The helmholtz free fnergy ($F$) is defined using the internal energy ($U$), the absolute temperature ($T$), and the entropy ($S$) as:

equation=14047

When we differentiate this equation, we obtain with the differential Helmholtz Free Energy ($dF$), the variation of the internal energy ($dU$), the entropy variation ($dS$), and the temperature variation ($dT$):

$dF = dU - TdS - SdT$

With the differential of internal energy and the variables the pressure ($p$) and the volume Variation ($\Delta V$),

equation=3471

we finally obtain:

equation

The differential Helmholtz Free Energy ($dF$) is a function of the variations of the absolute temperature ($T$) and the volume ($V$), as well as the slopes the partial derivative of the Helmholtz free energy with respect to temperature at constant volume ($DF_{T,V}$) and the partial derivative of the Helmholtz free energy with respect to volume at constant temperature ($DF_{V,T}$), expressed as:

equation=8187

Comparing this with the equation for the differential Helmholtz Free Energy ($dF$):

equation=3474

and with the first law of thermodynamics, it follows that the partial derivative of the Helmholtz free energy with respect to temperature at constant volume ($DF_{T,V}$) is equal to negative the entropy ($S$):

equation

The differential Helmholtz Free Energy ($dF$) is a function of the variations of the absolute temperature ($T$) and the volume ($V$), as well as the slopes the partial derivative of the Helmholtz free energy with respect to temperature at constant volume ($DF_{T,V}$) and the partial derivative of the Helmholtz free energy with respect to volume at constant temperature ($DF_{V,T}$), which is expressed as:

equation=8187

Comparing this with the equation for the differential Helmholtz Free Energy ($dF$):

equation=3474

and with the first law of thermodynamics, it follows that the partial derivative of the Helmholtz free energy with respect to volume at constant temperature ($DF_{V,T}$) is equal to negative the pressure ($p$):

equation

Since the differential Helmholtz Free Energy ($dF$) is an exact differential, we should note that the helmholtz free fnergy ($F$) with respect to the absolute temperature ($T$) and the volume ($V$) must be independent of the order in which the function is derived:

$D(DF_{T,V})_{V,T}=D(DF{V,T})_{T,V}$

Using the relationship between the slope the partial derivative of the Helmholtz free energy with respect to temperature at constant volume ($DF_{T,V}$) and the entropy ($S$)

equation=3550

and the relationship between the slope the partial derivative of the Helmholtz free energy with respect to volume at constant temperature ($DF_{V,T}$) and the pressure ($p$)

equation=3551

we can conclude that:

equation

Given that the helmholtz free fnergy ($F$) depends on the absolute temperature ($T$) and the volume ($V$), the differential Helmholtz Free Energy ($dF$) can be calculated using:

$dF = \left(\displaystyle\frac{\partial F}{\partial T}\right)_V dT + \left(\displaystyle\frac{\partial F}{\partial V}\right)_T dV$

To simplify this expression, we introduce the notation for the derivative of the helmholtz free fnergy ($F$) with respect to the absolute temperature ($T$) while keeping the volume ($V$) constant as:

$DF_{T,V} \equiv \left(\displaystyle\frac{\partial F}{\partial T}\right)_V$

and for the derivative of the helmholtz free fnergy ($F$) with respect to the volume ($V$) while keeping the absolute temperature ($T$) constant as:

$DF_{V,T} \equiv \left(\displaystyle\frac{\partial F}{\partial V}\right)_T$

thus we can write:

equation