ME 200 –Thermodynamics I

Spring 2016

Lecture 27:
Clausius inequality and Entropy
Chapter 6---Using Entropy

The objective: introduce entropy and show its use for

thermodynamic analysis

Yong Li
Shanghai Jiao Tong University
Institute of Refrigeration and Cryogenics
800 Dong Chuan Road Shanghai, 200240, P. R. China
Email : [email protected]
Phone: 86-21-34206056; Fax: 86-21-34206056 1.1
 Lecture Contents
 Last Chapter
» Two equivalent statements of the second law, the Clausius and Kelvin–Planck
statements
– Carnot corollaries
» The irreversibility, irreversible, reversible, and internally reversible processes
» Kelvin temperature scale, expressions for the maximum performance measures of
various cycles operating between two thermal reservoirs
» Carnot cycle ----a specific example of a reversible cycle operating between two
thermal reservoirs.

This Lecture
Clausius inequality, Entropy, Entropy change,
Retrieving entropy data 1.2
Entropy Change in Internally Reversible Processes
 Clausius Inequality

Q heat transfer at the boundary, is an

Cyclic Integral : inexact differential (for path functions)
Integrate over
All parts of boundary T at the boundary
All steps in the whole cycle
Integrand is evaluated at the
boundary of the system

1.3
Clausius Inequality---
demonstration I

1.4
 Clausius Inequality---
demonstration II

The equality and inequality is same as in the K–P statement

The equality applies when no internal irreversibilities in the cycle
The inequality applies when internal irreversibilities are present. 1.5
 “strength” of the inequality

=
 cycle = 0 no irreversibilities present within the system

 cycle > 0 irreversibilities present within the system

 cycle < 0 impossible

The equality in the Clausius inequality
holds for totally or just internally
reversible cycles and the inequality for the
irreversible ones.
1.6
Concepts A quantity is a property if, and only if, its

Entropy Change change in value between two states is

independent of the process

 Two internally reversible cycles.

A and B are arbitrary

The integral of Q/T has the same value for any internally
reversible process between the two states.
The value of the integral depends on the end states only.
The integral represents the change in some property of the system.
Symbol S to denote this property, called entropy
Entropy change::: J/K.
or kJ/K. 1.7
 Entropy--Note
 Clausius realized in 1865 that he had discovered a new thermodynamic property, and
he chose to name this property entropy. It is designated S and is defined as

 Notice
» Actually define the Change in Entropy instead of entropy itself, just
as define the change in energy instead of the energy itself when we
developed the first-law relation.
» Absolute values of entropy are determined on the basis of the third
law of thermodynamics
» To perform the integration in above Eq., needs to know the relation
between Q and T during a process. This relation is often not
available, and the integral can be performed for a few cases only.
1.8
» For the majority of cases have to rely on tabulated data
 Entropy--Notes
 Entropy is a property, it has fixed values at fixed states. S between two specified
states is the same no matter what path, reversible or irreversible.
 The integral of dQ/T gives S only if the integration is carried out along an
internally reversible path between the two states.

 The integral of dQ/T along an irreversible path is not a

property, and in general, different values will be obtained
when the integration is carried out along different
irreversible paths.
 For irreversible processes, S be determined by carrying
out this integration along some convenient imaginary
internally reversible path between the specified states.

1.9
 Entropy--Note

 Enthalpy is introduced without physical motivation and is shown

to be useful for thermodynamic analysis
 No accompanying physical picture is given for entropy
 To gain an appreciation for entropy, need to understand how it is
used and what it is used for

1.10
Retrieving Entropy Data--General Considerations

Sx is the reference value for entropy at

the specified reference state

 The use of entropy values determined relative to an arbitrary reference

state is satisfactory as long as they are used in calculations involving
entropy differences.

1.11
 Entropy Data for Water and Refrigerants
 Tables A-2 through A-18 (Specific Entropy)
» For water, the entropy of saturated liquid at 0.01oC is set to zero.

1.12
 Entropy Data for Water and Refrigerants
 Tables A-2 through A-18 (Specific Entropy)
» For water, the entropy of saturated liquid at 0.01oC is set to zero.
» For the refrigerants, the entropy of the saturated liquid at -40oC is assigned a
value of zero.

1.13
 Entropy Data for Water and Refrigerants
 Vapor data
 s tabulated as a function of either p or T

 Saturation data
» sf and sg are tabulated as a function of either psat or Tsat
» stwo-phase (liquid–vapor mixture) is calculated using the quality x

 Liquid data
» Compressed liquid data are presented for water in Tables A-5.
» In the absence of compressed liquid data, s can be estimated by using the
saturated liquid value at the given T

1.14
 Temperature–entropy(T-s) Diagram
 In the superheated vapor region, constant v lines
have a steeper slope than constant p lines.
 Constant h lines become nearly horizontal as p
is reduced (shaded area).
» states in this region, h is determined
primarily by the T : h(T, p)  h(T). ideal
gas model provides a reasonable
approximation.
» For superheated vapor states outside the
shaded area, both T and p are required to
evaluate h, IG model is not suitable.
 Lines of constant x are shown in the two-phase
liquid–vapor region. 1.15
 Enthalpy–Entropy diagram =
Mollier diagram
 Note the location of the critical point and the
appearance of lines of constant T and
constant p.
 Lines of constant x are shown in the two
phase liquid–vapor region (some figures give
lines of constant percent moisture).
 Intended for properties at superheated vapor
states and for two-phase liquid– vapor
mixtures. Liquid data are seldom shown.
 In the superheated vapor region, constant T
lines become nearly horizontal as p .
 The shaded area, IG model provides a 1.16
reasonable approximation.
 T dS equations
 A pure, simple compressible system undergoing an internally
reversible process.

first TdS equation

second TdS equation

On a unit On a per
mass basis mole basis
1.17
 s—2 phase region

 A change in phase from

saturated liquid to saturated dp  0
vapor at T=c and p=c

1.18
 s—Ideal Gas

Ideal gas, du=cv(T)dT, dh=cp(T)dT , and. pv=RT

cv =constant Special Cases cp =constant

1.19
 s—Using Ideal Gas Table
 The specific entropy is set to zero at 0 K and 1 atm.

 The symbol so(T) denotes the specific entropy at T and 1 atm

 so depends only on T, it can be tabulated versus T (Tables A-22)

1.20
s—Incompressible Substance

Applicable to liquids and solids modeled as incompressible.

cv =constant

1.21