Chemical Engineering Thermodynamics

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Topics from the Syllabus

First Law of Thermodynamics,

Energy Balance for Closed Systems,
Equilibrium,
The Phase Rule,
The Reversible Process,
Enthalpy, Heat Capacity,
Mass and Energy balances for Open Systems.

1
Objective of Chapter

 Basic Concept of Temperature, Pressure, Work, Energy

and Heat
 Microscopic and Macroscopic analysis in
Thermodynamics, Intensive and Extensive Properties
 Types of Thermodynamic System and Processes
 First Law of Thermodynamics and Other Basic Concept
 Energy Balance for Closed System
 Mass and Energy Balance for Open System

2
Specific and molar Quantities

Mass mole Molar mass Total Volume

m n M Vt

For specific quantities, divide by mass

For example, specific volume

For molar quantities, divide by mole

For example, molar volume

3
 Temperature Scale

Boiling
Point

Freezing
Point

4
 Pressure
In thermodynamics,
The collision of molecule on the wall of system constitutes
pressure by the system to the surrounding. In order to
maintain equilibrium same force should be applied by the
surrounding on the system.

Different Pressure Terms:

Aboslute

Atmospheric

Vacuum

Note: Generally, absolute pressure is used in thermodynamics

Gauge

5
Work

-ve sign imposed for sign convention to

make sure that the work done for
compression process should be positive and
vice versa is true for expansion process

6
Energy
On macroscopic approach, basically, energy constitutes kinetic and
potential energy (K.E & P.E) possessed by the particles. There may
exists other forms of energy

Work done by moving an object from u1 to u2 on the same baseline,

which is equal to the change in K.E,

Similarly, Potential energy is given by

7
Heat
Heat flows from hotter body to the colder body, i.e Q, which is usually
stored in the form of K.E and P.E.

8
Microscopic and Macroscopic
approach in Thermodynamics

Microscopic Macroscopic

Molecular level approach Quantity of matter (mass) level approach

Studied in statistical thermodynamics Studied in classical thermodynamics

9
Intensive and Extensive Property

Density P
Density
P

Property (P) remains same, which does

not depend on amount of substance,
called as intensive property
Example: Density will remain the same,
hence intensive property

Vice versa is true for extensive property

T, P, V, U, Cp, Concentration, entropy, gibbs energy

10
System and Surrounding
Closed system Open System
Control Volume

Surrounding
System

Control Surface

11
Some Keywords in Thermodynamics

Types of Thermodynamic System Types of Thermodynamic Process

Open System: E and M pass Isothermal: T constant

Closed System: Only E can pass Isochoric: V constant

Isolated System: Neither E nor M can pass

Isobaric: P constant

Adiabatic System: Neither heat (Q) nor M Adiabatic: No heat transfer through
can pass but energy of the system can boundary of system
change by work

12
First Law of Thermodynamics

Joule’s Experiment

Statement

Observed that when stirred different fluids, for each degree rise in temperature, a fixed
amount of work was required, and therefore concluded that there is relation between heat
an work.

First Law of thermodynamics:

Statement

Total energy is constant and when one form of energy disappears then it appears in another
form.

13
First Law of Thermodynamics

Energy Balance for Closed System

Q and W will be +ve when

energy added to the system
by transfer of heat and work
Surrounding from surrounding to system,
System Q and W never stored in the
system.

P.E and K.E stored in the closed system and appears as internal energy when added

14
First Law of Thermodynamics
For closed system, often only internal energy of the system changes

For differential change

and are extensive property and depends on the material

15
 First Law of Thermodynamics
Now Lets convert extensive property to intensive, For homogenous fluids only
Molar volume and specific volume Molar and specific internal energy

Already discussed in previous slides about specific quantity

Note: T and P for
homogenous fluid
are independent of
quantity of material
i.e intensive property

For n=1 and

16
First Law of Thermodynamics (Equilibrium)

All the forces Absence of any

should be in change or tendency
exact balance towards any change

Applicable to
macroscopic level

* Difference in Temperature, Pressure and chemical potential can cause imbalance

in the system

17
 Equilibrium and Phase Rule
Equilibrium
Absence of change and tendency towards change at macroscopic level.

At Equilibrium, all forces are in exact balance.

Phase Rule Phase is a homogenous region of matter

Try to assign the state of the homogenous fluid to be fixed

When two intensive variable are set at a constant value or known then the state of
the system is believed to be fixed
Justification: T and P are known then the other thermodynamic property can be
calculated, It means that the state of system is fixed after specifying T and P
When two phases are in equilibrium, the state of the system is fixed only when one
intensive property is known

Justification: water vapor and liquid water at 1 bar, always exists at 100 oC

18
Equilibrium and Phase Rule
For multiphase and non-reacting system
 Number of degree of freedom

 Number of phases

 Number of Chemical species

Phase rule provides the information about the how many number of variables
to be set in order to fix all other remaining variables and thus intensive state of the system

Phase rule variables are intensive properties

F=0, Invariant When and N=1

The above condition fulfills only when one species have three phases at equilibrium, i.e
Called as triple point (0.01 oC and 0.0061 bar)

19
First Law of Thermodynamics
State Function and Path Function
3
2

State Function: Does not depend on the path

between the final and initial state

Path Function: depends on the path

Between the final and initial state

20
First Law of Thermodynamics
State Function and Path Function

Differential of heat and work are not changes

But it is amount

Internal energy is a state function while heat and work are path function

21
 Reversible Process
A process is reversible when its direction can be reversed at any point by an infinitesimal
change in external condition
Is ideal and yield minimum work input and
maximum work output

22
Reversible Process
A process is reversible when its direction can be reversed at any point by an infinitesimal
change in external condition

I II III

23
Reversible Process
Chemical reversible reaction can be achieved when a differential pressure
or temperature is applied to the reactor.

Characteristics of a reversible process

• Frictionless
• Never change more than differential value from equilibrium
• A succession of equilibrium state can be achieved
• Can be reversed at any point by applying differential change in external
condition
• Ability to retrace the original path when reversed

24
Reversible Process: Constant V and P processes

For mechanical reversible, closed system process

To find work done in an irreversible process for
same process, one need the information of
efficiency

For homogenous fluid

a) Constant Volume Process i.e Work will be zero

(Constant V)

Heat transfer in a mechanical reversible, constant V and closed system process equals
the change in U of the system.

25
Reversible Process: Constant V and P processes

For mechanical reversible, closed system process

b) Constant Pressure Process

Collectively, we define a quantity called enthalpy U+PV=H

U, H and V are mass or molar quantities

Heat transfer in a mechanical reversible constant pressure, closed system

process equals the enthalpy change of the system.

26
Enthalpy

The usefulness of this terms appears where pressure is maintained to be constant

For flow processes, it is important in heat exchanger, pumps, turbines, engines,

distillation column for calculating heat and work

Specific volume, internal energy and enthalpy can be determined as a function of T and p,
Further Q and W can be easily evaluated.

U, P and V are all state function, therefore, H is also a state function and intensive property.

27
Heat Capacity

Capacity word means

Smaller the temperature change after given a quantity of heat to a substance greater the
heat capacity of that substance

C is a state function eventhough Q is a path function.

a) Heat Capacity at constant volume (also called sometime as specific heat)

Mechanical reversible, constant volume process

28
Heat Capacity

b) Heat Capacity at constant pressure

29
Mass Balance for Open System

Flow rate (F.R) measurement variables

Mass F.R Mole F.R volumetric F.R velocity

30
Mass Balance for Open System

Apply continuity equation on control volume

(when net FR into the

control volume)

(when net FR out of the

control volume)

Special cases like steady state flow process, incompressible fluid etc.

31
Mass Balance for Open System

Note: for molar rate, molar density will be used

Steady state flow process

Rate of change of mass/mole FR does not change with time

32
Energy Balance for Open System

Rate of change of energy within the control volume equals the net rate of
energy transfer into the control volume

U, u and z are all related to average property of stream (may be control volume
can be considered to be very small “micron size”)

Work can be of several forms: Work done by fluid particle at entry or exit of the
control volume, shaft work by rotating shaft (like in turbines and compressors)

33
Energy Balance for Open System

Sometimes, kinetic and potential energy can be assumed to

be negligible compared to other forms of energy

* For steady state processes Accumulation of energy will be zero

For steady state and steady flow process:

Compression and expansion

doesn’t takes place
So only shaft work

34
Energy Balance for Open System

When control volume has one entry side

and one exit side

Mass rate will be same at both entry and

exit

When K.E and P.E are negligible, then

35
Numerical Problems
Numerical Problems
Numerical Problems
Numerical Problems
Chemical Engineering
CHAPTER-3
Thermodynamics
 Volumetric Property of Pure Fluids

Overview
Generalized (Equation of State) EoS

Realistic Fluid behavior N, P, V, T U, H

Q, W

Ideal EoS

Metre-gauge steam train arriving at Kodai Road

station near Madurai in June 1965. Credit: Ian A diesel engine, photo credit: Steam turbine for power generation.
Manning and Poochi Venkat https://www.tellzauto.com Photo Credit: Mitsubishi Power

36
Volumetric Property of Pure Fluids

• 1-2 Sublimation Curve (Solid-Vapor)

• 2-3 Fusion Curve (Solid-Liquid)
• 2-C Vaporization Curve (Liquid-Vapor)

2  Triple point
C  Critical Point
F=0 When three phases
co-exists (Triple point)
F=1, Univarient, When two phases
co-exists

F=2, Divarient, When a single

phases occurs

Fluid exists at a temperature greater

than Tc, it is said to be supercritical PT diagram for a pure substance.

37
Volumetric Property of Pure Fluids
Boundary changed to region here in
PV diagram
Regions: solid/liquid; liquid/vapor;
solid/vapor co-exists in equilibrium

Line represents single phase which is

in equilibrium

Isotherms are shown as dotted lines

Isotherms below Tc shows three Segment BC: single phase liquid at

segments: where horizontal segment vaporization temp (boiling)
represents the liquid/vapor equilibrium Segment CD: single phase vapor
with all possible mixtures of both; left exists at condensation temperature
extreme of horizontal line shows 100%
liquid while right extreme represents
100% vapor

PV diagrams for a pure substance. (a) Showing solid, liquid, and gas regions. (b)
38
Showing liquid, liquid/vapor, and vapor regions with isotherms.
Volumetric Property of Pure Fluids… more

Curve BCD: represents saturation

segments, at each point on BCD, a
horizontal line is connected for co-
existence of both phases at saturation
pressure and temperature related to
isotherms.
That specific pressure can also be
called as vapor pressure, like a vertical
line crosses a vaporization curve in the
PT diagram

Left of the segment BC: Subcooled liquid region Vertical lines of isotherms are more
Right of the segment CD: Superheated vapor region steeper ??? Why ??

PV diagrams for a pure substance. (a) Showing solid, liquid, and gas regions. (b)
39
Showing liquid, liquid/vapor, and vapor regions with isotherms.
Virial Equation of State

From the experiment,

It was observed that the isotherms for the gases and vapor lying above and
to the right of CD can be expressed as

---(1)
or

From the experiment, it was found that

∗ (as P 0) --(3)

Statement: “a” only depends on the temperature and independent on chemical species
as P 0

40
Virial Equation of State

Here, we introduce a term called compressibility factor, which is dimensionless ratio given
by

From 2,3 &4

Alternate form

B’, C’ and D’, in addition B, C and D are the virial coefficients

B’ and B are the second virial coefficient (two body interaction)
C and C’ are the third virial coefficient (three body interaction)

41
Virial Equation of State

Establish a relation 1) B’, B, 2) C’ , B and C 3) D’,D,B,C

TC = 190.6 ± 0.3 K
PC = 46.1 ± 0.3 bar

Compressibility Factor Z for methane

42
Ideal Equation of State

From virial equation P 0 then B/V and C/V2 term will be very small and then Z 1

B/V and C/V2 , B and C tends to zero then the value of these terms becomes insignificant.

In the absence of molecular interaction, i.e contribution from P.E will be zero then the
internal energy will be the only function of temperature i.e contribution from K.E

(Ideal Gas)

(Ideal Gas)

43
Ideal Equation of State

(Ideal gas)

44
Ideal Equation of State

45
Process Calculation in Ideal Gas

Process calculations in ideal gas (Q and W)

Work done for mechanically reversible closed system is given by

For ideal gas in a closed system mechanical reversible process

After rearrangement,

Degree of freedom for 1 component and one phase system =2

The above equation is function of P, V and T where only two intensive variable is
independent.

46
Process Calculation in Ideal Gas
Equation 8 through 10, valid for
Ideal gas, closed and mechanical
reversible.

8-A)

also convert Cv to Cp

47
Process Calculation in Ideal Gas

Isothermal Process

48
Process Calculation in Ideal Gas

Isobaric Process

49
Process Calculation in Ideal Gas

Isochoric Process

50
Process Calculation in Ideal Gas

Adiabatic Process

Using equation 7,8 and 9

Cv is constant here with Temp.

After integration, we have

/ / /

We denote

51
Process Calculation in Ideal Gas

Therefore, It can be shorten as

( )/
10 (a to c)

The above equation (10) valid only when it is case of ideal gas with constant heat capacities
undergoing mechanical reversible adiabatic expansion or compression.

52
Process Calculation in Ideal Gas

For adiabatic closed system,

Cv is constant here with temperature

11

53
Process Calculation in Ideal Gas

Usually, T2 and V2 are unknown, therefore we can do the elimination of V2 using equation (10-c)

( )/ ( )/

Equation (12) is valid for ideal gas, adiabatic, closed system and reversible process with
constant heat capacities

Note that the Monoatomic gas

Diatomic gas

Polyatomic gas

54
Process Calculation in Ideal Gas

Polytropic Process

Isobaric, Isothermal, Adiabatic and isochoric

55
Cubic Equation of State (EoS)

Simple Cubic Equation of State (1873)

PVT behavior of the vapors and liquids

to account for attractive forces

between molecules

to account finite size of molecule

are the function of species

𝐴𝑡 ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒,
𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑖𝑑𝑒𝑎𝑙 𝑠𝑡𝑎𝑡𝑒 𝑖𝑠 𝑙𝑒𝑠𝑠 𝑡ℎ𝑎𝑛 𝑡ℎ𝑒 𝑟𝑒𝑎𝑙 And
pressure at ideal state is more than real

𝑁𝑜𝑡𝑒: 𝐻𝑒𝑟𝑒 𝑃 𝑎𝑛𝑑 𝑉 𝑖𝑛 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑎𝑟𝑒 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑎𝑛𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

56
Cubic Equation of State (EoS)

Roots of the simple cubic EoS

For T>Tc solution yields only one real root

For T=Tc solution yields three real roots, and

they are equal

For T<Tc all three roots are real and positive

and they have some different physical
significance

57
Cubic Equation of State (EoS)

Determination of simple cubic EoS parameter (a and b)

For simple cubic EoS

Isotherm posses horizontal inflection at the critical point

Which turns mathematically into

also

Since a root exists at infection point that is V=Vc

Expanding in cubic form

58
Cubic Equation of State (EoS)

---(A)

Rewrite simple cubic EoS

Plug T=Tc and P=Pc

Rearrange,

---(B)

Compare equation A and B

---(C)

59
Cubic Equation of State (EoS)

General Cubic EoS (started in 1949)

General cubic equation can be applied for

VdW, RK, SRK and PR equations

Redlich Kwong equation

Now, is also dependent on temperature.

Analogous to equation C, we can write

and

60
Cubic Equation of State (EoS)

Vapor and Vapor like Roots

Two new variable

We have from generic cubic EoS

---(V1)

Using substitution of and previous generic cubic EoS

---(V2)

Initial estimate should start from idea gas value i.e V=RT/P

61
Cubic Equation of State (EoS)

Liquid and Liquid like Roots

Solve for V from right side of above equation from V1

---(L1)

Solve for Z from right side of equation V2

---(L2)

Initial estimate should start from idea gas value i.e V=b and Z=

62
Cubic Equation of State (EoS)

Develop a graphing calculator to draw

the isotherm of various fluids
Let’s explore Python

 User should be given choice for the name of fluid to study

 User should be given the option to choose the type of EoS like
PR, SRK, RK etc.
 Should support a wide variety of units as input and output
 User should be given flexibility to choose a set of input parameter
 Plot graph after the complete analysis. (matplotlib)

Finally try for GUI Support (Atlas toolkit, tkinter).

63
Theorem of Corresponding States: Acentric Factor

Two Parameter Correlation (Example van der Waals, RK equations)

Experimental study shows that the compressibility factor Z for different fluid posses similar behavior
when correlated as a function of reduced temperature Tr and reduced pressure Pr

General statement from the experiment:

All fluid when compared at the same Tr and Pr, have approximately the same Z and all deviate from
the ideal gas behavior to about the same degree.
The above statement holds true for the simple fluids (Argon, Krypton, Xenon)

Three Parameter Correlation (Example SRK, PR equations)

Two parameter correlation shows deviation for complex fluids, therefore Pitzer and coworker introduced
third parameter known as acentric factor 𝜔, which is the characteristics of molecular structure

Acentric factor of a pure chemical species is defined with reference to Vapor Pressure

Where S is the slope, 𝑃 is the saturation

reduced vapor pressure and 𝑇 is the
saturation reduced temperature

64
Theorem of Corresponding States: Acentric Factor

Three Parameter Correlation

If we know Tc, Pc and Psat, then 𝜔 can be

found easily for any fluid

Approximate temperature dependence of the reduced vapor pressure

Statement from three parameter correlation: All fluids having the same value of 𝜔, when compared at
the same Tr and Pr, have about the same value of Z and all deviate from the ideal gas behavior to about
the same degree.

65
Generalized Correlations for Gases

A generalized Correlation was made for Z (Compressibility factor) and B (second virial coefficient)

Pitzer Correlation for compressibility Factor

--(1)
𝑍 and 𝑍 are function of both Pr and Tr

Slope between Z and 𝜔 will give 𝑍

Lee/Kesler correlation (Widely used)

Values of Z0 and 𝑍 are provided in tabular form

in the text books (Appendix D)
Fig: The Lee/Kesler correlation for Z 0 = F 0(Tr, Pr)

66
Generalized Correlations for Gases

Three-dimensional plot of the Lee/Kesler correlation for Z 0 = F 0(Tr, Pr)

67
Generalized Correlations for Gases

A generalized Correlation was made for Z (Compressibility factor) and B (second virial coefficient)
Tabular form of Z correlation is diadvantage
Pitzer Correlation for the 2nd Virial coefficient

is the reduced second virial coefficient

--(3)

--(4)

68
Generalized Correlations for Gases

Given by Abbott Equations:

.

Dotted as The virial-

coefficient correlation is
represented by the
straight lines; the
Lee/Kesler correlation,
by the points

69
Generalized Correlations for Gases

3rd Virial coefficient

Where and are the reduced second and third virial coefficient respectively

A Pitzer correlation for third virial coefficient is written as

70
Generalized Correlations for Gases

Expression for C0 and C1 given by Orbey and Vera, but a little modified and simple
term is given for C1

. .

Since equation 3V is the equation in cubic form of Z, which requires iteration method to
solve for Z, where Z=1 will be a good choice for the starting guess

71
Generalized Correlations for Liquids

The previous correlations for gases (Lee/Kesler) can also be used for liquids but
with a low accuracy, However Rackett proposed a simple correlation for finding
molar volume for saturated liquids
/

[ ]

Lydersen, Greenkorn, and Hougen’s correlation for liquid volume

72
Generalized Correlations for Liquids

Figure A: Generalized density correlation for liquids. 73

Example Problem

74
Example Problem

75
CHAPTER-4
Second Law of Thermodynamics

Some clarification was required in first law of thermodynamics,

Work can be transformed into various forms of energy like electrical, mechanical etc.

69
 Second Law of Thermodynamics

Counterparts of first Law with respect to second law

Statement 1: It is impossible by a cyclic process to convert the heat absorbed by

the system completely into work done by the system

Statement 2: No process is possible which consists solely in the transfer of heat

from one temperature level to a higher one.

Axiom1. There exists a property called entropy S, which for systems at internal
equilibrium is an intrinsic property, functionally related to the measurable state
variables that characterize the system. Differential changes in this property are given
by the equation:

is the system entropy

70
Second Law of Thermodynamics

Axiom2. (The Second Law of Thermodynamics), The entropy change of any system and
its surroundings, considered together, and resulting from any real process, is
positive, approaching zero when the process approached reversibility, Mathematically
given as,

By classical definition: Entropy is the measure of energy which is not available to do work.

You can see in real life situation, that all the available energy cannot be utilized to do work.
Otherwise efficiency of doing work will be 100%, which is not possible to achieve

71
Second Law of Thermodynamics

Application of the Second Law to Simple Heat Transfer

Let us consider two reservoir at temperature TH and TC, the heat transfer associated with
reservoir be the QH and QC respectively (heat exchange between both).

Entropy changes of the reservoir TH

HOT COLD

Entropy changes of the reservoir TC

72
Second Law of Thermodynamics

Application of the Second Law to Simple Heat Transfer

Assume one reservoir to be system and other be surrounding

Add equation S1 and S2

HOT COLD

In other sense, it confirms that the heat flows from higher temperature to lower

73
Second Law of Thermodynamics

Application of the Second Law to Heat Engine

Figure H) (a) Carnot engine; (b) Carnot heat pump or

refrigerator.
74
Second Law of Thermodynamics

Application of the Second Law to Heat Engine Internal-combustion engine and

the steam power plant.
heat engines: requires a high-temperature source of heat,
and discard heat to the environment.

Let us imagine, engine as system and two reservoir as

surrounding as shown in figure H
Sign convention: heat transfer from hot reservoir with respect to engine is equal to QH (+ve)
Sign convention: heat received by the cold reservoir with respect to engine is equal to QC (-ve)

From first law of thermodynamics:

Engines work in cycles therefore,

Engines work in cycles, therefore

75
Second Law of Thermodynamics

Application of the Second Law to Heat Engine

Total entropy change, when engine operating, therefore

Total entropy change, while operating engine, therefore

Combining (A) and (B), by eliminating QH , we have

76
Second Law of Thermodynamics

Application of the Second Law to Heat Engine

When, engine is not working then W=0

-ve sign is here because we are considering the engine also, while if there is a direct contact
between reservoirs +ve sign otherwise equation (C) and (D) are similar

If the process is reversible completely then

Therefore, is –ve, it means heat from the

engine and hence W is –ve, it means
work is done by the engine

Thus whenever a heat engine operates in a completely reversible manner, then the
engine is said to ideal engine, popularly known as Carnot’s engine (1824).

77
Second Law of Thermodynamics

Statement:
It is impossible to construct an engine that operating in a cycle, produces no effect, (in system
and surrounding) other than the extraction of heat from the reservoir and the performance of an
equivalent amount of work.

Replacing W from A and B, and rearranging, we have

78
Second Law of Thermodynamics

Thermal Efficiency of Heat Engine:

Can be defined as the ratio of work done “W” by engine after receiving an amount of heat QH
from the hot reservoir

Therefore, thermal efficiency of carnot engine will be

 cannot be improved as it operates in completely reversible process

 1 only when TH  inf or TC  0, which is not practically possible

Cold reservoir as atmosphere, river, ocean while hot reservoir as furnace, combustion chamber

Maximum efficiency can only be achieved by Carnot engine for same reservoir condition

79
Second Law of Thermodynamics

Heat Engine
Cycle of Carnot Engine

Important Conclusion on Carnot Engine

• Its efficiency depends on temperature levels

and not upon the working substance of the
engine.
• For two given heat reservoirs no engine can
have a thermal efficiency higher than that of a
Carnot engine.

PV diagram showing a Carnot

cycle for a working fluid in the
ideal-gas state.
80
Second Law of Thermodynamics

Heat Pump

Reversed process of Carnot engine is Carnot

heat pump also known as Carnot refrigerator

Here work is required and it is used as pump. 1 QH

It is used to pump heat from lower temperature
heat reservoir to the higher temperature heat P 4
reservoir. TH

Usually, measure of the quality of heat pump

2 TC
can be achieved as Coefficient of Performance. QC 3
It is defined as heat extracted at lower V
temperature divided by the work required
PV Diagram of a Carnot refrigerator or
reversed Carnot engine

81
Second Law of Thermodynamics

Carnot Engine with Ideal Gas State Working Fluid

a  b Adiabatic Compression
b  c Isothermal Expansion
c  d Adiabatic Expansion
d  a Isothermal Compression
In this case,
Ideal gas working fluid is regarded as system
For isothermal case, b  c and d  a

and

Dividing 1/2

PV diagram showing a Carnot

cycle for a working fluid in the
ideal-gas state.
82
 Second Law of Thermodynamics

Carnot Engine with Ideal Gas State Working Fluid

a  b Adiabatic Compression
c  d Adiabatic Expansion
For adiabatic process dQ=0 then

For both adiabatic case, a  b and c  d

Integrate for both adiabatic process from TC to TH

We have

PV diagram showing a Carnot

cycle for a working fluid in the
ideal-gas state.
83
Second Law of Thermodynamics

Entropy
D
A and B are two equilibrium state of a particular
fluid
ACB and ADB are two reversible process P
B
A

and C

Vt
is independent of path i.e

Then by definition, dSt=0, thus entropy of a system is constant during the reversible
Adiabatic process also called as isentropic.

84
Second Law of Thermodynamics

Characteristics of Entropy
D
1) No definition of entropy in context of classical
thermodynamics, only del S can be found
P
2) For finite reversible process, B
A

For irreversible process,

Vt
Choose an arbitrarily reversible process that undergo
same change of state as actual process and evaluate
change in entropy.

Entropy is a state function and hence entropy change

of irreversible or reversible process will be identical.

85
Second Law of Thermodynamics

Entropy change for the ideal gas state

Mechanically reversible process

We know

Eliminating dU

After rearrangement

For ideal gas state

and

86
Second Law of Thermodynamics

Entropy change for the ideal gas state

General equation for
calculation of
entropy change in
ideal gas state
Where is the molar entropy of ideal gas state regardless of the
process involved in
it.

Try to develop a relation for ideal gas, constant heat capacity and reversible adiabatic i.e.,
Isentropic process,

( )/

87
Second Law of Thermodynamics

Entropy Balance for Open System

Entropy is not conserved

Balance

Sum over all control volume

is the heat transfer w.r.to particular part of
the control surface associated with ,
,

88
Second Law of Thermodynamics

Entropy Balance for Open System

Divide by yield

For unit mass of fluid flowing through control volume

,

89
Second Law of Thermodynamics

Calculation of Ideal Work

In steady state flow process, which requires work, a minimum amount of work can be realized
through the control volume for a desired change in state.

While a maximum amount of work is produced for a given change of state through control
volume.

However, the above process is accomplished only when process is completely reversible.
For such a process, entropy generation equals to zero
For a uniform surrounding temperature

Or

Substitute the equation A in the energy balance for open system

90
Second Law of Thermodynamics

Calculation of Ideal Work

Shaft work is work of a completely reversible process,

which can be given a name ideal work

When K.E and P.E is negligible

can be factored when considering single stream flow condition

For reversible process

91
Second Law of Thermodynamics

For work required  or is +ve

Minimum work required which is smaller than the

Efficiency

will be maximum work produced (-ve), which is larger than Ws or

92
Second Law of Thermodynamics

Work which is lost because of the irreveribilities in the process is called the lost work.

Difference of actual work and the ideal work for same change of state

For capturing the lost work, we need to include energy generation term in our formulation
Using energy balance and entropy balance, we can write

.
.

We get
.

93
Second Law of Thermodynamics

For the case of a single surrounding temperature , the steady state entropy balance,

Equation E becomes

Multiplication by gives

Subtracting L1 and L2, we have

According to 2nd law of thermodynamics, and therefore

When a process is completely reversible, and

is the lost energy that is unavailable for work i.e +ve

94
Second Law of Thermodynamics

For the special case: single stream flowing through control volume, then mdot becomes a factor
Entropy change

. .

. .

Again we have

95
 Chemical Engineering Thermodynamics

Note: Readers can suggest any error or mistake in this ppt file.
Objective of Chapter

 Able to connect the fundamental property relations for U,

H, G and A in general form applicable to any closed PVT
system, also applied to 1 mole of homogenous fluid
 Establishing a Maxwell Relation and converting the various
PDF to make use of PVT data

Other objectives will be included later after the completion of this sections.

1
Partial Derivative Relations

Difference between inlet and outlet values for the enthalpy of gas, del_H must come from
experiment

But in this chapter our purpose is to develop

• Equations from 1st and 2nd law of thermodynamics to relate those properties
mathematically

• Derive equations that allow calculation of Del_S and Del_H values from PVT and heat
capacity data

• Develop generalized correlations that provides estimates of property values in the

absence of complete experimental information

2
 Partial Derivative Relations
First Law of Thermodynamics for Reversible Process

Apply previous relations for reversible process

Combined
1.1

Three important properties (H, A, and G) connected by P, V, T, and S as seen in the

equation 1.1
--(A)
--(C)
--(B)

3
 Partial Derivative Relations
A and G applied in phase change and chemical equilibrium calculation
--(A)
Multiply by n and differentiate equation (A)

Differentiation of nA and nG can be obtained similarly,

and

For n=1, and homogenous fluid of constant composition, all together written as

1.2 Not restricted to reversible

1.4 process since they all depend on
The state of system only.
Written for closed PVT system
1.3
1.5 Exact Differential Expression

4
Partial Derivative Relations
The equation 1.2 through 1.5 are the genral equation applicable regardless of number of
phases and nature of reactivity whether chemically inert or chemical reactions occurs.

Each special variables U, H, A and G related to some pair of independent variable

Given as

We can see that Gibbs energy (G) is of special kind as it depends on the T, P which
is readily available and under control during the experiment

Since the equations 1.2 through 1.5 are exact differential equations, then it can be
easily derived in the form of partial derivatives as follows

5
Partial Derivative Relations
For example, let’s remind the differential equation when a function is dependent on two or
more variables can be written as

---(1.6)

Right side of the equation (1.6) is exact differential equation only when

Check whether is the exact differential or not??

6
 Partial Derivative Relations
Now do the comaprision analysis on the equation 1.2,

−−−(1.7)

Similarly, we can write for equation 1.3, 1.4 and 1.5 as

−−−(1.8) −−−(1.9) −−−(1.10)

The equations from 1.7 through 1.10 are well known as Maxwell relations

The equations 1.7 through 1.10, can be remembered with some trick. (remind me once in the next lecture)

7
 -S U V
H F
-P G T
−−−(1.8) −−−(1.9) −−−(1.10)

−−−(1.7)

Good Physicists Have Studied Under Very Fine Teachers 8

DAY-2 Partial Derivative Relations,
Residual Properties and Two Phase
Systems
Partial Derivative Relations

Enthalpy and Entropy as Functions of T and P

Thinking about the

ideal gas situation

Theses are general equation for homogenous fluid of

constant composition

Note: Coefficients of the above equations can be obtained from experimental

PVT data and heat capacity data

9
 Partial Derivative Relations

Isobaric Compressibility

Isothermal Compressibility

Can be applied to change of state at constant volume

Note: and V are the weak functions of P for liquids, Therefore if required, can be
assumed as constant

10
Partial Derivative Relations

Internal energy as a function of P

Start from the basic

relation to get a

11
 Partial Derivative Relations

Internal energy and entropy as functions of T and V

For example, F(x,y), we can write

Similarly for U and S

The above general equation valid for homogenous fluids of constant composition

12
Numerical Problem

13
DAY-3 Partial Derivative Relations,
Residual Properties and Two Phase
Systems
 Partial Derivative Relations
Gibbs Energy as a Generating Function

Using mathematical
Identity

All terms are dimensionless and right side

includes enthalpy rather than entropy

The above equation transformed to partial differentiation at constant T

If as a function of T and P is given,

then, V/RT and H/RT can be known.
at constant P,

14
 Partial Derivative Relations
Gibbs Energy as a Generating Function

Simple equation shown below can be utilized for finding the remaining properties,

and Now see, why G or G/RT serves as

Generating function

15
 Residual Properties Relations

Residual Properties
Unfortunately no experimental method for the measurement of G or G/RT is known

General residual form can be written as mind that M is not

change in property
Rearranged as
Corrections to ideal state gas
Residual properties such as VR, UR, HR SR and GR (all molar properties)

Main purpose of this section is to obtain residual properties from PVT data or from EoS

Z can be obtained from PVT data or EoS and hence VR can be obtained
Finally Vactual can be obtained and similarly G, U and H can be obtained

16
 Residual Properties Relations

Some residual relations

Can be written as

Therefore, red text term will get eliminated since it is a constant value independent of T,
when change in property calculated. Or here we can arbitrarily omit red term.

17
Residual Properties Relations
G, S, U and H are accounted as change in property between two given
states, therefore

We know, Z=PV/RT, and then can be

obtained from PVT data. Integration can be
obtained numerically or by graphical method

18
 Residual Properties Relations
Enthalpy and entropy calculation from residual property

and

Reference state at
T0 and P0
Now use, and

Reference state data

Then finally, can be obtained from,
NIST Chemistry
Use ICPH or MCPH and Webbook,
ICPS or MCPS http://webbook.nist.gov

19
 Residual Properties Relations
Enthalpy and entropy calculation from residual property

Note that the reference

state is not required if
we are calculating
change in property

20
Numerical

21
 Residual Properties Relations
Residual Property from Virial EoS

It would be attractive if we solve the integration part using the EoS approach instead of
numerical or graphical methods.
For explicit formulation in V or Z, We can apply the EoS directly
For example:
Use previous
G relation

We can make independent of P

for our convenience if required

22
 Residual Properties Relations
Residual Property from Virial EoS

at const T

We can make use of this to substitute where possible, using

this relation we can transform the equation independent of P

Now we can
apply
pressure
explicit three
term Virial
EoS

23
 Residual Properties Relations
Residual Property from Virial EoS

24
 Residual Properties Relations
Generalized Properties correlations for gases

For calculation of thermodynamics properties, generally two data are needed i.e. Heat
capacity and PVT data.
Occasionally PVT data (experiment) are missing, therefore generalized methods taught
earlier can be applied to residual properties as well.

T D.5 to D.12 of 8th edition book of

Van Ness and Smit helps to
evaluate right side of the main
equation and hence HR and SR
Also, we know that can be found

If used correctly, it reduced to, and

25
26
 Residual Properties Relations
Alternate Form: Generalized second-virial-coefficient correlation

27
Residual Properties Relations

Computational Path

28
Numerical

29
Numerical

30
 Residual Properties Relations: Extension to Gas Mixture

Pseudo reduced parameter, Lee Kesler correlations can be used now to Calculate
from Tpr and Ppr values, and then HR/RTPc and SR/R can be computed

Example: Estimate V, HR, and SR for an equimolar mixture of carbon dioxide(1) and
propane(2) at 450 K and 140 bar by the Lee/Kesler correlations.

30
 Two Phase Systems

Curve shown in PT diagram of pure substance represent phase boundaries.

Molar or specific values (i.e V, U, H, and S) changes abruptly when crosses the
boundary of curve, however molar or specific gibbs energy G does not change upon
phase transition.

At constant T and P and n, we have

Hence for both the phases at equilibrium

and are change in entropy and volume respectively when phase change
from occurs at the eqb at T and P

31
 Two Phase Systems

Phase transition from liquid to vapor

OR

32
 Two Phase Systems

The equation reduces to famous

equation called Clausis/Clapeyron Slope
equation

latent heat of vaporization is

vapour phase is
directly connected to vapour
ideal and molar volume of liquid is
pressure curve.
negligible compared to molar
volume of vapor

Antoine
Equation

33
 Two Phase Systems

When saturated liquid and vapor co-exists at equilibrium, any extensive property can
be computed as

34
Numerical Problem

34
Numerical Problem

34
Duct Flow of Compressible
Fluids
Duct Flow of Compressible Fluids

35
 Duct Flow of Compressible Fluids

Assumptions: From 2nd law, irreversibilities due to fluid friction in

adiabatic flow cause entropy to increase in the
 Adiabatic Flow direction of flow as fluid flow approaches reversibilities,
 Steady state entropy increase approaches zero for change in
 One dimensional flow entropy
 Compressible fluid

The main governing equation (dP, dS and dA form)

Molar or specific volume

M  Mach number , M=u/c
 volume expansivity
A  Cross sectional area of
(dS and dA form) duct normal to direction of flow
dx  differential length of path

where M is the Mach number, defined as

the ratio of the speed of the fluid in the
duct to the speed of sound in the fluid,
u/c.
36
Duct Flow of Compressible Fluids

Pipe Flow
Horizontal pipe of constant cross sectional
area i.e dA/dx =0
Previous two equations reduces to

For subsonic flow M2 <1 then dP/dx < 0 and du/dx > 0
Pressure decreases and velocity increases,
Opposite in the case of supersonic fluid (M2 >1)

37
Nozzles

In a properly designed nozzle the area changes with length

in such a way as to make the flow nearly frictionless

In this situation,

Characteristics of flow in Nozzle

38
Nozzles

With Q, Ws and Δz all set

equal to zero
For isentropic flow,

39
 Duct Flow of Compressible Fluids

Throttling Process
When a fluid flow through restrictions such as orifice or partly closed valve or porous plug
without any significant change in K.E and P.E but the process cause pressure drop influid
then the process is said to be throttling process, where no shaft work is done, Hence in
the absence of heat transfer

So, throttling process occurs at constant enthalpy,

Now consider an ideal gas,

Since enthalpy is not changing then temperature is constant

But for real gas, reduction in pressure at constant enthalpy resulting to

decrease in temperature.
We will see three different cases in the next slide.

40
 Duct Flow of Compressible Fluids

Case I : 1000 kPa and 300 degree Celsius (steam) is throttled to a low pressure of 1 atm,
H2=H1= 3052.1 kJ/kg (see steam table or NIST data)

If we closely analyze that at 3052.1 kJ/kg and 1 bar, the temperature of steam comes down
at 288.8 degree Celsius. So we see a decrease in temperature (but not up to a
considerable value)

Case II :Consider wet steam (quality 0.96) throttled from 1000kPa (Tsat= 179.88 degree C)
to 101.325 kPa

Then H2=H1=0.04*762.6+0.96*2776.2 = 2695.7 kJ/kg (see steam table)

If we look at the steam at 1bar this enthalpy 2695.7 kJ/kg has a temperature of 109.8
degree C. This considerable temperature drop is due to the evaporation of liquid (liquid
converted to vapor) (because water vapor have low heat capacity than liquid water)

41
 Duct Flow of Compressible Fluids

Case III :If saturated liquid is throttled to low pressure then some of the liquid vaporizes or
flashes producing a mixture of saturated liquid and vapor.

Suppose a saturated liquid water at 1000kPa (Tsat =179.88 degree C) is flashed to 101.325
kPa
H2=H1=762.6 kJ/kg,
We see that quality of resulting steam is found from
762.6=˘(1-x)*419.1+x*2676.0
x= 0.152 i.e 15.2 % of liquid converted to vapor and a large temperature drop can be
observed due to evaporation of liquid

Application of Throttling process:

42
 Duct Flow of Compressible Fluids

Just think opposite to throttling process …….

Under what condition should we expect an increase in temperature ???

Sign of the temperature change can be achieved by a derivative as

Called as Joule’s Thomson

effect

Finally,

Locally it may be true for real gas, which

Separates the curves in two region

43
Duct Flow of Compressible Fluids

(means no temperature change, true for ideal gas)

44
Numerical Problem
Propane gas at 20 bar and 400 K is throttled in a steady-state flow process to 1 bar.
Estimate the final temperature of the propane and its entropy change. Properties of
propane can be found from suitable generalized correlations.
Duct Flow of Compressible Fluids

Turbines
Expansion of gas in a nozzle to produce a high velocity stream, which is a
process to convert internal energy into K.E. Which inturn used to rotate the
shaft and hence into shaft work.

Assumptions:
1. Change in P.E is negligible
2. Fluid velocities are roughly equal at inlet and outlet
Energy Balance

If the fluid in turbine expands reversibly and adiabatically (isentropic) then S2 = S1 then

is the maximum shaft work. Actual shaft work is less

than that the

Thus turbine efficiency can be given by

45
Duct Flow of Compressible Fluids

Discuss Nature of lines of 1 to 2

Irreversibilities

Reversibilities

Steady-state flow through a turbine or

expander

Adiabatic expansion process in a turbine or expander.

46
Numerical
Numerical
Duct Flow of Compressible Fluids

Compression Process
Compression brings pressure increase in the process.
For example: Compressors, pumps, Vacuum Pump etc.

In thermodynamics, we will be interested in the energy consumption to bring increase

in pressure under steady state compression.

Assumption

1. Change in P.E and K.E are negligible

2. Adiabatic Compression
3. Steady State

In isentropic process, the work required is the

minimum shaft work for compression of gas.

Thus compressor efficiency can be given by

 Duct Flow of Compressible Fluids

For special case ideal gas and constant heat capacities,

/

Compressor efficiencies are usually in the

range of 0.7 to 0.8.

Adiabatic compression process

 Numerical
Problem A

Problem B
Duct Flow of Compressible Fluids

PUMPS

Liquids are moved by pumps, which are generally rotating

equipment.

For isentropic process

CP, V, and β are constant

Numerical
 Chemical Engineering Thermodynamics

Note: Readers can suggest any error or mistake in this ppt file.
Production of Power From Heat

1
Objective of Chapter

 Qualitatively describe the idealized Carnot, Rankine, Otto, Diesel, and Brayton cycles
and sketch each of them on a PV or TS diagram
 Compute efficiency and heat and work flows for an air-standard Brayton cycle for
given combustor temperature and compressor and turbine efficiencies

 Explain, in simple terms, how jet and rocket engines generate thrust.

1
Topics to be Discussed
• Steam power plants in relation to the Carnot, Rankine, and regenerative cycles

• Internal-combustion engines in relation to the Otto, Diesel, and Brayton cycles

• Jet and rocket engines

2
THE STEAM POWER PLANT

Figure b: Carnot cycle on a TS diagram.

Figure a: Simple steam power plant

3
THE STEAM POWER PLANT

• Steady-state steady-flow cyclic process

• Reversible
• Behaves as Carnot cycle
• Consisting of two isothermal steps connected by two adiabatic steps

Step 1 → 2 is isothermal vaporization taking place in a boiler at temperature TH, wherein

heat is transferred to saturated-liquid water at rate QH, producing saturated vapor.

Step 2 → 3 is reversible adiabatic expansion of saturated vapor in a turbine producing a

two-phase mixture of saturated liquid and vapor at TC.

Step 3 → 4 is an isothermal partial-condensation process at lower temperature TC,

wherein heat is transferred to the surroundings at rate QC

Step 4 → 1 is an isentropic compression in a pump. Represented by a vertical line, it

takes the cycle back to its origin, producing saturated liquid water at point 1.

4
THE STEAM POWER PLANT

Analyze this relation

The net power output is equal to the difference between the rate of heat input in
the boiler and the rate of heat rejection in the condenser.

This efficiency may be used for comparison with practical power plant, but
unfortunately, there are several difficulties to follow the step 2  3 and 4  1

In reality, there are saturated steam taken by the turbine, produces a high liquid
content, which results into severe erosion problem in turbine (not been addressed
in carnot cycle). These problem led to the development of Rankine cycle, used
as a comparison purpose
Nevertheless, nuclear power plants generate saturated steam and operate with turbines designed to eject liquid at
various stages of expansion

5
THE STEAM POWER PLANT
Even more difficult is the design of a pump that takes in a mixture of
Rankine Cycle: liquid and vapor (point 4) and discharges a saturated liquid (point 1).

Figure c: Rankine cycle on a TS Figure b: Carnot cycle on a TS diagram.

diagram.

6
 THE STEAM POWER PLANT
Rankine Cycle:
1 → 2 A constant-pressure heating process in a boiler. The step lies along an isobar (the
pressure of the boiler) and consists of three sections: heating of subcooled liquid water to its
saturation temperature, vaporization at constant temperature and pressure, and superheating
of the vapor to a temperature well above its saturation temperature

2 → 3 Reversible, adiabatic (isentropic) expansion of vapor in a turbine to the pressure of the

condenser. The step normally crosses the saturation curve, producing a wet exhaust.
However, the superheating accomplished in step 1 → 2 shifts the vertical line far enough to
the right on Fig. c that the moisture content is not too large

3 → 4 A constant-pressure, constant-temperature process in a condenser to produce

saturated liquid at point 4.

4 → 1 Reversible, adiabatic (isentropic) pumping of the saturated liquid to the pressure of the
boiler, producing compressed (subcooled) liquid. The vertical line (whose length is exaggerated
in Fig c) is very short because the temperature rise associated with compression of a liquid is
small.

7
THE STEAM POWER PLANT
Deviation of Practical Power Cycle from Rankine Cycle:

In an irreversible environment
Assumption

Figure: Simple practical power cycle.

8
 THE STEAM POWER PLANT

Practice Problem:

Example8.1

Steam generated in a power plant at a pressure of 8600 kPa and a temperature of 500°C
is fed to a turbine. Exhaust from the turbine enters a condenser at 10 kPa, where it is
condensed to saturated liquid, which is then pumped to the boiler. (a) What is the thermal
efficiency of a Rankine cycle operating at these conditions? (b) What is the thermal
efficiency of a practical cycle operating at these conditions if the turbine efficiency and
pump efficiency are both 0.75? (c) If the rating of the power cycle of part (b) is 80,000 kW,
what is the steam rate and what are the heat-transfer rates in the boiler and condenser?

9
 THE STEAM POWER PLANT
Regenerative Cycle

The purpose of heating the feed

water in this manner is to raise
the average temperature at
which heat is added to the water
in the boiler. This increases the
thermal efficiency of the plant,
which is said to operate on a
regenerative cycle.

High boiler pressures and

temperatures favor high
efficiencies. Figure: Steam power plant with feedwater heating.

10
 Numerical
Example 8.2: Determine the thermal efficiency of the power plant shown in Fig. 8.5, assuming
turbine and pump efficiencies of 0.75. If its power rating is 80,000 kW, what is the steam rate
from the boiler and what are the heat-transfer rates in the boiler and condenser?
Internal Combustion Engine

In an internal-combustion engine, a fuel is burned within the engine itself, and the
combustion products serve as the working medium, acting for example on a piston in a
cylinder. High temperatures are internal and do not involve heat-transfer surfaces.
INTERNAL COMBUSTION ENGINES
The Otto Engine

Figure: Otto engine cycle. Figure: Air-standard Otto cycle.

11
INTERNAL COMBUSTION ENGINES
The Otto Engine

Four stroke engine

0 → 1 starts with an intake stroke at essentially constant pressure, during which a piston
moving outward draws a fuel/air mixture into a cylinder.

1 → 2 → 3 All valves are closed (During second stroke)

1 → 2 the fuel/air mixture is compressed, approximately adiabatically along line segment
2 → 3 the mixture is then ignited, by firing of a spark plug, and combustion occurs so
rapidly that the volume remains nearly constant while the pressure rises along line
segment
3 → 4 The high-temperature, high-pressure products of combustion expand,
approximately adiabatically along line segment
4 → 1. the exhaust valve then opens and the pressure falls rapidly at nearly constant
volume along line segment
1 → 0 During the fourth or exhaust stroke, the piston pushes the remaining combustion
gases (except for the contents of the clearance volume) from the cylinder

12
INTERNAL COMBUSTION ENGINES
The Otto Engine

An idealized cycle, called the air-standard Otto cycle

Two adiabatic and two constant-volume steps

Working fluid is air in its ideal-gas state with constant heat capacity

DA  Where sufficient heat is added to the air

at constant volume to raise its temperature and
pressure to the values resulting from AB  Adiabatic
combustion in an actual Otto engine. reversible expansion

CD  a reversible adiabatic AB  Cooling at

compression constant volume

thermal efficiency η
Air-standard Otto cycle
13
INTERNAL COMBUSTION ENGINES
The Otto Engine

Use Q= CV (del T)

Compression ratio, r = the ratio of the volumes at the beginning and end of compression
from point 1 to point 2 in Otto cycle
Relation between compression ratio and thermal efficiency

14
INTERNAL COMBUSTION ENGINES

The Otto Engine

Engine Knocking: Preignition of fuel before the completion of compression stroke leads
to a problem of engine knocking
When will it happen ?????

Response: When compression ratio will be set at a high value causing the temperature to
rise and suddenly leads to ignite the fuel

How can we control the preignition or knocking ????

Response: Compression ratio or extent upto what pressure we can compress the system
without causing preignition depends on the property of fuel.
Which property of fuel can be checked before designing the engine ????

Response: Octane number or octane rating of any fuel

15
 INTERNAL COMBUSTION ENGINES
Octane number or Octane rating of any fuel

Iso-Octane have a value of octane number to be 100, while n-heptane possess an octane
number of zero, this is used for benchmarking the fuel’s octane number

How can we increase the octane number in

gasoline????

Response: Addition of Oxygen-based compound,

aromatic compounds, and branched chain
hydrocarbons such as ethers, alcohols and
aromatic compounds

16
INTERNAL COMBUSTION ENGINES
Octane number or octane rating of any fuel

https://www.rushlane.com/100-octane-petrol-india-launch-price-12385313.html

17
Thank You

17
INTERNAL COMBUSTION ENGINES
The Diesel Engine

Only the air inside the compression chamber is compressed upto the actual compression
ratio value, which causes rise in temperature of the chamber, and suddenly, fuel is injected
, where combustion takes place spontaneously without any external flame.
Diesel fuel is having low value of autoignition temperature than gasoline, which helps to
burn the fuel spontaneously inside the compression chamber.

For the same compression ratio, the Otto engine has a higher efficiency than the Diesel
engine.
Compression ratios can exceed 20 in Diesel engines employing indirect fuel injection.

Expansion ratio re

18
INTERNAL COMBUSTION ENGINES
The Diesel Engine The air-standard Diesel cycle is the
same as the air-standard Otto cycle,
except that the heat-absorption step
(corresponding to the combustion
process in the actual engine) is at
constant pressure, DA.

Heat absorbed in DA and

rejected in BC

Figure: Air-standard Diesel cycle.

19
 INTERNAL COMBUSTION ENGINES
The Gas-Turbine Engine
Turbines are more efficient than reciprocating
engines, and the advantages of internal combustion
are combined with those of the turbine in the gas-
turbine engine

The idealization of the gas-turbine engine,

called the Brayton cycle

( )/

20
INTERNAL COMBUSTION ENGINES
The Gas-Turbine Engine ( )/

20
INTERNAL COMBUSTION ENGINES
JET ENGINES

• Hot gases are expanded through nozzle

• K.E of the gas product is used to drive the vehicle when leaves the nozzle with a high K.E.

• Turbine is used to further compress the product gases

• Then compressed gases are passes through nozzle to achieve a high K.E gas, which is
used to propel the jet by thrust force

• The simple cycle i.e., Brayton cycle can be used to analyze the jet engines. Only difference
is that the compression and expansion carried out in different device.

21
INTERNAL COMBUSTION ENGINES
ROCKET ENGINES

Rocket engine does not depend on the surrounding air for combustion, instead
oxidizing agent such as liquid oxygen, nitrogen tetraoxide is pumped into the combustion
chamber simultaneously with the fuel (liquid fuels as : hydrogen, kerosene,
monomethylhydrazine, while solid fuels: organic polymer with oxidizing agent ammonium
perchlorate)

The performance is much better than jet engine because the thrust force does not
cancels the friction force caused by surrounding air when operated in vacuum.

Note that, solid fuel does not require compression work, while liquid fuel possess a
little compression work.

22
 Chemical Engineering Thermodynamics

Note: Readers can suggest any error or mistake in this ppt file.
Refrigeration and Liquefaction:

1
 Topics to be Discussed

 The model refrigerator, operating on a reverse Carnot cycle

 Refrigeration via the vapor-compression cycle, as in the common household

refrigerator and air conditioner

 The choice of refrigerants as influenced by their properties

 Refrigeration based on vapor absorption, an alternative to vapor compression

 Heating or cooling by heat pumps with heat extracted from or rejected to the surroundings

 The liquefaction of gases by refrigeration

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THE CARNOT REFRIGERATOR
Refrigerator works as a heat pump that absorbs
heat from a region at a temperature below that
of the surroundings and rejects heat to the
surroundings

2
THE CARNOT REFRIGERATOR

The isothermal steps

2 --> 3 absorption of heat at lower
temperature TC
4  1 rejection of heat at higher
temperature TH
Two adiabatic process 1  2 and 3  4

The cycle also require the W work,

which will be minimum required work as
we know that Carnot cycle works in
reversible manner.

Highest possible efficiency will be

achieved in Carnot refrigerator

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THE CARNOT REFRIGERATOR

Since this is a cyclic process,

, Then according to first law, W= -(Qc +QH)

Effectiveness of a refrigerator can be measured as

coefficient of performance

2
The VAPOR COMPRESSION CYCLE

2
 The VAPOR COMPRESSION CYCLE
line 1 → 2 Liquid refrigerant evaporating at
constant T and P, producing refrigeration effect
Line 2  3 and 2  3’ , for isentropic
compression and actual compression process
respectively
3  4 at higher T and P, cooled and condensed
with rejection of heat to surrounding
4  1, liquid from condenser expands to
original pressure, usually carried out with help
of throttle valve at constant enthalpy

Heat absorbed in the evaporator and heat

rejected in the condenser are related as

Neglecting small change in PE and KE

Work of compression, W= H3-H2 and

coefficient of performance given by
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The VAPOR COMPRESSION CYCLE
To design the evaporator, compressor,
condenser, and other equipment, one must
know the rate of circulation of refrigerant

Rate of flow of refrigerant

PH diagram will be helpful instead of TS

diagram, while designing the equipment,
because required enthalpies can be known
from the process diagram.
Tons of refrigeration: heat absorption rate of
12660 kj per hour, which is equivalent to freeze Figure: Vapor-compression
1 ton of water at 0 degree Celsius. refrigeration cycle on a PH
diagram.

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CHOICE OF REFRIGERANT
To design the evaporator, compressor, condenser, and other equipment, one must
know the rate of circulation of refrigerant.

In addition, in vapor compression cycles, if we introduce irreversibilities then

coefficient of performance for practical refrigerator depends on the choice of
refrigerant.

Choice of refrigerant can be justified by its corrosion, toxicity, vapor pressure,

environmental concern and cost.

Ammonia, methyl chloride, carbon dioxide, propane, and other hydrocarbons can
serve as refrigerants, particularly in industrial applications

Fully halogenated Hydroflurocarbons

2,3,3,3-
chlorofluorocarbons tetrafluropropene
HFC-134a
(HFO-1234yf)
Deplete And R134a
stratospheric zone Global Warming
Issues

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LIQUEFACTION PROCESSES

Liquefaction results when a gas is cooled to a temperature in the

two-phase region. This may be accomplished in several ways:

1. By heat exchange at constant pressure.

2. By an expansion process from which work is obtained.
3. By a throttling process.

The Linde liquefaction process

Claude liquefaction process

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LIQUEFACTION PROCESSES

The Linde liquefaction process

The lower the temperature of the gas entering the throttle valve, the greater the fraction of
gas that is liquefied
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 LIQUEFACTION PROCESSES
Gas at an intermediate temperature is
extracted from the heat-exchange
system and passed through an
expander from which it exhausts as
a saturated or slightly superheated
vapor. The remaining gas is further
cooled and throttled through a valve to
produce liquefaction as in the Linde
process. The unliquefied portion,
which is saturated vapor, mixes with
the expander exhaust and returns for
recycle through the heat-exchanger
system.