Thermodynamics

Carnot Joule

Lord Kelvin Clausius

Josiah Willard Gibbs

Gases

Liquids

Solids

Systems to Be Considered Currently

Phase Equilibria

Chemical Equilibria

Electrochemical Systems

Colligative Properties

Systems to be Considered

Must Be in an Equilibrium State

No Flow or Turbulence

No Thermal Gradients

Independent of History

Droplets - Surface AreaBands - Length

Pizoelectrics - Electric Fields

Atmosphere - Gravitational Fields

Superconductors - Magnetic Fields

Systems that Could be Considered, but …..

Simple System

Macroscopically homogeneous, isotropic, uncharged, and chemically inert, that [is] sufficiently large that surface effects can be neglected, and that are not acted upon byelectric, magnetic or gravitational fields.

Herbert B. Callen

State Variable - Pressure

Barometer

Manometer

Evangelista Torricelli

State Variable - Volume

State Variable - Amount

Standard Kilogram

State Variable - TemperatureDaniel Gabriel Fahrenheit Three Fixed Points

• Brine Solution 0oF• Ice-Point 32oF• Body Temp 96oF

Anders Celsius Two Fixed Points• Ice Point 100oC• Boiling Point 0oC

Why a Limited Number of Variables?

Equations of StateIt is customarily assumed that an Equation of State can alwaysbe written in a form involving only intensive quantities …

Arthur W. Adamson

The state of a substance in thermal equilibrium can be fixed byspecifying any two of the three variables, pressure, molar volume and temperature.

g(P, Vm, T) = 0

Walter J. Moore

Such relationships, expressing intensive parameters in termsof the independent extensive parameters, are called equations of state.

Knowledge of a single equation of state does not constitute completeKnowledge of the thermodynamic properties of a system. We shallSee, subsequently, that knowledge of all the equations of state of a systemIs [now] thermodynamically complete.

Herbert B. Callen