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The intercalation of bromine- and iodine fluorosulfate derivatives in solutions of fluorosulfuric acid Cader, Mohamed Shah Roshan 1986

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THE INTERCALATION OF BROMINE- AND IODINE FLUOROSULFATE DERIVATIVES I N SOLUTIONS OF FLUOROSULFURIC ACID  BY  SHAH ROSHAN CADER  M. B.Sc.  (Hons.). University  o f P e t r o l e u m and M i n e r a l s ,  Dhahran,  A THESIS SUBMITTED I N PARTIAL FULFILLMENT OF THE REQUIREMENT FOR THE DEGREE OF MASTER OF SCIENCE  IN  THE FACULTY OF GRADUATE STUDIES (Department o f  We a c c e p t  this  Chemistry)  thesis  to the r e q u i r e d  as  conforming  standard  THE UNIVERSITY OF B R I T I S H COLUMBIA  ©  M.S.R.  CADER,  September  1986  1983  In  presenting  requirements of  British  it  freely  agree for  this f o r an  in partial  advanced  degree  Columbia, I agree that available  that  f o r reference  permission  scholarly  o r by  understood  that  financial  be  copying  and  I  October  granted  shall  n o t be  by  1986  Columbia  make  further  of this  t h e head  of this  thesis  of  my  I t i s thesis  a l l o w e d w i t h o u t my  Chemistry  8,  study.  copying  or publication  The U n i v e r s i t y o f B r i t i s h 1956 Main M a l l Vancouver, Canada V6T 1Y3 Date  University  h i s or her representatives.  gain  of  at the  the  shall  permission.  Department  fulfilment of  the Library  f o r extensive  p u r p o s e s may  department  for  thesis  written  ABSTRACT  The  oxidative  s u c h as I ( S 0 F ) , 3  solutions  of  The data,  the  type  acid  shifts, spectra  courses o f  of  c-axis s  o  first  layer i ) ,  3  lesser  of  solvated  r e s e a r c h as w e l l .  X - r a y powder  -^F-NMR  diffraction  spectroscopy  solutions  and  support  (about a f i v e  or  solvent  concentrations  distance 3  3  I  Br,  Hal  fold  (S0 F) 3  3  intercalate  I  three  excess and  the  without  -  c  C 2l(S0 F) , 3  observed.  the only  intercalate  3  3  2  is  HS0 F.  BrS0 F  3  intercalation  are used,  except  s t a g e compounds a r e f o r m e d .  C SO F.3HSO F.0-2I, 3 2  concentrations,  I(S0 F) ,  v  (SP-1 and t o a  4  reactions:  -  intercalation reactions  repeat  from  3  cointercalation.  low i n t e r c a l a n t  the  K[Br(S0 F) ]  required quantity)  Hal  f o u n d t o be t h e s o l v e n t  synthesis,  (  solvent  intermediate  In all  +  with  derivatives  intercalation  concentrations  [Hal(S0 F>4]",  is  the  the supernatant  anion  When  graphite  state  the i n t e r c a l a t i o n  3  and  4  included in this  Solid  the s t o i c h i o m e t r i c a l l y  c)  2  is  +  over  At  into  In addition,  At very high i n t e r c a l a n t  b)  3  supported by m i c r o a n a l y s i s ,  optical  noticeable  K[I(S0 F) ]  3  and N 0  +  Raman f r e q u e n c y  different  I  l2  of halogen f l u o r o s u l f a t e  BrS0 F,  3  studied.  results,  UV-visible  a)  3  fluorosulfuric  e x t e n t HOPG) i s cations  Br(S0 F) ,  3  in  intercalation  3  the  +  Br(S0 F) 3  3  the with  C HS0 F.0•5S0 F.xBrS0 F 1 1  3  s o  ^ ^  promoted  v  These s t a g e one G I C ' s  8.0 A are found f o r and  N0 ^  3  3  with  intercalants compositions (x  <  0.025)  iii  and  C 6.8  gave C  8 6  3  first  stage  products  K[Hal(S0 F) ] 3  with  4  formulae  <Hal = B r ,  I)  in  HSO3F  Cg4Br.11•22S0 F  and  3  I.10-51SO F. 3  The I  Br.4S0 F respectively.  2  c  NO (  ~ 1 0 . 6 A,  the  v  induced r e a c t i o n leads  t o a s t a g e t w o compound n  which  is  electrical  graphite-l2 ( +  radio  s o  and a g e n e r a l c o m p o s i t i o n o f C x S 0 F - y H S 0 F  product  basal plane  i )  +  s o  frequency  i ) v  compositionally conductivity  inhomogeneous.  enhancements a r e  and g r a p h i t e - I ( S 0 F )  i n d u c t i o n method.  3  3  3  3  with  i s proposed  for  In addition,  the  measured  systems e m p l o y i n g a  for  the  contactless  - iv  -  TABLE OF CONTENTS  Page ABSTRACT  ii  TABLE OF CONTENTS  iv  L I S T OF TABLES  ix  L I S T OF FIGURES  x  GLOSSARY  xii  ACKNOWLEDGEMENT  xiv  I.  INTRODUCTION  1  1.1  G e n e r a l Comments  2  1.2  H i s t o r i c a l Review  3  1.3  Graphite  4  1.4  Graphite  1.5  D o n o r I n t e r c a l a t i o n Compounds  11  1.6  Acceptor  16  1.7  Methods o f  Intercalation  7  I n t e r c a l a t i o n Compounds Intercalation  18  1.7.1  Direct  1.7.2  O x i d a t i o n by an E x t e r n a l  1.7.3  Anodic O x i d a t i o n o f Graphite c h e m i c a l Method)  1.7.4  Intercalation  Intercalate  18 Chemical Species  .  .  19  (Electro-  Exchange a n d S u b s t i t u t i o n  20 . . .  23  -  1.7.5 1.8  O x i d a t i o n or Reduction Intercalation  23 Compounds  .  .  24  1.8.1  G r a p h i t e - H a l o g e n a n d I n t e r h a l o g e n Compounds  .  .  24  1.8.2  Graphite-Fluorosulfate  1.8.4  Compounds  26  1.8.2a  Graphite  1.8.2b  Graphite-Acid Fluorosulfates  1.8.2c  Graphite-Bromine  Fluorosulfates  . . . . . .  Fluorosulfates  G r a p h i t e I n t e r c a l a t i o n Compounds Non-protonic Solvents  in  Graphite  I n t e r c a l a t i o n Compounds  in  Protonic  Solvents  1.8.4a  Graphite-Nitric  1.8.4b  Graphite-Solutions Agents i n P r o t o n i c  1.9  Intercalation  1.10  Enhanced E l e c t r i c a l Compounds  1.11  -  Review o f S e l e c t e d A c c e p t o r  1.8.3  II.  Intercalate  V  in Fluorosulfuric  Purpose o f T h i s  Conductance  27  . . . . .  27 .  29  31  32 A c i d Compounds  . . .  33  of Oxidizing Solvents . . . .  34  Acid in  37  Intercalated 41  Study  43  EXPERIMENTAL SECTION  45  G e n e r a l Comments  46  2.1  Apparatus  46  2.1.1  G l a s s Vacuum L i n e  46  2.1.2  Metal Fluorine  47  2.1.3  D r y A t m o s p h e r e Box  47  3.1.4  Reaction Vessels  48  3.1.5  Miscellaneous  50  Line  Glass Apparatus  - vi  2.2  Analytical  -  Equipment  56  2.2.1  Visible  and U l t r a v i o l e t  Spectrophotometer  2.2.2  I n f r a r e d Spectrophotometer  2.2.3  Nuclear Magnetic  .  .  56 56  Resonance  Spectrometer  57  2.2.4  Raman S p e c t r o p h o t o m e t e r  57  2.2.5  X - r a y Powder D i f f r a c t i o n  59  2.3  Elemental Analyses  2.4  Electrical  59  Conductivity  of  I n t e r c a l a t e d HOPG  Samples  60  2.5  Other Techniques  2.6  P r e p a r a t i o n and P u r i f i c a t i o n o f Reagents  61  2.6.1  S 0 F  61  2.6.2 2.6.3  HS0 F l2 (solv)  63  2.6.4  I(S0 F)  65  2.6.5  IS0 F  2.6.6  IBr S0 F  2.6.7  K[I(S0 F) ]  2.6.8  Br(S0 F)  2.6.9  BrS0 F  68  2.6.10  N0S0 F  69  2.7  2  6  . . . . .  2  3  +  3  61  6  3  3  65  3  2  66  3  3  3  4  and K [ B r ( S 0 F ) ] 3  66  4  68  3  3  3  Commercially A v a i l a b l e  Chemicals  2.7.1  Graphite  2.7.2  Other Chemicals Obtained Commercial Sources  .  69 69  from 70  - vii  III.  IV.  -  SYNTHETIC REACTIONS  72  G e n e r a l Comments  73  3.1  Intercalation of  l2 (solv)  3.2  I n t e r c a l a t i o n of  I(S0 F)  *-  +  3  Graphite  n t o  74  into Graphite  3  75  3.2.1  High c o n c e n t r a t i o n o f  I(S0 F)  3  75  3.2.2  Low c o n c e n t r a t i o n s  I(S0 F)  3  76  of  3  3  3.3  Intercalation  of K[I(S0 F>4]  into Graphite  3.4  Intercalation  of Br(S0 F)  3.5  I n t e r c a l a t i o n of K[Br(S0 F) ]  3.6  I n t e r c a l a t i o n of BrS0 F i n t o Graphite  80  3.7  I n t e r c a l a t i o n o f N0S0 F i n t o G r a p h i t e  81  3.8  Intercalation of  83  3.9  Reactions  3  3  78  into Graphite  3  3  4  79  into Graphite  . . . .  79  3  3  IBr S0 F 2  3  into Graphite  o f Halogen F l u o r o s u l f a t e s  83  3.9.1  Attempted Oxidation of K[I(S0 F>4]  3.9.2  Reaction of K[I(S0 F)4]  3.9.3  Reaction of  83  3  w i t h Excess B r  3  I(S0 F) 3  3  w i t h Excess B r  2  2  . . .  84  . . . .  85  RESULTS AND DISCUSSION  86  G e n e r a l Comments  87  4.1  Intercalant Preparation in A c i d and R e l a t e d S t u d i e s 4.1.1  I  4.1.2  IS0 F  4.1.3  I(S0 F)  4.1.4  K[I(S0 F) ]  + 2  (  s  o  i  v  Fluorosulfuric 88 .  )  89 91  3  3  3  93  3  4  and K [ B r ( S 0 F ) ] 3  4  95  - viii  4.2  4.3  -  4.1.5  Br(S0 F)  4.1.6  BrS0 F  97  4.1.7  NOS0 F  99  4.1.8  IBr S0 F  4.1.9  Attempted Oxidation of K [ I ( S 0 F ) ]  4.1.10  Reaction of K [ I ( S 0 F ) ]  4.1.11  Reaction of  3  96  3  3  3  2  100  3  3  3  I n t e r c a l a t i o n of  I(S0 F) 3  Iodine  w i t h Excess B r  4  w i t h Excess B r  3  2  C o n t a i n i n g Species  4.2.1  Intercalation of  4.2.2  Intercalation of I(S0 F)  4.2.3  Intercalation of K [ I ( S 0 F ) ]  4.2.4  Attempted I n t e r c a l a t i o n of  2  . . . .  .  102 .  . . . .  104  +  3  103 104  l2 (solv)  109  3  3  115  4  IS0 F  117  3  I n t e r c a l a t i o n o f B r o m i n e C o n t a i n i n g Compounds  .  .  .  119  4.3.1  I n t e r c a l a t i o n of BrS0 F  119  4.3.2  Intercalation of Br(S0 F)  4.3.3  Intercalation of K[Br(S0 F) ]  124  4.3.4  Intercalation of  125  3  3  3  (N0 )  2  Nitrosonium Ion  4.5  G e n e r a l Comments a n d C o n c l u s i o n  +  122  3  4  IBr S0 F  4.4  REFERENCES  101  4  3  Promoted I n t e r c a l a t i o n  . . . .  127 131  134  - ix  -  L I S T OF TABLES  Table  Page  1.1  Anisotropy  Factor  f o r V a r i o u s Types o f G r a p h i t e  1.2  P h y s i c a l and Thermochemical Fluorosulfuric Acid  Properties  . . .  8  of 38  2.1  Chemicals O b t a i n e d f r o m Commercial Sources  71  3.1  Microanalysis of I ( S 0 F )  77  3  D a t a o f Low C o n c e n t r a t i o n  3.2  Typical Microanalysis  4.1  Selected Physical Properties Fluorosulfates  4.2  Reactions  3  Data f o r N0S0 F R e a c t i o n s  .  3  of  .  Some H a l o g e n  T y p i c a l C o n d u c t i v i t y Measurements G r a p h i t e - l 2 ( s o l v ) Compound  94  for 108  +  4.3  Electrical  82  C o n d u c t i v i t y Values of C 2 l ( S 0 F ) 2  3  3  .  .  .  114  L I S T OF FIGURES  Figure  Page  1.1  The U n i t  1.2  Staging i n Graphite  1.3  The D a u m a s - H e r o l d M o d e l f o r  1.4  Apparatus of  1.5  C e l l Dimensions o f Hexagonal G r a p h i t e  for  . . .  Intercalation  13  Staging  the Electrochemical  15  Synthesis  I n t e r c a l a t i o n Compounds  Density  of States  i n Pure,  5  21 Reduced and  Oxidized  G r a p h i t e A c c o r d i n g t o t h e Band M o d e l  42  2.1  Two P a r t R e a c t i o n V e s s e l s  49  2.2  One P a r t R e a c t i o n V e s s e l s  51  2.3  One P a r t R e a c t i o n V i a l s  52  2.4  S 0 F  A d d i t i o n Trap  53  2.5  Vacuum F i l t r a t i o n A p p a r a t u s  55  2.6  B a c k - S c a t t e r i n g A r r a n g e m e n t Used  2  6  2  for  Raman S p e c t r a  2.7  Apparatus  for  2.8  Fluorosulfuric  58  the Preparation of  S 0gF 2  62  2  Acid D i s t i l l a t i o n Apparatus  . . . .  64  - xi  4.1  4.2  4.3  -  A b s o r p t i o n S p e c t r a o f 1 : 1 and 2 : 1 Solutions  A b s o r p t i o n Spectrum o f I S O 3 F Fluorosulfuric Acid  UV a n d V i s i b l e  I2/S2O6F2 90  Dissolved  in 92  Spectra i n H S O 3 F of  Br :S 0 F 2  2  6  2  i n Varying Ratios  4.4  1 9  4.5  1 9  4.6  1 9  4.7  1 9  4.8  1 9  98  F-NMR Spectrum o f C S 0 F . 3 H S 0 F . 0 • 2 1 3 2  F-NMR Spectrum o f C  2 2  3  107  3  I(S0 F)3  Ill  3  F-NMR Spectrum o f C g I . 1 0 • 5 1 S 0 F 6  118  3  F-NMR Spectrum o f C H S 0 F . - 5 S 0 F . x B r S 0 F 1 1  3  3  121  3  F - N M R S p e c t r u m o f G r a p h i t e + N O S O 3 F Compound  .  .  .  129  GLOSSARY  Acceptor Intercalation Compounds Compounds a c c e p t o r i n t e r c a l a n t s s u c h as B r and A S F 5 .  formed from  electron  2  Bounding Layers  - the carbon layers  Charge T r a n s f e r F a c t o r ( f ) g r a p h i t e l a t t i c e due t o  adjacent  the extent of oxidation.  t o an i n t e r c a l a t e  electron  layer.  removal  from  the  Deintercalation the process that occurs at elevated temperatures w h i c h p r o d u c e s t h e i n i t i a l i n t e r c a l a n t ( s ) as w e l l as o t h e r v o l a t i l e decomposition products.  Donor  Intercalation Compounds compounds d o n o r i n t e r c a l a n t s l i k e K a n d Cs.  E x f o l i a t i o n - the collapse of the tion-deintercalation cycle.  layer  Hexagonal Graphite infinite atoms, and s t a c k e d t o g e t h e r c-axis direction.  sheets in an  Intercalant(s) the vacant  synthesized from  structure  due t o  an  electron  intercala-  of hexagons, formed by carbon ABAB.... sequence along the  m o l e c u l e s , i o n s o r atoms c a p a b l e o f s i t e s o f the host l a t t i c e m a t e r i a l .  I n t e r c a l a t e ( s ) - the species a c t u a l l y present the process of i n t e r c a l a t i o n .  inside  insertion  the  between  lattice  after  I n t e r c a l a t i o n - t h e i n s e r t i o n o f i o n s , atoms o r m o l e c u l e s g e n e r a l l y a l a y e r s t r u c t u r e , and s p e c i f i c a l l y between c a r b o n layers of graphite l a t t i c e .  Interior Layers intercalate  the layer.  carbon  layers  not  in direct  contact with  into the  the  - xiii  -  L i m i t i n g Composition d u r i n g the i n t e r c a l a t i o n r e a c t i o n , intercalation w i l l not proceed a f t e r reaching a l i m i t i n g composition. T h i s composition may d i f f e r from stage one composition, e.g. the GIC C PFg(CH3N02)y r e f e r s t o a s t a g e two l i m i t i n g c o m p o s i t i o n p r o d u c t . n  R e s i d u a l Compound - t h e s o l i d m a t e r i a l  Stage  left  I n d e x - t h e number o f c a r b o n l a y e r s calate layers.  after  deintercalation.  separating  two n e a r e s t  inter-  S t a g i n g - t h e r e g u l a r a l t e r n a t i o n o f i n t e r c a l a t e l a y e r s and empty l a r spaces a l o n g t h e v e r t i c a l o r c - a x i s d i r e c t i o n .  lamel-  - xiv  -  ACKNOWLEDGEMENT  I  wish  to  F e l i x Aubke,  for  express  the guidance,  as my r e s e a r c h s u p e r v i s o r a r e a l s o due t o D r . has  been  an  my  sincere  d u r i n g the e n t i r e  throughout  Jocelyn W i l l i s ,  f o r her assistance  state  spectra.  ^ F-NMR 9  the graphite I the  and f o r  would also  this  use o f X - r a y f a c i l i t i e s .  excellent  c o w o r k e r s W.V. and h e l p .  work  done  C i c h a and J .  Professor  Special  I  discussions  Thanks  and  help  am i n d e b t e d t o  thanked f o r  the  Dr.  solid  supplying  regarding this  Trotter,  showed  study.  in obtaining  Professor J.G. Hooley i s  to thank Professor J .  this  cooperation  research.  and p a t i e n c e  and C o r i n n e Reimer f o r p r o o f - r e a d i n g the  course o f  whose u s e f u l  t h e many f r u i t f u l  like  to  u n d e r s t a n d i n g a n d e x t r e m e c a r e he  S. K a r u n a n i t h y ,  asset  t h a n k s and g r a t i t u d e  who k i n d l y  work. allowed  t h a n k s a r e e x t e n d e d t o S h a r o n Yap  this  thesis,  Rani  i n typing the manuscript, Christensen for  their  Theeparajah and f i n a l l y ,  pleasant  for t o my  friendship  - 1 -  CHAPTER 1  INTRODUCTION  - 2 -  1.1 General  Comments  Research on g r a p h i t e explosive  and r a p i d g r o w t h d u r i n g t h e l a s t  characterization fields  such  together,  to  The  material the  properties  use  or m a t r i x  popularity  from  1  very useful  The  intercalation  h a s made t h e m p r i m e  3  utilization  of  compounds  in  work struc-  group  electrical  as t h e  host  contributed  basic  of  candidates  graphite  c a t a l y s i s ^ has a l s o  solid  to  the chemical,  potentially  and  varying  chemistry,  i n t e r c a l a t i o n compounds as  i n heterogeneous  of  undergone  engineering  understanding of  conductors "  applications.  specialists  electrical  of this  has  The s y n t h e s i s  and s o l i d s t a t e  and  of graphite  (GIC's)  25 y e a r s .  many  physical  science  systems and p l a n a r  industrial  drawn  reach a b e t t e r  and e l e c t r o n i c  storage  have  inorganic,  material  and  compounds.  in  o f GIC's  as  state physics,  tural  i n t e r c a l a t i o n compounds  and  to  industrial  research. Detailed review a r t i c l e s by  Henning  and F i s c h e r Forsman  5  and R u d o r f f , 6  (1970),  1 0  et  al. ^  The f o l l o w i n g tion,  observation,  summarizes  "The s y n t h e s i s question under what  to  of  lamellar  the chemist:  conditions?"  species  1 1  7  (1965), (1980)  recent Ebert  and  8  advancements  (1975),  more  made b y a s p e c i a l i s t initial  compounds  challenge poses  which reagents  in to  the  graphite  following  9  by  period.  intercala-  the s y n t h e t i c  are capable of  Herold  recently  r e s p e c t i v e l y have appeared d u r i n g t h i s  the major,  More r e c e n t l y , ated  Herold et a l .  S e l i g and E b e r t  (1983)  1  s u m m a r i z i n g p a s t and  chemist:  fundamental insertion  and  1 3  new p r o b l e m s r e g a r d i n g t h e n a t u r e  once i n t e r c a l a t i o n has o c c u r r e d ,  of  the  intercal-  t h e mechanism b y w h i c h  it  - 3o c c u r s and t h e e x t e n t calate  and  sufficient  1.2  the  The f i r s t in  1840  tive  the  graphite  as  lamellar  have emerged,  of  or  i n t e r c a l a t i o n compound was made b y  Covalent graphite These compounds,  sodium  graphite^  to *  nitrate  compounds  providing  Schafheautl  produce  compounds  GIC a n d t h e f i r s t on  covalent  graphite  d u r i n g 1959-1960 w i t h  oxidizing  of  hence i n t e r e s t i n g  s  were  also  in  formula  to note that  role  systems  in sulfuric  or  such  as  reacting  Cg02(OH)2^ sulfuric of  as  oxide  acid  i n the discovery  graphite  oxida-  known  generally called graphite  o r permanganate  r e a c t i o n medium p l a y e d a n i m p o r t a n t  Research  inter-  researchers.  are s y n t h e s i z e d by s t r o n g l y  8°4^2^^'^"^-  their  lattice,  or  Review  1859^. acid,  solutions  first  between the guest  and 1859^0 b y r e a c t i n g g r a p h i t e w i t h oleum r e s u l t i n g  graphite  c  for  intercalation.  early  with  host,  stimulus  Historical  of electron transfer  or  a c i d as a both  the  compound.  i n t e r c a l a t i o n compounds f i r s t  the v a s t m a j o r i t y o f  the e f f o r t  reached a peak  directed  towards  and t h e use o f  physical  synthesis. In  methods present,  the  late  1970's,  i n the s t r u c t u r a l intense  mechanistic  elucidation of  research a c t i v i t y  dimensional physical properties, pathways  in their  studies GIC's  became  on the e l e c t r o n i c  novel synthetic  preparation continue  routes  prominent. structure and  In  1959,  a n d two  mechanistic  as t h e c a u s e o f p o t e n t i a l  c a t i o n o f G I C ' s becomes i n c r e a s i n g l y w i d e r .  At  Henning^  applilisted  - 4 -  about or  t h r e e d o z e n known compounds w h i c h s p o n t a n e o u s l y  lamellar  number  of  compounds.  products  Looking back, field,  challenging, this  multifaceted  Some i m p o r t a n t following  1.3  that  times  alone claim of a l l  larger  known  than i n  o f alchemy i n the M i d d l e Ages,  scientific  than  a  large  intercal-  1959.  r e s e a r c h o n G I C ' s h a s e v o l v e d f r o m an  endeavour.  m u s t go t o t h e d e v e l o p m e n t  results  intercalation  graphite,  Much o f  into  the c r e d i t  of chemically pure,  resulting  in a  greater  had been p o s s i b l e w i t h n a t u r a l  aspects of graphite  itself  a highly  will  for  highly repro-  graphites.  now b e d i s c u s s e d  in  the  section.  Graphite  The form,  structure  is  carbon  atoms,  less  sp^  electrons hence  system.  It  the  planar  to  i n atomic o r b i t a l s  this  t h e m o s t common p o l y m o r p h i c sheets o f hexagons,  to give a layer  C-C b o n d d i s t a n c e  C-C d i s t a n c e  orbitals  contribute is  Infinite  and bond angles o f  hybrid  reside  1.1.  The i n t r a l a y e r  than  w i t h i n the layers  hexagonal g r a p h i t e ,  are stacked together  lattice.  slightly  carbon  of  shown i n F i g .  graphite  and  appears  reminiscent  of  and t h e t o t a l  i s now s e v e r a l  and u n i f o r m s y n t h e t i c  ducibility  by  it  achievement  ordered,  the metal chlorides  i n t e r c a l a t i o n compounds,  a n t s and t h e i r  obscure  Today,  form  of  120°  form  is  structure 1.42  A,  1.54 A i n d i a m o n d . suggest  a-bonds.  perpendicular  the  to  the  which  is  Planarity  involvement  The r e m a i n i n g to  the  formed  infinite  of  valence sheets  t o d e l o c a l i z e d w-bonds t o produce a p o l y a r o m a t i c  w-electron density  in  the  valence  bond  which  is  Figure 1.1:  The Unit C e l l Dimensions of Hexagonal Graphite.  -  responsible plane. for  for  covalent  seen  bond  formation  1.1,  superimposable  nature  of  u s e as a s o l i d , easily  the  has  intercalation.  consistent w i t h the view t h a t  these  forces  not  i n hexagonal g r a p h i t e stacking  in graphite  lubricant,  been used e x t e n s i v e l y  A l l work described i n t h i s  in industrial  not  sequence.  responsible  where t h e  layers  The  for  can  graphite,  its slide  differs  This polymorphic  as a h o s t s p e c i e s thesis w i l l  and o r d e r .  into  graphite. the  in  involve  form  in is  graphite hexagonal  purity.  silicates  natural  It  and  many n a t u r a l  in  Usually carbonates  using  must meet t h e r e q u i r e m e n t s  of  graphite  iron,  calcium,  are  present  g r a p h i t e s have c r y s t a l  intercalation process^ results.  Nevertheless,  1  natural  g r a p h i t e may be  and s y n t h e t i c  in  graphite  graphite and  is  other  or  classipyrolytic  intercalation,  its  uncertain  minerals  as i m p u r i t i e s  defects,  and t h e  i n nuclear  used as  purposes,  natural  from graphite  reactors  Both have been used e x t e n s i v e l y disadvantage  variable  For p r a c t i c a l  two b r o a d g r o u p s :  differs  electrolysis,  high purity  of  are  only.  o r as c o m b u s t i o n m a t e r i a l .  lity  is  c a l l e d rhombohedral  moderators  both the  forces.  direction. graphite,  as e l e c t r o d e m a t e r i a l  but  much  basal long  Graphite used i n i n t e r c a l a t i o n r e a c t i o n s  fied  3 . 3 5 A,  i n the too  s t a c k i n g s e q u e n c e , w h i c h i s ABCABC.  and  graphite  is  a n d show a n ABAB  high temperature  in a horizontal  the layer  but  lattice  the carbon layers  interlayer  A second form o f  rare  spacing i n the  conductance  a r e h e l d t o g e t h e r b y r e l a t i v e l y weak V a n d e r W a a l s  from F i g .  directly weak  two d i m e n s i o n a l m e t a l l i c  The i n t e r l a y e r  carbon planes As  the  6 -  and,  in  such  graphite  which  has  as  addition,  which could i n t e r f e r e  i n t e r p r e t a t i o n and  and  with  reproducibibeen  sub-  - 7 -  jected  to  extensive  reactions.  Pyrolytic  p u r i f i c a t i o n processes graphite  is  a monolithic  h i g h degree o f p r e f e r r e d c r y s t a l l o g r a p h i c i s made b y p y r o l y s i s at  temperatures  which  of  available  nearly parallel  high  i n order  in plates,  exhibit  SP-1 synthetic  a  c  reactions,  50-100  is  Graphite  A  a highly  fairly  treatment  (above  2800  (HOPG) .  This  form  K)  HOPG,  2 2  ordered structure  and i t  It  has  was u s e d d u r i n g  with been this  conductivities.  natural  and  properties  synthetic  in  low f o r n a t u r a l  graphite  a- and c - a x e s . graphite  as  The  compared  graphite. (spectroscopic is  grade),  which  a highly purified natural  microns.  w i t h HC1 a n d HF t o remove  1.4  1.1,  physical is  (a /o )  graphite  temperature  Graphite  i n the basal plane.  Table  different  ratio  synthetic  exhibits  a  deposition-method.  temperatures  t o measure enhanced e l e c t r i c a l  quite  anisotropy  about  and  with  the c - a x i s .  and subsequent h e a t  in intercalation reactions,  As c a n b e s e e n f r o m  to  pressure  carbon layers  used e x t e n s i v e l y study  of small hydrocarbons  intercalation  graphite material  orientation of  so c a l l e d H i g h l y O r i e n t e d P y r o l y t i c  is  use i n  a b o v e 2100 K o r b y t h e c h e m i c a l v a p o r  Application produces  finds  It  was u s e d i n a l l  graphite  of grain  i s made f r o m M a d a g a s c a r g r a p h i t e basic  impurities.  A  t h e n a p p l i e d t o remove a n y m e t a l l i c  Cl  2  and  stream  components  our size  treated at  high  present.  Intercalation  number o f  terms unique t o g r a p h i t e  c h e m i s t r y a r e now  introduced.  - 8 -  Table 1.1  Anisotropy  factor  f o r various  types of  graphite  w  a  Material  T(K)  Natural graphite (Ceylon, Mexico)  300  8.3 x 1 0  Natural graphite (Ceylon)  300  10  Natural graphite (Ticonderoga)  300  1.5-2.3 x 10  Natural graphite (Ticonderoga)  300  2 x 10  Natural graphite (Ticonderoga)  300  3.3 x 1 0  Kish  300  1.3-1.5 x 10  P y r o l y t i c carbon (T = 2200°C)  300  125  5500  P y r o l y t i c carbon (T = 2500°C)  300  83  5000  Pyrolytic graphite •(HTT - 3000°C)  300  385  5200  HOPG (annealed  300  590  3800  graphite  cr-CohnT  1  m" ) 1  (  )  100  4  100  4  4  100-170  130  4  80  4  4  +  d  +  d  3500°)  from reference  +  T  d  = Deposition  89. temperature.  HTT = H e a t T r e a t m e n t  Temperature.  - 9 -  and d e f i n e d . molecules  Intercalation  generally  carbon layers in  the  of  host  intralayer  into  is  ions  or  intercalat ion  has  the  in  structure  'guest-host'  their  while i.e.  2  far  compounds, GIC's  the  of  the  the carbon  inside  the  such  intercalant  white  resulting  covalent  or grey i n color  non-planar contacts.  structure  and  as  Br  charge,  exists  may  molecular  of  the  and  2  of  as  F  intercalants  donor  reducing  agent,  is  2  used is  covalent  compounds a r e  compositions  of  i n t h e s e compounds w i t h F  agents, as  lost, C-F  the the bond  orbitals.  insulators,  -CF.  from  In  ASF5.  the g r a p h i t e and  guest-  synthesized  I s an e f f e c t i v e  destroyed  graphite  have  after  and i n t e r c a l a t e  f o r m a t i o n occurs w i t h b o n d i n g d e s c r i b e d by sp^ carbon h y b r i d The  termed  Depending on the  electronic  character is  extent  lattice  formed by r e l a t i v e l y m i l d o x i d i z i n g  layers  The  intercalation.  A c c e p t o r compounds a r e  polyaromatic  layers  identity.  Intercalant  are  the  lesser  o f G I C ' s may be b a s e d o n t h e n a t u r e  intercalants  or  between  such i n s e r t i o n are  When a s t r o n g o x i d i z i n g a g e n t s u c h  intercalant, planarity  a  called intercalate.  chemical  of  Donor G I C ' s a r e f o r m e d b y e l e c t r o n donor  acceptor  acceptor Br .  and s p e c i f i c a l l y  to  of  structure,  s u c h as p o t a s s i u m a n d c e s i u m .  intercalation  capable  interaction,  and even i n t h e i r  interaction:  electron  and  actually present  electronic  atoms  i n the i n t e r c a l a t i o n process.  separation,  is  ions,  The p l a n a r i t y  2  taken place  A classification host  structure  lattice^*•^ .  atoms  The s p e c i e s  differ  layer  insertion of  b o n d d i s t a n c e s may a l l be c h a n g e d due t o  intercalants.  of  to the  retained  interlayer  Molecules,  nature  a  the graphite  lattice  stacking order,  refers  A  often  sheet-like F  intralayer  - 10 -  The c h e m i c a l n a t u r e charge  transfer  during  of  the  intercalants  intercalation,  determines  resulting  the  direction  i n acceptor  or  donor  of GIC  formation. I n acceptor tion,  covalent  oxidation.  bond f o r m a t i o n  In contrast  partially usually  intercalation  reversible.  sensitive  compounds a r e  of  decomposition compound')  In  excess  case where  graphite aspect.  with  are  occurring as  molecular  at  well  elevated  as  left on  tempera-  other  volatile  (termed  'residue  the  e.g.  compounds  deintercalation  deintercalation fluorine  is  reversible,  an  layer  structure  surface  a dynamic  intercalants.  the  area.  inves-  interesting  (called  up  another  termed  capil-  can occur w h i c h a g a i n  vacuum  will  usually  cycle  exfoliation)  This brings  intercalant,  of  content.  p o o r l y u n d e r s t o o d and r a r e l y  o n t h e GIC s u r f a c e  adsorbed  low  an i n t e r c a l a t i o n - d e i n t e r c a l a t i o n  a larger  of  covalent  intercalation  compound w i t h a s m a l l  intercalation  the  whereas  volatile  from g r a p h i t e ,  Mere a d s o r p t i o n o f  Application  surface  of  in  formed by i n t e r c a l a t i o n solvents,  intercalant  results:  a collapse  case  is  while  CF4,  compounds a r e u s u a l l y  the  limiting  intercalation  produces  This process,  i n a residue  condensation,  ing case.  and  The  intercala-  conditions.  compounds  initial  application  interesting  thus  organic  a n d may b e d i f f e r e n t  lead to  yielding  formation,  dependent  residue  technical  bond  s e e n as t h e  has a c o m p o s i t i o n w h i c h i s  These  tigated.  is  material  may r e s u l t  lary  these  products.  C AsF5  will  under  and  s u c h as C O 2  the  i n CF)  compounds  water  formed by o x i d a t i v e  solid  temperature n  The  deintercalation. produces  (as  covalent  covalent  weight molecules  tures,  to  stable  Heating  undergo  to  compounds  is  a  remove  limitsuch  11 -  A of  final  comment i s  intercalation,  usually  C  + n  n  the  quantity bond  o x i d a t i o n and r e d u c t i o n .  -positively  C "-negatively termed  i.e.  g i v e n b e l o w r e g a r d i n g t h e two c o n t r a s t i n g  charged  charged l a y e r s ) .  charge t r a n s f e r  for  a g i v e n GIC.  (carrier  charged,  anisotropy ab-plane  in  of e l e c t r i c a l  results  anisotropy  in  reducing  level  of  (and  and r e p r e s e n t s  into and  in  the  valence  space w i t h  anions w i l l  and  opposi-  increase in  the the  direction.  a g e n t s a r e commonly atoms t h e empty conductance  o f c o n d u c t a n c e due t o  is  characteristic  w i t h enhanced conductance  i n the c-axis  n-type  removal  the Fermi l e v e l  interstitial  intercalate  a  generate  reduction,  electron  a lowering of  Filling  conductance,  and r e d u c e d conductance  Fermi  extent  (f),  generally molecular  donate e l e c t r o n s the  The  layers  The r e d u c e d e l e c t r o n d e n s i t y  density)  Conversely, will  graphite  factor  p - t y p e conductance enhancement. tely  Oxidation w i l l  types  bond  (e.g.  Li,  K)  which  causing  a  rise  c o n d u c t a n c e enhancement w i t h  the atomic nature  of  the  reduced  intercalate  anion. Interestingly,  donor  GIC's  have  found  extensive  use  as m o d e l  r e d u c i n g a g e n t s , w h e r e a s r e s e a r c h o n a c c e p t o r GICs h a s f o c u s s e d more the r e s u l t i n g e l e c t r o n i c  features.  1.5  Compounds  Donor I n t e r c a l a t i o n  While serves a)  to  two  not  directly  pertinent  to  this  study,  this brief  purposes:  illustrate  the unpredictable  nature  of  intercalation,  and  on  summary  - 12 -  b)  to  introduce  Lithium, with  and  a  important  potassium,  graphite  interlayer  the  to  satisfactory  donor  of  type  5 - 6 A.  galleries with  which i s  i n the graphite  stoichiometries  controlling  the  of  intercalation  t r a t i o n or by p a r t i a l  formula Cg Li25,26  This  is  while  due t o  The  time,  that  of  donor  in  regions  intercalant lattice  before  vacated. layers  will  This  or  f i l l  another will  index,  separating  galleries  layer  is  result  either in  a  favour  limiting  implying  compounds  staging is  the  concen-  a GIC  interlayer compounds. microatomic  nature. implies  that  where  the  situation completely  filled  shown i n F i g .  or g a l l e r y  attacked,  either  yields  are u s u a l l y  a  all  heating.  of acceptor  either  regular  a  stage  intercalation  or vacate a given layer  reaction  intercalant  aggregates by  are  c l a s s i c a l view of  and empty l a m e l l a r  The s t a g e layers  A  or  than that  graphite  interlaminar  with  The  be s y n t h e s i z e d b y  intercalants  compounds a t e q u i l i b r i u m  emptyl^.  Higher  temperature  are molecular  staging  react  intercalate,  with  s t a g e compound,  could  M  intercalation  totally  compound  r e a c t i o n under extreme c o n d i t i o n s  intercalants  concept  a  are f i l l e d .  t e n d t o be s m a l l e r  the f a c t  acceptor  t o be f o u n d .  I n i n t e r c a l a t e d donor compounds,  n  separation distances  still  deintercalation via controlled  The g r a p h i t e - l i t h i u m of  is  sodium does n o t  called a f i r s t  C^2n  vapors) 3  produces  lattice  their  i n t e r c a l a t i o n compounds^ .24  However,  explanation  between p o t a s s i u m and g r a p h i t e c o m p o s i t i o n o f CsK,  staging.  r u b i d i u m and cesium (and  give  separations  concept o f  1.2.  i n the  An  graphite  o p e n e d up a n d f i l l e d  alternation of  or  or  intercalant  spaces.  denoted by n,  two n e a r e s t  is  d e f i n e d as t h e number  intercalant  layers.  of  Hence a s t a g e  carbon index  - 13 -  OOO  — ooo ooo =  <ro  ooo  =  =  ooo ooo ooo First  Second  Carbon Layer Intercalate Layer  Figure 1.2:  Staging i n Graphite I n t e r c a l a t i o n .  TTiird  - 14 -  of  1 implies  the highest possible  carbon content of distance ate 's indeces  imply a lower  interlayer with  I  graphite  empty  layers  Due t o  with  as w e l l .  lattice  or a mixture  separation  in  some  intercalate  however,  layers which  observed.  The a b i l i t y  species, the  The h o s t  to  repeat  layer  the  result  accommodate  itself,  + (n-1)  c  takes  adjacent  the other  layers,  which  is  it  A,  stage  in  the  intercalate  not  In  direct  The  latter  similar  to  the  2  regular  by  the  stacking of  classical species  model,  layers  with  space  along  may  to distribute  i n the f o r m a t i o n o f mixed  not  be  between  the  stage  compounds.  t h i s macroscopic d i s t r i b u t i o n o f  Intercalate  pleated  layer)  i n i n t e r c a l a t e d compounds ** 2  layer  s t a c k i n g arrangement  t w o a n d t h r e e a r e shown i n F i g . that  3.35  place  t o an  the  sequences ^.  infinite  stacking pattern  is  interlayer  graphite  ordering  pattern,  intercalate  c a r b o n and i n t e r c a l a t e  concept  With  stage  b u t t h e b o u n d i n g l a y e r s may h a v e ABAB, AAA  implied of  intercal-  the corresponding f i r s t  Daumas a n d H e r o l d p r o p o s e d a d o m a i n ( o r  stage one, this  is  layers w i l l  order  in  the  i n s e r t e d i n every n t h intercarbon layer  the c - a x i s ,  graphite  as  separation  a r e t e r m e d Interior layers.  o f both these repeat  intercalate  A  lowest  with higher  ratio.  The c a r b o n l a y e r s  arrangement,  In practice,  of  3.35  intercalation,  the  compounds  carbon  a r e c a l l e d bounding l a y e r s , w h i l e  graphite  of  -  of  a s t a g e n compound becomes I  l a y e r s h a v e t h e ABAB l a y e r  for  to  the  interlayer  characteristic  Intercalation  interlayer  layers  contact  In  which is  c  intercalant  separation for  compound.  layer  in  the  c  I ,  requirement.  separations  concentration,  t h e compound a n d a s i n g l e u n i q u e  along the c-axis  space  intercalant  becomes e a s i e r  to  1.3.  (Fig.  model 1.3).  for  compounds  The b a s i c  advantage  explain  stage  transfor-  - 15 -  STAGE ONE  STAGE TWO  X  z.  CARBON LAYER INTERCALATE LAYER  Figure 1.3:  The Daumas-Herold Model f o r Staging.  -  mations  which,  according to  islands.  These i s l a n d s  all  interlayer  the  theoretical same  two  studies carbon  dimensional will  domains o f domains  •^,  layers  mixture of  domains,  exert  This w i l l with  an  eventually  stage  Mixed stage f o r m a t i o n them p u r e l y  ordering-^.  formed,  species  Intercalation  few  This  formation  of  takes is  place  when  observed along  a the  a this  section.  A  group w i l l  be summarized.  to determine  statistically  the  stage(s)  averaged  infor-  reveal  their  Presentday h i g h r e s o l u t i o n e l e c t r o n  micro-  and can  intercalated  r e l e v a n t members o f  the  lattice.  ( 0 . 1 mm)-* c r y s t a l s  comprise  lead to  layers  the  locate  These  of carbon  two  c o u l d be t e r m e d as s t a g i n g , w h i c h e x p l a i n s  s u p p o r t e d by computer s i m u l a t i o n s ,  Acceptor  form  of  scopy,  1.6  to  the  formation  o f an i n t e r c a l a t e d compound, u s u a l l y g i v e s  average  of  As shown b y  force  pairs  sizes.  The X - r a y d i f f r a c t i o n m e t h o d , u s e d w i d e l y  m a t i o n on t y p i c a l l y  occupation  species.  attractive  macroscopic  each o f  the graphite  intercalate  those between d i f f e r e n t  o f mixed stages. of  the  intercalate  i n t e r c a l a t e m o l e c u l e s o r atoms b e t w e e n  will  other.  intercalates  by  the  along the c-axis  existence  c-axis  each  i n v o l v e movement o f  are formed by the n o n - c o n t i n u o u s  islands while  repel  t h i s model,  regions 2 9  16  generally  c o u l d be  used  to  image  and  directly-* . 2  Compounds  rather group  large  group o f compounds,  a n d some more  will  be  a  introduced  g e n e r a l comments i n o r d e r Unlike  donor  to b e t t e r  intercalants,  in  subsequent  characterize which  are  this basi-  - 17 -  cally  restricted  to  metals,  acceptor  and v a r i e t y .  The f o l l o w i n g d i f f e r e n c e s  contribute  their  to  Acceptor  intercalants  anisotropy with leads  to  raised.  I  c  c)  capable  physical  and  intercalate  intercalant illustrate  In its this  are:  as  a) m o l e c u l a r  i n these  frequently of direct properties.  studies in  (e.g.  b)  in a  -  this  lowered rather  than  of  have  materials  i n t e r c a l a t i o n on a c c o u n t This  makes  graphite-Br2  structure.  greater  oxidizers  them  of  suitable  system).  a c c e p t o r G I C ' s may o r may n o t d i f f e r  molecular  GIC's,  interest.  - resulting  types  from  the  Two e x a m p l e s a r e g i v e n b e l o w  bis(fluorosulfuryl)peroxide  generates  w h i c h i n t u r n a c t as one e l e c t r o n o x i d i z e r  2.  donor  range  to  difference:  S2O5F2,  i o n on  to  and p r a c t i c a l  w i t h the Fermi l e v e l  interest  span a w i d e r  compared  v a l u e s o f a b o u t 8 A;  chemical  for mechanistic  The  chemistry  conductance  Intense p r a c t i c a l  systems  1.  typical  p-type  been shown; their  extensive  intercalants  and  'SO3F  produce  radicals, the  SO3F"  intercalation.  ASF5,  arsenic(V)  compound  of  intercalate 2e ^ = + -  fluoride  limiting appears  to  2AsFg' + A s F j .  oxidat ion, the various  intercalates  composition be  described  Therefore,  into  graphite  CgAsF5 . 3 3  to give  However,  by the e q u i l i b r i u m  in this  system  the  t h e e q u i l i b r i u m p o s i t i o n and t h e e x a c t c o n c e n t r a t i o n s intercalate  are not e a s i l y  species are subject  t o much c o n t r o v e r s y ,  deduced f r o m the s t o i c h i o m e t r i c  composition.  the  3ASF5  extent  a  + of of and  - 18  1.7  Methods o f  The  Intercalation  principal  methods  used  synthesis  c o u l d be c l a s s i f i e d a s :  external  chemical  oxidation of  species  graphite  intercalate  acceptor  is  of  graphite  (s)  the C X n  1.7.2);  an  anodic  intercalate A brief  below:  solvent,  Temperature,  for  the  to  both  +  The  method  could  be  illus-  equation:  X  (l,g,  HNO3  solution)  >  c  n (s) x  a n d BrSC^F c o u l d a c t as t h e  intercalant  X  product.  Some i m p l i c a t i o n s  factors  intercalate;  i n t e r c a l a t i o n compounds a n d a p p l i e s w e l l  Compounds s u c h as S 2 0 g F 2 ,  2.  method  o x i d a t i o n by  o x i d a t i o n or r e d u c t i o n .  a n d d o n o r compound p r e p a r a t i o n .  n C  suitable  itself  intercalation  t h e m o s t common a n d m o s t g e n e r a l t y p e u s e d  t r a t e d by the v e r y simple  to y i e l d  given  intercalation; not  of  acceptor  Intercalation  T h i s method i s synthesis  will  (modification  summary o f e a c h t e c h n i q u e  Direct  graphite  direct  which  exchange and s u b s t i t u t i o n ;  1.7.1  in  are: and  pressure,  controlling  1. hence  Solutions solvent  concentration,  the extent  c a l a t i o n b y w e i g h t becomes t h e  of  require  the  co-intercalation and  reaction  intercalation;  simplest  presence  method  3 . of  may  time  a  occur. are  Following  product  of  all  inter-  analysis,  -  termed tion  gravimetry.  19  T h i s m e t h o d may be u n r e l i a b l e  i n t e r c a l a t i o n due t o c o - i n t e r c a l a t i o n  physical  criteria  pressure  physical are  a liquid  or capable of  Finally,  taking place.  are used to c h a r a c t e r i z e  c a l a n t m u s t be a g a s ,  the  or  dissolving  composition  dimensions  a  intercalants,  solid  i n order of  the  i n t h e case o f  with  to  C X  is  n  which  Strictly an  inter-  measurable  vapor  intercalate  GIC  o f X and t h e degree t o  a  4.  solu-  i.e.  into  graphite.  i n f l u e n c e d by  interlamellar  the  spaces  filled.  1.7.2  Oxidation by an External Chemical Species  Three scope o f  contrasting  this  examples  are  presented  below t o  indicate  the  technique:  1.  Gaseous o x i d i z e r  2.  Solid molecular  - Cl£ a i d e d i n t e r c a l a t i o n oxidizer  - Cr03  acts  as  of A I C I 3 the  3 4  ;  oxidizer  in  H2SO4  i n t e r c a l a t i o n o f MFg" i o n ^ ;  M - P  Intercalation -*; 3  3.  Ionic or  oxidizer  molecules AICI3  CI2  allowing  t h e above s y s t e m s ,  intercalate  a  +  3  Sb.  In a l l  and  - N02  into  graphite.  the o x i d i z i n g species w i l l  It  facilitates  and a n i o n s by g i v i n g t h e g r a p h i t e vapor reacts w i t h graphite  stage  only  the  as t h e o x i d i z e r  is  evident  4  i n the  intercalation of  lattice  a positive  i n the presence of  one compound, C 3 Q A 1 C 1 " . 2 A 1 C 1 +  generally  3  following  is  obtained.  mechanism  not  neutral  charge. C I 2 gas,  The r o l e 3 7 , 3 8  :  3 4  of  - 20  C 1  1/2 A l C l 2  A l c l  C  + Cl .AlCl -  +  4  2 c l  In H2S0 compounds  4  ( a d s )  general  Pb0 . 2  manner,  3  d  s  C AlCl -.mAlCl  )  +  +  n  2(ads)  4  >  c l  3  Cl'  initially  with  graphite  CF C00H  intercalated  n  2  3  could  ( a d s )  2(g)  are  2  be  and  synthesized . 35  in  a  or other oxidants such as KMn04, Mn02 and  + 2 3 n  MF  6  N0  3 6  + 2  ion,  coming  from  (CH N0 ) could be obtained (M 3  and  Anodic Oxidation of Graphite  This  method  is  primarily  acids when graphite acts as anode  Sb  2  value of Y Is given as between 1.7  graphite  a  JK^SbFg  or  oxidizes the graphite i n a nitromethane s o l u t i o n , and a product  with formula C  1.7.3  (  3 ( a d s )  C 4 .HS04*.2H S04  As shown by B i l l a r d et a l .  N02PFg,  A I C I 4 -  c l +  +  and  Cr0  *  reacts  3  rAlCl  m  >  cl  formula  using  3 ( g )  3 ( g )  >  HCIO4  2(ads)  2(ads) ^  "(ads)  Strong acids such as similar  cl  intercalation, Cr0  of  cl  AlCl  + mAlCl  +  n  *  •  6 ( g )  3(ads)  2(g)^  the  or  P).  The  2.5.  (Electrochemical Method)  used f o r the i n t e r c a l a t i o n of protonic anode  (Fig.  1.4).  and the voltage drop between  continuously during the i n t e r c a l a t i o n process.  and C A  denotes 2  the  and Is monitored  non-aqueous  protonic  - 21  k2>J  Electrometer  Pt  V o l t a g e Recorder  Electrolyte C & C are Graphite E l e c t r o d e s Rj& R a r e R e s i s t a n c e s 2  2  2  Figure  Apparatus f o r Intercalation  the Electrochemical Comoounds.  Synthesis T r e s i s  of of  22 -  a c i d s u c h as H S 0 2  4  or H S O 3 F  functions  as e l e c t r o l y t e  sis)  cell.  As i n t e r c a l a t i o n p r o c e e d s ,  will  insert  into  place w i t h For reactions  the graphite  anions  anode,  and a  acids  CF3SO3H  i n the  and n e u t r a l  build-up  of  the  two  protonic  c o u l d be  written  3 9  and  >  CF3SO3H  2  2  An i n t e r e s t i n g  C  >  4  comment c o n c e r n s  dissociates  be o x i d i z e d  to  to give or  SO3F*  +  2 6  S 0gF  2  4  2  4  + 0.5  4  >  calation of  S 0gF 2  oxidation just 2  Some c o n d i t i o n a l involve  metal chlorides 4 0  a n d L i S b F g , w h i c h g i v e compounds o f These a r e e l e c t r o l y z e d  6  +  2  3  in protic  oxidation  lithium general  donor  can  2e"  an e x c e s s amount o f  s u c h as B i C l 3 or  This  HSO3F.  to:  systems where anodic  f u n c t i o n as e l e c t r o l y t e s  in  d i s c u s s e d may be i n t e r p r e t e d  i n the presence o f  2  The a n i o n S 0 F "  4  S 0 F 2  H  2.42)  oxidation  as H2S03F ".  2  1.63)  +  according  3  H  3  C 2 HS0 -.xH S0  as w e l l  3  2S0 F"  the anodic  following  C F 3 S 0 3 " . x C F S 0 3 H + 0.5  the anodic  S0 F" 2  the  4  (x -  melts  takes  :  24C + ( x + 1 ) H S 0  ize GIC's  molecules  voltage  H S0 ,  (x =  Hence,  acid  time.  26C + ( x + 1 )  acid  (electroly-  is  used to  4 1  .  synthes-  where  their  s u c h as L i P F g ,  LiAsFg  4  formula C  solvents  inter-  HSO3F.  and T e C l ,  salts  as  + 2 4  X".4  (solvent).  - 23 -  1.7.4  Intercalate  This  method  Exchange and  was  first  Substitution  u s e d i n t h e c o n v e r s i o n o f C 24HSC>4~ t o +  corresponding perchlorate product,  C 24HS04*  +  +  excess HC10  according  >  4  to^ : 2  C 24C10 "  +  +  4  H SC>4 2  R e c e n t w o r k done b y o u r g r o u p h a s p r o v i d e d some a d d i t i o n a l of  intercalate  exchange  +  C7SO3F  7  C 2 1  Substitution  B r S 0  3  F  +  3  excess SbF  5  — >  C 2  — >  CgSbFg  excess H S O 3 C F 3  reactions  interpretation of could  +  3  are  results  1.7.5  Intercalate  This  method  SbF , AsF 5  Oxidation or  is  5  3  C F  +  12  +  a n d e v e n when t h e y since equilibrium for  product and  +  C S03CF3  the r e a c t i o n :  was t r e a t e d w i t h NC^SbFg, t h e r e s u l t i n g 6  3  rare  c o u l d be d i f f i c u l t  SbF ~, AsFg",  S 0  1  — >  generally  form a t c e r t a i n stages o f  intercalates:  examples  reactions^ :  excess H S O 3 C F 3  C S0 F  the  AsF  mixtures  e x a m p l e , when C g A s F 5 n  showed W  3  occur,  the  following  .  Reduction  i l l u s t r a t e d by s t u d y i n g the redox r e a c t i o n o f  the  -  graphite-FeCl3  system.  t o FeCl2 by t r e a t i n g  The i n t e r c a l a t e d  the  i n an oxygen s t r e a m  halides  to pure metal,  4 0  .  Attempts  oxidation  has  also  compounds.  compound  composition C i g B r ( S O 3 F ) 3  later  undergo  C^ BrS03F,  3C  1.8  relevant  1.8.1  brief to  2  reduction,  following  Br(S0 F) 3  are  3  summary o f  t h i s work i s  +  3Br  2  some o f  intercalate  compounds.  The b r o m i n e  known s i n c e  1933,  4 7  was  the  Fe 03 2  by metal  i n t u r n c o u l d be  used  far ^. 4  reacted  to y i e l d  to  intercalated  observed  — >  4C  1 2  4 3  in  with  .  graphite2  a  This product  may  initial  BrS0 F  Intercalation  the graphite  S 0gF , 2  compound,  i.e.  intercalation  graphite  3  Compounds  acceptor  systems w h i c h  are  section.  Br  2  and p o s s i b l y  to give  compounds o f  and t h e c o m p o s i t i o n C  5BrS0 F  Compounds  only bromine, into  +  3  given i n the f o l l o w i n g  diatomic halogens, to  the  so  been  or  4 5 2  either  manner:  Selected Acceptor  known  reduce  was o b t a i n e d  G r a p h i t e - H a l o g e n and I n t e r h a l o g e n  Of t h e Cl  1 6  Review o f  A  When C ^ B r S G ^ F  intercalate  i n the  2  to  have n o t been s u c c e s s f u l  fluorosulfate of  H  where t h e r e s u l t i n g p r o d u c t  catalysts,  Intercalate  F e C l 3 c o u l d be r e d u c e d  intercalated product with  heating  as p o t e n t i a l  24 -  4 n  Br  true  graphite  chlorine,  intercalation have  ( n > 2) has been f o u n d  been for  -  these  compounds^.  It  composition corresponds as  C  + n  Br".3Br2  identify  transfer  such  and l a t e r  t o a stage  as  Intercalation  ( 3 < n < 5) w i t h  of  Intercalation  Br3"  compounds  in  indicated  that  that  the  Although  formulae  lattice is  very  lattice  in Br  l e d t o compounds  of  such  efforts  9  there  to  have  proven  little  charge  intercala-  2  formula  spacing of about  7.0  of  s u c h as I C 1 a n d  interhalogens  limiting  products** ,  the  and t h e h o s t  chlorine  interplanar  note  intercalation  or  intercalant  to  two c o m p o u n d .  early  Br"  research  between the  tion^.  interesting  were g i v e n t o  species  fruitless,  is  25 -  C  4 n  Cl  A ^-. 5  IBr  have  49 been only  known  for  sometime  r e c e n t l y been  characterized  The g r a p h i t e - B r C l disproportionate graphite, was  found With  usually  of  increasing  2  * IC1  Oxidation according  is  2BrCl  s u c h as C B r C l ^ . n  x  x  have  . rather -  complicated  » Br  + Cl .  2  f °  the  r  since  When  2  formula CgBrg.55CI0.45  coordination,  in  BrF3, the  of  the  ICI3  liquid  + ICI4";  + 2  polarization  and hence p o l y a t o m i c  abilities.  auto-ionization T <^c ,  5 2  ternaries  BrCl  reacted  richest  can with  compound  .  accentuated,  oxidizing  system  readily:  a product 5 2  , whereas  2IF5  graphite  -,  I F 5 all  5 3  the  interhalogens  and  phase  of  :  X-Y bond  have  undergo  2BrF3 — —  J" B r F  2IC1  + 2  + 2  + BrF4*;  * TF + + I F " . 4  lattice,  6  for  example,  may be c a r r i e d  2  +  stronger  appreciable  to^ :  2nC  is  2C  + n  +  IC1  +  -  I C1 2  6  out  - 26 -  The  observation that  in I F 5 intercalation,  the r e a c t i o n l e d to the p o s s i b l e  1F  +  5  IF  HF->  or B F 3  4  anion formation  + 4  mHF „  1  catalyses  1  mechanism ^, 1  I F ^ F ' m + l or  IF  +  5  This could take place  BF3  more  *IF/, BF/,' +  n  easily  i n t e r c a l a t i o n compounds o f I F 5 may, i n a d d i t i o n to the molecular  1.8.2  group c o n s i s t s  of  therefore,  by  autoionization,  contain H F 2 "  and  or B F 4 "  ions  pentafluoride.  Graphite-Fluorosulfate  This  than  Compounds  three  a)  Graphite  fluorosulfates  b)  Graphite acid fluorosulfates  c)  Graphite bromine  types of  intercalation  compounds:  - C SC>3F. n  - C S03F.(HSO3F),  and  n  fluorosulfates  -  C Br(S0 F) ,  w i l l be b r i e f l y  reviewed i n the f o l l o w i n g  n  3  m  m  -  1,  3  and  C oBrF(S03F) . 2  2  These tions.  compounds  Our r e s e a r c h  investigation of  group  has  group a) and  b)  g r o u p c ) w e r e r e p o r t e d b y us f o r complete  characterization  m e t h o d s s u c h as X - r a y p o w d e r  by  been  actively  graphite the f i r s t  compounds, w h i l e time  gravimetry, diffraction,  involved  4 3  .  In  all  microanalysis 1 9  F-NMR,  ^H-NMR  subsec-  in  the  all  GIC's  rein  instances, and p h y s i c a l and  Raman  - 27 spectroscopy,  1.8.2a  little  doubt  regarding  their  compositions  Graphite-Fluorosulfates  The into  leaves  oxidative  graphite  compound  of  intercalation  was f i r s t  of bis(fluorosulfuryl)peroxide,  undertaken by B a r t l e t t  composition  CgSC^F  et a l .  5  5  .  was r e p o r t e d b y t h i s  A first group,  r e s e a r c h c a r r i e d o u t b y H o o l e y ^ u s i n g gas phase i n t e r c a l a t i o n 5  into  various  Synthesis  the  above  has  by i t s e l f 5  by  Ubbelohde  produce  a  first  C 24•SO3F".mHSG^F, +  a "C^2  +  gas  S20gF2 C7SO3F.  phases** , 3  b o n d i n g model f o r C 7 S O 3 F has been are reported**  3  and  have  Fluorosulfates  well,  agent.  stage with m  2  and l a t e r  intercalation  = 2.0-2.5.  compound" b y o v e r o x i d a t i o n  is  only  a  acid,  HSC^F,  fifth  stage  s t a g e compounds w o u l d h a v e  Electrochemical  coworkers**  fluorosulfuric  producing  Hence t h e f o r m a t i o n o f l o w e r  and  of  later  sections.  intercalate  an o x i d i z i n g  and  stage  but  composition of  liquid  g e n e r a l l y been recognized t h a t  does n o t  material ^. Involve  The  both  a n d a number o f c o n v e r s i o n r e a c t i o n s  Graphite-Acid  It  in  results.  been mentioned i n e a r l i e r  1.8.2b  showed a l i m i t i n g  performed by our group,  confirmed proposed,  types o f graphite  S20gF2  oxidation,  first  by Herold et a l . * * 5  compound  Some e v i d e n c e  to  reported is  said  formulated  f o r the formation  f o u n d i n t h e same s t u d y w h e r e  to as of the  -  following  C +  sequence  24  S 0  With HS0 F i s  3 "• F  Cr0  m H S 0  3  >  F  as  3  proposed:  9  an o x i d i z e r ,  were i n t e r p r e t e d  the lamellar  carried  a first  i n terms o f  H  +  +  s t a g e compound o f  and t h e r e s u l t s  e"  f o r m u l a C^+-^  o f a Raman s t u d y o f  tightly  a l . ^ ° used HS0 F and S 0  out  3  synthetic  Madagascar g r a p h i t e . would  +  3  this  packed a c i d molecules  in  spaces.  Yaddaden e t  3  3  7  compound-*  S0  c2+.2S0 F-.(m-l)HS0 F  s a i d t o be o b t a i n e d - * ,  3  and  is  28  always  reactions  Although S0 be  present  3  or Cr0  3  as  3  between  was u s e d as  whenever  oxidizing  agents  the acid solutions an  HS0 F  oxidant, is  3  used  and  additional due  to  the  equilibrium.  HS0 F 3  First  3  w i t h compositions  a pronounced d e v i a t i o n from chemical o x i d a t i o n ^ • dilute  the  Cio  H S 0  3  F  values  solutions  of  S0  3  was f o u n d t o b e S 0 .  relatively  free  of  yield first  stage  intercalation products.  3  of  o f HS0 F i n t o 3  ( g )  reactions  to C HS0 F. 5  3  given  by  S0 , 3  Cr0  3  For  in  intercalant  the p u r i t y  HF  between  graphite  These v a l u e s other  show  authors  for  .  9  When  +  3 ( g )  s t a g e compounds w e r e o b t a i n e d f o r  and H S 0 F / S 0 , 3  S0  ( 1 )  the  HS0 F case  used,  where  the  the  main  acid  was  h a d t o be u s e d as t h e o x i d i z i n g a g e n t This  t h e a c i d c o u l d p l a y an i m p o r t a n t graphite.  were  3  study c l e a r l y role  i n the  shows  to  that  intercalation  29 -  The i n t e r c a l a t i o n p r o c e s s c a r r i e d o u t therefore,  have  one a t t e m p t s I n order  major  to explain possible  successive product,  example  2^6 2  vapor,  product  with  F  intercalation acid present ^2^6 2 F  t  o  1.8.2c  be  intercalation  for  stage  obtained** .  The  temperature stoichiometry  a n d h e n c e made  out  S O 3 free  i n our group** rather  The i n i t i a l  HSO3F  C14SO3F.1.05  and S 2 0 g F 2  i n the product.  intercalated  pathways.  3  showed  conveniently  stage  two  as that  by  This  t o g i v e a s t a g e one The  HSO3F.  and  due  to  simultaneous  the  greater  ability  of of  intercalation.  Fluorosulfates  was  reacted with B r S 0 3 F  one  product  reaction  (105-110°),  with  between  however,  a t ambient temperature,  composition  graphite gives  a  and  C^2BrS03F  BrS03F  different  at  3  2  2  The r o o m t e m p e r a t u r e r e a c t i o n i s  +  BrS0 F 3  assumed t o t a k e p l a c e  >  C  B 1  2  r  S  0  3  F  as:  an was  elevated  product  C oBrF(S03F) ** .  12C  ternary  i n d i c a t e d o n l y v e r y s m a l l amounts is  a  intercalation  3  composition  graphite  when  ^ S 0 F , w h i c h was s y n t h e s i z e d u s i n g g r a p h i t e  Graphite-Bromine  3  carried  method.  undergo o x i d a t i v e  When  may,  t h e a c i d u s e d i n o u r w o r k was  was r e a c t e d w i t h e x c e s s H S O 3 F  of  and m e c h a n i s t i c  Research performed e a r l i e r  intercalation could  HSO3F  compositions  successive d i s t i l l a t i o n s  much as p o s s i b l e .  acid  and c o u l d l e a d t o d i f f i c u l t i e s  t o a v o i d i m p u r i t y based problems,  p u r i f i e d by t h r e e  S  limitations  in fluorosulfuric  with  30  The h i g h t e m p e r a t u r e  r e a c t i o n s e q u e n c e i s p r o p o s e d as  3BrS0 F  Br  3  followed  +  2  Br(S0 F) 3  follows:  3  by,  Partial Br(S0 F) 3  >  3  BrF(S0 F) 3  +  2  S0  3  decomposition  20C  The gives  reaction  an  +  both  3  of  oxidative  However,  BrF(S0 F)  C^ BrS0 F 2  intercalation  unintercalated Br(S0 F) 3  is  3  intercalation  to a lesser  degree,  of  2  1 9  2  F-NMR  present  synthetic  graphite  of Br , 2  Cl , 2  as e x e m p l i f i e d b y t h e s y n t h e s i s  for  example  becomes n e c e s s s a r y dissolved  to  Iodine  relied  in a suitable  solvent.  that  excess  3  some  material  of  S 0gF , 2  3  a  the o x i d a t i v e  on  BrS0 F  2  (via  3  or  fluorosulfate  extensively  i n HS0 F  the and  chemical conversion  C^gBr(S0 F) . 3  t h e more u s e f u l  fluorosulfates  to consider d i r e c t  3  to both  IC1, IBr or BrCl,  o f a GIC,  C^gBr(S0 F) .  evidence suggest this  earlier,  product.  technique)  t o w i d e n t h e scope o f  formula  and  have  or  method,  ,  of  2  as shown  2  approaches  oxidizer  In order  4 3  on o x i d a t i o n o f g r a p h i t e  the electrochemical  3  excess S 0 g F ,  intercalation  seems t h a t  and h a l o g e n d e r i v a t i v e s  C ()BrF(S0 F)  compound  and  still  may be c h e m i - a b s o r b e d o n t h e  direct  and  3  stoichiometric  I n summary i t  >  2  3  direct  or perhaps  intercalation I  i n t e r c a l a t i o n w i t h the  2  itself,  it  intercalant  31  Two  general  types  been d e s c r i b e d and w i l l  of  now be  1.  The u s e o f n o n - p r o t o n i c  2.  HSO3F  1.8.3  intercalation  a c i d s as  works,  the  6  ,  will  first  and t h e n a t u r e oxidizer  1  in  of  be d i s c u s s e d b e l o w as p a r t  the  studies,  when  dissolved ions,  carried  be i l l u s t r a t e d  intercalated  b o t h systems.  s u c h as N O 2 B F 4 ,  of  Compounds I n N o n - p r o t o n i c  in  out  It  species.  the review  on  i n dry nitromethane,  6  (or  section.  ion  +  al.  and  the  two  3  compositions is  3  the n i t r o s y l produced N 0 2  graphite  al. **  Of  on p o s s i b l e N02  CH3NO2,  w h i c h were a b l e t o o x i d i z e  Solvents  Herold et  was shown b y H e r o l d e t  and N 0 2 S b F  N02PFg  by  this  m e n t i o n e d g i v e s more d e t a i l s  salts  NOSbFg)  solvents.  compounds.  intercalation  Forsman e t a l .  have  considered:  Graphite-Intercalation  Two  systems  solvents,  and o t h e r p r o t o n i c  These two systems w i l l selected  s o l v e n t promoted i n t e r c a l a t i o n  6  a  common  that  salt  nitryl NOSbFg)  (or N 0  +  to give  +  from  intercalation  compounds. Fluoroanions intercalated methods,  of  into pyrographite,  the  GIC's  C 23 MFg"(CH N02)y, +  3  n  1 9  F  product species.  and of  salts  3 1  were  such and  by  shown  where n I s  as  to  BF " ,  PFg"  4  chemical have  t h e s t a g e and y -  the  a n c i  analyses ideal  in  order  The m a i n r e a c t i o n  to e s t a b l i s h the nature is  thus  given  as:  were  and  X-ray  composition  1.7-2.5.  P NMR s t u d i e s h a v e b e e n c a r r i e d o u t o n t h e  PFg"  SbFg"  of  the  second  stage  intercalated  - 32 N0 PF 2  6  +  nC  >  The s e c o n d s t u d y b y F o r s m a n e t and  spectroscopic  into  graphite.  sulfone  evidence,  together  with  believed  to  N0 BF4  to give  anions  into  40°C  (together  with  depend on t h e  gave is  the  different  intercalation  It  in  in  chemical  SbFg" o r  tetramethylene  solvent  molecules  molecules  2  No i n f o r m a t i o n o n t h e was h o w e v e r from  BF4"  are  actual  observed t h a t those  run at  t h e amount  of  that  the room  solvent  inserts  may  temperature. has  t i o n of  FeCl  1.8.4  Graphite-Intercalation  6 2  of  N0 SbFg  products  also  been  was f o u n d as a n i n t e r c a l a t e 3  lacking  and t h e n e u t r a l m o l e c u l e s )  Solvent-cointercalation nitromethane  6  Neutral  e x p l a i n e d by assuming t h a t anions  PF  dissolved  graphite.  reactions  + n  intercalation  t h e above a n i o n s .  t h e p r o d u c t s was g i v e n .  This  C  , noticably  the  composition of  temperature.  +  a n d p o s s i b l y NG^BF^ o r  intercalate  at  2  were  2  2  the  al.  shows  N0 SbFg and  (sulfolane)  N0  noted  by  Hooley,  during the  solution  in Protonic  Solvents  where  intercala-  .  The t w o s o l v e n t  systems  a)  Oxidizing  (e.g.  b)  Solutions  Compounds  that  are  t o be d e s c r i b e d  in  this  section  and  graphite  are:  systems.  acids of  HNO3)  oxidizing  and g r a p h i t e  agents  in  systems  protonic  acids  33 -  1.8.4a  Graphite-Nitric  On a c c o u n t  of  its  Acid  strong  acting  b o t h as a s o l v e n t  gaseous  or  phite°  .  Compounds  oxidizing  a n d an o x i d i z i n g  liquid nitric  acid is  This  provided  p l a y e d by the  system  solvent  in  is  by the  the n i t r o n i u m  ion  self-dissociation  o b s e r v e d as a s u r f a c e The  3 7  in  useful  ' **. 3  of H N O 3 .  is  HNO3  towards  the  unique  graphite.  reaction  information  Only  with  regarding  in  gra-  the  role  reactions.  the active  adsorbed  agent  involved  intercalation  As s u g g e s t e d b y F o r s m a n , HNO3  ability,  N02  +  species is  in  intercalation  generated i n  the  liquid  I n v a p o r phase i n t e r c a l a t i o n ,  by  phase it  is  species.  f o l l o w i n g mechanism i s  proposed f o r  t h e v a p o r phase  intercala-  t i o n 38.  HN0  2HN0  c  n  N 0  3 ( a d s )  +  N  — v H N 0 3  3 ( g )  2 (ads)  — >  °2 (ads) +  N0 (ads) 2  C. + 'n  +  N 0  3"(ads)  The number o f n e u t r a l 4.5  and 4 . 3 ^ , 6  +  +  a  N 0  d  s  +  n  •>  )  3"(ads)  c +  N 0  +  H  2°  2(ads)  N0 (g) 2  C  +  a c i d molecules  respectively,  (  m in  w i t h m dependent  + n  .N0  _ 3  .mHN0  the product  3  is  on t h e p a r t i a l  stated  as  pressure  of  - 34 -  HNO3,  PHN03>  resulting  intercalation  of  frequently into  HNO3  i n stage  graphite similar  takes  planes^ .  This observation is  during the  intercalation of bromine^ > ^ .  9  The f o l l o w i n g c o n c l u s i o n s a)  HNO3  is  unique  intercalates b)  both  the  oxidizer  initial  the  basal  by  Hooley  t o t h e one made e a r l i e r  discussion: and t h e  (N02 ) +  HNO3).  to the  i n t e r c a l a t i o n by B r ( g ) 2  Co-intercalation  of acid molecules  being r e l a t i v e l y  easy.  1.8.4b  Graphite-Solutions  Since the focus o f GIC's  along  c a n be d r a w n f r o m t h e a b o v e  providing  and  (NO3"  place  The  Gas p h a s e i n t e r c a l a t i o n o c c u r s b y a c o m p l e x m e c h a n i s m , b u t a similarity  c)  in  transformations.  in  thesis  acid,  is  noted.  takes place w i t h removal o f  o f O x i d i z i n g Agents  this  fluorosulfuric  is  strong  on  a closer  in Protonic  the  Acids  synthesis  look at  HNO3  of  acceptor  some r e l a t e d s y s t e m s  is  now n e c e s s a r y . When c o n s i d e r i n g strong protonic 1)  acids,  Intercalation calation of  of  intercalation two q u i t e acid  into  distinct  graphite  using  objectives  anions, possibly w i t h concomitant  the n e u t r a l a c i d molecules  +  e x c e s s HX  +  Oxidizer  aided by s u i t a b l e  >  of  emerge:  agents:  nC  solutions  C X.mHX n  cointeroxidizing  35 -  This  2)  is  the  general  anodic  oxidation  within  this  in  by themselves  physical  as  for  acceptor  ionizing  s o l u t e Y,  furic  (HSO3F)  of  chlorides  s u c h as C u C l 2 ,  were d i s s o l v e d ,  was  used  Insertion CuCl , 2  layer  2  case  2  separation  I  c  is 3 5  of  is  interest  2  to  us  while  and  (HSO3CI) a l .  6  -  9  7  i n one s y s t e m ,  the  SbCl ,  BCI3,  5  were exposed t o  intercalated  FeCl , 2  o f - 8 . 0 3 A was  most  PCI5,  0  fluorosul-  .  Chloro-  and  elemental and  AUCI3  graphite  o r mechanisms were shown,  the  to  n  AICI3,  quoted f o r  PbCl ,  according  6  solutions  analyses  intercalate  ' **.  solvent  PbCl2,  to  acids  C Y  chlorosulfuric  the  intercalate  protonic  now i s  r e p o r t e d by H e r o l d e t  2  MnCl ,  the  6 9  .  follow-  products: of  the  NbCl ,  observed  5  halides,  etc.,  with  and an  stages  i.e. interranging  5.  Formation of  ternary  3 ) was f o u n d f o r c)  in  as  acid only  >  reviewed  are reported f o r  ZnCl ,  from 3 to  earlier,  special  not  in  acid cointercalation  and t h e r e s u l t i n g  of  which w i l l  objective  (solv)  ZnCl ,  A l t h o u g h no c h e m i c a l ing conclusions  as shown  as a  dissolved  the  reactions  a c i d s was f i r s t  acid  b)  Y  intercalation  sulfuric  a)  +  group has a l r e a d y been Graphite  reasons,  with possible  category  compounds,  solvents:  n C  The l a t t e r  and,  group. of  the  to acid salts,  s t r o n g a c i d s may be t r e a t e d  The i n t e r c a l a t i o n  acting  first  route  BCI3  + HSO3CI  compounds w i t h  I  c  ~8.36 A  (stage  BCI3.  Two p h a s e s y s t e m s w e r e shown t o  be  present:  one  graphite-HS0 C1 3  -  phase  In  ( I '  -  c  all  cases,  means o f p r o d u c t A similar CuF ,  NiF ,  2  8.10 A),  only  FeF3,  NbF , any  the f i r s t  SbF  5  5  etc.  reactions,  all  the  intercalate. stages  of  halides  2  chemical  stage graphite-SbF5  compound.  to  4  for  these  of  The many p o s s i b l e  difficult.  HSO3F  these  its  are p o o r l y  tion state  anion intercalate and m o l e c u l a r  ,  to  to  makes  in  the  accurate  It  occurs  o r perhaps even b o t h ,  form i n t e r c a l a t e d  solute  cases,  reaction  with  general represent  free  is  starting and SbF  fragmentary, is  unclear  or not, and i n  what  5  of and from  whether  present.  the with  interpretation  are r a t h e r  characterized.  intercalation  were  A,  For the  compound  No  proceed.  8.03  where X and X - l  SbF5  these studies  studies whether o x i d a t i v e  a c i d or  7 0  .  H S O 3 F was f o u n d as  7.90 A  ternary  and  I n most  complex a s s o c i a t i o n s between H S O 3 F  I n summary,  the r e s u l t i n g products  only  was p r o p o s e d  X  proportions  stage  c i t e d as t h e p r i m a r y c a u s e w h i c h  data  SbF5,  7 0  analyses  intercalation  intercalated products.  a first  X  mixtures. is  than  C7(HS03F) «(SbF5)i_ r  the f r a c t i o n a l  sole  fluorides  b y t h e same a u t h o r s  d i s t a n c e s were about  b e t w e e n SbF5 a n d g r a p h i t e , formula  SDCI3 phase.  metal  and  other  Interplanar  and  HSO3F  t h e t e m p e r a t u r e h a d t o be k e p t a t - 6 0 ° C f o r For  or  5  t e c h n i q u e was u s e d as t h e  s t u d y was c a r r i e d o u t u s i n g  for  SbCl  characterization.  mechanisms were g i v e n f o r shown  one g r a p h i t e - A u C l 3 o r  the X-ray d i f f r a c t i o n  AIF3,  2  36  the  oxida-  -  1.9  Intercalation  The  use o f  in Fluorosulfuric  fluorosulfuric  was c o n s i d e r e d a d v a n t a g e o u s is  HSO3F atmospheric pure. The  commercially pressure  Some p h y s i c a l acid's  reactions  broad  mobility. dynamic  such  will  liquid  HS0 F 3  ,  and  in graphite account  high  s t r e n g t h makes i t viscous used i n ric  this  acid,  or  to  vacuum  possible  does  is  not  also  that  1.2.  study  of  many  and enhances  temperature free  constant.  solvent  for  i n GIC s y n t h e s i s . ionization  is  spectroscopy. all  ionizing  Moreover,  non-volatile,  ion  via  a  of  surface  by  itself  resulting  transparent  Another  over  solvent  often  t o v a r y i n g degrees  in  in  medium on  the h i g h  Since almost a l l  show b a s i c b e h a v i o r HSO3F  intercalate  an e x c e l l e n t  which should allow monitoring  is  the  as a n u n c o m p l i c a t e d s o l v e n t  n e a r UV r e g i o n ,  research  when  simplifies  H2SO4  t o o b t a i n GIC's  In addition,  our  room t e m p e r a t u r e  transfer  Ion formation.  solutes v i a UV-visible  at  at  range.  compared  dielectric  work undergo  most s o l u t e s  reasons.  p u r i f i e d by d i s t i l l a t i o n  an a s s e t w h i c h p e r m i t s  HSO3F  It  an i d e a l  intercalants  Is  functions  intercalation. its  solvent  acid.  hence i d e a l l y  of  and c h e m i c a l  a c i d c a n be r e m o v e d a t r o o m  As d i s c u s s e d p r e v i o u s l y , 5 7  s t u d y as t h e  the a c i d are summarized i n Table  temperature  v a c u u m , w h i c h makes i t  adsorbed f l u o r o s u l f u r i c  well  of  filtration  excess  easily  not etch glass  range  of  i n our  several physical  properties  as  Also,  acid, H S O 3 F ,  for  and  The l o w v i s c o s i t y  Acid  available,  over a v e r y wide  operations  3 7 -  the  solid  intercalation  or  compounds  fluorosulfu-  increased  the  acid  visible of  S0 F" 3  and  absorbing  reason f o r using H S O 3 F  t h e compounds u s e d h a v e a common a n i o n ,  in i.e.  38 -  Table 1.2:  P h y s i c a l and Thermochemical Acid*  Properties  Property  (°C)  Freezing point  (D4  Viscosity  (°C)  -88.98  ) (centipoise)  Dielectric  constant (ohm"  (cal deg"  1  Heat o f f o r m a t i o n o f gas, (kcal mole" )  cm" )  1  25 25  1.56 1.72  25 25  1.08  1  0.28  g" ) 1  Latent heat of vaporization  (kcal  (from  mole" ) 1  Heat o f f o r m a t i o n o f (kcal mole" )  liquid,  8.4  elements) 181.9  1  (from  elements) 190.3 184  1  H e a t o f f o r m a t i o n o f gas f r o m g a s e o u s a n d HF ( k c a l m o l e " ) 1  from reference  1.726 1.728  -120  conductance  Heat c a p a c i t y  Temperature (°C)  162.7 164.4  25  Specific  Fluorosulfuric  Value  Boiling point  Density  of  71.  SO3 23.2  25 x  10"  4  25 25  -  SO3F",  with  respect  relatively  simple  extensive  use  to  ions  of  as w e l l  as i t s  S2O5F2  (which  has  tion  4 3  )  justifies  However, solutions  is  e.g.  a  acid  conditions.  synthetic  intercalation  of  H-microanalysis  are  results  this  may  could give  7 0  necessary  group  and  agents  such  as  intercala-  .  of  system.  Many  these  solutions  lead  to  to  carry  out  inert  oxidizing  an i n d i c a t i o n  In of  atmosphere  intercalants,  such the  acid  solvent  a n d as a c o n s e q u e n c e , formed.  are  difficul-  Fluorosulfuric  u n d e r vacuum o r  generally  The  by our  solvent  intercalation  the presence  acid.  regard to  and i f  results  may t a k e p l a c e  HSO3F  compounds  in  form  synthesis.  complex,  reactions  in  with  i n GIC  of  intercalants  oxidizing  previously  do o c c u r  the  reactions  with  w h i c h makes i t  Additionally,  co-intercalation  synthetic  studied  in graphite  3  and  fluorosulfuric  interpretation  to moisture,  manipulation  of  compatibility  SbF -HS0 F  sensitive  solution  are exceedingly  HSO3F  5  this,  in  some c o m p l i c a t i o n s  of  to  u s e as a s o l v e n t  u s e d as i n t e r c a l a n t s , ties;  in  been  its  Due  HSO3F.  the  others,  3 9 -  ternary  instances,  extent  of  acid  intercalation. In addition, consider  (a)  7 1  there  are  two  principal  equilibria  in  HS0 F 3  .  Self-ionization  2HS0 F „  or  »H S0 F 2  3  The H 2 S 0 F 3  +  3  ion is  autoprotolysis:  +  +  S0 F", 3  K  a p  -  3 . 8 x 1 0 "  termed a c i d i u m i o n and S O 3 F " ,  8  mole  base  2  kg  ion.  -  2  to  - AO -  (b)  Self-dissociation:  HSO3F  " HF  *  +  S 0  3  K  ,  s d  <3 x 1 0 *  The S O 3 t h u s p r o d u c e d c a n a i d o x i d a t i v e temperature  the extent  I n order  to  as w e l l  solvent  choice  (a)  of  Iodine tion  as b r o m i n e for  cations,  l 2  +  re  .  are k n o w n .  the  in particular in this  but  at  room  negligible.  to cationic  compounds,  2  iodine  species  becomes  HSO3F  the  reasons:  l 3  +  and i n s p i t e  solvent,  T h e y may be g e n e r a t e d  7 2  intercalation,  studies  fluorosulfate  following  stable  fl  kg*  2  o f d i s s o c i a t i o n c a n be c o n s i d e r e d  extend i n t e r c a l a t i o n  and i o d i n e  mole  7  of  and t h e i r in HSO3F  limited  dissocia-  UV-visible  by the  spectra  reaction,  HSO3F  nl  (b)  2  S 0 F 2  6  >  2  where n -  2 or  3.  I(S03F)  and  Br(S0 F)3  implies  (c)  +  3  that  The a n i o n s  3  4  of K[I(S0 F) ] 3  4  n  +  (  s  o  l  v  )  +  2 S 0  3  b e h a v e as n o n - e l e c t r o l y t e s  dissociation  I(S03F) "  2 I  is  extremely  or Br(S03F) " 4  or K [ B r ( S 0 F ) ] 3  4  in  slight. **' 9  may be o b t a i n e d HSO3F.  F -  (  s  o  l  v  )  in HSO3F,  which  9 7  by  dissolution  - 41 -  Enhanced E l e c t r i c a l  1.10  F o r a few compounds,  Conductance  t h e enhanced  measured u s i n g the c o n t a c t l e s s goal of  this  compounds, vities. since  thesis  is  the  Nevertheless, the  graphite  practical  explained (Fig.  synthesis  application i n the basal  by  1.5).  {it  antibonding  of  new  of  this  conductivity studying  the  gap,  conduction  (it  intercalation  ) band.  are the basic  carriers  between  layer  forces  would  o f charge  graphite  remove  b a n d (rc) r e s p e c t i v e l y . conductivity  of additional  layers,  as e l e c t r o n s  it  Therefore,  of states  this  "ideal",  i n donor GIC's directions  i n acceptor  for and  (7r)  the carbon atoms, band  separa-  (n-) b a n d t o holes  consideration  is not  samples  in  the the  lattice. the  since  nature  8 9  interacthe  inter-  .  and a c c e p t o r  from the conduction  However,  their  i n t h e c o n d u c t i o n band  a r e q u i t e weak b y  i n both a-and c - a x i s  electrons.  into  of  positive  w o u l d add e l e c t r o n s  electrons  necessary,  graphite  valence  i n the graphite  (Van d e r Waals t y p e ) intercalants  the  creates  m o d e l does n o t t a k e  the  Donor t y p e  from  process  T h e s e h o l e s as w e l l  Although t h i s tion  This  conducti-  the bonding  Due t o  8 8  can  is  density  I n an i s o l a t e d c a r b o n l a y e r ,  electrons  main  l a r g e l y based on  bands a r e formed f r o m p o r b i t a l s  )  band.  is  electronic  move  cal  Since the  acceptor  in intercalated  tion  ants  .  were  plane.  30-40 m e V .  valence  8 2  phenomenon  GIC's  w i t h an o v e r l a p e n e r g y o f about or  conductivities  frequency m e t h o d  an e x p l a n a t i o n o f  Enhanced e l e c t r i c a l be  radio  electrical  Compounds  o n l y a few samples were used t o o b t a i n b a s a l p l a n e  enhanced conductance  can  in Intercalated  intercal-  (TT*) band and v a l e n c e the enhanced  electri-  is  presence  due t o t h e  compounds,  holes,  which  - 42 -  %  i  Pristine  Energy  Figure  1.5:  D e n s i t y o f S t a t e s i n P u r e , Reduced and O x i d i z e d A c c o r d i n g t o t h e Band M o d e l .  Graphite  43  are  formed by t h e  along plane the  the  loss  basal  intercalate  species. the  9  Purpose o f  This  reasons  o f new a c c e p t o r  GIC's  carbon  would  factor  This  characteristics ^*  2D  The  Another  i n acceptor  i n t e r a c t i o n between  1.11  electrons,  plane.  conductivity  extreme  of  -  is  increase  the  which contributes the charge  process w i l l layers,  hence  conductance to high  localization  effectively giving  basal around  minimize  the  any  compounds  .  9 2  Study  that  initiated  this  graphite  intercalation  aim  intercalate  research  leading  compounds c a n  to  the  be  synthesis  summarized  as  follows:  a)  Synthetic iodine  b)  itself  Comparative viously  study of  providing  lead to  eliminated  or  Utilization  the  be  +  a  solvent,  a better  route  compounds  or  precursor.  s  intercalation  as  of  BrSC^F  reported  and w i t h e x t e n s i o n to  synthesis  ascertain  reaction  of  to  pre-  Br(S03F) , 3  C Br(S03F)3. n  conditions,  which  f o r m a t i o n o f G I C ' s where a c i d c o i n t e r c a l a t i o n  is  minimized.  of N 0  +  + e~  acid,  intercalation  compared  iodine-fluorosulfate  l2 (solv)  be made t o  fluorosulfuric direct  the  HSO3F  An a t t e m p t w i l l would  d)  by u t i l i z i n g  with  hopefully c)  to  to  the  > NO c o u p l e and  of  a comparison of  graphite N 0  to  +  by S 2 O 5 F 2 .  promoted  intercalate this This  synthetic  route  system w i l l  intercalation  in  SO3F"  systems  in  to  also non-  - 44 -  protonic  solvents.  Exploratory  reactions  which  pertinent  gated.  are  of non-intercalated to  halogen  intercalation chemistry,  fluorosulfates will  be  investi  - 45 -  CHAPTER 2  EXPERIMENTAL SECTION  - 46 -  EXPERIMENTAL  General  Comments  S i n c e m o s t compounds u s e d i n t h i s c a r e was t a k e n a t a l l  stages  synthetic  were  transfers fied  reactions  r e s e a r c h were m o i s t u r e  t o a v o i d any c o n t a c t w i t h m o i s t performed  in  o f m a t e r i a l s were c a r r i e d o u t  nitrogen  or  argon.  The  fumehoods  and  All volatile  with  puri-  compounds w e r e h a n d l e d i n inside  glass  fumehoods.  Apparatus  2.1.1  G l a s s Vacuum L i n e  S t a n d a r d h i g h vacuum t e c h n i q u e s were reactions. it  well ventilated  air.  i n a d r y box f i l l e d  vacuum l i n e s mounted on m e t a l f r a m e w o r k s  2.1  sensitive,  The  high reactivity  of  used  in  pyrex  other  The m a i n  v a c u u m l i n e was 600 mm i n l e n g t h a n d 20 mm O . D .  f i t t e d w i t h Kontes t e f l o n stem s t o p c o c k s were used and  the  apparatus  through  synthetic  t h e compounds t o w a r d s m o i s t u r e made  n e c e s s a r y t o keep t h e p r e s s u r e a t 0 . 0 0 1 t o r r .  the  all  to  manifold Five  attach  outlets reactors  B10 g r o u n d g l a s s c o n e a n d s o c k e t  joints.  The v a c u u m l i n e was c o n n e c t e d t o a W e l c h D u o - s e a l m e c h a n i c a l pump 1405)  via a l i q u i d nitrogen cold trap  to prevent  any c o r r o s i v e  of  (model  volatile  - 47  m a t e r i a l s b e i n g drawn t h r o u g h manifold  using  atmosphere. reaction  a  mercury  Transfer  vessel  of  the  -  pump.  manometer  liquids  Pressures  showed v a l u e s  and o t h e r v o l a t i l e  measured from 0.5 material  in  the  torr  to  from  t o a n o t h e r was c a r r i e d o u t u s i n g a T - c o n n e c t i n g  1  one  bridge,  w h i c h was a t t a c h e d t o t h e vacuum l i n e v i a a BIO c o n e .  2.1.2  Metal Fluorine  Line  I n t h e S20gF2 p r e p a r a t i o n flow  a p p a r a t u s were b u i l t  a t t a c h e d t o a m e t a l frame Research  Tool  Co.,  Engineering I n c . , l i n e were e i t h e r  2.1.3  work.  The  California;  the  silver  fluorine  valves  Hoke  used  Inc.,  Pennsylvania respectively.  Dry Atmosphere  recirculating unit molecular  sieves.  dry  box  for A  inch, from  the O.D.)  Whitey  New J e r s e y a n d A u t o c l a v e All  air  sensitive  connections  in  the  fittings.  "Dri-Lab",  compounds w e r e c a r r i e d o u t model  HE-43-2,  P 0 5 was k e p t 2  t h e d r y b o x t o remove a n y r e s i d u a l m o i s t u r e The  (1/4  and  Box  and p u r i f i e d n i t r o g e n o r a r g o n .  indicator.  line  were  s o l d e r e d o r made w i t h S w a g e l o c k  a Vacuum A t m o s p h e r e C o r p o r a t i o n  inside  2.7),  u s i n g copper o r monel t u b i n g  The m a n i p u l a t i o n o f a l l  dry  (Fig.  fitted  i n an open and  to  in  with  container  act  as  an  was e q u i p p e d w i t h a " D r i - T r a i n " m o d e l HE-93B  constant Mettler  circulation of nitrogen  or  argon  P160 t o p l o a d i n g b a l a n c e was u s e d  over inside  - 48 -  the d r y box i n o r d e r  2.1.4  Reaction  Primarily  a)  to weigh hygroscopic  Vessels  two t y p e s o f p y r e x v e s s e l s were u s e d .  Two P a r t G l a s s  Reactor  The r e a c t i o n f l a s k u s e d was e i t h e r round  materials.  bottom  a 50 m l E r l e n m e y e r  f l a s k w i t h a s t a n d a r d B19 g r o u n d g l a s s  t o p c o n s i s t e d o f an a d a p t e r w i t h a Kontes wiched to  Erlenmeyer graphite  for  reactions ^2°6 2  apparatus  and t h e f a c t  Also,  easily  (Figs.  2.1(A)  and  intercalation reactions.  raised  F  2.1(B)).  the  out  that during  the  i n t e r n a l pressure  in  a two p a r t  The o b v i o u s d i s a d v a n t a g e  products  due t o  f l u o r o c a r b o n grease  reactions  The  in exploratory  sand-  attachment  flat  surface  bottom area  of  of using  a  intercalation  HOPG  plates  glass reactor  was  the  (or  Quite obviously,  and  HSO3F  a t room t e m p e r a t u r e  t o be a p p l i e d a t t h e g r o u n d g l a s s j o i n t s t i o n s under vacuum.  for  its  contamination  two p a r t  leakproof  reactors  are  so  least  much  reaction products)  to maintain  studies.  to at  was  the  more  than i n a single  possible  a  reactor  stopcock  Obvious disadvantages  t h e a d d i t i o n o f r e a g e n t s and  carried  The  or  i n vacuum l i n e w o r k were t h e s m a l l volume o f  reactor.  useful  stem  f l a s k had the advantage o f exposing a l a r g e r  bottom  torr.  cone.  b e t w e e n a B19 s o c k e t a n d a BIO g r o u n d g l a s s c o n e ,  t h e g l a s s vacuum l i n e  flat  teflon  flask  5  more part of  which had connec-  particularly  -  49  - 50 -  b)  One P a r t G l a s s  Reactors  To a v o i d g r e a s e  contamination  altogether,  vessels  were used wherever n e c e s s a r y  one p a r t  reactor a  (Fig.  flask  or  cone.  The s i d e arm o f  stopcock,  round  2.2(A))  addition  of  the side  arm.  Both s i n g l e p a r t  ease  in  flame  a)  When an a d d i t i o n  stem  sealed  at  the  box,  constriction.  The  reaction vials  vessels  (Fig.  as w e l l  S20gF2 A d d i t i o n  teflon  through  (Fig.  2.2(B))  these types o f r e a c t o r s .  Miscellaneous  a n d a B19  Once t h e r e a g e n t s w e r e a d d e d i n t h e d r y  mm x 3 mm) w e r e u s e d i n o r d e r  2.1.5  Erlenmeyer  with a constriction  2.3)  Glass  and  reaction  were a l s o used.  a n d s o l i d o r l i q u i d r e a g e n t s c o u l d be  calation reactions  a pyrex  seal-off  r e a c t a n t s was c a r r i e d o u t v i a d i s t i l l a t i o n  w i t h a round bottom f l a s k SP1 g r a p h i t e  reaction  The  t h e r e a c t o r was f i t t e d w i t h a K o n t e s  c o u l d be  liquid  (50 m l ) ,  part  2.2 and 2 . 3 ) .  was made up o f e i t h e r  bottom f l a s k  a n d a BIO c o n e .  the capped r e a c t o r  (Figs.  single  The a d d i t i o n  done  T e f l o n coated magnetic  with  as i n p r i m a r y s y n t h e s i s  relative  stir  t o mix s o l i d and l i q u i d phases  of  in  bars  (10  inter-  reactions.  Apparatus  Trap  stoichiometric  a m o u n t s o f S20gF2 w e r e n e e d e d f o r  t r a p was u s e d ( F i g .  c o u l d be d i s t i l l e d u s i n g t h i s  2.4).  device.  E x a c t v o l u m e s o f up  a reaction, to  0.50  ml  The t r a p was made up o f a p i p e t t e  51 -  Figure  2.2:  One P a r t R e a c t i o n  Vessels,  (A)  "Seal o f f "  One P a r t  Reactor.  (B)  "Round B o t t o m " One P a r t  Reactor.  Figure  2.3:  One P a r t R e a c t i o n  Vials.  (A)  "Medium W a l l e d "  (B)  "Thick Walled"  Reactor. Reactor.  -  S  2°6 2 F  Addition  Trap.  53  -  (0.00-0.50 ml) a  Kontes  54  f i t t e d w i t h a 20 mm l o n g ( 1 0 mm O . D . )  t e f l o n s t e m s t o p c o c k was a t t a c h e d .  w i t h a B19 g r o u n d g l a s s  cone.  similar  b)  type of  to  The a p p a r a t u s  top of  the  (Fig.  glass  frit  made  amounts  of  to a  was u s e d .  2.5)  as  in a reaction mixture,  described  in  a n d t h e B19 s o c k e t ,  a Kontes  Shriver tube  t e f l o n stem  8 7  in  was f i t t e d w i t h a 100 m l r o u n d b o t t o m f l a s k , The f i l t r a t i o n was t h e n c a r r i e d  Once  the whole out  in  a  was which  bottom. socket. stopcock  the apparatus a l s o had a s i m i l a r  a b o v e w h i c h a B19 g r o u n d g l a s s c o n e was a t t a c h e d .  c o u l d be e v a p o r a t e d .  it  S2O5F2,  t u b e e n d e d i n a B19 c o n e a n d t h e b o t t o m i n a B19  The s i d e a r m o f  box.  trap  was s e t a b o u t one t h i r d f r o m t h e  was  socket  larger  c o n s i s t e d o f a 25 mm O . D . p y r e x g l a s s  frit  cock,  the  Apparatus  Between t h e g l a s s connected.  ended  thus p r o v i d i n g a n o t h e r method  For a d d i t i o n o f  apparatus  a medium c o a r s e n e s s The  A s i d e arm e x t e n s i o n  separate a s o l i d from a l i q u i d  vacuum f i l t r a t i o n used.  which  t r a p , w i t h a 4.00 ml c a p a c i t y p i p e t t e ,  Vacuum F i l t r a t i o n  I n order  to  The c o m p a c t n a t u r e o f  easy t o w e i g h i n an a n a l y t i c a l b a l a n c e , check t h e amounts added.  pyrex bulb  the  stopB19  apparatus the  dry  - 55 -  Figure  2.5:  Vacuum F i l t r a t i o n  Apparatus.  - 56 -  2.2  Analytical  2.2.1  Equipment  Visible  A  Cary  and U l t r a v i o l e t  17D  d o u b l e beam s p e c t r o p h o t o m e t e r was u s e d t o o b t a i n  t e m p e r a t u r e U.V.  and v i s i b l e  The  range  wavelength  optical  kept a i r t i g h t ferred  cells  Infrared  Infrared  and  spectra  windows  reference  for  i n 1.00  mm  nm.  All  cell  the path  England,  s o l u t i o n s w e r e made a n d  were  recorded  using a Perkin-Elmer  i n the wavelength range o f 4000-200 c m " . 1  reactive  a m u l l i n g agent. recorded  (0.042 all  750-300  and  trans-  Spectrophotometer  as  and m o i s t u r e  t h e Harshaw Chemical C o . ,  grating  Since  the  AgBr windows  Gaseous I . R .  A polystyrene  dry  spectra  w h i c h was f i t t e d w i t h v a c u u m  and t h e o p t i c a l windows Ohio.  598  The s a m p l e s w e r e p r e p a r e d i n t h e  inch thickness).  spectra,  sensitive,  s o o n as p o s s i b l e .  were t a k e n u s i n g a monel m e t a l c e l l , AgCl  =  o b t a i n e d from Thermal Syndicate L t d . ,  compounds u s e d w e r e h i g h l y were used w i t h o u t  A  box.  spectra  spectrophotometer,  box  Samples w e r e f i l l e d  with t e f l o n stoppers.  i n the dry  2.2.2  s p e c t r a i n t h e range o f  room  o f t h e s p e c t r o p h o t o m e t e r was 1 8 6 - 2 6 5 0 nm a n d  s p e c t r a l b a n d w i d t h 0 . 1 nm. quartz  Spectrophotometer  tight  f i l m was u s e d as a  were  obtained  from  -  2.2.3  57  N u c l e a r M a g n e t i c Resonance  Spectrometer  A B r u k e r CXP-200 FT-NMR s p e c t r o p h o t o m e t e r was u s e d t o r e c o r d state  1 9  F  spectra.  NMR t u b e s o f were  30 mm l e n g t h a n d 5 mm O . D . w e r e u s e d .  loaded  an e x t e r n a l were  inside  using  methylsilane  High r e s o l u t i o n  a  Varian  ^H  of  were r e c o r d e d on a V a r i a n EM-360, o p e r a t e d a t  s p e c t r a were t a k e n a t room  2.2.4  Raman  liquid  samples  60 MHz.  reference.  and e x t e r n a l  samples  F r e o n - 1 1 was u s e d as  spectra  (TMS) was u s e d as a n e x t e r n a l  1 8 8 . 1 5 MHz.  powder  EM-360, a t a f r e q u e n c y o f  a n d F r e o n - 1 1 w e r e u s e d as i n t e r n a l All  The  t h e d r y box and f l a m e s e a l e d .  reference.  taken  liquids  The s p e c t r o p h o t o m e t e r was o p e r a t e d a t  solid  Tetra-  spectra 5 6 . 4 5 MHz.  references  of  HSO3F  respectively.  temperature.  Spectrophotometer  Room t e m p e r a t u r e Raman s p e c t r a w e r e r e c o r d e d u s i n g a Spex R a m a l o g - 5 spectrophotometer, 514.5  nm,  graphite as  emitted  by  a  Spectra  Physics  a back-scattering  164 a r g o n i o n l a s e r .  the loss  of  a r r a n g e m e n t was u s e d ^ .  l a s e r power a t  and  i n c i d e n t beam ( F i g .  2.6).  any p o l a r i z a t i o n change i n t h e  cell,  w i t h q u a r t z w i n d o w s , was u s e d t o h o l d  manipulations  were  done i n t h e d r y b o x ,  s a m p l e p r e p a r a t i o n was  over.  the  samples.  well  geometry  also  All  at  Since  as  This  t h e q u a r t z windows  vents  as t h e  line  i n t e r c a l a t i o n compounds h a v e a v e r y h i g h r e f l e c t i v i t y  absorption,  minimizes  a n d t h e e x c i t a t i o n w a v e l e n g t h was t h e g r e e n  A  preteflon sample  a n d s p e c t r a w e r e t a k e n as  soon  B a c k - s c a t t e r i n g A r r a n g e m e n t Used f o r Raman S p e c t r a .  - 59  2.2.5  X - r a y Powder  X-ray of  powder p h o t o g r a p h s were t a k e n u s i n g a P h i l l i p s  57 mm r a d i u s ,  Cu-K  X-ray  Q  Diffraction  having a conventional  radiation  r e d u c e Kp r a d i a t i o n . the  samples,  (A «- 1 . 5 4 0 5 A)  r a n g e d f r o m 8-12 h r s .  NS-392 T t y p e  The d i f f r a c t i o n  lines,  2.3  Carbon, at  University  hydrogen,  1106 sulfur  box  and  film  for  flame  t h e measurement  into  sealed.  which  assembly, of  of  photographs.  illuminator,  location  to  nature  the  was  containing diffraction  i s ±0.03  A.  a n d n i t r o g e n a n a l y s e s w e r e done b y M r . Laboratory  Columbia.  elemental  glass  of  the  Chemistry  tubes  Borda The  A f l a s h o x i d a t i o n method, u s i n g a Carlo  analyzer,  All  P.  Department,  was  used  for  this  and h a l o g e n s were a n a l y z e d b y A n a l y t i s c h e  Gummersbach i n W e s t Germany. loaded i n t o  the  filter  Analyses  of B r i t i s h  E l b a model  dry  to which a measuring s l i d e  The a c c u r a c y o f  the M i c r o a n a l y t i c a l  Elemental  i n the  and a m a g n i f i e d c r o s s - h a i r  Elemental  was u s e d w i t h a n i c k e l  The p o w d e r s a m p l e s w e r e l o a d e d  l i n e s were measured on a  was a t t a c h e d .  camera  arrangement.  f i l m s were used t o o b t a i n X - r a y powder  made up o f a m e t e r s t i c k a Vernier  loading  The t i m e o f e x p o s u r e d e p e n d i n g on  0 . 5 mm L i n d e m a n n g l a s s c a p i l l a r i e s Kodak  Straumanis  powder  samples used  ( 6 - 7 mm O . D . )  for  purpose** . 1  Laboratorien,  microanalysis  i n the d r y box and flame  were  sealed.  - 60 -  2.4  Electrical  Conductivity  A contactless measure  the  insert  the  temperature  A circular sample  electrical  The  system  induction electrical  ferrite  tubes.  area were measured u s i n g micrometer.  I n t e r c a l a t e d HOPG Samples  radiofrequency  room  HOPG s a m p l e s .  of  core of  travelling  of  was  8 2  conductivity  60 mm  The t h i c k n e s s  a  technique  of  diameter  used  intercalated was  used  t h e sample and t h e  microscope  and  a  The o v e r a l l  AV  -  relationship  is  to  surface  toolmaker's  was c a l i b r a t e d u s i n g m e t a l s a m p l e s w i t h  conductivities.  to  known  given by:  kts cr 2  where, AV = o u t p u t v o l t a g e k  (mv)  — constant  s  surface  a  electrical conductivity 1 1 s a m p l e (ohm" - cm"- -)  area of  -1  t  =  thickness  of  Some o t h e r u s e f u l  a/o  g  k/kg  t h e sample  relationships  =  specific  conductivity.  =  specific  conductivity  g  Q  -  increase (k/k  in  thickness.  )/(t/t ). Q  of  1  (cm)  AV/AV . t/t  t h e sample  a r e as  follows:  (<7g = c o n d u c t i v i t y (normalized)  o f HOPG).  per plane of  graphite.  (cm ) the  - 61 -  2.5  Other  Techniques  Mass  spectra  operated at  were  70 e V .  obtained  A Thomas H o o v e r c a p i l l a r y  was u s e d t o g e t t h e m e l t i n g  2.6  S20gF  kilogram quantities) a  AgF2  experimental method i s  set-up  S20gF2,  at  a  prepared  fluorine  temperature  this preparation is  and  of  -180°C  route  to  Pressure r e g u l a t e d f l u o r i n e cylinder  react  containing  NaF.  from the f l u o r i n e with sulfur  r e a c t o r by a stream o f  dry  the  using a h e a t i n g mantle at  gas.  t o 50°C,  and t h e o v e r a l l  condensation i n the dry ice  products  free  sulfur  •  2.7.  This  as  kept  n i e  described through  a  i s necessary  to  fluorine  Excess  flow  was the of  counter. trioxide  was  heated  r e a c t i o n temperature  generated  t r a p s A , B a n d C,  trioxide  w h i c h was c a r r i e d t o  o i l bubble  the r e a c t i o n ,  The  trap  HF  several  83,84  passed  nitrogen.  y i e l d of  -180°C.  was This  trioxide,  f l u o r i n e was d e t e c t e d u s i n g a f l u o r o l u b e improve  shown  (in  sulfur  a modified v e r s i o n of the general synthetic  AgF2 c a t a l y t i c  maintained  was  Fig.  allowed  To  apparatus  Reagents  in  steel  for  remove a n y HF i m p u r i t i e s then  of  by the r e a c t i o n o f  catalyst  i n the l i t e r a t u r e . stainless  point  2  Bis(fluorosulfuryl)peroxide,  using  melting  spectrometer  points.  P r e p a r a t i o n and P u r i f i c a t i o n  2.6.1  w i t h a K r a t o s MS50 mass  were at  collected -78°C.  was by  Excess  -  62 -  Cosby P r e s s u r e  Guoge  To Flowmeter Copper  Gloss To f", cylinder  Reaclor  Copper  Gloss To S o d o - J I m e Trop  (J) Whitey Volve  B34  B34  B 34  Hoke 4 1 3 Valve  6  -Fluorolube Oil Tube  Autoclave Engineering, Valves  A  Ik Figure  2.7:  Apparatus  for  B  the P r e p a r a t i o n o f  C  S 06F . 2  2  -  fluorine  and b y - p r o d u c t  rendering with  purified Gas  phase  infrared  the p u r i t y  2.6.2  of  remove  any  the  spectroscopy  S 0gF2  into  and l i q u i d  1 9  reactor,  liquid sulfur  pyrex  was  hence  extracted  trioxide. storage  This  vessels.  F NMR w e r e u s e d t o  confirm  obtained.  2  HSO3F  Technical available  grade f l u o r o s u l f u r i c  sources  and  a c i d was o b t a i n e d  was p u r i f i e d b y a d o u b l e  d e s c r i b e d b y Thompson a n d G i l l e s p i e ^ • 8  method i s  shown i n F i g .  remove any m o i s t u r e , Distillation spheric  was  pressure,  collected  at  163°C.  stored  the  I  + 2  8 f )  The e n t i r e  .  from  commercially  distillation  The a p p a r a t u s u s e d s y s t e m was f i r s t  out under  nitrogen.  a blanket  fraction  dry box t o p r o t e c t  container it  for  this  about  15  dry nitrogen at  atmo-  s e c o n d f r a c t i o n was  was e v a c u a t e d  f r o m any  and  to h.  c o l l e c t e d was made HF f r e e b y  The c o n s t a n t b o i l i n g  The s t o r a g e  of  technique  flame d r i e d  a n d n i t r o g e n was f l u s h e d t h r o u g h f o r  and the. f i r s t  of  in  2.8.  carried  counterflow  2.6.3  a soda l i m e  unreacted  was t h e n vacuum d i s t i l l e d  S20gF2  to  The c o n d e n s e d c o l o r l e s s  to  H2SO4  -  F S O 3 F were c a r r i e d  them i n a c t i v e .  96-98%  63  a  then  the  acid  contamination.  (solv)  Preparation  of  this  d e s c r i b e d by G i l l e s p i e  r e a g e n t was c a r r i e d o u t a c c o r d i n g t o  and M i l n e  7 2  .  1.1057 g o f  I  2  and  the  0.4298  method g  of  - 64  Figure 2.8:  -  F l u o r o s u l f u r i c Acid D i s t i l l a t i o n Apparatus.  - 65 -  £>2°6 2 w e r e u s e d , a n d t h e r e a c t i o n t o o k p l a c e F  2I  The 2:1,  mole  ratio  S 0 F 2  of  6  I  >  2  t o S C>5F  2  2  a n d t h e r e a c t i o n was a l l o w e d t o  temperature.  2.6.4  3  and C a d y room  +  + 2  .  1.1952 g o f I  temperature,  The e x c e s s S 0 g F 2  2  of  3  take  place  for  for  to a value  18  h,  at  of  room  intercalation.  2  2  and excess S 0 g F 2  as shown b y  2  was u s e d , a n d when t h e r e a c t i o n  4.003 g o f y e l l o w viscous  I(S0 F) 3  had was  3  Roberts warmed  obtained.  was r e m o v e d b y v a c u u m .  I  The s o l u t i o n s  2S0 F*  was k e p t v e r y c l o s e  2  equation,  3  r e a g e n t was made f r o m I 7 3  2I  The s o l u t i o n was u s e d i m m e d i a t e l y  I(S0 F)  This  to  +  2  according to the  +  2  I(S0 F) 3  3S 0 F 2  3  6  >  2  were used f o r  2I(S0 F) 3  3  i n t e r c a l a t i o n w i t h HOPG a n d S P - 1  graphite.  2.6.5  IS0 F 3  Synthesis 1.05.  was  The m e t h o d i s  carried  out  u s i n g a mole r a t i o  d e s c r i b e d b y Aubke a n d C a d y  7 4  .  of  S 0gF 2  2  to  1.4096 g o f I  I 2  2  of and  -  1.1506  g  of  S20gF2  obtained according  were  used,  +  2  S 0 F 2  6  The p r o d u c t was u s e d i m m e d i a t e l y  and  2  vessel.  7 5  .  A large  The  IBr S03F  excess o f  is  product  for  2ISO3F  intercalation  reactions.  K[I(S0 F) ] 3  An excess o f  +  and  4  Two s y n t h e t i c  KI,  was  2  the  contained  stored  technique  p u b l i s h e d by  in  a  single  under n i t r o g e n  part  Wilson  distilled reaction  i n the dry box  since  sensitive.  excess  Br2  •>  IBr S0 F 2  3  K[Br(S0 F) ] 3  methods were  S 0gF  to  d r i e d a n d p u r i f i e d b r o m i n e was  ISO3F,  extremely moisture  ISO3F  dried  was  3  i n vacuo onto pre-weighed  a)  dark brown s o l i d product  IBr S0 F  and A u b k e  2.6.7  a  •>  2  P r e p a r a t i o n was done a c c o r d i n g  2  -  to:  I  2.6.6  66  2  (~3.00  to obtain K [ I ( S 0 3 F ) ] 4  4  used.  ml)  was d i s t i l l e d  o r o n t o KBr t o  onto about  synthesize  1.00  g  of  K[Br(S0 F) ], 3  4  -  according phases  to  of  mixture,  the method d e s c r i b e d by L u s t i g  the  reaction  took approximately  +  KI  b)  alternative  Dried KI  turn  2S 0 F 2  +  2S 0 F 2  6  to  the  30 m i n .  amount  of H S O 3 F  KI reactor,  w h i c h was k e p t a t excess o f  to  to  completion a f t e r  about  by slow pumping under  2 h.  completion.  4  3  overcome  via  4  this  problem.  reactor,  a T-bridge.  remove  any  ml)  which  The s a l t  residual  was t h e n d i s t i l l e d  (-3.00 ml)  the  was d i s t i l l e d  a m i l d exothermic yellow  into  reaction  in color.  The e x c e s s H S O 3 F  was was  moisture.  In a  s o l u t i o n was l i g h t  two  a homogeneous  l i q u i d nitrogen temperature.  Upon w a r m i n g t o room t e m p e r a t u r e , and t h e r e s u l t i n g  the  K[Br(S0 F) ]  (-2.00-3.00  S2O5F2  give  achieve  3  a one p a r t  vacuum l i n e  sufficient  an  to  to  Since  K[I(S0 F) ]  •>  2  .  did not  3 weeks  •>  2  g ) was a d d e d t o  u n d e r dynamic vacuum f o r  manner,  6  r o u t e was t r i e d  (-0.532  connected  and Cady'  and t h e p o t a s s i u m h a l i d e s  S2O5F2  KI  A novel  67 -  onto  A the  reactor.  took  were  kept  similar  place,  The r e a c t i o n  and S 2 0 g F 2  in  went  removed  vacuum.  HSO3F  KI  The  +  reaction  excess  was  p r o d u c t was o b t a i n e d .  S 0gF 2  2  monitored An i d e n t i c a l  by  •>  K[I(S0 F) ]  weight,  and a b o u t  technique  3  was  used  4  1.568 to  g of  the  synthesize  - 68 -  K[Br(S0 F) ]• 3  4  Br(S0 F)  2.6.8  3  3  Bromine(III)  Br  An  excess  fluorosulfate  2  +  of  excess  S20gF2  c o n t a i n e d i n a two p a r t temperature. 1.539  g of  The  light  2.6.9  was  excess  2Br(S0 F) 3  distilled  onto  and t h e m i x t u r e  S 0gF2 2  yellow solid.  •>  was  the  then  reaction  3  about  1.59  g of  a l l o w e d t o warm t o  pumped o f f ,  leaving  Br2 room  about  The r e a c t i o n was f o l l o w e d b y w e i g h t ,  and  spectroscopy.  BrS0 F 3  Bromine(I)  fluorosulfate  Aubke and G i l l e s p i e  7 7  The s m a l l e x c e s s o f of  BrS0 F. 3  was  prepared according to  by u s i n g a mole r a t i o  Br2  yield  S20gF2  reactor,  checked f o r p u r i t y by I . R .  was made a c c o r d i n g t o  In  +  S20gF2  o f S20gF2 t o B r  ->  S20gF2 was n e c e s s a r y the  the method 2  of  -1.018.  2BrS0 F 3  to  much  improved  i n t e r c a l a t i o n r e a c t i o n w i t h SP-1  graphite,  a b o u t 0 . 7 9 0 g o f t h e r e d - b r o w n l i q u i d was u s e d .  get  a  -  2.6.10  NOS0 F 3  Nitrosonium fluorosulfate and  according  S20gF2,  to  was p r e p a r e d u s i n g a s l i g h t  the  About  1.236  part  reactor,  white  s o l i d N O S O 3 F was o b t a i n e d ,  using  I.R.  The  method  g o f NO gas a n d - 2 . 0 0 w h i c h was k e p t  at  ml o f  excess o f  published by Qureshi e t S20gF2  liquid N2  were d i s t i l l e d  temperature.  NO  al.  into  About 4 . 2 0  a n d t h e p r o d u c t was c h e c k e d f o r  7  9  .  a one g of purity  Spectroscopy.  2N0  product  +  S 0 F 2  6  >  2  2NOSO3F  was w e i g h e d i n t h e d r y b o x a n d u s e d f o r  with  SP-1  2.7  Commercially A v a i l a b l e  2.7.1  69 -  intercalation  graphite.  Chemicals  Graphite  Two k i n d s reactions SP-1  of  graphite,  SP-1 g r a p h i t e  a n d HOPG w e r e u s e d ,  were c a r r i e d o u t u s i n g SP-1 g r a p h i t e graphite  (spectroscopic  grade,  Columbia.  J.G.  Hooley,  Department  of  purified natural  Chemistry,  HOPG ( H i g h l y O r i e n t e d P y r o l y t i c  Union Carbide L t d . ,  Parma,  Ohio.  most  only.  5 0 - 1 0 0 fi g r a i n s i z e was o b t a i n e d f r o m U n i o n C a r b i d e and f r o m D r .  but  Ltd.,  graphite) Parma,  University  Graphite)  of  of  Ohio, British  was p u r c h a s e d  from  - 70 -  The  HOPG  was  primarily  conductivity  studies,  tions.  obtain  To  intercalant,  2.7.2  used  to  synthesize GIC's  b u t S P - 1 g r a p h i t e was u s e d an  efficient  s m a l l amounts o f  mixing  graphite  sources w i t h t h e i r  table  lists  suppliers.  all  of graphite  electrical  other  and l i q u i d  reacphase  ( - 1 5 0 mg) w e r e u s e d .  Other Chemicals Obtained f r o m Commercial  The f o l l o w i n g  for  for  chemicals  Sources  purchased  from  commercial  Source  Remarks  A l l i e d Chemicals, M o r r i s t o w n , New J e r s e y  Doubly d i s t i l l e d  (2.6.2)  A l l i e d Chemicals, M o r r i s t o w n , New J e r s e y  M a t h e s o n o f Canada L t d .  98% p u r e , p a s s e d t h r o u g h NaF t o remove HF.  Mallinckrodt Inc. St. Louis, Missouri  A n a l y t i c a l reagent, stored o v e r P 2 O 5 t o remove m o i s t u r e a n d K B r t o remove Cl . 2  American S c i e n t i f i c Chemical, S e a t t l e  and  Reagent g r a d e , obtained.  u s e d as  Fischer S c i e n t i f i c New J e r s e y  Co.  Dried a t -70°C to any m o i s t u r e .  Fischer S c i e n t i f i c New J e r s e y  Co.  D r i e d as i n K I .  Matheson  o f Canada L t d .  remove  Passed t h r o u g h s i l i c a g e l (~-198°C) t o remove moist u r e and N 0 . 2  - 72 -  CHAPTER 3  SYNTHETIC REACTIONS  - 73 -  SYNTHETIC REACTIONS  General  Comments  All under  the synthetic  vacuum  reagents pounds  or  reactions  nitrogen  atmosphere c o n d i t i o n s .  a n d r e a c t a n t s was done i n t h e d r y b o x , were  transferred  from  distillation.  SP-1 g r a p h i t e  intercalation  reactions,  for  the products  synthesized solely  for  thus  from  (spectroscopic  weight percentage use o f for  a b o u t one h o u r  reaction  the  a  dynamic  d a t a were  intercalation  reactions analysis  the various  i n the r e a c t i o n s , in  r e a c t o r s b y vacuum  g r a d e ) was u s e d f o r  few  com-  all  the  obtained compounds  Graphite)  were  used  were  performed  values  shown  elements.  Prior  indicate to  t h e p o w d e r r e a c t a n t b u l k was  vacuum.  Magnetic  at  stirring  of  any dried the  m i x t u r e s was c a r r i e d o u t t o o b t a i n p h a s e h o m o g e n e i t y a n d h e n c e  an a c c e l e r a t e d reaction  all  for  volatile  of  measurements.  elemental  compositions  the graphite  all  into  Oriented Pyrolytic  conductivity  The  The  out  The m a n i p u l a t i o n  and X - r a y and m i c r o a n a l y s i s  (Highly  temperature.  and  vessels  synthesized.  HOPG  electrical  bulk  Unless otherwise mentioned, ambient  d e s c r i b e d i n t h i s work were c a r r i e d  intercalation  rate.  When  HOPG  m i x t u r e was k e p t u n d i s t u r b e d i n o r d e r  calated graphite  plates.  plates  were  to salvage  used,  intact  the inter-  -  3.1  Intercalation  The l 2 ( s o l v ) +  2:1.  w  a  I  s  (solv)  2  i  n  t  Graphite  o  p r e p a r e d b y u s i n g 1 2 and S 0 g F 2 , 2  6 . 0 m l o f H S O 3 F was u s e d as t h e r e a c t i o n m e d i u m ,  intercalant tion  of  stirred  a m o u n t was a b o u t was  I2SO3F  graphite.  At  of  74 -  t h e end o f  this  brown  period,  color.  The  i n a dynamic vacuum f o r  istic  metallic  blue  The i n t e r c a l a t e d two.  The d a r k  estimated  blue  solu-  the  reaction  tint,  the  suspension  intercalated  about  3 h.  grains  graphite  observed  g weight  showed s i z e  The s y n t h e s i s was r e p e a t e d f o u r  expansion by to  18 h . to  a  be then  character-  i n c r e a s e was  times  was  p r o d u c t was  The p r o d u c t h a d t h e  and a b o u t 0.468  graphite  was  g of  mixture  a n d t h e r e a c t i o n was a l l o w e d t o p r o c e e d f o r  time  in  and t h e  being  t h e n r e a c t e d a t room t e m p e r a t u r e w i t h 0.5123  dried  about  g (4.34 mmol).  To o b t a i n g o o d p h a s e h o m o g e n e i t y , magnetically,  reddish  1.530  the r a t i o  noticed.  factor  obtain  of  consistent  data. A similar but  p r o c e d u r e was f o l l o w e d  in  t h e s o l u t i o n m i x t u r e was a l l o w e d t o  t o k e e p t h e HOPG p l a t e s The c o m p o s i t i o n o f the microanalysis  Compound:  t h e c a s e o f HOPG stand without  intercalation,  stirring  in  order  agrees  with  intact. the product,  C32SO3F.3HS0 F.0•21, 3  results.  C32SO3F.3HS03F0-21  Microanalysis  data: Element  C  H  I  Calculated  47.5  0.37  3.14  Found  47.2  0.37  3.10  - 75 -  X-ray  d i f f r a c t i o n v a l u e s o f t h e s a m p l e s u g g e s t a compound w i t h a  layer  repeat distance  samples  (0.1746  I  g)  o f 7 . 9 9 ± 0 . 0 3 A.  were  were o b s e r v e d i n s i d e  Intercalation of  the  reactor.  The  the thermal decomposition  I(S0 F) 3  into  3  The c o n c e n t r a t i o n o f I ( S 0 F ) 3  o b t a i n e d were a n a l y z e d f o r  3.2.1  When  h e a t e d a t 200°C f o r 4 h ,  t h e one p a r t  t o be e x f o l i a t e d a f t e r  3.2  c  3  c-axis  intercalated  s m a l l amounts o f 1 2  HOPG  plates  appeared  process.  Graphite  i n H S O 3 F was v a r i e d ,  and t h e  products  composition.  High Concentration of  I(S0 F) : 3  (~1.20 M)  3  R e a c t i o n was c a r r i e d o u t u s i n g 4 . 1 0 3 g ( 9 . 4 4 3 mmol) o f l i g h t and  viscous  I(S03F)  as  3  the  d i s s o l v e d i n 8.10 ml o f H S 0 F 3  intercalant.  was  noted  3  solution,  immediately.  red t i n t .  and  all  the  The f i l t r a t e  2  the dry  3  h,  the  was  3  box.  0 . 5 2 3 g o f g r a p h i t e was  surface  of  of  had a green b l u e c o l o r .  the  solution  the  18 h .  product  The w e i g h t  The s y n t h e s i s was r e p e a t e d  p r o d u c t s were a n a l y z e d f o r  shown t o be C 2 I ( S 0 3 F > 3 .  inside  The r e a c t i o n was a l l o w e d t o p r o c e e d f o r  the g r a p h i t e had i n c r e a s e d by 0.7942 g. times,  3  and a green b l u e c o l o r  When d r i e d i n a d y n a m i c vacuum f o r appeared dark b l u e .  yellow  F r e s h l y made I ( S 0 F )  i n a two p a r t r e a c t o r  The homogeneous s o l u t i o n h a d a s l i g h t added t o t h e I ( S 0 3 F )  HOPG  composition,  of  four  w h i c h was  When HOPG p l a t e s w e r e u s e d , a b o u t f i v e  plates,  -  with  an  average  mmol)  of  I(S03F>3  for  the  weight for  of  76 -  0.0949  two d a y s .  g, were r e a c t e d w i t h  0.1765  g weight  observed  data:  Element  C  H  I  S  F  Calculated  38.37  0.0  18.46  13.95  8.28  Found  37.90  0.0  18.60  14.01  8.14  Mole r a t i o  powder  7.94 ± 0.03  1  data  indicated  solutions  a  c-axis  the product of  stoichiometric  of  I(S03F)  repeat  2.99  layer  :  2.93  distance  I  c  of  respectively.  I(S03F)3 amounts o f  3.3465  and  g  o f 0.395  For a t y p i c a l  between  concentrated  g r a p h i t e had a composition o f  I(S03F>3  (7.894  i n 2 0 . 0 0 ml o f H S O 3 F ,  a concentration  3  obtained from the r e a c t i o n  and g r a p h i t e  t h e p r o d u c t s were a n a l y z e d f o r  dissolved  :  A.  Low C o n c e n t r a t i o n s  Since  and  was  C22l(S03F>3  Microanalysis  3.2.2  increase  (8.589  products.  Compound:  X-ray  3.6411 g  carbon,  mmol)  of  C22l(S03F)3,  were r e a c t e d  in  hydrogen and i o d i n e freshly  and t h e s t o c k  made  solution  HSO3F, contents  I(S03F)  3  thus prepared  was had  M.  reaction  between  graphite  and  I(S03F)3,  (44C:0.5  - 77 -  I(S0 F) )), 3  0.1510  3  g of  graphite  and 0.0606  g ( 0 . 1 4 2 9 mmol)  w h i c h was o b t a i n e d f r o m 0 . 3 6 2 m l o f t h e s t o c k s o l u t i o n , react  in  observed,  a  two p a r t  reactor.  A blue-green color  color,  and t h e d r i e d p r o d u c t  3 h.  showed  a  The f i l t r a t e typical  was  I(S0 F) , 3  3  allowed  to  solution mixture  was  a n d t h e r e a c t i o n was a l l o w e d t o p r o c e e d f o r  was d r i e d i n a d y n a m i c vacuum f o r  of  24 h .  The  product  was b l u i s h g r e e n  metallic  blue  in  surface  lustre. The  following  mole r a t i o s  table  summarizes  o f c a r b o n and I ( S 0 F ) 3  3  in  the r e s u l t s ,  obtained for  various  HS0 F. 3  Table 3 . 1 :  Amount G r a p h i t e (g)  Amount I ( S 0 F ) (g) 3  0.1510  3  0.0606 (0.1429  0.2934  Mole r a t i o C:I(S0 F) 3  44:0.5  3  Elemental Analysis C H I*  47.48  0.35  0.0  73.33:0.3  47.74  0.34  0.0  27.5:0.8  47.43  0.27  0.0  mmol)  0.0424 ( 0 . 1 0 0 mmol)  0.1502  0.1544 (0.3642  I o d i n e was a b s e n t  mmol)  in all  the  samples.  - 78 -  3.3  Intercalation  In a typical with  0.7320  g  of K [ I ( S 0 F ) ] 3  synthesis, (1.302  K[I(S0 F) ]  was f i r s t  which  very  3  4  was  4  into  0.1145  mmol)  g o f g r a p h i t e was a l l o w e d  K[I(S0 F) ]. 3  light  green  yellow  When  HS0 F  and  3  color,  reactor.  the  the  p r o d u c t was f i l t e r e d  vacuum f o r  The p o w d e r  3 h,  i n vacuo, product  react  The  solution  a n d when c o m p l e t e l y d r y ,  the  mixture  18 h .  the f i l t r a t e  obtained  of  solution,  was t h e n a d d e d t o  a n d t h e r e a c t i o n was a l l o w e d t o p r o c e e d f o r  t o have a green c o l o r . dynamic  in  to  The c r e a m y w h i t e p o w d e r  4  d i s s o l v e d i n 6.0 ml o f  g r a p h i t e powder c o n t a i n e d i n a two p a r t turned green,  graphite  was  was  observed  dried  in  showed a m e t a l l i c  a  blue  color. The f o l l o w i n g c o m p o s i t i o n was o b t a i n e d f o r  the  sample  by  micro-  analysis.  Compound:  Cg I.10-51 6  S0 F. 3  Microanalysis:  Element  C  H  Calculated  46.92  0.0  Found  46.09  0.0  Mole  ratio  I  S  F  5.76  15.32  9.08  5.55  14.74  8.80  1  1.0  - 79 -  3.4  Intercalation of  For  a 3  3  golden yellow  Graphite  0.1502  g o f g r a p h i t e was u s e d t o 3  in  8.0  in color,  Total  ml o f HS0 F, 3  (4.5287 g;  react  2.015  mmol)  a n d t h e s o l u t i o n f o r m e d , w h i c h was  t i m e was 24 h a n d t h e  filtrate  i n a two still  surface  t h e s a m p l e was shown t o be C g 2  showed a b l u i s h t i n t .  part  had  The i n t e r c a l a t e d p r o d u c t was v a c u u m d r i e d f o r  and t h e powder p r o d u c t  C g  3  was a l l o w e d t o r e a c t w i t h g r a p h i t e  reaction  golden yellow c o l o r .  Compound:  into  The p a l e y e l l o w s o l i d B r ( S 0 F )  3  dissolved  reactor.  3  typical preparation,  with Br(S0 F) . was  Br(S0 F)  the 3 h,  The c o m p o s i t i o n  of  gBr.4S0 F. 3  gBr.4S0 F.  2  3  Microanalysis:  Element  C  H  Br  Calculated  40.33  0.0  10.02  9.53  Found  39.94  0.0  10.56  10.30  Mole r a t i o  1  X-ray d i f f r a c t i o n of  3.5  7.88 ±0.03  d a t a gave a GIC w i t h c - a x i s  3  a  layer  :  3.95  repeat  distance  I  c  A.  I n t e r c a l a t i o n of K[Br(S0 F)4"  In  F  typical  synthesis,  into  1.0325  Graphite  g  ( 2 . 0 0 5 mmol) o f w h i t e  creamy  80 -  powder K [ B r ( S 0 3 F ) ]  was d i s s o l v e d  4  golden  yellow  solution,  solution.  i n 6.0  0.1268  ml  of  The r e a c t i o n was a l l o w e d t o  take place  filtered  i n a d y n a m i c vacuum  filtrate  still  graphite  product  had  the  golden  Compound:  for  yellow  showed a d i s t i n c t  s a m p l e g a v e t h e c o m p o s i t i o n as  gave  g o f g r a p h i t e was t h e n a d d e d t o  a n d a s u s p e n s i o n o f d a r k b l a c k c o l o r was  i n vacuo and d r i e d  which  HSO3F,  blue  18 h .  formed  color,  tint.  this  immediately.  The p o w d e r p r o d u c t for  about  and  a  3  the  h.  was The  intercalated  The m i c r o a n a l y s i s  of  the  Cg Br.11.22.SO3F. 4  Cg Br.11•22S0 F. 4  3  Microanalysis:  Element  H  S  F  45.85  0.0  3.63  16.36  9.69  Found  45.63  0.0  3.63  16.42  9.68  ratio  Intercalation  For  a  of  typical  BrS0 F i n t o 3  preparation,  4 . 0 0 g ( 2 2 . 3 6 mmol)  B r S 0 3 F was a l l o w e d t o  react with  in  one  The  part  reactor.  B r S 0 3 F a n d t h e n t h e a c i d was distillation.  A  room t e m p e r a t u r e .  black-green  1  :  0.995  of  the  Graphite  liquid a  I  Calculated  Mole  3.6  C  0.1159  g ( 9 . 6 6 mmol)  amount o f H S O 3 F  transferred suspension  to  red-brown  of  u s e d was a b o u t  the  reactor  via  graphite 6.0  vacuum  was o b s e r v e d u p o n w a r m i n g  The m i x t u r e was a l l o w e d t o r e a c t  for  18  h,  ml.  and  to the  - 81 -  intercalated this  p r o d u c t was s e p a r a t e d b y v a c u u m d i s t i l l a t i o n  time p e r i o d .  A r e d d i s h brown f i l t r a t e  p o w d e r p r o d u c t was m e t a l l i c The  intercalated  f o l l o w i n g v a l u e s were  Compound:  blue  was o b s e r v e d ,  t h e end  and t h e  of  dried  color.  s a m p l e was a n a l y z e d f o r  its  composition,  and  the  obtained.  C HS0 F.0•5S0 F.x 1 1  in  at  3  3  BrS0 F.  (x <  3  0.025).  Microanalysis:  Element  C  H  Br  F  S  Calculated  46.16  0.35  0.69  10.13  17.10  Found  46.30  0.30  0.67  9.19  15.80  Mole r a t i o  The c - a x i s  layer  1  repeat distance  powder d i f f r a c t i o n  3.7  o f NOSO3F i n t o  For a t y p i c a l  synthetic  freshly  g ( 1 0 . 1 2 mmol) made,  were  transferred  of  1.02  as i n d i c a t e d  8.22 ±0.03  by  X-ray  A.  Graphite  reaction,  of white  0.1443  g ( 1 2 . 0 3 mmol)  solid crystalline into  a one p a r t  7 . 0 m l o f H S 0 F was t h e n d i s t i l l e d 3  t h e r e a c t i o n was a l l o w e d t o ture .  the sample,  gave a v a l u e  Intercalation  and 1.305  box.  data,  for  :  take place  N0S0 F, 3  reactor  i n vacuo i n t o  for  several  of  graphite  which  inside  the  the r e a c t o r ,  days a t  was dry and  room t e m p e r a -  - 82 -  The v o l a t i l e distillation.  products  For  this  from the r e a c t i o n were purpose,  thus  intercalated  collected  amounts o f  liquid  of  vacuum  N  2  dry  temperature.  t h e samples  c a r b o n and h y d r o g e n ,  and vacuum d r i e d f o r  (several  indicating  preparations) inhomogeneous  ice The  w e r e t h e n a n a l y z e d b y mass s p e c t r o s c o p y .  g r a p h i t e p r o d u c t was f i l t e r e d  Microanalyses  by  t h e r e a c t i o n t u b e was k e p t a t  t e m p e r a t u r e and the c o l l e c t i o n v e s s e l a t products  collected  The  3 h.  gave  varying  sample  composi-  tions .  Table  3.2:  Sample  Typical Microanalysis  Amount NO (mmol)  25.93  The  X-ray  data  Amount Graphite (mmol)  Reaction time  13.34  10 d  Composition C  H  N  67.49  0.28  0.0  70.62  0.0  0.0  15.20  12.07  18 h  69.30  0.20  0.0  43.49  12.03  10 d  76.0  0.30  0.0  77.0  0.16  0.0  diffraction  layer  repeat distance  gave  primarily  these spectra.  peaks  I  values c  obtained  showed a compound w i t h  = 1 0 . 5 9 ± 0 . 0 3 A. related  The a m o u n t s  of  to S i F . 4  carbon  The  mass  spectra  c-axis  analysis  NO c o u l d n o t be i d e n t i f i e d and  hydrogen  as  analyzed  in by  - 83  micro-analytical  methods,  time  or  concentrations  3.8  Intercalation  of  Approximately  3.50  reactant  dissolved  in  the  IB^SC^F  graphite  vacuum  was  filtered  following  Microanalysis  3.9.1  and d r i e d  reaction  Graphite  of brick  red  solid  graphite  the  in  solution  2 days.  a  two  blue  3  thus  was  f o r m e d was  part  reactor.  turned almost b l a c k .  The  The i n t e r c a l a t e d p r o d u c t  was  i n a d y n a m i c vacuum f o r  metallic  IBr2S0 F  color,  and  3 h.  The  dried  when  analyzed,  composition.  data:  of  Halogen  C  H  47.15  0.0  Fluorosulfates  Attempted Oxidation of  0.2697  of  go o n f o r  Found  Reactions  when t h e  The b l a c k b r o w n s o l u t i o n  added,  Element  3.9  into  significantly  changed.  g ( 9 . 0 7 mmol)  powder had t h e c h a r a c t e r i s t i c gave t h e  were  g ( 1 1 . 9 3 mmol)  r e a c t i o n was a l l o w e d t o then  not vary  7.0 ml o f H S O 3 F .  mixed w i t h 0.1432 When  did  -  K[I(S0 F)4] 3  g o f K [ I ( S 0 3 F J 4 was t r a n s f e r r e d  to  a one p a r t  reactor  inside  -  the dry box, into  the  mixture any  and 6 . 0  same  ml o f H S O 3 F  reactor.  change.  and excess S 2 0 g F 2  Magnetic  was  detected,  bath,  temperature  r e a c t i o n allowed to proceed f o r  one  and  S20gF2  dynamic vacuum f o r  o b t a i n e d as a p r o d u c t .  3.9.2  room  raised  3  4  no  90°C,  and  color and  and a v i s c o u s  w i t h Excess  the  the  excess  The r e a c t o r was k e p t red colored  The r e a c t i o n was m o n i t o r e d b y  Reaction of K [ I ( S 0 F ) ]  Since to  temperature  were removed v i a vacuum. several hours,  18 h .  day.  The r e a c t o r was t h e n c o o l e d t o HSO3F  was  5 h did  reaction  The r e a c t o r was t h e n h e a t e d u s i n g a w a t e r a t 75°C f o r  for  the  give  the  stirring  distilled  not  a n d t h e t e m p e r a t u r e was k e p t c o n s t a n t change  were vacuum  Upon w a r m i n g t o room t e m p e r a t u r e  showed a y e l l o w c o l o r .  observable  84  Br  under  liquid  was  weight.  2  R.T. K[I(S0 F) ] 3  +  4  excess B r  >  2  2 BrS0 F 3  +  K[IBr (S0 F) ] 2  3  2  2 days  Approximately  0.6322  g K[I(S03F) ]  was a d d e d t o a one p a r t  4  a n d e x c e s s B r 2 was t h e n v a c u u m d i s t i l l e d brick  red  color  was  2 d a y s a t room  The v o l a t i l e  of  volatile(s) brown  and  byproducts  in color  brick  red.  and c r y s t a l l i n e ,  A  dark  The r e a c t i o n was  temperature.  t h e r e a c t i o n were c o l l e c t e d  were a n a l y z e d by  was s t i l l  t h e same v e s s e l .  observed i n the r e a c t i o n tube.  allowed to proceed f o r  distillation  into  reactor,  The c o l o r  vacuum  observed f o r  the  The s o l i d p r o d u c t ,  w h i c h was l i g h t  red  was a n a l y z e d b y I . R .  Spectroscopy.  The  1 9  F-NMR.  via  -  85  r e a c t i o n was f o l l o w e d b y w e i g h t as w e l l .  3.9.3  Reaction of  I(S0 F) 3  3.4699 was  allowed  g of to  3  I(S0 F) 3  +  3  w i t h Excess  excess B r  I(S0 F) , 3  react  3  2  >  Br  2  IBr S0 F 2  w i t h excess B r  l i q u i d was o b s e r v e d .  u n d e r a dynamic vacuum f o r product  o b t a i n e d was s t i l l  2BrS0 F 3  2  a t room t e m p e r a t u r e (-65°C)  for  48 h w h i l e b e i n g  kept  a dark red very viscous liquid N  2  at  5 h.  about  liquid,  2 days. A  and  weight.  dark  evacuated 0°C.  temperature  The r e a c t i o n was f o l l o w e d b y  reactor,  for  The r e a c t i o n v e s s e l was t h e n  t o o b t a i n a s o l i d p r o d u c t by c o o l i n g a t p r o v e t o be s u c c e s s f u l .  +  w h i c h was f r e s h l y made i n a one p a r t  The r e a c t o r was t h e n h e a t e d u s i n g a w a t e r b a t h red viscous  3  The  attempts did  not  - 86 -  CHAPTER 4  RESULTS AND DISCUSSION  -  87  RESULTS AND DISCUSSION  General  Comments  This results  chapter  is  presented  maintain a logical  intended  to  i n the previous sequence,  rationalize sections  the chapter  of  is  the  this  divided  observations  thesis. into  I n order  the  and to  following  subsections:  4.1  Intercalant  Preparation  in  Fluorosulfuric  A c i d and  Related  Studies  The s y n t h e s i s intercalants discussed.  and t h e i r In addition  miscellaneous to  Solution considered,  reactions  of  intercalation  and t h e  results  are  are  I  reported reactions  ,  and  I(S0 F) , 3  discussed.  3  used  as be  properties,  of halogen f l u o r o s u l f a t e s ,  Containing  + 2  are  in HSO3F will  t o be i n c l u d e d i n t h i s  Iodine  of  species which  and c h e m i c a l b e h a v i o u r  to previously  chemistry,  Intercalation  fluorosulfate  physical  attempted  intercalation  4.2  of various  pertinent  section.  Species  K[I(S0 F) ] 3  4  and  IS0 F 3  is  -  4.3  Intercalation  The  following  discussed:  4.4  A  BrS0 F,  compounds a n d t h e i r  comparative  3  (N0 ) +  study  solvents w i l l  of  3  be  and  in  3  intercalation  +  be made i n t h i s  Preparation  2  Promoted I n t e r c a l a t i o n  N 0  are to  IBr S0 F.  4  G e n e r a l Comments o n H S 0 F a n d  Intercalant  Compounds  intercalated products  K[Br(S0 F) ],  3  NItrosonium Ion  4.5  Bromine C o n t a i n i n g  Br(S0 F)3,  3  non-protonic  4.1  of  88 -  of  in  S0 F~ 3  HS0 F 3  section.  Conclusion  in Fluorosulfuric  A c i d and R e l a t e d  Studies  Section A  The containing a)  system  allows  l2"S20gF2  one t o  generate  the  following  iodine  species:  Solvated ions possibly  l 5  +  formed i n  with non-integer  ,  strong protonic stabilize  I  existence  of  + 2  strong protonic  i  I$ +  acids hut  oxidation  available, on  in this  acids  HSO3F  account medium i s  of  is its  s u c h as l 2  states  of  .  iodine.  sufficiently oxidizing  questionable.  +  I 3  +  and  Of  the  acidic  to  ability  the  -  b)  Binary  fluorosulfates  formed i n  t h e absence o f  like  I3SO3F  will  concentrate  K[I(S03F) ] 4  to  the other  4.1.1  I  l 2  and I 7 S O 3 F  is  on  also  iodine, acid.  color  Other b i n a r y ,  and  ISO3F  I(S03F)3.  i n c l u d e d as a p o t e n t i a l  two b i n a r y  iodine 7  1 0 6  which  rich but  species  this  Finally,  intercalant  are  study ternary  in  addition  fluorosulfates.  c a n b e s t be g e n e r a t e d r e a s o n a b l y and M i l n e .  i n s o l u t i o n and an o p t i c a l  addition  magnetic  susceptibility  s p e c t r a are used i n the l2 (solv),  the  +  2:1,  and I ( S 0 3 F ) 3 ,  ISO3F  have been i d e n t i f i e d , " * '  by the method r e p o r t e d by G i l l e s p i e blue  i.e.  (solv)  + 2  ions  +  of  89  since  mole  study of ratio  In addition  to  of  quantitatively  The i o n h a s a n  7 2  spectrum  can  measurements  these  be  and  species. *'  HSO3F intense  obtained. resonance  For  9  the  In Raman  synthesis  has t o be m a i n t a i n e d c l o s e  l2:S20gF2  the p r i n c i p l e  in  of to  reaction  HSO3F  2I  other  cations  formed, ^2°6 2 F  +  a  t  r  (Fig.  the l 3  S 0 F  of  iodine  either o  o  sharp peaks l 2  +  2  +  6  > 2I  2  1  by the o x i d a t i o n  i n the o p t i c a l  of  (  s  o  lv)  +  excess  spectrum at  2 s  species  of  640, 490,  to:  F  I(S03F)3  can  o r b y t h e use o f  300 nm i n t h e  formed according  °3 "(solv)  like  iodine  Absorption studies  The s m a l l p e a k a t  which i s  + 2  s u c h as I 3 " " o r  temperature.  m  4.1).  ion,  2  l2 (solv) +  &i-  v e  be  excess three  a n d 410 nm, a s s i g n e d  to  2:1 solution  to  is  due  - 90 -  Figure 4.1:  Absorption Spectra of 1:1 and 2:1 I / S 0 F 2  2  6  2  Solutions: A ,  2:1 I / S 0 F ,  - 0.164, path length - 0.005 cm;  2:1 I / S 0 F , mj  - 0.372, path length - 0.01 cm; C, 1:1  2  2  2  2  6  6  2  2  I / S 0 F , mj 2  2  6  2  - 0.0186, path length - 0.01 cm.  from reference 72.  B.  - 91 -  8 I  However, l 3  +  at  the  the  presence  + 3  +  5S0 F"  +  3  I(S0 F) 3  3  e q u i l i b r i u m p r o d u c e s o n l y v e r y s m a l l amounts Therefore,  solution  I2/S2O6F2  4.1.2  of  it  c a n be s a f e l y  assumed  i s p r e d o m i n a n t l y made up o f low  13"*",  concentrations  l 2  were  +  that  ions.  used  of  in  To the  synthesis.  ISO3F  Iodine(I) (1:1.05) heated  fluorosulfate  amounts o f to  60°C  composition I S O 3 F readily  to  form  spectrum o f  ISO3F  diamagnetic,  to  this  lower concentrations.  preparative  is  5I  8SO3F*  in H S O 3 F ,  2:1  avoid  +  +  2  a very  synthesized  I 2 and S 0 g F 2 . " 7  2  for is a  -1  h,  blue  When t h e  When a d d e d  color  to  s o l u t i o n due t o l 2  shown i n F i g .  and h y g r o s c o p i c ,  for  the reactions  hydrolyzed,  some l 3  +  equimolar  crude product  HSO3F,  4.2.  +  ions.  solutions  of  it  with graphite.  green s o l u t i o n s  The  Since  are  the  of  optical  the  observed  be  compound  in HSO3F If  is  dissolves  ISO3F ions.  solid  I S O 3 F was f o u n d t o 7  be u s e d i m m e d i a t e l y  nearly  initial  i n d i c a t i n g covalent bonding. "*  strong oxidizer  become e v e n p a r t i a l l y  f  using  a dark b l a c k i s h brown h y g r o s c o p i c  obtained.  in H S O 3 F is  thereby  the formation of  is  had  samples due  to  -  Figure 4.2:  92  -  Absorption Spectrum of IOS0 F Dissolved i n Fluorosulfuric 2  from reference  74.  -  4.1.3  I(S0 F) 3  3  Iodine(III) excess  of  is  highly  a  yellow  S20gF2.  fluorosulfate 7  3  3  groups The  the  the presence  F-NMR  ionizations  in  +  3  I(S03F)  3  structure.  (Table 4.1)  an  product of  light  disproportionates  3  3  shows  amphoteric  as a b a s e .  spectrum o f  2  +  3  behavior  3  absorption  maximum  However,  shorter  is  in  3  +  HSO3F  observed  wavelengths,  maximum o f w h i c h h a s n o t b e e n  interpreted monodentate  HS0 F,  SO3F"  are  +  +  reported.  observed and  acidic  follows:  S0 F" 3  3  pale  is  of  ** T ( S 0 F ) "  ,  yellow  i n the o p t i c a l there  is  The b a s i c  9 4  2  capable  3  resonance  3  I(S0 F)  I(S03F)3  in  in HS0 F.  3  3  3  and  a c i d c a n b e r e p r e s e n t e d as  3  3  3S0  bridging  Only a s i n g l e  I(S0 F)  fluorosulfuric  behavior:  3  9 5  Acidic  at  with  2  and t h e  has been r e p o r t e d and  3  I(S0 F) ^z=r-^I(S0 F)  of  I(S0 F)  IF (S0 F)  Basic behavior:  Solutions  solid  of both bidentate  i n a polymeric  compound  1 9  a low m e l t i n g  IS0 F  liquid  r e a c t i n g as an a c i d o r in  exothermic,  50°C i n v a c u o ,  >  3  Raman s p e c t r u m o f  as i n d i c a t i n g S0 F  or  is mildly  I  9 3  2I(S0 F)  The  liquid  When h e a t e d t o  approximately:  can be s y n t h e s i z e d b y r e a c t i n g  The r e a c t i o n  3  viscous  color.  93 -  a  4  in  color  s p e c t r u m above  strong  and  no  300 nm.  absorption,  the  -  Table 4.1:  94 -  S e l e c t e d P h y s i c a l P r o p e r t i e s o f Some Halogen F l u o r o s u l f a t e s *  BrSOiF  CISO3F  melting p o i n t (*C)  +31.5  -84.3  b o i l i n g p o i n t (*C)  +117.3  +45.1  Property  density (g/ml)  2.238 @ 25'C  16.98  vapour pressure at 25*C (Torr)  s t a b i l i t y and color  F NMR chemical s h i f t r e l . t o CFC1 (ppm)  red l i q u i d s t a b l e up t o 150*C  ISO3F  +50.2  Br(S0 F) 3  3  +59.0  KS0 F) 3  3  +32.2  +114 @ 30 T o r r under decomp.  1.711 @  2.40 <? 25*C  20'C  363.1  yellow liquid  black-brown s o l i d , stable upto 150*C  pale yellow s o l i d , slowly decomposes a t room temp.  pale yellow s o l i d , or a high viscous l i q u i d slowl y decompose et room temp  1 9  3  from reference 93.  34.6  33.9  44.0  39.0  47.0  - 95 -  4.1.4  K[I(S0 F) ] 3  and  4  K[Br(S0 F> ] 3  4  The p r e p a r a t i v e m e t h o d f o r b o t h compounds r e p o r t e d Cady This  is  7 6  the  synthetic  oxidation route  is  of  rather  original  synthesis  solvent The  are o b t a i n e d .  impractical  I n order  at  the  as  the  solvent  reactions  least  the  2  proceed before  reaction,  the  amount o f H S 0 F as  the  3  as d e s c r i b e d i n  for  and  S 0gF2.  a f e w weeks  to accelerate  i s m o d i f i e d by adding a small 2  acts  since  require  t o g e t h e r w i t h excess S20gF ,  acid  Lustig  K I o r KBr b y a n e x c e s s amount o f  i n a h e t e r o g e n e o u s phase and u s u a l l y pure products  by  Section  2.6.7(b).  t h e two p r o d u c t s K [ I ( S 0 F ) ] 4  and  hours,  and  3  K[Br(S0 F) ). 3  4  The o x i d a t i o n p r o c e s s r e a c h e s c o m p l e t i o n w i t h i n a fine  crystalline  products  few  c a n be i s o l a t e d b y r e m o v i n g t h e e x c e s s  HS0 F 3  a n d S20gF2 i n a d y n a m i c v a c u u m . K[I(S0 F) ] 3  yellow  and K [ B r ( S 0 F ) ]  4  3  solutions  respectively. t i o n s were used So  far,  due  4  to  For the s y n t h e t i c  dissolve  the  anions  no  solution studies  of  similar.  1500 c m "  - 900 c m "  with tively  is  graphite,  as  and K [ B r ( S 0 F ) ] 3  Br(S0 F) " 3  these  4  solu-  suggest t h a t a l l monodentate  four  conclusion.  S0 F groups  i n bonding.  3  Also,  suggested i n both K [ I ( S 0 F ) ] 3  i n the region are  4  and  identical  a s i n g l e band  found at -835 c m "  A square p l a n a r environment  is  1  for  I  K[Br(S0 F) ]. 3  been  are known,  4  Three S-0 s t r e t c h i n g v i b r a t i o n s  9 6  1  4  t h e S-F s t r e t c h i n g v i b r a t i o n  this  and  4  pale  3  very  buted to  3  giving  t h e s e compounds i n H S 0 F h a s  are  3  described  3  immediately.  Raman s p e c t r a o f K [ I ( S 0 F ) ]  best  i n HS0 F,  I(S0 F) "  reactions with  reported.  1  readily  4  of and  attri-  consistent  and Br 9 6  and  respec-  -  96 -  Section B  As i n  the  compounds  of  synthesis bromine  system B r 2 - S 2 0 g F 2 compound  such  species  c o n t a i n bromine  4.1.5  Br(S0 F)  has  to  is  2  +  resulting  p r e s u m e d t o be  structure  in  2  in  light  yellow  solid  The  fluorosulfate  as  to  6  7  be  well,  ternary  IB^SC^F  since  both  are  these  >  2  the  it  u s i n g B r 2 and an  3  very moisture since  synthesized  2Br(S0 F) 3  sensitive  tends  formation  3  solid  compound  t o decompose s l o w l y  of  a  red  colored  t h e compound shows s t r u c t u r a l  state,  and  suggests  both Br(S0 F)3  and  KSC^F^.  3  Br(S03F>3  acid.  the  at  and room  product,  BrSG^F.  the  for  can  excess S 0 F  The Raman s p e c t r u m o f I(S03F>3  similar  compositions.  according  S20gF2  used immediately  temperature,  section  their  a pale yellow,  be  fluorosulfuric  interhalogen  fluorosulfate  Br  Br(S03F>3  fluorosulfates,  3  Bromine(III) amount o f  the  in this in  iodine  as BrSC^F a n d B r ( S 0 3 F > 3 c a n b e made b y  and  4  i n c l u d e d as i n t e r c a l a n t s  excess  binary  i n t h e absence o f  K[Br(S03F) ]  3  of  dissolves  in color.  readily  in HSO3F,  The U V - v i s i b l e  a  SO3F  similarity  bridged  with  associated  9 6  and t h e r e s u l t i n g  spectra of B r 2 : S 2 0 g F 2  solution at  is  various  -  ratios of  in HSO3F  the band a t  the  0.33  which r e l a t e s  acid,  corresponding  a shoulder to  It  9 2  ratio, at  the  formation  appears  tive  however,  that  during  In a super-acid as a n o n e l e c t r o l y t e ,  Br(S0 F) 3  4.1.6  3  the B r 3 to  Br3  shoulder  of  at  sufficiently  the  increases the  at  curve  S20gF2:Br2 no  quite is  in  in  to  B is  of  change  3, is  fluorosulfuric  observed.  differentiated  at  inten-  ratio  further  stable  intensity until  375 nm d e c r e a s e s  until  is  3  Br2,  formation,  +  Br(S03F>3,  Br(S0 F)3  of  cation,  +  disproportionation  are not  conclusions  the  On o x i d a t i o n  310 nm i n c r e a s e s  a n d no a p p r e c i a b l e  spectra  4.3  375 nm, a s s i g n e d t o  Above t h i s  but  noted.  shown i n F i g .  ratio,  observed. sity,  is  97  UV-visible  allow  quantita-  intercalation.  system l i k e but  SbF -3S03-HS03F,  functions  +  H S0 F 2  Br(S03F>3  5  as a  base:  >  +  3  does n o t  act  9 7  Br(S0 F) 3  +  + 2  2HS0 F 3  BrS0 F 3  An  exactly  synthesize sealed  pure B r S 0 3 F ,  pyrex  tube  reducing agents deep  red  of  a red brown  7  up t o  150°.  color.  Pure  It  Br2  liquid, is  for  vapor  pressure  transfer  in  a n d S20gF2 i s thermally  extremely  w h i c h cause  BrS03F  melts  of vacuo  the in  peak liquid a  it  -31.5°C at  35  (-17  grease  to  to  Torr  in  to a  moisture,  darken  and t h e ppm  free  required  stable  sensitive  grease,  t h e compound shows a s i n g l e  The  sufficient  7  mixture  and f l u o r o c a r b o n  brown  spectrum o f CFCI3.  equimolar  to 1 9  a  F-NMR  relative  to  at  is  line  25°C) to  avoid  - 98 -  Figure  4.3:  UV a n d V i s i b l e B,  1:0.33;  Spectra  C, 1 : 1 ;  from reference  97.  D,  in H S O 3 F . 1:3  and  Br :S 0 F 2  1:5.  2  6  2  ratio:  A,  1:0;  -  99 -  contamination. BrSC^F solutions,  dissolves  well  in  fluorosulfuric  and i n c o n d u c t o m e t r i c  conductivity  is  electrolyte.  As c o u l d b e s e e n f r o m F i g .  in  S2O5F2  but  assumed  the  that  and B r ( S 0 F ) 3  showing  approaches  HSO3F  intensity, be  observed,  studies,  unity,  is  HS0 F-3S0 -SbF5 3  3  cations:  increase  acid.  indicate  brown  in  the  BrSG^F b e h a v e s as a v e r y  weak  4.3,  when  the at  decreases.  +  stable  to  ratio  of  Br : 2  310 nm i n c r e a s e s  Therefore,  it  some e x t e n t  into  in  could Br3  +  9 7  data of  the  BrS03F i n t h e  presence  of  super  both B r  + 3  acid  and  Br  + 2  9 7  5BrS0 F 3  4BrS0 F 3  4.1.7  slight  the shoulder  Raman s p e c t r a a n d c o n d u c t o m e t r i c system  give  disproportionated  in fluorosulfuric  3  that  375 nm p e a k o f B r 3 BrS03F  a  acid to  +  2H2S03F+  +  -  H2S03F+  * 2Br  „  » Br  +  + 2  Br(S0 F) 3  +  + 3  Br(S0 F) 3  +  3  3  +  4HSO3F  2HSO3F  NOSO3F  Nitrosonium between 230°C.  N 0 ( g ) and S 0 g F  7 9  with K S O 3 F The  fluorosulfate, 2  The compound i s  2  NOSO3F,  to give a white rather  crystalline  a c i d a n d b e h a v e s as a s t r o n g ,  unit  material  and  appears  of  isostructural  cell.  is very  extensively  reaction  solid with a melting point  hygroscopic  i n h a v i n g an o r t h o r h o m b i c white  i s best prepared by the  soluble  in  fluorosulfuric  d i s s o c i a t e d base a c c o r d i n g  to:  - 100 -  HS0 F 3  N O  S0 F  >  3  N0  +  + (  £  o  l  v  )  S0 F3  (  s  o  l  v  )  The Raman s p e c t r u m o f N 0 S 0 F i n H S 0 F shows a s t r o n g a b s o r p t i o n a t 3  cm" ,  attributed  1  t o t h e N-0 s t r e t c h i n g v i b r a t i o n  in N0  ion.  +  The c o m p l e t e d i s s o c i a t i o n o f N 0 S 0 F i n H S 0 F i s u s e f u l 3  the synthetic  reactions with graphite.  expected  oxidize  to  Insertion of other  4.1.8.  the  graphite  i o n s and n e u t r a l  2  In solution, lattice,  N0  ions  to  could  be  facilitating  the  +  thereby  i n regard  molecules.  3  a r u s t brown s o l i d product most o f  the  sensitive follows  and  best  3  i s reacted w i t h f r e s h l y prepared  of composition IBr S0 F 2  stored  2  is  +  thermally  complex  structure  perturbed.  IBr S0 F  solutions, s t r o n g base.  2  and  X  is  3  formed.  IX S0 F 2  X -  3  7 5  extremely  under atmospheric p r e s s u r e .  >  2  is  3  IBr S0 F  the general a d d i t i o n r e a c t i o n according  3  IBr S0 F  2  interhalogen fluorosulfates,  IS0 F  a  3  9 8  IBr S0 F  When a l a r g e e x c e s s o f B r  2  2320  3  3  like  According  a  S0 F" 3  dissolves other to  in  The  Like  9 9  to:  C I , Br o r  I.  indicate strongly  3  3  '  synthesis  i o n where C y symmetry i s HS0 F  3  moisture  s t a b l e u p t o 90°C a n d Raman a n d I R s p e c t r a with  IS0 F,  readily  to  interhalogen  fluorosulfates,  conductometric  measurements,  give  stable  b e h a v e s as a IBr S0 F 2  3  is  -  completely  dissociated  to:'-  101 -  5  HSO3F  IBr S0 F 2  The  1 9  F-NMR  single  bands,  IBr  of  +  (  2  o  should  i ) v  are  IBr S0 F 2  X  m a x  +  + 2  (  s  o  in  3  l  v  )  dissociation  values  of  Hence, as  it  was  3  F -  and  acids  s  o  l  v  )  acid give S0 F"  455  that in  only  a  formation.  3  spectrum,  intercalant  (  show d i s t i n c t  560 ( s h o u l d e r ) ,  anticipated  an o x i d a t i v e  S 0  fluorosulfuric  observed i n the e l e c t r o n i c  ions.  function  I B r  in strong protonic  3  3  s  of  IBr S0 F  nm  >  indicating  and i n HS0 F,  232 2  spectra  resonance,  Solutions  and  —  3  absorption  (shoulder),  361  corresponding  IBr S0 F 2  in  3  to  HS0 F 3  the r e a c t i o n w i t h  gra-  phite .  4.1.9  Attempted Oxidation of  The  reaction  fluorosulfuric one d a y )  between  acid  i n order  K[I(S0 F) ]  was  3  4  excess  S 0gF 2  carried out  to oxidize  the  (at  latter  and  2  75°C f o r  K[I(S0 F) ] 3  18 h a n d a t  compound a c c o r d i n g  4  90°C  in for  to:  HS0 F 3  K[I(S0 F) ] 3  It  4  has been r e p o r t e d  oxidation, observed. ^ 7  +  that  excess S 0 F 2  6  >  2  solid K[I(S0 F) ] 3  4  is  a n d when e x p o s e d t o a s t r e a m o f F The e a s e w i t h w h i c h i o d i n e  is  2  K[I(S0 F) ] 3  stable at  6  towards  further  1 0 0 ° C , no r e a c t i o n was  oxidized  i n HS0 F from 3  -1  to  -  +3 s u g g e s t s ture  further  oxidation  and p r o l o n g e d r e a c t i o n  species  of  the  be r e c a l l e d IF (S0 F) 3  that  2  The  removal  of  viscous  red l i q u i d .  during  the  that  time  n  1 2 is  to obtain either  to  give  Reaction of  This  all  the  However,  excess a c i d and S 2 O 5 F 2  an o v e r a l l  weight  From t h e s e o b s e r v a t i o n s ,  Q*M>  4  it  has  It  the  i )  or  v  should  compound  3  highly  was  observed  t o be  concluded  K[I(S0 F) ]  did  6  reaction  K[I(S0 F)4" 3  is  w i t h excess  unprecedented.  Br  not  take  It  2  is  performed  the r e a c t i o n between i n t e r c a l a t e d  [I(S03F) ]"  may  some  nature  give  i n the  indication graphite  regarding  the  K[I(S0 F) ] 3  4  +  excess B r  R 2  '  T  -  >  Infrared  stretching  K[IBr2(S03F) ] 2  at  1225 c m "  1  +  3  the  which  intercalants  K[IBr (S03F) ] 2  and t h e d i f f e r e n c e  as a p o s s i b l e  s p e c t r a o b t a i n e d on  frequencies  of  and B r 2 ,  to  follows:  2 BrS0 F  The r e a c t i o n was m o n i t o r e d b y g r a v i m e t r y suggests  4  i n order  lattice.  The r e a c t i o n was e x p e c t e d t o p r o c e e d a s  However,  o  yielded a  decrease  understand  weight  s  anticipated.  4.1.10  present  tempera-  4.1.3).  3  as  elevated  [I(S03F)g]"(  o x i d i z e d b y S20gF2 i n o r d e r  synthesis.  at  s h o u l d S O 3 be e l i m i n a t e d .  n  t h e presumed r e a c t i o n K [ I ( S 0 F ) ]  place  -  t o +5 may be p o s s i b l e  [IF (S03F)g_ ]"  (see S e c t i o n  9 3  3  type  102  the  product  solid  a n d 1060 c m "  1  2  observed  i n the  product(s) respectively,  in  synthesis. show  S-0  suggest-  -  ing a nearly  ionic  interhalogen  fluorosulfate  showed  different BrSC^F  IBr S03F.  deviation  4.1.11  I(S0 F) 3  The a b o v e  5 h).  3  3  +  products  and excess B r  were (at  2  above s y n t h e t i c  general  reaction  IBr S03F 2  of  Br  +  X  2  The d a r k r e d v i s c o u s  at  no  F-NMR values  for  BrS03F  to  fluorocarbon  2  of  >  2  +  3  for  the  for  the  different IS03F,  solid  the  vola-  significantly  ppm),  grease,  IBr S0 F  made d u r i n g  the  of  but  this  since  observed  well.  Br£  room t e m p e r a t u r e  to  of  g r e a s e c o n t a m i n a t i o n as  excess  2  (34.6  9 3  anticipated  in a  presence  2BrS0 F 3  reaction  2 days and a t  preceding  to y i e l d  65°C  reaction,  to prepare  manner  between  from  IBr SC>3F,  7 5  2  for the  the  interhal-  the  original  as p a r t  of  a  reaction:  ISO3F  but  1 9  r e a c t i o n was a t t e m p t e d i n o r d e r  ogen f l u o r o s u l f a t e  the  45 a n d 62 ppm, w h i c h w e r e  with  3  excess B r  Based on o b s e r v a t i o n s  addition  compound.  sensitive  I(S0 F)  with  The r e d b r o w n c o l o r  7 5  i n NMR d a t a c o u l d b e due t o  Reaction of  I(S03F)3  this  t w o weak p e a k s a t  extremely  consistent  2  from the expected value  is  -  group which i s  SO3F  p r o d u c t may a l s o be due t o tiles  103  s o l i d product  liquid N  2  >  IX S0 F 2  3  X -  l i q u i d was i n i t i a l l y  CI,  Br o r  assumed t o  I  be  c o u l d be i s o l a t e d even by s u p e r c o o l i n g  temperature.  IBr SC>3F, 2  the  liquid  - 104 -  UV-visible -  4.19  x 10"  s p e c t r a o f t h e p r o d u c t were o b t a i n e d f o r moles/kg i n f l u o r o s u l f u r i c  3  concentrations  a c i d and t y p i c a l l y ,  s o l u t i o n s were o b s e r v e d , w h i c h i n d i c a t e d the presence o f The c o l o r assumed  to  is  be  m a x  .  The c  m a x  c  1273  490  0.311  429  395  0.420  579  for  of I  into  + 2  Br . 2  ratio  1  L)  -1:3  Hence,  The  (see  oxidizing ability,  mole"  1  species  generally  graphite  is  optical  the  Intercalation  is  5  t h e 635 a n d 490 nm p e a k s i s - 1 : 3 , w h i c h i s  Intercalation of  It  7  and  HSO3F,  (cm"  0.923  excess  4.2.1  m a x  635  in HSO3F  1 9  by G i l l e s p i e  and M i l n e .  Iodine  of  Containing  value the  I(S03F)3  showed t w o r e s o n a n c e s  o u t B r S 0 3 F as a p o t e n t i a l  at  product.  Species  l2 (solv) +  acknowledged t h a t Sec.  7 2  the r e a c t i o n between  F-NMR o f the v o l a t i l e s  4 4 . 1 6 a n d 4 9 . 7 2 ppm, w h i c h r u l e s  4.2  in  2  Typical data from  Absorbance  p r o d u c t o b t a i n e d seems t o b e l 2 B r S 0 3 F f o r and  cation  +  I B r S 0 3 F .  blue  follows:  (nm)  ratio  obtained  o f the l 2  formed by s o l v e n t o x i d a t i o n .  s p e c t r a w e r e as  A  characteristic  pale  1.8.1).  then the s t r o n g l y  If  I 2 itself this  will  I s due t o  oxidizing  l 2  +  not  intercalate  the r e l a t i v e l y  would o f f e r  a  low  better  -  chance  of  At S 0gF 2  iodine low  contains  disproportionation reaction with place  is  graphite  visually product  lattice  by  the  surface  a  solution  predominantly  observed. is  in a relatively  the graphite  -  intercalated.  concentrations,  in HSO3F  2  being  105  by I  time  (18 h ) ,  solution.  + 2  metallic  and by t h e  the  I  + 2  molar ions,  + 2  Therefore,  most l i k e l y  short  I  of  tint  swelling  of  and  7 2  2:1 in  I  very  little  the o x i d i z i n g  species  (solv)•  reaction  ^  indicating  observed the grains  e  a fast  Intercalation  blue  ratio  to  in  the  takes  oxidation  was a l s o  on t h e  to  2  of  confirmed  dried  a factor  graphite of  about  two. Interestingly, t h e end o f I  18 h showed  2 (solv)  has  +  color.  This  could  a  2 (solv) +  I  +  a  gives s  +  additional  analysis  intercalation  particular tion  of  the  SO3F"  This  l3 ( olv)> +  S  n  is  at  HSO3F  suggests  which  >  2 I  that  brown  in  3 (solv) +  the  reddish  suspension remained blue evidence  data of  that the  content,  and n e u t r a l  also HSO3F  a  color  the  This  role  of  a compound  with  synthesis.  the product  with  brown  in color.  confirms  indicate  The c a r b o n p e r c e n t a g e  compound  low i o d i n e groups  "  agent d u r i n g  formula C 3 2 S O 3 F . 3 H S O 3 F . 0 •21. an  e  and t h e  *-he o x i d i z i n g  The e l e m e n t a l  to  to  *  +  color.  s o l u t i o n was a d d e d ,  + 2  n o t be d e t e c t e d ,  *2 (solv)  brown  and l 2 ( s o l v )  c a n be shown a s :  when e x c e s s  observation  reddish  graphite  been reduced by g r a p h i t e  3 I  However,  the suspension of  low stage  value  of  index.  47.2  The d a t a ,  suggest p r e f e r e n t i a l molecules.  It  points  appears  in  intercalathat  this  -  synthesis  follows  intercalate In not  these  amount o f  retained  in  information  with  intercalated graphite  regarding  of  acids  an e x t e r n a l  the e x t e r n a l  together  i n the  -  where p r o t o n i c  the presence  systems,  intercalate  small is  only  precedents  106  iodine  but  the o x i d a t i o n  (e.g.  intercalant  suggests  lattice,  oxidizing  oxidizer  the other  s u c h as H 2 S O 4  state  of  agent.  Cr03)  the  HSO3F  3 5  '  3 6  usually  species.  some o f  little  or  does  The  very  oxidizing  agent  can be deduced f r o m iodine  in  the  this  intercalant  layers. The l o w s t a g e from  the  the value  HS0 F-20%  S0  3  1 9  environment graphite the  F-NMR of  free  The  solid  not  ated S O 3 F " spaced  and  the  to higher  state  1 9  to  a  and H S O 3 F ,  I  in  (lower  field  7.99  A agrees  is  the  intercalation  typical  for  of  graphite  acid molecules  adsorbed  are  the  chemical  or  condensed  those  formed  give  typical  frequencies). C32SO3F.3HS0 F.0•21  4.4).  due t o  exhibits  3  This value  to  C F C I 3 .  to d i f f e r e n t i a t e  37.4  to  compounds  as c o m p a r e d w i t h  resonances  been observed a t  of  which are c l o s e r  intercalated  technique  inferred  determining  a t 4 0 . 6 ppm r e l a t i v e  since  for  Surface  2 0 . 2 ppm ( F i g .  higher  be  value  and n e u t r a l  F-NMR spectrum o f  at  can  3 , 5 8  shifts  fields  al.  c  value  c  useful  whereas  compound  The I  groups  species.  show c h e m i c a l  be a s u i t a b l e  have  data.  GIC."*  are  intercalant  resonance w h i c h appears however  in  spectra  resonance  shifted  this  This  6 0  when b o t h S O 3 F  intercalant(s),  shifted  a single  cantly  the  products  resonances  only  graphite.  as i n t e r c a l a t e s  The  of  r e p o r t e d b y Yaddaden e t  with  3  acid fluorosulfates  for  ( s t a g e one)  X - r a y powder d i f f r a c t i o n  well with  present  index  these  the 4  3  is  signifi-  liquid 1 9  F-NMR  between  species  may  intercal-  are  a n d 4 0 . 6 ppm i n h i g h  HSO3F  closely  resolution  - 107 -  -120ppm  Figure 4.4:  20.2ppm  ^F-NMR Spectrum o f  115ppm  C S0 F.3HS0 F.O-2I 3 2  3  3  -  spectra. when  Iodine,  7 8  the  GIC  relatively  1 2 was f o u n d as  was  heated  long heating  intercalant  108  rather  to  -  a  deintercalated  200°C f o r  time confirm  than  a  the  surface  4 h.  sublimed  The h i g h  existence  adsorbed  temperature  of  species  product  iodine i n the  and  as  an  graphite  lattice. The e l e c t r i c a l  conductivity  enhanced conductance  of  intercalated  i n the basal planes.  Typical  HOPG  samples  show  d a t a o b t a i n e d were  as  follows:  Table 4 . 2 :  T y p i c a l C o n d u c t i v i t y Measurements Compound  Compound:  (ohm*  S  1  = 9.59 x 1 0 "  2  4  cm ,  2  t  2  -  i ) v  5.70 x 1 0 "  2  cm  o/ag*  k/kg  t/to  10.13  12.56  1.24  1  - 2.32 x 10 ohm" c m " (see Sec. 2 . 4 f o r t h e d e f i n i t i o n s 4  1  1  g  Interestingly, larger  intercalants almost  s o  cm" )  23.5  much  +  3  a x 10"  c r  Graphite-l2 (  C32SO3F.3HS0 F.0•21  Dimensions:  *  for  value are  1 0 0  •  1 0 1  than for  graphite  SO3F" a n d H S O 3 F .  comparable  compounds.  the c o n d u c t i v i t y  to  values  4 3  of  terms  observed i n  used)  this  compound  acid fluorosulfates  where  These h i g h c o n d u c t i v i t y  obtained for  graphite-ASF5  show  a  the  only  values  are  intercalation  - 109 -  4.2.2  Intercalation  The  synthetic  intercalant  of  showed a c l e a r 3  As shown e a r l i e r acid  I(S0 F)4", 3  agent,  species  using  3  or I ( S 0 F )  + 2  3  iodine  exists  oxidized  I(S0 F) 3  in  to  3  acid.  3  in  In  3  rather  short period  5e"  oxidizing  This  gives  The  points  >  . 2I  + 1  /2  or  I  s u c h as  the  graphite  (18 h ) b y t h e  according  base  the  of the f i l t r a t e  has been reduced by g r a p h i t e  first. a  ions  surface  that  +  later.  as  of the product  The g r e e n b l u e c o l o r  + 3  as  solutions.  3  intercalation.  2I  both cases,  may f u n c t i o n  I(S0 F) /HS0 F a  detail  i s t o be examined h e r e  9 4  the  on the concentra-  a +3 o x i d a t i o n s t a t e . 3  as  3  c o u l d behave e i t h e r  3  itself  and t h e d a r k b l a c k b l u e c o l o r  iodine(III)  I(S0 F)  dependence o f t h e r e a c t i o n s  fluorosulfuric  I(S0 F)  was  out  ( - 1 . 2 0 M) s y n t h e s i s  t y p i c a l pale yellow color lattice  carried  i n Sec. 4 . 1 . 3 ,  in  where  3  T h i s f a c t o r w i l l b e d i s c u s s e d i n more  3  The h i g h c o n c e n t r a t i o n  an  3  reactions  tion of I(S0 F) .  or  I(S0 F)  iodine  indicated to the  fact  to:  + 2  and/or, 3I  A mixture  of I  + 3  +  3  +  8e"  (yellow)  >  3I  + 1  /3  o  J3+  r  and 1+1/2 (blue)  green  color  identical  observed.  results.  21.5:1:2.99:2.93, Interestingly, sion  that  Also,  I  +  l/  The m i c r o a n a l y s i s points  to  a  and  2  I  results,  +  l/  3  with  produce (brown)  the  C  give  ratio 2 2  of  I(S0 F) . 3  3  which l e d to the conclu-  amount o f H S 0 F i n t e r c a l a t i o n h a d t a k e n 3  blue  can  C:I:S:F  compound w i t h c o m p o s i t i o n  h y d r o g e n was f o u n d t o b e a b s e n t ,  no a p p r e c i a b l e  can  place  - 110  in  the  sample.  strong  Therefore,  oxidative during  considered  for  2  That layer all  the  product,  is  separation value  to  i.e.  though  layer.  I(S03F)3  configuration frequency  is  for  shift  4 3  of  of  C 2l.3S03F.  1 9  F-NMR  resonance  at  compared  to  with other surface  •  1  0  7 . 9 4 ± 0 . 0 3 A. for  the  showed of  may  this  also  be  case, as  a and  the  compared  fall  with electron  I  seen f r o m the  inter-  has been n o t e d b e f o r e  fluorosulfates  that  w e l l below 8.0  transfer  from  value  c  as shown e a r l i e r  observed i s j u s t i f i e d if  4.1.3  planar  and 4 . 1 . 5 .  mode t o 1 6 4 0 - 1 6 4 2  and  (even  one assumes s q u a r e  i n Sec.  A,  gra-  a t t r a c t i o n between the carbon  a large molecule)  cm"--  The  in  agrees w i t h p u b l i s h e d d a t a r e p o r t e d from o t h e r  the  first  1 0 3 , 1 0 4  spectrum o f C 2 l ( S 0 3 F ) 2  2 3 . 6 ppm, w h i c h i s free  It  the E 2 g ^ v i b r a t i o n a l  I(S03F)3  reported values  (47.0 ppm). for  p r o d u c t s were  (Fig.  4.5)  This value  indicates  is  to  a  single  higher  i n good  field  agreement  i n t e r c a l a t e d halogen f l u o r o s u l f a t e s . is  s a m p l e was h e a t e d a t analyzed  peaks c o r r e s p o n d i n g  the remaining s o l i d  3  a b o u t a 2 3 . 4 ppm s h i f t  adsorbed o r condensed I ( S 0 3 F ) 3  The i n t e r c a l a t e d volatile  as  oxidant  different  s t a g e one c a n be c l e a r l y  The s m a l l  2  quite  of  compounds. The  acts  the  In  2  c a u s i n g Coulombic  iodine,  Raman s p e c t r a a l s o stage  as  formula  c o u l d be s i g n i f i c a n t l y  separations  intercalant  intercalant  both  An a l t e r n a t i v e  suggesting c l o s e l y packed s t r u c t u r e s phite  I(S03F)3  formation.  the product  interlayer  functioning  the synthesis.  intercalation  to C 2l(S03F)3  c a n be assumed t h a t  intercalant,  intercalant  mechanism o f  it  -  by  I.R.  observed i n 100°C f o r  these  t o C O 2 , S O 2 and p o s s i b l y  sample gave a r e s o n a n c e  at  The The  SO2F2.  2 1 ppm.  No  spectra.  seven days,  spectroscopy.  4 3  It  was  and  the  spectra 1 9  F-NMR noted  - Ill  39.2ppm  Figure  4.5:  1 9  F-NMR Spectrum o f  -  23.6ppm  C  2 2  I(S0 F) 3  -  earlier to  in  4.1.3  that  at  50°C i n v a c u o ,  I F 3 ( S C > 3 F ) 2 and S O 3 r e s p e c t i v e l y .  ISO3F,  that  Sec.  112  the  remaining  s o l i d product  I(SC>3F)3  Therefore,  Alternatively,  a mixture  of both these  be  in  as w e l l .  However,  unlikely the  1 9  since  F-NMR  the l a t t i c e only  a single  composition  interlayer the  t h e case o f  for  and  3  suggests  the  between  the  the  9 3  ideal  of  7.94  composition  calants,  of  BrSG^F.  A  is  or  could  possibility  the  is  product  in  intercalation,  the  gives  volume as  a of  is  C24.44  This  transfer  takes place  causing  a  closer  study  the  using  In a similar  1 0 2  as  gallery I(S0 F)3 3  follows: volume  at  25°C  the  I(S03F>3.  The  discrepancy microanalysis  assumed  p a c k i n g due t o  an i n c r e a s e  and in  is This  3  o b t a i n e d by  graphite  11.99  which  in  c a n a r i s e when a n a p p r e c i a b l e  between  the  of  as 293 A .  than that  the  manner,  calculated  packed s t r u c t u r e  situation  earlier  deduced  c o m p o s i t i o n and t h e v a l u e  above c a l c u l a t i o n s . charge  latter  calculated  reported density  molecular  ideal  been  density  may be due t o a more t i g h t l y  of  intercalants  graphite-BrSG^F  graphite-I(SO3F)3  and u s i n g the  g/cm ,  has  B r  separation  atom,  2.40  for  separation  interlayer 3  possible  graphite-ISO3F  r e s o n a n c e was o b s e r v e d f o r  C^2 S03F  ideal packing  A /C  the  is  spectra.  Interestingly, ideal  it  may b e composed o f  IF3(S03F)2present  disproportionates  the  the  amount inter-  electrostatic  attraction. I n order final  product  graphite  formation,  were r e a c t e d  The f i l t r a t e of  to  graphite  as b e f o r e by the  function of various  in H S O 3 F ,  stoichiometric  concentration amounts  of  based on t h e c o m p o s i t i o n o f  gave a b l u e  iodine  I(S03F)3  species.  green c o l o r , However,  indicating  in  I(S03F>3  the and  C22l(S03F)3. the  the microanalysis  oxidation data  on  113  the products percentage cant  showed t h e a b s e n c e o f  small values I(S03F)3 groups  were  relative  intercalate In  to carbon.  into  the  that  species,  as  and i f  an  I(SC>3F)3  sufficient  excess the  of  as t h e o x i d i z i n g  Initially,  could  not  I(SC>3F)3  a g e n t and  and  first  is  It  stage  place.  observed.  are a v a i l a b l e  to  lower  acts  from  This  in  fold these GIC's  can  as t h e  be  oxidizing  the  high  SO3F  a five  to obtain  solution,  preferential  concentrations,  function  which  only  intercalation  Instead,  At  signifi-  at  about  i s necessary  are present  carbon  and p o s s i b l y  intercalant.  take  intercalant,  that  seems c l e a r  I(S03F>3  it  a n d no  indicate  synthesis,  I(S03F)3  oxidizer  o f H S O 3 F and S O 3 F "  amounts o f  form  intercalant.  s m a l l amounts o f  intercalation  intercalation  to  The  w h i c h showed  acid molecules  concentration  follows: only  the products,  These r e s u l t s  graphite  high  w h i c h f u n c t i o n b o t h as rationalized  in all  only neutral  I ( S C > 3 F ) 3 was u s e d as t h e  observations  as an i n t e r c a l a n t .  seen i n hydrogen c o m p o s i t i o n s ,  concentrations,  compounds. excess  iodine  remained almost constant  variations  -  leads  to  simultaneously the  product  C 2l(S03F)3. 2  The  intercalated  conductivity  values  HOPG  samples  and t y p i c a l  results  were  used  w e r e as  to  obtain  follows:  electrical  - 114 -  Table 4 . 3 :  Electrical  C o n d u c t i v i t y Values o f  Compound:  C 2l(S03F)3  Dimensions:  s  = 9.51 x 1 0 "  2  lO * -  (ohm"  1  The  data  all  the  in  the  anions  ohm'  4  indicate  the basal plane, transfer  2  cm , 2  t = 3.50 x 1 0 "  2  cm  a/a*  k/kg  t/to  6.55  11.7  1.78  1  = 2.32 x 1 0  g  3  cm" )  15.2  <r  2  2  a x  *  C 2l(S0 F)3  1  cm'  1  a considerable  enhancement  a n d t h e a/ag v a l u e o f 6 . 5 5 p o i n t s  from graphite  to the i n t e r c a l a n t .  i n f o r m a t i o n p r e s e n t e d so f a r above  i n the c o n d u c t i v i t y  synthesis,  formed i n the  questions which s t i l l  the  intercalant need t o be  that  Although i t  I(S03F)3  exact extent layer  on  resolved.  to extensive is  a c t s as  electron  evident an  transfer  from  acceptor  o f charge t r a n s f e r  charge  along  are  and  the  major  -  4.2.3  Intercalation  The  I  rationale  [I(S03F)4]"  ion  2 (solv)•  which  +  initial would  impart  would lead to the  and t h a t  of  attempting from  the  positive  charges  electrostatic  the  intercalation  inability  i n Sec.  the graphite  must  4.2.1.  lattice on  to  of  the  clearly It  intercalate  was assumed t h a t  according  the graphite  solvated  to  C  — >  n  C  the  +  + n  e"  layers,  which i n  turn  r e p u l s i o n between the g r a p h i t e  lattice  and  indeed  rare  a l s o be r e c a l l e d  such simple  cations  intercalate  ants  s u c h as I ( S 0 3 F > 3  relatively  first  t i o n at  themselves.  s t a g e compounds  sufficiently  will  in fluorosulfuric  dissolves  in HSO3F  quite  following  charged  agent.  [I(S03F)4]"  in  +  the a c i d , is  i.e.  then  giving  T—»  intercala-  suggests  I(S03F)4" in  this  solution  ions.  3  4  +  a  hypothespecies  studies  although  the  of salt  Furthermore,  solution,  H[I(S0 F) ]  that  the anion is  to v e r i f y  4.1.4,  10.56  Interestingly,  provided that  i n Sec.  4.3.2),  18.60 and  show s o l v e n t  This  do  intercal-  was u s e d as t h e r e a c t i n g  also possible  HSO3F  but  Sec.  products.  I n order  As e x p l a i n e d  equilibrium  3  again,  in  h a v e n o t b e e n r e p o r t e d up t o n o w ,  easily  I(S0 F)4"  and b r o m i n e ,  intercalated  well  graphite,  discussed  concentrations.  intercalate  acid.  oxidize  is  i n t h e case o f n e u t r a l  ( t o be  iodine  +  thus obtained d i d not  strong oxidizing  the n e g a t i v e l y  K[I(S03F)4]  of  intercalation  or N02  +  However,  the  intercalant  [Hal(S03F)4]"  cation  N0  a n d Br(SC"3F)3  were found i n  high  that  like  high percentages  respectively,  the  for  3  was d i s c u s s e d  not  sis,  K[I(S0 F)4]  -  intercalant. It  the  of  comes  oxidation  115  SO3F"  -  Hence  the  clearly  exact  in this  filtrate  nature  of  synthesis.  indicates  that  I  +  116  the  oxidizing  However,  (from I(S03F>4"  3  to  the  process.  intercalation  during the graphite-I(S03F)3 The  elemental  analysis  Cg6l.10.51 S O 3 F . can  also  I+1/2  An a l t e r n a t i v e  be w r i t t e n  for  the  A  and/or  similar as  formula  a such  product.  as  a)  significant  intercalation  b)  t h e absence o f  solvent  These two f a c t o r s such  as I ( S 0 F ) 3  of  or  reasonable  stage one). groups value  to  this  taking  like  when  during  o b s e r v a t i o n was made in  C  g 6  Sec.  4.2.2.  composition  I(S0 F)4.6.5ISO3F 3  (5.55%),  features  can  and product.  to neutral  I(S0 F)4" 3  reacted  intercalants  i n H S O 3 F may  also  graphite.  The  with  charged i n t e r c a l a n t s whereas  seems t o  lead  intercalant  species  predominantly  solvent  compound C g g I . 1 0 . 5 I S O 3 F  makes  +  found f o r  formula,  the  the product  into  gi  v  e  is  consideration  of  low stage  that  there  t h e c o m p o s i t i o n seems t o  (most  are  indicate  probably  10.51 the  SO3F"  limiting  synthesis.  The -- F-NMR s p e c t r u m o f 9  anions  s u c h as l 2 ( s o l v )  assume t h a t  Also,  per u n i t for  3  (brown)  3  the  products.  The l o w c a r b o n c o n t e n t it  /  intercalated  in addition  intercalation,  charge  1  for  product:  i n the  negatively  solute  a positive  intercalated  that  intercalants  neutral  toward p r e f e r e n t i a l carrying  suggest  and B r ( S 0 3 F ) 3 ,  3  f u n c t i o n as o x i d a t i v e presence  (HSO3F)  +  Two i m p o r t a n t  the  iodine  I  deduced  H[I(S0 F)4])  compound w i t h  be observed i n t h e c o m p o s i t i o n o f amount o f  observed  discussed  indicate  final  c a n n o t be  or from n e u t r a l  (blue)  synthesis,  values  agent(s)  the green c o l o r  has been r e d u c e d by g r a p h i t e initial  -  the s o l i d  product  showed  only  a  single  117  broad  resonance  at  18 ppm, w h i c h e x c l u d e s  sorbed o r condensed i n t e r c a l a n t s The r e s u l t s ity  of  only It  HSO3F.  is  synthesis. greater  also  may  be  agent  of  a  reaction.  acid in  iodine it  While  a higher  [I(SC-3F)4]"  intercalation  for  acts  neutral  as  seems  iodine  Solutions other  graphite,  to  found  fluorosulfates  of  fluorosulfates  inhomogeneous dried  v  is  for  better  3 h,  since  the  to  the  intercalation which  good  oxidizing  ions  present,  achieved  than  3  due  intercalants  I(S03F)3  a  into  ^ j  s o  like  Br(S0 F)3  in HSO3F,  during in  the  the  GIC  l2 (solv) +  (and  a  n  Br(SC>3F)3)  opportunity  for  the  graphite.  IS0 F 3  graphite  discussed  so  in a far.  manner  a n d when t o t a l l y the product  dry  surfaces  the  similar  When m i x e d  suspension m i x t u r e s were o b s e r v e d .  for  intercalation  in  provide  I S O 3 F were r e a c t e d w i t h  iodine  vacuum  possible  of  intercalant  is  Attempted I n t e r c a l a t i o n  as  feasibil-  during  possibly  the S 0 3 F " ^  concentration  the  occur  a sufficiently  [I(SC>3F)4]"  medium  which of  However,  iodine  does  that K[I(S03F)4] is  4.6).  and  3  is  chemiad-  s o l v e n t medium  t o undergo o x i d a t i v e  appears  any  the  as i n I ( S 0 F ) 3  the product  species  indicate  a protonic  study,  of  compound ( F i g .  intercalation  intercalation.  intercalation,  were  the  competition  approximately  to  oxidative  I n summary,  to effect  4.2.4  from t h i s  in  d e f i n e d as a b a s e i n t h e a c i d ,  provide  when  clear  The a b s e n c e o f  with graphite.  i n the f i n a l  intercalation  that  ability  the presence  o b t a i n e d i n t h e above s y n t h e s i s  solute  intercalation,  -  The  samples  appeared t o  with  products indicated be  black  - 118 -  119 -  blue  in  color.  However,  the  1 9  F-NMR  s p e c t r a o f t h e compounds g a v e r e s o n a n c e s  t h e r e g i o n o f ~ 4 4 ppm, i n d i c a t i n g o n l y species.  Hence  it  was  surface  c o n c l u d e d t h a t no o x i d a t i v e  o c c u r r e d i n the s y n t h e s i s between I S O 3 F any the  oxidizing lack of  earlier  species  to  Iodine  phite,  it  does  since  galleries  4.3  4.3.1  itself, not  i n the graphite  Intercalation of  w h i c h does n o t  meet  lattice  the  B r  between cantly  w  different  manner.  <  of  of  the  0.025).  As  and a f i r s t  reported  c o u l d behave i n  intercalate  into  a  gra-  t o open t h e  the i n t e r c a l a t i o n  process.  4 3  • --  0 2  intercalation  graphite  lattice.  a compound o f  shown  by  these  fluorosulfate  and  graphite  s t a g e compound w i t h a c o m p o s i -  However,  in fluorosulfuric  short  1:1.02 i n d i c a t e  been  3  reported.  compounds  oxidation  (x  s  these  The r e l a t i v e l y  ratio  a  for  BrS0 F  been c a r r i e d out e a r l i e r  t i o n of Ci2 S°3F  may be r e s p o n s i b l e  Compounds  The r e a c t i o n b e t w e e n l i q u i d b r o m i n e ( I ) has  of  energy requirements  to i n i t i a t e  has  absence  The s o l u t i o n s  4 3  Bromine C o n t a i n i n g  Intercalation of  ISO3F  The  A comparable o b s e r v a t i o n has  intercalation.  manner s i m i l a r  of  fluorosulfate  intercalation  and g r a p h i t e .  i n the solutions  intercalation.  f o r pure I S O 3 F  adsorbed  in  time  the  synthetic  a c i d proceeds  (18  h)  indicates  The m i c r o a n a l y s i s formula results,  C]  L l  in a  reaction signifi-  a  fast  data with  F:S  HSO3F.0-5SO3F.xBrSO3F  only a small f r a c t i o n  of  - 120 -  bromine,  assumed  calate. i.e.  C  HS0 F.(0.5 lattice  values.  It  on c h a r g e  be  confirmed  8.22  product  i n Sec. 4 . 2 . 1  ( - 7 . 9 9 A).  points A  is  This  is  S0 F"  As shown b e f o r e ,  The  1 9  and  signal  at  3  agrees  for  a  S0 F  this  first  (or BrS0 F)  3  3  1 4 . 9 2 ppm i s  the  the s  t  *  low  value  layers  is  obtained  (Fig.  discussed  products  contain  interlayer  acid fluorosulfates .  4  between  This chemical n  it  is  intercalated  clear  compounds.  of quite  different  oxidizing  calate. but  agent  Solutions now  and  Direct  intercalation  as a r e s u l t ,  it  is  of BrS0 F i n f l u o r o s u l f u r i c 3  S0 F" 3  and  HS0 F 3  the  value  3  than  3  the  i n the  inter-  formation  e m p l o y s B r S 0 F as 3  f o u n d as t h e s o l e  are the predominant  intercalates  as a m i n o r  the  inter-  a c i d lead t o a stage  BrS0 F or a s i m i l a r bromine-S0 F species present  > ->  4 3  3  products.  3  3  single  shift  f r o m t h e above d i s c u s s i o n t h a t  3  and  separation  and c o n s e q u e n t l y o n l y a  4.7).  the  3  stage g r a p h i t e  observed  for  n e u t r a l HS0 F molecules  a typical  resonances,  content compound.  o x i d i z i n g agent,  i e  i.e.  carbon  intercalation  c a l a t i o n o f p u r e B r S 0 F a n d as a H S 0 F s o l u t i o n r e s u l t s  3  F-NMR)  more w i t h G I C ' s h a v i n g g e n e r a l c o m p o s i t i o n C . X H S 0 F . Y S 0 F ,  I n summary,  GIC,  1 9  intercalant  expected since both  intercalants,  w i t h halogen f l u o r o s u l f a t e  only  (or  F - N M R s p e c t r u m o f t h e compound d o e s n o t d i f f e r e n t i a t e  HS0 F  the  3  stage  to  +  same  observed  product,  o f B r S 0 F as s u c h i n  among t h e  and  c  to a f i r s t  with l2 (solv)  the  distance  I  close  predominantly groups.  the  microanalysis  species  repeat distance  intercalation  3  by  for  inter-  1 0 1  layer  of  also possible  The e x i s t e n c e  as a n a n i o n i c  microanalysis  value  c  cannot  transfer.  by  composition is 3  may e x i s t  The c - a x i s  i n t h e f o r m o f B r S 0 3 F , was f o u n d as a n  + x)S0 F.xBr.  3  graphite  The I  be  An a l t e r n a t i v e 1 1  found  to  one with  intercalate.  8  - 121 -  e 4.7:  F-NMR Spectrum o f (x < 0.025)  1 9  CnHSOoF-5S0,F 3  -  However, data or  neither 1 9  microanalysis,  i n t h e above  4.3.2  Intercalation  The  chemical  this  of  B r S 0  3  F  identification  1 9  F-NMR  possibly  and p h y s i c a l  properties  from  yields  for  is  quite  stable  virtually  that  adsorbed.  in HSO3F  direct  seems  is  species  in  observed  on  graphite  h)  confirms  indicates  analysis  results.  26.8  B r  (  S 0  3 >3F  Therefore,  S 0  a  are  the  F  that  with at  lattice  B r S 0  w h i c h shows a c a r b o n p e r c e n t a g e  3 F  3 S 0  not  previously  i n the  0 2  form  intercalated of  4.1.5,  F  Br(S03F>3  functions The  as  bluish  of only 33.8,  and  The  C g gBr.4SC>3F 2  (24  intercalated  derived from  compared t o  the tint  the r e a c t i o n period  3Br.4S03F,  s  and  9 7  graphite.  A  and  Br(S03F)3  micro-  t h e GIC c a n a l s o be f o r m u l a t e d 3 -  It  Br(SC>3F)3  dissociation  by Br(S03F>3.  2  2  A  to carbon r a t i o  little  t h e end o f  composition of C g  C 6.8  • --  room  temperature,  intercalation  observed.  The c o m p o s i t i o n o f 3  is  and  certain  surface of  4 3  As s e e n i n S e c .  acid,  reaction  intercalation  product  c  the  intercalate  attempted.  almost  oxidizing  the  inter-  a solid at  intercalation.  Br(S03F>3  in fluorosulfuric  it  X-ray  general composition C i g B r ^ C ^ F ) 3 .  some  no d i s p r o p o r t i o n a t i o n  Hence,  the  this  intercalated BrSC^F,  a compound o f  surface  solutions  all  o f Br(SC>3F)3,  towards decomposition a t  the o x i d a t i o n o f  spectrum  only  of  from  3  does, however appear f r o m b o t h the h i g h the  separation values  Br(S0 F)3  material unsuitable  reported route, C^2  interlayer  compound.  temperature w i t h a tendency  of  -  F-NMR s p e c t r a a l l o w a c l e a r  calates  makes  122  C  1 6  as  Br(SO3F)3,  suggests  a  -  product  closer  size. the  This  to  the l i m i t i n g  -  composition,  c a n be s e e n c l e a r l y  product.  123  from X-ray  The X - r a y p o w d e r v a l u e  for  considering  and the  1 9  the  F-NMR data o b t a i n e d  layer  repeat  t o a s t a g e one c o m p o u n d .  In addition,  also  extensive  between the g r a p h i t e  the  intercalate(s).  only  a  single  chemical  It  The  broad  shifts  compounds.  charge 1 9  transfer  F-NMR spectrum o f  resonance  observed  for  at other  interesting  to note  discussed e a r l i e r ,  a b r o a d peak i s  second  at  resonance  surface  The  360-750 or B r  + 2  .  or  However, obtained  (Fig.  4.3, they  detection  limit,  used  the  as  mmol g r a p h i t e 0.16  compound  ppm, w h i c h i s  I  I  c  =  value  c  lattice  and  consists  of  compatible  intercalated  SO3F"  ppm  that  6  10  (relative 2 6  the to  filtrates  with  graphite  to  detect  to  Br3  may  existed  i n very  +  mmol u n r e a c t e d B r ( S 0 3 F ) 3  the  1 9  t o be  range  F-NMR  (typical  w o u l d be p r e s e n t that neither  of  any  amounts,  see  in  in  the  below  the  mmol)  As a n e x a m p l e ,  +  The  Br(S03F>3  (-12.5  =  Br3  successful.  and i n the as  The A  s u c h as  low c o n c e n t r a t i o n s  i n the r e a c t i o n s .  a  product.  species  graphite  w o u l d be p r o d u c e d ,  appears  the  as  to  c a t i o n s had been p r e s e n t  as o n l y s m a l l a m o u n t s o f  +  final  t h e ones o b s e r v e d f o r  Even i f  3  in  any r e d u c e d bromine  were  Br  in  CFCI3)  i n the  d i d not prove  have  addition  3  these attempts similar  in  compound,  g B r . 4 S 0 F show t h e a b s e n c e o f  curve D).  it  ppm,  were t a k e n  a n d 2 . 0 2 mmol B r ( S 0 3 F ) 3  I n summary,  the C^ Br(S03F)3  condensed i n t e r c a l a n t s  reducing agent  mmol  for  seen a t  F-NMR spectra o f C  spectra of  filtrate,  only  38.3  nm, i n o r d e r  spectra HSO3F  1 9  adsorbed  UV-visible  small  for  4 3  is  spectrum.  12  the  the  distance  7.88 A p o i n t s suggests  intercalate  for Sec  same f i l t r a t e  were 12.5 3.4) 1.86  well.  microanalysis  nor  any  of  the  -  physical  techniques  intercalate Also,  it  not  calation of in  their  used are able  formulations  is  exactly  I(S0 F) 3  124 -  3  as  to d i f f e r e n t i a t e  either  with  a possible  case and a n e g a t i v e l y  charged species  4.3.3  of  Intercalation  As  in  the  case  3  of  4.2.3).  3  behaviour  in  pounds w i t h g r a p h i t e related  behavior  Since b o t h K [ I ( S 0 F ) ]  chemical  chemical  K[Br(SC"3F) ]  will  4  lead,  exist  as  4  Br  a c i d medium.  + 3  The 4  is  acid.  present  differ in  one  Br  + 1  3  2  i n order  study  the  (see  Sec.  acid,  both  exhibit  4  surprisingly,  oxidizing  /  the  to  4  and K [ B r ( S 0 F ) ]  it  synthesis,  [Br(SC-3F) ]~ w i t h g r a p h i t e  could  to  GIC's  Hence, I n the  the  3  4  In  to Br "--/ 4  may n o t be p r e s e n t  2  these  com-  closely  intercalation  and  H[Br(S0 F) ] 3  that  and/or  of  discussion.  analogy  assumed  inter-  similar  having  following  [Br(S0 F) ]"  be  very  the r e a c t i o n o f  agents.  reduced by g r a p h i t e  Br  4  with  the  during  the  in  the  species  in  composition  of  as a s t a b l e  + 1  /  3  9 7  microanalysis  Cg Br.ll.22S03F,  of  solutions,  4  reaction,  However,  fluorosulfuric  not  potential  K[I(SC>3F) ]-graphite synthesis,  4  was c a r r i e d o u t  be e x p l a i n e d o n l y b r i e f l y 3  inter-  other.  and p h y s i c a l p r o p e r t i e s .  3  the  4  fluorosulfuric  In HS0 F-K[Br(S0 F) ] can  i n the  SO3F".  in HSO3F,  intercalate  K[I(SC^F^] -graphite 4  intercalant  derived from  +  3  K[Br(S0 F) ]  c a l a t i o n r e a c t i o n o f K[Br(SC-3F) ] oxidative  neutral  possible  or Br(S03F)  both from solutions  3  compositions  BrCSC^F)^"  c l e a r why t h e p r o d u c t s  and B r ( S 0 F ) 3 ,  between two  results,  show a s u b s t a n t i a l  which  indicate  amount o f  bromine  a  in  the  product  -  (cf.  CggI.10.51SO3F).  compound  suggests  reaction,  the r e l a t i v e l y  solvent-free  t o a low stage is  clear  and K [ B r ( S C ^ F ) ^ ] take  a  place  in  Again,  the  intercalated  as i n t h e  seen  expressed  for  KflCSC^F)^] the  product  compound.  from the observations insertion  reactions  during the syntheses.  too.  I n summary,  functions  as a r e l a t i v e l y  concentrations  made so f a r  that  by u t i l i z i n g  KtlCSC^F)^]  intercalation  the conclusions  apply equally w e l l  a l t h o u g h K[Br(SC"3F)4]  good o x i d i z i n g  of  for both  oxidative  Therefore,  synthesis  reaction  effectively  GIC.  small carbon percentage  t h e K[ I ( S C ^ F ^ ] - g r a p h i t e  high  t h e compound c a n a l s o be  The a b s e n c e o f h y d r o g e n  3  It  -  The f o r m u l a o f  as C g 4 B r ( S 0 F ) 4 7 . 2 2 S O 3 F .  points  125  for  does  drawn  the  present  in fluorosulfuric  acid  agent,  the  intercalation  bromine-fluorosulfates  can  be  an  apparently  neutral  for  of  a c h i e v e d more  intercalant  such  as  Br(S0 F) . 3  3  4.3.4  Intercalation  It  was  seen  of  IBrjSC^F  earlier  In  Sec.  4.2.1  i n t e r c a l a t i o n produced GIC's w i t h predominantly molecules  as i n t e r c a l a t e s .  a similar  cation-promoted  the  intercalant.  s t r o n g base give  graphite,  +  it  synthetic  observed  in fluorosulfuric  IB 2 (solv) r  As  Therefore,  is  and S 0 3 F " (  possible  that  in  acid, s o  ^ j  + 2  I  SO3F"  2  (solv)  Sec.  in HSO3F 4.1.8,  using  to  HSO3F  carry  out  IBr S0 F  as  2  3  I B ^ S O ^ F b e h a v e s as a  undergoing complete Hence,  promoted  and n e u t r a l  seems i n t e r e s t i n g  reaction  ions.  v  IBr  it  that  dissociation  during the r e a c t i o n  may f u n c t i o n as t h e o x i d i z i n g  to with  agent.  - 126 -  A  relatively  synthesis, metallic initial  reaction  s u g g e s t i n g weaker blue  color  time  Due t o  the f i n a l  i s n o t c o m p l e t e a n d does n o t  this  reason,  product.  The  first  3.3,  I n order  In  in this  i n Sec. 4 . 4 ) , hydrogen  to  to confirm this  the  (i.e.  present  insertion.  cation  This  that  the  final  +  synthesis  the graphite In  lattice  summary,  and g r a p h i t e *2 (solv) +  o  N 0 +  c a n b e assumed t h a t  (solv)>  not  ^^(solv)  induced r e a c t i o n s ,  to  in  greater  compositions,  detail,  additional  X-ray d i f f r a c t i o n  and  1 9  (see  and falls  Sec.  X-ray  t  o  3.1,  diffrac-  D  reactions discussed  e  appreciable  the conclusion  Therefore, groups,  manner  that  It  is  and  possibly  of  halogen  very  in  analysis.  the r e a c t i o n between when  IB^SC^F  compared  t h e most i m p o r t a n t  b e i n g t h e a b s e n c e o f a c i d m o l e c u l e s as i n t e r c a l a t e s . system  stage  indicate  the presence  in a different  absence  account.  h a s t o be v e r i f i e d b y e l e m e n t a l  it  the  halogens  by m i c r o a n a l y s i s  contain S O 3 F "  However,  of  formulated  intercalation  leads  i n the GIC.  product w i l l  i n H S O 3 F proceeds r  a n c i  does  observation  h a l o g e n s p e c i e s as i n t e r c a l a t e s .  the  the  observation,  promoted  l2 (solv)  n e u t r a l a c i d m o l e c u l es a r e a b s e n t likely  obtained  The  confirmed  and t h e  to  s t a g e i n t e r c a l a t i o n compounds  other  thesis  include  regard  t h e sample have t o be t a k e n i n t o  contrast  discussed  with  this  ions.  +  analysis  the low carbon c o n t e n t  percentage  w i t h i n the range o f  t i o n values of  IBr2  a g e n e r a l f o r m u l a c a n n o t be  However,  carbon  3.5 and 3 . 6 ) .  of  The c o m p o s i t i o n a l  o f h y d r o g e n i n t h e GIC a r e s i g n i f i c a n t composition.  ability  o b s e r v e d on t h e g r a p h i t e powder s u r f a c e  product  and s u l f u r .  (2 d a y s ) was r e q u i r e d f o r  oxidizing  i n t e r c a l a t ion of the l a t t i c e .  intercalated  for  long  to  difference  To u n d e r s t a n d  d a t a s u c h as e l e m e n t a l  this  halogen  F - N M R have t o be o b t a i n e d f o r  the  -  intercalated  4.4  Nitrosonium Ion  the o x i d i z i n g  ( N 0  of  agent  M -  P or  used before  the  and S O 3 F "  ideal  solvents  For example,  4.1.7,  according  ionizing  MFg"(solvent)y, 2.5.  which  the  was  compounds  where n i s  the  3 6  ionizing.  in fluorosulfuric  is  as  +  solvent,  was f o u n d t h a t  strongly  dissolved  solid NOSO3F  NC>2 )  to carry out a similar  which i s  HSO3F,  + 3 n  to  seems i n t e r e s t i n g  like  it  (and  +  s u c h as n i t r o m e t h a n e ,  weakly  composition C2  intercalant  i n Sec.  compounds u s i n g N 0  c o o r d i n a t i n g and  1.8.3.  it  solvent  as  Intercalation  Sb, and y u s u a l l y - 1 . 7  Therefore, protonic  ) Promoted  in non-protonic  i n Sec.  t h u s made h a v e t h e stage,  +  intercalation  a moderately polar,  discussed  -  compound.  The s y n t h e s i s  is  127  extensively  study  in  was  NOSO3F  acid.  dissociated  a  As  shown  into  N 0  +  to:  HSO3F  N O S 0  In N 0 +  analogy (solv)  w  o  to u  l d  as h a d b e e n t h e  3  observe  GIC's  from  (  s  o  l  v  )  5 = f c  non-protonic  NC-  solvent  f u n c t i o n as t h e o x i d a n t case i n  The r e a c t a n t to  F  these  ( s o l v )  S 0  synthesis,  3  F -  it  (  s  o  l  v  )  was e x p e c t e d  i n the r e a c t i o n  with  that  graphite,  nitromethane.  concentrations  any e f f e c t  +  +  and r e a c t i o n  on the c o m p o s i t i o n o f  syntheses  were  times were v a r i e d  the  analyzed  final for  product.  in  order  When t h e  carbon, hydrogen  and  -  nitrogen, tion  varying compositions  gave i n c o n s i s t e n t  compositions observations  are  NO  or  any  Hence,  the  results  elemental analysis values  given  final  other role  groups,  +  that  microanalysis  compositions  reaction  value  with  remaining  these  agent  al.  for  (see Table  Similar  the GIC's (e.g.  measured,  for  I  c  neutral  in  -27.8%,  C-7 S03F.2 4HS03F, -  4  intercalation 1 9  which  i n the  F-NMR  ppm r e s p e c t i v e l y  the  final  of (Fig.  the  sample of  cointercalated. from  t h e GIC a r e  can  be  the  in  reactant data).  stage  index.  = 1 0 . 5 9 ± 0 . 0 3 A,  also  shows  a  of  the  However,  substantial  HSO3F  concentrations  X-ray  or  diffraction  72%  amount  do  indicate  a second  can  the  observa-  obtained  confirms  product  been  non-protonic  One g e n e r a l  The  from  have  solvent  The h i g h c a r b o n p e r c e n t a g e s  formula  a  n  on  SO3F"  derived  compositions  For average c a r b o n and h y d r o g e n c o m p o s i t i o n s  SO3F"  above  NOSO3F,  seems c l e a r  synthesized  numerical  are of a higher with  the  C23 MFg(solvent)y).  dependence  3.2  the  the presence  s p e c i e s has been  intercalants  compounds.  significant  the products  The  t h a t no  n  c a n be made s a f e l y :  compound.  indicate  t h e compounds f o r m e d i n t h e p r o t o n i c  a  times  suggests  of  o f CHN  compositions.  3  of  nature  data did not  as t h e o x i d i z i n g  v  nitromethane ^  suggest  that  ]_ )  An e x p l a n a t i o n f o r  inhomogeneous  This  same p r e p a r a -  (detailed values  f o r m u l a s u c h as C x S 0 3 F . y H S O 3 F  proposed by H e r o l d e t  tion  s o  the  for  like  3.2).  nitrogen containing  of N0 (  a general  solvent  Table  products.  obtained for product  Assuming  not  in  The m i c r o a n a l y t i c a l  i n the  -  were o b t a i n e d and even t h e  may b e f o u n d i n t h e  compositions. nitrogen  128  and  stage 0.20%,  be w r i t t e n  as  of  solvent  at  25 a n d 36  product. s a m p l e gave t w o b r o a d r e s o n a n c e s  4.8).  This  observation d i f f e r s  from the  earlier  129 -  - 130 -  1 9  F-NMR  values  given  fluorosulfates, and H S O 3 F  SO3F  Of ions  the  compositionally  homogeneous  w h e r e o n l y a s i n g l e b r o a d r e s o n a n c e was intercalates.  two  values,  intercalated  36 ppm t o  for  into  (see a l s o F i g .  4 3  the s i g n a l at  graphite.  intercalated H S O 3 F  C  14  S  0  and  a -- F r e s o n a n c e a t 9  25 ppm i s  3 -1' F  35.9  the  5  H  S  0  3  ppm  have S O 3 F in  0  F  w  a  respectively.  and a c i d m o l e c u l e s graphite  arrangement observed  lattice,  along  the  contrast,  the  large  suggests extensive i n the GIC. after  since,  3  formed  quite  transfer  in  subsequent  GIC,  in different  This  the  vapor phase.  further  reactions SO3  HSO3F formula  at  14.1  layers  l e a d t o a non-homogemeous  packing  The  of  small  upfield  (-4.6  SO3F"  HSO3F.  groups  for  This  a  shift  ppm) c o u l d be  to molecular  the  a n d - 1 2 . 0 mmol o f g r a p h i t e ,  of  adsorbed  alternate  unsuccessful.  example,  is  and  in  not  totally  formula  of  o n l y 0 . 1 6 2 mmol o f NO c o u l d  s m a l l f r a c t i o n o f NO may  HSO3F  SO3F  spectroscopy  as  a  dissolve volatile  I n a d d i t i o n o x i d a t i o n o f NO i n H S O 3 F 2  In  ( - 1 2 . 4 ppm)  lattice  general  hence never a p p e a r i n g  of N0  at  observation  t o d e t e c t NO i n t h e gas p h a s e b y mass  for  SO3F"  t h e p r e s e n t p r o d u c t may  F-NMR spectrum  shift  i n the excess H S O 3 F ,  amounts  1 9  the  F-NMR resonances  from graphite  d u r i n g the r e a c t i o n .  easily  product  small  i n the  upfield  1 9  direction.  i n t e r c a l a t i o n p r o v e d t o be  C 4S0 F.2-4HS03F be  which w i l l  both  a compound o f  charge t r a n s f e r between the g r a p h i t e  Attempts  unexpected, 7  intercalated  c-axis  i n regard to H S O 3 F  due t o a l i m i t e d c h a r g e  As i n t h i s  4 3  reported  surface  In addition,  4 3  for  the second v a l u e  i s based on an e a r l i e r  r e p o r t e d as s h o w i n g t w o  s  assigned to  The a s s i g n m e n t o f  39 p p m .  seen  acid  4 . 4 and 4 . 7 ) .  i n w h i c h a s a m p l e o f C 7 S O 3 F w i t h some r e s i d u a l showed  graphite  are  possible.  i n H S O 3 F may a c t as a n o x i d i z i n g a g e n t ,  and  Finally, resulting  -  in  the  formation of N 0  further.  The  2  overall  c a n be w r i t t e n  as  131 -  initially,  which  reaction,  could  subsequently  based on t h e r e s u l t s  interact  discussed  above,  follows:  HSO3F  C  +  n  where y - 2 . 4  >  NOSO3F  and n - 7 4 ,  which  C S0 F.y.HS0 F n  are  3  3  average  values  + N 0  of  (  g  )  several  sample  compositions. In not  lead to  albeit using or  summary, first  using this  HSO3F,  from  The l a r g e  compounds,  ions  like  general  is  account  in  obviously  does  nitromethane,  no advantage in  in  the  presence  is  initially  that  NOSO3F  is  rather  surprising.  of  is  unexpected.  [H(S03F) ]"  intercalated  1 9  F-NMR  1  0  Comments a n d  has  conclusions  based  realistic  not as  long  as  the  SO3F.  Conclusion  described  intercalation  resonances  are only  7  2  b e l o w one m o l e p e r m o l e  thesis  fluorosulfate  into  solvent  H-bridged  This  There  in HSO3F  S20gF2-  observation  General  oxidation  i n t e r c a l a t i o n by S 2 0 g F 2  taking  the  4.5  +  as h a d b e e n t h e c a s e  3  amount o f  is  by N 0  SO3F"  anions. ^  However,  acid content  of  over o x i d a t i v e  of  synthesized  stage  different  route  absence  intercalation  the  compounds on t h i s  synthesis  o f bromine-  in fluorosulfuric study  acid,  and  iodine  and  are summarized b e l o w .  some In  all  -  the  synthetic  resistant I(S03F>3 limited  reactions,  solvent  and B r ( S 0 3 F > 3 , thermal  its  tionation  make  Br(S0 F)3  to  c o n f i r m e d by the observed c o l o r 3  concentrations, intercalant  with  the  acid  m a t e r i a l when c a t i o n s Neutral  bromine  The N 0 SO3F"  are  synthetic because is  no  +  s  o  the  i  v  )  prepared from  a  i n the  n  d  N 0 +  graphite. variations  solute  dispropor-  since  both  species  in HSO3F  are  4  is  used  in  noted.  (solv)  S  products  i  v  GIC's  e  even  the conclusion  preferentially  a r e u s e d as  rise  to  and the  with  at  This  to  high  Cationic  little  leads  is  solutions.  and o n l y v e r y  high  iodine  into  interthat  the  host  oxidizers.  Br(S03F>3  or  formation of  anionic  iodine  and  HSO3F  and  compounds.  intercalation  the  into  intercalant  final  I(S03F>3  give  intercalation  over  and  HSO3F.  intercalation  solvated in H S O 3 F  promoted  the  intercalate  intercalates,  reaction, does n o t  graphite-S20gF2  only h i g h stage m a t e r i a l s  initially  in  +  s u c h as  in  by i o d i n e  l2 (solv)  and S O 3 F "  most p o s s i b l e  advantage  properties  uncomplicated  3  solvent  compounds.  4  (  extensive  K[Hal(S0 F) ]  NO s p e c i e s  K[Hal(S03F) ]  containing  and  as  intercalants  like  lattice  acid present  respective  fluorosulfuric  solutes  such  amounts o f  without  changes  3  no a p p r e c i a b l e  concentrations, in  3  species  substantial  calated  Br(S0 F)  3  wide  relatively  the graphite  I(S0 F) ,  like  physical  as weak e l e c t r o l y t e s  3  Whenever  their  oxidation  intercalants  temperature  syntheses  of  and s o l i d  the a c i d allows  form solutions  the  The o x i d a t i o n  to  excellent  directly  and I ( S 0 F ) 3 a c t  3  due  an  c a n n o t be i n t e r c a l a t e d  range o f  ability  as  highly viscous  which  stability  The b r o a d l i q u i d and  the  -  functions  HSO3F  for  132  S20gF2-  are obtained,  where offer  any  intercalation and f u r t h e r m o r e ,  distinct reaction NOSO3F  - 133 -  Finally, such  as  although  X-ray  powder  -• F-NMR a n d U V - v i s i b l e 9  cation  and  layers  still  graphite  ments,  remain,  microanalysis,  diffraction, spectroscopic  characterization  of  Raman  w i t h t h e above c i t e d p h y s i c a l  research f a c i l i t a t e ions present  i n the graphite  lattice.  intercalant  challenge  (EXAFS)  of  guest  in  Electron measure-  t e c h n i q u e s may i n  the complete c h a r a c t e r i z a t i o n  state  identifi-  The u s e o f h i g h r e s o l u t i o n structure  methods  Solid  I n the  t h e most d i f f i c u l t  and e x t e n d e d X - r a y a b s o r p t i o n f i n e  together  spectroscopy,  the species present  chemistry.  physical  t e c h n i q u e s were u s e d , t h e  to a large extent,  intercalation  microscopy  in addition to  future  molecules/  - 134 -  REFERENCES  - 135 -  REFERENCES  1.  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