1Why things spread
Lift the partition and a gas spreads through a whole box; it never gathers back into one half by itself, although that would conserve energy. The reason is counting. Four molecules can share two halves in 16 ways: all on one side in 1 way, 3 and 1 in 4 ways, 2 and 2 in 6 ways. With 100 molecules, all in one half is about 1 chance in ; with a real gas, it never happens.
- More spread out, more disordered → more ways → more entropy.
- Entropy is in J/K, is a state function, and adds up over the parts of a system.
- Entropy rises when ice melts, water evaporates or a gas spreads into a vacuum; it falls when water freezes, steam condenses or a gas is squeezed at constant temperature.
- At the same temperature, liquid water has more entropy than ice.
2Entropy from heat
At constant temperature, , with in kelvin. Heat in raises entropy; heat out lowers it; the same heat changes the entropy of a cold body more than that of a hot one. For a phase change, .
3The entropy law
When 1200 J flows from a body at 400 K to one at 300 K, the hot body loses J/K and the cold one gains J/K: the total rises by 1 J/K. In general
4Entropy of an ideal gas
Along a reversible path, with . Dividing by and integrating:
| Process | ΔS |
|---|---|
| Isothermal | |
| Isochoric | |
| Isobaric | |
| Reversible adiabatic | 0 (isentropic) |
| Phase change |
5Irreversible processes
Irreversible processes create entropy even with no heat. To find , use any reversible path between the same two states.
Copper blocks at 400 K and 200 K reaching 300 K: .
6Carnot and T–S diagrams
In a Carnot cycle the gas gains in step 1 and loses in step 3; the adiabatic steps change nothing. Since , these cancel, and so do the reservoirs' changes: a reversible engine creates no entropy. Example: 1000 J from 400 K to a 300 K sink: hot reservoir −2.5 J/K, cold +750/300 = +2.5 J/K, universe 0.
On a T–S diagram the Carnot cycle is a rectangle: flat isothermals and upright adiabatics (ΔS = 0). Since , the area under a path is the heat, and the area inside the loop is the work:
Summary
Key ideas
- Entropy counts the ways a state can happen: .
- Spread-out, disordered states have more ways, so more entropy.
- at a fixed temperature, in kelvin; unit J/K.
- The entropy of the universe never decreases; it stays constant only for reversible processes.
- Heat flowing from hot to cold increases the total entropy.
- A system's own entropy can fall if its surroundings gain more.
- A reversible adiabatic process is isentropic (ΔS = 0).
- Irreversible processes (free expansion, mixing, heat across a gap) create entropy even with Q = 0.
- On a T–S diagram the Carnot cycle is a rectangle whose area is the work.
Every equation
- Boltzmann
- Clausius
- Fixed T
- Phase change
- Second law
- Heat flow
- Ideal gas
- Isothermal
- Isochoric
- Isobaric
- Solids, liquids
- Two bodies
- T–S work