WEEK 2
Entropy
It is a measure of disorder or randomness. It was first used by Rudolf Clausius. Entropy increases
as the systems temperature increases for example,
ice ⃗
heat water molecules → water vapor
(more disorder,more randomess )
Entropy is represented by the symbol S and it depends on the state of the system not its history
(state function).
When an amount of energy is added to the system by some reversible process the change in
entropy of the system is defined as
Q
ΔS= at constant temperature
T
where,
Q=heat absorbed
T =Absolute temperature
If the temperature is not constant then we have infinitely small changes (infinitesimal changes =
extremely small, tiny or minute) in the entropy
Thus
dq
dS= rev [ at non-constant temperature]
T
For a system moving from the initial state 1to the final state 2
We can define the change in entropy as
2
dq
ΔS=S 2 −S 1=∫ rev
1 T
Note
For a reversible adiabatic change (no heat transfer)
dq rev =0 Implying that there is no change in entropy
The physical significance of entropy
A characteristic of spontaneous processes is that they are accompanied by increase “disorder or
chaos’’ of the system. An expansion of a gas into a vacuum is accompanied by an increase in
entropy of the system. Since the expansion of gas is accompanied by increase in disorder, so is
the increase in entropy.
Further, fusion and vaporization are accompanied by increase in entropy. This increase in
entropy causes an increase in disorder since the molecules of vapor are less orderly than those of
a liquid.
Systems tend to a state of maximum entropy. A gas will therefore tend to occupy all the space or
volume available to it.
Efficiency of a reversible cycle
The concept of entropy is used to derive an expression for the maximum efficiency of an engine.
For the conversion of heat into work such an engine must function in cycles. A cycle being
succession of changes as a result of which the system returns to the original state (all properties
of the system thus assuming their original value)
The internal energy change ∆U = 0 and hence the resultant work done is equal to the net heat
absorbed
w=q
Maximum work is obtainable from a process when that process is carried out reversibly. Thus
maximum efficiency for conversion of heat to work is obtained from a reversible cycle.
Entropy change for an ideal gas
For an ideal gas
dq rev =CvdT+Pdv [ where only presure-volume work are involved ]
Cv=molar heat capacity atconstant volume
Recall, from the 1 st law of themodynamics
dq v
Cv= at constant volume
dT
dq
Cp= p at constant pressure
dT
dq p =dU+Pdv [at constant P hence dp=dU
dU
Cv= therefore dU=CvdT
dT
dq rev =CvdT+Pdv Equation I
For 1mole of ideal gas
PV=RT
RT
P=
V
RT
dq rev =CvdT+ dv Equation II
V
dq rev
we know ds=
T
Divide equation II by T
we get
dq rev CvdT R
= + dv
T T V
T2 T V
dq rev 2
dT
2
dv
ΔS=S 2 −S 1=∫ =Cv ∫ +R ∫
T
T T T V
V
1 1 1
T2 V2
ΔS=Cvln +Rln EquationIII
T1 V1
The entropy change for a process involving the ideal gas depends on the initial and final
temperature and volume.
Since
P1 V 1 =RT 1 and P2 V 2 =RT 2
Then
V 2 T 2 P1
=
V 1 T 1 P2
substituting in equation III
yields,
T T P
ΔS=Cvln 2 +Rln 2 1
T1 T 1 P2
T2 T2 P2
ΔS=Cvln +Rln −Rln
T1 T1 P1
but Cv +R=Cp
and thus
T2 P2
ΔS=Cpln −Rln For1mole of the gas
T1 P1
Consider a case whose there is no change in temperature
That is T2 = T1 (This is an Isothermal change)
Then from the expression
T V
ΔS=Cvln 2 + Rln 2
T1 V1
We get
V2
ΔST =Cvln1+Rln
V1
V2
ΔST =Rln
V1
From the expression
T2 P2
ΔS=Cpln −Rln
T1 P1
we get,
P2
ΔST =Cpln1−Rln
P1
P
ΔST =−Rln 2
P1
Therefore at constant temperature
V2 P2
ΔST =Rln =−Rln
V1 P1
For an isothermal expansion
V2 > V1 and thus isothermal expansion is accompanied by increase in entropy. Likewise
isothermal compression is accompanied by a decrease in entropy.
Consider a case where there is no change in pressure (P1=P2)
This is an isobaric process (constant pressure)
Then from,
T2 P2
ΔS=Cpln −Rln
T1 P1
T2
ΔS p=Cpln
T1
Thus increase in temperature at constant pressure is accompanied by an increase in entropy
Consider a case where there is no change in volume (V1 = V2)
This is an isochoric change (constant volume)
from,
T2 V2
ΔS=Cvln + Rln
T1 V1
we get
T2
ΔS v=Cvln
T1
Summary
Maximum efficiency for conversion of heat to work is obtained from a reversible cycle. Isobaric
and isochoric processes take place at constant pressure and volume respectively. Isothermal
expansion is accompanied by increase in entropy while compression is accompanied by a
decrease in entropy
Assignment
a) Calculate the increase in entropy when 1 mole of NH 3 is heated from 298 K to 398 K if
the Cp is 25.87
b) Calculated the change in entropy when 3 moles of a perfect gas is allowed to expand at
300 K from a volume of 2dm3 to 13dm3
c) For an ideal gas Cp = 2.5R, calculate the change in entropy when 3 moles of this gas is
heated from 300 K to 600 K at: (a) Constant pressure (b) Constant volume.
d) Calculate the change in entropy when 3 moles of an ideal gas is heated and compressed
simultaneously from 300 K, 1 atm to 400 K, 5 atm. (Cp = 7R/2)
e) By how much does the entropy of 3 moles of an ideal gas change if pressure is reduced
from 2 bar to 1 bar without any change in temperature?