Chemical Engineering

Thermodynamics – I
ChE–214
Aqeel Ahmad TAIMOOR
 General Instructions
 Thermodynamics is not an easy subject!!!
 Never miss a class, knowledge is more important than
grades
 Imagination is more important than knowledge. Your
imagination is key in understanding this subject
 If you can’t see thermodynamics working in your daily
lives then you are not understanding it!
 To keep your imagination with in the canvas, class is
open for discussion/Q&A at any time
 Do not let me go further until you understand each and
every thing written on the slides
 General Instructions

 Keep a separate folder for this course with you

 Always refresh your lecture after going home/hostel, DO

IT TODAY!

 Bring your calculators (avoid mobile phones) in the class

 Do the home work regularly and preferably on the same

day in the class
 Grading Policy

 Mid Term Exam = 35% (8th week)

 Quiz = 20% (During the semester)

 Final Exam = 45% (15th week)

Text Books
 “Chemical, Biochemical, and Engineering
Thermodynamics”, Stanley I. Sandler, 5th
Edition, 2016, Wiley Inc.
 “Introduction to chemical engineering
thermodynamics”, Smith J. M.,Van Ness,H. C.,
Abbott M. M., 8th edition, 2010, McGraw Hill.

Reference Book
 “Thermodynamics and its Applications”, J W
Tester and M Modell, 3rd edition, 1999,
Prentice Hall.
Thermodynamics (Quran)

By Time. Indeed Mankind is in loss. Except for

those who have believed and done righteous deeds
and advised each other to truth and patience.
 Introduction
 A wise man/woman is the one, who knows his/her
limits.
 Engineering is a profession of determining limits
 In science and engineering these limits are
usually defined by “THERMODYNAMICS”
 Thermodynamics = Thermo + dynamics
 Thermo = heat, dynamics = continuous
change
 Origin of
Thermodynamics
 Hand Pump
 Origin of
Thermodynamics

 The concepts of
Thermodynamics originated
with the invention of steam
engines.
 Introduction
 Thermodynamics does not tell us
about the rates of chemical and
physical processes!

 It only tells us the maximum change

that can occur!
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world
 Understand the concepts of absolute temperature
 Understand the concept of absolute pressure
 Understand the relation between T, P and V
 Understand the work relation in chemical thermodynamics
 Understand the difference between reversible and irreversible
systems
 Understand that mass is a conserved quantity
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world
 Understand the concepts of absolute temperature
 Understand the concept of absolute pressure
 Understand the relation between T, P and V
 Understand the work relation in chemical thermodynamics
 Understand the difference between reversible and irreversible
systems
 Understand that mass is a conserved quantity
Fundamental Dimensions
Derived Units
Derived Units
 Dimensions and units
 How to measure amount or size
 Mass (m)
 Number of moles n = m/M (M is the molecular weight)
 Volume
 Specific volume (V/m) = 1/specific density
 Molar volume (V/n) = 1/molar density
 Force F = ma/gc (In SI system gC =1)

 F = ma (N=kg.m/s2)
 Problem

An Astronaut weighs 730N in Houstan, Texas, Where the

local acceleration of gravity is 9.792 m/s2. What is the
astronaut’s weight on the moon, where g = 1.67m/s2
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world

 Understand the concepts of absolute temperature

 Understand the concept of absolute pressure

 Understand the relation between T, P and V

 Understand the work relation in chemical thermodynamics

 Understand the difference between reversible and irreversible

systems

 Understand that mass is a conserved quantity

 Historic Times
 Galen 129-217 AD, developed a thermometer to
determine the degree of hotness or coldness.

 He mixed equal amount of ice and boiling water and

termed this mixture as neutral.

 He graduated the thermometer with nine degrees thus

developing a relative scale.

 What is the reason of this departure from the neutral

solution?

Average Energy of the molecules = Temperature

 Renaissance

 Knowledge of heat and work developed and simple heat

or energy balance yielded the Laws of Thermodynamics.
 Temperature
 Thermometer is a glass tube containing fluid.

 Fluid expand with increasing temperature.

 This glass tube was put in freezing water (ice in

equilibrium with liquid water) and the point is marked

 Then it is put in the boiling water (steam in equilibrium

with liquid water) and the point is marked

 In this way a thermometer is graduated by dividing the

two points in 100 parts. 1 part = 1°C
Absolute Temperature
 Temperature scales
 Centigrade scale °C

 Kelvin scale (SI scale K); T(K) = T(°C) + 273

 Fahrenheit Scale °F; T(°C) = (T(°F)-32)/1.8

 Rankine scale R; T(R) = T(°F) + 459.67; T(R) = 1.8T(K)

 Goals
 Be able to use the SI unit system which is used in the text
books and throughout the world

 Understand the concepts of absolute temperature

 Understand the concept of absolute pressure

 Understand the relation between T, P and V

 Understand the work relation in chemical thermodynamics

 Understand the difference between reversible and irreversible

systems

 Understand that mass is a conserved quantity

 Pressure
 Pressure: is determined by the rate
and force of collision of molecules
on the container or system
boundary.

 This implies that pressure is

dependent on the kinetic energy of
the molecules
 Pressure
 P = force/area = ma/A or mg/A (in case of weight)
 P = ρVg/A
 P = ρhAg/A
 P = ρgh
 Units = N/m2 = Pa
 1 atm = 101325Pa
 1bar = 100000Pa
 1 atm = 760mmHg at 0°C
Dead Weight Gauge
 Problem
A dead weight gauge with a 1 cm diameter piston is used to
measure pressures very accurately. In particular instance a
mass of 6.14 kg (including piston and pan) brings it into
balance. If the local acceleration of gravity is 9.82 m/s, what
is the gauge pressure being measured? If the barometric
pressure is 748 torr, what is the absolute pressure?
 Problem
At 300.15K the reading on a manometer filled with mercury
is 60.5 cm. The local acceleration of gravity is 9.784m/s2.
To what pressure does this height of mercury correspond?

Density of mercury at 300.15K = 13.53g/cm3

 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world

 Understand the concepts of absolute temperature

 Understand the concept of absolute pressure

 Understand the relation between T, P and V

 Understand the work relation in chemical thermodynamics

 Understand the difference between reversible and irreversible

systems

 Understand that mass is a conserved quantity

Relation between P, T and V
for an ideal gas

 Regression is conversion of a curve or line into a

mathematical equation

 Above is a straight line equation with intercept = 0

 Ideal Gas Constant

 PV = C + mT (where C = 0 and m = R)

 PV = RT

 The slope can be calculated very easily

 Thus the constant ‘R’ value is determined as

8.314J/mol/K
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world

 Understand the concepts of absolute temperature

 Understand the concept of absolute pressure

 Understand the relation between T, P and V

 Understand the work relation in chemical thermodynamics

 Understand the difference between reversible and irreversible

systems

 Understand that mass is a conserved quantity

 Work
 dW = F dl

 Piston cylinder example with variable volume

 dW = -PA d(V/A)

 dW = -PdV
V2
W = - ò P dV
V1
 Example
A gas is confined in a cylinder by a piston. The initial
pressure of the gas is 7 bar, and the volume is 0.01 m3. The
piston is held in place by latches in the cylinder wall. 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?
V2
W = - ò P dV
V1
 Example
If the process described in the previous example is repeated,
not in a vacuum but in air at atmospheric pressure of 101.3
kPa, what is the energy change of the apparatus? Assume
the rate of heat exchange between the apparatus and the
surrounding air is slow compared with the rate at which the
process occurs.
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world

 Understand the concepts of absolute temperature

 Understand the concept of absolute pressure

 Understand the relation between T, P and V

 Understand the work relation in chemical thermodynamics

 Understand the difference between reversible and irreversible

systems

 Understand that mass is a conserved quantity

 The reversible process
 A process is reversible when its direction can be reversed
at any point by an infinitesimal change in its external
conditions
 For this system to be reversible
 There should be no friction
 System and the piston does not
absorb or transmit heat
 Gravity effects on the gas are
negligible
 Infinitesimal in nature
 There should be no oscillation in
the system by removing the weight
 Irreversible process
 If the all of the energy is not converted to the work then
where did the rest of energy go; After all the total
amount of energy is constant.

 It is not in the system

 It is not converted to work

 Then it must result in increase in the internal energy of

the surroundings
 Problem
An initial pressure of 2.043 bar is maintained on 1 mol of air contained in a piston-
and-cylinder system by a set of weights , the weight of the piston, and the
surrounding atmosphere. Work is obtained by removing some of the weights and
allowing the air to isothermally expand at 25°C, thus lifting the piston and the
remaining weights. The process is repeated until all the weights have been removed.
The piston has a mass of ω = 5 kg and an area of 0.01 m2. For simplicity, the air can
be considered to be an ideal gas. Assume that, as a result of sliding friction between
the piston and the cylinder wall, all oscillatory motions of the piston after the
removal of a weight will eventually be damped. Compute the work obtained from the
isothermal expansion and the heat required from external sources for each of the
following:

a. The weight is W taken off in one step.

b. The weight is taken off in two steps, W/2 with removed each time.

c. The weight is taken off in four steps, W/4 with removed each time.

d. The weight is replaced by a pile of sand (of total weight ), and the grains of sand
are removed one at a time.

Processes are illustrated in the following figure

Problem Schematic
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world
 Understand the concepts of absolute temperature
 Understand the concept of absolute pressure
 Understand the relation between T, P and V
 Understand the work relation in chemical thermodynamics
 Understand the difference between reversible and irreversible
systems
 Understand that mass is a conserved quantity
Law of Mass Conservation

 It is always the mass that is conserved

 Sometimes a confusion persist that moles is also a

conserved quantity

 This is not TRUE!

 Mass in = Mass out + Accumulation

 Problem

A tank of volume 25 m3 contains 1.5 × 104 kg of water.

Over a two-day period the inlet to the tank delivers 2.0 × 103
kg, 1.3 × 103 kg leaves the tank through the outlet port, and
50 kg of water leaves the tank by evaporation. How much
water is in the tank at the end of the two-day period?
 Class Objectives
 Be able to use the SI unit system which is used in the text
books and throughout the world
 Understand the concepts of absolute temperature
 Understand the concept of absolute pressure
 Understand the relation between T, P and V
 Understand the work relation in chemical thermodynamics
 Understand the difference between reversible and irreversible
systems
 Understand that mass is a conserved quantity