ME 221 Thermodynamics 2 [Module 3: Processes of Pure Substance] Engr. Juanito M. Origines Jr.

Processes of Pure Substance

Definition:

Process – whenever a system undergoes any changes, it is said to have described a process.
Quasi-static process – a process in which system departs from equilibrium state only
infinitesimally at every instant.

Reversible process – process that can be reverse without leaving any trace on the surroundings. A
processes that are not reversible are called irreversible processes.

Internally Reversible – no irreversibilities that occur within the boundaries of the system during
the process. In this process the system proceeds through a series of equilibrium states, and when
the process is reversed, the system passes through exactly the same equilibrium states while
returning to its initial states. One example of this process is the quasi-equilibrium process.

Externally Reversible – no irreversibilities occur outside the system boundaries during the
process.

Total Reversible or simple Reversible – no irreversibilities within the system or its surroundings.

Energy Analysis:

Closed System (Control Mass):

𝑄 = ∆𝐸𝑠𝑦𝑠 + 𝑊𝑛𝑓 (General Energy Equation)

𝑄 = ∆𝑈 + 𝑊𝑛𝑓 (Stationary System)

where: 𝑊𝑛𝑓 = 𝑊𝑏 + 𝑊𝑜𝑡ℎ𝑒𝑟 = ∫ 𝑃𝑑𝑉 + 𝑊𝑜𝑡ℎ𝑒𝑟

Open System (Control Volume):

𝑄 = ∆𝑃. 𝐸. +∆𝐾. 𝐸. +∆𝐻 + 𝑊𝑠𝑓 (General Energy Equation for steady state, steady-flow)

𝑊𝑠𝑓 = 𝑄 − ∆𝐻 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

𝑊𝑠𝑓 = − ∫ 𝑉𝑑𝑃 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

Second Law Analysis:

Entropy: S
▪ Consequence of the second law of thermodynamics
▪ Entropy is a measure of randomness or disorder of the molecules of a substance
▪ An abstract property, best understood by studying its uses in commonly encountered
engineering processes.

Clausius Inequality: [by German physicist R.J.E. Clausius (1822 – 1888)]

- An important inequality that has a major consequences in thermodynamics

The cyclic integral of 𝛿𝑄/𝑇 is less than or equal to zero.

- For totally or internally reversible process/cycle:

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ME 221 Thermodynamics 2 [Module 3: Processes of Pure Substance] Engr. Juanito M. Origines Jr.

- Clausius realized in 1865 that he had discovered a new thermodynamic property, and he chose to name
this property entropy. It is designated by symbol S and is defined as

- The entropy change of a system during a process is found by integrating dS:

Note: Vapors (steam) and ideal gases have similarity in their processes but ideal gas equations are
not generally applicable to vapors.

I. Isometric (Isochoric/Isovolumic) Process:

- An internally reversible constant volume process of a pure substance.

a. P-V and T-S diagrams

b. Nonflow Work
𝑖𝑓 𝑊𝑛𝑓 = 𝑊𝑏 = ∫ 𝑃𝑑𝑉 = 0 𝑓𝑜𝑟 𝑑𝑉 = 0
c. Steady flow Work
𝑊𝑠𝑓 = 𝑄 − ∆𝐻 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

𝑊𝑠𝑓 = − ∫ 𝑉𝑑𝑃 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

𝑊𝑠𝑓 = −𝑚𝑣(𝑃2 − 𝑃1 ) − ∆𝑃. 𝐸. −∆𝐾. 𝐸.
d. Change in Internal Energy
∆𝑈 = 𝑚(𝑢2 − 𝑢1 )
e. Change in Enthalpy
∆𝐻 = 𝑚(ℎ2 − ℎ1 )

f. Change in Entropy

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ME 221 Thermodynamics 2 [Module 3: Processes of Pure Substance] Engr. Juanito M. Origines Jr.

∆𝑆 = 𝑚(𝑠2 − 𝑠1 )
g. Heat Transferred
𝑄 = ∆𝑈

II. Isobaric Process

An internally reversible constant pressure process of a pure substance

a. P-V and T-S diagrams

b. Nonflow Work
𝑖𝑓 𝑊𝑛𝑓 = 𝑊𝑏 = ∫ 𝑃𝑑𝑉 = 𝑃(𝑉2 − 𝑉1 ) = 𝑚𝑃(𝑣2 − 𝑣1 )
c. Steady flow Work
𝑊𝑠𝑓 = 𝑄 − ∆𝐻 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

𝑊𝑠𝑓 = − ∫ 𝑉𝑑𝑃 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

𝑊𝑠𝑓 = 0 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.
d. Change in Internal Energy
∆𝑈 = 𝑚(𝑢2 − 𝑢1 )
e. Change in Enthalpy
∆𝐻 = 𝑚(ℎ2 − ℎ1 )
f. Change in Entropy
∆𝑆 = 𝑚(𝑠2 − 𝑠1 )
g. Heat Transferred
𝑄 = ∆𝐻

III. Isothermal Process

- Internally reversible constant temperature process of a pure substance

a. P-V and T-S diagrams

b. Nonflow Work
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ME 221 Thermodynamics 2 [Module 3: Processes of Pure Substance] Engr. Juanito M. Origines Jr.

𝑊𝑛𝑓 = 𝑄 − ∆𝑈
c. Steady flow Work
𝑊𝑠𝑓 = 𝑄 − ∆𝐻 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

𝑊𝑠𝑓 = − ∫ 𝑉𝑑𝑃 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.

d. Change in Internal Energy
∆𝑈 = 𝑚(𝑢2 − 𝑢1 )
e. Change in Enthalpy
∆𝐻 = 𝑚(ℎ2 − ℎ1 )
f. Change in Entropy
∆𝑆 = 𝑚(𝑠2 − 𝑠1 )
g. Heat Transferred
𝑄 = 𝑇(∆𝑆)

IV. Isentropic Process ( Internally Reversible Adiabatic Process)

- Internally reversible constant entropy process of a pure substance

a. P-V and T-S diagrams

b. Nonflow Work
𝑊𝑛𝑓 = −∆𝑈
c. Steady flow Work
𝑊𝑠𝑓 = −∆𝐻 − ∆𝑃. 𝐸. −∆𝐾. 𝐸.
d. Change in Internal Energy
∆𝑈 = 𝑚(𝑢2 − 𝑢1 )
e. Change in Enthalpy
∆𝐻 = 𝑚(ℎ2 − ℎ1 )
f. Change in Entropy
∆𝑆 = 𝑚(𝑠2 − 𝑠1 ) = 0
g. Heat Transferred
𝑄=0

V. Isenthalpic Process or Throttling Process

- A constant enthalpy process of a pure substance. It is a process in which no work is being

done and is utilized in getting the quality of steam

a. P-V and T-S diagrams

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ME 221 Thermodynamics 2 [Module 3: Processes of Pure Substance] Engr. Juanito M. Origines Jr.

1
1

2 2

1 2 ℎ2 = ℎ1 = ℎ𝑓1 + 𝑥(ℎ𝑓𝑔1 )

b. Steady flow Work

𝑊𝑠𝑓 = 0
c. Change in Internal Energy
∆𝑈 = 𝑚(𝑢2 − 𝑢1 )
d. Change in Enthalpy
∆𝐻 = 0
e. Change in Entropy
∆𝑆 = 𝑚(𝑠2 − 𝑠1 )
f. Heat Transferred
𝑄=0

Summary of Formulas for Processes of Pure Substance

Process Isometric Isobaric Isothermal Isentropic Isenthalpic

V=C P=C T=C S=C 𝐻=𝐶

Non-Flow 𝑄 − ∆𝑈 𝑄 − ∆𝑈
If Wnf =Wb =0 −∆𝑈 N/A
Work 𝑊𝑏 = 𝑚𝑃(𝑣2 − 𝑣1 )

Steady-flow 𝑊𝑠𝑓 𝑊𝑠𝑓 𝑊𝑠𝑓

= 𝑄 − ∆𝐻 − ∆𝑃𝐸 𝑊𝑠𝑓 = −∆𝑃𝐸 − ∆𝐾𝐸 = 𝑄 − ∆𝐻 − ∆𝑃𝐸 = −∆𝐻 − ∆𝑃𝐸 0
Work − ∆𝐾𝐸 − ∆𝐾𝐸 − ∆𝐾𝐸
∆𝑈 𝑚(𝑢2 − 𝑢1 ) 𝑚(𝑢2 − 𝑢1 ) 𝑚(𝑢2 − 𝑢1 ) 𝑚(𝑢2 − 𝑢1 ) 𝑚(𝑢2 − 𝑢1 )
∆𝐻 𝑚(ℎ2 − ℎ1 ) 𝑚(ℎ2 − ℎ1 ) 𝑚(ℎ2 − ℎ1 ) 𝑚(ℎ2 − ℎ1 ) 0
∆𝑆 𝑚(𝑠2 − 𝑠1 ) 𝑚(𝑠2 − 𝑠1 ) 𝑚(𝑠2 − 𝑠1 ) 0 𝑚 𝑠2 − 𝑠1 )
(
𝑄 ∆𝑈 ∆𝐻 𝑇(∆𝑆) 0 0