JOULE THOMSON EFFECT ( POROUS PLUG EXPRESSION RESULT ) Consider a thermally insulated cylinder PQ divided into two portions

by a porous plug G and fitted with two non-conducting pistons A & B. Suppose the piston A forces slowly one gram mole of a gas through the porous plug at a constant pressure P. Now the escaping gas pushes back the piston B at a smaller constant pressure P. Let V and V be the volumes of the gas before and after passing through the porous plug respectively. External work done on the gas by the piston = PV External work done on the gas by the piston = PV Net amount of external work done by the gas = PV - PV In addition to this, the gas performs internal work also to pull its molecules further apart against their mutual attraction forces while passing through porous plug. The internal work done when one gram mole of gas expands from volume V to volume V. v v ( a/V )dV = a/V -a/V W = PV - PV + a/V -a/V Total work done by the gas, -----------1

According to Vander Waals equation ( P + a/v )( v - b ) = RT PV + a/V Pb ab/V = RT ab/V can be neglected because a and b are small. Therefore PV + a/V Pb = RT PV = RT a/V + Pb, PV = RT a/V +Pb PV = RT a/V + Pb

Therefore, PV - PV = a *1/V - 1/V + b (P - P ) Substituting the value of PV - PV in Equation 1

W = a *1/V - 1/V + b (P - P ) + a/V a/V = 2*a/V a/V + - b (P - P ) ------------2

Since (a/V) and (a/V ) are small quantities, we can use the approximate relation PV = RT V = RT/P therefore V = RT/P and V = RT/P Therefore a/V = Pa/RT and a/V = Pa/RT

Now equation 2 becomes W = 2 *Pa/RT - Pa/RT + - b (P - P ) = 2a/RT (P - P ) - b (P - P ) = (P - P ) *2a/RT b ] -------- 3

As the system is thermally insulated, this work is done utilizing the internal energy often gas. Hence the gas cools. Let dT be the fall in temperature and if Cp is the specidic heat at constant pressure, then the amount of heat must be supplied to restore the original temperature will be Cp dT calories or Cp dT Jergs. Hence W = Cp dT J = (P - P ) *2a/RT b ] dT = (P - P ) / CpJ *2a/RT b ] ----------4

the above expression for joule Thomson cooling. It is clear from the above equation that i) ii) iii) If 2a/RT > b, then dT = +ve and then there will be cooling effect because dT represents fall in temperature. If 2a/RT > b, then dT = -ve and then there will be heating effect. If 2a/RT = b, then dT = 0 and there will be no effect.

The temperature at which joule Thompson effect is zero and changes sign is known as inversion temperature T. 2a/RT = b T = 2a/Rb