Internal energy at constant temperature 2026-10-14
Constant temperature does not generally mean constant internal energy. At fixed amount and composition, within one smooth thermodynamic phase of a simple compressible system, an equilibrium identity isThe bracket vanishes for the ideal gas law . It need not vanish for a real gas: changing the volume changes the average interaction potential energy, even when the random-motion contribution stays at the same temperature. The identity follows by writing and using a Maxwell relation; it does not require the actual process to be reversible. [ref]
For a Van der Waals equation model with volume per mole , gives . Thus an isothermal expansion from to , at fixed amount of substance , increases internal energy bySeparating attractive particles makes their interaction potential energy less negative. For stipulated , , , , and , the calculated increase for this one-mole sample is , despite . This dilute stable-branch model example is not a measurement of a named gas. [ref]
A phase transition gives another reason. During equilibrium vaporization of a pure substance at fixed pressure, the temperature can stay at its phase coexistence value while the phase fraction changes. Molecular separation changes interaction potential energy.[ref]
1.5 Phase Changes. §1.5, figure 1.18 and equations 1.7–1.8: molecular attractions and constant-temperature phase conversion
If the closed system does only pressure-volume work, its latent heat input obeysHere is enthalpy. A vaporization latent heat therefore is not automatically the internal energy increment: some input supplies expansion work. A fixed temperature reading alone cannot tell how much internal energy changed. Latent heat Created 2026-09-24 Updated 2026-10-14
Latent heat is the heat absorbed or released in a first-order phase transition through its entropy jump. For an equilibrium conversion from thermodynamic phase to thermodynamic phase at fixed pressure, evaluate both thermodynamic phases at the same temperature and pressure on their phase coexistence curve:Use one normalization throughout: , and may all be per mole, giving in , or all per unit mass, giving in . Here is entropy and is enthalpy on that basis. Equal Gibbs free energies of the coexisting thermodynamic phases give . Identifying this enthalpy difference with supplied heat assumes a closed system and an equilibrium conversion with only pressure-volume work. [ref]
For a pure substance with positive latent heat per unit mass , let be the phase fraction of the higher-enthalpy thermodynamic phase, measured by mass. While both thermodynamic phases coexist at the fixed pressure,Adding heat changes rather than the temperature; this creates the horizontal portion of a heating curve. Once , additional heat raises the temperature according to specific heat capacity at constant pressure. Reversing the conversion releases heat. The plateau represents changing enthalpy, rather than a finite single-thermodynamic phase heat capacity satisfying . [ref]
For a constructed fixed-pressure model, take , initial temperature , transition temperature , solid specific heat capacity at constant pressure , latent heat , and liquid specific heat capacity at constant pressure . These are stipulated model parameters, not empirical properties of a named material. Heating the solid to takes of sensible heat; converting it fully to liquid takes another of heat; heating the liquid to takes . The total is . After a total heat input of , and the temperature is still . The corresponding per-unit-mass entropy jump is .
A continuous phase transition has no latent heat. Its heat capacity can have a jump or a singularity without a finite interval in which added heat converts coexisting thermodynamic phases at a constant temperature. A heating plateau therefore requires the stated phase coexistence conditions; it is not a feature of every phase transition. [ref]
Statistical Physics by David Tong. Tong, Statistical Physics, first-order and continuous transitions
Latent heat of fusion Created 2026-10-13 Updated 2026-10-18
An ice bath can absorb heat while its temperature barely changes: the heat converts ice into water. The latent heat of fusion quantifies this melting budget. For a pure substance at its equilibrium melting temperature and specified pressure , define it here per unit mass:Here and are the specific enthalpies of the coexisting bulk liquid and solid, and is enthalpy. For ordinary melting, , in ; an amount has a total fusion enthalpy in joules. A molar fusion enthalpy instead has units and equals , where is mass divided by amount of substance in . Always check the normalization before inserting a tabulated value into an energy balance.[ref] [ref]
For a closed system converting completely from solid to liquid at fixed pressure, with only pressure-volume work and negligible changes in bulk kinetic energy and potential energy, the first law of thermodynamics gives . Both endpoints are at : warming initially colder ice or subsequently warming the resulting water requires additional sensible heat. Since , the corresponding specific internal energy jump is , where ; includes the work associated with the change in volume. Heat is transferred energy, whereas enthalpy is a state function. [ref]
Let be the liquid phase fraction by mass, rather than by volume. Neglecting interfacial contributions to enthalpy, equilibrium phase coexistence at fixed pressure givesIn the model above, reaching takes of sensible heat; the plateau then absorbs , ending at a cumulative . At , half the mass is liquid and the temperature is still . The final warming takes another . The rounded and are inspired by the introductory ice-melting calorimetry values in Case Western's demonstration; constant properties and exact equilibrium throughout are stipulated model assumptions. [ref]
https://case.edu/artsci/phys/courses/demos/spec.htm. Case Western Reserve University, specific heat and heat of fusion demonstration
Within one thermodynamic phase, specific heat capacity at constant pressure is , in ; a sample's heat capacity at constant pressure is , in . The plateau is a finite enthalpy change at zero temperature change through varying , so neither a finite single-phase nor represents it. The heating curve needs separate sensible heat intervals and a fusion contribution. [ref]
The plateau assumes a pure substance, a stable bulk solid-liquid phase coexistence pair, fixed pressure, and sufficiently slow, uniform heating to remain near thermodynamic equilibrium. The total mass and composition must remain fixed, with negligible evaporation and no other phase transition. A fast heater can produce temperature gradients, so a local thermometer need not read the equilibrium . Neither nor is universal across pressures or compositions: common-pressure melting-point slope describes the pressure dependence of , while mixtures can melt over a temperature range as their coexisting compositions change. Their liquidus must be consulted instead of assuming a pure-substance plateau. [ref]
https://www2.tulane.edu/~sanelson/eens211/2compphasdiag.pdf#page=3. Stephen A. Nelson, Tulane, Two Component Phase Diagrams, pp. 2–4: melting ranges and liquidus
This makes ice useful as a temperature buffer: under these conditions it can absorb before the remaining solid mass disappears, after which the water warms. If a stipulated constant net input power goes entirely into melting, that buffer lasts . Reversing the equilibrium conversion releases the same fusion enthalpy during freezing. The beautiful thermodynamic connection is , with the specific entropy and absolute temperature: equal Gibbs free energies at phase coexistence allow different enthalpies and entropies. The nearly stationary thermometer hides a finite, measurable change of state. [ref]
Sensible heat Created 2026-10-14 Updated 2026-10-20
Sensible heat is transferred heat associated with a temperature change within a single thermodynamic phase. By contrast, latent heat can change the phase fraction while the temperature stays fixed during equilibrium phase coexistence. Neither name denotes an additional stored substance: both describe how transferred heat participates in a process.
For fixed mass and composition, use the heat capacity appropriate to the heating constraint. Under the quasistatic process assumptions in heat capacity, with only pressure-volume work and unchanged bulk kinetic energy and potential energy, fixed-pressure heating givesHere is specific heat capacity at constant pressure; fixed-volume heating instead uses specific heat capacity at constant volume . A cooling step has negative with the sign convention in heat. A temperature difference has the same numerical value in units of the kelvin or degree Celsius. The integral follows by adding the small transfers , rather than assuming a constant heat capacity.
As a stylized ice-to-water example for a fixed-composition closed system at fixed pressure , take , an initial temperature of , melting at , and a final temperature of . Assume constant specific heat capacity at constant pressure values and , and latent heat of fusion . These are stipulated, rounded model values; ignore the container and heat losses, retain all the material, and assume only pressure-volume work under the quasistatic process conditions above. The three steps areOnly the first and third terms are sensible heat; the middle term is latent heat. The plateau begins after and ends after of total supplied heat. At total input, half the mass is liquid water and the temperature remains . The equilibrium phase transition temperature depends on pressure; this example stipulates a single fixed pressure. [ref]
This split makes heating budgets easy to interpret: melting consumes of the supplied heat in this model despite causing no temperature rise. Within either single thermodynamic phase, the heating curve slope is ; a larger heat capacity makes the slope shallower. A flat interval represents changing phase fraction, so it cannot be modeled by applying across the phase transition. The complementary constructed example in latent heat tracks that phase fraction explicitly.


