Chemical Engineering

Thermodynamics (CB206)

Chemical and Biochemical Engineering

Indian Institute of Technology Patna

Atanu K Metya
atanu.metya@iitp.ac.in
 Chemical Engineering Thermodynamics
Course syllabus
Introductory Concepts of Thermodynamic Systems and variables, Work, Heat, Internal Energy,
Thermodynamic Equilibrium, Reversible and Irreversible Processes; PhaseRule; Significance of Chemical
Engineering Thermodynamics; Equations of State and Generalized Correlations for Prediction of Volumetric
Properties of Fluids; First Law: Closed and Open Systems, Steady and Transient Flow Processes; Second law
and Entropy; Entropy Balance and Availability, Isentropic Efficiency; Maxwell Relations and Fluid
Properties Estimation, Application to Flow Processes; Single Phase Mixtures and Solutions; Ideal Solutions;
Partial molar quantities; Gibbs-Duhem Equation; Criteria for Thermodynamic Equilibrium; Phase
Equilibrium Criteria, Non- ideal Solutions; Residual and Excess Properties; Fugacity and Activity Coefficient
models; Pure Component Phase Equilibria, Vapour-Liquid Equilibria (VLE), Raoult's Law and Modified
Raoult’s Law; High-Pressure VLE; Henry's law; Chemical Reaction Equilibrium: Homogeneous and
Heterogeneous reactions; Multi-reaction Equilibria; Liquid-Liquid Equilibria; Solid – Liquid Equilibria;
Solid – Vapour Equilibria
Text Books:
1. J.M. Smith, H.C. Van Ness, M.M. Abbott, Introduction to Chemical Engineering Thermodynamics, 6th Ed.,
McGraw-Hill, 2001
2. S.I. Sandler, Chemical, Biochemical and Engineering Thermodynamics, 4th Ed., Wiley India, 2006
3. Y. V. C. Rao, Chemical Engineering Thermodynamics, 1st Ed., Universities Press, India, 1997
 Chemical Engineering Thermodynamics

Grading
• Midterm test: 30%
• Final Exam. 40%
• Assignments and quiz 20%
• Questions, reflections, interactions and feedback 10%

Class Timings
Monday: 4:00 – 4:55 PM
Tuesday: 4:00 – 4:55 PM
Wednesday: 4:00 – 4:55 PM
 Chemical Engineering Thermodynamics
Application areas of Thermodynamics
Course Objectives
• Thermodynamics is a
prerequisite for understanding
the transfer processes

• To establish the general

thermodynamic principles and
key relations

• Real-world engineering
examples for how
thermodynamics is applied in
engineering practice
 Chemical Engineering Thermodynamics

Back ground and definition of thermodynamics

American biophysicist Donald Haynie claims that thermodynamics was
coined in 1840 from the Greek root therme, meaning heat and dynamics,
meaning power.

Thermodynamics:
• deals with heat and temperature, and their relation to energy, work, and
properties of bodies of matter.
• deals with the transfer of energy from one place to another and from one
form to another.

Engineering Thermodynamics:
 Chemical Engineering Thermodynamics

Thermodynamics:
• The behavior of these quantities is governed by the four laws of
thermodynamics:
• Zeroth law of thermodynamics
• First law of thermodynamics
• Second law of thermodynamics
• Third law of thermodynamics

• The thermodynamics laws are explained by classical thermodynamics

and by statistical mechanics.

• Macroscopic and Microscopic Approaches

Typical isothermal simulations: XS = 5.56 %
εC-S= 0.13 kcal/mol εC-S= 0.3 kcal/mol

7
 Chemical Engineering Thermodynamics

Basic Concepts
• System:

• Surroundings:

• Boundary:
• Fixed
• Movable
• Real, and
• Imaginary
 Chemical Engineering Thermodynamics

Systems: defined in terms of what is allowed to cross

their boundaries.

• Closed system/control mass:

• Isolated system:

• Open system/control system:

 Chemical Engineering Thermodynamics

Describing Systems

Properties of A System
• Intensive properties: independent of the mass of a system. Example,
temperature, pressure, and density.

• Extensive properties: depend on the size or extent of the system. Total

mass, total volume, and total momentum are some examples.
 Chemical Engineering Thermodynamics

State and Equilibrium

• State: At a given state, all the properties of a system have fixed values

• Equilibrium: A state of balance. Experiences no changes when it is isolated

from its surroundings
• Thermal equilibrium: no temperature differential
• Mechanical equilibrium: no change in pressure at any point of the
system with time
• Chemical equilibrium: chemical composition does not change with
time

• Non-equilibrium:
 Chemical Engineering Thermodynamics
Processes and Cycles

• Process:

• Path:

• Quasi-static or quasi-equilibrium process:

 Chemical Engineering Thermodynamics

Several commonly studied thermodynamic processes:

§ Isothermal process: the temperature remains constant
§ Isobaric process: the pressure remains constant
§ Isochoric (or isometric) process: the specific volume v remains constant
§ Adiabatic process: no heat is exchanged between a system and its
surroundings or no energy transfer in the form of heat
• Cycle: if it returns to its initial state at the end of the process
• Steady state process:

• Change of state
 Chemical Engineering Thermodynamics
Thermodynamics quantities:
Energy:
• The term energy was coined in 1807 by Thomas Young, and its use in
thermodynamics was proposed in 1852 by Lord Kelvin.
• The term internal energy and its symbol U first appeared in the works of
Rudolph Clausius and William Rankine in the second half of the 19th
century.
• The capacity for doing work
• Common forms of energy: kinetic, potential, thermal, chemical, elastic
energy, and nuclear, and their sum constitutes the total energy E of a
system
• Energy can cross the boundary of a closed system in two distinct forms:
heat and work
• Energy is a conserved quantity; the law of conservation of energy
 Chemical Engineering Thermodynamics
Thermodynamics quantities:
• Energy:
• Macroscopic and Microscopic forms of energy
• Internal Energy (U): sum of all forms of the
microscopic energies
 Chemical Engineering Thermodynamics
Thermodynamics quantities:
• Energy crosses the boundaries in the form of : Heat, Work, and
Mass flow

Heat: It is energy in transfer to or from a thermodynamic system by

virtue of a temperature difference

Work:
§ Mechanics: work is the energy transfer associate with a force
acting through a distance (W = F.s)
§ Thermodynamics: work is an energy interaction that is not
caused by a temperature difference
 Chemical Engineering Thermodynamics
Thermodynamics quantities:
• Many similarities b/w Heat and Work:

• Both heat and work are boundary phenomena

• Systems possess energy but not heat or work.
• Both are associated with a process, not a state.
• Both are path functions and not point functions.
 Chemical Engineering Thermodynamics
State function VS Path function
• A State Function
• Depends on the initial and final state of the system
• Exact differentials designated by d
• A Path Function
• Value depends on the nature of the process causing the change
• Inexact differentials designated by δ (δQ or δW) NOT dQ or dW.
Chemical Engineering Thermodynamics
 Chemical Engineering Thermodynamics

Energy Conservation
§ The work done on an accelerating body produces a change in its kinetic energy:
§ The work done on a body in elevating it produces a change in its potential energy:
§ An elevated body, allowed to fall freely (i.e., without friction or other resistance), gains
in kinetic energy what it loses in potential energy.
 Chemical Engineering Thermodynamics
Example: An elevator with a mass of 2500 kg rests at a level 10 m above the base of an
elevator shaft. It is raised to 100 m above the base of the shaft, where the cable holding it
breaks. The elevator falls freely to the base of the shaft and strikes a strong spring. The
spring is designed to bring the elevator to rest. Assuming the entire process to be
frictionless, and taking g = 9.8 m⋅s-2, calculate:
a) The potential energy of the elevator in its initial position relative to its base.
b) The work done in raising the elevator.
c) The potential energy of the elevator in its highest position.
d) The velocity and kinetic energy of the elevator just before it strikes the spring.
e) The potential energy of the compressed spring.
f) The energy of the system consisting of the elevator and spring
1. at the start of the process
2. when the elevator reaches its maximum height
3. just before the elevator strikes the spring
4. after the elevator has come to rest.
 Chemical Engineering Thermodynamics
The First Law of Thermodynamics
• Thermodynamic processes: the principle of conservation of energy.
• Total energy of an isolated system remains constant; it is conserved over time.
• The first law of thermodynamics states that energy can be neither created nor
destroyed during a process; it can only change forms.
 Chemical Engineering Thermodynamics
The First Law of Thermodynamics
• Heat transfer but no work interactions:
• The potato baked in the oven
• The heating of water in a pan
• A well-insulated (adiabatic) room heated by an electric heater
 Chemical Engineering Thermodynamics
The First Law of Thermodynamics
• For any process, the first law requires:
Δ(Energy of the system) + Δ(Energy of surroundings) = 0
• The total energy change of the surroundings equals the net energy
transferred to or from it as heat and work
Δ(Energy of surroundings) = ± Q ± W
• The choice of sign for numerical values of these quantities depends on
which direction of energy transfer with respect to the system is regarded as
positive.
• The numerical values of both quantities positive for transfer into the system
from the surroundings
 Chemical Engineering Thermodynamics
The First Law of Thermodynamics
• The change in the internal energy ΔU of a closed system is equal to the
amount of heat Q supplied to the system, minus the amount of work W done
by the system on its surroundings.
 Chemical Engineering Thermodynamics
Moving Boundary Work
• During the expansion or compression of a gas in a piston–cylinder
device, part of the boundary moves back and forth. Therefore, the
expansion and compression work is often called moving boundary
work, or simply boundary work
• A quasi-equilibrium process, also called a quasi- static process:
 Chemical Engineering Thermodynamics

• A typical industrial-scale wind turbine has a peak efficiency of about 0.44

for a wind speed of 9 m·s-1. That is, it converts about 44% of the kinetic
energy of the wind approaching it into usable electrical energy. The total air
flow impinging on such a turbine with a rotor diameter of 43 m is about
15,000 kg·s-1 for the given wind speed.
• How much electrical energy is produced when 1 kg of air passes through
the turbine?
• What is the power output of the turbine?
• If there is no heat transferred to the air, and if its temperature remains
unchanged, what is its change in speed upon passing through the turbine?
 Chemical Engineering Thermodynamics
• A rigid tank contains air at 500 kPa and 150°C. As a result of heat transfer to
the surroundings, the temperature and pressure inside the tank drop to 65°C
and 400 kPa, respectively. Determine the boundary work done during this
process.

• A piston–cylinder device initially contains 0.4 m3 of air at 100 kPa and

80°C. The air is now compressed to 0.1 m3 in such a way that the
temperature inside the cylinder remains constant. Determine the work done
during this process.
 Chemical Engineering Thermodynamics

• A gas is confined in a cylinder by a piston. The initial pressure of the gas is

7 bar, and the volume is 0.10 m3. The piston is held in place by latches.
• The whole apparatus is placed in a total vacuum. What is the energy change of the
apparatus if the restraining latches are removed so that the gas suddenly expands to
double its initial volume, the piston striking other latches at the end of the process?
• The process described in (a) is repeated, but in air at 101.3 kPa, rather than in a
vacuum. What is the energy change of the apparatus? Assume the rate of heat
exchange between the apparatus and the surrounding air is slow com- pared with the
rate at which the process occurs.
 Chemical Engineering Thermodynamics

• When a system is taken from state a to state b in the

accompanying figure along path acb, 100J of heat flows
into the system and the system does 40J of work.
• How much heat flows into the system along path aeb
if the work done by the system is 20J?
• The system returns from b to a along path bda. If the
work done on the system is 30J, does the system
absorb or liberate heat? How much?
 Chemical Engineering Thermodynamics
• Reversible Process: A process is reversible when its
direction can be reversed at any point by an
infinitesimal change in external conditions
• Irreversible Process: Once the process is initiated, no
infinitesimal change in external conditions can reverse
it.
• Irreversibilities: friction, unrestrained expansion,
mixing of two fluids, heat transfer across a finite
temperature difference, electric resistance, inelastic
deformation of solids, and chemical reactions.
• Quasi-static process
 Chemical Engineering Thermodynamics
• Work for Reversible Processes

• Polytropic Process

• Closed-system & Reversible Processes

• A constant-volume change of state
• A constant-pressure change of state:

• Enthalpy:
 Chemical Engineering Thermodynamics

• HEAT CAPACITY
• Heat Capacity at Constant Volume

• Heat Capacity at Constant Pressure

 Chemical Engineering Thermodynamics
• A horizontal piston/cylinder arrangement is placed in a constant-
temperature bath. The piston slides in the cylinder with negligible friction,
and an external force holds it in place against an initial gas pressure of 14
bar. The initial gas volume is 0.03 m3. The external force on the piston is
reduced gradually, and the gas expands isothermally as its volume doubles.
If the volume of the gas is related to its pressure so that PV is constant, what
is the work done by the gas in moving the external force?
 Chemical Engineering Thermodynamics

• Calculate ∆U and ∆H for 1 kg of water when it is vaporized at the constant

temperature of 100°C and the constant pressure of 101.33 kPa. The specific
volumes of liquid and vapor water at these conditions are 0.00104 and 1.673
m3·kg-1, respectively. For this change, heat in the amount of 2256.9 kJ is
added to the water.
 Chemical Engineering Thermodynamics
Air at 1 bar and 298.15 K is compressed to 3 bar and 298.15 K by two
different closed-system mechanically reversible processes:
a) Cooling at constant pressure followed by heating at constant volume.
b) Heating at constant volume followed by cooling at constant pressure.
Calculate the heat and work requirements and ∆U and ∆H of the air for each
path. The following heat capacities for air may be assumed independent of
temperature: CV = 20.785 and CP = 29.100 J·mol-1·K-1.
Assume also that air remains a gas for which PV/T is a constant, regardless of
the changes it undergoes. At 298.15 K and 1 bar the molar volume of air is
0.02479 m3·mol-1
 Chemical Engineering Thermodynamics
• Calculate the internal energy and enthalpy changes resulting if air changes
from an initial state of 5°C and 10 bar, where its molar volume is 2.312 ×
10-3 m3·mol-1, to a final state of 60°C and 1 bar. Assume also that air
remains a gas for which PV/T is constant and that CV = 20.785 and CP =
29.100 J·mol-1·K-1.
 Chemical Engineering Thermodynamics
• One mole of a gas which obeys the relation Pv=RT, where R= 8.314 J/mol.K
is initially at 300 K and 0.1MPa. The gas is heated at constant volume till
the pressure rises to 0.5 MPa and the allowed to expand at constant
temperature Till the pressure reduces to 0.1 MPa. Finally the gas is returned
to its original state by compressing at constant pressure. Calculate the work
done by the gas in each of the processes and also estimate the net work done
by the gas.