01 Gaseous State#### PDF

GASEOUS STATE
IIT–JEE Syllabus:
Gas laws; equation of state for an ideal gas; kinetic theory of gases; root mean
square velocity and its relation with temperature; average velocity; Van der Waal’s
equation, eudiometry.
A gas neither possesses definite volume nor definite shape but it has a definite mass. It
acquires the shape and volume of the container in which it is placed. So the volume of a gas is
simply the volume of the vessel in which it is kept. The temperature of the gas is measured by
suitable thermometer. It is expressed generally in two ways (celsius scale and kelvin scale),
which are related as
Temperature on kelvin scale = 273.15 + Temperature on celsius scale.
GAS LAWS
Boyle's Law
Robert Boyle discovered that there existed a relation between the pressure and the volume of
a fixed mass of gas at a fixed temperature. According to this law, volume of definite mass of
gas is inversely proportional to pressure at constant temperature.
1
 V (at constant T and n)
P
 PV = Constant or P1V1 = P2V2
V log P PV
P log V P
(a) (b) (c)
Charles' Law
Jacques Charles discovered that if the pressure is kept constant, the volume of a gas sample
increases linearly with the temperature for a fixed mass of gas. The unit of temperature used is
Kelvin.
 V  T ( at constant P and n)
V V1 V2
 = Constant or 
T T1 T2
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V log V
T log T
(a) (b)
GayLussac's Law
Gay Lussac discovered that if the volume P
is kept constant, the pressure of a fixed
mass of a gas increases linearly with the
rise in temperature. T
 PT (at constant V and n)

P P P
= Constant or 1  2
T T1 T2
Avogadro's Law
Amadeo Avogadro stated that samples of different gases which contain the same number of
molecules occupy the same volume at the same temperature and pressure. It follows from
Avogadro's hypothesis that V  n (when T and P are constant)
V V V
 constant or 1  2
n n1 n2
Ideal Gas Equation

Combining all these laws, a simple equation can be arrived at, which relates P, V, n and T for
a gas.
 PV = nRT
This is called as ideal gas equation.
Physical Significance of Universal Gas Constant (R)

PV = nRT
PV
R=
nT
Force
 Volume
= Area
Number of moles  Temperature in K
Force
2
 (Length )3
(Length )
=
Number of moles  Temperature in K
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Force  Length (or displacement )

=
Number of moles  Temperatur e in K
Work done
=
Number of moles  Temperatur e in K
Therefore, R signifies the work done when the temperature of one mole (n = 1) of an ideal gas
has been increased by 1 K.
R is expressed in work or energy unit mol1 K1.
R = 0.0821 L atm mol1 K1
= 8.314  107 erg mol1 K1
= 8.314 joule mol1 K1
= 1.987 cal mol1 K1
These values can be used as energy conversion factor.
Dalton's Law of Partial Pressure

According to this law total pressure of a mixture of non reacting gases is equal to the sum of
partial pressures of individual gases.
P = PA + PB + PC + ……………….. (in mixture of gases which do not react
chemically)
Let nA moles of A, nB moles of B and nC moles of C are filled in a vessel of volume V
maintained at temperature T. Then, total pressure will be
PV = (nA + nB + nC)RT (Gas equation) …..(i)
Let only nA moles of A is added in the vessel kept at same temperature then
PAV = nART …..(ii)
Similarly,
PBV = nBRT …..(iii)
PCV = nCRT …..(iv)
On adding, (ii), (iii) and (iv) we get
(PA + PB + PC)V = (nA + nB + nC) RT …..(v)
Now comparing equation (i) and (v) we get
P  PA  PB  PC
Alternatively
Dividing equation (ii) by (i)
PA V n A RT

PV (n A  n B  n C ) RT
PA nA
 = XA (mole fraction of A)
P (n A  n B  n C )
PA = PXA …..(i)
Similarly, PB = PXB …..(ii)
PC = PXC …..(iv)
on adding (i), (ii) and (iii) we get
(PA + PB + PC) = P (XA + XB + XC)
Now, XA + XB + XC =1
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So, P  PA  PB  PC
The law can even be applicable to a mixture of reacting gases under the condition when
they have attained equilibrium (at which the number of moles of each constituent species
remains fixed.
Amagat's Law Of Partial Volumes

It is a law which is similar to Dalton's law of partial pressure. According to this law total
volume occupied by a mixture of nonreacting gases is equal to the sum of partial volumes of
component gases of the mixture.
V = VA + VB + VC+………… (in mixture of gases)
PA
According to Dalton's law = mole fraction
P
V
So, According to Amagat's law A = mole fraction
V
Even though Dalton's assumption is more accurate and it is hard to imagine different gases
occupying different regions of space in the container, it is only a matter of convenience as to
which assumption we choose to make.
MOLECULAR MASS AND GAS DENSITIES

Actual Density
w
For an ideal gas, PV = nRT or PV = RT , where w = mass of the gas in grams and
M
M = Molecular weight in g/mole.
w
 PM = RT
V
or PM = RT, where  is the density of the gas.
PM
=
RT
Vapour Density
For gases, another term which is often used is vapour density. Vapour density of a gas is
defined as the ratio of the mass of the gas occupying a certain volume at a certain
temperature and pressure to the mass of hydrogen occupying the same volume at the same
PVM
temperature and pressure i.e. Wgas =
RT
PV  2
and WH 2  ( mol. weight of Hydrogen is 2)
RT
Wgas M
  = Vapour density of the gas
WH 2 2
Molecular weight of the gas
 Vapour density of a gas =
2
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Vapour density of a gas is same at any temperature, pressure and volume.
Molecular Weight And Effective Molecular Weight

Molecular weight of a gas mixture or effective molecular weight: Suppose we have to find
the molecular weight of air and we are told that air contains 79% nitrogen and 21% oxygen
(by mole or by volume).
First of all let us understand what is meant by molecular weight of a gas. Molecular weight of
a gas is the weight in gms of one mole of the gas (hence the unit gm/mole). Now if we take
one mole of air it would contain 79/100 moles of nitrogen and 21/100 moles of oxygen. The
weight of one mole of air would be (0.79  28) + (0.21  32) = 28.84 gm/mole.
 Meffective = XiMi =  mole fraction of a gas  mol. wt. of a gas

n moles of a gas
Xi (Mole fraction) of a gas = 
 n i Total moles of all the gases present in the mixture
EXAMPLE 1
To a good approximation air consists of 21% of O2 and 79% of N2 by volume.
(i) Calculate the mean molecular weight of dry air.
(ii) What volume would 40 gm of air occupy at 20°C and 745 mm of Hg pressure?
(iii) If relative humidity of air is 50% what will be the density of moist air at 20°C under
atmospheric pressure of 753.73 mm of Hg pressure? (Vapour pressure of water at
20°C = 17.5 mm of Hg)
SOLUTION
(i) Volume fraction of a gas= Mole fraction of the gas
Hence, 100 moles of air = 21 moles of O2 + 79 moles of N2
= 21  32 gm O2 + 79  28 gm N2
= 2884 gm N2 and O2
 Mean molecular weight of one mole of air = 2884 g = 28.84 g
100
(ii) The gas equation PV = nRT = w RT
M
Given that P = 745 mm of Hg = 745 atm = 0.98 atm
760
40  0.082  293
 V= = 34 litres
28.84  0.98
(iii)Since relative humidity is 50%
 Partial pressure of water vapour in atmospheric air = 50
 17.5 mm = 8.75 mm
100
Since atmospheric pressure of moist air = 753.75 mm
 Partial pressure of O2 + partial pressure of N2 = (753.758.75) mm
= 745 mm
In other words, total pressure of dry air = 745 mm
 Partial pressure of N2 = p N 2 = (Total pressure of dry air)  mole fraction of N2 in dry air
= 745  0.79 = 588.55 mm
Similarly, p O 2 = 745  0.21 = 156.45 mm
Let volume of moist air taken = 1 litre
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 Total wt. of 1 litre of moist air

= Wt. of water vapour + Wt. of N2 + Wt of O2 contained in moist air
To get the weight of individual constituents of air let us first calculate out their individual
moles by PV = nRT
8.75 1
moles of water vapour n = PV  = 0.000749
RT 760  0.082  293
 wt. of water vapour = 0.000749  18 gm = 0.00862 gm
588.55  1
moles of N2, n = PV =  0.0322
RT 760  0.082  293
 wt. of N2 = 0.0322  28 = 0.9016 gm
156.45  1
moles of O2, n = PV = = 0.00857
RT 760  0.082  293
 wt. of O2 = 0.0085  32 = 0.2742 gm
Hence, total wt. of 1 litre of moist air = (0.00862 + 0.9016 + 0.2742) = 1.1844 gm
 Density of moist air = 1.1844 gm/litre
Graham's Law
According to Graham's law of diffusion, when two gases are confined under the same
conditions of temperature and pressure, the rate of diffusion is equal to inverse root of their
r1 M2
respective molecular weights i.e. for two gases 1 and 2,  but this is valid only when
r2 M1
the two gases are at same pressure.
KP
Further research on this law showed that r = , where P is the pressure of the gas and K is
M
a constant.
When this was researched further, it was revealed that the rate of effusion (effusion is a
process in which the gas comes out of the container into vacuum through a pinhole, while
diffusion relates to the movement of the two gases in and out of the container or within the
container) of a gas from a container is given by
 PA
r= , where r is the rate of effusion of a gas from a container measured in
2π MRT
moles of the gas effused (or diffused) per second P is the difference in pressures of the gas
from the place it is effusing and to the place it is effused in Pa, A is the area of the orifice in
m2 assuming it to be very small (like a pin-hole), R is the universal gas constant with the value
of 8.314 J/mole Kelvin, T is the absolute temperature of the gas and M is the molecular
weight of the gas in kg/mole.
It should be noted that the rate of effusion or diffusion actually depends on the pressure
difference of the gas and not simply on its pressure. Moreover the pressure difference is to be
measured for this gas only i.e. if a container holds He at a pressure of 0.1 atm and if a small
pin-hole is made in the container and if the container is placed in a room, then the rate of
diffusion of the He gas from the container to outside depends only on its pressure difference,
which is 0.1  0 (as the there is no He in the atmosphere). This implies that the diffusion of a
gas is not dependent on the diffusion of any other gas.
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Whenever we consider the diffusion of a gas under experimental conditions, we always

assume that the gas diffuses in vacuum and during the time period for which the diffusion is
studied, the rate of diffusion (or the composition of the diffusing or effusion mixture of gases)
remains constant.
EXAMPLE 2
Two container A and B have the same volume. Container A contains 5 moles of O2 gas.
Container B contains 3 moles of He and 2 moles of N2. Both the containers are separately
kept in vacuum at the same temperature. Both the containers have very small orifices of the
same area through which the gases leak out . Compare the rate of effusion of O2 with that
of He gas mixture.
SOLUTION
Since both the containers are in the same conditions of P,V and T,
rO 2 Mmix
=
rm ix MO 2
As the mixture contains three moles of He and two moles of N2, the effective molecular
weight of the mixture would be.
3 2
 4   28 = 13.6
5 5
rO 2 13.6
 = = 0.652
rm ix 32
Though this solution looks OK, there is one big flaw in it. Find the error in the solution.
The error is that we have assumed that He and N2 from vessel B would effuse out with the
same rate. This assumption happened in because we have taken the composition of the gas
mixture coming out of the vessel to be same as that of the mixture that was inside the vessel .
It should be duly noted that the two mixtures (inside and those that are effused out) have
different compositions. Therefore first we must find the composition of the gas mixture
coming out of the vessel B.
rN2 2 4 2 1
  = 0.252
rHe 3 28 3 7
This means that initially the ratio of moles of N2 to the moles of He coming out of the
vessel are in the molar ratio of 0.252 and not 2 .
3
Let moles of the He coming out to be x
 moles of N2 coming out is 0.252 x
n N2 0.252 x
  = 0.2
n total 1.252 x
n He
= 0.8
n total
 Mmix = 0.2 28 + 0.84 = 8.8
rO2 8.8
  = 0.52
rmix 32
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EXAMPLE 3
The composition of the equilibrium mixture for the equilibrium Cl 2 2Cl at 1470 K
may be determined by the rate of diffusion of the mixture through a pin hole. It was found
that at 1470 K, the degree of dissociation of Cl2 is 0.14, then calculate the ratio of rate of
effusion of the equilibrium mixture to that of Krypton (atomic weight = 83.8) under similar
conditions.
SOLUTION
For the equilibrium Cl2(g) 2Cl(g)
Initial moles 1 0
At equilibrium 1x 2x
(x is the degree of dissociation)
Total moles at equilibrium = 1  x + 2x = 1 + x = 1 + 0.14 = 1.14
The composition of the gas mixture coming out would be
rCl 2 0.86 35.5
 = 2.17
rCl 0.28 71
Let the moles of Cl atom coming out be x, then the moles of Cl2 coming out would be 2.17 x.
2.17 x
 X Cl 2  = 0.68 and XCl = 0.32
3.17 x
 Mmix = (0.68  71) + (0.32  35.5) = 59.64
r M Kr 83.8
 mix   = 1.18
rKr M mix 59.64
EXAMPLE 4
The pressure in a bulb of constant volume dropped from 2000 to 1500 mm of Hg in
47 minutes when the contained He leaked through a small hole. Calculate the pressure of
CO2 in the same vessel after 20 minutes if the initial pressure of CO2 in the vessel is
2000 mm of Hg. Assume the gases are leaking through same hole to vacuum. Also assume
the rate of leakage of gas is directly proportional to the pressure of gas in the vessel under
given conditions.
SOLUTION
For He,
Po
k  t = 2.303 log
Pf
2.303 2000
kHe = log = 6.12  103 min1
47 1500
k He M CO2 44
 
k CO2 M He 4
k He 6.12  10 3
k CO2   = 1.85  103 min1
11 11
For CO2 ,
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Po
k CO2  t  2.303 log
Pf
2000
1.85  103  20 = 2.303 log
Pf
Pf = 1927 mm of Hg
KINETIC THEORY OF GASES

Maxwell, Boltazmann and Bernauli gave some generalization about gases called kinetic
theory. Postulates of the kinetic theory are given below
1. Gases are made up of small structural units called molecules or atoms. Volume of these
units is considered to be negligible as compared to total volume occupied by the gas.
2. Gas molecules are always in rapid random motion colliding with each other and with the
wall of container.
3. Collision between gas molecules is perfectly elastic, i.e, no momentum is lost during the
collision.
4. Pressure exerted by the gas is due to collision of gas molecules with the wall of container.
5. There is no interaction between gas molecules i.e., neither they attract nor they repell each
other.
6. Kinetic energy of gas molecules depends upon the temperature only.
KE  T (absolute temperature)
Derivation Of Kinetic Gas Equation

y
Let us consider a cubical vessel of edge
length (l). Let n’ molecules are moving with
velocity 'C'. For simplicity assume that n’/3
molecules are moving along each axis.
Momentum before collision = mC C
Momentum after collision = mC m
where, m = mass of each gas molecule. x
z l
Change in momentum= mC  (mC) = 2mC
Distance travelled by a molecule between two successive collisions on the same wall = 2.
From Newton’s law
C
No. of collisions per second on a wall =
2
Rate of change of momentum = Change in momentum  No. of collision per sec.
C mC 2
= 2mC  
2 
n' mC2
For n’/3 molecules, rate of change of momentum = 
3 
Now, from Newton’s law
Rate of change of momentum = Force = Pressure  Area = P   2
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n' mC 2
 = P  2 V = Volume of the container
3 
1
mn' C 2  P 3  PV Along any one axis
3
Thus, similarly we may write the expression for other two axes.
1
3  mn'C 2  3PV (for all three axes)
3
1
PV  mn'C 2 (kinetic gas equation )
3
where C is the RMS velocity of the gas.
Kinetic Energy Of Gases

Kinetic energy of a gas is directly proportional to temperature in Kelvin
1
KE of one molecule = mC 2
2
1
Now, we know PV = mn’C2
3
3 1
PV = mn’C2
2 2
3 1
nRT = mn’C2 (PV = nRT)
2 2
 Kinetic energy of one mole of a gas
1 3
NAmC2 = RT (where NA = Avogadro's Number)
2 2
3 R 3
KE of one molecule = T  kT
2 NA 2
(where k = Boltzmann constant = 1.38  1023 J K1 mol2)
DEVIATION FROM IDEAL BEHAVIOUR

Non Ideal or Real Gas
An ideal gas obeys gas laws (PV = nRT) at all temperatures and pressures. However, there is
no ideal gas in nature under normal conditions. Gases H2, N2, CO2 etc. are nonideal or real.
Extent of deviation from ideal behaviour of a real gas is expressed by a parameter called
compressibility factor (Z).
PV
Z= ; for ideal gases Z = 1
RT
Difference between unit compressibility and the compressibility factor of real gas is a
measure of nonideality of the gas under consideration.
When compressibility factor is plotted against pressure we get following curves.
At low pressure (up to 10 atm), value of compressibility factor for all gases is one. For
hydrogen, value of 'Z' increases with increase in pressure whose compressibility curve always
lies above ideal gas curve. For CO2 and the N2 value of Z first decreases then increase with
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increase in pressure. Variation of temperature on compressibility factor for N2 may be

represented as shown in the fig.
2.0 N2 4.0
H2 200K
1.5 3.0 500K
Z = PV/RT CO2
1.0 Z = PV/RT 2.0
Ideal gas 1000 K
0.5 1.0 Ideal gas
0 0
Pressure Pressure
From the plot it is clear that, gases behave ideally at appreciably higher temperature.
Thus we may conclude that
(1) At high temperature and low pressure, gases behave ideally.
(2) Near the liquification point; there is greater deviation from ideal behaviour, since force of
attraction among gas molecules comes into existence.
(3) At high pressure and low temperature, the gases behave nonideally.
Van der Waals Equation for Real Gases

Vander Waal proposed that non ideality of a gas may be attributed to the following two
assumptions of kinetic theory
(1) Volume occupied by gas molecules or atoms is negligible.
(2) There is no interaction among the gas molecules. Thus, ideal gas equation (PV = nRT)
may not be applied for real gases. Both pressure and volume should be corrected in order
to use it for real gases.
Correction of Volume
In ideal gas equation, volume of the gas is taken as the volume of the container since volume
occupied by the gas molecules is considered negligible in kinetic theory. Van der Waal
proposed that gas molecules occupy definite volume. Thus
Real gas volume = Ideal volume  Volume occupied by gas molecules.
Videal = (Vreal  b) for one mole of gas
= (Vreal  nb) for n mole of gas
(b = Van der Waal's constant called excluded volume; it is the effective volume of gas
per mole).
Excluded volume is never exactly equal to the volume occupied by the gas; it is equal to the
four times of actual volume of molecules.
Let two molecules of radius 'r' collide with Excluded Volume
each other
Excluded volume for pair of gas molecules
4
= π (2r) 3 r r
3
4 
= 8 π r 3 
3 
Excluded volume per molecule
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4 
= 4  π r 3  = 4  Vm
3 
where Vm = Actual volume occupied by a molecule.
4
 b = 4   r3  NAV
3
Thus, we may say that excluded volume of gas molecules will be four times the actual volume
occupied by the molecules.
Correction of Pressure Wall of
the container
We know, that pressure exerted by gas
molecules is due to the collision of gas
molecules with the wall of container. Gas
molecule lying in the interior side is equally
attracted from all side by the neighbouring Reduced
molecules and hence there will be no net Velocity
attraction on the molecule.
The molecule that collides with the wall is pulled back by the neighbouring molecules hence
the molecule strikes with the reduced velocity.
Thus, actual pressure of the gas will be less than the ideal pressure
 Preal = Pideal  Pcorrection
or Pideal = Preal + Pcorrection
Pcorrection is determined by calculating the force with which the molecules is attracted by the
neighbouring molecule.
Force with which the molecule is pulled back by neighbouring molecules while colliding with
the wall is proportional to
(i) Number of molecules colliding per unit time.
(ii) Number of molecules present in immediate vicinity of colliding molecule; both of these
factors are proportional to n/V (number of molecules present per unit volume).
n n
Thus, Pcorrection  
V V
n2
=a ….(i) where 'a' is Van der Waal's constant
V2
an 2
 Pideal = Preal +
V2
Thus pressure P in ideal gas equation may be replaced as

 an 2 
P  2 
 V 
Now, the Van der Waal's equation of state may be given as
 2 
 P  an  (V  nb) = nRT
 V2 
 
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Vander waal’s equation for 1 mole of gas becomes

 a 
 P   (V  b) = RT
 V2 
Here, a, b are called Vander Waal's constant.
Calculation of Van der waal constant 'a' and 'b'

Excluded volume is nb for n moles of gases
volume Litre
 b= 
n mole
Thus, unit of 'b' is Litre per mole or m3 mole 1
PV 2 (Pressure) (Volume) 2
From equation (i) a= 
n2 (mole) 2
(N m 2 ) (m 3 ) 2
= 2
= N m4 mole2 or atm Litre2 mole2
(mole)
Corollary of Van der Waal Equation

(i) When Pressure Is Extremely Low
Van der Waal equation for one mole of gas may be written as,
  a
 P  (V  b) = RT …(i)
 V2

a ab
or PV = RT  + Pb + 2 …(ii)
V V
when pressure is extremely low then a/V, Pb and ab/ V 2 will be negligibly small hence.
PV = RT; Thus at very low pressure, the gas behaves ideally.
(ii)When Pressure Is Extremely High
At high pressure a/V2 may be neglected as compared to P; Thus Van der Waal equation
becomes:
PV = RT + Pb
PV Pb Pb
or 1  or Z =1+
RT RT RT
where Z is compressibility factor.
Thus, at high pressure, compressibility factor is greater than 1 and it increases with
increase in pressure.
(iii) When Temperature Is Extremely High

At high temperature, the volumes of the gases are very high. Thus Van der Waal's
equation becomes ideal equation.
PV = RT
(iv) When Pressure Is Not Too Low

Van der Waal's equation may be written as
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 a 
 P   (V  b) = RT
 V2 
At low pressure, V is large and b may be neglected as compared to V.
a
Thus, PV = RT 
V
PV a a
or 1  or Z=1
RT VRT VRT
Thus, at not too low pressure, compressibility factor is less than one.
(v) Behaviour of Hydrogen

Molar mass of hydrogen is small hence value of 'a' will be small owing to smaller
intermolecular force. Thus the terms a/V and ab/V 2 may be ignored. The Van der Waal's
equation may now be given as
PV = RT + Pb
PV Pb Pb
=1+ or Z=1+
RT RT RT
Thus, in the case of hydrogen, compressibility factor is always greater than one.
CRITICAL STATE
Gases are usually liquefied by lowering of temperature and increase in pressure. Of these two
factors, the influence of temperature is more important. Most gases are liquefied at ordinary
pressure by suitably lowering the temperature. But many gases like O2, H2, N2 etc cannot be
liquefied at ordinary temperature however high the pressure may be. For every gas there is a
temperature above which liquefaction is not possible whatever the pressure be.
The limiting temperature above which liquefaction is not possible is called the
critical temperature (Tc) of the gas. The minimum pressure necessary to liquefy a gas at the
critical temperature is called its critical pressure (Pc). The volume occupied by a gmmole of
the gas at the critical temperature and pressure is called its critical volume (Vc).
Expressions of Critical Constants in Terms of Van der Waals Constants

a 8a
Vc = 3b ; Pc = ; Tc =
27b 2 27Rb
Boyle Temperature (TB)
It is the temperature at which real gases behave ideally over a wide range of pressure. It’s
relation with Van der Waals constants can be expressed as
a
TB =
Rb
EXAMPLE 5
Calculate the pressure exerted by one mole of CO2 gas at 273 K if the van der Waals
constant a = 3.592 dm6 atm mol2. Assume that the volume occupied by CO2 molecules is
negligible.
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SOLUTION
 2   a 
 P  n a  V  nRT ; Since n = 1,  P   V  RT
 V 2   V2 

RT a 0.082  273 3.592  22.4 3.592 
P=  2   =  V   atm
V V V V2  V2 
EXAMPLE 6
One way of writing the equation of state for real gases is
 B 
PV = RT 1   .....
 V 
where B is a constant. Derive an approximate expression for B in terms of the van der
Waals constants a and b.
SOLUTION
For one mole of a real gas, the Van der Waal’s equation of state is
 a 
 P  2 (V  b)  RT
 V 
a RT
 P+ 2 
V Vb
RT a
 P=  2
Vb V
RTV a
 PV = 
Vb V
 V a 
 PV = RT   
 V  b RTV 
 V  b 1 a 
 PV = RT    
 V  RTV 
 b
1
a 
 PV = RT 1    
 V  RTV 
1 2
 b b b
Now, 1    1      .....
 V V V
 b  b 2 a 
 PV = RT 1      ....  
 V  V  RTV 
 1 a  
 PV = RT 1   b    ...... …(i)
 V RT  
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Now comparing equation (i) with the given expression,

a
B=b
RT
VELOCITY OF GAS MOLECULES

Distribution Of Molecular Velocities
Maxwell and Boltzmann proposed that gas molecules are always in rapid random motion
colliding with each other and with the wall of container. Due to such collisions, their
velocities always changes. A fraction of molecules have a particular molecular velocity at a
time. James Clark Maxwell calculated the distribution of velocity among fraction of total
number of molecules, on the basis of probability.
The distribution of velocities of different gas molecules may be shown by the following curve.
Most probable
velocity
Average velocity
273 K
Fraction of 1273 K
Molecules 2773 K
Molecular velocity
From the curve it may be concluded that
(i) Only a small fraction of molecules have either very low or very high velocity.
(ii) Curve becomes flat when temperature is raised i.e. distribution around average velocity
becomes wider. Average molecular velocity increases with rise in temperature.
(iii)Most of the molecules have velocity closer to most probable velocity represented by the
top of curve.
(iv) At higher temperature greater number of molecules have high velocity, while few
molecules have lower velocity.
Types of Molecular Velocity

Based on statistical predictions the average velocity (VAV) and the most probable velocity
(VMP) have been calculated. The average velocity is the statistical average of the velocities of
all the molecules. The most probable velocity is the velocity which maximum number of
molecules possess.
c1  c2  c3  ......... cn
VAV =
n
where c’s are the velocity of different gas molecules and n is the total no. of gas molecules.
8RT
VAV = (where M is the molecular weight of the gas)
πM
2RT
VMP =
M
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Root mean square speed (rms) is defined as the square root of the average of the square of
speeds.
n 1c12  n 2 c 22  n 3 c 23  .....
C=
n 1  n 2  .......
(where n1 is the number of gas molecules having velocity c1,
n2 is the number of gas molecules having velocity c2 and so on).
From kinetic gas equation we have

1
PV = mn' C 2
3
For 1 mole gas n = NA
 m  NA = molecular wt. = M
1
 PV = M C2
3
We have PV = RT for 1 mole of ideal gas
3RT 3RT
or C 2 = or C=
M M
Replacing C by VRMS.
3RT
VRMS  (when temperature is given)
M
3PV
VRMS  (when pressure and volume are given)
M
3P
VRMS  (when pressure and densities are given)
d
4. Interrelation of Molecular Velocities:

VAV 8RT  M 4
   1.1286
VMP πM  2RT π
 VAV = 1.128  VMP
VAV 8RT  M 8
   0.9213
VRMS πM  3RT 3π
or VAV = 0.921  VRMS
or Average velocity = 0.921  VRMS
VMP 2RT  M 2
   0.816
VRMS M  3RT 3
VRMS : VAV : VMP : : 1 : 0.921 : 0.816
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GAS EUDIOMETRY
The relationship amongst gases, when they react with one another, is governed by two laws,
namely Gay-Lussac law and Avogardro’s law.
Gaseous reactions for investigation purposes are studied in a closed graduated tube open at
one end and closed at other end of which is provided with platinum terminals for the passage
of electricity through the mixture of gases. Such a tube is known as Eudiometer tube and
hence the name Eudiometry is also used for Gas analysis.
During Gas analysis, the Eudiometer tube filled with mercury is inverted over a trough
containing mercury. A known volume of the gas or gaseous mixture to be studied is next
introduced, which displaces an equivalent amount of mercury. Next a known excess of
oxygen is introduced and the electric spark is passed, whereby the combustible material gets
oxidised. The volumes of carbon dioxide, water vapour or other gaseous products of
combustion are next determined by absorbing them in suitable reagents. For example, the
volume of CO2 is determined by absorption in KOH solution and that of excess of oxygen in
an alkaline solution of pyrogallol. Water vapour produced during the reaction can be
determined by noting contraction in volume caused due to cooling, as by cooling the steam
formed during combustion forms liquid (water) which occupies a negligible volume as
compared to the volumes of the gases considered. The excess of oxygen left after the
combustion is also determined by difference if other gases formed during combustion have
already been determined. From the data thus collected a number of useful conclusions
regarding reactions amongst gases can be drawn.
(a) Volume-volume relationship amongst Gases or simple Gaseous reactions.
(b) Composition of Gaseous mixtures.
(c) Molecular formulae of Gases.
(d) Molecular formulae of Gaseous Hydrocarbons.
The various reagents used for absorbing different gases are

O3   turperntine oil
O2   alkaline pyrogallol
NO   FeSO4 solution
CO2,SO2   alkali solution (NaOH, KOH, Ca(OH)2, HOCH2CH2NH2, etc.)
NH3   acid solution or CuSO4 solution
Cl2  water, alkali solution
CO   Ammoniacal cuprous chloride
H2O vapour   Conc. H2SO4, fused CaCl2
General Assumptions
In all problems, it is assumed that the sparking occurs at room temperature. This implies that
water formed would be in liquid state and that nitrogen gas is inert towards oxidation.
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Let us see how eudiometry principle is used for determining the composition of gaseous
mixture.
For example, we have a mixture of CH4 (methane) and C2H6 (ethane) measuring V ml. This
mixture is subjected to electric sparking in a eudiometer tube along with excess of oxygen
(A ml). On sparking (explosion) both (CH4 and C2H6) get combusted and form gaseous CO2
and H2O vapours. Let the volume of CH4 in the mixture be x ml. The reactions can be
written as
CH4 + 2O2  CO2 + 2H2O …(i)
7
x A  2x  (V  x) x 2x
2
7
C2H6 + O2  2CO2 + 3H2O …(ii)
2
7
Vx A  2x  (V  x) 2(Vx) 3(V  x)
2
After explosion, the reaction mixture is brought to the room temperature i. e. cooled, so water
will exist as liquid.
Volume before explosion (VBE) = x + V  x + A = V + A
7 3
Volume after explosion (VAE) = A  2x  (V  x) + x + 2 (V  x) = A  x  (V  x)
2 2
 Contraction in volume after explosion = VBE  VAE
3 3 3 5 x
=V+AA+x+ (V  x) = V + x + V x= V
2 2 2 2 2
1
= (5 V  x)
2
Alternatively,
In first reaction, the number of moles of reactant are same as that of the product, so as per the
stoichiometry of the reaction there is no contraction but since H2O exists as liquid, so the
contraction due to first reaction is 2x.
In the second reaction, 4.5 moles of reactant gives 5 moles of product. This means there is
expansion of 0.5 mole as per the stoichiometry of the reaction but H2O exists as liquid so due
to this, contraction will be of 3 moles. Overall there is contraction of 2.5 moles, so the
5
contraction due to second reaction is (V  x).
2
Net contraction in volume = Contraction in volume due to I reaction
+
Contraction in volume due to II reaction
5
= 2x + (V  x)
2
1
= (5V  x)
2
Let this contraction is given as V1 ml.
1
 V1 = (5V  x)
2
Using the value of V1 and V, x can be calculated and then the % composition can also be
reported.
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EXAMPLE 7
50 ml. of a mixture of NH3 and H2 was completely decomposed by sparking into nitrogen
and hydrogen. 40 ml of oxygen was then added and the mixture was sparked again. After
cooling to the room temperature the mixture was shaken with alkaline pyrogallol and a
contraction of 6 ml was observed. Calculate the % of NH3 in the original mixture.
SOLUTION
Let the volume of NH3 be x ml.
 Volume of H2 = (50– x) ml
On sparking,
NH3   ½N2 + 3 H2
2
Since 40 ml of O2 is added and sparked, it must have reacted with H2 to form liquid water.
Moreover since 6 ml contraction occurs with alkaline pyrogallol, 34 ml is the volume of O2
used up.
 total volume of H2 is 68 ( 2H2 + O2 
 2H2O)
 (50 – x) + x = 68
3
2
x
50 + = 68 ; x = 36
2
 NH3 = 72%
EXAMPLE 8
When a certain quantity of oxygen was ozonised in suitable apparatus, the volume
decreases by 4 ml. On addition of turpentine oil, the volume decreases further by 8 ml. Find
the formula of ozone, assuming all measurements are made at same temperature and
pressure.
SOLUTION
The reaction occuring in the ozoniser is the conversion of oxygen to ozone and the
conversion is never 100%. Let the volume of oxygen in the beginning be a ml.
nO2 2On
Initial volume a 0
Volume after a–nx 2x
attainment of
equilibrium
The initial volume reduction is due to reaction alone.
 initial volume – volume at equilibrium = 4 ml
 a–(a–n x +2 x) = 4
nx–2x=4
n x = 4+ 2 x …(i)
The second decrease in volume is due to absorption of ozone by turpentine oil.
 2 x = 8 and x = 4
Putting the value of x in equation (i)
 n x = 4+8 = 12
12
n= =3
4
 Molecular formula of ozone is O3.
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EXAMPLE 9
15 ml of an oxide of nitrogen was taken in an eudiometer tube and mixed with hydrogen till
the volume was 42 ml. On sparking, the resulting mixture occupied 27 ml. To the mixture,
10 ml of oxygen was added and on explosion, again the volume fell to 19 ml. Find the
formula of the oxide of nitrogen that was originally admitted. Both explosions led to the
formation of water.
SOLUTION
There are two ways of solving this problem
Method I:
This is a method that most commonly thought of by a student.
Let the oxide of nitrogen be NxOy. On mixing with H2 the volume was 42 ml.
 the volume of H2 added was 27 ml
On sparking, the reaction would be
x
NxOy + yH2  yH2O + N2
2
Since on adding 10 ml of O2, combustion still takes place, it implies that hydrogen was in
excess (since N2 will not react)
x
 NxOy(g) + yH2(g)  yH2O (l) + N2 ( g )
2
Initially 15 ml 27 ml 0 0
15x
After the Rx. 0 (27–15y) ml ml
2
 Total volume after the first explosion = (27–15y) + 15x
= 27
2
 15x
 15 y = 0 ;  x = 2y ….(1)
2
Do not immediately write the formula as N2O, because this is a molecule and therefore N2O is
its empirical formula and not molecular formula.
In the next explosion, hydrogen reacts with 10 ml of O2 after the volume fell to 19 ml. Since
we do not know whether O2 or H2 is in excess, we consider all the possibilities.
(i) Hydrogen is in excess

H2(g) + ½O2(g)  H2O (l)
Initially (27–15y) 10
Finally (27–15y–20) 0
 Final volume of gases = Volume of remaining hydrogen + nitrogen
(27–15y–20) + 15x = 19
2
This equation violates the first equation namely, (x = 2y)
Therefore H2 cannot be in excess.
(ii) Hydrogen is exactly consumed by O2

 27–15 y = 20
7
y=
15
We know that x and y have to be integers. Therefore hydrogen can not completely
consume oxygen.
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(iii)oxygen is in excess
H2(g) + ½O2(g)  H2O(l)
Initially 27–15 y 10
10  27  15 y
1
Finally 0
2
 Final volume
  15 x
10  2 27  15 y   2
1
= 19
 
(oxygen) (nitrogen)
on solving: x = 2 and y = 1
Formula is N2O
Method II:
In this method we repeat method 1 till we get x = 2y.
Now, we know that H2 was left in excess after reacting with NxOy because we are told in the
problem that on adding O2 again explosion occurs.
If H2 were to be in excess after reacting with NxOy, it automatically implies y = 1. Because if
y =1, then 15 ml of NxOy would have 15 ml of O. Now 15 ml of O requires 15 ml of H2 to
form water. Since H2 is 27 ml, it immediately implies that H2 is in excess. If y =2, then 15 ml
of NxOy will have 30 ml of O and 30 ml of O would require 30 ml of H2 which is more than
what we have.
 y cannot be equal or greater than 2.
y=1
 Formula is N2O.
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SOLVED OBJECTIVE EXAMPLES

EXAMPLE 1
The average velocity of an ideal gas molecule at 27°C is 0.3 m s1. The average velocity
at 927°C will be
(a) 0.6 m s1 (b) 0.3 m s1
(c) 0.9 m s1 (d) 3 m s1
SOLUTION
8RT
uav =
M
u av (T2 ) T2 1200
  2
u av (T1 ) T1 300
uav(T2) = 2 uav (T1) = 0.6 m s1

 (a)
EXAMPLE 2
0.2 g of a gas X occupies a volume of 0.44 L at same pressure and temperature. Under
identical conditions of P and T, 0.1 g of CO2 gas occupies 0.32 L. Gas X can be
(a) O2 (b) SO2
(c) NO (d) C4H10
SOLUTION
0.1
0.1 g CO2 = moles of CO2 occupies = 0.32 L
44
0. 2
moles of X occupies = 0.44 L
M
PV = nRT
Vn
V(CO 2 ) n(CO 2 )

V ( X) n ( X)
0.32 0.1  M

0.44 44  0.2
M = 64
 (b)
EXAMPLE 3
A balloon filled with ethyne is pricked with a sharp pointed needle and quickly dropped
in a tank of H2 gas under identical conditions. After a while the balloon will be
(a) shrunk (b) enlarged
(c) completely collapsed (d) remain unchanged in size
SOLUTION
1
Rate of diffusion 
M
Hence H2 will diffuse into the balloon and its size will increase.
 (b)
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EXAMPLE 4
A flask contains 12 g of a gas of relative molecular mass 120 at a pressure of 100 atm
was evacuated by means of a pump until the pressure was 0.01 atm. Which of the
following is the best estimate of the number of molecules left in the flask
(No = 6  1023 mol1).
(a) 6  1019 (b) 6  1018
(c) 6  1017 (d) 6  1013
SOLUTION
n1
P1 = RT
V
n2
P2 = RT
V
[Volume of the flask and temperature remain constant]
n2 P
 2
n1 P1
n2 = n1  P2 = 12

0.01
P1 120 100
Number of molecules left in the flask = n2  No = 6  1018
 (b)
EXAMPLE 5
The ratio of the root mean square velocity of H2 at 50 K and that of O2 at 800 K is
(a) 4 (b) 2
(c) 1 (d) 1/4
SOLUTION
3RT
VRMS =
M
T
VRMS 
M
VRMS (H2 at 50 K ) 50 32
  1
VRMS (O2 at 800 K ) 2 800
 (c)
EXAMPLE 6
Vander Waal's equation for CH4 at low pressure is
(a) PV = RT  Pb (b) PV = RT  a
V
a
(c) PV = RT + (d) PV = RT + Pb
V
SOLUTION
 a 
 P   (V  b) = RT
 V2 
At low P, volume V is high
(V  b)  V
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 a 
  P   V = RT
 V2 
PV =  RT  a 
 V
 (b)
EXAMPLE 7
The rms velocity of hydrogen is 7 times the rms velocity of nitrogen. If T is the
temperature of the gas.
(a) T(H2) = T (N2) (b) T(H2) > T(N2)
(c) T(H2) < T(N2) (d) T(H2) = 7 T(N2)
SOLUTION
3RT
Vrms =
M
Vrms(H2 ) TH2  MN2
7  =
Vrms(N2 ) MH2  TN2
TH2 28
7= 
2 TN2
TN2  2TH2
 TH2  TN2
 (c)
EXAMPLE 8
The compressibility factor of a gas is less than unity at STP. Therefore,
(a) Vm > 22.4 litres (b) Vm < 22.4 litres
(c) Vm = 22.4 litres (d) Vm = 44.8 litres
SOLUTION
 a 
 P   ( V  b ) = RT
 V2 
Since Z < 1, V  b  V
 a 
  P   (V) = RT
 V2 
Since P = 1
Vr = RT
a
1
V2
a
If P + P=1
V2
then Vi = RT
 Vr < Vi
 Vr < 22.4 L
 (b)
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EXAMPLE 9
Assuming that air is 79% by mole of N2, 20 mole % O2 and 1% Ar, the density of air at
25°C and 1 atm is
(a) 1.18 g/lit (b) 1.08 g/lit
(c) 1.28 g/lit (d) 1.0 g/lit
SOLUTION
PV = nRT
w RT RT
P= 
M V M
PM eff .
=
RT
Meff = (0.79  28) + (0.20  32) + (0.01  39.9) = 28.9
28.9  1
 = = 1.18 g/lit.
0.0821  298
 (a)
EXAMPLE 10
What percent of a sample of nitrogen must be allowed to escape if its temperature,
pressure and volume are to be changed from 220°C, 3.0 atm and 1.65 L to 110°C, 0.7
atm and 1.0 L, respectively?
(a) 41.4% (b) 8.18%
(c) 4.14% (d) 81.8%
SOLUTION
3 1.65 0 .7  1 .0
n1 = n2 =
R  493 R  383
n 0.7  1.0 R  493
Fraction remaining = 2    0.182
n1 R  383 3  1.65
Fraction escaped = 1.0  0.182 = 0.818
Percent escaped = 81.8%
 (d)
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O - Level Subjective Problems

1. A certain quantity of a gas occupies 100 ml when collected over water at 15oC and 750mm
pressure. It occupies 91.9 ml in dry state at NTP. Find the vapour pressure of water
at 15oC.
2. A 15.0 L vessel containing 5.65 g N2 is connected by means of a valve to a 6.00 L vessel

containing 5.00 g oxygen. After the valves opened, the gases are allowed to mix. What
will be the partial pressure of each gas and total pressure at 27°C.
3. A gaseous compound is composed of 85.7% by mass of carbon and 14.3% by mass of

hydrogen. Its density is 2.314 g/l at 300 K and 1.00 atm pressure. Determine the molecular
formula of compound.
4. A bulb of 200 ml capacity is filled with a gas mixture of C2H6 and C4H10 to a pressure of
750 mm at 20oC. If the weight of gas in the bulb is 0.3846 g, what is mole % of butane in
mixutre ?
5. What percent of sample of oxygen should be allowed to escape if its temperature, pressure
and volume are to be changed from 100oC, 2 atm and 1.5 litre to 50oC, 1 atm and 1 litre.
6. A one litre flask at 30oC contains equimolar amounts of NO2 and N2O4 gases. If the total
mass of gas mixture in flask is 1.80 g. Calculate total pressure.
7. A sample of water gas has composition by volume of 50% H2, 45% CO and 5% CO2.
Calculate the volume in litre at STP of water gas, which on treatment with excess of steam
will contain 5 litre H2.
CO (g) + H2O(g)   CO2(g) + H2(g)
8. Compare the rms speed of O2 at 27oC and 54oC. Also find the temperature at which rms
speed of O2 is doubled to that of 27oC.
9. Calculate rms speed of O2 molecules having kinetic energy of 2 kcal/mole. At what

temperature would the molecules have this value of Urms.
10. The critical temperature and pressure of CO2 gas are 304.2 K and 72.8 atm respectively.
What is radius of CO2 molecule assuming it behaves as Van der Waal's gas.
11. 0.553 g of a Boron-Hydrogen compound created a pressure of 0.658 atm in a bulb of

407 ml at 100°C. Analysis showed it to be 85.7% boron. Calculate its molecular formula.
12. A mixture of methane, ethane and carbondioxide measuring 10 ml was exploded with
excess of air. After explosion there was a contraction of 17 ml and after treatment with KOH
solution, there was a further contraction of volume by 14 ml. What was the composition of
the mixture ? (Volume measurements refer to same P-T conditions)
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13. A certain gas occupies 0.418 L at 300 K and 740 mm Hg.

(i) What is its volume at STP?
(ii) If the same gas weighs 3.00 g, what is its molecular weight?
(iii)If we increase the weight of the gas to 7.50 g in the same vessel and the temperature is
changed to 280 K, what would be its pressure? Report the results in 3 significant figures.
14. Calculate the pressure exerted by 1023 gas molecules, each of mass 10-25 kg in a container of
volume 1 dm3 . Root mean square velocity of the gas molecule is 1 km/s. What is the total
kinetic energy of these molecules? What is the temperature of the gas? Using heat
exchangers, when the temperature is reduced to half its original value find the rms velocity
of the gas.
15. 2 g of a gas A are introduced into an evacuated flask kept at 25°C. The pressure is found to
be 1 atm. If 3 g of another gas B are added to the same flask, the total pressure becomes
1.5 atm, Assuming ideal gas behaviour, calculate:
(a) The ratio of mol. weight of MA and MB
(b) the volume of the vessel, if A is O2
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I - Level Subjective Problems

1. Assume that air contains 79% N2 and 21% O2 by volume. Calculate the density of moist air
at 25°C and 1 atm pressure when relative humidity is 60%. The vapour pressure of water at
25°C is 23.78 mm. Relative humidity is given by percentage relative humidity
100  partial pressure of Water
=
Vapour pressure of water at that temperature
2. The allowed threshold limit for the poisonous gas H2S is 10 mg/m3. What pressure does this
correspond to at 20°C assuming H2S as an ideal gas ? What is the volume of H2S required at
600°C & 1 atm pressure to carry out the sulphidation of 2.54 g copper to Cu2S?
3. The compressibility factor of O2 is 0.927 at 273 K under pressure of 100 atm. Calculate
the mass of O2 needed to fill a gas cylinder of 100 litre capacity at the given conditions.
4. A 4:1 molar mixture of He and CH4 is contained in a vessel at 20 bar pressure. Due to a
hole in the vessel the gas mixture leaks out. What is the composition of the mixture effusing
out initially?
5. Calculate the change in pressure when 1.04 mole of NO and 20 g O2 in a 20 litre vessel
originally at 27°C react to produce the maximum quantity of NO2 possible according to the
equation.
2NO (g) + O2 (g)   2NO2 (g)
6. At room temperature the following reaction goes to completion :

2NO + O2   2NO2   N2O4
Dimer N2O4 at 262 K is solid. A 250 ml flask and a 100 ml flask are separated by a stop
contraction cock. At 300 K , the nitric oxide in the large flask exerts a pressure of 1.053 atm
and the smaller one contains O2 at 0.789 atm. The gases are mixed by opening the stop cock
and after the end of the reaction, the flasks are cooled at 220 K. Neglecting the vapour
pressure of dimer find out the pressure and composition of gas remaining at 220 K.
7. 0.5 g of He gas effuses out from a balloon of 20 cm radius and containing 2 g of He gas
originally. What is the new radius of the balloon. (assume ideal behaviour of gas and
constant pressure and temperature)
8. The vapour pressure of a substance of low volatility can be measured by passing an inert gas
over a sample of the substance and analyzing the composition of the resulting gas mixture.
When Nitrogen was passed over mercury at 23° C the mixture analyzed to 0.7 mg. of Hg.,
50.25 mg. of N2, at a total pressure of 745 torr. Calculate the vapour pressure of mercury at
this temperature.
9. In a basal metabolism experiment timed at 6 minutes, a patient exhaled 52.5L of air

measured over water at 20° C. Vapour pressure of water at 20° C is 17.5 torr. Barometric
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pressure was 760 torr. The inhaled and exhaled air contained on a dry basis 20.3% and
16.8% by volume of oxygen. Neglecting other factors, such as, gas solubility in water,
volume difference of inhaled and exhaled air, calculate the rate of oxygen consumption in
ml. (STP) per minute by the patient.
10. An open flask contains air at 27°C. Calculate the temperature to which the air should be
heated so that
(a) One third of air measured at 27° C escapes.
(b) One third of air measured at the final temperature escapes.
11. 20 ml of a mixture of methane and a gaseous compound of acetylene series were mixed
with 100 ml of oxygen and exploded to complete combustion. The volume of the products
after cooling to original room temperature and pressure, was 80 ml and on treatment with
potash solution a further contraction of 40 ml was observed. Calculate
(a) the molecular formula of the compound of acetylene series and
(b) the percentage composition of the mixture.
12. A certain quantity of an organic liquid (mol. wt 85) was introduced into an air filled flask of
volume 6.5 litre and sealed at a temperature of 17° C and 760 mm of Hg. The flask was
heated to a temperature of 307° C where liquid is completely vaporized & the pressure is
registered 4.3 atm. Calculate the amount of organic liquid introduced into the flask.
13. The average speed of 0.1 mol of gas A at 300 K was 460 m/s. The average speed of
0.2 mol of another gas B at 400 K was 510 m/s. The above two samples were mixed
without any transfer of energy with the surrounding. Calculate the average speed of gas
mixture. Assume gases A and B do not react.
14. The mass of molecule A is twice the mass of molecule B. The rms speed of A is twice the
rms speed of B. If two samples of A and B contain same no. of molecules, what will be the
ratio of P of two samples in separate containers of equal volume.
15. Certain volume of a hydride of nitrogen is decomposed into its constituent elements by
electric spark. The volume of the resulting gas mixture becomes double of the initial
volume. Now oxygen has been added to the resulting gas mixture and sparked again and
then cooled to room temperature. After passing through alkaline pyrogallol solution the
volume becomes half of the initial volume of the nitrogen hydride. If all the volumes are
measured at same pressure and temperature then find the formula of the hydride.
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E - Level Subjective Problems

1. A 0.750 g sample of solid benzoic acid, C7H6O2 was placed in a 0.500 L pressurized
reaction vessel (autoclave) filled with O2 at 10.0 atm. pressure and 298 K. The combustion
products of benzoic acid are only water and CO2. Find the mole fractions of CO2 and H2O
vapour in the resulting gas mixture brought to the initial temperature ? (The vapour pressure
of water at 298 K is 23.8 torr)
2. Calculate the temperature values at which the molecules of the first two members of the
homologous series, CnH2n+2 will have the same rms speed as CO2 gas at 770 K. The normal
b.p. of n-butane is 273 K. Assuming ideal gas behaviour of n-butane upto this temperature,
calculate the mean velocity and the most probable velocity of its molecules at this
temperature.
3. 10 ml of a gaseous nitrogeneous hydrocarbon was sparked in a container to yield 15 ml of

products. 20 ml of oxygen were now added and again sparked. The volume is now 25 ml.
Out of this 10 ml were absorbed by alkali and 5 ml by alkaline pyrogallol. The remaining
10 ml was found to be nitrogen. All measurements were made at the same temperature
and pressure. Calculate the molecular formula of the gas.
4. A gas mixture having nitrogen and hydrogen in mole ratio of 1 : 3 is used to prepare
ammonia by the reaction,
N2(g) + 3H2(g) 2NH3(g)
The total pressure before the start of reaction is 1.1 atm at 25°C. Assuming 60% yield of
ammonia, calculate the final pressure at 300°C.
5. 50 ml of a compound of nitrogen and hydrogen (A) was sparked for a long time in an
eudiometer tube over mercury. After sparking, the volume becomes 97 ml. The gaseous
mixture is washed with water to remove undecomposed (A) and after drying, the volume
becomes 94 ml. This was mixed with 60.5 ml of oxygen and the mixture was sparked
again. After cooling to room temperature, the volume of residual gases was 48.75 ml.
Deduce the molecular formula of (A).
6. A mixture of two gases N2 and O2 in the molar ratio of 2 : 1 are taken in a container. The
mixture is allowed to escape through a pin-hole in the container. The initial mixture that
escapes out is collected after a very short interval of time and taken in a container of
double the initial volume. What is the ratio of the pressure exerted by N2 to that of O2 in
the new vessel at the same temperature?
7. Two flasks of equal volume connected by a narrow tube of negligible volume are at 27°C
and contain Cl2 at 1 atm pressure and Cl2O at 1.5 atm pressure respectively. The two
gases were allowed to mix and heated to react as given below:
Cl2O   Cl2 + ½O2
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After the reaction, one of the vessel was kept in a water bath maintained at 27°C while
the other vessel was kept in another water bath maintained at 52°C. Calculate the pressure
in both the vessels at this temperature.
8. For a real gas obeying van der Waal’s equation a graph is plotted between PVm (yaxis)
and P(xaxis) where Vm is molar volume. Find yintercept of the graph.
9. The total pressure of a mixture of H2 and O2 is 1 atm. The mixture is allowed to react to
form water, which is suddenly removed completely to leave only pure H2 at a pressure of
0.35 atm. Assuming ideal gas behaviour and that all pressure measurements were made
under the same temperature and volume conditions, calculate the composition of the
original mixture?
10. A narrow tube of negligible volume has joined two flasks of equal volume. Initially both
flasks are at 300K containing a total of 0.60 moles of O2 gas at 0.5 atm pressure. One of
the flasks is then placed in a thermostat at 600 K. Calculate final pressure and the number
of moles of O2 gas in each flask.
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O  Level Objective Problems

1. According to the ‘kinetic theory of gases’
(a) There are intermolecular attractions
(b) There is no intermolecular attraction
(c) The velocity of molecules decreases after each collision
(d) Molecules have considerable volume.
2. Helium atom is two times heavier than a hydrogen molecule. At 398 K, the average
translational kinetic energy of a helium atom is
(a) two times that of a hydrogen molecule (b) same as that of a hydrogen molecule
(c) four times that of a hydrogen molecule (d) half of that of a hydrogen molecule
3. If the absolute temperature of a gas is doubled and the pressure is reduced to one-half, the
volume of the gas will
(a) remain unchanged (b) be doubled
(c) increase to four-fold (d) be reduced to 1/4 th
4. Under constant pressure, a certain gas at 0°C was cooled until its volume was reduced to
one-half. The temperature at this stage is
(a) 0 K (b) 136.5 K
(c) 136.5°C (d) 273°C
5. A certain mass of a gas occupies a volume of 2 litres at S.T.P. Keeping the pressure
constant, at what temperature would the gas occupy a volume of 4 litres ?
(a) 546°C (b) 273°C
(c) 100°C (d) 50°C
6. The molecular weight of O2 and SO2 are 32 and 64 respectively. If one litre of O2 at 15°C
and 750 mm pressure contains N molecules, the number of molecules in two litres of SO2
under the same conditions of temperature and pressure will be
(a) N/2 (b) N
(c) 2N (d) 4N
7. Equal weights of methane and oxygen are mixed in an empty container at 25°C. The
fraction of the total pressure exerted by oxygen is
(a) 1/3 (b) 1/2
(c) 2/3 (d) 1/3  273/298
8. At 27°C the ratio of rms velocities of ozone to oxygen is
(a) 3 / 5 (b) 4 / 3
(c) 2/3 (d) 0.25
9. The root mean square velocity of an ideal gas at constant pressure varies with
density (d) as
(a) d2 (b) d
(c) d (d) 1 / d
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10. The density of neon will be highest at

(a) S.T.P. (b) 0°C, 2 atm
(c) 273°C, 1 atm (d) 273°C, 2 atm
11. X ml of H2 gas effuses through a hole in a container in 5 seconds. The time taken for the
effusion of the same volume of the gas specified below under identical condition is
(a) 10 seconds : He (b) 20 seconds : O2
(c) 25 seconds : CO (d) 55 seconds : CO2
12. The rates of diffusion of SO2 and O2 are in the ratio

(a) 1 : 2 (b) 1 : 32
(c) 1 : 2 (d) 1 : 4
13. A sample of gas has volume of 0.2 lit measured at 1 atm pressure and 0°C. At the same
pressure but at 273°C, its volume will become
(a) 0.1 litre (b) 0.4 litre
(c) 0.6 litre (d) 0.8 litre
14. At constant volume, for a fixed number of moles of gas, the pressure of the gas increases
with rise of temperature due to
(a) increase in average molecular speed
(b) increased rate of collisions amongst molecules
(c) increase in molecular attraction
(d) decrease in mean free path
15. The ratio between the root mean square velocity of H2 at 50 K and that of O2 at 800 K is
(a) 4 (b) 2
(c) 1 (d) 1/4
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I  Level Objective Problems
1. The average velocity of an ideal gas molecule at 27°C is 0.3 m/sec. The average velocity
at 927°C will be
(a) 0.6 m/sec (b) 0.3 m/sec
(c) 0.9 m/sec (d) 3.9 m/sec
2. At what temperature would N2 molecules have the same average speed as He atoms
at 330 K ?
(a) 1310 K (b) 2310 K
(c) 1130 K (d) 2130 K
3. In Van der Wall's equation of state for a non-ideal gas, the term that accounts for
intermolecular forces is
(a) (V  b) (b) RT
(c) [p+(a/V2)] (d) (RT)1
4. The constant 'a' in Van der Waal's equation is maximum in

(a) helium (b) hydrogen
(c) oxygen (d) ammonia
5. The value of Van der Waal's constant 'a' for the gases O2, N2 , NH3 and CH4 are 1.360,
1.390, 4.170 and 2.253 litre2atm.mole-2 . The gas which can most easily be liquefied is
(a) O2 (b) N2
(c) NH3 (d) CH4
6. At low pressure, the value of compressibility factor, Z of a real gas is

(a) greater than 1 (b) less than 1
(c) equal to 1 (d) can’t be predicted
7. 16 g of oxygen and 3 g of hydrogen are mixed and kept in 760 mm pressure at

0°C. The total volume occupied by the mixture will be nearly ?
(a) 22.4 l (b) 33.6 l
(c) 448 litres (d) 44800 ml
8. For an ideal gas, which of the following graphs, will not be a straight line when all the
other variables are held constant?
(a) P vs 1/V (b) V vs T
(c) P vs T (d) n vs T
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9. The unit of van der waal's constant 'a' is

(a) atmosphere (b) atm l2 mol2
(c) atm.l.mol1 (d) dimensionless
10. The minimum volume of air at STP containing 21% oxygen by volume needed to burn
completely 1 kg 90% pure sulphur will be
(a) 2000 L (b) 4000 L
(c) 8000 L (d) 3000 L
11. How many liters of ammonia could be prepared from a mixture of 19 litres of nitrogen and
34.7 liters of hydrogen, assuming complete conversion and with identical conditions of
temperature and pressure ?
(a) 19 (b) 23.1
(c) 34.7 (d) 38
12. On sparking, the volume of one liter of oxygen reduces to 0.8 L. The mole fraction of
ozone in the resultant mixture is
(a) 0.5 (b) 0.4
(c) 0.2 (d) 1
13. A mixture of methane and ethene in the mole ratio X : Y has a mean molecular
weight = 20. What would be the mean molecular weight if the same gases are mixed in the
ratio Y : X.
(a) 22 (b) 24
(c) 20.8 (d) 19
14. A balloon filled with Hydrogen at 0.1 atm is prickled with a sharp pointed needle and
quickly placed in a tank full of acetylene at atmospheric pressure. After a while the
balloon would have
(a) shrunk (b) enlarged
(c) completely collapsed (d) remain unchanged in size
15. At the same temperature, which of the following gases will have the least average
translational kinetic energy per mole?
(a) Helium (b) Hydrogen
(c) Neon (d) all will have the same
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E  Level Objective Problems

1. A gas of volume 100 ml is kept in a vessel at pressure 104 Pa maintained at temperature
24°C. If now the pressure is increased to 105 Pa, keeping the temperature constant, then
the volume of the gas becomes
(a) 10 ml (b) 100 ml
(c) 1 ml (d) 1000 ml
2. The rms speed of oxygen molecules in a gas is . If the temperature is doubled and the
oxygen molecules dissociate into oxygen atoms, the rms speed will become
(a)  (b)  2
(c) 2 (d) 4
3. At constant pressure, what would be the percentage decrease in the density of an ideal gas
for a 10% increase in the temperature?
(a) 10% (b) 9.1%
(c) 11% (d) 12.09%
4. If in an experiment 100 ml of ozonised oxygen was reduced in volume to 40 ml (at the

same temperature and pressure) when treated with turpentine, what would be the increase
in volume if the original sample was heated until no further change occurred and then
brought back to the same temperature and pressure?
(a) 20 ml (b) 30 ml
(c) 40 ml (d) 10 ml
5. Hydrogen gas diffuses four times as rapidly as a mixture of C2H4 and CO2. The molar ratio
of C2H4 to CO2 in the mixture is
(a) 1 : 1 (b) 2 : 1
(c) 3 : 1 (d) 3 : 2
6. Let the most probable velocity of hydrogen molecules at a temperature tC is Vo. Suppose
all the molecules dissociate into atoms when temperature is raised to (2 t + 273)C then
the new r.m.s velocity is
(a) 2/3 VO (b) 3(2  273/t) VO
(c) 2 3 VO (d) 6 VO
7. A small hole is pricked in a container containing a mixture of methane and oxygen and
placed in vaccum. What should be the molar ratio of methane to oxygen in the container
when the two gases are effusing out in the ratio of 2 : 1.
(a) 2 : 1 (b) 1 : 2
(c) 2 : 1 (d) 1 : 2
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8. The vander waals constant "a" is a correction factor to the ideal gas law for the
intermolecular attractions within a substance. ListI contains the substance and ListII
contains values of "a" (L2 atm mol2).
ListI ListII
(i) C6H6(g) (A) 0.217
(ii) C6H5CH3(g) (B) 5.464
(iii)Ne(g) (C) 18.000
(iv) H2O(g) (D) 24.060
Which one of the following combinations represents the correct matching of the substance
with the corresponding "a" value?
(a) (i)  A, (ii)  D, (iii)  C, (iv)  B (b) (i)  D, (ii)  A, (iii)  B (iv)  C
(c) (i)  C, (ii)  D, (iii)  A (iv)  B (d) (i)  B, (ii)  C, (iii)  A (iv)  D
9. A large cylinder of helium filled at 2000 mm of Hg had a small orifice through which
helium escaped into evacuated space at the rate of 6.4 moles/hour. How long would it take
for 10 mole of CO to leak through a similar orifice if the CO were confined at the same
pressure?
(a) 2.1 hour (b) 4.2 hour
(c) 5.6 hour (d) 11.2 hour
10. 88 g CO2 gas is confined to a 6 litre flask at 37°C. The pressure exerted by CO2 using
vander Waal’s equation is (Given, a = 4.17 atm lit–2 mol2 and b = 0.038 litre mol–1).
(a) 4.06 atm (b) 8.12 atm
(c) 9.16 atm (d) 16.12 atm
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More than one correct Option

1. Boyle's constant of a gas does not depend on
(a) Pressure of gas (b) Volume of gas
(c) Temperature of gas (d) Nature of gas
2. Which of the following statements about vapour density of a gas is/are false
(a) its value changes with change in both, temperature and pressure of a gas
(b) it is the same as density of the gas
(c) it is unitless because it is ratio of two density terms
(d) it is twice the molecular weight of gas
3. Which of the following graphs represent Boyle’s law?
PV
P (b)
(a)
T3
T2 P
T1
V
PV P
(c) (d)
V 1/V
4. What type of conclusion, you draw from the following graphs ?

P V
0K T 0K T
(273.15°C) (273.15°C)
(a) As the temperature is reduced the volume as well the pressure is increased.
(b) As the temperature is reduced the volume becomes zero and the pressure reaches
infinity.
(c) As the temperature reduces, both the volume and the pressure decreases
(d) At 0 K temperature, theoretically the volume as well the pressure become zero.
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5. Which of the following statements are correct?

(a) Helium diffuses at a rate of 8.65 times as much as CO does
(b) Helium escapes at a rate of 2.65 times as fast as CO does
(c) Helium escapes at a rate of 4 times as CO2 does
(d) Helium escapes at a rate 4 times as fast as SO2 does
6. According to kinetic theory of gases,

(a) pressure of the gas molecule is proportional to most probable velocity of the gas
molecules.
(b) pressure exerted by the gas molecule is proportional to root mean square velocity of
the gas molecules.
(c) root mean square velocity is directly proportional to square root of the Kelvin
temperature.
(d) kinetic energy of the gas molecule does not depend upon, P, V and molar mass of the
gas molecules.
7. Compared a mixture of O2(gas) and He gas kept in a container at 27°C. Then which of the
following statements are correct, when O2 is compared with He?
(a) O2 molecule will hit the wall of the container with smaller average speed as compared
to He
(b) O2 molecule will hit the wall of the container with greater average speed as compared
to He
(c) O2 molecule will hit the wall of the container with greater kinetic energy as compared
to He
(d) O2 molecule will hit the wall of the container with equal kinetic energy as compared to
He
8. A gas can be liquefied

(a) When its inversion temperature equals to the Boyle’s temperature.
(b) Under adiabatic expansion.
(c) Under pressure when it is cooled to below critical temperature.
(d) At pressure higher the critical pressure and the temperature lower than critical
temperature.
9. Which of the following is the correct for critical temperature?

(a) It is the highest temperature at which liquid and vapour can coexist.
(b) Beyond the critical temperature, there is no distinction between two phases and gas
cannot be liquefied by compression.
(c) At critical temperature, the surface tension of the system is zero.
(d) At critical temperature, the gas and the liquid phases have the different critical
densities.
10. Which of the following gases fairly deviates from ideal behaviour?
(a) NH3 (b) SO2
(c) CH4 (d) C2H6
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AssertionReason Type Questions

Each question in this section contains STATEMENT–1 (Assertion) and STATEMENT–
2 (Reason) as well as has 4 choices (A), (B), (C) and (D) out of which ONLY ONE is
correct. Mark the correct option considering the scheme:
Option (A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct
explanation for Statement-1
Option (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct
explanation for Statement-1
Option (C) Statement-1 is True, Statement-2 is False
Option (D) Statement-1 is False, Statement-2 is True
1. The pressure of a fixed amount of an ideal Frequency of collisions and their impact
gas is proportional to its temperature. both increase in proportion to the square
root of temperature.
2. The heat absorbed during the isothermal The volume occupied by the molecules of
expansion of an ideal gas against vacuum an ideal gas is zero.
is zero.
3. The value of Vander Waal’s constant ‘a’, Hydrogen bonding is present in ammonia.
is larger for ammonia than for nitrogen.
4. At higher peaks of mountains, people Air at sea level is dense because it is
suffer from high altitude sickness due to compressed by the mass of the air above
lesser oxygen intake at each breath. it. The atmospheric pressure at higher
peaks of mountains is lower causing the
air at those heights to be much less dense
than at sea level.
5. Helium (II) is unique liquid with He (II) is super fluid having so low energy
properties of gas. that thermal motion of atom do not take
place, however interatomic forces are also
so weak the it does not occupy solid state.
6. H2 and N2 molecules have same kinetic Kinetic energy does not depend on
energy at 350C temperature
7. The pressure of a gas is inversely The gas volume is directly proportional to
proportional to its volume at constant n at constant temperature and pressure.
temperature and n.
8. Nobel gas can be liquefied. Attractive force can exist between non
polar molecules.
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Match the following

1. Match gases under specified conditions listed in Column I with their properties/laws in
Column II.
Column I Column II
(A) hydrogen gas (P = 200 atm, T = 273 K) (p) compressibility factor  1
(B) hydrogen gas (P  0, T = 273 K) (q)attractive forces are dominant
(C) CO2 (P = 1 atm, T = 273 K) (r) PV = nRT
(D) real gas with very large molar volume (s) P(V-nb) = nRT
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Comprehensions
PASSAGE1
In 1662, Boyle investigated the relation between the pressure and volume of gases and
found that for a fixed amount of gas kept at a fixed temperature, pressure P and volume V
are inversely proportional i.e.
PV = a constant for constant value of n & T
Careful investigation shows that Boyle’s law holds only approximately for real gases.
Pressure P versus volume V curve for 1 mole of nitrogen at two different temperatures is
found as depicted in figure1. Plots of PV versus P for the same emerged as figure2.
28 T4
30
26
24
20 T3
PV/Latm
22
P/atm
20
10 T2 18 T1
T1 16
14
0
10 20 30 
0
100 200 300
V/L
P/atm
Fig.1 Fig.2
Boyle’s law is understandable from the picture of a gas as consisting of a huge number of
molecules moving essentially independently of one another.
The pressure exerted by the gas is due to the impacts of the molecules on the walls. A
decrease in volume causes the molecule to hit the walls more often, thereby increasing the
pressure.
Questions:
1. Boyle’s law does not hold exactly because
(a) Volume of real gas molecules is infinite
(b) The molecules of gas exert forces on one another.
(c) It is a hypothetical assumption
(d) Pressure of real gas molecules is not estimated accurately.
2. Under which condition Boyle’s law is not obeyed exactly

(a) the limit of zero density (b) the limit of zero pressure
(c) the limit of infinite temperature (d) the limit of infinite pressure
3. What information can we deduce from Figure1
(a) T1 > T2 (b) T2 > T1
(c) T2 = 0 (d) T1 = 0
4. Approximate value for temperature T1 is
(a) 25°C (b) 25°C
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(c) 75°C (d) 100°C

5. Arrange the temperatures T1, T3 and T4 in increasing order
(a) T1 < T3 < T4 (b) T4 < T3 < T1
(c) T3 < T4 < T1 (d) T1< T4 < T3
Passage-2
From the ideal gas equation PV = nRT, it is possible to determine the molar mass of a gas
once the other physical variables are known. One technique for doing this involves the
production of a known volume of the gas from one of the reactions in which it is produced
at a known temperature and pressure. In the reaction, stoichiometric amounts of the
reactants are used, or more commonly, one reactant is used in large excess. For example,
in order to determine the molar mass of carbon dioxide, one could utilize the reaction
between carbonates and acid as shown in Reaction I.
Reaction I: MgCO3 + 2HCl 

 MgCl2 + CO2(g) + H2O
The reaction is carried out in a closed vessel attached to a water manometer (a thin U-tube
filled with water) where the difference in the height of the two levels in the two arms can
be used to determine the pressure inside the vessel. This is due to the fact that the relative
levels in the two arms gives the difference in pressure between the atmosphere and the
vessel.
35.00 grams of MgCO3 were placed into the reaction vessel and 150 mL of 5 M HCl were
subsequently added. After all the MgCO3 had reacted, the difference in height of the water
in the two arms of the manometer was read.
Questions:
1. Given that the density of water is 1000 kg m-3, calculate the pressure inside the reaction
vessel if the level of water in the right arm of the manometer was 50 cm higher than in the
left arm.
(a) 4900 N m-2 + atmospheric pressure (b) 490 N m-2 + atmospheric pressure
(c) 9800 N m-2 + atmospheric pressure (d) 980 N m-2 + atmospheric pressure
2. How should the ideal gas equation be rearranged to allow for the determination of the
molecular mass of the gas? (The mass of the gas is designated by "w" and the molar mass
of the gas is designated by "M")
(a) M = wPT/(RV) (b) M = RV/(wPT)
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(c) M = wRT/(PV) (d) M = PV/(wRT)
3. If Reaction I was exothermic and the temperature of the reaction vessel ended up being
higher than expected, if the initial temperature was used in the equation how would the
recorded value of M compare to its predicted value?
(a) It would be higher than expected.
(b) It would be lower than expected.
(c) It would be the same.
(d) The direction of change of the value of M cannot be predicted from the data given.
4. CO2 happens to be quite soluble in water. How would this affect the value of M obtained
in the experiment?
(a) It would be higher than expected.
(b) It would be lower than expected.
(c) It would be the same.
(d) The direction of change of the value of M cannot be determined from the data given.
PASSAGE3
Real gases deviate from ideal behaviour due to the following two faulty assumptions of
kinetic theory of gases.
(i) Actual volume occupied by the gas molecule is negligible as compared to the total
volume of the gases.
(ii) Forces of attraction and repulsion among the gas molecules are negligible.
To explain, the extent of deviation of the real gas from ideal behaviour in terms of
compressibility or, compression factor (Z), which is function of pressure and temperature
for real gases.
PV
Z= o o
nRT
For ideal gases Z = 1
For real gases either Z > 1 or Z < 1
When Z > 1, then it is less compressible because force of repulsion dominates over force
of attraction. When Z < 1, force of attraction dominates over the force of repulsion and it
is more compressible.
t = 0°C
T4
T3
H2
Z Z T2
N2
T1
CH4 Ideal gas
Z=1 Ideal gas Z=1
CO2
P P
On increasing temperature, Z increases and approaches to unity.
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Questions:
1. What is the correct increasing order of liquefiability of the gases shown as in the above
graph?
(a) H2 < N2 < CH4 < CO2 (b) CO2 < CH4 < N2 < H2
(c) H2 < CH4 < N2 < CO2 (d) CH4 < H2< N2 < CO2
2. Which of the following statements are correct?

(a) The compressibility factor for ideal gases is dependent on temperature and pressure.
 dZ 
(b)   for real gas is independent of pressure.
 dP  T
 dZ 
(c)   for all real gases have same value
 dP  T
 dZ 
(d)   for different real gases have different values
 dP  T
3. Which of the following is the correct order of temperature shown in the above graph Z vs
P for the same gases
(a) T4 > T3 > T2 > T1 (b) T1 > T2 > T3 > T4
(c) T1 > T2 > T4 > T3 (d) T3 > T4 > T2 > T1
4. Which of the following statements is correct for gas A having molar mass 16 g and density
0.75 g/litre at 2 atmospheric pressure and 27°C temperature?
(a) Force of attraction are dominating than force of repulsion among the gas molecules.
(b) Force of repulsion are dominating than force of attraction among the gas molecules.
(c) Gas molecules are behaving ideally
(d) None of the above
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ANSWERS
O - Level Subjective Problems
1. 13.2 mm
2. PN  = 0.237 atm, PO  = 0.183 atm, Ptotal = 0.42 atm.
3. C4H8
4. 39.72 % C2H6 , 60.28 % C4H10
5. 61.5 %
6. 0.649 atm
7. 5.263 litres
8. 0.958 : 1 , 927°C
9. 22.795 m/s
10. 1.6198 Å
11. B5H9
12. CH4 = 3.5 ml, C2H4 = 4 ml. and CO2 = 2.5 ml
13. (i) 0.37 litre (ii) 182 g/mol (iii) 2.27 atm

14. 3.33  106 Pa, 5 kJ, 2414 K, kms1

15. 1 : 3, 1.529 litres
I - Level Subjective Problems
1. 1.171 g/litre
2. 7.1  10-6 atm, 1.4 litre
3. 15.45 kg
4. He : CH4 = 8 : 1
5. 0.64 atm
6. moles of NO left = 4.29  10-3, PNO(left) = 0.221 atm.
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7. 18.17 cm
8. 1.449 torr
9. 0.279 litre per minute
10. (a) 177°C (b) 127°C
11. C3H4 = 50%, CH4 = 50%
12. 26.69 g
13. 493.89 m/sec.
14. PA = 8 PB
15. Formula of nitrogen hydride is NH3
E - Level Subjective Problems
1. Mole fraction of CO2 = 0.213, mole fraction of H2O vapours = 0.0032

2. 280 k, 525 k, 3.157  102 m/s, 2.798 102 m/s
3. CH2N2
4. 1.48 atm.
5. Molecular formula of compound (A) is NH3.
6. 2.138:1
7. 1.7 atm
8. yintercept of the graph = RT
9. X H 2  0.78; X O 2  0.22
10. n O 2 at 600 K = 0.2; n O 2 at 300 K = 0.4
Final pressure = 0.66 atm
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O  Level Objective Problems
1. b 2. b 3. c 4. c 5. b
6. c 7. a 8. c 9. d 10. b
11. b 12. a 13. b 14. a 15. c
I  Level Objective Problems
1. a 2. b 3. c 4. d 5. c
6. b 7. d 8. d 9. b 10. d
11. b 12. a 13. b 14. b 15. d
E  Level Objective Problems
1. a 2. c 3. b 4. b 5. c
6. d 7. a 8. d 9. b 10. b
More than one correct option
1. a,b,d 2. a,b,d 3. a,b,c,d 4. c,d 5. b,d

6. c,d 7. a,d 8. a,b,c 9. a,b,d 10. a,b,c
AssertionReason Type Questions
1. 2. 3. 4. 5.
6. 7. 8.
Match the following

1. Ap, s, Br, Cp, q, Dp
Comprehensions
Passage1
1. c 2. d 3. b 4. c 5. a
Passage2
1. a 2. c 3. a 4. a
Passage3
1. a 2. d 3. a 4. b
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GASEOUS STATE

 PT (at constant V and n)

Ideal Gas Equation

Physical Significance of Universal Gas Constant (R)

Force  Length (or displacement )

Dalton's Law of Partial Pressure

Amagat's Law Of Partial Volumes

MOLECULAR MASS AND GAS DENSITIES

Vapour density of a gas is same at any temperature, pressure and volume.

Molecular Weight And Effective Molecular Weight

 Meffective = XiMi =  mole fraction of a gas  mol. wt. of a gas

 Total wt. of 1 litre of moist air

 Density of moist air = 1.1844 gm/litre

Whenever we consider the diffusion of a gas under experimental conditions, we always

KINETIC THEORY OF GASES

Derivation Of Kinetic Gas Equation

Kinetic Energy Of Gases

DEVIATION FROM IDEAL BEHAVIOUR

increase in pressure. Variation of temperature on compressibility factor for N2 may be

Van der Waals Equation for Real Gases

Thus pressure P in ideal gas equation may be replaced as

Vander waal’s equation for 1 mole of gas becomes

Calculation of Van der waal constant 'a' and 'b'

Corollary of Van der Waal Equation

(iii) When Temperature Is Extremely High

(iv) When Pressure Is Not Too Low

(v) Behaviour of Hydrogen

Expressions of Critical Constants in Terms of Van der Waals Constants

Now comparing equation (i) with the given expression,

VELOCITY OF GAS MOLECULES

Types of Molecular Velocity

From kinetic gas equation we have

4. Interrelation of Molecular Velocities:

The various reagents used for absorbing different gases are

(i) Hydrogen is in excess

(ii) Hydrogen is exactly consumed by O2

SOLVED OBJECTIVE EXAMPLES

uav(T2) = 2 uav (T1) = 0.6 m s1

O - Level Subjective Problems

2. A 15.0 L vessel containing 5.65 g N2 is connected by means of a valve to a 6.00 L vessel

3. A gaseous compound is composed of 85.7% by mass of carbon and 14.3% by mass of

9. Calculate rms speed of O2 molecules having kinetic energy of 2 kcal/mole. At what

11. 0.553 g of a Boron-Hydrogen compound created a pressure of 0.658 atm in a bulb of

13. A certain gas occupies 0.418 L at 300 K and 740 mm Hg.

I - Level Subjective Problems

6. At room temperature the following reaction goes to completion :

9. In a basal metabolism experiment timed at 6 minutes, a patient exhaled 52.5L of air

E - Level Subjective Problems

3. 10 ml of a gaseous nitrogeneous hydrocarbon was sparked in a container to yield 15 ml of

O  Level Objective Problems

10. The density of neon will be highest at

12. The rates of diffusion of SO2 and O2 are in the ratio

I  Level Objective Problems

4. The constant 'a' in Van der Waal's equation is maximum in

6. At low pressure, the value of compressibility factor, Z of a real gas is

7. 16 g of oxygen and 3 g of hydrogen are mixed and kept in 760 mm pressure at

9. The unit of van der waal's constant 'a' is

E  Level Objective Problems

4. If in an experiment 100 ml of ozonised oxygen was reduced in volume to 40 ml (at the

More than one correct Option

3. Which of the following graphs represent Boyle’s law?

4. What type of conclusion, you draw from the following graphs ?

5. Which of the following statements are correct?