6 Gases

6.1 The states of matter

• Matter exists in only three states:
– Solid
– Liquid
– Gas
• The most stable state of a particular
substance can be changed by varying
the temperature and/or pressure
6.2 Describing gases
• Gases expand to occupy all of the
space of their container
• This implies that the individual gas
atoms or molecules are free to move
anywhere within their container
• Therefore the forces between them
must be very weak
6.2 Describing gases
• The defining characteristic of gases is
the pressure they exert
• The pressure (p) exerted by a gas is
dependent on:
– The amount of gas present (n)
– The volume in which it is contained (V)
– Temperature (T)
6.2 Describing gases
• Pressure (p)
– At any temperature above absolute zero,
atoms/molecules are always in motion
– At the molecular level, atoms/molecules
exert forces through never-ending
collisions with each other and with the
walls of their container
– Pressure is the collective result of these
collisions
6.2 Describing gases
– The atmosphere exerts pressure on the
Earth’s surface
– The pressure of the atmosphere can be
measured with a barometer
 6.2 Describing gases
– A manometer
measures the
difference in
pressures exerted
by two gases
6.2 Describing gases
– The SI unit for pressure is pascal (Pa)
– 1 Pa = 1 N m-2
– A number of non-SI units are used:
• 1 atm is the pressure that will support a
column of mercury 760 mm in height
• 1 atm = 1.01325 x 105 Pa
• 1 torr is the pressure exerted by a column of
mercury 1 mm in height
• 1 atm = 760 torr
• 1 bar = 105 Pa
 6.2 Describing gases
• The gas laws
– The atoms or molecules of a gas move freely to fill
whatever volume is available

– The volume occupied by a gas changes in response to

changes in pressure, temperature and amount of gas
 6.2 Describing gases
– Boyle’s Law
• Boyle investigated gases in a J-shaped tube

• Determined that volume was inversely proportional to

pressure
 6.2 Describing gases
– Charles’ Law
• Determined the volume of
a gas is directly
proportional
to its temperature

– Avogadro’s Law
• Gas volume is directly
proportional to the
amount of gas
6.2 Describing gases
• The ideal gas equation
– All four variables (p, V, T and n) can be
related using a single constant
– This is known as the gas constant (R)
– In SI units, R = 8.314 J mol-1 K-1
– pV = nRT
– This is known as the ideal gas equation,
because it describes the behaviour of an
ideal gas
 6.3 Molecular view of
gases
• As gases are characterised by rapid
motion of their constituent atoms or
molecules, the most important energy
component to consider is their kinetic
energy, Ekinetic
• The kinetic energy of an object is
given by the equation:
 6.3 Molecular view of
gases
• Molecular speeds
– A molecular beam
apparatus measures
the speeds of
molecules in a gas

– Molecules in a gas
have a distribution of
speeds
 6.3 Molecular view of
gases
• Speed and energy
– The energy of a molecule is related to its
speed
– At a given temperature, all gases have the
same molecular
kinetic energy
distribution
 6.3 Molecular view of
gases
• Average kinetic energy
– The most probable kinetic energy is not
the same as the average kinetic energy
– The average kinetic energy of gas
molecules depends on the temperature
of the gas
6.3 Molecular view of gases

• Ideal gases
– An ideal gas has the following two
characteristics:
• The volume occupied by the molecules of an
ideal gas is negligible compared with the
volume of its container.
• The energies generated by forces among
ideal gas molecules are negligible compared
with molecular kinetic energies. (Small gas
molecules are not attracted to one another)
6.3 Molecular view of gases
– How does an ideal gas behave?
• Consider how changes in V, T or n affect the
pressure, p
• In an ideal gas each molecule is independent of
all others
• This independence means that the total
pressure is the sum of the pressure created by
each individual molecule
– Let’s consider the effect of changing one
property while holding the other properties
constant
6.3 Molecular view of
gases
– Increasing the amount of gas:
• Pressure is directly proportional to the
amount of gas
• This agrees with the ideal gas equation
6.3 Molecular view of
gases
– Changing the volume of the gas:
• Pressure is inversely proportional to volume
• This agrees with the ideal gas equation
6.3 Molecular view of
gases
– Changing the temperature:
• Pressure is directly proportional to
temperature
• This is in agreement with the ideal gas
equation
 6.4 Additional gas
properties
• Determination of molar mass
– The ideal gas equation can be combined
with n = m/M to find the molar mass of
an unknown gas
– pV = nRT can be used to calculate how
many moles are in the sample
– This information can then be used to
determine the molar mass of the gas
 6.4 Additional gas
properties
• Gas density
– The density of a gas varies significantly
with the conditions
– The ideal gas equation and n = m/M can
be combined and rearranged to obtain
an equation for density:
6.4 Additional gas
properties
– The equation reveals three features of
gas density:
• The density of an ideal gas increases linearly
with pressure at fixed temperature
• The density of an ideal gas decreases
linearly with temperature at a fixed pressure
• The density of an ideal gas increases linearly
with molar mass at a given temperature and
pressure
– Gas density has a significant effect on
interactions between molecules of a gas
6.4 Additional gas
properties
 6.4 Additional gas
properties
• Rates of gas movement
– The temperature of a gas determines the
average speed of the gas molecules of
which it is comprised
– To state this dependence quantitatively:

• This is called the root-mean-square speed

 6.4 Additional gas
properties
– Effusion
• The movement of molecules escaping from a
container into a vacuum
 6.4 Additional gas
properties
– Diffusion
• The movement of one type of molecule
through molecules of another type
 6.5 Gas mixtures
• Gas behaviour
depends on the
number of gas atoms
or molecules but not on
their identity
 6.5 Gas mixtures
• Dalton’s law of partial pressures
– In a mixture of gases in which no chemical
reaction occurs, each gas contributes to the
total pressure the amount that it would exert if
the gas were present in the container by itself
 6.5 Gas mixtures
• Describing gas mixtures
– Mole fraction (X)
• The number of moles of a substance as a fraction of the
number of moles of all substances in the mixture

• The partial pressure of a component in a gas mixture is

its mole fraction multiplied by the total pressure
6.5 Gas mixtures
– When referring to lower concentrations in
a gas mixture, scientists use parts per
million (ppm) or parts per billion (ppb)
– Mole fractions is moles per mole
– ppm is moles per million moles
– ppb is moles per billion moles
– 1 ppm is a mole fraction of 10-6
– 1 ppb is a mole fraction of 10-9
6.6 Gas stoichiometry
• The principles of stoichiometry apply
equally to solids, liquids and gases
• No matter what phase substances are
in, their chemical behaviour can be
described in molecular terms
• Stoichiometric calculations always
require amounts in moles
– For gases, amounts in moles are usually
calculated from the ideal gas equation
6.6 Gas stoichiometry
 6.7 Intermolecular
forces
• The halogens
– Exist as diatomic molecules
– Although they have similar
covalent bonding, bromine
and iodine differ from
chlorine and fluorine in their
macroscopic physical
appearance and in their
molecular behaviour
 6.7 Intermolecular
forces
– When the average kinetic energy is large
enough, molecules remain separated from
and the substance is a gas
– When intermolecular attractive forces are
large enough, molecules remain close to one
another and the substance is a liquid or solid
6.7 Intermolecular forces
• Real gases
– The ideal gas model makes two
assumptions:
• A gas has negligible forces between its
constituent atoms or molecules
• Gas atoms or molecules have negligible
volumes
– Neither of these assumptions is true for a
real gas
 6.7 Intermolecular
forces
– How close do real gases come to ideal
behaviour?
 6.7 Intermolecular
forces

– The ideal gas model can still be used to

discuss the properties of real gases, as long
as conditions do not become too extreme
 6.7 Intermolecular
forces
• The van der Waals equation
– A modified ideal gas equation that accounts for
attractive forces and molecular volumes

– Adds two correction terms to the ideal gas

equation
– Each correction term includes a constant that has
a specific value for every gas
6.7 Intermolecular
forces
6.7 Intermolecular forces
• Melting and boiling points
– Can be used as indicators of the strengths
of intermolecular forces
– The boiling point is the temperature at
which the average kinetic energy of
molecular motion balances the attractive
energy of intermolecular attractions
– When the pressure is 1.013 x 105 Pa, that
temperature is the normal boiling point
6.7 Intermolecular forces
– The conversion of a liquid into a gas is
called vaporisation
– Condensation is the reverse process
– At temperatures below the freezing point,
the molecules become locked in place
and the liquid solidifies. When the
pressure is 1.013 x 105 Pa, that
temperature is the normal freezing point
– Boiling and melting points depend on the
strengths of intermolecular forces
6.7 Intermolecular
forces
6.8 Types of intermolecular
forces
• There are three general types:
– Dispersion forces
• The attractions between the negatively
charged electron clouds and the positively
charged nuclei of neighbouring molecules
– Dipolar forces
• The attractions between oppositely charged
ends of neighbouring molecules
– Hydrogen bonds
• Between the lone pair of electrons on N, O or
F atom and a hydrogen atom
 6.8 Types of
intermolecular forces
• Dispersion forces
– Exists because the electron clouds of molecules
can be distorted

– Dispersion forces are the net attractive forces

between molecules generated by all these induced
charge imbalances
 6.8 Types of
intermolecular forces
– The magnitude of dispersion forces depends
on how easy it is to distort the electron cloud
of a molecule
– This ease of distortion is called the
polarisability
 6.8 Types of
intermolecular forces
– Dispersion forces increase in strength
with the number or electrons
 6.8 Types of
intermolecular forces
– For molecules with comparable numbers of
electrons, the shape of the molecule makes
an important secondary contribution to the
magnitude of dispersion forces
 6.8 Types of
intermolecular forces
• Dipolar forces
6.8 Types of intermolecular
forces
• Hydrogen bonds
– There are two requirements:
• First, there must be an electron-deficient
hydrogen atom that can be attracted to an
electron pair
• Hydrogen atoms in O-H, F-H and N-H bonds
meet this requirement
• Second, there must be a highly electronegative
atom with an electron pair that can interact with
the electron-deficient hydrogen atom
 6.8 Types of
intermolecular forces
6.8 Types of intermolecular
forces
• Hydrogen bonds can form between
different molecules
• Molecules can form more than one
hydrogen bond (eg glycine)
• Hydrogen bonds can form within a
molecule (eg salicylic acid)
• Hydrogen bonding is particularly
important in biochemical systems
 6.8 Types of
intermolecular forces
• Binary hydrogen compounds
– It is both the strength and number of
hydrogen bonds that a binary hydrogen
compound can form which determines its
boiling point
 Summary
• The three most important states of
matter are solid, liquid and gas
• Gases occupy all of the space in
which they are contained
• The pressure exerted by a gas is due
to the collisions of rapidly moving gas
atoms or molecules with the walls of
the container
 Summary
• Boyle’s Law, Charles’ Law and
Avogadro’s Law describe the
relationships between volume and
pressure, volume and temperature,
and volume and amount of a gas
respectively
• The combination of these laws gives
the ideal gas equation, pV = nRT
 Summary
• In order to determine the kinetic
energy of a gas molecule, it is
necessary to measure the speed with
which it is moving
• All gases have an identical molecular
kinetic energy distribution
• Real gases approximate ideal
behaviour under certain conditions
 Summary
• The movement of gas molecules can
be described as either effusion or
diffusion
• Each gaseous component in a
mixture of ideal gases exerts a partial
pressure
• The mole fraction of a substance
equals the ratio of moles to the total
number of moles
 Summary
• Intermolecular forces are partially
responsible for the fact that real gases
do not exactly obey the ideal gas laws
• The van der Waals equation for a real
gas makes corrections for the volume of
the gas molecules and for the attractive
force between them
• Melting and boiling points give good
indications of the strength of
intermolecular forces
 Summary
• There are three general types of
intermolecular forces:
– Dispersion forces
– Dipolar forces
– Hydrogen bonds