Fundamentals
of
Macroscopic Thermodynamics
Sadi Carnot Rudolf Clausius William Thomson Max Planck
1796 - 1832 1822-1888 Lord Kelvin 1858-1947
1824-1907
The Fundamental Problem
A B
• The piston is adiabatic, fixed and
impermeable
• The piston becomes diathermal
• The piston is now allowed to move
• The piston becomes porous
What happens?
The Postulates
• To proceed at the macroscopic level, it is
necessary to introduce some postulatory
basis. Without starting at the microscopic
level, we can’t say much about averages.
• The postulates we will use are those
described by Callen, “Thermodynamics,”
2nd Ed, John Wiley & Sons 1985
The Simplest Postulates
• We will use the simplest set of postulates.
• We will consider that they must be proved a
posteriori rather than be derived by an a
priori proof
Some Definitions
a priori - deduction, based on theory
a posteriori - induction, based on experiment
ab initio - from the beginning
ipso facto - by the fact
Postulate I
There exist certain states (called equilibrium states) of
simple systems that, macroscopically, are characterized
completely by the internal energy U, the volume V, and
the mole numbers, N1, N2,…….., Nr of the chemical
components, where r is the number of chemical
components.
(We could alternatively use mass, rather than moles)
Implications
• Previous history plays no role in
determining the final state
• All microscopic quantum states are allowed
(a priori probability)
• Violations - heat treated steel, non-
Newtonian fluid with hysterisis, ortho and
para hydrogen
Postulate II
There exists a function called the entropy, S, of the
extensive parameters of any composite system,
defined for all equilibrium states and having the
following property:
The values assumed by the extensive parameters are
those that maximize the entropy over the manifold of
constrained equilibrium states.
Extensive vs Intensive Parameters
• Extensive – Related to total extent of system.
– i.e. total energy U, total volume V, total mass M or
moles N. Also total entropy S, enthalpy H etc.
• Intensive – Normalized or not dependent on
system size.
– i.e. Temperature, pressure and chemical potential.
• Normalized Properties – Extensive properties
normalized on mass, moles or volume.
– i.e. u, h, s
Important Observations
• Only for equilibrium states
• The total entropy (all subsystems and
surroundings) is maximized
• We can solve the Fundamental Problem if
we know the Fundamental Relation:
S = S (U , V , N i )
Postulate III
The entropy of a composite system is additive over the
constituent subsystems. The entropy is continuous and
differentiable and is a monotonically increasing function
of energy.
Consequences
• Simplifies mathematics S = ∑Sj
j
• Entropy of each subsystem is a function of the
properties of that subsystem only
S j = S j (U j , V j , N i , j )
• Entropy is a 1st order function of the extensive
properties
S (λU , λV , λN1 ,...) = λS (U , V , N1 ,...)
Consequences
• The monotonic property implies
∂S #
! >0
∂U "V , N1 ,...
• Thus, S can be inverted with respect to U
U = U ( S , V , N1 ,...)
Consequences
• The extensive properties can be normalized
& U V N1 #
S = NS $ , , ,... !
U
u≡
%N N N " N
V
or v≡
s = s (u , v, y1 ,...) N
S
Where yi is the mole fraction s≡
N
Postulate IV
The entropy of any system vanishes in the state
for which
∂U #
! =0
∂S "V , N j 's
As we shall see, this implies that
S → 0 as T → 0
Examples of
Fundamental Relations
• Van der Waal’s Liquid
{
s = s0 + R ln ( v − b ) ( u + a / v )
c
}
• Ideal Gas
3 u v
s = s0 + R ln + R ln
2 u0 v0
