《物理化学实验》课程教学资源（书籍文献）Tables of Chemical Kinetics Homogeneous Reactions（Supplementary Tables，PDF电子书）

UNITED STATES DEPARTMENT OF COMMERCE·Luther H.Hodges, SecretaryNATIONAL BUREAUOF STANDARDS·A.V.Astin,DirectorTables of Chemical KineticsHomogeneous Reactions(Supplementary Tables)National Bureauof StandardsA. V. Astin, DirectorNational Research Council, Division of ChemistryCommittee on Kinetics of Chemical ReactionsM. L. Kilpatrick, ChairmanH. TaubeJ. BigeleisenR.NoyesM.WallensteinC. SatterfieldProject Office: Hepburn Hall, St. Lawrence University, Canton, New YorkC. H. Stauffer, Project DirectorA. R, AmellD.M.KernE. BuncelH. G. KuivilaH. B. FeldmanP.E. MerrittH.S.JohnstonH.TaubeNational Bureau of Standards Monograph 34Vol.2To Accompany National Bureau of Standards C510, Supplements 1 and 2,and Monograph 34—Vol.1Issued July 1,1964

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 M. Wallenstein C. Satterfield Project Office: Hepburn Hall, St. Lawrence University, Canton, New York C. H. Stauffer, Project Director A. R. Amell D. M. Kern E. Buncel H. G. Kuivila H. B. Feldman P. E. Merritt H. S. Johnston H. Taube National Bureau of Standards Monograph 34 Vol. 2 To Accompany National Bureau of Standards C510, Supplements 1 and 2, and Monograph 34 Vol. 1 Issued July 1, 1964

PrefaceThese tables have been prepared and organized as a supplement to the tables of chemicalkinetics in National Bureau of Standards Circular 510, Supplement 1 to National Bureau ofStandards Circular 510, and National Bureau of Standards Monograph 34. Code abbrevia-tions for literature references, definitions of symbols and quantities used in the tables are givenin the introduction of NBS Circular 510.A brief description of the method used in compilingthese tables and the limitation of coverage are given in the preface to Supplement 1 of theNBS Circular 510.A description of the numbering system used in classifying reactions forthe tables and an index are given in Supplement 2 of the NBS Circular 510.The present volume contains information pertaining to substitution, exchange, and elimi-nation reaction types and extends the material on these reaction types found in NBS Mono-graph 34, Volume I.The date on each page gives the year and month to which the literaturehad been surveyed.Significant omissions or errors should be reported to the Director of theProject: Dr. Charles H. Stauffer, Head, Department of Chemistry, St. Lawrence University,Canton, New York.The Director of the Project and his associates gratefully acknowledge the financial assist-ance provided by theOffice of OrdnanceResearch, Department of theArmy,Office of NavalResearch, Atomic Energy Commission, National Science Foundation, and the National Bureauof Standards to make the compilation of these data possible.The Director of the Projectgratefully acknowledges the able assistance of his associates and collaborators in the reviewand analysis of the material in the chemical literature.He also acknowledges the assistanceof the staff of the National Academy of Sciences and of the members of the Committee onChemical Kinetics of the National Academy of Sciences, Division of Chemistry.C.H.STAUFFER

Preface These tables have been prepared and organized as a supplement to the tables of chemical kinetics in National Bureau of Standards Circular 510, Supplement 1 to National Bureau of Standards Circular 510, and National Bureau of Standards Monograph 34. Code abbrevia tions for literature references, definitions of symbols and quantities used in the tables are given in the introduction of NBS Circular 510. A brief description of the method used in compiling these tables and the limitation of coverage are given in the preface to Supplement 1 of the NBS Circular 510. A description of the numbering system used in classifying reactions for the tables and an index are given in Supplement 2 of the NBS Circular 510. The present volume contains information pertaining to substitution, exchange, and elimi nation reaction types and extends the material on these reaction types found in NBS Mono graph 34, Volume I. The date on each page gives the year and month to which the literature had been surveyed. Significant omissions or errors should be reported to the Director of the Project: Dr. Charles H. Stauffer, Head, Department of Chemistry, St. Lawrence University, Canton, New York. The Director of the Project and his associates gratefully acknowledge the financial assist ance provided by the Office of Ordnance Research, Department of the Army, Office of Naval Research, Atomic Energy Commission, National Science Foundation, and the National Bureau of Standards to make the compilation of these data possible. The Director of the Project gratefully acknowledges the able assistance of his associates and collaborators in the review and analysis of the material in the chemical literature. He also acknowledges the assistance of the staff of the National Academy of Sciences and of the members of the Committee on Chemical Kinetics of the National Academy of Sciences, Division of Chemistry. C. H. STAUFFER

Contents(Supplementary Tables)PageiliPreface.ivSubjectindexTables..1

Contents (Supplementary Tables) Page Preface._-_-._.-_>._._._._._ iii Subject index_ iv Tables.-_-_-_._-_-_-_-_._-_-_-_- _._._ 1

Homogeneous Reaction KineticsSUBJECTINDEX300 EXCHANGE-SUBSTITUTIONTitle of TableISOTOPICEEXCHANGETable300(number of pages)number302Isotopic exchange ((liquia)(5)302.440Isotopic exchange;carbon-1sotope exchange(1)302.474.1halogen on Ivth grouphalide..*Ehalogen isotope exchange between Ivth group and(2)302.475Vth group atoms..(3)302.560exchange or oxygen on vth group element.E(1)302.575halogen exchangebetween Vth group halides：.E(2)302.590Vth group elements between oxidation states:."(1)302.6000.exchange with H,o and H,02En(1):hydrogen,D,exchange with water302.601n(2)n302.640:VIth group cyanide complex with CN.n(1)302.650:VIthgroup NH,complexwithNH"nexchange invoivingVithgroup element ascentral.SUPPLEMENT(9)302.660atom in both reactants.nvith group central element complexed with:(1)302.670exchangingVIIthgroupions1o(1)302.690Vith group element between oxidation states".:Vith group element involving complexed valence(2)states302.6961960-(1).302.740"cyanlde ion with Viith group cyanide complex..(2)302.760;exchange of oxygen attached to viith group element-n(3)VIIth group element between oxidation states302.790;-.(2)N-bonded complex exchanging on VIIIth group element302.850：-.(6)302.858VIIIth group lon exchange with N-bonded complex:-n(2)O-bonded complex exchanging on VIlIth group element302.860;?.halogen 1on exchange on vilith group complex(5)302.870;.n(6)302.890Vilith group element between oxidation states310HYDROGEN SUBSTITUTION312Hydrogen substitution (liquid)Hydrogen substitution; hydrogen substitution by oxygen (alkoxy)(5)(phenoxy)on boron hydrides312.301Fn: hydrogen replacing Ivth group element on(2)aromaticc312.402""(1)H on aliphatic Cwith group I metal312.411"+(1):hydrogen replacing halogen on aliphatic c312.417.";H on aromatic C replaced by C.Aromatic(26)alkylation312.442E.; H on nitrogen replaced by NC,(2)312.552330EXCHANGE OF SUBSTITUENTS332Exchange of substituents (tiquid)(1)Exchange of substituents; IInd group metal on aliphatic c exchange332.221:E;IInd group metal on aromatic-C replaced(a)by N332.252-En; IInd group metal on aliphatic C replaced(3)by acid radical332.261December, 1960Nationai Bureau of Standards-National Research Councii

Homogeneous Reaction Kinetics SUBJECT INDEX 3oo EXCHANGE-SUBSTITUTION 300 ISOTOPIC EXCHANGE Title of Table . . , ,. ., (number of pages) 302 IsDtofa exchange (liquid) ^ I so topic exchange it n n n n n « n n n n n n N n n n n it n n n W ft n n n fi n n « n ft n rt n N ft n ft n n carbon- Iso tope exchange halogen on ivth group hallde halogen Isotope exchange between ivth group and Vth group atoms exchange of oxygen on Vth group element halogen exchange between Vth group halldes Vth group elements between oxidation states 02 exchange with H2 0 and H202 hydrogen, Dg exchange with water VI th group cyanide complex with Chf Vlth group NHg complex with NH exchange Involving VI th group element as central atom In both reactants Vlth group central element complexed with exchanging VII th group Ions Vlth group element between oxidation states Vlth group element Involving complexed valence states cyanide Ion with VII th group cyanide complex exchange of oxygen attached to VII th group element Vllth group element between oxidation states N-bonded complex exchanging on Vlllth group element VIII th group Ion exchange with N-bonded complex 0- bonded complex exchanging on Vlllth group element halogen Ion exchange on Vlllth group complex Vlllth group element between oxidation states 310 HYDROGEN SUBSTITUTION 312 Hydrogen substitution (liquid) Hydrogen substitution; hydrogen substitution by oxygen, (alkoxy) (phenoxy) on boron hydrides " " ; hydrogen replacing ivth group element on aromatic C " « ; H on aliphatic C with group I metal " " ; hydrogen replacing halogen on aliphatic C M " ; H on aromatic C replaced by C. Aromatic alfcylation 11 " ; H on nitrogen replaced by NO 2 330 EXCHANGE OF SUBSTITUENTS 332 Exchange of substituents (liquid) Exchange of substituents; lind group metal on aliphatic C exchange " » " ; lind group metal on aromatlc-C replaced by N " " " ; lind group metal on aliphatic c replaced by acid radical (5) (1) (2) (5) (1) (2) (1) (1) (1) (1) (9) CD CD (2) (1) (2) (3) (2) (6) (2) (5) (6) (5) (2) (1) CD (26) (2) (1) (1) (3) Table number 302.440 302.474 302.475 302.560 302.575 302. 590 302.600 302.601 302. 640 302.650 302.660 302.670 302.690 302.696 302.740 302.760 302.790 302.850 302.858 302.860 302.870 302.890 312.301 312.402 312.411 312.417 312.442 312.552 332.221 332.252 332.261 National Bureau of Standards - National Research Council December, I960

Homogeneous Reaction XineticsSUBJECTINDEX(continued)Title of TableTable330EXCHANGE OF SUBSTITUENTS(continued)(number of pages)number332Exchange of substituents(liquid)Exchange or substituents, vth group element on aliphatic creplaced byC(1)332.541".;NO,(NO)replaced byN on aliphatic or(1)332.551aromaticcn...;ROSo,on aliphatie creplaced byR's(2)332.661"n.(2)332.672: S0.on aromatic C replaced by halogen"..(5)332.772;halogen forhalogen on aromatic carbonne.; halogen exchange ror halogen on Ivth(2)group element332.774380COORDINATIVE EXCHANGE382Coordinative exchange (liquia)(1)Coordinative exchange; H,o replaced by N compound in Group I complex382.1054:Ho or solvent replacing N compound on GroupISuppl ement(2)382.150complex(solvent not always shown on equation)n(1)382.170;H,o replacing halogen on Group I complexn.H,o replacing N compound in Group II complex(1)382.250n=H,o (oH) exchange with halogen on Group v(2)complex382.5701960-C compound replacing H,o in Group VI complex(4):382.604"N-compound replacing Ho on Group vI complex(2)382.605"n:H,o (H,o) replacing c-compound on vIth group(1)complex382.640nH,o(H,ot)(OH)replacingN-compoundon:(4)vIthgroupcomplex382.650n; halogen replaced by H,o (H,o (OH) on VIth groupcomplex (H,o not always showm in complex)(3)382.670n:H,o or oHreplacing carboxylate in VIIIth group(2)complex382.800nN-compound replacing H,o in vIlith group complex：(H,onotalwaysshownin formula or complex)(5)382.805n：s compound replacing H,o in vilIth group complex(H,o not always showm)(2)382.806n;haiogenreplacingH,oinVIIthgroupcomplex(2)382.807+; H,o replacing (CN)(sCN)(co,) on VIIIth groupcomplex(2)382.840n:Nor P-compound replacinga-compound in VIIIth(1)group complex382.845H,o(oH)replacing N compound in VIIth complex：(H,onotalways shown in formula or complex)(11)382.850;N orp-compoundreplacingNor p-compound in(5)ViIIthgroupcomplex382.855：S-compound replacing N-compound in vIIIth group(1)complex382.856NationaiResearch CounciiNational Bureau of StandardsDecember,1960

Homogeneous Reaction Kinetics SUBJECT INDEX (continued) Ti 11 e of Tabl e Tab 1 e 330 EXCHANGE OF SUBSTITUENTS (continued) (number of pages) number 332 Exchange of substituents (liquid) Exchange of substltuents vth group element on aliphatic c replaced by c (l) 332.541 N0 2 (N0 3 ) replaced by N on aliphatic or aromatic C (l) 332.551 ROS0 2 on aliphatic c replaced by R»S (2) 332.661 SO ~ on aromatic C replaced by halogen (2) 332.672 halogen for halogen on aromatic carbon (5) 332.772 halogen exchange for halogen on I Vth group element (2) 332.774 380 COORDINATIVE EXCHANGE 382 Coordinative exchange (liquid) Coordinative exchange; H S Q replaced by N compound in Group I complex (l) 382.105 " " J H^o or solvent replacing N compound on Group I Co ft " n n n n n fi " fi " " M n n n H complex (solvent not always shown on equation) " ! H 2o replacing halogen on Group I complex " ' H 2 o replacing N compound In Group II complex " '» H o (OH ) exchange with halogen on Group V complex " ; C compound replacing H 20 in Group VI complex " ; N-compound replacing H g o on Group VI complex N 5 H20 (H O 4) replacing c- compound on VI th group complex " '» H o (H 0+) (OH~) replacing N-compound on VI th group complex " ; halogen replaced by H o (H 0+) (OH~) on VI th group complex (H 2 o not always shown in complex) " I H o or OH~ replacing carboxylate in villth group complex « ; N-compound replacing H SO in Villth group complex (Hgo not always shown in formula of complex) 11 ; S compound replacing H SO in VI 11th group complex (H 2o not always shown) " ; halogen replacing E Q Q in Villth group complex " ' H 2Q replacing (CN~) (SCN~) (CO =) on VIII th group complex " ; N or p-compound replacing a c-compound in villth group complex " J H2 o(OH~) replacing N compound In Villth complex (H2o not always shown in formula of complex) " ; N or p-compound replacing N or p-compound in VI Ilth group complex " ; S-compound replacing N-compound in villth group complex (2) (1) (1) (2) (0 (2) (1) (0 (3) (2) (5) (2) (2) (2) (1) (11) (5) (1) 382.150 § 382. 170 ^ 382.250 § 7H- 382.570 382.604 Co o> 382.605 O 382.640 382.650 382.670 382.800 382.805 382.806 382.807 382.840 382.845 382.850 382.855 382.856 National Bureau of Standards - National Research Council -inrn December, I960

Homogeneous Reaction KineticsSUBJECTINDEX(continued)Title of Table(continued)380COORDINATIVE EXCHANGE(number of pages)382Coordinative exchange (liquid)Coordinative exchange;H_o replacing 8-compoundin vIIith group(1)382.860complex1;N-compoundreplacingS-compoundinVilIth(1)382.865group complex":H,O,OH or ORreplacing halogen in VIIIthgroup complex (H_o notalways shown In complex)(22)382.870nn; N-compound replacing halogen In VIIith group(6)complex382.875n;ROHRcoo",coorScompoundreplacing(2)382.876halogen in vIlith group complex:Halogenreplacinghalogen inViiith group(a)complex382.877400ELIMINATION400PROTON ELIMINATION Supplement402Protonelimination(liquid)Proton elimination; proton elimination from oH-bond (carboxylic acids(3)and phenols,ionization and recombination)402.461420BOND-UNSATURATION ELIMINATION1960422Bond-unsaturationelimination(liquid)Bond-unsaturation elimination; Hg(ll) from ethylenic addition(5)compound422.421430RING-CIOSURE ELIMINATION432Ring-closure elimination (liquid)Ring-closure elimination;elimination orhydrogenhalide from halo-(8)432.471hydrinswith ringclosure#elimination of hydrogen halide,or halide(11)lon to form N-containing ring432.475December,1960National Bureau of Standards -National Research Council

Homogeneous Reaction Kinetics SUBJECT INDEX (continued} Title of Tab Ie 380 COORDINATIVE EXCHANGE (continued) (number of pages) 382 Coordinative exchange (liquid) Coordinatlve exchange; H SO replacing s-compound in VI nth group complex (1) 382.860 " " ; N-compound replacing s-compound in Vlllth group complex (1) 382.865 " " ; H go, OH~ or OR~ replacing halogen in villth group complex (R^Q not always shown in complex) (22) 382.870 " " ; N-compound replacing halogen In Vlllth group complex (6) 382.875 " " J ROH, RCOO , CO ~ or S compound replacing halogen in Vlllth group complex (2) 382.876 M " ; Halogen replacing halogen in Vlllth group complex (1) 382.877 4oo ELIMINATION 400 PROTON ELIMINATION tl-02 Proton elimination (liquid) t§ Proton elimination; proton elimination from OH-bond (Carboxylic acids ^ and phenols, lonization and recombination) (3) 402.461 § (to ^ 420 BOND-UNSATURATION ELIMINATION ^ U22 Bond-unsaturation elimination (liquid) ^ Bond-unsaturatlon elimination; Hg(ll) from ethylenic addition S compound (5) 422.421 430 RING-CLOSURE ELIMINATION >432 Ring-closure elimination (liquid) Ring-closure elimination; elimination of hydrogen hallde from halo￾hydrins with ring closure (Q) 432.471 " " ; elimination of hydrogen hallde, or hallde ion to form N-containing ring (11) 432.475 National Bureau of Standards - National Research Council December, i960

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Homogeneous Reaction Kinetics 302.440 No. .13 .14 .15 .16 .17 React ion CH OAC VT\E )^ -. OOC 14CH 3 H OOCCC1 3 (2-0-t ri chloroacet y l-OC~D-g 1 ucopy ranose tetraacetate) CH2OAc H X| ° \ OOC 14CH 0 { / P \ i \ OAC H A 3 AcO \1 JX H H OOCCC1 3 (2-0-tri chloroacety 1-yS-D-g lucopyranose tetraacetate) (C H ) CHC 14H(C H )OOCCH — > 652 65 3 CH COO(C H )CHC 14H(C H ) 3 60 652 (C H ) CHCH(C*H )OOCCH —— > 652 66 3 (C H ) (C*H )CHCH(C H )OOCCH 6565 65 3 652 65 3 3 (C H ) CHCH(C H )OOCCH + CH C 14OOH 652 66 3 . 3 Sol vent (CHg CO) 2 0 + CH COOH 3 (CH3 CO) 20 + CH gCOOH CH 0 COOH o CHGCOOH j CH.COOH o Amount of reactant A=0.l;B=50# of solvent A=0.1;B=50% of solvent 10 A= 1.25 10A=1.25 10 A= 1.25 Addend H^^ H 2 S°4 A 4 #>-CH3C6H4 S03 H C H SO H 364 3 ^-CH3C8H4S0 3H H- O -o C c -S 1 * -1 0.5 0.5 0.126 0.126 0.126 0.276 e ~~ -o c c ~ *0 (tf feA k A * FE ftF E * FE 3 -*-1 k_ -t-" _J (°) ( / ( 8 ) ( 8) ( 8) CO 8 National Bureau of Standards - National Research Council December, I960