Gases (Chapter 10)

• Rather than considering the atomic Component Symbol Volume

N2
nature of matter we can classify it Nitrogen

Oxygen O2
78.084%

20.947%
based on the bulk property: Argon Ar 0.934%
99.998%

gaseous, liquid or solid. Carbon Dioxide CO2 0.033%

• Gases are the most easily Neon Ne 18.2 parts per million

understood form of matter (we Helium He 5.2 parts per million

shall see why). Krypton

Sulfur dioxide
Kr
SO2
1.1 parts per million

1.0 parts per million

Air is an example of a complex mixture of gases: Methane CH4 2.0 parts per million
gases form homogeneous mixtures regardless
of identities or proportions (unlike liquids and Hydrogen H2 0.5 parts per million

solids). Nitrous Oxide N2O 0.5 parts per million

Gases expand to fill any container, and are highly Xenon Xe 0.09 parts per million
compressible (unlike liquids and solids) Ozone O3 0.07 parts per million

These characteristics arise because Nitrogen dioxide NO2 0.02 parts per million

the molecules of gas are very far Iodine I2 0.01 parts per million

apart and don’t (mostly) interact. Carbon monoxide CO

NH3
trace

Different gases thus behave Ammonia trace

similarly.
 Pressure
• Pressure is the force that acts on a given area (P=F/A).
• Gravity on earth exerts a pressure on the atmosphere:
atmospheric pressure.
• We can evaluate this by calculating the force due to
acceleration (by gravity) of a 1m2 column of air extending
through the atmosphere (this has a mass of ~10,000kg).

F  m.a
F  10,000kg  9.8m / s 2  100,000kgm / s 2
1  105 N This unit is a Newton (N)
P  F/A  1  105
N / m 2

1m 2
This unit is a Pascal (Pa)
 Units of Pressure
S.I. unit of pressure is the N/m2, given the name Pascal (Pa).
A related unit is the bar (1x105 Pa) used because atmospheric
pressure is ~ 1x105 Pa (100 kPa, or 1bar).
Torricelli (a student of Galileo) was the first to recognise that the
atmosphere had weight, and measured pressure using a barometer
Standard atmospheric pressure was thus defined
as the pressure sufficient to support a mercury
column of 760mm (units of mmHg, or torr).
Another popular unit was thus introduced to
simplify things, the atmosphere (atm =
760mmHg).
 Pressure
• Atmospheric pressure and relationship between units
1 atm = 760 mmHg = 760 torr = 101.325kPa = 1.01325 bar)
Measuring Pressure: the manometer

Exercise:
On a certain day a barometer gives the atmospheric pressure as 764.7 torr. If a
metre stick is used to measure a height of 136.4mm in the open arm, and
103.8mm in the gas arm of a manometer, what is the pressure of the gas sample?
(give in torr, atm, kPa and bar).
 Result
 Difference in height is 32.6 mm. Gas inside
has greater pressure than prevailing
atmospheric pressure: 764.7 + 32.6 mmHg =
797.3 mmHg (Torr)
 Convert to atm: divide by 760 = 1.049 atm
 Convert to kPa: multiply by 101.325 = 106.3
kPa
 Convert to bar: divide by 100 = 1.063 bar
 Gas Laws
• A large number of experiments have determined that 4
variables are sufficient to define the physical condition (or
state) of a gas: the gas laws.
Boyle’s Law, Charles’ Law, Avogadro’s hypothesis

Robert Boyle: (1627-1691) the first modern chemist, known as

the father of chemistry.
His 1661 book The Sceptical Chymist marks the introduction of
the scientific method, a definition of elements and compounds
and a refutation of alchemy and magic potions.
Boyle biography
 Boyle’s Law
• Boyle investigated the variation of the volume occupied by a
gas as the pressure exerted upon it was altered and noted that
the volume of a fixed quantity of gas, at constant temperature
is inversely proportional to the pressure
1
V  constant  or PV  constant
p
 Charles’ Law
• A century later, a French scientist, Jacques Charles discovered that the
volume of a fixed amount of gas, as constant pressure, is proportional
to the absolute temperature. Cool a balloon, or a sealed plastic bottle, to
verify this!

V
V  constant  T or  constant
T
It was recognised (by
William Thomson, Lord Kelvin, a
Belfast born physicist) that if the
graph was extrapolated to zero
volume, an absolute zero of -
273.15 oC is obtained.
 Avogadro’s Law
• Relationship between quantity of gas and volume established by
Gay-Lussac (balloon science!) and Avogadro in the 19th Century.
Result was Avogadro’s hypothesis: equal volumes of gases at the
same temperature and pressure contain equal numbers of
molecules
Experiments show that 22.4L of gas at 0oC and 1atm
(STP), or 24.8L of gas at 298.15 K and 1 bar (SATP),
contains 6.022 x 1023 molecules (Avogadro’s number, NA)
Avogadro’s law: volume of gas at constant temperature and
pressure is proportional to the number of moles of gas (n)

V  constant  n Remember:
1 mole = Avogadro’s
number of objects
 Putting it all together
1
V  , V  T, V  n Boyle, Charles, Avogadro
P
nT
V Combine
P
 nT  Call proportionality constant R
V  R  (gas constant)
 P 
PV  nRT Ideal Gas Equation
 A note on units and dimensional analysis
SI unit for R is J/mol.K or m3.Pa/mol.K (R=8.315 of these units)
Need to use the units of Pa for pressure and m3(=1000L) for volume in any
calculation.

Alternatively you can use units of kPa and L.

If you wish to use atm and L (as in USA and Textbook) R=0.0826
L.atm/mol/K.

Always use absolute temperature scale (K)

 Exercises

• What is the volume of 1 mole of an ideal gas

under standard temperature and pressure (STP)?
• How many moles (g) of CO2 is liberated into a
250mL flask when a pressure of 1.3atm is found
upon heating calcium carbonate to 31oC?
• If a metal cylinder holds 50L of oxygen at
18.5atm and 21oC, what volume will the gas
occupy at 1atm and same T?
 More Exercises
If the pressure of a gas in an aerosol can is 1.5atm at 21 oC, what
would the pressure be if can is heated to 450oC?

What is the density of carbon tetrachloride vapour at 714torr

and 125oC?

Gases in chemical reactions

See student activities

If an air bag has a volume of 36L and is to be filled with nitrogen

gas at a pressure of 1.15atm and 26oC, how many grams of NaN3
must be decomposed?
 Gas mixtures
• Dalton’s Law of partial pressures
The total pressure of a mixture of gases equals the
sum of the pressures that each would exert if it
were present alone
PT=P1+P2+P3+….Pn

Exercise: A gaseous mixture is made from 6.00g oxygen and

9.00g methane placed in a 15L vessel at 0oC. What is the partial
pressure of each gas and the total pressure in the vessel?
 Aside: A wronged chemist?

John Dalton, is credited with the formulation of the

atomic theory. This was disputed by William
Higgins, an Irish chemist from Colloney, Sligo,
who claimed to have been the first to postulate the
theory in his book Comparative view of the
phlogistic and anti-phlogistic theories (1789) a
work very critical of the Galway chemist Richard
Kirwan.
(Atkinson, E. R. The Atomic Hypothesis of William Higgins, J. Chem. Ed. 1940, 17(1), 3-11).
 Mole Fractions
• The ratio n1/nT is called the mole fraction (denoted x1), a
dimensionless number between 0 and 1.
P1 n1RT / V n1
 
PT nT RT / V nT
 n1 
P1    PT
 nT 
Mole fraction of N2 in air is 0.78, therefore if the total
barometric pressure is 760 torr, the partial pressure of N 2 is
(0.78)(760) = 590 torr.
 Kinetic –Molecular Theory
Theory describing why gas laws are obeyed (explains both pressure and
temperature of gases on a molecular level).
• Complete form of theory, developed over 100 years or so, published by
Clausius in 1857.
 Gases consist of large numbers of molecules that are in continuous,
random motion
 Volume of all molecules of the gas is negligible, as are
attractive/repulsive interactions
 Interactions are brief, through elastic collisions (average kinetic energy
does not change)
 Average kinetic energy of molecules is proportional to T, and all gases
have the same average kinetic energy at any given T.

Because each molecule of gas will have an individual kinetic energy, and thus
individual speed, the speed of molecules in the gas phase is usually characterised
by the root-mean-squared (rms) speed, u,(not the same though similar to the
average speed). Average kinetic energy є = ½mu2
 Application to Gas Laws
• Increasing V at constant T:
Constant T means that u is unchanged.
But if V is increased the likelihood of
collision with the walls decreases,
thus the pressure decreases (Boyle’s
Law)
• Increasing T at constant V:
Increasing T increases u, increasing
collisional frequency with the walls,
thus the pressure increases (Ideal Gas
Equation).
 Molecular speeds and mass
• The average kinetic energy of gases has a specific value at
a given temperature. The rms speed of gas composed of
light particles, He, is higher than that for heavier particles,
Ne, at the same temperature.
• Can derive an expression for the rms speed (from kinetic
theory)

3RT
u M is the molar mass
M See student activities

This gives rise to interesting

consequences: effusion
 Effusion
• Thomas Graham (1846)
discovered that effusion is
inversely proportional to the
square root of molar mass.

r1 M2

r2 M1
Derived from comparison
of rms speeds
REAL GASES
Deviations from ideal gas law
WHY?
1. Molecules have volume
2. Molecules have attractive forces
(intermolecular)
1. V-nb
2. -a(n/V)2

Van der Waals Equation of State

2
nRT n
P  a 
V  nb V 
 Van der Waal’s constants
van der Waals Coefficients
Gas a (Pa m3) b(m3/mol)
Helium 3.46 x 10-3 23.71 x 10-6
Neon 2.12 x 10-2 17.10 x 10-6
Hydrogen 2.45 x 10-2 26.61 x 10-6
Carbon dioxide 3.96 x 10-1 42.69 x 10-6
Water vapor 5.47 x 10-1 30.52 x 10-6

a correlates with boiling point (see later)

b can be used to estimate molecular radii