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]
Carnot's theorem 2026-10-14
No cyclic heat engine exchanging heat only with two fixed thermal reservoirs at positive absolute temperatures can exceed the thermal efficiency of an engine whose cycle is a reversible thermodynamic process between them. All such reversible engines have the same thermal efficiency, regardless of their working substance. Let be heat absorbed from the hot thermal reservoir and the magnitude rejected to the cold one. Then
The work convention is the one in the first law of thermodynamics: is net output by the engine. Use absolute thermodynamic temperatures, such as values in kelvin; ratios of readings in degree Celsius are invalid because their zero is shifted.
For , and , the maximum thermal efficiency is . A reversible engine delivers and rejects . The thermal reservoirs have entropy changes and , which cancel. The engine's own entropy change is zero over its thermodynamic cycle.
Figure 1.
Carnot engine energy transfers and the reversible cycle between 600 K and 300 K
. Details.
A short derivation now becomes transparent: the Second law of thermodynamics gives , and the first law of thermodynamics gives . Together they yield the bound and, more precisely,
At fixed , every extra unit of total entropy production reduces output by units of energy. [ref]
Fixed thermal reservoirs are essential. Finite bodies cool and warm, so their initial temperature ratio cannot be used throughout an entire extraction process. As a computed contrast, the bodies with equal constant heat capacity in the entropy example would reach if a reversible engine extracted work until their temperatures matched. Zero total entropy change gives this geometric mean; the first law of thermodynamics then gives . Direct contact reaches and extracts no work.
Carnot's 1824 book asked whether the useful output of machines driven by heat was fundamentally limited and whether changing the working substance could improve that limit. Its reversible comparisons are the historical setting of Carnot's theorem. Carnot used the then-current caloric picture, treating heat as conserved in its passage through an engine; the modern balance should not be read back into that text.[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]
Degree Celsius 2026-10-14
The degree Celsius has the same size as the kelvin, with a shifted temperature origin: . Thus a change of one degree Celsius is a change of one kelvin, but temperature ratios in Carnot's theorem must use absolute thermodynamic temperature.[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-engine calorimetry 2026-10-14
Heat-engine calorimetry measures heat transfers so that observed work can be compared with the correct energy input. Measuring motion alone cannot supply the denominator of thermal efficiency.
The institutional Laboratory 16: Stirling Engine describes a modern teaching arrangement: an ethanol lamp drives a Stirling engine coupled to an electrical output device, which supplies a resistor immersed in water in a calorimeter. The prescribed readouts include fuel mass consumed, the pressure-volume loop, electrical readings, and water temperature. The sequence separates fuel input, gas-cycle work, electrical output, and Joule heating of the water. Warming of the water is the final useful output; it is not the engine's rejected . The handout distinguishes warm-up from steady operation and asks students to compare the final warming with direct heating by the lamp. It gives a procedure, not a table of measured efficiencies. Its pp. 1–3 therefore establish an apparatus and measurement design without supplying a new experimental result.
For a proposed calibration, use a known input of electrical work to determine the effective heat capacity of the water, vessel and immersed parts; stir to make the measured temperature representative. A matched run with no input estimates exchange with the room. For constant and no phase transition, the resulting model is
where is the signed net heat lost to the room during the measurement. Here is supplied electrical work when the resistor lies inside the calibration boundary; for a separate external heat input it is the received heat. These are proposed controls, not controls reported in that handout. Slow cooling, changing material properties and imperfectly matched room exchange limit this inference; the approach to thermal equilibrium and heat capacity matter as much as the thermometer reading.
To measure the actual engine-input , one must instrument its hot-side transfer separately, or close a calibrated energy balance around a specified heater boundary. A heater's electrical work includes changes in its stored internal energy and heat transfer that bypasses the engine. At periodic operation a cold-side flowing-water measurement can instead estimate , if mass flow rate and specific heat capacity at constant pressure are known, with negligible storage and other heat exchange in that measurement boundary. It measures only the rejection captured by that stream. Include all remaining transfers before using the residual to infer . This measurement discipline makes a comparison with Carnot's theorem meaningful.
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.
Heat-pump calorimetry 2026-10-14
A motivating bench experiment asks whether a hot bath receives more heat than the electrical work supplied to a heat pump. PHYWE's authored operating instructions, section 4, describe a sealed vapor-compression refrigeration apparatus with its cold and hot coils immersed in separate water vessels. The quantitative procedure calls for insulated vessels, stirring to reduce temperature gradients, timed temperature readings, and a wattmeter for the input. It waits about five minutes for operating conditions to settle before measurements and explicitly includes the glass vessel and immersed copper pipe when calculating the heated body's heat capacity. One bath cooling while the other warms makes the origin of the delivered energy observable. [ref]
The following analysis extends that procedure to simultaneous measurements of both finite baths. Weigh the water in each vessel; determine the effective heat capacities and , including immersed hardware, by a separate known electrical-input calibration over the working temperature range. A matched pair of calibrated thermometers placed in stirred water measures bulk and ; keeping probes away from the coils avoids mistaking a local contact temperature for the whole bath. Record the room temperature and synchronise the electrical meter and thermometry. Use short intervals after startup, with no boiling or freezing and small enough temperature changes that constant effective heat capacities are a reasonable approximation. These are proposed measurement controls, rather than reported results from the manual.
Over a common interval , the uncorrected bath estimates and measured electrical input are
Here the wattmeter records real electrical power . The integral handles changing input, and the signs make both estimated useful heat quantities positive during heating and cooling. The effective heat capacity includes water mass times its specific heat capacity plus the response of the vessel and immersed hardware. Without that correction, equal temperature changes need not imply equal heat transfers.
Insulation reduces heat leaks but does not establish an isolated system. A warmer bath can lose heat to the room while a colder bath gains it. As a proposed control, measure pump-off drift at matched bath and room temperatures, with the same stirring and insulation. Writing for outward hot-bath leak power and for inward cold-bath leak power, the bath balances give
Integrate these rates over the same interval before dividing by . For example, in a pump-off hot-bath control, ; in the cold-bath control, . Check that a stopped machine does not create a different leak path from the running one; otherwise use an independent bath calibration and keep that discrepancy as an uncertainty. Repeat at the same starting temperatures to distinguish drift from a change in COP as the baths separate.
Figure 1.
Heat-pump calorimetry: bath temperature slopes, electrical work, and heat-leak corrections
. Original apparatus schematic and stipulated constant-rate calculation, not measured data and not a performance claim for the cited apparatus. Each finite bath has effective heat capacity . The hypothetical machine takes , extracts , and delivers ; hot-bath loss is and cold-bath gain is . Over the hot bath warms by and the cold bath cools by . Correcting the two bath estimates restores the machine's heating COP and cooling COP. Details.
In the illustrated toy model, , , , , , and are stipulated constants for . The slopes are and . Consequently,
The raw heating and cooling ratios are and , whose difference is . Correcting the bath leaks gives and , whose difference is one. The apparent failure of was incomplete measurement of heat, not a violation of the first law of thermodynamics.
Real apparatus can also release motor heat and pipe heat directly to the room, and store internal energy during startup. For a machine boundary that receives electrical work, an additional outward heat transfer gives . The residual therefore tests the boundary and corrections; do not force it to zero. Include any auxiliary electrical work in the input if quoting whole-apparatus COP, and account separately for stirring work deposited in a bath. Ignoring vessel heat capacity, sensor lag or room leaks can bias the inferred result. These limitations follow from extending the measured energy budget, and the manual's explicit hardware correction illustrates why such boundaries matter.
Finally, these vessels are finite bodies whose temperatures change; they are not fixed thermal reservoirs. Their ratio of integrated useful heat to integrated input work is an interval COP. A Carnot's theorem comparison using simultaneous bath temperatures is a local approximation only when the machine settles much faster than the baths change. An exact reversible comparison for changing bath temperatures instead uses the bath entropy changes, for example for constant heat capacities, negligible net machine entropy change and no room leaks. The experiment's beauty is that two thermometers, known heat capacities and an electrical-energy measurement expose both conservation of energy and the practical gap from reversibility.
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.
Stirling engine 2026-10-14
A Stirling engine repeatedly heats and cools a confined gas, whose expansion and compression drive a moving mechanical load. This makes it a particularly accessible example of a heat engine: both the repeating motion and the two regions exchanging heat can be observed.
In the published Demonstration experiments with a Stirling engine by Christopher G Deacon and others, an electrical heater warms one end of a cylinder and flowing water cools the other at . A moving displacer shuttles gas through copper wool that temporarily stores and returns internal energy. A laser spot traces a closed pressure-volume path on a screen: mechanical motion controls one coordinate, pressure the other. Calibrating both scales converts the enclosed area to work per thermodynamic cycle; multiplying by rotation frequency gives gas-cycle power. At heater input, the paper reports gas-cycle power, while a separate Prony brake measures shaft output. The cold-side temperature is controlled and two higher heater settings are compared. The gas has a nonuniform temperature, and heater energy also escapes to the room: neither output/input ratio measures for an ideal two-thermal reservoir engine. These observations demonstrate work production and losses, not a direct measurement of the bound in Carnot's theorem. The inspected apparatus, readouts and results are on pp. 180–182, Figures 1–3 and Table 1.
Temperature Created 2026-09-24 Updated 2026-10-14
Temperature labels thermal equilibrium: two internally equilibrated bodies have the same temperature when contact permitting only heat exchange produces no net heat transfer. The zeroth law of thermodynamics makes the comparison transitive. If bodies A and B separately reach thermal equilibrium with the same thermometer without appreciably disturbing either body, they agree with each other. This is what lets a gas thermometer compare a metal block with water, despite their different internal energies and heat capacities. Insulation alone makes no such comparison: it can prevent heat transfer between bodies at different temperatures. [ref]
The zeroth law of thermodynamics establishes equality comparisons, but does not choose a numerical scale. Thermodynamic temperature supplies an absolute scale consistent with Carnot's theorem and entropy. For a simple compressible system at thermodynamic equilibrium with fixed particle number and composition,
Here is internal energy, is entropy, and is volume; the second equality assumes the derivative can be inverted. Temperature is a thermodynamic conjugate variable to entropy and belongs to the intensive and extensive thermodynamic quantities as an intensive quantity. Its partial derivative tells us how much internal energy must change per unit change of entropy under the stated constraints. More general systems require their other mechanical and material variables to be held fixed too. [ref]
For an infinitesimal quantity of heat transferred from A to B, with no work or matter exchange, the equilibrium entropy changes give
For ordinary positive temperatures, spontaneous heat transfer from increases total entropy; thermal equilibrium has . This comparison uses changes in entropy, rather than the total internal energy contained in either body. A small hot object can have less internal energy than a large cool one. See entropy maximization under thermal contact for the equilibrium criterion and negative temperature for the special case of bounded energy spectra.
Express absolute thermodynamic temperature in kelvin, and a Celsius reading in degree Celsius:
The offset is exact: corresponds to , and to . Their absolute temperature ratio is ; dividing their Celsius readings gives a different number. Thus gas thermometer pressure ratios and Carnot's theorem require thermodynamic temperature. The modern SI definition of the kelvin fixes the Boltzmann constant ; a reference bath realizes or transfers the scale rather than defining that constant.[ref]
Temperature is not universally the mean kinetic energy of a particle. In a classical, nonrelativistic ideal gas at thermal equilibrium, the equipartition theorem gives the mean translational kinetic energy relative to the gas's bulk motion:
Here is particle mass, its velocity, and the mean flow velocity. In this regime, different particle masses at the same temperature have equal mean translational kinetic energies but different characteristic speeds. A moving gas can also carry bulk kinetic energy without being hotter in its rest frame. Internal molecular modes and quantum statistics require further care; the equipartition theorem has classical assumptions, whereas the equilibrium entropy definition applies more widely. [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.