Sie sind auf Seite 1von 16

Chapter I: Introduction to ChE Thermodynamics

CHAPTER I

INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS

OBJECTIVES

1. To learn the concept of thermodynamics.


2. To calculate specific quantities utilized widely in thermodynamics.
3. To learn the variables that is being quantified and evaluated for most of the
phenomena happening relative to thermodynamics.

INTRODUCTION TO CHEMICAL ENGINEERING THERMODYNAMICS

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.

Lecture Notes for ChE 353 : ChE Thermodynamics I 1


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

Historically, thermodynamics developed out of a need to increase the efficiency of early


steam engines, particularly through the work of French physicist Nicolas Léonard Sadi Carnot
(1824) who believed that engine efficiency was the key that could help France win the
Napoleonic Wars. The first to give a concise definition of the subject was Scottish physicist
William Thomson who in 1854 stated that;

Thermo-dynamics is the subject of the relation of heat to forces acting between


“ contiguous parts of bodies, and the relation of heat to electrical agency. ”
Two derivatives of thermodynamics which emerged in the following decades were
statistical thermodynamics (or statistical mechanics) (1860), a subject concerned with statistical
predictions of the collective motion of particles from their microscopic behavior, and chemical
thermodynamics (1873), a subject concerned with the nature of the role of entropy in the process
of chemical reaction.

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.

In thermodynamics, interactions between large ensembles of objects are studied and


categorized. Central to this are the concepts of system and surroundings. A system is composed
of particles, whose average motions define its properties, which in turn are related to one another
through equations of state. Properties can be combined to express internal energy and
thermodynamic potentials, which are useful for determining conditions for equilibrium and
spontaneous processes.

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 present article is focused mainly on classical thermodynamics, which is concerned


with systems in thermodynamic equilibrium. It is wise to distinguish classical thermodynamics
from non-equilibrium thermodynamics, which is concerned with systems that are not in
thermodynamic equilibrium.

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 2


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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.

Connectivity diagram of the twelve founding schools of thermodynamics, Scottish


physicist William Thomson being the main connector in the original formation of the subject of
thermodynamics, via his travels to Paris to obtain a copy of Sadi Carnot’s 1824 Reflections on
the Motive Power of Fire, and his followup 1848-49 papers on this subject, and for his influence
and interactions in connecting Rudolf Clausius, James Maxwell, and Ludwig Boltzmann, thus
creating a linked framework for the five inception schools of thermodynamics.

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 3


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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

Concerned with macroscopic thermodynamic states and properties of large, near-


equilibrium systems. It is used to model exchanges of energy, work and heat based on the laws of
thermodynamics. The term "classical" reflects the fact that it represents the level of knowledge in
the early 1800s. An atomic interpretation of these principles was provided later by the
development of statistical mechanics. Nonetheless, classical thermodynamics is still a practical
and widely-used science.

Statistical mechanics

Or statistical thermodynamics, emerged only with the development of atomic and


molecular theories in the late 1800s and early 1900s, giving thermodynamics a molecular
interpretation. This field relates the microscopic properties of individual atoms and molecules to
the macroscopic or bulk properties of materials that can be observed in everyday life, thereby
explaining thermodynamics as a natural result of statistics and mechanics (classical and
quantum) at the microscopic level. This statistical approach is in contrast to classical
thermodynamics, which is a more phenomenological approach.

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 4


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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.

These four laws are:

"If two systems are in thermal equilibrium with a third, they are also in
thermal equilibrium with each other."

Systems are said to be in equilibrium if the small, random exchanges (due


to Brownian motion, for example) between them do not lead to a net
change in the total energy summed over all systems. This law is tacitly
assumed in every measurement of temperature. Thus, if we want to know if
two bodies are at the same temperature, it is not necessary to bring them
The zeroth law of
into contact and to watch whether their observable properties change with
thermodynamics
time.

This law was considered so obvious[citation needed] it was added as a virtual


afterthought, hence the designation Zeroth, rather than Fourth. In short, if
the temperature of material A is equal to the temperature of material B, and
B is equal to the temperature of material C, then A and C must also be
equal. This implies that thermal equilibrium is an equivalence relation on
the set of thermodynamic systems.
The first law of "In any process in an isolated system, the total energy remains the same."
thermodynamics
The first law of thermodynamics, an expression of the principle of
conservation of energy, states that energy can be transformed (changed
from one form to another), but cannot be created or destroyed.

It is usually formulated by saying that the change in the internal energy of a


closed thermodynamic system is equal to the amount of heat supplied to
the system, minus the amount of work done by the system on its

Lecture Notes for ChE 353 : ChE Thermodynamics I 5


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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."

The second law of thermodynamics is an expression of the universal


principle of decay observable in nature. The second law is an observation
of the fact that over time, differences in temperature, pressure, and
chemical potential tend to even out in a physical system that is isolated
from the outside world. Entropy is a measure of how much this evening-out
The second law of process has progressed. The entropy of an isolated system which is not in
thermodynamics equilibrium will tend to increase over time, approaching a maximum value
at equilibrium.

In classical thermodynamics, the second law is a basic postulate applicable


to any system involving heat energy transfer; in statistical thermodynamics,
the second law is a consequence of the assumed randomness of molecular
chaos. There are many versions of the second law, but they all have the
same effect, which is to explain the phenomenon of irreversibility in
nature.
"As a system approaches absolute zero, all processes cease and the entropy
of the system approaches a minimum value."

The third law of thermodynamics is a statistical law of nature regarding


entropy and the impossibility of reaching absolute zero of temperature.
This law provides an absolute reference point for the determination of
entropy. The entropy determined relative to this point is the absolute
The third law of
entropy. Alternate definitions are, "the entropy of all systems and of all
thermodynamics
states of a system is smallest at absolute zero," or equivalently "it is
impossible to reach the absolute zero of temperature by any finite number
of processes".

Absolute zero, at which all activity would stop if it were possible to


happen, is −273.15 °C (degrees Celsius), or −459.67 °F (degrees
Fahrenheit) or 0 K (kelvins, formerly sometimes called degrees absolute).

Objective of Studying Thermodynamics

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 6


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

transformation, storage and transfer of energy. Continuum means that the material in the system
is continuously distributed throughout the region of interest.

System, Control Volume, Boundary, Control Surface and Surrounding

A thermodynamic system is a three-dimensional region specified by volume in space or


quantity of matter selected to be studied. For some it is some definite quantifiable matter
flowing in or out in an enclosed space or control volume. There are three types of
thermodynamic systems:
1. Open system, a thermodynamic system for which there is exchange of energy and matter
with the surroundings or may cross the boundary of the control volume.
2. Closed system, a thermodynamic system for which there is only exchange of energy with
the surroundings, but the mass of the system remains constant.
3. Isolated System, special type of closed system that does not interact in any with its
surroundings. This can be differentiated into:
 Thermally isolated system where there is no exchange of energy and matter with
the surroundings, and
 Mechanically isolated system where there is no work done on the system or by the
system

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.

Properties and State of a System

Phase, state of agglomeration of the system. It refers to a quantity of matter that is


homogeneous throughout in both chemical composition and physical structure, e.g. gas, liquid,
or solid.

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 7


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

extensive property of the new system is the sum of the extensive


properties of the original two systems.

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.

State refers to the condition of a system as described by its properties.


State Function is the macroscopic quantities that are dependent only on the initial and
final state of the thermodynamic system, and independent of the process taken by the system, eg.
P, V, T, H, U, G, S, A. Using the symbol  to represent a property, that is stated mathematically
as
2

 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.

DIMENSIONS AND UNITS

Fundamental dimensions are primitives.


Derived dimensions are combination of fundamental dimensions.
Units are the arbitrary scales of measure of size.
Conversion factors values fixed interrelated by two system of units considered to convert one to
the other.

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 8


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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.

Table 1. Prefixes for SI units


Multiple Prefix Symbol Multiple Prefix Symbol
10-15 Femto f 102 hecto H
10-12 Pico p 103 kilo K
10-9 Nano n 106 mega M
10-6 Micro μ 109 giga G
10-3 Milli m 1012 tera T
-2
10 Centi c 1015 peta P

MEASURES OF AMOUNT OR SIZE

1. Mass (m) a primitive without definition.


2. Molar mass or molecular weight (M) is the mass per unit mole of a compound or
element.
3. Moles (mol)
4. Total Volume the product of three lengths.
5. Specific Volume is the total volume divided by its mass, an intensive property.
6. Molar Volume is the total volume divided by its number of moles, an intensive property.
7. Specific Density is the reciprocal of specific volume, also known as density, an intensive
property.
8. Molar Density is the reciprocal of molar volume, intensive property.

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.
Vn 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).

Lecture Notes for ChE 353 : ChE Thermodynamics I 9


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

FORCE

Force is the product of mass and acceleration.


1
F= ma
gc
gc = 32.1740 (lbm)(ft)(lbf)-1(s)-2 (English)
= 1 (kg)(m)(N)-1(s)-2 (SI)
Newton (N), SI unit of force, derived from Newton’s second law, mass of 1 kg produces an
acceleration of 1 m/s2.
Pound force (lbf), force which accelerates 1 pound mass 32.174 ft/s2.

TEMPERATURE

It is the degree of hotness or coldness of body or control volume.

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.

The Concept of Temperature and its Measurement

 Temperature the property that indicates the direction of the flow of energy through a
thermally conducting, rigid wall.

Two types of boundary

Lecture Notes for ChE 353 : ChE Thermodynamics I 10


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

 Diathermic: (thermally conducting) if a change of state is observed when two objects at


different temperatures are brought into contact.'
 Adiabatic: (thermally insulating) if no change occurs even though the two objects have
different temperatures.

 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.

 Gay Lussac’s Law lim V  CT ,


p0
C - constant

The ratio of temperature before and after the addition of heat:


T2 lim p 0
V2

T1 lim V1
p 0
Low-pressure limit of a gas is infinite:
T2 lim
p 0
 PV  2

T1 lim PV  1
p 0

Measuring device used:


1. Thermometers. Liquid expands when heated in a uniform tube, partially filled with
mercury, alcohol or some other fluid, where the numerical values are assigned to the
various degrees of hotness by arbitrary definition.
2. Thermocouple. Two different metallic wires which are interconnected and expands
differently on varying temperature conditions that gives a differential potential values that
gives the measure of degree of hotness.

Ideal gas thermometer: use gas that obeys Gay-Lussac’s law for all values of P and eqn. 1.26.

Triple point: (water-ice-water vapor equilibrium) at exactly 273.16K exactly.


New Celsius scale:

lim PV  T2
p 0
T2  273.16  0
(constant P and n)
lim PV  triple point
p 0

where lim PV  T  0 when T2  0


p 0

Lecture Notes for ChE 353 : ChE Thermodynamics I 11


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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.

Perfect-gas temperature scale and Thermodynamic Temperature Scale

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 Ahg
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.

4. Barometer: device in measuring atmospheric pressure. The original version of a barometer


(which was invented by Torricelli, a student of Galileo) was an inverted tube of mercury

Lecture Notes for ChE 353 : ChE Thermodynamics I 12


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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.

 Measurement based on distortion of an elastic pressure chamber:


 Bourdon-tube gauges: high pressure
 Diaphragm gauges: moderate pressure

 Measurement based on electrical sensors:


 Strain gauges: moderate range of vacuum pressure
 Pirani gauges or thermocouple gauges: 10-3 torr vacuum pressure
 Thermionic ionization gauges, cold cathode gauges, and Baynard-Alpert ion gauges

 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.

Absolute pressure. (Pabs) Total pressure exerted at a certain points of consideration.

Gauge pressure. (Pg) Pressure exerted in a confinement or trapped container of fluid, pressure
above atmospheric.

Vacuum pressure. (Pv) Pressure below atmospheric conditions.

Lecture Notes for ChE 353 : ChE Thermodynamics I 13


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

Atmospheric pressure. (Patm) Pressure exerted by the atmosphere.


Pabs  Patm  Pg
Pabs  Patm  Pv

h
h h

Gas pressure, Pgas, is Gas pressure, Pgas, is


Gas pressure, Pgas,
greater than atmos- less than atmospheric
pheric pressure pressure
Pgas = ρgh
Pgas = Patm + ρgh Pgas = Patm - ρgh

WORK

Work: can be readily transformed into other forms of energy. Force acting through a distance.
dW  F  dl  F cosdl

Constant force in the x-direction:


W   Fx dx  Fx  x  x0 
x

x0

where: xo = initial value of x (x0 = 0)

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 14


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

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

where: u (= dl/dt), velocity


m, mass

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

Given based on Newton’s Second Law:


du
F  ma  m
dt
t du u
W  m udt  m  udu
t0 dt u0

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

Lecture Notes for ChE 353 : ChE Thermodynamics I 15


by: Mary Rose B. Flores-Persincula
Chapter I: Introduction to ChE Thermodynamics

Where: P – Energy per unit mass


m – mass
g – gravitational constant
h – height, distance from the reference symbol

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

Where:Cv – heat capacity at constant volume

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

Where : Q – rate of heat transfer


U – empirical coefficient, over-all heat transfer coefficient
A – area for heat transfer
∆T – change in temperature

Q = ∫Cp ∆T if ∆KE, ∆PE, Ws = 0

PROBLEM SETS

Solve the problems at the end of Chapter 1 of ChE Thermodynamics by Van Ness and Abbott.

Lecture Notes for ChE 353 : ChE Thermodynamics I 16


by: Mary Rose B. Flores-Persincula

Das könnte Ihnen auch gefallen