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Thermodynamic system 1

Thermodynamic system
A thermodynamic system is a precisely defined macroscopic
region of the universe, often called a physical system, that is
studied using the principles of thermodynamics.
All space in the universe outside the thermodynamic system is
known as the surroundings, the environment, or a reservoir. A
system is separated from its surroundings by a boundary which
may be notional or real, but which by convention delimits a finite
volume. Exchanges of work, heat, or matter between the system
and the surroundings may take place across this boundary.
Thermodynamic systems are often classified by specifying the
nature of the exchanges that are allowed to occur across its
boundary.

A thermodynamic system is characterized and defined by a set of thermodynamic parameters associated with the
system. The parameters are experimentally measurable macroscopic properties, such as volume, pressure,
temperature, electric field, and others.
The set of thermodynamic parameters necessary to uniquely define a system is called the thermodynamic state of a
system. The state of a system is expressed as a functional relationship, the equation of state, between its parameters.
A system is in thermodynamic equilibrium when the state of the system does not change with time.
Originally, in 1824, Sadi Carnot described a thermodynamic system as the working substance under study.

Overview
Thermodynamics describes the physics of matter using the concept of the thermodynamic system, a region of the
universe that is under study. All quantities, such as pressure or mechanical work, in an equation refer to the system
unless labeled otherwise. As thermodynamics is fundamentally concerned with the flow and balance of energy and
matter, systems are distinguished depending on the kinds of interaction they undergo and the types of energy they
exchange with the surrounding environment.

Interactions of thermodynamic systems


Type of system Mass flow Work Heat

Open

Closed

Isolated

Isolated systems are completely isolated from their environment. They do not exchange heat, work or matter with
their environment. The only truly isolated system there could be is the universe, but even that is up for debate if the
Big Bang is considered. Closed systems are able to exchange energy (heat and work) but not matter with their
environment. A greenhouse is an example of a closed system exchanging heat but not work with its environment.
Whether a system exchanges heat, work or both is usually thought of as a property of its boundary. Open systems
may exchange any form of energy as well as matter with their environment. A boundary allowing matter exchange is
called permeable. The ocean would be an example of an open system.
In practice, a system can never be absolutely isolated from its environment, because there is always at least some
slight coupling, such as gravitational attraction. In analyzing a system in steady-state, the energy into the system is
Thermodynamic system 2

equal to the energy leaving the system [1].


An example system is the system of hot liquid water and solid table salt in a sealed, insulated test tube held in a
vacuum (the surroundings). The test tube constantly loses heat in the form of black-body radiation, but the heat loss
progresses very slowly. If there is another process going on in the test tube, for example the dissolution of the salt
crystals, it will probably occur so quickly that any heat lost to the test tube during that time can be neglected.
Thermodynamics in general does not measure time, but it does sometimes accept limitations on the time frame of a
process.

History
The first to develop the concept of a thermodynamic system was the French physicist Sadi Carnot whose 1824
Reflections on the Motive Power of Fire studied what he called the working substance, e.g., typically a body of water
vapor, in steam engines, in regards to the system's ability to do work when heat is applied to it. The working
substance could be put in contact with either a heat reservoir (a boiler), a cold reservoir (a stream of cold water), or a
piston (to which the working body could do work by pushing on it). In 1850, the German physicist Rudolf Clausius
generalized this picture to include the concept of the surroundings, and began referring to the system as a "working
body." In his 1850 manuscript On the Motive Power of Fire, Clausius wrote:


"With every change of volume (to the working body) a certain amount work must be done by the gas or upon it, since by its expansion it
overcomes an external pressure, and since its compression can be brought about only by an exertion of external pressure. To this excess of
work done by the gas or upon it there must correspond, by our principle, a proportional excess of heat consumed or produced, and the gas
cannot give up to the "surrounding medium" the same amount of heat as it receives."
The article Carnot heat engine shows the original piston-and-cylinder diagram used by Carnot in discussing his ideal
engine; below, we see the Carnot engine as is typically modeled in current use:

Carnot engine diagram (modern) - where heat flows from a high temperature TH furnace through the fluid of the "working body" (working
substance) and into the cold sink TC, thus forcing the working substance to do mechanical work W on the surroundings, via cycles of
contractions and expansions.

In the diagram shown, the "working body" (system), a term introduced by Clausius in 1850, can be any fluid or
vapor body through which heat Q can be introduced or transmitted through to produce work. In 1824, Sadi Carnot, in
his famous paper Reflections on the Motive Power of Fire, had postulated that the fluid body could be any substance
capable of expansion, such as vapor of water, vapor of alcohol, vapor of mercury, a permanent gas, or air, etc.
Although, in these early years, engines came in a number of configurations, typically QH was supplied by a boiler,
wherein water was boiled over a furnace; QC was typically a stream of cold flowing water in the form of a condenser
Thermodynamic system 3

located on a separate part of the engine. The output work W here is the movement of the piston as it is used to turn a
crank-arm, which was then typically used to turn a pulley so to lift water out of flooded salt mines. Carnot defined
work as "weight lifted through a height."

Boundary
A system boundary is a real or imaginary two-dimensional closed surface that encloses or demarcates the volume or
region that a thermodynamic system occupies, across which quantities such as heat, mass, or work can flow.[2] In
short, a thermodynamic boundary is a geometrical division between a system and its surroundings. Topologically, it
is usually considered to be nearly or piecewise smoothly homeomorphic with a two-sphere, because a system is
usually considered to be simply connected.
Boundaries can also be fixed (e.g. a constant volume reactor) or moveable (e.g. a piston). For example, in a
reciprocating 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. Boundaries may be real or
imaginary. For closed systems, boundaries are real while for open system boundaries are often imaginary. For
theoretical purposes, a boundary may be declared to be adiabatic, isothermal, diathermal, insulating, permeable, or
semipermeable, but actual physical materials that provide such idealized properties are not always readily available.
Anything that passes across the boundary that effects a change in the internal energy needs to be accounted for in the
energy balance equation. The volume can be the 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 hypothesized in quantum
thermodynamics.

Surroundings
The system is the part of the universe being studied, while the surroundings is the remainder of the universe that lies
outside the boundaries of the system. It is also known as the environment, and the reservoir. Depending on the type
of system, it may interact with the system by exchanging mass, energy (including heat and work), momentum,
electric charge, or other conserved properties. The environment is ignored in analysis of the system, except in
regards to these interactions.
Thermodynamic system 4

Open system
In open systems, matter may flow in
and out of the system boundaries. The
first law of thermodynamics for open
systems states: the increase in the
internal energy of a system is equal to
the amount of energy added to the
system by matter flowing in and by
heating, minus the amount lost by
matter flowing out and in the form of
work done by the system. The first law
for open systems is given by:

where Uin is the average internal


energy entering the system and Uout is During steady, continuous operation, an energy balance applied to an open system
the average internal energy leaving the equates shaft work performed by the system to heat added plus net enthalpy added.
system
The region of space enclosed by open system boundaries is usually called a control volume, and it may or may not
correspond to physical walls. If we choose the shape of the control volume such that all flow in or out occurs
perpendicular to its surface, then the flow of matter into the system performs work as if it were a piston of fluid
pushing mass into the system, and the system performs work on the flow of matter out as if it were driving a piston
of fluid. There are then two types of work performed: flow work described above which is performed on the fluid
(this is also often called PV work) and shaft work which may be performed on some mechanical device. These two
types of work are expressed in the equation:

Substitution into the equation above for the control volume cv yields:

The definition of enthalpy, H, permits us to use this thermodynamic potential to account for both internal energy and
PV work in fluids for open systems:

During steady-state operation of a device (see turbine, pump, and engine), any system property within the control
volume is independent of time. Therefore, the internal energy of the system enclosed by the control volume remains
constant, which implies that dUcv in the expression above may be set equal to zero. This yields a useful expression
for the power generation or requirement for these devices in the absence of chemical reactions:

This expression is described by the diagram above.


Thermodynamic system 5

Closed system
In a closed system, no mass may be transferred in or out of the system boundaries. The system will always contain
the same amount of matter, but heat and work can be exchanged across the boundary of the system. Whether a
system can exchange heat, work, or both is dependent on the property of its boundary.
Adiabatic boundary not allowing any heat exchange
Rigid boundary not allowing exchange of work
One example is fluid being compressed by a piston in a cylinder. Another example of a closed system is a bomb
calorimeter, a type of constant-volume calorimeter used in measuring the heat of combustion of a particular reaction.
Electrical energy travels across the boundary to produce a spark between the electrodes and initiates combustion.
Heat transfer occurs across the boundary after combustion but no mass transfer takes place either way.
Beginning with the first law of thermodynamics for an open system, this is expressed as:

where U is internal energy, Q is the heat added to the system, W is the work done by the system, and since no mass is
transferred in or out of the system, both expressions involving mass flow are zero and the first law of
thermodynamics for a closed system is derived. The first law of thermodynamics for a closed system states that the
increase of internal energy of the system equals the amount of heat added to the system minus the work done by the
system. For infinitesimal changes the first law for closed systems is stated by:

If the work is due to a volume expansion by dV at a pressure P than:

For a homogeneous system, in which only reversible processes can take place, the second law of thermodynamics
reads:

where T is the absolute temperature and S is the entropy of the system. With these relations the fundamental
thermodynamic relationship, used to compute changes in internal energy, is expressed as:

For a simple system, with only one type of particle (atom or molecule), a closed system amounts to a constant
number of particles. However, for systems which are undergoing a chemical reaction, there may be all sorts of
molecules being generated and destroyed by the reaction process. In this case, the fact that the system is closed is
expressed by stating that the total number of each elemental atom is conserved, no matter what kind of molecule it
may be a part of. Mathematically:

where Nj is the number of j-type molecules, aij is the number of atoms of element i in molecule j and bi0 is the total
number of atoms of element i in the system, which remains constant, since the system is closed. There will be one
such equation for each different element in the system.
Thermodynamic system 6

Isolated system
An isolated system is more restrictive than a closed system as it does not interact with its surroundings in any way.
Mass and energy remains constant within the system, and no energy or mass transfer takes place across the
boundary. 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.
Truly isolated physical systems do not exist in reality (except perhaps for the universe as a whole), because, for
example, there is always gravity between a system with mass and masses elsewhere.[3][4][5][6][7] However, real
systems may behave nearly as an isolated system for finite (possibly very long) times. The concept of an isolated
system can serve as a useful model approximating many real-world situations. It is an acceptable idealization used in
constructing mathematical models of certain natural phenomena.
In the attempt to justify the postulate of entropy increase in the second law of thermodynamics, Boltzmanns
H-theorem used equations which assumed a system (for example, a gas) was isolated. That is all the mechanical
degrees of freedom could be specified, treating the walls simply as mirror boundary conditions. This inevitably led to
Loschmidt's paradox. However, if the stochastic behavior of the molecules in actual walls is considered, along with
the randomizing effect of the ambient, background thermal radiation, Boltzmanns assumption of molecular chaos
can be justified.
The second law of thermodynamics for isolated systems states that the entropy of an isolated system not in
equilibrium tends to increase over time, approaching maximum value at equilibrium. Overall, in an isolated system,
the internal energy is constant and the entropy can never decrease. A closed system's entropy can decrease e.g. when
heat is extracted from the system.
It is important to note that isolated systems are not equivalent to closed systems. Closed systems cannot exchange
matter with the surroundings, but can exchange energy. Isolated systems can exchange neither matter nor energy
with their surroundings, and as such are only theoretical and do not exist in reality (except, possibly, the entire
universe).
It is worth noting that 'closed system' is often used in thermodynamics discussions when 'isolated system' would be
correct - i.e. there is an assumption that energy does not enter or leave the system.

Systems in equilibrium
At 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 analyzing a
thermodynamic process, it can be assumed that each intermediate state in the process is at equilibrium. This will also
considerably simplify the analysis.
In isolated systems it is consistently observed that as time goes on internal rearrangements diminish and stable
conditions are approached. Pressures and temperatures tend to equalize, and matter arranges itself into one or a few
relatively homogeneous phases. A system in which all processes of change have gone practically to completion is
considered to be in a state of thermodynamic equilibrium. The thermodynamic properties of a system in equilibrium
are unchanging in time. Equilibrium system states are much easier to describe in a deterministic manner than
non-equilibrium states.
In thermodynamic processes, large departures from equilibrium during intermediate steps are associated with
increases in entropy and increases in the production of heat rather than useful work. It can be shown that for a
process to be reversible, each step in the process must be reversible. For a step in a process to be reversible, the
system must be in equilibrium throughout the step. That ideal cannot be accomplished in practice because no step
can be taken without perturbing the system from equilibrium, but the ideal can be approached by making changes
slowly.
Thermodynamic system 7

References
[1] http:/ / www. tpub. com/ content/ doe/ h1012v1/ css/ h1012v1_94. htm
[2] Perrot, Pierre (1998). A to Z of Thermodynamics. Oxford University Press. ISBN 0-19-856552-6.
[3] I.M.Kolesnikov; V.A.Vinokurov; S.I.Kolesnikov (2001). Thermodynamics of Spontaneous and Non-Spontaneous Processes (http:/ / books.
google. com/ books?id=2RzE2pCfijYC& pg=PA136). Nova science Publishers. p.136. ISBN1-56072-904-X. .
[4] "A System and Its Surroundings" (http:/ / chemwiki. ucdavis. edu/ Physical_Chemistry/ Thermodynamics/
A_System_And_Its_Surroundings#Isolated_System). ChemWiki. University of California - Davis. . Retrieved May 2012.
[5] "Hyperphysics" (http:/ / hyperphysics. phy-astr. gsu. edu/ hbase/ conser. html#isosys). The Department of Physics and Astronomy of Georgia
State University. . Retrieved May 2012.
[6] Bryan Sanctuary. "Open, Closed and Isolated Systems in Physical Chemistry," (http:/ / quantummechanics. mchmultimedia. com/ 2011/
physical-chemistry/ open-closed-and-isolated-systems-in-chemistry/ ). Foundations of Quantum Mechanics and Physical Chemistry. McGill
University (Montreal). . Retrieved May 2012.
[7] Material and Energy Balances for Engineers and Environmentalists (http:/ / www. icpress. co. uk/ etextbook/ p631/ p631_chap01. pdf).
Imperial College Press. p.7. . Retrieved May 2012.

Abbott, M.M.; van Hess, H.G. (1989). Thermodynamics with Chemical Applications (2nd ed.). McGraw Hill.
Halliday, David; Resnick, Robert; Walker, Jearl (2008). Fundamentals of Physics (8th ed.). Wiley.
Moran, Michael J.; Shapiro, Howard N. (2008). Fundamentals of Engineering Thermodynamics (6th ed.). Wiley.

External links
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https://www.e-education.psu.edu/png520/m14_p4.html
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