On the temperature variation of the specific heats of hydrogen and nitrogen

Abstract

The energy of a gram molecule of an ideal gas can be calculated from the kinetic theory. From this, by the application of the Maxwell-Boltzmann hypothesis, the molecular specific heats at constant volume, S v , of ideal monatomic and diatomic gases are deduced to be 3R /2 and 5R/2 respectively at all temperatures. R is the gas constant per gram molecule = 1⋅985 gm. cal./° C. The corresponding molecular specific heats at constant pressure, S p , can be obtained by the addition of R. In the case of real gases, which obey some form of characteristic equation other than P. V = R. T, it can be shown from thermodynamical considera­tions that the value of S p depends upon the pressure, but as the term involving the pressure also includes the temperature, S p is not independent of the tempera­ture but it increases in value as the temperature is reduced. Assuming the characteristic equation proposed by Callendar, i. e. , v - b ­­= RT/ p - c (where b is the co-volume, c is the coaggregation volume which is a function of the temperature of the form c = c 0 (T 0 /T) n , n being dependent on the nature of the gas), it is easy to show from the relation (∂S p /∂ р ) T = -T(∂ 2 ν /∂Τ 2 ) р , hat S p = S p 0 + n (n + 1) cp /T; and, by combining this with S p – S v = T(∂ p /∂Τ) v (∂ v /∂Τ) p = R(1 + ncp /RT) 2 , the corresponding values of S v can be obtained.