Thermodynamics I

ENCH2102
Chapter 1
Introduction

Dr Rajan
Thermodynamics I
ENCH2102

Chapter 1
Introduction

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 History

• The name was coined in 1849 by Lord

Kelvin by combining Greek words for heat
(thermos) and power (dynamos)

• The science of thermodynamics was born

in the middle of 19th century to describe
the operation of steam engine and their
limit of operation.

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 Thermodynamics
Thermodynamics is the study of the inter-
relation between heat, work and internal
energy of a system.

It involves
• the science of heat and work and related
properties
• the basic science that deals with energy
the study of energy movements

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 Scope
• Thermodynamics can predict the
equilibrium yield in a chemical reaction
and help us in selecting the optimum
conditions for the reaction such as
temperature, pressure, concentration of
reactants etc.

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 Why Study Thermodynamics ?

Design of equipment such as

– steam turbines
– refrigerators and heat pumps
– compressors
– boilers
– condensers
– cooling towers and heat exchangers
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 Chemical Engineer and
Thermodynamics
The chemical engineer copes with a particularly
wide variety of problems. It includes

(a) Calculation of heat and work requirements

for physical and chemical processes

(b) Determination of equilibrium conditions for

chemical reactions

(c) Transfer of chemical species between

phases, etc.
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Chemical Engineer and Thermodynamics

Thermodynamic considerations do not

establish the rates of chemical or physical
processes.

• Rates depend on driving force and

resistance.

• Although driving forces are

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 Experiments and Laws
• The basis of thermodynamics is
‘experimental observation’
• These findings have formalized into
certain basic laws
• Zeroth law
• First law of thermodynamics
• Second law of thermodynamics
• Third law of thermodynamics

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 System & Dimensions
• The application of thermodynamics to any real
problem starts with the identification of a particular
body of matter as the focus of attention. This body
of matter is called the system and its
thermodynamic state is defined by a few
measurable macroscopic properties.

• These depend on the fundamental dimensions of

science, of which length, time, mass, temperature,
and amount of substance are of interest here.

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 Dimensions and Units?
• The fundamental dimensions are primitives,
recognized through our sensory perceptions and
not definable in terms of anything simpler.

• Their use, however, requires the definition of

arbitrary scales of measure, divided into specific
units of size.

• International agreement, and are codified as the

International System of Units (abbreviated SI, for
System International).
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Measures of Amounts or Size
• Common measures of amounts or size:

1. Mass, m 2. Number of moles, n 3. Total volume, Vt [m3]

 Relationships between the measures of the amounts or size:

m or
n= m = Mn
M
Where M is the molecular weight
 Specific or molar volume:
t
• Specific volume: V =
V or V t = mV
m
Vt or
• Molar volume: V = V t = nV
n
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Force

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 TEMPERATURE
• Temperature is commonly measured with
liquid-in-glass thermometers, wherein the
liquid expands when heated.

• SI Unit is oC or K ; Other units Rankine,

Fahrenheit

• Conversion
T (K) = T (oC) + 273.15

T (oF) = 1.8 T (oC) + 32 T (R) = 1.8 T (K); T (R) = 1.8 T (oF) + 459.67
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 Pressure
• The pressure P exerted by a fluid on a
surface is defined as the normal force
exerted by the fluid per unit area of the
surface.

Unit: in SI system N m-2 = [Pa]

In English engineering system: force per

square inch (psi)
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 Other units of pressure

1 atm = 101,325 Pa = 101.325 kPa = 0.101325

Mpa = 760 mm Hg

1 bar = 105 Pa = 0.986923 atm

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 Pressure
Normal force exerted by a fluid per unit area of the
acting surface
F
P =
A
For vertical Column
The pressure to which a fluid height corresponds is
determined by the density of the fluid (which depends
on its identity and temperature) and the local
acceleration of gravity.
F Ahρg
P= = = ρgh
A A

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 Gauge & Absolute Pressure
• Most pressure gauges give readings which
are the difference between the pressure of
interest and the pressure of the surrounding
atmosphere. These readings are known as
gauge pressures, and can be converted to
absolute pressures by addition of the
barometric pressure.

• Absolute pressures must be used in

thermodynamic calculations.
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 Important!!
 Thermodynamics deals with absolute pressure which is different than the
gauge reading:

Gauge reading = Absolute pressure – Atmospheric pressure

Pressure above atmospheric

Pressure gauge reading (+ve)
Atmospheric pressure (1 atm)
Vacuum gauge reading (-ve)
Absolute Barometer
pressure
Pressure below atmospheric
reads
(> atm) atmospheric Absolute pressure less
than atmospheric

Datum (zero pressure)

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 Work
 Force acting through distance: W  Fl W  Fdl F = PA
A
 Work caused by displacement of a piston,
e.g. compressing a fluid in a cylinder (work is positive) l

V t  V2
W  -(PA )d   W  -PdV t
W  -  PdV t

 A  V1

Note: V in these equations refers to total volume.

 Sign convention:
 +W: work done by the
surrounding on the system:
 -W: work done by the system on
the surrounding

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 Analogy between Heat and Work
1. Heat and work are both transient phenomena: system never posses heat or
work, but either or both cross the system boundary

2. Both heat and work are boundary phenomena: they are observed at the
boundary of the system and represent energy crossing the boundary

3. Both heat and work are path functions and inexact differential: a path
between initial state and final state should be specified in order to determine Q
or W

4. Sign convention is the same for both heat and work:

+ve: addition of Q or W
-ve : transfer of Q or W

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Energy
Kinetics Energy
If a body m, acted upon a force F, is displaced
F du
a distance dl during a differential time dt. The m dt
work done is given by:

mu 22 mu12
W  -
2 2
Where u is the velocity of the body

• Work done on a body in accelerating it from initial velocity u1 to a final

velocity u2 is equal to the change in kinetics energy of the body.
 mu 2 
  
 2 

1
E k  mu 2
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Potential Energy
If a body m is raised from an initial elevation Z1 m
to a final elevation Z2. The upward force exerted mg dZ
on the body is equal to its weight.
m

Work done on the body in raising it from Z1 to Z2 is equal to the

change of the quantity mgZ

W  E P    mgZ 

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 Work accelerating a body is said to produce a change in its kinetic energy, or

 mu 2 
W  E K    
 2 

 Work done on a body in elevating it is said to produce a change in its potential

energy, or

W  E P    mgZ 

 Potential Energy is defined as

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 Conservation of Energy
 If a body is given energy when it is elevated, then the body conserves or retains
this energy until it performs the work of which it is capable. An elevated body
allowed to fall freely gains in kinetic energy and loses potential energy.

Potential energy is converted into kinetic energy; or its capability for

doing work remains unchanged, or:
Total dW = EK + EP = 0

1 1
Or mu 2  mu12  mgZ 2  mgZ 1  0
2

2 2
 Other types of mechanical energies: Compression of spring by external force,
energy is stored in the spring; later when the spring expands, it performs this work
or releases this energy by a resisting force  spring has capability for doing work.

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 Work & Energy
• The generality of the principle of conservation of energy in
mechanics is increased if we look upon work itself as a form
of energy.

• This is clearly permissible, because both kinetic- and

potential-energy changes are equal to the work done in
producing them.

• However, work is energy in transit and is never regarded as

residing in a body.

• When work is done and does not appear simultaneously as

work elsewhere, it is converted into
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 Work
• The body or assemblage on which attention
is focused is called the system. All else is
called the surroundings.

• When work is done, it is done by the

surroundings on the system, or vice versa,
and energy is transferred from the
surroundings to the system, or the reverse.

• It is only during this transfer that the form of

energy known as work exists.
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 Energy
• In contrast, kinetic and potential energy reside with the
system. Their values, however, are measured with
reference to the surroundings.

• i.e., Kinetic energy depends on velocity with respect to

the surroundings
• Potential energy depends on elevation with respect to a
datum level.

• Changes in kinetic and potential energy do not depend

on these reference conditions, provided they are fixed.

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 Heat
• In the thermodynamic sense, heat is never
regarded as being stored within a body.

• Like work, it exists only as energy in transit

from one body to another, or between a
system and its surroundings.

• When energy in the form of heat is added to

a body, it is stored not as heat but as kinetic
and potential energy of the atoms and
molecules making up the body.
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