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Chemical Engineering Thermodynamics

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Chemical Engineering Thermodynamics

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

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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

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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)

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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

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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

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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

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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

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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.

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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


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Heat Capacity

b) Heat Capacity at constant pressure

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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

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