Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
Chemical Engineering Thermodynamics
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Topics from the Syllabus
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Objective of Chapter
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Specific and molar Quantities
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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.
Aboslute
Atmospheric
Vacuum
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Work
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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
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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.
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Microscopic and Macroscopic
approach in Thermodynamics
Microscopic Macroscopic
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Intensive and Extensive Property
Density P
Density
P
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System and Surrounding
Closed system Open System
Control Volume
Surrounding
System
Control Surface
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Some Keywords in Thermodynamics
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.
Statement
Total energy is constant and when one form of energy disappears then it appears in another
form.
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First Law of Thermodynamics
P.E and K.E stored in the closed system and appears as internal energy when added
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First Law of Thermodynamics
For closed system, often only internal energy of the system changes
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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
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First Law of Thermodynamics (Equilibrium)
Applicable to
macroscopic level
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Equilibrium and Phase Rule
Equilibrium
Absence of change and tendency towards change at macroscopic level.
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
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Equilibrium and Phase Rule
For multiphase and non-reacting system
Number of degree of freedom
Number of phases
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
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
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First Law of Thermodynamics
State Function and Path Function
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
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Reversible Process
Chemical reversible reaction can be achieved when a differential pressure
or temperature is applied to the reactor.
• 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
(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
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Enthalpy
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.
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Heat Capacity
Smaller the temperature change after given a quantity of heat to a substance greater the
heat capacity of that substance
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Mass Balance for Open System
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Mass Balance for Open System
Special cases like steady state flow process, incompressible fluid etc.
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Mass Balance for Open System
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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)
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Energy Balance for Open System
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Energy Balance for Open System
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Numerical Problems
Numerical Problems
Numerical Problems
Numerical Problems
Chemical Engineering
CHAPTER-3
Thermodynamics
Volumetric Property of Pure Fluids
Overview
Generalized (Equation of State) EoS
Ideal EoS
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Volumetric Property of Pure Fluids
2 Triple point
C Critical Point
F=0 When three phases
co-exists (Triple point)
F=1, Univarient, When two phases
co-exists
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Volumetric Property of Pure Fluids
Boundary changed to region here in
PV diagram
Regions: solid/liquid; liquid/vapor;
solid/vapor co-exists in equilibrium
PV diagrams for a pure substance. (a) Showing solid, liquid, and gas regions. (b)
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Showing liquid, liquid/vapor, and vapor regions with isotherms.
Volumetric Property of Pure Fluids… more
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)
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Showing liquid, liquid/vapor, and vapor regions with isotherms.
Virial Equation of State
---(1)
or
∗ (as P 0) --(3)
Statement: “a” only depends on the temperature and independent on chemical species
as P 0
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Virial Equation of State
Here, we introduce a term called compressibility factor, which is dimensionless ratio given
by
Alternate form
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Virial Equation of State
TC = 190.6 ± 0.3 K
PC = 46.1 ± 0.3 bar
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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)
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Ideal Equation of State
(Ideal gas)
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Ideal Equation of State
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Process Calculation in Ideal Gas
After rearrangement,
The above equation is function of P, V and T where only two intensive variable is
independent.
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Process Calculation in Ideal Gas
Equation 8 through 10, valid for
Ideal gas, closed and mechanical
reversible.
8-A)
also convert Cv to Cp
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Process Calculation in Ideal Gas
Isothermal Process
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Process Calculation in Ideal Gas
Isobaric Process
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Process Calculation in Ideal Gas
Isochoric Process
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Process Calculation in Ideal Gas
Adiabatic Process
We denote
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Process Calculation in Ideal Gas
( )/
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.
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Process Calculation in Ideal Gas
11
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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
Diatomic gas
Polyatomic gas
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Process Calculation in Ideal Gas
Polytropic Process
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Cubic Equation of State (EoS)
𝑁𝑜𝑡𝑒: 𝐻𝑒𝑟𝑒 𝑃 𝑎𝑛𝑑 𝑉 𝑖𝑛 𝑡ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑎𝑟𝑒 𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑎𝑛𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
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Cubic Equation of State (EoS)
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Cubic Equation of State (EoS)
also
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Cubic Equation of State (EoS)
---(A)
Rearrange,
---(B)
---(C)
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Cubic Equation of State (EoS)
and
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Cubic Equation of State (EoS)
---(V1)
---(V2)
Initial estimate should start from idea gas value i.e V=RT/P
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Cubic Equation of State (EoS)
---(L1)
---(L2)
Initial estimate should start from idea gas value i.e V=b and Z=
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Cubic Equation of State (EoS)
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Theorem of Corresponding States: Acentric Factor
Acentric factor of a pure chemical species is defined with reference to Vapor Pressure
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Theorem of Corresponding States: Acentric Factor
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