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INDUS 20190389723A1 IN ( 19 ) United States (12 ) Patent Application Publication ( 10) Pub . No .: US 2019/0389723 A1 Mills (43 ) Pub . Date : Dec. 26 , 2019

( 54 ) HYDROGEN -CATALYST REACTOR on Jan. 17 , 2008 , provisional application No. 61/022 , 112 , filed on Jan. 18 , 2008 , provisional application ( 71) Applicant: Brilliant Light Power, Inc., Cranbury , No. 61 /022,949 , filed on Jan. 23 , 2008 , provisional application No.61 / 023,297 , filed on Jan. 24 , 2008 , NJ (US ) provisional application No. 61/ 023,687 , filed on Jan. 25, 2008 , provisional application No. 61/ 024,730 , (72 ) Inventor: Randell L. Mills , Cranbury, NJ (US ) filed on Jan. 30 , 2008 , provisional application No. Assignee : Brilliant Light Power, Inc., Cranbury, 61/ 025,520 , filed on Feb. 1 , 2008, provisional appli ( 73 ) cation No. 61/ 028,605 , filed on Feb. 14 , 2008 , pro NJ (US ) visional application No. 61/ 030,468 , filed on Feb. 21 , 2008 , provisional application No. 61/ 064,453 , filed ( 21) Appl. No .: 16 /426,687 on Mar. 6 , 2008 , provisional application No.61/064 , 723 , filed on Mar. 21 , 2008, provisional application (22 ) Filed : May 30 , 2019 No. 61/ 071,191 , filed on Apr. 17 , 2008 . Related U.S. Application Data Publication Classification (63 ) Continuation of application No. 12/ 108,700 , filed on (51 ) Int. Ci. Apr. 24 , 2008 , now abandoned . COIB 3/02 ( 2006.01 ) (60 ) Provisional application No. 60 /913,556 , filed on Apr. (52 ) U.S. CI. 24 , 2007, provisional application No. 60 / 952,305, CPC filed on Jul. 27 , 2007 , provisional application No. COIB 3/02 ( 2013.01 ) 60 / 954,426 , filed on Aug. 7 , 2007 , provisional appli cation No. 60 / 935,373 , filed on Aug. 9 , 2007 , provi ( 57 ) ABSTRACT sional application No. 60 / 955,465 , filed on Aug. 13 , A power source and hydride reactor is provided comprising 2007, provisional application No. 60 /956,821 , filed a reaction cell for the catalysis of atomic hydrogen to form on Aug. 20 , 2007, provisional application No. 60/957 , novel hydrogen species and compositions of matter com 540 , filed on Aug. 23 , 2007 , provisional application prising new forms of hydrogen , a source of atomic hydro No. 60 /972,342 , filed on Sep. 14 , 2007 , provisional gen , a source of a hydrogen catalyst comprising a reaction application No. 60 /974,191 , filed on Sep. 21, 2007, mixture of at least one reactant comprising the element or provisional application No.60 / 975,330 , filed on Sep. elements that form the catalyst and at least one other 26 , 2007 , provisional application No. 60 /976,004 , element, whereby the catalyst is formed from the source and filed on Sep. 28 , 2007 , provisional application No. the catalysis of atomic hydrogen releases energy in an 60/ 978,435, filed on Oct. 9 , 2007 , provisional appli amount greater than about 300 kJ per mole of hydrogen cation No. 60 /987,552 , filed on Nov. 13 , 2007 , pro during the catalysis of the hydrogen atom . Further provided visional application No. 60 / 987,946 , filed on Nov. 14 , is a reactor wherein the reaction mixture comprises a cata 2007, provisional application No. 60 / 989,677 , filed lyst or a source of catalyst and atomic hydrogen or a source on Nov. 21 , 2007 , provisional application No.60/991 , of atomic hydrogen ( H ) wherein at least one of the catalyst 434 , filed on Nov. 30, 2007 , provisional application and atomic hydrogen is released by a chemical reaction of at No. 60 /991,974 , filed on Dec. 3 , 2007 , provisional least one species of the reaction mixture or between two or application No. 60 /992,601 , filed on Dec. 5 , 2007 , more reaction -mixture species. In an embodiment, the spe provisional application No. 61/ 012,717 , filed on Dec. ciesmay be at least one of an element, complex , alloy, or a 10 , 2007, provisional application No. 61/ 014,860 , compound such as a molecular or inorganic compound filed on Dec. 19 , 2007 , provisional application No. wherein each may be at least one of a reagent or product in 61/ 016,790 , filed on Dec. 26 , 2007, provisional appli the reactor. Alternatively , the species may form a complex , cation No. 61/ 020,023 , filed on Jan. 9 , 2008 , provi alloy , or compound with at least one of hydrogen and the sional application No. 61 /021,205 , filed on Jan. 15 , catalyst. Preferably , the reaction to generate at least one of 2008 , provisional application No. 61/ 021,808 , filed atomic H and catalyst is reversible .

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ENERGY COOLANT STEAM -70 POWER -54 TURBINE GEN . 62 ? BO COOLANT HEAT EXCHANGER 52 50 42 - CATALYTIC MATERIAL , 58 MATERIAL ,56 PRODUCTS Patent Application Publication Dec. 26 , 2019 Sheet 1 of 51 US 2019/0389723 A1

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HYDROGEN -CATALYST REACTOR (ps137 is an integer ) replaces the well known parameter n = integer in the Rydberg equation for hydrogen excited CROSS -REFERENCES TO RELATED states . He+ , Art , and K are predicted to serve as catalysts APPLICATIONS since they meet the catalyst criterion a chemical or physi [0001 ] This application is a Continuation of application cal process with an enthalpy change equal to an integer Ser. No. 12/ 108,700 filed Apr. 24 , 2008 which claims the multiple of the potential energy of atomic hydrogen , 27.2 benefit of ( 1 ) Application No. 60 /913,556 filed on Apr. 24 , eV. Specific predictions based on closed - form equations for 2007 ; ( 2 ) Application No. 60/ 952,305 filed on Jul. 27, 2007 ; energy levels were tested . For example , two H ( 1 / p ) may ( 3 ) Application No. 60 /954,426 filed on Aug. 7 , 2007 ; ( 4 ) react to form H2( 1/ p ) that have vibrational and rotational Application No. 60 / 935,373 filed on Aug. 9 , 2007 ; ( 5 ) energies that are p² times those of H2 comprising uncata Application No. 60 /955,465 filed on Aug. 13, 2007 ; (6 ) lyzed atomic hydrogen . Rotational lines were observed in Application No. 60 /956,821 filed on Aug. 20 , 2007 ; ( 7 ) the 145-300 nm region from atmospheric pressure electron Application No. 60 /957,540 filed on Aug. 23 , 2007 ; ( 8 ) beam excited argon -hydrogen plasmas . The unprecedented Application No. 60 / 972,342 filed on Sep. 14 , 2007 ; ( 9 ) energy spacing of 42 times that of hydrogen established the Application No. 60 / 974,191 filed on Sep. 21 , 2007 ; ( 10 ) internuclear distance as 1/4 that of H , and identified H2( 1/4 ) . Application No. 60 /975,330 filed on Sep. 26 , 2007 ; (11 ) [0003 ] The predicted products of alkali catalyst K are Application No. 60 /976,004 filed on Sep. 28 , 2007 ; ( 12 ) H-( 1/4 ) which form KH * X , a novel alkali halido ( X ) Application No. 60 /978,435 filed on Oct. 9 , 2007; ( 13 ) hydride compound , and H2( 1/4 ) which may be trapped in the Application No. 60 /987,552 filed on Nov. 13, 2007 ; ( 14 ) crystal. The ' H MAS NMR spectrum of novel compound Application No. 60 /987,946 filed on Nov. 14 , 2007 ; ( 15 ) KH * Cl relative to external tetramethylsilane (TMS ) showed Application No. 60 /989,677 filed on Nov. 21, 2007 ; ( 16 ) a large distinct upfield resonance at -4.4 ppm corresponding Application No. 60 / 991,434 filed on Nov. 30 , 2007 ; ( 17 ) to an absolute resonance shift of -35.9 ppm that matched the Application No. 60 / 991,974 filed on Dec. 3 , 2007 ; (18 ) theoretical prediction of H-( 1/ p ) with p = 4 . The predicted Application No. 60 /992,601 filed on Dec. 5 , 2007; (19 ) frequencies of ortho and para- H2 ( 1/4 ) were observed at 1943 Application No. 61/ 012,717 filed on Dec. 10 , 2007 ; (20 ) cm- and 2012 cm-' in the high resolution FTIR spectrum of Application No. 61/ 014,860 filed on Dec. 19, 2007 ; (21 ) KH * I having a -4.6 ppm NMR peak assigned to H-( 1/4 ). Application No. 61/ 016,790 filed on Dec. 26 , 2007 ; ( 22 ) The 1943/2012 cm - 1 -intensity ratio matched the character Application No. 61/ 020,023 filed on Jan. 9 , 2008 ; (23 ) istic ortho - to -para - peak - intensity ratio of 3 : 1, and the ortho Application No. 61 /021,205 filed on Jan. 15 , 2008 ; ( 24 ) para splitting of 69 cm matched that predicted . KH * C1 Application No. 61 /021,808 filed on Jan. 17 , 2008 ; (25 ) having H-( 1/4 ) by NMR was incident to the 12.5 keV Application No. 61/ 022,112 filed on Jan. 18 , 2008 ; ( 26 ) electron - beam which excited similar emission of interstitial Application No. 61 /022,949 filed on Jan. 23 , 2008 ; (27 ) H2( 1/4 ) as observed in the argon -hydrogen plasma. KNO3 Application No. 61 /023,297 filed on Jan. 24 , 2008 ; (28 ) and Raney nickel were used as a source of K catalyst and Application No. 61 /023,687 filed on Jan. 25 , 2008 ; ( 29 ) atomic hydrogen , respectively , to produce the corresponding Application No. 61/ 024,730 filed on Jan. 30 , 2008; (30 ) exothermic reaction . The energy balance was AH = -17,925 Application No. 61/ 025,520 filed on Feb. 1 , 2008 ; (31 ) kcal/ mole KNO3, about 300 times that expected for the most Application No. 61 /028,605 filed on Feb. 14 , 2008 ; (32 ) energetic known chemistry of KNO3, and -3585 kcal/ mole Application No. 61 /030,468 filed on Feb. 21, 2008 ; (33 ) H2, over 60 times the hypothetical maximum enthalpy of Application No. 61/ 064,453 filed on Mar. 6 , 2008 ; (34 ) –57.8 kcal mole H , due to combustion of hydrogen with Application No. 61/ filed on Mar. 21 , 2008 , and (35 ) atmospheric oxygen , assuming the maximum possible H , Application No. 61/ filed on Apr. 17 , 2008 , all of inventory. The reduction of KNO3 to water, potassium which are herein incorporated by reference in their entirety . metal, and NH , calculated from the heats of formation only releases -14.2 kcal /mole H , which cannot account for the DESCRIPTION OF THE INVENTION observed heat; nor can hydrogen combustion . But, the Field of the Invention results are consistent with the formation of H ( 1/4 ) and [0002 ] As disclosed in the paper R.Mills , J. He, Z. Chang, H2( 1/4 ) having enthalpies of formation of over 100 times W. Good , Y. Lu , B. Dhandapani, “ Catalysis of Atomic that of combustion . Hydrogen to Novel Hydrogen Species H-( 1/4 ) and H (1/4 ) [0004 ] In embodiments , the invention comprises a power as a New Power Source ” , Int. J. Hydrogen Energy, Vol. 32 , source and a reactor to form lower - energy -hydrogen species No. 12 , (2007 ) , pp . 2573-2584 which is herein incorporated and compounds . The invention further comprises catalyst by reference , the data from a broad spectrum of investiga reaction mixtures to provide catalyst and atomic hydrogen . tional techniques strongly and consistently indicates that [ 0005 ] Preferred atomic catalysts are lithium , potassium , hydrogen can exist in lower -energy states then previously and cesium atoms. A preferred molecular catalyst is NaH . thoughtpossible . The predicted reaction involves a resonant, nonradiative energy transfer from otherwise stable atomic Hydrinos hydrogen to a catalyst capable of accepting the energy . The [ 0006 ] A hydrogen atom having a binding energy given by product is H ( 1 / p ), fractional Rydberg states of atomic hydro gen wherein Binding Energy 13.6 eV ( 1 ) ( 1 / p ) 2 1 1 1 1 2 ' 3 ' 7 ? where p is an integer greater than 1 , preferably from 2 to 137 , is disclosed in R. L. Mills , “ The Grand Unified Theory US 2019/0389723 A1 Dec. 26 , 2019 2 of Classical Quantum Mechanics ” , October 2007 Edition , for One- through Twenty - Electron Atoms, ” Physics Essays, (posted at http ://www.blacklightpowercom/theory/book . Vol. 18 , (2005 ), 321-361; R.L. Mills , P. C. Ray, R.M. Mayo , shtml) ; R. Mills , The Grand Unified Theory of Classical M. Nansteel , B. Dhandapani, J. Phillips, " Spectroscopic Quantum Mechanics, May 2006 Edition , BlackLight Power, Study of Unique Line Broadening and Inversion in Low Inc., Cranbury , N.J., ( “ '06 Mills GUT” ) , provided by Black Pressure Microwave Generated Water Plasmas, " J. Plasma Light Power , Inc. , 493 Old Trenton Road , Cranbury , N.J., Physics , Vol. 71 , No 6 , (2005 ), 877-888 ; R. L. Mills , “ The 08512 (posted at www.blacklightpower.com ); R. Mills , The Fallacy of Feynman's Argument on the Stability of the Grand Unified Theory of Classical Quantum Mechanics , Hydrogen Atom According to Quantum Mechanics , ” Ann . January 2004 Edition , BlackLight Power , Inc. , Cranbury, Fund . Louis de Broglie , Vol. 30 , No. 2 , (2005 ), pp . 129-151 ; N.J., (“ '04 Mills GUT” ) , provided by BlackLight Power , R. L. Mills , B. Dhandapani, J. He, “ Highly Stable Amor Inc., 493 Old Trenton Road , Cranbury , N.J. , 08512; R.Mills , phous Silicon Hydride from a Helium Plasma Reaction , " The Grand Unified Theory of Classical Quantum Mechan Materials Chemistry and Physics, 94 / 2-3 , ( 2005 ), 298-307 ; ics , September 2003 Edition , BlackLight Power , Inc., Cran R. L. Mills , J. He, Z , Chang, W. Good , Y. Lu, B. Dhanda bury , N.J., (“ '03 Mills GUT” ) , provided by BlackLight pani, “ Catalysis of Atomic Hydrogen to Novel Hydrides as Power , Inc. , 493 Old Trenton Road , Cranbury, N.J. , 08512 ; a New Power Source , ” Prepr. Pap.-Am. Chem . Soc. Conf. , R. Mills , The Grand Unified Theory of Classical Quantum Div . Fuel Chem ., Vol. 50 , No. 2 , ( 2005 ) ; R. L. Mills , J. Mechanics, September 2002 Edition , BlackLight Power , Sankar, A. Voigt, J. He, P. Ray, B. Dhandapani , “ Role of Inc., Cranbury , N.J., (“ '02 Mills GUT” ) , provided by Black Atomic Hydrogen Density and Energy in Low Power CVD Light Power , Inc., 493 Old Trenton Road , Cranbury , N.J. , Synthesis of Diamond Films, ” Thin Solid Films , 478, (2005 ) 08512 ; R. Mills , The Grand Unified Theory of Classical 77-90 ; R. L. Mills , “ The Nature of the Chemical Bond Quantum Mechanics, September 2001 Edition , BlackLight Revisited and an Alternative Maxwellian Approach ,” Phys Power , Inc., Cranbury , N.J., Distributed by Amazon.com ics Essays, Vol. 17 , (2004 ) , 342-389; R. L. Mills , P. Ray , ( " P01 Mills GUT" ) , provided by BlackLight Power , Inc., 493 " Stationary Inverted Lyman Population and a Very Stable Old Trenton Road , Cranbury, N.J. , 08512 ; R. Mills , The Novel Hydride Formed by a Catalytic Reaction of Atomic Grand Unified Theory of Classical Quantum Mechanics , Hydrogen and Certain Catalysts , ” J. Opt. Mat ., 27 , ( 2004 ) , January 2000 Edition , BlackLight Power, Inc., Cranbury, 181-186 ; W.Good , P. Jansson , M.Nansteel , J. He, A. Voigt, N.J., Distributed by Amazon.com (“ '00 Mills GUT” ), pro “ Spectroscopic and NMR Identification of Novel Hydride vided by BlackLight Power , Inc., 493 Old Trenton Road , Ions in Fractional Quantum Energy States Formed by an Cranbury , N.J., 08512 ; R. L. Mills , “ Physical Solutions of Exothermic Reaction of Atomic Hydrogen with Certain the Nature of the Atom , Photon , and Their Interactions to Catalysts , ” European Physical Journal: Applied Physics, 28 , Form Excited and Predicted Hydrino States, ” Physics Essay, ( 2004 ) , 83-104 ; J. Phillips, R. L. Mills, X. Chen , “ Water in press; R. L.Mills , “ Exact Classical Quantum Mechanical Bath calorimetric Study of Excess Heat in ‘Resonance Solution for Atomic Helium which Predicts Conjugate Transfer Plasmas, ” J. Appl. Phys . , Vol. 96 , No. 6 , (2004 ) Parameters from a Unique Solution for the First Time, " 3095-3102 ; R. L.Mills , Y. Lu , M. Nansteel , J. He, A. Voigt, Physics Essays, in press ; R. L. Mills , P. Ray, B. Dhandapani, W. Good , B. Dhandapani, “ Energetic Catalyst -Hydrogen “ Excessive Balmer a Line Broadening of Water - Vapor Plasma Reaction as a Potential New Energy Source , ” Divi Capacitively -Coupled RF Discharge Plasmas, ” International sion of Fuel Chemistry , Session : Advances in Hydrogen Journal of Hydrogen Energy, Vol. 33 , ( 2008 ) , 802-815 ; R. L. Energy, Prepr. Pap.—Am. Chem . Soc. Conf. , Vol. 49 , No. 2 , Mills , J. He, M. Nansteel, B. Dhandapani, “ Catalysis of (2004 ) ; R. L. Mills, J. Sankar , A. Voigt , J. He, B. Dhanda Atomic Hydrogen to New Hydrides as a New Power pani, “ Synthesis of HDLC Films from Solid Carbon ,” J. Source ,” International Journal of Global Energy Issues Materials Science , J. Mater . Sci. 39 ( 2004 ) 3309-3318 ; R. L. ( IJGEI) . Special Edition in Energy Systems, Vol . 28 , issue Mills , Y. Lu , M. Nansteel, J. He, A. Voigt, B. Dhandapani, 2-3 , ( 2007 ), 304-324 ; R. L.Mills , H. Zea , J. He, B. Dhan “ Energetic Catalyst- Hydrogen Plasma Reaction as a Poten dapani, “ Water Bath calorimetry on a Catalytic Reaction of tial New Energy Source, ” Division of Fuel Chemistry , Atomic Hydrogen ,” Int . J. Hydrogen Energy, Vol. 32, Session : Chemistry of Solid , Liquid , and Gaseous Fuels , ( 2007 ), 4258-4266 ; J. Phillips, C. K. Chen , R. L. Mills , Prepr. Pap.-Am. Chem . Soc. Conf. , Vol. 49 , No. 1 , ( 2004 ) ; “ Evidence of Catalytic Production of Hot Hydrogen in R. L. Mills, “ Classical Quantum Mechanics , ” Physics RE -Generated Hydrogen / Argon Plasmas, " Int. J. Hydrogen Essays, Vol. 16 , ( 2003 ) , 433-498 ; R. L. Mills , P. Ray , M. Energy , Vol. 32 ( 14 ), ( 2007 ) , 3010-3025 ; R. L.Mills , J. He, Nansteel, J. He, X. Chen , A. Voigt, B. Dhandapani , “ Char Y. Lu , M. Nansteel , Z. Chang , B. Dhandapani, “ Compre acterization of an Energetic Catalyst -Hydrogen Plasma hensive Identification and Potential Applications of New Reaction as a Potential New Energy Source ,” Am . Chem . States of Hydrogen ,” Int. J. Hydrogen Energy, Vol. 32 ( 14 ) , Soc . Div . Fuel Chem . Prepr. , Vol . 48, No. 2 , (2003 ) ; R. L. ( 2007) , 2988-3009 ; R. L. Mills , J. He , Z. Chang, W.Good , Mills , J. Sankar , A. Voigt, J. He, B. Dhandapani, “ Spectro Y. Lu , B. Dhandapani, “ Catalysis of Atomic Hydrogen to scopic Characterization of the Atomic Hydrogen Energies Novel Hydrogen Species H-( 1/4 ) and H2( 1/4 ) as a New and Densities and Carbon Species During Helium -Hydro Power Source , ” Int. J. Hydrogen Energy, Vol. 32 (13 ) , gen -Methane Plasma CVD Synthesis of Diamond Films, " ( 2007 ) , pp . 2573-2584 ; R. L. Mills , “ Maxwell's Equations Chemistry of Materials , Vol. 15 , (2003 ), pp . 1313-1321 ; R. and QED : Which is Fact and Which is Fiction, ” Physics L. Mills , P. Ray , “ Extreme Ultraviolet Spectroscopy of Essays , Vol. 19, (2006 ) , 225-262 ; R. L. Mills , P. Ray, B. Helium -Hydrogen Plasma, ” J. Phys. D , Applied Physics , Dhandapani, Evidence of an energy transfer reaction Vol. 36 , (2003 ) , pp . 1535-1542 ; R. L. Mills , X. Chen , P. Ray, between atomic hydrogen and argon II or helium II as the J. He , B. Dhandapani, “ Plasma Power Source Based on a source of excessively hot H atoms in radio - frequency plas Catalytic Reaction of Atomic Hydrogen Measured by Water mas , J. Plasma Physics, Vol. 72 , No. 4 , (2006 ) , 469-484 ; R. Bath calorimetry, ” Thermochimica Acta , Vol. 406 /1-2 , L. Mills , “ Exact Classical Quantum Mechanical Solutions ( 2003 ) , pp . 35-53 ; R. L. Mills , B. Dhandapani, J. He, US 2019/0389723 A1 Dec. 26 , 2019 3

“ Highly Stable Amorphous Silicon Hydride, ” Solar Energy “ Comparison of Excessive Balmer a Line Broadening of Materials & Solar Cells , Vol. 80 , No. 1 , (2003 ) , pp . 1-20 ; R. Glow Discharge and Microwave Hydrogen Plasmas with L.Mills , P. Ray, R. M.Mayo , “ The Potential for a Hydrogen Certain Catalysts , ” J. of Applied Physics , Vol. 92 , No. 12 , Water- Plasma Laser, ” Applied Physics Letters , Vol. 82 , No. ( 2002 ), pp . 7008-7022 ; R. L.Mills , P. Ray , B. Dhandapani, 11, (2003 ) , pp . 1679-1681; R. L. Mills , P. Ray , “ Stationary M. Nansteel, X. Chen , J. He, “ New Power Source from Inverted Lyman Population Formed from Incandescently Fractional Quantum Energy Levels of Atomic Hydrogen that Heated Hydrogen Gas with Certain Catalysts, ” J. Phys. D , Surpasses Internal Combustion ,” J. Mol. Struct ., Vol. 643 , Applied Physics , Vol. 36 , ( 2003 ), pp . 1504-1509 ; R. L. No. 1-3, (2002 ) , pp . 43-54 ; R. L.Mills , J. Dong , W. Good , Mills , P. Ray , B. Dhandapani, J. He, “ Comparison of Exces P. Ray, J. He, B. Dhandapani, “Measurement of Energy sive Balmer a Line Broadening of Inductively and Capaci Balances of Noble Gas - Hydrogen Discharge Plasmas Using tively Coupled RF ,Microwave , and Glow Discharge Hydro Calvet calorimetry, " Int. J. Hydrogen Energy, Vol. 27 , No. 9 , gen Plasmas with Certain Catalysts ,” IEEE Transactions on ( 2002 ), pp . 967-978 ; R. L. Mills , P. Ray, “ Spectroscopic Plasma Science, Vol. 31, No. (2003 ) , pp . 338-355 ; R. L. Identification of a Novel Catalytic Reaction of Rubidium Ion Mills , P. Ray, R. M. Mayo , “ CW HI Laser Based on a with Atomic Hydrogen and the Hydride Ion Product ,” Int . J. Stationary Inverted Lyman Population Formed from Incan Hydrogen Energy, Vol . 27 , No. 9 , (2002 ) , pp . 927-935 ; R. L. descently Heated Hydrogen Gas with Certain Group I Cata Mills , A. Voigt, P. Ray , M.Nansteel , B. Dhandapani, “ Mea lysts , ” IEEE Transactions on Plasma Science , Vol. 31 , No. 2 , surement of Hydrogen Balmer Line Broadening and Ther ( 2003 ), pp . 236-247 ; R. L. Mills , P. Ray, J. Dong, M. mal Power Balances of Noble Gas- Hydrogen Discharge Nansteel, B. Dhandapani, J. He, “ Spectral Emission of Plasmas, ” Int. J. Hydrogen Energy , Vol. 27 , No. 6 , ( 2002 ) , Fractional- Principal - Quantum - Energy -Level Atomic and pp . 671-685 ; R. L. Mills , N. Greenig , S. Hicks, “ Optically Molecular Hydrogen ,” Vibrational Spectroscopy , Vol. 31, Measured Power Balances of Glow Discharges of Mixtures No. 2 , ( 2003 ) , pp . 195-213 ; H. Conrads, R. L. Mills , Th . of Argon , Hydrogen , and Potassium , Rubidium , Cesium , or Wrubel, “ Emission in the Deep Vacuum Ultraviolet from a Strontium Vapor, " Int. J. Hydrogen Energy, Vol. 27 , No. 6 , Plasma Formed by Incandescently Heating Hydrogen Gas (2002 ) , pp . 651-670 ; R. L. Mills , “ The Grand Unified with Trace Amounts of Potassium Carbonate , " Plasma Theory of Classical Quantum Mechanics, ” Int. J. Hydrogen Sources Science and Technology, Vol. 12 , (2003 ) , pp . 389 Energy, Vol. 27 , No. 5 , (2002 ) , pp . 565-590 ; R. L. Mills , P. 395; R. L. Mills , J. He , P. Ray, B. Dhandapani, X. Chen , Ray , “ Vibrational Spectral Emission of Fractional- Principal “ Synthesis and Characterization of a Highly Stable Amor Quantum - Energy - Level Hydrogen Molecular Ion , ” Int. J. phous Silicon Hydride as the Product of a Catalytic Helium Hydrogen Energy, Vol. 27 , No. 5 , (2002 ) , pp . 533-564 ; R. L. Hydrogen Plasma Reaction , ” Int. J. Hydrogen Energy, Vol. Mills and M.Nansteel , P. Ray, “ Argon -Hydrogen - Strontium 28 , No. 12 , (2003 ) , pp . 1401-1424 ; R. L. Mills , P. Ray , “ A Discharge Light Source , " IEEE Transactions on Plasma Comprehensive Study of Spectra of the Bound -Free Hyper Science, Vol. 30 , No. 2 , ( 2002 ) , pp . 639-653 ; R. L. Mills , P. fine Levels of Novel Hydride Ion H-( 1/2 ) , Hydrogen , Nitro Ray , " Spectral Emission of Fractional Quantum Energy gen , and Air, ” Int. J. Hydrogen Energy, Vol. 28 , No. 8 , Levels of Atomic Hydrogen from a Helium -Hydrogen ( 2003 ) , pp . 825-871; R. L. Mills , M. Nansteel , and P. Ray , Plasma and the Implications for Dark Matter ,” Int. J. Hydro " Excessively Bright Hydrogen - Strontium Plasma Light gen Energy , (2002 ), Vol. 27 , No. 3 , pp . 301-322 ; R. L.Mills , Source Due to Energy Resonance of Strontium with Hydro P. Ray, “ Spectroscopic Identification of a Novel Catalytic gen ,” J. Plasma Physics , Vol. 69 , (2003 ), pp . 131-158 ; R. L. Reaction of Potassium and Atomic Hydrogen and the Mills , “ Highly Stable Novel Inorganic Hydrides, ” J. New Hydride Ion Product, ” Int. J. Hydrogen Energy, Vol. 27 , No. Materials for Electrochemical Systems, Vol. 6 , (2003 ) , pp . 2 , (2002 ), pp . 183-192; R. L. Mills , E. Dayalan , “ Novel 45-54 ; R. L. Mills , P. Ray, “ Substantial Changes in the Alkali and Alkaline Earth Hydrides for High Voltage and Characteristics of a Microwave Plasma Due to Combining High Energy Density Batteries, ” Proceedings of the 17th Argon and Hydrogen ," New Journal of Physics , www.njp . Annual Battery Conference on Applications and Advances, org , Vol . 4 , (2002 ) , pp . 22.1-22.17; R. M.Mayo , R. L. Mills , California State University , Long Beach , Calif ., (Jan. 15-18 , M.Nansteel , “ Direct Plasmadynamic Conversion of Plasma 2002 ) , pp . 1-6 ; R. L. Mills , W. Good , A. Voigt , Jinquan Thermal Power to Electricity , ” IEEE Transactions on Dong , “ Minimum Heat of Formation of Potassium Iodo Plasma Science , October , (2002 ) , Vol. 30 , No. 5 , pp . 2066 Hydride, ” Int. J. Hydrogen Energy, Vol. 26 , No. 11 , (2001 ) , 2073 ; R. L. Mills , M. Nansteel, P. Ray , " Bright Hydrogen pp . 1199-1208 ; R. L. Mills , “ The Nature of Free Electrons Light Source due to a Resonant Energy Transfer with in Superfluid HeliumaTest of Quantum Mechanics and a Strontium and Argon Ions, " New Journal of Physics, Vol. 4 , Basis to Review its Foundations and Make a Comparison to ( 2002) , pp . 70.1-70.28 ; R. M. Mayo , R. L. Mills , M. Classical Theory ,” Int. J. Hydrogen Energy, Vol. 26 , No. 10 , Nansteel, " On the Potential of Direct and MHD Conversion (2001 ), pp . 1059-1096 ; R. L. Mills , “ Spectroscopic Identi of Power from a Novel Plasma Source to Electricity for fication of a Novel Catalytic Reaction of Atomic Hydrogen Microdistributed Power Applications, ” IEEE Transactions and the Hydride Ion Product, ” Int. J. Hydrogen Energy, Vol. on Plasma Science , August , (2002 ), Vol. 30 , No. 4 , pp . 26 , No. 10 , ( 2001 ), pp . 1041-1058 ; R. L. Mills , B. Dhan 1568-1578 ; R. M. Mayo , R. L. Mills , “ Direct Plasmady dapani, M. Nansteel, J. He, A. Voigt , “ Identification of namic Conversion of Plasma Thermal Power to Electricity Compounds Containing Novel Hydride lons by Nuclear for Microdistributed Power Applications ,” 40th Annual Magnetic Resonance Spectroscopy " , Int. J. Hydrogen Power Sources Conference , Cherry Hill , N.J., Jun . 10-13 , Energy, Vol. 26 , No. 9 , (2001 ) , pp . 965-979 ; R. L. Mills , T. ( 2002 ), pp . 1-4 ; R. L. Mills , E. Dayalan , P. Ray, B. Dhan Onuma, and Y. Lu, “ Formation of a Hydrogen Plasma from dapani, J. He, “ Highly Stable Novel Inorganic Hydrides an Incandescently Heated Hydrogen - Catalyst Gas Mixture from Aqueous Electrolysis and Plasma Electrolysis ,” Elec with an Anomalous Afterglow Duration , ” Int. J. Hydrogen trochimica Acta , Vol. 47 , No. 24 , (2002 ), pp . 3909-3926 ; R. Energy, Vol. 26 , No. 7 , July , (2001 ), pp . 749-762 ; R. L. L. Mills , P. Ray, B. Dhandapani, R. M. Mayo , J. He, Mills , “ Observation of Extreme Ultraviolet Emission from US 2019/0389723 A1 Dec. 26 , 2019 4

Hydrogen - KI Plasmas Produced by a Hollow Cathode Dis Nos. 6,024,935 and 7,188,033 , the entire disclosures of charge, ” Int . J. Hydrogen Energy, Vol. 26 , No. 6 , ( 2001) , pp . which are all incorporated herein by reference (hereinafter 579-592 ; R. L.Mills , B. Dhandapani, M.Nansteel , J. He, T. “Mills Prior Publications” ) . Shannon , A. Echezuria , “ Synthesis and Characterization of [0007 ] The binding energy of an atom , ion , or molecule , Novel Hydride Compounds , ” Int. J. of Hydrogen Energy, also known as the ionization energy , is the energy required Vol. 26 , No. 4 , (2001 ) , pp . 339-367 ; R. L.Mills , “ Temporal to remove one electron from the atom , ion or molecule . A Behavior of Light- Emission in the Visible Spectral Range hydrogen atom having the binding energy given in Eq. ( 1 ) is from a Ti -K2CO3 - H -Cell , ” Int. J. Hydrogen Energy , Vol. 26 , hereafter referred to as a hydrino atom or hydrino . The No. 4 , ( 2001 ) , pp . 327-332 ; R. L. Mills , M.Nansteel , and Y. designation for a hydrino of radius aqp , where ay is the Lu , “ Observation of Extreme Ultraviolet Hydrogen Emis radius of an ordinary hydrogen atom and p is an integer , is sion from Incandescently Heated Hydrogen Gas with Stron tium that Produced an Anomalous Optically Measured Power Balance, ” Int. J. Hydrogen Energy , Vol. 26 , No. 4 , [?? ( 2001) , pp . 309-326 ; R. L. Mills , “ BlackLight Power Tech nology — A New Clean Hydrogen Energy Source with the Potential for Direct Conversion to Electricity ,” Proceedings A hydrogen atom with a radius ay is hereinafter referred to of the National Hydrogen Association , 12th Annual U.S. as " ordinary hydrogen atom ” or “ normal hydrogen atom .” Hydrogen Meeting and Exposition , Hydrogen : The Common Ordinary atomic hydrogen is characterized by its binding Thread , The Washington Hilton and Towers , Washington energy of 13.6 eV . D.C., (Mar. 6-8 , 2001 ) , pp . 671-697 ; R.L. Mills , “ The Grand [0008 ] Hydrinos are formed by reacting an ordinary Unified Theory of Classical Quantum Mechanics, ” Global hydrogen atom with a catalyst having a net enthalpy of Foundation , Inc. Orbis Scientiae entitled The Role of Attrac reaction of about tive and Repulsive Gravitational Forces in Cosmic Accel m.27.2 eV ( 2 ) eration of Particles The Origin of the Cosmic Gamma Ray where m is an integer . This catalyst has also been referred to Bursts , ( 29th Conference on High Energy Physics and as an energy hole or source of energy hole in Mills earlier Cosmology Since 1964) Dr. Behram N. Kursunoglu , Chair filed patent applications. It is believed that the rate of man , Dec. 14-17 , 2000 , Lago Mar Resort, Fort Lauderdale , catalysis is increased as the net enthalpy of reaction is more Fla . , Kluwer Academic /Plenum Publishers , New York , pp . closely matched to m.27.2 eV. It has been found that 243-258 ; R. L. Mills , B. Dhandapani, N. Greenig , J. He, catalysts having a net enthalpy of reaction within + 10 % , “ Synthesis and Characterization of Potassium Iodo preferably 25 % , of m.27.2 eV are suitable for most appli Hydride, ” Int. J. of Hydrogen Energy, Vol . 25 , Issue 12 , cations . December , (2000 ) , pp . 1185-1203 ; R. L.Mills , “ The Hydro [ 0009 ] This catalysis releases energy from the hydrogen gen Atom Revisited ,” Int. J. of Hydrogen Energy , Vol. 25 , atom with a commensurate decrease in size of the hydrogen Issue 12 , December, (2000 ) , pp . 1171-1183 ; R. L. Mills , atom , in = nay . For example , the catalysis of H ( n = 1 ) to “ BlackLight Power Technology – A New Clean Energy H ( n = 1 / 2 ) releases 40.8 eV , and the hydrogen radius Source with the Potential for Direct Conversion to Electric decreases from ay to 1 /2ay . A catalytic system is provided ity ,” Global Foundation International Conference on by the ionization oft electrons from an atom each to a “ Global Warming and Energy Policy, ” Dr. Behram N.Kur continuum energy level such that the sum of the ionization sunoglu , Chairman , Fort Lauderdale , Fla . , Nov. 26-28 , 2000 , energies of the t electrons is approximately m.27.2 eV where Kluwer Academic / Plenum Publishers , New York , pp. 187 in is an integer. 202 ; R. L. Mills , J. Dong, Y. Lu , " Observation of Extreme [0010 ] One such catalytic system involves lithium metal. Ultraviolet Hydrogen Emission from Incandescently Heated The first and second ionization energies of lithium are Hydrogen Gas with Certain Catalysts , ” Int. J. Hydrogen 5.39172 eV and 75.64018 eV, respectively [ 1 ]. The double Energy, Vol. 25 , (2000 ) , pp . 919-943 ; R. L. Mills , “ Novel ionization ( t = 2 ) reaction of Li to Li2 + , then , has a net Inorganic Hydride, ” Int. J. of Hydrogen Energy, Vol. 25 , enthalpy of reaction of 81.0319 eV , which is equivalent to ( 2000 ), pp . 669-683 ; R. L. Mills , “ Novel Hydrogen Com m = 3 in Eq. (2 ). pounds from a Potassium Carbonate Electrolytic Cell ,” Fusion Technol. , Vol. 37 , No. 2 ,March , ( 2000 ) , pp . 157-182 ; R. L. Mills , W. Good , “ Fractional Quantum Energy Levels 81.0319 eV + Li( m ) + H ?? ( 3 ) of Hydrogen , ” Fusion Technology , Vol. 28 , No. 4 , Novem C ber , ( 1995 ) , pp . 1697-1719 ; R. L. Mills , W. Good , R. Li2 + + 2 € + H ?? + [ ( p + 3 ) 2 – p ? ] - 13.6 eV Shaubach , “ Dihydrino Molecule Identification ,” Fusion ( p + 3 ) Technol. , Vol. 25 , ( 1994 ) , 103 ; R. L.Mills and S. Kneizys , Li2 + + 2e ? Li( m ) +81.0319 eV Fusion Technol. Vol. 20 , ( 1991) , 65; and in prior published PCT application Nos . W090 /13126 ; W092 /10838 ; W094 / 29873 ; W096 /42085 ; W099 /05735 ; W099 / 26078 ; W099 / And , the overall reaction is 34322 ; W099/ 35698 ; W000 /07931 ; W000 / 07932 ; W001 / 095944 ; W001 / 18948 ; W001/ 21300 ; W001/ 22472 ; ?? ?? W001 /70627 ; W002 / 087291 ; WO02 /088020 ; W002 / H ? H + [( p + 3 )2 – p ? ] . 13.6 eV ( 5 ) 16956 ; WO03 /093173 ; WO03 /066516 ; W004 /092058 ; P (p + 3 ) WO05/ 041368 ; W005/ 067678 ; WO2005 / 116630 ; WO2007/ 051078 ; and WO2007 /053486 ; and prior U.S. Pat . US 2019/0389723 A1 Dec. 26 , 2019 5

[0011 ] In another embodiment , the catalytic system hydrino catalysis should have a higher reaction rate than that involves cesium . The first and second ionization energies of of the inorganic ion catalyst due to the better match of the cesium are 3.89390 eV and 23.15745 eV , respectively . The enthalpy to m.27.2 eV . double ionization ( t = 2 ) reaction of Cs to Cs2 + , then , has a net enthalpy of reaction of 27.05135 eV, which is equivalent to Further Catalysis Products of the Present Invention m = 1 in Eq. (2 ). [ 0013 ] The hydrino hydride ion of the present invention can be formed by the reaction of an electron source with a 27.05135 eV + Cs (m ) + H ?? (6 ) hydrino , that is , a hydrogen atom having a binding energy of p - about C32+ + 2 +41( 0 * 1) ] +[ p + 1) 2 –p ? 1-13.6 eV 13.6 eV Cs2 + + 2e ? Cs( m ) + 27.05135 eV ( 7 ) n2

And the overall reaction is where

?? ?? ? H (8 ) 1 ( p + 1 ) + [ ( p + 1 ) 2 – p ? ] 13.6 eV N = — ? [0012 ] An additional catalytic system involves potassium metal . The first , second , and third ionization energies of and p is an integer greater than 1. The hydrino hydride ion potassium are 4.34066 eV , 31.63 eV, 45.806 eV, respectively is represented by H-( n = 1 / p ) or Hº( 1 / p ): [ 1 ] . The triple ionization ( t = 3 ) reaction of K to K3 + , then , has a net enthalpy of reaction of 81.7767 eV , which is equivalent ?? ( 13) to m = 3 in Eq . ( 2 ) . H te + H (n = 1 / p ) ? + ?? (14 ) H + e + H ( 1 / p ) 81.7767 eV + K ( m ) + H M?? ( 9 ) ? K3+ + 3e + H ?? ( p + 3 ) + [ ( p + 3 )2 – p ? ] - 13.6 eV [0014 ] The hydrino hydride ion is distinguished from an ordinary hydride ion comprising an ordinary hydrogen K3 + + 3e ? K ( m ) +81.7426 eV ( 10 ) nucleus and two electrons having a binding energy of about 0.8 eV . The latter is hereafter referred to as “ ordinary hydride ion ” or “ normal hydride ion ” The hydrino hydride ion And , the overall reaction is comprises a hydrogen nucleus including proteum , deute rium , or tritium , and two indistinguishable electrons at a ?? ?? binding energy according to Eq . ( 15) . ? H + [ (p + 3 )2 – p ? ] . 13.6 eV (11 ) [0015 ] The binding energy of a novel hydrino hydride ion (p + 3) can be represented by the following formula : As a power source , the energy given off during catalysis is much greater than the energy lost to the catalyst. The energy Binding Energy = ( 15 ) released is large as compared to conventional chemical ti Vs( s + 1) 22 reactions . For example , when hydrogen and oxygen gases Aloe? # 2 / 1 + undergo combustion to form water 1 + Vs( s + 1) ma ay 1+ Vs( s + 1 ) 8Mea 00 H2( g ) +1/202( g ) ? H20 (1 ) ( 12 ) ? ? the known enthalpy of formation of water is AH = - 286 kJ/ mole or 1.48 eV per hydrogen atom . By contrast , each where ? is an integer greater than one , s = 1 / 2 , u is pi, ? is ( n = 1 ) ordinary hydrogen atom undergoing catalysis releases Planck's constant bar, u , is the permeability of vacuum , me, a net of 40.8 eV . Moreover, further catalytic transitions may is the mass of the electron , u , is the reduced electron mass occur : given by

1 1 1 1 n = memp 3 ' 3 44 5 Me = me + m and so on . Once catalysis begins, hydrinos autocatalyze further in a process called disproportionation . This mecha nism is similar to that of an inorganic ion catalysis . But, US 2019/0389723 A1 Dec. 26 , 2019 6 where mp is the mass of the proton , ay is the radius of the Hz , 22.6 eV (" ordinary trihydrogen molecular ion ” ) . hydrogen atom , a , is the Bohr radius, and e is the elementary Herein , with reference to forms of hydrogen , “ normal” and charge. The radii are given by “ ordinary ” are synonymous . r2 = ri = a0( 1 + Vs( s + 1) ) ; s = 1/ 2 ( 16 ) [0021 ] According to a further embodiment of the inven [0016 ] The binding energies of the hydrino hydride ion , tion , a compound is provided comprising at least one H = ( n = 1 / p ) as a function of p , where p is an integer, are increased binding energy hydrogen species such as ( a ) a shown in TABLE 1 . hydrogen atom having a binding energy of about

TABLE 1 13.6 eV The representative binding energy of the hydrino hydride ion H- ( n = 1 / p ) as a function of p , Eq . (15 ) . Binding Wavelength Hydride Ion ri Energy (eV ) ( ao) " (nm ) preferably within + 10 % , more preferably + 5 % , where p is an H- (n = 1) 1.8660 0.7542 1644 Hn 12 ) 0.9330 3.047 406.9 integer , preferably an integer from 2 to 137 ; (b ) a hydride ion Hn 14 ) 0.6220 6.610 187.6 ( H ) having a binding energy of about H- ( n = 1/4 ) 0.4665 11.23 110.4 Han 1/5 ) 0.3732 16.70 74.23 H (n 1/6 ) 0.3110 22.81 54.35 Binding Energy = Hn= 11 ) 0.2666 29.34 42.25 H- ( n 1/8 ) 0.2333 36.09 34.46 H- (n = 1/9 ) 0.2073 42.84 28.94 ti? V s (s + 1) Tuoe ?# ? / 1 22 H- ( n 1/10) 0.1866 49.38 25.11 1+ Vs( s + 1 ) m ? a 1 + Vs( s + 1 ) H- ( n 1/11) 0.1696 55.50 22.34 8???3 do H- ( n 1/12) 0.1555 60.98 20.33 ? ? Hin = 1/13 ) 0.1435 65.63 18.89 Han 1/14 ) 0.1333 69.22 17.91 Han 1/15 ) 0.1244 71.55 17.33 H- ( n = 1/16 ) 0.1166 72.40 17.12 preferably within + 10 % ,more preferably + 5 % , where p is an H ( n = 1/17) 0.1098 71.56 17.33 integer, preferably an integer from 2 to 24 ; ( c ) H4+ ( 1 /p ) ; ( d ) Hn 1/18 ) 0.1037 68.83 18.01 a trihydrino molecular ion , Hz+ ( 1 / p ) , having a binding H ( n 1/19 ) 0.0982 63.98 19.38 H- ( n 1/20) 0.0933 56.81 21.82 energy of about Hn 1/21) 0.0889 47.11 26.32 Hºn = 1/22 ) 0.0848 34.66 35.76 Hºn 1/23) 0.0811 19.26 64.36 22.6 H- ( n = 1/24) 0.0778 0.6945 1785 eV " Eq. ( 16 ) bEq. (15 ) © [0017 ] According to the present invention , a hydrino preferably within + 10 % , more preferably 5 % , where p is an hydride ion ( H ) having a binding energy according to Eqs. integer, preferably an integer from 2 to 137; ( e ) a dihydrino ( 15-16 ) that is greater than the binding of ordinary hydride having a binding energy of about ion ( about 0.8 eV ) for p = 2 up to 23, and less for p = 24 (H- ) is provided . For p = 2 to p = 24 of Eqs. ( 15-16 ) , the hydride ion binding energies are respectively 3 , 6.6 , 11.2 , 16.7 , 22.8 , 15.3 29.3 , 36.1 , 42.8 , 49.4 , 55.5 , 61.0 , 65.6 , 69.2 , 71.6 , 72.4 , 71.6 , eV 68.8 ,64.0 , 56.8 , 47.1 , 34.7 , 19.3 , and 0.69 eV . Compositions comprising the novel hydride ion are also provided . CTS [0018 ] The hydrino hydride ion is distinguished from an ordinary hydride ion comprising an ordinary hydrogen nucleus and two electrons having a binding energy of about preferably within + 10 % © , more preferably + 5 % , where p is 0.8 eV . The latter is hereafter referred to as “ ordinary hydride an integer , preferably and integer from 2 to 137 ; ( f ) a ion " or " normal hydride ion ” The hydrino hydride ion dihydrino molecular ion with a binding energy of about comprises a hydrogen nucleus including proteum , deute rium , or tritium , and two indistinguishable electrons at a 16.3 binding energy according to Eqs. ( 15-16 ) . ev [0019 ] Novel compounds are provided comprising one or more hydrino hydride ions and one or more other elements . C ) Such a compound is referred to as a hydrino hydride compound [0020 ] Ordinary hydrogen species are characterized by the preferably within + 10 % , more preferably 5 % , where p is an following binding energies ( a ) hydride ion , 0.754 eV (" ordi integer , preferably an integer from 2 to 137 . nary hydride ion " ) ; ( b ) hydrogen atom (“ ordinary hydrogen [0022 ] According to a further preferred embodiment of the atom " ) , 13.6 eV ; ( c ) diatomic hydrogen molecule , 15.3 eV invention , a compound is provided comprising at least one (" ordinary hydrogen molecule " ) ; (d ) hydrogen molecular increased binding energy hydrogen species such as ( a ) a ion , 16.3 eV (“ ordinary hydrogen molecular ion ” ) ; and ( e ) dihydrino molecular ion having a total energy of US 2019/0389723 A1 Dec. 26 , 2019 7

2e2 ( 17 ) € 2 2h ET = -p2 - ( 41n3 – 1 – 21n3) 41 €, (207 )3 8?? , ?? ?? 1 + p V mec2

-p ? 16.13392eV – p30.118755eV preferably within + 10 % , more preferably 15 % ,where p is an hydride ion . The increased binding energy hydride ion can integer, ? is Planck's constant bar, m , is the mass of the be reacted with one ormore cations to produce a compound electron , c is the speed of light in vacuum , u is the reduced comprising at least one increased binding energy hydride nuclear mass , and k is the harmonic force constant solved ion . previously [2 ] and ( b ) a dihydrino molecule having a total [0025 ] Novel hydrogen species and compositions ofmat energy of ter comprising new forms of hydrogen formed by the

ET = ( 18 )

2e2 2h -p? e2 V2 + V2 V2 + 1 v2 40 € , ( 20h ) 3 1 8????? ?? || 2v3 - V7 V2 -1 + 1 mec2 -p- 31.351eV – p0.326469eV preferably within + 10 % ,more preferably + 5 % , where p is an catalysis of atomic hydrogen are disclosed in “ Mills Prior integer and a , is the Bohr radius . Publications” . The novel hydrogen compositions of matter [0023 ] According to one embodiment of the invention comprise : wherein the compound comprises a negatively charged [0026 ] ( a ) at least one neutral , positive, or negative hydro increased binding energy hydrogen species , the compound gen species (hereinafter “ increased binding energy hydrogen further comprises one or more cations, such as a proton , ordinary Hz , or ordinary Hz . species" ) having a binding energy [0024 ] A method is provided for preparing compounds [ 0027 ] ( i) greater than the binding energy of the corre comprising at least one increased binding energy hydride sponding ordinary hydrogen species , or ion . Such compounds are hereinafter referred to as “ hydrino [0028 ] ( ii ) greater than the binding energy of any hydro hydride compounds " . The method comprises reacting gen species for which the corresponding ordinary atomic hydrogen with a catalyst having a net enthalpy of hydrogen species is unstable or is not observed because reaction of about the ordinary hydrogen species ' binding energy is less than thermal energies at ambient conditions ( standard ? .27eV , temperature and pressure , STP ), or is negative ; and [0029 ] (b ) at least one other element. The compounds of the invention are hereinafter referred to as " increased bind where m is an integer greater than 1 , preferably an integer ing energy hydrogen compounds " . less than 400 , to produce an increased binding energy [0030 ] By " other element” in this context is meant an hydrogen atom having a binding energy of about element other than an increased binding energy hydrogen species . Thus, the other element can be an ordinary hydro 13.6ev gen species , or any element other than hydrogen . In one group of compounds, the other element and the increased ) binding energy hydrogen species are neutral . In another group of compounds, the other element and increased bind ing energy hydrogen species are charged such that the other where p is an integer , preferably an integer from 2 to 137. A element provides the balancing charge to form a neutral further product of the catalysis is energy. The increased compound. The former group of compounds is characterized binding energy hydrogen atom can be reacted with an by molecular and coordinate bonding ; the latter group is electron source, to produce an increased binding energy characterized by ionic bonding . US 2019/0389723 A1 Dec. 26 , 2019 8

[0031 ] Also provided are novel compounds and molecular [0044 ] (i ) greater than the total energy of ordinary ions comprising molecular hydrogen , or [ 0032] ( a ) at least one neutral, positive , or negative hydro [0045 ] ( ii ) greater than the total energy of any hydrogen gen species (hereinafter “ increased binding energy hydrogen species for which the corresponding ordinary hydrogen species” ) having a total energy species is unstable or is not observed because the [0033 ] ( i ) greater than the total energy of the corre ordinary hydrogen species ’ total energy is less than sponding ordinary hydrogen species, or thermal energies at ambient conditions or is negative ; [0034 ] (ii ) greater than the total energy of any hydrogen species for which the corresponding ordinary hydrogen and species is unstable or is not observed because the ( 0046 ] ( b ) optionally one other element. The compounds ordinary hydrogen species ' total energy is less than of the invention are hereinafter referred to as “ increased thermal energies at ambient conditions , or is negative; binding energy hydrogen compounds” . and [ 0035 ] (b ) at least one other element. [0047 ] In an embodiment, a compound is provided , com The total energy of the hydrogen species is the sum of the prising at least one increased binding energy hydrogen energies to remove all of the electrons from the hydrogen species selected from the group consisting of (a ) hydride ion species. The hydrogen species according to the present having a binding energy according to Eqs . ( 15-16 ) that is invention has a total energy greater than the total energy of greater than the binding of ordinary hydride ion ( about 0.8 the corresponding ordinary hydrogen species . The hydrogen eV ) for p = 2 up to 23, and less for p = 24 (“ increased binding species having an increased total energy according to the energy hydride ion ” or “ hydrino hydride ion " ); (b ) hydrogen present invention is also referred to as an “ increased binding atom having a binding energy greater than the binding energy hydrogen species ” even though some embodiments energy of ordinary hydrogen atom (about 13.6 eV ) ( “ in of the hydrogen species having an increased total energy creased binding energy hydrogen atom ” or “ hydrino ” ) ; (c ) may have a first electron binding energy less that the first hydrogen molecule having a first binding energy greater electron binding energy of the corresponding ordinary than about 15.3 eV ( “ increased binding energy hydrogen hydrogen species . For example , the hydride ion of Eqs. molecule ” or “ dihydrino ” ) ; and ( d ) molecular hydrogen ion ( 15-16 ) for p = 24 has a first binding energy that is less than having a binding energy greater than about 16.3 eV the first binding energy of ordinary hydride ion , while the “ increased binding energy molecular hydrogen ion ” or total energy of the hydride ion of Eqs . (15-16 ) for p = 24 is much greater than the total energy of the corresponding " dihydrino molecular ion ” ) . ordinary hydride ion . [0036 ] Also provided are novel compounds and molecular Characteristics and Identification of Increased Binding ions comprising Energy Species [0037 ] ( a ) a plurality of neutral, positive, or negative [ 0048] A new chemically generated or assisted plasma hydrogen species (hereinafter “ increased binding energy source based on a resonant energy transfer mechanism hydrogen species " ) having a binding energy ( rt -plasma ) between atomic hydrogen and certain catalysts [0038 ] ( i ) greater than the binding energy of the corre sponding ordinary hydrogen species , or has been developed that may be a new power source . The [0039 ] (ii ) greater than the binding energy of any hydro products are more stable hydride and molecular hydrogen gen species for which the corresponding ordinary species such as H-( 1/4 ) and H ( 1/4 ). One such source hydrogen species is unstable or is not observed because operates by incandescently heating a hydrogen dissociator the ordinary hydrogen species ' binding energy is less and a catalyst to provide atomic hydrogen and gaseous than thermal energies at ambient conditions or is nega catalyst , respectively, such that the catalyst reacts with the tive ; and atomic hydrogen to produce a plasma. It was extraordinary [0040 ] ( b ) optionally one other element. The compounds that intense extreme ultraviolet (EUV ) emission was of the invention are hereinafter referred to as “ increased observed by Mills et al. [3-10 ] at low temperatures (e.g. binding energy hydrogen compounds” . -10 ° K ) and an extraordinary low field strength of about 1-2 [0041 ] The increased binding energy hydrogen species V /cm from atomic hydrogen and certain atomized elements can be formed by reacting one or more hydrino atoms with or certain gaseous ions which singly or multiply ionize at one or more of an electron , hydrino atom , a compound integer multiples of the potential energy of atomic hydrogen , containing at least one of said increased binding energy 27.2 eV . A number of independent experimental observa hydrogen species , and at least one other atom , molecule , or tions confirm that the rt -plasma is due to a novel reaction of ion other than an increased binding energy hydrogen spe atomic hydrogen which produces as chemical intermediates , cies. hydrogen in fractional quantum states that are at lower [0042 ] Also provided are novel compounds and molecular energies than the traditional “ ground ” (n = 1 ) state . Power is ions comprising released [ 3 , 9 , 11-13 ] , and the final reaction products are [ 0043] ( a ) a plurality of neutral, positive , or negative novel hydride compounds [ 3 , 14-16 ] or lower -energy hydrogen species ( hereinafter “ increased binding energy molecular hydrogen [ 17 ] . The supporting data include EUV hydrogen species” ) having a total energy spectroscopy [3-10 , 13 , 17-22 , 25, 27-28 ] , characteristic US 2019/0389723 A1 Dec. 26 , 2019 9

emission from catalysts and the hydride ion products [ 3 , 5 , accepts the nonradiative energy transfer from hydrogen 7 , 21-22, 27-28 ] , lower- energy hydrogen emission [ 12-13 , atoms and releases the energy to the surroundings to affect 18-20 ], chemically formed plasmas [ 3-10 , 21-22 , 27-28 ], electronic transitions to fractional quantum energy levels ). extraordinary ( > 100 eV ) Balmer a line broadening [3-5 , 7 , As a consequence of the nonradiative energy transfer, the 9-10 , 12 , 18-19 , 21, 23-28 ], population inversion of H lines hydrogen atom becomes unstable and emits further energy [ 3 , 21 , 27-29 ], elevated electron temperature [ 19 , 23-25 ] , until it achieves a lower -energy nonradiative state having a anomalous plasma afterglow duration [ 3 , 8 ], power genera principal energy level given by Eqs. ( 19) and (21 ) . Processes tion [ 3 , 9 , 11-13 ], and analysis of novel chemical com such as hydrogen molecular bond formation that occur pounds [ 3 , 14-16 ] . without photons and that require collisions are common [0049 ] The theory given previously [6 , 18-20, 30 ] is based [31 ] . Also , some commercial phosphors are based on reso on Maxwell's equations to solving the structure of the nant nonradiative energy transfer involving multipole cou electron . The familiar Rydberg equation (Eq . ( 19 ) ) arises for pling [ 32 ]. the hydrogen excited states for n > 1 of Eq . (20 ) . [0050 ] Two H ( 1 / p ) may react to form H ( 1 / p ) . The hydro gen molecular ion and molecular charge and current density functions, bond distances , and energies were exactly solved e ? 13.598eV ( 19 ) previously with remarkable accuracy [30 , 33 ] . Using the En = ?28?? , ?? Laplacian in ellipsoidal coordinates with the constraint of n = 1 , 2 , 3 , ... ( 20 ) nonradiation , the total energy of the hydrogen molecule having a central field of + pe at each focus of the prolate spheroid molecular orbital is

2e2 (22 ) 21 478,203 - = |( 207 - v7 + me 1 + p V mec2

-pº31.35 leV - p0.326469eV

An additional result is that atomic hydrogen may undergo a where p is an integer , ? is Planck's constant bar , me is the catalytic reaction with certain atoms, excimers , and ions mass of the electron , c is the speed of light in vacuum , u is the reduced nuclear mass , k is the harmonic force constant which provide a reaction with a net enthalpy of an integer solved previously in a closed - form equation with fundamen multiple of the potential energy of atomic hydrogen , m.27.2 tal constants only [ 30 , 33 ] and a , is the Bohr radius. The eV wherein m is an integer. The reaction involves a nonra vibrational and rotational energies of fractional -Rydberg diative energy transfer to form a hydrogen atom called a state molecular hydrogen H2( 1 / p ) are p? those of H2. Thus, hydrino atom that is lower in energy than unreacted atomic the vibrational energies , Evib , for the v = 0 to v = 1 transition hydrogen that corresponds to a fractional principal quantum of hydrogen -type molecules H2( 1 / p ) are [30 , 33 ] number. That is Evib = p20.515902 eV ( 23 ) where the experimental vibrational energy for the v = 0 to v = 1 transition of H2, E12 (v = 0 > V = 1 ), is given by Beutler [34 ] 1 1 (21 ) and Herzberg [35 ] . The rotational energies, Erot, for the J to N = is an integer J + 1 transition of hydrogen - type molecules H2( 1/ p ) are [30 , 2 ' 3'4 ' ? 33 ] t2 (24 ) replaces the well known parameter n = integer in the Rydberg Ero+ = E3 +1 – Es = () + + 1 ] = p *( 1 +1) 0.01509eV equation for hydrogen excited states. The n = 1 state of hydrogen and the where I is the moment of inertia , and the experimental rotational energy for the J = 0 to J = 1 transition of H , is given by Atkins [ 36 ]. The pa dependence of the rotational energies results from an inverse p dependence of the internuclear n = distance and the corresponding impact on I. The predicted integer internuclear distance 2c ' for H2( 1 / p ) is

states of hydrogen are nonradiative , but a transition between (25 ) two nonradiative states, say n = 1 to n = 1 / 2 , is possible via a 2c ' do va nonradiative energy transfer. Thus , a catalyst provides a net ? positive enthalpy of reaction ofm.27.2 eV ( i.e. it resonantly US 2019/0389723 A1 Dec. 26 , 2019 10

The rotational energies provide a very precise measure of I with an Evenson microwave cavity consistently yielded on and the internuclear distance using well established theory the order of 50 % more heat than non rt- plasma (controls ) [37 ] . such as He, Kr, Kr/ H2 ( 10 % ), under identical conditions of [0051 ] Ar + may serve as a catalyst since its ionization gas flow , pressure , and microwave operating conditions. The energy is about 27.2 eV . The catalyst reaction of Art to Ar2+ excess power density of rt -plasmas was of the order 10 forms H (1/2 ) which may further serve as both a catalyst and W.cm - . In addition to unique vacuum ultraviolet (VUV ) a reactant to form H ( 1/4 ) [ 19-20 , 30 ] . Thus, the observation lines , earlier studies with these same rt -plasmas demon of H ( 1/4 ) is predicted to be flow dependent since the strated that other unusual features were present including formation of H ( 1/4 ) requires the buildup of intermediates . The mechanism was tested by experiments with flowing dramatic broadening of the hydrogen Balmer series lines plasma gases. Neutral molecular emission was anticipated [ 3-5 , 7 , 9-10 , 12 , 18-19 , 21, 23-28 ] , and in the case ofwater for high pressure argon -hydrogen plasmas excited by a 12.5 plasmas, population inversion of the hydrogen excited states keV electron beam . Rotational lines for H2( 1/4 ) were antici [ 3 , 21, 27-29 ] . Both the current results and the earlier results pated and sought in the 150-250 nm region . The spectral are completely consistent with the existence of a hitherto lines were compared to those predicted by Eqs. ( 23-24 ) unknown predicted exothermic chemical reaction occurring corresponding to the internuclear distance of 1/4 that of H , in rt -plasmas . given by Eq . (25 ) . For p = 4 in Eqs. (23-24 ) , the predicted [ 0055 ] Since the ionization energy of Srt to Sr3 + has a net energies for the v = 1 > = 0 vibration -rotational series of enthalpy of reaction of 2 : 27.2 eV , Sr * may serve as catalyst H ( 1/4 ) are alone or with Art catalyst . It was reported previously that an rt -plasma formed with a low field (1V /cm ), at low tempera tures ( e.g. -10 ° K ), from atomic hydrogen generated at a Evib- rot = p EvibHz( v = O = v= 1) + p ? ( J + 1 )Erothy (26 ) tungsten filament and strontium which was vaporized by 8.254432V + ( 1 + 1 )0.24144eV , heating the metal [4-5 , 7 , 9-10 ] . Strong VUV emission was J = 0 , 1 , 2 , 3 ... observed that increased with the addition of argon , but not when sodium , magnesium , or barium replaced strontium or with hydrogen , argon , or strontium alone . Characteristic [0052 ] Het also fulfills the catalyst criterion a chemical emission was observed from a continuum state of Ar2 + at or physical process with an enthalpy change equal to an 45.6 nm without the typical Rydberg series of Ar I and Ar II integer multiple of 27.2 eV since it ionizes at 54.417 eV lines which confirmed the resonant nonradiative energy which is 2 : 27.2 eV. The product of the catalysis reaction of transfer of 27.2 eV from atomic hydrogen to Ar + [5 , 7, 22 ]. He , H ( 1/3) , may further serve as a catalyst to form H ( 1/4 ) Predicted Sr3 + emission lines were also observed from and H ( 1/2 ) [19-20 , 30 ) which can lead to transitions to other strontium - hydrogen plasmas ( 5 , 7 ] that supported the rt states H ( 1 / p ) . Novel emission lines with energies of q.13.6 plasma mechanism . Time- dependent line broadening of the eV where q = 1.2, 3 , 4 , 6 , 7 , 8 , 9 , or 11 were previously H Balmer a line was observed corresponding to extraordi observed by extreme ultraviolet ( EUV ) spectroscopy narily fast H (25 eV ). An excess power of 20 mW.cm - 3 was recorded on microwave discharges of helium with 2 % measured calorimetrically on rt -plasmas formed when Art hydrogen [18-20 ]. These lines matched H (1 /p ), fractional was added to Srt as an additional catalyst . Rydberg states of atomic hydrogen given by Eqs . ( 19 ) and (21 ) . [0056 ] Significant Balmer a line broadening correspond [0053 ] Rotational lines were observed in the 145-300 nm ing to an average hydrogen atom temperature of 14 , 24 eV , region from atmospheric pressure electron -beam excited and 23-45 eV was observed for strontium and argon - stron argon -hydrogen plasmas. The unprecedented energy spacing tium rt - plasmas and discharges of strontium -hydrogen , of 42 times that of hydrogen established the internuclear helium -hydrogen , argon - hydrogen , strontium -helium -hy distance as 1/4 that of H , and identified H2( 1/4 ) (Eqs . drogen , and strontium - argon -hydrogen , respectively , com ( 23-26 ) ). H2 ( 1 / p ) gas was isolated by liquefaction ofhelium pared to -3 eV for pure hydrogen , xenon - hydrogen , and hydrogen plasma gas using an high - vacuum ( 10-6 Torr ) magnesium -hydrogen . To achieve that same optically mea capable, liquid nitrogen cryotrap and was characterized by sured light output power , hydrogen -sodium , hydrogen -mag mass spectroscopy (MS ). The condensable gas had a higher nesium , and hydrogen -barium mixtures required 4000 , ionization energy than H , by MS [ 17 ] . H2( 1/4 ) gas from 7000 , and 6500 times the power of the hydrogen - strontium chemical decomposition of hydrides containing the corre mixture , respectively , and the addition of argon increased sponding hydride ion H- ( 1/4 ) as well from liquefaction of these ratios by a factor of about two . A glow discharge the catalysis -plasma gas was also identified by ' H NMR as plasma formed for hydrogen - strontium mixtures at an an upfield - shifted singlet peak at 2.18 ppm relative to H , at extremely low voltage of about 2 V compared to 250 V for 4.63 that matched theoretical predictions [ 13 , 17 ] . H2 ( 1/4 ) hydrogen alone and sodium -hydrogen mixtures, and 140 was further characterized by studies on the vibration - rota 150 V for hydrogen -magnesium and hydrogen -barium mix tional emission from electron -beam maintained argon -hy tures [ 4-5 , 7 ] . These voltages are too low to be explicable by drogen plasmas and from Fourier - transform infrared (FTIR ) conventional mechanisms involving accelerated ions with a spectroscopy of solid samples containing H-( 1/4 ) with inter high applied field . A low - voltage EUV and visible light stitial H_( 1/4 ). source is feasible [ 10 ] . [0054 ] Water bath calorimetry was used to determine that [0057 ] In general , the energy transfer of m : 27.2 eV from measurable power was developed in rt- plasmas due to the the hydrogen atom to the catalyst causes the central - field reaction to form states given by Eqs. (19 ) and (21 ) . Spe interaction of the H atom to increase by m and its electron cifically , He/ H , ( 10 % ) (500 m Torr) , Ar/ H , ( 10 % ) (500 to drop m levels lower from the radius of the hydrogen atom , mTorr ) , and H2O ( g ) (500 and 200 m Torr ) plasmas generated an, to a radius of US 2019/0389723 A1 Dec. 26 , 2019 11

?? do 1 + m [ 19 – 20 ] . i = ( 1 + Vs( s + 1 ) ) ; s = 2 Since K to K3+ provides a reaction with a net enthalpy equal to three times the potential energy of atomic hydrogen , From Eq . (27 ) , the calculated ionization energy of the 3.27.2 eV , it may serve as a catalyst such that each ordinary hydride ion is 0.75418 eV, and the experimental value given hydrogen atom undergoing catalysis releases a net of 204 eV by Lykke [ 38 ] is 6082.99-0.15 cm-- (0.75418 eV ) . [ 3 ] . K may then react with the product H ( 1/4 ) to form a yet [0059 ] Substantial evidence of an energetic catalytic reac lower- state H ( 1/7 ) or further catalytic transitionsmay occur : tion was previously reported [ 3 ] involving a resonant energy transfer between hydrogen atoms and K to form very stable novel hydride ions H- ( 1 / p ) called hydrino hydrides having 1 1 a predicted fractional principal quantum number p = 4 . Char 4 5 ° 5 65 ? acteristic emission was observed from K3+ that confirmed the resonant nonradiative energy transfer of 3.27.2 eV from and so , involving only hydrinos in a process called dispro atomic hydrogen to K. From Eq . (27 ) , the binding energy Eb portionation . Since the ionization energies and metastable of H-( 1/4 ) is resonant states of hydrinos due corresponding to the multi Eb = 11.232 eV (avac = 1103.88 ) ( 28 ) pole expansion of the potential energy are m -27.2 eV (Eds . ( 19 ) and ( 21) ) as given previously [ 19-20 , 30 ] once catalysis The product hydride ion H-( 1/4 ) was observed spectroscopi begins, hydrinos autocatalyze further transitions to lower cally at 110 nm corresponding to its predicted binding states. This mechanism is similar to that of an inorganic ion energy of 11.2 eV [ 3 , 21 ]. catalysis . An energy transfer of m.27.2 eV from a first [0060 ] Upfield - shifted NMR peaks are direct evidence of hydrino atom to the second hydrino atom causes the central the existence of lower -energy state hydrogen with a reduced field of the first atom to increase by m and its electron to radius relative to ordinary hydride ion and having an drop M levels lower from a radius of increase in diamagnetic shielding of the proton . The total theoretical shift

?? ? ABT B to a radius of for H- ( 1 / p ) is given by the sum of the shift of H ( 1/1 ) plus the contribution due to the lower - electronic energy state : ?? pum e (29 ) ABT = -Mo ( 1 + a2p) [0058 ] The catalyst product, H ( 1 / p ) , may also react with B 12m2a ( 1 + Vs( s + 1 ) ) an electron to form a novel hydride ion H- ( 1 / p ) with a = - (29.9 + 1.37p ) ppm binding energy EB [3 , 14 , 16 , 21, 30 ]: where p = integer > 1 . Corresponding alkali hydrides and ti? Vs( s + 1) Aloe ? ? / 1 22 (27 ) alkali hydrino hydrides (containing H- ( 1 / p )) were charac EB + 1+ s ( s + 1 ) m ? 1 + Vs( s + 1 ) terized by ' H MAS NMR and compared to the theoretical 8??? a values . A match of the predicted and observed peaks with no 27 ? alternative represents a definite test. [0061 ] The ' H MAS NMR spectrum of novel compound where p is an integer greater than one , s = 1 / 2 , ? is Planck's KH * Cl relative to external tetramethylsilane ( TMS ) showed constant bar, u , is the permeability of vacuum , m , is the a large distinct upfield resonance at -4.4 ppm corresponding mass of the electron , He is the reduced electron mass given to an absolute resonance shift of -35.9 ppm that matched the by theoretical prediction of p = 4 [ 3 , 14-16 ] . This result con firmed the previous observations from the rt - plasmas of intense hydrogen Lyman emission , a stationary inverted memp Lyman population , excessive afterglow duration , highly Me = me + mp energetic hydrogen atoms, characteristic alkali - ion emission 3 due to catalysis , predicted novel spectral lines, and the measurement of a power beyond any conventional chemistry [ 3 ] that matched predictions for a catalytic reaction of atomic hydrogen to form more stable hydride ions desig where mp is the mass of the proton , ay is the radius of the nated H-( 1 / p ). Since the comparison of theory and experi hydrogen atom , a , is the Bohr radius , and e is the elementary mental shifts of KH * C1 is direct evidence of lower -energy charge . The ionic radius is hydrogen with an implicit large exotherm during its forma US 2019/0389723 A1 Dec. 26 , 2019 12

tion , the NMR results were repeated with the further analysis BRIEF DESCRIPTION OF THE DRAWINGS by infrared (FTIR ) spectroscopy to eliminate any known explanation [ 39 ] . [0065 ] FIG . 1A is a schematic drawing of an energy [0062 ] Elemental analysis identified [ 14 , 16 ] these com reactor and power plant in accordance with the present pounds as only containing the alkaline metal, halogen , and invention . hydrogen , and no known hydride compound of this compo [0066 ] FIG . 1B is a schematic drawing of an energy sition could be found in the literature which has an upfield reactor and power plant for recycling or regenerating the shifted hydride NMR peak . Ordinary alkali hydrides alone fuel in accordance with the present invention . or mixed with alkali halides show down - field shifted peaks [0067 ] FIG . 1C is a schematic drawing of a power reactor [ 3 , 14-16 ] . From the literature , the list of alternatives to in accordance with the present invention . H-( 1 / p ) as a possible source of the upfield NMR peaks was [0068 ] FIG . 1D is a schematic drawing of a discharge limited to U centered H. The intense and characteristic power and plasma cell and reactor in accordance with the infrared vibration band at 503 cm - t due to the substitution present invention . ofH- for Cl- in KCl enabled the elimination of U centered [0069 ] FIG . 2A is the experimental set up comprising a H as the source of the upfield - shifted NMR peaks [ 39 ] . filament gas cell to form lithium - argon - hydrogen and [0063 ] As further characterizations, the X - ray photoelec lithium -hydrogen rt -plasmas . tron spectrum (XPS ) of the hydrino hydride KH * I was [0070 ] FIG . 2B is a schematic of the reaction cell and the performed to determine if the predicted H-( 1/4 ) binding cross sectional view of the water flow calorimeter used to energy given by Eq. ( 28 ) was observed , and FTIR analysis measure the energy balance of the NaH catalyst reaction to of these crystals with H (1/4 ) was performed before and form hydrinos . The components were : 1 — inlet and outlet after storage in argon for 90 days to search for interstitial thermistors ; 2_high - temperature valve ; 3 ceramic fiber H2 ( 1/4 ) having a predicted rotational energy given by Eq . heater; 4 copper water - coolant coil; 5 - reactor; 6 — insu ( 24 ) . The identification of single rotational peaks at this lation ; 7 - cell thermocouple , and 8 water flow chamber. energy with ortho -para splitting due to free rotation of a very [0071 ] FIG . 3 is a schematic of the water flow calorimeter small hydrogen molecule would represent definite proof of used to measure the energy balance of the NaH catalyst its existence since there is no other possible assignment [39 ] . reaction to form hydrinos . [ 0064 ] Since the rotational emission of H2( 1/4 ) was observed in crystals of KH * I having a peak assigned to [0072 ] FIG . 4 is a schematic of the stainless steel gas cell H ( 1/4 ) and the vibration - rotational emission ofH2 ( 1/4 ) was to synthesize LiH * Br, LiH * I , NaH * Cl and NaH * Br com observed from 12.5 keV -electron - beam -maintained plasmas prising the reaction mixture (i ) R -Ni , Li, LiNH2, and LiBr or of argon with 1 % hydrogen due to collisional excitation of Lil or ( ii ) Pt/ Ti dissociator, Na, NaH , and NaCl or NaBr as H ( 1/4 ), H2( 1/4 ) trapped in the lattice of KH * Cl, or H2( 1/4 ) the reactants . The components were : 101 — stainless steel formed from H- ( 1/4 ) or formed insitu from K catalysis of H cell; 117 — internal cavity of cell; 118_high vacuum conflat via electron bombardment was investigated by windowless flange ; 119 —mating blank conflat flange ; 102 — stainless EUV spectroscopy on electron -beam excitation of the crys steel tube vacuum line and gas supply line ; 103. -lid to the tals using the 12.5 keV electron gun at pressures below kiln or top insulation , 104 surrounding heaters coverer by which any gas could produce detectable emission (< 10-5 high temperature insulation ; 108 Pt / Ti dissociator; 109 Torr ) [39 ] . The rotational energy of H2( 1/4 ) was confirmed reactants ; 110 high vacuum turbo pump; 112 pressure by this technique as well. Consistent results from the broad gauge; 111 vacuum pump valve ; 113 — valve ; 114 — valve ; spectrum of investigational techniques provide definitive 115_regulator, and 116 hydrogen tank . evidence that hydrogen can exist in lower -energy states then [0073 ] FIG . 5 shows the 656.3 nm Balmer a line width previously thought possible in the form of H- ( 1/4 ) and recorded with a high -resolution visible spectrometer on ( A ) H2 ( 1/4 ) . In an embodiment , the products of the Li catalyst the initial emission of a lithium - argon -hydrogen rt -plasma reaction and NaH catalyst reaction are both H-( 1/4 ) and and ( B ) the emission at 70 hours of operation . Lithium lines H ( 1/4 ) and additionally H = ( 1/3 ) and H , ( 1/3 ) for NaH . The and significant broadening of only the H lines was observed present invention provides for their identification and the over time corresponding to an average hydrogen atom corresponding energetic exothermic reaction by EUV spec temperature of > 40 eV and fractional population over 90 % . troscopy , characteristic emission from catalysts and the [0074 ] FIG . 6 shows the 656.3 nm Balmer a line width hydride ion products , lower- energy hydrogen emission , recorded with a high -resolution ( +0.006 nm ) visible spec chemically formed plasmas, extraordinary Balmer a line trometer on the initial emission of a lithium -hydrogen broadening , population inversion of H lines , elevated elec rt -plasma and ( B ) the emission at 70 hours of operation . tron temperature , anomalous plasma afterglow duration , Lithium lines and broadening of only the H lines was power generation , and analysis of novel chemical com observed over time, but diminished relative to the case pounds. Preferred identification techniques for the species having the argon -hydrogen gas (95 / 5 % ) . The Balmer width H-( 1 / p ) and H2( 1p ) are NMR of H-( 1 / p ) and H ( 1/ p ) , FTIR corresponded to an average hydrogen atom temperature of 6 of H ( 1/ p ) trapped in a crystal, XPS of H-( 1 /p ) , ToF -SIMs eV and a 27 % fractional population . of H- ( 1 / p ) , electron -beam excitation emission spectroscopy [0075 ] FIG . 7 shows the results of the DSC ( 100-750 ° C.) of H2 ( 1 /p ) , electron beam emission spectroscopy of H ( 1 /p ) of NaH at a scan rate of 0.1 degree/ minute . A broad trapped in a crystalline lattice , and TOF - SIMS identification endothermic peak was observed at 350 ° C. to 420 ° C. which of novel compounds comprising H- (1 / p ) . Preferred charac corresponds to 47 kJ/ mole and matches sodium hydride terization techniques for the energetic catalysis reaction and decomposition in this temperature range with a correspond the power balance are line broadening, plasma formation , ing enthalpy of 57 kJ/ mole . A large exotherm was observed and calorimetry . Preferably , H-( 1 / p ) and H , ( 1 / p ) are H- ( 1 / under conditions that form NaH catalyst in the region 640 ° 4 ) and H2 ( 1/4 ), respectively . C. to 825 ° C. which corresponds to at least –354 kJ/mole H2, US 2019/0389723 A1 Dec. 26 , 2019 13

greater than that of the most exothermic reaction possible for in 60 s wherein the reaction liberated 11.7 kJ of energy in H , the –241.8 kJ/ mole H , enthalpy of combustion of hydro less time to develop a system - response - corrected peak gen . power in excess of 0.25 kW . [ 0076 ] FIG . 8 shows the results of the DSC (100-750 ° C.) [0086 ] FIG . 18 shows the coolant power with time for the of MgH , at a scan rate of 0.1 degree /minute . Two sharp hydrino reaction with the cell containing the reagents com endothermic peaks were observed . A first peak centered at prising the catalyst material , 15 g NaOH -doped R -Ni 2400 . 351.75 ° C. corresponding to 68.61 kJ/mole MgH , matches The numerical integration of the input and output power the 74.4 kJ mole MgH , decomposition energy. The second curves with the calibration correction applied yielded an peak at 647.66 ° C. corresponding to 6.65 kJ/mole MgH2 output energy of 195.7 kJ and an input energy of 184.0 kJ matches the known melting point of Mg( m ) is 650 ° C. and corresponding to an excess energy of 11.7 kJ. enthalpy of fusion of 8.48 kJ/mole Mg( m ). Thus, the [ 0087 ] FIG . 19 shows the positive ToF -SIMS spectrum expected behavior was observed for the decomposition of a ( m /e = 0-100 ) of LiBr. control, noncatalyst hydride . [0088 ] FIG . 20 shows the positive ToF - SIMS spectrum [0077 ] FIG . 9 shows the temperature versus time for the ( m / e = 0-10 of the LiH *Br crystals . calibration run with an evacuated test cell and resistive [0089 ] FIG . 21 shows the negative ToF -SIMS spectrum heating only (m /e =0-100 ) of LiBr. [ 0078 ] FIG . 10 shows the power versus time for the [ 0090) FIG . 22 shows the negative ToF - SIMS spectrum calibration run with an evacuated test cell and resistive ( m / e = 0-100 ) of the LiH * Br crystals . A dominant hydride , heating only . The numerical integration of the input and LiHBr , and Li ,H_Br peaks were uniquely observed . output power curves yielded an output energy of 292.2 kJ [ 0091 ] FIG . 23 shows the positive ToF -SIMS spectrum and an input energy of 303.1 kJ corresponding to a coupling ( m / e = 0-200 ) of Lil . of flow of 96.4 % of the resistive input to the output coolant. [ 0092 ] FIG . 24 shows the positive ToF - SIMS spectrum [ 0079 ] FIG . 11 shows the cell temperature with time for ( m / e = 0-200 ) of the LiH * I crystals . LiHI* , Li, H , I * , Li H , I , the hydrino reaction with the cell containing the reagents and LicH_I * were only observed in the positive ion spectrum comprising the catalyst material, 1 g Li, 0.5 g LINH2, 10 g of the LiH * I crystals . LiBr, and 15 g Pd / A1203. The reaction liberated 19.1 kJ of [ 0093] FIG . 25 shows the negative ToF - SIMS spectrum energy in less than 120 s to develop a system - response ( m / e = 0-180 ) of Lil . corrected peak power in excess of 160 W. [0094 ] FIG . 26 shows the negative ToF -SIMS spectrum [0080 ] FIG . 12 shows the coolant power with time for the ( m /e = 0-180 ) of the LiH * I crystals . A dominant hydride , hydrino reaction with the cell containing the reagents com LiHI , Li H21C , and NaHi“ peaks were uniquely observed . prising the catalyst material, 1 g Li, 0.5 g LINH , 10 g LiBr, [0095 ] FIG . 27 shows the negative ToF - SIMS spectrum and 15 g Pd / A1203. The numerical integration of the input ( m / e = 20-30 ) of NaH * -coated Pt/ Ti following the production and output power curves with the calibration correction of 15 kJ of excess heat. Hydrino hydride compounds NaH ; applied yielded an output energy of 227.2 kJ and an input were observed . energy of 208.1 kJ corresponding to an excess energy of [0096 ] FIG . 28 shows the positive ToF -SIMS spectrum 19.1 kJ. ( m / e = 0-100 ) of R - Ni reacted over a 48 hour period at 50 ° C. [0081 ] FIG . 13 shows the cell temperature with time for The dominant ion on the surface was Nat consistent with the R -Ni control power test with the cell containing the NaOH doping of the surface . The ions of the other major reagents comprising the starting material for R - Ni, 15 g elements of R -Ni 2400 such as Al* , Ni+ , Crt, and Fet were R -Ni / Al alloy powder , and 3.28 g of Na. also observed . [0082 ] FIG . 14 shows the coolant power with time for the [ 0097 ] FIG . 29 shows the negative ToF -SIMS spectrum control power test with the cell containing the reagents ( m / e = 0-180 ) of R -Ni reacted over a 48 hour period at 50 ° C. comprising the starting material for R -Ni , 15 g R - Ni / Al alloy A dominant hydride , NaHy and NaH , NaOH assigned to powder and 3.28 g of Na. Energy balance was obtained with sodium hydrino hydride and this ion in combination with the calibration -corrected numerical integration of the input NaOH , as well as other unique ions assignable to sodium and output power curves yielding an output energy of 384 kJ hydrino hydrides NaHx— ; in combinations with NaOH , and an input energy of 385 kJ. NaO , OH— and Owere observed . [ 0083 ] FIG . 15 shows the cell temperature with time for [0098 ] FIG . 30 show ' H MAS NMR spectra relative to the hydrino reaction with the cell containing the reagents external TMS . ( A ) LiH * Br showing a broad -2.5 ppm comprising the catalyst material, 15 g NaOH - doped R - Ni upfield -shifted peak and a peak at 1.13 ppm assigned to 2800 , and 3.28 g of Na. The reaction liberated 36 kJ of H-( 1/4 ) and H ( 1/4 ) , respectively . ( B ) LiH * I showing a energy in less than 90 s to develop a system - response broad -2.09 ppm upfield - shifted peak assigned to H- ( 1/4 ) corrected peak power in excess of 0.5 kW . and peaks at 1.06 ppm and 4.38 ppm assigned to H2( 1/4 ) and [0084 ] FIG . 16 shows the coolant power with time for the H2, respectively . hydrino reaction with the cell containing the reagents com [ 0099 ] FIG . 31 shows ' H MAS NMR spectra relative to prising the catalyst material, 15 g NaOH -doped R -Ni 2800 , external TMS. ( A ) KH * Cl showing a very sharp -4.46 ppm and 3.28 g of Na. The numerical integration of the input and upfield - shifted peak corresponding to an environment that is output power curves with the calibration correction applied essentially that of a free ion . ( B ) KH * I showing a broad yielded an output energy of 185.1 kJ and an input energy of -2.31 ppm upfield - shifted peak similar to the case of 149.1 kJ corresponding to an excess energy of 36 kJ. LiH * Br and LiH * I. Both spectra also had a 1.13 ppm peak [0085 ] FIG . 17 shows the cell temperature with time for assigned to H2( 1/4 ) . the hydrino reaction with the cell containing the reagents [0100 ] FIG . 32 shows ' H MAS NMR spectra relative to comprising the catalyst material, 15 g NaOH -doped R -Ni external TMS showing an H - content selectivity of LiH * X 2400. The cell temperature jumped from 60 ° C. to 205 ° C. formolecular species alone based on the nonpolarizability of US 2019/0389723 A1 Dec. 26 , 2019 14

the halide and the corresponding nonreactivity towards H [0110 ] FIG . 42 shows high resolution XPS spectra ( E6 = 0 ( 1/4 ). ( A ) LiH * F comprising a nonpolarizable fluorine eV to 50 eV ) for ( A ) Pt/ Ti and ( B ) NaH * -coated Pt / Ti showing peaks at 4.31 ppm assigned to H2 and 1.16 ppm following the production of 15 kJ of excess heat. The XPS assigned to H2( 1/4 ) and the absence of the H- ( 1/4 ) ion peak . spectrum ofNaH * -coated Pt/ Ti differs from that of Pt/ Ti by ( B ) LiH * Cl comprising a nonpolarizable chlorine showing having additional peaks at 6 eV , 10.8 eV , and 12.8 eV that peaks at 4.28 ppm assigned to H2 and 1.2 ppm assigned to could not be assigned to known elements and do not H2( 1/4 ) and the absence of the H- ( 1/4 ) ion peak correspond to any other primary element peak . The 10.8 eV, [0101 ] FIG . 33 shows the ' H MAS NMR spectra of NaH and 12.8 eV peaks match H (1/4 ) in two different chemical Br relative to external TMS showing a -3.58 ppm upfield environments , and the 6 eV peak matched and was assigned shifted peak , a peak at 1.13 ppm , and a peak at 4.3 ppm to H-( 1/3 ). Thus, both fractional hydrogen states , 1/3 and assigned to H- ( 1/4 ) , H ( 1/4 ) , and H2, respectively . 1/4 , were present as predicted by Eq . (27 ) . [0102 ] FIG . 34 shows the NaH * C1 ' H MAS NMR spectra [0111 ] FIG . 43 shows XPS survey spectrum ( E , = 0 eV to relative to external TMS showing the effect of hydrogen 120 eV ) of NaH * -coated Si with the primary - element peaks addition on the relative intensities of H2, H ( 1/4 ) , and identified . H-( 1/4 ) . The addition of hydrogen increased the H-( 1/4 ) [0112 ] FIG . 44 shows high resolution XPS spectrum peak and decreased the H2( 1/4 ) while the H , increased . ( A ) ( E = 0 eV to 120 eV ) of NaH * -coated Si having peaks at 6 NaH * C1 synthesized with hydrogen addition showing a -4 eV , 10.8 eV , and 12.8 eV that could notbe assigned to known ppm upfield -shifted peak assigned to H-( 1/4 ) , a 1.1 ppm elements and do not correspond to any other primary ele peak assigned to H2( 1/4 ) , and a dominant 4 ppm peak ment peak . The 10.8 eV , and 12.8 eV peaks match H-( 1/4 ) assigned to H ( B ) * Cl synthesized without hydrogen addition in two different chemical environments , and the 6 eV peak showing a -4 ppm upfield -shifted peak assigned to H-( 1/4 ) , matched and was assigned to H-( 1/3 ) . Thus, both fractional a dominant 1.0 ppm peak assigned to H2( 1/4 ) , and a small hydrogen states, 1/3 and 1/4 , were present as predicted by 4.1 ppm assigned to Hz. Eq . (27 ) matching the results of NaH * -coated Pt/ shown in FIG . 42 marked B. [0103 ] FIG . 35 shows the ' H MAS NMR spectrum rela [0113 ] FIG . 45 shows high resolution (0.5 cm-' ) FTIR tive to external TMS of NaH * C1 from reaction of NaCl and spectra ( 490-4000 cm-? ) for ( A ) LiBr and ( B ) LiH * Br the solid acid KHSO4 as the only source of hydrogen sample having a NMR peak assigned to H-( 1/4 ) that was showing both the H- ( 1/4 ) peak at -3.97 ppm and an heated to >600 ° C. under dynamic vacuum that retained the upfield - shifted peak at -3.15 ppm assigned to H-( 1/3 ) . The -2.5 ppm NMR peak . The amide peaks at 3314 , 3259, 2079 corresponding H , ( 1/4 ) and H (113 ) peaks are shown at 1.15 ( broad ) , 1567, and 1541 cm - 1 and the imide peaks at 3172 ppm and 1.7 ppm , respectively . Both fractional hydrogen (broad ) , 1953 , and 1578 cm + were eliminated ; thus, they states were present and the H2 peak was absent at 4.3 ppm were not the source of the -2.5 ppm NMR peak that due to the synthesis of NaH * Cl using a solid acid as the H remained . The -2.5 ppm peak in NMR spectrum was source rather that addition of hydrogen gas and a dissociator. assigned to the H-( 1/4 ) ion . In addition , the 1989 cm- FTIR ( SB = side band ). peak could not be assigned to any know compound , but [0104 ] FIG . 36 shows XPS survey spectra (Eh = 0 e V to matched the predicted frequency of para H2 ( 1/4 ) . 1200 eV ) for ( A ) LiBr. and ( B ) LiH * Br. [ 0114 ] FIG . 46 shows the 150-350 nm spectrum of elec [0105 ] FIG . 37 shows the 0-85 eV binding energy region tron -beam excited CsCl crystals having trapped H2 (1/4 ). A of a high resolution XPS spectrum ofLiH * Br and the control series of evenly spaced lines was observed in the 220-300 LiBr (dashed ). The XPS spectrum of LiH * Br differs from nm region that matched the spacing and intensity profile of that of LiBr by having additional peaks at 9.5 eV and 12.3 the P branch of H ( 1/4 ). eV that could not be assigned to known elements and do not [0115 ] FIG . 47 shows the 100-550 nm spectrum of an correspond to any other primary element peak . The peaks electron -beam excited silicon wafer coated with NaH * C1 match H-( 1/4 ) in two different chemical environments . having trapped H2( 1/4 ). A series of evenly spaced lines was [0106 ] FIG . 38 shows the XPS survey spectra ( E = 0 eV to observed in the 220-300 nm region that matched the spacing 1200 eV ) for ( A ) NaBr and ( B ) NaH * Br. and intensity profile of the P branch of H2( 1/4 ) [0107 ] FIG . 39 shows the 0-40 eV binding energy region of a high resolution XPS spectrum of NaH * Br and the DETAILED DESCRIPTION OF THE control NaBr (dashed ) . The XPS spectrum of NaH * Br PREFERRED EMBODIMENTS differs from that of NaBr by having additional peaks at 9.5 eV and 12.3 eV that could not be assigned to known Hydrogen Catalyst Reactor elements and do not correspond to any other primary ele [0116 ] A hydrogen catalyst reactor 50 for producing ment peak . The peaks match H ( 1/4 ) in two different chemi energy and lower- energy hydrogen species, in accordance cal environments . with the invention , is shown in FIG . 1A and comprises a [0108 ] FIG . 40 shows XPS survey spectra ( E , = 0 eV to vessel 52 which contains an energy reaction mixture 54, a 1200 eV ) for ( A ) PtITi and ( B ) NaH * -coated Pt/ Ti following heat exchanger 60 , and a power converter such as a steam the production of 15 kJ of excess heat. generator 62 and turbine 70. In an embodiment, the catalysis [0109 ] FIG . 41 shows high resolution XPS spectra ( Es = 0 involves reacting atomic hydrogen from the source 56 with eV to 100 eV ) for ( A ) PtI Ti and ( B ) NaH * -coated PtITI the catalyst 58 to form lower - energy hydrogen “ hydrinos” following the production of 15 kJ of excess heat. The Pt and produce power . The heat exchanger 60 absorbs heat 4f7/ 2, Pt 4f3/ 2, and 0 2s peaks were observed at 70.7 eV , 74 released by the catalysis reaction , when the reaction mixture , eV , and 23 eV , respectively. The Na 2p and Na 2s peaks were comprised of hydrogen and a catalyst, reacts to form lower observed at 31 eV and 64 eV on NaH * -coated Pt/ Ti, and a energy hydrogen . The heat exchanger exchanges heat with valance band was only observed for Pt/ Ti. the steam generator 62 which absorbs heat from the US 2019/0389723 A1 Dec. 26 , 2019 15

exchanger 60 and produces steam . The energy reactor 50 plus or minus 1 eV . The catalysts include those given herein further comprises a turbine 70 which receives steam from and the atoms, ions, molecules , and hydrinos described in the steam generator 62 and supplies mechanical power to a Mills Prior Publications ( e.g. TABLE 4 of PCT /US90 /01998 power generator 80 which converts the steam energy into and pages 25-46 , 80-108 of PCT/ US94 /02219 ) which are electrical energy, which can be received by a load 90 to incorporated herein by reference. In embodiments , the cata produce work or for dissipation . lyst may comprise at least one species selected from the [0117 ] In an embodiment, the energy reaction mixture 54 group of molecules of AIH , BiH , CIH , COH , GH , InH , comprises an energy releasing material 56 such as a solid NaH , RuH , SbH , SeH , SiH , SnH , C2, N2,02, CO2 , NO2, and fuel supplied through supply passage 42. The reaction NO3 and atoms or ions of Li, Be, K , Ca , Ti , V , Cr, Mn, Fe , mixture may comprise a source of hydrogen isotope atoms Co , Ni, Cu , Zn , As , Se , Kr, Rb , Sr, Nb , Mo, Pd , Sn , Te , Cs , or a source of molecular hydrogen isotope , and a source of Ce , Pr, Sm , Gd, Dy, Pb , Pt, Kr, 2K + , He+ , Na + , Rb + , Sr+ , catalyst 58 which resonantly remove approximately m.27.2 Fe3 + , Mo2+ , Mo7 + , In3 + , He + , Ar * , Xe + , Ar2 + and H ™ , and eV to form lower - energy atomic hydrogen where m is an Net and H + . integer, preferably an integer less than 400 wherein the reaction to lower energy states of hydrogen occurs by Hydrogen Catalyst Reactor and Electrical Power System contact of the hydrogen with the catalyst . The catalyst may be in the molten , liquid , gaseous , or solid state . The catalysis [0121 ] In an embodiment of a power system , the heat is releases energy in a form such as heat and forms at least one removed by a heat exchanger having a heat exchange of lower- energy hydrogen isotope atoms, molecules, hydride medium . The heat exchanger may be a water wall and the ions, and lower -energy hydrogen compounds. Thus, the medium may be water. The heat may be transferred directly power cell also comprises a lower -energy hydrogen chemi for space and process heating. Alternatively , the heat cal reactor. exchanger medium such as water undergoes a phase change [0118 ] The source of hydrogen can be hydrogen gas, such as conversion to steam . This conversion may occur in dissociation of water including thermal dissociation , elec a steam generator. The steam may be used to generate trolysis of water , hydrogen from hydrides , or hydrogen from electricity in a heat engine such as a steam turbine and a metal- hydrogen solutions. In another embodiment, molecu generator. lar hydrogen of the energy releasing material 56 is dissoci [0122 ] An embodiment of a hydrogen catalyst energy and ated into atomic hydrogen by a molecular hydrogen disso lower- energy -hydrogen species -producing reactor 5 , for ciating catalyst of the mixture 54. Such dissociating recycling or regenerating the fuel in accordance with the catalysts may also absorb hydrogen , deuterium , or tritium Invention , is shown in FIG . 1B and comprises a boiler 10 atoms and / or molecules and include, for example , an ele which contains a solid fuel reaction mixture 11 , hydrogen ment, compound , alloy, or mixture of noble metals such as source 12, steam pipes and steam generator 13 , a power palladium and platinum , refractory metals such as molyb converter such as a turbine 14 , a water condenser 16 , a denum and tungsten , transition metals such as nickel and water -make -up source 17 , a solid - fuel recycler 18 , and a titanium , inner transition metals such as niobium and zirco hydrogen -dihydrino gas separator 19. At Step 1 , the solid nium , and other such materials listed in the Prior Mills fuel comprising a source of catalyst and a source of hydro Publications. Preferably , the dissociator has a high surface gen reacts to form hydrinos and lower- energy hydrogen area such as a noble metal such as Pt, Pd , Ru , Ir, Re , or Rh , products . At Step 2 , the spent fuel is reprocessed to re - supply or Ni on Al2O3, SiO2, or combinations thereof . the boiler 10 to maintain thermal power generation . The heat [0119 ] In an embodiment, a catalyst is provided by the generated in the boiler 10 forms steam in the pipes and steam ionization of t electrons from an atom or ion to a continuum generator 13 that is delivered to the turbir 14 that in turn energy level such that the sum of the ionization energies of generates electricity by powering a generator. At Step 3 , the the telectrons is approximately m.27.2 eV where t and in are water is condensed by the water condenser 16. Any water each an integer . A catalyst may also be provided by the loss may be made up by the water source 17 to complete the transfer of t electrons between participating ions. The trans cycle to maintain thermal to electric power conversion . At fer of t electrons from one ion to another ion provides a net Step 4 , lower - energy hydrogen products such as hydrino enthalpy of reaction whereby the sum of the t ionization hydride compounds and dihydrino gas may be removed , and energies of the electron -donating ion minus the ionization unreacted hydrogen may be returned to the fuel recycler 18 energies of t electrons of the electron - accepting ion equals or hydrogen source 12 to be added back to spent fuel to approximately m.27.2 eV where r and m are each an integer . make -up recycled fuel . The gas products and unreacted In another preferred embodiment, the catalyst comprises hydrogen may be separated by hydrogen -dihydrino gas MH such as NaH having an atom M bound to hydrogen , and separator 19. Any product hydrino hydride compounds may the enthalpy of m.27.2 eV is provided by the sum of the be separated and removed using solid - fuel recycler 18. The M - H bond energy and the ionization energies of the t processing may be performed in the boiler or externally to electrons . the boiler with the solid fuel returned . Thus, the system may [0120 ] In a preferred embodiment, a source of catalyst further comprise at least one of gas and mass transporters to comprises a catalytic material 58 supplied through catalyst move the reactants and products to achieve the spent fuel supply passage 41, that typically provides a net enthalpy of removal , regeneration , and re -supply . Hydrogen make -up approximately for that spent in the formation of hydrinos is added from the source 12 during fuel reprocessing and may involve recycled , unconsumed hydrogen . The recycled fuel main tains the production of thermal power to drive the power 2 27.2 eV plant to generate electricity . [0123 ] In a preferred embodiment, the reaction mixture comprises species that can generate the reactants of atomic US 2019/0389723 A1 Dec. 26 , 2019 16

or molecular catalyst and atomic hydrogen that further react present invention is shown in FIG . 1C . Reactant hydrinos to form hydrinos, and the product species formed by the are provided by a catalytic reaction with catalyst . Catalysis generation of catalyst and atomic hydrogen can be regener may occur in the gas phase or in solid or liquid state . ated by at least the step of reacting the products with [0127 ] The reactor of FIG . 1C comprises a reaction vessel hydrogen . In an embodiment, the reactor comprises a mov 207 having a chamber 200 capable of containing a vacuum ing bed reactor that may further comprise a fluidized - reactor or pressures greater than atmospheric . A source of hydrogen section wherein the reactants are continuously supplied and 221 communicating with chamber 200 delivers hydrogen to side products are removed and regenerated and returned to the chamber through hydrogen supply passage 242. A con the reactor. In an embodiment , the lower- energy hydrogen troller 222 is positioned to control the pressure and flow of products such as hydrino hydride compounds or dihydrino hydrogen into the vessel through hydrogen supply passage molecules are collected as the reactants are regenerated . 242. A pressure sensor 223 monitors pressure in the vessel . Furthermore, the hydrino hydride ions may be formed into A vacuum pump 256 is used to evacuate the chamber other compounds or converted into dihydrino molecules through a vacuum line 257. during the regeneration of the reactants . [0128 ] In an embodiment , the catalysis occurs in the gas [ 0124 ] The power system may further comprise a catalyst phase. The catalyst may bemade gaseous bymaintaining the condensor means to maintain the catalyst vapor pressure by cell temperature at an elevated temperature that, in turn , a temperature controlmeans which controls the temperature determines the vapor pressure of the catalyst . The atomic of a surface at a lower value than that of the reaction cell . and /or molecular hydrogen reactant is also maintained at a The surface temperature is maintained at a desired value desired pressure that may be in any pressure range . In an which provides the desired vapor pressure of the catalyst . In embodiment, the pressure is less than atmospheric , prefer an embodiment, the catalyst condensor means is a tube grid ably in the range about 10 millitorr to about 100 Torr . In in the cell. In an embodiment with a heat exchanger, the flow another embodiment, the pressure is determined by main rate of the heat transfer medium may be controlled at a rate taining a mixture of source of catalyst such as a metal source that maintains the condensor at the desired lower tempera and the corresponding hydride such as a metal hydride in the ture than the main heat exchanger . In an embodiment, the cell maintained at the desired operating temperature . working medium is water , and the flow rate is higher at the condensor than the water wall such that the condensor is the [0129 ] A source of catalyst 250 for generating hydrino lower, desired temperature . The separate streams of working atoms can be placed in a catalyst reservoir 295 , and gaseous media may be recombined to be transferred for space and catalyst can be formed by heating . The reaction vessel 207 process heating or for conversion to steam . has a catalyst supply passage 241 for the passage of gaseous [0125 ] The present energy invention is further described in catalyst from the catalyst reservoir 295 to the reaction Mills Prior Publications which are incorporated herein by chamber 200. Alternatively , the catalyst may be placed in a reference . The cells of the present invention include those chemically resistant open container, such as a boat, inside described previously and further comprise the catalysts , the reaction vessel . reaction mixtures, methods, and systems disclosed herein . [ 0130 ] The source of hydrogen can be hydrogen gas and The electrolytic cell energy reactor, plasma electrolysis the molecular hydrogen . Hydrogen may be dissociated into reactor, barrier electrode reactor, RF plasma reactor, pres atomic hydrogen by a molecular hydrogen dissociating surized gas energy reactor, gas discharge energy reactor, catalyst. Such dissociating catalysts or dissociators include, microwave cell energy reactor, and a combination of a glow for example , Raney nickel ( R -Ni ) , precious or noble metals , discharge cell and a microwave and or RF plasma reactor of and a precious or noble metal on a support. The precious or the present invention comprises: a source of hydrogen ; one noble metal may be Pt, Pd , Ru , Ir , and Rh , and the support of a solid , molten , liquid , and gaseous source of catalyst ; a may be at least one of Ti, Nb , A1203, SiO2 and combinations vessel containing hydrogen and the catalyst wherein the thereof. Further dissociators are Pt or Pd on carbon thatmay reaction to form lower- energy hydrogen occurs by contact of comprise a hydrogen spillover catalyst , nickel fiber mat, Pd the hydrogen with the catalyst or by reaction of MH catalyst ; sheet , Ti sponge, Pt or Pd electroplated on Ti or Ni sponge and a means for removing the lower- energy hydrogen prod or mat , TiH , Pt black, and Pd black , refractory metals such uct. For power conversion , each cell type may be interfaced as molybdenum and tungsten , transition metals such as with any of the converters of thermal energy or plasma to nickel and titanium , inner transition metals such as niobium mechanical or electrical power described in Mills Prior and zirconium , and other such materials listed in the Prior Publications as well as converters known to those skilled in Mills Publications In a preferred embodiment, hydrogen is the Art such as a heat engine , steam or gas turbine system , dissociated on Pt or Pd . The Pt or Pd may be coated on a Sterling engine , or thermionic or thermoelectric converter. support material such as titanium or Al2O3. In another Further plasma converters comprise the magnetic mirror tungstenembodiment or molybdenum, the dissociator , and isthe a dissociatingrefractory metal material such may as magnetohydrodynamic power converter, plasmadynamic be maintained at elevated temperature by temperature con power converter, gyrotron , photon bunching microwave trolmeans 230 , which may take the form of a heating coil power converter , charge drift power , or photoelectric con as shown in cross section in FIG . 1C . The heating coil is verter disclosed in Mills Prior Publications. In an embodi powered by a power supply 225. Preferably, the dissociating ment, the cell comprises at least one cylinder of an internal material is maintained at the operating temperature of the combustion engine as given in Mills Prior Publications . cell. The dissociator may further be operated at a tempera ture above the cell temperature to more effectively dissoci Hydrogen Gas Cell and Solid Fuel Reactor ate , and the elevated temperature may prevent the catalyst [0126 ] According to an embodiment of the invention , a from condensing on the dissociator . Hydrogen dissociator reactor for producing hydrinos and power may take the form can also be provided by a hot filament such as 280 powered of a hydrogen gas cell. A gas cell hydrogen reactor of the by supply 285 . US 2019/0389723 A1 Dec. 26 , 2019 17

[ 0131] In an embodiment , the hydrogen dissociation be maintained at a pressure that is lower than that which occurs such that the dissociated hydrogen atoms contact forms a significant mole fraction of LiH at the reservoir gaseous catalyst to produce hydrino atoms. The catalyst temperature . The pressures and temperatures that achieve vapor pressure is maintained at the desired pressure by this condition can be determined from the data plots of controlling the temperature of the catalyst reservoir 295 with Mueller et al . such as FIG . 6.1 [ 40 ] of H2 pressure versus a catalyst reservoir heater 298 powered by a power supply LiH mole fraction at given isotherms. In an embodiment, the 272. When the catalyst is contained in a boat inside the cell reaction chamber containing a dissociator is operated at reactor, the catalyst vapor pressure is maintained at the a higher temperature such that the Li does not condense on desired value by controlling the temperature of the catalyst the walls or the dissociator. The H , may flow from the boat , by adjusting the boat's power supply . The cell tem reservoir to the cell to increase the catalyst transport rate . perature can be controlled at the desired operating tempera Flow such as from the catalyst reservoir to the cell and then ture by the heating coil 230 that is powered by power supply out of the cell is a means to remove hydrino product to 225. The cell ( called a permeation cell) may further com preventhydrino product inhibition of the reaction . In other prise an inner reaction chamber 200 and an outer hydrogen embodiments , K , Cs, and Na replace Li wherein the catalyst reservoir 290 such that hydrogen may be supplied to the cell is atomic K , atomic Cs, and molecular NaH . by diffusion of hydrogen through the wall 291 separating the [0135 ] Hydrogen is supplied to the reaction from a source two chambers . The temperature of the wall may be con of hydrogen . Preferably the hydrogen is supplied by perme trolled with a heater to control the rate of diffusion . The rate ation from a hydrogen reservoir . The pressure of the hydro of diffusion may be further controlled by controlling the gen reservoir may be in the range of 10 Torr to 10,000 Torr , hydrogen pressure in the hydrogen reservoir . preferably 100 Torr to 1000 Torr, and most preferably about [ 0132 ] To maintain the catalyst pressure at the desire level , atmospheric pressure. The cell may be operated in the the cell having permeation as the hydrogen source may be temperature of about 100 ° C. to 3000 ° C., preferably in the sealed . Alternatively , the cell further comprises high tem temperature of about 100 ° C. to 1500 ° C., and most pref perature valves at each inlet or outlet such that the valve erably in the temperature of about 500 ° C. to 800 ° C. contacting the reaction gas mixture is maintained at the [0136 ] The source of hydrogen may be from decomposi desired temperature . The cell may further comprise a getter tion of an added hydride . A cell design that supplies H , by or trap 255 to selectively collect the lower -energy -hydrogen permeation is one comprising an internal metal hydride species and /or the increased -binding -energy hydrogen com placed in a sealed vessel wherein atomic H permeates out at pounds and may further comprise a selective valve 206 for high temperature . The vessel may comprise Pd, Ni, Ti , or releasing dihydrino gas product . Nb. In an embodiment, the hydride is placed in a sealed tube [ 0133 ] The catalyst may be at least one of the group of such as a Nb tube containing a hydride and sealed at both atomic lithium , potassium , or cesium , NaH molecule and ends with seals such as Swagelocks. In the sealed case , the hydrino atoms wherein catalysis comprises a disproportion hydride could be an alkaline or alkaline earth hydride . Or, in ation reaction . Lithium catalyst may be made gaseous by this as well as the internal -hydride - reagent case, the hydride maintaining the cell temperature in the 500-1000 ° C. range . could be at least one of the group of saline hydrides, titanium Preferably , the cell is maintained in the 500-750 ° C. range . hydride, vanadium , niobium , and tantalum hydrides , zirco The cell pressure may be maintained at less than atmo nium and hafnium hydrides, rare earth hydrides , yttrium and spheric, preferably in the range about 10 m II torr to about scandium hydrides, transition element hydrides, intermetal 100 Torr. Most preferably , at least one of the catalyst and lic hydrides, and their alloys given by W. M. Mueller et al . hydrogen pressure is determined by maintaining a mixture [ 40 ] . of catalyst metal and the corresponding hydride such as [0137 ] In an embodiment the hydride and operating tem lithium and lithium hydride, potassium and potassium perature -200 ° C., based on each hydride decomposition hydride, sodium and sodium hydride, and cesium and temperature is at least one of the list of: cesium hydride in the cell maintained at the desired oper ( 0138 ] a rare earth hydride with an operating temperature ating temperature . The catalyst in the gas phase may com of about 800 ° C .; lanthanum hydride with an operating prise lithium atoms from the metal or a source of lithium temperature of about 700 ° C .; gadolinium hydride with an metal. Preferably , the lithium catalyst is maintained at the operating temperature of about 750 ° C .; neodymium hydride pressure determined by a mixture of lithium metal and with an operating temperature of about 750 ° C .; yttrium lithium hydride at the operating temperature range of 500 hydride with an operating temperature of about 800 ° C .; 1000 ° C. and most preferably , the pressure with the cell at scandium hydride with an operating temperature of about the operating temperature range of 500-750 ° C. In other 800 ° C .; ytterbium hydride with an operating temperature of embodiments , K , Cs, and Na replace Li wherein the catalyst about 850-900 ° C .; titanium hydride with an operating is atomic K , atomic Cs, and molecular NaH . temperature of about 450 ° C .; cerium hydride with an [0134 ] In an embodiment of the gas cell reactor compris operating temperature of about 950 ° C .; praseodymium ing a catalyst reservoir or boat, gaseous Na, NaH catalyst, or hydride with an operating temperature of about 700 ° C .; the gaseous catalyst such as Li, K , and Cs vapor is main zirconium - titanium (50 % / 50 % ) hydride with an operating tained in a superheated condition in the cell relative to the temperature of about 600 ° C .; an alkali metal/ alkali metal vapor in the reservoir or boat which is the source of the cell hydride mixture such as Rb /RbH or K /KH with an operating vapor. In one embodiment, the superheated vapor reduces temperature of about 450 ° C., and an alkaline earth metal/ the condensation of catalyst on the hydrogen dissociator or alkaline earth hydride mixture such as Ba/ BaH , with an the dissociator of at least one of metal and metal hydride operating temperature of about 900-1000 ° C. molecules disclosed infra . In an embodiment comprising Li [0139 ] Metals in the gas state comprise diatomic covalent as the catalyst from a reservoir or boat, the reservoir or boat molecules. An objective of the present Invention is to is maintained at a temperature at which Li vaporizes .Hy may provide atomic catalyst such as Li as well as K and Cs . Thus, US 2019/0389723 A1 Dec. 26 , 2019 18

the reactor may further comprise a dissociator of at least one the subject invention , the term “ hydrogen ” , unless specified of metal molecules ( “MM ” ) and metal hydride molecules otherwise , includes not only proteum ( ' H ), but also deute (“ MH ” ) . Preferably , the source of catalyst, the source ofH2 , rium ( H ) and tritium ( H ) . and the dissociator of MM , MH , and HH , wherein M is the atomic catalyst are matched to operate at the desired cell Hydrogen Gas Discharge Power and Plasma Cell and conditions of temperature and reactant concentrations for Reactor example . In the case that a hydride source of Hy is used , in [0144 ] A hydrogen gas discharge power and plasma cell an embodiment, its decomposition temperature is in the and reactor of the present invention is shown in FIG . 4A . range of the temperature that produces the desired vapor The hydrogen gas discharge power and plasma cell and pressure of the catalyst . In the case of that the source of reactor of FIG . 4A , includes a gas discharge cell 307 hydrogen is permeation from a hydrogen reservoir to the comprising a hydrogen gas - filled glow discharge vacuum reaction chamber , preferable sources of catalysts for con vessel 315 having a chamber 300. A hydrogen source 322 tinuous operation are Sr and Li metals since each of their supplies hydrogen to the chamber 300 through control valve vapor pressures may be in the desired range of 0.01 to 100 325 via a hydrogen supply passage 342. A catalyst is Torr at the temperatures for which permeation occurs. In contained in the cell chamber 300. A voltage and current other embodiments of the permeation cell , the cell is oper source 330 causes current to pass between a cathode 305 and ated at a high temperature permissive of permeation , then an anode 320. The current may be reversible . the cell temperature is lowered to a temperature which [0145 ] In an embodiment, the material of cathode 305 may maintains the vapor pressure of the volatile catalyst at the be a source of catalyst such as Fe , Dy, Be, or Pd . In another desired pressure . embodiment of the hydrogen gas discharge power and [ 0140] In an embodiment of a gas cell, a dissociator plasma cell and reactor, the wall of vessel 313 is conducting comprises a means to generate catalyst and H from sources. and serves as the cathode which replaces electrode 305 , and Surface catalysts such as Pt on Ti or Pd , iridium , or rhodium the anode 320 may be hollow such as a stainless steel hollow alone or on a substrate such as Ti may also serve the role as anode. The discharge may vaporize the catalyst source to a dissociator of molecules of combinations of catalyst and catalyst. Molecular hydrogen may be dissociated by the hydrogen atoms. Preferably , the dissociator has a high discharge to form hydrogen atoms for generation of hydri surface area such as Pt/ A1203 or Pd / Al2O3. nos and energy . Additional dissociation may be provided by [ 0141] The H , source can also be H2 gas. In this case , the a hydrogen dissociator in the chamber . pressure can be monitored and controlled . This is possible [0146 ] Another embodiment of the hydrogen gas dis with catalyst and catalyst sources such as K or Cs metal and charge power and plasma cell and reactor where catalysis LiNH2, respectively , since they are volatile at low tempera occurs in the gas phase utilizes a controllable gaseous ture which is permissive of using a high - temperature valve . catalyst. The gaseous hydrogen atoms for conversion to LINH , also lowers the necessary operating temperature of hydrinos are provided by a discharge ofmolecular hydrogen the Li cell and is less corrosive which is permissive of gas. The gas discharge cell 307 has a catalyst supply passage long -duration operation using a feed through in the case of 341 for the passage of the gaseous catalyst 350 from catalyst plasma and filament cells wherein a filament serves as a reservoir 395 to the reaction chamber 300. The catalyst reservoir 395 is heated by a catalyst reservoir heater 392 hydrogen dissociator. having a power supply 372 to provide the gaseous catalyst [0142 ] Further embodiments of the gas cell hydrogen to the reaction chamber 300. The catalyst vapor pressure is reactor having NaH as the catalyst comprise a filament with controlled by controlling the temperature of the catalyst a dissociator in the reactor cell and Na in the reservoir . H2 reservoir 395 , by adjusting the heater 392 by means of its may be flowed through the reservoir to main chamber . The power supply 372. The reactor further comprises a selective power may be controlled by controlling the gas flow rate, H2 venting valve 301. A chemically resistant open container, pressure , and Na vapor pressure . The latter may be con such as a stainless steel, tungsten or ceramic boat, positioned trolled by controlling the reservoir temperature . In another inside the gas discharge cell may contain the catalyst. The embodiment, the hydrino reaction is initiated by heating catalyst in the catalyst boat may be heated with a boatheater with the external heater and an atomic H is provided by a using an associated power supply to provide the gaseous dissociator . catalyst to the reaction chamber. Alternatively , the glow gas [0143 ] The invention is also directed to other reactors for discharge cell is operated at an elevated temperature such producing increased binding energy hydrogen compounds that the catalyst in the boat is sublimed , boiled , or volatilized of the invention , such as dihydrino molecules and hydrino into the gas phase . The catalyst vapor pressure is controlled hydride compounds. A further products of the catalysis is by controlling the temperature of the boat or the discharge plasma, light, and power. Such a reactor is hereinafter cell by adjusting the heater with its power supply. To prevent referred to as a “ hydrogen reactor ” or “ hydrogen cell” . The the catalyst from condensing in the cell, the temperature is hydrogen reactor comprises a cell for making hydrinos. The maintained above the temperature of the catalyst source , cell for making hydrinos may take the form of a gas cell, a catalyst reservoir 395 or catalyst boat . gas discharge cell , a plasma torch cell , or microwave power [0147 ] In a preferred embodiment, the catalysis occurs in cell, for example . These exemplary cells which are not the gas phase , lithium is the catalyst, and a source of atomic meant to be exhaustive are disclosed in Mills Prior Publi lithium such as lithium metal or a lithium compound such as cations and are incorporated by reference . Each of these LiNH , is made gaseous by maintaining the cell temperature cells comprises: a source of atomic hydrogen ; at least one of in the range of about 300-1000 ° C. Most preferably, the cell a solid , molten , liquid , or gaseous catalyst for making is maintained in the range of about 500-750 ° C. The atomic hydrinos ; and a vessel for reacting hydrogen and the catalyst and / or molecular hydrogen reactant may be maintained at a for making hydrinos. As used herein and as contemplated by pressure less than atmospheric , preferably in the range of US 2019/0389723 A1 Dec. 26 , 2019 19 about 10 millitorr to about 100 Torr. Most preferably , the perature valves at each inlet or outlet such that the valve pressure is determined by maintaining a mixture of lithium contacting the reaction gas mixture is maintained at the metal and lithium hydride in the cell maintained at the desired temperature . desired operating temperature . The operating temperature [ 0152] The plasma cell temperature can be controlled range is preferably in the range of about 300-1000 ° C. and independently over a broad range by insulating the cell and most preferably, the pressure is that achieved with the cell at by applying supplemental heater power with heater 380 . the operating temperature range of about 300-750 ° C. The Thus, the catalyst vapor pressure can be controlled indepen cell can be controlled at the desired operating temperature dently of the plasma power . by the heating coil such as 380 of FIG . 4A that is powered [0153 ] The discharge voltage may be in the range of about by power supply 385. The cell may further comprise an inner 100 to 10,000 volts . The current may be in any desired range reaction chamber 300 and an outer hydrogen reservoir 390 at the desired voltage. Furthermore , the plasma may be such that hydrogen may be supplied to the cell by diffusion pulsed as disclosed in Mills Prior Publications such as of hydrogen through the wall 313 separating the two cham PCT /US04 / 10608 entitled “ Pulsed Plasma Power Cell and bers . The temperature of the wall may be controlled with a Novel Spectral Lines ” which is herein incorporated by heater to control the rate of diffusion . The rate of diffusion reference in its entirety . may be further controlled by controlling the hydrogen [ 0154 ] Boron nitride may comprise the feed - throughs of pressure in the hydrogen reservoir . the plasma cell since this material is stable to Li vapor . [0148 ] An embodiment of the plasma cell of the present Crystalline or transparent alumina are other stable feed invention regenerates the reactants such as Li and LiNH2. In through materials of the present invention . an embodiment, the reaction given by Eqs. ( 32 ) and (37 ) occurs to generate the hydrino reactants Li and H with a Solid Fuels and Hydrogen Catalyst Reactor large excess of energy released due to hydrino production . [0155 ] Metals in the gas state comprise diatomic covalent The products are then hydrogenated by a hydrogen source . molecules . An objective of the present Invention is to In the case that LiH is formed , one reaction to regenerate the provide atomic catalyst such as Li as well as K and Cs and lower- energy -hydrogen - catalysis reactants is given by Eq. molecular catalyst NaH . Thus, in a solid - fuels embodiment, (66 ). This may be achieved with the reactants placed in a the reactants comprise alloys, complexes, or sources of reactive region in the plasma cell such as at the cathode complexes that reversibly form with a metal catalyst M and region in a hydrogen plasma cell. The reaction may be decompose or react to provide gaseous catalyst such as Li. LiH + e- to Li and H In another embodiment, at least one of the catalyst source ( 30 ) and atomic hydrogen source further comprises at least one and then the reaction reactant which reacts to form at least one of the catalyst and atomic hydrogen . In an embodiment, the source or sources LizNH + H , to Li + LINH2 (31 ) comprise at least one of amides such as LiNH2, imides such as Li, NH , nitrides such as LizN , and catalyst metal with may occur to some extent to maintain a steady - state level of NHz. Reactions of these species provide both Li atoms and Li+ LiNH2. The H2 pressure , electron density , and energy atomic hydrogen . These and other embodiments are given may be controlled to achieve the maximum or desired extent infra ., wherein , additionally , K , Cs, and Na may replace Li of the reaction to regenerate hydrino reactants Li+ LiNH2. and the catalyst is atomic K , atomic Cs, and molecular NaH . [0149 ] In an embodiment, the mixture is stirred or mixed ( 0156 ] The present invention comprises an energy reactor during the plasma reaction . In a further embodiment of the comprising a reaction vessel constructed and arranged to plasma regeneration system and method of the present contain pressures lower , equal to , and higher than atmo invention , the cell comprises a heated flat- bottom stainless spheric pressure , a source of atomic hydrogen for chemically steel plasma chamber . LiH and Li, NH comprise a mixture in producing atomic hydrogen in communication with the molten Li. Since stainless steel is not magnetic , the liquid vessel , a source of catalyst comprising at least one of atomic mixture may be stirred with a stainless- steel - coated stirring lithium , atomic cesium , atomic potassium , and molecular bar driven by a stirring motor upon which the flat -bottom NaH in communication with the vessel , and may further plasma reactor sits . The Li-metal mixture may serve as a comprise a getter such as source of an ionic compound for cathode. The reduction of LiH to Li and H- and the further binding or reacting with a lower - energy hydride . The source reaction of Hº + Li, NH to Li and LiNH , can be monitored by of catalyst and reactant atomic hydrogen may comprise a XRD and FTIR of the product . solid fuel that may be continuously or batch -wise regener ated inside or outside of the cell wherein a physical process [0150 ] In another embodiment of a system having a reac or chemical reaction generates the catalyst and H from a tion mixture comprising species of the group of Li, LiNH2, source such that H catalysis occurs and hydrinos are formed . Li, NH , LizN , LINO3, LiX , NH_X ( X is a halide) , NH3, and Thus, embodiments of the present invention of hydrino H2, at least one of the reactants is regenerated by adding one reactants comprise solid fuels , and preferable embodiments or more of the reagents and by a plasma regeneration . The comprise those solid fuels that can be regenerated . Solid plasma may be one of the gases such as NHz and H2. The fuels can used in many applications ranging from space and plasma may be maintained in situ ( in the reaction cell) or in process heating , electricity generation , motive applications , an external cell in communication with the reaction cell . In propellants , and others applicants well known to those other embodiments , K , Cs, and Na replace Li wherein the skilled in the Art . catalyst is atomic K , atomic Cs, and molecular NaH . [0157 ] A gas cell or plasma cell of the present invention [0151 ] To maintain the catalyst pressure at the desire level, such as those shown in FIGS. 1C and 4D comprises a means the cell having permeation as the hydrogen source may be for the formation of catalyst and H atoms from sources . In sealed . Alternatively , the cell further comprises high tem solid - fuels embodiments , the cell further comprises reac US 2019/0389723 A1 Dec. 26 , 2019 20

tants to provide catalyst and H upon initiation of a chemical separate one or more components based on a differential or physical process . The initiation may be by means such as phase change or reaction . In an embodiment, the phase heating or plasma reaction . Preferably the external power change comprises melting using a heater, and the liquid is requirement to maintain the production of hydrinos is low or separated from the solid by means known in the Art such as zero based on the large power of the H catalysis reaction to gravity filtration , filtration using a pressurized gas assist, and form hydrinos. With a large energy gain , the reactants can be centrifugation . The reaction may comprise decomposition regenerated with a net release of energy for each cycle of such as hydride decomposition or reaction to from a hydride , reaction and regeneration . and the separations may be achieved by melting the corre [0158 ] In other embodiments , the reactor shown in FIG . sponding metal followed by its separation and by mechani 1C comprises a solid - fuels reactor wherein a reaction mix cally separating the hydride, respectively . The latter may be ture comprises a source of catalyst and a source of hydrogen . achieved by sieving . In an embodiment, the phase change or The reaction mixture can be regenerated by supplying a flow reaction may produce a desired reactant or intermediate . In of reactants and by removing products from the correspond embodiments , the regeneration including any desired sepa ing product mixture. In an embodiment, the reaction vessel ration steps may occur inside or outside of the reactor. 207 has a chamber 200 capable of containing a vacuum or pressures equal to or greater than atmospheric . At least one Chemical Reactor source of reagent such a gaseous reagent 221 is in commu [0162 ] A chemical reactor of the present invention further nication with chamber 200 and delivers reagent to the comprises a source of inorganic compound such as MX chamber through at least one reagent supply passage 242. A wherein M is an alkali metal and X is a halide . Additionally controller 222 is positioned to control the pressure and flow to halides, the inorganic compound may be an alkali or of reagent into the vessel through reagent supply passage alkaline earth salt such a hydroxide, oxide , carbonate , sul 242. A pressure sensor 223 monitors pressure in the vessel. fate , phosphate , borate , and silicate (other suitable inorganic A vacuum pump 256 is used to evacuate the chamber compounds are given in D. R. Lide, CRC Handbook of through vacuum line 257. Alternatively , line 257 repre Chemistry and Physics , 86th Edition , CRC Press , Taylor & sents at least one output path such as a product passage line Francis , Boca Raton , (2005 June ), pp . 4-45 to 4-97 which is to remove material from the reactor. The reactor further herein incorporated by reference ). The inorganic compound comprises a source of heat such as a heater 230 to bring the may further serve as a getter in the generation of power by reactants up to a desired temperature that initiates the solids preventing product accumulation and a consequent back fuel chemistry and the hydrino - forming catalysis reaction . In reaction or other product inhibition . A preferred Li chemical an embodiment, the temperature is in the range of about 50 type power cell comprises Li, LiNH2, LiBr or Lil, and R - Ni to 1000 ° C .; preferably it is in the range of about 100-600 ° in a hydrogen cell run at about 760 Torr H , and about 700 + ° C., and for reactants comprising at least the Li / N - alloy C. A preferred NaH chemical- type power cell comprises Na , system , the desired temperature is in the range of about NaX ( X is a halide , preferably Br or I) and R -Ni in a hydrogen cell run at about 760 Torr H , and about 700 + ° C. 100-500 ° C. The cell may further comprise at least one of NaH and [ 0159 ] The cell may further comprise a source of hydro NaNH2. À preferred K chemical- type power cell comprises gen gas and dissociator to form atomic hydrogen . The vessel K , KI, and Ni screen or R -Ni dissociator in a hydrogen cell may further comprise a source of hydrogen 221 in commu run at about 760 Torr H , and about 700+ ° C. In an embodi nication with the vessel for regenerating at least one of the ment, the H2 pressure range is about 1 Torr to 105 Torr . source of atomic catalyst such as atomic lithium and the Preferably , the H pressure is maintained in the range of source of atomic hydrogen . The hydrogen source may be about 760-1000 Torr. LiHX such as LiHBr and LiHI is hydrogen gas . The H2 gas may be supplied by a hydrogen typically synthesized in the temperature range of about line 242 or by permeation from a hydrogen reservoir 290. In 450-550 ° C., but can be run at lower temp ( ~ 350 ° C. ) with exemplary regeneration reactions, the source of atomic LiH present. NaHX such as NaHBr and NaHI is typically lithium and atomic hydrogen may be generated by hydrogen synthesized in the temperature range of about 450-550 ° C. addition according to Eqs. (66-71 ). The first step of an KHX such as KHI is preferably synthesized in the tempera alternative regeneration reaction may given by Eq. (69 ) . ture range of about 450-550 ° C. In embodiments of the [0160 ] In an embodiment , the cell size and materials are NaHX and KHX reactors , NaH and K are supplied from a such that a high operating temperature is archived . The cell source such as catalyst reservoir wherein the cell tempera may be appropriately sized to the power output to achieve ture is maintained at a higher level than that of the catalyst the desired operating temperature . High -temperature mate reservoir. Preferably , the cell is maintained at the tempera rials for the cell construction are niobium and a high ture range of about 300-550 ° C. and the reservoir is main temperature stainless steel such as Hastalloy. The source of tained in a temperature range of about 50 to 200 ° C. lower . H , may be an internal metal hydride that does not react with [0163 ] Another embodiment of the hydrogen reactor hav LiNH2, but releases H only at very high temperature . Also , ing NaH as the catalyst comprises a plasma torch for the even in the cases that the hydride does react with LiNH2, it can be separated from the reagents such as Li and LiNH , by production of power and increased -binding -energy hydro placing it in an open or closed vessel in the cell. A cell design gen compounds such as NaHX wherein H is increased that supplies H , by permeation is one comprising an internal binding - energy hydrogen and X is a halide. At least one of metal hydride placed in a sealed vessel wherein atomic H NaF , NaCl, NaBr, Nal may be aerosolized in the plasma gas permeates out at high temperature . such as H , or a noble gas /hydrogen mixture such as He/ H2 [0161 ] The reactor may further comprise means to sepa or Ar/ H rate components of a product mixture such as sieves for General Solid Fuels Chemistry mechanically separating by differences in physical proper [0164 ] A reaction mixture of the present invention com ties such as size . The reactor may further comprise means to prises a catalyst or a source of catalyst and atomic hydrogen US 2019/0389723 A1 Dec. 26 , 2019 21 or a source of atomic hydrogen ( H ) wherein at least one of or alloy may comprise at least one of M ( catalyst atom ) , H , the catalyst and atomic hydrogen is released by a chemical A1, B , Si, C , N , Sn , Te , P , S , Ni, Ta, Pt, and Pd . The first and reaction of at least one species of the reaction mixture or the second compound may be one of the group of H2, NH3, between two or more reaction -mixture species . Preferably , NH_X where X is a couterion such as halide , MMX ,MNO3 , the reaction is reversible . Preferably , the energy released is MAIH ,, M2A1H , MBH ,, M2N , M2NH , and MNH , greater than the enthalpy of reaction of the formation of wherein M is an alkali metal that may be the catalyst . The catalyst and reactant hydrogen , and in the case that the catalyst may be one of Li, K , and Cs, and NaH molecule . reactants of the reaction mixture are regenerated and The source of catalyst may be M - M such as LiLi, KK , CsCs , recycled , preferably , net energy is given off over the cycle of and NaNa. The source of H may be MH such as LiH , KH , reaction and regeneration due to the large energy of forma CsH , or NaH ( s ) . tion of product H states given by Eq . ( 1 ) . The species may [0167 ] Li catalyst may be alloyed or react to form a be at least one of an element, alloy , or a compound such as compound with at least one other element or compound such a molecular or inorganic compound wherein each may be at that the energy barrier for the release of H from LiH or Li least one of a reagent or product in the reactor. In an from LiH and Lili molecules is lowered . The alloy or embodiment , the species may form an alloy or compound compound may also release H or Li by decomposition or such as a molecular or inorganic compound with at least one reaction with further reaction species . The alloy or com of hydrogen and the catalyst . One or more of the reaction pound may be one or more of LiAlH4, LizAIH . , LiBH4, mixture species may form one or more reaction product LizN , Li ,NH , LINH ,, Lix , and LiNOz. The alloy or a species such that the energy to release H or free catalyst is compound may be one or more of Li/ Ni , Li/ Ta , Li/ Pd , Li/ Te, lowered relative to the case in the absence of the formation Li / C , Li /Si , and Li/ Sn wherein the stoichiometry of Li and of the reaction product species . In embodiments of the any other element of the alloy or compound is varied to reactants to provide a catalyst and atomic hydrogen to form achieve the optimal release of Li and H which subsequently states with energy levels given by Eq . ( 1 ), the reactants react during the catalysis reaction to form lower energy comprise at least one of solid , liquid ( including molten ), and states of hydrogen . In other embodiments , K , Cs, and Na gaseous reactants. The reactions to form the catalyst and replace Liwherein the catalyst is atomic K , atomic Cs, and atomic hydrogen to form states with energy levels given by molecular NaH . Eq. ( 1 ) occurs in one or more of the solid , liquid ( including [0168 ] In an embodiment , the alloy or compound has the molten ), and gaseous phase . Exemplary solid -fuels reactions formula ME, wherein M is the catalyst such as Li, K , or Cs , are given herein that are certainly not meant to be limiting or it is Na, E is the other element, and x and y designate the in that other reactions comprising additional reagents are stoichiometry. M and E , may be in ant desired molar ratio . within the scope of the Invention . In an embodiment x is in the range of 1 to 50 and y is in the [0165 ] In an embodiment, the reaction product species is range of 1 to 50 , and preferably x is in the range of 1 to 10 an alloy or compound of at least one of the catalyst and and y is in the range of 1 to 10. In another embodiment, the hydrogen or sources thereof. In an embodiment, the reac alloy or compound has the formula M ,EE wherein M is tion -mixture species is a catalyst hydride and the reaction the catalyst such as Li, K , or Cs, or it is Na, E , is a first other product species is a catalyst alloy or compound that has a element, E , is a second other element, and x , y , and z lower hydrogen content. The energy to release H from a designate the stoichiometry . M , E ,, and E , may be in any hydride of the catalyst may be lowered by the formation of desired molar ratio . In an embodiment, x is in the range of an alloy or second compound with the at least one another 1 to 50 , y is in the range of 1 to 50 , and z is in the range of species such as an element or first compound . In an embodi 1 to 50 , and preferably x is in the range of 1 to 10 , y is in ment, the catalyst is one of Li, K , Cs, and NaH molecule and the range of 1 to 10 , and z is in the range of 1 to 10. In the hydride is one of LiH , KH , CsH , NaH ( s ) and the at least preferred embodiments , E , and E , are selected from the one other element is selected from the group of M (catalyst ), group of H , N , C , Si, and Sn . The alloy or compound may A1, B , Si , C , N , Sn , Te, P , S , Ni, Ta , Pt, and Pd . The first and be at least one of Li_C, Si,, Li, Sn, Si ., Li, N , Si,, Li Sn , Cz, the second compound may be one of the group of H2, H2O , Li, N , Sn , Li, CN ,, Li, C , H , Li, Sn H ,, Li, N H ,, and Li Si NH3, NH_X , ( X is a couterion such as halide (other anions „ H ,. In other embodiments , K , Cs, and Na replace Li are given in D. R. Lide, CRC Handbook of Chemistry and wherein the catalyst is atomic K , atomic Cs , and molecular Physics , 86th Edition , CRC Press, Taylor & Francis , Boca NaH . Raton , ( 2005 Jun .) , pp . 4-45 to 4-97 which is herein incor [0169 ] In another embodiment, the alloy or compound has porated by reference ) MX , MNO3, MAIH ,, MzAIH . , the formula ME„ E , E , wherein M is the catalyst such as Li, MBH4, M2N , M ,NH , and MNH , wherein M is an alkali K , or Cs, or it is Na, E. is a first other element , E , is a second metal that may be the catalyst. In another embodiment, a other element, E , is a third other element, and x , w , y , and z hydride comprising at least one other element than the designate the stoichiometry . M , E , E , and E ,may be in any catalyst element releases H by reversible decomposition . desired molar ratio . In an embodiment, x is in the range of [0166 ] One or more of the reaction -mixture species may 1 to 50 , w is in the range of 1 to 50 , y is in the range of 1 form one or more reaction product species such that the to 50 , and z is in the range of 1 to 50 , and preferably x is in energy to release free catalyst is lowered relative to the case the range of 1 to 10 , w is in the range of 1 to 10 , y is in the in the absence of the formation of the reaction product range of 1 to 10 , and z is in the range of 1 to 10. In preferred species . A reaction species such as an alloy or compound embodiments , Ew , Ey, and E , are selected from the group of may release free catalyst by a reversible reaction or decom H , N , C , Si, and Sn. The alloy or compound may be at least position . Also , the free catalyst may be formed by a revers one of Li H.C.Si,, Li H.Sn Si. , Li H „ N , Si,, Li, H.Sn.cz, ible reaction of a source of catalyst with at least one other Li, H „ N , Sn , and Li H. CN . In other embodiments , K , Cs, species such as an element or first compound to form a and Na replace Li wherein the catalyst is atomic K , atomic species such as an alloy or second compound . The element Cs, and molecular NaH . Species such as ME„ E , E , are US 2019/0389723 A1 Dec. 26 , 2019 22

exemplary and are certainly not meant to be limiting in that a source of free radical initiators/ propagators such as per other species comprising additional elements are within the oxides, azo -group compounds, and UV light . scope of the Invention . [0174 ] In an embodiment , the reactant mixture to form [0170 ] In an embodiment, the reaction contains a source of lower- energy hydrogen comprises a source of hydrogen , a atomic hydrogen and a source of Li catalyst . The reaction source of catalyst , and at least one of a getter for hydrino and contains one or more species from the group of a hydrogen a getter for electrons from the catalyst as it is ionized to dissociator, H2, a source of atomic hydrogen , Li, LiH , resonantly accept energy from atomic hydrogen to form LiNO. , LINH, LINH , LiN, LX, NH?, LiBH , LiAlH , hydrinos having energies given by Eq . ( 1 ) . The hydrino LizA1H , NH3, and NH X wherein X is a counterion such getter may bind to lower - energy hydrogen to prevent the halide and those given in the CRC [41 ]. The weight % of the reverse reaction to ordinary hydrogen . In an embodiment , reactants may be in any desired molar range . The reagents the reaction mixture comprises a getter for hydrino such as may be well mixed using a ball mill . LiX or Li_X ( X is halide or other anion such anions from the [0171 ] In an embodiment, the reaction mixture comprises CRC [41 ] ) . The electron getter may perform at least one of a source of catalyst and a source of H. In an embodiment, the accepting electrons from the catalyst and stabilizing the reaction mixture further comprises reactants which undergo catalyst - ion intermediate such as a Li2 + intermediate to reaction to form Li catalyst and atomic hydrogen . The allow the catalysis reaction to occur with fast kinetics . The reactants may comprise one or more of the group of Hz, getter may be an inorganic compound comprising at least hydrino catalyst , MNH2, M2NH , M3N , NH3, LiX , NH_X ( X one cation and one anion . The cation may be Li* . The anion is a couterion such as a halide ), MNO3, MAIH4, M3A1H6, may be a halide or other anion given in the CRC [41 ] such and MBH4, wherein M is an alkali metal that may be the as one of the group comprising F-, Cl- , Br ", 1 " , NO3 , NO ,, catalyst. The reaction mixture may comprise reagents SO_2-, HSO ,, Co02 , 103 , 104 , TiO3 , Cro4 , FeO ,, selected from the group of Li , LiH , LINO3, LiNO , LINO2, PO3- , HPO 2- , H2P04 , 103 , C104 and Cr20,2- and Li, N , LINH, LINH , LIX , NHÀ, LiBH , LiAlH , Lin AlH other anions of the reactants . The hydride binder and / or LiOH , Li, S , LIHS , LiFeSi, Li, C03, LiHCO3, Li, SO4, stabalizer may be at least one of the group of LiX (X = halide) LiHSO4, LizPO4, Li HPO4, LiH2PO4, LizM004, LiNbO3, and the other compounds comprising the reactants . Li_B_0 ( lithium tetraborate ) , LiBO2, Li, WO4 , LiAICI , [0175 ] In an embodiment of the reaction mixture such as LiGaC14 , Li Cr04, Li2Cr2O7, Li TiO3, LiZrOz, LiA102, Li, LiNH2, and X wherein X is the hydride binding com LiC002, LiGaO2, Li, GeOz , LiMn, O4 , Li SiO4, Li SiO3, pound , X is at least one of LiHBr, LiHI, a hydrino hydride LiTaOz, LiCuCl2 , LipdC1j, LiVoz, LilOz, LiFeO , Li104, compound , and a lower -energy hydrogen compound . In an LiC104, LiScOne LiTiOn , LiVOn LiCrOn LiCr2One embodiment, the catalyst reaction mixture is regenerated by LiMnO ,, LiFeO ,, LiCo , LiNiO ,, LiNi On, LiCuo ,,, and addition of hydrogen from a source of hydrogen . LiZnOn, where n = 1 , 2 , 3 , or 4 , an oxyanion , an oxyanion of [0176 ] In an embodiment, the hydrino productmay bind to a strong acid , an oxidant, a molecular oxidant such as V203, form a stable hydrino hydride compound . The hydride 1205, MnO2, Re207, CrOz , RuO2, AgO , PdO , PdO2, PTO , binder may be LiX wherein X is a halide or other anion . The PtO2, and NH_X wherein X is a nitrate or other suitable hydride binder may react with a hydride that has an NMR anion given in the CRC [41 ], and a reductant. In each case , upfield shift greater than that of TMS. The binder may be an the mixture further comprises hydrogen or a source of alkali halide , and the product of hydride binding may be an hydrogen . In other embodiments , other dissociators are used alkali hydride halide having an NMR upfield shift greater or one may not be used wherein atomic hydrogen , and , than that of TMS . The hydride may have a binding energy optionally , atomic catalyst, are generated chemically by determined by XPS of 11 to 12 eV . In an embodiment , the reaction of the species of the mixture . In a further embodi product of the catalysis reaction is the hydrogen molecule ment, the reactant catalyst may be added to the reaction H2 (1/4 ) having an solid NMR peak at about 1 ppm relative mixture . to TMS and a binding energy of about 250 eV that is trapped [0172 ] The reaction mixture may further comprise an acid in a crystalline ionic lattice. In an embodiment, the product such as H2SO3, H2SO4, H , CO3, HNO2, HNO3, HC104, H2( 1/4 ) is trapped in the crystalline lattice of an ionic H3PO3, and H3PO4 or a source of an acid such as an compound of the reactor such that the selection rules for anhydrous acid . The latter may comprise at least one of the infrared absorption are such that the molecule becomes IR list of SO2, SO3, CO2, NO2 , N2O3, N2O5, C1207, PO2, P203, active and a FTIR peak is observed at about 1990 cm- . and P205. ( 0177 ] Additional sources of atomic Li of the present [0173 ] In an embodiment, the reaction mixture further invention comprise additional alloys of Li such as these comprises a reactant catalyst to generate the reactants that comprising Li and at least one of alkali, alkaline earth serve as a lower -energy -hydrogen catalyst or a source of metals , transitions, metals , rare earth metals , noble metals , lower- energy -hydrogen catalyst and atomic hydrogen or a tin , aluminum , other Group III and Group IV metal , source of atomic hydrogen . Suitable reactant catalysts com actinides , and lanthanides . Some representative alloys com prise at one of the group of acids, bases , halide ions, metal prise one or more members of the group of LiBi, LiAg , LiIn , ions and free radical sources. The reactant catalyst may be LiMg, LiAl, LiMgSi, LiFeSi, LiZr, LiAlCu , LiAlZr, at least one of the group of a weak -base -catalysts such as LiAlMg, LiB , LiCa , LiZn , LiBSi, LiNa , LiCu , LiPt, Li2SO4, a weak - acid catalyst such as a solid acid such as LiCaNa, LiAlCuMgZr, LiPb , LiCaK , LIV , LiSn , and LiNi. LiHSO4, a metal ion source such as TiCiz or AlCl3 which In other embodiments , K , Cs, and Na replace Li wherein the provide Ti3 + and A13 + ions, respectively , a free radical source catalyst is atomic K , atomic Cs, and molecular Nah , such a Cox , wherein X is a halide such as C1 wherein Co2 + [0178 ] In another embodiment, an anion can form a hydro may react with O , to form the O2 radical, metals such as Ni, gen - type bond with a Li atom of a covalently bound Li — Li Fe, Co preferably at a concentration of about 1 mol % , a molecule . This hydrogen - type bond can weaken the Li — Li source of X - ion ( X is halide) such as Cl- or F- from LiX , bond to the point that a Li atom is at vacuum energy US 2019/0389723 A1 Dec. 26 , 2019 23

( equivalent to free a atom ) such that it can serve as a catalyst tants , atomic Li and H , involving the reaction mixtures atom to form hydrinos . In other embodiments , K , Cs, and Na comprising Li with at least one of S , Sn , Si , and C are replace Li wherein the catalyst is atomic K , atomic Cs, and molecular NaH . SH + Li- Li to Li + H + LIS (33 ) [0179 ] In an embodiment, the function of the hydrogen SnH + Li - Li to Li + H + LiSn (34 ) dissociator is provided by a chemical reaction . Atomic H is generated by the reaction of at least two species of the SiH + Li- Li to Li + H + LiSi, and (35 ) reaction mixture or by the decomposition of at least one species . In an embodiment, Li — Li reacts with LiNH , to CH + Li - Li to Li + H + LiC, ( 36 ) form atomic Li, atomic H , and Li, NH . Atomic Limay also [0185 ] Preferred embodiments of the Li/ S alloy -catalyst form by the decomposition or reaction of LiNO3. In other system comprises Li with Li, S and Li with LiHS. In other embodiments , K , Cs, and Na replace Li wherein the catalyst embodiments , K , Cs, and Na replace Li wherein the catalyst is atomic K , atomic Cs, and molecular NaH . is atomic K , atomic Cs, and molecular NaH . [0180 ] In further embodiments , in addition to a catalyst or source of catalyst to form lower -energy hydrogen , the reac Primary Li/ Nitrogen Alloy Reactions tion mixture comprises heterogeneous catalysts to dissociate MM and MH such as LiLi and LiH as to provide M and H [0186 ] Lithium in the solid and liquid states is a metal, and atoms. The heterogeneous catalystmay comprise at leastone the gas comprises covalent Li, molecules. In order to gen element from the group of transition elements, precious erate atomic lithium , the reaction mixture of the solid fuel metals , rare earth and other metals and elements such as Mo, comprises Li/ N alloy reactants . The reaction mixture may W , Ta , Ni, Pt, Pd , Ti , A1, Fe, Ag, Cr, Cu , Zn , Co , and Sn . comprise at least one of the group of Li, LiH , LINH2, [0181 ] In an embodiment of the Li carbon alloy, the Li, NH , LizN , NH3, a dissociator , a hydrogen source such as reaction mixture comprises an excess of Li over the Li H2 gas or a hydride , a support , and a getter such as LiX ( X carbon intercalation limit . The excess may be in the range of is a halide) . The dissociator is preferably Pt or Pd on a high 1 % and 1000 % and preferably in the range of 1 % to 10 % . surface area support inert to Li. It may comprise Pt or Pd on The carbon may further comprise a hydrogen spillover carbon or Pd/ A1203. The latter support may comprise a catalyst having a hydrogen dissociator such as Pd or Pt on protective surface coating of a material such as LiA102. activated carbon . In a further embodiment, the cell tempera Preferred dissociators for a reagent mixture comprising a ture exceeds that at which Li is completely intercalated into Li/ N alloy or Na/ N alloy are Ptor Pd on A1,02, Raney nickel the carbon . The cell temperature may be in the range of ( R -Ni ) , and Pt or Pd on carbon . In the case that the about 100 to 2000 ° C., preferably in the range of about 200 dissociator support is Al2O3, the reactor temperature may be to 800 ° C., and most preferably in the range of about 300 to maintained below that which results in its substantial reac 700 ° C. In other embodiments , K , Cs, and Na replace Li tion with Li. The temperature may be below the range of wherein the catalyst is atomic K , atomic Cs, and molecular about 250 ° C. to 600 ° C. In another embodiment, Li is in the NaH . form of LiH and the reaction mixture comprises one or more [0182 ] In an embodiment of the Li silicon alloy, the cell of LiNH2, Li, NH , LizN , NH3, a dissociator , a hydrogen temperature is in the range over which the silicon alloy source such as H2 gas or a hydride, a support, and a getter further comprising H releases atomic hydrogen . The range such as LiX ( X is a halide ) wherein the reaction of LiH with may be about 50-1500 ° C., preferably about 100 to 800 ° C., A1203 is substantially endothermic . In other embodiments, and most preferably in the range of about 100 to 500 ° C. The the dissociator may be separate from the balance of the hydrogen pressure may be in range of about 0.01 to 10 % Torr , reaction mixture wherein the separator passes H atoms. preferably in the range of about 10 to 5000 Torr , and most [0187 ] Two preferred embodiments comprise the first preferably in the range of about 0.1 to 760 Torr. In other reaction mixture of LiH , LINH ,, and Pd on Al2O3 powder embodiments , K , Cs, and Na replace Li wherein the catalyst and a second reaction mixture of Li, LizN , and hydrided Pd is atomic K , atomic Cs, and molecular NaH . on Al2O3 powder that may further comprise H2 gas . The first [0183 ] The reaction mixture, alloys, and compounds may reaction mixture can be regenerated by addition of H2, and be formed by mixing the catalyst such as Li or a source of the second mixture can be regenerated by removing H2 and catalyst such as catalyst hydride with the other element( s ) or hydriding the dissociator or by reintroducing H2. The reac compound ( s ) or a source of the other element( s ) or com tions to generate catalyst and H as well as the regeneration pound ( s ) such as a hydride of the other element( s ) . The reactions are given infra . catalyst hydride may be LiH , KH , CsH , or NaH . The [0188 ] In an embodiment, LiNH , is added to the reaction reagents may be mixed by ball milling . An alloy of the mixture . LiNH , generates atomic hydrogen as well as catalyst may also be formed from a source of alloy com atomic Li according to the reversible reactions prising the catalyst and at least one other element or com Liz + LiNH2 ? Li+ Li2NH + H ( 37 ) pound [0184 ] In an embodiment, the reaction mechanism for the and Li/ N system to form hydrino reactants of atomic Li and H is Liz + Li2NH - Li+ LizN + H (38 ) LiNH2+ Li- Li to Li + H + Li2NH (32 ) [0189 ] In an embodiment, the reaction mixture comprises In embodiments of the other Li- alloy systems, the reaction about 2 : 1 Li and LiNH2. In the hydrino reaction cycle , mechanism is analogous to that of the Li/ N system with the Li — Li and LiNH , react to form atomic Li, atomic H , and other alloy element( s ) replacing N. Exemplary reaction Li, NH , and the cycle continues according to Eq . ( 38 ) . The mechanisms to carryout the reaction to form hydrino reac reactants may be present in any wt % US 2019/0389723 A1 Dec. 26 , 2019 24

[0190 ] The mechanism of the formation of Li NH from hydrogen source such a H , and a dissociator or form a LiNH , involves a first step that forms ammonia [ 42 ] : hydride undergoing decomposition gives 2LiNH to LizNH + NH3 (39 ) LisN + H to Li- NH + Li ( 43 ) The atomic Li catalyst can then react with additional atomic With LiH present, the ammonia reacts to release H2 H to form hydrinos. The side products such as LiH , Li ,NH , LiH + NH3 to LiNH2+ H2 (40 ) and LiNH , can be converted to LizN by evacuating the and the net reaction is the consumption of LiNH , with the reaction vessel of H2. Representative Li/ N alloy reactions formation of Hz: are as follows: LINH2+ LiH to LizNH + H2 (41 ) LizN + H ™ Li2NH + Li ( 44 ) With Li present, the amide is not consumed due to the LizN + LiH „ Li2NH + 2Li (45 ) energetically much more favorable back reaction of Li with ammonia : Li NH + LiH - Li3N +H2 (46 ) Li- Li + NH3 to LiNH2 + H + Li (42 ) Li2NH + H LINH2+ Li (47 ) Thus , in an embodiment, the reactants comprise a mixture of Li NH + LiH + LiNH + 2Li ( 48 ) Li and LiNH , to form atomic Li and atomic H according to [0195 ] LizN , a source of H , and a hydrogen dissociator are Eqs. ( 37-38 ) . in any desired molar ratio . Each are in molar ratios of greater [0191 ] The reaction mixture of Li and LiNH , that serves than 0 and less than 100 % . Preferably the molar ratios are as a source of Li catalyst and atomic hydrogen may be similar . In an embodiment, the ratios of LizN , at least one of regenerated . During the regeneration cycle , the reaction LiNH2, Li?NH , LiH , Li, and NH3, and a H source such as product mixture comprising species such as Li, Li , NH , and a metal hydride are similar. In other embodiments , K , Cs , LizN can be reacted with H to form LiH and LiNH2. LiH has and Na replace Li wherein the catalyst is atomic K , atomic a melting point of688 ° C .; whereas, LiNH , melts at 380 ° C., Cs, and molecular NaH . and Li melts at 180 ° C. LiNH , liquid and any Li liquid that [0196 ] In an embodiment, lithium amide and hydrogen is forms can be physically removed from the LiH solid at about reacted to form ammonia and lithium : 380º C., and then LiH solid can be heated separately to form Li and H2. The Li and LiNH , can be recombined to regen 1 /2H + LiNH + NH + Li ( 49 ) erate the reaction mixture . And , the excess HQ from LiH The reaction can be driven to form Li by increasing the H2 thermal decomposition can be reused in the next regenera concentration . Alternatively , the forward reaction can be tion cycle with some make -up H , to replace any H2 con driven via the formation ofatomic H using a dissociator. The sumed in hydrino formation . reaction with atomic H is given by [0192 ] In a preferred embodiment , the competing kinetics of the hydriding or dehydriding of one reactant over another H + LiNH + NH , + Li (50 ) is exploited to achieve a desired reaction mixture comprising In an embodiment of the reaction mixture that comprises one hydrided and non -hydrided compounds. For example , or more compounds that react with a source of Li to form Li hydrogen can be added under appropriate temperature and catalyst , the reaction mix comprises at least one species from pressure conditions such that the reverse of reactions of Eqs . the group of LiNH2, Li, NH , LizN , Li, LiH , NH3, H , and a (37 ) and (38 ) occur over the competing reaction of the dissociator. In an embodiment, Li catalyst is generated from formation of LiH such that the hydrogenated products are a reaction of LiNH , and hydrogen , preferably atomic hydro predominantly Li and LiNH . Alternatively , a reaction mix gen as given in reaction Eq. (50 ) . The ratios of reactants may ture comprising compounds of the group of Li, Li, NH , and be any desired amount. Preferably the ratios are about LizN may be hydrogenated to form the hydrides and the LiH stoichiometric to those of Eqs. ( 49-50 ). The reactions to can be selectively dehydrided by pumping at the temperature form catalyst are reversible with the addition of a source of and pressure ranges and duration which achieves the selec H such as H2 gas to replace that reacted to form hydrinos tivity based on differential kinetics . wherein the catalyst reactions are given by Eqs . ( 3-5 ) , and [0193 ] In an embodiment, Li is deposited as a thin film lithium amide formsby the reaction of ammonia with Li: over a large area and a mixture of LiH and LiNH , is formed NHz+ Li - LiNH2 + H (51 ) by addition of ammonia . The reaction mixture may further [0197 ] In other embodiments , K , Cs, and Na replace Li comprise excess Li. Atomic Li and H are formed according wherein the catalyst is atomic K , atomic Cs, and molecular to Eqs. (37-38 ) with the subsequent reaction to form states NaH . In a preferred embodiment, the reaction mixture with energies given by Eq . ( 1 ) . Then , the mixture can be comprises a hydrogen dissociator, a source of atomic hydro regenerated by H , addition followed by heating and pump gen , and Na or K and NHz. In an embodiment, ammonia ing with selective pumping and removal of H2. reacts with Na or K to form NaNH , or KNH , that serves as [0194 ] A reversible system of the present invention to a source of catalyst . Another embodiment comprises a generate atomic lithium catalyst is the LizN + H system source of K catalyst such as K metal, a hydrogen source such which can be regenerated by pumping. The reaction mixture as at least one of NH3, H ,, and a hydride such as a metal comprises at least one of LizN and a source of LizN such as hydride, and a dissociator . A preferred hydride is one com Li and N2, and a source of H such as at least one of H , and prising R -Ni that also may serve as a dissociator. Addition a hydrogen dissociator , LiNH , LINH , LiH, LÁ, NH3 , and a ally , a hydrino getter such as KX may be present wherein X metal hydride. The reaction of H2with LizN gives LiH and is preferably a halide such as Cl, Br, or I. The cell may be Li NH ; whereas , the reaction of LizN and H from an atomic run continuously with the replacement of the hydrogen US 2019/0389723 A1 Dec. 26 , 2019 25

source . The NHz may act as a source of atomic K by the removing the excess hydrogen by evacuating the cell. While reversible formation of KN alloy compounds from K - K excess Li is present or is added to be in excess, the R -Ni can such as at least one of amide , imide , or nitride or by be used in repeated cycles by selectively hydriding alone. formation of KH with the release of atomic K. This can be achieved by adding hydrogen in the temperature [ 0198 ] In a further embodiment, the reactants comprise the and pressure ranges that achieve the selective hydriding of catalyst such as Li and an atomic hydrogen source such H2 R -Ni and then by removing the excess hydrogen before the and a dissociator or a hydride such as hydrided R - Ni. H can vessel is heated to initiate the reactions that form atomic H react with Li— Li to form LiH and Li which can further and atomic Li and the subsequent hydrino reaction . Further serve as the catalyst to react with additional H to form hydrides and sources of catalysts can be used in place of Li hydrinos. Then , Li can be regenerated by evacuating H2 and R - Ni in this procedure . In a further embodiment, the released from LiH . The plateau temperature at 1 Torr for LiH R - N is hydrided to a great extent in a separate preparation decomposition is about 560 ° C. LiH can be decomposed at step using elevated temperature and high -pressure hydrogen about 0.5 Torr and about 500 ° C., below the alloy - formation or by using electrolysis . The electrolysis may be in basic and sintering temperatures of R -Ni . The molted Li can be aqueous solution . The base may be a hydroxide. The counter separated from R -Ni , the R - Ni may be rehydrided , and Li electrode may be nickel. In this case , R - Ni can provide and hydrided R -Ni can be returned to another reaction cycle . atomic H for a long duration with the appropriate tempera [ 0199] In an embodiment, Li atoms are vapor deposited on ture, pressure , and temperature ramp rate. a surface. The surface may support or be a source of H [ 0203 ] LiH has a high melting point of688 ° C. which may atoms. The surface may comprise at least one of a hydride be above that which sinters the dissociator or causes the and hydrogen dissociator. The surface may be R -Ni which dissociator metal to form an alloy with the catalyst metal . may be hydrided . The vapor deposition may be from a For example , an alloy of LiNimay form at temperatures in reservoir containing a source of Li atoms. The Li sourcemay excess of about 550 ° C. in the case that the dissociator is be controlled by heating . One source that provides Li atoms R - Ni and the catalyst is Li. Thus , in another embodiment, when heated is Limetal . The surface may be maintained at LiH is converted to LiNH , that can be removed at its lower a low temperature such as room temperature during the melting point such that the reaction mixture can be regen vapor deposition . The Li- coated surface may be heated to erated . The reaction to form lithium amide from lithium cause the reaction of Li and H to form H states given by Eq. hydride and ammonia is given by ( 1 ) . Other thin - film deposition techniques that are well known in the ART comprise further embodiments of the LiH + NH3 LINH2+ H2 (52 ) Invention . Such embodiments comprise physical spray, elec Then , molten LiNH , can be recovered at the melting point tro - spray, aerosol, electro -arching , Knudsen cell controlled of 380 ° C.LiNH , may be converted to Li by decomposition . release , dispenser- cathode injection , plasma -deposition , [0204 ] In an embodiment comprising the recovery of sputtering, and further coating methods and systems such as molten LiNH2, gas pressure is applied to the mixture com melting a fine dispersion of Li, electroplating Li , and chemi prising LiNH , to increase the rate of its separation from solid cal deposition of Li. In other embodiments , K , Cs, and Na components . A screen separator or semipermeable mem replace Li wherein the catalyst is atomic K , atomic Cs, and brane may retain the solid components . The gas may be an molecular NaH . inert gas such as a noble gas or a decomposition product [0200 ] In the case of vapor- deposited Li on a hydride such as nitrogen to limit the decomposition of LiNH2. surface, regeneration can be achieved by heating with pump Molten Li can be separated using gas pressure as well. To ing to remove LiH and Li, the hydride can be rehydrided by clean any residue from a dissociator, gas flow can be used . introducing H2, and Li atoms can be redeposited onto the An inert gas such as a noble gas is preferable . In the case that regenerated hydride after the cell is evacuated in an embodi residual Li adheres to the dissociator such as R -Ni , the ment. In other embodiments , K , Cs, and Na replace Li residue can be removed by washing with a basic solution wherein the catalyst is atomic K , atomic Cs, and molecular such as a basic aqueous solution which may also regenerate NaH . the R -Ni . Alternatively, the Li may be hydrided and the [ 0201 ] Li and R -Ni are in any desired molar ratio . Each of solids of LiH and R -Ni and any additional solid compounds Li and R -Ni are in molar ratios of greater than 0 and less than present may be separated mechanically by methods such as 100 % . Preferably the molar ratio of Li and R – Ni are sieving . In another embodiment, the dissociator such as similar . R -Ni and the other reactants may be physically separated but [ 0202] In a preferred embodiment, the competing kinetics maintained in close proximity to permit diffusion of atomic of the hydriding or dehydriding of one reactant over another hydrogen to the balance of reactant mixture . The balance of is exploited to achieve a reaction mixture comprising reaction mixture and dissociator may be placed in open hydrided and non -hydrided compounds. For example , the juxtaposed boats, for example . In other embodiments , the formation of LiH is thermodynamically favored over the reactor further comprises multiple compartments indepen formation of R - Ni hydride. However, the rate of LiH for dently containing the dissociator and balance of the reaction mation at low temperature such as the range of about 25 ° mixture . The separator of each compartment allows for C.- 100 ° C. is very low ; whereas , the formation of R - Ni atomic hydrogen formed in a dissociator compartment to hydride proceeds at a high rate in this temperature range at flow to the balance -of - reaction - mixture compartment while modest pressures such as the range of about 100 Torr to 3000 maintaining the chemical separation . The separator may be Torr. Thus , the reaction mixture of Li and hydrided R -Ni can a metallic screen or semipermeable , inert membrane which be regenerated from LiH R - Ni by pumping at about 400 may be metallic . The contents may be mechanically mixed 500 ° C. to dehydride LiH , cooling the vessel to about during the operation of the reactor. The separated balance of 25-100 ° C., adding hydrogen to preferentially hydride R -Ni the reaction mixture and its products can be removed and for a duration that achieves the desired selectivity, and then reprocessed outside of the reaction vessel and returned US 2019/0389723 A1 Dec. 26 , 2019 26

independently of the dissociator , or either may be indepen [0212 ] In another embodiment, the reaction mixture fur dently reprocessed within the reactor. ther comprises the reactants and products of the Haber [ 0205 ) Other embodiments of systems to generate atomic process [43 ]. The products may be NH , x = 0 , 1, 2 , 3 , 4. These catalyst Li and atomic H involve Li, ammonia , and LiH . products may react with Li or compounds comprising Li to Atomic Li catalyst and atomic H can be generated by form atomic Li and atomic H. For example , Li - Li may reaction of Liz and NHz: react with NH , to form Li and possibly H : Liz + NH3 to LINH2 + Li+ H (53 ) Li- Li+ NH3 to Li + LiNH2+ H (63 ) LiNH , is a source of NH3 by the reaction : Li - Li + NH to LiNH + Li (64 ) 2LINH ) to Li- NH + NH (54 ) In a preferred embodiment, the Li is dispersed on a support Li - Li + NH ) to Li - NH + H (65 ) having a large surface area to react with ammonia . Ammonia In other embodiments , K , Cs, and Na replace Li wherein the can also react with LiH to generate LiNH2: catalyst is atomic K , atomic Cs, and molecular NaH . [0213 ] A mixture of compounds may be used which melts LiH + NHz to LINH2+ H2 (55 ) at a lower temperature than that of one or more of com And , H , can react with Li, NH to regenerate LiNH2: pounds individually . Preferably , a eutectic mixture may form that is a molten salt that mixes the reactants such as Li and H2 + Li NH to LINH2+ LiH (56 ) LiNH2 [0206 ] In another embodiment, the reactants comprise a [0214 ] The chemistry of the reaction mixture can change mixture of LiNH , and a dissociator. The reaction to form very substantially based on the physical state of the reactants atomic lithium is : and the presence or absence of a solvent or added solute or LINH2+ H to Li+ NH3 ( 57) alloy species. Objectives of the present invention for chang ing the physical state are control the rate of reaction and The Li can then react with additional H to form hydrino . to alter the thermodynamics to achieve a sustainable lower [0207 ] Other embodiments of systemsto generate atomic energy hydrogen reaction with the addition of H from a catalyst Li and atomic H involve Li and LiBH4 or NH_X ( X source of H. For the Li/ N alloy system comprising reactants is an anion such as halide ) . Atomic Li catalyst and atomic H such as Li and LiNH2, alkali metals , alkaline earth metals , can be generated by reaction of Li , and LiBH4: and their mixtures may serve as the solvent. For example , Liz + LiBH4 to LiBHz+ Li + LiH (58 ) excess Li can serve as a molten solvent for LiNH , to comprise solvated Li and LiNH , reactants that will have NH_X can generate LiNH , and H2 different kinetics and thermodynamics of reaction relative to Liz +NH_X to LiX + LiNH2 + H2 (59 ) those of the solid - state mixture. The former effect, control of the kinetics of the lower -energy hydrogen reaction , can be [0208 ] Then , atomic Li can be generated according to the adjusted by controlling the properties of the solute and reaction of Eqs. (32 ) and ( 37 ) . In another embodiment, the solvent such as temperature, concentration , and molar ratios. reaction mechanism for the Li/ N system to form hydrino Following the reaction to generate atomic catalyst and reactants of atomic Li and H is atomic hydrogen , the latter effect can be used to regenerate NH_X + Li- Li to Li+ H +NHz + LiX (60 ) the initial reactants . This is a route when the products cannot where X is a counterion , preferably a halide. be directly regenerated by hydrogenation . [0209 ] Atomic Li catalyst can be generated by reaction of [0215 ] One embodiment where the regeneration of the Li_NH or LizN with atomic H formed by the dissociation of reactants is facilitated by a solvent or added solute or alloy H : species involves lithium metal wherein the hydriding of Li is not to completion so that Li remains a solvent and a Li2NH + H to LINH2 + Li (61 ) reactant. In Li solvent, the following regeneration reaction LisN + H to Li- NH + Li (62 ) may occur with the addition of H from a source to form LiH : [0210 ] In a further embodiment, the reaction mixture LiH + Li2NH to 2Li+ LINH2 (66 ) comprises nitrides ofmetals in addition to Li such as those [0216 ] For the Li/ N alloy system comprising reactants of Mg Ca Sr Ba Zn and Th . The reaction mixture may such as Li and LiNH2, alkali metals , alkaline earth metals , comprise metals that exchange with Li or form mixed -metal and their mixtures may serve as the solvent . In an embodi compounds with Li. The metals may be from the group of ment, the solvent is selected such that it can reduce LiH to alkali, alkaline earth , and transition metals . The compounds Li and form an unstable solvent hydride with the release of may further comprise N such as amides , imides, and nitrides . H. Preferably , the solvent may be one or more of the group [0211 ] In an embodiment, the catalyst Li is generated of Li ( excess ), Na , K , Rb, Cs, and Ba that have the ability chemically by an anion exchange reaction such as a halide to reduce Lit and a corresponding hydride having a low ( X ) exchange reaction . For example , at least one of Limetal thermal stability . In a case that the melting point of the and Li — Limolecules are reacted with a halide compound to solvent is higher than desired such as in the case of Ba with form atomic Li and LiX . Alternatively , LiX is reacted with a high melting point of 727 ° C., the solvent can be mixed a metal M to form atomic Li and MX . In an embodiment, with other solvents such as metals to from a solvent with a lithium metal is reacted with a lanthanide halide to form Li lower melting point such as one comprising a eutectic and the LiX where X is halide. An example is the reaction mixture . In an embodiment, one or more alkaline earth of CeBrz with Li , to form Li and LiBr. In other embodi metals can be mixed with one or more alkali metals to lower ments , K , Cs , and Na replace Li wherein the catalyst is the melting point, add the capability to reduce Li* , and atomic K , atomic Cs, and molecular NaH . decrease the stability of the corresponding solvent hydride . US 2019/0389723 A1 Dec. 26 , 2019 27

[0217 ] Another embodiment where the regeneration of the The balanced H , reduction reaction of the released H2 (Eq . reactants is facilitated by a solvent or added solute or alloy (72 )) with LiNO3 to form water and lithium amide is species involves potassium metal. Potassium metal in a mixture of LiH and LiNH , may reduce LiH to Li and form 4H2+ LINO3 ? L?NH2 + 3H2O ( 73 ) KH . Since KH is thermally unstable at intermediate tem Then , reaction Eq . (72 ) can proceed with the generated peratures such as 300 ° C., it may facilitate the further LiNH , and the balance of Li, and the coupled reactions hydrogenation of Li ,NH to Li and LiNH . given by Eqs. (72 ) and ( 73 ) can occur until the Li is [0218 ] Thus, K may catalyze the reaction given by Eq . completely consumed . The overall reaction is given by (66 ) . The reaction steps are LiNO3+ 8Li + 3LiNH2 ? + 3H2O + 4Li3N ( 74 ) LiH K to Li + KH (67 ) The water may be dynamically removed by methods such as condensation or reacted with a getter to prevent its reaction KH + Li, NH to K + Li+ LiNH2 (68 ) with species such as Li, LiNH , Li, NH , and LizN . wherein H is added at the rate at which it is consumed by lower -energy hydrogen production . Alternatively, K cata Exemplary Regeneration of Li Catalyst Reactants lytically generates Li and H from LiH wherein LiNH , is formed directly from hydrogenation of Li, NH . The reac [ 0221] The present invention further comprises methods tions steps are and systems to generate , or regenerate the reaction mixture to form states given by Eq . ( 1 ) from any side products that Li2NH + 2H to LiH + LiNH2 (69 ) form during said reaction . For example , in an embodiment LiH + K to KH + Li of the energy reactor, the catalysis reaction mixture such as ( 70 ) Li, LiNH2, and LiNO3 is regenerated from any side products KH to K + H ( g ) (71 ) such as LiOH and Li20 by methods known to those skilled In addition to the favorable condition of the instability of the in the Art such as given in Cotton and Wilkinson [43 ] . hydride (KH ) , the amide (KNH2 ) is also unstable so that the Components of the reaction mixture including side products exchange of lithium amide with potassium amide is not may be liquid or solids. The mixture is heated or cooled to thermodynamically favorable . In addition to K , Na is a a desired temperature, and the products are separated physi preferred metal solvent since it can reduce LiH and has a cally by means known by those skilled in the Art. In an lower vapor pressure . Other examples of suitable metal embodiment, LiOH and Li20 are solid , Li, LiNH2, and solvents are Rb, Cs, Mg . Ca , Sr, Ba, and Sn . The solvent may LiNO3 are liquid , and the solid components are separated comprise a mixture of metals such as a mixture of two or from the liquid ones. The LiOH and Li20 may be converted more alkaline or alkaline earth metals . Preferable solvents to lithium metal by reduction with H , at high temperature or are Li (excess ) and Na above 380 ° C. since Li is miscible in by electrolysis of the molten compounds or a mixture Na above this temperature . containing them . The electrolysis cell may comprise a [0219 ] In another embodiment, an alkali or alkaline earth eutectic molten salt comprising at least one of LiOH , Li2O , metal serves as a regeneration catalyst according to Eqs . LiCl, KCl, CaCl2 and NaCl. The electrolysis cell is com (70-71 ) . In an embodiment, LiNH , is first removed from the prised of a material resistant to attack by Li such as a Beo LiH /LiNH , mixture by melting the LiNH2. Then , the metal or BN vessel. The Liproduct may be purified by distillation . Mmay be added to catalyze the LiH to Liconversion . M can LiNH , is formed by meansknown in the Art such as reaction be selectively removed by distillation . Na, K , Rb , and Cs of Li with nitrogen followed by hydrogen reduction . Alter form hydrides that decompose at relatively low temperatures natively , LiNH , can be formed directly by reaction of Li and form amides that thermally decompose ; thus , in another with NHz. embodiment, at least one can serve as a reactant for the [0222 ] In the case that the initial reaction mixture com catalytic conversion of LiH to Li and H according to the prises at least one of Li, LiNH2, and LiNO3, Limetal may corresponding reaction for K given by Eqs. (67-71 ) . In be regenerated by methods such as electrolysis , LiNO3 can addition , some alkaline earths such as Sr can form very be generated from Limetal . One key step that eliminates the stable hydrides which can serve to convert LiH to Li by difficult nitrogen fixation step is the reaction of Limetal with reaction of LiH and an alkaline earth metal to form the stable N2 to form LizN even at room temperature . LizN can be alkaline earth hydride . By operating at an elevated tempera reacted with H , to form Li2NH and LiNH2. LizN can be ture , hydrogen may be supplied from the alkaline earth reacted with an oxygen source to form LiNO3. In an hydride via decomposition with the lithium inventory being embodiment, LizN is used in the synthesis of lithium nitrate primarily as Li. The reaction mixture may comprise Li, (LiNO3 ) involving reactants or intermediates of at least one LiNH2, X , and a dissociator wherein X may be a lithium or more of lithium (Li ), lithium nitride (LizN ) , oxygen (O2 ) , compound such as LiH , Li ,NH , LizN with a small amount an oxygen source, lithium imide (Li , NH ) , and lithium amide of an alkaline earth metal that forms a stable hydride to ( LiNH ) . generate Li from LiH . The source of hydrogen may be HQ In an embodiments , the oxidation reactions are gas . The operating temperature may be sufficient such that H LINH2+ 202 > LiNO3+ H2O (75 ) is available . [0220 ] In an embodiment, LiNO , can serve to generate the Li2NH + 202 > L?NO3+ LIOH ( 76 ) LiNH , source of Li and H in a set of coupled reactions . Consider an embodiment of the catalysis reaction mixture LizN + 202 ? LINO3 + Li20 (77 ) comprising Li, LiNH ,, and LiNO3. The reaction of Li and [0223 ] Lithium nitrate can be regenerated from Li20 and LiNH , to LizN and release H , is LiOH using at least one of NO2, NO , and O2 by the LINH2+ 2Li H2 + LizN (72 ) following reactions US 2019/0389723 A1 Dec. 26 , 2019 28

3Li2O + 6NO2 + 3/ 202 > L?NO3 (78 ) may further undergo electrolysis to the desired anion which may be precipitated out as LilOz or Li104, dried , and Li2O + 3N022L?NO3 + NO (79 ) dehydrated . NO + 1 /202 - NO2 ( 80 ) NaH Molecular Catalyst LiOH + NO2+ NOLINO2 + H20 ( industrial process) (81 ) [0226 ] In a further embodiment , a compound comprising hydrogen such as MH where His hydrogen andMis another 2LiOH + 2NO2 -> L?NO3 + LiNO2+ H2O (82 ) element serves as a source of hydrogen and a source of Lithium oxide can be converted to lithium hydroxide by catalyst . In an embodiment, a catalytic system is provided by reaction with steam : the breakage of the M - H bond plus the ionization of electrons from an atom M each to a continuum energy level Li2O + H20- LiOH (83 ) such that the sum of the bond energy and ionization energies In an embodiment, Li20 is converted to LiOH followed by of the t electrons is approximately one of m.27.2 eV and reaction with NO , and NO according to Eq. (81 ) . [ 0224 ] Both lithium oxide and lithium hydroxide can be 27.2 converted to lithium nitrate by treatment with nitric acid m . eV followed by drying : Li2O + 2HNO3 ? L?NO3 + H2O ( 84 ) where m is an integer. [ 0227 ] One such catalytic system involves sodium . The LiOH + HNO3 ? LiNO3+ H2O (85 ) bond energy of NaH is 1.9245 eV [ 44 ]. The first and second [0225 ) LiNO , can be made by treatment of lithium oxide ionization energies of Na are 5.13908 eV and 47.2864 eV , or lithium hydroxide with nitric acid . Nitric acid , in tern , can respectively [ 1 ]. Based on these energies NaH molecule can be generated by known industrial methods such as by the serve as a catalyst and H source since the bond energy of Haber process followed by the Ostwald process and then by NaH plus the double ionization (t = 2 ) of Na to Na² + , is 54.35 hydration and oxidation of NO as given in Cotton and eV (2x27.2 eV ) which is equivalent to m = 2 in Eq. ( 2 ). The Wilkinson [43 ]. In one embodiment, the exemplary catalyst reactions are given by sequence of steps are : 54.35 eV + NaH Na2 + + 2e + + [( 3 )2 – 1 ? ] . 13.6 eV (88 ) H2 (86 ) N2 NH3 02 NO O2 + H2O> HNO3 Haber Ostwald Na2 + + 2e + H + NaH + 54.35 eV (89 ) process process LiOH + HNO3 ? LINO3 + H2O ( 87 ) And , the overall reaction is

Specifically , the Haber process may be used to produce NH3 ?? from N2 and H , at elevated temperature and pressure using H ? H + [( 3 ) 2 – 12 ]. 13.6 eV (90 ) a catalyst such as a - iron containing someoxide . The ammo nia may be used to form LiNH , from Li. The Ostwald process may be used to oxidize the ammonia to NO at a [0228 ] As given in Chp . 5 of Ref [ 30 ] , and Ref. [20 ] , catalyst such as a hot platinum or platinum - rhodium cata hydrogen atoms H ( 1 / p ) p = 1 , 2 , 3 , . . . 137 can undergo lyst . The NO may be further reacted with oxygen and water further transitions to lower - energy states given by Eq . ( 1 ) to form nitric acid which can be reacted with lithium oxide wherein the transition of one atom is catalyzed by a second or lithium hydroxide to form lithium nitrate . The crystalline that resonantly and nonradiatively accepts m.27.2 eV with a lithium nitrate reactant is then obtained by drying . In another concomitant opposite change in its potential energy. The embodiment, NO and NO2 are reacted directly with the one overall general equation for the transition of H ( 1 / p ) to or more of lithium oxide and lithium hydroxide to form H ( 1 / ( p +m ) ) induced by a resonance transfer of m : 27.2 eV to lithium nitrate . The regenerated Li, LiNH2, and LiNO3 are H ( 1 / p ') is represented by then returned to the reactor in desired molar ratios . In further H ( 1/ p ') + H ( 1/ p ) -> H * + e + H (1 / (p + m ) ) +[ 2 pm+m2-p2 ] exemplary regeneration reactions, an embodiment of the .13.6 eV ( 91 ) reactor comprises the reactants of Li, LiNH2, and LiCo02 . LiOH , Li20 , and Co and its lower oxides are the side In the case of high hydrogen concentrations, the transition of products . The reactants can be regenerated by electrolysis of H ( 1/3 ) ( p = 3 ) to H ( 1/4 ) ( p + m = 4 ) with H as the catalyst ( p = 1 ; LiOH and Li2O to Li . LiNH , can be regenerated by reaction m = 1 ) can be fast: of Li with NHz or N , and then H2. The Coo , and its lower oxides can be regenerated by reaction with oxygen . The LiCoo , can be formed by reaction of Li with Co02. Li, H (1/3 ) H (1/4 ) +81.6 eV (92 ) LINH2, and LiCoO2 are then returned to the cell in a batch or continuous regeneration process . In the case that LilO3 or Li104 is a reagent of the mixture, 10 , - and or 104 may be Due to the stable binding of H-( 1/4 ) in halides and its regenerated by reaction of iodine or iodide ion with base and stability to ionization relative to other reaction species , it and US 2019/0389723 A1 Dec. 26 , 2019 29

the corresponding molecule formed by the reactions 2H ( 1 / intermetallic of R - Ni. Further exemplary reagents are an 4 ) H (1/4 ) and H-( 1/4 ) + H + H (1/4 ) are favored products alkaline or alkaline earth metal and an oxidant such as AIX3, of the catalysis of hydrogen . MgX , LaXz, CeX3 , and Tix ,, where X is a halide, prefer [0229 ] The NaH catalyst reaction may be concerted since ably Br or I. Additionally , the reaction mixture may com the sum of the bond energy of NaH , the double ionization prise another compound comprising a getter or a dispersant ( t= 2 ) of Na to Na2 + , and the potential energy of H is 81.56 such as at least one of Na2CO3, Na2SO4, and Na3PO4 that eV ( 3.27.2 eV ) which is equivalent to m = 3 in Eq. ( 2 ) . The may be doped into the dissociator such as R -Ni . The reaction catalyst reactions are given by mixture may further comprise a support wherein the support may be doped with at least one reactant of the mixture . The support may have preferably a large surface area that favors 81.56 eV + NaH + H ? (93 ) the production of NaH catalyst from the reaction mixture . Na2 + + 2e + H + + e + H ?? The support may comprise at least one of the group of R -Ni , fast + [ (4 )2 – 12 ] - 13.6 eV Al, Sn , Al2O3 such as gamma, beta , or alpha alumina , sodium aluminate ( according to Cotton [ 45 ] beta - aluminas Na2 + + 2e + H + H fast + é ? NaH + H + 81.56 eV ( 94 ) have other ions present such as Na+ and possess the ideal ized composition Na20 : 11A1,03) , lanthanide oxides such as And , the overall reaction is M203 (preferably M = La, Sm , Dy, Pr , Tb , Gd, and Er ), Si, silica , silicates , zeolites, lanthanides , transition metals, metal alloys such as alkali and alkali earth alloys with Na, rare (95 ) earth metals , SiO2 - A1203 or SiO2 supported Ni, and other H ? HCM H + [( 4 )2 – 12 ] . 13.6 eV supported metals such as at least one of alumina supported platinum , palladium , or ruthenium . The support may have a where Hfaszt is a fast hydrogen atom having at least 13.6 eV high surface area and comprise a high - surface - area (HSA ) of kinetic energy materials such as R -Ni , zeolites , silicates, aluminates, alu [0230 ] In an embodiment, the reaction mixture comprises minas, alumina nanoparticles , porous Al2O3, Pt, Ru, or at least one of a source of NaH molecules and hydrogen . The Pd/ Al2O3, carbon , Pt or Pd / C , inorganic compounds such as NaH molecules may serve as the catalyst to form H states Na2CO3, silica and zeolite materials , preferably Y zeolite given by Eq. ( 1 ) . A source ofNaH molecules may comprise powder . In an embodiment , the support such as Al2O3 (and at least one of Na metal, a source of hydrogen , preferably the Al2O3 support of the dissociator if present ) reacts with atomic hydrogen , and NaH ( s ) . The source of hydrogen may the reductant such as a lanthanide to form a surface -modified be at least one of H2 gas and a dissociator and a hydride . support. In an embodiment, the surface Al exchanges with Preferably , the dissociator and hydride may be R -Ni . Pref the lanthanide to form a lanthanide - substituted support. This erably , the dissociator may also be Pt/ Ti , Pt/ Al2O3, and support may be doped with a source of NaH molecules such Pd /A1,03 powder . Solid NaH may be a source of at least one as NaOH and reacted with a reductant such as a lanthanide . of NaH molecules , H atoms, and Na atoms. The subsequent reaction of the lanthanide - substituted sup [0231 ] In a preferred embodiment, one of atomic sodium port with the lanthanide will not significantly change it, and and molecular NaH is provided by a reaction between a the doped NaOH on the surface can be reduced to NaH metallic , ionic , or molecular form of Na and at least one catalyst by reaction with the reductant lanthanide. other compound or element. The source of Na or NaH may [0232 ] In an embodiment, wherein the reaction mixture be at least one of metallic Na , an inorganic compound comprises a source of NaH catalyst, the source of NaH may comprising Na such as NaOH , and other suitable Na com be an alloy of Na and a source of hydrogen . The alloy may pounds such as NaNH2, Na2CO3, and Na20 which are given comprise at least one of those known in the Art such as an in the CRC [41 ] , NaX ( X is a halide ), and NaH ( s ) . The other alloy of sodium metal and one or more other alkaline or element may be H , a displacing agent, or a reducing agent. alkaline earth metals , transition metals , Al, Sn, Bi, Ag, In , The reaction mixture may comprise at least one of (1 ) a Pb , Hg, Si, Zr, B , Pt, Pd , or other metals and the H source source of sodium such as at least one of Na( m ), Nah , may be H , or a hydride. NaNH , Na2SO4, Na2O, NaOH , NaOH doped - R - Ni, NaX [0233 ] The reagents such as the source of NaH molecules , ( X is a halide ) , and NaX doped R -Ni , ( 2 ) a source of the source of sodium , the source of NaH , the source of hydrogen such as H2 gas and a dissociator and a hydride, ( 3 ) hydrogen , the displacing agent, and the reducing agent are in a displacing agent such as an alkali or alkaline earth metal, any desired molar ratio . Each is in a molar ratio of greater preferably Li, and ( 4 ) a reducing agent such as at least one than 0 and less than 100 % . Preferably , the molar ratios are of a metal such as an alkaline metal, alkaline earth metal, a similar. lanthanide, a transition metal such as Ti, aluminum , B , a [0234 ] A preferred embodiment comprises the reaction metal alloy such as AlHg, NaPb , NaAl, LiAl, and a source mixture of NaH and Pd on A1203 powder wherein the of a metal alone or in combination with reducing agent such reaction mixture may be regenerated by addition of Hz. as an alkaline earth halide , a transition metal halide, a [0235 ] In an embodiment , Na atoms are vapor deposited lanthanide halide, and aluminum halide . Preferably , the on a surface. The surface may support or be a source of H alkalimetal reductant is Na. Other suitable reductants com atoms to form NaH molecules . The surface may comprise at prise metal hydrides such as LiBH4, NaBH4, LiAlH4, or least one of a hydride and hydrogen dissociator such as Pt, NaAIH . Preferably , the reducing agent reacts with NaOH to Ru , or Pd /Al2O3 which may be hydrided . Preferably , the form a NaH molecules and a Na product such as Na, NaH ( s) , surface area is large . The vapor deposition may be from a and Na20 . The source of NaH may be R - Ni comprising reservoir containing a source of Na atoms. The Na source NaOH and a reactant such as a reductant to form NaH may be controlled via heating . One source that provides Na catalyst such as an alkali or alkaline earth metal or the Al atoms when heated is Na metal . The surface may be main US 2019/0389723 A1 Dec. 26 , 2019 30 tained at a low temperature such as room temperature during wherein M is a lanthanide . The dissociatormay be separated the vapor deposition . The Na - coated surface may be heated from the rest of the reaction mixture wherein the separator to cause the reaction of Na and H to form NaH and may passes atomic H. further cause the NaH molecules to react to form H states [0238 ] A preferred embodiment comprises the reaction given by Eq. ( 1 ) . Other thin - film deposition techniques that mixture of NaH , La, and Pd on Al2O3 powder wherein the are well known in the ART comprise further embodiments of reaction mixture may be regenerated in an embodiment, by the Invention . Such embodiments comprise physical spray, adding H2, separating NaH and lanthanum hydride by siev electro - spray, aerosol, electro - arching , Knudsen cell con ing , heating lanthanum hydride to form La , and mixing La trolled release , dispenser - cathode injection , plasma -deposi and NaH . Alternatively , the regeneration involves the steps tion , sputtering, and further coating methods and systems of separating Na and lanthanum hydride by melting Na and such as melting a fine dispersion of Na, electroplating Na , removing the liquid , heating lanthanum hydride to form La , and chemical deposition of Na . Na metal may be dispersed hydriding Na to NaH , and mixing La and NaH . The mixing on a high - surface area material , preferably Na2CO3, carbon , may be by ball milling . silica , alumina , R - Ni, and Pt, Ru , or Pd /A1203 , to increase [ 0239 ] In an embodiment , a high -surface - area material the activity to form NaH when reacted with another reagent such as R - Ni is doped with NaX ( X = F , C1, Br, I ) . The doped such as H or a source of H. Other dispersion materials are R -Ni is reacted with a reagent that will displace the halide known in the Art such as those given in Cotton et al. [46 ] . to form at least one of Na and NaH . In an embodiment, the [ 0236 ] In an embodiment, at least one reactant comprising reactant is at least an alkali or alkaline earth metal, prefer the reductant or source of NaH such as Na and NaOH ably at least one of K , Rb , Cs. In another embodiment, the undergoes aerosolization to create a corresponding reactant reactant is an alkaline or alkaline earth hydride, preferably vapor to react to form NaH catalyst. Na and NaOH may react at leastone of KH , RbH , CsH , MgH , and CaH2. The reactant in the cell to form NaH catalyst wherein at least one species may be both an alkali metal and an alkaline earth hydride. undergoes aerosolization . The aerosolized species may be The reversible general reaction may be given by transported into the cell to react to form NaH catalyst . The NaX + MH NaH +MX (97 ) means to carry the aerosolized species may be a carrier gas . The aerosolization of the reactant may be achieved using a mechanical agitator and a carrier gas such as a noble gas to NaOH Catalyst Reactions to Form Nah Catalyst carry the reactant into the cell to form NaH catalyst . In an [0240 ] The reaction of NaOH and Na to Na20 and NaH is embodiment, Na which may serve as a source of NaH and a reductant is aerosolized by becoming charged and electri NaOH + 2Na - Na2O + NaH ( 98 ) cally dispensed . The reactants such as at least one of Na and The exothermic reaction can drive the formation of NaH ( g ) . NaOH may be aerosolized mechanically in a carrier gas or Thus , Na metal can serve as a reductant to form catalyst they may undergo ultrasonic aerosolization . The reactant NaH (g ). Other examples of suitable reductants that have a may be forced through an orifice to form a vapor . Alterna similar highly exothermic reduction reaction with the NaH tively , the reactant may be heated locally to very high source are alkali metals , alkaline earth metals such as at least temperature to be vaporized or sublimed to form a vapor. one of Mg and Ca , metal hydrides such as LiBH4, NaBH4, The reactants may further comprise a source of hydrogen . LiAlH4, or NaAlH4, B , Al, transition metals such as Ti, The hydrogen may react with Na to form NaH catalyst . The lanthanides such as at least one of La, Sm , Dy , Pr, Tb , Gd , Na may be in the form of a vapor. The cell may comprise a and Er, preferably La , Tb , and Sm . Preferably, the reaction dissociator to from atomic hydrogen from H2. Other means mixture comprises a high - surface - area material (HSA mate of achieving aerosolization that are known to those skilled in rial ) having a dopant such as NaOH comprising a source of the Art are part of the Invention . NaH catalyst. Preferably , conversion of the dopant on the [ 0237 ] In an embodiment, the reaction mixture comprises material with a high surface area to the catalyst is achieved . at least one species of the group comprising Na or a source The conversion may occur by a reduction reaction . The of Na , NaH or a source of NaH , a metal hydride or source reductantmay be provided as a gas stream . Preferably, Na is of a metal hydride, a reactant or source of a reactant to form flowed into the reactor as a gas stream . In addition to the a metal hydride, a hydrogen dissociator, and a source of preferred reductant, Na, other preferred reductants are other hydrogen . The reaction mixture may further comprise a alkalimetals , Ti, a lanthanide , or Al. Preferably , the reaction support. A reactant to form a metal hydride may comprise a mixture comprises NaOH doped into a HSA material pref lanthanide, preferably La or Gd. In an embodiment, La may erably R -Ni wherein the reductant is Na or the intermetallic reversibly react with NaH to form LaH , ( n = 1 , 2 , 3 ). In an Al. The reaction mixture may further comprise a source of embodiment, the hydride exchange reaction forms NaH H such as a hydride or H2 gas and a dissociator. Preferably catalyst . The reversible general reaction may be given by the H source is hydrided R -Ni . NaH + M Na +MH (96 ) [0241 ] In an embodiment, the reaction temperature is maintained below that at which the reductant such as a The reaction given by Eq . ( 96 ) applies to other MH - type lanthanide forms an alloy with the source of catalyst such as catalysts given in TABLE 2. The reaction may proceed with R -Ni . In the case of lanthanum , preferably the reaction the formation of hydrogen that may be dissociated to form temperature does not exceed 532 ° C. which is the alloy atomic hydrogen that reacts with Na to form NaH catalyst. temperature ofNi and La as shown by Gasser and Kefif [47 ] . The dissociator is preferably at least one of Pt, Pd , or Additionally , the reaction temperature is maintained below Ru /A1,03 powder, Pt/ Ti , and R - Ni. Preferentially , the dis that at which the reaction with the A1203 of R -Ni occurs to sociator support such as Al2O3 comprises at least surface La a significant extent such as in the range of 100 ° C. to 450 ° substitution for Al or comprises Pt, Pd , or Ru /M203 powder C. US 2019/0389723 A1 Dec. 26 , 2019 31

[0242 ] In an embodiment, Na2O formed as a product of a added to form at least one of Na and NaH molecules . The Na reaction to generate NaH catalyst such as that given by Eq. may further react with H from a source such as H2 gas or a ( 98 ) , is reacted with a source ofhydrogen to form NaOH that hydride such as R -Ni to form NaH catalyst. The subsequent can further serve as a source of NaH catalyst . In an embodi catalysis reaction of NaH forms H states given by Eq. ( 1 ) . ment, a regenerative reaction of NaOH from Eq. (98 ) in the The addition of an alkali or alkaline earth metal M may presence of atomic hydrogen is reduce Na + to Na by the reactions: Na2O + H - NaOH + Na AH = -11.6 kJ /mole NaOH (99 ) NaOH + M to MOH + Na ( 104 ) NaH » Na + H ( 1/3 ) AH = -10,500 kJ/ mole H ( 100 ) 2NaOH + M to M (OH ) 2 + 2Na ( 105 ) and M may also react with NaOH to form H as well as Na NaH-> Na + H ( 1/4 ) AH = -19,700 kJ/ mole H ( 101) 2NaOH + M to Na2O + H2+ MO ( 106 ) Thus , a small amount of NaOH and Na with a source of Na2O + M to M2O + 2Na ( 107) atomic hydrogen or atomic hydrogen serves as a catalytic source of the NaH catalyst, that in turn forms a large yield Then , the catalyst NaH may be formed by the reaction of hydrinos via multiple cycles of regenerative reactions such as those given by Eqs. ( 98-101) . In an embodiment, Na + H to NaH ( 108 ) from the reaction given by Eq . (102 ) , Al( OH ) , can serve as by reacting with H from reactions such as that given by Eq . a source of NaOH and NaH wherein with Na and H , the ( 106 ) as well as from R — Ni and any added source of H.Na reactions given by Eqs . (98-101 ) proceed to form hydrinos . is a preferred reductant since it is a further source of NaH . 3Na + Al( OH ) 3 - NaOH + NaAlO2 + NaH + 1/ 2H2 ( 102 ) [ 0247 ] Hydrogen may be added to reduce NaOH and form In an embodiment, the Al of the intermetallic serves as the NaH catalyst : reductant to form NaH catalyst The balanced reaction is given by NaOH + H2 to NaH + H2O ( 109 ) 3NaOH + 2A1 - Al2O3 + 3NaH ( 103 ) The H in R -Ni may reduce NaOH to Na metal, and water that may be removed by pumping . This exothermic reaction can drive the formation of NaH ( g ) to drive the very exothermic reaction given by Eqs. (88-92 ) In an embodiment, the reaction mixture comprises one or wherein the regeneration of NaH occurs from Na in the more compounds that react with a source of NaH to form presence of atomic hydrogen . NaH catalyst. The source may be NaOH . The compounds [0243 ] Two preferred embodiments comprise the first may comprise at least one of a LiNH2, Li ,NH , and LizN . reaction mixture of Na and R - Ni comprising about 0.5 wt The reaction mixture may further comprise a source of % NaOH wherein Na serves as the reductant and a second hydrogen such as Hz. In embodiments , the reaction of reaction mixture of R - Ni comprising about 0.5 wt % NaOH sodium hydroxide and lithium amide to form NaH and wherein intermetallic Al serves as the reductant. The reac lithium hydroxide is tion mixture may be regenerated by adding NaOH and NaH NaOH + LiNH2 LiOH + NaH + 1 /2N2 + LiH ( 110 ) that may serve as an H source and a reductant. [ 0244 ] In an embodiment, of the energy reactor, the source [0248 ] The reaction of sodium hydroxide and lithium of NaH such as NaOH is regenerated by addition of a source imide to form NaH and lithium hydroxide is of hydrogen such as at least one of a hydride and hydrogen ( 111) gas and a dissociator. The hydride and dissociator may be NaOH + LizNHnLi2O + NaH + 1 /2N2 + 1 /2H2 hydrided R -Ni . In another embodiment, the source of NaH And , the reaction of sodium hydroxide and lithium nitride to such as NaOH -doped R - Ni is regenerated by at least one of form NaH and lithium oxide is rehydriding , addition of Nah , and addition of NaOH wherein the addition may be by physicalmixing . Themixing NaOH + LizN > Li2O + NaH + 1 / 2Nz + Li ( 112 ) may be performed mechanically by means such as by ball milling . Alkaline Earth Hydroxide Catalyst Reactions to Form NaH [ 0245 ] In an embodiment, the reaction mixture further Catalyst comprises oxide- forming reactants that react with NaOH or Na2O to form a very stable oxide and NaH . Such reactants [ 0249 ] In an embodiment, a source of H is provided to a comprises a cerium , magnesium , lanthanide , titanium , or source of Na to form the catalyst NaH . The Na source may aluminum or their compounds such as AIX , MgX , LaXz, be the metal. The source of H may be a hydroxide . The CeXz, and TiX , where X is a halide, preferably Br or I and hydroxide may be at least one of alkali, alkaline earth a reducing compound such as an alkali or alkaline earth hydroxide , a transition metal hydroxide, and Al( OH ) 3 . In an metal . In an embodiment, the source of NaH catalyst com embodiment, Na reacts with a hydroxide to form the corre prises R -Ni comprising a sodium compound such as NaOH sponding oxide and NaH catalyst. In an embodiment on its surface . Then , the reaction of NaOH with the oxide wherein the hydroxide is Mg( OH )2 , the product is Mgo . In forming reactants such as AlXz, MgX2, LaXz, CeXz , and an embodiment wherein the hydroxide is Ca (OH ) 2, the TiX , and alkalimetal M forms NaH , MX , and Al2O3, MgO , product is CaO . Alkaline earth oxides may be reacted with La , 03, Ce , O3, and Ti 03, respectively . water to regenerate the hydroxide as given in Cotton [48 ] . [ 0246 ] In an embodiment, the reaction mixture comprises The hydroxide can be collected as a precipitate by means NaOH doped R -Ni and an alkaline or alkaline earth metal such as filtration and centrifugation . US 2019/0389723 A1 Dec. 26 , 2019 32

[0250 ] For example , in an embodiment , the reaction to In an embodiment , this reaction is reversible . The reaction form NaH catalyst and regeneration cycle for Mg( OH ) 2 , are can be driven to form NaH by increasing the H , concentra given by the reactions : tion . Alternatively , the forward reaction can be driven via the formation of atomic H using a dissociator. The reaction is 3Na +Mg ( OH ) 2 -> 2NaH +MgO + Na20 (113 ) given by MgO + H20Mg( OH ) 2 ( 114 ) 2H + NaNH2NH3 + NaH ( 122) [0251 ] In an embodiment , the reaction to form NaH cata The exothermic reaction can drive the formation of NaH ( g ) . lyst and regeneration cycle for Ca (OH ) 2, are given by the [0257 ] In an embodiment, NaH catalyst is generated from reactions : a reaction of NaNH , and hydrogen , preferably atomic 4Na + Ca (OH ) 2 ? 2NaH + CaO + Na O ( 115 ) hydrogen as given in reaction Eqs . (121-122 ) . The ratios of reactants may be any desired amount . Preferably the ratios CaO + H2O + Ca ( 116 ) are about stoichiometric to those of Eqs . (121-122 ). The reactions to form catalyst are reversible with the addition of Na/ N Alloy Reactions to Form NaH Catalyst a source of H such as H gas or a hydride to replace that reacted to form hydrinos wherein the catalyst reactions are [ 0252 ] Sodium in the solid and liquid states is a metal, and given by Eqs. (88-95 ), and sodium amide forms with addi the gas comprises covalent Na , molecules . In order to generate NaH catalyst , the reaction mixture of the solid fuel tional NaH catalyst by the reaction of ammonia with Na: comprises NaN alloy reactants . In an embodiment, the NH3 + Na ? NaNH2+ NaH ( 123 ) reaction mixture , solid - fuel reactions , and regeneration reac [0258 ] In an embodiment, a HSA material is doped with tions comprise those of the Li/ N system wherein Na replaces NaNH2. The doped HSA material is reacted with a reagent Li and the catalyst is molecular NaH except that the solid that will displace the amide group to form at least one of Na fuel reaction generates molecular NaH rather than atomic Li and NaH . In an embodiment, the reactant is an alkali or and H. In an embodiment, the reaction mixture comprises alkaline earth metal , preferably Li. In another embodiment, one or more compounds that react with a source of NaH to the reactant is an alkaline or alkaline earth hydride, prefer form NaH catalyst . The reaction mixture may comprise at ably LiH . The reactant may be both an alkali metal and an least one of the group of Na, NaH , NaNH2, Na NH , NazN , alkaline earth hydride . A source of H such as H? gas may be NH3, a dissociator, a hydrogen source such as H2 gas or a further provided in addition to that provided by any other hydride, a support , and a getter such as NaX ( X is a halide ). reagent of the reaction mixture such as a hydride, HSA The dissociator is preferably Pt, Ru , or Pd/ A1203 powder. material , and displacing reagent. For high - temperature operation , the dissociator may com In an embodiment, sodium amide undergoes reaction with prise Pt or Pd on a high surface area support suitably inert lithium to form lithium amide , imide, or nitride and Na or to Na . The dissociator may be Pt or Pd on carbon or NaH catalyst. The reaction of sodium amide and lithium to Pd / A1,03. The latter support may comprise a protective form lithium imide and NaH is surface coating of a material such as NaA102. The reactants may be present in any wt % . 2Li+ NaNH2 > Li2NH + (124 ) [ 0253 ] A preferred embodiment comprises the reaction The reaction of sodium amide and lithium hydride to form mixture of Na or NaH , NaNH2, and Pd on A1,03 powder lithium amide and NaH is wherein the reaction mixture may be regenerated by addition of H2 LiH + NaNH2 ? LINH2+ NaH ( 125 ) [0254 ] In an embodiment, NaNH , is added to the reaction The reaction of sodium amide, lithium , and hydrogen to mixture. NaNH , generates NaH according to the reversible form lithium amide and NaH is reactions Li + 1 / 2HP + NaNH) * LINH , + NaH ( 126 ) Na2 + NaNH > NaH + NaNH ( 117 ) In an embodiment, the reaction of themixture forms Na , and and the reactants further comprise a source of H that reacts with Na to form catalyst NaH by a reaction such as the following : 2NaH +NaNH2 > NaH ( g ) + Na NH + H2 ( 118 ) Li + NaNH2 to LiNH + Na ( 127) [ 0255 ] In the hydrino reaction cycle, Na - Na and NaNH2 react to form NaH molecule and Na NH , and the NaH forms and hydrino and Na. Thus, the reaction is reversible according to the reactions : Na + H to NaH (128 ) Na NH + H2 > NaNH + NaH ( 119 ) LiH + NaNH , to LINH2 + NaH ( 129) In an embodiment, the reactants comprise NaNH2, a reactant and to displace the amide group of NaNH , such as an alkali or Na?NH + Na + H?NaNH + Na2 ( 120 ) alkaline earth metal, preferably Li, and may additionally comprise a source of H such as at least one of MH ( M = Li, [0256 ] In an embodiment , NaH of Eq. ( 119 ) is molecular Na, K , Rb, Cs, Mg, Ca , Sr, and Ba) , H2 and a hydrogen such that this reaction is another to generate the catalyst . dissociator, and a hydride. The reaction of sodium amide and hydrogen to form ammo [0259 ] The reagents of the reaction mixture such as M , nia and sodium hydride is MH , NaH , NaNH2, HSA material, hydride, and the disso H2 + NaNH2 > NH + NaH ( 121 ) ciator are in any desired molar ratio . Each of M , MH , US 2019/0389723 A1 Dec. 26 , 2019 33

NaNH2, and the dissociator are in molar ratios of greater pressure ranges and durations which achieve the selectivity than 0 and less than 100 % , preferably the molar ratios are based on differential kinetics. similar. [0264 ] In an embodiment having powder reactants such as [0260 ) Other embodiments of systems to generate molecu a powder source of catalyst and a reductant, the reductant lar catalyst NaH involve Na and NaBH4 or NH_X ( X is an powder is mixed with the catalyst - source powder. For anion such as halide) . Molecular NaH catalyst can be example , NaOH -doped R - Ni that provides NaH catalyst is generated by reaction of Na , and NaBH ,: mixed with a metal or metal hydride powder such as a lanthanide or NaH , respectively . In an embodiment of the Naz + NaBH4 to NaBHz+ Na + NaH ( 130 ) reaction mixture having a solid material such as a dissocia NH_X can generate NaNH , and H2 tor , support , or HSA material that is doped or coated with at least one other species of the reaction mixture , the mixing Naz + NH4X to NaX + NaNH2 + H2 (131 ) may be achieved by ball milling or the method of incipient [0261 ] Then , NaH catalyst can be generated according to wetness. In an embodiment, the surface may be coated by the reaction of Eqs. ( 117-129 ). In another embodiment, the immersing the surface into a solution of the species such as reaction mechanism for the Na/ N system to form hydrino NaOH or NaX ( X is a counter anion such as halide ) followed catalyst NaH is by drying . Alternatively , NaOH may be incorporated into Ni/ Al alloy or R - Ni by etching with concentrated NaOH NH4X + Na -Na to NaH + NH3 + NaX ( 132 ) (deoxygenated ) using the same procedure as used to etch R - Ni as is well known in the Art [49 ] . In an embodiment , the Preparation and Regeneration of NH Catalyst Reactants HSA material such as R - Ni doped with a species such as NaOH is reacted with a reductant such as Na to form NaH [0262 ] In an embodiment NaH molecules or Na and catalyst that reacts to form hydrinos. Then , the excess hydrided R -Ni can be regenerated by systems and methods reductant such as Na may be removed from the products by after those disclosed for the Li- based reactant systems. In an evaporation , preferably, under vacuum at elevated tempera embodiment, Na can be regenerated from solid NaH by ture . The reductant may be condensed to be recycled . In evacuating H , released from NaH . The plateau temperature another embodiment, at least one of the reductant and a at about 1 Torr for NaH decomposition is about 500 ° C. NaH product species is removed by using a transporting medium can be decomposed at about 1 Torr and 500 ° C., below the such as a gas or liquid such as a solvent, and the removed alloy - formation and sintering temperatures of R -Ni . The species is isolated from the transporting medium . The spe molten Na can be separated from R -Ni , the R -Ni may be cies can be isolated by means well known in the Art such as rehydrided , and Na and hydrided R -Ni can be returned to precipitation , filtration , or centrifugation . The species may another reaction cycle . In the case of vapor- deposited Na on be recycled directly or further reacted to a chemical form a hydride surface, regeneration can be achieved by heating suitable for recycling . In addition , the NaOH may be regen with pumping to remove Na, the hydride can be rehydrided erated by H reduction or by reaction with a water- vapor gas by introducing H2, and Na atoms can be redeposited onto the stream . In the former case, excess Na may be removed by regenerated hydride after the cell is evacuated in an embodi evaporation , preferably, under vacuum at elevated tempera ment . ture . Alternatively , the reaction products can be removed by [ 0263 ] In a preferred embodiment, the competing kinetics rinsing with a suitable solvent such as water, the HSA of the hydriding or dehydriding of one reactant over another material may be dried , and the initial reactants may be is exploited to achieve a reaction mixture comprising added . Separately , the products may be regenerated to the hydrided and non -hydrided compounds. For example , the original reactants by methods known to those skilled in the formation of NaH solid is thermodynamically favored over Art . Or, a reaction product such as NaOH separated by the formation of R - Ni hydride . However, the rate of NaH rinsing R -Ni can be used in the process of etching R - Ni to formation at low temperature such as the range ofabout 25 ° regenerate it. In an embodiment comprising a reactant that C.- 100 ° C. is low ; whereas, the formation of R -Ni hydride reacts with the HSA material , the product such as an oxide proceeds at a high rate in this temperature range at modest may be treated with a solvent such as dilute acid to remove pressures such as the range of about 100 Torr to 3000 Torr . the product. The HSA material may then be re -doped and Thus, the reaction mixture of Na and hydrided R -Ni can be reused while the removed product may be regenerated by regenerated from NaH solid and R - Ni by pumping at about known methods . 400-500 ° C. to dehydride NaH , cooling the vessel to about [0265 ] The reductant such as an alkali metal can be 25-100 ° C., adding hydrogen to preferentially hydride R - Ni regenerated from the product comprising a corresponding for a duration that achieves the desired selectivity , and then compound , preferably NaOH or Nazo , using methods and removing the excess hydrogen by evacuating the cell. While systems known to those skilled in the Art as given in Cotton excess Na is present or is added to be in excess , the R - Ni can [48 ]. One method comprises electrolysis in a mixture such be used in repeated cycles by selectively hydriding alone . as a eutectic mixture . In a further embodiment, the reductant This can be achieved by adding hydrogen in the temperature product may comprise at least some oxide such as a lan and pressure ranges that achieve the selective hydriding of thanide metal oxide ( e.g. La203) . The hydroxide or oxide R -Ni and then by removing the excess hydrogen before the may be dissolved in a weak acid such as hydrochloric acid vessel is heated to initiate the reactions that form atomic H to form the corresponding salt such as NaCl or LaC1z . The and molecular NaH and the subsequent reaction to yield H treatment with acid may be a gas phase reaction . The gases states given by Eq. (1 ). Alternatively , a reaction mixture may be streaming at low pressure. The salt may be treated comprising Na and a hydrogen source such as R - Nimay be with a product reductant such as an alkali or alkaline earth hydrogenated to form the hydrides , and the NaH solid can be metal to form the original reductant. In an embodiment, the selectively dehydrided by pumping at the temperature and second reductant is an alkaline earth metal, preferably Ca US 2019/0389723 A1 Dec. 26 , 2019 34 wherein NaCl or LaClz is reduced to Na or La metal. ment, the NaOH solution is oxygen free . The molarity is in Methods known to those skilled in the Art are given in the range of about 1 to 10 M , preferably in the range of about Cotton [48 ] which is herein incorporated by reference in its 5 to 8 M , and most preferably about 7 M.In an embodiment, entirety . The additional product of CaCl2 is recovered and the alloy is reacted with the NaOH for about 2 hours at about recycled as well. In alternative embodiment, the oxide is 50 ° C. The solution is then diluted with water such as reduced with H2 at high temperature . deionized water until Al( OH ) 3 precipitate forms. In that [ 0266 ] In an embodiment wherein NaAlH4 is the reduc case, the amphoteric reaction of NaOH with Al( OH ) 3 to tant, the product comprises Na and Al that need not be form water- soluble Na [Al ( OH ) 4 ] is at least partially pre separated from the R -Ni product. The R - Ni is regenerated as vented such that NaOH is incorporated into the R - Ni. The a source of catalyst without separation . Regeneration may be incorporation may be achieved by drying the R - Ni without by the addition of NaOH . The NaOH may partially etch Al decanting. The pH of the diluted solution may be in the of R - Ni [49 ] which is dried [50 ] for reuse . Alternatively , Na range of 8 to 14 , preferably in the range of 9 to 12 , and most and Al are reacted insitu or separated from the reaction preferably about 10-11. Argon may be bubbled through the product mixture and reacted with H , to form NaAlH4 solution for about 12 hours , and then the solution may be directly as given by Cotton [51 ] or by reaction of the dried . recovered NaH with Al to form NaAlH4. [0270 ] Following the reaction of the reductant and source [0267 ] R - Ni is a preferred HSA material having NaOH as of catalyst to form hydrino ( H with states given by Eq . ( 1 )) , a source of NaH catalyst . In an embodiment, the Na content the reductant and catalyst source are regenerated . In an from the manufacturer is in the range of about 0.01 mg to embodiment, the reaction products are separated . The reduc 100 mg per gram of R -Ni , preferably in the range of about tantproduct may be separated from the product of the source 0.1 mg to 10 mg per gram of R -Ni , and most preferably in of catalyst. In an embodiment wherein at least one of the the range of about 1 mg to 10 mg Na per gram of R -Ni . The reductant and source of catalyst are powders , the products R - Ni or an alloy of Nimay further comprise promoters such are separated mechanically based on at least one of particle as at least one of Zn , Mo, Fe, and Cr. The R -Ni or alloy may size , shape, weight, density , magnetism , or dielectric con be at least one of W. R. Grace Davidson Raney 2400 , Raney stant. Particles having a significant difference in size and 2800 , Raney 2813 , Raney 3201 , and Raney 4200 , preferably shape can be mechanically separated using sieves. Particles 2400 , or etched or Na -doped embodiments of these mate with large differences in density can be separated by buoy rials . The NaOH content of the R -Ni may be increased by a ancy differences . Particles having large differences in mag factor in the range of about 1.01 to 1000 times . Solid NaOH netic susceptibility can be separated magnetically . Particles may added by mixing by means such as ball milling , or it with large differences in dielectric constant can be separated may be dissolved in a solution to achieve a desired concen electrostatically . In an embodiment, the products are ground tration or pH . The solution may be added to R -Ni and the to reverse any sintering . The grinding may be with a ball water evaporated to achieve the doping. The doping may be mill . in the range of about 0.1 ug to 100 mg per gram of R - Ni, [0271 ] Methods known by those skilled in the Art that can preferably in the range of about 1 ug to 100 ug per gram of be applied to the separations of the present Invention by R - Ni, and most preferably in the range of about 5 ug to 50 application of routine experimentation . In general, mechani ug per gram of R -Ni . In an embodiment, 0.1 g of NaOH is cal separations can be divided into four groups: sedimenta dissolved in 100 ml of distilled water and 10 ml of the NaOH tion , centrifugal separation , filtration , and sieving as solution is added to 500 g of non - decanted R -Ni from W. R. described in Earle [ 52 ] which is incorporated herein in its Grace Chemical Company such lot # 2800 /05310 having an entirety by reference. In a preferred embodiment, the sepa initial total content of Na of about 0.1 wt % . The mixture is ration of the particles is achieved by at least one of sieving then dried . The drying may be achieved by heating at 50 ° C. and use of classifiers. The size and shape of the particle may under vacuum for 65 hours . In another embodiment, the be selected in the starting materials to achieve the desired doping may be achieved by ball milling NaOH with the R - Ni separation of the products . such as about 1 to 10 mg of NaOH per gram of R -Ni . [0272 ] In a further embodiment, the reductant is a powder [0268 ] The R -Ni may be dried dry according to the or is converted to a powder andmechanically separated from standard R - Ni drying procedure [50 ] . The R -Ni may be the other components of the product reaction mixture such decanted and dried in the temperature range of about as a HSA material. In embodiments , Na, NaH , and a 10-500 ° C. under vacuum , preferably , it is dried at 50 ° C. lanthanide comprise at least one of the reductant and a The duration may be in the range of about 1 hr to 200 hours , source of the reductant , and a HSA material component is preferably , the duration is about 65 hours . In an embodi R -Ni . The reductant product may be separated from the ment, the H content of the dried R -Ni is in the range of about product mixture by converting any unreacted non - powder 1 ml- 100 ml H / g R - Ni, preferably the H content of the dried reductant metal to the hydride. The hydride may be formed R -Ni is in the range of about 10-50 ml H / g R -Ni (where ml by the addition of hydrogen . The metal hydride may be gas are at STP ) . The drying temperature , time , vacuum ground to form a powder. The powder may then be separated pressure and flow of gases, if any, such as He, Ar, or H2 from the other products such as that of the source of the during and after drying is controlled to achieve dryness and catalyst based on a difference in the size of the particles . The the desired H content. separation may be by agitating the mixture over a series of [ 0269 ] In an embodiment of the R - Nidoped with a source sieves that are selective for certain size ranges to cause the of NaH catalyst such as NaOH , the preparation of R -Ni from separation . Alternatively , or in combination with sieving , the Ni/ Al alloy comprises the step of etching the alloy with R -Ni particles are separated from themetal hydride or metal aqueous NaOH solution . The concentration of NaOH , etch particles based on the large magnetic susceptibility differ ing times, and rinsing exchanges , may be varied to achieve ence between the particles. The reduced R -Ni product may the desired level of incorporation of NaOH . In an embodi be magnetic . The unreacted lanthanide metal and hydrided US 2019/0389723 A1 Dec. 26 , 2019 35 metal and any oxide such as La 03 are weakly paramagnetic distillation , transport, gas -stream process , or related pro and diamagnetic , respectively . The product mixture may be cesses of the reactants may further comprise a carrier gas. agitated over a series of strong magnets alone or in combi The carrier gas may be an inert gas such as a noble gas . nation with one or more sieves to cause the separation based Further steps may comprise mechanical mixing or separa on at least one of the stronger adherence or attraction of the tion . For example , NaOH and NaH can be also be deposited R - Ni product particles to themagnet and a size difference of or removed mechanically by methods such as ball milling the two classes of particles . In an embodiment of the use of and sieving , respectively . sieves and an applied magnetic field , the latter adds an [0274 ] In the case that the redundant is an element other additional force to that of gravity to draw the smaller R -Ni than a desired first element such as Na, the other element product particles through the sieve while the weakly para may be replaced by a second such as Na using methods magnetic or diamagnetic particles of the reductant product known in the Art. A step may comprise evaporation of are retained on the sieve due to their larger size . The alkali excess reductant . The large surface - area material such as metal may be recovered from the corresponding hydride by R -Ni may be etched . The etching may be with a base , heating and optionally by applying vacuum . The evolved preferably NaOH . The etched productmay be decanted with hydrogen can be reacted with alkali metal in another batch substantially all of any solvent such as water removed of a repetitive reaction - regeneration cycle . There may be mechanically such as by decanting and possibly centrifuga more than one batch in the cycle at various stages. The tion . The etched R -Ni may be dried under vacuum and hydride and any other compound ( s ) may be separated , and recycled . then reacted to form the metal separately from the formation of the metal from the hydride . Additional MH - Type Catalysts and Reactions [0273 ] In an embodiment, the reaction mixture is regen erated by vapor deposition techniques , preferably in the case [0275 ] Another catalytic system of the type MH involves that the reactants are on the surface of a HSA material such aluminum . The bond energy of AlH is 2.98 eV [44 ]. The first as R - Ni. In further embodiments , having other coated and second ionization energies of Al are 5.985768 eV and desired reactants comprising at least one of a source of NaH 18.82855 eV , respectively [ 1 ]. Based on these energies AIH catalyst on a surface and a material that supports the molecule can serve as a catalyst and H source since the bond formation of NaH catalyst such as a HSA material , the energy of AIH plus the double ionization ( t = 2 ) of Al to A12 + , reactants are provided by reacting gas streams with the HSA is 27.79 eV (27.2 eV ) which is equivalent to in = 1 in Eq. ( 2 ) . material such as R -Ni . The deposited reactants may com The catalyst reactions are given by prise at least one of the group NaH , Na20 , NaOH , A1, Ni, Nio , NaAl( OH ) 4 , B - alumina , Na20.nAl2O3 ( n = integer from 1 to 1000 , preferably 11) , Al( OH ) 3 , and A1,0 , in alpha, 27.79 eV + AIH ? A12 + + 2e ++ H[ % ]+ [ (2 ) 2 – 12) .13.6 ev ( 133 ) beta , and gamma forms. Vapor - deposited elements , com pounds, intermediates, and species that are the desired A12 + + 2e + H ? AIH + 27.79 eV (134 ) reactants or are converted into the desired reactants as well as the sequence and composition of the gas streams and the chemistry to form the reactants from the gas streams are well And , the overall reaction is by those skilled in the Art of vapor deposition . For example , H ? H ?? ( 135 ) alkalimetals can be directly vapor deposited and any metals H ]+ [( 2 ) 2 – 12 ] . 13.6 eV with low vapor pressure such as Al can be vapor deposited from the gaseous halide or hydride. Furthermore , oxide products such as Na20 may be reacted with a source of [0276 ] In an embodiment, the reaction mixture comprises hydrogen to form the hydroxide such as NaOH . The source at least one of AlH molecules and a source of AlH mol of hydrogen may comprise a water - vapor gas stream to ecules . A source of AlH molecules may comprise Almetal regenerate NaOH . Alternatively, the NaOH can be formed and a source of hydrogen , preferably atomic hydrogen . The using H , or a source of H2. In addition , the hydriding of the source of hydrogen may be a hydride, preferably R -Ni . In HSA material such as R -Ni can be achieved by supplying another embodiment, the catalyst AIH is generated by the hydrogen gas, and removing excess hydrogen by means reaction of an oxide or hydroxide of Al with a reductant. The such as pumping . The NaOH may be regenerated stoichio reductant comprises at least one of the NaOH reductants metrically by precisely controlling the total moles of reacted given previously . In an embodiment, a source of H is H from a source such as water vapor or hydrogen gas. Any provided to a source of Al to form the catalyst AIH . The Al additional Na or NaH formed at this stage may be removed source may be the metal . The source of H may be a by evaporation , and decomposition and evaporation , respec hydroxide . The hydroxide may be at least one of alkali , tively . Alternative , an oxide or hydroxide product such as alkaline earth hydroxide , a transition metal hydroxide , and Na2O or excess NaOH can be removed . This can be Al( OH ) achieved by conversion to a halide such as Nal which may [0277 ] Raney nickel can be prepared by the following two be removed by distillation or vaporization . The vaporization reaction steps: can be achieved with heating and by maintaining a vacuum at elevated temperature . The conversion to a halide may be Ni + 3Al ? NiAlz (or Ni2Al3 ) ( 136 ) achieved by reaction with an acid such as HI. The treatment may be by a gas stream comprising the acid gas . In another NiAl (skeleton , porous Ni) + (137 ) embodiment, any excess NaOH is removed by sublimation . NiAls + 2NaOH + 6H30 - ( 2Na[ Al( OH ) 4 ] + 3H2 This occurs under vacuum in the temperature range of 350-400 ° C. as given by Cotton [53 ] . Any evaporation , US 2019/0389723 A1 Dec. 26 , 2019 36

Na[ Al( OH ) 4 ] is readily dissolved in concentrated NaOH . It ments , AiH molecules or Al and hydrided R - Ni can be can be washed in de -oxygenated water. The prepared Ni regenerated by systems and methods after those disclosed contains Al ( ~ 10 wt % , that may vary ) , is porous, and has a for the other reactant systems. large surface area . It contains large amounts of H , both in the [0282 ] Another catalytic system of the type MH involves Ni lattice and in the form of Ni- A1H , ( x = 1 , 2 , 3 ) . chlorine . The bond energy of HCl is 4.4703 eV [44 ] . The [0278 ] R - Nimay be reacted with another element to cause first, second , and third ionization energies of Cl are the chemical release of AIH molecules which then undergo 12.96764 eV , 23.814 eV , and 39.61 eV , respectively [ 1 ] . catalysis according to reactions given by Eqs . (133-135 ) . In Based on these energies HCl can serve as a catalyst and H an embodiment, the AIH release is caused by a reduction source since the bond energy of HCl plus the triple ioniza reaction , etching , or alloy formation . One such other ele tion ( t = 3 ) of Cl to C13 + , is 80.86 eV ( 3.27.2 eV ) which is ment M is an alkali or alkaline earth metal which reacts with equivalent to m = 3 in Eq . ( 2 ) . The catalyst reactions are given the Ni portion of R -Ni to cause the AIH , component to by release A1H molecules that subsequently under go catalysis . In an embodiment, M may react with Al hydroxides or ?? oxides to form Almetal that may further react with H to form 80.86 eV + HCl ? Cl3+ + 3 + H ( 138 ) AIH . The reaction can be initiated by heating , and the rate )+ ( ( 4 ) 2 – 1? ) . 13.6ev may be controlled by controlling the temperature. M ( alkali C13 + + 3e + H ? HC1 + 80.86 eV (139 ) or alkaline earth metal) and R - Ni are in any desired molar ratio . Each of M and R -Ni are in molar ratios of greater than O and less than 100 % . Preferably the molar ratio of M and And , the overall reaction is R -Ni are similar.

[ 0279 ] In an embodiment, Al atoms are vapor deposited on ?? a surface . The surface may support or be a source of H atoms H ? H + [ (4 )2 – 12 ] . 13.6 eV ( 140 ) to form AlH molecules . The surface may comprise at least ( 4 ) one of a hydride and hydrogen dissociator. The surface may be R - Ni which may be hydrided . The vapor deposition may [0283 ] In an embodiment , the reaction mixture comprises be from a reservoir containing a source of Al atoms. The Al HCl or a source of HCl. A source may be NH4Cl or a solid source may be controlled by heating . One source that acid and a chloride such as an alkali or alkaline earth provides Al atomswhen heated is Almetal . The surface may chloride. The solid acid may be at least one of MHSO4, be maintained at a low temperature such as room tempera MHCO3, MH ,PO4 , and MHPO4 wherein M is a cation such ture during the vapor deposition . The Al- coated surface may as an alkali or alkaline earth cation . Other such solid acids be heated to cause the reaction of Al and H to form AIH and are known to those skilled in the Art . In an embodiment, the may further cause the AlH molecules to react to form H reactants comprise HCl catalyst in an ionic lattice such as states given by Eq. ( 1 ) . Other thin - film deposition tech HC1 in an alkali or alkaline earth halide, preferably a niques that are well known in the ART to form layers of at chloride. In an embodiment, the reaction mixture comprises least one of Al and other elements such as metals comprise a strong acid such as H2SO4 and an ionic compound such as further embodiments of the Invention . Such embodiments NaCl. The reaction of the acid with the ionic compound such comprise physical spray , electro - spray, aerosol, electro - arch as NaCl generates HCl in the crystalline lattice to serve as ing, Knudsen cell controlled release , dispenser- cathode a hydrino catalyst and H source. injection , plasma- deposition , sputtering, and further coating [ 0284 ] In general , MH type hydrogen catalysts to produce methods and systems such as melting a fine dispersion of Al, hydrinos provided by the breakage of the M - H bond plus the electroplating Al, and chemical deposition of Al. ionization of t electrons from the atom M each to a con [0280 ] In an embodiment, the source of AlH comprises tinuum energy level such that the sum of the bond energy R -Ni and other Raney metals or alloys of Al known in the and ionization energies of the t electrons is approximately Art such as R -Ni or an alloy comprising at least one of Ni, m.27.2 eV where m is an integer are given in TABLE 2 . Cu , Si, Fe , Ru , Co , Pd , Pt, and other elements and com Each MH catalyst is given in the first column and the pounds. The R -Ni or alloy may further comprise promoters corresponding M - H bond energy is given in column two . such as at least one of Zn , Mo , Fe, and Cr. The R -Ni may be The atom M of the MH species given in the first column is at least one of W. R. Grace Raney 2400 , Raney 2800 , Raney ionized to provide the net enthalpy of reaction of m.27.2 eV 2813 , Raney 3201, Raney 4200 , or an etched or Na doped with the addition of the bond energy in column two . The embodiment of these materials . In another embodiment of enthalpy of the catalyst is given in the eighth column where the AlH catalyst system , the source of catalyst comprises a m is given in the ninth column. The electrons , that partici Ni/ Al alloy wherein the Al to Niratio is in the range of about pate in ionization are given with the ionization potential 10-90 % , preferably about 10-50 % , and more preferably ( also called ionization energy or binding energy ) . For about 10-30 % . The source of catalyst may comprise palla example , the bond energy of NaH , 1.9245 eV [44 ] , is given dium or platinum and further comprise Al as a Raney metal. in column two . The ionization potential of the nth electron [ 0281 ] The source of AlH may further comprise A1Hz. The of the atom or ion is designated by IP , and is given by the AIHzmay be deposited on or with Nito form a NiAlH , alloy . CRC [ 1 ] . That is for example , Na+ 5.13908 eV Na ++ e- and The alloy may be activated by the addition of a metal such Na * + 47.2864 eV > Na2++ e ”. The first ionization potential , as an alkali or alkaline earth metal. In an embodiment the IP 1 = 5.13908 eV , and the second ionization potential, reaction mixture comprises AIHz, R -Ni , and a metal such as IP2 = 47.2864 eV, are given in the second and third columns , an alkali metal. The metal may be supplied by vaporization respectively . The net enthalpy of reaction for the breakage of from a reservoir or by gravity feed from a source that flows the NaH bond and the double ionization of Na is 54.35 eV down on the R - Ni at an elevated temperature . In an embodi as given in the eighth column , and m = 2 in Eq . ( 2 ) as given US 2019/0389723 A1 Dec. 26 , 2019 37

in the ninth column. Additionally , H can react with each of about 500 Torr to 2 atm . In other embodiments , the source the MH molecules given in TABLE 2 to form a hydrino of hydrogen is from a hydride such as an alkali or alkaline having a quantum number p increased by one (Eq . ( 1 ) ) earth metal hydride or a transition metal hydride. relative to the catalyst reaction product ofMH alone as given [0289 ] Atomic hydrogen in high density can undergo by exemplary Eq. (92 ) . three -body -collision reactions to form hydrinos wherein one TABLE 2 MH type hydrogen catalysts capable of providing a net enthalpy of reaction of approximately m : 27.2 eV. M - H Bond Catalyst Energy IP 1 IP2 IP3 IP4 IPS Enthalpy m ??? 2.98 5.985768 18.82855 27.79 BiH 2.936 7.2855 16.703 26.92 1 CIH 4.4703 12.96763 23.8136 39.61 80.86 ??? ??? 2.538 7.88101 17.084 27.50 1 GeH 2.728 7.89943 15.93461 26.56 1 InH 2.520 5.78636 18.8703 27.18 1 NaH 1.925 5.139076 47.2864 54.35 2 RuH 2.311 7.36050 16.76 26.43 1 SbH 2.484 8.60839 16.63 27.72 1 SeH 3.239 9.75239 21.19 30.8204 42.9450 107.95 4 SiH 3.040 8.15168 16.34584 27.54 1 SnH 2.736 7.34392 14.6322 30.50260 55.21 2

[ 0285 ] In other embodiments of the MH type catalyst, the H atom undergoes the transition to form states given by Eq . reactants comprise sources of SbH , SiH , SnH , and InH . In ( 1 ) when two additional H atoms ionize . The reaction are embodiments providing the catalyst MH , the sources com given by prise at least one of M and a source of H2 and MH , such as at least one of Sb , Si, Sn , and In and a source of H2, and SbH3, SiH4, SnH4 , and InHz. 27.21 eV + 2H [ah ] + H [ay ] ? ( 141) [ 0286 ] The reaction mixture may further comprise a 2H + + 2e + H ?? + [ (2 ) 2 – 121.13.6 eV source of H and a source of catalyst wherein the source of at least one of H and catalyst may be a solid acid or NH_X 2H + + 2e ? 2H [ an ] + 27.21 eV (142 ) where X is a halide , preferably Cl to form HCl catalyst. Preferably , the reaction mixture may comprise at least one of NH_X , a solid acid , Nax , LiX , KX , NaH , LiH , KH , Na, Li, And , the overall reaction is K , a support, a hydrogen dissociator and H , where X is a halide , preferably Cl. The solid acid may be NaHSO4, ?? (143 ) KHSO4, LiHSO4, NaHCO3, KHCO3, LiHCO3, Na2HPO4, ? [ ?? ] ? H +- [( 2 ) 2 – 12 ] 13.6 eV K HPO4, Li, HPO4 , NaH , PO4, KH PO4, and LiH , PO4. The Mel catalyst may be at least one of NaH , Li, K , and HCl. The reaction mixture may further comprise at least one of a In another embodiment, the reaction are given by dissociator and a support . [ 0287 ] Other thin - film deposition techniques that are well 54.4 eV + 2H [an ] + H [ah ] ? (144 ) known in the ART comprise further embodiments of the ?? Invention . Such embodiments comprise physical spray, elec 2H +fast + 2e + H + [ ( 3 ) 2 – 1 ? ] 13.6 eV tro -spray , aerosol, electro - arching , Knudsen cell controlled ( 3 ) release , dispenser- cathode injection , plasma- deposition , 21+ + 2e 2H [ ay ] + 54.4 eV (145 ) sputtering , and further coating methods and systems such as I fast melting a fine dispersion of M , electroplating M , and chemi cal deposition of M where MH comprises a catalyst. And , the overall reaction is [0288 ] In each case of a source of MH comprising an M alloy such as AlH and Al, respectively, the alloy may be hydrided with a source of H , such as H2 gas. H2 can be H [ an ] ? H ?? + [ ( 3 )2 – 12 ] - 13.6 eV ( 146 ) supplied to the alloy during the reaction , or H may be HD supplied to form the alloy of a desired H content with the H pressure changed during the reaction . In this case, the initial [0290 ] In an embodiment , the material that provides H H2 pressure may be about zero . The alloy may be activated atoms in high density is R -Ni . The atomic H may be from at by the addition of a metal such as an alkali or alkaline earth least one of the decomposition of H within R -Ni and the metal. For MH catalysts and sources of MH , the hydrogen dissociation of H , from an Hy source such as Hy gas supplied gas may be maintained in the range of about 1 Torr to 100 to the cell . R - Ni may be reacted with an alkali or alkaline atm , preferably about 100 Torr to 10 atm , more preferably earth metal M to enhance the production of layers of atomic US 2019/0389723 A1 Dec. 26 , 2019 38

H to cause the catalysis . R -Ni can be regenerated by [0304 ] 14. R.Mills , B. Dhandapani, M. Nansteel, J. He, T. evaporating the metal M followed by addition of hydrogen Shannon , A. Echezuria , “ Synthesis and Characterization to rehydride the R -Ni . of Novel Hydride Compounds” , Int. J. of Hydrogen Energy, Vol. 26 , No. 4 , ( 2001) , pp . 339-367. REFERENCES [0305 ] 15. R.Mills , B.Dhandapani , M.Nansteel , J. He, A. [0291 ] 1. D. R. Lide, CRC Handbook of Chemistry and Voigt, “ Identification of Compounds Containing Novel Physics, 78 th Edition , CRC Press, Boca Raton , Fla ., Hydride Ions by Nuclear Magnetic Resonance Spectros ( 1997 ), p . 10-214 to 10-216 ; hereafter referred to as copy ” , Int. J. Hydrogen Energy, Vol. 26 , No. 9 , ( 2001 ) , pp . " CRC ” . 965-979 . [ 0292 ] 2. R. L. Mills , “ The Nature of the Chemical Bond [0306 ] 16. R. Mills , B. Dhandapani, N. Greenig , J. He, Revisited and an Alternative Maxwellian Approach ” , “ Synthesis and Characterization of Potassium lodo Physics Essays , Vol. 17 , No. 3 , ( 2004 ), pp . 342-389 . Hydride ” , Int. J. of Hydrogen Energy , Vol. 25 , Issue 12 , Posted at http://www.blacklightpower.com/pdf/technical/ December, ( 2000 ), pp . 1185-1203 . H2Paper TableFiguresCaptions111303.pdfwhich is incor [0307 ] 17. R. L. Mills , Y. Lu , J. He, M. Nansteel, P. Ray , porated by reference . X. Chen , A. Voigt , B. Dhandapani, “ Spectral Identifica [ 0293] 3. R. Mills , P. Ray, B. Dhandapani, W. Good , P. tion of New States of Hydrogen ” , submitted . Jansson , M.Nansteel , J. He, A. Voigt, “ Spectroscopic and [0308 ] 18. R. L.Mills , P. Ray, “ Extreme Ultraviolet Spec NMR Identification of Novel Hydride Ions in Fractional troscopy of Helium -Hydrogen Plasma” , J. Phys. D , Quantum Energy States Formed by an Exothermic Reac Applied Physics , Vol. 36 , ( 2003 ) , pp . 1535-1542 . tion of Atomic Hydrogen with Certain Catalysts ” , Euro [0309 ] 19. R. L. Mills , P. Ray, B. Dhandapani, M. Nan pean Physical Journal -Applied Physics, Vol. 28 , (2004 ) , steel, X. Chen , J. He, “ New Power Source from Fractional pp. 83-104. Quantum Energy Levels of Atomic Hydrogen that Sur [0294 ] 4. R. Mills and M. Nansteel, P. Ray , “ Argon passes Internal Combustion ” , J Mol. Struct ., Vol. 643 , No. Hydrogen - Strontium Discharge Light Source " , IEEE 1-3 , (2002 ), pp . 43-54 . Transactions on Plasma Science , Vol. 30 , No. 2 , (2002 ) , [0310 ] 20. R. Mills , P. Ray, “ Spectral Emission of Frac pp . 639-653 . tional Quantum Energy Levels of Atomic Hydrogen from [0295 ] 5. R. Mills and M. Nansteel, P. Ray, “ Bright a Helium -Hydrogen Plasma and the Implications for Dark Hydrogen - Light Source due to a Resonant Energy Trans Matter” , Int. J. Hydrogen Energy, Vol. 27 , No. 3 , (2002 ) , fer with Strontium and Argon Ions” , New Journal of pp . 301-322. Physics, Vol. 4 , (2002 ), pp . 70.1-70.28 . [0311 ] 21. R. L.Mills , P.Ray , “ A Comprehensive Study of [0296 ] 6. R. Mills , J. Dong , Y. Lu , " Observation of Spectra of the Bound -Free Hyperfine Levels of Novel Extreme Ultraviolet Hydrogen Emission from Incandes Hydride Ion Hº( 1/2 ), Hydrogen , Nitrogen , and Air ” , Int. cently Heated Hydrogen Gas with Certain Catalysts ” , Int. J. Hydrogen Energy , Vol . 28 , No. 8 , ( 2003 ), pp. 825-871. J. Hydrogen Energy , Vol. 25, (2000 ), pp. 919-943 . [0312 ] 22. R. Mills , “ Spectroscopic Identification of a [ 0297 ] 7. R.Mills , M. Nansteel , and P. Ray, “ Excessively Novel Catalytic Reaction of Atomic Hydrogen and the Bright Hydrogen - Strontium Plasma Light Source Due to Hydride Ion Product" , Int. J. Hydrogen Energy , Vol 26 , Energy Resonance of Strontium with Hydrogen ” , J. of No. 10 , (2001 ) , pp . 1041-1058 . Plasma Physics, Vol . 69 , (2003 ) , pp . 131-158 . [0313 ] 23. R. L. Mills , P. Ray, B. Dhandapani, R. M. [ 0298 ] 8. H. Conrads, R.Mills , Th . Wrubel , “ Emission in Mayo , J. He, “ Comparison of Excessive Balmer a Line the Deep Vacuum Ultraviolet from a Plasma Formed by Broadening of Glow Discharge and Microwave Hydrogen Incandescently Heating Hydrogen Gas with Trace Plasmas with Certain Catalysts ” , J. of Applied Physics, Amounts of Potassium Carbonate” , Plasma Sources Sci Vol. 92 , No. 12 , ( 2002 ) , pp . 7008-7022 . ence and Technology, Vol. 12 , (3003 ), pp . 389-395 . [0314 ] 24. R. L. Mills , P. Ray , B. Dhandapani, J. He, [0299 ] 9. R. L.Mills , J. He, M. Nansteel, B. Dhandapani, “ Comparison of Excessive Balmer a Line Broadening of “ Catalysis of Atomic Hydrogen to New Hydrides as a Inductively and Capacitively Coupled RF, Microwave , New Power Source ” , submitted . and Glow Discharge Hydrogen Plasmas with Certain [0300 ] 10. R. L. Mills , M.Nansteel , J. He, B. Dhandapani, Catalysts ” , IEEE Transactions on Plasma Science, Vol. “ Low - Voltage EUV and Visible Light Source Due to 31, No. (2003 ), pp . 338-355 . Catalysis of Atomic Hydrogen ” , submitted . [0315 ] 25. R. L. Mills , P. Ray, “ Substantial Changes in the [0301 ] 11. J. Phillips , R. L. Mills , X. Chen , “ Water Bath Characteristics of a Microwave PlasmaDue to Combining calorimetric Study of Excess Heat in ‘Resonance Trans Argon and Hydrogen ” , New Journal of Physics , www . fer’ Plasmas” , Journal of Applied Physics , Vol. 96 , No. 6 , njp.org , Vol. 4 , ( 2002 ), pp . 22.1-22.17 . pp . 3095-3102 . [0316 ] 26. J. Phillips, C. Chen , “ Evidence of Energetic [0302 ] 12. R. L. Mills , X. Chen , P. Ray , J. He, B. Dhan Reaction Between Helium and Hydrogen Species in RF dapani, " Plasma Power Source Based on a Catalytic Generated Plasmas” , submitted . Reaction of Atomic Hydrogen Measured by Water Bath [0317 ] 27. R. Mills , P. Ray , R. M.Mayo , “ CW HI Laser calorimetry " , Thermochimica Acta , Vol. 406 / 1-2, ( 2003 ), Based on a Stationary Inverted Lyman Population Formed pp . 35-53 . from Incandescently Heated Hydrogen Gas with Certain [ 0303 ] 13. R. L.Mills , Y. Lu, M.Nansteel , J. He, A. Voigt, Group I Catalysts ” , IEEE Transactions on Plasma Sci B. Dhandapani, “ Energetic Catalyst -Hydrogen Plasma ence, Vol. 31 , No. 2 , (2003 ), pp . 236-247 . Reaction as a Potential New Energy Source ” , Division of [ 0318 ] 28. R. L.Mills , P.Ray , “ Stationary Inverted Lyman Fuel Chemistry , Session : Chemistry of Solid , Liquid , and Population Formed from Incandescently Heated Hydro Gaseous Fuels , 227th American Chemical Society gen Gas with Certain Catalysts ” , J. Phys. D , Applied National Meeting , Mar. 28 - Apr. 1 , 2004 , Anaheim , Calif . Physics, Vol. 36 , (2003 ) , pp . 1504-1509 . US 2019/0389723 A1 Dec. 26 , 2019 39

[0319 ] 29. R. Mills , P. Ray, R. M.Mayo , “ The Potential [0336 ] 46. F. A. Cotton , G. Wilkinson , C. A. Murillo , M. for a Hydrogen Water- Plasma Laser ” , Applied Physics Bochmann , Advanced Inorganic Chemistry , Sixth Edi Letters , Vol. 82 , No. 11 , ( 2003 ), pp . 1679-1681. tion , John Wiley & Sons, Inc., New York , ( 1999) , p . 95 . [0320 ] 30. R.Mills , The Grand Unified Theory of Clas [0337 ] 47. J - G . Gasser , B. Kefif, “ Electrical resistivity of sical Quantum Mechanics; October 2007 Edition , posted liquid nickel- lanthanum and nickel- cerium alloys” , Physi at http://www.blacklightpower.com/theory/bookdown cal Review B , Vol. 41, No. 5 , ( 1990 ) , pp . 2776-2783 . load.shtml. [0338 ] 48. F. A. Cotton , G. Wilkinson , C. A. Murillo , M. Bochmann , Advanced Inorganic Chemistry , Sixth Edi [0321 ] 31. N. V. Sidgwick , The Chemical Elements and tion , John Wiley & Sons, Inc. , New York , (1999 ) . Their Compounds, Volume I , Oxford , Clarendon Press, [0339 ] 49. V. R. Choudhary, S. K. Chaudhari , “ Leaching ( 1950 ) , p . 17 . of Raney Ni — Al alloy with alkali ; kinetics of hydrogen [0322 ] 32.M. D.Lamb , Luminescence Spectroscopy , Aca evolution ” , J. Chem . Tech . Biotech , Vol . 33a , (1983 ) , pp . demic Press, London , ( 1978 ), p . 68 . 339-349 . [0323 ] 33. R. L.Mills , “ The Nature of the Chemical Bond [0340 ] 50. R. R. Cavanagh , R. D. Kelley , J. J. Rush , Revisited and an Alternative Maxwellian Approach ” , sub “ Neutron vibrational spectroscopy of hydrogen and deu mitted ; posted at http: //www.blacklightpowercom/pdf/ terium on Raney nickel” , J. Chem . Phys ., Vol. 77 ( 3 ) , technical /H2Paper TableFiguresCaptions111303.pdf. ( 1982) , pp . 1540-1547. [0324 ] 34. H. Beutler, Z. Physical Chem ., “ Die dissozi [0341 ] 51. F. A. Cotton , G. Wilkinson , C. A. Murillo , M. ationswarme des Wasserstoffmolekuls H2, aus einem Bochmann , Advanced Inorganic Chemistry , Sixth Edi neuen ultravioletten resonanzbandenzug bestimmt” , Vol. tion , John Wiley & Sons, Inc. , New York , ( 1999 ), pp . 27B , ( 1934 ) , pp . 287-302 . 190-191 . [0325 ] 35.G. Herzberg , L. L. Howe , “ The Lyman bands of [0342 ] 52. R. L. Earle , M. D. Earle , Unit Operations in molecular hydrogen ” , Can . J. Phys. , Vol. 37 , ( 1959) , pp . Food Processing , The New Zealand Institute of Food 636-659 . Science & Technology ( Inc. ), Web Edition 2004 , avail [0326 ] 36. P. W. Atkins , Physical Chemistry , Second Edi able at http://www.nzifst.org.nz/unitoperations/ . tion , W. H. Freeman , San Francisco , ( 1982 ) , p . 589 . [0343 ] 53. F. A. Cotton , G. Wilkinson , C. A.Murillo , M. [ 0327] 37. M. Karplus , R. N. Porter, Atoms and Molecules Bochmann , Advanced Inorganic Chemistry , Sixth Edi an Introduction for Students of Physical Chemistry , The tion , John Wiley & Sons, Inc., New York , ( 1999 ) , p . 98 . Benjamin /Cummings Publishing Company, Menlo Park , Calif ., ( 1970 ) , pp . 447-484 . EXPERIMENTAL [ 0328 ] 38. K. R. Lykke , K.K. Murray, W. C. Lineberger, [0344 ] Equation numbers , section numbers , and reference “ Threshold photodetachment of H-” , Phys. Rev. A , Vol. numbers given hereafter in this Experimental section refer to 43 , No. 11, ( 1991 ) , pp . 6104-6107 . those given in this Experimental section of the Disclosure . [0329 ] 39. R. Mills , J. He, Z. Chang , W.Good , Y. Lu , B. Dhandapani, " Catalysis of Atomic Hydrogen to Novel Abstract Hydrogen Species H-( 1/4 ) and H2( 1/4 ) as a New Power [0345 ] The data from a broad spectrum of investigational Source” , Int. J. Hydrogen Energy, Vol. 32 , No. 12, (2007 ) , techniques strongly and consistently indicates that hydrogen pp . 2573-2584 . can exist in lower - energy states than previously thought [0330 ] 40. W. M. Mueller, J. P. Blackledge, and G. G. possible . The predicted reaction involves a resonant , non Libowitz . Metal Hydrides, Academic Press, New York , radiative energy transfer from otherwise stable atomic (1968 ), Hydrogen in Intermetallic Compounds 1, Edited hydrogen to a catalyst capable of accepting the energy . The by L. Schlapbach , Springer- Verlag , Berlin , and Hydrogen in Intermetallic Compounds II , Edited by L. Schlapbach , product is H ( 1 / p ) , fractional Rydberg states of atomic hydro Springer - Verlag , Berlin which is incorporate herein by gen called “ hydrino atoms” wherein reference . 1 [0331 ] 41. D. R. Lide, CRC Handbook of Chemistry and 1 = Physics, 86th Edition , CRC Press , Taylor & Francis , Boca 2 ' 3 ' 4 P Raton , ( 2005 Jun .) , pp . 4-45 to 4-97 which is herein incorporated by reference . (ps137 is an integer ) replaces the well - known parameter [ 0332 ] 42. W. I. F. David , M. O. Jones , D. H. Gregory , C. n = integer in the Rydberg equation for hydrogen excited M. Jewell , S. R. Johnson , A. Walton , P. Edwards, “ A states . Atomic lithium and molecular NaH served as cata Mechanism for Non - stoichiometry in the Lithium Amide / lysts since they meet the catalyst criterion a chemical or Lithium Imide Hydrogen Storage Reaction , ” J. Am . physical process with an enthalpy change equal to an integer Chem . Soc. , 129 , ( 2007 ) , 1594-1601 . multiple m of the potential energy of atomic hydrogen , 27.2 [ 0333 ] 43. F. A. Cotton , G. Wilkinson , Advanced Inor eV ( e.g. m = 3 for Li and m = 2 for Nah ) . Specific predictions ganic Chemistry , Interscience Publishers , New York , based on closed - form equations for energy levels of the ( 1972 ) . corresponding hydrino hydride ions H-( 1/4 ) of novel alkali [0334 ] 44. D. R. Lide , CRC Handbook of Chemistry and halido hydrino hydride compounds (MH * X ; M = Li or Na , Physics , 86th Edition , CRC Press , Taylor & Francis , Boca X = halide ) and dihydrino molecules H2( 1/4 ) were tested Raton , (2005 Jun . ) , pp . 9-54 to 9-59 . using chemically generated catalysis reactants . [0335 ] 45. F. A. Cotton , G. Wilkinson , C. A. Murillo , M. [0346 ] First, Li catalyst was tested . Li and LiNH , were Bochmann , Advanced Inorganic Chemistry , Sixth Edi used as a source of atomic lithium and hydrogen atoms. tion , John Wiley & Sons, Inc., New York , ( 1999 ) , Chp 6 . Using water - flow , batch calorimetry , the measured power US 2019/0389723 A1 Dec. 26 , 2019 40

from 1 g Li, 0.5 g LINH2, 10 g LiBr, and 15 g Pd / Al2O3was I. Introduction about 160 W with an energy balance of AH = -19.1 kJ. The [0349 ] Mills [ 1-12 ] solved the structure of the bound observed energy balance was 4.4 times the maximum theo electron using classical laws and subsequently developed a retical based on known chemistry . Next, Raney nickel unification theory based on those laws called the Grand ( R -Ni ) served as a dissociator when the power reaction Unified Theory of Classical Physics (GUTCP ) with results mixture was used in chemical synthesis wherein LiBr acted that match observations for the basic phenomena of physics as a getter of the catalysis product H ( 1/4 ) to form LiH * X as and chemistry from the scale of the quarks to cosmos. This well as to trap H (1/4 ) in the crystal. The ToF - SIMs showed paper is the first in a series of two that covers two specific LiH * X peaks. The ' H MAS NMR LiH * Br and LiH * I predictions of GUTCP involving the existence of lower showed a large distinct upfield resonance at about -2.5 ppm energy states of the hydrogen atom , which represents a that matched H-( 1/4 ) in a LiX matrix . An NMR peak at 1.13 powerful new energy source and the transitions of atomic ppm matched interstitial H2( 1/4 ) , and the rotation frequency hydrogen to lower -energy states [ 2 ]. of H ( 1/4 ) of 42 times that of ordinary H , was observed at [0350 ) GUTCP predicts a reaction involving a resonant, 1989 cm - l in the FTIR spectrum . The XPS spectrum nonradiative energy transfer from otherwise stable atomic recorded on the LiH * Br crystals showed peaks at about 9.5 hydrogen to a catalyst capable of accepting the energy to eV and 12.3 eV that could not be assigned to any known form hydrogen in lower - energy states than previously elements based on the absence of any other primary element thought possible . Specifically , the product is H ( 1 / p ), frac peaks , but matched the binding energy of H- ( 1/4 ) in two tional Rydberg states of atomic hydrogen wherein chemical environments . A further signature of the energetic process was the observation of the formation of a plasma called a resonant transfer- or rt -plasma at low temperatures 1 1 1 N = ( e.g. -10 ° K ) and very low field strengths of about 1-2 V / cm 2 ' 3'4 P when atomic Li was present with atomic hydrogen . Time dependent line broadening of the H Balmer a line was observed corresponding to extraordinarily fast H ( > 40 eV ) . (ps137 is an integer ) replaces the well known parameter n = integer in the Rydberg equation for hydrogen excited [ 0347 ] NaH uniquely achieves high kinetics since the states . He , Art, Sr * , Li, K , and NaH are predicted to serve catalyst reaction relies on the release of the intrinsic H , as catalysts since they meet the catalyst criterion a chemi which concomitantly undergoes the transition to form H ( 1 / cal or physical process with an enthalpy change equal to an 3 ) that further reacts to form H ( 1/4 ) . High - temperature integermultiple of the potential energy of atomic hydrogen , differential scanning calorimetry (DSC ) was performed on 27.2 eV . The data from a broad spectrum of investigational ionic NaH under a helium atmosphere at an extremely slow techniques strongly and consistently support the existence of temperature ramp rate (0.1 ° C./min ) to increase the amount these states called hydrino , for “ small hydrogen " , and the of molecular NaH formation . A novel exothermic effect of corresponding diatomic molecules called dihydrino mol -177 kJ/ mole NaH was observed in the temperature range of ecules . Some of these prior related studies supporting the 640 ° C. to 825 ° C. To achieve high power , R - Ni having a possibility of a novel reaction of atomic hydrogen , which surface area of about 100 m²/ g was surface - coated with produces hydrogen in fractional quantum states that are at NaOH and reacted with Na metal to form NaH . Using lower energies than the traditional “ ground " (n = 1 ) state , water - flow , batch calorimetry , the measured power from 15 include extreme ultraviolet ( EUV ) spectroscopy , character g of R -Ni was about 0.5 kW with an energy balance of istic emission from catalysts and the hydride ion products , AH = -36 kJ compared to AH - 0 kJ from the R -Ni starting lower- energy hydrogen emission , chemically - formed plas material , R -NiAl alloy, when reacted with Na metal . The mas, Balmer a line broadening, population inversion of H observed energy balance of the NaH reaction was -1.6x10 + lines, elevated electron temperature , anomalous plasma kJ/ mole H2, over 66 times the -241.8 kJ/ mole H , enthalpy afterglow duration , power generation , and analysis of novel of combustion . chemical compounds [ 13-40 ] . [ 0348 ] The ToF - SIMs showed sodium hydrino hydride, [0351 ] Recently , there has been the announcement of NaHx, peaks. The ' H MAS NMR spectra of NaH * Br and some unexpected astrophysical results that support the exis NaH * C1showed large distinct upfield resonance at -3.6 ppm tence of hydrinos. In 1995 , Mills published the GUTCP and -4 ppm , respectively , that matched H- ( 1/4 ) , and an prediction [41 ] that the expansion of the universe was NMR peak at 1.1 ppm matched H2( 1/4 ). NaH * C1 from accelerating from the same equations that correctly pre reaction of NaCl and the solid acid KHSO4 as the only dicted the mass of the top quark before it was measured . To source of hydrogen comprised two fractional hydrogen the astonishment of cosmologists , this was confirmed by states . The H- ( 1/4 ) NMR peak was observed at -3.97 ppm , 2000. Mills made another prediction about the nature of dark and the H- ( 1/3 ) peak was also present at -3.15 ppm . The matter based on GUTCP that may be close to being con corresponding H2( 1/4 ) and H (1/3 ) peaks were observed at firmed . Based on recent evidence , Bournaud et al. [42-43 ] 1.15 ppm and 1.7 ppm , respectively . The XPS spectrum suggest that dark matter is hydrogen in dense molecular recorded on NaH * Br showed the H-( 1/4 ) peaks at about 9.5 form that somehow behaves differently in terms of being eV and 12.3 eV that matched the results from LiH * Br and unobservable except by its gravitational effects . Theoretical KH * I; whereas, sodium hydrino hydride showed two frac models predict that dwarfs formed from collisional debris of tional hydrogen states additionally having the H-( 1/3 ) XPS massive galaxies should be free of nonbaryonic dark matter . peak at 6 eV in the absence of a halide peak . The predicted So , their gravity should tally with the stars and gas within rotational transitions having energies of 42 times those of them . By analyzing the observed gas kinematics of such ordinary H , were also observed from H2( 1/4 ) which was recycled galaxies , Bournaud et al. [ 42-43 ] have measured excited using a 12.5 keV electron beam . the gravitationalmasses of a series of dwarf galaxies lying US 2019/0389723 A1 Dec. 26 , 2019 41

in a ring around a massive galaxy that has recently experi electron energy levels are required to be present with atomic enced a collision . Contrary to the predictions of Cold -Dark hydrogen to catalyze the process . The reaction involves a Matter (CDM ) theories, their results demonstrate that they nonradiative energy transfer followed by q : 13.6 eV emission contain a massive dark component amounting to about twice or q : 13.6 eV transfer to H to form extraordinarily hot, the visible matter. This baryonic dark matter is argued to be excited - state H [13-17 , 19-20 , 32-39 ] and a hydrogen atom cold molecular hydrogen , but it is distinguished from ordi that is lower in energy than unreacted atomic hydrogen that nary molecular hydrogen in that it is not traced at all by corresponds to a fractional principal quantum number . That traditional methods, such as emission of CO lines. These is results match the predictions of the dark matter being dihydrino molecules . 1 1 1 (2c ) [ 0352 ] Emission lines recorded on cold interstellar regions n = 1 , - ; p < 137 is an integer containing dark matter matched H ( 1/ p ) , fractional Rydberg 2 ' 3 ' 4 ? states of atomic hydrogen given by Eqs. ( 2a ) and (2c ) [29 ] . Such emission lines with energies of q : 13.6 eV ,where q = 1 , 2 , 3 , 4 , 6 , 7 , 8 , 9 , or 11 were also observed by extreme replaces the well known parameter n = integer in the Rydberg ultraviolet (EUV ) spectroscopy recorded on microwave dis equation for hydrogen excited states. The n = 1 state of charges of helium with 2 % hydrogen [27-29 ] . These Het hydrogen and the fulfills the catalyst criterion a chemical or physical process with an enthalpy change equal to an integer multiple of 27.2 1 eV since it ionizes at 54.417 eV , which is 2 :27.2 eV . The N = product of the catalysis reaction of He* , H ( 1/3 ) ,may further integer serve as a catalyst to lead to transitions to other states H ( 1 / p ) [0353 ] J. R. Rydberg showed that all of the spectral lines states of hydrogen are nonradiative , but a transition between of atomic hydrogen were given by a completely empirical two nonradiative states , say n = 1 to n = 1 / 2 , is possible via a relationship : nonradiative energy transfer . Thus , a catalyst provides a net positive enthalpy ofreaction of m.27.2 eV ( i.e. it resonantly ( 1 ) accepts the nonradiative energy transfer from hydrogen V = R atoms and releases the energy to the surroundings to affect electronic transitions to fractional quantum energy levels ) . As a consequence of the nonradiative energy transfer , the where R = 109,677 cm-?, n , 1 , 2 , 3 , ... n , = 2 , 3 , 4 , ... and hydrogen atom becomes unstable and emits further energy n > n , Bohr, Schrödinger, and Heisenberg , each developed a until it achieves a lower -energy nonradiative state having a theory for atomic hydrogen that gave the energy levels in principal energy level given by Eqs . (2a ) and (2c ). agreement with Rydberg's equation . [0355 ] The catalyst product, H ( 1 / p ) , may also react with an electron to form a novel hydride ion H- ( 1 / p ) with a binding energy EB [1 , 13-14 , 18 , 30 ]: e2 13.598 eV (2a ) En n287 € , ah n2 EB = ( 3 ) n = 1 , 2 , 3 , ... ( 2b ) ti? Vs(s + 1) ??, e? h? 22 1+ s( s + 1) m ? 1+ s( s + 1 ) where e is the elementary charge, & , is the permittivity of 8??? vacuum , and an is the radius of the hydrogen atom . The p ? excited energy states of atomic hydrogen are given by Eq . ( 2a ) for n > 1 in Eq . (2b ) . The n = 1 state is the “ ground ” state for “ pure ” photon transitions ( i.e. the n = 1 state can absorb a where p = integer > 1 , s = 1 / 2 , ? is Planck's constant bar, u , is photon and go to an excited electronic state , but it cannot the permeability of vacuum , m , is the mass of the electron , release a photon and go to a lower - energy electronic state ). ?e is the reduced electron mass given by However, an electron transition from the ground state to a lower- energy state may be possible by a resonant nonradia memp tive energy transfer such as multipole coupling or a resonant Me = me collision mechanism . Processes such as hydrogen molecular +mp bond formation that occur without photons and that require collisions are common [44 ]. Also , some commercial phos phors are based on resonant nonradiative energy transfer involving multipole coupling [45 ] . where mp is the mass of the proton , a is the Bohr radius, and [0354 ] The theory reported previously [ 1 , 13-40 ] predicts the ionic radius is that atomic hydrogen may undergo a catalytic reaction with certain atoms, excimers , ions , and diatomic hydrides which provide a reaction with a net enthalpy of an integer multiple do ri = ( 1 + Vs( s + 1 ) ) . of the potential energy of atomic hydrogen , En = 27.2 eV ? where E , is one Hartree . Specific species ( e.g. He * , Art, Sr* , K , Li, HCl, and NaH ) identifiable on the basis of their known US 2019/0389723 A1 Dec. 26 , 2019 42

From Eq . ( 3 ), the calculated ionization energy of the hydride fundamental constants only [ 1, 6 ]. The total energy of the ion is 0.75418 eV , and the experimental value given by hydrogen molecule having a central field of + pe at each Lykke [46 ] is 6082.99 + 0.15 cm-? (0.75418 eV ) . focus of the prolate spheroid molecular orbital is

e2 ( 7 ) 2v2 2h 4????? V2 + V2 + 1 V2 || 1 + p V ?? Et = -p ? 8n?, QH v2 V2-1 mec2

= -p - 31.351 eV - p30.326469 eV

[0356 ] Upfield - shifted NMR peaks are a direct evidence of [0358 ] The bond dissociation energy , Ed , of hydrogen the existence of lower -energy state hydrogen with a reduced molecule H ( 1 / p ) is the difference between the total energy radius relative to ordinary hydride ion and having an of the corresponding hydrogen atoms and E increase in diamagnetic shielding of the proton . The shift is given by the sum of that of ordinary hydride ion H- and a ED = E ( 2H ( 1 / p ) ) - ET ( 8 ) component due to the lower- energy state [ 1 , 15 ] : where [ 47 ] E ( 2H ( 1 / p ) ) = - p227.20 eV ( 9 ) ABT e2 ( 4 ) = -uo ( 1 + a2ap) = - ( 29.9+ 13.7p ) ppm B 12m200( 1 + Vs( s + 1) ) En is given by Eqs. (8-9 ) and ( 7 ) : where for Hºp = 0 and p = integer > 1 for H-( 1 / p ) and a is the Ep = -p227.20 eV – Er ( 10 ) fine structure constant. [ 0357 ] H ( 1 / p ) may react with a proton and two H ( 1 / p ) may = - p227.20 eV - ( - p231.351 eV – p30.326469 eV ) react to form H ( 1 / p ) and H ( 1 /p ) , respectively . The hydro gen molecular ion and molecular charge and current density = p24.151 eV + p30.326469 eV functions, bond distances , and energies were solved previ ously [ 1 , 6 ] from the Laplacian in ellipsoidal coordinates with the constraint of nonradiation . The calculated and experimental parameters of H2, D2, H2' , and D2* from Ref. [ 1 , 6 ] are given in TABLE 3 . a ?? ( 5 ) (n- ) RE af |Re over + TABLE 3 (6-5 ) R , ,( Roy )+18 –np . z oo ) =0 The Maxwellian closed - form calculated and experimental parameters of H2, D2 , H2+ and D2 +. The total energy Eq of the hydrogen molecular ion having a central field of +pe at each focus of the prolate spheroid Parameter Calculated Experimental molecular orbital is H , Bond Energy 4.478 eV 4.478 eV D2 Bond Energy 4.556 eV 4.556 eV 2e2 ( 6 ) H2+ Bond Energy 2.654 eV 2.651 eV 41 € (207 )3 Dz Bond Energy 2.696 eV 2.691 eV e ? 2hV 1 + pl me 31.677 eV 31.675 eV Et = -p ? 8????? (11-12.2013 mec2 H , Total Energy D2 Total Energy 31.760 eV 31.760 eV k H , Ionization Energy 15.425 eV 15.426 eV 2 V ? D2 Ionization Energy 15.463 eV 15.466 eV = -p216.13392 eV - p30.118755 eV H2+ Ionization Energy 16.253 eV 16.250 eV D2 + Ionization Energy 16.299 eV 16.294 eV where p is an integer, c is the speed of light in vacuum , u is H2+ Magnetic Moment 9.274 x 10-24 JT - 1 9.274 x 10-24 JT- 1 the reduced nuclear mass , and k is the harmonic force (UB ) constant solved previously in a closed - form equation with US 2019/0389723 A1 Dec. 26 , 2019 43

TABLE 3 - continued where ? is an integer, I is the moment of inertia , and the experimental rotational energy for the J = 0 to J = 1 transition The Maxwellian closed - form calculated and experimental of H2 is given by Atkins [50 ] . parameters of H2, D2 , Ht and D , +. [0362 ] The p dependence of the rotational energies results Parameter Calculated Experimental from an inverse p dependence of the internuclear distance Absolute H , Gas - Phase -28.0 ppm -28.0 ppm and the corresponding impact on the moment of inertia I. NMR Shift The predicted internuclear distance 2c' for H2 ( 1 / p ) is H2 Internuclear Distance 0.748 Å 0.741 Å VZao D , Internuclear Distance 0.748 Å 0.741 Å ( 15 ) VZao 2c' = ao V2 H2 Internuclear 1.058 Å 1.06 Å ? Distance 220 D2 + Internuclear 1.058 Å 1.0559 Å Distance 2ao H2 Vibrational Energy 0.517 eV 0.516 eV [0363 ] The formation of new states of hydrogen is very D2 Vibrational Energy 0.371 eV 0.371 eV energetic . A new chemically generated or assisted plasma H2WX 120.4 cm - 1 121.33 cm source based on the resonant energy transfer mechanism D2 W X 60.93 cm 61.82 cm 1 H2 + Vibrational Energy 0.270 eV 0.271 eV ( rt- plasma ) has been developed that may be a new power D + Vibrational Energy 0.193 eV 0.196 eV source . One such source operates by incandescently heating H , J = 1 to J = 0 0.0148 eV 0.01509 eV a hydrogen dissociator and a catalyst to provide atomic Rotational Energy hydrogen and gaseous catalyst, respectively , such that the D2 J = 1 to J = 0 0.00741 eV 0.00755 eV Rotational Energy catalyst reacts with the atomic hydrogen to produce a H2 + J = 1 to J = 0 0.00740 eV 0.00739 eV plasma. It was extraordinary that intense EUV emission was Rotational Energy observed by Mills et al. [ 13-21, 38-39 ] at low temperatures D2 + J = 1 to J = 0 0.00370 eV 0.003723 eV ( e.g. -10 ° K ), as well as an extraordinary low field strength Rotational Energy of about 1-2 V /cm from atomic hydrogen and certain atom ized elements or certain gaseous ions, which singly or " Not corrected for the slight reduction in internuclear distance due to Eose multiply ionize at integer multiples of the potential energy of [0359 ] The ' H NMR resonance of H ( 1 / p ) is predicted to atomic hydrogen , 27.2 eV. be upfield from that of H , due to the fractional radius in [0364 ] K to K3+ provides a reaction with a net enthalpy elliptic coordinates [ 1 , 6 ] wherein the electrons are signifi equal to three times the potential energy of atomic hydrogen . cantly closer to the nuclei. The predicted shift , It was reported previously [ 13-21 , 38-39 ] that the presence of these gaseous atoms with thermally dissociated hydrogen formed an rt- plasma having strong EUV emission with a ABT stationary inverted Lyman population . Other noncatalyst B metals such as Mg produced no plasma. Significant line broadening of the Balmer a , b , and y lines of 18 eV was observed . Emission from rt- plasmas occurred even when the for H2( 1 / p ) derived previously [ 1 , 6 ] is given by the sum of electric field applied to the plasma was zero . Since a that of H , and a term that depends on p = integer > 1 for conventional discharge power source was not present, the H2( 1 / p ) : formation of a plasma would require an energetic reaction . The origin of Doppler broadening is the relative thermal e2 ( 11) motion of the emitter with respect to the observer. Line ABT 2 + 1 - (1 + nap ) broadening is a measure of the atom temperature, and a B ---off- v2 in 2-1 | 36aome significant increase was expected and observed for catalysts , ??? ( 28.01 + 0.64p )ppm (12 ) K as well as Sr * or Ar * [ 13-21, 38-39 ] , with hydrogen . The B observation of a high hydrogen temperature with no con ventional explanation would indicate that an rt -plasma must have a source of free energy . An energetic chemical reaction where for H2 p = 0 . was further implicated since it was found that the broaden [ 0360 ] The vibrational energies , Exin , for the v = 0 to v = 1 ing is time dependent [ 13-14 , 20 ) . Therefore , the thermal transition of hydrogen - type molecules H ( 1 / p ) are ( 1 , 6 ] power balance was measured calorimetrically . The reaction Evib = p20.515902 eV was exothermic since excess power of 20 mW.cm - 3 was (13 ) measured by Calvet calorimetry [ 20 ]. In further experi where ? is an integer and the experimental vibrational ments , KNO3 and Raney nickel were used as a source of K energy for the v = 0 to v = 1 transition of H2, Eh ,( v =0- > 01 ) is catalyst and atomic hydrogen , respectively , to produce the given by Beutler [48 ] and Herzberg [ 49 ] . corresponding exothermic reaction . The energy balance was [ 0361] The rotational energies, Eroth for the J to J + 1 AH = -17 , 925 kcal /mole KNO3, about 300 times that transition of hydrogen -type molecules H_ ( 1 / p ) are [ 1 , 6 ] expected for the most energetic known chemistry of KNO3 , and –3585 kcal/ mole H2, over 60 times the hypothetical maximum enthalpy of –57.8 kcal/ mole H , due to combus h2 (14 ) tion of hydrogen with atmospheric oxygen , assuming the Eros = Es+ 1 – Ey = [ + 1] = p *( 1 + 1) 0.01509 eV maximum possible H , inventory [ 14 ). Additional substantial evidence of an energetic catalytic reaction was previously reported [ 13-15 , 24-26 , 30-31 ] involving a resonant energy US 2019/0389723 A1 Dec. 26 , 2019 44

transfer between hydrogen atoms and K to form very stable having intense hydrogen Lyman emission , a stationary novel hydride ions and molecules H-( 1/4 ) and H2( 1/4 ) , inverted Lyman population , excessive afterglow duration , respectively . Characteristic emission was observed from K3+ highly energetic hydrogen atoms, characteristic alkali - ion that confirmed the resonant nonradiative energy transfer of emission due to catalysis , predicted novel spectral lines , and 3.27.2 eV from atomic hydrogen to K that served as a the measurement of a power beyond any conventional predicted catalyst. From Eq . ( 3 ) , the binding energy Eg of chemistry [ 13-40 ] that matched predictions for a catalytic H-( 1/4 ) is reaction of atomic hydrogen to form more stable hydride ions designated H = ( 1 / p ) . Since the comparison of theory and Ep = 11.232 eV (avac = 110.38 nm ) (16 ) experimental energies is direct evidence of lower- energy [0365 ] The product hydride ion H-( 1/4 ) was observed by hydrogen with an implicit large exotherm during its forma EUV spectroscopy at 110 nm corresponding to its predicted tion , we report in this paper the results when these experi binding energy of 11.2 eV [ 13-15 , 24-26 , 30-31 ]. The ments were repeated with additionally predicted catalysts Li identification of H- ( 1/4 ) was confirmed previously by the and NaH . XPS measurement of its binding energy . The XPS spectrum [0367 ] A catalytic system used to make and analyzed of KH * I differed from that of KI by having additional predicted hydride compounds involves lithium atoms. The features at 8.9 eV and 10.8 eV that did not correspond to any first and second ionization energies of lithium are 5.39172 other primary element peaks but did match the H- (1/4 ) eV and 75.64018 eV , respectively [52 ]. The double ioniza E = 11.2 eV hydride ion ( Eq . ( 3 )) in two different chemical tion ( t = 2 ) reaction of Li to Li2 + then , has a net enthalpy of environments . The ' H MAS NMR spectrum of novel com reaction of 81.0319 eV, which is equivalent to 3.27.2 eV . pound KH * Cl relative to external tetramethylsilane ( TMS) showed a large distinct upfield resonance at -4.4 ppm corresponding to an absolute resonance shift of –35.9 ppm 81.0319 eV + Li( m ) + H ? (17 ) that matched the theoretical prediction of p = 4 [ 13-15 , 25-26 , H ; ] 30-31 ] . Elemental analysis identified [ 13-15 , 25-26 , 30-31 ] Li2 + + 2 € + H these compounds as only containing the alkaline metal, Hp+ 3 , ] + [p +3 ) 2 – p ? 1-13.6 eV halogen , and hydrogen , and no known hydride compound of Li2 + + 2e ? Li( m ) +81.0319 eV ( 18 ) this composition could be found in the literature that had an upfield - shifted hydride NMR peak . Ordinary alkali hydrides alone or mixed with alkali halides show down - field shifted And , the overall reaction is peaks [ 13-15 , 25-26 , 30-31 ] . From the literature , the list of alternatives to H-( 1 /p ) as a possible source of the upfield NMR peaks was limited to U centered H. This was elimi ( 19 ) nated by the absence of the intense and characteristic H )-41073 ) ]+ [ { p + 3) 2 – pºj.13.6 ev infrared vibration band at 503 cm - 1 due to the substitution of H- for Cl- in KCl [ 51] . [0368 ] Lithium is a metal in the solid and liquid states , and [ 0366 ] As a further characterization , FTIR analysis of the gas comprises covalent Li, molecules [53 ] , each having KH * I crystals with H- ( 1/4 ) was performed and interstitial a bond energy of 110.4 kJ/ mole [54 ] . In order to generate H2( 1/4 ) having a predicted rotational energy given by Eq. atomic lithium , LiNH , was added to the reaction mixture . ( 14 ) was observed . Rotational lines were observed previ LiNH , generates atomic hydrogen as well, according to the ously [ 13-14 ] in the 145-300 nm region from atmospheric reversible reactions [55-64 ] : pressure electron beam - excited argon -hydrogen plasmas . The unprecedented energy spacing of 42 times that of Lib + LINH2 > Li + Li- NH + H (20 ) hydrogen established the internuclear distance as 1/4 that of and H , and identified H ( 1/4 ) ( Eqs. (13-15 ) ) . The spectrum was asymmetric with the P branch dominant corresponding to the Li_ + Li2NH Li+ LizN + H ( 21) absence of populated rotational states in the exited v = 1 The energy for the reaction of lithium amide to lithium vibrational state . This was due to the high rotational energy ( 10 times the thermal energy ), the short lifetime of the nitride and lithium hydride is exothermic [65-66 ]: rotational excited states, and the low cross section for 4Li + KiNH2 > Li3N + 2LIH AH = -198.5 kJ/ mole electron - beam rotational excitation ; whereas, the vibrational LINH2 (22 ) dipole excitation was allowed . Thus, only the v = 1 , J = 0 state Thus , it should occur to a significant extent. The specific was populated significantly from e -beam excitation , and predictions of the energetic reaction given by Eqs . (17-19 ) transitions occurred with AJ > 0 during the v = 1 to u = 0 were tested by rt -plasma formation and H line broadening . transition . KH * Cl having H-( 1/4 ) by NMR was incident to The power developed was measured using water- flow , batch the 12.5 keV electron beam , which excited similar emission calorimetry . Then , the predicted products of H (1/4 ) and H , of interstitial H , ( 1/4 ) as observed in the argon -hydrogen ( 1/4 ) having the energies given by Eqs. ( 3 ) and (5-15 ) , plasma [ 13-14 ] . Specifically , H2( 1/4 ) trapped in the lattice of respectively , were tested by magic angle solid proton nuclear KH * Clwas investigated by windowless EUV spectroscopy magnetic resonance spectroscopy (MAS ' H NMR ) , X - ray on electron -beam excitation of the crystals using the 12.5 photoelectron spectroscopy (XPS ), time of flight secondary keV electron gun at pressures below which any gas could ion mass spectroscopy ( ToF -SIMs ) , and Fourier transform produce detectable emission (< 10-5 Torr ) . The rotational infrared spectroscopy (FTIR ). energy of H2 ( 1/4 ) was confirmed by this technique as well . [0369 ] A compound comprising hydrogen such as MH , These results confirmed the previous observations from the where M is element other than hydrogen , serves as a source plasmas formed by the energetic hydrino - forming reaction ofhydrogen and a source of catalyst. A catalytic reaction is US 2019/0389723 A1 Dec. 26 , 2019 45

provided by the breakage of the M - H bond plus the where Hfast + is a fast hydrogen atom having at least 13.6 eV ionization of t electrons from the atom M each to a con of kinetic energy . H ( 1/4 ) forms stable halidohydrides and is tinuum energy level such that the sum of the bond energy a favored product together with the corresponding molecule and ionization energies of the t electrons is approximately formed by the reactions 2H (1/4 ) > H2( 1/4 ) and H-( 1/4 ) + H + 27.2 eV where m is an integer . One such catalytic system ? H , ( 1/4 ) [ 13-15 , 24-26 , 30-31] . The corresponding involves sodium . The bond energy of NaH is 1.9245 eV hydrino atom H ( 1/4 ) is a preferred final product consistent [ 54 ] , and the first and second ionization energies of Na are with observation since the p = 4 quantum state has a multi 5.13908 eV and 47.2864 eV , respectively [52 ]. Based on polarity greater than that of a quadrupole giving it a long these energies NaH molecule can serve as a catalyst and H theoretical lifetime. H ( 1/4 ) may be formed directly from source, since the bond energy of NaH plus the double He.g. Eqs. (36-38 ) ) or via multiple transitions ( e.g. Eqs . ionization ( t= 2 ) of Na to Na2+ is 54.35 eV ( 2 : 27.2 eV ) . The ( 23-27 )) . In the latter case, the higher - energy H ( 1 /p ) states catalyst reactions are given by with quantum numbers p = 2 ; 1 = 0 , 1 and p = 3 ; e = 0 , 1 , 2 corresponding to dipole and quadrupole transitions, respec tively , have theoretically allowed , fast transitions . (23 ) [ 0371 ] Sodium hydride is typically in the form of an ionic 54.35 eV + NaH -- Na²+ + 2€ + H [ * ] + [ 32 – 12) . 13.6 eV crystalline compound formed by the reaction of gaseous Na2 + + 2e + H ? NaH + 54.35 eV ( 24 ) hydrogen with metallic sodium . And , in the gaseous state , sodium comprises covalent Na , molecules [53 ] with a bond energy of 74.8048 kJ/ mole [54 ] . It was found that when And , the overall reaction is NaH (s ) was heated at a very slow temperature ramp rate ( 0.1 ° C./min ) under a helium atmosphere to form NaH ( g ), the predicted exothermic reaction given by Eqs. (23-25 ) was H ? H (25 ) observed at high temperature by differential scanning calo 4105 ]+ [ 32 – 12 ] . 13.6 eV rimetry (DSC ) . To achieve high power , a chemical system was designed to greatly increase the amount and rate of [0370 ] As given in Chp . 5 of Ref [ 1 ], and Ref. [ 29 ] , formation of NaH ( g ) . The reaction of NaOH and Na to Na20 hydrogen atoms H ( 1 / p ) p = 1 , 2 , 3 , . . . 137 can undergo and NaH ( s ) calculated from the heats of formation [ 54 , 65 ] further transitions to lower -energy states given by Eqs . (2a ) releases AH = -44.7 kJ/ mole NaOH : and (2c ) wherein the transition of one atom is catalyzed by NaOH + 2Na - Na2O + NaH (s ) AH = -44.7 /mole NaOH ( 31 ) a second that resonantly and nonradiatively accepts m.27.2 This exothermic reaction can drive the formation of NaH ( g ) eV with a concomitant opposite change in its potential and was exploited to drive the very exothermic reaction energy. The overall general equation for the transition of given by Eqs . ( 23-25 ). The regenerative reaction in the H ( 1 / p ) to H ( 1 / ( p + m )) induced by a resonance transfer of presence of atomic hydrogen is m.27.2 eV to H ( 1 / p ') is represented by H ( 1/ p ') + H ( 1/ p ) -> H * + e + H (1 / (p + m ) ) +[ 2 pm+m2-p2 ] Na2O + H - NaOH + Na AH = -11.6 kJ/ mole NaOH (32 ) -13.6 eV ( 26 ) NaH-> Na + H ( 1/3) AH = -10,500 kJ/mole H ( 33 ) In the case of a high hydrogen atom concentration , the transition of H ( 1/3 ) ( p = 3 ) to H ( 1/4 ) (p + m = 4 ) with H as the and catalyst ( p = 1 ; m = 1 ) can be fast: NaH » Na + H ( 1/4 ) AH = -19,700 kJ/ mole H ( 34 ) Thus , a small amount of NaOH , Na, and atomic hydrogen ? serves as a catalytic source of the NaH catalyst that in turn H ( 1/3 ) ? H ( 1/4 ) +81.6 eV ( 27 ) forms a large yield of hydrinos via multiple cycles of regenerative reactions such as those given by Eqs. ( 31-34) . R -Ni having a high surface area of about 100 m²/ g and The NaH catalyst reactionsmay be concerted since the sum containing H was surface coated with NaOH and reacted of the bond energy of NaH , the double ionization ( t = 2 ) ofNa with Na metal to form NaH ( g ) . Since the energy balance in to Na2 + , and the potential energy of H is 81.56 eV ( 3.27.2 the formation of NaH ( g ) was negligible due to the small eV ) . The catalyst reactions are given by amounts involved , the energy and power due to the hydrino reactions given by Eqs . ( 23-25) were specifically measured using water - flow , batch calorimetry . Next, R - Ni 2400 was 81.56 eV + NaH + H ? ( 28 ) prepared such that it comprised about 0.5 wt % NaOH , and Na2 + + 2 € + Hdfast + e + HHL ] +[ 42 – 12) . 13.6 ev the Al of the intermetallic served as the reductant to form NaH catalyst during calorimetry measurement. The reaction Na2 + + 24 + H + HFast + é ? NaH + H + 81.56 eV ( 30 ) of NaOH + Al to Al2O3+ NaH calculated from the heats of formation [65 ] is exothermic by AH = -189.1 kJ I mole NaOH . The balanced reaction is given by And , the overall reaction is 3NaOH + 2A1 - Al2O3 + 3NaH A = -189.1 kJ/ mole NaOH ( 35 ) (30 ) This exothermic reaction can drive the formation of NaH ( g ) H - H ( * ) + [42 - 12) . 13.6 eV and was exploited to drive the very exothermic reaction given by Eqs . (23-25 ) wherein the regeneration of NaH occurred from Na in the presence of atomic hydrogen . For US 2019/0389723 A1 Dec. 26 , 2019 46

0.5 wt % NaOH , the exothermic reaction given by Eq. (35 ) lated stainless steel cell with a cap that incorporated ports for gave a negligible AH = -0.024 kJ background heat during gas inlet , and outlet . A titanium filament (55 cm long , 0.5 measurement. mm diameter} that served as a heater and hydrogen disso [0372 ] It was reported previously [28-29 ] that the reaction ciator was in the cell . 1 g of LiNH , (Alfa Aesar 99.95 % ) was products H ( 1 / p ) may undergo further reaction to lower placed in the center of the cell under 1 atm of dry argon in energy states. For example , the catalyst reaction of Art to a glove box . The cell was sealed and removed from the glove Ar2+ forms H ( 1/2 ), which may further serve as both a box . The cell was maintained at 50 ° C. for 4 hours with catalyst and a reactant to form H ( 1/4 ) [ 1 , 13-14 , 28-29 ] and helium flowing at 30 sccm at a pressure of 1 Torr. The the corresponding favored molecule H2( 1/4 ), observed using filament power was increased to 200 W in 20 W increments different catalysts [ 13-14 ] . Thus, predicted products of NaH every 20 minutes . At 120 W , the filament temperature was catalyst from Eqs. (23-25 ) and Table 1 of Ref. [29 ] are estimated to be in the range 800 to 1000 ° C. The external cell H-( 1/3) and H2( 1/4 ) having the energies given by Eqs. ( 3 ) wall temperature was about 700 ° C. The cell was then and (5-15 ), respectively . They were tested by MAS ' H NMR operated with and without an argon -hydrogen (95 / 5 % ) flow and ToF - SIMs. rate of 5.5 sccm maintained at 1 Torr . Additionally , the cell [0373 ] Another catalytic system of the type MH involves was operated with hydrogen gas flow replacing argon chlorine . The bond energy of HCl is 4.4703 eV [54 ]. The hydrogen (95 / 5 % ) . The LiNH , was vaporized by the fila first , second , and third ionization energies of Cl are ment heater as evidence the presence of Li lines. The 12.96764 eV , 23.814 eV , and 39.61 eV , respectively [52 ]. presence of an argon - hydrogen or hydrogen plasma was Based on these energies, HCl can serve as a catalyst and H determined by recording the visible spectrum over the source , since the bond energy of HClplus the triple ioniza Balmer region with a Jobin Yvon Horiba 1250 M spectrom tion (t = 3 ) of Cl to C13 + is 80.86 eV ( 3.27.2 eV ) . The catalyst eter with a CCD detector described previously [15-21 ] using reactions are given by entrance /exits slits of 80/80 um and a 3 second integration time. The width of the 656.3 nm Balmer a line emitted from the argon -hydrogen ( 95/5 % ) -LiNH , or hydrogen -LiNH , rt ( 36 ) plasma having a titanium filament was measured initially 80.86 eV + HCI – C13+ + 36 " + HC4 % ] + [42 - 12) .13.6 ev and periodically during operation . As further controls , the C13 + + 3 + H HCl + 80.86 eV (37 ) experiment was run with each of the flowing gases in the absence of LiNH . [0376 ] Differential Scanning calorimetry (DSC ) Measure And , the overall reaction is ments . Differential scanning calorimeter (DSC ) measure ments were performed using the DSC mode of a Setaram HT- 1000 calorimeter (Setaram , France ). Two matched alu H 1-21 ? % ]+ [42 – 12) . 13.6 eV (38 ) mina glove fingers were used as the sample compartment and the reference compartment . The fingers permitted the control of the reaction atmosphere . 0.067 g NaH was placed The anticipated product then is H2( 1/4 ) . in a flat -base Al- 23 crucible ( Alfa -Aesar , 15 mm highx10 [0374 ] Alkali chlorides contain both Cl and H , typically mm ODx8 mm ID ) . The crucible was then placed in the from H2O contamination . Thus, some HCl can form inter bottom of the sample alumina glove finger cell . As a stitially in the crystalline matrix . Since H + can most easily reference , an aluminum oxide sample ( Alfa - Aesar , -400 substitute for Lr, and the substitution is least likely in the Mesh powder, 99.9 % ) with matching weight of the sample case of cs + , it was anticipated that alkali chlorides may form was placed in a matched Al- 23 crucible . All samples were HCl that undergoes catalysis to form H ( 1/4 ) with the trend handled in a glove box . Each alumina glove finger cell was of the rate of formation increasing in the order of the Group sealed in the glove box, removed from the glove box , and I elements . Due to the difference in lattice structure ,MgCl2 then quickly attached to the Setaram calorimeter. The system may not form HCl catalyst; thus, it serves as a chlorine was immediately evacuated to pressure of 1 mTorr or less . control. This condition applies to other alkaline earth halides The cell was back filled with 1 atm of helium , evacuated and transition metal halides such as those of copper that can again , and then refilled with helium to 760 Torr. The cells serve as controls for the formation of Hz( 1/4 ) . One exception were then inserted into the oven , and secured to their from this set is Mg2 + in a suitable lattice, since the ionization positions in the DSC instrument. The oven temperature was ofMg2 + to Mg3 + is 80. 1437 eV [ 52 ] which is close to 3.27.2 brought to the desired starting temperature of 100 ° C. The eV These hypotheses were tested by electron beam - excita oven temperature was scanned from 100 ° C. to 750 ° C. at a tion emission spectroscopy on alkali halides, MgX2 ( X = F , ramp rate of 0.1 degree /minute . As a control, MgH replaced CI, Br, I } , and CuXZ ( X = F , C1, Br ) with the goal of NaH . A 0.050 g MgH , sample (Alfa -Aesar , 90 % , reminder determining whether the predicted emission of H ( 1/4 ) is Mg) was added to the sample cell , while a similar weight of selectively observed when a catalyst reaction is possible and aluminum oxide (Alfa - Aesar) was added to the reference not otherwise . NMR was recorded on these compounds to cell. Both samples were also handled in a glove box . search for the corresponding predicted H , ( 1/4 ) peak to be [0377 ] Water- Flow , Batch calorimetry. The cylindrical compared with the emission results . stainless steel reactor of approximately 60 cm volume ( 1.0 " outside diameter (OD ) , 5.0 " length , and 0.065 " wall thick II . Experimental Methods ness ) is shown in FIG . 2B . The cell further comprised a [ 0375 ] Rt- plasma and Line Broadening Measurements . welded -in 2.5 " long , cylindrical thermocouple well with a LiNH , argon -hydrogen (95 / 5 % ) and LiNH , hydrogen rt wall thickness of 0.035" along the centerline that held a Type plasmas was generated in the experimental set up described K thermocouple (Omega ) read by a meter ( DAS ). For the previously [ 15-21 ] (FIG . 2A ) comprising a thermally insu cell sealed with a high temperature valve , a 3/8" OD , 0.065 " US 2019/0389723 A1 Dec. 26 , 2019 47

thick SS tube welded at the end of the cell 1/4 " off - center centage recovery of the total energy applied by the heater . served as a port to introduce combinations of the reagents The energy recovery was determined by integrating the total comprising the group of (i ) 1 g Li, 0.5 g LINH ,, 10 g LiBr, output power P , over time. The power was given by and 15 g PdIA1203, ( ii ) 3.28 g Na , 15 g Raney (R- ) NilAl alloy , (iii ) 15 g R - Ni doped with NaOH , and ( iv ) 3 wt % Pr= ?CAT ( 39 ) Al( OH ) 3 doped NilA1 alloy. In the case that this port was where ? was the mass flow rate , Cp was the specific heat of spot- weld sealed , the SS tube had a 1/4 " OD and a 0.02 " water , and AT was the absolute change in temperature wall -thickness . The reactants were loaded in a glove box , between the inlet and outlet where the two thermistors were and a valve was attached to the port tube to seal the cell matched to correct any offset using a constant flow with no before it was removed from the glove box and connected to input power . In first step of the calibration test , an empty a vacuum pump. The cell was evacuated to a pressure of 10 reaction cell, that was identical to the latter tested power cell mTorr and crimped . The cell was then sealed with the valve containing the reactants , was evacuated to below 1 Torr and or hermetically sealed by spot- welding 1/2 " from the cell inserted into the calorimeter vacuum chamber. The chamber with the remaining tube cut off . was evacuated and then filled with helium to 1000 Torr . The [0378 ] The reactor was installed inside a cylindrical calo unpowered assembly reached equilibrium over an approxi rimeter chamber shown in FIG . 3. The stainless steel cham mately two- hour period at which time the temperature ber had 15.2 cm ID , 0.305 cm wall thickness, and 40.4 cm difference between the thermistors became constant. The length . The chamber was sealed at both ends by removable system was run another hour to confirm the value of the stainless steel plates and Viton o - rings. The space between difference due to absolute calibrations of the two sensors . the reactor and the inside surface of the cylindrical chamber The magnitude of the correction was 0.036 ° C., and it was was filled with high temperature insulation . The gas com confirmed to be consistent over all of the tests performed position and pressure in the chamber was controlled to over the reported data set . modulate the thermal conductance between the reactor and [0380 ] To increase the temperature of the cell per input the chamber. The interior of the chamber was first filled with power, ten minutes before the end of the ten -hour equili 1000 Torr helium to allow the cell to reach ambient tem bration period , helium was evacuated from the chamber by perature , the chamber was then evacuated during the calo the vacuum pump , and the chamber was maintained under rimetric run to increase the cell temperature . Afterwards, dynamic pumping at a pressure below 1 Torr. 100.00 W of 1000 Torr helium was added to increase the heat transfer rate power was supplied to the heater (50.23 V and 1.991 A ) for from the hot cell to the coolant and balance any heat a period of 50 minutes. During this period , the cell tem associated with P - V work . The relative dimensions of the perature increased to approximately 650 ° C., and the maxi reactor and the chamber were such that heat flow from the mum change in water temperature ( outlet minus inlet ) was reactor to the chamber was primarily radial. Heat was approximately 1.2 ° C. After 50 minutes, the program removed from the chamber by cooling water which flowed directed the power to zero . To increase the rate of heat turbulently through 6.35 mm OD copper tubing , which was transfer to the coolant, the chamber was re- pressurized with wound tightly (63 turns) onto the outer cylindrical surface of 1000 Torr of helium and the assembly was allowed to fully the chamber. The reactor and chamber system were designed reach equilibrium over a 24 - hour period as confirmed by the to safely absorb a thermal power pulse of 50 kW with one observation of full equilibrium in the flow thermistors. a minute duration . The absorbed energy was subsequently [0381 ] The hydrino -reaction procedure followed that of released to the cooling water stream in a controlled manner the calibration run , but the cell contained the reagents . The for calorimetric measurement. The temperature rise of the equilibration period with 1000 Torr helium in the chamber cooling water was measured by precision thermistor probes was 90 minutes . 100.00 W of power was applied to the (Omega , OL -703 -PP , 0.01 ° C.) at the cooling coil inlet and heater, and after 10 minutes , the helium was evacuated from exit. The inlet water temperature was controlled by a Cole the chamber. The cell heated at a faster rate post evacuation , Parmer (digital Polystat, model 12101-41) circulating bath and the reagents reached a hydrino reaction threshold tem with 0.01 ° C. temperature stability and 900 W cooling perature of 190 ° C. at 57 minutes. The onset of reaction was capacity at 20 ° C. A well insulated eight- liter damping tank confirmed by a rapid rise in cell temperature that reached was installed just downstream of the bath in order to reduce 378 ° C. at about 58 minutes . After ten minutes , the power temperature fluctuations caused by cycling of the bath . was terminated , and helium was reintroduced into the cell Coolant flow through the system was maintained by an FMI slowly over a period of 1 hour at a rate of 150 sccm . model QD variable flow rate positive displacement lab [0382 ] The reactants 0.1 wt % NaOH -doped R - Ni 2800 or pump. Cooling water flow rate was set by a variable area 0.5 wt % NaOH -doped R -Ni 2400 ( elemental analysis was flow meter with a high - resolution control valve. The flow provided by the manufacturer, W. R. Grace Davidson , and meter was calibrated directly by water collection in situ . A the wt % NaOH was confirmed by elemental analysis secondary flow rate measurement was performed by a (Galbraith ) performed on samples handled in an inert atmo turbine flow meter (McMillan Co., G111 Flometer, 11 % ) sphere ) and the products following the reaction of these which continuously output the flow rate to the data acqui reactants as well as those of the reaction mixture comprising sition system . The calorimeter chamber was installed in a Li ( 1 g ) and LiNH , (0.5 g ) ( Alfa Aesar 99 % ) , LiBr (10 g ) covered HDPE tank which was filled with melamine foam ( Alfa Aesar ACS grade 99 + % ), and Pd/ A1,03 (15 g ) ( 1 % Pd , insulation to minimize heat loss from the system . Careful Alfa Aesar ) were analyzed by quantitative X - ray diffraction measurement of the thermal power release to the coolant and (XRD ) using hermetically sealed sample holders (Bruker comparison with the measured input power indicated that Model # A100B37) loaded in a glove box under argon and thermal losses were less than 2-3 % . analyzed with a Siemens D5000 diffractometer using Cu [0379 ] The calorimeter was calibrated with a precision radiation at 40 kV/ 30 mA over the range 10 ° -70° with a step heater applied for a set time period to determine the per size of 0.02º and a counting time of eight hours . In addition , US 2019/0389723 A1 Dec. 26 , 2019 48

a weighed sample of R - Ni in a 16.5 cc stainless steel cell samples were loaded into 4 mm OD Suprasil quartz tubes connected to a vacuum system having a total volume of 291 and evacuated to a final pressure of 10-4 Torr . ESR spectra cc was heated with a temperature ramp from 25 ° C. to 550 ° were recorded with a Bruker ESP 300 X -band spectrometer C. to decompose any physically absorbed or chemisorbed at room temperature and 77 K. The magnetic field was gasses and to identify and quantify the released gasses . The calibrated with a Varian E - 500 gauss meter. The microwave hydrogen content was determined by mass spectroscopy, frequency was measured by a HP 5342A frequency counter . quantitative gas chromatography (HP 5890 Series II with a [0385 ] Elemental analysis was performed at Galbraith ShinCarbon ST 100/120 micropacked column ( 2 m long, Laboratories to confirm the product composition and to 1/16 " OD ), N2 carrier gas with a flow rate of 14 ml/ min , an eliminate the possibility of NMR -detectable amounts of any oven temperature of 80 ° C., an injector temperature of 100 ° transition metal hydrides or other exotic hydrides that may C., and thermal- conductivity detector temperature of 100 ° give rise to upfield - shifted peaks. Specifically , the abun C. ) , and by using the ideal gas law and the measured dance of all elements present in the product (Li , H , X ) and the pressure , volume, and temperature. Hydrogen dominated stainless steel reaction vessel and R -Ni (Ni ,Fe ,Cr , Mo , Mn , each analysis with trace water only detected by mass spec Al) were determined . troscopy , and < 2 % methane was also quantified by gas [0386 ] NaH * Cl and NaH * Br were synthesized by reaction chromatography. The trace water of the R -Ni and controls of hydrogen with Na ( 3.28 g ) and NaH ( 1 g ) ( Aldrich was quantified independently of the hydrogen by liquefying Chemical Company 99 % ) as a source of NaH catalyst and the H2O in a liquid nitrogen trap , pumping off the hydrogen , intrinsic atomic H with the corresponding alkali halide ( 15 and allowing all the water to vaporize by using a sample size g ) , NaCl or NaBr (Alfa Aesar ACS grade 99 + % ) , as an of 0.5 g which is less than that which gives rise to a saturated additional reactant. The compounds were prepared in a water - vapor pressure at room temperature . stainless steel gas cell (FIG . 4 ) further containing Pt/ Ti (Pt [0383 ] Synthesis and Solid 'H MAS NMR of LiH * Br, coated Ti (15 g ) ; Titan Metal Fabricators, platinum plated LiH * I , NaH * Cl and NaH * Br. Lithium bromo and iodohy titanium mini- expanded anode , 0.089 cmx0.5 cmx2.5 cm drinohydride (LiH * Br and LiH * I) were synthesized by with 2.54 um of platinum ) as the hydrogen dissociator. Each reaction of hydrogen with Li ( 1 g ) and LiNH , (0.5 g ) ( Alfa synthesis was run according to the methods described for Li Aesar 99 % ) as a source of atomic catalyst and additional except that the kiln was maintained at 500 ° C., and , the atomic H with the corresponding alkali halide ( 10 g ), LiBr NaH * C1 synthesis was repeated without the addition of ( Alfa Aesar ACS grade 99 + % ) or Li/ ( Alfa Aesar 99.9 % ), as hydrogen gas to determine the effect of using NaH (s ) as the an additional reactant. The compounds were prepared in a sole hydrogen source. XPS was performed on NaH * Cl since stainless steel gas cell (FIG . 4 ) further containing Raney Ni no primary element peaks were possible in the region for ( 15 g ) (W. R. Grace Davidson ) as the hydrogen dissociator H- ( 1/4 ), and NMR investigations of both products were according to the methods described previously ( 13-14 ]. The preformed . reactor was run at 500 ° C. in a kiln for 72 hours with make- up hydrogen addition such that the pressure ranged [0387 ] NaH * C1 was also synthesized from NaCl ( 10 g ) cyclically between 1 Torr to 760 Torr. Then , the reactor was and the solid acid KHSO4 (1.6 g ) as the only source of cooled under helium atmosphere. The sealed reactor was hydrogen with the kiln maintained at 580 ° C. NMR was then opened in a glove box under an argon atmosphere . performed to test whether H-( 1/3 ) formed by the reactions NMR samples were placed in glass ampules , sealed with of Eqs. (23-25 ) could be observed when the rapid reaction rubber septa , and transferred out of the glove box to be flame to H-( 1/4 ) according to Eq. (27 ) was partially inhibited due sealed . ' H MAS NMR was performed on solid samples of to the absence of a high concentration of H from a disso LiH * X ( X is a halide ) at Spectral Data Services, Inc. , ciator with H , or a hydride . Champaign , Ill. as described previously [ 13-14 ]. Chemical [ 0388 ] A silicon wafer ( 2 g , 0.5x0.5x0.05 cm , Silicon shifts were referenced to external TMS . XPS was also Quest International , silicon ( 100 ) , boron - doped , cleaned by performed on crystalline samples that were handled as heating to 700 ° C. under vacuum ) was coated by the product air -sensitive materials . NaH * Cl and NaH * by placing it in reactants comprising Na [0384 ] Since the synthesis reaction comprised LiNH ,, and ( 1.7 g ) , NaH ( 0.5 g ) , NaCl (10 g ), and Pr / Ti ( 15 g ) wherein Li NH was a reaction product , both were run as controls the NaCl that was initially heated to 400 ° C. under vacuum alone and in a LiBr or Lil matrix . The LiNH , was the to remove any H2 ( 1/4 ) . The reaction was run at 550 ° C. in commercial starting material, and Li NH was synthesized the kiln for 19 hours with an initialhydrogen pressure of 760 by the reaction of LiNH , and LiH [67 ] and by decomposition Torr . XPS was performed on a spot comprising only sodium of LiNH2 [68 ] with the Li, NH product confirmed by X - ray hydrino hydride coated silicon wafer (NaH * -coated Si) . The diffraction (XRD ) . To eliminate the possibility that the alkali NaH * Cl- coated silicon wafer (NaH * Cl- coated Si) was halide influenced the local environment of the protons or investigated by electron -beam excitation spectroscopy . An that any given known species produced an NMR resonance emission spectrum of a pressed pellet of the NaH * Cl crystals that was shifted upfield relative to the ordinary peak , con was also recorded . trols comprising LiH ( Aldrich Chemical Company 99 % ) , [ 0389 ] TOF - SIMS Spectra . The crystalline samples of LiNH2, and Li NH with an equimolar mixture of LiX were LiH * Br, LiH * I, NaH * CI, NaH * Br, and the corresponding run . The controls were prepared by mixing equimolar alkali halide controls were sprinkled onto the surface of a amounts of compounds in a glove box under argon . To double -sided adhesive tape and characterized using a Physi further eliminate F centers as a possible contributor to the cal Electronics TFS - 2000 TOF - SIMS instrument. The pri local environment of the protonsof any given known species mary ion gun utilized a 69Gat liquid metal source. A region to produce an upfield - shifted NMR resonance , electron spin on each sample of (60 pm ) 2 was analyzed . In order to resonance spectroscopy (ESR ) was performed on the remove surface contaminants and expose a fresh surface , the LiH * Br and LiH * I samples . For the ESR studies, the samples were sputter - cleaned for 60 seconds using a 180