SUPPLEMENT19600961r-U0 01y pus 6+8yi/n u ole shunony(g)CC26ee!1sesecjoqwoboo*sauan**0LE988at艺&or14-I591312055v1-VI-1223805n222010747463290.91l333853335Ie626O0So3'T~2227222t0业05855555S1885058855555[_0,ga-ssew pouioda'+a'?M81 uo170msoiaeee7aHpuoppe380.8o6Ob6c036Joqunowy58opueppyTOH--08--8,0 :00-9-,0me1228g01 :02-8-Vg 0101-s'T-Vg002-8g00"=8-81ouno12202e0*100ToAO"09s9+*98"od++o$++ ++++ <+8+9saeueasotodrnsrory snaro 0+98 + 6+98tos +t0d+*1*+ +8+*g06200+10suoten234'ON-
Homogeneous Reactions 302.590 ISOTOPIC EXCHANGE Vth group element between oxidation states Liquid phase Amounts are in M/I. Rates and rate con stants are in gram atoms/I and sec. No. .1 .2 .3 .4 React i on P*C1 + PCI — > PCI + P*C1 35 3 6 Sb** 3 + Sb* 0 — > Sb+3 + sb*"*" 8 Sb*Cl + SbCl — > SbCl + Sb*Cl 38 35 Y3r^2 _j_ Y • — "^ Y + y5^^ Solvent cci 4 H 2Q cci 4 H 0 2 Amount of reactant 10 3A=5-60; 10 3B=5-20 10 2A=2-30; 10 2B=2 2.1 2.1 0.8-2 0.08-4 2.1 2.1 10 2A=1.5-10; 10 3B=5-70 10 2A=4-13; 10 2B=4-12 ^=2.0 Addend HC1 ! of Amount ! addend 2.3 5.8 8.8 10.8 11.7 5.9 HCl,NaCl 5-6 HC10 4 " 5.9 1.00 0.198 0.5-0.12 1 Defined massact i on 1 aw feB fcAB fe f A' 6B 1 * 1 [H"f] 4 [ci~] 9 feAB fe = * + k [H*]"* 1 + fe 3 [ci~] Temperature 0 25 50 25 25 25 25 25 10 25 35 50 50 68 68 81 81 25 25 25 25 25 k — k° x 2.5 2.9 2.3 -1.5 2.7 1.3 7.5 6.0 2.0 2.5 9.7 V-8 k 7.5 *26 -° fe 2. 1 V-B 1.4 3.2 fe i.o fe^M.4 o 10" n -7 -6 -5 -1 -2 -2 -3 -3 -15 -14 -14 -7 -4 -7 -4 -6 -3 -2 -2 -2 -3 • 16 27 19 15 13. A A° x A° 1.2 1 4 Ast -25 10n n 6 6 6 Comments * * * Li terature ( 2) < 6) ( 3) (') ( 5) National Bureau of Standards - National Research Council December, I960
1960Supplement096taoqwe0oCCS*SoOL282=ota etaee()naaeeeeateneo o o o aeei reaaaoaeieinea eens eaeeoaareaesees()asn()ea-8V(9')ne eneersan s&511429"A2-0533(g)ates pappe se'Ta0'8o492I~ar aueerat esnou aae seensseari aoedessen oaoeeatageteotdoost ue8584e1-[+H] aVneoseeemel uo17n-ssewpouitooralla eiase see seeaam eaoran eseaiean2-90a-90pueppeJunouf0puappvOTOH"OTOeeanrereseea9--o so-0*-[e+1SEE9-1-g01 -I-V01JounoeS'a=ees(g)e0°m ()esonoieeseeeuhenpaepueis aneegeuoiieno-0t ×a-y susn e++ 12+OA + 8+H0*4es++0 + e+*A ( +*A + e+tteen +OA +g+HO6920'ON58
Homogeneous Reaction Kinetics 302.590 -*-> c No. Reaction > o CO .5 V+3 4- vV2 — > V*+ 3 + VO+2 H 2 .6 VOH- + V*0- -^ V*OH- + VOAmount of reactant 0 10 2A=1-5J 10 2B=l-5 /X=2.5 0 [ V J = . 0 1~ . 0 5» 10 B^ 1- 5 COMMENTS Addend HC1 ° 4 HC10 4 Reaction: (.1) Exchange rate and rate law in gram atoms per liter was 0 -a t • 5 "° o "S 1 " 0.5-2 0.5-2 i , s i e — T3 ^ 0 0 .5 £ •*- % 0) «* o k AB [H4"] 1 feAB ID l_ 3 rt i_ 03 O. E 0) »— 25 32 40 25 k = / te° x if/1 A° E k° n A° 2.6 -3 8.0 -3 1.44 -2 21 5 ~1 0 li 1 x I0n » • •£ 3 C +j ® <tf 1 • O +j n o _J ( 4) 12 8 * ( 4) Identical for phosphorous exchange using P 32 and chlorine exchange using Cl 36 for labeling, see 302.575.1. Addition of small amounts of molecular or increased glass surface had no measurable effect on either exchange rate. feet on phosphorous exchange rate but definite catalytic effect on chlorine ly determined by ( 3) considered to have no fundamental significance. Addition of HCI or exchange rate. oxygen, illumination H o had no measurable ef- (.2) Rate law empirlcal- ( 6) determines exchange rate under non- equilibrium conditions by preparing stock Sbci and SbCl solutions in concentrated HCI and diluting at start of reaction, under these 5 3 conditions exchange is found to be more rapid in the more dilute HCI solutions. different rate controlling steps in dilute The complex kinetics is attributed to acid and concentrated acid. It is suggested that in trolling step is the rate of formation of the Sbci ~ Ion, while in reaction of the SbCl " ion with the Sbci dilute acid the rate conconcentrated acid the rate controlling step is the species capable of exchanging with it. Experiments performed with either reactant isotopically labelled. Reaction vessel packed with glass beads gave no to accelerate exchange reaction, packing with glass beads had no observable exchange rate by light, glass surface, doubling ionic strength or replacing sumed to be rate determining step for (.5) of V+3 using K =2 x io~ 3 - n (*) F. Barker, M- Kahn, ACS ( 3) N.A. Bonner, ACS 1949, 71, 3909. and calculated from constant for LITERATURE change effect. NaCIO in exchange (-4) rate. NO (.3) Light said observable effect on by Li CIO as added salt. (.6) As- (.5) on basis of rapid reversible hydrolysis 1956, 78, 1317. ( 2 ) W. E. Becker, R. ( 4) S. C. Furman, C. S. Garner, ACS E. Johnson, ACS 1957, 79, 5157. 1952, 74, 2336. Krlshnamurty, A. C. Wahl, ACS 1958, 80, 5921. ( 6) H.M. Neumann, H. Brown, ACS 1956, ( 5) K.V. 78, 1843. OS National Bureau of Standards - National Research Council December, I960
SUPPLEMENT19600961$ow!+ +ieh 'des1/n ul oun shunouy CCoetloqwaooseee*508*u!000*6eaealaateeons&pue0=0Ot43-16222222[_HO] 090982e0[-0°g]292696961Pmsseeaoased see a tesrie asaoue raeerjo tunow{900°-100pueppe一SLTJti-Ha192900*寳seera20°0“0"H pup 0H 4ym abupyxo"0E-spueppyHOBNSENEEE890v'a1:6L'l=v,0110000tunouyuopioos"Noelr*4888eseseneeaseunogTRs0T2eoi50eui+en"0+o0'm+gtrensaos()anr19100to“0+00200eeaneuoi+0H"0"H2"ON1
Homogeneous Reactions 302.600 ISOTOPE EXCHANGE 0 exchange with H 0 and HO. under rate law Indicates that rate constant Is for pseudo first order rate of Isotoplc equilibration. Liquid phase Amounts are in M/I. Rates and rate con stants are in M/ I and sec. Half ti mes are in sec. No. React i on Amount of reactant Addend Amount of addend k = io .1 H 20 QO 18 H 20 B sat. at 0.5 a tin. H 20 10 4A=1.79; 10 3B=1.19 buffer S 0 2 8 NaOH NaOH NaOH .006251 PH 2- 11J .ooi-.ooe] 0.03 J .006251 >0.2 J PH 11.75 60 60 60 25 -4 3.2 2.3 -2 9,000 COMMENTS Reaction: (.1) Oxygen exchange catalyzed by persulfate generated free radicals. Below pH=ll chain length of free radical reaction approximately 4. Above pH=ll chain length increases rapidly then levels off to about 450 at [OH~] = 0.2. Pseudo first order exchange rate constant corrected for the fraction of oxygen in the gas phase. LITERATURE ( 1 ) C.R. Gulliano, N. Schwartz, W. K. Wllmarth, J.P.C. 1959, 63, 353. ( 2 ) E.J. Hart, S. Gordon, D. A. Hutchinson, ACS 1953, 75, 6165. National Bureau of Standards- National Research Council December, I960
1960SUPPLEMENT096t (1eque080 n r rn shunowy52Caspyd pabatieiesiueie**saen1oospu339TE1x×xxu 4d () (2)(8")"LL8'T044e261posueuoxe%RuOT×o41O33333422042727230141o336536W'OO+'0or:0010OOT0080SOTraaeaeeosesane HMEI U0130FssroiePuappes=B=osunowyttpueppy+xam uxoQH%eCOOTOa0'TOA福288.288'jotunowyuei0eeSEE.161581O29'0O'908woon ue日8S29618000TIOUesTEOTENarnT(")saeees+_ + H 个_HO + CH*(2") pueSroanoaaroo"H'M1Jo/15109200_HO + QH_a0 +_HO +-a-0121?0
Homogeneous Reactions 302.601 1SOTOPIC EXCHANGE Hydrogen, D exchange with water Liquid phase Amounts are in M^l. Rates and rate con stants are in M/I and sec. No. .1 .2 .3 React! on H 4- OD~ — ^ HD + OH" 2 HD 4- OH — * H 2 + OD D2 + OH~ — > HD * °D~ c o > o CO V H a° H 0 Amount of reactant sat. with A at 1 atm. and room temp. B = 0.1 0.2 0.5 1.0 D +up to 50 vol. % HD 2 sat.; B = . 1246 .534 .882 sat. with D ; B = .1246 .534 .882 13 C C TJ -a «c K+ K4" K+ H- 0 T3 - g = -o H ~° 1 * = B = B = B iscd rt E — ^ s <D 0 C """ ^ s 0 «1 0 feAB feAB 05 U•3 -H 1. 0) 0. e 4} t— 100 100 100 100 100.4 100.4 100.4 94 101 105 k = fe° x 10n fe° n % exchanged 7.2 12.0 7.4 12.8 3.2 3.3 3.9 5.1 6.1 5.4 -3 -3 -3 -3 -3 -3 S time 1.8 x io 5 1.8 x 10 5 4 x io 4 4 x io 4 CO -H C O E E 0 O * * 0 l_ 3 -H Of i. 4) -*-> _J < 2 > C 1) f 1) COMMENTS Reaction: (.1) Data gives little more than order of magnitude of exchange rate. Authors observed exchange rate in IN KOH to be about 8 times faster than in IN HC1 and 25 times faster than in neutral D go. (.2) (.3) Rate con stant calculated from integrated form of differential rate equation for two consecutive first order reactions, (.3) and (.2). LITERATURE (*) W.K. Wllmarth, J. C. Dayton, J.M. Flournoy, ACS 1953, 75, 4549. ( 2) K. Wirtz, K.F. Bonhoeffer, ZPCh 1936, 177, 1. National Bureau of Standards - National Research Council December, I960