Single Pressure Absorption Heat Pump Analysis

Single Pressure Absorption Heat Pump Analysis
A Dissertation
Presented to
The Academic Faculty
by
Laura Atkinson Schaefer
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy in Mechanical Engineering
Georgia Institute of Technology

May 2000
ii
Single Pressure Absorption Heat Pump Analysis
Approved:
Samuel V. Shelton, Chairman
Richard Barke
Alan Larson
Amyn Teja
William Wepfer
Date Approved
iii
DEDICATION
To Andrew James Schaefer,
my wonderful husband
iv
ACKNOWLEDGEMENTS
During my time at Georgia Tech, I have received support from too many people
to list them all. I am deeply grateful to everyone who has encouraged and aided me.
However, there are certain professors, colleagues, friends, and family members to
whom I would like to individually express thanks.
First, I would like to give thanks to God. Without You, Lord, none of this
would have been possible.
Dr. Sam Shelton has been my advisor in not just the typical but also the
traditional sense of the word. He has provided me with direction and encouragement
in my research, my graduate studies, and my academic job search. He has had faith
in my abilities even when I doubted them, and I truly appreciate the intellectual and
moral support that he has given me. I will miss our discussions on topics ranging
from thermodynamics to environmental concerns. I would also like to thank his wife,
Mrs. Sharon Shelton, for her encouragement and advice.
Dr. William Wepfer has also been an integral part of my graduate career
at Georgia Tech. Dr. Wepfer helped me to publish my first paper in the field of
mechanical engineering, and has called numerous scholarship and career opportunities
to my attention. I appreciate his help during my job search and the time that he
devoted to serving on my reading committee.
I am also grateful to Dr. Alan Larson for his support of my job search and for
his contributions to my dissertation. Dr. Larson has the unique ability to combine a
deep, overall understanding of a work with a meticulous attention to detail.

v
I am very thankful to Dr. Amyn Teja and Dr. Richard Barke for serving
on my reading committee. Their backgrounds and perspectives have enriched my
doctoral work.
My office mates and friends at Georgia Tech have been an invaluable source of
help. I would like to thank Andy Delano for his technical support and Comas Haynes
for his prayer support. I would also like to recognize my friends Claudia Zettner, Bill
Anderson, and Jason Brown.
Finally, I would like to thank the most important people in my life: my family.
My dear husband, Andrew Schaefer, has been my rock and my foundation during
the occasionally stormy years of graduate school. His love, kindness, and humor have
sustained me. The past seven years with Andrew have been a blessing, and I look
forward to the exciting future that lies ahead of us.
My mother and father, Michael and Sherry Atkinson, my brother and sister,
Seth and Terra Atkinson, and all of my grandparents have been an unfailing source of
support. Thank you for your love, faith, and encouragement. You were there for me
even during the darkest times. I am also thankful for the love and support provided
by my husband’s parents, sister, and grandmothers. I feel that you have taken me
into your hearts, and I am so grateful for that.

vi
TABLE OF CONTENTS
DEDICATION iii
ACKNOWLEDGEMENTS iv
LIST OF TABLES x
LIST OF ILLUSTRATIONS xi
NOMENCLATURE xiv
SUMMARY xvii
CHAPTER
I INTRODUCTION 1
Heat Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Heat Sources and Sinks . . . . . . . . . . . . . . . . . . . . . 5
Heat Pump Cycles . . . . . . . . . . . . . . . . . . . . . . . . 7
The Einstein Cycle . . . . . . . . . . . . . . . . . . . . . . . . . 13
Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Literature Review . . . . . . . . . . . . . . . . . . . . . . . . 15
Current Research . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Modeling the Einstein Cycle . . . . . . . . . . . . . . . . . . 16
Alterations of the Cycle Configuration . . . . . . . . . . . . . 17
Gas Water Heating: An Application for the Einstein Cycle . 18
II THERMODYNAMIC MODEL OF THE CYCLE 20

Overall Description of the Cycle . . . . . . . . . . . . . . . . . . 20
Component Analysis . . . . . . . . . . . . . . . . . . . . . . . . 22
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
The Evaporator . . . . . . . . . . . . . . . . . . . . . . . . . 23
The Precooler . . . . . . . . . . . . . . . . . . . . . . . . . . 26
The Condenser/Absorber . . . . . . . . . . . . . . . . . . . . 28
The Generator . . . . . . . . . . . . . . . . . . . . . . . . . . 29
The Bubble Pump . . . . . . . . . . . . . . . . . . . . . . . . 33
Second Law Analysis . . . . . . . . . . . . . . . . . . . . . . . . 41
vii
The Coefficient of Performance . . . . . . . . . . . . . . . . . 41

An Illustrative Case: The Internal Generator Heat Exchanger 45
III THE PRINCIPLE OF CORRESPONDING

STATES MODEL 48
The van der Waals Equation of State . . . . . . . . . . . . . . . 48
Two-Parameter Principle of Corresponding States . . . . . . . . 49
Three-Parameter Principle of Corresponding States . . . . . . . 50
Calculation of Compressibility . . . . . . . . . . . . . . . . . . . 51
Calculation of the Enthalpy Departure Function . . . . . . . . . 56
Ideal Gas Theory . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Incompressible Liquid Theory . . . . . . . . . . . . . . . . . . . 59
Saturated Liquid and Vapor Behavior: Enthalpy Versus Temper-
ature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Implementation of the Ideal Gas and Incompressible Solution
Theories . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Determining Enthalpy Differences . . . . . . . . . . . . . . . . . 65
IV THE IDEAL SOLUTION MODEL 67

Vapor-Liquid Equilibrium . . . . . . . . . . . . . . . . . . . . 67
Mole and Mass Fractions . . . . . . . . . . . . . . . . . . . . 68
Mixing Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
V IDEAL SOLUTION PARAMETER RESULTS

AND FLUID SELECTION 73
System Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Searching for Optimum Properties . . . . . . . . . . . . . . . . . 73
Matching the Ideal Properties to Actual Fluids . . . . . . . . . . 81
Dimensions of the Search . . . . . . . . . . . . . . . . . . . . 81
Absorbing Fluid . . . . . . . . . . . . . . . . . . . . . . . . . 81
Pressure-Equalizing Fluid . . . . . . . . . . . . . . . . . . . . 82
Refrigerant . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Selection of Fluid Triplets . . . . . . . . . . . . . . . . . . . . . 83
VI THE PATEL-TEJA MODEL 87

The Patel-Teja Equation of State . . . . . . . . . . . . . . . . . 87
Single Substances . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Determination of the Patel-Teja Coefficients . . . . . . . . . . 88
Equilibrium Conditions . . . . . . . . . . . . . . . . . . . . . 89
Enthalpy and Entropy Departure Functions . . . . . . . . . . 90
Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Mixing Rules . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Equilibrium Conditions . . . . . . . . . . . . . . . . . . . . . 92
viii
Enthalpy and Entropy . . . . . . . . . . . . . . . . . . . . . . 93
VII THE PATEL-TEJA MODEL RESULTS 96

System Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
Binary Interaction Parameters . . . . . . . . . . . . . . . . . . . 96
Equation of State Coefficients . . . . . . . . . . . . . . . . . . 96
Fitting the Experimental Data . . . . . . . . . . . . . . . . . 97
Parameter Values . . . . . . . . . . . . . . . . . . . . . . . . 98
Actual Fluid Behavior . . . . . . . . . . . . . . . . . . . . . . . 99
Ammonia-Water-Butane Results . . . . . . . . . . . . . . . . . . 101
Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
Effect of State Point Properties . . . . . . . . . . . . . . . . . 103
Correspoding States/Ideal Solution Model Parameters . . . . 105
VIII GAS WATER HEATING: AN APPLICATION

AND ITS IMPLICATIONS 106
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
Water Heating Efficiency . . . . . . . . . . . . . . . . . . . . . . 107
Electric versus Gas Water Heating . . . . . . . . . . . . . . . 107
Einstein Cycle Gas Water Heating . . . . . . . . . . . . . . . 109
Savings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Economic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
Environmental . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Implementation . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Configuration of the Einstein Cycle as a Gas Water Heater . 114
Market Potential . . . . . . . . . . . . . . . . . . . . . . . . . 114
Barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
IX SUMMARY, CONCLUSIONS AND

RECOMMENDATIONS 118
Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . 118
Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . 123
APPENDIX
A GENERATOR PROGRAMS 125

Generator Configuration 1 . . . . . . . . . . . . . . . . . . . . . 125
Generator Libraries . . . . . . . . . . . . . . . . . . . . . . . . . 134
ix
B IDEAL SOLUTION MODEL PROGRAMS 137

Ideal Solution Model EES Program . . . . . . . . . . . . . . . . 137
Ideal Solution Model Libraries . . . . . . . . . . . . . . . . . . . 143
C PATEL-TEJA MODEL PROGRAMS 145

EES Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Program Libraries . . . . . . . . . . . . . . . . . . . . . . . . . . 148
BIBLIOGRAPHY 170
VITA 176
x
LIST OF TABLES
Table Page
3-1 Constants for Calculating Compressibility . . . . . . . . . . . . . . . 53

5-1 Parameter Variation for Increased Efficiency . . . . . . . . . . . . . . 81
5-2 Pressure Equalizing Fluids . . . . . . . . . . . . . . . . . . . . . . . 82

5-3 Refrigerants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7-1 Patel-Teja Coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . 97
7-2 Binary Interaction Parameters . . . . . . . . . . . . . . . . . . . . . 98
7-3 COP for Tca = 325 K, Tevap = 295 K . . . . . . . . . . . . . . . . . 101

7-6 Ammonia-Water-Butane Results . . . . . . . . . . . . . . . . . . . . 102
7-7 Comparison of Refrigerant Performance . . . . . . . . . . . . . . . . 103

7-8 Comparison of Pressure-Equalizing Fluid Performance . . . . . . . . 104
7-9 Theoretical Fluids and the Effect on the COP . . . . . . . . . . . . . 105
xi
LIST OF ILLUSTRATIONS
Figure Page
1-1 A Vapor Compression Cycle (Anderson, 1972) . . . . . . . . . . . . . 2

1-2 An Ammonia Absorption Cycle (Anderson, 1972) . . . . . . . . . . . 3
1-3 An Ice Plant (Anderson, 1972) . . . . . . . . . . . . . . . . . . . . . 3

1-4 Lord Kelvin’s Warming Machine . . . . . . . . . . . . . . . . . . . . 4
1-5 The Zurich Town Hall Heat Pump . . . . . . . . . . . . . . . . . . . 6
1-6 A Vapor Compression Cycle . . . . . . . . . . . . . . . . . . . . . . . 8
1-7 A Dual Pressure Absorption Cycle . . . . . . . . . . . . . . . . . . . 10

1-8 A Single Pressure Absorption Cycle . . . . . . . . . . . . . . . . . . 12
1-9 The Einstein Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2-1 The Einstein Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2-2 The Evaporator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2-3 The Ideal Solution Evaporator Model . . . . . . . . . . . . . . . . . 25
2-4 The Precooler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2-5 The Condenser/Absorber . . . . . . . . . . . . . . . . . . . . . . . . 29
2-6 The Generator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2-7 The Ideal Solution Model Generator . . . . . . . . . . . . . . . . . . 32

2-8 A Bubble Pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2-9 Vertical Flow Regimes . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2-10 Collier Flow Pattern Map . . . . . . . . . . . . . . . . . . . . . . . . 38
2-11 Baker Flow Pattern Map . . . . . . . . . . . . . . . . . . . . . . . . 38

xii
2-12 Effect of Diameter on Liquid and Vapor Flow Rates (Submergence

Ratio = 0.2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2-13 Effect of Diameter on Liquid Flow Rate and Heat Transferred to the
Bubble Pump (Submergence Ratio = 0.2) . . . . . . . . . . . . . . . 40
2-14 Pumping Capacity for h/L = 0.2, D = 8.6 mm . . . . . . . . . . . . 42
2-15 Heat Transfer To And From The Einstein Cycle . . . . . . . . . . . . 42
2-16 Alternate Generator Configurations . . . . . . . . . . . . . . . . . . . 46

3-1 Intersection of Equations 3.12 and 3.13 . . . . . . . . . . . . . . . . . 55
3-2 Saturated Liquid and Vapor Enthalpy . . . . . . . . . . . . . . . . . 60
3-3 Saturated Liquid and Vapor Enthalpies . . . . . . . . . . . . . . . . 61

5-1 The Effect of Generator Temperature on COP . . . . . . . . . . . . . 74
5-2 COP versus cp,l . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5-3 COP versus Tc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

5-4 COP versus Pc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5-5 COP versus ω . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5-6 COP versus M . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5-7 COP versus Absorbing Fluid Critical Temperature for Varying Gen-
erator Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5-8 Alternative Fluid Triplets . . . . . . . . . . . . . . . . . . . . . . . . 85
7-1 Methyl Amine-Butane, T = 288 K . . . . . . . . . . . . . . . . . . . 99
7-2 Hydrogen Chloride-Butane, P = 4 bar . . . . . . . . . . . . . . . . . 100
7-3 Ammonia-Propane, T = 293 K . . . . . . . . . . . . . . . . . . . . . 100

8-1 An Einstein Cycle Gas Heat Pump Water Heater . . . . . . . . . . . 106
8-2 Water Heater Losses . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
xiii
8-3 Residential and Commercial Natural Gas Water Heating . . . . . . . 113

xiv
NOMENCLATURE
Symbols
·m 4
a Attractive Force Correction Factor ( Nmol 2 )
m 3
b Volume Correction Factor ( mol )
J
c Specific Heat ( kg·K )
COP Coefficient of Performance (-)

D Diameter (m)
f Fugacity (kP a, bar)
J
G Gibbs Energy ( mol )
g Gravity ( sm2 )
J
H Total Enthalpy ( mol )
J
h Specific Enthalpy ( kg )
kg
M Molecular Weight ( kg·mol )
ṁ Mass Flow Rate ( kg

s
)
P Pressure (kP a, bar)
Q̇ Heat Transfer Rate (kW )
·P a
3 m3 ·P a
R Gas Constant ( m
mol·K
, kg·K
)
J
S Total Entropy ( mol·K )
J
s Specific Entropy ( kg·K )
T Temperature (◦ C, K)
J
u Specific Internal Energy ( kg )
m 3
V Total Volume ( mol )
3
v Specific Volume ( m
kg
)
xv
x Liquid Mass or Mole Fraction (-)

y Vapor Mass or Mole Fraction (-)
Z Compressibility (-)
Greek Characters
ζc Patel-Teja Coefficient (-)
kg
ρ Density ( m3)
σ Surface Tension ( N
m
)
ω Acentric Factor (-)
Subscripts
abs Absorbing Fluid
c Critical Point
f Liquid
g Vapor
m Mixture
p Constant Pressure
pe Pressure-Equalizing Fluid
r Reduced Property
ref rg Refrigerant
s Entropic Average
sv Superheated Vapor
u Universal
v Constant Volume
xvi
Superscripts
∗ Ideal State
0 Simple Fluid
L Liquid
r Reference Fluid
sat Saturated State
V Vapor
xvii
SUMMARY
Thermally-driven absorption heat pump cycles have several advantages over

conventional vapor compression cycles. They do not require a costly electric power
plant and they use environmentally-benign natural fluids. Current absorption sys-
tems are dominated by dual-pressure cycles using a solution pump (which still re-
quires a small electrical power source). Single-pressure cycles remove the need for
a pump and any electrical power. This makes them portable, inexpensive, reliable,
and silent. An entirely different approach to a single-pressure absorption cycle was
taken by Einstein and Szilard in the 1930s. Their cycle decouples the temperature
lift from the generator temperature, which allows the selection of a refrigerant that
matches the application temperature requirements.
The configuration of the Einstein cycle was examined, and changes were made
to increase the coefficient of performance. These changes were primarily implemented
on the generator side. The bubble pump performance was increased through selection
of optimum operating parameters. An external heat exchanger was added between
the generator and the condenser/absorber to improve heat recovery, and the par-
tial internal heat exchanger in the generator was expanded to a full internal heat
exchanger in order to minimize entropy generation.
The Einstein Cycle has been modeled using two separate property models: 1)
a corresponding states/ideal solution property model, and 2) a Patel-Teja/Panagio-
topoulos and Reid property model. The first model was used to predict which pa-
rameters would increase the COP and the second model was used to more accurately
predict the behavior the cycle

xviii
For this study, three temperature conditions were evaluated: 1) Tcondens−absorb

= 325 K and Tevaporator = 295 K, 2) Tca = 325 K and Tevap = 306 K, and 3) Tca =
316 K and Tevap = 295 K. As outlined in the introduction, each of these temperature
levels are suitable for using the Einstein cycle for gas heat pump water heating. The
highest COP for the first set of temperatures, which can produce 125◦ F water from
ambient conditions (flue gases could be used to help to maintain the evaporator at
72◦ F), is 1.51. The best COP for the second set of temperatures, which require a
hotter evaporator, is 1.88. Finally, the COP for the third set of temperatures, where
the Einstein cycle would be used as a preheater, is 1.76.
With a COP of 1.5, an Einstein cycle gas heat pump water heater would cut
the operating costs of a conventional gas water heater by 33%. This could result in
large economic and environmental savings.
1
CHAPTER I
INTRODUCTION
Heat Pumps
Definition
Using input energy, heat pump cycles pump thermal energy from low tempera-
tures to high temperatures. Heat pumps can transfer heat from natural or man-made
thermal sources to a building or an application. Heat pumps can also be used for
cooling by transferring heat from the application to be cooled to higher-temperature
surroundings. Heat pumps are used in refrigeration, air-conditioning, space heating,

and other applications.
History
Initially, refrigeration was the primary thrust of heat pump development. The
first attempt to produce refrigeration mechanically occurred in 1755, when William
Cullen created ice with an air pump (Anderson, 1972). Cullen, however, was unable
to consistently maintain refrigeration temperatures. The first reliable refrigeration
machine was constructed by Perkins in 1834, and by the 1850s, there was an explosion
of interest in mechanical refrigeration.
Vapor compression (Figure 1-1) and ammonia absorption (Figure 1-2) cycles
were both vigorously studied in the 1860s and 1870s. The focus at that time, how-
ever, was not to provide direct refrigeration. Instead, the cycles were used to produce
2
Figure 1-1: A Vapor Compression Cycle (Anderson, 1972)
large quantities of ice (Figure 1-3) that could then be used in commercial or residen-
tial applications (such as an icebox). Breweries were the first to implement direct
refrigeration on a large scale, followed by the food-processing industries.
By the end of World War I, public utilities started to offer incentives to residen-
tial customers to purchase home refrigerators. The public slowly began to abandon
the icebox: in 1921, only five thousand domestic refrigerators were sold, but by 1930,
that number had grown to 850,000 units (Anderson, 1972). Simultaneously, heat
pumps used for air-conditioning moved from industrial to commercial and then to
residential applications by the 1950s.
In 1852, Lord Kelvin demonstrated that a heat pump (or heat engine) could
be used for heating rather than cooling when he published a paper that described
a “warming machine” driven by an engine. Kelvin’s machine, shown in Figure 1-4,
would produce heat for a building that was greater than the heat of combustion of
the coal used to drive the engine. Kelvin outlined the heating of air from 50 ◦ F to
3
Figure 1-2: An Ammonia Absorption Cycle (Anderson, 1972)
Figure 1-3: An Ice Plant (Anderson, 1972)

4
Steam Engine Drive

To
Building T1
T3
Ingress External
Cylinder Atmosphere
Egress Receiver
Cylinder T2
Figure 1-4: Lord Kelvin’s Warming Machine
80 ◦ F as an example. He stated that an ideal machine could deliver one pound of air
per second at those temperatures from a driving power of 0.28 hp, which is equivalent
to 0.2 BTU. To directly heat one pound of air from 50 ◦ F to 80 ◦ F requires 7 BTU.
Therefore, under ideal conditions, direct heating required approximately thirty-five

times the heat equivalent of the work (Morley, 1922).
Despite Kelvin’s early work, the use of heat pumps for heating water or air
was not seriously investigated until the 1920s and 30s. Morley revived Kelvin’s work
in 1922, and laid out the configuration previously shown in Figure 1-4. Haldane
(1938) analyzed experimental data from a refrigerating plant from 1891 to 1926 to
demonstrate the heating potential of a heat pump. He also constructed an exper-
imental heat pump for his own home, and tested various heat sinks and sources
(Heap, 1983). Homkes also conducted heat pump research in the early 1930s, with a
focus on producing hot water.
5
The worldwide economic depression of the 1930s greatly stimulated heat pump
development. For heating applications, large-scale implementations proved to be
more financially favorable than smaller domestic appliances. The Zurich Town Hall
used a heat pump to provide a portion of its peak heating requirements as early as
1939 (Figure 1-5). The Town Hall heat pump worked so successfully that a second
heat pump was installed in the Zurich Public Baths (Fearon, 1978).
The use of heat pumps for domestic heating applications began to be explored
in the 1950s. The Ferranti Fridge-Heater, which was marketed in Britain in 1954, was
a hybrid refrigerator-water heater with a heating output of 1.2 kW in the summer
and 0.7 kW in the winter. Unfortunately, the fridge-heater failed to establish a
substantial consumer base, and soon disappeared from the market. Since that time,
both ground and air-source heat pumps have been investigated for residential use.
Currently, electric-driven heat pumps are available for air and water heating.
Heat Sources and Sinks
Both the Town Hall and the Public Baths in Zurich had a large supply of water
that could be used as a source of low-grade energy for the evaporator. Obviously,
though, not all heat pump installations can rely on a water source. Two other
potential sources of energy that have been investigated through the years are the
earth and the air.
Air source heat pumps have a number of obvious advantages. Air is abun-
dantly available, and the evaporator can be easily incorporated into a number of
possible configurations. However, there are problems with air source heat pumps.
The heat exchangers may be quite large, and noise is produced from the large vol-
ume of air flow. Additionally, when air source heat pumps are used to supply space
heating or cooling, difficulties can arise at the extremes. For instance, in certain
6
Figure 1-5: The Zurich Town Hall Heat Pump

7
climates, frost can form on the evaporator, which blocks the airways.
The earth is a less commonly used source of low-grade heat. The vast majority
of the heat in the earth comes from the stored energy of the sun, while only a
fraction is from geothermal energy. The main problem with this large source of
energy is finding the means to extract it. Coils must be buried in the ground, limiting
the flexibility of ground source heat pump implementations. Where this can be
overcome, though, ground source heat pumps can be an appropriate choice. Various
coil configurations have been investigated since the 1940s, and it has been found that
consistent extraction rates of 30 BTU/hr/ft of pipe can be achieved.
Water and air can not only serve as good sources of free low-grade energy, they
can also be used as heat sinks for the condenser and/or absorber. One configuration
is the use of air as a heat source and water as a sink. For that case, the evaporator
can be used to provide space cooling while the condenser provides hot water for a
number of household applications.
Heat Pump Cycles
The cycles that drive the heat pumps described in preceding history can fall
into two categories: vapor compression and absorption. Additionally, absorption

cycles can be further delineated by the number of operating pressure levels. In this
study, dual pressure and single pressure absorption cycles are of particular interest.
Vapor Compression Cycles
Vapor compression cycles are the most common type of heat pump cycle.
The most basic vapor compression cycle consists of a compressor, an evaporator,

a condenser, and a throttling valve, as shown in Figure 1-6. Work is supplied to
the compressor, which increases the pressure of the working fluid. This increase in
8

Q cd

W
Condenser cp
Compressor
Throttling
Valve
Evaporator

Q e
Figure 1-6: A Vapor Compression Cycle
pressure raises the temperature of the refrigerant, and causes the vapor to become
superheated. The refrigerant then passes through the condenser, where it rejects heat
to its lower-temperature surroundings (which can be water or air) and condenses into
a saturated or subcooled liquid.
Next, the refrigerant passes through a throttling valve, which expands the
refrigerant down to the lower, original pressure. This process also reduces the tem-
perature of the refrigerant, so that it can absorb low-temperature heat. This heat is
absorbed in the evaporator, where the refrigerant is boiled back into a vapor state.
9
Absorption Cycles
When examined as an isolated system, a vapor compression cycle can be

highly efficient. However, large losses can occur in creating the work that drives
the compressor. For example, coal may be combusted to produce electricity in a
power plant, a process that has an average efficiency of only thirty percent. By using
direct thermal energy, absorption cycles can lessen or completely avoid the need to
convert heat to work and then back to heat.
Dual Pressure Absorption Cycles
The dual pressure absorption cycle shown in Figure 1-7 replaces the compres-
sor with an absorption-generation process. Dual pressure absorption cycles use two
fluids rather than a single refrigerant. The changes in pressure, temperature, and
state that occur in the condenser, throttling valve, and evaporator are the same as
in the vapor compression cycle.
When the refrigerant leaves the evaporator, however, it is not mechanically
compressed, but is instead absorbed by a second working fluid. This absorption

process causes heat to be rejected. The liquid mixture of absorbent and refrigerant is
pumped to a higher pressure and into the generator. The pumping process is driven
by a work input, but the amount of work that is required is an order of magnitude less
than in a vapor compression cycle. Direct thermal energy from a high-temperature

source is transferred to the refrigerant-absorbent mixture in the generator. This
heating process generates refrigerant vapor, which flows into the condenser. The
remaining liquid absorbent is then throttled back to the lower system pressure as it
falls from the generator into the absorber.
10

Q
Q
cd gen
Generator
Condenser

W cp
Throttling Pump
Valve
Evaporator
Absorber

Q
Q
e abs
Figure 1-7: A Dual Pressure Absorption Cycle

11
Single Pressure Absorption Cycles
Single pressure absorption cycles have a number of advantages over vapor

compression cycles. They do not require a costly electric power plant, use environ-
mentally benign natural fluids, and have waste heat available at the user site rather
than at the central power plant. Since they have no moving parts, they are also
inexpensive, reliable, and quiet.
In order to eliminate the need for any work input, single pressure absorption
cycles add a third working fluid and replace the mechanical pump with a bubble
pump. A bubble pump can move fluids across a difference in height simply by using
a heat input. One single pressure absorption cycle is illustrated in Figure 1-8. This
is the Platen and Munters diffusion-absorption cycle, which was patented in 1928.
The Platen and Munters cycle uses ammonia as a refrigerant, hydrogen as an inert
gas, and water as an absorbent. The diffusion of hydrogen in the cycle is the kinetic
limiting process.
Although some of the components in a single pressure absorption cycle resem-
ble those of a vapor compression or dual pressure absorption cycle, there are impor-
tant differences in the way that they operate. In the generator, high-temperature
heat is applied to a liquid mixture of the refrigerant and the absorbent. This gener-
ates refrigerant vapor, which is first used to “pump” the liquid absorbent through the
bubble pump into the absorber. The refrigerant vapor then flows into the condenser,
where it rejects its thermal energy to the surroundings and condenses into a liquid.
Next, the liquid refrigerant flows into the evaporator and mixes with an inert
gas. This mixing process lowers the partial pressure of the refrigerant so that it
evaporates at a lower temperature. The vapor mixture of refrigerant and inert gas
flows into the absorber, where the liquid absorbent absorbs the refrigerant. The
12

Q
Q
Q cd
bubblepump gen
Generator
Condenser
Evaporator Absorber

Q
Q
e abs
Figure 1-8: A Single Pressure Absorption Cycle

13
inert gas then returns to the evaporator, and the liquid mixture of absorbent and
refrigerant flows into the generator.
The Einstein Cycle
Description
In 1928, Albert Einstein and Leo Szilard also patented a single pressure ab-
sorption cycle. Unlike the Platen and Munters cycle, however, the Einstein cycle uses
a pressure-equalizing absorbate fluid rather than an inert gas. In the Einstein cycle,
butane is the refrigerant, water remains the absorbent, and ammonia becomes the
pressure-equalizing fluid.
A basic diagram of the Einstein cycle is given in Figure 1-9. The generator,
bubble pump, and evaporator remain from the Platen and Munters cycle, but the
condenser and absorber are combined into a single unit. In the evaporator, gaseous
ammonia is bubbled into liquid butane. This reduces the partial pressure of the
butane to below the system pressure, which causes to butane to evaporate at a lower
temperature. The resultant vapor mixture of butane and ammonia flows into the
condenser/absorber.
A liquid film of water falls down the side of the condenser/absorber, which ab-
sorbs the ammonia from the ammonia-butane vapor. This causes the partial pressure
of the butane to rise to the system pressure, so that the butane condenses at a higher
temperature than in the evaporator. The liquid mixture of ammonia and water is
immiscible with the butane, so it separates and flows out of the condenser/absorber
into the generator while the liquid butane flows back into the evaporator.
In the generator, the ammonia-water mixture is heated to the highest temper-

ature in the system. This high temperature causes the ammonia to evaporate from
14

Q cd / abs
Condenser/
Absorber

Q gen
Generator

Q bubblepump
Evaporator

Q e
Figure 1-9: The Einstein Cycle

15
the liquid water. The liquid water is pumped back into the condenser/absorber by
the bubble pump, and the vapor ammonia flows into the evaporator, completing the
cycle.
Literature Review
Very little has been published on the Einstein cycle. In 1980, Alefeld briefly
outlined the cycle in a Physics Today guest comment. That same year, the Johns
Hopkins University Applied Physics Laboratory produced an internal report on the
Einstein cycle (Follin and Yu, 1980). The Hopkins study investigated possible alter-
native power sources for an Einstein cycle (such as solar or geothermal energy), and
calculated a maximum cooling coefficient of performance (COP) for the cycle of 0.25.
In 1984, a patent was issued to Rojey for a variation on the Einstein cycle.
While the physical cycle configuration is nearly the same as in Einstein and Szilard’s
patent, Rojey used carbon dioxide rather than ammonia for the inert fluid. He also
suggested possible alternatives for the Einstein absorbing fluid (water) and refrigerant
(butane).
One decade later, Razi et al. (1994) examined the result of powering the
Einstein cycle with solar energy for use in Morocco. They used both n-butane and
iso-butane as the refrigerant in a simple model, and found possible cooling COPs
of 0.13 to 0.19. A recent article in Scientific American also mentioned the Einstein
cycle (Dannen, 1997). However, the article focused on the partnership of Einstein
and Szilard rather than on the properties of the cycle.

The most recent and comprehensive work on the Einstein cycle was performed
by Delano for his M.S. thesis (1997) and Ph.D. dissertation (1998) at Georgia Tech.
Delano developed an Engineering Equation Solver (EES) model of the cycle using
the first and second laws. The primary emphasis of Delano’s work was to gain an un-
16
derstanding of the performance of the cycle through an analysis of the processes and
the properties of various working fluids. To model the fluids’ properties, the Patel-
Teja equation of state was fitted to experimental data using the Panagiotopoulos and
Reid mixing rules. Simplifying assumptions for both the fluid and the component
behavior were made. Delano also developed a bubble pump performance model, but
no optimization of its operating parameters was carried out.
With the EES model, Delano was able to test various refrigerant fluids, such
as i-butane, neopentane, and i-pentane, and monitor their effect on the COP and
the temperature lift from the evaporator to the condenser/absorber. He also ran
parametric studies for varying pressures, temperatures, and pinch points. While the
maximum reversible cooling COP was found to be 0.86, component irreversibilities

reduced the calculated COP to 0.15.
In addition to the computational model, Delano built a conceptual demon-
stration prototype from welded stainless steel tubing. The prototype was charged
with iso-butane, ammonia, and water. By supplying the generator with between 150
and 250 watts and the bubble pump with 50 to 70 watts, and by cooling the con-
denser/absorber with 21 ◦ C tap water, the evaporator was able to maintain tempera-
tures as low as -2 ◦ C. This prototype operated silently and reliably, and demonstrated
the viability of the Einstein cycle.
Current Research
Modeling the Einstein Cycle
The examination of the Einstein cycle performed by Delano (1998) increased
the understanding of the limitations and potential of the cycle. This study builds
on Delano’s work by using a methodical approach to increase the efficiency of the
17
Einstein cycle.
Both the cycle configuration and the fluids that are used are examined. An
ideal gas/incompressible solution model of the Einstein cycle has been completed.
This model uses the three parameter theory of corresponding states to model in-
dividual fluid behavior and Raoult’s Law to model fluid mixing, and so gives the
performance of the cycle entirely in terms of the least number of fluid properties
(such as the specific heats, masses, critical temperatures, etc.). Using this model,
an optimization of the properties has been performed in order to find the optimal
hypothetical fluids that maximize the efficiency.
Once the optimal properties were found, a number of actual fluids were chosen
that most closely matched those properties. The various fluid combinations were
then evaluated using a complex cycle model that could more accurately represent
the behavior of polar substances. The complex model uses the Patel-Teja equation
of state and Panagiotopoulos and Reid mixing rules to model fluid behavior.
Alterations of the Cycle Configuration
Changing the physical configuration of the cycle can also improve its efficiency.
A second law analysis of each cycle component can reveal sources of entropy gener-
ation. Entropy generation degrades the overall efficiency of the cycle, and so should
be minimized. The entropy generated in each component has been examined, and
appropriate improvements have been implemented. In addition, the relationship of
the diameter, submergence ratio, mass flow rate, and heat input have been analyzed
for the bubble pump, and its physical geometry has been altered to maximize its
performance.
18
Gas Water Heating: An Application for the Einstein Cycle
Previously, single (and dual) pressure absorption cycles have been primarily
used for refrigeration applications. The Einstein cycle, however, is able to produce
temperatures that are suitable for water heating. Three temperature configurations
will be explored in this study. The first will produce hot water at 52◦ C (125◦ F) from
ambient air temperatures of 22◦ C (72◦ F). The second configuration will use flue gas
exhaust to heat the evaporator, and will produce 52◦ C hot water from an evaporator
temperature of 33◦ C (91◦ F). In the final configuration, the Einstein cycle will be used
as a preheater that will raise the water temperature to 43◦ C (109◦ F) from ambient air
temperatures of 22◦ C (72◦ F). The cycle performance for each of these configurations
is detailed in Chapter VII.
These temperatures were selected based on current water heater regulations.
Due to safety considerations, water heater temperatures have been reduced so that
140◦ F is the upper limit on the tank thermostat. Furthermore, scalding temperatures
are at 120-125◦F, and 105◦ F is the maximum temperature need for most applications.
These temperature levels are ideal for domestic water heating and service (commer-
cial) water heating, resulting in an increase in efficiency. The efficiency, which is
defined as the amount of heating provided to the water divided by the amount of
heating provided by the gas flame, can be increased from the current levels of 66%
to over 100%.
The higher coefficient of performance means that an Einstein cycle natural gas
heat pump water heater is a feasible alternative to traditional gas water heating. Gas
water heaters comprise over fifty-five percent of the United States’ residential water
heating market, and consume 1.3 quads of energy each year. In the commercial sector,
gas water heating accounts for 13% of the total gas usage, and consumes 0.35 quads
19
per year. An alternative gas water heater that uses less energy has the potential to
significantly reduce carbon emissions, and provide savings for the consumer. These
economic and environmental savings are analyzed, and implementation strategies and
market barriers are also discussed.
20
CHAPTER II
THERMODYNAMIC MODEL OF THE CYCLE
Overall Description of the Cycle
The Einstein cycle is a single-pressure, thermally-driven refrigeration cycle
that uses three fluids. One fluid acts as a refrigerant, one as a pressure-equalizing
fluid, and one as an absorbing fluid. Because the Einstein cycle operates at a single
pressure, no moving parts, such as a pump, are required. In order to facilitate fluid
motion, there are some slight pressure variations due to height differences in the
cycle, but they are considered to be insignificant for the purposes of this evaluation.
Figure 2-1 shows a general diagram of the Einstein cycle. The cycle shown
in this figure has been modified from Einstein’s original configuration. Various heat
exchangers, such as the internal generator solution heat exchanger, have been added
in order to create a cycle with a higher efficiency.

At point 1, liquid refrigerant leaves the condenser/absorber, passes through
a precooler, and arrives in the evaporator at point 2. The pressure-equalizing fluid
enters the evaporator as a vapor at point 4. The refrigerant and pressure-equalizing
fluids combine at a low temperature. The refrigerant evaporates and leaves the evap-
orator at point 3. The evaporation process requires heat transfer from the surround-
ings. The refrigerant and pressure-equalizing vapor mixture becomes superheated in
the precooler, and is bubbled into the condenser/absorber at point 6.
Liquid absorbing fluid from the generator is sprayed into the condenser/-
absorber (point 11). The absorbing fluid absorbs the pressure-equalizing vapor from
9g
Reservoir
3
4
11
9f
Bubble Pump
Evaporator
Figure 2-1: The Einstein Cycle
4b
Pre-Cooler
6
External
5 10 Heat Exchanger 1 2
7 Qevaporator
8 Qcondenser/absorber
Condenser/Absorber
Generator
Butane (Refrigerant)
Qgenerator Water (Absorbing Fluid)
Ammonia (Pressure-Equalizing Fluid)

9 Qbub pump
21
22
the mixture entering at point 6. The refrigerant vapor and the remaining pressure-
equalizing vapor are then cooled until they condense. Heat of absorption and con-
densation is rejected to the environment. The refrigerant is then siphoned into the
evaporator (as noted above), and the pressure-equalizing/absorbing fluid mixture
leaves the condenser/evaporator at point 7.
The mixture stream then exchanges heat with the liquid absorbing fluid that
is to be sprayed into the condenser/absorber, and enters the generator at point 8. In

the generator, the fluid mixture is heated to separate the absorbing fluid from the
pressure-equalizing fluid. The pressure-equalizing vapor leaves the generator at point
5, and mixes with additional pressure-equalizing vapor from the bubble pump. The
two vapor streams combine at point 4b, and then pass through the precooler to point
4. To remove most of the pressure-equalizing fluid that remains in the liquid mixture,
that mixture is pumped through a bubble pump to a reservoir (point 9). The residual
pressure-equalizing vapor (point 9g) is combined with the pressure-equalizing vapor
leaving the generator, as noted above. The liquid absorbing fluid then exchanges
heat with the entering mixture stream, and leaves the generator at point 10.
Component Analysis
Introduction
In order to model the behavior of the Einstein cycle, a first and second law
analysis is applied to each component. The entropy that is generated by each process
is evaluated, and energy, mass, and species conservation equations have been devel-
oped. Two separate property models are used in order to both improve the efficiency
through optimization and accurately describe the cycle. The ideal solution model
presents simplifications for analysis of the cycle processes, and utilizes the three-
23
3
4
Qevaporator
2
Figure 2-2: The Evaporator
parameter theory of corresponding states, as outlined in Chapters III and IV. The
more accurate property model uses the Patel-Teja equation of state and Panagiotopo-
lus and Reid mixing rules, and is described in Chapter VI. Differences between the
two models in their evaluation of the various components are noted in the following
sections.
The Evaporator
The evaporator is presented in Figure 2-2 . In the evaporator, saturated liquid

refrigerant enters at point 2, while a mixture of saturated vapor pressure-equalizing
fluid from the generator and the bubble pump is bubbled in (point 4) after passing
through the precooler. The partial pressure of the refrigerant is reduced, causing it to
evaporate and leave the evaporator as a vapor mixture with the pressure-equalizing
fluid at point 3.
The conservation of energy for the evaporator is:
24
Q̇evaporator = ṁ3 h3 − ṁ2 h2 − ṁ4 h4 (2.1)
Mass and species conservation equations can also be written:
ṁ3 = ṁ2 + ṁ4 (2.2)
ype,3ṁ3 = xpe,2 ṁ2 + ype,4ṁ4 (2.3)
where ype,3 is the vapor mass fraction of the pressure equalizing fluid at point 3 and
x is the liquid mass fraction. Because there are only two fluids, the mixture mass
conservation equation and a single species conservation equation completely specify
the states.
In order to accurately model the vapor-liquid-liquid equilibrium that can occur

in the evaporator, the Patel-Teja equation of state must be used. Since the ideal
solution model cannot accurately represent the evaporator’s internal processes, an
approximation must be formulated instead. This approximate model is shown in
Figure 2-3.
For the ideal solution model, it is assumed that the control volume in the
lower section of the evaporator is in vapor-liquid equilibrium and is at a constant
temperature. It is also assumed that all of the heat transferred to the evaporator is
transferred at that temperature. Given these assumptions, the conservation equations
become:
ṁ2 + ṁ3p + ṁ4 = ṁ2p + ṁ3 + ṁ4p (2.4)
ṁ2 xref r,2 + ṁ3p yref r,3p + ṁ4 yref r,4 = ṁ2p xref r,2p + ṁ3 yref r,3 + ṁ4p yref r,4p (2.5)
25
4 3
2p
3p
4p
Qevaporator
Figure 2-3: The Ideal Solution Evaporator Model
ṁ3p = ṁ2p + ṁ4p (2.6)
ṁ3p ype,3p = ṁ2p xpe,2p + ṁ4p ype,4p (2.7)
The conservation of energy for the evaporator is still equation 2.1, but a further
energy conservation statement is also needed:
Q̇evaporator = ṁ3p h3p − ṁ2p h2p − ṁ4p h4p (2.8)
Returning to a more realistic model of the evaporator, in addition to these
energy, species, and mass conservation equations, a second law analysis should also
be performed. For the evaporator, the entropy generation is:
Q̇evaporator
Ṡevaporator = ṁ3 s3 − ṁ2 s2 − ṁ4 s4 − (2.9)
T evaporator,s
The temperature in equation 2.9, T evaporator,s , is the entropic average temper-

26
ature. When heat is transferred over a temperature difference, entropy is generated.

The entropic average temperature is a means of determining the average temperature
at which this generation occurs. Mathematically, it is defined as:
Q̇
T̄s = δQ (2.10)
T
The Precooler
Prior to entering the precooler, the pressure-equalizing vapor from the genera-
tor mixes with pressure-equalizing vapor from the bubble pump. (It should be noted
that the ideal solution model does not include a bubble pump.) This combination of
the pressure-equalizing streams can be quantified through mass, species, and energy
conservation equations:
ṁ4b = ṁ4 + ṁ9g (2.11)
ype,4bṁ4b = ype,4ṁ4 + ype,9g ṁ9g (2.12)
ṁ4b h4b = ṁ4 h4 + ṁ9g h9g (2.13)
Within the precooler, as presented in Figure 2-4, no mixing occurs between
the three streams, and no external heat is added or released. Two pinch points
(minimum temperature differences) are required, since three streams are exchanging
heat. These pinch points will be specified to occur between points 2 and 4 and points
4b and 6.
T2 = T4 + pinch24 (2.14)
T4b = T6 + pinch4b6 (2.15)

27
4b 4
6 3
1 2
Figure 2-4: The Precooler
The ideal solution model does not include the bubble pump, so equation 2.15
becomes:
T5 = T6 + pinch56 (2.16)
where state point 5 is equivalent to state point 4b.
Because the streams do not mix, neither the species concentrations nor the
mass flow rates change (i.e. ṁ1 = ṁ2 ), and the conservation of mass is satisfied
through the evaporator and condenser/absorber equations. Only a single equation is
then needed to specify the states of the precooler:
ṁ1 h1 + ṁ3 h3 + ṁ4b h4b = ṁ2 h2 + ṁ4 h4 + ṁ6 h6 (2.17)
The precooler transfers heat across finite temperature differences, generating
entropy:
Ṡprecooler = ṁ2 s2 + ṁ4 s4 + ṁ6 s6 − ṁ1 s1 − ṁ3 s3 − ṁ5 s5 − ṁ9g s9g (2.18)
This equation also includes the entropy generated by mixing the pressure-
equalizing vapor streams from the generator and the bubble pump.
28
The Condenser/Absorber
Rather than utilizing a separate condenser and absorber, these units are com-
bined in the Einstein cycle (Figure 2-5). A weak liquid mixture of absorbing fluid
and pressure-equalizing fluid falls in a film down the side of the unit. A vapor mix-
ture of refrigerant and pressure-equalizing fluid is bubbled into the film, and the
pressure-equalizing fluid is absorbed, generating useful heat. The entering liquid
mixture increases its pressure-equalizing fluid concentration as it falls down the con-
denser/absorber, while the partial pressure of the pressure-equalizing vapor decreases
as it rises, thereby maximizing the absorption potential of the liquid throughout the
unit. A liquid mixture of absorbing fluid and pressure-equalizing fluid is immiscible

with the refrigerant, and is siphoned from the bottom of the condenser/absorber into
the generator. As the pressure-equalizing fluid is absorbed, the refrigerant’s partial
pressure returns to the system pressure, so it condenses at a higher temperature than
in the evaporator. Some pressure-equalizing fluid condenses as well, and that liquid
mixture then enters the precooler.
The amount of heat transferred from the condenser/absorber is found from
the conservation of energy:
Q̇cond/abs = ṁ1 h1 + ṁ7 h7 − ṁ6 h6 − ṁ11 h11 (2.19)
The species and mass conservation equations state that:
ṁ1 + ṁ7 = ṁ6 + ṁ11 (2.20)
xi,1 ṁ1 + xi,7 ṁ7 = yi,6 ṁ6 + xi,11 ṁ11 (2.21)
where i represents one of the fluids. Since there are three fluids present in the
29
11
7
Qcondenser/absorber
Figure 2-5: The Condenser/Absorber
condenser/absorber, the species equation must be stated for any two to completely
specify this control volume.

The entropy generation in the condenser/absorber is:
Q̇cond/abs
Ṡcond/abs = ṁ1 s1 + ṁ7 s7 − ṁ6 s6 − ṁ11 s11 − (2.22)
T cond/abs,s
The Generator
The generator control volume will be defined as including the external solution
heat exchanger, the internal solution heat exchanger, the bubble pump, the reser-
voir, and the generator unit, as shown in Figure 2-6. The external heat exchanger
and a full internal solution heat exchanger are departures from Einstein’s original
patent. Combined, these elements produce pressure-equalizing fluid vapor for both
the evaporator and the condenser/absorber and liquid absorbing fluid for the con-
30
denser/absorber from a liquid pressure-equalizing/absorbing fluid mixture and a heat

input.
The conservation of energy for the entire control volume states that
Q̇generator = ṁ5 h5 + ṁ9g h9g + ṁ10 h10 − ṁ8 h8 (2.23)
Again, since only two fluids are present, only a single species mass conservation
equation is needed in addition to the mixture conservation of mass:
ṁ5 + ṁ9g + ṁ11 = ṁ7 (2.24)
ype,5ṁ5 + ype,9g ṁ9g + xpe,11 ṁ11 = xpe,7ṁ7 (2.25)
The processes in the external and internal solution heat exchangers must also
be accounted for. No mixing occurs in either the external or the internal heat ex-
changer, so the mass flow rates remain constant in each stream:
ṁ7 = ṁ8 (2.26)
ṁ9f = ṁ10 = ṁ11 (2.27)
To account for the heat transferred in the internal and external solution heat
exchangers, additional mass, species, and energy equations are required:
ṁ8 = ṁ5 + ṁ9 (2.28)
xpe,8 ṁ8 = ype,5ṁ5 + xpe,9 ṁ9 (2.29)
ṁ7 h7 + ṁ11 h11 = ṁ8 h8 + ṁ10 h10 (2.30)

31
9g
Reservoir
9f
5 10 11
8 7
Qgenerator
9
Qbub pump
Figure 2-6: The Generator

32
5 10 11
8 7
9
Qgenerator
Figure 2-7: The Ideal Solution Model Generator
Finally, a pinch point must also be defined:
T11 = T7 + pinch7,11 (2.31)
As noted previously, for simplicity, the ideal solution model does not include
the bubble pump, which results in the configuration shown in Figure 2-7. The mass,
species, and energy conservation equations must be modified to reflect this change.
Equations 2.28-2.31 remain the same, but equation 2.23 becomes:
Q̇generator = ṁ5 h5 + ṁ10 h10 − ṁ8 h8 (2.32)
Returning to a model that includes the bubble pump, the entropy generated
by the generator is:
33
Q̇generator
Ṡgenerator = ṁ5 s5 + ṁ9g s9g + ṁ11 s11 − ṁ7 s7 − (2.33)
T generator,s
The entropy generated by the internal and external solution heat exchangers
is also accounted for in equation 2.33.
The Bubble Pump
Although the bubble pump is part of the generator subsystem, it merits a
separate review. The performance of the bubble pump (or vapor lift pump) is a
function of both its physical geometry and the properties of the fluid mixture that
it carries. A bubble pump is a heated tube that lifts fluid from a lower reservoir
to a higher reservoir, as shown in Figure 2-8. Heat applied at the bottom of the
tube causes vapor bubbles to form and to rise. This creates a balance between the
buoyancy and the friction forces, which “pumps” the liquid to the upper reservoir.
Two-phase flow in a vertical pipe falls into one of five flow regimes: bubbly,
slug, churn, wispy-annular, or annular flow. These flow regimes are illustrated in
Figure 2-9 (Collier, 1981). As the heat that is added to the pipe increases, the two-
phase flow moves sequentially through these flow patterns. The first stage is bubbly
flow, where the vapor exists as discrete bubbles within the liquid phase. In the second
stage, the bubbles expand until they are bullet-shaped and nearly span the diameter
of the tube. These bubbles are separated by “slugs” of liquid, which may contain
smaller gas bubbles. The next stage is churn flow, where the large gas bubbles begin
to break down in an oscillatory fashion, so that the center of the tube is alternately
filled with the liquid and the vapor phases. The fourth stage, wispy-annular flow, can
be difficult to differentiate from annular flow. In wispy-annular flow, the liquid phase
is present both as a film on the wall of the pipe and as long filaments of agglomerated
34
Heat
Figure 2-8: A Bubble Pump

35
droplets dispersed throughout the central core of the flow. The final stage is annular
flow, which is characterized by a liquid film surrounding a vapor core (Collier, 1981;
Azbel, 1981).
Delano has shown that a bubble pump operates most efficiently in the slug
flow regime (1998). There are numerous methods which can be used to determine
the flow regime. Tutu (1984) recommends using a dimensionless approach that em-
ploys the liquid Froude number, which represents a ratio of the inertial force to the
gravitational force. His derivation provides the boundary between the bubbly and
slug flow regimes:
—
Vg
= F rf−0.075 − 0.84F rf0.075 (2.34)
—
Vf
where —
V is the volume flow rate of the liquid (f ) or the vapor (g). Taitel et al.
(1980) provide an alternate correlation for the same transition from bubbly to slug
flow:
0.25
—
Vf —
Vg g(ρf − ρg )
= 3.0 − 1.15 σ (2.35)
A A ρ2f
where g is gravity, σ is the surface tension, ρ is the density, and A is the cross-
sectional area of the pipe. An upper bound for slug flow is provided by Chisholm
(1983), which predicts a transition from slug to churn flow at:

σ/ρf
D = 19 (2.36)
g(1 − ρg /ρf )
Flow maps can also be useful in predicting the nature of the flow. For example,
Collier (1981) plots the flow regimes on axes of the vapor momentum flux versus the
liquid momentum flux, as shown in Figure 2-10. A commonly used flow map was
36
Figure 2-9: Vertical Flow Regimes

37
developed by Baker in 1954. He plotted
G —
V g ρg
= 1.0212 × 105 √ (2.37)
λ πD 2 ρg ρf
versus
3 1 1
Lλψ 0.1844V
—f ρ 2 f µf 3
= (2.38)
G σV
—g ρg ρ2f
where G is the mass velocity of the gas phase, L is the mass velocity of the liquid
phase, and λ and ψ are functions of the fluid densities and viscosities.
Baker developed his transition lines from experimental data. Some similiarities
can be noted between the Baker flow map of Figure 2-11 and the Collier flow map
of Figure 2-10. It should be noted that all of the flow regime correlations and flow
maps described above have been developed using a homogeneous flow model. In
the homogeneous flow model, two-phase flow is treated as a single-phase flow with
properties that are a weighted average of the individual phases.
A complete derivation has been given by Delano (1998) for the dependence
of the submergence ratio (which is the ratio of the reservoir height, H, to the tube
length, L) on the fluid properties of the bubble pump:
H 1 Vf2
= + (1 + K + KsR + 2sR ) (2.39)
L 1 + sR /s 2gLA2
Vg
s=
Vf
—
Vg
sR =
—
Vf
Griffith (1961) has given a correlation to calculate s for slug flow:

38
Vapor Momentum Flux

Wispy
Annular Annular
Churn
Bubbly
Slug Bubbly-
Slug
Liquid Momentum Flux
Figure 2-10: Collier Flow Pattern Map
Figure 2-11: Baker Flow Pattern Map

39
√
V g 0.35A gD
—
s = 1.2 + 0.2 + (2.40)
—
Vf —
Vf
Furthermore, the friction coefficient (K) is a function of the pipe losses, including
those due to friction. Friction losses are derived from the friction factor (Reinemann
et al., 1990):
0.316
f= (2.41)
(Re)0.25
where
4ρ(V
—g + —
V f)
Re =
πµD
Since boiling produces the vapor bubbles, the amount of heat transferred to
V g:
the bubble pump determines —
Q̇bubblepump
—
Vg= (2.42)
ρg · hf g
In order to minimize the heat transfer that needs to be added to the bubble
pump, an optimization must be performed. The relationship between the bubble
pump tube diameter and the liquid and vapor flow rates can be seen in Figures 2-12.
A similar relationship is seen for the diameter, the liquid flow rate, and the amount
of heat transferred to the bubble pump.
Returning to the use of the bubble pump within the Einstein cycle, the goal
is to minimize the amount of heat transfer needed to pump the desired amount of
liquid and vapor. This can be expressed as the pumping efficiency:

40
0.8
0.7
d = 8.6 mm
0.6
m liq (k g /s ) 0.5
d = 7.6 mm
0.4
0.3
0.2 d = 6.6 mm
0.1
0
0 1 2 3 4 5
m v ap (k g /m in )
Figure 2-12: Effect of Diameter on Liquid and Vapor Flow Rates (Submergence Ratio
= 0.2)
0.8
0.7
d = 8.6 m m
0.6
m liq (k g /s )
0.5
d = 7.6 m m
0.4
0.3
0.2 d = 6.6 m m
0.1
0
0 20 40 60 80
Q bubpump
Figure 2-13: Effect of Diameter on Liquid Flow Rate and Heat Transferred to the
Bubble Pump (Submergence Ratio = 0.2)
41
ṁ
ηpump =
Q̇bubblepump
Fixing the submergence ratio as a reasonable 0.2, the diameter with the opti-
mal slope that will still fall within the slug flow regime is 8.6 mm. For these values,
the optimum pump capacity per amount of heat transferred will obviously fall to
the left of point A on the curve of Figure 2-14. This section of the curve can be
approximated as a straight line so that
ṁliq = 1.22x10−2 · Q̇bp (2.43)
This is an improvement of 7.9% over Delano’s bubble pump efficiency. The liquid
and vapor flow rates for this section of the curve can be approximated as:
ṁliq = 28.6 · ṁvap (2.44)
These two equations describe the bubble pump’s performance within the cycle.
Second Law Analysis
The Coefficient of Performance
The heating efficiency of the cycle, or coefficient of performance (COPh), is

directly related to the cycle’s entropy generation. This can be demonstrated by
combining a first and second law analysis. By defining a control volume to include
the entire cycle, as in Figure 2-15, conservation of energy states that
42
0.8
A h/L = 0.2
0.7 d = 8.6 mm
m liq 0.6
0.5
0.4
0.3
0.2
0 20 40 60 80 100 120 140
Q b u b pu mp
Figure 2-14: Pumping Capacity for h/L = 0.2, D = 8.6 mm
Qca
Condenser/
Absorber
Generator Evaporator
Qgen Qevap
Figure 2-15: Heat Transfer To And From The Einstein Cycle

43
Q̇evap + Q̇gen − Q̇ca = 0 (2.45)
This assumes that the sign of the rate of heat transfer is always positive in the
direction indicated in Figure 2-15.
A second law balance on a control volume that includes the entire cycle is:
Q̇ca Q̇evap Q̇gen

Ṡi = − − (2.46)
T̄c/a,s T̄evap,s T̄gen,s
Ṡi is the entropy that is generated in component i, and T̄s is defined as the entropic
average temperature, as outlined in the description of the evaporator.
Equation 2.45 can be rearranged as
Q̇evap = −Q̇gen + Q̇ca
and substituted into equation 2.46 to yield
Q̇ca (−Q̇gen + Q̇ca ) Q̇gen

Ṡi = − − (2.47)
T̄ca,s T̄evap,s T̄gen,s
This can then be restated as
T̄evap,s − T̄ca,s T̄gen,s − T̄evap,s

T̄evap,s Ṡi = Q̇ca ( ) + Q̇gen ( ) (2.48)
T̄ca,s T̄gen,s
The heating coefficient of performance is defined as the useful heating that is

desired divided by the high-temperature heating input that must be provided or pur-
chased. For the Einstein cycle, this is the heating provided by the condenser/absorber
divided by the heating required by the generator:
44
Q̇ca
COPh = (2.49)
Q̇gen
Dividing equation 2.48 by Q̇gen therefore produces

Ṡi T̄evap,s − T̄ca,s T̄gen,s − T̄evap,s
T̄evap,s = COP h ( )+( ) (2.50)
Q̇gen T̄ca,s T̄gen,s
Furthermore, the reversible, or ideal, heating coefficient of performance for a

system operating at three temperatures is:
TM (TH − TL )
COP hrev = (2.51)
TH (TM − TL )
where TH , TM , TL are the high, middle, and low temperatures, respectively (Delano,
1998). For the Einstein cycle, this is equivalent to:
T̄ca,s (T̄gen,s − T̄evap,s )

COP hrev = (2.52)
T̄gen,s (T̄ca,s − T̄evap,s )
Given this definition, manipulating equation 2.50 yields:

T̄evap,s · T̄ca,s Ṡi
COP h = COP hrev − · (2.53)
T̄ca,s − T̄evap,s Q̇gen
Therefore, the ideal COP is reduced to the actual COP by:

T̄evap,s · T̄ca,s Ṡi
degradation
COP h,i = · (2.54)
T̄ca,s − T̄evap,s Q̇gen
This relation illustrates that if the amount of entropy generated by a component (Ṡi )
can be reduced, the degradation of the COP can also be lessened, and the performance
of the cycle can be improved.
45
An Illustrative Case: The Internal Generator Heat Exchanger
Examining the causes of entropy generation in each component is obviously of

interest. Entropy generation can be caused by friction, by transferring heat across a
finite temperature difference, or by mixing. The generator is presented as an example
of how a component second law analysis can provide insight on how to improve the
efficiency of the cycle.
Without an internal solution heat exchanger, and by assuming that the exter-
nal heat is added at the temperature of the mixture at each point in the generator,
the processes that occur there can be treated as fully reversible. In Delano’s study, a
partial internal solution heat exchanger was used in the generator to heat the pres-
sure equalizing/absorbing fluid mixture entering from the condenser (1998). This
heat exchanger improved the internal heat recovery, and increased the COP. How-
ever, the heat exchanger also caused the internal heat transfer to occur at quite large
temperature differences, resulting in entropy generation. By reducing the magnitude

of the temperature differences, the amount of entropy that is generated can also be
reduced.
When the partial internal solution heat exchanger is replaced by a full inter-
nal solution heat exchanger, as illustrated in Figure 2-16, the temperature differences
across which heat is transferred are lessened. The temperature differences are inher-
ent and cannot simply be eliminated through the creation of a larger heat exchanger.
The temperature profiles of the fluids inside and outside the tube are not parallel,
and a pinch point must occur at one end. An external heat exchanger was also added
between the condenser/absorber and the generator in order to preheat the entering
ammonia-water liquid mixture to thermal and vapor-liquid equilibrium conditions.
For given inlet and outlet conditions, three configurations were examined: 1)
46
5 10 5 10
8 8
9 9
Qgenerator
Qgenerator
Partial Internal Full Internal
Heat Exchanger Heat Exchanger
Figure 2-16: Alternate Generator Configurations

47
No internal or external heat exchange, 2) Partial internal and no external heat ex-
change, and 3) Full internal and external heat exchange. The amount of supplied heat
was approximately 522 kW for configuration 1, 311 kW for configuration 2, and 248
kW for configuration 3. The heating coefficient of performance is an inverse function
of the amount of heat transferred to the generator, so it can be seen that the COPh
is indeed the highest for configuration 3. (Since the inlet and outlet conditions are
fixed, the heat transferred to and from the evaporator and the condenser/absorber are
constant.) EES programs for each of the configurations are included in Appendix A.
48
CHAPTER III
THE PRINCIPLE OF CORRESPONDING

STATES MODEL
The van der Waals Equation of State
The ideal gas equation of state (P V = Ru T ) treats all substances as if they
behave as a gas at pressures approaching zero. (A capital letter designates a molar

property and a lower-case letter designates a mass-based property.) In 1873, van
der Waals formulated an equation of state that could model a substance in both the
liquid and the vapor regions. His cubic equation of state
Ru T a
P = − 2 (3.1)
V −b V
was developed from molecular principles, and accounts for both intermolecular forces,
a, and the volume occupied by a molecule, b (van der Waals, 1873).

In order to match actual fluid behavior, the isotherms generated from the van
der Waals equation of state must have an inflection point at the critical point. This
is defined mathematically as

∂P ∂2P
=0 =0 (3.2)
∂V T
∂V 2 T
at T = Tc , P = Pc , and V = Vc .
Simultaneously solving these equations yields
49
9 1
a = Ru Tc Vc b = Vc (3.3)
8 3
Substituting a and b into equation 3.1 at the critical point shows that
P c Vc 3
= (3.4)
Ru Tc 8
Combining equations 3.1, 3.3, and 3.4:
9
Ru T R TV
8 u c c
P = −
V − 3Vc
V2
9

Ru Tc T /Tc
P = − 8
Vc (V /Vc ) − 1
3
(V /Vc )2
8Tr 3
Pr = − 2 (3.5)
3Vr − 1 Vr
where
T P V
Tr ≡ Pr ≡ Vr ≡
Tc Pc Vc
are defined as the reduced temperature, pressure, and volume (Abbott and Van
Ness, 1989).
Two-Parameter Principle of Corresponding States
The significance of equation 3.5 is that it asserts that the reduced pressure
of any substance is solely a function of that substance’s reduced temperature and
50
volume. Furthermore, reduced pressure, temperature, and volume are characterized

by the same relationship for all substances.
Unfortunately, this two-parameter corresponding states model can be highly

inaccurate. Hougen and Watson (1948) calculated that errors of up to 35% can
result from this van der Waals-based model. The reason for this high level of error
is that the van der Waals equation of state does not take into account the molecular
variability that can occur in actual substances.

One way of measuring this variability is to examine the compressibility factor
(Z) of a substance. The compressibility factor is defined as
Pv
Z= (3.6)
RT
where Z = 1 for an ideal gas. The critical compressibility factor is
Pc vc
Zc = (3.7)
RTc
Therefore, from equation 3.4, it can be deduced that the two-parameter principle of
corresponding states assumes that the critical compressibility is equal to 0.375 for all
substances.
Three-Parameter Principle of Corresponding States
In actuality, the critical compressibility can vary greatly between substances.

This would suggest that utilizing Zc as a third parameter could increase the accuracy
of the principle of corresponding states. To calculate Zc , vc must be known. Unfor-
tunately, since the differential compressibility, (∂v/∂P )T , approaches infinity at the

critical point, the critical volume cannot be accurately measured.
51
Pitzer et al. (1955) suggested an alternate third parameter that they termed
the acentric factor:
ω = log10 (Pr sat )Simple Fluid at Tr =0.7 − log10 (Pr sat )Tr =0.7 (3.8)
The acentric factor measures the deviation of intermolecular potential from a
simple fluid. A simple fluid is defined as one with a spherical shape and an inverse
sixth power potential, such as the heavier rare gases (Pitzer, 1955). Simple fluids all
exhibit a reduced saturation pressure of approximately 0.1 at a reduced temperature
of 0.7, so equation 3.8 becomes
ω = −1 − log10 (Pr sat )Tr =0.7 (3.9)
The acentric factor can therefore be determined from the critical temperature and
pressure and from one saturation pressure measurement.

With three parameters (Pc , Tc , and ω), the principle of corresponding states
becomes highly accurate for subcooled and superheated nonpolar and slightly polar
substances. While the accuracy is lessened in the saturated region and near the
critical point, the three-parameter model still provides a reasonable approximation.
Calculation of Compressibility
Pitzer and Curl (1957) used the three-parameter principle of corresponding

states to demonstrate that the compressibility factor can be expressed as a function
of the acentric factor for a given reduced temperature and pressure:
Z(Tr , Pr , ω) = Z (0) (Tr , Pr ) + ωZ (1) (Tr , Pr ) + · · · (3.10)

52
This equation is based on an expansion of the compressibility factor as a simple

power series in the acentric factor. Pitzer et al. (1955) determined that the first two
terms are sufficient to accurately describe the compressibility factor in almost all
regions.
Lee and Kesler (1975) expanded this work to provide increased accuracy and to
include a wider range of temperatures (Tr ≥ 0.3). They found that the compressibility
factor of any fluid is a function of the compressibility of a simple fluid (Z (0) ), the
compressibility of a reference fluid (Z (r) ), and the acentric factor, where Z (0) and Z (r)
are functions of Tr and Pr :
ω
Z = Z (0) + (Z (r) − Z (0) ) (3.11)
ω (r)
Lee and Kesler chose n-octane as the reference fluid.

Through a combination of experimental data and the modified Benedict-
Webb-Rubin equation of state, the reduced compressibilities (Zr = Z/Zc) for both
the simple and reference cases were found to conform to:

B C D c4 γ γ
Zr = 1 + + 2 + 5 + 3 2 β + 2 exp − 2 (3.12)
Vr Vr Vr Tr Vr Vr Vr
where
b2 b3 b4
B = b1 − − 2− 3
Tr Tr Tr
c2 c3
C = c1 − + 3
Tr Tr
53
Table 3-1: Constants for Calculating Compressibility

Constant Simple Fluid (0) Reference Fluid (r)
b1 0.1181193 0.2026579
b2 0.265729 0.331511
b3 0.15479 0.027655
b4 0.030323 0.203488
c1 0.0236744 0.0313385
c2 0.0186984 0.0503618
c3 0 0.016901
c4 0.042724 0.041577
4
d1 x 10 0.155488 0.48736
4
d2 x 10 0.623689 0.0740336
β 0.65392 1.226
γ 0.060167 0.03754
d2
D = d1 +
Tr
A set of constants was determined for the simple fluid and the reference fluid, as
shown in Table 3-1.

Recalling equations 3.6 and 3.7, the reduced compressibility is also
Pr Vr
Zr = (3.13)
Tr
To find Z (0) , the simple fluid coefficients listed in Table 3-1 are used in equation 3.12.
That equation is then set equal to equation 3.13, a reduced temperature and pressure
are chosen, and the reduced volume is found. This is not an actual reduced volume,
but rather a pseudo-reduced volume. Once Vr (0) is calculated, equation 3.13 is used
to find Z (0) . This process is then repeated using the reference fluid coefficients to
find Vr (r) and Z (r) .
Due to the highly nonlinear nature of equation 3.12, solving for Vr is not a
54
simple calculation. For every reduced temperature and pressure, there are either one
or three real roots which satisfy the equations. If there is only one root, that point
corresponds to either a liquid state (Figure 3-1a) or a vapor state (Figure 3-1b). If
three real roots exist (Figure 3-1c), one root is at a liquid state (point 1), one root is
at a vapor state (point 3), and one root (point 2) has no physical significance because
it does not represent a stable state.
For superheated or subcooled substances, only one root is present, so Z (0) and
Z (r) can be calculated solely from equations 3.12 and 3.13. In the saturated region,
however, the state of the substance must be known in order to determine which root
to utilize. The definition of the acentric factor and the principle of corresponding
states dictates that the reduced saturation pressure of a substance is a function of

Tr and ω (Wong et al., 1990):
ln(Pr sat ) = f (0) + ωf (1) (3.14)
where
f (0) = 5.92714 − 6.09648/Tr − 1.28862 ln(Tr ) + 0.16934Tr 6
f (1) = 15.2518 − 15.6875/Tr − 13.4721 ln(Tr ) + 0.43577Tr 6
Therefore, when Pr > Pr sat , the root that corresponds to the vapor state should be
used, and when Pr < Pr sat , the root that corresponds to the liquid state should be
chosen.
Once Z (0) and Z (r) have been found, they can then be substituted into equation
3.11 to determine the fluid’s compressibility at the given reduced temperature and
55
Reduced Pressure
0 0.5 1 1.5 2 2.5 3
Reduced Volume
Reduced Pressure
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25
Reduced Volume
Reduced Pressure
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2
Reduced Volume
Figure 3-1: Intersection of Equations 3.12 and 3.13

56
pressure. The reference acentric factor (ω (r) ) is a known constant, and is equal to
0.3978.
Calculation of the Enthalpy Departure Function
Once the compressibility is known, many other properties can be calculated

by using the three-parameter corresponding states model. These properties include
departure functions for enthalpy, entropy, isochoric specific heat, and isobaric specific
heat. A departure function is the difference between an actual property and the value
of that property if it behaved as an ideal gas at the same temperature and pressure.
This analysis is primarily concerned with enthalpy, so the derivation of the enthalpy
departure function will be presented.
Lee and Kesler found that a fluid’s enthalpy departure is a function of the
enthalpy departures of the simple fluid and the reference fluid:
(0)
(r) (0)
H − H∗ H − H∗ ω H − H∗ H − H∗
= + − (3.15)
Ru Tc Ru Tc ω (r) Ru Tc Ru Tc
where H ∗ is the ideal gas enthalpy and H is the actual enthalpy on a mole basis.
Using fundamental property relations, the enthalpy departure function can be
related to the Gibbs energy:

H − H∗ ∂((G − G∗ )/Ru T )
= −T (3.16)
RT ∂T P
The Gibbs energy is also related to the compressibility:
P
G − G∗ dP
= (Z − 1) (constant T) (3.17)
Ru T 0 P
57
so equation 3.16 becomes:
P
H − H∗ ∂Z dP
= −T (constant T) (3.18)
Ru T 0 ∂T P P
Replacing Z with equation 3.12 yields

H − H∗ b2 + 2b3 /Tr + 3b4 /Tr 2
= Tr Z − 1 −
Ru Tc Tr Vr

c2 − 3c3 /Tr 2
d2
− + + 3E (3.19)
2Tr Vr 2 5Tr Vr 5
where

c4 γ γ
E= 3 β + 1 − β + 1 + 2 exp − 2
2Tr γ Vr Vr
As with the compressibility, the simple fluid constants and reduced volume
are used to find ((H − H ∗ )/Ru Tc )(0) , and ((H − H ∗ )/Ru Tc )(r) is calculated using
the reference fluid constants and reduced volume. The usefulness of these enthalpy
departure function and saturation pressure calculations in determining ideal fluid
properties is demonstrated in the next sections.
Ideal Gas Theory
Since the theory of corresponding states produces functions that are depar-
tures from the ideal gas state, the principles of that state should be examined. Ideal
gas internal energy (u) can be represented as a function of temperature and volume:

∂u ∂u
du = dT + dv (3.20)
∂T v
∂v T
58
Constant-volume specific heat is defined as:

δq ∂u
cv ≡ ≡ (3.21)
dT v
∂T v
so, substituting this into equation 3.20 results in

∂u
du = cv dT + dv (3.22)
∂v T
Recalling that P v = RT for an ideal gas,

∂u
=0
∂v T
so this equation can be further simplified to
du = cv dT (3.23)
From equation 3.23, it is then evident that the internal energy of an ideal gas
is solely a function of temperature (Black and Hartley, 1991).
Enthalpy (H) is defined as a function of internal energy, pressure and volume:
dh ≡ du + d(P v) (3.24)
Returning again to the ideal gas equation of state, this equation becomes
dh = du + d(RT ) = du + RdT (3.25)
and the enthalpy of an ideal gas is also shown to be only a function of temperature.
By defining constant-pressure specific heat:

59

δq ∂h
cp ≡ ≡ (3.26)
dT p
∂T p
the differential enthalpy can then be stated as
dh = cp dT (3.27)
Incompressible Liquid Theory
For the ideal solution model, all liquid states will be assumed to behave as
an incompressible liquid at saturated liquid conditions. This is not an unreasonable
assumption, since the majority of processes in the Einstein cycle depend on operation
in the saturation region. The enthalpy at any point can be determined in a manner
similar to that employed in the previous ideal gas analysis.
Saturated Liquid and Vapor Behavior: Enthalpy Versus Temperature
For a given substance, the enthalpies of the saturated vapor (hg ) and the
saturated liquid (hf ) vary with temperature in the manner illustrated by Figure 3-
2. While the slope and curvature of the lines are dependent on the substance, this
general behavior is universal. While there is a great deal of curvature demonstrated
close to the critical point, hg and, particularly, hf are primarily linear in the non-
critical region.
At a given temperature, the difference in the saturated vapor enthalpy and

the saturated liquid enthalpy is the heat of vaporization (hf g ) for that temperature.
The slope of the saturated vapor line is equal to the gas specific heat at constant
pressure (cp,g ), and the slope of the saturated liquid line is the fluid specific heat
60
3000
hg
2500
Enthalpy (kJ/kg K )
2000 W ater
1500
hf
1000
500
400 450 500 550 600 650
Temper ature (K )
Figure 3-2: Saturated Liquid and Vapor Enthalpy

61
700
650
h g Is o b u ta n e
600
E n t h a lp y ( k J / k g K )
550
h f Is o b u ta n e
500
450
400
350
300
250
300 316 331 347 363 379 394 410
Tem perature (K )
1600
1400
h g A m m o n ia
E n t h a lp y ( k J / k g K )
1200
1000
800 h f A m m o n ia
600
400
200
300 315 330 345 360 375 390
Tem p eratu re (K )
Figure 3-3: Saturated Liquid and Vapor Enthalpies

62
Enthalpy
3
href
1
Tref
Temperature
at constant pressure (cp,f ). In deciding which specific heat to use as an additional

parameter, the shape of the saturation lines should be considered. By observing a
variety of saturation curves away from the critical point, as in Figure 3-3, it can be
seen that the saturated liquid line tends to behave in a more linear fashion than the
saturated vapor line. Therefore, the fluid specific heat at constant pressure will be
selected as the specified parameter, and will be assumed to be constant.
Implementation of the Ideal Gas and Incompressible Solution Theories
Returning to the ideal gas analysis, the enthalpy of a vapor at any point can
be found by integrating equation 3.27 from a reference state (point 0) to the point
of interest:
63
h T
dh = cP dT (3.28)
h0 T0
It is helpful to assign the value of the enthalpy at a reference state, and to use
this to calculate the enthalpy at any other state. Therefore, reference values (h0 , P0
and T0 ) are assigned for each fluid. The reference pressure for all three fluids should be
equal, and has been set to the atmospheric pressure (101 kPa) for this analysis. The
reference temperature for each fluid is the saturation temperature at the universal
reference pressure, and the reference enthalpy is the saturated liquid enthalpy at that
temperature and pressure, which is set to zero. The reference temperature therefore
varies between fluids.

Equation 3.28 can be represented graphically on the enthalpy versus tempera-
ture plots of the previous section. For example, the enthalpy of a saturated vapor can
be traced as path 1-2-3 in Figure 3-4. (This figure is a simplification of the saturation
curves from Figures 3-2 and 3-3.) Therefore, the saturated vapor enthalpy at any
temperature is:
hg = h0 + cp,f (T − T0 ) + hf g (T ) (3.29)
For a superheated vapor, the path of integration is 1-2-3-4, and the enthalpy
is:
hshv = h0 + cp,f (T − T0 ) + hf g (T ) + hsv−g (T ) (3.30)
where hsv−g is the difference in enthalpy between the superheated and saturated
vapor at T .
For an incompressible liquid, determining the enthalpy is even more basic.

64
3 5 7
Enthalpy
hfg,3
hfg,2
hfg,1
6
4
href 2
1
Tref
Temperature
Enthalpy is a function of both temperature and pressure, but it is only a weak
function of pressure when it is a liquid and close to the reference pressure. Since all
liquid states are assumed to be the saturated liquid state, determining the enthalpy
of a liquid is represented by path 1-2, so that
hf = h0 + cp,f (T − T0 ) (3.31)
It should be noted that while this method of determining the enthalpy assumes
that the fluid specific heat is a constant, it does allow for variation in the gas specific
heat curve. For example, even if the saturated vapor line flattens out or develops a
negative slope, the magnitude of the heat of vaporization will account for this. This
is illustrated through paths 1-2-3, 1-4-5, and 1-6-7 in Figure 3-5.
65
Determining Enthalpy Differences
While the fluid specific heats and the reference states are given, the differences
in enthalpy (hf g and hsv−g ) used in the above equations can be accurately calculated
using corresponding states. Recall that if Tc , Pc , and ω are known, the enthalpy
departure function can be calculated in conjunction with the compressibility and
the pseudo-reduced volume. Furthermore, P sat can also be determined from equa-
tion 3.14, so the saturated liquid and vapor roots can also be determined. Therefore,
at a given temperature (T1 ),

h − h∗ h − h∗
and (3.32)
RTc T =T1 RTc T =T1
x=0 x=1
are known.
The enthalpy of vaporization (hf g ) at T1 is defined as:
hf g (T1 ) = hg (T1 ) − hf (T1 ) = h T =T1 − h T =T1

x=1 x=0
and the enthalpies at the saturation conditions can be further expanded to:

h − h∗
h T =T1 = RTc + h∗T =T1
x=1 RTc T =T1 x=1
x=1
and

h − h∗
h T =T1 = RTc + h∗T =T1
x=0 RTc T =T1 x=0
x=0
So the enthalpy of vaporization becomes

66
 
h − h∗ h − h∗  + (h∗T =T
hf g (T1 ) = RTc  − 1 − h∗T =T1 ) (3.33)
RTc T =T1 RTc T =T1 x=1 x=0
x=1 x=0
However, recalling that the change in enthalpy for an ideal gas is only a func-
tion of temperature, the second term in equation 3.33 is equal to zero:
h∗T =T1 − h∗T =T1 = cp (T1 − T1 ) = cp (0) = 0

x=1 x=0
Therefore, the enthalpy of vaporization can be represented as a function of

the critical temperature, the molecular mass, and two calculated enthalpy departure
functions:
 
Ru  h − h∗ h − h∗ 
hf g (T1 ) = Tc − (3.34)
M RTc T =T1 RTc T =T1
x=1 x=0
The difference in enthalpy between a superheated vapor and a saturated vapor

at the same temperature (hsv−g ) can be derived in a similar manner, such that:
 
∗ ∗
h−h h−h
hsv−g (T1 ) = RTc  −  (3.35)
RTc T =T1 RTc T =T1
P =P actual P =P sat
where the departure functions are calculated at the same temperature but different
pressures.
67
CHAPTER IV
THE IDEAL SOLUTION MODEL
In the previous chapter, the enthalpies of the individual fluids are calculated
for saturated liquid, saturated vapor, and superheated vapor states. Next, the indi-
vidual fluids must be combined using equilibrium conditions and mixing rules.
Vapor-Liquid Equilibrium
The most basic statement of equilibrium for a mixture in a vapor and a liquid
phase is that the fugacities of the individual substances must be equal:
fiV = fiL (4.1)
However, this form of the fugacity relationship does not present an explicit represen-
tation of the mole fractions, temperature, and pressure. To provide a more useful
form of this equation, some simplifying assumptions can be made.
1) At constant temperature and pressure, the fugacity of the liquid for substance
i is equal to the liquid fugacity of that substance multiplied by the liquid mole
fraction of that substance:
fiL = xi fpure
L
i
2) At moderate pressures, pressure has no effect on the fugacity of a liquid.

68
Additionally, the vapor phase is assumed to be an ideal gas:
L sat
fpure i = Pi
3) As in assumption 1, at constant temperature and pressure, the fugacity of the

vapor for substance i is equal to the vapor fugacity of that substance multiplied
by the vapor mole fraction of that substance:
fiV = yi fpure
V
i
4) Finally, as previously stated in assumption 2, the vapor phase is assumed to

be an ideal gas, so that the vapor fugacity of the pure component is equal to
the total pressure:

V
fpure i = P
Given these assumptions, equation 4.1 is reduced to:
yi P = xi Pisat (4.2)
This is Raoult’s Law (Prausnitz et al., 1986).
Mole and Mass Fractions
The total number of moles (Nm ) in a vapor or a liquid is equal to the sum of
the number of moles of each component (Ni ):

n
Nm = Ni (4.3)
i
69
The vapor mole fraction is defined as the number of moles of a component of

the vapor divided by the total number of moles of the vapor:
Ni
yi ≡ (4.4)
Nm, vapor
and the liquid mole fraction is similarly defined:
Ni
xi ≡ (4.5)
Nm, liquid
The sum of the vapor mole fractions can be demonstrated to be equal to one:
n

n
n
Ni i Ni Nm
yi = = = =1 (4.6)
i i Nm, vapor Nm Nm
Therefore, it also holds that the sum of the liquid mole fractions is equal to one
(Black and Hartley, 1991):

n
xi = 1 (4.7)
i
At each point in the Einstein cycle, only a two-component mixture need be

considered, so equations 4.6 and 4.7 reduce to y1 + y2 = 1 and x1 + x2 = 1. In
combination with equation 4.2, the liquid and vapor mole fractions can then be
stated solely as functions of the absolute and saturations pressures:
P −P1sat P2sat
x2 = P2sat −P1sat
y2 = x2 P
(4.8)
x1 = 1 − x2 y1 = 1 − y2
The partial pressures and the mass fractions can also now be determined:
70
pi = y i P (4.9)
xm,2 = (x2 m2 )/(x1 m1 + x2 m2 ) ym,2 = (y2 m2 )/(y1 m1 + y2 m2 )

(4.10)
xm,1 = 1 − xm,2 ym,1 = 1 − ym,2
Mixing Rules
Once the mass fractions and the individual component enthalpies are known,
the enthalpy of a vapor or a liquid mixture can be calculated. To determine the
mixing rules which govern this calculation, the Gibbs energy must be examined. The
Gibbs energy of an ideal gas mixture is a function of its chemical potential (µ) and
vapor mole fractions:

n
Gig = y i µi (4.11)
i
The component chemical potential is in turn a function of temperature, vapor mole

fraction, and individual component Gibbs energy:
µi = Gig
i + Ru T ln(yi ) (4.12)
Substituting equation 4.12 into equation 4.11 results in:

n
n
Gig = yiGig
i + Ru T yi ln(yi ) (4.13)
i i
Enthalpy is a function of the Gibbs energy, entropy, and temperature (H =

71
G + T S). The molar mixture entropy is further related to the Gibbs energy as:

∂G
S=−
∂T P,y
Combining these relations with equation 4.13 reveals that the enthalpy of an ideal
gas mixture is equal to:

n
H ig = yi Hiig (4.14)
i
where Hiig is the molar ideal gas enthalpy of component i.

Similar to equation 4.12, the chemical potential for an ideal liquid solution is
defined as following:
µi ≡ Gi + Ru T ln(xi ) (4.15)
It can clearly be seen that the derivation of the mixture enthalpy for an ideal liquid
solution will follow a similar path as the derivation for an ideal gas. The ideal liquid
solution mixture enthalpy is therefore analogous to the ideal gas mixture enthalpy
(Abbott and Van Ness, 1989):

n
H ideal soln = xi Hi (4.16)
i
Equations 4.14 and 4.16 can also be restated in terms of specific properties
and mass fractions such that:

n
ig
h = ym,i hig
i (4.17)
i
and
72

n
hideal soln = xm,i hi (4.18)
i
The enthalpy at any point in the cycle can now be expressed by combining
these expressions for enthalpy with the relations for individual component enthalpies
and mass fractions that were derived earlier in this chapter.
73
CHAPTER V
IDEAL SOLUTION PARAMETER RESULTS

AND FLUID SELECTION
System Model
Using the corresponding states and ideal solution thermodynamic property
model outlined in Chapter II and the mixture property relations of Chapters III
and IV, an EES program was created that describes the system behavior. This
program and its libraries can be found in Appendix B.
In order to produce conditions suitable for domestic and commercial water
heating, the temperature of the condenser was set at 325 K (125◦F) and the evapora-
tor temperature was specified to be 295 K (72◦ F). For the base case of the ammonia-
water-butane mixture, the generator temperature that produced the highest heating
coefficient of performance was found to be 495 K. However, the COP was only slightly
degraded by lowering the generator temperature to 425 K, as shown in Figure 5-1.
The lower generator temperature provided more stability to the solver when the fluid
parameters were varied.
Searching for Optimum Properties
Initially, a full-scale nonlinear optimization of the cycle model was attempted,
in which all the parameters were varied simultaneously. Unfortunately, this technique
caused the solver to become unstable and crash before a solution could be found. To
74
1 .7 5
T = 495
1 .7 3
T = 425
h
1 .7 2
CO P
1 .7 0
1 .6 8
350 400 450 500 550 600
T g e ne ra tor (K)
Figure 5-1: The Effect of Generator Temperature on COP
avoid this problem, each fluid property was instead individually varied, and the effect
on the COP was noted.
The starting point for each parameter variation was the default value from
the ammonia-water-butane triplet. Figure 5-2 shows the effect of varying the liquid
specific heat at constant pressure for the refrigerant (()ref rg ), pressure-equalizing fluid
(()pe ), and absorbing fluid(()abs ). In each graph, the dashed line denotes the base case
coefficient of performance. Figures 5-3 and 5-4 show the effect of varying the critical
temperature and critical pressure, respectively, and Figure 5-5 examines the acentric
factor’s effect. Finally, Figure 5-6 plots the changing COP versus the molecular mass.
In addition to testing the effects of parameter deviation, the contribution of
the generator temperature was also examined. As the generator temperature was
lowered from its optimum, the trend for each parameter remained the same, but the
magnitude of the COP improvement or degradation increased. Identical behavior

75
1.75
1.73
1.71
COPh
1.69
1.67
1.65
1.0 1.5 2.0 2.5 3.0 3.5 4.0
c pl,re frg
1.75
1.73
1.71
COPh
1.69
1.67
1.65
4.8 5.2 5.7 6.1 6.6 7.0
c pl,pe
1.75
1.73
1.71
COPh
1.69
1.67
1.65
3.1 3.5 3.9 4.4 4.8 5.2
c p l,abs
Figure 5-2: COP versus cp,l

76
1.75
1.73
COPh 1.71
1.69
1.67
1.65
415 418 421 423 426 429 432
T c,re frg
1.75
1.73
1.71
COPh
1.69
1.67
1.65
401 406 411 416 421 425 430 435 440
T c,pe
1.75
1.73
1.71
COPh
1.69
1.67
1.65
632 641 649 658 666 675 683 692 700
T c,abs
Figure 5-3: COP versus Tc

77
1.75
1.73
1.71
COPh
1.69
1.67
1.65
35 39 43 46 50
P c,re frg
1.75
1.73
1.71
COPh
1.69
1.67
1.65
105 110 115 120 125
P c,pe
1.75
1.73
1.71
COPh
1.69
1.67
1.65
130 173 215 258 300
P c,abs
Figure 5-4: COP versus Pc

78
1.85
1.80
COPh
1.75
1.70
1.65
0.05 0.08 0.10 0.13 0.15 0.17 0.20 0.22 0.25
ω re frg
1.85
1.80
COPh
1.75
1.70
1.65
0.25 0.30 0.35 0.40 0.45 0.50 0.55
ω pe
1.85
1.80
COPh
1.75
1.70
1.65
0.22 0.29 0.36 0.44 0.51 0.58 0.65
ω abs
Figure 5-5: COP versus ω

79
1.75
1.73
1.71
COPh
1.69
1.67
1.65
51 53 55 57 59 60 62 64 66
M re frg
1.75
1.73
1.71
COPh
1.69
1.67
1.65
16 19 22 25 28 31
M pe
1.75
1.73
1.71
COPh
1.69
1.67
1.65
16 17 18 19 20 21
M abs
Figure 5-6: COP versus M

80
1.80
Tg e n = Tg e n ,o p tim u m
1.75
COPh
Tg e n > Tg e n ,o p tim u m
1.70
Tg e n < Tg e n ,o p tim u m
1.65
630 640 650 660 670 680 690 700
T c ,a b s o r b
Figure 5-7: COP versus Absorbing Fluid Critical Temperature for Varying Generator
Temperature
occurred when the generator temperature was raised above the optimum. This is
illustrated for the critical temperature of the absorbing fluid in Figure 5-7.
Table 5-1 summarizes the manner in which each of the parameters must be
changed in order to increase the COP. The magnitudes of the variations are illustrated
in Figures 5-2 through 5-6, and are denoted by “+” signs in the table.
One potential difficulty with this method of optimization, however, was that
the effects of the parameters might be interrelated. In fact, once the parameters
were matched to actual fluids, this was indeed found to be the case. Constraints that
specify the maximum and minimum temperature differences between the evaporator
and the condenser/absorber must be met, and the effect of varying the refrigerant
81
Table 5-1: Parameter Variation for Increased Efficiency
Pressure-Equalizing Fluid Refrigerant Absorbing Fluid

cp,l Increase (+) Decrease (+) Decrease (++)
M Increase (+) Increase (+) Decrease (+)
Pc Decrease (+) Increase (++) Decrease (+)
Tc Increase (++) Decrease (++) Increase (++)
ω Increase (++) Decrease (+++) Increase (++)
parameters on the pressure-equalizing fluid parameters (and vice-versa) should be

explored. These difficulties are explained in more detail in the final section of this
chapter.
Matching the Ideal Properties to Actual Fluids
Dimensions of the Search
Three databases were used to gather property information on a total of 612
fluids (Cranium, 2000; PhysProp, 2000; Reid et al., 1987). For each fluid type (re-
frigerant, pressure-equalizing fluid, and absorbing fluid), the parameters were ranked
in order of their greatest effect on the COP, and the best matches were determined.
Absorbing Fluid
Einstein and Szilard used water as their absorbing fluid. The only viable alter-
native to water that was found in the fluid search was hydrazine (H4 N2 ). Hydrazine
has the potential to raise the system’s COP since it has a higher critical temperature
and a lower critical pressure and liquid heat capacity than water. Unfortunately,
hydrazine also has a higher molecular weight and a lower acentric factor. These
variations combine to actually lower the coefficient of performance. Since water has
82
Table 5-2: Pressure Equalizing Fluids

kJ
Component M Tc (K) Pc (bar) w cp,l kg·K
Ammonia 17.031 405.69 112.8 0.2526 5.272
Formaldehyde 30.0263 408.04 65.9 0.2818 2.382
Methyl Amine 31.058 430 74.5752 0.275 1.774
Hydrogen Chloride 36.4606 324.69 83.1 0.1315 2.112
Sulfur Dioxide 64.0648 430.79 78.84 0.2454 1.369
Nitrogen Dioxide 46.0055 431.19 101.33 0.8511 3.25
Methyl Bromide 94.9388 467.04 80 0.1922 0.857
Sulfur Trioxide 80.0642 490.89 82.1 0.424 3.224
Methanol 32.0422 512.68 80.97 0.564 2.842
Ethanol 46.069 513.96 61.48 0.6452 2.861
unique properties, water was kept as the absorbing fluid for alternative mixtures.
Pressure-Equalizing Fluid
In contrast to the previous case, a number of alternatives were found for am-
monia. These are listed in Table 5-2, where the values of the parameters for ammonia
are also given. However, in addition to satisfying the parameter requirements, the
toxicity and environmental impact of the alternatives were also examined (Environ-
mental Defense Scorecard, 2000). For example, nitrogen dioxide initially appears to
be a viable alternative, but it is actually a pollutant that is extremely harmful to
humans and the environment. Including this sort of consideration, the list of alter-
natives was narrowed so that only formaldehyde, hydrogen chloride, methyl amine,
methanol, and ethanol were considered.
Refrigerant
As with the pressure-equalizing fluid, there were a number of alternate fluids

found for butane. Table 5-3 contains a list of these, where, as before, the values
83
Table 5-3: Refrigerants

kJ
Component M Tc (K) Pc (bar) w cp,l kg·K
Butane 58.1234 425.22 37.97 0.1993 2.631
Vinyl Fluoride 46.0442 327.84 52.38 0.1889 2.411
Hydrogen Bromide 80.9119 363.19 85.52 0.0693 0.759
Vinylacetylene 52.0758 454.04 48.6 0.092 2.059
Hydrogen Sulfide 34.0819 373.57 89.63 0.0942 2.19
2-Butyne 54.0916 488.19 50.8 0.1301 2.387
Propylene 42.0806 365.61 46.65 0.1398 2.63
Propane 44.0965 369.86 42.49 0.1531 3.159
Methyl Chloride 50.4875 416.29 66.8 0.1531 1.716
Pentane 72.15 469.8 33.75 0.251 2.314
Nitrous Oxide 44.0129 309.61 72.45 0.1409 1.943
Acetylene 26.0379 308.36 61.39 0.1873 1.774
Ethyl Chloride 64.5144 460.39 52.7 0.1906 1.762
Dimethyl Ether 46.069 400.14 53.7 0.2036 2.805
Ketene 42.0373 370.04 58.1 0.1257 2.413
Isobutane 58.1234 408.2 36.5 0.183 2.219
Chlorodifluoromethane 86.4684 369.34 49.71 0.2192 1.375
Methyl Acetylene 40.0648 402.43 56.28 0.2161 2.448
Ethyl Fluoride 48.0601 375.35 50.28 0.222 2.2
of the parameters for butane (the base case fluid) are also given. As a secondary
screen, toxicity was again considered, and certain choices, such as methyl chloride,
were eliminated.
Selection of Fluid Triplets
The Patel-Teja equation of state and Panagiotopoulos and Reid mixing rules
were selected to model the actual fluid behavior. In order to accurately do so, bi-
nary interaction parameters needed to be found for each absorbing fluid/pressure-

equalizing fluid and refrigerant/pressure-equalizing fluid pair. As outlined in the next
84
chapter, these interaction parameters are found through correlations with experimen-
tal equilibrium data.
The availability of this experimental data further narrowed the choices as to

which alternatives could be considered. For example, while there were data avail-
able for water-formaldehyde vapor-liquid equilibrium, no data could be found for
formaldehyde and any of the refrigerant fluid alternatives. Therefore, formaldehyde
was eliminated as a pressure-equalizing fluid alternative.

The various possible matches were extensively explored, which resulted in four-
teen alternative fluid triplets. These are outlined in Figure 5-8, which also includes
the base case triplet of ammonia-water-butane.
Unfortunately, once the vapor-liquid equilibrium behavior of the fluid pairs

was modeled, some of the alternatives had to be eliminated. The optimum system
pressure has been found to be that which allows the refrigerant to begin to condense
at its partial pressure and the condenser/absorber temperature. At that pressure,
the minimum evaporator temperature is then either the saturation temperature of

the pressure-equalizing fluid or the minimum boiling azeotrope of the fluid pair,
whichever is lower. For a water heating application, the temperature of the con-
denser/absorber should be 325 K and the maximum temperature of the evaporator
should be approximately 295 K.
Although the ideal model optimization indicated that using either methanol
or ethanol as the pressure-equalizing fluid would increase the COP, it was found
that the triplets containing those fluids could not produce a suitably low evaporator
temperature for a condenser/absorber temperature of 325 K. In addition to matching
actual fluids to parameter trends, parameter boundaries must also be specified. A

constraint must be used that states that the saturation temperature of the pressure-
equalizing fluid must be less than or equal to the condenser/absorber temperature
85
Propane
Propylene
Ammonia
Butane
Pentane
Methyl Pentane
Amine Butane
Propane
Hydrogen
Water Propylene
Chloride
Butane
Propane
Methanol Propylene
Butane
Propane
Ethanol Propylene
Isobutane
Figure 5-8: Alternative Fluid Triplets

86
minus the lift at the system pressure.

Equation 3.14 from the corresponding states theory relates the saturation
temperature and pressure to the acentric factor. Using that equation, the above
constraint can be stated mathematically as:
0 1
Pc,refrg exp[frefrg + wrefrg frefrg ] = Pc,pe exp[fpe0 + wpe fpe1 ] (5.1)
where

0 1 Tcond−abs
frefrg , frefrg = Fn
Tc,refrg

Tevap
fpe0 , fpe1 = Fn
Tc,pe
and
Tcond−abs − Tevap ≥ Tlif t
Since methanol and ethanol do not meet this criterion, they were eliminated
from consideration. The effect of each of the remaining fluid triplets on the system
performance was examined using the complex cycle model. As stated previously, the
following chapter explains the bases for this model: the Patel-Teja equation of state
and Panagiotopoulos and Reid mixing rules.
87
CHAPTER VI
THE PATEL-TEJA MODEL
The Patel-Teja Equation of State
As with the principle of corresponding states, the development of the Patel-

Teja equation of state begins with the cubic van der Waals equation, which was
described in Chapter III:
RT a
P = − 2
v−b v
The van der Waals equation incorporates an intermolecular force parameter (a) and
a volume correction parameter (b). Furthermore, there is an inflection point at the
critical point, which is expressed as equation 3.2.

The Patel-Teja equation of state:
RT a
P = − (6.1)
v − b v(v + b) + c(v − b)
is clearly similar in form to the van der Waals equation. Patel-Teja adds a third
parameter (c). Furthermore, in addition to the constraints that (∂P/∂V )T = 0 and
(∂ 2 P/∂V 2 )T = 0 at the critical point, they added:
Pc Vc
ζc = (6.2)
Ru Tc
where ζc is empirically determined. It should be noted that ζc is not equal to the

88
experimental value of the critical compressibility, but instead corresponds to the

minimum deviation in saturated liquid densities when the fugacities are equal.
Single Substances
Determination of the Patel-Teja Coefficients
In equation 6.1, b and c are constants, and a is a function of temperature.

Their values can be determined by applying the constraints of equations 3.2 and 6.2
to the Patel-Teja equation of state. The value of c is straightforward:

Ru Tc
c = Ωc (6.3)
Pc
where
Ωc = 1 − 3ζc (6.4)
Determining b is slightly more complicated:

Ru Tc
b = Ωb (6.5)
Pc
The value of Ωb is the smallest positive root of
Ω3b + (2 − 3ζc )Ω2b + 3ζc2Ωb − ζc3 = 0 (6.6)
Finally, as mentioned previously, a is dependent on the temperature:

Ru2 Tc2
a = Ωa α (6.7)
Pc
While Ωa is a constant:
89
Ωa = 3ζc2 + 3(1 − 2ζc )Ωb + Ω2b + 1 − 3ζc (6.8)
α is a function of the reduced temperature:

α = [1 + F (1 − TR )]2 (6.9)
Like ζc , F is an empirically-determined constant. Therefore, there are four

parameters that are required by the Patel-Teja equation of state: Tc , Pc , ζc , and F .
In their original paper on the equation of state, Patel and Teja calculated the values
of ζc and F for thirty-eight substances (1982). Furthermore, they determined that ζc
and F can be expressed as functions of the acentric factor for nonpolar fluids:
ζc = 0.329032 − 0.076799ω + 0.0211947ω 2 (6.10)
F = 0.452413 + 1.30982ω − 0.295937ω 2 (6.11)
Equilibrium Conditions
The emperical values of ζc and F previously discussed were determined by ex-
amining the saturation curve at the equilibrium condition. Vapor-liquid equilibrium

occurs when the fugacity of the vapor phase is equal to the fugacity of the liquid
phase (as discussed in Chapter IV):
fL = fV
The fugacity can be expressed as a function of temperature, volume, and

90
pressure:
P

f v 1
ln = − dP (6.12)
P 0 Ru T P
The Patel-Teja equation of state can then be substituted into the above inte-
gral to result in the following fugacity relationship (Patel and Teja, 1982):

f bP a Z +M
ln = Z − 1 − ln Z − + ln (6.13)
P Ru T 2Ru T N Z+Q
where
−1/2
(b + c)2
N = bc + (6.14)
2

P b+c
M= −N (6.15)
Ru T 2

P b+c
Q= +N (6.16)
Ru T 2
In equations 6.13 through 6.16, Z is the compressibility and a, b, and c are the
parameters that were defined in the previous subsection.
Enthalpy and Entropy Departure Functions
In addition to providing the fugacity and the pressure, volume, and temper-
ature of the state of a substance, the Patel-Teja equation of state can also be used
to determine the enthalpy and entropy. As discussed in Chapter III, a departure
function is the difference between an actual property of a substance and the value
of that property if the substance behaved as an ideal gas at the same temperature
91
and pressure. For the Patel-Teja equation of state (1982), the enthalpy and entropy
departure functions are:

H − H∗ 1 ∂a Z +M
= Z −1− T − a ln (6.17)
Ru T 2Ru T N ∂T Z +Q
S − S∗ P 1 ∂a Z + M
= − ln − ln (6.18)
Ru Z − (bP/Ru T ) 2Ru N ∂T Z +Q
The values of N, M, and Q are given in equations 6.14 through 6.16. The differential
∂a/∂T is found by taking the derivative with respect to temperature of equation 6.7,
which results in:

∂a Ru2 Tc α
=− Ωa F (6.19)
∂T Pc TR
Mixtures
Mixing Rules
In addition to predicting the behavior of individual substances, the Patel-Teja

equation of state can also be used to model mixtures. To do so, mixture parameters
(am , bm , and cm ) must be used in equation 6.1 rather than the individual substance
parameters. The mixture parameters are a function of the component parameters
and mole fractions:

am = xi xj aij (6.20)
i j

bm = xi bi (6.21)
i
92

cm = xi ci (6.22)
i
The values of bi and ci for each component can be found using equations 6.5 and 6.3,
respectively.
Determing aij is more complicated. That term is a “cross-interaction parame-
ter,” and is a function of the individual component parameters (ai and aj , calculated
using equation 6.7) and one or more binary interaction coefficients. In this study, the
Panagiotopoulos and Reid rule was used to determine aij :
√
aij = [1 − kij + xi (kij − kji)] ai aj (6.23)
The parameters kij and kji are binary interaction coefficients (1985). They are de-
termined by minimizing the difference between experimentally and analytically de-
termined equilibrium points.
Equilibrium Conditions
The computationally determined equilibrium points are found by using the

fugacity. For mixtures, in addition to vapor-liquid equilibrium, liquid-liquid equi-
librium (fiL1 = fiL2 ) and vapor-liquid-liquid equilibrium (fiL1 = fiL2 = fiV ) can also
exist. The expression for the fugacity of a component in a mixture is more compli-
cated than the expression for the fugacity of a single substance. For component i,
the fugacity is equal to (Patel and Teja, 1982; Smith, 1995):

fi yi v b + b a D a v
ln = ln + + + (b2 + c2 + 6bc
P v−b v − b RT RT QD
93
1 2
+ b b + 3b c + 3bc + c c) + (b c + b2 c − b bc − c cb) (6.24)
QD

D
+ (−b2 − c2 − 6bc + b b + 3b c + 3bc + c c) − ln (Z)
Q
where:
Q = −b2 − 6bc − c2
D = v 2 + vb + vc − bc
√
2v + b + c − −Q
D = (−Q) − 12
ln √
2v + b + c + −Q
√ √
a = −2 yj yk (1 − kjk ) aj ak − 3 yj2 yk (kjk − kkj ) ak aj
j k j k
√ √
+ 2 yi yj (kij − kji) ai aj + yj [2 − kij − kji + yj (kij − kji)] ai aj
j j
b = bi − b
c = ci − c
Enthalpy and Entropy
The enthalpy and entropy departure functions for each component in the mix-
ture are given by equations 6.17 and 6.18. However, since a, b, and c are now mixture
94
parameters, to determine ∂am /∂T an expression must be found for ∂aij /∂T from
equations 6.7 and 6.23:
 

∂aij Ωa,i R2 Tc,i
2 2
Ωa,j R2 Tc,j Fi Tc,j αj TR,j − Fj Tc,i αi TR,i
=   (6.25)
∂T Pc,i Pc,j 2Tc,iTc,j TR,i TR,j
The departure functions can be used to determine the enthalpy and entropy
of the mixture at any point. For each substance, the reference pressure is the at-
mospheric pressure, and the reference temperature is the saturation temperature of
that substance at the reference pressure. At the reference point, the enthalpy and
entropy of the saturated liquid for each substance are defined to be zero.
First, each component is evaluated as if it acted like an ideal gas at the ref-
erence temperature and pressure. The ideal gas enthalpy and entropy of each com-
ponent at this point are the negatives of the departure functions. The state of each
component is then moved from the reference temperature to the actual temperature
(the pressure remains at the reference condition). For an ideal gas, the change in
enthalpy for that process is equal to the specific heat multiplied by the difference in
temperature. Ideal gas specific heats were found in the DIPPR database (1999) and
in Assael et al. (1996). The change in entropy is the specific heat multiplied by the
natural logarithm of the actual temperature divided by the reference temperature.

Up to this point, the components have been evaluated individually; now, they are
mixed.
Once the substances are mixed, the liquid or vapor composition can be deter-
mined from the fugacities. The mixture is still treated as if it is an ideal gas at the
reference pressure and system temperature. The enthalpy of the mixture is:
95
hmix = zi hi + zj hj (6.26)
where zi and zj represent either the liquid or the vapor mole fractions of components
i and j. The entropy, which incorporates an additional term that accounts for the
increase from mixing, is:
smix = zi si + zj sj − R[zi ln (zi ) + zj ln (zj )] (6.27)
Finally, the mixture must move from the reference pressure to the actual pres-
sure. For this transition, the enthalpy and entropy departure functions are calculated
for the mixture at the actual temperature and pressure. In summary, the enthalpy
and entropy of a mixture at any point are:
h = zi [−hdep,liq
i p,i (Tsys − Tref,i )]
(Tref,i , Pref ) + cid.g.
+ zj [−hdep,liq
j p,j (Tsys − Tref,j )]
(Tref,j , Pref ) + cid.g.
+ hdep
mixture (Tsys , Psys , zi , zj ) (6.28)

s = zi −sdep,liq
i p,i ln (Tsys /Tref,i ) − R ln (zi )
(Tref,i , Pref ) + cid.g.

+ zj −sdep,liq
j p,j ln (Tsys /Tref,j ) − R ln (zj )
(Tref,j , Pref ) + cid.g.
+ sdep
mixture (Tsys , Psys , zi , zj ) (6.29)
These two equations can be used to find the enthalpy and entropy for any subcooled,
saturated, or superheated state.
96
CHAPTER VII
THE PATEL-TEJA MODEL RESULTS
System Model
Using the equation of state relations of Chapter VI and the thermodynamic

model of Chapter II, a highly accurate cycle model was created. The EES program
that describes the model can be found in Appendix C.
Binary Interaction Parameters
Equation of State Coefficients
The first step in using the Patel-Teja equation of state to model the behavior
of the alternate fluid triplets is to determine their binary interaction parameters
(kij and kji ). Binary interaction parameters are found by minimizing the differences
between experimentally and analytically determined vapor-liquid (or vapor-liquid-
liquid) equilibrium points.

Experimental data were gathered from a number of sources for the various
fluid pairs. An effort was made to use data at temperatures and pressures similar
to the desired system operating conditions. The Patel-Teja fugacity relationship was
used to find the calculated equilibrium data. In order to use this expression for
the fugacity, the Patel-Teja equation of state coefficients were calculated from the
expressions given in the previous chapter. Some of the coefficients were previously
97
Table 7-1: Patel-Teja Coefficients
Fluid F ζc Ωa Ωb Ωc b c
Water 0.6898 0.269 0.50455 0.06510 0.193 0.01588 0.04078
Ammonia 0.6271 0.282 0.48808 0.06934 0.154 0.02073 0.04604
H Chloride 0.6214 0.319 0.44349 0.08179 0.042 0.02657 0.05236
Methyl Amine 0.7902 0.310 0.45474 0.07851 0.071 0.03764 0.03425
Butane 0.6784 0.309 0.44882 0.08023 0.056 0.0747 0.05236
Propane 0.6481 0.317 0.44602 0.08105 0.049 0.0587 0.03546
Propylene 0.6613 0.324 0.43799 0.083 0.028 0.05437 0.01824
Pentane 0.7465 0.308 0.45653 0.078 0.076 0.09038 0.08807
known from Patel and Teja’s paper on their equation of state (1982). Table 7-1 lists
the constant coefficients for each fluid.
Fitting the Experimental Data
One of two types of equilibrium data was available for each fluid pair. Either
the temperature was fixed and the pressure varied with concentration, or the pressure
was fixed and the temperature varied with concentration. For the first case, to
reduce the error between the experimental and computation values, the following
relationship was minimized:

N
100 Pi,calculated
Pdeviation (%) = 1 − (7.1)
N i=1 Pi,experimental
where N is the number of data points, and i is each data point. For the second case,
temperature deviation was minimized:
N

100 Ti,calculated
Tdeviation (%) = 1 − (7.2)
N i=1 Ti,experimental
When more than one data set was available, the sum of the deviation of each data
98
Table 7-2: Binary Interaction Parameters
Pair kij kji Reference

Ammonia-Water -0.264 -0.294 (Gmehling et al., 1977)
Ammonia-Butane 0.283 0.128 (Wilding et al., 1996)
Ammonia-Pentane 0.283 0.128 Butane: (Wilding et al., 1996)
Ammonia-Propylene 0.205 0.1 Propane: (Wilding et al., 1996)
Ammonia-Propane 0.29 0.13 (Wilding et al., 1996)
Methyl Amine-Water -0.205 -0.423 (Stumm et al., 1993)
Methyl Amine-Butane 0.123 0.057 (Gmehling et al., 1977)
Methyl Amine-Pentane 0.123 0.057 (Gmehling et al., 1977)
Hydrogen Chloride-Water -1.4 -0.18 (Brandani et al., 1994)
HCl-Propane 0.15 0.058 (Ashley and Brown, 1972)
HCl-Propylene 0.142 0.025 Propane: (Ashley and Brown, 1972)
HCl-Butane 0.15 0.058 (Ottenweller et al., 1943)
set was minimized.

Unfortunately, due to solver instabilities, EES could not automatically find
the minimum point, so the values of kij and kji were manually varied. For each guess
value of the binary interaction parameters, the fugacity of the liquid and vapor phase
were set equal to each other, and the pressure and temperature were calculated at
the experimental concentrations. The values of kij and kji were then changed, and
the effect on the average deviation was noted. Furthermore, in addition to math-
ematically minimizing the error, the correlation to experimental data was visually
checked.
Parameter Values
The kij and kji values for each fluid pair are given in Table 7-2. The source for
each pair’s experimental data is listed in the Reference column (a refrigerant listed in
that column indicates that the interaction parameters were extrapolated from that
data).
99
3 .2 5
2 .9 5
P re s s ur e (ba r )
2 .6 5
2 .3 5
Calc ulated V LE
2 .0 5 Ex perimental Data
1 .7 5
0 .0 0 0 .2 0 0 .4 0 0 .6 0 0 .8 0 1 .0 0
M ole Fr a c tion M e thyl Am ine
Figure 7-1: Methyl Amine-Butane, T = 288 K
For most cases, visual inspection shows that the computational results are
fairly accurate. Azeotropic pairs (Figure 7-1), zeotropic pairs (Figure 7-2), and vapor-
liquid-liquid equilibrium points (Figure 7-3) can all be modeled.
Actual Fluid Behavior
Once the binary interaction parameters are found, the equation of state co-
efficients and entropy and enthalpy departure functions can be used to find the cy-
cle COP for the alternate fluid triplets. As explained earlier, the system pressure
for each triplet is set such that the partial pressure of the refrigerant in the con-
denser/absorber is equal to the refrigerant’s saturation pressure at the temperature
of the condenser/absorber. The desired evaporator temperature ranges from 295 K
to 306 K, which may or may not be the minimum possible temperature. For each
triplet, the generator temperature was varied to find the maximum COP.
100
320
Calc ulated VLE

298
T e m p e ra tu re (K ) Experimental Data
276
254
232
210
0 0.2 0.4 0.6 0.8 1
M o le F ra c tio n HC l
Figure 7-2: Hydrogen Chloride-Butane, P = 4 bar
17
16
15
P r e s s u r e (b a r )
14
13
12
11
C a lc ula te d V LL E
10 E x p e rim e n tal D a ta
8
0 .0 0 .2 0 .4 0 .6 0 .8 1 .0
M o le F r a c tio n Ammo n ia
Figure 7-3: Ammonia-Propane, T = 293 K

101
Table 7-3: COP for Tca = 325 K, Tevap = 295 K
Triplet COP Psystem

Ammonia-Butane-Water 1.51 5.25
Ammonia-Propane-Water 1.49 18.3
Methyl Amine-Pentane-Water 1.44 1.7
Hydrogen Chloride-Propane-Water 1.41 18
Hydrogen Chloride-Propylene-Water 1.39 21.7
Hydrogen Chloride-Butane-Water 1.39 5.25
Ammonia-Pentane-Water 1.38 1.78
Triplet COP Psystem

Methyl Amine-Butane-Water 1.61 5.2
Ammonia-Propylene-Water 1.52 21.7
As outlined in the introduction, three temperature configurations were exam-
ined. The results for the first configuration, a condenser/absorber temperature of

325 K and and evaporator temperature of 295 K, are given in Table 7-3. The second
configuration’s (Tca = 325 K, Tevap = 306 K) results are in Tables 7-4, and the results
for the third configuration (Tca = 316 K, Tevap = 295 K) are in Table 7-5.
Ammonia-Water-Butane Results
The behavior of the cycle for the ammonia-water-butane case and the first
operating configuration is summarized in Table 7-6. The pressure is 5.25 bar, which
102
Triplet COP Psystem

Ammonia-Propylene-Water 1.61 17.6
Methyl Amine-Butane-Water 1.53 4.2
Table 7-6: Ammonia-Water-Butane Results
COPact = 1.51 COPid = 3.46 Qevap = 439.2 kW Qca = 1307 kW

Qg,tot = 867.6 kW m1 = 1.24 kg/s m3 = 1.76 kg/s m5 = 0.47 kg/s
m7 = 1.47 kg/s m10 = 0.96 kg/s mbp,in = 1.0 kg/s h1 = 134.2 kJ/kg
h2 = 58.15 kJ/kg h3 = 694.1 kJ/kg h4 = 1519 kJ/kg h5 = 1529 kJ/kg
h6 = 752.7 kJ/kg h7 = -170 kJ/kg h9 = 220.1 kJ/kg h11 = -198 kJ/kg
xmb1 = 0.9957 yma6 = 0.2645 xma7 = 0.3279 xma9 = 0.0128
provides a maximum temperature lift of 53.1 K. With an evaporator temperature of
295 K and a condenser/absorber temperature of 325 K, 54% of this lift is used.
Analysis
Unfortunately, none of the alternate fluid triplets provide a better coefficient

of performance. For all three temperature cases, the water-ammonia-propane COP is
close to the water-ammonia-butane COP, with differences so small that they can be
neglected. To analyze this result, the relationship of the COP to the various states
throughout the cycle will be explored. The validity of the corresponding states/ideal
solution model will also be reexamined.
103
Table 7-7: Comparison of Refrigerant Performance
Pair COP P Q̇bubpump Q̇gen,actual

Ammonia-Butane 1.51 5.25 88.5 779.1
Ammonia-Pentane 1.38 1.78 258.2 912.8
Pair ṁbubp ṁpe,5 ṁ7 ṁrefrg,3

Ammonia-Butane 1 0.465 1.465 1.293
Ammonia-Pentane 2.931 0.509 3.44 1.264
Effect of State Point Properties
For the first set of operating temperatures, the ammonia-water-butane and
ammonia-water-pentane triplets display the most disparate COPs. There are various
reasons for this degradation in the COP, as can be seen in Table 7-7, where the
evaporator cooling capacity has been set to 439.2 kW. The pentane case requires
a much larger mass flow rate of ammonia leaving the generator and entering the
evaporator. As a result of this, more ammonia must be absorbed by the water

stream in the condenser/absorber, and thereby desorbed in the generator.
Furthermore, the decreased pressure in the pentane case means that the con-
centration of ammonia is much higher in the liquid stream entering the bubble pump.
For that case, the bubble pump must receive nearly three times as much heat transfer
in order to remove the remaining ammonia and circulate the liquid water. In fact,
twenty-five percent of the heat that is applied to the generator goes to the bubble
pump. Previously, the bubble pump heat input has been treated as a minor factor
in the efficiency, but this is obviously no longer true. The higher bubble pump heat
transfer rate can be traced to the ammonia concentration differences between the
ammonia-butane and ammonia-pentane cases. For the ammonia-pentane mixture,
104
Table 7-8: Comparison of Pressure-Equalizing Fluid Performance
Pair COP P Q̇bubpump Q̇gen,actual

Methyl Amine-Pentane 1.44 1.7 140.4 863.6
Ammonia-Pentane 1.38 1.78 258.2 912.8
Pair ṁbubp ṁpe,5 ṁ7 ṁrefrg,3

Methyl Amine-Pentane 2.035 1.003 3.04 1.265
Ammonia-Pentane 2.931 0.509 3.44 1.264
the relative difference in concentration between the ammonia-water mixture enter-

ing the generator and the ammonia-water mixture entering the bubble pump dictates
that more water must be pumped to provide the given ammonia requirement. Similar
results occur in both alternative temperature configurations.

The effect of changing the pressure-equalizing fluid can be seen by examining
the water-methyl amine-pentane and water-ammonia-pentane triplets for the first set
of operating temperatures (Table 7-8). Again, the evaporator load is set to 439.2 kW.
In this instance, the pressures and generator temperatures are comparable, but the
methyl amine case requires nearly twice as much pressure-equalizing fluid vapor to be
produced in the generator to meet the refrigerant’s partial pressure requirements in
the evaporator. This stems from the difference in molecular weight between ammonia
and methyl amine. The provide the same evaporator partial pressure, more mass of
pressure-equalizing fluid is required since the molecular weight of methyl amine is

nearly twice that of ammonia.
Once again, though, a driving force in lowering the COP is the amount of heat
added to the bubble pump. The bubble pump for the ammonia-pentane mixture
requires approximately twice as much heat transfer as for the methyl amine-pentane
mixture. This “parasitic pumping power” has a large influence on the COP.
105
Table 7-9: Theoretical Fluids and the Effect on the COP
Base Fluid Parameter Alteration COP COPincrease

Butane Tc to 415 from 425.2 1.52648 0.02028
Butane Pc to 50 from 37.9 1.52824 0.02204
Butane ω to 0.10 from 0.199 1.5278 0.0216
Ammonia M to 30 from 17 1.50905 0.00285
Correspoding States/Ideal Solution Model Parameters
To test the validity of the parameter trends indicated by the corresponding

states/ideal solution model, four theoretical fluids have been created as examples.
Three of the fluids are a hypothetical alkane with properties similar to butane. One
parameter has been changed for each of the fluids to a value that was predicted
to increase the COP. The fourth fluid is an ammonia alternative with a different
molecular mass. Appropriate changes were made to each cycle model to reflect the
new parameter values, and the COP was calculated for a condenser temperature of
325 K and an evaporator temperature of 295 K. Each of the changes and the effect
on the COP is summarized in Table 7-9.

In each case, the COP was increased as predicted in Chapter V. Unfortunately,
these properties cannot be matched to actual fluids.
106
CHAPTER VIII
GAS WATER HEATING: AN APPLICATION

AND ITS IMPLICATIONS
Introduction
The temperatures that were chosen for the condenser/absorber and the evap-
orator in this study were selected for gas water heating. Configuring the Einstein
cycle as a gas heat pump water heater would produce hot water from ambient air
conditions and a gas flame, and would thereby provide an increase over conventional
gas water heating efficiency. The basic principle behind this configuration is shown
in Figure 8-1.
Residential and small commercial water heating is an energy use that is often
overlooked. Fifty-five percent of U.S. households utilize a gas water heater, and,
among those households, water heating accounts for nearly 25% of their gas usage.
In the commercial sector, natural gas water heating requires approximately 0.35
Heat From Condenser/

Absorber to Tank
Cond/Abs
Einstein Cycle
Generator Evaporator
Heat From Heat From

Gas Flame Ambient Air
Figure 8-1: An Einstein Cycle Gas Heat Pump Water Heater

107
quads per year, which is 13% of the total commercial gas usage. For an average
residential gas cost of $6.10 per thousand cubic feet and an average commercial gas
cost of $5.10 per thousand cubic feet, this translates into a cost of approximately $10
billion annually.
In addition to the fuel operating costs, gas water heaters contribute to global
warming emissions from the carbon dioxide formed during combustion. Each year,
approximately twenty-four million metric tons of carbon are emitted due to gas water
heating. An improvement in the efficiency of these gas water heaters would reduce
fossil fuel depletion, provide economic savings for the consumer, and reduce green-
house gas emissions.
Water Heating Efficiency
Electric versus Gas Water Heating
Residential water heating is a major energy use. The DOE estimates daily
hot water demand to be 64 gallons at 135◦F with an inlet city water temperature
of 58◦ F, and requires testing and labeling of gas and electric water heaters at these
conditions (DOE 10CFR430, 1998). This test procedure measures the efficiency of
the water heater by comparing the energy supplied in heated water to the total daily
consumption of the water heater.

For an electric water heater using electric resistance heaters immersed in the
tank, the only losses are the stand-by losses from the stored hot water to the sur-
roundings. This is shown in Figure 2. The minimum efficiency rating for electric
water heating is 0.86, with the best available being 0.95. For discussion here, the
average will be taken to be the DOE recommended rating of 0.92. This means 92%
of the energy added to water is delivered from the tank, with the remaining 8% lost
108
Delivered Delivered
ot Water Flue Loss
Hot Water
92% 34%
61%
Standby Standby
Loss Loss
8% 5%
Electrical Energy Gas Combustion

100% Energy - 100%
Electric Water Heater Gas Water Heater
Figure 8-2: Water Heater Losses
to the air in stand-by losses from the tank.

In a gas water heater, in addition to the stand-by losses there is a flue loss due
to the hot combustion gases exiting the flue as shown in Figure 8-2. The minimum
efficiency rating for gas water heating is 0.53, and the best available is 0.66. For
discussion here, it is assumed that the average is the DOE recommended efficiency
level of 0.61, and that the absolute stand-by heat losses are same as for electric water
heaters. This results in a gas flue efficiency (percentage of gas combustion energy
added to the water in the tank) of (0.61/0.92) = 0.66, so that the flue efficiency
(percentage of combustion energy being transferred to the water storage tank) is:
Qtank
Effflue = = 66% = Effwater heater (8.1)
Qgas
Therefore, 34% of the gas combustion energy is going up the flue and 5% is
lost to the air in stand-by losses from the storage tank. The stand-by losses as a
percent of the gas input energy are less than the electric water heater (5% versus
8%) due to the gas input being greater for the same delivered hot water.
109
Einstein Cycle Gas Water Heating
Recall that for the Einstein cycle, the heat transfer available from the con-
denser/absorber for water heating relative to the heat transfer received from the gas
combustion is given by:
Qtank Qgen + Qevap

= COPheating = ≥1 (8.2)
Qgen Qgen
Heat transfer to the evaporator is at the relatively high temperature of 72◦ F, so it
can be taken from the ambient air and is free to the consumer.
Using the typical 66% flue efficiency for gas water heaters for the heat pump,
which assumes that 66% of the gas combustion energy is transferred to the heat pump
generator:
Qtank Effflue Qtank
EffHP,water heater = = (8.3)
QHP,gas Qgen
Combining equations 8.1, 8.2, and 8.3:
Qtank
EffHP,water heater = = Effflue × COPh = Effwater heater × COPh (8.4)
QHP,gas
This shows that the heat pump water heater will have an efficiency higher
than the conventional water heater by the value of the heat pump cycle COP, which
is always greater than one.
Savings
Energy
U.S. residential and commercial water heating consumes approximately three

quadrillion Btu of primary energy each year. In the residential sector, fifty-percent
110
of households use natural gas water heaters. This translates into 1.3 quads of energy
use each year, which accounts for nearly 25% of residential natural gas usage. In
the commercial sector, gas water heaters consume 0.35 quads of primary energy each
year, which is 70% of the primary energy used for water heating. The residential and
commercial gas water heater installed base is estimated at 48 million and 1 million.
From equation 8.4, it can be seen that an Einstein Heat Pump Water Heater
with a heating COP of 1.5 would result in a 50% improvement over current natural
gas water heating technologies. This improvement would reduce gas consumption by
33%. In the residential sector, this means that 0.54 quads of energy could be saved
each year, and in the commercial sector, 0.12 quads could be saved. The reduced
energy consumption provides both economic savings and environmental benefits.
Economic
Reducing the energy consumed by water heating would provide economic sav-
ings for the consumer. Gas water heaters are already more beneficial for consumers
than electric resistance water heaters. Operation of an electric resistance water heater
for a typical household would cost approximately $300 each year. Electric heat pump
water heaters provide some improvement, but due to the required electrically-driven
compressor, their initial cost is two to three times higher than the cost of an electric
water heater, so the market penetration is limited.
However, just as electric heat pump water heaters improve upon resistance
water heaters, an affordably-priced gas heat pump water heater would be an im-
provement on existing gas water heating technology. As previously discussed, a gas
heat pump water heater that uses the Einstein cycle would have no machined or
moving parts, so it could be constructed out of inexpensive materials and would re-
quire no additional maintenance. Therefore, while the purchase cost of a natural gas
111
Einstein Heat Pump Water Heater would be slightly greater than that of a conven-
tional gas water heater, lower operating costs should compensate for the extra initial
purchase price.
The current average retail cost of a gas water heater is between $250 and $300.
It appears reasonable that the Einstein cycle gas heat pump could be manufactured
for about $120 above the production cost of a convention gas water heater. Once
the manufacturer’s gross margin of 30% and the distribution costs are included, the
total cost to the consumer would be approximately $550.
For a residential consumer, the average cost for natural gas is $6.10 per thou-
sand cubic feet. A family of four uses approximately 320 therms per year for natural
gas water heating, resulting in an average annual cost of $190. Overall, the residential
sector spends over $8 billion each year on gas water heating. With a 25% penetration
of the residential gas water heating market, $660 million could be saved each year.
A typical household would reduce their gas bill by $70 annually, and larger families
would be able to save even more.

The internal rate of return (IRR) is a useful quantity in evaluating the eco-
nomic value of purchasing an Einstein gas heat pump water heater rather than a
conventional gas water heater. IRR is calculated from:

12
In
0 = I0 + n
(8.5)
n=1 (1 + IRR)
The initial incremental cost of an Einstein gas water heater (I0 ) is -$275, and the
yearly energy savings (In ) are $70. Given that a gas water heater can be expected
to last for 12 years (n), equation 8.5 returns an IRR of 24%. Compared to a bank
account (IRR ≈ 4%) or an investment in the stock market (IRR ≈ 8%), it can be
seen that this would be a very attractive return.
112
In the commercial sector, the average cost for natural gas is $5.10 per thousand
cubic feet. Annually, the commercial sector spends $1.8 billion for natural gas water
heating. Due to the larger daily hot water usage, this sector should have better
economics than the residential sector, so gas heat pump water heaters would thereby
be expected to reach a higher market penetration of 33%, and $600 million could be
saved each year.
Environmental
In addition to the operating costs detailed above, combustion of natural gas

results in carbon emissions. With the Kyoto treaty of 1997, global warming resulting
from carbon emissions became an issue of great interest to the public. As a result,
numerous studies have been published that detail the costs associated with reducing
the United States’ greenhouse gas emissions to the treaty target levels. By using top-
down economic models, which include numerous difficult and debatable assumptions,
economists have calculated the cost for reducing annual carbon emissions to be $100
to $200 per ton of carbon. This is approximately equal to the current cost of fossil
fuels, meaning the effective cost of energy would double. Economists have calculated
that this economic cost would lead to a reduction in gross domestic production, a
societal cost that is both heavy and politically unacceptable (Passel, 1997).
Conversely, a bottom-up analysis that looks at high efficiency technology
shows that the use of such technology can give a positive economic payoff (Jacard et
al., 1996). Furthermore, by utilizing higher efficiency systems, the benefits enjoyed
by the end-user are not affected. An Einstein cycle gas heat pump water heater is
an example of this type of technology.
To provide hot water for a year for a family of four, 0.46 metric tons of carbon
are released from a natural gas water heater. In the residential sector, nearly 19
113
25.0
1.715
(Million Metric Tons Carbon)

Primary Energy Consumption
Carbon Dioxide Emissions

1.620
1.525
(Quads)
21.5
1.430
1.335
1.240 18.0
1985 1987 1989 1991 1993 1995 1997
Year
Figure 8-3: Residential and Commercial Natural Gas Water Heating
million metric tons of carbon are released each year due to gas water heating, while
over 5 million metric tons of carbon are released due to commercial gas water heating.
The total annual energy usage and emissions for gas water heaters can be seen in
Figure 8-3.
A 25% penetration of the residential gas water heater market by an Einstein
gas heat pump water heater would reduce carbon emissions by 1.6 million metric
tons each year. Annual carbon emissions from the commercial sector may also be
reduced by up to 1.7 million metric tons.

Under the Kyoto agreement, the U.S. must be at or below 93% of its 1990
greenhouse gas emission levels by 2008-2012. In 1990, the U.S. emitted 477 mil-
lion metric tons of carbon. By 1998, that number had grown to 517 million tons
(DOE/EIA-0383(98)). The annual carbon savings of 3.3 million metric tons outlined
above would result in meeting nearly 5% of that goal. If residential penetration

increased to approach 100%, 11% of the Kyoto target could be reached.
114
Once again, it should be emphasized that this carbon savings comes with
economic benefits (as detailed in the previous subsection) and not costs.
Implementation
Configuration of the Einstein Cycle as a Gas Water Heater
An Einstein cycle heat pump water heater could be built as an integral part
of the tank, with an external natural convection ambient heat exchanger. Within
this general framework, there are two ways that the cycle can be configured. In a
series configuration, the Einstein cycle condenser/absorber would heat the water to
an intermediate temperature, and direct heating would then increase the temperature
of the water to the final desired level.

In a quick recovery configuration, the Einstein cycle heat pump would heat
the water to the required temperature level. If the hot water level dropped below the
minimum set point, the gas flame would over-fire in a direct heat transfer mode, just
as a conventional water heater. In a configuration similar to an electric water heater,

two thermostats would provide temperature feedback to determine if the heat pump
alone should be operated, or if over-firing should be instigated.
For either configuration, the hot flue gases could be used in heat recovery. A
two-stage evaporator could be constructed that would take advantage of the heat
transfer available from both ambient temperatures and the higher-temperature vent
gases.
Market Potential
According to the Gas Appliance Manufacturers Association, over 4 million

residential and 95,000 commercial gas water heaters were shipped in 1998. These
115
numbers include both installations in new buildings and replacements for existing
units. The installed base of residential gas water heaters is estimated to be about 48
million. The short payback from the after-tax energy cost savings on the increased
Einstein heat pump water heater installed costs would be expected to yield a signif-
icant market penetration that would rise over a 10 year period to 25 percent. With
25% of the 4 million annual units, at an estimated installed cost of $550, the total
retail sales would be $350 million. A 3% penetration would yield annual sales of $42
million annually.
Barriers
An analogous case study that was performed for electric heat pump water
heaters provides insight into the barriers to implementation that might be encoun-
tered (Shelton and Schaefer, 1998). Essentially, all electric water heaters used in U.S.
residences are electric resistance water heaters. Assuming ideal thermal insulation,
one unit of electricity will generate one unit of hot water in an electric resistance
heater. However, electric heat pump water heaters pump free thermal energy from
the atmosphere rather than create it, and thereby use fifty to seventy percent less
electricity than resistance heaters. There are currently forty million electric resistance
water heaters in U.S. residential use (DOE/EE-0009(93)). If each electric resistance
water heater were replaced by a heat pump water heater, twenty-four million metric
tons of carbon would be saved per year.
In addition to reducing carbon emissions, electric heat pump water heaters

can also help the consumer to save money. While heat pumps are more expensive to
purchase and install, the reduced electricity costs are significant. At the end of an
electric heat pump water heater’s average twelve-year lifespan, the present value of
the consumer’s total lifetime expenditures will be only $1960, compared to $3120 for
116
an electric resistance water heater, a savings of nearly $1200 (DOE/EE-0009(93)).

Based on numbers similar to those given above, the DOE formally suggested
in 1994 that the minimum efficiency standard for electric water heaters be raised from
0.86 to 1.89. In homes with electric-powered water heating, this standard would ef-
fectively mandate that heat pump water heaters be installed in all new homes and
that all replacement water heaters in existing houses utilize heat pumps. Further-
more, the DOE study found that not only would consumers benefit from the raised
standard, but utilities and manufacturers would as well. The manufacturing sector
would incur some short-term retooling costs, but would then increase its profitability
(DOE/EE-0009(93); Proposed Rules, 1994).
Unfortunately, the response from utilities and manufacturers was strongly

negative. Electric utilities claimed that there was an inadequate infrastructure of
technicians who could install and service electric heat pump water heaters. They
also stated that the initial financial burden was too high for many consumers, and
that increasing the efficiency of appliances in the home, such as water heaters, would
reduce the incentive to improve power plant efficiency (Pacific Northwest National
Laboratory, 1998). Based on the public comment session, the DOE decided not to
raise the minimum efficiency standard.
A DOE-mandated higher minimum efficiency standard would greatly aid in
the commercialization of Einstein cycle gas heat pump water heaters. As in the above
case, though, obstacles from manufacturers and gas utilities would probably arise.
However, new considerations, such as the need to reduce greenhouse gas emissions,
may outweigh the concerns expressed in 1994.
Furthermore, an Einstein gas heat pump water has a number of qualities that
make it more attractive than an electric heat pump water heater. The simplicity of
the unit’s construction would greatly reduce the incremental initial cost, so that it
117
would be more affordable to a larger percentage of consumers. The relatively high

temperature of the evaporator also means that the Einstein cycle can successfully
operate in a variety of climates, so marketing efforts would not be limited to only

certain regions.
Additionally, one of the inventors of the cycle also increases its appeal. The
Einstein name is widely recognized, and is associated with genius and unique insight.
Recent presentations on the cycle at a number of universities have been strongly

attended, not only by professionals familiar with the energy field, but also by students
and other lay people. Audience members at these presentations have expressed a
great deal of enthusiasm for an Einstein cycle gas heat pump water heater, and have
been eager to learn when it might be available commercially (Schaefer, 2000a-2000e).

118
CHAPTER IX
SUMMARY, CONCLUSIONS AND

RECOMMENDATIONS
Summary and Conclusions
Previously, the Einstein cycle has been investigated primarily for refrigera-
tion applications. The cycle can also be used for heating, however, and has been
investigated at temperature levels that are suitable for natural gas water heating.
The configuration of the Einstein cycle was examined, and changes were made
to increase the heating coefficient of performance. These changes were primarily im-
plemented on the generator side. An external heat exchanger was added between the
generator and the condenser/absorber to improve heat recovery. The partial internal
heat exchanger in the generator was expanded to a full internal heat exchanger in
order to minimize entropy generation.

Additionally, the bubble pump performance was increased through selection
of optimum operating parameters. The submergence ratio of the bubble pump was
set to 0.2, and an optimum diameter was found to be 8.6 mm. These values resulted
in a 7.9% improvement in bubble pump performance over previously used operating
parameters.
The Einstein Cycle has been modeled using two separate property models: 1)
a corresponding states/ideal solution property model, and 2) a Patel-Teja/Panagioto-
poulos and Reid property model. The first model was used to predict fluid charac-
teristic parameters which would increase the heating COP and the second model was
119
used to more accurately predict the behavior of the cycle using the alternative fluids
selected from the results of the first model.
The first property model uses departure functions calculated from the three-
parameter theory of corresponding states to find the properties of individual fluids.
Corresponding states is based on the cubic equation of state first formulated by van
der Waals. In addition to van der Waals’ dependence on critical temperature and
pressure, however, corresponding states incorporates Pitzer’s acentric factor to model

fluid behavior. Corresponding states has been found to provide accurate results for
individual fluid properties at pressures and temperatures away from the critical point.
Once the properties of the individual fluids are calculated, the properties of the fluid
mixtures were found by utilizing Raoult’s Law and ideal solution mixing rules.
The corresponding states/ideal solution model requires only five characteristic
fluid parameters per fluid to model the system behavior. These are the critical
temperature, critical pressure, acentric factor, molecular weight, and the specific
heat at constant pressure. By varying these parameters, trends were observed that
could increase the COP.
Differences in the molecular weight of each of the fluids causes only small to
negligible changes in the COP. Varying the acentric factor and the critical temper-
ature results in the largest increase in the COP, with the refrigerant acentric factor
producing the largest effect. Lowering the refrigerant acentric factor from 0.20 to
0.08 should increase the COP by 6%.
For the base case of ammonia-water-butane, the generator temperature that
produced the highest heating COP was 495 K. Generator temperatures both above
(up to 575 K) and below (down to 425 K) this level lowered the COP, but not
significantly. The non-optimum generator temperatures also altered the magnitude
of the changes in the COP for the parameter variations, but did not alter the observed
120
trends.
Varying the critical temperature, critical pressure, and acentric factor of the
refrigerant affects the optimum system pressure. These three parameters determine
the saturation pressure of the refrigerant, which is needed to find the optimum system
pressure at the condenser/absorber temperature. Increasing the refrigerant critical
pressure increases the optimum system pressure, while increasing the critical tem-
perature or acentric factor lowers the system pressure.

Additionally, a constraint was developed to limit the corresponding states/-
ideal solution search. In order for the cycle to operate, the minimum available tem-
perature lift must be greater than or equal to the difference in the desired con-
denser/absorber and evaporator temperatures. At the optimum system pressure,

the temperature lift is the saturation temperature of the refrigerant at its partial
pressure in the condenser/absorber minus either the saturation temperature of the
pressure-equalizing fluid or the minimum boiling azeotrope, whichever is lower.
Unfortunately, due to computational limitations, the corresponding states/-

ideal solution model could not be optimized by varying all of the parameters si-
multaneously. This limits the corresponding states parameter optimization to single
parameter variations. Based on the results of the corresponding states/ideal solution
model, alternative fluids were sought for the three Einstein cycle working fluids.
No viable alternative was found for water, the absorbing fluid. For the pressure-
equalizing fluid, methyl amine and hydrogen chloride were selected for study as re-
placements for ammonia. Propane, propylene, and pentane were chosen for study as
refrigerant alternatives. Experimental equilibrium data were found in the literature
for each of these alternative mixtures. To model the behavior of these alternatives,
the Patel-Teja equation of state and Panagiotopoulos and Reid mixing rules were
used.
121
Like van der Waals and corresponding states, Patel-Teja is a cubic equation
of state. Using fluid parameters such as critical temperature and critical pressure,
the Patel-Teja equation of state can predict the behavior of individual fluids. In
conjunction with mixing rules, such as those developed by Panagiotopoulos and Reid,
the Patel-Teja equation of state can also accurately model fluid mixtures.
The Patel-Teja fugacity relations and the Panagiotopoulos and Reid mix-
ing rules were used to find the binary interaction parameters (kij and kji) for the
refrigerant/pressure-equalizing fluid pairs and the water/pressure-equalizing fluid
pairs. The binary interaction parameters were varied to match the calculated equilib-
rium states with experimental data. Excellent agreement was achieved for zeotropes,
vapor-liquid equilibrium azeotropes, and vapor-liquid-liquid equilibrium azeotropes.

Using the binary interaction parameters and the other characteristic fluid pa-
rameters, the effect of using the alternative fluid triplets on the cycle performance
was evaluated. Three operating conditions were examined. For the first case, the con-
denser/absorber temperature is 325 K and the evaporator temperature is 295 K. This

configuration can produce 125◦ F water from ambient conditions (flue gases could be
used to help to maintain the evaporator at 72◦ F). The condenser/absorber temper-
ature remains the same for the second operating configuration, but the evaporator
temperature is increased to 306 K, which would again utilize the higher temperature
thermal energy available from the flue vent gases. In the third operating configu-
ration, the Einstein cycle would be used as a water preheater, with an evaporator
temperature of 295 K and a condenser/absorber temperature of 316 K.
The Patel-Teja/Panagiotopoulos and Reid property model demonstrated that
none of the alternative refrigerants or pressure-equalizing fluids improved the COP.

One alternate refrigerant, propane, produced COPs comparable to those of the origi-
nal ammonia-water-butane mixture, but the remaining alternatives actually degraded
122
the COP. Using either ammonia-water-butane or ammonia-water-propane as the

working fluids, the Einstein cycle has a COP of 1.5 for the first operating config-
uration, 1.88 for the second configuration, and 1.76 for the third.
To test the validity of the indicated trends of the corresponding states model,
three hypothetical refrigerants and one hypothetical pressure-equalizing fluid were
also modeled using the Patel-Teja equation of state. The properties of those fluids
were altered to exactly match the improved parameters of the corresponding states
model. The hypothetical fluids each increased the COP, but to a lesser degree than
that predicted by the corresponding states/ideal solution model.
For a set evaporator load, the cycle conditions were compared for fluid com-
binations that resulted in disparate COPs. It was found that the pressure of the
system affects the absolute pressure-equalizing fluid concentration in the water. This
affects the required water mass flow per unit of ammonia circulated. When more
water must be pumped by the bubble pump, the heat input to the bubble pump is
raised to a level that can seriously degrade the COP.

Across all alternative cases, it was found that the maximum temperature lift
does not provide the highest COP. Furthermore, matching the temperature lift to the
temperature requirements also does not improve the COP. When the maximum lift
is greater than the temperature difference between the condenser/absorber and the
evaporator, the best system performance occurs at a pressure such that the partial
pressure in the condenser/absorber is the saturation pressure of the refrigerant.
It appears possible that ammonia-water-butane may be the ideal fluid triplet
for the Einstein cycle. However, ammonia-water-propane and methyl amine-water-
pentane are acceptable alternatives that do not significantly lower the COP.
With a heating COP of 1.5 from the first operating configuration, an Einstein
cycle gas heat pump water heater would cut the operating costs of a conventional gas
123
water heater by 33%. That efficiency level would result in yearly economic savings of
$70 and environmental savings of 0.15 metric tons of carbon for an average family. At
a hypothetical 100% market penetration, the national savings would be $2.6 billion
dollars and 6.4 million metric tons of carbon per year. In the commercial sector, $600
million and 1.7 million metric tons of carbon could be saved annually. The Kyoto
agreement states that the U.S. must be at or below 93% of its 1990 greenhouse
gas emission levels by 2008-20012. Currently, that means that 75 million metric
tons of carbon emissions must be eliminated. The carbon emission reductions from
widespread implementation of Einstein cycle gas heat pump water heaters would
meet nearly 11% of that goal.
While an Einstein cycle gas heat pump water heater appears to have a large
market potential, there are barriers to implementation. These might be overcome in
three ways: 1) through DOE’s minimum efficiency regulatory program, 2) through
implementation of a strategic national policy to reduce global warming emissions, and
3) through the enhanced marketing potential of a cycle named after Albert Einstein.
Recommendations
A more robust corresponding states model computer program may be able to

overcome the property optimization limitations encountered in this study. Nondi-
mensionalizing the parameters and application of nonlinear optimization solver tech-
niques may also prove beneficial. The level of potential COP improvement, however,
appears to be relatively small. Additionally, the interrelation of the various processes
in the Einstein cycle may prove to be too complicated to be accurately represented
by a corresponding states/ideal solution simplification.
When used as a gas heat pump water heater, alternate configurations for the
124
evaporator should be examined. A higher evaporator temperature raises the COP

and increases the number of potential fluid triplets. A two-stage evaporator may be
able to take advantage of both ambient-temperature heat transfer and heat transfer
from the higher-temperature flue gases.
Multistage Einstein cycles could also be investigated. The heat transferred
from the condenser/absorber of one cycle could be used to power the generator of
another cycle. This would increase the generator heat input temperature and improve
the ideal COP.
Finally, the viability of creating a mesoscopic or microscopic Einstein refrig-
eration cycle could be studied. Recently, microscopic vapor-compression cycles have
been developed for a variety of applications. Since it is a completely sealed system

with no moving parts, the Einstein cycle is a natural candidate for miniaturization.
The Einstein cycle eliminates the need for a mechanical compressor, and a compres-
sor’s machined moving parts increase the failure rate. On the microscale, however,
the continuum assumption is discarded, so the importance of boundary properties

must be explored. Capillary-driven flow will also be of importance on a microscopic
scale.
125
APPENDIX A
GENERATOR PROGRAMS
Generator Configuration 1
$INCLUDE amwatbut.txt
"Specified Points"
m_dot_1=1
T_1=315 "K"
T_2=T_1
T_3=375
P_conv=convert(bar,kPa)
P=4.5*P_conv
"Finding the Pressure of the Stream Entering

the Generator (P_1)"
T_e=289.9
x_ae=0.45
Pea|s=pressure(AMMONIA,T=T_e,x=0)
Peb|s=pressure(R600,T=T_e,x=0)
P_e=x_ae*(Pea|s-Peb|s) + Peb|s P_1=Pea|s*x_ae
"Point 1 - Entering the Generator"

P1a|s=pressure(AMMONIA,T=T_1,x=0)
P1w|s=pressure(WATER,T=T_1,x=0)
"Raoult’s law and fugacities"

x_w1=(P_1-P1a|s)/(P1w|s-P1a|s)
y_w1=(P1w|s/P_1)*x_w1
x_a1=1-x_w1 y_a1=1-y_w1
P_a1=y_a1*P_1 P_w1=y_w1*P_1
xm_w1=(x_w1*m_w)/(x_w1*m_w+x_a1*m_a)
ym_w1=(y_w1*m_w)/(y_w1*m_w+y_a1*m_a)
xm_a1=(x_a1*m_a)/(x_w1*m_w+x_a1*m_a)
126
ym_a1=(y_a1*m_a)/(y_w1*m_w+y_a1*m_a)
"Properties"
h_a1=P_1*v_f_a + u_0_a + c_v_f_a*(T_1 - T_ref_a)
h_w1=P_1*v_f_w + u_0_w + c_v_f_w*(T_1 - T_ref_w)
s_a1=s_0_a + c_p_f_a*ln(T_1/T_ref_a)
s_w1=s_0_w + c_p_f_w*ln(T_1/T_ref_w)
h_1=xm_a1*h_a1+xm_w1*h_w1
s_1=xm_a1*s_a1+xm_w1*s_w1-(xm_a1*R_a*ln(xm_a1)
+xm_w1*R_w*ln(xm_w1))
"Point 2 - Vapor Leaving"


x_w2=(P-P2a|s)/(P2w|s-P2a|s)
y_w2=(P2w|s/P)*x_w2
x_a2=1-x_w2
y_a2=1-y_w2
P_a2=y_a2*P
P_w2=y_w2*P
"Properties"
h_a2=R_a*T_2 + u_0_a + c_v_g_a*(T_2 - T_ref_a) + u_fg_a
h_w2=R_w*T_2 + u_0_w + c_v_g_w*(T_2 - T_ref_w) + u_fg_w
s_a2=s_0_a + s_fg_a + c_p_f_a*ln(T_2/T_ref_a)
- R_a*ln(P_a2/P_ref_a)
s_w2=s_0_w + s_fg_w + c_p_f_w*ln(T_2/T_ref_w)
- R_w*ln(P_w2/P_ref_w)
s_2=xm_a2*s_a2+xm_w2*s_w2
"Point3 - Solution Leaving"


127
x_w3=(P-P3a|s)/(P3w|s-P3a|s)
y_w3=(P3w|s/P)*x_w3
x_a3=1-x_w3
y_a3=1-y_w3
P_a3=y_a3*P
P_w3=y_w3*P
"Properties"
h_a3=P*v_f_a + u_0_a + c_v_f_a*(T_3 - T_ref_a)
h_w3=P*v_f_w + u_0_w + c_v_f_w*(T_3 - T_ref_w)
"Generator Control Volume"

m_dot_1=m_dot_2+m_dot_3
m_dot_1*xm_a1=m_dot_2*ym_a2+m_dot_3*xm_a3
Q_dot_g=m_dot_2*h_2+m_dot_3*h_3-m_dot_1*h_1
T_bar_g_s=Q_dot_g/(m_dot_2*s_2+m_dot_3*s_3-m_dot_1*s_1)
"Specified Points"
m_dot_1=1
P=4.5*P_conv
"Finding the Pressure of the Stream Entering the

Generator (P_1)"
T_e=289.9
x_ae=0.45
128
P_e=x_ae*(Pea|s-Peb|s) + Peb|s
P_1=Pea|s*x_ae
T_1=315 "K"
"Point 1 - Entering the Generator"


y_w1=(P1w|s/P_1)*x_w1
x_a1=1-x_w1
y_a1=1-y_w1
P_a1=y_a1*P_1
P_w1=y_w1*P_1
"Properties"

T_2=T_1
P_2=P

y_w2=(P2w|s/P_2)*x_w2
x_a2=1-x_w2
y_a2=1-y_w2
129
P_a2=y_a2*P_2
P_w2=y_w2*P_2
"Properties"
"Point3 - Solution Leaving Lower CV/Entering SHX"

T_3=375
P_3=P

y_w3=(P3w|s/P_3)*x_w3
x_a3=1-x_w3
y_a3=1-y_w3
P_a3=y_a3*P_3
P_w3=y_w3*P_3
"Properties"
130
"Point4 - Solution Leaving SHX"

T_4=T_1
P_4=P
xm_a4=xm_a3
xm_w4=xm_w3
"Properties"
"Point 5 - Solution Leaving SHX internally"

P_5=P

y_w5=(P5w|s/P_5)*x_w5
x_a5=1-x_w5
y_a5=1-y_w5
P_a5=y_a5*P_5
P_w5=y_w5*P_5
"Properties"
131
"Point 6 - Vapor Entering the SHX"

T_6=T_5
P_6=P

y_w6=(P6w|s/P_6)*x_w6
x_a6=1-x_w6
y_a6=1-y_w6
P_a6=y_a6*P_6
P_w6=y_w6*P_6
"Properties"
"Generator Control Volumes"

"Internal SHX"
m_dot_3*h_3+m_dot_1*h_1+m_dot_6*h_6=
m_dot_2*h_2+m_dot_4*h_4+m_dot_5*h_5
m_dot_4=m_dot_3
m_dot_1+m_dot_6=m_dot_2+m_dot_5
m_dot_1*xm_a1+m_dot_6*ym_a6=m_dot_2*ym_a2+m_dot_5*xm_a5
"Lower Section of the Generator"

132
T_bar_g_s=Q_dot_g/(m_dot_6*s_6+m_dot_3*s_3-m_dot_5*s_5)
"Specified Points"
m_dot_1=1
m_dot_2=m_dot_1
m_dot_4=m_dot_3
m_dot_5=m_dot_4
T_1=315 "K"
T_2=324.52
T_3=375
T_5=T_1
T_6=T_2
P=4.5*P_conv
"Finding the Pressure of the Stream Entering the Generator (P_1)"

T_e=289.9
x_ae=0.45
P_e=x_ae*(Pea|s-Peb|s) + Peb|s
P_1=Pea|s*x_ae
"Point 1 - Solution Entering External Hxgr"

CALL raoul(T_1,P_1:x_a1,x_w1,xm_a1,xm_w1,y_a1,y_w1,ym_a1,
ym_w1,P_a1,P_w1)
CALL fluprop(P_1,T_1,T_ref_a,v_f_a,c_v_f_a,c_p_f_a,u_0_a,
s_0_a:h_a1,s_a1)
CALL fluprop(P_1,T_1,T_ref_w,v_f_w,c_v_f_w,c_p_f_w,u_0_w,
s_0_w:h_w1,s_w1)
CALL fluidmix(xm_a1,xm_w1,h_a1,h_w1,s_a1,s_w1,R_a,R_w:h_1,s_1)
"Point 2 - Solution Leaving External Hxgr/Entering Generator"

CALL raoul(T_2,P:x_a2,x_w2,xm_a2,xm_w2,y_a2,y_w2,ym_a2,
ym_w2,P_a2,P_w2)
133
{xm_a2=xm_a1
***NEED TO ACHIEVE THIS BY CHOICE OF T_2***
xm_w2=xm_w1}
CALL fluprop(P,T_2,T_ref_a,v_f_a,c_v_f_a,c_p_f_a,u_0_a,
s_0_a:h_a2,s_a2)
CALL fluprop(P,T_2,T_ref_w,v_f_w,c_v_f_w,c_p_f_w,u_0_w,
s_0_w:h_w2,s_w2)
"Point3 - Solution Leaving Generator/Entering Internal Hxgr"

ym_w3,P_a3,P_w3)
s_0_a:h_a3,s_a3)
s_0_w:h_w3,s_w3)
"Point 4 - Solution Leaving Internal/Entering External Hxgr"

xm_a4=xm_a3
xm_w4=xm_w3
s_0_a:h_a4,s_a4)
s_0_w:h_w4,s_w4)
"Point 5 - Solution Leaving External Hxgr"

xm_a5=xm_a3
xm_w5=xm_w3
s_0_a:h_a5,s_a5)
s_0_w:h_w5,s_w5)

ym_w6,P_a6,P_w6)
CALL gasprop(P_a6,P_ref_a,T_6,T_ref_a,c_v_g_a,c_p_g_a,
u_0_a,u_fg_a,s_0_a,s_fg_a,R_a:h_a6,s_a6)
CALL gasprop(P_w6,P_ref_w,T_6,T_ref_w,c_v_g_w,c_p_g_w,
134
u_0_w,u_fg_w,s_0_w,s_fg_w,R_w:h_w6,s_w6)
CALL gasmix(xm_a6,xm_w6,h_a6,h_w6,s_a6,s_w6:h_6,s_6)
{Mass, Species, and Energy Balances}

0=m_dot_5*h_5-m_dot_4*h_4+m_dot_1*h_1-m_dot_2*h_2
FoM = m_dot_6*ym_a6/Q_dot_g
MassAmm=m_dot_6*ym_a6
Generator Libraries
amwatbut.txt
c p f a=4.7259088 c p f b=2.4305380 c p f w=4.6397774
c p g a=2.0942909 c p g b=1.6581138 c p g w=1.9486486

c v f a=4.2377115 c v f b=2.2874990 c v f w=4.1782731
c v g a=1.6060936 c v g b=1.5150747 c v g w=1.4871443
m a=17.030 m b=58.124 m w=18.015
P ref a=101.32 P ref b=101.32 P ref w=101.32

R a=0.4881973 R b=0.1430390 R w=0.4615043
T ref a=239.8458447 T ref b=272.4120042 T ref w=373.1676851
u 0 a=28.5827757 u 0 b=88.3527653 u 0 w=418.846656
u fg a=1292.2284431 u fg b=348.8636657 u fg w=2087.4236029

v f a=0.0014677 v f b=0.0016631 v f w=0.0010433
s 0 a=0.1212995 s 0 b=0.3498070 s 0 w=1.3063770
s fg a=5.7236373 s fg b=1.4167022 s fg w=6.0509762
raoul.lib
PROCEDURE raoul (T,P:x1,x2,xm1,xm2,y1,y2,ym1,ym2,P1,P2)

135
mw1=17.03
mw2=18.015
P1|s=pressure(AMMONIA,T=T,x=0)
P2|s=pressure(WATER,T=T,x=0)
x2=(P-P1|s)/(P2|s-P1|s)
y2=(P2|s/P)*x2
x1=1-x2
y1=1-y2
P1=y1*P
P2=y2*P
xm2=(x2*mw2)/(x2*mw2+x1*mw1)
ym2=(y2*mw2)/(y2*mw2+y1*mw1)
xm1=(x1*mw1)/(x2*mw2+x1*mw1)
ym1=(y1*mw1)/(y2*mw2+y1*mw1)
END
fluprop.lib
PROCEDURE fluprop(P,T,Tref,v,cv,cp,u0,s0:h,s)
h=P*v + u0 + cv*(T - Tref)

s=s0 + cp*ln(T/Tref)
END
gasprop.lib
PROCEDURE gasprop(P,Pref,T,Tref,cv,cp,u0,ufg,s0,sfg,R1:h,s)
h=R1*T + u0 + cv*(T - Tref) + ufg

s=s0 + sfg + cp*ln(T/Tref)- R1*ln(P/Pref)
END
fluidmix.lib
PROCEDURE fluidmix(xm1,xm2,h1,h2,s1,s2,R1,R2:h,s)
136
h=xm1*h1+xm2*h2
s=xm1*s1+xm2*s2-(xm1*R1*ln(xm1)+xm2*R2*ln(xm2))
END
gasmix.lib
PROCEDURE gasmix(xm1,xm2,h1,h2,s1,s2:h,s)
h=xm1*h1+xm2*h2
s=xm1*s1+xm2*s2
END
137
APPENDIX B
IDEAL SOLUTION MODEL PROGRAMS
Ideal Solution Model EES Program
$INCLUDE cst_sat.LIB
$INCLUDE cst_h_vap.LIB
$INCLUDE cst_h_liq.LIB
$INCLUDE fluidmix.lib
PROCEDURE fluprop2(T,Tc,Tref_r,cpl,h0:h1)
h1=h0+cpl*(T-Tref_r*Tc)
END
PROCEDURE gasprop2(T,Tc,Tref_r,P,Pc,w,M,h0,cpl:h)
$Common R
Pr=P/Pc
Tr=T/Tc
w=w
Call cst_sat(Tr,w:Prg)
CALL cst_h_vap(Tr,Pr,w:hdepvap1)
CALL cst_h_liq(Tr,Prg,w:hdepliq)
Call cst_h_vap(Tr,Prg,w:hdepvapg)
hdiff=(R/M)*(Tc)*(hdepvapg-hdepvap1)
hfg2=(R/M)*(Tc)*(hdepliq-hdepvapg)
h = h0 + cpl*(T - Tref_r*Tc) + hfg2 + hdiff
END
PROCEDURE raoul2(T,Tc1,Tc2,P,Pc1,Pc2,M1,M2,w1,w2:x1,x2,
xm1,xm2,y1,y2,ym1,ym2,P1,P2)
138
mw1=M1
mw2=M2
Tr1=T/Tc1
Tr2=T/Tc2
CALL cst_sat(Tr1,w1:Pr1|s)
CALL cst_sat(Tr2,w2:Pr2|s)
P1|s=Pr1|s*Pc1
P2|s=Pr2|s*Pc2
x2=(P-P1|s)/(P2|s-P1|s)
y2=(P2|s/P)*x2
x1=1-x2
y1=1-y2
P1=y1*P
P2=y2*P
xm2=(x2*mw2)/(x2*mw2+x1*mw1)
ym2=(y2*mw2)/(y2*mw2+y1*mw1)
xm1=(x1*mw1)/(x2*mw2+x1*mw1)
ym1=(y1*mw1)/(y2*mw2+y1*mw1)
END
Tcw=647.3
Tca=405.6
Tcb=425.25
ww=0.344
wa=0.25
wb=0.199
h0w=0
h0a=0
h0b=0
Mw=18.015
Ma=17.03
Mb=58.124
Pcw=221.2
Pca=112.8
Pcb=37.92
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cplw=4.5
cpla=5.32
cplb=2.64
R=8.31434
water=1
ammonia=2
butane=3
TconF=125
TconF=converttemp(’K’, ’F’, Tcon)
T7=Tcon
TevapF=72
TevapF=converttemp(’K’, ’F’, Tevap)
Tgen=425
TgenF=converttemp(’K’, ’F’, Tgen)
T9=Tgen
Tcontrol=(Tcon+0.1)/Tcb
CALL cst_sat(Tcontrol,wb:P/Pcb) "Sets System Pressure"
m9=1
CALL cst_sat(Tref_rw,ww:1/Pcw)
CALL cst_sat(Tref_ra,wa:1/Pca)
CALL cst_sat(Tref_rb,wb:1/Pcb)
CALL raoul2(T7,Tca,Tcw,Pa3,Pca,Pcw,Ma,Mw,wa,ww:xa7,xw7,
xma7,xmw7,ya7,yw7,yma7,ymw7,Pa7,Pw7)
CALL fluprop2(T7,Tca,Tref_ra,cpla,h0a:ha7)
CALL fluprop2(T7,Tcw,Tref_rw,cplw,h0w:hw7)
CALL fluidmix(xma7,xmw7,ha7,hw7:h7)
xma8=xma7
xmw8=xmw7
T8=T10-3
m8=m7
140
Qext1=m7*(h8-h7)
CALL raoul2(T9,Tca,Tcw,P,Pca,Pcw,Ma,Mw,wa,ww:xa9,xw9,
T5=T8
CALL gasprop2(T5,Tca,Tref_ra,Pa5,Pca,wa,Ma,h0a,cpla:ha5)
CALL gasprop2(T5,Tcw,Tref_rw,Pw5,Pcw,ww,Mw,h0w,cplw:hw5)
CALL fluidmix(yma5,ymw5,ha5,hw5:h5)
T11=Tcon
m11=m9
Qext2=m9*(h10-h11)
Qext1=Qext2
xma10=xma9
xmw10=xmw9
m10=m9
Qint=m9*(h9-h10)
Qg = m10*h10 + m5*h5 -m8*h8
m8*xma8 = m5*yma5 + m9*xma9

m8=m9+m5
CALL raoul2(Tcon,Tca,Tcb,P,Pca,Pcb,Ma,Mb,wa,wb:xaca,xbca,
xmaca,xmbca,yaca,ybca,ymaca,ymbca,Paca,Pbca)
xmb1=ymbca
CALL raoul2(T1ca,Tca,Tcb,P,Pca,Pcb,Ma,Mb,wa,wb:xa1,xb1,
141
xma1,xmb1,ya1,yb1,yma1,ymb1,Pa1,Pb1)
T1=Tcon
CALL fluprop2(T1,Tcb,Tref_rb,cplb,h0b:hb1)
CALL fluidmix(xma1,xmb1,ha1,hb1:h1)
T2p=Tevap
T3p=T2p
T4p=T2p
CALL raoul2(T2p,Tca,Tcb,P,Pca,Pcb,Ma,Mb,wa,wb:xa2p,xb2p,
xma2p,xmb2p,ya2p,yb2p,yma2p,ymb2p,Pa2p,Pb2p)
CALL fluprop2(T2p,Tca,Tref_ra,cpla,h0a:ha2p)
CALL fluprop2(T2p,Tcb,Tref_rb,cplb,h0b:hb2p)
CALL fluidmix(xma2p,xmb2p,ha2p,hb2p:h2p)
CALL gasprop2(T4p,Tca,Tref_ra,P,Pca,wa,Ma,h0a,cpla:ha4p)
h4p=ha4p
CALL raoul2(T3p,Tca,Tcb,P,Pca,Pcb,Ma,Mb,wa,wb:xa3p,xb3p,
xma3p,xmb3p,ya3p,yb3p,yma3p,ymb3p,Pa3p,Pb3p)
CALL gasprop2(T3p,Tca,Tref_ra,Pa3p,Pca,wa,Ma,h0a,cpla:ha3p)
CALL gasprop2(T3p,Tcb,Tref_rb,Pb3p,Pcb,wb,Mb,h0b,cplb:hb3p)
CALL fluidmix(yma3p,ymb3p,ha3p,hb3p:h3p)
xma2=xma1
xmb2=xmb1
m2=m1
CALL fluprop2(T2,Tcb,Tref_rb,cplb,h0b:hb2)
CALL fluidmix(xma2,xmb2,ha2,hb2:h2)
T4=T2
CALL fluprop2(T4,Tca,Tref_ra,cpla,h0a:ha4l)
CALL fluprop2(T4,Tcw,Tref_rw,cplw,h0w:hw4l)
CALL fluidmix(xma4,xmw4,ha4l,hw4l:h4l)
CALL gasprop2(T4,Tca,Tref_ra,Pa4,Pca,wa,Ma,h0a,cpla:ha4v)
CALL gasprop2(T4,Tcw,Tref_rw,Pw4,Pcw,ww,Mw,h0w,cplw:hw4v)
CALL fluidmix(yma4,ymw4,ha4v,hw4v:h4v)
142
{VP=vapor percentage}
yma5 = VP*yma4 + (1-VP)*xma4
h4=VP*h4v + (1-VP)*h4l
m4=VP*m5
m4v=m4
m4l=m5-m4v
CALL raoul2(T3,Tca,Tcb,P,Pca,Pcb,Ma,Mb,wa,wb:xa3,xb3,
xma3,xmb3,ya3,yb3,yma3,ymb3,Pa3,Pb3)
CALL gasprop2(T3,Tcb,Tref_rb,Pb3,Pcb,wb,Mb,h0b,cplb:hb3)
CALL fluidmix(yma3,ymb3,ha3,hb3:h3)
m2+m3p=m2p+m3
m2*xmb2+m3p*ymb3p=m2p*xmb2p+m3*ymb3
m3p=m2p+m4p
m3p*yma3p=m2p*xma2p+m4p
m3*h3 - m2*h2 - m4*h4v = m3p*h3p - m4p*h4p - m2p*h2p

Qe = m3*h3 - m2*h2 - m4*h4v
m6=m3
yma6=yma3
ymb6=ymb3
T6=T5
CALL gasprop2(T6,Tcb,Tref_rb,Pb3,Pcb,wb,Mb,h0b,cplb:hb6)
CALL fluidmix(yma6,ymb6,ha6,hb6:h6)
Qpc1=m2*h2 + m4v*h4v + m6*h6 + m4l*h4l

Qpc2=m1*h1 + m3*h3 + m5*h5
Qpc1=Qpc2
m7+m1=m11+m6+m4l
Qca=m7*h7+m1*h1-m4l*h4l-m6*h6-m11*h11
Qcheck=Qca+Qg+Qe
COP_h = -Qca/(Qg)
COP_h_ideal = ((Tgen-Tevap)/(Tgen))/((Tcon-Tevap)/Tcon)
143
Ideal Solution Model Libraries
cst sat.lib
PROCEDURE cst_sat(Tr,w:Pr)
Pr := exp(5.92714 - (6.09648/Tr) - 1.28862*ln(Tr)
+ 0.169347*(Tr^6) + w*(15.2518 - (15.6875/Tr)
- 13.4721*ln(Tr) + 0.43577*(Tr^6)))
END
cst h liq.lib
PROCEDURE cst_h_liq(Tr,Pr,w:hdepliq)
col_num := Pr*100
row_num := 100*(Tr-0.29)
IF (col_num<1) THEN
h_0_liq := lookup(’hzeroliq’,row_num,1) -
- ((Pr-0.01)/0.01)*(lookup(’hzeroliq’,row_num,1)
- lookup(’hzeroliq’,row_num,2))
h_1_liq := lookup(’honeliq’,row_num,1)
- ((Pr-0.01)/0.01)*(lookup(’honeliq’,row_num,1)
- lookup(’honeliq’,row_num,2))
hdepliq := h_0_liq + w*h_1_liq
ELSE
h_0_liq := lookup(’hzeroliq’,row_num,col_num)
h_1_liq := lookup(’honeliq’,row_num,col_num)
hdepliq := h_0_liq + w*h_1_liq
ENDIF
END
cst h vap.lib
PROCEDURE cst_h_vap(Tr,Pr,w:hdepvap)
col_num := Pr*100
row_num := 100*(Tr-0.29)
IF (col_num<1) THEN
h_0_vap := (Pr/0.01)*(lookup(’hzerovap’,row_num,1))
h_1_vap := (Pr/0.01)*(lookup(’honevap’,row_num,1))
hdepvap := h_0_vap + w*h_1_vap
ELSE
144
h_0_vap := lookup(’hzerovap’,row_num,col_num)
h_1_vap := lookup(’honevap’,row_num,col_num)
hdepvap := h_0_vap + w*h_1_vap
ENDIF
END
fluidmix.lib
PROCEDURE fluidmix(xm1,xm2,h1,h2:h)
h=xm1*h1+xm2*h2
END
145
APPENDIX C
PATEL-TEJA MODEL PROGRAMS
EES Program
$include Pteosambtl.LIB
$include Pteosambtv.LIB
$include Pteosawl.lib
$include Pteosawv.lib
$include ptabvlehsv.LIB
$include ptawvlehsv.LIB
$include ptamwtsc.LIB
$include ptamhsv.LIB
P=5.25
{State 1: Ammonia-Butane saturated liquid leaving condenser}

{This sets T1}
xa1=0.001
CALL ptabvlehsv(T1,P,xa1,ya1:xam1,yam1,xbm1,ybm1,hv1,hl1,sv1,sl1,
vl1,vv1,fal1,fav1,fbl1,fbv1)
fal1=fav1
fbl1=fbv1
{States 3: Ammonia-Butane sat. liquid/vapor in evaporator}

T3=295
fal3=fav3
fbl3=fbv3
{State 5: Superheated Ammonia entering PC}

T5=T1
CALL ptamhsv(T5,P:hl5,hv5,sl5,sv5,vl5,vv5)
146
{State 2: Butane subcooled liquid leaving pre-cooler}

T2=T3+pinch23
pinch23=0
xa2=xa1
ya2=ya1
{State 6: Super-Heated Ammonia-Butane leaving PC}

T6=T5-pinch65
pinch65=0
ya6=ya3
xa6=xa3
{State 7: Ammonia-Water sat. liquid leaving condenser}

T7=T1
Pa7=P*ya3
CALL ptawvlehsv(T7,Pa7,xa7,ya7:xam7,yam7,xwm7,ywm7,hv7,hl7,sv7,sl7,
vl7,vv7,fal7,fav7,fwl7,fwv7)
fal7=fav7
fwl7=fwv7
{State 9: Ammonia-Water sat. liquid Generator heat input}

T9=424
CALL ptawvlehsv(T9,P,xa9,ya9:xam9,yam9,xwm9,ywm9,hv9,hl9,sv9,sl9,
vl9,vv9,fal9,fav9,fwl9,fwv9)
fal9=fav9
fwl9=fwv9
{State 11: Ammonia-Water sub-cooled liquid leaving

Generator Ext Hxgr}
T11=T7+pinch97
pinch97=0
xa11=xa9
ya11=ya9
xam11=xam9
CALL ptamwtsc(T11,P,xa11:h11,s11)
{Bubble Pump}
mbp=1
147
m9v=mbp/28.6
m9=mbp-m9v
m11=m9
{Evaporator: conservation of mass and energy}

m2=m1
m6=m3
m2+m4=m3
{ammonia}
yam4=1
m5=m4
xam2*m2+m4*yam4=m3*yam3
{Condenser/Absorber overall}
m1+m7=m11+m6+m9v
m1*xam1+m7*xam7=m11*xam11+m6*yam6+m9v*yam9
{Pre-cooler}
m3*hv3+m1*hl1+m5*hv5=m6*hv6+m2*hl2+m4*hv4
Qc=m1*hl1+m7*hl7-m11*h11-m6*hv6-m9v*hv9
Tc=T1
Qe=m3*hv3-hl2*m2-hv4*m4
Tg=T9
Te=T3
merr1=m4+m11+m9v-m7 "Error Checking"

merr2=m4*yam4+xam11*m11+yam9*m9v-m7*xam7
{Intermediate State 5a}

y5a=1
m5a=m5
xa8=xa7
m8=m7
m10=m11
xa10=xa9
T5a=348.8 "Determined from an external program"
T8=T5a
CALL ptamhsv(T5a,P:hl5a,hv5a,sl5a,sv5a,vl5a,vv5a)
Qdump1=m5*(hv5a-hv5)
148
Qget1=m8*(h8 - hl7)
Qdump2=m10*(h10-h11)
Qdump1+Qdump2=Qget1
Qg=m10*h10+m9v*hv9+m5a*hv5a-m8*h8
Q_bp=m9v*(hv9-hl9)
Qgact=Qg-Q_bp
Qerr=Qg+Qe+Qc "Error checking"
COP=-Qc/(Qg)
COPi=((Tg-Te)/(Tg))/((Tc-Te)/Tc)
Program Libraries
pteosambtl.lib
PROCEDURE pteosambtl(T,P,xa,k_ab,k_ba:f_ial,f_ibl,v_ml,xb,xa_mass,
xb_mass,h_depl,s_depl)
k_aa=0
k_bb=0
R = 8.314/100000 {m^3*bar/mol K}
{ammonia}
omega_a=.25
Tc_a=405.6
Pc_a=112.8
Tr_a=T/Tc_a
F_a=.627090
Zeta_a=.282
Omega_2a=.06934
Omega_1a=3*Zeta_a^2+3*(1-2*Zeta_a)*Omega_2a+Omega_2a^2+1-3*Zeta_a
Omega_3a=1-3*Zeta_a
a_Tc_a=(R^2*Tc_a^2/Pc_a)
b_Tc_a=(R*Tc_a/Pc_a)
alpha_a=(1+F_a*(1-Tr_a^.5))^2
a_a=a_Tc_a*alpha_a*Omega_1a
149
b_a=Omega_2a*b_Tc_a
c_a=Omega_3a*b_Tc_a
Aa=(a_a*P)/(R^2*T^2)
Ba=b_a*P/(R*T)
Ca=c_a*P/(R*T)
Na=(b_a*c_a+((b_a+c_a)/2)^2)^.5
Ma=((b_a+c_a)/2-Na)*P/(R*T)
Qa=((b_a+c_a)/2+Na)*P/(R*T)
{butane}
omega_b=.199
Tc_b=425.2
Pc_b=38
Tr_b=T/Tc_b
F_b=.678389
Zeta_b=.309
Omega_2b=0.07834
Omega_1b=3*Zeta_b^2+3*(1-2*Zeta_b)*Omega_2b+Omega_2b^2+1-3*Zeta_b
Omega_3b=1-3*Zeta_b
a_Tc_b=(R^2*Tc_b^2/Pc_b)
b_Tc_b=(R*Tc_b/Pc_b)
alpha_b=(1+F_b*(1-Tr_b^.5))^2
a_b=a_Tc_b*alpha_b*Omega_1b
b_b=b_Tc_b*Omega_2b
c_b=b_Tc_b*Omega_3b
Ab=(a_b*P)/(R^2*T^2)
Bb=b_b*P/(R*T)
Cb=c_b*P/(R*T)
Nb=(b_b*c_b+((b_b+c_b)/2)^2)^.5
Mb=((b_b+c_b)/2-Nb)*P/(R*T)
Qb=((b_b+c_b)/2+Nb)*P/(R*T)
xb=1-xa
a_aa=a_a
a_ab=(a_a*a_b)^.5*(1-k_ab+(k_ab-k_ba)*xa)
a_bb=a_b
a_ba=(a_b*a_a)^.5*(1-k_ba+(k_ba-k_ab)*xb)
a_mx=xa*xa*a_aa+xb*xb*a_bb+xa*xb*a_ab+xb*xa*a_ba
b_mx=xa*b_a+xb*b_b
c_mx=xa*c_a+xb*c_b
A_m=(a_mx*P)/(R^2*T^2)
B_m=b_mx*P/(R*T)
150
C_m=c_mx*P/(R*T)
N_m=(b_mx*c_mx+((b_mx+c_mx)/2)^2)^.5
M_m=((b_mx+c_mx)/2-N_m)*P/(R*T)
Q_m=((b_mx+c_mx)/2+N_m)*P/(R*T)
ap_1=-2*(xa*xa*a_a+xa*xb*(a_a*a_b)^.5*(1-k_ab)+xb*xb*a_b
+xb*xa*(a_b*a_a)^.5*(1-k_ba))
ap_2=-3*(xa^2*xb*(a_a*a_b)^.5*(k_ab-k_ba)
+xb^2*xa*(a_b*a_a)^.5*(k_ba-k_ab))
ap_3a=2*xa*xb*(a_a*a_b)^.5*(k_ab-k_ba)
ap_3b=2*xb*xa*(a_b*a_a)^.5*(k_ba-k_ab)
ap_4a=2*xa*a_a+xb*(a_a*a_b)^.5*(1-k_ab+1-k_ba+(k_ba-k_ab)*xb)
ap_4b=2*xb*a_b+xa*(a_b*a_a)^.5*(1-k_ba+1-k_ab+(k_ab-k_ba)*xa)
ap_a=ap_1+ap_2+ap_3a+ap_4a
ap_b=ap_1+ap_2+ap_3b+ap_4b
bp_a=b_a-b_mx
bp_b=b_b-b_mx
cp_a=c_a-c_mx
cp_b=c_b-c_mx
c_1=1
c_2=(C_m-1)
c_3=(-2*B_m*C_m-B_m^2-B_m-C_m+A_m)
c_4=(B_m^2*C_m+B_m*C_m-A_m*B_m)
pp=c_2/c_1
qq=c_3/c_1
rr=c_4/c_1
A_cubic=1/3*(3*qq-pp^2)
B_cubic=1/27*(2*pp^3-9*pp*qq+27*rr)
D_cubic=(A_cubic)^3/27+(B_cubic)^2/4
IF D_cubic<0 THEN
phi=arccos(((B_cubic^2/4)/(-A_cubic^3/27))^.5)
yr1=2*(-A_cubic/3)^.5*cos(phi/3)
yr3=2*(-A_cubic/3)^.5*cos(phi/3+4.18879020479)
yr2=2*(-A_cubic/3)^.5*cos(phi/3+2.09439510239)
Z_mv=yr1-pp/3
Z_ml=yr2-pp/3
Zr3=yr3-pp/3
ENDif
IF D_cubic>0 THEN
M_cubic=(-B_cubic/2+(D_cubic)^.5)^(1/3)
N_cubic=(-B_cubic/2-(D_cubic)^.5)^(1/3)
151
Z_mv=M_cubic+N_cubic-pp/3
Z_ml=-(M_cubic+N_cubic)/2-pp/3
endif
v_ml=Z_ml*R*T/P
Q=-(b_mx^2+6*b_mx*c_mx+c_mx^2)
D_l=v_ml^2+v_ml*(b_mx+c_mx)-b_mx*c_mx
D1_l=(1/(-Q)^.5)*ln((2*v_ml+(b_mx+c_mx)-(-Q)^.5)/(2*v_ml
+(b_mx+c_mx)+(-Q)^.5))
F_1al=v_ml/(Q*D_l)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_a
+3*bp_a*c_mx+3*b_mx*cp_a+c_mx*cp_a)
+1/(Q*D_l)*(bp_a*c_mx^2+b_mx^2*cp_a
-b_mx*bp_a*c_mx-b_mx*c_mx*cp_a)+D1_l/Q*(b_mx*bp_a
+3*b_mx*cp_a-b_mx^2+3*bp_a*c_mx+c_mx*cp_a-c_mx^2
-6*b_mx*c_mx)
phi_ial=(ln(v_ml/(v_ml-b_mx))+(b_mx+bp_a)/(v_ml-b_mx)
+(ap_a*D1_l)/(R*T)+a_mx/(R*T)*(F_1al)-ln(Z_ml))
f_ial1=exp(ln(v_ml/(v_ml-b_mx))+(b_mx+bp_a)/(v_ml-b_mx)
f_ial2=xa*P
f_ial=f_ial1*f_ial2
F_1bl=v_ml/(Q*D_l)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_b
+3*bp_b*c_mx+3*b_mx*cp_b+c_mx*cp_b)
+1/(Q*D_l)*(bp_b*c_mx^2+b_mx^2*cp_b
-b_mx*bp_b*c_mx-b_mx*c_mx*cp_b)+D1_l/Q*(b_mx*bp_b
+3*b_mx*cp_b-b_mx^2+3*bp_b*c_mx+c_mx*cp_b-c_mx^2
-6*b_mx*c_mx)
phi_ibl=(ln(v_ml/(v_ml-b_mx))+(b_mx+bp_b)/(v_ml-b_mx)
+(ap_b*D1_l)/(R*T)+a_mx/(R*T)*(F_1bl)-ln(Z_ml))
f_ibl1=exp(ln(v_ml/(v_ml-b_mx))+(b_mx+bp_b)/(v_ml-b_mx)
+(ap_b*D1_l)/(R*T)+a_mx/(R*T)*(F_1bl)-ln(Z_ml))
f_ibl2=xb*P
f_ibl=f_ibl1*f_ibl2
mwa=17.03 {ammonia kg/kmol}

mwb=58.124 {butane kg/kmol}
mwml=mwa*xa+mwb*xb
xa_mass=xa*mwa/mwml
xb_mass=1-xa_mass
aTcab=((a_Tc_a*Omega_1a)*(a_Tc_b*Omega_1b))^.5
152
daabdT=-(aTcab*F_a*(1+F_b*(1-Tr_b^.5)))/(2*(Tr_a)^.5*Tc_a)
-(aTcab*F_b*(1+F_a*(1-Tr_a^.5)))/(2*(Tr_b)^.5*Tc_b)
daadT=(Omega_1a*R^2*Tc_a/Pc_a)*(-F_a*alpha_a^.5*Tr_a^(-.5))
dabdT=(Omega_1b*R^2*Tc_b/Pc_b)*(-F_b*alpha_b^.5*Tr_b^(-.5))
daasrdT=-(Omega_1a*R^2/Pc_a)^.5*F_a/(2*(Tr_a)^.5)
dabsrdT=-(Omega_1b*R^2/Pc_b)^.5*F_b/(2*(Tr_b)^.5)
damxdT2=xa*xa*daadT*(1-k_aa)+xa*xb*(daabdT)*(1-k_ab
+(k_ab-k_ba)*xa)+xb*xb*dabdT*(1-k_bb)
+xb*xa*(daabdT)*(1-k_ba+(k_ba-k_ab)*xb)
damxdT=xa*xa*daadT*(1-k_aa)+(daasrdT*a_b^.5
+dabsrdT*a_a^.5)*xa*xb*(1-k_ab+(k_ab-k_ba)*xa)
+xb*xb*dabdT*(1-k_bb)+(daasrdT*a_b^.5
+dabsrdT*a_a^.5)*xb*xa*(1-k_ba+(k_ba-k_ab)*xb)
h_depl=100000*R*T*(Z_ml-1)-100000*(T*damxdT-a_mx)
*(1/(2*N_m))*ln((Z_ml+M_m)/(Z_ml+Q_m))
s_depl=100000*(-R*ln(P/(Z_ml-B_m))-damxdT*((1/(2*N_m))
*ln((Z_ml+M_m)/(Z_ml+Q_m))))
END
pteosambtv.lib
PROCEDURE pteosambtv(T,P,ya,k_ab,k_ba:f_iav,f_ibv,v_mv,yb,
ya_mass,yb_mass,h_depv,s_depv)
k_aa=0
k_bb=0
R = 8.314/100000 {m^3*bar/mol K}
{ammonia}
omega_a=.25
Tc_a=405.6
Pc_a=112.8
Tr_a=T/Tc_a
F_a=.627090
Zeta_a=.282
Omega_2a=.06934
Omega_3a=1-3*Zeta_a
153
alpha_a=(1+F_a*(1-Tr_a^.5))^2
b_a=Omega_2a*b_Tc_a
c_a=Omega_3a*b_Tc_a
Aa=(a_a*P)/(R^2*T^2)
Ba=b_a*P/(R*T)
Ca=c_a*P/(R*T)
Na=(b_a*c_a+((b_a+c_a)/2)^2)^.5
{butane}
omega_b=.199
Tc_b=425.2
Pc_b=38
Tr_b=T/Tc_b
F_b=.678389
Zeta_b=.309
Omega_2b=0.07834
Omega_1b=3*Zeta_b^2+3*(1-2*Zeta_b)*Omega_2b+Omega_2b^2+1-3*Zeta_b
Omega_3b=1-3*Zeta_b
a_Tc_b=(R^2*Tc_b^2/Pc_b)
b_Tc_b=(R*Tc_b/Pc_b)
alpha_b=(1+F_b*(1-Tr_b^.5))^2
a_b=a_Tc_b*alpha_b*Omega_1b
b_b=b_Tc_b*Omega_2b
c_b=b_Tc_b*Omega_3b
Ab=(a_b*P)/(R^2*T^2)
Bb=b_b*P/(R*T)
Cb=c_b*P/(R*T)
Nb=(b_b*c_b+((b_b+c_b)/2)^2)^.5
Mb=((b_b+c_b)/2-Nb)*P/(R*T)
Qb=((b_b+c_b)/2+Nb)*P/(R*T)
yb=1-ya
a_aa=a_a*(1-k_aa)
a_ab=(a_a*a_b)^.5*(1-k_ab+(k_ab-k_ba)*ya)
a_bb=a_b*(1-k_bb)
a_ba=(a_b*a_a)^.5*(1-k_ba+(k_ba-k_ab)*yb)
a_mx=ya*ya*a_aa+yb*yb*a_bb+ya*yb*a_ab+yb*ya*a_ba
b_mx=ya*b_a+yb*b_b
c_mx=ya*c_a+yb*c_b
154
A_m=(a_mx*P)/(R^2*T^2)
B_m=b_mx*P/(R*T)
C_m=c_mx*P/(R*T)
N_m=(b_mx*c_mx+((b_mx+c_mx)/2)^2)^.5
ap_1=-2*(ya*ya*a_a*(1-k_aa)+ya*yb*(a_a*a_b)^.5*(1-k_ab)
+yb*yb*a_b*(1-k_bb)+yb*ya*(a_b*a_a)^.5*(1-k_ba))
ap_2=-3*(ya^2*yb*(a_a*a_b)^.5*(k_ab-k_ba)
+yb^2*ya*(a_b*a_a)^.5*(k_ba-k_ab))
ap_3a=2*ya*yb*(a_a*a_b)^.5*(k_ab-k_ba)
ap_3b=2*yb*ya*(a_b*a_a)^.5*(k_ba-k_ab)
ap_4a=2*ya*a_a*(1-k_aa)+yb*(a_a*a_b)^.5*(1-k_ab+1
-k_ba+(k_ba-k_ab)*yb)
ap_4b=2*yb*a_b*(1-k_bb)+ya*(a_b*a_a)^.5*(1-k_ba+1
-k_ab+(k_ab-k_ba)*ya)
ap_b=ap_1+ap_2+ap_3b+ap_4b
bp_a=b_a-b_mx
bp_b=b_b-b_mx
cp_a=c_a-c_mx
cp_b=c_b-c_mx
c_1=1
c_2=(C_m-1)
c_3=(-2*B_m*C_m-B_m^2-B_m-C_m+A_m)
pp=c_2/c_1
qq=c_3/c_1
rr=c_4/c_1
IF D_cubic<0 THEN
phi=arccos(((B_cubic^2/4)/(-A_cubic^3/27))^.5)
yr1=2*(-A_cubic/3)^.5*cos(phi/3)
yr3=2*(-A_cubic/3)^.5*cos(phi/3+4.18879020479)
yr2=2*(-A_cubic/3)^.5*cos(phi/3+2.09439510239)
Z_mv=yr1-pp/3
Z_ml=yr2-pp/3
Zr3=yr3-pp/3
155
ENDIF
IF D_cubic>0 THEN
M_cubic=(-B_cubic/2+(D_cubic)^.5)^(1/3)
N_cubic=(-B_cubic/2-(D_cubic)^.5)^(1/3)
Z_mv=M_cubic+N_cubic-pp/3
Z_ml=-(M_cubic+N_cubic)/2-pp/3
ENDIF
v_ml=Z_ml*R*T/P
v_mv=Z_mv*R*T/P
D_v=v_mv^2+v_mv*(b_mx+c_mx)-b_mx*c_mx
D1_v=(1/(-Q)^.5)*ln((2*v_mv+(b_mx+c_mx)-(-Q)^.5)/(2*v_mv
+(b_mx+c_mx)+(-Q)^.5))
F_1av=v_mv/(Q*D_v)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_a
+1/(Q*D_v)*(bp_a*c_mx^2+b_mx^2*cp_a-b_mx*bp_a*c_mx
-b_mx*c_mx*cp_a)+D1_v/Q*(b_mx*bp_a+3*b_mx*cp_a-b_mx^2
+3*bp_a*c_mx+c_mx*cp_a-c_mx^2-6*b_mx*c_mx)
f_iav=ya*P*exp(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_a)/(v_mv-b_mx)
+(ap_a*D1_v)/(R*T)+a_mx/(R*T)*(F_1av)-ln(Z_mv))
f_iav1=exp(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_a)/(v_mv-b_mx)
f_iav2=ya*P
phi_iav=(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_a)/(v_mv-b_mx)
F_1bv=v_mv/(Q*D_v)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_b
+3*bp_b*c_mx+3*b_mx*cp_b+c_mx*cp_b)
+1/(Q*D_v)*(bp_b*c_mx^2+b_mx^2*cp_b-b_mx*bp_b*c_mx
-b_mx*c_mx*cp_b)+D1_v/Q*(b_mx*bp_b+3*b_mx*cp_b-b_mx^2
+3*bp_b*c_mx+c_mx*cp_b-c_mx^2-6*b_mx*c_mx)
f_ibv=yb*P*exp(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_b)/(v_mv-b_mx)
+(ap_b*D1_v)/(R*T)+a_mx/(R*T)*(F_1bv)-ln(Z_mv))
f_ibv1=exp(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_b)/(v_mv-b_mx)
f_ibv2=yb*P
phi_ibv=(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_b)/(v_mv-b_mx)

mwmv=mwa*ya+mwb*yb
156
ya_mass=ya*mwa/mwmv
yb_mass=1-ya_mass
aTcab=((a_Tc_a*Omega_1a)*(a_Tc_b*Omega_1b))^.5
daabdT=-(aTcab*F_a*(1+F_b*(1-Tr_b^.5)))/(2*(Tr_a)^.5*Tc_a)
-(aTcab*F_b*(1+F_a*(1-Tr_a^.5)))/(2*(Tr_b)^.5*Tc_b)
dabdT=(Omega_1b*R^2*Tc_b/Pc_b)*(-F_b*alpha_b^.5*Tr_b^(-.5))
dabsrdT=-(Omega_1b*R^2/Pc_b)^.5*F_b/(2*(Tr_b)^.5)
damxdT2=ya*ya*daadT*(1-k_aa)+ya*yb*(daabdT)*(1-k_ab+(k_ab
-k_ba)*ya)+yb*yb*dabdT*(1-k_bb)+yb*ya*(daabdT)*(1
-k_ba+(k_ba-k_ab)*yb)
damxdT=ya*ya*daadT*(1-k_aa)+(daasrdT*a_b^.5+dabsrdT*a_a^.5)*ya*yb*
(1-k_ab+(k_ab-k_ba)*ya)+yb*yb*dabdT*(1-k_bb)
+(daasrdT*a_b^.5+dabsrdT*a_a^.5)*yb*ya*(1-k_ba+(k_ba-k_ab)*yb)
{mixture enthalpy and entropy departures:

h (kJ/kmol) and s (kJ/kmol*K)}
h_depv=100000*R*T*(Z_mv-1)-100000*(T*damxdT-a_mx)*(1/(2*N_m))
*ln((Z_mv+M_m)/(Z_mv+Q_m))
s_depv=100000*(-R*ln(P/(Z_mv-B_m))-damxdT*((1/(2*N_m))
*ln((Z_mv+M_m)/(Z_mv+Q_m))))
END
pteosawl.lib
PROCEDURE pteosawl(T,P,xa:f_ial,f_iwl,v_ml,xw,xa_mass,xw_mass,
h_depl,s_depl)
k_aa=0
k_ww=0
k_aw=-0.26328
k_wa=-0.29368
R = 8.314/100000 {m^3*bar/mol K}
{ammonia}
omega_a=.25
Tc_a=405.6
Pc_a=112.8
Tr_a=T/Tc_a
F_a=.627090
157
Zeta_a=.282
Omega_2a=.06934
Omega_3a=1-3*Zeta_a
alpha_a=(1+F_a*(1-Tr_a^.5))^2
b_a=Omega_2a*b_Tc_a
c_a=Omega_3a*b_Tc_a
Aa=(a_a*P)/(R^2*T^2)
Ba=b_a*P/(R*T)
Ca=c_a*P/(R*T)
Na=(b_a*c_a+((b_a+c_a)/2)^2)^.5
{water}
omega_w=.344
Tc_w=647.3
Pc_w=221.2
Tr_w=T/Tc_w
F_w=.689803
Zeta_w=.269
Omega_2w=0.065103
Omega_1w=3*Zeta_w^2+3*(1-2*Zeta_w)*Omega_2w+Omega_2w^2+1-3*Zeta_w
Omega_3w=1-3*Zeta_w
a_Tc_w=(R^2*Tc_w^2/Pc_w)
b_Tc_w=(R*Tc_w/Pc_w)
alpha_w=(1+F_w*(1-Tr_w^.5))^2
a_w=a_Tc_w*alpha_w*Omega_1w
b_w=b_Tc_w*Omega_2w
c_w=b_Tc_w*Omega_3w
Aw=(a_w*P)/(R^2*T^2)
Bw=b_w*P/(R*T)
Cw=c_w*P/(R*T)
Nw=(b_w*c_w+((b_w+c_w)/2)^2)^.5
Mw=((b_w+c_w)/2-Nw)*P/(R*T)
Qw=((b_w+c_w)/2+Nw)*P/(R*T)
xw=1-xa
a_aa=a_a*(1-k_aa)
158
a_aw=(a_a*a_w)^.5*(1-k_aw+(k_aw-k_wa)*xa)
a_ww=a_w*(1-k_ww)
a_wa=(a_w*a_a)^.5*(1-k_wa+(k_wa-k_aw)*xw)
a_mx=xa*xa*a_aa+xw*xw*a_ww+xa*xw*a_aw+xw*xa*a_wa
b_mx=xa*b_a+xw*b_w
c_mx=xa*c_a+xw*c_w
A_m=(a_mx*P)/(R^2*T^2)
B_m=b_mx*P/(R*T)
C_m=c_mx*P/(R*T)
N_m=(b_mx*c_mx+((b_mx+c_mx)/2)^2)^.5
ap_1=-2*(xa*xa*a_a*(1-k_aa)+xa*xw*(a_a*a_w)^.5*(1-k_aw)
+xw*xw*a_w*(1-k_ww)+xw*xa*(a_w*a_a)^.5*(1-k_wa))
ap_2=-3*(xa^2*xw*(a_a*a_w)^.5*(k_aw-k_wa)
+xw^2*xa*(a_w*a_a)^.5*(k_wa-k_aw))
ap_3a=2*xa*xw*(a_a*a_w)^.5*(k_aw-k_wa)
ap_3w=2*xw*xa*(a_w*a_a)^.5*(k_wa-k_aw)
ap_4a=2*xa*a_a*(1-k_aa)+xw*(a_a*a_w)^.5*(1-k_aw+1-k_wa
+(k_wa-k_aw)*xw)
ap_4w=2*xw*a_w*(1-k_ww)+xa*(a_w*a_a)^.5*(1-k_wa+1-k_aw
+(k_aw-k_wa)*xa)
ap_w=ap_1+ap_2+ap_3w+ap_4w
bp_a=b_a-b_mx
bp_w=b_w-b_mx
cp_a=c_a-c_mx
cp_w=c_w-c_mx
c_1=1
c_2=(C_m-1)
c_3=(-2*B_m*C_m-B_m^2-B_m-C_m+A_m)
pp=c_2/c_1
qq=c_3/c_1
rr=c_4/c_1
Q_r=(c_2^2-3*c_3)/9
R_r=(2*c_2^3-9*c_2*c_3+27*c_4)/54
159
theta_r=arccos(R_r*Q_r^(-1.5))
Z_ml=-2*(Q_r^.5)*(cos(theta_r/3))-c_2/3
v_ml=Z_ml*R*T/P
D_l=v_ml^2+v_ml*(b_mx+c_mx)-b_mx*c_mx
D1_l=(1/(-Q)^.5)*ln((2*v_ml+(b_mx+c_mx)-(-Q)^.5)/(2*v_ml
+(b_mx+c_mx)+(-Q)^.5))
F_1al=v_ml/(Q*D_l)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_a
+1/(Q*D_l)*(bp_a*c_mx^2+b_mx^2*cp_a-b_mx*bp_a*c_mx
-b_mx*c_mx*cp_a)+D1_l/Q*(b_mx*bp_a
+3*b_mx*cp_a-b_mx^2+3*bp_a*c_mx+c_mx*cp_a
-c_mx^2-6*b_mx*c_mx)
f_ial=xa*P*exp(ln(v_ml/(v_ml-b_mx))+(b_mx+bp_a)/(v_ml-b_mx)
F_1wl=v_ml/(Q*D_l)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_w
+3*bp_w*c_mx+3*b_mx*cp_w+c_mx*cp_w)
+1/(Q*D_l)*(bp_w*c_mx^2+b_mx^2*cp_w-b_mx*bp_w*c_mx
-b_mx*c_mx*cp_w)+D1_l/Q*(b_mx*bp_w+3*b_mx*cp_w-b_mx^2
+3*bp_w*c_mx+c_mx*cp_w-c_mx^2-6*b_mx*c_mx)
f_iwl=xw*P*exp(ln(v_ml/(v_ml-b_mx))+(b_mx+bp_w)/(v_ml-b_mx)
+(ap_w*D1_l)/(R*T)+a_mx/(R*T)*(F_1wl)-ln(Z_ml))

mww=18.015 {water kg/kmol}
mwml=mwa*xa+mww*xw
xa_mass=xa*mwa/mwml
xw_mass=1-xa_mass
aTcaw=((a_Tc_a*Omega_1a)*(a_Tc_w*Omega_1w))^.5
daawdT=-(aTcaw*F_a*(1+F_w*(1-Tr_w^.5)))/(2*(Tr_a)^.5*Tc_a)
-(aTcaw*F_w*(1+F_a*(1-Tr_a^.5)))/(2*(Tr_w)^.5*Tc_w)
dawdT=(Omega_1w*R^2*Tc_w/Pc_w)*(-F_w*alpha_w^.5*Tr_w^(-.5))
dawsrdT=-(Omega_1w*R^2/Pc_w)^.5*F_w/(2*(Tr_w)^.5)
damxdT2=xa*xa*daadT*(1-k_aa)+xa*xw*(daawdT)*(1-k_aw+(k_aw
-k_wa)*xa)+xw*xw*dawdT*(1-k_ww)+xw*xa*(daawdT)*(1
-k_wa+(k_wa-k_aw)*xw)
damxdT=xa*xa*daadT*(1-k_aa)+(daasrdT*a_w^.5+dawsrdT*a_a^.5)*xa*
xw*(1-k_aw+(k_aw-k_wa)*xa)+xw*xw*dawdT*(1-k_ww)
160
+(daasrdT*a_w^.5+dawsrdT*a_a^.5)*xw*xa*(1-k_wa+(k_wa
-k_aw)*xw)

h (kJ/kmol) and s (kJ/kmol*K)}
h_depl=100000*R*T*(Z_ml-1)-100000*(T*damxdT-a_mx)*(1/(2*N_m))
*ln((Z_ml+M_m)/(Z_ml+Q_m))
s_depl=100000*(-R*ln(P/(Z_ml-B_m))-damxdT*((1/(2*N_m))
*ln((Z_ml+M_m)/(Z_ml+Q_m))))
END
pteosawv.lib
PROCEDURE pteosawv(T,P,ya:f_iav,f_iwv,v_mv,yw,ya_mass,yw_mass,
h_depv,s_depv)
k_aa=0
k_ww=0
k_aw=-0.26328
k_wa=-0.29368
R = 8.314/100000 {m^3*bar/mol K}
{ammonia}
omega_a=.25
Tc_a=405.6
Pc_a=112.8
Tr_a=T/Tc_a
F_a=.627090
Zeta_a=.282
Omega_2a=.06934
Omega_3a=1-3*Zeta_a
alpha_a=(1+F_a*(1-Tr_a^.5))^2
b_a=Omega_2a*b_Tc_a
c_a=Omega_3a*b_Tc_a
Aa=(a_a*P)/(R^2*T^2)
Ba=b_a*P/(R*T)
Ca=c_a*P/(R*T)
161
Na=(b_a*c_a+((b_a+c_a)/2)^2)^.5
{water}
omega_w=.344
Tc_w=647.3
Pc_w=221.2
Tr_w=T/Tc_w
F_w=.689803
Zeta_w=.269
Omega_2w=0.065103
Omega_1w=3*Zeta_w^2+3*(1-2*Zeta_w)*Omega_2w+Omega_2w^2+1-3*Zeta_w
Omega_3w=1-3*Zeta_w
a_Tc_w=(R^2*Tc_w^2/Pc_w)
b_Tc_w=(R*Tc_w/Pc_w)
alpha_w=(1+F_w*(1-Tr_w^.5))^2
a_w=a_Tc_w*alpha_w*Omega_1w
b_w=b_Tc_w*Omega_2w
c_w=b_Tc_w*Omega_3w
Aw=(a_w*P)/(R^2*T^2)
Bw=b_w*P/(R*T)
Cw=c_w*P/(R*T)
Nw=(b_w*c_w+((b_w+c_w)/2)^2)^.5
Mw=((b_w+c_w)/2-Nw)*P/(R*T)
Qw=((b_w+c_w)/2+Nw)*P/(R*T)
yw=1-ya
a_aa=a_a*(1-k_aa)
a_aw=(a_a*a_w)^.5*(1-k_aw+(k_aw-k_wa)*ya)
a_ww=a_w*(1-k_ww)
a_wa=(a_w*a_a)^.5*(1-k_wa+(k_wa-k_aw)*yw)
a_mx=ya*ya*a_aa+yw*yw*a_ww+ya*yw*a_aw+yw*ya*a_wa
b_mx=ya*b_a+yw*b_w
c_mx=ya*c_a+yw*c_w
A_m=(a_mx*P)/(R^2*T^2)
B_m=b_mx*P/(R*T)
C_m=c_mx*P/(R*T)
N_m=(b_mx*c_mx+((b_mx+c_mx)/2)^2)^.5
162
ap_1=-2*(ya*ya*a_a*(1-k_aa)+ya*yw*(a_a*a_w)^.5*(1-k_aw)
+yw*yw*a_w*(1-k_ww)+yw*ya*(a_w*a_a)^.5*(1-k_wa))
ap_2=-3*(ya^2*yw*(a_a*a_w)^.5*(k_aw-k_wa)
+yw^2*ya*(a_w*a_a)^.5*(k_wa-k_aw))
ap_3a=2*ya*yw*(a_a*a_w)^.5*(k_aw-k_wa)
ap_3w=2*yw*ya*(a_w*a_a)^.5*(k_wa-k_aw)
ap_4a=2*ya*a_a*(1-k_aa)+yw*(a_a*a_w)^.5*(1-k_aw+1
-k_wa+(k_wa-k_aw)*yw)
ap_4w=2*yw*a_w*(1-k_ww)+ya*(a_w*a_a)^.5*(1-k_wa+1
-k_aw+(k_aw-k_wa)*ya)
ap_w=ap_1+ap_2+ap_3w+ap_4w
bp_a=b_a-b_mx
bp_w=b_w-b_mx
cp_a=c_a-c_mx
cp_w=c_w-c_mx
c_1=1
c_2=(C_m-1)
c_3=(-2*B_m*C_m-B_m^2-B_m-C_m+A_m)
pp=c_2/c_1
qq=c_3/c_1
rr=c_4/c_1
Q_r=(c_2^2-3*c_3)/9
R_r=(2*c_2^3-9*c_2*c_3+27*c_4)/54
theta_r=arccos(R_r*Q_r^(-1.5))
Z_mv=2*(Q_r)^.5*(.5*cos(theta_r/3)
+(3^.5/2)*sin(theta_r/3))-(c_2/3)
v_mv=Z_mv*R*T/P
D_v=v_mv^2+v_mv*(b_mx+c_mx)-b_mx*c_mx
D1_v=(1/(-Q)^.5)*ln((2*v_mv+(b_mx+c_mx)-(-Q)^.5)/(2*v_mv
+(b_mx+c_mx)+(-Q)^.5))
F_1av=v_mv/(Q*D_v)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_a
+1/(Q*D_v)*(bp_a*c_mx^2+b_mx^2*cp_a-b_mx*bp_a*c_mx
-b_mx*c_mx*cp_a)+D1_v/Q*(b_mx*bp_a+3*b_mx*cp_a
163
-b_mx^2+3*bp_a*c_mx+c_mx*cp_a-c_mx^2-6*b_mx*c_mx)
f_iav=ya*P*exp(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_a)/(v_mv-b_mx)
F_1wv=v_mv/(Q*D_v)*(b_mx^2+c_mx^2+6*b_mx*c_mx+b_mx*bp_w
+3*bp_w*c_mx+3*b_mx*cp_w+c_mx*cp_w)
+1/(Q*D_v)*(bp_w*c_mx^2+b_mx^2*cp_w
-b_mx*bp_w*c_mx-b_mx*c_mx*cp_w)+D1_v/Q*(b_mx*bp_w
+3*b_mx*cp_w-b_mx^2+3*bp_w*c_mx+c_mx*cp_w-c_mx^2
-6*b_mx*c_mx)
f_iwv=yw*P*exp(ln(v_mv/(v_mv-b_mx))+(b_mx+bp_w)/(v_mv-b_mx)
+(ap_w*D1_v)/(R*T)+a_mx/(R*T)*(F_1wv)-ln(Z_mv))
mwmv=mwa*ya+mww*yw
ya_mass=ya*mwa/mwmv
yw_mass=1-ya_mass
aTcaw=((a_Tc_a*Omega_1a)*(a_Tc_w*Omega_1w))^.5
daawdT=-(aTcaw*F_a*(1+F_w*(1-Tr_w^.5)))/(2*(Tr_a)^.5*Tc_a)
-(aTcaw*F_w*(1+F_a*(1-Tr_a^.5)))/(2*(Tr_w)^.5*Tc_w)
dawdT=(Omega_1w*R^2*Tc_w/Pc_w)*(-F_w*alpha_w^.5*Tr_w^(-.5))
dawsrdT=-(Omega_1w*R^2/Pc_w)^.5*F_w/(2*(Tr_w)^.5)
damxdT2=ya*ya*daadT*(1-k_aa)+ya*yw*(daawdT)*(1-k_aw+(k_aw
-k_wa)*ya)+yw*yw*dawdT*(1-k_ww)+yw*ya*(daawdT)*(1
-k_wa+(k_wa-k_aw)*yw)
damxdT=ya*ya*daadT*(1-k_aa)+(daasrdT*a_w^.5+dawsrdT*a_a^.5)*ya
*yw*(1-k_aw+(k_aw-k_wa)*ya)+yw*yw*dawdT*(1-k_ww)
+(daasrdT*a_w^.5+dawsrdT*a_a^.5)*yw*ya*(1-k_wa
+(k_wa-k_aw)*yw)

h (kJ/kg) and s (kJ/kg*K)}
h_depv=100000*R*T*(Z_mv-1)-100000*(T*damxdT-a_mx)*(1/(2*N_m))
*ln((Z_mv+M_m)/(Z_mv+Q_m))
s_depv=100000*(-R*ln(P/(Z_mv-B_m))-damxdT*((1/(2*N_m))
*ln((Z_mv+M_m)/(Z_mv+Q_m))))
END
164
ptabvlehsv.lib
PROCEDURE ptabvlehsv(T,P,xa,ya:xa_mass,ya_mass,xb_mass,yb_mass,
hmv,hml,smv,sml,v_ml,v_mv,f_ial,f_iav,f_ibl,f_ibv)
R=8.314 {kJ/kmol-K}
k_ab=0.2692
k_ba=0.1402
CALL pteosambtl(T,P,xa,k_ab,k_ba:f_ial,f_ibl,v_ml,xb,xa_mass,
xb_mass,h_depl,s_depl)
CALL pteosambtv(T,P,ya,k_ab,k_ba:f_iav,f_ibv,v_mv,yb,ya_mass,
yb_mass,h_depv,s_depv)
{Molecular weights}
mwml=xa*mwa+xb*mwb
mwmv=ya*mwa+yb*mwb
{Ideal Gas Enthalpy and Entropy}
c_pa=27.31+.02383*T+1.707e-5*T^2+-1.185e-8*T^3 {ideal gas}
c_pb=9.487+.3313*T+-1.108e-4*T^2+-2.822e-9*T^3 {J/mol*K}
Tra=238.8
Trb=272.3
Pref=1
hiar=23184/mwa
hia=c_pa*(T-Tra)/mwa+hiar
siar=96.94/mwa
sia=c_pa*ln(T/Tra)/mwa+siar
hibr=22669/mwb
hib=c_pb*(T-Trb)/mwb+hibr
sibr=82.97/mwb
sib=c_pb*ln(T/Trb)/mwb+sibr
hdv=h_depv/mwmv
hdl=h_depl/mwml
sdv=s_depv/mwmv
sdl=s_depl/mwml
{Mixture Enthalpy and Entropy (massbased)}

hmv=ya_mass*hia+yb_mass*hib+hdv
hml=xa_mass*hia+xb_mass*hib+hdl
smv=ya_mass*sia+yb_mass*sib+sdv-(ya_mass*R/mwa*ln(ya)
165
+yb_mass*R/mwb*ln(yb))
sml=xa_mass*sia+xb_mass*sib+sdl-(xa_mass*R/mwa*ln(xa)
+xb_mass*R/mwb*ln(xb))
END
ptawvlehsv.lib
PROCEDURE ptawvlehsv(T,P,xa,ya:xa_mass,ya_mass,xw_mass,yw_mass,
hmv,hml,smv,sml,v_ml,v_mv,f_ial,f_iav,f_iwl,f_iwv)
R=8.314 {kJ/kmol-K}
CALL pteosawl(T,P,xa:f_ial,f_iwl,v_ml,xw,xa_mass,xw_mass,
h_depl,s_depl)
CALL pteosawv(T,P,ya:f_iav,f_iwv,v_mv,yw,ya_mass,yw_mass,
h_depv,s_depv)

mwv=ya*mwa+yw*mww
mwl=xa*mwa+xw*mww
c_pw=32.24+.001924*T+1.055e-5*T^2+-3.596e-9*T^3 {J/mol*K}
Pref=1
Tra=238.8
Trw=372.5
hiar=23184/mwa
siar=96.94/mwa
hiwr=40761/mww
hiw=c_pw*(T-Trw)/mww+hiwr
siwr=109.4/mww
siw=c_pw*ln(T/Trw)/mww+siwr
hdl=h_depl/mwl
hdv=h_depv/mwv
sdl=s_depl/mwl
sdv=s_depv/mwv
{Mixture Molar Enthalpy and Entropy}

166
hmv=ya_mass*hia+yw_mass*hiw+hdv
hml=xa_mass*hia+xw_mass*hiw+hdl
smv=ya_mass*sia+yw_mass*siw+sdv-(ya_mass*R/mwa*ln(ya)
+yw_mass*R/mww*ln(yw))
sml=xa_mass*sia+xw_mass*siw+sdl-(xa_mass*R/mwa*ln(xa)
+xw_mass*R/mww*ln(xw))
END
ptamwtsc.lib
PROCEDURE ptamwtsc(T,P,xa:hml,sml)
R=8.314 {kJ/kmol-K}
CALL pteosawl(T,P,xa:f_ial,f_iwl,v_ml,xw,xa_mass,xw_mass,
h_depl,s_depl)

mwl=xa*mwa+xw*mww
c_pw=32.24+.001924*T+1.055e-5*T^2+-3.596e-9*T^3 {J/mol*K}
Pref=1
Tra=238.8
Trw=372.5
hiar=23184/mwa
siar=96.94/mwa
hiwr=40761/mww
hiw=c_pw*(T-Trw)/mww+hiwr
siwr=109.4/mww
siw=c_pw*ln(T/Trw)/mww+siwr
hdl=h_depl/mwl
sdl=s_depl/mwl
{Mixture Molar Enthalpy and Entropy}

hml=xa_mass*hia+xw_mass*hiw+hdl
sml=xa_mass*sia+xw_mass*siw+sdl-(xa_mass*R/mwa*ln(xa)
+xw_mass*R/mww*ln(xw))
167
END
ptamhsv.lib
PROCEDURE ptamhsv(T,P:hl,hv,sl,sv,vl,vv)
mwa=17.03 {kg/kmol}
R = 8.314/100000 {m^3*bar/kmol K}
c_pa=27.31+.02383*T+1.707e-5*T^2+-1.185e-8*T^3
Patm=1
Tra=238.8
hir=23184/mwa
hi=c_pa*(T-Tra)/mwa+hir
sir=96.94/mwa
si=c_pa*ln(T/Tra)/mwa+sir
omega_a=.25
Tc_a=405.6
Pc_a=112.8
Tr_a=T/Tc_a
F_a=.627090
Zeta_a=.282
Omega_2a=.06934
Omega_3a=1-3*Zeta_a
Omega_1a=3*Zeta_a^2+3*(1-2*Zeta_a)*Omega_2a
+Omega_2a^2+1-3*Zeta_a
alpha_a=(1+F_a*(1-Tr_a^.5))^2
b_a=Omega_2a*b_Tc_a
c_a=Omega_3a*b_Tc_a
Aa=(a_a*P)/(R^2*T^2)
Ba=b_a*P/(R*T)
Ca=c_a*P/(R*T)
Na=(b_a*c_a+((b_a+c_a)/2)^2)^.5
c_1a=1
c_2a=(Ca-1)
c_3a=(-2*Ba*Ca-Ba^2-Ba-Ca+Aa)
168
c_4a=(Ba^2*Ca+Ba*Ca-Aa*Ba)
ppa=c_2a/c_1a
qqa=c_3a/c_1a
rra=c_4a/c_1a
A_cubica=1/3*(3*qqa-ppa^2)
B_cubica=1/27*(2*ppa^3-9*ppa*qqa+27*rra)
D_cubica=(A_cubica)^3/27+(B_cubica)^2/4
IF D_cubica<0 THEN
phi=arccos(((B_cubica^2/4)/(-A_cubica^3/27))^.5)
ycubic1=2*(-A_cubica/3)^.5*cos(phi/3+2.09439510239*0)
Z_av=ycubic1-ppa/3
Z_al=ycubic2-ppa/3
Z_a3=ycubic3-ppa/3
endif
IF D_cubica>0 THEN
Mcubic=(-B_cubica/2+D_cubica^.5)^(1/3)
Ncubic=(-B_cubica/2-D_cubica^.5)^(1/3)
ycubic1=Mcubic+Ncubic
ycubic2=-.5*(Mcubic+Ncubic)
ycubic3=-.5*(Mcubic+Ncubic)
Z_av=ycubic1-ppa/3
Z_al=ycubic2-ppa/3
Z_a3=ycubic3-ppa/3
endif
daadT=(Omega_1a*R^2*Tc_a/Pc_a)
*(-F_a*alpha_a^.5*Tr_a^(-.5))
hdepl=100000*R*T*(Z_al-1)-100000*(T*daadT-a_a)*(1/(2*Na))
*ln((Z_al+Ma)/(Z_al+Qa))
hdepv=100000*R*T*(Z_av-1)-100000*(T*daadT-a_a)*(1/(2*Na))
*ln((Z_av+Ma)/(Z_av+Qa))
sdepl=100000*(-R*ln(P/(Z_al-Ba))-daadT*((1/(2*Na))
*ln((Z_al+Ma)/(Z_al+Qa))))
sdepv=100000*(-R*ln(P/(Z_av-Ba))-daadT*((1/(2*Na))
*ln((Z_av+Ma)/(Z_av+Qa))))
vl=Z_al*R*T/P
vv=Z_av*R*T/P
{Enthalpy and Entropy in kJ/kg}

hl=hi+hdepl/mwa
169
hv=hi+hdepv/mwa
sl=si+sdepl/mwa
sv=si+sdepv/mwa
END
170
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VITA
Laura Schaefer was born Laura Michelle Atkinson in Danville, Illinois, on

January 13, 1973. She is the oldest of three children, and was raised in Springfield,
Illinois, The Woodlands, Texas, and Gaithersburg, Maryland. Laura graduated from
Thomas Wootton High School in Rockville, Maryland, in 1991.
Laura attended Rice University in Houston, Texas, where she was a resident
of Wiess College. She held in summer internships at the National Air and Space
Museum in Washington, D.C., and at Lawrence Livermore National Lab in Califor-
nia. During her time at the Air and Space Museum, Laura designed and created a
longitudinal wave device for inclusion in How Things Fly, NASM’s first interactive
gallery. Laura received a B.A. in English and a B.S. in Mechanical Engineering in
May 1995. Upon graduation, she spent three months traveling through Europe by
train.
In September 1995, Laura entered graduate school at the Georgia Institute

of Technology. She received a Master of Science degree in December 1997. Laura’s
M.S. thesis focused on developing an analytical mean temperature difference relation-
ship for refrigerant mixtures that have been designated as replacements for ozone-
depleting CFCs and HCFCs. Laura’s M.S. and Ph.D. research at Georgia Tech was
supported by NSF, DuPont, ASME, and ASHRAE.

Laura married Andrew James Schaefer on June 21, 1997. Andrew is receiving
a Ph.D. in Operations Research from Georgia Tech’s School of Industrial and Systems
Engineering. In her spare time, Laura enjoys reading, gardening, and homebrewing.

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Single Pressure Absorption Heat Pump Analysis

Laura Atkinson Schaefer

Georgia Institute of Technology

Single Pressure Absorption Heat Pump Analysis

Samuel V. Shelton, Chairman

To Andrew James Schaefer,

whom I would like to individually express thanks.

would have been possible.

Mrs. Sharon Shelton, for her encouragement and advice.

devoted to serving on my reading committee.

deep, overall understanding of a work with a meticulous attention to detail.

on my reading committee. Their backgrounds and perspectives have enriched my

Anderson, and Jason Brown.

forward to the exciting future that lies ahead of us.

into your hearts, and I am so grateful for that.

II THERMODYNAMIC MODEL OF THE CYCLE 20

The Coeﬃcient of Performance . . . . . . . . . . . . . . . . . 41

III THE PRINCIPLE OF CORRESPONDING

IV THE IDEAL SOLUTION MODEL 67

V IDEAL SOLUTION PARAMETER RESULTS

VI THE PATEL-TEJA MODEL 87

Enthalpy and Entropy . . . . . . . . . . . . . . . . . . . . . . 93

VII THE PATEL-TEJA MODEL RESULTS 96

VIII GAS WATER HEATING: AN APPLICATION

IX SUMMARY, CONCLUSIONS AND

A GENERATOR PROGRAMS 125

B IDEAL SOLUTION MODEL PROGRAMS 137

C PATEL-TEJA MODEL PROGRAMS 145

3-1 Constants for Calculating Compressibility . . . . . . . . . . . . . . . 53

5-2 Pressure Equalizing Fluids . . . . . . . . . . . . . . . . . . . . . . . 82

7-3 COP for Tca = 325 K, Tevap = 295 K . . . . . . . . . . . . . . . . . 101

7-7 Comparison of Refrigerant Performance . . . . . . . . . . . . . . . . 103

1-1 A Vapor Compression Cycle (Anderson, 1972) . . . . . . . . . . . . . 2

1-3 An Ice Plant (Anderson, 1972) . . . . . . . . . . . . . . . . . . . . . 3

1-7 A Dual Pressure Absorption Cycle . . . . . . . . . . . . . . . . . . . 10

2-2 The Evaporator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

2-7 The Ideal Solution Model Generator . . . . . . . . . . . . . . . . . . 32

2-11 Baker Flow Pattern Map . . . . . . . . . . . . . . . . . . . . . . . . 38

2-12 Eﬀect of Diameter on Liquid and Vapor Flow Rates (Submergence

2-16 Alternate Generator Conﬁgurations . . . . . . . . . . . . . . . . . . . 46

3-4 Saturated Liquid and Vapor Enthalpy . . . . . . . . . . . . . . . . . 62

5-3 COP versus Tc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

7-3 Ammonia-Propane, T = 293 K . . . . . . . . . . . . . . . . . . . . . 100

8-3 Residential and Commercial Natural Gas Water Heating . . . . . . . 113

COP Coeﬃcient of Performance (-)

ṁ Mass Flow Rate ( kg

x Liquid Mass or Mole Fraction (-)

Thermally-driven absorption heat pump cycles have several advantages over

predict the behavior the cycle

For this study, three temperature conditions were evaluated: 1) Tcondens−absorb

surroundings. Heat pumps are used in refrigeration, air-conditioning, space heating,

Figure 1-1: A Vapor Compression Cycle (Anderson, 1972)

Figure 1-2: An Ammonia Absorption Cycle (Anderson, 1972)

Figure 1-3: An Ice Plant (Anderson, 1972)

Steam Engine Drive

Figure 1-4: Lord Kelvin’s Warming Machine

Therefore, under ideal conditions, direct heating required approximately thirty-ﬁve

Heat Sources and Sinks

Figure 1-5: The Zurich Town Hall Heat Pump

Heat Pump Cycles

into two categories: vapor compression and absorption. Additionally, absorption

Vapor Compression Cycles