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In
thermodynamics, a 'thermodynamic system', originally called a ''working substance'', is defined as that part of the universe that is under consideration. A real or imaginary
boundary separates the system from the rest of the universe, which is referred to as the environment or
surroundings (sometimes called a reservoir.) A useful classification of thermodynamic systems is based on the nature of the boundary and the quantities flowing through it, such as matter, energy, work, heat, and entropy. A system can be anything, for example a
piston, a
solution in a
test tube, a living
organism, or a
planet, etc.
History of term
The first to develop the concept of a "thermodynamic system" was the French physicist
Sadi Carnot who in 1824 studied what he called the ''working substance'' (system), i.e. 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 to use the term "working body" when referring to the system. From his 1850 manuscript On the Motive Power of Fire Clausius states:
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 ''T
H'' furnace through the fluid of the "working body" (working substance) and into the cold sink ''T
C'', 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 ''Q
H'' was supplied by a boiler, wherein water was boiled over a furnace; ''Q
C'' was typically a stream of cold flowing water in the form of a
condenser 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”.
Overview
Thermodynamics is conducted under a ''system-centered view'' of the universe. All quantities, such as
pressure or
mechanical work, in an equation refer to the system unless labeled otherwise. Thermodynamics is basically concerned with the flow and balance of energy and matter in a thermodynamic system. Three types of thermodynamic systems are distinguished depending on the kinds of interaction and
energy exchange taking place between the system and its surrounding environment:
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Isolated systems are completely isolated in every way from their environment. They do not exchange heat, work or matter with their environment. An example of an isolated system would be an insulated rigid container, such as an insulated gas cylinder.
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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.
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Open systems: exchanging energy (heat and work) and matter with their environment. A boundary allowing matter exchange is called ''permeable''. The ocean would be an example of an open system.
In reality, a system can never be absolutely isolated from its environment, because there is always at least some slight coupling, even if only via minimal gravitational attraction. In analyzing a system in steady-state, the energy into the system is equal to the energy leaving the system
[1].
As an example, consider 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 does not measure time, but it does sometimes accept limitations on the timeframe of a process.)
Systems in equilibrium
It is a fact that, for isolated systems, as time goes by, internal differences in the system tend to even out. Pressures and temperatures tend to equalize, as do density differences. A system in which all these equalizing processes have gone practically to completion, is considered to be in a state of
thermodynamic equilibrium. Its thermodynamic 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.
Open systems
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:

During
steady, continuous operation, an energy balance applied to an open system equates shaft work performed by the system to heat added plus net
enthalpy added.
:
where ''U
in'' is the
average internal energy entering the system and ''U
out'' is the average internal energy leaving the 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''), 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.
See also
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Physical system