In the most general sense thermodynamics is the study of energy -- its transformations and
its relationship to the properties of matter. In its engineering applications thermodynamics
has two major objectives. One of these is to describe the properties of matter when it exists
in what is called an equilibrium state, a condition in which its properties show no tendency
to change. The other objective is to describe processes in which the properties of matter
undergo changes and to relate these changes to the energy transfers in the form of heat and
work which accompany them. These objectives are closely related and a text such as this,
which emphasizes primarily the description of equilibrium properties, must include as well a
discussion of the basic principles involved in accomplishing these two objectives.
Thermodynamics is unique among scientific disciplines in that no other branch of
science deals with subjects which are as commonplace or as familiar. Concepts such as
"heat", "work", "energy", and "properties" are all terms in everyone's basic vocabulary.
Thermodynamic laws which govern them originate from very ordinary experiences in our
daily lives. One might think that this familiarity would simplify the understanding and
application of thermodynamics. Unfortunately, quite the opposite is true. In order to
accomplish these objectives, one must almost entirely forget a life-long acquaintance with
the terms of thermodynamics and redefine them in a very scientific and analytical manner.
We will begin with a discussion of the various properties of matter with which we will be
concerned.
1 Thermodynamic and Non-Thermodynamic Properties
A property of matter is any characteristic which can distinguish a given quantity of
a matter from another. These distinguishing characteristics can be classified in several
different ways, but for the purposes of this text it is convenient to divide them into what
may be called thermodynamic and non-thermodynamic properties.
The non-thermodynamic properties describe characteristics of what are often called
the "ultimate particles" of matter. An ultimate particle from a thermodynamic view point
is the smallest subdivision of a quantity of matter which does not undergo any net internal
changes during a selected set of processes which alter properties of the entire quantity. The
ultimate particles with which we will be concerned are generally considered to be molecules
or atoms, or in some cases groups of atoms within a molecule. When the meaning is clear
we will some times delete the adjective "ultimate" and refer to them simply as "particles".
Because it has no internal changes an ultimate particle can always be regarded as a
rigid mass. Its only alterable distinguishing characteristics which could possibly be
detected, if some experimental procedure could do so, are its position and its motion. As a
result, the fundamental properties of this particle, which cannot be calculated or derived
from any others, consist only of its mass and shape plus the vectors or coordinates needed to
describe its position and motion. It is convenient to combine the mass and motion
characteristics and represent them as a momentum property. These fundamental
characteristics, mass, position, and momentum, are called "microstate" properties and as a
group they give a complete description of the actual behavior of an ultimate particle.
Everyone realizes of course, that molecules are not actually inert rigid masses. The
forces of attraction and repulsion which we ascribe to them are in reality the consequence of
variations in the quantum states of a deformable electron cloud which fills practically all the
space occupied by a molecule so that when we represent it as a rigid mass we are
constructing a model which allows us to apply classical mechanics to relate its energy
changes to changes in its microstate properties. For example, an effective model for a
complex molecule is to regard it as a group of rigid spheres of various size and mass held
together by flexible springs. The only justification for this model is that calculations of its
energy, when properly averaged, give good agreement with values of energy per molecule
obtained from experimental measurements using bulk quantities of the substance.
Constructing models is important in all aspects of thermodynamics, not only for individual
molecules, but also in describing the behavior of bulk matter.
Values which can be calculated from the microstate properties of an individual
particle or of a cluster containing only a few particles represent another group of nonthermodynamic
properties. We will refer to these derived values as "molecular" properties.
Examples are the translational, vibrational, or rotational energies of an individual molecule,
and also the calculated potential energy at various separation distances in a pair of
molecules or between other small groups of near neighbors. In some cases we wish to
calculate special functions of the potential energy within a group composed of a few
neighbors. An important feature of all of these combinations of fundamental microstate
properties is that they can produce the same value of a calculated molecular property. For
example, assigning values to the microstate properties of a molecule determines its energy
but specifying the energy of a molecule does not specify any one particular set of values for
its microstate properties.
Whereas the non-thermodynamic properties pertain to a single or to only a few
ultimate particles, the characteristics of matter which are called thermodynamic properties
are those which result from the collective behavior of a very large number of its ultimate
particles. Instead of only one or a few particles, this number is typically on the order of
Avogadro's number. In a manner analogous to the way in which molecular properties can
be calculated from the fundamental microstate properties of an individual or small group of
particles, the various thermodynamic properties likewise depend upon the vastly greater
number of all the microstate properties of the very large group. Furthermore, an even larger
number of different sets of microstate properties can produce the same overall
thermodynamic property value. In contrast to non-thermodynamic properties,
thermodynamic properties can always be measured experimentally or calculated from such
measurements.
Establishing relationships between non-thermodynamic and thermodynamic
properties of matter in equilibrium states is the task of statistical thermodynamics while the
study of relationships among the thermodynamic properties alone is generally the topic of
classical thermodynamics. In the past it has been customary for textbooks and their readers
to make a sharp distinction between the two disciplines. The historical development of
classical thermodynamics and its applications to a wide range of engineering problems took
place without any reference at all to ultimate particles or molecular properties. This
development is entirely rigorous and has the merit of establishing the validity of general
thermodynamic principles to all types of matter regardless of its molecular character.
However, the problem of predicting and correlating thermodynamic properties of an
increasing diversity of substances both in pure form and in mixtures with the accuracy
needed in modern technology requires a combination of the classical and molecular
viewpoints. It is this combination which is the objective of this text.
2 The Selection of a System
The first concept which must be understood in applying thermodynamics is the
necessity to begin with the definition of what is called a "system". In thermodynamics this
is any region completely enclosed within a well defined boundary. Everything outside the
system is then defined as the surroundings. Although it is possible to speak of the subject
matter of thermodynamics in a general sense, the establishment of analytical relationships
among heat, work, and thermodynamic properties requires that they be related to a
particular system. We must always distinguish clearly between energy changes taking place
within a system and energy transferred across the system boundary. We must likewise
distinguish between properties of material within a system and properties of its
surroundings.
In accordance with their definition, thermodynamic properties apply to systems
which must contain a very large number of ultimate particles. Other than this there are no
fundamental restrictions on the definition of a system. The boundary may be either rigid or
movable. It can be completely impermeable or it can allow energy or mass to be transported
through it. In any given situation a system may be defined in several ways; although with
some definitions the computations to be performed are quite simple, with others they are
difficult or even impossible.
For example, it is often impossible by means of thermodynamic methods alone to
make heat transfer calculations if a system is defined so that both heat transfer and
diffusional mass transfer occur simultaneously through the same area on the boundary of
the system. For processes in which mass transfer takes place only by bulk stream flow this
problem can be avoided easily by a proper definition of the system. In a flow process of this
type the system is defined so that it is enclosed by moveable boundaries with no stream flows
across them. Heat transfer then always occurs across a boundary not crossed by mass.
3 Microstates and Thermodynamic States
The state of a system is an important concept in thermodynamics and is defined as
the complete set of all its properties which can change during various specified processes.
The properties which comprise this set depend on the kinds of interactions which can take
place both within the system and between the system and its surroundings. Any two
systems, subject to the same group of processes, which have the same values of all properties
in this set are then indistinguishable and we describe them as being in identical states.
A process in thermodynamics is defined as a method of operation in which specific
quantities of heat and various types of work are transferred to or from the system to alter its
state. As we pointed out, one of the objectives of thermodynamics is to relate these state
changes in a system to the quantity of energy in the form of heat and work transferred
across its boundaries.
In discussing non-thermodynamic processes, a system may be chosen as a single
ultimate particle within a larger quantity of matter. In the absence of chemical reactions the
only processes in which it can participate are transfers of kinetic or potential energy to or
from the particle. In this case we would like to relate these energy transfers to changes in
the microstate of the system. A microstate for this one-particle system is a set of coordinates
in a multi-dimensional space indicating its position and its momenta in various vector
directions. For example, a simple rigid spherical monatomic molecule would require a total
of six such coordinates, three for its position and three for its momentum in order to
completely define its microstate.
Now consider a system containing a large number of these ultimate particles. A
microstate of this system is a set of all position and momentum values for all the particles.
For example, if there were N rigid spherical molecules we would then need 6N coordinates
to give a complete set of all the microstate properties and define a microstate for this system.
In a multiparticle system a particular microstate exists only for an instant and is then
replaced by another so that there is no experimental way to measure the set of positions and
motions which comprise one microstate among the vast number of them which occur
sequentially.
Because the microstates of a multiparticle system represent exactly what all the
particles are doing, all thermodynamic properties of the group are thus determined by them.
With this common origin all the thermodynamic properties are therefore related to each
other and we need to develop this relationship. The set of all the thermodynamic properties
of a multiparticle system its temperature, pressure, volume, internal energy, etc., is defined
as the thermodynamic state of this system.
An important aspect of this relationship between thermodynamic properties is the
question of how many different thermodynamic properties of a given equilibrium system are
independently variable. The number of these represents the smallest number of properties
which must be specified in order to completely determine the entire thermodynamic state of
the system. All other thermodynamic properties of this system are then fixed and can be
calculated from these specified values. The number of these values which must be specified
is called the variance or the degrees of freedom of the system.
4 The Concept of Energy
In elementary physics energy is often defined as "the capacity to produce work". At
a descriptive level the idea expressed is correct, but for thermodynamics which is to be
applied quantitatively this definition is not a good one because the term "work" itself
requires a more precise definition than the general idea it ordinarily conveys. A better
definition of energy from the viewpoint of thermodynamics would be "the capacity to induce
a change in that which inherently resists change". This capacity represents a combination
of an effort, expended in overcoming resistance to a particular type of change, with the
change it produces. The combination is called energy.
The effort involved is measured quantitatively by what is defined as a "driving
force" in thermodynamics. A driving force is a property which both causes and also
controls the direction of change in another property. The quantitative value of this change
is called a "displacement". The product of a driving force and its associated displacement
always represents a quantity of energy, but in thermodynamics this quantity has meaning
only in relation to a specifically defined system.
Relative to a particular system there are generally two ways of locating a driving
force and the displacement it produces. In one way both the driving force and the
displacement are properties of the system and are located entirely within it, so that the
energy calculated from their product represents a change in the internal energy of the
system. Similarly, both the driving force and its displacement could be located entirely
within the surroundings so that the calculated energy is then a change in the total energy of
the surroundings.
In another way, however, the displacement occurs within the system but the driving
force producing it is a property of the surroundings and is applied externally at the system
boundary. By definition, the boundary of a system is a region of zero thickness containing
no matter at all so that the energy calculated in this way is not a property of matter either in
the system or in its surroundings but represents a quantity of energy in transition between
the two. In any quantitative application of thermodynamics it is always important to make
a careful distinction between energy changes within a system or within its surroundings
and energy in transition between them.
5 Microstate Driving Forces
In order to explain the nature of driving forces, suppose we consider first a system
defined as a single ultimate particle of a simple fluid, either a gas or a liquid. The system in
this case is a rigid spherical mass with no possibilities for any internal changes and obeying
Newtonian mechanics. In its surroundings are similar ultimate particles of this fluid.
From a Newtonian point of view the mass of this system resists any change in its condition
of motion and a specific change occurs only with the application of an external force to
overcome the inertial resistance inherent in the mass. In the presence of mutual attraction
and repulsion between this system and neighboring particles it may be considered to resist
any displacement from a position in which this attraction and repulsion are balanced. In
this situation a force vector directed toward the center of mass must be applied for a fixed
time period to produce a change. This force is produced by the environment around the
particle chosen as the system. The mechanism for its generation is by the action of
neighboring particles in exerting attraction or repulsion or in colliding with the system.
The scalar product of the vector force generated in this manner with other vectors which
represent the resulting displacements in position and velocity of the system determine the
energy added to the system when its velocity is increased, when its position is moved away
from attracting neighbors, or when moved toward neighbors which repel it.
Since these displacements represent changes in microstate properties, we define the
force vector producing them as a "microstate driving force." According to Newtonian
mechanics this applied force is always opposed by an equal and opposite force representing
the resistance of the system to change. Although mechanically we could position these two
forces anywhere along their line of action, in terms of the system it is convenient to think of
them as opposing one another at the boundary of the system to describe energy in transition
across it and then as opposing one another within the system when we describe this
quantity of energy as the energy change of the system. An important characteristic of
microstate driving forces is that they are true force vectors in the Newtonian sense and there
is never a condition of unbalanced driving forces. This is not at all the case for what we will
define as "thermodynamic driving forces" which are the agents of change for
thermodynamic properties in multiparticle systems.
6 Thermodynamic Driving Forces
In contrast to the one-particle system which we have discussed in section 5, for
thermodynamic systems consisting of many particles we are usually as interested in
internal energy changes as we are in changes in position or motion of the entire system. In
this case we wish to define these internal energy changes in terms of thermodynamic
properties, each of which are the collective results of the enormous number of microstates for
all the ultimate particles of the system. Because the fundamental agents of change within
the system are microstate driving forces, the corresponding agents of change or driving
forces in thermodynamic systems are the composite result of all the microstate driving force
vectors in the system. However, the only case in which the collective behavior of all these
microstate driving force vectors defines a thermodynamic property is the one in which these
microstate vectors for all the individual particles are oriented in a completely random
manner in every conceivable direction. In this case their overall resultant in the entire
system is completely scalar in nature and a thermodynamic property of the system. We
define this resultant as a "thermodynamic driving force."
Likewise, the cumulative effect of all the microstate changes induced, which are also
vectors, produces in this case a completely scalar thermodynamic property change for the
multiparticle system. This overall change is the displacement induced by the
thermodynamic driving force.
Because these thermodynamic driving forces are not true vector forces in the
Newtonian sense but are scalar properties, the thermodynamic driving forces tending to
cause a change are not always balanced by equal and opposite driving forces opposing the
change. Changes in internal thermodynamic properties within a system can be controlled
as to direction, and in some instances as to their rates, by the degree of difference between
the value of a particular thermodynamic driving force property outside the system at its
boundary and a value of this same property somewhere within the system. Between
thermodynamic driving forces this difference can be of any magnitude, finite or
infinitesimal. When they are exactly equal there is then no net change induced and no
energy is transferred
its relationship to the properties of matter. In its engineering applications thermodynamics
has two major objectives. One of these is to describe the properties of matter when it exists
in what is called an equilibrium state, a condition in which its properties show no tendency
to change. The other objective is to describe processes in which the properties of matter
undergo changes and to relate these changes to the energy transfers in the form of heat and
work which accompany them. These objectives are closely related and a text such as this,
which emphasizes primarily the description of equilibrium properties, must include as well a
discussion of the basic principles involved in accomplishing these two objectives.
Thermodynamics is unique among scientific disciplines in that no other branch of
science deals with subjects which are as commonplace or as familiar. Concepts such as
"heat", "work", "energy", and "properties" are all terms in everyone's basic vocabulary.
Thermodynamic laws which govern them originate from very ordinary experiences in our
daily lives. One might think that this familiarity would simplify the understanding and
application of thermodynamics. Unfortunately, quite the opposite is true. In order to
accomplish these objectives, one must almost entirely forget a life-long acquaintance with
the terms of thermodynamics and redefine them in a very scientific and analytical manner.
We will begin with a discussion of the various properties of matter with which we will be
concerned.
1 Thermodynamic and Non-Thermodynamic Properties
A property of matter is any characteristic which can distinguish a given quantity of
a matter from another. These distinguishing characteristics can be classified in several
different ways, but for the purposes of this text it is convenient to divide them into what
may be called thermodynamic and non-thermodynamic properties.
The non-thermodynamic properties describe characteristics of what are often called
the "ultimate particles" of matter. An ultimate particle from a thermodynamic view point
is the smallest subdivision of a quantity of matter which does not undergo any net internal
changes during a selected set of processes which alter properties of the entire quantity. The
ultimate particles with which we will be concerned are generally considered to be molecules
or atoms, or in some cases groups of atoms within a molecule. When the meaning is clear
we will some times delete the adjective "ultimate" and refer to them simply as "particles".
Because it has no internal changes an ultimate particle can always be regarded as a
rigid mass. Its only alterable distinguishing characteristics which could possibly be
detected, if some experimental procedure could do so, are its position and its motion. As a
result, the fundamental properties of this particle, which cannot be calculated or derived
from any others, consist only of its mass and shape plus the vectors or coordinates needed to
describe its position and motion. It is convenient to combine the mass and motion
characteristics and represent them as a momentum property. These fundamental
characteristics, mass, position, and momentum, are called "microstate" properties and as a
group they give a complete description of the actual behavior of an ultimate particle.
Everyone realizes of course, that molecules are not actually inert rigid masses. The
forces of attraction and repulsion which we ascribe to them are in reality the consequence of
variations in the quantum states of a deformable electron cloud which fills practically all the
space occupied by a molecule so that when we represent it as a rigid mass we are
constructing a model which allows us to apply classical mechanics to relate its energy
changes to changes in its microstate properties. For example, an effective model for a
complex molecule is to regard it as a group of rigid spheres of various size and mass held
together by flexible springs. The only justification for this model is that calculations of its
energy, when properly averaged, give good agreement with values of energy per molecule
obtained from experimental measurements using bulk quantities of the substance.
Constructing models is important in all aspects of thermodynamics, not only for individual
molecules, but also in describing the behavior of bulk matter.
Values which can be calculated from the microstate properties of an individual
particle or of a cluster containing only a few particles represent another group of nonthermodynamic
properties. We will refer to these derived values as "molecular" properties.
Examples are the translational, vibrational, or rotational energies of an individual molecule,
and also the calculated potential energy at various separation distances in a pair of
molecules or between other small groups of near neighbors. In some cases we wish to
calculate special functions of the potential energy within a group composed of a few
neighbors. An important feature of all of these combinations of fundamental microstate
properties is that they can produce the same value of a calculated molecular property. For
example, assigning values to the microstate properties of a molecule determines its energy
but specifying the energy of a molecule does not specify any one particular set of values for
its microstate properties.
Whereas the non-thermodynamic properties pertain to a single or to only a few
ultimate particles, the characteristics of matter which are called thermodynamic properties
are those which result from the collective behavior of a very large number of its ultimate
particles. Instead of only one or a few particles, this number is typically on the order of
Avogadro's number. In a manner analogous to the way in which molecular properties can
be calculated from the fundamental microstate properties of an individual or small group of
particles, the various thermodynamic properties likewise depend upon the vastly greater
number of all the microstate properties of the very large group. Furthermore, an even larger
number of different sets of microstate properties can produce the same overall
thermodynamic property value. In contrast to non-thermodynamic properties,
thermodynamic properties can always be measured experimentally or calculated from such
measurements.
Establishing relationships between non-thermodynamic and thermodynamic
properties of matter in equilibrium states is the task of statistical thermodynamics while the
study of relationships among the thermodynamic properties alone is generally the topic of
classical thermodynamics. In the past it has been customary for textbooks and their readers
to make a sharp distinction between the two disciplines. The historical development of
classical thermodynamics and its applications to a wide range of engineering problems took
place without any reference at all to ultimate particles or molecular properties. This
development is entirely rigorous and has the merit of establishing the validity of general
thermodynamic principles to all types of matter regardless of its molecular character.
However, the problem of predicting and correlating thermodynamic properties of an
increasing diversity of substances both in pure form and in mixtures with the accuracy
needed in modern technology requires a combination of the classical and molecular
viewpoints. It is this combination which is the objective of this text.
2 The Selection of a System
The first concept which must be understood in applying thermodynamics is the
necessity to begin with the definition of what is called a "system". In thermodynamics this
is any region completely enclosed within a well defined boundary. Everything outside the
system is then defined as the surroundings. Although it is possible to speak of the subject
matter of thermodynamics in a general sense, the establishment of analytical relationships
among heat, work, and thermodynamic properties requires that they be related to a
particular system. We must always distinguish clearly between energy changes taking place
within a system and energy transferred across the system boundary. We must likewise
distinguish between properties of material within a system and properties of its
surroundings.
In accordance with their definition, thermodynamic properties apply to systems
which must contain a very large number of ultimate particles. Other than this there are no
fundamental restrictions on the definition of a system. The boundary may be either rigid or
movable. It can be completely impermeable or it can allow energy or mass to be transported
through it. In any given situation a system may be defined in several ways; although with
some definitions the computations to be performed are quite simple, with others they are
difficult or even impossible.
For example, it is often impossible by means of thermodynamic methods alone to
make heat transfer calculations if a system is defined so that both heat transfer and
diffusional mass transfer occur simultaneously through the same area on the boundary of
the system. For processes in which mass transfer takes place only by bulk stream flow this
problem can be avoided easily by a proper definition of the system. In a flow process of this
type the system is defined so that it is enclosed by moveable boundaries with no stream flows
across them. Heat transfer then always occurs across a boundary not crossed by mass.
3 Microstates and Thermodynamic States
The state of a system is an important concept in thermodynamics and is defined as
the complete set of all its properties which can change during various specified processes.
The properties which comprise this set depend on the kinds of interactions which can take
place both within the system and between the system and its surroundings. Any two
systems, subject to the same group of processes, which have the same values of all properties
in this set are then indistinguishable and we describe them as being in identical states.
A process in thermodynamics is defined as a method of operation in which specific
quantities of heat and various types of work are transferred to or from the system to alter its
state. As we pointed out, one of the objectives of thermodynamics is to relate these state
changes in a system to the quantity of energy in the form of heat and work transferred
across its boundaries.
In discussing non-thermodynamic processes, a system may be chosen as a single
ultimate particle within a larger quantity of matter. In the absence of chemical reactions the
only processes in which it can participate are transfers of kinetic or potential energy to or
from the particle. In this case we would like to relate these energy transfers to changes in
the microstate of the system. A microstate for this one-particle system is a set of coordinates
in a multi-dimensional space indicating its position and its momenta in various vector
directions. For example, a simple rigid spherical monatomic molecule would require a total
of six such coordinates, three for its position and three for its momentum in order to
completely define its microstate.
Now consider a system containing a large number of these ultimate particles. A
microstate of this system is a set of all position and momentum values for all the particles.
For example, if there were N rigid spherical molecules we would then need 6N coordinates
to give a complete set of all the microstate properties and define a microstate for this system.
In a multiparticle system a particular microstate exists only for an instant and is then
replaced by another so that there is no experimental way to measure the set of positions and
motions which comprise one microstate among the vast number of them which occur
sequentially.
Because the microstates of a multiparticle system represent exactly what all the
particles are doing, all thermodynamic properties of the group are thus determined by them.
With this common origin all the thermodynamic properties are therefore related to each
other and we need to develop this relationship. The set of all the thermodynamic properties
of a multiparticle system its temperature, pressure, volume, internal energy, etc., is defined
as the thermodynamic state of this system.
An important aspect of this relationship between thermodynamic properties is the
question of how many different thermodynamic properties of a given equilibrium system are
independently variable. The number of these represents the smallest number of properties
which must be specified in order to completely determine the entire thermodynamic state of
the system. All other thermodynamic properties of this system are then fixed and can be
calculated from these specified values. The number of these values which must be specified
is called the variance or the degrees of freedom of the system.
4 The Concept of Energy
In elementary physics energy is often defined as "the capacity to produce work". At
a descriptive level the idea expressed is correct, but for thermodynamics which is to be
applied quantitatively this definition is not a good one because the term "work" itself
requires a more precise definition than the general idea it ordinarily conveys. A better
definition of energy from the viewpoint of thermodynamics would be "the capacity to induce
a change in that which inherently resists change". This capacity represents a combination
of an effort, expended in overcoming resistance to a particular type of change, with the
change it produces. The combination is called energy.
The effort involved is measured quantitatively by what is defined as a "driving
force" in thermodynamics. A driving force is a property which both causes and also
controls the direction of change in another property. The quantitative value of this change
is called a "displacement". The product of a driving force and its associated displacement
always represents a quantity of energy, but in thermodynamics this quantity has meaning
only in relation to a specifically defined system.
Relative to a particular system there are generally two ways of locating a driving
force and the displacement it produces. In one way both the driving force and the
displacement are properties of the system and are located entirely within it, so that the
energy calculated from their product represents a change in the internal energy of the
system. Similarly, both the driving force and its displacement could be located entirely
within the surroundings so that the calculated energy is then a change in the total energy of
the surroundings.
In another way, however, the displacement occurs within the system but the driving
force producing it is a property of the surroundings and is applied externally at the system
boundary. By definition, the boundary of a system is a region of zero thickness containing
no matter at all so that the energy calculated in this way is not a property of matter either in
the system or in its surroundings but represents a quantity of energy in transition between
the two. In any quantitative application of thermodynamics it is always important to make
a careful distinction between energy changes within a system or within its surroundings
and energy in transition between them.
5 Microstate Driving Forces
In order to explain the nature of driving forces, suppose we consider first a system
defined as a single ultimate particle of a simple fluid, either a gas or a liquid. The system in
this case is a rigid spherical mass with no possibilities for any internal changes and obeying
Newtonian mechanics. In its surroundings are similar ultimate particles of this fluid.
From a Newtonian point of view the mass of this system resists any change in its condition
of motion and a specific change occurs only with the application of an external force to
overcome the inertial resistance inherent in the mass. In the presence of mutual attraction
and repulsion between this system and neighboring particles it may be considered to resist
any displacement from a position in which this attraction and repulsion are balanced. In
this situation a force vector directed toward the center of mass must be applied for a fixed
time period to produce a change. This force is produced by the environment around the
particle chosen as the system. The mechanism for its generation is by the action of
neighboring particles in exerting attraction or repulsion or in colliding with the system.
The scalar product of the vector force generated in this manner with other vectors which
represent the resulting displacements in position and velocity of the system determine the
energy added to the system when its velocity is increased, when its position is moved away
from attracting neighbors, or when moved toward neighbors which repel it.
Since these displacements represent changes in microstate properties, we define the
force vector producing them as a "microstate driving force." According to Newtonian
mechanics this applied force is always opposed by an equal and opposite force representing
the resistance of the system to change. Although mechanically we could position these two
forces anywhere along their line of action, in terms of the system it is convenient to think of
them as opposing one another at the boundary of the system to describe energy in transition
across it and then as opposing one another within the system when we describe this
quantity of energy as the energy change of the system. An important characteristic of
microstate driving forces is that they are true force vectors in the Newtonian sense and there
is never a condition of unbalanced driving forces. This is not at all the case for what we will
define as "thermodynamic driving forces" which are the agents of change for
thermodynamic properties in multiparticle systems.
6 Thermodynamic Driving Forces
In contrast to the one-particle system which we have discussed in section 5, for
thermodynamic systems consisting of many particles we are usually as interested in
internal energy changes as we are in changes in position or motion of the entire system. In
this case we wish to define these internal energy changes in terms of thermodynamic
properties, each of which are the collective results of the enormous number of microstates for
all the ultimate particles of the system. Because the fundamental agents of change within
the system are microstate driving forces, the corresponding agents of change or driving
forces in thermodynamic systems are the composite result of all the microstate driving force
vectors in the system. However, the only case in which the collective behavior of all these
microstate driving force vectors defines a thermodynamic property is the one in which these
microstate vectors for all the individual particles are oriented in a completely random
manner in every conceivable direction. In this case their overall resultant in the entire
system is completely scalar in nature and a thermodynamic property of the system. We
define this resultant as a "thermodynamic driving force."
Likewise, the cumulative effect of all the microstate changes induced, which are also
vectors, produces in this case a completely scalar thermodynamic property change for the
multiparticle system. This overall change is the displacement induced by the
thermodynamic driving force.
Because these thermodynamic driving forces are not true vector forces in the
Newtonian sense but are scalar properties, the thermodynamic driving forces tending to
cause a change are not always balanced by equal and opposite driving forces opposing the
change. Changes in internal thermodynamic properties within a system can be controlled
as to direction, and in some instances as to their rates, by the degree of difference between
the value of a particular thermodynamic driving force property outside the system at its
boundary and a value of this same property somewhere within the system. Between
thermodynamic driving forces this difference can be of any magnitude, finite or
infinitesimal. When they are exactly equal there is then no net change induced and no
energy is transferred
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