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Dr.-Eng. Zayed Al-Hamamre
Thermodynamics I
Energy Analysis for Closed Systems
Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
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Content
Energy balance for Closed Systems
Moving boundary work
W
b
for an isothermal process
W
b
for a constant-pressure process
W
b
for a polytropic process
Energy balance for closed systems
Energy balance for a constant-pressure expansion or compression
process
Specific heats
Constant-pressure specific heat, c
p
Constant-volume specific heat, c
v

Internal energy, enthalpy, and specific heats of ideal gases
Specific heat relations of ideal gases
Internal energy, enthalpy, and specific heats of incompressible substances
(solids and liquids)
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The General Energy Balance for A System
Energy balance for any system
undergoing any process
Energy balance in the rate form
For constant rate, 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
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Change in amount of
energy contained within
the system during some
time interval
=
Net amount of energy
transferred in across the system
boundary by heat transfer
during the time interval
-
Net amount of energy
transferred out across the
system boundary by work
during the time interval
Energy Balance: Closed Systems
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Energy Balance: Closed Systems
dE Q W o o =
Differential Form:
Time Rate Form:
dE
Q W
dt
- -
=
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Gas Compressor
Energy Balance: Closed Systems
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Energy Balance: Closed Systems
The work (boundary) done on an
adiabatic system is equal to the
increase in the energy of the system
The energy change of a system
during a process is equal to the net
work and heat transfer between the
system and its surroundings
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Cycle Energy Balance
The energy balance for any system undergoing a thermodynamic cycle takes the form
For the cycle, since the system is returned to its initial state after the cycle, there is no net
change in its energy
E = 0
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Cycle Energy Balance
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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.
For a cycle AE = 0, thus Q = W.
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.
The General Energy Balance for A System
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Moving Boundary Work
Moving boundary work (P dV work): The
expansion and compression work in a piston-
cylinder device.
The work associated with
a moving boundary is
called boundary work.
A gas does a differential
amount of work oW
b
as it
forces the piston to move
by a differential amount ds.
Quasi-equilibrium process: A process
during which the system remains nearly
in equilibrium at all times.
W
b
is positive for expansion
W
b
is negative for compression
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The area under the process
curve on a P-V diagram
represents the boundary
work.
The boundary work done during
a process depends on the path
followed as well as the end
states.
The net work done during a
cycle is the difference between
the work done by the system
and the work done on the
system.
Moving Boundary Work
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Polytropic, Isothermal, and Isobaric processes
Polytropic process: C, n (polytropic exponent) constants
Polytropic process
Polytropic and for ideal gas
When n = 1 (isothermal process)
Schematic and P-V diagram
for a polytropic process.
Constant pressure process
What is the boundary work for a
constant-volume process?
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A rigid tank contains air at 500 kPa and 150C. As a result of heat transfer to the surroundings,
the temperature and pressure inside the tank drop to 65C and 400 kPa, respectively. Determine
the boundary work done during this process.
Example
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Example
A frictionless pistoncylinder device contains 10 lbm of steam at 60 psia and 320F. Heat is now
transferred to the steam until the temperature reaches 400F. If the piston is not attached to a shaft
and its mass is constant, determine the work done by the steam during this process.
the specific volumes are determined using tabulated superheated data
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Example
A pistoncylinder device initially contains 0.4 m
3
of air at 100 kPa and 80C. The air is now
compressed to 0.1 m
3
in such a way that the temperature inside the cylinder remains constant.
Determine the work done during this process.
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Example
A gas in a pistoncylinder assembly undergoes an expansion process for which the relationship
between pressure and volume is given by
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Example Cont.
P = constant
V

=

c
o
n
s
t
a
n
t

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Example
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Summary
For a closed system:
2 1
1 2
constant
P V
P V
n
n
PV =
| |
=
|
\ .
Expansion/Compression (Moving Boundary)
Work (Ideal Gas OR liquid):
2
2 2 1 1
1
2
2
1 1
1 1
, ( 1)
1
ln , ( 1)
P V PV
P d V n
n
V
P d V PV n
V

= =

| |
= =
|
\ .
}
}
Ideal Gases ONLY:
( 1) / ( 1)
2 2 1
1 1 2
2
2 1
1
2
2
1 1
( )
, ( 1)
1
ln
n n n
T P V
T P V
mR T T
P dV n
n
V
P dV mRT
V

| | | |
= =
| |
\ . \ .

= =

| |
=
|
\ .
}
}
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Energy balance for a constant-pressure expansion or
compression process
H W U
b
A = + A
For a constant-pressure expansion or
compression process:
An example of constant-pressure process
General analysis for a closed system
undergoing a quasi-equilibrium constant-
pressure process. Q is to the system and W is
from the system.
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Constant-Volume and Constant-Pressure Processes
Since for closed systems, n is also constant
zero
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Constant-Volume and Constant-Pressure Processes
Since
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Specific Heat
Specific heat at constant volume, c
v
: The energy required to raise the temperature of the unit
mass of a substance by one degree as the volume is maintained constant.
Specific heat at constant pressure, c
p
: The energy required to raise the temperature of the
unit mass of a substance by one degree as the pressure is maintained constant.
Specific heat is the energy required to raise
the temperature of a unit mass of a substance
by one degree in a specified way.
Constant-volume and constant-
pressure specific heats c
v
and c
p
(values are for helium gas).
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The equations in the figure are valid for any substance undergoing any process.
c
v
and c
p
are properties.
c
v
is related to the changes in internal energy and c
p
to the changes in enthalpy.
A common unit for specific heats is kJ/kg C or kJ/kg K. Are these units identical?
The specific heat of a substance changes with temperature.
True or False?
c
p
is always greater than c
v
.
Formal definitions of c
v
and c
p
.
Specific Heat
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Ideal-gas constant-pressure
specific heats for some
gases (see Table A2c for
c
p
equations).
At low pressures, all real gases approach ideal-gas
behavior, and therefore their specific heats depend
on temperature only.
The specific heats of real gases at low pressures are
called ideal-gas specific heats, or zero-pressure
specific heats, and are often denoted c
p0
and c
v0
.
u and h data for a number of gases
have been tabulated.
These tables are obtained by choosing
an arbitrary reference point and
performing the integrations by treating
state 1 as the reference state.
In the preparation of ideal-gas
tables, 0 K is chosen as the
reference temperature.
U, H and Specific Heat of Ideal Gas
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(kJ/kg)
For small temperature intervals, the specific
heats may be assumed to vary linearly with
temperature.
Internal energy and enthalpy change when specific
heat is taken constant at an average value
The relation A u = c
v
AT is valid for any kind
of process, constant-volume or not.
U, H and Specific Heat of Ideal Gas
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1. By using the tabulated u and h data. This
is the easiest and most accurate way
when tables are readily available.
2. By using the c
v
or c
p
relations (Table A-
2c) as a function of temperature and
performing the integrations. This is very
inconvenient for hand calculations but
quite desirable for computerized
calculations. The results obtained are
very accurate.
3. By using average specific heats. This is
very simple and certainly very
convenient when property tables are not
available. The results obtained are
reasonably accurate if the temperature
interval is not very large.
Three Ways of Calculating Au and Ah
Three ways of calculating Au.
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Specific Heat Relations of Ideal Gases
The c
p
of an ideal gas can be determined
from a knowledge of c
v
and R.
On a molar basis
The relationship between c
p
, c
v
and R
Specific heat ratio
The specific ratio varies with temperature,
but this variation is very mild.
For monatomic gases (helium, argon, etc.),
its value is essentially constant at 1.667.
Many diatomic gases, including air, have a
specific heat ratio of about 1.4 at room
temperature.
dh = c
p
dT and du = c
v
dT
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Equations for Process Calculations: Ideal Gases
Since
For an ideal gas in any mechanically reversible closed-system process
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Equations for Process Calculations: Ideal Gases
But
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Isothermal Process
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Isobaric Process
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lsochoric (Constant- V) Process
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Adiabatic Process: Constant Heat Capacities
An adiabatic process is one for which there is no heat transfer between the system and its
surroundings
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Adiabatic Process: Constant Heat Capacities
Apply to an ideal gas with constant heat capacities undergoing a mechanically reversible
adiabatic process
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Adiabatic Process: Constant Heat Capacities
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Polytropic Process: Constant Heat Capacities
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Polytropic Process
Isobaric process: = 0.
Isothermal process:, = 1.
Adiabatic process: = .
Isochoric process: dV/dP = V/P; for constant V,
=
Paths of polytropic processes
characterized by specific values
of
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The specific volumes of incompressible
substances remain constant during a process.
The c
v
and c
p
values of incompressible
substances are identical and are denoted by c.
Incompressible substance: A substance whose specific volume (or density) is
constant. Solids and liquids are incompressible substances.
U, H and Specific Heat of Solids and Liquids
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Internal Energy Changes
Enthalpy Changes
The enthalpy of a compressed liquid
A more accurate relation than
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Approximations for liquids and solids
Using Saturated Liquid Data
(Compressed Liquid Rule)
Using Incompressible Substance
Model
f
f
f
f
v v
h h
u u
s s
~
~
~
~
2 1 2 1
2 1 2 1 2 1
2 1 2 1
( )
( ) ( )
( )
p v
c c c
u u c T T
h h c T T v P P
h h c T T
= =
=
= +
~
Generalized equations for the estimation of molar volumes of saturated liquids ( Rackett equ.)