PRE-MEDICAL CAREER POINT .

KINETIC THEORY OF GASES

1. ASSUMPTION OF KINETIC THEORY
(e) The number of collisions per unit volume in a
(i) Assumptions regarding the molecule : gas remains constant.
(a) Every gas consists of extremely small particles
known as molecules. The molecules of a given (v) Assumptions regarding force :
gas are all identical but are different than those (a) No attractive or repulsive force acts between
another gas. gas molecules.
(b) The molecules of a gas are identical, spherical, (b) Gravitational attraction among the molecules is
rigid and perfectly elastic point masses. ineffective due to extremely small masses and
(c) Their size is negligible in comparison to inter very high speed of molecules.
molecular distance (10–9 m)
(vi) Assumptions regarding pressure :
(ii) Assumptions regarding volume :
Molecules constantly collide with the walls of
The volume of molecules is negligible in
container due to which their momentum
comparison to the volume of gas. (The volume of
changes. This change in momentum is
molecules is only 0.014 % of the volume of gas.)
transferred to the walls of the container.
Consequently pressure is exerted by gas
(iii) Assumptions regarding motion :
molecules on the walls of container.
(a) Molecules of a gas keep on moving randomly in
all possible direction with all possible (vii)Assumptions regarding density :
velocities. The density of gas is constant at all points of the
(b) The speed of gas molecules lie between zero container.
and infinity (very high speed).
(c) The number of molecules moving with most
2. SOME DEFINITIONS
probable speeds is maximum.
Definition :

(iv) Assumptions regarding collision : (i) Gram mol. or Kilogram mol. :

(a) The quantity of matter in which the number of
(a) The gas molecules keep on colliding among
molecules is equal to the Avogadro's number, is
themselves as well as with the walls of defined as gram mol.
containing vessel. These collision are perfectly (b) The molecular weight of any substance
elastic. (i.e. the total energy before collision = expressed in kilogram is defined as 1 kilogram
total energy after the collisions). mol of that substance.
(b) Molecules move in a straight line with constant (c) The molecular weight of any substance
speeds during successive collisions. expressed in grams is defined as 1 gram mol of
that substance.
(c) The distance covered by the molecules between
(d) 1 Kg mol of H2 = 2 kg.,
two successive collisions is known as free path
1 Kg mol of N2 = 28 kg.
and mean of all free paths is known as mean
1 Kg mol of O2 = 32 kg.,
free path. 1 Kg mol of CO2 = 44 kg.
(d) The time spent is a collision between two (e) No. of molecules in 1 mol
molecules is negligible in comparison to time Total number of molecules
=
between two successive collisions. Number of mols.

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Mass of gas Symbols used in this chapter
(f) Number of moles =
Molecular wt. of gas
R = Universal gas constant = 8.314 J/mol-K
m
or n = = 0.082 Lit-atm/mol-K = 1.986 cal /mol-K
M
(g) The mass of 1 mol of a gas is equal to its M = Molecular wt in Kg = mass of 6.023 × 10 23
molecular weight. molecules of the gas
m = Mass of each molecule in Kg = M/N0
(ii) Avogadro's Number (NA ) : N0 = Avogadro's constant = 6.023 × 1023
(a) The number of molecules present in 1 mol of a k = Boltzman's constant =R/N0 =1.38×10–23J/K
gas is defined as Avogadro's number. P = Pressure of the gas in N/m2
(b) NA = 6.01 × 1023 per gm. mol.
= 6.02 × 1026 per Kg. mol. T = Temperature in Kelvin
N = Total number of molecules
(iii) Molar volume and Molar mass (V m ) : d = Density of gas = nM/V
(a) Molar volume Vm : The volume of 1 mol of gas n = No. of moles
is known as molar volume (Vm).
V
(b) Vm = 3. IDEAL GAS EQUATIONS
n
(c) The unit of Vm is m3/mol. PV = RT …………. For  = 1 mole = 1 gm. Molecule
PV = RT………… For  = Amount of mole
Molecular weight (M) : M
PV  RT [Mw = N0 m]
Mw
(a) The quantity in 1 mol of matter is its molecular
 mN   R 
weight. PV =   RT PV =   NT  PV  NKT
(b) M = mNA (m = mass of a single molecule)  mN 0   N0 

 R
(iv) Meaning of NTP : NTP means normal  K N
 0
temperature and pressure. N  n  
V m
(a) Temperature at NTP = 0º C = 273 K    mn

(b) Pressure at NTP = 76 cm of Hg - column 
= 1.013 × 105 Newton/meter2 or Pascal
N
= 1 atmosphere. P = K   T  P  nKT Imp.
V
(c) Volume of 1 mol of gas at NTP = 22.4 litre.
TK TK
P= or m  Imp.
m P
(v) Absolute zero temperature (0º K) :

(a) The minimum possible temperature at which all QUESTIONS FOR PRACTICE
the gas molecules come to rest, is defined as Q.1 Some container contains on average
absolute zero temperature (i.e. 0º K). 5 molecules/cm3. If the gas has temperature of
3K, then its pressure will be (N/m2) : (Hint : P = nKT)
(b) The temperature at which the kinetic energy of [Ans. 2 × 10–16]
gas molecules become zero is defined as Q.2 State equation for 1 gm. of H2 = ?
absolute zero temperature. [Ans. PV = RT/2]
(c) At this temperature the volume of the gas Q.3 For He, if 4PV = RT then amount of mass M = ?
becomes zero. [Ans. M = 1 gm]

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4. GAS LAW'S
Name of Law Constant terms Basic concept Graph
1. Boyle's Law (i) Mass of gas PV = constant
(ii) Temperature V  1/P P P
P1V1  P2 V2 1
V V

2. Charle's Law (i) Mass of gas V/T = constant

V
(ii) Pressure VT V
Slope = V0
V0
V1 V2
 T(K) –273ºC temp.(ºC)
T1 T2
( volume expansion coefficient = 1/273 per ºC)
Vt  V0 (1  t )

3. Gay-Lussac's Law (i) Mass of gas P/T = constant

P
(ii) Volume PT P
Slope = P0
P0
P1 P2
 T(K) –273ºC temp.(ºC)
T1 T2
( pressure expansion coefficient = 1/273 per ºC)
Pt  P0 (1  t )

4. Avogadro's Law:- At same temperature and

5. CALCULATION OF PRESSURE OF GAS
pressure equal volumes of all gases contains equal
number of molecules. Y

5. Dalto's Law:- According to this law, the pressure exerted

by a mixture of several gases equals the sum of the pressure
exerted by each component gas present in the mixture i.e.
Pmax. = P1 + P2 + P3…………. X

 RT  L
P=    Pmix. 
 V  L
Z
RT
 Pmax = [ 1 +  2 + 3] 1. Consider an ideal gas enclosed in a cubical
V
vessel of edge 'L'

2. Consider a molecule moving with velocity v in
6. Graham's Law of diffusion:- According to this
any direction
law, at same temperature and pressure, the rate of  ^ ^ ^
v = v x i  v y j v z k
diffusion of gas is inversely proportional to the
3. This molecule collides with the shaded wall
square root of the density of gas i.e.
with velocity vx.
1 1 (a) momentum before collision = mvx
Rate of diffusion rd  ; Vrms  ; So, Vrms  rd
  (b) momentum after collision = – mvx
(assuming elastic collision)
[For H2 gas (Max)]
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   change in momentum of the molecule 1 1
= – mvx – mvx = – 2mvx or PV = m0 v 2rms or PV = Nm v 2rms
3 3
4. By the law of conservation of momentum
10. As we know , energy of each molecule
change in momentum of the wall = equal in
magnitude but opposite in direction to that of 1
= m v 2rms
molecule P = 2mvx 2
5. The distance travelled parallel to the 1
Total energy = E0 = Nm v 2rms
x-direction = L. Thus, the time between two 2
successive collisions with the shaded wall is   Nm v 2rms = 2E0
2L
t = 2 2
vx   PV = E0 or P = E
3 3
   number of collisions per second (n) is
where E = Energy per unit volume
vx
n=
2L
6. The momentum imparted per unit time to the 11. Dependence of pressure :
wall by this molecule is  (a) P  n (Total number of moles)
(b) P  m ( Total mass of the gas)
v mv 2x
  F = nP = x 2mvx = (c) P  v 2rms
2L L
7. The total force on the wall (d) P  1/V (V = Volume)
(e) P  d (d = Density)

m 2 m
=F=  vx = v 2x (f) PE (E = Energy per unit volume)
L L
8. Assuming average velocity in all direction to be Examples
Calculation of pressure of a gas
based on
equal, we have 
Ex.1 A flask of 10–3 m3 volume contains 3 × 1022
1
   v 2x =  v 2y = v 2z =  v 2x + v 2y + v 2z ) molecules of oxygen at a certain temperature.
3
The mass of one molecule of oxygen is
1 1 m 2 5.3 × 10–26 Kg and rms velocity of its molecules
= v2  F = v
3 3 L
at the same temperature is 400 m/s. Calculate
9. If N is the total number of molecules in the the pressure of the gas.
1 mN  v 2 Sol. Pressure of the gas
sample, F =
3 L N 1 mN 2
P= v rms
Pressure on the wall = Force /Area 3 V
Here V = 10–3m3 N = 3 × 1022
F 1 mN  v 2
P= 2 = m = 5.3 × 10–26 Kg, vrms = 400 m/s
L 3 L3 N
1 m 0  v2 1 5.3 10 –26  3 10 22  (400) 2
P=   P=
3 V N 3 10 – 3
where,m0 = Total mass of the gas = mN = 8.48 × 104 N/m2.
V = Volume of the vessel
m = mass of each molecule Ex.2 The pressure of an ideal gas is written as
1   v 2 
 (d = density = m 0 ) 2 E
   P= d P= . Here E refers to –
3  N 
 V 3V
(1) Translational kinetic energy
1  v2
  P = d v 2rms  (vrms = ) (2) Rotational kinetic energy
3 N

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(3) Vibrational kinetic energy (3) 1 : 10 (4) 10 : 1
(4) Total kinetic energy
Sol.[4] Let's consider the wall perpendiculars to x-axis
Sol.[1] Pressure of the gas number of collisions per second are given by
1 mN 2 vx
P= v rms Now, vx = vrms/ 3
3 V 2L
1 'L' and 'T' is same of both. Then, Ratio of speed
  Energy E = v 2rms
2 given by
1  v 2  v 22  ...  v 2n 
= mN 1  v rms,H 2 M Ne 20
2  N  = = = 10 :1
  v rms, Ne M H2 2
1 1 1
= mv12  mv 22  .... mv 2n
2 2 2 Ex.6 Two containers of equal volumes contain H2
So energy is basically the sum of energies of all and O2 at same temperature. If the number of
molecules which represents translational kinetic molecules of these gases is also equal then the
energy. ratio of pressure exerted by these will be -
(1) 1 : 1 (2) 4 : 1
Ex.3 Which of the following parameters is the same (3) 8 : 1 (4) 16 : 1
for molecules of all gases at a given temperature ? Sol.[1] Pressure of the gas
(1) Mass (2) Speed 1 nM 2 1 nM 3RT nRT
P= v rms = . =
(3) Momentum (4) Kinetic energy 3 V 3 V M V
Given, nH = nO , TH = TO
Sol.[4] Kinetic energy according to kinetic theory of 2 2 2 2

gases is given by, VH = V O

2 2
3    PH = PO
E = RT 2 2
2
R is a universal constant and temperature Ex.7 The density of carbon dioxide gas at 0ºC and at
remains same for all gases. So kinetic energy is a pressure of 1.0 × 105 newton/metre2 is
1.98kg/m3. Find the root mean square velocity
same for molecules of all gases at a given
of its molecules at 0ºC. Pressure is constant
temperature. (1) 39 metre/sec (2) 3.09 metre/sec
(3) 389 metre/sec (4) 38.9 metre/sec
Ex.4 A gas is filled in a container at pressure 'P 0' . If Sol.[3] We know that
the mass of each molecule is halved and speeds 1
are double, then resulting pressure will be - P =  v2
3
(1) 4P0 (2) 2P0 / 2
 3P 
  vrms =  
(3) P0 (4) 4P0/ 2   
1 Nm 2 Given that  = 1.98kg/m3 and
Sol.[2] P0 = v rms (m = mass of each molecule, P = 1.0 × 105 N/m2
3 V
V = volume of the gas) 3  1.0  10 5
Now , m' = 1/2 m   vrms =
1.98
v'rms = 2vrms
 vrms = 389 m/s
1 Nm.4 v 2rms 1 Nm 2
P' = = 2. v rms = 2P0
3 2V 3 V 6. DIFFERENT K.E. OF GAS

Ex.5 The ratio of number of collisions per second at 1. Translatory kinetic energy (Er)
the walls of containers by H2 and Ne gas 1 3
Er = Mv 2rms  PV
molecules kept at same volume and temperature 2 2
is – Total internal energy of ideal gas is kinetic
(1) 10 : 1 (2) 1 : 10
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 5.32  10 26  (11.1 10 3 ) 
  T=  
 3  (1.38  10  23 ) 
 
2. Energy per unit volume or energy density (Ev) : (J/M3)
  T = 1.6 × 105 K
Total Energy E 1M
Ev   ; Ev =   v 2rms ; Ex.9 The first excited state of hydrogen atom is
Volume V 2 V 
10.2 eV above its ground state. What temperature
1
Ev = v 2rms is needed to excite hydrogen atoms to first excited
2 level –
2 1  (1) 7.88 × 104K (2) .788 × 104 K
 P   v 2rms  (By pressure expression) 4
3 2  (3) 78.8 × 10 K (4) 788 × 104 K
Sol.[1] K.E. Per atom = 3/2 KT
2 3
P= Ev ; E v  P Imp. K.E. of the hydrogen atom = 10.2 eV
3 2   10.2 eV = 10.2 × (1.6 × 10–19) Joule
3. Molar K.E. or Mean Molar K.E. (E):- (K.E. of N0 2 K.E. per atom
molecules or K.E. of Mw grams gas) T= ×
3 K
1 3 3
E  M w v 2rms E  RT  N 0 KT …(1) 2 10.2 1.6 10 19
2 2 2  T= ×
3 1.38 10 23
4. Molecular kinetic energy or mean molecular K.E. Where k = 1.38 × 10–23 J/mole. ºK
( E ) :- [K.E. of a gas molecule]   T = 7.88 × 104 K
E 3 RT 3 Ex.10 At what temperature does the average
E ; E E  KT …(2)
N0 2 N0 2 translational kinetic energy of a molecule in a
5. Gram K.E. or Mean gram K.E. (Em):- (K.E. of 1 gas equal to the kinetic energy of an electron
gram gas) accelerated from rest through a potential
E 3 RT 3 KT difference of 5 volt.
Em  ; Em   …(3)
Mw 2 Mw 2 m (1) 386.5 × 103K (2) 3.865 × 103K
3
(3) .38 × 10 K (4) 38.65 × 103 K
1
Em  Sol.[4] K.E. of the electron is
Mw
5 eV = 5 × 1.6 × 10–19J
But K.E. = 3/2 KT
  5 × 1.6 × 10–19 = 3/2 (1.38 × 10–23) × T
E E
5 1.6  10 19  2
 T=
temp. in ºC temp. in K 3 1.38 10  23
  T = 38. 65 × 103 K
Examples
based on
Different kinetic energy of gas
Ex.8 At what temperature will the root mean square 7. DIFFERENT TYPE OF SPEED:
velocity of oxygen molecules be sufficient so as 1. Average velocity:- ( v )
the escape from the earth ?
(1) 1.6 × 105 K (2) 16 × 105K v1  v 2  .......... v N
v 0
(3) .16 × 105 K (4) 160 × 105 K N
3 1 Because molecules are in random motion in all
Sol.[1]  KT = mve2 possible direction in all possible velocity.
2 2
Therefore, the velocity of the gas container is
Where ve = escape velocity of earth = 11.1 km/sec zero.
m = mass of 1 molecule of oxygen = 5.34 × 10–26
 mv e2  2. Rms speed of molecules:-(vrms)
T=  
 3K 
  Vrms =
3P

3RT

3KT
 Mw m

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0  2  3  4  4  4  5  5  6  9 42
= 1.732
KT
……(1) vav = 
m 10 10
= 4.2 ms–1
3. Mean speed of molecules:- (By maxwell's
velocity distribution law) (vM or < | v | >)
(ii) R.M.S. speed,
8P 8RT 8KT
vMean =  
 M w m  (0) 2  (2) 2  (3) 2  (4) 2  (4) 2  (4) 2  (5) 2  (5) 2  (6) 2  (9) 2 
1/ 2

Vr.m.s   
KT  10 
= 1.595 ……..(2) 1/ 2
m  228 
  = 4.77 ms–1
| v |  | v 2 | ..... | v n |  10 
 | v |  v mean = 1
N
(iii) most probable speed vmp = 4m/s
4. Most probable speed of molecules :-(vmp)
At a given Temperature the speed to which Ex.12 At what temperature, will the root mean square
maximum number of molecules belongs is
velocity of hydrogen be double of its value at
called as most probable speed (vmp)
S.T.P. , pressure remaining constant ?
2P 2RT 2KT
vmp =   Sol. Let V1 be the r.m.s. velocity at S.T.P. and V2 be
 Mw m the r.m.s. velocity at unknown temperature T 2.
V
KT
…(3)
= 1.414 Here T1 = 273 K, T2 = ? 2  2
m V1
5. Velocity of sound in gas medium:- (vs) We know, V2  T
P RT KT V12 T1 V 
2
vsound =   [ 1 <  < 2]   or T2 = T1  2 
 Mw m 2
V2 T2  V1 
= 273 × (2)2 = 273 × 4 = 1092K
Special points :-
T2 = (1092 – 273) = 819ºC
1. At any temperature (always)
vrms > vMean > vmp > vsound Ex.13 Calculate rms velocity of oxygen molecule at 27ºC
2. For a gas at any temperature (T) Sol. Temperature, T = 27ºC  273 + 27 = 300 K,
Molecular weight of oxygen = 32 × 10–3kg,
v rms 3 v rms 3 R = 8.31 J mol–1 K–1
 , 
vsound  v mp 2 Now, r.m.s. velocity is
3. At temp is not possible at which above order can be 3RT 3  8.31 300
V  = 483.5 ms–1
M 32  10 3
changed. Always vrms  vMean  vmp  vsound
Ex.14 Calculate the kinetic energy of a gram molecule
4. At any given temperature of argon at 127ºC.
Sol. Temperature, T = 127ºC = 273 + 127 = 400 K,
Any speed  T;
R = 8.31 J/mol K
graph v r.m.s.v / sT  parabola Now, K.E. per gram molecule of argon
3 3
= RT  × 8.31 × 400 J = 4986 J
2 2
Examples
based on
Different Type of Speed
QUESTIONS FOR PRACTICE
Ex.11 The velocities of ten particles in ms–1 are
Q.1 The ratio of number of collision per second at
0, 2, 3, 4, 4, 4, 5, 5, 6, 9. Calculate
(i) Average speed and the walls of containers by H2 and Ne gas
(ii) r.m.s. speed molecules kept at same volume and temperature
(iii) most probable speed
Sol. (i) Average speed, (Hint : fc = Vrms/2) [Ans. 10 : 1 ]

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Q.2 At what temperature will rms velocity of O2 2. AT TK, energy of each degree of freedom is KT/2.
molecules be equal to that of H2 at 200 K. 3. If 'f' is the degree of freedom per molecule for a gas,
then
[Ans. 3200 K] (i) Total energy of each molecule = fKT/2
(Vrms )He 5 (ii) Total energy per mole of gas = fRT/2
Q.3 If  and temperature of H2 is 0ºC 4. For '' mole of a gas
(Vrms )H 7
fRT
Internal energy at temperature TK is U  = CvT
then the temperature of He will be. [Ans.5.5º C] 2
Q.4 What should be temp of O2 gas molecules from Imp.
escaping the earth. [Ans. TO2 = 16 × 104 K] 5. Change is internal energy is given by
fR
U  (T) = CvT
Q.5 If speeds of 3 molecules are 0.5, 1 & 2m/sec. 2
respectively then ratio of their root mean square This change is process independent.
speed and the average speed is. [Ans. 1.1 : 1]
Q.6 The rms velocity of smoke particles of mass 9. MAXWELL'S LAW OF DISTRIBUTION OF
3 × 10–17kg. at 27º C in m/sec. is. VELOCITIES:
[Ans. 2 × 10–2 m/sec.]
Q.7 If at STP velocity of sound in a gas is 400 ms–1 Nmax
T1

number of molecules (N) 

500K
( = 1.5), then what will be the rms velocity of
vmp = most probable speed
gas molecules at NTP. [Ans. 400 2 m/sec–1]
Vmax = maximum speed of molecule

Q.8 When gas temperature becomes twice by Nmax T2

1000K T3
heating then gas dissociate from molecular 2000K
Nmax
form to atomic form. What will be the effect on
vrms. [Ans. v'rms = 2vrms]
0– 0–
Q.9 At what temperature will the average velocity of 0–
oxygen molecules be sufficient so as to escape 0 Vmp Vmp Vmax Vmp Vmax Vmax
from the earth ? Escape velocity of earth is
molecule velocity V 
11.0 kms–1 [Ans. 1.56 × 105 K]

Q.10 An electric bulb of volume 250 cm3 has been
sealed at a pressure of 10–3 mm of mercury and
temperature 27ºC. Find the number of air
molecules in the bulb. [Ans. 80 × 1014]
Q.11 The temperature of a gas is –68ºC. To what
temperature should it be heated so that (i) the
average kinetic energy of the molecules be
doubled, (ii) the root mean square velocity of the
molecules be doubled ? [Ans. (i) 137ºC, (ii)547ºC]
Q.12 Calculate for hydrogen at 27ºC : (i) kinetic
energy of one gram-molecule of the gas, (ii)
kinetic energy of one gram gas and (iii) root
mean square velocity of the molecules.
[Ans. (i) 3.74 × 103 J, (ii) 1.87 × 103J (iii) 1933.73 ms–1]
8. MAXWELL'S LAW OF EQUIPARTITION
OF ENERGY
The total kinetic energy of a gas molecules is
equally distributed among its all degree of freedom
and the energy associated with each degree of
freedom at absolute temperature T is 1/2 KT
Special point:-
1. At T = 0K, energy of each degree of freedom is 0,
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Special point:-
1. At any given temperature graph drawn in
between molecular velocity & number of
molecules is known as velocity distribution
curve (v.d.c.)
2. The velocities of molecules of a gas are in
between zero and infinity (0 – )
3. With the increase in the temperature, the most
probable velocity and maximum molecule
velocity are increases.
4. The number of molecules within certain
velocity range is constant although the velocity
of molecule changes continuously at particular
temperature
5. The area enclosed between the (N-v) curve and
the velocity axis presents the total number of
molecules.
Special Conclusion:-
On the basis of velocity distribution Maxwell's
gives the law of equipartition of energy for
gases of any temperature
10. MEAN FREE PATH OF GAS MOLECULES:
KTG 116
 CAREER POINT . PRE-MEDICAL
"The distance between any two consecutive collision is  For one mole real gas
called free path. The average distance travelled by a  a 
molecule between successive collision is called the mean  Preal  2 (VIdeal  b)  RT
free path".  V 
 For  mole of real gas
PMT95 b  m3  M0L3T0 a
1 a  Nm4  ML5T–2 (a & b Vanderwaal's gas
m = d = diameter of molecule
2 d 2 n constant )
m N (B) Amaghat Experiment:-
m = d = molecular density n = PV
2 d (mn )
2 V
m M mN
m =  = density of gas =  = = = mn H2
2d 2 V V Ideal gas
V V KT
m = PV = NKT   O2
2 d 2 N N P
KT
m = P
2 d 2 P
At low temperature and high pressure gases shows
deviation from Boyle's law.
Special point:- Graphs are drawn between PV and P at 0ºC for
1. At equal temperature pressure condition mean H2 and O2
free path will be maximum for molecule of
lightest gas (H2) Conclusions:-
2. By increasing amount of gas in a container of (1) All real gases shows deviation at high pressure
definite volume then m decreases. and low temperature, deviation of CO2 gas is max.
3. If pressure reduces by taken out some gas from (2) According to Amaghat every real gas has
container then m increases. definite and specific temperature at which it
follows Boyle's law this is known as Boyle's
Specific Coefficient of gas:- temperature of real gas
1 Boyle's coefficients :-
1. Thermal conductivity coefficient K = Cvvrmsm
3 TB  TC [TB = Boyle's temperature,
1
2. Viscosity coefficient of gas n =  vrmsm TC = Critical temperature] TB 
a
where a
3 Rb
1
m  & b are Vanderwaal's constant for real gas.
v rms
1 (C) Dr. Andrewz's Experiment:- (Isothermal curve
3. diffusion coefficient of gas D= vrmsm of real gas)
3
Dr. Andrewz drawn graphs in between volume
11. REAL GAS and pressure for different constant temperature
and curves are obtained these curves are known
(A) Vanderwaal's Equation:- (For real gas) as isothermal curve
Ideal gas equation PV = RT Example:- CO2 curves at different temperature
two correction are made in ideal gas model
1. Volume correction (Due to finite size of
molecules):-
Vreal = V – b
b = decrease in volume for 1 mole gas
2. Pressure correction (Due to inter molecular
forces):-
(i) Pressure decreases  (density)2
RT a
(ii) Preal =  2
Vb V
 a 
 Preal  2 (VIdeal  b)  RT
 V 
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 PRE-MEDICAL CAREER POINT .
P 8a a 8
ideal gas behaviour 1. VC = 3b ; TC = ; PC = 2
; TC  TB
27 Rb 27b 27
PC VC 3
liquid
48.1ºC 2. 
Pc C
35.5ºC RTC 8
d
3. Critical element of gas are derive from vanderwall's
liquid

TC = 31.1ºC gas equation at critical position for which.

cirtical temp. curve  dP 
c
Liquid and gas b   0
liquification 21.5ºC gas  dV critical
a vapour behaviour
13.1ºC
At critical point, slope of the graph is zero.
0 VC
(Isothermal curves for CO2 gas at different temperature) Sp. Results for Real gas:-
1. All real gases follow Vanderwaal's gas equation
at every possible temperature and pressure so
these are known as vanderwaal's gases.
Special points:- 2. At a given temperature volume and pressure for
(1) By meeting edge of horizontal part of these real gas are comparatively low than for ideal
curve parabola is obtained. It peak point is
known as critical point gas.
(2) Thermodynamic element corresponding to 3. Internal energy of real gas depends upon its
critical point is known as critical parameters temperature pressure and volume If U 
(TC, VC, PC) Change in Internal energy
(i) Critical temp (TC)- It is that temperature
Ideal gas U = CvT
below which a gas can be liquified only by U = f(T)
increase in pressure and above which no
 = 1 mole
liquification is possible whatever the
pressure may be incresed. a
(U)Real= Cv T + V
Real gas TC Real gas V2
UReal = f(T, P, V)
He  –268ºC
H2  –240ºC 
N2  –147ºC 4. Internal Energy of Real gas is always (–ve) at
O2  –118ºC absolute zero temperature.
CO2(CPMT-94)  31.1ºC
5. Specific heat of Real gas increases By
Steam  +365ºC increasing temperature and decreases By
decreasing temperature
(ii) Critical pressure:-(PC)
Minimum pressure required to liquiefy a
12. SPECIAL POINT FOR IDEAL GAS:
gas when it is at critical temperature is
called critical pressure (1) A gas which follows all gas laws and gas
For He PC = 2 atmospheric pressure equation at every possible temperature and
For CO2 PC = 76 atmospheric pressure pressure is known as ideal or perfect gas.
For O2 PC = 49.7 atmospheric pressure (2) Molecule of gas can do only and only
translational Motion and kinetic energy related
(iii) Critical volume:-(VC) to this is known as translational kinetic
At critical pressure and temperature the energy. E trans  T
volume of one mole of gas is called its critical
(3) Potential energy of ideal gas is zero. So
volume (VC).Critical volume for CO2 gas
internal energy of ideal gas is perfectly
= 95 × 106 m3
translational K.E. of gas. It is directly
proportional to absolute temperature. So,
Special Results:
internal energy depends only its temperature.
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 CAREER POINT . PRE-MEDICAL
For a substance U = Ukinetic + Upotential
UKE – depends only on temperature,
UPE – depends upon intermolecular forced
(Always (–) Ve)
Note:- By taking same amount of mono atomic gas
and diatomic gas and same heat energy is given
then rise in temp of mono atomic gas is
comparatively more.
(T)Mono > (T)dia > (T)tri –
f=3 for monoatomic (100% trans)
f=5 for diatomic (60% T + 40% R)
E Trans  T
f=7 for triatomic (T : R : V : : 3 : 2 : 2)
E Trans  T
4. According to Dr. Andrewz ideal gas cannot be
liquidified and solidified. There are no critical
elements for ideal gas (Tc, Pc, & Vc)
Critical Temperature for CO2 gas = 31.1ºC
5. Specific heat of ideal gas is constant quantity
and it does not change with temperature

ideal gas Real gas

Cv Cv

temperature temperature

Imp.6. All real gases behaves as ideal gas at high

temperature and low pressure.
7. Volume expansion coefficient () and pressure
expansion coefficient () is same for a ideal gas
and value of each is 1/273 per ºC
 =  = 1/273 per ºC
8. Gas molecule have point mass and negligible
volume and velocity is very high (107 cm./sec.)

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SOLVED EXAMPLE
Ex.1 The mass of hydrogen molecules is number of their molecules are n1 and n2
3.32 × 10–27kg. If 1023 hydrogen molecules respectively, the temperature of the mixture
strike a fixed wall of area 2 cm2 at an angle 45º will be
to the normal and rebound elastically with a T  T2 T T
(1) 1 (2) 1  2
speed of 103m/s calculate the pressure exerted n1  n 2 n1 n 2
on the wall –
n 2 T1  n1T2 n1T1  n 2 T2
(1) 2.347 × 103 N/m2 (2) 23.47 × 104 N/m2 (3) (4)
n1  n 2 n1  n 2
(3) 234.7 × 103 N/m2 (4) 23.47 × 103 N/m2
Sol.[1]
A Sol.[4] Total energy of molecules of first gas
Wall
3
= n1 K T1
2
Total energy of molecules of second gas
45º 3
= n2 KT2
N O 2
45º Total energy of molecules of mixture
3
= K (n1T1 + n2T2)
2
3 3
B   (n1 + n2) KT = K(n1T1 + n2T2)
2 2
The molecule strikes the wall along AO and
n1T1  n 2 T2
rebound along OB such that   T=
(n1  n 2 )
AON = NOB = 45º
The change in component momentum of each Ex.3 The atomic weight of iodine is 127. A standing
H2 molecule in a perpendicular direction the wave in a tube filled with iodine gas at 400 K
wall =P = 2 mv cos, has nodes that are 6.77cm apart when the
where mv = momentum of molecule frequency is 1000 vib/sec. iodine is
P = (3.32 ×10–27) ×103 cos 45º (1) Monoatomic (2)Diatomic
P = 4.692 ×10–24 kg m/sec (3) Triatomic (4) None of these
Force exerted by N molecules on the wall Sol.[2]  = 2 × 6.77 cm = 13. 54cm
= P × N  = n = 1000 × 13.54 = 1.354 × 104cm/sec.
if A is the area of the wall on which the we know that
molecule strike, then pressure VR
= where molecular weight
N  P 10 23  4.692  10 24 T/M
P = F/A = =
A 2  10  4 M = Ax with x = 1 if iodine is monoatomic
= 2.347 × 103 N/m2 x = 2 it diatomic and A is atomic weight
Ax  2
Ex.2 Two ideal gases at temperature T 1 and T2 are  = = 0.7x
RT
mixed. There is no loss of energy. If the masses Where x = 2 as iodine is diatomic
of molecules of the two gases are m1 and m2 and    = 1.4 (right value of diatomic gas)

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 CAREER POINT . PRE-MEDICAL
Ex.4 Certain perfect gas is found obey (P + gh) V0 = PV
PV3/2 = const. during adiabatic process. If such
 gh 
a gas at initial temperature T is adiabatically or V = V0  1  
compressed to half the initial volume, in final  P 
temperature will be –
(1) 2T (2) 2T Ex.7 Two gases occupy two containers A and B the
(3) 2 2 T (4) 4T gas in A, of volume 0.10m3, exerts a pressure
Sol.[1]  PV3/2 = constant of 1.40 MPa and that in B of volume 0.15 m3
(given) exerts a pressure 0.7 MPa. The two containers
nRT are united by a tube of negligible volume and
Put P=
V the gases are allowed to intermingle. Then it
 nRT  3/2 the temperature remains constant, the final
    (V ) = constant
 V  pressure in the container will be (in MPa) –
When V changes to V/2 the temperature (1) 0.70 (2) 0.98
becomes 2 T. (3) 1.40 (4) 2.10
Ex.5 In a certain process the pressure of one mole Sol.[2] We Know that
ideal gas varies with volume according to the PAVA = nART, PBVB = nB RT
a and Pf (VA + VB) = (nA + nB) RT
relation P = , where a, b are
 V 2 Pf (VA + VB) = PAVA + PBVB
1    
  b    P V  PB VB 
 Pf =  A A 
constants, when the volume of gas V = b, then  VA  VB 
temperature of the gas will be - 1.4  0.1  0.7  0.15
= MPa
ab 0.1  0.15
(1) (2) ab/R
2R = 0.98 MPa
(3) ab (4) zero
PV Ex.8 If the pressure of a gas contained in a closed
Sol.[1]  T=
R vessel is increased by 0.5% when heated by
a a 2ºC, then the initial temperature must be
at V = b, P = =
(1  1) 2 (1) 127ºC (2) 273ºC
(3) 400ºC (4) 673ºC
ab
  T= Sol.[1] Using PV = nRT, we note that
2R
P1V = nRT1
Ex.6 An air bubble of volume V0 is released by a fish P1 (1.005)V = nR (T1 + 2)
at a depth h in a lake. The bubble rises to the (note P = P2 – P1 = 0.005 P1 and 
surface. Assume constant temperature and   T = 2ºC = 2K
standard atmospheric pressure above the lake.
T1  2
The volume of the bubble just before touching Dividing we get 1.005 =
T1
the surface will be (density) of water is 
(1) V0 (2) V0(gh/P) or 0.005T1 = 2  T1 = 400
Thus in 0ºC, t1 = 400 – 273 = 127ºC.
V0  gh 
(3) (4) V0 1  
 gh   P 
1   Ex.9 What is the degree of freedom of gas ? If at
 P 
Sol.[4] As the bubble rises the pressure gets reduced for STP the velocity of sound in it is 330 m/sec
constant temperature, if P is the standard and gas density = 1.3 mg/cm3.
atmospheric pressure, then (1) 2 (2) 3

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 PRE-MEDICAL CAREER POINT .
(3) 5 (4) 4 V
or M = V   =
P Mw
Sol. [3]  =
 PVM w PM w
From equation (1), T = 
P = 1.013 × 10 N/m ,  = 1.3kg/m , v = 330 m/s
5 2 3 VR R
Given : P = 1.4 × 109 atmosphere
v2P
= = 1.4 = 1.4 × 109 × 1.01 × 105 Nm–2

 = 1.4 g cm–3 = 1.4 × 1000 kg m–3,
Let f be the number of degree of freedom then
Mw = 2 × 10–3 kg/mol
Cv = f R/2 and Cp= fR/2 + R = R (1 + f/2)
Substituting values,
C 2f
  = P = = 1.4
CV f 1.4 109 1.01105  2 103
T K
1.4 1000  8.4
 (f = 5)
= 2.4 × 107 K

Ex.10 A closed container of volume 0.02 m3 contains a

mixture of neon and argon gases at temperature Ex.12 The speed of ten particles in ms–1 are
of 27ºC and pressure of 1 × 105 Nm2. The total 0, 1.0, 2.0, 3.0, 3.0, 3.0, 4.0, 4.0, 5.0 and 6.0.
mass of the mixture is 28 g. If the gram Find (a) the average speed, (b) the root-mean
molecular weights of neon and argon are 20 and square speed, and (c) the most probable speed
40 respectively, find the masses of the of these particles.
individual gases in the container, assuming Sol. (a) The average speed is
them to be ideal. Given R = 8.314 J/mol/K. 0  1.0  2.0  3.0  3.0  3.0  4.0  4.0  5.0  6.0
v
Sol. Let m g be the mass of neon. Then, the mass of 10
argon is (28 – m)g. (b) The mean-square speed is
Total number of moles of the mixture, 1
v2  [0 + (2.0)2 + (1.0)2 + (3.0)2 + (3.0)2
m 28  m 28  m 10
=   …(1)
20 40 40 + (3.0)2 + (4.0)2 + (4.0)2 + (5.0)2 + (6.0)2 ]

PV 1105  0.02 = 12.5 m2 s–2,

Now, =   0.8 …(2) and the root-mean square speed is
RT 8.314  300
28  m vrms = 12.5 m 2s 2 = 3.5 ms–1
Equating (1) and (2), = 0.8
40
(c) Of the ten particles, three have speed of
or 28 + m = 32
3.0 ms–1, two have speed of 4.0 ms–1 and each
or m = 4g mass of argon = (28 – 4)g = 24 g
of the other five has a different speed. So the
most probable speed of the particle is 3.0 ms–1.
Ex.11 Calculate the temperature of the Sun if density
is 1.4 g cm–3, pressure is 1.4 × 109 atmosphere
Ex.13 Calculate the total number of degrees of
and average molecular weight of gases in the
freedom possessed by the molecules in one cm3
Sun in 2 gm/mole Given R = 8.4 J mol–1K–1.
of H2 gas at NTP.
PV
Sol. We know that PV = RT or T = …(1) Sol. 22400 cm3 of every gas constains 6.02 × 1023
R
molecules
M M
But   and    Number of molecules in 1 cm3 of H2 gas
Mw V

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 CAREER POINT . PRE-MEDICAL
6.02 1023 P R  M 
= = 0.26875 × 1020 or  as V  
22400 T M w  
Number of degrees of freedom of a H2 gas Now as M and R are same for top and
molecule = 5 bottom
 Total number of degrees of freedom of  P   P   P T
     i.e., T  T  B
0.26875 × 1020 × 5 = 1.34375 × 1020.  T  T  T  B B PB TT

 T 70 300 75
Ex.14 A vessel of volume 8.0 × 10–3 m3 contains So    = 0.9868
 B 76 280 76
an ideal gas at 300 K and 200 kPa. The gas
is allowed to leak till the Pressure falls to
Ex.16 During an experiment an ideal gas is found
125 kPa. Calculate the amount of the gas to obey an additional law VP 2 = constant.
(in moles) leaked asssming that the The gas is initially at temperature T and
temperature remains constant. volume V. What will be the temperature of
the gas when it expands to a volume 2V.
Sol. As the gas leaks out, the volume and the Sol. According to given problem VP2 = constant.
temperature of the remaining gas do not So gas equation PV = RT in the light of
change. The number of moles of the gas in above (eliminating P) yields.
PV
the vessel in given by n . The  K  R
RT  V  RT , i.e., V T
 V K
number of moles in the vessel before the
leakage is, V1 T  V T
   1  i.e., 
P1V V2  T2  2V T'
n1 =
RT
or T ' = ( 2 )T
and that after the leakage is,
P2 V
n2  Ex.17 The specific heat of argon at constant
RT
Thus, the amount leaked is, volume is 0.075 kcal/kg K. Calculate its
( P1  P2 ) V atomic weight, [R = 2cal/mol K]
n1 – n2 =
RT Sol. As argon is monatomic, its molar specific
= n1 – n2 heat at constant volume will be

(200  125)  103 N / m 3  8.0  10 3 m 3 3 3

CV  R  2  3 cal/mol K
= 2 2
(8.3J / mol  K )  (300K )
Now as CV = McV with CV = 0.075 cal/gK
3 = M × 0.075
Ex.15 At the top of a mountain a thermometer
3
reads 7ºC and barometer reads 70 cm of Mw = = 40 gm/mole
0.075
Hg. At the bottom of the mountain they
read 27ºC and 76 cm of Hg respectively.
Compare the density of the air at the top
with that at the bottom.
Sol. According to gas equation = PV = RT
M  M 
PV = RT as   
Mw  Mw 

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