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Electromagnetism describes how electric charge and electric current interact through the electric field $\mathbf{E}$ and magnetic field $\mathbf{B}$. The Maxwell equations describe the fields and their sources; the Lorentz force describes the response of a particle of electric charge $q$ and velocity $\mathbf{v}$:The electric field can change the particle's energy. The magnetic part of the Lorentz force is perpendicular to velocity, so magnetic forces do no work; they can bend a trajectory. These are local interactions: a particle responds to the electromagnetic field at its position. ^[ref].

The remarkable unification is that the same Maxwell equations connect Coulomb's law, Faraday's law of induction, and freely propagating electromagnetic waves. A changing electric field contributes to magnetic circulation through displacement current; together with Faraday's law, this permits waves in vacuum without conducting matter. The Poynting theorem then explains how the fields store and transport energy. This connects the force on a charge to the energy carried by light.

In his 1865 paper, James Clerk Maxwell derived transverse disturbances and compared the propagation speed inferred from electrical measurements with independently measured light speeds. Part VI, especially §§95–97, argues that their agreement supports identifying light as an electromagnetic wave. This was a comparison with finite experimental accuracy, rather than a numerical identity between the historical measurements. ^[ref]; ^[ref].

The Maxwell-Boltzmann distribution describes the random velocities and speeds of particles in a classical ideal gas at thermal equilibrium. Individual particles keep changing velocity through collisions, while the equilibrium probability distribution stays fixed. For one species of particle mass $m$ at positive temperature $T$, the characteristic scale iswhere $k_B$ is the Boltzmann constant. A signed velocity component follows a normal distribution; the nonnegative magnitude follows the Maxwell speed distribution. Their peaks differ because a speed measurement groups together all directions of motion.

Use the gas rest frame, three spatial dimensions, and nonrelativistic particles, with $k_{B}T\ll m{c}^2$ where $c$ is the speed of light. Assume a dilute gas whose interactions between encounters can be neglected in the ideal gas approximation and whose translational motion is classical. A sufficient condition for negligible quantum exchange effects is $n{\lambda }^3\ll 1$, where $n$ is the number density and $\lambda$ the thermal de Broglie wavelength. Diluteness alone does not guarantee thermal equilibrium; the gas must have equilibrated. These are the assumptions behind the classical Maxwell-Boltzmann velocity distribution. ^{[ref] [ref]}

The connection to Maxwell–Boltzmann statistics is the Boltzmann factor for translational kinetic energy, $E_{\mathrm{kin}}=m|\mathbf{v}{|}^2/2$. Normalizing $e^{-E_{\mathrm{kin}}/(k_{B}T)}$ over velocity gives a probability density; an occupation factor $e^{(\mu -E)/(k_{B}T)}$ instead specifies a mean occupation, with chemical potential $\mu$. Their normalizations serve different purposes. ^[ref]

This connects microscopic motion to measurements: a gas thermometer uses the ideal gas law, collisions and the mean free path govern transport, and measurements of spectral lines use thermal Doppler broadening to infer temperature. Each probes a different aspect of the same thermal motion.

In 1860, James Clerk Maxwell presented the component and speed laws in Part I, Proposition IV of Illustrations of the Dynamical Theory of Gases, pp. 22–23. His argument combined independence of the three velocity components with isotropy, and he explicitly compared the component law with the normal distribution of observational errors. Independence is an assumption of that argument; perpendicular coordinate axes alone do not establish it. ^[ref]

Maxwell relations turn pressure, volume and temperature measurements into information about entropy. For example, the pressure rise when heating a rigid sealed vessel determines the entropy change when expanding the same sample isothermally:The quantities on the two sides describe different experiments, yet both are mixed partial derivatives of one Helmholtz free energy. This is the useful surprise: a mechanical measurement can reveal a thermal property. Similarly, the coefficient of thermal expansion gives $(\partial S/\partial P{)}_{T,N}=-\alpha V$. ^[ref]

For a simple compressible system, hold particle number $N$ and composition fixed, and allow only pressure-volume work. Write $U$ for internal energy, $H=U+PV$ for enthalpy, $F=U-TS$ for Helmholtz free energy, and $G=H-TS$ for Gibbs free energy. Their natural-variable differentials areThus the first partial derivatives, with the subscript recording the variables kept fixed, areThe symmetry of second derivatives produces all four standard Maxwell relations, including their signs:For a brief derivation of the $F$ relation, differentiate $F_T=-S$ with respect to $V$ and $F_V=-P$ with respect to $T$: $-S_V=F_{TV}=F_{VT}=-P_T$. Each other row follows in the same way. Assume continuous second partial derivatives of the relevant thermodynamic potential in the region considered. At a phase transition, the equilibrium potential may lose this smoothness; apply the identities within each smooth thermodynamic phase, and handle latent heat and phase coexistence separately. If particle numbers vary, the potential differentials acquire chemical potential terms, so the fixed-$N$ constraints must remain explicit. ^[ref]

For an ideal gas with fixed $N$, the ideal gas law gives $P=N{k}_{B}T/V$. At fixed volume, heating changes the pressure at rate $N{k}_B/V$. Consequently an isothermal expansion at positive temperature hasFor one mole with $R=8.314\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$ and $V_2=2V_1$, this is $\Delta S=R\ln 2\simeq 5.763\mathrm{J}{\mathrm{K}}^{-1}$. At $300\mathrm{K}$, a reversible isothermal expansion absorbs $Q=T\Delta S\simeq 1728.85\mathrm{J}$ and performs equal work, since its internal energy is unchanged. The entropy difference is a state function difference: the same equilibrium endpoints give the same $\Delta S$ in an insulated free expansion, although there $Q=0$ and the process is irreversible.

The same Maxwell relations let thermal measurements determine the difference between constant-pressure and constant-volume heat capacities. In a smooth single thermodynamic phase,using heat capacity at constant volume, heat capacity at constant pressure, coefficient of thermal expansion and isothermal compressibility. Along fixed pressure, $dV=\alpha VdT$, soThus measured expansion and compression responses determine a heat capacity difference without measuring both heat capacities separately. They do not determine the absolute heat capacities or absolute entropy by themselves; an independent thermal measurement supplies that missing information. For an ideal gas, $\alpha =1/T$ and ${\kappa }_T=1/P$ reduce the result to $C_P-C_V=PV/T=N{k}_B$, which is Mayer's relation.

When the necessary higher partial derivatives exist and commute, differentiating the Maxwell relations once more also givesIntegrating these slopes determines how a heat capacity changes with volume or pressure at fixed temperature. For an ideal gas, both right-hand sides vanish because the ideal gas law is linear in temperature at either fixed volume or fixed pressure. Consequently $C_V$ and $C_P$ depend only on temperature at fixed $N$, although they need not be constant in temperature. ^[ref]

Historically, James Clerk Maxwell's Theory of Heat, first published in 1871, presents these connections using the geometry of isothermal processes and reversible adiabatic processes. His fourth edition, page 167, explicitly relates expansion on heating at fixed pressure to heat emitted during an isothermal compression: the modern $G$ relation gives $\delta Q_{\mathrm{rev}}=TdS=-T\alpha VdP$. This explains why a substance with positive coefficient of thermal expansion emits heat when compressed isothermally, whereas one with negative coefficient absorbs it. ^{[ref] [ref]}