Understanding the basics

1. Thermodynamic system
Any quantity of matter or any region in space that is subjected to a thermodynamic
analysis is called a thermodynamic system. What is external to the system is called
surroundings.
Thermodynamic systems are finite in nature, and hence macroscopic, rather than
microscopic.
Envelop which separates a system from its surroundings is called the system boundary.
System boundary can:
a. Isolate a system from its surroundings.
b. Permit transfer of matter or energy between the system and the surroundings.
Transfer of energy can be in two ways:
a. Heat.
b. Work.
2. Isolated system
An isolated system can neither exchange any matter or energy with the surroundings.
The system is unaffected by the surroundings. Imagine a perfectly insulated vessel with
no inlets and outlets, and chemical reactions between the substances within the vessel is
going on. Any heat of reaction associated with the process is not interchanged with the
surroundings, as the vessel is perfectly insulated. Neither any material transfer takes
place with the surroundings as the vessel has no inlet or outlet connections. The system
thus described is an isolated system.
3. Closed system
In a closed system, there is no transfer of matter between the system and the
surroundings, and hence the mass of a closed system is essentially constant. As there is
no transfer of matter across the boundary, there is no transfer of internal energy,
associated with the mass, across the boundary. All exchange of energy between a closed
system and the surroundings appears as heat and work. The energy change of the
surroundings is the net energy transferred to or from the system as heat and work.
When change in a system starts with the fluid in a state of rest and ends with the fluid
in a state of rest, the system can be thermodynamically analyzed as a closed system,
permitting quantitative computations. Some of the examples relevant to the process
industry are given below:
a. Heating of water in a vessel with live steam.
b. Cooling of hot water in a vessel by adding cold water.
c. Vaporization of liquid LPG in the storage tank during transfer by pipeline to
customers.
4. Control volume
For thermodynamic analysis of an open system, certain volume in space that surrounds
the system is called control volume. The control volume is bounded by a surface called
control surface. If a heat exchanger is considered for thermodynamic study, certain
volume in space surrounding the heat exchanger is the control volume. The boundary
of the control volume in which the heat exchanger is present is called the control
surface. Streams can flow in and out of the control surface with accompanying energy
depending upon whether they are hot or cold.
5. Open system
 In an open system, surrounded by a control volume, mass and energy transfer can take
place across the control surface.
Mass and energy balance relationships can be developed for the thermodynamic system
within the control volume. These relationships can be developed for unsteady state
transfer of mass and energy across the control surface, steady state transfer being a
special case.
Industrial applications of thermodynamic analysis of open systems are many. Some
common situations are described below:
a. Unsteady state cooling of a tank containing hot fluid by introduction of a cold fluid.
b. Heat removal during compression of gas.
c. Steady state flow problems.
d. Quantity of gas required to raise the pressure in a closed vessel by connecting it to a
source of high pressure gas.
e. To determine the condition of a gas in a closed vessel after some of the gas has been
bled out of the vessel in unsteady state flow.
f. To determine the conditions of a flowing gas after throttling.
g. Expansion of a gas through an orifice.
6. Intensive and extensive properties
a. Intensive properties
Properties of a system which are independent of quantity of the material present are
called intensive properties. Examples are temperature, pressure, density,
concentration, specific heat, viscosity, refractive index etc.
b. Extensive properties
Properties that depend on the quantity material present in the system are called
extensive properties. Examples are volume, internal energy, enthalpy, entropy, work
etc.
When the extensive properties are expressed per unit mass or unit mole, these are
known as specific or molar properties. Examples are specific volume, molar
enthalpy, molar entropy etc.
To represent total properties of a system, it is necessary to multiply the specific or
molar properties by mass or number of moles of a system. Specific properties are
intensive, independent of the quantity of material present in the system.

7. State functions and path dependant functions

a. State functions
Water at 25⁰C and atmospheric pressure has fixed intensive properties, such as a
fixed specific internal energy, specific volume etc. If the water is heated to 100⁰C
and beyond, it is converted to steam. If the steam is cooled, it will condense to water
at 100⁰C and further cooling to 25⁰C will bring back the water to the initial state,
and the intensive properties are restored to the original values. Values of such
intensive properties do not depend on the history of the path that the water gone
through to reach the initial state. They only depend on the present state, however it
may be reached. Such intensive properties, which describe the internal or
thermodynamic state of a system, are called state functions. For a homogeneous
pure substance, if two intensive properties are fixed, the thermodynamic state of the
 system is fully described. If water is at 120⁰C and atmospheric pressure, it will
always be in the superheated vapor state.

b. Path dependant functions

When we take air at atmospheric pressure and ambient temperature and compress
it in a compressor, the pressure of the air will increase, as also the temperature of
the air due to heat of compression. If there is cooling water flowing in the
compressor jacket, some of the heat of compression will be transferred to the
cooling water. The work required for compression will not depend only on the
initial and final state of the air, but also in the manner the process of compression
took place. Path functions are functions that depend on the path taken to reach
from the initial state to the final state. Hence work and heat are known as path
dependant functions. The paths could be constant pressure, constant temperature,
constant volume, constant entropy and adiabatic.

(insert after “Relation between internal energy, heat and work)

Important relationships from internal energy and enthalpy

Internal energy

From the First law of Thermodynamics,

dU = dQ – dW

If the only force acting on the system is pressure,

dU = dQ – PdV

For a constant volume process,

dU = dQ

This implies that for a constant volume process, change in internal energy between initial
and final equilibrium states is equal to the heat added or removed from the system in
bringing about the change, i.e.

Uf – Ui = Q
---------------------------------------------------------------------------------------------------------------------
--(1)
It follows that,

(dU/dT)V = (dQ/dT)V = CV
----------------------------------------------------------------------------------------------------(2)

The change in internal energy for a constant volume process, between two equilibrium
states,
f
Uf – Ui = ∫ CV dT
----------------------------------------------------------------------------------------------------------------(3)
i

For an adiabatic process, there is no flow of heat into and out of the system, i.e. Q = 0.

dU = - PdV

Thus, the change in internal energy for an adiabatic process between two equilibrium
states is given by,
f
Uf – Ui = -∫ P dV
----------------------------------------------------------------------------------------------------------------(4)
i

In free expansion of a gas from an initial state to a final state, the gas expands into an
insulated and evacuated chamber in an irreversible manner. No work is done by the gas
and there is no transfer of heat. For an ideal gas, the temperature of the gas does not
change during free expansion. As internal energy of an ideal gas is a function of
temperature only, it follows that during free expansion of an ideal gas, there is no change in
internal energy. Hence,

Ui = Uf
---------------------------------------------------------------------------------------------------------------------
--------(5)

Enthalpy

The enthalpy of a system is defined as:

H=U+V

For an initial state of equilibrium to a final state of equilibrium, the change is represented
by:

dH = dU + d(PV)
Differentiating,

dH = dU + PdV + VdP

From First law of Thermodynamics,

dU = dQ – PdV

It follows that,

dH = dQ + VdP

This implies that for a constant pressure process, change in enthalpy between initial and
final equilibrium states is equal to the heat added or removed from the system in bringing
about the change, i.e.

Hf – Hi = Q
---------------------------------------------------------------------------------------------------------------------
--(1)

It follows that,

(dH/dT)P = (dQ/dT)P =
CP-----------------------------------------------------------------------------------------------------(2)

The change in enthalpy for a constant pressure process, between two equilibrium states,
f
Hf – Hi = ∫ CP dT
----------------------------------------------------------------------------------------------------------------(3)
i

For an adiabatic process, there is no flow of heat into and out of the system, i.e. Q = 0.

dH = VdP

Thus, the change in enthalpy for an adiabatic process between two equilibrium states is
given by,

f
Hf – Hi = ∫ V dP
----------------------------------------------------------------------------------------------------------------(4)
i
A throttling process is an irreversible process where the gas passes from an initial
equilibrium state to a final equilibrium state through a non equilibrium process, such that
the enthalpies of the initial and final equilibrium states are equal. Hence,
Hi = Hf
---------------------------------------------------------------------------------------------------------------------
--------(5)

Heat capacity of ideal gases

By definition,
CV = (dU/dT)V
CP = (dH/dT)P
A system in gas state can be fully specified by any two properties of the system. U can be
considered as a function of temperature and volume.
U = U(T,V)
dU = (dU/dT)VdT + (dU/dV)TdV
From First Law of Thermodynamics,
dU = dQ – PdV
For a constant volume process, dV = 0
Hence,
CV = (dU/dT)V = (dQ/dT)V
Similarly, H can be considered as a function of temperature and pressure.
H = H(T,P)
dH = (dH/dT)PdT + (dH/dP)TdP
By definition,
H = U + PV
dH = dU + PdV
Combining with First of Law of Thermodynamics,
dH = dQ – pdV + pdV
dH = dQ
Hence,
CP = (dH/dT)P = (dQ/dT)P
For an ideal gas:
1. PV = RT
2. The internal energy of an ideal gas depends only upon its temperature.
Since U is a function of only T, the relationship dU = (dU/dT) VdT + (dU/dV)TdV for any
gas reduces to
dU = (dU/dT)VdT for an ideal gas. Hence,
dU = CVdT
As H = U + PV, for an ideal gas H will also be a function of only T as U is a function of T.
Hence, for an ideal gas,
dH = (dH/dT)PdT consequent to the relationship dH = (dH/dT) PdT + (dH/dP)TdP for any
gas. Hence,
For finite changes,
∆U = ∫ CVdT, and
∆H = ∫ CPdT
Now,
 1. For small temperature changes, CP and CV may be assumed to be constant.
2. For larger temperature changes, CP and CV do not vary significantly with respect to
temperature.
In such cases,
dU = CVdT
dH = CPdT
U2 – U1 = CV (T2 – T1)
H2 – H1 = CP (T2 – T1)
These relations can be used for calculating finite changes in internal energy and enthalpy
provided the specific heats CP and CV are constant.
The specific heats for an ideal gas can be related to the gas constant, R. From the First of
Law of Thermodynamics,
dU = dQ – dW
dQ = dU + dW = dU + PdV
From definition of enthalpy,
dH = dU + PdV + VdP
dH = dQ – PdV + PdV + VdP
Hence, dQ = dH – VdP
dH – VdP = dU + PdV
CPdT – VdP = CVdT + PdV
(CP – CV)dT = PdV + VdP = d(PV)
For an ideal gas, PV = RT. Then,
d(PV) = RdT
Hence,
CP – CV = R
Denote CP / CV = γ
Then,
CV = R/(γ – 1)
CP = γR/(γ – 1)
Things to remember for ideal gases:
1. CV is a function of T only.
2. CP is a function of T only.
3. CP – CV = R
4. Specific heat ratio γ is function of T only and is greater than unity.
5. An ideal gas with constant specific heats (C P and CV – independent of temperature)
is called a perfect gas.
6. Specific heat ratio γ for mono atomic gases (He, Ne, Ar, most metallic vapors) is
nearly equal to 1.67 over a wide temperature range.
7. Specific heat ratio γ for di atomic gases (H 2, O2, N2, air, NO, CO) is nearly equal to
1.4 over a temperature range of 150 K to 600 K, and decreases above this
temperature.
8. CP and CV, and specific heat ratio for polyatomic gases (CO 2, NH3, CH4, Freons etc.)
vary with temperature. The variation is different for each gas. For high molecular
weight gases (as compared to diatomic gases), the value of γ is closer to unity.
9. The relationships given in the foregoing do not apply to real gases, as both U and H
depend not only on temperature, but also on pressure.
Using thermodynamic diagrams
Basics:
It is often necessary to know about relationships between different thermodynamic
properties like pressure, temperature, volume, enthalpy, entropy of substances in a manner
that is convenient for doing process engineering work. Relationships between such
thermodynamic properties, when shown on a single plot, are known as thermodynamic
diagrams, and can be used for evaluating thermodynamic properties of substances, or
representing thermodynamic cycles or paths. However, sometimes all thermodynamic
properties may not be shown on a single plot, but the term “thermodynamic diagrams” are
used for all such plots.
There are many types of thermodynamic diagrams. The more common thermodynamic
diagrams are given below:
1. Temperature – Enthalpy Diagrams.
2. Pressure – Enthalpy Diagrams, commonly lnP – H Diagrams.
3. Temperature – Entropy Diagrams.
4. Enthalpy – Entropy Diagrams, commonly known as Mollier Diagrams.
Temperature – Enthalpy Diagram:
 Figure 1: Temperature Enthalpy Diagram for Water
A temperature – enthalpy (t-h) diagram is a representation of the phase diagram of any
substance in a two dimensional plot, temperature and enthalpy being the two axes. A t-h
diagram for water is shown in Figure 1. The left hand side of the phase envelope is the
saturated water line, while the right hand side is the dry saturated steam line. The
saturated water line and the dry saturated steam line meet at the critical point. Left hand
side of the saturated water line is the region of sub cooled water. Right hand side of the dry
saturated steam line is the superheated steam region. A horizontal line between the
saturated water line and the dry saturated steam line represents the latent heat of
vaporization at the given pressure. Beyond the critical point (at temperatures higher than
the critical temperature), the sub cooled water region and the superheated steam region
cannot be distinguished, and is treated as supercritical fluid.
The phase envelope within the saturated water line and dry saturated steam line is a region
where both liquid water and steam coexist as a two phase mixture. Amount of steam in the
mixture at any point in the phase envelope is defined as the dryness fraction of the two
phase mixture. It can vary from 0 on the saturated water line to 1 on the dry saturated
steam line. Lines of constant dryness fraction are also shown with in the phase envelope.
As water at any temperature and pressure in the sub cooled region is heated, the water
becomes saturated as it reaches the saturated water line at the given pressure. Further
heating of the water evaporates the water at the given pressure at constant temperature, as
shown in Figure 1 as evaporation lines. Further heating the dry saturated steam superheats
the steam, and the enthalpy of the steam increases along the constant pressure lines.
t-h diagrams are available for all substances including hydrocarbons. The main utility of a
t-h diagram is evaluation of enthalpy of a substance for preparing heat balances.
Pressure Enthalpy Diagram:
 Figure 2: Pressure Enthalpy Diagram
Another useful thermodynamic diagram is the pressure-enthalpy diagram, shown in Figure
2, where pressure axis is shown on a rectangular scale. This diagram is a way of describing
the liquid and gas phase behavior of a substance. On the vertical axis is pressure, and on
the horizontal is enthalpy. The curved line on the left hand side is called the saturated
liquid line, and it defines the boundary between the sub cooled liquid region and the two
phase vapor/liquid mixture. The curved line on the right hand side is the saturated vapor
line, and defines the boundary between two phase vapor/liquid mixture and pure vapor or
gas. As the pressure is raised, a pressure known as critical pressure is reached, where the
saturated liquid line and the saturated vapor line converge at a point known as the critical
point. Above this pressure the gas cannot be liquefied.

As liquid in the sub cooled liquid region is heated at a given pressure, the liquid attains the
saturation temperature defined by the intersection of constant temperature lines and the
saturated liquid line. Further heating the liquid vaporizes the liquid at constant
temperature, till the saturated vapor line is reached, where the liquid is completely
vaporized. Within the envelope of saturated liquid line and saturated vapor line, the liquid
is partially vaporized, and the percentage of vapor in the mixture is seen from the constant
quality lines.

As the saturated vapor is further heated at constant pressure, the temperature of the gas
will increase in the right hand region of the saturated vapor line. The final temperature to
which the gas is heated will lie at the intersection of the horizontal pressure line and the
constant temperature lines. The horizontal distance between the saturated vapor line and
the constant temperature line represents the heat added.

Constant specific volume lines and constant entropy lines are also shown on the diagram.
p-h diagram are available for most substances including hydrocarbons and water. The
main use of p-h diagrams is for carrying out refrigeration calculations.

Temperature Entropy Diagram:

Figure 3: Temperature Entropy Diagram

One of the most useful thermodynamic diagrams is the temperature-entropy diagram. It
represents the phase behavior of a substance with entropy as the horizontal axis and
temperature as the vertical axis. As shown in Figure 3, the saturated liquid line and the
saturated vapor line meet at the critical point. A vertical line in the diagram indicates an
isentropic process (constant entropy). It is marked as “Isentropic Process” in the diagram.
In an “Actual Process” as marked in the diagram, the entropy does not remain constant,
but increases. System pressures outside the phase envelope have rising slopes, and within
the phase envelope they are horizontal lines, indicating vaporization as a constant pressure
and constant temperature process. Constant quality and constant specific volume lines are
also shown in the diagram. A temperature entropy diagram is useful for performing the
following engineering calculations:
a. Steam nozzle calculations.
b. Steam turbine and compressor calculations.
c. Gas turbine calculations.
d. Power plant calculations.
e. Refrigeration calculations.

Enthalpy Entropy Diagram:

 Figure 4: Enthalpy Entropy Diagram
Another very useful thermodynamic diagram is the enthalpy entropy diagram. It
represents the phase behavior of a substance with entropy as the horizontal axis and
enthalpy as the vertical axis. In addition to the lines of constant pressure and temperature
lines, this diagram also shows lines of constant quality of the substance within the two
phase envelope. In this diagram, vertical lines represent reversible processes and horizontal
lines represent constant enthalpy processes. The most important use of this diagram is for
doing power generation and refrigeration calculations, as the work done can be directly
taken from the vertical distances, as opposed to temperature entropy diagram.
Inefficiencies due to irreversibility in real processes can be shown in the same way as in
temperature entropy diagram. An enthalpy entropy diagram for water is shown in Figure
4.
Examples of process engineering calculations using thermodynamic diagrams:
Temperature Enthalpy Diagram:
1. Water at 315 K is pumped to a boiler operating at 700 kPa. The saturated steam
produced in the boiler is superheated by 11.9 K. Calculate the amount of heat
required to convert the water to superheated steam.
There are three parts for calculating the heat required:
a. Heat required to heat the water from 315 K to saturation temperature of
water at 700 kPa pressure.
b. Heat required to vapourize the water in the boiler at 700 kPa pressure.
c. Heat required to heat the produced saturated steam to obtain a 11.9 K
superheat.
These three steps are shown in the following temperature enthalpy diagram.
Thermodynamic data of water in the saturated and superheated region are taken
from Basic Principles and Calculations in Chemical Engineering by David M.
Himmelblau, 6th Edition.
T – h diagram for the problem
For required thermodynamic data for solving the problem is given in the following table
(ref.
Himmelblau):

Temp Press Enthalpy Temp Press Enthalpy

K kPa kJ/kg     K kPa kJ/kg
    Liquid Vapour       Vapour
315 8.143 175.1 2577.1   450 700 2791.3
435 647.4 705 2759.7        
440 733.2 771.1 2765        
438.1 700.0 745.5 2762.9        

Basis : 1 kg of water
Heat required to heat water from 315 K to saturation temp. at 700 kPa = mass of water x
(enthalpy of
saturated water at 700 kPa - enthalpy of water at 315 K)

= 1*(745.5 - 175.1) = 570.4 kJ/kg

Heat required to vaporize 1 kg of water at 700 kPa = mass of water x latent heat of
vapourization of water =
=1*(2762.9 - 745.5) = 2017.42634 kJ/kg
Heat required to superheat 1 kg of saturated steam at 700 kPa by 11.9 K =
= 1*(2791.3 - 2762.9) = 28.35081585 kJ/Kg
Total heat required to convert water at 315 K to superheated steam at 700 kPa and 11.9 K
superheat =
= 515.4 + 2017.4 + 28.4 = 2561.2 kJ/kg
 2. The following problem illustrates use of temperature enthalpy diagrams for
hydrocarbons, along with using other hydrocarbon system diagrams. For solving
the problem, hydrocarbon data has been taken from “Data Book on Hydrocarbons,
Applications to Process Engineering” by J.B.Maxwell, Ninth Printing. The book can
be downloaded for free from SCRIBD.

Problem 1 statement:
In order to be able to use the “Data Book on Hydrocarbons, Applications to Process
Engineering”, American units of measurement will be used throughout this problem
and its solution.

Vaporized heavy naphtha is used as fuel for a refinery heater. The header pressure
of vaporized heavy naphtha is maintained at 3.4 atm abs by pressure control, in
order to achieve the required heat release from heavy naphtha burners. It is
intended to supply heavy naphtha to the burners at 500F, to avoid condensation in
burner piping. Calculate the heat required to vaporize and superheat the heavy
naphtha from an initial liquid state at 100F. The ASTM 10% distillation of heavy
naphtha is as follows:

% Off ∘F
5 280
10 326
50 365
70 380
90 389 Other properties of heavy naphtha are as follows;
1. API: 51.3
2. Vol. Average
Boiling point: 361.25F
3. Mean Average
boiling point: 361.25F
4. K factor: 12.1
5. MW: 139
6. 100% EFV
Temperature: 477F @ 3.4 atm abs.
The solution to the problem requires calculation of latent heat of vaporization of heavy
naphtha, and heat of superheating the heavy naphtha vapors from 477F to 500F, from an
initial liquid state at 100F.
The latent heat of vaporization of heavy naphtha can be calculated from the relation that
heavy naphtha will have the same molal heat of vaporization as a normal paraffin at the
mean average boiling point of heavy naphtha.
For heavy naphtha:
Vapor pressure = system pressure = 3.4 atm abs.
Pseudo critical pressure = 250 psia (17 atm abs) for 361.25F mean average boiling point
and 51.3API
Reduced pressure of heavy naphtha = 3.4/17 = 0.2

For normal paraffin:

Vapor pressure = unknown = x
MW of normal paraffin = 148 for 361.25F mean average boiling point.
Critical pressure of normal paraffin = 20.8 atm abs for MW = 148.
Reduced pressure of normal paraffin = x/20.8
Vapor pressure of normal paraffin = 0.2 x 20.8 = 4.16 atm abs.

Latent heat of vaporization of normal paraffin = 98 Btu/lb for 361.25F mean average
boiling point and 4.16 atm abs vapor pressure.
Molal latent heat of heavy naphtha = 98 x 148 Btu/lb. mol
Hence, latent heat of vaporization of heavy naphtha = (98 x 148)/139 = 104.3 Btu/lb.
Calculate the heat required to raise temperature of liquid heavy naphtha from 100F to
saturation temperature of 477F:
Pseudo critical temperature of heavy naphtha = 685F for 361.25F mean average boiling
point and 51.3API. It is not within 50F of the temperatures in question i.e. 100F and
477F.
At 100F, Cp+B from chart = 0.565 for 100F and 51.3API.
B = 0.05 for Vol. Average boiling point of 361.25F.
Hence Cp at 100F = 0.565 – 0.05 = 0.515 Btu/lb/F
At 477F, Cp+B from chart = 0.755 for 477F and 51.3API.
B = 0.05 for Vol. Average boiling point of 361.25F.
Hence Cp at 477F = 0.755 – 0.05 = 0.705 Btu/lb/F
Average specific heat = (0.515+0.705)/2 = 0.61 Btu/lb/F.
Heat required to raise temperature of liquid heavy naphtha from 100F to saturation
temperature of 477F = (477-100) x 0.61 = 230 Btu/lb.
Calculate heat required to superheat heavy naphtha vapors from 477F to 500F:
Specific heat of petroleum vapors at 477F and 51.3API at 0 - 1 atm pressure = 0.585
Btu/lb/F
Specific heat of petroleum vapors at 500F and 51.3API at 0 - 1 atm pressure = 0.595
Btu/lb/F
As deviation of specific heat of naphtha vapors at system pressure of 3.4 atm abs will be
very small compared to a perfect gas, the specific heat is considered to be a function of
temperature alone.
Average specific heat between 477F and 500F = 0.59 Btu/lb/F.
Hence, heat required to superheat heavy naphtha vapors from 477F to 500F = (500 – 477)
x 0.59 = 13.6 Btu/lb.
Total heat to vaporize heavy naphtha from liquid state at 100F to vapor state at 500F and
3.4 atm abs pressure = 230 + 104.3 + 13.6 = 347.9 Btu/lb.

Calculate using enthalpy-temperature diagram of petroleum fractions:

For mean average boiling point of 300 F and K = 12.1
Liquid enthalpy at 100 F = 50 Btu/lb
For mean average boiling point of 400 F and K = 12.1
Liquid enthalpy at 100 F = 45 Btu/lb
Liquid enthalpy at 361.25 F mean av. bp and 100 F = 47 Btu/lb.

For mean average boiling point of 300 F and 3.4 atm abs and K = 12.1
Vapour enthalpy at 500 F = 395 Btu/lb
For mean average boiling point of 400 F and 3.4 atm abs and K = 12.1
Vapour enthalpy at 500 F = 388 Btu/lb

Heat required to raise heavy naphtha from liquid state at 100 F to vapor state at 500 F and 3.4 atm abs
Pr. = 343.7 Btu/lb.

This compares well 347.9 Btu/lb considering same molal heat of vaporization between heavy naphtha
and normal paraffin with same boiling point, and specific heats for liquid and vapor. The result is within
1.2% error.

Pressure Enthalpy Diagram:

Problem 1

Refrigerant - 134a enters the compressor of a refrigerator as superheated va

por at 1.4 Kg/cm2 and -10 deg C at a rate of 0.05 kg/s and leaves at 8.0 Kg/cm2
and 50 deg C. The refrigerant is cooled in the condenser to 26 deg C and
7.2 Kg/cm2 and is throttled to 1.5 Kg/cm2. Disregarding any heat transfer and
pressure drops in the connecting lines between the components, determine:
(a) The rate of heat removal from the reefrigerated space and the power input
to the compressor.
(b) The isentropic efficiency of the compressor.
(c) The coefficient of performance of the refrigerator.
Solution:
P – h diagram:

On the p-h diagram of R-134a, construct:

1. Horizontal lines through pressure isobars at 1.4, 1.5, 7.2 and 8.0 Kg/cm2.
2. Locate the point of intersection between 1.5 and 7.2 Kg/cm2 isobars and
saturated vapor line.
3. Locate Point 1 at the intersection of 1.4 Kg/cm2 isobar and -10C isotherm.
4. Locate Point 2 at the intersection of 8.0 Kg/cm2 isobar and 50 C isotherm.
5. Locate Point 3 at the intersection of 7.2 Kg/cm2 isobar and 26 C isotherm.
6. Locate Point 4 at the intersection of 1.5 Kg/cm2 isobar and vertical line from Point 3.
7. Locate Point 2s at the intersection of isentropic line through Point 1 and
intersection of line 2 - 3.
From the p-h diagram constructed as above:
At Point 1, h1 = 97.2 Kcal/Kg
At Point 2, h2 = 105.6 Kcal/Kg h2s = 103.2 Kcal/Kg
At Point 3, h3 = approx. hf @ 26 C = 57.2 Kcal/Kg
At Point 4, h4 = 57.2 Kcal/Kg (isenthalpic process)

(a) Rate of heat removal from the refrigerated space =( h1 - h4)*0.05 = (97.2 - 57.2)*0.05 =
40*0.05 Kcal/s = 2 Kcal/s = QL
Power input to compressor = h2 - h1 = (105.6 - 97.2)*0.05 = 0.42*3600*0.0012 = 1.8 KW =
Win
(b) Isentropic efficiency of the compressor = (h2s -h1)/(h2 - h1) = (103.3 - 97.2)/(105.6 -
97.2) = 72.6%
(c) Coefficient of performance of refrigerator = QL / Win = (h1 - h4)/(h2-h1) = (97.2 -
57.2) / (105.6 - 97.2) = 4.76
Problem 2

Consider a two - stage cascade refrigeration system operating between the pressure limits
of 8 Kg/cm2 and 1.4 Kg/cm2. Each stage operates on an ideal vapor compression
refrigeration cycle with refrigerant 134a as the working fluid. Heat rejection from the
lower cycle to the upper cycle takes place in an adiabatic counter flow heat exchanger
where both streams enter at about 3.2 Kg/cm2. Ignore that the lower cycle has to operate at
a higher pressure and temperature for effective heat transfer. Consider no sub-cooling of
the liquid in the condenser and vapor at compressor inlet is saturated. If the mass flow
rate of the refrigerant through the upper cycle is 0.05 Kg/s, evaluate:
(a) Mass flow rate of the refrigerant through the lower cycle.
(b) The rate of heat removal from the refrigerated space and the power input to the
compressor.
(c) The coefficient of performance of the cascade refrigerator.

Solution:
Operating principle of cascade refrigeration system:
See figure below:

The cascade refrigeration system consists of two stages of vapor copression refrigeration
cycles. However, the condenser of Stage II evaporates the refrigerant of Stage I in a
countercurrent heat exchanger. Both stages are independent of each other, and working
fluid can either be the same in both stages or different for each stage. The two stages can
operate at different operating temperatures and pressures, and can produce lower
refrigerated space temperatures than a single stage cycle with a lower compression ratio.

P – h diagram:

The P – h diagram for the above problem is given below:

Construction of operating points on the p - h digram:
1. Draw horizontal lines through 1.4 Kg/cm2, 3.2 Kg/cm2 and 8.0 Kg/cm2 isobars on the
vertical axis.
2. Locate Point 1 at the intersection of 1.4 Kg/cm2 isobar and saturated vapor line.
3. Locate Point 2 at the intersection of 3.2 Kg/cm2 isobar and the isentropic line through
Point 1.
4. Locate Point 5 at the intersection of 3.2 Kg/cm2 isobar and the saturated vapor line.
5. Locate Point 6 at the intersection of 8.0 Kg/cm2 isobar and the isentropic line through
Point 5.
6. Locate Point 7 at the intersection of 8.0 Kg/cm2 isobar and the saturated liquid line.
7. Locate Point 8 at the intersection of 3.2 Kg/cm2 isobar and the vertical line (isoenthalpic
line) through Point 7.
8. Locate Point 4 at the intersection of 1.4 Kg/cm2 isobar and the vertical line (isoenthalpic
line) through Point 3.

From the p - h diagram, read the enthalpy values as follows:

h1= 94.32 Kcal/kg
h4 = 49.92 Kcal/kg
h2 = 99.6 Kcal/kg
h5 = 97.2 Kcal/kg
h7 = 60 Kcal/kg
h8 = 60 Kcal/kg
h3 = 49.92 Kcal/kg
h6 = 102 Kcal/kg

(a) Mass flow rate of the refrigerant through the lower cycle:
Heat balance:
ma * ( h5 - h8) = mb* (h2 - h3)
ma = 0.05 Kg/s
mb = ma* (h5 - h8) / (h2 - h3)
= 0.05 *(97.2 - 60) / (99.6 - 49.92) = 0.037 Kg/s
(b) The rate of heat removal from the refrigerated space and the power input to the
compressor:
Rate of heat removal = QL = mb * (h1 - h4)
QL = 0.037 * (94.32 - 49.92) = 1.64 Kcal / s
Power input to the compressor:
Win = ma * (h6 - h5) + mb * (h2 - h1)
= 0.05 * (102 - 97.2) + 0.037 * (99.6 - 94.32) = 0.435 Kcal / s
= 0.435 * 3600 * 0.0012 = 1.88 Kw

(c) The cofficient of performance of the cascade refrigerator:

COP = QL / Win
= 1.64 / 0.435 = 3.77

Problem 3
Consider a two-stage compression refrigeration system operating between 8.0 Kg/cm2 and
1.4 Kg/cm2. The working fluid is refrigerant R - 134a. The refrigerant leaves the condenser
as a saturated liquid and is throttled to a flash chamber operating pressure of 3.2 Kg/cm2.

With reference to the figure below, the refrigerant leaves the condenser as a saturated
liquid and is throttled to a flash operating pressure of 3.2 Kg/cm2. Part of the refrigerant
evaporates during this flashing process, and this vapour is mixed with refrigerant leaving
the low pressure compressor. The mixture is then compressed to the condenser pressure by
the high pressure compressor. The liquid in the flash chamber is throttled to the
evaporator pressure and cools the refrigerated space as it vapourizes in the evaporator.
Assuming the refrigerant leaves the evaporator as a saturated vapour and both
compressors are isentropic, determine:
(a) The fraction of the refrigerant that evaporates as it is throttled to the flash chamber.
(b) The amount of heat removed from the refrigerated space and the compressor work per
unit mass of refrigerant flowing through the condenser.
(c) The coefficient of performance.

Refer the P – h diagram given below:

Construction of operating points on the P - h diagram:
1. Draw horizontal line through pressure isobars of 1.4 Kg/cm2, 3.2 Kg/cm2 and 8.0
Kg/cm2.
2. Locate Point 1 at the intersection of 1.4 Kg/cm2 isobar and saturated vapor line.
3. Locate Point 2 at the intersection of 3.2 Kg/cm2 isobar and isentropic line through
Point 1.
4. Locate Point 3 and Point 7 at the intersection through 3.2 Kg/cm2 isobar and saturated
vapour and saturated liquid line respectively.
5. Locate Point 5 at the intersection of 8.0 Kg/cm2 isobar and the saturated liquid line.
6. Locate Point 6 at the intersection of 3.2 Kg/cm2 isobar and vertical line through Pont 5.
7. Locate Point 9 at the intersection of the Enthaly value at Point 9 and 3.2 Kg/cm2 isobar.
8. Calculate Enthalpy value at Point 9 as follows:
(a) Point 6 lies at the intersection of 3.2 Kg/cm2 isobar and the constant quality line of 0.2.
(b) Let 0.2 = x6
(c) Denote Enthalpy by symbol h.
(d) From p - h diagram, read h3 = 97.92 Kcal/kg.
(e) From p - h diagram, read h2 = 99.6 Kcal/kg.
(f) h9 = x6 * h3 + (1 - 0.x6) * h2
(g) Solving h9 = 99.26 Kcal/kg
9. From the p - h diagram, read Enthalpy values at other points as follows:
(a) h1 = 94.8 Kcal/kg
(b) h7 = h8 = 49.2 Kcal/kg
(c) h4 = 103.2 Kcal/kg
10. Let QL = amount of heat removed from the refrigerated space.
QL = (1-x6) * (h1 - h8) = (1 - 0.2) * (94.8 - 49.2) = 36.48 Kcal/s
11. Compressor work per unit mass of refrigerant flowing through the condenser.
Let compressor work = Win
Win = (1-x6) * (h2 - h1) + 1 * (h4 - h9)
= (1 - 0.2) * (99.6 - 94.8) + 1 * (103.2 - 99.26) = 7.78 Kcal/s
= 7.78 * 3600 * 0.0012 = 33.61 Kw
12. The coefficient of performance, COP.
COP = QL / Win
= 36.48 / 7.78 = 4.69

Temperture Entropy Diagram

Problem 1
A back pressure steam turbine, driving a centrifugal pump, is operating with inlet steam
pressure at 14 Kg/cm2 and 500 C. The exhaust steam pressure is 0.1 Kg/cm2, and exhaust
steam quality is found to be 0.99, using a separating/throttling calorimeter. Find the thermal
efficiency of the steam turbine. Show the results on a temperature - entropy diagram of
steam.
Solution:
On a temperature - entropy diagram of steam, construct the following:

1. For an inlet steam condition of 500 C (vertical axis of temperature entropy diagram)
and 14 kg/cm2, locate point H1 at the intersection of the horizontal line for 500 C
and and constant pressure isobar of 14 Kg/cm2. Note that H1 lies in the vapor phase
portion of temperature entropy diagram and is above the critical temperature of
steam. On the horizontal axis of entropy, read the entropy at H1 as S2 = 1.8
Kcal/Kg-C.
2. For a turbine exhaust steam pressure of 0.1 Kg/cm2, note that the exhaust steam
quality is in the two phase region of the temperature - entropy diagram. Read point
H2 (saturation temperature of steam at 0.1 Kg/cm2 = 46 C) at the intersection of
the horizontal line through 46 C and the vertical line through point H1.The vertical
line through H2 also has an entropy of S2 = 1.8 Kcal/Kg-C. The quality of steam
 passing through point H2 is calculated as follows from the temperature entropy
diagram:
a. Read the entropy of saturated liquid at the intersection of the saturated
liquid line and saturation temperature of 46 C, and dropping a vertical line
through this intersection to the horizontal axis. Read SsatdL = 0.16 Kcal/Kg-
C.
b. Read the entropy of saturated vapor at the intersection of the saturated
vapor line and saturation temperature of 46 C, and dropping a vertical line
through this intersection to the horizontal axis. Read SsatdV = 1.9 Kcal/Kg-
C.
c. The quality of steam at S2 = (1.8 – 0.16) / (1.9 – 0.16) = 0.94.
d. This is the quality had the expansion through the steam turbine been
reversible.
3. The actual steam quality at the turbine exhaust is given as 0.99. Since the actual
turbine operation is irreversible, the entropy of the actual exhaust will be more than
the entropy of the reversible exhaust given by point H2. On the temperature –
entropy diagram, the exhaust condition of steam is represented by point H2 on the
0.1 Kg/cm2 isobar. Since the exhaust steam quality is less than 1.0, point H2 will lie
on the two phase region of the temperature – entropy diagram.
4. The efficiency of the steam turbine is given by the ratio of the actual enthalpy drop
between inlet steam to the turbine and exhaust steam from the turbine, and
enthalpy drop between inlet steam to the turbine and exhaust steam from the
turbine for the reversible operation.
5. We have to first evaluate the enthalpy drop for the reversible operation for a
reversible exhaust steam quality of 0.94. This is evaluated as follows:
a. From the temperature – entropy diagram enthalpy of saturated liquid at 0.1
Kg/cm2 = 46.0 Kcal/Kg.
b. From the temperature – entropy diagram enthalpy of saturated vapor at 0.1
Kg/cm2 = 620.0 Kcal/Kg.
c. Enthalpy of steam at point H2 = 46 + (620 – 46)*0.94 = 585.6 Kcal/Kg.
d. Enthalpy of steam at turbine inlet is the isenthalpic line passing through
point H1 = 834 Kcal/Kg.
e. Enthalpy drop for the reversible operation = H2 - H1 = 585.6 - 834 = - 248.4
Kcal/Kg
6. Next assume the enthalpy of the exhaust steam as H2 for the actual operation for a
steam exhaust quality of 0.99. Evaluate H2 as follows:
a. (H2 – 46) / (620 – 46) = 0.99.
b. H2 = 46 + (620 – 46) * 0.99 = 614.5 Kcal/Kg
c. Enthalpy drop for actual operation = H2 – H1 = 614.5 – 834 = - 219.5
Kcal/Kg
7. Steam turbine efficiency = (H2 – H1) / (H2 - H1) = - 219.5 / - 284.4 = 0.77 or 77%