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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.

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 astrophysicist studying stellar black holes and X-ray binaries.

Astronomer and author of research on X-ray plasma spectroscopy.

A physicist.^[ref]

The Van der Waals equation connects a dilute gas model to the possibility of a liquid-gas critical point. Its usefulness includes showing how attractions and excluded volume can change an equation of state; its simple constants do not make it an exact model for every fluid.

Chemist whose Experiments and Observations on Different Kinds of Air by Joseph Priestley (1775) describes the investigation of dephlogisticated air.

In his paper published in 1845, Joule connected two copper receivers with stopcocks, filled one with compressed dry air, and evacuated the other with an air pump. He immersed the connected receivers in water in an insulated arrangement, stirred the water, and read a sensitive thermometer. He then opened the stopcocks, let the air redistribute, stirred again, and compared the water's temperature with its initial value. Alternating control trials accounted for effects such as stirring and evaporation. The observation was no detectable net cooling of the common bath, rather than a record of the gas temperature at every instant. ^{[ref] [ref]}

Joule also immersed the receivers and their connecting piece in separate water vessels. The source receiver cooled while the receiving side warmed, with nearly cancelling thermal effects. ^[ref]

This distinguishes local transient changes from the final observation for the combined apparatus. Insulating its outer boundary suppresses external heat exchange; it does not prevent heat exchange between the gas, the receivers and the water inside that boundary.

An idealized modern version can use two rigid chambers joined by a valve, with thermometers in the chambers and on the walls. Prepare one chamber with gas and the other evacuated, disconnect the pump, close the apparatus to matter exchange, and let the initial temperature settle. Record initial and final equilibrium pressure and temperature, along with the wall response. Repeated closed-valve runs can reveal drift and valve-actuation effects; independent heating calibrations can estimate the heat capacity of the participating apparatus. This is a proposed measurement protocol, not a claim of a particular measured result. Fast local readings can characterize the release, but they cannot replace the final equilibrium readings in the endpoint internal energy balance.

The Joule-Thomson effect is the temperature response of a fluid flowing from higher to lower pressure through a valve or a plug of porous medium, when the throttle is insulated and the other steady-flow energy balance assumptions hold. Its equilibrium endpoints have equal specific enthalpy. The Joule-Thomson coefficient determines whether a small drop cools or warms; cooling is not universal.

A useful contrast is between three insulated expansions. In free expansion of a gas-only closed system into a vacuum, no external work occurs and $U_2=U_1$; an ideal gas returns to its initial equilibrium temperature. In a throttle, continuous flow carries pressure work across the boundary and preserves specific enthalpy under the stated assumptions; an ideal gas again has no endpoint temperature change. In a reversible adiabatic expansion of a loaded closed system, the gas supplies work, loses internal energy and cools, even if it is an ideal gas. That process preserves entropy; throttling generally produces entropy. For a small constant-enthalpy step, $dH=TdS+Vdp=0$ gives $dS=-Vdp/T>0$ when $dp<0$ and $T,V>0$. This equilibrium comparison computes endpoint entropy differences without supplying a reversible path through the plug.

The effect is useful in refrigerators because an appropriately prepared real gas can cool while passing through a simple valve. The inlet must lie in a suitable positive-Joule-Thomson coefficient region. The Joule-Thomson inversion curve makes that requirement precise; a pressure drop by itself is not a guarantee of refrigeration.

Physician and natural philosopher who contributed to the conservation-of-energy programme in the 1840s, including an argument for the mechanical equivalent of heat.

In a dilute gas whose mean free path $\lambda$ is short compared with macroscopic gradient lengths, particles carry properties from their previous collisions over distances of order $\lambda$. A first-gradient isotropic estimate gives a transported flux $-n\overline{v}\lambda \nabla a/3$ for a property $a$ carried per particle. Applying this reasoning to species abundance, directed momentum $m{u}_x$ and thermal energy with per-particle heat capacity $c_v$ gives diffusivity $D\sim \overline{v}\lambda /3$, dynamic viscosity $\eta \sim nm\overline{v}\lambda /3$ and thermal conductivity $\kappa \sim n{c}_v\overline{v}\lambda /3$. These numerical prefactors are estimates, not exact collision-integral results.

For a constant hard-sphere diameter $d$, $\lambda \propto 1/(n{d}^2)$ and $\overline{v}\propto \sqrt{T/m}$. Consequently $\eta \propto \sqrt{mT}/d^2$, $\kappa \propto c_v\sqrt{T/m}/d^2$ and $D\propto \sqrt{T/m}/(n{d}^2)$. At fixed pressure the last scales as $T^{3/2}/p$. The near pressure-independence of viscosity and thermal conductivity applies only while gas-gas collisions, rather than apparatus walls, determine the mean free path. Temperature-dependent cross-sections and internal molecular excitations change the simple power laws.

Landau diamagnetism is the orbital response of mobile electrons to an applied magnetic field, arising from quantization of their transverse motion. For a noninteracting three-dimensional isotropic electron gas with quadratic dispersion, electron spin with $g=2$ and magnetic fields weak enough for the smooth-response limit, its susceptibility is ${\chi }_L=-{\chi }_P/3$, where ${\chi }_P$ is the Pauli paramagnetism susceptibility. Band effective masses, interactions, dimensionality and resolved magnetic quantum oscillations can change this simple relation.

Consider an ideal gas in chemical equilibrium with homogeneous, identical adsorption sites at fixed temperature. Each intact molecule occupies one site; only one monolayer is allowed. Occupation of distinct sites is independent: neighboring bound molecules do not change binding or release rates. The simplest Langmuir adsorption model has one adsorbing chemical species, no splitting of molecules, and no competitors. Irving Langmuir's 1918 paper treats simple adsorption alongside more complicated cases; its scope exceeds this particular model.^[ref]

The derivation is a balance between arrivals finding vacancies and departures from occupied adsorption sites. Let $k_{\mathrm{a}}P$ be the arrival-and-binding rate per vacant site and $k_{\mathrm{d}}$ the departure rate per occupied site. Thus $k_{\mathrm{a}}$ has units of inverse pressure per unit time, whereas $k_{\mathrm{d}}$ has units of inverse time. The mean surface coverage obeysAt chemical equilibrium, setting the two terms equal givesThe product $bP$ is dimensionless. Here $P$ is the adsorbing gas's partial pressure, expressed in modern bar, with $1\mathrm{bar}=10^5\mathrm{Pa}$, and $b$ is expressed in ${\mathrm{bar}}^{-1}$. The pascal is the SI unit of pressure. This dimensional $b$ is not itself a dimensionless thermodynamic equilibrium constant. A larger $b$ gives greater surface coverage at the same $P$ and temperature, but does not specify how quickly chemical equilibrium is reached: multiplying both rate coefficients by the same factor leaves $b$ unchanged.

Choose $b=0.5$, $2$, and $8{\mathrm{bar}}^{-1}$ as illustrative parameters at one fixed temperature, without assigning a particular material. At $P=0.5\mathrm{bar}$, substitution gives, respectively,Solving $\theta =1/2$ gives $P_{1/2}=1/b$: the three half-occupation pressures are $2$, $0.5$, and $0.125\mathrm{bar}$. For $b=2{\mathrm{bar}}^{-1}$, reaching $\theta =0.9$ instead requires $bP=9$, or $P=4.5\mathrm{bar}$. If the complete-monolayer capacity is stipulated to be $q_{\mathrm{m}}=10\mathrm{mmol}{\mathrm{g}}^{-1}$, then $q=q_{\mathrm{m}}\theta$ predicts $q=5\mathrm{mmol}{\mathrm{g}}^{-1}$ at $P=0.5\mathrm{bar}$. This last number is an original hypothetical example, not a measured uptake.

The shape follows directly from the finite number of adsorption sites. For $bP\ll 1$, $\theta \approx bP$: nearly every arriving molecule finds a vacancy. For $bP\gg 1$, $1-\theta =1/(1+bP)\approx 1/(bP)$: vacancies become scarce. More formally,Thus surface coverage rises with diminishing slope and approaches one only as $P\to \infty$. This saturation is a site-capacity limit, not a claim that the gas has reached its condensation pressure. A second layer, different site binding strengths, interactions between bound molecules, or a changing surface invalidate parts of the setup. A good fit alone does not establish identical adsorption sites: a restricted pressure range can hide such differences. The Langmuir adsorption model is useful because it makes the capacity and the pressure scale of filling separate, testable quantities.

In 1918, Irving Langmuir measured adsorption using freshly split mica strips, handled at their edges, separated by iron spacers and held with brass fasteners. A glass bulb contained the bundle; a similar blank contained matching iron and brass but no mica. Evacuated glass connections, Mercury seals, liquid air traps, and McLeod gauges provided controlled gas handling. Calibrated compartment volumes and pressure readings before and after expansion gave free-gas amounts; their deficit indicated uptake. Lowering pressure and measuring released gas tested desorption.^[ref]

Hydrogen blank runs calibrated cooling-related pressure differences. Irving Langmuir pre-cooled the bulbs to reduce thermal delay; he suggested slow diffusion between strips could control the remaining approach to equilibrium. Critically, blank uptake was not subtracted: he estimated the mica-bulb results were 10–30% too high. Liquid air temperature drift was unrecorded. These limits constrain inference of intrinsic binding from the uptake curve. The paper's pressure unit called “bar” was $1\mathrm{dyn}\mathrm{c}{\mathrm{m}}^{-2}=0.1\mathrm{Pa}$, unlike the modern bar used above.^[ref]

Within the ideal-vapor Clausius-Clapeyron approximation, a local slope of the natural logarithm of saturation pressure against inverse temperature estimates the molar latent heat:In the stipulated vapor-pressure calculation, the slope is $-4811.16\mathrm{K}$, which recovers $40.0\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$. For variable $L_m(T)$, a two-point estimate gives an average weighted by $T^{-2}$, rather than the latent heat at an arbitrary midpoint. Differentiating noisy pressure measurements amplifies their errors. Outside the ideal-vapor regime, use independently determined molar volumes in $L_m=T\Delta v_{m}dp/dT$; a straight-looking graph alone cannot establish that the gas is ideal.

A rechargeable aqueous sulfuric-acid cell using lead and lead dioxide electrodes. Discharge converts both active materials to lead sulfate; charging reverses that conversion subject to corrosion, gas evolution and morphology limitations.

The Lenard cathode-ray window experiment lets cathode rays leave a gas-discharge tube through a thin aluminium foil while preserving the tube's vacuum. This separates production from propagation.

Philipp Lenard's lecture, delivered on 28 May 1906, describes sealing a small hole in a metal plate with aluminium foil. Luminous phosphor grains first rested on the window, then glowed above it in air. His improved tube separated production and observation chambers; coated paper served as a fluorescent screen. An aperture revealed spreading beyond a narrow straight beam. Evacuating the observation chamber reduced spreading and attenuation without interrupting production. Interposed layers and stepped foil stacks gave shadow comparisons; approximate scaling with mass had exceptions.^[ref]

The experimental advantage is unusually clean: reducing the gas content in the observation chamber tests whether gas is needed to carry the cathode rays, while retaining the conditions needed to generate them. The window is a boundary that transmits some electrons while confining the source environment. A spot outside establishes a transmitted effect; the aperture and changed observation environment provide additional ways to distinguish propagation from the source's behavior. This logic is useful whenever a complicated source would otherwise be changed by the very intervention intended to test the emitted beam.

Several inferences require care. A darker fluorescent screen can mean fewer arriving electrons, less deposited energy per electron, or redistribution by electron scattering beyond the observed area. A visible endpoint depends on the screen's sensitivity and background. It is not an intrinsic electron range independent of initial kinetic energy, gas density, and observation geometry. For a modern comparison, measure a reference at fixed source conditions, use background subtraction, and compare the whole luminous patch as well as a small central region. A wider collection area tests redistribution; changing source-to-screen separation also changes collection geometry. These are proposed controls for interpreting a readout, not additional historical observations attributed to Lenard.

Nor is fluorescence a unique signature of cathode rays: X-rays can also excite it. Lenard notes that a later tube could transmit both, and that slow cathode rays failed to pass its window.^[ref] In modern terms, cathode rays are electrons carrying negative electric charge, whereas X-rays are photons with zero electric charge. Magnetic bending of the incident electrons, interpreted through the Lorentz force, supplies a discrimination that brightness alone cannot. Passage through foil alone determines neither the sign of electric charge nor its magnitude, and it does not measure charge-to-mass ratio. The separate Thomson charge-to-mass experiment explains that inference. Even a measured charge-to-mass ratio needs an independent electric charge measurement to determine mass.

Deposition in which material travels approximately ballistically from a source to the substrate. Shadowing produces poor coverage of hidden surfaces; gas mean free path must substantially exceed the relevant source-substrate path.