CHAPTER 2

FIRST LAW OF
THERMODYNAMICS-
CLOSED SYSTEM

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OUTLINE
Energy and Energy Transfer
First law of thermodynamics
Energy balance for closed system (control mass)
Introduction of internal energy (U) and enthalpy (H)
Specific Heat, (Cv ),(Cp ).
Mass and Energy balance for open system (control volume)

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ENERGY TRANSFER
For a closed system, the only
two forms of energy interactions
associated with it are heat
transfer and work.

The difference between heat

transfer and work: An energy
interaction is heat transfer if its
driving force is a temperature
difference. Otherwise it is work.

For an open system (control

volume), energy interactions may
include heat transfer, work and
mass transfer.

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ENERGY TRANSFER BY HEAT
Heat: The form of energy that is transferred between two systems (or
a system and its surroundings) by virtue of a temperature difference.
Heat is energy in transition. It is recognized only as it crosses the
boundary of a system.

Temperature difference is the driving force for heat Energy is recognized as heat transfer only
transfer. The larger the temperature difference, the as it crosses the system boundary.
higher is the rate of heat transfer.
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Adiabatic process: A process Heat transfer per unit mass:
during which there is no heat Q = Amount of heat
transfer transferred (kJ)
System is well insulated
System and surroundings are at Amount of heat transfer when heat transfer
the same temperature rate is constant:

Amount of heat transfer when heat transfer

rate changes with time:

During an adiabatic process, a system exchanges

no heat with its surroundings.

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Heat transfer mechanisms:
Conduction: The transfer of energy from the more energetic particles of a
substance to the adjacent less energetic ones as a result of interaction
between particles.
Convection: The transfer of energy between a solid surface and the
adjacent fluid that is in motion, and it involves the combined effects of
conduction and fluid motion.
Radiation: The transfer of energy due to the emission of electromagnetic
waves (or photons).

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ENERGY TRANSFER BY WORK
Work: The energy transfer associated with a force acting through a distance.
If the energy crossing the boundary of a closed system is not heat, it
must be work.
(i.e. rising piston, rotating shaft, electric wire crossing the system boundaries)

Work done per unit mass:

 Heat and work are directional quantities; requires specification on both
the magnitude and direction.

Formal sign convention:

Heat transfer to a system Heat transfer from a system

Work done by a system Work done on a system
Positive (+ve) Negative (-ve)

Alternative to sign convention: Used in Cengel & Boyles

Use subscripts in and out to indicate direction.
Work input = Win
Heat loss = Qout

If direction is not known, assume a direction for

the interaction.
+ve assumed direction is correct
-ve direction of interaction is
opposite of the assumed
Specifying the directions of heat and work.
Heat and Work
Both are boundary phenomena. They are
recognized as they cross the boundaries
of a system.
Systems possess energy, but not heat or
work.
Both are associated with a process, not a
state. Unlike properties, heat or work
has no meaning at a state.
Both are path functions (i.e., their
magnitudes depend on the path followed
during a process as well as the end
states).
Properties are point functions and have exact
differentials (d ).
Example: The total volume change during a process
between states 1 and 2 is:

Path functions have inexact differentials ( ).

Example: The total work done during process 1-2 is: 9
MECHANICAL FORMS OF WORK
There are two requirements for a work interaction between a system and
its surroundings to exist:
there must be a force acting on the boundary.
the boundary must move.

Work = Force Distance

When force is not constant

In many thermodynamic problems, mechanical work is the only form of

work involved. 10
 For quasi-equilibrium
MOVING BOUNDARY WORK process

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.

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Consider a gas enclosed in a piston-cylinder device.
If the piston is allowed to move a distance ds in a quasi-equilibrium
manner, the differential work (boundary work) done during this process is:

Where
P = initial pressure
dV = volume change
P is the absolute pressure and is always positive.
When dV is positive, Wb is positive for expansion
When dV is negative, Wb is negative for compression

Total boundary work from initial state to final state:

To calculate total boundary work, the process by

which the system changed states must be
known, i.e. the functional relationship between P
and V during the process.
P = f (V ) should be available:
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equation of the process path on a P-V diagram.
P-V diagram of quasi-equilibrium
expansion process:

The boundary work = Area under the process

curve plotted on a P-V
diagram

Differential area is equal to differential work:

dA = PdV

Total area under the process curve:

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.

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 A gas can follow several different paths
(with different area underneath) as it
expands from state 1 to state 2.
Each process path gives a different value
for boundary work.

The boundary work done during a process depends

on the path followed as well as the end states.

The net work output is produced during

a cycle if the work done by the system
during the expansion process (area
under path A) is greater than the work
done on the system during the
compression part of the cycle (area
under path B). 14
Some typical processes
(a) Boundary work for a constant-volume process

If the volume is held constant, dV = 0.

Boundary work equation becomes

P
1

V
P-V diagram for V = Constant

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(b) Boundary work for a constant-pressure process

If the pressure is held constant, the boundary work equation becomes

P
2 1

V
P-V diagram for P = Constant

For the constant pressure process shown above, is the boundary work
positive or negative and why? 16
The above equation is the result of applying the ideal gas assumption for
the equation of state. For real gas undergoing an isothermal process, the
integral in the boundary work equation would be done numerically.

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Process Exponent n
Constant pressure 0
Constant volume
Isothermal & ideal gas 1
Adiabatic & ideal gas k = Cp/Cv
Where
Cp= specific heat at constant pressure;
Cv= specific heat at constant volume 18
How to determine the boundary work for polytropic process?
2
n
Wb PdV P CV
1
2 C
n
dV
1 V
1 1
2 1 V2 n V1 n
C dV C
1 V n
n 1
P2V2 P1V1
since C = P1V1n =P2V2n
1 n

For an ideal gas (PV=mRT), this equation can also be written as

mR T2 T1
Wb ,n 1
1 n
For special case of n=1 the boundary work becomes
2 2 V2 V2 Isothermal
Wb PdV CV 1dV PV ln mRT ln
1 1 V1 V1 process
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 EXAMPLE 2.1 Heating of a Potato in an Oven

A potato initially at room temperature (25oC) is being baked in an oven

that is maintained at 200oC. Taking the potato as the system, is there any
heat transfer during this baking process?

Since the potato is the system, the outer surface of the skin of the potato can be
viewed as the system boundary. Part of the energy in the oven will pass through
the skin to the potato. Since the driving force for this energy transfer is a
temperature difference, this is a heat transfer process.
EXAMPLE 2.2 Boundary Work for a Constant-Volume Process

A rigid tank contains air at 500 kPa and 150oC. As a result of heat transfer to the
surroundings, the temperature and pressure inside the tank drop to 65oC and 400
kPa, respectively. Determine the boundary work done during this process.

Solution:
The boundary work can be determined to be
EXAMPLE 2.3 Boundary Work for a Constant-Pressure Process

A frictionless piston-cylinder device contains 5 kg of steam at 400 kPa

and 200oC. Heat is now transferred to the steam until the temperature
reaches 250oC. If the piston is not attached to a shaft and its mass is
constant, determine the work done by the steam during this process.

P, kPa

P0 = 400 kPa
400

m = 5 kg
P = 400 kPa

v1 = 0.53434 v2 = 0.59520 v, m3/kg

EXAMPLE 2.3 Boundary Work for a Constant-Pressure Process

Solution:
Assumption: The expansion process is quasi-equilibrium.
Analysis: Even though it is not explicitly stated, the pressure of the steam within the cylinder
remains constant during this process since both the atmospheric pressure and the weight of the
piston remain constant. Therefore, this is a constant-pressure process, and

or

since V = mv. From the superheated vapor table, the specific volumes are determined to be
v1 = 0.53434 m3/kg at state 1 (400 kPa, 200oC) and v2 = 0.59520 m3/kg at state 2 (400 kPa, 250oC).
Substituting these values yields

Discussion: The positive sign indicates that the work is done by the system. That is, the steam
used 122 kJ of its energy to do this work. The magnitude of this work could also be determined by
calculating the area under the process curve on the P-V diagram, which is simply P0 V for this case.
 EXAMPLE 2.4 Isothermal Compression of an Ideal Gas

A piston-cylinder device initially contains 0.4 m3 of air at 100 kPa and

80oC. The air is now compressed to 0.1 m3 in such a way that the
temperature inside the cylinder remains constant. Determine the work
done during this process.
EXAMPLE 2.4 Isothermal Compression of an Ideal Gas (Cont.)

Solution:
Assumption: 1 The compression process is quasi-equilibrium. 2 At specified condition, air can be
considered to be an ideal gas since it is at a high temperature and low pressure relative to its critical-
point values.
Analysis: For an ideal gas at constant temperature T0,
C
PV mRT0 C or P
V
where C is a constant. Substituting this into boundary work equation, we have
2 2 C 2 dV V2 V2
Wb PdV dV C C ln P1V1 ln
1 1 V 1 V V1 V1
P1V1 can be replaced by P2V2 or mRT0. Also, V2 / V1 can be replaced by P2 / P1 for this case since
P1V1= P2V2.
Substituting the numerical values yields
0.1 1 kJ
Wb (100 kPa)(0.4 m3 ) ln 55.5 kJ
0.4 1 kPa.m3
Discussion: The negative sign indicates that this work is done on the system (a work input), which
is always the case for compression processes.
 EXAMPLE 2.5 Polytropic Process ( )

During some actual expansion and compression processes in piston-

cylinder devices, the gases have been observed to satisfy the
relationship between PVn = C, where n and C are constants. Determine
the work done when a gas expands from 150kPa and 0.03m3 to a final
volume of 0.2m3 for the case of n=1.3

Solution:
Assumption: 1 The process is quasi-equilibrium.
Analysis: The boundary work for this polytropic process can be determined directly from

Discussion: The positive sign indicates that work is done by the system (work output)
Class Activity

A cylinder fitted with a piston contains 0.15kg of air initially

at 2MPa and 350oC. The air is first expanded isothermally to
500kPa, then compressed polytropically with a polytropic
exponent of 1.2 to the initial pressure, and finally compressed
at the constant pressure to the initial state.

i. Determine the work done for each process and the net
work of the cycle.

ii. Sketch the cycle path on a PV diagram

(Given gas constant of air, R=0.287kJ/kg.K, molar mass

of air = 28.96 kg/kmol)
 First law of thermodynamics
First Law of Thermodynamics
(also known as the conservation of energy principle)
Energy can neither be created nor destroyed; it can only change form.

The First Law of

Thermodynamics is the
relationship between heat Q,
work W and the total energy E
of the system and its
surroundings.
ENERGY BALANCE For any system undergoing any process

The net change (increase or decrease) in the total energy of the system during
a process is equal to the difference between the total energy entering and the
total energy leaving the system during that process.

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Energy Change of a System, Esystem

For simple compressible systems

(No electric/ magnetic/ surface
tension effects)
Where
Internal, kinetic, and potential energy changes are

Note:
Energy is a property & its value does
not change unless the state of system
changes.
E = 0 if state of system does not
change during the process.
Mechanisms of Energy Transfer, Ein and Eout
Energy can be transferred to or from a system in three forms:
(1)Heat (2) Work (3) Mass flow

Closed system (fixed mass)

Q = 0 for adiabatic system

W = 0 for systems that involve no work interaction
Emass = 0 for systems that involve no mass flow across boundaries

General Energy Balance

For any system undergoing

any process

In the rate form

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Per unit mass basis
ENERGY BALANCE FOR CLOSED SYSTEMS
Energy balance relation in the case for a closed system:
Qnet,in Wnet,out Esystem or Q W E

where
Q = Qnet, in = Qin Qout is the net heat input Sign convention:
Qin and Wout (positive)
W = Wnet, out = Wout Win is the net work output Qout and Win (negative)

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ENERGY BALANCE FOR CLOSED SYSTEMS
For a closed system undergoing a cycle,
initial states = final states

no mass flow across boundaries, so energy

balance can be expressed in terms of heat and
work interactions For a cycle
E = 0, thus Q = W.

The net work output during a cycle is equal to the net heat input

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Energy balance for a constant-pressure
expansion or compression 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.

For stationary system

W = Wb + Wother

For constant P process,

P0 = P1 = P2

For a constant-pressure expansion

or compression process:

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ENTHALPY, H

Enthalpy for water/steam

Enthalpy H, is a thermodynamic property

Appears in energy balances to calculate Q and W
H U + PV

For Constant P process, enthalpy (kJ)

H = U + PV = Q

where H is simply H2 H1 or Hout Hin

 For a unit mass or mole of substance, enthalpy It can also
be expressed as:
~ ~ ~
Molar enthalpy (kJ/mole) H U PV
H U PV
Specific enthalpy (kJ/kg)

* You can find data(s) for enthalpy(water) in Table F.

SPECIFIC HEATS
Definition: The energy required to raise the temperature of a unit mass of a
substance by one degree.
Specific heat at constant volume, cv:
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, cp:

The energy required to raise the temperature of the unit mass of a substance by one
degree as the pressure is maintained constant.

cp > cv because at constant P,

energy for expansion work
must be supplied

Constant-volume and
constant-pressure
specific heats cv and cp
(values are for helium
gas).
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Express the specific heats in terms of other thermodynamic properties.

change in u with T at constant V

change in h with T at constant P

The equations are valid for any substance undergoing any process.
cv and cp are properties.
cp is always greater than cv .
cv is related to the changes in internal energy and cp to the changes in enthalpy.
common units: kJ/kg. C or kJ/kg.K
molar basis: kJ/kmol. C or kJ/kmol.K

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INTERNAL ENERGY, ENTHALPY,
AND SPECIFIC HEATS OF IDEAL GASES
The differential changes in the internal energy and enthalpy of an ideal gas can
be expressed as
and

Integrating these equations, we can obtain the change in internal energy or

enthalpy for an ideal gas during a process from state 1 to state 2

and

When specific heat is taken constant at an average value

and

For ideal gases, Three ways of

u, h, cv, and cp calculating u.
vary with
temperature only. 39
Specific Heat Relations of Ideal Gases
The relationship between cp, cv and R

dh = cpdT and du = cvdT On a molar basis

Specific heat ratio

A-2

The specific ratio varies with

temperature, but this variation is very
mild.
For mono atomic 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
The cp of an ideal gas can be determined at room temperature.
from a knowledge of cv and R.
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Example 2.7
Neon is compressed from 100kPa and 20oC to 500kPa in isothermal compressor.
Determine:
i) The change in the specific volume
ii) Specific enthalpy of neon caused by this compression.
(given R for neon = 0.4119kJ/kg.K , Cp = 1.0299kj/kg.K)
Solution:
Assumption: At specified conditions, neon behaves as an ideal gas.
Analysis: The compressor inlet, the specific volume is
 END

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