THERMODYNAMICS

CHAPTER 1
BASIC CONCEPTS

Thermodynamics is a way of addressing systems with lots of basic elements in a macroscopic

state of equilibrium.

THERMODYNAMIC SYSTEMS

System: everything macroscopic limited by a surface that can be real or imaginary, which is the
boundary, and its choice depends on measurements as variables and energies.

Surroundings: the region outside the system that interacts with it.

Universe: surroundings plus system, excluding the objects that don’t interact with the system.

Types of boundaries:

 No permissive
o Isolating: no mass or energy exchange.
o Adiabatic: no heat exchange.
o Impermeable: no mass exchange.
o Fixed and rigid: no work exchange.
 Permissive:
o Permeable: mass and energy exchange.
o Diathermic: energy exchange (except work).
o Mobile: change of volume and energy exchange.

Types of systems:

 Open: exchange mass and energy, permeable boundary.

 Closed: exchange energy, impermeable boundary.
 Isolated: don’t exchange, isolating boundary.

STATE VARIABLES

Thermodynamic variables: properties that characterize the state of a system in one moment.
State of a system: conditions in which a system can be found, characterized by the state
variables.

State variables: parameters that allow the description of the state to be chosen according the
information available to be obtained.

Types of state variables:

 External: value depends on the position in space of external bodies.

 Internal: the rest.
 Extensive: proportional to the mass.
 Intensive: non proportional to the mass, as pressure and temperature.

STATE OF THERMODYNAMIC EQUILIBRIUM

A system is in equilibrium when all the properties are constant along time and uniform over
space.

Only isolated systems can be, the other ones just can reach it when aren’t interacting with the
surroundings, so there are no unbalanced driving forces.

THERMODYNAMIC PROCESSES

It is a passage from a state of equilibrium to another as a result of the interaction between the
system and its surroundings.

The process can be tracked through:

 State functions: depend only on initial and final states.

 Process functions: depend also on the path followed.

Types of thermodynamic processes:

 Cyclic: initial and final state are the same.

 Open: initial and final states are not the same.
 Infinitesimal: implies an infinitesimal change in any of the state variables, and the
intermediary states are in equilibrium.
 Finite: changes are not infinitesimal and intermediary states are not necessary in
equilibrium.
 Relaxation process: takes place when a state in equilibrium reaches a new equilibrium
state after being disturbed, and the time it takes is the relaxation time.
 Quasistatic: changes in the system variables are really slow, being the system always in
equilibrium. Changes in state functions cannot be calculated.
 Non-static: time between initial and final state is similar to the relaxation time.
POSTULATES OF THERMODYNAMICS

 First postulate:

Any isolated system evolves in time until it reaches a thermodynamic equilibrium state which
cannot abandon spontaneously.

As a consequence, this lies out of the scope of thermodynamics and cannot be applied to
systems with infinite constituents.

 Second postulate:

Two systems in thermal equilibrium are also in thermal equilibrium with a third one.

Temperature is one additional magnitude to check the equilibrium, and is internal and
intensive.

 Zeroth law:

When two bodies have equality of temperature with a third body, then they have equality of
temperature.

Internal parameters are a function of external parameters and of temperature.