6. GASEOUS STATE.

 State Boyle's law.

For a fixed mass of a gas, at constant temperature, the volume is inversely
proportional to its pressure.
1
V 
P
1
V = k 
P
PV = k
 Derive the pressure- density relationship from Boyle’s law.
The pressure-density relationship can be derived from the Boyle’s law.
P1V1 = P2V2
 m  m
P1   = P2  
 d1   d2 
Where “m” is the mass, d1 and d2 are the densities at pressure P1 and P2.
 P1   P2 
 = 
 d1   d2 
The density of a gas is directly proportional to pressure.
 State Charle’s law.
For a fixed mass of a gas, at constant pressure, the volume is directly proportional to
its temperature (K).
V∝𝑇
V = k𝑇
V
=k
𝑇
If the temperature of the gas increases, the volume also increases in direct
proportion, so that V/T is a constant.
V1 𝑉2
= = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇1 𝑇2
 A balloon filled with air at room temperature and cooled to a much lower
temperature can be used as a model for Charle’s law (BQ27)
 Yes. It can be used as a model for Charle’s law.
 Charle’s law relates volume of a gas with its temperature. A balloon filled with air
at room temperature, when it is cooled to a much lower temperature, the
temperature of the gas decreases. As a result, the gas molecules inside the
balloon move slower and gas shrinks. Hence, the volume decreases.

Unit-6: gaseous state ↻ The Turning Point ↻ 1

 Variation of volume with temperature at constant pressure
 The plot of the volume (V) of the gas against its temperature (T) at a given
pressure is shown in the figure.

 The volume of the gas linearly increases with temperature at a given pressure.
Such lines are called isobars. It can be expressed by the following straight-line
equation.
V = mT + C
 Where T is the temperature in degree Celsius and m & C are constants. When 𝑇 =
0℃ , the volume becomes 𝑉0 . Hence, 𝑉0 = 𝐶 and slope of the straight-line m is
𝛥𝑉
equal to . Therefore
∆𝑇
∆𝑉
V = ( ) 𝑇 + 𝑉0 (n, P are constant)
∆𝑇
Divide this equation by Vo
V 1 ∆𝑉
= ( )𝑇 +1
𝑉0 𝑉0 ∆𝑇
 Charles and Gay Lussac found that under constant pressure, the relative increase
𝟏 ∆𝑽
in volume per degree increase in temperature { ( ) = 𝜶 } is same for all
𝑽𝟎 ∆𝑻
gases.
V
= α𝑇 + 1
𝑉0
𝑉 = 𝑉0 (α𝑇 + 1)
 The coefficient of expansion (𝜶) is approximately equal to 1/273. That is at
constant temperature for a given mass, for each degree rise in temperature, all
gases expand by 1/273 of their volume at 0 0C.
 If we extrapolate the straight line beyond the experimental measurements, the
straight line intersects the temperature axis (x-axis) at −273℃. This shows that
the volume of the gas becomes zero at −273℃, more precisely this temperature
is −273.15℃.
 This temperature was defined as absolute zero by Kelvin.

Unit-6: gaseous state ↻ The Turning Point ↻ 2

 State Gay-Lussac’s Law.
Gay-Lussac stated that, “For a fixed mass of a gas, at constant volume, the pressure
of is directly proportional to its temperature”.
P∝𝑇
P = k𝑇
P
=k
𝑇
If P1 𝑎𝑛𝑑 𝑃2 are the pressures at temperatures T1 𝑎𝑛𝑑 𝑇2 respectively then
P1 𝑃2
= = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇1 𝑇2
 What is Avogadro’s hypothesis?
Avogadro hypothesised that equal volumes of all gases under the same conditions of
temperature and pressure contain equal number of molecules.
V∝𝑛
V1 V2
= = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑛1 𝑛2
Where V1 & n1 are the volume and number of moles of a gas and V 2 & n2 are a
different set of values of volume and number of moles of the same gas at same
temperature and pressure.
 What is an Ideal gas equation?
1
Boyle’s law : V∝
𝑃
Charle’s law : V ∝T
Avogadro’s law : V∝n
When these equations are combined
nT
V ∝
𝑃
nT
V=R
𝑃
Where, R - universal gas constant.
The above equation can be rearranged to give the ideal gas equation
𝑃𝑉 = 𝑛𝑅𝑇
 Units of R – gas constant:
𝑃𝑉
𝑅 =
𝑛𝑇
𝑅 = 8.314 𝐽 𝐾 −1𝑚𝑜𝑙−1
𝑅 = 0.0821 𝑑𝑚3 𝑎𝑡𝑚 𝐾 −1 𝑚𝑜𝑙−1

Unit-6: gaseous state ↻ The Turning Point ↻ 3

 State Dalton’s law of partial pressures.
"The total pressure of a mixture of non-reacting gases is the sum of partial pressures
of the gases present in the mixture".
For a mixture containing three gases 1, 2 and 3 with partial pressures 𝑝1 , 𝑝2 𝑎𝑛𝑑 𝑝3
in a container with volume V, the total pressure 𝑃𝑡𝑜𝑡𝑎𝑙 will be
Ptotal = P1 +P2 +P3 +..
Assuming that the gases behave ideally,
𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑝1 = 𝑛1 ( ) ; 𝑝2 = 𝑛2 ( ) ; 𝑝3 = 𝑛3 ( )
𝑉 𝑉 𝑉
𝑅𝑇 𝑅𝑇 𝑅𝑇
P𝑡𝑜𝑡𝑎𝑙 = 𝑛1 ( ) + 𝑛2 ( ) + 𝑛3 ( )
𝑉 𝑉 𝑉
𝑅𝑇
P𝑡𝑜𝑡𝑎𝑙 = (𝑛1 + 𝑛2 + 𝑛3 ) ( )
𝑉
𝑅𝑇
P𝑡𝑜𝑡𝑎𝑙 = 𝑛𝑇𝑜𝑡𝑎𝑙 ( )
𝑉
𝑅𝑇
( ) can be expressed as
𝑉
𝑅𝑇 𝑝1 𝑝2 𝑝3 𝑝𝑖
( )= = = =
𝑉 𝑛1 𝑛2 𝑛3 𝑛𝑖
Therefore
𝑅𝑇
P𝑡𝑜𝑡𝑎𝑙 = 𝑛𝑇𝑜𝑡𝑎𝑙 ( )
𝑉
𝑝𝑖
P𝑡𝑜𝑡𝑎𝑙 = 𝑛𝑇𝑜𝑡𝑎𝑙 ( )
𝑛𝑖
𝑛𝑖
p𝑖 = ( )P
𝑛𝑡𝑜𝑡𝑎𝑙 𝑡𝑜𝑡𝑎𝑙
p𝑖 = 𝑋𝑖 P𝑡𝑜𝑡𝑎𝑙
 What is diffusion?
When two non -reactive gases are allowed to mix, the gas molecules migrate from
region of higher concentration to a region of lower concentration.
“The property of gas which involves the movement of the gas molecules through
another gases is called diffusion”.
 State Graham’ s Law of Diffusion.
The rate of diffusion or effusion of a gas is inversely proportional to the square root
of its molar mass. Mathematically
1
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 (𝑟) ∝
√𝑀
𝑟𝐴 𝑀𝐵
= √
𝑟𝐵 𝑀𝐴
Where 𝑟𝐴 and 𝑟𝐵 are the rates of diffusion of A and B and the M A and MB are their
respective molar masses.

Unit-6: gaseous state ↻ The Turning Point ↻ 4

 An unknown gas diffuses at a rate of 0.5 time that of Nitrogen at the same
temperature and pressure. Calculate the molar mass of the unknown gas.
Solution:
𝑟𝑢𝑛𝑘𝑛𝑜𝑤𝑛 𝑀𝑁2
=√
𝑟𝑁2 𝑀𝑢𝑛𝑘𝑛𝑜𝑤𝑛

28 𝑔 𝑚𝑜𝑙 −1
0.5 = √
𝑀𝑢𝑛𝑘𝑛𝑜𝑤𝑛
28 𝑔 𝑚𝑜𝑙−1
(0.5 = )2
𝑀𝑢𝑛𝑘𝑛𝑜𝑤𝑛
28 𝑔 𝑚𝑜𝑙−1
𝑀𝑢𝑛𝑘𝑛𝑜𝑤𝑛 =
(0.5)2
𝑀𝑢𝑛𝑘𝑛𝑜𝑤𝑛 = 112 𝑔 𝑚𝑜𝑙 −1
 A flammable hydrocarbon gas of particular volume is found to diffuse through a
small hole in 1.5minutes. Under the same conditions of temperature and pressure
an equal volume of bromine vapour takes 4.73 min to diffuse through the same
hole. Calculate the molar mass of the unknown gas and suggest what this gas might
be, (Given that molar mass of bromine = 159.8 g/mole)
Solution:
𝑟𝐻𝐶 𝑀𝐵𝑟2
=√
𝑟𝐵𝑟2 𝑀𝐻𝐶
1
𝑚𝑖𝑛 159.8 𝑔 𝑚𝑜𝑙−1
1.5 =√
1 𝑀𝐻𝐶
𝑚𝑖𝑛
4.73
4.73 159.8 𝑔 𝑚𝑜𝑙−1
=√
1.5 𝑀𝐻𝐶

159.8 𝑔 𝑚𝑜𝑙 −1
3.15 = √
𝑀𝐻𝐶
159.8 𝑔 𝑚𝑜𝑙−1
(3.15)2 =
𝑀𝐻𝐶
159.8 𝑔 𝑚𝑜𝑙−1
𝑀𝐻𝐶 =
(3.15)2
𝑀𝐻𝐶 = 16 𝑔 𝑚𝑜𝑙 −1
The hydrocarbon must be 𝐶𝐻4

Unit-6: gaseous state ↻ The Turning Point ↻ 5

 What is effusion?
Effusion is another process in which a gas escapes from a container through a very
small hole.
 What is compressibility factor?
A ratio of PV to nRT is termed as compressibility factor. The deviation of real gases
from ideal behaviour is measured in terms of compressibility factor.
𝑃𝑉
Z=
𝑛𝑅𝑇
For ideal gases PV = nRT, hence the compressibility factor, Z = 1 at all temperatures
and pressures.
 What is Boyle temperature?
The temperature at which a real gas obeys ideal gas law over an appreciable range
of pressure is called Boyle temperature or Boyle point.
 Derive compressibility factor for real gases.
The compressibility factor Z for real gases can be rewritten
𝑃𝑉𝑟𝑒𝑎𝑙
Z= − − − − − (1)
𝑛𝑅𝑇
but
𝑛𝑅𝑇
V𝑖𝑑𝑒𝑎𝑙 = − − − − − (2)
𝑃
substituting (2)𝑖𝑛 (1)
𝑉𝑟𝑒𝑎𝑙
Z=
𝑉𝑖𝑑𝑒𝑎𝑙
Where Vreal is the molar volume of the real gas and V ideal is the molar volume
of it when it behaves ideally.
 Write the Van der Waals equation for a real gas. Explain the correction term for
pressure and volume (or) Derive van der waals equation for real gases.
Van der Waals modified the ideal gas equation PV = nRT by introducing two
correction factors, namely, pressure correction and volume correction.
Pressure Correction:
 The pressure of a gas is directly proportional to the force created by the
bombardment of molecules on the walls of the container.
 The speed of a molecule moving towards the wall is reduced by the attractive
forces exerted by its neighbours.
 Hence, the measured gas pressure is lower than the ideal pressure of the gas.
 Hence, van der Waals introduced a correction term to this effect.

Unit-6: gaseous state ↻ The Turning Point ↻ 6

  The forces of attraction experienced by a molecule near the wall are directly
proportional to the square of the density of the gas.
P′ ∝ 𝜌2
𝑛
𝜌=
𝑉
′
𝑛2
𝑃 ∝ 2
𝑉
′
𝑛2
𝑃 =𝑎 2
𝑉
 Where a is proportionality constant and depends on the nature of gas Therefore,
𝑛2
𝑃𝑖𝑑𝑒𝑎𝑙 = 𝑃 + 𝑎 2
𝑉
Volume Correction
 As every individual molecule of a gas occupies a certain volume, the actual volume
is less than the volume of the container (V).
 Van der Waals introduced a correction factor V’ to this effect. Let us calculate the
correction term by considering gas molecules as spheres.

V – Excluded volume
4
𝐸𝑥𝑐𝑙𝑢𝑑𝑒𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑜𝑟 2 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 = 𝜋(2𝑟)3
3
4
𝐸𝑥𝑐𝑙𝑢𝑑𝑒𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑜𝑟 2 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 = 8 ( 𝜋𝑟 3)
3
𝐸𝑥𝑐𝑙𝑢𝑑𝑒𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑜𝑟 2 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 = 8 𝑉𝑚

Unit-6: gaseous state ↻ The Turning Point ↻ 7

 Where Vm is a volume of a single molecule
𝐸𝑥𝑐𝑙𝑢𝑑𝑒𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑜𝑟 𝑠𝑖𝑛𝑔𝑙𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = 4 𝑉𝑚 = 𝑏
𝐸𝑥𝑐𝑙𝑢𝑑𝑒𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑜𝑟 𝑛 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑉′ = 𝑛 (4𝑉𝑚 ) = 𝑛𝑏
Where b is the van der Waals constant.
𝑉𝑖𝑑𝑒𝑎𝑙 = 𝑉 − 𝑛𝑏
 Replacing the corrected pressure and volume in the ideal gas equation PV=nRT ,
we get the van der Waals equation of state for real gases as below,
𝑎𝑛2
(P + 2 ) (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
𝑉

 The constants ‘a’ and ‘b’ are van der Waals constants and their values vary with
the nature of the gas.

 Andrew's isotherm
 Thomas Andrew plotted isotherms
of CO2 at different temperatures.
 At 130 C isotherm, as the pressure
increases, the volume decreases
along AB and is a gas until the point
B is reached.
 At B, a liquid separate along the
line BC, both the liquid and gas co-
exist and the pressure remains
constant.

 At C, the gas is completely converted into liquid. If the pressure is higher than at
C, only the liquid is compressed so, there is no significant change in the volume.
 The successive isotherms shows similar trend with the shorter flat region. i.e. The
volume range in which the liquid and gas coexist becomes shorter.
 At the temperature of 31.10C the length of the shorter portion is reduced to zero
at point P. In other words, the CO2 gas is liquefied completely at this point. This
temperature is known as the liquefaction temperature or critical temperature of
CO2.At this point the pressure is 73 atm.
 Above this temperature CO2 remains as a gas at all pressure values.
 It is then proved that many real gases behave in a similar manner to carbon
dioxide.

Unit-6: gaseous state ↻ The Turning Point ↻ 8

 Define Critical temperature.
Critical temperature ( Tc) of a gas is defined as the temperature above which it cannot
be liquefied even at high pressure.
 Define Critical pressure.
Critical pressure (Pc) of a gas is defined as the minimum pressure required to liquefy
1 mole of a gas at its critical temperature.
 Define Critical volume.
Critical volume (Vc) is defined as the volume occupied by 1 mole of a gas at its critical
temperature and critical pressure.
 What is Joule Thomson effect?
The phenomenon of lowering of temperature when a gas is made to expand
adiabatically from a region of high pressure into a region of low pressure is known as
Joule Thomson effect. This effect is observed only below a certain temperature,
which is a characteristic one for each gas.
 What is inversion temperature?
The temperature below which a gas obeys Joule-Thomson effect is called inversion
temperature ( Ti ). This value is given using van der Waals constants a and b.
2𝑎
T𝑖 =
𝑅𝑏
Gases like O2, He, N2 and H2 have very low Tc, and hence Joule-Thomson effect can
be applied for cooling effectively.
 List the different methods used for liquefaction of gases.
 Linde’s method:
Joule-Thomson effect is used to get liquid air or any other gas.
 Claude’s process:
The gas is allowed to perform mechanical work in addition to Joule-Thomson
effect so that more cooling is produced.
 Adiabatic process:
Cooling is produced by removing the magnetic property of magnetic material
such as gadolinium sulphate. By this method, a temperature of 10 -4 K i.e. as low
as 0 K can be achieved.

Unit-6: gaseous state ↻ The Turning Point ↻ 9

 Derive the values of critical constants from van der Waals constant. (or)
Derive the values of van der Waals equation constants in terms of critical constants.
The van der Waals equation for n moles is
𝑎𝑛2
(𝑃 + 2 ) (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇 − − − − − (1)
𝑉
For 1 mole
𝑎
(𝑃 + 2 ) (𝑉 − 𝑏) = 𝑅𝑇 − − − − − (2)
𝑉
On expanding the above equation
𝑎 𝑎𝑏
𝑃𝑉 + − 𝑃𝑏 − 2 − 𝑅𝑇 = 0 − − − − − (3)
𝑉 𝑉
V2
Multiply equation (3) by
𝑃
2
𝑉 𝑎 𝑎𝑏
(𝑃𝑉 + − 𝑃𝑏 − 2 − 𝑅𝑇) = 0
𝑃 𝑉 𝑉
3
𝑎𝑉 2
𝑎𝑏 𝑅𝑇𝑉 2
𝑉 + − 𝑏𝑉 − − = 0 − − − − − (4)
𝑃 𝑃 𝑃
When the above equation is rearranged in powers of V
𝑅𝑇 𝑎 𝑎𝑏
𝑉 3 − [ + 𝑏] 𝑉 2 + [ ] 𝑉 − = 0 − − − − − (5)
𝑃 𝑃 𝑃
The equation (5) is a cubic equation in V. On solving this equation, we will get three
solutions. At the critical point all these three solutions of V are equal to the critical
volume VC. The pressure and temperature becomes Pc and Tc respectively i.e.,
𝑉 = 𝑉𝐶
(𝑉 – 𝑉𝐶 ) = 0
(𝑉 – 𝑉𝐶 )3 = 0
𝑉 3 − 3𝑉𝐶 𝑉 2 + 3𝑉𝐶2 𝑉 − 𝑉𝐶3 = 0 − − − − − (6)
As equation (6) is identical with equation (5), we can equate the coefficients of V2, V
and constant terms in (5) and (6).
𝑅𝑇𝐶
−3𝑉𝐶 = − [ + 𝑏]
𝑃𝐶
𝑅𝑇𝐶
3𝑉𝐶 = + 𝑏 − − − − − (7)
𝑃𝐶
𝑎
3𝑉𝐶2 = − − − − − (8)
𝑃𝐶
𝑎𝑏
𝑉𝐶3 = − − − − − (9)
𝑃𝐶

Unit-6: gaseous state ↻ The Turning Point ↻ 10

 Divide (9) by (8)
𝑎𝑏
𝑉𝐶3 ( )
𝑃𝐶
2 = 𝑎
3𝑉𝐶 ( )
𝑃𝐶
𝑉𝐶 = 3𝑏 − − − − − (10)
When (10) is substituted in (8)
𝑎
3(3𝑏)2 =
𝑃𝐶
𝑎
27 𝑏2 =
𝑃𝐶
𝑎
𝑃𝐶 = − − − − − (11)
27𝑏2
Substituting the values of Vc and Pc in equation (7),
𝑅𝑇𝐶
3(3𝑏) = 𝑎 +𝑏
( )
27𝑏2
𝑅𝑇𝐶
9𝑏 − 𝑏 = 𝑎
( )
27𝑏2
8𝑎
𝑇𝐶 = − − − − − (12)
27𝑅𝑏
The critical constants can be calculated using the values of van der waals constant of
a gas and vice versa.
𝑉𝐶
𝑎 = 3𝑉𝐶2 𝑃𝐶 ; 𝑏 =
3

Unit-6: gaseous state ↻ The Turning Point ↻ 11