MSE 308

Thermodynamics of
Extensive and Intensive
Materials
Parameters/Properties
Consider a System:
9 At Equilibrium
9 No gradients within the system
9 Described by a parameter say yi.

Extensive
y1 + y2 = y Parameter
Or Variable

Intensive
y1 = y2 = y Parameter
Or Variable

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MSE 308
Thermodynamics of
Materials
Other Parameters/Properties/Variables
Classification of Variables/Properties/Parameters:
9 Extensive:
o Additive
o State variables (only sometimes)
9 Intensive:
o Not additive
o Field Variables
o Point Variables (i.e., same at each point in a system at equilibrium)
9 Normalized Extensive are Intensive:
o Ratio of Extensive:Intensive (Extensive/Intensive )
o Densities
o Not additive
9 Process:
o Path dependent dependent on past history
o Inexact differentials
9 Conjugate Variables: (see next page)
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MSE 308
Thermodynamics of
Extensive and Intensive
Materials
Parameters/Properties/Variables
Extensive Parameters: Intensive Parameters:
9Q 9P
o indeed is an extensive parameter 9T
o Process variable (not a quantity 9
but transfers from one state to the
next)
9 (electric field)
9 W (work) 9 Any field variable
o indeed is an extensive parameter 9 Ratio of Extensive/Extensive
o Process variable (not a quantity o N/M or N/V or M/V
but transfers from one state to the o These are known as specific
next) properties
9 U (and other free energies)
9 N
9 V
9 M (mass)
9 C (heat capacity)
9 n moles
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MSE 308
Conjugate Variables
W = YdX
Thermodynamics of
Materials

Table 2.1: Types of thermodynamic work in differential form

Work
Thermodynamic Intensive or Extensive or State
Differential
Work Field Variable Variable
(dW)

thermal TdS T = temperature S = entropy

hydrostatic PdV P = pressure V = volume
= chemical N = number of
chemical dN
potential particles
strain
d = stress = strain
mechanical
electrical EdP o E = electric field P o = polarization and: Voltage dq
magnetic HdM g H = magnetic field M g = magnetization
time
P wdt P w = power t = time
dependent

Momentum Mass &

madr r = distance
transfer acceleration
mg = mass &
gravitational mgdr gravitational r = distance
acceleration

Note: The intensive and extensive variable

pairs are known as conjugate variables. For
Knowlton example, T and S are conjugate variables. 4

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MSE 308
Thermodynamics of
Materials
Equilibrium
Types of Equilibrium States:
9 Stable
9 Metastable
9 Unstable 10

8
Transition State
Some Thermodynamic Potential, E 6

4 Unstable
Equilibrium
2 State
0

-2 Metastable
Equilibrium
-4 State

-6
Stable Equilibrium State
-8
-2 -1 0 1 2
Reaction Coordinates,
Knowlton

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MSE 308
Thermodynamics of
Materials
Comments on Energy, Entropy, Heat & Work
Energy and Entropy:
9 "It would be preferable, but for the need for economy of words, to speak
always of 'energy function' and 'entropy function' rather than of energy
and entropy.
9 They are not material entities, but are mathematical functions having
certain properties.
Versus Heat and Work:
9 It is always permissible to speak of the energy and entropy content of a
body relative to some other State.
9 In the same light, it is not permissible to speak of a body's heat or work
content.
9 Heat and work are modes of transfer of energy between one body and
another. Hence, they are path dependent and process variables.

Bridgman, The Nature of Thermodynamics (Harvard, 1941)

Denbigh, The Principles of Chemical Equilibrium (Cambridge University Press,
Knowlton 1981)
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