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Emissivity compares thermal emission from a surface with emission from an ideal blackbody at the same absolute temperature, using the same wavelength and angular averaging convention. For ordinary passive surfaces in the far field at local thermal equilibrium, the ratio lies between zero and one. A blackbody has emissivity one. Unless a spectral or directional qualification is given, the $ϵ$ in $M=ϵ\sigma T^4$ is total hemispherical emissivity: a ratio of emitted radiant exitances, not of all outgoing radiant flux including reflected radiation.^[ref]

Emissivity belongs to a specified surface state, not just a bulk material name. Coating, oxidation and surface finish can change it; wavelength, viewing direction and temperature also matter. A surface that looks white in visible light need not have low infrared emissivity. This distinction is useful when choosing a radiator coating or interpreting a radiation-based temperature measurement: a narrow-band detector needs the appropriate spectral emissivity, and its signal can include reflected surrounding radiation. The grey body and diffuse thermal emitter assumptions are separate simplifications, addressing wavelength and direction respectively.

The first law applies conservation of energy to a thermodynamic system. For a closed system with unchanged bulk kinetic energy and potential energy, writeHere $U$ is internal energy, $Q>0$ is heat entering the system and $W>0$ is work done by the system on its surroundings. Compression therefore gives negative $W$. Some references define work positive when done on the system; their plus sign represents the same balance with a different convention. If bulk kinetic energy or potential energy changes, include it in the total energy balance. ^[ref]

Supplying $1000\mathrm{J}$ of heat while a gas does $300\mathrm{J}$ of work increases its internal energy by $700\mathrm{J}$. Compressing it with $200\mathrm{J}$ of input work in an adiabatic process instead gives $Q=0$, $W=-200\mathrm{J}$ and $\Delta U=200\mathrm{J}$.

The distinction between $d$ and $\delta$ records state versus path: internal energy is a state function, whereas heat and work depend on the process. For an ideal gas expanding reversibly at constant temperature, $W=N{k}_{B}T\log (V_2/V_1)$ and $Q=W$, since internal energy of an ideal gas depends only on temperature. Choose $N{k}_{B}T=1000\mathrm{J}$ and $V_2=2V_1$: then $Q=W=693.15\mathrm{J}$. An insulated free expansion into vacuum between the same equilibrium endpoints has $Q=W=0$. Both have $\Delta U=0$, yet their transfers differ. Their common entropy increase is $N{k}_B\log 2$. ^[ref]

For a simple compressible equilibrium system of fixed composition, combining the laws givesHere $p$ is pressure and $V$ is volume. This identity relates neighboring equilibrium states. Identifying $TdS$ with actual heat and $pdV$ with actual work requires a suitable reversible thermodynamic process; an irreversible piston calculation uses the external resisting pressure for boundary work. This distinction prevents applying a reversible ideal-gas adiabat to an irreversible adiabatic piston compression.

A grey body has spectral emissivity independent of wavelength over the range in which the approximation is used. Under Kirchhoff's law of thermal radiation, the corresponding radiometric absorptance is also wavelength-independent. This allows the same factor to weight emission at $T$ and black-enclosure irradiation at a different $T_s$ in net radiative heat exchange. The factor can still depend on temperature; treating it as constant over a cooling curve is an additional assumption. Wavelength independence alone does not imply direction independence.^[ref]

For a small, uniform surface at temperature $T$, enclosed by much larger black walls all at temperature $T_s$, the outward net heat transfer by thermal radiation isAssume an opaque grey body that is a diffuse thermal emitter, with the same emissivity $ϵ$ and radiometric absorptance at the surface's current temperature. Its emitting area $A$ sees only the enclosure: the view factor to the walls is one, with no self-viewing surface, opening or intervening obstruction. The intervening medium must neither absorb nor emit appreciable thermal radiation; a vacuum supplies a useful idealization. The enclosure is maintained at uniform $T_s$. The small-body assumption makes that reservoir description physically reasonable; genuinely black isothermal walls supply the incoming irradiance even without an infinite area ratio. Positive ${\dot{Q}}_{\mathrm{rad}}$ means net loss by the surface; negative means net gain. This expression counts thermal radiation alone, not all heat transfer.^[ref]

The reasoning is a two-way energy balance. Black walls supply irradiance $E=\sigma T_s^4$, so the surface absorbs $P_{\mathrm{abs}}=ϵAE$ and emits $P_{\mathrm{emit}}=ϵA\sigma T^4$. Subtract these to obtain ${\dot{Q}}_{\mathrm{rad}}$. For an opaque surface the remaining fraction $1-ϵ$ of incoming radiant flux is reflected; counting emitted plus reflected outgoing radiant flux minus total incoming radiant flux gives the same result. Kirchhoff's law of thermal radiation justifies equal spectral absorption and emission factors; the grey body assumption lets one factor be taken outside both spectral integrals.

Choose $ϵ=0.8$, $A=0.01{\mathrm{m}}^2$, $T=500\mathrm{K}$ and $T_s=300\mathrm{K}$. These are stipulated model inputs, not measured material properties. Using $\sigma \approx 5.670374419\times 10^{-8}\mathrm{W}{\mathrm{m}}^{-2}{\mathrm{K}}^{-4}$ givesThe incoming irradiance is $459.300\mathrm{W}{\mathrm{m}}^{-2}$, corresponding to $4.5930\mathrm{W}$ incident on the surface; only $80\%$ is absorbed. At $T=T_s=300\mathrm{K}$, emitted and absorbed powers are both $3.6744\mathrm{W}$, so radiative equilibrium has zero net exchange despite continuing emission. Changing only emissivity to $0.2$ reduces both one-way powers and the net loss by a factor of four, giving $6.1694\mathrm{W}$ net. A low-emissivity coating therefore suppresses both radiative cooling to colder walls and radiative heating from hotter walls.

Near equal temperatures, write $T=T_s+\Delta T$. Taylor's theorem givesFor constant emissivity, the radiative heat transfer coefficient $h_{\mathrm{rad}}$ is approximately $4.8992\mathrm{W}{\mathrm{m}}^{-2}{\mathrm{K}}^{-1}$ at $T_s=300\mathrm{K}$ and $ϵ=0.8$. This local linear approximation is useful for small temperature differences; the $200\mathrm{K}$ difference in the worked example needs the full fourth-power expression.

A cooling experiment requires a wider first law of thermodynamics balance. In a uniform-temperature model without a heater,where $C(T)$ is the sample's heat capacity and the last two terms are signed outward convection and thermal conduction losses. A vacuum suppresses convection but does not eliminate thermal conduction through supports or sensor leads. A cooling slope therefore cannot establish emissivity unless these paths and heat capacity are independently constrained. Multiple wall temperatures, incomplete view factors, wavelength-selective materials or appreciable intervening absorption require a more complete radiative transfer calculation.

A state function assigns a value to each equilibrium thermodynamic state of a specified thermodynamic system. Its change depends only on the initial and final states. Internal energy $U$, entropy $S$ and enthalpy $H=U+pV$ are state functions; here $p$ is pressure and $V$ is volume. Transferred heat $Q$ and work $W$ belong to a thermodynamic process, rather than to a state. A system stores internal energy; it does not store separate inventories of “heat received” and “work received”.^[ref]

Use the explicit convention $Q>0$ for heat entering and $W_{\mathrm{by}}>0$ for work done by the thermodynamic system on its surroundings. For a closed system with unchanged endpoint bulk kinetic energy and external potential energy, the first law of thermodynamics readsThe notation $dU$ denotes an exact differential of a state function; $\delta Q$ and $\delta W_{\mathrm{by}}$ denote incremental transfers. Along a reversible thermodynamic process of a simple compressible system,where $T$ is absolute temperature. These are rules for particular thermodynamic processes, not definitions of stored heat or stored work. In particular, a quasistatic process with friction can remain near thermodynamic equilibrium while producing entropy.^[ref]

For any state function $F$ and two equilibrium states $A,B$, an integral of its exact differential givesThe proof is telescoping: add the changes $F(x_{i+1})-F(x_i)$ along a subdivided path, and all intermediate values cancel. The smooth limit gives the integral. Conversely, if an integrable differential form has zero integral around every accessible closed path in a connected region, define $F(B)$ by integrating from a reference state. Two routes differ by a closed path, so the definition is unambiguous. This argument needs every accessible loop, rather than a local test that might miss a hole in the domain; see path independence.

The same cancellation does not hold separately for heat and work. A thermodynamic cycle has $\Delta U=0$ but can have nonzero net transfers, with $\oint \delta Q=\oint \delta W_{\mathrm{by}}$. Nor does the fact that entropy is a state function make $Q/T$ its general change: the formula $dS=\delta Q_{\mathrm{rev}}/T$ uses a reversible thermodynamic process and its varying temperature.

This distinction makes endpoint calculations powerful. We can compute an internal energy, entropy or enthalpy difference along a convenient reversible reference path even when the actual thermodynamic process is irreversible. Its actual heat and work must still be obtained from its own boundary interactions. The appealing cancellation is visible in two reversible ideal-gas paths between the same states: a different mechanical output requires a matching difference in thermal input, while stored internal energy arrives at the same value.

For steady flow through a fixed control volume with one inlet and one outlet, the first law of thermodynamics and conservation of mass giveHere $\dot{m}$ is the mass flow rate, $\dot{Q}$ incoming heat per unit time, ${\dot{W}}_s$ outgoing non-flow work per unit time, $w$ the flow speed, $z$ elevation and $g$ gravitational acceleration. The specific enthalpy $h=u+p/\rho$ includes both the transported internal energy per unit mass $u$ and the pressure work needed to push volume through the boundary; $\rho$ is mass density. The inlet supplies that pressure work, while the outlet consumes it to displace the downstream fluid.^[ref]

For an insulated stationary throttle, require negligible heat transfer, no shaft or other non-flow work, and negligible changes in bulk kinetic energy and gravitational potential energy. Then $h_2=h_1$. With unchanged composition this is also equality of molar enthalpy. The upstream and downstream states must admit equilibrium pressure, temperature and property values, although the constriction itself is irreversible and can be far from thermodynamic equilibrium. Start-up storage of energy in the walls and fluid, heat leakage, or a large outlet speed invalidates the reduced balance. A nozzle can convert specific enthalpy into bulk kinetic energy even when it is insulated.

The same accounting for a fixed transported amount is $U_2-U_1=p_1{V}_1-p_2{V}_2$, hence $U_1+p_1{V}_1=U_2+p_2{V}_2$. This explains why dropping the two pressure work terms would give the wrong conserved quantity.^[ref]

The Stefan–Boltzmann law gives the total hemispherical radiant exitance of an ideal blackbody at absolute temperature $T$:Here $\sigma$ is the Stefan-Boltzmann constant. Total means integrated over all wavelengths; hemispherical means integrated over all outward directions with the projected area weighting. Thus $M_b$ is emitted power per actual emitting area, rather than directional radiance or spectral radiance. Absolute temperature must be in kelvin; raising a Celsius reading to the fourth power gives the wrong result. A uniform surface of area $A$ emits radiant flux $P_{\mathrm{emit}}=A{M}_b$. A real surface instead has $M=ϵ(T)\sigma T^4$, where $ϵ(T)$ is its total hemispherical emissivity. The older symbol $F$ in the formula above denotes this emitted radiant exitance.^[ref]

For an ideal blackbody, doubling absolute temperature multiplies radiant exitance by $16$. With the approximate Stefan-Boltzmann constant $5.670374419\times 10^{-8}\mathrm{W}{\mathrm{m}}^{-2}{\mathrm{K}}^{-4}$, the radiant exitances at $300\mathrm{K}$ and $600\mathrm{K}$ are approximately $459.300$ and $7348.805\mathrm{W}{\mathrm{m}}^{-2}$. This steep response explains why thermal radiation becomes so consequential at high temperature. It also enables heat transfer through a vacuum, where thermal conduction through a gas and convection are absent.

A short derivation integrates Planck's law in its frequency form. For a blackbody, direction-independent spectral radiance is $B_{\nu }(T)=2h{\nu }^3/[c^2(e^{h\nu /(k_{B}T)}-1)]$, where $h$ is the Planck constant, $k_B$ the Boltzmann constant and $c$ the speed of light. The outward hemisphere contributes $\int \cos \theta d\Omega =\pi$, soExpanding $(e^x-1{)}^{-1}={\sum }_{n=1}^{\infty }{e}^{-nx}$, nonnegative terms allow termwise integration. Repeated integration by parts gives ${\int }_0^{\infty }{x}^3{e}^{-nx}dx=6/n^4$; the Riemann zeta function value $\zeta (4)={\pi }^4/90$ gives the remaining integral as ${\pi }^4/15$. Hence $M_b=\sigma T^4$ with the coefficient in Stefan-Boltzmann constant. The angular integral is essential: omitting it confuses radiance with radiant exitance.

An equilibrium thermodynamic state specifies sufficient independent macroscopic properties, together with material identity and constraints, to determine the other equilibrium properties. For a uniform fixed-composition ideal gas, its amount of substance, temperature and volume determine its pressure through the ideal gas law. These properties specify a state, without specifying a thermodynamic process that prepared it.^[ref]

A thermodynamic system is the part of the physical world selected for an energy and matter balance. Draw its boundary before classifying an interaction as heat, work or transported matter. The boundary may move: a sealed piston encloses a closed system even while its volume changes. An isolated system additionally excludes all external energy transfers.^[ref]

Boundary choice changes the ledger. If an electrical heater warms water, choosing only the water counts incoming heat; including the heater counts electrical work entering through its leads. The combined internal energy records storage, without separate stored categories for the two transfer mechanisms.^[ref]

Take a closed system consisting of one mole of a classical monatomic gas, idealized as an ideal gas with constant heat capacity at constant volume $C_V=3nR/2$. Stipulate amount of substance $n=1\mathrm{mol}$ and molar gas constant $R=8.314\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$ for this calculation. Set initial temperature $T_0=300\mathrm{K}$ and volume $V_0=0.010{\mathrm{m}}^3$, and define $E_0=nR{T}_0=2.4942\mathrm{kJ}$ and $p_0=E_0/V_0=249.42\mathrm{kPa}$. The specified equilibrium endpoints areThus $B$ has volume $0.030{\mathrm{m}}^3$, temperature $600\mathrm{K}$ and pressure $166.28\mathrm{kPa}$. The fixed material inventory and ideal gas law make these complete endpoint specifications for this model. All numbers below are calculated values, rather than measurements of a particular gas.

Use a frictionless piston, ignore bulk mechanical energy changes, and allow only pressure-volume work. Each step is the limit of a reversible thermodynamic process: adjust loads by infinitesimal pressure differences, and supply heat through infinitesimal temperature differences. Heating with changing temperature requires a succession of matching thermal reservoirs; contact with a single hotter heat bath would give an irreversible finite difference. On a fixed-volume leg the piston is locked. These assumptions justify using the actual equilibrium path's pressure inAn endpoint chord is not the path; substituting a guessed straight line would compute a different thermodynamic process.^[ref]

The upper route heats at fixed volume from $A$ to $C=(V_0,2T_0,2p_0)$, then undergoes isothermal expansion at $2T_0$ to $B$. The lower route undergoes isothermal expansion at $T_0$ from $A$ to $D=(3V_0,T_0,p_0/3)$, then heats at fixed volume to $B$. The tuples use the same $(V,T,p)$ ordering as the endpoints. Vertical legs do zero expansion work, and the two curved legs have different pressures at every shared intermediate volume.

The internal energy of an ideal gas gives the same endpoint difference for both routes:On either fixed-volume heating leg, $W_{\mathrm{by}}=0$ and $Q=3E_0/2$. On each isothermal expansion, $\Delta U=0$, so the first law of thermodynamics gives $Q=W_{\mathrm{by}}$. The ideal gas law and the integral of $1/V$ then giveHere $\ln$ is the natural logarithm. Rounded to $0.001\mathrm{kJ}$, the upper route has $(Q,W_{\mathrm{by}},\Delta U)=(9.222,5.480,3.741)\mathrm{kJ}$ and the lower route has $(6.481,2.740,3.741)\mathrm{kJ}$. Subtracting separately rounded entries can differ by $0.001\mathrm{kJ}$; the unrounded balances are exact in the stipulated model.

The shaded area between the curves explains the entire difference:Following the upper route forward and the lower route backward makes a thermodynamic cycle with this positive net work and matching net heat. Its internal energy change is zero. The two open routes themselves are reversible, so their different work outputs should not be mistaken for a loss caused by entropy production: they receive different heat transfers at different temperatures.

Two other state functions provide independent endpoint checks. With enthalpy $H=5nRT/2$ in this model,To obtain the entropy change along either route, integrate $C_{V}dT/T$ on its heating leg, giving $C_V\ln 2$, and $nRdV/V$ on its isothermal expansion, giving $nR\ln 3$. Reordering the legs changes their heat totals but leaves the sum of their entropy changes unchanged. In particular, neither route's total $Q$ divided by its final temperature equals $\Delta S$, and neither total $Q$ equals $\Delta H$: both routes include an isothermal expansion, rather than a single fixed-pressure heating step.

The view factor $F_{i\to j}$ is the fraction of uniformly distributed, diffuse outgoing radiant flux from surface $i$ that directly reaches surface $j$. It depends on geometry, including obstruction, rather than on temperature or emissivity. All destinations in a closed enclosure have fractions summing to one. For a convex body fully enclosed by walls, $F_{\mathrm{body}\to \mathrm{walls}}=1$; the reverse view factor is generally smaller. Reciprocity gives $A_i{F}_{i\to j}=A_j{F}_{j\to i}$. Two unobstructed spheres with outer radius ten times the inner radius have $F_{\mathrm{inner}\to \mathrm{outer}}=1$ and $F_{\mathrm{outer}\to \mathrm{inner}}=1/100$. Do not multiply both directions by an assumed identical view factor.^[ref]