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Some reactions of singlet delta oxygen Kubo, Masayoshi 1967

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SOME REACTIONS OF SINGLET DELTA OXYGEN by MASAYOSHI KUBO B.Eng., U n i v e r s i t y o f Osaka P r e f e c t u r e , I 9 6 0 . A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF. MASTER OF SCIENCE i n the Department of Chemistry  We accept t h i s t h e s i s as conforming required  to the  standard  THE UNIVERSITY OF BRITISH COLUMBIA September, 1967•  In p r e s e n t i n g t h i s  for that  an a d v a n c e d the  Study. thesis  degree.at  Library  Department  f u l f i l m e n t of  the U n i v e r s i t y it  freely  of  British  available  for  o r by h.iJ's r e p r e s e n t a t i v e s .  w i t h o u t my w r i t t e n  the  this  thesis  for  permission.  of  The U n i v e r s i t y o f B r i t i s h V a n c o u v e r 8, Canada  Columbia  It  requirements  Columbia,  I agree  reference  and  agree that permission f o r e x t e n s i v e  s c h o l a r l y p u r p o s e s may be g r a n t e d by t h e  or p u b l i c a t i o n of  Department  in p a r t i a l  s h a l l make  I further for  thesis  copying of  Head o f my  is understood that  financial  gain  this  shall  n o t be  copying allowed  II  ABSTRACT ' In Part I of t h i s work, the decay o f O g ^ A g ) s t u d i e d a t room temperature absence  of oxygen atoms.  into f i r s t  i n the f l o w system i n the  The  decay of C ^ l ^ g ) was  .of  o r d e r decay w i t h r e s p e c t  C ^ l ^ g ) , which i s c o n s i d e r e d to be caused by C ^ ^ A g ) w i t h w a l l o f the r e a c t i o n tube, was  0.25  classified  and second o r d e r decay with r e s p e c t to ( ^ ( ^ g ) .  The r a t e c o n s t a n t o f the main f i r s t to  collisions found to be  sec. The t o t a l second o r d e r decay c o n s t a n t was  to  was  be 2.9 x 10^  found  1/mole sec.  In Part II the r e a c t i o n s o f e x c i t e d oxygen molecules w i t h some o l e f i n s vrere i n v e s t i g a t e d . 3-hydroperoxybutene-l was  i d e n t i f i e d as the product o f the  . reaction.-of e x c i t e d oxygen m o l e c u l e s w i t h 3-Methyl  hydroperoxybutene-1  peroxybutene-1  was  2,3-dimethylbutene-2.  and 2-methyl-3hydro-  vrere produced by the r e a c t i o n o f e x c i t e d  oxygen molecule w i t h ... The  2,3-Dimethyl-  2-methylbutene-2.  decay o f 0 ( A g ) w i t h 4  2  2,3-dimethylbutene-2  a l s o s t u d i e d but the r e s u l t s c o u l d not be e x p l a i n e d by  any simple mechanism.  III.  CONTENTS Page Introduction  1  Experimental  12  1.)  Material  12  2)  Apparatus  ]_3  3)  Excited oxygen molecule measurement  4)  Gas chromatography  19  5)  I d e n t i f i c a t i o n of products  23  Experimental r e s u l t s  24  ' 1)  Decay of 02('Ag) without o l e f i n  24  Analysis of products  30  2)  i ) Oxidat ion of  2;3-dimethylbutene-2--with 30  excited oxygen molecules. i i ) Oxidation of 2-methylbutene-2  with 31  excited oxygen molecules. i i i ) Oxidation of cis-butene-2 with excited oxygen molecules.  38"  iv) Oxidation of iso-butene and propene with 38  excited oxygen molecules. 3)  Decay of 0 ( ' A g ) with 2,3-dimetliylbutene-2 47 2  52  Discussion  1)  Decay of 0 ( ' A g )  .  2)  I d e n t i f i c a t i o n of products  2  i ) The reaction product of with excited oxygen  5 2  ' 5 9  2,3-dimethylbutene-2 59  IV.  i i ) The reaction products of 2-methylbutene-2 with excited oxygen 3)  Decay of 0 ( ^ g ) v/ith 2  butene-2 References  •  69  2,3-dimethyl78 84  V.  . LIST OF TABLES Page  1.  Reactions of 0 ( ' A g ) .  6  2.  Oxidation products of o l e f i n .  9  3.  Optimum operating condition of gas chromatograph.  19  4.  Decay of 0 ( ' A g ) .  26  5.  2  2  and kg  30  6.  Decay of" 16340 with o l e f i n .  47  7.  Decay rate of I-634O at t = 0 .  51  3.  Comparison of rate constants.  58  9.  Comparison of NMR  60  10.  Comparison of IR and NIR spectrograms.  6l  11.  Comparison of NMR  74  spectrograms.  spectrograms.  VI. IjISTjOg  FIGURES.  Page 1.  Plow diagram o f the system.  14  2.  Diagram o f d e t e c t o r c i r c u i t .  17  3.  R e l a t i o n s h i p between HETP and f l o w r a t e o f c a r r i e r gas.20  4.  I n t e n s i t i e s o f 6340A band as a f u n c t i o n o f d i s t a n c e .  25  5.  Gas chromatograms o f the p r o d u c t s o f the r e a c t i o n s o f s i n g l e t oxygen with, t h r e e o l e f i n s .  32  6.  NIR s p e c t r o g r a m o f t h e p r o d u c t from the r e a c t i o n o f 2 , 3 - d i m e t h y l b u t e n e - 2 w i t h s i n g l e t oxygen.  33  IR s p e c t r o g r a m o f the p r o d u c t from the r e a c t i o n o f 2 , 3 - d i m e t h y l b u t e n e - 2 w i t h s i n g l e t oxygen.  34  8.  Mass s p e c t r o g r a m o f the p r o d u c t from the r e a c t i o n o f 2 , 3 - d i m e t h y l b u t e n e - 2 w i t h s i n g l e t oxygen.  35  9(a).  HMR s p e c t r o g r a m o f the p r o d u c t from the r e a c t i o n o f 2 , 3 - d i m e t h y l b u t e n e - 2 v / i t h s i n g l e t oxygen.  36a  7.  9 ( b ) . NMR  s p e c t r o g r a m o f the p r o d u c t from the r e a c t i o n o f  2 , 3 - d i m e t h y l b u t e n e - 2 w i t h s i n g l e t oxygen. ("C= 10.  5)  C a l i b r a t i o n curve of the product.  36b 37  1 1 ( a ) . Gas chromatogram o f f r a c t i o n (A.) from reaction. 1 1 ( b ) . Gas chromatogram o f f r a c t i o n (B) from reaction.  2-methylbutene-2 39 2-methylbutene-2 40  1 2 ( a ) . IR s p e c t r o g r a m o f f r a c t i o n (A) from reaction.  2-methylbutene-2  1 2 ( b ) . IR s p e c t r o g r a m o f f r a c t i o n (B) from reaction.  2-methylbutene-2;  41 42  1 3 ( a ) . NMR s p e c t r o g r a m o f f r a c t i o n (A) f r o m reaction.  2-methylbutene-2  1 3 ( b ) . NMR s p e c t r o g r a m o f f r a c t i o n (B) from reaction.  2-methylbutene-2  43 44  1 4 ( a ) . Mass s p e c t r o g r a m o f f r a c t i o n (A) from reaction.  2-methylbutene-2  1 4 ( b ) . Mass s p e c t r o g r a m o f f r a c t i o n (B) from reaction.  2-methylbutene-2  45 46  LIST OP  VII.  FIGURES...continued  Page 15.  Mass s p e c t r o g r a m o f 2 , 3 - d i m e t h y l - 3 - h y d r o p e r o x y b u t e n e - 1 -taken by Winer and Bayes. 62  16.  MR  s p e c t r o g r a m o f 3-methyl-3-hydroxybutene--1.  63  17.  NMR  s p l i t t i n g due t o AB system.  65  18.  HMR  s p e c t r o g r a m o f 3-methyl-3-hydroxybutene--1.  67  19.  C a l c u l a t e d s p e c t r o g r a m o f ABC  20.  R e l a t i o n s h i p between log(-'U.) and  log(R ).  21.  R e l a t i o n s h i p between l o g ( - V ^ T p f )  and  22o  R e l a t i o n s h i p between e x c e s s energy i n t h e stream and  23.  R e l a t i o n s h i p between  system.  e  (At/AandA.  71 80  c  log(I ). 0  80  29b  VIII.  ACKNOWLEDGEMENTS To Dr. E. A. Ogryzlo suggested  (my Research  D i r e c t o r ) who  t h i s study and t o whom I am i n d e b t e d f o r h i s  generous h e l p and support; To Dr. D.P. Chong who generously gave o f h i s time -to s u p e r v i s e my r e s e a r c h d u r i n g Dr. O g r y z l o ' s absence-and for criticizing  this  manuscript;  To the many members o f the t e c h n i c a l s t a f f , and to Miss Barbara A. A l b e r s f o r t y p i n g t h i s  J  manuscript.  Introduction -Even though excited oxygen molecules were described :by Mulliken"^ as early as 1928 and had thereafter been observed In ...the upper atmosphere of the . earth^'^ .and  i n l i q u i d ^ oxygen  i n e l e c t r i c a l l y discharged gaseous oxygen^>?'^>9, very  l i t t l e was known about .the behaviour of excited oxygen -molecules u n t i l I960.  Most of the early investigations were  concerned with the recombination of oxygen atoms.  This i s  mainly because of the d i f f i c u l t y i n getting excited oxygen molecules which are not mixed with oxygen atoms. -Some -properties and reactions of excited oxygen molecules already investigated are described below. 1).  Species i n the products of e l e c t r i c a l l y discharged oxygen. .By applying mass spectroscopy to e l e c t r i c a l l y -discharged oxygen,  Poner  and Hudson-^ and l a t e r  - Herron and S c h i f f  showed the presence of oxygen  . atoms and a species with an appearance potential -0.93iO.leV below-that of ground state oxygen '(02( Xg)). >  By a comparison of t h i s energy separation  with the spectroscopic separation of the 02(*Ag) and . - 0 ( 2 £ g ) , which i s .7882.39 cm" (0.9772eV), they 1  2  •suggested that i t might be 0 ( t A g ) , i n which case 2  --the 20%.  concentration of 0 (-*Ag) would be between 10 and 2  Elias, electrically  Ogryzlo  discharged  and  Schiff ^ studied  oxygen by means o f  i s o t h e r m a l c a l o r i m e t r i c d e t e c t o r and w i t h N O 2 , and  found a d i s c r e p a n c y  titration  between the atom  c o n c e n t r a t i o n s as d e t e r m i n e d by these They c o n f i r m e d  that;it  was  an  methods.  because o f the  presence  o f some o t h e r s p e c i e s , w h i c h d i d not r e a c t w i t h NO2,  and whose c o n c e n t r a t i o n c o r r e s p o n d e d to about  10% o f the t o t a l oxygen i f the s p e c i e s were 0 2 ( ' A g ) . L a t e r , Bader and  OgryzloA^ e s t a b l i s h e d  the method t o get r i d o f oxygen atoms f r o m the e l e c t r i c a l l y d i s c h a r g e d  completely  oxygen by  d i s t i l l i n g mercury t h r o u g h the d i s c h a r g e coating mercuric  o x i d e j u s t a f t e r the  T h i s makes e l e c t r i c a l l y f o r k i n e t i c and  discharged  and  discharge.  oxygen s u i t a b l e  spectroscopic studies.  More r e c e n t l y Arnold"*"^ measured the c o n c e n t r a t i o n o f the e x c i t e d s p e c i e s under the c o n d i t i o n s e s t a b l i s h e d by Bader and found about 6 o r 8% o f 0 ( * A g ) and 2  Ogryzlo 0.03%  and of  0 2 ( X g ) i n the oxygen' stream. !  From the f a c t s d e s c r i b e d above discharged  oxygen c o n t a i n s a p p r o x i m a t e l y  atoms w h i l e a n o t h e r 10% i s e x c i t e d t o the  electrically 10% oxygen *Ag s t a t e .  When mercury i s d i s t i l l e d through the d i s c h a r g e i n o r d e r to d e s t r o y the oxygen s e v e r a l percent 0 ( * A g ) i s s t i l l 2  atoms,  present i n the  oxygen stream and another s p e c i e s , ( ^ ( ^ g ) , i s a l s o present i n v e r y s m a l l amounts. V i s i b l e emission bands from 02(*Ag) The o b s e r v a t i o n t h a t a red-orange chemiluminescenee was produced d u r i n g the r e a c t i o n -of hydrogen p e r o x i d e and sodium h y p o c h l o r i t e i n aqueous s o l u t i o n was r e p o r t e d by S e l i g e r - ^ .  The  r e p o r t e d wavelength of the red-orange chemiluminescence was 6 3 4 $ A , but he made no attempt t o i d e n t i f y the  source o f the emission. -l £  •Khan and Kasha chemiluminescence which was ©  6334 and  7030A, under almost  measured  the same r e d  composed of two emissions the. same c o n d i t i o n s .  A r n o l d ,Ogryzlo and Whitzke^? i n v e s t i g a t e d the  e l e c t r i c a l l y ' d i s c h a r g e d oxygen f l o w s p e c t r o s c o p -  i - c a l l y and a l s o observed e m i s s i o n s at 6340 and 7030A. When oxygen atoms were removed  by the  d i s t i l l a t i o n o f mercury through the d i s c h a r g e , the .two .peaks, remained u n a l t e r e d w h i l e the 7600. and. 8600A peaks, which are (0,0) and (0,1)  transitions  i n the '51 g — > X g system, were o n l y s l i g h t l y lowered. 3  4.  The p o s s i b i l i t y that impurities (water and N O 2 ) could give r i s e to emission i n t h i s region were -eliminated by the measurements of i n t e n s i t i e s of these emissions with s p e c i a l l y dried and nitrogenfree oxygen and by addition of water and N O 2 , before and a f t e r the discharge.  The two emissions  were e s s e n t i a l l y unaltered by these changes. -More evidence that the 634OA r a d i a t i o n i s due to C>2('A.g), was found by Bader and 0gryzlol3. They showed that the i n t e n s i t y of the 6340A emission was proportional to the square of the concentration of 02('Ag) measured by an isothermal calorimetric detector.  On the other hand, March, Furnival and  S c h i f f - ^ monitored the concentration of 02('Ag) by i t s emission at 12700A and found that the emitted i n t e n s i t y at 6340A was proportional to the f i r s t power of the 02('Ag)  concentration.  Later, whitlow  and Findlay-^-9 investigated the r e l a t i o n s h i p between' the i n t e n s i t y of 6 3 4 0 ! ( 7 0 3 0 A )  and that of 12,700A*  -by-using an RCA V i c t o r PD523 detector to measure o  t h e - i n t e n s i t y of 12,700A, and concluded that the ©  -intensity of o340A emission was proportional to the square of the i n t e n s i t y of 12,700A.  Arnold and  Ogryzlo also showed, that the . i n t e n s i t i e s of both "634O and 7030A emissions were proportional to the  square o f t h e c o n c e n t r a t i o n o f 0 ( ' A g ) measured 2  ' by an i s o t h e r m a l c a l o r i m e t r i c d e t e c t o r . and M a h a n  Falick  d e t e c t e d 0 ( ' A g ) by EPR s p e c t r o s c o p y ,  21  2  w h i c h has the a d v a n t a g e s o f s p e c i f i c i t y and s e n s i t i v i t y , and o b t a i n e d t h e r e s u l t t h a t t h e i n t e n s i t y o f 6 3 4 0 A " was p r o p o r t i o n a l t o t h e square of.the concentration of 0 ('Ag).  I t i s quite  2  d i f f i c u l t t o d e t e c t 0 ('Ag) q u a n t i t a t i v e l y by i t s 2  e m i s s i o n a t 12,700A u s i n g a p h o t o m u l t i p l i e r because o f l o w s e n s i t i v i t y o f p h o t o m u l t i p l i e r s i n t h i s spectral region.  On t h e o t h e r hand, though  the i s o t h e r m a l c a l o r i m e t r i c technique  has the  r e q u i r e d s e n s i t i v i t y , i t h a s been c r i t i c i z e d f o r i t s unknown t h e r m a l  e f f i c i e n c y and l a c k o f  21  specificity.  However i t s h o u l d be n o t e d t h a t  -the c o n c e n t r a t i o n o f 0 2 ('2Ig) was shown by A r n o l d t o • be n e g l i g i b l e compared t o 0 ( A g ) i n d i s c h a r g e d 2  oxygen w i t h oxygen atoms removed by-mercury.  Since  the q u a d r a t i c r e l a t i o n .between 0 ( A g ) and i n t e n s i t y 2  l  o f e m i s s i o n a t o340A i s r e a s o n a b l y  well established  the i n t e n s i t y o f e m i s s i o n a t 6340A p r o v i d e s a convenient 3 i.)  Reactions  way o f e s t i m a t i n g 0 (*Ag) 2  concentration.  o f 0 ( ' A g ) i n Pure Oxygen Systems. 2  Reactions  o f 0 ( ' A g ) have been s t u d i e d by 2  • s e v e r a l i n v e s t i g a t o r s - ^ > 21?22,23-, 24 > 25. r e s u l t s a r e summarized i n Table 1.  Their  6.  Reactions of 0 ( ' A g ) .  TABLE 1. No.  2  Reaction  Rate Constant  1.  0 ( ^ g ) ->  2.  0 ('Ag) — » 0 ( Xg")  3..  0 ( A g ) + 0 ( 3 £ g ) —> 2 0 ( * g )  4.  20 ( A.g)  2  0 ( Zg-)+h*>(l2680A) 3  2  2  2  ,  2  2  2  ,  20  3  5. 6.  3  20 ( Ag) 2  ,  2  —-» 0 ( Z g ) - 0 ( X g - ) 2  1  22 14  - 1  ^ 2 . 7 7 x l 0 X m o l e secl8 ^1.53x10 " 23 2  t  (3xg~)  2  o r [o ( ^g-)3- -rhP(6340 and 7030A) 2  1 . 5 x lO-A-sec" 0.178 s e c  3  2  Ref.  /  i  2  20 ('Ag) — > products 2  ?  0 . 2 8 J U o l e sec (3*0.6)xl0~2 n  24 21  1.3x103 1.8x107*0 0  "  14 25  "  14  ^4.3xl0  2  A l l of these reactions except the f i r s t vrere investigated i n e l e c t r i c a l l y discharged systems.  ii)  Reaction of 0 ( ' A g ) with organic compounds. 2  While.there are many papers 2D,27,28,29  o  n  photosen-  s t i z e d autoxidation and hydrogen p e r o x i d e oxidation -of organic compounds, few p a p e r s ^ J 0 > ^ 3  3  3  ..published about the reaction of s i n g l e t  have been oxygen  . molecules with organic compounds i n the gas phase. ^0 F i r s t Corey and Taylor^  used discharged  oxygen flow to oxidize organic compounds i n the l i q u i d phase.  They oxidized anthracene, 9>10 —  diphenylanthracene  and 9;10-dimethylanthracene  with  7.  the d i r e c t products o f d i s c h a r g e d oxygen, and converted them to the corresponding 9,10 — endoperoxides.  They concluded t h a t the oxygen  which r e a c t e d w i t h anthracene was  0 (Ag) 2  and i t s d e r i v a t i v e s  o r 0 ('.2Lg) because: 2  1) Gaseous oxygen, which was not d i s c h a r g e d , d i d not r e a c t w i t h them and i t a l s o seemed  improbable  that v i b r a t i o n a l l y e x c i t e d 0 ( 2Tg) c o u l d p e r s i s t 3  2  long enough t o e f f e c t o x i d a t i o n i n s o l u t i o n . 2) Ozone and atomic  oxygen would l e a d to o t h e r  32 types o f p r o d u c t s ^ . They a l s o attempted to a l l y l i c  to convert o l e f i n s  hydroperoxides but they d i d not succeed  i n the cases o f ramethylethylerve  -pinene, I - p h e n y l c y d o K e x e n e  ,, t e t -  and cholest-4-en-3^ - o l . 31  F a l i c k , Mahan and Myers^  noted a p o s s i b l e  r e a c t i o n o f 0 ( ' A g ) w i t h ethylene i n the homogeneous 2  gas phase because o f the r e d u c t i o n o f the EPR.signal from 0 ( ' ^ g ) by a d d i t i o n o f ethylene but they d i d 2  not.attempt  to get r e a c t i o n products.  Even though Corey and T a y l o r c o u l d not succeed i n g e t t i n g a product from the o x i d a t i o n o f t e t r a m e t h y l e t h y l e n e by 0 ('Ag) o r 0 ( ' Z I g ) , 2  2  Winer and  Bayes  3  got a product  i n the homogeneous gas  •reaction of t e t r a m e t h y l e t h y l e n e product  was  ene—1.  i d e n t i f i e d as 2p  I t s h o u l d be noted  w i t h (^('Ag)..  The  —dimethyl-3-hydroxybutt h a t they put a s m a l l  amount of water i n t o the system a f t e r the -•which was  phase  discharge  enough to d e s t r o y any G^ClEIg) which might  be produced by the r e a c t i o n . 2 0 ( ' A ) -> 2  g  0 {l£g)+0 CZ-g) 2  2  As i s a l r e a d y known, s i n g l e t oxygen molecules peroxide  are produced by the r e a c t i o n of hydrogen w i t h sodium h y p o c h l o r i t e or a h a l o g e n  and  3 3  s e v e r a l papers have been p u b l i s h e d on the o x i d a t i o n o f o r g a n i c compounds w i t h t h i s s i n g l e t  oxygen.  I t i s i n t e r e s t i n g to compare the  products  of o r g a n i c compound o x i d a t i o n s by oxygen gas  with  p h o t o s e n s i t i z e r and l i g h t , r e a c t i o n of hydrogen peroxide w i t h sodium h y p o c h l o r i t e or halogen, d i s c h a r g e d oxygen  and  gas.  These comparisons are shown i n Table In the o x i d a t i o n s i n v o l v i n g an  2.  electrical  d i s c h a r g e there i s no q u e s t i o n t h a t G^f'Ag) i s the a c t i v e reagent. .be present i n . t h e  Since (^('Ag) has been observed -H2O2 systems and  the  to  products  -9.  are the same i t seems reasonable to assume that O^C'Ag) i s the active reagent i n t h i s system too. Furthermore  because the photochemical oxidations of  these systems produces i d e n t i c a l products i n the same r a t i o i t has been p r o p o s e d ^ t h a t 3  :oxygen i s also involved i n these TABLE 2.  Reactant \ /*=\  y,  <K  Ratio of the products oxid.with H 02_ discharged ^2 26,27,28,29 23,30 2  a)  /  /~^OH  1  aj"  Ton  X.  a;  ^ - < ^  0  0  ^  W  2)  :H 0  * ;*  H  W~  0  0  1  48  49  52  51 51  51  49  96  94  >  >—>-  ^poH  1  49  Y~Y_  A  systems.  Oxidation of Olefins.  Photosensit i z e d autoxidation 26,27,28  Product  singlet  •  , 6  100  ?  49  48  31  34  11  9  0  °  B  )  10.  Ho..  21  IB  10 Ho,  3  7  25  24  100  ^/(yAd> - 4 A  d)  100 d)  100  100  100  100  fa  30%  e)  100 e)  100 f )  100 ) f  a)  P r o d u c t s were r e d u c e d by t r i m e t h y l p h o s p h i t e o r sodium b o r o h y d r i d e (MaBH^)  b)  The p r o d u c t was found a s a h y d r o p e r o x i d e i n s t e a d o f h y d r o x i d e  c) ~ Methanol was used as a s o l v e n t . d)  Other p r o d u c t s were unknown.  e)  B r was used i n s t e a d o f sodium h y p o c h l o r i t e . 2  f ) ^ D i s c h a r g e d oxygen m o l e c u l e s Were bubbled i n t o t h e s o l u t i o n containing reactant.  11.  Present work.  \ The present work i n v o l v e s  1) homogeneous gas phase r e a c t i o n o f s i n g l e t oxygen molecules [ " ( ^ ( ' A g j J '  i n the absence o f any added  reagent. 2) i d e n t i f i c a t i o n o f products by the r e a c t i o n o f singlet  oxygen molecules with 2,3— dimethylbutene  -2 and w i t h 2— methylbutene-2. 3) k i n e t i c  study o f decay o f s i n g l e t oxygen molecules  w i t h 2,3-dimethylbutene-2.  12  Experimental 1)  Materials i)  Oxygen Matheson Company oxygen (extra dry grade), found to contain much l e s s nitrogen than oxygen obtained from Canadian Liquid A i r , was used as a source of excited oxygen molecules without any p u r i f i c a tion.  .ii)  2,3- Dimethylbutene-2 2,3- Dimethylbutene-2 from K and K Inc. Ltd. was found by gas chromatography to contain at least f i v e impurities, among which were water and 2,3dimethyl b u t a T i o ( - 2 .  The crude 2,3-dimethylbute ne  -2 was p u r i f i e d with a spinning band column d i s t i l l a t o r which had more than 20 t h e o r e t i c a l plates.  The d i s t i l l a t e , more than 98% pure by  chromatogram area, was used f o r the experiments. Iii)  2-Methylbutene-2 Research grade 2-methyl bute.ne-Z ( P h i l l i p s Petroleum Co.; mani/f acturers specif i c a t i o n :  99.7  mole %) was used without further p u r i f i c a t i o n . iv)  cis —  Butene—2  Research grade cis-butene-2 ( P h i l l i p s Petroleum Co, manufactures s p e c i f i c a t i o n : 99*91 mole %) was used without further p u r i f i c a t i o n .  iso —  Butene  Research  grade  was  without  used  iso-butene further  (Phillips  Petroleum Co.)  p u r i f i c a t i o n .  Propylene Research  grade  manufactures -without  propylene  (Phillips  s p e c i f i c a t i o n :  further  99*99  Petroleum C o . ; mole  %)  was used  of the flow  reaction  p u r i f i c a t i o n .  Apparatus A  schematic  .system, i s shown tube  i n F i g . I.  had an i n t e r n a l  length  o f about The  pyrex  tube  diagram  120  diameter  10  cm i n l e n g t h  internal  diameter  In  t h e case  o f reactions  o l e f i n  tube the  reaction  an i n l e t  a  a  cold  temperature  A Raytheon 'which  a n d 1.0  the reaction  o f 02( Ag) into  the  cm  tube.  with  l  j e t which  reaction  conventional  proper  i n a  olefins,  reaction  extended  into  tube.  The i n  above  gas was introduced  through  cm a n d a  g a s was d i s c h a r g e d  in  the  o f 2.5  reaction  cm a n d w a s n o t j a c k e t e d .  oxygen  o f about  The p y r e x  was used  products trap  were  which  collected  was kept  (-196°C o r - 7 0 G ) ' . o  Generator  to obtain  an  N o . KV-IO4SB  electrodeless  at  rOi  .  ?  cb  -e-  TO PUtAP  CYLINDER  1_ AfR  0  DISCHARGE. TO  Mc.LS.OQ  ro  McL  EOO GAU3£  RELACTfON  TUP.£  ro PUMP  0.  PHOTO MULT I PLItLff  Figure I : Flew diagram of t h e system  1  0  d i s c h a r g e , generates a continuous 2450. megacycle wave w i t h a maximum power output of 125  Watts.  When the output i s d i r e c t e d at a stream of oxygen through a d i r e c t o r , a d i s c h a r g e may under the proper c o n d i t i o n s  be  initiated  of p r e s s u r e , f l o w and  tube s i z e by the a p p l i c a t i o n of a spark from a Tesla  coil. The f l o w rates of oxygen and  olefin  gases were c o n t r o l l e d and measured by systems.  identical  The f l o w r a t e s were v a r i e d by Edward  f i n e - c o n t r o l needle v a l v e s .  The p r e s s u r e d i f f e r e n c e  e s t a b l i s h e d a c r o s s a c a p i l l a r y was measured by a U-tube manometer f i l l e d with mercury  i n the case  of oxygen and w i t h O c t o i l i n the.case of o l e f i n vapor.  The f l o w r a t e of oxygen was  determined  c o l l e c t i n g the gas and by a soap f i l m  by  flow-meter  at the e x i t of the mechanical pump when the steady state conditions  had been e s t a b l i s h e d .  rate of 2,3-dimethylbutene-Z  was  The flow  determined  c o l l e c t i n g the gas i n a l i q u i d n i t r o g e n  by  trap,  t r a n s f e r i n g i t to a weighing b o t t l e and weighing i t . The a b s o l u t e pressure i n the r e a c t i o n tube was  measured w i t h t i l t i n g McLeod gauges with  a range of 0.1  to 5rs\m Hg,  the r e a c t i o n tube.  There was  •drop i n the r e a c t i o n tube..  l o c a t e d at e i t h e r end of at most 1.5% p r e s s u r e  16.  E x c i t e d oxygen molecule measurement. The  e x c i t e d oxygen molecules f l o w i n g i n the r e a c t i o n  tube were measured by an i s o t h e r m a l c a l o r i m e t r i c -detector developed by Ogryzlo.  This  detector  c o n s i s t e d of a h e l i c a l l y wound s p i r a l of  platinum.; j  wire e l e c t r o p l a t e d with c o b a l t , which c o u l d f i x e d i n the r e a c t i o n tube.  The  platinum  be  wire  coated with c o b a l t formed one  r e s i s t a n c e arm  the Wheatstone bridge c i r c u i t  shown i n F i g . 2.  -With the discharge  off,, that i s , no  e x c i t e d oxygen molecules flowing., c u r r e n t was •through the d e t e c t o r , and  of  the b r i d g e was  passed  balanced  by a d j u s t i n g the c u r r e n t and/or the r e s i s t a n c e of decade r e s i s t a n c e box. d e t e c t o r was potentiometer the 1 ohm  The  c u r r e n t through the  then measured oh an  accurate  by measuring the p o t e n t i a l drop  across  precision resistor. . With the microwave d i s c h a r g e  on  and  •excited oxygen molecules present„ the e x c i t e d m o l e c u l e s were d e a c t i v a t e d on t h e -' /Pt <  r e l e a s i n g 23  0  coil  Kcal/mole ( d e a c t i v a t i o n energy o f  OgC'Ag) to ground s t a t e ) i n the ftorm of heat. -the b r i d g e to be -balanced  the  For  under tlhese c o n d i t i o n s ,  -the c u r r e n t through the d e t e c t o r Ihad to be decreased, r e t u r n i n g the c o i l to i t s o r i g i n a l  P  P"OT£. N TIO •/? C7*£ R  G  C A i V A NO MET  •7 Figuiv  2:  Diagram  of d e t e c t o r  TAP  circuit.  PI  <V  a  B R K £ Y.  IB.  temperature and thus i t s o r i g i n a l resistance. From' the magnitude of decrease i n the squares of the currents  A  ( i ^ ) , the excited molecule flow  incident on the detector could be calculated by the following formula, i f the e x c i t a t i o n energy o f t h e excited oxygen molecules  i s known.  0 (excited) flow = A ( i ) R  moles/  2  ?  4-18E  sec  where A ( i ) i s the current squared decrease, i . e . 2  • A (±2) = ± 2 ±  - i |  R i s the resistance of the detector and E i s the average e x c i t a t i o n energy of excited oxygen molecules.  Since i t i s known that more than 99%  of the excited state oxygen molecules are 02('Ag) under these p a r t i c u l a r experimental conditions, E can be taken as 23 KCA\/mole which i s the excitation energy of 02('Ag) from the ground state. Once i t had -been established that the i n t e n s i t y of the 6340A band was. proportional to the square of the 02(2Vg) concentration,  changes i n the  02(^\g) concentration as a function of time, position or added gases could be e a s i l y and r a p i d l y determined by measuring changes i n the i n t e n s i t y of 6340A band with an RCA  7265  photomultiplier which  was mounted on an o p t i c a l bench p a r a l l e l to the reaction tube.  Gas  chromatography  An Aerograph gas chromatograph Model A 90 P-3 (Wilkins Instruments & Research Inc.) was used f o r detection and separation of reaction products. To f i n d the optimum operating conditions of the gas chromatograph, the r e l a t i o n s h i p between the height equivalent t h e o r e t i c a l plate (HETP) and flow rate at d i f f e r e n t column temperatures .was investigated. F i g . 3.  These relationships are shown i n  The s t a b i l i t y of the product of the  reaction between 2 , 3 - d i m e t h y l b u t e n e - 2 depends on column temperature.  , and (^('Ag)  For example at a  column temperature of 80°C, a new peak i n trace amounts was detected with a retention time between those of reactant and product. column temperature was used.  Therefore, a 60°C  The operating'  condition of the gas chromatograph i s shown i n the Table 3. . TABLE 3. optimum operating conditions of gas chromatograph. column temperature : 62°C detector temperature •: 77°C c a r r i e r gas : He 60 l/min column ' : SE -30, "5 f t . detector current : 150 mA (SE-30: S i l i c o n e gum r u b b e r ) ra  *I0 Ir^cL  rz.o  5:  /o.o  O  20  40  GO  80  /oo  .  12.0  Plow r a t e o f c a r r i e r gas  F i g u r e C3(b5:: R e l a t i o n s h i p ibetween IIETP,.and . . flow r a t e . o f c a r r i e r gas. . '•.:'••"••:/'•'•.  (column temperature: 62°c)  -20  40  60  So  /oo  Flow r a t e of c a r r i e r gas Figure 3 ( c ) :  /to  '^4.-//L.  7/  (Relationship: between H E T F and - f l o w rate, o f c a r r i e r  .. • ••'  /xo  (column temperature: . 45°C)  gas. '  23.  Q u a n t i t a t i v e a n a l y s i s of the o x i d a t i o n 2 3-d«7nethyl b u f c e n e - 2  p r o d u c t of :  ?  by  gas  chromatography under the optimum c o n d i t i o n s was also investigated. product was  The peak area of r e a c t a n t and  c a l i b r a t e d by NMR  Identification  of Products.  Identification made by t a k i n g IR, NMR each product was distillation  spectroscopy.  of o x i d a t i o n products  and mass spectrograms  separated by  trap-to-trap  The f o l l o w i n g spectrometers were  used.  ,  I.R.:  Model 21 Double Beam IR (Perkin-Elmer Corp.). :  after  i n the vacuum system and/or by gas  chromatography.  NMR  was  A-60 Analytical•NMR (Varian Associates)  .. Spectrophotometer  Spectrometer  JEOL - h i g h r e s o l u t i o n NMR instrument (Japan E l e c t r o n O p t i c s Lab. Co. Ltd..) Mass  Spectrometer: Model M.S.9 Ltd.).  (Associated E l e c t r i c a l  Industries  24.  Experimental r e s u l t s 1)  Decay of 0 ( A g ) without o l e f i n . y  2  The i n t e n s i t y of emission at o340A was measured as a function of distance (a) along the reaction tube.. A t y p i c a l plot of t h i s kind i s shown i n F i g . 4A series of -such measurements were taken at a. constant flow rate of oxygen and various powers of. the discharge. As can be seen i n F i g . 4« the decay of the concentration of 0 ('Ag) i s very small. 2  The square  root of the i n t e n s i t y along the reaction tube i s almost a perfect straight l i n e over the distance measured, with a c o e f f i c i e n t of c o r r e l a t i o n of more than 0.98.  Therefore, the slope of l i n e was  taken as the rate of decay at the middle of the measured "distance. The flow rate of 0 ('Ag) was determined by 2  the formula 0 (lAg) = a f i 2  where jo  -6340  .6340  i s the i n t e n s i t y of emission at 6340A  and a i s a constant obtained by isothermal calorimetric c a l i b r a t i o n . i n Table 4-.  The r e s u l t s are shown  -  0  io  2.0 3o  4-o  Df STANCE  F i g u r e 4:  so  6o  ALONG  70  So  9o  OBSERVATION  I n t e n s i t i e s o f 6.340 A band. as a f u n c t i o n of d i s t a n c e .  •.  C  r  n  TUBE  TABLE 4(a) -d/T/dz. arb. unit/em x 10^ 0.617 0.596 0.500 0.378  Decay of 0 ('Ag) 2  Jl 0 ('Ag) a r b i t r a r y Unit, /a mole/sec 2  4.93 4-76 4.12 3.51  10.8 10.4 8.98 7.65  Total flow rate of oxygen Pressure linear velocity  TABLE 4(b)  0.625 0.675 O.563 0.501 0.413  -dA/dt/A ., sec" 0.449 0.449 0.436,O.388  180 u mole/s-ec 2.08 rnmHg 359 cm/sec  Decay of 0 ('Ag) 2  10.6 10.6 9.33 8.61 7.13  4.85 4.87 4.28 3.95 3.27  Total flow rate of oxygen Pressure linear velocity  0.495 O.5O6 0.480 0.462 0.459  "200 p. mole/sec 2.03 rnmHg 364 cm/sec  TABLE 4 (c) Decay of 0 ('Ag) 2  O.55O 0.995 0.910 0.715  4.20 6.55  6.23  5.24  Total flow rate of oxygen Pressure linear velocity  .  9.16 14.3 13.6 11.4  0.495 0.575  0.552 O.5I4  u mole/sec 3.78 rnmHg. 378 cm/sec. 380  1  TABLE  -dyr/dz.  4(d) Decay o f 0 ('Ag) 2  yr  0.660 0.570 0.400 0.795 0.725  o ('A ) u mole/sec  -dVdt/A ' sec  10.8 9.79 7.52 12.4 11.8  0.501 0.475 0.434 0.524 0.501  2  a r b . unit/cm x 10^ a r b i t r a r y U n i t 4.94 4-49 3.45 5.67 5.43  G  275 p mole/sec 2.77 mmHg 374 cm/sec  T o t a l f l o w r a t e the oxygen Pressure linear velocity  TABLE 4(e) 0.455 0.475 0.400 0.375 0.275  Decay o f 0 ('Ag) 2  4.20 4.29 3.86 3.61 2.95  T o t a l f l o w r a t e the oxygen Pressure linear velocity TABLE 4 ( f ) 0.430 O.638 O.588 0.530  11.1 11.4 10.2 9-57 7.82  0.391 0.402 0.376 0.376 0.340  183 j u mole/sec 1.90 mmHg 362 cm/sec  Decay o f 0?('Ag)  4-05 5.06 4.90 4.57  T o t a l f l o w r a t e the oxygen Pressure linear velocity  10.7 13.4 13.0 12.1  0.394 O.443 0.446 0.432  277 P mole/sec 2.80 mmHg 372 cm/sec  TABLE 4(g)  Decay o f 0 ('Ag) 2  -dJT/dz. TT a r b . unit/cm x 10^ a r b i t r a r y 0.775 0.405 O.485 0.725  Unit  A  -dA/dt/A 'sec" 1  0.518 0.431 0.420 O.48 •4-  443 p mole/sec 4.40 mmHg 378 cm/sec  T o t a l f l o w r a t e o f oxygen Pressure linear velocity  0.520 0.625. O.58O 0.415  (  15.0 9.43 11.5 15.0  5.67 3.56 4.35 5.65  TABLE 4(h)  2 ' sl JJL mole/sec 0  Decay o f 0 ('&g)  4.64 5.29 5.04 3.92  T o t a l f l o w r a t e o f oxygen Pressure linear velocity  2  12.3 14.0 13.4 10.4  0.419 0.441 0.430 0.393  318 u mole/sec 3.20 rnmHg 374 cm/sec  29.  On the assumption that the decay of 02( Ag) i s a sum of two terms, f i r s t order and l  second order with respect to 02('Ag), the rate equation f o r the decay can be expressed as .-ft.-k *tkBtf A  where  ( 1 )  and kg are t o t a l rate constants of f i r s t  order and second order decays respectively and A  i s the concentration of 02('Ag). Dividing both sides" by A  , one gets  d£ A plot of -^fV dt/A  (2)  against A  showed a straight l i n e  whose intercept and slope are t o t a l f i r s t order and second order rate constants respectively.  The  calculated k^ and kg by t h i s analysis are shown i n Table 5F i g u r e 23.  The p l o t of-^/  A  a g a i n s t A i s a l s o shown i n  30.  TABLE 5 Total flow rate of oxygen mole/sec.  and kg ,  A  . . k.' ." sec .  .  •  kg x 10 L/rnole sec.  -Zf  1  180 200 380 275 183 277 443 318 av.  2)  k  0.273 0.351 0.350 0.304 0.216 0.189 0.277 0.259  3-05 2.54 2.82 3.39 2.84 3.56 2.73 2.39 2.92  Analysis of products i)  Oxidation of 2,3-dimethylbute"ne-2  with excited  oxygen molecules Oxidation products of 2,3-dimethyl butene-2 with non-discharged and discharged oxygen were investigated.  In the former case, that i s ,  the oxidation of the o l e f i n with ground  state  oxygen molecules, no product was found except trace amounts of water which may the oxygen from the cylinder.  have come from  With the discharge  on, only one product was found by gas.i chromatography.  The product has a f a i r l y high b o i l i n g  point and was separated from reactant by trap-totrap d i s t i l l a t i o n i n the vacuum system. to peak (a)  In addition  due to the unreacted material and  31 peak (b) due t o the product two be seen.  s m a l l peaks can  These were found to be due to i m p u r i t i e s  i n the r e a c t a n t which were c o n c e n t r a t e d i n the trapping a n d _ d i s t i l l a t i o n I n f r a - r e d , MIR,  process. (Figure 5(a)). mass and NMR  spectro  grams o f t h i s p u r i f i e d product were taken to I d e n t i f y the product. shown i n  Fig.6,7,8,9.  gas chromatography was calibration  spectrograms'-are  Q u a n t i t a t i v e a n a l y s i s by also u n d e r c a k ^ i .  The  curve of the r e a c t i o n mixture i s shown  i n F i g . 10. was  These  The r e l a t i v e c o n c e n t r a t i o n by  found by comparing  NMR  the i n t e r g r a t e d area of  some p a r t i c u l a r protons b e l o n g i n g to the r e a c t a n t and the product. O x i d a t i o n o f 2-methyl butene-2 w i t h e x c i t e d oxygen m o l e c u l e s . One  of the t y p i c a l gas .chromatograms  of the r e a c t i o n mixture i s shown i n I t was  F i g . 5(b).  taken under the same c o n d i t i o n s of gas  chromatography as was  used to d e t e c t the product  of 2j3-dimethylbuterte — 2  oxidation.  The gas chromatogram  ;  shows two main  p r o d u c t s and two o t h e r minor products whose r e l a t i v e a r e a to those o f main products i n c r e a s e d w i t h time.  From t h i s p o i n t of view,  those' two  minor p r o d u c t s are secondary products which may  be polymers  of main product.  A f t e r the two .  4  10 (a)  A  M r MUT£  ts  S  20  2,3-Dimethylbutene-2.-  e 10  ts  /VJ//VUT£ S  (b) '2-Methylbutene-2."  S O  I"  20  F i g u r e 5:  Gas chromatograms o f the p r o d u c t s o f the r e a c t i o n s of s i n g l e t oxygen w i t h t h r e e  olefins.  1200  1000  900  . 8 0 0  IR s p e c t r o g r a m o f t h e p r o d u c t from t h e r e a c t i o n . o f 2,3-dimethylbutene-2 w i t h singlet  oxygen.  -700  TO  iii  JJJLL  J2.0  3>0  F i g u r e 8:  II i  — L i _  60  4-0  70  80  Mass s p e c t r o g r a m o f t h e p r o d u c t from t h e r e a c t i o n of 2,3-dimethyl"butene-2 with, singlet  oxygen.  /oo  //o  12.0  J  5 & >  '  '  1  i - l  I I  I  r .  .  1  _  1  1  1  1  1  F i g u r e 9b: '  !  1—I  1  i  1  1  •  | '  •  ,  i '  •  1  .  1  1  1  '"l  . . . ! . i  i'" i  '  '  1  r  i'  t  1  t  I  ,  i  .  "  1  1  1  1  1  I  i  •  HMR .spectrogram o f t h e p r o d u c t from t h e r e a c t i o n of 2,3-dimethylbutene-2 w i t h s i n g l e t oxygen.  _. j 5  1  !  PRODUCT HoLB  FRACTION  (NMR) F i g u r e 10: ' C a l i b r a t i o n curve of the product.  (Product: • 2,3-dimethyl-3-hydro- ' peroxybutene-1 )  3&\ main p r o d u c t s were separated by gas chromatography, attempts were made t o i d e n t i f y them by .IR, NMR and niass spectrometry. it  I t was found t h a t  i s e a s i e r t o separate the one w i t h the s h o r t e r  r e t e n t i o n time from the o t h e r but " t a i l i n g " o f the f i r s t  product peak made c o l l e c t i o n o f the  .second q u i t e d i f f i c u l t under .the gas chromatog r a p h i c c o n d i t i o n s used.  Thus, f o r the- i d e n t i -  f i c a t i o n o f the second main product, the f r a c t i o n (B) c o n t a i n i n g both main p r o d u c t s . w as used. r  Gas chromatograms, IR, NMR and miass  spectrograms  of these separated f r a c t i o n s .are shown i n F i g . 11,  12, 13, 14. O x i d a t i o n o f cis-butene-2 The gas chromatograrn. o f the r e a c t i o n .mixture i s shown i n F i g . 5(c) •  A very s m a l l  amount o f product and a t r a c e o f water trapped by l i q u i d n i t r o g e n were found, b u t no f u r t h e r i n v e s t i g a t i o n o f t h i s product.was made. -Oxidation o f iso-butene and propene with  excited  oxygen m o l e c u l e s . Nothing d e t e c t a b l e by g a s chromatography was trapped by l i q u i d n i t r o g e n except the r e a c t a n t s and a t r a c e o f water,.'  ,  -itvrrj-jt.v  xi.ivn .'.u vovn.^.ut javii-.'  :os j o i n t l y M » I . » '-owT w.oj,  •  j r i iiuVHJ'uuv utvii  vuviiyj tn.juvn  'oa wn«iHiu(  ... •  ,  ,  —-f,—  -  — - — -  - - - - - —  ' ... _ —  —  '  " — : •  —  —  ;  —  '  .  —  _  —  — '  ..'  . —  ~  —:  r  — „ . _ _  — - — -  ...  •;  _  ....  1...  •-  -  — — —  —  '  - - — - —  — : —  — ~  —  r—  — - — —  -  —  •-  —  .  —  -•:  '-  :  . . . . — . —  .  - - - - - —  .  ' •-  -—--—  —  -  ---——••  ••• •  - - —  i  _ .  . '  —  •—  --  •  _  _  —  -  :  —  -  ..-••  —  -  ..  • — • • -  ;  —  _:1  ..:  T . V f.  •  !  U. .  •-  —  ,  - —  •'  —  .  -  _  - - : -••  >  —  \  i  - ' -  y ' '" 1.  • ~ —  ...J  *  i — ~ l  ._. — : — •  .:  1  U——-  ' \  .  —  »  — •  •  :  L.  —  ~—--  /  1—.  :  .  ^  - — _  -  —  t  \  _  —  — • — —  f  —  —  —  -  :  ]  1 /— 1 — y ~"  —  —-7-Y—  _  -  —  :  — '  •  \ -  _  —  ., — .  C  900009 " ° N — — •  :  —  * r  •—  — _ .  900C09 ' H  -  -  •  —  '  F i g u r e 11 ( a ) : Gas chromatogram o f f r a c t i o n (A) from 2-methylbutene~2 r e a c t i o n .  •  900009 '°H  '•-  F i g u r e 13 ( a ) : BMR  s p e c t r o g r a m o f f r a c t i o n (A) from  2-methyl"butene-2' r e a c t i o n .  2- metliyl'butene-2 r e a c t i o n . j  2.0  30  40  so'-  60  70  —i—  80  Figure_!14 ( a ) : Mass s p e c t r o g r a m o f f r a c t i o n (A) from 2-methylbutene-2 r e a c t i o n *  ?0  114 30  4-0  ~\—  GO  LLJLJ 70  SO  F i g u r e 14 ( b ) : Mass s p e c t r o g r a m o f f r a c t i o n • (B) f r o m 2-methylbutene-2 r e a c t i o n .  to  47.  3)  Decay of 0  2  ('Ag)  with  2,3-dimethylbutene-2  The i n t e n s i t i e s  of emission at 6340A  as a function of distance from o l e f i n i n l e t tube are tabulated i n the tables under constant t o t a l oxygen and d i f f e r e n t  flow rate of  rates of 32('Ag) ( and o l e f i n . TABLE 6 (a ) distance from i n l e t tube. cm 2 5  10 15 20 30  40 50  60 70  80  90  Decay ' 70% 27.2 26.7 25.8 25.2 24.4 23.6 22.2 21.4 20.5 20.0 19.1 18.4  o f  I  6340 50%  25-4 24.8 24.1 23.2 22.3 21.3 20.2 19.3 18.6 17.9 17.2 16.4  (Table 6)  with o l e f i n at d i f f e r e n t pi Power of discharge 20% 30% 22.2 21.4 20.5 19-7 19.0 17.8 16.7 15.7 15.2 14-5 13-9 . 13.4  A =-(2.18)2 2  flow  19.1 18.3 17.3 16.4 15.5 14.6 13.5 12.8 12.1 11.6 11.0 10.5  10% 12.1 11.2 10.2 9.2 8.5 7.3 6.5 5-7 5.2 4.8 4*4 4.2  16340  flow rate of o l e f i n  : 0.14  t o t a l flow rate of oxygen:  mole/sec 180 :|A mole/sec  TABLE 6 (b) distance from i n l e t tube. cm 2 5 10 15 20 30 40 50  60 70  80 90  Decay of I5340.with o l e f i n at d i f f e r e n t Power of discharge  70%  50%  30%  26.4 25.7  24-9 24.2 23.2  21.4 20.5 19.6  24.7 24.1 23.0  18.6  22.4 21.7 20.4  22.0 20.6 19.7  17.9  16.5 15.4 14.5 13.9 13.2 12.7 12.2  19.4  18.2 17.6 16.8 16.1 15.4  18.9  18.2 17.3 16.6  flow rate of o l e f i n ;  TABLE 6 (c)  5 1.0 20 30 40 50  60 70  80  90  Decay of  X  6340  19%  18.0  17.0 15.9 15.0 13.9 12.6 11.3 10.8 10.1 9.6 9.0 8.4  0.41  *  powers.  10%  11.3 10.5 9.2 8.4  7.2  6.3 5.2 4.7 4.1 3.8 3.4 3.2  mole/  with o l e f i n at d i f f e r e n t  powers  70%  50%  30%  20%  10%  25.1  23.5  20.4 18.9  16.4  11.4 9.9 7.4 6.2 4.8 4.2 3.4 3.1  23.9 21.7  19.9 18.3 17.2  16.3 15.4 14.8 14.0  22.2 20.1 18.2  16.7 14.9  16.8 15.5 14.8  13.8 13.1 12.5  "  13.5 12.3 11.7 10.9 10.3 9.9  flow rate of o l e f i n :  14.9 12.4 10.8 9-4 8.6 7.9 7.2 6.9 6.4  2.8 2.5  0.82 ./A mole/sec  49.  TABLE 6 (d) distance from i n l e t tube cm. 2 5 10 20 30 40 50 60 70  80  90  Decay o f I^-^O  v /  i t h o l e f i n at d i f f e r e n t  70%  50%  Power o f d i s c h a r g e 30% 20% 20%  25-7 24-3 22.6 19.9 18.0 16.2 15.0 14.0 13.2 12.2 11.6  23.6 22.2 20.6 17-8 15-9 14-2 13.0 12.2 11.4 10.6 10.0  20.6 19.2 17.5 14.7 13.0 11.4 10.3 9.4 8.7 8.0 7-5  TABLE 6 (e) distance from i n l e t tube  2 cm 5 10 20 30 40 50  60 70  80 9.0  10.0  8.8  7-1 4.6 3.0 2.1 1.5 •1.1  7.8  8.8  7-7 7.0 6.3 5-9  6.7 6.0 5-4 4-9 4•4  5-4  flow rate of o l e f i n  10$p  16.7 15.2 13.5 10.9 9.0  17.5 16.1 14-5 12.0 10.0  powers.  0.8 0.7 0.5  1.10 jJ- mole/ sec.  at d i f f e r e n t  low r a t e s  Flow r a t e o f o l e f i n 1.07 1.79 1.54  JUL mole  0.72  0.34  17.1 15-6  17.4 16.0 14.2 11.6 10.1 8.8 8.1 7.2 6.9 6.2 5-9  17.5 16.3 15.0 13.0 11.6 10.7 9.8 .9.2 8.7 8.2 7.8  16.7  17.1  12.5 9.0 7.2 5-5 4.8 4.0 3.5 3.0 2.6  13.3 10.2 8.3 6.9 5.8 5.1 4.5 4.0 '3.6  15.0  15-5  13-6 -• 10.9 9.0 7-5 6.6 5-9 • 5-4 4-9 4.4  TABLE 6 (f)  distance from i n l e t tube  Decay of I5340 of o l e f i n ,  2.00  5 cm 10 20 30 40 50  23.3  21.6  18.4 15.9 13.8  60  12.1 10.9  80 90  8.0  9.8 8.8  70  d i f f e r e n t low rates  a t  Flow rate of o l e f i n  kA.  mo le/sec. 0.24  1.33  0.82  0.76  24-7 23.0  25.1 23.9  25.7 24-5  18.3  18.4  20.1 17.9 16.0 14.6 13.6 12.5 11.7 11.0  21.7 19.9  17.2 16.3 15.4 14.8 14.0  26.0  25.0 23.2 21.8  21.9 20.1  20.4 19.4  17.0 16.2 15.2 14.5 13.9  18.6 17.8 17.1 16.6  The attempt to f i n d the rate equation was made assuming a simple decay mechanism.  For t h i s purpose, i t  i s quite convenient to f i n d an i n i t a l - r a t e under certain conditions.  The plot of l o g ( - / 4 z ) against-distance 6  (z) showed a f a i r l y good straight l i n e e s p e c i a l l y at high flow rate of o l e f i n .  Therefore,  the i n i t i a l rates (Vo)  were determined as intercepts o-f these l i n e s .  The r e a l  i n i t i a l rates (vo) of decay of 02('Ag) with the e f f e c t of o l e f i n were determined by subtracting the rates (U ) of 0  decay of O^t'Ag) i t s e l f from the rates (Vo) determined by tke above method.  The summarized r e s u l t s are shown i n Table 7.  Decay rate of 15340  TABLE 7  s  e  t  o  I  Ro . >mole ' sec  12.6 • • • 0.14 19.6 0.14 1 22.6. 0.14 • 25-3 0.14 27.6 0.14 " 1270 0T4~I 18.6 O.41 2 22.0 . 0.41 • 25.4 0.41 27.0 0.41 13.0 . 0.82 18.3 0.82 3 22.0 0.82 25.0 0.82 26.8 0.82 11.0 1.10 17.6 1.10 18.4 1.10 4 21.8 1.10 24.7 1.10 • • - •- 27.11.10 27-5 0.24 5 27.5 0.76 27.5 0.82 27.5 1.33 27.5 2.00 18.5 O.34 18.5 0..72 6 18.5 1.07 18.5 1.54 18.5 1.79  a  t  t=o.  Vo . I434O'' .— 10 cm 2.90 2.67 2.20 2.11 I.64 J7U5 2.95 2.54 2.21 2.06 3.91 3.95 3.40 3.01 3.00 -4.91 4.37 4-45 4.47 •4.43 .4.39 2.33 3.06 3.13 4.15 4.17 3.47 4.78 5.22 5-52 6.68  Uo 634C,  I  10 cm . 0.271 0.476 0.573 0.676 0.738 0.258 0.444 0.550 O.665 0.720 0.283 0.437 0.550 0.651 0.710 0.230 0.416 0.439 0.545 0.642 0.722 0.736 0.736 0.736 0.736 0.736 0.441 0.441 0.441 0.441 0.441  YD  *6340 —10 cm 2.63 2.19 1.63' 1.42 0.90 '. ~T779~ 2.51 1.99 1-54 1.34 3.63 3.51 2.85 2.36 2.29 4.68 3-95 4.01 3.92 3.79 3.67 1.59 2.32 2.39 3.41 .3.43. 3.02 4.34 4.78 5.08 6.24  Discussion 1) -- • • - Decay o f :  '.-..].  0 (^g). 2  -The f o l l o w i n g processes could c o n t r i b u t e to the decay o f 0 (!Ag)  i n the absence of any added  reagent- .  .  0 ('Ag)  J_>  0 ('Ag)  + wall  0 ('Ag)  + 0 ( Xg)  2  2  2 2  0 (*£g)  k  2  h,P(l2700A)  2  0 ( X'g) + w a l l  JM>  2  (4.)  J  20  M>  3  2  (3)  CZg)  2  (5)  0 (kg) -Mils. 2 0 f Z l g ) -r-hP (6340A) 0 ( ' A g ) -M% 0 flg) + 0 ( ^ g )  (6)  2  ?  2  2 0 ('Ag)  2 0  2  (7)  2  2  (8)  2  where k(L), k(2), k(3),  k(5), and k(6) are r a t e c o n s t a n t s .  - The r a t e constants^ f o r r a d i a t i v e k(L) and k(4) are 1.5/ (3±0.6)x 10~2  xlO  - / f  .'...''sec" and 0.2S 1  l/raole sec. r e s p e c t i v e l y .  are many o r d e r s o f magnitude  decay  or These  too s m a l l to con-  t r i b u t e to the decay i n our f l o w system and w i l l not be c o n s i d e r e d f u r t h e r . The experimental f i r s t constant  order decay  (kA). and the second order decay  (kB) can be expressed ky, k(5), and k  i n terms o f k0J,  constant  k(2), kO),  k(6).  = k(L) + kfc) + kp) 0 f e g )  A  ' . k  2  B  * 144) + k(5) +  k(6)  Let T r e p r e s e n t the t o t a l c o n c e n t r a t i o n o f oxygen  (9)  (10)  T, = 0 ( Z l g ) + 0 ( ' A ) + o t h e r s p e c i e s j  2  ^  2  0 fcg)  g  2  Then the e q u a t i o n 9 and 10 k  A  k  B  kO)T  =  k(5)+  -  (n)  + 0 ('A ) ,  2  k(6)-  g  can be e x p r e s s e d  as (12)  kD)  (13)  F i r s t o r d e r decay p r o c e s s . By p r o t t i n g k^  a g a i n s t the  total  c o n c e n t r a t i o n o f oxygen ( T ) , k^) and k(3) can  be  o b t a i n e d from the i n t e r c e p t and s l o p e r e s p e c t i v e l y . From.a l e a s t squares p l o t o f the d a t a l i s t e d i n Table  5,  we have c a l c u l a t e d v a l u e s o f k(2) =  ( 0 . 2 4 6 +.0.072) s e c "  l/mol'e s e c .  1  and  kfc) = ( 6 . 2  + 13.5)  x  10  S i n c e the v a l u e o f kp) l i e s w i t h i n  the p r o b a b l e e r r o r , i t i s o f l i t t l e  significance.  Twice t h e p r o b a b l e e r r o r i n a d d i t i o n t o the v a l u e w i l l be used as an upper l i m i t f o r kt3). i ^ e . k(?)^  0.33  x 10-  1/rnole sec.  the f r a c t i o n o f c o l l i s i o n s  One  can  t h a t are  by a p p l y i n g c o l l i s i o n t h e o r y .  calculate effective  L e t E be  s p e c i f i c e f f i c i e n c y o f d e a c t i v a t i o n by  the reaction  ( 5 ) ' w h i c h i s e x p r e s s e d by the equation,' Number o f m o l e c u l e s d e a c t i v a t e d by \ k  E •=  t h e r e a c t i o n (5)  /  — : — _  (  T o t a l c o l l i s i o n number between  \  0 .('Ag) and 0 t Z L g ) i n an u n i t volume) J  2  2  54. k3  N  A  N V B  ^2  B  k'3  (14) 2  AB  k3:  rate constant (cm /sec. molecule),  k:.  Boltzman constant.  T:  Kelvin temperature °K.  JU.:  reduced mass of 0 (& g) and  where  2  •  0 fe g) i n t h i s case. 2  ($~AB radius of oxygen.. :  N  Ng: number of molecules of 02(!Ag)  A  and 0 f.Zg) i n an unit volume. 2  Then the maximum e f f i c i e n c y of deactivation by reaction (5)  becomes 2.2  x 10  to one deactivation in>4«5 x An analogous (4)  which corresponds  10  collisions.  e f f i c i e n c y of deactivation by reaction  can be calculated using a similar equation : 7  E  ^ r a t e of decay by reaction (4)  (  Total number of c o l l i s i o n s of  0 ( J ^ g ) with the wall. 2  NA  V  k2  i N US A  ^  55.  (15) where V i s volume and S i s s u r f a c e  area c o r r e s -  ponding to V. (2)  k(2):  r a t e constant o f r e a c t i o n  c:  i s mean m o l e c u l a r v e l o c i t y which i s • expressed by the formula  r:  i s diameter o f r e a c t i o n tube.  N^:  i s number o f molecule o f 0 ( A g ) 2  i n an u n i t volume. Then the e f f i c i e n c y o f d e a c t i v a t i o n by w a l l c o l l i s i o n becomes 6 x 1 0 ~  6  which corresponds to  one d e a c t i v a t i o n i n every 1.7 x. 10^ c o l l i s i o n s on the w a l l . a t room temperature  (23°C).  to the w a l l might c o n t r o l the r e a c t i o n t h i s i s . t r u e the average time  Diffusion (4)-  If  (tj)) r e q u i r e d f o r  a molecule to d i f f u s e to the w a l l i s much l a r g e r than the average time [ty) deactivated  a t the w a l l .  f o r a molecule to be The v a l u e o f t ^ can be  c a l c u l a t e d from the theory o f Rrownian which  gives  motion  where D is.the d i f f u s i o n c o e f f i c i e n t •  -2 X  i s the mean square p a r t i c l e  displacement during the time tjj Since the d i f f u s i o n c o e f f i c i e n t i s inversely proportional to the pressure i.e.• D = D^ef) P^efyP  The  (17)  c r i t i c a l pressure P above which d i f f u s i o n i s  important may be calculated from the r e l a t i o n s t  D  >  t  . (18)  ¥  and . 1  t The  w  -~W)  (19)  c r i t i c a l pressure i s found to be 7lJ rnm Hg at  273°K under these conditions, i f the value 2 0.18 cm /sec i s taken as the s e l f - d i f f u s i o n c o e f f i c i e n t at 273°K.  This pressure i s much  higher than the pressure i n the experiments. Therefore,  the process of wall deactivation i s  not d i f f u s i o n limited'Under  these experimental  . conditions and wall deactivation w i l l be independent of pressure.  For the reactions which are  second order i n 02('^g), the c o l l i s i o n e f f i c i e n c y can be calculated applying equation (14)., shown before.*  Then the e f f i c i e n c y o f deactivation  * A factor of one h a l f must be applied since the formula would count each c o l l i s i o n  twice.  by a l l second order reactions becomes 9.6 x 10" which corresponds to one deactivation i n every 7 10 collisions. Second order decay processes From Table 5 the average values of the t o t a l second order rate constant k  B  = 2 . 9 2 x lcA  I •'mole' sec".'  .  which from equation (13) is.equal to k(5) + k(6)-k(3) Since k(3) i s about 1% of kg i t w i l l be neglected i . e . i t w i l l be assumed k(5)+ k(6) = 2 . 9 x 10  4  £ mole'sec"/  The;.most r e l i a b l e value of k(5) available i s that obtained by Arnold who 02^^^  formation.  1.3 x 103.  observed the-rate of  The value she obtained i s  I f t h i s i s correct then the dominant  second order decay i n our system must be reaction ( z ) . , . I f the reaction produces two ground state oxygen molecules then the process i s spin allowed and could conceivably be rapid. hand Arnold's value of k5 may  On the other  be low (see Tablets)  and hence i t i s s t i l l possible that k(5) = 2 . 9 x 10 . 4  As i s shown i n Table-8, the values of the rate constants found i n t h i s study are comparable to the values obtained by some e a r l i e r workers e s p e c i a l l y those of Arnold's.  58.  TABLE 8  . Comparison o f r a t e c o n s t s . obs. by other :  k(2)  0.178  k(3)  C  1.3 x 1 0  ^  4.3  2  3  ^3.3  x  //mole, s e c , 7 ± 0 , 5  10  2  sec  - 1  J^/mole. s e c ,  J2/mole. sec  1.8 x 1 0 k(6)  0.25  - 1  2.77 x 1 0  1.53 k(5)  sec  P r e s e n t work  investigators  sec.  i / m o l e . sec.  ) H  f/mole s e c . ) I/mole.  x 10  ) J  2 . 9 x 10^ A/mole. s e c .  I d e n t i f i c a t i o n of Products The r e a c t i o n product of 2.3-dimethyl  butene-2  with e x c i t e d oxygen NMR.  IR. and NIR  spectrograms of the  product are compared i n Table 9, 10, to those o f 2j3-dimethyl-3-hydroperoxybc/tene--L  taken  35 36 by Schenk,-^ Wexler, and o t h e r workers. The mass spectrogram of  ^7  2 3-dimethyl-3-hydro;  peroxy b o l e n e - 1 taken by Winer and B a y e s ^ i s shown i n F i g . 15. The NMR  spectrogram o f the product i s  q u i t e c o n s i s t e n t with t h a t of 2.3-diniethyl-3r) hydroperoxy butene-1 which was  produced by  photosensitized a u t o x i d a t i o n and ^2®2 of 2,3-dimethyl butene-2,  oxidation  except X. ( p o s i t i o n )  and shape o f the proton of the hydroperoxide group.  D i f f e r e n t v a l u e s o f -c are p o s s i b l e  because, as i n the case of h y d r o x y l proton, i n t e r m o l e c u l a r hydrogen bonding e f f e c t s can cause .the spectrogram to show a c o n c e n t r a t i o n and temperature  dependence.  For the-NMR measurement  of the product, the product was not d i l u t e d with any s o l v e n t ; on the o t h e r hand Wexler  used  carbon t e t r a c h l o r i d e as a s o l v e n t to measure the NMR  spectrogram of 2 3  butene-1.  ;  dimethyl-3-hydroperoxy  60.  TABLE 9  NMR  comparison obs.  A B  -6-CH, =C—CH3  C  -C = CH  D  -00  H (?)  (A:3:C:D)  Wexler  '8.67 ( s i n g l e t )  .8.70  8.21 ( d o u b l e t )  8.22  5.10 (broad)  5-08  1.07 ( s h a r p )  1.62  . - 1: 1.98: obs.  2.99:  (A:B:C:D) = ?: 2: 3: 6 Wexler  6.03  (doublet)  (broad)  TABLE 10, Product Wave No. cm" 831 (M) 900 (3) 960 1012 1039 1148 (S) 1170 1207 (!•:) 1298 1360 (S) 1375 (S) 1452 (S) 1642 (Ii) 1800 2985(S) 3400 (S)  IR,'and NIR comparison (95-5%) Wave length* 12.0 11.1 10.4 9.88 ' 9.63 8.71 8.55 •8.28 7.70 7.36 7.28 6.88 6.09 5-56 3.35 2.94 N.I.R. 2.107 2.067 1.765 1.730 1.689 1.676 1.628 1.443  WexleP Wave 1 e.ngtb' 6 )  Shenck Wave I £)ig b'-v  11.9V 11.04 - '  9.83 8.69 8.51 8.27 7.68 7.32 7.25 6.86 6.04  6.04  .2.84  2.94  ( 3 7 )  2.118  1.63 1.45  a  (37)  { 3 7 )  b  b  J  _u_ /o  20  1UJ_[_  •9-0  F i g u r e 15:  J  L  60  7o  8o  i 11 i  Mass spectrogram of 2,3-diraethyl-3-hydroperoxybutene-l taken by Winer and Bayes.  — * - i — /00  /.20  64.  To determine whether the hydroperoxy •group exists i n the product-, an NIR  spectrogram  was taken to check f o r 1.45^ absorption which i s c h a r a c t e r i s t i c f o r -00H i n the case of 2,3-dimethyl-3-hydroperoxy butene-1. at 1.443/* was found.  Absorption  This confirms the presence  of -00H group i n the product.  There i s another  p o s s i b i l i t y that the functional group was instead of -00H.  -OH  I f i t i s true,' there should  be an absorption at 1.425P- and also i n the  NMR  - spectrogram of t h i s product there should be a peak between  TD=6  and 7 (see F i g . 16); but both  of these were absent.  .  -  •  i The existence of CH =C- can be shown 2  by IR and NMR  spectrograms.  The IR absorption  of .-6.09JLI shows the evidence of a terminal double bond and the NMR  spectrogram can be explained  In .terms of the d i f f e r e n t c h a r a c t e r i s t i c s of the  two protons attached to terminal double  bond ( C H o = C - C H 3 ) . (Hj_ and H ) 2  For these two protons  of the ethylenic group, the unperturbed  A B type quartet due to F i g . 17. •with the H  and H  2  i s shown i n  The components of the doublet associated 2  proton are s p l i t into quartets by the  Hi  r  1  1  I  1 1 1  Figure 17: NMR  splitting  doe t o A 8 system  methyl group adjacent to the ethylenic group. Thus the value f o r the coupling constant between the ethylenic protons (H^ and.H2) i s found to be 1,4 cps which i s consistent with that of reference 40 H r . 4 cps). For the mass spectrogram, i t i s not surprising that the mass number of the parent could not be detected because t h i s hydroperoxide i s probably unstable under electron bombardment. The cleavage of the 0-0 bond i s expected to be easy because of i t s r e l a t i v e l y low bond energy (~5lK al/mole c  i n the case of hydrogen peroxide).  Some of the main peaks are explained as follows.  -tn««  FjCCOCH  I  |  I  I  j •  I •i^  UXI-..X\K.—L  F i g u r e 18:  M l IS spectrogram of 3-methyl-3-hydroxybutene-1.  on  r  H  i  4  C OOH  /  4  ^ HC  c—c-o  + . .-'OH  .CH,  4  >  HA  CH  3  t -  i t  C  + -CH,  Q  4 <CH  4  = 4-1  He, (C H,-c =q) + • cH, C -  0  or  H c/ 3  C-"C.-=0  a  T h i s i s merely one c r a c k i n g schemes.  of many p o s s i b l e  Most of the  small peaks are  q u i t e d i f f i c u l t to e x p l a i n e x a c t l y , mainly because of the complicated  cleavages and  arrangements of the product.  Winer and  a l s o took a mass spectrogram of the  reBayes  product  produced under the gas phase o x i d a t i o n of dimethylt>utene-2  with  s i n g l e t oxygen.  spectrogram showed a c r a c k i n g p a t t e r n from the present The  ;  Their different  work e s p e c i a l l y a t h i g h v ^  reason the b r a c k i n g  the same i s not  2 3-  clear.  value.  p a t t e r n s were not  exactly  I f they separated  the  product from the r e a c t i o n mixture by gas  chroma-  tography i t i s q u i t e p o s s i b l e t h a t there  existed  some decomposed p r o d u c t s which may d i f f e r e n t cracking patterns.  show q u i t e  However i t should  be noted t h a t c r a c k i n g p a t t e r n s depend g r e a t l y . on the o p e r a t i o n  c o n d i t i o n s as w e l l as on  the  type of instrument used. The  NMR,  IR and  NIR  q u i t e c o n s i s t e n t with those of  spectrograms are 2,3-dimethyl-3-  hydroperoxybutene-1. Hence, i t may  be concluded t h a t  the  product of the r e a c t i o n of 2,3-demethylbutene-2  with (^('Ag)  i s "the hydroperoxide, whose formula  V  i s  CH =C A  \  5  -C-CH,  GhU  1  00 H  (2 3-dimethyl-3-hydroperoxybutene-l) ;  Reaction product of 2-methylbutene-2 with excite oxygen As i s shown i n the gas chromatogram, there are four main products (A.B.C.D.),  Identi  f i c a t i o n was attempted only f o r two (A and B). Product A A was separated from the reactant and other products by gas chromatography.  Even  -though the separation was quite successful there were s t i l l small amounts of impurities a l l of which vrere unknown. The collected samples contained more than 90 area% of A, NMR,  IR and mass spectro-  grams were taken f o r t h i s separated f r a c t i o n . According to the WMR  spectrogram,. the r a t i o of  protons i n the quartet, t r i p l e t and singlet whose ~C(PPM) are approximately 4-0, 4.8 and 8.7 respectively i s about 1: 2: 6.  The whole  spectrogram was compared with that of 3-methyl41 ' 3-hydroxybutene-l (See F i g . 18). The two  spectrograms are almost i d e n t i c a l except f o r the p o s i t i o n o f the proton the NMR other  o f -OH group.'  However  spectrogram o f the f r a c t i o n has some  s m a l l peaks which were a s s i g n e d  of impurities.  as those  Hence, the s k e l e t o n o f t h i s  product A i s taken to be  T h i s compound has a. t e r m i n a l  ethylene  group which i s an ABC system.  T h i s i s one o f  the more complex s p i n - c o u p l i n g  systems, and s e t s  o f c a l c u l a t e d spectrograms, with v a r i o u s  coupling  c o n s t a n t s and s i g n s are g i v e n by Wiberg and 42 ' ' ' . " Nist . One witk a s i m i l a r p a t t e r n t o the i^-Ii;  " "  spectrogram"'of t h i s p r o d u c t a i s shown i n F i g . 19.  T h i s proposed s k e l e t o n o f A i s q u i t e reasonable  from a c o n s i d e r a t i o n o f the r e a c t i o n  of 2,3-dimethyl butene-2 producing 2-hydroperoxybutene—1.  2^, 3-dimethyl -  Foote e t . a l .  oxidized  2-methylbutene-2 by oxygen.'gas w i t h the help o f a p h o t o s e n s i t i z e r under the i r r a d i a t i o n o f l i g h t and  a l s o by the oxidant  of hydrogen peroxide  produced by the r e a c t i o n  with  sodium h y p o c h l o r i t e .  A f t e r the o x i d a t i o n , the products were reduced immediately by t r i m e t h y l phosphite to  7/ it  **  -• •  x >• »> >  CO  o P j—' o e  :4 r x >• x  (—*  p c+  CD  Pi  >• x x *• >» >  f * J t C£C  > »• K  o CQ  o 'E5  o. w  rk>|i>>>>>Kk><>)ii>»  •O  5  j - > > V >• X >>•> » >  fc>^»xxx>x»'x  •- — —  r  x  72.  corresponding alcohols..  One o f t h e a l c o h o l s ,  which was a main p r o d u c t f o r b o t h p r o c e s s e s was i d e n t i f i e d t o be an u n s a t u r a t e d a l c o h o l whose s t r u c t u r e was  CH,= C - C M  CH 3 OH  T h i s a l c o h o l a l s o s u p p o r t s t h e proposed s t r u c t u r e o f A because 0 2 ( ' A g ) heterolytjc.:  i s produced by  c l e a v a g e o f hydrogen p e r o x i d e .  An e f f o r t was made t o l o c a t e a p r o t o n resonance o f t h e -00H group i n t h e range o f ~C = 0 t o t  = 3, but no d e f i n i t e peak was f o u n d .  T h i s may be because o f t h e b r o a d e n i n g o f t h a t peak f o r somedunknown r e a s o n s . The IR s p e c t r o g r a m o f t h i s shows t h e p r e s e n c e o f an -OH group. i b i l i t y that the  fraction The p o s s -  -OH group e x i s t s as a hydroxy  group i s e x c l u d e d by the absence o f any s i n g l e t peak i n t h e NMR spectrum i n t h e range *"C = 5 • 5 t o "C = 7-0.  There i s a l s o no p o s s i b i l i t y t h a t t h e  p r o d u c t A i s a compound whose s t r u c t u r e i s  ^c-c-oo-c-c^ because o f t h e a b s o r p t i o n o f t h e -OH group i n the IR spectrum and a l s o because o f i t s e x p e c t e d  72.  high b o i l i n g point. Hence product A may  be 3-methy1-3-  hydroperoxy-butene-1, i . e .  n  The mass spectrogram  OOH of A i s much too complicated  to explain. • Some of the mass numbers can be explained by the same scheme shown i n the case of 2 3-dimethyl-3-hydroperoxy-butene-l, ;  but  some of the highest peaks, f o r example, M/e  =  7 l and 59, are quite d i f f i c u l t to r a t i o n a l i z e . This may  be because of the i n s t a b i l i t y of A  under the high potential of many complicated  f i e l d and production  fragments.  Product B As shown i n the gas chromatogram after the separation, the separated f r a c t i o n , which was expected to be mcstly B, contained only about 50%.  The main impurity was around 5C;t,ofVA. There-  fore, NMR,  IR, and mass spectra-.;. f t h i s f r a c t i o n 0  showed both c h a r a c t e r i s t i c s  of A and B equally.  To f i n d new peaks i n the NMR spectrogram f o r 3, spectrograms of both fractions were compared and the peaks from A were cancelled out. By t h i s operation, four sets of peaks were found belonging to product B with "C of 5-06  (broad),  74. •5.58 ( q u a r t e t ) ,  8.27''(doublet),  in  5.8:  the  which "also  ratio is  of  roughly  compared  2.6:  2:  with  1:  •is. a s s i g n e d  to  the  -ethylene  group  a  group.  methyl  protons .The  two  broad  geminal  whose-other peak  of  seen  at  quartet  is  also  expected  proton  ••methyl, g r o u p . these  two  They  are  that  from  -arison  both  is  The  the  =  i f  spin-spin  a  of  includes  coupling protons  ( 6 - 8 of  an  group  adjacent  to  to  a  constants  are  compared.  consistent  with  cps).  comp-  the  The  B with  in  table  that  is  ;  shown  .  11. In.the  NMR  (diluted  considered  as  hydroperoxide depend  is  being  C Cl^") , about  due  group. on  spectrogram  with  p e a k . w h o s e "C v a l u e  to  The  mentioned  the  this  there  broad  can  of  of  of For 3  is  be  a  this  because  product  separated a  This  effects.  the  is  proton  position  bonding above,  of  2.35-  concentration  -•molecular ' h y d r o g e n reasons  = 5«06)  carbon,  2 3-dimethyl-3-hydroperoxybutene-l  might  are  doublet.  of  fraction  sets  methyl  the  is  c p s . . ^'7hich i s  spectrogram  as  8.27  characteristic 7  (~C  protons  these  attached,  reference^  of  t  peak  substituent  be  the  These  2,3-dimethyl-3-  can  ^which  of  The  The  respectively,  7.2  of  (doublet)  8.79  3'-'- 3-  those  •hydroperoxybutene-2.  7»3-  and  peak  interthe thought  75  to be 2-methyl-3-hydroperoxy  C ti ^ ^ C -  / CH  C - H  C  butene-1 i . e .  3  Foote e t . a l a l s o found the c o r r e s p o n d i n g *  a l c o h o l , t h a t i s , 2-methyl-3-hydroxybutene-l, a f t e r the r e d u c t i o n of the o x i d a t i o n mixture o f 2-methylbutene-2  with" hydrogen peroxide  (and.sodium h y p o c h l o r i t e ) or by p h o t o s e n s i t i z e d autoxidation. proposal that  T h i s f a c t a l s o supports the 2-methyl-3-hydroperoxybutene-l  i s one o f the p r o d u c t s under the c o n d i t i o n s used.  TABLE 11  Comparison  o f NMR  spectrograms  product B  2.3-dimethyl~3hydroperoxy-butene-1  5-06  (broad)  5.10  (broad)  8.27  (doublet)  8.21  (doublet)  -CH3  8.79  (doublet)  8.67  (singlet)  hyC-C-H  5-58  (quartet)  -00H  2.35  (broad)  1.07  (singlet  = CH  2  =a - CH  3  (?)  sharp)  From mass and IR spectrograms i t can be s a i d  that  both A and B are q u i t e s i m i l a r compounds but no f u r t h e r i n v e s t i g a t i o n has been made because the f r a c t i o n used f o r mass and IR spectrograms i s ;  found to be an almost e q u i v a l e n t mixture o f A and. B. I t i s very i n t e r e s t i n g to know that the p r o d u c t s produced by the r e a c t i o n o f o l e f i n s w i t h C^l'Ag)  i n the gas phase are i d e n t i c a l to those  produced by p h o t o s e n s i t i z e d a u t o x i d a t i o n • a n d by hydrogen p e r o x i d e ( w i t h  'sodium h y p o c h l o r i t e )  oxidation of o l e f i n s .  In the case o f gas phase  o x i d a t i o n w i t h d i s c h a r g e d oxygen (with  distill-  a t i o n o f mercury) and hydrogen peroxide it  oxidation,  I s c l e a r t h a t the s i n g l e t oxygen molecule  i s the o x i d a n t .  T h e r e f o r e , the mechanism  could  be c o n s i d e r e d to i n v o l v e a s i n g l e t oxygen molecule on the o t h e r hand, i n the case o f p h o t o s e n s i t i z e d a u t o x i d a t i o n , two p o s s i b l e mechanisms were d i s c u s s e d by Foote and Wexler i.e:;.  A)  Sens 1  Sens  3  Sens +  "'"Sens > 3  0  • Sens - 0 0 .  2  3  sens >  + A —> A 0  • Sens - 0 0 • 2  + Sens  77  B)  Sens  "'"Sens  ISens 3  ——>  S e n s + CU  >  3  10  2  .+ A  3sens Sens + 0 1  A0  —->  2  2  Where Sens i s a p h o t o s e n s i t i z e r and A i s an a c c e p t o r .  In view o f the r e s u l t s  experiments i n which s i n g l e t  o f those  oxygen molecules  were used as an o x i d a n t , mechanism B) i s preferable.  I f t h i s i s t r u e , the mechanism o f  o x i d a t i o n o f o l e f i n s w i t h s i n g l e t oxygen molecules can  be suggested. The s i n g l e t oxygen molecule may be  electrophilic.  '0  = a  <—>  |0 = 0.i  As i n the case o f bromination o f o l e f i n s , electrophilic  singlet  this  oxygen molecule might  a t t a c k the double bond o f an o l e f i n g i v i n g some intermediate.  Then the m i g r a t i o n o f hydrogen  (proton) might make a hydroperoxide. the  Therefore,  h i g h e r t h e . e l e c t r o n d e n s i t y o f the double bond  becomes the more p r e f e r a b l e i t i s f o r the o l e f i n to be a t t a c k e d by t h i s e l e c t r o p h i l i c oxygen molecule i f we n e g l e c t s t e r i c e f f a c t s .  The methyl  group has a tendency to donate e l e c t r o n s to an  78.  adjacent carbon.  T h e r e f o r e , the more methyl  groups t h e r e are a t t a c h e d to the double bond the more e a s i l y an a t t a c k might ; e l e c t r o p h i l i c oxygen molecule.  be made by Qualitatively  t h i s i s confirmed by the o b s e r v a t i o n that ;2 3-dimethylbutene-2 7  r e a c t e d with e x c i t e d oxygen  -molecules more e a s i l y than 2-methylbutene-2. In the case.of propylene no product -was found w i t h the r e a c t i o n o f s i n g l e t oxygen molecules.  The r a t i o o f p r o d u c t s o f o x i d a t i o n  •'-•of. 2-methylbutene-2 with s i n g l e t oxygen molecules . i . e . the r a t i o o f  3-methyl-3-hydroperoxybutene-l  to 2-methyl-3-hydroperoxybutene-l  was two.  28  Foote et a l _ r e p o r t e d a p r o d u c t r a t i o o f one. Both o f these r a t i o s are u n l i k e l y -mediate  shown below has an equal  •of a hydrogen  i f the i n t e r probability  m i g r a t i o n from any methyl  group  a t t a c h e d to the double bond carbons;  but they are a c c e p t a b l e i f the s h i f t of the oxygen molecule a t t a c h e d t o the double bond i s e a s i e r to the carbon atom with' more methyl  group.  Thus the mechanism o f t h e o x i d a t i o n of mono-olefins with the s i n g l e t  s t a t e o f oxygen  molecules  might  V  uc  of  Decay  not t r i e d  log  (-vo)  olefin)  of  to  find  f o r runs  with  This  t o one h a l f .  Ogt'Ag),  ensity  If equation against  i s  of  l o g I?  the value  l o g le  at  expressed should  on one l i n e .  that  with  of  as  i s  that  respect  molecules amounts.  i d e n t i f i e d  flow  shown  rates  i n F i g  to find  6340A" a t t of  olefin  i n a  simple  show a i s  or  i t  i t s  These  i s  rate  slopes  i s  quite  with  respect  l o g I^. F i g  and the  the plot  of  oxygen  The  (See  right  form  (int-  21) rate  log(--VO/7RO )  line..  i n Fig.21,.  the points  of these  decreases  observed  flow  20.  against  = o).  olefin,  of total  the order  the trend  l o g ( - V § / Ro )  the  of o l e f i n  straight  seen  to  ( i n i t i a l  the order  Moreover  increases.  reaCtiOfi  small  products  l o g Ro  t h e same  Hence,  the order  However, not  i t s very  log(-V0//R0) w a s p l o t t e d  of emission  oxygen  the  2,3-dimethylbutene-2  against  graph  show  of  t o be 3 - h y d r o p e r o x y b u t e n e - l  the order  was p l o t t e d  of  other  with  the two l i n e s  close  of  o f 0 ('Ag) 2  singlet  because  products.  C^'Ag).  and  of the product  with  a knowledge  estimated  u  oort  decomposed  To  follows  •  /-- <  cis-butene-2  From  3)  /  i d e n t i f i c a t i o n  was  is  •  as  c  ••->  The  be w r i t t e n  as  facts  are  points  the  shows  value  simply  mean  0.5  F i g u r e 20:  R e l a t i o n s h i p between log(-v ) and logR,. 0  3 V ^ir-c J 5 f T /  i.&  o  A  5  D  ?  V  •r O 6  ^ o  °  [• o  -l-O  F i g u r e 21:  l.l  I.J2-  •1-3  R e l a t i o n s h i p between  Jog log(-Tg//R).  I,  and l o g 1^.  1.6  0  t h a t the. formula o f the r a t e equation f o r the decay o f O^l'^g) w i t h t h i s o l e f i n i s not simple. I t might be doubted  that the i n t e n s i t y o f emission  o  a t 6340 A had a l i n e a r r e l a t i o n s h i p a g a i n s t the square of  (^('.Ag)  under these r e a c t i o n c o n d i t i o n s .  t h i s l i n e a r r e l a t i o n s h i p the excess energy  To c o n f i r m i n the f l o w  and the i n t e n s i t y o f e m i s s i o n a t 634OA were measured by the i s o t h e r m a l c a l o r i m e t r i c d e t e c t o r and p h o t o m u l t i p l i e r respectively. F i g 22.  It  i  s h i p between  The r e l a t i o n s h i p ' between them i s shown i n seen i n F i g . 22 t h a t a good l i n e a r  s  V / I ^ ^ Q  relation-  (square r o o t i n t e n s i t y of 6340A)  and the .concentration o f e x c i t e d oxygen molecule have been kept d u r i n g the r e a c t i o n .  The l i n e does not pass  through  the o r i g i n , presumably because the i n t e n s i t y a t 6340A was measured a few cm (around 4 cm) ahead o f the d e t e c t o r . The negative o r d e r o f ( ^ ( A g ) ± to understand.  s  quite d i f f i c u l t  T h i s may be because o f the f a c t s which were  not taken i n t o account. prevent the decay o f 0  F o r example, some s p e c i e s may  (!^g).  the reason i s the inhomogeneity  I t might be c o n s i d e r e d that o f the temperature.  To  check t h i s p o i n t , the f l o w o f e x c i t e d oxygen molecules was c o o l e d down q u i c k l y from o u t s i d e o f the r e a c t i o n  tube  w i t h water j u s t a f t e r the d i s c h a r g e but no d i f f e r e n c e was observed.  Because o f the reason d i s c u s s e d above, i t i s  concluded t h a t the decay i s q u i t e complicated.  process o f (^('Ag) with  olefin  7  0 < 0  1  . '  2  •—<—•  3  1  4  1  5  1  6  •  7  •  8  •  <?  •i  i  10  II  i  \x  .. 13  ( ca. lor j meter ) F i g u r e 22:  R e l a t i o n s h i p between excess energy i n 'the stream and  .  83-  I t should be p o s s i b l e to i n v e s t i g a t e these r e a c t i o n s at v e r y h i g h and v e r y low c o n c e n t r a t i o n s o f r e a c t a n t and s i n g l e t d e l t a , or by d i l u t i o n w i t h an i n e r t gas. these c o n d i t i o n s s i m p l e r k i n e t i c observed  r e l a t i o n s h i p s may  Under be  so t h a t the reason f o r the complex behavior  i n the present work c o u l d be  understood.  observed  REFERENCES.  . Phys. Rev., }2>  1. R.S. M u l l i k e n , 2. G. Herzberg,  Nature,  880 (1923)  133, 759 (1934)  3. J . F. Noxon and A.V. Jones,  Nature, 196, 157 (1962)  4. J.F. Noxon and T.P. Markham, J . Geophys. Res., 68 • 6059 (1963) 5- J . W . ' E l l i s , and H.O. Kneesr, 6. J . Kaplan,  Nature,  7- L.M. Banscorab,  Z. 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