Remerie, Klaas

Welsh

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   University of GroningenSolvent structure and solvation effects in aqueous solutions of 1,3- and 1,4- dioxane. Amolecular dynamics, NMR-spectroscopic and Kinetic StudyRemerie, KlaasIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1984Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Remerie, K. (1984). Solvent structure and solvation effects in aqueous solutions of 1,3- and 1,4- dioxane. Amolecular dynamics, NMR-spectroscopic and Kinetic Study. s.n.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 13-02-2023SUWARYT h i s  t h e s i s  d e s c r i b e s  a  s t u d y  o f  ( 1 )  m i c r o s c o p i c  d e t a i l s  f o r  t h e  h y d r a -t . i o n  o f ' 1 , 4 - d i o x a n e  ( 1 , 4 - D )  a n d  1 , 3 - d i o x a n e  ( 1 , 3 - D )  i n  w a t e r ,  ( 2 )  p r e f e r e n -t r ' a l  s o l v a t i o n  o f  1 , 3 - d i s u l f o n e s  i n  1 , 4 - D - w a t e r ,  1 , 3 - D - w a t e r ,  a n d  1 , z - d i -me thoxye thane  (DME) -wa te r  m ix tu res ,  and  (3 )  so l ven t  e f f ec t s  on  the  wa te r -c a t a l y z e d  h y d r o l y s i s  o f  a r y l s u l f o n y l m e t h y l  p e r c h l o r a t e s  i n  1 , 4 - D - w a t e r ,  1 , 3 -D-wa te r ,  and  DME-wa te r  m ix tu res .T h e  c o n c e p t  o f  p r e f e r e n t i a l  s o l v a t i o n  i s  o u t l  i n e d  i n  c h a p t e r  I .  I n  t h es a m e  c h a p t e r  t h e  p r o p e r t i e s  o f  c o o 1 ,  l i q u i d  w a t e r  a n d  a q u e o u s  o l u t i o n s  a r eb r i e f l y  r e v i e w e d .  F u r t h e r m o r e ,  a d e t a i l e d  r e v i e w  o f  a v a i l a b l e  l  i t e r a t u r ed a t a  o n  t h e  p r o p e r t i e s  o f  1 , 4 - D - w a t e r ,  i , 3 - D - w a t e r , a n d  D M E - w a t e r  i s g i v e n .In fo rma t i on  conce rn ing  the  1 ,3 -D-wa te r  and  DME-wa te r  sys tems  i s  sca rce  whenc o m p a r e d  w i t h  t h e  t h o r o u g h l y  s t u d i e d ' 1 , 4 - D - w a t e r  s y s t e m .  I n  s p i t e  o f  t h ee x t e n s i v e  d a t a  c o n c e r n i n g  1 , 4 - D - w a t e r ,  u n t i l  n o w  a l m o s t  i n s u r m o u n t a b l e  d i f -f i c u l t i e s  h a v e  b e e n  i n v o l v e d  i n  l i n k i n g  t h e r m o d y n a m i c  a n d  s p e c t r o s c o p i cd a t a  w i t h  a  m i c r o s c o p i c  p i c t u r e  o f  i n t e r m o l e c u l a r  i n t e r a c t i o n s  a t  t h e  m o l e c u -l a r  l e v e l  .W e  a p p l i e d  t h e  M o l e c u l a r  D y n a m i c s  ( 1 " 1 D )  c o m p u t e r  s i m u l a t i o n  m e t h o d  i no r d e r  t o  o b t a i n  a  d e t a i l e d  p i c t u r e  o f  i n t e r a c t i o n s  a t  t h e  m o l e c u l a r  l e v e li n  h i g h l y  a q u e o u s ' 1 , 4 - D - w a t e r  a n d  1 , 3 - D - w a t e r .  A s  a  s t a r t i n g  p o i n t  f o r  t h el 4 D  s i m u l a t i o n  o f  p r e f e r e n t i a l  s o l v a t i o n  p h e n o m e n a ,  b i s ( m e t h y l s u l f o n y l  ) -m e t h a n e  i n  w a t e r  h a s  a l s o  b e e n  s t u d i e d  b y  t h i s  m e t h o d .C h a p t e r  I I  p r o v i d e s  a n  i n t r o d u c t i o n  t o  t h e  a p p l i e d  M D  c o m p u t e r  s i m u l a t i o nme thod .  The  p repa ra t i ons  f o r  an  MD run ,  t he  pe r fo rmance  o f  t he  run ,  and  them e t h o d  o f  a n a l y s i s  o f  t h e  n u m e r i c a l  r e s u l t s  a r e  d e s c r i b e d  i n  d e t a i l .  P a r t i c -u l a r  a t t e n t i o n  i s  g i v e n  t o  b o t h  t i m e - a v e r a g e d  ( 1 . e .  ( p a i r )  i n t e r a c t i o n  e n -e r g i e s ,  r a d i a l  p a i r  c o r r e l a t i o n  f u n c t i o n s ,  o r i e n t a t i o n a l  d i s t r i b u t i o n s  o fh y d r a t i o n  s h e l l  a n d  b u l k  w a t e r ,  a n d  h y d r o g e n  b o n d i n g )  a n d  d y n a m i c  ( 2 . e .  s e l fd  i f f u s i o n ,  r a d i a l  d i f f u s i o n ,  a n d  m o l e c u l a r  e o r i e n t a t i o n )  p r o p e r t i e s .O u r  a n a l y s i s  o f  t h e  M D  r e s u l t s  i s  d e s c r i b e d  i n  c h a p t e r  I I I .  T h e  a q u e o u sd i o x a n e s  ( 1  m o l e  o f  d i o x a n e  i n  1 2 ?  m o l e s  o f  w a t e r )  h a v e  b e e n  s i m u l a t e d  b o t ha t  cons tan t  t empera tu re  and  vo lume  (T ,V )  and  a t  cons tan t  t empera tu re  andp r e s s u r e  ( T , P ) .The  (T ,V )  s imu la t i ons  gene ra l l y  show a  good  co r respondence  be tween  com-pu ted  and  expe r imen ta l  mac roscop i c  p rope r t i es .  The  wa te r  mo lecu les  a roundt h e  d i o x a n e s  a r e  o r d e r e d  i n  a  o a r t i a l l y  d i s t u r b e d  c l a t h r a t e - l  i k e  f a s h i o n .Th is  d i s tu rbance  i s  caused  by  d ipo la r  i n te rac t i ons  be tween  wa te r  and  thes o l u t e  o x _ v g e n  a t o m s .  I t  i s  c o n c l u d e d  t h a t  1 , 3 - D  e x e r t s  a  c o n s i d e r a b l e  s t r u c -tu re -b reak ing  i n f l uence  on  the  th ree -d imens iona l  hyd rogen -bonded  ne twork  o fw a t e r ,  w h e r e a s  i n  t h e  c a s e  o f  1 , 4 - D  t h e r e  i s  a  d e l i c a t e  b a l a n c e  b e t w e e ns t ruc tu re -b reak ing  and  s t ruc tu re -mak ing  e f f ec t s .  The  resu l t s  show tha t  t hem o b i l i t y  o f  w a t e r  m o l e c u l e s  i n  t h e  h y d r a t i o n  s h e l l  o f  1 , 3 - D  i s  s i g n i f i c a n t -1 y  e n h a n c e d  r e l a t i v e  t o  t h a t  o f  w a t e r  m o l e c u l e s  ' i n  t h e  1 , 4 - D  h y d r a t i o n  s h e l l .I t  i s  a l s o  e m p h a s i z e d  t h a t  t h e  a v e r a g e  s t r u c t u r e  f o u n d  o n  t h e  b a s i s  o f  as i m u l a t i o n  o f  a  f e w  p s  o r  e v e n  l e s s ,  i s  n o t  n e c e s s a r i l y  c o m p a r a b l e  t o  t h e( r e a l )  t i m e - a v e r a g e d  s t r u c t u r e  o f  t h e  s y s t e m  s t u d i e d .A l t hough  s imu la t i ons  a t  cons tan t  t e rnpe ra tu re  and  p ressu re  a re  more  rea l -i s t i c ,  t h e s e  c o n d i t i o n s  l e a d  t o  a n  a d d i t i o n a l  p r o b l e m .  D u e  t o  t h e  s m a l l  s i z eo f  t h e  t r u n c a t e d  o c t a h e d r o n ,  t h e  a p p l i e d  p e r i o d i c i t y  i n d u c e s  p o o r  w a t e r -w a t e r  c o n t a c t s ,  r e s u i t i n g  i n  a n  e x p a n s i o n  o f  a b o u t  9 . 5 1 / "  o f  t h e  a q u e o u sd i o x a n e  s y s t e m s .  A l t h o u g h  p a r t i c u l a r l y  t h e  a b s o l u t e  v a l u e s  o f  d y n a m i c  p r o p e r -t i e s  a r e  i n f l u e n c e d  s i g n i f i c a n t l y  b y  t h e  l o w e r  d e n s i t y ,  t h e  m a j o r  c o n c l u s i o n sd r a w n  o n  t h e  b a s i s  o f  t h e  ( T , V )  s i m u l a t i o n s  a r e  n o t  a f f e c t e d .The  tempera tu re  dependence  o f  t he  p rope r t i es  o f ' t he  1 ,4 -D-wa te r  sys temo v e r  a  s m a l l  t e m p e r a t u r e  r a n g e  o f ' 1 0 o  i s  a s  e x p e c t e d .  H o w e v e r ,  t h e  1 , 3 - D -wa te r  sys tem behaves  ve ry  d i f f e ren t l y ,  wh i ch  i s  i n te rp re ted  i n  t e rms  o f  ac h a n g e  f r o m  a  s i t u a t i o n  w h e r e  s o l v e n t - s o l v e n t . i n t e r a c t i o n s  d o m i n a t e  s o l u t e -s o l v e n t  i n t e r a c t i o n s  a t  t h e  l o w e r  t e m p e r a t u r e  t o  t h e  o p p o s i t e  s i t u a t i o n  a tt he  h ighe r  t empera tu re .A  c o m p a r i s o n  o f  1 , 4 - D - w a t e r  a n d  1 , 3 - D - w a t e r  a t  ( T , P )  w i t h  a  s i m u l a t i o no f  an  emp ty  cav i t y  o f  co r respond ing  cav i t y  s i ze  a l so  shows  some in te res t i ngfea tu res .  I f  i t  i s  assumed ,  t ha t  t he  cav i t y  i s  t he  co r rec t  s tanda rd  f o r  t hed e f i n i t i o n  o f  s t r u c t u r e - m a k i n g  a n d  s t r u c t u r e - b r e a k i n g  p r o p e r t i e s ,  i n d e e d  i n1 ,4 -D-wa te r  s t ruc tu re -mak ing  and  s t ruc tu re -b reak ing  p rope r t i es  a re  abou te q u a l l y  b a l a n c e d ,  w h e r e a s  1 , 3 - D  i s  d e f i n i t e l y  s t r u c t u r e - b r e a k i n g .  M o r e o v e r ,ex i s t i ng  con t rove rsy  conce rn ing  s lower  d i f f us ion  and  reo r i en ta t i on  ra tes  o fW a t e r  m o l e c u l e s  i n  t h e  h y d r a t i o n  s h e l l  o f  s t r u c t u r e - b r e a k i n g  s o l u t e s ,  a sc o m p a r e d  t o  b u l k  w a t e r ,  i s  r e l i e v e d  c o m p l e t e l y  w h e n  t h e  c a v i t y  i s  a d o p t e da s  a  s t a n d a r d .The  s t ruc tu re -b reak ing  cha rac te r  o f  su l f ony l  compounds  has  been  con f i rm-e d  i n  t h e  M D  s i m u l a t i o n  o f  b i s ( m e t h y l s u l f o n y l ) m e t h a n e  i  w a t e r .  T h e  w a t e rm o l e c u l e s  i n  t h e  f i r s t  s o l v a t i o n  s h e l l  a r e  f o u n d  t o  a d o p t  c l a t h r a t e - l i k eo r . i e n t a t i o n s  a r o u n d  t h e  m e t h y l  g r o u p s ,  w h i l e  w a t e r  m o l e c u l e s  a r o u n d  t h e  s u l -f ony l  and  me thy lene  g roups  i n te rac t  s t rong l y  w i t h  t he  so lu te  v i a  hyd rogenb o n d i n g .  D e s p i t e  t h e  r e l a t i v e l y  1 o w  c h a r g e  o n  t h e  m e t h y l e n e  h y d r o g e n  a t o m s ,hyd rogen  bond ing  to  t he  me thy lene  mo ie t y  i s  much  s t ronge r  t han  su l f ony loxygen -wa te r  hyd rogen  bond ing .  Neve r the less ,  wa te r  mo lecu les  wh i ch  a re  hy -d rogen  bonded  to  t he  me thy lene  hyd rogens  how enhanced  ro ta t i ona l  mob i l i t y .T h e  r e s u l t s  o f  a n  l H - N M R  c h e m i c a l  s h i f t  s t u d 5 ,  o f  t h e  B - d i s u l f o n e s  1 - 4a n d  t h e  B - k e t o s u l f o n e  5  i n  1 , 4 - D - w a t e r ,  1 , 3 - D - w a t e r , a n d  D M E - w a t e r  a e  p r e -s p n t e d  i n  c h a n t e r  T V .  A s  p x n e r ^ t e d  n n  h a s i s  o f  t h e  r e s u l t s  o f  t h e  M D  s i m u -1 ,AR1so2cH2so2R2R r = R r = M eR,  =  I \ {e ;  R ,  - -  E tR r = R r = E tR t  =  E t ;  R ,  =  v i n Y lR1s02cH2coR25 ,  R .  =  R ^  =  I t l eI Zl a t i on  o f  1  i n  wa te r ,  t he  me thy lene  N l l lR  chemica l  sh i f t  r esponds  c lose l y  t ot h e  c o m p o s i t i o n  o f  t h e  f r ' r s t  m e t h y l e n e  s o l v a t i o n  s h e l l .  T h e  e x n e r i m e n t a lme thy lene  chemica l  sh i f t  cu rves  a re  ana l yzed  quan t i t a t i ve l y  i n  t e rms  o f  t heth ree  Cov ing ton  equa t i ons  and  a  f ou r th  equa t i on ,  wh i ch  comb ines  two  o f  t heC o v i n g t o n  t r e a t r n e n t s ,  u s i n g  a  n o n l  i n e a r  l e a s t - s q u a r e s  f i t  r o u t i n e .  T h e  b e s tr e s u l t s  a r e  o b t a i n e d  b y  u s i n g  C o v i n g t o n ' s  n o n s t a t i s t i c a l  d i s t r i b u t i o n  a p -p r o a c h ,  a n d  i n d i c a t e  p r e f e r e n t i a l  s o l v a t i o n  o f  t h e  o r g a n i c  s o l u t e  b y  t h ec o s o l  v e n t .F rom a  comb ina t i on  o f  t he  ca l cu la ted  and  the  expe r imen ta l  f r ee  ene rgyo f  t r a n s f e r  o f  t h e  B - d i s u l f o n e s  1  a n d  3  f r o m  n H Z 0  =  1 . 0  t o  n H 2 0  =  0 . 9  a n d0 . 8 ,  t h e  n u m b e r  o f  w a t e r  m o l e c u l e s  i n  t h e  s o l v a t i o n  s h e l l  t h a t  i n f l u e n c et h e  m e t h y l e n e  c h e m i c a l  s h i f t  s i g n i f i c a n t l y  i s  e s t i m a t e d  t o  b e  a b o u t  4 .C h a p t e r  V  p r e s e n t s a n  a n a l y s i s  o f  t h e  s o l v e n t  c o m p o s i t i o n  d e p e n d e n c e  o ft he  pseudo - f i r s t -o rde r  ra te  cons tan ts  and  i soba r i c  ac t i va t . i on  pa rame te rsfo r  t he  wa te r - ca ta l yzed  hyd ro l ys i s  o f  t he  cova len t  a ry l su l f ony lme thy l  pe r -c h l o r a t e s  6  a n d  7  i n  1 , 4 - D - w a t e r , 1 , 3 - D - w a t e r , a n d  D M E - w a t e r .  T h e  i n c r e a s eo f  t h e  p s e u d o - f i r s t - o r d e r  r a t e  c o n s t a n t  u p o n  a d d i t i o n  o f  c o s o l v e n t  u n t i ln H Z O  =  0 . 8  i s  a t t r i b u t e d  t o  a n  i n c r e a s e d  k i n e t i c  b a s i c i t y  o f  w a t e r  a s  aresu l t  o f  coso l ven t -wa te r  hyd rogen  bond ing .  The  behav iou r  o f  t he  ra te  con -s tan ts  be tween  r tH .0  =  0 .8  and  nH^n  r y  0 .3  i s  de te rm ined  by  t he  sh i f t  o f  t he" a -  " t -hyd rogen -bond ing  equ i l  i b r i um f rom I coso l  ven t .4  H t0J  t o  I coso l  ven t .  z1  H r0Jq ,qq ,7 ,ATSO2CH2OCI03Ar -  p-NOTCUH*Ar = p-CHaCUHnATSOTCHTOSOTCH,Ar = p-NOTCUH.Ar = p-CHTCUH'a s  t h e  m a j o r  h y d r o g e n - b o n d e d  c o m p l e x .  B e l o w  n H Z O  =  0 . 3  a  s i m p l e  d i l u t ' i o n  o fh y d r o g e n - b o n d e d  s p e c i e s  d e t e r m i n e s  t h e  b e h a v i o u r  o f  k o b r .  T h e  a p p a r e n t  s e c -ond -o rde r  ra te  cons tan t  f o r  hyd ro l ys i s  o f  6  and  7  i n  1 ,4 -D-wa te r  has  a  nea r -1 y  c o n s t a n t  v a l u e  b e l o w  n H 2 0  o  0 . 8 .  T h i s  b e h a v i o u r  m a y  b e  a t t r i b u t e d  t op r e f e r e n t i a l  s o l v a t i o n  o f  t h e  s u b s t r a t e  b y  1 , 4 - D .  I n  o r d e r  t o  d i s s e c t  t h ec h a n g e s  i n  t h e  a c t i v a t i o n  p a r a m e t e r s  f o r  h y d r o l y s i s  o f  6  a n d  7  i n t o  i n i t i a ls ta te  and  t rans i t i on  s ta te  con t r i bu t i ons ,  t he rmodynam. i c  t r ans fe r  pa rame te rsfo r  t he  i n i t i a l  s ta te  o f  6  and  7  have  been  app rox ima ted  by  t he  use  o f  mode lcompounds  B  and  9 .  The  de r i ved  t rans fe r  pa rame te rs  i nd i ca te  t ha t  t he  de -^  . . +c r e a s e  o f  a H *  u p o n  i n i t i a l  a d d i t i o n  o f  c o s o l v e n t  ( u n t i l  n H 2 0  =  0 . 8 )  i sp r imar i l y  due  to  a  t r ans i t i on  s ta te  e f f ec t .  l , l he reas  the  con t r i bu t . i on  o f  t het rans fe r  pa rame te rs  o f  wa te r  t o  t he  t r ans fe r  pa rame te rs  f o r  t he  i n i t i a ls ta te  may  sa fe l y  be  neg lec ted ,  t he re  may  be  s ign i f i can t  med ium e f fec t s  onthe  reac t i on  wa te r - so l ven t  i n te rac t i ons  wh i ch  pa r t l y  de te rm ine  the  changesin  t he  t rans fe r  pa rame te rs  f o r  t he  t r ans i t i on  s ta te .  Good  and  coworke rss u g g e s t e d  t h a t  t h e  l a t t e r  e f f e c t s  a r e  p h . v s i c a l l y  r e l a t e d  t o  t h e  a c t i v a t i o np r o c e s s  f o r  f l u i d  m o t i o n  i n  t h e  s o l v e n t  m i x t u r e  u n d e r  i n v e s t i g a t i o n .  0 n enoss ib le  ann roach  t . o  accoun t  f o r  t h i s  con t r i bu t i on  has  been  advanced .  Fo r' _  * r r 'a  q u a n t i t a t i v e  a n a l y s i s ,  h o w e v e r ,  m o r e  e x t e n s i v e  k i n e t i c  d a t a  a r e  n e c e s s a r y .

Solvent structure and solvation effects in aqueous solutions of 1,3- and 1,4- dioxane. A molecular dynamics, NMR-spectroscopic and Kinetic Study

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Solvent structure and solvation effects in aqueous solutions of 1,3- and 1,4- dioxane. A molecular dynamics, NMR-spectroscopic and Kinetic Study

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