Carnot cycle ($W=(T_h-T_c)\Delta S$)

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 $\delta Q_{\mathrm{rev}}=TdS$, its width is $\Delta S=Q_h/T_h$. For the illustrated engine, $\Delta S=5/3\mathrm{J}{\mathrm{K}}^{-1}$: the upper step absorbs $600\times 5/3=1000\mathrm{J}$, the lower step rejects $300\times 5/3=500\mathrm{J}$, and the enclosed area is the $500\mathrm{J}$ 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]

The reversible heat-engine efficiency between absolute temperatures $T_H$ and $T_C$, ${\eta }_C=1-T_C/T_H$. Real conversion between the same reservoirs cannot exceed it.

An isothermal process changes a thermodynamic system while keeping its temperature constant. It need not keep its pressure, volume or internal energy constant, and it does not generally have zero heat transfer. An adiabatic process specifies zero heat transfer instead. For example, a slowly expanding ideal gas can absorb heat from a heat bath and deliver the same amount of work while its temperature stays fixed.

For a fixed amount of substance and composition, internal energy of an ideal gas depends only on temperature. With $Q>0$ for heat entering and $W_{\mathrm{by}}>0$ for work delivered to the surroundings, the first law of thermodynamics therefore givesThis equality does not determine either transfer until the path is specified. Isothermal ideal-gas work gives the reversible value; an insulated free expansion has a different value even when its equilibrium endpoints have the same temperature. The closed system convention here excludes changes in bulk kinetic energy and external potential energy.

A conducting cylinder in a large, stirred heat bath approximates an isothermal process when the piston moves slowly enough for thermal conduction to keep up. A quasistatic process keeps the gas close to internal thermodynamic equilibrium; a reversible thermodynamic process additionally requires negligible friction and vanishing driving differences in pressure and temperature. Exact equality of the gas and heat bath temperatures gives no finite heat transfer rate through a finite thermal resistance. The reversible description is a limit of arbitrarily small differences and arbitrarily slow motion, illustrated by the finite-rate isothermal piston model.^[ref]

For a real gas, internal energy at constant temperature can change with volume because molecular interaction potential energy changes. In one smooth thermodynamic phase of a fixed-composition simple compressible system,Thus an isothermal process generally has $Q=\Delta U+W_{\mathrm{by}}$, with no reason to set $\Delta U=0$. The right-hand side vanishes for the ideal gas law, but not generally for another equation of state.^[ref]

An isotherm is a curve of equilibrium states at fixed temperature, often drawn in the pressure-volume plane. For an ideal gas of fixed amount it obeys $pV=\mathrm{constant}$. The curve is not itself a specification of the rate, reversibility or experimental mechanism by which the states are visited.

For a reversible thermodynamic process that changes the volume of a fixed amount of ideal gas at absolute temperature $T$, the work done by the gas isHere $n$ is the amount of substance, $R$ the molar gas constant, $p$ the pressure, and $\ln$ the natural logarithm. The ideal gas law supplies $p=nRT/V$; the integral is the signed area under the pressure-volume curve. Isothermal expansion gives positive work; isothermal compression gives negative work. A convention counting work done on the gas instead has $W_{\mathrm{on}}=-W_{\mathrm{by}}$.^[ref]

For a calculated example, let $n=1\mathrm{mol}$, $T=300\mathrm{K}$ and $V_i=10\mathrm{L}$, $V_f=20\mathrm{L}$. The pressure falls from approximately $249.4$ to $124.7\mathrm{kPa}$, andTraversing the same isothermal process backward changes both transfer signs: $W_{\mathrm{by},\mathrm{rev}}=Q\approx -1.729\mathrm{kJ}$. Neither direction changes internal energy of an ideal gas. These stipulated values illustrate the energy balance; they are not experimental measurements.

The shaded geometric area is positive in both panels; the direction of the integral supplies the sign of work. Knowing only the two equilibrium endpoints does not justify shading this curve for an irreversible process. For an idealized piston moving against a specified external resisting pressure, boundary work is $W_{\mathrm{by}}=\int p_{\mathrm{ext}}dV$. Substitution of the equilibrium gas pressure requires the appropriate reversible limit. In free expansion into vacuum, $p_{\mathrm{ext}}=0$ and this boundary work is zero.

Why must a conducting piston move slowly? A simple model couples the first law of thermodynamics to Newton's law of cooling. Assume a fixed amount of ideal gas with uniform temperature $T(t)$ and constant whole-sample heat capacity at constant volume $C_V$, a heat bath maintained at $T_b$, negligible friction, and mechanically slow motion. Let $G>0$ be the effective thermal conductance, the reciprocal of the thermal resistance, in $\mathrm{W}{\mathrm{K}}^{-1}$. ThenPositive heat transfer must offset expansion work to keep $T$ near $T_b$. A finite $G$ and nonzero piston speed therefore require a temperature difference. This uniform-temperature model neglects spatial temperature gradients, sensor response, cylinder heat capacity and any change of $G$ with piston position; it is an illustrative calculation, not a fit to the isothermal gas syringe experiment.

For a prescribed exponential volume change $V=V_i{e}^{\lambda t}$, define $\tau =C_V/G$, $s=t/\tau$ and $ϵ=nR\lambda /G$. The dimensionless temperature $\theta =T/T_b$ obeys a linear ordinary differential equation with initial value $\theta (0)=1$:The plotted expansion uses stipulated $C_V=(5/2)nR$ and stops at $V_f=2V_i$, at $s_f=\ln 2/[(5/2)ϵ]$. During expansion, the larger $ϵ$ produces the larger temperature deficit; once the piston is held fixed, the deficit undergoes exponential decay as $e^{-(s-s_f)}$. Reducing $|ϵ|$ makes the path more nearly an isothermal process, while increasing its duration. Reversing the piston with $\lambda <0$ produces a temperature excess and outward heat transfer; the small-$|ϵ|$ regime is the intended near-isothermal approximation. Mechanical slowness alone does not ensure sufficient heat transfer.

Boyle's law states that a fixed amount of substance of an ideal gas at constant absolute thermodynamic temperature has constant product of absolute pressure and total volume:Here $p$ is measured relative to a vacuum, not relative to the surrounding atmospheric pressure. Halving the volume doubles the absolute pressure; doubling the volume halves it. A real gas approximately follows Boyle's law when it is sufficiently dilute and far from a phase transition.^[ref]

For an original calculated example, suppose a sealed gas sample has $p_1=100\mathrm{kPa}$ and $V_1=100\mathrm{c}{\mathrm{m}}^3$. After isothermal compression to $V_2=50\mathrm{c}{\mathrm{m}}^3$,Both states have $C=10000\mathrm{kPa}\mathrm{c}{\mathrm{m}}^3=10\mathrm{J}$, since $1\mathrm{kPa}\mathrm{c}{\mathrm{m}}^3=10^{-3}\mathrm{J}$. The volume ratio is dimensionless, so using the same volume units in numerator and denominator leaves the pressure in kilopascals. Although $pV$ has units of energy, its value is not the compression work: isothermal ideal-gas work involves an integral along the path.

The blue curves show calculated ideal gas states, not measurements. The left panel is a branch of a hyperbola; the right panel plots exactly the same absolute pressures against $1/V$. The dashed line uses gauge pressure with a stipulated constant atmospheric pressure of $100\mathrm{kPa}$. Its displaced intercept explains why absolute pressure in Boyle's law matters.

A short derivation starts from the ideal gas law, $pV=nRT$. Fixing the amount of substance $n$ and absolute thermodynamic temperature $T$ fixes $C=nRT$, where $R$ is the molar gas constant. The microscopic picture in ideal gas pressure from wall collisions is equally appealing: at fixed temperature, the typical particle kinetic energy stays fixed, while compression increases the number density and wall momentum transfer per unit surface area and time. A larger absolute pressure follows without requiring hotter particles.

The constraints are essential. A leak changes the amount of substance. Rapid compression can raise the temperature before heat transfer restores thermal equilibrium, as in the isothermal gas syringe experiment. Molecular size and interactions in a dense real gas invalidate the ideal gas approximation; the Van der Waals equation describes one such correction. Equal endpoint temperatures allow an endpoint test of Boyle's law, but do not establish that every intervening state lies on an isothermal process.

For fixed mass $m$, mass density satisfies $\rho =m/V=mp/C$, so it is proportional to absolute pressure. In a dilute bubbly flow, Boyle's law allows bubble volume and its contribution to buoyancy to increase as hydrostatic pressure decreases, provided gas mass is retained, dissolution is negligible, and the temperature stays approximately fixed. Its usefulness is that a simple ratio predicts a substantial size change without tracking individual molecules.

With gauge pressure $p_g$ referenced to atmospheric pressure $p_{\mathrm{atm}}$, absolute pressure is $p=p_g+p_{\mathrm{atm}}$. Thus Boyle's law becomesEven a constant atmospheric pressure cannot be dropped from these sums. For the calculated $100\mathrm{kPa}$ to $200\mathrm{kPa}$ example, take $p_{\mathrm{atm}}=100\mathrm{kPa}$. The initial and final gauge pressures are $0$ and $100\mathrm{kPa}$; their products with the respective volume are $0$ and $5000\mathrm{kPa}\mathrm{c}{\mathrm{m}}^3$, which are unequal. Zero gauge pressure means balance with the surroundings, not absence of gas or absence of wall momentum transfer.

For a frictionless piston of surface area $A$ with its outer face exposed to atmospheric pressure, the additional inward force required for mechanical equilibrium is $F=(p-p_{\mathrm{atm}})A=p_{g}A$. This is why a mechanical load can reveal a pressure difference even though the equation of state requires absolute pressure. With piston friction, the load alone no longer determines $p_{g}A$; a direct pressure sensor avoids that particular inference.

A linearized plot of Boyle's law uses $x=1/V$ as its horizontal coordinate. Then absolute pressure satisfies $p=Cx$: the slope is $C=nRT$, and the ideal intercept is zero. In the figure, $(V,p)=(100,100)$ and $(50,200)$ in $\mathrm{c}{\mathrm{m}}^3$ and $\mathrm{kPa}$ become $(x,p)=(0.010,100)$ and $(0.020,200)$ in $\mathrm{c}{\mathrm{m}}^{-3}$ and $\mathrm{kPa}$. Both give slope $10000\mathrm{kPa}\mathrm{c}{\mathrm{m}}^3$. The Vernier experiment includes this reciprocal-volume graph as its extension.^[ref]

At constant atmospheric pressure, gauge pressure instead obeys $p_g=Cx-p_{\mathrm{atm}}$, with the same slope and a negative intercept. A nonzero fitted intercept in an intended absolute pressure plot can indicate sensor bias or an incorrect volume correction, but is not by itself a unique diagnosis. The origin is a mathematical extrapolation to infinite volume and zero absolute pressure, rather than an additional measured state.

Vernier's Boyle's Law: Pressure-Volume Relationship in Gases, Experiment 6 of Chemistry with Vernier, specifies a graduated $20\mathrm{mL}$ gas syringe, a pressure sensor and LabQuest recording. Preparation sets the disconnected syringe to $10.0\mathrm{mL}$, then attaches it to the sensor valve, trapping air. At several plunger positions, the displayed pressure is allowed to stabilize before the paired volume is entered. The analysis tests whether $pV$ remains approximately constant. It adds $0.8\mathrm{mL}$ to each syringe reading for the sensor's internal volume; this correction belongs to that apparatus. The worksheet supplies a blank results table, not measured values.^[ref]

The manufacturer's Gas Pressure Sensor User Manual identifies a membrane sensor referenced to a vacuum, hence an absolute pressure readout. Its calibration section uses the actual local atmospheric pressure for an ambient reference check, rather than a weather report corrected to sea level. Checking this baseline before sealing separates an offset error from compression physics.^[ref]

Additional controls follow from the model. Keep the same sealed amount of substance, connections and ambient temperature; persistent pressure drift at held volume after thermal equilibrium suggests a leak or another uncontrolled change. Small steps and waiting allow compression heat to leave the gas; avoiding hand warming reduces another heat input. Compare settled readings when approaching a position from either direction. Plunger friction affects the applied force and position reproducibility, so record actual pressure and actual plunger position rather than predicting pressure from the load. These are proposed controls, not reported experimental outcomes.

Nearly constant $pV$ across equilibrated states supports the fixed-temperature ideal gas approximation over the tested range. Stabilized pressure alone does not demonstrate uniform or constant temperature; the isothermal gas syringe experiment adds a temperature readout to distinguish a transient from its cooled endpoint. Finite sensor accuracy and uncertain total volume limit the test, and agreement does not establish ideal behavior at every pressure. Repeated return readings help distinguish reproducibility from a one-direction trend.

In a gas syringe, the graduated barrel reading $V_{\mathrm{read}}$ can omit a fixed connecting or sensor volume $V_d$ occupied by the same sealed gas. For a common settled temperature, Boyle's law then requiresThis second relation makes a graph of $1/p$ against $V_{\mathrm{read}}$ a straight line; its intercept divided by its slope estimates $V_d$ under these assumptions. Unequal temperatures between the barrel and the connecting space require a different correction, analogous to the gas thermometer dead-space correction.

For an original hypothetical example, let $V_d=1\mathrm{c}{\mathrm{m}}^3$, $V_{\mathrm{read},1}=20\mathrm{c}{\mathrm{m}}^3$, $p_1=100\mathrm{kPa}$, and $V_{\mathrm{read},2}=10\mathrm{c}{\mathrm{m}}^3$. The total volume falls from $21$ to $11\mathrm{c}{\mathrm{m}}^3$, so $p_2=100(21/11)\mathrm{kPa}\approx 190.91\mathrm{kPa}$, rather than $200\mathrm{kPa}$. The omitted volume makes the total compression ratio smaller than the barrel-reading ratio. These stipulated values are independent of the manufacturer's apparatus correction and are not measurements.

An isothermal compression reduces the volume of a thermodynamic system at fixed temperature. For a fixed-composition ideal gas compressed reversibly from $V_i$ to $V_f<V_i$, isothermal ideal-gas work givesThe surroundings supply positive work $W_{\mathrm{on}}$, and the gas rejects the same amount of heat to the heat bath. Compressing $1\mathrm{mol}$ at $300\mathrm{K}$ from $20$ to $10\mathrm{L}$ requires approximately $1.729\mathrm{kJ}$ of work input and rejects $1.729\mathrm{kJ}$ of heat. If that heat transfer cannot keep up, the temperature rises: the process departs from isothermal compression toward adiabatic compression. The finite-rate isothermal piston model explains the required small temperature excess.

A gas syringe makes the distinction between a constant-temperature path and equal-temperature endpoints observable. The Ideal Gas Law Apparatus (TD-8596A), Instruction Manual 012-08420B by PASCO scientific specifies a TD-8596A gas syringe with a mechanical stop, an internal thermistor, an attached pressure sensor and data acquisition. Record the stop volume with the coupling disconnected, then set $40\mathrm{mL}$ and seal the coupling. Record pressure and temperature, compress quickly to the stop near $20\mathrm{mL}$, and hold until both readouts settle. The manual gives roughly $30\mathrm{s}$ for settling and about $0.5\mathrm{s}$ for the thermistor response. Releasing the plunger gives a second transient and a final volume to record.^[ref]

The manual describes a pressure overshoot and temperature rise during rapid compression, followed by cooling at the held volume; the settled pressure remains higher than initially. This illustrates approximately adiabatic compression followed by heat rejection, rather than an isothermal compression throughout. Use the settled initial and compressed readings to test Boyle's law, correcting both syringe readings by the unmarked tubing volume $V_d$:Use absolute pressure, not gauge pressure. A transient comparison of $pV/T$ must pair simultaneous pressure and temperature readings: the sensor lag can separate their peaks.^[ref]

For an additional test of the path, repeat with small compression steps, wait for stable temperature and pressure at every step, and repeat in reverse. Keep the sealed amount of substance, connecting tubing and ambient temperature fixed; prevent hand warming of the barrel and check for leaks by watching for continued pressure drift at held volume after thermal equilibrium. These are proposed controls, rather than reported measurements. Agreement of equilibrated points with Boyle's law supports the fixed-temperature ideal gas law approximation, but does not prove that the rapid segments between them were isothermal processes. A single local temperature sensor can miss temperature gradients; plunger friction can produce direction-dependent readings. The pressure and volume data estimate reversible work only insofar as the path approaches a reversible thermodynamic process; they do not directly measure heat. After motion stops, cooling at fixed volume has zero boundary work and $Q=\Delta U<0$, even though the complete equal-endpoint-temperature ideal gas run has $\Delta U=0$.

A gas syringe traps a gas in a graduated barrel with a movable plunger, allowing its volume to be varied and read. In an isothermal gas syringe experiment, the relevant total volume also includes any connected tubing and sensor cavity containing the same gas.

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 $Q=W_{\mathrm{by},\mathrm{rev}}=nRT\ln (V_f/V_i)$ and $\Delta U=0$. 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, $Q=W_{\mathrm{by}}=0$. 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 $\Delta S=nR\ln (V_f/V_i)$; 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]