Page 1 of 6 SPH 2202 – Thermal Physics I Lecture notes

Thermodynamic work
Definition of terms
 Thermodynamic transformation – when a thermodynamic system undergoes a change in state, say,
from an initial state (𝑃𝑖 , 𝑉𝑖 , 𝑇𝑖 ) to a final state (𝑃𝑓 , 𝑉𝑓 , 𝑇𝑓 ).
A thermodynamic transformation can be either reversible or irreversible.

 Reversible transformation – when a thermodynamic system undergoes a thermodynamic transformation

that has well-defined initial and final states as well as well-defined values for all its state variables
throughout the transformation.
o The system is therefore in (very nearly) thermodynamic equilibrium throughout the transformation,
and transforms from an initial state to a final state and in the reverse direction along the same path.
o The transformation can thus be plotted (on a P-V diagram).

𝑃
𝑖

o In order to achieve a reversible transformation (a necessary condition for reversibility),

 The transformation must be very slow ⇒ quasi-static transformation (infinitely slow).
Quasi-static transformation – a sufficiently slow process, any intermediate state can be considered
as an equilibrium state.
 There must be no friction or other energy dissipation effects.
o A reversible transformation is an idealised transformation.
o Examples of reversible processes:
 Extension of springs.
 Electrolysis (with no resistance in the electrolyte).
 The frictionless motion of solids.
 Slow adiabatic compression or expansion of gases.
 Slow isothermal compression or expansion of gases.

 Irreversible transformation – when a thermodynamic system undergoes a thermodynamic

transformation that has well-defined initial and final states but no well-defined values for all its state
variables (i.e. the transformation path is not well-defined).
o The system is therefore not in thermodynamic equilibrium at any given time, and can thus not be
plotted.

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Page 2 of 6 SPH 2202 – Thermal Physics I Lecture notes

𝑃
𝑖
?
𝑓

𝑉
o Examples of irreversible processes:
 Relative motion with friction.
 Heat transfer.
 Diffusion.
 Electricity flow through a resistance.

 Most real processes are irreversible. However, a few processes, such as adiabatic processes, can
approach the reversible idealisation.

 Although real thermodynamic processes are most certainly irreversible, reversible transformations have
to be assumed in order to develop thermodynamic principles. This helps us understand how to make real
processes more efficient.

 Thermodynamic work – illustration: a gas enclosed in a vessel by a movable piston:

o The gas molecules exert a force on each other and against the walls of the vessel and the piston,
hence causing some uniform pressure (𝑃). This pressure causes the piston to go through an
infinitesimally small displacement (𝑑𝑥).
o Thus, force on the piston,
𝐹 = 𝑃𝐴
o And, work done by the gas on the surrounding,
𝑑𝑊 = 𝐹 ∙ 𝑑𝑥
𝑑𝑊 = (𝑃 ∙ 𝐴) ∙ 𝑑𝑥
𝑑𝑊 = 𝑃 ∙ (𝐴 ∙ 𝑑𝑥)

𝑑𝑊 = 𝑃 ∙ 𝑑𝑉 = 𝑃(𝑉𝑓 − 𝑉𝑖 )

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Page 3 of 6 SPH 2202 – Thermal Physics I Lecture notes

 For an expansion (i.e. 𝑉𝑓 > 𝑉𝑖 ) ⇒ system does work on the surrounding i.e. the system loses energy
→ value of the work done is assigned a negative value.

 For a compression (i.e. 𝑉𝑓 < 𝑉𝑖 ) ⇒ work is done on the system by the surrounding i.e. the system
gains energy → value of the work done is assigned a positive value.

Instead of assigning a negative value for work done during an expansion (system losses energy) and
a positive value for work done during a compression (system gains energy), by convention, a
negative sign is inserted in front of the formula for the work done. This has the same end result: a
negative value for work done during an expansion, and a positive value for work done during a
compression.
Thus, the formula becomes,
𝑑𝑊 = −𝑃 ∙ 𝑑𝑉

 If the gas transforms from an initial state 𝑖 to a final state 𝑓, with the corresponding volume 𝑉𝑖 and 𝑉𝑓
respectively, work done by the gas is the integral,
𝑉𝑓
𝑊𝑖𝑓 = − ∫ 𝑃 ∙ 𝑑𝑉
𝑉𝑖

 𝑊𝑖𝑓 → the work equation for a hydrostatic system that transforms quasi-statically and reversibly from an
initial state 𝑖 to a final state 𝑓.
 The unit for the work done is the Joule (J).

 Illustrative examples:

1. Determine the work done on an ideal gas that is expanded to twice its original volume of 1.00 m3 in a
quasi-static process for which 𝑃 = 𝛼𝑉 2 (where, 𝛼 = 5.00 𝑎𝑡𝑚⁄𝑚6 ) as shown in the figure below. Take
1 𝑎𝑡𝑚 = 1.01 × 105 𝑃𝑎.

Solution:
𝑉 𝑉 𝑉 1
- 𝑊𝑖𝑓 = − ∫𝑉 𝑓 𝑃 ∙ 𝑑𝑉 = − ∫𝑉 𝑓 (𝛼𝑉 2 ) ∙ 𝑑𝑉 = −𝛼 ∫𝑉 𝑓 𝑉 2 ∙ 𝑑𝑉 = − 3 𝛼(𝑉𝑓3 − 𝑉𝑖3 )
𝑖 𝑖 𝑖
Note: In integral calculus, this is equivalent to the area under the curve 𝑃 = 𝛼𝑉 2 .

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Page 4 of 6 SPH 2202 – Thermal Physics I Lecture notes

- 𝛼 = 5.00 𝑎𝑡𝑚⁄𝑚6 = 5.00 × 1.01 × 105 𝑃𝑎⁄𝑚6 ; 𝑉𝑖 = 1.00 𝑚3 ; 𝑉𝑓 = 2.00 𝑚3

1
- 𝑊𝑖𝑓 = − 3 (5.05 × 105 𝑃𝑎⁄𝑚6 )[(2.00𝑚3 )3 − (1.00𝑚3 )3 ] 𝑃𝑎 ∙ 𝑚3 =
𝑁
∙ 𝑚3 = 𝑁 ∙ 𝑚 ≡ 𝐽
𝑚2

- 𝑊𝑖𝑓 = −1.18 × 106 𝑃𝑎 ∙ 𝑚3 = −1.18 × 106 𝐽

- 𝑊𝑖𝑓 = −1.18 𝑀𝐽

NB: The negative result for the work done indicates the transformation was an expansion.

2. A hydrostatic system transforms from an initial state 𝑖 to a final state 𝑓 characterized by the
thermodynamic coordinates 𝑃𝑖 , 𝑉𝑖 , 𝑇𝑖 and 𝑃𝑓 , 𝑉𝑓 , 𝑇𝑓 respectively. In doing so, three different paths are used
where the system transforms from the initial state 𝑖 to the final state 𝑓 through 𝑎, through 𝑏, and through
a straight line from 𝑖 to 𝑓, as illustrated in the figure below:

Determine the work done in each of the three paths.

Solution:
 Option I: 𝑑𝑊 = −𝑃 ∙ 𝑑𝑉
Note: for an isovolumetric process (also called isochoric process), 𝑑𝑉 = 0 and hence 𝑊 = 0
Thus,
i. 𝑊𝑖 𝑡𝑜 𝑓 𝑡ℎ𝑟𝑜′ 𝑎 = 𝑊𝑖 𝑡𝑜 𝑎 + 𝑊𝑎 𝑡𝑜 𝑓 = −2𝑃0 (2𝑉0 − 𝑉0 ) + 0 = −2𝑃0 𝑉0

ii. 𝑊𝑖 𝑡𝑜 𝑓 𝑡ℎ𝑟𝑜′ 𝑏 = 𝑊𝑖 𝑡𝑜 𝑏 + 𝑊𝑏 𝑡𝑜 𝑓 = 0 + −𝑃0 (2𝑉0 − 𝑉0 ) = −𝑃0 𝑉0

 Option II: 𝑊 ≡ 𝑎𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑡ℎ𝑒 𝑔𝑟𝑎𝑝ℎ 𝑓𝑜𝑟 𝑒𝑎𝑐ℎ 𝑝𝑎𝑡ℎ.

Thus,
i. Path 𝑖 to 𝑓 through 𝑎:- area under the graph is a rectangle of area 2𝑃0 × 𝑉0 = 2𝑃0 𝑉0 .
And since the transformation is an expansion, assign the area obtained a negative sign. Thus,
𝑊𝑖 𝑡𝑜 𝑓 𝒕𝒉𝒐𝒖𝒈𝒉 𝒂 = −2𝑃0 𝑉0
ii. Path 𝑖 to 𝑓 through 𝑏:- area under the graph is a rectangle of area 𝑃0 × 𝑉0 = 𝑃0 𝑉0 . Therefore,
𝑊𝑖 𝑡𝑜 𝑓 𝒕𝒉𝒐𝒖𝒈𝒉 𝒃 = −𝑃0 𝑉0

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Page 5 of 6 SPH 2202 – Thermal Physics I Lecture notes
(2𝑃0 +𝑃0 ) 3
iii. Straight path 𝑖 to 𝑓:- area under the graph is a trapezium of area × 𝑉0 = 2 𝑃0 𝑉0 .
2
3
Therefore, 𝑊𝑖 𝑡𝑜 𝑓 (𝒔𝒕𝒓𝒂𝒊𝒈𝒉𝒕 𝒑𝒂𝒕𝒉) = − 2 𝑃0 𝑉0

 NOTE: In transforming from initial state 𝑖 to the final state 𝑓, three different paths have been
considered. Each of these different paths has resulted into a unique value of the work done.
⇒ the magnitude of thermodynamic work done depends on the path taken.

3. A two moles ideal gas kept at a constant temperature of 20°C is compressed from a volume of 4 liters to
1 liter. Calculate the work done during the process (take universal gas constant 𝑅 = 8.314 𝐽/𝑚𝑜𝑙 ∙ 𝐾).
Solution:
𝑉
- From the formula, 𝑊 = − ∫𝑉 𝑓 𝑃 ∙ 𝑑𝑉
𝑖
𝑛𝑅𝑇
But for an ideal gas, 𝑃 = . Thus,
𝑉
𝑉𝑓 𝑉𝑓 𝑉𝑓
𝑛𝑅𝑇 1
𝑊 = −∫ ∙ 𝑑𝑉 = −𝑛𝑅𝑇 ∫ ∙ 𝑑𝑉 = −𝑛𝑅𝑇(ln 𝑉𝑓 − ln 𝑉𝑖 ) = −𝑛𝑅𝑇 ln
𝑉𝑖 𝑉 𝑉𝑖 𝑉 𝑉𝑖

- Work done in compressing the gas is thus,

1
𝑊 = −(2 𝑚𝑜𝑙)(8.314 𝐽𝑚𝑜𝑙 −1 𝐾 −1 )(293.15 𝐾) (ln ) = 6753 𝐽
4

- The answer is positive because work is done by the surrounding on the system (compression).

- Generally, work done during a quasi-static isothermal compression/expansion of an ideal gas is

given by the formula,
𝑉𝑓
𝑊𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛 𝑜𝑟 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛 𝑜𝑓 𝑎𝑛 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 = −𝑛𝑅𝑇 ln
𝑉𝑖

4. The pressure on 10 g of solid copper is increased quasi-statically and isothermally at 20°C from 0 to
1000 atm (1 𝑎𝑡𝑚 = 1.013 × 105 Pa). Calculate the work done (take 𝜅𝑐𝑜𝑝𝑝𝑒𝑟 = 7.16 × 10−12 Pa−1 ,
𝜌𝑐𝑜𝑝𝑝𝑒𝑟 = 8.96 × 103 kgm−3 ).
Solution:
- Recall: 𝑑𝑉 = 𝑉 ∙ 𝛽 ∙ 𝑑𝑇 − 𝑉 ∙ 𝜅 ∙ 𝑑𝑃
Where, 𝛽 ≡ volume expansivity and 𝜅 ≡ isothermal compressibility.
But, since the process is isothermal, 𝑑𝑇 = 0 and thus 𝑑𝑉 = −𝑉 ∙ 𝜅 ∙ 𝑑𝑃.
- From the equation for work done i.e.
𝑉𝑓
𝑊 = − ∫ 𝑃 ∙ 𝑑𝑉
𝑉𝑖
The volume integral can be replaced with a pressure integral by substituting 𝑑𝑉 with −𝑉 ∙ 𝜅 ∙ 𝑑𝑃.
Thus,
𝑉𝑓 𝑃𝑓 𝑃𝑓
𝑊 = − ∫ 𝑃 ∙ 𝑑𝑉 = − ∫ 𝑃 ∙ (−𝑉 ∙ 𝜅 ∙ 𝑑𝑃) = ∫ 𝜅 ∙ 𝑉 ∙ 𝑃 ∙ 𝑑𝑃
𝑉𝑖 𝑃𝑖 𝑃𝑖
On integrating,
𝜅∙𝑉 2
𝑊= (𝑃𝑓 − 𝑃𝑖2 )
2

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Page 6 of 6 SPH 2202 – Thermal Physics I Lecture notes
- Work done on the solid copper is thus,
𝜅∙𝑉 2 𝜅 𝑚 𝑚
𝑊= (𝑃𝑓 − 𝑃𝑖2 ) ≈ ∙ (𝑃𝑓2 − 𝑃𝑖2 ) ; 𝑠𝑖𝑛𝑐𝑒 𝑉 = , 𝑚 ≡ mass and 𝜌 ≡ density
2 2 𝜌 𝜌
(7.16 × 10−12 Pa−1 )(10−2 kg)
≈ (1000 × 1.013 × 105 Pa) ≈ 4.08 Pa ∙ m3 = 4.08 J
2(8.96 × 103 kgm−3 )

- Generally, work done during a quasi-static isothermal increase of pressure on a solid is given by
the formula,
𝜅∙𝑉 2
𝑊𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒/𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑜𝑓 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑛 𝑎 𝑠𝑜𝑙𝑖𝑑 = (𝑃𝑓 − 𝑃𝑖2 )
2

 Note: Work equations for other types of thermodynamic systems are different. They relate to, for instance,
work done in,
i. changing the length of a wire,
ii. changing the area of a thin film,
iii. moving charge in an electrochemical cell,
iv. etc.

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