Thermodynamics
1. What this chapter covers
| Textbook section | Topic |
|---|---|
| 11.1 | Introduction |
| 11.2 | Thermal equilibrium |
| 11.3 | Zeroth law of thermodynamics |
| 11.4 | Heat, internal energy and work |
| 11.5 | First law of thermodynamics |
| 11.6 | Specific heat capacity |
| 11.7 | Thermodynamic state variables and equation of state |
| 11.8 | Thermodynamic processes |
| 11.9 | Second law of thermodynamics |
| 11.10 | Reversible and irreversible processes |
| 11.11 | Carnot engine |
Thermodynamics does not care what a system is made of. Whether it is a gas in a cylinder, a chemical reaction, or a star, the same handful of laws governs how heat and work move in and out of it. That is also why this chapter is short on things to memorise and long on things to reason through — every quantity here traces back to just two laws.
2. Systems, state variables, and what "equilibrium" actually means
| System type | Exchanges with surroundings | Example |
|---|---|---|
| Open | Matter and energy | Tea in an open cup |
| Closed | Energy only, no matter | Gas in a cylinder with a movable piston |
| Isolated | Neither | Gas in a rigid, insulated container |
A gas in a closed cylinder is described by a handful of state variables — pressure, volume, temperature, mass, composition. Not all state variables behave the same way when you split the system in two. Take a gas in equilibrium and imagine dividing it into two equal halves:
- Intensive variables — pressure, temperature, density — stay the same in each half.
- Extensive variables — volume, mass, internal energy — halve along with the system.
This is a genuinely useful check, not a classification exercise: in any correct thermodynamic equation, both sides must carry the same extensive/intensive character. In , every term is extensive — is intensive, but is the product of an intensive and an extensive quantity, so it comes out extensive too, matching and .
A gas obeying is said to satisfy an equation of state — a relation connecting the state variables so that, for a fixed amount of gas, only two of them are independent.
State variables describe equilibrium states only. A gas expanding freely into a vacuum, or an explosive combustion, passes through states where pressure is not even uniform through the container — those in-between states have no well-defined and cannot be plotted on a state diagram at all.
3. The zeroth law: how temperature gets a rigorous meaning
Before the zeroth law, "temperature" was just a feeling of hot and cold. The law that finally pins it down mathematically is almost embarrassingly simple, which is exactly why it was named after the first and second laws were already numbered — it was formulated by R.H. Fowler in 1931, decades later, once physicists realised the first and second laws silently assumed it.
Picture systems A and B, each separated from a third system C by a wall that conducts heat, while A and B are kept apart by an insulating wall. Left long enough, A and C reach thermal equilibrium, and separately, B and C reach thermal equilibrium. Now replace the A–B insulating wall with a conducting one. Experimentally, nothing changes — A and B are already in equilibrium with each other.
Zeroth law: If two systems are each in thermal equilibrium with a third system, they are in thermal equilibrium with each other.
The payoff is that this guarantees a shared quantity exists — call it temperature — such that and imply . Without the zeroth law, there would be no guarantee that "same temperature" is even a consistent, transitive property to assign to bodies at all.
4. Heat, work, and internal energy — three ideas the chapter insists you keep separate
Internal energy is the sum of the kinetic and potential energies of a system's molecules, measured in the frame where the system's centre of mass is at rest — so a fast-moving bullet is not "hotter" just because it is fast; its internal energy is about the disordered motion of its molecules, not the bullet's overall flight. Crucially, is a state variable: its value depends only on the system's current state, never on how it got there.
Heat and work are not state variables. They are the two ways a system's internal energy can change:
- Heat — energy transfer caused by a temperature difference between system and surroundings.
- Work — energy transfer by any other means (moving a piston, stirring, compressing).
This distinction sounds pedantic until you try to use it: "this gas contains 500 J of heat" is meaningless — heat is not a thing a system has, only a thing that flows. "This gas absorbed 500 J of heat" and "this gas has 500 J more internal energy than before" are both perfectly meaningful, and they are not the same statement.
5. The First Law: energy bookkeeping with a sign convention to fix first
- — heat supplied to the system by the surroundings (positive when added)
- — work done by the system on the surroundings (positive when the system expands and pushes outward)
- — change in internal energy
Rearranged, this is the more familiar . Both forms say exactly the same thing; the only way to get it wrong is to mix sign conventions mid-problem — for instance treating "work done on the system" as positive while still using this formula, which silently flips every answer's sign. Fix the convention before touching a number.
Because is a state variable and , are not, depends only on the initial and final states — but and individually can differ across two different paths connecting the same two states, even though stays fixed. This single fact is the whole reason isothermal and adiabatic processes between the same two temperatures give different work done, while tracks only .
Worked example (from the textbook). One gram of water turns to steam at atmospheric pressure. Its latent heat is 2256 J/g, so J. At atmospheric pressure, the volume goes from (liquid) to (vapour):
Most of the heat supplied does not go into pushing back the atmosphere — it goes into pulling the water molecules apart against their own attraction, which is exactly what "internal energy" was defined to capture.
6. Specific heat capacity — and where actually comes from
For a substance of mass absorbing heat for a temperature rise , specific heat capacity is . Per mole instead of per unit mass, it is the molar specific heat capacity .
For solids, the law of equipartition of energy — which is properly the subject of the next chapter, Kinetic Theory, but the textbook borrows the result here — predicts each of atoms vibrating in three dimensions carries average energy , giving total energy per mole and therefore (the Dulong-Petit law).
It matches experiment well at ordinary temperatures for most solids (carbon is a known exception), and is known to break down at low temperature.
For gases, specific heat depends on how the heat is supplied — at constant volume or constant pressure — because at constant pressure some of the heat also does work pushing the gas's own boundary outward. Starting from for one mole:
- At constant volume, , so — heat only builds internal energy.
- At constant pressure, . Since for an ideal gas depends only on , the first term is the same either way. Using for one mole, .
This is Mayer's relation, and it only holds for an ideal gas — the derivation leans on depending on temperature alone, which is an ideal-gas property.
7. Thermodynamic processes: the quasi-static idealisation, and five named cases
If you suddenly drop the external pressure on a gas, the piston accelerates outward and the gas passes through states where pressure is not even uniform inside the container — not equilibrium states, and therefore not describable by a single .
To keep the mathematics tractable, thermodynamics idealises processes as quasi-static: infinitely slow, so the system stays in equilibrium with its surroundings — differing in pressure and temperature only infinitesimally — at every instant. A quasi-static process is, strictly, a hypothetical construct; real "slow enough" processes are just good approximations to it.
| Process | Held fixed | First law becomes | Work done by gas |
|---|---|---|---|
| Isothermal | |||
| Adiabatic | |||
| Isochoric | |||
| Isobaric | |||
| Cyclic | returns to start | net area enclosed on - diagram |
Isothermal work, derived directly: for an ideal gas at fixed , , so
Because depends only on for an ideal gas, here, so all of this work is paid for entirely by heat absorbed from the surroundings: .
Adiabatic, by contrast, has by definition, so any work the gas does comes directly out of its own internal energy — the gas cools as it expands adiabatically, and heats as it is compressed adiabatically. For an ideal gas undergoing an adiabatic change,
On a – diagram, the adiabatic curve through any point is steeper than the isothermal curve through the same point — an isothermal expansion loses pressure only because volume rises; an adiabatic expansion loses pressure for that and because temperature is falling too, so pressure drops faster for the same .
8. The Second Law: why the First Law alone allows nonsense
The First Law permits a book on a table to spontaneously cool the table and hop into the air, converting the table's lost internal energy exactly into the book's gained potential energy — total energy is conserved throughout. It never happens. Something beyond energy conservation is needed to rule it out, and that something is the Second Law.
Kelvin-Planck statement: No process is possible whose sole result is the absorption of heat from a reservoir and its complete conversion into work.
Clausius statement: No process is possible whose sole result is the transfer of heat from a colder body to a hotter one.
These read as two different claims but are provably equivalent — each can be shown to imply the other. In practice, they say the same thing two ways: a perfect heat engine (100% efficient) is impossible, and a perfect refrigerator (moving heat uphill for free) is impossible.
9. Reversible and irreversible processes
A process is reversible if it can be run backward so that both system and surroundings return exactly to their original states, with no trace left anywhere in the universe. Nearly nothing in nature qualifies. Two separate reasons break reversibility:
- Non-equilibrium states — free expansion, explosive combustion, sudden mixing — the system passes through states with no well-defined pressure or temperature, and there is no way to walk that path backward in the same steps.
- Dissipation — friction, viscosity, electrical resistance — always converts ordered mechanical or electrical energy into disordered heat, and that conversion cannot be un-done without external help.
A vessel's base cools by conducting heat to its cooler sides, never the reverse. A stirred liquid's kinetic energy becomes heat in the liquid; the liquid never spontaneously un-stirs itself and cools the stirring rod. Reversibility requires both quasi-static behaviour and zero dissipation — a slow isothermal expansion in a frictionless cylinder is about as close as physics gets.
10. The Carnot engine — and why nothing can beat it
A heat engine absorbs heat from a hot reservoir, delivers work , and rejects the rest, , to a cold reservoir; efficiency is . Sadi Carnot asked, in 1824, what the best possible efficiency between two fixed temperatures could be — and worked out the answer before heat was even properly understood as energy.
An ideal reversible engine operating between just two temperatures must use only isothermal steps (to absorb and reject heat without a finite temperature gap) and adiabatic steps (to change temperature without exchanging heat at all) — any other process would need a whole ladder of intermediate reservoirs. That gives the four-step Carnot cycle:
- Isothermal expansion at : absorbs , does work .
- Adiabatic expansion: , no heat exchanged.
- Isothermal compression at : rejects , work done on gas .
- Adiabatic compression: , back to the start.
Working through the algebra (the two adiabatic legs force ), the volume ratios cancel and the efficiency collapses to a strikingly clean result:
depending on nothing but the two reservoir temperatures — not on the working substance, not on the gas used to derive it.
Why can no engine beat this — and this is provable, not asserted. Suppose an irreversible engine I could exceed a Carnot engine's efficiency, , both running between the same two reservoirs. Couple them: let I absorb from the hot reservoir and deliver work , and run R backward, as a refrigerator, driven by a smaller work input , to pump exactly back into the hot reservoir.
Since (that is what means for the same ), the combined I+R system takes heat from the cold reservoir alone and converts it entirely into work, with the hot reservoir completely unchanged. That is exactly what the Kelvin-Planck statement forbids.
So the assumption fails: no engine, reversible or not, can exceed the Carnot efficiency between the same two temperatures. The same coupling argument shows a reversible engine's efficiency cannot depend on what it is made of — one Carnot engine cannot beat another built from a different substance either, which is why using an ideal gas to derive is enough to fix the answer for every Carnot engine.
One more consequence worth carrying forward: since for any Carnot engine regardless of substance, is a relation that involves no material property at all — it can be used to define a temperature scale from heat ratios alone, independent of what thermometer or gas is used to measure it.
Summary
- The zeroth law makes "temperature" a rigorous, transitive property: two systems each in equilibrium with a third are in equilibrium with each other.
- Internal energy is a state variable; heat and work are not — they are the two paths by which changes, and their individual values depend on the path taken even when does not.
- The first law, , is energy conservation with heat included. Fix the sign convention before solving anything.
- holds only for an ideal gas, and follows directly from applied at constant and constant .
- Isothermal, adiabatic, isochoric, isobaric, and cyclic processes are five named cases of the same first law, distinguished by what is held fixed.
- The second law forbids what the first law alone allows: a heat engine can never be 100% efficient (Kelvin-Planck), and heat never flows spontaneously from cold to hot (Clausius) — the two statements are equivalent.
- Reversibility demands both a quasi-static process and zero dissipation; almost nothing in nature meets both conditions.
- The Carnot engine's efficiency, , is not just the best known efficiency — Carnot's theorem proves it is the best possible one, using nothing but the Kelvin-Planck statement and a thought experiment coupling two engines.
