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Camille M.

Velasco
Dianne M. Villanueva

Thermodynamics I

1.0 ENTROPY DEFINITION

The term entropy was first used by Rudolf Clasius to state the second law of
thermodynamics.
It is taken from a Greek word tropee which means transformation.
Defined as the quantitative measure of disorder or randomness in a system. The
concept comes out of thermodynamics, which deals with the transfer of heat energy
within a system.
Unit of measurement is J/K (Joule per degree Kelvin).
Entropy is denoted by S, while specific entropy is denoted by s in all
mathematical calculations.

1.1 CALCULATING ENTROPY


In an is isothermal process, the change in entropy (delta-S) is the change in heat (Q)
divided by the absolute temperature (T):

delta-S = Q/T

In any reversible thermodynamic process, it can be represented in calculus as the


integral from a process initial state to its final state of dQ/T.

In a more general sense, entropy is a measure of probability and the molecular disorder
of a macroscopic system. In a system that can be described by variables, there are a
certain number of configurations those variables may assume. If each configuration is
equally probable, then the entropy is the natural logarithim of the number of
configurations, multiplied by Boltzmanns constant.

S=KB In W

Where S is entropy, kB is Boltzmanns constant, In is the natural logarithm and W


represents the the number of possible states. Boltzmanns constant is equal to 1.38065
x 10-23 J/K

1.2 UNITS OF ENTROPY


Entropy is considered to be an extensive property of matter that is expressed in terms
of energy divided by temperature. The SI units of entropy are J/K (joules/degrees
Kelvin)
1.3 MISCONCEPTIONS ABOUT ENTROPY
This view of the of the second law of thermodynamics is very popular, and it has been
misused. Some argue that the second law of thermodynamics means that a system can
never become more orderly. Not true, It just means that in order to become more orderly
(for entropy to decrease), you must transfer energy from somewhere outside the system,
such as when a pregnant women draws energy from food to cause the fertilized egg to
become a complete baby, completely in line with the second lines provisions

2.0 PRINCIPLES OF ENTROPY

Form the Clausius inequality, Q / T 0


As the entropy is a property of the system, therefore the cyclic integral of a property is zero
and the above equation can also be written as:
Q / T dS
SQ / T dS
dS Q / T
for isolated system, SQ = 0

therefore
(dS)iso 0
For a reversible process: (dS) iso = 0
Or
S = constant
For an irreversible process: dS) iso > 0 or entropy increases.

Thus it may be concluded that entropy of an isolated system can never decrease. It always
increases with every irreversible process and remains constant when the process is reversible.
This is known as principle of entropy increase or in other words the entropy of principle.

3.0 SAMPLE PROBLEMS

3.1 What is the change in entropy when 100 grams of ice at 0 o C melt into 100 grams of water
at 0 o C?

Solution:

Using the 8,000 calories calculated above and converting the temperature of 0 o C into 273 K,
we find
temperature change in the heat of the system change in entropy =

S = Q = 8,000 cal = 29.3 cal/K


T 273K

3.2 Calculate the standard-state entropy of reaction for the following reactions and explain the
sign of S for each reaction.

(a) Hg(l) Hg(g)

(b) 2NO2(g) N2O4(g)

(c) N2(g) + O2(g) 2NO(g)

Solutions:

(a) Using a standard-state entropy data table, we find the following information:

Compound S(J/mol-K)

Hg(l) 76.02

Hg(s) 174.96

The balanced equation states that 1 mole of mercury vapor is produced for each mole of liquid
mercury that boils. The standard-state entropy of reaction is therefore calculated as follows:

So = So(products) - So(reactants)

= [1 mol Hg(g) x 174.96 J/mol-K] - [1 mol Hg(l) x 76.02 J/mol-K]

= 98.94 J/K

The sign of So is positive because this process transforms a liquid into a gas, which is
inherently more disordered.

(b) Using a standard-state entropy data table, we find the following information:

Compound S(J/mol-K)

NO2(g) 240.06

N2O4(g) 304.29
In this equation, 1 mole of N2O4 is formed for every mole of NO2 consumed, and the value
of So is calculated as follows:

So = So(products) - So(reactants)

= [1 mol N2O4(g) x 304.29 J/mol-K] - [2 mol NO2(l) x 240.06 J/mol-K]

3.3 Determine if the entropy change will be positive or negative for the following reactions:

A) (NH4)2Cr2O7(s) Cr2O3(s) + 4 H2O(l) + CO2(g)

B) 2 H2(g) + O2(g) 2 H2O(g)

C) PCl5 PCl3 + Cl2(g)

Solutions:

Entropy of a reaction refers to the positional probabilities for each reactant. An atom in gas
phase has more options for position than the same atom in a solid phase. This is why gases
have more entropy than solids.

In reactions, the positional probabilities must be compared for all the reactants to the
products produced.

If the reaction involves only gases, the entropy is related to the total number of moles on
either side of the reaction. A decrease in the number of moles on the product side means
lower entropy. An increase in the number of moles on the product side means higher entropy.

If the reaction involves multiple phases, the production of a gas typically increases the
entropy much more than any increase in moles of a liquid or solid.

Reaction A

(NH4)2Cr2O7(s) Cr2O3(s) + 4 H2O(l) + CO2(g)

The reactant side contains only one mole where the product side has six moles produced.

The was also a gas produced. The change in entropy will be positive.

Reaction B

2 H2(g) + O2(g) 2 H2O(g)

There are 3 moles on the reactant side and only 2 on the product side. The change in entropy
will be negative.

Reaction C

PCl5 PCl3 + Cl2(g)

There are more moles on the product side than on the reactant side, therefore the change in
entropy will be positive.

ANSWERs:

Reactions A and C will have positive changes in entropy.


Reaction B will have negative changes in entropy.

= -175.83 J/K

The sign of So is negative because two molecules combine in this reaction to form a larger,
more ordered product.

(c) Using a standard-state entropy data table, we find the following information:

Compound S(J/mol-K)

NO(g) 210.76

N2(g) 191.61

O2(g) 205.14

The balanced equation for this reaction indicates that 2 mole of NO are produced when 1
mole of N2 reacts with 1 mole of O2 . Thus, the standard-state entropy of reaction is
calculated as follows:

So = So(products) - So(reactants)

= [2 mol NO x 210.76 J/mol-K] - [1 mol N2 x 191/61 J/mol-K + 1 mol O2 x

205.14 J/mol-K]

= 24.77 J/K

So for this reaction is small but positive because the product of the reaction (NO) is slightly
more disordered that the reactants ( N2 and O2).
4.0 ENTROPY BALANCE DEFINITION
an expression of the second law of thermodynamics that is particularly convenient for
thermodynamic analysis
a basic equation for non-equilibrium thermodynamics
The increase of entropy principle is expressed as
Entropy change = Entropy transfer + Entropy generation

Ssystem Stransfer Sgen


This is called the entropy balance.
This equation shows the relation between the three thermodynamic quantities: the
entropy change, the entropy production and the entropy flow. The entropy change is
the time derivative of the entropy of the system, S/t, and is given as the sum of two
integrals (the entropy production and the entropy flow) taken over the system:

5.0 CALCULATION OF ENTROPY BALANCE EQUATION


5.1 ENTROPY BALANCE ON OPEN SYSTEMS


Q j
ds
m isi m ese s gen
m
dt Tj

Rate at which the entropy of the system changes


=
Rate at which entropy changes due to heat transfer into or out of the system
+
Rate at which entropy flows into the system
-
Rate at which entropy flows out of the system
+
Rate at which entropy is generated within the system

5.2 ENTROPY BALANCE ON CLOSED SYSTEMS

Qj
s m s
gen
Tj

6.0 ENTROPY TRANSFER

Entropy can be transferred to or from a system by two mechanisms: heat transfer and mass
flow. Note that no entropy is transferred by work.
Entropy can be transferred to or from a system by two mechanisms: heat transfer and mass
flow. Note that no entropy is transferred by work.

6.1 Heat Transfer

Heat transfer to a system increases the entropy of the system, and heat transfer out of a
system decreases the entropy of the system.

During a process 1-2 of a system as defined above, If heat transfer Q happens at the system
boundary which has an absolute temperature T, the entropy transfer associated with this heat
transfer process is

If the entire boundary temperature remains as a constant T, the above equation can be
simplified as

Sheat = Q/T

where Q = total heat transfer during process 1-2

When the temperature T is not a constant, but a function of its location, the entropy
change can be approximated as

where
Qk = heat transfer at boundary location k
Tk = temperature at boundary location k

6.2 Mass Transfer

Mass contains entropy as well as energy. Mass m, which has a specific entropy s, contains
a total entropy of ms. When a mass flows in a system, the entropy increase in the system
is ms. In the same manner, mass m flowing out of a system will result in a decrease of
entropy in amount of ms in the system.

Smass = ms
6.0 SAMPLE PROBLEMS
6.1 Saturated liquid water at 100 C is contained in a pistoncylinder assembly. The water
undergoes a process to the corresponding saturated vapor state, during which the piston
moves freely in the cylinder. There is no heat transfer with the surroundings. If the change
of state is brought about by the action of a paddle wheel, determine the network per unit
mass, in kJ/kg, and the amount of entropy produced per unit mass, in kJ/kg.K.

Assumptions:
1 The water in the pistoncylinder assembly is a closed system.
2 There is no heat transfer with the surroundings.
3 The system is at an equilibrium state initially and finally. PE = KE = 0.

Solution:
The network can be calculated by using the law:
U + KE + PE = Q W
That is simplifies to:
U = W

On a unit mass basis, the energy balance becomes:


W / m = (ug uf)
From Table A4,
W / m = 2087.6 kJ/kg
The negative sign indicates that the work input by the stirring is greater than the work
done by the water as it expands.

Using an entropy balance, the amount of entropy produced can be found. Since there is
no heat transfer,

On a unit mass basis, this becomes:

Using Table A4
Sgen / m = 6.048 kJ / kg.K Ans.
6.2 Steam enters a turbine with a pressure of 3 MPa, a temperature of 400 C, and a
velocity of 160 m/s. Saturated vapor at 100 C exits with a velocity of 100 m/s. At
steadystate, the turbine develops work equal to 540 kJ/kg. Heat transfer between the
turbine and its surroundings occur at an average outer surface temperature of 350 K.
Determine the rate at which entropy is produced within the turbine per kg of steam
flowing, in kJ/kg.K. Neglect the change in potential energy between inlet and exit.

Assumptions:
1 Steady state operation in CV. PE = 0.
2 Turbine outer surface is at a specified average temperature.

Solution:
From the mass balance, we know that m = m1 = m2
Since the process is steadystate, one can write:

The heat transfer occurs at Tb = 350 K, the first term of the right hand side of the entropy
balance reduces to Q/ Tb

We need to calculate the rate of heat transfer. The first law (energy balance) can be used
to find the heat transfer rate. Combining the mass balance and the first law, one finds:

From Table A6, h1 = 3230.9 kJ/kg, and From A4 h2 = 2676.1 kJ/kg. After substitution,
and converting the units, one finds:

22.6 kJ / kg

From Table A4, s2 = 7.3549 kJ/kg.K and from Table A6, s1 = 6.9212 kJ/kg.K. Inserting
values into the expression for entropy production:
0.4983 kJ / kg Ans.

References:
Engineering Thermodynamics by P K Nag
https://www.thoughtco.com/entropy-definition-calculation-and-misconceptions-2698977
https://www.thoughtco.com/entropy-change-problem-609481
http://petrowiki.org/Second_law_of_thermodynamics
http://www.mdpi.com/journal/entropy

1.0 REFRIGERATORS
The second law of thermodynamics says that heat can
flow from high temperature reservoir to low temperature
reservoir only, however, if you want to move the heat from low
temperature to high temperature reservoir, then the external work
has be supplied.
Refrigerators are devices that will transfer heat from a
low temperature environment to a high temperature environment.
Normally, heat will only flow from a hotter environment to a
colder environment. This makes it seem like the concept of a
refrigerator breaks the second law of thermodynamics.

From the diagram it can be seen that a refrigerator consist of four basic components. These are:
-a compressor
-a condenser
-an expansion valve (also known as a throttling valve)
-an evaporator.

Refrigeration is a process of maintaining low temperature in comparison to surrounding


temperature. It is also the process of removing heat from an enclosed space, and rejecting it
elsewhere for the primary purpose of lowering the temperature of the enclosed space or
substance and then maintaining that lower temperature.
It is usually done with the aid of a mechanical device (heat pump) using a substance
(refrigerant) which absorbs heat from low temperature and releases heat elsewhere at high
temperatures,

1.1COEFFICIENT OF PERFORMANCE
The coefficient of performance represents the amount of heat removed in comparison to
work in, and the higher the number the better that refrigerator is performing. It is also
defined as the ratio of the refrigerating effect (QL) to the work added to the system
(Wnet). This number can be greater than 1, which means that this number doesn't
represent the efficiency of the refrigerator and should not be confused with efficiency.
The coefficient of performance, which indicates how well the refrigerator is functioning,
can be calculated by using:
QC QC 1
COPR where:
Wnet QH QC QH COPR = Coefficient of Performance of a Refrigerator
1 Wnet = net work done by the refrigerator
QC
QC = heat rejected TC = lower temperature
TC 1 QH = heat absorbed TH = higher temperature
COPR
TH TC TH
1 Manipulation of given data can be used to find other
TC
missing values.

2.0 PROCESS OF REFRIGERATION


Work is input into the compressor to compress the refrigerant to a high pressure as it enters
the condenser, which is the network of tubes seen on the back of the refrigerator. While the
refrigerant is being compressed to a high pressure, the temperature also increases to a higher
temperature then the environment outside of the refrigerator, which in turn will cause the outside
environment to act like a sink. After the refrigerant has gone through the condenser it will reach
the expansion valve. The expansion valve will cause the pressure and temperature of the
refrigerant to drop drastically. The temperature of the refrigerant will now be lower than the
environment inside refrigerator. The cooled refrigerant will then enter the evaporator, which
is a series of tubes inside of the refrigerator. As the refrigerant flows through the evaporator, the
refrigerators environment will act like a source and heat will be transferred into the refrigerator
causing it to evaporate. The refrigerant, which is now a gas, will enter the compressor again,
where it will be compressed back into a liquid at a high pressure and temperature, and the
process will repeat.

3.0 SAMPLE PROBLEMS


3.1 A vapor compression refrigeration system has to handle a cooling load of 2 tons. Find
the power of the compressor in kW if the COP is given as 3.5

3.2 A Carnot cycle operates between thermal reservoirs at 55C and 560C. Calculate the
COP if it is a refrigerator. Determine if the COP is good or bad. Explain.

3.3 In the set-up, the heat lost is 25000kJ/kg and the COP is 1.6. Find
the net work in MW.