GASESOUS STATE Page # 3

PARAMETERS TO DESCRIBE A GAS

 (a) Pressure :

 The force per unit area exerted on the wall of container due to constant bombardment of gas
molecules on the wall of container is called pressure.
 Units: 1 N/m2 = 1 Pa
1 atm = 1.013 × 105 Pa
1 atm = 76 cm = 760 mm of Hg = 760 torr
1 torr = 1 mm Hg
1 bar = 105 Pa
1 atm = 1.013 bar

 Constraints : P = constant

1atm
Free to
move

1atm

 (b) Volume (V) :

Volume of a gas is equal to volume of container.
 Units :
1cc = 1 cm3 = 1 mL
1000 cc = 1000 cm3 = 1000 mL = 1 L = 1 dm3
1000 L = 1000 dm3 = 1 m3
Volume = Constant

Piston hindered from moving

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Page # 4 GASESOUS STATE

 (c) Temperature :
T (K) = to(C) + 273.15

 (d) no. of moles (n) :

n = moles

Gas Laws
 (1) Boyle’s law
 (2) Charle’s law
 (3) Gay-lussac’s law (Amonton’s law)
 (4) Avogadro’s law

(1)Boyle’s law

 P1 < P2

1 P1
P  
V V1 P2 V2
V1 > V2
k
 P
V

 PV = k ; T = Constant

 P1 V1 = P2V2 = - - - - - = Pn Vn

m
   = Constant
V
1
 
V
 P

   P

P
 K ; T = Constant


P1 P2 Pn
 1 = 2 =---- --- 
n

 ‘’ For a fixed amount of gas at constant temperature, the gas volume is inversely propor-
tional to the gas pressure‘’.

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 GASESOUS STATE Page # 5

(2) Charle’s law

1ºC
V0
 V0 
V0     1
 273 .15 
 V0 
   2
2ºC  273.15 
V0 V0

0ºC  V0 
V0     2
 273.15 
 V0 
–1ºC  273 .15 
 
V0
Vo
 Vo –
273.15

 Vo 
 = Vo +   (– 1)
 273.15 

Vo
 V = Vo +
273.15
×t

Vo = volume at 0oC

t = change in temp (oC)

y=V

V0

-273.15ºC 0ºC t=x

+273.15ºC
Vo
V= t + Vo
0ºK 273
y = mx + C

 T = t + 273.15 2
From 1

 t   273 .15  t   Vo 
 V = Vo  1  ,  V = Vo  ,  V =  
 273 . 15   273.15   273.15 

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Page # 6 GASESOUS STATE

V
 or,
T
= Constant

V
 V  T ; P = Constant

[V =KT] T

y = Kx

 V = Vo + Vo   t
V0

Coefficient of superficial expansion

 V = Vo ( 1 +  t) (solid)

 1 
 V = Vo  1   t Coefficient of superficial expansion of a gas
 273 .15 

 Charle’s law states that, ‘’volume of a gas increases by 1/273.15 part of that volume which
the gas had at 0oC for every 1o rise in temperature is called Charle’s law ‘’

OR

 ‘’Volume of a gas is directly proportional to absolute temp keeping pressure constant‘’.

(3) Amonton’s law (Gay lussac’s law)

 1 
 P = Po  1  t
 273.15 

P
 T
= Constant  V = constant

1
 273.15
= Coeff. of pressure change.

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 GASESOUS STATE Page # 7

(4) Avogadro’s law

V1 V2
n1 n2

n2 > n1 T = constant
V 
n
V2 > V1 P = constant

V = kn

V
 n
= constant

V1 V2 Vn
 n1 = n2 = - - - - - - - = nn

 Avogadro’s law states that , ‘’volume of a gas is directly proportional to no. of moles keeping
pressure and temp constant.’’

V V
(I) (II)

T 1/T

1/V 1/V
(III) (IV)

T 1/T

log V log 1/V

(V) (VI)

log T log T

 Ideal gas equation

1
 V 
P
(Boyle’s law)–––––––––– 1

 V  T (Charle’s law)––––––––––2

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Page # 8 GASESOUS STATE

 V  n (Avogadro’s law)––––––– 3
 from (1) (2) (3)
nT kn T
V   V=
P P
[ PV = Kn T ]

K = R = universal gas constant.

 PV = n R T
w
 n=
M

w
 PV =
M
RT

w
PM = RT
V

 PM =  R T
At S.T.P  P = 1 atm
R = 0.0821
T = 273 k

M M
= =
 RT  (0.0821)  273 
   
P
   1 
M
 S T P =
22.4

Universal gas constant

F
PV  AL work
R= = A =
nT mole  temp
nT
 Is independent of P, V, n, T.
 Value of ‘R’ depends on unit

P V R

Pa, N/m 2
m 3
8.31 J K mol–1 –1

atm L 0.0821 Latm K mol –1 –1

––– ––– 1.97 cal K mol 2 cal K mol

–1 –1 –1 –1

––– ––– 8.31 × 10 ergs K mol

7 –1 –1

––– ––– 5.189 × 10 eV K mol 19 –1 –1

 Note : 1 atm L = 101.3 J

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 GASESOUS STATE Page # 9

 Dalton’s law of partial pressure

A B nA nB
nA nB
PT =PA+PB
PA PB 
T,V T,V T,V

 Dalton’s law of partial pressure states that ‘’ in a mixture of two non reacting gases taken in
a closed volume & a constant temp behaves as if they are present alone in the container’’
 Generalisation

A, B, C, D, - - - - - - -

nA, nB, nC, nD - - - - - -

PA, PB, PC, PD - - - - - -

PT V

 PA V = nA RT

RT
 PA = nA
V
––––– (1)
RT
 PB = nB
V
––––– (2)
RT
 PC = nC
V
––––– (3)
- - - - - - - - - - - - - - -

- - - - - - - - - - - - - - -

 PT . V = (nA + nB + nC + - - - - ) RT
RT
 PT = (nA + nB + nC + - - - - - - )
V
–––––(n)

from (1) & (n) - - - - - -

RT
PA nA
V
PT =
 RT
( n A  n B  - - - - - - - -)
V

 nA 
 PA =  n  n  - - - -  . PT
 A B 

 PA = XA PT
PB = XB PT
PC = XC PT
- - - - - - - - - - - - - - - - - - - - - - - - - - -

- - - - - - - - - - - - - - - - - - - - - - - - - - -

 nA 
  XA  
 n A  nB  nC  - - - - - - 

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Page # 10 GASESOUS STATE

WA
MA
XA 
 WA W W
 B  C  --- -- ---
MA MB M C

Amagat’s law of Partial Volume

A+B+C+ -----

nA + nB + n C + - - - -

PA + PB + PC + - - - - -

PT , V T

PT . VA = nA RT (1)

PT . VT = (nA + nB + nC + - - - - - ) RT (2)

from (1) & (2).

VA
 XA
VT
or [ V A = XA . V T ]

[ PA = XA . PT ]

VA VT
 PA = PT

 Amagat’s law of partial volume states that, ‘’ partial volume of any gas is equal to its mole
fraction times its total volume .’’

PN2=1atm
V=1L
T=298

Gas is collected
over water.

Pwet gas
= Pdry gas + PH2 O

PT = PN2 + PH2 O

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 GASESOUS STATE Page # 11

1 atm = PN2 + PH2O

PN2 = (1 atm – PH2O )

 Whenever we apply ideal gas equation for a gas which is collected over water , take care that
the pressure substituted is that of a dry gas.

 (2) Relative humidity :

c c
w c
PV = RT  P  w
M
c

WH2O (present)
 RH= Wmax H2O vapour

Partial vapour pressure of H2 O

= maximum partial pressure of H O (Aqueoustension)
2

 R .H% = R .H × 100

 Effusion & Diffusion

EFFUSION DIFFUSION
 The process of leakage  The movement of molecules
of a gas through a very from a region of high conc. to
fine hole is called effusion. low conc. is called diffusion.

Effusion 

– – –
– – –
– – –
– – –
– – –
V = constant P = constant

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Page # 12 GASESOUS STATE

 Definition of rates of Effusion & Diffusion

Effusion Diffusion

n distan ce
rate of = rate of =
t time

V = Constant P = Constant

c c c c c c

PV = n R T PV = n R T

P n V n
 
t t t t

n P n V
rate = = rate of effusion = =
t t t t

 Graham’s law of diffusion or effusion

rate  P (Pressure of gas) ..................... (1)

rate  A (Area of hole) ..................... (2)

1
rate  (  = density of gas) ..................... (3)

PA
rate 

KPA
rate = 
PM =  R T
M  

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 GASESOUS STATE Page # 13
KP A KP A
rate = =
 M
K K
rate =  = M

 Graham’s law states that ‘’ the rate of diffusion or effusion of gas is directly proportional to
the product of pressure & area of orifice and is inversely proportional to the density of gas ‘’
 Variations in Graham’s law

 Case - I Case - II
(leaking alone) (leak together)

A B A+B

A+B
n'A
nA
Case I - A Case I - B n'B
nB
V = constant P = constant

nA ' nA PB
 Case I -A : (V = constant) Case-II nB' = nB × PA

A n1  B  n2

t1  t2

 n1 k  n2 k
  t1 = M1 ,  t2 = M2

 n1  t2 M2   n1 M2 
   
 t1 ×  n2 = M1   n 2 M1 

 t2 M2 
  
  t 1 M1 

asn  P

 P1  t2 M2
  t1 ×  P2 = M1

 t2 M2 
  
  t 1 M1 

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Page # 14 GASESOUS STATE

  P1 M2 
  
  P2 M1 

 Case I - B : (P = Constant)

 n1 k  n2 k
  t1 = M1
;  t2 = M2

 n1  t2 M2   n1 M2 
   
 t1 ×  n2 = M1   n 2 M1 

 t2 M2 
  
  t 1 M1 

as  n  V

 V1  t2 M2   V1 M2 
×   
 t1  V2 = M1   V2 M1 

 t2 M2 
  
  t 1 M1 

Kinetic theory of gases

 Postulates of Kinetic Theory of gases :

 (1) Vol . of free space

Vf s = V – Vmolecules  V

 The gases are composed of very small particles with their volume almost neglegible as compared
to the volume of the container.
 (2) Gas molecules are in constant random motion.
 (3) All the collisions in the gas molecules are assumed to be perfectly elastic.
 (4) There is intermolecular attraction or repulsion between the gas molecules.
 (5) The pressure exerted by the gas on the wall of the container is due to constt. bombard-
ment of molecules on the wall of container.
 (6) It was assumed that the K . E. of the gas molecule is directly proportional to the absolute
temperature.
K . E.  T
 (7) There is no effect of gravity on the gas molecules.

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 GASESOUS STATE Page # 15

 Molar heat capacity of gases

V = constant P = constant
Q = n Cv  T Q = n CP  T

molar heat capacity molar heat capacity

at constant volume at constant pressure.

CP – CV = R
CP

CV =

 Degree of freedom

(1) The no. of terms in the expression of energy of a gas is known as ‘’degree of freedom ‘’ symbal ‘f’.
(2) Monoatomic gas molecules possess only translational motion while diatomic & polyatomic molecules
possess translational as well as rotational and vibrational energy.

(3) At ordinary temp. the vibrational mode is neglected.

(4) monoatomic Ne  f=3

diatomic Cl Cl  f=5

polyatomic O CO  f=6

f
 Cv =
2
R

f   f 2
 Cp =   1 R =  R
2   2 

 f  2
 R
 Cp   2  2
=1+
   f f
 Cv    R
2

2
  = 1+
f

 Energy of a molecule at T kelvin is 12 kT per degree of freedom

 
where K = Boltzmann’s constant.
R 8.31
= N = = 1.38 × 10–23 J K–1 mol–1
A 6 . 023  10 23

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Page # 16 GASESOUS STATE

f f
 K . E. of one gas molecule is equal to
2
KT K.E=
2
KT

f
 Total energy of 1 mole of molecule is
2
RT

f R
1 molecule  T
2 NA

f R  f
1 mole   2  N  T × NA = RT
 A  2

f
Total energy = RT
2

Boltzmann Velocity Distribution Curve

T3
0.7 T2
0.6
T1
0.5
Fraction of
molecule

0.1
Vmp1 <Vmp2 <Vmp3

 The value of most probable velocity increases with temp.

 The fraction of molecules possessing the most probable velocity also increases with the
temperature .

 Velocities of gases

(a) Most probable (b) Average (c) Root mean

velocity velocity square velocity
Vmp Vav Vrms

 (a) Most probable velocity : (Vmp) :

 Possessed by maximum number of molecules .

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 GASESOUS STATE Page # 17

2R T 2P 2 PV 2 PVm
VmP = = = =
M  nm M

PV
P V = n RT  RT =
n

P RT
P M =  RT  =
 M
n  V
V 
1    Vm  .
n 

 (b) Average velocity :

V1  V2  V3  - - - - - - - - Vn
 Vav =
n

8 RT 8P 8 PV 8 PVn
 Vav =
M
=

=
 nM
=
M

 (c) Root mean square velocity (Vrms) :

V12  V22  V32  - - - - - - Vn2

 Vrms =
n

was defined for K E . of gas

3 RT 3P 3 PV 3 PV
m
 Vrms =
M
=

=
nM
=
M

 VmP < Vav < Vrms

 8 
 VmP : Vav : Vrms  2 : : 3 
   
  1: 1.128 : 1.224 
 Kinetic energy

 Total K . E of gas molecules Average K E per molecules

3 3 W 3
KE= nRT = RT n moles  n RT
2 2 M 2
3
n = n moles 1 mole  RT
2

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 Page # 18 GASESOUS STATE
3
K . E possessed by NA particle  RT
2
3 R 3
n moles of any gas 1 particle  × N T = KT
2 A 2

Boltzmann constant
= 1.38 × 10–23 J K–1 mol–1
3
K E (av) = KT
2
(per molecule)
 Compressibility factor (Z)

PV P Vn
Z = =
n RT RT
Z = 1  Ideal gas
Z  1  Real gas

Z>1 Z<1

 Real gas  Real gas

 Positive deviation from  Negative deviation from

ideal behaviour ideal behaviour

 intermolecular repulsion  intermolecular attraction

 can’t be liquefied  can be easily liquefied

Positive
Z deviation

H
)
ve
He (+ ve
)
N2 (+ )
4
CH ve
(+
Ideal behaviour
2
(-ve) CO

(-ve)

(P)

Question : Why H and He have Z always greater than 1?

Answer :

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 GASESOUS STATE Page # 19

Vander Waals equation

Pi Vf s = n R T

V – Vmoles = Vfs  Vfs  V

assumed no intermolecular forces.

To be vander waal equation

(a) Pressure Correction (b) Volume Correction

 (a) Pressure Correction

Pi PR
P i> P R
Pi=PR>PC

n
 PC 
V
 Conc. of gas molecules colliding per unit time within the wall of container..
n
 PC 
V
 Conc. of gas molecules behind every colliding molecule.
2
n
PC  2
V

an 2
 or , Pc =
V2
[a= Vander Waal’s constant]

Unit of a = atm L2 mol-2

 (b) Volume Correction 2t

4
2 molecules  (2r)3
3 t t
4
2 molecules 8x  r3
3
4
1 molecules 4x  r3
3
4
1 mole molecules 4x  r3 × NA
3
 Let the volume occupied by 1 mole molecule

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Page # 20 GASESOUS STATE

4 3b
 b = 4 NA x  r3 r= 3
3 16N A 

b = 4 NA x V

 Unit of b = L mole–1
Vmolecules (n moles) = n b

Vfs = Vcontainer – Vmolecules

Vfs = V – nb
Vfs = V + Vc
Vc = nb

 Vander Waal’s equation can be written as :

Pi Vfs = nRT

2 
 P  an 

 2  (V – nb) = nRT
 V 

 Variations in Vander Waals equation

 an 2 
  P  2  (V – nb) = nRT
 V 


(a) Low pressure :- neglected

P  V  V – nb  V

an 2
V  
V2

an 2
P  hence, is net neglegible
V2

 Vander Waal’s equation changes to

 an 2 
 P  2  (V) = nRT
 V 


an 2
PV + = nRT
V

PV an 2
 =1
nRT V  nRT

an
Z+ =1
VRT

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 GASESOUS STATE Page # 21

 an 
 Z  1  VRT
 

for n = 1

a
Z=1–  Z<1
VRT

 At low pressure :-

(1) Intermolecular attraction

(2) Can be liquify
(c) Negative deviation from ideal behaviour

 (b) High pressure :-

 an 2 
 P  2  (V – nb) = nRT
 V 


P  V  = V – nb  remain as it is

an 2 an 2
V =  but it very less as compared to P hence can be neglected.
V2 V2

 Now, Vander Waal’s equation changes :

P (V – nb) = nRT PV – nPb = nRT

PV nPb Pb
 =1 Z– =1
nRT nRT RT

Pb
Z=1+  Z>1
RT

 Rx

 Presure   Real gas

(a) intermolecular repulsion

(b) cannot liquefy

(c) positive deviation from ideal behaviour

Isotherm : A plot between pressure and volume keeping temprature constant called isotherm.

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Page # 22 GASESOUS STATE

 Isotherm of water

375 K Local
P 374.5 K
liquid 374.4 K
374.1 K PC,373
gas 374.0 K TC
373.9 K
373.8 K
101.1ºC

0 k solid liquid vapour k gas

mp Bp
TC
273 k
373 k
374.1k

 Critical temp (Tc) : The temp above which a gas can never be liquify is called critical temp.
8a
 Tc =
27 Rb
a, b = Vander waal constant.

a
 Critical Pressure (Pc) : Pc =
27 b 2
 Critical Volume (Vc ): Volume of one mole of gas at critical point is called critical volume.

Vc = 3 b

Calculation of Critical Constants

 a 
 P  2  (V – b) = R T
 V 
(V2P + a) (V – b) = V2 RT
PV3 – PbV2 + aV – ab = V2 RT
 RT a ab
V3 –  b   V2 + V– = 0 .....(I)
 P p P
At critical point
 b  RTc  a ab
V3 –   V2 +
 Pc . V – Pc = 0
 Pc 
At Critical Point :
(V – Vc)3 = O

V3 – 3Vc.V2 + 3V 2c V – V 3c = O .... (II)

By (i) and (ii)
R Tc
3Vc = b + P
c

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 GASESOUS STATE Page # 23

a
3V 2c = P
c
ab
V 2c = P
c

Vc3 ab / Pc
2 = a /P
3Vc c

 Vc = 3b
a
Pc =
27 b 2
8a
Tc =
27 Rb
Virial equation
 Whenever compressibility factor of a gas is expanded in the terms of 1/ Vm or P, the expansion is
called Viral equation

P Vm B C D
Z= =1+ + + +----- 
RT Vm Vm 2 Vm 3
2 3
P Vm  P  P  P
Z= =1+B   +C   + D  + - - - - - - 
RT  RT  RT  RT

Boyle’s temperature (Tb)

Z=1

Tb
a
Tb =
Rb

 The temperature at which a real gas behaves like an ideal gas is called ‘’Boyle’s temperature.’’

Inversion temperature (Ti)

gas expand  warms up


- - - - - - - - - - - - - - -(Ti )

gas expand  cools downs
2a
Ti = = 2Tb
Rb

 A temp below which a gas is expanded, it cools down and vice versa happens above that
temperature , is called ‘’inversion temperature ‘’

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 Page # 24 GASESOUS STATE
SOLVED EXAMPLES

Ex.1 When 2 gm of a gaseous substance A is introduced into an initially evacuated flask at 25°C, the
pressure is found to be 1 atm. 3 gm another gaseous substance B is then added to it at the
same temperature and pressure. The final pressure is found to be 1.5 atm. Assuming ideal gas
behaviour, calculate the ratio of the molecular weights of A and B.
Sol. Let MA and MB be the molecular weights of A and B.
Using PV = nRT for A, we get :
2
,RT
M
I A ...(i)
v

 2 3 
(n A  nB )RT   RT
and using Dalton’s Law : PTotal =  1.5 =  MA MB  ...(ii)
V
V

MA 1
Solving (i) and (ii), we get 
MB 3

Ex.2 Which of the two gases, ammonia and hydrogen chloride, will diffuse faster and by what factor ?
Sol. By Graham’s Law :

rNH3 MHCl 36.5

   1.46  r
rHCl MNH3 17 NH3  1.46 rHCl

Thus, ammonia will diffuse 1.46 times faster than hydrogen chloride gas.

Ex.3 The ratio of rate of diffusion of gases A and B is 1 : 4 and their molar mass ratio is 2 : 3. Calculate
the composition of the gas mixture intially effusing out.
Sol. By Graham’s Law :

rA PA MB 1 PA 3 PA 1 2
    
rB PB MA 4 PB 2 PB 4 3

1 2
 Mole ratio of gas A and B effusing out = [moles  pressure]
4 3
Ex.4 At 30°C and 720 mm of Hg, the density of a gas is 1.5 g/lt. Calculate molecular mass of the gas.
Also find the number of molecules in 1 cc of the gas at the same temperature.
Sol. Assuming ideal behaviour and applying ideal gas equation :
PV = nRT
Another form of gas equation is PM0 = dRT

dRT 1.5  0.0821  303

 M0 = = (T = 30 + 273 K)
T 720 / 760
 M0 = 39.38
Now number of molecules = n × N0

PV 720 / 760  1 10 –3
  N0   6.023  10 23
RT 0.0821  303
= 2.29 × 1019

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 GASESOUS STATE Page # 25

Ex.5 The pressure exerted by 12 gm of an ideal gas at temperature t°C in a vessel of volume V litre
is one atm. When the temperature is increased by 10° at the same volume, the pressure rises
by 10% calculate the temperature t and volume V. (molecular mass of the gas = 120 gm/
mole)
Sol. Using Gas equation : PV = nRT
We have, P × V = 0.1 × R × t ...(1)
and 1.1 P × V = 0.1 × R × (t + 10) ...(2)

t 1
Using (i) and (ii), we have : 
t  10 1.1
 t = 100 k or t = – 173°C
Putting the value of t in (i), we get :
 1 × V = 0.1 × 0.0821 × 100  V = 0.821 L

Ex.6 Assuming that the air is essentially a mixture of nitrogen and oxygen in mole ratio of 4 : 1 by
volume. Calculate the partial pressures of N2 and O2 on a day when the atmospheric pressure
is 750 mm of Hg. Neglect the pressure of other gases.
Sol. From Dalton’s Law of partial pressure, we have

Partial pressure of nitrogen = pN2  N2 × P and Partial pressure of oxygen = p O2   O2  P

Now, N2  4 / 5 , and  O2  1/ 5

4 1
 p N2  × 750 = 600 mm of Hg and p O 2   750 = 150 mm of Hg
5 5
Ex.7 An open vessel at 27°C is heated until three fifth of the air has been expelled, Assuming that
the volume of the vessel remains constant, find the temperature to which the vessel has been
heated.
Sol. In the given questions, volume is constant. Also, as the vessel is open to atmosphere, the pressure is
constant. This means that the gas equation is simply reduced to the following form :
nT = constant(Use PV = nRT)
or n1 T1 = n2 T2
Now let n1 = initial moles and n2 = final moles
 n2 = 2/5 × n1 (as 3/5th of the air has been expelled)

n1T1 n1T1 5
 T2 = n = 2 / 5n = T1
2 1 2

5
 T2 = (300 ) = 750 K = 477°C
2
Ex.8 When 3.2 gm of sulphur is vaporized at 450° C and 723 mm pressure, the vapour occupies a
volume of 780 m, what is the formula for the sulphur under these conditions ?
Sol. The molecular weight = no. of atoms × atomic mass
So let us find the molecular weight of S from the data given.

gRT 3.2  0.082  723

M0    256
PV (723  760)  (780 / 1000)

256
 Number of atoms = 8
32
Hence, molecular formula of sulphur = S8

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 Page # 26 GASESOUS STATE
Ex.9 A spherical ballon of 21 cm diameter is to be filled with H2 at NTP from a cylinder containing the
gas at 20 atm at 27°C. If the cylinder can hold 2.80L of water, calculate the number of ballons
that can be filled up.
Sol. The capacity of cylinder = 2.80 L
Let n = moles of hydrogen contained in cylinder and n0 = moles of hydrogen required to fill one balloon.

PV 20  280
n=   2.273
RT 0.0821  300

volume of balloon
n0  (Note : the balloons are being filled at S.T.P.)
22400

4 / 3 r 2 4 / 3  3.14  (10.5 )3
= =  0.2164
22400 22400

n
 Number of balloons that can be filled = n  10.50  10
0

Ex.10 A mixture containing 1.12L of H2 and 1.12L of D2 (deuterium) at S.T.P. is taken inside a bulb
connected to another bulb by a stop-cock with a small opening. The second bulb is fully evacu-
ated; the stop-cock is opened for a certain time and then closed. The first bulb is found to
contain 0.05 gm of H2. Determine the % age composition by weight of the gases in the second
bulb.
Sol. In the first bulb :
Initial moles of H2 = 1.12 / 22.4 = 1/20
Initial moles of D2 = 1.12/22.4 = 1/20
Now after opening of stop-cock, mass of H2 left in the first bulb = 0.05
 Moles of H2 = 0.05/2 = 1/40
 Moles of H2 effused into second bulb = 1/20 – 1/40 = 1/40
Let n be number of moles of D2 effused.
From Graham’s Law :

n 2

1/ 40 4

2
 n = moles of D2 in second bulb.
80
In the second bulb :
The mass of H2 gas = 1/40 × 2 = 0.05 gm
The mass of D2 gas = 2/80 × 4 = 0.07 gm
 Total mass = 0.05 + 0.07 = 0.12 gm
 % of H2 = 0.05/1.12 × 100 = 41.67 %
 % of D2 = 0.07/1.12 × 100 = 58.13 %

Ex.11 The pressure in a bulb dropped from 2000 mm to 1500 mm of Hg in 47 min when the contained
O2 leaked through a small hole. The bulb was then completely evacuated. A mixture of oxygen
and another gas (B) of molecular weight 79 in the molar ratio of 1 : 1 at a total pressure of 4000
mm of Hg was introduced. Find the molar ratio of the two gases remaining in the bulb after a
period of 74 min.
Sol. Now as P  n (moles), we define the rate of diffusion as the drop in the pressure per second. First we
try to find the rate of diffusion of the gas B.

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 GASESOUS STATE Page # 27

The rate of diffusion of O2 = R0 = (2000 – 1500)/47 = 10.638 mm/min.

Assuming that gas B was present alone in the bulb. Let the rate of dffusion of B = RB.
From Graham’s Law of diffusion, we have :

RB MO2 32
   0.636
RO MB 79

 RB  10.638  0.636  6.77 mm / min

Now the bulb contains mixture of O2 and B in the mole ration of 1 : 1 at total pressure of 4000 mm Hg.
 PO2  PB  2000 mm of Hg
As the pressure and temperature conditions are same for both gases in the second case (same bulb),
so the rate of diffusion will remain same in the second case also.
Let X0 and XB be the final pressure in the bulb after leakage for 74 minutes.

2000  X 0
RO   10.638
74
 X 0  1212 .78

2000  XB
RB   6.77  XB  1498 .96
74
As P  n
 Ratio of moles is given as : XO : XB = 1 : 1235

Ex.12 A 672 ml of a mixture of oxygen-ozone at N.T.P. were found to be weigh 1 gm. Calculate the
volume of ozone in the mixture.
Sol. Let V ml of ozone are there in the mixture
 (672 – V) m; = vol. of oxygen

V
Mass of ozone at N.T.P. =  48
22400

672  V
Mass of oxygen at N.T.P.   32
22400

V 672  V
  48   32  1  On solving we get : V  56 ml
22400 22400

Ex.13 A 20 L flask contains 4.0 gm of O2 & 0.6 gm of H2 at 100º C. If the contents are allowed to react
to form water vapors at 100º C, find the contents of flask and there partial pressures.
Sol. H2 reacts with O2 to form water [H2O(g)]
2 H2( g)  O 2( g)  2 H2O( g)

 2 moles of H2 = 1 mole of O2 = 2 moles of H2O

Here masses of H2 and O2 are given, so one of them can be in excess. So first check out which of the
reactants is in excess.
Now, Moles of O2 = 4/32 = 0.125 and Moles of H2 = 0.6/2 = 0.3
Since 1 mole of O2  2 moles of H2
 0.125 moles of O2  2 × 0.125 moles of H2
i.e. 0.25 moles of H2 are used, so O2 reacts completely whereas H2 is in excess.
 Moles of H2 in excess = 0.3 – 0.25 = 0.05 moles.

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 Page # 28 GASESOUS STATE
Also, 2 moles of H2  2 moles of H2O
 0.25 moles of H2  0.25 moles of H2O are produced.
 Total moles after the reaction = 0.05 (moles of H2) + 0.25 (moles of H2O) = 0.3
 The total pressure PTotal at the end of reaction is given by :

nRT 0.3  0.0821 373

PTotal    0.459 atm
V 20
Now partial pressure of A = mole fraction of A × PTotal
 PH2  0.05 / 0.3  0.459  0.076 atm

 PH2O  0.25 / 0.3  0.459  0.383 atm

Ex.19 The compressibility factor for 1 mole of a van Waals gas at 0ºC and 100 atm pressure is found
to be 0.5. Assuming that the volume of gas molecular is negligible, calculate the van der Waals
constant ‘a’.
Using van der Waal’s equation of state :
2 
 P  an  ( V  nb)  nRT


 V 2 

Now : V – nb  V(given)

 a 
 The equation is reduced to :  P  2  V  RT
 V 

PV V  RT a  a
or Z    2   1
RT RT  V V  RTV

100  V
0. 5   V  0.112 L
0.0821 273

a
Also, 0.5  1 
RTV
Substitute the values of V and T :
 a = 1.25 litre2 mol–2 atm.

Ex.20 Calculate the pressure exerted by 5 mole of CO2 in one litre vessel at 47ºC using van der waals
equation. Also report the pressure of gas if it behaves ideally in nature.
(a = 3.592 atm litre2 mol–2, b = 0.0427 litre mol–1)
Using van der waals equation of state :
3
 P  an
 
 ( V  nb)  nRT

 V2 


2 
Substituting the given values, we get :  P  3.592  5  (1  t  0.0427)  5  0.0821 320


 12 


 P  77.218 atm
If the gas behaves ideally, then using : PV = nRT

5  0.0821  320
 P atm  131.36 atm
1

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