Apparatus for powerful energy transfer technique

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PRODUCT 378 OUT

CERAMIC

TUBE

REACTION

CHAMBER B

EMITTER

FLAMENTS

I/ STANLESS

STEELTUBE

CERAMC N X 376

NIN in R the reach 382

/ REACTION

CHAMBER A

FEEDSTOCK NN

NYYYY NW

\ YYY

Nina W. N.

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chromium or nickel, for example, metallic coatings may

APPARATUS FOR POWERFUL ENERGY be employed which are reflective to visible and infrared TRANSFERTECHNIQUE frequencies but are relatively transparent to shorter wavelength ultraviolet radiation.

REFERENCE TO RELATED PATENT 5 The use of mercury vapor gas in discharge tubes APPLICATIONS having quartz envelopes is preferred, in view of the This application is a continuation-in-part of my two many spectral lines of mercury vapor which are useful prior co-pending Pat. applications: for pumping the laser-type material. Ruby laser mate U.S. Pat. Application Ser. No. 790,320, filed Apr. 25, rial, aluminum oxide doped with chromium, may suit 1977, entitled "High Intensity Energy Transfer Tech 10 ably be employed as the laser-type material; but other nique', and these chain reactions involve the generation laser-type materials having different output radiation and regeneration of excited atoms of oxygen or other frequencies should be used as required to match the substances; and absorption bands of the feedstocks supplied to the reac

19, 1977, entitled "High Efficiency Energy Transfer Another feature of the invention involves the beating Technique", now U.S. Pat. No. 4,113,589, granted Sep. together of radiation at different frequencies in the pres 12, 1978. ence of media discontinuities in the form of the feed FIELD OF THE INVENTION stock to be irradiated, and the resultant generation of

sum and difference frequencies appropriate to couple

This invention related to highly efficient photochemi strongly with absorption bands of the feedstock mate cal techniques. rial. This technique is particularly advantageous when BACKGROUND OF THE INVENTION the feedstock has absorption bands in the ultraviolet frequency spectrum.

It has been proposed heretofore to apply coherent In accordance with another specific aspect of the radiation from conventional lasers to gases to dissociate 25 invention, the feedstock may be water vapor and air them. However, such application of laser energy is may also be supplied to the reaction chamber. When highly inefficient, and is not economically practical for high intensity radiation within the ultraviolet or other commercial processes.

Accordingly, a principal object of the present inven absorption band of water vapor is radiated throughout tion is to practically and economically apply intense 30 the reaction chamber, the water vapor is split into hy drogen and activated oxygen atoms. These activated relatively coherent radiation to chemical substances to oxygen atoms combine with additional water vapor to dissociate them, and initiate additional reactions. form hydrogen and/or hydrogen peroxide, in additional SUMMARY OF THE INVENTION reactions forming part of a chain reaction initiated by In accordance with one aspect of the invention, a 35 theInbasic irradiation.

reaction chamber is provided with a number of gas invention, at leastwith accordance two another important feature of the feedstocks are supplied to a reac discharge tubes, and closely associated material capable tion chamber, and the reaction chamber is flooded with of being pumped to excited states and emitting rela radiation within at least one of the absorption bands of tively coherent radiation of high intensity. Feedstock is one of said feedstocks at an intensity level sufficient to supplied to the reaction chamber and is exposed to the 40 dissociate the feedstock and the dissociation products radiation, which floods the reaction chamber. Further, are maintained in said reaction chamber at concentra the feedstock has absorption bands at certain frequen cies, and the gas discharge and the associated laser-type tions sufficient to create a chain reaction with the in material are chosen to provide intense output radiation coming feedstocks.

at one or more of the absorption bands of the feedstock. 45 Another feature of the invention involves applying Additional gases may be supplied to the reaction radiation of different frequencies to the input section as chamber to react with the products formed when the compared with the output section of the reaction cham basic feedstock is dissociated. ber, to facilitate relatively complete irradiation and In accordance with one particular aspect of the in dissociation of the incoming feedstock and avoiding vention the laser-type material may be in the form of 50 dissociation of the desired product gases. For example, filaments, wires or spheres, and may also be provided in the case of water vapor as one of the feedstocks and with one or more semi-transparent concentric reflecting hydrogen peroxide as one of the product gases, both surfaces accurately spaced to reinforce the coherent water vapor and hydrogen peroxide have high absorp output radiation. tion bands in the ultraviolet frequency spectrum; and One particularly advantageous form of the invention 55 water vapor, but not hydrogen peroxide, has absorption involves the use of a large number of spheres of laser bands in the infrared frequency range. Accordingly, the type material secured to the outer surface of the gas more powerful U-V radiations may be employed in the discharge tubes. The spheres are provided with a semi input section of the reaction chamber, to dissociate reflecting outer metallic coating, but this is not present water vapor; but in the output section where a substan on that portion of the spheres adjacent the gas discharge tial proportion of hydrogen peroxide will be present, tubes to permit easy entry of the pumping radiation infrared radiation may be employed to selectively disso from the gas discharge tube. When it is desired to pro ciate the water vapor without dissociating the hydrogen vide increased high frequency output radiation, by the peroxide. Similar considerations are of course applica generation of harmonics of the basic output radiation ble to other feedstock and product gases, taking into frequency of the laser type material, the reflective coat 65 consideration their absorption characteristics, and rela ing should be in the order of 70% to 90% reflecting. tive responsiveness to radiation of different frequencies. In accordance with a subordinate feature of the in A feature of the invention involves the introduction vention, instead of normal reflecting materials such as of additional air into the reaction chambers to combine

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with the hydrogen which is dissociated from water FIG. 28 is a schematic showing of another type of vapor to produce hydrogen peroxide, with the collat filament which may be wrapped on the gas discharge eral advantage of supplying heat to the reaction cham tubes of FIG. 24;

ber from this exothermic reaction. FIG. 29 includes a pair of graphs of the absorption Other objects, features, and advantages of the inven coefficient of water vapor in the ultraviolet frequency tion will become apparent from a consideration of the range;

following detailed description, and from the accompa FIG. 30 is a showing of a plurality of spheres of laser nying drawings. type material which may be mounted on the outer sur BRIEF DESCRIPTION OF THE DRAWINGS 10 25 of the drawings; face of the gas discharge tubes shown in FIGS. 24 and FIG. 1 is a schematic representation of one illustra FIG. 31 is a schematic showing of pumping radia tive embodiment of the system of the present invention; tionapplied to a laser-type material sphere mounted on FIG. 2 is a perspective view of the hydrogen bur the exterior surface of one of the gas discharge tubes, ner/heating means which may be employed as part of and the corresponding coherent output radiation from the system; 15 the sphere; and

FIG. 3 is a vertical cross-section of the hydrogen FIG. 32 is a schematic showing of the generation of burner of FIG. 2; pumping radiation from the gas discharge tubes and its FIG, 4 is a perspective view partially broken away application to the laser-type spheres that are in close for illustrative clarity of a reaction chamber; proximity to the feedstock and product gases in the FIG. 5 is a perspective view, also partially broken 20 reaction chamber.

away, of a complete system; Initially, before considering the drawings in detail, it FIG. 6 is a block diagram of a system illustrating may be noted that FIG. 1 through 23 were included in certain principles of the present invention; the prior co-pending patent applications, Ser. Nos. FIG. 7 is a pressure versus time plot for a multiple 790,320, and 834,682, of which this specification is a reaction chamber system; 25 Continuation-in-Part. FIGS. 24 through 32 are newly FIG. 8 is a cross-sectional view of a portion of a added in the present specification and represent the reaction chamber assembly which may be employed; preferred embodiments of the invention. The following FIG.9 is a schematic diagram of the structural rela description of FIGS. 1 through 23 will closely parallel tionship of a plurality of reaction chambers, central that set forth in the prior patent application, Ser. No. burner, and enclosing insulating housing for use in a 30 834,682 cited hereinabove.

system of the present invention;

FIG. 10 is a plot of the absorption characteristics of DETAILED DESCRIPTION water vapor versus wave length; Turning now to FIG. 1, the system of the present FIG. 11 is a showing of the contents of each of the invention is generally designated by the numeral 10 and reaction chambers employed in the one embodiment of 35 it comprises reaction chambers 12, 14, 16 and 18, heat the invention; ing means generally designated 20, and a hydrogen and FIG. 12 is a schematic diagram indicating the genera hydrogen peroxide reservoir or accumulator 22. Water tion of concentrated radiation and its application to a enters the system at conduit 24, passes through flow feedstock; control valve 26 and conduit 28 to manifold 30. Water FIG. 13 shows an alternative apparatus involving the may then be supplied to heat exchange coil 32 through continuous flow of feedstock. valve 34 and conduit 36, to heat exchange coil 38 FIG. 14 is a plot of Photon Emission from a “Black through valve 40 and conduit 42, to heat exchange coil Body" at 1000 K. versus Wavelength; 44 through valve 46 and conduit 48, and to heat ex FIG. 15 is a plot of Radiant Emittance vs. Wave change coil 50 through valve 52 and conduit 54. It will length for a 1000 K. black body; 45 be seen that conduit 36 is the inlet end of heat exchange FIG. 16 shows a wire coated with radiation-produc coil 32, the outlet of heat exchange coil 32 being conduit ing material; 56 which is connected to one end of reaction chamber FIGS. 17 and 19 show reaction chambers for apply 12. Similarly, the outlet end of heat exchange coil 38 is ing high frequency radiant energy to feedstocks; - conduit 58 connected to one end of reaction chamber FIG. 18 is a diagram showing the reaction chambers 50 14, the outlet end of heat exchange coil 44 is connected of FIGS. 17 and 19 includes in an operative system; to one end of reaction chamber 16 through conduit 60, FIG. 20 is a detailed showing of one arrangement for and the outlet end of heat exchange coil 50 is connected supporting the radiating wires of FIGS. 16, 17 and 19; to one end of reaction chamber 18 through conduit 62. FIG. 21 shows the ultraviolet absorption characteris Vacuum is applied to the system, for purposes which tic of hydrogen peroxide, H2O2; 55 will become apparent as the description proceeds, FIGS. 22 and 23 are side and sectional views, respec through conduit 64, flow control valve 66, and conduit tively, of a reaction chamber which is irradiated by light 68 which is connected to one end of a conventional gas from two lasers of different frequencies; burner 70. It will be appreciated that heating means 20 FIG. 24 is a schematic view of reaction chamber comprises burner 70 and heat exchange coils 32, 38, 44, containing gas discharge tubes, in accordance with the and 50, and their respective conduits and valves. invention; As will also become apparent as the description pro FIG. 25 is an enlarged cross-sectional view of one ceeds, hydrogen and hydrogen peroxide generated in end of the reaction chamber of FIG. 24; the reaction chambers 12, 14, 16, and 18 passes through FIG. 26 is an enlarged schematic view of one of the conduits 72, 74, 76 and 78, respectively and valves 80, plates which divides the reaction chamber of FIG. 24; 65 82, 84 and 86, respectively, to manifold 88. The hydro FIG. 27 is a cross-sectional view through one of the gen and/or hydrogen peroxide then passes through filaments including laser-type material which may be conduit 90 with check valve 92 to hydrogen accumula wrapped on the discharge tube of FIG. 24; tor 22 where it is then drawn off for use through con

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duit 94, flow control valve 96, and conduit 98. Conduit cally about 60 seconds), depending on the reactant used, 100, flow control valve 102 and conduit 104 are pro the particulate size, the temperature, and the pressure. vided to allow atmospheric air to enter the system when Valves 108, 110, and 112 are fully opened to allow the and if needed, as will be described more fully hereinbe vacuum evacuation of all residual gases in the other low. reaction chambers and their respective heat exchangers Before proceeding further with a description of the and piping. It should be noted that since a predeter system, it should be distinctly understood that while the mined amount of water was to be passed to heat ex example given herein for purely illustrative purposes change coil 32, valve 34 was opened for just a brief includes four reaction chambers, there is, in fact, no period and then closed.

limit other than practical considerations of size and 10 Steam having entered and permeated reactant 126 in weight as to the number of reaction chambers used. In reaction chamber 12, valve 40 is then opened briefly to fact, the invention could be practiced with as few as one allow a metered amount of water into heat exchange reaction chamber and as many reaction chambers as coil 38, with the steam generated therein then passing desired, there being no reason why a bank of dozens or through conduit 58 to reaction chamber 14. Valve 40 is even a hundred reaction chambers could not be used. 15 then closed. The steam which passes into reaction For this reason, applicant is not limiting himself to the chamber 14, as with the steam wich had passed into use of four reaction chambers except for illustrative reaction chamber 12, is converted into hydrogen and purposes. Obviously, one skilled in the art would easily /or hydrogen peroxide and then held restrained in the be able to include the necessary valve elements and reaction chamber for the predetermined control time. other hardware if he were adding more reaction cham 20 In the meantime, valve 80 is opened so that the pressure bers. built up in reaction chamber 12 will force the hydrogen With the foregoing understood, the description of the to exit through conduit 72 and valve 80 into manifold 88 instant inventive system will proceed. The system runs and then through check valve 92 into the hydrogen at about 900 K. or 1000 K. and may be pre-heated by accumulator 22. Valve 80 is then closed and valve 106 is any well-known electrical heating means such as that 25 opened to allow the vacuum to empty the residual hy described in the parent application. drogen and oxygen tailings from reaction chamber 12 Alternatively, pre-heating can be accomplished by and pass it to burner 70 where the mixture is burned burning hydrogen in burner 70, the hydrogen being the using disproportionated oxygen from reaction cham "tailings' left in one or more of the reaction chambers bers 12, 16, and 18 along with additional atmospheric from a previous run of the system. For this pre-heating 30 oxygen supplied through conduit 100, if necessary. It cycle, flow control valve 26 is opened to allow water to should be noted that when valve 80 was opened to pass enter the system filling manifold 30. Valves 34, 40, 46 the hydrogen and/or hydrogen peroxide out of cham and 52 remain closed during this cycle. Valves 106, 108, ber 12, and then vacuum was applied by opening valve 110 and 112 are opened. Vacuum is applied at conduit 106, the oxidized reactant in chamber 12 disproportion 64 with valve 66 opened. Thus, it will be seen that vac 35 ated to release the bound oxygen since the temperature uum is applied via conduit 68 to burner 70. Since the in the reaction chamber remained high and the presure other end of burner 70 is connected to conduit 114 was lowered.

which, in turn, is connected to manifold 116, manifold With valve 106 still open, valve 82 is also opened to 116 is under vacuum. Then, since valves 106, 108, 110, allow the hydrogen and/or hydrogen peroxide gener and 112 are open, the vacuum is applied to reaction ated in reaction chamber 14 to flow into the manifold 88 chambers 12, 14, 16 and 18, respectively, through con from which it is directed into the hydrogen reservoir duits 118, 120, 122 and 124, respectively. Thus, any 22. In the meantime, valve 46 had briefly opened to residual hydrogen tailings remaining in any of the reac allow a metered amount of water into heat exchange tion chambers is drawn into the inlet end of burner 70 to coil 44 and then the steam formed in heat exchange coil be burned along with any residual oxygen tailings or 45 44 passes to the inlet end of reaction chamber 16. At this with atmospheric air drawn in through conduit 100 and point, valve 84 is still closed. Valves 106 and 112 are still valve 102 by the vacuum which also affects this air line. open to allow vacuum to exhaust chambers 12 and 18. It should also be noted that in event of a "cold' start Valve 82 then closes and valve 108 opens along with where there are no hydrogen tailings to be burned, a valves 106 and 112 which are also open. Thus, hydro combustible gas, such as hydrogen, could be drawn in 50 gen and/or hydrogen peroxide and oxygen tailings are through conduit 100 and valve 102 to provide the initial being conveyed through valve 108 to burner 70 for start-up heat. The burning of hydrogen in burner 70 combustion with the combustion gases being exhausted provides considerable heat which, by radiation and through conduit 68.

conduction is passed to the reaction chambers which Then, valve 84 is opened to pass the hydrogen and/or are filled with reactant 126. When the system is pre 55 hydrogen peroxide from reaction chamber 16 to mani heated to a sufficiently high temperature, we are ready fold 88. Valves 106 and 108 are opened to allow vacuum to proceed with the generation of hydrogen and hydro to exhaust the respective chambers 12 and 14 while gen peroxide. valve 52 has been allowed to briefly open to pass a Valve 34 is opened to allow a predetermined amount metered amount of water to heat exchange coil 50 with of water to enter heat exchange coil 32 which is, in the steam being formed then passing to reaction cham essence, a steam generator. The water is "flashed" to ber 18. The steam in reaction chamber 18 reacts with steam and delivered through conduit 56 to the inlet end reactant 126 to form hydrogen and/or hydrogen perox of reaction chamber 12. The steam enters reaction ide which is restrained since valve 86 is still closed. chamber 12 containing reactant 126 to fill the total void Valves 106, 108 and 110 are all open so that the other volume and is constrained in this volume because all 65 reaction chambers are being exhausted. outlet valves are closed. The residence time, or reaction Valve 88 is then opened to relieve the pressure on time, may be controlled from a few seconds (typically reaction chamber 18 and allow the hydrogen and/or about 2 to about 3 seconds) to a rather long time (typi hydrogen peroxide to pass to manifold 88. At this point,

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the whole cycle starts again and valve 14 is briefly other gases are removed from the vicinity of the reac opened to allow a metered amount of water to pass to tant, preferably by a reduction in pressure to less than heat exchange coil 32, valve 86 is closed, and valve 112 atmospheric, with about one-tenth atmosphere being is opened. The whole cycle then repeats. successfully employed. As can be appreciated, by using While the system of the invention is shown schemati temperatures and pressures well above and below criti cally, it will be readily understood by one skilled in the cal levels during the two phases of the cycle, increased art that it can be easily constructed. The valves are all of speeds of operation may be obtained. a mechanical type which are cam operated so that a Reference is now made to FIGS. 2 and 3 wherein the precise timed sequence of events can be carried out in a heating means 20 is shown in more detail. Heating predetermined manner, the timing of the opening and 10 means 20, as already discussed, comprises burner 70 and closing of the valves being controlled by the size, shape, heat exchange coils 32, 38, 44, and 50. Burner 70 com configuration and speed at which the cams are moving. prises casing 128 made of any suitable metallic material The following "steps” are identifiable in the total lined with a porous fire brick insulation 130 which is reaction cycle involving gases and solids: carved or otherwise formed to fit casing 128 and has an (1) Supply of the water vapor (steam) in the direction of 15 axial hollow core running longitudinally through most flow.

of its length. The hollow core is, in turn, filled with a (2) Diffusion of this steam into contact with the particu suitable surface catalyst 132 for "burning" hydrogen lates of manganese oxides or to the reacting interface and oxygen to form steam. Through the center of heat which may be on the surface, or inside the particu ing means 30 is a conventional electrical resistance heat late, depending on the oxidation level of that particu 20 ing element 140 which is used, when necessary, for lar particulate in the gradient (overall). pre-heating the system for a cold start. At the lower end (3) Interface reaction (intrinsic rate), including seques of heating means 20 as in the drawings, are atmospheric tering of oxygen and the release of the gaseous prod air inlet 104 and residual tailings inlet 114. At the upper uct H2. end is exhaust line 68.

(4) Diffusion of product from the interface. 25 The next sub-system under consideration is the reac (5) Removal of product, H2, in the direction of flow. tion chambers 12, 14, 16 and 18. For an understanding (6) Concurrently with Steps 2-5, the water vapor is also of the construction of the reaction chambers, attention being directly dissociated by photon action, produc is directed to FIG. 4 where a single reaction chamber ing both H2 and H2O2, as described in detail below. designated generally as 142 is shown. Reaction chamber (7) Diffusion of combined oxygen from the interior of 30 142 comprises an outer casing 144 made of any suitable the reactant to the interface, and then away from the material such as "thick stainless steel or as discussed in reactant in the direction of flow of the H2 and O2 the aforementioned co-pending application. It is filled residual tailings. with reactant 126 as discussed above and as shown and (8) Combustion of the H2 and O2 tailings in the centrally described below in connection with FIGS. 8, 11 and 12. located burner. 35 Passing axially through the reactant is a conventional (9) Removal of products of combustion from the burner electrical resistance heating element 146, this heater in its separate direction of flow. being essentially the same as heater 140 in FIG. 22. This The instant process is a process in which a relatively may be used for pre-heat in a cold start. As already small amount of heat-energy input, (in the form of pre discussed, however, the exact means used for pre-heat heat for the reactant) provides conditions for the reac ing the system is not critical to the invention and any tant to effect changes of state, during which a gaseous means well-known in the art for accomplishing this end chemical molecule is completely dissociated into its may be used. The reactant 126, including sensitizer and separate gaseous atoms by two distinct phenomena. In host materials, is placed in casing 144 leaving a space at the course of one of these phenomena, the solid reactant each end, these spaces being designated in FIG. 23 as concurrently effects a "change of state' by means of an 45 148 and 150. Spaces 148 and 150 essentially serve the exothermic transformation from one oxidation product function of surge tanks, manifolds, or the like. Steam level to another oxidation product level; and in the inlet 152 and vacuum inlet 154 are provided at one end course of the second phenomena, to be described in of reaction chamber 142 and hydrogen outlet 156 is detail below, the H2O molecules are directly dissociated provided at the other end. Steam inlet 152 corresponds by photon energy, forming H2 and also H2O2, hydrogen 50 to conduit 56, for instance, vacuum outlet 154 corre peroxide. sponds to conduit 118, for instance, and hydrogen outlet It should also be noted that pressure changes play an 156 corresponds to conduit 72, for instance, in FIG. 1. important part in the system. Specifically, the reactant is Turning now to FIG. 5, the preferred configuration heated to a temperature well above the dissociation of the apparatus is shown along with the sub-system temperature for oxygen from the metallic oxide of 55 which includes the valves and driving mechanism for higher oxidation number at room temperature. This the same as well as the "plumbing". It will be seen that temperature for MnO2 is given in handbooks as 535 C., the valves which are described above are arrayed in a and at atmospheric pressure this MnO2 will dissociate to single line. The valves are of a conventional type which Mn2O3 at temperatures above 535 C. Accordingly, it is are operated by pushing or releasing a plunger desig desired to operate at temperatures well above 535 C. nated, for convenience of illustration, as 158 in conjunc such as 600 C. to 950 C. In addition, during the hydro tion with valve 34. It will be appreciated that while the gen formation portion of the cycle, the pressure must be description of the valves refers to valve 34 and plunger well above atmospheric so that the oxygen will be ab 158 for exemplary purposes, each of the valves operates sorbed by the Mn2O3 (the oxide of lower oxidation in the same manner. A variable speed motor 160 turns a number), with a pressure of about at least 75 psi or 100 65 drive shaft 162 which is journaled in mounting plates being preferred, and preferably between 100 psi and 150 164 and 166. Fixedly mounted on drive shaft 162 are psi to as high as 200 psi or more. In addition, during the cams 168, with one cam corresponding to each of the oxygen disproportionation phase, the free oxygen and valves and mounted on drive shaft 162 in such a way as

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to cooperate with plunger 158 of each valve. Thus, as tion form hereinbelow, and supplies heat to the system. motor 160 turns drive shaft 162 and, in turn, cams 168, The hydrogen and hydrogen peroxide is stored in reser the valves are opened and closed in a manner which is voir 216, which is maintained at a relatively high pres predetermined by the positioning of cams 168. This, of sure level by the check valve 218 which prevents loss of course, will be readily understood by one skilled in the hydrogen back toward the reaction chamber 202 be art. tween the intermitent withdrawing of hydrogen from Referring further to FIG. 5, it will be seen that the the reaction chamber 202. Hydrogen and hydrogen reaction chambers are set vertically in an enclosure that peroxide may be withdrawn as needed from the reser is square in cross-section and are shown in the drawing voir 216 through an output line 220. By closing both with reaction chamber 12 in the front left-hand corner, 10 valve 213 and valving 215, the amount of hydrogen reaction chamber 14 in the rear left-hand corner, reac peroxide which is generated is severely limited, and the tion chamber 16 in the front right-hand corner, and bulk of the output will be hydrogen, rather than H2O2. reaction chamber 18 in the rear right-hand corner. Vacuum pump 221 may be employed to speed up Heating means 20 is disposed in the center. The enclo separation of oxygen, hydrogen tailings, and other re sure or, more specifically, inner enclosure 170 is prefer 5 sidual gases from the reactant during dissociation or ably made of magnesium oxide packed in a stainless disproportionation.

steel container. This material was chosen because it With regard to the block diagram of FIG. 6, it is to be distributes heat evenly throughout the volume of the understood that the components shown in this figure enclosure 170. Surrounding inner enclosure 170 is outer may be employed in connection with any system de enclosure 172 which is made of any suitable material 20 scribed hereinabove in the present specification. Specif such as stainless steel and filled with a high quality ically, the various input and output control valves have insulation such as alumina fibers. It will be appreciated been, for the most part, omitted from FIG. 6 for pur by one skilled in the art that any high quality, high poses of simplicity. Similarly, the precise physical ar temperature, insulating material may be used. rangement, with the units 202,204 and 212, for example, Returning to a consideration of the drawings, FIG. 6 25 being in intimate heat-conducting relationship with is a block schematic drawing showing in a central posi each other, and insulated from the atmosphere, is not tion the reaction chamber or chambers 202 and an im shown in FIG. 6, but may be in accordance with disclo mediately associated steam generator 204. A reservoir sures of other units disclosed in the present specifica of water 206 supplies water to the steam generator 204, tion.

which may be of any of the types described in connec 30 FIG. 7 shows a typical pressure versus time cycle for tion with earlier figures of the drawings. In this connec a system in accordance with the present invention using tion, it may be noted that all of the arrangements shown manganese oxide as the reactant, and four reaction in FIG. 6 are applicable to the hydrogen generation chambers. This is, for example, of the type described apparatus shown hereinabove in the present specifica hereinabove in connection with FIGS. 1 through 5 of tion. 35 the drawings.

Steam or water vapor is supplied to the reaction The pressure is "gauge' pressure in pounds per chamber or chambers 202 through line 208 which may square inch (psi). With this pressure scale, atmospheric of course be internally connected between the immedi pressure is of course indicated by Zero. ately adjacent and thermally connected units 202 and Considering the cycles shown in FIG. 7 from an 204. Hydrogen from reaction chamber or chambers 202 overall standpoint, the complete cycle for each reaction may be routed through output line 210 to the venturi chamber including both breaking up the water vapor tube combining unit 212 which is also in intimate heat and dissociating the oxygen from the reactant may be 40 conducting relationship with reaction chamber 202 and seconds. However, the cycles of the reaction chambers the stream generator 204. As mentioned above, in con are evenly staggered in operation, by 10 seconds in the nection with manganese oxide the temprature of the 45 example so that hydrogen is generated on a substantially entire assembly, including the venturi unit 212, may be continuous basis. In FIG. 7 the pressure cycle for reac in the order of 600 to 950 C. tion chamber No. 1 is shown in the lower characteristic, Hydrogen peroxide may be formed in either of two and the pressure cycle for reaction chamber No. 2 is ways, and the proportion of hydrogen peroxide to hy shown in the upper characteristic. The pressure versus drogen gas may be controlled by valves 213 and 215. 50 time characteristics for reaction chambers Nos. 3 and 4 Initially, considering the formation of H2O2 within the are substantially the same as those of chambers No. 1 reactor chambers, by photon action, valving 215 would and 2, but are displaced by additional 10 second inter be opened while steam is present in the reaction cham vals.

bers and while the H2 gas is being drawn off, and oxy Now, referring specifically to the lower characteris gen at high pressure, corresponding to the pressure of 55 tic 230 in FIG. 7, the cycle starts with the opening of the reaction chamber is admitted to chambers 202 via the water inlet valve for a couple of seconds at the conduit 217 from pump 219. beginning of the cycle. Steam is promptly generated Now considering the subsequent formation of H2O2, and fills the first reaction chamber. At about 6 seconds, valve 215 would be permanently closed, and valve 213 the hydrogen outlet output valve is opened as indicated would be open. When hydrogen starts to flow rapidly by arrow 232. Hydrogen and/or H2O2 continues to through the Venturi unit 212 the check valve 214 will flow until about 16 or 17 seconds of the cycle, when the open and oxygen will be combined with hydrogen to hydrogen pressure drops to the hydrogen reservoir form hydrogen peroxide. The Venturi unit 212 is in pressure, indicated as equal to 80 pounds by the dash intimate heat conducting relationship with reaction dot line 234 in FIG. 7. The closure of the hydrogen chamber 202 and during the preheat period, absorbs 65 reservoir check valve 218, as shown in FIG. 6, is indi heat from the reaction chamber. Later, during opera cated by the arrow 236 in FIG. 7. Soon after the closure tion, the combination of hydrogen with oxygen is an of check valve 236 the pressure release and vacuum exothermic reaction as set forth quantitatively in equa pump valve is opened, as indicated by arrow 238 and

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the pressure drops along characteristic 240 to the nega refractory lining and the granular refractory material tive pressure of about one-tenth of an atmosphere indi such as is shown at 130 and 132, respectively, in FIG. 3. cated by line 242. During the interval from about 20 The unit of FIG. 9 is also provided with heavy upper seconds to 40 seconds the disproportionation phase and lower plates 320 and 322, which are bolted together takes place. Then at approximately 40 seconds the 5 with a series of bolts 324 spaced around the periphery of water inlet valve is opened again, and the cycle repeats. the plates 320 and 322. With this arrangement the reac The upper characteristic in FIG. 7 shows the same tion chambers 302, 304, 306, and 308 are rigidly to cycle for reaction chamber No. 2 as described above for gether in intimate heat conducting relationship, and can reaction chamber No. 1. In the upper characteristic the withstand very high pressures even at very high tem same reference numerals are employed, but primes are 10 peratures without deformation of the reaction cham employed in place of the unprimed numbers used in bers.

connection with the lower plot of FIG. 7. The reaction chamber assembly is mounted on any FIG. 8 is a fragmentary view of a portion of a reac suitable insulating support as indicated by the blocks tion chamber such as that shown in FIGS. 1 and 4 de 326. A lower metal base 328 and lighter gauge stainless scribed hereinabove. In FIG. 8 the outer cylindrical steel metal sidewalls 330 are also provided. High tem wall 252 may for example be made of one-quarter or perature heat insulating ceramic wool encloses the reac three-eights inch stainless steel. tion chamber assembly and reduces heat radiation to Referring more specifically to FIG. 8, in order to very low levels. The ceramic wool is indicated by refer expose the manganese oxide powder fully to the space 20 ence numeral 332 in FIG. 9. In passing, it may be noted within reaction chamber 258, this chamber is filled with that the use of flat donut-shaped reaction chambers a large number of hollow stainless steel screen elements which may be formed by taking small strips of stainless provides a geometry which is superior to the set of five cylinders shown in FIG. 5, in that the reaction cham steel and folding them over upon themselves and weld bers ing or otherwise securing them together to form a hol 25 with are one in more intimate heat conducting association another and with the central burner, than in low enclosed space. The chamber 258 is initially filled the arrangement of FIG. 5.

with these stainless steel, hollow mesh cells 260. Then a Apart from the physical arrangement of the four large quantity of manganese oxide is poured into the reaction chambers and the central burner, the "plumb reaction chambers and is shaken down in among the ing" and mode of operation of the system as described stainless steel mesh cells to completely fill the entire 30 in connection with FIGS. 1 through 8, remains un chamber 258. In FIG. 8 a number of these stainless steel changed.

mesh cells designated 560 are shown, and the manga A more detailed consideraion of the absorption char nese oxide powder 262 between the cells is also indi acteristic of water vapor and other possible feedstocks, cated. It is to be understood, of course, that other tech niques may be employed for exposing the reactant to 35 and the matching of the host and sensitizer materials to the feedstock absorption characteristic will now be the space within the reaction chamber, but the forego undertaken.

ing system has proved eminently satisfactory in at least one 4-reaction chamber apparatus which has been suc of Inwater FIG. 10 the relative transmittance and absorption vapor at different wavelengths is shown. By cessfully operated.

In addition, the host and sensitizer material may be 40 way of example, note that at wavelengths of about 2.5 to 2.6 microns, the curve which represents transmit included in the fabrication of the wire mesh cells 260.

With waver vapor within these wire mesh cells, this tance has a dip designated 342 in FIG. 10. This is in contrast to the peaks 344 and 346 which are centered feedstock is fully exposed to the intense radiation from just the sensitizer. above 2 microns, and in the vicinity of 4 microns, FIG. 9 shows an improved structural arrangement of 45 respectively. A combined host material and sensitizer the reaction chambers in which the four reaction cham which will provide intense coherent radiation in the bers 302, 304, 306 and 308 are donut-shaped and are vicinity of 2.5 and 2.6 microns, and which absorbs en stacked up on top of one another in intimate heat con ergy in the vicinity of 1.2 to 1.3 microns, will be em ducting and transferring relationship. Each of the four ployed as one set of materials for concentrating energy reaction chambers is provided with two manifolds 310 50 and applying it to water vapor. The particular host and 312 to supply gases to the reaction chambers and to material and sensitizer which provides this wavelength remove gases therefrom. These input and output mani of absorbing heat energy and radiating energy is cal folds serve the same functions as the spaces 148 and 150 cium fluoride CaF2 as the host material, and uranium-3 at the top and bottom of the cylindrical reaction cham as the sensitizer.

bers as shown in FIG. 4, for example. 55 Before considering FIGS. 11 and 12 some back Each of the reaction chambers 302,304,306, and 308 . ground relative to the phenomena which are taking contain reactant, such as manganese oxide, and voids place will now be included.

created by wire mesh cells as described above, or other Initially, it may be noted that the theory of Masers structure which will be described below, with which and Lasers of course forms a background for the present the sensitizer and host materials are associated. 60 invention. The word "LASER'' is an acronym which A burner 314 extends through the central opening of stands for the Light Amplification by the Stimulated all of the four donut-shaped reaction chambers. The Emission of Radiation. Although related to some extent burner 314 has the general configuration shown in FIG. to Maser and Laser theory, the present invention does 3, but is provided with upper and lower apertured plates not involve the intense collimated beams of energy 316 and 318 for ease in applying the hydrogen and oxy- 65 characteristic of Masers and Lasers; and of course, Ma gen to the burner and for ease of withdrawning the sers and Lasers do not derive their energy from a heat burned gaseous products from the unit. Although the reservoir made up of a body of material at elevated details of the burner 314 are not shown, it includes the temperatures.

Page 28

The TOTAL THERMAL EMISSIVE POWER PT

Types of Radiation of a perfect black body increases as T, according to the There are two separate processes by which a material STEFAN-BOLTZMANN LAW:

can become a generator (or producer) or radiation en Pr=25k4T/15C2h.3=5.7x10-5T4 erg cm-2sec-1 (52) ergy after absorbing suitable quantities of primary en 5 ergy. In the first process the absorbed energy is con At room temperature (about 200 K.), \pk is in the far verted (degraded) into a low-quantum-energy heat that infrared at 97,000 A, and PT is only 4.6x 105erg cm-2 diffuses through the material which then emits radiation sec, so that there is not an appreciable amount of called thermal radiation. radiation in the VISIBLE region between 4000 and In the second process an appreciable part of the ab 10 7000 A.

sorbed energy is temporarily localized as relatively At the temperature of an incandescent lamp filament high-quantum-energy excitation of atoms or small (about 2800 K.), Apk is about 10,000 A, and PT is groups of atoms which then emit radiation called lumi 3.5x 109 erg cm-2 sect, so that there is an appreciable nescense radiation. emission in the visible part of the spectrum. In the tem Specifically, "luminescence" is a process whereby 15 perature range between about 700 and 1000 K. there is matter generates nonthermal radiation which is charac an overlapping offeeble luminescence and feeble incan teristic of the materials involved and not the tempera descence.

tures. Sometimes, however, the radiation as generated is The present invention involves temperatures from a also called "luminescence'. It is in fact luminescence lower limit of about 900' to 1000' Kelvin or about 600 only when the radiated energy is in excess of the ther 20 to 700 Centigrade and ranges upward from these tem mal radiation produced by heat. peratures with the upper limit controlled only by the Thermal radiation from solids is generally a broad strengths of the materials utilized (1) as the reactant or continuous spectrum of radiation, especially infrared, host/sensitizer, (2) for the reaction chamber, and (3) for which is emitted in increasing amount as the tempera 25 the tanks, tubing, etc.

ture of the solid is increased.

The quality and quantity of thermal radiation depend THE HASER CONCEPT almost exclusively on the temperature rather than the The Maser/Laser type of acronym may also be ap nature of the emitting solid material. Broadly and objec plied to another system termed "Haser', an acronym tively speaking, luminescence describes emission of 30 for "Heat Amplification by Stimulted Emission of Radi radiaton (of subatomic origin) in excess of thermal radi ation." As will be developed below, however, the term ation; that is, luminescence yields photon emission in "Amplification' is not used in the sense of increasing excess of the photon emission produced entirely by signal strength, but in the sense of amplifying the effec thermal agitation. tiveness of heat energy. Luminescence is generally excited by primary pho 35 The Haser application depends not as much on coher tons or charged material particles having individual ence or monochromaticity per se, but rather on the energies ranging from about 2 ev to over 106 ev and unprecedented energy per unit area. This radiated en affords emitted photons with energies in excess of 1 ev. ergy is a by-product of the coherence of the radiation, When luminescence is excited by energy liberated dur and can be many orders of magnitude greater in energy ing chemical reactions, the liberated energy per emit 40 than normal incoherent thermal radiation. To under ting atom or molecule usually exceeds 1 ev. These exci stand why this is possible, it is necessary to review tation energies are hundreds to millions of times greater briefly a few of the basic differences between the inco than the energies of individual phonons in solids. A herent radiation produced by an ordinary bright source single phonon can increase the energy of an electron or and the coherent light (radiation) produced by a laser or atom in a solid by at most a few hundredths of an elec 45 aSc.

tron volt, whereas the individual primary particles nor mally used to excite luminescence can provide energy gas)In aareconventional source the atoms of a solid (or a agitated either thermally or electrically to increases up to the total amount of energy carried by higher energy states. When these atoms return sponta the primary particle (except for rest-mass energy), that neously to their lower levels, they radiate some of their is, tens to millions of electron volts. excess energy as light. Since each atom behaves inde In order to obtain barely visible emissions of thermal 50 pendently at this state, its emission is at a random time radiation from a solid, the temperature of the solid must be raised above 900 K. to obtain an appreciable proba andIt infollows a random direction with a random polarization. that the light radiated in a single direction bility of getting 1.7 eV (or greater) electronic excitations in the complex sum of all the light from the individual by the cumulative action of phonons. 55 atoms. The phases of any two atoms will tend to cancel The thermal radiations from real solids cannot exceed their radiation in some directions and enhance it in the emission which would be obtained from a perfect others. The total energy of the source will on the aver black body at the given temperature and frequency. age be radiated uniformly in all accessible directions, Most solids emit somewhat less thermal radiation than the maximum which is expressed by: and the amount of energy observed in a given direction will be proportional to the solid angle substituted by the

P84=(thv3C-3(Ehv/kT-1)-lerg cm-2 sec- (50) observing device. In the Haser interior the observing device is either a water-vapor molecule (or other feed

The peak wavelength Mpk of the broad emission band stock) or another particulate of reactant. of black body radiation is inversely proportional to T, The maximum total energy that can be radiated by a according to WIEN'S displacement equation. 65 given source depends on two factors: the surface area of the source and the maximum temperature to which the

Apk=0.29T cm =2.7 x 107 T-1A (51) source has been heated. Therefore, in practice, the only way to increase the power output from an ordinary

Page 29

source beyond the limitations imposed by the source In the case of the HASER, the principle emissions of material is to increase the surface area of the source. radiation designed and produced to dissociate the chem Power output, however, is only half the solution. ical product may be emitted from the woven wire mesh Concentrated power is much more important than cavity balls or cells 260 (FIG. 8) that fill the entire power itself. A 40-watt fluorescent lamp, for example, Haser cavity.

produces more light than a 40-watt incandescent lamp, The “preheat' energy can be electrical and inserted but the fluorescent lamp is not nearly as effective as the (through resistance heaters) into the internal cavity or incandescent light source for a spotlight. the heaters may also be external to the cavity and heat Now, in a laser or maser, the energy is also emitted when atoms drop from a higher energy level to a lower 1 O theAlso, mass by conduction and radiation through solids.

the "preheat" energy may be inserted by com one; however, in this case the atoms are triggered and busting suitable fuels such as hydrogen, hydrogen per emit radiation (to a large percentage) in unison. In the oxide, alcohol, and other hydrocarbons, directly in the case of the Haser, the atoms are triggered to emit radia internal cavity of the unit or within a "center-core' tion in unison by phonon/photon waves within the unit 5 burning unit as is designed into the unit of FIG. 9, for cavity or cell interior. Enough of the energy previously example.

generated is retained within the mass of particulates to As the reactive mass reaches temperature levels maintain emission in a compatible phase, polarization which excite the molecules and atoms to a radiating and direction. This phonon wave interacts with the level of energy, phonons and photons evolve which - excited atoms and causes them (to a large degree) to O distribute the thermal energy within the mass. Inciden emit their excess energy in phase with the stimulating 2 tally, relative to the use of the terms "photon" and wave before they have a chance to do it randomly. "phonon', when a photon traveling through space im As a result, the Haser generates a good percentage of pinges on a solid, the resultant wave in the solid is its radiated energy so that it travels in synchronism with termed a "phonon'.

the standing phonon waves, therefore concentrating the 25 The ability of "atoms' to store energy has to do with energy emitted as photons. the electrons within the individual atoms. The electrons In effect, the radiated photons from the Haser partic exist as a cloud of negative charge around the positively ulates are all relatively concentrated, monochromatic, charged nucleus. Each election occupies a state of en and therefore, relatively coherent energy sources. This ergy and angular momentum that cannot be occupied results in an excellent energy density even though the 3 by any other election.

photons are traveling in practically an infinite number 0 Therefore, the electrons tend to fill stable shells sur of directions, due to the fact that the particulate sources rounding the nucleus.

number in hundreds of millions. The photons moving The electrons of the outermost shell are the ones most from particulate to particulate impact and are absorbed easily affected by outside forces because of their acces by other particulates. Then, this STORAGE, BUILD 5 sibility. These outer electrons can be moved to higher UP, AND RELEASE of the “phase and amplitude of energy states, but they always tend to return to their radiated energy,” combined with the fine particulate lowest energy state: the ground state. Electrons at cer geometry of the Haser power (energy) source, which tain levels decay (fall to a lower state) more easily than provides surface area to emit photons in extremes, al electrons at other levels, lows a "maximum efficiency utilization' of the radiated Each excited electronic state of the atom has a char energy within the Haser cavity. acteristic lifetime that indicates the average time it takes The act of controlling the spectral emissions to most an electron to fall to a lower level and therefore radiate effectively dissociate (for example) water vapor, by a photon. Most excited states have lifetimes of about sensitizing the host compound properly is another very 10-8 second.

important point. The monochromatic waves may be 45 There are some excited states or levels in all atoms in come distorted in passing through substances, so that which the electron cannot decay easily by giving up a harmonic waves are generated at two or more times photon. Such atoms must therefore wait for other their original frequency. means of giving up their energy, such as colliding with Infrared wavelengths may be converted into visible other atoms or with the walls of the system. Electrons light, and visible light into ultraviolet waves. 5O in this state of energy tend to stay there for relatively This new system utilizes fine (small) particulates of long periods of time (0.001 second or more), and are solids comprised of oxides which are predetermined by referred to as being in metastable states. This is an im design within which some of the host atoms are re portant part of the storing of energy, which can then be placed by other frequency sensitive atoms also prede retrieved in the excitation process by stimulation. termined by design, which, provide stimulated absorp 5 5 the normal radiative decay from a higher electronic tion and emission at predetermined wavelengths. state to a lower one is termed spontaneous emission. As An ohmic (or other) pre-heat provides to the heat discussed earlier, processes exist that can force an reservoir mass the original energy to liberate a massive atomic electron to a higher state or stimulate it to jump volume of photons at the frequency range which will to a lower state. An example of forcing, as discussed activate the sensitive atoms included in the host com earlier, is provided when a photon collides with an atom pound; the fine multi-faceted particulates absorb the and excites the outer electron to a higher level, which photons which normally proceed as phonons through can happen when the energy or wavelength of the pho the particulate to generate and provide large numbers of ton corresponds exactly to the difference in energy cavity resonances which stimulates emission with each between the state the electron is in and some higher internal excursion; therefore, again, the gain by this 65 possible state. This process is known as absorption be regenerative amplifier when driven by the thermal cause the photon (energy) is actually absorbed by the noise fluctuations from the cavity walls, can be signifi atom and all the photon's energy goes into raising the Cant.

electron to a higher state.

Page 30

Similarly, as discussed earlier, the stimulated electron inversion. This type of "laser' has produced continuous can move to a lower level, provided that such a level powers as high as 60 kw.

exists and that the difference between the two levels The HASER phenomenon as utilized in the present corresponds to the energy of the incoming photon ex invention, actually uses a thermochemical excitation actly. The energy given up by the electron in jumping 5 mechanism. The original preheat energy prepares the to a lower state goes into creating an additional photon reactant material within the reaction chamber by bring with the same characteristics as the colliding photon. ing the material to photon emitting temperatures. A large number of atoms can provide an increase in When water vapor is introduced into the chamber of the radiated energy at the desired frequency or energy FIGS. 1 and 8, for example, the excited billions of pho level, if the population of electrons in the excited states 10 tons emitted and traveling between particulates, strikes of the atoms is suitably arranged. Consider two excited the sensitized "Cvities' with a barrage of photons de levels of a system of identical atoms with the electrons signed to provide frequency, amplitude, and steric fac divided between the upper and lower levels. If a radi tor impact adequate to dissociate the H2O molecules. ated photon having a wavelength corresponding to the On dissociation, the 2H2, and O2 molecules are vibrat difference in energy between the two levels is allowed 15 ing at very high temperatures and pressures which are to pass through the system medium, it will be amplified compatible with recombining these molecules through if there are more atoms with electrons in the upper state the "activated complex' mechanism into their (high and absorbed if there are more atoms with electrons in temperature) preferential H2O+ H2 molecules, which the lower state. The condition of having more atoms in incidentally evolves more than 33 KCal/mole heat en the upper state is called a "population inversion'- 20 ergy. As the steam enters and traverses the cavity, an (because it goes against the normal processes of nature, amount of the steam (depending upon the design of the which tend to keep more electrons at lower energies contents of the reactor chamber and the relative amount than at higher energies). of reactant, manganese oxide or other similar metal The search for new Haser "systems' is therefore not oxide, and the host/sensitizer material), combines with easy, because one is working against the natural tenden 25 the reactant, which raises the oxidation level through cies of the electrons. the process of oxidation; and this of course, evolves heat Another important consideration is the actual "life energy (because this is an exothemic reaction), which, times' of the ion energy levels of the impurity atoms broadcasts more photons of energy throughout the involved in the population inversion. The upper level of cavity interior, to react with the sensitizers and activa a two-level system with a population inversion radiates 30 tors; and this in turn creates massive amounts of new energy corresponding exactly to the difference between photons of energy to dissociate the H2O vapor and the two levels. maintain the reaction temperatures within the host ma The electrons that have thus yielded energy by radia terials.

tion, end up at the lower level. If they remained there, HASER CAVITIES the situation would result wherein there would be more 35 atoms at the lower level than at the upper level, and as Referring again to FIG. 8, the cavities 260 can be discussed earlier, there would be absorption instead of fabricated of very fine mesh woven wire, which is cut gain. For continuous operation, one must find impurity into small sections, stamped, folded, and the outer edges atoms with combinations of levels such that the lower of the wire mesh are secured together to form a hollow level has a short lifetime and the upper level is preferen 40 cell. The wire, of a diameter approximately equal to tially populated. This necessity rules out the ion ground 0.002 inch, is made up of the elements, compounds, and state as a possible Haser level, since allion ground states a metal carrier (inert to the process), and is initially are metastable. the pair (or more) of ion energy levels woven and formed into the cells as described above. It which will provide amplificiation must be energetically is then transformed into the desired host and sensitizer above the ground state but still below the metastable 45 materials through oxidation in an atmospherically con States. trolled furnace or kiln.

Although the original gas laser utilized electrical excitation of electronic transitions, later versions use vibrational transistions in molecules such as carbon CERAMICHASER TUBES dioxide, and the excitation mechanism may involve 50 Instead of the wire mesh cells 260 as shown in FIG. electrical or chemical excitation, or the burning of fuel. 8, the preferred form of Haser cavity is shown in FIG. In the chemical laser, atomic species such as hydrogen 11 in which a large number of ceramic tubes 352 are and fluorine can be reacted to produce molecules in an present. These tubes are preferably extruded from mull excited vibrational state which in turn yields amplifica ite, which is a common clay having the approximate tion or oscillation. 55 chemical structure of 2Al2O3. SiO2 with a range to An entirely new excitation process was announced by 3Al2O3. 2SiO2. Suitable quantities of host and sensitizer Garry in 1970. In this, the gas dynamic laser, an appro materials, as described below, are added to, and thor priate fuel is burned to produce carbon dioxide and oughly mixed with the mullite prior to extrusion. Subse nitrogen at high temperature and pressure. When re quent to extrusion the tubes are fired in a suitable kiln or leased through a nozzle into the optical resonator re 60 furnace. The tubes may suitably have a diameter of gion, the gas cools rapidly in terms of its kinetic or about inch or inch and be from 1 to 12 inches in translational energy, but the population of the vibra length. The sidewalls may suitably be from 1/32 to 1/16 tional energy levels of the carbon dioxide molecules of an inch in thickness, but none of the foregoing dimen becomes inverted since the lower level of the laser sions are critical. After firing, the tubes 352 are pro transition relaxes more rapidly. In addition, the vibra 65 vided with filters 354 in both ends. The filters may be of tionally excited nitrogen molecules are in near reso any suitable structure, for example, several layers of nance with the upper laser state of the carbon dioxide metal gauze, to prevent the intrusion of the reactant 356 and transfer energy with high efficiency to maintain the which may, for example, be manganese oxide. In prac

Page 31

tice the ceramic tubes 352...with their associated filters crons and also at 1.3372 microns as set forth in examples 354 may be initially placed in one of the reaction cham (a) and (b). It may be noted that the absorption wave bers such as reaction chamber 302,304,306, and 308 of lengths for the two output emissions differ correspond. FIG. 9, or the chambers 126 of FIG. 1; and then pow ingly. The combination tabulated in examples (c) and dered metallic manganese or manganese oxide may be 5 8d) set forth above include yttrium aluminum oxide as poured in and the entire unit vibrated until the manga the host material and erbium as the sensitizer. In this nese oxide 356 as shown in FIG. 11 fills all the space case, the emitted radiation for both (c) and (d) is at around the ceramic tubes 352. With this arrangement, of 1.6602 microns; however, the absorption for the two course, the water vapor is present within all of the ce examples is at different frequencies. The final example ramic tubes 352; heat is provided by the manganese 10 (e) using calcium fluoride as the host material and urani oxide 356; and radiation from the host/sensitizer combi nation forming part of the ceramic walls 352 radiates um-3 as the sensitizer was mentioned above intense coherent energy in one or more of the absorp With regard to the matching of the emitted radiation tion bands of water vapor; and this intense radiation from the sensitizers with the absorption bands shown in serves to dissociate the hydrogen and oxygen atoms 15 FIG. 10 for water vapor as a feedstock, the high absorp making up the water vapor molecule. tion band for water vapor extending from about 2.4 The foregoing action is shown diagrammatically in microns to about 3.1 microns is well located to receive FIG. 12 in which the tube 352 is shown centrally lo emitted energy in the 2.5 microns to 2.6 micron wave cated and the surrounding particles of manganese oxide length region from example (e) tabulated above. With 356 are shown radiating broad spectrum thermal radia 20 regard to examples (a) through (d), a cursory review of tion 358 in all directions including into the ceramic tube the emission wavelengths and the corresponding mod 352. The water vapor particles 360 shown as small cir erately sharp absorption bands between 1 and 2 microns cles within the tube 352 may be directly impacted by the would indicate that there is not necessarily an exact coherent radiation 362 which is emitted by the host/- correspondence. However, it has been determined that sensitizer combination included in the walls of ceramic 25 there is a certain amount of broadening of the radiation tubes 352. It may be noted, that for convenience in and of the absorption characteristics which occurs at illustration, the magnanese oxide particles are shown high temperatures; accordingly, with the basic location spaced apart in FIG. 12; however, in practice they of the emission lines and the absorption points as indi would be filling all of the space within the reaction cated in the above table and in FIG. 10, the practical chambers which is not filled with the ceramic tubes 352. 30 result is good coupling from the emitted radiation to the HOST/SENSITIZERS FORWATER VAPOR water vapor molecules at the 1,000 Kelvin temperature FEEDSTOCK at which the system is operative.

With regard to the relative quantities of the host and

In the tabulation which will be set forth below, suit sensitizer material in the mullite, the quantity of host able host materials and sensitizers for applying radiation 35 material should be approximately 25 to 1,000 times to water vapor will be set forth. In this tabulation the chemical symbols for the elements will be employed, greater rial. A than the amount of associated sensitizer mate ratio is approximately 0.5% of sensitizer of the and the host material will be listed first followed by the amount of host material is the general order of magni sensitizer material. In each case the absorption band for tude which should be employed. In addition, the quan the host material will initially be given and then the tity of each particular category of host and sensitizer emission wavelength of the sensitizer will be sent forth. material such as those set forth in the tabulation of con Following the tabulation, the absorption characteristic binations (a) through (e) set forth above, should be of water vapor as shown in FIG. 10 will be reviewed and the relationship of the emisson lines of the sensitiz proportioned to the absorption bands of the feedstock which is being irradiated. Thus, in the particular exam ers to the absorption bands of the water vapor will be 45 ple under consideration, where the host/sensitizer com discussed.

bination (e) using calcium fluoride and uranium-3, is matched to a broad absorption band of water vapor, a (a) Ca WO4: Nd’t Where larger quantity of this host/sensitizer combination Absorption = 0.74 microns-0.76 microns

Emission = 1.065 microns

should be employed as compared with combination (a), 50 (b) and combination (c), (d). Thus, in the making of the (b) Caa WO4:

Ndt Nd,(Neodymium) ceramic tubes, the material which is being prepared Absorption = 0.87 microns–0.89 microns (Same) might include approximately 88% by weight of mullite, Emission = 1.3372 microns 8% by weight of the host/sensitizer combination (e), (c) Y3Al5O12: Ert Where and 2% by weight of each of host/sensitizer combina Absorption = 0.46 microns-0.47 microns Y,(Yttrium) 55 tions (a), (b) and (c), (d). Similarly, in the event that the

Er,(Erbium) wire mesh is employed, the host sensitizer/sensitizer (d) Y3Al5O12: Ert combinations may be added in the same proportions to Absorption = 0.52 microns-0.54 microns (Same) stainless steel wire and the combination material drawn (e) CaF2: Ut Where into wires and formed into mesh. Alternatively, after Absorption = 1.2 = microns-l.3 microns Ca,(Calcium)

Emission = 2.51 11 microns-2.613 F(Fluorine) the preparation of the stainless steel wire cells, mullite microns U(Uranium) together with the host sensitizer combinations could be applied in several bands in the plastic state around the stainless steel wire mesh cells, and then fired, to pro

In the foregoing tabulation it may be noted that there duce the desired result. This result, as mentioned above, are only three separate combinations of host and sensi 65 involves the provision of spaces throughout a body of tizer materials which are being employed. More specifi material constituting a heat reservoir, and locating cally, the combination of calcium tungstate and neo host/sensitizer combinations around the boundaries of dymium produce output radiations both at 1.065 mi these spaces or voids in the material.

Page 32

The chemical formula for mullite was given above, favored in a low-symmetry environment. As long as the and it is again noted that mullite includes aluminum emission transitions are few in number, the low symme oxide Al2O3 and silicon dioxide SiO2 in certain propor try environment may prove to be advantageous by tions noted above. In order to enhance the "HASER' virtue of a broader absorption coverage. action and increase the energization of the host/sensit Different classes of active ions seldom find optimum izer combinations (a) through (e) set forth above, a environments in the same host structure. Different acti material such as chromium, which acts as a sensitizer in vator ions are best accommodated in oxides or fluo cooperation with the aluminum oxide in mullite which rides, where the cations of the matrix are approximately acts as the host material. The chromium-aluminum ox equal in size to the activator. Al2O3, MgO, MgF2, and ide, sensitizer-host combination produces strong output 10 ZnF2 are typical matrices for transition-metal ions, radiation at a number of wavelengths, including output CaF2 is particularly useful for divalent rare-earth ions, radiation centered at 0.6934 microns, when the Al2O3 is and CaWO4, LaF3, and Y2O3 are best suited for triva absorbing energy at 0.5 microns. The radiation centered lent rare-earth ions for lasers. Y3Al5O12 can readily at 0.6934 is broadened at the high operating conditions accommodate both trivalent rare-earth ions and triva so that the radiation extends from 0.6 or 0.65 to 0.75 or 15 lent 3d transition-metal ions. Certain crystals have con 0.8 microns, thus providing supplemental input energy veniently disposed matrix absorption bands and these to example (a) set forth hereinabove, which involves can be used to absorb pumped radiation over a broad absorption at about 0.74 to 0.76 microns. The Al2O3/Cr spectrum.

combination may also directly apply energy to the feed The excitation may be subsequently transferred to stock when the output radiation is of the proper fre 20 trivalent rare-earth ions contained in the matrix and quency and may also pump other host/sensitizer combi therefore, greatly enhance the overall efficiency of nations. When chromium is used it will be present in fluorescence. It probable is essential to move into the quantities in the order of five per cent by weight or less visible region, to obtain continuous operation for mo of the mullite employed as the basic material of the lybdates or niobates.

tubes 352 as shown in FIGS. 11 and 12. 25 In comparison, materials which have their matrix absorption edges well above the excitation range but

MATERIAL REQUIREMENTS absorb strongly as a result of the active ions having The primary requirements for potential solid-state strong absorption bands of their own, together with Maser/Haser materials are, first, that the composition narrow emission lines, can afford very favorable pump should fluoresce with a suitably high intensity at ele 30 ing conditions.

vated temperatures by means of thermal energy alone Ions such as, Cr3+, Chromium, and. Dy2, Dyspro and, second, that the matrix should be transparent or sium offer this advantage.

has no absorption transition at the operation frequency; The past decade has provided rapid extension of it should also be chemically stable and have no caustic spectral measurements and theoretical analysis, such characteristic. 35 that the properties of most of the divalent and trivalent Preferably, the terminal level of the Haser transition activator species are well understood. The interest in of the active ion should be far enough above the ground solid-state masers and lasers, has motivated the prepara state so that three or four-level operation is possible and tion of various crystals containing divalent rare-earth at elevated temperatures. ion species and the extensive study of their infrared The lifetime of the metastable level from which the characteristics. Parallel studies of the infrared proper Haser transition originates should be, insofar as possible, ties of the transition-metal ions and trivalent rare-earth equal to the lifetime for spontaneous emission with no ions have been equally productive.

constraints imposed by competitive dissipation to the The selection of materials for Hasers which will oper matrix. In four-level operation of the lifetime of the ate in the infrared region depends on the disposition of terminal level of the transition must be smaller than that 45 the vibrational bands in the matrices. Because vibra of the metastable level; otherwise, a suitable excess tional levels may drain an electronic state, they should population in the upper level cannot be maintained. not be too close below the metastable level, or the latter This condition is generally obtained when the termi should lie below the vibrational levels in energy. nal level lies in the phonon absorption region, prefera Suitable coupled pairs which provide a mutual cross bly between 6000 and 19,000 cm 1. In addition, it is 50 relacation can also be used advantageously to minimize helpful for the excited active ion to be unable to absorb loss of efficiency due to fluorescence from levels lying photons corresponding in energy to the Haser transi higher than the metastable level of interest and loss to tion. Where such absorption into a higher level or band the phonon spectrum. It is also desirable to increase the is possible, the photon/phonon flux in the particulate efficiencies of masers that terminate on phonon levels. cavity is reduced and the metastable level depleted. 55 This mechanism of operation offers the possibility of a For best coherence the active ions should occupy maser that can be tuned over a broad range of frequen equivalent positions in the host structure, so that there CleS.

will not be a multiplicity of spectra. When these ions are PREFERRED LATTICES in completely unique sites, the emission spectrum has the minimum detail and line width consistent with the Oxygen-dominated compounds are those in which site symmetry, the crystal field, and the active-ion con oxygen is a major chemical constituent of the host lat centration. In general, the higher the site symmetry the tice. They may be classified according to their chemical more degenerate the electronic states of the active ion. composition into four groups.

Therefore, fewer distinct transitions should be observed The first group, comprising the simplest compounds, in fluorescence and, on the average, each emission tran 65 has the generic formula MO, representative numbers sition should flouresce a greater portion of the absorbed being the alkaline earth oxides and Al2O3, Y2O3, and energy. However, there are also fewer distinct absorp ThC2, with Cr3+, Mn2+, and the rare earths as com tion transitions, and certain emission transitions may be mon activators. Other compounds included in the ge

Page 33

neric formula are CuO, and ZnS and the other II-VI Luminescence is generally investigated as a steady wide-band-gap compounds.

The second and largest group are the binary oxides, with the excitation source andtheemits state phenomenon, wherein compound interacts radiated energy

MAOz, where M is any element of Group II, A or B, continuously. The thermodynamic parameters of the and Period 2 to 6, and A is Ti, Zr, V, Nb, Mo, B, Al, Si, compound remain time independent at every point in Ge, P, As, Sb, or S. the system, despite the occurrence of excitation, emis In many cases x=4y, the oxygens nearly tetrahe sion, and dissipative processes. drally arranged arond the multivalent atom, A. Irreversible thermodynamics is concerned with just The common activators are Mn2+, Mn, Ag,

Sn2t, Tlt, Pb2+, and the rare earths. Included in this O such open systems, which interact with their environ ment in a stationary way.

group also are the wwell-known self-activated com pounds comprised of tungstates and molybdates, which theItentropyis a principle of irreversible thermodynamics that are commonly called scheelites (although some do not region of theproduction system is positive in every macroscopic undergoing irreversible processes.

have the scheelite structure). These require no activat ing impurity, because the energy transitions take place 15 forMacroscopic regions refer to regions large enough microscopic fluctuations to exist but small enough within the anion, although impurity-activated lumines for approximate equilibrium to exit within each region. cence is also observed.

Of the impurity-activated members of the binary We are especially interested in the more complex exci tation mechanisms involving energy transfer between oxides, the borates, phosphates and silicates are the 20 different most numerous. macroscopic regions not in equilibrium with each other.

Ternary systems, M.A.B.O., constitute the third category. M and A and B are the elements listed in the LIGHT ABSORPTION AND COLOR binary systems plus the alkali metals.

The most common activators, other than the rare An electromatic radiation, (such as radiowave, light, earths, are those listed with the binary oxides. There are 25 and X-ray) can be characterized by its particular wave a few ternary compounds not containing tungsten or length, LAMBDA, A (measured in cm or A), or by its molybdenum which are believed to be self-activated. wave number, N, v (the reciprocal of the wave length), v= 1/N, commonly expressed in reciprocal cen

There are many other oxygen-containing inorganic timeters, luminescent solids, including a large number of rare 30 cm-l.

earth salts and impurity-activated nitrites, carbonates, Each unit of radiation (a photon) corresponds to a etc. The work on the latter is largely incomplete. The quantum of radiant energy, E, which is directly propor work on the rare-earth salts constitutes a well-studied tional to the wave number, v. Since chemical calcula separate discipline (Diecke et al., 1961). tions are founded on a mole basis, in discussing the Considering the small number of possible combina relationship between radiant energy and chemical pro tions of simple oxides and activators, it is surprising that 35 cesses (responsive activators and hosts) it is convenient new prospects in this group continue to be found. New to express radiant energy in kcal/mole of photons. We compounds, however, consisting of oxides of antimony, can do so with this accepted relationship: the radiant germanium, thorium, calcium, strontium, yttrium, and energy in 1 mole of photons, with v=350 cm, is equal gadolinium with various activators have been devel to 1 kcal.

oped over the last few years. Therefore, we can obtain the energy (expressed in The valence of manganese in phosphors or com kcal/mole) for photons of a given wave number simply pounds is interesting because of its use as an activator in by multiplying the value of v expressed in cm by the many lattices. Kroger (1948) showed that the broad conversion factor structureless red or green emission spectra of man 45 ganese-activated compounds is generally due to Mn2+, 1 kcal/mole of photons whereas the red narrow-banded emission is due to 350 cm

SUMMARY For example, the energy of light photons with

In the same way that the spectroscopy of atoms pro vided basic information on atomic structure, careful study of controlled luminescence of solids provide in energy = 20,000 x kcal/mole of photons

formation on band structures and energy levels of impu 57.1 Kcal/mole of photons rities and imperfections. In some cases, the spectra of 55 impurities yield, through the application of crystal field and the energy of a single photon of v=20,000 cm is: theory, information on the symmetry and strength of the crystal field at the impurity site. The absorption or excitation spectra involve electronic states of the system energy 1 photon = 57.1 kcal/mole of ph. with equilibrium nuclear coordinates characteristic of 60 6.02 x 10 photons/mole of ph. the ground state; luminescent emission spectra involves 9.48 x 102. Kcal/photon. electronic states with the equilibrium nuclear coordi nates of the emitting state. The wave number, and the energy, of electromag Additionally, detailed theoretical knowledge of band netic radiations varies within an extremely wide range structure and of impurities and imperfections obtained 65 -v= 101 cm 1 for the y-rays emitted in nuclear reac from semiconductor and photoconductor research pro tions to v = 10-6cm for radiowaves. In between these wides understanding of the luminescence of these mate two extremes, there is a continuum of radiations of rials.

intermediate wave numbers-the "visible region',

Page 34

which extends approximately from 27,000 cm to (3.2) Expansion of the interaction hamiltonia Differ 13,500 cm-l. ent types of radiation. In general, when white light strikes a substance, part (3.3) Density of final states. . . . . of the light is absorbed and part is transmitted (if the (3.4) Transition probability per unit time. substance is transparent) or part is reflected (if the sub (3.5) Dipole radiation. stance is opaque). A substance may absorb preferen (3.6) Selection rules for radiative transiting tially the light photons of one (or more) region(s) of the (3.7) Selection rules for transitions between eigen spectrum, so that the transmitted light or the reflected states of angular momentum. light is relatively richer in the radiations of the remain 10 (3.8) Selection rules for atomic systems. ing regions. (3.9) Electric dipole radiation. The combined effect of these remaining radiations is (3.10) Magnetic dipole radiation. observed as a particular color (when it is in the visible (3.11) Electric quadrupole radiation. spectrum) (3.12) Selection rules for ions in crystals. For example, a substance that, when exposed to white 15 (3.13) Intensities of radiative transitions light, absorbs almost all photons in the entire yellow-to (4.) Ion-Vibration Interaction: Radiationless Processes, violet region (say from 17,000 to 27,000 cm) will Thermal Shift, and Broadening of Sharp Spectral "appear red', because only the radiations in the red Lines region of the spectrum (13,500 to about 17,000 cm), (4.1) Ion-vibration interaction. which are not absorbed, remain to be observed. (4.2) Radiationless processes in a crystal absorption Similarly, a substance that "appears yellow' absorbs 20 and emission of a phonon. photons of both the green-to-violet region (from 19,000 (4.3) Raman processes.

cm 1 to 27,000 cm-1) and the red region (from 13,500 (4.4) Orbach processes. to 16,000 cm-1) of the visible spectrum. (4.5) Multiphonon processes. Since light (radiation) is energy, the absorption of 25 (4.6) Line broadening mechanisms radiation is absorption of energy; it is well known, that, (4.7) Probability densities and superposition of proba if a substance absorbs light, the corresponding absorbed bility densities: Voigt profile energy may be used to promote certain atoms, ions, or (4.8) Thermal broadening of sharp lines. molecules of a substance from "ground-state' to an (4.9) Raman scattering of phonons "excited state". For example, an atom, ion, or molecule 30 (5.) Vibrational-Electronic Interaction which absorbs a photon of a given wave number takes (5.1) Ion-vibration interaction in molecular com on a "quantum' of energy that may serve to promote one plexes.

electron from a lower energy orbital to a higher (avail (5.2) Vibronic spectra of molecular complexes able) energy orbital. In general, different electronic (5.3) Vibronic lines in absorption. transitions involve the absorption of different quanta of 35 (5.4) Selection rules for vibronic processes. energy. (5.5) Space groups and lattice vibrations.

HASER DESIGN CONSIDERATIONS

(5.6) Normal modes of vibrations in crystals.

(5.7) Lattice absorption in perfect crystals.

Some of the factors which are involved in the design (5.8) Phonon activation due to impurity ions in crys of Haser apparatus include the following: 40 tals.

(a) Thermally isolated chamber. (5.9) Selection rules for vibronic transitions due to (b) Sensitizers-activators responsive to input heaten magnetic impurities in crystals. ergy frequencies. SPECIFIC EXAMPLES (c) Design amounts of "impurity' sensitizers re quired. 45 Some underlying principles involved in the selection (d) Design the host solid while considering the fol of Haser systems have been set out hereinabove and a lowing: preferred embodiment has been described which in volves water vapor as a feedstock and the generation of (1.) Lattice Vibrations hydrogen and/or hydrogen peroxide. It is to be under (1.1) Geometry of crystalline solids. 50 stood that the Haser concept is not limited to the spe (1.2) Crystal lattice and reciprocal lattice. p1 (1.3) cific embodiment described herein but has more general Brillouin zone and g-space. applicability in the conversion of broad spectrum heat (1.4) Lattice vibrations of an infinite crystal with one energy or radiation to particular frequencies which lie atom per unit cell. within the absorption band or bands of any selected (1.5) Lattice vibrations of a finite crystal with one 55 feedstock.

atoms per unit. cell. The feedstock may be gaseous or liquid or even a (1.6) Lattice vibrations of a crystal with more than slurry, and may be brought into proximity with the heat one atom per unit cell. reservoir and associated host and sensitizer material in (2.) Thermodynamics of Phonons any desired and practical manner. The heat in the heat (2.1) Density matrix of an ensemble reservoir may be generated in any suitable manner in (2.2) Internal energy of a phonongas. cluding the use of the exothermic reactor for generating (2.3) Einstein and Debye approximations of the den hydrogen and hydrogen peroxide and/or the combus sity of (A) phonon states. tion of the hydrogen and hydrogen peroxide. (2.4) Phonons and photons: similarities and differ The feedstock may for example be directed through ences. 65 the heat reservoir by a pipe suitable coiled to provide (3.) Ion-Photon Interaction: Absorption and Emission for adequate exposure to the radiation. The pipe may be of Radiation transparent to the radiation being applied to the feed (3.1) Ion-radiation interaction. stock; or alternatively, the pipe may be made of material

Page 35

containing the specially selected host and sensitizer Example No. 6 material.

In the following examples, a number of reactions are .

set forth and these are followed by an identification of a B2H, PhNO2 -- host and sensitizer material which will concentrate the B2OH, SEVERAL NITROGEN COMPOUNDS = (Reaction) broader spectrum heat energy to one of the absorption bands of the feedstock. Incidentally, in the following Absorption = 0.5 micron Emission = 1.0612 microns examples, in addition to the standard symbols for the elements, the following abbreviations are used: Et for 10 ethyl, C2H5; Ph for phenyl, C6H5; Pr for propyl, C3H7; Example No. 7 and Bu for butyl, C4H9. In addition to the host and sensitizers shown in each of the following examples,

Al2O3 in mullite and Cr +3 may advantageously be 5 Me2CO, Et2O (solution) - 150 - PROPYL ALCOHOL, ADDITIONAL COMPOUNDS = (Reaction) used (absorption at 0.5 microns; emission centered at CaWO4: Ndt 0.6934 microns). As noted above, the mullite may con Absorption = 0.57-0.60 micron veniently be employed to physically support the host Emission is 0.9145 micron and sensitizer materials. The actual examples follow:

Example No. 1 Example No.8 B2H, Et2O (solution) -- CYCLOHEXANONE - CAPROIC ACID, HYDROBENZOIN, ISOHYDROBENZOIN = (Reaction) 25 RESEN, ALDEHYDE = (Reaction) Al2O3 (malite): Crit Sr. F. : Sm't CaF2: Tm't Absorption = 0.5 microns --- Absorption = 0.58-0.68 micron Absorption = 0.39-0.46 micron Emission = 0.6934 - 0.1 micron Emission = 0.6967 micron Emission = 1.16 microns

Example No. 2 Example No. 9

AcH,NH3,HCNCaq.) -- C6H12O3N2 = (Reaction) CARVONE, EtOH (aq)- KETONE RESEMBLING CAMPHOR, RESIN = (Reaction)

LaP: Pr’t 35 Ca WO4: Prit

Absorption = 0.43-0.48 micron Absorption =0.43–0.49 micron Emission = 0.5985 micron Emission = .0468 microns

Example No. 3 Example No. 10

PARALDEHYDE, O2- H2O2 = (Reaction) CAMPHOR, EtOH (aq) - CAMPHOLENIC ACID, = (Reaction) AcH,CoH6O

CaF2 : Sm't CaF2: Dy?" : Sm't

Emission = 0.7085 micron Absorption = 0.58-0.68 } 0.8-1.0 micron Emission = 0.6967 micron 2.36 microns

Example No. 11

HCHO, FeCls (aq) - FeCl2, HCO2H, HCL = (reaction) (glycolaldehyde) COUMARIN, EtOH, PARALDEHYDE, -, HYDRO - Y2O3: Eut D - COUMARIN or C6H6 (solution) = (Reaction)

Absorption = 0.2-0.28 micron

Emission = 0.613 micron Absorption = 0.57-0.6 0.74-0.76

Emission = 0.9145 micron 1.065 microns

Example No. 5 2.046 microns

B2H, AROMATIC KETONES - POLYMERS, other KETONES, Example No. 12 BENZOATES = (Reaction)

Y3Al5O12 : Yb't 65 BENZOIN, EtOH (solution) - HYDROBENZOIN, Achs, Absorption = 0.9-1.0 microns ISOFORM RESIN = (Reaction) Emission = .01 microns

Y2O3: Eut

Absorption = 0.87 micron

Page 36

-continued cluded in tubes 412, as described above. Hydrogen H2 BENZOIN, EtOH (solution) - HYDROBENZOIN, Ach3, and hydrogen peroxide H2O2 are drawn off through the

ISOFORM RESIN = (Reaction) upper manifold 404 and the connecting line 434 through Emission = 0.6113 micron valve 436. During the hydrogen displacement phase of the cycle, additional oxygen may be supplied through line 438 via valve 440. The additional oxygen promotes.

Example No. 13 the formation of hydrogen peroxide, which is, with the hydrogen, drawn off through line 434.

The overall cycle of reaction chamber 402 may be

O substantially as indicated by one of the two plots shown

QUINONE, Et2O (solution) - HYDROQUINONE, RESINS = (Reaction) in FIG. 7. Accordingly with the steam valve 432 and Same Host/Sensitizer; Absorption; and Emission as the valve 436 to the hydrogen storage tank both closed,

the vacuum may be applied to the reaction chamber 402

so that disproportionation of the oxygen from the reac

Example No. 14 tant takes place.

While the hydrogen displacement at high pressure and the oxygen disproportionation phase of the cycle at

THYMOQUINONE, Et2O (solution) - POLYMER low pressure is occurring in the main reaction chamber (POLYTHYMOQUINONE) = (Reaction) 20 402, the feed stock may be continuously passed throgh

Same Host/Sensitizer; Absorption; and Emission as the heat and radiation exchanger 414, 416, 418, at a Nos. 1 and 3 suitable rate to maintain the desired high temperature and high level of radiation of the feedstock. Incidentally

Example No. 15 the tubes 418 interconnecting the upper chamber 414 25 and the lower chamber 416 may be made of mullite including the host/sensitizer materials mentioned in the 4 - Me QUINOLINE - RESEN, ALKALI SOLUBLE various examples given above. Similarly the manifolds PRODUCT = (Reaction) 414 and 416 may be made of such materials. Alterna Same Host/Sensitizer; Absorption; and Emission as tively the elements 414, 416, and 418, may be made of Nos. 5, 6, and 8 30 metal, such as stainless steel, to which suitable quantities of host/sensitizer materials have been added in order to

FIG. 13 is a schematic showing of an apparatus for a give the desired intimate irradiation action with regard continuously processing feed stock such as the materials to the feed stock.

disclosed in the foregoing examples, or steam, of course. Instead of using a single reaction chamber as shown In FIG. 13 the reaction chamber 402 is provided with 35 in FIG. 13, a heat and irradiation exchange unit could upper and lower manifold chambers 404 and 406 which be employed with a multiple reaction chamber appara are separated from the main portion of the reaction tus such as that shown in FIG. 9. When used with a chamber 402 by apertured plates 408 and 410. Within multiple reaction chamber arrangement such as that the reaction chamber 402 are a large number of the shown in FIG. 9, of course the heat exchange elements ceramic tubes 412 such as those shown in FIG. 11. All must make sealing engagement with the walls of the of the space within chamber 402 apart from that occu individual reaction chambers which will be at different pied by the tubes 354 is filled with a reactant such as pressures during different portions of the individual manganese oxide or other reactants disclosed elsewhere in the present case and in my prior co-pending specifica staggered cycles in the different reaction chambers. It may be noted that, in accordance with disclosures tion cited above. 45 in my prior co-pending patent application cited above, A heat or radiation exchanger including upper and and teachings found elsewhere in the present specifica lower manifold structures 414 and 416 as well as the tion, the hydrogen and H2O2 "tailings', obtained as a interconnecting tubes or pipes 418 exposes the feed vacuum stock, which is applied through input tube 420 and hydrogenisand/or being drawn on line 438, and such output hydrogen peroxide from line 434 as brought out through tube 422, to the high temperatures 50 may be desired, may be applied through line 426 to the and radiation present within the main reaction chamber central burner 424. This may serve the purpose of sup

plying additional heat to

At the center of the apparatus shown in FIG. 13 is a rapid flow of feed stock throughthe entire unit to permit more burner 424 to which a lower inlet pipe 426 and an upper out lines 420 and 422 with outlet pipe 428 are connected. This central burner unit 55 loss of temperature in reaction chamber 402. may be of the type shown in FIG.9 of the drawings and ENERGY BALANCE as described hereinabove. The entire reaction chamber 402 shown in FIG. 13 is fully insulated and mounted as In my prior co-pending patent application an "En shown in FIG. 9, and equipped with suitable automatic ergy Balance' section was included. In the present valving of the type described above in connection with specification, a portion of the prior analysis will be set other embodiments of the invention. forth, and a more thorough energy analysis involving In operation, steam is initially supplied to the reaction the new material in this application will be included. chamber 402 through inlet line 430 when valve 432 is In view of the fact that the apparatus of the present opened. Of course prior to this initial step, the reaction type and as disclosed in my prior application are exo chamber 402 has been preheated to a temperature in the 65 thermic on a net basis and also produces hydrogen or order of 1000 Kelvin, and the steam is supplied under hydrogen peroxide which can be burned, there have high pressure. Hydrogen is then displaced by the action been some suggestions that certain so-called Laws of of the reactant, and the host/sensitizer materials in Thermodynamics are being violated. This is of course

Page 37

not the case, as will be developed by the Energy. Bal ance analysis set forth below.

From an overall standpoint, the present system may POTENTIAL ENERGY OUT: be viewed as providing an energy balance and not vio K. Ca lating any "Laws of Thermodynamics' as a result of the (4) 2HO 43.2 low energy content gaseous products which are re (5) H--O-4-O--H 223.96

leased in the course of the process. These low energy (6) H2, or 63.479 ot gaseous products may include HO and HO2, which are (7), H2O2 114.262 381.422 K. Cal (H2O2. Out) less well known gaseous products. When these gaseous Efficiency (H Out) = 0.78 products are released into the atmosphere, it is believed 10 Efficiency (HO Out) = 0.90 that they absorb high frequency radiations, and eventu ally change state to become hydrogen gas, oxygen gas, Actually, there is often a combination of H2 and H2O water vapor, atomic hydrogen and atomic oxygen. In resulting in an intermediate efficiency. one sense, therefore, the present systems may be consid Now, from a Gibbs Free Energy (G) Analysis stand ered to utilize solar energy. 15 point involving Enthalpy (Heat, H), Entropy (S), and The stoichiometric reactions set forth below repre temperature T, the following analysis obtains: sent one of several modes of operation which may ob In the following analyses, the enthalpies and entrol. tain in implementations of the present invention. pies of the starting reactants are subtracted from the The foregoing equations may be analyzed from two enthalpies and entropies, respectively, associated with different standpoints. Incidentally, it may be noted that 20 products. The letters "in' have been associated with the the "2HO' designated (4) in the upper equation is actu initial values relating to the starting products. ally evolved in the disproportionation phase. In addi tion, a portion of the hydrogen gas H2 from (6) in the Oxygen Sequestering Reaction upper equation is an input in the lower equation which (Upper combines with the disproportionated oxygen to form 25 AH/orm:Equation designated "Stoichiometric Reaction")

HO. Also, of course, the incident photons are applied in - 43.2 - 33.96 the atmosphere, and not in the apparatus per se. It Sform: 20+45.11) (in)2(+26.4) (in) 4(+12.7) - 43.89 should also be noted that the O2 input designated (2) is -- 43.89 - 56.01 essentially optional and may involve the venturi unit AHea: -627.16-(-598.4) -28.76 Kcal/Mol-Egn 212 or inlet 217, of FIG. 6, whereby additional O2 is 30 AS: -- 194.59-(-- 143.02) +51.57 Cal/Mol-Egn X Deg. supplied to generate H2O2, as noted above. TAS: 1000ge X (+51.57) = +51.57 Kcal/Mol-Egn

STOICHIOMETRIC REACTION (ONE OF SEVERAL MODES)

PHOTONS

CATALYST

2 H2O(n >2Mn2O3- GeMO2 + H2O2S H. - O - O - H --Ge2HO-S-H2O2(g) G

REVERSE REACTION

Now, the upper equation will be analyzed from a potential energy standpoint: 60 AG: AH - TAS = -28.76-(+51.57)

Reverse Reaction

POTENTIAL ENERGY IN:

K. Cai AH"form: 4(-126.7) (in)2(-228.6) - 43.2

(1) 2 H2O 41.2 65 AH": -500.4-(-506.8) = + 6.40 Kcal/Mol-Egn (2) O2 + H2 ) = 421.543 K. Cal. AS: +96.69-(+50.8) = + 45.89 Cal/Mol-Egn X Deg. (3) hv 237.43 TAS: 1000degrees x (+45.89) = +45.89 Kcal/Mol-Egn

Page 38

-continued mode emphasizes the production of hydrogen peroxide, H2O2, and carries over its use in the disproportionation

Complete Cycle *. . . part of the cycle. It may also be noted that the first (B)- -28.76 -- (-6.40) = -22.36 Kcal/Mol-Egn mode and second mode presentations are not precisely 5 comparable as H2O(e) is assumed as an input for the first

(S)- +51.57 + (+45.89) = +97.46 Kcal/Mol-Egn mode, and H2O) is assumed as an input for the second mode as set forth below. As indicated by the negative

From the foregoing analysis, it may be noted that the value of the enthalpy for the two reactions of the sec heat or enthalpy for the hydrogen generation portion of ond mode, the cycle is equal to -28.76 K Cal/Mol-Eqn, which O The equations it is also exothermic on an overal basis. means that the reaction is exothermic. For the "Reverse for (1) hydrogen displacement and (2) oxygen disproportionation, are set forth below, to

Reaction' or the oxygen disproportionation part of the gether with their associated Enthalpy cycle, the heat or enthalpy figure is +6.40 K. Cal/Mol and Gibbs Free Energy functions. (H), Entropy (S)

DISPLACING HYDROGEN

AH 2(-59,24)2(-228.39) 4(- 23.63) 0 O 20-33.96) g 2C+55.59) 20-40.13) 4(+ 19.46) 2C-39.70) 20-49.00) 20-70.94)

R -562.44 - (-575.26) - +12.82 kcal/Mol - Eqn.

ASE --397.12 - (-191.44) = 205.68 Cal/Mol - Eqn. x Degrees

TAS: top 2009 +205.68 Kcal/Mol - Eqn.

OXYGEN

DISPROPORTIONATION

e. hwa ( 1200A

exit machine

1000 K. w w

AHE: 4(-123.63) 20-228.39) -59,240 0 s: 4(+1946) 2C-- 40.3) --55.59 --SS.3 - 42.83

AH: -516.02 - (-494.52) =w -21.50 Kcal/Mol - Eqn.

AG = AH - TAS = -21.50 - (+156.14) = -177,64 Kcal/Mol - Eqn.

Eqn. This means that the disproportionation part of the cycle is endothermic, but that the heat required is much less than that generated in the other portion of the cy cle. With thoroughly insulated equipment the heat gen 55 The values for Enthalpy (H) and Entrophy (S) used erated during the exothermic portion of the cycle, in the in the foregoing analyses are all taken from published same or other adjacent reaction chambers, is more than texts as follows:

sufficient to provide the heat needed during the dispro portionation part of the cycle. It may also be noted that 1.

the positive entropy value for the “Reverse Reaction', MnO2 Enthalpy (H) 900 K. = 123.63 or the disproportionation cycle, indicates that this reac 60 MnO2 Entropy (S) 900 K. = 19.46 tion will go forward spontaneously.

ENERGY BALANCE-SECOND MODE Mn2O3 Entropy (S) 1000 K. =40.13 Another pair of (1) Displacement of Hydrogen and 65 Selected values of Chemical Thermodynamic Prop (2) Disproportionation reactions appears below, to erties, by F. D. Rossini et al, and U. S. Government gether with a classical Gibbs Free Energy Analysis. National Bureau of Standards Accession No. Also included are the text citations for the entropy and 6500390, N.B.S. Circular No. 500, dated Feb. 1952, enthalpy values used in the analysis. The following pages 122 (MnO2) and 123 (Mn2O3)

Page 39

Thermodynamic Properties of the Elements Pub ...(1.130859375x109)x(3.64x10) lished November 1956, American Chemical Society, 1155 Sixteenth Street, N.W., Washington 6, D.C. Photons=4.116.328.125x1023 (second) 4. H2 Enthalpy (H) 1000 K. =0 (By Definition). . . 5 C. Assuming a continuum of 15 seconds

6. O2 Entropy (S) 1000 K. =49.0 . . . .. 15.0x(4.1163281.25 x 1023)

H2O Enthalpy (H) 1000 K. =59.24 Photons in 15.0 Seconds=6.174492188)X 1024 H2O Entropy (S) 1000 K. =55.59 D. Since there are 6.02x 1023 photons in 1. mole (of "Thermodynamic Properties of Minerals and Related photons)

Substances . . . '-Geological Survey Bulletin 1259

Washington, D.C., U.S. Dept. of the Interior, 1968, 6.174492188 x 1024 p. 114. 6.02 x 1023 8. OH Enthalpy (H) 1000 K. =9.13 15

10, OH Entropy (S) 1000 K. =52.49 Energy (15 sec.)= 10.256632 moles photons 11. H2O2 Entropy (S) 1000 K. = 70.94 E. Converting to Kilocalories

TRC Tables, Selected Values of Properties of Chemi 10.256632X26.48 cal Compounds, Thermodynamics Research Center, Energy=271.60 Kilocalories (average) Texas A&M University; Table 2 IT for items 9-12 F. Energy Required to Dissociate (1) Mole H2O) above; Table 2 I W for items 7 and 8 above. Mole=59.24 Kcal From the negative value of -8Kcal/Mol-Eqn. of the 25 enthalpy (heat) of the entire reaction, including both 271.6

displacing hydrogen from water vapor and dispropor tionating oxygen from the reactant, it is clear that the process is exothermic, in addition to generating hydro G.

gen and/or hydrogen peroxide. And this surprising 30 result, in one or the other or a combination of the modes (1) Dissociation by Reactant 2.00 Moles H2O) described in the foregoing equations has been con (2) Dissociation by Radiant Energy 4.58 Moles H2O(g) firmed by the operation of prototypes using manganese Total 6.58 Moles H2O) oxide as the reactant.

Set forth below is a further analysis involving the 35 H. 6.58 Moles H2O)=5.22 cu. ft. H2O2) photon dissociation of H2O, and an examination of the I.

energy "borrowed from nature' and "returned to na 1. cu. ft. H2O2=318 BTU ture', or to the environment. In connection with the 5.22 (cu. ft.)x318 (BTU)= 1660.00 BTU - following analyses, it may be noted that the energy for 15.0 seconds = 1.660.00 (BTU)=418.49 Kcal (Po photon dissociation of the H2O is obtained from the tential) heat reservoir of hot reactant which is of course main J. Energy Required to Operate Unit for 15.0 Seconds

(1) Dissociating 6.58 Moles Liquid water at 70.6 Kcal/Mole = 389.8 (2) Sensible Heat Lost in Gases and Cooling Water a 22.4 (3) Radiated Heat Losses (all surfaces) 5.29 (4) Vacuum PUmp (1.0 H.P.) 0.27 (5) Water Pressure Pump (1.0 H.P.) a 0.27 (6) Cooling Fan (Electronic Controls) (0.3 H.P.) 0,10 (7) Cam-Motor and DC Controls (0.3 H.P.) t 0.10 (8) Digital Readouts Power (0.1 H.P.) 0.03 (9) Compressed Air (0.5 H.P.) 0.4 (10) Compressed Hydrogen (0.5 H.P.) 0.14

tained at an elevated temperature by the net exothermic nature of the hydrogen displacement and oxygen dis 55 proportionation cycle. When mention is made of the combustion of H2O2 in the following analysis, this com K. Energy Balance=Output Minus Input bustion is in the course of performing useful work such as driving an engine, or the like, apart from the reaction 60 48.5-418.50 chamber as described herein. a

PHOTON DISSOCIATION OF HO BORROWED FROM NATURE (during 15.0 sec. period)

A. Average number of <(0.008)> particulates in 539.0 A. Energy Kcal Cu. in. reaction chamber.

65 1.658 Moles H2O(1) x 70.6 Kcal/Mol ar 389.8 = 1.1308593.75 x 109 2. Peripheral Equipment (15.0 sec.) 28.69 (Kcal) TOTAL 48.5

B. Assuming radiated energy frequency averages

Page 40

eutetics, and with other materials to obtain desired tem

RETURNED TO NATURE

perature and mechanical properties.

FIGS. 14 and 15 are particularly useful in analyzing

A. Potential Energy the apparatus of the present invention from a radiation B. Combustion of 5.22 cu. ft., H2O2 x 318 BTU/cu. ft. standpoint. FIG. 14 shows spectral radiant emittance,

= 418.5 Kilocalories or power in watts radiated at various wavelengths from Required Energy (from J) 418.5. Kcal a "black body" having a temperature of 1000 Kelvin, - Energy from Combustion, 418.5 Kcal = 0 while FIG. 15 is a similar plot showing photon emis sion, or the number of photons emitted at various wave

In closing, reference is again made to my copending 10 lengths. The FIG. 14 plot drops off more rapidly than patent application Ser. No 768,808, filed Feb. 15, 1977, that of FIG. 15 because shorter wavelength photons are in which more detail is presented relative to the temper more energetic and have higher power. In accordance atures, pressures, and other reactions which may be with known principles, the energy is directly propor used. As noted in the prior specification, the tempera 15 tional to the frequency and inversely proportional to the ture of operation should be above the dissociation tem wavelength. It may also be noted that, in the plots of perature for oxygen for the reactant being employed at FIGS. 14 and 15 the visible range is from about 0.4 to atmospheric pressure. Advantageous high speed results 0.7 microns. Accordingly for the temperature of 1000 have been achieved with the reactant in the pyroplastic Kelvin (about 727 Centigrade and about 1341 Fahren state of incipient fusion. Concerning pressures, the pres 20 heit), which is plotted in FIGS. 14 and 15, the radiation sure during dissociation should be at least as low as peaks in the spectrum at wavelengths somewhat longer atmospheric pressure, and preferably a vacuum should and at frequencies slightly lower than the visible band. be applied to reduce the pressure to a fraction of atmo FIGS. 16, 17, and 18 show a system for applying spheric. The vacuum may be applied to draw the tail radiant energy to a feedstock. In FIG. 17 the feedstock ings through the burner to extract additional heat from 25 is applied to reaction chamber 302 by inlet tube 304 the tailings. During the hydrogen displacement portion which is connected to manifold 306. Manifold 306 is of the cycle the pressure should be well above atmo supported by insulating ceramic material 308 which spheric to facilitate sequestering of the oxygen by the may either be in the form of a ring or a series of support reactant. Successful results may be achieved with reac ing blocks.

tants such as MnO with gauge pressures of about 100 to 30 The reaction chamber has an outer cylindrical stain 130 or 150 and up to 500 pounds per square inch. Even less steel wall 310 secured to upper and lower stainless higher pressures may be employed. Concerning the steel end plates 312 and 314. The chamber 302 is pro active reactant, as mentioned in my prior copending vided with a cylindrical ceramic liner 316 and upper specification, it preferably includes at least one metal and lower inner ceramic end plates 318 and 320. Suit having a plurality of valence states. It should also have 35 able insulation 322 such as ceramic foam and an outer an oxide which will, when subjected to water vapor at casing 324 are also provided.

elevated temperature and/or pressure, and preferably A series of coated wires 326 extend for most of the both, combine with the oxygen and displace the hydro length of the chamber 302 between upper and lower gen in gaseous form exothermically. The reactant also electrically conducting support members 328 and 330. preferably has the property of disproportionation or 40 As shown in FIG. 16, the wires 326 are made up of an dissociation to release the combined oxygen when the inner wire 332 of conducting or resistive material and temperature is raised or preferably when the pressure is an outer coating 334 of ceramic material of radiation reduced, and when the evolved oxygen is separated emitting material of one or more of the types previously from the reactant. Advantageously, the heat required in described.

the disproportionation part of the cycle is significantly 45 The upper and lower wire supporting members 328 less than that generated in the exothermic portion of the and 330 may be held apart by the elongated ceramic cycle when the reactant combines with the oxygen in member, and the metal rod 338 which extends into the the steam and releases hydrogen, so the entire cycle is lower hollow end of ceramic member 336. The coated exothermic. Also, the reactant should be susceptible of wires 326 are heated up by the application of electricity remaining in the pyroplastic state of incipient fusion 50 to power input conductors 340 and 342 to a temperature during the change in state from one oxidation level to in the order of 1000' Kelvin. This causes a certain another, and back again, under the described condi amount of thermal expansion in the wires, and by using tions. a suitable metal rod 338 which has a slightly higher Some of the metals and oxides thereof which fulfill coefficient of thermal expansion, the wires 326 may be the foregoing requirements include (1) antimony, (2) 55 maintained in operative positions relative to each other. cesium, (3) barium, (4) iron, (5) manganese, (6) chro In the case of a process involving steam as the feed mium, (7) iridium, (8) nickel, and (9) thallium. Other stock and where it is desired to have hydrogen gas and metals which have multiple valence states are known, H2O2 as the output product, air may be supplied either but most of these have practical problems which pre through input tube or pipe 304 and/or through separate clude their use. Thus, for example, mercury has too low 60 input 344 to the apertured ring shaped manifold 346 a melting point, and its oxides are unstable. In the case which is held in position by supports 348. Output prod of other metals having multiple valence states, their uct is drawn off through pipe 350. oxides may be poisonous, they may be caustic or are not In practice, and as indicated in the block diagram of available in practical or commercially available quanti FIG. 18, air may be supplied to the reaction chamber ties. Other metals having multiple valence states have 65 302 either through input 304 along with the input feed oxides which will not readily disproportionate. Combi stock such as steam, or through input 344 at the upper nations of reactants satisfying the requirements indi zone of the reaction chamber. When the air is supplied cated above may be employed in the form of alloys, through input 344, toward the upper end of 302, it com

Page 41

bines with the previously-formed hydrogen, resulting More specifically, before going into the example in from dissociation of the water vapor, to form H2O2. detail, it may be noted that various units are used in the Other blocks shown in FIG. 18 include a source of present specification in reference to the wavelength of electrical power 354, a supply of liquid water at 356, a the radiations which are employed. For reference pur steam formation unit 358, and a storage container 360 poses and for ease in converting various units, it may be for fuel gas such as gaseous hydrogen H2 and hydrogen noted that the visible range extends from about 4000 peroxide H2O2. The supply line for water is indicated at Angstrom units to 7000 Angstrom units, with an Ang 362, and that for air at line 364. strom unit being equal to 10-8 centimeters. Expressed As indicated by line 366, a portion of the fuel gas in microns this visible range corresponds to wave which is formed may be fed back to the steam formation 10 lengths from 0.4 to 0.7 microns, with a micron being unit 358 to increase the temperature of the water vapor equal to 10 centimeters. Similarly, when millimicrons being supplied to reaction chamber 302. After the unit is are employed to measure wavelength, they correspond in operation for a short period of time, the steam is to 107 centimeters, and the visible spectrum range is supplied to the reaction chamber 302 at a temperature from 400 to 700 millimicrons.

well above the intended operating temperature of reac 15 It may also be noted, in converting frequency to tion chamber 302 so that little or no electricity need be wavelength and vice versa that the frequency of light is supplied from the source 354. Thus, for example, with equal to 3 times 100 cms. per sec. and that the product steam being supplied at between 1100 and 1200' Kel of frequency and wavelength is equal to the velocity of win, the temperature of 1000' Kelvin desired within the light. Accordingly, using this simple expression that the reaction chamber 302 may be sustained with the supply 20 product of the frequency times the wavelength is equal of very little or no electricity over line 368. to the velocity of light, easy conversion may be made With reference to FIG. 20, the coated wires 326 are from frequency to wavelength, and vice versa. For shown supported by a screen 370 which may be made of convenience, reference is also made to Table I which any suitable high temperature resistant conducting ma indicates the location of the visible light band relative to terial. The wires 326 are woven in and out of the surface 25 the infrared and ultraviolet frequency bands, in addition of the screen 370 to form the array as shown in FIG. 17. to the remainder of the electromagnetic radiation spec It may be noted that the frame or support members 328 tum.

TABLE I

TABLE 1-2 The Wavelength Frequency, and Energy of Typical Electromagnetic Radiation

Approximate Typical Frequency, Wave Number, Energy,

Description Wavelength, A cycles/sec cm kcal/cinstein

Radio wave 1.00 + 103(1000 m) 3.00 x 10(300 kc) 1.00 x 10-5 0.0000000286 Short-wave radio 1.00 x 10(10 m) 3.00 x 107(30 Mc) 1.00 x 10-2 0.00000286

Wave

Microwave 1.00 x 108(1 cm) 3.00 x 100 1.00 0.00286

Far infrared 1.00 x 10(10) 3.00 x 103 100 x 10 2.86

Near infrared 1.00 x 10"(1) 3.00 x 1014 1.00 x 10 28.6

Wisible light

Red 7.00 x 10(700 mp) 4.28 x 1014 1.43 x 10 40.8

Orange 6.20 x 103 484 x 1014 1.61 x 10 46.

Yellow 5.80 x 10 5.17 x 104 1.72 X 10. 49.3

Green 5.30 x 10 5.66 x 1014 1.89 x 10 53.9

Blue 4.70 x 10 6.38 x 1014 2.13 x 10 60.8 Photo Wiolet 4.20 x 10 7.14 X 1014 2.38 x 10 68.1 chemistry Near ultraviolet 3.00 x 10 1.00 x 105 3.33 x 101 953 region Far ultraviolet 2.00 x 103 1.50 x 1015 5.00 x 10 142.9

Schumann ultra- 1.50 x 10 2.00 x 105 6.67 x 10 190.6 violet

Long X-ray 3.00 x 102 1.00 x 1016 3.33 x 105 953.0 Radiation Short X-ray 1.00 3.00 x 108 1.00 x 105 285,910 ):

Gamma ray 1.00 x 10-2 3.00 x 1020 1.00 x 100 28,591,000 / region

and 330 of FIG. 17 are shown as being formed of two With the foregoing background, reference is again parts. These two parts are open frame members which made to examples Nos. 1 and 2 of the 15 numbered clamp the screen 370 as shown in FIG. 20 and support examples set forth earlier in the present specification. It it. If desired or if the conductivity of the particular may be noted that the emission, for Example No. 1 was coating employed in the system is relatively low, the 55 approximately 0.69 microns corresponding to a fre coated wires 326 may be scraped bare and welded quency of approximately 4.34x10 cycles per second. contacts made at points such as those indicated at 372 in This corresponds to a red color in the visible spectrum. FIG. 20 to make better conductive engagement with Example No. 2 provides a yellow output light with a the screen 370 by which electricity is initially supplied wavelength of approximately 0.59 microns correspond to these wires. It is also noted that, instead of using the ing to a frequency of approximately 5.08 times 10 screen as shown in FIG. 20, the supporting structures cycles per second. Incidentally, another yellow line is 328 or 330 may be simple perforated plates with the produced by the materials of Example 12, with a wave coated wires 326 threaded through them. length of 0.61 micron, corresponding roughly to 4.91 Now, considering one specific example, the wires 326 times 1014 cycles per second.

of FIG. 17 may be coated with the host and sensitizer 65 Referring back to FIG. 17, one-half of the wires ex materials set forth in examples Nos. 1 and 2 of the 15 tending from support 328 to support 330 are coated examples set forth hereinabove in the present specifica with material providing red output radiation such as

specified in Example No. 1 referred to above, and one

Page 42

half of the wires are coated with material providing a above in connection with FIG. 17 to produce ultravio yellow output radiation. These wires are threaded let radiation.

through the supports 328 and 330 so as to be inter The lower set of wires 386, however, are coated to spersed with one another so that the yellow and red provide strong output radiation in the infrared radiation output radiation wires are not grouped together but are 5 spectrum, as disclosed hereinabove in connection with entirely interspersed with one another. examples A, B, and C. Accordingly, the arrangement of When feedstock is supplied to the reaction chamber FIG. 19 is organized to provide powerful radiation in 302, the radiation will be directed from the wires to theportion 380 which willimpinge vigorously on the feed medium and the radiation of different frequencies will stock and provide an initial very substantial dissociative impinge upon the discontinuities provided by the feed 10 effect on the water vapor. Then, in the upper portion stock vapors and will beat with one another and will be 378 of the reaction chamber the dissociation of the converted into sum and difference frequencies. More water vapor is continued, but at a frequency in the near specifically, cnsidering examples Nos. 1 and 2, the fre ultraviolet range which is clearly at a frequency spec quency for the red radiation of Example 1 was approxi trum with respect to the hydrogen peroxide, H2O2, mately 4.34 times 101 cycles per secod, and the fre 15 product gas which will not adversely affect or dissoci quency for Example No. 2 was approximately 5.084 ate it. The combined effect of the two stage radiation times 101 cycles per second. One frequency which will chamber with different radiation frequencies being em be formed as these radiations impinge on the feedstock ployed in each of the two chambers, is such as to maxi will be the sum frequency equal to approximately 9.42 mize the production of the desired output gas. times 101 cycles per second. This corresponds to a 20 Of course, in connection with FIGS. 16 through 21, wavelength of about 0.32 microns, in the near ultravio two specific examples of reaction chamber arrange let frequency spectrum. Water vapor has a number of ments employing radiation to produce desired product absorption peaks in the near ultraviolet frequency spec gases have been set forth. It is to be understood that trum and these peaks are broadened by the elevated through the examination of the spectral absorption temperature present at 1000 Kelvin at which the reac 25 characteristics of the feedstocks and products, and by tion chamber 302 is operated. Accordingly, in addition suitably providing radiation within the reaction cham to the dissociation action produced by the direct radia ber matched to the characteristics of the feedstock and tion at the red and yellow frequency bands, the power the product, many other similar combinations may be ful ultraviolet radiations will have a strong dissociative developed by those skilled in the art. effect on the water vapor being transmitted through the 30 It is also particularly to be noted that through the use reaction chamber 302. Incidentally, the energetic nature of coated wires, the amount of intial heat input required of the radiations in the near ultraviolet may be noted to raise the reaction chamber to operating temperature from the far right-hand column in Table No. I in which conditions, is greatly reduced.

the radiation in the near ultraviolet is shown to have an For completeness, one set of dimensions for the wires energy level in the order of double that in the red and 35 326,384 and 386 will now be given. The overall diame yellow regions of the visible spectrum. ter of the coated wires may be 0.00257 inch, and the Attention is also directed to the plot of FIG.21 show diameter of the inner metal wire is 0.00157 inch with the ing the absorption characteristic for hydrogen peroxide coating being about 0.0005 inch thick, adding about H2O2 which is being formed in the radiation chamber one-thousandth of an inch to the diameter. The inner 302. More specifically, it may be seen that the absorp metal wires may, for example, be made of tungsten or tion coefficient increases rapidly from the near ultravio other metal having a relatively high melting point and let range of 3000 Angstrons, or about 0.3 microns, to adequate strength at 1,000 Kelvin.

the far ultraviolet range toward the left of FIG. 21. FIGS. 22 and 23 show an alternative arrangement for Accordingly, with near ultraviolet radiation being em applying high frequency radiation to feedstock supplied ployed in the chamber of FIG. 17 (reaction chamber 45 to a reaction chamber. In FIG. 22 the reaction chamber 302) to dissociate water vapor, it may be noted that the perse is made up of two hemispheres 402 and 404 which desired product gas H2O2 will be little affected and will are secured together by bolts 406 which extend through be essentially transparent to this near ultraviolet radia the mating flanges 408 and 410 of the hemispheres 402 tion and will thus remain in its H2O2 chemical state, and 406. An outer sheet metal housing 412 is provided after it is formed, without adverse effect from the near 50 to enclose the unit and to support the various enclosed ultraviolet radiation. elements of the system. Thus, for example, the hemi FIG. 19 shows a alternative reaction chamber 376 spheres 402 and 404 are supported from brackets 414 which is divided into an upper section 378 and a lower secured to the housing 412. Between the reaction cham section 380. Dividing these two sections of the chamber ber 402,404 and the housing 412 is suitable insulation is a perforated ceramic plate 382. In addition, two dif 55 for 416 of the ceramic foam insulation type. ferent sets of coated wires 384 in the upper section and Feedstock is supplied to the reaction chamber 402, 386 in the lower section, are provided. These two sets of 404 through input pipe 418, and product gases are with wires are electrically interconnected by the links 388 drawn from the reaction chamber through pipe 420. which extend through the ceramic plate 382 and join Input radiation is supplied to the reaction chamber the lower support 390 for the upper set of wires 384 to 402,404 through the window 422 which may, for exam the upper support 392 for the lower set of wires 386. ple, be made of high temperature resistant quartz glass. Apart from being divided into two chambers with two FIG. 23 is taken along line 23-23 of FIG. 22. Shown sets of different coated wires in the upper and lower to advantage in FIG. 23 are the two lasers 424 and 426 portions 378 and 380 of the reaction chamber 376, the which direct coherent radiation of different colors chamber of FIG. 19 is generally similar in configuration 65 through the window 422 into the reaction chamber 402, to that of FIG. 17. 404 which has a highly polished interior surface. One of With regard to the nature of the coatings on the wires the lasers 424, 426 is a ruby laser with output radiation 384 and 386, the upper wires 384 are coated as described in the red spectral region, while the other laser is an

Page 43

yttrium aluminum garnet, or Yag laser with output applications of which the present patent application is a radiation in the green frequency band. These lasers are continuation-in-part. New FIGS. 24 through 32 will directed at an acute angle through the window 422 so now be described.

that the radiation of the two lasers beat to produce a FIG. 24 represents an alternative form of reaction higher frequency in the ultraviolet spectrum, as dis chamber which may be employed in a system substan cussed and developed hereinabove in connection with tially conforming to FIG. 18 of the present drawings. the radiation from the wires of FIGS.17 and 19. Ac More particularly, the reaction chamber 502 of FIG. 24 cordingly, the feedstock supplied to the reaction cham could be employed as the reaction chamber 302 of FIG. ber through the pipe 418 will be irradiated not only with 18. - the red and green direct laser illumination, but also by 10 Referring more particularly to FIG. 24, it includes an the beat frequencies which arise when the red and green outer cylindrical shell 504 which may, for example, radiation impinge on the discontinuities provided by the have a stainless steel interior surface, and contains a feedstock materials supplied to the chamber. substantial number of closely spaced mercury vapor It may also be noted that in all of the embodiments lamps 506 having quartz envelopes. The mercury vapor described herein, where additional oxygen is supplied, 15 discharge tubes 506 may, for example, be cold cathode and hydrogen peroxide, or H2O2, is formed, this reac tubes and have electrical terminals 508 at one end of the tion is exothermic and supplies heat to the reaction chamber, and 510, at the lower end of the reaction chanmber. This factor is useful in increasing the effi chamber 502. The mercury vapor discharge tubes 506 ciency of the processes, and contributes to the self-sus may be supported by the upper and lower aluminum taining nature of the processes, as discussed above. 20 plates 512 and 514.

On a general basis, the processes described herein Apertured transverse plates 516, 518 and 520 extend provide a mechanism for the transformation of low transversely across the reaction chamber 502, and plate grade thermal radiation into specific coupled modes of 518 may serve much the same function as the transverse intense monochromatic radiation providing new higher baffle 382 in FIG. 19. Feedstock is applied to reaction frequencies and shorter wavelengths with considerably 25 chamber 502 through inlet 522 at the bottom of the increased power. reaction chamber, and the output products from reac The energy change is accomplished through the cre tion chamber 502 are carried off through tube 524. The ation of controlled spatial harmonics beating together space below baffle 516 serves as an input manifold, while passing through media discontinuities within a while that above baffle 520 serves as an output mani non-linear medium. The effect is much like a parametric 30 fold. In accordance with the reaction which is to be amplifier which controls the disposition of the electro undertaken, the radiation in the input portion of the magnetic energy conveyed by the waves. On a compre reaction chamber 502, between baffle plates 516 and hensive basis, the transformation of the broad black 518, may be of a somewhat different frequency of radia body radiation into specific monochromatic frequencies tion, than that in the output irradiation portion of the of high energy which are matched to the absorption 35 reaction chamber 502 between baffle plates 518 and 520. bands of the feedstock and to the transmission bands of The design factors going into the irradiation and to the product, make for process efficiencies which are specific frequencies in the input and output sections of extremely high. - -- - - the reaction chamber were discussed hereinabove in With regard to the operating temperatures and pres connection with the embodiment of FIG. 19. Similar sures for the apparatus of FIGS. 16 through 19, and that considerations, of course, apply here. of FIGS. 22 and 23, the temperatures and pressures are The physical mounting arrangements and electrical less critical than for the embodiments disclosed earlier connections for each mercury vapor tube may be pro in the present case. In general, in order to provide radia vided as indicated in FIG. 25. More particularly, as tion in the desired spectral range the apparatus of FIGS. shown in FIG. 25, the mercury arc lamps 506 are pro 16 through 19 should be operated at a temperature in 45 vided with conducting terminals 508 which are silver the order of 1000 Kelvin; however, other temperatures soldered to the existing pins extending from the ends of may be employed which produce adequate radiation at commercially available mercury arc lamps. A thick the desired frequencies, and a departure of 100 or 200" silicone rubber sheet 526 is provided to support, cushion above or below 1000 K. would be operative, it is ex and locate the ends of the mercury arc lamps 506. In pected, with radiation drop off toward the lower end of 50 addition, the silicone rubber heavy wall tubes 528 en this temperature range and possible materials failure close the electrical terminals 508 and insulate them from problems toward the upper end of the range. Concern the aluminum conducting end plate 512. The sheet 526 ing the embodiment of FIGS. 22 and 23, a lower tem and tubes 528 may be either integral or separate, with perature such as 250 F., above the boiling point for the tubes ending even with the lower surface of plate water at the pressure which is employed, would be 55 512.

adequate. Helically wrapped around the outer cylindrical sur Concerning pressures, somewhat lower pressures are face of the mercury arc tubes 506 are filaments 532 adequate, as compared with the embodiments involving which are formed of laser-type material. The laser-type the use of metallic oxides, and no change in pressure is material included in the filaments 532 may be of the host needed. For the embodiments of FIGS. 22 and 23, a and sensitizer type as discussed hereinabove, or they gauge pressure of 3 or 4 pounds would be adequate, may be of ruby laser-type material, if desired. although higher pressures of up to several hundred The mercury arc tubes 506 extend through clearance pounds, for example, could be employed where higher holes in the plates 516, 518 and 520. As indicated in fuel gas reservoir pressures are desired. Similar pressure FIG. 26, the plate 520 is provided with holes 534 which considerations are applicable to the apparatus of FIGS. 65 are of slightly larger diameter than the outer diameter 16 through 20. v of the tubes 506. If desired, the tubes may be firmly The apparatus of FIGS. 1 through 23, described here supported as indicated in FIG. 25 at both ends of the inabove, were also described in the co-pending patent reaction chamber and merely pass freely through the

Page 44

plates such as plate 520 of FIG. 26. Alternatively, each radiation is within the U. V. absorption band of water of the apertures in plate 520 may be grooved to receive vapor as shown in FIG. 29 of the drawings. Accord a lamp retaining spring which will provide additional ingly, by way of example, this combination of frequen support and location to each of the mercury vapor cies may usefully be employed in the input section of lamps. These lamp retaining springs 536 are shown 5 the chamber of FIG. 24 between the baffles 516 and 518. schematically in FIG. 26. This is particularly useful in this area in view of the high The filaments 532 and 532 of FIGS. 27 and 28, re energy content of the 1.7X 10 Angstrom unit ultravio spectively, may include a central metal filament 538 let radiation, and the low concentration of hydrogen which may be of resistive material as disclosed herein peroxide in the input section of the reaction chamber. above in connection with FIG. 16 of the drawings, or 10 As noted in FIG. 21, H2O2 has a relatively high absorp the filaments may be made up entirely of laser-type tion coefficient for 1.7X 10 Angstrom radiation, and it material, as indicated in FIG. 28. The central metal is preferred that far ultraviolet radiation of this type not filaments 538 may be employed to ohmically heat the be used in the output section of the reaction chamber filaments to an elevated temperature to produce the 502, between baffle plates 518 and 520, where high desired output radiation as discussed above in connec- 15 concentrations of H2O2 are present, for most efficient tion with the embodiments of FIGS. 17 and 19, for use of the radiated energy. On the other hand, in this example. Under these operating conditions, electricity output region, it would be preferable to have irradiation would be applied both to the individual filaments to of the water vapor at lower frequencies and longer heat them to the proper temperature, and also across the wavelengths, to couple to selected water vapor absorp terminals 508 and 510 of the mercury gas discharge 20 tion bands that are present at longer wavelengths as tubes to appropriately energize them. shown in FIG. 10 of the drawings, thereby avoiding The laser-type materials for use in the coating 540 of absorption of the radiation by hydrogen peroxide. Suit FIG. 27 or as the entire filament in FIG. 28 may be of able materials for producing such radiation are dis any of the host-sensitizer types as discussed hereinabove closed hereinabove in Examples (a) through (e) in the in connection with other embodiments of the invention. 25 section

Alternatively, other known laser materials such as suit for Water of this specification entitled "Host/Sensitizers Vapor Feedstock'. Similarly, other design ably doped aluminum oxide, used in the ruby laser, may controlled radiation be employed. Other known laser materials may also be the input sections andsystems may be developed for both the output sections of the reaction used.

To enhance laser action, the filaments 532 or 532 of 30 chamber 502 to smoothly facilitate the desired dissocia FIGS. 27 and 28, respectively, may be provided with tionFIGS. and recombination chemical reactions. 30, 31, and 32 of the drawings show an impor one or more semi-transparent, or partially reflective tant embodiment of the invention in which spheres are layers 544 and 546 (see FIG. 27), or 548 constituting an employed in proximity to the outer surface of the gas outer peripheral partially transparent metallic coating on the outer surface of filament 532, in FIG. 28. The 35 discharge tubes, instead of the filaments shown herein semi-transparent surfaces 544, 546, and 548 may be surface above. Specifically, as shown in FIG. 30, the outer made by depositing a thin layer of chromium or other of all of the quartz mercury vapor tubes 506 are provided with a large number of spheres 556. These good reflecting material on the filament 532 or 532 as spheres they are being formed. The distance between substan may be formed of any of the laser type materi tially perpendicular surface areas of the semi-transpar- 40 als, or the host-sensitizer materials discussed herein ent layers 544 and 546, for example, along the line seg above, and they are preferably coated with a semitrans ment 550, should be an integral multiple of half wave parent metallic coating to facilitate the radiation of lengths, in order to maximize lasing effect and to prod substantially coherent radiation. With regard to dimen uct essentially coherent output radiation. Similarly, the sions, the quartz tubes 506 may be in the order of; inch diametral distance 552 in FIG. 28 should be an integral 45 in diameter; the spheres 556 may be in the order of 0.002 number of half wavelengths at the desired output radia to 0.004 inches in diameter, and the semireflecting coat tion frequency. ings are preferably spaced apart along a diametral line Concerning the radiation within the reaction cham by an integral number of half wavelengths at the output ber, it is a function of the output radiation both of the radiation frequency of the laser type material. The mercury arc lamps 506, and also the radiation produced 50 spheres 556 may be secured in proximity to the outer by the filaments 532 and/or 532". With media disconti surface of the tubes 506 in any desired manner, prefera nuities within the reaction chamber caused by the pres bly by the use of glass frit, fired when the spheres are ence of feedstock within the reaction chamber, the firmly held against the quartz envelope by a suitable different frequencies which are generated will "beat' high temperature wrapping. The spheres may occupy in with one another and produce sum and difference fre- 55 the order of 50% of the area of the tube, or a greater or quencies. Thus, for example, if ruby laser-type material lesser area depending on the scheduled relative radia is employed as the laser-type material as indicated by tion from the mercury vapor lamps and the laser the reference numerals 540 and 542 in FIGS. 27 and 28, spheres, which is desired for the reaction being under respectively, the radiation wavelength is approximately taken.

7.0x 103 Angstron units. The output radiation from the 60 As more clearly shown in the diagram of FIG. 31, the mercury arc lamps includes a prominent spectral line at reflective coating extends over most of the outer sur 2.537x103 Angstrom units, and a very broad emissions face of sphere 556 but stops at line 558. With the reflec band which peaks at about 3.0X 10 Angstrom units. tive coating not present where sphere 556 engages the When these radiations impinge on the media discontinu outer surface of gas discharge tube 506, the pumping ities provided by water vapor feedstock, for example, 65 radiation from the mercury gas discharge, indicated by the resultant sum frequency has a wavelength of ap rays 560, has easy access to the laser material within proximately 1.752 x 103 Angstrom units, in the ultravio sphere 556, by passing through the transparent glass frit let frequency spectrum. This high frequency ultraviolet 566.

Page 45

In the diagram of FIG. 31, the pumping radiation 560 Background texts relating to this subject matter in serves to raise the atoms in the laser-type material to the clude "Photochemistry of Gases', by William Albert excited state; and the rays 562 represent the coherent Noyes, Jr. and Philip Albert Leighton, published in radiation characteristic of laser materials, which is gen- 1941 by Rheinhold Publishing Company; "Combustion, erated as atoms drop from the excited state to lower 5. Flames and Explosions of Gases', published by Aca energy levels triggered by arriving radiation from other demic Press, Inc., 1961, by Lewis and Von Elbe; and transitions within the sphere. The reflecting coating on "Photochemistry', by Calvert and Pitts, published by the outer surface of sphere 556 is preferably in the order Wiley, in 1966.

of 70% to 90% reflecting and only 30% to 10% trans- One form of chain reaction which is diagramed below missive in order to enhance the generation of harmonic 10 involves the absorption by molecule A by radiation radiation. Accordingly, the output radiation as indi- such as light, and its dissociation into identical frag cated by the rays 564 may have a significant energy ments. The secondary reactions involve a chain which content which is at a frequency which is a multiple of may be stopped at low pressures by the removal of the the basic output frequency of the laser material in carriers at the walls, and at high pressures by a homoge sphere 556. 15 neous recombination involving a third body or reactant. - For example, with the ruby laser having a fundamen- The overall reaction produced by the chain is tal radiation wavelength of just under 7,000 Angstrom A+B-2C. Various examples are to be found among units, the fourth harmonic would have a wavelength of “halogenation" and “hydrogen-oxygen" reactions. The about 1,750 Angstrom units, in the far ultraviolet. mechanism is as follows:

CHAIN LOW-PRESSURE (4) D + S-3A -- . . .

Incidentally, as shown in FIG. 31, the transparent Concerning radiated energy effects, when a molecule glass frit 566 is shown securing the spheres 556 onto the 30 or a polyatomic ion is irradiated by electromagnetic quartz envelopes 506. With suitably transmissive mate- energy of a wavelength appropriate to couple with the rial being selected for the frit 566, and with the semi- molecule or ion, this radiation may be absorbed, and the reflective coating stopping at line 558, the mercury energy of the molecule or polyatomic ion may be in vapor radiation from within the discharge tubes readily creased; the molecule or ion may be excited rotation passes into the spheres 556. 35 ally, vibrationally, or electronically, or one or more of In the diagram of FIG. 32 the quartz envelope 506 the covalent bonds that hold the molecule together may separates the gas discharge region 572 from the reaction be broken. This bond-breaking gives rise to the forma chamber region 574. In the gas discharge region 572, tion of atoms, or groups of atoms, which have one "un electrons 576 are shown moving at high velocities paired' electron each and are called "free radicals'. downward, and the heavy ionized mercury molecules 40 Accordingly, the absorption of radiated energy by a 578 are drifting upwardly. Collisions cause the radiation molecule may cause it to decompose into fragments or of energy from the mercury vapor, and the complex free radicals, which are extremely more reactive than atomic structure of mercury produces radiation at a the original molecule. When this is the case, the se large number of spectral lines. The resultant radiation is quence of reaction steps leading to the final products shown schematically at 582, 584, and 586. 45 involves these free radicals (even though they may exist Within the reaction chamber region 574 are shown only temporarily in the reaction mechanism), rather water vapor molecules 592, oxygen molecules 594 and than the original molecules of the reactant. hydrogen molecules 596, with the showings being in the form of circles of progressively reduced size. It is also CHAIN REACTION EXAMPLE NO. 1 interesting to note that some of the radiation from the 50 The first example of chain reactions which we will ionized mercury vapor provides pumping energy to consider involves the reaction of hydrogen gas H2 with spheres 556, and some of the radiation passes directly Chlorine gas Cl2 to form HCL gas. When a Cl2 mole into the radiation chamber region 574. cule absorbs radiated energy it passes to a higher energy or an excited state, and if the energy of this excited state

CHAIN REACTIONS 55 is sufficiently high, the bond of the Cl2 molecule may be The apparatus of the present invention are particu- broken to form two Cl atoms. In this connection it may larly well suited for the implementation of chain reac- be noted that in order to dissociate a Cl2 molecule into tions. This is particularly true of the reaction chambers its two atoms, a relatively large quantity of energy, in shown in FIGS. 19 and 24, in which different frequen- the order of 58.16 kilocalories per mole of Cl2 gas must cies of radiation may be applied to incoming feedstocks 60 be supplied. The decomposition of Cl2 molecules by as compared with feedstocks during the subsequent absorption of radiated energy is illustrated by the fol portion of the chain reactions. lowing equations, which also involve the presence of In considering the mechanisms involved in photo- hydrogen gas:

chemical kinetics, it is important to recognize that most complete photochemical reactions may be divided into 65 three somewhat overlapping stages: (1) The initial act of (1) Cl2 -hy d2 Cl (AH = +58. 16) absorption of radiant energy, (2) the primary process, and (3) secondary reactions. (2) C1 + H2-GHC1 + H (AH = +7.02)

Page 46

-continued than an H atom of CH3Cl2, and similarly for CHCl3. In the present case, the C-H bond becomes more readily (3) H + Cl2-GHCl + Cl (AH = -51. 14) susceptible to substitution by a C-Cl bond as the num 7.02 -- (-5.14) = - 44.12. KCAL ber of Cl atoms already attached to the C atom in creases. In terms of energetics, the compound CH3Cl is

The chain reaction is eventually broken when a Cl thermodynamically stable with respect to a mixture of atom collides with another Cl atom, perhaps absorbed CH4 and Cl2, but the di-, tri-, and tetra- substituted on the wall of the reaction chamber, to reform a Cl2 compounds, CH2 and Cl2, CHCl3, and CCl4, are even molecule. The chain reaction may also be interrupted 10 more stable, their stability increasing with the number when a Cl atom reacts with some impurity present in of Cl atoms in the molecule. the system to form a product which no longer contrib If a reaction chamber were irradiated unevenly, with utes to maintaining the chain reaction. certain localized areas of very intense radiation, and

CHAIN REACTION EXAMPLE NO. 2

others where there was little irradiation, then the reac

tion would proceed to the (undesired) final product

This second chain reaction example involves the CC14. However, in the present case, by using reaction reaction of methane CH4 with Chlorine Cl2 to form chambers which are very uniformly flooded with radia methyl chloride, CH3Cl, and hydrogen chloride HCl. tion, the bulk of the methane is only subject to a single The primary reaction is as follows: substitution of the activated chlorine atom Cl, and it occurs very soon after these highly activated chlorine

CH4+ Cle-hye CH3Cle) + HCl (AH = Kcal -237) atoms are formed by the impact of radiation on the chlorine gas Cl2. In addition, a substantial excess of

CH4 is provided. Therefore, under these conditions,

The chain initiation step involves the absorption of CH3Cl is the principal product of the chlorination of radiated energy by the Cl2 molecule to break the bond 25 methane, although the more substituted products may as in the previous example: also be formed in much smaller yields. In accordance with the teachings of the present invention, and the h apparatus disclosed therein, precise amounts of energy

Cl, Ye C1 + Cl (1) of the proper energy level are delivered evenly 30 throughout the reaction chamber, with the photons

Various chain propagation steps now follow. First, a bombarding the target molecules, atoms or fragments of Cl atom of high kinetic energy comes in contact with a molecules from all directions simultaneously. In addi CH4 molecule, a carbon-hydrogen bond is broken, tion, as mentioned above, large amounts of intense en while a hydrogen-chlorine bond is formed. By losing an ergy of controlled wavelengths coupled to absorption H atom, the CH4 molecule becomes a CH3 radical: 35 bands of specific molecules or atoms is provided. This eliminates the steric factor, which is a normally ex pected problem.

(activated complex) PHOTOCHEMISTRY OF WATER VAPOR

H3C + H-Cl (AH = + 1600) 40 The absorption spectrum of water vapor in the ultra violet region is shown in FIG. 29. As compared with

Now, a methyl radical CH3 comes in contact with a FIG. 10, it may be noted that FIG. 29 is directed to a Cl2 molecule; a chlorine-chlorine bond is broken, while band which starts just below 2,000 angstrom units. This a carbon-chlorine bond is formed. The products are a would correspond to 0.2 microns. As mentioned herein methyl chloride molecule and a chlorine atom: 45 above, the visible spectrum ranges from about 4,000 to about 7,000 angstroms, which is equal to 0.4 to 0.7 mi 3 crons. Accordingly, the plot of FIG. 29 is in the ultravi

H3C + C1-C - Ge H3C- - C -- Cl-G (3) olet, well below the visible spectrum, and the plot of (activated complex) FIG. 10 is in the infrared, above the visible spectrum. In H3C-C - C1 (AH = - 183.0) 50 comparing FIGS. 10 and 29 it may also be noted that in 65 - 1830 -- (-|- 160,0) = -23.0 Kcal FIG. 29 peaks of absorption extend upwardly, whereas in FIG. 10 peaks of transmittance are plotted upwardly,

The two chain propagation steps 2 and 3 are repeated and peaks for absorption extend down toward Zero on many times before the chain reaction is broken by ad the vertical scale.

verse reactions or one of several chain terminating reac-55 There is considerable evidence that the photolysis of tions of the type mentioned hereinabove. water at all wavelength regions leads to hydrogen and The uniformity of radiation extending throughout the OH radicals. The following primary reactions are prob reaction chambers as disclosed in the present patent ably significant:

application is particularly advantageous in reactions such as the formation of methyl chloride CH3Cl. This 60 advantage arises particularly from the fact that the sub H'o - hvos3.

stitution of chlorine atoms can proceed further, forming the di-, tri-, and finally the tetra-chlorocompound,

CH2Cl2, CHCl3, and CCl4.

It is understood that an H atom of CH3C is more 65

readily substituted, or replaced by a Cl atom than is an These reactions become possible energetically at H atom of methane, CH4. Also, an H atom of CH2Cl2 is wavelengths less than 2,420 angstron and are probably more susceptible to further substitution by a C atom the major reactions in the longer wavelength absorption

Page 47

bands of ultraviolet radiation. At wavelengths less than initiating a chain and/or a branching chain reaction, by 1,356 A units, another reaction leading directly to the destroying a normal H2O, H2, or O2, and H2O2 mole obtaining of excited individual oxygen atoms, is under- cule.

As the dissociation/formation processes proceed in 5 CHAIN REACTION EXAMPLE NO. 3 our examples, the cleavage or fragmenting of the H2O, In this and the next example, chain reactions involv O2, or H2 molecules yield H-OH, O-H, HO-OH, ing water vapor and oxygen will be considered:

(1) 2H2O"(1) + 202. G2H2O2) + Q + O. AH = - 47.66

CHAIN

REACTIONS

AVAILABLE FOR

(2) H2O(1) + O2 + 6-S H2O2) + O + O AH = -23.83

(3) H2O"(1) + O2 + 6-G> H2O2) +Q + O AH = -23.83

CHAIN

TERMINATING

(4) H2O"(1) + O2 +O-GH2O2 + O2 AH = -95.27

HO2-H, H-O2, HO-O, H-H, and O-O products. The foregoing chain reaction number 3 will now be Among these are very "hot" radicals, fragments, or 25 analyzed from a Gibbs free energy standpoint, with the atoms, because as described earlier, the greater part of numbers in the following analysis corresponding to the the surplus energy that is absorbed is carried away by equations set forth above.

- TAS 298.0 peo x 56.72/1000 = + 16.90 Kcal/Mole - EQN AG' = AH - TAS = -47.66 - (-- 16.90) = -64.56 Kcal/Mole - EQN

NOTE:

PRODUCT YIELD = (5) MOLESHO

(B.) (OUTPUT) MINUS (INPUT) = (NET)

(c) PRODUCT QUANTUMYIELD = --

the latter fragments or atoms. Although in the case of an , - oxygen or hydrogen molecule, where scission of either of these molecules results in an equivalent weight distri- 65 CHAIN REACTION EXAMPLE NO. 4 bution, actually, either or both atoms may become hot This example like the previous example, involved the atoms, especially under constant bombardment. Then, reaetion of water vapor and oxygen when high intensity each single atom or fragment, or radical, is capable of and high frequency radiant energy is applied to it.

Page 48

Drawing sheet — no readable text.

Page 49

NOTE:

(A.) PRODUCT YIELD = (4) MOLES H2 + (3) MOLES H2O2

(C.) PRODUCT QUANTUM YIELD, d = 370.94

CHAIN REACTION EXAMPLE NO. 5 20 -continued When water vapor alone, or when air including oxy- BONDS OF INTEREST gen, and water vapor, are supplied to one of the reac- foLIRE, tion chambers, chain reactions occur which involve in Kcal plexes only the water vapor. The following example will con- 3. HO-OH = 51.0 3.06 sider such a chain reaction. In actual practice the reac- 25 4. Ho, H-900 5.46 tions may follow a large number of branching patters, 5. H-H = 104.2 6.25 but it has been determined that the example set forth 6. O-O = 19.1 7.5 below includes the principal reaction mechanisms which occur.

Initially, the activation energies of the bonds of inter- 30 est will be tabulated: The activation energy will amount of -5.5 percent minimum of the bond energy of the bond to be broken.

BONDS OF INTEREST Then, for the reaction A--BC2AB+C, if the reaction Activation Energies is exothermic from left to right, the activation energy For Activated Complexes 35 estimated by the semiempirical method will be ~5.5 in Kcal percent of the molecule BC. The activation energy of . H-O2 = 47.0 2.82 the reverse endothermic step will be this amount, plus 2. HO-O 64.0 3.84 the heat of the reaction. For our purposes, we used the figure of 0.06 (6.0) percent for our calculations.

REACTION MECHANISMS (Probable Average)

ACTIVATED

COMPLEX

(ENERGY OF ACTIVATION)

(ENERGY OF ACTIVATION)

Page 50

REACTION MECHANISMS (Probable Average)

H- HasaC) --

(ENERGY OF ACTIVATION)

B. 2(H2O) + 26-> O -Ge2(H2) + 2CO2)

(ENERGY OF ACTIVATION)

H Hoo H

H HOOH

(ENERGY OF ACTIVATION)

(ENERGY OF ACTIVATION)

(1) We have determined that we would like to supply 1550

the equivalent of 315.0 Kcal per second, so we con 24.0 vert this: 24.0 s .

315.0 Kcal/sec (= DISTRIBUTION)

(a) 1.0 Kcal - Sec = 4.186 Kwatts - sec. 24.0

Kwatts - sec.

45 A. INPUT

(2) 1318.59 Kwatts-sec=1.318,590 Joules per sec. 315.0 (Kcal-Per-Unit-Time) (3) Joule-sec. = 1.5258x1033 quanta. B. OUTPUT (Per-Same-Unit-Time) (Assuming 100% (4) efficiency on reactions shown.) 33 50 1. 12 Moles H2 gas 1.5258 x 10' (joule-sec.) = 2.53455 x 10' quanta ... 12 x 68.3 (Kcal) = 819.6 Kcal 6.02 x 102 (Avogadro's Number) (Per Joule) * 3: 2.60 = 0 = Product Quantum Yield.

55 C. OUTPUT (Per-Same-Unit-Time) (Assuming 50.0% efficiency on reactions shown.)

Total Quanta-Sec. = 3.342 x 105 (INPUT) 1. 6.0 Moles H2 gas

(6) "Power" will be obtained in watts if Wis expressed 60 2. 1.30 = d = Product Quantum. Yield. in joules (107 ergs) and t in seconds.

In summary, the apparatus described hereinabove

- - - 1,318,590. ,318,590 Watt-Sec. may clearly be designed to provide the staged and com P=- 1,318.59 (Dwatt-Sec.) partmentalized irradiation of reactions to obtain condi = 35.0 (Kcal-Sec.) 65 tions which are favorable to the reaction mechanisms of interest. Different radiation frequencies may be em (7) INFRARED=2.5 (Peak)= -240 Kcal/Mole/Pho ployed at the input feedstock area and at the output tOS feedstock area to enhance the desired reaction. Certain

Page 51

selected reactions have been considered in some detail. 3125.6 through 4046.6 are available for pumping Exam Other reactions involving breaking molecular bonds ple No. 1. ...

and substituting new elements or radicals may be imple Concerning another point, the use of the spheres of mented by the same type of technique used in the appa laser type material mounted on the quartz envelope of ratus as disclosed herein or similar apparatus. Typical the mercury vapor tube has been noted. As discussed in products which may be input feedstocks include meth detail, the mercury vapor discharge provides the radi ane, ethane, propane, isobutane, N-pentane, isopentane, ant energy to pump the laser type material to the de neopentane, and the alkyl amines. The apparatus as described in the present application are also particularly sired excited-state to initiate coherent radiation. Instead suited to hydrogenation and olefin formation, the dehy 10 of the mercury vapor discharge, the pumping energy dration of alcohols, addition reactions of olefins, and to for the laser-type material spheres may be provided reactions involving polysubstituted saturated hydrocar from heated filaments coated with mullite suitably bons, benzene, unsaturated hydrocarbons including the doped to provide the desired pumping frequency. The alkyne series, alcohols, carboxylic acids, aldehydes, and filaments could be of the configuration disclosed in ketones. 15 FIG. 16, coated with an outer transparent sealing coat For completeness, certain matters relating to the gas ing, to which the spheres could be secured as shown in discharge tubes and certain laser-type materials which FIG. 30, for example. Suitable variation in operating may be used will now be reviewed. Initially, as men conditions could then be obtained by varying the power tioned above, the gas discharge tubes are preferably applied to the filaments, and their resultant temperature, made of quartz and are mercury gas discharge lamps. 20 and output radiation.

One typical lamp available from Westinghouse is rated In closing, it is to be understood that the principles set by the manufacturer at 39.0 watts, 0.420 amperes, for forth in the foregoing description may be implemented 115 volts A.C. operation. The emitted ultraviolet radia by a number of different apparatus, with the construc tions are rated by the manufacturer at 38.5 percent of tions and materials specified herein only being exem input power, or at about 15-watts. Quartz, depending 25 plary of the types of apparatus and materials which may on its quality will transmit ultraviolet radiations with a be employed. Reaction chambers of different configura cut-off of between 1000 Angstrom units and 2,000 Ang tions, and different laser type materials, as well as differ strom units.

The lines in the ultraviolet emission spectrum of mer entI feedstocks claim:

and products could be employed.

cury are set forth below, with particularly strong lines 30 1. A radiation apparatus comprising:

appearing at 2536 A and at 1849 A. a filament composed at least in part of means includ ing solid state material for producing substantially

LINES IN THE ULTRAVOLET. coherent output radiation at a predetermined fre EMISSIONSPECTRUM OF MERCURY quency;

(Wavelength in Angstrom Units) 35 said filament including semi-reflective surface means

extending generally concentric with the axis of said 1592.0 2534.8 3131.8 filament, said semi-reflective surface means includ 599.0 2536.0 3341.5 ing generally perpendicular surfaces spaced apart

by a distance substantially equal to an integral num 1783.3 2752.8 -3662.8 ber of half-wave lengths at said predetermined 798.7 2803.5 3663.3 frequency.

1849.0 2847.7 3906.4 2. An apparatus as defined in claim 1 wherein two 942.0 . . . . . . . 2893.6 - 3983.9 concentric semi-reflective surfaces are provided.

2378.3 302.5 - 45 3. An apparatus as defined in claim 1 wherein said filament is made up of a central resistive wire and an

Four known laser type materials which may be used outer coating of said solid state material for producing are as follows: substantially coherent radiation. 1. Aluminum Oxide (Al2O3) doped with chromium 4. An apparatus as defined in claim 1 further compris

(Cr3+), requiring input pumping radiation of from 0.32 50 means for applying pumping energy to said solid state to 0.42 microns, or from 3200 A to 4200 A, and having a fundamental output wavelength of 6934 A. material to raise said material to an excited state for 2. Yttrium Oxide (Y2O3) doped with europium producing coherent radiation. (Eu3+), requiring input pumping radiation of from 2000. ing:5. An apparatus as defined in claim 1 further compris A to 2800 A, and having an output wavelength of 55 a reaction chamber,

3. Calcium Tungstate (CaWO4) doped with erbium means for mounting a plurality of said filaments in (Ert) requiring input pumping radiation between 2000 said reaction chamber; and means

A and 2800 A and having a fundamental output wave 60. material for applying pumping energy to said solid state length of 16,120 A. - to raise said material to an excited state, 4. Aluminum Oxide (Also 12) doped with erbium whereby said, reaction chamber is flooded with (Eri+) requiring input pumping; radiation of between output radiation from said solid state material. 3200 A and 4200 A, and having a fundamental output 6. An apparatus as defined in claim 5 wherein said wavelength of 16,602 A. means for producing substantially coherent radiation Considering. Example No. 1. and Example No. 2, it is 65 includes solid state materials having different radiating clear that mercury vapor spectral lines from 1942 A. frequencies in different ones of said filaments, whereby through 2803.5 A, are available...to, supply pumping radiation of at least two different frequencies is applied radiation, for Example. No. 2; and that mercury lines to said reaction chamber.

Page 52

7. An apparatus as defined in claim 6 further compris radiating substantially coherent energy into said ing means for supplying feedstock to said reaction reaction chamber at a different frequency. chamber, thereby producing media discontinuities 17. An apparatus as defined in claim 16 wherein said within said chamber, whereby sum and difference fre solid state material is in the form of filaments wound quencies derived from different radiation frequencies 5 onto said gas discharge tubes.

present in said reaction chamber, are formed and are 18. An apparatus as defined in claim 16 wherein said coupled to said feedstock. solid state material is in the form of spheres mounted on 8. An apparatus as defined in claim 7 further compris said gas discharge tubes.

ing means for supplying to said reaction chamber feed 19. An apparatus as defined in claim 16 wherein said stock having an absorption band at the sum frequency 10 solid statematerial intercepts only a fraction of the of two or more radiations present in said reaction cham- radiation from said gas discharge tubes, whereby said ber, to cause dissociation of said feedstock. reaction chamber is flooded with radiation of different 9. An apparatus as defined in claim 5 further compris- frequencies forming sum and difference frequencies at ing means for supplying feedstock having an absorption themedia discontinuities formed by the presence of the band at said predetermined frequency of said radiation, 15 feedstock; and wherein said gas discharge tubes and said to said reaction chamber, to cause dissociation of said solid state material include means for producing at least feedstock. - one of the sum frequencies in an absorption band of said 10. An apparatus as defined in claim 9 further com- feedstock.

prising means for supplying a second feedstock to said 20. An apparatus as defined in claim 16 further com reaction chamber to react with one or more of the disso- 20 prising reflective coating means associated with said ciation products of the first feedstock. solid state material for increasing the coherency of said 11. An apparatus as defined in claim 1 further com- radiation prising a plurality of gas discharge tubes, and wherein a 21 An apparatus as defined in claim 20 wherein said plurality of said filaments are helically wrapped around reflective coating means reflects from 70% to 90% of said gas discharge tubes. incident visible radiation 12. An apparatus as defined in claim 11 wherein said 22. An apparatus aS defined in claim 16 further com Edischarge tubes are mercury vapor gas discharge prising reflective coating means associated with said 13. An apparatus as defined in claim 1 wherein said solid state material for reflecting infared and visible solid state material includes host and sensitizer material 30 frequencies and for transmitting shorter wavelength for receiving incoherent radiant energy and for radiat- ultraviolet radiations to supply coherent harmonic radi ing substantially coherent monochromatic radiation at a ations to said reaction chamber. 1 different frequency than that of the input radiant en- 23. An apparatus for efficiently accomplishing photo ergy. chemical reactions comprising: 14. An apparatus as defined in claim 1 wherein means 35 chamber; - are provided for directing radiation outward from said means for applying feedstock to said reaction cham filament substantially transverse to the axis thereof. ber, said feedstock having predetermined fre 15. An apparatus for controlled photochemical reac- quency absorption band or bands; tions comprising: teaS located within said chamber for flooding said a reaction chamber; 40 reaction chamber with substantially coherent en means for supplying feedstock to said reaction cham ergy within one of the absorption bands of said ber, said feedstock having a predetermined fre feedstock at energy levels sufficient to dissociate quency absorption band or bands; and said feedstock, said radiation supplying means in means for flooding said reaction chamber with radia cluding solid state material; and tion within at least one of the absorption bands of 45 low cost incoherent energy source means immedi said feedstock; ately adjacent said supplying means for pumping said means including at least one gas discharge tube said solid state material to an excited state. having output radiation of a lower frequency than 24. A source of radiant energy comprising: said predetermined band or bands and means in means including a sphere of solid state material for physical proximity to said gas discharge tube and 50 producing substantially coherent radiations; also exposed to said reaction chamber for receiving a semi-reflective coating on at least the major portion said lower frequency radiation from said gas dis- of the outer surface of said sphere; and charge tube and for supplying intense radiation to means for pumping said solid state material to an said reaction chamber within said predetermined excited state, whereby substantially coherent en band or bands. 55 ergy is radiated through said semi-reflective coat 16. An apparatus for controlled photochemical reac- ing from said solid state material to an excited state, tions comprising: whereby substantially coherent energy is radiated a reaction chamber; through said semi-reflective coating from said ma means for supplying feedstock to said reaction cham- terial.

ber, said feedstock having predetermined absorp- 60 25. A source of radiant energy as defined in claim 24 tion bands; wherein a plurality of said coated spheres are provided, means including a plurality of gas discharge tubes for and wherein said pumping means directs pumping radi flooding said reaction chamber with radiation ation into said material through a portion of the surface within at least one of the absorption bands of said of each of said spheres that is not coated with said semi feedstock; and 65 reflecting coating.

means including solid state material in close proxim 26. A source of radiant energy as defined in claim 25 ity to said gas discharge tubes for receiving pump wherein transparent envelope means are provided for ing energy from said gas discharge tubes and for supporting said spheres, and said pumping means

Page 53

supplies radiant energy to said spheres through said 38. An apparatus for controlled photochemical reac transparent envelope. tions comprising: . . .

27. A source of radiant energy as defined in claim 26 a reaction chamber; -- wherein said pumping means is a mercury vapor gas means for supplying feedstock to said reaction cham discharge tube. ber, said feedstock having a predetermined energy 28. A source of radiant energy as defined in claim 26 absorption vs. frequency characteristic, including wherein said pumping means includes means for con at least one high energy absorption region; verting electrical power to radiant energy of the proper means located within said radiation chamber for high frequency required to pump said laser material to flooding said reaction chamber with high intensity the excited state. 10 radiation within said high energy absorption region 29. A source of radiant energy as defined in claim 24 of said feedstock;

wherein said semi-reflective coating reflects from 70% said radiation flooding means including solid state to 90% of the incident visible radiation. means having outer surfaces of substantially circu 30. A source of radiant energy as defined in claim 24 lar cross-section for producing substantially coher wherein said semi-reflective coating comprises means 15 ent output radiation within or in immediate prox for reflecting infrared and visible frequencies and for imity to said reaction chamber; and transmitting shorter wavelength ultra-violet radiations means for exciting said means for producing substan whereby coherent harmonic radiations emanate from tially coherent radiation to an excited state to radi said spheres. ate relatively coherent high frequency radiation 31. An apparatus for controlled photochemical reac- 20 through said outer surfaces at intensity levels suffi tions including the radiant energy source as defined in cient to modify the form of a substantial proportion claim 24 and further comprising: of said feedstock.

means defining a reaction chamber for receiving the 39. An apparatus as defined in claim 38 wherein said major portion of the radiation from said source; 25 means for producing substantially coherent radiation is means for supplying a reactant to said chamber, said in the form of a plurality of elements of solid state mate reactant having a frequency absorption band corre rial spaced apart within said reaction chamber. sponding to the frequency of radiation from said 40. An apparatus as defined in claim 38 wherein said SOC. solid state means are substantially spherical. 32. An apparatus for obtaining hydrogen or hydrogen 30 41. An apparatus as defined in claim 38 wherein said peroxide from water vapor comprising: solid state means are elongated and are of substantially means for directing water vapor through a predeter constant circular cross section.

mined reaction zone, said water vapor having pre 42. An apparatus as defined in claim 41 wherein said determined absorption frequency bands; solid state means include cylindrical rods. means including at least one gas discharge tube 35 43. An apparatus as defined in claim 41 wherein said within said reaction Zone, for flooding said reaction solid state means include cylindrical filaments. zone with radiation within at least one of said ab 44. An apparatus as defined in claim 41 wherein said sorption frequency bands, at sufficiently high inten solid state means have a substantially cylindrical outer sities to produce combustible hydrogen or hydro radiating surface.

gen peroxide from said water vapor, said means for 45. An apparatus as defined in claim 38 wherein flooding said reaction zone with radiation further semireflective coating means are provided on the out including means in immediate proximity with said side of said solid state means.

gas discharge tube for receiving radiation from said 46. An apparatus as defined in claim 38 wherein gas discharge tube having a predetermined fre semireflective coating means are provided on said solid quency output, and for supplying higher frequency 45 state means to enchance the production of high fre radiation to said reaction zone. quency harmonic radiation and to supply it to said reac 33. An apparatus as defined in claim 32 further com tion chamber, said semi-reflecting coating being formed prising solid state means for producing substantially of material which is reflective to frequencies below coherent output radiation within at least one of said ultraviolet radiation and which is relatively transparent absorption bands. 50 to ultraviolet radiation.

34. An apparatus as defined in claim 32 wherein said 47. An apparatus for controlled photochemical reac gas discharge means includes mercury vapor gas dis tions comprising:

charge means. a reaction zone;

35. An apparatus as defined in claim 32 further com means for supplying feedstock to said reaction zone, prising means for directing said water vapor into inti 55 said feedstock having a predetermined energy ab mate reactive proximity to said means for supplying soprtion vs. frequench characteristic, including at higher frequency radiation into said reaction zone. least one high energy absorption region; 36. An apparatus as defined in claim 32 further com means located inside said reaction zone for flooding prising means for continuously flowing water vapor said reaction zone with high intensity radiation through said reaction zone to continuously form com 60 within said high energy absorption region of said bustible hydrogen or hydrogen peroxide. feedstock;

37. An apparatus as defined in claim 32 wherein said said means including at least one elongated gas dis gas discharge means is elongated; and wherein said charge device within said reaction zone; and means for receiving radiation from said gas discharge means spaced around said gas discharge device for means is also elongated, and is spaced around said gas 65 receiving radiation from said gas discharge device discharge means, and includes means for radiating said and for radiating high intensity radiation having a higher frequency radiation outward substantially trans higher frequency content than the radiation from verse to the elongated gas discharge means. said gas discharge device, into said reaction zone.

Page 54

48. An apparatus as defined in claim 47 including 51. A system as defined in claim 49 wherein said means for supplying water vapor to said reaction zone system includes means for supplying water vapor as said and means for drawing off hydrogen or hydrogen per reactant to said reaction chamber, and means for draw oxide from said reaction zone. ing off hydrogen and/or hydrogen peroxide from said 49. In a system for subjecting material to high fre reaction chamber.

quency radiation; 52. An apparatus for controlled photochemical reac reaction chamber means for holding a reactant hav tions comprising:

ing a predetermined high frequency absorption a reaction zone;

band;

means for supplying water vapor to said reaction a high power source of lower frequency radiation; 10 zone, said water vapor having predetermined ab interface means located between said source of lower sorption band or bands in the ultra-violet frequency spectrum;

frequency radiation and said reaction chamber at least one elongated gas discharge tube mounted means for receiving said lower frequency radiation within said reaction Zone and producing a prede and for flooding said reaction chamber with high 15 termined lower frequency radiation output; and intensity radiation in said predetermined absorp means spaced around said gas discharge tube for tion band, at an intensity level sufficient to dissoci receiving said lower frequency radiation output ate said reactant, said interface means including from said gas discharge tube, and for flooding said means mounted adjacent said reaction chamber for reaction zone with higher frequency output radia reflecting the major portion of said lower fre 20 tion within said predetermined absorption band or quency radiation but transmitting the major por bands in the ultraviolet frequency spectrum, and at tion of radiation at said predetermined high fre an intensity level sufficient to dissociate the greater quency. portion of said water vapor and to form hydrogen 50. A system as defined in claim 49 wherein said and/or hydrogen peroxide.k is reflecting means is a thin metal layer. 25