Chestermiller said:
This last equation is incorrect. The analysis starts out with $$dU=TdS-PdV$$You then write:
$$dS=\left(\frac{\partial S}{\partial T}\right)_VdT+\left(\frac{\partial S}{\partial V}\right)_TdV$$so
$$dU=T\left[\left(\frac{\partial S}{\partial T}\right)_VdT+\left(\frac{\partial S}{\partial V}\right)_TdV\right]-PdV$$or
$$dU=T\left(\frac{\partial S}{\partial T}\right)_VdT+\left[\left(\frac{\partial S}{\partial V}\right)_T-P\right]dV$$
So the term in brackets comes partially from the effect of volume on entropy at constant temperature. Finally, ##T\left(\frac{\partial S}{\partial T}\right)_V=C_v##, so:
$$dU=C_VdT+\left[\left(\frac{\partial S}{\partial V}\right)_T-P\right]dV$$
You then substitute the Maxwell relation.
whew this is hard... I hate programming...
The internal Pressure $$Π_T = \left(\frac{\partial U}{\partial V}\right)_T$$
Fundamental Equation for Internal Energy $$dU = TdS - PdV$$
Divide by dV and impose constant T $$ \left(\frac{\partial U}{\partial V}\right)_T = T \left(\frac{\partial S}{\partial V}\right)_T-P $$
Introduce the third Maxwell relation $$ \left(\frac{\partial P}{\partial T}\right)_V = T \left(\frac{\partial S}{\partial V}\right)_T$$
The internal Pressure as a function of P, V, and T: $$Π_T = \left(\frac{\partial U}{\partial V}\right)_T = T \left(\frac{\partial P}{\partial T}\right)_V - P$$
Considering the internal Energy as a function of T and V $$dU\left({T , V}\right) = \left(\frac{\partial U}{\partial T}\right)_VdT + \left(\frac{\partial U}{\partial V}\right)_TdV$$
The First Partial Derivative is the thermodynamic observable known as the constant volume heat capacity
$$C_V = \left(\frac{\partial U}{\partial T}\right)_V$$
The second Partial Derivative is the thermodynamic observable known as the internal Pressure
$$Π_T = \left(\frac{\partial U}{\partial V}\right)_T$$
One of the main ways to express the energy is therefore:
$$dU = C_VdT + Π_TdV$$Is this correct?This brings up a next question. when it says first and second partial derivative. what is the original function it is referring to. What are we taking the partial derivative of to get internal pressure and heat capacity. I probably know this already, but I forgot.
edit: well it appears like it is the first and second partial derivative of that dU function...