Reduced Reduced

pressure temperature
Pseudo-reduced
Z can also be determined from
specific volume
a knowledge of PR and vR.

Comparison of Z factors for various gases. 1

2
3
 OTHER EQUATIONS OF STATE

Several equations have been proposed to

represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals Critical isotherm

Equation of State of a pure
substance has
an inflection
point at the
critical state.

This model includes two effects not considered

in the ideal-gas model: the intermolecular
attraction forces and the volume occupied by the
molecules themselves. The accuracy of the van
der Waals equation of state is often inadequate. 4
Beattie-Bridgeman Equation of State

The constants are given in

Table 3–4 for various
substances. It is known to be
reasonably accurate for
densities up to about 0.8ρcr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 3–4. This equation can handle substances
at densities up to about 2.5 ρcr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are

functions of temperature alone are called virial coefficients.
5
6
7
8
 Summary
• Pure substance
• Phases of a pure substance
• Phase-change processes of pure substances
✔ Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
✔ Saturation temperature and Saturation pressure
• Property diagrams for phase change processes
✔ The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface
• Property tables
✔ Enthalpy
✔ Saturated liquid, saturated vapor, Saturated liquid vapor mixture, Superheated
vapor, compressed liquid
✔ Reference state and reference values
• The ideal gas equation of state
✔ Is water vapor an ideal gas?
• Compressibility factor
• Other equations of state
✔ van der Waals Equation of State, Beattie-Bridgeman Equation of State
✔ Benedict-Webb-Rubin Equation of State, Virial Equation of State

9
 Thermodynamics: An Engineering Approach
8th Edition
Yunus A. Çengel, Michael A. Boles
McGraw-Hill, 2015

CHAPTER 4
ENERGY ANALYSIS OF
CLOSED SYSTEMS

Adapted from the lecture slides by Mehmet Kanoglu Copyright © The McGraw-Hill Education.
Permission required for reproduction or display.
 Objectives
• Examine the moving boundary work or P dV work commonly
encountered in reciprocating devices such as automotive engines
and compressors.
• Identify the first law of thermodynamics as simply a statement of
the conservation of energy principle for closed (fixed mass)
systems.
• Develop the general energy balance applied to closed systems.
• Define the specific heat at constant volume and the specific heat at
constant pressure.
• Relate the specific heats to the calculation of the changes in
internal energy and enthalpy of ideal gases.
• Describe incompressible substances and determine the changes in
their internal energy and enthalpy.
• Solve energy balance problems for closed (fixed mass) systems
that involve heat and work interactions for general pure
substances, ideal gases, and incompressible substances.
11
BOUNDARY WORK
Moving boundary work (P dV work):
The expansion and compression work
in a piston-cylinder device.
Quasi-equilibrium process:
A process during which the system
remains nearly in equilibrium at all
times.
Wb is positive → for expansion
Wb is negative → for compression
12
 The boundary
work done
during a process
depends on the
path followed as
well as the end
states.

The area under the process curve on a P-V

diagram is equal, in magnitude, to the work
done during a quasi-equilibrium expansion or
compression process of a closed system. 13
Boundary Work for a Constant-Pressure Process

14
Boundary Work for a Constant-Volume Process
What is the boundary
work for a
constant-volume
process?

15
Boundary Work for an Isothermal Compression Process

16
Boundary Work for a Polytropic Process

For ideal gas

17
Expansion of a Gas against a Spring

18
ENERGY BALANCE FOR CLOSED SYSTEMS
Energy balance for any system
undergoing any process

Energy balance
in the rate form

The total quantities are related to the quantities per unit time is

Energy balance per

unit mass basis
Energy balance in
differential form

Energy balance
for a cycle

19
Energy balance when sign convention is used: (i.e., heat input and
work output are positive; heat output and work input are negative).

Various forms of the first-law relation

for closed systems when sign
convention is used.

The first law cannot be proven mathematically, but no process in nature is known
to have violated the first law, and this should be taken as sufficient proof.
20