Chapter 1

Introduction & Review

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 1

DISCLAIMER!
The material required from the students to
understand is not restricted to the lecture notes
attached herein.

The designated textbook sections should be the

basic source of information for the students.

Class discussions, beyond the lecture notes, are

also required.

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 2

Some Important Notations used in
the Main Text (Introduction to
Chemical Engineering
Thermodynamics; 7th Edition, by
Smith, Van Ness, and Abbott, 2005)

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 3

 Plant Design

Equipment Design

Energy Calculations Chemical Equilibrium Phase Equilibrium

➢ Turbines ➢ Reactor Design ➢ Distillation
➢ Heat Exchangers ➢ Adsorption
➢ Evaporators ➢ Evaporation

Laws of
Thermodynamics
Thermodynamics
Properties
1st & 2nd
Mathemati

Physics
cs

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 4

 Why is thermodynamics important to a
Chemical Engineer?
Key Variables
Temperature (T), Pressure (P), Volume (V),
Mole (n), Composition (xi)
Energy (Heat (Q) & Work (W))

Process Applications in
Useful Variables & Concepts Chemical Engineering
Z, Psat, Tc, Pc, ω
Thermo 1
Flow Process with Multiple Units
Intensive & Extensive
Compressors & Turbines
Open & Closed Systems
Power Cycles & Refrigeration
U, H, S, G, A, Cp, Cv
Optimum Work / Availability
Maxwell Relationship
Heat and Volume of Mixing
Thermo 2

Mig, Mid, M, ME, MR, ∆Mmix

Separation Process Design
Gibbs-Duhem Equation
Chemical Reaction Equilibrium/
µ, f, φ, γ
Key Concepts Reactor Design
Gibbs’ Phase Rule
Equations of State (EOS) K, ∆Grxn, ∆Hrxn
Mass Balance
1st Law & 2nd Law
Reversibility
Mixture Behavior
Phase Equilibrium
Chemical Equilibrium
CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 5
 Chemical & Physical Processes

Thermodynamics
Heat Transfer Process
Mass Transfer
Kinetics Rate

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 6

System & Surroundings

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 7

Law of Thermodynamics

0th Law of Thermodynamics:

If two thermodynamic systems are
separately in thermal equilibrium
with a third, they are also in thermal
equilibrium with each other.

1st Law of Thermodynamics:

The change in the energy of a thermodynamic
system is equal to the sum of the amount of
energy interactions between the system & its
surroundings.

Closed system
Both Q & W are positive
Transfer into the system from the surroundings
CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 8
Law of Thermodynamics

2nd Law of Thermodynamics:

The total entropy of any isolated
thermodynamic system tends to
increase over time, approaching a
maximum value.

3rd Law of Thermodynamics:

The entropy of all systems & of all
states of a system is zero at
absolute zero temperature.

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 9

 Chapter 2
First Law & Other Basic Concepts

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 10

Energy balance for a homogeneous fluid
in a closed system:

Constant V & P Processes:

( ) ( )
d nU = nQ + W
Where work for mechanically-reversible process is;

W = − Pd nV ( ) Total for all the

molecules in the
system
Constant V Processes: work is 0 ➔
Therefore;
dQ = d ( nU ) We will relate this change
to physical quantities to
 dQ =  d ( nU ) solve problems
 Q = nU
Change in property
Quantity
CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 11
Constant P Processes:

( )
Q = d nU + Pd nV ( )
for P const.
( ) ( )
Q = d nU + d nPV
Q = d  n (U + PV )
Q = d (nH )
Enthalpy Enthalpy is described as the
Q = nH "heat content" of a system for a
given pressure.
H = U + PV
As a result, the word "heat" is
sometimes used in place of the
word "enthalpy".

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 12

Reversible process
A reversible process is a process whose direction can be "reversed"
by inducing infinitesimal changes to some property of the system via its
surroundings.

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 13

2nd Law - Carnot’s theorem:

For a reversible cyclic process

dQrev
dS = 
T
Qrev = TdS

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 14

 Chapter 3
PVT Behavior of Pure Substances

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 15

PT Diagram for Pure Substance
How to calculate the quantities of heat & work necessary to carry out
industrial processes?
Knowledge of thermodynamics properties such as internal energy &
enthalpy.
PVT relations (such as PV = RT)

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 16

PV Diagram for Pure Substance

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 17

Vapor-Liquid Equilibrium on PT Diagram

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 18

3.2. Virial Equations of State
We would like to express every property in terms of analytical
equations.
Most important properties are:
Pressure
Volume
Temperature

With the relations of these among each

other helps us to get other properties.

PV = a + bP + cP 2 + ...

if b  aB ' and c  aC ' etc... then

(
PV = a 1 + B ' P + C ' P 2 + D ' P 3 + ... )
PV
Since Z =  then
RT

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 19

Two Forms of the Virial Equation

Page 72
Virial Equation
and (Eq. 3.11 & 3.12)

Both of these equations are known as virial Two Forms of Virial

expansions, and the parameters B′, C′, D′, etc., EOS: One in terms of
Pressure, & another in
& B, C, D, etc., are called virial coefficients.
terms of Volume
Parameters B′ and B are second virial coefficients;
C′ and C are third virial coefficients, and so on.
For a given gas the virial coefficients are functions of
temperature only.

(13.3 a) (13.3 b) (13.3 c)

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 20

3.4 APPLICATION OF THE VIRIAL EQUATIONS Page 87

The Equation may be truncated to

two terms for application at low
pressures:

(3.39)

When the virial equation is truncated to

three terms, the appropriate form is:

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 21

3.5. Cubic Equations of State (EOS) Page 90
Cubic equations are in fact the simplest equations capable of representing
both liquid & vapor behavior.
Cubic equations of state are called such because they can be rewritten as
a cubic function of molar volume.
Example on Cubic Equations of State:
van der Waals EOS:

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 22

A Generic Cubic Equation of State
Redlich/Kwong (RK) equation, initiated in 1949

Subsequent enhancements have produced an important class of equations,

represented by a generic cubic equation of state:

For a given equation, ɛ and σ are pure numbers, the same for all
substances, whereas parameters a(T) & b are substance
dependent.
The temperature dependence of a(T) is specific to each equation of
state.

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 23

Generic Form of the Cubic Equation of state
Equation
numbers in
V = ZRT/P
textbook

𝑹𝑻 𝒂 𝑻 𝑽−𝒃
𝑽= +𝒃 − (3.49)
𝑷 𝑷 𝑽+𝝐𝒃 𝑽+ 𝝈𝒃
Or:
𝒁− 𝜷
𝒁=𝟏+ 𝜷 −𝒒𝜷 (3.52)
𝒁+𝝐𝜷 𝒁+ 𝝈𝜷
Where:
(3.53) (3.54)

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 24

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 25
Example 3.9 Page 98
Given that the vapor pressure of n-butane at 350 K is 9.4573 bar, find
the molar volumes of saturated-vapor of n-butane at these conditions
as given by the Redlich/Kwong equation.

Solution: T P
Tr = Pr =
Tc Pc

The RK form that results upon substitution of appropriate values

for ε and σ from Table 3.1:

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 26

Solution cont.:

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 27

3.6 GENERALIZED CORRELATIONS FOR GASES
Pitzer Correlations for the Compressibility Factor

= Pitzer acentric factor

Of the Pitzer-type correlations available, the one developed by

Lee and Kesler (LK) is the most widely used.

It takes the form of tables that present values of Z0 and Z1 as functions of

Tr & Pr. These are given in Appendix E as Tables E.1-E.4.

T P Tr = Reduced Temperature
Tr = Pr =
Tc Pc Pr = Reduced Pressure

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 28

 E1

E2

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 29

Pitzer Correlations for the Second Virial Coefficient

The simplest form of the virial equation:

(3.62) (3.63)

(3.65) (3.66)

Study Example 3.10-3.12 Page 105-108

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 30

3.3. Ideal Gas
Assuming:
Z =1
- No molecular interactions
- No molecular volume occupancy

Because the terms in Virial Equation arise on

account of molecular interactions → They are zero
for ideal gas case where no interactions are
assumed.

For ideal gas in a closed system:

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 31

Recall that P=RT/V & V=RT/P
we obtain the following equations for ideal gas:

dV (3.22)
dQ = c v dT + RT
V
dP
dQ = c p dT − RT (3.24)
P Page 75
dV
dW = −RT (3.23)
V
dP
dW = −RdT + RT (3.25)
P

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 32

Ideal Gas - Processes

Isothermal Process:

U = H = 0
V2 P2
Q = −W = RT ln = −RT ln
V1 P1

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 33

Page 76

Isobaric Process: Adiabatic Process:

Pressure = constant
R cv
Q = H T2  V1 
= 
Q = H = c p dT T1  V2 
R cp
T2  P2 
Isochoric Process: = 
Volume = constant T1  P1 
cp cv
Q = U P2  V1 
= 
Q = U = c v dT P1  V2 

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 34

Polytropic Process:
Polytropic process suggest a model of some versatility (process can occur in
many directions, ways)…A process which occurs with an interchange of both heat
and work between the system & its surroundings. The non-adiabatic expansion or
compression of a fluid is an example of a polytropic process.


Isobaric Process:  =0
PV = constant Isothermal Process:  =1
TV  = constant Adiabatic Process:  =
TP (1- )/ = constant
( -1)/
RT1  P2  
W=   − 1
 − 1  P1  
( −1)/
( −  )RT1  P2  
Q=   − 1
( − 1)( − 1)  P1  

 = cp / cv

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 35

Intensive & Extensive Properties

Intensive Extensive
Properties Properties

DO NOT DEPEND DEPEND ON THE

ON THE AMOUNT AMOUNT

➢ Temperature
➢ Volume
➢ Pressure
➢ Length
➢ Color
➢ Shape
➢ Taste
➢ Mass
➢ Density
➢ Boiling Point

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 36

 Height is an
Volume is an
extensive property
extensive property

Adding matter Increasing the volume Removing matter Decreasing the height

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 37

 Closed & Open Systems

Closed System

Open System

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 38

Homogeneous & heterogeneous thermodynamic
systems

A homogeneous thermodynamic system is defined as the one whose

chemical composition and physical properties are the same in all parts
of the system.

Pure Mixture

A heterogeneous system is defined as one consisting of two or more

homogeneous bodies.

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 39

Equilibrium
Equilibrium is a point of balance.

The rate of the forward reaction

is equal to …

the rate of the backward reaction

CHEMICAL ENGINEERING THERMODYNAMICS II CHME312 (FALL 2020) 40

 Reference

Smith J.M., Van Ness H.C., & Abbott M. M., Introduction to Chemical Engineering
Thermodynamics, 7th Edition, McGraw Hill, New York, 2001.

CHEMICAL ENGINEERING THERMODYNAMICS II, CHME 312 (FALL 2020) 41