B48BC/B58TB

Thermodynamics
Topic 3
The Second Law of Thermodynamics

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November 2020 1
Thermodynamics
 Worked Example 3.4.1 – Problem
Check whether or not it is possible to operate a heat engine that
takes heat from a hot reservoir and releases the same amount of
heat to a cold reservoir but produces no net work:
• First, check whether or not the cycle is consistent with the first
law.
• Then, check whether or not this cycle violates the second law.

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November 2020 2
Engineering B
 Worked Example 3.4.1 – Solution
It is convenient to visualise the cycle:

• Here, heat is spontaneously flowing from a

higher to a lower temperature.

• Notice that no work is done by this cycle,

so that |wnet| = 0.

• Experience leads to the conclusion that

this can happen.

The first law may be applied to this cycle by examining the energy
flows entering and leaving the working fluid. The energy flows are
absolute values and their directions are indicated by arrows.

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November 2020 3
Thermodynamics
 Worked Example 3.4.1 – Solution
Starting with:
wnet = q H − qC
For this cycle, no net work is produced |wnet| = 0, giving:
 qC = q H
This heat engine, although useless, does not in any way violate the
first law…..energy is still conserved, even if no useful work is done.

Checking the consistency with the second law is straightforward, as

this heat engine is one of the examples used to introduce the
second law!

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November 2020 4
Thermodynamics
 Worked Example 3.4.1 – Solution
If |wnet| = 0, the thermal efficiency of a given cycle is:
wnet
h= =0
qH
Since TH and TC are both non-zero and different from each other, η
for a Carnot cycle operating between these two reservoirs must be
larger than zero: TH − TC
 CARNOT = 0
TH
Thus:
   CARNOT
Therefore the cycle is feasible, spontaneous, and doesn’t violate
the second law. However, its reversal (a Clausius machine) is not
possible. The result also shows that heat transfer through a finite
temperature difference is irreversible.
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November 2020 5
Thermodynamics
 Worked Example 3.4.1 – Solution
Looking at energy quality, it is observed that the cycle transforms
higher quality heat at higher temperature to lower quality heat at a
lower temperature.

According to the “quality interpretation” of the second law, the

cycle is feasible, spontaneous and irreversible, as the cycle only
reduces the overall energy quality.

The cycle is irreversible because it extracts none of the work that,

transferring this amount of heat, is capable of doing.

The larger the difference in temperature the more work remains

unextracted…….thus, the more irreversible is the cycle.

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November 2020 6
Thermodynamics
 Worked Example 3.4.1 – Solution
There is a case that has not been considered where TH = Tc:
wnet
= =0
qH
However, ηCarnot is now also zero:
TH − TC
 CARNOT = =0
TH
Thus, the two efficiencies are equal. Thus, for this special case, the
cycle is reversible (no work can be extracted). This is also
consistent with the energy quality interpretation of the second law,
as there is no change in energy quality and no driving force.

It also means that the transfer of heat through an infinitesimal

temperature difference is reversible. In the previous case heat
transfer through finite temperature difference was irreversible.
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November 2020 7
Thermodynamics
 Worked Example 3.4.2 – Problem
Consider the heat engine below:

• It operates between reservoir

temperatures of TH = 600 K and TC = 300 K.

• Check whether or not it is possible to

operate this heat engine with energy flows
of |qH| = 100 kJ/kg and |wnet| = 60 kJ/kg.

• Apply the first law to this cycle and check

whether or not the cycle violates the
second law.

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November 2020 8
Thermodynamics
 Worked Example 3.4.2 – Solution
From the first law:
wnet = q H − qC

 qC = q H − wnet  qC = 100 kJ/kg − 60 kJ/kg = 40 kJ/kg

Thus the first law has been applied to this heat engine cycle and
energy is conserved, but this does not mean the cycle is feasible.

The simplest way of checking compliance with the second law is to

use thermal efficiency:
wnet 60kJ/kg
= = = 0.6
qH 100kJ/kg

TH − TC 600K − 300K
 CARNOT = = = 0.5
TH 600K

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November 2020 9
Thermodynamics
 Worked Example 3.4.2 – Solution
η > ηCarnot, but it was shown before that the highest efficiency
possible, between any two heat reservoirs, is a reversible cycle.
Thus this cycle clearly violates the second law (even though the
first law was satisfied).

Too much work is being extracted in comparison to the amount of

heat being discarded to the cold reservoir.

From an energy quality perspective, there is an overall increase in

energy quality, which simply means that the cycle is impossible.

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November 2020 10
Thermodynamics
 Worked Example 3.4.3 – Problem
Consider the heat engine below:

• That it that the heat engine operates

between reservoir temperatures of
TH = 600 K and TC = 300 K.

• Check whether or not it is possible to

operate this heat engine with energy
flows of |qH| = 100 kJ/kg and |wnet| =
50 kJ/kg

• Apply the first law to this cycle and

check whether or not the cycle
violates the second law.

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November 2020 11
Thermodynamics
 Worked Example 3.4.3 – Solution
Apply the first law to conserve overall energy quantity:
wnet = q H − qC  qC = q H − wnet
 qC = 100 kJ/kg − 50 kJ/kg = 50 kJ/kg
Again, check the second law using efficiencies:
w net 50 kJ/kg TH − TC 600K − 300K
= = = 0.5  CARNOT = = = 0.5
qH 100 kJ/kg TH 600K

As η = ηCarnot the cycle is permitted by the second law (just

feasible).

It can also be concluded that the cycle is reversible. The increase

and decrease in energy quality balance, giving no net change.
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November 2020 12
Thermodynamics
 Worked Example 3.4.4 – Problem
Consider the heat engine below:

• The heat engine operates between

reservoir temperatures of TH = 600 K
and Tc = 300 K.

• Check whether it is possible to operate

this heat engine with energy flows of
|qH| = 100kJ/kg and |wnet| = 25kJ/kg.

• Apply the first law to this cycle and

check whether or not this cycle
violates the second law

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November 2020 13
Thermodynamics
 Worked Example 3.4.4 – Solution
Apply the first law to conserve overall energy quantity:
wnet = q H − qC  qC = q H − wnet
qC = 100 kJ/kg − 25 kJ/kg = 75 kJ/kg

Now check the second law using efficiencies:

wnet 25 kJ/kg TH − TC 600 K − 300 K
= = = 0.25  CARNOT = = = 0 .5
qH 100 kJ/kg TH 600 K

As η < ηCarnot the cycle is permitted by the second law and the cycle
is irreversible……… only 25% of heat supplied is converted to work,
and the maximum is 50%.

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November 2020 14
Thermodynamics
 Worked Example 3.4.4 – Solution
Here, less work is being extracted in comparison to a Carnot cycle
and more heat is being discarded to the cold reservoir.
Consequently, the decrease in quality, when moving (a larger
amount of) heat from the hot to the cold reservoir, is more than
the increase in quality when (a smaller amount of) net work is
produced from heat.
Overall, taking both effects into account, there is a net decrease in
energy quality and this cycle is permitted by the second law – it is
an irreversible heat engine cycle.
The irreversibility is caused by not extracting the maximum
possible work the cycle is capable of doing (given the two
reservoirs available).

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November 2020 15
Thermodynamics
 3.7.1 Problem
To show how the second law can be applied to molecules or
atoms and not just to flows of energy, consider 1 kg of
ammonia vapour with heat capacity at constant pressure of
2175 (J/kg K).

Take this vapour at 100oC and cool is down to 20oC using an

isobaric process (an isobaric compression or expansion may be
accomplished using a piston cylinder device with a mass on
top of the moveable piston).

Thus, heat and work may be exchanged between the system

and surroundings, but the pressure inside the system is fixed
by the constant force (acting down) over a constant area.
Calculate the total entropy change for such a process.
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November 2020 16
Thermodynamics
 3.7.1 Solution
Perhaps the first step is to find the entropy change of the
system which may always be found from
 dQ 
2
S SYS =  
1
T  REV
• For a constant pressure process dQ = dH , so that the
above becomes
H2
 dH 
S SYS = 
H1

 T



• It is also known that dH = mc P dT . Thus, substitute for dH

T2
 mc dT  T2
dT
S SYS =  P  >> Const. CP>> S SYS = mc P 
T1 
T  T
T1

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November 2020 17
Thermodynamics
 After completing integration, the system entropy change is
given by
T2
S SYS = mc P ln
T1
J 293 K
 S SYS = 1 kg  2175 ln
kg K 373 K
 S SYS = −525.1 J/K SYSTEM ∆s

• To calculate the entropy change of the surroundings the

amount of heat exchanged between the system and
surroundings must first be found.
• This is best accomplished by starting with the definition of
heat capacity
 dq   dh 
cP =   = 
 dT  P  dT  P
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Thermodynamics
 For a constant pressure process this becomes
T2

Q = H =  mcP dT
T1

• Assuming that the heat capacity is constant, this may be

integrated to give
T2

Q = mcP  dT
T1

 Q = mc P (T2 − T1 )
J
Q = 1kg  2175 (293 K − 373 K)
kg K
 Q SYS = −174 kJ >>> QSURR = +174 kJ

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Thermodynamics
 The entropy change of the surroundings is given by
QSURR
S SURR =
TSURR

• Taking the surroundings temperature to be the final

temperature of the system (20oC) yields
174000  1 
S SURR = + (J ) 
293 K
 S SURR = +593.9 J/K SURROUNDINGS ∆s

• The entropy change of the surroundings is positive since

heat is transferred into the surroundings.
• The total entropy change of system and surroundings
together may then be found
S TOTAL = S SYS + S SURR = −525.1 + 593.9 J/K

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November 2020 20
Thermodynamics
 Thus, the total entropy change of system and surroundings

 S TOTAL = +68.8 J/K

• Therefore, this process does indeed satisfy the second law

S SYS + S SURR  0 and the process is feasible.
• The fact that the total entropy change is greater than zero
indicates that overall the process is irreversible.
• This result is a little puzzling because, the first law for a
closed system is Q + W = U 2 − U1 . While for a reversible
constant pressure process W = − P(V2 − V1 ).
• Combining these two results led to Q = H
>> This is puzzling because, on the one hand, the work
exchanged was assumed to be reversible while, on the other
hand, STOTAL = +68.8 J/K; surely one would expect STOTAL = 0 ??
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Thermodynamics
 For any process to be completely reversible:
1. The work done on or by the system must be reversible.

2. The heat transferred to or from the system must be

reversible.
In this example the volume work done on the system as the
piston compresses the ammonia gas was assumed to be
reversible.
• However, the heat transfer was through a finite
temperature difference, therefore, this component was
transferred irreversibly.
• Any irreversibility, either due to “1” or “2”, makes the
overall process irreversible and, with the heat transfer
being irreversible, it is to be expected that……………
Overall the process is irreversible, even when
STOTAL  0
the work transfer step is reversible!!
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November 2020 22
Thermodynamics
 3.7.2 Problem
Take it that a heat engine cycle operates between hot and cold
reservoir temperatures of 600 K and 300 K respectively.

100 kJ/kg of heat is supplied to the cycle by the hot reservoir,

while 50 kJ/kg of net work is delivered by the cycle.

Calculate whether or not this cycle is feasible using   CARNOT

and then use the entropy changes to confirm these findings.

Notice that energy flows are expressed in terms of specific

quantities.

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November 2020 23
Thermodynamics
 3.7.2 Solution
The heat engine cycle is shown below. All energy flows are
absolute
Care values
must be taken when (the signs
analysing have
a heat enginebeen
cycle: removed):

Hot Reservoir
•-• Now
First find signs
The eliminate
working outwithin
fluid if the cycle is possible
for “ the device
TH undergoes a cycle s = 0.
using
q , q & w ” as follows:
H C net
SYS

qH
• There are two heat reservoirs
 
(surroundings)
CARNOT the hot and the cold
wnet qH = q
reservoir. 12  …(kJ/kg)
•• Find the
= q34Carnot
qC entropy
The
cycle
change(kJ/kg)
s
efficiency
of
qC SURR − H

T −T
the hot reservoir decreases.
wnet = w23 + w41H(kJ/kg)C 600 K − 300 K
TC  CARNOT = =
Cold Reservoir • The entropy change s SURR −C of
T 600 K
wnet = wNET (kJ/kg)
H
the cold reservoir increases.
•
At these hot & cold reservoir temperatures
1
CARNOT = only 50% of the heat supplied (maximum)
2 may be converted into net work!!

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November 2020 24
Thermodynamics
 Then find the efficiency of the cycle as stated in the problem
wnet 50 1
= = >>> =
qH 100 2
• Comparing this cycle to a Carnot cycle, leads to
 = CARNOT
• This means that the cycle in question is feasible since it
satisfies    CARNOT .
• In addition, since  = CARNOT it follows that it must be a
reversible cycle.
• It should also be possible to test for feasibility/
reversibility/ irreversibility using entropy. The total entropy
change sTOTAL is the sum of three entropy changes:

sSYS sSURR − H sSURR −C

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November 2020 25
Thermodynamics
 Thus, the total entropy change is
sTOTAL = s SYS + s SURR, H + s SURR,C
• The working fluid within the device undergoes a cycle and
periodically returns to its original state, so that sSYS = 0 .
• The entropy change of the hot reservoir sSURR , H is easily
found from the expression discussed previously
qH 100 kJ/kg
s SURR , H = =− = −0.167 kJ/kg K
TH 600 K
• To calculate sSURR ,C the heat transferred to the cold
reservoir must be found.
>> This is easily done by constructing an energy envelope
around the inner circle of the heat engine cycle
>>> This inner circle represents the cyclic operation of the
system which experiences no overall energy change over a cycle.
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Thermodynamics
 These energy flows are absolute values and the direction of
the arrows represent the direction in which energy enters and
leaves the system, either as heat or net work.
• The first law then simply states that quantity of energy
entering & leaving the cycle must be equal.
qH − qC = wnet
 qC = 100 − 50 = 50 kJ/kg
• Thus, entropy change of the cold reservoir and the total
entropy change are given by
qC 50 kJ/kg These results are
s SURR ,C = =+ = +0.167 kJ/kg K consistent with
TC 300 K previous ones. The
cycle is just feasible
 sTOTAL = 0 − 0.167 kJ/kg K + 0.167 kJ/kg K = 0
and is REVERSIBLE.

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November 2020 27
Thermodynamics
 3.7.3 Problem
Take it that an ideal (reversible) refrigerator operates between
a low temperature reservoir of 276 K and a high temperature
reservoir of 298 K.

Take it that the net power input is 0.08 (kW) and that the heat
withdrawal rate from the cold space is 1 (kW).

Calculate whether or not this cycle is feasible using COP  COPfridge

rev

and then use the entropy changes to confirm these findings.

Notice that this time energy flows are expressed in terms of

total quantities – either approach is possible.

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November 2020 28
Thermodynamics
 3.7.3 Solution
The heat and work flows are reversed and total quantities
(kW) are used – again these are absolute values:
Hot Reservoir

TH • First find out if this cycle is possible

using
wnet
COP  COPfridge
rev

qC
• Find the COP of a reversible fridge
TC
Cold Reservoir
TC 276 K
See Topic 4 for this  COP rev
= =
TH − TC 298 K - 276 K
fridge
derivation; also repeated
in topic 5 notes. At these hot & cold reservoir temperatures
this determines the minimum net work
 COPfridge
rev
= 12.5 input needed to move unit amount of heat
between these reservoirs.
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Thermodynamics
 Then find the COP of the cycle as stated in the problem
Q C 1
COP = = >>> COP = 12.5
W net 0.08
• Comparing this cycle to a reversible cycle, leads to
 COP = COPfridge
rev

• This means that the cycle in question is feasible since it

satisfies COP  COPfridge
rev
.
• In addition, since COP = COPfridge rev
it follows that it must
be a reversible cycle.
• Again, it should also be possible to test for feasibility/
reversibility/ irreversibility using entropy. The total entropy
change STOTAL is the sum of three entropy changes:

SSYS SSURR − H SSURR −C

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Thermodynamics
 Once again, the total entropy change is still
STOTAL = SSYS + SSURR , H + SSURR ,C
• The working fluid within the device undergoes a cycle and
periodically returns to its original state, so that SSYS = 0 .
• Once again, the entropy change of the cold reservoir SSURR ,C
is easily found from

Q 1 kW
SSURR ,C = C = − = −0.0036 kW/K
TC 276 K
• To calculate SSURR , H the heat transferred to the hot
reservoir must be found.
>> Once again constructing an energy envelope around the
inner circle of this refrigeration cycle.
>>> This inner circle represents the cyclic operation of the
system which experiences no overall energy change over a cycle.
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November 2020 31
Thermodynamics
 Again, these energy flows are absolute values and the
direction of the arrows represent energy entering and leaving
the system, either as heat or net work.
• Again, the first law then simply states that the rate at which
energy enters & leaves the cycle must be equal.
Q H − Q C = W net

 Q H = 1 kW + 0.08 kW = 1.08 kW
• Thus, entropy change of the hot reservoir and the total
entropy change are given by
Q H 1.08 kW These results are
SSURR , H =+ =+ = +0.0036 kW/K consistent with
TH 298 K
previous ones. This
 STOTAL = 0 + 0.0036 kW/K − 0.0036 kW/K = 0 cycle is just feasible
and is REVERSIBLE.

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November 2020 32
Thermodynamics