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The entropy of mixing is the entropy change between initially separate components and their final mixture, with initial and final temperatures, pressures and component amount of substance values specified. For an ideal solution made from pure liquids at the same temperature and pressure, let $n={\sum }_i{n}_i$. ThenThe right-hand expression is the ideal solution result; the general definition does not require ideality. Each interior mole fraction has a negative logarithm, so mixing distinct components gives positive entropy of mixing. At a pure endpoint, use the limit $x\ln x\to 0$ as $x\to 0^{+}$.

For one mole of the chosen A/B ideal solution with $x_A=0.4$,For the same total amount of substance, equal mole fractions maximize this binary entropy of mixing: the composition function $s(x)=-x\ln x-(1-x)\ln (1-x)$ hasso its unique maximum is $s(1/2)=\ln 2$. This is a comparison between different prepared compositions, not a prediction that a closed sample changes its component inventory to become equimolar.

An equilibrium stage models a contact whose outgoing liquid and vapor satisfy vapor-liquid equilibrium at the stage's temperature and pressure. It is a composition model, not a claim that each piece of packing reaches thermodynamic equilibrium.^[ref]

Evaporation transfers molecules from a liquid surface into the surrounding vapour. It can occur below the boiling temperature, and competes with condensation from the vapour. Its net rate depends on the surrounding vapor pressure and transport conditions. Removing latent heat through evaporation can cool the remaining liquid.

A fluid is a material that flows under sustained shear stress and cannot maintain a static shear stress in its fluid state. Liquids and gases are the usual examples. A Newtonian fluid has deviatoric stress proportional to its rate-of-strain tensor, whereas more general fluid constitutive equations can be nonlinear or have memory. In a porous medium, the fluid occupies connected voids within a load-bearing solid framework. The important distinction is the response to a continuing tangential force: an ordinary elastic solid can settle into a fixed deformation, while an ordinary fluid continues to deform. A fluid can nevertheless be at rest when no unbalanced shear stress drives it. ^[ref]

For a worked example, place a Newtonian fluid between parallel plates separated by $h=1\mathrm{mm}$, keep the lower plate fixed and move the upper one at $U=0.10\mathrm{m}{\mathrm{s}}^{-1}$. With no-slip boundary conditions, steady flow, no imposed pressure gradient and negligible edge effects, Couette flow has $u(y)=Uy/h$. For dynamic viscosity $\mu =0.001\mathrm{Pa}\mathrm{s}$, the shear stress magnitude isThe velocity gradient describes neighbouring layers sliding at different speeds. Doubling $U$ doubles the required shear stress; maintaining the same velocity keeps producing deformation, rather than fixing a final shape. This gives viscosity a concrete meaning: resistance to a rate of motion, not a prohibition on motion.

Fluid mechanics studies the motion and forces of liquids and gases. Its central simplification is the continuum approximation: replace individual molecules by bulk properties defined at every position and time. The averaging region must contain many molecules while remaining small compared with the distances over which those properties vary. A fluid element is such a small material parcel, rather than a single molecule. This connects fluid mechanics to continuum mechanics and makes calculus useful for describing flow. ^[ref]

Three basic fields are the velocity field $\mathbf{u}(\mathbf{x},t)$, the mass density $\rho (\mathbf{x},t)$ and the pressure $p(\mathbf{x},t)$. The first gives a parcel's instantaneous velocity; the second gives mass per unit volume. The pressure contributes an inward normal traction $-p\mathbf{n}$ across a surface with outward unit normal $\mathbf{n}$. Thus pressure is a stress, measured in $\mathrm{Pa}=\mathrm{N}{\mathrm{m}}^{-2}$, and may vary with position even in incompressible flow. Additional viscous stresses can act tangentially. ^[ref]

The guiding questions are what must be conserved and which forces matter. Mass conservation constrains the velocity field; momentum conservation determines its response to pressure gradients, viscosity and body forces. An incompressible flow model, a Reynolds number estimate and Bernoulli's principle answer different parts of a problem. Their appeal is that a few carefully stated assumptions can determine useful quantities before the entire velocity field is known.

A dispersion of gas bubbles in a liquid or solid matrix. Thin intervening films and interfacial forces govern stability; bubble diameter need not itself lie below a micrometre.

Fractional distillation brings rising vapor into contact with descending liquid in a fractionating column. Packing supplies contact area; it does not act as a sieve for individual molecules. Repeated exchange can enrich the rising vapor in the more volatile component. Some condensed liquid returns downward as reflux, rather than all being withdrawn as distillate.^[ref]

An equilibrium stage is an idealization of this contact. A real fractionating column has finite contact time and imperfect wetting and mixing; its length is not automatically a count of equilibrium stages. Product withdrawal and reflux affect the separation together. Thus the repeated ideal-stage enrichment example illustrates the composition advantage of repeated equilibration, but supplies neither a column design nor a specified reflux requirement.^[ref]

A fractionating column provides contact between rising vapor and returning liquid during fractional distillation. Packing or trays provide contact area; the resulting separation depends on both vapor-liquid equilibrium and the actual flow and exchange between the thermodynamic phases.^[ref]

The Gibbs free energy of mixing compares the final mixture's Gibbs free energy with that of its initially separate components at the same temperature and pressure. For an ideal solution, subtract the pure-component reference from $G={\sum }_i{n}_i{\mu }_i$:For one mole of the chosen A/B ideal solution at $300\mathrm{K}$ and $x_A=0.4$,The individual chemical potential changes are $RT\ln 0.4\approx -2.28554\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ for A and $RT\ln 0.6\approx -1.27417\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$ for B. Weighting these by $0.4\mathrm{mol}$ and $0.6\mathrm{mol}$ reproduces the total Gibbs free energy of mixing.

If ideality holds in a neighborhood of the specified temperature and pressure, differentiation at fixed component amounts givesThus the ideal mixing Gibbs free energy decrease comes entirely from the entropy increase; the mixing enthalpy and volume changes vanish. Ideality at a single isolated state alone does not determine temperature or pressure derivatives.^[ref]

The same formula rules out spontaneous separation into two liquid thermodynamic phases within this model. Per mole, the mixing Gibbs free energy $g_{\mathrm{mix}}=RT[x\ln x+(1-x)\ln (1-x)]$ hasAdding the pure-component reference contributions changes only a term linear in $x$. The total molar Gibbs free energy is therefore a strictly convex function: a separated pair of different compositions has a larger composition-weighted Gibbs free energy than the uniform sample with the same inventory. Such phase separation requires physics beyond this ideal solution model.

A gravity-capillary wave has restoring contributions from both gravity and surface tension. Consider an initially resting, horizontally unbounded liquid layer of constant depth $h$, with uniform mass density $\rho$, incompressible flow, inviscid flow and irrotational flow. The upper gas exerts constant pressure and has negligible inertia. Assume a clean interface with constant surface tension $\gamma$: no surfactant stresses, imposed current or wind. The wave amplitude $a$ must satisfy $ka\ll 1$ and $a\ll h$, so linearized boundary conditions apply. Deep water means $kh\gg 1$, rather than a particular depth in metres. ^[ref]

Let $z=0$ be the undisturbed free surface, with liquid below it. Potential flow gives a velocity potential $\varphi$ with $\mathbf{u}=\nabla \varphi$, and incompressible flow gives the Laplace equation. The linearized kinematic boundary condition for a free-surface graph and the Unsteady Bernoulli equation, including gravity and the Young–Laplace equation, giveHere $\eta (x,t)$ is the interface displacement; the signed small-slope pressure jump is $p_{\mathrm{liquid}}-p_{\mathrm{gas}}=-\gamma {\eta }_{xx}$. A wave crest has ${\eta }_{xx}<0$, so its capillary pressure is positive. Choose a right-travelling Fourier mode of positive wavenumber $k$ and angular frequency $\omega$:The factor $e^{kz}$ decays into the deep liquid, satisfies the Laplace equation, and makes ${\varphi }_z={\eta }_t$ at $z=0$. Substituting in the dynamic boundary condition leavesThis derivation displays the two restoring contributions with the same sign. Dimensional analysis also checks the result: $\gamma /\rho$ has units ${\mathrm{m}}^3{\mathrm{s}}^{-2}$, so both $gk$ and $(\gamma /\rho )k^3$ have units ${\mathrm{s}}^{-2}$. ^[ref]

At finite depth, a flat impermeable bottom at $z=-h$ requires ${\varphi }_z=0$. Replacing $e^{kz}$ by the normalized vertical factor $\cosh (k(z+h))/\cosh (kh)$ makes the surface ratio ${\varphi }_z/\varphi =k\tanh (kh)$. Eliminating the mode amplitudes then givesThus the same model supplies its own depth check: use the deep-water formula only when $\tanh (kh)$ is sufficiently close to one for the required accuracy. For example, $kh=3$ reduces $\omega$ by about $0.248\%$ relative to deep water, while $kh=1$ reduces it by about $12.7\%$. These percentages are calculations from this factor. ^[ref]

In deep water the phase velocity magnitude follows a wave crest, while the group velocity magnitude follows the wave envelope of a narrow wave packet. Differentiating the positive-frequency dispersion relation givesFor $k{\ell }_c\ll 1$, the surface gravity wave limit has $c_g\simeq c_p/2$. For $k{\ell }_c\gg 1$, the deep-water capillary-wave dispersion relation has $c_g\simeq 3c_p/2$: a wave crest slips backward relative to the faster wave envelope, even while both advance. Neither speed is the oscillating fluid element's own velocity. ^[ref]

There is a particularly neat coincidence at the crossover. Differentiate $c_p^2=g/k+\gamma k/\rho$: its unique minimum is at $k_c=\sqrt{\rho g/\gamma }=1/{\ell }_c$, exactly where the restoring terms are equal. ThereforeFor the stipulated parameters in capillary length, the minimum is $0.231\mathrm{m}{\mathrm{s}}^{-1}$. At $\lambda =3\mathrm{mm}$, direct substitution gives $f=\omega /(2\pi )\simeq 131\mathrm{Hz}$, $c_p\simeq 0.394\mathrm{m}{\mathrm{s}}^{-1}$ and $c_g\simeq 0.580\mathrm{m}{\mathrm{s}}^{-1}$. This short wavelength is capillary dominated, but its group velocity is still slightly below the pure-capillary ratio $3c_p/2$ because gravity has not vanished.

Erwin Louis Hahn's 1950 apparatus enclosed liquid samples in the coil of a tuned LC circuit, coupled to a gated radio transmitter and radio receiver. One transmitter quadrupled a crystal oscillator's 7.5 MHz to 30 MHz. A separate proton resonance regulator stabilized the static magnetic field.^[ref]

Waiting for thermal equilibrium prepared nuclear polarization. Oscilloscope photographs compared glycerol proton echoes at different field homogeneity: echo width changed; echo time followed twice the pulse separation. Receiver saturation obscured early free induction decay; transmitter leakage required care. The delayed signal tested refocusing; diffusion could still attenuate it.^[ref]

Hahn analyzed equal pulses as well as noting improved recovery with a second pulse twice as long; the ideal sequence above isolates that latter case.^[ref]

David Morris Lee, Douglas Dean Osheroff and Robert Coleman Richardson compressed coexisting liquid and solid helium-3 in a cell precooled by a dilution refrigerator. Helium-4 pressure drove coupled bellows and a piston; a capacitance diaphragm gauge read pressure and platinum nuclear magnetic resonance supplied thermometry. Uniform compression revealed a slope break A and a small pressure drop B; decompression and varied solid fraction checked reproducibility. Their April 1972 paper, Evidence for a New Phase of Solid He3, interpreted a new solid phase, without establishing liquid superfluidity. ^[ref]

The October follow-up replaced the thermometer assembly with a sample nuclear magnetic resonance coil. An applied magnetic field gradient selected different sample layers, separating strong solid signals from the liquid background. At A the liquid resonance shifted; at B its shift disappeared and its magnetic susceptibility fell. Removing the gradient resolved the frequency shift directly. Independence from solid fraction and distinct relaxation times supported the liquid assignment. Thus the reinterpretation rested on phase-selective evidence, rather than relabeling the first paper's title. These magnetic observations identify changed liquid phases; they do not directly measure frictionless flow. ^[ref]

Douglas Dean Osheroff recalls the subsequent p-wave interpretation. ^[ref]

The inference has a useful limit. A pressure anomaly in two coexisting phases cannot, by itself, identify which phase changed: both contribute to the common phase coexistence curve. Thermometer lag, a temperature gradient or slow equilibration can also separate indicated temperature from the sample state. Correlating another response with the anomaly provides information that repeating the same pressure trace cannot supply. Conversely, a shifted magnetic resonance alone does not measure a frictionless flow rate.

Helium-3 superfluidity involves Cooper pairs of fermions; helium-4 atoms are bosons. Individual helium-3 atoms do not undergo Bose-Einstein condensation. ^[ref]

The helium-3 superfluid discovery experiment connects an unexpected pressure feature to a change in the state of a liquid. Its lesson is unusually instructive: finding a reproducible anomaly and identifying the material that changed are separate experimental achievements. Pomeranchuk cooling explains how the experiment reached its operating regime; an independent nuclear magnetic resonance channel distinguishes the phases.

Helium liquefaction converts helium gas into a collectable liquid. It creates a bath for investigating material properties at very low temperatures, including superconductivity. The central question is how the incoming specific enthalpy compares with the specific enthalpies of the outgoing liquid and vapor. The liquefaction enthalpy budget makes that comparison explicit; a temperature decrease by itself does not specify a liquid yield.

In a Joule-Thomson effect cooling stage, a throttling pressure drop approximately preserves enthalpy under the assumptions of the steady-flow energy balance. For an ideal gas, specific enthalpy depends only on temperature: with positive specific heat capacity at constant pressure, equal specific enthalpy means equal temperature. Thus its Joule-Thomson coefficient is zero. An ideal gas also supplies no liquid branch. Cooling by throttling depends on real gas properties; expansion is not an automatic source of refrigeration.

For a local drop $dp<0$, $dT={\mu }_{\mathrm{JT}}dp$ cools only where the Joule-Thomson coefficient is positive. Precooling must bring the real gas into a useful cooling region, with enough cooling to overcome unwanted heat transfer. A finite expansion can cross a Joule-Thomson inversion curve; its final state requires the full enthalpy balance, including phase coexistence if liquid forms. Kamerlingh Onnes's 1908 helium liquefaction experiment combined external precooling with regeneration to reach that regime. The Joule-Thomson effect article develops the throttling identities and their assumptions.

Hess's law states that compatible chemical reaction enthalpies add when their equations add. Reversing a chemical reaction reverses its enthalpy change; multiplying the entire chemical reaction equation by a factor multiplies that change by the same factor. The reason is that enthalpy is a state function: intermediate states cancel from the differences. A cycle supplies one independent balance relation; it cannot determine two unknown inputs without further information.

The law is named after Germain Henri Hess.

For specified initial and final thermodynamic states, the change is $\Delta H=H_{\mathrm{final}}-H_{\mathrm{initial}}$. Because enthalpy is an extensive variable, a quoted reaction $\Delta H$ belongs to the amount of substance specified for each species in its chemical equation. Reversing the equation changes the sign; scaling every coefficient scales $\Delta H$; adding compatible equations adds their $\Delta H$ values. A per-mole value must say which chemical equation and normalization it uses. Match temperature, pressure, thermodynamic phases, chemical solution compositions and reference states before cancellation; the same formula in a gas and a liquid represents different states.^[ref]

The value of Hess's law is that an inaccessible reaction enthalpy can be obtained from measurable transformations. The algebra does not require those transformations to be steps of the actual reaction mechanism. Neither an activation energy nor a reaction rate follows from the endpoint difference: a catalyst may change the reaction rate while preserving the compatible initial and final enthalpies.

A bubble chamber using liquid hydrogen as both target and recording medium. For a beam interaction on a proton, the target's initial momentum can usually be approximated as zero on the scale of the beam momentum. This makes four-momentum conservation especially useful: the initial state does not include the unknown motion of a proton bound inside a heavier atomic nucleus. The approximation still neglects molecular binding and thermal motion.

A floating density instrument. At equilibrium, Archimedes' principle gives $\rho V_{\mathrm{displaced}}=m$ for fixed instrument mass $m$, so it displaces more volume in a less dense liquid. A graduated narrow stem converts this volume change into a visible immersion reading. Calibration specifies a temperature and a reading convention for the meniscus; a sample's other dissolved substances can affect a sugar-calibrated scale.

With tension taken positive, hydrostatic stress is the stress tensor $\mathbf{\sigma }=-p\mathbf{I}$, where $\mathbf{I}$ is the identity matrix. Every plane has the same compressive normal stress, and no tangential traction. More generally,where $\mathbf{s}$ is deviatoric stress. Two samples can share the same mean pressure while experiencing different deviatoric stresses. A stationary liquid cannot sustain equilibrium shear stress; a solid transmitting medium can support it. Consequently, a load divided by surface area does not by itself establish hydrostatic sample conditions. A transmitting medium's state at the actual pressure and temperature, and contact between sample and walls, matter.

Bridgman's Figure 4 compares mild steel fractured in tension at atmospheric pressure with steel stretched further in a liquid at $25000\mathrm{kgf}\mathrm{c}{\mathrm{m}}^{-2}$.^[ref] The imposed tension remains a directional load: the experiment combines confinement with deformation, rather than measuring a hydrostatic stress alone. Its comparison motivates recording the loading path and the surrounding medium as well as pressure; it does not establish a universal fracture threshold for all steels.

For the stipulated A/B ideal solution, put $x=x_A$. At the fixed temperature $300\mathrm{K}$, Raoult's law reduces toThe relative volatility is $\alpha =p_A^{\ast }/p_B^{\ast }=4$. For $0<x<1$,Hence every interior vapor-liquid equilibrium pair in this chosen model has A-enriched vapor; neither pure endpoint is enriched. Conversely,For example, $y_A=1/2$ corresponds to $x_A=1/5$, $p_A=p_B=16\mathrm{kPa}$ and $P=32\mathrm{kPa}$. Equal vapor mole fractions therefore need not mean equal liquid mole fractions.

These are fixed-temperature predictions. During boiling at a specified external pressure, the temperature instead adjusts until ${\sum }_i{x}_i{p}_i^{\ast }(T)=P_{\mathrm{external}}$. The two stipulated vapor pressures specify only one temperature; they provide no boiling-temperature curve.

An ideal solution is a chemical solution whose component chemical potentials depend on composition throughHere $n_i$ is an amount of substance, $x_i$ its mole fraction, $R$ the molar gas constant, and ${\mu }_i^{\ast }$ the pure-component liquid reference at the same temperature $T$ and pressure $P$. This model applies to every component across the composition range; it is stronger than an approximation valid only near a pure solvent.^[ref]

With this pure-liquid standard state convention, the thermodynamic activity satisfies ${\mu }_i={\mu }_i^{\ast }+RT\ln a_i$, so an ideal solution has $a_i=x_i$, or activity coefficient ${\gamma }_i=a_i/x_i=1$.^[ref] This statement concerns the liquid. Assuming that a coexisting vapor is an ideal gas mixture is an additional approximation. Its mole fractions $y_i$ generally differ from the liquid mole fractions $x_i$.

For an original two-component example, stipulate $T=300\mathrm{K}$ and pure-component vapor pressures $p_A^{\ast }=80\mathrm{kPa}$ and $p_B^{\ast }=20\mathrm{kPa}$. A and B are invented distinguishable components; these numbers are chosen model inputs, not material data. Combine an ideal solution with an ideal gas vapor, neglect the pure-liquid reference's pressure correction, and exclude other gases. At liquid mole fractions $x_A=0.4$ and $x_B=0.6$, Raoult's law and addition of partial pressures giveThus the coexisting vapor contains about $72.73\%$ A by amount of substance, although the liquid contains only $40\%$. The total pressure is neither pure-component vapor pressure, and $x_A$ cannot be substituted for $y_A$. This enrichment is the basis of distillation.

The usefulness of the ideal solution is that one composition law connects chemical potentials, vapor-liquid equilibrium, entropy of mixing and Gibbs free energy of mixing. Its liquid components can interact strongly: the defining condition is their composition dependence, rather than the absence of all interactions as in an ideal gas model.