GAS LAWS

Boyle's law:
This law states that, "If temperature remains constant, the volume (V) of the gas of given mass of gas is inversely
proportional to the pressure (P) of the gas".
Mathematically,
1
Volume (V)  pressure (P)

1
or, VP or, or, PV = constant

If any gas at certain temperature (T) has initial volume (V 1) and pressure (P1) and there is change in volume
(V2) and pressure (P2) at the same temperature (T). Then we can say.
P1V1 = P2V2 = constant
If we plot a graph pressure (P) and volume (V) we get a graph as shown in fig. (a) if we plot a graph Pressure
1
(P) and volume (V) , we get a graph as shown in fig. (b).
 
P P

V 1/V
(a) (b)
Fig. Boyles Law

Charle's Law
In 1787, jacqes Charle had found two laws of gas. They are;
1. Charle's law at constant pressure (Law of volume)
2. Charle's law at constant volume (Law of pressure)
1. Charle's law at constant pressure This law states that, "If pressure of gas remains constant, the volume
of the given mass of the gas increases or decreases by a constant fraction of the volume of the gas at 0°C
for each degree rise or fall in temperature.
Let us consider Vo be the volume of the gas at 0°C and V be the volume of the gas at °C having definite
constant pressure (P).
From Charle's law at constant pressure
Final volume (V) = Initial volume (Vo) + Constant fraction (P) × Initial volume (Vo) × Change in
Temperature ().
or, V = Vo + P Vo, where P = volume coefficient of gas at constant pressure.
or, V = Vo (1 + P) ……………….. (ii)
1
Experimentally it is found that P = 273

So, equation (i) can be written as,

 1
V = Vo 1 + 273 
 
273 + 
or, V = Vo  273 
 
But 273 +  = Tθ, absolute temperature of gas at θ0C and 273 = To, absolute temperature of gas at 00C
So, the above expression becomes.

V = Vo × Tθ
To
Vθ = Vo
Tθ To
Simply we can say,
V
V
T = Constant
P = Constant
i.e. V  T
Thus it may states that at constant pressure the volume of
given mass of gas is directly proportional to the absolute V0
temperature.
This is Charle's law at constant pressure (Law of –273°C O 
volume). Fig. Graphical Representation of Charleꞌs Law

2. Charle's law at constant volume

This law states that "If volume of a gas remains constant, the pressure of the given mass of the gas
increases or decreases by a constant fraction of the pressure of the gas at 0°C for each degree rise or fall
in temperature.
Let us consider Po be the pressure of certain mass of gas at 0°C and P be the pressure of the gas at °C
having definite constant volume (V). From Charle's law at constant volume,
Final pressure (P) = Initial pressure (Po) + constant fraction (V) × Initial pressure (Po) × Change in
temperature (),
or, P = Po + V Po , where, V = pressure coefficient of gas at constant volume
or, P = Po (1 + V ) …………………. (i)
1
Experimentally it is found that value of V = 273/0C

So, equation (i) can be written as,

1
P = Po 1 + 273 
 
273 + 
or, P = Po  273  …………………. (ii)
 
But 273 +  = Tθ, absolute temperature of gas at θ0C and 273 = To, absolute temperature of gas at 00C
So, equation (ii) becomes.

P = Po × Tθ
To
Pθ = Po
Tθ To
 Simply we can say,
P
T = Constant
i.e. P  T
Thus it may states that at constant volume the pressure of given mass of gas is directly proportional to
the absolute temperature.
This is Charle's law at constant volume (Law of pressure),

V = Constant P

P0

–273°C O 
Fig. Graphical Representation of Charleꞌs Pressure Law

Relationship in between pressure coefficient (V) and volume coefficient (p) of gas.

Pressure  Const. Temperature const.

P0, V0, 0 P0, V,  P, V0, 

(a) (b) (c)

Fig. Changing temperature, pressure and volume of a gas.
Consider any gas inside a cylinder having original pressure (P o) volume (Vo) and temperature 0°C. The gas is
heated upto °C at constant pressure so that its new volume becomes V. Now, from Charle's law at constant
pressure,
V = Vo [1 + P ] …………….. (i)
Where P is the volume coefficient of gas at constant pressure.
Again the gas is compressed until its original volume is recorded at constant temperature. The new pressure
becomes P as shown in fig. (c) Now from Boyle's law,
P0V = PV0
or, P Vo = PoV …………………. (ii)
Now from equation (i) and (ii)
PVo = PoVo [1 + P]
P = Po [1 + P ] ……………… (iii)
But from Charle's law at constant volume,
P = Po [1 + V] ………………. (iv)
 Where v is the pressure coefficient of gas at constant volume.
Now, from equation (iii) and (iv)
Po [1 + V ] Vo = PoVo [1 + P ]
or, 1 + V = 1 + P 

or, V = P

In this way volume and pressure coefficient are numerically equal.

The equation of state or combined gas equation (Ideal gas equation)
Ideal gas is the one which strictly follow Boyle's and Charle's law. The gas equation which is formulated with
the help of Boyle's and Charle's law is known as ideal gas equation. It is ideal because it is an ideal concept till
now.
Consider one mole of an ideal gas kept inside a cylinder having non conducting walls and containing movable,
air tight and frictionless piston. Let, P1, V1 and T1 be the original pressure, volume and temperature of the gas.
For first step, the gas is compressed slowly at constant temperature then the pressure and volume of the gas is
changed to P2 and V respectively. So the process is isothermal for which Boyle's law holds true.

Temperature const. Pressure const.

P1, V1, T1 P2, V, T1 P2, V2, T2

(a) (b) (c)

Fig. Changing temperature, pressure and volume of a gas.

Then, from Boyle's law
P1V1 = P2V
P1V1
or, V = P2 ……………….. (i)
For second step, the gas is expanded at constant pressure P 2 until its volume changed to V2 and
temperature of the gas changed to T2.
Now from Charle's law at constant pressure,
V V2
T1 = T2
V2 T1
or, V = T2 …………………….. (ii)
Now, from equation (i) and (ii)
P1V1 V2T1
P2 = T2
P1V1 P2V2
or, T1 = T2
PV
or, T = Constant.
 But for one mole of an ideal gas, the value of the constant always found to be same which is known as
universal gas constant and is denoted by R.
PV
So, T = R

or, PV = RT
This is the ideal gas equation for one mole of an ideal gas.
If we consider n mole of an ideal gas, the ideal gas equation can be written as,
PV = nRT

Postulates of kinetic theory of gas

1. A gas consists of large number of identical tiny particles known as molecules. The molecules of different
gases are different.
2. Molecule of gas is assumed to be perfectly elastic sphere.
3. The molecules of gas move in straight path in constant speed between two successive collisions and obey
Newton's laws of motion.
4. The molecules of gas can move in random direction with different possible velocities.
5. When the molecules of gas collide with each other or with the wall of the container, the collision is
considered as perfectly elastic.
6. The actual volume occupied by the gas is negligibly small in comparison to the volume of the vessel containing
gas.
7. When the molecules of gas strike on the wall of container, they exert mechanical pressure on it.
Pressure exerted by molecules of gas to the wall of container
Consider a cube having length 'l' contains N number of molecules of an ideal gas. Let C 1, C2, ….., CN are the
velocity of the molecules at the temperature T and u1,u2,…..,uN are the components of C1, C2, ….., CN along X-axis
respectively. Similarly the components of C1, C2, ….., CN along Y and Z axes are (v1,v2,…..,vN ) and (w1,w2,…..,wN )
respectively . let ' mp ' be the mass of a gas molecule. Then total mass of gas, m = Nmp
The mean square speed of gas can be expressed as,
Y

C12=u12+v12+w12 B E
C22=u22+v22+w22
C32=u32+v32+w32 A F
v
c

m u
w
Cn2=un2+vn2+wn2………..(i) C H
X

Z D l G

If the first molecule moves from the face ABCD to EFGH with velocity u 1, then the linear momentum possessed
by it can be written as,
Initial momentum = mpu1
When the molecule strikes to the face EFGH and rebounds towards the face ABCD, it moves with the speed '–
u1' because the collision is perfectly elastic.
So, final momentum = – mpu1
Now,
 Change in momentum = initial momentum – Fina momentum
= mpu1 - mp(-u1)
The change in linear momentum = 2 mpu1
When the molecules travels from the face ABCD to EFGH and rebounds to the face ABCD in time t second, it
travels '2l' distance with same speed u1.
2l
So, time taken (t) = u ……………… (iv)
1

Hence, the force exerted on the first molecule by the face EFGH is given by
change in momentum
F1x = Time taken
2mpu1
or, F1x = 2l × u1
2
mpu1
or, F1x = l
Similarly forces exerted on the other molecules by the face EFGH are given by
2 2 2
mpu2 mpu3 mpuN
F2x = l , F3x = l ……..FNx = l
 Total force exerted on all the molecules by the face EFGH is
Fx = (F1x + F2x + …………+ FNx)
2
mpu21 mpu22 mpuN
Fx =( l + l + ……….+ l )
mp
(
Fx = l u21 + u22 + ………+ uN2 )
As we know that the force exerted by the face EFGH on the gas is equal in magnitude but opposite in
direction to the force exerted by the gas on the face, the force by the gas on the wall along x-axis is given
by
mp
(
Fx = l u21 + u22 + ………+ uN2 )
So, the pressure along X-axis is
Fx Fx
Px = A = l 2
mp
(
or, Px = l3 u21 + u22 + ………+ uN2)
Similarly,
Pressure along Y-axis is
mp
(
Py = l3 v21 + v22 + ………+ vN2)
and pressure along Z-axis is
mp
(
Pz = l3 w21 + w22 + ………+ wN2 )
Thus, the total average pressure (P) is equal to the average of P x, Py and Pz.
Px+Py+Pz
∴P= 3
mp
or, P= 3l3[( ) ( ) ( )]
u21 + u22 …….+ uN2 + v21 + v22 + vN2 + w21 + w22 + ……. wN2
 mp
or, P= 3V [(u + v 2
1
2
1 ) ( ) (
+ w21 + u21 + v22 + w22 + ………+ uN2 + vN2 + ……. wN2 )] ( using equation i ) we get,
mp
[
P= 3V c21 + c22 + …….. cN2 ]
c21 + c22 + …….. cN2 — —
here, N = c2 where c2 is called mean square speed of gas.
—
or, c21 + c22 + ….. + cN2 = N c2
mp —
 P = 3V N c2
1 mpN —
or, P = 3 V c2
1m —
or, p = 3 V c2
1 —
or, P = 3 c2 ; where,  = density of gas and m is the total mass of the gas.
This is the expression for the total pressure exerted by gas on the wall of container.
—
Root mean square speed of gas crms or c ( )
—
(
It is defined as the square root of mean square speed of gas molecules. It is denoted by crms or c .Since we )
have from kinetic theory of gas,
1 —
P = 3  c2
— 3P
or, c2 = 

Taking square root on both sides, we get

3PV m
or, crms = , where  = V , m = mass of gas
m
for n-mole of ideal gas PV =n RT
3nRT
then, crms = m
3RT m
or, crms =
M , since, n = M , M = molecular mass of gas and n is the number of moles of the gas. For a given
gas 3R/M is a constant.
 crms  T
Thus, the rms speed of a gas is directly proportional to the square root of its absolute temperature.
Average kinetic energy per mole of gas
Consider one mole of ideal gas at Pressure, Volume and Temperature P, V and T respectively.
Then, from ideal gas equation
PV = RT………..(i)
Again from kinetic theory of gas,
1 —
P = 3 c2

1M —
or, P = 3 V c2 , where M = molar mass of gas

1 —
or, PV = 3 Mc2 ………(ii)
 from equation (i) and (ii)
1 —2
3 Mc = RT
1 —2 3
2 Mc =2 RT……….(ii)
1 —
Here, 2 Mc2 be the average kinetic energy of one mole of gas.

3
or, K.E per mole of gas = 2 RT……(iv)

Similarly, let NA be the number of molecules in 1 mole of gas (Avogadro's number) and 'mp' be the mass of each
molecule.
Then, mass of one mole gas is
M = NA mp………(v)
From equation (iii) and (v)
1 — 3
2 NAmpc = 2 RT
2

1 —2 3 R
2 mpc =2 NA T
1 —2 3 R
2 mpc = 2 KT, where K = NA , is called Boltzmann's constant and its value is 1.38×10 JK ,
-23 -1

3
or, KE per molecule of gas = 2 KT……..(vi)

From equation (iv) and (vi)

K.E of gas ∝ Temperature
i.e. KE∝T
It means that the kinetic energy of gas depends upon temperature of the gas. Increase in temperature increases
molecular vibration which increases the kinetic energy of the gas. At absolute zero i.e. T = 0K, the kinetic energy
of the molecule will be zero which indicates that all molecules of gas stop.

Derivation of Gas laws from Kinetic theory of gas:

Boyles law:
As we know, from kinetic theory of gas.
1 —
P = 3 c2

1 𝑚— 𝑚
P = 3 c2 [ ∵ Density () = ]
𝑉 𝑉

1 —
PV = 3 m c2
— 1 —
Since, c2  T , 3 m c2 will be the constant quantity for the given mass of gas at a given temperature.

Hence, PV = constant
or, V1
P

or, P1
V
Thus, the pressure exerted by a given mass of gas is inversely proportional to the volume occupied by it at
constant temperature which is Boyle's law.

b. Charle’s Law at Constant Volume:

As we know from kinetic theory of gas,
Pressure exerted by gas on the wall of container (P) can be written as,
1 —
P = 3  c2

1𝑚 — 𝑚
or, P = 3 c2 ………………………. (i) [ ∵ Density () = ]
𝑉 𝑉

1𝑚
3 𝑉 is a constant quantity for the given mass of the gas occupying a fixed volume V .So, we can write
—
P  c2 ………………………. (ii)
But, we have,
—
c2  T ………………………. (iii)
Now, from equations (ii) and (iii)
PT
P
or, T = Constant
Thus, the pressure of given mass of gas occupying a fixed volume is directly proportional to the
absolute temperature which is Charle's law at constant volume.
c. Charle’s law at constant pressure:
As we know, from kinetic theory of gas, pressure exerted by gas (P) on the wall of container can be
written as,
1 —
P = 3  c2

1𝑚 — 𝑚
or, P = 3 c2 [ ∵ Density () = ]
𝑉 𝑉

1𝑚 —
or, V = 3 c2 ………………………. (i)
𝑃

1𝑚
But 3 is a constant quantity for a given mass of gas at constant pressure.
𝑃

So we can write,
—
V  c2 ………………………. (ii)
But also we have,
—
c2  T ………………………. (iii)
So, from equation (ii) and (iii)
V T
V
or, T = constant
Thus, the volume of a given mass of gas at constant pressure is directly proportional to the absolute
temperature which is Charle's law at constant pressure.
d. Ideal or prefect gas equation
 From kinetic theory of gas
1 —
P = 3 c2
1 𝑚— 𝑚
or, P = 3 c2 [∵Density (ρ) = ]
𝑉 𝑉

1 —
or, PV = 3 mc2
1
But 3 m be constant quantity for a given mass of gas.
So, we can write
—
PVc2
—
Since, c2 T
or, PVT
PV
or, T = constant
or, PV = RT Where, R is universal gas constant .
For n moles of gas
PV = nRT
which is the ideal gas equation or the equation of state.
1. A cylinder of gas has a mass of 10.0kg and a pressure of 8.0 atmospheres at 27°C. When
some gas is used in a cold room at –3°C, the gas remaining in the cylinder at this
temperature has a pressure of 6.4 atmosphere. Calculate the mass of gas used.
2. Two glass bulbs of equal volume are joined by a narrow tube and are filled with a gas
at S.T.P. When one bulb is kept in melting ice and the other is placed in a hot bath, the
new pressure is 877.6 mm mercury. Calculate the temperature of the bath.
3. A cylindrical tank has a tight-fitting piston that allows the volume of the tank to be
changed. The tank originally contains 0.110m3 of air at a pressure of 3.40atm. the piston
is slowly pulled out until the volume of the gas is increased to 0.390m3. If the temperature
remains constant, what is the final value of the pressure?
4. Find the rms speed of nitrogen at NTP. Density of N 2 = 1.29 kg /m3 at NTP.
5. Assuming the density of nitrogen at STP to be 1.251kgm –3, find the root mean square
velocity of nitrogen molecules at 127°C.
6. Air at 273 K and 1.01 × 105 N/m2 pressure contains 2.70 × 1025 molecules per cubic
meter. How many molecules per cubic meter will there be at a place where the
temperature is 223K and the pressure is 1.33× 10–4 Nm–2?
7. Air at 273 K and 1.01105 N/m2 pressure contains 2.701025 molecules per cubic meter,
How many molecules per cubic meter will there be at a place where the temperature is
223 K and the pressure is 1.33104 N/m2?
Ans: 4.351024 mol m3

8. The root mean square (rms) speed of a gas molecule is 600 ms –1 at 500oC. Calculate
the rms speed of the gas at 100oC.
Ans: 416.97 m/s
9. A cylindrical tank has a tight fitting piston that allows the volume of the tank to be
changed. The tank originally contains 0.110m 3 of air at a pressure of 3.4 atm. The
piston is slowly pulled out until the volume of the gas is increased to 0.390 m3. If the
temperature remains constant what is the final value of the pressure?
Ans: 0.95 atm
10.At a pressure of 700 mm of Hg the root mean square speed of the molecules of a gas
 is 400 ms–1. What is its density?
Ans: 1.785 kg m–3
11.What is average translational K.E. of a molecule of an ideal gas at a temperature of
27oC? What is the total random translational kinetic energy of the molecules in mole of
this gas? What is the root-mean-square speed of oxygen molecules at this temperature?

Ans: 484.4 m/sec

12.At what temperature will the average speed of oxygen molecule be sufficient so as to
escape from the earth? [Escape velocity from the earth is 11.2 km/s and mass of one
oxygen molecule is 53.4 10–24 g]
Ans: 1.62106 K
13.Air at a temperature of 273 K and 1.01  10 Nm pressure contains 2.7  1025
5 –2

molecules per cubic meter. How many molecules per cubic meter will there be at place
where the temperatures is 223 K and pressure 1.33  10–4Nm–2?
Ans: 4.35  1016/m3
14.Taking the density of Nitrogen at STP to 1.251 kgm–3, find the root mean square velocity
of Nitrogen molecules at 127C.
Ans: 596.6 m/s
15.A cylinder of gas has a mass of 10 kg. and pressure of 8 atmosphere at 27C. When
some gas is used in a cold room at –3C, the gas remaining in the cylinder at this
temperature has a pressure of 6.4 atmospheres. Calculate the mass of gas used.
Ans: 1.1 kg.
16.Helium gas occupies a volume of 0.04m 3 at a pressure of 2  105Nm–2 and temperature
300K. Calculate the mass of the helium and root mean square speed of its molecules.
(Relative molecular mass of helium = 4, molar gas constant = 8.3 J mol –1K–1)
Ans: 0.0129 kg, 1364 m/sec.
17.Two glass bulbs of equal volume are joined by a narrow tube and are filled with a gas
at s.t.p. When one bulb is kept in melting ice and the other is placed in a hot bath, the
new pressure is 877.6 mm of Hg. Calculate the temperature of the bath.
Ans: 373 K