[Topic: Reversible Process (Contd…)]

Reversible Work
First condition is internal equilibrium. So 𝑇, 𝑃, etc. are uniform throughout.

Second, is mechanical equilibrium. 𝐹𝑒𝑥𝑡 = 𝑃𝑒𝑥𝑡 𝐴. The 𝑃𝑒𝑥𝑡 is external pressure, but because of
mechanical equilibrium, 𝑃𝑒𝑥𝑡 = 𝑃. This 𝑃 is the system’s pressure. Therefore we use equation
𝐹𝑒𝑥𝑡 = 𝑃𝐴.
𝑉𝑡
So we write the formula: 𝑊 = − ∫𝑉 𝑡2 𝑃𝑑𝑉 𝑡
1

𝑉 𝑡 , 𝑚; 𝑉 𝑡 /𝑚 = 𝑉

𝑇, 𝑃 inherently intensive properties.

𝑉
Then, 𝑊 = − ∫𝑉 2 𝑃𝑑𝑉
1

Summary
1) Frictionless.
2) Never more than differentially removed from equilibrium. Quasi-static equilibrium.
3) Traverses a succession of equilibrium states.
4) Driven by forces whose imbalance is differential in magnitude.
5) Can be reversed at any point by infinitesimal change in external conditions.
6) When reversed, retraces the forward path, and restores the initial state of system and
surroundings.

Pure homogeneous substance, 𝑇, 𝑃. Then you can calculate 𝑉 (you cannot decide a value for volume
if you have decided the values of 𝑇 and 𝑃).

For example: 𝑃𝑉 = 𝑅𝑇

Constant 𝑉 and Constant 𝑃 Closed System Processes

𝑛 moles of homogeneous fluid.

𝑑(𝑛𝑈) = 𝑑𝑄 + 𝑑𝑊
𝑑𝑊 = −𝑃𝑑(𝑛𝑉) (Mechanically reversible)

𝑑(𝑛𝑈) = 𝑑𝑄 − 𝑃𝑑(𝑛𝑉)
Constant 𝑉: Work is zero. Moreover, 𝑛 and 𝑉 are both constants:

𝑑(𝑛𝑈) = 𝑑𝑄 (Const 𝑉) (1A)

𝑄 = 𝑛∆𝑈 (Const 𝑉) (1B)

Constant 𝑃:

𝑑𝑄 = 𝑑(𝑛𝑈) + 𝑃𝑑(𝑛𝑉)
𝑑𝑄 = 𝑑(𝑛𝑈) + 𝑑(𝑛𝑃𝑉) = 𝑑[𝑛(𝑈 + 𝑃𝑉)] (const P)
𝐻 ≡ 𝑈 + 𝑃𝑉 (2)

𝑑𝑄 = 𝑑(𝑛𝐻) (Const 𝑃) (3A)

𝑄 = 𝑛∆𝐻 (Const 𝑃) (3B)

So enthalpy plays a role in const 𝑃 process analogous to internal energy in const 𝑉 process.

Enthalpy
Like internal energy, enthalpy is for both closed as well as open systems.

In fact it is much more useful for open systems as it appears in energy balance for open systems (we
will discuss ahead).

Because the values of 𝑄 and 𝑊 are path dependent, they cannot be tabulated.

Intensive State functions can be tabulated. So tables of intensive state functions of many substances
are available, for example steam tables for water. Pls search internet and see your textbook for
steam tables.

All the terms in Eq. (2) have the same units, those of energy / mass or energy / mole. E.g. J/kg, or
cal/lb-mol etc.

𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)= dU+PdV+VdP

∆𝐻 = ∆𝑈 + ∆(𝑃𝑉)

Heat Capacity
Historically it was thought that a body has a capacity to retain heat. Now we know heat is energy in
transit, but the name heat capacity is still used.

𝐶 ≡ 𝑑𝑄/𝑑𝑇

Heat Capacity at Constant Volume

𝐶𝑉 ≡ (𝜕𝑈/𝜕𝑇)𝑉
d and partial derivative are same. Except, that partial derivative is used when the dependent
function is dependent on two or more independent variables. Molar heat capacity as well as specific
heat capacity (usually called specific heat).

For a constant-volume process in a closed system:

𝑑𝑈 = 𝐶𝑉 𝑑𝑇 (const 𝑉)
𝑇
∆𝑈 = ∫𝑇 2 𝐶𝑉 𝑑𝑇 (const 𝑉)
1

For mechanically reversible constant volume process, combination with Eqs (1):
𝑇
𝑄 = 𝑛∆𝑈 = 𝑛 ∫𝑇 2 𝐶𝑉 𝑑𝑇 (Const 𝑉)
1

Constant volume process: the volume remains const throughout the course of process.

If process is not const 𝑉, but only 𝑉2 = 𝑉1. Then ∆𝑉 = 0.

Changes in state functions are independent of path. Because 𝑈, 𝐶𝑉 , 𝑉, and 𝑇 are all state functions,
𝑇
so even then also 𝑛∆𝑈 = 𝑛 ∫𝑇 2 𝐶𝑉 𝑑𝑇.
1

𝑇
However, because 𝑄 is a path function, so 𝑄 = 𝑛∆𝑈 = 𝑛 ∫𝑇 2 𝐶𝑉 𝑑𝑇 only for a const volume process.
1

For the calculation of property changes, but not for Q and W, an actual process may be replaced
by any other process that accomplishes the same change in state. The choice is made based on
convenience, with simplicity a great advantage.

Heat Capacity at Constant Pressure

𝐶𝑃 ≡ (𝜕𝐻/𝜕𝑇)𝑃
Both molar and specific.

For a closed system, constant pressure process:

𝑑𝐻 = 𝐶𝑃 𝑑𝑇 (const 𝑃)
𝑇
∆𝐻 = ∫𝑇 2 𝐶𝑃 𝑑𝑇 (const P)
1

For a mechanically reversible, constant pressure process combination with Eqs (3):
𝑇
𝑄 = 𝑛∆𝐻 = 𝑛 ∫𝑇 2 𝐶𝑃 𝑑𝑇 (const P)
1

𝑇
Again even when process is not const P, however 𝑃2 = 𝑃1 , even then 𝑛∆𝐻 = 𝑛 ∫𝑇 2 𝐶𝑃 𝑑𝑇.
1

𝑇
However, 𝑄 = 𝑛∆𝐻 = 𝑛 ∫𝑇 2 𝐶𝑃 𝑑𝑇 is true only when the process is truly const P. And only then
1
𝑊 = −𝑃𝑛∆𝑉.

Example 2.10

T
V

P P

Law of Balances
ALLAH (SWT) has created things in balance. For example total mass in = total mass out, total energy
in = total energy out, total reactants in = total products out. Similarly good deeds in = good results
out, bad deeds in = bad results out.

Deeds Worldly Life Results

Solve Problems 2.1, 2.3 to 2.18. Solve all examples up to Example 2.10.

Mass and Energy Balances for Open Systems

Laws apply equally well for open systems. Open systems are far more common and so important.

Measures of Flow
Mass flowrate, 𝑚̇ Molar flowrate, 𝑛̇ Volumetric flowrate, 𝑞 Velocity, 𝑢

𝑚̇ = 𝑀𝑛̇ 𝑞 = 𝑢𝐴
𝜌 = 𝑚/𝑉 𝑡 = 𝑚̇/𝑞 = 𝑚̇/𝑢𝐴 𝑚̇ = 𝑢𝐴𝜌 𝑛̇ = 𝑢𝐴𝜌 (4)