Gaseous State 225

60
Chapter

E3
Gaseous state

(i) The volume, V, of the gas.

The state of matter in which the molecular forces
of attraction between the particles of matter are
minimum, is known as gaseous state. It is the simplest
state and shows great uniformity in behaviour.
Characteristics of gases
ID (ii) Its pressure, P
(iii) Its temperature, T
(iv) The amount of the gas (i.e., mass or number
of moles).
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(2) Volume : (i) Since gases occupy the entire
(1) Gases or their mixtures are homogeneous in
space available to them, the measurement of volume of
composition.
a gas only requires a measurement of the container
(2) Gases have very low density due to negligible
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confining the gas.

intermolecular forces.
(ii) Volume is expressed in litres (L),
(3) Gases have infinite expansibility and high
compressibility. millilitres (mL) or cubic centimetres (cm 3 ) or cubic
(4) Gases exert pressure. metres (m 3 ) .
(5) Gases possess high diffusibility.
(iii) 1L  1000 mL ; 1 mL  10 3 L ; 1 L  1 dm 3  10 3 m 3
(6) Gases do not have definite shape and volume
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like liquids. 1 m 3  10 3 dm 3  10 6 cm 3  10 6 mL  10 3 L
(7) Gaseous molecules move very rapidly in all
(3) Mass : (i) The mass of a gas can be
directions in a random manner i.e., gases have highest
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determined by weighing the container in which the gas

kinetic energy.
(8) Gaseous molecules collide with one another and
also with the walls of container with perfectly elastic
ST
is enclosed and again weighing the container after
removing the gas. The difference between the two
weights gives the mass of the gas.

collisions.
(ii) The mass of the gas is related to the
(9) Gases can be liquified, if subjected to low
number of moles of the gas i.e.
temperatures (below critical) or high pressures.
M ass in grams m
(10) Thermal energy of gases >> molecular moles of gas (n)  
attraction. M olar mass M

(11) Gases undergo similar change with the
change of temperature and pressure. In other words,
gases obey certain laws known as gas laws.
Measurable properties of gases
(1) The characteristics of gases are described fully
in terms of four parameters or measurable properties :
(4) Temperature : (i) Gases expand on increasing
the temperature. If temperature is increased twice, the
square of the velocity (v 2 ) also increases two times.
(ii) Temperature is measured in centigrade
degree ( o C) or celsius degree with the help of
 226 Gaseous State
thermometers. Temperature is also measured in Absolute pressure = Gauge pressure + Atmosphere
Fahrenheit (Fo). pressure.
(iii) S.I. unit of temperature is kelvin (K) or (xi) When the pressure in a system is less than
absolute degree. atmospheric pressure, the gauge pressure becomes
negative, but is frequently designated and called
K  o C  273
vacuum. For example, 16 cm vacuum will be
o
C F o  32 76  16
(iv) Relation between F and o C is   1 .013  0 .80 bar .
5 9 76
(5) Pressure : (i) Pressure of the gas is the force (xii) If ‘h’ is the height of the fluid in a column or
exerted by the gas per unit area of the walls of the the difference in the heights of the fluid columns in the

60
container in all directions. Thus, Pressure two limbs of the manometer, d is the density of the
Force( F) Mass(m)  Accelerati on (a) fluid
(P)  
Area( A) Area(a) (Hg  13 .6  10 3 Kg / m 3  13 .6 g / cm 3 ) and g is the gravity,
(ii) Pressure exerted by a gas is due to kinetic then pressure is given by, Pgas  Patm  h dg
1
energy (KE  mv 2 ) of the molecules. Kinetic energy of

E3
2
(xiii) Two sets of conditions are widely used as
'standard' values for reporting data.
the gas molecules increases, as the temperature is
increased. Thus, Pressure of a gas  Temperature (T). Condition T P Vm (Molar
volume)
(iii) Pressure of a pure gas is measured by
manometer while that of a mixture of gases by S.T.P./N.T. 273.15 K 1 atm 22.414 L
barometer.
(iv) Commonly two types of manometers are used,
(a) Open end manometer;
manometer
(b) Closed end
ID P.
S.A.T.P*. 298.15 K 1 bar
* Standard ambient temperature and pressure.
Boyle's law
24.800 L
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(v) The S.I. unit of pressure, the pascal (Pa), is (1) In 1662, Robert Boyle discovered the first of
defined as 1 newton per metre square. It is very small several relationships among gas variables (P, T, V).
unit. (2) It states that, “For a fixed amount of a gas at
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constant temperature, the gas volume is inversely

1 Pa  1 Nm 2  1 kg m 1 s 2 proportional to the gas pressure.”
Thus, P  1 / V at constant temperature and
(vi) C.G.S. unit of pressure is dynes cm 2 .
mass
(vii) M.K.S. unit of pressure is kgf / m 2 . The unit or P  K / V (where K is constant)
kgf / cm 2 sometime called ata (atmosphere technical or PV  K or P1 V1  P2 V2  K (For two or more
absolute). gases)
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(viii) Higher unit of pressure is bar, KPa or MPa. (3) Graphical representation of Boyle's law :
1 bar  10 5 Pa  10 5 Nm 2  100 KNm 2  100 KPa Graph between P and V at constant temperature is
called isotherm and is an equilateral (or rectangular)
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(ix) Several other units used for pressure are, hyperbola. By plotting P versus 1 / V , this hyperbola
Name Symbol Value can be converted to a straight line. Other types of
isotherms are also shown below,
bar bar 1bar  10 Pa
5
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atmosphe atm 1 atm  1 .01325  10 5 Pa T3

re T2
T1 < T 2 < T3
Torr Torr 101325
1 Torr  Pa  133 . 322 Pa P P
T1
760
millimetr mm Hg 1 mm Hg  133 .322 Pa
T3
e of T2 T1 < T2 < T3
mercury T1
O O
V or 1/V or
(x) The pressure relative to the atmosphere is 1/d d
called gauge pressure. The pressure relative to the
perfect vacuum is called absolute pressure. T1 < T2 < T 3
PV T3
T2
T1 log P

O O
P log
 Gaseous State 227

1/d or
V

1/d
or 22.4 L mol–1 =
V V0
O t(oC)
(4) At constant mass and temperature density of a – 0o
T(k 273.15oC C
gas is directly proportional to its pressure and
inversely proportional to its volume. (5) At constant
) mass and pressure density of a gas
is inversely proportional to it absolute temperature.
1  mass 
Thus, d  P   V  d 

60
V   1 1  mass 
Thus, d    V  d 
d1 P V T V  
or  1  2  .......  K
d 2 P2 V1
d1 T2 V2
(5) At altitudes, as P is low d of air is less. That is or    ......  K
d 2 T1 V1

why mountaineers carry oxygen cylinders.
Charle's law
(1) French chemist, Jacques Charles first studied
variation of volume with temperature, in 1787.
(2) It states that, “The volume of a given mass of a
gas is directly proportional to the absolute temperature
( o C  273 ) at constant pressure”.
Thus, V  T at constant pressure and mass
or V  KT  K (t( o C)  273 .15 ) ,
constant),
V V V
K or 1  2  K (For two or more gases)
T T1 T2
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(6) Use of hot air balloons in sports and
meteorological observations is an application of
Charle's law.
Gay-Lussac's law (Amonton's law)
(where k is
ID (1) In 1802, French chemist Joseph Gay-Lussac
studied the variation of pressure with temperature and
extende the Charle’s law so, this law is also called
Charle’s-Gay Lussac’s law.
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(2) It states that, “The pressure of a given mass of
a gas is directly proportional to the absolute
temperature ( o C  273 ) at constant volume.”

(3) If t  0 o C , then V  V0 Thus, P  T at constant volume and mass

hence, V0  K  273 .15 or P  KT  K(t(o C)  273 .15 ) (where K is

V0 constant)
 K
273 .15 P P P
K or 1  2  K (For two or more gases)
 
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V0 t T T1 T2
V [t  273 .15 ]  V0 1    V0 [1   v t]
273 .15  273 . 15 
(3) If t  0 o C , then P  P0
where  v is the volume coefficient,
Hence, P0  K  273 .15
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V  V0 1
v    3 .661  10  3 o C 1 P0
tV0 273 .15  K
273 .15
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Thus, for every 1 o change in temperature, the P0  t 

P [t  273 . 15 ]  P0 1    P0 [1  t]
1  1  273 . 15  273 . 15 
volume of a gas changes by   of the
273 . 15  273 
where  P is the pressure coefficient,
volume at 0 o C .
P  P0 1
P    3 .661  10  3 o C 1
(4) Graphical representation of Charle's law : tP0 273 .15
Graph between V and T at constant pressure is called
isobar or isoplestics and is always a straight line. A plot Thus, for every 1 o change in temperature, the
1  1 
of V versus t( o C ) at constant pressure is a straight line pressure of a gas changes by   of the
273 . 15  273 
cutting the temperature axis at  273 .15 o C . It is the
pressure at 0 o C .
lowest possible temperature.
 228 Gaseous State
(4) This law fails at low temperatures, because If all the above law's combines, then
the volume of the gas molecules be come significant. nT
V
(5) Graphical representation of Gay-Lussac's P
law : A graph between P and T at constant V is called nRT
or V ( R  Ideal gas constant)
isochore. P
V 1 < V 2< V 3 < V 4 or PV  nRT
V1
V2 This is called ideal gas equation. R is called ideal
V3 gas constant. This equation is obeyed by isothermal
P V4
P and adiabatic processes.
(2) Nature and values of R : From the ideal gas

60
PV Pressure  Volume
equation, R  
nT mole  Temperatur e
O O
T(k T Force
 Volume
) Area Force  Length
Avogadro's law  
mole  Temperatur e mole  Temperatur e

E3
(1) According to this law, “Equal volumes of any Work or energy
two gases at the same temperature and pressure contain  .
mole  Temperatur e
the same number of molecules.”
R is expressed in the unit of work or energy
Thus, V  n (at constant T and P) 1 1
mol K .
or V  Kn (where K is constant)
V V
or 1  2  .......  K
n1 n 2

Example, 2 H 2 (g) O 2 (g)  2 H 2 O(g)

ID :
Since different values of R are summarised below

R  0 .0821 L atm mol 1 K 1

 8 .3143 joule mol 1 K 1 (S.I. unit)

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2 moles 1 mole 2 moles
 8 . 3143 Nm mol 1 K 1
2 volumes 1 volume 2 volumes
2 litres 1 litre 2 litres
1 litre 1 / 2 litre 1 litre
1n litre 1 / 2 n litre 1n litre  8 .3143 KPa dm 3 mol 1 K 1
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(2) One mole of any gas contains the same  8 . 3143 MPa cm 3 mol 1 K 1
number of molecules (Avogadro's number  6 .02  10 ) 23
 5 .189  10 19 eV mol 1 K 1
and by this law must occupy the same volume at a
given temperature and pressure. The volume of one  1 .99 cal mol 1 K 1
mole of a gas is called molar volume, Vm which is 22.4
(3) Gas constant, R for a single molecule is called
L mol 1 at S.T.P. or N.T.P. Boltzmann constant (k)
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(3) This law can also express as, “The molar gas R 8 .314  10 7
volume at a given temperature and pressure is a specific k  ergs mole 1 degree 1
N 6 .023  10 23
constant independent of the nature of the gas”.
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 1 .38  10 16 ergs mol 1 de gree 1

Thus, Vm  specific constant  22 .4 L mol 1 at
or 1 .38  10 23 joule mol 1 degree 1
S.T.P. or N.T.P.
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Ideal gas equation (4) Calculation of mass, molecular weight and

density of the gas by gas equation
(1) The simple gas laws relating gas volume to
m
pressure, temperature and amount of gas, respectively, PV  nRT  RT
M
are stated below :
 mass of the gas (m) 
 n  
Molecular weight of the gas (M ) 
1 1
Boyle's law : P or V  (n and T 
V P
constant) mRT
 M
PV
Charle's law : VT (n and P
constant) PM  m
d  d  
Avogadro's law : V  n (T and P RT  V
constant)
 Gaseous State 229
dT M M (4) Applications : This law is used in the
or  ,  Constant
P R R calculation of following relationships,
(  M and R are constant for a particular gas) (i) Mole fraction of a gas (X 1 ) in a mixture
dT d T d T Partial pr essure of a gas (P1 )
Thus, or 1 1  2 2 = Constant of gas 
P P1 T2 PTotal

(For two or more different temperature and (ii) % of a gas in mixture

pressure) Partial pr essure of a gas (P1 )
  100
(5) Gas densities differ from those of solids and PTotal
liquids as, (iii) Pressure of dry gas collected over water :

60
(i) Gas densities are generally stated in When a gas is collected over water, it becomes moist
g/L instead of g / cm 3 . due to water vapour which exerts its own partial
pressure at the same temperature of the gas. This
(ii) Gas densities are strongly dependent on
partial perssure of water vapours is called aqueous
pressure and temperature as, d  P  1 / T
tension. Thus, Pdry gas  Pmoist gas or PTotal  Pwater vapo ur
Densities of liquids and solids, do depend

E3
somewhat on temperature, but they are far less or Pdry gas  Pmoist gas  Aqueous tension (Aqueous
dependent on pressure. tension is directly proportional to absolute
(iii) The density of a gas is directly proportional temperature)
to its molar mass. No simple relationship exists (iv) Relative humidity (RH) at a given temperature
between the density and molar mass for liquid and is given by,
solids.

(iv) Density of a gas at STP 

d( N 2 ) at STP 
28
molar mass
22 . 4

 1 .25 g L1 ,
ID RH 
Partial pr essure of water in air
Vapour pre ssure of water
.

(5) Limitations : This law is applicable only when

the component gases in the mixture do not react with
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22 .4 each other. For example, N 2 and O 2 , CO and CO 2 , N 2
32 and Cl 2 , CO and N 2 etc. But this law is not applicable
d(O2 ) at STP   1 .43 g L1
22 .4 to gases which combine chemically. For example, H 2
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Dalton's law of partial pressures
(1) According to this law, “When two or more
gases, which do not react chemically are kept in a closed
vessel, the total pressure exerted by the mixture is equal
to the sum of the partial pressures of individual gases.”
Thus, Ptotal  P1  P2  P3  .........
D
and Cl 2 , CO and Cl 2 , NH 3 , HBr and HCl, NO and O 2
etc.
(6) Another law, which is really equivalent to the
law of partial pressures and related to the partial
volumes of gases is known as Law of partial volumes
given by Amagat. According to this law, “When two or

more gases, which do not react chemically are kept in a

Where P1 , P2 , P3 ,...... are partial pressures of gas
closed vessel, the total volume exerted by the mixture is
number 1, 2, 3 ......... equal to the sum of the partial volumes of individual
(2) Partial pressure is the pressure exerted by a
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gases.”
gas when it is present alone in the same container and Thus, VTotal  V1  V2  V3  ......
at the same temperature.
Where V1 , V2 , V3 ,...... are partial volumes of gas
Partial pressure of a gas
ST

Number of moles of the gas (n1 )  PTotal number 1, 2, 3.....

(P1 )   Mole fraction (X 1 )  PTotal
Total number of moles (n) in the mixture Graham's law of diffusion and Effusion
(3) If a number of gases having volume
(1) Diffusion is the process of spontaneous
V1 , V2 , V3 ...... at pressure P1 , P2 , P3 ........ are mixed
spreading and intermixing of gases to form
together in container of volume V, then, homogenous mixture irrespective of force of gravity.
P1 V1  P2 V2  P3 V3 ..... While Effusion is the escape of gas molecules through
PTotal 
V a tiny hole such as pinhole in a balloon.
RT  All gases spontaneously diffuse into one another
or  (n1  n 2  n 3 .....) ( PV  nRT )
V when they are brought into contact.
RT  Diffusion into a vacuum will take place much
or  n ( n  n1  n2  n3 .....)
V more rapidly than diffusion into another place.
 230 Gaseous State
 Both the rate of diffusion of a gas and its rate of (iv) The volume of gas effused through a given
effusion depend on its molar mass. Lighter gases surface per unit time is also called rate of effusion.
diffuses faster than heavier gases. The gas with highest (5) Applications : Graham's law has been used as
rate of diffusion is hydrogen. follows,
(2) According to this law, “At constant pressure (i) To determine vapour densities and
and temperature, the rate of diffusion or effusion of a molecular weights of gases.
gas is inversely proportional to the square root of its (ii) To prepare Ausell’s marsh gas
vapour density.” indicator, used in mines.
1
Thus, rate of diffusion (r)  (T and P (iii) Atmolysis : The process of separation of two
d gases on the basis of their different rates of diffusion

60
constant) due to difference in their densities is called atmolysis.
For two or more gases at constant pressure and It has been applied with success for the separation of
temperature, isotopes and other gaseous mixtures.
r1

d2 Kinetic theory of gases
r2 d1

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(1) Kinetic theory was developed by Bernoulli,
(3) Graham's law can be modified in a number of Joule, Clausius, Maxwell and Boltzmann etc. and
ways as, represents dynamic particle or microscopic model
(i) Since, 2  vapour density (V.D.) = for different gases since it throws light on the
Molecular weight behaviour of the particles (atoms and molecules) which
r1 d2 d2  2 M2 constitute the gases and cannot be seen. Properties of
  
then,

of the two gases.

(ii)
r2

Since,
d1 d1  2

rate
M1
where, M 1 and M 2 are the molecular weights

of
ID
diffusion
gases which we studied earlier are part of macroscopic
model.
(2) Postulates
(i) Every gas consists of a large number of
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small particles called molecules moving with very high
Volume of a gas diffused
(r)  then, velocities in all possible directions.
Time taken for diffusion
(ii) The volume of the individual molecule
r1 V /t w /t d2
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 1 1  1 1  is negligible as compared to the total volume of the gas.

r2 V2 / t 2 w 2 / t 2 d1
(iii) Gaseous molecules are perfectly elastic so that
(a) When equal volume of the two gases
there is no net loss of kinetic energy due to their
diffuse, i.e. V1  V2
collisions.
r1 t 2 d2 (iv) The effect of gravity on the motion of the
then,  
r2 t1 d1 molecules is negligible.
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(b) When volumes of the two gases diffuse in the (v) Gaseous molecules are considered as point
same time, i.e. t1  t 2 masses because they do not posses potential energy. So
the attractive and repulsive forces between the gas
r1 V d2
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then,  1  molecules are negligible.

r2 V2 d1
(vi) The pressure of a gas is due to the continuous
(iii) Since, r  p (when p is not constant)
bombardment on the walls of the containing vessel.
ST

r1 P M2  P  (vii) At constant temperature the average K.E. of

then,  1  r  
 M 
r2 P2 M1  all gases is same.
(4) Rate of diffusion and effusion can be (viii) The average K.E. of the gas molecules is
determined as, directly proportional to the absolute temperature.
(i) Rate of diffusion is equal to distance (3) Kinetic gas equation : On the basis of above
travelled by gas per unit time through a tube of postulates, the following gas equation was derived,
uniform cross-section.
1
(ii) Number of moles effusing per unit time PV  2
mnu rms
3
is also called rate of diffusion.
where, P = pressure exerted by the gas
(iii) Decrease in pressure of a cylinder per unit
time is called rate of effusion of gas. V = volume of the gas
m = average mass of each molecule
 Gaseous State 231
n = number of molecules (ii) The total number of bimolecular
1
u = root mean square (RMS) velocity of the gas. collision per unit time are given by, Z AA   2 u av. n 2
(4) Calculation of kinetic energy 2
(iii) If the collisions involve two unlike molecules,
We know that,
the number of bimolecular collision are given by,
1
K.E. of one molecule  mu 2 2  (M A  M B ) 
1/ 2
2 Z AB   AB 8RT 
 MAMB 
1 3
K.E. of n molecules  mnu 2  PV  A  B
2 2 where,  AB 
2
1
( PV  mnu 2 ) M A , M B are molecular weights (M  mN 0 )

60
3
3 (iv) (a) At particular temperature; Z  p 2
n = 1, Then K.E. of 1 mole gas  RT
2 (b) At particular pressure; Z  T 3 / 2
( PV  RT ) (c) At particular volume; Z  T 1 / 2
(3) During molecular collisions a molecule covers

E3
3
  8 .314  T  12 .47 T Joules . a small distance before it gets deflected. The average
2
distance travelled by the gas molecules between two
Average K.E. per mole 3 RT 3
   KT successive collision is called mean free path ().
N (Avogadro number ) 2 N 2
Average distance travelled per unit time( u av )
 .
 R  No. of collisions made by single molecule per unit time (Z A )
K   Boltzmann constant 
 N

This equation shows that K.E. of translation of a

gas depends only on the absolute temperature. This is
known as Maxwell generalisation. Thus average K.E. 

ID 
u av
2 2 u avr.n

1
2n  2
(4) Based on kinetic theory of gases mean free
T
path,   . Thus,
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T. P
(i) Larger the size of the molecules,
If T  0 K (i.e.,  273 .15 o C) then, average K.E. = 0.
1
Thus, absolute zero (0K) is the temperature at which smaller the mean free path, i.e.,  
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(radius) 2
molecular motion ceases.
(ii) Greater the number of molecules per
Molecular collisions
unit volume, smaller the mean free path.
(1) The closest distance between the centres of (iii) Larger the temperature, larger the mean free
two molecules taking part in a collision is called path.
molecular or collision diameter (). The molecular (iv) Larger the pressure, smaller the mean free
diameter of all the gases is nearly same lying in the
D

path.
order of 10 8 cm . (5) Relation between collision frequency (Z) and
u
mean free path () is given by, Z  rms

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
Molecular
diameter
Molecular speeds or velocities
(1) At any particular time, in the given sample of
ST

(2) The number of collisions taking place in unit gas all the molecules do not possess same speed, due to
time per unit volume, called collision frequency (z). the frequent molecular collisions with the walls of the
(i) The number of collision made by a container and also with one another, the molecules
single molecule with other molecules per unit time are move with ever changing speeds and also with ever
given by, Z A  2 2uav.n changing direction of motion.
(2) According to Maxwell, at a particular
where n is the number of molecules per unit
temperature the distribution of speeds remains
molar volume,
constant and this distribution is referred to as the
Avogadro number( N 0 ) 6.02  10 23 3
n  m Maxwell-Boltzmann distribution and given by the
Vm 0.0224 following expression,
3/2
dn 0  M  2
 4   .e  Mu / 2 RT
.u 2 dc
n  2RT 
 232 Gaseous State
where, dn 0  Number of molecules out of total (ii) Average velocity (v av ) : It is the average
number of molecules n, having velocities between c and of the various velocities possessed by the molecules.
c  dc , dn 0 / n  Fraction of the total number of v1  v 2  v 3  ...... v n 8 RT 8 kT
v av  ; v av  
molecules, M = molecular weight, T = absolute n M m
(iii) Most probable velocity ( mp ) : It is the
2
temperature. The exponential factor e  Mu / 2 RT is called
Boltzmann factor. velocity possessed by maximum number of molecules of
(3) Maxwell gave distribution curves of molecular a gas at a given temperature.
speeds for CO 2 at different temperatures. Special 2 RT 2 PV 2P
 mp   
features of the curve are : M M d
(i) Fraction of molecules with two high or two low

60
(5) Relation between molecular speeds or
speeds is very small. velocities,
(ii) No molecules has zero velocity. (i) Relation between u rms and v av :
(iii) Initially the fraction of molecules increases
vav  0.9213  urms
in velocity till the peak of the curve which pertains to
or urms  1.085  vav

E3
most probable velocity and thereafter it falls with
increase in velocity. (ii) Relation between  mp and u rms :
Ump  mp  0.816  urms
300 K (T1) or u rms  1.224   mp
T1<T2<T3
Ump
Uav (iii) Relation between  mp and v av :
UrmsU
mp

ID v av  1.128   mp
Fraction of
molecules

1500 K (T2) 1800 K (T3) (iv) Relation between  mp , v av and u rms

 mp : v av : u rms
Molecular speed
U
2 RT 8 RT 3 RT
: :
(4) Types of molecular speeds or Velocities M M M
(i) Root mean square velocity (urms) : It is 8
YG

the square root of the mean of the squares of the 2 : : 3


velocity of a large number of molecules of the same
1.414 : 1.595 : 1.732
gas.
1 : 1.128 : 1.224 i.e.,
u12  u 22  u 32  ..... u n2  mp  v av  u rms
u rms 
n
Real and Ideal gases
(1) Gases which obey gas laws or ideal gas
D

u rms 
3 PV

3 RT

3 RT

3kT

3P equation (PV  nRT ) at all temperatures and pressures
(mN 0 )  M (mN 0 )  M M m d are called ideal or perfect gases. Almost all gases
R deviate from the ideal behaviour i.e., no gas is perfect
U

where k = Boltzmann constant 

N0 and the concept of perfect gas is only theoretical.

(a) For the same gas at two different (2) Gases tend to show ideal behaviour more and
temperatures, the ratio of RMS velocities will be, more as the temperature rises above the boiling point
ST

of their liquefied forms and the pressure is lowered.

u1 T1
 Such gases are known as real or non ideal gases. Thus, a
u2 T2
“real gas is that which obeys the gas laws under low
(b) For two different gases at the same pressure or high temperature”.
temperature, the ratio of RMS velocities will be,
(3) The deviations can be displayed, by plotting
u1 M2 the P-V isotherms of real gas and ideal gas.

u2 M1
H2
(c) RMS velocity at any temperature t o C
3 P(273  t) He
may be related to its value at S.T.P. as, u t  .
273 d
PV
Z 
nRT
O2
N2
CH4
CO2
P
 Gaseous State 233
(2) Vander Waal's equation is obeyed by the real
gases over wide range of temperatures and pressures,
hence it is called equation of state for the real gases.
(3) The Vander Waal's equation for n moles of the
(4) It is difficult to determine quantitatively the
gas is,
deviation of a real gas from ideal gas behaviour from
the P-V isotherm curve as shown above.  2 
P  n a  [V  nb ]  nRT
Compressibility factor Z defined by the equation,  V 2 
 Volume correction for
PV  ZnRT or Z  PV / nRT  PVm / RT Pressure correction
for molecular attraction
finite size of molecules

is more suitable for a quantitative description of a and b are Vander Waal's constants whose values

the deviation from ideal gas behaviour.
(5) Greater is the departure of Z from unity, more
is the deviation from ideal behaviour. Thus, when
(i) Z  1 , the gas is ideal at all
temperatures and pressures. In case of N 2 , the value of
60
depend on the nature of the gas. Normally for a gas
a  b .
(i) Constant a : It is a indirect measure of
magnitude of attractive forces between the molecules.
Greater is the value of a, more easily the gas can be

Z is close to 1 at 50 o C . This temperature at which a
real gas exhibits ideal behaviour, for considerable
range of pressure, is known as Boyle's temperature or
Boyle's point (TB ) .
(ii) Z  1 , the gas is less compressible than
expected from ideal behaviour and shows positive
deviation, usual at high P i.e. PV  RT .
(iii) Z  1 , the gas is more compressible than
expected from ideal behaviour and shows negative
ID
deviation, usually at low P i.e. PV  RT .
U
(iv) Z  1 for H 2 and He at all pressure i.e.,
always shows positive deviation.
YG
E3
liquefied. Thus the easily liquefiable gases (like
SO 2  NH 3  H 2 S  CO 2 ) have high values than the
permanent gases (like N 2  O2  H 2  He) .
Units of 'a' are : atm. L2 mol 2 or atm. m 6 mol 2 or
N m 4 mol 2 (S.I. unit).
(ii) Constant b : Also called co-volume or
excluded volume,
4
3

b  4 N 0 v  4 N 0  r 3 

It's value gives an idea about the effective size
of gas molecules. Greater is the value of b, larger is the
size and smaller is the compressible volume. As b is the

(v) The most easily liquefiable and highly
soluble gases (NH 3 , SO 2 ) show larger deviations from
ideal behaviour i.e. Z  1 .
(vi) Some gases like CO 2 show both negative and
positive deviation.
(6) Causes of deviations of real gases from
D
effective volume of the gas molecules, the constant
value of b for any gas over a wide range of temperature
and pressure indicates that the gas molecules are
incompressible.
Units of 'b' are : L mol 1 or m 3 mol 1 (S.I. unit)
(iii) The two Vander Waal's constants and Boyle's

temperature (TB ) are related as,

ideal behaviour : The ideal gas laws can be derived
from the kinetic theory of gases which is based on the a
TB 
following two important assumptions, bR
U

(i) The volume occupied by the molecules is (4) Vander Waal's equation at different
negligible in comparison to the total volume of gas. temperature and pressures
(ii) The molecules exert no forces of attraction (i) When pressure is extremely low : For
one mole of gas,
ST

upon one another. It is because neither of these

assumptions can be regarded as applicable to real gases  a  a ab
 P  2  (V  b )  RT or PV  RT   Pb  2
that the latter show departure from the ideal  V  V V
behaviour. (ii) When pressure is extremely high : For
Vander Waal's equation one mole of gas,
PV Pb Pb
(1) To rectify the errors caused by ignoring the PV  RT  Pb ; 1 or Z  1 
RT RT RT
intermolecular forces of attraction and the volume where Z is compressibility factor.
occupied by molecules, Vander Waal (in 1873) modified (iii) When temperature is extremely high : For
the ideal gas equation by introducing two corrections,
one mole of gas,
(i) Volume correction (ii) Pressure PV  RT .
correction (iv) When pressure is low : For one mole of gas,
 234 Gaseous State
 a  a ab
(iii) Wohl equation : P 
RT a c
 P  2  (V  b )  RT or PV  RT  Pb   2  
 V  V V (V  b) V (V  b) V 2
PV a a RT
or 1 or Z  1  (iv) Dieterici equation : P  .e a / RTV .
RT VRT VRT V b
(v) For hydrogen : Molecular mass of The expression is derived on the basis of the
hydrogen is small hence value of 'a' will be small owing concept that molecules near the wall will have higher
a potential energy than those in the bulk.
to smaller intermolecular force. Thus the terms and
V (v) Kammerlingh Onnes equation : It is
ab the most general or satisfactory expression as equation
may be ignored. Then Vander Waal's equation
V2 expresses PV as a power series of P at a given

60
becomes, temperature.

PV  RT  Pb or
PV
1
Pb PV  A  BP  CP 2  DP 3  ......
RT RT Here coefficients A, B, C etc. are known as first,
Pb second and third etc. virial coefficients.
or Z  1 

E3
RT (a) Virial coefficients are different for different
In case of hydrogen, compressibility factor is gases.
always greater than one. (b) At very low pressure, first virial coefficient, A
(5) Merits of Vander Waal's equation = RT.
(i) The Vander Waal's equation holds good for (c) At high pressure, other virial coefficients also
real gases upto moderately high pressures. become important and must be considered.
(ii) The equation represents the trend of the
isotherms representing the variation of PV with P for
various gases.
(iii) From the Vander Waal's equation it is
ID The critical state
(1) A state for every substance at which the
vapour and liquid states are indistinguishable is known
as critical state. It is defined by critical temperature
U
possible to obtain expressions of Boyle's temperature, and critical pressure.
critical constants and inversion temperature in terms
(2) Critical temperature (Tc) of a gas is that
of the Vander Waal's constants 'a' and 'b'.
temperature above which the gas cannot be liquified
YG

(iv) Vander Waal's equation is useful in obtaining however large pressure is applied. It is given by,
a 'reduced equation of state' which being a general 8a
equation of state has the advantage that a single curve Tc 
27 Rb
can be obtained for all gases when the equation if
(3) Critical pressure (Pc) is the minimum
graphically represented by plotting the variables.
pressure which must be applied to a gas to liquify it at
(6) Limitations of Vander Waal's equation
a
its critical temperature. It is given by, Pc 
D

(i) This equation shows appreciable 27b 2

deviations at too low temperatures or too high
(4) Critical volume (Vc) is the volume occupied
pressures.
by one mole of the substance at its critical temperature
U

(ii) The values of Vander Waal's constants a and critical pressure. It is given by, Vc  3b
and b do not remain constant over the entire ranges of
(5) Critical compressibility factor (Zc) is given
T and P, hence this equation is valid only over specific
PV 3
range of T and P. by, Z c  c c   0 .375
ST

RT c 8
(7) Other equations of state : In addition to
Vander Waal's equation, there are also equations of A gas behaves as a Vander Waal’s gas if its critical
state which have been used to explain real behaviour of compressibility factor (Zc ) is equal to 0.375. A
gases are, substance is the gaseous state below Tc is called vapour
(i) Clausius equation : and above Tc is called gas.
 a 
P  2 
(V  b)  RT . Here 'c' is another constant Degrees of freedom of a gaseous molecule
 T (V  c ) 
(1) The motion of atoms and molecules is
besides a, b and R.
generally described in terms of the degree of freedom
 a  which they possess.
(ii) Berthelot equation :  P   (V  b )  RT .
 TV 2  (2) The degrees of freedom of a molecule are
defined as the independent number of parameters
 Gaseous State 235
required to describe the state of the molecule (v) For monoatomic gas,
completely. 5
Cp R
(3) When a gaseous molecule is heated, the ( )   2  1.66 .
Cv 3
energy supplied to it may bring about three kinds of R
motion in it, these are, 2
7
(i) The translational motion (ii) The Cp R
rotational motion (iii) The vibrational (vi) For diatomic gas ( )   2  1.40
Cv 5
motion. R
2
This is expressed by saying that the molecule Cp 8R
(vii) For triatomic gas ( )    1 .33
possesses translational, rotational and vibrational degrees of Cv 6R

60
freedom.
Liquefaction of gases
(4) For a molecule made up of N atoms, total
degrees of freedom = 3N. Further split up of these is as (1) A gas may be liquefied by cooling or by the
follows, application of high pressure or by the combined effect
of both. The first successful attempt for liquefying
Translational Rotational

Vibrational
For linear molecule : 3 2
For non-linear molecule : 3 3
Specific and Molar heat capacity of gases
(1) Specific heat (or specific heat capacity) of a
substance is the quantity of heat (in calories, joules,
kcal, or kilo joules) required to raise the temperature of
1g of that substance through 1 o C . It can be measured
at constant pressure (c p ) and at constant volume (c v ) .
U
(2) Molar heat capacity of a substance is the
quantity of heat required to raise the temperature of 1
mole of the substance by 1 o C .
YG
E3
gases was made by Faraday.
(2) Gases for which the intermolecular forces of
3N – 5
attraction are small such as H 2 , N 2 , Ar and O 2 , have
3N – 6
low values of Tc and cannot be liquefied by the
application of pressure are known as “permanent
ID gases” while the gases for which the intermolecular
forces of attraction are large, such as polar molecules
NH 3 , SO 2 and H 2 O have high values of Tc and can be
liquefied easily.
(3) Methods of liquefaction of gases : The modern
methods of cooling the gas to or below their Tc and hence
of liquefaction of gases are done by Linde's method and
Claude's method.

 Molar heat capacity = Specific heat capacity 
Molecular weight, i.e.,
Cv  cv  M and C p  c p  M .
(3) Since gases upon heating show considerable
tendency towards expansion if heated under constant
pressure conditions, an additional energy has to be
D
(i) Linde's method : This process is based
upon Joule-Thomson effect which states that “When a
gas is allowed to expand adiabatically from a region of
high pressure to a region of extremely low pressure, it
is accompained by cooling.”
(ii) Claude's method : This process is

based upon the principle that when a gas expands

supplied for raising its temperature by 1 o C relative to
adiabatically against an external pressure (as a piston
that required under constant volume conditions, i.e.,
in an engine), it does some external work. Since work
C p  Cv or C p  Cv  Work done on expansion, PV ( R)
is done by the molecules at the cost of their kinetic
U

where, C p  molar heat capacity at constant energy, the temperature of the gas falls causing
pressure; Cv  molar heat capacity at constant volume. cooling.
(4) Some useful relations of Cp and Cv (iii) By adiabatic demagnetisation.
ST

(i) C p  Cv  R  2 calories  8.314 J (4) Uses of liquefied gases : Liquefied and gases
compressed under a high pressure are of great importance
3
(ii) Cv  R (for monoatomic gas) and in industries.
2
(i) Liquid ammonia and liquid sulphur
3
Cv   x (for di and polyatomic gas), where x varies dioxide are used as refrigerants.
2
(ii) Liquid carbon dioxide finds use in soda
from gas to gas.
Cp fountains.
(iii)   (Ratio of molar capacities) (iii) Liquid chlorine is used for bleaching and
Cv
disinfectant purposes.
(iv) For monoatomic gas Cv  3 calories whereas,
(iv) Liquid air is an important source of oxygen in
C p  Cv  R  5 calories rockets and jet-propelled planes and bombs.
 236 Gaseous State
(v) Compressed oxygen is used for welding
purposes.
(vi) Compressed helium is used in airships.
(5) Joule-Thomson effect : When a real gas is
allowed to expand adiabatically through a porous plug
or a fine hole into a region of low pressure, it is
accompanied by cooling (except for hydrogen and
helium which get warmed up).
Cooling takes place because some work is done to
overcome the intermolecular forces of attraction. As a
 1 Cal = 4.2 Joule, 1 Kcal = 4200 Joule
 The gas which has least mean free path has
maximum value of a, is easily liquefied and has
maximum value of Tb.
 Tc < Tb < Ti
 For critical constants, compression factor Z is < 1.
 Boyle’s law and Avogadro’s law are applicable
under limiting condition. This limiting condition
is P  0.

60
result, the internal energy decreases and so does the
temperature.  Tc = 0.296 Tb ; Ti = 6.75 Tc
Ideal gases do not show any cooling or heating
 Mean free path increases if H2 is replaced by He.
because there are no intermolecular forces of attraction
i.e., they do not show Joule-Thomson effect.

E3
During Joule-Thomson effect, enthalpy of the
system remains constant.
Joule-Thomson coefficient.   (T / P)H .

For cooling,   ve (because dT and dP will be

ve )
For heating   ve (because dT  ve, dP  ve) .

For no heating or cooling   0 (because dT  0 ) .

ID
U
(6) Inversion temperature : It is the temperature
at which gas shows neither cooling effect nor heating
effect i.e., Joule-Thomson coefficient   0 . Below this
temperature, it shows cooling effect and above this
YG

temperature, it shows heating effect.

Any gas like H 2 , He etc, whose inversion
temperature is low would show heating effect at room
temperature. However, if these gases are just cooled
below inversion temperature and then subjected to
Joule-Thomson effect, they will also undergo cooling.
D
U
ST

 If the number of molecules present in 1 c.c. of

the gas or vapour at S.T.P., then that is called
loschmidt number. Its value is 2.687  1019 per
c.c.
 CO2 > SO2 > SO3 > PCl3 is order of rate of
diffusion.
 Vapour density is independent of temperature
and has no unit while absolute density is
dependent of temperature and has unit of gm–1
 The isotherms of CO2 were first studied by
Andrews.