GENERAL CHEMISTRY

Chapter 4
Gas, Intermolecular Forces, Liquids,
and Solids

Dr. Huỳnh Kỳ Phương Hạ

Office: 112 B2 Building
Phone: 38650484
Email: hkpha@hcmut.edu.vn
Gases You Have Encountered
Characteristics of Gases
 Gases always form homogeneous mixtures
with other gases
 Gases are highly compressible and occupy
the full volume of their containers. (Chapter 1)
 When a gas is subjected to pressure, its
volume decreases.
.
Pressure

• Pressure is the force acting on an object per unit area:

F
P
A
• Gravity exerts a force on the earth’s atmosphere
• A column of air 1 m2 in cross section exerts a force of 105
N.
• The pressure of a 1 m2 column of air is 100 kPa.
• SI Units: 1 N = 1 kg.m/s2; 1 Pa = 1 N/m2.
Atmosphere Pressure and The Barometer
 If a tube is inserted into a container of mercury
open to the atmosphere, the mercury will rise
760 mm up the tube.
 Atmospheric pressure is measured with a
barometer.
 Standard atmospheric pressure is the pressure
required to support 760 mm of Hg in a column.
 Units: 1 atm = 760 mmHg = 760 torr = 1.01325
 105 Pa = 101.325 kPa.
Class Guided Practice Problem
 (a) Convert 0.527 atm to torr
 (b) Convert 760 torr to kPa

Class Practice Problem

 (c) Convert 147.2 kPa to (1) atm and (2) torr
Atmosphere Pressure and The
Manometer
• The pressures of gases not open
to the atmosphere are measured
in manometers.
• A manometer consists of a bulb
of gas attached to a U-tube
containing Hg:
– If Pgas < Patm then Pgas + Ph2 = Patm.
– If Pgas > Patm then Pgas = Patm + Ph2.
(See example problem 10.2)
Defining States of Gases

• Gas experiments revealed that four variables will affect

the state of a gas:
• Temperature, T
• Volume, V
• Pressure, P
• Quantity of gas present, n (moles)
• These variables are related through equations know as the
gas laws.
The Ideal Gas Equation

• Consider the three gas laws.

1
V  (constant n, T )
• Boyle’s Law: P

• Charles’s Law: V  T (constant n, P)

• Avogadro’s Law: V  n (constant P, T )
• We can combine these into a general gas law:
nT
V
P
The Gas Laws: Boyle’s Law
The Pressure-Volume Relationship:
 Weather balloons are used as a practical consequence
to the relationship between pressure and volume of a
gas.
 As the weather balloon ascends, the volume increases.
 As the weather balloon gets further from the earth’s
surface, the atmospheric pressure decreases.
 Boyle’s Law: the volume of a fixed quantity of gas is
inversely proportional to its pressure.
 Boyle used a manometer to carry out the
experiment.
Boyle’s Law
The Pressure-Volume Relationship

• Mathematically:
1
V  constant  PV  constant
P

• A plot of V versus P is a hyperbola.

• Similarly, a plot of V versus 1/P must be a straight line
passing through the origin.
• The Value of the constant depends on the temperature
and quantity of gas in the sample.
Charles’s Law
The Temperature-Volume Relationship:
• We know that hot air balloons expand when they are
heated.
• Charles’s Law: the volume of a fixed quantity of gas at
constant pressure increases as the temperature increases.
• Mathematically:
V
V  constant  T  constant
T
Plotting Charles’s Law
 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.
 Note the value of the constant reflects the
assumptions: amount of gas and pressure.
All gases will solidify or liquefy before reaching zero volume.
 Avogadro’s Law
The Quantity-Volume Relationship:
• Gay-Lussac’s Law of combining volumes: at a given
temperature and pressure, the volumes of gases which
react are ratios of small whole numbers.
Avogadro’s Law
 Avogadro’s Hypothesis: equal volumes of
gas at the same temperature and pressure
will contain the same number of
molecules.
 Avogadro’s Law: the volume of gas at a
given temperature and pressure is directly
proportional to the number of moles of
gas.
Expressing Avogadro’s Law
 Mathematically:
V  constant  n
 We can show that 22.4 L of any gas at 0C
contain 6.02  1023 gas molecules.
The Ideal Gas Constant
• If R is the constant of proportionality (called the gas
constant), then
 nT 
V  R 
 P
• The ideal gas equation is:

PV  nRT
L  atm J
R  0.08206  8.314
mol  K mol  K
 Applying The Ideal Gas Equation

• We define STP (standard temperature and pressure) =

0C, 273.15 K, 1 atm.
• Volume of 1 mol of gas at STP is:
nRT 1 mol 0.08206 L·atm/mol·K  273.15 K 
V   22.41 L
P 1.000 atm
 Class Guided Practice Problem

• For an ideal gas, calculate the following quantities: (a)

the pressure of the gas if 1.04 mol occupies 21.8 L at 25
o
C; (b) the volume occupied by 6.72 x 10-3 mol at 265 oC
and pressure of 23.0 torr;
Class Practice Problem
• (c) the number of moles in 1.50 L at 37 oC and 725 torr;
(d) the temperature at which 0.270 mol occupies 15.0 L
at 2.54 atm.
Relating the Ideal-Gas Equation and the
Gas Laws
 If PV = nRT and n and T are constant, then PV =
constant and we have Boyle’s law.
 Other laws can be generated similarly.
 In general, if we have a gas under two sets of
conditions, then

P1V1 P2V2

n1T1 n2T2
 Class Guided Practice Problem

• A sample of argon gas is confined to a 1.00-L tank at

27.0 oC and 1 atm. The gas is allowed to expand into a
larger vessel. Upon expansion, the temperature of the gas
drops to 15.0 oC, and the pressure drops to 655 torr.
What is the final volume of the gas?

Two ways to work this problem.

 Molar Mass
• Density has units of mass over volume.
• Rearranging the ideal-gas equation with M as molar mass
we get PV  nRT
n P

V RT
nM PM
d 
V RT
 Gas Densities
• The molar mass of a gas can be determined as follows:

dRT
M
P
.
 Class Guided Practice Problem

• What is the density of carbon tetrachloride vapor at 714

torr and 125 oC?
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
 Class Guided Practice Problem

• The safety air bags in automobiles are inflated by

nitrogen gas generated by the rapid decomposition of
sodium azide, NaN3:
2 NaN3(s)  2 Na(s) + 3N2(g)
If an air bag has a volume of 36 L and is filled with
nitrogen gas at a pressure of 1.15 atm at a temperature of
26 oC, how many grams of NaN3 must be decomposed?
 Gas Mixtures and Partial Pressures
 Since gas molecules are so far apart, we can
assume they behave independently.
 Dalton’s Law: in a gas mixture the total pressure is
total  P1  P2  P3  
given by the Psum of partial pressures of each
component:

 RT 
  niideal
Each gas obeysPithe  gas equation:
V 

 RT 
 CombiningPtotal  n1  n2  n3    
the equations we get:
V 
Collecting Gases over Water
 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:

Ptotal  Pgas  Pwater

 Class Guided Practice Problem
• A gaseous mixture made form 6.00g O2 and 9.00g CH4 is
placed in a 15.0-L vessel at 0 oC. What is the total
pressure in the vessel?
 Kinetic Molecular Theory
• Theory developed to explain gas behavior.
• Theory of moving molecules.
• Assumptions:
– Gases consist of a large number of molecules in constant
random motion.
– Volume of individual molecules negligible compared to
volume of container.
– Intermolecular forces (forces between gas molecules)
negligible.
 Kinetic Molecular Theory
• Assumptions:
– Energy can be transferred between molecules, but total kinetic
energy is constant at constant temperature.
– Average kinetic energy of molecules is proportional to
temperature.
• Kinetic molecular theory gives us an understanding of
pressure and temperature on the molecular level.
• Pressure of a gas results from the number of collisions
per unit time on the walls of container.
 Kinetic Molecular Theory
 Magnitude of pressure
given by how often
and how hard the
molecules strike.
 Gas molecules have
an average kinetic
energy.
 Each molecule has a
different energy.
 Kinetic Molecular Theory

• As kinetic energy increases, the velocity of the gas

molecules increases.
• Root mean square speed, u, is the speed of a gas molecule
having average kinetic energy.
• Average kinetic energy, , is related to root mean square
speed:
  mu1
2
2
 Application to Gas Laws
• 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.
• If temperature increases at constant volume, the average
kinetic energy of the gas molecules increases. Therefore,
there are more collisions with the container walls and the
pressure increases.
 Real Gases: Deviations from Ideal
Behavior

• From the ideal gas equation, we have

PV
n
RT

• For 1 mol of 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.
 Real Gases: Deviations from Ideal
Behavior
• From the ideal gas equation, we have
PV
n
RT
• For 1 mol of gas, PV/RT = 1 for all temperatures.
• As temperature increases, the gases behave more ideally.
• The assumptions in 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
• .
 Real Gases: Deviations from Ideal
Behavior

• As the pressure on a gas increases, the molecules are

forced closer together.
• As the molecules get closer together, the volume of the
container gets smaller.
• The smaller the container, the more space the gas
molecules begin to occupy.
• Therefore, the higher the pressure, the less the gas
resembles an ideal gas.
Real Gases: Deviations from Ideal
Behavior

• As the gas
molecules get
closer together,
the smaller the
intermolecular
distance.
 Real Gases: Deviations from Ideal
Behavior

• The smaller the distance between gas molecules, the

more likely attractive forces will develop between the
molecules.
• Therefore, the less the gas resembles and ideal gas.
• As temperature increases, the gas molecules move faster
and further apart.
• Also, higher temperatures mean more energy available to
break intermolecular forces.
Real Gases: Deviations from Ideal
Behavior

• Therefore, the higher the

temperature, the more ideal the
gas.
 The van der Waals Equation
• We add two terms to the ideal gas equation one to correct
for volume of molecules and the other to correct for
intermolecular attractions
• The correction terms generate the van der Waals
equation: 2
nRT n a
P  2
V  nb V
where a and b are empirical constants.
The van der Waals Equation
2
nRT n a
P  2
V  nb V

Corrects for Corrects for

molecular volume molecular attraction

 n2a 
 P  2 V  nb   nRT
 V 
 Viscosity in Liquids
• Viscosity is the resistance of a liquid to flow.
• A liquid flows by sliding molecules over each other.
• Viscosity depends on:
• The attractive forces between molecules:
– Stronger the intermolecular forces, the higher the viscosity.
• The temperature:
– Higher temperatures tend to decrease the viscosity.
• The tendency of molecules to become entangled:
– tangled molecules increases the viscosity
 Trends in the Viscosities of
Hydrocarbons

Notice that as molecular weight increases, viscosity increases.

Surface Tension
• Water tends to “bead up” on
waxy surfaces.
• Beading is due to an
imbalance of intermolecular
forces at the surface of the
liquid.
• The Inward force causes the
molecules to pack closer at
the surface (forming a skin).
• A measure of inward forces
that must be overcome to
expand the surface area of a
liquid is termed surface
tension.
 Surface Tension in Liquids
• Surface tension is the amount of energy needed to
increase the surface area of a liquid by 1 unit area.
• Surface tension is affected by intermolecular forces.
• Strong intermolecular forces results in a higher surface
tension.
– Water has high surface tension (H-bonding).
– Hg has even higher surface tension (metallic bonds).
– Metallic bonds form when by metal to metal bonding.
– Cohesive and adhesive forces are intermolecular forces.
• Capillary Action: When a narrow glass tube is placed in
water, the meniscus pulls the water up the tube.
 Phase Changes
• Phase changes are changes of state (i.e., matter in one
state is converted into another state)
• Sublimation: solid  gas.
• Vaporization: liquid  gas.
• Melting or fusion: solid  liquid.
• Deposition: gas  solid.
• Condensation: gas  liquid.
• Freezing: liquid  solid.
Energy Trend in Phase
Changes
 Energy Changes Accompanying
Phase Changes
• Sublimation: Hsub > 0 (endothermic).
• Vaporization: Hvap > 0 (endothermic).
• Heat of Vaporization
• Melting or Fusion: Hfus > 0 (endothermic).
• Heat of fusion
• Deposition: Hdep < 0 (exothermic).
• Condensation: Hcon < 0 (exothermic).
• Freezing: Hfre < 0 (exothermic).
 Phase Changes
• Generally heat of fusion (enthalpy of fusion) is
less than heat of vaporization:
– it takes more energy to completely separate molecules,
than partially separate them.
• All phase changes are possible under the right
conditions
Heating Curves
 Critical Temperature and
Pressure
• Gases liquefied by increasing pressure at some
temperature.
• Critical temperature: the minimum temperature for
liquefaction of a gas using pressure.
• Critical pressure: pressure required for liquefaction.
 Vapor Pressure
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
at the vapor pressure.
• This is called an equilibrium vapor pressure.
 Vapor Pressure Cont.
Explaining Vapor Pressure on the
Molecular Level
• Dynamic Equilibrium: the point when as many molecules
escape the surface as strike the surface.
• Vapor pressure is the pressure exerted when the liquid
and vapor are in dynamic equilibrium.
• If equilibrium is never established then vapors continues
to form.
• Eventually, the liquid evaporates to dryness.
• Volatile substances evaporate rapidly.
• The Higher the temperature, the faster the liquid
evaporates.
 Vapor Pressure
Volatility, Vapor Pressure, and Temperature
 Phase Diagrams
• Phase diagram: A plot of pressure vs. temperature
showing all equilibria between phases.
• Given a temperature and pressure, phase diagrams tell us
which phase will exist.
• Any temperature and pressure combination not on a
curve represents a single phase.
 Features of a Phase Diagram
• Triple point: temperature and pressure at which all three
phases are in equilibrium.
• Vapor-pressure curve: generally as pressure increases,
temperature increases.
• Critical point: critical temperature and pressure for the
gas.
• Melting point curve: as pressure increases, the solid
phase is favored if the solid is more dense than the liquid.
• Normal melting point: melting point at 1 atm.
Phase Diagram Example
Phase Diagrams of H2O and CO2

Notice that the line separating the liquid and gas phases
end rather than continuing to infinite pressure and
temperature. (?)
 Reading a Phase Diagrams
• Water:
• The melting point curve slopes to the left because ice is less
dense than water.
• Triple point occurs at 0.0098C and 4.58 mmHg.
• Normal melting (freezing) point is 0C.
• Normal boiling point is 100C.
• Critical point is 374C and 218 atm.
• Carbon Dioxide:
• Triple point occurs at -56.4C and 5.11 atm.
• Normal sublimation point is -78.5C. (At 1 atm CO2 sublimes
it does not melt.)
• Critical point occurs at 31.1C and 73 atm.
 Structures of Solids
• Crystalline solid: well-ordered, definite arrangements of
molecules, atoms or ions.
• Crystals have an ordered, repeated structure.
• The smallest repeating unit in a crystal is a unit cell.
• Unit cell is the smallest unit with all the symmetry of the
entire crystal.
• Three-dimensional stacking of unit cells is the crystal
lattice.
• Amorphous solid: no definite arrangement of molecules,
atoms, or ions (i.e., lack well-defined structures or
shapes).
• Amorphous solids vary in their melting points.
Structures of Solids
Unit Cells

The smallest repeating unit that shows

the symmetry of the pattern is called the
unit cell.
 Types of Unit Cells
• Primitive Cubic
• Body-centered Cubic (BCC)
• Face-centered Cubic (BCC)
• Hexagonal Close Pack (HCP)
• Rhombohedral
• Cubic Diamond
 Common Types of Unit Cells
• Three common types of unit cell.
• Primitive cubic, atoms at the corners of a simple cube
– each atom shared by 8 unit cells;
• Body-centered cubic (bcc), atoms at the corners of a cube
plus one in the center of the body of the cube,
– corner atoms shared by 8 unit cells, center atom completely
enclosed in one unit cell;
• Face-centered cubic (fcc), atoms at the corners of a cube
plus one atom in the center of each face of the cube,
– corner atoms shared by 8 unit cells, face atoms shared by 2
unit cells.
Unit Cells
Unit Cells
Table showing Atom Fractions in
Unit Cells
 Problem Solving

Determine the number of NaCl ions

in a unit cell?
 Structures of Solids
The Crystal Structure of Sodium
Chloride
• Two equivalent ways of defining 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 same number of
Na+ and Cl- ions.
• Note the unit cell for CaCl2 needs twice as many Cl- ions
as Ca2+ ions.
Crystal Structure of NaCl
Closer View of a NaCl Unit Cell
 Structures of Crystalline Solids
• Crystalline solids have structures that maximize
intermolecular forces between particles.
• These particles can be represent by spheres
• Atoms and ions are spheres.
• Molecular crystals are formed by close packing of the
molecules.
• We rationalize maximum intermolecular force in a crystal
by the close packing of spheres.
• The spaces between spheres are called interstitial.
• A crystal is built up by placing close packed layers of
spheres on top of each other.
 Packing of Spheres
• A crystal is built up by placing close packed layers of
spheres on top of each other.
• There are two choices for the third layer of spheres:
• Third layer eclipses the first (ABAB arrangement). This is
called hexagonal close packing (hcp);
• Third layer is in a different position relative to the first
(ABCABC arrangement). This is called cubic close packing
(ccp).
 Bonding in Solids
• There are four types of solid:
• Molecular (formed from molecules) - usually soft with low
melting points and poor conductivity.
• Covalent network (formed from atoms) - very hard with
very high melting points and poor conductivity.
• Ions (formed form ions) - hard, brittle, high melting points
and poor conductivity.
• Metallic (formed from metal atoms) - soft or hard, high
melting points, good conductivity, malleable and ductile.
Types of Crystalline Solids