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THE USE OF AMMONIUM CARBAMATE AS A

HIGH SPECIFIC THERMAL ENERGY DENSITY


MATERIAL FOR THERMAL MANAGEMENT OF
LOW GRADE HEAT
Thesis
Submitted to
The School of Engineering of the
University of Dayton

In Partial Fulfillment of the Requirements for


The Degree of
Master of Science in Chemical Engineering

By
Joel Edward Schmidt
Dayton, OH
August 2011

THE USE OF AMMONIUM CARBAMATE AS A HIGH SPECIFIC THERMAL


ENERGY DENSITY MATERIAL FOR THERMAL MANAGEMENT OF LOW
GRADE HEAT

Name: Schmidt, Joel Edward


APPROVED BY:

Kevin J. Myers, D.Sc., P.E.


Advisory Committee Chairman
Professor, Chemical and Materials
Engineering Department

Douglas S. Dudis, Ph.D.


Research Advisor
Principal Research Chemist
Air Force Research Laboratory

Robert J. Wilkens, Ph.D., P.E.


Committee Member
Associate Professor, Chemical and
Materials Engineering Department

John G. Weber, Ph.D.


Associate Dean
School of Engineering

Tony E. Saliba, Ph.D.


Dean, School of Engineering
& Wilke Distinguished Professor

ii

ABSTRACT

THE USE OF AMMONIUM CARBAMATE AS A HIGH SPECIFIC THERMAL


ENERGY DENSITY MATERIAL FOR THERMAL MANAGEMENT OF LOW
GRADE HEAT

Name: Schmidt, Joel Edward


University of Dayton
Research Advisor: Dr. Douglas Dudis

The specific energy storage capacities of phase change materials (PCMs) increase
with temperature, leading to a lack of thermal management (TM) systems capable of
handling high heat fluxes in the temperature range from 20C to 100C. State of the art
PCMs in this temperature range are usually paraffin waxes with energy densities on the
order of a few hundred kJ/kg or ice slurries with energy densities of the same magnitude.
However, for applications where system weight and size are limited, it is necessary to
improve this energy density by at least an order of magnitude. The compound ammonium
carbamate (AC), [NH4][H2NCOO], is a solid formed from the reaction of ammonia and
carbon dioxide which endothermically decomposes back to ammonia and carbon dioxide
in the temperature range of 20C to 100C with an enthalpy of decomposition of 2,010
kJ/kg. Various methods to use this material for TM of low-grade, high-flux heat have
iii

been evaluated including: bare powder, thermally conductive carbon foams, thermally
conductive metal foams, hydrocarbon based slurries, and a slurry in ethylene glycol or
propylene glycol. A slurry in glycol is a promising system medium for enhancing heat
and mass transfer for TM. Small-scale system level characterizations of AC in glycol
have been performed and results indicate that AC is indeed a promising material for TM
of low-grade heat. It has been shown that pressures on the order of 200 torr will achieve
rapid decomposition and thermal powers of over 300 W at 60C have been found,
demonstrating the capability of AC.

iv

I would like to dedicate my work to my father and mother and thank them for all of the
support they have always given me and for serving as an example to follow. I know that
without them I would not have completed this process.

ACKNOWLEDGEMENTS

I would first like to thank the Air Force Research Laboratory for providing the funding
for this work as well as extensive technical expertise. This work was performed at the
Thermal Sciences and Materials Branch in the Materials and Manufacturing Directorate
of the Air Force Research Laboratory at Wright Patterson Air Force Base. I would
specifically like to thank Dr. Douglas Dudis (AFRL/RXBT) for serving as the research
advisor for the thesis work and Dr. Karla Strong (AFRL/RXBT) for assuring the funding
was in place for the project. Additionally, I would like to thank Dr. Douglas Miller
(AFRL/RXBT) for all of his assistance with the effort. Dr. Soumya Patnaik
(AFRL/RZPS) and Stephen Emo (AFRL/RZPS) provided great collaborations and advice
for the project, especially in scale-up efforts. I would like to thank Dr. Kevin Myers for
serving on my committee as well as for serving as my academic advisor and I would like
to thank Dr. Robert Wilkens for serving on my committee.

vi

TABLE OF CONTENTS

ABSTRACT ....................................................................................................................... iii


LIST OF FIGURES ............................................................................................................ x
LIST OF TABLES ............................................................................................................ xv
LIST OF ABBREVIATIONS AND SYMBOLS .......................................................... xviii
CHAPTER I: INTRODUCTION........................................................................................ 1
1.1. Overview of Current Thermal Management Solutions .......................................... 2
1.1.1. Phase Change Materials ................................................................................ 2
1.1.1.1. Water .................................................................................................... 2
1.1.1.2. Ammonia.............................................................................................. 3
1.1.1.3. Carbon Dioxide .................................................................................... 3
1.1.1.4. Paraffin Waxes ..................................................................................... 4
1.1.2. Chemical Reaction Systems .......................................................................... 5
1.1.2.1. Gas-Gas Reaction Systems .................................................................. 6
1.1.2.2. Gas to Solid Reactions ......................................................................... 8
1.2. Ammonium Carbamate Background ................................................................... 11
1.2.1. Kinetics of Ammonium Carbamate Formation and Decomposition .......... 14
1.2.2. Previous Uses of Ammonium Carbamate for Thermal Management ......... 15

vii

1.2.3. Ammonium Carbamate for Thermal Management ..................................... 18


1.2.4. Activation Energy of Decomposition ......................................................... 19
CHAPTER II: EXPERIMENTAL METHODOLOGY AND ANALYSIS ..................... 21
2.1. Thermal Management Proof of Concept.............................................................. 21
2.2. Thermal Conductivity .......................................................................................... 22
2.3. System Concept Evaluation ................................................................................. 24
2.3.1. Metal and Carbon Foams ............................................................................ 24
2.3.2. Liquid Ammonia Evaluation....................................................................... 26
2.3.3. Additional Solvents ..................................................................................... 29
2.3.4. Aluminum Foam ......................................................................................... 32
2.3.5. Foam Impregnation Summary .................................................................... 36
2.3.6. Heat Transfer Fluid Evaluation ................................................................... 36
2.3.6.1. Experimental Procedure ..................................................................... 38
2.3.6.2. Heat Transfer Fluid Analysis ............................................................. 39
2.3.7. Ammonium Carbamate Materials Compatibility........................................ 49
2.3.8. Hysteresis .................................................................................................... 50
2.3.9. Heat of Solution .......................................................................................... 52
2.3.10. Born-Harber Cycle for Ammonium Carbamate ....................................... 56
2.3.11. Specific Heat of Ammonium Carbamate .................................................. 57
2.4. Decomposition Pressure....................................................................................... 59
2.5. Ammonium Carbamate Decomposition Test System .......................................... 62
2.5.1. Reactor Sizing ............................................................................................. 63
2.5.2. Vacuum Pump Selection ............................................................................. 65

viii

2.5.3. Vacuum Controller...................................................................................... 66


2.5.4. Vacuum Gauge Selection............................................................................ 67
2.5.5. Temperature Measurement ......................................................................... 67
2.5.6. Tubing Selection ......................................................................................... 68
2.5.7. Simulated Thermal Load............................................................................. 68
2.5.8. Completed Experimental Apparatus ........................................................... 68
2.6. Ammonium Carbamate Decomposition Test System Experimental Work ......... 69
2.6.1. Decomposition Test System Experimental Procedure ................................ 71
2.6.2. Experimental Data Analysis ....................................................................... 72
2.6.3. Discussion of Experimental Results ........................................................... 73
2.6.4. Conclusions from Ammonium Carbamate Decomposition System Tests .. 78
CHAPTER III: CONCLUSIONS AND FUTURE WORK .............................................. 80
REFERENCE LIST .......................................................................................................... 81
APPENDIX ....................................................................................................................... 93

ix

LIST OF FIGURES

Figure 1. Dissociation pressure of ammonium carbamate ................................................ 13


Figure 2. Thermal camera image showing thermal management potential of ammonium
carbamate ........................................................................................................ 22
Figure 3. Vessel used to impregnate carbon foam with methanol and ammonium
carbamate ........................................................................................................ 31
Figure 4. Duocel aluminum foam ..................................................................................... 33
Figure 5. Ammonium carbamate in aluminum foam ........................................................ 35
Figure 6. Schematic of system used to measure the rate of decomposition of ammonium
carbamate ........................................................................................................ 38
Figure 7. Comparison of ammonium carbamate conversion in ethylene glycol, tetraglyme
and bare powder at two times solubility and 30C ......................................... 40
Figure 8. Comparison of ammonium carbamate conversion in ethylene glycol and
tetraglyme at four times solubility and 30C .................................................. 40
Figure 9. Conversion as a function of time for ammonium carbamate in ethylene glycol at
two times its solubility limit ........................................................................... 42
Figure 10. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 40C ............................ 44
x

Figure 11. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 30C ............................ 44
Figure 12. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 20C ............................ 45
Figure 13. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 10C ............................ 45
Figure 14. Comparison of different initial loadings of ammonium carbamate in ethylene
glycol at 30C ................................................................................................. 47
Figure 15. Rate of thermal power versus conversion for the decomposition of ammonium
carbamate in ethylene glycol at 30C ............................................................. 48
Figure 16. Comparison of ammonium carbamate in ethylene glycol and propylene glycol
at 30C ............................................................................................................ 49
Figure 17. Conversion as a function of time for the hysteresis measurements of
ammonium carbamate in ethylene glycol at 30C .......................................... 52
Figure 18. Heat of solution of ammonium carbamate in ethylene glycol as a function of
molality ........................................................................................................... 55
Figure 19. Born-Harber cycle for the decomposition of ammonium carbamate .............. 57
Figure 20. Temperature dependent specific heat of ammonium carbamate ..................... 59
Figure 21. Experimental decomposition pressure of ammonium carbamate powder ....... 60
Figure 22. Decomposition pressure of ammonium carbamate in ethylene glycol ............ 62
Figure 23. Ammonium carbamate decomposition test system ......................................... 63
Figure 24. Experimental test apparatus ............................................................................. 69
Figure 25. Decomposition of ammonium carbamate in reactor ....................................... 71

xi

Figure 26. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 30C ............................................................................................................ 95
Figure 27. Pressure and T for ammonium carbamate in propylene glycol at 30C ....... 95
Figure 28. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
30C ................................................................................................................ 96
Figure 29. Pressure and T for ammonium carbamate in ethylene glycol at 30C.......... 96
Figure 30. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 45C ............................................................................................................ 97
Figure 31. Pressure and T for ammonium carbamate in propylene glycol at 45C ....... 97
Figure 32. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
45C ................................................................................................................ 98
Figure 33. Pressure and T for ammonium carbamate in ethylene glycol at 45C.......... 98
Figure 34. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 50C ............................................................................................................ 99
Figure 35. Pressure and T for ammonium carbamate in propylene glycol at 50C ....... 99
Figure 36. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 55C .......................................................................................................... 100
Figure 37. Pressure and T for ammonium carbamate in propylene glycol at 55C ..... 100
Figure 38. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C .......................................................................................................... 101
Figure 39. Pressure and T for ammonium carbamate in propylene glycol at 60C ..... 101
Figure 40. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with two pressure settings ................................................................ 102

xii

Figure 41. Pressure and T for ammonium carbamate in propylene glycol at 60C at two
pressures ........................................................................................................ 102
Figure 42. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C .............................................................................................................. 103
Figure 43. Pressure and T for ammonium carbamate in ethylene glycol at 60C........ 103
Figure 44. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at two pressures ................................................................................... 104
Figure 45. Pressure and T for ammonium carbamate in ethylene glycol at 60C at two
pressures ........................................................................................................ 104
Figure 46. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C at three pressures.............................................................................. 105
Figure 47. Pressure and T for ammonium carbamate in propylene glycol at 60C at
three pressures ............................................................................................... 105
Figure 48. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at three pressures ................................................................................. 106
Figure 49. Pressure and T for ammonium carbamate in ethylene glycol at 60C at three
pressures ........................................................................................................ 106
Figure 50. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with double ammonium carbamate loading ..................................... 107
Figure 51. Pressure and T for ammonium carbamate in propylene glycol at 60C with
double ammonium carbamate loading .......................................................... 107
Figure 52. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with reused propylene glycol ........................................................... 108

xiii

Figure 53. Pressure and T for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol ................................................................................ 108
Figure 54. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with twice reused propylene glycol ................................................. 109
Figure 55. Pressure and T for ammonium carbamate in propylene glycol at 60C with
twice reused propylene glycol ...................................................................... 109

xiv

LIST OF TABLES

Table 1. Chemical reaction heat storage working pairs ...................................................... 7


Table 2. Heat of reaction of ammonium carbamate .......................................................... 18
Table 3. Energy densities of common thermal management materials ............................ 19
Table 4. Activation energy of decomposition of ammonium carbamate .......................... 20
Table 5. Thermal conductivity of ammonium salts .......................................................... 23
Table 6. Solubilities in liquid ammonia at 25C (g/100 g ammonia)85 ............................ 27
Table 7. Solubility of ammonium carbamate in methanol ................................................ 30
Table 8. Dimensions and masses of aluminum foam samples.......................................... 34
Table 9. Temperature-time records for ammonium carbamate in aluminum foam .......... 35
Table 10. Solubility of ammonium carbamate in ethylene glycol .................................... 37
Table 11. Amounts of ammonium carbamate and tetraglyme added for decomposition
studies ............................................................................................................... 41
Table 12. Error analysis for ammonium carbamate decomposition ................................. 43
Table 13. Initial amounts of ethylene glycol and ammonium carbamate to test rate of
reaction at different initial loadings of ammonium carbamate in ethylene glycol
.......................................................................................................................... 47

xv

Table 14. Hysteresis measurements of ammonium carbamate in ethylene glycol at 30C


.......................................................................................................................... 51
Table 15. Experimental details and results for the heat of solution of ammonium chloride
in water ............................................................................................................. 53
Table 16. Uncertainty in the heat of solution calculation ................................................. 54
Table 17. Experimental data for determination of heat of solution of ammonium
carbamate in ethylene glycol ............................................................................ 56
Table 18. Specific heat of ammonium carbamate96 .......................................................... 58
Table 19. Test matrix for ammonium carbamate system (see key and text for explanation)
.......................................................................................................................... 65
Table 20. Summary of ammonium carbamate test system experimental data .................. 73
Table 21. Experimental data for ammonium carbamate in propylene glycol at 30C...... 95
Table 22. Experimental data for ammonium carbamate in ethylene glycol at 30C ........ 96
Table 23. Experimental data for ammonium carbamate in propylene glycol at 45C...... 97
Table 24. Experimental data for ammonium carbamate in ethylene glycol at 45C ........ 98
Table 25. Experimental data for ammonium carbamate in propylene glycol at 50C...... 99
Table 26. Experimental data for ammonium carbamate in propylene glycol at 55C.... 100
Table 27. Experimental data for ammonium carbamate in propylene glycol at 60C.... 101
Table 28. Experimental data for ammonium carbamate in propylene glycol at 60C with
two pressure settings ...................................................................................... 102
Table 29. Experimental data for ammonium carbamate in ethylene glycol at 60C ...... 103
Table 30. Experimental data for ammonium carbamate in ethylene glycol at 60C at two
pressures ......................................................................................................... 104

xvi

Table 31. Experimental data for ammonium carbamate in propylene glycol at 60C at
three pressures ................................................................................................ 105
Table 32. Experimental data for ammonium carbamate in ethylene glycol at 60C at three
pressures ......................................................................................................... 106
Table 33. Experimental data for ammonium carbamate in propylene glycol at 60C with
double AC loading.......................................................................................... 107
Table 34. Experimental data for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol.................................................................................. 108
Table 35. Experimental data for ammonium carbamate in propylene glycol at 60C with
twice used propylene glycol ........................................................................... 109

xvii

LIST OF ABBREVIATIONS AND SYMBOLS

AC
CFCs
Cp
EG
HCFCs
k
m
mt
n
P
PCMs
Peq
PG
Q
rnet
T
TES
TM
wx
H
H
m
H
H
T
C
L m

Ammonium carbamate
Chlorofluorocarbons
Specific heat
Ethylene glycol
Hydrochlorofluorocarbons
Reaction rate constant
Mass flow rate
Total mass of solvent
Number of moles
Pressure
Phase change materials
Equilibrium pressure
Propylene glycol
Rate of heat flow
Net rate of reaction
Temperature
Thermal energy storage
Thermal management
Error of a measurement
Change in enthalpy
Heat of solution at a known molality
Standard heat of reaction
Standard heat of solution at infinite dilution
Temperature change
Apparent molal heat capacity of a solute
Correction factor for the heat of solution at infinite dilution

xviii

CHAPTER I: INTRODUCTION
Ever increasing power loads for various electronic devices have created a demand
for novel thermal management (TM) technologies to allow these devices to operate in
their ideal temperature ranges to ensure efficiency and lifetime. Most electronic devices
need to operate between 20C and 100C. Cooling these devices with air or conventional
liquid coolants can be energy intensive, require a large TM system, or even be impossible
with high thermal fluxes.1 One class of materials being explored to stabilize these devices
is graphitic foams impregnated with paraffin wax phase change materials (PCMs).1-6
However, the growth in heat fluxes and thermal loads is outpacing the capability of
conventional cooling systems.7,8 This TM problem becomes further complicated when
these high-flux loads are confined to weight and volume limited environments.
Therefore, the need exists to investigate novel methods for the TM of high heat fluxes
near room temperature.
The TM challenge which will be explored in this thesis, herein referred to as this
work, is one which has the following characteristics. The system of this work will be
capable of maintaining temperature in the range of 30C to 60C and amenable to volume
and weight limited applications. It will also operate on a reasonable time scale, defined
by a high thermal power, and will scale well. For this work all materials and proposed
system architectures will be evaluated based on these benchmark characteristics.

1.1. Overview of Current Thermal Management Solutions


Current material options for TM include traditional fluids such as water, ammonia
(NH3), or carbon dioxide (CO2), commercially available PCMs such as paraffin waxes,
alternatives like metal hydride decomposition reactions, and other chemical reaction and
sorption technologies that are in the experimental phase. This section gives a brief
overview of these various TM techniques.

1.1.1. Phase Change Materials


The following materials rely on either a solid-liquid phase change, solid-gas phase
change or liquid-gas phase change for TM.
1.1.1.1. Water
Water is the best known and most widely used PCM and TM material. For TM
purposes water has exceptional properties for its phase changes. At atmospheric pressure
the liquid-gas phase change has a latent heat of 2452 MJ/m3 or 2450 kJ/kg while its latent
heat of melting is 306 MJ/m3 or 330 kJ/kg.9 The usable temperature range can be
extended beyond the normal liquid range of 0C to 100C by using pressure to elevate the
vaporization temperature or creating water-salt solutions to lower the melting point.
Water, and to a greater extent salt solutions, suffer from corrosion issues in application.
Additionally, water is difficult to use for this work since keeping a device at room
temperature relies only on the specific heat of water and not the much higher energy
associated with vaporization.9

1.1.1.2. Ammonia
Ammonia has been used as a PCM in many industrial refrigeration applications.
Its low boiling point at one atmosphere of pressure of -33.4C makes it suitable for low
temperature refrigeration. It has a high latent heat of vaporization of 1371 kJ/kg or 935
MJ/m3 of liquid, which is an order of magnitude increase over conventional refrigerants,
making it one of the most efficient refrigerants.10,11 The major drawbacks of NH3 for use
in refrigeration are that it is both flammable and toxic in small concentrations. Toxicity is
the primary reason NH3 has not been applied to domestic cooling and only to industrial
and secondary cooling systems where some non-toxic fluid, such as water, serves as a
heat transfer medium between NH3 and the air to be cooled.12,13 However, over 100
years of use have led to numerous strategies and a history of experience in dealing with
NH3. The flammability of NH3 is also of concern, as it has a flammable range of 15% to
28% by volume in air. However, NH3 is not considered highly flammable since its flame
temperature is usually below its ignition temperature, so another fuel source must be
present for any fire to propagate.14
1.1.1.3. Carbon Dioxide
The most common use of CO2 as a phase change material is to use its solid-gas
phase change for portable cooling. The enthalpy of sublimation for CO2 is 512 kJ/kg.15
Additionally, CO2 has a long history as a refrigerant which began in 1930s and 1940s as a
refrigerant on ships. However, it fell out of use with the advent of CFCs
(chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). Carbon dioxide is being
reexamined as a refrigerant now that the detrimental environmental impacts of CFCs and
HCFCs are better understood. It can also be used as a pressurized refrigerant in the
3

temperature range of -30C to 0C by employing the evaporation of liquid CO2.16,17 An


alternative method for using CO2 as a refrigerant is to use liquid CO2 to generate a twophase flow stream of solid and gaseous CO2, which can be used to achieve cryogenic
temperatures below -56.6C on a continuous basis as opposed to using dry ice for
portable refrigeration. This system was only proposed in 2008 but carries the possibility
of using CO2 as a cryogenic refrigerant.18
For the scope of this work, the use of CO2 as a TM material is interesting since it
can be used as a solid to gas transformation but the temperatures of use are too low to be
practical.
1.1.1.4. Paraffin Waxes
Various paraffins hold potential as solid-liquid PCMs for use in electronics
because their melting temperatures can be tuned over a range for which water is not
applicable, mainly between 5C and 95C. They also have gravimetric melting enthalpies
around 200 kJ/kg, and densities of 750-800 kg/m3, which lead to volumetric melting
enthalpies of ~150 MJ/m3 for the pure materials.9 The main drawback to using paraffins
as PCMs is that they have very low thermal conductivities of around 0.2 W/mK.9 In
practice paraffins also suffer from reversibility issues which stem from a density change
associated with the solid-liquid transformation. The change in density can lead to a loss
of thermal contact with heat transfer surfaces and lower the thermal power rating.
Furthermore, paraffins require encapsulation to prevent leakage, which is an ever present
possibility.
The low thermal conductivity of paraffins inhibits heat transfer and thus leads to
long thermal charging and discharging times, making them difficult to use as PCMs.
4

However, work has been done with impregnating various types of thermally conductive
graphitic foams with paraffins to increase the thermal conductivity. A study conducted in
2000 found that impregnating compressed expanded natural graphite with paraffin
loadings from 65 wt% to 95 wt% led to thermal conductivities of 4 W/mK to 70 W/mK,
equivalent to those of the foam matrix itself. This tremendous, near two order of
magnitude increase from 0.24 W/mK for the pure material, demonstrates how this
system level approach can make a low thermal conductivity material into a system with a
good thermal power rating by increasing the thermal conductivity, something necessary
for this work.19 Other studies have found similar results, that using thermally conductive
matrices can greatly enhance the thermal conductivity of paraffin PCM systems.1,2,4 A
drawback with using a heat transfer enhancing medium is that it increases system size
and weight, which lowers the system specific properties. Additionally, as the system size
is increased, the system properties will scale linearly as the same amount of thermally
conductive medium must be used, so there is no advantage to make a larger system.
Overall, paraffins are promising PCMs. However, they do suffer from long cycle
times, reversibility issues which lead to long-term performance degradation, the liquid
phase introduces the possibility of a liquid leak in the system and paraffins are not
suitable for applications requiring high energy densities. Therefore, they are not suitable
for this work.

1.1.2. Chemical Reaction Systems


Chemical reaction systems are promising for transporting and storing heat
because the enthalpies of reactions are fundamentally higher than those of phase changes

since chemical bonds are being broken and formed. These types of materials generally fit
into two categories: those with a gas-gas reaction and those with a solid-gas reaction.
1.1.2.1. Gas-Gas Reaction Systems
There have been many chemical reaction working pairs suggested which are difficult
to use for this work because of the high operation temperatures, bulky containment
systems required for high pressures, and the corrosive or toxic nature of some of the
species.
One proposed chemical reaction system is the conversion of methane in a steam
reforming plant powered by heat from a nuclear reactor.20 The methane is reacted with
steam at 950C by the endothermic reactions in Equations 1 and 2.

CO

CO

3H
4H

H = 205.2 kJ/mol

(1)

H = 163.3 kJ/mol

(2)

The methane can then be catalytically reformed in an exothermic process by the reverse
reactions which take place at 450C and the heat used to make steam. The purpose of this
process is to react the methane at a central location to store the heat in the reaction
products and then be able to distribute the product gases and reform them in locations
where steam is needed. While impractical for the type of problem which is the focus of
this work, it shows that chemical reaction systems have a very high energy change and
are serious contenders for thermal energy storage (TES).
A similar process is the CO2 reforming-methanation cycle shown in Equation 3.
2

(3)

This process has been proposed to use a catalyzed reaction at 700C to 900C to form
the CO and H2 which are then transported to the place of use where they recombine
6

exothermically at 350C to 450C to form steam.21 The main advantage of this reaction
over methane-steam reformation is that there are no condensable species. This feature
makes the system operation much simpler and does not require the gases to be
transported at high temperature to prevent condensation.
Other possible reaction pairs proposed in the literature are listed in Table 1.22-24
All operate at too high of a temperature to be practical for this work (300C to 700C)
and many are hazardous, but collectively they provide background to the motivation for
using a chemical reaction heat transformer rather than a phase change TES material.

2
2
2
2

Table 1. Chemical reaction heat storage working pairs


Reaction
66.5 /
3
98 /
2
108 /
129 /
3

Equation
(4)
(5)
(6)
(7)

At lower temperatures from 150C to 200C the decomposition of methanol is a


candidate chemical reaction system. The reaction and enthalpy are shown in Equation 8.
95

(8)

This reaction is promising for large scale applications due to the low cost of methanol
and the relatively low temperatures required, which are still much higher than those
required by this work.
In the above reaction pairs all species are gaseous provided that condensation is
prevented. This is ideal for large scale processes since it allows for easy transportation of
the reactants and products over relatively large distances. It also presents difficulties
since the high pressure gases require expensive support equipment. While these systems

are possible for large scale operations, they are not viable for a small system or where the
system energy density needs to be maximized. Additionally, they are not practical for the
temperature range of this work. Overall, these pairs demonstrate the difficulty of
identifying a suitable system for low-grade, high-flux waste heat. The toxicity,
flammability and reactivity of the materials shown attest to the difficulty of finding a
better system and underscore the need for this work.
1.1.2.2. Gas to Solid Reactions
Gas-solid reactions are promising for energy storage and TM because of their
high specific enthalpy changes. In addition to using the high energy change from a
reaction they also benefit from a large entropy change for the solid to gas transformation
which increases their specific properties. However, many have discounted these types of
TES materials because the large change in volume makes them difficult to handle and
also makes cycling problematic.25-27 Three types of solid-gas reactions are considered:
metal hydrides, ammoniates and complete decomposition reactions.
Many solid-gas reactions are of the form of sorption with reaction. Metal hydrides
are one example of this type of system and can have very high gravimetric thermal
energy densities. There are many possible metal-hydrogen storage material systems
which have been reported elsewhere.25,28 These materials are candidates for thermal
energy storage because hydrogen is able to chemically bind to the metal, with a high
binding energy, in a process which is controlled by temperature and pressure. Much of
the research into metal hydrides is being conducted for hydrogen storage for fuel cells,
especially those on vehicles. Hydrogen storage requires minimization of the thermal load
associated with the sorption process; however, metal hydride systems with a high thermal
8

load may be good candidates for TM. The Mg/MgH2 system is well characterized with a
thermal energy storage density of 1850 kJ/kg while LiAlH4 has been reported to have an
extremely high thermal density of 4200 kJ/kg.22,29
Metal hydrides appear to be promising materials for TM applications as well as
other energy applications but they suffer from many shortcomings that need to be
addressed before they can be used. The first is that of safety. Hydrogen is dangerous to
handle because of its extreme flammability and danger of explosions. Additionally, metal
hydrides are often violently reactive to water, including atmospheric water, making their
storage a serious concern. Finally, these materials suffer from slow kinetics, poor
reversibility, a very high desorption temperature and little familiarity outside of
laboratories. For these reasons metal hydrides are still a far off goal for thermal energy
storage.
A second popular class of sorption working pairs is ammoniates which utilize
NH3 and various metal salts such as LiCl, MgCl2, PbCl2, ZnCl2, CuCl2, FeCl2 and other
period 4, 5 and 6 metal chlorides.30-32 These systems take advantage of the exothermic
reaction of the NH3 with metal salts and the endothermic desorption reaction to upgrade
waste heat to usable temperatures. While these can operate at lower temperatures than the
metal hydrides, the systems require high pressures and large masses of adsorbent
materials, which make them impractical for any application requiring a high specific
energy density at the system level. The low thermal conductivity of the sorbent salts also
presents cycling challenges. These systems generally operate above 150C and at high
pressures.32

The final type of gas-solid reaction considered is that of complete decomposition


reactions in which the precursors are solids and the only products are gases. These are
different from the various adsorption reactions since no solid is left behind, which can
present cycling challenges. This type of reaction can also present extremely high energy
densities for TM, especially at temperatures from 30C to 60C, which are the focus of
this work. Three candidate, complete decomposition reaction materials proposed here are
ammonium carbonate ((NH4)2CO3), ammonium bicarbonate ((NH4)HCO3), and
ammonium carbamate (NH2COONH4), (AC). Thermogravimetric analysis of their
decomposition (ramp rate 0.4C/minute) showed complete decomposition of AC by 60C
while ammonium carbonate and ammonium bicarbonate showed complete decomposition
by 85C.33 The heat of decomposition of ammonium carbamate is 2.01 MJ/kg while it is
1.97 MJ/kg for ammonium carbonate, and estimated to be 2.12 MJ/kg for ammonium
bicarbonate from standard heats of formation.34-36 Ammonium carbamate is clearly the
preferred material among these three for two important reasons. First, the decomposition
temperature of AC is lower than that of ammonium carbonate and ammonium
bicarbonate by 25C, which makes AC the only viable material for this work. Second AC
decomposition does not form water, which would readily condense below 100C and
pose serious problems for system operation.
Ammonium carbamate is formed from NH3 and CO2 by the reversible reaction in
Equation 9.
2

(9)

This reaction can be controlled by temperature and pressure. The reaction to form AC
and its disassociation are well documented. It is a simple reaction and fairly safe with

10

NH3 gas being the only toxic product. It is even used in a Physical Chemistry laboratory
textbook as an undergraduate student experiment to study the kinetics and
thermodynamics of a heterogeneous gas phase reaction by studying the decomposition
pressure of the material as a function of temperature and is a suggested experiment in the
Journal of Chemical Education.34,37

1.2. Ammonium Carbamate Background


Ammonium carbamate is formed by mixing NH3 and CO2. The normal
stoichiometric equation for the formation of AC was shown in Equation 9. AC has been
described in literature for over 140 years, normally as a mixture with ammonium
carbonate.38-41 It was first characterized as a mixture of salts formed with NH3, CO2 and
water. The first patent in the United States that discusses AC was granted in 1907. It
describes the use of AC as an intermediate product for making either ammonium
carbonate by treating AC with superheated steam or heated to produce ammonium
carbonate and urea.42 The next patent to reference AC, issued in 1915, claims the use of
AC to neutralize lactic acid produced in acid fermentation.43 In 1918 AC was mentioned
in a patent for petroleum refining where it was used to neutralize acid.44 By 1920 AC was
a well known industrial chemical. After this point AC was primarily used as an
intermediate in urea synthesis for fertilizers.45-47 Another industrial use of AC is in the
manufacture of metal carbamates, such as sodium carbamate (NaNH2CO2), potassium
carbamate (KCO2NH2) or calcium carbamate (Ca(NH2CO2)2) which can then be
converted into valuable products such as calcium cyanamide or potassium carbonate.48-50
AC has also found use as an agent to expand tobacco, in deicing compositions, and in the
production of melamine.51-53 In more modern patents the most prevalent use of AC is as
11

an intermediate in urea synthesis.54-56 Today the global urea production is over


100,000,000 tons annually, and AC is used as an intermediate in the process;
additionally, as of 1983 (the most recent figure available) over 4,000 tons of AC were
produced annually for other purposes.57,58 This makes AC particularly attractive for TM
applications because of its low cost and broad experience in its use and handling.
Therefore, the scope of this project is not in material development, but in the
development of a material system for a new application.
Industrially, several methods to produce AC exist. If high purity is not necessary,
the AC is normally produced in an aqueous stream. This is accomplished in a
supersaturated aqueous solution of NH3 and CO2, with NH3 content greater than 30%,
and the AC is precipitated out of the solution by cooling.59 However, this method only
has a yield of about 60% and produces a mixture of AC, ammonium carbonate and
ammonium bicarbonate; this mixture is acceptable for urea production for use in
fertilizers. A second method to produce high purity AC is to pass anhydrous CO2 and
NH3 gases through cooled vertical columns where AC forms on cooled walls. This
method has the disadvantage of requiring large cooling surfaces, due to the poor thermal
conductivity of the AC and its high heat of formation, and requires mechanical removal
of the carbamate, but does produce high purity AC.59 A third method to produce AC
industrially is to use a fluidized bed cooled below 25C with CO2 circulated as the
fluidizing agent and NH3 introduced to form AC.59 A fourth method to produce AC is to
introduce liquid NH3 and liquid CO2 together in the tip of a spray nozzle so that the AC
forms as a fine powder just outside of the nozzle. This method is reported to produce high
purity AC at nearly 100% yield.51

12

The dissociation pressure of AC as a function of temperature has been published


several times; in addition its determination is an experiment in college undergraduate
chemistry laboratories. The first study of AC dates back to 1838 as an experiment in the
equilibrium between NH3, CO2 and AC.60,61 The dissociation pressure as a function of
temperature is shown for four literature sources in Figure 1 and there is excellent
agreement among the data.34,60,62,63 These data give a good indication of the pressures
necessary to cause AC to decompose as a function of temperature. A pressure below
atmospheric is necessary for rapid decomposition since the desired temperature range for
this work is from 30C to 60C. The overhead pressure is important since it will
determine the necessary system pressure in order to cause a rapid decomposition.
1000
Egan, Potts, Potts

900

Joncich, Solka, Bower

800

Briggs and Migrdichian

Pressure (Torr)

700

Bennett, Rithie, Roxburgh, Thomson

600
500
400
300
200
100
0
10

20

30

40
Temperature (C)

50

Figure 1. Dissociation pressure of ammonium carbamate

13

60

70

1.2.1. Kinetics of Ammonium Carbamate Formation and Decomposition


At least three different mechanisms have been proposed for the formation and
disassociation of AC. The two most recent reports were made in 1988 and 1998 and are
summarized below.64,65
Claudel and Boulamri studied the reaction forming AC as well as its
decomposition and found the rate expression of the form in Equation 10.
(10)
In this equation P is the total pressure of the stoichiometric mixture of the gases, Peq is the
pressure at equilibrium conditions, and the rate constant k has the units of torr-1min-1. The
constant k depended primarily on the surface state and surface area of the reactive species
and was only a weak function of temperature. As this is a second order rate law, the
authors proposed that it is governed by the rate of crystal growth or decrease. They point
out that this is normally seen in crystal growth kinetics in solution but has also been
proposed for gas-solid reactions in the case of HCl and NH3 forming ammonium
chloride. The authors proposed that this rate is governed by Equations 11 and 12.
(11)
(12)
They suggest that the formation of carbamic acid (NH2CO2H) in the first reaction is the
limiting step. Theoretical studies have pointed to the presence of the carbamic acid
intermediate, but no direct evidence of its existence has been found.64,66-68 While this
does not invalidate this mechanism, it does allow for other possible explanations.
The most recent study on AC kinetics was published in 1998 by Ramachandran,
Halpern, and Glendening65 and summarized prior mechanistic studies. They critiqued the

14

Claudel and Boulamri64 reaction mechanism as being implausible since it breaks down
for P > Peq as it predicts that for this case the pressure would increase in time, not
decrease towards Peq. Additionally Ramachandran, Halpern, and Glendening point out
that the correlation between kobs and 1/T was poor. The authors considered two different
scenarios for the kinetic mechanism. The first mechanism involves NH3, CO2 and
carbamic acid in the gas phase. However, they found this type of mechanism to be
improbable and to lack evidence since IR analysis of the gas phase did not show any
evidence of carbamic acid. The second mechanism proposed still involved a carbamic
acid intermediate, but the carbamic acid did not leave the surface of the AC. The authors
found this mechanism to be the most promising for the reaction. In their publication they
alluded to future work on determining rate constants, but that was apparently never
published.
For the purpose of this work, knowing the exact mechanism of reaction is not
critical. Rather, establishing pressure as the primary driving force of the reaction as well
as understanding the impact that surface area will have on reaction rate is key. This
conclusion will need to be considered in any system design since a large pressure
gradient resulting from a low pressure system will be desirable to achieve a maximum
rate of reaction. It will also be desirable to process the AC to a small particle size to
maximize the surface area available for reaction.

1.2.2. Previous Uses of Ammonium Carbamate for Thermal Management


The use of AC to upgrade heat and store thermal energy has been proposed in two
previous, but unimplemented systems. Both concepts use heat from solar energy or some
other low grade heat source, such as geothermal, to decompose the AC and then store the
15

CO2 and NH3 separately. These stored gases can then be brought back together to reform
the AC, an exothermic process, to provide heat for space heating and generating steam.
Ammonium carbamate is good for this system since the gases can be stored indefinitely
and then reacted to provide heat as needed, creating an on-demand, regenerable heat
source.
The first system was presented in a patent from 1979 and was intended to use
solar energy to decompose the AC, then reform it later to take advantage of its
exothermic formation.69 The patent presents a few different operation modes. In the first
the carrier fluid is water. However, this is undesirable to the system because of the
formation of urea, which in a mixture of water, is corrosive. In the second operational
method an anhydrous heat transfer medium such as Therminol or Dowtherm is used
instead of water, avoiding urea formation and corrosion problems. The principle of
operation of the system is to dissociate AC at a temperature of 100C to 200C under
pressure using solar energy. The NH3 and CO2 are then used immediately to provide heat
at a different location or are separated using compression and stored indefinitely. The
separation is simple in principle because at a pressure of 10 atmospheres at ambient
temperature the NH3 is a liquid while the CO2 remains a gas. They can be separated
easily, the NH3 stored as a liquid, and the CO2 stored as a compressed gas. When
recombined, the heat can be used for a wide range of purposes. The authors suggest a
radiator, air heater or hot water heater. They also claim this system is advantageous
because of the low operating temperatures and the relatively low hazards associated with
AC as compared with other systems such as phosgene and carbon monoxide. However,
using a system similar to this is not practical for this work because the operating

16

temperatures of 100C to 200C are too high. Importantly, this paper elaborates a simple
method of separating the CO2 and NH3, as the patent suggests a compression to ~10
atmospheres is sufficient to separate the species.
The second system is similar to the first since it uses solar energy but is
specifically designed to use solar energy to disassociate the AC and then store the gases,
and finally use them to provide space and water heating.70 The proposed system was also
very large, enough to provide heating to a Greek settlement of 500 people for 15 winter
days. Such a large system would be used to heat 11,800 kg/hr of water from 20C to
90C by reacting 820 kg/hr of NH3 and 1060 kg/hr of CO2, the water would then be used
as the heat transfer medium. This system runs based on the same principles of the
previous patent but relies totally upon an anhydrous system to avoid urea formation.
Another distinction is that this analysis also included the idea of using CO2 that was
produced as a byproduct of fermentation or combustion processes. In this mode of
operation the NH3 was recycled and was separated using ethanol. This is a simple
separation since the solubility of NH3 in ethanol at 0C is over 20% by weight at 1
atmosphere of pressure. The NH3 can then be reacted with the CO2 in the ethanol
solution, the heat of reaction will cause all components to volatilize, then the ethanol can
be condensed and reused. The study found that using CO2 obtained from fermentation to
be the most practical since it avoided costly compression, the closed loop cycle involving
CO2 compression to be the second most desirable and that obtaining CO2 from
combustion would be the least economical due to the expensive purification required of
the effluent gas. Like the previous patent, the operating temperatures and pressures are

17

well above those required for this work, but the system does suggest an additional
separation method using inexpensive alcohols at ambient pressure.
The two aforementioned systems demonstrate that AC has been considered for
large scale, terrestrial-based thermal energy storage. However, the operating temperatures
are significantly above room temperature. Important insights that can be drawn from
these proposed systems are methods for separating the NH3 as well as the idea of using a
carrier fluid to enhance heat transfer and aid in mass transfer.

1.2.3. Ammonium Carbamate for Thermal Management


The decomposition reaction of AC is remarkable from a TM perspective since it
occurs in the desired temperature range of 30C to 60C and with a high heat of reaction
on a gravimetric basis. Table 2 gives literature values for the heat of reaction.

Table 2. Heat of reaction of ammonium carbamate


Source
(MJ/kg)
Joncich et al34
2.00
71
Janjic
2.07
Bennett63
1.96
62
Egan, Potts and Potts
2.01
Clark and Hetherington72
1.94
73
Claudel, Brousse, Shehadeh
2.05
69
Patent 4,169,499
1.99
The average of these values is 2.01 MJ/kg which was used for the purpose of this work as
the accepted heat of reaction. As a comparison the heat of vaporization of water is 2.45
MJ/kg and the heat of vaporization of NH3 is 1.3 MJ/kg. To put this on a volumetric basis
the density of the AC or of the system must be known. A single crystal analysis was
performed by Adams and Small in 1973 and gave a calculated density of 1.38 g/cm3, and
18

they measured the density to be 1.36 g/cm3.74 Bulk AC available from BASF chemicals
in 25 kg bags has a density range of 780-850 kg/m3.75 According to patent 4,567,294 the
bulk density of AC is 780 kg/m3.59 A density of 780 kg/m3 corresponds to a volumetric
energy density 1.57 GJ/m3. A comparison to other commonly used materials for TM is
given in Table 3, all volumetric measurements are based on the solid bulk density. Thus
the energy density of decomposition for the material is quite competitive and at a lower
temperature than the liquid to gas phase change of water but higher than that of NH3.
Even though the phase change of NH3 occurs at a lower temperature, the use of NH3
requires bulky pressure containment systems and presents a significant toxicity risk,
which is not encountered with solid AC.

Table 3. Energy densities of common thermal management materials


Gravimetric
Volumetric
System
Enthalpy
Enthalpy
Temperature (C)
3
Ammonium carbamate
2010 MJ/kg
1570 MJ/m
25-60
Water freezing
330 kJ/kg
306 MJ/m3
0
3
Water vaporization
2450 kJ/kg
2452 MJ/m
100
Ammonia
1371.2 kJ/kg
935 MJ/m3
-33.5
Dry Ice
571 kJ/kg
856 MJ/m3
-78.5
3
Paraffins
200 kJ/kg
150 MJ/m
5-95
Metal Hydrides
Up to 4200 kJ/kg
Varies by material
1.2.4. Activation Energy of Decomposition
The activation energy of the decomposition of solid AC has been measured by
two different groups as shown in Table 4. These values are significantly different,
however the important conclusion is that it may be possible to lower the activation energy
of decomposition through a catalyst which could increase the rate of reaction. This will
be important to maximize the rate of reaction to give the system a high power rating. No
measurements of the activation energy in solution have been reported.
19

Table 4. Activation energy of decomposition of ammonium carbamate


Source
(kJ/mol)
Janjic71
79
73
Claudel, Brousse, Shehadeh
42

20

CHAPTER II: EXPERIMENTAL METHODOLOGY AND


ANALYSIS
2.1. Thermal Management Proof of Concept
In order to demonstrate the tremendous potential of AC for TM, a thermal camera
was used to show how AC can quickly reduce the temperature of ethylene glycol (EG).
Two Erlenmeyer flasks were filled with 75 mL of EG and placed on a hot plate. Each was
heated to ~100C. Ammonium carbamate was then added to the flask on the right
through a funnel. Once the AC came in contact with the EG it vigorously decomposed
and lowered the temperature of the fluid. The images in Figure 2 show the time
progression of the temperature of the flasks with time increasing from left to right. The
first image was taken before the AC was added. There is a 10 second delay between each
image. A color of yellow corresponds to a temperature of ~100C and a color of green
corresponds to a color of ~60C. As the image progression shows the addition of the AC
lowered the temperature by over 40C within 40 seconds. It should be noted that what the
thermal camera detects is the infrared emission of the glass and not of the fluid inside the
glass. This underscores the rapid cooling of the EG since the thermal transfer between the
EG and the inner surface of the glass and then to the outer surface of the glass will delay
the visual appearance of the temperature drop. The dark red at the bottom of the images is
from the hot plate.

21

t=0s

t = 10 s

t = 20 s

t = 30 s

t = 40 s

Figure 2. Thermal camera image showing thermal management potential of ammonium


carbamate

2.2. Thermal Conductivity


An inherent problem in the use of AC as a TES system is that it has a low thermal
conductivity, though no exact value can be found in literature. A patent gives a
description for a prior process to produce AC which involves its formation from NH3 and
CO2 gases on a chilled metal surface.59 The patent states that the poor thermal
conductivity of the salt necessitates large cooling surfaces, which gives evidence to the
idea that the thermal conductivity could be problematic. The thermal conductivities of
other NH3 salts are listed in Table 5. From this table it can be assumed that the thermal
conductivity of AC is low. All thermal conductivities are reported as close to room
temperature and pressure as possible

22

Table 5. Thermal conductivity of ammonium salts


Compound
Source
Thermal Conductivity
(W/mK)
NH4Br
Ross and
~1
Anderson76
~0.8
NH4I
Ross and
Anderson76
NH4Cl
Ross and
~1.5
Anderson76
CaCl2 (powder)
Wang et al.77
0.31
CaCl2 (pellet)
Wang et al.77
0.11
77
CaCl2 2NH3 (powder) Wang et al.
0.37
77
CaCl2 4NH3 (powder) Wang et al.
0.42
CaCl2 6NH3 (powder) Wang et al.77
0.48
78
Mg(NO3)26H2O
Frusteri et al.
0.47
MgCl26H2O
NH4NO3
NH4SCN
Osman et al.79
2.9
79
NH4HCO2
Osman et al.
2.7
CH3COONH4
Osman et al.79
2.4
79
NH4NO3
Osman et al.
2.0

Measurement
Technique
Hot wire using
pressed sample
pellets 7mm
thick

Hot wire method


Hot wire on bulk
material

Hot wire

As part of this work the thermal conductivity of a bulk AC sample was


experimentally determined by the guarded hot plate method (ASTM E1530). The sample
used was a pressed pellet of AC made by pressing powdered AC in a pellet die in a
hydraulic jack to 10 tons of pressure, the pellet was held at this pressure for 60 seconds.
The resulting pellet was 28.82 mm in diameter and 7.15 mm thick with a mass of 5.557 g
and a density of 1.19 g/cm3. The thermal conductivity of the pellet, which was measured
at 12.9C to avoid decomposition, was determined to be 0.531 W/mK. This result is in
good agreement with the data available on other NH3 compounds.
The low thermal conductivity of the pellet demonstrates that it will be necessary to
provide some mechanism to enhance the heat transfer of the system. This will be even

23

more important since in practice the AC used will be in powder form and will have an
even lower thermal conductivity.

2.3. System Concept Evaluation


A number of possible methods exist for enhancing the heat transfer in an AC
system. Some of the possible solutions are:

Metal foam to enhance heat transfer

Carbon foam to enhance heat transfer

Using a heat exchanger with AC dissolved in liquid NH3

Using a heat exchanger with AC suspended in a heat transfer liquid like


Dowtherm or Therminol in which it is insoluble

Using a heat exchanger with AC in a heat transfer liquid in which it is soluble


such as ethylene glycol

2.3.1. Metal and Carbon Foams


Because of the low thermal conductivity, it will be inherently difficult to use neat AC
for TES. The low conductivity would lead to exceptionally long cycling times, or an
excessively large system, and be impractical. Therefore, the heat transfer will need to be
enhanced for any practical device to be made.
The problem of low thermal conductivity has been encountered in other PCM
TES systems. The use of thermally conductive carbon foams has been described in the
literature and has been shown to greatly reduce cycling times in wax systems. The use of
carbon foams is analogous to the use of extended surface area in any heat exchanger. For
instance, in shell and tube heat exchangers a large number of tubes are used to increase
24

the heat transfer area. Therefore, impregnating a foam with AC would enhance heat
transfer and lead to improved cycling times in a TES system.
The difficulty in impregnating a foam lies in the fact that AC exists only as a
solid. The method used to impregnate carbon foams with paraffin PCMs is to melt them
into the foam in a vacuum oven to degas the foam and draw the wax into the pores. This
method has been shown to fill around 80% of the available pore space.2 A similar method
has been used to impregnate foams with salts such as CaCl22H2O or MnCl2. In this
process the salt is dissolved in water and then put in a vacuum chamber to allow the salt
solution to fill the pores. Finally the water is removed at high temperature, leaving the
salt in the foam.80,81
Based on this previous research, there exists the possibility of dissolving the AC
in a liquid and using a vacuum technique to impregnate it in a foam and then removing
the liquid. The difficulty for doing this with AC is its limited solubility and the fact that it
cannot be taken above ~20C while the liquid is removed. This restriction eliminates
using many liquids, such as water, since they could not be effectively removed without
also decomposing the AC. Liquid NH3 has a good possibility of being used to
impregnate AC by two different methods. One method would be to use a low temperature
vacuum technique to impregnate the foam and then slightly raise the temperature to
remove the NH3 but leave the carbamate in the foam pores. A second method would be to
use the same procedure to impregnate the foam but not remove the NH3. The TES device
could then rely on the heat of vaporization of NH3 and the heat of decomposition of the
AC, possibly enhancing the overall thermal energy density of the system. The second
design would necessitate a pressure containment system to prevent the NH3 from

25

evaporating during storage. It may also be possible to use other solvents in which AC
may be soluble to impregnate the foam.

2.3.2. Liquid Ammonia Evaluation


A literature survey was conducted to determine if liquid NH3 would be a possible
solvent for AC impregnation in the foams. The solubility of NH3 salts in liquid NH3
varies considerably. Table 6 details the solubilities of many different NH3 salts in liquid
NH3. One reference states that AC is slightly soluble in liquid NH3 while a patent states
that it is very readily soluble in liquid NH3 which is anhydrous or contains very little
water.49,82 A 1926 reference gives an approximate solubility of 1.5 g/L.83 The
conditions of this solubility are not clear but it is assumed that the solubility experiment
was performed at room temperature in sealed glass tubes. Additionally, as is shown in
Table 6, the solubility of NH3 salts varies considerably. Another literature source
supported the idea that the addition of AC to NH3 could possibly lower the vapor
pressure of the liquid NH3, by reporting this effect with other ammonium salts in liquid
NH3.84 One example of this is that a saturated solution of ammonium nitrate in liquid
NH3 is stable at room temperature.84 If this occurred with AC it would reduce the
pressure containment system needed, and lead to higher system level specific properties.

26

Table 6. Solubilities in liquid ammonia at 25C (g/100 g ammonia)85


Compound
Solubility Compound Solubility
NH4I
368.4
AgCl
0.83
NH4ClO4
137.9
AgBr
5.92
(NH4)2S
120
AgI
206.84
Na2SO4
0
AgNO3
86.04
KNH2
3.6
Ca(NO3)2
80.22
KClO3
2.52
Sr(NO3)2
87.08
(NH4)2HPO4
0
Ba(NO3)2
97.22
(NH4)HCO3
0
BaCl2
0
KBrO3
0.002
MnI2
0.02
(NH4)(CH3COO)
253.2
ZnI2
0.1
LiNO3
243.66
ZnO
0
Li2SO4
0
H3BO3
1.92
NaNH2
0.004
The solubility of AC in liquid NH3 was determined in this work at two
temperatures as follows. Gaseous NH3 (Aldrich, 99.99%) was passed from a lecture
bottle and condensed into a flame dried 100 mL round bottom flask in a dry ice/acetone
bath. Approximately 50 mL of liquid NH3 was obtained to which 0.206

g of AC were

added. The solubility at -78.5C was determined by stirring the mixture with a magnetic
stir bar in a dry ice/acetone bath. From visual observation it did not appear that a
significant amount of the AC went into solution, leading to the conclusion that AC is
virtually insoluble at that temperature in liquid NH3. The solubility at -41C was then
evaluated using an acetonitrile slush bath. Once the NH3/AC mixture was warmed to this
temperature the solubility did not appear to change appreciably.
The room temperature solubility of AC in liquid NH3 was also determined. At this
temperature the vapor pressure of NH3 is ~8 atmospheres. A sealed, flame dried heavy
walled Schlenk tube was filled with ~25 mL of liquid NH3. To this 0.5 g of AC were
added. The tube was allowed to slowly heat to room temperature while stirring using a
magnetic stir bar. As the mixture heated, it first turned a violet color, this color went

27

away after 1 hour. After the mixture reached room temperature (20C) the entire solid
was not dissolved. The source of the violet color is unknown. However, it is known that
when metals dissolve in liquid NH3 they form similar colored solutions as the result of
free electrons, so it is possible that the color came from the metal cannula that was used
to put the NH3 inside the tube.
Since AC was not readily soluble in liquid NH3, additional methods were
explored to increase its solubility. According to a 1935 patent, adding ammonium
chloride (NH4Cl) will increase the solubility of AC in liquid NH3.48 This patent claims
the solubility of ammonium chloride to be 134.0 g/(100 g NH3) at 30C. The solution
made previously to find the solubility of AC in liquid NH3 was used to find the effect on
solubility of adding ammonium chloride. Since there were ~15 g of NH3, it should be
possible to dissolve ~19.5 g NH4Cl. For the first attempt 5 g of NH4Cl were added while
the NH3/AC was in a dry ice/acetone bath to prevent evaporation. Once the solution had
warmed to room temperature all the solids dissolved, confirming the patents assertion
that the NH4Cl would increase the solubility of AC in liquid NH3. To find the maximum
amount of AC that would dissolve with the NH4Cl, additional AC was added in the
following increments: 0.5 g, 0.5 g, 1 g, 1 g, 1 g. The procedure at each addition was to
cool the solution in dry ice/acetone, add the solid and then allow the mixture to heat up to
room temperature slowly. Each time the solution was cooled a good amount of solid
came out of solution and had a fluffy white appearance but when the mixture was
brought up to room temperature all the solid redissolved. Eventually 4.5 g AC were
added to the 5 g NH4Cl and at that point no more AC would go into solution, giving a
mass ratio of AC:NH4Cl of 1:1.1 and a molar ratio of 1:1.6. Although this result shows

28

one way to increase the solubility of AC in liquid NH3, it is not expected to be useful in
an actual system because the melting point of NH4Cl is 340C and the effect of adding
such a large amount of ammonium chloride would lower the energy density by mass of
the system by more than a factor of two and will still require pressure to maintain the
NH3 as a liquid at room temperature.
All of these experiments show that NH3 is impractical in a system involving AC
since the solubility of AC in liquid NH3 is so small that for any practical system it can be
considered negligible.

2.3.3. Additional Solvents


There also exists the possibility of using other solvents besides NH3. For example,
a synthetic procedure for metal carbamates states that AC can make a solution in
methanol and a dilute solution in ethanol.50 This motivated an experiment to determine
the solubility of AC in anhydrous methanol and ethanol. The experimental apparatus
consisted of an Erlenmeyer flask on a stir plate. A titration burette was used to measure
the amount of solvent added to the flasks. The amount of 100 mL of ethanol and
methanol were used in the experiment, and both were put in an Erlenmeyer flask with a
stir bar and an argon purge to prevent water accumulation. The AC was slowly added
until no more would dissolve in the liquids. At ambient temperature and pressure the
methanol dissolved ~7 g AC/100 mL methanol and the ethanol dissolved ~2 g AC/100
mL ethanol. Since methanol dissolved more AC it was used as the solvent of choice for
the impregnation of carbon foam.
To more accurately determine the solubility of AC in methanol, the experiment
was repeated three times with the following procedure. Approximately 1 g of AC was put
29

in a 50 mL Erlenmeyer flask. Methanol was added to a titration burette and slowly added
to the stirring methanol/AC solution until all of the AC had just dissolved. Exact amounts
used in each experimental run are listed in Table 7.

Table 7. Solubility of ammonium carbamate in methanol


AC Added (g) Methanol Added (mL) Solubility (g/mL)
1.031
20.71
0.0498
1.061
19.59
0.0542
1.188
20.94
0.0567
Average:
0.0536
Standard Deviation:
0.0035
The first method used to impregnate the foam was the vacuum method. This is
similar to techniques used to impregnate carbon foams with paraffin wax. The carbon
foam used was not thermally conductive due to the expense of conductive foams. The
experimental setup was a small, skinny polymer vessel equipped with a stopcock valve
shown in Figure 3. A small piece of carbon foam was put in the vessel and a Teflon
coated stir bar placed on top of it to prevent it from floating. The saturated methanol/AC
solution was poured over the foam. The vessel was immersed in an acetone/dry ice bath
to minimize the amount of methanol that evaporated during the impregnation. A Schlenk
line was used to create a vacuum and remove the air from the foam and replace it with the
AC solution. The excess solvent was removed under vacuum in an ice/water bath to
ideally allow the methanol to escape but not the AC.

30

Vacuum Vessel
Methanol with
AC
Weight
Carbon Foam

Figure 3. Vessel used to impregnate carbon foam with methanol and ammonium
carbamate
After the liquid evaporated, the carbon foam was removed. It was cut in half using
a razor blade and examined visually under a microscope. No AC was observed in the
pores although the odor of NH3 was noticeable. Because no AC could be seen it was
apparent that most of the AC had been removed along with the methanol. A series of
experiments are subsequently detailed to test this.
Approximately 2 g of AC powder were added to the previously used polymer
reactor. The vessel was immersed in an ice/water bath. The system was connected to the
Schlenk line and the system was exposed to a vacuum of 10 mTorr for three hours. After
this time it did not appear that any significant amount of AC had evaporated. Next a
saturated solution of AC/methanol was placed in the vessel and the same vacuum was
applied with the vessel in ice water. Under these conditions all of the methanol
evaporated and no AC was left in the vessel. These experiments show that it is not
possible to remove the methanol without the AC.
To test if the reason the AC was being removed with the methanol was its
solubility, an experiment was performed with the AC in pentane, in which it is insoluble.
31

The boiling point of pentane at one atmosphere of pressure is 36.1C and that of
methanol is 64.7C, so the pentane should be much easier to remove using vacuum. A
slurry of pentane and AC was placed in the previously used vessel and immersed in ice
water. When the vessel was evacuated the pentane was removed, leaving the AC behind.
This experiment demonstrates that using a liquid medium in which the AC is insoluble
will not cause the AC to decompose while the liquid evaporates, but one in which it is
soluble will cause the AC to decompose as the liquid evaporates. The practical
implication is that using a solvent will not allow the impregnation of foams followed by
solvent removal in which the AC is left in the foams. Additionally, a liquid in which AC
is insoluble will not allow the pores to be infiltrated with AC, so the foams cannot be
impregnated with this type of fluid either. These limitations show that it will not be
possible to impregnate a foam with AC through a vacuum technique.

2.3.4. Aluminum Foam


Metal foams can be made in what is known as an open cell foam, making them
much easier to impregnate. Open cell versions of carbon foam are available but are
thermally non-conductive unless some sort of surface treatment is applied and these are
prohibitively expensive. Therefore, as an initial trial aluminum foam was used to test an
open cell foam.
Open cell Duocel Aluminum Foam samples were obtained from ERG Aerospace.
The samples are shown in Figure 4. Three different porosities were obtained and the
pores are rated by pores per inch (PPI). As would be expected, the higher the volume
percent aluminum, the higher the thermal conductivity will be. The tradeoff between
additional weight and volume the aluminum occupies versus the gain in system thermal
32

conductivity will have to be evaluated for any use of a foam to maximize energy density
and minimize cycling time. Surface area increases with both increasing density and pores
per inch. The amount of surface area will be the amount of heat transfer area for the AC,
so increasing surface area will increase the rate of heat transfer, and this will lead to a
tradeoff similar to that for thermal conductivity.

Figure 4. Duocel aluminum foam


The dimensions and masses of the foam samples received are given in Table 8. A
simple experiment was conducted to demonstrate how well the bulk AC powder would
pack into the foam. The procedure was to first ball-mill the AC powder to reduce particle
size so that it could easily fit inside the foam pores. Next the foam samples were encased
in aluminum foil. The powder was then manually packed into the foam. The density of
the powder inside the foam is given below. Note these densities are only approximate but

33

show that it is possible to pack the AC inside metal foam close to its bulk powder density
of approximately 780 kg/m3.
Sample
10 PPI
20 PPI
40 PPI

Table 8. Dimensions and masses of aluminum foam samples


Mass
AC
AC
Dimensions
Volume
(g)
Mass
Density
(mm)
(cm3)
(g)
(g/cm3)
38.20 x 12.45 x 88.26
41.98
10.236 26.784
0.638
37.60 x 12.73 x 88.50
42.36
7.356 26.030
0.614
38.14 x 12.93 x 89.35
44.06
9.879 22.583
0.512

To quickly examine the effect that AC would have on the heat transfer in an
aluminum foam, a simple experiment was run with the foam on a hot plate. The 10 PPI
foam was filled with 26.784 g of AC powder and placed on a hot plate. The 20 PPI foam
had no AC in it and served as the control for temperature. A thermocouple was placed
inside each foam sample as well as on the surface of the hot plate. The experimental
setup is shown in Figure 5. The temperatures of the hot plate surface, bare metal foam
and impregnated metal foam are given in Table 9. The experiment clearly demonstrates
that the AC is effective at removing heat from the foam through its decomposition. It is
apparent from this that a thermally conductive open celled foam would be able to
enhance the heat transfer to the AC.

34

Hot place surface


temperature
measurement

Weight to ensure
good contact

Hot plate surface

Foam with AC

Thermocouple
wires

Control Foam

Figure 5. Ammonium carbamate in aluminum foam


Table 9. Temperature-time records for ammonium carbamate in aluminum foam
Time (hr)
Hot Plate (C)
20 PPI (C)
10 PPI/AC (C)
0
57.2
51.9
40.8
0.8
58.2
50.1
40.3
1.3
58
50.2
40.4
17
53.9
45.8
54.1 (AC gone)
It may be difficult to impregnate the foam at the device level and may also lead to
a difficulty in mass transfer. This same problem has been observed in other sorption
systems where foams are used to increase thermal conductivity: that the small pore size
can have a detrimental effect on mass transfer which lowers the overall rate of reaction
and thus heat transfer.31,32,86-88 Additionally, using foams could lead to an explosion
hazard at high thermal power ratings because of the large volume change associated with
a solid to gas reaction. Also there is no pragmatic way to pack the foams and using a
foam does not offer any scalability advantage since the system specific properties would
scale linearly.

35

2.3.5. Foam Impregnation Summary


The small, closed cell pores of carbon foam make it difficult to impregnate. The
previous experiments show that the vacuum methods, which have been used to
impregnate the foam with other materials, will not work for AC since it readily
decomposes. Because of this, carbon foams were abandoned as a method for increasing
the heat transfer of bulk AC.
It was possible to mechanically pack open cell aluminum foams and initial testing
showed that the AC did lower the foam temperature through its decomposition. Although
this was a success the foams in general suffer from several problems which will inhibit
their use for this application. The first is that the nature of the foams leads to inherent
mass transfer limitations, which would lead to an upper limit for a power rating.
Associated with this, mass transfer is a safety problem since high thermal power ratings
would lead to a high decomposition rate and could cause the foams to explode. Also, a
system utilizing foams to enhance thermal conductivity will scale linearly, offering no
advantage at a larger system size which is undesirable for this work. For all of these
reasons foams will not be a viable system level solution to increasing the thermal power
rating.

2.3.6. Heat Transfer Fluid Evaluation


Heat transfer fluids as a system medium will provide good heat transfer to the AC
and could also lead to simple system operation as well as good scalability. The good
scalability should exist since the AC could be stored as a solid and then injected into the
system, so the specific properties should increase for a larger system needing a greater
amount of TES reserves. Two general classes of heat transfer fluids exist, those in which
36

AC is soluble and those in which it is insoluble. A heat transfer fluid in which it is


soluble may well be advantageous compared to one in which it is insoluble. A reason for
this is that in any flow system a soluble heat transfer fluid should prevent clogging.
Additionally, in aforementioned experiments in section 2.3.3, the use of methanol, in
which AC is soluble, led to complete decomposition of the AC under vacuum, while in
the pentane, in which AC is insoluble, the AC remained behind when the pentane was
removed using vacuum. Both classes of heat transfer fluids will need to be evaluated to
determine which leads to the best performance. As a selection criteria for heat transfer
fluids, they should have a low vapor pressure to ensure that the fluid will not be
consumed through evaporative losses. It may also be possible to use a vacuum to greatly
increase the rate of AC decomposition through Le Chatliers principle and therefore
increase the rate of cooling. In order to establish a baseline for the maximum rate of
decomposition as a function of temperature several experiments were conducted.
The first solvent chosen was EG. Ethylene glycol has a high boiling point at one
atmosphere of pressure (197.3C) and a very low vapor pressure in the temperature range
of interest. The solubility of AC in EG was determined using the same experimental
technique which was used to determine the solubility of AC in methanol and is shown in
Table 10.

Table 10. Solubility of ammonium carbamate in ethylene glycol


AC Added (g) EG (mL) Solubility (g/mL)
3.364
18.09
0.186
2.387
13.15
0.182
1.601
8.52
0.188
Average:
0.185

37

The schematic of the experimental apparatus used to measure the maximum rate
of decomposition of AC as a function of temperature is shown in Figure 6. The lowest
pressure that the system could achieve was lower than the gauge resolution of 1 x 10-5
torr. However, given that the gauge was located much closer to the diffusion pump than
the reaction vessel, it is likely that the pressure was higher at the reaction vessel. For the
temperature range for the experiment the water bath could be regulated between 5 and
50C.

Figure 6. Schematic of system used to measure the rate of decomposition of ammonium


carbamate
2.3.6.1. Experimental Procedure
The EG (Sigma-Aldrich, 99%) was dried using 3 molecular sieves to remove any
residual water. The glassware was dried to remove water prior to use. All decomposition
reactions were conducted using heavy wall Schlenk flasks. The EG was degassed using a
freeze-thaw procedure. All measurements of the EG during the experiment were
gravimetric and the reaction vessel mass was determined before the EG was added. The
38

AC was added to the flask, its mass determined, and then the Schlenk flask was
immersed in the temperature controlled water bath for at least twenty minutes to allow
thermal equilibrium. The air was then evacuated from the system to a pressure no greater
than 5 x 10-4 Torr on the pressure transducer. Next the valve between the liquid nitrogen
trap and the vacuum pump was closed. In this way the liquid nitrogen worked to keep the
pressure low in the vacuum manifold as well as to trap any decomposed AC. This setup
prevented AC from being pulled through the system into the pump. The valve on the
reaction vessel was opened and the AC was allowed to decompose for five minutes. After
this time the vessel was backfilled with nitrogen and weighed to find the mass change.
The procedure to evacuate the system, allow it to come to thermal equilibrium and then
run the decomposition for five minutes was repeated for a total decomposition time of at
least thirty minutes. At each temperature an initial run with just EG was conducted to find
its baseline rate of evaporation and loss.
2.3.6.2. Heat Transfer Fluid Analysis
The first experiment which was conducted was to determine whether EG, in which
AC is soluble, or a heat transfer fluid in which it is insoluble, would lead to a greater rate
of decomposition. Tetraglyme (boiling point at one atmosphere pressure is 275C) was
selected as the heat transfer fluid in which AC is insoluble due to its high boiling point.
Both tetraglyme and EG were evaluated at 30C using equal fluid volumes and amounts
of AC using the aforementioned experimental procedure. They are also compared to the
bare powder at twice the solubility multiple in Figure 7 and at four times the solubility
multiple in Figure 8. The amounts used are shown in Table 11 and the solubility
multiples correspond to the solubility of AC in EG.
39

Conversion

1.00
0.90

Ethylene Glycol

0.80

Tetraglyme

0.70

Bare Powder

0.60
0.50
0.40
0.30
0.20
0.10
0.00
0

10

20

30

40

50

60

Time (min)

Figure 7. Comparison of ammonium carbamate conversion in ethylene glycol, tetraglyme


and bare powder at two times solubility and 30C

1.00
Ethylene
Glycol
Tetraglyme

0.90
0.80

Conversion

0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0

10

20

30

40

50

Time (min)

Figure 8. Comparison of ammonium carbamate conversion in ethylene glycol and


tetraglyme at four times solubility and 30C

40

Table 11. Amounts of ammonium carbamate and tetraglyme added for decomposition
studies
Solubility Multiple Tetraglyme (mL) AC (g)
2x
49.8
18.79
4x
51.1
37.51
As these profiles show, the reaction rate is greatly depressed in tetraglyme at the
same experimental conditions of temperature, pressure, amount of solvent and amount of
carbamate. Additionally, the conversion rate is nearly identical in tetraglyme as it is in
bare powder showing that merely having a heat transfer fluid is not sufficient to increase
the conversion rate. This leads to the conclusion that the fact that AC is soluble in EG
must play a role in the rapid decomposition under vacuum conditions. This was suspected
with the initial experiments in methanol where the AC was removed when methanol was
the fluid but not when pentane was used. Therefore, EG will be further evaluated and the
study of heat transfer fluids in which AC is insoluble will be discontinued.
Since EG was demonstrated to be the superior heat transfer fluid, the experiment
in EG was repeated at 50C, 40C, 30C, 20C and 10C, and the results are shown in
Figure 9. For a first run at each temperature, the AC was added to the vessel at twice its
solubility limit at room temperature (18.5g/100mL EG). As expected, as temperature
increased the rate of reaction increased as well. The 40C and 50C conversion profiles
are nearly identical. This is most likely because the rate of reaction was limited in these
cases by how quickly the gases could be removed. The rapid rate of decomposition
limited how far the valve on the Schlenk tube could be opened because with the valve
fully open, the rapid gas removal rate led to liquid entrainment into the vacuum system.
This meant the rate of decomposition was effectively throttled to keep the EG inside
the tube. At lower temperatures this problem was not as pronounced since the
41

decomposition was slower. Because the 40C and 50C profiles were nearly identical it
was decided to not run further trials at 50C on this system. A limitation of the system is
the inherently low rate of mass transfer found in high vacuum systems, which are
designed to achieve low pressure but not high flow rates. This means that the rate of
reaction may have been limited at all temperatures by mass transfer.
1
0.9
0.8

Conversion

0.7
0.6
0.5
0.4
0.3

50
40
30
20
10

0.2
0.1
0
0

10

15

20

25

30

35

40

Time (min)

Figure 9. Conversion as a function of time for ammonium carbamate in ethylene glycol at


two times its solubility limit
As there are an extensive number of variables in the procedure, many of which
cannot be measured, the uncertainty of the conversion was estimated by repeating the
procedure several times at each temperature to find the standard deviation in the
conversion as a function of time calculation. These standard deviations were then

42

averaged at each temperature and the results are shown in Table 12 and are reflected as
the error bars on the plots.

Table 12. Error analysis for ammonium carbamate decomposition


Temperature (C) System Average standard deviation in conversion
10
Slurry
0.01
10
Powder
0.02
20
Slurry
0.06
20
Powder
0.06
30
Slurry
0.07
30
Powder
0.04
40
Slurry
0.05
40
Powder
0.03
Results of the decomposition experiments at 40C, 30C, 20C and 10C for a
slurry in EG and the bare powder are shown in Figure 10 through 13. A sharp difference
can be seen between the powder and slurry at 40C and 30C, while at the lower
temperatures this difference is not as evident due to the low reaction rates. These profiles
demonstrate the advantage of using some sort of heat transfer medium in which AC is
soluble to increase the rate of reaction.

43

1.00
Run 1 Powder

0.90

Run 2 Powder

Conversion

0.80

Run 3 Powder

0.70

Run 1 Slurry

0.60

Run 2 Slurry

0.50

Run 3 Slurry

0.40
0.30
0.20
0.10
0.00
0

10

15

20

25

30

35

40

Time (min)

Figure 10. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 40C

1.00
0.90
0.80

Conversion

0.70
0.60
Run 1 Powder

0.50

Run 2 Powder

0.40

Run 3 Powder

0.30

Run 1 Slurry

0.20

Run 2 Slurry

0.10

Run 3 Slurry

0.00
0

10

20

30

40

50

Time (min)

Figure 11. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 30C

44

1.00
0.90
0.80

Conversion

0.70
0.60
0.50

Run 1 Slurry

0.40

Run 2 Slurry

0.30

Run 3 Slurry
Run 1 Powder

0.20

Run 2 Powder

0.10

Run 3 Powder

0.00
0

10

15

20

25

30

35

40

45

Time (min)

Figure 12. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 20C
1.00
Run 1 Slurry
Run 2 Slurry
Run 3 Slurry
Run 1 Powder
Run 2 Powder
Run 3 Powder

0.90
0.80

Conversion

0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0

10

15

20

25

30

Time (min)

Figure 13. Conversion as a function of time for ammonium carbamate powder and
ammonium carbamate in ethylene glycol solution at 10C
As this work developed, it was determined that the optimum desired operating
temperature for the system is ~30C. Therefore, attempts were undertaken to run
45

additional trials at 30C with different loadings of AC in the EG. Trials were run at 2, 3,
4, 5 and 6 times the solubility limit of AC in EG. A larger Schlenk tube had to be used for
these trials because the decomposition was so rapid. Use of the smaller tube resulted in
material being pulled out of the small tube. Because of this, the valve could not be fully
opened, which would lower the reaction rate, forcing a change to a larger tube. The
conversion as a function of time is shown in Figure 14 and the bare powder conversion is
included for comparison. Table 13 shows the initial amounts of solvent and AC.
1.00

2x Solubility
3x Solubility
4x Solubility
5x Solubility
6x Solubility
Powder

0.90
0.80

Conversion

0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0

10

15
Time (min)

46

20

25

30

1.00
2x Solubility

0.90

3x solubility
0.80

4x solubility

Conversion

0.70

5x Solubility
6x Solubility

0.60

Powder
0.50
0.40
0.30
0.20
0.10
0.00
0

10

15

20

25

30

Time (min)

Figure 14. Comparison of different initial loadings of ammonium carbamate in ethylene


glycol at 30C

Table 13. Initial amounts of ethylene glycol and ammonium carbamate to test rate of
reaction at different initial loadings of ammonium carbamate in ethylene glycol
Solubility Multiple EG (mL) AC (g)
2x
50.3
19.45
3x
51.0
28.17
4x
49.2
35.25
5x
49.3
46.18
6x
49.2
54.27
In each trial approximately the same amount of solvent was used, but as the
amount of AC was increased the conversion as a function of time decreased only slightly,
meaning a greater rate of decomposition occurred at increasing solubility multiples. The
amounts of AC were increased to determine the maximum rate of decomposition that
47

could be accomplished in this system. In order to determine this, a plot of the average
thermal energy consumed in the decomposition (in kW) was plotted as a function of
conversion. The power needed was determined from the reaction enthalpy change. The
plot is shown in Figure 15 which shows that a maximum rate of ~0.065 kW is reached for
the three systems with 4x, 5x and 6x loadings of AC.
0.07

Power Rating (kW)

0.06
0.05
0.04
0.03

2x Solubility
3x solubility

0.02

4x solubility
5x Solubility

0.01

6x Solubility
0
0.00

0.20

0.40

0.60

0.80

1.00

Conversion

Figure 15. Rate of thermal power versus conversion for the decomposition of ammonium
carbamate in ethylene glycol at 30C
Propylene glycol (PG) was evaluated as an alternative heat transfer fluid in which
AC is soluble. This is because EG is toxic and bad for the environment while PG is foodsafe and considered to be environmentally friendly. Propylene glycol was tested with AC
at 30C with 18.58 g of AC in 50 mL of PG and is graphically compared to AC in EG at
30C with 19.45 g of AC in 50 mL of EG in Figure 16. In the figure the run in PG shows
a conversion of greater than 1 which occurred since a larger amount of PG was entrained
than with EG. The experiment was also repeated with the same result. While it is not

48

possible to find the amount of PG entrained the fact that conversion as a function of time
is comparable to that of AC in EG lends support to using PG instead of EG. The greater
amount of liquid entrainment can be explained by comparing the viscosity of the two
liquids. The viscosity of PG at room temperature is 50 centipoise and the viscosity of EG
at room temperature is 11 centipoise.89,90 The greater viscosity would lead to a greater
amount of PG being entrained which explains a conversion greater than one.
1.20
1.00

Conversion

0.80
0.60
0.40
PG

0.20

EG
0.00
0

10

15

20

25

30

35

40

45

Time (min)

Figure 16. Comparison of ammonium carbamate in ethylene glycol and propylene glycol
at 30C
2.3.7. Ammonium Carbamate Materials Compatibility
No data on corrosion specific to AC exists, so corrosion considerations will focus
on issues arising from CO2 and NH3. The Handbook of Corrosion Data presents
information on the corrosion of a wide variety of compounds with many metals.91 Only
NH3 is considered since it is generally more corrosive than CO2 or the heat transfer fluids
used in this work. Metals suitable for use with NH3 are stainless steels, aluminum and
titanium. Copper and copper alloys must be avoided when working with NH3 as NH3 and
49

ammonium compounds can lead to stress corrosion cracking in copper. Ammonium


bicarbonate is a related ammonium compound, and it is not corrosive to stainless steel.
Ammonium carbonate is similar to AC but it contains water as well and it is not corrosive
to aluminum or stainless steel.
Based on the data available for corrosion, both stainless steel and aluminum
should be good materials to work with AC, especially in heat transfer applications.
Aluminum will probably prove to be a more advantageous material since its thermal
conductivity is 250 W/mK at room temperature and that of stainless steel is only 16
W/mK and it is also considerably less dense than stainless steel which should lead to
higher system level specific properties.

2.3.8. Hysteresis
As this has been envisioned as a system where AC could be continuously loaded
into a glycol slurry and the glycol not recycled or treated in any way, it is desirable to
have an idea of the effect of reusing the glycol. The solubility of CO2 in EG has been
reported to be 39.4 mmol/L at 25C and a partial pressure of 760 Torr.92 However, the
solubility of CO2 in EG increases with increasing pressure, so at the vacuum conditions of
the system the solubility will be lower.93 The solubility of NH3 in EG has been reported
in terms of mole fraction to be very high. At atmospheric pressure and 25C it has been
reported to be a mole fraction of 0.406.94 It is been conjectured that this extremely high
solubility is due to a reversible chemical reaction between the NH3 gas and solvent
forming ammonium radicals at the hydroxyl groups.94 It is possible that this high
solubility of NH3 will affect the system of AC and EG. However, under lower pressure

50

the solubility will decrease which should help avoid any effects due to a large amount of
dissolved NH3 on the reaction equilibrium.
The possibility of hysteresis on the EG was tested by repeating the previous
experiment to remove the AC from the EG at 30C under vacuum. The same EG was
used for four consecutive experimental runs. Initially, 50.0 mL of EG were loaded into
the Schlenk tube. For each run ~28 g of AC was added. Table 14 shows the initial and
final amounts of solvent for reach run and how much AC was added. The amount of
solvent was found using the baseline solvent evaporation rate of 0.05 g/min, which was
found by subjecting the Schlenk tube with only EG to vaccum to find its rate of
evaporation. It should be noted that the mass of material remaining in the flask after the
final run was 55.21 g. This can be attributed to NH3 or CO2 dissolved in the EG.
However, even though the reaction products are soluble in the EG it is evident from the
conversion time profiles in Figure 17 that the rate of decomposition is relatively
unaffected by the reuse of EG, so the EG could be successfully reused in a system level
application.

Table 14. Hysteresis measurements of ammonium carbamate in ethylene glycol at 30C


Run
Initial Solvent (g)
Final Solvent (g)
AC added (g)
1
55.62
54.12
28.12
2
54.12
52.62
30.72
3
52.62
51.12
28.85
4
51.12
49.62
27.87

51

1.00
0.90
0.80

Conversion

0.70
0.60
0.50
0.40
0.30

Run 1
Run 2

0.20

Run 3

0.10

Run 4

0.00
0

10

15

20

25

30

Time (min)

Figure 17. Conversion as a function of time for the hysteresis measurements of


ammonium carbamate in ethylene glycol at 30C

2.3.9. Heat of Solution


Upon dissolution in a solvent, salts normally have either endothermic or
exothermic heats of solution. During the course of the experiments conducted it was
observed that AC has an endothermic heat of solution in EG. This could be valuable to
the project since it could provide additional cooling to a slurry based system. The
experiment to find the heat of solution of AC is based on a procedure by NIST which
gives the heats of solution for a wide variety of salts at infinite dilution.95 In this work the
heat of solution at infinite dilution,

, is given by Equation 13.

(13)

52

where

is the heat of solution at a known molality and

is a correction for

the heat of dilution to infinite dilution. It is also necessary to know the apparent molal
heat capacity of the solute,

. It is possible to estimate to both

variety of concentrations and to estimate

. In the

is to take the measurements of

literature the normal way to estimate

to extrapolate to

and

at a

by the differences between points and then

. The value of

is calculated from Equation 14.


T

(14)

where mt is the mass of solvent and solute, Cp is the specific heat, T is the temperature
change, and n is the moles of solute added. This value is determined experimentally by
adding a known quantity of solute to a known amount of solvent and finding the
maximum temperature change in an adiabatic vessel.
The experimental methodology was validated by finding the heat of solution of
NH4Cl in water. Data were collected for three trials of NH4Cl in water and the
experimental details and results are shown in Table 15. The heat of solution must be
adjusted for the dilution using Equation 13 where

at 1.5 molarity from NIST is

560 J/mol, giving an average value of 14,840 J/mol.

Table 15. Experimental details and results for the heat of solution of ammonium chloride
in water
Mass H2O (g) Mass NH4Cl (g) T(C) Heat of Solution (kJ/mol)
103.73
8.47
-5.2
15.4
Trial 1
103.79
8.35
-5.1
15.3
Trial 2
104.97
8.49
-5.2
15.2
Trial 3

53

The experimental uncertainty was evaluated using the method in Equation 15 and
the variables are defined along with their values in Table 16. All error values are from the
instrument manufacturers.

(15)

Table 16. Uncertainty in the heat of solution calculation


Variable
Meaning
Value
wy
Error of heat of solution
Unknown
y
Heat of solution
15,400 J/mol
Error of water mass measurement
0.05g
x1
Water mass measurement
103.73 g
Error of solid mass measurement
0.003g
x2
Solid mass measurement
8.470 g
Error of thermocouple measurement 1
0.31C
x3
Thermocouple measurement 1
20.6C
Error of thermocouple measurement 2
0.31C
x4
Thermocouple measurement 2
15.4C
The resulting uncertainty is 310 J/mol or 2.0%. Therefore, the final value for the
experiment is 14,840310 J/mol. Comparison to the value of 14,780 60 J/mole from
literature validates the experimental procedure since the percent difference is only 0.4%
and lies well within the uncertainty estimation.95
The same procedure was used to find the heat of solution of AC in EG. The
uncertainty was evaluated using the same method as used for the NH4Cl in water. The
plot in Figure 18 gives the heat of solution as a function of molality with error bars and
gives the line used to extrapolate the heat of solution to infinite dilution. Multiple
measurements were conducted at each concentration and the details of each experiment

54

can be found in Table 17. The heat of solution of AC in EG was determined to be 9,700
J/mol. This value is lower than that of ammonium chloride in water and quantifies the
cooling effect observed when the AC was dissolved in EG; it also shows that merely
adding AC to EG will lower the system temperature.
12000

Heat of Solution (J/mol)

10000
8000
6000
4000
2000
y = -2379.3x + 9686.4
R = 0.9647
0
0

0.2

0.4

0.6

0.8

1.2

1.4

1.6

Molality

Figure 18. Heat of solution of ammonium carbamate in ethylene glycol as a function of


molality

55

Table 17. Experimental data for determination of heat of solution of ammonium


carbamate in ethylene glycol
Molality Trial T
EG Mass
AC Mass
Heat of Solution Uncertainty
(C)
(g)
(g)
(J/mole)
(J/mol)
0.25
1
1
100
1.952
9787
1370
0.25
2
0.9
100
1.954
8809
1370
0.25
3
0.9
100
1.952
8809
1370
0.5
1
1.7
100
3.908
8471
698
0.5
2
1.7
100
3.905
8478
698
0.5
3
1.8
100
3.905
8977
698
0.75
1
2.3
100
5.867
7792
474
0.75
2
2.2
100
5.874
7453
474
0.75
3
2.2
100
5.87
7453
474
1
1
2.9
100
7.809
7504
362
1.25
1
3.1
100
9.675
6528
295
1.5
1
3.5
100
11.721
6252
250

2.3.10. Born-Harber Cycle for Ammonium Carbamate


The Born-Harber cycle for the decomposition of AC in EG is presented
graphically in Figure 19, and represented in Equations 16 through 19. There are three
main conclusions which apply to this work which can be drawn from this cycle. The first
is that the heat of solution could be used to provide subambient cooling at a system level
which could be important for achieving the desired temperature range. The second point
is that although the endothermic heat of solution could be used to provide subambient
cooling, it does not have an overall effect, since as Figure 19 illustrates, the total amount
of energy consumed by the decomposition is the same whether or not the AC goes into
solution. The final point is that this heat of solution could even be detrimental depending
on the mixing point. If the mixing takes place away from the heat exchange vessel then it
is possible that the solution could warm again to room temperature, which would result in
a loss of 6.2% of the total heat rejection capability of the AC.
56

CO g

2NH g

NH COONH solid
NH COONH solution
NH COONH solid

NH COONH solid
9.7 kJ

157 kJ

NH COONH solution

147.3 kJ
157 kJ

CO g
CO g

2NH g
2NH g

(16)
(17)
(18)
(19)

Figure 19. Born-Harber cycle for the decomposition of ammonium carbamate

2.3.11. Specific Heat of Ammonium Carbamate


It is essential to know the specific heat of AC for any calculations requiring a
temperature change of the AC. The specific heat of AC from 20C to 180C, given in
Table 18, have been reported in the Kirk-Othmer Encyclopedia of Chemical Technology
but no reference to primary literature or experimental technique is available.96
57

Table 18. Specific heat of ammonium carbamate96


T (C) Cp (J/gK)
20
1.67
60
1.92
100
2.18
140
2.43
180
2.59
To validate the literature data, DSC was used to find a single point measurement
of the specific heat of AC at 0C. Two values of 1.39 J/gK and 1.56 J/gK were found
and the average of 1.48 J/gK was used. This point was plotted with the literature data
from 20C to 100C to verify the data. Only the points from 20C to 100C were used
since the others were well outside the operating parameters of the experimental work.
The R2 of 0.99 for the linear fit suggests that the data from the literature is valid
compared to the experimental work, so the literature value for the specific heat was used.
The data used to find the linear trendline is below in Figure 20 and shows the relationship
in Equation 20.
Cp (J/gK) = 0.0069T(C) + 1.5018

58

(20)

2.5

Specific Heat (J/gK)

1.5

y = 0.0069x + 1.5018
R = 0.9937

0.5

0
0

20

40

60

80

100

120

Temperature (C)

Figure 20. Temperature dependent specific heat of ammonium carbamate

2.4. Decomposition Pressure


The decomposition pressure of AC has been reported in literature. Since the focus
is now a system using AC for TM that will have the AC in a liquid heat transfer medium
such as EG, it is advantageous to know the decomposition pressure of AC in a liquid
medium. For this study the decomposition pressure of the solid was first measured and
compared to literature to validate the experimental procedure. Next, the decomposition
pressure of AC in EG was measured from 10C to 50C.
The experimental setup consisted of a glass Schlenk vessel 100 mL in volume. It
was connected to a VacuumBrand VSK 3000 absolute pressure diaphragm gauge which
is capable of measuring pressure from 795 torr to 1 torr, independent of gas species
present. To measure the pressure, the vessel was filled with AC powder, solution or
slurry. The non-condensable gases were removed from the vessel by evacuating the
system and then allowing it to come up to its equilibrium pressure several times. Then the
59

vessel was immersed in a thermostated water bath and the material in the vessel was
allowed to equilibrate for at least 30 minutes at each temperature before a reading was
taken.
The first experiment conducted was to measure the decomposition pressure of the
neat powder to compare to published results. The results of the experiment are shown in
Figure 21. The black squares are experimental data and all other points are from literature
sources. As the data shows the experimental setup gives accurate data so it can be used
for decomposition pressure experiments.
1000
Egan, Potts, Potts (62)

900

Joncich, Solka, Bower (34)

800

Briggs and Migrdichian (60)

Pressure (Torr)

700

Bennett, Rithie, Roxburgh, Thomson (63)

600

Experimental Bare Powder

500
400
300
200
100
0
10

20

30

40

50

60

70

Temperature (C)

Figure 21. Experimental decomposition pressure of ammonium carbamate powder


The vapor pressure of pure EG was measured as a baseline over the temperature
range from 10C to 50C. It was found to be less than 1 torr throughout the measurement
range, which was the lower limit of the sensor. Therefore, the vapor pressure of the

60

solvent is well below the decomposition pressure of the solid, so it should not play a
significant role in the experiment.
The vapor pressure of the AC in EG was measured by making a slurry of AC in
EG. The same experimental procedure was used as with the neat powder. The results are
shown in Figure 22, the literature references in this figure are the same as in Figure 21.
Up to 40C, the results for the slurry are identical to the bare power and show a slightly
higher pressure above 40C. This can be explained by examining the components that
contribute to the total pressure in the vessel. Equation 21 shows that the total pressure in
the vessel will be a combination of the partial pressures of the EG, CO2 and NH3. It is
likely that the sum of these terms will be greater than the sum of the partial pressures of
CO2 and NH3 above the neat solid for two reasons. The first is that the partial pressures
above the solution will likely be higher due to the entropy dependence of the
decomposition pressure which will show a dependence on concentration and temperature.
This will not exist for the neat powder and the temperature dependence explains why the
deviation was only noticed at higher temperatures. The second reason is that the addition
of the EG term should also slightly raise the equilibrium pressure. Although the
experiment shows a slight elevation in the decomposition pressure for the EG slurry, it is
unlikely that this small deviation explains the markedly different decomposition rates
observed.
(21)

61

1000
Literature Bare Powder

900

Experimental Bare Powder

800

AC in EG

Pressure (Torr)

700
600
500
400
300
200
100
0
10

20

30

40
Temperature (C)

50

60

70

Figure 22. Decomposition pressure of ammonium carbamate in ethylene glycol

2.5. Ammonium Carbamate Decomposition Test System


In order to evaluate the use of AC for heat rejection, a test system was constructed.
This system needed to be capable of quantitatively determining the amount of thermal
energy rejected by the AC as a function of temperature as well as control the overhead
pressure on the AC. A schematic of the proposed system is in Figure 23. The principle
behind this system is that the amount of heat rejected by the AC can be quantified using
an energy balance over the simulated thermal load. The steps in the design process are
detailed in the subsequent sections.

62

Figure 23. Ammonium carbamate decomposition test system

2.5.1. Reactor Sizing


The first consideration in the design of this system was determining the reactor
size. A test matrix was developed and is shown in Table 19. The basis for this matrix is
the rejection of 20 MJ of thermal energy for the full scale system, which would require
11.1 kg of AC. The solubility multiple number is based on 18.5 g AC per 100 mL of EG.
For the purposes of a laboratory scale demonstration unit, a system size of less than 1
liter is necessary and less than 500 mL is desirable to operate in practical limits. It was
assumed that the system size would be two times the liquid volume used. In the matrix
below those combinations that are possible with a 1 liter system are shown in yellow and
those possible with a 500 mL system are shown in orange. From this test matrix it was
determined that a 500 mL reactor would be sufficient for laboratory scale experiments as
63

it would be capable of running measurements at a scale of 1:50 and below, depending on


the solubility multiple. A 500 mL jacked reactor from Chemglass (CG-1926-01) was
selected, and the jacket evacuated with a rotary vein vacuum pump to ensure that the
vessel is well insulated so the assumption of an adiabatic reactor can be made.
On a system level the reactor size will need to be more carefully selected to match
the peak thermal load required to avoid unnecessary dead space in the reactor. This is to
limit oversizing the reactor which will lower the specific properties and to avoid a large
gas volume to fill with decomposed AC as bringing this volume to equilibrium would
cause unnecessary decomposition.

64

Table 19. Test matrix for ammonium carbamate system (see key and text for explanation)
Solubility
Multiple
0.5

1:1
Scale
11.1
120
240
11.1
60
120
11.1
30
60
11.1
20
40
11.1
15
30
11.1
12
24
11.1
10
20

1:5
Scale
2.22
24
48
2.22
12
24
2.22
6
12
2.22
4
8
2.22
3
6
2.22
2.4
4.8
2.22
2
4

1:10
Scale
1.11
12
24
1.11
6
12
1.11
3
6
1.11
2
4
1.11
1.5
3
1.11
1.2
2.4
1.11
1
2

1:25
Scale
0.444
4.8
9.6
0.444
2.4
4.8
0.444
1.2
2.4
0.444
0.8
1.6
0.444
0.6
1.2
0.444
0.48
0.96
0.444
0.4
0.8
Key

1:50
1:100
1:200
Scale
Scale
Scale
0.222
0.111
0.0555
2.4
1.2
0.6
4.8
2.4
1.2
0.222
0.111
0.0555
1.2
0.6
0.3
2.4
1.2
0.6
0.222
0.111
0.0555
0.6
0.3
0.15
1.2
0.6
0.3
0.222
0.111
0.0555
0.4
0.2
0.1
0.8
0.4
0.2
0.222
0.111
0.0555
0.3
0.15
0.075
0.6
0.3
0.15
0.222
0.111
0.0555
0.24
0.12
0.06
0.48
0.24
0.12
0.222
0.111
0.0555
0.2
0.1
0.05
0.4
0.2
0.1
AC Needed (kg)
Liquid Volume (liters)
System Size (liters)

2.5.2. Vacuum Pump Selection


One of the most common laboratory vacuum pumps is the rotary vein pump.
These are generally able to obtain pressures less than 10-3 torr, but they rely on the
pumping mechanism being immersed in vacuum pump oil. This presents a problem for
use with this system since the AC would likely accumulate in the vacuum pump oil and at
worst destroy the pump or at least necessitate frequent oil changes. Diaphragm pumps
present a good option for this experimental application. Although they are only capable
of an ultimate vacuum of ~1 torr, this pressure should be sufficient for the AC based on
65

the decomposition pressure as a function of temperature curves. The advantages of


diaphragm pumps are that they are oil free and the only surfaces that the removed gases
come into contact with are polymer membranes which are resistant to chemical attack.
Additionally, if AC were to condense inside of the pump, the pump can be quickly
disassembled and cleaned. The diaphragm vacuum pump chosen for this application is
the Vacuubrand MD1C three stage chemistry diaphragm pump. It is capable of obtaining
an ultimate vacuum of 1.5 torr and a pumping speed of 1.5 m3/hr. This pump speed
corresponds to a maxium rate of decomposition of AC of 1.6 kg/hr which sets an upper
limit to the power obtainable by the system. It would be possible to achieve a higher
pump speed with a larger pump but every vacuum pump has an upper limit to its
pumping speed so at the system level the pump speed will need to be selected to meet the
thermal power needs.

2.5.3. Vacuum Controller


A vacuum controller is necessary so that the effect of various overhead pressures
on the rate of decomposition can be measured. Although the lowest possible pressure will
always lead to the most rapid rate of decomposition, operating at the lowest possible
pressure may not be optimal at the system level. Accordingly it is important for a system
design to know if achieving a 1 torr pressure is necessary or if a higher pressure such as
200 torr or 400 torr would be sufficient to achieve rapid decomposition and yield good
system performance. The necessary pressure will drive pump selection, so it will be
important to fully understand the pressure dependence of the rate of decomposition.
Vacuubrand sells a vacuum controller which, when coupled with a fast-acting solenoid
valve between the vacuum pump and system, is able to control the system pressure. The
66

Vacuubrand CVC 3000 vacuum controller was selected for the process. The controller
measures pressure using an external vacuum gauge on the reaction vessel and regulates
the vacuum through the Vacuubrand VV-B 6C solenoid vacuum valve. The valve is made
with a corrosion resistant flowpath which prevents the NH3 from causing any problems to
the valve.

2.5.4. Vacuum Gauge Selection


The CVC 3000 vacuum controller comes with an integrated vacuum gauge inside
the controller unit. However, it was determined that an external gauge should be used that
is connected directly to the reactor to prevent any delay in pressure reading caused by the
tubing. The Vaccubrand VSK 3000 ceramic diaphragm gauge was chosen for this
application. It is corrosion resistant to almost any environment since the only part of the
gauge that comes in contact with the process is a ceramic. Additionally, a diaphragm type
gauge was chosen since it is capable of measuring pressure independent of gas species.
This feature is important since the two gas species which will be present in the vessel are
NH3 and CO2, and vacuum gauges are not normally calibrated to these gases. The gauge
is capable of measuring pressures from 0.1 to 810 torr.

2.5.5. Temperature Measurement


The underlying principle to the system is to perform an energy balance around the
reactor vessel to determine the amount of heat rejected to the AC. In order to do this the
temperatures of the water inlet and outlet as well as the internal reactor temperature must
be accurately measured and recorded. The Omega Portable Handheld Data Logger (OMDAQPRO-5300) was selected for this purpose along with thermistor temperature probes.

67

The data logger is capable of up to 8 temperature input channels and can store up to
512,000 temperature points.

2.5.6. Tubing Selection


For all the areas under vacuum exposed to AC, clear Tygon vacuum tubing (3/8
ID, 7/8 OD, wall) was selected so that any accumulation of AC could be visually
observed and the lines cleaned if necessary.

2.5.7. Simulated Thermal Load


For the purposes of this project it is important to have flexibility in a simulated
thermal load. A general purpose laboratory circulator (Polyscience Model 9005) was
chosen to represent any generic thermal load placed on the system. This circulator is
capable of operation from -20C to 150C depending on the circulating fluid selected. It
has a reservoir capacity of 6 liters and has two flow rates of 15 liters per minute or 7 liters
per minute. The recirculator was filled with distilled water as the working fluid.
For the energy balance on the water circulator, the water flow rate must be
known. The liquid flow rate through the system was determined by measuring the mass
of water that passed into the circulator at its inlet in a certain amount of time. This
procedure was repeated at each temperature to ensure accuracy.

2.5.8. Completed Experimental Apparatus


The completed experimental apparatus is shown in Figure 24. The water
circulator and the reactor jacket vacuum pump are in the bottom of the cart. The
circulator fluid loop is equipped with two valves so the reactor can be bypassed if

68

necessary. The entire system was assembled according to the schematic in Figure 23. The
exhaust from the diaphragm pump was vented into a laboratory hood.

Pressure
Transducer

Solenoid valve

Reaction vessel

Diaphragm
vacuum pump

Magnetic stir plate

Temperature
logger

Pressure controller
Thermal load

Figure 24. Experimental test apparatus

2.6. Ammonium Carbamate Decomposition Test System Experimental

Work
The decomposition system allows for the thermal power rating to be calculated
for the system by using the time dependent temperature data. This is a measurement
based on an energy balance around a recirculator and is different than the earlier
measurements which calculated the energy based on the amount of AC decomposed. For
each experiment conducted with the system, 650 mL of heat transfer fluid was used as it
was determined that this was the amount necessary to cover the heat transfer coils.
Although it was initially planned to use less heat transfer fluid in the system design
process, it was necessary to use this amount of fluid to completely cover the heat transfer
69

coils. The fluid was brought into thermal equilibrium at the test temperature before the
addition of the AC. Before the AC was added the temperature logger was started. The
amount of AC that was added was recorded as well as the time when the AC was added
and the time when the vacuum pump was started. The overhead pressure could be
controlled for each experiment. By using the time dependent temperature data, circulator
flow rate and the specific heat of water, the thermal power for the system could be found
by Equation 22.
(22)

where

is the rate of heat flow (W),

is the mass flow rate of the water (g/s), Cp is the

specific heat of water, and T is the water temperature change between the inlet and
outlet of the reactor. The time dependent power rating was then integrated with respect to
time using the trapezoid rule to find the total amount of energy consumed by the AC
decomposition. This result was compared with the amount of energy consumed by the
decomposition and the amount of energy necessary to heat the AC to the reactor
temperature. The amount of energy consumed by the decomposition was determined
from the mass of the AC added and the literature value of the heat of decomposition of
2.01 kJ/g. The amount of energy necessary to bring the AC from room temperature to the
reactor temperature was calculated using the heat capacity of the AC, which was assumed
to be constant. The heat loss through the reactor walls was neglected and a vacuum
insulated reactor was used to assure that this was a reasonable assumption.
Both EG and PG were used as heat transfer fluids in the decomposition
experiments so that their performance could be compared to give a recommendation of
the optimal heat transfer fluid for the system. Tests were conducted at the following

70

temperatures: 30C, 45C, 50C, 55C and 60C. The greatest number of experiments
was conducted at 60C since this is the highest temperature that would be of practical
value for this work and as the highest temperature should give the best thermal power
rating by providing the most rapid decomposition. For an initial run at each temperature,
the pressure controller was set to 0 torr so that the vacuum pump would run continuously
and result in the maximum rate of decomposition available from the system. At 60C
higher pressures of 200 and 400 torr were tested as well. A representative picture of the
decomposition reaction occurring is shown in Figure 25. Bubbles of the product gases
can be seen in the image.

Figure 25. Decomposition of ammonium carbamate in reactor

2.6.1. Decomposition Test System Experimental Procedure


Heat transfer fluid (650 mL) was added to the reactor. The fluid was agitated with
a magnetic stir bar to optimize the heat transfer. The circulator was set to the test
temperature, and the reactor contents were allowed to come to the desired test
71

temperature as measured by the reactor thermistor probe. The vacuum pump to the
reactor jacket was turned on. The approximate amount of AC was measured; the exact
amount added for the reaction was determined by weighing the jar with the AC and then
the empty jar after addition. The temperature logger was started at least one minute prior
to the test so that the initial temperatures could be recorded. The pressure controller was
set to the appropriate pressure for the test. Next, the AC was quickly added to the reactor,
the reactor was closed and the vacuum pump was turned on using the pressure controller.
The time when the AC was added to the reactor and the time when the vacuum pump was
started were recorded. The pressure displayed on the vacuum controller was manually
recorded at appropriate intervals throughout the experiment. The decomposition was
allowed to continue until the reactor contents, water inlet and water outlet were at steady
state.

2.6.2. Experimental Data Analysis


The experimentally collected parameters for each test were the time dependent
temperature of the reactor contents, the time dependent circulator fluid temperature at the
reactor inlet and outlet, the time dependent pressure in the reactor, the amount of AC
added and the room temperature. Specific information for each run including
experimental parameters and graphs can be found in the appendix. Since the AC was
stored on the laboratory bench, its initial temperature was assumed to be that of the room.
For each run the lower bound of integration is the time when the AC was added to the
reactor and the upper bound of integration is the time when thermal equilibrium was
reached. For runs where the pressure was subsequently lowered once thermal equilibrium
was reached, the lower bound of integration is when the pressure controller was changed.
72

The bounds of integration are shown for each run in the form of vertical lines on the
graphs which can be found in the appendix. For each run the percent difference between
energy found from the integration and AC mass value is shown. The T shown is that
between the reactor inlet and outlet for the circulator. Each experimental run is
summarized in Table 20. In this table the difference is negative when the predicted
energy value is higher than amount of energy found using numerical integration.

Table 20. Summary of ammonium carbamate test system experimental data


Temp
(C)

Solvent

AC
(g)

Decomp.
(kJ)

Cp (kJ)

Integration
(kJ)

Difference

Peak
Power (W)

105.2

Set
Pressure
(torr)
0

30

PG

211.53

1.88

161.32

-24.4%

39.3

30

EG

104.0

208.95

1.86

107.99

-48.8%

52.2

45

PG

104.6

210.31

6.01

255.98

18.3%

138

45

EG

104.3

209.59

5.92

225.05

4.4%

145.5

50

PG

102.4

205.73

7.40

190.67

-10.5%

144.7

55

PG

101.4

203.76

6.96

206.31

-2.1%

203.8

60

PG

100.9

202.89

7.05

186.82

-11.0%

223.9

60

PG

102.6

200, 0

206.27

7.18

195.37

-8.5%

223.3, 42.0

60

EG

102.0

204.99

6.58

206.64

-2.3%

241.5

60

EG

101.7

200, 0

204.34

6.30

219.50

4.2%

238.8, 74.2

60

PG

102.2

205.39

7.38

236.12

11.0%

60

EG

103.0

207.02

7.41

208.73

-2.7%

60

PG

204.4

400, 200,
0
400, 200,
0
0

410.75

14.77

530.85

24.8%

174.2,
101.3, 44.0
159.4,
134.1, 87.7
319.2

60

PG, reused

100.3

201.53

7.16

248.90

19.3%

266.9

60

PG, reused

102.3

205.59

7.27

256.73

20.6%

269.8

2.6.3. Discussion of Experimental Results


An analysis of the results shows several trends that were expected from the early
decomposition experiments conducted under high vacuum. Experimental trends that will

73

be discussed are the effect of temperature, pressure, solvent, and the amount of AC added
on the amount of heat removed by the AC and the peak power rating that was achieved.
The early decomposition experiments conducted for this work indicated that
temperature would have a strong effect on the rate of decomposition and therefore on the
thermal power achieved. This trend is clearly demonstrated since the peak power
increases as the temperature increases from a minimum of 39.3 W at 30C to a maximum
319.2 W at 60C. Hence, for situations in which it is desired to have a high thermal
power rating, it is shown that the decomposition reaction vessel should operate at the
highest possible temperature. The current system has mass transfer limitations because
the vacuum pump being used limits mass transfer capability. Therefore, one way to
overcome the temperature limitation would be to install a more powerful vacuum pump,
or multiple pumps, to achieve a greater rate of mass transfer.
The pressure set by the vacuum pump also has an effect on the peak power
achieved by the system. The data collected only allows analysis at 60C, but it is
expected that similar trends would also be found at other temperatures. At 60C, setting
the pressure controller to either 200 torr or 0 torr did not have an appreciable effect on the
peak power. With EG the peak powers were observed to be 241.5 and 238.8 W at 0 and
200 torr, respectively, and with PG the peak powers were 223.9 and 223.3 W at 0 and
200 torr respectively. A way to explain this observation is that the equilibrium pressure of
AC at 60C is approximately 850 torr which is considerably higher than 200 torr.
Additionally, examining the pressure data for the experiments in Figure 39 and Figure 43
shows that even when the pressure controller was set to 0 torr it remained considerably
above this pressure for much of the experiment. This means that while the controller was

74

set low, the pressure in the reactor was much higher due to rapid decomposition.
However, a more marked difference is noted when the pressure was set to 400 torr. With
EG the peak power was 159.4 and 241.5 W for 400 torr and 0 torr, respectively, and for
PG the peak power was 174.2 W and 223.9 W for 400 torr and 0 torr respectively. The
difference observed in changing the set overhead pressure from 200 to 400 torr shows
that the pressure certainly has a strong effect on the system thermal power and therefore
must be considered in any system design.
An important result of the pressure tests is that while it is necessary to lower the
pressure of the system for high power ratings a high vacuum will not be needed. In the
early decomposition testing, all runs were conducted with a high vacuum system. It was
suspected that a system capable of that level of vacuum was not needed for rapid
decomposition. The fact that there was no difference in peak power at both a system set
to 0 and 200 torr makes the idea of using a system at reduced pressure more realistic. In
an application, it is foreseeable to lower system pressure to this level, but it would be in
no way reasonable to lower the system pressure to 1 x 10-5 torr as was used in the early
decomposition experiments.
It was noted when the system was set to different pressures that the amount of AC
which decomposed until the system reached steady state changed. This is evaluated using
numerical integration to find the amount of heat rejected to the thermal load. For the case
of AC in PG at 400 torr, 200 torr and 0 torr, as seen in Figure 47 and Table 31, the
amount of energy that was rejected to the AC at each pressure was 173 kJ, 44.6 kJ and
18.4 kJ, respectively, for a total of 236.1 kJ, compared to a predicted total of 212.8 kJ.
The reason that steady state was reached at each pressure is that some amount of AC, or

75

its decomposition products, will be soluble in the PG at each pressure. This is evident
since as the pressure was reduced from a value where the system was at steady state, the
vessel temperature fell as the AC decomposed and caused the system to reject more heat
to the simulated thermal load. Visually, it was evident in the system since when the set
pressure was changed from 400 torr to 200 torr or from 200 torr to 0 torr, the heat transfer
fluid began to bubble. The source of this bubbling could either be dissolved AC
decomposing or decomposition products being removed from solution in an endothermic
process which lowered the vessel temperature. It is likely that ammonia could be the
decomposition product removed since it is extremely soluble in EG, and presumably in
PG, as discussed in Section 2.3.8. Therefore, it is plausible that once the pressure was
lowered, additional ammonia was removed from the solution, lowering the temperature.
On a full scale system this steady state limitation can be overcome by continuously
adding AC to the decomposition system to keep the reactor contents far from equilibrium
conditions to maintain a high power rating.
Early experiments showed that using a heat transfer fluid in which AC is soluble
showed a drastic increase in the rate of decomposition as compared to a heat transfer
fluid in which it is insoluble. Ethylene glycol was the first heat transfer fluid which was
found to satisfy both the solubility criteria and have a very high boiling point so that it
would not be consumed during the process. Propylene glycol was also considered since it
is similar to EG but is much less toxic, to the point where it is considered to be food safe.
Both EG and PG were considered in testing to determine if EG had an appreciable
advantage over the preferred PG. It was found at each temperature that EG had a slightly
higher peak power than PG. The comparisons can be found in Table 20 and showed

76

percent differences of 28%, 5% and 8% for 30C, 45C and 60C, respectively. The
larger percent difference at 30C can be explained since the peak powers were relatively
low so a small difference of only 12.9 W leads to a difference of 28% while at 60C a
difference of 17.6 W leads to a difference of 8%. Since, especially at higher temperatures,
the two solvents offer comparable performance it can be concluded that using nontoxic
PG should not lead to performance degradation compared to EG.
The amount of AC initially added to the system has an effect on the peak power.
This can be shown by comparing the experiments conducted in PG at 60C where initial
charges of 100.9 g and 204.4 g of AC were added. The peak power found at 100.9 g was
223.9 W, while that for the 204.4 g charge was 319.2 W. Part of this increase in peak
power arises from the heat capacity of the AC. Adding more AC will cause a greater
initial temperature depression in the reactor contents since it is at a lower temperature
than the PG and a greater amount of AC will further lower the temperature of the PG.
The heat capacity of AC at 60C is 1.92 kJ/kgC and the heat capacity of PG at 60C is
2.73 kJ/kgC.90,96,97 Therefore, adding 100.0 g of AC at 20C to 650 mL PG at 60C
should cause the temperatures to stabilize at approximately 56C while adding 204.4 g of
AC at 20C should cause the temperature to stabilize at 53C. It was observed that adding
100.9 g of AC caused the reactor contents to reach a temperature minimum of 47.6C,
while adding 204.4 g of AC caused the reactor contents to reach a minimum of 45.6C.
These temperature differences are approximately the same as would be expected from the
specific heats alone. However, this is not sufficient to account for a peak power
difference of 35%. A second explanation for the marked increase in peak power is that
adding a greater amount of AC kept the reactor contents farther from equilibrium

77

conditions and therefore increased the rate of decomposition which increases the power
rating. This makes sense in light of the aforementioned discussion of the effect of
equilibrium in the system. For system design recommendations this shows that keeping a
greater amount of AC in the slurry will increase the system power rating by maximizing
the rate of decomposition.

2.6.4. Conclusions from Ammonium Carbamate Decomposition System Tests


The tests conducted in this work have demonstrated several concepts that will be
necessary to incorporate into the next generation test system. The first result is that
running the system at higher temperatures will lead to much higher thermal power
ratings. Although this was initially expected and was shown with the early decomposition
tests using a high vacuum system, it reinforces that in any larger system design, every
effort should be made to use a high temperature for maximum thermal power. The second
important conclusion, which was not previously demonstrated, is the effect of pressure on
the rate of decomposition and therefore on thermal power. Many tests were conducted
with the system pressure set to 0 torr, but as the results in the appendix show, the pressure
in the reactor during the experiment was far from this value since rapid decomposition
kept the system pressure higher than the set pressure. Experiments were then conducted
using the pressure controller to maintain a higher pressure in the system. It was found that
a higher pressure could be set and still maintain a rapid rate of decomposition.
Specifically, the tests conducted at 60C showed essentially no difference in the peak
power between the system set at 0 torr and the system set at 200 torr but did show a
difference in the total amount of AC that would be decomposed before equilibrium is
reached at a pressure, a limitation which can be overcome by continuously adding AC.
78

The conclusion from the pressure effect is positive from a real system perspective since it
is much more realistic to obtain a pressure on the order of 200 torr than 10-5 torr. The
choice of either EG or PG led to comparable results, so PG seems preferable as the
system heat transfer medium, since it is non-toxic and environmentally friendly. Finally,
the amount of AC in the reactor does have an effect on the thermal power and adding a
greater amount of AC to the system should function to increase the thermal power rating.
This can be tested by using a method to continuously add AC to the system and then
evaluate the optimal amount of AC to maintain in the reactor.

79

CHAPTER III: CONCLUSIONS AND FUTURE WORK


Ammonium carbamate shows promise as a high energy density thermal energy
storage material with the ability to effectively manage high-flux low-grade heat. This
project has demonstrated that AC will best function when integrated with a heat transfer
fluid. Testing has shown that both EG and PG are effective heat transfer fluids for AC
with PG the preferred fluid since it does not have the toxicity problems that are
associated with EG. It has also been found that reducing the overhead pressure on the
system will greatly enhance the power rating through improving the rate of mass transfer.
This had been expected from the equilibrium decomposition pressure and was reinforced
with all experiments. It was also shown that it is not necessary to reduce the pressure to
very low vacuum levels (10-5 torr), but that a vacuum on the order of 200 torr (0.25 atm)
will be effective. The small scale test system has shown peak thermal power ratings of
over 300 W or over 340 W/kg of AC and PG, which demonstrates the capability of AC.
Future work should focus on developing more temperature-pressure-power rating
relationships for the decomposition test system. Additionally, a method should be
developed to continuously add AC to the reactor during an experiment without the need
to bring the system to atmospheric pressure and remove the lid.

80

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92

APPENDIX
The data presented in the appendix has a data table and two graphs for each
experimental run. In the data tables the initial bulk temperature is the temperature of the
heat transfer fluid prior to the addition of the AC. The initial AC temperature is the room
temperature, which is assumed to be the AC temperature since it was stored on the
laboratory bench. The heat from decomposition is the amount of energy required to
completely decompose the mass of AC added. The heat from the temperature change of
the AC accounts for the temperature change of the AC using the heat capacity. The
bounds of integration were chosen based on the time when the AC was added or the
pressure changed and the time when steady state was reached. The percent difference is
negative when the energy from the integration is less than that from the calculated energy
based on the AC mass. In the first figure for each run the bulk temperature is the
temperature of the heat transfer fluid. The temperature in is the water temperature
measured from the recirculator immediately before it enters the heat transfer coil into the
reactor. The temperature out is the water temperature measured from the recirculator
immediately after its leaves the heat transfer coil in the reactor. The heat rejected is the
thermal power calculated from the energy balance around the recirculator heat exchanger
in the reactor. In the second figure the pressure was manually recorded as displayed on
the pressure controller. The T is the reactor inlet and outlet recirculator water
temperature difference. The vertical lines on each graph represent the bounds of
93

integration. Where there is more than one area of integration different colors were used
for each zone of integration.

94

Table 21. Experimental data for ammonium carbamate in propylene glycol at 30C

Heat Rejected (Watts)

300

30.0
19.3
105.241
12.00
211.5
1.88
100
9500
161.3
-24.41%
PG

Heat Rejected
Bulk Temperature
Temp In
Temp Out

250
200
150
100
50
0
0

2000

4000

6000

35
34
33
32
31
30
29
28
27
26
25

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper bound of integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

8000

Time (s)

50
45
40
35
30
25
20
15
10
5
0

2.00
1.80
1.60
1.40
1.20
1.00
0.80
0.60
0.40
0.20
0.00
10000

Pressure
T

2000

4000

6000

8000

T (C)

Pressure (torr)

Figure 26. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 30C

Time (s)

Figure 27. Pressure and T for ammonium carbamate in propylene glycol at 30C

95

Table 22. Experimental data for ammonium carbamate in ethylene glycol at 30C
30.0
19.3
103.957
12.00
208.9
1.86
180
10000
108.0
-48.77%
EG

Heat Rejected (Watts)

300.00
Heat Rejected
Bulk Temperature
Temp In
Temp Out

250.00
200.00
150.00
100.00
50.00
0.00
0

2000

4000

6000

8000

35
34
33
32
31
30
29
28
27
26
25
10000

Temp (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

Figure 28. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
30C
40

30
25
20
15
10
5
0
0

2000

4000

6000

8000

T (C)

35
Pressure (torr)

2
1.8
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
10000

Pressure

Time (s)

Figure 29. Pressure and T for ammonium carbamate in ethylene glycol at 30C

96

Table 23. Experimental data for ammonium carbamate in propylene glycol at 45C

200
180
160
140
120
100
80
60
40
20
0
0

1000

2000

3000

45.2
28.2
104.632
12.79
210.3
6.00
60
3700
256.0
18.34%
PG

50
48
46
44
42
Heat Rejected
40
Bulk Temperature
38
Temp In
36
Temp Out
34
32
30
4000
5000
6000

Temperature (C)

Heat Rejected (Watts)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

140

Pressure (torr)

120
100
80
60
40
20
0
0

1000

2000

3000

4000

5000

5
4.5
Pressure
4
T
3.5
3
2.5
2
1.5
1
0.5
0
6000 7000

T (C)

Figure 30. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 45C

Time (s)

Figure 31. Pressure and T for ammonium carbamate in propylene glycol at 45C

97

Table 24. Experimental data for ammonium carbamate in ethylene glycol at 45C

200
180
160
140
120
100
80
60
40
20
0
0

1000

2000

3000

45.3
28.6
104.274
12.79
209.6
5.92
20
5500
225.1
4.43%
EG

50
48
46
44
42
Heat Rejected
40
Bulk Temperature
38
Temp In
36
Temp Out
34
32
30
4000
5000
6000

Temperature (C)

Heat Rejected (Watts)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

Figure 32. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
45C
120
T

80
60
40
20
0
0

1000

2000

3000

4000

5000

6000

T (C)

100
Pressure (torr)

5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
7000

Pressure

Time (s)

Figure 33. Pressure and T for ammonium carbamate in ethylene glycol at 45C

98

Table 25. Experimental data for ammonium carbamate in propylene glycol at 50C
49.8
19.3
102.353
12.71
205.7
7.40
50
2500
190.7
-10.54%
PG

300

55

250

50

200

Heat Rejected
Bulk Temperature
Temp In
Temp Out

150
100

45
40

50

35

30
4000

1000

2000

3000

Temperature (C)

Heat Rejected (Watts)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

Pressure (torr)

160
140

Pressure

120

100
80
60
40
20
0
0

1000

2000

3000

5.00
4.50
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00

T (C)

Figure 34. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 50C

4000

Time (s)

Figure 35. Pressure and T for ammonium carbamate in propylene glycol at 50C
99

Table 26. Experimental data for ammonium carbamate in propylene glycol at 55C

Heat Rejected (Watts)

300
250
200
150
100
50
0
0

500

1000

1500

55.2
21.5
101.372
12.18
203.8
6.95
90
2200
206.3
-2.09%
PG

60
58
56
54
52
Heat Rejected
50
Bulk Temperature
48
Temp In
46
Temp Out
44
42
40
2000
2500
3000

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

300

Pressure (torr)

250
200
150
100
50
0
0

500

1000

1500

2000

5.00
Pressure
4.50
4.00
T
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
2500
3000

T (C)

Figure 36. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 55C

Time (s)

Figure 37. Pressure and T for ammonium carbamate in propylene glycol at 55C
100

Table 27. Experimental data for ammonium carbamate in propylene glycol at 60C
60.1
20.8
100.94
11.57
202.9
7.05
39
2000
186.8
-11.01%
PG

300

70

250

65

200

60

150

Heat Rejected
Bulk Temperature
Temp In
Temp Out

100
50
0
0

500

1000

1500

55
50

45
2500

2000

Temperature (C)

Heat Rejected (Watts)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Theoretical Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

Figure 38. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C
300

7
Pressure
T

200

6
5
4

150

100

T (C)

Pressure (torr)

250

50

0
0

500

1000

1500

2000

0
2500

Time (s)

Figure 39. Pressure and T for ammonium carbamate in propylene glycol at 60C

101

Table 28. Experimental data for ammonium carbamate in propylene glycol at 60C with
two pressure settings

Heat Rejected (Watts)

300

60.2
20.7
102.624
11.57
206.3
7.18
60
1700
195.4
-8.47%
PG

Heat Rejected
Bulk Temperature
Temp In
Temp Out

250
200

70
65
60

150
55

100
50

50

45
0

1000

2000

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

3000

Time (s)

Figure 40. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with two pressure settings
7
Pressure

Pressure (torr)

300

250

6
5

200

150

100

50

0
0

1000

2000

T (C)

350

3000

Time (s)

Figure 41. Pressure and T for ammonium carbamate in propylene glycol at 60C at two
pressures
102

Table 29. Experimental data for ammonium carbamate in ethylene glycol at 60C
60.3
24
101.986
11.57
205.0
6.58
50
1900
206.6
-2.33%
EG

300

70

250

65

200

60

150

Heat Rejected
Bulk Temperature
Temp In
Temp Out

100
50
0
0

500

1000

1500

2000

2500

55

Temperature (C)

Heat Rejected (Watts)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

50
45
3000

Time (s)

300

Pressure (torr)

250
200
150
100
50
0
0

500

1000

1500

2000

10
9
Pressure
8
T
7
6
5
4
3
2
1
0
2500
3000

T (C)

Figure 42. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C

Time (s)

Figure 43. Pressure and T for ammonium carbamate in ethylene glycol at 60C
103

Table 30. Experimental data for ammonium carbamate in ethylene glycol at 60C at two
pressures
Initial Bulk Temperature (C)
Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration 1 (s)
Upper Bound of Integration 1 (s)
Lower Bound of Integration 2 (s)
Upper Bound of Integration 2 (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Heat Rejected
Bulk Temperature
Temp In
Temp Out

250
200

70
65
60

150
55

100
50

50

45
5000

1000

2000

3000

4000

Temperature (C)

Heat Rejected (Watts)

300

60.3
22
101.661
11.57
204.3
6.30
121
2200
2800
4200
219.5
4.21%
EG

Time (s)

300

Pressure (torr)

250
200
150
100
50
0
0

1000

2000

3000

10
Pressure
9
8
T
7
6
5
4
3
2
1
0
4000
5000

T (C)

Figure 44. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at two pressures

Time (s)

Figure 45. Pressure and T for ammonium carbamate in ethylene glycol at 60C at two
pressures
104

Table 31. Experimental data for ammonium carbamate in propylene glycol at 60C at
three pressures

Heat Rejected (Watts)

300

59.7
19.3
102.184
11.57
205.4
7.38
60
2300
2380
3200
3580
4100
236.1
10.97%
PG

Heat Rejected
Bulk Temperature
Temp In
Temp Out

250
200

70
65
60

150
55

100
50

50

45
5000

1000

2000

3000

4000

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration 1 (s)
Upper Bound of Integration 1 (s)
Lower Bound of Integration 2 (s)
Upper Bound of Integration 2 (s)
Lower Bound of Integration 3 (s)
Upper Bound of Integration 3 (s)
Sum of integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

450
400
350
300
250
200
150
100
50
0

Pressure
T

4.00
3.50
3.00
2.50
2.00
1.50

T (C)

Pressure (Torr)

Figure 46. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C at three pressures

1.00
0.50
0

1000

2000

3000

4000

0.00
5000

Time (s)

Figure 47. Pressure and T for ammonium carbamate in propylene glycol at 60C at
three pressures
105

Table 32. Experimental data for ammonium carbamate in ethylene glycol at 60C at three
pressures

Heat Rejected (Watts)

300

59.7
19.5
102.997
11.57
207.0
7.41
60
900
1400
2500
3150
3900
208.7
-2.66%
EG

Heat Rejected
Bulk Temperature
Temp In
Temp Out

250
200

64
62
60
58

150

56

100

54

50

52

50
5000

1000

2000

3000

4000

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration 1 (s)
Upper Bound of Integration 1 (s)
Lower Bound of Integration 2 (s)
Upper Bound of Integration 2 (s)
Lower Bound of Integration 3 (s)
Upper Bound of Integration 3 (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

450
400
350
300
250
200
150
100
50
0

Pressure
T

3.5
3
2.5
2
1.5

T (C)

Pressure (Torr)

Figure 48. Temperatures and heat rejected for ammonium carbamate in ethylene glycol at
60C at three pressures

1
0.5
0

500

1000

1500

2000

2500

3000

0
3500

Time (s)

Figure 49. Pressure and T for ammonium carbamate in ethylene glycol at 60C at three
pressures
106

Table 33. Experimental data for ammonium carbamate in propylene glycol at 60C with
double AC loading

500
450
400
350
300
250
200
150
100
50
0
0

1000

2000

59.8
19.1
204.355
11.57
410.7
14.8
110
2700
530.8
24.75%
PG

65
63
61
59
57
55
Heat Rejected
Bulk Temperature
53
Temp In
51
Temp Out
49
47
45
3000
4000

Temperature (C)

Heat Rejected (Watts)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

Figure 50. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with double ammonium carbamate loading
300
T

200
150
100
50
0
0

500

1000

1500

2000

2500

3000

T (C)

250
Pressure (torr)

10
9
8
7
6
5
4
3
2
1
0
3500

Pressure

Time (s)

Figure 51. Pressure and T for ammonium carbamate in propylene glycol at 60C with
double ammonium carbamate loading
107

Table 34. Experimental data for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol

Heat Rejected (Watts)

300
250
200
150
100
50
0
0

500

1000

1500

59.8
19.6
100.264
11.57
201.5
7.16
70
1500
248.9
19.27%
PG Reused

65
63
61
59
57
Heat Rejected
55
Bulk Temperature
53
Temp In
51
Temp Out
49
47
45
2000
2500
3000

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

Figure 52. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with reused propylene glycol
300
T

200
150
100
50
0
0

500

1000

1500

2000

2500

T (C)

250
Pressure (torr)

10
9
8
7
6
5
4
3
2
1
0
3000

Pressure

Time (s)

Figure 53. Pressure and T for ammonium carbamate in propylene glycol at 60C with
reused propylene glycol
108

Table 35. Experimental data for ammonium carbamate in propylene glycol at 60C with
twice used propylene glycol

Heat Rejected (Watts)

300
250
200
150
100
50
0
0

500

1000

1500

59.9
19.9
102.285
11.57
205.6
7.27
100
1600
256.7
20.61%
PG Reused

65
63
61
59
57
Heat Rejected
55
Bulk Temperature
53
Temp In
51
Temp Out
49
47
45
2000
2500
3000

Temperature (C)

Initial Bulk Temperature (C)


Initial AC Temperature (C)
AC Added (g)
Water Flow Rate (g/s)
Heat from Decomposition (kJ)
Heat from Temperature Change of AC (kJ)
Lower Bound of Integration (s)
Upper Bound of Integration (s)
Sum of Integration (kJ)
Difference (integration and theoretical)
Solvent

Time (s)

300
Pressure

Pressure (torr)

250

200
150
100
50
0
0

500

1000

1500

2000

2500

10
9
8
7
6
5
4
3
2
1
0
3000

T(C)

Figure 54. Temperatures and heat rejected for ammonium carbamate in propylene glycol
at 60C with twice reused propylene glycol

Time (s)

Figure 55. Pressure and T for ammonium carbamate in propylene glycol at 60C with
twice reused propylene glycol
109

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