ENTROPY

Reference: J.M. Smith, H.C. Van Ness,

M.M. Abbott. Introduction to Chemical
Engineering Thermodynamics7th
edition
• Limitation of first law
1. Failure to establish the direction of change
2. Failure to establish qualitative difference between
heat and work
• Thus, it is clear that apart from the first law, there
should be some principle (complementary to first
law) to deal with the spontaneous processes and
their direction
• With the help of the tools provided by the second
law, we can find answers to many problems that are
not answered by the first law.
• The second law of thermodynamics states that all
spontaneous processes are, to some extent,
irreversible and are accompanied by a degradation
of energy.
• To make the statements of second law of
thermodynamics quantitative, some function that
always changes in a certain way during a
spontaneous process is required to characterize
changes.
• Entropy is fundamental to the development of
second law of thermodynamics.
• Entropy is the thermodynamic property, which
serves as a measure of the unavailability or
degradation of energy.
• An increase in unavailability of the total energy of
a system is quantitatively expressed by a
corresponding increase in its entropy
• The entropy of a system is affected only by the
nature of matter under consideration and by the
state in which it exists.
 Entropy and Heat
• Whenever a certain form of energy gets
transformed to heat the total energy gets
degraded with a corresponding increase in the
entropy of the system.
• Entropy of the system also increases by the
direct supply of heat to the system.
• In short, the entropy of the system is
increased by the addition of heat through any
mechanism or from any source.
 Entropy and Temperature
• The amount of heat added to a system also
depends upon the temperature of the system to
which heat is added.
• The transfer of heat within an isolated system to a
region of lower temperature increases the
unavailability of energy and the entropy of the
system.
• The addition of heat to a system at a lower
temperature leads to a greater degradation of energy
than that resulted by the addition at a higher
temperature.
• Since entropy measures the degree of degradation or
the extent of irreversibility, it should therefore, be
related not to Q, but to Q/T, where Q is the heat
received by the reservoir and T is its temperature.
 Entropy and the Nature of the Process
• It has been established that quantitative description for
entropy should take into account the heat transferred
and the temperature level at which it is transferred.
• In addition, in order to complete the definition of
entropy, the nature of the process should also be
specified.
• Consider:
1. Free expansion of gas to a lower pressure within a
closed system, which is completely isolated from the
surroundings thermally and mechanically.
2. An engine operating within the system that
continuously converts the work done into heat by
means of friction.
• In case 1, the process is irreversible resulting in
degradation of energy of the system and
consequently an increase in its entropy. However, no
heat is added, no work is done, and for an ideal gas,
the process is isothermal.
• How is then the increase in entropy for this process
measured?
• In case 2, heat is added to the system by degradation
of mechanical work. The amount of heat added
increases with the efficiency of the engine, and
reaches a maximum when the engine operates
reversibly.
• when the amount of heat transferred is used to
measure the increase in entropy , logically, entropy
𝑄𝑅𝑒𝑣
should be measured using because the
𝑇
maximum possible degradation of higher forms of
energy into heat is possible only in a reversible
process.
Carnot Cycle
• The equation for a Carnot cycle is given as:
𝑄𝐻 𝑄𝐶
= 4.1
𝑇𝐻 𝑇𝐶
• When the heat quantities refer to working fluids
rather than heat reservoirs,
𝑄1 −𝑄2
= (4.2)
𝑇1 𝑇2
𝑄1 𝑄2
+ =0 (4.3)
𝑇1 𝑇2
• Equation (4.3) means that the sum of the
𝑄Τ
quantities 𝑇 associated with the absorption
and rejection of heat by the working fluid in a
Carnot cycle is zero.
• Any reversible cyclic operation may be regarded as
made up of several imaginary Carnot cycles and for
each such cycle we can write equation similar to
Equation (4.3)
𝑑𝑄1 𝑑𝑄2
+ =0 (4.4)
𝑇1 𝑇2
• where 𝑑𝑄1 and 𝑑𝑄2 are the heat absorbed and
heat rejected respectively during one such an
imaginary cycle.
• Combining all such equations that are written for
the separate Carnot cycles which the original
reversible cycle of interest consists, we get:
𝑑𝑄𝑟𝑒𝑣
ර =0 (4.5)
𝑇
 𝑑𝑄𝑟𝑒𝑣
• The quantities sums to zero for the
𝑇
arbitrary cycle of interest
• For a complete cycle, sum of changes in each of
its property is zero.
• Hence, for a cycle of interests, the property
whose differential changes are given by
𝑑𝑄𝑟𝑒𝑣
quantities is called entropy:
𝑇
𝑑𝑄𝑟𝑒𝑣
𝑑𝑆 = (4.6)
𝑇
• Entropy is a measure of irreversibility
• For a system undergoing reversible process
between states 1 and 2, the change in entropy is
given by:
2
𝑑𝑄𝑟𝑒𝑣
∆𝑆 = න (4.7)
1 𝑇
• For a reversible process, the change in entropy
for the surroundings is equal in magnitude but
opposite in sign to that of the system
• Hence, the net entropy change of a system plus
that of the surrounding is zero for a reversible
process:

∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟 = 0 (4.8𝑎)

• After the occurrence of an irreversible process, the
system and surrounding can never both be
restored to their original states
• In practice, real processes are irreversible,
therefore a measure of irreversibility is desirable.
• For a irreversible process, the sum of entropy
changes of the system plus that of the surrounding
is always greater than zero:
∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟 > 0 (4.8𝑏)
• Equations (4.8a) and (4.8b) are the mathematical
statement of the second law of thermodynamics.
In words, the second law may be stated as
follows:
• The entropy of an isolated system increases in an
irreversible process and remains unchanged in a
reversible process. It can never decrease.
∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟 ≥ 0 (4.9)
• Thus, either ∆𝑆𝑠𝑦𝑠 or ∆𝑆𝑠𝑢𝑟𝑟 can be a negative
quantity for a particular process, but their sum
can never be less than zero
• Since entropy is a state property, the entropy
change due to direct transfer of heat or the
degradation of higher forms of energy into heat
can always be calculated using equation (4.6)
irrespective of if the transfer is accomplished
reversibly or irreversibly.
• However, if a process is irreversible because of
a finite difference in another driving force, such
as pressure, calculation of entropy change is
done by devising a suitable reversible process
for accomplishing the change
 Entropy change in phase transitions
• For phase transitions like fusion, vaporization, or
transition from one crystalline form to another,
entropy change can be evaluated from the values
of the latent heat of phase change and the
temperature at which the change is carried out.
• The phase changes can be treated as changes
occurring reversibly at constant temperature.
• For example, the entropy of vaporization is given
as:
∆𝐻𝑣
∆𝑆𝑣 = (4.10)
𝑇
 WORKED EXAMPLE
• Calculate the entropy of evaporation of dry
saturated steam at 500 kPa.
• Data: From the steam tables, latent heat of
vaporization, ∆𝐻𝑣 = 2106 kJ/kg; Saturation
temperature of steam = 425 K.
• Solution: By equation 10, entropy change
accompanying vaporization is ∆𝑆𝑣 =
2106/425 = 4.96 kJ/kg K
 Entropy Change for Processes
involving Ideal Gases
• For a differential change in the thermodynamic
state of a closed system, the first law of
thermodynamics can be written as:
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 (4.11)
• When the process is reversible and the work
involved is only work of expansion, equation (4.11)
can be modified as:
𝑑𝑄𝑟𝑒𝑣 = 𝑑𝑈 + 𝑃𝑑𝑉 (4.12)
• Substituting (4.12) into (4.6), we have:
𝑑𝑈 + 𝑃𝑑𝑉
𝑑𝑆 = (4.13)
𝑇
𝑅𝑇
• For an idea gas, 𝑑𝑈 = 𝑐𝑉 𝑑𝑇 and 𝑃 = ;
𝑉
putting these expressions into equation, we
have:
𝑑𝑉
𝑐𝑉 𝑑𝑇 + 𝑅𝑇
𝑑𝑆 = 𝑉
𝑇
𝑑𝑇 𝑑𝑉
= 𝑐𝑉 +𝑅 (4.14)
𝑇 𝑉
• Assuming that 𝑐𝑉 is independent of temperature,
equation (4.14) can be integrated for a finite
change from state 1 to state 2 giving for one mole
of an ideal gas
𝑇2 𝑉2
∆𝑆 = 𝑐𝑉 ln + 𝑅 ln (4.15)
𝑇1 𝑉1
• Equation (4.15) can be used to evaluate entropy
change accompanying the change in states of
ideal gases.
• The equation can also be modified thus:
𝑉2 𝑃1 𝑇2
• For ideal gases; 𝑐𝑉 = 𝑐𝑃 − 𝑅 and = ; putting
𝑉1 𝑃2 𝑇1
these expressions into equation, we have:
 𝑇2 𝑃2
∆𝑆 = 𝑐𝑃 ln − 𝑅 ln (4.16)
𝑇1 𝑃1
• For constant volume process, equation (4.15)
reduces to:
𝑇2
∆𝑆 = 𝑐𝑉 ln (4.17)
𝑇1
• For constant pressure process, equation (4.16)
reduces to:
𝑇2
∆𝑆 = 𝑐𝑃 ln (4.18)
𝑇1
• For an isothermal process, we have:
𝑉2 𝑃1
∆𝑆 = 𝑅 ln = 𝑅 ln (4.19)
𝑉1 𝑃2
 WORKED EXAMPLE
• Determine the change in entropy when 2 kg of a
gas at 277 K is heated at constant volume to a
temperature of 368𝐾. Take the specific heat at
constant volume = 1.42 kJ/kg K.
• Solution Entropy change accompanying a
constant volume process is given by Eq. (4.17).
For m = 2 kg,
𝑇2 368
• ∆𝑆 = 𝑐𝑉 ln = 2(1.42) ln = 0.8067𝑘𝐽/𝐾
𝑇1 277
 WORKED EXAMPLE
• Calculate the entropy change when 1 kmol of an
ideal gas at 300 K and 10 bar expands through a
throttle to a pressure of 1 bar.
• Solution During throttling enthalpy is unchanged.
For an ideal gas enthalpy being a function of
temperature alone, the temperature remains
unchanged during the process. Therefore,
entropy change accompanying the process can be
computed by Eq. (4.19).
𝑃1 10
• ∆𝑆 = 𝑅 ln = 8.314 ln = 19.14𝑘𝐽/𝑘𝑚𝑜𝑙 𝐾
𝑃2 1
 WORKED EXAMPLE
• What is the change in entropy when 1 kmol of
an ideal gas at 335 𝐾 and 10 bar is expanded
irreversibly to 300 𝐾 and 1 bar? 𝑐𝑃 = 29.3
𝑘𝐽/𝑘𝑚𝑜𝑙 𝐾.
• Solution The entropy change in this process is
given by Eq. (16)
𝑇2 𝑃2
∆𝑆 = 𝑐𝑃 ln − 𝑅 ln
𝑇1 𝑃1
300 1
= 29.3 ln − 8.314 ln
335 10
= 15.91𝑘𝐽/𝑘𝑚𝑜𝑙 𝐾
 Entropy Change for Adiabatic Mixing
Process
• When two substances at different temperatures
are mixed together adiabatically, both will attain
an intermediate temperature, say, T. The change
in entropy of each is calculated as:
𝑇
𝑑𝑄𝑟𝑒𝑣 𝑑𝑇
∆𝑆 = න = න 𝑐𝑃 4.20
𝑇 𝑇1 𝑇
where 𝑇1 denotes its initial temperature.
Equation (4.20) can be used for the calculation of
change in entropy in processes like mixing of two
fluid streams or quenching of metallic bodies in
liquids.
 WORKED EXAMPLE
• 10 kg water at 375 K is mixed adiabatically with 30 kg
water at 275 K. What is the change in entropy? Assume
that the specific heat of water is 4.2 kJ/kg K and is
independent of temperature
Heat balance:
10 375 − 𝑇 = 30 𝑇 − 275
The final temperature T, attained by the mixture is:
𝑇 = 300𝐾
300
∆𝑆1 = 10 × 4.2 × ln = −9.37𝑘𝐽/𝐾
375
300
∆𝑆2 = 30 × 4.2 × ln = 10.96𝑘𝐽/𝐾
275
• Total entropy change is:
∆𝑆 = ∆𝑆1 + ∆𝑆2 = 1.59𝑘𝐽/𝐾
 WORKED EXAMPLE
• A steel casting at a temperature 725 𝐾 and weighing 35 𝑘𝑔
is quenched in 150𝑘𝑔 oil at275𝐾. If there are no heat
losses, determine the change in entropy. The specific heat
𝑐𝑃 of steel is 0.88 𝑘𝐽/𝑘𝑔 𝐾 and that of oil is2.5 𝑘𝐽/𝑘𝑔 𝐾.

35 × 0.88 × 725 − 𝑇 = 150 × 2.5 × 𝑇 − 275

𝑇 = 309.15𝐾
309.15
∆𝑆1 = 35 × 0.88 × ln = −26.25𝑘𝐽/𝐾
725
309.15
∆𝑆2 = 150 × 2.5 × ln = 43.90𝑘𝐽/𝐾
275
• Total entropy change for casting and oil is:
∆𝑆 = ∆𝑆1 + ∆𝑆2 = 17.65𝑘𝐽/𝐾
Entropy Change for Isothermal Mixing
of Ideal Gases
• The entropy change resulting from the
irreversible process of mixing of ideal gases in
their pure state at temperature T and pressure P
to form the mixture at the same temperature and
pressure can be computed by the following
equation:
∆𝑆 = −𝑛𝑡𝑜𝑡𝑎𝑙 𝑅 ෍ 𝑥𝑖 ln 𝑥𝑖 (4.21)
𝑖
 Worked Example
• Estimate the entropy change of mixing 2 moles of
argon, 1 mole of helium and 3 moles of hydrogen at
constant temperature and pressure
• Solution:
−𝑛𝑅 𝑥𝐴𝑟 ln 𝑥𝐴𝑟 + 𝑥𝐻𝑒 ln 𝑥𝐻𝑒 + 𝑥𝐻2 ln 𝑥𝐻2
−1 −1
2 2 1 1 3 3
− 6𝑚𝑜𝑙 8.314𝐽𝐾 𝑚𝑜𝑙 ln + ln + ln
6 6 6 6 6 6
= 50.45𝐽𝐾 −1
 Entropy Change in Chemical Reaction
• The entropy changes accompanying chemical
reactions are evaluated through the use of
absolute entropies of the various components
taking part in the reaction.
• Considering an hypothetical reaction:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
the change in entropy is given by:
∆𝑆 𝑜 = ෍ 𝜐𝑆ҧ 𝑜𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝜐𝑆ҧ 𝑜𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 (4.22)

where 𝜐 represents the stoichiometric coefficient

 Worked Example
• Calculate Δ𝑆𝑠𝑦𝑠 , Δ𝑆𝑠𝑢𝑟𝑟 , and Δ𝑆𝑢𝑛𝑖𝑣 for the
synthesis of ammonia at 25℃ using the
information in the table below:
Table 1: Entropy at 25℃
Substance Molar Entropy
(J.K-1.mol-1)
N2 191.61
H2 130.68
NH3 192.45
 𝑁2 𝑔 + 3𝐻2 𝑔 → 2𝑁𝐻3 𝑔 ∆𝐻 ° = −92.6𝑘𝐽𝑚𝑜𝑙−1

∆𝑆𝑠𝑦𝑠 = 2𝑆ҧ 𝑜 𝑁𝐻3 − 𝑆ҧ 𝑜 𝑁2 + 3𝑆ҧ 𝑜 𝐻2

= 2 192.5𝐽𝐾 −1 𝑚𝑜𝑙 −1 − 191.6𝐽𝐾 −1 𝑚𝑜𝑙 −1 + 3 130.6𝐽𝐾 −1 𝑚𝑜𝑙 −1
= −198.4𝐽𝐾 −1 𝑚𝑜𝑙−1

∆𝐻𝑠𝑢𝑟𝑟 = −∆𝐻𝑠𝑦𝑠
∆𝐻𝑠𝑢𝑟𝑟
∆𝑆𝑠𝑢𝑟𝑟 =
𝑇
−1
− −92.6 × 1000 𝐽𝑚𝑜𝑙
= = 311𝐽𝐾 −1 𝑚𝑜𝑙 −1
298𝐾

• The change in entropy for the universe is

∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟
= −198 + 311𝐽𝐾 −1 𝑚𝑜𝑙 −1
= 113𝐽𝐾 −1 𝑚𝑜𝑙 −1