UNITED STATES DEPARTMENT OF COMMERCELuther H.Hodges, SecretaryNATIONAL BUREAU OF STANDARDS·A.V.Astin,DirectorTablesof ChemicalKineticsHomogeneous Reactions(SupplementaryTables)National Bureau of StandardsA.V.Astin,DirectorNational Research Council, Division of ChemistryCommittee on Kinetics of Chemical ReactionsM.L.Kilpatrick,ChairmanH.TaubeJ. BigeleisenR.NoyesK.WibergC.SatterfieldProject Office:Hepburn Hall, St.Lawrence University,Canton, Naw YorkC.H.Stauffer,ProjectDirectorA.R.AmellD.M.KernE.BuncelH.G.KuivilaT.W.DavisP.E.MerrittJ.O.EdwardsM.SzwarcH.B.FeldmanH.TaubeC.L.GageM.H. J. WijnenH.S. JohnstonNational Bureauof Standards Monograph 34To Accompany National Bureau of Standards C510, Supplements I and 2Issued September15,1961
UNITED STATES DEPARTMENT OF COMMERCE • Luther H. Hodges, Secretary NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director Tables of Chemical Kinetics Homogeneous Reactions (Supplementary Tables) National Bureau of Standards A. V. Astin, Director National Research Council, Division of Chemistry Committee on Kinetics of Chemical Reactions M. L. Kilpatrick, Chairman J. Bigeleisen H. Taube R. Noyes K. Wiberg C. Satterfield Project Office: Hepburn Hall, St. Lawrence University, Canton, Nave York C. H. Stauffer, Project Director A. R. Amell D. M. Kern E. Buncel H. G. Kuivila T. W. Davis P. E. Merritt J. O. Edwards M. Szwarc H. B. Feldman H. Taube C. L. Gage M. H. J. Wijnen H. S. Johnston National Bureau of Standards Monograph 34 To Accompany National Bureau of Standards C510, Supplements 1 and 2 Issued September 15, 1961
National Bureau of CtendardsJUN21965130,262QC100U556Cop.aContents(Supplementary Tables)PageiiPreface.SubjectindexivTables.10
Katronal Bureau of Standards JUN I 1955 QClOO r \ } : ^ \ Contents ^ / (Supplementary Tables) Page Preface iii Subject index iv Tables 1 II
SUPPLEMENT3.TOTABLESOFCHEMICALKINETICSHOMOGENEOUSREACTIONSPREFACEA description of these Tables and derinition of the terms and abbreviations used may befound Inthe introduction to the 195i pubiication. A brlef description of the method used incompiling these tables and the limitation or coverage is given in the preface to Supplement 1.Adescription ofthe nunberingsystem usedinclassifyingreactions forthetablesis given InSupplement 2.Thepresent supplement contains information pertainingto Substitution,Exchangeand Elimination reaction types.It isnot complete asstiil more material falling in these groupsis being prepared.The amount of kinetic data to be studiedmade it seem advisableto presentall thematerial completed to datewithoutfurtherdelayThedateoneachsection gives the yearand month to which the literature had been surveyed.Significant omissions or errors should bereported to Dr. Charles H.,Stauffer, Head, Department of Chenistry,St.Lawrence University,Canton, New York.TheDirectorandhis associates gratefully acknowledge the financial assistance provided bythe orrice or Ordnance Research, Department of the Army which made this work possible.The Di-rector of the Project gratefully acknowledges the able assistance of his associates and collab-orators, thehelp of theNational Bureau of standards,the National Academy of Sciences and themembers of the Committee on Chemical Kineticsof N.R.C.Division of Chemistry.c.H.StaurferDecember,1959National Bureau of Standards - National Research CouncilII
SUPPLEMENT 3 TO TABLES OF CHEMICAL KINETICS HOMOGENEOUS REACTIONS PREFACE A description of these Tables and definition of the terms and abbreviations used may be found In the Introduction to the 1951 publication. A brief description of the method used In compiling these tables and the limitation of coverage Is given in the preface to Supplement 1. A description of the numbering system used In classifying reactions for the tables is given In Supplement 2. The present supplement contains information pertaining to Substitution, Exchange and Elimination reaction types. It is not complete as still more material falling in these groups Is being prepared. The amount of kinetic data to be studied made it seem advisable to present all the material completed to date without further delay. The date on each section gives the year and month to which the literature had been surveyed. Significant omissions or errors should be reported to Dr. Charles H. Stauffer, Head, Department of Chemistry, St. Lawrence university. Canton, New York. The Director and his associates gratefully aclmowledge the financial assistance provided by the Office of Ordnance Research, Department of the Army which made this work possible. The Di- rector of the Project gratefully acknowledges the able assistance of his associates and collaborators, the help of the National Bureau of Standards, the National Academy of Sciences and the members of the Committee on Chemical Kinetics of N. R. C. Division of Chemistry. C.H. Stauffer National Bureau of Standards - National Research Council December, 1959 III
1Homogeneous Reactlon KineticsSUBJECT INDEXTableTitle of Table300EXCHANGE-SUBSTITUTIONnumber(number of pages)300ISOTOPIC EXCHANGE301Isotopic exchange (gas)Isotopic exchange;hydrogen exchange on301.401aliphaticc(2)oxide or carbon(2)301.464Isotopic exchange;(4)301.471halogen on aliphatic cIsotopic exchange;Isotopic exchange;halogen in Ivth group301.474halide(1)oxides or nitrogen(1)301.565Isotopic exchange,(1)301.701hydrogen-hydrogen halideIsotopic exchange;(3)301.770halogen-halogen halideIsotopic exchange;302Isotopic exchange (liquid)Isotopic exchange;ammonia(amine)complex302.150(1)on group I elementIsotopic exchange;halogen complex on302.170group I element (1)Isotopic exchange;valence state group I302.1901ons(1)Isotopic exchange;cyanide complex group II302.240element(2)Isotopic exchange;valence state group I11(11)lons302.390Isotopic exchange;H-D, (T) exchange onaliphaticC(12)302.401Isotopic exchange;H-D,exchange on302.402aromaticc(1o)H-D exchange on C inIsotopicexchange;(1)heterocyclic ring302.403Isotopic exchange;oxygen isotope exchange(6)302.461on carbonIsotopic exchange;sulrur exchange between(2)302.466disulfide and thiolIsotopic exchange;halogen on Ivth group(1)halide302.474Isotopic exchange;halogen for halogen in(23)302.477organic conpoundsIsotopic exchange;hydrogen isotope exchangebetween Vth group element and H-o bond(3)302.506hydrogen Isotope exchangeIsotopicexchange;(1)onNinVIIIthgroup complex302.508Isotopic exchange;hydrogen 1sotope exchangeonNwithmolecularhydrogen(1)302.511December,1959National Bureau of Standards -National Research CouncilIV
Homogeneous Reaction Klnetlbs 1 SUBJECT INDEX 3oo EXCHANGE-SUBSTITUTION 300 ISOTOPIC EXCHANGE 301 302 Title of Tab I e (number of pages) Isotopic exchange (gas) hydrogen exchange on Tab I e number Isotopic exchange; aliphatic C (2) Isotopic exchange; Isotopic exchange; Isotopic exchange; hallde (1) Isotopic exchange; Isotopic exchange; Isotopic exchange; oxide of carbon (2) halogen on aliphatic C halogen In IVth group (4) oxides of nitrogen (l) hydrogen-hydrogen hallde (l) halogen-halogen hallde (3) Isotopic exchange (liquid) Isotopic exchange; ammonia (amine) complex on group I element (l) Isotopic exchange; halogen complex on group I element (l) Isotopic exchange; valence state group I ions (1) Isotopic exchange; element (2) Isotopic exchange; Ions (11) Isotopic exchange; aliphatic C (12) Isotopic exchange; aromatic C (10) Isotopic exchange; heterocyclic ring Isotopic exchange; on carbon (6) Isotopic exchange; disulfide and thiol Isotopic exchange; hallde (l) Isotopic exchange; organic compounds Isotopic exchange; cyanide complex group II valence state group III H-D, (T) exchange on H-D, exchange on H-D exchange on C In (1) oxygen Isotope exchange sulfur exchange between (2) halogen on ivth group halogen for halogen In (25) hydrogen Isotope exchange between Vth group element and H-0 bond (3) Isotopic exchange; hydrogen Isotope exchange on N In VI nth group complex (l) Isotopic exchange; hydrogen Isotope exchange on N with molecular hydrogen (l) 301.401 301.464 301.471 301.474 301.565 301.701 301.770 302.150 302. 170 302. 190 302. 240 302. 390 302.401 302.402 302.403 302.461 302.466 302.474 302.477 302.506 302.508 302.511 National Bureau of Standards - National Research Council December, 1959
Homogeneous Reactlon Kinetics2SUBJECTINDEX(continued)Title of TableTable310HYDROGEN SUBSTITUTION(number of pages)number311Hydrogen substitution (gas)Hydrogen substitution;halogen replaced byHonaliphaticc(4)311.417Hydrogen substitution;H replaced by halogenon aliphatic c (4)311.471Hydrogen substitution; hydrogen-cyanogen(2)311.540312Hydrogen substitution (liquia)Hydrogen substitution;H on aliphaticCwith group II metal(2)312.421Hydrogen substitution;H of aromatic compoundwith group II metal(8)312.422Hydrogen substitution;nitration or aliphaticcompounds(1)312.451Hydrogen substitution;nitratlon of aromaticcompounds(22)312.452Hydrogen substitution;arylhydrogen substitution by azo (Diazonium coupling)(15)312.455Hydrogen substitution;sulfonation ofaromatic compounds(7)312.462Hydrogen substitution;aryl sulfone(2)formatlon312.467Hydrogen substitution;Hbyhalogen onaliphaticc(21)312.471Hydrogen substitution;H byhalogen onaromatic C(50)312.472Hydrogen substitution;Hbyhalogen onheterocyclic ring (3)312.473Hydrogen substitution;replacement or Hbyhalogen on $1(4)312.474Hydrogen substitution;Hby halogen onNH, or amine(3)312.570Hydrogen substitution;H by halogen on Ninamide(3)312.571330EXCHANGE OF SUBSTITUENTS331Exchange of substituents (gas)Exchange of substituents; replacement ofhalogen by NH,and :NH (1)331.754332Bxchange of substituents (liquia)Exchange of substituents,alkali metalreplaced by C(3)332.141National Bureau of Standards -National Research CouncilDecember,1959V
Homogeneous Reaction Kinetics 2 SUBJECT INDEX ( continiied) 310 HYDROGEN SUBSTITUTION Title of Table Table (number of pages) number 311 Hydrogen substitution (gas) Hydrogen substitution; halogen replaced by H on aliphatic C (4) 311.417 Hydrogen substitution; H replaced by halogen on aliphatic C (4) 311.471 Hydrogen substitution; hydrogen-cyanogen (2) 311.540 312 Hydrogen substitution (liquid) Hydrogen substitution; H on aliphatic C with group II metal (2) 312.421 Hydrogen substitution; H of aromatic compound with group II metal (s) 312.422 Hydrogen substitution; nitration of aliphatic compounds (l) 312.451 Hydrogen substitution; nitration of aromatic compounds (22) 312.452 Hydrogen substitution; aryl hydrogen sub- stitution by azo (Dlazonlum coupling) (15) 312.455 Hydrogen substitution; sulfonatlon of aromatic compounds (7) 312.462 Hydrogen substitution; aryl sulfone formation (2) 312.467 Hydrogen substitution; H by halogen on aliphatic C (21) 312.471 Hydrogen substitution; H by halogen on aromatic C (50) 312.472 Hydrogen substitution; H by halogen on heterocyclic ring (3) 312.473 Hydrogen substitution; replacement of H by halogen on SI (4) 312.474 Hydrogen substitution; H by halogen on NHg or amine (3) 312.570 Hydrogen substitution; H by halogen on N m amide (3) 312.571 330 EXCHANGE OF SUBSTITUENTS 331 Exchange of substituents (gas) Exchange of substituents; replacement of halogen by NH^ and :NH (l) 331.754 332 Exchange of substituents (Liquid) Exchange of substituents; alkali metal replaced by C (3) 332.141 National Bureau of Standards - National Research Counci December, 1959V
Homogeneous Reaction Kinetics3SUBJECT INDEX(continued)Title of TableTable330EXCHANGE OF SUBSTITUENTS(number of pages)number(continued)332Exchangeof substituents(liquid)Exchange of substituents;replacement or(3)332.363Boron by o on aromatic CExchange of substituents;replacement ofBoron by halogen on aromatic c(6)332.373Exchange-of substituents;replacement ofCbyN on aromaticC(3)332.452Exchange of substituents;replacement ofC by sulfate on Sf (i)332.464replacement ofExchange of substituents;(2)332.472C by halogen on aromatic CExchange or substituents;replacement of332.473Si by halogen on aromatic c(1)Exchange of substituents;replacement or N by332.501Oon aliphaticc(2)Exchange orsubstituents;replacement of N= byO=on aromatic c(6)332.503Exchange of substituents;replacement ofAr(SO,), (ArSO,),(ArSO) Dy NR'R"Rm(2)332.653Exchange of substituents;replacement of(2)halogen by C (of enolate)332.741replacement orExchange of substituents,halogen on Si by C(2)332.744replacement ofExchange of substituents,halogen byNo,and (or)ono on aliphatic C(4)332.750Exchange or substituents;replacement of(3)332.751halogen by NO,Exchange of substituents;replacement of332.753halogen by azide(2)Exchange of substituents,replacementofhalogen by NH,and :NH(1)332.754replacement ofExchange of substituents,332.761halogen by So,=(15)Exchange of substituents;replacement ofhalogen by Thio alkyl (aryl)(8)332.763Exchange ofsubstituents:replacement ofhalogen by thiocyanate(2)332.765replacement ofExchange of substituents,halogen by S of thiourea(2)332.766Exchange of substituents;halogen for halogen332.771on aliphatic carbon(34)National Bureau of Standards - National Research CouncilDecember,1959VI
Homogeneous Reaction Kinetics 3 SUBJECT INDEX (continued) 330 EXCHANGE OF SUBSTITUENTS Title of Table Table (number of pages) number (continued) 332 Exchange of substituents (liquid) Exchange of substituents; replacement of Boron by 0 on aromatic C (3) 332.363 Exchange of substituents; replacement of Boron by halogen on aromatic C (6) 332.373 Exchange of substituents; replacement of C by N on aromatic C (3) 332.452 Exchange of substituents; replacement of C by sulfate on SI (l) 332.464 Exchange of substituents; replacement of C by halogen on aromatic C (2) 332.472 Exchange of substituents; replacement of SI by halogen on aromatic C (l) 332.473 Exchange of substituents; replacement of N by 0 on aliphatic C (2) 332.501 Exchange of substituents; replacement of N= by 0= on aromatic C (6) 332.503 Exchange of substituents; replacement of Ar(SOg), (ArSOg), (ArSO) by NR' R"R'" (2) 332.653 Exchange of substituents; replacement of halogen by C (of enolate) (2) 332.741 Exchange of substituents; replacement of halogen on SI by C (2) 332.744 Exchange of substituents; replacement of halogen by NO^ and (or) ONO on aliphatic C (4) 332.750 Exchange of substituents; replacement of halogen by NOg~ (3) 332.751 Exchange of substituents; replacement of halogen by azlde (2) 332.753 Exchange of substituents; replacement of halogen by NH^ and :NH (l) 332.754 Exchange of substituents; replacement of halogen by S^Og^ (15) 332.761 Exchange of substituents: replacement of halogen by Thlo alkyl (aryl) (8) 332.763 Exchange of substituents; replacement of halogen by thlocyanate (2) 332.765 Exchange of substituents; replacement of halogen by S of thiourea (2) 332.766 Exchange of substituents; halogen for halogen on aliphatic carbon (34) 332.771 National Bureau of Standards - National Research Council December, 1959
Homogeneous Reaction Kinetics1SUBJECTINDEX(continwed)Title of TableTabie350EXCHANGE ON Vth GROUP ELEMENT(number of pages)number(continued)352Exchangeon Vth group element (liquid)Exchange on Vth group element,halogen replacedby nitrogen on P(2)352.750Exchange on vth group elemernhalogen forhalogen on P (1)352.770400ELIMINATION400PROTON ELIMINATION402Protonelimination(liquid)Proton elimination;from CH bond activatedbyadjaeent Co, (CoOR).(CN),(NO,)402.450(8)420BOND-UNSATURATION ELIMINATION422Bond-unsaturation elimination (liquid)Bond-unsaturation elmination; or C,H.N and H*422.450to form c:(1)Bond-unsaturation elimination;of HNO,and (or)HNO, from nitrate ester:(9)422.451or N0o, andBond-unsaturation elimination;halide ion to form C:c (1)422.457Bond-unsaturation elimination;thio ether andHfrom alkyl sulfonium 1on422.461(5)Bond-unsaturation elimination;aryl sulfonic(10)422.463acid from alkyl arylsulfonateArsog andBond-unsaturation elimination;422.467halideion to formc:c(1)hydrogenBond-unsaturationelimination;(41)422.471halide to form C:Bond-unsaturation elimination;halogenmolecule by halide 1on(15)422.477430RING-CLOSURE ELIMINATION432Ring-closure elimination (liquid)co,tromRing-closure elimination;432.404dicarboxylate(2)Ring-closure elimination;of H,O Or ROH(6)432.441Ring-closure eliminatlon;of H,o.with432.442(2)formation of aromatic ring(1)432.455orNo,Ring-closure elimination;Ring-closure elimination;of halogen from(1)432.476halo thio etherNational Bureau of Standards - National Research CouncilDecember, 1959VII
Homogeneous Reaction Kinetics 4 SUBJECT INDEX (continued) 350 EXCHANGE ON Vth GROUP ELEMENT Title of Table Table (number of pages) number (continued) 352 Exchange on Vth group element (liquid) Exchange on Vth group element; halogen replaced by nitrogen on P (2) 352.750 Exchange on Vth group elemenu. halogen for halogen on P (1) 352.770 4oo ELIMINATION 400 PROTON ELIMINATION 1^02 Proton elimination (liquid) Proton elimination; from CH bond activated by adjacent CO. (COO R), (CN), (NO^) (s) 402.450 420 BOND-UNSATURATIOfI ELIMINATION U22 Bond-unsaturation elimination (liquid) Bond-unsaturatlon elimination; of C H N and h"^ 5 "5 to form C: C (l) 422.450 Bond-unsaturatlon elimination; of HNOg and (or) HNOg from nitrate ester (9) 422.451 Bond-unsa1;urat Ion elimination; of NO^" and hallde Ion to form C: C (1) 422.457 Bond-unsaturatlon elimination; thlo ether and H"*" from alkyl sulfonlum Ion (5) 422.461 Bond-unsaturatlon elimination; aryl sulfonic acid from alkyl arylsulfonate (10) 422.463 Bond-unsaturatlon elimination; ArSOg" and hallde Ion to form C:C (1) 422.467 Bond-unsaturatlon elimination; hydrogen hallde to form C:C (4l) 422.471 Bond-unsaturatlon elimination; halogen molecule by hallde Ion (15) 422.477 430 RING-CLOSURE ELIMINATION 432 Ring-closure elimination (liquid) Ring-closure elimination; CO^" from dlcarboxylate (2) 432.404 Ring-closure elimination; of H^o or ROH (6) 432.441 Ring- closure elimination; of H^o with formation of aromatic ring (2) 432.442 Ring-closure elimination; of NOg" (l) 432.455 Ring-closure elimination; of halogen from halo thlo ether (l) 432.476 National Bureau of Standards - National Research Council December, 1959 VU
Homogeneous Reaction Kinetics5SUBJECTINDEX(continued)Title of TableTable450ELIMINATIONFROMVthGROUPELEMENT(number of pages)number(continued)452Fliminationfrom Vthgroupelement(iiquid)Elimination from Vth group element;carboniumlon from quaternary ammonium salt(1)452.474460ELIMINATIONFROMFUNCTIONAL GROUPElimination from functional group (liquid)462Elimination from functional group;N,ofromaciform of nitroalkane(i)462.451National Bureau of Standards - National Research CouncilDecember,1959VIHI
Homogeneous Reaction Kinetics 5 SUBJECT INDEX (continued) 450 ELIMINATION FROM Vth GROUP ELEMENT Title of Table Table (number of pages) number (continued) ^52 Elimination from Vth group elenent (liquid) Elimination from Vth group element; carbonlum Ion from quaternary ammonium salt (l) 452.474 460 ELIMINATION FROM FUNCTIONAL GROUP tie 2 Elimination from functional group (liquid) Elimination from functional group; N^G from acl form of nltro alkane (l) 462.451 National Bureau of Standards - National Research Council December, 1959 vni
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