ENTROPY

Prepared by
Engr. Joseph R. Ortenero
Mapua Institute of Technology at Laguna
Malayan Colleges Laguna
 The quantity dQ/T is the cyclic integral of the heat transfer
divided by the absolute temperature at which the heat transfer
occurs. Since the temperature TH is constant during the heat
transfer QH, and TL is constant during heat transfer QL, the
integral is given by:

Where the heat QL leaving the Carnot engine is considered to be

positive.
Entropy is defined as:

For a finite change:

 The heat transfer during a reversible process can be expressed
in differential form as:

 The first law of thermodynamics, for a reversible infinitesimal

change is:

 To relate the entropy change to the enthalpy change:

Entropy for an Ideal Gas
 Entropy for an ideal gas with constant specific heat:

 The integrated form assuming constant specific heats:

For one mole or a unit mass of fluid undergoing a mechanically reversible
process in a closed system, if the specific heat is temperature dependent:

Fr an ideal gas, dH = CpdT and V =RT/P.

The Inequality of Clausius
 The Carnot cycle is a reversible cycle and produces work
referred to as Wrev. Consider an irreversible cycle operating
between the same reservoirs. Since the Carnot cycle
possesses the maximum possible efficiency, the efficiency of
the irreversible cycle must be less than that of the Carnot
cycle.

 From the first law applied to cycle (W= QH –QL), assuming

(QH)irr and (QH)rev are the same:
Therefore;

Hence, for all cycles, reversible or irreversible:

Entropy change for an Irreversible Cycle:

For the reversible Cycle:

For the cycle involving

irreversible process:

This is according to Clausius Inequality.

Thus for reversible and irreversible process:

For an isolated system in which it exchanges no work or heat

with its surroundings:

The result can be generalized to include the surroundings:

Where the equality applies to (ideal) reversible process and the

inequality to a (real)irreversible process. This relation is called
the Principle of Entropy Increase and is often used as the
mathematical statement for the second law.
IDEAL WORK
In a steady-state flow process requiring work, there is an
absolute minimum amount which must be expended to
accomplish the desired change of state of the fluid flowing
through the control volume.
In a process producing work, there is an absolute maximum
amount which may be accomplished as the result of a given
change of state of the fluid flowing through the control volume.
LOST WORK
Work that is wasted as the result of the irreversibilities in a
process and is defined as the difference between the actual
work of a process and the ideal work for the process.
Wlost = Ws - Wideal
The actual work rate is:
Ws = Δ[(H + ½ u2 + zg)m]fs – Q
The ideal work rate is given by:
Wideal = Δ[(H + ½ u2 + zg)m]fs – TσΔ(Sm)fs
The lost work is:
Wlost = TσSG
 The absolute entropy is zero for all perfectly crystalline
substances at absolute zero temperature.

The means for expressing disorder in a quantitative way was

developed by L. Boltzmann and J. W. Gibbs through a quantity Ω,
defined as the number of ways that microscopic particles can be
distributed among the “states” accesible to them. It is given by the
formula:
 In the equation, n is the total number of particles, and n1, n2,
n3, etc., represent the number of particles in “states”
1,2,3,etc. The term “state” denotes the condition of the
microscopic particles, and the quotation marks distinguish this
idea of state from the usual thermodynamic meaning as
applied to a microscopic system.

The connection established by Boltzmann between the

entropy S and Ω is given by the equation:

Where k is Boltzmann constant equal to R/NA.

 Integration between states 1 and 2 yields:

 Substituting values for 1 and 2 into this expression gives:

 Since NA is very large, using Stirling’s formula for the

logarithm of factorials of large numbers:
END OF MODULE