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A motivating bench experiment asks whether a hot bath receives more heat than the electrical work supplied to a heat pump. PHYWE's authored operating instructions, section 4, describe a sealed vapor-compression refrigeration apparatus with its cold and hot coils immersed in separate water vessels. The quantitative procedure calls for insulated vessels, stirring to reduce temperature gradients, timed temperature readings, and a wattmeter for the input. It waits about five minutes for operating conditions to settle before measurements and explicitly includes the glass vessel and immersed copper pipe when calculating the heated body's heat capacity. One bath cooling while the other warms makes the origin of the delivered energy observable. ^[ref]

The following analysis extends that procedure to simultaneous measurements of both finite baths. Weigh the water in each vessel; determine the effective heat capacities $C_c$ and $C_h$, including immersed hardware, by a separate known electrical-input calibration over the working temperature range. A matched pair of calibrated thermometers placed in stirred water measures bulk $T_c(t)$ and $T_h(t)$; keeping probes away from the coils avoids mistaking a local contact temperature for the whole bath. Record the room temperature and synchronise the electrical meter and thermometry. Use short intervals after startup, with no boiling or freezing and small enough temperature changes that constant effective heat capacities are a reasonable approximation. These are proposed measurement controls, rather than reported results from the manual.

Over a common interval $[t_0,t_1]$, the uncorrected bath estimates and measured electrical input areHere the wattmeter records real electrical power $P_{\mathrm{el}}$. The integral handles changing input, and the signs make both estimated useful heat quantities positive during heating and cooling. The effective heat capacity includes water mass times its specific heat capacity plus the response of the vessel and immersed hardware. Without that correction, equal temperature changes need not imply equal heat transfers.

Insulation reduces heat leaks but does not establish an isolated system. A warmer bath can lose heat to the room while a colder bath gains it. As a proposed control, measure pump-off drift at matched bath and room temperatures, with the same stirring and insulation. Writing $L_h>0$ for outward hot-bath leak power and $L_c>0$ for inward cold-bath leak power, the bath balances giveIntegrate these rates over the same interval before dividing by $W_{\mathrm{el}}$. For example, in a pump-off hot-bath control, $L_h=-C_{h}d{T}_h/dt$; in the cold-bath control, $L_c=C_{c}d{T}_c/dt$. Check that a stopped machine does not create a different leak path from the running one; otherwise use an independent bath calibration and keep that discrepancy as an uncertainty. Repeat at the same starting temperatures to distinguish drift from a change in COP as the baths separate.

In the illustrated toy model, $C_h=C_c=4500\mathrm{J}{\mathrm{K}}^{-1}$, $P_{\mathrm{el}}=50\mathrm{W}$, ${\dot{Q}}_h=150\mathrm{W}$, ${\dot{Q}}_c=100\mathrm{W}$, $L_h=15\mathrm{W}$, and $L_c=5\mathrm{W}$ are stipulated constants for $180\mathrm{s}$. The slopes are $d{T}_h/dt=0.030\mathrm{K}{\mathrm{s}}^{-1}$ and $d{T}_c/dt=-19/900\mathrm{K}{\mathrm{s}}^{-1}$. Consequently,The raw heating and cooling ratios are $2.7$ and $1.9$, whose difference is $0.8$. Correcting the bath leaks gives $3$ and $2$, whose difference is one. The apparent failure of $Q_h=Q_c+W$ was incomplete measurement of heat, not a violation of the first law of thermodynamics.

Real apparatus can also release motor heat and pipe heat directly to the room, and store internal energy during startup. For a machine boundary that receives electrical work, an additional outward heat transfer $Q_{\mathrm{room}}$ gives $Q_h+Q_{\mathrm{room}}=Q_c+W_{\mathrm{el}}-\Delta U_{\mathrm{machine}}$. The residual $Q_h-Q_c-W_{\mathrm{el}}$ therefore tests the boundary and corrections; do not force it to zero. Include any auxiliary electrical work in the input if quoting whole-apparatus COP, and account separately for stirring work deposited in a bath. Ignoring vessel heat capacity, sensor lag or room leaks can bias the inferred result. These limitations follow from extending the measured energy budget, and the manual's explicit hardware correction illustrates why such boundaries matter.

Finally, these vessels are finite bodies whose temperatures change; they are not fixed thermal reservoirs. Their ratio of integrated useful heat to integrated input work is an interval COP. A Carnot's theorem comparison using simultaneous bath temperatures is a local approximation only when the machine settles much faster than the baths change. An exact reversible comparison for changing bath temperatures instead uses the bath entropy changes, for example $C_h\ln (T_{h,1}/T_{h,0})+C_c\ln (T_{c,1}/T_{c,0})$ for constant heat capacities, negligible net machine entropy change and no room leaks. The experiment's beauty is that two thermometers, known heat capacities and an electrical-energy measurement expose both conservation of energy and the practical gap from reversibility.

Heat transfer asks how quickly heat crosses a boundary and how the temperature varies along its path. Its principal mechanisms are thermal conduction, convection and thermal radiation. A warm wall can conduct heat through its interior while exchanging heat with moving air and emitting thermal radiation at its surfaces. Identifying these paths lets us estimate heating requirements and cooling times.

Distinguish the accumulated heat $Q$ from its rate $\dot{Q}=dQ/dt$, a power measured in $\mathrm{W}$. The heat flux $q$ is the rate per unit area, measured in $\mathrm{W}{\mathrm{m}}^{-2}$: a uniform normal heat flux across area $A$ gives $\dot{Q}=Aq$. The steady bar in thermal conduction carries $q=400\mathrm{W}{\mathrm{m}}^{-2}$ through $A=0.01{\mathrm{m}}^2$, hence $\dot{Q}=4\mathrm{W}$; maintained for $60\mathrm{s}$, it transfers $Q=240\mathrm{J}$. This distinction makes a surface's intensity and a whole object's heating load easy to compare.

Ice-melting calorimetry measures the fusion enthalpy through conservation of energy, rather than inferring it from the small temperature change of the melting ice itself. In a mixing experiment, warm water and the container cool while added ice melts and the resulting water warms. Their combined energy balance separates fusion from sensible heat.

Weigh the container and stirrer, then weigh the added warm water to obtain $m_w$. Let the container and water reach a common initial temperature $T_i$. Prepare ice in a clean ice-water mixture near $T_m$, rather than assuming freezer ice is already at $T_m$; drain and blot its surface immediately before transfer. Add it without splashing, stir gently, and record temperature before addition and until after the last ice disappears. Reweigh to find the added mass $m_i$. Wisconsin's laboratory guide specifies drying each piece, weighing before and after, and recording the temperature history; it places the initial and final temperatures on opposite sides of the jacket temperature to reduce net environmental exchange. ^[ref]

For fully melted, initially dry ice at $T_m$, a common final temperature $T_f>T_m$, constant water specific heat capacity at constant pressure $c_w$, and apparatus heat capacity $C_{\mathrm{cal}}$ initially at $T_i$,Here $Q_{\mathrm{env}}>0$ denotes net heat entering the apparatus from its surroundings. The left side supplies the fusion enthalpy and the sensible heat on the right; the water produced by melting must be warmed too. The balance extends Case Western's mixing demonstration by including the apparatus and environmental terms. If the specific heat capacities vary appreciably, replace their products with the corresponding temperature integrals. ^[ref]

Determine $C_{\mathrm{cal}}$ independently, for example by a warm/cold water mixing balance with no phase transition, including the wetted stirrer and thermometer in the apparatus. Check the thermometer calibration, keep the lid in place between transfers, and monitor the surroundings. Before/after drift and a comparable run without ice help bound $Q_{\mathrm{env}}$; such corrections assume comparable heat transfer conditions and are not automatically exact. Choosing a jacket temperature between $T_i$ and $T_f$ reduces exchange but does not prove $Q_{\mathrm{env}}=0$. Ensure all the ice has melted and the contents are well mixed before using the measured $T_f$: with residual ice, the weighed addition is not the mass that has undergone fusion. Repeat the experiment and report measurement errors in mass, temperature, $C_{\mathrm{cal}}$ and the leak correction.

An independent way to see the plateau is David Roundy's Oregon State experiment: heat an ice-water mixture slowly with a waterproof resistor in an insulated cup, stir, and record temperature, heater electric current $I(t)$, electric potential difference $V(t)$ and elapsed time. Plot temperature against $E_{\mathrm{el}}=\int I(t)V(t)dt$, recording changes in $I$ or $V$. The initial solid mass must exclude accompanying water. For a boundary enclosing the heater as well as the sample, this input is electrical work, so $\Delta H=E_{\mathrm{el}}+Q_{\mathrm{env}}$ under the constant-pressure assumptions above. Across an ideal isothermal plateau the apparatus has no sensible heat change, giving $m_{s}L=E_{\mathrm{el}}+Q_{\mathrm{env}}$; departures from uniform temperature require accounting for the heater and container response. ^[ref]

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, $PV=N{k}_{B}T$. ^{[ref] [ref]}

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 $300\mathrm{K}$ in $0.025{\mathrm{m}}^3$ has pressure approximately $99.774\mathrm{kPa}$, 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] [ref]}

The ideal gas law is the equation of state relating the absolute pressure $P$, volume $V$, particle count $N$, and absolute thermodynamic temperature $T$ of a classical ideal gas:Here $k_B$ is the Boltzmann constant, $N_{\mathrm{A}}$ is the Avogadro constant, $R$ is the molar gas constant, and $n_{\mathrm{mol}}$ is the amount of substance in moles. The distinct symbol $n_{\mathrm{mol}}$ avoids confusing amount of substance with the number density $n=N/V$, measured in ${\mathrm{m}}^{-3}$: the same law can be written $P=n{k}_{B}T$. Use absolute pressure, relative to a vacuum, rather than an unconverted gauge pressure. ^[ref]

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]}

For $n_{\mathrm{mol}}=1\mathrm{mol}$, $T=300\mathrm{K}$, and $V=0.025{\mathrm{m}}^3$, direct substitution givesAt fixed temperature and particle count, doubling the volume to $0.050{\mathrm{m}}^3$ halves the pressure to approximately $49.887\mathrm{kPa}$: this is Boyle's law. At fixed volume and particle count, doubling the temperature from $300\mathrm{K}$ to $600\mathrm{K}$ doubles the pressure to approximately $199.547\mathrm{kPa}$. These ratios use kelvins, not readings in the degree Celsius scale: $300\mathrm{K}$ is $26.85{}^{\circ }\mathrm{C}$, and $600\mathrm{K}$ is $326.85{}^{\circ }\mathrm{C}$.

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 $T=0$ 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 $P=\mathcal{R}\rho T/\mu$, where $\rho$ is mass density and $\mathcal{R}$ 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]

Infrared is electromagnetic radiation with wavelengths longer than the red end of ordinarily visible light. A useful named convention is the CIE range $780\mathrm{nm}$ to $1\mathrm{mm}$; the approximate visible range $400$–$700\mathrm{nm}$ used in some teaching texts puts the boundary nearer $700\mathrm{nm}$. ^[ref]. Neither number is a sharp physical cutoff of human vision. The CIE divisions IR-A, IR-B and IR-C are respectively $0.78$–$1.4\mu \mathrm{m}$, $1.4$–$3\mu \mathrm{m}$ and $3$–$1000\mu \mathrm{m}$; the boundaries of near-, middle- and far-infrared vary between applications. ^[ref].

Use vacuum wavelength $\lambda$ when comparing these ranges. With frequency $\nu$, speed of light $c$, Planck constant $h$ and photon energy $E$,Thus the CIE infrared interval corresponds approximately to $3.00\times 10^{11}$–$3.84\times 10^{14}\mathrm{Hz}$ and $1.99\times 10^{-22}$–$2.55\times 10^{-19}\mathrm{J}$ per photon, with the smaller energy at the longer wavelength. A $940\mathrm{nm}$ infrared photon has $E\simeq 2.11\times 10^{-19}\mathrm{J}$, whereas a $254\mathrm{nm}$ ultraviolet photon has $E\simeq 7.82\times 10^{-19}\mathrm{J}$. These are calculations from $hc/\lambda$, not measurements of a particular source. A television remote is a familiar approximately $940\mathrm{nm}$ source; its information is carried by variations in the emitted radiant flux. ^[ref].

Detection and visual perception answer different questions. A photodetector can respond to infrared even when an observer perceives no light; a thermometer detects an increase in temperature after photon absorption. Conversely, a small readout can reflect a small spectral responsivity, rather than absence of incident electromagnetic radiation. Images made from infrared readouts use display colors chosen by the imaging system; those colors are not the colors of the incoming infrared.

The important microscopic mechanisms also differ. In infrared spectroscopy, photon absorption often increases the energy of a normal mode in which chemical bonds stretch or bend. The corresponding optical spectrum helps distinguish molecules by their motions. For the usual electric dipole mechanism, the motion must change the electric dipole moment; matching the frequency alone is not sufficient. ^[ref]. Electronic processes can also emit or absorb infrared, so it is not exclusively radiation from molecular motion. ^[ref]; ^[ref].

Infrared is especially useful for observing thermal radiation from objects near everyday temperatures. For an ideal $300\mathrm{K}$ blackbody, Wien's displacement law gives a wavelength peak near $9.66\mu \mathrm{m}$. A thermal camera's readout nevertheless depends on emissivity, reflected surroundings and transmission along the path, as well as temperature. ^[ref]. A source emitting infrared need not be hot: an infrared remote is useful precisely because a photodetector can distinguish its signal from a background. Visible light and ultraviolet can also cause heating when absorbed; “infrared” names a wavelength range, not a unique form of heat.

Herschel's 1800 discovery made the distinction between sight and detection experimentally concrete. His report describes a optical prism spreading sunlight across a white, ruled receiving surface, with three thermometers at different positions near the end of the visible optical spectrum. He observed heating beyond the red edge where no visible color appeared. The result established that sunlight contained invisible radiation less strongly refracted by that optical prism than the visible red; it did not measure a photon energy or establish today's infrared boundaries. ^[ref]; ^[ref].

A documented modern version by Caltech/IPAC uses a glass optical prism, white paper in a shaded box and three blackened liquid-filled thermometers. Initial readings in shade provide each thermometer's baseline; subsequent readings compare blue, yellow and just beyond red after the bulbs have had time to warm. The measured quantity is the rise in temperature, not a “temperature of a color”. The lesson reports the expected largest rise beyond visible red and specifically discusses matching the bulb coatings and thermometer calibration. Clouds and changes in the projected optical spectrum affect the comparison. ^[ref].

For a stronger modern interpretation, an additional shaded thermometer would monitor ambient drift, exchanging bulbs between positions would test differences between thermometers, and blocking the incident beam would distinguish beam-dependent heating from warmed supports or air. These are suggested controls, not claims about Herschel's historical procedure. Thermal conduction through the mounting and convection can change the readout. A broad bulb also samples a range of wavelengths; the optical prism's transmission and optical dispersion, the bulb's absorption and heat loss all affect the position of the largest rise. In particular, the result does not show that an infrared photon carries more energy than a visible photon.

A simple analytical illustration makes those limitations explicit. Let $\theta =T-T_{\mathrm{amb}}$ be the bulb's excess temperature, $C$ its heat capacity, $G$ its effective heat-loss coefficient in $\mathrm{W}{\mathrm{K}}^{-1}$, and $P_{\mathrm{abs}}$ the absorbed power. Assume one uniform bulb temperature, constant ambient temperature, constant $C,G$, and losses linear in $\theta$. Thenfor a beam switched on at $t=0$ with $\theta (0)=0$. After switching the beam off at $t=t_s$, $\theta (t)=\theta (t_s)e^{-(t-t_s)/\tau }$. The exponential function follows by solving this linear differential equation. The steady excess temperature measures $P_{\mathrm{abs}}/G$; it is not a direct measurement of the optical spectrum. With illustrative $C=0.020\mathrm{J}{\mathrm{K}}^{-1}$ and $G=0.0010\mathrm{W}{\mathrm{K}}^{-1}$, $\tau =20\mathrm{s}$. Absorbed powers of $1.0$ and $0.5\mathrm{mW}$ give steady rises of $1.0$ and $0.5\mathrm{K}$, regardless of which wavelengths supplied that absorbed power.

The upper schematic represents the logic of the optical prism experiment; its light ray positions are not a calibrated wavelength scale. The lower curves use the illustrative heat-balance model, with the beam blocked at $60\mathrm{s}$; they are not historical or modern measured data. The beauty of the experiment is that a simple change of detector extends observation beyond what the eye can perceive.

Internal energy $U$ is the energy stored in the microscopic degrees of freedom of a thermodynamic system: random molecular kinetic energy, internal molecular excitations, and interaction potential energy. Its value requires a specified system and an energy reference. In thermodynamic equilibrium, internal energy is a state function; it records the present state, without remembering whether a previous change came from stirring, compression or heat transfer. This makes internal energy the common accounting quantity connecting mechanical experiments to thermal ones.^[ref]

Heat and work describe energy crossing the system boundary during a process. They are not separately stored contents of the system. For a closed system whose bulk kinetic energy and external potential energy have unchanged endpoint values, the first law of thermodynamics givesHere $Q_{\mathrm{in}}$ is positive for incoming heat, and $W_{\mathrm{on}}=-W_{\mathrm{out}}$ is positive for net work done on the system. Two routes between the same equilibrium states have the same $\Delta U$, although their heat and work can differ. The infinitesimal notation $dU=\delta Q_{\mathrm{in}}+\delta W_{\mathrm{on}}$ distinguishes a state function change from path-dependent transfers.^[ref]

For a calculated example, take one mole of a classical monatomic gas in the ideal gas regime, at fixed volume, from $300$ to $310\mathrm{K}$. With stipulated molar gas constant $R=8.314\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$, its internal energy change is $3nR\Delta T/2=124.71\mathrm{J}$. A purely thermal route supplies $Q_{\mathrm{in}}=124.71\mathrm{J}$ with $W_{\mathrm{on}}=0$. An ideal insulated stirring route supplies $W_{\mathrm{on}}=124.71\mathrm{J}$ with $Q_{\mathrm{in}}=0$, measured between equilibrium endpoints after the motion dies away. The same stored increment has two different transfer histories; neither history defines a separate kind of stored energy.

The familiar internal energy of an ideal gas is a useful special case. Neglect intermolecular interactions, hold the amount of substance $n$ and composition fixed, and suppose that $f$ independent quadratic terms per particle obey the classical equipartition theorem. Choosing the constant reference contribution as zero givesHere $T$ is absolute temperature, $R$ is the molar gas constant, and $C_V$ is the whole sample's heat capacity at constant volume. A monatomic gas has $f=3$ translational terms. A rigid diatomic molecule has $f=5$ when its two rotational terms are active and vibration is frozen; activating one harmonic oscillator vibration adds two terms, one kinetic energy and one potential energy, giving $f=7$. The counting is of quadratic contributions, so a vibrational coordinate is not just one contribution.^[ref]

This constant-$f$ formula applies only over a regime with those same active terms, classical translational statistics, nonrelativistic motion and unchanged composition. Quantum freezing, quantum degeneracy, chemical reactions or appreciable intermolecular interactions invalidate that simple counting. More generally, at fixed amount and composition an ideal gas can still have $U=U(T)$ with varying heat capacity at constant volume, so use $\Delta U={\int }_{T_1}^{T_2}{C}_V(T)dT$. A nonzero constant reference adds $U_{\ast }$ to $fnRT/2$ without altering $\Delta U$.