Enthalpy Created 2026-09-24 Updated 2026-10-18
Enthalpy is the state function obtained by adding pressure times volume to internal energy:Here denotes internal energy, also written in some references. Like internal energy, enthalpy is measured in joules and is an extensive variable. Its definition packages the internal energy change and expansion work into one useful quantity for fixed-pressure calculations. It does not define a body's stored heat. [ref]
For a fixed amount and composition of a simple compressible system, the relation between neighboring equilibrium states isHere is absolute temperature and is entropy. Thus entropy and pressure are the natural variables of this thermodynamic potential, with partial derivatives and . Fixed composition matters: changing composition adds further terms. The formula follows in one line from the equilibrium first law of thermodynamics identity:The cancellation of is the reason enthalpy replaces volume with pressure as a natural variable. This identity concerns equilibrium states; it does not identify with actual irreversible heat transfer. [ref]
For a closed system undergoing a quasistatic process at constant pressure, require fixed amount and composition, only pressure-volume work, no friction, and unchanged bulk kinetic energy and potential energy. Then the actual first law of thermodynamics balance givesThe symbol means transferred heat for this fixed-pressure process. If the piston example in heat additionally meets these conditions, its of incoming heat equals , while and . The example shows exactly what enthalpy adds to internal energy: the expansion work required at the imposed pressure.
Within a single thermodynamic phase, heat capacity at constant pressure giveswith the amount and composition fixed. Constant gives ; dividing by mass gives specific heat capacity at constant pressure. At equilibrium melting, enthalpy can instead change through latent heat while temperature stays fixed. The sensible heat example therefore adds two single-thermodynamic phase enthalpy changes and one latent heat contribution.
The usefulness of enthalpy lies in matching the imposed constraint: a fixed-pressure experiment naturally reports , while fixed-volume heating with no other work reports . Neither equality is universal. Additional work or changing pressure alters the relation between supplied heat and ; irreversible entropy production also prevents identifying actual with . The separate Joule-Thomson coefficient branch uses enthalpy to describe throttling under its own assumptions.
Heat Created 2026-09-24 Updated 2026-10-14
Heat is energy transferred across a thermodynamic system's boundary because of a temperature difference. It is measured in joules, like work and internal energy. A hot cup transfers heat to cooler surroundings; its temperature describes its state, while the transferred heat describes a process. The cup stores internal energy, rather than a substance called heat. [ref]
https://openstax.org/books/university-physics-volume-2/pages/1-4-heat-transfer-specific-heat-and-calorimetry. Ling, Moebs and Sanny, OpenStax, University Physics Volume 2, section 1.4: heat and internal energy
For a closed system with unchanged bulk kinetic energy and potential energy, choose for heat entering and for work done by the system. The first law of thermodynamics givesHere is the stored internal energy. For example, a sealed piston cylinder receiving of heat and delivering of work gains of internal energy. A closed system retains its matter while exchanging energy; it need not be an isolated system. [ref]
https://openstax.org/books/university-physics-volume-2/pages/3-3-first-law-of-thermodynamics. Ling, Moebs and Sanny, OpenStax, First law of thermodynamics and sign conventions
Unlike internal energy, heat is not a state function: different paths between the same equilibrium states can transfer different , with compensating differences in work. The symbol records this dependence on the path; there is no stored quantity whose difference is always . The two paths in first law of thermodynamics illustrate this directly. Supplied heat can raise temperature as sensible heat, change a phase fraction through latent heat, or help supply expansion work. Measuring temperature alone therefore does not determine transferred heat.
For a reversible thermodynamic process, , where is absolute temperature and is entropy. This identification requires reversibility: an irreversible adiabatic process has and can nevertheless increase entropy. Likewise , with enthalpy , requires the particular fixed-pressure conditions in enthalpy. These distinctions make heat useful as a precise boundary-transfer quantity in heat engines, refrigerators and heating calculations.
Historically, James Prescott Joule's paddle experiments showed that stirring water with input work could raise its temperature, helping establish conservation of energy. The lesson is still useful: a temperature rise can result from work even without incoming heat. [ref]
https://openstax.org/books/university-physics-volume-2/pages/1-4-heat-transfer-specific-heat-and-calorimetry. Ling, Moebs and Sanny, OpenStax, section 1.4: Joule's paddle experiment
Heating curve 2026-10-14
A heating curve records temperature against accumulated supplied heat under a specified constraint. Within one thermodynamic phase, its slope is , where is the constrained heat capacity. A latent heat plateau instead records changing phase fraction at the phase coexistence temperature. The sensible heat example combines two sloping intervals and a melting plateau in one heating budget.
Ice-melting calorimetry 2026-10-14
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 . Let the container and water reach a common initial temperature . Prepare ice in a clean ice-water mixture near , rather than assuming freezer ice is already at ; 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 . 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]
https://badger.physics.wisc.edu/trash/lab_old/manual/node30.html. University of Wisconsin, H-2: Latent heat of fusion of ice, procedure
For fully melted, initially dry ice at , a common final temperature , constant water specific heat capacity at constant pressure , and apparatus heat capacity initially at ,Here 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]
https://case.edu/artsci/phys/courses/demos/spec.htm. Case Western, mixing-calorimetry energy balance
Determine 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 ; such corrections assume comparable heat transfer conditions and are not automatically exact. Choosing a jacket temperature between and reduces exchange but does not prove . Ensure all the ice has melted and the contents are well mixed before using the measured : with residual ice, the weighed addition is not the mass that has undergone fusion. Repeat the experiment and report measurement errors in mass, temperature, 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 , electric potential difference and elapsed time. Plot temperature against , recording changes in or . 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 under the constant-pressure assumptions above. Across an ideal isothermal plateau the apparatus has no sensible heat change, giving ; departures from uniform temperature require accounting for the heater and container response. [ref]
https://paradigms.physics.oregonstate.edu/act/handout/2108. David Roundy, Oregon State, Ice Calorimetry Lab: apparatus, stirring and electrical input
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]
Past exam of the geophysical fluid dynamics course of the University of Oxford 2023 1 c Solution 2026-10-25
Take eastward , upward , positive wavenumbers , and a real instantaneous amplitude . A common growing factor does not affect the phase geometry. Put and , using the hyperbolic cosine and hyperbolic sine. The prescribed streamfunction iswhereFollowing a fixed phase givesTherefore the streamfunction pattern tilts westward with height. The lower boundary leads the upper boundary eastward.
In the conventional quasi-geostrophic streamfunction normalization, hydrostatic balance gives . ThereforeFor the phase calculation, multiplication by the constant is immaterial. Define a continuous phase ; this avoids a spurious discontinuity at . ThenThe buoyancy perturbation pattern tilts eastward with height, opposite to the streamfunction pattern. At , while , so the two fields are a quarter wavelength apart there.
Both perturbation amplitudes are largest at the boundaries. Indeed,which increase with . The physical reason is particularly clear through stratified quasi-geostrophic inversion: the Eady model has no interior background potential-vorticity gradient, and a growing normal mode has zero interior potential vorticity anomaly. The independent thermal anomalies reside at the rigid upper and lower boundaries, where meridional motion advects the basic horizontal buoyancy gradient. Each Eady edge wave induces an interior balanced flow that decays away from its boundary on scale . Their interacting, phase-locked combination produces the growing baroclinic instability. Boundary confinement of the thermal sources, rather than a rigid-wall requirement , explains the amplitude pattern.
For a sketch with a quarter-wavelength difference between the boundary streamfunction patterns, chooseAn upper positive streamfunction crest is then west of its lower counterpart, where . The buoyancy perturbation crests slope the other way. The quarter-wavelength boundary assumption is used for the streamfunction; differentiating in fixes the buoyancy perturbation and does not generally give it the same boundary phase separation.
Original Eady model sketch: streamfunction crests tilt westward and buoyancy perturbation crests eastward. Dashed curves follow positive maxima; the streamfunction boundary phase difference is a quarter wavelength.
Details. The connection to poleward heat transport can be checked without relying on the sketch. The meridional geostrophic flow and buoyancy perturbation areAverage over one zonal wavelength, using equal averages for squared sine and cosine and zero for their product:In the Northern Hemisphere this is positive: warm anomalies preferentially move northward and cold anomalies southward. For the same eastward-increasing basic thermal wind in the Southern Hemisphere, and the basic buoyancy gradient reverses; the negative northward eddy buoyancy flux is again poleward. For thermal expansion coefficient and specific heat capacity at constant pressure , the corresponding sensible heat flux in a thermal Boussinesq approximation is . The growing amplitude makes this flux grow as . The tilt supplies the correlation absent in an untilted disturbance and reduces the background available potential energy.
Write for the fixed surface temperature and . The heat capacity per unit volume is . Per unit horizontal area the layer stores sensible heat . Its increase equals the input less the output:The same equation holds for because is constant. It assumes the supplied constant-property, fixed-thickness layer, without internal heat production, latent heat, or mechanical contributions to its heat budget. The infinite horizontal area is handled by taking the budget per unit area.
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.
Specific heat capacity at constant pressure Created 2026-09-28 Updated 2026-10-14
The specific heat capacity at fixed pressure and composition is , where is specific enthalpy. Equivalently, it is heat capacity at constant pressure divided by mass. Under the process assumptions in heat capacity, it includes expansion work as well as the internal energy change. The sensible heat example uses this response separately for ice and water.
Wet-ice bias in fusion calorimetry 2026-10-14
Surface water counted as ice needs warming but has already undergone melting. Its presence therefore biases a dry-ice estimate of latent heat of fusion downward. This is why drying the added ice is a quantitative control in ice-melting calorimetry, rather than cosmetic preparation. Let be the total added mass at , of which a fraction is already liquid and remains solid. The correct constant-property balance isIf an analysis incorrectly treats all as solid and sets , it obtainsThus gives a low estimate with no heat leak. Unaccounted incoming heat also lowers the estimate; outgoing heat raises it. These signs follow directly from the displayed energy balance. Conversely, dry ice initially below absorbs additional sensible heat; neglecting that term overestimates . These are different biases and may partially cancel, so agreement with a reference value alone does not validate the controls.
For this model with and , the balance predicts , with consumed by fusion and by warming the melted water. At with the same zero leak, it predicts and . A net incoming shifts downward by a further because . The warmer final water in the wet case is evidence of a smaller fusion budget, not a larger true .





