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CHAPTER I
OBJECTIVES
Definition of Thermodynamics
Thermodynamics is the science that deals with the study of energy transformation and the
relationships of the physical properties of substances that are affected by these transformations. It
is a science in which the storage, the transformation, and the transfer of energy are studied.
Energy is stored as internal energy (associated with temperature), kinetic energy (due to motion),
potential energy (due to elevation) and chemical energy (due to chemical composition); it is
transformed from one of these forms to another; and it is transferred across a boundary as either
heat or work. It stems from the Greek words therme, which means heat; and dynamics, which
means force.
This is a macroscopic science that deals with the average changes that occur among large
number of molecules rather than the detailed changes that occur in a single molecule. In
thermodynamics we will develop mathematical equations that relate the transformations and
transfers of energy to material properties such as temperature, pressure, or enthalpy. Substances
and their properties thus become an important secondary theme. Much of our work will be based
on experimental observations that have been organized into mathematical statements, or laws;
the first and second laws of thermodynamics are the most widely used.
In science, thermodynamics (from the Greek θέρμη therme, meaning "heat" and δύναμις,
dynamis, meaning force) is the study of energy conversion between heat and mechanical work,
and subsequently the macroscopic variables such as temperature, volume and pressure.
The starting point for most thermodynamic considerations are the laws of
thermodynamics, which postulate that energy can be exchanged between physical systems as
heat or work. They also postulate the existence of a quantity named entropy, which can be
defined for any isolated system that is in thermodynamic equilibrium.
With these tools, thermodynamics can be used to describe how systems respond to
changes in their surroundings. This can be applied to a wide variety of topics in science and
engineering, such as engines, phase transitions, chemical reactions, transport phenomena, and
even black holes. The results of thermodynamics are essential for other fields of physics and for
chemistry, chemical engineering, aerospace engineering, mechanical engineering, cell biology,
biomedical engineering, materials science, and economics, to name a few.
The history of thermodynamics as a scientific discipline generally begins with Otto von
Guericke who, in 1650, built and designed the world's first vacuum pump and demonstrated a
vacuum using his Magdeburg hemispheres. Guericke was driven to make a vacuum in order to
disprove Aristotle's long-held supposition that 'nature abhors a vacuum'. Shortly after Guericke,
the English physicist and chemist Robert Boyle had learned of Guericke's designs and, in 1656,
in coordination with English scientist Robert Hooke, built an air pump. Using this pump, Boyle
and Hooke noticed a correlation between pressure, temperature, and volume. In time, Boyle's
Law was formulated, which states that pressure and volume are inversely proportional. Then, in
1679, based on these concepts, an associate of Boyle's named Denis Papin built a bone digester,
which was a closed vessel with a tightly fitting lid that confined steam until a high pressure was
generated.
Later designs implemented a steam release valve that kept the machine from exploding.
By watching the valve rhythmically move up and down, Papin conceived of the idea of a piston
and a cylinder engine. He did not, however, follow through with his design. Nevertheless, in
1697, based on Papin's designs, engineer Thomas Savery built the first engine, followed by
Thomas Newcomen in 1712. Although these early engines were crude and inefficient, they
attracted the attention of the leading scientists of the time. Their work led 127 years later to Sadi
Carnot, the "father of thermodynamics", who, in 1824, published Reflections on the Motive
Power of Fire, a discourse on heat, power, and engine efficiency. The paper outlined the basic
energetic relations between the Carnot engine, the Carnot cycle, and motive power. It marked the
start of thermodynamics as a modern science.
The term thermodynamics was coined by James Joule in 1849 to designate the science of
relations between heat and power. By 1858, "thermo-dynamics", as a functional term, was used
in William Thomson's paper An Account of Carnot's Theory of the Motive Power of Heat. The
first thermodynamic textbook was written in 1859 by William Rankine, originally trained as a
physicist and a civil and mechanical engineering professor at the University of Glasgow.The first
and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the
works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin).
The foundations of statistical thermodynamics were set out by physicists such as James
Clerk Maxwell, Ludwig Boltzmann, Max Planck, Rudolf Clausius and J. Willard Gibbs.
During the years 1873-76 the American mathematical physicist Josiah Willard Gibbs
published a series of three papers, the most famous being On the Equilibrium of Heterogeneous
Substances, in which he showed how thermodynamic processes could be graphically analyzed,
by studying the energy, entropy, volume, temperature and pressure of the thermodynamic system
in such a manner, one can determine if a process would occur spontaneously. During the early
20th century, chemists such as Gilbert N. Lewis, Merle Randall, and E. A. Guggenheim began to
apply the mathematical methods of Gibbs to the analysis of chemical processes.
Classical thermodynamics
Statistical mechanics
Chemical thermodynamics
The study of the interrelation of energy with chemical reactions or with a physical change
of state within the confines of the laws of thermodynamics.
Equilibrium thermodynamics
The systematic study of transformations of matter and energy in systems as they approach
equilibrium. The word equilibrium implies a state of balance. In an equilibrium state there are no
unbalanced potentials, or driving forces, within the system. A central aim in equilibrium
thermodynamics is: given a system in a well-defined initial state, subject to accurately specified
constraints, to calculate what the state of the system will be once it has reached equilibrium.
Non-equilibrium thermodynamics
Branch of thermodynamics that deals with systems that are not in thermodynamic equilibrium.
Most systems found in nature are not in thermodynamic equilibrium because they are not in
stationary states, and are continuously and discontinuously subject to flux of matter and energy
to and from other systems. The thermodynamic study of non-equilibrium systems requires more
general concepts than are dealt with by equilibrium thermodynamics. Many natural systems still
today remain beyond the scope of currently known macroscopic thermodynamic methods.
In thermodynamics, there are four laws that do not depend on the details of the systems
under study or how they interact. Hence these laws are very generally valid, can be applied to
systems about which one knows nothing other than the balance of energy and matter transfer.
Examples of such systems include Einstein's prediction of spontaneous emission, and ongoing
research into the thermodynamics of black holes.
"If two systems are in thermal equilibrium with a third, they are also in
thermal equilibrium with each other."
surroundings. Work and heat are due to processes which add or subtract
energy, while internal energy is a particular form of energy associated with
the system. Internal energy is a property of the system whereas work done
and heat supplied are not. A significant result of this distinction is that a
given internal energy change can be achieved by many combinations of
heat and work.
"Heat cannot spontaneously flow from a colder location to a hotter
location."
This is used in the analysis and design of large scale or small scale system which serve as
a continuum in which the activity of the constituent molecules is averaged into measurable
quantities such as pressure, temperature, and volume for which will help evaluate the
transformation, storage and transfer of energy. Continuum means that the material in the system
is continuously distributed throughout the region of interest.
The boundary may be real or imagined, may be at rest or in motion, and may change in size
or shape. The surface that completely surrounds the control volume is called a control surface.
The consideration in determining specific boundaries:
1. what is known about a possible system particularly at its boundaries.
2. objective of analysis
The surrounding is the region of physical space outside the boundaries of the system.
The first step in any thermodynamic analysis must be the selection of the system, its
boundaries, and its surroundings.
Property is any quantity which serves to describe the system. It is the macroscopic
characteristic of a system, i.e. mass, volume, energy, pressure and temperature. Mass flow rate, Q
or heat, and W or work, are not thermodynamic properties. The essential feature of a property is
that it has a unique value when a system is in a particular state, and this value does not depend on
the previous states that the system passed through. It can be:
1. Extensive Variable : are properties that are dependent on the amount of matter in the system,
e.g. volume and heat capacity. If two systems are brought together the
2. Intensive Variable : are properties that are independent of the amount of matter in the system,
e.g. viscosity, temperature, and pressure. If we bring two systems together,
intensive properties are not summed.
d
1
2 1
This requires that d be an exact differential; 2 1 represents the change in the property as
the system changes from state 1 to state 2. There are quantities which we will encounter, such as
work, that are path functions for which an exact differential does not exist.
The essential feature of a property is that it has a unique value when a system is in a
particular state, and this value does not depend on the previous states that the system passed
through; that is, it is not a path function. Since a property is not dependent on the path, any
change depends only on the initial and final states of the system.
Path Function : macroscopic quantities that are dependent on the process taken by the
system, eg. Q, W.
Thermal Reservoir: reservoir, a special kind of system that always remains at constant
temperature even through energy or removed by heat transfer.
System of units
1. International System of Units (SI)
a. Meter-kilogram-second (MKS)
b. Centimeter-gram-second (CGS)
2. English engineering system
Primary units
1. Second (s), SI unit of time, the duration of 9,192,631,770 cycles of radiation associated
with a specified transition of the cesium atom.
2. Meter (m), SI unit of length, the distance light travels in a vacuum during 1/299,792,458
of a second.
3. Kilogram (kg), SI unit of mass, mass of a platinum/iridium cylinder kept at the
International Bureau of Weights and Measures at Sevres, France.
4. Kelvin (K), SI unit of temperature, equal to 1/273.16 of the thermodynamics temperature
of the triple point of water.
5. Mole (mol), the amount of substance represented by as many elementary entities (e.g.,
molecules) as there are atoms in 0.012 kg of carbon-12.
Amedeo Avogadro (1776-1856): in 1811, hypothesize that a given volume of any gas (at a fixed
temperature and pressure) must contain the same number of independent particles which can be
atoms or combinations of atoms, molecules.
Vn or V C ' ' ' n (valid at constant P and T )
Where: n amount of substance, moles
Mole: amount of any substance containing the same number of elementary entities (atoms,
molecules, ions) as there are in exactly 0.012 kg of carbon-12.
Avogadro’s constant: 6.022137 x 1023 mol-1, the number of elementary entities on a mole,
symbol L (after Joseph Loschmidt (1821-1895) who first measured its magnitude).
FORCE
TEMPERATURE
International Temperature Scale of 1990 (ITS-90) is used for calibration of scientific and
industrial instruments, based on assigned values of temperature for a number of reproducible
phase-equilibrium states of pure substances (fixed points) and on standard instruments calibrated
at these temperatures.
t ( o C ) T ( K ) 273.15
T ( R ) 1.8T ( K )
t ( o F ) T ( R ) 459.67
t ( o F ) 1.8t ( o C ) 32
When two objects at different temperatures are placed in contact with each other through
a diathermic boundary for a long period of time, their temperature will become equal.
Zeroth Law of Thermodynamics: Two bodies in thermal equilibrium with a third are in
equilibrium with each other.
Temperature the property that indicates the direction of the flow of energy through a
thermally conducting, rigid wall.
Olaus Romer (1644-1710): First Thermometer using the freezing point and boiling point
of water as references. The freezing point was fixed at 0 deg C and boiling point at 100 deg C.
Anders Celsius (1701-1744): Swedish astronomer where the Celsius scale named was
derived, Latin centum, hundred; gradus, step; also called as the Celsius scale.
Ideal gas thermometer: use gas that obeys Gay-Lussac’s law for all values of P and eqn. 1.26.
lim PV T2
p 0
T2 273.16 0
(constant P and n)
lim PV triple point
p 0
Celsius scale: temperatures were related to the length of a column of liquid, and the difference in
lengths shown when the thermometer was first in contact with melting ice and then with boiling
water was divided into 100 steps called' degrees', the lower point being labeled 0.
Degrees. Distance between the two marks, divided into 100 equal spaces.
Kelvin Scale
T
0 273.15
K C
PRESSURE
It is the normal force exerted by the fluid per unit area of the surface.
Units: Pascal or N/m2 (SI), lbf/in2 or psi (English), mmHg or torrs, atm, bars.
F mg Ahg
P gh
A A A
Measuring devices:
1. Dead-weight gauges. Piston is carefully fitted to the cylinder making the clearance small.
Weights are placed on the pan until the pressure of the oil, which tends to make the piston
rise, is just balanced by the force of gravity on the piston and all that is supports.
2. Bourdon gauges. Element expands making the arm of the reading device move relative to
the pressure exerted on the tappings.
3. Manometer. A vertical column of a given fluid under the influence of gravity exerts a
pressure at its base in direct proportion to its height.
Manometer: u-tube filled with a liquid of low volatility (such as mercury or silicone oil). The U-
tube can be open on both ends or just one end only.
Manometer
With closed end: sample pressure is directly proportional to the height difference of the
two columns.
Open-end: pressure is proportional to the difference in height of the two columns and the
atmospheric pressure.
sealed at the upper end. When the column of mercury is in mechanical equilibrium with the
atmosphere, the pressure at its base is equal to that exerted by the atmosphere.
Evangelista Torricelli: made the barometer, where there is a vacuum trapped by the mercury
which is filling the tube, which is placed inverted in the pool of mercury.
Barometric formula P P0 e h / H
where Po is the pressure at sea level and H is a constant approximately equal to 8 km.
RT
H
Mg
where M is the average molar mass of air and T is the temperature.
Others
Bayard-Alpert pressure gauge: is based on the ionization of the molecules present in the gas
and the resulting current of ions is interpreted in terms of the pressure.
Capacitance manometer: the deflection of a diaphragm relative to a fixed electrode is
monitored through its effect on the capacitance of the arrangement.
Solid-state pressure gauges: semiconductors also respond to pressure and are used as
transducers.
Mechanical Equilibrium: If two gases are in separate containers that share a common movable
wall, the gas that has the higher pressure will tend to compress (reduce the volume of) the gas
that has lower pressure. The pressure of the high -pressure gas will fall as it expands and that of
the low-pressure gas will rise as it is compressed. There will come a stage when the two
pressures are equal and the wall has no further tendency to move. This condition of equality of
pressure on either side of a movable wall (a 'piston') is a state of mechanical equilibrium between
the two gases.
Gauge pressure. (Pg) Pressure exerted in a confinement or trapped container of fluid, pressure
above atmospheric.
h
h h
WORK
Work: can be readily transformed into other forms of energy. Force acting through a distance.
dW F dl F cosdl
x0
Work form of energy that represents a transfer between the system and surroundings. Work is
positive when done on the system.
W = ∫ F dS = ∫V2 P dV
V1
Electrical work energy transferred to the system under the voltage potential, voltage is applied
to a resistance in a system that results in current flow that in turn increases the internal
energy of the system.
Shaft work is the work done if the system turns the shaft of a motor or compressor.
KINETIC ENERGY
The energy of a system possesses because of its velocity relative to the surrounding at rest.
KE = ½ mv2 KE = ½ v2
Where:v - velocity
m – mass
KE – energy per unit mass
1
Ek mu 2
2
Velocity: instantaneous rate of change of the position vector with respect to time.
l l dl l
W F (l )dl F (l ) dt F (l )udt
l0 l0 dt l 0
l 1 1
W F (l )dl mu12 mu22 Ek1 Ek 2
l0 2 2
POTENTIAL ENERGY
The energy of the system possesses because of the body force exerted on its mass by a
gravitational or electromagnetic field with respect to reference surface.
P = mgh P = gh
F (l ) dl dE p (l )
x x 1
EP Fdx k h xdx k h x 2
0 0 2
Conservation Law l
W F (l )dl E P0 EP1 EK1 EK 0
l0
E P0 E K 0 E P1 E K1
INTERNAL ENERGY
Macroscopic measure of the molecular, atomic and subatomic energies, all which follow definite
macroscopic conservation rules for dynamic systems.
∆U = ∫T2 Cv dT
T1
HEAT
That part of the total energy flow across a system boundary that is caused by the temperature
difference between the system and the surroundings. This is positive when transferred to
the system.
Q = UA ∆T
PROBLEM SETS
Solve the problems at the end of Chapter 1 of ChE Thermodynamics by Van Ness and Abbott.