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]
Clausius statement of the second law Created 2026-09-24 Updated 2026-10-14
No cyclic device can have as its sole effect the transfer of heat from a colder thermal reservoir to a hotter thermal reservoir. The word “sole” includes the surroundings: the device must return to its starting state, and there must be no net supplied work, depletion of a stored resource, or accompanying change elsewhere. The statement excludes a self-running refrigerator, while allowing an ordinary refrigerator or heat pump supplied with work.[ref]
For a proposed transfer from a fixed cold thermal reservoir at to a fixed hot thermal reservoir at , with no other effect, the total entropy change would be
The first law of thermodynamics permits this energy balance; the Second law of thermodynamics forbids the negative total entropy change. For , and , it is . Direct heat transfer in the opposite direction has positive total entropy change. A powered heat pump has a different budget: it supplies work and delivers more heat to the hot side than it extracts from the cold side.
A short equivalence argument links this restriction to the Kelvin-Planck statement of the second law. Couple a hypothetical device that moves from cold to hot with no other effect to the heat engine illustrated above, which absorbs , rejects , and delivers . The cold-side transfers cancel; the combined cyclic device takes from the hot thermal reservoir and delivers exactly of work, violating the Kelvin-Planck statement of the second law. Matching transfers is an ideal composition argument, not a claim that such a device exists.[ref]
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 Created 2026-09-24 Updated 2026-10-14
Heat is energy transferred across a thermodynamic system's boundary because of a temperature difference. It is measured in joules, like work and internal energy. A hot cup transfers heat to cooler surroundings; its temperature describes its state, while the transferred heat describes a process. The cup stores internal energy, rather than a substance called heat. [ref]
For a closed system with unchanged bulk kinetic energy and potential energy, choose for heat entering and for work done by the system. The first law of thermodynamics gives
Here is the stored internal energy. For example, a sealed piston cylinder receiving of heat and delivering of work gains of internal energy. A closed system retains its matter while exchanging energy; it need not be an isolated system. [ref]
Figure 1.
Heat input and work output determine the internal energy increase
. The dashed boundary encloses a closed system in a sealed piston cylinder. The incoming arrow carries of heat; the outgoing arrow carries of work done by the system. With unchanged bulk kinetic energy and potential energy, . No matter crosses the boundary. Details.
Unlike internal energy, heat is not a state function: different paths between the same equilibrium states can transfer different , with compensating differences in work. The symbol records this dependence on the path; there is no stored quantity whose difference is always . The two paths in first law of thermodynamics illustrate this directly. Supplied heat can raise temperature as sensible heat, change a phase fraction through latent heat, or help supply expansion work. Measuring temperature alone therefore does not determine transferred heat.
For a reversible thermodynamic process, , where is absolute temperature and is entropy. This identification requires reversibility: an irreversible adiabatic process has and can nevertheless increase entropy. Likewise , with enthalpy , requires the particular fixed-pressure conditions in enthalpy. These distinctions make heat useful as a precise boundary-transfer quantity in heat engines, refrigerators and heating calculations.
Historically, James Prescott Joule's paddle experiments showed that stirring water with input work could raise its temperature, helping establish conservation of energy. The lesson is still useful: a temperature rise can result from work even without incoming heat. [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.
Heat pump 2026-10-14
A heat pump uses work to deliver heat to the region we want to keep warm. Its useful output is the hot-side delivery . The same operating machine can be described as a refrigerator when the cold-side extraction is the objective: which output is useful changes the coefficient of performance, while the energy balance stays . Heating a water bath by taking heat from a colder water bath makes this distinction visible in the heat-pump calorimetry experiment below. [ref]
In the illustrative budget from refrigerator, supplying of work delivers of useful heat, giving a heating coefficient of performance of . The additional came from the colder region. Compare an ideal electrical heater whose entire input work becomes heat in the target region: it delivers for that input. The appeal of a heat pump is this ability to move existing energy, while the Second law of thermodynamics limits the work saving for a given pair of temperatures.
Figure 1.
One energy budget, two useful outputs, and Carnot's theorem bounds on the coefficient of performance
. Original quantitative diagram, with stipulated , and . Arrow widths follow the transfer magnitudes. The curves are reversible bounds for fixed cold temperature and varying hot temperature ; they are not measured performance. At , the bounds are for cooling and for heating, above the illustrative machine's and . Details.
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.
Refrigerator 2026-10-14
A refrigerator removes heat from the region we want to keep cold and releases heat to warmer surroundings. Here we consider a work-driven cyclic device: its useful output is the cold-side extraction , and its input is net work . A food compartment is a familiar example; the same cooling objective applies when removing heat from a room. The coefficient of performance measures extraction per unit work, rather than the fraction of input energy converted into output. [ref]
Choose the complete machine as the thermodynamic system. Let be heat entering from the colder side, be heat delivered to the hotter side, and be net work supplied, all over the same complete cycle. Assume these are its only energy transfers, no matter crosses the outer boundary, and there is no net change in stored energy. Returning to the initial state gives , so the first law of thermodynamics reads
The heat leaving the warmer side includes both the extracted heat and the supplied work. For instance, stipulated transfers and require ; the cooling coefficient of performance is . This is an illustrative budget, not measured performance. At steady operation the same balance holds for average transfer rates, , where is input power.
This budget explains a useful counterexample: operating a refrigerator with its door open inside an otherwise isolated room cannot cool the room as a whole. If both heat transfers occur within the room and the electrical input comes from outside, the room gains each cycle. Locally cold air does not imply net cooling. The Second law of thermodynamics permits cold-to-hot transfer because work is supplied; it forbids a cyclic device whose sole effect is that transfer. See the Clausius statement of the second law.
Second law of thermodynamics Created 2026-09-24 Updated 2026-10-14
For an isolated system, the second law requires . More generally, include all affected surroundings to obtain
Equality describes the reversible limit; irreversible macroscopic processes produce entropy. A closed system can lose entropy by exporting heat, so nondecrease does not apply to that system alone. The Clausius statement of the second law forbids a cyclic device whose sole effect is transferring heat from cold to hot. The Kelvin-Planck statement of the second law forbids a cyclic device whose sole effect is converting heat from one thermal reservoir completely into work. "Sole effect" matters: a refrigerator moves heat from cold to hot by consuming work. [ref]
For direct transfer of from a thermal reservoir at to one at , with no work extracted,
The reverse transfer alone would have negative total entropy change. Both directions conserve energy, but only the hot-to-cold direction is spontaneous. The finite-body example under entropy replaces these constant temperatures by changing ones.
Friction, free expansion and heat transfer across a finite temperature difference all introduce irreversibility. Moving arbitrarily slowly is insufficient if friction remains. A reversible thermodynamic process must permit restoration of both the system and surroundings. This gives engineers a useful ideal benchmark: irreversibility spends an opportunity to obtain work, even though energy itself is conserved. [ref]
Thermodynamics Created 2026-09-24 Updated 2026-10-13
Thermodynamics studies energy transfers and the constraints on macroscopic changes. Its vocabulary connects internal energy, entropy, temperature, pressure and volume to heat and work. The first law of thermodynamics balances energy; the Second law of thermodynamics decides which changes can occur spontaneously and limits how much work a heat engine can deliver. These principles let us bound performance before choosing a material or a detailed machine design. Applications include power generation, propulsion and refrigerators. [ref]
Start by choosing a system boundary. A closed system can exchange energy but no matter; an isolated system exchanges neither. A state function, such as internal energy or entropy, depends on the equilibrium state. A process specifies how that state changes. Thus a body's temperature is a property it has, whereas heat records energy crossing its boundary during a process. A body contains internal energy, rather than a stored quantity of heat.
Two insulated bodies initially at different positive temperatures approach thermal equilibrium when brought into thermal contact. Their combined energy is conserved, but their combined entropy increases. They do not spontaneously separate again into a hotter body and a colder one. This familiar asymmetry makes thermodynamics interesting: conserving energy leaves many imaginable changes available, and entropy supplies a further constraint. The same distinction underlies both entropy maximization under thermal contact and the thermal efficiency limit in Carnot's theorem.
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]