Thermodynamic Processes
- The four main thermodynamic processes are
- Isovolumetric
- Isobaric
- Isothermal
- Adiabatic
Constant pressure (isobaric)
- An isobaric process is defined as:
A process in which no change in pressure occurs
- This occurs when gases are allowed to expand or contract freely during a change in temperature
- When there is a change in volume ΔV at a constant pressure p, work done W is equal to
- From the first law of thermodynamics:
- The ± sign reflects whether work has been done on or by the gas as a result of the change in volume
Representing an isobaric process on a p-V diagram
Constant volume (isovolumetric)
- An isovolumetric process is defined as:
A process where no change in volume occurs and the system does no work
- If there is no change in volume, then there is no work done on or by the gas, so
- Therefore, from the first law of thermodynamics:
Representing an isovolumetric process on a p-V diagram
Constant temperature (isothermal)
- An isothermal process is defined as:
A process in which no change in temperature occurs
- If the temperature does not change, then the internal energy of the gas will not change, so
- Therefore, from the first law of thermodynamics:
Representing an isothermal process on a p-V diagram
Constant thermal energy (adiabatic)
- An adiabatic process is defined as:
A process where no heat is transferred into or out of the system
- If there is no heat entering or leaving the system then
- Therefore, from the first law of thermodynamics:
- This means that all the work done is at the expense of the system's internal energy
- Hence, an adiabatic process will usually be accompanied by a change in temperature
Representing an adiabatic process on a p-V diagram
Entropy in Thermodynamic Processes
- At a constant temperature T, the change in entropy is related to heat by
- When heat is gained by a system , entropy increases
- When heat is lost from a system , entropy decreases
- For a reversible process that returns the system to its original state
Process | Heat gained or lost, ΔQ | Change in entropy, ΔS | |
Isothermal |
Expansion |
Heat gained = work done by gas |
Increases |
Compression |
Heat lost = work done on gas |
Decreases |
|
Isobaric |
Expansion |
Heat gained = increase in internal energy + work done by gas |
Increases |
Compression |
Heat lost = decrease in internal energy + work done on gas |
Decreases |
|
Isovolumetric |
Pressure rise |
Heat gained due to temperature rise |
Increases |
Pressure drop |
Heat lost due to temperature drop |
Decreases |
|
Adiabatic |
Expansion |
Pressure & temperature decrease with no heat gained or lost |
No change |
Compression |
Pressure & temperature increase with no heat gained or lost |
No change |
Worked example
A quantity of energy Q is supplied to three ideal gases, X, Y and Z.
Gas X absorbs Q isothermally, gas Y isovolumetrically and gas Z isobarically.
Complete the table by inserting the words ‘positive’, ‘zero’ or ‘negative’ for the work done W, the change in internal energy ΔU and the temperature change ΔT for each gas.
X | |||
Y | |||
Z |
Answer:
- X: Isothermal = constant temperature, no change in internal energy
- Temperature:
- Internal energy: , so,
- Work done:
- Y: Isovolumetric = constant volume, no work done
- Work done: , so,
- Internal energy:
- Temperature: , so,
- Z: Isobaric = constant pressure
- Work done: , so , so
- Internal energy: , so
- Temperature: , so
X | positive | 0 | 0 |
Y | 0 | positive | positive |
Z | positive | positive | positive |
Worked example
A heat engine operates on the cycle shown in the pressure-volume diagram. One step in the cycle consists of an isothermal expansion of an ideal gas from state A of volume V to state B of volume 2V.
- an isovolumetric change from state B to state C
- an adiabatic compression from state C to state A
Answer:
(a)
- Isovolumetric = constant volume, no work done
- Next step is a compression (where pressure increases), so this step should involve a pressure drop
- Hence, B to C: line drawn vertically down
- Adiabatic = no heat supplied or removed, compression = work is done on the gas, volume decreases
- Hence, C to A: line curves up to meet A
(b)
- Entropy and heat (at a constant T) are related by
- From state A to state B:
- In an isothermal expansion, entropy increases
- Because T = constant but the volume increases so work is done by gas, ΔQ > 0 so ΔS > 0
- From state B to state C:
- In an isovolumetric change where pressure decreases, entropy decreases
- Because temperature decreases, so energy has been removed, ΔQ < 0 so ΔS < 0
- From state C to state A:
- In an adiabatic compression, entropy is constant
- Because it is an adiabatic process, ΔQ = 0 so ΔS = 0
- Therefore, entropy is greatest at B