions, to calculate the density of teh
substance.

AP11-7,8-03

Describe the most efficient packing patterns of equal-sized spheres.
AP11-7,8-04 Predict the type of solid (molecular, covalent network, ionic, of metallic)
formed by a substances, ,and predict its general properties.



Anderson - MCHS States of Matter AP Chem. Unit 03
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Schedule & Assignments
Text Readings, Notes & Practice --- Option 1
Complete the readings before discussions in class. Carefully read through the sample
exercises and attempt the practice exercise in the text. Pay particular attention to vocabulary
& concept reviews. After class discussion practice a min. of 5 EOCs for each section.
(Correct answers are in the back of the book or on MCHS AP CHEMISTRY.COM) Do what
you need to MASTER each concept. You should be able to summarize the main concepts in
the section both conceptually and mathematically.



Assignments for Unit: Option 1
Chapter 10 Gases
Text Section EOCQs
Date
completed Topic
10-1 Characteristics of gases Pg 394-395 11-24
10-2 Pressure Pg 395 - 398 11-24
Chemistry & Life Blood Pressure Pg 398
10-3 The Gas Laws Pg 398 - 402 25-28
10-4 The Ideal Gas Equation Pg 402 - 406 29-44
10-5 Further Applications of the ideal gas
equation
Pg 406 - 410 45-58
Chemistry put to Work Gas Pipelines Pg 409
10-6 Gas Mixtures and Partial Pressures Pg 410 - 413 59-70
10-7 Kinetic Molecular Theory Pg 414 - 416 71-82
A Closer Look The ideal gas equation*** Pg 416
10-8 Molecular Effusion and Diffusion Pg 417 - 420 71-82
Chemistry Put to Work Gas Separations Pg 420
10-9 Real Gas Deviations from Ideal Behavior Pg 420 - 424 83-88
Visualizing Concepts MUST DO1-10
Additional Exercises MUST DO94,99,100,102,107
Integrative Exercises MUST DO112,113,116,120,121

Chapter 11 IMFs, Liquids & Solids
Text Section EOCQs
Topic
11-1 A Molecular Comparison of Gases,
Liquids and Solids
Pg 436 - 439 9-12
11-2 Intermolecular Forces Pg. 439 - 447 13-28
11-3 Some Properties of Liquids Pg 447 - 448 29-32
11-4 Phase Changes Pg 449 - 452 33-42
Chemistry Put to Work.
Supercritical fluid extraction
pg 453

11-5 Vapor Pressure Pg 453 - 455 43-50
Anderson - MCHS States of Matter AP Chem. Unit 03
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A Closer Look
The Clausius Clapeyron
Equation

11-6 Phase Diagrams Pg 456 - 458 51-56
11-7 Structure of Solids Pg 458 - 464 57-68
11-8 Bonding in Solids Pg 464 - 469 69-78
A Closer Look
X ray diffraction by Crystals
Pg 465

A closer Look
The Third form of Carbon Pg
468


Chapter Review, Key Skills & Key Equations Pg 469 -471
Visualizing Concepts Pg 471 MUST DO1-8
Additional Exercises Pg 477-478 MUST DO79,81,8385,89,90
Intergrative Exercises 478 479 MUST DO100,101,102




Chapter 10. Gases
Common Student Misconceptions
Common Student Misconceptions
Students need to be told to always use temperature in Kelvin in gas problems.
Students should always use units in gas-law problems to keep track of required
conversions.
Due to several systems of units, students often use ideal gas constants with units
inconsistent with values.
Students often confuse the standard conditions for gas behavior (STP) with the
standard conditions in thermodynamics.
Ideal gas behavior should discussed as just that, ideal; students should be
reminded that real gases do not behave ideally, especially at high pressures and/or
low temperatures.
Students expect a change in the gas particle distribution upon temperature changes
at constant V.
Students commonly confuse effusion and diffusion.
Students often think that all atoms of the same element must have the same
oxidation number and that this number is uniquely related to the atoms location
in the periodic table.
It is important that students know that titrations can be conducted not only using
acids and bases, but also in precipitation and oxidationreduction reactions.
Anderson - MCHS States of Matter AP Chem. Unit 03
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Lecture Outline
10.1 Characteristics of Gases(EOCQS 15,16,19,22,23)

All substances have three phases: solid, liquid, and gas.
Substances that are liquids or solids under ordinary conditions may also exist
as gases.
These are often referred to as vapors.
Many of the properties of gases differ from those of solids and liquids:
Gases are highly compressible and occupy the full volume of their containers.
When a gas is subjected to pressure, its volume decreases.
Gases always form homogeneous mixtures with other gases.
Gases only occupy a small fraction of the volume of their containers.
As a result, each molecule of gas behaves largely as though other molecules
were absent.
FORWARD REFERENCES
Thermodynamics of phase changes will be discussed in Ch. 19.
Such important gaseous reactions as the Haber process or equilibria involving
nitrogen oxides will be covered in Ch. 15.
10.2 Pressure(EOCQS 15,16,19,22,23)
Pressure is the force acting on an object per unit area:
Atmospheric Pressure and the Barometer

The SI unit of force is the newton (N).
1 N = 1 kg-m/s
2

The SI unit of pressure is the pascal (Pa).
1 Pa = 1 N/m
2
A related unit is the bar, which is equal to 10
5
Pa.
Gravity exerts a force on the Earths atmosphere.

A column of air 1 m
2
in cross section extending to the upper atmosphere
exerts a force of 10
5
N.
Thus, the pressure of a 1 m
2
column of air extending to the upper
atmosphere is 100 kPa.
Atmospheric pressure at sea level is about 100 kPa or 1 bar.
The actual atmospheric pressure at a specific location
depends on the altitude and weather conditions.
Atmospheric pressure is measured with a barometer.
A
F
P =
Anderson - MCHS States of Matter AP Chem. Unit 03
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If a tube is completely filled with mercury and then inverted into a
container of mercury open to the atmosphere, the mercury will rise 760 mm up
the tube.

Standard atmospheric pressure is the pressure required to support 760
mm of Hg in a column.
Important non-SI units used to express gas pressure include:
atmospheres (atm)
millimeter of mercury (mm Hg) or torr
1 atm = 760 mm Hg = 760 torr = 1.01325 x 10
5
Pa = 101.325 kPa.
FORWARD REFERENCES
Osmotic pressure (in atm) will be calculated in Ch. 13 (section 13.5).
K
p
s and thermodynamic equilibrium constants in Ch. 15 will use pressure (in atm).
Pressure and Le Chteliers principle will be discussed in Ch. 15 (section 15.7).
10.3 The Gas Laws (EOCQS 25-28)
The equations that express the relationships among T (temperature), P (pressure),
V (volume), and n (number of moles of gas) are known as gas laws.
The PressureVolume Relationship: Boyles Law

Weather balloons are used as a practical application of the relationship between
pressure and volume of a gas.
As the weather balloon ascends, the volume increases.
As the weather balloon gets further from Earths surface, the
atmospheric pressure decreases.
Boyles law: The volume of a fixed quantity of gas, at constant temperature, is
inversely proportional to its pressure.
Mathematically:
A plot of V versus P is a hyperbola.

A plot of V versus 1/P must be a straight line passing through the origin.
The working of the lungs illustrates Boyles law.
As we breathe in, the diaphragm moves down, and the ribs expand;
therefore, the volume of the lungs increases.
According to Boyles law, when the volume of the lungs increases, the
pressure decreases; therefore, the pressure inside the lungs is less than
atmospheric pressure.
Atmospheric pressure then forces air into the lungs until the pressure
once again equals atmospheric pressure.
As we breathe out, the diaphragm moves up and the ribs contract.
Therefore, the volume of the lungs decreases.
By Boyles law, the pressure increases and air is forced out.
constant or t
1
constan = = PV
P
V
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 8


The TemperatureVolume Relationship: Charless Law

We know that hot-air balloons expand when they are heated.
Charless law: The volume of a fixed quantity of gas at constant pressure is
directly proportional to its absolute temperature.

Mathematically:
Note that the value of the constant depends on the pressure and number
of moles of gas.
A plot of V versus T is a straight line.
When T is measured in C, the intercept on the temperature
axis is 273.15 C.
We define absolute zero, 0 K = 273.15 C.
The QuantityVolume Relationship: Avogadros Law

Gay-Lussacs law of combining volumes: At a given temperature and pressure the
volumes of gases that react with one another are ratios of small whole numbers.
Avogadros hypothesis: Equal volumes of gases at the same temperature and
pressure contain the same number of molecules.

Avogadros law: The volume of gas at a given temperature and pressure is
directly proportional to the number of moles of gas.
Mathematically:
V = constant n
We can show that 22.4 L of any gas at 0 C and 1 atmosphere contains
6.02 x 10
23
gas molecules.
FORWARD REFERENCES
Vapor pressure vs. temperature will be discussed in Ch. 13 (section 13.5).
Increasing entropy of gases with temperature as well as entropy of
gases vs. other states of matter will be discussed in Ch. 19 (section 19.3).

10.4 The Ideal-Gas Equation

(EOCQS 29-44 split)

Summarizing the gas laws:
Boyle: V o 1/P (constant n, T)
Charles: V o T (constant n, P)
Avogadro: V o n (constant P, T)
Combined: V o nT/P
Ideal gas equation: PV = nRT
constant or constant = =
T
V
T V
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 9

constant = = nR
T
PV
An ideal gas is a hypothetical gas whose P, V, and T behavior is
completely described by the ideal-gas equation.
R = gas constant = 0.08206 L-atm/mol-K
Other numerical values of R in various units are given in Table
10.2.
Define STP (standard temperature and pressure) = 0 C, 273.15 K, 1 atm.
The molar volume of 1 mol of an ideal gas at STP is 22.41 L.
Relating the Ideal-Gas Equation and the Gas Laws

If PV = nRT and n and T are constant, then PV is constant and we have Boyles
law.
Other laws can be generated similarly.
In general, if we have a gas under two sets of conditions, then
We often have a situation in which P, V, and T all change for a fixed number of
moles of gas.
For this set of circumstances,
Which gives

FORWARD REFERENCES
The ideal gas constant will be used in Ch. 14 in the Arrhenius equation (section
14.5).
The ideal gas constant will be used in Ch. 15 in conversions between K
c
and K
p

(section 15.2) and to relate Gibbs free energy with the equilibrium constant in Ch.
19 (section 19.7) as well as with the cell EMF in Ch. 20 (section 20.6).
2 2
2 2
1 1
1 1
T n
V P
T n
V P
=
2
2 2 1
1
1
T
V P
T
V P
=
Anderson - MCHS States of Matter AP Chem. Unit 03
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10.5 Further Applications of the Ideal-Gas Equation (EOCQS
45-58 split)
Gas Densities and Molar Mass
Density has units of mass over volume.
Rearranging the ideal-gas equation with M as molar mass we get



The molar mass of a gas can be determined as follows:
Volumes of Gases in Chemical Reactions

The ideal-gas equation relates P, V, and T to number of moles of gas.
The n can then be used in stoichiometric calculations.
FORWARD REFERENCES
Solubility of gases vs. temperature (Henrys law) will be covered in Ch. 13 (section
13.3).


10.6 Gas Mixtures and Partial Pressures (EOCQS 59-70 split)

Since gas molecules are so far apart, we can assume they behave
independently.
Dalton observed:
The total pressure of a mixture of gases equals the sum of the pressures
that each would exert if present alone.
Partial pressure is the pressure exerted by a particular component of a
gas mixture.
Daltons law of partial pressures: In a gas mixture the total pressure is given by
the sum of partial pressures of each component:
P
t
= P
1
+ P
2
+ P
3
+
RT
PM
d =
P
dRT
M =
RT
P
V
n
=
RT
PM
V
nM
=
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 11

V
RT
n
V
RT
n n n P
t t
= + + + = ) (
3 2 1

Each gas obeys the ideal gas equation.
Thus,


Partial Pressures and Mole Fractions
Let n
1
be the number of moles of gas 1 exerting a partial pressure P
1
, then
P
1
= X
1
P
t

Where X
1
is the mole fraction (n
1
/n
t
).
Note that a mole fraction is a dimensionless number.
Collecting Gases over Water

It is common to synthesize gases and collect them by displacing a volume of
water.

To calculate the amount of gas produced, we need to correct for the partial
pressure of the water:
P
total

= P
gas
+ P
water

The vapor pressure of water varies with temperature.
Values can be found in Appendix B.
FORWARD REFERENCES
Vapor pressure, volatility and temperature relationships will be introduced in Ch. 11
(section 11.5) and further applied to Raoults Law in Ch. 13 (section 13.5).
Aira mixture of gaseswill be discussed in Ch. 18 (section 18.1) and 22 (section
22.7).
10.7 Kinetic-Molecular Theory (EOCQS 71-82 all)

The kinetic-molecular theory was developed to explain gas behavior.
It is a theory of moving molecules.
Summary:
Gases consist of a large number of molecules in constant random motion.
The combined volume of all the molecules is negligible compared with
the volume of the container.
Intermolecular forces (forces between gas molecules) are negligible.
Energy can be transferred between molecules during collisions, but the
average kinetic energy is constant at constant temperature.
The collisions are perfectly elastic.
The average kinetic energy of the gas molecules is proportional to
the absolute temperature.
Kinetic-molecular theory gives us an understanding of pressure and
temperature on the molecular level.
The pressure of a gas results from the collisions with the walls of the
container.

Anderson - MCHS States of Matter AP Chem. Unit 03
Page 12

The magnitude of the pressure is determined by how often and how hard
the molecules strike.
The absolute temperature of a gas is a measure of the average kinetic energy.

Some molecules will have less kinetic energy or more kinetic
energy than the average (distribution).
There is a spread of individual energies of gas molecules in any sample
of gas.
As the temperature increases, the average kinetic energy of the gas
molecules increases.
As kinetic energy increases, the velocity of the gas molecules increases.
Root-mean-square (rms) speed, u, is the speed of a gas molecule
having average kinetic energy.
Average kinetic energy, c, is related to rms speed:
c = mu
2

where m = mass of the molecule.
Application to the Gas Laws
We can understand empirical observations of gas properties within the framework
of the kinetic-molecular theory.
Effect of an increase in volume (at constant temperature):
As volume increases at constant temperature, the average kinetic of the
gas remains constant.
Therefore, u is constant.
However, volume increases, so the gas molecules have to travel
further to hit the walls of the container.
Therefore, pressure decreases.
Effect of an increase in temperature (at constant volume):
If temperature increases at constant volume, the average kinetic energy
of the gas molecules increases.
There are more collisions with the container walls.
Therefore, u increases.
The change in momentum in each collision increases (molecules
strike harder).
Therefore, pressure increases.
FORWARD REFERENCES
The collision model in Ch. 14 (section 14.5) will be based on the kinetic-molecular
theory.
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 13

1
2
2
1
M
M
r
r
=
M
RT
u
3
=
10.8 Molecular Effusion and Diffusion (EOCQS 71-82all)

The average kinetic energy of a gas is related to its mass:
c = mu
2

Consider two gases at the same temperature: the lighter gas has a higher rms speed
than the heavier gas.

Mathematically:



The lower the molar mass, M, the higher the rms speed for that gas at a
constant temperature.
Two consequences of the dependence of molecular speeds on mass are:
Effusion is the escape of gas molecules through a tiny hole into an
evacuated space.
Diffusion is the spread of one substance throughout a space or
throughout a second substance.

Grahams Law of Effusion

The rate of effusion can be quantified.
Consider two gases with molar masses, M
1
and M
2
, and with effusion rates, r
1

and r
2
, respectively:
The relative rate of effusion is given by Grahams law:




Only those molecules which hit the small hole will escape through
it.
Therefore, the higher the rms speed the more likely that a gas molecule
will hit the hole.
We can show





1
2 1
2 2
1
M
M
u
u
r
r
= =
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 14

Diffusion and Mean Free Path

Diffusion is faster for light gas molecules.
Diffusion is significantly slower than the rms speed.
Diffusion is slowed by collisions of gas molecules with one another.
Consider someone opening a perfume bottle: It takes awhile to detect the
odor, but the average speed of the molecules at 25 C is about 515 m/s (1150
mi/hr).
The average distance traveled by a gas molecule between collisions is called
the mean free path.

At sea level, the mean free path for air molecules is about 6 x 10
6
cm.
FORWARD REFERENCES
Similar molar mass related issues (e.g., passing of particles of solute through
semipermeable membranes) for solutions will be discussed in Ch. 13 (section 13.5).
10.9 Real Gases: Deviations from Ideal Behavior
(EOCQS 83,85,88)

From the ideal gas equation:
For 1 mol of an ideal gas, PV/RT = 1 for all pressures.
In a real gas, PV/RT varies from 1 significantly.

The higher the pressure the more the deviation
from ideal behavior.
For 1 mol of an ideal gas, PV/RT = 1 for all temperatures.

As temperature increases, the gases behave more ideally.
The assumptions in the kinetic-molecular theory show where ideal gas
behavior breaks down:
The molecules of a gas have finite volume.
Molecules of a gas do attract each other.
As the pressure on a gas increases, the molecules are forced closer together.

As the molecules get closer together, the free space in which the
molecules can move gets smaller.
The smaller the container, the more of the total space the gas molecules
occupy.
Therefore, the higher the pressure, the less the gas resembles an ideal
gas.
As the gas molecules get closer together, the intermolecular distances
decrease.
The smaller the distance between gas molecules, the more likely that
attractive forces will develop between the molecules.

Therefore, the less the gas resembles an ideal gas.
n
RT
PV
=
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 15

|
|
.
|

\
|
2
2
V
a n
As temperature increases, the gas molecules move faster and further apart.
Also, higher temperatures mean more energy available to break
intermolecular forces.
As temperature increases, the negative departure from ideal-gas behavior
disappears.
The van der Waals Equation

We add two terms to the ideal gas equation to correct for
The volume of molecules:

For molecular attractions:


The correction terms generate the van der Waals equation:
where a and b are empirical constants that differ for each gas.
van der Waals constants for some common gases can be
found in Table 10.3.
To understand the effect of intermolecular forces on pressure, consider a molecule
that is about to strike the wall of the container.
The striking molecule is attracted by neighboring molecules.
Therefore, the impact on the wall is lessened.
Chapter 11. Intermolecular Forces,
Liquids, and Solids
Common Student Misconceptions
Students confuse intermolecular and intramolecular forces.
Students often do not appreciate how important information from earlier chapters
is for the understanding of concepts in this chapter.
Students have difficulty predicting the relative strength of intermolecular forces
involved in different materials.
Students are unaware that there can be intramolecular hydrogen bonding.
Iondipole interactions are technically interparticular forces.
Students confuse cohesion and adhesion.
Students do not realize that, under the right set of conditions, water also sublimes.
The term volatile is often used incorrectly, especially in the media.
Students often think that more viscous necessarily means more dense.
( ) nRT nb V
V
a n
P =
|
|
.
|

\
|
+
2
2
( ) nb V
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 16


Lecture Outline
11.1 A Molecular Comparison of Gases, Liquids, and Solids


(EOC QS 9,11)

Physical properties of substances are understood in terms of kinetic-molecular
theory:
Gases are highly compressible and assume the shape and volume of their
container.
Gas molecules are far apart and do not interact much with one another.

Liquids are almost incompressible, assume the shape but not the volume of
the container.
Liquids molecules are held together more closely than gas molecules but
not so rigidly that the molecules cannot slide past each other.
Solids are incompressible and have a definite shape and volume.
Solid molecules are packed closely together.
The molecules are so rigidly packed that they cannot easily slide
past each other.
Solids and liquids are condensed phases.
Solids with highly ordered structures are said to be crystalline.
Converting a gas into a liquid or solid requires the molecules to get closer to
each other.
We can accomplish this by cooling or compressing the gas.
Converting a solid into a liquid or gas requires the molecules to move further
apart.
We can accomplish this by heating or reducing the pressure on the gas.
The forces holding solids and liquids together are called intermolecular forces.
Physical properties of liquids and solids are due to intermolecular forces.
These are forces between molecules.
FORWARD REFERENCES
A comparison of phases in terms of entropy will be performed in Ch. 19 (section
19.3).


Anderson - MCHS States of Matter AP Chem. Unit 03
Page 17

11.2 Intermolecular Forces (EOC QS 13 27 split)
The attraction between molecules is an intermolecular force.
Intermolecular forces are much weaker than ionic or covalent bonds.
When a substance melts or boils, intermolecular forces are broken.
When a substances condenses, intermolecular forces are formed.
Boiling points reflect intermolecular force strength.
A high boiling point indicates strong attractive forces.
Melting points also reflect the strength of attractive forces.
A high melting point indicates strong attractive forces.
van der Waals forces are the intermolecular forces that exist between neutral
molecules.
These include London dispersion forces, dipoledipole forces, and
hydrogen-bonding forces.
Iondipole interactions are important in solutions.
These are all weak (<15% as strong as a covalent or ionic bond)
electrostatic interactions.
Ion-Dipole Forces
An iondipole force is an interaction between an ion (e.g., Na+) and the partial
charge on the end of a polar molecule/dipole (e.g., water).
It is especially important for solutions of ionic substances in polar liquids.
Example: NaCl(aq)

DipoleDipole Forces
Dipoledipole forces exist between neutral polar molecules.
Polar molecules attract each other.
The partially positive end of one molecule attracts the partially negative
end of another.
Polar molecules need to be close together to form strong dipoledipole
interactions.
Dipoledipole forces are weaker than iondipole forces.
If two molecules have about the same mass and size, then dipoledipole forces
increase with increasing polarity.
For molecules of similar polarity, those with smaller volumes often have
greater dipoledipole attractions.


Anderson - MCHS States of Matter AP Chem. Unit 03
Page 18

London-Dispersion Forces
These are the weakest of all intermolecular forces.
It is possible for two adjacent neutral molecules to affect each other.
The nucleus of one molecule (or atom) attracts the electrons of the
adjacent molecule (or atom).
For an instant, the electron clouds become distorted.
In that instant a dipole is formed (called an instantaneous dipole).
One instantaneous dipole can induce another instantaneous dipole
in an adjacent molecule (or atom).
These two temporary dipoles attract each other.
The attraction is called the London dispersion force, or simply a
dispersion force.
London dispersion forces exist between all molecules.


What affects the strength of a dispersion force?
Molecules must be very close together for these attractive forces to
occur.
Polarizability is the ease with which an electron distribution can be
deformed.
The larger the molecule (the greater the number of electrons) the
more polarizable it is.
London dispersion forces increase as molecular weight increases.
London dispersion forces depend on the shape of the molecule.
The greater the surface area available for contact, the greater the
dispersion forces.
London dispersion forces between spherical molecules are smaller
than those between more cylindrically shaped molecules.
Example: n-pentane vs. neopentane.








Anderson - MCHS States of Matter AP Chem. Unit 03
Page 19

Hydrogen Bonding
Experiments show that the boiling points of compounds with HF, HO, and
HN bonds are abnormally high.
Their intermolecular forces are abnormally strong.
Hydrogen bonding is a special type of intermolecular attraction.
This is a special case of dipoledipole interactions.
H-bonding requires:
H bonded to a small electronegative element (most important for
compounds of F, O, and N).
an unshared electron pair on a nearby small electronegative ion or
atom (usually F, O, or N on another molecule).
lement) lie
much closer to X than H.

bare proton to the X-.
Bond energies of hydrogen bonds vary from about 4 kJ/mol to 25
kJ/mol.
They are much weaker than ordinary chemical bonds.
Intermolecular and intramolecular hydrogen bonds have exceedingly
important biological significance.
They are important in stabilizing protein structure, in DNA structure and
function, etc.
An interesting consequence of H-bonding is that ice floats.
The molecules in solids are usually more closely packed than those in
liquids.
Therefore, solids are usually more dense than liquids.
Ice is ordered with an open structure to optimize H-bonding.
Water molecules in ice are arranged in an open, regular hexagon.
Each o+ H points towards a lone pair on O.
Therefore, ice is less dense than water.
Ice floats, so it forms an insulating layer on top of lakes, rivers, etc.
Therefore, aquatic life can survive in winter.
Water expands when it freezes.
Frozen water in pipes may cause them to break in cold weather.
Comparing Intermolecular Forces
Dispersion forces are found in all substances.
Their strength depends on molecular shapes and molecular weights.
Anderson - MCHS States of Matter AP Chem. Unit 03
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Dipoledipole forces add to the effect of dispersion forces.
They are found only in polar molecules.
H-bonding is a special case of dipoledipole interactions.
It is the strongest of the intermolecular forces involving neutral species.
H-bonding is most important for H compounds of N, O, and F.
If ions are involved, iondipole (if a dipole is present) and ionic bonding are
possible.
Iondipole interactions are stronger than H-bonds.
Keep in mind that ordinary ionic or covalent bonds are much stronger than
these interactions!
FORWARD REFERENCES
Molecular materials held together by intermolecular forces will be called soft
materials in Ch. 12.
Intermolecular forces between polymer chains and in liquid crystals will be
mentioned in Ch. 12 (sections 12.6 and 12.8).
Breaking of solutesolute and solventsolvent intermolecular forces and replacing
them with solutesolvent interactions will take place in the solution process (Ch.
13).
The binding between the substrate and the active site in the enzyme action thanks to
the intermolecular forces will be discussed in Ch. 14 (section 14.7).
Hydrogen bonding and the formation of hydrated hydronium ions will be discussed
in Ch. 16 (section 16.2).
Hydrogen bonding will be partially responsible for the relative weakness of HF
compared to the strength of other binary acids involving halides (section 16.10).
Hydrogen bonding and high heat capacity, high melting, and boiling points of water
will be mentioned again in Ch. 18 (section 18.5).
Intermolecular attractions in ice will be discussed in Ch. 19 (section 19.3).
Hydrogen bonding in alcohols will be discussed in Ch. 25 (section 25.5).
Hydrogen bonding in the o helix of a protein will be discussed in
Ch. 25 (section 25.9).
11.3 Some Properties of Liquids (EOC QS 29,31)

Viscosity
Viscosity is the resistance of a liquid to flow.
A liquid flows by sliding molecules over one another.
Viscosity depends on:
the attractive forces between molecules.
The stronger the intermolecular forces, the higher the viscosity.
the tendency of molecules to become entangled.
Viscosity increases as molecules become entangled with one
another.
Anderson - MCHS States of Matter AP Chem. Unit 03
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the temperature.
Viscosity usually decreases with an increase in temperature.
Surface Tension
Bulk molecules (those in the liquid) are equally attracted to their neighbors.
Surface molecules are only attracted inward towards the bulk molecules.
Therefore, surface molecules are packed more closely than bulk
molecules.
This causes the liquid to behave as if it had a skin.
Surface tension is the amount of energy required to increase the surface area of
a liquid by a unit amount.
Stronger intermolecular forces cause higher surface tension.
Water has a high surface tension (H-bonding)
Hg(l) has an even higher surface tension (there are very strong
metallic bonds between Hg atoms).
Cohesive and adhesive forces are at play.
Cohesive forces are intermolecular forces that bind molecules to one
another.
Adhesive forces are intermolecular forces that bind molecules to a
surface.
Illustrate this by looking at the meniscus in a tube filled with liquid.
The meniscus is the shape of the liquid surface.
If adhesive forces are greater than cohesive forces, the
liquid surface is attracted to its container more than the bulk molecules.
Therefore, the meniscus is U-shaped (e.g., water in glass).
If cohesive forces are greater than adhesive forces, the meniscus is
curved downwards (e.g., Hg(l) in glass)
Capillary action is the rise of liquids up very narrow tubes.
The liquid climbs until adhesive and cohesive forces are balanced by
gravity.
FORWARD REFERENCES
Viscosity of liquid crystals will be discussed in Ch. 12 (section 12.8).
Viscosity of organic compounds, such as polyhydroxyl alcohols,
will be mentioned in Ch. 25 (section 25.5).
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 22


11.4 Phase Changes (EOC QS 33 36 ALL, 37,39,41)

Phase changes are changes of state.
Matter in one state is converted into another state.
Sublimation: solid gas.
Melting or fusion: solid liquid.
Vaporization: liquid gas.
Deposition: gas solid.
Condensation: gas liquid.
Freezing: liquid solid.
Energy Changes Accompanying Phase Changes
Energy changes of the system for the above processes are:
melting or fusion: Hfus > 0 (endothermic).
The enthalpy of fusion is known as the heat of fusion.
vaporization: Hvap > 0 (endothermic).
The enthalpy of vaporization is known as the heat of vaporization.
sublimation: Hsub > 0 (endothermic).
The enthalpy of sublimation is called the heat of sublimation.
deposition: Hdep < 0 (exothermic).
condensation: Hcon < 0 (exothermic).
freezing: Hfre < 0 (exothermic).
Generally the heat of fusion (enthalpy of fusion) is less than heat of
vaporization.
It takes more energy to completely separate molecules than to partially
separate them.
All phase changes are possible under the right conditions (e.g., water sublimes
when snow disappears without forming puddles).
The following sequence is endothermic:
heat solid melt heat liquid boil heat gas
The following sequence is exothermic:
cool gas condense cool liquid freeze cool solid

Heating Curves
Plot of temperature change versus heat added is a heating curve.
During a phase change adding heat causes no temperature change.
Anderson - MCHS States of Matter AP Chem. Unit 03
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The added energy is used to break intermolecular bonds rather than
cause a temperature change.
These points are used to calculate Hfus and Hvap.
Supercooling: When a liquid is cooled below its freezing point and it still
remains a liquid.
Critical Temperature and Pressure
Gases may be liquefied by increasing the pressure at a suitable temperature.
Critical temperature is the highest temperature at which a substance can exist
as a liquid.
Critical pressure is the pressure required for liquefaction at this critical
temperature.
The greater the intermolecular forces, the easier it is to liquefy a
substance.
Thus the higher the critical temperature.
FORWARD REFERENCES
Supercritical fluids in green chemistry will be discussed in Ch. 18 (section 18.7).
Thermodynamics of phase changes will be further discussed throughout Ch. 19.
11.5 Vapor Pressure (EOC QS 43-49 ODD)

Explaining Vapor Pressure on the Molecular Level
Some of the molecules on the surface of a liquid have enough energy to escape
the attraction of the bulk liquid.
These molecules move into the gas phase.
As the number of molecules in the gas phase increases, some of the gas phase
molecules strike the surface and return to the liquid.
After some time the pressure of the gas will be constant.
A dynamic equilibrium has been established.
Dynamic equilibrium is a condition in which two opposing
processes occur simultaneously at equal rates.
In this case, it is the point when as many molecules escape the
surface as strike the surface.
Vapor pressure of a liquid is the pressure exerted by its vapor when the
liquid and vapor are in dynamic equilibrium.
The pressure of the vapor at this point is called the equilibrium
vapor pressure.


Anderson - MCHS States of Matter AP Chem. Unit 03
Page 24

Volatility, Vapor Pressure, and Temperature
If equilibrium is never established the vapor continues to form.
Eventually, the liquid evaporates to dryness.
Liquids that evaporate easily are said to be volatile.
The higher the temperature, the higher the average kinetic energy, the
faster the liquid evaporates.
Vapor Pressure and Boiling Point
Liquids boil when the external pressure at the liquid surface equals the vapor
pressure.
The normal boiling point is the boiling point at 760 mm Hg (1 atm).
The temperature of the boiling point increases as the external pressure
increases.
Two ways to get a liquid to boil increase temperature or decrease pressure.
Pressure cookers operate at high pressure.
At high pressure the boiling point of water is higher than at 1 atm.
Therefore, food is cooked at a higher temperature.
FORWARD REFERENCES
Vapor pressure reduction of the solvent in a solutiona colligative propertywill
be discussed in Ch. 13 (section 13.5).

11.6 Phase Diagrams (EOC QS 51 56 ALL)

A phase diagram is a plot of pressure vs. temperature summarizing all
equilibria between phases.
Phase diagrams tell us which phase will exist at a given temperature and
pressure.
Features of a phase diagram include:
vapor-pressure curve: generally as temperature increases, vapor pressure
increases.
critical point: critical temperature and pressure for the gas.
normal melting point: melting point at 1 atm.
triple point: temperature and pressure at which all three phases are
in equilibrium.
Any temperature and pressure combination not on a curve represents a
single phase.


Anderson - MCHS States of Matter AP Chem. Unit 03
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Phase Diagrams of H
2
O and CO
2

Water:
In general, an increase in pressure favors the more compact phase of the
material.
This is usually the solid.
Water is one of the few substances whose solid form is less dense than
the liquid form.
The melting point curve for water slopes to the left.
The triple point occurs at 0.0098 C and 4.58 mm Hg.
The normal melting (freezing) point is 0 C.
The normal boiling point is 100 C.
The critical point is 374 C and 218 atm.
Carbon Dioxide:

The normal sublimation p
sublimes, it does not melt.)
The critical point occurs at 31.1 C and 73 atm.
Freeze drying: Frozen food is placed in a low pressure (< 4.58
torr) chamber.
The ice sublimes.
FORWARD REFERENCES
Phase diagrams for a pure solvent and for a solution of a nonvolatile solute will be
discussed in Ch. 13 (section 13.5).
Phase equilibria at melting and boiling points will be further analyzed in Ch. 19.
11.7 Structures of Solids(EOC QS 57,59)

A crystalline solid has a well-ordered, definite arrangements of molecules,
atoms, or ions.
Examples are quartz, diamond, salt, and sugar.
The intermolecular forces are similar in strength.
Thus they tend to melt at specific temperatures.
In an amorphous solid, molecules, atoms or ions do not have an orderly
arrangement.
Examples are rubber and glass.
Amorphous solids have intermolecular forces that vary in strength.
Thus they tend to melt over a range of temperatures.


Anderson - MCHS States of Matter AP Chem. Unit 03
Page 26

Unit Cells
Crystalline solids have an ordered, repeating structure.
The smallest repeating unit in a crystal is a unit cell.
The unit cell is the smallest unit with all the symmetry of the entire
crystal.
The three-dimensional stacking of unit cells is the crystal lattice.
Each point in the lattice is a lattice point which represents an
identical environment within the solid.
There are three types of cubic unit cells.
Primitive cubic.
The lattice points are at the corners of a simple cube with each
atom shared by eight unit cells.
Body-centered cubic (bcc).
Lattice points occur at the corners of a cube and in addition there
is a lattice point in the center of the body of the cube. The corner
lattice points are shared by eight unit cells, and the center atom is
completely enclosed in one unit cell.
Face-centered cubic (fcc).
There are lattice points at the corners of a cube plus one lattice
point in the center of each face of the cube. Eight unit cells share
the corner lattice points and two unit cells share the face lattice
points.
The Crystal Structure of Sodium Chloride
It has a face-centered cubic lattice.
There are two equivalent ways of defining this unit cell:
Cl (larger) ions at the corners of the cell, or
Na+ (smaller) ions at the corners of the cell.
The cation to anion ratio in a unit cell is the same for the crystal.
In NaCl each unit cell contains the same number of Na+ and Cl ions.
Note that the unit cell for CaCl2 needs twice as many Cl ions as Ca2+ ions.

Close Packing of Spheres
Crystalline solids have structures that maximize the attractive forces between
particles.
Their particles can be modeled by spheres.
Each atom or ion is represented by a sphere.
Molecular crystals are formed by close packing of the molecules.
Anderson - MCHS States of Matter AP Chem. Unit 03
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Maximum intermolecular forces in crystals are achieved by the close packing
of spheres.
A crystal is built up by placing close packed layers of spheres on top of
each other.
There is only one place for the second layer of spheres.
There are two choices for the third layer of spheres:
The third layer eclipses the first (ABAB arrangement).
This is called hexagonal close packing (hcp).
The third layer is in a different position relative to the first
(ABCABC arrangement).
This is called cubic close packing (ccp).
Note that the unit cell of a ccp crystal is face-
centered cubic.
In both close-packed structures, each sphere is surrounded by 12 other s
pheres (6 in one plane, 3 above, and 3 below).
Coordination number is the number of spheres directly surrounding a
central sphere.
When spheres are packed as closely as possible, there are small spaces
between adjacent spheres (interstitial holes).
If unequally sized spheres are used, the smaller spheres are placed in the
interstitial holes.
For example: Li
2
O
The larger O
2
ions assume the cubic close-packed structure
with the smaller Li
+
ions in the holes.
FORWARD REFERENCES
Coordination numbers will be used in Ch. 23 for transition metal complexes.
11.8 Bonding in Solids(EOC QS 69 78 ALL)

The physical properties of crystalline solids depend on the:
attractive forces between particles and on
the arrangement of the particles.
Molecular Solids
Molecular solids consist of atoms or molecules held together by intermolecular
forces.
Weak intermolecular forces give rise to low melting points.
Intermolecular forces include dipoledipole, London dispersion and H-
bonds.
Anderson - MCHS States of Matter AP Chem. Unit 03
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Molecular solids are usually soft.
They are often gases or liquids are room temperature.
Efficient packing of molecules is important (since they are not regular
spheres).
Molecular solids show poor thermal and electrical conductivity.
Examples: Ar(s), CH
4
(s), CO
2
(s), sucrose.

Covalent-Network Solids
Covalent-network solids consist of atoms held together, in large networks or
chains, with covalent bonds.
They have much higher melting points and are much harder than molecular
solids.
This is a consequence of the strong covalent bonds that connect the
atoms.
Examples are diamond, graphite, quartz (SiO
2
), and silicon carbide (SiC).
In diamond:
each C atom has a coordination number of 4.
each C atom is tetrahedral.
there is a three-dimensional array of atoms.
Diamond is hard, and has a high melting point (3550C).
In graphite:
each C atom is arranged in a planar hexagonal ring.
layers of interconnected rings are placed on top of each other.
the distance between adjacent C atoms in the same layer is close
to that seen in benzene (1.42 vs. 1.395 in benzene).
electrons move in delocalized orbitals (good conductor).
the distance between layers is large (3.41 ).
the layers are held together by weak dispersion forces.
They slide easily past each other.
Graphite is a good lubricant.
Ionic Solids
Ionic solids consist of ions held together by ionic bonds.
They are hard, brittle and have high melting points.
Ions (spherical) are held together by electrostatic forces of attraction.
Recall:
The larger the charges (Q1, Q2) and smaller the distance (d) between ions, the
stronger the ionic bond.
Anderson - MCHS States of Matter AP Chem. Unit 03
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The structure of the ionic solid depends on the charges on the ions and on the
relative sizes of the atoms.
Examples of some ionic lattice types are:
NaCl structure.
Each ion has a coordination number of six.
It has a face-centered cubic lattice.
The cation to anion ratio is 1:1.
Other similar examples: LiF, KCl, AgCl, and CaO.
CsCl structure.
Cs+ has a coordination number of eight.
It is different from the NaCl structure (Cs+ is larger than Na+).
The cation to anion ratio is 1:1.
Zinc blende (ZnS) structure.
S
2
ions adopt a face-centered cubic arrangement.
Zn
2+
ions have a coordination number of four.
The S
2
ions are placed in a tetrahedron around the Zn
2+
ions.
Another example is CuCl.
Fluorite (CaF
2
) structure.
Ca
2+
ions are in a face-centered cubic arrangement.
There are twice as many F ions as Ca
2+
ions in each unit cell.
Other examples are BaCl
2
and PbF
2
.
Metallic Solids
Metallic solids consist entirely of metal atoms.
Metallic solids are soft or hard.
They have high melting points.
They show good electrical and thermal conductivity.
They are ductile and malleable.
Examples are all metallic elements (i.e., Al, Cu, Fe, Au)
Metallic solids have metal atoms in hexagonal close-packed, face-centered
cubic or body-centered cubic arrangements.
Thus the coordination number for each atom is either 8 or 12.
A problem that needs to be explained:
The bonding is too strong to be explained by London dispersion forces
and there are not enough electrons for covalent bonds.
Resolution:
The metal nuclei float in a sea of delocalized valence electrons.
Anderson - MCHS States of Matter AP Chem. Unit 03
Page 30

Metals conduct heat and electricity because the valence electrons are
delocalized and are mobile.

X-Ray Diffraction
When waves are passed through a narrow slit they are diffracted.
When waves are passed through a diffraction grating (many narrow slits in
parallel) they interact to form a diffraction pattern (areas of light and dark
bands).
Efficient diffraction occurs when the wavelength of light is close to the size of
the slits.
The spacing between layers in a crystal is 220 , which is the wavelength
range for X-rays.
X-ray diffraction (X-ray crystallography):
X-rays are passed through the crystal and are detected on a photographic
plate.
The photographic plate has one bright spot at the center (incident beam)
as well as a diffraction pattern.
Each close-packing arrangement produces a different diffraction pattern.
Knowing the diffraction pattern, we can calculate the positions of
the atoms required to produce that pattern.
We calculate the crystal structure based on a knowledge of the
diffraction pattern.
FORWARD REFERENCES
Classes of materials will be discussed throughout Ch. 12, [e.g., carbon nanotubes
(section 12.9)].
Perfectly crystalline solids will be mentioned in Ch. 19 (Third Law of
Thermodynamics).
Electrolysis of ionic salts will be further discussed in Ch. 20 (section 20.9).
Allotropic forms of carbon will be discussed in Ch. 22 (section 22.1).
Lubricating properties of silicate sheets will be mentioned in Ch. 22 (section 22.10).
Electron-sea model for metallic bonding as well as alloys will be
discussed in Ch. 23.