Fundamental Relations

•Introduction
•Enthalpy and entropy dependence on P and T
•Gibbs free energy dependence on P and T
•The Helmholtz Free Energy
•Chemical Potential
•Maxwell’s Equations
•H and S as Function of T at Constant P
•G as Function of T at Constant P
•Reading Chap. 5, 6.1, 6.3, 6.4, 6.5, 6.7
 Introduction
Combined statement of 1st and 2nd Laws of Thermodynamics: dU = TdS – PdV. This
equation provides:
Relationship between U versus V and S:
U = U(S,V) or dU = (∂U/∂S)VdS + (∂U/∂V)SdV
The criteria for equilibrium: in a system of constant V and S; the internal energy has its
minimum value, or, in a system of constant U and V, the entropy has its maximum value.

The problem is that the pair of independent variables (S,V) is rather inconvenient since
entropy is hard to measure or control. Therefore it is desired to have fundamental equations
with independent variables that are easier to control. The two convenient choices are:

• P and T
•V and T
The practical usefulness of thermo of materials is determined by the practicality of the
equations of state for the system (or the relationships which can be established among the
thermo properties).
From practical point of view, P and T pair is the best choice because they are easy to
control and measure.
-For systems with constant pressure the most suitable state function is the Gibbs free
energy G = H - TS
On the other hand, V and T pair is easy to examine in statistical mechanics.
-For systems with constant volume (and variable pressure), the most suitable state
function is the Helmholtz free energy A = U – TS

In principle, any state function can be used to describe any system

at equilibrium, but for a given system some are more convenient
than others. The most convenient one for materials (usually under
constant pressure) is the Gibbs free energy.
 Gibbs Free Energy

G = H – TS = U + PV – TS Combine both:
⇒ dG = dU+PdV+VdP–TdS–SdT
⇒ dG = VdP – SdT
From 1st law: dU = TdS – PdV

G = G(P,T) ⇒ dG = (∂G/∂P)TdP + (∂G/∂T)PdT

⇒ dG = VdP – SdT

Comparing the two equations we see that:

V = (∂G/∂P)T and S = – (∂G/∂T)P

For isothermal-isobaric system the equilibrium state corresponds to the

minimum of the Gibbs Free Energy (dG=0).
- From G = H – TS, we see that low values of G are obtained with low values
of H and high values of S.
 The Helmholtz Free Energy

A = U – TS
⇒ dA = dU–TdS–SdT Combine both:
From 1st law: dU = TdS – PdV ⇒ dA = -PdV – SdT

A = A(V,T) ⇒ dA = (∂A/∂V)TdV + (∂A/∂T)VdT

Comparing the two equations we see that:

P = – (∂A/∂V)T and S = – (∂A/∂T)V

At constant T and V the equilibrium state corresponds to the minimum of

the Helmholtz Free Energy (dA=0).
From A = U – TS, we see that low values of A are obtained
with low values of U and high values of S.
 The Helmholtz Free Energy

•This figure illustrates the criterion for

equilibrium in a closed solid-vapor system at
constant V and T.
•The transfer of one atom to vapor increases U
by a sublimation energy, whereas increase of
entropy is slowing down with increasing
number of atoms in the vapor phase, nv.
T1 < T2

Figure 5.3 - Gaskell

Often, entropy and energies are opposed to each other: High entropies mean low
energies and vice versa. And the entropy part becomes more important at high
temperatures.
 Gibbs Free Energy

G = H – TS Equilibrium is a tradeoff between enthalpy and entropy

•A change to a lower enthalpy state (H < 0, exothermic) usually decreases
the randomness (S < 0). (e.g. solidification and oxidation)
•A change to a higher entropy state (S > 0) usually increases the enthalpy
(H > 0, endothermic). (e.g. melting and evaporation processes)
•All of these processes are characterized by a lowering of the Gibbs free
energy: ∆G = ∆(H - TS) < 0
•A crystal at equilibrium has its minimum Gibbs energy.
Fundamental equations for a closed system:

1st law: U=q– w dU = TdS – PdV

Enthalpy: H=U+PV dH = TdS + VdP
Gibbs energy: G = H – TS dG = VdP – SdT
Helmholtz energy: A = U – TS dA = -PdV – SdT
 Chemical Potential
•If the composition of the system changes during a process, then two
independent variables are not sufficient to describe the state of the system.
•Chemical reactions or exchange with surroundings can lead to the change in
composition (number of moles of different species, ni, nj, nk, ….).
•The Gibbs free energy (as well as other thermodynamic potentials) is an
extensive property, i.e. depends on mass of the system and on number of
different species, G = G(T,P,ni,nj,nk,…..).

If nivaries:
If composition is not changing, dG = VdP – SdT ⇒
⇒ S = – (∂G/∂T)P,ni,nj and V = (∂G/∂P)T,ni,nj,…

where nj is the number of moles of

every species other than the ith species.
 Chemical Potential

This is called the chemical potential of the species i

The chemical potential of the species i is the rate of increase of G with

ni when species i is added to the system at constant T and P and number of
i
moles of all the other species.
•The above equation can be applied to open systems that exchange both matter
and heat with their surroundings, as well as to closed systems where changes in
composition may occur due to chemical reactions.
Similar equations can be written for U, H, and A:
 Chemical Potential

Also, we can rewrite the 1st law for a closed system undergoing a reversible change in composition due to a chemical reaction:

Also, we can obtain the following relations:

These fundamental
relations can be
used to derive
Maxwell equations.
 Maxwell’s Equations

Since U is a state function, the order of differentiation for its second derivative does not matter:

Therefore, for a system with constant composition:

And from other fundamental equations we have:

Maxwell’s equations allow one to derive dependences among

experimentally measurable quantities.
 Maxwell’s Equations: Example 1
Consider the dependence of the entropy of an ideal gas on the
independent variables T and V: S = S(T,V)

For a reversible constant volume process TdS = δqv = dU = CvdT and

Using the following Maxwell equation

and the ideal gas law, PV = RT, which gives

Integration between states 1 and 2 gives

 Maxwell Equations: Example 2

Recall that

While P and can be directly measured experimentally,

It would be useful to express this term through other variables.
•Differentiating the combined 1st and 2nd laws, dU = TdS - PdV by V at constant T we have

Using Maxwell’s equation:

this is valid for any system, we have not

used any approximation.
 Maxwell Equations: Example 2

Considering V = V(P,T):

and differentiating by T at constant V

we have:

⇒
since
(∂V/∂T)P and (∂V/∂P)T are extensive properties
It would be more convenient to express cp - cv through intensive properties. For isotropic
materials we can define

coefficient of volume expansion

isothermal compressibility

α is small for solids

(e.g. 1.7×10-5 K-1 for
Cu, 1.0×10-6 K-1 for
diamond at T = 300 K)
 H and S as Function of T at Constant P
•In a closed one-component system equilibrium, at temperature T
and pressure P, corresponds to the state with ………… Gibbs
free energy G.
•Therefore, in order to predict what phases are stable under
different conditions, we have to examine the dependence of G
on T and P.
•Let us use thermodynamic relations to predict the
temperature dependence of H, S, and G at constant P.

For H(T) :

For S(T):
 G as Function of T at Constant P

G = H - TS , dG = -SdT +VdP
Therefore for constant P:

G(T) for a single phase at P = const

•At all temperatures, the liquid has a higher internal
energy U and enthalpy H as compared to the solid.
Therefore Gl > Gs at low T.
•The liquid phase, however, has a higher entropy S than
the solid phase at all T. Therefore Gl decreases more
rapidly with T as compared to Gs.
•At Tm Gl(T) crosses Gs(T) and both liquid and solid
phases can co-exist in equilibrium (Gl = Gs)
 G as Function of T at Constant P

G(T) for two phases at P = const

At Tm the heat supplied to the system will not rise its temperature
but will be used to supply the heat of melting ∆Hm that is required
to convert solid into liquid.
At Tm the heat capacity Cp = (∂H/∂T)P is infinite,
i.e. addition of heat does not increase T.