GAS LAWS

BOYLE’S LAW:
Boyle’s law states that for a fixed mass of gas at constant temperature, its pressure is inversely
proportional to its volume.
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Pressure   If temperature is constant 
V

PV  constant (1)

The apparatus shown in the figure below may be used to establish this result

Figure 1: Boyle’s Law apparatus

Here, a fixed mass of air is trapped at the top of a uniform vertical tube as shown above. To
compress the air, the value is opened and air is pumped from a foot pump. When the gas is in
thermal equilibrium with the surrounding, the volume V of the air is measured and the pressure
P is recorded from the pressure gauge. To ensure that thermal equilibrium is attained, enough
time is left in taking one reading and the next. In this manner the temperature of the gas is
maintained at the temperature of the surroundings which is assumed to be constant during the
experiment. The pressure is increased in steps at each step the corresponding volume is
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measured. A graph of Pressure P against is plotted.
Volume V
The graph is a straight line passing through the origin (Figure 2). If the experiment is repeated
for other fixed temperatures of the gas, the gradient of each straight line increases with
temperature.

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Figure 2: Boyle's law P 
V

If a graph of pressure P is plotted against the volume V, the graph shown in Fig 3 is obtained.
Each curve is obtained from measurements of P and V at the respective constant temperatures.
The constant temperature curves are known as isothermals.

Figure 3: Isothermals

Boyle’s law can also be illustrated in the graph of PV against P {Figure 4 or PV against V
(Figure 4b)}

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 Figure 4: A graph of PV against P (a) and a graph of PV against V (b)

Boyle’s law is not obeyed for all gases or at all temperatures and pressures. Most gases obey
Boyle’s law at low pressure and deviate from it at high pressures. A gas that obeys Boyle’s law
for all pressures and temperatures as known as an ideal gas. None of the real gases such as
Nitrogen, oxygen, nitrogen or neon are ideal.

Example 12: A beaker of volume V is pushed vertically downwards into a pool of water with
its mouth downwards. If the atmospheric pressure is equivalent to 10 m of water, how far below
the water surface must the beaker be pushed so that the volume of air in it becomes 0.8V? The
temperature of the pool may be considered to be constant.

Solution:
On the surface of the pool, volume of air in the beaker V1 = V , pressure P1 = 10 m

Let h = depth below surface of pool when volume of air in beaker V2 = 0.8V

Pressure P2 = 10 + h  m

Using Boyle's law, P2 V2 = P1V1

(10 + h) (0.8V) = 10.0 x V

10 + h = 12.5
∴ h = 2.5 m

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CHARLES’ LAW:
Charles’ law states that for a fixed mass of gas at constant pressure, its volume increases by
1/237 of its volume V0 at 0 ℃ for each degree centigrade raise in temperature

 1 
i.e Volume of gas θ °C, V = V0 1 + θ
 273 
The relationship between volume and temperature of a fixed mass of gas at constant pressure
can be investigated using the apparatus shown in Fig 5

Figure 5: Charles’ law

Here, air is trapped in a capillary tube by a thread of paraffin. The capillary tube is tied to a
millimeter scale and placed inside a water bath which is heated. The temperature of the trapped
air is assumed to be the same as the water temperature which is measured using a thermometer.
The length of trapped air in the tube is directly proportional to its volume. The pressure of the
trapped air remains constant throughout at the atmospheric pressure. Before taking any reading,
the water is stirred with a stirrer. The length l, of the trapped air is measured for different
temperatures and a graph of volume (V) is plotted against temperature (Fig 6)

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Figure 6: (a) Graph of V against 𝜃 (℃) (b) Graph of V against T (K)

The graph is a straight line which when extrapolated cuts the temperature axis at – 237.15 ℃,
the temperature – 273.15 ℃ when the volume is zero is known as the absolute zero of
temperature. The equation of the straight line in Fig 6 (a) can be written as
V = K  θ + 273.15

V = KT Where T  θ + 273.15
Thus, the volume V of a fixed mass of gas at constant pressure is directly proportional to its
thermodynamic temperature, T
i.e V  T
V
= Constant, If P = Constant (2)
T
Which is an alternative statement of Charles’ law
The value of the constant K in the equation V = KT, depends on the pressure of the gas and its
mass as illustrated below.

Figure 7:

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Example 13: If there are 2.7 x 1019 molecules in 1 cm3 of a gas at 273 K and pressure 1 x 105
pa, how many molecules are there in 1 cm3 of the gas at 350 K and pressure 1 x 105 pa?
Solution:
Since the pressure is constant, at 1.0x105 pa, using Charles’ law,
V2 V1
=
T2 T1

T 
Volume at 350 K, V2 = V1  2 
 T1 

 350  3
= 1.0 ×   cm
 273 
In this volume  V2  of the gas, the number of molecules is 2.7 x 1019.

∴ The number of molecules in 1 cm3 of the gas at 350k and 1 x 105 Pa

2.7  1019
= 1.0 ×
 350 
1  
 273 
 2.1  1019

The Ideal Gas Equation

An ideal gas obeys Boyle’s law and Charles law perfectly. In practice, an ideal gas does not
exist at all. However, real gases can behave almost like ideal gases at low pressure and high
temperature. At higher pressures the real gases deviate from the ideal gas behavior as shown
below.

Figure 8: PV = constant for an ideal gas at constant temperature

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The state of an ideal gas is determined by the three parameters, pressure P, volume V and
temperature T. These three parameters P, V and T are related by an equation known as the ideal
gas equation
To derive the ideal gas equation, we assume that we have a fixed mass of ideal gas in a cylinder
fitted with a smooth light piston as shown below in Figure 9 (a)

Figure 9: The ideal gas equation

Suppose that the initial pressure, volume and temperature of the gas are P1, V1 and T1,
respectively. If the pressure of the gas is changed to P2 at constant temperature, according to
Boyle’s law, the volume V of the gas is given by
P2 V2 = P1V1

If the temperature of the gas is then changed to T2 at constant pressure, according to Charles’
law, the new volume is given by
V2 V
=
T2 T1
V2 V
      P2V2  = P1V1 
T2 T1
P2 V2 P1V1
=
T2 T1
PV
⟹ = Constant
T
The value of this constant depends on the mass and type of gas
For a mole of gas, the value of the constant is the same for all gases and is known as the molar
gas constant. The symbol for the molar gas constant is R.

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  3a 
PV
= Constant
T

 3b  
PV
=R  3
T 
PVm = RT  3c  


Where Vm is the volume of 1 mole of gas. This equation is known as the ideal gas equation.
The value of R, the molar gas constant, can be calculated from the fact that at standard
temperature i.e when T = 273 K, P = 101.3 kpa, V = 22.4 x 10-3 m3
From (3)
PVm = RT

PVm
R=
T

101.3  10  22.4  10   8.31 J K

3 3
1
mol1
273
The ideal gas equation can also be written in other forms as follows:
V
1. If the volume of a mole of an ideal gas is V, then volume of 1 mole, Vm =
n
From
PVm = RT

V
P = RT
n
PV = nRT (4)
2. If the mass of a gas of volume V is m, and M is the mass of 1mole of the gas, then the
m
number of mole n =
M
From (4),
PV = nRT
m
PV = RT (5)
M
3. Also, if N = number of molecules in the volume V and NA = Avogadro’s number,
N
number of molecules in a mole of gas, then the number of mole n =
NA
From (4),
PV = nRT

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 N
PV = RT (6)
NA
Example 14: In the diagram below, the volume of flask X is twice that of flask Y. The system
is filled with an ideal gas and a steady state is established with flasks held at 200 K and 400 K
respectively. If the mass of gas in X is m, what is the mass of gas in Y?

Solution
During the steady state, the pressure in X and Y are the same
If V = volume of Y and M = mass of 1 mole of gas
m
Then using PV = RT ,
M
 m' 
For Y: PV =   R400 (1)
M
m
For X: P  2V  =   R200 (2)
M
Dividing (1) by (2),
1 m'
=2
2 m
m
∴ m' =
4

Example 15: After the pressure of the air in a bicycle tyre has been incrased slightly by
pumping air into the tire, it was found that the number of moles of air in the tyre has increased
by 2 %, the thermodynamic temperature by 1 %, and the internal volume of the tyre by 0.2 %.
By what percentage has the pressure of the air in the tyre increased?

Solution:
Suppose initially, pressure = P, volume = V, temperature = T and n = number of moles of air.
And finally, pressure = Pʹ, volume = 1.002V, temperature = 1.01T and number of moles =
1.02n
Using, PV = nRT Using

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Initially, PV = nRT (1)

Finally, P' 1.002V  = 1.02n  R 1.01T  (2)

Dividing (2) by (1)

P' 1.002V  1.02n  R 1.01T 
=
PV nRT
P'
1.002 = 1.02 1.01
P
1.0302
P' = P
1.002
P' = P 1.028

The pressure has increased by 2.8%

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