Diagrams involving entropy

We have used P-v and T-v diagrams in the study of the first law of
thermodynamics. In the second law analysis, we have new property that
is called entropy, so it is very helpful to plot the processes on diagrams
one of their coordinates is the entropy. The two diagrams commonly used
in the second-law analysis are the temperature-entropy and the
enthalpy-entropy diagrams.

T-S diagram

Consider an internally rev. process that is drawn on the T-S diagram as

shown. From the second law,

𝛿𝑄
𝑑𝑆 = ( )
𝑇 𝑖𝑛𝑡.𝑟𝑒𝑣

Re arrange the equation

𝛿𝑄𝑖𝑛𝑡.𝑟𝑒𝑣 = 𝑇. 𝑑𝑆

𝛿𝑄𝑖𝑛𝑡.𝑟𝑒𝑣 corresponds to a differential area element

(𝑇. 𝑑𝑆)on a T-S diagram as shown in the figure. By
integration the above equation,

2
𝑄𝑖𝑛𝑡.𝑟𝑒𝑣 = ∫ 𝑇. 𝑑𝑆 𝑘𝐽
1

which corresponds to the area under the process curve on a T-S diagram.
Therefore, we conclude that the area under the process curve on a T-S
diagram represents heat transfer during an internally reversible
process.

Note

For irreversible Process, the area under process curve on T-S diagram has
no meaning.

Per unit mass:

2
𝑞𝑖𝑛𝑡.𝑟𝑒𝑣 = ∫ 𝑇. 𝑑𝑠 𝑘𝐽⁄𝑘𝑔
1

Special processes:

1- Int. rev. isothermal process (T= c)

In this case, the above equation yields,

2
𝑞𝑖𝑛𝑡.𝑟𝑒𝑣 = 𝑇 ∫1 𝑑𝑠 = 𝑇(𝑠2 − 𝑠1 ) = 𝑇∆𝑠 = ± according to heat added or
rejected

2- Int. rev. adiabatic process

From 2nd law,

𝛿𝑞
∆𝑠 = ∫ + 𝑠𝑔𝑒𝑛
𝑇

Int. rev. process means 𝑠𝑔𝑒𝑛 = 0 Expansion process

Adiabatic process means 𝑞 = 0

∆𝑠 = 0

𝑠2 − 𝑠1 = 0

𝑠2 = 𝑠1
Compression process
𝑠 = 𝑐𝑜𝑛𝑠𝑡.

It is called isentropic process. An isentropic process on a T-s diagram is

easily recognized as a vertical-line segment as shown.

EXAMPLE (The T-S Diagram of the Carnot Cycle)

Show the Carnot cycle on a T-S diagram and indicate the areas that
represent the heat supplied QH, heat rejected QL, and the net-work output
Wnet,out on this diagram.

Recall that the Carnot cycle is made up of two reversible isothermal,

T=constant, (heat addition and heat rejection) processes and two
isentropic, s = constant, (expansion and compression) processes. These
four processes form a rectangle on a T-S
diagram, as shown.

On a T-S diagram, the area under the process

curve represents the heat transfer for that
process. Thus the area A12B represents QH, the
area A43B represents QL, and the difference
between these two (the area in color) represents
Qnet which in turn equal the net-work according
to the 1st law

Wnet= Qnet =QH - QL

Therefore, the area enclosed by the path of a cycle (area 1234) on a T-S
diagram represents the net-work. Recall that the area enclosed by the path
of a cycle also represents the net work on a P-V diagram.

T-S diagram for pure substance

The behavior of the T-s diagram is the

same as T-v diagram. The pure
substance (water and refrigerant) has 3
possible phases, pure liquid
(compressed), saturated liquid- vapor
mixture and pure vapor (superheated).

The 2nd figure shows constant

pressure lines (which also constant
temperature in the mixture region)
and constant volume lines.
The T ds relations:

From 2nd law,

𝛿𝑄
∆𝑆 = ∫ + 𝑆𝑔𝑒𝑛
𝑇

The above equation can be performed only if

- The process is int. rev. (→ 𝑆𝑔𝑒𝑛 = 𝑜)

- The process is isothermal (→ 𝑇 = 𝐶), then

𝑄12
∆𝑆 =
𝑇

But when the temperature varies during the process, we have to have a
relation between Q and T to perform this integration. Finding such
relations is difficult and we will determine 𝑑𝑠 in a different way that we
will do in this section.

The differential form of the 1st law equation for a closed stationary
system (a fixed mass) can be expressed for an internally reversible
process as

𝛿𝑄𝑖𝑛𝑡.𝑟𝑒𝑣. − 𝛿𝑊𝑖𝑛𝑡.𝑟𝑒𝑣. = 𝑑𝑈

But

𝛿𝑊𝑖𝑛𝑡.𝑟𝑒𝑣. = 𝑃𝑑𝑉

And from 2nd law 𝛿𝑄𝑖𝑛𝑡.𝑟𝑒𝑣. = 𝑇𝑑𝑆

Thus

𝑇𝑑𝑆 − 𝑃𝑑𝑉 = 𝑑𝑈 𝑘𝐽
 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 𝑘𝐽

Or per unit mass

𝑇𝑑𝑠 = 𝑑𝑢 + 𝑃𝑑𝑣 𝑘𝐽⁄𝑘𝑔 (1) #

It is the first T ds, or Gibbs, equation.

Since ℎ = 𝑢 + 𝑃𝑣, then

𝑑ℎ = 𝑑𝑢 + 𝑃𝑑𝑣 + 𝑣𝑑𝑃

From equation (1),

𝑑ℎ = 𝑇𝑑𝑠 + 𝑣𝑑𝑃

And then

𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑃 𝑘𝐽⁄𝑘𝑔 (2) #

It is the second T ds relation.

The T ds relations are extremely valuable since they

relate entropy changes of a system to the changes in
𝛿𝑄
other properties. Unlike 𝑑𝑆 = ( ) , they are
𝑇 𝑖𝑛𝑡.𝑟𝑒𝑣

property relations and therefore are independent of the

type of the processes (reversible or irreversible). They
are applicable for a closed system when its state is
changed from state to another. Also, it can be used for
open system when the inlet state is changed from state to another.