B48BC Topic 1 Lecturer Slides

B48BC
Process Engineering B
Thermodynamics
© Heriot-Watt University, B48BC, Process

October 2014 v1 1
Engineering B
Process Engineering B Course
• Process Engineering B is a basic “Engineering
Thermodynamics” course and relies heavily on
mathematical derivations.
• Thus, like mathematics itself, it is important for
students to do all the tutorials and practise
derivations.

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Engineering B
Syllabus:
• First Law of Thermodynamics and basic concepts: Definitions, state
functions, reversible and irreversible processes, heat, work, internal
energy, enthalpy. Closed systems and open systems.
• Throttling & multi-stage compression
• Second Law of Thermodynamics. Applications of the energy
balance to other engineering topics.
• Basic Heat effects: sensible and latent heats, changes of phase,
heats of reaction
• Heat & Work conversions: Cyclic processes, Ideal Work, Efficiency.
• Determining heat and work effects on pure substances.
• Introduction to modelling single phase behaviour: ideal gas law,
van der Waals equations
• Entropy
• Chemical reactions

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Summative Assessments:
Assessable Elements Weightings
Web Test - 1 10%
Web Test - 2 10%
Web Test - 3 10%
Final Exam 70%

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• Summative assessments (3 WEB tests)
• Summative assessments will be organized during
weeks 5, 8 and 12
Summative assessments are written into the tutorial
slots and are designed to give both course lecturer
and students feedback on how well students are
absorbing and understanding the written material
and tutorial exercises.

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TOPIC 1:
CLOSED SYSTEMS & PROCESSES

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Learning Objectives
After studying this topic you should be able to:
• Define the First law of Thermodynamics as it
applies to closed systems involving non-flow
processes.
• Derive equations for the “volume work”
associated with a variety of processes.
• Derive expressions for isochoric, isobaric,
isothermal, adiabatic, and polytropic processes
involving ideal gases.

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1.1 Introduction
Consider a gas being compressed, using a massless and
frictionless piston, from state “1” to state “2”. The
compression is achieved by applying a force FP (in addition to
the external pressure force) to the top of the piston:
Fext
Pext Fext FP
Compression of gas Pext
F1int P1 V1 T1
PF22 int
V 2 T2P2 V2 T2

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1.1 Introduction
In state “1” the external and internal forces acting above and
below the piston are Fext and F1int respectively. Given that
pressure is P = F/A then:
Fext = PextA F1int = P1A
The system and the piston are at rest when:
F1int = Fext P1= Pext
Applying this to state “2”:
F2int = Fext + FP
∴P2A = PextA + FP
FP
P2 = Pext +
A
P2 is now known

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Engineering B
1.1 Introduction
But what about T2 & V2. An Equation of State (EOS) connects
P2, T2 & V2, which for an ideal gas is:
Here, only the ratio of V2 to T2 is known, not the absolute

values. Equations are needed to describe the change from
state “1” to state “2”.
How the system changes state is called the “process” or the

“path” followed.
An expression known as the “volume work” must be

developed for the work done by a closed system.
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1.2 First Law for Closed Systems
The first law may be stated as:
The Change in Total The Sum of All the Energy
Energy Stored Within = Exchanges Between the
the System System and the Surroundings
A closed system is one where no mass can cross the
boundary, only energy in the form of heat or work.
These are both “path functions” because they depend on how

the system moves from state “1” to “2”, as opposed to “state
functions” which are path-independent.
Note that heat and work are also energy exchange terms.
They are manifest only at the boundary as the system changes
state and do not reside within the system.

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The first law of Thermodynamics applied to closed systems is:
∆E = Q + W
Where:
∆E = ∆U + ∆EK + ∆EP
The total change in energy stored by the system ∆E includes:

• Internal Energy Changes, ΔU (J)
1
• Kinetic Energy Changes, ΔEK = mv2(J)
2
• Potential Energy Changes, ΔEP = mgh (J)

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In ∆E = Q + W a general work term W is used. This is because:
• Work by a stirrer or rotating paddle, known as shaft work
(WS) cannot be transferred from a closed system.
• Work by an electrical current (We) cannot be transferred
from a closed system.
• Piston/cylinder devices can used to transfer work from or to
a closed system. This is known as volume work (WV)
Assuming the system is stationary, kinetic and potential energy

terms drop out from ΔE, which reduces the first law to:
∆U = Q + W
You will also see this equation written in lower case, which
typically refers to molar or specific quantities

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In Thermodynamics we need a sign convention for heat and
work. The convention is: Energy into the system is positive.
Energy out of the system is negative.
W
Q
The equations earlier in this lecture have been following this

convention, and thus any of the terms previously used can be
positive or negative.
Note: Other sign conventions are in use. Always check!

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1.3 Volume Work
Work is done on or by a system by moving its boundaries against
an external force. Thus, a stationary boundary does no work.
• By Newton’s first law the forces acting inside and outside a
stationary boundary are the same.
• It follows that a moving boundary must be acted on by an
unbalanced force, which may be arbitrarily small.
• Here it will be assumed that the unbalanced force is so
small that it may be ignored, although not zero.
• If this assumption is made, then any change in state is called
a “quasi-static” process (more about this below).
Quasi-static process lead to maximum work output for an
expansion and minimum work input for a compression

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Volume work WV (also called “Boundary Work”) is done on or
by a closed system as the boundary moves.
Specifically as its volume changes, whenever some external

force F(s) is moved through distance, then volume work will be
done on/by the system.
The mechanical work of moving from position s1 to s2 against a

force F(s) is defined as:
s2
W = − න F s ds
s1

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1.3 Volume Work
Applying our work equation to a typical piston/cylinder gives:
Fext (z )
The work is done on or by the system
moving its boundaries against an
external force Fext(z) is then:
z PV T
Z2
0 W = − න Fext z dz
Z1
In a quasi-static process, the external force Fext(z) is only

infinitesimally different from the internal force Fint(z) .
Z2
W = − න Fint z dz
Z1
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1.3 Volume Work
Transforming the variables as follows:
dV dV
V = zA → =A → dz =
dz A
Substitute this into our expression for work to give:

V2
dV
W = − න Fint V
A
V1
This internal force is generated by the gas pressure acting over

the internal area of the piston (F = PA) giving:
V2
W = − න P V dV
V1
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1.3 Volume Work
Often dependencies, such as the fact that internal pressure P(V)
depends on volume and temperature, are omitted which leads to:
V2
WV = − න PdV
V1
The index “V” is added to the work term to denote that this is
volume work rather that shaft work or work done by an electric
current.
The next step is to apply the first law and a work equation to a
sequence of processes involving an ideal gas, each of which is a
“path specific” process.

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1.3.1 Isothermal Process
Our aim is to derive an expression for the volume work done of an
ideal gas system undergoing an isothermal (T=Constant)
compression or expansion.
For a piston/cylinder device, the starting point for finding the

volume work is: V2
WV = − න PdV
V1
To integrate this expression the relationship between P & V must

be known. For an ideal gas, this relationship is:
nRT
P=
V

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Substituting the ideal gas EOS into the work equation gives:
V2
nRT
WV = − න dV
V
V1
As the process is isothermal:
V2
1 V2
WV = −nRT න dV → WV = −nRTln
V V1
V1
Boyle’s Law is: P1V1 = P2V2 = PV
Which allows Wv to be written as:

P2
WV = nRTln
P1

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In order to solve a WV equation shown previously, either the
pressure ratio or the volume ratio, and two inlet properties must
be known (these are required to fix state “1”).
All processes must comply with the first law: ∆U=Q+WV

It has already been shown that for an ideal gas, the internal
energy is a function of temperature only:
U = U(T)
As the process is isothermal, ΔU = 0 and the first law reduces to:
Q = −WV

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Thus, for an ideal gas undergoing an isothermal compression, the
quantity of energy (in the form of work) entering the system is
equal to the quantity of energy (in the form of heat) leaving the
system.
Once the volume work is known, the direction and amount of

heat transferred is automatically known, so long as the process is
isothermal.
An isothermal compression is sketched on a P-V diagram on the

next slide. The area under the curve P = P(V) is the volume work:
V2
WV = − න P V dV
V1
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2 Isothermal
Process
V
From this, volume work could be estimated graphically by
estimating the shaded area, although of course this is not as
accurate as using the equations!

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1.3.2 Isobaric Process
The aim this time is to derive an expression for the volume work
of an ideal gas system undergoing isobaric compression or
expansion.
As before, two end states must be fixed and the process path
defined to develop an expression. The starting point for this is:
V2
WV = − න PdV
V1
But as the process is isobaric, pressure is constant and so
removed from the integral:
V2
WV = −P න dV → WV = −P(V2 − V1)
V1
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Engineering B
Using the ideal gas law with our WV equation, we get:
WV = −nR(T2 − T1)
All processes must comply with the first law: ∆U = Q + WV
For an isobaric process this may be written as:

U2 − U1 = Q − P V2 − V1
Which can be rearranged to:
Q = U2 − U1 + P V2 − V1

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Enthalpy is defined as H = U + PV . Substituting this into the
final equation of the previous slide gives:
Q = ∆H
It has been shown, for an ideal gas, that enthalpy is a function of
temperature only:
Q = ∆H=ncP T2−T1
This assumes that cP (molar heat capacity at constant pressure) is
independent of T.
On the next slide is a P-V diagram of an isobaric process. The area

under the isobaric line (P = Constant) is the work done on or by
the system.

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P
2 1
P
V2 V1 V
As before, volume work can be estimated graphically from this,
but can be found with more precision through equations.

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1.3.3 Isochoric Process
An isochoric process (V = Constant) is represented below:
 Q (J )
If the volume is constant, then no
volume work can be done on or by the
system. This can occur if the system is
placed in a rigid container (e.g. gas in a
gas cylinder).
2
The volume work is still given by: WV = − න PdV

1
If the piston is locked, then dV = 0 and thus WV = 0.

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Engineering B
1.3.3 Isochoric Process
An isochoric process is shown here. Note
P
that there is no area below the Isochoric 2
P2
process line, confirming that WV = 0
The first law for this process is: P1 1
∆U = Q
V V
For an ideal gas undergoing an isochoric process, so long as cv ≠
cv(T):
Q = ∆U = ncv T − T
2 1

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1.3.4 Heat Capacity
Heat capacity expresses how well a fluid stores the heat
transferred to it. Since heat transfer is a path function, the path
must be specified. Thus, for any general “path”, molar heat
capacity is given by:
dq
cpath =
dT path
The first law for closed systems is given by: ∆u = q + w𝑉
The differential form of this is: dq = du + Pdv
If the process is isochoric, dv = 0 and thus: dq = du

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Engineering B
1.3.4 Heat Capacity
Thus, any energy supplied to the fluid as heat, under isochoric
conditions, is stored as internal energy:
du
cv =
dT v
For isobaric conditions, we start with the molar enthalpy h:
h = u + Pv → dh = du + d(Pv) → dh = du + Pdv + vdP
For an isobaric process, dP = 0: dh = du + Pdv
From the first law du = dq − Pdv
Substitute the first law into previous equation gives dq = dh , so
that
dh
cp =
dT p

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Engineering B
1.3.4 Heat Capacity
In an earlier course on the kinetic theory of gases, it was shown:
2 𝑚𝑣 2
PV = N
3 2
While independent experimental evidence based on the gas laws
gives: N
PV = nRT = RT
NA
Equating the LHS of these two equations gives:
3 𝑚𝑣 2
RT = NA = ekinetic energy
2 2
𝑚𝑣 2
The term is the average molecular kinetic energy of a
NA
2
monoatomic ideal gas, having units of (J/mol).

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1.3.4 Heat Capacity
Since a monoatomic ideal gas can store energy only in the form of
translational kinetic energy, u = ekinetic energy and therefore:
𝑚𝑣 2 3
u = NA and u = RT
2 2
This shows that the internal energy of an ideal gas is a function of
temperature only (independent of pressure and volume).
du
cv was found to be: cv =
dT v
Differentiating w.r.t temperature gives cv for a monoatomic ideal gas:

3
cv = R
2

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Engineering B
1.3.4 Heat Capacity
The previous equation only applies to monoatomic ideal gases. For
diatomic ideal gases, the equipartition theorem states that energy
may be stored using additional modes:
• Two modes, 2 x (1/2R), are from the two rotational modes that
are active at low temperature.
• Vibrations contribute (1R) per mode, but are active only at higher
temperature
• Evaluation of this vibrational contribution is derived from
Quantum Mechanics
Each rotational mode stores 1/2R so for diatomic gases at lower

temperatures, cv becomes:
5
cv = R
2
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Engineering B
1.3.4 Heat Capacity
The definition of enthalpy h for any fluid is:
h = u + Pv
For an ideal gas, this can be rewritten using the ideal gas EOS:
h = u + RT
As internal energy depends solely on temperature for ideal gases, it
follows that enthalpy is also a function of temperature only.
Differentiating the last equation w.r.t temperature gives:
dh du dT →
= +R cp = cv + R
dT dT dT
Thus, for an ideal gas, the difference in heat capacity at constant

pressure and constant volume is always constant and equal to the
universal gas constant.
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Engineering B
1.3.4 Heat Capacity
5
Therefore, for a monoatomic ideal gas, cp is given by: cp = R
2
7
And for a diatomic gas at low temperature, cp is: cp = R
2
For general polyatomic gases (including diatomic gases), the ideal gas
heat capacities are temperature dependent.
Note that for ideal gases, the heat capacities are functions of
temperature only, independent of pressure and molar volume.
Finally, cp and cv can vary, but for an ideal gas are always related by:
cp=cv + R

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1.3.5 Adiabatic Process
It has already been shown that volume work is given by:
V2
WV = − න PdV
V1
For compression or expansion of an ideal gas, this becomes:

V2
nRT
WV = − න dV
V
V1
Taking constants outside the integral gives:

V2
T
WV = −nR න dV
V
V1

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At this point, the derivation is interrupted, as T might depend on V.
The function depends on exactly how the gas is being compressed or
expanded.
The additional restriction is that the process is adiabatic (Q = 0).

therefore, this must somehow determine the T-V relationship.
Start with the first law in differential form:
dU=dQ+dWv
This is used because, regardless of the relationship, energy must be

conserved, and if the system temperature changes, then so will the
internal energy.

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Engineering B
For an adiabatic process, the differential first law reduces to:
dU = dWv
Applying this to the differential change volume work gives:
dU = −PdV
When the process involves an ideal gas, this becomes:
nRT
dU = − dV
V
From the heat capacity at constant volume, the following is deduced:
du
cv = → du = cv dT → dU = ncv dT
dT
The final expression here allows the internal energy change to be

found for any process (by integrating between the two states).

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Engineering B
nRT
Substituting dU=ncv dT into dU = − dV gives:
V
nRT
ncVdT = − dV
V
This gives the desired dependency of T and V, although in differential
form. Thus, integrate this expression:
T2 V2
1 R1 1 R 1
dT = − dV → න dT = − න dV
T cv V T cv V
T1 V1
↙
R
−
T2 R V2 T2 V2 cv
ln = − ln → =
T1 cv V1 T1 V1

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Engineering B
For an ideal gas, the difference between two heat capacities is
constant at all temperatures:
R = cP − cv
Substituting this into our last expression gives:
cv−cp cp
1−
T2 V2 cv V2 cv
= =
T1 V1 V1
The ratio of heat capacities is defined as follows:
cp
γ=
cv
So, for an ideal gas undergoing adiabatic compression or expansion:
T2 V2 1−γ V1 γ−1
= =
T1 V1 V2
T1V1γ−1 = T2V2γ−1 = TV γ−1 = const.
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The assumption is that cv is temperature independent. This is true
for monoatomic ideal gases, but deviations must be expected.
The heat capacities for diatomic gases are nearly constant if the
temperature is low enough.
For poly and diatomic gases, it is possible to use a simple arithmetic

mean heat capacity if temperature changes are small enough.
Integrated mean heat capacities are necessary for larger changes.

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It is instructive to compare the adiabatic process to the isothermal
process on T-V diagram. An isothermal process must follow a
horizontal line (T = const.) from state “1” to “2”. An adiabatic process
must follow a line (TV γ―1 = const.) from state “1” to “2”.
A line of constant TV γ―1 would have the following shape on a T-V

2
sketch: − γ−1 −
T∝V T∝V 5
2
−5
T • For a diatomic ideal gas, where T ∝ V
3 • If the volume is halved, then the
Adiabatic
Process temperature must increase by a factor of
1.32.
2 1 • Therefore, an adiabatic compression curves
up from right to left.
October 2014 v1
V © Heriot-Watt University, B48BC, Process
44
Engineering B
Example 1.3.1 – Problem
T1V1γ−1 = T2V2γ−1 = TV γ−1 = const.
The above equation shows that an ideal gas undergoing an adiabatic

compression or expansion must follow a single curve on a T-V
diagram; moreover, all points on this curve must satisfy the
relationship TV γ―1 = const.
Derive an expression showing what single process path an ideal gas,

undergoing the same adiabatic compression or expansion, would
follow on a P-V diagram

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Example 1.3.1 – Solution
The starting point is the equation given, which indicates how an
adiabatic process can be sketched on a T-V diagram:
TV γ−1 = const.
However, for any ideal gas, all points on this curve must also satisfy
the combined gas law:
PV
= const.
T
Multiplying these two expressions together will cancel the

temperature:
γ−1
PV
TV = PVγ = const.
T
P1V1γ = P2V2γ = PV γ = const.

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Consider a P-V diagram of two process, one isothermal and one
adiabatic:
• The isothermal process follows the hyperbola from state “1” to
“2” and all points on the line satisfy the condition PV = Const. or
P ∝ 1/V
• An adiabatic process must follow a curve from state “1” to “3”
that satisfies the condition PVγ = Const.
• For diatomic gases at low temperature:
cp7Τ2 R 7
γ= = = ≈ 1.4
Τ
cv 5 2 R 5

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A line of constant PVγ would have the following shape on a P-V:
7
−γ −
P∝V or P∝V 5
• For an adiabatic process involving a diatomic

P gas, if the volume is halved, then the
temperature must increase by a factor of
3 2.64
Adiabatic
Process
2 • If the process is isothermal, then when the
Isothermal volume is halved the pressure doubles.
1
Process

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On a P-V diagram, both processes follow an upward curve when an
ideal gas is compressed.
For a fixed degree of compression, the pressure will be raised more

for an adiabatic process than an isothermal process. This is expected,
because:
• For an isothermal compression, all the volume work energy supplied to the
ideal gas is lost when heat energy flows back to the surroundings.
• Thus, the pressure rises only because the particle-wall collision frequency
increases, due to the decreased volume (compression) of the gas.
• For an adiabatic compression, none of the work energy supplied to the
ideal gas is lost as heat energy (in fact, Q = 0).
• Thus, the pressure rises as a result of two factors; the particle-wall collision
frequency rises due to the decreased volume; but the mean-squared
velocity also rises due to the higher temperature.
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P1V1γ = P2V2γ = PV γ = Constant
The above equation fixes any point on an adiabatic line (adiabate)

and is suitable for a P-V sketch.
Repeat the exercise from Example 1.3.1 and find an expression,

showing how an adiabate would look if sketched on a P-T diagram.

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If the process is to be sketched on a P-T diagram, then V should be
eliminated by modifying our initial equation to:
1
Pγ V = const.
For any ideal gas, all points on this curve must also satisfy the
combined gas law: PV
= const.
T
If the first expression is divided by the second, we eliminate volume:
1 T
Pγ V = const.
PV
This gives:
1 1−γ
−1
TP γ = const. or TP γ = const.

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The previous result leads to the curve that an adiabatic compression
or expansion (of an ideal gas) that must follow on a P-T diagram:
1−γ 1−γ 1−γ
T1P1 γ = T2P2 γ = TP γ = const.
Consider how a T-P sketch of two processes might look; one is
isothermal, the other adiabatic. The isothermal process must follow
a straight horizontal line from state “1” to “2” on a T-P sketch.
The adiabatic process must follow a curve that satisfies the above
equation at state “1” and “3”, and at all points between these two
end-states.
For diatomic gases at low temperatures, it has been shown that the
ratio of heat capacities is approximately given by γ ≈ 1.4.
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An adiabate for an ideal gas would have the following shape on a T-P
sketch: γ−1 2
T∝P γ Or T ∝ P7
T • For an adiabatic process involving a diatomic

gas, if the pressure doubles, the
Adiabatic 3 temperature only increases by a factor of
Process 1.22.
• Thus, the adiabatic process line curves
upwards on a T-P sketch approximately as
1 Isothermal 2 shown.
Process

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1.3.6 Volume Work for an Adiabatic Process
For any process, the volume work is given by:
V2
Wv = − න PdV
V1
To integrate this expression, the type of process must be specified,

otherwise the relationship between the P and V variables cannot be
known.
For an adiabatic process, the relation between the variables P & V is

known to be:
P1V1γ = P2V2γ = PV γ = const.
Substituting this into the volume work integral equation gives….

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V2
1 P1V1γ 1−γ 1−γ
Wv = −P1V1γ න γ dV → Wv = − V2 − V1
V 1−γ
V1
Expanding V1γ = V1γ -1 V1, leaving V1 outside the brackets and moving
V1γ -1 inside the brackets gives:
P1V1 γ−1 1−γ γ−1 1−γ
Wv = − V1 V2 − V1 V1
1−γ
Combining the last two terms inside the brackets gives:

γ−1 γ−1
P1V1 V1 P1V1 V1
Wv = − γ−1 − 1 × −1 = 1−
1−γ V 1−γ V2
2

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An alternative expression may be found by replacing the volume
ratio by the pressure ratio, starting from:
γ γ V1 γ P2
P1 V1 = P2 V2 → =
V2 P1
Raising both sides to the same power of (γ – 1)/γ gives:
γ−1
γ−1
V1 P2 γ
=
V2 P1
Substituting this back into the volume work expression gives:
γ−1 γ−1
P1V1 P2 γ P1V1 P2 γ
Wv = 1− =− 1−
1−γ P1 γ−1 P1

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The Ideal Gas Equation can be used to alter the expression:
γ−1
nRT1 P2 γ
Wv = − 1−
γ−1 P1
Sometimes the pressure ratio isn’t known, but the temperature ratio
is. For these cases, we can alter the equation using:
γ−1
1−γ 1−γ
γ γ T2 P2 γ
T1 P1 = T2 P2 → =
T1 P1
Substituting this result into our volume work equation above gives:
nRT1 T2
Wv = −1
γ − 1 T1
The first and last equations of this slide are key for adiabatic
processes within closed systems.
October 2014 v1 57
Engineering B
Take the following equation:
nRT1 T2
Wv = −1
γ − 1 T1
Show that a much simpler expression may be obtained for the
volume work in terms of the temperature difference and molar heat
capacity

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Rearrange the given equation to:
nR
Wv = T2 − T1
γ−1
Substituting cp/cv for γ gives:
nR cvnR
Wv = c T 2 − T1 → Wv = T2 − T1
P−1 cp − cv
cv
↙
Wv = cvn T2 − T1 → Wv = cvn∆T

October 2014 v1 59
Engineering B
This simplified equation can also be derived from the first Law:
∆U = Q + WV
For any adiabatic process, Q = 0. If the adiabatic process involves an
ideal gas, this becomes:
WV = ∆U = ncv ∆T
This applies to any adiabatic process involving an ideal gas, and may
be used if both the initial and final temperatures are known.

October 2014 v1 60
Engineering B
1.3.7 Polytropic Process
In this final section it will be shown that the expressions obtained for
a polytropic process are very similar to those that apply to an
adiabatic process.
Consider a closed system undergoing a polytropic process – this is

the general case where both P and V may change, but only in
accordance with the polytropic law:
PV α = const.
Where α is the Polytropic index. For any gas, the following apply:
• For α = 0 it reduces to the isobaric case.
• For α = ∞ it reduces to the isochoric case.
• Intermediate values of α are general polytropic cases.

October 2014 v1 61
Engineering B
For an ideal gas, additional cases apply:
• For α = 0 it reduces to the isobaric case.
• For α = 1 it reduces to the isothermal case.
• For α = γ it reduces to the adiabatic case.
• For α = ∞ it reduces to the isochoric case.
Note that the polytropic index is very similar to our PVγ, but note
that the polytropic index is empirical and applies to any fluid
undergoing a polytropic process.
PVγ is exact, but only applies to ideal gases undergoing quasi-static

adiabatic processes

October 2014 v1 62
Engineering B
A typical polytropic process is shown below:
P 2
W
Polytropic Process
Q P1V1n  P2V2n  PV n  const
V
When a gas undergoes a polytropic process within a piston/cylinder
device the volume work is given by the area below the polytropic
curve on a P-V diagram.

October 2014 v1 63
Engineering B
Once again, volume work is given by:
V2
WV = − න PdV
V1
This is integrated using the relationship between P and V. For a

polytropic process, this is:
α α α
const.
P1V1 = P2V2 = PV = const. and P=
Vα
Substitute this into the volume work equation to get:
V2
dV
𝑊𝑉 = −P1 V1 α න
Vα
V1

October 2014 v1 64
Engineering B
This expression can be generalised below:
α−1
P1V1 P2 α
WV = − 1−
α−1 P1
It also follows that, for an ideal gas undergoing a polytropic process:
1−α 1−α 1−α
T1 P1 α = T2 P2 α = TP α
Rearrangement of this and use of the ideal gas law leads to:
nRT1 T2
WV = −1
α − 1 T1
Note the similarity of all of these terms with the adiabatic terms,
except that gamma is replaced with the polytropic index.
October 2014 v1 65
Engineering B
All of these relationships are derived in standard textbooks. Some
lean more towards theory (Rogers and Mayhew, 1992) and some
more towards practice (Eastop and McConkey, 1996).
General chemical engineering texts list many important physical

properties (Felder and Rousseau, 2008) and (Perry and Green, 2008).
Standard chemical engineering thermodynamic texts (Smith, Van

Ness, Abbott, 2000) are more discipline-specific.

October 2014 v1 66
Engineering B

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B48BC

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Web Test - 1 10%

Web Test - 2 10%

Web Test - 3 10%

Final Exam 70%

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CLOSED SYSTEMS & PROCESSES

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Here, only the ratio of V2 to T2 is known, not the absolute

How the system changes state is called the “process” or the

An expression known as the “volume work” must be

These are both “path functions” because they depend on how

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The total change in energy stored by the system ∆E includes:

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Assuming the system is stationary, kinetic and potential energy

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The equations earlier in this lecture have been following this

Note: Other sign conventions are in use. Always check!

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Specifically as its volume changes, whenever some external

The mechanical work of moving from position s1 to s2 against a

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In a quasi-static process, the external force Fext(z) is only

Substitute this into our expression for work to give:

This internal force is generated by the gas pressure acting over

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For a piston/cylinder device, the starting point for finding the

To integrate this expression the relationship between P & V must

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Boyle’s Law is: P1V1 = P2V2 = PV

Which allows Wv to be written as:

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All processes must comply with the first law: ∆U=Q+WV

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Once the volume work is known, the direction and amount of

An isothermal compression is sketched on a P-V diagram on the

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For an isobaric process this may be written as:

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On the next slide is a P-V diagram of an isobaric process. The area

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The volume work is still given by: WV = − න PdV

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The first law for this process is: P1 1

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The differential form of this is: dq = du + Pdv

If the process is isochoric, dv = 0 and thus: dq = du

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Differentiating w.r.t temperature gives cv for a monoatomic ideal gas:

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Each rotational mode stores 1/2R so for diatomic gases at lower

Thus, for an ideal gas, the difference in heat capacity at constant

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