Thermodynamics

From Wikipedia, the free encyclopedia

Jump to: navigation, search
In physics, thermodynamics (from the Greek θερμ-<θερμότης, therme, meaning "heat"[1] and
δυναμις, dynamis, meaning "power") is the study of the conversion of energy into work and heat
and its relation to macroscopic variables such as temperature,volume and pressure. Its
underpinnings, based upon statistical predictions of the collective motion of particles from their
microscopic behavior, is the field of statistical thermodynamics (or statistical mechanics), a
branch of statistical physics.[2][3][4] Historically, thermodynamics developed out of need to
increase the efficiency of early steam engines.[5]

Typical thermodynamic system, showing input from a heat source (boiler) on the left and
output to a heat sink (condenser) on the right. Work is extracted, in this case by a series of
pistons.

Contents
[hide]
• 1 Starting point and relevance
• 2 History
• 3 The laws of thermodynamics
• 4 Thermodynamic potentials
• 5 Classical thermodynamics
• 6 Statistical mechanics
• 7 Chemical thermodynamics
• 8 Thermodynamic systems
• 9 Conjugate variables
• 10 Thermodynamic instruments
 • 11 Thermodynamic states
• 12 Thermodynamic processes
• 13 See also
○ 13.1 Approaches and applied fields
○ 13.2 Other
○ 13.3 Wikibooks
• 14 References
• 15 Further reading
• 16 External links

[edit] Starting point and relevance

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.[6] They
also postulate the existence of a quantity named entropy, which can be defined for any isolated
system that is in thermodynamic equilibrium.[7] 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, the usage of thermodynamics describes 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.[8][9]
[edit] History

Sadi Carnot (1796-1832): was the father of thermodynamics

Main article: History of thermodynamics
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 Irish
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.[10] 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. 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. This marks the start of thermodynamics as a modern science.[3]
The term thermodynamics was coined by James Joule in 1849 to designate the science of
relations between heat and power.[3] 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.[11] 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.[12]
[edit] The laws of thermodynamics
Main article: Laws of thermodynamics
The present article is focused on classical thermodynamics, which is focused on 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.
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, around the turn of the 20th century, of spontaneous
emission, and ongoing research into the thermodynamics of black holes.
These four laws are:
• Zeroth law of thermodynamics, about thermal equilibrium:
If two thermodynamic systems are separately in thermal equilibrium with a third, they are
also in thermal equilibrium with each other.
 If we grant that all systems are (trivially) in thermal equilibrium with themselves, the
Zeroth law implies that thermal equilibrium is an equivalence relation on the set of
thermodynamic 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 into contact and to watch whether their observable properties
change with time.[13]
• First law of thermodynamics, about the conservation of energy:
The change in the internal energy of a closed thermodynamic system is equal to the sum
of the amount of heat energy supplied to or removed from the system and the work done
on or by the system.
• Second law of thermodynamics, about entropy:
The total entropy of any isolated thermodynamic system always increases over time,
approaching a maximum value.
• Third law of thermodynamics, about the absolute zero of temperature:
As a system asymptotically approaches absolute zero of temperature all processes
virtually cease and the entropy of the system asymptotically approaches a minimum
value; also stated as: "the entropy of all systems and of all states of a system is zero at
absolute zero" or equivalently "it is impossible to reach the absolute zero of temperature
by any finite number of processes".
See also: Bose–Einstein condensate and negative temperature.
[edit] Thermodynamic potentials
Main article: Thermodynamic potentials
As can be derived from the energy balance equation (or Burks' equation) on a thermodynamic
system there exist energetic quantities called thermodynamic potentials, being the quantitative
measure of the stored energy in the system. The five most well known potentials are:

Internal energy

Helmholtz free energy

Enthalpy

Gibbs free energy

Grand potential

Other thermodynamic potentials can be obtained through Legendre transformation. Potentials are
used to measure energy changes in systems as they evolve from an initial state to a final state.
The potential used depends on the constraints of the system, such as constant temperature or
pressure. Internal energy is the internal energy of the system, enthalpy is the internal energy of
the system plus the energy related to pressure-volume work, and Helmholtz and Gibbs energy
are the energies available in a system to do useful work when the temperature and volume or the
pressure and temperature are fixed, respectively.
[edit] Classical thermodynamics
Main article: Classical thermodynamics
Classical thermodynamics is the original early 1800s variation of thermodynamics concerned
with thermodynamic states, and properties as energy, work, and heat, and with the laws of
thermodynamics, all lacking an atomic interpretation. In precursory form, classical
thermodynamics derives from chemist Robert Boyle’s 1662 postulate that the pressure P of a
given quantity of gas varies inversely as its volume V at constant temperature; i.e. in equation
form: PV = k, a constant. From here, a semblance of a thermo-science began to develop with the
construction of the first successful atmospheric steam engines in England by Thomas Savery in
1697 and Thomas Newcomen in 1712. 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).
[edit] Statistical mechanics
Main article: Statistical mechanics
With the development of atomic and molecular theories in the late 1800s and early 1900s,
thermodynamics was given a molecular interpretation. This field, called statistical mechanics or
statistical thermodynamics, 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. The statistical approach is in contrast to classical
thermodynamics, which is a more phenomenological approach that does not include microscopic
details. 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.
[edit] Chemical thermodynamics
Main article: Chemical thermodynamics
Chemical thermodynamics is 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. 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 to
determine if a process would occur spontaneously.[14] 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.[15]
[edit] Thermodynamic systems
Main article: Thermodynamic system
An important concept in thermodynamics is the “system”. Everything in the universe except the
system is known as surroundings. A system is the region of the universe under study. A system is
separated from the remainder of the universe by a boundary which may be imaginary or not, but
which by convention delimits a finite volume. The possible exchanges of work, heat, or matter
between the system and the surroundings take place across this boundary. Boundaries are of four
types: fixed, moveable, real, and imaginary.
Basically, the “boundary” is simply an imaginary dotted line drawn around a volume of
something when there is going to be a change in the internal energy of that something. Anything
that passes across the boundary that effects a change in the internal energy of the something
needs to be accounted for in the energy balance equation. That something can be the volumetric
region surrounding a single atom resonating energy, such as Max Planck defined in 1900; it can
be a body of steam or air in a steam engine, such as Sadi Carnot defined in 1824; it can be the
body of a tropical cyclone, such as Kerry Emanuel theorized in 1986 in the field of atmospheric
thermodynamics; it could also be just one nuclide (i.e. a system of quarks) as some are theorizing
presently in quantum thermodynamics.
For an engine, a fixed boundary means the piston is locked at its position; as such, a constant
volume process occurs. In that same engine, a moveable boundary allows the piston to move in
and out. For closed systems, boundaries are real while for open system boundaries are often
imaginary. There are five dominant classes of systems:
1. Isolated Systems – matter and energy may not cross the boundary
2. Adiabatic Systems – heat must not cross the boundary
3. Diathermic Systems - heat may cross boundary
4. Closed Systems – matter may not cross the boundary
5. Open Systems – heat, work, and matter may cross the boundary (often called a control
volume in this case)
As time passes in an isolated system, internal differences in the system tend to even out and
pressures and temperatures tend to equalize, as do density differences. A system in which all
equalizing processes have gone practically to completion, is considered to be in a state of
thermodynamic equilibrium.
In thermodynamic equilibrium, a system's properties are, by definition, unchanging in time.
Systems in equilibrium are much simpler and easier to understand than systems which are not in
equilibrium. Often, when analysing a thermodynamic process, it can be assumed that each
intermediate state in the process is at equilibrium. This will also considerably simplify the
situation. Thermodynamic processes which develop so slowly as to allow each intermediate step
to be an equilibrium state are said to be reversible processes.
[edit] Conjugate variables
Main article: Conjugate variables (thermodynamics)
The central concept of thermodynamics is that of energy, the ability to do work. By the First
Law, the total energy of a system and its surroundings is conserved. Energy may be transferred
into a system by heating, compression, or addition of matter, and extracted from a system by
cooling, expansion, or extraction of matter. In mechanics, for example, energy transfer equals the
product of the force applied to a body and the resulting displacement.
Conjugate variables are pairs of thermodynamic concepts, with the first being akin to a "force"
applied to some thermodynamic system, the second being akin to the resulting "displacement,"
and the product of the two equalling the amount of energy transferred. The common conjugate
variables are:
• Pressure-volume (the mechanical parameters);
• Temperature-entropy (thermal parameters);
• Chemical potential-particle number (material parameters).
[edit] Thermodynamic instruments
Main article: Thermodynamic instruments
There are two types of thermodynamic instruments, the meter and the reservoir. A
thermodynamic meter is any device which measures any parameter of a thermodynamic system.
In some cases, the thermodynamic parameter is actually defined in terms of an idealized
measuring instrument. For example, the zeroth law states that if two bodies are in thermal
equilibrium with a third body, they are also in thermal equilibrium with each other. This
principle, as noted by James Maxwell in 1872, asserts that it is possible to measure temperature.
An idealized thermometer is a sample of an ideal gas at constant pressure. From the ideal gas law
PV=nRT, the volume of such a sample can be used as an indicator of temperature; in this manner
it defines temperature. Although pressure is defined mechanically, a pressure-measuring device,
called a barometer may also be constructed from a sample of an ideal gas held at a constant
temperature. A calorimeter is a device which is used to measure and define the internal energy of
a system.
A thermodynamic reservoir is a system which is so large that it does not appreciably alter its
state parameters when brought into contact with the test system. It is used to impose a particular
value of a state parameter upon the system. For example, a pressure reservoir is a system at a
particular pressure, which imposes that pressure upon any test system that it is mechanically
connected to. The Earth's atmosphere is often used as a pressure reservoir.
It is important that these two types of instruments are distinct. A meter does not perform its task
accurately if it behaves like a reservoir of the state variable it is trying to measure. If, for
example, a thermometer were to act as a temperature reservoir it would alter the temperature of
the system being measured, and the reading would be incorrect. Ideal meters have no effect on
the state variables of the system they are measuring.
[edit] Thermodynamic states
Main article: Thermodynamic state
When a system is at equilibrium under a given set of conditions, it is said to be in a definite state.
The state of the system can be described by a number of intensive variables and extensive
variables. The properties of the system can be described by an equation of state which specifies
the relationship between these variables. State may be thought of as the instantaneous
quantitative description of a system with a set number of variables held constant.
[edit] Thermodynamic processes
Main article: Thermodynamic processes
A thermodynamic process may be defined as the energetic evolution of a thermodynamic
system proceeding from an initial state to a final state. Typically, each thermodynamic process is
distinguished from other processes, in energetic character, according to what parameters, as
temperature, pressure, or volume, etc., are held fixed. Furthermore, it is useful to group these
processes into pairs, in which each variable held constant is one member of a conjugate pair. The
seven most common thermodynamic processes are shown below:
1. An isobaric process occurs at constant pressure.
2. An isochoric process, or isometric/isovolumetric process, occurs at constant volume.
3. An isothermal process occurs at a constant temperature.
4. An adiabatic process occurs without loss or gain of energy by heat.
5. An isentropic process (reversible adiabatic process) occurs at a constant entropy.
6. An isenthalpic process occurs at a constant enthalpy.
7. A steady state process occurs without a change in the internal energy of a system