Introduction to

Thermodynamics!

Mathematical
Preliminaries
Differentiate the following:
Explicit from implicit equation
Total derivative from partial derivative

Physical significance of the first and

second derivative
Difference of total and partial
derivative
Optimum point
Physical significance of an integral

Thermodynamics
Study of the transformation of
energy and the relationships of the
physical properties of substances
that are affected by these
transformations.
Phenomenological/ Empirical
Cannot be proven by mathematics

Thermodynamic Systems and

Surroundings
A thermodynamic system is a threedimensional
region
in
space
selected to be studied.
Surroundings is the region of physical
space outside the boundaries of the
system. The boundary may be real
or imagined, may be at rest or in
motion, and may change in size or
shape.

Systems
Open system a thermodynamic system for which there
is exchange of energy and matter with the surroundings
Closed system a thermodynamic system for which
there is only exchange of energy with the surroundings,
but the mass of the system remains constant

Isolated System, which can be differentiated into

Thermally isolated system where there is no exchange of
energy and matter with the surroundings, and
Mechanically isolated system where there is no work done on
the system or by the system

Boundary
Adiabatic wall, perfectly insulated
system, well-lagged system
Rigid vessel
Diathermal wall

Examples
Open System
Unsteady state

A tank with a vent

Closed tank with supply line
Closed tank with a bled line or exit line
Unsteady state operation of any equipment or setup

Steady state operation of any equipment or

setup
pipe
Turbine, compressor, pump
Boiler, heat exchanger, condenser

Examples
Closed System
Closed tank
Piston-cylinder setup

Isolated System
Well-insulated closed tank

Extensive and Intensive

Variables
Extensive Variable those variables
that are dependent on the amount of
matter in the system. Examples are
volume, heat capacity
Intensive Variable those variables
that are independent of the amount of
matter in the system. Examples are
viscosity, temperature, and pressure

Total, Molar, Specific

Quantities
Total Energy
kJ
Molar Energy kJ/kgmole
Specific Energy kJ/kg
Total Volume
m3
Molar Volume
m3/kgmole
Specific Volume m3/kg (reciprocal of
density)

State and Path Functions

State Functions- macroscopic quantities that are
dependent only on the initial and final state of
the thermodynamic system, and independent of the
process taken by the system, eg. P, V, T, H, U, G, S, A
Path Function- macroscopic quantities that are
dependent on the process taken by the system,
eg. Q, W.
Differential and Finite Changes of State and Path
Functions

Measurable and Derived

Properties
Measurable: P, V, T
Derived: H, U, G, A, S

Thermodynamic
Definitions

Thermodynamic
Processes
A thermodynamic process is a change of a
system from one state to another.

isothermal constant temperature process

isobaric- constant pressure process
isometric or isochoric constant volume process
adiabatic process a process where there is no
heat evolved from or heat added to the system
isentropic constant entropy process
isenthalpic- constant enthalpy process

Thermodynamic
Processes
polytropic

Gibbs Free Energy

Gibbs Free energy is that portion of
the total system energy that is
available for useful work

Equilibrium
State of Balance
Mechanical Equilibrium- the state in which the
sum of the forces, and torque, on each particle of the
system is zero
Thermal Equilibrium- the states in which two
bodies have the same temperature
Chemical Equilibrium- the state in which there is
no gradient in chemical potential
Chemical Reaction Equilibrium- the state in
reversible reactions in which the rate of the forward
reaction is equal to backward reaction

Zeroth Law of
Thermodynamics
When each of two systems are in
thermal equilibrium with a third
system, the said two systems are in
thermal equilibrium with each other.

Macrostates and
Microstates
Macrostate defined P, V, T
Microstate defined on atomic level
Value of X in a macrostate =
ensemble average of X = sum
(probability that a microstate occurs
with value Xi * microstate value Xi)

Ensembles

Grand Canonical
Canonical
Microcanonical
Isobaric-isothermal


Reversible and Irreversible Processes

A case of a piston-cylinder setup containing

gas inside the cylinder. The top of the
cylinder contains
Case 1: 1 kg of rock
Case 2: 1 kg of sand

Describe Equilibrium States in Case 1

Describe Quasi-static process and
Equilibrium in Case 2
Define Reversible and Irreversible
Processes

Heat

What is heat?
Convention
Heat gained, heat added
Heat losses, heat lost, heat evolved,
heat dissipated

Work
PV-type
Shaft work
Convention
Work added, work consumed, work
supplied, work done on the system
Work produced, work generated, work
done by the system