6 Gaseous State 2023
6 Gaseous State 2023
6 Gaseous State 2023
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.
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
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
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.