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DEPARTMENT OF CHEMICAL ENGINEERING

College of Engineering and Agro-Industrial Technology


University of the Philippines Los Baos
College, Laguna 4031 Philippines Telefax No. (063) 49-536-2315

ChE 142 CHEMICAL ENGINEERING THERMODYNAMICS I


Handout #1
Prepared by: Prof. Myra G. Borines

A. Definition of Thermodynamics

Thermodynamics - A science which deals with transformation of heat and other forms of
energy and with the laws governing such conversions of energy

It is an experimental science based on principles (1st and 2nd Laws) that


are generalized from experience

These principles have no proof in the mathematical sense but their


validity lies in the absence of contrary experience.

B. Scope of Thermodynamics

Thermodynamic considerations do not establish the rates of chemical or physical


processes
Thermodynamics cannot reveal the molecular mechanisms of physical and
chemical processes
Molecular behavior can be useful in the calculation of thermodynamic
properties
Chemical engineer deals with many chemical species and experimental data are
often lacking
Development of generalized correlations to provide property
estimates

C. Applications of Thermodynamics

Every engineering activity involves an interaction between energy and matter


Many household utensils and appliances are designed in whole or in part, using
thermodynamic principles

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D. Historical Background of Thermodynamics

Thermodynamics was formulated in the 18th and 19th centuries investigating the
transformation of different forms of energy
Thermodynamics was then formulated as a science about temperature, heat, and
also interconvertibility of heat and work into each other.
The term was derived from the Greek words, therme" (heat), and "dynamis",
(strength or power).
The first attempt to build a steam engine and the need to describe its operation
paved the way to the development of thermodynamics as a science
Thermodynamics was first used in a publication by Lord Kelvin in 1849
The first textbook was written in 1859 by W. Rankine, professor at the University
of Glasgow

Concept of Temperature

The history of thermodynamics started with G. Galilei (1597) who introduced the
concept of temperature and invented one of the first thermometers.
Galileo (ca 1630): temperature measured (but not understood)
Fahrenheit (1715) measured Temperature by expansion of a fluid (gas or
mercury)
Celsius (1742): defined 0C as the melting point of ice; 100C as the boiling point of
water; scale in between linear with expansion of fluid
Realization that matter is composed of discrete atoms and molecules, Lavoisier
(1780)
Dalton (1808), temperature was seen as a measure of the particles speed (gas) or
vibration (solid)
Kelvin (ca 1885) introduced the notion of absolute zero temperature where all
atomic motion stops based on the Carnot cycle
International Committee (1954): defines the unique state of water: the triple
point (ice, water, and water vapor coexist) as 0.01C at 611 Pa (0.00611 atm)

Notion of Heat

Since the 18th Century, heat was viewed as a fluid (caloric) that moves from a
body at high temperature to one at low temperature
Caloric theory was postulated by the French chemist Antoine Lavoisier.

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Rumford disproved the caloric theory by his investigation of canon boring
Count Rumford (Benjamin Thompson) began the quantitative study of the
conversion of work into heat by means of his famous cannon-boring experiments.
In 1799, Sir Humphry Davy studied the conversion of work into heat by means of
his ice-rubbing experiments.
In 1772 G. Wilke introduced the unit of measuring the amount of heat, a calorie.
During the 19th Century., the correct view of heat was uncovered: it is energy in
motion from hot to cold regions
Heat and temperature are fundamentally different

Work

Known from mechanics since Newton (1687) as force distance


Heat and Work are two aspects of energy in motion; work is completely
convertible to heat (Rumford, Joule (1840))

Steam Engine

Nicolas Leonard Sadi Carnot developed the physical elements of the steam engine using
a thought-experiment (Carnot cycle).
Carnot published his famous thesis Reflections on the Motive Power of Fire," which
includes the new concept of cycle and the principle that the reversible cyclic engine
operating between two heat reservoirs depends only on the temperatures of the
reservoirs and not on the working substance.

Energy and the First Law

Energy comes in many interconvertible forms: internal (atomic vibrations); chemical (in
chemical bonds); electrical, kinetic and potential
Mayer (1842), postulated the principle of conservation of energy :
Energy can be neither created nor destroyed
In 1847, Helmholtz formulated the principle of conservation of energy independent of
Mayer and Joule
Helmholtz, Clausius (ca 1850), energy is related to heat and work by the First Law of
Thermodynamics: E = Q W
o Energy is a property of a body; Q and W are not
Joule (ca 1850) was the first thermodynamic experimentalist

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o He laid the experimental foundation of the first law of thermodynamics by
performing experiments to establish the equivalence of work and heat
o measured the Mechanical Equivalent of Heat heat in calories (to raise the
temperature of water 1C); work in Joules (exerting a force of 1 Newton over 1
meter); Joules per calorie: 4.184
With energy, heat and work in the same units, the 1st Law could be written:
U = Q W
where: Q = heat added to the system
W = work done by the system

Energy and the Second Law

development of steam engines showed that heat is not completely convertible to work
-Watt (1778)
o Carnot (1824) showed theoretically why this is so

Statements of the Second Law

Max Planck: "It is impossible to construct an engine which, working in a complete cycle,
will produce no effect other than the raising of a weight and the cooling of a heat
reservoir."
Kelvin and Planck: It is impossible for any engine to transfer heat from cold source to a
hot source without work being done.
Clausius: It is impossible to convert heat completely to work

Entropy and the Second Law

Clausius and Kelvin developed the concept of reversible and irreversible processes
Clausius (ca 1850) uncovers a new thermodynamic property, entropy, as S = Q/T for
reversible processes
19th Century, Practical cycles of converting (partially) heat to work are developed
(Rankine, Otto, Brayton)

Foundation of Thermodynamics

In 1850, Clausius was probably the first to see that there were two basic principles: the
First and Second Laws of Thermodynamics

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He also introduced the concept of U, which we now call the internal energy.
In 1865, Clausius stated the First and Second Laws Thermodynamics in two lines:
1. The energy of the universe is constant
2. The entropy of the universe tends toward a maximum.

Chemical Thermodynamics

Deals with the dependence of thermodynamic properties of substances on their


composition, structure, and existence conditions.
Josiah Willard Gibbs published his monumental work " On the Equilibrium of
Heterogeneous Substances," which extends thermodynamics in a general form to
heterogeneous systems and chemical reactions.
Gibbs introduces the chemical potential as equivalent to thermal potential
(temperature) and mechanical potential (pressure difference)
Deals with the equilibrium of molecular species in a reacting mixture
Chemistry based on the atomic theory of matter (Dalton)

Statistical Thermodynamics
based on representations of the molecular (atomic) structure of physical bodies. Its
tools are statistical methods and the mathematical apparatus of probability theory.
Links atomic motions to thermodynamic properties
Boltzmann (ca 1885) discovers the formula for the absolute temperature S = klnW
Planck (1900), quantization of energy states
Einstein, Debye (1905), atomic explanation of internal energy
Fermi, Dirac, Bose, quantum statistical thermodynamics

Third Law of Thermodynamics


Giauque (1930): The entropy of a body is zero at absolute zero temperature.

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Thermodynamics Timeline

Date Event

1798 Count Rumford (Benjamin Thompson) began the quantitative study of the
conversion of work into heat by means of his famous cannon-boring
experiments.
1799 Sir Humphry Davy studied the conversion of work into heat by means of his
ice-rubbing experiments.
1824 Sadi Carnot published his famous thesis " Reflections on the Motive Power
of Fire," which includes the new concept of cycle and the principle that the
reversible cyclic engine operating between two heat reservoirs depends only
on the temperatures of the reservoirs and not on the working substance.
1842 Mayer postulated the principle of conservation of energy.
1847 Helmholtz formulated the principle of conservation of energy, independent
of Mayer.
1843-1848 James Prescott Joule laid the experimental foundation of the first law of
thermodynamics by performing experiments to establish the equivalence of
work and heat. We now honor
this great scientist by using J to denote the mechanical equivalent of heat
1848 Lord Kelvin (William Thomson) defined an absolute temperature scale based
on the Carnot cycle.
1865 Clausius stated the first and second laws of thermodynamics in two lines:
1. The energy of the universe is constant.
2. The entropy of the universe tends toward a maximum.
1875 Josiah Willard Gibbs published his monumental work " On the Equilibrium of
Heterogeneous Substances," which extends thermodynamics in a general
form to heterogeneous systems and chemical reactions. This work includes
the important concept of chemical potential.
1897 Max Planck stated the second law of thermodynamics in the following form:
"It is impossible to construct an engine which, working in a complete cycle,
will produce no effect other than the raising of a weight and the cooling of a
heat reservoir."
1909 Caratheodory published his structure of thermodynamics on a new
axiomatic basis, which is entirely mathematical in form.

References:
"Engineering Thermodynamics - Fundamentals and Applications by Francis F. Huang
Introduction to Chemical Engineering Thermodynamics 7th ed. by Smith, Van Ness and Abbott
http://www.mhtl.uwaterloo.ca/courses/me354/past.html
http://wikipedia

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