SUPPLEMENT1060096oo21/W/w ul on runoeyC53CPon atee pueeteee penba!ireies***san*oospueuaitnsrs8Met aeH(t') ()98-aaaiESBItOTRX2e1:S5ega~92~35eA&AouitaaSeaeeaersenaeeuait uns asip ut puoa se ueur ssat ut11-9°611-9'6'OT1THd&'NHOX0puoppyee9*2-1-g01 9*8-Vg0r2-9'-1 ta-1-g02-9'-01 12-1-g0enaanHuntoed +o tunowys200-VCSEEEEane*892O"HLL[uaaen996180pepas ruel daao [8 do [] Jo auepuedepe6_N0 +,-1410)40 _N0 +g-(4,10)1 (00)M_NO ++-(410) (NO)M 0 +e-(Mr)"e(a")"goaoon(0)0spaepues< h108 ++(0)40(T)11NTONro+e-r-N10 +1-n0)M2rn+6-Go eaneoten07(NO)M(D)'ON2314
Homogeneous Reactions 302.640 ISOTOPIC EXCHANGE Vlth group cyanide complex with CN" Liquid phase Amounts are in M/ I. Rates and rate con stants are in M/ I and sec. No. React ion Amount of reactant PH Cr(CN) e Cr(CN) W(CN) g W(CN) 6 -3 C 14N~ —> Cr(CN) (C 14N)~ 3 + CN B 6C 14N~ —> Cr(C14N) ~ 4 -•- 6CN~ 6 : 14N" —> W(CN) (c 14N)~ 3 •+• CN" H 2° W(CN) (C 14N)~ 4 + CN 10 2A=2.5; 10 2B=l-2.5 A=B=0.025 10 2A=l-2; 10B-1.5-3 10 2A=1-2J 10B= 1.5-3 KOH KOH 10.4 11.3 9.5-11 9.5-11 feA kA very fast 85 25 <6 <5 -8 COMMENTS Reaction: (.1) Exchange rate Independent of [B] over range studied. Rate of exchange Increased 1000 times In sun light over dark reaction. (.2) Exchange complete in less than 35 seconds in diffuse sun light. (.3) (.4) Rate law not verified and value given represents probable maximum. Reaction much faster in light and rate of light reaction In dependent of [A] or [B] over range studied. LITERATURE E.L. Goodenow, C. S. Garner, ACS 1955, 77, 5268. ( 2 ) A. C. MacDiarmld, N. F. Hall, ACS 1954, 76, 4222. National Bureau of Standards - National Research Council Decemb-er, I960
1960SUPPLEMENT096110q00003isasaei/ ur eie shunowyren*sodpinrt0os pur 1/w"2LOT × o4三42T5MEUOITOn-ssew pauiyeoateseaefotunowy2TO'O=VSetoend(wntpaw)UeOs"HNEOHoINO +*CoN)CHN)40sNi0e()"HNO +"CoN)HgWe920-0
Homogeneous Reactions 302.650 ISOTOPIC EXCHANGE Vlth group NH complex with NH, Liquid phase Amounts are in M/I. Rate constants are in M/l and sec. No. .1 React ion Cr(N 15H ) (NO ) + 6NH ——> Gr(NH ) 3633 3 So I vent (Med i urn) NH. Amount of reactant A = 0.013 fcAB 10n 1.3 COMMENTS Reaction: (.1) Rate law not verified as B In very large excess and concentration of A not varied. Value gives only order of magnitude of exchange as mass-spectrometer analyses were erratic. LITERATURE H.U. D. Welsendanger, W. H. Jones, C. S. Garner, J.O.P. 1957, 27, National Bureau of Standards - National Research Council December, I960
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Homogeneous Reactions 302.660 ISOTOP1C EXCHANGE Exchange involving Vlth group element as central atom in both reactants Liquid phase Amounts are in M/I. Rates and rate con stants are in M/ I and sec. 10 V R under rate law indicates that constant listed is the rate of the chemical process responsible for exchange ( &F£ under rate law indicates rate constant Is for measured pseudo first order rate of Isotopic equilibration. * Isotopically labeled atom indicated with No. .1 React i on H SO + H 0* —— > H SO 0* + H 0 242 23 2 c I H 2 0 Amount of reactant A=14.0;B=19.8 14.5 18. £ 15.0 16.6 15.5 15.0 16.0 13.1 3.00 49.1 4.00 46.7 5.00 44.4 6.00 41.9 7.00 39.2 8.00 36.5 9.00 33.9 10.0 31.0 11.0 £8.£ 11.8 £6.0 13.0 £2.5 13.8 19.8 15.0 16.0 1.04 51.2 1.72 49.6 -a c 0) •o -o H- O -0 c -H 0> c -o 3 T3 O «J E A i « E (U c ^_, Q R . -H O Q. E 0 10 10 10 10 10 £5 25 £5 £5 £5 £5 £5 £5 £5 £5 £5 £5 £5 100 100 fe = k° x lon fe* £.41 3.60 7.77 1.40 £.06 £.16 1.40 3.58 1.62 5.72 £.70 8.53 £.08 6. £5 £.42 6.53 1.41 4.56 5.28 £.£5 n -3 -3 -3 -2 -2 -8 -7 -7 -6 -6 -5 -5 -4 -4 -3 -3 -£ -2 -5 -4 £ 24.6 20.4 A = « A° x ion A° n V) c E E O O * 0) c<D _J < 12) National Bureau of Standards - National Research Council December, I960
Supplement196009612(ar)(ta)5CaoaaoooneSio*****福tox国0:2812g'2o333433334333333333211LL90T93952'9391eo8227e.55333800'9215233570888288882888888050e0ssewpoui+9oMelooeseoaouaaueroxaRRououoepuappe2aT-Hd0*SHdST-HE9=HdHOEN 'TOENTOH.0=710-puappyHOENa=4"TOEN00-001 :1013690010821O0Jounoy1100O1-TgO132es282O10-VgOT8O0'32o"H10ATUOATOS0.98 +800euoitenspaepueisongteuoien"0S+'0"H(2u0s)rr111-0.+.0s20.8.0$+0s*0m+*"0s+'0s'099202+'os"ne0%??-ON345
Homogeneous Reaction Kinetics 302.660 No. .1 .2 .3 .4 .5 React ion H 2 S°4 * H 2°* — > (contj S 0~ 2 + S*0~ 2 — > SO ~ 2 + SS*0~ 2 23 3 3 3 H S*0 + SO — > H SO + S*0 24 2 24 2 S 0 = + S *0 24 23 S 0 = + 3*0 = 46 4 -»-• c 0> > o CO V H ao A «20 H 2° Amount of reactant A=2.85;B=46.9 3.52 45.3 4 . 40 43.2 10AM; 10 2B=2-20 10 2A=20 12 6.3 2.1 -10 10 2B=1-10 A=B=0.015 A=B=0.015 Addend NaCl, HC1 fJF 2.0 1? " n NaCl, NaOH ^=2.0 NaOH buffer Amount of addend PH=5.0 PH=12.7 PH=13 PH=6 Defined massac t i on 1 aw R feAB R no exchange no exchange <D U 3 -»-» id o> 0- E V I— 100 100 100 62 70 80 89 96 60 70 79 89 89 89 89 89 98 101 136 160 211 k = k° x ion k° 7.49 1.43 3.30 6.2 1.05 1.65 3.3 4.8 7.5 1.77 2.8 4.2 3.3 3.8 5.0 7.9 7.4 1.2 5.5 2.5 1.2 n -3 -3 -3 -4 -3 -3 -3 -3 -4 -3 -3 -3 -3 -3 -3 -3 -3 -3 -2 -1 + 1 E 31.3 14.5 A = A° x ion ,4° 2 n 6 CO -»-• c 4) E E O 0 * * * * * 0 3 td u. 0> —I (») C 1) ( 21) 0 (") I <s> r-v CO National Bureau of Standards - National Research Council December, I960