[Physics] Does specific heat change with pressure? If so, why

thermodynamics

As pressure is increased, do we require more energy to increase the temperature from given temperature for the same mass. For example, if we heat water at 1 atm to raise its temperature by 20 degree Celsius, will the heat required be the same when pressure is 3 atm?

Best Answer

I shall try to explain using first law of thermodynamics and Maxwell' relations. For simplicity I am considering $C_v$ . You may extend the argument to $C_p$ as well. Let us consider the change in $C_v$ with w.r.t $V$. From the definition of $C_v$ we can write,

$\left(\frac{dC_v}{dV}\right)_T = \left[\frac{d}{dV}\left(\frac{dU}{dT}\right)_V\right]_T ...(1)$

Switch order of differentiation and from the first law of thermodynamics we can write

$\left[\frac{d}{dT}\left(\frac{dU}{dV}\right)_T\right]_V = \left[\frac{d}{dT}\left(T \frac{dS}{dV} - P \right)_T\right]_V .. (2)$

From Maxwell's relation we have

$ \left(\frac{dS}{dV}\right)_T = \left(\frac{dP}{dT}\right)_V .. (3) $

Substitute Eqn $(3)$ in $(2)$ and after applying product rule, you may obtain

$\left(\frac{dC_v}{dV}\right)_T = T \left(\frac{d^2P}{dT^2}\right)_V$

For an ideal gas or a gas having an equation of state of the form $PV = kT$ or a linear function of $T$, the second derivative of $P$ w.r.t $T$ vanishes and therefore no dependence. For any other equation of state, this is the dependence of specific heat w.r.t to pressure or volume. You may work out in a similar fashion for $C_p$ w.r.t $P$. Only difference is that the thermodynamic quantity will be Enthalpy and not Internal Energy