1960SUPPLEMENT0961e)/w u! eib siue+sesuouoe e seree!5C0C22eaoqwoooosrewon***0ospueOT*24o&ao?1104D5443322444(e) aas323H202'2e8222208S635583W0585610O423oes05055555Ooo0oO000o00pue[00] -ssew peuijonMB.IT/NuT[tHva[4HYitnRua ee dnoi a uo uabao o aounaxeerotosunouy9_O1×OT-T9_01×9-2pueppe28118083L'S45:-90'"-LT:Eoirosst etaoe eaanarsiBNOO0"Ho!HOODHOJpuappy3ONHx4aTeR0-00-[.0m4427863110.9901-920-1"05324009-9*-H-818iounonoeeseneoaeneeepurisONTOT-T-VO1884ounowO4812713 $-L-,0o44455切085=V0H0"H + o0'0NHtr←0°H+00'm+o0'm+ouBOONH09200"ONH0!2
Homogeneous Reactions 302.560 ISOTOPIC EXCHANGE Exchange of oxygen on Vth group element R listed under defined mass action law is isotopic exchange rate in M/l and sec. See ( ). Liquid phase Amounts are in M/I. Rates and rate con stants are in M/l and sec. No. .1 .2 Reac t i on HNO + H O 18 —— > 2 2 HNOO18 4- H 0 2 HNO + H O 18 — > 3 2 HNO O 18 -H H 0 2 2 vent Sol H 0 2 H 2 0 Amount of reactant 10 4A=7-14J [NO "l^.Ol-.l 10 2A=1-10; [N0 2~]=0.5-2 [N0 2~] = .02^.165 pH=4.6-6.0 [N0 2~] = .005-0.5 ionic strength=1.0 A = 14. 8; B = 25.8 15.4 24.4 15.8 23.4 17.1 20.2 18.2 16.7 18.7 15.6 19 .3 13. 6 19.9 12.3 4.30 48.1 4.30 48.1 5.40 46.0 Addend + fCH 3COOH |CH COONa L 3 phosphate buffer phthalate HNO 2 Amount of addend 3-6X10" 5 1-10X10" 5 .05-. 2 .17-. 8 PH 8.0 6.3 5.7 4.4 5.7 .0016 .0026 .0012 Defined massaction law feA[H+] feA 2 feA[H+] [CH-COO"] 3 kA[n+] R Temperature 0 0 25 0 25 25 25 25 25 0 0 0 0 0 0 0 0 0 0 0 fe 2.3 5.1 6 3 8 5 3.8 2.2 1.2 3.3 6.9 1.11 5.2 3.2 6.2 1.6 4.3 2.0 3.3 3.4 n +2 -1 0 +3 +4 +3 +3 +3 +4 -5 -5 -4 -4 -3 -3 -2 -2 -4 -4 -4 * A A° > A° ' 10n n Comments * * Li terature ( 8) ( 5) ( 8) c 1 ) ( 7 ) ( 2) ( 3) ( 4) National Bureau of Standards - National Research Council December, I960
1960Supplement09610qw00002(or)**sronuOTY=x"a2'613RMOtxu4332222985584.51644555445444Y28'190'1698'10%9"sWT49*6929a9'7256'O.4e8:88'T9'96886HY21A8204088808888880800080988990000-ssnwpouigoMEIOORRttunowypuoppe8200088.88088puoppyONH88081818*3sueoreSR818=1880-L'T29o66779A6°6I.0970*202S0006180998D8raenseeaeaeJosunouy818881C2o.221'9TC26.8L28.118eo.o.S9'2155a城D城2855o8"9=Y功功版城E5TA002-V0"HTOO("400)m+000m10'm +*0dmO↑00%+0208°ONH"ON?
Homogeneous Reaction Kinetics 302.560 No. .2 .3 Reaction HNO + H O18 — > (cont.) H PO + H O 18 — > 34 2 H PO O 18 + Ho 33 * Solvent H 0 2 Amount of reactant A = 5.40JB = 46.0 7.88 41.4 7.88 41.4 10.9 35.3 10.9 35.3 12.5 31.7 12.5 31.7 A = 17. 8; B = 2.81 17.8 2.81 15.1 9.9 17.8 2.81 15.1 9.9 12.2 19.7 17.8 2.81 15.1 9.9 12.2 19.7 17.8 2.81 15.1 9.9 12.2 19.7 8.8 30.0 17.8 2.81 15.1 9.9 12.2 19.7 8.8 30.0 15.1 9.9 12.2 19.7 8.8 30.0 Addend HN0 2 Amount of addend .0026 .0010 .0026 .0012 .0024 .0010 .0022 Def i n ed massact ion 1 aw R R Temperature 0 0 0 0 0 0 0 25 40 40 60 60 60 80 80 80 90 90 90 90 100 100 100 100 110 110 110 k k° x k° 8.8 1.5 6.8 1.8 5.6 3.1 7.9 1.48 7.0 1.37 4.6 1.06 2.9 2.0 6.7 2.2 4.5 1.59 5.1 1.41 9.5 3.4 1.14 3.4 8.6 2.6 7.8 "ion n -4 -3 -3 -2 -2 -2 -2 -6 -6 -4 -5 -5 -6 -4 -5 -5 -4 -4 -5 -5 -4 -4 -4 -5 -4 -4 -5 f 19.7 23.1 24.0 26.5 A A° x A° 10n n Comments * * 0 k. 3 9 ( 3)(*) ( 10 ) to National Bureau of Standards - National Research Council December, I960
Supplement196050961 neqw000058325332533aeeSsrosa aee arseeeeesereiaseeeT O te [eeererssn06 ne(g)"W"(。)[o[0ee e a (taesAI-ensine eoaees seereen8oaeiae idorost ouera eoaod ea st [ + [g ns eueaaeseereeas deaaearee0818Hai eeoeo noeenseeseeen)(or)8HLe99OAO()2(e)000920
Homogeneous Reaction Kinetics 302.560 COMMENTS General: For general treatment of Isotoplc exchange reactions see ( 9 ). Where rate constant for chemical process responsible for exchange has not been explicitly determined the value listed under k will be indicated under the defined mass-action law as either R, the rate of the chemical process responsible for exchange, orfeF a pseudo first order con stant for rate of Isotoplc equilibration. R Is calculated from the equation R=-^~AjJL in(l-x); m and n are the number of exchangeable atoms of the labeled species In A and B respectively. 4 represents l:he sum [A] + [L] and g represents the sum [B] + M * X is the fractional extent of Isotoplc equilibration at time t. The pseudo first order rate constant fcF_ for Isotoplc equilibration Is calculated from the expression feF ==- 7 in(l-x) where x and t are the same as defined A A £ above. Reaction: (.1) At low concentrations of NO "<.05 M rate law Is first order in A and first order In [H+]. At higher concentrations of NO ~ rate law Is second order In A and mechanism Is thought to Involve N o formation. Rate constants of f 1) converted from form k' [NO ~] [H4] 2 to fe[HNO ] [H*] by multiplying by Ka=5.0xio~ 4 used by (*) to correct total nitrite for HNO formed. [H+] calculated from pH. ( 6) studied catalysis of exchange by acetate buffer, and corrected exchange rate for uncatalyzed reaction. At most concentrations correction less than 10% of rate, on basis of: R/[NO "]=feK~ 1 [H+] 2 [OAC~] found fe^SxiO 3 while on basis of R/ [NO "] = fe K if 1 [ffl [HOAc] calculated fe^3X!0 3 . Latter c 2 HNOg 2 HOAcikHNO value favored as salt effect on the HOAc and HNO g equilibria should cancel. (.2) Exchange rates and concentrations converted from Mol % of authors to moles/liter but densities not corrected to o°C. HNO shown to be a catalyst for the exchange with an apparent order varying between 1 and 2. (.3) Authors show that rate of oxygen exchange is approxcp Imately equal to rate of H4Pao? hydrolysis under same conditions. Suggest rate law probably involves three simultaneous paths and suggest that the expression R=fe [H PO ] [HOO] + fe [H PO ] 2 + k [H PO ]°[H o]' 1 fits the data well. 1342 234 334 2 LITERATURE (*) M. Anbar, H. Taube, ACS 1954, 76, 6243. ( 2) C.A. Bunton, E. A. Halevi, D. R. Llewellyn, CSL 1952, 4913. ( 3) C.A. Bunton, E.A. Halevi, D.R. Llewellyn, CSL 1952, 4917. ( 4) C.A. Bunton, E.A. Halevi, D.R. Llewellyn, CSL 1953, 2653. ( ) C.A. Bunton, D.R. Llewellyn, 0. Stedman, CSL 1959, 568. ( 6) C.A. Bunton, M. Masui, CSL I960, 304. ( 7) C.A. Bunton, 0. Stedman, CSL 1958, 2420. ( 8) C.A. Bunton, 0. Stedman, CSL 1959, 3466. ( 9 ) O.M. Harris, f.f.S. 1951, 47, 716. ( 10) B. Keisch, J.W. Kennedy, A. C. Wahl, ACS 1958, 80, 4778. I National Bureau of Standards - National Research Council December, I960
1960SUPPLEMENT09615Seepue /ewore weib u!ioqaaoon9-i/w ui oln ehunoyared penbataueesuotesirowon*wOT9nto*599oaeteaoiensssassata ereien e arere oaeatee40的r795r63e2a2B8O1919910TOmMBIBsoooepydonaueaeebueaueroaer--0g0 -9-0-VgSEE*t0oTugATOss51-09202 a03uTeeT 10 ed pue+'tod +'odoitrensarouodorr1r"tod+*Jo(T)123+tod'ON1
Homogeneous Reactions 302.575 ISOTOPIC EXCHANGE Halogen exchange between Vth group halides Liquid phase Amounts are in M/I. Rate constants are i n gram atoms/1 and sec. No. React» on Amount of reactant k = .1 CC1 10 3A=5-60; 10 3B=5~2Q feB 0 25 50 2.5 2.9 2.3 -7 -6 -5 16 1.2 C 1) COMMENTS (.1) Exchange rate and rate law In gram atoms/1 was identical for chlorine exchange and phosphorous exchange using Cl 36 and P 32 for labeling. See 302.590.1. Rate of exchange was unaffected by increasing glass surface, Illumination or small amounts of 0 . Addition of HC1 or HO Increased rate of exchange of halogen but had no measurable effect on rate of ex change of phosphorous. LITERATURE f 1) W.E. Decker, R.E. Johnson, ACS 1957, 79, 5157. National Bureau of Standards - National Research Council December, I960
