Scribd
Upload
4 views

CET-1 -Unit-1-Lect-6,- notes

The document discusses the second law of thermodynamics and the concept of entropy, highlighting its role as a state function and its calculation in reversible and irreversible processes. It includes examples and homework problems related to ideal gas states, entropy changes during heat transfer, and the implications of the third law of thermodynamics. Additionally, it addresses the concept of lost work in thermodynamic processes and the conditions for maximum work realization.

Uploaded by

jeelradadiya758
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
4 views

CET-1 -Unit-1-Lect-6,- notes

The document discusses the second law of thermodynamics and the concept of entropy, highlighting its role as a state function and its calculation in reversible and irreversible processes. It includes examples and homework problems related to ideal gas states, entropy changes during heat transfer, and the implications of the third law of thermodynamics. Additionally, it addresses the concept of lost work in thermodynamic processes and the conditions for maximum work realization.

Uploaded by

jeelradadiya758
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 18

Chemical Engineering

Thermodynamics-1
th
B. Tech 3 sem Chemical Engg.
Lect-6
2nd law of thermodynamics and its application (chapter 5
page no 173)
ENTROPY

Entropy is a point function or state


function (not a path function)

Points A and B on the PVt diagram


represent two equilibrium states of a
particular fluid, and paths ACB and ADB
represent two arbitrary reversible
processes connecting these
points. Entropy can be calculated as
The characteristics of entropy may be summarised as follows:

✓ Entropy relates to the second law in much the same way that internal energy relates
to the first law.

✓ The ultimate source of all equations that connect entropy is ∫dQ / T

✓ This equation Δ∫S = dQ / T provides the means for calculating changes in this
property. (The change in entropy of any system undergoing a finite reversible process)

✓ When a system undergoes an irreversible process between two equilibrium states,


the entropy change of the system Δ S is evaluated as ΔS = Q / T

✓ entropy changes of the irreversible and reversible processes are identical.

✓ The entropy change of a system resulting only from the transfer of heat can always be
calculated by ∫dQ / T, whether the heat transfer is accomplished reversibly or
irreversibly
ENTROPY CHANGES FOR THE IDEAL-GAS STATE

For one mole or a unit mass of fluid undergoing a mechanically


reversible process in a closed System, Entropy can be
calculated as

this equation relates properties only, independent of the process


causing the change of state, and is therefore a general equation
for the calculation of entropy changes in the ideal-gas state.
Question: Homework problem
For the ideal-gas state and constant heat capacities, T P ( 1 − γ ) /γ = constant for a reversible adiabatic (and therefore
isentropic) process can be written:
(T2/T1)= (P2/P1)(γ−1)/γ
Show that this same equation results from application of (Δ Sig/R)= ∫T T(C P ig / R ) (dT/T)− ln (P/ P0) with ΔSig = 0.
0

Solution:
Data Given:
Gas is ideal
Cp is constant
The process is reversible and adiabatic
T
Because C P ig is constant, (Δ Sig/R)= ∫T0 (CP ig /R ) (dT/T)− ln (P/P0) becomes:
0 = (C P ig /R) ln (T2 /T1) − ln (P2/P1) = ln(T2 /T1) − (R/ C P ig )(ln (P2 /P1)
By C P ig = C V ig + R for the ideal-gas state, with γ = C P ig / C V ig :
C P ig = CV ig + R or (R/ C P ig )=(γ−1)/γ
Whence,
ln (T2/T1 )=((γ−1)/γ) ln (P2/P1)

Exponentiating both sides, (T2/T1)= (P2/P1)(γ−1)/γ


Question: Homework problem
Methane gas at 550 K and 5 bar undergoes a reversible adiabatic expansion to 1 bar. Assuming ideal-
gas-state methane at these conditions, find its final temperature.

Solution:
Question: Homework problem
A 40 kg steel casting (CP = 0.5 kJ⋅kg−1⋅K−1) at a temperature of 450°C is quenched in 150 kg of oil
(CP = 2.5 kJ⋅kg−1⋅K−1) at 25°C. If there are no heat losses, what is the change in entropy of (a) the
casting, (b) the oil, and (c) both considered together?
Solution:
Data given:
Mass of steel casting, ms = 40 kg
Mass of oil, mo =150 kg
Specific heat capacity of steel casting, CPs = 0.5 kJ⋅kg−1⋅K−1
Specific heat capacity of oil, CPo = 2.5 kJ⋅kg−1⋅K−1
Temperature of steel casting, Ts= 450°C
Temperature of oil, To = 25 °C

Let the final temperature be t °C


Since the change in energy of the oil and steel together must be zero, The final temperature t of the
oil and the steel casting is found by an energy balance.
ms ⋅ CPs ⋅(t- Ts) + mo ⋅ CPo ⋅(t- To) = 0
(40)(0.5)(t− 450) + (150)(2.5)(t − 25) = 0 ; 20 ⋅ t – 9000 + 375 ⋅ t – 9375 = 0
395⋅t = 18375 or t = 46.52 °C

a) Change in entropy of the casting:


Δ S t s= m ∫(C P /T)dT = ms CPs ln (t/Ts )
= (40)(0.5) ln {(273.15 + 46.52)/( 273.15+450)}
= −16.33 kJ⋅ K −1

(b) Change in entropy of the oil:


Δ S to= m ∫(C P /T)dT = mo CPo ln (t/To )
= (150 ) ( 2.5 ) ln{(273.15 + 46.52)/( 273.15+ 25)}
= 26.13 kJ⋅ K −1

(c) Total entropy change:


Δ S total = Δ S t s + Δ S to
= −16.33 + 26.13
= 9.80 kJ⋅ K −1
ENTROPY BALANCE FOR OPEN SYSTEMS

Entropy is not conserved. The second law states that the


total entropy change associated with any process must be positive, with a
limiting value of zero for a reversible process.

The entropy balance equation for an open system can be written as


Example 5.6 (Home work problem)
An inventor claims to have devised a process which takes in only saturated steam at
100°C and which by a complicated series of steps makes heat continuously available
at a temperature level of 200°C, with 2000 kJ of energy available at 200°C for every
kilogram of steam taken into the process.
Show whether or not this process is possible.
To give this process the most favorable conditions, assume cooling water available
in unlimited quantity at a temperature of 0°C.
Date given:
From the energy balance, maximum energy transfer can be calculated
CALCULATION OF IDEAL WORK
In a process producing work, an absolute maximum amount of work can be realized
when the change of state associated with the process is accomplished completely
reversibly.

That means maximum work can be obtained by a reversible process only


For such a process, the entropy generation is zero.

Wideal = ΔH − Tσ ΔS

A completely reversible process is hypothetical, devised here solely for determination of


the ideal work associated with a given change of state.

The sole connection between an actual process and an imagined hypothetical


reversible process employed for determining ideal work is that they both
apply to the same changes of state.
LOST WORK
Work that is wasted as the result of irreversibilities in a process is called lost
work, Wlost, and is defined as the difference between the actual work of a change
of state and the ideal work for the same change of state. Thus by definition,
THE THIRD LAW OF THERMODYNAMICS
The postulate of the THIRD LAW OF THERMODYNAMICS: The absolute entropy is zero
for all perfect crystalline
substances at absolute zero temperature.

Measurements of heat capacities at very low temperatures provide data for the
calculation of entropy changes down to 0 K.

When these calculations are made for different crystalline forms of the same chemical
species, the entropy at 0 K appears to be the same for all forms.

When the form is noncrystalline, e.g., amorphous or glassy, calculations show that the
entropy of the disordered form is greater than that of the crystalline form.

You might also like