Heat and Thermodynamics


   
 
Deductions from Kinetic Theory
Boyle's law
At a given temperature, the pressure of a given mass of a gas is inversely proportional to its volume. This is Boyle's law.
 
From equation (vi), we have
 
-----(a)
 

As for a given gas, µ T , the value of   is constant at a given temperature. In addition, for a given mass of the gas, m and N are constants. Thus, from (a)

 
pV=constant
 
 
Charles' Law
At a given pressure, the volume of a given mass of a gas is proportional to its absolute temperature. This is Charles' law.
 
From (a), if p is constant in expression (a),
 
 
 
we get , which is Charles' law
 
Charles' Law of Pressure
Regnault's or Gay-Lussac's Law
 
At a given volume, the pressure of a given mass of a gas is proportional to its absolute temperature. This is Charle's law for pressure.
 
This is the definition of the absolute temperature, T. If one starts from
 
the fact that µ T and uses the fact that V is constant, one gets from (a),
 
 
Avogadro's Law
At the same temperature and pressure, equal volumes of all gases contain equal number of molecules. This is Avogadro's law.
 
Consider equal volumes of two gases kept at the same pressure and temperature. Let,
 
m1 = mass of a molecule of the first gas
 
m2 = mass of a molecule of the second gas
 
N1 = number of molecules of the first gas
 
N2 = number of molecules of the second gas
 
p = common pressure of the two gases
 
V = common volume of the two gases
 
From equation (vi)
 
 
where v1 and v2 are rms speeds of the molecules of the first and the second gas respectively. Thus,
 
-----(b)
 
As the temperatures of the gases are the same, the average kinetic energy per molecule is same for the two gases (equation ix), i.e.,
 
 
From (b) and (c),
 
N1 = N2, which proves Avogadro's law.
 
Graham's Law of Diffusion
When two gases at the same pressure and temperature diffuse into each other, the rate of diffusion of each gas is inversely proportional to the square root of the density of the gas. This is Graham's law of diffusion.
 
It is reasonable to assume that the rate of diffusion is proportional to the rms speed of the molecules of the gas. Then, if r1 and r2 be the rates of diffusion of the two gases,
 
-----(d)
 
From equation (iv),
 
 
If the pressure of the two gases are the same,
 
 
So that from (d)
 
 
Dalton's Law of Partial Pressure
Dalton's law of partial pressure says that the pressure exerted by a mixture of several gases or vapors (which do not interact in any) equals the sum of the pressures exerted by each gas occupying the same volume as that of the mixture.
 
In Kinetic theory, we assume that the pressure exerted by a gas on the walls of a container is due to the collisions of the molecules with the walls. The total force on the wall is the sum of the forces exerted by the individual molecules. Suppose there are N1 molecules of gas 1, N2 molecules of gas 2, etc., in the mixture.
 
The force on a wall of surface area A is,
 
F = force exerted by N1 molecules of gas 1
 
      +  force exerted by N2 molecules of gas 2
 
      +…… = F1 + F2 + …….
 
Thus, the pressure is
 
          
 
If the first gas alone is in the container, its N1 molecules exerts a force F1 on the wall. If the pressure in this case is p1,
 
 
It is the same for other gases.
 
 
Ideal Gas Equation
Consider a sample of an ideal gas at pressure , volume V and temperature T. Let m be the mass of each molecule and v the rms speed of the molecules. Also, let vtr be the rms speed of the gas at the triple point 273.16K.
 
 
From equation (vi),
 
-----(1)
 
And from equation (viii)
 
 
 
Substituting this expression for v2 in (1),
 
 

Now is the average kinetic energy of a molecule at the triple point 273.16K. As the average kinetic energy of a molecule is the same for all gases at a fixed temperature (equation ix), is an universal constant. Accordingly, the quantity in the brackets, in equation (2), is also a universal constant. Writing this constant as k, equation (2) becomes,

 
 
The universal constant k is the Boltzmann constant and its value is
 
 
upto three significant digits. If the gas contains n moles, the number of molecules is
 
 
 
Using this, equation (x) becomes
 
 
 
where R = NA k, is another universal constant known as the universal gas constant. Its value is
 
R = 8.314 J/mol-K
 
Equation (xi) is known as the equation of state of an ideal gas.
 
 
     
   
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