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# 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

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

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

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Second Law Analysis . . . . . . . . The Precooler . . . . . The Evaporator . . . . . . . . . . . . . Description . . . . . . . . . . . Heat Pump Cycles . . . . . . . . . . . . . . . . . . . . . . CYCLE . . . . . . . . . . . . . . . . . . . . Introduction . . . . . . . . . . . . . . . . . . . . . . . Literature Review . . . . . . . . . . . . . . . . .vi TABLE OF CONTENTS DEDICATION ACKNOWLEDGEMENTS LIST OF TABLES LIST OF ILLUSTRATIONS NOMENCLATURE SUMMARY CHAPTER I INTRODUCTION Heat Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Generator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii iv x xi xiv xvii 1 1 1 1 5 7 13 13 15 16 16 17 18 20 20 22 22 23 26 28 29 33 41 II . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Bubble Pump . . . . . . . . . . . . . . . . . . . . . . . . . . Current Research . . . . The Condenser/Absorber . . . . . Deﬁnition . . . . Component Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Gas Water Heating: An Application for the Einstein Cycle THERMODYNAMIC MODEL Overall Description of the Cycle . . . Alterations of the Cycle Conﬁguration . . . . . . . . . . . OF THE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Einstein Cycle . . . Heat Sources and Sinks . . . . . . . . Modeling the Einstein Cycle . . . . . . . .

. . . . . . . Single Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . THE PATEL-TEJA MODEL The Patel-Teja Equation of State . Enthalpy and Entropy Departure Functions Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mole and Mass Fractions . . . . . . . . . . . . . . . . Selection of Fluid Triplets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Implementation of the Ideal Gas and Incompressible Solution Theories . Dimensions of the Search . . . An Illustrative Case: The Internal Generator Heat Exchanger III THE PRINCIPLE OF CORRESPONDING STATES MODEL The van der Waals Equation of State . . . . . . . . .vii The Coeﬃcient of Performance . . . . . . . . . . Mixing Rules . . Searching for Optimum Properties . . . . . . . . . . . . . . . . . . . . . Pressure-Equalizing Fluid . . . . . . . . . . . . . . . . . . . . . Absorbing Fluid . . Mixing Rules . . . . . . . . . . . . . . . Calculation of the Enthalpy Departure Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Two-Parameter Principle of Corresponding States . . . . . . . . . . . . . . . . . . . . . . . . . . . . IDEAL SOLUTION PARAMETER RESULTS AND FLUID SELECTION System Model . . . . . . . . Calculation of Compressibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Incompressible Liquid Theory . . . . . . . . . . . . . . . . . . Saturated Liquid and Vapor Behavior: Enthalpy Versus Temperature . . . . . . . . . . . . . . . Equilibrium Conditions . Determining Enthalpy Diﬀerences . 41 45 48 48 49 50 51 56 57 59 59 62 65 67 67 68 70 73 73 73 81 81 81 82 82 83 87 87 88 88 89 90 91 91 92 IV V . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ideal Gas Theory . . . . . . . . . . . . . . . VI . . . . . . . . . . . . . . . . . . . . . . . . Matching the Ideal Properties to Actual Fluids . . . . . . . . . . . . . . . . . . THE IDEAL SOLUTION MODEL Vapor-Liquid Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Three-Parameter Principle of Corresponding States . . . . . . . . . . . . . . . . . . . Refrigerant . . . . . . . . . . . . . . . . . . . . . . . Determination of the Patel-Teja Coeﬃcients Equilibrium Conditions . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . Parameter Values . Correspoding States/Ideal Solution Model Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .viii Enthalpy and Entropy . . . . . . . . . . . . VII THE PATEL-TEJA MODEL RESULTS System Model . . . . . . . . . . . . . . . . . . . . . . Savings . . . . . . . . . . Electric versus Gas Water Heating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Einstein Cycle Gas Water Heating . . . . . . . . . . . . . . . . . . . . . . . Conﬁguration of the Einstein Cycle as a Gas Water Heater Market Potential . . . . . . . . . . . . . . . . . . . . Generator Libraries . . . . . . . Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . Water Heating Eﬃciency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125 125 127 132 134 . . . . . . . . . . Ammonia-Water-Butane Results . 93 96 96 96 96 97 98 99 101 102 103 105 106 106 107 107 109 109 109 110 112 114 114 114 115 VIII GAS WATER HEATING: AN APPLICATION AND ITS IMPLICATIONS Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Barriers . . Eﬀect of State Point Properties . . . . . . . . . . . . . . . . . . Implementation . . . . Generator Conﬁguration 3 . . . . . . . . . . . Fitting the Experimental Data . . . . . . . . . . . . . . . . . . Economic . . . . . . . . . . . . . . . CONCLUSIONS AND RECOMMENDATIONS 118 Summary and Conclusions . . . . . . . . . . . . . Environmental . Binary Interaction Parameters . . . . . . . . . . . Generator Conﬁguration 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Actual Fluid Behavior . . . . . . . . . . . . . . . . . . . . Equation of State Coeﬃcients . . . 118 Recommendations . . . . . . . . . . 123 APPENDIX A GENERATOR PROGRAMS Generator Conﬁguration 1 . . . IX SUMMARY. . . . . .

ix

B

IDEAL SOLUTION MODEL PROGRAMS 137 Ideal Solution Model EES Program . . . . . . . . . . . . . . . . 137 Ideal Solution Model Libraries . . . . . . . . . . . . . . . . . . . 143 PATEL-TEJA MODEL PROGRAMS 145 EES Program . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145 Program Libraries . . . . . . . . . . . . . . . . . . . . . . . . . . 148 170 176

C

BIBLIOGRAPHY VITA

x

LIST OF TABLES

Table

Page

3-1 5-1 5-2 5-3 7-1 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9

Constants for Calculating Compressibility . . . . . . . . . . . . . . . Parameter Variation for Increased Eﬃciency . . . . . . . . . . . . . . Pressure Equalizing Fluids . . . . . . . . . . . . . . . . . . . . . . .

53 81 82 83 97 98

Refrigerants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Patel-Teja Coeﬃcients . . . . . . . . . . . . . . . . . . . . . . . . . . Binary Interaction Parameters . . . . . . . . . . . . . . . . . . . . . COP for Tca = 325 K, Tevap = 295 K COP for Tca = 325 K, Tevap = 306 K COP for Tca = 316 K, Tevap = 295 K

. . . . . . . . . . . . . . . . . 101 . . . . . . . . . . . . . . . . . 101 . . . . . . . . . . . . . . . . . 102

Ammonia-Water-Butane Results . . . . . . . . . . . . . . . . . . . . 102 Comparison of Refrigerant Performance . . . . . . . . . . . . . . . . 103 Comparison of Pressure-Equalizing Fluid Performance . . . . . . . . 104 Theoretical Fluids and the Eﬀect on the COP . . . . . . . . . . . . . 105

xi

LIST OF ILLUSTRATIONS

Figure

Page

1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-11

A Vapor Compression Cycle (Anderson, 1972) . . . . . . . . . . . . . An Ammonia Absorption Cycle (Anderson, 1972) . . . . . . . . . . . An Ice Plant (Anderson, 1972) . . . . . . . . . . . . . . . . . . . . . Lord Kelvin’s Warming Machine . . . . . . . . . . . . . . . . . . . . The Zurich Town Hall Heat Pump . . . . . . . . . . . . . . . . . . . A Vapor Compression Cycle . . . . . . . . . . . . . . . . . . . . . . . A Dual Pressure Absorption Cycle . . . . . . . . . . . . . . . . . . . A Single Pressure Absorption Cycle . . . . . . . . . . . . . . . . . . The Einstein Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Einstein Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Evaporator . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2 3 3 4 6 8 10 12 14 21 23 25 27 29 31 32 34 36 38 38

The Ideal Solution Evaporator Model . . . . . . . . . . . . . . . . . The Precooler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

The Condenser/Absorber . . . . . . . . . . . . . . . . . . . . . . . . The Generator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Ideal Solution Model Generator . . . . . . . . . . . . . . . . . . A Bubble Pump . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Vertical Flow Regimes . . . . . . . . . . . . . . . . . . . . . . . . . . Collier Flow Pattern Map . . . . . . . . . . . . . . . . . . . . . . . . Baker Flow Pattern Map . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . 108 . . . . . . . . . . . . . . . . 80 85 99 5-8 7-1 7-2 7-3 8-1 8-2 Alternative Fluid Triplets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Saturated Liquid and Vapor Enthalpy . . . . . . . . . . . . . . . . . . . . . COP versus Absorbing Fluid Critical Temperature for Varying Generator Temperature . . . . . . . . . Saturated Liquid and Vapor Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . COP versus M . . . . . . . . . . . . . . . . . Saturated Liquid and Vapor Enthalpy . . .13 . . . T = 293 K . .l . . T = 288 K . . . . . . . . . The Eﬀect of Generator Temperature on COP . . . . . . . . .2) . . . . . . . . . . . . . . . .2) . . . . . . . . . . . . . . . . . Alternate Generator Conﬁgurations . . . . . . . . . . . . COP versus Pc . . . . . . . . . . . Saturated Liquid and Vapor Enthalpies . . . . . . . . . . . . .2. . . . . . . . 40 42 42 46 55 60 61 62 64 74 75 76 77 78 79 2-14 2-15 2-16 3-1 3-2 3-3 3-4 3-5 5-1 5-2 5-3 5-4 5-5 5-6 5-7 Pumping Capacity for h/L = 0. Hydrogen Chloride-Butane. . . . . . . . . . COP versus ω . . . . . . . . . . . . . . .12 and 3. . . . . . . . 100 Ammonia-Propane. . . . . . . . . . . . Methyl Amine-Butane. . . . . . . . . . . . COP versus cp. . . . . . . . . . . . . . . . 100 An Einstein Cycle Gas Heat Pump Water Heater . . . . . . . . . . . . . . . 106 Water Heater Losses . . . . . . . . Intersection of Equations 3. . . . . . . . . . D = 8. . . . . . .xii 2-12 Eﬀect of Diameter on Liquid and Vapor Flow Rates (Submergence Ratio = 0. . P = 4 bar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 2-13 Eﬀect of Diameter on Liquid Flow Rate and Heat Transferred to the Bubble Pump (Submergence Ratio = 0. . . . . . Heat Transfer To And From The Einstein Cycle . . . . . . . . . . . . . . . . . . . . COP versus Tc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 mm . . .

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

bar) Heat Transfer Rate (kW ) Gas Constant ( m ·P a . K) J Speciﬁc Internal Energy ( kg ) m Total Volume ( mol ) 3 Speciﬁc Volume ( m ) kg 3 .xiv NOMENCLATURE Symbols a b c COP D f G g H h M m ˙ P ˙ Q R S s T u V v Attractive Force Correction Factor ( N ·m2 ) mol 4 m Volume Correction Factor ( mol ) J Speciﬁc Heat ( kg·K ) 3 Coeﬃcient of Performance (-) Diameter (m) Fugacity (kP a. bar) J Gibbs Energy ( mol ) m Gravity ( s2 ) J Total Enthalpy ( mol ) J Speciﬁc Enthalpy ( kg ) kg Molecular Weight ( kg·mol ) Mass Flow Rate ( kg ) s Pressure (kP a. mol·K 3 m3 ·P a ) kg·K J Total Entropy ( mol·K ) J Speciﬁc Entropy ( kg·K ) Temperature (◦ C.

xv x y Z Liquid Mass or Mole Fraction (-) Vapor Mass or Mole Fraction (-) Compressibility (-) Greek Characters ζc ρ σ ω Patel-Teja Coeﬃcient (-) kg Density ( m3 ) Surface Tension ( N ) m Acentric Factor (-) Subscripts abs c f g m p pe r ref rg s sv u v Absorbing Fluid Critical Point Liquid Vapor Mixture Constant Pressure Pressure-Equalizing Fluid Reduced Property Refrigerant Entropic Average Superheated Vapor Universal Constant Volume .

xvi Superscripts ∗ 0 L r sat V Ideal State Simple Fluid Liquid Reference Fluid Saturated State Vapor .

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

which can produce 125◦ F water from ambient conditions (ﬂue gases could be used to help to maintain the evaporator at 72◦ F). an Einstein cycle gas heat pump water heater would cut the operating costs of a conventional gas water heater by 33%. With a COP of 1. The highest COP for the ﬁrst set of temperatures. . The best COP for the second set of temperatures.88. three temperature conditions were evaluated: 1) Tcondens−absorb = 325 K and Tevaporator = 295 K. each of these temperature levels are suitable for using the Einstein cycle for gas heat pump water heating. where the Einstein cycle would be used as a preheater. This could result in large economic and environmental savings. 2) Tca = 325 K and Tevap = 306 K.76. is 1. and 3) Tca = 316 K and Tevap = 295 K. Finally.51. is 1. As outlined in the introduction.xviii For this study. the COP for the third set of temperatures. which require a hotter evaporator.5. is 1.

The ﬁrst reliable refrigeration machine was constructed by Perkins in 1834. the cycles were used to produce . Heat pumps can also be used for cooling by transferring heat from the application to be cooled to higher-temperature surroundings. History Initially. when William Cullen created ice with an air pump (Anderson. was unable to consistently maintain refrigeration temperatures. was not to provide direct refrigeration. there was an explosion of interest in mechanical refrigeration. and other applications. however. Heat pumps are used in refrigeration. Heat pumps can transfer heat from natural or man-made thermal sources to a building or an application. space heating. refrigeration was the primary thrust of heat pump development. Cullen. The ﬁrst attempt to produce refrigeration mechanically occurred in 1755. The focus at that time. Instead. and by the 1850s. however. Vapor compression (Figure 1-1) and ammonia absorption (Figure 1-2) cycles were both vigorously studied in the 1860s and 1870s.1 CHAPTER I INTRODUCTION Heat Pumps Deﬁnition Using input energy. heat pump cycles pump thermal energy from low temperatures to high temperatures. air-conditioning. 1972).

2 Figure 1-1: A Vapor Compression Cycle (Anderson. 1972). heat pumps used for air-conditioning moved from industrial to commercial and then to residential applications by the 1950s. By the end of World War I. The public slowly began to abandon the icebox: in 1921. Simultaneously. 1972) large quantities of ice (Figure 1-3) that could then be used in commercial or residential applications (such as an icebox). Kelvin’s machine. only ﬁve thousand domestic refrigerators were sold. Kelvin outlined the heating of air from 50 ◦ F to . 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. but by 1930. that number had grown to 850. Breweries were the ﬁrst to implement direct refrigeration on a large scale. shown in Figure 1-4.000 units (Anderson. public utilities started to oﬀer incentives to residential customers to purchase home refrigerators. followed by the food-processing industries. would produce heat for a building that was greater than the heat of combustion of the coal used to drive the engine. In 1852.

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

with a focus on producing hot water. Therefore.4 Steam Engine Drive To Building T3 T1 Ingress Cylinder External Atmosphere Egress Cylinder Receiver T2 Figure 1-4: Lord Kelvin’s Warming Machine 80 ◦ F as an example. and laid out the conﬁguration previously shown in Figure 1-4. 1922). He stated that an ideal machine could deliver one pound of air per second at those temperatures from a driving power of 0. under ideal conditions. Morley revived Kelvin’s work in 1922.2 BTU.28 hp. He also constructed an experimental heat pump for his own home. and tested various heat sinks and sources (Heap. Haldane (1938) analyzed experimental data from a refrigerating plant from 1891 to 1926 to demonstrate the heating potential of a heat pump. the use of heat pumps for heating water or air was not seriously investigated until the 1920s and 30s. which is equivalent to 0. . 1983). Homkes also conducted heat pump research in the early 1930s. To directly heat one pound of air from 50 ◦ F to 80 ◦ F requires 7 BTU. direct heating required approximately thirty-ﬁve times the heat equivalent of the work (Morley. Despite Kelvin’s early work.

1978). when air source heat pumps are used to supply space heating or cooling. The Ferranti Fridge-Heater. The use of heat pumps for domestic heating applications began to be explored in the 1950s. Air source heat pumps have a number of obvious advantages. Obviously. Additionally. The Town Hall heat pump worked so successfully that a second heat pump was installed in the Zurich Public Baths (Fearon. which was marketed in Britain in 1954. and the evaporator can be easily incorporated into a number of possible conﬁgurations. Air is abundantly available. Two other potential sources of energy that have been investigated through the years are the earth and the air. was a hybrid refrigerator-water heater with a heating output of 1. 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. Since that time. electric-driven heat pumps are available for air and water heating. The Zurich Town Hall used a heat pump to provide a portion of its peak heating requirements as early as 1939 (Figure 1-5). there are problems with air source heat pumps.2 kW in the summer and 0. Unfortunately. The heat exchangers may be quite large. However. though. the fridge-heater failed to establish a substantial consumer base.5 The worldwide economic depression of the 1930s greatly stimulated heat pump development. Currently. For instance. and soon disappeared from the market. and noise is produced from the large volume of air ﬂow.7 kW in the winter. large-scale implementations proved to be more ﬁnancially favorable than smaller domestic appliances. For heating applications. both ground and air-source heat pumps have been investigated for residential use. in certain . not all heat pump installations can rely on a water source. diﬃculties can arise at the extremes.

6 Figure 1-5: The Zurich Town Hall Heat Pump .

Work is supplied to the compressor. while only a fraction is from geothermal energy. Water and air can not only serve as good sources of free low-grade energy. a condenser. One conﬁguration is the use of air as a heat source and water as a sink. an evaporator. Additionally. Heat Pump Cycles The cycles that drive the heat pumps described in preceding history can fall into two categories: vapor compression and absorption. as shown in Figure 1-6. For that case. The earth is a less commonly used source of low-grade heat. The main problem with this large source of energy is ﬁnding the means to extract it. Vapor Compression Cycles Vapor compression cycles are the most common type of heat pump cycle. though. The vast majority of the heat in the earth comes from the stored energy of the sun. and it has been found that consistent extraction rates of 30 BTU/hr/ft of pipe can be achieved. The most basic vapor compression cycle consists of a compressor. limiting the ﬂexibility of ground source heat pump implementations. This increase in . Coils must be buried in the ground.7 climates. frost can form on the evaporator. Where this can be overcome. In this study. ground source heat pumps can be an appropriate choice. which increases the pressure of the working ﬂuid. absorption cycles can be further delineated by the number of operating pressure levels. which blocks the airways. and a throttling valve. they can also be used as heat sinks for the condenser and/or absorber. Various coil conﬁgurations have been investigated since the 1940s. dual pressure and single pressure absorption cycles are of particular interest. the evaporator can be used to provide space cooling while the condenser provides hot water for a number of household applications.

which expands the refrigerant down to the lower. where the refrigerant is boiled back into a vapor state. Next. . where it rejects heat to its lower-temperature surroundings (which can be water or air) and condenses into a saturated or subcooled liquid. and causes the vapor to become superheated. original pressure. the refrigerant passes through a throttling valve. The refrigerant then passes through the condenser. so that it can absorb low-temperature heat. This process also reduces the temperature of the refrigerant. This heat is absorbed in the evaporator.8 Q cd Wcp Compressor Throttling Valve Condenser Evaporator Qe Figure 1-6: A Vapor Compression Cycle pressure raises the temperature of the refrigerant.

temperature. The remaining liquid absorbent is then throttled back to the lower system pressure as it falls from the generator into the absorber. throttling valve. it is not mechanically compressed. When the refrigerant leaves the evaporator. but is instead absorbed by a second working ﬂuid. and state that occur in the condenser. Dual pressure absorption cycles use two ﬂuids rather than a single refrigerant. By using direct thermal energy. This absorption process causes heat to be rejected. Dual Pressure Absorption Cycles The dual pressure absorption cycle shown in Figure 1-7 replaces the compressor with an absorption-generation process. a vapor compression cycle can be highly eﬃcient. large losses can occur in creating the work that drives the compressor. For example. which ﬂows into the condenser. . The changes in pressure. coal may be combusted to produce electricity in a power plant. This heating process generates refrigerant vapor. absorption cycles can lessen or completely avoid the need to convert heat to work and then back to heat. and evaporator are the same as in the vapor compression cycle. a process that has an average eﬃciency of only thirty percent. but the amount of work that is required is an order of magnitude less than in a vapor compression cycle. The liquid mixture of absorbent and refrigerant is pumped to a higher pressure and into the generator. However.9 Absorption Cycles When examined as an isolated system. however. Direct thermal energy from a high-temperature source is transferred to the refrigerant-absorbent mixture in the generator. The pumping process is driven by a work input.

10 Q cd Q gen Generator Condenser Throttling Valve Evaporator Absorber Wcp Pump Qe Q abs Figure 1-7: A Dual Pressure Absorption Cycle .

which was patented in 1928. The refrigerant vapor then ﬂows into the condenser. and have waste heat available at the user site rather than at the central power plant. and quiet. single pressure absorption cycles add a third working ﬂuid and replace the mechanical pump with a bubble pump. where the liquid absorbent absorbs the refrigerant.11 Single Pressure Absorption Cycles Single pressure absorption cycles have a number of advantages over vapor compression cycles. The vapor mixture of refrigerant and inert gas ﬂows into the absorber. hydrogen as an inert gas. they are also inexpensive. high-temperature heat is applied to a liquid mixture of the refrigerant and the absorbent. The diﬀusion of hydrogen in the cycle is the kinetic limiting process. the liquid refrigerant ﬂows into the evaporator and mixes with an inert gas. which is ﬁrst used to “pump” the liquid absorbent through the bubble pump into the absorber. there are important diﬀerences in the way that they operate. This generates refrigerant vapor. The Platen and Munters cycle uses ammonia as a refrigerant. Since they have no moving parts. Although some of the components in a single pressure absorption cycle resemble those of a vapor compression or dual pressure absorption cycle. They do not require a costly electric power plant. In the generator. and water as an absorbent. This is the Platen and Munters diﬀusion-absorption cycle. use environmentally benign natural ﬂuids. A bubble pump can move ﬂuids across a diﬀerence in height simply by using a heat input. This mixing process lowers the partial pressure of the refrigerant so that it evaporates at a lower temperature. The . One single pressure absorption cycle is illustrated in Figure 1-8. In order to eliminate the need for any work input. where it rejects its thermal energy to the surroundings and condenses into a liquid. Next. reliable.

12 Q cd Q bubblepump Q gen Generator Condenser Evaporator Absorber Qe Q abs Figure 1-8: A Single Pressure Absorption Cycle .

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

14 Q cd / abs Condenser/ Absorber Q gen Generator Q bubblepump Evaporator Qe Figure 1-9: The Einstein Cycle .

One decade later. He also suggested possible alternatives for the Einstein absorbing ﬂuid (water) and refrigerant (butane). A recent article in Scientiﬁc American also mentioned the Einstein cycle (Dannen. Alefeld brieﬂy outlined the cycle in a Physics Today guest comment.S. 1980). In 1980. They used both n-butane and iso-butane as the refrigerant in a simple model. The Hopkins study investigated possible alternative power sources for an Einstein cycle (such as solar or geothermal energy). In 1984. thesis (1997) and Ph. While the physical cycle conﬁguration is nearly the same as in Einstein and Szilard’s patent.19. That same year. However. a patent was issued to Rojey for a variation on the Einstein cycle. Razi et al.25. the article focused on the partnership of Einstein and Szilard rather than on the properties of the cycle. 1997). Delano developed an Engineering Equation Solver (EES) model of the cycle using the ﬁrst and second laws. (1994) examined the result of powering the Einstein cycle with solar energy for use in Morocco. The primary emphasis of Delano’s work was to gain an un- . Rojey used carbon dioxide rather than ammonia for the inert ﬂuid. and found possible cooling COPs of 0.13 to 0. Literature Review Very little has been published on the Einstein cycle. The most recent and comprehensive work on the Einstein cycle was performed by Delano for his M. and calculated a maximum cooling coeﬃcient of performance (COP) for the cycle of 0. the Johns Hopkins University Applied Physics Laboratory produced an internal report on the Einstein cycle (Follin and Yu. The liquid water is pumped back into the condenser/absorber by the bubble pump.15 the liquid water. and the vapor ammonia ﬂows into the evaporator. completing the cycle.D. dissertation (1998) at Georgia Tech.

the evaporator was able to maintain temperatures as low as -2 ◦ C. To model the ﬂuids’ properties. By supplying the generator with between 150 and 250 watts and the bubble pump with 50 to 70 watts. and pinch points. ammonia. and i-pentane. With the EES model. 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. but no optimization of its operating parameters was carried out. Simplifying assumptions for both the ﬂuid and the component behavior were made. and monitor their eﬀect on the COP and the temperature lift from the evaporator to the condenser/absorber. and by cooling the condenser/absorber with 21 ◦ C tap water.15.16 derstanding of the performance of the cycle through an analysis of the processes and the properties of various working ﬂuids. component irreversibilities reduced the calculated COP to 0. Delano also developed a bubble pump performance model. such as i-butane. He also ran parametric studies for varying pressures. The prototype was charged with iso-butane. neopentane. the PatelTeja equation of state was ﬁtted to experimental data using the Panagiotopoulos and Reid mixing rules. and water. While the maximum reversible cooling COP was found to be 0. Delano was able to test various refrigerant ﬂuids.86. This study builds on Delano’s work by using a methodical approach to increase the eﬃciency of the . Delano built a conceptual demonstration prototype from welded stainless steel tubing. This prototype operated silently and reliably. and demonstrated the viability of the Einstein cycle. temperatures. In addition to the computational model.

the relationship of the diameter. etc. an optimization of the properties has been performed in order to ﬁnd the optimal hypothetical ﬂuids that maximize the eﬃciency. A second law analysis of each cycle component can reveal sources of entropy generation. a number of actual ﬂuids were chosen that most closely matched those properties. Entropy generation degrades the overall eﬃciency of the cycle. critical temperatures.). The entropy generated in each component has been examined. and so should be minimized. Once the optimal properties were found. and appropriate improvements have been implemented. mass ﬂow rate. Both the cycle conﬁguration and the ﬂuids that are used are examined. In addition. masses. 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. An ideal gas/incompressible solution model of the Einstein cycle has been completed. and so gives the performance of the cycle entirely in terms of the least number of ﬂuid properties (such as the speciﬁc heats. and heat input have been analyzed for the bubble pump. . and its physical geometry has been altered to maximize its performance. Using this model. The various ﬂuid combinations were then evaluated using a complex cycle model that could more accurately represent the behavior of polar substances. This model uses the three parameter theory of corresponding states to model individual ﬂuid behavior and Raoult’s Law to model ﬂuid mixing.17 Einstein cycle. submergence ratio.

The second conﬁguration will use ﬂue gas exhaust to heat the evaporator. Gas water heaters comprise over ﬁfty-ﬁve percent of the United States’ residential water heating market. These temperatures were selected based on current water heater regulations. single (and dual) pressure absorption cycles have been primarily used for refrigeration applications. and 105◦ F is the maximum temperature need for most applications. and consumes 0. resulting in an increase in eﬃciency. 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 heating accounts for 13% of the total gas usage.18 Gas Water Heating: An Application for the Einstein Cycle Previously.3 quads of energy each year. These temperature levels are ideal for domestic water heating and service (commercial) water heating. The eﬃciency. and consume 1. The cycle performance for each of these conﬁgurations is detailed in Chapter VII. The ﬁrst will produce hot water at 52◦ C (125◦ F) from ambient air temperatures of 22◦ C (72◦ F). which is deﬁned as the amount of heating provided to the water divided by the amount of heating provided by the gas ﬂame. Three temperature conﬁgurations will be explored in this study. In the commercial sector. 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). Furthermore. Due to safety considerations.35 quads . water heater temperatures have been reduced so that 140◦ F is the upper limit on the tank thermostat. The Einstein cycle. can be increased from the current levels of 66% to over 100%. is able to produce temperatures that are suitable for water heating. In the ﬁnal conﬁguration. and will produce 52◦ C hot water from an evaporator temperature of 33◦ C (91◦ F). however. scalding temperatures are at 120-125◦F.

19 per year. . These economic and environmental savings are analyzed. and implementation strategies and market barriers are also discussed. An alternative gas water heater that uses less energy has the potential to signiﬁcantly reduce carbon emissions. and provide savings for the consumer.

Figure 2-1 shows a general diagram of the Einstein cycle. At point 1. and is bubbled into the condenser/absorber at point 6. One ﬂuid acts as a refrigerant. The absorbing ﬂuid absorbs the pressure-equalizing vapor from . have been added in order to create a cycle with a higher eﬃciency. no moving parts. liquid refrigerant leaves the condenser/absorber. The refrigerant and pressure-equalizing vapor mixture becomes superheated in the precooler. Various heat exchangers. In order to facilitate ﬂuid motion. thermally-driven refrigeration cycle that uses three ﬂuids. passes through a precooler. Because the Einstein cycle operates at a single pressure. but they are considered to be insigniﬁcant for the purposes of this evaluation. and one as an absorbing ﬂuid. and arrives in the evaporator at point 2. are required. there are some slight pressure variations due to height diﬀerences in the cycle. one as a pressure-equalizing ﬂuid. such as the internal generator solution heat exchanger.20 CHAPTER II THERMODYNAMIC MODEL OF THE CYCLE Overall Description of the Cycle The Einstein cycle is a single-pressure. The refrigerant evaporates and leaves the evaporator at point 3. The pressure-equalizing ﬂuid enters the evaporator as a vapor at point 4. The evaporation process requires heat transfer from the surroundings. Liquid absorbing ﬂuid from the generator is sprayed into the condenser/absorber (point 11). such as a pump. The cycle shown in this ﬁgure has been modiﬁed from Einstein’s original conﬁguration. The refrigerant and pressure-equalizing ﬂuids combine at a low temperature.

9g Reservoir 4 9f 11 3 Bubble Pump Evaporator Generator Figure 2-1: The Einstein Cycle 4b Pre-Cooler 6 5 External 10 Heat Exchanger 7 8 1 2 Qevaporator Qcondenser/absorber Condenser/Absorber Butane (Refrigerant) Qgenerator Water (Absorbing Fluid) Ammonia (Pressure-Equalizing Fluid) 9 Qbub pump 21 .

The two vapor streams combine at point 4b. a ﬁrst and second law analysis is applied to each component. and mixes with additional pressure-equalizing vapor from the bubble pump. The refrigerant is then siphoned into the evaporator (as noted above). Two separate property models are used in order to both improve the eﬃciency through optimization and accurately describe the cycle. The mixture stream then exchanges heat with the liquid absorbing ﬂuid that is to be sprayed into the condenser/absorber. The refrigerant vapor and the remaining pressureequalizing vapor are then cooled until they condense. Component Analysis Introduction In order to model the behavior of the Einstein cycle. that mixture is pumped through a bubble pump to a reservoir (point 9). and energy. and then pass through the precooler to point 4. The ideal solution model presents simpliﬁcations for analysis of the cycle processes. To remove most of the pressure-equalizing ﬂuid that remains in the liquid mixture. The pressure-equalizing vapor leaves the generator at point 5. In the generator. and the pressure-equalizing/absorbing ﬂuid mixture leaves the condenser/evaporator at point 7. The residual pressure-equalizing vapor (point 9g) is combined with the pressure-equalizing vapor leaving the generator. and utilizes the three- . mass. The liquid absorbing ﬂuid then exchanges heat with the entering mixture stream. The entropy that is generated by each process is evaluated. and leaves the generator at point 10. Heat of absorption and condensation is rejected to the environment. and species conservation equations have been developed. as noted above. the ﬂuid mixture is heated to separate the absorbing ﬂuid from the pressure-equalizing ﬂuid. and enters the generator at point 8.22 the mixture entering at point 6.

saturated liquid refrigerant enters at point 2. The more accurate property model uses the Patel-Teja equation of state and Panagiotopolus and Reid mixing rules. Diﬀerences between the two models in their evaluation of the various components are noted in the following sections. 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 conservation of energy for the evaporator is: . The Evaporator The evaporator is presented in Figure 2-2 .23 4 3 2 Qevaporator Figure 2-2: The Evaporator parameter theory of corresponding states. as outlined in Chapters III and IV. In the evaporator. The partial pressure of the refrigerant is reduced. and is described in Chapter VI. causing it to evaporate and leave the evaporator as a vapor mixture with the pressure-equalizing ﬂuid at point 3.

3 + m4p yref r.3 is the vapor mass fraction of the pressure equalizing ﬂuid at point 3 and x is the liquid mass fraction.4m4 ˙ ˙ ˙ (2. the conservation equations become: ˙ ˙ ˙ ˙ ˙ m2 + m3p + m4 = m2p + m3 + m4p ˙ m2 xref r. the Patel-Teja equation of state must be used. an approximation must be formulated instead. 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. For the ideal solution model.3m3 = xpe. This approximate model is shown in Figure 2-3. It is also assumed that all of the heat transferred to the evaporator is transferred at that temperature.4) (2. the mixture mass conservation equation and a single species conservation equation completely specify the states.2 + m3p yref r.3p + m4 yref r.2p + m3 yref r.3) where ype.1) m3 = m2 + m4 ˙ ˙ ˙ ype. In order to accurately model the vapor-liquid-liquid equilibrium that can occur in the evaporator.24 ˙ Qevaporator = m3 h3 − m2 h2 − m4 h4 ˙ ˙ ˙ Mass and species conservation equations can also be written: (2.4 = m2p xref r.4p ˙ ˙ ˙ ˙ ˙ ˙ (2.5) .2 m2 + ype. Since the ideal solution model cannot accurately represent the evaporator’s internal processes.2) (2. Because there are only two ﬂuids. Given these assumptions.

2p + m4p ype. is the entropic average temper- .4p ˙ (2. and mass conservation equations.8) Returning to a more realistic model of the evaporator.1.s (2.3p = m2p xpe. species.s . but a further energy conservation statement is also needed: ˙ Qevaporator = m3p h3p − m2p h2p − m4p h4p ˙ ˙ ˙ (2.9. the entropy generation is: ˙ Qevaporator ˙ ˙ ˙ ˙ Sevaporator = m3 s3 − m2 s2 − m4 s4 − T evaporator. T evaporator.25 4 2 3 2p 4p 3p Qevaporator Figure 2-3: The Ideal Solution Evaporator Model ˙ ˙ m3p = m2p + m4p ˙ ˙ ˙ m3p ype. in addition to these energy.6) (2. a second law analysis should also be performed. For the evaporator.7) The conservation of energy for the evaporator is still equation 2.9) The temperature in equation 2.

14) (2.4bm4b = ype.13) Within the precooler.4m4 + ype. it is deﬁned as: ˙ Q ¯ Ts = δQ T (2.9g m9g m4b h4b = m4 h4 + m9g h9g ˙ ˙ ˙ (2.26 ature. and no external heat is added or released. Two pinch points (minimum temperature diﬀerences) are required. species. When heat is transferred over a temperature diﬀerence. since three streams are exchanging heat.) This combination of the pressure-equalizing streams can be quantiﬁed through mass.15) .10) The Precooler Prior to entering the precooler.12) (2. Mathematically. the pressure-equalizing vapor from the generator mixes with pressure-equalizing vapor from the bubble pump. as presented in Figure 2-4. (It should be noted that the ideal solution model does not include a bubble pump. entropy is generated. The entropic average temperature is a means of determining the average temperature at which this generation occurs. T2 = T4 + pinch24 T4b = T6 + pinch4b6 (2. These pinch points will be speciﬁed to occur between points 2 and 4 and points 4b and 6. no mixing occurs between the three streams.11) (2. and energy conservation equations: ˙ ˙ m4b = m4 + m9g ˙ ˙ ˙ ˙ ype.

.27 4b 6 1 4 3 2 Figure 2-4: The Precooler The ideal solution model does not include the bubble pump. m1 = m2 ). Only a single equation is then needed to specify the states of the precooler: ˙ ˙ ˙ ˙ ˙ m1 h1 + m3 h3 + m4b h4b = m2 h2 + m4 h4 + m6 h6 ˙ (2.18) This equation also includes the entropy generated by mixing the pressureequalizing vapor streams from the generator and the bubble pump.17) The precooler transfers heat across ﬁnite temperature diﬀerences.15 becomes: T5 = T6 + pinch56 where state point 5 is equivalent to state point 4b. generating entropy: ˙ Sprecooler = m2 s2 + m4 s4 + m6 s6 − m1 s1 − m3 s3 − m5 s5 − m9g s9g ˙ ˙ ˙ ˙ ˙ ˙ ˙ (2.e. and the conservation of mass is satisﬁed ˙ through the evaporator and condenser/absorber equations. (2. neither the species concentrations nor the ˙ mass ﬂow rates change (i.16) Because the streams do not mix. so equation 2.

so it condenses at a higher temperature than in the evaporator. the refrigerant’s partial pressure returns to the system pressure.1 m1 + xi.20) (2. A liquid mixture of absorbing ﬂuid and pressure-equalizing ﬂuid is immiscible with the refrigerant.7 m7 = yi. Some pressure-equalizing ﬂuid condenses as well. while the partial pressure of the pressure-equalizing vapor decreases as it rises.19) ˙ ˙ ˙ m1 + m7 = m6 + m11 ˙ ˙ ˙ ˙ ˙ xi. and that liquid mixture then enters the precooler. The amount of heat transferred from the condenser/absorber is found from the conservation of energy: ˙ ˙ ˙ ˙ ˙ Qcond/abs = m1 h1 + m7 h7 − m6 h6 − m11 h11 The species and mass conservation equations state that: (2.28 The Condenser/Absorber Rather than utilizing a separate condenser and absorber. Since there are three ﬂuids present in the . and is siphoned from the bottom of the condenser/absorber into the generator.6 m6 + xi.11 m11 (2. A vapor mixture of refrigerant and pressure-equalizing ﬂuid is bubbled into the ﬁlm. A weak liquid mixture of absorbing ﬂuid and pressure-equalizing ﬂuid falls in a ﬁlm down the side of the unit. thereby maximizing the absorption potential of the liquid throughout the unit. and the pressure-equalizing ﬂuid is absorbed. these units are combined in the Einstein cycle (Figure 2-5).21) where i represents one of the ﬂuids. generating useful heat. As the pressure-equalizing ﬂuid is absorbed. The entering liquid mixture increases its pressure-equalizing ﬂuid concentration as it falls down the condenser/absorber.

the internal solution heat exchanger. The external heat exchanger and a full internal solution heat exchanger are departures from Einstein’s original patent. and the generator unit.22) . these elements produce pressure-equalizing ﬂuid vapor for both the evaporator and the condenser/absorber and liquid absorbing ﬂuid for the con- (2.s The Generator The generator control volume will be deﬁned as including the external solution heat exchanger. as shown in Figure 2-6. Combined. the species equation must be stated for any two to completely specify this control volume. the bubble pump. the reservoir.29 11 1 7 Qcondenser/absorber 6 Figure 2-5: The Condenser/Absorber condenser/absorber. The entropy generation in the condenser/absorber is: ˙ Qcond/abs ˙ ˙ ˙ ˙ ˙ Scond/abs = m1 s1 + m7 s7 − m6 s6 − m11 s11 − T cond/abs.

29) (2.23) Again.5m5 + xpe.25) The processes in the external and internal solution heat exchangers must also be accounted for.27) To account for the heat transferred in the internal and external solution heat exchangers. No mixing occurs in either the external or the internal heat exchanger.9 m9 ˙ ˙ ˙ ˙ ˙ ˙ m7 h7 + m11 h11 = m8 h8 + m10 h10 ˙ (2.26) (2.9g m9g + xpe. only a single species mass conservation equation is needed in addition to the mixture conservation of mass: ˙ ˙ ˙ m5 + m9g + m11 = m7 ˙ ype.30) .8 m8 = ype. The conservation of energy for the entire control volume states that ˙ ˙ ˙ ˙ ˙ Qgenerator = m5 h5 + m9g h9g + m10 h10 − m8 h8 (2.24) (2.11 m11 = xpe. since only two ﬂuids are present.30 denser/absorber from a liquid pressure-equalizing/absorbing ﬂuid mixture and a heat input. species.28) (2. so the mass ﬂow rates remain constant in each stream: ˙ m7 = m8 ˙ m9f = m10 = m11 ˙ ˙ ˙ (2. additional mass.7m7 ˙ ˙ ˙ ˙ (2. and energy equations are required: m8 = m5 + m9 ˙ ˙ ˙ xpe.5m5 + ype.

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

23 becomes: ˙ ˙ ˙ ˙ Qgenerator = m5 h5 + m10 h10 − m8 h8 (2. the entropy generated by the generator is: . a pinch point must also be deﬁned: T11 = T7 + pinch7.31) As noted previously. The mass.31 remain the same. which results in the conﬁguration shown in Figure 2-7. species.28-2.32) Returning to a model that includes the bubble pump.11 (2. Equations 2.32 5 10 11 8 7 9 Qgenerator Figure 2-7: The Ideal Solution Model Generator Finally. and energy conservation equations must be modiﬁed to reﬂect this change. for simplicity. but equation 2. the ideal solution model does not include the bubble pump.

which may contain smaller gas bubbles. In wispy-annular ﬂow. which “pumps” the liquid to the upper reservoir. or annular ﬂow. 1981). the liquid phase is present both as a ﬁlm on the wall of the pipe and as long ﬁlaments of agglomerated . can be diﬃcult to diﬀerentiate from annular ﬂow. slug. A bubble pump is a heated tube that lifts ﬂuid from a lower reservoir to a higher reservoir.33) The entropy generated by the internal and external solution heat exchangers is also accounted for in equation 2. These ﬂow regimes are illustrated in Figure 2-9 (Collier. where the large gas bubbles begin to break down in an oscillatory fashion. In the second stage. Heat applied at the bottom of the tube causes vapor bubbles to form and to rise. wispy-annular ﬂow. so that the center of the tube is alternately ﬁlled with the liquid and the vapor phases. the twophase ﬂow moves sequentially through these ﬂow patterns.33 ˙ Qgenerator ˙ Sgenerator = m5 s5 + m9g s9g + m11 s11 − m7 s7 − ˙ ˙ ˙ ˙ T generator. it merits a separate review. The next stage is churn ﬂow. wispy-annular. As the heat that is added to the pipe increases. churn.s (2. The Bubble Pump Although the bubble pump is part of the generator subsystem. the bubbles expand until they are bullet-shaped and nearly span the diameter of the tube. 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. These bubbles are separated by “slugs” of liquid.33. This creates a balance between the buoyancy and the friction forces. as shown in Figure 2-8. The fourth stage. where the vapor exists as discrete bubbles within the liquid phase. The ﬁrst stage is bubbly ﬂow. Two-phase ﬂow in a vertical pipe falls into one of ﬁve ﬂow regimes: bubbly.

34 L d H Heat Figure 2-8: A Bubble Pump .

36) Flow maps can also be useful in predicting the nature of the ﬂow. An upper bound for slug ﬂow is provided by Chisholm (1983). There are numerous methods which can be used to determine the ﬂow regime. 1981. The ﬁnal stage is annular ﬂow.0 − 1.25 (2.84F rf —f V (2.15 σ A A ρ2 f 0. Delano has shown that a bubble pump operates most eﬃciently in the slug ﬂow regime (1998). Taitel et al.075 0.075 = F rf − 0. as shown in Figure 2-10.35 droplets dispersed throughout the central core of the ﬂow. ρ is the density. Tutu (1984) recommends using a dimensionless approach that employs the liquid Froude number. Azbel.35) where g is gravity. which represents a ratio of the inertial force to the gravitational force. 1981). which predicts a transition from slug to churn ﬂow at: σ/ρf g(1 − ρg /ρf ) D = 19 (2. For example. σ is the surface tension. and A is the crosssectional area of the pipe.34) where — is the volume ﬂow rate of the liquid (f ) or the vapor (g). Collier (1981) plots the ﬂow regimes on axes of the vapor momentum ﬂux versus the liquid momentum ﬂux. A commonly used ﬂow map was . which is characterized by a liquid ﬁlm surrounding a vapor core (Collier. His derivation provides the boundary between the bubbly and slug ﬂow regimes: —g V −0. V (1980) provide an alternate correlation for the same transition from bubbly to slug ﬂow: —g V g(ρf − ρg ) —f V = 3.

36 Figure 2-9: Vertical Flow Regimes .

He plotted —g ρg V G = 1. to the tube length.37) µf ρ2 f 1 3 (2. Some similiarities can be noted between the Baker ﬂow map of Figure 2-11 and the Collier ﬂow map of Figure 2-10.0212 × 105 √ λ πD 2 ρg ρf versus 0. Baker developed his transition lines from experimental data. two-phase ﬂow is treated as a single-phase ﬂow with properties that are a weighted average of the individual phases. and λ and ψ are functions of the ﬂuid densities and viscosities.39) Griﬃth (1961) has given a correlation to calculate s for slug ﬂow: .37 developed by Baker in 1954. L is the mass velocity of the liquid phase. L) on the ﬂuid properties of the bubble pump: Vf2 1 H (1 + K + KsR + 2sR ) = + L 1 + sR /s 2gLA2 s= sR = Vg Vf —g V —f V (2. A complete derivation has been given by Delano (1998) for the dependence of the submergence ratio (which is the ratio of the reservoir height.1844V f — Lλψ = G σV g — ρ3 f ρg 1 2 (2. It should be noted that all of the ﬂow regime correlations and ﬂow maps described above have been developed using a homogeneous ﬂow model.38) where G is the mass velocity of the gas phase. H. In the homogeneous ﬂow model.

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

including those due to friction.39 √ —g 0. an optimization must be performed.316 (Re)0.42) In order to minimize the heat transfer that needs to be added to the bubble pump.40) Furthermore.2 —f V —f V (2.35A gD V + s = 1.41) Re = 4ρ(V g + —f ) — V πµD Since boiling produces the vapor bubbles. Returning to the use of the bubble pump within the Einstein cycle.. 1990): 0. and the amount of heat transferred to the bubble pump. the liquid ﬂow rate. This can be expressed as the pumping eﬃciency: . Friction losses are derived from the friction factor (Reinemann et al.2 + 0. the friction coeﬃcient (K) is a function of the pipe losses. A similar relationship is seen for the diameter. the amount of heat transferred to the bubble pump determines —g : V ˙ Qbubblepump ρg · hf g —g = V (2. the goal is to minimize the amount of heat transfer needed to pump the desired amount of liquid and vapor. The relationship between the bubble pump tube diameter and the liquid and vapor ﬂow rates can be seen in Figures 2-12.25 f= where (2.

2) 0.6 m m m liq (k g /s ) 0.6 d = 8.7 0.5 d = 7.6 mm 0.40 0.2) .8 0.2 0.3 0.8 0.6 m m Q bubpump Figure 2-13: Eﬀect of Diameter on Liquid Flow Rate and Heat Transferred to the Bubble Pump (Submergence Ratio = 0.6 mm m v ap (k g /m in ) Figure 2-12: Eﬀect of Diameter on Liquid and Vapor Flow Rates (Submergence Ratio = 0.1 0 0 1 2 3 4 5 d = 6.4 0.6 mm m liq (k g /s ) 0.3 0.1 0 0 20 40 60 80 d = 6.6 m m 0.7 0.5 d = 7.4 0.6 d = 8.2 0.

By deﬁning a control volume to include the entire cycle. This section of the curve can be approximated as a straight line so that ˙ mliq = 1. 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. or coeﬃcient of performance (COPh). Second Law Analysis The Coeﬃcient of Performance The heating eﬃciency of the cycle. conservation of energy states that . For these values. This can be demonstrated by combining a ﬁrst and second law analysis.43) This is an improvement of 7.6 · mvap ˙ ˙ (2. The liquid and vapor ﬂow rates for this section of the curve can be approximated as: mliq = 28.41 ηpump = m ˙ ˙ Qbubblepump Fixing the submergence ratio as a reasonable 0.22x10−2 · Qbp ˙ (2.9% over Delano’s bubble pump eﬃciency.2. the diameter with the optimal slope that will still fall within the slug ﬂow regime is 8. is directly related to the cycle’s entropy generation.6 mm. as in Figure 2-15.44) These two equations describe the bubble pump’s performance within the cycle.

6 mm 0.3 0.2 d = 8.42 0.6 mm Qca Condenser/ Absorber Generator Evaporator Qgen Qevap Figure 2-15: Heat Transfer To And From The Einstein Cycle .5 0.7 0.8 A h/L = 0. D = 8.2.2 0 20 40 60 80 100 120 140 Q b u b pu mp Figure 2-14: Pumping Capacity for h/L = 0.6 m liq 0.4 0.

48) 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 purchased.46) ¯ ˙ Si is the entropy that is generated in component i.s Tgen.45 can be rearranged as ˙ ˙ ˙ Qevap = −Qgen + Qca and substituted into equation 2.s Tgen. this is the heating provided by the condenser/absorber divided by the heating required by the generator: . as outlined in the description of the evaporator.s ) ˙ Si = Qca ( ¯ ¯ Tca.s Tevap.45) This assumes that the sign of the rate of heat transfer is always positive in the direction indicated in Figure 2-15. and Ts is deﬁned as the entropic average temperature.s (2.47) ¯ Tevap. A second law balance on a control volume that includes the entire cycle is: ˙ ˙ ˙ Qca Qevap Qgen ˙ Si = ¯ − ¯ − ¯ Tc/a.s − Tevap.s This can then be restated as ¯ ¯ ¯ ¯ ˙ ˙ Tevap.s (2. For the Einstein cycle.43 ˙ ˙ ˙ Qevap + Qgen − Qca = 0 (2.s Tgen.s (2.s − Tca.s ) + Qgen ( Tgen. Equation 2.s Tevap.46 to yield ˙ ˙ ˙ ˙ Qca (−Qgen + Qca ) Qgen ˙ Si = ¯ − − ¯ ¯ Tca.

50 yields: ¯ ¯ ˙ Tevap.s Si degradation COP h.s ) COP hrev = ¯ ¯ ¯ Tgen.s − Tevap.s Tgen.s ¯ Tevap. TM . and low temperatures.s − Tevap.s Si · COP h = COP hrev − ¯ ¯ ˙ Tca.i = ¯ · ¯ ˙ Tca.50) Furthermore.s − Tca. or ideal.s − Tevap.s (Tca.s )+( ) ¯ ¯ Tca. the reversible.s Qgen (2. For the Einstein cycle. this is equivalent to: ¯ ¯ ¯ Tca.s = COP h ( (2.54) ˙ This relation illustrates that if the amount of entropy generated by a component (Si ) can be reduced. the degradation of the COP can also be lessened.44 COPh = ˙ Qca ˙ Qgen (2. heating coeﬃcient of performance for a system operating at three temperatures is: TM (TH − TL ) TH (TM − TL ) COP hrev = (2. middle. and the performance of the cycle can be improved.s (Tgen. manipulating equation 2. . respectively (Delano.s · Tca.49) ˙ Dividing equation 2.53) (2.52) (2.s − Tevap.s · Tca.s Qgen Therefore. the ideal COP is reduced to the actual COP by: ¯ ¯ ˙ Tevap.48 by Qgen therefore produces ˙ Si ˙ Qgen ¯ ¯ ¯ ¯ Tevap. TL are the high. 1998).s Tgen.s ) Given this deﬁnition.s − Tevap.51) where TH .

45 An Illustrative Case: The Internal Generator Heat Exchanger Examining the causes of entropy generation in each component is obviously of interest. In Delano’s study. For given inlet and outlet conditions. the processes that occur there can be treated as fully reversible. By reducing the magnitude of the temperature diﬀerences. and by assuming that the external heat is added at the temperature of the mixture at each point in the generator. resulting in entropy generation. When the partial internal solution heat exchanger is replaced by a full internal solution heat exchanger. by transferring heat across a ﬁnite temperature diﬀerence. 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. 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. three conﬁgurations were examined: 1) . the amount of entropy that is generated can also be reduced. However. and increased the COP. The temperature proﬁles of the ﬂuids inside and outside the tube are not parallel. the temperature diﬀerences across which heat is transferred are lessened. Entropy generation can be caused by friction. Without an internal solution heat exchanger. the heat exchanger also caused the internal heat transfer to occur at quite large temperature diﬀerences. and a pinch point must occur at one end. as illustrated in Figure 2-16. or by mixing. a partial internal solution heat exchanger was used in the generator to heat the pressure equalizing/absorbing ﬂuid mixture entering from the condenser (1998). This heat exchanger improved the internal heat recovery. The temperature diﬀerences are inherent and cannot simply be eliminated through the creation of a larger heat exchanger.

46 5 10 5 10 8 8 9 9 Qgenerator Qgenerator Partial Internal Heat Exchanger Full Internal Heat Exchanger Figure 2-16: Alternate Generator Conﬁgurations .

the heat transferred to and from the evaporator and the condenser/absorber are constant. and 3) Full internal and external heat exchange.) EES programs for each of the conﬁgurations are included in Appendix A. . The amount of supplied heat was approximately 522 kW for conﬁguration 1. 2) Partial internal and no external heat exchange. The heating coeﬃcient of performance is an inverse function of the amount of heat transferred to the generator. and 248 kW for conﬁguration 3.47 No internal or external heat exchange. 311 kW for conﬁguration 2. (Since the inlet and outlet conditions are ﬁxed. so it can be seen that the COPh is indeed the highest for conﬁguration 3.

b (van der Waals.) In 1873. 1873).1) was developed from molecular principles. Simultaneously solving these equations yields . the isotherms generated from the van der Waals equation of state must have an inﬂection point at the critical point. and the volume occupied by a molecule.2) at T = Tc . (A capital letter designates a molar property and a lower-case letter designates a mass-based property.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. and accounts for both intermolecular forces. This is deﬁned mathematically as ∂P ∂V ∂2P ∂V 2 =0 T =0 T (3. a. His cubic equation of state a Ru T − 2 V −b V P = (3. van der Waals formulated an equation of state that could model a substance in both the liquid and the vapor regions. P = Pc . and V = Vc . In order to match actual ﬂuid behavior.

4: 9 Ru Tc Vc Ru T − 8 Vc V2 V − 3 (3.5) Pr ≡ P Pc Vr ≡ V Vc are deﬁned as the reduced temperature. 3. pressure.3) Substituting a and b into equation 3.49 9 a = Ru Tc Vc 8 1 b = Vc 3 (3.4) P = P = T /Tc Ru Tc Vc (V /Vc ) − 1 3 − 9 8 (V /Vc )2 Pr = where Tr ≡ T Tc 3 8Tr − 2 3Vr − 1 Vr (3.5 is that it asserts that the reduced pressure of any substance is solely a function of that substance’s reduced temperature and .1 at the critical point shows that P c Vc 3 = Ru Tc 8 Combining equations 3. Two-Parameter Principle of Corresponding States The signiﬁcance of equation 3. and 3. and volume (Abbott and Van Ness. 1989).3.1.

the critical volume cannot be accurately measured. vc must be known. . Three-Parameter Principle of Corresponding States In actuality. To calculate Zc .375 for all substances. Unfortunately. it can be deduced that the two-parameter principle of corresponding states assumes that the critical compressibility is equal to 0. The compressibility factor is deﬁned as Pv RT Z= (3. approaches inﬁnity at the critical point. The critical compressibility factor is Pc vc RTc Zc = (3.50 volume. the critical compressibility can vary greatly between substances.7) Therefore. 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. Furthermore. and volume are characterized by the same relationship for all substances. (∂v/∂P )T .4. This would suggest that utilizing Zc as a third parameter could increase the accuracy of the principle of corresponding states. 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. temperature. Unfortunately. One way of measuring this variability is to examine the compressibility factor (Z) of a substance.6) where Z = 1 for an ideal gas. reduced pressure. from equation 3. since the diﬀerential compressibility.

1955).7 − log10 (Pr sat )Tr =0. such as the heavier rare gases (Pitzer.7.8) The acentric factor measures the deviation of intermolecular potential from a simple ﬂuid.10) . Simple ﬂuids all exhibit a reduced saturation pressure of approximately 0. the principle of corresponding states becomes highly accurate for subcooled and superheated nonpolar and slightly polar substances. Pr ) + · · · (3.8 becomes ω = −1 − log10 (Pr sat )Tr =0. 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 . so equation 3. Tc .9) The acentric factor can therefore be determined from the critical temperature and pressure and from one saturation pressure measurement. A simple ﬂuid is deﬁned as one with a spherical shape and an inverse sixth power potential. Pr .7 (3. and ω). While the accuracy is lessened in the saturated region and near the critical point. Pr ) + ωZ (1) (Tr . ω) = Z (0) (Tr .51 Pitzer et al. With three parameters (Pc . the three-parameter model still provides a reasonable approximation.1 at a reduced temperature of 0.7 (3. (1955) suggested an alternate third parameter that they termed the acentric factor: ω = log10 (Pr sat )Simple Fluid at Tr =0.

3).52 This equation is based on an expansion of the compressibility factor as a simple power series in the acentric factor. They found that the compressibility factor of any ﬂuid is a function of the compressibility of a simple ﬂuid (Z (0) ).11) Lee and Kesler chose n-octane as the reference ﬂuid. and the acentric factor. where Z (0) and Z (r) are functions of Tr and Pr : ω (Z (r) − Z (0) ) ω (r) Z = Z (0) + (3. Pitzer et al. Through a combination of experimental data and the modiﬁed BenedictWebb-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 + 2 + 5 + 3 2 β + 2 exp − 2 Vr Vr Vr Tr Vr Vr Vr Zr = 1 + where (3. (1955) determined that the ﬁrst two terms are suﬃcient to accurately describe the compressibility factor in almost all regions.12) B = b1 − b2 b3 b4 − 2− 3 Tr Tr Tr C = c1 − c2 c3 + 3 Tr Tr . the compressibility of a reference ﬂuid (Z (r) ). Lee and Kesler (1975) expanded this work to provide increased accuracy and to include a wider range of temperatures (Tr ≥ 0.

0236744 0. the reduced compressibility is also Pr Vr Tr Zr = (3.0503618 c3 0 0. equation 3. and the reduced volume is found.030323 0.13) To ﬁnd Z (0) . a reduced temperature and pressure are chosen.155488 0. That equation is then set equal to equation 3.6 and 3.041577 4 d1 x 10 0. Once Vr (0) is calculated. Due to the highly nonlinear nature of equation 3.48736 4 d2 x 10 0.0186984 0.203488 c1 0.331511 b3 0.53 Table 3-1: Constants for Calculating Compressibility Constant Simple Fluid (0) Reference Fluid (r) b1 0. This is not an actual reduced volume.027655 b4 0. solving for Vr is not a . as shown in Table 3-1. but rather a pseudo-reduced volume.12.03754 D = d1 + d2 Tr A set of constants was determined for the simple ﬂuid and the reference ﬂuid.12.2026579 b2 0.0313385 c2 0.13.15479 0. the simple ﬂuid coeﬃcients listed in Table 3-1 are used in equation 3.060167 0.226 γ 0.0740336 β 0.65392 1. Recalling equations 3. This process is then repeated using the reference ﬂuid coeﬃcients to ﬁnd Vr (r) and Z (r) .042724 0.13 is used to ﬁnd Z (0) .1181193 0.7.016901 c4 0.265729 0.623689 0.

the root that corresponds to the liquid state should be chosen.54 simple calculation. the root that corresponds to the vapor state should be used.28862 ln(Tr ) + 0. the state of the substance must be known in order to determine which root to utilize. one root is at a vapor state (point 3). however. that point corresponds to either a liquid state (Figure 3-1a) or a vapor state (Figure 3-1b).6875/Tr − 13. For superheated or subcooled substances.14) f (1) = 15.12 and 3.11 to determine the ﬂuid’s compressibility at the given reduced temperature and .43577Tr 6 Therefore. and one root (point 2) has no physical signiﬁcance because it does not represent a stable state. Once Z (0) and Z (r) have been found. 1990): ln(Pr sat ) = f (0) + ωf (1) where f (0) = 5. For every reduced temperature and pressure. when Pr > Pr sat .2518 − 15.16934Tr 6 (3. 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. If three real roots exist (Figure 3-1c). In the saturated region..09648/Tr − 1. one root is at a liquid state (point 1). so Z (0) and Z (r) can be calculated solely from equations 3.92714 − 6. and when Pr < Pr sat . only one root is present.4721 ln(Tr ) + 0. there are either one or three real roots which satisfy the equations.13. they can then be substituted into equation 3. If there is only one root.

5 1 1.5 3 Reduced Volume Reduced Pressure 0 0.13 .55 Reduced Pressure 0 0.75 2 2.5 2 2.75 2 Reduced Volume Figure 3-1: Intersection of Equations 3.25 0.25 0.5 0.25 Reduced Volume Reduced Pressure 0 0.75 1 1.5 1.12 and 3.5 1.5 0.25 1.75 1 1.25 1.

so the derivation of the enthalpy departure function will be presented. and is equal to 0. entropy.3978.17) . Calculation of the Enthalpy Departure Function Once the compressibility is known. 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. and isobaric speciﬁc heat.15) where H ∗ is the ideal gas enthalpy and H is the actual enthalpy on a mole basis. isochoric speciﬁc heat. This analysis is primarily concerned with enthalpy. the enthalpy departure function can be related to the Gibbs energy: ∂((G − G∗ )/Ru T ) H − H∗ = −T RT ∂T The Gibbs energy is also related to the compressibility: G − G∗ = Ru T P 0 (3. many other properties can be calculated by using the three-parameter corresponding states model. These properties include departure functions for enthalpy.16) P (Z − 1) dP P (constant T) (3. 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: H − H∗ H − H∗ = Ru Tc Ru Tc (0) + ω ω (r) H − H∗ Ru Tc (r) − H − H∗ Ru Tc (0) (3. The reference acentric factor (ω (r) ) is a known constant.56 pressure. Using fundamental property relations.

Ideal gas internal energy (u) can be represented as a function of temperature and volume: ∂u ∂T ∂u ∂v du = dT + v dv T (3. and ((H − H ∗ )/Ru Tc )(r) is calculated using the reference ﬂuid constants and reduced volume. the principles of that state should be examined.57 so equation 3.20) . The usefulness of these enthalpy departure function and saturation pressure calculations in determining ideal ﬂuid properties is demonstrated in the next sections.16 becomes: H − H∗ = −T Ru T P 0 ∂Z ∂T P dP P (constant T) (3.18) Replacing Z with equation 3.19) E= As with the compressibility. Ideal Gas Theory Since the theory of corresponding states produces functions that are departures from the ideal gas state.12 yields b2 + 2b3 /Tr + 3b4 /Tr 2 H − H∗ = Tr Z − 1 − Ru Tc Tr Vr 2 c2 − 3c3 /Tr d2 − + + 3E 2 2Tr Vr 5Tr Vr 5 where γ γ c4 β + 1 − β + 1 + 2 exp − 2 3 2Tr γ Vr Vr (3. the simple ﬂuid constants and reduced volume are used to ﬁnd ((H − H ∗ )/Ru Tc )(0) .

22) Recalling that P v = RT for an ideal gas. it is then evident that the internal energy of an ideal gas is solely a function of temperature (Black and Hartley.24) dh = du + d(RT ) = du + RdT (3.58 Constant-volume speciﬁc heat is deﬁned as: δq dT ∂u ∂T cv ≡ ≡ v (3. substituting this into equation 3. By deﬁning constant-pressure speciﬁc heat: . this equation becomes (3.25) and the enthalpy of an ideal gas is also shown to be only a function of temperature.23.21) v so.20 results in ∂u ∂v du = cv dT + dv T (3. Enthalpy (H) is deﬁned as a function of internal energy. ∂u ∂v =0 T so this equation can be further simpliﬁed to du = cv dT (3. pressure and volume: dh ≡ du + d(P v) Returning again to the ideal gas equation of state. 1991).23) From equation 3.

27) Incompressible Liquid Theory For the ideal solution model. At a given temperature. all liquid states will be assumed to behave as an incompressible liquid at saturated liquid conditions.26) p the diﬀerential enthalpy can then be stated as dh = cp dT (3. The slope of the saturated vapor line is equal to the gas speciﬁc heat at constant pressure (cp. since the majority of processes in the Einstein cycle depend on operation in the saturation region. hg and.59 cp ≡ δq dT ≡ p ∂h ∂T (3. While the slope and curvature of the lines are dependent on the substance. The enthalpy at any point can be determined in a manner similar to that employed in the previous ideal gas analysis. this general behavior is universal. the diﬀerence in the saturated vapor enthalpy and the saturated liquid enthalpy is the heat of vaporization (hf g ) for that temperature. While there is a great deal of curvature demonstrated close to the critical point. hf are primarily linear in the noncritical region. particularly. Saturated Liquid and Vapor Behavior: Enthalpy Versus Temperature For a given substance. and the slope of the saturated liquid line is the ﬂuid speciﬁc heat . the enthalpies of the saturated vapor (hg ) and the saturated liquid (hf ) vary with temperature in the manner illustrated by Figure 32.g ). This is not an unreasonable assumption.

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 ) 550 500 h f Is o b u ta n e 450 400 350 300 250 300 1600 316 331 347 363 379 394 410 Tem perature (K ) 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 4 Enthalpy 3 2 href 1 Tref Temperature Figure 3-4: Saturated Liquid and Vapor Enthalpy at constant pressure (cp.27 from a reference state (point 0) to the point of interest: . In deciding which speciﬁc heat to use as an additional parameter. Therefore. the ﬂuid speciﬁc heat at constant pressure will be selected as the speciﬁed parameter. the enthalpy of a vapor at any point can be found by integrating equation 3. it can be seen that the saturated liquid line tends to behave in a more linear fashion than the saturated vapor line.f ). Implementation of the Ideal Gas and Incompressible Solution Theories Returning to the ideal gas analysis. and will be assumed to be constant. By observing a variety of saturation curves away from the critical point. as in Figure 3-3. the shape of the saturation lines should be considered.

and the enthalpy is: hshv = h0 + cp. reference values (h0 .63 h T dh = h0 T0 cP dT (3. the saturated vapor enthalpy at any temperature is: hg = h0 + cp. For example. Therefore. which is set to zero.28) It is helpful to assign the value of the enthalpy at a reference state.f (T − T0 ) + hf g (T ) + hsv−g (T ) (3. the path of integration is 1-2-3-4. The reference pressure for all three ﬂuids should be equal.) Therefore. and the reference enthalpy is the saturated liquid enthalpy at that temperature and pressure.f (T − T0 ) + hf g (T ) (3. and has been set to the atmospheric pressure (101 kPa) for this analysis.28 can be represented graphically on the enthalpy versus temperature plots of the previous section.30) where hsv−g is the diﬀerence in enthalpy between the superheated and saturated vapor at T . (This ﬁgure is a simpliﬁcation of the saturation curves from Figures 3-2 and 3-3. For an incompressible liquid. and to use this to calculate the enthalpy at any other state. the enthalpy of a saturated vapor can be traced as path 1-2-3 in Figure 3-4. P0 and T0 ) are assigned for each ﬂuid.29) For a superheated vapor. determining the enthalpy is even more basic. The reference temperature therefore varies between ﬂuids. Equation 3. . The reference temperature for each ﬂuid is the saturation temperature at the universal reference pressure.

1-4-5. the magnitude of the heat of vaporization will account for this.1 hfg.64 3 5 7 Enthalpy hfg.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. Since all liquid states are assumed to be the saturated liquid state. even if the saturated vapor line ﬂattens out or develops a negative slope. This is illustrated through paths 1-2-3.f (T − T0 ) (3.2 hfg. determining the enthalpy of a liquid is represented by path 1-2. so that hf = h0 + cp. For example.3 6 4 href 1 Tref 2 Temperature Figure 3-5: Saturated Liquid and Vapor Enthalpy Enthalpy is a function of both temperature and pressure. . and 1-6-7 in Figure 3-5. but it is only a weak function of pressure when it is a liquid and close to the reference pressure.

so the saturated liquid and vapor roots can also be determined.14. the diﬀerences in enthalpy (hf g and hsv−g ) used in the above equations can be accurately calculated using corresponding states. the enthalpy departure function can be calculated in conjunction with the compressibility and the pseudo-reduced volume. at a given temperature (T1 ).32) T =T1 x=1 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∗ RTc h T =T1 = RTc x=1 + h∗ =T1 T T =T1 x=1 x=1 and h − h∗ RTc + h∗ =T1 T T =T1 x=0 x=0 h T =T1 = RTc x=0 So the enthalpy of vaporization becomes . Therefore. Recall that if Tc . P sat can also be determined from equation 3. Pc . and ω are known. The enthalpy of vaporization (hf g ) at T1 is deﬁned as: h − h∗ RTc and T =T1 x=0 (3.65 Determining Enthalpy Diﬀerences While the ﬂuid speciﬁc heats and the reference states are given. h − h∗ RTc are known. Furthermore.

recalling that the change in enthalpy for an ideal gas is only a function of temperature. .33 is equal to zero: h∗ =T1 − h∗ =T1 = cp (T1 − T1 ) = cp (0) = 0 T T x=1 x=0 Therefore. the second term in equation 3. the molecular mass. the enthalpy of vaporization can be represented as a function of the critical temperature.35) where the departure functions are calculated at the same temperature but diﬀerent pressures. such that: hsv−g (T1 ) = RTc h−h RTc ∗ T =T1 P =P actual − h−h RTc ∗ T =T1 P =P sat (3.66 h − h∗ hf g (T1 ) = RTc RTc T =T1 x=1 h − h∗ − RTc + (h∗ =T T T =T1 x=0 1 x=1 − h∗ =T1 ) T x=0 (3. and two calculated enthalpy departure functions: Ru h − h∗ Tc hf g (T1 ) = M RTc T =T1 x=1 h − h∗ − RTc T =T1 x=0 (3.34) 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.33) However.

and pressure. pressure has no eﬀect on the fugacity of a liquid. the individual ﬂuids must be combined using equilibrium conditions and mixing rules. the enthalpies of the individual ﬂuids are calculated for saturated liquid.1) However. and superheated vapor states. saturated vapor. temperature. Next. 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) At constant temperature and pressure. To provide a more useful form of this equation. this form of the fugacity relationship does not present an explicit representation of the mole fractions.67 CHAPTER IV THE IDEAL SOLUTION MODEL In the previous chapter. 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: L fiL = xi fpure i 2) At moderate pressures. some simplifying assumptions can be made. .

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: V fiV = yi fpure i 4) Finally.2) 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 = i Ni (4. at constant temperature and pressure.1 is reduced to: yi P = xi Pisat This is Raoult’s Law (Prausnitz et al..68 Additionally. the vapor phase is assumed to be an ideal gas. 1986). equation 4. the vapor phase is assumed to be an ideal gas: L fpure i = Pisat 3) As in assumption 1. as previously stated in assumption 2. so that the vapor fugacity of the pure component is equal to the total pressure: V fpure i = P Given these assumptions.3) . Mole and Mass Fractions (4.

4) and the liquid mole fraction is similarly deﬁned: Ni Nm.6) Therefore. only a two-component mixture need be considered. it also holds that the sum of the liquid mole fractions is equal to one (Black and Hartley.7) At each point in the Einstein cycle. liquid xi ≡ (4. the liquid and vapor mole fractions can then be stated solely as functions of the absolute and saturations pressures: sat P −P1 sat sat P2 −P1 sat P2 P x2 = y2 = x2 (4.5) The sum of the vapor mole fractions can be demonstrated to be equal to one: n n yi = i i Ni Nm. In combination with equation 4.6 and 4.7 reduce to y1 + y2 = 1 and x1 + x2 = 1. so equations 4.2. vapor yi ≡ (4.69 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 Nm. 1991): n xi = 1 i (4. vapor = n i Ni Nm = Nm =1 Nm (4.8) x1 = 1 − x2 y1 = 1 − y2 The partial pressures and the mass fractions can also now be determined: .

2 Mixing Rules ym.70 pi = y i P (4.1 = 1 − ym.10) xm.9) xm.2 = (y2 m2 )/(y1 m1 + y2 m2 ) (4.2 Once the mass fractions and the individual component enthalpies are known. the enthalpy of a vapor or a liquid mixture can be calculated.1 = 1 − xm.13) Enthalpy is a function of the Gibbs energy.11 results in: n n (4.12) Gig = i yiGig + Ru T i i yi ln(yi ) (4.11) The component chemical potential is in turn a function of temperature. 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 = i y i µi (4. and temperature (H = . and individual component Gibbs energy: µi = Gig + Ru T ln(yi) i Substituting equation 4.2 = (x2 m2 )/(x1 m1 + x2 m2 ) ym. To determine the mixing rules which govern this calculation.12 into equation 4. entropy. vapor mole fraction.

The molar mixture entropy is further related to the Gibbs energy as: ∂G ∂T S=− P. Similar to equation 4.12.15) 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.71 G + T S). the chemical potential for an ideal liquid solution is deﬁned as following: µi ≡ Gi + Ru T ln(xi ) (4. 1989): n H ideal soln = i xi Hi (4.14) where Hiig is the molar ideal gas enthalpy of component i. The ideal liquid solution mixture enthalpy is therefore analogous to the ideal gas mixture enthalpy (Abbott and Van Ness.16 can also be restated in terms of speciﬁc properties and mass fractions such that: n h = i ig ym.17) and .i hig i (4.13 reveals that the enthalpy of an ideal gas mixture is equal to: n H ig = i yi Hiig (4.y Combining these relations with equation 4.16) Equations 4.14 and 4.

.i hi (4.72 n hideal soln = i xm.18) 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.

The lower generator temperature provided more stability to the solver when the ﬂuid parameters were varied. To .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. the temperature of the condenser was set at 325 K (125◦F) and the evaporator temperature was speciﬁed to be 295 K (72◦ F). Searching for Optimum Properties Initially. in which all the parameters were varied simultaneously. This program and its libraries can be found in Appendix B. a full-scale nonlinear optimization of the cycle model was attempted. However. For the base case of the ammoniawater-butane mixture. Unfortunately. an EES program was created that describes the system behavior. the generator temperature that produced the highest heating coeﬃcient of performance was found to be 495 K. this technique caused the solver to become unstable and crash before a solution could be found. In order to produce conditions suitable for domestic and commercial water heating. the COP was only slightly degraded by lowering the generator temperature to 425 K. as shown in Figure 5-1.

and absorbing ﬂuid(()abs ). Figures 5-3 and 5-4 show the eﬀect of varying the critical temperature and critical pressure. Finally.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. In addition to testing the eﬀects of parameter deviation. Identical behavior . Figure 5-2 shows the eﬀect of varying the liquid speciﬁc heat at constant pressure for the refrigerant (()ref rg ). and the eﬀect on the COP was noted. the contribution of the generator temperature was also examined.7 5 T = 495 1 . but the magnitude of the COP improvement or degradation increased.7 3 T = 425 h CO P 1 . and Figure 5-5 examines the acentric factor’s eﬀect. pressure-equalizing ﬂuid (()pe ). the dashed line denotes the base case coeﬃcient of performance.7 0 1 . Figure 5-6 plots the changing COP versus the molecular mass. As the generator temperature was lowered from its optimum. The starting point for each parameter variation was the default value from the ammonia-water-butane triplet.7 2 1 . each ﬂuid property was instead individually varied.74 1 . the trend for each parameter remained the same. In each graph. respectively.

75 1.73 1.pe 1.75 1.2 5.69 1.5 2.1 6.5 3.0 2.7 6.re frg 1.75 1.0 3.73 1.75 1.0 c pl.65 3.8 5.67 1.65 1.73 COPh 1.l .71 COPh 1.1 3.0 c pl.abs Figure 5-2: COP versus cp.67 1.69 1.8 5.65 4.0 1.2 c p l.5 4.69 1.6 7.9 4.67 1.71 1.5 3.4 4.71 COPh 1.

69 1.67 1.69 1.75 1.65 415 1.75 418 421 423 426 429 432 T c.re frg 1.73 1.76 1.69 1.65 632 641 649 658 666 675 683 692 700 T c.67 1.71 COPh 1.73 COPh 1.abs Figure 5-3: COP versus Tc .pe 1.73 1.65 401 406 411 416 421 425 430 435 440 T c.71 1.67 1.71 COPh 1.75 1.

73 COPh 1.69 1.75 1.67 1.71 COPh 1.75 39 43 46 50 P c.73 1.65 130 173 215 258 300 P c.65 35 1.73 1.67 1.71 COPh 1.pe 1.re frg 1.69 1.67 1.abs Figure 5-4: COP versus Pc .77 1.75 110 115 120 125 P c.69 1.65 105 1.71 1.

65 0.80 COPh 1.35 ω 0.05 0.65 0.51 0.85 1.75 1.55 1.36 0.75 1.22 0.70 1.85 0.58 0.30 0.15 ω 0.85 1.22 0.70 1.65 0.80 COPh 1.10 0.40 pe 0.80 COPh 1.25 re frg 1.50 0.70 1.20 0.25 1.44 0.29 0.75 1.45 0.13 0.08 0.65 ω abs Figure 5-5: COP versus ω .78 1.17 0.

69 1.69 1.67 1.65 51 1.79 1.69 1.73 1.71 COPh 1.75 1.73 1.67 1.75 53 55 57 59 60 62 64 66 M re frg 1.65 16 17 18 19 20 21 M abs Figure 5-6: COP versus M .65 16 1.71 COPh 1.67 1.73 1.75 19 22 25 28 31 M pe 1.71 COPh 1.

80 Tg e n = Tg e n . In fact.75 COPh Tg e n > Tg e n . Constraints that specify the maximum and minimum temperature diﬀerences between the evaporator and the condenser/absorber must be met.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. however.o p tim u m 1. this was indeed found to be the case. was that the eﬀects of the parameters might be interrelated. and are denoted by “+” signs in the table. One potential diﬃculty with this method of optimization.o p tim u m 1.65 630 640 650 660 670 680 690 700 T c . Table 5-1 summarizes the manner in which each of the parameters must be changed in order to increase the COP. once the parameters were matched to actual ﬂuids. and the eﬀect of varying the refrigerant . This is illustrated for the critical temperature of the absorbing ﬂuid in Figure 5-7.o p tim u m 1.80 1. The magnitudes of the variations are illustrated in Figures 5-2 through 5-6.70 Tg e n < Tg e n .

1987). Unfortunately. pressure-equalizing ﬂuid. Since water has . 2000. These variations combine to actually lower the coeﬃcient of performance. For each ﬂuid type (refrigerant. 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. and the best matches were determined.. 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. hydrazine also has a higher molecular weight and a lower acentric factor.81 Table 5-1: Parameter Variation for Increased Eﬃciency Pressure-Equalizing Fluid Increase (+) Increase (+) Decrease (+) Increase (++) Increase (++) Refrigerant Absorbing Fluid Decrease (+) Decrease (++) Increase (+) Decrease (+) Increase (++) Decrease (+) Decrease (++) Increase (++) Decrease (+++) Increase (++) cp. PhysProp. the parameters were ranked in order of their greatest eﬀect on the COP.l M Pc Tc ω 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. Reid et al. The only viable alternative to water that was found in the ﬂuid search was hydrazine (H4 N2 ). 2000. and absorbing ﬂuid). Absorbing Fluid Einstein and Szilard used water as their absorbing ﬂuid.

but it is actually a pollutant that is extremely harmful to humans and the environment. For example.9 74.0263 31.424 0.l kJ kg·K 5.1922 0.842 2.69 408. in addition to satisfying the parameter requirements.97 61.5752 83.0642 32. the list of alternatives was narrowed so that only formaldehyde.382 1.89 512. and ethanol were considered.9388 80. Including this sort of consideration.069 Tc (K) 405. These are listed in Table 5-2.69 430. 2000).2818 0. Refrigerant As with the pressure-equalizing ﬂuid.0422 46.1 80.0648 46.564 0.96 Pc (bar) 112.058 36.25 0. a number of alternatives were found for ammonia.2454 0.84 101.224 2.1 78.369 3.861 unique properties.774 2.6452 cp. where.1315 0.275 0. there were a number of alternate ﬂuids found for butane. water was kept as the absorbing ﬂuid for alternative mixtures.04 490. hydrogen chloride.48 w 0.33 80 82. However. nitrogen dioxide initially appears to be a viable alternative.82 Table 5-2: Pressure Equalizing Fluids Component Ammonia Formaldehyde Methyl Amine Hydrogen Chloride Sulfur Dioxide Nitrogen Dioxide Methyl Bromide Sulfur Trioxide Methanol Ethanol M 17.8511 0. Pressure-Equalizing Fluid In contrast to the previous case. as before.857 3.272 2.79 431. Table 5-3 contains a list of these.4606 64.04 430 324. where the values of the parameters for ammonia are also given.68 513. the values . the toxicity and environmental impact of the alternatives were also examined (Environmental Defense Scorecard.19 467.0055 94.8 65.031 30.2526 0. methyl amine.112 1. methanol.

092 0.762 2.0442 80.19 365.0965 50.8 33.0373 58.805 2.0129 26.1531 0.069 42.448 2.2 of the parameters for butane (the base case ﬂuid) are also given.0379 64.04 408. were eliminated.6 89.1 36.04 373.7 58.0806 44.86 416.1531 0.28 w 0.65 42.63 3.52 48.34 402.2 369.45 61.35 Pc (bar) 37.774 1.0601 Tc (K) 425.1257 0.759 2.8 46.251 0. In order to accurately do so.314 1.631 2.059 2.61 308.413 2. such as methyl chloride.219 1.2161 0.1398 0.28 50.1409 0. toxicity was again considered.97 52.1234 46.71 56. Selection of Fluid Triplets The Patel-Teja equation of state and Panagiotopoulos and Reid mixing rules were selected to model the actual ﬂuid behavior.9119 52.1234 86.7 53.2192 0.0758 34.38 85.15 44.49 66. and certain choices.387 2.1301 0.222 cp.0648 48.5144 46.2036 0.39 400.43 375.63 50.0819 54.84 363.716 2.22 327.1873 0.183 0.1889 0.159 1.0916 42.0942 0. As outlined in the next .39 52.8 309.943 1.4875 72.411 0. As a secondary screen.61 369.1906 0.4684 40.57 488.19 2.14 370.5 49.36 460.375 2.83 Table 5-3: Refrigerants Component Butane Vinyl Fluoride Hydrogen Bromide Vinylacetylene Hydrogen Sulﬁde 2-Butyne Propylene Propane Methyl Chloride Pentane Nitrous Oxide Acetylene Ethyl Chloride Dimethyl Ether Ketene Isobutane Chlorodiﬂuoromethane Methyl Acetylene Ethyl Fluoride M 58.l kJ kg·K 2.0693 0.75 72.19 454.29 469. binary interaction parameters needed to be found for each absorbing ﬂuid/pressureequalizing ﬂuid and refrigerant/pressure-equalizing ﬂuid pair.1993 0.

once the vapor-liquid equilibrium behavior of the ﬂuid pairs was modeled. At that pressure. The various possible matches were extensively explored. Although the ideal model optimization indicated that using either methanol or ethanol as the pressure-equalizing ﬂuid would increase the COP. which resulted in fourteen alternative ﬂuid triplets. no data could be found for formaldehyde and any of the refrigerant ﬂuid alternatives. A constraint must be used that states that the saturation temperature of the pressureequalizing ﬂuid must be less than or equal to the condenser/absorber temperature . These are outlined in Figure 5-8. which also includes the base case triplet of ammonia-water-butane. For example. while there were data available for water-formaldehyde vapor-liquid equilibrium. these interaction parameters are found through correlations with experimental equilibrium data. For a water heating application. 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. the temperature of the condenser/absorber should be 325 K and the maximum temperature of the evaporator should be approximately 295 K. whichever is lower. 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.84 chapter. formaldehyde was eliminated as a pressure-equalizing ﬂuid alternative. Unfortunately. In addition to matching actual ﬂuids to parameter trends. the minimum evaporator temperature is then either the saturation temperature of the pressure-equalizing ﬂuid or the minimum boiling azeotrope of the ﬂuid pair. Therefore. parameter boundaries must also be speciﬁed. some of the alternatives had to be eliminated. The availability of this experimental data further narrowed the choices as to which alternatives could be considered.

85 Propane Ammonia Propylene Butane Pentane Methyl Amine Pentane Butane Propane Water Hydrogen Chloride Propylene Butane Propane Methanol Propylene Butane Propane Ethanol Propylene Isobutane Figure 5-8: Alternative Fluid Triplets .

14 from the corresponding states theory relates the saturation temperature and pressure to the acentric factor. fpe = F n and Tcond−abs − Tevap ≥ Tlif t Since methanol and ethanol do not meet this criterion. they were eliminated from consideration. the above constraint can be stated mathematically as: 0 1 0 1 Pc. Equation 3. frefrg = F n Tcond−abs Tc. . The eﬀect of each of the remaining ﬂuid triplets on the system performance was examined using the complex cycle model.refrg Tevap Tc.pe 0 1 fpe .refrg exp[frefrg + wrefrg frefrg ] = Pc. As stated previously.1) where 0 1 frefrg . Using that equation.pe exp[fpe + wpe fpe ] (5. the following chapter explains the bases for this model: the Patel-Teja equation of state and Panagiotopoulos and Reid mixing rules.86 minus the lift at the system pressure.

which is expressed as equation 3. It should be noted that ζc is not equal to the . Furthermore. Furthermore.2) where ζc is empirically determined. The Patel-Teja equation of state: a RT − v − b v(v + b) + c(v − b) P = (6. they added: Pc Vc Ru Tc ζc = (6.1) is clearly similar in form to the van der Waals equation. the development of the PatelTeja equation of state begins with the cubic van der Waals equation. Patel-Teja adds a third parameter (c). in addition to the constraints that (∂P/∂V )T = 0 and (∂ 2 P/∂V 2 )T = 0 at the critical point.2. which was described in Chapter III: a RT − 2 v−b v P = The van der Waals equation incorporates an intermolecular force parameter (a) and a volume correction parameter (b).87 CHAPTER VI THE PATEL-TEJA MODEL The Patel-Teja Equation of State As with the principle of corresponding states. there is an inﬂection point at the critical point.

7) . but instead corresponds to the minimum deviation in saturated liquid densities when the fugacities are equal.88 experimental value of the critical compressibility. The value of c is straightforward: Ru Tc Pc c = Ωc where (6.3) Ωc = 1 − 3ζc Determining b is slightly more complicated: Ru Tc Pc (6. and a is a function of temperature. as mentioned previously. b and c are constants.2 and 6.6) Finally.2 to the Patel-Teja equation of state.1. Single Substances Determination of the Patel-Teja Coeﬃcients In equation 6.4) b = Ωb (6. a is dependent on the temperature: 2 Ru Tc2 α Pc a = Ωa While Ωa is a constant: (6. Their values can be determined by applying the constraints of equations 3.5) The value of Ωb is the smallest positive root of 2 3 Ω3 + (2 − 3ζc )Ω2 + 3ζc Ωb − ζc = 0 b b (6.

9) Like ζc . Therefore. ζc . and F . Furthermore.8) α is a function of the reduced temperature: α = [1 + F (1 − TR )]2 (6.30982ω − 0. they determined that ζc and F can be expressed as functions of the acentric factor for nonpolar ﬂuids: ζc = 0.452413 + 1. there are four parameters that are required by the Patel-Teja equation of state: Tc .10) F = 0.89 2 Ωa = 3ζc + 3(1 − 2ζc )Ωb + Ω2 + 1 − 3ζc b (6.329032 − 0. volume.295937ω 2 Equilibrium Conditions (6. Pc . Patel and Teja calculated the values of ζc and F for thirty-eight substances (1982).0211947ω 2 (6. F is an empirically-determined constant. and .076799ω + 0. In their original paper on the equation of state.11) The emperical values of ζc and F previously discussed were determined by examining 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.

Z is the compressibility and a. As discussed in Chapter III.90 pressure: f P P ln = 0 1 v − Ru T P dP (6.12) The Patel-Teja equation of state can then be substituted into the above integral to result in the following fugacity relationship (Patel and Teja.16) In equations 6.13) (b + c)2 N = bc + 2 −1/2 (6. and temperature of the state of a substance. volume. b.15) Q= P Ru T b+c +N 2 (6. 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.14) M= P Ru T b+c −N 2 (6. 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 .16.13 through 6. 1982): f P bP Ru T Z +M a ln 2Ru T N Z+Q ln where = Z − 1 − ln Z − + (6. the Patel-Teja equation of state can also be used to determine the enthalpy and entropy.

which results in: 2 Ru Tc ∂a =− Ωa F ∂T Pc α TR (6.16. and Q are given in equations 6. mixture parameters (am . the Patel-Teja equation of state can also be used to model mixtures.21) . bm . and cm ) must be used in equation 6. The mixture parameters are a function of the component parameters and mole fractions: am = i j xi xj aij (6.17) P 1 ∂a Z + M S − S∗ = − ln − ln Ru Z − (bP/Ru T ) 2Ru N ∂T Z +Q (6. To do so. For the Patel-Teja equation of state (1982). The diﬀerential ∂a/∂T is found by taking the derivative with respect to temperature of equation 6.20) bm = i xi bi (6.18) The values of N.14 through 6. M.1 rather than the individual substance parameters.91 and pressure. the enthalpy and entropy departure functions are: H − H∗ 1 = Z −1− Ru T 2Ru T N ∂a Z +M − a ln ∂T Z +Q T (6.19) Mixtures Mixing Rules In addition to predicting the behavior of individual substances.7.

They are determined by minimizing the diﬀerence between experimentally and analytically determined equilibrium points. in addition to vapor-liquid equilibrium. Determing aij is more complicated.22) The values of bi and ci for each component can be found using equations 6. In this study. That term is a “cross-interaction parameter. the Panagiotopoulos and Reid rule was used to determine aij : √ aij = [1 − kij + xi (kij − kji)] ai aj (6. liquid-liquid equilibrium (fiL1 = fiL2 ) and vapor-liquid-liquid equilibrium (fiL1 = fiL2 = fiV ) can also exist. the fugacity is equal to (Patel and Teja.23) The parameters kij and kji are binary interaction coeﬃcients (1985). 1995): ln fi yi P = ln a v v b+b aD + (b2 + c2 + 6bc + + v−b v−b RT RT QD . The expression for the fugacity of a component in a mixture is more complicated than the expression for the fugacity of a single substance.3. Equilibrium Conditions The computationally determined equilibrium points are found by using the fugacity.5 and 6. For mixtures.” and is a function of the individual component parameters (ai and aj . respectively.92 cm = i xi ci (6. calculated using equation 6. 1982.7) and one or more binary interaction coeﬃcients. Smith. For component i.

18. b. However. since a.17 and 6. and c are now mixture .93 + b b + 3b c + 3bc + c c) + + 1 (b c2 + b2 c − b bc − c cb) QD (6.24) 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 D = (−Q) −1 2 √ 2v + b + c − −Q √ ln 2v + b + c + −Q a = −2 j k √ yj yk (1 − kjk ) aj ak − 3 yi yj (kij − kji) ai aj + √ j k √ 2 yj yk (kjk − kkj ) ak aj + 2 j √ yj [2 − kij − kji + yj (kij − kji)] ai aj j b = bi − b c = ci − c Enthalpy and Entropy The enthalpy and entropy departure functions for each component in the mixture are given by equations 6.

23: ∂aij = ∂T 2 2 Ωa. Once the substances are mixed.j (6.j TR. the enthalpy and entropy of the saturated liquid for each substance are deﬁned to be zero.iTc.7 and 6.i TR.j − Fj Tc. to determine ∂am /∂T an expression must be found for ∂aij /∂T from equations 6. At the reference point. they are mixed.i Pc. and the reference temperature is the saturation temperature of that substance at the reference pressure. The ideal gas enthalpy and entropy of each component at this point are the negatives of the departure functions. For an ideal gas. the reference pressure is the atmospheric pressure.i R2 Tc. The state of each component is then moved from the reference temperature to the actual temperature (the pressure remains at the reference condition). the components have been evaluated individually. Up to this point.94 parameters.25) The departure functions can be used to determine the enthalpy and entropy of the mixture at any point. The enthalpy of the mixture is: .j 2Tc.i Ωa. For each substance.j αj TR. the liquid or vapor composition can be determined from the fugacities.i αi TR.j R2 Tc.j Fi Tc. (1996).i Pc. now. Ideal gas speciﬁc heats were found in the DIPPR database (1999) and in Assael et al. The mixture is still treated as if it is an ideal gas at the reference pressure and system temperature. First. the change in enthalpy for that process is equal to the speciﬁc heat multiplied by the diﬀerence in temperature. The change in entropy is the speciﬁc heat multiplied by the natural logarithm of the actual temperature divided by the reference temperature. each component is evaluated as if it acted like an ideal gas at the reference temperature and pressure.

i . Pref ) + cid. .j ) − R ln (zj ) j p.g.liq (Tref. the enthalpy and entropy of a mixture at any point are: h = zi [−hdep.i + zj −sdep.g.29) These two equations can be used to ﬁnd the enthalpy and entropy for any subcooled. saturated.g.i + zj [−hdep. or superheated state. Psys .j )] j p.28) s = zi −sdep. For this transition.i )] i p. zi . which incorporates an additional term that accounts for the increase from mixing. the mixture must move from the reference pressure to the actual pressure. Pref ) + cid.j + hdep mixture (Tsys .g.liq (Tref. The entropy.95 hmix = zi hi + zj hj (6. ln (Tsys /Tref. Pref ) + cid.27) Finally.i . (Tsys − Tref.liq (Tref. zi . ln (Tsys /Tref. (Tsys − Tref. Psys . is: smix = zi si + zj sj − R[zi ln (zi ) + zj ln (zj )] (6. zj ) (6. Pref ) + cid. In summary.i ) − R ln (zi ) i p. zj ) (6.j .26) where zi and zj represent either the liquid or the vapor mole fractions of components i and j.j .liq (Tref.j + sdep mixture (Tsys . the enthalpy and entropy departure functions are calculated for the mixture at the actual temperature and pressure.

Some of the coeﬃcients were previously . a highly accurate cycle model was created. the Patel-Teja equation of state coeﬃcients were calculated from the expressions given in the previous chapter. Experimental data were gathered from a number of sources for the various ﬂuid pairs. Binary interaction parameters are found by minimizing the diﬀerences between experimentally and analytically determined vapor-liquid (or vapor-liquidliquid) equilibrium points. The Patel-Teja fugacity relationship was used to ﬁnd the calculated equilibrium data. An eﬀort was made to use data at temperatures and pressures similar to the desired system operating conditions. The EES program that describes the model can be found in Appendix C.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. 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 ). In order to use this expression for the fugacity.

08023 0.03764 0.310 0.02073 0.06934 0.03425 0.44882 0.0587 0.01588 0.076 b 0.6898 0.45653 Ωb 0.324 0.experimental Pdeviation (%) = (7.193 0.056 0.50455 0.calculated 1− N i=1 Ti.317 0.6613 0.0747 0.083 0.028 0.44602 0.7902 0.48808 0. For the second case.06510 0.02657 0.08105 0.01824 0.269 0.09038 c 0. temperature deviation was minimized: 100 N Ti. Fitting the Experimental Data One of two types of equilibrium data was available for each ﬂuid pair.6784 0.03546 0.45474 0.calculated 1− N i=1 Pi.6481 0.042 0.experimental Tdeviation (%) = (7.309 0.1) where N is the number of data points. Either the temperature was ﬁxed and the pressure varied with concentration. the following relationship was minimized: 100 N Pi. the sum of the deviation of each data .6214 0.308 Ωa 0.154 0.282 0.05437 0. or the pressure was ﬁxed and the temperature varied with concentration.071 0.04604 0.08807 known from Patel and Teja’s paper on their equation of state (1982).05236 0. For the ﬁrst case.049 0.6271 0.2) When more than one data set was available.44349 0.08179 0.43799 0. Table 7-1 lists the constant coeﬃcients for each ﬂuid.07851 0.7465 ζc 0.97 Table 7-1: Patel-Teja Coeﬃcients Fluid Water Ammonia H Chloride Methyl Amine Butane Propane Propylene Pentane F 0.05236 0. and i is each data point. to reduce the error between the experimental and computation values.319 0.078 Ωc 0.04078 0.

.123 0. For each guess value of the binary interaction parameters. The values of kij and kji were then changed.058 (Ottenweller et al. EES could not automatically ﬁnd the minimum point.025 Propane: (Ashley and Brown..057 (Gmehling et al.264 -0. and the eﬀect on the average deviation was noted. Parameter Values The kij and kji values for each ﬂuid pair are given in Table 7-2.15 0. 1972) 0..205 0. in addition to mathematically minimizing the error.058 (Ashley and Brown.. 1996) 0. Unfortunately.13 (Wilding et al.142 0.423 (Stumm et al..98 Table 7-2: Binary Interaction Parameters Pair Ammonia-Water Ammonia-Butane Ammonia-Pentane Ammonia-Propylene Ammonia-Propane Methyl Amine-Water Methyl Amine-Butane Methyl Amine-Pentane Hydrogen Chloride-Water HCl-Propane HCl-Propylene HCl-Butane kij kji Reference -0. 1994) 0.128 Butane: (Wilding et al.4 -0.283 0..1 Propane: (Wilding et al. the fugacity of the liquid and vapor phase were set equal to each other. 1996) 0.29 0. 1993) 0. 1977) -1. 1977) 0. and the pressure and temperature were calculated at the experimental concentrations.. the correlation to experimental data was visually checked. 1977) 0..057 (Gmehling et al. 1996) -0...128 (Wilding et al.18 (Brandani et al. 1943) set was minimized. 1972) 0.294 (Gmehling et al. due to solver instabilities. 1996) 0. Furthermore.15 0.283 0.. so the values of kij and kji were manually varied. 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).123 0.205 -0.

As explained earlier. which may or may not be the minimum possible temperature. the generator temperature was varied to ﬁnd the maximum COP.7 5 0 . Azeotropic pairs (Figure 7-1). For each triplet.0 0 M ole Fr a c tion M e thyl Am ine Figure 7-1: Methyl Amine-Butane. zeotropic pairs (Figure 7-2).0 5 Ex perimental Data 1 . The desired evaporator temperature ranges from 295 K to 306 K.9 5 P re s s ur e (ba r ) 2 .2 5 2 .3 5 Calc ulated V LE 2 . the equation of state coeﬃcients and entropy and enthalpy departure functions can be used to ﬁnd the cycle COP for the alternate ﬂuid triplets.2 0 0 . and vaporliquid-liquid equilibrium points (Figure 7-3) can all be modeled. the system pressure for each triplet is set such that the partial pressure of the refrigerant in the condenser/absorber is equal to the refrigerant’s saturation pressure at the temperature of the condenser/absorber. Actual Fluid Behavior Once the binary interaction parameters are found.4 0 0 . T = 288 K For most cases.99 3 .8 0 1 .6 0 0 .0 0 0 . visual inspection shows that the computational results are fairly accurate.6 5 2 . .

T = 293 K .6 0.100 320 298 Calc ulated VLE Experimental Data T e m p e ra tu re (K ) 276 254 232 210 0 0.2 0.0 E x p e rim e n tal D a ta 0 .2 0 .4 0 .4 0.8 1 M o le F ra c tio n HC l Figure 7-2: Hydrogen Chloride-Butane.0 M o le F r a c tio n Ammo n ia Figure 7-3: Ammonia-Propane.6 0 . 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 9 8 0 .8 1 .

49 18.38 1.44 1. Tevap = 295 K Triplet Ammonia-Butane-Water Ammonia-Propane-Water Methyl Amine-Pentane-Water Hydrogen Chloride-Propane-Water Hydrogen Chloride-Propylene-Water Hydrogen Chloride-Butane-Water Ammonia-Pentane-Water COP Psystem 1. are given in Table 7-3. a condenser/absorber temperature of 325 K and and evaporator temperature of 295 K. three temperature conﬁgurations were examined.41 18 1.63 1.66 21. The second conﬁguration’s (Tca = 325 K.101 Table 7-3: COP for Tca = 325 K.25 bar.25 1.61 5.52 21.39 5.78 1. Tevap = 306 K) results are in Tables 7-4.7 1.51 5.75 1.7 1. which .39 21.66 5.87 18.25 1.68 18 1.7 1. The pressure is 5.25 1. and the results for the third conﬁguration (Tca = 316 K.3 1. 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. Tevap = 295 K) are in Table 7-5.7 As outlined in the introduction.78 Table 7-4: COP for Tca = 325 K.88 5.25 1. Tevap = 306 K Triplet Ammonia-Butane-Water Ammonia-Propane-Water Methyl Amine-Pentane-Water Hydrogen Chloride-Propane-Water Hydrogen Chloride-Propylene-Water Hydrogen Chloride-Butane-Water Ammonia-Pentane-Water Methyl Amine-Butane-Water Ammonia-Propylene-Water COP Psystem 1.2 1.7 1.3 1. The results for the ﬁrst conﬁguration.

0 kg/s h1 = 134.tot = 867.4 1.62 17.51 Qg. the relationship of the COP to the various states throughout the cycle will be explored.2 kW Qca = 1307 kW m3 = 1. .46 m1 = 1.2645 Qevap = 439.2 Table 7-6: Ammonia-Water-Butane Results COPact = 1.15 kJ/kg h6 = 752.61 17.3279 xma9 = 0. The validity of the corresponding states/ideal solution model will also be reexamined.1 kJ/kg h11 = -198 kJ/kg xma7 = 0.47 kg/s mbp.75 4.1 kJ/kg h7 = -170 kJ/kg yma6 = 0.2 1.0128 provides a maximum temperature lift of 53.102 Table 7-5: COP for Tca = 316 K.76 kg/s m5 = 0.61 15 1.8 1.6 kW m7 = 1.in = 1.56 4.76 15.9957 COPid = 3.53 4. the water-ammonia-propane COP is close to the water-ammonia-butane COP.47 kg/s h2 = 58.3 1. For all three temperature cases.59 1.96 kg/s h3 = 694.3 1.1 K.7 kJ/kg xmb1 = 0.24 kg/s m10 = 0. With an evaporator temperature of 295 K and a condenser/absorber temperature of 325 K. none of the alternate ﬂuid triplets provide a better coeﬃcient of performance. 54% of this lift is used.7 1.2 kJ/kg h4 = 1519 kJ/kg h5 = 1529 kJ/kg h9 = 220. Analysis Unfortunately.6 1. with diﬀerences so small that they can be neglected.2 1. To analyze this result. Tevap = 295 K Triplet Ammonia-Propane-Water Ammonia-Butane-Water Methyl Amine-Pentane-Water Hydrogen Chloride-Propylene-Water Hydrogen Chloride-Propane-Water Ammonia-Propylene-Water Ammonia-Pentane-Water Hydrogen Chloride-Butane-Water Methyl Amine-Butane-Water COP Psystem 1.

twenty-ﬁve percent of the heat that is applied to the generator goes to the bubble pump. For that case.465 1. as can be seen in Table 7-7. more ammonia must be absorbed by the water stream in the condenser/absorber.25 88.1 912.actual 779.2 ˙ Qgen.465 0. the ammonia-water-butane and ammonia-water-pentane triplets display the most disparate COPs. the decreased pressure in the pentane case means that the concentration of ammonia is much higher in the liquid stream entering the bubble pump.2 kW. the bubble pump must receive nearly three times as much heat transfer in order to remove the remaining ammonia and circulate the liquid water. Furthermore.51 5. . Previously.509 m7 mrefrg. As a result of this.5 ˙ 0. The pentane case requires a much larger mass ﬂow rate of ammonia leaving the generator and entering the evaporator. In fact. the bubble pump heat input has been treated as a minor factor in the eﬃciency.264 Eﬀect of State Point Properties For the ﬁrst set of operating temperatures.78 258. For the ammonia-pentane mixture. There are various reasons for this degradation in the COP. and thereby desorbed in the generator.103 Table 7-7: Comparison of Refrigerant Performance Pair Ammonia-Butane Ammonia-Pentane ˙ COP P Qbubpump 1.38 1.3 ˙ ˙ 1. where the evaporator cooling capacity has been set to 439. The higher bubble pump heat transfer rate can be traced to the ammonia concentration diﬀerences between the ammonia-butane and ammonia-pentane cases.8 Pair Ammonia-Butane Ammonia-Pentane mbubp ˙ 1 2.931 mpe. but this is obviously no longer true.44 1.5 1.293 3.

3 ˙ ˙ 3. though.44 1.38 ˙ P Qbubpump 1.104 Table 7-8: Comparison of Pressure-Equalizing Fluid Performance Pair Methyl Amine-Pentane Ammonia-Pentane COP 1.6 912. This stems from the diﬀerence in molecular weight between ammonia and methyl amine. 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. Once again. The provide the same evaporator partial pressure.actual 863.2 kW.4 1.2 ˙ Qgen. Again. In this instance.7 140.78 258. the evaporator load is set to 439. the pressures and generator temperatures are comparable. more mass of pressure-equalizing ﬂuid is required since the molecular weight of methyl amine is nearly twice that of ammonia.8 Pair Methyl Amine-Pentane Ammonia-Pentane mbubp ˙ 2. The bubble pump for the ammonia-pentane mixture requires approximately twice as much heat transfer as for the methyl amine-pentane mixture. a driving force in lowering the COP is the amount of heat added to the bubble pump. 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).509 m7 mrefrg. .931 mpe. Similar results occur in both alternative temperature conﬁgurations.04 1.5 ˙ 1.264 the relative diﬀerence in concentration between the ammonia-water mixture entering the generator and the ammonia-water mixture entering the bubble pump dictates that more water must be pumped to provide the given ammonia requirement.44 1. This “parasitic pumping power” has a large inﬂuence on the COP.265 3.003 0.035 2.

Appropriate changes were made to each cycle model to reﬂect the new parameter values.50905 0. Unfortunately.52648 0. The fourth ﬂuid is an ammonia alternative with a diﬀerent molecular mass. In each case. the COP was increased as predicted in Chapter V. four theoretical ﬂuids have been created as examples.00285 Correspoding States/Ideal Solution Model Parameters To test the validity of the parameter trends indicated by the corresponding states/ideal solution model. Each of the changes and the eﬀect on the COP is summarized in Table 7-9. One parameter has been changed for each of the ﬂuids to a value that was predicted to increase the COP.0216 M to 30 from 17 1.52824 0.9 1.02204 ω to 0.02028 Pc to 50 from 37.199 1.10 from 0. and the COP was calculated for a condenser temperature of 325 K and an evaporator temperature of 295 K. .105 Table 7-9: Theoretical Fluids and the Eﬀect on the COP Base Fluid Butane Butane Butane Ammonia Parameter Alteration COP COPincrease Tc to 415 from 425. Three of the ﬂuids are a hypothetical alkane with properties similar to butane.5278 0. these properties cannot be matched to actual ﬂuids.2 1.

among those households. and. households utilize a gas water heater. water heating accounts for nearly 25% of their gas usage. and would thereby provide an increase over conventional gas water heating eﬃciency.106 CHAPTER VIII GAS WATER HEATING: AN APPLICATION AND ITS IMPLICATIONS Introduction The temperatures that were chosen for the condenser/absorber and the evaporator in this study were selected for gas water heating. In the commercial sector.S. Residential and small commercial water heating is an energy use that is often overlooked.35 Heat From Condenser/ Absorber to Tank Cond/Abs Einstein Cycle Generator Heat From Gas Flame Evaporator Heat From Ambient Air Figure 8-1: An Einstein Cycle Gas Heat Pump Water Heater . natural gas water heating requires approximately 0. Fifty-ﬁve percent of U. Conﬁguring the Einstein cycle as a gas heat pump water heater would produce hot water from ambient air conditions and a gas ﬂame. The basic principle behind this conﬁguration is shown in Figure 8-1.

and requires testing and labeling of gas and electric water heaters at these conditions (DOE 10CFR430. An improvement in the eﬃciency of these gas water heaters would reduce fossil fuel depletion. this translates into a cost of approximately $10 billion annually.95. Water Heating Eﬃciency Electric versus Gas Water Heating Residential water heating is a major energy use. Each year. 1998). For an average residential gas cost of $6. 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. and reduce greenhouse gas emissions.10 per thousand cubic feet and an average commercial gas cost of $5. The minimum eﬃciency rating for electric water heating is 0. which is 13% of the total commercial gas usage.107 quads per year. This means 92% of the energy added to water is delivered from the tank.10 per thousand cubic feet. gas water heaters contribute to global warming emissions from the carbon dioxide formed during combustion. approximately twenty-four million metric tons of carbon are emitted due to gas water heating. In addition to the fuel operating costs.92. the only losses are the stand-by losses from the stored hot water to the surroundings. the average will be taken to be the DOE recommended rating of 0.86. For an electric water heater using electric resistance heaters immersed in the tank. with the remaining 8% lost . For discussion here. with the best available being 0. The DOE estimates daily hot water demand to be 64 gallons at 135◦F with an inlet city water temperature of 58◦ F. This is shown in Figure 2. provide economic savings for the consumer.

In a gas water heater. For discussion here. so that the ﬂue eﬃciency (percentage of combustion energy being transferred to the water storage tank) is: Qtank = 66% = Eﬀwater Qgas Eﬀﬂue = heater (8.92) = 0.66.1) Therefore. The minimum eﬃciency rating for gas water heating is 0. and the best available is 0. .61.53. it is assumed that the average is the DOE recommended eﬃciency level of 0. 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. and that the absolute stand-by heat losses are same as for electric water heaters.100% Gas Water Heater Figure 8-2: Water Heater Losses to the air in stand-by losses from the tank. 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. This results in a gas ﬂue eﬃciency (percentage of gas combustion energy added to the water in the tank) of (0. 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.108 Delivered ot Water 92% Delivered Flue Loss Hot Water 34% 61% Standby Loss 8% Standby Loss 5% Electrical Energy 100% Electric Water Heater Gas Combustion Energy .61/0.66.

4) 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 assumes that 66% of the gas combustion energy is transferred to the heat pump generator: EﬀHP.water heater = heater (8.1.2) Heat transfer to the evaporator is at the relatively high temperature of 72◦ F.gas Qgen (8. the heat transfer available from the condenser/absorber for water heating relative to the heat transfer received from the gas combustion is given by: Qgen + Qevap Qtank = COPheating = ≥1 Qgen Qgen (8. which is always greater than one.gas × COPh EﬀHP.water heater = Qtank Eﬀﬂue Qtank = QHP.3) Combining equations 8. ﬁfty-percent . so it can be taken from the ambient air and is free to the consumer. residential and commercial water heating consumes approximately three quadrillion Btu of primary energy each year. 8. Savings Energy U. Using the typical 66% ﬂue eﬃciency for gas water heaters for the heat pump. In the residential sector.109 Einstein Cycle Gas Water Heating Recall that for the Einstein cycle. and 8.2.3: Qtank = Eﬀﬂue × COPh = Eﬀwater QHP.S.

Gas water heaters are already more beneﬁcial for consumers than electric resistance water heaters. Therefore.35 quads of primary energy each year. Electric heat pump water heaters provide some improvement. just as electric heat pump water heaters improve upon resistance water heaters.3 quads of energy use each year. an aﬀordably-priced gas heat pump water heater would be an improvement on existing gas water heating technology. The reduced energy consumption provides both economic savings and environmental beneﬁts. a gas heat pump water heater that uses the Einstein cycle would have no machined or moving parts. However.54 quads of energy could be saved each year. In the residential sector. their initial cost is two to three times higher than the cost of an electric water heater. so the market penetration is limited. Economic Reducing the energy consumed by water heating would provide economic savings for the consumer. it can be seen that an Einstein Heat Pump Water Heater with a heating COP of 1. while the purchase cost of a natural gas . The residential and commercial gas water heater installed base is estimated at 48 million and 1 million. Operation of an electric resistance water heater for a typical household would cost approximately $300 each year.12 quads could be saved. As previously discussed. this means that 0. In the commercial sector. This translates into 1. but due to the required electrically-driven compressor.4. This improvement would reduce gas consumption by 33%. which is 70% of the primary energy used for water heating.110 of households use natural gas water heaters. so it could be constructed out of inexpensive materials and would require no additional maintenance.5 would result in a 50% improvement over current natural gas water heating technologies. which accounts for nearly 25% of residential natural gas usage. 0. and in the commercial sector. From equation 8. gas water heaters consume 0.

10 per thousand cubic feet. and larger families would be able to save even more. A typical household would reduce their gas bill by $70 annually. it can be seen that this would be a very attractive return. Given that a gas water heater can be expected to last for 12 years (n). the average cost for natural gas is $6. equation 8. the residential sector spends over $8 billion each year on gas water heating. . With a 25% penetration of the residential gas water heating market.5 returns an IRR of 24%. The internal rate of return (IRR) is a useful quantity in evaluating the economic value of purchasing an Einstein gas heat pump water heater rather than a conventional gas water heater. IRR is calculated from: In n n=1 (1 + IRR) 12 0 = I0 + (8. Compared to a bank account (IRR ≈ 4%) or an investment in the stock market (IRR ≈ 8%). The current average retail cost of a gas water heater is between $250 and $300. resulting in an average annual cost of $190. Once the manufacturer’s gross margin of 30% and the distribution costs are included. A family of four uses approximately 320 therms per year for natural gas water heating.111 Einstein Heat Pump Water Heater would be slightly greater than that of a conventional gas water heater. lower operating costs should compensate for the extra initial purchase price.5) The initial incremental cost of an Einstein gas water heater (I0 ) is -$275. and the yearly energy savings (In ) are $70. the total cost to the consumer would be approximately $550. For a residential consumer. 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. Overall. $660 million could be saved each year.

0. Annually. To provide hot water for a year for a family of four.112 In the commercial sector. the beneﬁts enjoyed by the end-user are not aﬀected. With the Kyoto treaty of 1997. By using topdown economic models. As a result. economists have calculated the cost for reducing annual carbon emissions to be $100 to $200 per ton of carbon. a societal cost that is both heavy and politically unacceptable (Passel.. Environmental In addition to the operating costs detailed above. Furthermore. Economists have calculated that this economic cost would lead to a reduction in gross domestic production. An Einstein cycle gas heat pump water heater is an example of this type of technology. the average cost for natural gas is $5. This is approximately equal to the current cost of fossil fuels. which include numerous diﬃcult and debatable assumptions. In the residential sector.10 per thousand cubic feet. the commercial sector spends $1.46 metric tons of carbon are released from a natural gas water heater. by utilizing higher eﬃciency systems. and $600 million could be saved each year. so gas heat pump water heaters would thereby be expected to reach a higher market penetration of 33%. this sector should have better economics than the residential sector. Conversely. combustion of natural gas results in carbon emissions. 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.8 billion for natural gas water heating. global warming resulting from carbon emissions became an issue of great interest to the public. nearly 19 . 1996). meaning the eﬀective cost of energy would double. numerous studies have been published that detail the costs associated with reducing the United States’ greenhouse gas emissions to the treaty target levels. Due to the larger daily hot water usage. 1997).

3 million metric tons outlined above would result in meeting nearly 5% of that goal.335 1. Under the Kyoto agreement. In 1990.S.6 million metric tons each year.0 Figure 8-3: Residential and Commercial Natural Gas Water Heating million metric tons of carbon are released each year due to gas water heating. that number had grown to 517 million tons (DOE/EIA-0383(98)). A 25% penetration of the residential gas water heater market by an Einstein gas heat pump water heater would reduce carbon emissions by 1.0 Carbon Dioxide Emissions (Million Metric Tons Carbon) 1. must be at or below 93% of its 1990 greenhouse gas emission levels by 2008-2012. . By 1998. Annual carbon emissions from the commercial sector may also be reduced by up to 1.430 1. while over 5 million metric tons of carbon are released due to commercial gas water heating. 11% of the Kyoto target could be reached. the U.S. The total annual energy usage and emissions for gas water heaters can be seen in Figure 8-3. emitted 477 million metric tons of carbon. The annual carbon savings of 3.525 21.715 Primary Energy Consumption (Quads) 25.5 1. the U. If residential penetration increased to approach 100%.240 1985 1987 1989 1991 Year 1993 1995 1997 18.620 1.113 1.7 million metric tons.

or if over-ﬁring should be instigated. two thermostats would provide temperature feedback to determine if the heat pump alone should be operated. These . the Einstein cycle condenser/absorber would heat the water to an intermediate temperature. 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. In a conﬁguration similar to an electric water heater. In a series conﬁguration. the gas ﬂame would over-ﬁre in a direct heat transfer mode. with an external natural convection ambient heat exchanger. there are two ways that the cycle can be conﬁgured.114 Once again. Market Potential According to the Gas Appliance Manufacturers Association. the hot ﬂue gases could be used in heat recovery. For either conﬁguration.000 commercial gas water heaters were shipped in 1998. In a quick recovery conﬁguration. 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. and direct heating would then increase the temperature of the water to the ﬁnal desired level. just as a conventional water heater. Within this general framework. the Einstein cycle heat pump would heat the water to the required temperature level. over 4 million residential and 95. If the hot water level dropped below the minimum set point. it should be emphasized that this carbon savings comes with economic beneﬁts (as detailed in the previous subsection) and not costs.

With 25% of the 4 million annual units.S. While heat pumps are more expensive to purchase and install. Assuming ideal thermal insulation. the reduced electricity costs are signiﬁcant. electric heat pump water heaters pump free thermal energy from the atmosphere rather than create it. residential use (DOE/EE-0009(93)). At the end of an electric heat pump water heater’s average twelve-year lifespan. the total retail sales would be $350 million. the present value of the consumer’s total lifetime expenditures will be only $1960. 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 significant market penetration that would rise over a 10 year period to 25 percent.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. one unit of electricity will generate one unit of hot water in an electric resistance heater. all electric water heaters used in U. compared to $3120 for . twenty-four million metric tons of carbon would be saved per year. A 3% penetration would yield annual sales of $42 million annually.S. In addition to reducing carbon emissions. Essentially. Barriers An analogous case study that was performed for electric heat pump water heaters provides insight into the barriers to implementation that might be encountered (Shelton and Schaefer. at an estimated installed cost of $550. 1998). residences are electric resistance water heaters. and thereby use ﬁfty to seventy percent less electricity than resistance heaters. If each electric resistance water heater were replaced by a heat pump water heater. However. electric heat pump water heaters can also help the consumer to save money. There are currently forty million electric resistance water heaters in U.

the DOE formally suggested in 1994 that the minimum eﬃciency standard for electric water heaters be raised from 0. a savings of nearly $1200 (DOE/EE-0009(93)). Electric utilities claimed that there was an inadequate infrastructure of technicians who could install and service electric heat pump water heaters. Furthermore.86 to 1. an Einstein gas heat pump water has a number of qualities that make it more attractive than an electric heat pump water heater. 1998). obstacles from manufacturers and gas utilities would probably arise. such as water heaters. Furthermore. but would then increase its proﬁtability (DOE/EE-0009(93). In homes with electric-powered water heating. the response from utilities and manufacturers was strongly negative. Proposed Rules. 1994). this standard would effectively mandate that heat pump water heaters be installed in all new homes and that all replacement water heaters in existing houses utilize heat pumps. may outweigh the concerns expressed in 1994. As in the above case. However. Unfortunately. A DOE-mandated higher minimum eﬃciency standard would greatly aid in the commercialization of Einstein cycle gas heat pump water heaters. and that increasing the eﬃciency of appliances in the home. new considerations.89. such as the need to reduce greenhouse gas emissions. so that it . but utilities and manufacturers would as well. They also stated that the initial ﬁnancial burden was too high for many consumers. The simplicity of the unit’s construction would greatly reduce the incremental initial cost. would reduce the incentive to improve power plant eﬃciency (Paciﬁc Northwest National Laboratory. Based on the public comment session. the DOE study found that not only would consumers beneﬁt from the raised standard. Based on numbers similar to those given above. The manufacturing sector would incur some short-term retooling costs. the DOE decided not to raise the minimum eﬃciency standard.116 an electric resistance water heater. though.

not only by professionals familiar with the energy ﬁeld. Audience members at these presentations have expressed a great deal of enthusiasm for an Einstein cycle gas heat pump water heater. and is associated with genius and unique insight. 2000a-2000e). but also by students and other lay people. so marketing eﬀorts would not be limited to only certain regions. The Einstein name is widely recognized. one of the inventors of the cycle also increases its appeal. Additionally. and have been eager to learn when it might be available commercially (Schaefer. . The relatively high temperature of the evaporator also means that the Einstein cycle can successfully operate in a variety of climates. Recent presentations on the cycle at a number of universities have been strongly attended.117 would be more aﬀordable to a larger percentage of consumers.

the Einstein cycle has been investigated primarily for refrigeration applications. These values resulted in a 7.9% improvement in bubble pump performance over previously used operating parameters.6 mm. The partial internal heat exchanger in the generator was expanded to a full internal heat exchanger in order to minimize entropy generation. however. and changes were made to increase the heating coeﬃcient of performance. These changes were primarily implemented on the generator side.2. and an optimum diameter was found to be 8. the bubble pump performance was increased through selection of optimum operating parameters. Additionally. CONCLUSIONS AND RECOMMENDATIONS Summary and Conclusions Previously. The submergence ratio of the bubble pump was set to 0. An external heat exchanger was added between the generator and the condenser/absorber to improve heat recovery. and has been investigated at temperature levels that are suitable for natural gas water heating. The ﬁrst model was used to predict ﬂuid characteristic parameters which would increase the heating COP and the second model was .118 CHAPTER IX SUMMARY. The Einstein Cycle has been modeled using two separate property models: 1) a corresponding states/ideal solution property model. The cycle can also be used for heating. and 2) a Patel-Teja/Panagiotopoulos and Reid property model. The conﬁguration of the Einstein cycle was examined.

Varying the acentric factor and the critical temperature results in the largest increase in the COP.119 used to more accurately predict the behavior of the cycle using the alternative ﬂuids selected from the results of the ﬁrst model. the properties of the ﬂuid mixtures were found by utilizing Raoult’s Law and ideal solution mixing rules. Diﬀerences in the molecular weight of each of the ﬂuids causes only small to negligible changes in the COP. with the refrigerant acentric factor producing the largest eﬀect.20 to 0. corresponding states incorporates Pitzer’s acentric factor to model ﬂuid behavior. trends were observed that could increase the COP. The non-optimum generator temperatures also altered the magnitude of the changes in the COP for the parameter variations. Generator temperatures both above (up to 575 K) and below (down to 425 K) this level lowered the COP. but did not alter the observed . The ﬁrst property model uses departure functions calculated from the threeparameter theory of corresponding states to ﬁnd the properties of individual ﬂuids. Corresponding states has been found to provide accurate results for individual ﬂuid properties at pressures and temperatures away from the critical point. however. Lowering the refrigerant acentric factor from 0. molecular weight. Once the properties of the individual ﬂuids are calculated. In addition to van der Waals’ dependence on critical temperature and pressure. By varying these parameters. the generator temperature that produced the highest heating COP was 495 K. These are the critical temperature. and the speciﬁc heat at constant pressure. critical pressure. The corresponding states/ideal solution model requires only ﬁve characteristic ﬂuid parameters per ﬂuid to model the system behavior. acentric factor. but not signiﬁcantly. Corresponding states is based on the cubic equation of state ﬁrst formulated by van der Waals.08 should increase the COP by 6%. For the base case of ammonia-water-butane.

the absorbing ﬂuid. alternative ﬂuids were sought for the three Einstein cycle working ﬂuids. Increasing the refrigerant critical pressure increases the optimum system pressure. At the optimum system pressure. No viable alternative was found for water. due to computational limitations. propylene. critical 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. Experimental equilibrium data were found in the literature for each of these alternative mixtures. and acentric factor of the refrigerant aﬀects the optimum system pressure. methyl amine and hydrogen chloride were selected for study as replacements for ammonia. . In order for the cycle to operate. whichever is lower. the minimum available temperature lift must be greater than or equal to the diﬀerence in the desired condenser/absorber and evaporator temperatures. while increasing the critical temperature or acentric factor lowers the system pressure. Additionally.120 trends. Based on the results of the corresponding states/ideal solution model. the corresponding states/ideal solution model could not be optimized by varying all of the parameters simultaneously. For the pressureequalizing ﬂuid. a constraint was developed to limit the corresponding states/ideal solution search. which is needed to ﬁnd the optimum system pressure at the condenser/absorber temperature. Unfortunately. This limits the corresponding states parameter optimization to single parameter variations. Varying the critical temperature. To model the behavior of these alternatives. the Patel-Teja equation of state and Panagiotopoulos and Reid mixing rules were used. These three parameters determine the saturation pressure of the refrigerant. and pentane were chosen for study as refrigerant alternatives. Propane.

the Einstein cycle would be used as a water preheater. which would again utilize the higher temperature thermal energy available from the ﬂue vent gases. such as those developed by Panagiotopoulos and Reid. and vapor-liquid-liquid equilibrium azeotropes. the Patel-Teja equation of state can also accurately model ﬂuid mixtures. vapor-liquid equilibrium azeotropes.121 Like van der Waals and corresponding states. The Patel-Teja fugacity relations and the Panagiotopoulos and Reid mixing 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 condenser/absorber temperature is 325 K and the evaporator temperature is 295 K. Patel-Teja is a cubic equation of state. the eﬀect of using the alternative ﬂuid triplets on the cycle performance was evaluated. In the third operating conﬁguration. propane. the Patel-Teja equation of state can predict the behavior of individual ﬂuids. with an evaporator temperature of 295 K and a condenser/absorber temperature of 316 K. Three operating conditions were examined. The Patel-Teja/Panagiotopoulos and Reid property model demonstrated that none of the alternative refrigerants or pressure-equalizing ﬂuids improved the COP. This conﬁguration can produce 125◦ F water from ambient conditions (ﬂue gases could be used to help to maintain the evaporator at 72◦ F). but the remaining alternatives actually degraded . Using ﬂuid parameters such as critical temperature and critical pressure. For the ﬁrst case. Excellent agreement was achieved for zeotropes. One alternate refrigerant. In conjunction with mixing rules. Using the binary interaction parameters and the other characteristic ﬂuid parameters. The binary interaction parameters were varied to match the calculated equilibrium states with experimental data. but the evaporator temperature is increased to 306 K. produced COPs comparable to those of the original ammonia-water-butane mixture. The condenser/absorber temperature remains the same for the second operating conﬁguration.

the Einstein cycle has a COP of 1. 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 properties of those ﬂuids were altered to exactly match the improved parameters of the corresponding states model. 1. an Einstein cycle gas heat pump water heater would cut the operating costs of a conventional gas . ammonia-water-propane and methyl amine-waterpentane are acceptable alternatives that do not signiﬁcantly lower the COP. With a heating COP of 1. It appears possible that ammonia-water-butane may be the ideal ﬂuid triplet for the Einstein cycle. the heat input to the bubble pump is raised to a level that can seriously degrade the COP. For a set evaporator load. the cycle conditions were compared for ﬂuid combinations that resulted in disparate COPs. To test the validity of the indicated trends of the corresponding states model.88 for the second conﬁguration. However. it was found that the maximum temperature lift does not provide the highest COP.5 for the ﬁrst operating conﬁguration.122 the COP.76 for the third. When more water must be pumped by the bubble pump. It was found that the pressure of the system aﬀects the absolute pressure-equalizing ﬂuid concentration in the water. the best system performance occurs at a pressure such that the partial pressure in the condenser/absorber is the saturation pressure of the refrigerant.5 from the ﬁrst operating conﬁguration. Using either ammonia-water-butane or ammonia-water-propane as the working ﬂuids. This aﬀects the required water mass ﬂow per unit of ammonia circulated. The hypothetical ﬂuids each increased the COP. but to a lesser degree than that predicted by the corresponding states/ideal solution model. Across all alternative cases. and 1. three hypothetical refrigerants and one hypothetical pressure-equalizing ﬂuid were also modeled using the Patel-Teja equation of state.

That eﬃciency level would result in yearly economic savings of $70 and environmental savings of 0. Nondimensionalizing the parameters and application of nonlinear optimization solver techniques may also prove beneﬁcial. The carbon emission reductions from widespread implementation of Einstein cycle gas heat pump water heaters would meet nearly 11% of that goal. $600 million and 1. must be at or below 93% of its 1990 greenhouse gas emission levels by 2008-20012. that means that 75 million metric tons of carbon emissions must be eliminated. The level of potential COP improvement. In the commercial sector. appears to be relatively small. At a hypothetical 100% market penetration.4 million metric tons of carbon per year.15 metric tons of carbon for an average family. 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. Recommendations A more robust corresponding states model computer program may be able to overcome the property optimization limitations encountered in this study. and 3) through the enhanced marketing potential of a cycle named after Albert Einstein.7 million metric tons of carbon could be saved annually. 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.6 billion dollars and 6. While an Einstein cycle gas heat pump water heater appears to have a large market potential. alternate conﬁgurations for the . When used as a gas heat pump water heater. there are barriers to implementation. Currently. Additionally.123 water heater by 33%. the national savings would be $2. however. The Kyoto agreement states that the U.S.

Finally. Capillary-driven ﬂow will also be of importance on a microscopic scale. Multistage Einstein cycles could also be investigated. and a compressor’s machined moving parts increase the failure rate. A higher evaporator temperature raises the COP and increases the number of potential ﬂuid triplets. however. the continuum assumption is discarded. On the microscale. the Einstein cycle is a natural candidate for miniaturization.124 evaporator should be examined. the viability of creating a mesoscopic or microscopic Einstein refrigeration cycle could be studied. microscopic vapor-compression cycles have been developed for a variety of applications. Recently. so the importance of boundary properties must be explored. 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. The heat transferred from the condenser/absorber of one cycle could be used to power the generator of another cycle. Since it is a completely sealed system with no moving parts. . This would increase the generator heat input temperature and improve the ideal COP. The Einstein cycle eliminates the need for a mechanical compressor.

125 APPENDIX A GENERATOR PROGRAMS Generator Conﬁguration 1 $INCLUDE amwatbut.T=T_1.x=0) P1w|s=pressure(WATER.x=0) Peb|s=pressure(R600.5*P_conv "Finding the Pressure of the Stream Entering the Generator (P_1)" T_e=289.9 x_ae=0.T=T_e.T=T_e.Entering the Generator" P1a|s=pressure(AMMONIA.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) .txt "Specified Points" m_dot_1=1 T_1=315 "K" T_2=T_1 T_3=375 P_conv=convert(bar.45 Pea|s=pressure(AMMONIA.T=T_1.x=0) P_e=x_ae*(Pea|s-Peb|s) + Peb|s P_1=Pea|s*x_ae "Point 1 .kPa) P=4.

T_ref_w) + u_fg_w s_a2=s_0_a + s_fg_a + c_p_f_a*ln(T_2/T_ref_a) .Vapor Leaving" P2a|s=pressure(AMMONIA.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 .T=T_2.Solution Leaving" P3a|s=pressure(AMMONIA.T=T_3.T_ref_a) h_w1=P_1*v_f_w + u_0_w + c_v_f_w*(T_1 .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) .x=0) P3w|s=pressure(WATER.x=0) "Raoult’s law and fugacities" 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 xm_w2=(x_w2*m_w)/(x_w2*m_w+x_a2*m_a) ym_w2=(y_w2*m_w)/(y_w2*m_w+y_a2*m_a) xm_a2=(x_a2*m_a)/(x_w2*m_w+x_a2*m_a) ym_a2=(y_a2*m_a)/(y_w2*m_w+y_a2*m_a) "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=T_3.x=0) P2w|s=pressure(WATER.R_w*ln(P_w2/P_ref_w) h_2=xm_a2*h_a2+xm_w2*h_w2 s_2=xm_a2*s_a2+xm_w2*s_w2 "Point3 .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 .x=0) "Raoult’s law and fugacities" .T=T_2.

kPa) P=4.45 .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 xm_w3=(x_w3*m_w)/(x_w3*m_w+x_a3*m_a) ym_w3=(y_w3*m_w)/(y_w3*m_w+y_a3*m_a) xm_a3=(x_a3*m_a)/(x_w3*m_w+x_a3*m_a) ym_a3=(y_a3*m_a)/(y_w3*m_w+y_a3*m_a) "Properties" h_a3=P*v_f_a + u_0_a + c_v_f_a*(T_3 .9 x_ae=0.5*P_conv "Finding the Pressure of the Stream Entering the Generator (P_1)" T_e=289.T_ref_w) s_a3=s_0_a + c_p_f_a*ln(T_3/T_ref_a) s_w3=s_0_w + c_p_f_w*ln(T_3/T_ref_w) h_3=xm_a3*h_a3+xm_w3*h_w3 s_3=xm_a3*s_a3+xm_w3*s_w3-(xm_a3*R_a*ln(xm_a3) +xm_w3*R_w*ln(xm_w3)) "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) Generator Conﬁguration 2 $INCLUDE amwatbut.T_ref_a) h_w3=P*v_f_w + u_0_w + c_v_f_w*(T_3 .txt "Specified Points" m_dot_1=1 P_conv=convert(bar.

Vapor Leaving" T_2=T_1 P_2=P P2a|s=pressure(AMMONIA.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) 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 .x=0) P1w|s=pressure(WATER.T=T_1.x=0) P_e=x_ae*(Pea|s-Peb|s) + Peb|s P_1=Pea|s*x_ae T_1=315 "K" "Point 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 .T=T_e.128 Pea|s=pressure(AMMONIA.T=T_1.x=0) P2w|s=pressure(WATER.T_ref_a) h_w1=P_1*v_f_w + u_0_w + c_v_f_w*(T_1 .T=T_e.x=0) "Raoult’s law and fugacities" x_w2=(P_2-P2a|s)/(P2w|s-P2a|s) y_w2=(P2w|s/P_2)*x_w2 x_a2=1-x_w2 y_a2=1-y_w2 .x=0) Peb|s=pressure(R600.T=T_2.Entering the Generator" P1a|s=pressure(AMMONIA.T=T_2.

T_ref_a) h_w3=P_3*v_f_w + u_0_w + c_v_f_w*(T_3 .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) .T_ref_a) + u_fg_a h_w2=R_w*T_2 + u_0_w + c_v_g_w*(T_2 .R_w*ln(P_w2/P_ref_w) h_2=xm_a2*h_a2+xm_w2*h_w2 s_2=xm_a2*s_a2+xm_w2*s_w2 "Point3 .T_ref_w) s_a3=s_0_a + c_p_f_a*ln(T_3/T_ref_a) s_w3=s_0_w + c_p_f_w*ln(T_3/T_ref_w) h_3=xm_a3*h_a3+xm_w3*h_w3 .x=0) P3w|s=pressure(WATER.x=0) "Raoult’s law and fugacities" x_w3=(P_3-P3a|s)/(P3w|s-P3a|s) 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 xm_w3=(x_w3*m_w)/(x_w3*m_w+x_a3*m_a) ym_w3=(y_w3*m_w)/(y_w3*m_w+y_a3*m_a) xm_a3=(x_a3*m_a)/(x_w3*m_w+x_a3*m_a) ym_a3=(y_a3*m_a)/(y_w3*m_w+y_a3*m_a) "Properties" h_a3=P_3*v_f_a + u_0_a + c_v_f_a*(T_3 .Solution Leaving Lower CV/Entering SHX" T_3=375 P_3=P P3a|s=pressure(AMMONIA.T=T_3.129 P_a2=y_a2*P_2 P_w2=y_w2*P_2 xm_w2=(x_w2*m_w)/(x_w2*m_w+x_a2*m_a) ym_w2=(y_w2*m_w)/(y_w2*m_w+y_a2*m_a) xm_a2=(x_a2*m_a)/(x_w2*m_w+x_a2*m_a) ym_a2=(y_a2*m_a)/(y_w2*m_w+y_a2*m_a) "Properties" h_a2=R_a*T_2 + u_0_a + c_v_g_a*(T_2 .T=T_3.

T_ref_w) s_a4=s_0_a + c_p_f_a*ln(T_4/T_ref_a) s_w4=s_0_w + c_p_f_w*ln(T_4/T_ref_w) h_4=xm_a4*h_a4+xm_w4*h_w4 s_4=xm_a4*s_a4+xm_w4*s_w4-(xm_a4*R_a*ln(xm_a4) +xm_w4*R_w*ln(xm_w4)) "Point 5 .130 s_3=xm_a3*s_a3+xm_w3*s_w3-(xm_a3*R_a*ln(xm_a3) +xm_w3*R_w*ln(xm_w3)) "Point4 .T_ref_a) h_w5=P_5*v_f_w + u_0_w + c_v_f_w*(T_5 .T_ref_w) s_a5=s_0_a + c_p_f_a*ln(T_5/T_ref_a) s_w5=s_0_w + c_p_f_w*ln(T_5/T_ref_w) h_5=xm_a5*h_a5+xm_w5*h_w5 .x=0) P5w|s=pressure(WATER.T=T_5.T_ref_a) h_w4=P_4*v_f_w + u_0_w + c_v_f_w*(T_4 .Solution Leaving SHX" T_4=T_1 P_4=P xm_a4=xm_a3 xm_w4=xm_w3 "Properties" h_a4=P_4*v_f_a + u_0_a + c_v_f_a*(T_4 .T=T_5.Solution Leaving SHX internally" P_5=P P5a|s=pressure(AMMONIA.x=0) "Raoult’s law and fugacities" x_w5=(P_5-P5a|s)/(P5w|s-P5a|s) 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 xm_w5=(x_w5*m_w)/(x_w5*m_w+x_a5*m_a) ym_w5=(y_w5*m_w)/(y_w5*m_w+y_a5*m_a) xm_a5=(x_a5*m_a)/(x_w5*m_w+x_a5*m_a) ym_a5=(y_a5*m_a)/(y_w5*m_w+y_a5*m_a) "Properties" h_a5=P_5*v_f_a + u_0_a + c_v_f_a*(T_5 .

x=0) "Raoult’s law and fugacities" x_w6=(P_6-P6a|s)/(P6w|s-P6a|s) 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 xm_w6=(x_w6*m_w)/(x_w6*m_w+x_a6*m_a) ym_w6=(y_w6*m_w)/(y_w6*m_w+y_a6*m_a) xm_a6=(x_a6*m_a)/(x_w6*m_w+x_a6*m_a) ym_a6=(y_a6*m_a)/(y_w6*m_w+y_a6*m_a) "Properties" h_a6=R_a*T_6 + u_0_a + c_v_g_a*(T_6 .131 s_5=xm_a5*s_a5+xm_w5*s_w5-(xm_a5*R_a*ln(xm_a5) +xm_w5*R_w*ln(xm_w5)) "Point 6 .T_ref_w) + u_fg_w s_a6=s_0_a + s_fg_a + c_p_f_a*ln(T_6/T_ref_a) .T=T_6.x=0) P6w|s=pressure(WATER.T=T_6.T_ref_a) + u_fg_a h_w6=R_w*T_6 + u_0_w + c_v_g_w*(T_6 .R_w*ln(P_w5/P_ref_w) h_6=xm_a6*h_a6+xm_w6*h_w6 s_6=xm_a6*s_a6+xm_w6*s_w6 "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" Q_dot_g=m_dot_6*h_6+m_dot_3*h_3-m_dot_5*h_5 m_dot_5=m_dot_6+m_dot_3 .R_a*ln(P_a5/P_ref_a) s_w6=s_0_w + s_fg_w + c_p_f_w*ln(T_6/T_ref_w) .Vapor Entering the SHX" T_6=T_5 P_6=P P6a|s=pressure(AMMONIA.

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m_dot_5*xm_a5=m_dot_6*ym_a6+m_dot_3*xm_a3 T_bar_g_s=Q_dot_g/(m_dot_6*s_6+m_dot_3*s_3-m_dot_5*s_5)

Generator Conﬁguration 3

$INCLUDE amwatbut.txt "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_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 - 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)

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{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) CALL fluidmix(xm_a2,xm_w2,h_a2,h_w2,s_a2,s_w2,R_a,R_w:h_2,s_2) "Point3 - Solution Leaving Generator/Entering Internal Hxgr" CALL raoul(T_3,P:x_a3,x_w3,xm_a3,xm_w3,y_a3,y_w3,ym_a3, ym_w3,P_a3,P_w3) CALL fluprop(P,T_3,T_ref_a,v_f_a,c_v_f_a,c_p_f_a,u_0_a, s_0_a:h_a3,s_a3) CALL fluprop(P,T_3,T_ref_w,v_f_w,c_v_f_w,c_p_f_w,u_0_w, s_0_w:h_w3,s_w3) CALL fluidmix(xm_a3,xm_w3,h_a3,h_w3,s_a3,s_w3,R_a,R_w:h_3,s_3) "Point 4 - Solution Leaving Internal/Entering External Hxgr" xm_a4=xm_a3 xm_w4=xm_w3 CALL fluprop(P,T_4,T_ref_a,v_f_a,c_v_f_a,c_p_f_a,u_0_a, s_0_a:h_a4,s_a4) CALL fluprop(P,T_4,T_ref_w,v_f_w,c_v_f_w,c_p_f_w,u_0_w, s_0_w:h_w4,s_w4) CALL fluidmix(xm_a4,xm_w4,h_a4,h_w4,s_a4,s_w4,R_a,R_w:h_4,s_4) "Point 5 - Solution Leaving External Hxgr" xm_a5=xm_a3 xm_w5=xm_w3 CALL fluprop(P,T_5,T_ref_a,v_f_a,c_v_f_a,c_p_f_a,u_0_a, s_0_a:h_a5,s_a5) CALL fluprop(P,T_5,T_ref_w,v_f_w,c_v_f_w,c_p_f_w,u_0_w, s_0_w:h_w5,s_w5) CALL fluidmix(xm_a5,xm_w5,h_a5,h_w5,s_a5,s_w5,R_a,R_w:h_5,s_5) "Point 6 - Vapor Leaving" CALL raoul(T_6,P:x_a6,x_w6,xm_a6,xm_w6,y_a6,y_w6,ym_a6, 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,

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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} m_dot_2=m_dot_6+m_dot_3 m_dot_2*xm_a2=m_dot_6*ym_a6+m_dot_3*xm_a3 0=m_dot_5*h_5-m_dot_4*h_4+m_dot_1*h_1-m_dot_2*h_2 Q_dot_g=m_dot_6*h_6+m_dot_4*h_4-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 g a=2.0942909 c v f a=4.2377115 c v g a=1.6060936 m a=17.030 P ref a=101.32 R a=0.4881973 c p f b=2.4305380 c p g b=1.6581138 c v f b=2.2874990 c v g b=1.5150747 m b=58.124 P ref b=101.32 R b=0.1430390 c p f w=4.6397774 c p g w=1.9486486 c v f w=4.1782731 c v g w=1.4871443 m w=18.015 P ref w=101.32 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 w=2087.4236029 v f w=0.0010433 s 0 w=1.3063770 s fg w=6.0509762

u fg a=1292.2284431 u fg b=348.8636657 v f a=0.0014677 s 0 a=0.1212995 s fg a=5.7236373 raoul.lib v f b=0.0016631 s 0 b=0.3498070 s fg b=1.4167022

PROCEDURE raoul (T,P:x1,x2,xm1,xm2,y1,y2,ym1,ym2,P1,P2)

u0.s0.sfg.015 P1|s=pressure(AMMONIA.s2.T=T.cp.Pref.u0.s0:h.xm2.03 mw2=18.Tref) s=s0 + cp*ln(T/Tref) END gasprop.R1:h.lib PROCEDURE gasprop(P.cv.v.lib PROCEDURE fluidmix(xm1.h1.T.135 mw1=17.Tref) + ufg s=s0 + sfg + cp*ln(T/Tref).s1.lib PROCEDURE fluprop(P.ufg.s) h=P*v + u0 + cv*(T .T.cp.T=T.R1*ln(P/Pref) END ﬂuidmix.R2:h.cv.s) .s) h=R1*T + u0 + cv*(T .Tref.h2.R1.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.Tref.x=0) P2|s=pressure(WATER.

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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 $INCLUDE $INCLUDE $INCLUDE

cst_sat.LIB cst_h_vap.LIB cst_h_liq.LIB 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)

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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

Pcw.Tcw.Tcw.wb:1/Pcb) CALL raoul2(T7.xmw8.Tref_rw. Tgen) T9=Tgen Tcontrol=(Tcon+0.hw8:h8) .h0a:ha8) CALL fluprop2(T8.Ma. ’F’.Tca.cpla.xmw7.ha7.Tca.Mw.5 cpla=5.64 R=8. xma7.cplw.hw7:h7) xma8=xma7 xmw8=xmw7 T8=T10-3 m8=m7 CALL fluprop2(T8. ’F’.Pa7.Tca.h0a:ha7) CALL fluprop2(T7.xw7.ha8.h0w:hw8) CALL fluidmix(xma8. Tcon) T7=Tcon TevapF=72 TevapF=converttemp(’K’. ’F’.1)/Tcb CALL cst_sat(Tcontrol.wa:1/Pca) CALL cst_sat(Tref_rb.31434 water=1 ammonia=2 butane=3 TconF=125 TconF=converttemp(’K’.ymw7.xmw7.ww:xa7.cpla.139 cplw=4.Tcw.h0w:hw7) CALL fluidmix(xma7.yw7.Tref_ra.yma7.32 cplb=2.Tref_ra.ya7.wb:P/Pcb) "Sets System Pressure" m9=1 CALL cst_sat(Tref_rw.Tref_rw.Pw7) CALL fluprop2(T7.wa.Pca.Pa3.cplw.ww:1/Pcw) CALL cst_sat(Tref_ra. Tevap) Tgen=425 TgenF=converttemp(’K’.

h0w.h0a.hw5:h5) T11=Tcon m11=m9 CALL raoul2(T11.xmw9.ymw9.xmw11.xmw9.cpla.xmbca.yw9.Tref_rw.xbca.Tca.Tref_rw.h0a:ha10) CALL fluprop2(T10.Mb.Tref_ra.Pw5.Ma.Pcw.cplw:hw5) CALL fluidmix(yma5. xma11.hw11:h11) Qext2=m9*(h10-h11) Qext1=Qext2 xma10=xma9 xmw10=xmw9 m10=m9 CALL fluprop2(T10.Tref_rw.yma11.Pbca) xmb1=ymbca CALL raoul2(T1ca.h0w:hw10) CALL fluidmix(xma10.Pa11. xma9.Ma.yma9.h0a:ha9) CALL fluprop2(T9.cpla.ha5.Tcw.Pw5) CALL gasprop2(T5.wa.ha10.ymw11.Tcw.cplw.P.wa.Tca.Pcb.wa.h0a:ha11) CALL fluprop2(T11.cpla.Pca.cplw.Tca.h0w:hw11) CALL fluidmix(xma9.Tref_ra.ybca.wa.ymw5.xb1.ww:xa11.xw5.Pw9) CALL fluprop2(T9.Ma.Mw.Tcb.Tca.xmw9.Tref_ra.xw9.Mw.ya11.yw11.Tcw.Pca.Ma.Pa5.xw11.Tca.Pca. .P.ha9.yaca. xma5.ha11.Pcb.hw10:h10) Qint=m9*(h9-h10) Qg = m10*h10 + m5*h5 -m8*h8 m8*xma8 = m5*yma5 + m9*xma9 m8=m9+m5 CALL raoul2(Tcon.cpla:ha5) CALL gasprop2(T5.Tca.Tcb.Pcw.Ma.Mw.ya5.Ma.Tref_rw.Pca.Mb. xmaca.hw9:h9) T5=T8 CALL raoul2(T5.h0w:hw9) CALL fluidmix(xma9.wb:xaca.Pcw.Tca.Tca.xmw10.Paca.wa.Tcw.yma5.ymw5.ya9.yw5.Tref_ra.wb:xa1.Pca.P.ww:xa9.Tca.Pcw.P.Tcw.wa.140 Qext1=m7*(h8-h7) CALL raoul2(T9.ymbca.Tcw.Pw11) CALL fluprop2(T11.ymaca.ww:xa5.xmw5.Pca.ww.Pa9.cplw.P.Tcw.Pa5.Mw.

Tcw.h0a:ha1) CALL fluprop2(T1.Tca.xmb1.wa.Mw.wa.Ma.Tcb.P.Mw.cplb:hb3p) CALL fluidmix(yma3p.xmw4.h0b:hb1) CALL fluidmix(xma1.cpla:ha4v) CALL gasprop2(T4.Tca.Ma.Tca.Tca.h0a.Tref_rb.cplw:hw4v) CALL fluidmix(yma4.ww:xa4.Ma.xmw4.cpla.xmb3p.Pca.Tref_rb.Pa4.ya1.ymw4.xmb2.Tcw.cpla.Pca.hb2p:h2p) CALL gasprop2(T4p.Tca.yw4.yma2p.ya3p.yb1.ha4v.Tcb.Tca.h0w:hw4l) CALL fluidmix(xma4. xma3p.cplb.xmb2p.Tca.h0w.cpla:ha3p) CALL gasprop2(T3p.Tcb.Pa3p.ha2p.cpla.Pa2p.Tcb.ymb3p.Tca.ww.ya4. xma2p.Pca.xw4.wa.h0b:hb2p) CALL fluidmix(xma2p.ymw4.Tcb.Tref_ra.wb:xa2p.xmb1.P.Pw4) CALL fluprop2(T4.ymb1.cpla.P.ymb3p.xmb2p.Tca.ha2.ymb2p.141 xma1.cplw.Ma.cpla:ha4p) h4p=ha4p CALL raoul2(T3p.Tcb.h0b:hb2) CALL fluidmix(xma2.Pa3p.Mb.Pcw.Tref_rw.yb3p.Tcw.Pa1.Tref_rw.Pw4.xb2p.Pcb.h0a:ha2p) CALL fluprop2(T2p.Tref_ra.h0a:ha2) CALL fluprop2(T2.Pcb.wa.Tref_ra.ha1.Tref_ra.hb1:h1) T2p=Tevap T3p=T2p T4p=T2p CALL raoul2(T2p.wa.Pca.Tca.Pb3p) CALL gasprop2(T3p.yma4.yma1.h0a.Pca.Mb.Tref_rb.yma3p.Pa4.Pcw.Tref_ra.Tref_ra.ha4l.hw4l:h4l) CALL gasprop2(T4.h0a:ha4l) CALL fluprop2(T4.wa.ya2p.xb3p.cplb.Pb2p) CALL fluprop2(T2p.Tref_ra.Pb3p.Pcb.P.hb2:h2) T4=T2 CALL raoul2(T4.hb3p:h3p) xma2=xma1 xmb2=xmb1 m2=m1 CALL fluprop2(T2.Mb. xma4.yb2p.h0b.cplb.Pca.Ma.Ma.wb.ha3p.hw4v:h4v) .Tref_rb.wb:xa3p.Pb1) T1=Tcon CALL fluprop2(T1.h0a.

Tcb.Tcb.Ma.ymb6.xmb3.xb3.Tca.Tref_rb.P.Ma.cplb:hb6) CALL fluidmix(yma6.yb3.yma3.cplb:hb3) CALL fluidmix(yma3.m4*h4v = m3p*h3p .Pb3.Pca.Pb3) CALL gasprop2(T3.Mb.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) .m2p*h2p Qe = m3*h3 .wa.hb3:h3) m2+m3p=m2p+m3 m2*xmb2+m3p*ymb3p=m2p*xmb2p+m3*ymb3 m3p=m2p+m4p m3p*yma3p=m2p*xma2p+m4p m3*h3 .Tca.ymb3.m2*h2 .m2*h2 .wb.ya3.m4p*h4p .ha3.wa.Tref_rb.Pcb.Tca.cpla:ha6) CALL gasprop2(T6.ha6.142 {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.wa.Pca.ymb3. xma3.Mb.h0b.Pcb.Pca.Ma.Tcb.Pcb.Pa3.m4*h4v m6=m3 yma6=yma3 ymb6=ymb3 T6=T5 CALL gasprop2(T6.Pb3.cpla:ha3) CALL gasprop2(T3.Tref_ra.Mb.h0a.h0a.h0b.Pa3.Pa3.wb.wb:xa3.Tref_ra.

01)*(lookup(’honevap’.row_num.28862*ln(Tr) + 0.143 Ideal Solution Model Libraries cst sat.(6.w:Pr) Pr := exp(5.29) IF (col_num<1) THEN h_0_liq := lookup(’hzeroliq’.col_num) hdepliq := h_0_liq + w*h_1_liq ENDIF END cst h vap.col_num) h_1_liq := lookup(’honeliq’.1) .((Pr-0.92714 .row_num.29) IF (col_num<1) THEN h_0_vap := (Pr/0.01)/0.row_num.1) .13.2518 .Pr.01)*(lookup(’honeliq’.lib PROCEDURE cst_h_liq(Tr.((Pr-0.row_num.row_num.row_num.1) .row_num.09648/Tr) .6875/Tr) .01)*(lookup(’hzerovap’.row_num.01)/0.lib PROCEDURE cst_sat(Tr.row_num.lib PROCEDURE cst_h_vap(Tr.lookup(’hzeroliq’.w:hdepvap) col_num := Pr*100 row_num := 100*(Tr-0.2)) h_1_liq := lookup(’honeliq’.01)*(lookup(’hzeroliq’.row_num.1)) hdepvap := h_0_vap + w*h_1_vap ELSE .4721*ln(Tr) + 0.1) .w:hdepliq) col_num := Pr*100 row_num := 100*(Tr-0.lookup(’honeliq’.2)) hdepliq := h_0_liq + w*h_1_liq ELSE h_0_liq := lookup(’hzeroliq’.169347*(Tr^6) + w*(15.Pr.1)) h_1_vap := (Pr/0.(15.43577*(Tr^6))) END cst h liq.1.

xm2.144 h_0_vap := lookup(’hzerovap’.col_num) hdepvap := h_0_vap + w*h_1_vap ENDIF END ﬂuidmix.h1.row_num.lib PROCEDURE fluidmix(xm1.row_num.h2:h) h=xm1*h1+xm2*h2 END .col_num) h_1_vap := lookup(’honevap’.

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APPENDIX C

PATEL-TEJA MODEL PROGRAMS

EES Program

$include $include $include $include $include $include $include $include P=5.25

Pteosambtl.LIB Pteosambtv.LIB Pteosawl.lib Pteosawv.lib ptabvlehsv.LIB ptawvlehsv.LIB ptamwtsc.LIB ptamhsv.LIB

{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 CALL ptabvlehsv(T3,P,xa3,ya3:xam3,yam3,xbm3,ybm3,hv3,hl3,sv3,sl3, vl3,vv3,fal3,fav3,fbl3,fbv3) 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 CALL ptabvlehsv(T2,P,xa2,ya2:xam2,yam2,xbm2,ybm2,hv2,hl2,sv2,sl2, vl2,vv2,fal2,fav2,fbl2,fbv2) {State 6: Super-Heated Ammonia-Butane leaving PC} T6=T5-pinch65 pinch65=0 ya6=ya3 xa6=xa3 CALL ptabvlehsv(T6,P,xa6,ya6:xam6,yam6,xbm6,ybm6,hv6,hl6,sv6,sl6, vl6,vv6,fal6,fav6,fbl6,fbv6) {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) CALL ptamwtsc(T8,P,xa8:h8,s8) Qdump1=m5*(hv5a-hv5)

lib PROCEDURE pteosambtl(T.s10) 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.25 Tc_a=405.8 Tr_a=T/Tc_a F_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^.148 Qget1=m8*(h8 .P.627090 Zeta_a=.6 Pc_a=112.s_depl) k_aa=0 k_bb=0 R = 8.f_ibl.P. xb_mass.v_ml.5))^2 a_a=a_Tc_a*alpha_a*Omega_1a .xb.k_ab.xa_mass.314/100000 {m^3*bar/mol K} {ammonia} omega_a=.h_depl.xa10:h10.k_ba:f_ial.hl7) Qdump2=m10*(h10-h11) Qdump1+Qdump2=Qget1 Qg=m10*h10+m9v*hv9+m5a*hv5a-m8*h8 CALL ptamwtsc(T10.xa.

678389 Zeta_b=.5*(1-k_ab+(k_ab-k_ba)*xa) a_bb=a_b a_ba=(a_b*a_a)^.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^.309 Omega_2b=0.2 Pc_b=38 Tr_b=T/Tc_b F_b=.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) .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))^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 Ma=((b_a+c_a)/2-Na)*P/(R*T) Qa=((b_a+c_a)/2+Na)*P/(R*T) {butane} omega_b=.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)^.199 Tc_b=425.

5*cos(phi/3+4.5*(1-k_ab+1-k_ba+(k_ba-k_ab)*xb) ap_4b=2*xb*a_b+xa*(a_b*a_a)^.150 C_m=c_mx*P/(R*T) N_m=(b_mx*c_mx+((b_mx+c_mx)/2)^2)^.5*(k_ba-k_ab)) ap_3a=2*xa*xb*(a_a*a_b)^.5*(1-k_ab)+xb*xb*a_b +xb*xa*(a_b*a_a)^.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) .5*cos(phi/3) yr3=2*(-A_cubic/3)^.5)^(1/3) N_cubic=(-B_cubic/2-(D_cubic)^.5*(k_ab-k_ba) +xb^2*xa*(a_b*a_a)^.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)^.18879020479) yr2=2*(-A_cubic/3)^.5*(1-k_ba)) ap_2=-3*(xa^2*xb*(a_a*a_b)^.5*cos(phi/3+2.5) yr1=2*(-A_cubic/3)^.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_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))^.

03 {ammonia kg/kmol} mwb=58.5)*ln((2*v_ml+(b_mx+c_mx)-(-Q)^.5)/(2*v_ml +(b_mx+c_mx)+(-Q)^.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 .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)) 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) +(ap_a*D1_l)/(R*T)+a_mx/(R*T)*(F_1al)-ln(Z_ml)) 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.

5*F_b/(2*(Tr_b)^.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.5)))/(2*(Tr_b)^.k_ab. ya_mass.s_depv) k_aa=0 k_bb=0 R = 8.25 Tc_a=405.6 Pc_a=112.P.5*Tc_a) -(aTcab*F_b*(1+F_a*(1-Tr_a^.5) dabsrdT=-(Omega_1b*R^2/Pc_b)^.5)) dabdT=(Omega_1b*R^2*Tc_b/Pc_b)*(-F_b*alpha_b^.5 +dabsrdT*a_a^.314/100000 {m^3*bar/mol K} {ammonia} omega_a=.yb_mass.5)*xa*xb*(1-k_ab+(k_ab-k_ba)*xa) +xb*xb*dabdT*(1-k_bb)+(daasrdT*a_b^.8 Tr_a=T/Tc_a F_a=.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)))/(2*(Tr_a)^.h_depv.5*Tr_b^(-.5*Tr_a^(-.152 daabdT=-(aTcab*F_a*(1+F_b*(1-Tr_b^.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) .627090 Zeta_a=.yb.5*F_a/(2*(Tr_a)^.5)) daasrdT=-(Omega_1a*R^2/Pc_a)^.5*Tc_b) daadT=(Omega_1a*R^2*Tc_a/Pc_a)*(-F_a*alpha_a^.f_ibv.282 Omega_2a=.ya.5 +dabsrdT*a_a^.k_ba:f_iav.v_mv.lib PROCEDURE pteosambtv(T.

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 Ma=((b_a+c_a)/2-Na)*P/(R*T) Qa=((b_a+c_a)/2+Na)*P/(R*T) {butane} omega_b=.5))^2 a_a=a_Tc_a*alpha_a*Omega_1a 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)^.2 Pc_b=38 Tr_b=T/Tc_b F_b=.199 Tc_b=425.309 Omega_2b=0.5*(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 .678389 Zeta_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)^.153 alpha_a=(1+F_a*(1-Tr_a^.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*cos(phi/3+2.5*cos(phi/3) yr3=2*(-A_cubic/3)^.5*(k_ba-k_ab) ap_4a=2*ya*a_a*(1-k_aa)+yb*(a_a*a_b)^.09439510239) Z_mv=yr1-pp/3 Z_ml=yr2-pp/3 Zr3=yr3-pp/3 .5) yr1=2*(-A_cubic/3)^.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*(ya*ya*a_a*(1-k_aa)+ya*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*(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*(1-k_ba+1 -k_ab+(k_ab-k_ba)*ya) 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*cos(phi/3+4.5*(1-k_ba)) ap_2=-3*(ya^2*yb*(a_a*a_b)^.5*(1-k_ab) +yb*yb*a_b*(1-k_bb)+yb*ya*(a_b*a_a)^.18879020479) yr2=2*(-A_cubic/3)^.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*(k_ab-k_ba) ap_3b=2*yb*ya*(a_b*a_a)^.

03 {ammonia kg/kmol} mwb=58.5)) F_1av=v_mv/(Q*D_v)*(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_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) +(ap_a*D1_v)/(R*T)+a_mx/(R*T)*(F_1av)-ln(Z_mv)) f_iav2=ya*P phi_iav=(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_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) +(ap_b*D1_v)/(R*T)+a_mx/(R*T)*(F_1bv)-ln(Z_mv)) f_ibv2=yb*P phi_ibv=(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)) mwa=17.5)*ln((2*v_mv+(b_mx+c_mx)-(-Q)^.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 Q=-(b_mx^2+6*b_mx*c_mx+c_mx^2) D_v=v_mv^2+v_mv*(b_mx+c_mx)-b_mx*c_mx D1_v=(1/(-Q)^.124 {butane kg/kmol} mwmv=mwa*ya+mwb*yb .5)^(1/3) N_cubic=(-B_cubic/2-(D_cubic)^.155 ENDIF IF D_cubic>0 THEN M_cubic=(-B_cubic/2+(D_cubic)^.5)/(2*v_mv +(b_mx+c_mx)+(-Q)^.

f_iwl.25 Tc_a=405.314/100000 {m^3*bar/mol K} {ammonia} omega_a=. h_depl.lib PROCEDURE pteosawl(T.5*Tc_b) daadT=(Omega_1a*R^2*Tc_a/Pc_a)*(-F_a*alpha_a^.26328 k_wa=-0.5+dabsrdT*a_a^.6 Pc_a=112.5*Tr_b^(-.5)))/(2*(Tr_a)^.5*F_a/(2*(Tr_a)^.5)) daasrdT=-(Omega_1a*R^2/Pc_a)^.5+dabsrdT*a_a^.P.8 Tr_a=T/Tc_a F_a=.5)))/(2*(Tr_b)^.v_ml.5*Tr_a^(-.5*F_b/(2*(Tr_b)^.s_depl) k_aa=0 k_ww=0 k_aw=-0.xw.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.5 daabdT=-(aTcab*F_a*(1+F_b*(1-Tr_b^.5)) dabdT=(Omega_1b*R^2*Tc_b/Pc_b)*(-F_b*alpha_b^.5) dabsrdT=-(Omega_1b*R^2/Pc_b)^.xw_mass.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^.627090 .156 ya_mass=ya*mwa/mwmv yb_mass=1-ya_mass aTcab=((a_Tc_a*Omega_1a)*(a_Tc_b*Omega_1b))^.5*Tc_a) -(aTcab*F_b*(1+F_a*(1-Tr_a^.xa:f_ial.29368 R = 8.5)*ya*yb* (1-k_ab+(k_ab-k_ba)*ya)+yb*yb*dabdT*(1-k_bb) +(daasrdT*a_b^.xa_mass.

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))^2 a_a=a_Tc_a*alpha_a*Omega_1a 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)^.157 Zeta_a=.2 Tr_w=T/Tc_w F_w=.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) .344 Tc_w=647.5 Ma=((b_a+c_a)/2-Na)*P/(R*T) Qa=((b_a+c_a)/2+Na)*P/(R*T) {water} omega_w=.3 Pc_w=221.269 Omega_2w=0.06934 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^.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^.282 Omega_2a=.689803 Zeta_w=.

5*(1-k_wa+1-k_aw +(k_aw-k_wa)*xa) ap_a=ap_1+ap_2+ap_3a+ap_4a 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) 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 Q_r=(c_2^2-3*c_3)/9 R_r=(2*c_2^3-9*c_2*c_3+27*c_4)/54 .5*(k_aw-k_wa) +xw^2*xa*(a_w*a_a)^.5*(1-k_aw) +xw*xw*a_w*(1-k_ww)+xw*xa*(a_w*a_a)^.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 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*(1-k_aa)+xa*xw*(a_a*a_w)^.5*(1-k_wa)) ap_2=-3*(xa^2*xw*(a_a*a_w)^.5*(k_wa-k_aw) ap_4a=2*xa*a_a*(1-k_aa)+xw*(a_a*a_w)^.5*(k_wa-k_aw)) ap_3a=2*xa*xw*(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)^.158 a_aw=(a_a*a_w)^.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*(k_aw-k_wa) ap_3w=2*xw*xa*(a_w*a_a)^.

5)*(cos(theta_r/3))-c_2/3 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*F_w/(2*(Tr_w)^.5)*ln((2*v_ml+(b_mx+c_mx)-(-Q)^.5*Tc_w) daadT=(Omega_1a*R^2*Tc_a/Pc_a)*(-F_a*alpha_a^.5)) Z_ml=-2*(Q_r^.5)/(2*v_ml +(b_mx+c_mx)+(-Q)^.5*Tr_w^(-.5)*xa* xw*(1-k_aw+(k_aw-k_wa)*xa)+xw*xw*dawdT*(1-k_ww) .03 {ammonia kg/kmol} mww=18.5*Tc_a) -(aTcaw*F_w*(1+F_a*(1-Tr_a^.5*Tr_a^(-.5 daawdT=-(aTcaw*F_a*(1+F_w*(1-Tr_w^.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) f_ial=xa*P*exp(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_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)) mwa=17.015 {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) dawsrdT=-(Omega_1w*R^2/Pc_w)^.5)) daasrdT=-(Omega_1a*R^2/Pc_a)^.159 theta_r=arccos(R_r*Q_r^(-1.5*F_a/(2*(Tr_a)^.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)))/(2*(Tr_a)^.5)) dawdT=(Omega_1w*R^2*Tc_w/Pc_w)*(-F_w*alpha_w^.5)))/(2*(Tr_w)^.5+dawsrdT*a_a^.

yw_mass.v_mv.25 Tc_a=405.f_iwv.314/100000 {m^3*bar/mol K} {ammonia} omega_a=.8 Tr_a=T/Tc_a F_a=.6 Pc_a=112.06934 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^.s_depv) k_aa=0 k_ww=0 k_aw=-0. h_depv.P.5+dawsrdT*a_a^.ya:f_iav.yw.26328 k_wa=-0.lib PROCEDURE pteosawv(T.282 Omega_2a=.ya_mass.29368 R = 8.160 +(daasrdT*a_w^.627090 Zeta_a=.5))^2 a_a=a_Tc_a*alpha_a*Omega_1a 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) .5)*xw*xa*(1-k_wa+(k_wa -k_aw)*xw) {mixture enthalpy and entropy departures: 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.

689803 Zeta_w=.5*(1-k_aw+(k_aw-k_wa)*ya) a_ww=a_w*(1-k_ww) a_wa=(a_w*a_a)^.2 Tr_w=T/Tc_w F_w=.3 Pc_w=221.5 Ma=((b_a+c_a)/2-Na)*P/(R*T) Qa=((b_a+c_a)/2+Na)*P/(R*T) {water} omega_w=.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))^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)^.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*(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 M_m=((b_mx+c_mx)/2-N_m)*P/(R*T) Q_m=((b_mx+c_mx)/2+N_m)*P/(R*T) .161 Na=(b_a*c_a+((b_a+c_a)/2)^2)^.344 Tc_w=647.

162 ap_1=-2*(ya*ya*a_a*(1-k_aa)+ya*yw*(a_a*a_w)^.5*(k_wa-k_aw)) ap_3a=2*ya*yw*(a_a*a_w)^.5*(1-k_aw) +yw*yw*a_w*(1-k_ww)+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)) F_1av=v_mv/(Q*D_v)*(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_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 .5*(.5)/(2*v_mv +(b_mx+c_mx)+(-Q)^.5)*ln((2*v_mv+(b_mx+c_mx)-(-Q)^.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*cos(theta_r/3) +(3^.5*(k_aw-k_wa) +yw^2*ya*(a_w*a_a)^.5*(k_aw-k_wa) ap_3w=2*yw*ya*(a_w*a_a)^.5)) Z_mv=2*(Q_r)^.5/2)*sin(theta_r/3))-(c_2/3) v_mv=Z_mv*R*T/P Q=-(b_mx^2+6*b_mx*c_mx+c_mx^2) D_v=v_mv^2+v_mv*(b_mx+c_mx)-b_mx*c_mx D1_v=(1/(-Q)^.5*(1-k_wa+1 -k_aw+(k_aw-k_wa)*ya) ap_a=ap_1+ap_2+ap_3a+ap_4a 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) 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 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*(1-k_wa)) ap_2=-3*(ya^2*yw*(a_a*a_w)^.

5 daawdT=-(aTcaw*F_a*(1+F_w*(1-Tr_w^.5)) daasrdT=-(Omega_1a*R^2/Pc_a)^.5+dawsrdT*a_a^.5*F_a/(2*(Tr_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) +(ap_a*D1_v)/(R*T)+a_mx/(R*T)*(F_1av)-ln(Z_mv)) 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)) mwa=17.5*Tc_a) -(aTcaw*F_w*(1+F_a*(1-Tr_a^.015 {water kg/kmol} 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) 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)))/(2*(Tr_w)^.5)*yw*ya*(1-k_wa +(k_wa-k_aw)*yw) {mixture enthalpy and entropy departures: 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 .5*Tc_w) daadT=(Omega_1a*R^2*Tc_a/Pc_a)*(-F_a*alpha_a^.5)))/(2*(Tr_a)^.03 {ammonia kg/kmol} mww=18.5) dawsrdT=-(Omega_1w*R^2/Pc_w)^.5)) dawdT=(Omega_1w*R^2*Tc_w/Pc_w)*(-F_w*alpha_w^.5*F_w/(2*(Tr_w)^.5*Tr_w^(-.5)*ya *yw*(1-k_aw+(k_aw-k_wa)*ya)+yw*yw*dawdT*(1-k_ww) +(daasrdT*a_w^.5*Tr_a^(-.5+dawsrdT*a_a^.

f_ibv.f_ibl.k_ba:f_iav.lib PROCEDURE ptabvlehsv(T.k_ab.1402 CALL pteosambtl(T.sml.94/mwa sia=c_pa*ln(T/Tra)/mwa+siar hibr=22669/mwb hib=c_pb*(T-Trb)/mwb+hibr sibr=82.164 ptabvlehsv.xb.P. yb_mass.487+.ya_mass.108e-4*T^2+-2.97/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) .s_depl) CALL pteosambtv(T.3313*T+-1.xa.8 Trb=272. xb_mass.ya.314 {kJ/kmol-K} k_ab=0.02383*T+1. hmv.P.smv.f_ial.v_mv.h_depv.xa_mass.yb.707e-5*T^2+-1.822e-9*T^3 {J/mol*K} Tra=238.P.h_depl.2692 k_ba=0.f_iav.v_ml.xa.f_ibv) R=8.ya_mass.v_mv.03 {ammonia kg/kmol} mwb=58.yb_mass.k_ba:f_ial.ya:xa_mass.124 {butane kg/kmol} mwml=xa*mwa+xb*mwb mwmv=ya*mwa+yb*mwb {Ideal Gas Enthalpy and Entropy} c_pa=27.k_ab.185e-8*T^3 {ideal gas} c_pb=9.s_depv) {Molecular weights} mwa=17.3 Pref=1 hiar=23184/mwa hia=c_pa*(T-Tra)/mwa+hiar siar=96.31+.v_ml.f_ibl.hml.xb_mass.

03 {ammonia kg/kmol} mww=18.v_mv.v_mv.xw.f_iwl.f_ial.yw_mass.hml.ya:f_iav.707e-5*T^2+-1.f_iav.f_iwl.24+.yw.055e-5*T^2+-3.596e-9*T^3 {J/mol*K} Pref=1 Tra=238.sml.P.ya_mass.ya:xa_mass.31+.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} .314 {kJ/kmol-K} CALL pteosawl(T.lib PROCEDURE ptawvlehsv(T.xw_mass.xa_mass.xw_mass.xa:f_ial.02383*T+1.f_iwv) R=8.015 {water kg/kmol} mwv=ya*mwa+yw*mww mwl=xa*mwa+xw*mww {Ideal Gas Enthalpy and Entropy} c_pa=27.165 +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.P. h_depv.s_depv) mwa=17.v_ml.f_iwv. hmv.ya_mass.001924*T+1.v_ml.5 hiar=23184/mwa hia=c_pa*(T-Tra)/mwa+hiar siar=96.8 Trw=372.smv.185e-8*T^3 {ideal gas} c_pw=32.s_depl) CALL pteosawv(T.yw_mass.xa.94/mwa sia=c_pa*ln(T/Tra)/mwa+siar hiwr=40761/mww hiw=c_pw*(T-Trw)/mww+hiwr siwr=109. h_depl.P.

xa:hml.001924*T+1.94/mwa sia=c_pa*ln(T/Tra)/mwa+siar hiwr=40761/mww hiw=c_pw*(T-Trw)/mww+hiwr siwr=109.xa:f_ial.s_depl) mwa=17.31+.8 Trw=372.166 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.055e-5*T^2+-3.P.24+.015 {water kg/kmol} mwl=xa*mwa+xw*mww {Ideal Gas Enthalpy and Entropy} c_pa=27.707e-5*T^2+-1.xw.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)) .314 {kJ/kmol-K} CALL pteosawl(T.5 hiar=23184/mwa hia=c_pa*(T-Tra)/mwa+hiar siar=96.596e-9*T^3 {J/mol*K} Pref=1 Tra=238.xa_mass.v_ml.xw_mass.03 {ammonia kg/kmol} mww=18. h_depl.f_iwl.185e-8*T^3 {ideal gas} c_pw=32.02383*T+1.sml) R=8.

94/mwa si=c_pa*ln(T/Tra)/mwa+sir omega_a=.vv) mwa=17.707e-5*T^2+-1.185e-8*T^3 Patm=1 Tra=238.282 Omega_2a=.6 Pc_a=112.P:hl.02383*T+1.vl.hv.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 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^.lib PROCEDURE ptamhsv(T.03 {kg/kmol} R = 8.8 Tr_a=T/Tc_a F_a=.sv.25 Tc_a=405.8 hir=23184/mwa hi=c_pa*(T-Tra)/mwa+hir sir=96.314/100000 {m^3*bar/kmol K} c_pa=27.31+.sl.5 Ma=((b_a+c_a)/2-Na)*P/(R*T) Qa=((b_a+c_a)/2+Na)*P/(R*T) c_1a=1 c_2a=(Ca-1) c_3a=(-2*Ba*Ca-Ba^2-Ba-Ca+Aa) .167 END ptamhsv.627090 Zeta_a=.5))^2 a_a=a_Tc_a*alpha_a*Omega_1a 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)^(1/3) ycubic1=Mcubic+Ncubic ycubic2=-.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*cos(phi/3+2.09439510239*0) ycubic2=2*(-A_cubica/3)^.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 .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*(Mcubic+Ncubic) ycubic3=-.5*cos(phi/3+2.5*cos(phi/3+2.5)^(1/3) Ncubic=(-B_cubica/2-D_cubica^.5) ycubic1=2*(-A_cubica/3)^.09439510239*1) ycubic3=2*(-A_cubica/3)^.09439510239*2) 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^.

169 hv=hi+hdepv/mwa sl=si+sdepl/mwa sv=si+sdepv/mwa END .

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DuPont. on January 13.D. Laura’s M. in English and a B. 1997.A. 1973. Laura attended Rice University in Houston. NASM’s ﬁrst interactive gallery. and homebrewing.S. Illinois. She held in summer internships at the National Air and Space Museum in Washington. D. where she was a resident of Wiess College. The Woodlands. In September 1995. Upon graduation.S. Andrew is receiving a Ph. Laura designed and created a longitudinal wave device for inclusion in How Things Fly. in Mechanical Engineering in May 1995. During her time at the Air and Space Museum.. research at Georgia Tech was supported by NSF. Maryland. she spent three months traveling through Europe by train. and Gaithersburg. and was raised in Springﬁeld. In her spare time. thesis focused on developing an analytical mean temperature diﬀerence relationship for refrigerant mixtures that have been designated as replacements for ozonedepleting CFCs and HCFCs. Laura enjoys reading. Maryland. Laura married Andrew James Schaefer on June 21. Laura’s M. . ASME. in 1991.176 VITA Laura Schaefer was born Laura Michelle Atkinson in Danville. She is the oldest of three children. and Ph. and ASHRAE. Laura graduated from Thomas Wootton High School in Rockville. Texas. Illinois. Laura entered graduate school at the Georgia Institute of Technology. gardening. and at Lawrence Livermore National Lab in California. She received a Master of Science degree in December 1997.C. in Operations Research from Georgia Tech’s School of Industrial and Systems Engineering.D. Texas. Laura received a B.S.