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.

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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

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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

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 Temperature Scale

Boiling
Point

Freezing
Point

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 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

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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

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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

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

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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

Molecular level approach Quantity of matter (mass) level approach

Studied in statistical thermodynamics Studied in classical thermodynamics

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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

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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

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.

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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

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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

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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

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

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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

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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

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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.

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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.

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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

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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.

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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

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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

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

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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

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Numerical Problems
Numerical Problems
Numerical Problems
Numerical Problems