Adiabatic expansion Created 2026-10-05 Updated 2026-10-14
Adiabatic expansion increases the accessible volume without heat transfer. In a loaded piston expansion of the fixed-composition ideal gas considered in adiabatic process, positive outward work comes from internal energy, so the final temperature decreases. This provides a cooling mechanism without removing heat during the stroke. In the Carnot cycle, reversible adiabatic expansion connects two different temperatures between its isothermal processes.[ref]
For the same constant- reversible ideal-gas adiabat, put . The scaling and first law of thermodynamics give
With the figure's stipulated , and , the final ratios are and . Outward work is and . Reversing this particular path from its cooled endpoint would require the same work input; the figure's separate compression starts at the original state, so its input is different. Endpoint entropy supplies another independent check:
The two logarithm terms cancel using , confirming the reversible path is an isentropic process. [ref]
PASCO's expansion demonstration first compresses trapped air and waits for thermal equilibrium before the rapid expansion. Its manual warns that friction-warmed cylinder regions contact the gas during expansion, compromising quantitative comparison. [ref] The hold separates cooling caused by expansion from simply undoing the earlier hot compression. As proposed controls, observe the temperature dip and subsequent warming, compare rapid and slow strokes from matched initial states, and assess wall heat transfer and probe lag before fitting a reversible model.
Cooling is not a universal consequence of adiabatic expansion: free expansion of an ideal gas has no outward work and returns to the same equilibrium temperature. Its entropy increases, so the reversible power laws do not describe it. Reuse free expansion, Joule's free-expansion experiment and temperature sensitivity of a free-expansion experiment for that apparatus, its energy budget and the real-gas qualifications. The useful distinction is the load: expansion cools this ideal gas when it must spend internal energy doing work.
For constant-pressure heat addition and two reversible ideal-gas adiabats, set . The Brayton cycle has , maximum temperature and minimum . A Carnot cycle using those extreme temperatures has the strictly greater efficiency displayed whenever . Reversibility of the isobaric heating requires continuously matched reservoir temperatures, rather than heat transfer solely at the maximum temperature.
Carnot cycle Created 2026-09-29 Updated 2026-10-14
A Carnot cycle realizes the reversible bound in Carnot's theorem. Its four steps for an ideal gas working substance are:
The temperature versus entropy plot in the Carnot's theorem figure is therefore a rectangle traversed clockwise. Because , its width is . For the illustrated engine, : the upper step absorbs , the lower step rejects , and the enclosed area is the net work. Geometry displays the thermal efficiency without solving the gas motion. The two vertical steps are isentropic processes, not constant-temperature steps. [ref] [ref]
Reversible heat transfer is a limit of vanishing temperature differences; ordinary finite-rate transfer introduces entropy production. The Carnot cycle is a performance benchmark rather than a guarantee of useful power. Running it backward gives the ideal operation of a refrigerator or heat pump, with work supplied to move heat toward the hotter thermal reservoir. [ref]
Coefficient of performance Created 2026-10-14 Updated 2026-10-18
For the cyclic two-side energy balance in refrigerator, define the dimensionless cooling and heating coefficients by
This identity applies even to irreversible machines, provided both coefficients refer to the same operating point, work input and boundary with no additional energy transfer or storage. It does not compare two separately operated appliances. Unlike thermal efficiency of a heat engine, a COP can exceed one: its numerator counts heat moved, including energy taken from another region. [ref]
To obtain temperature-only bounds, impose stronger assumptions: a cyclic machine exchanges heat only with two ideal thermal reservoirs maintained at uniform, fixed absolute thermodynamic temperatures , and receives work through an ideal input carrying no entropy. Include the machine and the heat transfer interfaces in the entropy production accounting. Because its own entropy returns to its initial value each cycle, the Second law of thermodynamics gives
Combining this inequality with gives
Equality requires a reversible thermodynamic process for the entire cycle and its contacts, as in a reversed Carnot cycle. These are Carnot's theorem bounds independent of the working substance. Use kelvin values, not degree Celsius readings, in the numerators; the temperature difference can be expressed in either unit. [ref] [ref]
The diagram fixes and sets , so the reversible bounds are and . The stipulated machine with and satisfies both. Its reservoir entropy production per cycle is . Increasing the temperature lift at fixed lowers both bounds. Equivalently, delivering fixed needs at least
These expressions reveal why a small temperature lift is attractive. Their divergence as is an ideal reversible limit, not a promise of infinite heating or cooling power. For finite heat transfer rates, the working fluid must be colder than the cold bath and hotter than the hot bath; these contact differences produce entropy and increase the internal temperature lift. Dissipative compression and the pressure-reducing restriction of vapor-compression refrigeration supply further departures from reversibility. Thus bath temperatures set an outer bound, not a prediction of real COP. [ref]
Heat engine 2026-10-14
A heat engine uses a repeating thermodynamic cycle to turn part of an incoming heat transfer into net outgoing work. In the two-thermal reservoir model, the hot thermal reservoir supplies heat at fixed temperature , and the cold thermal reservoir receives heat of magnitude at fixed temperature . A Stirling engine makes the repeated motion visible; the abstract energy budget applies independently of its particular mechanism.[ref]
Choose the entire cyclic device as a closed system, with no net change in bulk kinetic energy or potential energy. Count heat entering as positive and net work delivered as positive, as in the first law of thermodynamics. Thus enters with a plus sign and , although a positive magnitude, enters with a minus sign. Assume these two heat transfers and the net work are the only transfers across the boundary. Over one complete thermodynamic cycle, all stored energy, including internal energy , returns to its starting value:
The device does not accumulate heat from cycle to cycle. More precisely, heat is a transfer, while internal energy is what can be stored; even a component that temporarily stores internal energy must return to its initial state for this boundary to be cyclic.[ref]
For engine operation, and . Its thermal efficiency is
Use net work, after subtracting any work supplied during compression or required by auxiliaries included in the chosen device. For periodic operation, average power satisfies and , with the rates averaged over complete thermodynamic cycles.[ref]
For a stipulated model at and , let and per thermodynamic cycle. Then and . At two thermodynamic cycles per second, these become incoming heat transfer, outgoing heat transfer, and net power. These are constructed values, not measurements.
Figure 1.
Two-thermal reservoir heat engine: in, of net work, and rejected
. Illustrative transfers per complete thermodynamic cycle, with positive magnitudes labeled on the arrows. The closed system returns to its initial state. Arrow widths represent the energy split; the thermal reservoirs remain at and . Details.
Different signs describe different tasks. With the same directions of heat transfer, gives : a device transmitting heat without net work output. If , net work is supplied to that device. A refrigerator or heat pump instead extracts heat from the cold side and delivers heat to the hot side, using positive input work and the balance . Their useful output is heat transfer, measured by a coefficient of performance. Finally, a one-time isothermal expansion can have and while leaving the volume changed: it is not a complete thermodynamic cycle. A warming device also fails the cyclic assumption, and a fuel-consuming device requires an accounting of matter crossing its boundary.
For two fixed thermal reservoirs at positive thermodynamic temperatures, the Second law of thermodynamics strengthens the energy balance to
Equality requires the overall operation to be a reversible thermodynamic process, including its heat transfer to the thermal reservoirs. The Carnot cycle explains how the reversible benchmark is constructed, and Carnot's theorem explains its universality and the entropy production penalty. Use kelvin values, never ratios of degree Celsius readings. The example above lies below the bound: its total entropy production is per thermodynamic cycle.
Figure 2. . The upper curve is the reversible bound in Carnot's theorem. The lower curve is the stipulated model , not experimental data or a universal engine law. At , the curves give and , matching the energy budget above. The endpoint is a zero-output limit. Details.
This is useful before building a machine: warmer cooling surroundings reduce the possible thermal efficiency, even if the mechanism is unchanged. A small observed thermal efficiency does not by itself test the Second law of thermodynamics; heat leaks, friction, incomplete recovery of work, and the measurement boundary can all reduce the reported ratio. A meaningful comparison requires the actual thermal reservoir temperatures, matched heat and net work measurements, and the hypotheses of Carnot's theorem. Finite bodies whose temperatures change are treated separately there.
The practical question already appears in the 1824 Réflexions sur la puissance motrice du feu et sur les machines propres à développer cette puissance by Sadi Carnot: pp. 6–8 ask whether machines driven by heat have a fundamental limit and whether changing the working substance can improve their output. Pages 9–11 describe heating and cooling in real machines, but use the historical caloric theory, rather than the modern first law of thermodynamics balance. The historical discussion under Carnot's theorem explains that distinction.
Isothermal expansion Created 2026-10-05 Updated 2026-10-14
An isothermal expansion increases the volume of a thermodynamic system at fixed temperature. For a reversible ideal gas path, the gas delivers positive work and absorbs positive heat, with and . The heat bath supplies the expansion energy; without sufficient heat transfer, doing work instead lowers the temperature. This transfer is the hot step of a Carnot cycle, and it is why an expanding gas need not cool when its surroundings continuously replenish its internal energy.
An insulated free expansion into an evacuated compartment is different. In the idealization with no heat exchange, no external work and no container energy change, . Since internal energy of an ideal gas depends only on temperature, its final equilibrium temperature equals its initial value. The transient need not have a uniform temperature or pressure, so equal endpoint temperatures do not make it a reversible isotherm. Do not apply the logarithmic isothermal ideal-gas work formula to this irreversible process. Its entropy still increases by ; entropy change in free expansion evaluates this state function difference using a hypothetical reversible path.[ref]
For a real gas, even equal-temperature equilibrium endpoints need not have equal internal energy. An insulated free expansion can therefore change the temperature, while a controlled isothermal expansion must provide the heat needed for both its internal energy change and its delivered work. The internal energy at constant temperature article gives the Van der Waals equation example.[ref]
Kelvin-Planck statement of the second law Created 2026-09-24 Updated 2026-10-14
No cyclic device can have as its sole effect the extraction of heat from one thermal reservoir and its complete conversion into net work. A putative device absorbing and returning to its starting state with and no other transfer would conserve energy, yet violate the Second law of thermodynamics. Rejecting heat to colder surroundings is an essential part of the ordinary two-thermal reservoir heat engine budget.[ref]
The cyclic and sole-effect qualifications matter. A single isothermal expansion of an ideal gas can absorb heat and deliver equal work while leaving its volume changed; restoring the initial state must also be counted. Likewise, a device discharging stored internal energy or consuming fuel has another effect. Converting supplied electrical work completely to heat through Joule heating reverses the proposed conversion and is allowed. The statement also allows cyclic devices that exchange heat with one thermal reservoir while consuming net work; it forbids positive net work output with that single heat source as the only external change.
Conversely, a hypothetical complete-conversion device could take from the hot thermal reservoir and supply of work to an ideal refrigerator that extracts from the cold thermal reservoir and delivers to the hot one. At and , that refrigerator is itself admissible: its reservoir entropy changes cancel. The composite would consume no external work and move a net from cold to hot, violating the Clausius statement of the second law. Together with the construction there, this proves the equivalence of the two impossibility statements.[ref]
For the two fixed positive-temperature thermal reservoir hypotheses, Carnot's theorem gives the sharper restriction . A reversible thermodynamic process reaches that bound in the ideal Carnot cycle; an ordinary device's smaller thermal efficiency reflects its entropy production and measurement boundary. An inefficient observed engine is compatible with the Second law of thermodynamics, rather than evidence that the bound has been experimentally determined.
A clockwise engine Carnot cycle has four reversible steps. At hot temperature , isothermal expansion absorbs and does positive work by the gas. Adiabatic expansion then cools it to , with zero heat and positive work by the gas. Isothermal compression at emits and requires work on the gas. Finally adiabatic compression returns it to , with zero heat and work on the gas.
For an ideal gas, the isotherms obey and the adiabats , the latter being steeper. In the plane, the isotherms are horizontal and the adiabats vertical, forming a clockwise rectangle. Heat occurs only on the horizontal legs, while work occurs on all four legs.
Reversing the arrows gives a refrigerator, reversing the heat and work signs.
Macroscopically, an adiabatic process exchanges no heat with its surroundings: . A reversible adiabatic process is therefore isentropic, since . Microscopically, the system is thermally isolated, so changes in its energy arise from work done by changing external parameters rather than random energy exchange with a heat bath; in a sufficiently slow change, the populations of the corresponding microscopic states are carried along without producing entropy.
For repeated operation the working substance must execute a thermodynamic cycle. Reversible isothermal contact at absorbs heat , a reversible adiabat changes the temperature to , reversible isothermal contact at rejects heat , and a second adiabat returns to the initial state. This is the Carnot cycle. Reversibility and zero net entropy change give
The thermal efficiency is the net work output divided by the absorbed heat:
Consequently
The Carnot theorem shows that any irreversible cycle has smaller efficiency, so the two isotherms joined by two adiabats are optimal.
In the Carnot cycle, let be reversible isothermal expansion at , reversible adiabatic expansion, isothermal compression at , and adiabatic compression. The pressure–volume curve is clockwise. The entropy–temperature figure below uses temperature on the horizontal axis and entropy on the vertical axis, literally an – plot: isotherms are vertical and adiabats horizontal. The hot isotherm increases entropy by and absorbs ; the cold one rejects . Thus and .
For the second engine, choose the working direction with heat addition during at and rejection during at . A reversible ideal-gas adiabat obeys . Define
The two constant-pressure heat transfers are and , where rejected heat is quoted positive. Therefore the Brayton cycle efficiency is
for . All heat-capacity amount conventions cancel in the ratio.
Since and , , the maximum is at B and the minimum at D. The Brayton-Carnot efficiency comparison is
The inequality is strict for a nondegenerate cycle with positive heat input. Although each process can be reversible, the isobaric heat transfer spans a range of temperatures; making the whole cycle reversible requires a succession of matched-temperature reservoirs, rather than just the hottest and coldest reservoirs.
For an ideal diatomic gas with active rotation and frozen vibration, and
Here . This comparison holds at the same pressure ratio and assumes temperature-independent heat capacities in the stated mode regime. Frozen rotation or excited vibration would require their actual heat capacities.
The reversible working substance changes entropy by on its hot isotherm and on its cold isotherm, with zero change on the two reversible adiabats. Closure requires . The substance has zero entropy change over a cycle, while the reservoirs have changes and . Thus for the complete Carnot cycle.
The Second law of thermodynamics restricts which energy-conserving processes can occur. In the Kelvin-Planck statement of the second law, no cyclic engine can have as its sole effect the extraction of heat from one reservoir and its complete conversion into work. In the Clausius statement of the second law, no process can have as its sole effect transferring heat from a colder reservoir to a hotter one. An engine or refrigerator combined with the reverse of a reversible device shows that a violation of either statement would violate the other.
A heat engine takes heat from a reservoir at , rejects to one at , and returns its working substance to the initial state. Energy conservation gives and efficiency . Carnot's theorem states that no engine between these reservoirs is more efficient than a reversible one, and that all reversible engines between them have the same efficiency. Otherwise, drive a reversible engine backwards with the work of a more efficient engine; the composite cycle transfers heat from cold to hot without external work, contradicting the Clausius statement.
A reversible Carnot cycle consists of two isotherms joined by two reversible adiabats. For an ideal gas, and . The adiabats give , so
Carnot's theorem makes this independent of the working substance and defines the thermodynamic absolute-temperature scale consistently with ideal-gas temperature.[ref]
For any reversible cycle, . This makes the integral between two equilibrium states independent of the reversible path, defining the state function entropy:
Heat itself is path dependent; entropy is not. An irreversible change can be evaluated using any imagined reversible path between its equilibrium endpoints. For example, a fixed amount of ideal gas with constant has .
For a general cycle the Clausius inequality is . The entropy balance for a process is , with equality for reversible heat exchange and no entropy production. The surroundings' entropy must be included, giving . A system's own entropy can decrease by exporting entropy; an isolated system's cannot.
The engine's reservoirs have net entropy change , so
with equality for a reversible engine. Friction, heat flow through a finite temperature difference and unrestrained expansion produce entropy and reduce usable work. Thus energy conservation fixes the balance of heat and work, while the second law fixes their direction and the attainable efficiency.[ref]
A Carnot cycle consists of two reversible isothermal branches joined by two reversible adiabatic branches. Let the hot isothermal expansion run from volume to , and the cold isothermal compression from to . For moles of an ideal gas, their absorbed and rejected heat magnitudes are
On a reversible ideal-gas adiabat, is constant. Applying this to the two joining branches gives . Therefore
The result is independent of the gas's heat-capacity ratio. This derivation presumes the usual constant-heat-capacity ideal-gas model; more generally the equal entropy changes on the two isotherms give the same heat ratio without that restriction.
To establish the upper bound, suppose an engine were more efficient between these same two reservoirs. Use its output work to drive a reversed Carnot cycle, scaled so that the work magnitudes match. For fixed work , the hypothetical engine would take from the hot bath, whereas the reversed Carnot cycle would return to it. The combined device would transfer heat from the cold bath to the hot bath without any net external work. That contradicts the Clausius statement of the second law. Hence no such two-reservoir engine can exceed .
For the triangular cycle, call the three successive vertices , and measure energies in units of . For one mole of a monatomic ideal gas, , and positive work done by the gas is . The net values on the three complete branches are
Thus the net work is , equal to the triangle's enclosed area.
There is a small but important distinction between the net heat on a branch and its total positive heat input to a cycle. On the sloping branch put , so , with . Then
There is a heat-flow reversal along a thermodynamic path at . The first part absorbs heat; the final part rejects it. Integrating the two signed contributions separately gives
The true total absorbed and rejected heats and thermal efficiency are therefore
For clarity, the positive heat input on is , on it is , and on it is zero. Using just the positive net heats of the complete branches would give and ; that shortcut misses the short heat-rejection interval on .
Figure 1.
Original pressure-volume cycle with the interior temperature maximum and the late reversal of heat flow
. Details.
Finally, put . The minimum temperature is at . Along ,
which has its maximum at , not at either endpoint. Thus the corresponding two-reservoir Carnot efficiency is
The triangular cycle receives heat at a range of temperatures below and rejects it at temperatures above . It therefore makes less work per unit input heat than a Carnot cycle using only those extrema. The geometric path alone does not prove irreversibility: it could in principle exchange heat reversibly with a continuum of matched-temperature reservoirs, while still having this lower efficiency. Restricting it to only the two extreme-temperature reservoirs would introduce additional irreversible heat transfers.
A Carnot cycle consists of four reversible stages: isothermal expansion at the hot-reservoir temperature , adiabatic expansion to , isothermal compression at , and adiabatic compression back to the starting state. The adiabatic stages exchange no heat. For one mole of an ideal gas, the two isothermal stages have heats and in magnitude. The reversible adiabatic relations ensure .
More generally, the total entropy change over any reversible cycle is zero. The two heat exchanges therefore satisfy
With work output , its thermal efficiency is
The temperatures must be absolute. The second law makes this the maximum efficiency for an engine exchanging heat only with those two reservoirs; irreversible entropy production lowers the efficiency.
Use an ideal gas to illustrate the Carnot cycle, with hot and cold heat baths at and . The four processes are all reversible thermodynamic processes. Lettered states below belong only to this illustration; the engine later in the question uses numbered states.
Figure 1.
An ideal-gas Carnot cycle: two isotherms joined by two reversible adiabats
. Details.
Starting at , perform the following four stages:
The clockwise enclosed area in the pressure-volume diagram is the positive net work per cycle, .
The complete cycle must be a reversible thermodynamic process: no friction, viscous dissipation, unrestrained expansion, or other source of entropy. Each moving boundary must be arbitrarily close to mechanical equilibrium. Heat transfer to or from a bath must occur across an infinitesimal temperature difference, and the insulated stages must be genuinely adiabatic processes. There must also be no direct heat leak between the heat baths.
For an engine exchanging heat only with these two heat baths, the Second law of thermodynamics gives
and thus
Practical engines generate entropy through finite temperature differences, friction and other dissipative effects. They therefore fall below the Carnot cycle limit. Approaching reversible heat exchange generally requires vanishingly slow operation for a finite heat-transfer apparatus, limiting useful power.
For a diatomic ideal gas in the usual regime with three translational and two rotational quadratic degrees of freedom, but frozen vibrational excitation, the equipartition theorem gives
The Brayton cycle efficiency is therefore
The constant-pressure expansion has , while the compression has . The same relations give . Thus, in units of the minimum temperature,
The maximum and minimum temperatures are and . A Carnot cycle between those extremes has
The difference is about percentage points. In the Brayton cycle, heat is supplied and rejected over ranges of temperature; the whole input is not supplied at , nor is the whole rejection made at . This explains the lower efficiency even for mechanically ideal stages. Absolute state temperatures are not supplied, so is an explicit standard diatomic-gas approximation rather than a conclusion about all possible rotational and vibrational excitation regimes.
For an ideal Diesel cycle with compression ratio , cutoff ratio and constant heat-capacity ratio , its thermal efficiency is . As the quotient tends to , giving . The maximum-to-minimum temperature ratio tends to , so the limiting efficiency equals that of a Carnot cycle between those temperatures. Both heat input and net work vanish in this limit: the result is a limit of their ratio, not a finite-work engine at exactly zero cutoff interval.
Vapor-compression refrigeration Created 2026-10-14 Updated 2026-10-18
Vapor-compression refrigeration circulates a working fluid through cold and hot coils. In the cold coil, liquid becomes gas while absorbing heat from the refrigerated region. Compression supplies work and raises the pressure and temperature; the hot coil releases heat as the gas returns to liquid. A restriction reduces the pressure before the next cold-side passage. Changing the pressure changes the temperature of the phase transition, letting one circulating fluid receive and release heat at different temperatures. This physical implementation serves both refrigerators and heat pumps; its ordinary dissipative operation differs from the reversible Carnot cycle used to bound performance. [ref] [ref]