Disposal of Toxic and Non-Toxic Waste Through Lasers

Masters Thesis, KTH- Royal Institute of Technology, Stockholm Sweden Disposal of Toxic and Non-Toxic Waste through Lasers

Destruction of toxic solids, liquids and gases Models and Experimental Results

Author: Ali Islam Date: 30-05-2013 Supervisor :Dr. Muhammad Muddassir Silvio Gualini, Dr. Anders Eliasson, Dr. Hasse Fredriksson Masters Thesis in Materials Processing Department of Materials Science and Engineering KTH-Royal Institute of Technology, Stockholm Sweden

Abstract

The report discusses the destruction of toxic and non-toxic solids, liquids and gases through lasers. In order to completely understand the project first chapters describes the basics about laser and plasma separately, from definition to types, components and categories. Differences between laser and microwave system are covered in this chapter as well. Besides lasers there are different technologies that are currently being used to destroy toxic and non-toxic materials. These technologies were studied and comparison tables are made in order to discern between different destruction technologies. For the destruction of toxic and non-toxic materials through lasers two mathematical models have been developed, molecular dissociation model and plasma exploitation model, and later the experimental work was carried out on one of the toxic material. Mathematical modeling and experimental work is in accordance with each other as discussed in results and discussion. Mathematical model shows that all the materials discussed in the report can be destroyed by lasers but in order to carry further experiments on all other toxic and non- toxic materials, a proposal is made for the laser reactor using CAD model (Solid Edge) and drawing software (AutoCAD). Tables and mathematical calculations have been placed in appendix at the end of the report.

Preface:

This project is a portion of a big idea of Dr. Muhammad Muddassir Silvio Gualini which is to generate electrical power through solar pumped lasers. The original idea was to use solar pumped lasers to destroy toxic and non-toxic waste materials. Solid, liquid and gas toxic materials listed were supplied by AMIAT, the public company in Torino collecting house and toxic waste. The laser action on the waste materials will produce plasma and a catalyst will transform the extremely hot and high pressure plasma into a high temperature and high pressure inert gas (not-toxic, not-smelling). Generation of high temperature gas can be used to generate electricity through gas turbine. In order to obtain the optimal turbine parameters of gas temperature and pressure the inert gas is previously cooled through heat exchangers generating hot water to be supplied to for house hold purposes. The focus of this report is on the destruction of toxic and non-toxic materials through lasers. The destruction of toxic materials is studied by two mathematical models. First the molecular dissociation model is used to calculate the destruction of toxic materials and then the plasma exploitation model is used. There are different ways of destruction of toxic materials as well which are currently being employed as well but either their cost is extremely high or they produce by products which are dangerous. A solar pumped laser or a laser powered by part of the energy generated by the gas turbine (co- generation) or by a solar panel or thermal unit. In any case one of these three solutions would eliminate the running cost factor of the laser can be almost eliminated. In any case the proposed and discussed method grants the 99.5% destruction of toxic and non-toxic materials. The mathematical models prove the assertion.

Contents

1. Basics about laser and plasma ...... 1 1.1. Laser ...... 1 1.1.1. Abbreviation ...... 1 1.1.2. Definition...... 1 1.1.3. How to produce laser light? ...... 1 1.1.4. Components of lasers ...... 2 1.1.5. Categories of lasers ...... 4 1.2. Plasma ...... 4 1.2.1. Common forms of Plasma ...... 5 1.2.2. Degree of Ionization ...... 5 1.2.3. Temperature measurement of plasma ...... 6 1.2.4 Density of plasma ...... 6 1.2.5. Potential of Plasma ...... 7 1.2.6. Magnetization ...... 7 1.2.7. Mathematical description of plasma ...... 7 1.3. Laser confinement of plasma ...... 8 1.3.1. LIBS in brief...... 8 1.3.2. Life cycle of LIBS process ...... 10 1.3.3. Advantages of LIBS ...... 11 1.4. Differences between laser and microwave systems...... 15 2. Overview of current technologies to treat toxic material ...... 16 2.1. Thermal Energy: Incineration and pyrolysis ...... 16 2.2. Plasma Energy: ...... 19 2.3. Microwave Energy: ...... 21 3. Comparison tables for destruction of selected toxic materials through different technologies ...... 24 4. Molecular dissociation model ...... 27 4.1. Solids ...... 27 4.1.1. Zinc Sulfide, ZnS ...... 27 4.2. Gases ...... 31 4.2.1. NO ...... 31

4.2.2. NO2 ...... 32 4.3. Calculations for number of photons to destroy toxic materials ...... 32

4.4. Material destroyed rate by CO2 Gas Dynamic Laser ...... 37 4.4.1. Solids ...... 38 4.4.2. Gases ...... 39 4.4.3. Liquids ...... 40 5. Plasma exploitation ...... 47 5.1. Solids ...... 50 5.2. Gases ...... 52 5.3. Liquids ...... 53 6. Proposal of laser reactor for decomposition of toxic materials ...... 63

7. Experimental decomposition of NOx...... 70 8. Results and Discussion ...... 73 8.1. Experimental Results and Discussion ...... 73 8.2. Methematical models results and discussion ...... 75 8.3. Conclusions from results and discussion ...... 80 9. Acknowledgments ...... 81 10. References ...... 82 Appendix ...... 103 1. Solids ...... 103 1.1. Phosphors ...... 103 1.2. Asbestos ...... 108 2. Gases ...... 114

2.1. NOx ...... 114 2.2. CFC ...... 123 2.3. HCFC ...... 136 3. Liquids ...... 143 3.1. Acids ...... 143 3.2. Bases ...... 161 3.3. Organic Solvents ...... 179 4. Liquids ...... 199

4.1 Sulfuric Acid, H2SO4 ...... 199

4.2 Nitric Acid, HNO3 ...... 199

4.3 Acetic Acid, CH3COOH ...... 200 4.4 Hydrochloric Acid, HCl...... 200 4.5 Hydrogen Bromide, HBr ...... 201 4.6 Hydrogen Iodide, HI ...... 201

4.7 Boric Acid, H3BO3 ...... 202

4.8 Oxalic Acid, C2H2O4 ...... 202 4.9 Formic Acid, HCOOH ...... 203

4.10 Citric Acid, C6H8O7 ...... 203

4.11 Benzoic Acid, C7H6O2 ...... 204

4.12 Hydrogen Peroxide, H2O2 ...... 204

4.13 Ammonia, NH3 ...... 205

4.14 Calcium Hydroxide, Ca(OH)2 ...... 205 4.15 Calcium Oxide, CaO ...... 206

4.16 Sodium Bicarbonate, NaHCO3 ...... 206

4.17 Sodium bicarbonate, NaHCO3 ...... 207

4.18 Sodium Carbonate, Na2CO3 ...... 207

4.19 Barium Hydroxide, Ba(OH)2, Born Haber cycle ...... 208

4.20 Strontium Hydroxide, Sr(OH)2 ...... 209

4.21 Aluminum Hydroxide, Al(OH)3 ...... 210 4.22 Sodium Hydride, NaH ...... 211 4.23 Sodium Hydride, NaH ...... 211 4.24 Potassium Hydroxide, KOH ...... 212 4.25 Lithium Hydroxide, LiOH ...... 212

4.26 Magnesium Hydroxide, Mg (OH) 2...... 213 4.27 Sodium Hydroxide, NaOH ...... 214

4.28 Ethanol, C2H5OH ...... 215

4.29 Methanol, CH3OH ...... 215 4.30 Propanol, C3H7OH ...... 216

4.31 Tetrachloroethylene, C2Cl4 ...... 216

4.32 Toulene, C7H8 ...... 217

4.33 Chloroform, CHCl3 ...... 217

4.34 Benzene, C6H6 ...... 218

4.35 Acetone, C3H6O ...... 218

4.36 Methyl tert-butyl ether, C5H12O ...... 219

4.37 Propylene carbonate, C4H6O3 ...... 219

4.38 Methylene Chloride, CH2Cl2 ...... 220

4.39 n-heptane, C7H16 ...... 220

4.40 Isopropanol, C3H8O ...... 221

1. Basics about laser and plasma

1.1. Laser

1.1.1. Abbreviation

Laser stands for Light amplification by stimulated emission of radiations. The way laser light is different from the monochromatic, bulb light and sunlight is demonstrated Table 1.1.1.

Table 1.1.1: Comparison of laser light with other sources of light, [1]

Type Color Direction of all the waves Light bulb Not monochromatic Not same Sunlight Not monochromatic same Monochromatic Monochromatic Not same Laser Monochromatic same

1.1.2. Definition

To be a laser light has to fulfill following two criteria, [1]

 It should be monochromatic. Which means it should have the same color. That means all the wave lengths are equal. I.e. crests and troughs line up with each other.  All the waves move in the same direction or all the particles are moving in the same direction

1.1.3. How to produce laser light?

When a photons coming at a high speed hits an atom. Electron jumps to a higher energy level. When it jumps back to lower energy level, it emits photon of the same color but in random direction, whereas incoming photon disappears. [1]

When a photon coming at a high speed hits an atom, which is already excited the electrons jumps to a higher energy level and when it jumps back to the lower energy level. It emits photon of the same color and in the same direction. This time the incoming photon is not disappeared. This process is called “stimulated emission”. [1]

When one high speed photon hits an excited atom two photons are created. When these two photons hit two other excited atoms four photons are created. In this way “light amplification” occurs by stimulated emission. [1]. It is demonstrated in Figure 1.1.1.

Figure 1.1.1: Dual nature of light shown as photons [1] Light has a dual nature. It behaves as particle as well as waves. When an electromagnetic waves hits an excited atom. After interaction it takes the energy of the atom. The wavelength remains the same whereas amplitude increases [1]. Wave nature of light is demonstrated in Figure 1.1.2.

Figure 1.1.2: Dual nature of light shown as wave [1]

Excitation of atoms is called “Population Inversion” and it can be done in two ways, [1]

 Pumping electrical energy to the atoms which have to be excited  Shinning different colored light at the atoms which have to be excited

1.1.4. Components of lasers

There are four primary components of lasers [2]

1.1.4.1 Active Medium

Active medium is excited by the external energy source to generate photons

There can be four types of active medium

 Solid Crystals for example Nd:YAG, Ruby  Liquid dyes  Gases such as CO2 or Helium/Neon  Semiconductors such as GaAs

1.1.4.2 Excitation Mechanism

Excitation mechanism is used to pump energy into the active medium and excite it. It can be done by three different methods. Electrical, optical or chemical

1.1.4.3 Mirror with high reflection

On one side there is a mirror which has very high reflection. It should ensure 100% reflection.

1.1.4.4. Mirror with partial transmission

On the other side there is a mirror which has ordinary reflection. It transmits some of the light and reflects some of the light.

Figure 1.1.3. demonstrates that there is electrical source which is used as excitation mechanism which is used to excite the Chromium atoms in Ruby. The photons oscillate between the two mirrors and transmitted through one of the mirror in the form of laser beam.

Figure 1.1.3: Excitation of Chromium atoms in Ruby [2]

1.1.5. Categories of lasers

Lasers can be classified in two categories, [3]

1.1.5.1. Continuous Lasers

Continuous lasers use gas as active medium. They operate for periods more than a second. Laser pointer is their example. They have high average power (average power means total energy produced in one second) in comparison with pulsed lasers.

1.1.5.2. Pulsed Lasers

Pulsed lasers use solid crystal, glass or a semiconductor as active medium. They operate for periods less than one second. They have very low average power in comparison with continuous lasers.

Pulsed lasers have two types, [3]

1.1.5.2.1. Short Pulsed Lasers

Short pulsed lasers have the duration of one picosecond.

1.1.5.2.2. Long Pulsed Lasers

Long pulsed lasers have the duration of one nanosecond.

1.2. Plasma

Plasma is known as fourth state of matter. In simple words plasma is defined as an ionized gas. It can consist of electrons, protons, ions which are called as free charge particles. Due to free charge particles plasma can carry electric current and generate magnetic field. [8]

Atoms of a gas contain equal number amount of negative and positive charge. The number of protons inside the nucleus is equal to the number of electrons revolving around the nucleus. When the electrons revolving around the nucleus are ejected out of the atoms by providing them energy, the gas atom becomes ionized. When the number of ions formed to reach to an extent that they affect the electrical characteristics of the gas then it is called as plasma. [8]

1.2.1. Common forms of Plasma

There are three forms of plasma [4]

 Artificially produced plasma  Terrestrial plasmas  Space and astrophysical plasmas

Table 1.2.1 demonstrates the examples of three different forms of plasma

Table 1.2.1: Different forms of plasma, [4]

Artificially produced plasma Terrestrial plasma Space plasma Plasma displays, e.g. TV Fire Sun and stars Fluorescent lamps Lightning Solar wind Area in front of spacecraft’s St. Elmo’s fire Space between planets heat shield during entering into atmosphere Plasma torch, Electric Arc Sprites, elves, jets Space between stars Plasma globe Ionosphere Space between galaxies Dielectric layers Polar aurorae Interstellar nebulae

1.2.2. Degree of Ionization

For plasma, degree of ionization is directly proportional to the atoms which have lost the electrons and it depends upon the temperature. The mathematical relation for degree of ionization is given by following relation where ni = number density of ions and na = number density of neutral atoms [4]

1.2.3. Temperature measurement of plasma

The temperature of plasma is measured either in Kelvin or electron volts and this temperature is the measurement of the thermal kinetic energy of all the particles. There may be a difference between the ion temperature and the electron temperature. There is a huge difference between the mass of electrons and the ions; this helps electrons to reach thermal equilibrium much earlier than then ions or neutral atoms. On this temperature difference basis plasmas can be divided into two types. [4]

1.2.3.1. Thermal plasma

The plasmas in which electrons and the ions or the neutral particles have the same temperature are called as thermal plasmas.

1.2.3.2. Non Thermal Plasma

The plasmas in which ions and the electrons are not at the same temperature are called as non- thermal plasmas. In this case, the ions or the neutral atoms can have as low temperature as room temperature.

1.2.3.3. Hot Plasma

The plasma which has high degree of ionization is called as hot plasma.

1.2.3.4. Cold Plasma

The plasma which has low degree of ionization is called as cold plasma.

1.2.4 Density of plasma

Density of plasma is defined as number of free electrons per unit volume [4]

1.2.5. Potential of Plasma

The potential which exists between the charged particles i.e. ions is called as the potential of plasma. When an electrode is inserted in the plasma, the potential on the electrode will be less than that of the plasma due to the formation of Debye Sheath. Electric fields in the plasma are very small because of good electrical conductivity. There is a concept called quasineutrality, according to which the density of negative charges can be approximated equal to the density of positive charges considering large volume. But the concept of quasineutrality may not hold true at Debye Length. To produce plasma which does not hold the concept of quasinuterality is also a possibility. [4]

1.2.6. Magnetization

Only that plasma is called magnetized in which the motion of the charged particles can be influenced by the magnetic field. It can also happen that electrons get magnetized whereas the ions remain non-magnetized. The special thing about magnetized plasma is that its properties in the direction of magnetic field are different than the properties in the perpendicular direction.

The relation between electric and magnetic field is given by [4]

E= Electric field

V= Velocity

B= Magnetic field

1.2.7. Mathematical description of plasma

There are two ways to describe the mathematical model for plasma [4]

1.2.7.1. Fluid Model

With the help of fluid model the average velocity around each position and density can be measured. When the plasma velocity distribution is close to Maxwell-Boltzmann distribution which means collisionality is very high, fluid models are very accurate.

1.2.7.2. Kinetic Model

With the help of kinetic model the velocity of the particle at each point in a plasma can be measured which requires no need for Maxwell-Boltzmann distribution.

1.3. Laser confinement of plasma

1.3.1. LIBS in brief

It is one of the methods of atomic emission spectroscopy (AES).High powered lasers are used to produce plasma. Pulses from a laser are focused on the mirror. Mirror reflects the laser pulse towards the target. Between the target and the mirror and center lens is placed. Fiber optic cable is then used to collect the plasma light. Spectrometer is used to collect the signal. Each laser pulse from the laser gives one reading of LIBS (Laser Induced breakdown spectrometry) measurement. Seen from a naked eye, plasma appears like a flash of a focal volume of bright white light. This flash of bright white light is accompanied by a loud sound as well. As the optical breakdown results in the shock waves which produce the loud sound. When the spherical lens is used for the formation of plasma, the plasma formed is spherical. It happens because the gas breaks down first at the focal point and then it is extended towards the spherical lens [5]. Figure 1.3.1 demonstrates the apparatus for LIBS.

Figure 1.3.1: LIBS apparatus, L=Laser, M=Mirror, LP=Laser Pulse, CL=Lens, P=Plasma, T=target, FOC=fiber optic cable, S=Spectrograph, AD=Array detector, GE=Gating Electronics, C=Computer, [5] Figure 1.3.2 and figure 1.3.3 demonstrate the two examples for the formation of plasma with the help of spherical and cylindrical lens on soil and filter respectively.

Figure 1.3.2: Laser Plasma formed on soil by a spherical lens (4-5 mm in length), [5]

Figure 1.3.3: Laser plasma formed on a filter by a cylindrical lens (7-8 mm in length), [5]

1.3.2. Life cycle of LIBS process

There are two steps involved in the laser induced breakdown. In the first step, with the help of few photons free electrons are generated. These free electrons are the initial receptors of energy. In the second step, avalanche ionization occurs in the focal region. As the number of free electrons grow, collisions occur which result in ionization and eventually result in the generation of more free electrons and eventually avalanche occurs. Breakdown threshold can be defined as,

“Minimum irradiance required for the generation of plasma”. [5]

The generation of plasma occurs in a focal volume. After the breakdown, the plasma from the focal point tends to expand in all directions. But this expansion is more in the direction of the lens as the laser energy is coming form that direction. When the plasma expands in all directions, it can have a pear shaped or cigar shaped appearance. The plasma goes through different transient phases from its initiation to the decay time. The propagation and expansion of the plasma can be described by three different wave models. [5]

 Laser-Supported Combustion (LSC)  Laser-Supported Detonation (LSD)  Laser-Supported Radiation (LSR)

The models of LSC and LSD describe the experiments in case of low irradiances. Plasma at low irradiance has low temperature and density. When the plasma is expanding, plasma itself and its boundary with the atmosphere is allowing transmittance to the laser radiation. During expansion plasma emits different signals and loses the energy in different ways. Afterwards plasma starts cooling and decaying. Eventually the electrons and the ions recombine and form neutrals. The mode of heat transfer is either conduction or radiation. The temperature of plasma can rise to tens of thousands of degrees. [5]. LIBS life cycle is demonstrated by Figure 1.3.4.

Figure 1.3.4: LIBS life cycle, [5]

1.3.3. Advantages of LIBS

Like all AES methods, LIBS has following to advantages over non-AES methods. [5]

 Ability to detect all the elements  Simultaneous multi-element detection capability

Comparing with other AES-methods, LIBS has following advantages [5]

 Rapid  Real time analysis  Simple  Preparation of sample is not a requirement

 Allows in situ analysis, requiring only optical access to the sample  Can be used on solid, liquid and gaseous samples  Robust plasma can be formed which is not possible under conventional plasmas  Variety of measurement scenarios

1.3.3.1. Variety of measurement scenarios

There are different methods devised for the direction of laser light on the sample. In some methods the target is very close to the laser and in other methods the target is meters away from the laser. [5]

1.3.3.1.1. Direct analysis

In direct analysis the lens used has a short focal length. Laser light passes through this short focal length laser and falls on the target to form plasma. The target can be either solid, gas or liquid. Fiber optic cable collects the plasma light and transfers it to the spectrograph. Instead of optic cable a lens can be used as well.

1.3.3.1.2. Fiber optic delivery

By this method the laser pulse at a distance of 100 m can be transferred. Megawatts per centimeter square power densities can be transferred from one end of the optical fiber to the other end. After the generation of plasma, energy in the range of tens of mJ can be transported back. For the back transportation either the same cable can be used or another optical cable can be used. Figure 1.3.5 demonstrates fiber optic delivery.

Figure 1.3.5: Fiber optic delivery; P=Plasma; T=Target; CL=Lens; FOC= fiber optic cable; I=Pulse Injector for FOC; B= Beam splitter; L=Laser; AD=Array Detector; S=Spectrograph, [5]

1.3.3.1.3. Compact probe

Portability is the benefit achieved by this method. It has laser, focusing optics and fiber optics which ensure the collection of laser pulse and the transportation of plasma light. Both the laser and the spectrometer are connected to the probe through the electrical cables and they are placed away from the probe. Compact probe has an edge over the fiber optic deliver because of the small spot size which results in the delivery of high power density. Figure 1.3.6 demonstrates compact probe.

Figure 1.3.6: Compact probe; T=Target; P=Plasma, CL=Lens; LP=Laser Pulse; L=Laser; FOC=Fiber optic cable; EC=Electrical cables; AD=Array detector; S=spectrograph; LPS=Laser power supply, [5]

1.3.3.1.4. Stand-off analysis

In this method there is a distance between the laser and the target. Thus a lens of long focal length is used. The distance between the laser and the target depends upon the laser power, laser

13 pulse energy, beam divergence, spatial profile and the focal length of the optical system. Figure 1.3.7 demonstrates stand-off analysis.

Figure 1.3.7: Stand-off analysis; T=Target; P=Plasma, LP=Laser pulse; B=Beam-splitter; BE=Beam expander; FOC=fiber optic cable; S=Spectrograph; AD= Array detector, [5]

1.3.3.2. No Sample Preparation

Most of the AES methods require sample preparation between LIBS does not require sample preparation or very little. It is because it’s the same focal volume where the ablation and excitation occur. Non-conducting and refractory compounds can be vaporized even because of the high focused power densities. Though no sample preparation is required yet in case of bad surface ablation pulses can be used. [5]

1.3.3.3. In Situ Analysis

Sample in case of AES methods is brought close to the sample whereas in LIBS source is brought to the sample. But the distance between the sample and the instrument can be as short as a few centimeters but in case of standoff analysis this distance can be in meters. [5]

1.3.3.4. Speed of analysis

In case of LIBS, analysis speed is very short because of following reasons [5]

 No sample preparation

 Simplicity of LIBS  Short life time of plasma  Minimal processing time for the spectrum

1.4. Differences between laser and microwave systems

Laser stands for “Light amplification by stimulated emission of radiation” and maser stands for

“Microwave amplification by stimulated emission of radiation” [6].Both the lasers and the masers depend upon stimulated emission discovered by Einstein. The purpose of both the devices is the generation and amplification of a radiation. But the difference is that lasers are used to produce photons of high energy either in the ultraviolet region or the visible region. Masers produce photons of higher wavelength thus the Energy of those photons is low. -8 When the atoms are excited because of spontaneous emission the average life time is 10 sec [6]. The atoms go to high energy state and then emit photon and the life cycle as mentioned is 10-8 -3 sec. When the atoms are in metastable state the life time can become as short as 10 sec [6]. This life time is important for MASER.

Maser is good for generation of coherent long wavelength radiation and it’s amplification but moving towards short wavelengths with masers is a problem and they are listed below, [7]

 For lasers a large number of electromagnetic oscillations are required in the cavity whereas maser cavity requires only one oscillation.  For lasers especially in the optical region unless the stimulated emission reaches a higher level it is submerged by the spontaneous emission which is incoherent as well.  Energy differences for masers to generate microwaves are small whereas energy differences for lasers to generate optical radiation or UV radiation are very high and comparable to kT.  Tuneable and monochromatic signal generators are used to excite the atoms for the generation of microwaves but not for the lasers. Untuneable, monochromatic and broadband radiators are used for the lasers.

2. Overview of current technologies to treat toxic material

2.1. Thermal Energy: Incineration and pyrolysis

Pyrolysis is a process in which waste materials are thermally decomposed into gas and solid phases in the absence of oxygen. Majority of pyrolysis reactions occur at temperature of around

500 °C. [9]

There can be different applications of pyrolysis but the commercially used applications are [9]

 Waste to Energy  Carbonization  Soil Remediation

These applications are vital because they convert waster toxic materials into vital products. This fact is demonstrated by Table 2.1.

Table 2.1: Applications, input materials and products of pyrolysis, [9]

Applications Input toxic waste materials Products by pyrolysis 1 Carbonization  Wooden chips  Fertilizer  Organic sludge  Solid fuel 2 Waste to Energy  Municipal solid waste  Electrical  Waste plastics Energy  Medical waste  Steam  Rubber and tires  Black Carbon  E-waste  Oil  Biomass/wood  Non-oxidized  Organic sludge (sewage, oil , paper metals sludge) 3 Soil remediation  Contaminated soil (dioxins, oil,  Cleaned soil mercury, organics

The plants for pyrolysis can be operated both batch as well as continuous mood. There are 5 main steps of batch process which include loading the toxic waste material, heating it up in the system, pyrolysis, after pyrolysis system is cooled and then the products are unloaded from the system. Batch process has it’s attraction for the investment cost comparing with continuous

16 pyrolysis units but it requires extensive manual labor so the company’s prefer to have continuous pyrolysis units. [9]

In continuous pyrolysis unit, there is a rotary kiln that is heated to a temperature of around 400- 600 °C. Absence of oxygen in the kiln is ensured. Toxic waste material is moved in the rotary kiln where it is heated to generate syngas and flue gas. Syngas is sent to the boiler where it produces steam. Whereas flue gas is sent to emission control system. The efficiency of pyrolysis unit heavily depends upon the toxic waste material composition. [9]

Pyrolysis can be used for the treatment of [9]

 Biomass  Plastics  Medical waste  Tires  E-waste  Soil

Biomass consists of wood waste, agricultural waste. Pyrolysis is done on these waste products and the gas which is produced can be directly used for power generation. Generated electricity depends upon the moisture and biomass type.

1.25 t/h wooden chips (14 MJ/kg) with moisture content nearly 25% generate about 1.2 MWe. [9]

4 t/h of poultry liter nearly 10 MJ/kg generate 2.3 MWe. [9]

As plastic wastes are contaminate most of the times, so their directly recycling is not a possibility in most of the cases. Plastic wastes contain bio waste, metal, food, beverage packing. So it really becomes difficult to separate the plastic waste from at the pyrolysis facility. By the pyrolysis of plastic bags not only energy is generated but oil condensing as well. This oil can either be used in diesel generators or as heating oil. Automotive shredded Residue (ASR) which consists of plastics, rubber, glass, wood products, cloth paper, dirt and electrical wiring has higher efficiency for power generation than municipal solid waste. [9]

Generally hospital waste that is sent to the waste deposit facility is incinerated. This hospital waste consists of pharmaceutical waste, textile, pathological wastes, plastics, polyvinylchloride, needles etc. But this incineration results in production of carbon monoxide, dioxins. This incineration of medical waste is banned in California just because of this reason. Pyrolysis is a better option for the treatment of medical waste but the output entirely depends upon the type of medical waste. [9]

Doing incineration is not a good option on tiers as 450 kg of toxic gases are produced by burning just a single ton of tires [9]. Pyrolysis is surely an option but the oil generated through the pyrolysis of tires has high sulfur content as well as residual content. Therefore the oil produced through pyrolysis of tires needs further refinement. Carbon black which is physically and chemically distinct is also a part of this oil. So carbon black, sulfur at the big issues which add to the cost of oil produced through the pyrolysis of tires. Normally 315 kg/h of oil is produced from

800 kg/h tires pyrolysis. 6.5 MW electricity can be generated through 3 t/h of tires pyrolysis. [9]

Electronic waste is a big problem right now in the world. But printed circuit boards which are made of ceramics, fiberglass, noble metals and organic resins are not a problem. Soil contaminated with dioxin, PCB, organic pollutants can be easily cleaned through pyrolysis. [9]

The whole process of incineration is demonstrated by Figure 2.1. [10]

1. Waste deposit area by trucks 2. It’s a hopper and the waste material is moved into it through yellow colored lifters. 3. It’s the incineration unit which gets the waste material from hopper. The temperature of incineration is around 750 °C 4. It’s the boiler which receives steam produced by incineration and sends it to power generation facility. 5. Ash content is moved to 5 and from this position ash is passed over electromagnetic facility in order to separate metal content from it

6. It’s a scrubber which receives flue gases from incineration unit. It is where SO2 and dioxins are treated. 7. It’s a system to remove fine particles. 8. Chimney

Figure 2.1: Incineration process, [10] European Union has applied strict operation conditions on incineration because of the toxic emissions produced by the process. These emissions polluted air, water and soil and dangerous for human health. The conditions include permits, delivery and reception of waste, the operating conditions, air emissions limit values, water discharges from the cleaning of exhaust gases, residues, monitoring and surveillance, access to information and public participation, implementation reports and penalties. [11]

There is a difference between pyrolysis and incineration [9]

 During commercial usage, emission of harmful products is much easier to control comparing with incineration.  The energy required to start up the process is the only energy required for the process in case of pyrolysis  Pyrolysis does not generate waste water effluent from gas cleaning system.  In pyrolysis the metals obtained are without oxides  The waste treated by pyrolysis can be both, high calorific and low calorific

2.2. Plasma Energy:

Plasma is a mixture of electrons, ions and neutral particles but it’s overall electrically neutral. Temperature defines the degree ionization of plasma. Higher the temperature higher the number of electrons lost by the atoms and higher the degree of ionization. When electrical current is

19 passed through the gas, due to electrical resistivity heat is generated which results in creation of plasma (ionized gas). [12]

Asbestos containing residues can be destroyed through plasma in the presence of argon gas. Asbestos can be converted into a rocklike structure by plasma. There is a water of crystallization in asbestos and introducing it to plasma reduces volume by 5% and weight by 70% but that is only partial treatment. [12]

In France at a commercial facility (INERTAM), high temperature plasma vitrification of asbestos is carried out in the presence of air. [12]

Tetronics in UK use 1600 °C temperature for asbestos destruction through plasma. They are successful in destroying asbestos by 100%. [12]

Health care wastes are divided into two types. One which is not dangerous and does not required special handling. Other type of waste is dangerous as it contains pathogenic microorganisms, it requires special handling. [12]

Plasma can kill all bacteria and microorganisms because of its high temperature and ultra violet radiation. Drug structures are also destroyed by plasma.

Technical University in Poland, have destroyed hospital fly ashes. Molten waste was kept at

1500-1600 °C for 30 mins and then air cooled. [12]

Institute of plasma research in India compared plasma technology with other waste treatment technologies for hospital waste. The waste contained cotton and plastic in a ratio of 2:1. Plasma destroyed all bacteria but pyrolysis couldn’t. Pyrolysis results contained hydrogen, carbon mono oxide and lower molecular weight hydro carbons. [12]

Steel making wastes generally consists of stable oxides (calcia, silica, and alumina), oxides (Iron, chromium, Nickel, Manganese, and Phosphorous), volatile metals (Zinc, lead, Cadmium). Oxides can be reduced by using reduced plasma. Volatile metals can be collected from the vapor phase. [12]

Technologies such as PLASMADUST, plasma arc centrifugal technology have been used for the treatment of steel making wastes. [12]

Electroplating on metals is done in order to save them from corrosion. Zinc, Chromium, Nickel plays a vital role in that. Waste water coming out of electroplating industry contains Zinc, Chromium, and Nickel. The waste water can be cleaned with the help of plasma with different gas atmospheres at reduced pressure. After the treatment of waste water, powders can be collected from the walls of reactor. There elements are present in the forms of ferrite, chromite. [12]

Aluminum dross is the result of Aluminum reaction with atmosphere as well as entrapped oxides into the flux which form slag. This dross can be 1-5% of the total melt and my contain upto 10% Aluminum by weight. Because of the flux used, it becomes toxic and contains fluoride and chlorides. The dross can be dissolved by thermal plasma. [12]

Thermal plasma treatment of carbonaceous wastes is very efficient by the gasification of the carbon waste to reduce its weight and volume and result in the production of synthesis gas. [12]

Incineration is not a good technique for chlorine containing wastes. Combination of pyrolysis and plasma is an efficient way of destroying chlorine containing wastes. It’s because incineration of Chlorine results in dioxins and furans whereas plasma treatment suppress it. [12]

Plasma is an efficient way of destroying toxic materials but its economic viability is not clear on large scale. Though different feasibility reports have been presented for many toxic materials. [12]

2.3. Microwave Energy:

The biggest advantage of microwave technology is that, if the process is properly controlled, uniform heating can be ensured. Instead of heating material, from external source heat is generated inside the material. So different materials give different response to microwave technology. The materials which don not absorb microwaves cannot be destroyed by microwave technology. On the contrary, those materials which absorb microwaves and are called as dielectrics must possess two properties. [13]

 Upon exposure to an external electrical field, there must be very low number of charge carriers in the material.  Dipole movement must be exhibited by the atoms/molecules of the material.

When a dielectric material is placed in an external field, the dipoles realign themselves according to the external applied filed. When the electromagnetic field is alternating, the dipoles realign themselves 2.5 billion timers per second. This realignment causes friction and that generates heat. [13]

Volatile organic compounds can be destroyed using microwave technology. Conversion for tetrachloroethylene and trichloroethane are 99% effective and they are converted into less noxious compounds. [14]

In USA, Las Alamos National Laboratory a microwave fluidized bed reactor was made so that waste of organic compounds can be treated by oxidation reaction. [14]

Soil which contains toluene and xylene can be decontaminated by the use of microwave technology. It was studied by the researchers in Mississippi University USA. [14]

Microwave technology has been successful in dewatering of low level of nuclear waste. It reduces the waste volume by 5%. The product obtained by the dewatering of low level nuclear waste met Canadian Atomic Energy central Board acceptance criteria. [14]

Microwave treatment of Plutonium is a possibility made by Kobe Steel Limited. They developed a method at Power reactor and Nuclear Fuel development corporation Japan. [14]

University of Florida and Savannah River Technology worked together on microwave technology to study the waste management. They found out that different electronic components could be treated by 1-step hybrid heated microwave processes. The reduction in volume they achieved was significant and was greater than 50%. [14]

Metal components could be separated from the glass using microwave technology. Through microwave technology they were even able to separate metals like gold and silver and the metals obtained were in reusable conditions. [14]

Scrap tires can also be treated by microwave technology, it’s an expensive process but important by-products are formed which may make the destruction of tires through microwave technology a feasible process. [13]

SO2 and NOx have been destroyed through microwave technology as well by using NH3 and water as reagents. At 1.2 kW 90% destruction efficiency is achieved for SO2 but gaseous mixture of NOx does not give good efficiency. In case of NOx the reaction rate of destruction is higher than the rate of destruction. But this condition exists only below 400 W. A combination of electron beam microwave irradiation is more efficient for the destruction of NOx gaseous mixture. [13]

Microwaves can give 90% efficiency to clean soil when it comes to the destruction of PCBs and heavy metals. But often commercial methods can give the destruction efficiency as high as 90%. [13]

Sewage Sludge volume can be reduced to 80% by using microwave technology. First it dries the sludge at 200 °C, then to achieve temperature of 900 °C some microwave absorbent material is inserted in the sludge and it is pyrolysed. [13]

In US, 170 sewage sludge incineration plants are functioning at this time. But they emit pollutants which include metals, carbon monoxide, NOx, SO2 and unburned hydrocarbons. [13]

3. Comparison tables for destruction of selected toxic materials through different technologies

Toxic materials in all three states of matter were studied. i.e. solids, liquids and gases.

 Solid material studied are Phosphors and Asbestos

 Gaseous material studied is NOx (NO, NO2)  Liquid materials studied are a) Acids 1. Hydrogen Iodide, HI 2. Oxalic Acid, H2C2O4 3. Formic Acid, HCOOH 4. Nitric Acid, HNO3 5. Hydrogen Peroxide, H2O2 6. Acetic Acid, CH3COOH 7. Boric Acid, H3BO3 8. Nucleic Acids 9. Sulfuric Acid, H2SO4 10. Citric Acid, C6H8O7 11. Benzoic Acid, C6H5COOH 12. Yeast Nucleic Acid 13. Hydrogen Bromide, HBr 14. Chromic Acid, H2CrO4 15. Hydrochloric Acid, HCl b) Bases 1. Sodium bicarbonate, NaHCO3 2. Sodium Carbonate, Na2CO3 3. Ammonia, NH3 4. Barium Hydroxide, Ba(OH)2 5. Potassium Hydroxide, KOH 6. Aluminum Hydroxide, Al(OH)3 7. Magnesium Hydroxide, Mg(OH)2

8. Sodium Hydride, NaH 9. Lithium Hydroxide, LiOH 10. Calcium Hydroxide, Ca(OH)2 11. Strontium Hydroxide, Sr(OH)2 12. Sodium Hydroxide, NaOH 13. Nickel Hydroxide, Ni(OH)2 14. Calcium Oxide, CaO c) Organic Solvents 1. Acetic Acid, CH3COOH 2. Methanol, CH3OH 3. Propanol, CH3CH2CH2OH 4. Triethylamine alane, TEAA 5. Ethanol, CH3CH2OH 6. Isopropanol, (CH3)2CHOH 7. Methylene Chloride, CH2Cl2 8. n-heptane, C7H16 9. toluene, C7H8 10. Propylene carbonate, C4H6O3 11. Alkylamines (propyl amine, diethyl amine, triethylamine) 12. Benzene, C6H6 13. Acetone, (CH3)2CO 14. Methyl tert-butyl ether, C5H12O 15. Formic Acid, HCOOH 16. Chloroform , CHCl3 17. Tetrachloro-ethylene, C2Cl4 18. Diethyl ketone, C5H10O

In the appendix there are tables that show the conventional technologies used to destroy toxic materials. Different technologies have been written in a tabulated form by considering the factors as follows:

Destruction technology: The technology which is used to destroy the toxic material.

Efficiency: toxic material destroyed divided by the toxic material at the beginning of the process.

Amount of destruction: The amount of toxic material that has been destroyed

By products: The by-products which are formed after the destruction of the toxic material.

Skilled Labor: It is judged through the machines used in the process.

Dangerous process: It has been decided on the basis of handling the toxic materials

Automatic process: It has been decided on the basis that whether the technology used needs handling of the toxic material during destruction or not.

Pre-treatment of toxic material before destruction (PTOTMBD): It has been judged on the fact whether the toxic material needs any pre-treatment before destruction or not.

Pre-treatment of destroying agent before destruction (PTODABD): It he been judged on the fact whether destroying agent needs any pre-treatment before destroying toxic material or not.

Investment cost: It has been decided upon the equipment and machines used in the destruction process as well as the analysis

Running cost: It has been decided upon the materials required for the start of destruction process and as well as analysis once the machines and equipment for the process are already there

Working area: It has been based on the equipment and machines used in the destruction process as well as its analysis

Number of Labor: It has been decided on the fact whether the destruction process can be carried out by a single person or more than one person is required.

Comments: For some technologies there was a need to give some comments at the end, which are mentioned in comments.

4. Molecular dissociation model

In this section a simple mathematical model is developed in order to simulate the destruction of toxic waste primarily. Obviously the simulation can be extended to the non-toxic materials. The energy of molecular dissociation is calculated for every chemical formula. This energy value is then utilized as energy of the Planck equation, which in turn is exploited to find a virtual photon of such wavelength capable to dissociate the molecule thus destroying it. Then it is assumed that this photon has an energy which is n-times the energy of a real photon associated to the wavelength of the selected laser, which is in turn n-times the virtual photon wavelength. So the value of n is therefore extracted as the ration between the selected laser wavelength and the virtual wavelength. Basically n is also the number of photons that ideally shall be used to dissociate the molecules. This value of n is utilized in relation to the value of the number of photons in a commercially available laser, for example a rather exotic but already realized Nd:YAG of 100 J per pulse of 10 ns and repetition frequency of 20 Hz. The real total laser energy found to supply the number of photons necessary to dissociate the toxic molecule under evaluation is considered to be the sum of the energy at every laser pulse. This is a condition that should be validated experimentally. Due to budget limitations only the theoretical part has been developed.

4.1. Solids

4.1.1. Zinc Sulfide, ZnS

Energy required to decompose ZnS [197] is calculated as follows using Hess’s Law

Eqn1 2ZnS(s) + 3O2 (g) → 2ZnO(s) + 2SO2 (g) ΔH= -927.54 kJ

Eqn2 2SO2 (g) + O2 (g) → 2SO3 (g) ΔH= -196.04 kJ

Eqn3 No(s) + SO3 (g) → ZnSO4(s) ΔH= -230.32 kJ

Eqn4 8Zn(s) + S8(s) + 16O2 (g) → 8ZnSO4(s) ΔH= -7808.24 kJ

Reverse Eqn1 x 4 => 8ZnO(s) + 8SO2 (g) → 8ZnS(s) + 12O2 (g) ΔH= 3710.16 kJ

Reverse Eqn3 x 8 => 8ZnSO4(s) → 8ZnO(s) + 8SO3 (g) ΔH= 1842.56 kJ

Eqn4 => 8Zn(s) + S8(s) + 16O2 (g) → 8ZnSO4(s) ΔH= -7808.21 kJ

Reverse Eqn2 x 4 => 8SO3 (g) → 8SO2 (g) + 4O2 (g) ΔH= 784.16 kJ

8Zn(s) + S8(s) → 8ZnS(s) ΔH= -1471.12 kJ

ZnS(s) → Zn(s) + 1/8S8(s) ΔH= 183.89 kJ/mol [197]

According to Max Planck Energy equation

Total energy is given by

λL of laser to destroy toxic material

Comparing the two ET equations

To find out the material destroyed in kilogram per hour, following mathematical calculations were applied on all toxic materials that follow. The results are shown in the tabulated form at the end of the dissociation energy calculations. The steps for ZnS are shown below.

 λT calculations  Number of photons to destroy 1 mole of toxic material  Energy of one photon of the selected laser  Number of photons in laser beam  Number of pulses to destroy 1 mole of toxic material  Number of pulses generated in one second  Time to generate the pulse that is sufficient enough to destroy 1 mole of toxic material  Amount of toxic material destroyed in kg/hrs.

λT calculations

Putting the values of planks constant, speed of light and the energy calculated through Hess’s law to destroy ZnS can be calculated for each mole

Number of photons to destroy 1 mole of toxic material

As derived about the number of photons to destroy 1 mole of toxic material can be calculated through following relation

Energy of one photon of the selected laser

This case shows the usage of gas dynamic laser developed by Professor Apollonov

Putting the values of plank’s constant, speed of light and value of wavelength of gas dynamic laser developed by Professor Apollonvo, the energy of one photon of the laser can be calculated as follows

Number of photons in laser beam

Number of photons in the 2.86 J Laser beam of Infra-Red CO2 is calculated as

Putting the values of Infra-Red CO2 laser in the above relation, number of photons in laser beam is calculated

Number of pulses to destroy 1 mole of toxic material

Putting the values of number of photons to destroy 1 mole of ZnS as calculated above and putting the value of number of photons in 1 laser beam we can have following result

Number of pulses generated in one second

Number of pulses generated in one second for gas dynamic laser developed by Professor Apollonov is 350,000.

Time to generate the pulse that is sufficient enough to destroy 1 mole of toxic material

Putting the above calculated values in the mathematical relation gives the value of time to generate the pulse that is sufficient enough to destroy 1 mole of toxic material

Amount of toxic material destroyed in kg/hrs.

Molar Mass of ZnS= 97.474

Mass of ZnS in kg= 0.097474 kg

The above calculations have been repeated for all the toxic materials and written in tabulated form at the end of the equations

4.2. Gases

4.2.1. NO

Energy required to decompose NO [198] is calculated as follows using Hess’s Law

Eqn1 2NH3 (g) → N2 (g) + 3H2 (g) ΔH= 91.8 kJ

Eqn2 2H2 (g) + O2 (g) → 2H2O (g) ΔH= -483.6 kJ

Eqn3 4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g) ΔH= -1628.2 kJ

Eqn1 x 2=> 6H2 (g) + 2N2 (g) → 4NH3 (g) ΔH= -183.6 kJ

Eqn2 x 3=> 6H2O (g) → 6H2 (g) + 3O2 (g) ΔH= 1450.8 kJ

Eqn3=> 4NH3 (g) + 5O2 (g) → 4NO (g) + 6H2O (g) ΔH= -1628.2 kJ

2N2 (g) + 2O2 (g) → 4NO (g) ΔH= -361 kJ

NO (g) → 1/2N2 (g) + 1/2O2 (g) ΔH= 90.25 kJ/mol [198]

4.2.2. NO2

Energy required to decompose NO2 [199] is calculated as follows using Hess’s Law

Eqn1 N2 (g) + 2O2 (g) → N2O4 (g) ΔH= -9.16 kJ

Eqn2 N2O4 (g) → 2NO2 (g) ΔH= -57.2 kJ

Eqn1=> N2 (g) + 2O2 (g) → N2O4 (g) ΔH= -9.16 kJ

Eqn2=> N2O4 (g) → 2NO2 (g) ΔH= -57.2 kJ

N2 (g) + 2O2 (g) → 2NO2 (g) ΔH= -66.36 kJ

NO2 (g) → 1/2N2 (g) + O2 (g) ΔH= 33.13 kJ/mol [199]

The mathematical model for liquids is in the appendix.

4.3. Calculations for number of photons to destroy toxic materials

There are four lasers which are under consideration as shown in the following table. Decomposition energies, wavelength required to decompose the toxic material, wavelength of the lasers and the energy associated with one of photon of each laser is used to calculate the number of photons required to destroy the toxic material. Table 4.3.1 shows the wavelength and energy of one photon associated with each laser.

Table 4.3.1: Wavelength and energy of one photon for four different types of lasers [200]

Energy of one Lasers Wavlength (nm) Wavelenght (m) photon (J) Infrad Red CO2 Laser 10064 0,000010064 1,97379E-20 Nd:YAG 1064 0,000001064 1,86694E-19 Green Laser,frequency doubled Nd:YAG 532 0,000000532 3,73388E-19 UV Laser, frequency tripled Nd:YAG 266 0,000000266 7,46776E-19

Number of photons to destroy one mole of toxic liquid is demonstrated by the equation

Table 4.3.2 the number of photons required by each laser in above to destroy toxic solid (ZnS).

Table 4.3.2: No of photons to destroy 1 mole of toxic solids by 4 different lasers No.of photons to No.of photons to No.of photons No.of photons destroy on mole of destroy one mole to destroy one to destroy one toxic solid by Infra of toxic solid by mole of toxic mole of toxic Toxic Decomposition Red CO2 Nd:YAG solid by Green solid by UV Sr.No solids Energy (J/mol) laser,n1/mol laser,n2/mol laser,n3/mol laser,n4/mol 1 ZnS 183890 9,31658E+24 9,8498E+23 4,9249E+23 2,46245E+23

Table 4.3.3 demonstrates the number of photons required by each laser shown in Table4.3.1 to destroy toxic gases (NO, NO2).

Table 4.3.3: No of photons to destroy 1 mole of toxic gases by 4 different lasers

No.of photons to No. of photons to No.of photons No.of photons destroy one mole destroy on mole of to destroy on to destroy on of toxic gas by toxic gas by mole of toxic mole of toxic Toxic Decomposition Infra Red CO2 Nd:YAG gas by Green gas by UV Sr.No Gases Energy (J/mol) Laser,n1/mol laser,n2/mol laser,n3/mol laser,n4/mol 1 NO 90250 4,57242E+24 4,83411E+23 2,41706E+23 1,20853E+23 2 NO2 33130 1,67849E+24 1,77456E+23 8,8728E+22 4,4364E+22

Table 4.3.4 demonstrates the number of photons required by each laser shown in Table 4.3.1 to destroy liquids

Table 4.3.4: No of photons to destroy 1 mole of toxic liquids by 4 different lasers

No.of photons to No.of photons to No. of photons No.of photons Decompo destroy one mole destroy one mole to destroy one to destroy one sition of toxic liquid by of toxic liquid by mole of toxic mole of toxic Sr. Energy Infra Red CO2 Nd:YAG liquid by Green liquid by UV No Toxic Liquids (J/mol) laser,n1/mol laser,n2/mol Laser,n3/mol laser, n4/mol 1 Hydrogen Iodide -26000 -1,31726E+24 -1,39265E+23 -6,96326E+22 -3,48163E+22 2 Oxalic Acid 252620 1,27987E+25 1,35312E+24 6,76561E+23 3,38281E+23 3 Formic Acid 40531 2,05346E+24 2,17098E+23 1,08549E+23 5,42746E+22 4 Nitric Acid 174000 8,81552E+24 9,32006E+23 4,66003E+23 2,33002E+23 5 Hydrogen peroxide 187600 9,50454E+24 1,00485E+24 5,02426E+23 2,51213E+23 6 Acetic Acid 485000 2,4572E+25 2,59783E+24 1,29892E+24 6,49458E+23 7 Boric Acid 7195 3,64527E+23 3,8539E+22 1,92695E+22 9,63475E+21 8 Sulfuric Acid 72000 3,6478E+24 3,85658E+23 1,92829E+23 9,64144E+22 9 Citric Acid 1384000 7,01188E+25 7,4132E+24 3,7066E+24 1,8533E+24 10 Benzoic Acid 385070 1,95091E+25 2,06257E+24 1,03129E+24 5,15643E+23 11 Hydrogen Bromide 36400 1,84417E+24 1,94971E+23 9,74857E+22 4,87428E+22 12 Hydrochloric Acid 92330 4,6778E+24 4,94552E+23 2,47276E+23 1,23638E+23 13 Sodium bicarbonate 91630 4,64233E+24 4,90803E+23 2,45401E+23 1,22701E+23 14 Sodium bicarbonate 950800 4,81712E+25 5,09282E+24 2,54641E+24 1,27321E+24 15 Sodium carbonate 1130680 5,72846E+25 6,05633E+24 3,02816E+24 1,51408E+24 16 Ammonia 46050 2,33307E+24 2,4666E+23 1,2333E+23 6,16651E+22 17 Barium Hydroxide -512000 -2,59399E+25 -2,74245E+24 -1,37123E+24 -6,85614E+23 18 Potassium Hydroxide 487000 2,46733E+25 2,60855E+24 1,30427E+24 6,52136E+23 19 Aluminium Hydroxide 1274900 6,45914E+25 6,82882E+24 3,41441E+24 1,7072E+24 20 Magnesium Hydroxide 924750 4,68514E+25 4,95329E+24 2,47665E+24 1,23832E+24 21 Sodium Hydride 78000 3,95178E+24 4,17796E+23 2,08898E+23 1,04449E+23 22 Lithium Hydroxide 485000 2,4572E+25 2,59783E+24 1,29892E+24 6,49458E+23 23 Calcium Hydroxide 985000 4,99039E+25 5,27601E+24 2,63801E+24 1,319E+24 24 Strontium Hydroxide -506000 -2,56359E+25 -2,71032E+24 -1,35516E+24 -6,77579E+23 25 Sodium Hydroxide 425130 2,15387E+25 2,27715E+24 1,13857E+24 5,69287E+23 26 Calcium Oxide 635000 3,21716E+25 3,40129E+24 1,70064E+24 8,50322E+23 27 Acetic Acid 485000 2,4572E+25 2,59783E+24 1,29892E+24 6,49458E+23 28 Methanol 240000 1,21593E+25 1,28553E+24 6,42763E+23 3,21381E+23 29 Propanol 318730 1,61481E+25 1,70723E+24 8,53616E+23 4,26808E+23 30 Ethanol 275420 1,39538E+25 1,47525E+24 7,37624E+23 3,68812E+23 31 Isopropanol 303730 1,53881E+25 1,62689E+24 8,13443E+23 4,06722E+23 32 Methylene Chloride 91500 4,63575E+24 4,90107E+23 2,45053E+23 1,22527E+23 33 n-heptane 190970 9,67528E+24 1,0229E+24 5,11452E+23 2,55726E+23 34 Toulene -48130 -2,43845E+24 -2,57801E+23 -1,28901E+23 -6,44504E+22 35 Propylene carbonate 624340 3,16315E+25 3,34419E+24 1,67209E+24 8,36047E+23 36 Benzene 49000 2,48253E+24 2,62461E+23 1,31231E+23 6,56154E+22 37 Acetone 248120 1,25707E+25 1,32902E+24 6,6451E+23 3,32255E+23 38 methly tert-butyl ether 313600 1,58882E+25 1,67975E+24 8,39877E+23 4,19938E+23 39 Formic Acid 405310 2,05346E+25 2,17098E+24 1,08549E+24 5,42746E+23 40 Chloroform 134470 6,81277E+24 7,20269E+23 3,60135E+23 1,80067E+23 41 tetrachloro-ethylene 10760 5,45143E+23 5,76344E+22 2,88172E+22 1,44086E+22

Figure 4.3.1 to figure 4.3.5 demonstrate the graphs drawn between numbers of photons required to destroy one mole of toxic material for four different lasers as mentioned above, against the type of material.

No. of photons to destroy one mole of toxic solid by lasers

IR CO2 Laser Nd:YAG Laser Green Laser UV Laser

9,31658E+24 1E+25 8E+24 6E+24 No. of photons 4E+24 9,8498E+23 4,9249E+23 2E+24 2,46245E+23 0

ZnS

Figure 4.3.1: Number of photons to destroy one mole of toxic solid by lasers

No. of photons to destroy one mole of toxic gas by lasers

IR CO2 Laser Nd:YAG Laser Green Laser UV Laser

5E+24 4,57242E+24

4E+24

No of photons 3E+24

2E+24 1,67849E+24 4,83411E+23 1E+24 2,41706E+23 1,20853E+23 1,77456E+23 8,8728E+22 0 4,4364E+22 NO NO2

Type of gas

Figure 4.3.2: Number of photons to destroy one mole of toxic gas by lasers

Figure 4.3.3: Number of photons to destroy one mole of acids by lasers

Figure 4.3.4: Number of photons to destroy one mole of base by laser

Figure 4.3.5: Number of photons to destroy one mole of organic solvent by laser

At present there is no laser available with the pulse rate and the very demanding specifications imposed by the dissociation energies calculated. One of the biggest limits is the pulse frequency rate. Only the Gas Dynamic Laser developed by Professor Apollonov producing 100 KW of peak power (2.86 J) with pulses of 5 ns at prf of 350 KHz is the solution to be utilized to demolish the toxic materials evaluated. The other laser sources may be utilized exploiting laser plasma interaction and not molecular dissociation.

4.4. Material destroyed rate by CO2 Gas Dynamic Laser

CO2 Gas Dynamic Laser developed by Apollonov [236] is the ideal laser and the calculations are made using its specifications Wavelength of 10640 nm 1 MW peak power (It can deliver 250 MW in 3 seconds) 2.86 J @ 5 ns pulsed width prf 350 kHz. The procedure used to calculate the values written in the tables is elaborated under heading 4.1.1.

4.4.1. Solids

Table 4.4.1.1 demonstrates the results obtained by mathematical calculations as mentioned in section 4.1.1, for ZnS. Values of CO2 Gas Dynamic Laser developed by Apollonov are used. Table 4.4.1.1

Infrad Red Planks Speed of CO2 Laser Constant 6,63E-34 Light 299792458 λL(m) 1,06E-05 No of Energy of No.of photons No.of pulses Decompositio photons to one photon in 2.86J Laser to destroy Sr. Toxic n Energy destroy toxic of Infra Red beam of Infra toxic No solids (J/mol) λt=hc/E material CO2, Laser Red CO2,n material 1 ZnS 183890 1,08E-30 9,85E+24 1,87E-20 1,53E+20 6,43E+04

By following the procedure mentioned in section 4.1.1, Table 4.4.1.2 demonstrates the results of material destroyed in kg/hr for ZnS.

Table 4.4.1.2

Time to generate required pulses to Material Material Sr. Number of pulses destroy one mole of Molar Mass in detroyed destroye No generated in 1 sec toxic mat,sec Mass kg , kg/sec d, kg/hr 1 350000 1,84E-01 97,474 0,097474 5,31E-01 1,91E+03

Amount of ZnS destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in Figure 4.4.1.1 for laser energy of 2.86 J.

ZnS destroyed by 2.86 J Laser

1,91E+03

2,00E+03

1,50E+03

kg/hr 1,00E+03

5,00E+02

0,00E+00 ZnS

Figure 4.4.1.1: Destruction of ZnS through a laser of energy 2.86 J

4.4.2. Gases

Table 4.4.2.1 demonstrates the results obtained by mathematical calculations as mentioned

in section 4.1.1 for gases. Values of CO2 Gas Dynamic Laser developed by Apollonov are

used. Table 4.4.2.1

Planks Ligh Infrad Red CO2 Constant 6,63E-34 Speed 299792458 Laser λL(m) 1,06E-05

No of photons Energy of one No.of photons in No.of pulses Sr. Toxic Decomposition to destroy toxic photon of Infra 2.86J Laser beam to destroy No Gases Energy (J/mol) λt=hc/E material Red CO2, Laser of Infra Red CO2,n toxic material 1 NO 90250 2,20E-30 4,83E+24 1,87E-20 1,53E+20 3,16E+04 2 NO2 33130 6,00E-30 1,77E+24 1,87E-20 1,53E+20 1,16E+04

Table 4.4.2.2 demonstrates the material destroyed in kg/hr for gases, by following the procedure mentioned in section 4.1.1.

Table 4.4.2.2

Number of Time to generate pulses required pulses to Material Material Material Sr. generated destroy one mole Molar Mass, detroyed, destroyed, Dens destoyed No in 1 sec of toxic mat,sec Mass kg kg/sec kg/hr ity m3/hr 1 350000 9,02E-02 30 0,03 3,33E-01 1,20E+03 1270 9,43E-01 2 350000 3,31E-02 46 0,046 1,39E+00 5,00E+03 2620 1,91E+00

Amount of gases destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in a graphical form in the figure 4.4.2.1 for the laser of energy 2.86 J.

Gases destruction by 2.865 J Laser

1,91E+00 2,00E+00

1,50E+00 9,43E-01

m3/hr 1,00E+00

5,00E-01

0,00E+00 NO NO2

Figure 4.4.2.1: Nitrogen oxide destruction through lasers of energy 2.865 J

4.4.3. Liquids Table 4.4.3.1 demonstrates the results obtained by mathematical calculations as mentioned in section 4.1.1, for liquids. Values of CO2 Gas Dynamic Laser developed by Apollonov are used.

Table 4.4.3.1

Planks Speed of Infrad Red CO2 Constant 6,63E-34 Light 299792458 Laser λL(m) 1,06E-05 No.of photons in No.of No of photons Energy of 1 2.86J Laser beam pulses to Sr. Toxic Decomposition to destroy photon of Infra of Infra Red destroy No Liquids Energy (J/mol) λt=hc/E toxic material Red CO2, Laser CO2,n toxic 1 HI 26000 7,64E-30 1,39E+24 1,87E-20 1,53E+20 9,09E+03 2 H2C2O4 252620 7,86E-31 1,35E+25 1,87E-20 1,53E+20 8,83E+04 3 HCOOH 405310 4,90E-31 2,17E+25 1,87E-20 1,53E+20 1,42E+05 4 HNO3 174000 1,14E-30 9,32E+24 1,87E-20 1,53E+20 6,08E+04 5 H2O2 187600 1,06E-30 1,00E+25 1,87E-20 1,53E+20 6,56E+04 6 CH3COOH 485000 4,10E-31 2,60E+25 1,87E-20 1,53E+20 1,70E+05 7 H3BO3 7195 2,76E-29 3,85E+23 1,87E-20 1,53E+20 2,52E+03 8 H2SO4 72000 2,76E-30 3,86E+24 1,87E-20 1,53E+20 2,52E+04 9 C6H8O7 1384000 1,44E-31 7,41E+25 1,87E-20 1,53E+20 4,84E+05 10 C6H5COOH 385070 5,16E-31 2,06E+25 1,87E-20 1,53E+20 1,35E+05 11 HBr 36400 5,46E-30 1,95E+24 1,87E-20 1,53E+20 1,27E+04 12 HCl 92330 2,15E-30 4,95E+24 1,87E-20 1,53E+20 3,23E+04 13 NaHCO3 91630 2,17E-30 4,91E+24 1,87E-20 1,53E+20 3,20E+04 14 NaHCO3 950800 2,09E-31 5,09E+25 1,87E-20 1,53E+20 3,32E+05 15 Na2CO3 1130680 1,76E-31 6,06E+25 1,87E-20 1,53E+20 3,95E+05 16 NH3 46050 4,31E-30 2,47E+24 1,87E-20 1,53E+20 1,61E+04 17 Ba(OH)2 512000 3,88E-31 2,74E+25 1,87E-20 1,53E+20 1,79E+05 18 KOH 487000 4,08E-31 2,61E+25 1,87E-20 1,53E+20 1,70E+05 19 Al(OH)3 1274900 1,56E-31 6,83E+25 1,87E-20 1,53E+20 4,46E+05 20 Mg(OH)2 924750 2,15E-31 4,95E+25 1,87E-20 1,53E+20 3,23E+05 21 NaH 78000 2,55E-30 4,18E+24 1,87E-20 1,53E+20 2,73E+04 22 LiOH 485000 4,10E-31 2,60E+25 1,87E-20 1,53E+20 1,70E+05 23 Ca(OH)2 985000 2,02E-31 5,28E+25 1,87E-20 1,53E+20 3,44E+05 24 Sr(OH)2 506000 3,93E-31 2,71E+25 1,87E-20 1,53E+20 1,77E+05 25 NaOH 425130 4,67E-31 2,28E+25 1,87E-20 1,53E+20 1,49E+05 26 CaO 635000 3,13E-31 3,40E+25 1,87E-20 1,53E+20 2,22E+05 27 CH3COOH 485000 4,10E-31 2,60E+25 1,87E-20 1,53E+20 1,70E+05 28 CH3OH 240000 8,28E-31 1,29E+25 1,87E-20 1,53E+20 8,39E+04 29CH3CH2CH2OH 318730 6,23E-31 1,71E+25 1,87E-20 1,53E+20 1,11E+05 30 CH3CH2OH 275420 7,21E-31 1,48E+25 1,87E-20 1,53E+20 9,63E+04 31(CH3)2CHOH 303730 6,54E-31 1,63E+25 1,87E-20 1,53E+20 1,06E+05 32 CH2Cl2 91500 2,17E-30 4,90E+24 1,87E-20 1,53E+20 3,20E+04 33 C7H16 190970 1,04E-30 1,02E+25 1,87E-20 1,53E+20 6,68E+04 34 C7H8 48130 4,13E-30 2,58E+24 1,87E-20 1,53E+20 1,68E+04 35 C4H6O3 624340 3,18E-31 3,34E+25 1,87E-20 1,53E+20 2,18E+05 36 C6H6 49000 4,05E-30 2,62E+24 1,87E-20 1,53E+20 1,71E+04 37 (CH3)2CO 248120 8,01E-31 1,33E+25 1,87E-20 1,53E+20 8,68E+04 38 C5H12O 313600 6,33E-31 1,68E+25 1,87E-20 1,53E+20 1,10E+05 39 HCOOH 405310 4,90E-31 2,17E+25 1,87E-20 1,53E+20 1,42E+05 40 CHCl3 134470 1,48E-30 7,20E+24 1,87E-20 1,53E+20 4,70E+04 41 C2Cl4 10760 1,85E-29 5,76E+23 1,87E-20 1,53E+20 3,76E+03

By following the procedure mentioned in section 4.1.1, table 4.4.3.2 demonstrates the results of material destroyed in kg/hr for liquids.

Table 4.4.3.2 Number of Time to generate pulses required pulses to Material Material Material Sr. generated destroy one mole Molar Mass, detroyed, destroye Dens destoyed No in 1 sec of toxic mat,sec Mass kg kg/sec d, kg/hr ity m3/hr 1 350000 2,60E-02 128 0,128 4,93E+00 1,77E+04 2850 6,22E+00 2 350000 2,52E-01 90 0,09 3,57E-01 1,28E+03 1900 6,76E-01 3 350000 4,05E-01 46 0,046 1,14E-01 4,09E+02 1220 3,35E-01 4 350000 1,74E-01 63 0,063 3,62E-01 1,30E+03 1510 8,64E-01 5 350000 1,87E-01 34 0,034 1,81E-01 6,53E+02 1450 4,50E-01 6 350000 4,85E-01 60 0,06 1,24E-01 4,46E+02 1050 4,25E-01 7 350000 7,19E-03 62 0,062 8,63E+00 3,11E+04 1440 2,16E+01 8 350000 7,19E-02 98 0,098 1,36E+00 4,90E+03 1840 2,67E+00 9 350000 1,38E+00 192 0,192 1,39E-01 5,00E+02 1665 3,00E-01 10 350000 3,85E-01 122 0,122 3,17E-01 1,14E+03 1270 8,99E-01 11 350000 3,64E-02 81 0,081 2,23E+00 8,02E+03 1490 5,38E+00 12 350000 9,22E-02 36 0,036 3,90E-01 1,41E+03 1490 9,43E-01 13 350000 9,15E-02 84 0,084 9,18E-01 3,30E+03 2200 1,50E+00 14 350000 9,50E-01 84 0,084 8,84E-02 3,18E+02 2200 1,45E-01 15 350000 1,13E+00 106 0,106 9,38E-02 3,38E+02 2540 1,33E-01 16 350000 4,60E-02 17 0,017 3,70E-01 1,33E+03 682 1,95E+00 17 350000 5,11E-01 171 0,171 3,34E-01 1,20E+03 3743 3,22E-01 18 350000 4,87E-01 56 0,056 1,15E-01 4,14E+02 2044 2,03E-01 19 350000 1,27E+00 78 0,078 6,12E-02 2,20E+02 2420 9,11E-02 20 350000 9,24E-01 58 0,058 6,28E-02 2,26E+02 2340 9,66E-02 21 350000 7,79E-02 24 0,024 3,08E-01 1,11E+03 1400 7,92E-01 22 350000 4,85E-01 24 0,024 4,95E-02 1,78E+02 1460 1,22E-01 23 350000 9,84E-01 74 0,074 7,52E-02 2,71E+02 2211 1,22E-01 24 350000 5,05E-01 122 0,122 2,41E-01 8,69E+02 3625 2,40E-01 25 350000 4,25E-01 40 0,04 9,42E-02 3,39E+02 2130 1,59E-01 26 350000 6,34E-01 56 0,056 8,83E-02 3,18E+02 3350 9,49E-02 27 350000 4,85E-01 60 0,06 1,24E-01 4,46E+02 1050 4,25E-01 28 350000 2,40E-01 32 0,032 1,33E-01 4,80E+02 792 6,07E-01 29 350000 3,18E-01 60 0,06 1,88E-01 6,78E+02 803 8,45E-01 30 350000 2,75E-01 46 0,046 1,67E-01 6,02E+02 789 7,63E-01 31 350000 3,03E-01 60 0,06 1,98E-01 7,12E+02 786 9,06E-01 32 350000 9,14E-02 85 0,085 9,30E-01 3,35E+03 1330 2,52E+00 33 350000 1,91E-01 100 0,1 5,24E-01 1,89E+03 684 2,76E+00 34 350000 4,81E-02 92 0,092 1,91E+00 6,89E+03 867 7,94E+00 35 350000 6,24E-01 102 0,102 1,64E-01 5,89E+02 1205 4,89E-01 36 350000 4,90E-02 78 0,078 1,59E+00 5,74E+03 876 6,55E+00 37 350000 2,48E-01 58 0,058 2,34E-01 8,42E+02 791 1,06E+00 38 350000 3,13E-01 88 0,088 2,81E-01 1,01E+03 740 1,37E+00 39 350000 4,05E-01 46 0,046 1,14E-01 4,09E+02 1220 3,35E-01 40 350000 1,34E-01 119 0,119 8,86E-01 3,19E+03 1483 2,15E+00 41 350000 1,07E-02 166 0,166 1,54E+01 5,56E+04 1620 3,43E+01

Amount of acids destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in figure 4.4.3.1 in a graphical form for the laser of energy 2.86 J.

Acids destroyed by 2.86 J Laser 2,50E+01 2,16E+01 2,00E+01

1,50E+01 m3/hr 1,00E+01 5,38E+00 6,22E+00 2,67E+00 5,00E+00 6,76E-01 8,64E-01 4,25E-01 8,99E-01 3,35E-01 4,50E-01 3,00E-01 9,43E-01 0,00E+00

Figure 4.4.3.1: Destruction of acids by 2.86J Laser

Amount of bases destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in figure 4.4.3.2 in a graphical form for the laser of energy 2.86

Bases destroyed by 2.86 J Laser 2,50E+00

1,95E+00 2,00E+00

1,50E+00 1,50E+00 m3/hr 1,00E+00 7,92E-01

3,22E-01 9,11E-02 1,22E-01 1,59E-01 5,00E-01 1,33E-01 2,03E-01 2,40E-01 1,45E-01 9,66E-02 1,22E-01 9,49E-02 0,00E+00

J. Figure 4.4.3.2: Destruction of bases through a laser of energy 2.86J

Amount of organic solvents destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in figure 4.4.3.3 in a graphical form for the laser of energy 2.86 J.

Organic Solvents destoyed by 2.86 J Laser 4,00E+01 3,43E+01 3,50E+01 3,00E+01 2,50E+01 m3/hr 2,00E+01 1,50E+01 7,94E+00 1,00E+01 6,55E+00 7,63E-01 2,76E+00 1,37E+00 5,00E+00 6,07E-01 2,52E+00 2,15E+00 4,25E-01 8,45E-01 9,06E-01 4,89E-01 1,06E+00 3,35E-01 0,00E+00

Figure 4.4.3.3: Destruction of organic solvents through a laser of energy 2.86 J

The above calculations were made with a laser of 286.5 J Laser and the values obtained are shown in the following graphs. They showed an increasing trend with increasing the input energy.

Amount of acids destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in figure 4.4.3.4 in a graphical form for the laser of energy 286.5 J.

Acids destroyed by 286.5 J Laser 2,50E+03 2,15E+03 2,00E+03

1,50E+03 m3/hr 1,00E+03 6,22E+02 5,38E+02 5,00E+02 8,63E+01 4,24E+01 6,75E+01 2,66E+02 8,98E+01 3,35E+01 4,50E+01 3,00E+01 9,42E+01 0,00E+00

Figure 4.4.3.4: Destruction of acids through laser of energy 286.5J

Amount of bases destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in figure 4.4.3.5 in a graphical form for the laser of energy 286.5 J.

Bases destroyed by 286.5 J Laser 2,50E+02

1,95E+02 2,00E+02

1,50E+02 1,50E+02 m3/hr 1,00E+02 7,91E+01

1,45E+01 3,21E+01 1,22E+01 1,59E+01 5,00E+01 9,65E+00 2,03E+01 2,39E+01 1,33E+01 9,10E+00 1,22E+01 9,48E+00 0,00E+00

Figure 4.4.3.5: Destruction of bases through laser of energy 286.5J

Amount of organic solvents destroyed per hour using CO2 Gas Dynamic Laser developed by Apollonov as calculated above is demonstrated in figure 4.4.3.6 for the laser of energy 286.5 J.

Organic solvents destroyed by 286.5 J Laser 4,00E+03 3,43E+03 3,50E+03 3,00E+03 2,50E+03 m3/hr 2,00E+03 1,50E+03 7,94E+02 6,54E+02 1,00E+03 2,51E+02 6,06E+01 7,62E+01 1,37E+02 2,15E+02 5,00E+02 2,76E+02 4,24E+01 8,44E+01 9,05E+01 4,88E+01 1,06E+02 3,35E+01 0,00E+00

Figure 4.4.3.6: Destruction of organic solvents through laser of energy 286.5J

5. Plasma exploitation

In this section we are interested to model, investigate and evaluate the rate of transformation into plasma of each of the most common and dangerous toxic materials. The list of those toxic materials has been provided by AMIAT, Torino, Italy. This investigation is useful to dimension the experimental setup in order to realize a table-top demonstrator. Therefore the laser sources considered in the present simulation are comparatively small respect those which will be utilized in reality. In order to find the most suitable material to conduct the experiment and also to test the simulation model, calculations were carried for each of the listed toxic materials (list supplied by the Director general of AMIAT, Torino, Italy. The purpose was to identify the most suitable material for preliminary experiments. Once the table-top prototype will be developed and the simulation model verified calculations will be made utilizing the selected laser source. Determining the closest values of the destruction rates (measured in kg/s) for each material will enable to develop a grid of comparison between the proposed laser waste destruction method and the methods with conventional technologies presently in use to destroy the same types of toxic materials.

The laser beam aimed at the toxic material vaporizes it and then transforms the vapor into plasma. Increasing the exposure of the vapor to the laser beam will transform it into a hot plasma. It is quite obvious that for plasma generation, laser beam fluence [237- 238] must be greater than vaporization threshold [237, 239]. So first the laser beam will transform toxic material into vapors and then plasma [237], finally the addition of a suitable catalyst will turn the hot plasma into a hot, high pressure inert gas.

The mathematical relation for the power density in order to achieve vaporization threshold is given by following relation [237].

[ ( ) ]√ ⁄

Where [237]

Sv = Power density

3 values used are fixed while the others vary from material to material. They are listed below tp = pulse duration of laser i.e. pulse width. In the calculations it’s fixed as 5 ns. Its range varies from 500 ps to 10 ns

α = Coefficient of absorption of the material at the specific laser wavelength and it is dimensionless. Its range varies from 0.01 to 0.3 but in this case fixed value of 0.1 is used.

To = 300 K

The variable values are as follows and depend upon the toxic material

ρ = Density of toxic material in kg/m3

Tv = Vaporization temperature of the targeted toxic material

D = Thermal diffusivity measured in m2/s (k=thermal conductivity)

Lm = Heat of fusion J/kg

C = Heat Capacity in J/kg K

All the values for all the materials are not available on the internet. So there were problems in finding vaporization temperature and thermal diffusivity of some materials. So in some cases the thermal diffusivities and vaporization temperatures are mentioned for the element of the material which has high molar mass.

Example for ZnS is shown below and then the results of other materials are presented in tabulate form.

The values of ZnS are

ρ = 4090 kg/m3

Tv = 1458 K; Melting point is written, vaporization temperature hasn’t been determined yet

D = 4.14*10-5 m2/s; thermal diffusivity of Zn is listed. (Thermal diffusivity of most of the materials is not known so the thermal diffusivity of heavier element is used in those cases)

Lm = 2099021

C = 515 J/kg-K

Putting these values in the following equation [237]

[ ( ) ]√ ⁄

If we have a Nd:YAG laser with 5 ns pulse and 10 J energy we will have a peak power of

10 J/5*10-9 =2.0*109 W, thus the beam area will be

2*109 W/1.012x1010 = 0.19 m2 ~ 0.2 m2 with a beam spot diameter of 0.5 m.

With a Nd:YAG laser of 10 J @ 5 ns pulse width we can vaporize a surface of 0.2 m2 of ZnS

Energy deposited per pulse can be calculated with the help of following relation [237]

Mass vaporized per pulse can be calculated from the following relation [237]

√

The mass vaporized in one minute of laser action depends on the prf of the laser, for example 10 J laser may have a 5 Hz prf, from the period T we can calculate the number of pulses in one minute and that is

-9 Np = 60 s * 5 Hz = 30 thus the vaporization interaction time is ty is Np * tp = 30*5*10 = 0.15* 10-6 = 0.15 µs, thus total mass evaporated and transformed in one minute of laser operation is given by [237]

√

All the materials have been calculated in the same way and the results are expressed in the tabulated form.

5.1. Solids

Table 5.1.1 demonstrates the data, required in order to find mass evaporated and transformed for ZnS.

Table 5.1.1: Data table for Solids (ZnS)

Vaporization Thermal Heat of Heat Density temperature diffusivity fusion,Lm, Capacity, Sr.No Toxic solids (kg/m3) Tv,K , D,m2/s J/kg C,J/kgK 1 ZnS 4090 1458 4.14E-5 2099021 515 Power density calculations for ZnS are demonstrated in Table 5.1.2.

Table 5.1.2: Power density calculations for ZnS

Power Density Vaporizat ion Thermal Heat of Density temperat diffusivity fusion,Lm Power Sr.No Toxic solids (kg/m3) ure Tv,K , D,m2/s , J/kg Heat Capacity,C,J/kgK Density 1 ZnS 4090 1458 4,14E-05 2099021 515 7,836E+12

Energy deposited per pulse is demonstrated in Table 5.1.3 using the result of power density.

Table 5.1.3: Energy deposited per pulse calculations for ZnS

Energy deposited per pulse Sr.No W α Sv tp pi Energy deposited per pulse 1 0,25 0,1 7,84E+12 5*10^(-9) 3,14159 7,69E+02

Mass evaporated of ZnS per pulse is demonstrated in Table 5.1.4.

Table 5.1.4: Mass vaporized per pulse for ZnS

Mass vaporized per pulse

Thermal Density diffusivit Sr.No (kg/m3) pi w y, D,m2/s tp Mass vaporized per pulse 1 4090 3,14159 0,25 4,14E-05 5*10^(-9) 3,65E-04

Table 5.1.5 demonstrates the results of mass evaporated and transformed in 1 hr by laser operation.

Table 5.1.5: Mass evaporated and transformed per hour for laser operation

Mass evaporated and transformed/hr of laser operation Mass evapoarted Thermal Mass evaporated and and transformed in Density diffusivit transformed in 1 min 1hr by laser Sr.No (kg/m3) w y, D,m2/s Np tp by laser operation operation 1 4090 0,25 4,14E-05 30 5*10^-9 2,00E-03 1,20E-01 Figure 5.1 demonstrates the graph drawn between the material and its mass evaporated and transformed per kg in an hour.

Mass evaporated and transformed

2,00E-01 1,20E-01

kg/hr 1,00E-01

0,00E+00 ZnS

Figure 5.1: Mass Evaporated and transformed for ZnS

5.2. Gases

Table 5.2.1 demonstrates the data, required in order to find mass evaporated and transformed for gases.

Table 5.2.1: Data table for nitrogen oxides

Vaporization Thermal Heat of Heat Density temperature diffusivity, fusion,Lm, Capacity,C,J Sr.No Toxic Gases (kg/m3) Tv,K D,m2/s J/kg /kgK 1 NO 1270 121 1,99E-08 76667 Cp= 966 2 NO2 2620 294 1,99E-08 142174 Cp= 781 Thermal diffusivity values demonstrated in Table 5.2.1 are of oxygen.

Power density calculations for gases are demonstrated in Table 5.2.2.

Table 5.2.2: Power Density calculations for nitrogen oxides

Power Density Vaporizat ion Thermal Heat of Heat Density temperat diffusivit fusion,L Capacity, Sr.No Toxic Gases(kg/m3) ure Tv,K y, D,m2/s m, J/kg C,J/kgK Power Density 1 NO 1270 121 1,99E-08 76667 966 -253540455,2 2 NO2 2620 294 1,99E-08 142174 781 7308496267

Table 5.2.3: Energy deposited per pulse calculations for nitrogen oxides

Energy deposited per pulse Sr.No w α Sv tp pi Energy deposited per pulse 1 0,25 0,1 2,54E+08 5*10^(-9) 3,14159 2,49E-02 2 0,25 0,1 7,31E+09 5*10^(-9) 3,14159 7,17E-01 Mass evaporated of gases per pulse is demonstrated in Table 5.2.4.

Table 5.2.4: Mass vaporized per pulse calculations for nitrogen oxides Mass vaporized per pulse

Thermal Density diffusivit Sr.No (kg/m3) pi w y, D,m2/s tp Mass vaporized per pulse 1 1270 3,14159 0,25 1,99E-08 5*10^(-9) 2,49E-06 2 2620 3,14159 0,25 1,99E-08 5*10^(-9) 5,13E-06

Table 5.2.5 demonstrates the results of mass evaporated and transformed in 1 hr by laser operation.

Table 5.2.5: Mass evaporated and transformed per hour of laser operations for nitrogen oxides Mass evaporated and transformed/hr of laser operation

Thermal Mass evaporated and Mass evaporated Density diffusivit transformed in 1 min and transformed Sr.No (kg/m3) w y, D,m2/s Np tp by laser operation in 1 hr 1 1270 0,25 1,99E-08 30 5*10^-9 1,36E-05 8,17E-04 2 2620 0,25 1,99E-08 30 5*10^-9 2,81E-05 1,69E-03 Figure 5.2 demonstrates the graph drawn between the gases and their mass evaporated and transformed per kg in an hour.

Mass evaporated and transformed

0,002 0,001686375

0,0015 0,000817441 kg/hr 0,001 0,0005 0 NO NO2

Figure 5.2: Mass Evaporated and transformed for Nitrogen mono-oxide and Nitrogen dioxide

5.3. Liquids

Table 5.3.1 demonstrates the data, required in order to find mass evaporated and transformed for liquids.

Table 5.3.1: Data table for acids, bases and organic solvents

Vaporizat ion Thermal Heat of Heat Density temperat diffusivit fusion,L Capacity, Sr.No Toxic Liquids (kg/m3) ure Tv,K y, D,m2/s m, J/kg C,J/kgK 1 Hydrogen Iodide (HI) 2850 238 2,12E-07 22437 228,3 2 Formic Acid (HCOOH) 1220 374 1,99E-08 275472 2200 3 Nitric Acid (HNO3) 1510 356 1,99E-08 166640 1740 4 Hydrogen peroxide (H2O2) 1450 423 1,99E-08 367488 1267 5 Acetic Acid (CH3COOH) 1050 392 1,99E-08 195330 2043 6 Boric Acid (H3BO3) 1440 573 1,99E-08 360666 1392 7 Sulfuric Acid (H2SO4) 1840 610 1,99E-08 109197 1340 8 Benzoic Acid (C6H5COOH) 1270 522 8,70E-05 147559 1238 9 Hydrogen Bromide (HBr) 1490 206 4,16E-08 29786 351 10 Hydrochloric Acid (HCl) 1490 188 5,95E-09 54853 798 11 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043 12 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043 13 Sodium carbonate (Na2CO3) 2540 1906 1,19E-04 280188 1060 14 Ammonia (NH3) 682 240 9,90E-09 332335 2061 15 Potassium Hydroxide (KOH) 2044 1600 1,99E-08 140806 1228 17 Lithium Hydroxide, LiOH 1460 1197 1,99E-08 872651 2071 18 Sodium Hydroxide, NaOH 2130 1661 1,19E-04 165000 1488 19 Calcium Oxide, CaO 3350 3123 1,99E-04 1426599 749 20 Acetic Acid, CH3COOH 1050 391 1,99E-08 195330 2053 21 Methanol, CH3OH 792 338 1,99E-08 100343 2531 22 Propanol, CH3CH2CH2OH 803 370 8,70E-05 89357 2395 23 Ethanol CH3CH2OH 789 352 8,70E-05 107036 2438 24 Isopropanol, (CH3)2CHOH 786 356 8,70E-05 90016 2604 25 Methylene Chloride, CH2Cl2 1330 313 5,95E-09 54162 1192 26 n-heptane, C7H16 684 371 8,70E-05 140005 2242 27 Toulene, C7H8 867 384 8,70E-05 72064 1707 28 Propylene carbonate, C4H6O3 1205 513 1,99E-08 78362 2141 29 Benzene, C6H6 876 353 8,70E-05 126360 1055 30 Acetone, (CH3)2CO 791 330 8,70E-05 99345 2175 31 methly tert-butyl ether, C5H12O 740 328 8,70E-05 86216 2127 32 Formic Acid, HCOOH 1220 374 1,99E-08 275472 2151 33 Chloroform, CHCl3 1483 334 5,95E-09 79577 956 34 tetrachloro-ethylene, C2Cl4 1620 394 5,95E-09 65609 864

As mentioned earlier there were few values whose data were not available so those values are used for a material which has high molar mass. It is demonstrated in Table 5.3.2.

Table 5.3.2: Variations used in data search. As the data for all the materials was not available

Sr.No Toxic Liquids Variables 1 Hydrogen Iodide (HI) Cp is of gas phase, thermal diffusivity of iodine 2 Formic Acid (HCOOH) Cp at 20-100C, thermal diffusivity of oxygen 3 Nitric Acid (HNO3) Thermal diffusivity of oxygen 4 Hydrogen peroxide (H2O2) Cp of gas, thermal diffusivity of oxygen 5 Acetic Acid (CH3COOH) Thermal diffusivity of oxygen 6 Boric Acid (H3BO3) Thermal diffusivity of oxygen 7 Sulfuric Acid (H2SO4) Thermal diffusivity of oxygen 8 Benzoic Acid (C6H5COOH) Thermal diffusivity of graphite 9 Hydrogen Bromide (HBr) Thermal diffusivity of bromine 10 Hydrochloric Acid (HCl) Thermal diffusivity of chlorine 11 Sodium bicarbonate (NaHCO3) Thermal diffusivity of oxygen 12 Sodium bicarbonate (NaHCO3) Thermal diffusivity of oxygen 13 Sodium carbonate (Na2CO3) Thermal diffusivity of Sodium 14 Ammonia (NH3) Thermal diffusivity of Nitrogen 16 Sodium Hydride NaH Thermal diffusivity of Sodium 17 Lithium Hydroxide, LiOH Thermal diffusivity of oxygen 18 Sodium Hydroxide, NaOH Thermal diffusvity of Sodium 19 Calcium Oxide, CaO Thermal diffusivity of Calcium 20 Acetic Acid, CH3COOH Thermal diffusivity of oxygen 21 Methanol, CH3OH Thermal diffusivity of oxygen 22 Propanol, CH3CH2CH2OH Thermal diffusivity of graphite 23 Ethanol CH3CH2OH Thermal diffusivity of graphite 24 Isopropanol, (CH3)2CHOH Thermal diffusivity of graphite 25 Methylene Chloride, CH2Cl2 Thermal diffusivity of chlorine 26 n-heptane, C7H16 Thermal diffusivity of graphite 27 Toulene, C7H8 Thermal diffusivity of graphite 28 Propylene carbonate, C4H6O3 Thermal diffusivity of oxygen 29 Benzene, C6H6 Cp of gas, thermal diffusivity of graphite 30 Acetone, (CH3)2CO Thermal diffusivity of graphite 31 methly tert-butyl ether, C5H12O Thermal diffusivity of graphite 32 Formic Acid, HCOOH Thermal diffusivity of oxygen 33 Chloroform, CHCl3 Thermal diffusivity of chlorine 34 tetrachloro-ethylene, C2Cl4 Thermal diffusivity of chlorine

Power density calculations for liquids are demonstrated in Table 5.3.3.

Table 5.3.3: Power density calculations for acids, bases and organic solvents Densi Vaporizat ty ion Thermal Heat of Heat (kg/m temperat diffusivit fusion,L Capacity, Power Sr.No Toxic Liquids 3) ure Tv,K y, D,m2/s m, J/kg C,J/kgK Density 1 Hydrogen Iodide (HI) 2850 238 2,12E-07 22437 228,3 3760419934 2 Formic Acid (HCOOH) 1220 374 1,99E-08 275472 2200 8690851951 3 Nitric Acid (HNO3) 1510 356 1,99E-08 166640 1740 6491274914 4 Hydrogen peroxide (H2O2) 1450 423 1,99E-08 367488 1267 1,289E+10 5 Acetic Acid (CH3COOH) 1050 392 1,99E-08 195330 2043 6065200324 6 Boric Acid (H3BO3) 1440 573 1,99E-08 360666 1392 1,5833E+10 7 Sulfuric Acid (H2SO4) 1840 610 1,99E-08 109197 1340 1,1652E+10 8 Benzoic Acid (C6H5COOH) 1270 522 8,70E-05 147559 1238 2,5069E+11 9 Hydrogen Bromide (HBr) 1490 206 4,16E-08 29786 351 787921604 10 Hydrochloric Acid (HCl) 1490 188 5,95E-09 54853 798 -440122777 11 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043 3,1969E+10 12 Sodium bicarbonate (NaHCO3) 2200 1124 1,99E-08 297594 1043 3,1969E+10 13 Sodium carbonate (Na2CO3) 2540 1906 1,19E-04 280188 1060 1,1412E+12 14 Ammonia (NH3) 682 240 9,90E-09 332335 2061 2345921752 15 Potassium Hydroxide (KOH) 2044 1600 1,99E-08 140806 1228 3,8372E+10 16 Sodium Hydride NaH 1400 1073 1,19E-04 1517 1,6417E+10 17 Lithium Hydroxide, LiOH 1460 1197 1,99E-08 872651 2071 5,254E+10 18 Sodium Hydroxide, NaOH 2130 1661 1,19E-04 165000 1488 5,8533E+11 19 Calcium Oxide, CaO 3350 3123 1,99E-04 1426599 749 9,6051E+12 20 Acetic Acid, CH3COOH 1050 391 1,99E-08 195330 2053 6053303824 21 Methanol, CH3OH 792 338 1,99E-08 100343 2531 2347184318 22 Propanol, CH3CH2CH2OH 803 370 8,70E-05 89357 2395 9,5996E+10 23 Ethanol CH3CH2OH 789 352 8,70E-05 107036 2438 1,124E+11 24 Isopropanol, (CH3)2CHOH 786 356 8,70E-05 90016 2604 9,4475E+10 25 Methylene Chloride, CH2Cl2 1330 313 5,95E-09 54162 1192 991910895 26 n-heptane, C7H16 684 371 8,70E-05 140005 2242 1,2741E+11 27 Toulene, C7H8 867 384 8,70E-05 72064 1707 8,3659E+10 28 Propylene carbonate, C4H6O3 1205 513 1,99E-08 78362 2141 7378994623 29 Benzene, C6H6 876 353 8,70E-05 126360 1055 1,465E+11 30 Acetone, (CH3)2CO 791 330 8,70E-05 99345 2175 1,0417E+11 31 methly tert-butyl ether, C5H12O 740 328 8,70E-05 86216 2127 8,4598E+10 32 Formic Acid, HCOOH 1220 374 1,99E-08 275472 2151 8646614751 33 Chloroform, CHCl3 1483 334 5,95E-09 79577 956 1769400792 34 tetrachloro-ethylene, C2Cl4 1620 394 5,95E-09 65609 864 2475148903

Energy deposited per pulse is demonstrated in Table 5.3.4 using the result of power density.

Table 5.3.4: Energy deposited per pulse for acids, liquids and organic solvents

Energy deposited per pulse Energy deposited per Sr.No Toxic liquids w α Sv tp pi pulse 1 HI 0,25 0,1 3760419934 5*10^(-9) 3,14159 3,69E-01 2 HCOOH 0,25 0,1 8690851951 5*10^(-9) 3,14159 8,53E-01 3 HNO3 0,25 0,1 6491274914 5*10^(-9) 3,14159 6,37E-01 4 H2O2 0,25 0,1 12890170233 5*10^(-9) 3,14159 1,27E+00 5 CH3COOH 0,25 0,1 6065200324 5*10^(-9) 3,14159 5,95E-01 6 H3BO3 0,25 0,1 15833410707 5*10^(-9) 3,14159 1,55E+00 7 H2SO4 0,25 0,1 11651750887 5*10^(-9) 3,14159 1,14E+00 8 C6H5COOH 0,25 0,1 2,50688E+11 5*10^(-9) 3,14159 2,46E+01 9 HBr 0,25 0,1 787921603,8 5*10^(-9) 3,14159 7,74E-02 10 HCl 0,25 0,1 -440122777 5*10^(-9) 3,14159 -4,32E-02 11 NaHCO3 0,25 0,1 31968863638 5*10^(-9) 3,14159 3,14E+00 12 NaHCO3 0,25 0,1 31968863638 5*10^(-9) 3,14159 3,14E+00 13 Na2CO3 0,25 0,1 1,14116E+12 5*10^(-9) 3,14159 1,12E+02 14 NH3 0,25 0,1 2345921752 5*10^(-9) 3,14159 2,30E-01 15 KOH 0,25 0,1 38372156874 5*10^(-9) 3,14159 3,77E+00 16 NaH 0,25 0,1 16416974000 5*10^(-9) 3,14159 1,61E+00 17 LiOH 0,25 0,1 52539856048 5*10^(-9) 3,14159 5,16E+00 18 NaOH 0,25 0,1 5,85327E+11 5*10^(-9) 3,14159 5,75E+01 19 CaO 0,25 0,1 9,60512E+12 5*10^(-9) 3,14159 9,43E+02 20 CH3COOH 0,25 0,1 6053303824 5*10^(-9) 3,14159 5,94E-01 21 CH3OH 0,25 0,1 2347184318 5*10^(-9) 3,14159 2,30E-01 22 CH3CH2CH2OH 0,25 0,1 95995822132 5*10^(-9) 3,14159 9,42E+00 23 CH3CH2OH 0,25 0,1 1,12399E+11 5*10^(-9) 3,14159 1,10E+01 24 (CH3)2CHOH 0,25 0,1 94475234272 5*10^(-9) 3,14159 9,28E+00 25 CH2Cl2 0,25 0,1 991910895,2 5*10^(-9) 3,14159 9,74E-02 26 C7H16 0,25 0,1 1,27409E+11 5*10^(-9) 3,14159 1,25E+01 27 C7H8 0,25 0,1 83659279013 5*10^(-9) 3,14159 8,21E+00 28 C4H6O3 0,25 0,1 7378994623 5*10^(-9) 3,14159 7,24E-01 29 C6H6 0,25 0,1 1,46502E+11 5*10^(-9) 3,14159 1,44E+01 30 (CH3)2CO 0,25 0,1 1,04173E+11 5*10^(-9) 3,14159 1,02E+01 31 C5H12O 0,25 0,1 84598483359 5*10^(-9) 3,14159 8,31E+00 32 HCOOH 0,25 0,1 8646614751 5*10^(-9) 3,14159 8,49E-01 33 CHCl3 0,25 0,1 1769400792 5*10^(-9) 3,14159 1,74E-01 34 C2Cl4 0,25 0,1 2475148903 5*10^(-9) 3,14159 2,43E-01

Mass evaporated of liquids per pulse is demonstrated in Table 5.3.5.

Table 5.3.5: Mass vaporized per pulse for acids, bases and organic solvents

Mass vaporized per pulse Densit y Thermal (kg/m3 diffusivit Mass vaporized Sr.No Toxic liquids ) pi w y, D,m2/s tp per pulse 1 HI 2850 3,14159 0,25 2,12E-07 5*10^(-9) 1,82E-05 2 HCOOH 1220 3,14159 0,25 1,99E-08 5*10^(-9) 2,39E-06 3 HNO3 1510 3,14159 0,25 1,99E-08 5*10^(-9) 2,96E-06 4 H2O2 1450 3,14159 0,25 1,99E-08 5*10^(-9) 2,84E-06 5 CH3COOH 1050 3,14159 0,25 1,99E-08 5*10^(-9) 2,06E-06 6 H3BO3 1440 3,14159 0,25 1,99E-08 5*10^(-9) 2,82E-06 7 H2SO4 1840 3,14159 0,25 1,99E-08 5*10^(-9) 3,60E-06 8 C6H5COOH 1270 3,14159 0,25 8,70E-05 5*10^(-9) 1,64E-04 9 HBr 1490 3,14159 0,25 4,16E-08 5*10^(-9) 4,22E-06 10 HCl 1490 3,14159 0,25 5,95E-09 5*10^(-9) 1,60E-06 11 NaHCO3 2200 3,14159 0,25 1,99E-08 5*10^(-9) 4,31E-06 12 NaHCO3 2200 3,14159 0,25 1,99E-08 5*10^(-9) 4,31E-06 13 Na2CO3 2540 3,14159 0,25 1,19E-04 5*10^(-9) 3,85E-04 14 NH3 682 3,14159 0,25 9,90E-09 5*10^(-9) 9,42E-07 15 KOH 2044 3,14159 0,25 1,99E-08 5*10^(-9) 4,00E-06 16 NaH 1400 3,14159 0,25 1,19E-04 5*10^(-9) 2,12E-04 17 LiOH 1460 3,14159 0,25 1,99E-08 5*10^(-9) 2,86E-06 18 NaOH 2130 3,14159 0,25 1,19E-04 5*10^(-9) 3,23E-04 19 CaO 3350 3,14159 0,25 1,99E-04 5*10^(-9) 6,56E-04 20 CH3COOH 1050 3,14159 0,25 1,99E-08 5*10^(-9) 2,06E-06 21 CH3OH 792 3,14159 0,25 1,99E-08 5*10^(-9) 1,55E-06 22 CH3CH2CH2OH 803 3,14159 0,25 8,70E-05 5*10^(-9) 1,04E-04 23 CH3CH2OH 789 3,14159 0,25 8,70E-05 5*10^(-9) 1,02E-04 24 (CH3)2CHOH 786 3,14159 0,25 8,70E-05 5*10^(-9) 1,02E-04 25 CH2Cl2 1330 3,14159 0,25 5,95E-09 5*10^(-9) 1,42E-06 26 C7H16 684 3,14159 0,25 8,70E-05 5*10^(-9) 8,86E-05 27 C7H8 867 3,14159 0,25 8,70E-05 5*10^(-9) 1,12E-04 28 C4H6O3 1205 3,14159 0,25 1,99E-08 5*10^(-9) 2,36E-06 29 C6H6 876 3,14159 0,25 8,70E-05 5*10^(-9) 1,13E-04 30 (CH3)2CO 791 3,14159 0,25 8,70E-05 5*10^(-9) 1,02E-04 31 C5H12O 740 3,14159 0,25 8,70E-05 5*10^(-9) 9,58E-05 32 HCOOH 1220 3,14159 0,25 1,99E-08 5*10^(-9) 2,39E-06 33 CHCl3 1483 3,14159 0,25 5,95E-09 5*10^(-9) 1,59E-06 34 C2Cl4 1620 3,14159 0,25 5,95E-09 5*10^(-9) 1,73E-06

Table 5.3.6 demonstrates the results of mass evaporated and transformed in 1 hr by laser operation.

Table 5.3.6: Mass evaporated and transformed per hour for acids, bases and organic solvents Mass evaporated and transformed/hr of laser operation Densit Mass Mass y Thermal evaporated and evaporated and (kg/m3 diffusivit transformed in 1 transformed in 1 Sr.No Toxic liquids ) w y, D,m2/s Np tp min by laser hr 1 HI 2850 0,25 2,12E-07 30 5*10^-9 9,98E-05 5,99E-03 2 HCOOH 1220 0,25 1,99E-08 30 5*10^-10 1,31E-05 7,85E-04 3 HNO3 1510 0,25 1,99E-08 30 5*10^-11 1,62E-05 9,72E-04 4 H2O2 1450 0,25 1,99E-08 30 5*10^-12 1,56E-05 9,33E-04 5 CH3COOH 1050 0,25 1,99E-08 30 5*10^-13 1,13E-05 6,76E-04 6 H3BO3 1440 0,25 1,99E-08 30 5*10^-14 1,54E-05 9,27E-04 7 H2SO4 1840 0,25 1,99E-08 30 5*10^-15 1,97E-05 1,18E-03 8 C6H5COOH 1270 0,25 8,70E-05 30 5*10^-16 9,01E-04 5,40E-02 9 HBr 1490 0,25 4,16E-08 30 5*10^-17 2,31E-05 1,39E-03 10 HCl 1490 0,25 5,95E-09 30 5*10^-18 8,74E-06 5,24E-04 11 NaHCO3 2200 0,25 1,99E-08 30 5*10^-19 2,36E-05 1,42E-03 12 NaHCO3 2200 0,25 1,99E-08 30 5*10^-20 2,36E-05 1,42E-03 13 Na2CO3 2540 0,25 1,19E-04 30 5*10^-21 2,11E-03 1,26E-01 14 NH3 682 0,25 9,90E-09 30 5*10^-22 5,16E-06 3,10E-04 15 KOH 2044 0,25 1,99E-08 30 5*10^-23 2,19E-05 1,32E-03 16 NaH 1400 0,25 1,19E-04 30 5*10^-24 1,16E-03 6,97E-02 17 LiOH 1460 0,25 1,99E-08 30 5*10^-25 1,57E-05 9,40E-04 18 NaOH 2130 0,25 1,19E-04 30 5*10^-26 1,77E-03 1,06E-01 19 CaO 3350 0,25 1,99E-04 30 5*10^-27 3,59E-03 2,16E-01 20 CH3COOH 1050 0,25 1,99E-08 30 5*10^-28 1,13E-05 6,76E-04 21 CH3OH 792 0,25 1,99E-08 30 5*10^-29 8,50E-06 5,10E-04 22 CH3CH2CH2OH 803 0,25 8,70E-05 30 5*10^-30 5,70E-04 3,42E-02 23 CH3CH2OH 789 0,25 8,70E-05 30 5*10^-31 5,60E-04 3,36E-02 24 (CH3)2CHOH 786 0,25 8,70E-05 30 5*10^-32 5,58E-04 3,35E-02 25 CH2Cl2 1330 0,25 5,95E-09 30 5*10^-33 7,80E-06 4,68E-04 26 C7H16 684 0,25 8,70E-05 30 5*10^-34 4,85E-04 2,91E-02 27 C7H8 867 0,25 8,70E-05 30 5*10^-35 6,15E-04 3,69E-02 28 C4H6O3 1205 0,25 1,99E-08 30 5*10^-36 1,29E-05 7,76E-04 29 C6H6 876 0,25 8,70E-05 30 5*10^-37 6,21E-04 3,73E-02 30 (CH3)2CO 791 0,25 8,70E-05 30 5*10^-38 5,61E-04 3,37E-02 31 C5H12O 740 0,25 8,70E-05 30 5*10^-39 5,25E-04 3,15E-02 32 HCOOH 1220 0,25 1,99E-08 30 5*10^-40 1,31E-05 7,85E-04 33 CHCl3 1483 0,25 5,95E-09 30 5*10^-41 8,70E-06 5,22E-04 34 C2Cl4 1620 0,25 5,95E-09 30 5*10^-42 9,50E-06 5,70E-04

Figure 5.3.1 demonstrates the graph drawn between the different acids and their mass evaporated and transformed per kg in an hour.

Acids mass evaporated/transformed 6,00E-02 5,40E-02

5,00E-02

4,00E-02

kg/hr 3,00E-02

2,00E-02 5,99E-03 5,24E-04 1,00E-02 7,85E-04 6,76E-04 1,18E-03 9,72E-04 9,33E-04 9,27E-04 1,39E-03 0,00E+00

Figure 5.3.1: Mass evaporated and transformed for liquids

Figure 5.3.2 demonstrates the graph drawn between the different bases and their mass evaporated and transformed per kg in an hour.

Bases mass evaporated/transformed 2,50E-01 2,16E-01

2,00E-01

1,50E-01 1,26E-01 kg/hr 1,06E-01 1,00E-01 6,97E-02

5,00E-02 1,42E-03 1,42E-03 1,32E-03 3,10E-04 9,40E-04 0,00E+00 NaHCO3 NaHCO3 Na2CO3 NH3 KOH NaH LiOH NaOH CaO

Figure 5.3.2: Mass evaporated and transformed for Bases

Figure 5.3.3 demonstrates the graph drawn between different organic solvents and their mass evaporated and transformed per kg in an hour.

Organic solvents mass evaporated/transformed

4,00E-02 3,69E-02 3,73E-02 3,35E-02 3,37E-02 3,50E-02 3,42E-02 3,36E-02 3,15E-02 2,91E-02 3,00E-02

2,50E-02

kg/hr 2,00E-02

1,50E-02 7,85E-04 1,00E-02 5,10E-04 5,22E-04 5,00E-03 6,76E-04 4,68E-04 7,76E-04 5,70E-04 0,00E+00

Figure 5.3.3: Mass evaporated and transformed for Organic solvents

6. Proposal of laser reactor for decomposition of toxic materials

Though the funding was not available for the project but the reactor was designed incase funds become available and experiments can be carried out for all the toxic materials in order to support the mathematical models. This project only contains the experiments of NOx. With reference to the above figure, drawn in Solid Edge (3D modeling software); we can observe that the stainless steel reactor is formed with a multilayer of materials that can diffuse and resist the heat. The internal layer is made of a highly reflective and high temperature resistance ceramic (Shuttle technology coated with hard super white ceramic). A layer of copper will fast transmit the heat to the main frame. Figure 6.1 demonstrates the reactor drawn in solid edge.

Figure 6.1: Stainless steel reactor for the decomposition of toxic materials through laser made in Solid Edge

The dimensions are purely indicative. Final dimension values will be determined using finite element analysis and suitable software (COMSOL) in order to have the best cooling efficiency along with perfect sealing in order to avoid leakages of toxic materials. In this respect it is

63 obvious that the experimental set-up will be inside a special with all the safety measure to protect the laboratory staff and external environment.

The drawings do not show the laser and the ancillary instruments but only the optical window interfaces to all the devices. The experiment will use:

1- A series of lasers: a- Low cost semiconductor laser with NIR, Green and UV lines, with low energy (12 µJ) but very short pulse with (0.1 ns) and high pulse repetition frequency (prf > 5 kHz) b- Medium energy laser 2.5 J @ 1064 nm fundamental wavelength with outputs at 532 nm e 266 nm and very high energy > 100 J @106 nm

2. Spectrometers 3. Strike camera in the visible 4. Strike camera in the IR 5. Series of standard video camera 6. Thermal imagers (FLIR) 7. Gas analyzers 8. Oscilloscopes 9. Multi-meters 10. Flow controllers for liquids and gases

Beside software (COMSOL, Mathematica, etc.) and lap tops Why spherical shape? First of all the sphere is the best black-body absorber and producer of standing waves, thus enhancing the mechanism of optical breakdown of molecular bonds. The inner spherical shape of the bottom parts allow its use for liquids and solids whereas gases can be adiabatically expanded through one of the access in the horizontal plane and the laser beam secured at the opposite of the adiabatic expansion nozzle. The single block with square shape in which the bottom half sphere is realized enables absorbing and diffusing the excess of heat in the

64 reaction chamber. We could select a less complicated geometry adopting a cylindrical structure for the reactor. But, this solution is less effective than the spherical geometry.

Figure 6.2 demonstrates the cross section that shows the internal layout of the reactor. In order to contain the extremely hot plasma temperature and do not affect metals a multi-layer structure has been conceived. Dimensions of layers are not defined and not in proportion. The ceramic is full reflecting white absolving two functions: 1. Reflecting back to the center of the sphere the wavelength packets emitted by the plasma activated by the laser 2. Shielding the heat and dumping the temperature transmission.

Figure 6.2: Cross-sectional view of stainless steel reactor made in AutoCAD

The external upper part of the reactor is made in stainless steel as demonstrated in Figure 6.3.

Figure 6.3

The external bottom part of the reactor also made in stainless steel. The external part of the bottom is flat for easy positioning. It is demonstrated in figure 6.4.

Figure 6.4

The two half portion of the sphere in copper for fast cooling and transmission to the external shield. They are demonstrated in figure 6.5 and figure 6.6.

Figure 6.5

Figure 6.6

The inner two half spheres made in ceramic. They are demonstrated in Figure 6.7 and Figure 6.8.

Figure 6.7

Figure 6.8

Figure 6.9

Particular of the sapphire windows supports. O-ring seals are not visible. These duct support are deigned to ensure perfect sealing of the sphere, they will be tested with high pressure pumping inside the sphere air at 10 ATM in order to ensure that no leaks may occur during operation for safety reasons. AS already stated these are preliminary drawings and do not show details like seals sits and lenses or optical windows seats. Windows are necessary in this experimental reactor in order to ensure the access to optical devices like spectrometers, high speed strike camera, IR camera, thermal vision units, and Schlieren camera.

7. Experimental decomposition of NOx

Lasers can be used to efficiently decompose NOx, and research in this direction may pay back when efficient (optical/electrical power >60%) solar powered solid state lasers can be employed. Laser beams can be easily and efficiently manipulated and controlled, maintaining the required field values. Laser beams can be transformed into thin blades of light and very rapidly scan matrices of nozzles.

A NOx environmental mixture of N2O, Nitrous oxide 397 ppmmol, NO (Nitrogen mono-oxide)

890 ppmmol and NO2 (Nitrogen Dioxide) 9 ppmmol were flown into an insulate reactor. The reactor has two sections which were separated by a diaphragm of 1mm diameter. The flow of

NOx could be controlled by mass flow controller. In the second section, the diaphragm enables

NOx adiabatic expansion under the action of a high pulse energy laser beam focused on the 1mm aperture. The decomposed gas flows into the spectrometer when the depression pump is active; this reduces the gas in second section of reactor.

A sapphire window ensures that all the gases will flow into the spectrometer. The polluted gas flow is actively controlled with a commercially available feedback system. A laser beam is fed through a protective pipe into the reactor, and its minimum beam waist was perfectly aligned on the circular aperture of the diaphragm. Pre-alignment of the system was done using a 5 MW, 532 nm green laser beam. The minimum beam waist must not touch the diaphragm walls since the laser beam will increase their temperature and consequently, NOx population will increase.

Actually, this misalignment was utilized as trivial test to check if really NOx were decomposed by the laser heating up the diaphragm body.

The laser used was Q-switched Nd:YAG with fundamental wavelength of 1064 nm with pulse trains having a fixed duration of 8ns each. The lamp repetition frequency ranging from 1 Hz to 20 Hz with energy variation from 0 J to 1.6 J.

Energy setting is quite accurate as the lamp current is preset through a 3 digits code having the threshold at the digit code 135 and the maximum at the digit code 210. The diagram of figure 5 shows the correspondence between the 3 code system (in the figure reported as “bit” for sake of simplicity) and the energy output outside the focusing lens. Values were previously factory

70 measured with the high quality Thermopile Analog Laser Power Meter PMW1 calibrated on the Ophir-Spiricon energy meter.

NOx flow set was 450 ml. The values of the flow range combined with the spectrometer depression enables NOx not to dissipate outside the reactor due to leaks in the reactor’s joints.

Laser interaction time was 10’. At 10’ the laser was put off and the NOx concentration in ppm was measured reaching the starting value in almost 2’ time. The delay was due to the pipe length between the reactor and the spectrometer.

Experimental setup is demonstrated in Figure 7.1, Figure 7.2, and Figure 7.3.

Figure 7.1: Layout of the experiment

Figure 7.2: NOx bottle, Reactor, Mass Flow Controller and spectrometer

Figure 7.3: Reactor where adiabatic expansion occurs NOx decomposition

8. Results and Discussion

In order to understand behavior of materials when exposed to lasers two mathematical models are made and experiments are carried out on NOx. As NOx is the only material on which experiments were carried out so the results of the experiments are given below and later they are compared with the mathematical model results of NOx.

8.1. Experimental The results obtained from the experiments are shown in the following curves. The following curves are drawn between parts per million of NOx against time the NOx is exposed to the laser. They have two curves because the tests were repeated twice in order to have reliability of the readings. The laser energy demonstrated in curves of Figure 8.1, Figure 8.2, Figure 8.3, and

Figure 8.4 have been increased and with that the ppm of NOx decreases. The curves show NOx concentration in the adiabatic expansions room versus laser beam-on time at 20 Hz for a total exposure time of 96 µs in 10’ time interval at increasing laser energy: 0.532 J, 0.64 J, and 0.961 J.

NOx vs Time 0.532J & 20.0Hz

850

800

750

ppm 700

650

600

550 0 2 4 6 8 10 12

t '

Figure 8.1: ppm v/s time for 0.532 J

NOx vs Time 0.64J & 20.0Hz

800

700 ppm

600

500

0 2 4 6 8 10 12

t '

Figure 8.2: ppm v/s time for 0.64 J

NOx vs Time 0.96J & 20.0Hz

800

700

600 ppm 500

400

300

0 2 4 6 8 10 12

t '

Figure 8.3: ppm v/s time for 0.96 J

When the test was being conducted at 1.17 J the sapphire window broke and the readings were not taken twice. The sapphire window was broken due to excess heat deposited at 1.17 J per pulse. Despite the broken window the gas flow was basically contained inside the reactor volume and still consistent NOx decomposition was observed.

NOx vs Time 1.17J & 20.0Hz

800

700

600

ppm 500

400

300

0 2 4 6 8 10 12

t '

Figure 8.4: The NOx concentration in the adiabatic room at sapphire break (a 2.2 mm hole)

The results obtained from the experiments show that the concentration of NOx decreases when it’s exposed to lasers. Secondly, the experiments have shown that with the increase in energy the concentration of NOx decreases, which means with the increase in energy the toxic material destruction increases as well. Experiments show that with the increase of laser energy the destruction of NOx increases.

8.2. Methematical models

Now we look at the results of two mathematical models and see their results. In case of molecular dissociation model using laser of higher energy gives higher value for material destroyed. It can be seen in the following comparative graphs for molecular dissociation model.

Gases destruction by 2.865J Laser

1,91E+00 2,00E+00

1,50E+00 9,43E-01

m3/hr 1,00E+00

5,00E-01

0,00E+00 NO NO2

Figure 8.5: Destruction of NOx according to molecular dissociation model using 2.865J Laser

Gases destruction by 286.5J Laser

2,00E+02 1,91E+02

1,50E+02 9,42E+01

m3/hr 1,00E+02

5,00E+01

0,00E+00 NO NO2

Figure 8.6: Destruction of NOx according to molecular dissociation model using 286.5J Laser

Destruction of NOx according to molecular dissociation model shown in the above two figures reveal that with the increase of the energy of laser the amount of destruction of the material has increased. The exact same relationship has been found in the experiment as well.

Plasma exploitation model shown in Figure 8.7 when compared with molecular dissociation model shows the same trend for NO and NO2 destruction amount per hour. Higher is for NO2 and lower amount of NO. This is because the decomposition energy for NO is higher than that of

NO. But plasma exploitation model also ensure the destruction of NOx.

Mass evaporated and transformed/hr

0,002 0,001686375

0,0015 0,000817441 m3/hr 0,001

0,0005

0 NO NO2

Figure 8.7: Destruction of NOx according to plasma exploitation model

From the above results of the same material it can be concluded that the mathematical models as well as the experiments are in agreement about the destruction of NOx by lasers. Moreover, experiment and molecular dissociation model show a directly proportional relationship between the laser energy and amount of destruction. Graphical results of two mathematical models predict that amount of destruction of NO2 is more than that of NO. It’s because of difference of decomposition energies.

The same relationship for the increase of laser energy is observed in all the toxic materials that have been studied. Following two graphs also show the increase of laser energy increases the amount of destruction of toxic material.

Acids destroyed by 2.86J Laser 2,50E+01 2,16E+01

2,00E+01

1,50E+01 m3/hr 1,00E+01 6,22E+00 5,38E+00 2,67E+00 5,00E+00 6,76E-01 8,64E-01 4,25E-01 8,99E-01 3,35E-01 4,50E-01 3,00E-01 9,43E-01 0,00E+00

Figure 8.8: Destruction of acids according to molecular dissociation model using 2.865J Laser

Acids destroyed by 286.5J Laser 2,50E+03 2,15E+03

2,00E+03

1,50E+03 m3/hr 1,00E+03 6,22E+02 2,66E+02 5,38E+02 5,00E+02 8,63E+01 4,24E+01 6,75E+01 8,98E+01 3,35E+01 4,50E+01 3,00E+01 9,42E+01 0,00E+00

Figure 8.9: Destruction of acids according to molecular dissociation model using 2.865J laser

As the laser energy is increased by 100 times the amount of destruction of toxic material is also increased by the same factor. Different materials have a difference response towards the same energy of Laser. It is because of the material’s decomposition energy. H3BO3 having the highest amount of destruction has lowest decomposition energy of 7195 J/mol. The lowest amount of destruction is for C6H8O7 and it has the highest decomposition energy of 1384000 J/mol. This is same with bases as well as organic solvents.

Plasma exploitation model for acids shown in following figure also show the destruction of acids but the amount of destruction of acids is not proportional to the amount of destruction predicted by molecular dissociation method.

Acids mass evaporated/transformed per hr 6,00E-02 5,40E-02

5,00E-02

4,00E-02

m3/hr 3,00E-02

2,00E-02 9,72E-04 9,27E-04 1,39E-03 1,00E-02 5,99E-03 1,18E-03 7,85E-04 9,33E-04 6,76E-04 5,24E-04 0,00E+00

Figure 8.10: Results for plasma exploitation model of acids

The difference between the values of the two models is because in molecular dissociation the values are calculated for the decomposition of materials into elements but in plasma exploitation model values are calculated for the decomposition of materials into plasma. This is the reason for the change in values but both the models ensure the destruction of toxic and non-toxic waste.

In case of laser molecular dissociation we found that the dissociation energies involved demand very high energy lasers. The only laser which can be utilized delivering in rapid sequence packets of photons equivalent to the total amount required is the Gas Dynamic pulsed CO2 laser developed by Prof. Viktor Apollonov, with 100 kW peak power and 5ns pulse width (2.86 J) with a typical pulse repetition frequency of 350 kHz at a 10640.0 nm wavelength. Delivery of photons must be faster than relaxation times of molecule contribute to further decompose the toxic material. This part was not developed further owing to the problems of patenting this technology. A U.S. patent, presently expired, was already issued in past but laser source and applications were not complete.

As already stated, both the methods lead to theoretical confirmation that there are available laser sources capable to destroy toxic materials at reasonable rates but with greater efficiencies with respect to prevailing conventional methods, whose maximum efficiency reach 98%. A third process, photolysis could not be thoroughly evaluated. But, our experimental results on NOx confirm that also photolysis can be utilized especially in case of gases and vapors.

8.3. Conclusions from results and discussion

In conclusion lasers do effectively demolish toxic materials in a selective and most efficient way. Not only, the three methods - being complimentary - may be combined in a way to ensure total, 100%, total destruction of extremely dangerous toxic waste, like those produced in hospitals containing also contaminants.

In case of laser plasma interaction the laser splits molecules in ions and electrons confining this plasma within the same beam. The interactions increase the plasma temperature until laser sustained combustion appears. But, the laser interaction with the plasma produces a very wide band of secondary photons, which enhanced and confined in a black-body spherical cavity

9. Acknowledgments

I would like to express my great thanks to Dr. .Muhammad Muddassir Silvio Gualini for his dedication and commitment for the completion of this project even after great hurdles. His constant supervision, great motivation and extreme interest lead me to the completion of this project. Dr. Anders Eliasson and Dr. Hasse Fredriksson have played a key role in the completion of my degree and I thank them for allowing me to work on this project. I would also like to thank R. Angelo Ferrario, Quanta system and GAP Laser & Photonics management for supplying lasers and ancillary equipment. Finally I thank my parents from whom I always got great comfort for the completion of this project.

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Appendix

1. Solids

1.1. Phosphors

Table 1: Conventional technology to destroy Scheelite and Scheelite Wolframite concentrates

SCHEELITE AND SCHEELITE-WOLFRAMITE CONCENTRATES

Items to compare Conventional technology

Destruction Caustic decomposition through mechanical activation technology Efficiency 98% Amount of destruction By Products No Skilled Labor Yes Dangerous No process Automatic Yes PTOTMBD No Investment cost High Running cost High but it is used in 11 plants in China Working Area Very Large Number of Labor More than 1 Comments Short life of equipment for the friction between steel ball and cylinder “Caustic decomposition of scheelite and scheelite-wolframite concentrates through mechanical activation”, Li Honggui, Liu Maosheng, Sun Peimei, Li Yunjiao, J.CENT. South Univ. Technol. Vol.2 No.2, [15]

Table 2: Conventional technology to destroy Scheelite and Scheelite Wolframite mixed concentrates

SCHEELITE AND SCHEELITE-WOLFRAMITE MIXED CONCENTRATES

Items to compare Conventional technology

Destruction caustic soda digestion technology Efficiency 98% Amount of destruction By Products No Skilled Labor No Dangerous No but it can become if the pressure in the autoclave exceeds safe

103 process value Automatic Yes PTOTMBD No Investment cost Low as just an autoclave required Running cost Small as just an autoclave is required and the raw materials with few additives Working Area Small Number of Labor 1 Comments ”Decomposition scheelite and scheelite-wolframite mixed concentrated by caustic soda digestion”, Sun Pei-mei, Li Hong-gui, LI Yun-Jiao, ZHAO Zhong-wei, HUO Guang-sheng, SUN Zhao-ming, LUI Mao-Sheng, J.CENT. South. Univ. Technol. Vol.20, No4, [16]

Table 3: Conventional technology to destroy KH2PO4 Crystals

KH2PO4 CRYSTALS

Items to compare Conventional technology

Destruction Laser induced decomposition technology Efficiency 98% Amount of Yes as lasers and examination tools are sophisticated destruction By Products No Skilled Labor No Dangerous Yes process Automatic High because of Raman Scattering, photoluminescence and soft X-ray absorption near edge structure spectrometers are required PTOTMBD Low Investment cost 1 Running cost Laser induced material decomposition at surface damage sites but not at bulk damage sites Working Area Number of Labor Comments ”Decomposition of KH2OP4 crystals during laser-induced breakdown”, R.A. Negres, S.O. Kucheyev, P. DeMange, C.Bostedt, T.van Buuren, A.J. Nelson, S.G. Demos, Applied Physics Letters 86, 171107, [17]

Table 4: Conventional technology to destroy Scheelite

SCHEELITE

Items to compare Conventional technology

Destruction Acid-alcohol solution i.e. HCl and absolute ethanol technology Efficiency 100%

104

Amount of Tungstic Acid destruction By Products No Skilled Labor No Dangerous No process Automatic No PTOTMBD Low Investment cost Low Running cost Small Working Area 1 Number of Labor Comments ”Decomposition of scheelite in acid-alcohol solutions”, S.Ozdemir, I. Girgin, Minerals Engineering Vol.4 No.2, pp.179-184, 1991, [18]

Table 5: Conventional technology to destroy LiGDF4 Scheelite

LIGDF4 SCHEELITE

Items to compare Conventional technology

Destruction high pressure (11GPa) and temperature technology Efficiency LiF Amount of Yes destruction By Products No Skilled Labor Yes Dangerous No process Automatic High as we need X-rays PTOTMBD Low Investment cost Running cost 1 Working Area Number of Labor Comments ”Decomposition of LiGdF4 scheelite at high pressures”, Andrzej Grzechnik, Wilson A Crichton, Pierre Bouvier, Vladimir Dmitriev, Han’Peter Weber, Jean Yves Gesland, Journal of Physics: Condensed Matter, [19]

Table 6: Conventional technology to destroy Zinc Sulphide

ZINC SULPHIE

Items to compare Conventional technology

Destruction Decomposition by the reaction of atomic hydrogen with ZnS

105 technology Efficiency Amount of destruction By Products No Skilled Labor Dangerous process Automatic PTOTMBD No Investment cost Running cost Working Area Number of Labor Comments ”Electron-hole mechanism for the decomposition of zinc sulfide in a hydrogen atmosphere”, V.F. Kharlamov, V.V. Styrov, A.P. Il’in and I.Z. Gorfunkel, Russian Physics Journal Volume 19, Number 10, 1273-1277, [20]

Table 7: Conventional technology to destroy Sodium Tungsten

SODIUM TUNGSTEN

Items to compare Conventional technology

Destruction Decomposition using melt of NaCl-NaF-NaCO3 salt system technology and using Al Efficiency 90% Amount of destruction By Products Skilled Labor Yes Dangerous process Automatic No PTOTMBD No Investment cost High as X-Ray diffractometer is required Running cost High as the mixture is kept over 1000 °C for 1 hour Working Area Number of Labor Comments ”Obtaining tungsten powder from the scheelite concentration in Ion Melts”, V.V. Gostishchev and V.F. Boiko, Theoretical Foundations of Chemical Engineering 2008, Vol.42, No.5, pp. 728-730, [21]

Table 8: Conventional technology to destroy Co2, Ni2, Cu2, Zn2, Cd2 and Pb2 m-benzenedisulphates in air and in nitrogen atmospheres

Co2,Ni2,Cu2,Zn2,Cd2 and Pb2 m-benzenedisulphates in air and in nitrogen atmospheres

106

Items to compare Conventional technology

Destruction Thermal decomposition in air and in nitrogen atmospheres technology Efficiency Amount of destruction By Products Skilled Labor Yes to operate DTA, DSC and X-ray diffractometer Dangerous No process Automatic No PTOTMBD Yes Investment cost High due to DTA,DSC and TG, X-ray diffractometer Running cost Low Working Area Large as X-ray diffractometer, DTA, DSC and TG are required Number of Labor 1 Comments

”Synthesis and thermal decomposition of Co2, Ni2, Cu2, Zn2, Cd2 and Pb2 m-benzenedisulphates” Araceli Ramirez Garcia, Alejandro Guerrero Laverat, C. Victoria Ragel Prudencio and Antonio Jerze Mendez, Thermochimica Acta, 213(1993) 199-210, [22]

Table 9: Conventional technology to destroy Co2, Ni2, Cu2, Zn2, Cd2, and Pb2 hydroxy-p-toluenesulphonates

Co2,Ni2,Cu2,Zn2,Cd2 and Pb2 hydroxy-p-toluenesulphonates

Items to compare Conventional technology

Destruction Thermal decomposition in air and in nitrogen atmospheres technology Efficiency Amount of destruction By Products Different products for air and nitrogen atmospheres Skilled Labor Yes for diffractometer, spectrophotometer, DTA, TG Dangerous No process Automatic No PTOTMBD Yes Investment cost High due to DTA, TG, X-ray diffractometer, spectrophotometer Running cost Low Working Area Large as spectrophotometer, TG,DSC and diffractometer are required Number of Labor 1 Comments

”Thermal decomposition of Co2, Ni2, Cu2, Zn2, Cd2 and Pb2 hydroxy-p-toluenesulphonates”, Mercedes Bombin, MA Martinez- Zaporta, Araceli Ramirez, Alejandro Geurero and Antonio Jerez Mendez, Thermochimica Acta, 224 (1993) 151-163, [23]

107

Table 10: Conventional technology to destroy artificial scheelite

ARTIFICAL SCHEELITE

Items to compare Conventional technology

Destruction Mechanism of artificial scheelite decomposition in Nitric Acid technology Efficiency Amount of destruction By Products Skilled Labor Dangerous process Automatic PTOTMBD Investment cost Running cost Working Area Number of Labor Comments The spaces are left as the paper discusses only the mechanism ”Investigation of the Mechanism of Decomposition of artificial Scheelite in Nitric Acid”, Eshmurat A. Pirmatov, Chemistry for sustainable development 11 (2003) 635-637, [24]

1.2. Asbestos

Table 11: Conventional technology to destroy Friable Asbestos

FRIABLE ASBESTOS

Items to compare Conventional technology

Destruction Decomposition using acidic gas (HF and HCl) generated by the technology decomposition of CHClF2 with superheated steam Efficiency 100% Amount of 10 g / 30 mins destruction By Products Just exhaust gas Skilled Labor Yes Dangerous No process Automatic Yes PTOTMBD No Investment cost High because of X-ray diffractometer and SEM Running cost Working Area

108

Number of Labor 1 Comments

” A novel decomposition technique of friable asbestos by CHClF2-decomposed acidic gas”, Kazumichi Yanagisawa, Journal of Hazardous Materials, [25]

Table 12: Conventional technology to destroy Asbestos

ASBESTOS

Items to compare Conventional technology

Destruction Decomposition through Sulfuric acid technology Efficiency Amount of destruction By Products Silica Skilled Labor Dangerous No. There is high degree of safety process Automatic PTOTMBD Investment cost Running cost Low running cost because of the cheap chemical compounds Working Area Number of Labor Comments By-products are solidified ”Asbestos Decomposition”, Song-Tien Chou, Manhattan, Kans, ASD, Inc. Houston, Tex, [26]

Table 13: Conventional technology to destroy Chrysotile Asbestos

CHRYSOTILE ASBESTOS

Items to compare Conventional technology

Destruction Decomposition by Fluorosulfonic Acid technology Efficiency Amount of destruction

By Products SiO2 Skilled Labor Yes for XRD,SEM, Spectrometer but not for experiments Dangerous No process Automatic Yes PTOTMBD No Investment cost High because of FT-IR, Spectrometer, XRD and SEM

109

Running cost Low as only chemical reagents are required Working Area Very small except for the examination machines Number of Labor 1 Comments ”Decomposition of Chrysotile Asbestos by Fluorosulfonic Acid”, T.Sugama, R.Sabatini, L.Petrakis, Ind.Eng.Chem.Res. 1998, 37, 79-88, [27]

Table 14: Conventional technology to destroy Asbestos Fibers

ASBESTOS FIBERS

Items to compare Conventional technology

Destruction Low temperature sintering technology Efficiency Amount of destruction By Products No Skilled Labor Yes Dangerous No process Automatic No PTOTMBD Yes Investment cost High Running cost High because furnace is operated over 1000 °C for 1-2 hrs. Working Area Large Number of Labor 1 Comments ”Destruction of Asbestos fibers by sintering asbestos-volcanic tuff mixtures”, Ottavio Marino, Maria Palumbo, Giuseppe Mascolo, Environmental Technology, Vol 16. pp. 89-94, [28]

Table 13: Conventional technology to destroy Asbestos

ASBESTOS

Items to compare Conventional technology

Destruction Hydrolysis between asbestos and supercritical steam at high temp and technology pressure Efficiency 1 Amount of destruction By Products Forsterite Skilled Labor Yes to operate XRD,SEM and planetary grinding mill Dangerous No but can become if the pressure exceeds safe limits in autoclave process Automatic Yes

110

PTOTMBD Yes as it is ground in a planetary grinding mill Investment cost High because of XRD, SEM, autoclave Running cost Low Working Area Small area except the examination machines Number of Labor 1 Comments ” Hydrothermal conversion of chrysotile asbestos using near supercritical conditions”, Kalliopi Anastasiadou, Dimosthenis Axiotis, Evangelos Gidarakos, Journal of Hazardous Materials, [29]

Table 16: Conventional technology to destroy Chrysotile Asbestos

CHRYSOTILE ASBESTOS

Items to compare Conventional technology

Destruction technology Thermal decomposition Efficiency Amount of destruction By Products Forsterite, Enstatite Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No Investment cost High because of ESEM, XRD Running cost Working Area Number of Labor 1 Comments ”In situ ESEM study of the thermal decomposition of chrysotile asbestos in view of safe recycling of the transformation product”, Alessandro F. Gualtieri, Magdalena Lassinantti Gualtieri, Massimo Tonelli, Journal of Hazardous Materials, [30]

Table 17: Conventional technology to destroy Asbestos

ASBESTOS

Items to compare Conventional technology

Destruction technology Non-combustion mechano-chemical process Efficiency 1 Amount of destruction By Products No Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No Investment cost High Running cost High

111

Working Area Large Number of Labor 1 Comments ”Safe Decomposition of Asbestos by Mechano-chemical Reaction”, Ryo Inoue, Junya Kano, Kaoru Shimme and Fumio Saito, Materials Science Forum Vols. 561-565 pp. 2257-2260, [31]

Table 14: Conventional technology to destroy Asbestos

ASBESTOS

Items to compare Conventional technology

Destruction technology Mechanochemical treatment Efficiency Amount of destruction By Products No Skilled Labor Yes to operate planetary ball mill, XRD, SEM, phase contrast microscope Dangerous process No Automatic Yes PTOTMBD No Investment cost High because of SEM,XRD,phase-contrast microscope, Energy dispersion microanalysis Running cost High Working Area Large because of number of machines Number of Labor 1 Comments ”Mechanochemical treatment to recycling asbestos- containing waste” P.Plescia, D.Gizzi, S. Benedetti, L.Camilucci, C.Fanizze, P.DE Simone, F. Paglietti, Waste Management 23 (2003) 209-218, [32]

Table 19: Conventional technology to destroy Chrysotile

CHRYSOTILE

Items to compare Conventional technology

Destruction Low temperature decomposition of chrysotile asbestos by acidic gas formed technology by decomposition of Freon (by superheated steam at 150 °C for 30-60 mins) Efficiency 99.99% Amount of destruction By Products Chrysotile fibers=No, Chrysotile containing slates=Quartz Skilled Labor Yes for XRD, SEM, PCM Dangerous process No Automatic Yes PTOTMBD No Investment cost High

112

Running cost Low Working Area Small Number of Labor 1 Comments ”Low Temperature Decomposition of Chrysotile Asbestos by Freon-Decomposed Acidic Gas”, Takahiro Kozawa, Ayumum Onda, Koji Kajiyoshi, Kazumichi, Yanagisawa, Junichi Shinohara, Tetsuro Takanami, Masatsugu Shiraishi and Masazumi Kanazawa, Proceedings of International Symposium on Eco Topia Science 2007, ISETS07 (2007) , [33]

Table 20: Conventional technology to destroy Asbestos

ASBESTOS

Items to compare Conventional technology

Destruction Thermal decomposition of asbestos and recycling in traditional technology ceramics Efficiency 100% Amount of destruction By Products Forsterite and Estatite Skilled Labor Yes Dangerous process Automatic PTOTMBD Investment cost High Running cost High Working Area Number of Labor 1 Comments ”Thermal decomposition of asbestos and recycling in traditional ceramics”, A.F. Gualtieri, A. Rartaglia, Journal of the European Ceramic Society 20 (2000) 1409-1418, [34]

Table 21: Conventional technology to destroy Chrysotile Asbestos

CHRYSOTILE ASBESTOS

Items to compare Conventional technology

Destruction technology Thermal decomposition Efficiency 100% Amount of destruction 100 g/3 hours By Products Forsterite and Enstatite Skilled Labor Yes for XRD, SEM, DTA, Thermogravimetric analysis Dangerous process No Automatic Yes PTOTMBD No Investment cost High because of XRD, SEM, DTA, Thermogravimetric analysis, box furnace

113

Running cost High as observations are made after coating the samples with thin layer of gold Working Area Large area Number of Labor 1 Comments ”Study on the thermal decomposition of chrysotile asbestos”, T.Zaremba, A.Krzakala, J. Piotrowski, D.Garczorz, Journal of thermal analysis and calorimetry, [35]

2. Gases

2.1. NOx

Table 22: Conventional technology to destroy Nitric Oxide

NITRIC OXIDE

Items to compare Conventional technology

Destruction technology Catalytic decomposition of nitric oxide in oxygen rich gases using Cu ion-exchanged ZSM-5 zeolites Efficiency 75% Amount of destruction

By Products N2 Skilled Labor No Dangerous process No but care must be taken as it’s a high temp process Automatic No PTOTMBD No but the mixture was made before introducing it into the reactor PTODABD Yes Investment cost High because of muffle furnace, plasma emission spectrometer, electrically heated furnace, mass flow controller, NO-NOx analyzer Running cost High because of high temperature operation Working Area Large Number of Labor 1 Comments ”Catalytic Decomposition of Nitric Oxide over Promoted Coper-Ion-Exchanged ZSM-5 Zeolites”, Yanping Zhang and Maria Flytzani-Stephanopoulos, American Chemical Society, [36]

Table 23: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition of NOx with Low-temperature plasmas at atmospheric pressure: Neat and in the presence of oxidants, reductants, water and carbon dioxide Efficiency > 90%

114

Amount of destruction

By Products N2 , O2 and NO2 at low conversions Skilled Labor No Dangerous process No Automatic No PTOTMBD No but just a standard mixture is made PTODABD No Investment cost High Running cost Low Working Area Large Number of Labor 1 Comments All quartz reactors have much higher efficiency than metal reactors of

NOx decomposition

”Decomposition of Nox with Low-Temperature Plasmas at Atmospheric Pressure: Neat and in the Presence of Oxidants, Reductants, Water and Carbon Dioxide”, Jian Luo, Steven L.Suib, Manuel Marquez,Yuji Hayashi and Hiroshige Matsumoto, J.Phys.Chem.A 1998, 102, 7954-7963, [37]

Table 24: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction Effective NOx decomposition and storage/reduction over mixed oxides technology derived from layered double hydroxides Efficiency 55 – 75 % Amount of destruction

By Products N2, O2 Skilled Labor No Dangerous No but care must be taken as it’s a high temperature process process Automatic No PTOTMBD No PTODABD No but the catalysts are derived from precursors Investment cost High Running cost High Working Area Small Number of Labor Comments ”Effective Nox decomposition and storage/reduction over mixed oxides derived from layered double hydroxides”, Jun Jie Yu. Xiao Ping Wang, Yan Xin Tao, Zheng Ping Hao and Zhi Ping Xu, Ind.Eng.Chem.Res.2007, 46.5794-5797, [38]

Table 25: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

115

Destruction technology Decomposition of NO(x) using electrochemical reactor with a multilayer catalytic cathode Efficiency 90% Amount of destruction

By Products NO, N2 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No but just a standard mixture is made PTODABD Yes in a way that the reactor is prepared with catalytic layers Investment cost High Running cost Low Working Area Number of Labor > 1 Comments Although in it’s called as a low temperature process but the high temperature is required for the preparation of catalysts ” Low Temperature NO(x) decomposition using electrochemical reactor”, K.Hamamoto, Y.Fujishiro, M.Awano, ECS Transactions, 11(33) 181-188 (2008) 10.1149/1.3038921, [39]

Table 26: Conventional technology to destroy NOx

NOX

Items to compare Conventional technology

Destruction Direct decomposition of NOx using catalysts at high temperature technology Efficiency Amount of destruction By Products Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Investment cost Running cost Working Area Number of Labor Comments It was all theoretical with the recommendations at the end for the conditions of preparation of model catalyst ”Fundamental study on the NO(x) direct decomposition catalysts”, Yasunori Yokomichi, toshiro Nakayama, Osamu Okada, Yasuharu Yokoi, Iruru Takahashi, Hiroshi Uchida, Hideyuki Ishikawaka, Ryuichi Yamaguchi, Hisaji Matsui, tokio Yamabe, Catalysis Today 29 (1996) 155-160, [40]

116

Table 27: Conventional technology to destroy NO2

NO2

Items to compare Conventional technology

Destruction technology Photo dissociation of NO2 in the region 217-237 nm using a one- laser photo fragmentation/fragment-detection technique Efficiency Amount of destruction By Products Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Investment cost Running cost Working Area Number of Labor Comments ”Photo dissociation of NO2 in the Region 217-237nm: Nascent NO Energy Distribution and Mechanism”, H.S. Im and E.R. Bernstein, J.Phys.Chem.A 2002, 106, 7565-7572, [41]

Table 28: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Short duration of pulsed power to create streamer discharges Efficiency Amount of destruction 5000 Nm3/h

By Products HNO2, HNO3 Skilled Labor Yes Dangerous process No but care is definitely required dealing with high voltage reactor Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Number of Labor 1 Comments The shorter the pulse width the higher the destruction efficiency ” Application of Pulsed Power for the Removal of Nitrogen Oxides from Polluted Air”, R.Hackam, H.Akiyama, IEEE Electrical Insulation Magazine Vol.17, No.5, [42]

117

Table 29: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition using UV light Efficiency Decreases with increasing removal rate Amount of destruction

By Products N2O, CO2 Skilled Labor No but just for analytical equipment Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Lab Scale Number of Labor 1 Comments ” An experimental study on photochemical effect of UV Light on NO(x) decompositions”, R.Sakuma, R.Ohyama, IEEE, Annual Report Conference on Electrical Insulation and Dielectric Phenomena, [43]

Table 30: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition using electrochemical cell with a multi-layer cathode with high oxygen ion conducting materials Efficiency 80% Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No but the reactor is prepared with the catalytic layers before destruction Investment cost High Running cost Low Working Area Number of Labor 1 Comments Decomposition temperature is above 550 °C ”Intermediate temperature electrochemical reactor for NO(x) decomposition”, K.Hamamoto, Y.Fujishiro, M.Awano, ECS Transactions, 1(7) 389-396(2006) 10.1149/1.2215572, The Electrochemical Society, [44]

118

Table 31: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Plasma-assisted chemical reactor for NOx decomposition- Plasma

combined with chemical scrubber, which uses 5% Na2SO3 as a chemical solution and will convert from NO2 to N2 and O2 Efficiency Nearly 100% Amount of destruction

By Products Minimum N2O formation and nontoxic Na2SO4 Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No but the gas mixture is made PTODABD No Investment cost High Running cost Low Working Area Lab Scale Number of Labor 1 Comments ”Plasma-assisted chemical reactor for NO(x) decomposition”, Toshiaki Yamamoto, Chen-Lu Yang, Michael R.Beltran and Zhorzh Kravets, IEEE Industry Application Society Annual Meeting, New Orleans, Louisiana, [45]

Table 32: Conventional technology to destroy NO

Items to compare Conventional technology

Destruction technology NO removal from a simulated combustion gas using the reciprocal pulse generator Efficiency Low Amount of destruction By Products Yes Skilled Labor Yes Dangerous process Yes Automatic No but the gas mixture is made PTOTMBD No PTODABD Investment cost Moderate Running cost Low Working Area Small Number of Labor 1 Comments ”NO(x) decomposition with repetitive discharges caused by reciprocal voltage pulse in a coaxial cable”, K.Kadowaki, S.Nishimoto and I.Kitani, [46]

119

Table 33: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition in simulated flue gases by means of a pulsed discharge plasma generated in a cylinder type reactor Efficiency 65% Amount of destruction 2 l/min

By Products N2O, NO2, O3, CH3COOH, CO2 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost Low Working Area Large on lab scale Number of Labor 1 Comments ” NO(x) removal process using pulsed discharge plasma”, Akira Mizuno, Kazuo Shimizu, Alokkumar Chakrabarti, Lucian Dascalescu and Satoshi Furuta, IEEE Transactions on industry applications, Vol 32, no 5, September/October 1995, [47]

Table 34: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition using Xe discharge lamp as the vacuum UV source within a photochemical reactor Efficiency Efficiency increases with increasing VUV radiated intensity Amount of destruction

By Products HNO3 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments ” NO(x) treatment in Diesel Engineer Combustion Exhaust Gases by Vacuum Ultra-Violet Irradiation”, K.Ueno and R Ohyama, 2007 Annual Report Conference on Electrical Insulation and Dielectric Phenomena, [48]

120

Table 35: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition at 350-450 °C using a multilayered electrochemical cell Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No but the catalytic layers are made before destruction Investment cost High Running cost Low Working Area Number of Labor 1 Comments ”Multilayered electrochemical cell fro NO(x) decomposition at moderate temperatures”, Vitali Sinitsyn, Koichi Hamamoto, Yoshinobo Fujishiro, Sergei Bredikhin, Masanobu Awano, Ionics (2006) 12: 211-213, DOI: 10.1007/s11581-006-0030-6, [49]

Table 36: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Decomposition using pulsed microwave discharges at atmospheric pressure Efficiency 95% Amount of destruction

By Products NO2 production is reduced Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No but the gas mixture is made PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments ”Pulsed microwave discharge at atmospheric pressure for NO(x) decomposition”, M Baeva, H Gier, A Pott, J Uhlenbusch, J Hoschele and J Steinwandel, Plasma Sources Sci, Technol. 11(2002) 1-9, [50]

121

Table 37: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Destruction using microwave and electron beam processing Efficiency 55% only with microwave processing but MW and EB increase it up to 95% Amount of destruction

By Products NH4NO3 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No but the gas mixture is made PTODABD No Investment cost High because of gaseous mixture preparation system, microwave source, electron beam source, multimode rectangular cavity Running cost Low Working Area Large on lab scale Number of Labor 1

Comments This process enable simultaneous removal of NOx and SO2 ”SO2 and Nox removal by microwave and electron beam processing”, Daneil Lghigeanu, Ioan Calinescu, Diana Martin, Constantin Materi, Anca Bulearca, Adelina Ighigeanu, Journal of Microwave Power and Electromagnetic energy 43, No 1, 2009, [51]

Table 38: Conventional technology to destroy NOx

NOx

Items to compare Conventional technology

Destruction technology Adsorption, desorption followed by non-thermal plasma decomposition Efficiency 90% Amount of destruction Different flow rates were used, 1 L/min,2 L/min By Products Skilled Labor No Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost Moderate Running cost Low Working Area Small Number of Labor 1 Comments Cost efficient technology

122

”Nobel Nox and VOC Treatment using concentration and Plasma decomposition”, Toshiaki Yamamoto, Souma Asada, Tomohiro Lida and Yoshiyasu Ehara, IEEE 978-1-4244-6395-4/10, [52]

2.2. CFC

Table 39: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Catalytic hydrolysis of CFC-12 over WO3/SnO2 solid acid Efficiency 99.50% Amount of destruction By Products CFC-13 Skilled Labor Skilled person for X-ray diffractometer Dangerous process Yes, as CFC-13 is released Automatic No PTOTMBD No PTODABD Investment cost High because of X-ray diffractometer Running cost High because it is a high temperature process Working Area Small Number of Labor 1 Comments No deactivation of catalysis during whole process ”A novel CFC-12 Hydrolysis Catalyst: WO3/SnO2”, Zhen MA, Wei Ming HUA, Yi TANG, Zi GAO, Chinese Chemical Letters Vol. 11, No.1, pp. 87-88, 2000, [53]

Table 40: Conventional technology to destroy CFC-13

CFC-13

Items to compare Conventional technology

Destruction technology Decomposition by non-thermal plasma chemical decomposition technology using ferroelectric plasma reactor Efficiency 95% with 0.5 L/min and 86% with 1 L/min Amount of destruction

By Products Different by-products for different background gases, e.g. CHCl2F, CHCl3, CHClF2 , CCl3F, CCl2F2, CH2ClF, CCl2F2, C2H5Cl, C2H5Cl Skilled Labor Yes Dangerous process Yes as dangerous by-products are released Automatic Yes PTOTMBD No PTODABD Investment cost High due to flame ionization detector, gas chromatograph detector, Laser aerosol spectrometer, ferroelectric plasma reactor

123

Running cost Low Working Area Small as it’s laboratory scale Number of Labor 1

Comments By products were high for dry H2 followed by dry N2, wet N2, wet air and dry air ”Aerosol Generation and Decomposition of CFC-113 by the Ferroelectric Plasma Reactor”, Toshiaki Yamamoto, Ben W.L. Jang, IEEE Transactions on Industry applications, Vol 34, No.4, July/August 1999, [54]

Table 41: Conventional technology to destroy CFC-112 and CFC-113

CFC-112 and CFC-113

Items to compare Conventional technology

Destruction technology Catalytic decomposition of CFC-112 and CFC-113 in the presence of ethanol with iron(3) chloride catalyst supported on active charcoal at low temperature Efficiency Amount of destruction Decreases with time

By Products For CFC-112( C2F2Cl2, CHFClCFCl2,CFCl2CFCl2) For CFC-113 (C2F3Cl, C2F2Cl2, CHFClCF2Cl,CF2ClCFCl2) Skilled Labor No Dangerous process No Automatic Yes PTOTMBD Yes PTODABD Investment cost Low Running cost Low Working Area Small Number of Labor 1 Comments It is a low temperature process ”Catalytic Decomposition of CFC-112 and CFC-113 in the presence of Ethanol”, Daisaku MIYATANI, Kiyonori SHINODA, Tadashi NAKAMURA, Minoru OTHA and Kensei YASUDA, The Chemical Society of Japan Chemistry Letters, pp. 795-798, 1992, [55]

Table 42: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Catalytic decomposition of CFC-12 using Mo2O3/ZrO2 as catalyst with varying ZrO2 content in the presence of water vapor and oxygen Efficiency Amount of destruction

By Products CClF3 Skilled Labor Yes Dangerous process No

124

Automatic Yes PTOTMBD No PTODABD Investment cost High because of X-ray diffractometer, fixed bed reactor, tubular flow reactor made of stainless steel, gas chromatograph, mass spectrometer, Carlo Erba analyzer Running cost High Working Area Large Number of Labor 1 Comments Very long process, took 100 hours Catalytic decomposition of CFC-12 over Solid Super Acid Mo2O3/ZrO2, Ping Ning, Xianyu Wang, Hasn-Jorg bart, Tiancheng Liu, Jun Huang, Yaming Wang and Hong Gao, Journal of Environmental Engineering, Vol. 136, No.12 December 2010, pp. 1418-1423, doi 10.1061/(ASCE) EE. 1943-7870.0000287, [56]

Table 43: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Decomposition of CFC-12 using WO3/TiO2 catalysis in the presence of water vapors Efficiency 99.80% Amount of destruction By Products CFC-13 (very little) Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No PTODABD Investment cost Low Running cost Low Working Area Small Number of Labor 1 Comments ”Catalytic decomposition of CFC-12 over WO3/TiO2”, Zhen MA, Weiming Hua, Yi Tang and Zi Gao, Chemistry Letters, [57]

Table 44: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Catalytic decomposition of CFC-12 in the presence of water

vapors over a series of solid acids WO3/ZrO2 Efficiency 98% Amount of destruction By Products

125

Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Investment cost High because of X-ray diffractometer, gas chromatography Running cost High because of calcinations Working Area Small Number of Labor 1 Comments In other decomposition of processes of HF and HCl are produced which corrode the catalyst but in this reaction HF and HCl are neutralized ”Catalytic hydrolysis of chlorofluorocarbon (CFC-12) over WO3/ZrO2”, Weiming Hua, Feng Zhang, Zhen Ma, Yi Tang and Zi Gao, Chemistry Letters 65 (2000) 85-89, [58]

Table 45: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Destruction of CFC-11 using moderate power microwave torch discharge in atmospheric pressure flowing nitrogen Efficiency 100% Amount of destruction 300 g/h By Products No unwanted by products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Investment cost High but a low cost prototype is proposed Running cost Not that high Working Area Small Number of Labor 1 Comments Superior than other methods as there is no generation of any unwanted by-products plus 100% efficiency ”CFC-11 destruction by microwave torch generated atmospheric-pressure nitrogen discharge”, Mariusz Jasinski, Jerzy Mizeraczyk, Zenon Zakrzewski, Toshikazu Ohkubo and Jen-Shih Chang, Journal of Physics D: Applied Physics. 35(2002) 2274- 2280, [59]

Table 46: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Decomposition of CFC12 using shell wastes by direct reaction

126

between CFC12 and alkaline based materials at low temperatures Efficiency 99.9% Amount of destruction

By Products CCl3F,CCl2F2,CClF3 Skilled Labor Yes Dangerous process No but plant can cause problems if not handled with care Automatic Yes PTOTMBD No PTODABD Yes Investment cost High as calcination at high temperature is required in start for 12 hours, fluorescence spectrometer, thermo gravimetric analyzer, SEM Running cost High Working Area Large Number of Labor > 1 Comments ”CFC12 Decomposition over Shell Wastes Based Reactants”, Yoshiki Kawamoto, Daisuke Hirabayashi, Kenzi Suzuki, Hideki Inagaki, Akihiro Takeuchi, Chouyuu Watanabe, Proceedings of International Symposium on Eco Topia Science 2007, ISETS07(2007) , [60]

Table 47: Conventional technology to destroy CFCs

CFCs

Items to compare Conventional technology

Destruction technology Complete destruction of CFCs by reductive dehalogenation using sodium naphthalenide Efficiency > 99% Amount of destruction By Products No Skilled Labor Yes for x-ray analysis Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High Running cost High but can be reduced Working Area Small Number of Labor 1 Comments ”Complete Destruction of Chlorofluorocarbons by Reductive Dehalogenation Using Sodium Naphthalenide”, Akira Oku, Kenji Kumura and Masaya Sato, Ind. Eng. Chem. Res. 1989, 28, 1055-1059, [61]

Table 48: Conventional technology to destroy CFC Gases

CFC GASES

127

Items to compare Conventional technology

Destruction technology Decomposition of CFC gases by surface discharge induced plasma chemical processing in atmospheric air, pure oxygen gas or pure nitrogen gas Efficiency 90% for CFC-22 and 99% for CFC-113 Amount of destruction By Products Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Not high but a bit expensive Running cost Low Working Area Small Number of Labor 1 Comments ”Decomposition of Fluorocarbon Gaseous Contaminants by Surface Discharge-Induced Plasma Chemical Processing”, Tetsuji Oda, Tadashi Takahashi, Hiroshi Nakano, Senichi Masuda, IEEE Transactions on Industry Applications, Vol 29, No.4, July/August 1993, [62]

Table 49: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Decomposition of CFC-12 by adding hydrogen in a cold plasma system Efficiency > 95% Amount of destruction

By Products CH4,C2H2, HCl, HF, SiF4 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High because of spectrometer, FTIR, Plasma reactor Running cost Low Working Area Large Number of Labor 1 Comments ”Decomposition of Dichlorodifluoromethane by Adding Hydrogen in a Cold Plasma System”, Ya Fen Wang, Wen Jhy Lee, Chuh Yung Chen, Lien Te Hsieh, Environmental Science Technology 1999, 33, 2234-2240, [63]

128

Table 50: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Catalytic decomposition of CFC-12 on TiO2/SiO2 Efficiency > 97% Amount of destruction

By Products CH4 Skilled Labor Yes for analysis Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High because of X-ray diffractometer, Spectrophotometer Running cost High Working Area Large Number of Labor 1 Comments ”Decomposition of Dichlorodifluoromethane on TiO2/SiO2”, Seiichiro Imamura, Toshihiko Shiomi, Shingo Ishida, Kazunori Utani, Hitoshi Jindai, Ind. Eng. Chem. Res. 1990, 29, 1758-1761, [64]

Table 51: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Decomposition of CFC-12 by surface discharge induced plasma chemical process using a reactor Efficiency 92.70% Amount of destruction By Products Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments Decomposition efficiency increases with time ”Decomposition of Chlorofluorocarbon by Non-thermal Plasma”, Hyun-Choon Kang, J.Ind. Eng. Chem, Vol., No.5, (2202) 488- 492, [65]

129

Table 52: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Decomposition of CFC-12 by 12 kind of metal supported gas diffusion electrodes causing defluorination and dechloroination Efficiency 100% Amount of destruction

By Products HFC-32,CH4, C2H4, C2H6, H2, CHClF2,CH2F2 Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments ”Electrochemical Decomposition of CFC-12 Using Gas Diffusion Electrodes”, Noriyuki Sonoyama and Tadayoshi Sakata, Environ. Sci. Technol. 1998, 32, 375-378, [66]

Table 53: Conventional technology to destroy CFCs

CFCs

Items to compare Conventional technology

Destruction technology Decomposition of chlorofluorocarbons by water plasma Efficiency Amount of destruction

By Products Cl2 Skilled Labor Dangerous process Automatic PTOTMBD No PTODABD No Investment cost High Running cost High Working Area Number of Labor Comments High temperature process, so very expensive ”Thermodynamic consideration of the water plasma decomposition process of chlorofluorocarbons”, S Takeuchi, M Itoht, K Takeda, K Mizuno, T Asakuras and A Kobayashi, Plasma Sources Sci. Technol. 2 (1993) 63-66, [67]

130

Table 54: Conventional technology to destroy CFC-13

CFC-13

Items to compare Conventional technology

Destruction technology Decomposition of CFC-13 with 13 kinds of metal supported porous carbon diffusion electrodes by dechlorination and defluorination Efficiency 77.70% Amount of destruction

By Products CH4, HFC-23 Skilled Labor No Dangerous process Yes because of HFC-23 Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments ”Electrochemical Hydrogenation of CFC-13 Using Metal-Supported Gas diffusion electrodes”, Noriyuki Sonoyama and tadayoshi Sakata, Environ. Sci, Technol. 1998, 32, 4005-4009, [68]

Table 55: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Hydrolytic decomposition of CFC-12 on modified ZrO surfaces and charcoal at 450 °C Efficiency 100% Amount of destruction

By Products CO2, HCl, HF, CFC-13 Skilled Labor No Dangerous process Yes Automatic No PTOTMBD No PTODABD Yes Investment cost High Running cost High Working Area Small Number of Labor 1 Comments Recommended only where condensation procedures due to low CFC concentration are too expensive

131

”Heterogeneously catalyzed hydrolytic decomposition of CFCS”, Kai-Uwe Niedersen, Lefriede Lieske and Erhard Kemnitz, Green Chemistry October 1999, [69]

Table 56: Conventional technology to destroy CFC

CFC

Items to compare Conventional technology

Destruction technology Decomposition of CFC in the troposphere with the aid of natural lightning Efficiency Amount of destruction 900 kg/yr. By Products Skilled Labor No Dangerous process No Automatic No PTOTMBD No PTODABD No Investment cost High Running cost High Working Area Very large Number of Labor More than 1 Comments CFC production rate is 800 tons/year and lightning decompose only 930 kg/year ”The decomposition of CFCs in the troposphere by lightning”, Mengu Cho and Michael J. Rycroft, Journal of Atmospheric and Solar Terrestrial Physics Vol.59, No.12, pp. 1373- 1379, 1997, [70]

Table 57: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction Hydrolytic decomposition of CFC-12 on various method Zirconium oxide technology surfaces at 500 °C Efficiency > 90% Amount of destruction

By Products Limited formation of CFC-13,CFC-12,CO2 Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD No PTODABD Yes Investment cost High due to XRD, FTIR, Spectrometer, autoclave Running cost High as it is a high temperature process Working Area Large because of XRD and spectrometer

132

Number of Labor 1 Comments Deactivation of catalysis after long time operation ”Hydrolytic decomposition of dichlorodifluoromethane on modified zirconium oxide surfaces”, A. Hess and E. Kemnitz, Catalysis Letters 49 (1997) 199-205, [71]

Table 58: Conventional technology to destroy CFC-11 and CFC-113

CFC-11 and CFC-113

Items to compare Conventional technology

Destruction technology Sonochemical destruction of CFC-11 and CFC-113 in dilute aqueous solution using ultrasonic energy Efficiency > 90% Amount of destruction 23 mg/6 mins for batch process, 38 mg/30 mins for circulating process Kg/s By Products HF, HCl Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No but like most of the processes a solution is made with water PTODABD No Investment cost High Running cost Low Working Area Couldn’t be judged Number of Labor 1 Comments This approach does not require transference of target molecule from an aqueous phase as would be required in combustion, catalytic or otherwise ”Sonochemcial Destruction of CFC-11 and CFC-13 in dilute aqueous solution”, H, Michael Cheung and Shreekumar Kurup, Environ. Sci. Technol. 1994, 28, 1619-1622, [72]

Table 59: Conventional technology to destroy CFC

CFC

Items to compare Conventional technology

Destruction CFC decomposition caused by energy transfer from electronically excited species technology within a non-thermal plasma in nitrogen at atmospheric pressure Efficiency Amount of destruction

By Products Skilled Labor Yes Dangerous process Yes Automatic Yes

133

PTOTMBD No PTODABD No Investment cost High because of electrical discharge reactor, gas analyzer, soap film flow meter, oscillator, high voltage amplifier, electric furnace, positive generator, FTIR spectrometer Running cost High because of electric furnace operation Working Area Large Number of Labor 1 Comments ”Mechanism of the Dissociation of Chlorofluorocarbons during No thermal Plasma Processing in Nitrogen at Atmospheric Pressure”, Arkadiy Gal, Atsushi Ogata, Shigeru Futamura and Koichi Mizuno, J.Phys. Chem. A 2003, 107, 8859-8866, [73]

Table 60: Conventional technology to destroy CFC-12

CFC-12

Items to compare Conventional technology

Destruction technology Non-thermal atmospheric pressure plasma with TiO2 catalyst combination to decompose CFC-12 in nitrogen and air Efficiency Amount of destruction

By Products CO,CO2,COF2,HCl,N2O for Nitrogen gas streams and CO,CO2,COF2,HCOCl,NO,NO2,N2O in air Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of plasma rector, oscilloscope, mass flow controller, FTIR spectrometer Running cost High but not that much Working Area Large Number of Labor 1 Comments ”Plasma-assisted catalysis for the destruction of CFC-12 in atmospheric pressure gas steams using TiO2”, Anna E. Waalis, J. Christopher Whitehead, Kui Zhang, Catalysis Letters vol. 113 Nos. 1-2, January 2007, DOI: 10.1007/s 10562-006-9000-x, [74]

Table 61: Conventional technology to destroy Freon-12

Freon-12

Items to compare Conventional technology

Destruction technology Catalytic decomposition of Freon-12 on BPO4 catalyst Efficiency 100% Amount of destruction

By Products CO2

134

Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High because of electron spectroscopy, X-ray diffractometer, SEM Running cost High Working Area Large Number of Labor 1

Comments BPO4 is the highest durable catalyst but it was deactivated during the prolong use, it’s efficiency can be improved by using CaO which saves it from poisoning from inorganic fluorine’s ” Decomposition of Dichlorodifluoromethane on BPO4 Catalyst” Henrik K.Hansen, Peter Rasmusen, Aage Fredenslund, Martin Schiller, Jurgen Gmehling, Ind. Eng. Chem. Res. 1991, 30, 2355-2358, [75]

Table 62: Conventional technology to destroy CFC

CFC

Items to compare Conventional technology

Destruction technology Decomposition in presence of water over different catalysts in which

TiO2-ZrO2 had highest activity Efficiency 100% Amount of destruction

By Products CFC, HCF, CO, CO2 Skilled Labor Yes Dangerous process No, specially HF and HCl are removed in the reaction which is a big advantage Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of XRD, gas chromatographer, spectrophotometer Running cost High Working Area Large Number of Labor 1 Comments ” Decomposition of Chlorofluorocarbones on TiO2-ZrO2”, Masahiro Tajima, Mki Niwa, Yasushi Fujii, Yutaka Koinuma, Reiji Aizawa, Satoshi Kushiyama, Satoru Kobayashi, Koici Mizuno, ideo Ohuchi, [76]

Table 63: Conventional technology to destroy CFCs,

CFCs

Items to compare Conventional technology

Destruction technology Decomposition of CFCs in the presence of water over different solid acid catalysts

135

Efficiency 40% Amount of destruction

By Products CFCs, CO, CO2 Skilled Labor Yes but for analytical tools but not for experimentation Dangerous process Yes Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost High Working Area Large Number of Labor 1 Comments HCl and HF produced are easily removed by neutralization ”Decomposition of chlorofluorocarbonsn in the presence of water over zeolite catalyst”, Masahiro Tajima, Miki Niwa, Yasushi Fujii, Yutaka Koinuma, Reiji Aizawa, Satoshi, Kushiyama, Satoru Kobayashi, Koichi Mizuno, Hideo Ohuchi [77]

2.3. HCFC

Table 64: Conventional technology to destroy HCFC-22

HCFC-22

Items to compare Conventional technology

Destruction Catalytic decomposition of HCFC-22 by adding platinum to sulfated and technology non-sulfated TiO2-ZrO2 mixed oxides Efficiency 90% Amount of destruction

By Products CHClF2, CO, CO2, CHF3, HCl, HF Skilled Labor Yes Dangerous No process Automatic No PTOTMBD No PTODABD Yes Investment cost High because of diffractometer and spectrometer Running cost High because of high temperature and long process Working Area Large Number of Labor 1 Comments ”Catalytic decomposition of chlorodifluoro methane (HCFC-22) over platinum supported on TiO2-ZrO2 mixed oxides”, Hongxia Zhang, Ching Fai Ng, Suk Yin Lai, Applied Catalysis B: Environmental 55 (2005) 301-307, [78]

Table 65: Conventional technology to destroy HCFC-123 and HCFC-141b

HCFC-123 and HCFC-141b

136

Items to compare Conventional technology

Destruction technology Decomposition by Chlorine as oxidizing agent Efficiency Amount of destruction

By Products CF3C(O)Cl, COFCl, CO Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High because of spectrometer, interferometer, Mercury-Cadmium- tellurdie detector, heat gun, ultraviolet lamps, infra-red source Running cost Low Working Area Large Number of Labor 1 Comments ” Chlorine Initiated Oxidation Studies of Hydro chlorofluorocarbons: Results of HCFC-123 (CF3CHCl2) and HCFC-141b (CFCl2CH3), E.O. Edney, B.W. Gay Jr and D.J. Driscoll, Journal of Atmospheric Chemistry 12: 105-120, 1991, [79]

Table 66: Conventional technology to destroy HCFCs and HCFs

HCFCs and HCFs

Items to compare Conventional technology

Destruction technology Photochemical oxidation studies by chlorine initiated photo oxidation Efficiency Amount of destruction

By Products C(O)F2,HFC(O),CF3CF(O),C(O)F2,HFC(O),CF3CF(O),C(O)F2,C(O)F2 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High because of spectrometer, interferometer, Mercury-Cadmium- Telluride detector, heat gun, UV lamps, infrared source Running cost Low Working Area Large Number of Labor 1 Comments Chlorine Initiated Photooxidation Studies of Hydrochlorofluorocarbons(HCFCs) and Hydrofluorocarbons(HFCs): Results for HCFC- 22(CHClF2);HFC-41(CH3F);HCFC-124(CClFHCF3);HFC-125(CF3CHF2);HFC-134a(CF3CH2F);HCFC-142b(CCLF2CH2); and HFC- 152A(CHF2CH3) , [80]

137

Table 67: Conventional technology to destroy CFCs and HCFCs

CFCs and HCFCs

Items to compare Conventional technology

Destruction technology Decomposition in water by ultrasonic radiation Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic No PTOTMBD Yes PTODABD No Investment cost High Running cost Low Working Area Number of Labor 1 Comments ”Decomposition of Chlorofluorocarbons and hydrofluorcarbons in water by ultrasonic irradiation”, K.Hirai, Y.Nagata, Y. Maeda, Ultrasonics Sonochemistry 3 (1996) S205-S207, [81]

Table 68: Conventional technology to destroy HCFC-22

HCFC-22

Items to compare Conventional technology

Destruction technology Catalytic decomposition by using gold nano particles and TiO2-ZrO2 as catalyst Efficiency 100% can be achieved by increasing temperature Amount of destruction

By Products HF, HCl,CO,CO2,CHClF2,CHF3 Skilled Labor No Dangerous process Yes Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments Gold nano particles are catalytically active from CO oxidation ”Deactivation of gold catalysts supported on sulfated TiO2-ZrO2 mixed oxides for CO oxidation during catalytic decomposition of chlorodifluoromethane (HCFC), Suk Yin Lai, Hongxia Zhang and Ching Fai Ng, Catalysis Letters Vol. 92, Nos. 3-4, February 2004, [82]

138

Table 69: Conventional technology to destroy HCFC-22

HCFC-22

Items to compare Conventional technology

Destruction technology Decomposition by using cold plasma controlled by pulse high voltage apparatus Efficiency 97% Amount of destruction By Products HF Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate Running cost Low Working Area Small Number of Labor 1 Comments ”Decomposition of HCFC-22 in a cold plasma system”, Shinya Hayashi, Takaki Inaoka, Wataru Minami, Hee-Joon Kim, Department of Ecological Engineering, Toyohashi University of Technology Japan, [83]

Table 70: Conventional technology to destroy CHF2Cl

CHF2Cl

Items to compare Conventional technology

Destruction technology Decomposition of CHF2Cl in a non-thermal atmospheric pressure plasma reactor with a perforated dielectric barrier Efficiency Depends upon various factors Max 62% Min 5% Amount of destruction

By Products CO2, N2O, CO, COF2, NO2 Skilled Labor Yes Dangerous process Yes Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of FTIR, spectrometer, transformer, oscilloscope Running cost Low Working Area Small Number of Labor 1 Comments

139

”Destruction of Chlorodifluoromethane(CHF2Cl) by Using Dielectric Barrier Discharge Plasma”, Young Sun Mok, Sang-Baek Lee and Myung Shik Chang, IEEE Transactions on plasma science, Vol.37, no.3, March 2009, [84]

Table 71: Conventional technology to destroy CF2HCl

CF2HCl

Items to compare Conventional technology

Destruction technology Decomposition by pyrolysis at 670-750 °C Efficiency Amount of destruction

By Products HF, HCl, C2F4, CF2HCl Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost High Working Area Lab Scale Number of Labor 1 Comments Thermal decomposition processes are very expensive for all toxic material decomposition ”The thermal decomposition of chlorodifluoromethane”, F.Gozzo, C.R. Patrick, Tetrahedron, 1966, Vol.22, pp. 3329-3336, [85]

Table 72: Conventional technology to destroy CHClF2

CHClF2

Items to compare Conventional technology

Destruction technology Decomposition under non-equilibrium oxidizing plasma conditions Efficiency .99 conversion Amount of destruction

By Products CO, Cl, F, CCl2F2, CClF3 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Lab Scale/Medium Number of Labor 1 Comments

140

”Plasma-induced decomposition of chlorodifluoromethan”, Anna Opalska, Teresa Opalinska, Jerzy Polaczek, Pawel Ochman, Instytut Chemii Przemyslowej, Rydygiera 8, 01-793 Warsaw, POLAND, [86]

Table 73: Conventional technology to destroy Hydrogenolyzing

HYDROGENOLYZING

Items to compare Conventional technology

Destruction technology Decomposition of hydrogenolyzing in presence of RhCl3(py)3 and other homogeneous catalysts Efficiency 96.5% max Amount of destruction

By Products CHF3, CH4, are main products, CHF2Cl, CH2F2, NH3C2H6 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High because of different spectrometer, gas chromatographs, autoclave Running cost Low Working Area Large Number of Labor 1 Comments ”Homogeneous catalytic hydrogenolysis of chlorodifluoromethane”, Otoo Balazs Simon, Attila Sisak, Applied Catalysis A: General 342(2008) 131-136, [87]

Table 74: Conventional technology to destroy Freon21 and Freon-142-B

FREON21 and FREON-142-B

Items to compare Conventional technology

Destruction technology Decomposition of Freon 21 and Freon 142-B using high-voltage glow discharge plasma Efficiency 100% by using higher voltages Amount of destruction

By Products CO2, HF, Cl, HCl, CO Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1

141

Comments ”Destruction of Freons by the Use of High-Voltage Glow Plasmas”, Franz-Josef Spiess, Xiao Chen, Stephanie L.Brock, Steven L.Suib, Yuji Hayashi and Hiroshige Matsumoto, J.Phys. Chem. A 2000, 104, 11111-11120, [88]

Table 75: Conventional technology to destroy HCFC-22

HCFC-22

Items to compare Conventional technology

Destruction technology Electrochemical hydrogenation of HCFC-22 using metal and metal- phthalocyanine supported gas diffusion electrodes and only Co-PC GDE showed catalytic activity for HCFC-22 hydrogenation Efficiency Increases with negative increase in potential during electrolysis Amount of destruction

By Products CH4, HFC-32 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate Running cost Moderate Working Area Small Number of Labor 1 Comments ”Electrochemical hydrogenation of chlorodifluoromethane (HCFC-22) at metal and metal-phthalocyanine-supported gas diffusion electrodes”, Noriyuki Sonoyama, Tadayoshi Sakata, Advances in Environmental Research 8 (2004) 287-291, [89]

Table 76: Conventional technology to destroy Carbon-12 Substituted Chlorodifluoromethane

CARBON-12 SUBSTITUTED CHLORODIFLUOROMETHANE

Items to compare Conventional technology

Destruction technology Infrared multi-photon produced through CO2 laser pulse used for decomposition of carbon-13 substituted chlorodifluoromethane molecules Efficiency Amount of destruction

By Products C2F4 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost Low

142

Working Area Small Number of Labor 1 Comments ”Efficient Production of C2F4 in the Infrared Laser Photolysis of CHClF2”, M.Gauthier, C.G. Cureton, P.A. Hackett and C.Willis, Appl. Phys. B 28, 43-50, 1982, [90]

3. Liquids

3.1. Acids

Table 77: Conventional technology to destroy Hydrogen Iodide

HYDROGEN IODIDE

Items to compare Conventional technology

Destruction Decomposition of HI using a fixed bed reactor in the range of 523-823 K using technology Pt/C catalysts Efficiency 25% Amount of destruction By Products Skilled Labor Yes but for analytical instruments Dangerous No process Automatic Yes PTOTMBD No PTODABD Yes Investment cost High as SEM, EDS and XRD analysis were carried out Running cost High as it’s a high temperature process because of pre-treatment of toxic material Working Area Large Number of Labor 1 Comments ”Decomposition of hydrogen iodide on Pt/C-based catalysts for hydrogen production”, Jung-Min Kim, Jung-Eun Park, Young-Ho Kim, Kyoung-Soo Kang, Chang-Hee Kim, Chu-Sik Park, Ki-Kwang Bae, International Journal of hydrogen energy 33 (2008) 4974- 4980, [91]

Table 78: Conventional technology to destroy Oxalic Acid

OXALIC ACID

Items to compare Conventional technology

2+ Destruction Decomposition of oxalic acid with HNO3 in the presence of Mn ions by reacting technology KMnO4 and oxalic acid Efficiency 99.90% Amount of

143 destruction By Products Skilled Labor No Dangerous process No Automatic No PTOTMBD No PTODABD No Investment cost Low Running cost Low Working Area Small Number of Labor 1 Comments ”Decomposition of oxalic acid with nitric acid”, M.Kubota, Journal of Radioanalytical Chemistry Vol.75, No’s 1-2 (1982) 39-49, [92]

Table 79: Conventional technology to destroy Formic Acid

FORMIC ACID

Items to compare Conventional technology

Destruction Decomposition of formic acid using clean and partially oxidized surfaces by technology temperature programmed reaction spectroscopy Efficiency Amount of destruction

By Products CO2, CO, H2 Skilled Labor Yes Dangerous No process Automatic No PTOTMBD No PTODABD Yes Investment cost High Running cost Moderate Working Area Number of Labor 1 Comments ”Formic acid decomposition from clean and oxidized nickel/iron(100) alloy surfaces”, E.M. Silverman and R.J. Madix, C.R. Brundle, J. Vac. Sci. Technol. 18(2), March 1981, [93]

Table 80: Conventional technology to destroy Nitric Acid

NITRIC ACID

Items to compare Conventional technology

Destruction Decomposition of nitric acid vapor at low pressures in two vycor bulbs at

144 technology temp b/w 375-424 with and without addition of argon, CO2, oxygen, water, nitrogen oxide and nitric oxide Efficiency Nearly 100% Amount of destruction By Products Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD Yes PTODABD No Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments ”Kinetic of the thermal decomposition of nitric acid vapor 3. Low pressure results”, Harold S. Johnston, Lousie Foering, James R.White, J.Am. Chem. Soc. 1955, 77(16), pp. 4208-4212, [94]

Table 81: Conventional technology to destroy Hydrogen Iodide

HYDROGEN IODIDE

Items to compare Conventional technology

Destruction technology Destruction of HI using Ni catalysts Efficiency Amount of destruction 0.1 mL/min

By Products NI2 which causes the deactivation of catalyst Skilled Labor No Dangerous process Automatic No PTOTMBD No PTODABD Yes Investment cost High Running cost High because it’s a high temperature process and catalyst preparation Working Area Small Number of Labor 1 Comments ”Ni catalyst deactivation in the reaction of hydrogen iodide decomposition”, Favuzza P, Felici C, Mazzocchia C. Spadoni A. Tarquini P. Tito A.C., AIDIC Conference Series, Vol. 9,2009 DOI: 10.3303/ACOS0909016, [95]

Table 82: Conventional technology to destroy Hydrogen Peroxide

HYDROGEN PEROXIDE

Items to compare Conventional technology

145

Destruction technology Decomposition by peroxocarbonic acid anion Efficiency Amount of destruction By Products Skilled Labor No Dangerous process No Automatic No PTOTMBD No PTODABD No Investment cost High because of spectrometer, deinking mill Running cost Low Working Area Small Number of Labor 1 Comments ”On the decomposition of hydrogen peroxide via the peroxocarbonic acid anion”, Dr. H.U. Suess, Dr. M. Janik, Technical association of the pulp and paper industry of southern Africa, [96]

Table 83: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction Photo catalytic decomposition on TiO2 in an inert atmosphere by two parallel path technology ways at room temperature Efficiency Amount of destruction

By Products CO2, C2H6, CH4, H2O Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High because of UV lamps, radiometer, pyrex reactor, mass spectrometer Running cost High as the reactor is maintained at 723 K for 30 mins before the start of each experiment Working Area Small Number of Labor 1 Comments In first pathway lattice oxygen is required but not in the second pathway ”Photo catalytic decomposition of acetic acid on TiO2”, Darrin S. Muggli, Sarah A. Keyser and John L. Falconer, Catalysis Letters 55 (1998) 129-132, [97]

Table 84: Conventional technology to destroy Boric Acid

BORIC ACID

Items to compare Conventional technology

146

Destruction technology Decomposition through pressure induced chemical decomposition Efficiency Amount of destruction

By Products Cubic metabolic acid (HBO2) Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High because of X-ray powder diffraction, infrared spectroscopy measurements Running cost Low Working Area Large Number of Labor 1 Comments ”Structural changes and pressure-induced chemical decomposition of boric acid”, A. Yu. Kuznetsov, A.S. Pereira, J. Haines, L. Dubrovinsky, V. Dmitriev, P. Pattision, Joint 20th Airapt- 43th EHPRG, June 27-July 1, Karlsruhe/ Germany 2005, [98]

Table 85: Conventional technology to destroy Nucleic Acids

NUCELIC ACIDS

Items to compare Conventional technology

Destruction technology Selective decomposition by high temperature and pressure region around a gold nanoparticle, generated when a gold nano-particle was irradiated with a pulsed laser in aqueous solution Efficiency 100% Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic No PTOTMBD Yes PTODABD No Investment cost High Running cost High Working Area Number of Labor 1 Comments ” Selective decomposition of nucleic acids by laser irradiation on probe-tethered gold nanoparticles in solution”, Yoshihiro Takeda, Tamotsu Kondow and Fumitaka Mafune, Physics Chemistry Chemical Physics, DOI: 10.1039/c0cp00770f, [99]

Table 86: Conventional technology to destroy Boric Acid

BORIC ACID

147

Items to compare Conventional technology

Destruction technology Decomposition through pressure induced chemical decomposition as it suffers a high anisotropic compression Efficiency Amount of destruction

By Products Cubic HBO2, ice-VI, ice-VII Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High because of X-ray powder diffraction, infrared spectroscopy measurements Running cost Low Working Area Large Number of Labor 1 Comments ”Pressure-Induced Chemical Decomposition and Structural Changes of Boric Acid”, Alexei Yu. Kuznetsov, Altair S. Pereira, Andrei A. Shiryaev, Julien Haines, Leonid Dubrovinsky, Vladimir Dmitriev, Phil Pattison and Nicolas Guignot, J.Phys. Chem. B 2006, 110, 13858-13865, [100]

Table 87: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction Photo catalytic decomposition (UV-Lamp) using fluidized reactor which technology increases contact between photo source and catalyst

Efficiency Over 70% can reach to 90% using Al/TiO2 Amount of destruction By Products Skilled Labor No Dangerous No process Automatic Yes PTOTMBD No PTODABD Yes Investment cost Moderate as major investment is UV lamp and fluidizer bed Running cost High because of high temperature catalyst preparation Working Area Small Number of Labor 1

Comments Comparing photo catalytic decomposition over TiO2 and Al/TiO2, Al/TiO2 had higher removal rate than TiO2. It was because that Al metal increased acidic site and acidic site was used as active site. Calculated mass coefficient supported the

148

results ”Photo catalytic decomposition of gaseous acetic acid in fluidized reactor”, Y.H. Son, J.Y. Ban, S.C. Lee, M. Kang and S.J. choung, [101]

Table 88: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction Decomposition using UV light and thin films of TiO2 and TiO2/SiO2 prepared by the technology sol-gel method Efficiency Amount of destruction

By Products H2O, CO2 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High because of thermogravimeteric differential thermal analysis(TG-DTA), fourier transformation and infrared spectroscopy, specific area analysis (BET), X-ray diffraction (XRD), transmission electron microscopy (TEM), batch photo reactor Running cost High because of high temperature for thin film preparation Working Area Large Number of Labor 1

Comments TiO2/SiO2 thin film having a pure-anatase phase showed a higher photo catalytic activity than did the pure-anatase SiO2 ”Photo catalytic decomposition of Acetic Acid over TiO2 and TiO2/SiO2 thin films prepared by the sol-gel method”, Man Sig Lee, Ju Dong Lee and Seong-Soo Hong, J.Ind. Eng. Chem. Vol.11, No.4, (2005) 495-501, [102]

Table 89: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction Photo-catalytic oxidation (PCO) and decomposition (PCD) of acetic acid on TS-1 technology and Ti-MCM-4 1 catalysts Efficiency Amount of destruction

By Products CO2,CH4,C2H6 for P-25 TiO2,CO2 and CH4 on TS-1 and Ti-MCM-41 Skilled Labor Yes Dangerous No process

149

Automatic No PTOTMBD No PTODABD Yes Investment cost Yes because of spectrometer, XRD, UV-DRS Running cost Low Working Area Large Number of Labor 1 Comments The rates of product formation during PCD were lower compared with PCO ”Photo catalytic Oxidation and Decomposition of Acetic acid over TiO2, TS-1 and Ti-MCM-41 Catalysts”, J.H Park, S.G. Kim, S.S. Park, S.S. Hong and G.D Lee, Materials Science forum Vols. 510-511(2006) PP34-37, [103]

Table 90: Conventional technology to destroy Hydrogen Peroxide

HYDROGEN PEROXIDE

Items to compare Conventional technology

Destruction technology Catalytic decomposition using Potassium Iodide Efficiency Amount of destruction

By Products O2, H2O Skilled Labor No Dangerous process Yes Automatic No PTOTMBD No PTODABD No Investment cost Low Running cost Low Working Area Small Number of Labor 1 Comments It’s a very cheap process ”Catalytic decomposition of Hydrogen Peroxide by Iodide”, [104]

Table 91: Conventional technology to destroy Sulfuric Acid

SULFURIC ACID

Items to compare Conventional technology

Destruction technology Catalytic thermal decomposition using catalysts Pd-Ag alloy and

Fe2O3 Efficiency Amount of destruction

By Products N2, H2SO4, SO3, SO2, O2, H2O Skilled Labor Yes Dangerous process Yes Automatic Yes PTOTMBD No

150

PTODABD Yes Investment cost High Running cost High Working Area Small Number of Labor 1 Comments ”Catalytic thermal decomposition of sulphuric acid in sulphur-iodine cycle for hydrogen production”, V.Barbarossa, S.Brutti, M.Diamanti, S.Sau, G. De Maria, International Journal of Hydrogen Energy 31 (2006) 883-890, [105]

Table 92: Conventional technology to destroy Nitric Acid esters

NITRIC ACID ESTERS

Items to compare Conventional technology

Destruction technology Thermal decomposition of explosive nitric acid esters in waste water effluents of the explosive industry Efficiency Amount of destruction By Products Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Investment cost Running cost Working Area Number of Labor Comments ”Process for the decomposition of explosive nitric acid esters dissolved in wastewaters”, Wilhelm Gresser, Klaus Schelhase, Heinz Frisch, Klaus Kaschel, Berent Reinecke, Wilelm, H.Trautmann, United States Patent, Patent number 5,011,614, [106]

Table 93: Conventional technology to destroy Acetic Acid Monomer and Dimer

ACETIC ACID MONOMER AND DIMER

Items to compare Conventional technology

Destruction technology Decomposition of acetic acid monomer and dimer on Ni(100) using temperature programmed reflection absorption infrared spectroscopy in concert with reflection absorption infrared spectroscopy Efficiency Amount of destruction

By Products CO2, H2 Skilled Labor Yes Dangerous process No Automatic Yes

151

PTOTMBD Yes PTODABD No Investment cost High Running cost High Working Area Small Number of Labor 1 Comments ”Acetic Acid Decomposition on Ni(100):Intermediate Adsorbate Structures by Reflection Infrared Spectroscopy”, Eric W. Scharpf and Jay B. Benziger, The Journal of Physical Chemistry, Vol.91, No.22, 1987, [107]

Table 94: Conventional technology to destroy Sulfuric Acid

SULFURIC ACID

Items to compare Conventional technology

Destruction technology Decomposition using gamma rays by the direct action of the radiation on the acid and for reactions of the acid with H and OH radicals produced by decomposition of water Efficiency Amount of destruction

By Products SO2 Skilled Labor Dangerous process Yes Automatic PTOTMBD Yes PTODABD No Investment cost Running cost Working Area Number of Labor

Comments SO2 was produced at a rate which increased with increasing acid concentration and decreased with increasing dose ”The Decomposition of Sulfuric Acid by cobalt gamma rays”, C.J. Hochanadel, J.A.Ghormley and t.J. Sworski, [108]

Table 95: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction technology Decomposition of acetic acid using a non-degradable organic compound, with in 120 mins of UV radiation under the initial concentration of 500 ppm. Hydrogen per oxide is used for oxidation Efficiency 100% Amount of destruction 500 ppm solution for 120 mins MUST BE L/min By Products

152

Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost Moderate Running cost Low Working Area Small Number of Labor 1 Comments Acetic acid was completely decomposed within 120 mins of UV radiation under the initial concentration of 500 ppm. Acetic acid

was efficiently decomposed with TiO2-UV-H2O2, Fe-H2O2-UV and UV-H2O2 except TiO2-UV system. UV-H2O2 reaction was the most efficient oxidation method ”Decomposition of acetic acid by advanced oxidation processes”, Ju Young Park and In Hwa Lee”, Korean J.Chem.Eng. 26(2), 387-391(2009), [109]

Table 96: Conventional technology to destroy Hydrogen Iodide

HYDROGEN IODIDE

Items to compare Conventional technology

Destruction technology Decomposition of hydrogen iodide at constant temperature Efficiency 11.26% Amount of destruction By Products Iodine, HI Skilled Labor Yes Dangerous process No Automatic No PTOTMBD Yes PTODABD No Investment cost Moderate as the entire apparatus was made of pyrex Running cost High as it’s a high temperature process Working Area Small Number of Labor 1 Comments ”The decomposition of Hydrogen Iodide”, H.Austin Taylor, J.Phys.Chem, 1928, 28(9), pp984-991, DOI: 10.1021/j150243a007, [110]

Table 97: Conventional technology to destroy Citric Acid

CITRIC ACID

Items to compare Conventional technology

Destruction technology Decomposition of citric acid using sulfuric acid as catalyst Efficiency 92-97%

153

Amount of destruction

By Products CO, H2O, acetone, dicarboxylic acid Skilled Labor No Dangerous process No Automatic No PTOTMBD Yes PTODABD Yes Investment cost Low Running cost Low Working Area Small Number of Labor 1 Comments ”The decomposition of citric acid by sulfuric acid”, Edwin O.Wiig, [111]

Table 98: Conventional technology to destroy Benzoic Acid

BENZOIC ACID

Items to compare Conventional technology

Destruction technology Thermal decomposition of benzoic acid and its derivatives containing (OH) and

(NH2) , (COOH) and (SO3H) to define the influence of chemical structure on their thermal decomposition Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process Automatic PTOTMBD PTODABD Investment cost High as DTA, TG and DTG are the requirement Running cost Low Working Area Large feasible for lab scale Number of Labor 1 Comments ”Studies on the thermal decomposition of benzoic acid and its derivatives”, M.Wesolowski and T.Konarski, Journal of Thermal Analysis and Calorimetry Vol.55 (1999) 995-1002, [112]

Table 99: Conventional technology to destroy Formic Acid

FORMIC ACID

Items to compare Conventional technology

Destruction technology The thermal decomposition of formic acid (HCOOH) adsorbed on Pd(100) surface Efficiency

154

Amount of destruction

By Products CO, CO2, H2 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD PTODABD Investment cost High Running cost High Working Area Large feasible for lab scale Number of Labor 1 Comments ”The decomposition of formic acid on Pd (100)”, D.Sander and W.Erley, J.Vac.Sci. Technol. A8(4), Jul/Aug 1990, [113]

Table 100: Conventional technology to destroy Formic Acid

FORMIC ACID

Items to compare Conventional technology

Destruction technology The adsorption and decomposition of formic acid (HCOOH) on Ni (111) surface Efficiency Amount of destruction

By Products CO2, H2, CO Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost High Working Area Large Number of Labor 1 Comments ”The adsorption and decomposition of formic acid on Ni (111): The identification of formic anhydride by vibrational spectroscopy”, W.Erley and D.Sander, J.Vac.Sci.Technol. A7 (3), May/Jun 1989, [114]

Table 101: Conventional technology to destroy Benzoic Acid

BENZOIC ACID

Items to compare Conventional technology

Destruction technology Anaerobic decomposition of Benzoic acid during methane fermentation. II. Fate of Carbons one and seven Efficiency Amount of destruction

155

By Products CO2, CH4 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD Yes PTODABD Yes Investment cost Running cost Low Working Area Number of Labor More than 1 Comments ”The Anaerobic Decomposition of Benzoic Acid During Methane Fermentation.II. Fate of Carbons One and Seven”, L.R.Fina and A:M.Fiskin, Archives of Biochemistry and Biophysics 91, 163-165, [115]

Table 102: Conventional technology to destroy Benzoic Acid

BENZOIC ACID

Items to compare Conventional technology

Destruction technology Anaerobic decomposition of benzoic acid during methane fermentation IV. Dearomatization of the ring and volatile fatty acid formed on ring rupture Efficiency Amount of destruction

By Products CO2, CH4 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD Yes PTODABD Yes Investment cost High Running cost Low Working Area Number of Labor More than 1 Comments ”The Anaerobic Decomposition of Benzoici Acid during Methane Fermentation IV.Dearomatization of the Ring andn Volatile Fatty acid Formed on Ring Rupture”, C.L.Keith, R.L.Bridges, L.R.Fina,K.L.Iverson, J.A.Cloran, Archives of Microbiology 118, 173- 176, [116]

Table 103: Conventional technology to destroy Hydrogen Iodide

HYDROGEN IODIDE

Items to compare Conventional technology

Destruction technology Catalytic decomposition of HI for IS thermo chemical cycle were performed at high temperatures (300-500 °C) using three kinds of

156

catalysts ; Pt/activated carbon, Pt/Alumina and only activated carbon Efficiency Amount of destruction By Products Hydrogen Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD Yes Investment cost High because of SEM, XRD, EDAX, BET analysis, gas chromatographer Running cost High Working Area Large Number of Labor 1 Comments HI conversion of all the tested catalysts increased with the increasing decomposition temperature and the HI conversion of platinum supported catalysts was higher than that of only activated carbon ”The catalytic decomposition of hydrogen iodide in the IS thermochemical cycle”, Chu-Sik Park, Jung-Min KIM, Kyoung-Soo Kang, Gab-Jin Hwang, Ki-Kwang Bae,WHEC 16/13-16 June 2006-Lyon France, [117]

Table 104: Conventional technology to destroy Yeast Nucleic Acid

YEAST NUCLEIC ACID

Items to compare Conventional technology

Destruction technology The decomposition of yeast nucleic acid by a heat-resistant enzyme Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic PTOTMBD Yes PTODABD Yes Investment cost Running cost Working Area Number of Labor 1 Comments ”The decomposition of yeast nucleic acid by a heat-resistant enzyme”, Rene J. Dubos and R.H.S Thompson, The Journal of Biological Chemistry, [118]

Table 105: Conventional technology to destroy Nitric Acid

NITRIC ACID

Items to compare Conventional technology

157

Destruction technology Thermal decomposition of nitric acid vapor in two glass cells of considerably different surface-to-volume ration from 100 to 465 °C Efficiency Amount of destruction

By Products NO2, water and oxygen Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD Yes PTODABD No Investment cost Moderate Running cost High Working Area Lab Scale Number of Labor 1 Comments ”The Kinetics of the Thermal Decomposition of Nitric Acid Vapor”, Harold S. Johnston, Louise Foering, Yu-sheng Tao and G.H. Messerly, J.Am.Chem.Soc, 1951, 73(5), pp2319-2321, DOI: 10.1021/ja01149a120, [119]

Table 106: Conventional technology to destroy Hydrogen Bromide

HYDROGEN BROMOIDE

Items to compare Conventional technology

Destruction technology The radiochemical formation of HBr and then it’s decomposition using ion pair yield for a stoichiometric mixture Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD Yes PTODABD Yes Investment cost High Running cost High Working Area Number of Labor 1 Comments ”The Radiochemical synthesis and decomposition of Hydrogen Bromide”, S.C.Lind and Robert Livingston, [120]

Table 107: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

158

Destruction technology Decomposition of acetic acid by making use of reliable molecular orbital methods Efficiency Amount of destruction By Products Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Investment cost Running cost Working Area Number of Labor Comments Ab Initio MO Calculations were used ”Theoretical Study of the Thermal Decomposition of Acetic Acid: Decarboxylation Versus Dehydration”, Minh Tho Nguyen, Debasis Sengupta, Grett Raspoet, Luc G. Vanquickenborne, J.Phys.Chem.1995,99,11883-11888, [121]

Table 108: Conventional technology to destroy Aqueous Chromic Acid

AQUEOUS CHROMIC ACID

Items to compare Conventional technology

Destruction technology Decomposition of aqueous chromic acid solutions in sulfuric acid solutions Efficiency Amount of destruction

By Products Chromium dioxide, HCrO2 Skilled Labor Yes Dangerous process Yes Automatic Yes PTOTMBD Yes PTODABD No but the vessel should be well prepared Investment cost High because of X-ray diffraction Running cost Moderate as the thermal decomposition temperature is 300-324 °C Working Area Number of Labor 1 Comments ”The Thermal Decomposition of Aqueous Chromic Acid and Some Properties of the Resulting Solid Phases”, B.J.Thamer, R.M.Douglass, E. Starizky, J.Am.Chem.Soc, 1957, 79(3), pp. 547-550, DOI: 10.1021/ja01560a013, [122]

Table 109: Conventional technology to destroy Hydrogen Chloride

HYDROGEN CHLORIDE

Items to compare Conventional technology

159

Destruction technology Thermal decomposition of HCl measured by ARAS and IR diode Laser Spectroscopy. ARAS stands for Atomic resonance absorption spectroscopy measurements Efficiency Amount of destruction By Products Hydrogen Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of atomic resonance absorption spectroscopy and infrared diode laser Running cost Very high as the operating temperature is 2500-4600 K Working Area Lab Scale Number of Labor 1 Comments ”Thermal Decomposition of HCl Measured by ARAS and IR Diode Laser Spectroscopy”, G.N.Schading and P.Roth, Combustion and Flame 99:467-474(1994), [123]

Table 110: Conventional technology to destroy Formic Acid

FORMIC ACID

Items to compare Conventional technology

Destruction Photo catalytic decomposition of formic acid under visible light irradiation technology over V-ion implanted TiO2 thin film photo catalysts prepared on quartz substrate by ionized cluster beam (ICB) deposition method Efficiency 100% Amount of destruction

By Products CO2, H2O Skilled Labor Yes Dangerous No process Automatic Yes PTOTMBD No PTODABD Yes Investment cost Very High Running cost High Working Area Large Number of Labor 1 Comments ”Photo catalytic decomposition of formic acid under visible light irradiation over V-ion implanted TiO2 thin film photo catalysts prepared on quartz substrate by ionized cluster beam (ICB) deposition method”, Jinkai Zhou, Masato Takeuchi, X.S.Zhao, Ajay K.Ray, Masakazu Anpo, Catalysis Letters Vol.106, Nos.1-2, January 2006, DOI: 10.1007/s10562-005-9192-5, [124]

160

3.2. Bases

Table 111: Conventional technology to destroy Sodium Bi Carbonate

SODIUM BI CARBONATE

Items to compare Conventional technology

Destruction technology Thermal decomposition of NaHCO3 under different atmospheres (dry nitrogen, air and CO2) with various heating rates Efficiency Amount of destruction

By Products CO2, H2O Skilled Labor No Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of TGA, DTG and milling cost Running cost Low Working Area Large Number of Labor 1 Comments With the reduction in the particle size of sodium bicarbonate, the decomposition reaction was accelerated ”A method of assessing solid state reactivity illustrated by thermal decomposition experiments on sodium bicarbonate”, Pavan K.Heda, David Dollimore, Kenneth S. Alexander, Dun chen, Emmeline Lae, Paul Bicknell, Thermochimica Acta 255(1995) 255-272, [125]

Table 112: Conventional technology to destroy Sodium Carbonate

SODIUM CARBONATE

Items to compare Conventional technology

Destruction technology Decomposition of Na2CO3 in temperature range of 25-1040 °C using different crucible materials and atmospheres Efficiency Amount of destruction By Products Skilled Labor No Dangerous process Automatic PTOTMBD Yes PTODABD Yes Investment cost Moderate Running cost High as the decomposition doesn’t occur below 800 °C

161

Working Area Number of Labor 1 Comments ”Drying and decomposition of Sodium Carbonate”, Arthur E. Newkirk and Ifigenia Aliferis, Analytical Chemistry Vol.30, No.5 May 1958, [126]

Table 113: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Thermal adsorption and decomposition of NH3 on Ni(110) surface by means of thermal desorption and high resolution electron energy loss (HREEL) spectroscopy in the temperature range of 110-500 K Efficiency Amount of destruction By Products NH+H Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of UHV chamber, LEED, AES, quadrupole mass spectrometer, rotatable single pass high resolution electron energy loss spectrometer Running cost High Working Area Large Number of Labor 1 Comments ”Adsorption and thermal decomposition of ammonia on a Ni (110) surface: isolation and identification of adsorbed NH2 and NH”, I.C.Bassignana, K.Wagemann J. Juppers and G.Ertl, Surface Science 175(1986) 22-44 North Holland, Amsterdam, [127]

Table 114: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Ammonia adsorption and decomposition on a Ni(110) surface Efficiency Amount of destruction By Products Surface nitrides are formed Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No

162

PTODABD Yes Investment cost High Running cost High Working Area Number of Labor 1

Comments Decomposition reaction of NH3 on Ni(110) resembles the pattern and efficiency found on an iron (110) single crystal ”Ammonia adsorption and decomposition on a Ni (110) surface”, M.Grunze, M. Golze, R.K.Driscoll, P.A. Dowben, J.Vac.Sci.Technol.18 (2), March 1981, [128]

Table 115: Conventional technology to destroy Barium Hydroxide

BARIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process Automatic PTOTMBD Yes PTODABD No Investment cost High because of DAT, TG, DTG, high temperature X-ray diffractometer, high temperature Raman Scattering Running cost Low Working Area Large Number of Labor 1 Comments ”Hydrates of Barium Hydroxide. Preparation, thermal decomposition and X-ray data”, H.D.Lutz, W.Eckers, H.Christan and B.Engelen, Thermochimica Acta, 44(1981) 337-343, [129]

Table 116: Conventional technology to destroy Potassium Hydroxide

POTASSIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Formation of KOH on Ag(111) and its conversion to carbonate studies through x-ray photo electron spectroscopy , ultraviolet photo electron spectroscopy, temperature programmed desorption Efficiency Amount of destruction By Products Skilled Labor Yes

163

Dangerous process No Automatic No PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Large Number of Labor 1

Comments Carbonate formation from KOH and CO2 is facile at 300 K but not at 100 K. K2CO3 is stable at 800 K and thermally decomposes to CO2, O2 and K ”Carbonate formation and decomposition on KOH/Ag(111) P.M. Blass, X.L. Zhou and J.M. White, J.VAC.Sci.Technol.A 7(3), May/Jun 1989, [130]

Table 117: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Catalytic decomposition of NH3 to produce hydrogen using different catalysts Efficiency 99% Amount of destruction By Products Hydrogen, Nitrogen Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Yes Investment cost Running cost Working Area Number of Labor Comments The absence of any undesirable by-products makes this process an ideal source of hydrogen for fuel cells ”Catalytic ammonia decomposition: Cox-free hydrogen production for fuel cell applications”, T.V.Choudhary, C. Sivadinarayana and D.W.Goodman, Catalysis Letters Vol.72, No.3-4, 2001, [131]

Table 118: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Catalytic decomposition of NH3 at low temperature in micro- fabricated reactors using ruthenium catalysts promoted with barium Efficiency

164

Amount of destruction By Products Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Yes Investment cost Running cost Working Area Number of Labor Comments ”Catalytic ammonia decomposition: miniaturized production of Cox-free hydrogen for fuel cells”, Rasmus Zink Sorensen, Laerke J.E. Nieslsen, Soren Jense, Ole Hansen, tue Johannessen, Ulrich Quaade, Claus Hvidd Christensen, Catalysis Communications 6 (2005) 229-232, [132]

Table 119: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Decomposition of NH3 with Ru catalysts using fly ash, whose enhanced surface area improves dispersion of Ru particles, resulting in higher catalytic activity Efficiency 94.60% Amount of destruction By Products Hydrogen Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of gas chromatographer, vertical fixed bed flow reactor, X-ray diffractometer, adsorption analyzer, X-ray photoelectron spectroscopy Running cost Moderate Working Area Large Number of Labor 1 Comments ”Catalytic decomposition of ammonia over fly ash supported Ru catalysts”, Li, Shaobin Wang, Zhonghua Zhu, Xiangdong Yao, Zifeng Yan, Fuel Processing Technology 89(2008) 1106-1112, [133]

Table 120: Conventional technology to destroy Ammonia

AMMONIA

165

Items to compare Conventional technology

Destruction technology Catalytic decomposition of NH3 using a cracking-cell filled with Al2O3 fiber using a quadrupole mass spectrometer Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate because of ultrahigh vacuum chamber, cracking cell, quadrupole mass spectrometer Running cost Moderate Working Area Large scale/Small Number of Labor 1

Comments NH3 decomposition rate increased with the increase of the cracking cell temperature until 500 °C and decreased above 500 °C ”Catalytic decomposition of ammonia gas using aluminum oxide for GaN formation”, Seikoh Yoshida and Masahiro Sasaki, Journal of Crystal Growth 135 (1994) 633-35, [134]

Table 121: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Catalytic decomposition of NH3 on heated W and Ru-coated W wires Efficiency Amount of destruction

By Products NH2, H Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of mass flow controller, cylindrical stainless steel reaction chamber, X-ray photo electron spectroscopy, YAG pumped dye laser, solar blind photomultiplier, oscilloscope, mass spectrometer Running cost Low Working Area Large Number of Labor 1 Comments Decomposition efficiency of both the wires was the same

166

Catalytic decomposition of NH3 on heated Ru and W surfaces”, Hironobu Umemoto, Yuta Kashiwagi, Kesiuke Ohdaira, Hiroyuki Kobayashi, Kanji Yasui, TSF-28821; doi:10.1016/j.tsf.2011.01.289, [135]

Table 122: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Catalytic decomposition of Ammonia over Nitrided MoNx/alpha-

Al2O3 and NiMoNy/alpha-Al2O3 catalysts Efficiency 98 – 99 % Amount of destruction

By Products NH3 Skilled Labor Yes Dangerous process Automatic PTOTMBD No PTODABD Yes Investment cost High Running cost Moderate Working Area Lab Scale Number of Labor 1 Comments In this paper, it is found that the nitride catalysts are very active for

NH3 decomposition and the conversion can be as high as 99.8% even at 650 °C which is far below the temp of commercial process ”Catalytic decomposition of Ammonia over Nitrided MoNx/alpha-Al2O3 and NiMoNy/alpha-Al2O3 catalysts”, Changhai Linag, Wenzhen Li, Zhaobin Wei,Qin Xin and Can Li, Ind.Eng.Chem.Res.2000,39,3694-3697, [136]

Table 123: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Catalytic decomposition of NH3 to nitrogen by selective oxidation over a bimetallic CuO/CeO2 nanoparticle catalyst at temp b/w 423- 673 K Efficiency 98% Amount of destruction

By Products NO, N2 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of SEM/EDS, BET surface are analyzer, ATR-FTIR

167

spectrometer, PSA, TEM Running cost Low Working Area Large but lab scale Number of Labor 1 Comments The processes involving catalysts for the decomposition are expensive mostly because of the cost required for catalyst preparation ”Catalytic decomposition of Ammonia over Bimetallic CuO/CeO2 Nanoparticle Catalyst”, Chang-Mao Hung, Hung, Aerosol and Air Quality Research, Vol.8, No.4, pp.447-458, [137]

Table 124: Conventional technology to destroy Aluminum Hydroxide and Magnesium Hydroxide

ALUMINUIM HYDROXIDE AND MAGNESIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition of Al(OH)3 and Mg(OH)2 to form Alumina and Magnesia at high tempt 973-1123 K Efficiency More than 95% Amount of destruction By Products Skilled Labor No but just for the analytical instruments Dangerous process No Automatic N/A PTOTMBD Yes PTODABD No Investment cost High but only x-ray diffractometer, Lindberg box furnace and thermogravimeteric analyzer were used Running cost High Working Area Large Number of Labor 1 Comments ”Chemical Kinetics and Reaction Mechanism of Thermal Decomposition of Aluminum Hydroxide and Magnesium Hydroxide at High Temperatures (973-1123)”, Lenwhei chen, Shuh-Kwei Hwang, Shyan Chen, Ind.Eng.Chem.Res.1989,28,738-742, [138]

Table 125: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Decomposition of NH3 to N2 over limestone to reduce NOx emission from fluidized bed combustors and effect of CO2 and H2O on product of NH3 decomposition over limestone Efficiency Amount of destruction

By Products NO, N2, N2O Skilled Labor

168

Dangerous process Automatic PTOTMBD No PTODABD No Investment cost Running cost High as it’s a high temperature process Working Area Number of Labor

Comments From NH2-CO2 mixture (NH2)2CO was formed though NH3 decomposition over both calcined and uncalcined limestone but from NH2-CO2-H2O mixture (NH2)2CO was not formed ”Decomposition of NH3 over calcined and uncalcined limestone under fluidized bed combustion conditions”, Tadaaki Shimizu, Eisuke Karahashi, Takuya Yamaguchi, Makoto Inagaki, Energy and Fuels 1995, 9, 962-965, [139]

Table 126: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Solid-catalyzed decomposition reaction of NH3 over quartz sand at 840-960 °C Efficiency Amount of destruction

By Products NH3, N2, H2, H2O Skilled Labor No Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate as the main investment costs are mass spectrometer and fluidized bed reactor Running cost Moderate, not low as it’s a high temperature process Working Area Small Number of Labor 1 Comments Fluidized bed technology is an economic and efficient method of burning a verity of fuels with low SO2 and NOx emissions ”Decomposition of NH3 over Quartz Sand at 840-960C”, D.A.Cooper and E.B. Ljungstrom, Energy and Fuels, Vol.2, No.5, 1988, [140]

Table 127: Conventional technology to destroy Sodium Bi Carbonate

SODIUM BI CARBONATE

Items to compare Conventional technology

Destruction technology Thermal decomposition of NaHCO3 in a closed system

169

Efficiency Amount of destruction

By Products Na2CO3, CO2, H2O Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost Low Working Area Lab Scale Number of Labor 1 Comments ”Differential thermal analysis of the decomposition of sodium bicarbonate and its simple double salts”, Edward M.Barrall, L.B.Rogers, J.Inorg.Nucl.Chem, 1966, Vol.28, pp.41 to 51, [141]

Table 128: Conventional technology to destroy Sodium Hydride

SODIUM HYDRIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition of sodium hydride (500 K-800 K) Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High Running cost Low Working Area Lab Scale Number of Labor 1 Comments ”DTA study of the kinetics of sodium hydride decomposition”,Jsubrt and K.tobola, Journal of Thermal Analysis Vol.10 (1976) 5- 12, [142]

Table 129: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Electrolytic decomposition characteristics of ammonia to nitrogen

at IrO2 anode Efficiency

170

Amount of destruction

By Products N2 Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Investment cost High Running cost Low Working Area Number of Labor 1 Comments ”Electrolytic decomposition characteristics of ammonia to nitrogen at IrO2 anode”, Kwang-Wook Kim, Young-Jun Kim, In-Tae Kim, Geun-II Park, Eil Hee Lee, [143]

Table 130: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Electrolytic decomposition of ammonia to nitrogen Efficiency 100% Amount of destruction By Products Nitrogen Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD Yes Investment cost Moderate Running cost Low Working Area Lab scale/small Number of Labor 1 Comments The electrolytic decomposition efficiency of ammonia is affected by the PH change of ammonia solution ”Electrolytic decomposition of ammonia to nitrogen in a multi-cell-stacked electrolyzer with a self-pH-adjustment function”, Kwang-Wook Kim, In-Tae Kim Geun-IL Park, Eil Hee Lee, Journal of Applied Electrochemistry (2006) 36: 1415-1426 DOI: 10.1007/s10800-006-92348, [144]

Table 131: Conventional technology to destroy Magnesium Hydroxide

MAGNESIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition at 300-600 °C

171

Efficiency Amount of destruction By Products Water, hydrogen, oxygen Skilled Labor No Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost High as it’s a high temperature process 1000 °C Working Area Large Number of Labor 1 Comments ”Hydrogen Release during the Thermal Decomposition of Magnesium Hydroxide to Magnesium Oxide”, R.Martens, H.Gentsch and F.Freund, Journal of Catalysis 44, 366-372 (1976), [145]

Table 132: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Photo decomposition of NH3 using Pt-TiO2 as a photo catalyst Efficiency 21.60% Amount of destruction

By Products H2, N2 Skilled Labor Yes Dangerous process Automatic PTOTMBD No PTODABD Yes Investment cost High Running cost Low Working Area Lab Scale Number of Labor 1 Comments ”Photodecomposition of ammonia to dinitrogen and dihydrogen on platinized TiO2 nanoparticles in an aqueous solution”, Junichi Nemoto, Norihiko Gokan, Hirohito Ueno, Masao Kaneko, Journal of Photochemistry and Photobiology A: Chemistry 185(2007) 295-300, [146]

Table 133: Conventional technology to destroy Magnesium Hydroxide

MAGNESIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology The decomposition of Mg(OH)2 in an electron microscope Efficiency

172

Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost No Working Area Large but lab scale Number of Labor 1 Comments ”The Decomposition of Magnesium Hydroxide in an Electron Microscope”, J.F.Goodman, Proceeding of the Royal Society of London. Series A, Mathematical and Physical Sciences, Vol.247, No.1250 (Sep.30, 1958), pp.346-352, [147]

Table 134: Conventional technology to destroy Sodium Carbonate

SODIUM CARBONATE

Items to compare Conventional technology

Destruction technology Thermal decomposition of Na2CO3 by effusion method Efficiency Amount of destruction

By Products CO2 Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD PTODABD Investment cost High Running cost High as it’s a high temperature process Working Area Number of Labor Comments The experiment conducted were not accurate ”The thermal decomposition of sodium carbonate by the effusion method” Ketil Motzfeldt, J.Phys.Chem, 1955, 59(2), pp. 139- 147, DOI: 10.1021/j150524a0II, [148]

Table 135: Conventional technology to destroy Lithium Hydroxide

LITHIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition of LiOH at 500-1300 K Efficiency Amount of destruction By Products

173

Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of laser induced fluorescence method and quadrupolemass spectrometery, TG, DTA Running cost High because of its high temperature 500-1300 K Working Area Lab Scale Number of Labor 1 Comments ”Gas-Phase Hydroxyl Radical Emission in the Thermal Decomposition of Lithium Hydroxide”, Suguru Noda, Masateru Nishioka Masayoshi Sadakata, J.Phys.Chem.B 1999, 103, 1954-1959, [149]

Table 136: Conventional technology to destroy Calcium Hydroxide

CALCIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition of Ca(OH)2 by depositing Ca(OH)2 particles on substrate Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes as the solution is made PTODABD No Investment cost High because of DSC, DTA, X-ray diffractometer, SEM Running cost Low Working Area Large Number of Labor 1 Comments ”Thermal decomposition of calcium hydroxide deposited on the substrate”, Y.Sawada, Y.Ito, Thermochimica Acta, 232(1994) 47- 54, [150]

Table 137: Conventional technology to destroy Strontium Hydroxide

STRONTIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition of Sr(OH)2 Efficiency Amount of destruction

By Products H2O

174

Skilled Labor Yes Dangerous process Yes as it is done in open air Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of X-ray diffraction Spectroscopy Running cost High as it’s a high temperature process (700 °C) Working Area Lab scale large Number of Labor 1 Comments ”Thermal decomposition of strontium hydroxide”, R.Dinescu and M.Preda, Journal of Thermal Analysis, Vo.5 (1973) 465-473, [151]

Table 138: Conventional technology to destroy Sodium Hydroxide

SODIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal dissociation of NaOH upon evacuation at varied temperatures Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Running cost High as it’s a high temperature process 750-1023 K Working Area Number of Labor 1 Comments ”Thermal dissociation of Sodium Hydroxide upon Evacuation”, V.P.Yurkiniskii, E.G.Firsova, S.A.Proskura, Russian Journal of Applied Chemistry, Vol. 78 No.3 2005, pp.360-362, [152]

Table 139: Conventional technology to destroy Barium Hydroxide

BARIUM HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition at 400-600 °C Efficiency Amount of destruction By Products BaO Skilled Labor Yes specially because of analytical instruments

175

Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of DTA, X-ray diffraction, TGA Running cost High because of high temp Working Area Large Number of Labor 1 Comments ”Thermal decomposition of the hydrates of Barium Hydroxide”, G.M.Habashy and G.A. Kolta, J.Inorg, Nucl.Chem, 1972, Vol.34, pp. 57-67, [153]

Table 140: Conventional technology to destroy Sodium Bi Carbonate

SODIUM BI CARBONATE

Items to compare Conventional technology

Destruction technology Thermal decomposition of NaHCO3 by DTA Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost High but not as other as only DTA is required Running cost Working Area Lab Scale Small Number of Labor 1 Comments The decomposition of sodium bicarbonate was studied at different particle sizes and different heating rates ”Thermal decomposition kinetics of sodium bicarbonate by differential thermal analysis”, K.S. Subramanian, T.P. Radhakrishnan and A.K. Sundaram, Journal of Thermal Analysis, Vol.4 (1972), 89-93, [154]

Table 141: Conventional technology to destroy Nickel Hydroxide

NICKLE HYDROXIDE

Items to compare Conventional technology

Destruction technology Thermal decomposition mechanism of Ni(OH)2 determined using X- ray diffraction and thermal analysis Efficiency Amount of destruction

By Products H2O Skilled Labor Yes

176

Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of X-ray diffraction and thermogravimeteric analysis Running cost High because of high temp Working Area Large Number of Labor 1 Comments ”X-ray Diffraction Studies on the thermal decomposition Mechanism of Nickel Hydroxide”, Thimmasandra Narayan Ramesh, J.Physc.Chem.B 2009, 113, 13014-13017, [155]

Table 142: Conventional technology to destroy Sodium Carbonate

SODIUM CARBONATE

Items to compare Conventional technology

Destruction technology Thermal decomposition of Na2CO3 Efficiency Amount of destruction

By Products NaOH, CO2 Skilled Labor Yes Dangerous process No but it can become because of autoclave Automatic Yes PTOTMBD Yes as the solution is made PTODABD No Investment cost Moderate Running cost Moderate Working Area Large but associated with the size of autoclave Number of Labor 1 Comments Conversion rate decreased as sodium carbonate concentration decreased at the same steaming rate and temperature ”Thermal decomposition of sodium carbonate solutions”, Authur M.Thomas.Jr., J.Chem.Eng.Data, 1963, 8(1), pp51-54, DOI: 10.1021/je60016a014, [156]

Table 143: Conventional technology to destroy Calcium Carbonate

CALCIUM CARBONATE

Items to compare Conventional technology

Destruction technology Thermal decomposition of CaCO3 using analytical and instrumental techniques to produce CaO Efficiency Amount of destruction

By Products CaO, CO2

177

Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of TGA, MS, XRD, SEM Running cost High Working Area Large Number of Labor 1 Comments ”Thermal Decomposition and Solid Characterization of Calcium Oxide in Limestone Calcination”, B.D. soares, C.E.Hori, C.E.A Batista, H.M.Henriuqe, Materials Science Forum vols. 591-593 (2008) pp. 352-357, doi: 10.4028/22.scientific.net/MSF.591.593.352, [157]

Table 144: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology The decomposition of ammonia with wavelength of 2025-2140 Angstrom Efficiency Amount of destruction

By Products N2 (4%), H2 (96%) Skilled Labor Yes Dangerous process No as long as the safety measures are ensured Automatic Yes PTOTMBD Yes PTODABD No Investment cost High Running cost Low Working Area Lab Scale Number of Labor 1 Comments ”The Photochemical decomposition of Ammonia”, Edwin O.Wiig, G.B.Kistiakowsky, J.Am.Chem.Soc, 1932, 54(5), pp. 1806-1820, DOI: 10.1021/ja01344a012, [158]

Table 145: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology The mercury photosensitized decomposition of NH3 and NH3- propane mixtures Efficiency Amount of destruction

178

By Products H2, N2, CH4 Skilled Labor Dangerous process Automatic PTOTMBD PTODABD Investment cost Moderate Running cost Low Working Area Lab Scale/Small Number of Labor 1 Comments ”The Mercury Photosensitized decomposition of ammonia and ammonia-propane mixtures”, S.Takamuku and R.A.Back, Canadian Journal of Chemistry, Volume 42(1964), [159]

Table 146: Conventional technology to destroy Ammonia

AMMONIA

Items to compare Conventional technology

Destruction technology Thermal decomposition of NH3 using Mo as catalyst Efficiency Amount of destruction

By Products Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD Yes PTODABD No Investment cost Moderate Running cost High as 1097-1228 K is operating temperature Working Area Small Number of Labor More than 1 Comments ”The thermal decomposition of ammonia upon the surface of a molybdenum wire”, Robert E.Burk, Proc Natl Acad Sci USA 1972 February, 13 (2): 67-74, [160]

3.3. Organic Solvents

Table 147: Conventional technology to destroy Acetic Acid Monomer and DIMER

ACETIC ACID MONOMER and DIMER

Items to compare Conventional technology

Destruction technology Decomposition of acetic acid monomer and dimer on Ni(100)

179

using temperature programmed reflection absorption infrared spectroscopy Efficiency Amount of destruction

By Products CO, CO2, H2, C(ad), O(ad) Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes PTODABD No Investment cost High because of temperature programmed reactor (TPR), mass analyzer, TPRAIS, RAIS, Auger electron spectroscopy Running cost High as it involves high temperatures Working Area Lab Scale Large Number of Labor 1 Comments ”Acetic Acid Decomposition on Ni (100): Intermediate Adsorbate Structures by Reflection Infrared Spectroscopy”, Eric W. Scharpf and Jay B. Benziger, J.Phys. Chem, 1987, 91(22), pp. 5531-5534 DOI: 10.1021/j100306a005, [161]

Table 148: Conventional technology to destroy CH3OH

CH3OH

Items to compare Conventional technology

Destruction technology Adsorption and thermal decomposition of CH3OH on clean polycrystalline Al Efficiency Amount of destruction

By Products CH4, CO, CO2, H2 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes as Al was heated upto 900 K as well as cleaning Investment cost High because of electron spectrometer, UPS, XPS, He resonance lamp, quadrupole mass spectrometer Running cost Moderate Working Area Lab Scale Large Number of Labor 1 Comments Decomposition starts after 630 K ”Adsorption and decomposition of methanol on aluminium”, J.W.Rogers, Jr. and J.M. White, J.Vac.Sci. Technol, Vol.16, No.2. Mar/Apr.1979, [162]

Table 149: Conventional technology to destroy Primary Alcohols and 1-Propanol

PRIMARY ALCOHOLS and 1-PROPANOL

180

Items to compare Conventional technology

Destruction technology Adsorption and thermal decomposition of 1-Propanol and other primary alcohols on the Si(100) surface Efficiency Amount of destruction By Products Aldehydes Skilled Labor Yes Dangerous process No but it can become if high vacuum chamber is not operated properly Automatic Yes PTOTMBD Yes PTODABD Yes Investment cost High due to AES, TDA, Ultra high vacuum chamber (UHV), quadrupole mass spectrometer Running cost High Working Area Lab Scale Large Number of Labor 1 Comments ”Adsorption and thermal decomposition Chemistry of 1-Propanol and other primary alcohols on the Si (100) Surface”, Linhu Zhang, April J. Carman, Sean M. Casey, J.Physc. Chem. B2003, 107, 8424-8432, [163]

Table 150: Conventional technology to destroy Triethylamine Alane

TRIETHYLAMINE ALANE

Items to compare Conventional technology

Destruction technology Triethylamine alane decomposes on Al(111) single crystal surface at temperatures above 310 K Efficiency Amount of destruction By Products Hydrogen, Triethylamine Skilled Labor Dangerous process Automatic PTOTMBD Yes PTODABD Yes Investment cost High because of auger electron spectroscopy Running cost Low as it’s a low temperature process Working Area Number of Labor Comments ”Aluminum thin film growth by the thermal decomposition of triethylamine alane”, Lawrence H.Dubois, Bernard R. Zegarski, Mihal E. Gross and Ralph G. Nuzzo, Surface Science 244(1991) 89-95, [164]

181

Table 151: Conventional technology to destroy Methanol

METHANOL

Items to compare Conventional technology

Destruction technology Decomposition of Methanol over a series of bimetallic Pt-M catalysts with M=Au,Pd,Ru,Fe Efficiency Amount of destruction

By Products PtO, PtO2 Skilled Labor Yes Dangerous process No Automatic Not completely PTOTMBD No PTODABD Yes Investment cost High because of XPS, AFM, TEM, Mass spectrometery, Packed-bed mass flow reactor Running cost High Working Area Large Number of Labor 1 Comments ”Bimetallic Pt-Metal catalysts for the decomposition of methanol: Effect of secondary metal on the oxidation state, activity and selectivity of Pt”, Jason R.Croy, S.Mostafa, L.Hickman, H.Heinrich, B.Roldan Cuenya, Applied Catalysis A: General 350(2008) 207- 216, [165]

Table 152: Conventional technology to destroy Ethanol

ETHANOL

Items to compare Conventional technology

Destruction Catalytic decomposition of ethanol on V2O5/AlPO4 catalysts technology Efficiency More than 97% Amount of destruction By Products Ethene Skilled Labor Yes Dangerous process No Automatic Not completely PTOTMBD Yes PTODABD Yes Investment cost High because of TG, DTG, DSC, X-ray diffraction Running cost High because of temp (500 °C) Working Area Large Number of Labor 1 Comments The higher degree of conversion of ethanol to ethane for the samples

182

containing V2O5 may not only be due to the optimum ration of V4+/V5+ but also due to the value of the activation energy of charge carriers ”Catalytic decomposition of ethanol on V2O5/AlPO4 catalysts”, Abd El-Aziz A Said, Kamal MS Khalil, J Chem Technol Biotechnol 75: 196-204 (2000), [166]

Table 153: Conventional technology to destroy Isopropanol

ISOPROPANOL

Items to compare Conventional technology

Destruction technology Decomposition of isopropanol by heteropolyanion-doped polyanilines Efficiency Amount of destruction By Products Acetone, propene Skilled Labor Dangerous process Automatic PTOTMBD Yes as it was diluted with Nitrogen PTODABD Yes Investment cost Running cost Working Area Number of Labor Comments ”Catalytic decomposition of isopropanol over polyaniline doped by heteropolyanions”, W.Turek, M. Lapkowski, G. Bidan, Materials Science Forum Vol.122 (1993) pp.65-76, [167]

Table 154: Conventional technology to destroy Methanol

METHANOL

Items to compare Conventional technology

Destruction Decomposition of methanol over single and different bimetallic exchange technology combinations of Co, Cr, Cu and Zeolite Beta using a fixed-bed catalytic reactor in temp range of 100-500 °C Efficiency 90% over 350 °C Amount of destruction

By Products CO2, CO Skilled Labor Yes Dangerous process No but care is required to deal with compressor Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of BET, compressor, gas chromatographer, reactor

183

Running cost Moderate Working Area Small Number of Labor 1 Comments 100% conversion over 450 °C ”Catalytic decomposition of methanol in air over different combinations of bimetallic exchanged H-Bea Zeolite with Cobalt, chromium and Copper”, Ahmad Zuhairi Abdullah, Mohamad Zailani Abu Bakar and Subhash Bhatia, Journal of Industrial Technology 11 (2), 2002, 47-55, [168]

Table 155: Conventional technology to destroy Methylene chloride

METHYLENE CHLORIDE

Items to compare Conventional technology

Destruction technology Catalytic decomposition of methylene chloride in air with a concentration of 959 ppm and 160-275 °C with three different sulfated oxide catalysts Efficiency 100% using sulfated Titanium dioxide catalyst Amount of destruction

By Products HCl, CO, CO2 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High because of fixed bed reactor, mass flow controller, gas chromatographer, thermogravimeteric analyzer Running cost Very high Working Area Lab Scale Large Number of Labor 1 Comments ”Catalytic decomposition of methylene chloride by sulfated oxide catalysts”, Xuan-Zhen Jiang, Li-Qing Zhang, Xiao-Hua Wu, Lei Zheng, Applied Catalysis B: Environmental 9(1996) 229-237, [169]

Table 156: Conventional technology to destroy Methylene chloride

METHYLENE CHLORIDE

Items to compare Conventional technology

Destruction Decomposition of methylene chloride using chromium oxide catalysts technology with the help of TGA and XPS Efficiency Amount of destruction

By Products HCl, CO, CO2 Skilled Labor Yes Dangerous No

184 process Automatic No PTOTMBD No PTODABD Yes Investment cost High because of XPS, TGA, BET, TPD, fixed bed reactor Running cost High as prolonged heating at high temperature Working Area Lab Scale Large Number of Labor 1 Comments ”Catalytic decomposition of methylene chloride on oxidative carbon supported metal oxide catalysts 2. Chromium oxide catalyst”, Min Kang, Min Woo song and Chang Ha Lee, React. Kinet.Catal. Lett. Vol.80, No.1, 131-138, [170]

Table 157: Conventional technology to destroy Methylene Chloride

METHYLENE CHLORIDE

Items to compare Conventional technology

Destruction Decomposition of methylene chloride using Cobalt oxide catalysts with technology the help of BET, XRD, TGA Efficiency Amount of destruction

By Products HCl, CO, CO2 Skilled Labor Yes Dangerous No process Automatic No PTOTMBD No PTODABD Yes Investment cost High because of BET, XRD, TGA, chromatographers Running cost High as prolonged heating at high temp Working Area Lab Scale Large Number of Labor 1 Comments ”Catalytic decomposition of methylene chloride on oxidative carbon supported metal oxide catalysts 1. Cobalt Oxide Catalyst”, Min Kang, Min Woo song and Chang Ha Lee, React. Kinet. Catal. Lett. Vol.80, No.1, 123-129, [171]

Table 158: Conventional technology to destroy N-Heptane

N-HEPTANE

Items to compare Conventional technology

Destruction technology Catalytic decomposition of n-heptane for the growth of high quality single wall carbon nanotubes Efficiency Amount of destruction

185

By Products Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High as it is used TEM, spectrometer Running cost High as it involves high temperatures Working Area Lab Scale Large Number of Labor 1 Comments ”Catalytic decomposition of n-heptane for the growth of high quality single wall carbon nanotubes”, D. Grimm, A.Gruneis, C. Kramberger, M.Rummeli, T.Gemming, B.Buchner, M.Rummeli, T.Gemming, B.Buchner, A.Barreiro, H.Juzmany, R.Pfeiffer, T.Pichler, Chemical Physics Letter 428 (2006) 416-420, [172]

Table 159: Conventional technology to destroy Toulene

TOULENE

Items to compare Conventional technology

Destruction technology Catalytic decomposition of toluene using various dielectric Barrier Discharge Reactors Efficiency 95% Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost Moderate Working Area Small Number of Labor 1 Comments Use of in-plasma catalysis were more helpful to enhance the destruction and removal efficiency and reducing the O3 formation than that of either post-plasma catalysis or plasma alone ”Catalytic decomposition of toulene using various dielectric Barrier Discharge Reactors”, YE Daiqi, Huang Haibao, Chen Weili, Zeng Ronghui, Plasma Science and Technology, Vol.10, No.1, Feb 2008, [173]

Table 160: Conventional technology to destroy Methanol

METHANOL

Items to compare Conventional technology

Destruction technology Decomposition of methanol at 250 °C using nickel-silica composites

186

prepared by sol gel method Efficiency 64.10% Amount of destruction

By Products CO, H2, CH4, H2O Skilled Labor Yes but just for analytical equipments Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of XRD, BET, chromatographer Running cost High because of high temp (400 °C for 5 hours) Working Area Lab Scale Large Number of Labor 1 Comments ”Catalytic methanol decomposition to carbon monoxide and hydrogen over Ni/SiO2 of high nickel content”, Yasuyuki Matsumura, Naoki Tode, Tetsuo Yazawa, Masatake Haruta, Journal of Molecular Catalysis A: Chemical 99(1995) 183-185, [174]

Table 161: Conventional technology to destroy Propylene Carbonate

PROPYLENE CARBONATE

Items to compare Conventional technology

Destruction technology Decomposition of propylene carbonate at graphite electrode in 1 M

LiClO4 employing a variety of transient electrochemical techniques Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process Yes Automatic No PTOTMBD No PTODABD Yes Investment cost Moderate Running cost Low Working Area Small Number of Labor 1 Comments ”Cathodic Decomposition of Propylene Carbonate at Graphite Electrodes2, Tiehua Piao, Chil Hon Doh, Sung In Moon and Su- Moon Park, Battery Conference on Applications and Advances, 1997, Twelfth Annual, DOI: 10.1109/BCAA.1997.574113, [175]

Table 162: Conventional technology to destroy N-Propyl amine, Diethylamide and Triethylamine

N-PROPYLAMINE,DIETHYLAMINE AND TRIETHYLAMINE

Items to compare Conventional technology

Destruction technology Decomposition over ZrO2, SiO2-Al2O3 and MgO studied by temperature

187

programmed desorption and catalytic conversion Efficiency 95.8% for n-propyl amine, 63.5% for diethyl amine, 88% for triethylamine Amount of destruction By Products Acetonitrile Skilled Labor Yes Dangerous process No Automatic No PTOTMBD Yes PTODABD Yes Investment cost High because of XRD, BET, spectrometer, gas chromatographer Running cost High as catalyst preparation demands 873 K for 24 hours Working Area Large Number of Labor 1 Comments ”Characteristic Action of Zirconium Dioxide in the Decomposition of Alkyl amines”, B.Q XU, T.Yamaguchi and K.Tanabe, Applied Catalysis, 64(1990) 41-54, [176]

Table 163: Conventional technology to destroy Benzene and Toulene

BENZENE AND TOULENE

Items to compare Conventional technology

Destruction technology Decomposition of Benzene, toluene and particulate condensed matter by

the use of thermally excited holes in TiO2 at high temperatures Efficiency 100% Amount of destruction

By Products H2O and CO2 at 350 °C Skilled Labor Yes Dangerous process No but it can become if autoclave is not used properly Automatic Yes PTOTMBD Yes PTODABD Yes Investment cost High because of autoclave, DSC, TGa, spectrophotometer, spectrometer Running cost Moderate Working Area Lab Scale Large Number of Labor 1 Comments ”Complete decomposition of Benzene, Toulene and Particulate Matter Contained in the exhaust of diesel engines by means of thermally excited holes in Titanium Dioxide at high temperatures”, Takashi Makino, Keiji Matsumoto, Toru Ebara, Takashi Mine, Takumi Ohtsuka and Jin Mizuguchi, Japanese Journal of Applied Physics Vol.46, No.9A, 2007, pp.6037-6042, [177]

Table 164: Conventional technology to destroy Toulene

TOULENE

Items to compare Conventional technology

188

Destruction Decomposition of toluene using UV light from plasma and an external UV technology lamp in a dielectric barrier discharge plasma/UV system, as well as in a plasma/photo catalysis system Efficiency 73% Amount of destruction

By Products CO, CO2, benzene, toluene Skilled Labor Yes Dangerous process Yes Automatic Yes PTOTMBD Yes PTODABD Yes Investment cost High because of plasma reactor, gas chromatographer, spectrometer Running cost Moderate Working Area Lab Scale Large Number of Labor 1 Comments UV light from DBD reactor was very weak. Introduction of external UV light to the plasma significantly improves the removal efficiency of toluene by 20% ”Contribution of UV light to the decomposition of toulene in dielectric barrier discharge plasma/photo catalysis system”, Hai Bao Huang, Dai Qi Ye, Ming Li Fu, Fa Da Feng, Plasma Chem Plasma Process (2007) 25:577-588, DOI: 10.1007/s11090-007-9085-z, [178]

Table 165: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction technology Acetic acid efficiently decomposed within 120 mins of UV radiation and with

different oxidation processes such as TiO2-UV-H2O2,Fe-H2O2-UV,UV-H2O2 and TiO2-UV Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No but laser safety precautions should be ensured Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate Running cost Low Working Area Lab Scale Small Number of Labor 1

Comments Decomposition efficiency of acetic acid was fastest in the UV-H2O2 process ”Decomposition of acetic acid by advanced oxidation processes”, Ju Young Park and In Hwa Lee”, Korean J.Chem.Eng. 26(2), 387-391 (2009), [179]

189

Table 166: Conventional technology to destroy Acetone

ACETONE

Items to compare Conventional technology

Destruction technology Photo catalytic decomposition UV/TiO2 of gaseous acetone with a fixed- bed annular reactor using TiO2 as the photo catalyst at room temperature Efficiency Amount of destruction

By Products CO2, H2O Skilled Labor Yes Dangerous process No but laser safety precautions should be ensured Automatic Yes PTOTMBD No PTODABD No Investment cost High because of BET, FESEM, flow meter, flow controller, mass flow meter Running cost Low Working Area Lab Scale Large Number of Labor 1 Comments In this study, the direct photolysis of acetone in air stream by 365 nm UV irradiation was studied and the decomposition of acetone was found to be negligible. Decomposition was increased by increasing UV Intensity “Decomposition of gaseous acetone in an annular photo reactor coated with TiO2 thin film”, Young Ku, Kun-Yu Tseng and Wen- Yu Wang, Water, Air and Soil Pollution, Volume 168, Numbers 1-4, 313-323, DOI:10,1007/s11270-005-1778-4, [180]

Table 167: Conventional technology to destroy Methanol

METHANOL

Items to compare Conventional technology

Destruction technology Plasma decomposition of methanol using AC and DC corona discharges at ambient condition Efficiency 80% Amount of destruction

By Products H2, CO, CO2 Skilled Labor Yes Dangerous process Safer than other technologies Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate Running cost Cheap Working Area Lab Scale Number of Labor 1

190

Comments A major advantage of methanol decomposition using corona discharge is that only a very small discharge space is enough for sufficiently high decomposition ”Novel Plasma Methanol Decomposition to Hydrogen Using Corona Discharges”, Hui-qing Li, Ji-jun Zou, Yue-ping Zhang, Chang- jun Liu, Chemistry Letters Vol.33, No. 6(2004), [181]

Table 168: Conventional technology to destroy Isopropanol

ISOPROPANOL

Items to compare Conventional technology

Destruction technology Decomposition of isopropanol over V2O5 using UV-visible photo irradiation Efficiency Amount of destruction

By Products Propene, H2O Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost Low Working Area Lab Scale Large Number of Labor 1 Comments ”Photo enhanced catalytic decomposition of isopropanol on V2O5”, A.Z.Moshfegh and A.lgnatiev, Catalysis Letters 4 (1990) 113- 122, [182]

Table 169: Conventional technology to destroy Toulene

TOULENE

Items to compare Conventional technology

Destruction technology Photo catalytic decomposition of toluene over TiO2 nanoparticles embedded on activated carbon Efficiency 98% Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High

191

Running cost Low Working Area Lab Scale Large Number of Labor 1 Comments ”Photocatalytic decomposition of gaseous toulene by TiO2 nanoparticles coated on activated carbon”, A.Rezaee, Gh.H.Pourtaghi, A.Khavanin, R.Sarraf Mamoory, M.T. Ghaneian, H.Godini, Iran.J.Environ.Helath.Sci.Eng,.2008,Vol.5,No.4,pp.305-310, [183]

Table 170: Conventional technology to destroy Methyl Tert-Butyl Ether

METHYL TERT-BUTYL ETHER

Items to compare Conventional technology

Destruction technology Photo catalytic decomposition of methyl tert-butyl ether in

aqueous slurry of TiO2 particles irradiated with Xe Lamp in a batch reactor Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD Yes as the solution is made PTODABD No Investment cost Moderate Running cost Low Working Area Lab Scale Small Number of Labor 1 Comments ”Photo catalytic decomposition of methyl tert-butyl ether in aqueous slurry of titanium dioxide”, Yujing Zhang, Ramin Farnood, Applied Catalysis B: Environmental 57(2005) 275-282, [184]

Table 171: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction technology Decomposition of acetic acid photo catalytically on TiO2 in an inert atmosphere by two parallel pathways at room temperature Efficiency Amount of destruction

By Products CO2, C2H6, CH4, H2O Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No

192

PTODABD No Investment cost High Running cost High Working Area Small Number of Labor 1 Comments ”Photo catalytic decomposition of acetic acid on TiO2”, Darrin S. Muggli, Sarah A.Keyser and John L.Falconer, Catalysis Letters 55(1998) 129-132, [185]

Table 172: Conventional technology to destroy Acetic Acid

ACETIC ACID

Items to compare Conventional technology

Destruction technology Decomposition of acetic acid using UV light and thin films of TiO2 and TiO2/SiO2 Efficiency Amount of destruction

By Products H2O, CO2 Skilled Labor Yes Dangerous process No Automatic No PTOTMBD No PTODABD Yes Investment cost High Running cost High Working Area Large Number of Labor 1

Comments TiO2/SiO2 thin film having a pure-anatase phase showed a higher photo catalytically activity than did the pure-anatase SiO2 ”Photo catalysis decomposition of acetic acid over TiO2 and TiO2/SiO2 thin films prepared by the Sol Gel Method”, Man Sig Lee, Ju Dong Lee and Seong Soo Hong, J.Ind.Eng.Chem.Vol 11, No.4, (2005) 459-501, [186]

Table 173: Conventional technology to destroy Formic Acid

FORMIC ACID

Items to compare Conventional technology

Destruction technology Decomposition of formic acid photo catalytically by V-ions

implantation into TiO2 thin film Efficiency 100% Amount of destruction

By Products CO2, H2O Skilled Labor Yes Dangerous process No Automatic Yes

193

PTOTMBD No PTODABD Yes Investment cost Very high because of XRD, UV-vis, XPS, FE-SEM, AFM, Spectrometer Running cost High Working Area Large Number of Labor 1 Comments ”Photo catalytic decomposition of formic acid under visible light irradiation over V-ion implanted TiO2 thin film photo catalysts prepared on quartz substrated by ionized cluster beam(ICB) deposition method”, Jinkai Zhou, Masato Takeuchi, X.S.Zhao, Ajay K.Ray, Masakazu Anpo, Catalysis Letters Vol.106, Nos.1-2, January 2006, DOI: 10.1007/s10562-005-91921-5, [187]

Table 174: Conventional technology to destroy Toulene

TOULENE

Items to compare Conventional technology

Destruction technology Photo catalytic decomposition of toluene over TiO2 film, prepared by sol-gel method and coated on porous nickel Efficiency Yes Amount of destruction By Products Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost Low Working Area Small Number of Labor 1 Comments Toulene can be decomposed effectively by this method ”Photo catalytic decomposition of toulene by TiO2 filmed as photo catalyst”, Xiaodong Duan, Dezhi Sun, Zhibin Zhu, Xiangqun Chen, Pengfei Shi, J.Environ.Sci.Helath, A37(4), 679-692(2002) , [188]

Table 175: Conventional technology to destroy LaTi(O,N)3

LaTi(O,N)3

Items to compare Conventional technology

Destruction technology Photo catalytic activity of LaTi(O,N)3 nanoparticles for the gas phase decomposition of acetone under visible light Efficiency Amount of destruction

By Products CO2, H2O Skilled Labor Yes

194

Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High because of XRD, TEM, BET, UV-V spectroscopy Running cost High as catalyst preparation is very expensive Working Area Large Number of Labor 1 Comments Catalyst preparation is very expensive in this experiment ”Photo catalytic decomposition of acetone using LaTi(O,N)3 nanoparticles under visible light irradiation”, Rosiana Aguiar, Andreas Kalytta, Armin Reller, Anke Weidenkaff, Stefan G. Ebbinghaus, Journal of Materials Chemistry, DOI: 10.1039/b806794e, [189]

Table 176: Conventional technology to destroy Benzene

BENZENE

Items to compare Conventional technology

Destruction technology Photo catalytic decomposition of benzene over TiO2 in the gas phase at room temperature using a fixed bed flow reactor in a humified airstream Efficiency 100% Amount of destruction

By Products CO2, CO, benzene, phenol Skilled Labor Yes Dangerous process No but can become if cylinders are not safe Automatic Yes PTOTMBD Yes as the reaction gas was made PTODABD Yes as it was pre-heated Investment cost Moderate Running cost Moderate Working Area Lab Scale/Small Number of Labor 1 Comments ”Photo catalytic decomposition of benzene over TiO2 in a humified airstream”, Hiahiro Einaga, Shigeru Fuamura and Takaashi Ibusuki, Chem.Chem.Phys.1999, 1, 4903-4908, [190]

Table 177: Conventional technology to destroy HCCl3

HCCl3

Items to compare Conventional technology

Destruction technology Photo catalytic decomposition of HCCl3 in a fully irradiated photo reactor by varying the concentrations of chloroform, dissolved oxygen, titania, the local volumetric rate of energy absorption using titanium oxide particulate suspensions

195

Efficiency Amount of destruction By Products Skilled Labor Yes Dangerous process Automatic No PTOTMBD No PTODABD No Investment cost Moderate Running cost Moderate Working Area Small Number of Labor 1 Comments ”Photo catalytic decomposition of chloroform in a fully irradiated heterogeneous photo reactor using titanium oxide particulate suspensions”, Carlos A.Martin, Miguel A.Baltanas, Alberto E.Cassano, Catalysis Today 27(1996) 221-227, [191]

Table 178: Conventional technology to destroy Gas Acetone

GAS ACETONE

Items to compare Conventional technology

Destruction technology Gas acetone was decomposed in an annular photo reactor coated

with TiO2 or Pt/TiO2 catalysts using a UV or a fluorescent lamp as light source Efficiency 90% Amount of destruction

By Products CO2 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD High Investment cost Low Running cost Lab Scale Large Working Area 1 Number of Labor Almost complete decomposition and mineralization of gaseous acetone were accomplished for experiments conducted with higher UV light intensities Comments ”Photocatalyic decomposition of gaseous acetone using TiO2 and Pt/TiO2 catalysts”, Young Ku, Kun-Yu Tseng, Chih-Ming Ma, International Journal of Chemical Kinetics-INT J CHEM KINET, Vol 40, no.4, pp.209-216, [192]

Table 179: Conventional technology to destroy Ftetrachloroethylene

FTETRACHLOROETHYLENE

Items to compare Conventional technology

196

Destruction Gas phase photo catalytic destruction of tetrachloroethylene by using technology an in situ photo catalytic reactor with FT-IR analysis in batch mode,

using TiO2 as catalyst Efficiency Amount of destruction

By Products CO2, COCl2(phosgene) Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No but just preheating Investment cost Moderate Running cost Low Working Area Small Number of Labor 1 Comments ”Photo catalytic decomposition of tetrachloro-ethylene in the gas phase with titanium dioxide as catalyst”, Marta Hegedus, Andras Dombi and Imre Kiricsi, React. Kinet.Catal.Lett.Vol.74, No.2, 209-215(2001), [193]

Table 180: Conventional technology to destroy Acetic Acid5

ACETIC ACID

Items to compare Conventional technology

Destruction technology Photo catalytic oxidation and decomposition of acetic acid over TiO2, TS-1 and Ti-MCM-41 catalysts Efficiency Amount of destruction

By Products CO2, CH4, C2H6 for P-25 TiO2, CO2, CH4 for TS-1 and Ti-MCM-41 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD Yes Investment cost High Running cost Moderate Working Area Large Number of Labor 1 Comments ”Photo catalytic oxidation and decomposition of acetic acid over TiO2, TS-1 and Ti-MCM-41 catalysts”, J.H.Park, S.G. Kim, S.S. Park, S.S. Hong and G.D. Lee, Materials Science Forum Vols. 510-511(2006) pp. 34-37, [194]

Table 181: Conventional technology to destroy Diethyl Ketone

DIETHYL KETONE

197

Items to compare Conventional technology

Destruction technology Decomposition of diethyl ketone by IR-laser and comparing

with SiF4-sensitized decomposition of diethyl ketone and n- butane Efficiency 100% Amount of destruction

By Products CO, H2, CH4, C2H6, C2H4, C3H8, C2H2, C3H6, C4H10 Skilled Labor Yes Dangerous process No Automatic Yes PTOTMBD No PTODABD No Investment cost Moderate Running cost High as it’s high temperature process Working Area Small Number of Labor 1 Comments ”IR Laser-Induced decomposition of diethyl ketone and n-butane”, W. Braun, J.R. Mcnesby and M.J. Pilling, Journal of Photochemistry, 17 (1981) 281-295, [195]

Table 182: Conventional technology to destroy Ethanol

ETHANOL

Items to compare Conventional technology

Destruction technology Infrared multiphoton absorption and decomposition of ethanol vapor Efficiency Amount of destruction

By Products H2O, C2H4 through other channels, CH3CHO, C2H6, CH4, C2H2 Skilled Labor Yes Dangerous process No Automatic PTOTMBD Yes PTODABD No Investment cost Moderate Running cost High as it’s a high temperature process Working Area Small Number of Labor 1 Comments ”Infrared multiphoton adsorption and decomposition of ethanol vapour”, R.A. Back, D.K. Evans, Robert D.Mcalpine, E.M. Verpoorte, Mike Ivanco, J.W. Goodale, H.M.Adams, Can.J.Chem.66,857 (1988) , [196]

198

4. Liquids

4.1 Sulfuric Acid, H2SO4

Energy required to decompose H2SO4 [197] is demonstrated using Hess’s Law

Eqn1 H2S (g) + 2O2 (g) → H2SO4 (l) ΔH= -235.5 kJ

Eqn2 H2S (g) + 2O2 (g) → SO3 (g) + H2O (l) ΔH= -207 kJ

Eqn3 H2O (l) → H2O (g) ΔH= 44 kJ

Reverse Eqn1=> H2SO4 (l) → H2S (g) + 2O2 (g) ΔH= 235.5 kJ

Eqn2=> H2S (g) + 2O2 (g) → SO3 (g) + H2O (l) ΔH= -207 kJ

Eqn3=> H2O (l) → H2O (g) ΔH= 44 kJ

H2SO4 (l) → SO3 (g) + H2O (g) ΔH= 72 kJ/mol [197]

4.2 Nitric Acid, HNO3

Energy required to decompose HNO3 [201] is demonstrated using Hess’s Law

Eqn1 2N2 (g) + 5O2 (g) → 2N2O5 (g) ΔH= 6.8 kcal/mol

Eqn2 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -136.6 kcal/mol

Eqn3 N2O5 (g) + H2O (l) → 2HNO3 (l) ΔH= -18.3 kcal/mol

Eqn1=> 2N2 (g) + 5O2 (g) → 2N2O5 (g) ΔH= 6.8 kcal/mol

Eqn2=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -136.6 kcal/mol

Eqn3 x 2=> 2N2O5 (g) + 2H2O (l) → 4HNO3 (l) ΔH= -36.6 kcal/mol

2H2 (g) + 2N2 (g) + 6O2 (g) → 4HNO3 (l) ΔH= -166.4 kcal/mol

HNO3 (l) → 1/2H2 (g) + 1/2N2 (g) + 3/2O2 (g) ΔH= 174 kJ/mol [201]

199

4.3 Acetic Acid, CH3COOH

Energy required to decompose CH3COOH [202] is demonstrated using Hess’s Law

Eqn1 CH3COOH (l) + 2O2 (g) → 2CO2 (g) + 2H2O (l) ΔH= -875 kJ/mol

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Reverse Eqn1=>2CO2 (g) + 2H2O (l) → CH3COOH (l) + 2O2 (g) ΔH= 875 kJ/mol

Eqn2 x 2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -789.02 kJ/mol

Eqn3 x2=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.6 kJ/mol

2C (s) + 2H2 (g) + O2 (g) → CH3COOH (l) ΔH= -485 kJ/mol

CH3COOH (l) → 2C (s) + 2H2 (g) + O2 (g) ΔH= 485 kJ/mol [202]

4.4 Hydrochloric Acid, HCl

Energy required to decompose HCl [203] is demonstrated using Hess’s Law

Eqn1 NH3 (g) + HCl (g) → NH4Cl (s) ΔH= -176 kJ

Eqn2 N2 (g) + 3H2 (g) → 2NH3 (g) ΔH= -92.2 kJ

Eqn3 N2 (g) + 4H2 (g) + Cl2 (g) → 2NH4Cl (s) ΔH= -628.86 kJ

Reverse Eqn1 x 2=> 2NH4Cl (s) → 2NH3 (g) + 2HCl (g) ΔH= 352 kJ

Reverse Eqn2=> 2NH3 (g) → N2 (g) + 3H2 (g) ΔH= 92.2 kJ

Eqn3=> N2 (g) + 4H2 (g) + Cl2 (g) → 2NH4Cl (s) ΔH= -628.86 kJ

H2 (g) + Cl2 (g) → 2HCl (g) ΔH= -184.66 kJ

HCl (g) → 1/2H2 (g) + 1/2Cl2 (g) ΔH= 92.33 kJ/mol [203]

200

4.5 Hydrogen Bromide, HBr

Energy required to decompose HBr [204] is demonstrated using Hess’s Law

Eqn1 2C + 2H2 → C2H4 ΔH= 52.2 kJ/mol

Eqn2 C2H4 + HBr → C2H5Br ΔH= -106.3 kJ/mol

Eqn3 2C + 5/2H2 + 1/2Br2 → C2H5Br ΔH= -90.5 kJ

Reverse Eqn2=> C2H5Br → C2H4 + HBr ΔH= 106.3 kJ/mol

Eqn3=> 2C + 5/2H2 + 1/2Br2 → C2H5Br ΔH= -90.5 kJ

Reverse Eqn1=> C2H4 → 2C + 2H2 ΔH= -52.3 kJ/mol

1/2H2 + 1/2Br2 → HBr (l) ΔH= -36.4 kJ/mol

HBr (l) → 1/2H2 + 1/2Br2 ΔH= 36.4 kJ/mol [204]

4.6 Hydrogen Iodide, HI

Energy required to decompose HI [205] is demonstrated using Hess’s Law

Eqn1 I2 (g) → I2 (s) ΔH= -124.8 kJ

Eqn2 3I2 (g) + 3H2 (g) → 6HI (g) ΔH= -219 kJ

Eqn2/3=> I2 (g) + H2 (g) → 2HI (g) ΔH= -73 kJ

Reverse Eqn1=> I2 (s) → I2 (g) ΔH= 124.8 kJ

H2 (g) + I2 (g) → 2HI (g) ΔH= 51.8 kJ

HI (g) → 1/2H2 (g) + 1/2I2 (s) ΔH= -26 kJ/mol [205]

201

4.7 Boric Acid, H3BO3

Energy required to decompose H3BO3 [206] is demonstrated using Hess’s Law

Eqn1 H3BO3 (aq) → HBO2 (aq) + H2O (l) ΔH= -.02 kJ

Eqn2 H2B4O7 (aq) + H2O (l) → 4HBO2 (aq) ΔH= -11.3 kJ

Eqn3 H2B4O7 (aq) → 2B2O3 (s) + H2O (l) ΔH= 17.5 kJ

Reverse Eqn1 x 4=> 4HBO2 (aq) + 4H2O (l) → 4H3BO3 (aq) ΔH= .02 kJ

Reverse Eqn3=> 2B2O3 (s) + H2O (l) → H2B4O7 (aq) ΔH= -17.5 kJ

Eqn2=> H2B4O7 (aq) + H2O (l) → 4HBO2 (aq) ΔH= -11.3 kJ

2B2O3 (s) + 6H2O (l) → 4H3BO3 (aq) ΔH= -28.78 kJ

H3BO3 (aq) → 1/2B2O3 (s) + 3/2H2O (l) ΔH= 7.195 kJ/mol [206]

4.8 Oxalic Acid, C2H2O4

Energy required to decompose C2H2O4 [207] is demonstrated using Hess’s Law

Eqn1 C2H2O4 (s) + 1/2O2 (g) → 2CO2 (g) + H2O (l) ΔH= -822.2 kJ/mol

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Reverse Eqn1=>2CO2 (g) + H2O (l) → C2H2O4 (s) + 1/2O2 (g) ΔH= 822.2 kJ/mol

Eqn2 x 2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -789.02 kJ/mol

Eqn3=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

2C (s) + H2 (g) + 2O2 (g) → C2H2O4 (s) ΔH= -252.62 kJ/mol

C2H2O4 (s) → 2C (s) + H2 (g) + 2O2 (g) ΔH= 252.62 kJ/mol [207]

202

4.9 Formic Acid, HCOOH

Energy required to decompose HCOOH [208] is demonstrated using Hess’s Law

Eqn1 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn3 HCOOH (l) + 1/2O2 (g) → CO2 (g) + H2O (l) ΔH= -275 kJ

Reverse Eqn3=>CO2 (g) + H2O (l) → HCOOH (l) + 1/2O2 (g) ΔH= 275 kJ

Eqn1=> C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

C (s) + O2 (g) + H2 (g) → HCOOH (l) ΔH= -405.31 kJ/mol

HCOOH (l) → C (s) + O2 (g) + H2 (g) ΔH= 405.31 kJ/mol [208]

4.10 Citric Acid, C6H8O7

Energy required to decompose C6H8O7 [209] is demonstrated using Hess’s Law

Eqn1 C6H8O7 (s) + 9/2O2 (g) → 6CO2 (g) + 4H2O (g) ΔH= -1950 kJ/mol

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (g) ΔH= -241.8 kJ/mol

Reverse Eqn1=>6CO2 (g) + 4H2O (g) → C6H8O7 (s) + 9/2O2 (g) ΔH= 1950 kJ/mol

Eqn2 x 6=> 6C (s) + 6O2 (g) → 6CO2 (g) ΔH= -2367 kJ/mol

Eqn3 x 4=> 4H2 (g) + 2O2 (g) → 4H2O (g) ΔH= -967.2 kJ/mol

6C (s) + 4H2 (g) + 7/2O2 (g) → C6H8O7 (s) ΔH= -1384 kJ/mol

C6H8O7 (s) → 6C (s) + 4H2 (g) + 7/2O2 (g) ΔH= 1384 kJ/mol [209]

203

4.11 Benzoic Acid, C7H6O2

Energy required to decompose C7H6O2 [207] is demonstrated using Hess’s Law

Eqn1 C7H6O2 (s) + 15/2O2 (g) → 7CO2 (g) + 3H2O (l) ΔH= -3226.9 kJ/mol

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1=> C7H6O2 (s) + 15/2O2 (g) → 7CO2 (g) + 3H2O (l) ΔH= -3226.9 kJ/mol

Reverse Eqn2 x 7=> 7CO2 (g) → 7C (s) + 7O2 (g) ΔH= 2754.57 kJ/mol

Reverse Eqn2 x 3=> 3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.4 kJ/mol

C7H6O2 (s) → 7C (s) + 3H2 (g) + O2 (g) ΔH= 385.07 kJ/mol [207]

4.12 Hydrogen Peroxide, H2O2

Energy required to decompose H2O2 [210] is demonstrated using Hess’s Law

Eqn1 H2O2 (l) → H2O (l) + 1/2O2 (g) ΔH= -98.2 kJ/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Reverse Eqn1=> H2O (l) + 1/2O2 (g) → H2O2 (l) ΔH= 98.2 kJ/mol

Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

H2 (g) + O2 (g) → H2O2 (l) ΔH= -187.6 kJ/mol

H2O2 (l) → H2 (g) + O2 (g) ΔH= 187.6 kJ/mol [210]

204

4.13 Ammonia, NH3

Energy required to decompose NH3 [211] is demonstrated using Hess’s Law

Eqn1 2CH4 (g) → 2C (s) + 4H2 (g) ΔH= 149.8 kJ

Eqn2 H2 (g) + 2C (s) + N2 (g) → 2HCN (g) ΔH= 270.3 kJ

Eqn3 CH4 (g) + NH3 (g) → HCN (g) + 3H2 (g) ΔH= 255.95 kJ

Reverse Eqn3 x 2=>2HCN (g) + 6H2 (g) → 2CH4 (g) + 2NH3 (g) ΔH= -511.9 kJ

Eqn1=> 2CH4 (g) → 2C (s) + 4H2 (g) ΔH= 149.8 kJ

Eqn2=> H2 (g) + 2C (s) + N2 (g) → 2HCN (g) ΔH= 270.3 kJ

N2 (g) + 3H2 (g) → 2NH (g) ΔH= -92.1 kJ

NH3 (g) → 1/2N2 (g) + 3/2H2 (g) ΔH= 46.05 kJ/mol [211]

4.14 Calcium Hydroxide, Ca(OH)2

Energy required to decompose Ca (OH) 2[212] is demonstrated using Hess’s Law

Eqn1 CaO (s) + H2O (l) → Ca(OH)2 (s) ΔH= -15.260 kcal/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -68.370 kcal/mol

Eqn3 Ca (s) + 1/2O2 (g) → CaO (s) ΔH= -151.8 kcal/mol

Eqn1=> CaO (s) + H2O (l) → Ca(OH)2 (s) ΔH= -15.260 kcal/mol

Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -68.370 kcal/mol

Eqn3=> Ca (s) + 1/2O2 (g) → CaO (s) ΔH= -151.8 kcal/mol

Ca (s) + O2 (g) + H2 (g) → Ca(OH)2 (s) ΔH= -235.43 kcal/mol= -985 kJ/mol

Ca(OH)2 (s) → Ca (s) + O2 (g) + H2 (g) ΔH= 985 kJ/mol [212]

205

4.15 Calcium Oxide, CaO

Energy required to decompose CaO[212] is demonstrated using Hess’s Law

Eqn1 CaO (s) + H2O (l) → Ca (OH) 2 (s) ΔH= -15.260 kcal/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -68.370 kcal/mol

Eqn3 Ca (s) + O2 (g) + H2 (g) → Ca (OH) 2 (s) ΔH= -235.43 kcal/mol

Reverse Eqn1=> Ca(OH)2 (s) → CaO (s) + H2O (l) ΔH= 15.260 kcal/mol

Eqn3=> Ca (s) + O2 (g) + H2 (g) → Ca(OH)2 (s) ΔH= -235.43 kcal/mol

Reverse Eqn2=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 68.370 kcal/mol

Ca (s) + 1/2O2 (g) → CaO (s) ΔH= -151.8 kcal/mol

CaO (s) → Ca (s) + 1/2O2 (g) ΔH= 635 kJ/mol [212]

4.16 Sodium Bicarbonate, NaHCO3

Energy required to decompose NaHCO3 [213] is demonstrated using Hess’s Law

Eqn1 NaHCO3 (s) → Na (s) + 1/2H2 (g) + C (s) + 3/2O2 (g) ΔH= 950.81 kJ/mol

Eqn2 2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol

Eqn3 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol

Eqn4 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1 x 2=> 2NaHCO3 (s) → 2Na (s) + H2 (g) + 2C (s) + 3O2 (g) ΔH= 1901.62 kJ/mol

Eqn2=> 2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol

Eqn3=> C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol

Eqn4=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

206

2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ [213]

4.17 Sodium bicarbonate, NaHCO3

Energy required to decompose NaHCO3[213] is demonstrated using Hess’s Law

Eqn1 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol

Eqn2 2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol

Eqn3 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol

Eqn4 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1=> 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol

Reverse Eqn2=> Na2CO3 (s) → 2Na (s) + C (s) + 3/2O2 (g) ΔH= 1130.68 kJ/mol

Reverse Eqn3=> CO2 (g) → C (s) + O2 (g) ΔH= 393.5 kJ/mol

Reverse Eqn4=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 285.8 kJ/mol

2NaHCO3 (s) → 2Na (s) + 2C (s) + H2 (g) + 3O2 (g) ΔH= 1901.61 kJ

NaHCO3(s) → Na (s) + C (s) + 1/2H2 (g) + 3/2O2 (g) ΔH= 950.8 kJ/mol [213]

4.18 Sodium Carbonate, Na2CO3

Energy required to decompose Na2CO3 [213] is demonstrated using Hess’s Law

Eqn1 NaHCO3 (s) → Na (s) + 1/2H2 (g) + C (s) + 3/2O2 (g) ΔH= 950.81 kJ/mol

Eqn2 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol

Eqn3 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol

Eqn4 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

207

Reverse Eqn1 x 2=>2Na (s) + H2 (g) + 2C (s) + 3O2 (g) → 2NaHCO3(s) ΔH= -1901.62 kJ/mol

Eqn2=> 2NaHCO3 (s) → Na2CO3 (s) + CO2 (g) + H2O (l) ΔH= 91.63 kJ/2mol

Reverse Eqn3=> CO2 (g) → C (s) + O2 (g) ΔH= 393.5 kJ/mol

Reverse Eqn4=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 285.8 kJ/mol

2Na (s) + C (s) + 3/2O2 (g) → Na2CO3 (s) ΔH= -1130.68 kJ/mol

Na2CO3 (s) → 2Na (s) + C (s) + 3/2O2 (g) ΔH= 1130.68 kJ/mol [213]

Lattice Dissociation Energy

The energy required when one mole of a solid ionic compound is converted into its constituents gaseous ions, measured under standard conditions of temperature and pressure. [214]

Enthalpy of Hydration

The energy released when one mole of gaseous ions dissolved in excess water, measured under standard conditions of temperature and pressure. [214]

Enthalpy of Solution

The energy changed which occurs when one mole of a substance dissolves in excess water, measured under standard conditions of temperature and pressure. [214]

4.19 Barium Hydroxide, Ba(OH)2, Born Haber cycle

Energy required to decompose Ba(OH)2 [215] is demonstrated using Born Haber Cycle

ΔHsolution = ΔH hydration - ΔHlattice

2+ - ΔHsolution = ΔHhydration of Ba + ΔHhydration of OH - Lattice dissociation energy

ΔHsolution = (-1360)+ 2(-460)-(-1768)

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ΔHsolution = -512kJ/mol [215]

Ba(OH)2 Lattice Energy Ba2+(g) + 2OH-(g)

ΔHsolution

ΔHhydration

Ba2+(aq) + 2OH-(aq)

Energy= Plank’s Constant x Frequency

4.20 Strontium Hydroxide, Sr(OH)2

Energy required to decompose Sr(OH)2 [215] is demonstrated using Born Haber Cycle

ΔHsolution = ΔH hydration - ΔHlattice

2+ - ΔHsolution = ΔHhydration of Sr + ΔHhydration of OH - Lattice dissociation energy

ΔHsolution = -1480 + 2(-460) - (-1894)

ΔHsolution = -506kJ/mol [215]

209

Sr(OH)2 Lattice Energy Sr2+(g) + 2OH-(g)

ΔHsolution

ΔHhydration

Sr2+(aq) + 2OH-(aq)

Energy= Plank’s Constant x Frequency

4.21 Aluminum Hydroxide, Al(OH)3

Energy required to decompose Al (OH) 3 [216] is demonstrated using Hess’s Law

Eqn1 Al2O3 (s) + 3H2O (g) → 2Al (OH) 3 (s) ΔH= -149 kJ/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (g) ΔH= -241.6 kJ/mol

Eqn3 2Al (s) + 3/2O2 (g) → Al2O3 (s) ΔH= -1676 kJ/mol

Eqn1=> Al2O3 (s) + 3H2O (g) → 2Al (OH) 3 (s) ΔH= -149 kJ/mol

Eqn2 x 3=> 3H2 (g) + 3/2O2 (g) → 3H2O (g) ΔH= -724.8 kJ/mol

Eqn3=> 2Al (s) + 3/2O2 (g) → Al2O3 (s) ΔH= -1676 kJ/mol

210

2Al (s) + 3H2 (g) + 3O2 (g) → 2Al (OH) 3 (s) ΔH= -2549.8 kJ/mol

Al (OH) 3 (s) → Al (s) + 3/2H2 (g) + 3/2O2 (g) ΔH= 1274.9 kJ/mol [216]

4.22 Sodium Hydride, NaH

Energy required to decompose NaH [217] is demonstrated using Hess’s Law

Eqn1 4H2 (g) + 2O2 (g) → 4H2O (l) ΔH= -1144 kJ

Eqn2 2NaO2 (s) → 2Na (s) + 2O2 (g) ΔH= 274 kJ

Eqn3 2NaO2 (s) + 5H2 (g) → 2NaH (s) + 4H2O (l) ΔH= -1026 kJ

Eqn3=> 2NaO2 (s) + 5H2 (g) → 2NaH (s) + 4H2O (l) ΔH= -1026 kJ

Reverse Eqn2=>2Na (s) + 2O2 (g) → 2NaO2 (s) ΔH= -274 kJ

Reverse Eqn1=> 4H2O (l) → 4H2 (g) + 2O2 (g) ΔH= 1144 kJ

2Na (s) + H2 (g) → 2NaH (s) ΔH= -156 kJ

NaH (s) → Na (s) + 1/2H2 (g) ΔH= 78 kJ/mol [217]

4.23 Sodium Hydride, NaH

Energy required to decompose NaH [218] is demonstrated using Hess’s Law

Eqn1 SbH3 (s) + 3NaOH (s) → Sb (OH) 3 (s) + 3NaH (aq) ΔH= -22.8 kJ

Eqn2 3H2 (g) + 2Sb (s) → 2SbH3 (s) ΔH= -655 kJ

Eqn3 Sb (OH) 3 (s) + 3Na (s) → Sb (s) + 3NaOH (s) ΔH= 32.6 kJ

Reverse Eqn1 x 2 =>6NaH (aq) + 2Sb (OH) 3 (s) → 6NaOH (s) + 2SbH3 (s) ΔH= 45.6 kJ

Reverse Eqn3 x 2=>6NaOH (s) + 2Sb (s) → 6Na (s) + 2Sb (OH) 3 (s) ΔH= -65.2 kJ

Reverse Eqn2=> 2SbH3 (s) → 3H2 (g) + 2Sb (s) ΔH= 655 kJ

211

6NaH (aq) → 6Na (s) + 3H2 (g) ΔH= 635.4 kJ

NaH (aq) → Na (s) + 1/2H2 (g) ΔH= 105.9 kJ/mol [218]

4.24 Potassium Hydroxide, KOH

Energy required to decompose KOH [214] is demonstrated using Hess’s Law

Eqn1 KOH (aq) + HCl (aq) → KCl (aq) + H2O (l) ΔH= -57.3 kJ/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -286 kJ/mol

Eqn3 1/2H2 (g) + 1/2Cl2 (g) +aq → HCl (aq) ΔH= -164 kJ/mol

Eqn4 KCl (s) + aq → KCl (aq) ΔH= 18 kJ/mol

Eqn5 K (s) + 1/2Cl2 (g) + aq → KCl (s) ΔH= -440.3 kJ/mol

Reverse Eqn1=>KCl (aq) + H2O (l) → KOH (aq) + HCl (aq) ΔH= 57.3 kJ/mol

Reverse Eqn3=>HCl (aq) → 1/2H2 (g) + 1/2Cl2 (g) +aq ΔH= 164 kJ/mol

Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -286 kJ/mol

Eqn4=> KCl (s) + aq → KCl (aq) ΔH= 18 kJ/mol

Eqn5=> K (s) + 1/2Cl2 (g) + aq → KCl (s) ΔH= -440.3 kJ/mol

1/2H2 (g) + 1/2O2 (g) + K (s) → KOH (aq) ΔH= -487 kJ/mol

KOH (aq) → 1/2H2 (g) + 1/2O2 (g) + K (s) ΔH= 487 kJ/mol [214]

4.25 Lithium Hydroxide, LiOH

Energy required to decompose LiOH [201] is demonstrated using Hess’s Law

Eqn1 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -286 kJ

Eqn2 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.33 kJ

Eqn3 LiOH (aq) + HCl (aq) → LiCl (aq) + H2O (l) ΔH= 760.83 kJ

212

Eqn4 LiOH (aq) → LiOH (s) ΔH= 19 kJ

Eqn5 LiCl (s) → LiCl (aq) ΔH= -36 kJ

Eqn6 Li (s) + 1/2Cl2 (g) → LiCl (s) ΔH= 407.5 kJ

Eqn7 HCl (aq) → HCl (g) ΔH= 75 kJ

Reverse Eqn4=> LiOH (s) → LiOH (aq) ΔH= -19 kJ

Eqn3=> LiOH (aq) + HCl (aq) → LiCl (aq) + H2O (l) ΔH= 760.83 kJ

Reverse Eqn7=> HCl (g) → HCl (aq) ΔH= -75 kJ

Eqn2=> 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.33 kJ

Reverse Eqn5=> LiCl (aq) → LiCl (s) ΔH= 36 kJ

Reverse Eqn6=> LiCl (s) → Li (s) + 1/2Cl2 (g) ΔH= -407.5 kJ

Reverse Eqn1=> H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 286 kJ

LiOH (s) → 1/2H2 (g) + 1/2O2 (g) + Li (s) ΔH= 485 kJ/mol [201]

4.26 Magnesium Hydroxide, Mg (OH) 2

Energy required to decompose Mg (OH) 2 [219] is demonstrated using Hess’s Law

Eqn1 2Mg (s) + O2 (g) → 2MgO (s) ΔH= -1203.6 kJ

Eqn2 Mg (OH) 2 (s) → MgO (s) + H2O (l) ΔH= 37.1 kJ

Eqn3 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.7 kJ

Reverse Eqn2 x 2 => 2MgO (s) + 2H2O (l) → 2Mg (OH) 2 (s) ΔH= -74.2 kJ

Eqn1=> 2Mg (s) + O2 (g) → 2MgO (s) ΔH= -1203.6 kJ

Eqn3=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.7 kJ

2Mg (s) + 2H2 (g) + 2O2 (g) → 2Mg (OH) 2 (s) ΔH= -1849.5 kJ

Mg (s) + H2 (g) + O2 (g) → Mg (OH) 2 (s) ΔH= -924.75 kJ/mol

213

Mg (OH) 2 (s) → Mg (s) + H2 (g) + O2 (g) ΔH= 924.75 kJ/mol [219]

4.27 Sodium Hydroxide, NaOH

Energy required to decompose NaOH [201,220,214]] is demonstrated using Hess’s Law

Eqn1 NaOH (aq) + HCl (aq) → H2O (l) + NaCl (aq) ΔH= -57.3 kJ/mol

Eqn2 H2O (l) → H2 (g) + 1/2O2 (g) ΔH= 285.8 kJ/mol

Eqn3 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.3 kJ/mol

Eqn4 HCl (g) → HCl (aq) ΔH= -75 kJ/mol

Eqn6 NaCl (aq) → NaCl (s) ΔH= -25.2 kJ/mol

Eqn7 NaOH (s) → NaOH (aq) ΔH= -43.22 kJ/mol

Eqn8 Na (s) + 1/2Cl2 (g) →NaCl (s) ΔH= -433.15 kJ/mol

Reverse Eqn7=> NaOH (aq) → NaOH (s) ΔH= 43.22 kJ/mol

Reverse Eqn1=> H2O (l) + NaCl (aq) → NaOH (aq) + HCl (aq) ΔH= 57.3 kJ/mol

Reverse Eqn6=> NaCl (s) → NaCl (aq) ΔH= 25.2 kJ/mol

Eqn8=> Na (s) + 1/2Cl2 (g) →NaCl (s) ΔH= -433.15 kJ/mol

Reverse Eqn4=> HCl (aq) → HCl (g) ΔH= 75 kJ/mol

Reverse Eqn3=> HCl (g) → 1/2H2 (g) + 1/2Cl2 (g) ΔH= 92.3 kJ/mol

Reverse Eqn2=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Na (s) + 1/2H2 (g) + 1/2O2 (g) → NaOH (s) ΔH= -425.13 kJ/mol

NaOH (s) → Na (s) + 1/2H2 (g) + 1/2O2 (g) ΔH= 425.13 kJ/mol [201,220,214]

214

4.28 Ethanol, C2H5OH

Energy required to decompose C2H5OH [221, 214] is demonstrated using Hess’s Law

Eqn1 C2H5OH (l) + 3O2 (g) → 2CO2 (g) + 3H2O (l) ΔH= -1371 kJ/mol

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Reverse Eqn1=>2CO2 (g) + 3H2O (l) → C2H5OH (l) + 3O2 (g) ΔH= 1371 kJ/mol

Eqn2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -789.02 kJ/mol

Eqn3 x 3=> 3H2 (g) + 3/2O2 (g) → 3H2O (l) ΔH= -857.4 kJ/mol

3H2 (g) + 2C (s) + 1/2O2 (g) → C2H5OH (l) ΔH= -275.42 kJ/mol

C2H5OH (l) → 3H2 (g) + 2C (s) + 1/2O2 (g) ΔH= 275.42 kJ/mol [221, 214]

4.29 Methanol, CH3OH

Energy required to decompose CH3OH [222] is demonstrated using Hess’s Law

Eqn1 CH3OH (l) + 3/2O2 (g) → CO2 (g) + 2H2O (l) ΔH= -726 kJ/mol

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Reverse Eqn1=>CO2 (g) + 2H2O (l) → CH3OH (l) + 3/2O2 (g) ΔH= 726 kJ/mol

Eqn2=> C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 x 2=> 2H2 (g) + O2 (g) → 2H2O (l) ΔH= -571.6 kJ/mol

2H2 (g) + C (s) + 1/2O2 (g) → CH3OH (l) ΔH= -240 kJ/mol

CH3OH (l) → 2H2 (g) + C (s) + 1/2O2 (g) ΔH= 240 kJ/mol [222]

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4.30 Propanol, C3H7OH

Energy required to decompose C3H7OH [223] is demonstrated using Hess’s Law

Eqn1 C3H7OH (l) + 9/2O2 (g) → 3CO2 (g) + 4H2O (l) ΔH= -2008 kJ

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -394.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Reverse Eqn1=>3CO2 (g) + 4H2O (l) → C3H7OH (l) + 9/2O2 (g) ΔH= 2008 kJ

Eqn2 x 3=> 3C (s) + 3O2 (g) → 3CO2 (g) ΔH= -1183.53 kJ/mol

Eqn3 x 4=> 4H2 (g) + 2O2 (g) → 4H2O (l) ΔH= -1143.2 kJ/mol

3C (s) + 4H2 (g) + 1/2O2 (g) → C3H7OH (l) ΔH= -318.73 kJ/mol

C3H7OH (l) → 3C (s) + 4H2 (g) + 1/2O2 (g) ΔH= 318.73 kJ/mol [223]

4.31 Tetrachloroethylene, C2Cl4

Energy required to decompose C2Cl4 [224,225,226] is demonstrated using Hess’s Law

Eqn1 C2H2 (g) + 3Cl2 (g) → C2Cl4 (g) + 2HCl (g) ΔH= -422.1 kJ

Eqn2 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.33 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn5 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol

Eqn6 C2H2 (g) + 5/2O2 (g) → 2CO2 (g) + H2O (l) ΔH= -1299.5 kJ

Eqn1=> C2H2 (g) + 3Cl2 (g) → C2Cl4 (g) + 2HCl (g) ΔH= -422.1 kJ

Reverse Eqn2 x 2=> 2HCl (g) → H2 (g) + Cl2 (g) ΔH= 184.66 kJ

Reverse Eqn6=> 2CO2 (g) + H2O (l) → C2H2 (g) + 5/2O2 (g) ΔH= 1299.5 kJ

Eqn3=> H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn5 x 2=> 2C (s) + 2O2 (g) → 2CO2 (g) ΔH= -787.02 kJ/mol

216

2C (s) + 2Cl2 (g) → C2Cl4 (g) ΔH= -10.76 kJ/mol

C2Cl4 (g) → 2C (s) + 2Cl2 (g) ΔH= 10.76 kJ/mol [224,225,226]

4.32 Toulene, C7H8

Energy required to decompose C7H8 [227, 223] is demonstrated using Hess’s Law

Eqn1 C7H8 (l) + 9O2 (g) → 7CO2 (g) + 4H2O (l) ΔH= -3945.9 kJ

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1=> C7H8 (l) + 9O2 (g) → 7CO2 (g) + 4H2O (l) ΔH= -3945.9 kJ

Reverse Eqn2 x 7=> 7CO2 (g) → 7C (s) + 7O2 (g) ΔH= 2754.57 kJ

Reverse Eqn3 x 4=> 4H2O (l) → 4H2 (g) + 2O2 (g) ΔH= 1143.2 kJ

C7H8 (l) → 7C (s) + 4H2 (g) ΔH= -48.13 kJ/mol [227, 223]

4.33 Chloroform, CHCl3

Energy required to decompose CHCl3 [228] is demonstrated using Hess’s Law

Eqn1 1/2H2 (g) + 1/2Cl2 (g) → HCl (g) ΔH= -92.30 kJ/mol

Eqn2 C (s) + 2H2 (g) → CH4 (g) ΔH= -74.87 kJ/mol

Eqn3 CHCl3 (l) + 3HCl (g) → CH4 (g) + 3Cl2 (g) ΔH= 336.5 kJ

Eqn3=> CHCl3 (l) + 3HCl (g) → CH4 (g) + 3Cl2 (g) ΔH= 336.5 kJ

Eqn1 x 3=> 3/2H2 (g) + 3/2Cl2 (g) → 3HCl (g) ΔH= -276.9 kJ

Reverse Eqn2=>CH4 (g) → C (s) + 2H2 (g) ΔH= 74.87 kJ/mol

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CHCl3 (l) → C (s) + 1/2H2 (g) + 3/2Cl2 (g) ΔH= 134.47 kJ/mol [228]

4.34 Benzene, C6H6

Energy required to decompose C6H6 [229] is demonstrated using Hess’s Law

Eqn1 C6H6 (l) + 15/2O2 (g) → 6CO2 (g) + 3H2O (l) ΔH= -3169.4 kJ

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.5 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1=> C6H6 (l) + 15/2O2 (g) → 6CO2 (g) + 3H2O (l) ΔH= -3169.4 kJ

Reverse Eqn2 x 6=> 6CO2 (g) → 6C (s) + 6O2 (g) ΔH= 2361 kJ

Reverse Eqn3 x 3=> 3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.4 kJ

C6H6 (l) → 6C (s) + 3H2 (g) ΔH= 49 kJ/mol [229]

4.35 Acetone, C3H6O

Energy required to decompose C3H6O [230] is demonstrated using Hess’s Law

Eqn1 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.83 kJ/mol

Eqn3 C3H6O (l) + 4O2 (g) → 3CO2 (g) + 3H2O (l) ΔH= -1789.9 kJ/mol

Eqn3=> C3H6O (l) + 4O2 (g) → 3CO2 (g) + 3H2O (l) ΔH= -1789.9 kJ/mol

Reverse Eqn1 x 3=>3CO2 (g) → 3C (s) + 3O2 (g) ΔH= 1180.53 kJ

Reverse Eqn2 x 3=>3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.49 kJ

C3H6O (l) → 3C (s) + 3H2 (g) + 1/2O2 (g) ΔH=248.12 kJ/mol [230]

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4.36 Methyl tert-butyl ether, C5H12O

Energy required to decompose C5H12O [231,214] is demonstrated using Hess’s Law

Eqn1 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol

Eqn2 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.83 kJ/mol

Eqn3 C5H12O (l) + 15/2O2 (g) → 5CO2 (g) + 6H2O (l) ΔH= -3368.93 kJ/mol

Eqn3=> C5H12O (l) + 15/2O2 (g) → 5CO2 (g) + 6H2O (l) ΔH= -3368.93 kJ/mol

Reverse Eqn2 x 6=> 6H2O (l) → 6H2 (g) + 3O 2(g) ΔH= 1714.98 kJ

Reverse Eqn1 x 5=> 5CO2 (g) → 5C (s) + 5O2 (g) ΔH= 1967.55 kJ

C5H12O (l) → 5C (s) + 6H2 (g) + 1/2O2 (g) ΔH= 313.6 kJ/mol [231,214]

4.37 Propylene carbonate, C4H6O3

Energy required to decompose C4H6O3 [230,232] is demonstrated using Hess’s Law

Eqn1 C4H6O3 (l) + 4O2 (g) → 4CO2 (g) + 3H2O (l) ΔH= -1807.1 kJ

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.83 kJ/mol

Eqn1=> C4H6O3 (l) + 4O2 (g) → 4CO2 (g) + 3H2O (l) ΔH= -1807.1 kJ

Reverse Eqn2 x 4=> 4CO2 (g) → 4C (s) + 4O2 (g) ΔH= 1574.04 kJ

Reverse Eqn3 x 3=> 3H2O (l) → 3H2 (g) + 3/2O2 (g) ΔH= 857.4 kJ

C4H6O3 (l) → 4C(s) + 3H2 (g) + 3/2O2 (g) ΔH= 624.34 kJ/mol [230,232]

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4.38 Methylene Chloride, CH2Cl2

Energy required to decompose CH2Cl2 [233] is demonstrated using Hess’s Law

Eqn1 CH4 (g) + 2Cl2 (g) → CH2Cl2 (g) + 2HCl (g) ΔH= -202 kJ

Eqn2 C (s) + 2H2 (g) → CH4 (g) ΔH= -74.5 kJ

Eqn3 H2 (g) + Cl2 (g) → 2HCl (g) ΔH= -185 kJ

Eqn1=> CH4 (g) + 2Cl2 (g) → CH2Cl2 (g) + 2HCl (g) ΔH= -202 kJ

Eqn2=> C (s) + 2H2 (g) → CH4 (g) ΔH= -74.5 kJ

Reverse Eqn3=>2HCl (g) → H2 (g) + Cl2 (g) ΔH= 185 kJ

C (s) + H2 (g) + Cl2 (g) → CH2Cl2 (g) ΔH= -91.5 kJ/mol

CH2Cl2 (g) → C (s) + H2 (g) + Cl2 (g) ΔH= 91.5 kJ/mol [233]

4.39 n-heptane, C7H16

Energy required to decompose C7H16 [234] is demonstrated using Hess’s Law

Eqn1 C7H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2O (l) ΔH= -4850 kJ

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ/mol

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1=> C7H16 (l) + 11O2 (g) → 7CO2 (g) + 8H2O (l) ΔH= -4850 kJ

Reverse Eqn2 x 7=> 7CO2 (g) → 7C (s) + 7O2 (g) ΔH= 2754.57 kJ

Reverse Eqn3 x 8=> 8H2O (l) → 8H2 (g) + 4O2 (g) ΔH= 2286.4 kJ

C7H16 (l) → 7C (s) + 8H2 (g) ΔH= 190.97 kJ/mol [234]

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4.40 Isopropanol, C3H8O

Energy required to decompose C3H8O [235] is demonstrated using Hess’s Law

Eqn1 C3H8O (l) + 9/2O2 (g) → 3CO2 (g) + 4H2O (l) ΔH= -2020 kJ

Eqn2 C (s) + O2 (g) → CO2 (g) ΔH= -393.51 kJ

Eqn3 H2 (g) + 1/2O2 (g) → H2O (l) ΔH= -285.8 kJ/mol

Eqn1=> C3H8O (l) + 9/2O2 (g) → 3CO2 (g) + 4H2O (l) ΔH= -2020 kJ

Reverse Eqn2 x 3=> 3CO2 (g) → 3C (s) + 3O2 (g) ΔH= 1180.53 kJ

Reverse Eqn3 x 4=> 4H2O (l) → 4H2 (g) + 2O2 (g) ΔH= 1143.2 kJ

C3H8O (l) → 3C (s) + 4H2 (g) + 1/2O2 (g) ΔH= 303.73 kJ/mol [235]

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