GAS LAWS

 Gas laws are based on experiments on the physical properties of gases that were carried out
different scientists over several centuries.
 They describe macroscopic behavior of gaseous substances

Boyle’s Law (The Pressure – Volume Relationship)

 It is a pressure-volume relationship law based on experiments by Robert Boyle, an English
Chemist (1627–1691)
 Using apparatus similar to one in Figure 3, Boyle showed how pressure is related to volume
for a gas of fixed amount at a given temperature.

Figure 3 Apparatus for studying the relationship between pressure and volume of a gas
In Figure 3
(a) The levels of mercury are equal and the pressure of the gas is equal to the atmospheric
pressure (760 mmHg). The gas volume is 100 mL.
(b) Doubling the pressure by adding more mercury reduces the gas volume to 50 mL.
(c) Tripling the pressure decreases the gas volume to one-third of the original value.
The temperature and amount of gas are kept constant.
 Boyle observed that the volume (V) of a given amount of a gas decreases as the total
applied pressure (P)—atmospheric pressure plus the pressure due to the added mercury is
increased at constant temperature
 Conversely, if the applied pressure is decreased, the gas volume becomes larger at constant
temperature.
 The results of several such experiments done by Boyles are tabulated in the following table:

 Boyle's law and is stated as follows:

The volume of a fixed quantity of gas maintained at constant temperature is inversely

proportional to the pressure.

Mathematical presentation of Boyle’s Law:

1 1
V or V  constant x
P P
or PV = constant

Where V is volume, P is pressure for fixed number of moles at a fixed temperature.

Example

Consider a 1.47 litre sample of gaseous SO2 at a pressure of 4.6 x 103 Pa. If the pressure is

changed to 1.4 x 104 Pa at a constant temperature, what will be the new volume of the

gas?

We know from rearrangement of Boyle's law that

PV = constant

This relationship should therefore hold before and after the pressure is changed

provided the temperature is kept constant. So we can write:

 P1V1 = P2V2

Rearranging we have:
P1V1
V2 
P2

4.6 x 103 Pa x 1.47 l

V2   0.48 L
1.4 x 10 4 Pa

A quick check on the answer shows that the volume decreased from 1.47 litres at the

lower pressure to 0.48 litres at the higher pressure, consistent with Boyle's law.

Charles’s Law (The Volume–Temperature Relationship)

 Charles studied how volume of a gas is related to temperature at constant pressure.

 Charles's law states that:

The volume of a fixed quantity of gas maintained at constant pressure is directly

proportional to its absolute temperature.

 Figure 4 shows the change in volume upon increasing temperature.

Figure 4 The effect of temperature on volume for a fixed quantity of gas

 The mathematical presentation of Charles's law proceeds as follows:

V  T (for fixed n and P)

V = constant x T or
V
 k for fixed n and P.
T
Where n is the amount (mol) of the gas and k is a constant.

 Figure 5 shows the relationship of volume and temperature for several gases.

Figure 5 Response of selected gases when subjected to temperature change

 The condition of zero volume is never realised as all gases liquefy or solidify before

reaching - 273.2 °C. Note that on the Celsius scale -273.15 °C is equivalent to the

absolute zero.

Example

A sample of gas at 17 °C and 1 atm has a volume of 2.42 l. What volume will this gas

occupy at 48 °C and 1 atm?

From Charles's law we know that V  T and we therefore rewrite Charles law as:
 V
 constant
T
We expect this situation to remain constant according to Charles's law before and after

the volume and temperature have changed as long as the pressure remains constant.

We can therefore say:

V1 V
 constant  2
T1 T2

Therefore we can solve for V2 as follows:

T   321 K 
V2   2 V1    x 2.42 l  2.68 L
 T1   290 K 

Always remember to ensure that the temperature used is in the calculation is based on

the Kelvin scale.

1.4 Avogadro’s Law (Volume – amount of gas relationship)

 Avogadro’s principle which relates the quantity of gas to the volume it occupies.

 This is stated thus: Under the same conditions of temperature and pressure, a given

number of molecules occupy the same volume, regardless of their chemical identity.

 Further, Avogadro’s law was formulated by Amedeo Avogadro stating that:

At constant pressure and temperature, the volume of a gas is directly proportional to the

number of moles of the gas present.

 Alternatively the law can be expressed as:

At a fixed temperature and pressure, equal volumes of any ideal gas contain equal

numbers of particles (or moles).

 Mathematically Avogadro’s law (at constant temperature and pressure) can be

expressed as follows:

V  n or
 V = constant x n
V
k where k is a constant.
n
Doubling the number of moles of a gas will cause the volume to double if T and P

remain constant. From Avogadro's law, we can state:

V1 V
 k  2 (T and P kept constant)
n1 n2

The Ideal Gas Equation

 If we revisit the three Laws that we have studied so far we summarise by making

volume V, the subject for all the laws and proceed as follows:
1
Boyle’s Law: Vα (constant n, T)
P

Charles’s Law: V  T (constant n, P)

Avogadro’s Law: V  n (constant P, T)

 A more general law by combining the above 3 laws would be :

nT
V
P
If we introduce a proportionality constant, and call it R, then we can write :

 nT 
V  R 
 P 

Rearranging the equation we have:

PV = nRT known as the ideal gas equation.

  An ideal gas is a hypothetical gas whose pressure, volume, and temperature

behaviour is completely described by the ideal gas equation. The term, R, in the

ideal gas equation is known as the gas constant. The value and units of R depend

on the units of P, V, n and T. The units for T are always in Kelvin, n is normally

expressed in mol and in most countries other than the United States of America,

SI unit of Pa for pressure is employed. Table 1.1 lists numerical values of the gas

constant, R, in various units.

Table 1.1 List of numerical values of R, the Gas Constant

Units Numerical Value of R

l.atm/mol.K 0.08206

J/mol.K 8.314

Cal/mol.K 1.987

m3.Pa/mol.K 8.314

l.torr/mol.K 62.36

l.bar/K.mol 0.08314

Note, 1 Pa = 1 N/m2

1Pa.m3 = 1 J 1 kg.m2/s2 = 1 l kPa

Unless you are asked otherwise, there is no need to try to remember the values of the Gas

Constant; it is usually made available for calculations but when presented with a problem it is

expected that you will choose the correct R value.

 Suppose we have 1.000 mol of an ideal gas at 1.000 atm and 0.00 °C, the volume of

the gas would be:

nRT (1.000mol) x (0.08206 l.atm/mol. K) x (273.15 K)

V 
P 1.000 atm

= 22.41 L

The conditions, 0 °C and 1 atm are referred to as Standard Temperature and

Pressure (STP). The volume occupied by 1 mole of ideal gas at STP, 22.41 litres is

known as the molar volume of an ideal gas at STP. Note in the example, the

numerical value of R is 0.08206 was used so that it is consistent with the units of the

other parameters given in the problem.

Example

A sample of diborane gas (B2H6), a substance that burst into flames when exposed to air,

has pressure of 345 torr at a temperature of -15 °C and a volume of 3.48 l. If conditions

are changed so that the temperature is 36 °C and the pressure is 468 torr what will be

the volume of the sample?

Solution

Note that in this problem there are two variables, temperature and pressure. In that case

then you need to rearrange the ideal gas equation such that all variables are on one side

and those that are not changing are left on the other side.

Since the ideal gas law is: PV = nRT, in this problem it is only n and R that are

not changing, so we rearrange it as follows:

 PV
 nR and by implication this should be the same before and after the
T
conditions are changed.

P1V1 PV P1V1 P2 V2
So we can write:  nR  2 2 or 
T1 T2 T1 T2

We can now solve for V2

T2 P1V1 (309 K)(345 torr)(3.48 l)

V2    3.07 L
T1P2 (258 K)(468 torr)

The ideal gas equation is also a very useful tool when measuring and calculating

densities and molar masses of gases. Density has units of mass per unit volume. The

ideal gas equation can be rearranged as follows.

n P

V RT
If we multiply both sides of the equation with Mr the molar mass of the gas, then we

have:
nM r PM r

V RT
We know that the product nMr gives the mass of the substance and dividing this mass

by V gives the density, d, therefore we can write:

nM r PM r
 d 
V RT
This equation tells us that a gas with higher molar mass and pressure will have a higher

density in the absence of mixing.