Boyle's law 2026-10-14
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 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]
2.1 Molecular Model of an Ideal Gas. §2.1, The Gas Laws, Figure 2.4, and equations 2.1–2.2: fixed temperature and particle number, absolute pressure, and the dilute-gas limit
For an original calculated example, suppose a sealed gas sample has and . After isothermal compression to ,Both states have , since . The volume ratio is dimensionless, so using the same volume units in numerator and denominator leaves the pressure in kilopascals. Although 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 . The dashed line uses gauge pressure with a stipulated constant atmospheric pressure of . Its displaced intercept explains why absolute pressure in Boyle's law matters.
A short derivation starts from the ideal gas law, . Fixing the amount of substance and absolute thermodynamic temperature fixes , where 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 , mass density satisfies , 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.
Gas thermometer 2026-10-14
A gas thermometer infers temperature from the equation of state of a confined gas. The constant-volume version measures pressure; the constant-pressure version measures volume. For an ideal gas,Here is particle number, is amount of substance, is the Boltzmann constant, and is the molar gas constant. The reference and test states must be internally equilibrated, and must be known on the absolute thermodynamic temperature scale. A pressure ratio cancels the unknown gas inventory and bulb size in the ideal constant-volume limit. This cancellation is the method's appeal: a mechanical measurement transfers an absolute temperature scale between different materials. The Maxwell speed distribution and ideal gas pressure from wall collisions explain the microscopic origin of the response. [ref]
2.1 Molecular Model of an Ideal Gas. OpenStax, University Physics Volume 2, section 2.1: the ideal gas law
For an original ideal-model calculation, choose , and . Then . These are stipulated values, not observations. Both pressures must be absolute, referred to vacuum. If the surrounding atmospheric pressure were , the corresponding gauge pressures would be and ; their ratio is three, which would incorrectly predict . A pressure difference from the atmosphere cannot be substituted into the ideal gas law.
An original schematic of constant-volume gas thermometer measurements
. Simplified measurement layout inspired by the NBS apparatus, not a replica or a report of measurements. A controlled bath thermalizes the bulb, separate calibrated thermometers check its surroundings, and a diaphragm transmits pressure to an absolute-pressure standard without mixing gases. The connecting tube contains gas at other temperatures; its inventory belongs in the gas thermometer dead-space correction. Details.A motivating calibration experiment. Schooley's account of the NBS/NIST work describes a helium-filled metal bulb, a capillary, a capacitance diaphragm gauge, and a mercury pressure standard. Circulating bath liquid passed the bulb assembly and platinum resistance thermometers. The resistance probes checked the surrounding temperature; gas pressure supplied the independent thermodynamic comparison. In an early series, workers filled the cleaned bulb with purified helium at the highest test temperature, checked pressure over three hours, then measured at lower temperatures and near a reference at . Six filling pressures allowed extrapolation toward zero pressure. [ref]
To turn this principle into a readable measurement protocol, use the following controls. These steps are a proposed teaching interpretation of the cited apparatus, rather than additional reported NBS observations:
- Define the inventory. Evacuate and clean the bulb and connecting tube, fill with a known pure gas, close the filling valve, and keep the same total particle number during each reference/test comparison. Monitor pressure at a maintained temperature before and after a run. A leak changes ; a slow drift can also reflect contamination, sorption, or imperfect equilibration, so pressure stability alone does not identify its cause.
- Measure the reference. Place the bulb in a controlled environment with independently assigned . Record after thermalization, together with the independent thermometer readings and their spread. A reference near has an absolute temperature near , rather than zero temperature. Repeating reference readings tests whether the inventory or apparatus changed during the comparison.
- Measure the test state. Change the bath setting, allow the bulb and gas to settle, and record only when the surrounding thermometers and pressure are sufficiently stable for the intended accuracy. Compare readings at different positions and vary the settling time. Record the connecting tube's temperature profile too: uniform bath temperature does not make the entire connecting tube isothermal.
- Measure the volume changes. Determine the bulb's thermal expansion and its deformation from differences between inside and outside pressure. Measure the connecting tube's dimensions and the effective valve volume. “Constant volume” is the ideal model; a real vessel expands. These measurements supply corrections, even though the absolute bulb volume cancels in the simplest pressure ratio.
- Measure pressure against a reference. For a liquid-column pressure standard, measure the vertical column height, the liquid's temperature-dependent mass density, local gravitational acceleration, and the reference-side pressure. Include diaphragm offsets and the gas's hydrostatic pressure change between the sensor and bulb. The pressure needed in the equation of state is at the bulb, not automatically at the remote gauge.
The corresponding NBS apparatus used a protective case with an outer helium layer held close to the bulb pressure, reducing pressure deformation while aiding thermal contact. Thermal expansion was measured on bulb material. Gas in the capillary remained partly outside the hot region, requiring a measured tube temperature profile and geometry. Pure working gas also mattered: contaminants that sorb on surfaces can change the freely circulating inventory. These are physical effects to measure or bound, rather than scatter that disappears by averaging. [ref]
https://nvlpubs.nist.gov/nistpubs/Legacy/IR/nbsir85-3133.pdf. J. F. Schooley, Thermometry, NBS IR 85-3133, chapter V, gas thermometry and the NBS experiment
For illustration, neglect connecting-tube gas and describe a uniform bulb with a dilute virial expansion in particle number density :Here and is the second virial coefficient in the particle-density convention; a molar-density convention rescales the coefficient. The second relation follows exactly from the definition of for the same , and shows the signs of the corrections. If the bulb expands by and at both states, the toy pressure ratio above gives , rather than . Improved expansion and helium nonideality models really changed the temperatures inferred from the 1989 NIST data: Harvey's 2023 reanalysis found expansion updates of roughly – and nonideality updates of roughly to . Those are reported corrections to historical results, not the much larger illustrative correction just calculated. [ref]
With equal corrected bulb volumes, negligible or corrected connecting-tube gas, fixed reference and test temperatures, and a dilute classical single gas phase,Repeat the reference/test comparison for several sealed fills, reducing between comparisons but keeping it fixed within each pair. The extrapolation varies density at fixed endpoint temperatures; it does not cool one fill toward zero temperature. Real gases have different finite-density corrections but share the classical ideal gas intercept under these assumptions. The limit does not remove leaks, bulb expansion, gauge offsets, or the gas thermometer dead-space correction. At very low pressures, thermal transpiration can make remote sensor and bulb pressures differ through a nonisothermal capillary; this must be corrected too. The NBS work measured this pressure correction using a separate comparison of narrow and wider tubes. [ref]
At , the toy models give and , respectively, although their imposed true test temperature is the same. Their zero-density intercept is the reusable quantity. Measuring several low-density points permits a fit and a check for curvature; asserting a straight line from one finite-density point supplies neither. A practical fit must balance nonideality against increasing relative pressure error and the capillary corrections, and keep its extrapolation uncertainty.
Ideal gas Created 2026-09-24 Updated 2026-10-14
An ideal gas is a model of a dilute gas whose particle centres move according to classical mechanics and occupy negligible volume compared with their container. Treating the particles as point masses removes the molecular-size correction; neglecting interactions between separated particles removes the intermolecular contribution to potential energy. The usual kinetic theory model retains brief elastic collisions with the walls and, optionally, with other particles: these transfer momentum while conserving the total kinetic energy of the colliding bodies. There is no appreciable interaction energy stored between collisions. These assumptions lead to the ideal gas law, . [ref]
2.1 Molecular Model of an Ideal Gas. OpenStax University Physics Volume 2, section 2.1: molecular model and ideal gas law
[ref]https://openstax.org/books/university-physics-volume-2/pages/2-2-pressure-temperature-and-rms-speed. OpenStax University Physics Volume 2, section 2.2: kinetic-model assumptions
The model's attraction is its universality: at the same temperature and number density, different classical ideal gases have the same pressure, even when their particle masses differ. In ideal gas pressure from wall collisions, heavier particles move more slowly at a given temperature, and the two effects cancel. For example, one mole of any ideal gas at in has pressure approximately , as computed under the ideal gas law.
The ideal gas law describes the translational contribution to pressure; it does not specify all of the internal energy or the heat capacity. A monatomic gas has three classical translational degrees of freedom, whereas a gas of molecules can also store rotational kinetic energy and energy in vibrational normal modes. An equation of state alone therefore does not determine how much heat a chosen temperature increase requires. It also does not select a process: isothermal expansion and adiabatic expansion need different additional constraints. [ref]
A real gas departs from this approximation when particle size or interactions become important, especially at high number density or low temperature near a phase transition. The Van der Waals equation adds such corrections. Independently, at sufficiently low temperature or high number density, quantum statistics can become essential: even particles with negligible interactions need not obey the classical ideal gas law. The classical statistical assumption is the nondegenerate gas regime, which is distinct from neglecting interactions. [ref]
2.1 Molecular Model of an Ideal Gas. OpenStax University Physics Volume 2, section 2.1: departures from ideal-gas behavior
[ref] Ideal gas law Created 2026-10-14 Updated 2026-10-14
The ideal gas law is the equation of state relating the absolute pressure , volume , particle count , and absolute thermodynamic temperature of a classical ideal gas:Here is the Boltzmann constant, is the Avogadro constant, is the molar gas constant, and is the amount of substance in moles. The distinct symbol avoids confusing amount of substance with the number density , measured in : the same law can be written . Use absolute pressure, relative to a vacuum, rather than an unconverted gauge pressure. [ref]
2.1 Molecular Model of an Ideal Gas. OpenStax University Physics Volume 2, section 2.1: particle-count and molar forms
The exact SI definitions of the Avogadro constant and Boltzmann constant giveThis numerical value is exact; the applicability of the ideal gas model to a real gas is an approximation. [ref] [ref]
https://www.bipm.org/en/si-base-units/kelvin. BIPM, exact Boltzmann constant in the kelvin definition
For , , and , direct substitution givesAt fixed temperature and particle count, doubling the volume to halves the pressure to approximately : this is Boyle's law. At fixed volume and particle count, doubling the temperature from to doubles the pressure to approximately . These ratios use kelvins, not readings in the degree Celsius scale: is , and is .
Ideal gas law: pressure versus volume at fixed temperatures, and pressure versus absolute temperature at fixed volume
. Details. The curved slices show Boyle's law at three temperatures; the straight slice shows proportionality to absolute temperature at one fixed volume. They are relations among equilibrium states, rather than a prescribed process history. Compression could hold the temperature fixed through heat transfer, or raise it during adiabatic compression. To calculate a process's heat or work, supplement the ideal gas law with the process constraint, the first law of thermodynamics, and the relevant internal energy or heat capacity information. The graph's extrapolation toward is mathematical; it does not assert that a real gas remains classical or gaseous there.
For a stellar mixture with fixed mean molecular weight, the ideal gas law can be written , where is mass density and is the stellar gas constant. It assumes negligible interaction corrections and a nondegenerate gas; excitation or ionization can change the particle count and thermodynamic response.
In his 1834 memoir on the motive power of heat, Émile Clapeyron combined gas laws into a relation between pressure, volume, and temperature while analysing heat engines (printed page 164). The equation above uses modern SI notation and absolute thermodynamic temperature; it is not a transcription of his historical temperature convention. [ref]
https://www3.nd.edu/~powers/ame.20231/clapeyron1834.pdf. Clapeyron, Mémoire sur la puissance motrice de la chaleur (1834), page 164



