4.

0 MATTER
4.1 GASES
CHARACTERISTICS OF GASES
- A gas assumes the shape and volume of its container
- Gases are readily compressible, the volume of a gas
can be altered significantly (expand or contract) by
changing the applied external force or temperature
- Gases have relatively low viscosities and can flow
freely. Diffusion of gases occurs from a region of
higher concentration to a region of lower
concentration
- Most gases have relatively low densities under
normal conditions
- Gases are miscible and form a homogenous mixture
when confined in a container
KINETICS THEORY OF GASES
- Gases are made up of a large number of tiny
particles negligible volume, spaced far apart
- There are no attractive or repulsive forces between
the particles
- The particles of a gas are in a state of continuous
random motion with a distribution of speeds
- The rapidly moving particles collide with each other
and with the walls of the container. The collisions are
perfectly elastic with no loss of kinetic energy
- The average kinetic energy of the particles is directly
proportional to the absolute temperature (K). With
the increase in temperature, the particles move faster
as they gain kinetic energy
GAS PRESSURE
- Gas pressure arises from the force exerted by
collisions of gas molecules with the walls of the
container
- Gases exert pressure on any surface on which they
come in contact because gas molecules are constantly
in motion
- Pressure is commonly measured in units of
kilopascal (kPa), pascal (Pa), atmosphere (atm) and
mm Hg

MAXWELL-BOLTZMANN DISTRIBUTION CURVE

- The Maxwell-Boltmann distribution curve shows
how the speeds (or energy) of a mixture of moving
particles vary at particular temperature
- The particles of a gas at a constant temperature, are
always in constant random motion. The speed of the
particles varies over a wide range, from very slow
particles (low energy) to very fast particles (high
energy)
- Most of the particles at a speed very close to the
average, only a small fraction of the particles has very
low speed or very high speed
- The peak of each curve represents the most
probable speed, that is the speed of largest number
of particles
- The area under the curve represents the total
number of gas particles. The areas under both curves
are equal as there is no change in the number of
particles at the 2 temperatures
- An increase in temperature of the gas from T1 to T2
results in an increase in the molecular motion. The
distribution curve shifts to the right and flattens out.
This indicates that at higher temperature, there are
fewer particles with the most probable speed but
there are a greater proportion of high speed particles
- The average kinetic energy of the molecules of
different gases at the same temperature is identical.
Nevertheless, lighter molecules move faster on
average than heavier ones

 GAS LAWS
- The physical behaviour of a sample of a gas can be
described by 4 variables: pressure (P), volume (V),
absolute temperature (T) and amount (number of
moles, n)
- The following gas laws express the effect of one
variable on another
Boyle’s Law
Boyle’s law states that at constant temperatures, the
volume occupied by a fixed amount of gas is inversely
proportional to the applied pressure.
1
V α P (n and T constant)
As long as the amount of gas and the temperature are
held constant, for a given sample of gas under 2
different sets of conditions,
P1V1 = P2V2
Where V1 and V2 are the volume at pressures P1 and
P2 respectively

Example 4.1:
50 cm3 of a gas at 100 kPa is compressed to a volume of 20
cm3 at constant temperature. Determine the final pressure
of the gas

Solution:
P1V1 = P2V2
100 kPa x 50 cm3 = P2 x 20 cm3
100 � 50
P2 = = 250 kPa
20

Example 4.2:
An inflated balloon with a volume of 0.6 dm3 at sea level
(1.0 atm) is allowed to rise to a height of 6.0 km, where the
pressure is 0.4 atm. Assuming that the temperature
remains unchanged, what is the final volume of the balloon?

Solution:
P1V1 = P2V2
1.0 atm x 0.6 dm3 = 0.4 atm x V2
1.0 � 0.6
V2 = = 1.5 dm3
0.4
We can compare 2 sets of volume-temperature
conditions for a given sample of gas at constant
pressure which give
V1 V 2
T1 = T 2
Where V1 and V2 are the volume at temperature T1
and T2 respectively
Example 4.3:
50 cm3 of a sample of chlorine gas is heated from 25oC to
200oC. Calculate the final volume of the gas if the pressure
remains constant

Solution:
V1 V 2
T1 = T 2
50 V2
(273  25) = (273  200)

50 x 473
V2 = 298 = 79 cm3

Example 4.4:
A sample of gas at 30oC was heated. At what temperature
would the volume of the gas be doubled, assuming no
change in pressure?

Solution:
V1 V 2
T1 = T 2
V 2V
(273  30) = (273  T 2)

T2 = 2 x 303 - 273 = 333 K = 60oC

General Gas Law
A combination of Boyle’s law and Charles’ law gives
the combined general gas law that shows the
relationship between the 3 variables of gases: volume,
V, pressure, P, and absolute temperature, T
PV
T = constant
When comparing 2 sets of conditions, we have
P1V 1 P 2V 2
T1 = T 2

Example 4.5:
At 60oC and 1.50 x 105 Pa, a sample of gas occupies a
volume of 400 cm3. What is the volume occupied by the
gas at s.t.p?

Solution:
P1V 1 P 2V 2
T1 = T 2
(1.50 x 105 Pa) (400 cm3) = (1.01 x 105 Pa) (V)
(273 + 60)K 273K
V = 487 cm3
Avogadro’s law
Avogadro’s law states that at the same temperature
and pressure, equal volume of any gas contains the
same number of particles
V α n (T and P constant)
The volume occupied by 1 mol of gas (molar volume)
is the same for all gases
Molar volume of any gas at standard temperature
and pressure, s.t.p (0oC, 1 atm) = 22.4 dm3
Molar volume of any gas at room temperature and
pressure, r.t.p (25oC, 1 atm) = 24.4 dm3

Example 4.6:
Ethane, C2H6 burns in air according to the equation:
C2H6(g) + bO2(g) → cCO2(g) + dH2O(g)
a) Balance the above equation to determine the values of
b, c and d
b) What is the volume of O2 (in dm3) required for
complete combustion of 5.2 dm3 of C2H6?
c) What is the volume of CO2 produced? Assume all
gases are measured at the same temperature and pressure
Solution:
a) b = 7/2, c = 2, d = 3

b) V α n
V 1 n1
V 2 = n2
1 mol C2H6 of reacts with 7/2 mol of O2
VO2 = nO2
VC2H6 nC2H6
VO2 = 7/2
5.2 1
VO2 = 7/2 x 5.2 = 18.2 dm3

c) 1 mol of C2H6 produces 2 mol of CO2

VCO2 = 2
5.2 1
VCO2 = 5.2 x 2 = 10.4 dm3
Combined the 3 gas laws into one relationship called
the ideal gas equation or ideal gas law
PV = nRT
Where, P is the pressure of the gas
V is the volume
n is the number of moles of a substance
R is the gas constant (8.31 J K-1 mol-1)
T is the absolute temperature

Units of P, V and T used in the ideal gas law:

P V T
Pa m3 K
kPa dm3 K
The ideal gas equation can be rearranged to
determine the density and molar mass of a gas
mRT
PV = nRT = Mr
m PMr
Density, d = V = RT
mRT dRT
Molar mass, Mr = PV = P

Example 4.7:
0.01 mol of a sample of gas occupies 250.0 cm3 at 27oC. If
the temperature is raised to 35oC , calculate
a) The volume occupied if the pressure remains
unchanged
b) The pressure of the gas if the volume is fixed
c) The volume occupied by the gas at s.t.p (273K, 101 kPa)

Solution:
a)
V1 V 2
T1 = T 2
250.0 V2
(273  27) = (273  35)

V2 = 256.7 cm3
b) PV = nRT
nRT
P= V
= (0.01 mol)(8.31)(273 + 35)K
(250.0 x 10-3 dm3)
= 102 kPa

c) PV = nRT
nRT
V = P
= (0.01 mol)(8.31)(273K)
101 kPa
= 0.2246 dm3 = 224.6 cm3

Example 4.8:
A small hypodermic syringe containing 0.15 g of a volatile
liquid was injected into a graduated gas syringe at a
temperature of 90oC and a pressure of 101 kPa. The
expanded vapour was found to occupy a volume of 62.2
cm3. Determine the relative molecular mass of the volatile
liquid.

Solution:
mRT
Mr = PV
= (0.15 g)(8.31)(273 + 90)K = 72.0
(101 kPa)(62.2 x 10-3 dm-3)
Partial Pressure of a gas in a mixture is the pressure
exerted by the gas if it alone occupies the container
at the same temperature.
- Each component in a mixture contributes a fraction
of the total number of moles (n) in the mixture, which
is the mole fraction, X of that component
nT = nA + nB
nA
XA = n T
The partial pressure of gas A = mole fraction x total pressure
nA
P A = XA x P T = n T x P T
- The sum of the mole fractions off all components in
any mixture equals 1
XA + XB = 1

Example 4.10:
A gas mixture consists of 4.4 g of carbon dioxide and 6.4 g
of oxygen. Calculate the partial pressures of carbon dioxide
and oxygen in the mixture with the total pressure of 150
kPa

Solution:
4.4
Number of moles of CO2 = 12.0  (2 x 16.0) = 0.10
6.4
Number of moles of O2 = 2 x 16.0 = 0.20
0.10
Mole fraction of CO2 in the mixture = 0.10  0.20 = ⅓
 0.20
Mole fraction of O2 in the mixture = 0.10  0.20 = ⅔
PCO2 = ⅓ x 150 = 50 kPa
PO2 = ⅔ x 150 = 100 kPa

Example 4.11:
A mixture of gases at a pressure 1.01 x 105 Pa has the
volume composition of 30% CO, 50% O2 and 20% CO2
a) Calcultate the partial pressure of each gas
b) If the carbon dioxide is removed by the addition of
some pellets of sodium hydroxide
i) What will be the partial pressure of O2 and CO?
ii) What is the total pressure then?

Solution:
a) Vαn
V 1 n1
V 2 = n2
VA nA
VT = nT = XA
30
PCO = 100 x 1.01 x 105 = 3.03 x 104 Pa
50
PO2 = 100 x 1.01 x 105 = 5.05 x 104 Pa
20
PCO2 = 100 x 1.01 x 105 = 2.02 x 104 Pa
b) i) PO2 = 5.05 x 104 Pa
PCO = 3.03 x 104 Pa
ii) PT = PO2 + PCO = 5.05 x 104 + 3.03 x 104
= 8.08 x 104 Pa

REAL GAS: DEVIATIONS FROM IDEAL BEHAVIOUR

- A gas that obeys the ideal gas law is called an ideal
gas. A real gas that obeys the ideal gas equation is
said to exhibit ideal gas behaviour
Assumptions made about ideal gas:
 The volume of the gas molecules is negligible
compared to the total volume of the gas.
 There is no intermolecular forces of attraction or
repulsion.

Deviation of real gas from ideal behaviour because

 Gas molecules have finite volume that cannot be
ignored.
 Intermolecular forces of attraction exist between
the gas molecules and cannot be ignored.
- All gases exhibit near ideal behaviour at low
pressure and high temperature
a. At low pressure, the volume occupied by the gas is
large. The volume of gas molecules is comparatively
small and can be ignored. As the molecules are far
apart, the intermolecular attractive forces can be
ignored
b. At high temperature, the kinetic energy of the
molecules is so high that the intermolecular forces is
insignificant and can be ignored
- Real gases deviate significantly from ideal behaviour
at high pressure and low temperature
a. At high pressure, the volume occupied by the gas is
small and the volume of the gas molecules cannot be
ignored. At very high pressure, repulsive forces
between molecules become significant, and make the
gas less compressible
b. At low temperature, the kinetic energy of the
molecules is low. The intermolecular forces become
more apparent
- PV/RT curve decreases below ideal value at
moderately high pressure and then rises above it as
pressure increases further. The arises from 2
overlapping effects of the 2 characteristics of real gas
molecules
a. Negative deviation (PV/RT ˂ 1)
At moderately high pressure, intermolecular
attractions lower the force of collision of molecules
with the walls of the container
b. Positive deviation (PV/RT > 1)
At very high pressure, more gas molecules are packed
within the container. The volume of these gas
molecules though small, cannot be ignored
- H2 and He show positive deviation only at all
pressures due to the small molecular size and non-
polarity of the molecule, the intermolecular attractive
force is insignificant. The molecular volume effect
predominated at all pressures
- Gases with large and polar molecules deviate more
from ideal behaviour due to stronger intermolecular
forces of attraction