MADHAPUR

Gaseous State
Introduction:
In gaseous state molecules or atoms are far apart indicating that Vander
Waal’s forces of attraction are negligible.
In general, in case of homoatomic molecules molecular weight is directly
proportional to Vander Waal’s forces of attraction. For instance, among
H2 and Cl2 the easily liquefiable gas is Cl2 due to relatively more attractive
forces.
Among polar and non-polar molecules polar molecules have more attractive
forces and therefore they condense easily.

Intermolecular forces

London dispersion forces

symmetrical e Asymmetrical
distribution of e distribution of e
LDF is the weakest intermolecular forces. It is a temporary attractive force
that results when the e − in two adjacent atoms occupy position that makes
the atom to form temporary dipole. Hence it is also referred as induced dipole
– induced dipole attraction.
Because of constant motion of electron, an atom or a molecule can develop a
temporary dipole
These forces increase with
a) Increase in No. of e − in a molecule
b) Increase in molecular weight
c) Increase in molecular size.
Dipole – Dipole Forces

These forces are stronger than LDF. These forces exist between polar-molecules
where the positive end of one molecule attracts the negative end of another
molecule.

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 The polar molecules must be close to each other for the attractive forces to be
significant.
These forces increase with
a) Increase in molecular size
b) Increase in molecular weight
c) Increase with increase of polarity.
Dipole – induced dipole forces :

spherical atom with no dipole

  
Upon approach of a molecule with dipole the spherical atom develops a
dipole.
These forces operate between polar molecules having permanent dipole &
molecule having no permanent dipole
These dipole – induced dipole attraction is a weak attraction that results
when a polar molecule induces a dipole in an atom or in a non-polar
molecule by disturbing the arrangement of e − in the non-polar molecule.
Gas Laws
1. Boyle’s Law:
The pressure of a given mass of a gas is inversely proportional to its volume at
constant temperature.
1
Pr essure  ;(T = constant)
volume
PV = constant, Log PV = constant;
P1V1 = P2 V2 → Log p + log V = constant
The graph obtained at constant temperature is known as isotherm 1)

T2  T1
V V PV
2) 3)
T2
T1
P 1/p P (or) V

log p log P
4) 5)

log v log 1/v

The working of LPG cylinder is based upon Boyle’s law.
*In a closed container at a constant temperature when some amount of gas is
removed the pressure decreases and simultaneously volume increases.
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 Hence at any given point of time, the volume of gas is equal to volume of the
close container.
When a gas in a closed container which is at a high pressure is consumed, the
pressure of the gas in the container decreases and a stage it reached when
pressure of gas in closed container is equal to the surrounding atmospheric
pressure. Therefore, at that point the volume of gas that cannot be utilized or
available is equal to the volume of the container
*Adiabatic expansion does not follow Boyles law as temperature is not
constant.
2. Charles Law :
At constant pressure, the volume of a given mass of a gas is directly
proportional to its temperature in Kelvin scale.
V  T(P = constant)
V
= constant
T
V1 T1
=
V2 T2
Log V – log T = constant

Charles law may also be stated as for every10 C rise in temperature, the volume
1
of a given mass of a gas increases by times of its original volume.
273
 V0 
VT =   T has a constant value at a given pressure.(Another form of
 273.15k 
Charles Law)
Vo → volume of gas at 0°C
 VT = kT ;  VT
V0
Vt = a + bt a → Intercept; b → slope =
273.15
Graphs obtained at constant pressure are known as Isobars
The theoretically possible temperature at which the volume of a gas becomes
zero is known as absolute zero temperature which corresponds to – 273°C.At
absolute zero all molecular motion ceases and volume of gas become zero.
Therefore, at absolute zero no substance exists in gaseous state.
At absolute zero the total kinetic energy of the molecules becomes zero and
hence molecular motion ceases. When the temperature of the substance is
lowered thermal energy reduces. At absolute zero possible thermal energy has
been removed from the substance.
A substance cannot be cooled any further after thermal energies has been
removed.

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 Vt = a + bt
b
pe-
1) V 2) Vt slo 3)
V
a

T (k) t°C (-273.15°C t (°C)

log V
4) 5) T

log T 1/V
3. Charles Law- 2 (Gay-Lussac’s law)
At constant volume, the pressure of given mass of gas is directly proportional
to its absolute temperature.
P
P  T (v = constant) = constant
T
Log p – log T = constant
P1 P2
=
T1 T2
The graphs obtained at constant volume are known as “Isochore”

P
log P
P T P

T log T T (or) P 1/T

1) 2) 3) 4)
V1
V2
P

T (k)

4. Avogadro’s Law
Equal volumes of all gases under same conditions of ‘T’ and ‘P’ contain
same no. of moles or molecules.
At NTP or STP
1 mole or 1 molar Of any Occupies And
mass or 1gram mol. gas 22.4 or Contains
wt. or 1 GMW or1 22400CC Avagadro no.
gram molecule or1 (GMV) of “Structural
gram atomor1GAW or units (No)
1 gm ion
wt V S.U.
1 mole = = =
at wt or mol.wt 22.4 6 1023

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 The volume occupied by 1 mole of gas at NTP or STP is known as gram molar
volume (GMV)
The mass of a substance that contain Avagadro no. of structural units is
referred as a mole (No = 6.023 × 1023 )
According to Avogadro’s Law ‘Volume of a given gas is directly proportional
V
to n (P, T is constant) = constant
n
V2 V2
n → No. of moles ; =
n1 n 2
Ideal Gas Equation
1
i) At constant T V  → Boyles Law
P
ii) At constant P V  T → Charles law
iii) At constant T and P V  n → Avogadro’s law
from 1,2,3
nT
V  PV  nT
P
 PV = nRT R → Universal gas constant
Physical Significances of “R”
PV F / area  V f  l−2  l3
R= = =
nT amt.of gas  K amt. of gas  K
force  length work (or energy)
R= =
amt. of gas  K amt. of gas  K
R = 0.0821 lt. atm k −1 mole −1
= 8.314 jk −1mole −1 or 8.314  107 erg k −1 mole −1 or 2 cal.k −1mole −1
A gas which obeys the gas laws at all conditions of ‘T’ and ‘P’ is known as an
ideal gas i.e. a gas which behaves ideally obeys PV = nRT
The dimension of ‘R’ are energy per mole per Kelvin and hence it represents
the amount work or energy that can be obtained from one mole of a gas
when the temperature is raised by 1 Kelvin.
Note: Practically an ideal gas does not exist.
Graham’s Law of Diffusion
The spontaneous intermixing of two or more gases irrespective of gravity is
known as diffusion.
The ejection of a gas through minute aperture from a region of high pressure
to a region of low pressure is known as effusion.
The rate of effusion from an orifice or minute aperture is equal to
PA
r=
2RTM
P → partial pressure of gas ; A → Area of cross section of orifice
M → molecular mass of gas.

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 Graham’s law of diffusion states that at constant temperature the rate of
diffusion of a gas is inversely proportional to the square root density at
constant temperature
1 r1 d r1 2  d2 M2
r ; = 2; = = ( 2  v  d = m.wt )
d r2 d1 r2 2  d1 M1

r1 P1 M2 r1 n1 M2
* = =
r2 P2 M1 r2 n 2 M1

volume of gas diffused ( V )

Rate of diffusion =
( t ) time taken
V1 / t1 M2
 =
V2 / t 2 M1
Applications of Graham’s Law
*Based upon the rate of diffusion gases, molecules weight of unknown gas can
be determined.
*Ansil’s Marsh gas detector used in coal mines is based upon the principle of
diffusion.
The isotopes of uranium present in solid state are converted to their gaseous
hexafluorides and are separated based upon the rate of diffusion. The
phenomenon is known as Atmolysis. In case of uranium mineral, it contains
0.7 % of U 235 while the rest is U 233 . By reacting the mixture with Fluorine,
gaseous hexafluoride is obtained and uranium can be enriched.
M2
Enrichment factor =
M1
n1' / n '2
separation factor f = . Where, n1;n 2 are concentration of isotopes before
n1 / n 2
diffusion, where n1' , n '2 are after diffusion.
w RT dRT
Note : PV = nRT ;  PV =  ; P= ;  PM = dRT
M V M
For a given gas m = constant
P1 P
 = 2
d1T1 d 2T2
Dalton’s Law of Partial Pressure : Partial pressure is defined as the pressure
exerted by a gas over a mixture of gases in a closed container which is equal
to the pressure exerted by the same gas when it is taken alone in the same
container.
The term partial pressure is applicable for chemically non-reacting gases.
Dalton’s Law states that at constant temperature the pressure exerted by a
mixture of chemically non-reacting gases taken in a closed container is
equal to the sum of their partial pressures.
If P1 , P2 and P3 are the partial pressure of the gases then total pressure p is
equal to P1 + P2 + P3 .
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 Let P1 , P2 and P3 be the partial pressure of chemically non-reacting gases
containing n1 , n 2 and n 3 moles respectively taken in a closed container of
volume ‘V’ litre at a temperature ‘T’, then
nRT n RT n RT
P1 = , P2 = 2 , P3 = 3
V V V
PT = P1 + P2 + P3
RT
 P= ( n1 + n 2 + n 3 )
V
nRT
 P= ( n = n1 + n 2 + n3 )
V
P1 n1RT / V n1
 = =
P nRT / V n
n1
 P1 = P 
n
Partial pressure = Total Pressure x Mole fraction
*The pressure exerted by the water vapour on surface of the liquid with it is in
equilibrium in a closed container is known as Aqueous tension.
The limitation of Dalton’s law is that it is applicable for a mixture of
chemically non-reacting gases.
For instance, it is inapplicable for a mixture of NH 3 and HCl gases, since they
reacts to form NH4Cl a solid which exerts zero pressure and has zero velocity.
Applications :
1) In distillation Techniques
2) During the collection of gas either by downward or upward
displacement of water, pressure of dry gas can be calculated.
Pwet gas = Pdrygas + Aq.tension
 Pdrygas = Pwetgas − Aq.tension
Relative Humidity
Vapour pressureof water at room T in air or gas PH O
Relative Humidity = = RH =  2
saturated VP of water at room T in air or gas PH2O
Dew Point:
Temperature at which under given set of condition a gas becomes saturated
with water vapour, then RH = 100% or unity.
When RH increases rate of evaporation will be low.
Saturated vapours do not obey gas lows except Daltons law.
*Amagat’s Law of Partial Volume
VT = V1 + V2 + V3 ;
Partialvolume = Totalvolume  Molefraction
Kinetic Energy Theory of Gases
Maxwell, Boltzmann, Clausius and other group of scientists proposed kinetic
theory of gases.

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 The important postulates of this theory are :
1) Every gas is made up of tiny spherical particles known as molecules.
2) Gaseous molecules exhibit random motion i.e. theory move in all
possible directions leading to collisions.
3) They collision between the gas molecules are perfectly elastic i.e., the
momentum is conserved.
4) The pressure of the gas is due to the collision of the molecules with the
walls of the container in which they are enclosed.
5) There is no effect of gravity on the motion of molecule.
6) The Vander walls’ forces of attraction between the gas molecules are
negligible.
7) The volume occupied by gas molecule is negligible when compared to
the total volume of gas.
8) The average K.E of the gaseous molecule is directly proportional to its
absolute temperature.
K.E  T (The K.E. of individual gas molecules may differ but the average
K.E remain same at a given T)
Kinetic Gas Equation:

1
PV = mnc2 ; m× n = molar mass = m
3

Mean free path: : The mean free path (  ) is the average distance travelled by a
molecule between two successive collisions
Average distance travelled per unit time
=
no. of collisions made by a single molecule per unit time
URMS
Collision frequency refers to no. of collisions taking place in unit time =

Effect of temperature and pressure on mean free path of molecular collision.
PV = nRT
N RT N  R 
 P=  ;  P = kT  = k  ;  P = N* kt ( k → Boltzmann constant )
NA V V  NA 
P N P
 N* = k   N*  ;  N*  U RMS  T
T V T
1
 =
22 N* .
 → mean free path
1 T
 *

N P
Universal gas constant per molecule ( R / N A ) is known as Boltzmann constant
(k) k = 1.38× 10−16 erg / k / molecule;  is collision diameter. For identical
molecules  is diameter of molecules.
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 1
When T → constant,   ; when P → constant   T
P
When T, P are constants the  remains same and '  ' value remains constant.
3RT 3PV 3P  M 1
Note : c =   d =  ; c 
M M d  V d
T
Crms = 1.58 104 cmsec−1 ;
M
T C1 TM
C ; = 1 2
M C2 T2 M1
Problems

1. What will be the pressure required to reduce 600 ml of dry gas at 750 mm of
pressure to 500 ml at the same temperature.
2. A gas cylinder containing cooking gas can withstand a pressure of 14-9atm
the pressure gauze of the cylinder indicates 12atm at 27°C due to sudden fire
in the building temperature starts rising. At what temperature will cylinder
explode.
3. When 2g of a gaseous substance ‘A’ is introduced into an initially evacuated
flask at 25°C the pressure was found to be ‘1 atm.’ 3g of another substance ‘B’ is
then added at same temperature and pressure and the final pressure is found
to be 1.5 atm. Assuming ideal behaviour calculate the ratio of molecular
weight of A and molecular weight of ‘B’
4. A compound can exist in gaseous state as a monomer as well as dimer. The
molecular weight of monomer is 48. In an experiment 96g of the compound is
taken in a vessel of volume 33.6 L and heated to 273°C. Find the pressure
developed if this compound exists as a dimer to the extent of 50% by weight.

5. 10g of a gas is present in 2.5 L of a flask at 0°C to raise the temperature of the
gas to 273°C without changing the pressure. How much amount of gas should
be added or removed.?
6. A flask contains air at 27°C calculate the temperature at which it should be
heated so that 1/3rd of the mass of air measured at 27°C escapes out.
7. At room temperature ammonia had 1 atm pressure and HCl gas at pressure ‘P’
are allowed to effuse through identical pin holes of opposite ends of glass tube
of 1m length and uniform cross selection and NH4Cl is formed at a distance
of 60 cm through which NH 3 is sent. Calculate the value of ‘p’.
8. Equal masses of CH 4 , and O 2 are mixed in an empty container at 25°C. Then the
fraction of total pressure exerted by O2 is
1 1 1 2
A) 1/ 3  B) rd C) D)
273 3 2 3

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9. A Balloon of 21 cm diameter is to be filled with Hydrogen gas at NTP from a
cylinder containing H2 gas at 20 atm and 300 k, the capacity of the cylinder
is 2.82. Calculate the no. of balloons that can be filled.
10. Diameter of bubble at the surface of the lake is 4mm and bottom of lake is
1mm. If atmospheric pressure is 1 atm. Temperature of lake and atmosphere
are equal. What is the depth of the lake? (density of water and mercury are
1g per ml and 13.6 g)
11. 1 cc of a gas is as heavy as 4 cc of O2 under identical conditions the amount
of ‘x’ that occupies 2.24 litres at STP is
12. A Bulb of unknown volume contains an Ideal gas at 650 mm of pressure. A
certain amount of gas was withdrawn and was found to occupy 2ml of 1 atm
pressure, the pressure of gas remaining in the bulb was 600 mm. If all the
measure were made at constant temperature. Calculate the volume of the
bulb.
13. The rate of diffusion of Ozonised oxygen is 0.95 times that of pure oxygen
under same condition. Calculate the percentage volume of ozonised oxygen
in the sample?
14. 1120 ml of ozonised oxygen at STP weight 1.76g calculate the volume of O2 in
the ozonised oxygen
a) 996 ml b) 896 ml c) 796 ml d) 784 ml
15. Calculate the rms velocity of CO2 at 440C
16. What will be the pressure exerted by a mixture of 3.2 g of methane and 4.4 g of
CO2 contained in 1L flask at 27°C.
17. Two bulbs A and B of equal capacity are filled with helium and SO2 gas
respectively at the same temperature. If the pressure in the two bulbs is same
than
a) What will be the ratio of velocity of molecules of two gases) At what
temperature velocity of SO 2 gas becomes half the velocity of He gas at 27OC c)
How will the velocity be effective volume becomes 4 times that of A D)How will
the velocity be affected if half of SO2 molecules are removed from the bulb?
18. Two glass bulbs of equal volumes are connected by narrow tube and filled
with a gas at O0C with a pressure of 75 cm one of the bulbs is placed at a water
both maintained at 62°C. What is the new volume of pressure inside the bulb
(volume of connecting tube is negligible)?
19. 4g of argon (M.W = 40) in bulb at temperature of T K had a pressure P atm.
When the bulb was placed in a hotter bath at temperature 500 more, 0.8g of
gas had to be removed to get original pressure. The value of T is

A) 100K B) 400K C) 200K D) 250K

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 Deviations from Ideal Gas Behaviour
PV
= Z ( compressibility factor )
RT
He T4T3
H2
N2 T2
ide H2 CH 4 T1
1. P
al
ga 2. z=1.0 CO2 3. z=1.0
T1  T2  T3  T4
s

V P 0 200 400 600

Reason for deviation for ideal gas behaviour is the point No.6 and 7. Of
Kinetic theory of gases.

From graph (2) conclusion drawn are

a) Z is always greater than 1 for H2 and He
b) for easily liquefiable gases ‘z’ dips sharply below the ideal line in a low-
pressure region.
From graph (3) illustrates the facts that the determining factor for deviation
is the temperature relative to critical temperature.
Evidence for Molecular Attractions:
When a compressed gas is allowed to expand in adiabatic condition (change
in heat remains constant). The emerging gas is found to be cooler, this is
because an expansion work is done to overcome attractive forces which
requires energy and this provided by the system.
Vander Waal’s Equation of State for Real Gases
Derivation:
Volume correction Term: Vr = ( Vi − nb )
Ideal volume refers to the volume which is available for the motion of the
molecules.
In a real gas part of the total volume is occupied by the molecules of the gas.
Hence real volume gas = Actual volume of gas in container – volume occupied
by molecules in motion.
excluded volume

r r

If a bimolecular collision is considered then excluded volume per pair of

4 4
 ( 2r )  8  r 3
3
molecules is equal to
3 3
1 4 4 
 for one molecule =  8  r 3  4  r 3 
2 3 3 
Therefore, the numerical value of ‘b’ is 4 times the actual volume occupied by
gas molecule.
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 4
For N A molecules b = N A  4  r 3
3
Correction for forces of attraction (pressure)

A B

For the molecule ‘A’ present in the bulk of the vessel due to symmetrical
attraction, there is no net force of attraction.
In case of molecule ‘B’ which is a about to strike the wall of the container the
molecule experiences net attraction i.e. it is dragged by other molecules as a
result its velocity decreases and thereby the force with which it strikes the
walls of the container decreases leading to decrease in pressure therefore
pressure of real gas less than pressure of ideal gas.
No. of molecules
present per unit
volume of vessel
Correction term
(n/v)
depends upon
(n/v) No. of
molecules striking
the side of the vessel
per unit volume

 correction term  n 2 / v2
Correction term = an 2 / v 2
Where a → proportionality constant, which is a measure of force of attraction
between the molecules.
an 2
 Pr = Pr + 2
v
(Real pressure = pressure developed due to collision + pressure lost due to
attraction)
Substituting in Ideal gas equation.
 an 2  
 P + 2  ( V − nb ) = nRT 
 V  
Pv2 v
a = 2 = K  Pa  dm6 mole−2 ; b = = dm3mole−1
n n
Note : 1) If two gases have same value of ‘b’ but different values of ‘a’ then the
gas having larger value of ‘a’ denotes that the attractive forces are high
and the gas can be readily compressed.
2) Lower the ‘b’ value readily is the gas compressed.
3) If the value of ‘b’ remains constant over a wide range of temperature it
infers gas cannot be compressed.
Vanderwaal’s equation for 1 mole of gas can be written as
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  a 
 P + 2 ( V − b ) = RT 
 V 
At low pressures
volume being high ‘b’ can be neglected.
 a  a
  P + 2  v = RT ; Pv + = RT ; dividing by RT throughout
 v  v
a
Z+ = 1 (since Z = PV/RT);
RTV
 a 
Z = 1 − 
 RTV 

At high pressure
a
is neglected then P ( v − b ) = RT ; PV − Pb = RT
v2
Pb
Dividing by RT throughout Z − = 1;
RT
 Pb 
Z = 1 + 
 RT 
For H2 and He gases “a = 0” (Hence, they are referred to as permanent gases)

 P ( v − b ) = RT
PV – Pb = RT Dividing by RT throughout
Pb
Z− =1
RT
 Pb 
Z = 1 + 
 RT 
At high temperature and low-pressure volume is large, attractions are
a
negligible and therefore the terms and v are negligible. Hence, the
v2
vanderwalls’ equation is reduced to ideal gas equation. *Therefore, an ideal
gas exists at high temperature and low pressures.
Limitations of Vander Waal’s Equation
The limitation of vanderwaal’s equation is the generality of this equation is
lost as it contains two constant whose value depends upon nature of gas.
Virial equation:
PV 1 1 1 a
Z= = 1 + B  + C  2 + D  3 + ...... B = b − ; c = b2
RT V V V RT
When B, C, D are temperature dependent constant and are known as virial
constant.
Boyles Temperature (TB)
The range of temperature at which a gas shows ideal behaviour is known as
Boyles Temperature.

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 a
TB =
Rb
At Boyles temperature ‘Z (vs) ‘P’ line of an ideal gas is tangent to that of real
gas as pressure approaches ‘Zero”
a
B= b− ;
RT
a  Rb
  a 
when T=TB B= b−  Tb = ; B = 0
 
Ra Rb 
Boyles temperature for some gases are H 2 − ( −156C ) ; He-(-249°C), N2 (59°C),

CH4 (224°C), NH3 ( 587C ) H2 and He the temperature of zero (0°C) is greater
than TB.
The other gases at 0°C are below that TB and Hence z is less than 1 in low
pressure zone.
Inversion Temperature (Ti)
The temperature below which when a gas is expanded, it cools is known as
inversion temperature.
2a
Ti =
Rb
Ti = 2Tb
A gas cools when the temperature is less than Ti and gets heated up above
inversion temperature.
*For ideal gases, since a = 0 Joule Thomson cooling effect is inapplicable.
 JT = positive - cooling effect
 JT = negative – heating effect
Note : Ideal gas are very difficult to liquefy since a = 0
Liquefaction of Gases
Andrew’s Isotherm of CO2

____________________
Regular hyperbola.
Conclusion:
1. Isotherms below 31.1°C
a) Isotherm ABCD
A to B follows Boyles law i.e. as ‘p’ increases volume decreases.
B to C, slight increase in pressure leads to sharp decrease in volume
indicating liquefaction of CO2 up to C

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 At point ‘C’ CO2 is completely converted to liquid.
Along CD, even though the pressure increases enormously, change in
volume of CO2 is negligible indicating that CO2 is almost
incompressible.
b) Isotherm EFGH :
It is similar to ABCD Isotherm, the difference being at higher
temperature, the difference between volume of gas and volume of liquid
obtained is decreases.
In other words, with rise in temperature more pressure is required.

C) Isotherm above 31.1°C.

There is no possibility of liquefaction of CO2 gas irrespective of any
amount of pressure applied. This temperature is referred as critical
temperature. Therefore critical temperature of CO2 is 31.1°C and this Isotherm
is referred to as critical Isotherms.
Critical Constants :
1. Critical temperature (Tc)
The maximum temperature below which a gas can be liquefied by the
application of pressure.
8a
Tc =
27 Rb
In a given set of gases, higher the critical temperature of gas more is the ease
in which it can be liquefied with the application of pressure.
If the Tc of gases above 25°C then such gases can be readily liquefied. For
instance, Tc of CO2 is 31.1°C. Hence, at the room temperature of 25°C. It can be
easily liquefied by the application of pressure.
*In case of ideal gases since a=0; Tc=0 they cannot be liquified
2. Critical pressure: (Pc)
The pressure below which a gas can be liquefied by the lowering at
a
temperature Pc = .
27b 2

3. Critical Volume (Vc)The volume occupied by the one mole of a gas at critical
temperature and critical pressure is known as Critical volume.
Vc = 3b
PV
The value of at critical state:
RT
PV PcVc a.3b 27R 3
= = =
RT RTc 27b2 R  8a 8
PcVc 3
= R = 0.375 R
Tc 8
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 If this value of ‘R’ is compared with experimental value It is found that it is
not very accurate at critical state.

Law of corresponding states

(Reduced equation of state)
Any equation of state which involves only two constants in addition to ‘R’ can
be written in terms of reduced variables
P V T
Pr = ( reduced pressure ) ; Vr = ( reduced volume ) ; Tr = ( reduced temperature )
Pc Vc Tc
 P = Pr  Pc , V = Vr  Vc , T = Tr  Tc
for 1 mole Vander Waal’s equation is
 a 
 P + 2  ( V − b ) = RT
 V 
by substituting the values Of P, V & T
 a 
2 ( r
  Pr  Pc +  V  Vc − b ) = RTr  Tc
 ( Vr  Vc ) 

 a a  8a
  Pr  +
 27b V ( 3b )
( V  3b − b )  = RT

 r

2 2 2 r
 r  27Rb

 3 
 Pr +  ( 3Vr − 1) = 8Tr
 Vr 2 

This referred to as reduced equation of state and it doesn’t contain any

constant characteristic of a gas and thus, is applicable for all gases.
If two gases have same value of reduced pressure and reduced temperature
then they have same reduced volume. Thus they correspond to each other and
this is known as Law of corresponding states.
Molecular Distribution of Velocities
Maxwell – Boltzmann Curves

CpCav C
fraction of molecule

rms

T2  T1

T1
T2

velocity
At a given temperature different fraction of the same gas possess different
velocity are explained by Maxwell Boltzmann Curves.

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 The important conclusions derived from these curves are
1) The velocity of a gas molecule is always greater than zero indicating
that the molecule exhibits random motion.
2) With the increase in temperature, the graph becomes flatter, since the
fraction of molecules possessing higher velocity increases.
3) The velocity possessed by most of the molecule is known as most probable
velocity (Cp)
2RT 2PV 2P  M 1 V
Cp = = = d = , − 
M M d  V d M
With the rise in temperature fraction of molecules possessing Cp
decreases.
4) The average of all the velocities possessed by the gas molecules is known
8RT 8PV 8P
as average velocity Cav = = =
M M d
C1 + C2 + C3
If C1 , C 2 , C3 are the velocities of gas molecules then Cav =
3
5) The root of mean of square of all the velocities possessed by the gas
molecules is known as rms velocity

3RT 3PV 3P T
Crms = = = = 1.58 104 cms−1
M M d M
Cp = 0.8166 ×Crms
Cav = 0.9213 × Crms
CP: Cav: Crms = 1 :1.128 :1.224
Problems
n
1. An ideal gas at 350 K contains ‘n’ no. of molecules. fraction of the
10
n
molecules moves with the velocity of v m/s and fraction moves with a
20
velocity of 8.83 m/while the rest of the molecule moves with a velocity of 6.53
m/s. Calculate the rms velocity of gaseous molecules.
2. The rms velocity of CO2 gas at a certain temperature is 4.4 × 104 cm/s.
Calculate the rms velocity of ethane at same temperature.
3. The compressibility factor for 1 mole of a real gas at 0°C and 1000 atm is
found to be 0.5 assuming the volume of the gas to be negligible. Calculate the
vanderwaal’s constant ‘a’

Lifting capacity of gas filled Balloon

(PAYLOAD)

When a balloon is filled with a gas lighter than air or hot air, raises up due
to the difference in density of gas and air.

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 PAYLOAD = [Weight of air – weight of gas present in same volume at same T
and P] – [weight of balloon]

1. A rubber balloon weight 10 g is 40 cm in diameter when inflated with helium

at 1 atm pressure and 300 k. Calculate the payload of the balloon if the
density of air is 1.2 g / mg under these conditions.
2. Determine the payload of 10 Litre balloon filled with he gas and 27°Cand 1
atm pressure. Composition of air can be considered as 79% nitrogen and 21%
of oxygen by volume and the balloon is massless.
3. 3.7 g of a gas at 25°C occupies the same as 0.184 g of H2 at 17°C and at the
same pressure what is the molecular weight of a gas.
4. The density of a gas is 0.259 g/m at 400 k and 190 mm of pressure. Find its
molar mass.
5. 0.553 g of boron. Hydrogen compound created a pressure of 0.658 atm in a
bulb of 407 ml at 100°C. Analysis showed it as 85.7% boron. Calculate the
molecular formula. Atomic weight of boron is 10.8 .Mol. wt. of compound is
6. The density of mixture of oxygen and nitrogen at 0°C and 1 atm is 1.3 g.
Calculate the partial pressure of a gas.
7. The rate of effusion of an un known gas ‘x’ at 480 k is 1.60 times the rate of
effusion of SO2 gas at 300 k. The molecular weight of x is yx10. Find the value
of ‘y’
8. The no. of collision of gas molecules on the walls of the container per unit
nc
area per second is where ‘n’ is the no. of molecules per unit volume and c
4
nc
is the mean speed. Calculate at STP for helium.
4
9. The second and third virial coefficient of oxygen are –21.7 cc and 1200 cm6
per mole2 respectively at 300 k. Determine the values of vanderwaal’s
constant a and b.

10) The temperature at which the most probable velocity of oxygen is equal to the
RMS velocity of ozone at 500C is

A) 323K B) 484.5K C) 215.3K D) 646K

11) The temperature at which the RMS velocity of SO2 is half the RMS velocity of He
at 300K

A) 300K B) 150K C) 600K D) 1200K

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12) SO2 molecule is twice as heavy as O2 molecule. Hence at 250 C the ratio of the
average kinetic energy of SO2 and O2 is

A) 2:1 B) 1:2 C) 1:1 D) 4:1

14) One mole of N2 gas at 0.8atm. takes 38sec to diffuse through a pinhole, where
as one mole of an unknown gas at 1.6atm. takes 57sec to diffuse through the
same pinhole. The molecular weight of unknown gas is

A) 126 B) 64 C) 80 D) 252

* * *

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