States of Matter: Thermal Energy

STATES OF MATTER [1]
STATES OF MATTER
Chemical properties of a substance do not change with the change of its physical state; but rate of
chemical reactions do depend upon the physical state. Many times in calculations while dealing with
data of experiments we require knowledge of the state of matter. Therefore, it becomes necessary for a
chemist to know the physical laws which govern the behaviour of matter in different states. In this
unit, we will learn more about gaseous state of mater.
Thermal Energy :
Thermal energy is the energy of a body arising from motion of its atoms or molecules. It is directly
proportional to the temperature of the substance. It is the measure of average kinetic energy of the
particles of the matter and is thus responsible for movement of particles. This movement of particles is
called thermal motion.
Intermolecular forces vs thermal energy :

Three states of matter are the result of balance between intermolecular forces and the thermal energy
of the molecules.
When molecular interactions are very weak, molecules do not cling together to make liquid or solid
unless thermal energy is reduced by lowering the temperature.
Predominance of thermal energy and the molecular interaction energy of a substance in three states is
depicted as follows :
(Predominance of intermolecular interactions)
(Predominance of thermal energy)
The gaseous state :

In the case of the gaseous state there are negligible attraction forces - between the molecules allowing
them to move freely hence there is maximum random motion in the gaseous state as compared to other
states therefore they have neither a fixed volume nor a fixed geometry. The different measurable
quantities of any gas are Pressure, Volume, Temperature, and amount of the gas.
The gases are characterised by:
(i) Volume :
The volume of a gas is the space that it occupies. They do not have fixed volume but occupy
the volume of container in which they kept. It is expressed in mL (cm3), L(dm3) or m3 (1 m3
=1000L).
IIT KALRASHUKLA [2]
(ii) Pressure :
Gases exert pressure on the walls of the container in all directions by collision of molecules. It
is defined as the force per unit area and is uniform in all the directions. It is measured in N/m2
or mm of Hg or atm or torr or bar. The device used to measure the pressure of the atmosphere
is called barometer. 1 Pascal = 1 kg/m. s2
1 atm = 1.01325 x 105 Pa 100 K Pa, 1 bar = 1,00,000 Pa = 0.987 atm
(iii) Temperature :
It is measured in terms of hotness or coldness. The measurement is based on the expansion of
certain material (mostly it is mercury) with increasing temperature. It is measured in celsius
scale or absolute scale (Kelvin scale). For gases-, STP (Standard Temperature and Pressure)
conditions are 273 K (0°C) and 1 atm pressure. A gas at this temperature & pressure is said to
be at S.T.P.
Note : That the standard temperature for gas measurements (0°C or 273 K) is not the same as that
usually assumed for thermodynamic measurements (25°C or 298 K is said to be SATP
condition or Standard Ambient Temperature and Pressure).
 F 32 
K = °C + 273.15 °C = 5  
 9 
Kelvin or absolute scale :

A new temperature scale was introduced known as Kelvin scale or absolute scale named after the
British physicist and mathematician Lord Kelvin. The lower limit of the scale is called absolute zero
which corresponds to –273°C. At absolute zero or –273°C, all molecular motions would stop and the
volume of the gas would become zero. The gas would become a liquid or solid. Thus, absolute zero is
that temperature at which no substance exists in the gaseous state. The temperature in absolute scale is
always obtained by adding 273 to the temperature expressed in °C.
K = (t°C + 273)
The concept of absolute zero temperature can also be derived fro7m the laws of thermodynamics.
According to the first law of thermodynamics, the absolute zero of temperature is the lowest possible
temperature on the thermodynamic scale and according to the second law of thermodynamics, this
temperature can’t be attained.
(iv) Expansibility :
Gases have limitless expansibility. They expand to fill the entire vessel they are placed in and
take the shape and volume of the vessel.
(v) Compressibility :
Gases are easily compressed by application of pressure through a movable piston fitted to the
container since the molecules are very far from each other.
(vi) Diffusibility:
Non-reacting gases can diffuse rapidly through one another to form a homogeneous mixture.
Gas Laws :
The volume of a given sample of gas depends on the temperature and pressure applied to it. Any
change in temperature or pressure will affect the volume of the gas. These relationships between
measurable properties (P, V, n, T) which describe the general behaviour of gases, are called gas laws.
When a gas obeys these laws, it is said to be ideal or perfect gas. These laws are applicable only to
gases which do not undergo a change in chemical complexity, when the temperature or pressure is
varied.
Boyle’s Law:
It relates the volume and the pressure of a given mass of a gas at constant temperature.
The relationship between the volume and the pressure of a gas was studied by Robert Boyle in 1662.
He found that increasing the pressure at constant temperature on a sample of a gas causes the volume
of the gas to decrease proportionately, i.e., if the pressure is doubled, the volume becomes half and so
on. Boyle’s law states that, “At constant temperature, the volume of a sample of a gas varies inversely
with the pressure”.
1
 P (when temperature and number of moles are kept constant)
V
The proportionality can be changed into an equality by introducing a constant k, i.e.,
k
P= or PV = k
V
Alternatively, Boyle’s law can also be stated as follows:
“Temperature remaining constant, the product of pressure and volume of a given mass of a gas is
constant”.
The value of the constant depends upon the amount of a gas and the temperature.
Mathematically, it can be written as,
P1V1 = P2V2 = P3V3 = PnVn
Boyle’s law can be verified by any one of the following three ways graphically.
The first curve shows the variation of volume of a given mass of gas with pressure at constant
temperature. The shape of the curve is rectangular hyperbola. This curve is also called isotherm.
IIT KALRASHUKLA [4]
The second curve showing the relationship between volume and reciprocal of pressure is a straight
line. It confirms the statement that at constant temperature, volume of a given mass of gas is inversely
proportional to the pressure. The third curve shows a straight line parallel to pressure-axis. This
confirms that the product of pressure and volume of a given mass of a gas at constant temperature is
constant.
Location of straight line and curve changes with temperature in the isotherm shown in the following
figures.
According to Boyle’s law, PV = Constant at constant temperature

log P + log V = constant
log P = –log V + constant
Charles’ Law:
It relates the volume and temperature of a given mass of a gas at constant pressure.
Experiments have shown that when 273 mL sample of a gas at 0°C is heated to 1°C, its volume
increases by 1 mL, i.e., it becomes 274 mL. At 5°C, the volume increases to 278 mL if the pressure
remains constant in both cases. Similarly, when 273 mL sample of gas at 0°C is cooled to –1°C, its
volume decreases to 272 mL while at –5°C, the volume decreases to 268 mL if the pressure remains
constant.
Thus, all gases expand or contract by the same fraction of their volume at 0°C per degree change of
temperature, i.e., for each degree change of temperature, the volume of a sample of a gas changes by
1
the fraction of its volume at 0°C.
273
Let the volume of a given amount of gas be V0 at 0°C. The temperature is increased by t°C and the
new volume becomes Vt
V0  t   273  t 
Thus, Vt = V0  t  V0 1   or Vt = V0   …(i)
273  273   273 
Now Kelvin scale may be used for deducing Charles’ law.
By substituting T for (273 + t) and T0 for 273 in Eq. (i).
V0  T Vt V0 V
Vt = or  or = constant, if pressure is kept constant
T0 T T0 T
For two or more conditions of temperature of a fixed amount of gas at constant pressure Charles’ law
can be related as:
V1 V2 V
= =....... n = constant
T1 T2 Tn
Now the Charles’ law can be stated as follows :

“The volume of a given amount of a gas at constant pressure varies directly as its absolute
temperature”.
V  T (if pressure is kept constant)
IIT KALRASHUKLA [6]
Charles’ law can be verified experimentally by plotting the values of volumes of a given amount of a
gas under respective absolute temperature at constant pressure. The straight line confirms the above
statement.
Gay Lussac’s law (Pressure-Temperature Relationship):

It relates the pressure and absolute temperature of a given mass of a gas at constant volume. “Volumes
1
remaining constant, the pressure of given mass of a gas increases or decreases by of its pressure
273
at 0°C per degree change of temperature”.
P t  t 
Pt  P0  0 or Pt  P0 1  
273  273 
 273  t  T Pt P0 P P P
or Pt  P0    P0 or  or 0  2 ...... n  cons tan t
 273  T0 T T0 T1 T2 Tn
or P  T (if volume and number of moles are kept constant)
Hence the law can be stated as “At constant volume, the pressure of a given amount of a gas is directly
proportional to its absolute temperature”.
Avogadro’s Law (Volume amount relationship) :
Let us take a balloon containing a certain mass of gas. If we add to it more mass of gas, holding the
temperature (T) and pressure (P) constant, the volume of gas (V) will increase. It was found
experimentally that the amount of gas in moles is proportional to the volume. That is,
Vn (T and P are constant) or V = Kn
where K is a constant of proportionality or V/n = constant.
Thus, for equal volumes of two gases at fixed T and P, number of moles are also equal. This is the
basis of Avogadro’s law which states that:
“Equal volumes of gases at the same temperature and pressure contain equal number of moles or
molecules”. It has been observed that 1mole of gas at a temperature of 273 K and a pressure of
1atmosphere (STP or NTP) occupies 22.4 Litres. This is called the molar volume of a gas.
Ideal Gas Equation :

1
V (Boyles law) V  T (Charles law) V  n (Avogadro’s law)
P
nT
V PV = nRT
P
where R = universal gas constant
Numerical values of R :
PV
R=
nT
At STP for one mole of gas
P = 1 atm V = 22.4 lit T = 273K n = 1m
1 22.4
   R= = 0.0821 lit atm K–1 mol–1
1 273
(76 13.6  981)22400
R= = 8.314 107 erg K–1 mol–1
1 273
= 8.31 JK–1 mol–1
 R = 1.99 Cal K–1 mol–1
Relation of Density with Ideal gas Equation :

PV = nRT
amount of gas w
n = number of moles = =
Mol. wt of gas M0
w
 PV = × RT
M0
w
  PM0 = RT = DRT
V
D = Density of gas
PM0 = DRT
P1 DT
(a) For same gas   1 1 
P2 D 2 T2
P1 D
(b) For same gas at same temperature   1  P  D at (constant T and m)
P2 D2
P1M1 DT
(c) For two gas  = 1 1 
P2 M 2 D 2 T2
   (d) For two gases at constant temperature
P1M1 D
= 1
P2 M 2 D2
(e) For two Gases at constant pressure
M1 DT
= 1 1
M2 D 2 T2
For same gas at constant pressure
IIT KALRASHUKLA [8]
D1T1 = D2T2
1
 D  
T
Physical Significance of R. For one mole of gas
PV (Force/area)(Area  Length) Force  Length Work done
R= = = =
T Temperature Temperature Temperature change
Thus ‘R’ represents work done per degree per mole of the gas.
DALTON’S LAW OF PARTIAL PRESSURES

The total pressure exerted by mixture of non-reacting gases in a definite volume at a constant
temperature is equal to the sum of individual pressure which each gas would exert if it occupies the
same volume at the same constant temperature.
(n RT)
PTotal = Total Let nA moles of A, nB mole of B etc be the non-reacting gases present in a
V
container of volume V at constant temperature.
(n  n B  n C  n D  ...)RT
PT = A
V
(n RT) n BRT n C RT n D RT
= A     .....
V V V V
= PA + PB + PC + PD + ....
Where PA, PB etc. are partial pressures of individual gases if they were present alone in the same
container of volume V(litres) and same constant temperature T.
The partial pressure can be calculated as follows –
PA is also equal to mole fraction of gas multiply by the total pressure exerted by the mixture of gases.
n
PA = A  PT = XAPT where XA = mole fraction of gas
nT
Pressures of moist gas = Pressure of Dry gas + Pressure of water vapour
P moist = Pdry gas + vapours PMoist gas > PDry gas
Dalton’s Law is also applicable for gaseous system at equilibrium.
DIFFUSION AND EFFUSION
1. Diffusion:
When two or more non - reacting gases are kept side by side, they have the tendency to mix
with one another spontaneously and form a homogeneous mixture. This phenomenon can
occur even against gravity. This mixing ability of gases is known as diffusion.
2. Effusion:
It is a process in which a gas is allowed to escape under pressure gradient through a fine hole
(orifice).
The difference between diffusion and effusion is that the latter occurs even when there is no
pressure gradient, but the former continues to occur only as long as there is pressure gradient.
Otherwise, both processes are essentially the same.
3. Rate of Diffusion:
It can be defined as
(i) Volume or number of moles of gas diffused per unit time.
(ii) Distance travelled by a gas per unit time through a tube of uniform cross- section.
Graham’s Law of Diffusion :

The rate of diffusion (r) of a gas at constant temperature is directly proportional to its pressure
as well as inversally proportional to the square root of its density or molecular weight.
rP
1
r
M
P
r at constant temperature
M
1/2
r1 P M 
 = 1× 2 at constant temperature
r2 P2  M1 
r1 M2 D2
 = = at constant temperature and pressure
r2 M1 D1
r1 D2
= where d1 and d2 are vapour density of gases
r2 D1
V
Rate of diffusion = where V = volume of gas diffuse
t
t = time taken for diffusion
n
r = where n is number of moles of gas diffuses in time t
t
d
= where d is distance travelled by gas molecules in time t
t
At Constant T At constant T and P
V1 t 2 M 2  P1  V1 t 2 M2
 = ×   =
t1 V2 M1  P2  t1 V2 M1
n1 t 2 M2 P  n1 t 2 M2
 = × 1  =
t1 n 2 M1  P2  t1 n 2 M1
d1 t 2  M 2   P1  d1 t 2 M2
 =     =
t1 d 2  M1   P2  t1 d 2 M1
IIT KALRASHUKLA [10]
FACTORS DETERMINING THE RATE OF DIFFUSION & EFFUSION
1. Pressure:
It is quite-logical to understand that more is the partial pressure difference more will be the rate
of diffusion. When a gas is kept in a container with pressure P and it is placed in environment
where the pressure of the gas is P’, then obviously the rate of gas flow should proportional to
(P - P’) and the flow will take place in the direction of high pressure to low pressure.
2. Area:
The rate of gas flow should be directly related to the area of the orifice. Greater the orifice
area, greater should be the number of molecules coming out per unit time.
3. Molecular weight:
Heavier the gas, slower should be its movement.
4. Temperature:
It would have been expected that temperature increase should have increased the rate of gas
flow from a container. This follows because increase of gas temperature, would increase the
energy of the molecules and would therefore increase the velocities of gas molecules. But it
should be noted that when a gas molecule moves out of a container through a small orifice, it is
required to move in a very restricted path to be able to come out of the orifice. An increase in
temperature no doubt would increases the velocity, but it would also hamper the ability of the
molecule to orient itself properly with the orifice so the rate of effusion decreases. If the orifice
is large then the rate of effusion would increase with increase in temperature as the orientation
would not matter much for effusion to take place.
If temperature of two gases are T1 and T2 at constant pressure then,
r1 M2 T1
= 
r2 M1 T2
The Kinetic Molecular Theory of Gases :

In order to derive the theoretical aspect of the various gas laws based on simple experimental facts,
Maxwell proposed the following postulates under the heading of kinetic theory of gases:
The postulates of kinetic theory of gases are
(i) Each gas is made up of a large number of small (tiny) particles known as molecules.
(ii) The volume of a molecule is so small that it may be neglected in comparison to total volume of
gas.
(iii) The molecules are never in stationary state but they are believed to be in chaotic (random)
motion. They travel in straight line in all possible directions with altogether different but
constant velocities. The direction of motion is changed by the collision with container or with
the other molecules.
(iv) The collision between molecules is perfectly elastic i.e., there is no change in the energies of
the molecules after collision.
(v) The effect of gravity on molecular motion is negligible.
(vi) The kinetic energy of the gases depends on the temperature.
(vii) The pressure of the gas arises due to collision of molecules with the walls of the container.
CLASS PRACTICE PROBLEM (CPP-1)
1. Find the pressure of the gas inside a container if the open manometer attached to the container
shows a difference of 60 mm.
1. Pgas = 700 mm
2. A sample of gas occupied 100 dm3 at 1 bar pressure and at T °C. If the volume of the gas is
reduced to 5 dm3 at the same temperature, what additional pressure must be applied?
2. P = 20 bar
3. A certain amount of a gas at 27°C and 1 bar pressure occupied a volume of 25 m 3. If the
pressure is kept constant and the temperature is raised to 77°C, what will be the volume of the
gas?
3. V2 = 27.19 m3
4. LPG is a mixture of n-butane and iso-butane. What is the volume of oxygen needed to bum 1
kg of LPG at 1 atm, 273 K?
4. 2510 L
5. 2 moles of NH3(g) and 1 mole of HCl(g) are taken in a container of capacity 8.21 lit at 300K to
produce NH4Cl(s). Find the total pressure after the reaction.
5. 3 atm
7
6. A balloon is inflated to of its maximum volume at 27°C then calculate the minimum
8
temperature above which it will burst.
6. T = 342.8 K
7. A bulb of unknown volume containing air is heated from 27°C to 227°C at constant pressure.
The expelled air is measured at different temperature of determine volume of container. What
will be volume of container if-
(a) 200 ml of air measured at 227°C was expelled.
(b) 200 ml of air measured at 27°C was expelled.
(c) 200 ml of air measured at 127°C was expelled.
7. (a) V = 300 mL, (b) V = 500 mL, (c) V = 375 mL
8. An open flask contains air at 27°C. Calculate the temperature at which it should be heated so
that
(a) 1/3rd of air measured in the container at 27°C
(b) 1/3rd of air measured in the container at final temperature escape out.
8. (a) T = 450 K or 117°C, (b) T = 400 K or T = 127°C
9. A tyre tube of maximum volume 8.21 lit. can withstand a pressure of 100 atm. Initially the tube
is empty.
(i) Calculate the number of moles required to inflate completely the tube upto a pressure of
1 atm & 300 K temperature.
(ii) Calculate the minimum number of moles required to burst the tyre tube at 300 K.
1 10
9. (i) n1  , (ii) n 2 
3 3
10. A container of 8.21 lit. capacity is filled with 1 mole of H2 at 300 K and it is connected to
another container of capacity 2 × 8.21 lit. containing 4 moles of O2 at 300 K, then find the final
pressure and partial pressure of each gas.
10. PH2  1atm PO2  4atm
11. At 1200°C, mixture of Cl2 and Cl atoms (both in gaseous state) effuses 1.16 times as fast as
krypton effuses under identical conditions. Calculate the fraction of chlorine molecules
dissociated into atoms. M(Kr) = 83.8 g mol–1.
11. % dissociation = 14%
The Kinetic Gas Equation

1
Maxwell also derived an equation on the basis of above assumptions as PV = mnu2
3
where P = Pressure of gas
V = Volume of gas
m = mass of one molecule of gas
n = no. of molecules of gas
u = root mean square velocity of molecules
For 1 mole n = N (Avogadro number)
m × N = Molecular mass M.
1 3PV 3RT 3PV 3RT
 PV  Mu 2 or u 2   or u  
3 M M M M
Derivation of The Kinetic Gas Equation :
Imagine a cube of edge length , containing N molecules, each having a

mass of m. Molecules are moving randomly in all directions, with speed
covering a considerable range of values.
The velocity u, of any molecule may be resolved into three component

velocities designated as ux, uy, uz. These are in the three directions at right
angles to each other and parallel to the sides of the cube as shown in above
figure. The component velocities are related by the expression,
u2 = ux2 +uy2 + uz2
Considering the x-component velocity of a molecule, we will have
Momentum of the molecule before collision with the side ABCD = mux
Momentum of the molecule after collision with the side ABCD = - mux
Change of momentum of the molecule in a single collision with the side ABCD = |2mux|
Since  is the edge length of the cube, the molecule has to travel a distance 2 to arrive back at the wall
ABCD.
ux
The number of collisions per unit time with the wall ABCD will be equal to
2l
The total change in momentum per unit time due to such impacts is
 ux  mu x
2
2mu x  =
 2l  l
According to Newton’s second law of motion
Force = mass × acceleration
d(velocity)
= mass×
dt
d(mass × velocity)
=
dt
d(momentum)
= = rate of change of momentum.
dt
mu 2x
Hence, total force due to impacts of a single molecule with the wall ABCD of the vessel is
l
The area of the wall is l2 Hence, the pressure exerted due to the collision of x-component velocity of a
single molecule with the side ABCD is
mu 2x /1 mu 2x
Px  
12 V
where V is the volume of the vessel. Since each molecule will exert similar pressure, the total pressure
exerted on the wall ABCD will be
N
m N 2
P=  Pix 
i 1
 uix
V i 1
N
1
Defining the mean square speed as u 2x =
N
u 2
ix
i=1
We can write,
mN
P= u 2x …(i)
V
Since the direction x, y and z are equivalent, we will also have
u 2x = u 2y = u z2
But we know that
u 2 = u 2x + u 2y + u 2z
Hence from above two expressions, we get

1
u 2x = u 2y = u z2 = u 2
3
Substituting this in equation (i)
mN  1
2  1
 u  or 2
P= PV= mN u
V 3  3
Application of Kinetic Gas Equation :

The kinetic gas equation can be used to derive various gas laws and to define expressions for some
useful quantities such as the root mean square speed and the average kinetic energy.
(1) Average kinetic energy :
1 2 1  1 3 R 
PV= mNu 2 = N mu 2 or mu 2 =   T
3 
3 2  2 2 N
1 3 R
mu 2 /mol = KT for one mole K = (Boltzman constant )
2 2 NA
Now, we proceed to derive the various gas laws from this equation
2. Boyle’s Law :
The essential conditions for Boyle’s law to be applicable are:
(i) Temperature (T) should remain constant.
(ii) Mass of the gas should remain constant. In other words, the total number of molecules
(N) remains unchanged.
2
Under these conditions, equation PV  NKT yields
3
1
PV = constant or P 
V
which is the expression for Boyle’s law.
3. Charles’ Law:
In this case
(i) Pressure (P) remains fixed.
(ii) Mass of the gas remains unchanged, i.e., N is constant with these conditions, equation
yields
 2 NK 
V=   T i.e., V = (constant) T or V  T
3 P 
as required by Charles’ law.
(4) Avogadro’s Law:

It states that under similar conditions of pressure and temperature, equal volume of all gases
contains equal number of molecules. Considering two gases, we have
2 2
P1V1 = N1KT1 and P2 V2 = N 2 KT2
3 3
Since P1 = P2 and T1 = T2, therefore
P1V1 (2/3)N1KT1 V N
=  1= 1
P2 V2 (2/3)N 2 KT2 V2 N 2
If volumes are identical, obviously N1 = N2, it also follows that mole ratio = volume
ratio, when both the gases are present at same T and P.
Molecular Speeds :
Molecular speeds are of 3 types :
(i) The RMS speed
(ii) The average speed
(iii) The most probable speed
The root mean square speed (urms) :

1
This is the type of speed we used in kinetic gas equation, PV = mnu2 It is the hypothetical speed
3
possessed by all the gas molecules when the total kinetic energy is equally distributed amongst them.
Total kinetic energy of a sample containing n number of molecules
1 1 1
mu12  mu 22  .......  mu n2
2 2 2
If velocity possessed by all the molecules is same and that is u,
1
Total kinetic energy = n× mu 2
2
1 1 1 1
n  mu 2  mu12  mu 22  ....  mu 2n
2 2 2 2
u12  u 22  ....  u 2n
u2 
n
u12  u 22  ....u n2
u 
n
Thus RMS velocity is defined as the square root of the mean of the squares of the speeds of all the
molecules present in the given sample of the gas. The value of u is determined by using the following
expressions.
3PV 3RT 3P
u  
M M d
In applying any of these equations care must be taken to use consistent units. If SI units are used for R
(= 8.31 kgm2/(s2. k. mol)), T(K) and M(kg/mol), the rms speed will be in meters per second.
Average speed (uav) : It is arithmetic mean of the various speeds of the molecules.
u1 +u 2 +......+u n
Average speed u =
n
8RT
It is equal to
M
Most probable Speed (ump):

This is defined as the speed possessed by maximum number of molecules of a gas at a given
temperature.
2RT
It is equal to
M
The three kinds of molecular speeds are related to each other as :
8
Most probable speed : Average speed : RMS speed = 2: : 3

ump: uav: urms = 1 : 1.128 : 1.224
Maxwell’s Distribution of Molecular speeds (Velocities) :

Maxwell and Boltzmann proposed that gas molecules are always in rapid random motion colliding
with each other and with the walls 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.
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 close 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.
Collision Diameter :
The kinetic theory of gases treats molecules as point masses, when two such
molecules approach each other, a point is reached at which mutual repulsion
between the molecules becomes so strong that it causes reversal of direction of
there motions. The distance between the centres of the two molecules at the point
of their closest approach is known as collisions diameter.
Collision Number :
The number of collisions with which a single molecule will collide per unit time is given by
2 Cav
Where cav = average velocity  = number density i.e., number of molecules per unit volume of a gas
Hence Z1 = 2 Cav
The total number of molecules colliding per unit time per unit volume of the gas is given by
cavSince each collision involves two molecules, the number of collision of like molecules
occurring per unit time per unit volume of the gas is given by
1
Z11 = ( 2 2 cav 2)
2
1
= (2 cav 2)
2
This is also called collision frequency

Also it follows that number of collision of the molecules of type 1 with those of type 2 would be called
1
Z12 = ( Cav 12)
2
P
Also  = = number density
KT
1 P2
Z11 = ×  cav ×
2 (KT) 2
Frequency of collision is  P2
Frequency of collision is  T3/2
It should be noted that z1 is expressed in s–1 where as z11 as s–1m–3
Mean Free Path :
It is the mean distance travelled by a gas molecule between two successive collision
Average distance travelled per second
=
Number of collision by a molecule per sec
c av cav KT
= = =
z1 2πσ cav P/KT
2
2πσ 2 P
1
  at constant temperature
P
  T at constant pressure
Equipartition of energy :
The total energy of a molecule is divided equally amongst the various degrees of freedom of a
molecule.
The distribution of kinetic energy along x, y and z-axis is EK = EKx + EKy + EKz
Since the motion of the molecular along the three cartesian axis is equally probable
1 1 3  1 R
Ekx = Eky = Ekz = of Ek =  kT  = kT where k = Boltzman constant = .
3 3 2  2 NA
This shows that each component of kinetic motion contributes equal l to the total kinetic energy and
1 1
that the kinetic energy for each degree freedom is kT per molecule or RT per mole.
2 2
As regards vibrational motions the two atoms oscillate against each other. The molecule therefore
possesses both potential and kinetic energy. This means that energy of vibration involves two degree
of freedom.
The vibrational motion in a molecule is thus associated with energy.
1
(a) kT for potential energy
2
1
(b) kT for kinetic energy
2
Hence total vibration energy
= Potential vibrational energy + Kinetic vibrational energy per molecule
1 
= 2  kT 
2 
1  R
= 2  RT  per mole (Since k =  R = kNA)
2  NA
Thus if a gaseous species has n1 translation degree of freedom, n2 rotational degrees of freedom and n3
vibrational degrees of freedom then the total energy of species is given by
  kT  
n1   + n2   + n 3    2
kT kT
 2   2    2  
DEGREE OF FREEDOM :
Mono Atomic :
Translational 3
Rotational 0
Vibrational 0
Diatomic Linear
Translational 3
Rotational 2
Vibrational (3n – 5) = 1
Polyatomic Linear Non-linear

Translational 3 3
Rotational 2 3
Vibrational (3n–5) [3n–6]
Note : vibrational mode of degree of freedom or motion = (3n – sum of translational and rotational
mode)
H2O molecules:
Modes of freedom
translational = 3
Rotational =3
Vibrational = 3
1  1    1 
ETotal = 3  kT  + 3  kT  + 2 3  2 kT  
2  2    
= 6 kT
CO2 molecule :
The degrees of freedom are as follows
Translational = 3
Rotational = 2
Vibrational = 4
1  1    1   13
ET = 3  kT  + 2  kT  + 2  4  2 kT   = 2 kT
2  2    
Internal Energy and Cv of Molecules :

According to Born oppenheimer approximation the total energy of a molecule is given by
ETotal = ETrans + ERot + Ev
 dE 
  = Cv
 dT  v
 Differentiating both sides w.e.t dT keeping V constant we get
CV(Total) = CV(trans) + CV(rot) + CV(vib)
Computation of Cv for :
Also at room temperature it has been observed that the vibrational motion donot contribute hence;
vibrational contributions become more prominent at high temperature e.g., Ev
(i) He
3
ET = ETrans = RT
2
dE 3
 CV = = R
dT 2
5
Also CP = CV + R CP = R
2
(ii) O2 molecule
ET = ETrans + ERot + Evib
ET = RT + RT + RT
dE 3
CV = = R+R+R
dT 2
At low temperature Evib to CV is not prominent.
 CV = CV(trans) + CV(Rot)
3
= R+R
2
5
CV = R
2
Also CP = CV + R
5 7
= R+R= R
2 2
1. Calculate the kinetic energy of 8 gram methane (CH4) at 27°C temperature.

1. K.E. = 1870.65 J
2. Calculate the pressure exerted by 1023 gas molecules, each of mass 10–25 kg, in a container of
volume 1 × 10–3 m3 and having root mean square velocity of 103 ms–1. Also calculate total
kinetic energy and Temperature of the gas.
2. T = 2415 K
3. Four particles have peed 2, 3, 4 and 5 cm/s respectively. Find their avg. and rms speed:
54
3. U rms  cm / s
2
4. At what temperature do the average speed of CH4(g) molecule equal the average speed of O2
molecule at 300 K?
4. T = 150 K
5. Calculate  , ZI and ZII for oxygen at 298 K and 10–3 mm Hg. Given   3.61108 cm.
5. ZI = 8.32 × 103 s–1, ZII = 13.48 × 10 ms–3 s–1
6. How many times is the rms speed of molecules in 8 gm O2 gas at 1200 K and 10 bar, relative to
rms speed of molecules in 16 gm O2 gas at 300K and 20 bar?
6. ()
7. Average translational kinetic energy of an ideal gas molecule at 27°C is 3.88 × 10 –x eV. Hence x
is (1 eV = 1.602 × 10–19 J)
7. ()
8. When the temperature of an ideal gas is increased from 27°C to 927° the kinetic energy will be
increased by x times. Find the value of x?
8. ()
9. Two flask A and B have equal volume at 100 K and 200 K and have pressure 4 atm and 1 atm
respectively. The flask A contains H2 gas and B contains CH4 gas. The collision diameter of CH4
is twice that of H2. Calculate ratio of mean free path of CH4 to H2.
9. ()
10. If the mean free path is 10 cm at one bar pressure then its value at 5 bar pressure, if temperature
is kept constant.
10. ()
Deviations from Ideal Behaviour :
An ideal gas is one which obeys the gas laws of the gas equation PV = RT at all pressure and
temperatures. However no gas in nature is ideal. Almost all gases show significant deviations from the
ideal behaviour. Thus the gases H2, N2 and CO2 which fail to obey the ideal-gas equation are termed as
non-ideal or real gases.
Compressibility Factor :
The extent to which a real gas departs from the ideal behaviour may be depicted in terms of a new
PV
function called the compressibility factor, denoted by Z. It is defined as Z = for one mole of an
nRT
ideal gas.
(PV)real
RT = (PV)ideal so Z =
(PV)ideal
The deviations from ideality may be shown by a plot of the compressibility factor Z, against P.
For an ideal gas, Z = 1 and it is independent of temperature and pressure. The deviations from ideal
behaviour of a real gas will be determined by the value of Z being greater or less than 1. The
difference between unity and the value of the compressibility factor of a gas is a measure of the degree
of non ideality of the gas.
For a real gas, the deviations from ideal behaviour depend on (i) pressure; and (ii) temperature. This
will be illustrated by examining the compressibility curves of some gases discussed below with the
variation of pressure and temperature.
Greater is the departure of Z from unity, more is the deviation from ideal behaviour.
(i) When Z < 1, this implies that gas is more compressible (PV)real < (PV)ideal
(ii) When Z > 1, this means that gas is less compressible (PV)real > (PV)ideal
(iii) When Z = 1, the gas is ideal (PV)real = (PV)ideal
Effect of Pressure Variation on Deviations :

Figure shows the compressibility factor, Z, plotted against pressure for H2, N2 and CO2 at a constant
temperature. At very low pressure, for all these gases Z is approximately equal to one. This indicates
that at low pressures (upto 10 atm), real gases exhibit nearly ideal behaviour. As the pressure is
increased, H2 shows a continuous increase in Z (from Z = 1).Thus the H2 curve lies above the ideal gas
curve at all pressure.
For N2 and CO2, Z first decrease (Z< 1). It passes through a minimum and then increases continuously
with pressure (Z > 1). For a gas like CO2 the dip in the curve is greatest as it is most easily liquified.
Effect of Temperature on Deviations :

Figure shows plots of Z or PV/RT against P for N2 at different temperatures. It is clear from the shape
of the curves that the deviations from the ideal gas behaviour become less and less with increase of
temperature.
At lower temperature, the dip in the curve is large and the slope of the curve is negative. That is, Z < 1.
As the temperature is raised, the dip in the curve decreases. At a certain temperature, the minimum in
the curve vanishes and the curve remains horizontal for an appreciable range of pressures. At this
temperature, PV/RT is almost unity and the Boyle’s law is obeyed. Hence this temperature for the gas
is called Boyle temperature. The Boyle temperature of each gas is characteristic e.g., for N2 it is 332
K.
Conclusion: From the above discussions we conclude that:

1. At low pressure and fairly high temperatures, real gases show nearly ideal behaviour and the
ideal- gas equation is obeyed.
2. At low temperatures and sufficiently high pressures, a real gas deviates significantly from
ideality and the ideal-gas equation is no longer valid.
3. The closer the gas is to the liquefication point, the larger will be the deviation from the ideal
behaviour.
Van der Waals Equation of State for a Real Gas:

The equation of state generated by Vander Waals in 1873 reproduces the observed behaviour with
 n 2a 
moderate accuracy. For n moles of gas, the Vander Waals equation is  P  2  (V  nb)  nRT
 V 
where a and b are constants characteristic of a gas.
On comparing above equation with ideal gas equation. We get
an 2
Pideal  Preal  2  (Pideal  Preal  correction term)
V
Videal  Vrea  nb  (Videal  Vreal  correction term)
This equation can be derived by considering a real gas and converting it to an ideal gas.
Volume correction:
We know that for an ideal gas P × V = nRT. Now in a real gas the
molecular volume cannot be ignored and therefore let us assume that
‘b’ is the volume excluded (out of the volume of container) for the
moving gas molecules per mole of a gas. Therefore due to n moles of a
gas the volume excluded would be nb.
 a real gas in a container of volume V has only available volume of

(V – nb) and this can be thought of, as an ideal gas in a container of
volume (V – nb).
If we consider only bimolecular collisions, then the volume occupied by the sphere of radius 2r
represents the excluded volume per pair of molecules as shown in given figure.
Thus, excluded volume per pair of molecules

4 4 
 (2r)3  8  r 3 
3 3 
Excluded volume per molecule
1   4 3  4 
8  r    4  r 3   4 (volume occupied by a molecule)
2 3  3 
Since b represents excluded volume per mole of the gas, it is obvious that
 4 
b  N A  4  r 3  
 3 
The Vander Waals constant b (the excluded volume) is actually 4 times the volume of a single
molecule. i.e. b = 4 NAV where NA is Avogadro number.
b = 4 × 6.023 × 1023 × V
Pressure correction:
Let us assume that the real gas exerts a pressure P. The molecules that exert the force on the container
will get attracted by molecules of the immediate layer which are not assumed to be exerting pressure.
It can be seen that pressure the real gas exerts would be less than the pressure an ideal gas would have
exerted. The real gas experiences attractions by its molecules in the reverse direction. Therefore if a
real gas exerts a pressure P, then an ideal gas would exert a pressure equal to (P + P’-correction term)
(P’ is the pressure lost by the real gas molecules due to attractions). This small pressure p would be
directly proportional to the extent of attraction between the molecules which are hitting the container
wall and the molecules which are attracting these.
n
Therefore P' (concentration of molecules which are hitting the container’s wall)
V
n
and P' (concentration of molecules which are attracting these molecules )
V
an 2
P'  Hence Pideal = Preal + P’
V2
 an 2 
or  ideal
P = P+ 
 V2 
 n 2a 
Substituting these corrections in ideal gas equation we get  P  2  (V  nb)  nRT where a is the
 V 
constant of proportionality which depends on the nature of gas. Higher value of ‘a’ reflects the
increased attraction between gas molecules.
The Van der Waals constant a and b:

Vander Waals constant for attraction (a) and volume (b) are characteristic for a given gas. Some
salient features of ‘a’ and ‘b’ are:
(i) The gas having higher value of ‘a’ can be liquified easily and therefore H2 and He are not
liquified easily.
(ii) The unit of a = litre2 atm mole–2 and that of b = litre mole–1
EXPLANATION OF DEVIATION BY VAN DER WAALS EQUATION :

(i) At lower pressure :
‘V’ is large and ‘b’ is negligible in comparison with V. Then Vander Waals equation reduces
to :
 a 
 P+ 2  V=RT
 V 
a
PV+ =RT
V
a
PV = RT - or PV < RT or (PV)real < (PV)ideal
V
Hence Z < 1
This accounts for the depression in PV vs P isotherm at low pressure.
(iii) At fairly high pressures:

a
may be neglected in comparison with P.
V2
The Vander Waals equation becomes.
P ( V–b) = RT
PV – Pb = RT
PV = RT + Pb or PV > RT or (PV)real > (PV)ideal Hence Z > 1
This accounts for the rising parts of the PV vs P isotherm at high pressures.
(iv) At very low pressure:

a
V becomes so large that both b and become negligible and the Vander Waals equation
V2
reduces to PV = RT. Here (PV)real = (PV)ideal, hence Z = 1. This shows why gases approach
ideal behaviour at very low pressures.
(v) Hydrogen and Helium:
These are two lightest gases known. Their molecules have very small masses. The attractive
a
forces between such molecules will be extensively small. So is negligible even at ordinary
V2
temperatures. Thus PV > RT. In this way Vander Waals equation explains quantitatively the
observed behaviour of real gases and so is an improvement over the ideal gas equation.
Vander Waals equation accounts for the behaviour of real gases.
At low pressures, the gas equation can be written as,
a
RT-
 a  PV m Vm
 P+ 2  (Vm )=RT or Z= =
 Vm  RT RT
 a 
 PV  RT  at low pressure 
 V 
where Z is known as compressibility factor. Its value at low pressure is less than 1 and it
decreases with increase of P. For a given value of Vm, Z has more value at higher temperature.
At higher pressure, the gas equation can be written as
P (Vm – b) = RT
PVm RT+Pb Pb
Z= = =1+ {Q PVm =RT + Pb at high pressure)
RT RT RT
Here, the compressibility factor increases with increase of pressure at constant temperature and
it decreases with increase of temperature at constant pressure. For the gases H2 and He, the
above behaviour is observed even at low pressures, since for these gases, the value of ‘a’ is
extremely small.
1. Boyle Temperature :
As already mentioned, the temperature at which a real gas obeys Boyle’s law, is known as the
Boyle temperature, TB. It is given by the expression
TB = a/bR .... (10)
2. Viral equation :
The virial equation is an equation common to all three equations of state (van der Waals,
Berthelot, Dietetic). All the three equations of state can be expressed approximately by the
virial equation of state. The virial equation of state for 1 mol of a gas is
PVm 1 1 1
Z=  1 B  C 2  D 3  ...
RT Vm Vm Vm
where B, C, D, ...... are temperature-dependent constants known as second, third, fourth, .....
viral coefficients.
Boyle’s temperature (TB) :
It is the temperature at which a real gas exhibits almost ideal behaviour for a considerable range of
pressure. Different gases have different values of TB, which is related to the van der Waals constants a
and b as follows.
TB = a/Rb
1. Calculate the pressure exerted by 5 mole of CO2 in one litre vessel at 47°C using van der
waal’s equation. Also report the pressure of gas if it behaves ideal in nature.
Given that a = 3.592 atm It2 mol–2, b = 0.0427 L/mol. Also, if the volume occupied by CO2
molecules is negligible, then calculate the pressure exerted by one mole of CO2 gas at 273 K.
1. P = 0.9922 atm
 B 
2. One way of writing the equation of state for real gases is PV = RT 1   ... where B is a
 V 
constant. Derive an approximate expression for B in terms of van der Waal’s constants a and b.
a
2. B b
RT
3. Calculate the volume occupied by 2 moles of a vanderwall gas at 5 atm 800 K.
Given: a = 4.0 atm l2 mol–2, b = 0.0625 l mol–1, R = 0.08 l- atm/K-mol.
3. V = 25.6 L
4. Derive the expression for compressibility factor of a vanderwaal gas at Boyle temperature.
b2
4. Z  1
Vm (Vm  b)
5. Calculate the temperature of gas if it obeys vander waal’s equation from the following data. A
flask of 25 litre contains 10 moles of a gas under 50 atm. Given a = 5.46 atm litre –2 and b =
0.31 litre mol–1.
5. T = 1529.93 K
6. Calculate vander waal’s constant a and b if critical temperature and critical pressure are 30°C
and 72 atm respectively.
6. b = 0.043 L mol–1, a = 3.59 L2 atm mol–1
LIQUEFACTION OF GASES
According to the kinetic theory of gases, gases consist of tiny molecules widely separated from one
another by large empty spaces (voids). The molecules are in a state of continuous rapid motion with
negligible attractive forces between them. Ever molecule has almost independent existence. This is
particularly so when temperature is high and pressure is low. When the temperature of the gas is
lowered, the volume of the gas and also the kinetic energy of the molecules decrease. The molecules
become sluggish, and molecular motion becomes slow. The molecules come closer because they are
unable to resist the attractive forces that start operating between them. As the process of decrease in
temperature continues, the gas molecules go on moving closer and closer. Ultimately, at a sufficiently
low temperature, the voids between the molecules become less than 10–5 cm and the gas changes into
liquid. The effect of bringing the gas molecules closer and closer can also be achieved by increasing
the pressure because this also causes a decrease in the volume of the gas. Thus, liquefaction of gas can
be achieved by a decrease in temperature and by an increase in pressure as shown in Fig 5.31.
Fig. Liquefaction of gases

Concept of critical constants (Andrew Isotherm) :
In the previous section, we studied that a gas can be liquefied both by decreasing temperature and by
increasing pressure. For example, sulphur dioxide can be liquefied at 265 K if pressure is 1 atm. It can
also be liquefied at 293 K if the pressure is increased to 3.25 atm.
The effect of temperature, however, is more significant than pressure. This was proved by Thomas
Andrew (1861) who studied the effect of temperature and pressure on a volume of CO2 gas. He
measured the volumes of carbon dioxide at different pressure keeping the temperature constant in his
experiments. The plots of P vs V at different temperatures (called isotherms of carbon dioxides) have
been given in Fig. 5.32.
At a low temperature (13.1°C, i.e., 286.2 K), CO2 exists as gas at low pressure as shown by point A.
As the pressure is increased, the volume of gas decreases along the curve AB. At point B, liquefaction
starts. Hence, volume decreases rapidly along the line BC because a liquid has much less volume than
a gas. At the point C, liquefaction is complete. Now a further increase in pressure has very little effect
upon the volume because liquids are very less compressible. Hence, a steep curve (CD is obtained as
shown in the figure. Thus, along the portion AB, carbon dioxide exists only as gas, along the portion
CD only as liquid and along the portion BC, the liquid and the vapour are in equilibrium with each
other.
Fig.: Volume isotherms of carbon dioxide

The isotherm EFGH at 21.5°C (294.6 K) is similar to that at 13.1°C (286.2K) except that the
horizontal portion over which the liquefaction occurs is shorter. In fact, as the temperature is raised,
this portion becomes smaller and smaller (as indicated by the dotted boundary curve), and finally at
30.98°C (304.1 K), it is reduced only to a point. In the isotherms above 30.98°C (304,1K), the
horizontal portion completely disappears. This shows that above 30.98°C, the gas does not liquefy at
all however high pressure may be applied.
The point X is called the critical point, and the temperature corresponding to point X is called the
critical temperature. The experimental study of carbon dioxide and other gases revealed that for every
gas there is a certain temperature above which it cannot be liquefied however high the pressure may
be. The kinetic energy of gas molecules above this temperature is sufficient enough to overcome the
attractive forces. This temperature is referred to as critical temperature of the gas. The critical
temperature of gas may be defined as the temperature above which it cannot be liquefied by
application of pressure. In other words, a gas remains in the gaseous state above its critical
temperature. In order to liquefy it by compression, it has to be cooled to its critical temperature.
Critical temperature is denoted by TC. For example, TC of CO2 is 304.1 K = 30.98°C
Critical pressure (PC):

The pressure required to liquefy a gas at critical temperature is called critical pressure. For example,
the value of PC for CO2 is 73.9 bar.
Critical volume (VC) :

The volume of 1 mol of a gas at critical temperature and critical pressure is called critical volume. For
example, the value of VC for CO2 is 94.0 cm3 mol–1.
It may be noted that the parameters TC, PC, and VC for a gas are collectively critical constants.
At a high temperature (i.e., 50°C), the isotherms look like that of an ideal gas and no liquefaction
occurs even if the pressure is very high (isotherm given at 50°C).
Relationship between critical constant and van der Waals constants :

The critical constants of a gas are related to its van der Waals constants as follows. These relations
have been derived from the calculations based on the van der Waals equation.
(a) VC = 3b
(b) PC = a/27b2
(c) TC = 8a/27Rb
(d) The critical compressibility factor ZC is given by
PC VC (a / 27 b 2 ) (3b)
ZC = 
RTC R[8a / 27 Rb]
a  3b  27 Rb 3
=   0.375
R  8a  27b2 8
CRITICAL POINT :
Critical point refers to the state of a substance at critical temperature and critical pressure. Some
significant features are as follows :
 At the critical point, the density of the substance in gaseous and liquid states remains same.
 The surface of separation between liquid and gas disappears, and there is no distinction
between liquid and gaseous states.
 No second phase is formed irrespective of the pressure of the system.

 Gases below their critical temperatures are called vapour.
 Fluids above critical temperature are called super critical fluids. Such fluids dissolve many
organic substances. These are used for speedy separation of a mixture into its components.
Carbon dioxide above 31.1°C and 600 bar pressure has a density around 1 g cm–3 and is used
to remove caffeine from coffee beans instead of using chlorofluorocarbons, which are not
environment friendly.
The Law of Corresponding States :
Reduced equation of state : The van der Waals equation can be written in a form which does not
contain any constant characteristic of individual gases. Such an equation is applicable to all gases. In
order to obtain this equation, we need to define reduced pressure, reduced temperature, and reduced
volume as follows :
P
Reduced pressure (Pr) =
PC
T
Reduced temperature (Tr) =
TC
V
Reduced volume (Vr) =
VC
Thus, P = PrPc, T = TrTc, and V = VrVc
Substituting these expressions of pressure (P), temperature (T), and volume (V) in the van der Waals
equation.
 a 
P 2  (Vm – b) = RT
 Vm 
We get
 a 
 Pr PC  2 
(VrVc – b) = RTrTc
 (Vr VC ) 
We know that
a 8a 8a
PC = 2
, TC = , TC = , VC = 3b
27b 27Rb 27Rb
So on replacing PC, VC, and TC in terms of a, b, and R, we get
 a a   8a 
Pr  2 2
{Vr(3b) – b} = RTr  
 27Rb 
2
 27b Vr (3b) 
 3 
or  Pr  2  (3Vr – 1) = 8Tr
 Vr 
Equation (i) is known as the reduced equation of state. It does not contain any constant which is
characteristic of a gas and, therefore, it is applicable to all gases.
According to the law of corresponding states, if two gases have the same values of reduced pressure
and pressure and temperature, they will have the same reduced volume.
Relationship between Z and the reduced equation of state :

The compressibility factor (Z) is PVm/RT. Substituting P, Vm, and T in terms of reduced Pr, Tr, and Vr,
we get
PVm
Z=
RT
(P T ) (Vr Vc )  Pc Vc   Pr Vc 
= r c   
R (Tr Tc )  Tc   Tc 
Pc Vc 3

Tc 8
3 Pr Vr
Z=
8 Tr
The right hand side of equation (ii) does not contain any constant and is independent of the nature of
gas, and hence the value of Z is same for all gases.
1. The van der Waals constants for gases A, B and C are as follows
Gas a[atm/L2 mol–2] b[L mol–1]
A 8.21 0.050
B 4.105 0.030
C 1.682 0.040
Which gas has (i) the highest critical temperature, (ii) the largest molecular volume, and (iii)
most ideal behaviour around 500 K?
1. ()
2. For a real gas, if at critical conditions molar volume of gas is 8.21 litre at 3 atm, then critical
temperature (in K) will be:
2. 800
3. An unknown gas behaves ideally at 540K in low pressure region, then calculate the
temperature (in K) below which it can be liquified by applying pressure.
3. 160 K
4. For real gas the P-V curve was experimentally plotted and it had the following appearance.
With respect to liquification, choose the incorrect statement:
(A) At T = 500 K, P = 40 atm, the state will be liquid

(B) At T = 300 K, P = 50 atm, the state will be gas
(C) At T < 300 K, P = 20 atm, the state will be gas

(D) At 300 K < T < 500 K, P > 50 atm, the state will be liquid
4. ()
LIQUID STATE
The liquid state is the intermediate state between the gaseous and solid states. The intermolecular
forces are stronger in the liquid state than in the gaseous state. The molecules of liquids are held
together by attractive intermolecular forces. They are so close that there is very little empty space
between them, and under normal conditions, liquids are denser than gases. Liquids have definite
volume because their molecules do not separate from each other. However, the molecules can past one
another freely. Therefore, liquids can be made to flow, can be poured, and can assume the shape of the
container in which they are stored.
PROPERTIES OF LIQUIDS :
(a) Shape :
Liquids have no definite shape. They take up the shape of the vessel in which they are put. This
is because their molecules are in a state of constant rapid motion.
(b) Volume :
Liquids have a definite volume. Their volumes do not depend upon the size or shape of the
container. In liquids, the forces of attraction between the molecules are stronger and the
molecules are closer to each other. Liquid molecules are closer to each other. Liquid molecules
are not completely free to move.
(c) Density :
Liquids have much higher density than gases. In liquids, molecules are quite closely packed.
Therefore, their densities are much higher than the densities of gases under comparable
conditions. For example, the density of water at 373 K land 1 atm pressure is 0.958 g cm –3,
while that of water vapours at the same temperature and pressure is equal to 0.000588 g cm–3.
(d) Compressibility :
Liquids are much less compressible than gases. This is because the space between the
molecules of liquids is reduced almost to a minimum by intermolecular attraction.
(e) Diffusion :
Liquids diffuse like gases, but the diffusion is much slower. The slow diffusion in liquids can
be explained in terms of smaller intermolecular spaces and restricted motion of molecules.
(f) Evaporation :
When a liquid is placed in an open vessel, its molecules constantly move in different directions
with different velocities. Thus, as these molecules are moving with different speeds, they
possess different kinetic energies.
Factors affecting the rate of evaporation :

The factors that affect the rate of evaporation are as follows :
(a) Temperature :
The rate of evaporation increases with an increase in temperature. At a higher temperature, the
fraction of molecules having sufficient kinetic energy to escape from the surface increases.
This results in an increase in the rate of vaportion. Fig. 5.35 shows the change in evaporation
with a rise in temperature.
Fig.5.35 Energy distribution graph
(b) Surface area of liquid:

Evaporation is a surface phenomenon. High energy molecules from the liquid can go into the
gaseous phase only through the surface. Therefore, the greater the surface area of the liquid,
the greater the rate of evaporation.
(c) Nature of liquid:

Liquids having weaker intermolecular forces of attraction can easily pass into the gaseous
phase from the liquid phase. Therefore, the rate of evaporation is higher in such liquids. For
example, dimethyl ether evaporates at a much faster rate than ethyl alcohol. A liquid which
evaporates more readily is described as being more volatile.
Vapour Pressure:
If a liquid is placed in a closed vessel, its molecules may go into the gaseous phase from the liquid
phase due to vaporation.
As time passes, more and more molecules leave the liquid and come above the surface of the liquid.
The molecules present above the liquid surface are called vapours. These molecules in the vapour
phase are also constantly moving, and some of them strike the surface of the liquid, which may be
recaptured by the liquid. The process is called condensation.
In the beginning, the rate of evaporation is high. However, as more and more molecules with higher
energy leave the liquid, the rate of evaporation decreases with time. On the other hand, as the number
of molecules in the vapour phase is very small in the beginning, the rate of condensation is very low.
However, with the passage of time, as the number of molecules in the vapour phase increases, the rate
of condensation also increases (Fig.5.36). Ultimately, a stage is reached when the rate of evaporation
becomes equal to the rate of condensation, i.e., equal number molecules leave and re-enter the liquid at
the same time.
Fig.(a) Attainment of equilibrium
This state is called the state of equilibrium. The pressure exerted by the vapour at this stage (as
indicated by a manometer) is called the vapour pressure. It is sometimes called the saturated vapour
pressure because the vapour is saturated at this stage.
Fig.(b) Diagrammatic presentation of attainment of equilibrium

(Liquid Gas)
Hence, the vapour pressure of a liquid at any temperature is defined as the pressure exerted by the
vapours in equilibrium with the liquid at that temperature.
The vapour pressure of a liquid depends upon the following factors :

a. Nature of liquids :
More volatile liquids have higher vapour pressures.
b. Temperature :
As temperature increases, the vapour pressure increases because at higher temperatures, larger
number of molecules escape into the vapour phase.
Boiling :
Boiling is a special case of evaporation. It is the rapid conversion of a liquid into vapours by means of
formation of bubbles. During boiling, evaporation is not restricted to the surface only but takes place
throughout the bulk of the liquid.
Difference between boiling and evaporation :
Both boiling and evaporation involve conversion of liquid into vapours and appear to be similar.
However, they differ in some respect. The differences are listed below :
Table : Difference between boiling and evaporation :

Evaporation Boiling
a. Evaporation occurs at the a. It involves the formation of bubbles even
surface of a liquid. below the surface within the bulk of the
liquid.
b. It occurs spontaneously at all b. It occurs only at a specific temperature at
temperatures. which the vapour pressure equals the
imposed pressure on the liquid surface.
c. It is a slow phenomenon. c. It is a rapid phenomenon.
Heat of vaporisation or enthalpy of vaporisation (vapH) :

The amount of enthalpy required to convert a liquid into gas at a constant temperature is known as the
enthalpy of vaporisation.
Molar enthalpy of vaporisation (vapH) :

Is defined as the amount of enthalpy required to convert 1 mol of a liquid to gas at the boiling point of
the liquid.
The greater the intermolecular forces of attraction present in a liquid, the greater the enthalpy of
vaporisation and the higher the boiling point. For example, the enthalpy of vaporisation and boiling
point of water are more than those of ether, acetone, benzene, etc.
Surface Tension :
This property of liquids is related to the strength of interparticle forces. A molecule well within the
bulk of a liquid is uniformly attracted in all directions by the neighbouring molecules.
Fig. Forces acting on a molecule on the surface and on a molecule inside the liquid
The net force of attraction acting on such a molecule is almost zero. A molecule at the surface of the
liquid has no upper molecules to participate in attraction. This creates an imbalance of forces at the
surface as shown in Fig.5.39. Consequently, the molecules at the surface experience a resultant inward
pull and the surface behaves as if it was a stretched membrane or were under tension. For a plane
surface, the force acting parallel to the surface and perpendicular to a line of unit length anywhere in
the surface is called surface tension. It is represented by a Greek letter gamma, , and is expressed in
the units of dyn cm–1 or newton per meter (N m–1)
Due to surface tension, the molecules tend to leave the surface, and the surface of a liquid tends to
minimise the surface area as far as possible. In order to increase the surface area of the liquid, some
energy has to be supplied against the inward pull. This is referred to as surface energy. Thus, surface
energy is the energy required or work required to be done to increase the surface area of the liquid by a
unit amount. It is expressed in J m–2 or N m–1. [J m–2 = Nm (m–2) = Nm–1]. It may be noted that
surface tension and surface energy have same dimensions.
Effect of temperature on surface tension :

The magnitude of the surface tension of a liquid depends on the attractive forces between the
molecules. When the attractive forces are large, the surface tension is large. An increase in
temperature increases the kinetic energy of the molecules, and the effectiveness of intermolecular
attraction decreases. So the surface tension decreases as the temperature is raised.
The effect of temperature on surface tension is gives by an equation deduced by Eotvas.

2/3
 d 
 = k (Tc – t)  
M
Here,  is the surface tension, k is the constant, d is density, M is molecular mass, Tc is the critical
temperature, and T is temperature.
Evidently as T approaches the critical temperature, the surface tension becomes zero. At this stage, the
meniscus between the liquid and vapours disappears.
Effect of adding surface active solutes :

The addition of surface active solutes to a liquid also lowers the surface tension. For example, the
addition of ethanol, soaps, detergents, etc., to water lowers its surface tension. The cleansing action of
soap is based on this fact.
Some effects of surface tension :

Let us now study some important phenomena that can be explained by surface tension :
a. Spherical shape of drops :
Surface tension causes liquid drops (or gas bubbles) to acquire spherical
shape. This is because the lowest energy state of a liquid is attained when
the surface area is minimum. Spherical shape satisfies this condition; that
is why mercury drops are spherical in shape. This is why sharp glass edges
are heated for making them smooth. On heating, the glass melts and the
surface liquid tends to take the rounded shape at the edges, which makes
the edges smooth. This is called fire polishing of glass. For a given
volume, the sphere has a minimum surface area, as shown in Fig.
b. Capillary action :
The surface tension of a liquid depends upon the forces between the molecules of the liquid.
The attractive forces between the molecules of the same substance are called cohesive forces,
while that in the molecules of different substances are called adhesive forces. When water is
taken in a glass tube (such as burette), there are cohesive forces between water molecules and
adhesive forces between glass and water. In this case, the adhesive forces are stronger than
cohesive forces. As a result, water acquire a concave upward surface [see Fig.(A)] Such a
curved surface of a liquid is known as meniscus. In case of mercury, cohesive forces are
stronger than adhesive forces, and hence mercury has concave downward meniscus [see Fig.
(B)]. The rise or fall of liquids in capillary action) can also be explained in terms of surface
tension.
(A) (B)
Capillary action
Viscosity :
It is one of the characteristic properties of liquids. It is a well known fact that some liquids such as
honey, castor oil, glycerine, etc., flow slowly, where as others such as water, petrol, ethanol, etc., flow
rapidly. This means that every liquid has some internal resistance to flow, which is referred to as
viscosity. Liquids which flow slowly are said to be more viscous than the liquids which flow rapidly.
Viscosity is a measure of resistance to flow arising due to the internal friction between layers of fluid
as they slip past one another when the liquid flows. Strong intermolecular forces between molecules
hold them together and resist movement of layers past one another.
To understand the nature of internal resistance or friction existing within a liquid, consider a liquid
flowering through a narrow tube. All parts of the liquid do not move through the tube with the same
velocity. Imagine the liquid to be made up of a large number of thin cylindrical coaxial layers. The
layer in contact with the walls of the tube is almost stationary.
Fig. Flow through a narrow tube
When a liquid flows over a fixed surface, the layer of

molecules in immediate contact with the surface is
stationary. The velocity of upper layers increases as the
distance of layers from the fixed layer increases. This type of
flow in which there is a regular gradation of velocity in
passing from one layer to the next is called laminar flow. If
we choose any layer in the flowing liquid (Fig.), the layer above it accelerates its flow and the layer
below it retards its flow.
If the velocity of the layer at a distance dz is change by a value, du, then the velocity gradient is given
by the amount du/dz. A force is required to maintain the flow of layers. This force is proportional to
the area of contact of the layers and the velocity gradient, i.e.,
F  A (A is the area of contact)
du
F
dz
where du/dz is the velocity gradient, the change in velocity with distance.
du
F  A.
dz
du
 F = A
dz
 is the proportionality constant and is called coefficient of viscosity.
Now, if A = 1 cm2, u = 1 cm s–1, and Z = 1 cm, then F = .
Thus, coefficient of viscosity may be defined as the force of friction required to maintain the velocity
difference of 1 cm s–1 sec–1 between two parallel layers 1 cm apart and having an area of 1 cm2.
Units of viscosity :
Units of viscosity are dyn cm–2s. This quantity is also called 1 paise (after the name of Poiseuille).
However, the SI units of viscosity are N m–2 s or kg m–1 s
Poise = gm cm–1s
Poise is 1/10 of SI unit.
Effect of temperature :
With an increase in temperature, the magnitude of interparticle forces decreases and the kinetic energy
of molecules increases. This causes a decrease in the viscosity of the liquid.
JEE MAIN EXERCISE

SINGLE OPTION CORRECT QUESTIONS …………………………………………...
1. Gaseous Laws 4. A 0.5 dm3 flask contains gas A and 1 dm3

1. A gas cylinder containing cooking gas can flask contains gas B at the same
withstand a pressure at 14.9 atm. The temperature. If density of A = 3 g/dm3 and
pressure gauge of the cylinder indicates 12 that of B = 1.5 g/dm3 and the molar mass
atm. at 27ºC. Due to a sudden fire in the of A = 1/2 of B, the ratio of pressure
building its temperature starts rising. At exerted by gases is:
what temperature will be cylinder P P
(A) A = 2 (B) A = 1
explode? PB PB
(A) 372.5 K (B) 3.725 K P P
(C) 37.25 K (D) 353.5 K (C) A = 4 (D) A = 3
PB PB
1. (A)
Sol. …………………………………………... 4. (C)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
2. A balloon weighting 50 kg is filled with
685.2 kg of Helium at 1 atm. pressure and 5. Two containers A and B contain the same
at 25ºC. What will be its pay load, if it gas. The pressure, volume, and absolute
displaced 5108 kg of air? temperature of the gas in A are twice that
(A) 437.28 kg (B) 43.728 kg of the gas in B. If the mass of the gas in B
(C) 4843.2 kg (D) 4372.8 kg is ‘x’ gram, the mass of gas A will be
2. (D) (A) 4xg (B) x/2 g
Sol. …………………………………………... (C) 2x g (D) x g
5. (C)
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
3. A rigid vessel of volume 0.50 m3 …………………………………………...
containing H2 at 20.5°C and a pressure of
611×103 Pa is connected to a second rigid 6. A gas occupied a volume of 250 mL at
vessel of volume 0.75 m3 containing Ar at 700 mm mercury pressure and 25°C
31.2°C at a pressure of 433×103 Pa. A temperature. How much additional
valve separating the two vessels is opened pressure is required to reduce the volume
and both are cooled to a temperature of of the gas to four-fifth its values at the
14.5°C. What is the final pressure in the same temperature?
vessels?
(A) 225 mm Hg (B) 175 mm Hg
(A) 2 × 105 (B) 3.22 × 105 Pa
(C) 4840 Pa (D) 4.84 × 105 Pa (C) 150 mm Hg (D) 265 mm Hg
3. (D) 6. (B)
Sol. …………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
7. A vessel with a capacity of 1 L contains …………………………………………...

hydrogen at 300 mm pressure. Another
vessel with a capacity of 2 L contains 10. For a closed (not rigid) container
oxygen at 600 mm pressure. The two containing n = 10 moles of an ideal gas
vessels are connected by a valve. If the fitted with movable, frictionless,
temperature is kept constant, the final weightless piston operating such that
pressure of the gas is pressure of gas remains constant at 0.0821
atm, which graph represents correct
(A) 500 mm (B) 900 mm variation of log V vs log T where V is in
(C) 450 mm (D) 300 mm litre and T in Kelvin.
7. (A)
Sol. …………………………………………...
(A)
…………………………………………...
…………………………………………...
8. A spherical balloon of 21 cm diameter is

to be filled up with hydrogen at N.T.P. (B)
from a cylinder containing the gas at 20
atm. at 27ºC. If the cylinder can hold 2.82
litre of water, the number of balloon that
can be filled up are
(A) 5 (B) 10
(C) 20 (D) 25 (C)
8. (B)
Sol. …………………………………………...
…………………………………………...
(D)
…………………………………………...
9. A weather balloon is inflated with helium.

The balloon has a volume of 100 m3 and it 10. (C)
Sol. …………………………………………...
must be inflated to a pressure of 0.10 atm.
If 50 L gas cylinders of helium at a …………………………………………...
pressure of 100 atm are used, how many
…………………………………………...
cylinders are needed? Assume that the
temperature is constant. 11. A box of 1 L capacity is divided into two
(A) 2 (B) 3 equal compartments by a thin partition
which are filled with 2g H2 and 16 g CH4
(C) 4 (D) 1 respectively. The pressure in each
9. (A) compartment is recorded as P atm. The
Sol. …………………………………………... total pressure when partition is removed
will be:
(A) P (B) 2P 13. (C)

(C) P/2 (D) P/4
11. (A) Sol. …………………………………………...
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... 14. If a mixture containing 3 moles of
12. At 0°C, the density of a certain gaseous hydrogen and 1 mole of nitrogen is
oxide at 2 bar is same as that of dinitrogen converted completely into ammonia, the
at 5 bar. What is the molecular mass of the ratio of initial and final volume under the
oxide? same temperature and pressure would be:
(A) 70 g/mol (B) 35 g/mol (A) 3 : 1 (B) 1 : 3
(C) 140 g/mol (D) 280 g/mol (C) 2 : 1 (D) 1 : 2
12. (A) 14. (C)
Sol. …………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
13. Which curve does not represent Boyle’s 15. At a pressure of 760 torr and temperature
law? of 273 K, the indicated volume of which
system is not consistent with the
observation
(A) (A) 14 g of N2 + 16g of O2; volume =
22.4 L
(B) 4 g of He + 44 g of CO2; volume =
44.8 L
(C) 7 g of N2 + 36g of O3; volume =
22.4 L
(D) 17 g of NH3 + 36.5g of HCl; volume
(B)
= 44.8L
15. (D)
Sol. …………………………………………...
…………………………………………...
(C) …………………………………………...
16. A student forgot to add the reaction

mixture to the round bottomed flask at
27°C but instead he/she placed the flask
on the flame. After a lapse of time, he
realized his mistake and using a pyrometer
(D)
he found the temperature of the flask was
477°C. What fraction of air would have …………………………………………...

been expelled out?
(A) 5/3 (B) 5/6 20. A gas cylinder contains 0.3 mol of N2, 0.2
mol of O2 and 0.5 mol of helium. If the
(C) 3/5 (D) 6/5
total pressure is P atmospheres, what will
16. (C) be the partial pressure of nitrogen?
Sol. …………………………………………...
(A) P/5 atm
…………………………………………... (B) 0.3 × P × 760 mm
P
…………………………………………... (C) × 760 mm
0.3
17. Pressure of 1g of an ideal gas A at 27°C is P
(D) atm
found to be 2 bar. When 2g of another 0.3
ideal gas B is introduced in the same flask 20. (B)
at the same temperature, the pressure Sol. …………………………………………...
becomes 3 bar. Find a relationship
between their molecular masses. …………………………………………...
(A) MA= 4MB (B) MB = 4 MA …………………………………………...
(C) MA= 2MB (D) MB = 2MA
17. (B) 21. When 2 g of a gas A is introduced into an
Sol. …………………………………………... evacuated flask kept at 25ºC, the pressure
is found to be one atmosphere. If 3 g of
…………………………………………... another gas B is then added to the same
flask, the total pressure becomes 1.5
…………………………………………... atmosphere. Assuming ideal gas
18. Dalton’s law of partial pressure will not behaviour, calculate the ratio of molecular
apply to which of the following mixture of wt. MA: MB.
gases (A) 3 : 1 (B) 1 : 4
(C) 1 : 3 (D) 2 : 5
(A) NH3 & HCl (B) H2 and O2
21. (C)
(C) H2 and CO2 (D) CO2 and Cl2
Sol. …………………………………………...
18. (A)
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... 22. Equal weights of CH4 and O2 are mixed in

an empty container at 25°C. The fraction
19. If the pressure of nitrogen and hydrogen of the total pressure exerted by oxygen is :
mixture in a closed vessel is 100 atm. and (A) 1/2 (B) 1/3
20% of the mixture reacts, the pressure at (C) 2/3 (D) 2/3 × 273/298
the same temperature will be 22. (B)
(A) the same (B) 110 atm Sol. …………………………………………...
(C) 90 atm (D) 80 atm …………………………………………...
19. (C)
Sol. …………………………………………... …………………………………………...
…………………………………………...
23. What will be the pressure exerted by a …………………………………………...

mixture of 3.2 g of methane and 4.4 g of
carbon dioxide contained in a 9 dm3 flask 26. A straight glass tube has two inlets X and
at 27°C ? Y at the two ends. The length of the tube
(A) 8.314 Pa (B) 8.314×102 Pa is 200 cm. HCl gas through inlet X and
(C) 2×102 Pa (D) 8.314×104 Pa NH3 gas through inlet Y are allowed to
23. (D) enter the tube at the same time. White
Sol. …………………………………………... fumes first appear at a point p inside the
tube. The distance of p from X is
…………………………………………... (A) 81.12 cm (B) 0.8112 cm
(C) 8.112 cm (D) 4.28 cm
…………………………………………...
26. (A)
24. V ml of H2 gas effuses through a hole in a Sol. …………………………………………...
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 27. A certain gas diffuses from two different
vessels A and B. The vessel A has a
(B) 20 Seconds : O2
circular orifice while vessel B has a square
(C) 25 Seconds : CO orifice of length equal to the radius of the
(D) 25 Seconds : CO2 orifice of vessel A. Calculate the ratio of
24. (B) the rates of diffusion of the gas from
Sol. …………………………………………... vessel A to vessel B, assuming same
temperature and pressure is;
…………………………………………... (A)  (B) 7 : 22
(C) 1 : 1 (D) 2 : 1
…………………………………………...
27. (A)
25. Which of the assumption of the kinetic Sol. …………………………………………...
molecular theory best explains. Dalton's
…………………………………………...
law of partial pressure?
(A) Gas molecules move at random with …………………………………………...
no attractive force between them
(B) the velocity of gas molecules is 28. Equal time is taken by 100 ml hydrogen
proportional to the absolute and 25 ml of a gas to diffuse through a
temperature porous partition. The mol wt. of the gas is
(C) the amount of space, occupied by a (A) 16 (B) 64
gas is much greater than the space, (C) 32 (D) 35
occupied by the actual gas molecules. 28. (C)
(D) collisions with the wall of the
…………………………………………...
container or with other molecules are Sol.
elastic. …………………………………………...
25. (A)
Sol. …………………………………………... …………………………………………...
…………………………………………...
29. The ratio of the rate of diffusion of helium of gases A and B having densities A and
and methane under identical condition of B are related by the expression :
pressure and temperature will be (A) rA = rB. (A / B)2
(A) 4 (B) 2 (B) rA = rB (B / A)1/2
(C) 1 (D) 0.5 (C) rA = (rB. B/A)1/2
29. (B) (D) rA = rB (A / B)1/2
Sol. …………………………………………... 33. (B)
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
30. X ml of H2 gas effused through a hole in a …………………………………………...

container in 5 second. The time taken for
34. Values of Vender Waal’s constant ‘a’ for
the effusion of the same volume of the gas
specified below under identical conditions three gases A, B and C are 5.6, 3.6 and 2.4
is : unit respectively. The increasing order of
(A) 10 sec : He (B) 20 sec : O2 their ease of liquefaction will be
(C) 25 sec : CO (D) 55 sec : CO2 (A) A, B, C (B) C, B, A
30. (B) (C) B, A, C (D) B, C, A
Sol. …………………………………………... 34. (B)
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
31. At what temperature will be rate of …………………………………………...

effusion of N2 be 1.625 times the rate of
35. The van der Waal’s equation for one mole
effusion of SO2 at 500°C ?
may be expressed as
(A) 273 K (B) 830 K
 RT  2 aVm ab
(C) 110 K (D) 173 K Vm3   b   Vm   0
31. (B)  P  p p
Sol. …………………………………………... where Vm is the molar volume of the gas.
Which of the following is incorrect?
…………………………………………... (A) For a temperature less than TC, V
has three real roots.
…………………………………………...
(B) For a temperature less than TC, V
32. The rate of diffusion of O2 and H2 at same has three imaginary roots
P and T are in the ratio (C) For a temperature equal to TC all
(A) 1 : 4 (B) 1 : 8 three root of V are real and
(C) 1 : 16 (D) 4 : 1 identical.
32. (A) (D) On increasing the temp. (T < TC),
Sol. …………………………………………... the three roots become closer to one
another.
…………………………………………... 35. (B)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
33. At constant volume and temperature
conditions, the rates of diffusion rA and rB …………………………………………...
36. If 10–4 dm3 of water is introduced into a

1.0 dm3 flask at 300 K, how many moles
of water are in the vapour phase when (B)
equilibrium is established?
(Given : Vapour pressure of H2O at 300 K
is 3170 Pa; R = 8.314 JK–1 mol–1) (C)
(A) 5.56 × 10–3 mol
(B) 1.53 × 10–2 mol (D)
(C) 4.46 × 10–2 mol
(D) 1.27 × 10–3 mol 38. (A)
36. (D)
Sol. …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
39. A closed container of volume 30 litre
37. The product for PV is plotted against P at contains a mixture of nitrogen and oxygen
two temperatures T1 and T2 and the ‘result gases, at a temperature of 24°C and
is shown in figure. What is correct about pressure 4 atm. The total mass of the
T1 and T2? mixture is 148 g. The moles of individual
gases in the container are (Take R = 0.08
L atm K–1mol–1)
(A) n N2  2, n O2  3
(B) n N2  1, n O2  3.75
(C) n N2  4, n O2  1
(A) T1 > T2 (B) T2 > T1
(D) n N2  3, n O2  2
(C) T1 = T2 (D) T1 + T2 = 1
37. (B) 39. (D)
Sol. …………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
38. In which of the following cases is the 40. A bottle of dry NH3 and a bottle of dry
pressure of air in air column maximum : HCl connected through a long tube are
(Assume same length of Hg column ins opened simultaneously under identical
each case) : conditions at both ends. The white
ammonium chloride ring first formed will
be:
(A) at the centre of the tube
(A)
(B) near the HCl bottle
(C) near the NH3 bottle
(D) throughout the length of tube
40. (B)
Sol. …………………………………………...
…………………………………………... 44. The root mean square speed of SO2 gas

becomes the same as that of oxygen at
…………………………………………... 27ºC when the temperature is
(A) 227ºC (B) 127ºC
2. Kinetic theory of gases (C) 300 K (D) 327ºC
41. The temperature at which the average
speed of the gas molecules is double that 44. (D)
at a temperature of 127ºC is Sol. …………………………………………...
(A) 1600 K (B) 1200 K
…………………………………………...
(C) 800 K (D) 400 K
41. (A …………………………………………...
Sol. …………………………………………...
45. The average speed of an ideal gas at 0ºC is
…………………………………………... 0.4 ms–1. If the temperature. of gas is
increased to 546ºC, its average speed will
…………………………………………... be
(A) 0.8 ms–1 (B) 1.6 ms–1
42. The root mean square velocity of one
(C) 0.346 ms–1 (D) 0.692 ms–1
mole of a monoatomic gas having molar
45. (D)
mass M is ur.m.s The relation between the
Sol. …………………………………………...
translational kinetic energy per mole (E)
of the gas and ur.m.s is …………………………………………...
3E 2E
(A) ur.m.s. = (B) ur.m.s.= …………………………………………...
2M 3M
2E E 46. The K.E. of N molecule of O2 is x Joules
(C) ur.m.s. = (D) ur.m.s. = at –123°C. Another sample of O2 at 27°C
M 3M
has a KE of 2x Joules. The latter sample
42. (C)
contains
Sol. …………………………………………... (A) N molecules of O2
…………………………………………... (B) 2N molecules of O2
(C) N/2 molecules of O2
…………………………………………... (D) N/4 molecule of O2
46. (A)
43. The kinetic energy of a hydrogen Sol. …………………………………………...
molecule travelling at 1900 m/s is
(A) 1.21 × 10–20 J (B) 3.02 × 10–21 J …………………………………………...
(C) 5.99 × 10–21 J (D) 6.04 × 10–18 J …………………………………………...
43. (C)
47. In two vessels of 1 litre each at the same
Sol. …………………………………………... temperature 1 g of H2 and 1g of CH4 are
taken, for these :
…………………………………………...
(A) Vrms values will be same
…………………………………………... (B) Kinetic energy per mol will be same
(C) Total kinetic energy will same
(D) Pressure will be same
47. (B)
Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
48. The rms speed of N2 molecules in a gas is 51. For an ideal gas, number of moles per litre
u. If the temperature is doubled and the in terms of its pressure P, gas constant R
nitrogen molecules dissociate into and temperature T is
nitrogen atoms, the rms speed becomes : (A) PT/R (B) PRT
(A) u/2 (B) 2u (C) P/RT (D) RT/P.
(C) 4u (D) 14u 51. (C)
48. (B) Sol. …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
52. According to the kinetic theory of gases,
49. The ratio among most probable velocity, in an ideal gas, between two successive
mean velocity and root mean square collisions a gas molecule travels.
velocity is given by (A) in a wavy path
(A) 1 : 2 : 3 (B) in a straight line path
(B) 1 : 2: 3 (C) with an accelerated velocity
(C) 2 : 3: 8/  (D) in a circular path
52. (B)
(D) 2 : 8 /  : 3
Sol. …………………………………………...
49. (D)
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... 53. As the temperature is raised from 20°C to
40°, the average kinetic energy of neon
50. The Ne atom has 10 times the mass of H2. atoms changes by a factor of which of the
Which of the following statements is true? following ?
(I) At 25°C they both pressure as one
313
mole of H2 at STP. have the same (A) (B) (313 / 293)
translational kinetic energy. 293
(II) Ten moles of H2 would have the 1
(C) (D) 2
same volume as 1 mole of Ne at same 2
temperature and pressure. 53. (A)
(III) One mole of Ne exerts the same Sol. …………………………………………...
(IV) A H2 molecule travels 10 times faster
than Ne atom at same temperature. …………………………………………...
(V) At STP, one litre of Ne has 10 times
…………………………………………...
the density of 1 litre of H2.
(A) II, IV, V (B) I, III, V
54. In van der Waals equation of state of the
(C) I, II, II (D) I, II
gas law, the constant ‘b’ is a measure of
50. (B)
Sol. …………………………………………... (A) volume occupied by the molecules
(B) intermolecular attraction
(C) intermolecular repulsions 57. (C)

(D) intermolecular collisions per unit Sol. …………………………………………...
volume
…………………………………………...
54. (A)
Sol. …………………………………………... …………………………………………...
…………………………………………...
58. The graphs representing distribution of
…………………………………………... molecular speeds at 300 K for gases Cl2
and N2 are as shown below (Atomic mass
55. Which one of the following statements is N = 14, Cl = 35.5)
NOT true about the effect of an increase
in temperature on the distribution of
molecular speeds in a gas ?
(A) The area under the distribution curve
remains the same as under the lower
temperature
(B) The distribution becomes broader (A) I graph is for N2 and II is for Cl2
(C) The fraction of the molecules with (B) II graph is for N2 and I is for Cl2
the most probable speed increases. (C) either graph can be taken for N2 for
Cl2
(D) The most probable speed increases
(D) information is not sufficient
55. (C)
58. (B)
Sol. …………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
56. Pressure of a gas is the result of: 59. The density of Nitrogen gas is maximum
(A) Molecular speed only at:
(B) Molecular speed and mass (A) STP
(C) Molecular mass only
(B) 273 K and 0.5 atm
(D) Intermolecular forces
(C) 546 K and 4 atm
56. (B)
(D) 546 K and 1 atm
Sol. …………………………………………...
59. (C)
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
57. The molecular velocity of any gas is : …………………………………………...

(A) inversely proportional to absolute 60. Two gases A and B having molecular
temperature. weights 60 and 40 respectively are
(B) directly proportional to square of enclosed in a vessel. The weight of A is
temperature. 0.6 g and that of B is 0.2 g. The total
(C) directly proportional to square root pressure of the mixture is 750 mm.
of temperature. Calculate the partial pressure of the two
(D) inversely proportional to the square gases :
root of temperature. (A) pA = 500 mm, pB = 250 mm
(B) pA = 250 mm, pB = 500 mm 63. (C)

(C) pA = 600 mm, pB = 150 mm Sol. …………………………………………...
(D) pA = 150 mm, pB = 600 mm
…………………………………………...
60. (A)
Sol. …………………………………………... …………………………………………...
…………………………………………... 64. Consider a real gas placed in a container.
If the intermolecular attractions are
…………………………………………... supposed to disappear suddenly which of
the following would happen?
61. Pressure remaining the same, the volume
(A) The presence decreases
of a given mass of an ideal gas increases
(B) The pressure increases
for every degree centigrade rise in
(C) The pressure remains unchanged
temperature by definite fraction of its
(D) The gas collapses
volume at:
64. (B)
(A) 0°C Sol. …………………………………………...
(B) Its critical temperature
(C) Absolute zero …………………………………………...
(D) Its Boyle temperature
…………………………………………...
61. (A)
Sol. …………………………………………... 65. The correct graph to H2 gas it :
…………………………………………...
…………………………………………... (A)
3. Compressibility factor
62. The compressibility of a gas is less than
unity at 1 atm and 273 K. Therefore,
(A) Vm > 22.4 litre (B) Vm < 22.4 litre
(C) Vm = 22.4 litre (D) Vm = 44.8 litre (B)
62. (B)
Sol. …………………………………………...
…………………………………………...
…………………………………………... (C)
PV
63. Consider the equation Z = . Which of
RT (D) All of these
the following statements is correct? 65. (A)
(A) When Z > 1, real gases are easier to Sol. …………………………………………...
compress than the ideal gas
(B) When Z = 1, real gases get …………………………………………...
compressed easily
(C) When Z > 1, real gases are difficult …………………………………………...
to compress
(D) When Z = 1, real gases are difficult 66. At 273 K temperature and 9 atm pressure,
to compress the compressibility for a gas is 0.9. The
volume of 1 mili-mole of gas of this (D) (P + a/V2)(V) = RT

temperature and pressure is : 69. (D)
(A) 2.24 litre (B) 0.020 Ml Sol. …………………………………………...
(C) 2.24 mL (D) 22.4 mL
66. (C) …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
70. The values of van der Waals constant ‘a’
…………………………………………... for the gases O2, N2, NH3 and CH4 are
1.360, 1.390, 4.170 and 2.253 L2 atm mol–
2
67. Compressibility factor for H2 behaving as respectively. The gas which can most
real gas is : easily be liquified is
 a  (A) O2 (B) N2
(A) 1 (B) 1   (C) NH3 (D) CH4
 RTV 
70. (C)
 Pb  RTV Sol. …………………………………………...
(C) 1   (D)
 RT  (1  a)
67. (C) …………………………………………...
Sol. …………………………………………... …………………………………………...
…………………………………………... 71. In van der Waals equation of state for a
non-ideal gas, the term that accounts for
…………………………………………...
intermolecular forces is
68. At low pressures (For 1 mole), the Vander (A) (V - b) (B) RT
Waal’s equation is written as  a 
(C)  P  2  (D) (RT)–1
 a   V 
 p  V 2  V  RT 71. (C)
Sol. …………………………………………...
The compressibility factor is then
equation to : …………………………………………...
 a   RTV 
(A) 1   (B) 1   …………………………………………...
 RTV   a 
 a   RTV  72. The pressure of real gases is less than the
(C) 1   (D) 1  
 RTV   a  pressure of an ideal gas because of :
68. (A) (A) Increase in number of collisions
Sol. …………………………………………... (B) Finite size of molecule
(C) Increases in KE of molecules
…………………………………………... (D) Intermolecular forces of attraction
72. (D)
…………………………………………... Sol. …………………………………………...
…………………………………………...
4. Vander Waal’s equation or Real gases
69. At very low pressure, the Vander Waal’s …………………………………………...
equation for one mole is written as
73. A real gas obeying Vander Waal’s
(A) PV – Pb = RT
equation will resemble ideal gas, if the :
(B) PV + a = RT
(A) constants a & b are small
(C) PV = RT
(B) a is large & b is small …………………………………………...

(C) a is small & b is large
…………………………………………...
(D) constant a & b are large
73. (A) 77. ‘a’ and ‘b’ are Van der Waals’ constants
Sol. …………………………………………... for gases. Chlorine is more easily
liquefied than ethane because
…………………………………………...
(A) a and b for Cl2 > a and b for C2H6
…………………………………………... (B) a and b for Cl2 < a and b for C2H6
(C) a for Cl2 < a for C2H6 but b for Cl2 >
74. For the non-zero values of force of b for C2H6
attraction between gas molecules, gas (D) a for Cl2 > a for C2H6 but b for Cl2 <
equation will be : b for C2H6
n 2a 77. (D)
(A) PV = nRT –
V Sol. …………………………………………...
(B) PV = nRT + nbP
(C) PV = nRT …………………………………………...
nRT …………………………………………...
(D) P =
Vb
74. (A) 78. When r, P and M represent rate of
Sol. …………………………………………... diffusion, pressure and molecular mass,
respectively, then the ratio of the rates of
…………………………………………... diffusion (rA/rB) of two gases A and B, is
given as :
…………………………………………...
(A) PA/PB) (MB/MA)1/2
75. The compressibility factor a real gas at (B) (PA/PB)1/2 (MB/MA)
high pressure is : (C) (PA/PB) (MA/MB)1/2
RT (D) (PA/PB)1/2 (MA/ B)1/2
(A) 1 + (B) 1 78. (A)
pb
Sol. …………………………………………...
pb pb
(C) 1 + (D) 1 –
RT RT …………………………………………...
75. (C)
Sol. …………………………………………... …………………………………………...
5. Liquification of gases.
…………………………………………... 79. Select incorrect statement:
(A) we can condense vapour simply by
…………………………………………... applying pressure
76. The van der Waal’s constant ‘b’ of a gas is (B) to liquefy a gas one must lower the
temperature below TC and also apply
4104 L / mol. How near can the pressure
centres of the two molecules approach (C) at TC, there is no distinction between
each other? [Use : NA = 6 × 1023] liquid and vapour state hence density
(A) 10–7 m (B) 10–10 m of the liquid is nearly equal to
(C) 5 × 10–11 m (D) 5 × 10–9 m density of the vapour
76. (B) (D) However greater the pressure applied,
Sol. …………………………………………... a gas cannot be liquified below it’s
critical temperature
79. (D) 83. Two vessels of the same capacity and at

Sol. …………………………………………... the same temperature are filled with 4.4 g
of hydrogen gas in one and 44 g of CO2 in
…………………………………………... the other. If the pressure of CO2 in the
…………………………………………... second container is 1 atm that of hydrogen
in the first container would be at _______
80. The excluded volume of a gas will be atm
T 83. (2.2)
larger, if C is:
PC Sol. …………………………………………...
(A) small (B) large
…………………………………………...
(C) equal to 1 (D) less than unity
80. (B) …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
84. How many times should the temperature
…………………………………………... be increased so that the rms speed of gas
molecules in a closed container of fixed
NUMERICAL VALUE TYPE QUESTIONS volume is increased from 3 × 102 cms–1 to
6 × 102 cms–1 is-
1. Gaseous Laws
84. (4)
81. Two gases contained separately in flasks
Sol. …………………………………………...
of equal pressures of 1 atmosphere each.
What will be the resultant pressure (atm) …………………………………………...
if the flasks are connected?
81. (1) …………………………………………...
Sol. …………………………………………... …………………………………………...
…………………………………………...
85. 0.2 g of a gas X occupies 320 mL but
…………………………………………... under the same conditions 0.1 g of O2
occupies 290 mL. The molar mass of gas
…………………………………………...
‘X’ is
82. At 25ºC and 750 mm pressure 380 ml of 85. (58)
dry oxygen was collected. If the Sol. …………………………………………...
temperature is constant what volume (ml)
…………………………………………...
will oxygen occupy at 760 mm pressure?
82. (375) …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
86. Density of a gas is found to be 5.46 g/dm3
…………………………………………... at 27°C at 2 bar pressure. What will be its
density (gm/lit.) at STP?
…………………………………………...
86. (3)
Sol. …………………………………………...
…………………………………………...
…………………………………………... 90. (5)

Sol. …………………………………………...
…………………………………………...
…………………………………………...
87. What will be the pressure (bar) of the
gaseous mixture when 0.5 L of H2 at 0.8 …………………………………………...
bar and 2.0 L of dioxygen at 0.7 bar are …………………………………………...
introduced in a 1 L vessel at 27°C ?
87. (1.8) 91. Given a one meter long glass tube closed
Sol. …………………………………………... at one end having a uniform cross-section
containing a mercury column of 10 cm
…………………………………………... length, at a distance of 39 cm from the
closed end. By what distance (in cm)
…………………………………………... would this column move down, if the tube
is held vertical with the open end
…………………………………………... downwards.? [Take atom spheric pressure
to be 75 cm of Hg)
88. 50 ml of hydrogen diffuse through a small
hole from a vessel in 20 minutes. Time
taken for 40 ml of oxygen to diffuse under
similar conditions through a same hole
will be _______ minutes.
88. (64) 91. (6)
Sol. …………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
89. At identical temperature and pressure, the 92. A bottle of cold drink has 200 ml of liquid
in which concentration of CO2 is 0.1 M. If
rate of diffusion of hydrogen gas is 3 3 CO2 behaves as ideal gas, the volume of
times that of a hydrocarbon having CO2 at 0°C and 1 atm equivalent to the
molecular formula CnH2n–2. What is the one in cold drink is ___ litres
value of n? 92. (0.448))
89. (4) Sol. …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
93. A plot of the density versus the pressure
90. The stopcock, connecting the two bulbs of for air at 27°C has the limiting slope = 1.2
volume 8 litre and 10 litre containing an × 10–5 kg m–3 Pa–1. The composition of air
ideal gas at 6.25 atm and 4 atm (contains only N2 and O2) in volume ratio
respectively, is opened. What is the final of N2 and O2 is (R = 8.0 J/K-mol) x : 1
gas pressure (atm), if the temperature then x is –
remains same? 93. (4)
Sol. …………………………………………... 97. At what temperature (K) will the total

translational kinetic energy of 0.80 mole
…………………………………………... of He gas be the same as the total
translational kinetic energy of 0.40 mol of
…………………………………………... Ar at 400 K?
…………………………………………... 97. (200)
Sol. …………………………………………...
94. A sample of gas in a closed container of
fixed volume is at 250 K and 400 mm of …………………………………………...
Hg pressure. If the gas is heated to 375 K, …………………………………………...
its pressure increases to 600 mm of Hg.
By what factor will be the average speed …………………………………………...
of the molecules increases?
94. (1.22) 4. Vander Waal’s equation or Real gases
Sol. …………………………………………... 98. If the pressure of a gas contained in a
closed vessel is increased by 0.4% when
…………………………………………...
heated by 1°C its initial temperature must
…………………………………………... be. ---- K
98. (250)
…………………………………………... Sol. …………………………………………...
95. The rate of effusion of helium gas at a …………………………………………...

pressure of 1000 torr is 10 torr min–1.
What will be the rate of effusion (torr …………………………………………...
min–1) of hydrogen gas at a pressure of
2000 torr at the same temperature? …………………………………………...
[take 2 =1.41 and 3 = 1.73)
95. (28.2) 5. Liquification of gases.
Sol. …………………………………………... 99. The volume of 6 g hydrogen at 1.5 atm
and 273ºC is – (If volume of 1 mole gas at
…………………………………………... 1 atm, 273 K is 22.4 L)
…………………………………………... 99. (89.6)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
2. Kinetic theory of gases …………………………………………...

96. The average velocity of an ideal gas
…………………………………………...
molecule at 27°C is 0.3 m/sec. The
average velocity at 927°C will be ____ 100. The critical pressure and temperature of a
m/sec. van der Waal gas are 48 atm and 128 K,
96. (0.6) respectively. The critical volume of the
Sol. …………………………………………... gas is _____ litre.
[Take R = 0.08 lit-atm/mole K)
…………………………………………... 100. (0.08)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
JEE ADVANCED EXERCISE

SINGLE OPTION CORRECT QUESTIONS
3. The critical density of O2 at 300 K is
0.45 gm/cm3. The Vander Waal’s
1. Gaseous Laws
constant b is
1. The apparatus shown consists of three
(A) 237 litre/mole
bulbs connected by stopcocks of
(B) 0.237 litre/mole
negligible volume. The temperature is
(C) 0.0237 litre/moles
constant.
(D) 2.37 litre/mole
3. (C)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
PA = 2.13 atm PB = 0.861 atm – PC = …………………………………………...

1.15 atm – VA = 1.50 LVB = 1.0 L VC =
2.0 L. When all the stopcocks are opened, 4. If at top of a hill 2000 m above sea level,
the atmospheric pressure is 50 cm of Hg
the pressure in the bulb ‘B’ will be
and at the sea level the atmospheric
(A) 1.41atm (B) 0.861 atm pressure is 74.5 cm of Hg, and you need
(C) 1.38 atm (D) 1.18 atm as much oxygen to breath at sea level as
1. (A) on the top of the hill, how much faster
Sol. …………………………………………... need you breathe on the hill top?
(A) 2.44 times (B) 1.49 times
…………………………………………... (C) 5 times (D) 7 times
…………………………………………... 4. (B)
Sol. …………………………………………...
2. 10 g each of sulphur dioxide, Phosphine
and hydrogen are kept in three flasks. …………………………………………...
Decreasing order of number of atoms is …………………………………………...
(A) Phosphine, sulphur dioxide,
hydrogen …………………………………………...
(B) Hydrogen, Phosphine, sulphur
dioxide 5. The ratio of the rate of diffusion of
(C) Sulphur dioxide, Phosphine, helium and methane under identical
hydrogen condition of pressure and temperature
(D) Hydrogen, sulphur dioxide, will be
Phosphine (A) 4 (B) 2
2. (B) (C) 1 (D) 0.5
Sol. …………………………………………... 5. (B)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
6. What is the density of wet air with 75% (A) H2 > N2 > O2 > HBr
relative humidity at 1 atm and 300 K? (B) HBr > O2 > N2 > H2
Given : vapour pressure of H2O is 30 torr
(C) HBr > H2 > O2 > N2
and average molar mass of dry air is 29 g
mol–1. (D) N2 > O2 > H2 > HBr
(A) 1.614 g/L (B) 0.96 g/L 9. (A)
(C) 1.06 g/L (D) 1.164 g/L Sol. …………………………………………...
6. (D)
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………...
10. Which of the following statements false-
(A) The ratio of the mean speed to the
2. Kinetic theory of gases rms speed is independent of
7. The root mean square velocity of an ideal temperature of gas.
gas at constant pressure varies with (B) The square of the mean speed of the
density (d) as molecules is equal to the mean
(A) d2 (B) d square speed at a certain
(C) d (D) 1/ d temperature.
(C) Mean translational kinetic energy of
7. (D)
the gas molecules at any given
Sol. …………………………………………...
temperature is independent of the
…………………………………………... molecular mass of gas.
(D) The difference between rms-speed
…………………………………………... and mean speed at any temperature
for different gases diminished as
…………………………………………... larger and yet larger molar masses
are considered.
10. (B)
8. The average velocity of gas molecules is Sol. …………………………………………...
400 m/sec. Calculate its rms velocity at
the same temperature. …………………………………………...
(A) 234 m/s (B) 434 m/s
…………………………………………...
(C) 400 m/s (D) 124 m/s
8. (B) …………………………………………...
Sol. …………………………………………... 3. Compressibility factor
…………………………………………... 11. The compressibility 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
9. At STP, the decreasing order of root (D) Vm= 44.8 litres
mean square velocity of molecules of H2, 11. (B)
N2, O2 and HBr is- Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... 14. If the intermolecular forces vanish away,

the volume occupied by the molecules
12. The compression factor (compressibility contained in 4.5kg water at 0°C and 1
factor) for one mole of a van der Waals atm will be given by
gas at 0°C and 100 atmospheric pressure (A) 4.5 m3 (B) 5.6 m3
is found to be 0.5. Assuming that the (C) 11.2 m 3
(D) 11.2 litre
volume of a gas molecule is negligible, 14. (B)
calculate the van der Waals constant ‘a’. Sol. …………………………………………...
(A) 1.253 atm L2 mol–2
(B) 0.253atm L2 mol–2 …………………………………………...
(C) 2.253 atm L2 m–2
(D) 1.0 atm L2 m–2 …………………………………………...
12. (A)
…………………………………………...
Sol. …………………………………………...
…………………………………………... 4. Vander Waal’s equation or Real gases

15. The temperature at which 5 moles of SO2
…………………………………………... will occupy a volume of 10 litres at a
pressure of 15 atm. using Vander Waal’s
…………………………………………... constants a = 6.71 litre2 atm mole–1, b =
0.0564 litre mol–1
13. Refer to the figure given : (A) 395.3 K (B) 39.53 K
(C) 3953 K (D) 365.85
15. (A)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
Which of the following statements is …………………………………………...
wrong?
(A) For gas A, a = 0 and Z will linearly 16. If the molecules of a gas are spherical of
depend on pressure radius 1.0 A, the van der waals’s constant
(B) For gas B, b = 0 and Z will linearly b of the gas is
depend on pressure (A) 0.0025LMol (B) 0.0101 LMol–1
(C) Gas C is a real gas and we can find (C) 0.0371 LMol–1 (D) 0.0224LMol–1
‘a’ and ‘b’ if intersection data is 16. (B)
given. Sol. …………………………………………...
(D) All van der Waal gases will behave
like gas C and give positive slope at …………………………………………...
high pressure
…………………………………………...
13. (B)
Sol. …………………………………………... …………………………………………...
…………………………………………...
17. At 100°C and 1 atm, if the density of …………………………………………...

liquid water is 1.0 g cm–3 and that of
water vapour is 0.0006 g cm–3, then the 5. Liquification of gases.
volume occupied by water molecules in 1 20. The critical constant PC and TC for four
litre of steam at that temperature is: gases are
(A) 6 cm3 (B) 60 cm3 Gas Critical Critical
temperature pressure
(C) 0.6 cm3 (D) 0.06 cm3
O2 153 K 50 bar
17. (C)
Cl2 417 K 76 bar
Sol. …………………………………………... H2 33.9 K 13.5 bar
…………………………………………... He 5.12 2.2 bar
The gas with smallest value of Van der
…………………………………………... Waal’s constant b is
(A) O2 (B) Cl2
…………………………………………... (C) H2 (D) He
20. (D)
18. The Van der Waal’s constants for three Sol. …………………………………………...
gases R, S and T are given below
Gas a(atm b(l/mol) …………………………………………...
2
L /mol ) 2
R 5.2 0.420 …………………………………………...

S 3.8 0.038
…………………………………………...
T 2.3 0.032
The correct sequence of placing the easily MULTIPLE OPTION CORRECT QUESTIONS
liquefiable gas last and the one difficult to
liquefy first is 1. Gaseous Laws
(A) R,S,T (B) S,T,R 21. If the pressure of the gas contained in a
(C) T,S,R (D) S,R,T closed vessel is increased by 20% when
18. (C) heated by 273°C then it’s initial
Sol. …………………………………………...
temperature must have been
…………………………………………... (A) 1092°C (B) 1092K
(C) 1365°C (D) 1365K
…………………………………………... 21. (A, D)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
19. When the volume of a fixed mass of a gas
(y-axis) is plotted against temperature, in …………………………………………...
°C, (X-axis), at constant pressure of 5
atm, the graph is straight line with slope …………………………………………...
0.08 1/°C cutting the volume axis at V0.
The value of V0 is
(A) 0 (B) 0.08 22. Two flask A and B have equal volumes.
(C) 21.84 l (D) 21.84 ml Flask A contains hydrogen at 600 K
19. (C) while flask B has same mass of CH4 at
Sol. …………………………………………... 300 K. Then choose the correct options.
(A) In flask A the molecules move faster
…………………………………………... than B
…………………………………………...
(B) In flask B the molecules move faster Sol. …………………………………………...

than A
(C) Flask A contains greater number of …………………………………………...
molecules than B …………………………………………...
(D) Flask B contains more molecules
than A …………………………………………...
22. (A, C)
Sol. …………………………………………... 25. The mutual attraction of molecules in a
real gas is an important aspect of
…………………………………………... (A) Avogadro’s law
(B) Graham’s law
…………………………………………... (C) van der Waal’s theory
(D) Intermolecular forces
…………………………………………...
25. (C, D)
Sol. …………………………………………...
23. With reference to the above graph,
choose the correct alternatives …………………………………………...
…………………………………………...
…………………………………………...
(A) PB > PA
2. Kinetic theory of gases
(B) PA > PB
26. Which of the following statements is/are
(C) Pressure first increases then
wrong ?
decreases
(A) At a given temperature the
(D) Pressure first decreases then
transitional K.E. of one mole of
increases
every gas is same which is equal to
23. (B, C)
3/2 RT
Sol. …………………………………………...
(B) K.E. of a gas depends on its mass
…………………………………………... (C) K.E. depends on the volume
(D) K.E. depends on the pressure
…………………………………………... 26. (C, D)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
24. Precisely 1 mol of helium and 1 mol of
neon are placed in a container. Indicate …………………………………………...
the correct statements about the system :
…………………………………………...
(A) Molecules of the two gases strike the
wall of the container with same 27. Consider a sample of equimolar mixture
frequency. of He gas and Ne gas both at 300K and 1
(B) Molecules of helium strike the wall atmosphere. Assuming ideal behaviour
more frequently. which of the following quantities are
(C) Molecules of helium has greater equal for two samples ?
average molecular speed. (A) Root mean square speed of
(D) Helium exerts larger pressure. molecules
24. (B,C) (B) Mean translational kinetic energy of
molecules
(C) Number density of molecules …………………………………………...

(D) Kinetic energy of molecules
27. (B, C, D) …………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………... 4. Vander Waal’s equation or Real gases

30. Actual volume of one mol of CO2
…………………………………………... molecules is 0.0107 L. If 220 g of CO2
placed in a 10.0 L container, the free
28. If the rms velocity of nitrogen and space available for the molecules to move
oxygen molecule are same at two about is
different temperature and same pressure (A) 10.0L (B) 9.9465L
then (C) 9.9572 L (D) 9.7860 L
(A) Average speed of molecules is also 30. (D)
same Sol. …………………………………………...
(B) density (gm/lt.) of nitrogen and
oxygen is also equal. …………………………………………...
(C) Number of moles of each gas is also
equal. …………………………………………...
(D) most probable velocity of molecules
is also equal. …………………………………………...
28. (A, B, D)
Sol. …………………………………………... PARAGRAPH BASED QUESTIONS
…………………………………………... PARAGRAPH – 2
…………………………………………... 1. Gaseous Laws

…………………………………………...
On the recently discovered 10th planet it has been
found that the gases follow the relationship PeV/2
3. Compressibility factor = nCT where C is constant other notation are as
29. Which of the following statements is/ are usual
correct? (V in lit., P in atm and T in Kelvin). A curve is
(A) All real gases are less compressible plotted between P and V at 500 K & 2 moles of
than ideal gas at high pressures? gas as shown in figure
(B) Hydrogen and helium are more
compressible than ideal gas for all
values of pressure.
(C) Except H2 and He, the
compressibility factor
 PV 
Z   1 for all gases at low
 nRT  31. The value of constant C is
pressures. (A) 0.01 (B) 0.001
(D) The compressibility factor of real (C) 0.005 (D) 0.002
gases is independent of temperature.
31. (B)
29. (A, C) Sol. …………………………………………...
Sol. …………………………………………...
…………………………………………... u = root mean square velocity.

Translational kinetic energy of n moles
…………………………………………... 1 3 3
Mu 2  (PV)  (nRT)
…………………………………………... 2 2 2
Average translational kinetic energy per
32. Find the slope of the curve plotted 3  RT  3
between P Vs T for closed container of
molecule =    (KT)
2  N0  2
volume 2 lit. having same moles of gas
3PV 3RT 3P
e u rms   
(A) (B) 2000 e M M d
2000
2 8RT
(C) 500 e (D) and u av 
1000e M
32. (D)
Sol. …………………………………………... 34. 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
A and B contain same number of
…………………………………………... molecules, what will be the ratio of
…………………………………………... pressures of 2 samples in 2 separate
containers of equal volume?
33. If a closed container of volume 200 lit. of P P
(A) A  2 (B) A  3
O2 gas (ideal gas) at 1 atm & 200 K is PB PB
taken to planet. Find the pressure of
PA PA
oxygen gas at the planet at 821 K in same (C) 4 (D) 8
container PB PB
10 20 34. (D)
(A) 100 (B) 50 Sol. …………………………………………...
e e
(C) 1 atm (D) 2 atm …………………………………………...
33. (A)
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………...
35. Under 3 atm; 12.5 litre of a gas weigh 15
…………………………………………... gm. What will be the average speed of
gaseous molecules?
(A) 8.028 104 cm / sec
PARAGRAPH – 1 (B) 6.028 102 cm / sec
(C) 8.028 106 cm / sec
2. Kinetic theory of gases
(D) 6.028 104 m / sec
Pressure of an ideal gas is obtained from kinetic
35. (A)
gas equation. The kinetic gas equation is :
Sol. …………………………………………...
1 1
PV  (m N 0 ) u 2  Mu 2
3 3 …………………………………………...
where, (molar mass)
Avogadro's number …………………………………………...
…………………………………………... N0 N0
N0
2 4
36. Three closed vessels A, B and C are at (D) t = 0 t = 100 sec t = 200 sec
the same temperature and contain gases N0 N0
N0
which obey the Maxwellian distribution 4 16
of velocities. Vessel A contains only O2, 37. (C)
B only N2, and C, a mixture of equal Sol. …………………………………………...
quantities of O2 and N2. If the average
sped of the O2 molecules in vessel A is …………………………………………...
V1, that of the N2 molecules in vessel B is
V2, the average speed of the O2 molecules …………………………………………...
in vessel C is
(A) (V1 + V2)/2 (B) V1 …………………………………………...
(C) V1V2 (D) 3k T / M
where M is the mean molar mass of the 38. Identify the correct option regarding
mixture. sequence of (True) & (False) statements
36. (B) (i) The time required for moles of gas I
Sol. …………………………………………... to get reduced to half of original &
that of gas II to reduced to half of
…………………………………………... original is independent of initial
moles of gas I & gas II.
…………………………………………... (ii) The rate at which initially
molecules will come out in gas I as
…………………………………………...
compared to gas II will be greater in
PARAGRAPH – 3 gas II if initial no. of molecules are
same.
2. Kinetic theory of gases (iii) The time required for moles to get
reduced from 1 to 0.8 in gas I and 2
Under a given condition, it is found that two to 1.6 in gas II will be same
separate gases effuse out of two separate (iv) For the two gases, moles remaining
container in such a way that they follows the on the container after same interval
dN dN should be in geometrical
equation = – K1N & = – K2N, K1 = progression.
dT dT
6.93 × 10–3 sec–1, K2 = 6.93 × 10–5 sec–1, where N (A) TFFT (B) TFTT
(C) FTFT (D) TTFF
is no. of molecules remaining in the container. 38. (A)
(ln 2 = 0.693) Sol. …………………………………………...
37. Which one of the following may …………………………………………...

represent no. of molecules present after
the given interval for gas-I? …………………………………………...
(A) t = 0 t = 100sec t = 200 sec
N0 N0 …………………………………………...
N0
2 8 PARAGRAPH – 4
(B) t = 0 t = 100 sec t = 200 sec 2. Kinetic theory of gases
N0 N0
N0
8 16 Maxwell and Boltazmann proposed that gas
(C) t = 0 t = 100 sec t = 200 sec molecules are always in rapid random motion
colliding with each other and with the wall of
container. Due to such collisions, their velocities PARAGRAPH – 5

always change. A fraction of molecules have a
particular molecular velocity at a time. James
Sketch shows the plot of Z v/s P for of a
Clark Maxwell calculated the distribution of
hypotherical gas for one mole at three distinct
velocity among fraction of total number of
temperature.
molecules, on the basis of probability
8RT
VAV 
M
2RT
VMP 
M
3RT Boyle’s temperature is the temperature at which
VRMS 
M a gas shows ideal behaviour over a pressure
Where VA = Average velocity range in the low pressure region. Boyle’s
VMP = most probable velocity a
temperature (Tb )  . If a plot is obtained at
VRMS = Root mean square velocity Rb
R = Gas constant temperature well below Boyle’s temperature then
T = Temperature on absolute scale the curve will show negative deviation, in low
M = Molecular weight of the gas pressure region and positive deviation in the high
39. The ratio VRMS : VAV : VMP pressure region. Near critical temperature the
(A) 1 : 0.921 : 0.816 curve is more likely as CO2 and the temperature
(B) 2 : 0.0921 : 1 well above critical temperature curve is more like
(C) 3 : 0.0921 : 8 H2 at 0°C as shown above. At high pressure
(D) 4 : 0.0921 : 0.816 suppose all the constant temperature curve varies
39. (A) linearly with pressure according to the following
Sol. …………………………………………... Pb
equation : Z  1  (R = 2 cal mol–1 K–1).
RT
…………………………………………...
…………………………………………... 41. For 500 K plot value of Z changes from 2

to 2.2. If pressure is varied from 1000
…………………………………………... atm to 1200 atm (high pressure) then the
b
value of will be
40. The rms velocity of hydrogen is 7 RT
times the rms velocity of nitrogen. If T is (A) 10–3 atm–1 (B) 2 × 10–3 atm–1
–4 –1
the temperature of the gas (C) 5 × 10 atm (D) 10–4 atm–1
(A) T(H2) = T(N2) (B) T(H2) > T(N2) 41. (A)
(C) T(H2) < T (N2) (D) T (H2) = T(N2) Sol. …………………………………………...
40. (C)
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... 42. As shown in the figure at 200 K and 500

atm value of compressibility factor is 2
(approx). Then molar volume of the gas
at this point will be
(A) 0.01 L (B) 0.09 L
(C) 0.065 L (D) 0.657 L …………………………………………...

42. (C)
Sol. …………………………………………... 45. Statement-1: The pressure of a fixed
amount of an ideal gas is proportional to
…………………………………………... its temperature at constant volume.
Statement-2: Frequency of collisions and
…………………………………………... their impact both increase in proportion
to the square root of temperature.
…………………………………………... 45. (B)
ASSERTION & REASON BASED QUESTIONS Sol. …………………………………………...
…………………………………………...
In the following questions each equation contains
Statement I (Assertion) and Statement II 46. Statement-1: The value of the van der
(Reason). Each question has 4 choices (A), Waal’s constant ‘a’ is larger for ammonia
(B)(C), and (D) out of which only one is correct than for nitrogen.
(A) Statement I: is true; Statement II is true; Statement-2: Hydrogen bonding is
Statement II is a correct explanation for present in ammonia.
Statement I. 46. (A)
(B) Statement I is True; Statement II is True; Sol. …………………………………………...
Statement II is Not a correct explanation
…………………………………………...
for statement I.
(C) Statement I is True; Statement II is false 47. Statement-1: Van der Waal’s equation
(D) Statement I is False, statement II is True is applicable only to non-ideal gases.
Statement-2: Ideal gases obey the
equation PV = nRT.
4. Vander Waal’s equation or Real gases 47. (B)
Sol. …………………………………………...
43. Statement-1: AT low pressure Vander
Waal’s equation is reduced to …………………………………………...
 a 
 P  v2  V  RT because MATRIX MATCHING QUESTIONS
Statement-2: The compressibility factor

corresponding to low pressure is given by 4. Vander Waal’s equation or Real gases
RTV
1 48. Match the term (in Column – I) with its
a
43. (C) expression (in Column – II)
Sol. …………………………………………... Column – I
(A) Most probable speed
…………………………………………... (B) Average kinetic energy of gas
44. Statement-1: Absolute zero is a (C) Van der Waals constant “a”
theoretically possible temperature at (D) Compression factor
which the volume of the gas becomes Column -II
zero. (P) (3/2) KT
Statement-2: The total kinetic energy of (Q) Vreal/Videal
the molecule is zero at this temperature. (R) correction factor for the force of
44. (B) attraction
Sol. …………………………………………...
(S) 2RT / M
48. (A-S, B-P, C-R, D-Q) = 0.0426 litre mole–1)

(D) H2O (a = 5.464 litre2-atm mol–2 ;
Sol. …………………………………………... b = 0.03049 litre mole–1)
…………………………………………... Column -II
(P) Maximum boiling point
…………………………………………... (Q) Minimum boiling point
(R) Critical temperature < Boyle
…………………………………………...
temperature
3. Compressibility factor (S) Minimum critical temperature
(T) Minimum Boyle temperature
49. Match the conditions (in Column – I) 50. (A-R; B-Q,R,S,T; C-R; D-P,R)
with its expression (in Column – II)
Column – I Sol. …………………………………………...
(A) At high pressure of gas …………………………………………...
(1 mole)
(B) At low pressure of gas …………………………………………...
(1 mole)
(C) 1 mole N2 gas at 0°C and 2 …………………………………………...
atm pressure
NUMERICAL VALUE TYPE QUESTIONS
(D) 1 mole H2 gas at 0°C and 10
atm pressure 1. Gaseous Laws
Column -II 51. What will be the temperature difference
(P) PVm = RT + Pb needed in a hot air balloon to lift 1.0 kg
(Q) Attractive forces are weight. Assume that the volume of
dominating balloon is 100 m3, the temperature of
(R) Z > 1 atmosphere is 25°C and pressure is 1.0
(S) a atm. Average molar mass of air is 29
PVm = RT  amu.
Vm
51. (3)
(T) Repulsive forces are dominant Sol. …………………………………………...
49. (A-P, R, T, B-Q, S, C – Q, S, D – P, R, T)
Sol. …………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... 52. When 3.2 g of sulphur is vaporized at

450ºC and 723 mm pressure the vapour
5. Liquification of gases. occupies a volume of 780 ml. What is the
atomicity of sulphur vapour under this
50. Match the following : condition.
Column – I 52. (8)
(A) H2 (a = 0.244 litre2-atm mol–2 ; b Sol. …………………………………………...
= 0.02 litre mol–1)
…………………………………………...
(B) He (a = 0.03412 litre2-atm mole–2;
b = 0.02370 litre mole–1) …………………………………………...
(C) CO2 (a = 3.592 litre2-atm mol–2 ; b
…………………………………………... Sol. …………………………………………...
53. A glass tube with a sealed end is …………………………………………...

completely submerged in a vessel with
mercury. The air column is 15 cm long. …………………………………………...
To what height must the upper end be
…………………………………………...
raised above the level of Hg so that the
level of Hg inside the tube is at the level 56. The density of a mixture of CH4 and SO2
of Hg in the vessel? (Atmospheric gases at 1 atm, 273 K is 1.25 g litre–1.
pressure = 75 cm of Hg column]. Calculate partial pressure (in atm) of
53. (18) CH4.
Sol. …………………………………………... 56. (0.75)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
54. An ideal gas is trapped between a
mercury column and the closed lower end 57. A bulb of constant volume is attached to
of a narrow vertical tube of uniform bore. a manometer tube open at other end as
The upper end of the tube is open to shown in figure. The manometer is filled
atmosphere (atmospheric pressure = 76 with a liquid of density (1/3)rd that of
cm of Hg). The length of mercury and the mercury. Initially h was 228 cm.
trapped gas columns are 20 cm and 43 cm
respectively. What will be the length of
the gas column when the tube is tilted
slowly at constant temperature in a
vertical plane through an angle of 60°?
54. (48)
Sol. …………………………………………...
Through a small hole in the bulb gas
…………………………………………... leaked assuming pressure decreases as
dp
 kP. If value of h is 114 cm after
…………………………………………... dt
14 minutes. What is the value of k (in
…………………………………………... hour–1)?
[Use : ln(4/3) = 0.28 and density of Hg =
13.6 g/mL].
57. (1.2)
Sol. …………………………………………...
55.
…………………………………………...
…………………………………………...
If the above tube is kept vertically with
open end downward then find the length …………………………………………...
of the air column (in cm) in the 2nd
column [Hg = 13.6 gm/ml]
55. (90)
2. Kinetic theory of gases …………………………………………...

58. 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 fraction of
the mixture effusing out initially.
60. One mole of gas occupied 0.5 l at 27°C.
58. (8)
The compressibility factor of gas at this
Sol. …………………………………………...
temperature is 0.8. If b = 0.04 l mol–1,
…………………………………………... what is the value of van der Waal’s
constant a for the gas?
…………………………………………... [Take R = 0.08 lit-atm/mole k)
60. (3.36)
…………………………………………... Sol. …………………………………………...
59. Calculate rms speed (m/sec) of O2 …………………………………………...

molecules having translation kinetic
energy 1 kJ/mole. …………………………………………...
59. (250) …………………………………………...
Sol. …………………………………………...
…………………………………………...
PREVIOUS YEAR (IIT JEE-MAIN / ADVANCED)
JEE MAIN 1 : 4.The ratio of number of their

1. For gaseous state, if most probable speed molecule is : [2014]
is denoted by C*, average speed by C (A) 1 : 8 (B) 3 : 16
and mean square speed by C, then for a (C) 1 : 4 (D) 7 : 32
large number of molecules the ratios of Sol. …………………………………………...
these speeds are : [2013]
…………………………………………...
(A) C* : C : C = 1.225 : 1.128 : 1
(B) C* : C : C = 1.128 : 1.225 : 1 …………………………………………...
(C) C* : C : C = 1 : 1.128 : 1.1225
5. If Z is a compressibility factor, van der
(D) C* : C : C = 1 : 1.1225 : 1.128 Waals equation at low pressure can be
Sol. …………………………………………... written as : [2014]
…………………………………………... Pb Pb
(A) Z = 1 – (B) Z = 1 +
RT RT
…………………………………………...
RT a
(C) Z = 1 + (D) Z = 1 –
2. Sulphur dioxide and oxygen were Pb VRT
allowed to diffuse through a porous Sol. …………………………………………...
partition. 20 dm3 of SO2 diffuses through
the porous partition in 60 seconds. The …………………………………………...
volume of O2 in dm3 which diffuses under
…………………………………………...
the similar condition in 30 seconds will
be (atomic mass of sulphur = 32 u): 6. When does a gas deviate the most from
[2014] its ideal behaviour? [2015]
(A) 7.09 (B) 14.1 (A) At low pressure and low temperature
(B) 10.0 (D) 28.2 (B) At low pressure and high
Sol. …………………………………………... temperature
…………………………………………... (C) At high pressure and low
temperature
…………………………………………... (D) At high pressure and high
temperature
3. The initial volume of a gas cylinder is Sol. …………………………………………...
750.0 mL. If the pressure of gas inside
the cylinder changes from 840.0 mm …………………………………………...
Hg to 360.0 mm Hg, the final volume the
gas will be [2014] …………………………………………...
(A) 1.750 L (B) 3.60 L
(C) 4.032 L (D) 7.50 L 7. Which of the following is not an
Sol. …………………………………………... assumption of the kinetic theory of gases?
(A) A gas consists of many identical
…………………………………………... particles which are in continual
motion. [2015]
…………………………………………...
(B) Gas particles have negligible
volume.
4. The ratio of masses of oxygen and
nitrogen in a particular gaseous mixture is
(C) At high pressure, gas particles are gas) in it has escaped from the vessel.
difficult to compress. Assuming that the volume of the vessel
(D) Collisions of gas particles are remains constant, the temperature at
perfectly elastic. which the vessel has been heated is:
Sol. …………………………………………... (A) 750°C (B) 500°C [2019]
(C) 750 K (D) 500 K
…………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
8. Two closed bulbs of equal volume (V) …………………………………………...
containing an ideal gas initially at
pressure pi and temperature T1 are 11. The combination of plots which does not
connected through a narrow tube of represent isothermal expansion of an
negligible volume as shown in the figure ideal gas is: [2019]
below. The temperature of one of the
bulbs is then raised to T2. The final
pressure pf is : [2016] (1) (2)
 TT   TT 
(A) 2pi  1 2  (B) pi  1 2  (3) (4)
 T1  T2   T1  T2 
 T1   T2 
(C) 2pi   (D) 2pi   (A) (1) and (3) (B) (1) and (4)
 T1  T2   T1  T2 
(C) (2) and (4) (D) (2) and (3)
Sol. …………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
9. The volume of gas A is twice than that of 12. 0.5 moles of gas A and x moles of gas B
gas B. The compressibility factor of gas exert a pressure of 200 Pa in a container
A is thrice than that of gas B at same of volume 10 m3 at 1000 K. given R is
temperature. The pressures of the gases the gas constant in JK–1 mol–1 then, x is :
for equal number of moles are : [2019]
2R 2R
(A) 2PA = 3PB (B) PA = 3PB (A) (B) [2019]
4  12 4R
(C) PA = 2PB (D) 3PA = 2PB
4R 4R
Sol. …………………………………………... (C) (D)
2R 2R
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………...
10. An open vessel at 27°C is heated until
two fifth of the air (assumed as an ideal
13. Consider the van der Waals constants, a (C) Gas C will occupy more volume than
and b, for the following gases . [2019] gas A; gas B will be more
Gas Ar Ne Kr Xe compressible than gas D
a / (atm dm6 mol2 ) 1.3 0.2 5.1 4.1 (D) Gas C will occupy lesser volume
2 3 1 than gas A; gas B will be more
b / (10 dm mol ) 3.2 1.7 1.0 5.0
compressible than gas D
Which gas is expected to have the highest Sol. …………………………………………...
critical temperature?
(A) Kr (B) Ar …………………………………………...
(C) Xe (D) Ne …………………………………………...
Sol. …………………………………………...
16. Points I, II and III in the following plot
…………………………………………... respectively correspond to [2019]
(Vmp : most probable velocity)
…………………………………………...
14. At a given temperature T, gases Ne, Ar,

Xe and Kr are found to deviate from ideal
gas behaviour. Their equation of state is
RT
given as p  at T. [2019]
Vb
Here, b is the van der Waals constant.
Which gas will exhibit steepest increase
in the plot of Z (compression factor) vs (A) Vmp of N2 (300 K); Vmp of H2 (300
p? K); Vmp of O2 (400 K)
(B) Vmp of H2 (300 K) ; Vmp of N2(300
(A) Ne (B) Kr
K); Vmp of O2 (400 K)
(C) Ar (D) Xe (C) Vmp of N2 (300 K) ; Vmp of O2 (400
Sol. …………………………………………... K); Vmp of H2 (300 K)
(D) Vmp of O2 (400 K); Vmp of N2 (300
…………………………………………... K) ; Vmp of H2 (300 K)
Sol. …………………………………………...
…………………………………………...
…………………………………………...
15. Consider the following table : [2019]
Gas a/(k Pa dm6 b/(dm mol–1)
3
…………………………………………...
–1
mol )
A. 64232 0.05196 17. Identify the correct labels of A, B and C
B. 155.21 0.04136 in the following graph from the options
C. 431.91 0.5196 given below : [2020]
D. 155.21 0.4382
a and b are Van der Waals constants. The
correct statement about the gases is:
(A) Gas C will occupy more volume than
gas A; gas B will be lesser
(B) Gas C will occupy lesser volume
than gas A; gas B will be lesser
Root mean square speed (Vrms); most …………………………………………...

probable speed (Vmp); Average speed
(Vav) 20. A spherical balloon of radius 3 cm
(A) A-Vrms ; B-Vmp; C-Vav containing helium gas has a pressure of
(B) A-Vmp ; B-Vrms; C-Vav 48 × 10–3 bar. At the same temperature,
(C) A-Vmp ; B-Vav; C-Vrms the pressure, of a spherical balloon of
(D) A-Vav ; B-Vrms; C-Vmp radius 12 cm containing the same amount
Sol. …………………………………………... of gas will be ______ × 10–6 bar. [2020]
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
18. Which one of the following graphs is not
correct for ideal gas? [2020] JEE ADVANCE
21. Match gases under specified conditions

listed in Column I with their properties /
laws in Column II. [2007]
Column-I
(A) hydrogen gas (P = 200 atm, T = 273
K)
(B) hydrogen gas (P~0, T = 273 K)
(C) CO2 (P = 1 atm, T = 273K)
(D) real gas with very large molar
volume
Column-II
d =Density, P=Pressure, T = Temperature (P) compressibility factor  1
(A) IV (B) III (Q) attractive forces are dominant
(C) I (D) II
(R) PV = nRT
Sol. …………………………………………...
(S) P(V - nb) = nRT
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
19. A mixture of one mole each of H2, He …………………………………………...

and O2 each are enclosed in a cylinder of
…………………………………………...
volume V at temperature T. If the partial
pressure of H2 is 2 atm, the total pressure 22. The atomic masses of ‘He’ and ‘Ne’ are 4
of the gases in the cylinder is: [2020] and 20 a.m.u., respectively. The value of
(A) 6 atm (B) 14 atm the de Broglie wavelength of ‘He’ gas at
(C) 38 atm (D) 22 atm — 73°C is “M” times that of the de
Sol. …………………………………………... Broglie wavelength of ‘Ne’ at 727°C ‘M’
is [2013]
…………………………………………... Sol. …………………………………………...
…………………………………………...
…………………………………………... 25. Which of the following statement(s) is

(are) correct regarding the root mean
…………………………………………... square speed (Urms) and average
translational kinetic energy (  av ) of a
23. The diffusion coefficient of an ideal gas
molecule in a gas at equilibrium? [2019]
is proportional to its mean free path and
(A) Urms is inversely proportional to the
mean speed. The absolute temperature of
square root of its molecular mass
an ideal gas is increased 4 times and its
pressure is increased 2 times. As a result, (B)  av is doubled when its temperature
the diffusion coefficient of this gas is increased four times.
increases x times. The value of x is (C) Urms is doubled when its temperature
[2016] is increased four times.
(D)  av at a given temperature does not
Sol. …………………………………………...
depend on its molecular mass
…………………………………………... Sol. …………………………………………...
…………………………………………... …………………………………………...
…………………………………………... …………………………………………...
24. A closed tank has two compartments A …………………………………………...

and B, both filled with oxygen (assumed
to be ideal gas). The partition separating 26. I f the distribution of molecular speeds of
the two compartments is fixed and is a a gas is as per the figure shown below,
perfect heat insulator (Figure 1). If the then the ratio of the most probable, the
old partition is replaced by a new average, and the root mean square speeds,
partition which can slide and conduct respectively, is [2020]
heat but does NOT allow the gas to leak
across (Figure 2), the volume (in m3) of
the compartment A after the system
attains equilibrium is ____. [2018]
(A) 1 : 1 : 1 (B) 1 : 1 : 1.224

(C) 1 : 1.128 : 1.224 (D) 1 : 1.128 : 1
Sol. …………………………………………...
…………………………………………...
…………………………………………...
Sol. …………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
…………………………………………...
ANSWERS
JEE MAIN EXERCISE
1. (A) 2. (D) 3. (D) 4. (C) 5. (C)

6. (B) 7. (A) 8. (B) 9. (A) 10. (C)
11. (A) 12. (A) 13. (C) 14. (C) 15. (D)
16. (C) 17. (B) 18. (A) 19. (C) 20. (B)
21. (C) 22. (B) 23. (D) 24. (A) 25. (B)
26. (C) 27. (C) 28. (D) 29. (D) 30. (A)
31. (A) 32. (B) 33. (B) 34. (D) 35. (A)
36. (A) 37. (C) 38. (B) 39. (B) 40. (B)
41. (A) 42. (B) 43. (B) 44. (D) 45. (C)
46. (B) 47. (C) 48. (C) 49. (B) 50. (B)
51. (D) 52. (A) 53. (A) 54. (C) 55. (A)
56. (C) 57. (A) 58. (B) 59. (D) 60. (C)
61. (B) 62. (A) 63. (A) 64. (C) 65. (B)
66. (D) 67. (D) 68. (A) 69. (C) 70. (C)
71. (B) 72. (B) 73. (C) 74. (A) 75. (A)
76. (A) 77. (B) 78. (D) 79. (B) 80. (B)
81. (1) 82. (375) 83. (2.2) 84. (4) 85. (58)
86. (89.6) 87. (250) 88. (3) 89. (1.8) 90. (0.6)
91. (64) 92. (4) 93. (5) 94. (6)
95. (0.448)) 96. (4) 97. (1.22) 98. (28.2)
99. (0.08) 100. (200)
JEE ADVANCED EXERCISE
1. (A) 2. (B) 3. (C) 4. (A) 5. (B)
6. (B) 7. (C) 8. (D) 9. (A) 10. (B)
11. (A) 12. (B) 13. (B) 14. (B) 15. (B)
16. (D) 17. (D) 18. (C) 19. (C) 20. (B)
21. (C, D) 22. (B, C, D) 23. (A, B, D) 24. (A, C)
25. (A, D) 26. (A, C) 27. (B, C) 28. (B,C)
29. (D) 30. (C, D) 31. (D) 32. (A) 33. (B)
34. (B) 35. (D) 36. (A) 37. (C) 38. (A)
39. (A) 40. (C) 41. (A) 42. (C) 43. (C)
44. (B) 45. (B) 46. (A) 47. (B)
48. (A-S, B-P, C-R, D-Q) 49. (A-P, R, T, B-Q, S, C – Q, S, D – P, R, T)
50. (A-R; B-Q,R,S,T; C-R; D-P,R) 51. (3) 52. (8) 53. (8)
54. (18) 55. (48) 56. (250) 57. (3.36) 58. (90)
59. (0.75) 60. (1.2)
PREVIOUS YEAR (IIT JEE-MAIN / ADVANCED)
1. (C) 2. (B) 3. (A) 4. (D) 5. (D)
6. (C) 7. (C) 8. (D) 9. (A) 10. (D)
11. (C) 12. (C) 13. (A) 14. (D) 15. (C)
16. (C) 17. (C) 18. (D) 19. (A)
20. (750.00) 21. A–(p,s); B–(r); C–(p,q); D–(r)
22. (5) 23. (4) 24. (2.22) 25. (A,C,D ) 26. (B)

States of Matter: Thermal Energy

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States of Matter: Thermal Energy

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STATES OF MATTER [1]

Intermolecular forces vs thermal energy :

(Predominance of intermolecular interactions)

(Predominance of thermal energy)

The gaseous state :

Kelvin or absolute scale :

According to Boyle’s law, PV = Constant at constant temperature

Now the Charles’ law can be stated as follows :

Gay Lussac’s law (Pressure-Temperature Relationship):

or P  T (if volume and number of moles are kept constant)

Avogadro’s Law (Volume amount relationship) :

Ideal Gas Equation :

Relation of Density with Ideal gas Equation :

DALTON’S LAW OF PARTIAL PRESSURES

DIFFUSION AND EFFUSION

Graham’s Law of Diffusion :

At Constant T At constant T and P

FACTORS DETERMINING THE RATE OF DIFFUSION & EFFUSION

The Kinetic Molecular Theory of Gases :

CLASS PRACTICE PROBLEM (CPP-1)

The Kinetic Gas Equation

Derivation of The Kinetic Gas Equation :

Imagine a cube of edge length , containing N molecules, each having a

The velocity u, of any molecule may be resolved into three component

But we know that

Hence from above two expressions, we get

Application of Kinetic Gas Equation :

(4) Avogadro’s Law:

The root mean square speed (urms) :

Most probable Speed (ump):

Maxwell’s Distribution of Molecular speeds (Velocities) :

From the curve it may be concluded that

This is also called collision frequency

It should be noted that z1 is expressed in s–1 where as z11 as s–1m–3

Mean Free Path :

Polyatomic Linear Non-linear

Internal Energy and Cv of Molecules :

CLASS PRACTICE PROBLEM (CPP-2)

1. Calculate the kinetic energy of 8 gram methane (CH4) at 27°C temperature.

Deviations from Ideal Behaviour :

Effect of Pressure Variation on Deviations :

Effect of Temperature on Deviations :

Conclusion: From the above discussions we conclude that:

Van der Waals Equation of State for a Real Gas:

 a real gas in a container of volume V has only available volume of

Thus, excluded volume per pair of molecules

The Van der Waals constant a and b:

EXPLANATION OF DEVIATION BY VAN DER WAALS EQUATION :

(iii) At fairly high pressures:

(iv) At very low pressure:

CLASS PRACTICE PROBLEM (CPP-3)

Fig. Liquefaction of gases

Fig.: Volume isotherms of carbon dioxide

Critical pressure (PC):

Critical volume (VC) :

Relationship between critical constant and van der Waals constants :

 No second phase is formed irrespective of the pressure of the system.

The Law of Corresponding States :

Relationship between Z and the reduced equation of state :

CLASS PRACTICE PROBLEM (CPP-4)

(A) At T = 500 K, P = 40 atm, the state will be liquid

(C) At T < 300 K, P = 20 atm, the state will be gas

Factors affecting the rate of evaporation :