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Radiochemical studies of cobalt carbonyl hydride derivatives Day, Alison E. 1950

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L'lS- 3  6f  RADIOCHEMICAL STUDIES of COBALT CARBONYL HYDRIDE DERIVATIVES.  by A l i s o n E» Day  Submitted i n p a r t i a l f u l f i l m e n t of the requirements f o r the degree of Master of A r t s .  The U n i v e r s i t y  o f ' B r i t i s h Columbia  Vancouver, B.C. A p r i l , 1950.  d ^ ^ k y  .^  My  2  >9s*  ABSTRACT. 1.  The compound  [?°(C0)^J 1 C o C p h t h ^ j was 2  by a p r e v i o u s l y d e s c r i b e d method found t o be unstable  (15).  prepared I t was  I n the d r y s t a t e and In s o l -  u t i o n i n v a r i o u s organic s o l v e n t s . 2.  The s o l u b i l i t y  o f the compound  In v a r i o u s  organic  compounds was determined. 3.  Conductance measurements i n benzaldehyde and acetophenone were made.  The molar conductances  i n d i c a t e t h a t the compound 4»  Transference solution.  i s a true  obtained  salt.  measurements were made i n an acetone  The c o n c e n t r a t i o n s were determined by  making one or other of the c o b a l t atoms a c t i v e . The r e s u l t s obtained are probably  i n v a l i d because  of exchange between the two c o b a l t atoms. 5.  Exchange between the two c o b a l t atoms i n |Tco(CO)^j^£co(phth)3j  was s t u d i e d , and no exchange was found  under the e o n d i t i o n s o f the experiment. 6.  The exchange between a c t i v e , c o b a l t (11)  ions and  the c o b a l t phenanthrolene complex i o n was s t u d i e d . The exchange was found t o be very r a p i d , r e a c h i n g an e q u i l i b r i u m i n a few minutes. 7.  The exchange between a c t i v e , c o b a l t metal and d i c o b a l t o c t a c a r b o n y l was s t u d i e d , no exchange being found.  ACKNOWLEDGEMENT. I would  l i k e to thank Dr. J . G. Hooley, without  whose able a s s i s t a n c e  t h i s work would have never been  completed. I would a l s o l i k e to express my thanks t o the N a t i o n a l Research C o u n c i l of Canada whose  financial  a s s i s t a n c e enabled work on t h i s p r o j e c t to be on d u r i n g the summer of 19-48.  carried  TABLE o f CONTENTS  Abstract. I.  Historical  1  Introduction  Methods of P r e p a r a t i o n of  \Co(GO)  4  and Co(CO)^H P r o p e r t i e s of ^0(00)4] 2 and Co(CO)^H.... Reactions  of [po'fcoj^g  a  n  d  9 10  Co(GO)^H  14  S t r u c t u r e of Metal Carbonyls II*  19  Introduction.  20  I I I * Experimental Preparation o f Dicobalt Octacarbonyl.....  21  P r e p a r a t i o n o f {Co ( 0 0 ) ^ 2 [cotphthJ^J  23  Solubility  o f \GO(GO)JJ (bo(ph.th)3"].  25  2  Conductance of j C o f C O ) ^ ^ ( p o f p h t h ) ^ i n 27  Benzaldehyde and Acetophenone....... • Transference  31  Measurements..  Study o f Exchange Between the Two Cobalt Atoms i n [00(00)4] f 2  G  o  < P  h  t  h  ) •  3  9  Study o f the Exchange between Co and Co(phth)^ . +  40  Study of the Exchange between Cobalt Metal and D i c o b a l t O c t a c a r b o n y l . . . . .  48  IV*  D i s c u s s i o n of R e s u l t s .  49  V.  Suggestions f o r F u r t h e r Work  52  VI.  Bibliography................  53  (1)  I . HISTORICAL INTRODUCTION Carbonyl chemistry began i n 1890 w i t h the discovery by LudwigMond of n i c k e l carbonyl, Ni(CO),.  Since t h i s  4  time many m e t a l l i c carbonyls and a l l i e d compounds have been discovered, and t h e i r p h y s i c a l and chemical p r o p e r t i e s extensively studied. The covalent m e t a l l i c carbonyls so f a r known are r e s t r i c t e d to the elements of the t r a n s i t i o n groups V i a , V i l a , V i l l a , b, c, a nd l b of the p e r i o d i c t a b l e .  Some  of these elements a l s o form carbonyl hydrides, c o n t a i n i n g one or more atoms of hydrogen, and carbonyl n i t r o s y l s i n which one or more of the CO molecules are replaced by NO. The carbonyls, carbonyl hydrides, and n i t r o s y l carbonyls so f a r known arB shown i n Table I . The metal carbonyls d i f f e r i n t h e i r p h y s i c a l prope r t i e s from a l l other compounds formed by the t r a n s i t i o n elements.  A l l of the monomeric carbonyls are extremely  v o l a t i l e , and most of the polymeric carbonyls can be sublimed.  This v o l a t i l i t y connotes l a c k of cohesion be-  tween the molecules, caused by l a c k of e x t e r n a l f i e l d . A c l o s e d e l e c t r o n i c s t r u c t u r e i s i n d i c a t e d by the f a c t that a l l of the simple carbonyls and t h e i r s u b s t i t u t i o n products are dimagnetic.  The carbonyls and carbonyl  hydrides are soluble In non p o l a r organic s o l v e n t s , and i n s o l u b l e i n polar s o l v e n t s . The carbonyl hydrides are extremely v o l a t i l e substances, e x i s t i n g normally only at temperatures  well  (2)  below room temperature.  Above t h i s temperature they  spont-  aneously decompose i n t o the carbonyl, w i t h the e v o l u t i o n of hydrogen.  They are weakly a c i d i c i n nature and w i l l  form s a l t s w i t h the a l k a l i metals and bulky amine c a t i o n s . The present work e n t a i l e d the preparation and a study of some of the p r o p e r t i e s of cobalt carbonyl hydride, Co(CO)^H, d i c o b a l t octacarbonyl, C c o ( C 0 ) ^ ] , and a s a l t 2  of cobalt carbonyl phth-o-phenanthroline,  using r a d i o a c t i v e Co  60  as a t r a c e r .  Group Via M(C0)  Vila  Villa  VHIb  VIIIc  lb  6  Cr, Mo, W.  r  [M(CO) J 5  Re  2  M(CO)  5  Pe, Ru, Os.  Carbonyls  M (C0) 2  9  Pe, Ru, Os. [M(CO) ] 4  3  [M(COH1  Pe, Ru.  M(CO)  2  Co,Rh,Ir.  [M(CO) J 3  [M(CO) ]  X  3  Pe.  Ni.  4  Co,Rh,Ir. M (CO) 4  4  ^(co) ] , 3  ;  Cu.  I:L  Rh. Carbonyl  Carbonyls.  M(C0) H  Re?  Fe,Ru?,Os.  5  Hydrides Nitrosyl  M(CO) H  1  4  M(C0)^H  2  Co,Rh?,Ir?. 1  M(C0) (N0) 2  Pe  2  M(CO) NO 3  Co  U) Methods of P r e p a r a t i o n of CCo(CO)/~U and Co(CO)/H. ' ''t ti ' '•* (1).  High Pressure The  Synthesis.  o r i g i n a l and u s u a l l y the simplest method of  f o r m a t i o n of the c a r b o n y l s i s by the d i r e c t of the metal w i t h carbon monoxide.  interaction  The metal must be i n  a f i n e l y d i v i d e d s t a t e , and the r e a c t i o n i s u s u a l l y c a r r i e d out under h i g h pressure and temperature.  The  techniques  of t h i s method have been g r e a t l y improved by Heiber  and cu  h i s co-workers ( 1 ) ,  who  used a r o t a t i n g autoclave  of w i t h s t a n d i n g p r e s s u r e s up t o 350 D i c o b a l t o c t a c a r b o n y l was manner by Mond and H i r t z  capable  At.  f i r s t prepared  i n this  (2), by p a s s i n g carbon monoxide  over pure c o b a l t at 30-250 A t . and 150-220 °C.  T h i s method  i s somewhat inconvenient however, as the metal must be i n a c a r e f u l l y reduced, In 1939  f i n e l y divided state.  I t was  (3)  found by S c h u l t e n  that d i c o b a l t  o c t a c a r b o n y l c o u l d c o n v e n i e n t l y be produced from anhydrous c o b a l t h a l i d e s i n Hieber's a u t o c l a v e .  CoF  l s 2  without  r e a c t i o n , whereas the other h a l i d e s i n c r e a s e i n r e a c t i v i t y In the  order C o C l < CoBr <CoI 2  2  2  The r e a c t i o n preceeds  (1)  (A)  according to the  equation  2CoX +-ACu -r-800—* Co (C0)g+• 4CuX 2  2  the Cu coming from the autoclave l i n i n g . t i o n no c a r b o n y l h a l i d e (COX)2 was  During the r e a c -  formed, so the r e a c t i o n  d i d not seem to occur through the r e d u c t i o n of the h a l i d e  (5)  t o  t h e  m e t a l  i o d i d e  w a s  b y  c a r b o n  s h o w n  t o  r e a c t  t e m p e r a t u r e  g i v i n g  a p p r e c i a b l y  v o l a t i l e .  c o p p e r  a n d  t o  o r  t h e  a c t  a n d  i  s i l v e r  c o p p e r  a s  t  d i v i d e d  2 0 0  d i n g  A t .  t o  w a l l s  t o  a n d  g e n e r a l  t h e  i  p o l a r i z a b l e  l a t t i c e  +  t  highly  i  l  l  r e a c t  c o p p e r  a t  i s  t h e  t o  o r  t h e  o f  w i t h  p r o d u c e  s i l v e r  p r o c e s s ,  t h e  i n c r e a s e d  t r e a t e d  r o o m  f o r m  a d m i x t u r e  h a l i d e  a t  w h i c h  2  t o  e s s e n t i a l  a l s o  8 C 0  b e e n  c o m p o u n d s  h i g h  c o n t a i n  t r a c e s  h y d r i d e  a l s o  a r e  f i n e l y  t h e  y i e l d .  c a r b o n  t h e  m o n o x i d e  c a r b o n y l  o f  2 C o S  8 C 0  +  h a s  w h e n  a c c o r -  8 0 0 - v  H  ( 5 0  —  2  H  5  »  4  A t . )  a n d  S  i o n i c  s h o w n  n i c k e l  o r  c a r b o n  t o  b e  t h e  — > 2 C o ( C 0 ) , H  w i t h  n  w h i c h  f o r m e d  r e a c t a n t s  i n t o  c o b a l t  m o n o x i d e .  2 C o ( C 0 - ) ^ H  -4CU  i  *  b e  t y p e .  c o n v e r s i o n  c o b a l t  c a n  s o l i d e s  w h e n e v e r  P a r t i a l  m e t a l l i c  a n d  f r o m  b e e n  s y n t h e s i s  m o i s t u r e .  +  i . e .  2  c a r b o n y l s  c o b a l t  p u r e l y  h y d r i d e  h y d r o g e n  -e  o f  2 C u  +  t h a t  i r o n ,  n o t  p r e s s u r e  o c c u r s  2 C o  o f  f o u n d  n o n - m e t a l s ,  c a r b o n y l  i s heated i n  > > L C o ( C 0 ) / [ 2  h a s  f o r c e s  C o b a l t  the  o f  e v e n  c o b a l t  e q u a t i o n  by  in  w  b e l i e v e d  t h e  h a n d ,  C o I C 0  c o m p o u n d ,  p r e s e n c e  w h e n  o t h e r  m o n o x i d e  t o  c o b a l t  (1)  t h e  v e s s e l  i s  t h a t  2 0 0 ° C .  f o r m e d  (1)  t h e  T h e  t h e  2 C 0 S + - 4 C u  the  o f  O n  c a r b o n  i s  a c c e p t o r  s u l p h i d e  t h e  I n  T h i s  f o u n d  m e t a l s  w i t h  a d d i t i o n  h a l i d e .  b e e n  C o b a l t  a t  a n  h a l o g e n  h a s  m o n o x i d e .  2 C u  P  S  t h e  s u l p h i d e  (6) (2)  Preparation i n Solution* Carbonyls can be prepared by a number of reactions' i n  s o l u t i o n In which the r e d u c t i o n of the metal i s brought about by s u l p h i d e s , c y a n i d e s , or even carbon monoxide i n strongly alkaline In 1926  Itself  solution.  Job and h i s co-workers  (5) observed t h a t the  r e a c t i o n between carbon monoxide and the G r i g n a r d reagent was  a c c e l e r a t e d by the presence of s a l t s of the t r a n s i t i o n  metals, and from the r e a c t i o n mixture they separated an e t h e r s o l u b l e compound of chromium which was  proven t o be  chromium hexacarbonyl. The mechanism of the r e a c t i o n appears t o be the p a r t i a l r e d u c t i o n o f the metal s a l t , and the combination of carbon monoxide w i t h one of the r e d u c t i o n products, which upon a c i d decomposition y i e l d s , among other products, the metal carbonyl. it  The product by t h i s method i s very pure,  and  has proved to be the best method f o r p r e p a r i n g chromium  hexacarbonyl. A l k a l i n e s o l u t i o n s of c o b a l t and n i c k e l s a l t s  absorb  carbon monoxide i n the presence of c y s t e i n e , a s u l p h i d e , cyanide, t a r t r a t e , or amino a c i d , which on  acidification  g i v e N i ( C 0 ) 4 and Co(C0)^H r e s p e c t i v e l y . C y s t e i n e , SH.CH .CH(WH )C02H^(H SR), forms w i t h b i v 2  2  2  a l e n t c o b a l t a complex s a l t of the type  which In a l k a l i n e s o l u t i o n i s s e n s i t i v e to oxygen and  also  (?) absorbs (6),  one  The  molecule  of carbon  monoxide p e r  complex u n d e r g o e s d i s p r o p o r t i o n a t i o n ,  being recovered  K3 [ C o ( S R ) 3 ]  and  .3H 0, 2  2  The  cobalt carbonyl hydride being  cobalt  regenerated  salt  other  Absorption cobalt  y- Co(0H) -r-20o(C0)^H 2  so t h a t a s m a l l  place with cobalt  of carbon  monoxide f i r s t (9)  KX  2  which f u r n i s h e s c o b a l t Thus w i t h  A  +  alkaline  ence o f c y a n i d e  suspension will  is  and  absorb  The  Gilmont potassium  •+ Co(CO)^H i n the  pres-  cyanide  T h i s method has  developed  as  salt  octacarbonyl  been  a means o f p r o d u c i n g of cobalt carbonyl  T h i s decomposes a t room t e m p e r a t u r e  i n v o l v e d are? as f o l l o w s :  2  carbon monoxide, the  formed, which upon a c i d i f i c a t i o n  to give d i c o b a l t  2  of a cobalt salt  a g a i n a c t i n g as a c a r r i e r .  (11)•  potassium  *12KC1+ 4 C o X 3 + C o ( C O ) 5.EtOH  5  (10)  carbonyl  A  A  Blanchard  (8).  forms a s u b s t i t u t e d  C o ( C O ) . E t O H + 2 H — V E t O H + Co" + CO -f | H  by  salts  (X *CoH^.O.CS.S~)  A  6 C o C l + 1 2 K X + 5C0 + E t O H  An  (II)  t h i o compounds t h a t f o r m i n n e r complex s a l t s  carbonyl derivative  xanthate,  the  (7).  h y d r i d e when decomposed w i t h a c i d .  2  amount  t o b r i n g about n e a r l y complete c o n v e r s i o n o f  Analogous r e a c t i o n s take and  cysteine  formed.  ..3  2  c y s t e i n e i s thus  suffices  The  i n the form o f a c o b a l t ( I I I ) complex,  9iGo(SR) j-^8G0 + 2 H 0 — » 6 C o ( S R ) 3  •  atom o f c o b a l t  and  yields or  the  [00(00)4] hydride  free  hydride.  on g e n t l e warming  hydrogen.  The  2  reactions  (3)  2Co(N03), ^- 12KCN-*2K^Go(CN) -»-4KN0 2  6  12K0H + 2K4Co (CN) 6  3  11C0 —^3K CO3 + 12KCN + 6H 0 •+ 2KCo (C0) ^ 2  2  2Co(N03) -r-12K0H -VllCO—HKNO3 + 3K COj 2  2  KCo(C0)4-»-H *—iCo(CO)^H+K -  +  2Co(C0) H—i£co(CO) 7 +H 4  4  2  2  + 6H 0 "t~KCo (CO) ^ 2  (9) Properties of [ C o ( C 0 ) ^  2  and Co(GO)^H  D i c o b a l t o c t a c a r b o n y l u s u a l l y e x i s t s as a dark brown m i c r o c r y s t a l l i n e s o l i d , but when pure yellow c r y s t a l s .  I t i s obtained as  I f i t stands i n a vacuum i t s l o w l y sub-  l i m e s , forming a few  c l e a r orange c r y s t a l s on the w a l l s .  C r y o s c o p i c m o l e c u l a r weight  d e t e r m i n a t i o n s i n benzene  and Fe(CO)(j (9) i n d i c a t e the d i m e r i c f o r m u l a . vapour p r e s s u r e of 0.07mm. at 15*C.  I t has a  and melts at 51*0.,  decomposing at s l i g h t l y above t h i s temperature c o b a l t dodecacarbonyl  £co(C0)oJ^,  F u r t h e r h e a t i n g produces [co(CO)* e t h e r , naphtha,  into  and carbon monoxide.  the f r e e m e t a l .  i n s o l u b l e i n water, s o l u b l e i n  a  a l c o h o l and N i ( C O ) ^ ( 2 ) .  CS , 2  I f these  ions are kept f o r some time or warmed: decomposition The pure c a r b o n y l i s u n s t a b l e i n a i r , b a s i c carbonate. of CO or  tetra-  solutensues.  forming a v i o l e t  I t i s s t a b l e however i n an atmosphere  H . 2  C o b a l t c a r b o n y l hydride i s a y e l l o w gas which Is extremely poisonous  and has a very bad odor.  I f cooled  t o below -33°C i t forms a pale y e l l o w s o l i d , which on warming melts to a l i g h t y e l l o w l i q u i d , which darkens to decomposition  into  [co(C0)^j  2  has been shown to be r e v e r s i b l e ,  and H . 2  due  This r e a c t i o n  [Co(C0)^  D  e  i  2  converted i n t o the hydride when heated i n H CO,  rapidly  2  n  S  partly  (120 At.)  and  at 165°C. ( 1 ) . The  hydride Is r e l a t i v e l y s t a b l e i n CO,,and can be  d i s t i l l e d i n a stream o f CO w i t h p r a c t i c a l l y no  decomposition.  (10) It  dissolves  a l t h o u g h the  out  of  such a stream,  s o l u t i o n decomposes  i n water  l o n g , enough f o r a r o u g h e s t i m a t e  strength  t o be made.  of  this  CO c a r r y i n g  t h r o u g h a r o t a r y a b s o r p t i o n tower tilled  water  quickly  Postulating  HCo(C0) -^tiH  +  +  4  and m a k i n g r o u g h e s t i m a t e s  of  salt  acetic  Indicate  a c i d 1.8*10  More r e c e n t l y simiifcar  method,  values  -5  Reactions  of  g o i n g a wide  the  the  of  ^Co(CO)^]2 i s w i t h the  2  acid  orange  nature:  amount o f  of  a c i d and  its  between  that  formic a c i d ,  Ionization constant  accuracy.  has  Using a  -14  were  2*10  of  -4  •  the  been  deter-  potentiomet-  apparatus,  obtained for  the  the  constants.  and C o ( C 0 ) ^ H are reajtive  substitution  reactions  carbonyl Involve  C o ( C O ) ^ i o n as  bases,  the  and t h a t  carbonyls  v a r i e t y of  A g o o d many o f  the  of  ionization  [Co(C0)^  As a c l a s s  cobalt  the  dis-  4  and K^" 4X10  p r i m a r y and s e c o n d a r y  an e x p e r i m -  The m e t h y l  a n d e x c l u d i n g a l l a i r f r o m the  K ^ a 4"<L0  acid  Co(C0) "  (13) t h e  degree  it  hydride vapours  i r o n carbonyl hydride, FelCOj^R^,  mined w i t h a f a i r ric  ,  its  out  an i o n i z a t i o n constant -5  and  containing 2 0 0 c . c .  a n d some m e t h y l o r a n g e .  turned red.  neutral  of  Coleman ( 1 2 ) c a r r i e d  type by p a s s i n g  0°G.,  i n a few m i n u t e s ,  persists  ent  at  the  that  and a d d i t i o n  have b e e n  formation of  a primary step  i n the  hydrolized in either  formation of  the  compounds,  hydride  the  under-  reactions.  studied  for  hydride,  or  reaction. s t r o n g o r weak (14) ( 1 5 ) .  With  (11) s u c h as B a ( 0 H )  strong bases  3  CoCCO)^  2  o r KOH the  2  3  is:  V40H^-V4Co(C0)^H + 2 C 0 + 2 [ c o ( C 0 ) [ p o l y m e r 3  =  3  At lower hydroxy1 Ion c o n c e n t r a t i o n s given  reaction  (NH^) t h e  reaction  is  by:  C o ( C O ) ^ 2 ^ 4 H 0 - > 4 C o ( G 0 ) ^ H + 2 C o ( 0 H ) + 8C0 2  2  The d i l u t e blue,  solutions  and a r e v e r y e a s i l y  giving cobalt Cobalt  but  s a l t s w i t h the It  as  or m i l d  methylene oxidants,  a l s o forms  b u t have  a weak m o n o b a s i c  a l k a l i metals  have  conductivities  acid,  and w i t h b u l k y  compounds w i t h the  t h e s e compounds do n o t  salts,  reduce  tetracarbonyl.  ammine c a t i o n s . metals,  o x i d i z e d by a i r  carbonyl hydride acts  forming true  true  o b t a i n e d by h y d r o l y s i s  the  heavier  properties  c o r r e s p o n d i n g to  of  weak  salts. Prom t h e  reaction  of  an ammonia s o l u t i o n  o b t a i n e d by h y d r o l y s i s  of  the  heavy m e t a l ounds o f  salts,  the  Co(CO)^H,  carbonyl, with solutions  H i e b e r and S c h u l t e i i  following  of  (14) o b t a i n e d  of  comp-  type:  H C o ( C O ) ^ +- [MeAh]" "-  y[Go(CO)4] [MeAn]-r-2H  1  +  2  An *NHo , a m i n e . j  Me - v a l e n c e W i t h hexamine no r e a c t i o n was W i t h hexamine obtained. was  formed.  cations  2 metal. of valence  2 metals  o b t a i n e d w i t h Z n , Cd o r Cu s a l t  CoCl  2  solutions  With NiClg Gaseous  it  was  found  solutions.  [ C o ( C 0 ) 4 ] [ C o ( N H 3 ) j was 2  6  a s i m i l i a r compound [ C o ( C O ) ^ J [Ni (NH3) J 2  ammonia w i l l  also react  directly  6  with  that  (12) cobalt  carbonyl:  3 [ 0 0 ( 0 0 ) ^ 2 +12NH —>>2 [ C o ( C 0 ) ] 2 L c o ( N H ) ] + 8 C 0 4  3  3  6  Both the c o b a l t and n i c k e l compound are extremely s o l u b l e i n water, and t h e r e f o r e d i f f i c u l t  to isolate.  They are char-  a c t e r i z e d by ease of spontaneous decomposition and ammonia loss • With t r i s p h e n a n t h r o l e n e  c a t i o n s s a l t s of the type  Jco(CG)^J t M ( p h t h ) ^ | are formed, where M <&Co, N i . These comp2  ounds are very i n s o l u b l e i n water and can be used as a method of a n a l y s i s f o r Co(C0),H. They are r e a s o n a b l y s t a b l e i n t h e 4  dry s t a t e . With HgCl2 and ammoniacal  Co(C0)^H the compound Co(C0)^Hg  i s p r e c i p i t a t e d . T h i s compound i s i n s o l u b l e i n water, s o l u b l e In o r g a n i c  solvents.  I t s formation  the presence o f Co(C0)^H.  can be used t o d e t e c t  I t i s unstable,  and decomposes i n  a short time t o a grey powder. With ammoniacal AgNO^ the compound can be i s o l a t e d .  T h i s compound i s a l s o i n s o l u b l e In water  and s o l u b l e i n organic In order considered  Co(CO)^ Ag^CO^HgO  solvents.  t o determine whether  or not they could be  as true s a l t s o f the h y d r i d e ,  Hieber  (16) made  s t u d i e s o f the c o n d u c t i v i t i e s o f these compounds and the s i m i l i a r compounds o f i r o n c a r b o n y l  hydride.  He found that  i n s o l u t i o n s o f methanol and of acetone, the s a l t s formed w i t h the hexammine and w i t h the  trisphenanthroline  had molar c o n d u c t i v i t i e s corresponding electrolytes.  cations  t o s o l u t i o n s of s t r o n g  These compounds may t h e r e f o r e be  considered  (13) as t r u e s a l t s decreased  of the carbonyl hydrides.  w i t h time,  ounds i n s o l u t i o n .  i n d i c a t i n g decomposition With the mercury s a l t s  c o n d u c t i v i t y was v e r y l o w (0.4 and  The c o n d u c t i v i t i e s  I t c a n be i n f e r r e d  o f t h e comp-  however, t h e m o l a r  f o r Co(CO).HgCl i n acetone) 4  t h a t these  compounds a r e n o t t r u e  salts. Hieber  expresses  the view t h a t s t r u c t u r e s such  Go(CO)  as  a r e n o t s t a b l e , a n d c a n o n l y be s t a b i l i z e d b y t h e f o r m a t i o n o f s a l t s w i t h complex c a t i o n s . s o l u t i o n s o f the hydride normal s a l t s metal as  (13)  c o n t a i n aquo s a l t s r a t h e r  not yet prepared,  i s b y f a r n o t as g e n e r a l  t o be I n a n o r d i n a r y f o r m a t i o n  p r e p a r a t i o n o f t h e anhydrous s a l t s Fe(C0)^K a n d measurement o f t h e I o n i z a t i o n c o n s t a n t  as a weak a c i d , The  seem t o d i s p r o v e t h i s  o f Pe(C0)^H  that i n general  forming  t h e amines d i s p l a c e a p a r t o f t h e  the f o r m a t i o n  o f mixed complexes.  e f f e r v e s c e n c e due t o e s c a p i n g  compound 003(00)^(C^H^N)^  2  and h i s coworkers ( 1 7 ) .  t e t r a c a r b o n y l or cobalt t r i c a r b o n y l  pyridene,  and Pe(CO)^KH  r e a c t i o n o f c o b a l t c a r b o n y l w i t h complex  c a r b o n y l group w i t h cobalt  2  of salts.  view.  amines haa a l s o b e e n s t u d i e d b y H i e b e r They f i n d  than  and t h a t t h e f o r m a t i o n o f  d e r i v a t i v e s of the hydrides  I t I s supposed  The  He a l s o s t a t e s - t h a t a l k a l i n e  crystallizes  f a s h i o n t h e complex 00(00)3(phth)  2  When  are placed i n  CO e n s u e s , and t h e out.  In a s i m i l i a r  i s formed w i t h a phenanth-  roline. W i t h a l c o h o l s t h e compounds C o ( C O ) 5 . C H 3 O H a n d Co_(CO) .1.5C H_0H a r e o b t a i n e d , and w i t h t h i o a l c o h o l s 2 J 2 5 2  c  o  00(00)3.SC H 2  5  (18).  when t r e a t e d w i t h  A l l o f these  acids  compounds l i b e r a t e  Co(CO)^H  (14) The S t r u c t u r e of Metal C a r b o n y l s . A theory f o r the s t r u c t u r e of the monomeric c a r b o n y l s has been worked out, which f i t s  In w i t h t h e i r  peculiar  p r o p e r t i e s , such as v o l a t i l i t y , and agrees w i t h the ental facts.  experim-  Although a number of s t r u c t u r a l t h e o r i e s have  been proposed f o r the polymeric c a r b o n y l s , none of these has as yet been completely s a t i s f a c t o r y , and t h e i r is s t i l l  structure  somewhat i n doubt.  The use.Sdf e f f e c t i v e atomic number (E.A.N.) i n c l a s s i f y i n g the v o l a t i l e monomeric c a r b o n y l s has been found extremely h e l p f u l and the p r o p e r t i e s of the c a r b o n y l s show a.marked u n i f o r m i t y a c c o r d i n g to t h i s c l a s s i f i c a t i o n .  The  E.A.N, i s d e f i n e d as the t o t a l number o f e l e c t r o n s h e l d w i t h i n the sphere o f the atom, and i n c l u d e s those f u r n i s h e d by the atom I t s e l f , those added by e l e c t r o n t r a n s f e r ,  and  those added through establishment of c o v a l e n t and c o o r d i n a t e bonds.  Whenever the E.A.N, of the c e n t r a l metal stom of  the compound Is equal to t h a t of an i n e r t gas i t i s p o s s i b l e f o r the compound to be  volatile.  In the v o l a t i l e c a r b o n y l s I t can be shown that the CO groups e x i s t as such i n the molecule and r e t a i n on the whole the bond nature o f the CO atom, i . e . :C::sO::. l i n k c o u l d thus be r e p r e s e n t e d by M:C:::0:;.  The CO  I t can be  metal seen  that each CO molecule thus donates one p a i r of e l e c t r o n s to the c e n t r a l metal atom. ility  T h e n i f the c r i t e r i o n f o r v o l a t -  i s the attainment by the metal of the E.A.N, of an  (15) inert  gas,  28, w h i c h  t h e n f o r example n i c k e l w i t h an a t o m i c i s eight  less  than the atomic  s h o u l d t a k e up f o u r m o l e c u l e s  o f CO,  number  of  number o f k r y p t o n ,  forming Ni(CO)..  It  A has b e e n f o u n d t h a t this rule,  having c e n t r a l metal  rare gases* the  This  diamagnetism Elements  of  rare  and do  a l l o f t h e monomeric c a r b o n y l s f o l l o w  accounts f o r t h e i r  volatility  the  atomic  number c a n n o t  simple c o o r d i n a t i o n  n o t f o r m monomeric c a r b o n y l s .  c a r b o n y l s the elements belongs,  o f group  structure,  The  lower c a r b o n y l s formed  way  t h e n combine  Vlllb.,  suggested  t h e E.A.N, o f a r a r e  c a n f o r m two  less  as w o u l d  t h a n the  be  rare  are  also  i n some  sublimed. octacarbonyl Sidgwick  a general principle  on t h e h y p o t h e s i s t h a t  acquire  groups  cobalt  p o l y m e r i c c a r b o n y l s a r e not  p o l y n u c l e a r c a r b o n y l s and  based  to which  t h e atoms a r e s t a b i l i z e d  i n most c a s e s c a n be  (19)  pairs,  to form d i m e r i c m o l e c u l e s .  e x p l a i n the case o f d i c o b a l t  and B a i l e y  t h e E.A.N,  by many o f t h e e l e m e n t s  b y p o l y m e r i z a t i o n . The  To  ing  and  suggesting that  v o l a t i l e , but  also  In t h e i r h i g h e s t  e x p e c t e d t o g i v e them as E.A.N, o f one gas  attain  of e l e c t r o n  c o o r d i n a t e s u c h a number o f CO  polymeric,  and  o f the m o l e c u l e s .  o f odd  gas b y  atoms w i t h t h e E.A.N, o f  nitrosyls.  f o r formulat-  Their  theory  was  a l l the m e t a l  atoms s h o u l d  gas,  t h e CO  and  that  group  —0= c-«  collinear  coordinate links. one  a second c o o r d i n a t e l i n k  CO  molecule  forms  t h r o u g h t h e o x y g e n as d o n o r ,  leading  (16)  t o the  This  structure:  ( o=?c —O^Co*- o^c-^Co  gives  35#  the  the  latter  one  extra  cobalt  A good d e a l proposed by  A  This  similiar  the  e a c h the  studies  krypton  3  the  other  passed along  on  been c a s t  the  on  the  structures cry-  eneacarbonyl of i r o n ,  b e e n shown t o have t h e  for  Co(CO)^  to  structure.  B a i l e y , mainly through X-ray  compound has  structure  and  former being  o f d o u b t has  S i d g w i c k and  stallographic (20).  atom an S.A.N, o f 37  e l e c t r o n on  to give  L * - o ^ a )  w 2  °uld  Fe^iGO)^  structure:  be:  <LZo These s t r u c t u r e s electronic  however l e a v e  s p i n , and  the  T h e i r diamagnetism can that  the  two  K.A. o f the  M This  are  Jensen  bridge  fits  o n l y be  paired,  (21)  has  g r o u p s by  [A the  molecules  m e t a l atoms a r e  electron spins  e a c h atom w i t h one should  explained  be by  paramagnetic. the  so c l o s e t o g e t h e r  e v e n t h o u g h no  unpaired  hypothesis that  the  bond Is  formed.  more r e c e n t l y s u g g e s t e d  linking  resonance between the  M  i i v  observed bond l e n g t h s  n  forms  \A  o f Fe^CO)*?, a n d a c c o u n t s  (17) for  the  diamagnetism of  the  molecule.  The s t r u c t u r a l p r i n c i p l e u n d e r l y i n g t h e of the  composition  series Pe(CO) H 4  seems t o be  the  i g u r a t i o n of i n the  Go(CO)^H  2  attainment  Ni(CO)^  of  the  closed  electronic  conf-  Ni(CO)^. carbonyl hydrides  odd a t o m i c number t o  attain  of  It  a r a r e gas,  since  it  the  is  effective  c a n be assumed  atom d o n a t e s one  electron  may e x p l a i n why,  i n many r e a c t i o n s ,  is formed i n p r e f e r e n c e  possible  to  to  the  the  for  atomic  that  cobalt  of  number  the  c e n t r a l metal  atoms  hydrogen atom.  This  carbonyl hydride  octacarbonyl.  The c a r b o n y l  h y d r i d e s have b e e n shown b y e l e c t r o n d i f f r a c t i o n m e a s u r ements of  ( 2 2 ) t o be  linkage  of  the  a b l i s h e d b y the (24)  holds  the  w i t h 111(00)^.  isoelectronic hydrogen i s  electron view  however  not d e f i n i t e l y  d i f f r a c t i o n data.  Hieber  the  are  that  h y d r o g e n atoms  o r a t e d i n some way as  p r o t o n s w i t h i n the  and i r o n a t o m s .  structure  w i t h the  This  observed  a c i d nature  E v a n s and L i s t e r is s i t u a t e d ture  at  (25)  end o f  agrees w i t h e l e c t r o n  i s i n agreement rarely not  the  as  w i t h the  a t i o n of  the  the  however  of  have  the  core  of  does n o t  of  chain M-C-O-H.  of  four,  hydrogen i s  a h y d r o g e n atom a c c o u n t s  (23),  the  cobalt  conform  hydrides.  suggested that  properties  est-  incorp-  the This  d i f f r a c t i o n measurements  sumes a c o v a l e n c y  s u r p r i s i n g that  The mode  the  for  the  strucand  hydrides.  and i t easily  hydrogen  is  also Oxygen  therefore  lost. reducing  Liberpower  (18)  and I n s t a b i l i t y of these compounds;, which decompose at a temperature w e l l below room temperature.  They may  also  d i s s o c i a t e as an i o n : M:C:::0:H^=i MrC:::Or+H  +  allowing the hydride to form s a l t s such as f o r example Co(CO)^K and  [ C o ( C 0 ) ^ [Co(phth)-J . 2  While the chemical  p r o p e r t i e s of the hydrides seem to agree w i t h t h i s s t r u c t u r e , there has as yet been no evidence advanced to show that there are two types of M-C  and C-0 bond dimensions  w i t h i n the molecule, as would be expected f o r a s t r u c t u r e of t h i s type.  (19)  II*  Introduction. The  object of t h i s work was t o prepare the compound  [co(CO)4] [Oo(phth)-3j (phth e o-phenanthroline), 2  and by  t r a n s f e r e n c e measurements to determine i f p o s s i b l e the r e l a t i o n which i t bears t o the the  Co(CO)^  i o n or the  Co(CO)^  Co(phth)  by the use o f r a d i o a c t i v e c o b a l t ,  ion. Either  i o n c o u l d be t r a c e d i ^ w a s assumed t h a t  there was no exchange between the two c o b a l t atoms  in  the compound, but t h i s was l a t e r proved not t o be the case.  D i f f i c u l t i e s were encountered because of the  extreme I n s t a b i l i t y of the compound, and only very rough measurements were obtained. o f the m o l a l  Approximate measurements  c o n d u c t i v i t y i n benzaldehyde and acetophen-  one were a l s o made, and these  compared f a v o r a b l y w i t h  measurements made on s i m i l i a r cimpounds (16), that the compound i s a s t r o n g The  indicating  electrolyte.  s o l u b i l i t y of t h e compound and i t s s t a b i l i t y  i n v a r i o u s organic s o l v e n t s were determined* Because o f the r e s u l t s o b t a i n e d  i n the t r a n s f e r e n c e  measurements, the exchange between c o b a l t ++  and  the  Co(phth),  i o n was s t u d i e d .  (11) ions  (20)  III.  Experimental. The  at  radioactive Co^  G  used was prepared i n the p i l e  Chalk R i v e r by i r r a d i a t i n g C 0 2 O 3 .  o l v e d i n concentrated  hydrochloric  The oxide was d i s s -  a c i d and the s o l u t i o n  n e u t r a l i z e d w i t h ammonium hydroxide.  Por the experiments  an exchange CoC^.SH^O was added t o the s o l u t i o n of a c t i v e c o b a l t t o g i v e the d e s i r e d s p e c i f i c a c t i v i t y , and t h e amount o f c o b a l t i n a g i v e n volume was determined the^-nitroso^3 -napthol  method (26).  portions  using  of the  s o l u t i o n were then counted to o b t a i n the number of counts per gram o f c o b a l t . The filled  counting  circuit  consisted  G-eiger tube attached  of an argon methonal  to a s c a l i n g c i r c u i t .  The tube  had  a p l a t e a u o f about 300 v o l t s w i t h about a 1% r i s e .  The  background remained constant  ation.  over the p e r i o d of oper-  The samples were counted on s m a l l watch g l a s s e s ,  h e l d i n p o s i t i o n on an aluminum t r a y , and were t h i n enough that i n t e r n a l a b s o r p t i o n standard  c o u l d be n e g l e c t e d .  The  and samples were counted under i d e n t i c a l cond60  i t i o n s o f geometry.  The h a l f l i f e  o f f i v e years f o r Co  i s l o n g enough so that decay of the a c t i v e c o b a l t , over the p e r i o d o f measurement; c o u l d be  neglected.  Figure  I.  (21) Preparation of Dloobalt Qctacarbonyl. Dicobalt  o c t a c a r b o n y l was  p r e p a r e d b y t h e method  o u t l i n e d by Gilmont  and B l a n c h a r d  amounts  as d e s c r i b e d b y them,  of reagents  edure  the a l k a l i  first  p r e p a r e d b y s h a k i n g an a l k a l i n e  suspension  was  of c o b a l t  i n the presence  of t h e type ide  salt  (11) u s i n g t h e samB  i n a slow  easily  stream  o x i d i z e d and i t was  In t h e a p p a r a t u s  no Co(CO)^K was  the  exit  found  t h a t any t r a c e  To p r e v e n t  just  a i r entering  T h i s procedure  was f o u n d  t o be e f f e c t i v e  flask.  i n preventing  o x i d a t i o n of the Co^Oj^K* Cobalt  c a r b o n y l h y d r i d e was  u t i o n of t h e p o t a s s i u m chloric  acid.  tube  t e n hours  liberated  from  the  s a l t b y t h e a d d i t i o n o f 12N  The s e t - u p u s e d  shown i n f i g . 2 .  about  for collecting  The s o l u t i o n was  temperature.  at - 7 9 °  hydro-  the hydride  i n a U-shaped  c o o l e d t o -79°C. In dry i c e - a l c o h o l mixture.  evacuated  sol-  swept w i t h CO f o r  and t h e h y d r i d e c o l l e c t e d  t h e h y d r i d e had b e e n c o l l e c t e d was  attached  t o u c h i n g the s u r f a c e of  o f w a t e r c o n t a i n e d i n a 500ml.  is  of a i r  o f the suspension,  a s m a l l amount  the  .  The Co(CO)^K f o r m e d i s v e r y  obtained.  o f a g l a s s tube  shaker  and t h e c a r b o n monox-  s i d e a r m d u r i n g t h e s h a k i n g a t r a p was  consisting  cyanide  through the apparatus  l e d to darkening  and  cobalt(II)  of c a r b o n m o n o x i d e . . A  d u r i n g the shaking p r o c e s s .  proc-  t e t r a c a r b o n y l hydride i s  shown i n f i g . l was u s e d  passed  i n this  t h e tube  When  containing i t  and t h e n a l l o w e d t o come t o room  The C o ( C O ) . H m e l t s  to a light  yellow  liquid  Figure  II.  (22)  which darkens  The  r a p i d l y due  dicobalt  to decomposition  o c t a c a r b o n y l formed  a d a r k brown m i c r o c r y s t a l l i n e  solid.  into^Co(CO))  i n t h i s manner i s I t decomposes i n  the presence  of a i r to give a v i o l e t basic  It  i n an a t m o s p h e r e o f c a r b o n monoxide o r  i s stable  ogen, and  i t was  found  that  i t c o u l d be  decomposition  i n the tube  if  allowed to enter.  no  a i r was Most  Any  that  prepared  of the  removed I n t h i s manner was  out w i t h the p a r t i c u l a r c o n c e n t r a t e d NH/OH.  sides  solvent  t o be  used,  hydr-  without  c o u l d be removed f r o m  by g e n t l y t a p p i n g t h e  c o u l d not be  kept  i n w h i c h i t had b e e n  o f t h e [Co ( 0 0 ) 4 ^ 2  t u b e f o r use  carbonate.  the  tube. washed  usually  (23) P r e p a r a t i o n of [ 0 0 ( 0 0 ) 4 ] 2  (p°(phth)^  \ p ° ( C 0 ) ^ 2 [Co(phth)3] was  prepared by shaking f o r  ^00(00)4^2 w i t h c o n c e n t r a t e d  36 hours  1.25gms. [ 0 0 ( 0 0 ) 4 ] 2 P  e r  150mls.  NH4OH,  NH4OH.  i n the r a t i o  I t was  found t h a t  a i r must be excluded from the apparatus d u r i n g shaking, or a dark r e d s u l u t i o n i s obtained which w i l l not p r e c i p i t a t e the phenanthroline complex. a stopcock was  To accomplish  this  attached to the shaking f l a s k so that the  system c o u l d be evacuated weighed, and the  NH4OH  a f t e r the c a r b o n y l had been  then added.  The c o l o r l e s s or  f a i n t l y pink s o l u t i o n prepared i n t h i s way  was  added  to an e q u a l volume of s o l u t i o n c o n t a i n i n g 0.6gms. CoCl2»  6H2O and 1.4gms. o-phenanthroline monohydrate per 50mls. water*  The heavy f l o c c u l e n t r e d d i s h brown p r e c i p i t a t e  which immediately formed was  f i l t e r e d through a Gooch  c r u c i b l e , washed w i t h water, and d r i e d i n a vacuum dessi c a t o r under h i g h vacuum.  I t was  found to be u n s t a b l e ,  decomposing t o a grey brown substance which would not d i s s o l v e In any of the s o l v e n t s which d i s s o l v e the compound.  The decomposition  l a r g e degree  original  of the product depends to a  on the r a p i d i t y w i t h which i t i s d r i e d .  Washing the p r e c i p i t a t e w i t h Water and d r y i n g i t i n a vacuum d e s s i c a t o r was  found to g e n e r a l l y r e s u l t  in partial  decomposition, u n l e s s the amount of p r e c i p i t a t e  was  extremely s m a l l , a l l o w i n g r a p i d d r y i n g .  precipitate  I f the  was washed w i t h e t h e r or a l c o h o l to remove the water, i t was  found to decompose very l i t t l e d u r i n g d r y i n g and  (24)  eould be kept f o r s e v e r a l days over P 2 O 5 .  The p r e c i p i t -  ate i s s l i g h t l y s o l u b l e i n these substances, but the r a t e of s o l u t i o n seems t o be slow and the amount of product l o s t d u r i n g the washing was amply compensated f o r by l a c k of decomposition d u r i n g d r y i n g . Hieber and S c h u l t e n (14.) s t a t e that the compound Is r e l a t i v e l y s t a b l e i n the d r y s t a t e .  I t was found however  t h a t even when thoroughly d r y i t c o u l d not be kept more than a few days without c o n s i d e r a b l e decomposition place.  taking  Storage i n an atmosphere of carbon monoxide d i d  not seem t o a l t e r the r a t e of decomposition.  These  workers p u r i f i e d the product by d i s s o l v i n g i t In a l i t t l e acetone, f i l t e r i n g the s o l u t i o n and r e p r e c i p i t a t i n g the compound w i t h water.  T h i s procedure however l e a d s to f u r t h e r  decomposition d u r i n g the d r y i n g , and no attempt was made i n these experiments  t o p u r i f y the compound i n t h i s manner.  I f p a r t i a l decomposition had s e t i n the compound was d i s s o l v e d i n the p a r t i c u l a r s o l v e n t t o be used, and t h e i n s o l uble r e s i d u e f i l t e r e d o u t . In t r a n s f e r e n c e and exchange measurements one or other o f the two c o b a l t atoms was r a d i o a c t i v e . p o s s i b l e the c o b a l t i n C o ( p h t h ) ^  4  Wherever  was made a c t i v e ,  since  making the c a r b o n y l c o b a l t atom a c t i v e i n v o l v e s the handl i n g of the extremely v o l a t i l e Co (CO)^H. In order t o make the c o b a l t atom i n the p h e n a n t h r o l i n e complex a c t i v e a g i v e n volume o f s t a n d a r d r a d i o a c t i v e s o l u t i o n was added t o orthophenanthroline and enough  (25) enough CoCl2»6H20 then added t o g i v e the necessary of CoCI • [ c o f C O ) ^ ^ [Cofphth)^]  weight  was then p r e c i p i t a t e d by the  a d d i t i o n o f ammoniacal c o b a l t c a r b o n y l s o l u t i o n . I f i t was necessary  t o make the c o b a l t c a r b o n y l a c t i v e ,  the a c t i v e c o b a l t c h l o r i d e s o l u t i o n was added i n the prepa r a t i o n o f the c a r b o n y l . S o l u b i l i t y o f [00(00)4]  2  jpo(phth) J 3  [coCCO)^! 2  |J  .  i s s o l v e s r e a d i l y i n acetone  forming an orange-brown s o l u t i o n . s o l u t i o n g r a d u a l l y turns cloudy,  Upon standing  and e v e n t u a l l y a f l o c c -  u l e n t dark brown p r e c i p i t a t e i s formed. atom i n the phenanthrollne  I f the c o b a l t  complex i s made a c t i v e , almost  a l l o f the a c t i v i t y i s removed by f i l t e r i n g ipitate.  When analysed  active cobalt.  this  off this  prec-  r a d i o c h e m i c a l l y i t showed 2.5$  I t Is s o l u b l e i n water, forming a p a l e  yellow s o l u t i o n . I t was thought t h a t the decomposition o f the compound i n acetone might be due t o the presence of s m a l l ampunts of water i n the acetone used.  The acetone was a c c o r d i n g l y  r e d i s t i l l e d over a c t i v a t e d alumina t o remove any t r a c e s o f water. unstable The  I t was found however that the compound was s t i l l , i n this  solvent.  s o l u b i l i t y and s t a b i l i t y  measured i n v a r i o u s other to f i n d a s o l v e n t obtained  organic  of the compound were s o l v e n t s i n an e f f o r t  i n which i t was more s t a b l e .  are g i v e n i n t a b l e I I .  The r e s u l t s  The acetone used was  (26)  C.P. grade and was d r i e d i n the method d e s c r i b e d . a b o i l i n g p o i n t of 56.5 C.  I t had  No attempt was made t o p u r i f y  any of the other s o l v e n t s used, but they were a l l of C.P. The JCO(CO)^J .|Co(phth)^1 was p u r i f i e d by d i s s o l v i n g  grade. it  2  i n acetone,  f i l t e r i n g o f f the i n s o l u b l e r e s i d u e , and  e v a p o r a t i n g the s o l u t i o n - t o dryness The  compound prepared  under reduced  pressure.  i n t h i s manner was completely  sol-  uble In acetone. The  s o l u b i l i t y of equal amounts of compound i n equal  amounts of s o l v e n t were t e s t e d at room temperature f o r the following solvents. Table I I . Solvent.  Solubility  Stability. heavy p p t . overnight  acetone. methyl e t h y l ketone.  -r-  s l i g h t p p t . overnight  acetophenone. methyl p a r a t o l y l ketone.  slight ppt. 1 hr. heavy o v e r n i g h t  si. sol.  p p t . i n few h r s .  formaldehyde no , p p t .  benzaldehyde sallcylaldehyde Cannamaldehyde  -r-  •h  no p p t . no p p t .  benzene si. sol.  ether absolute ethyl  ethanol  acetate  dissolves slowly heavy p p t . i n few h r s .  (27)  If is  the s t a b i l i t y  judged by  itate  it  i t would appear  i n ketones,  precipitate and  the r a p i d i t y w i t h which  Is formed,  unstable  formed  t o be  stable  tested soluble.  compound i n a l d e h y d e s the  solubility  i n various solvents an  that  insoluble  precip-  t h e compound  i n aldehydes.  i n an a c e t o n e  i t s solubility i s found  o f t h e compound  Is  However i f t h e  solution  is filtered off,  i n the v a r i o u s aldehydes The  apparent  therefore  appears  used,  stability t o be due  of the products of d i s i n t e g r a t i o n  o f the only to  i n these  solvents•  The C o n d u c t a n c e and  LCo(C0)^j2 [ p ( P  of  0  n t ] a  )-J  fact  a result  that  o f the s o l u b i l i t y  measurements and  [co(CO) 4J ( C o f p h t h ) ^ ] a p p e a r s  t o be more  2  i n benzaldehyde  or acetophenone  m o l a l conductance  o f t h e compound  was  determined  I f t h e y w o u l d be  t o see  the  stable  than i t i s i n acetone,  the  ents f o r t r a n s f e r e n c e measurements.  the  Benzaldehyde  n  Acetophenone. As  of  i  i n these  solvents  suitable  as  S i n c e the  solv-  Instability  t h e compound p r e c l u d e s m a k i n g a c c u r a t e measurements conductance, The  o n l y very approximate  resistance  f o l l o w i n g manner. bottle,  and  two  silver  s q u a r e , were i n s e r t e d stopper.  v a l u e s were o b t a i n e d .  o f the s o l u t i o n s was The  s o l u t i o n was electrodes,  contained i n a  i n t o the s o l u t i o n  w i t h a Simpson r e s i s t a n c e meter.  m e a s u r e d i n the  approximately  R e s i s t a n c e across, t h e two  through a  e l e c t r o d e s was  The  of  cell  was  weighing  1cm. rubber measured  standar-  (28) d i z e d by measuring t h e r e s i s t a n c e  o f a n e q u a l volume o f  O.lM  r e s u l t s were  KC1 s o l u t i o n .  The f o l l o w i n g  obtained:  Benzaldehyde: c o n e . - O.OOO84.M resistance  o f p u r e b e n z a l d e h y d e - 1.2x10  -d-  III.  Table  Time  Resistance  Time  Resistance  0 min.  8*10^ -TV  45 min.  5  1 7.5*10 4  60  10  7.8*10*  150  6.5*10^ 4 6.0>10 4 5.3-*10  17  7.8/10*  1110  6.2*10  26  1 7.4*10*"  1170  6.2*10  j  4  4  Acetophenone: cone.  - 0.0023M  4 resistance Table Time  IV.  o f pure acetophenone  -  24*10 -H—  Resistance  Time  Resistance  0 min.  3 *10*  105 m i n .  17.0x10^  5  3.6*10*  18 h r s .  13.5x10*  10  4.0X10  19  13.0*10*  15  4.4X10  20  12.7*10*  25  5.3vlO  22  11.7*10*  40  8.0X10  23  11.0*10*  75  16.0vl0*  24  10.5*10*  P o r a O.lM KC1 R-1500  4  4,  4 4  soln: T - 20°C  4  S\-  (29) Prom t h e r e s i s t a n c e i n t h e c e l l cell  constant J  J was  - LR  o f 0.1M  calculated, using  where L = t h e  specific  the  K C l , the  relation  conductance  R =the measured r e s i s t a n c e At is  18°C. the s p e c i f i c  0.011166-A-  1  c o n d u c t a n c e o f 0.1  The demal s o l u t i o n IS  (27).  defined  as a s o l u t i o n c o n t a i n i n g a gram m o l . o f s a l t ^  demal K C l  dissolved i n  . . ^ ^  a c u b i c d e c i m e t e r o f s o l u t i o n a t /-zero degrees-2 ections are  involved  outside  i n changing t h i s  the accuracy  t o molar  obtained  The  corr-  concentration  I n t h e above  conductance  measurements. Knowing t h e c e l l  constant,  [cotCOj^^L ^* ** ^] 00  of the  1  1  the s p e c i f i c  conductance  s o l u t i o n s were c a l c u l a t e d  f r o m t h e m e a s u r e d r e s i s t a n c e s , t h e c o n d u c t a n c e due t o t h e solvent being ution. the  subtracted  The m o l a r  from the conductance  c o n d u c t a n c e was  o f the  sol-  then c a l c u l a t e d using  relation,  A  m - 1000 L 0  where/\m - m o l a r  conductance  0 = concentration of solution in moles/liter. The v a l u e s the  g i v e n are f o r the i n i t i a l  s o l u t i o n s had decomposed  Table  V.  Molar C o n d u c t i v i t y  Solvent  J  Acetophenone  *  extent. |  ?  -A m r v ^  L£}?~  O.84  10"  2.3  10 ^  7  only,  o f Cco(CO)/ 1?CCo(phth) 3  Cone.  Benzaldehyde 1 6  t o any  readings  3  -3  1.95  lO"  5.57  10  4 -  -/ 4  232 212  before  (30)  Hieber similiar  (16) has m e a s u r e d t h e c o n d u c t i v i t y  to this,  I n methanol and a c e t o n e .  o f compounds  Some o f h i s  r e s u l t s a r e shown i n t a b l e V I t Table V I . Compound  A m. -Q-  Solvent  1  [FeH(C0)4] [Ni(phth) ]  Cfi^OH  129.7  [FeH(C0)4] [Ni(phth) l  Acetone  114.0  ^G(C0)j2[Ni(phth) ]  Acetone  248.8-280.15  JFeHtCO)^] 2 [ C o ( p h t h ) 3 ]  Acetone  2  3  2  3  3  Measurements made i n a c e t o n e  168.4  solutions  c o n d u c t i v i t i e s decreased with  showed t h a t t h e  time.  Table V I I Compound  miv  ^FeE(C0)j.] [E±(m ) \  1]L  3 6  2  4.5  1  88.4(75')  7A.2.(4hr.)  44.1(25hrs.) [FeH(C0) ] [Co(NH )g 4  133.5  3  2  102.4(15')  99.5(25')  95.6(50') From c o n d u c t i v i t y measurements o f ( C o t C O ^ ^ f c o t p h t h ) ^ i n benzaldehyde  i t c a n be s e e n t h a t  eases w i t h time, This  indicating  an i n c r e a s e  r e s u l t may be due t o t h e f a c t  easily  oxidized to benzoic  to the c o n d u c t i v i t y In acetophenone then increases  the r e s i s t a n c e  decr-  i n conductivity.  that benzaldehyde  a c i d , which would  is  contribute  of the s o l u t i o n . the c o n d u c t i v i t y decreases  slightly.  The d e c r e a s e  at f i r s t ,  i n activity  c a n be  (31)  attributed  to d e c o m p o s i t i o n o f  i n c r e a s e may be due omposition ions, soluble  to the  s u c h as  i n acetophenone  the  fact  Co  solute.  that  The  i n the  , may be  subsequent  course  of  dec-  formed w h i c h are  and l e a d t o an i n c r e a s e  in  the  is  equal  conductivity. Since t o the  the molar c o n d u c t i v i t y of  sum o f  the molar c o n d u c t i v i t i e s  the molar c o n d u c t i v i t y of c a l c u l a t e d from the c a l c u l a t i o n gives  higher  dielectric aldehyde therefore  d a t a g i v e n by H i e b e r  of  be t h e  are 20.4,  of  present,  o f 3 0 3 . 2 - 334«6X\3" f o r  the  (co(phth) ^ 3  constant  of  the  acetone,  the  in  solvent.  acetophenone  values  o f 232  This  acetone.  solvent,  18.6 and 18 r e s p e c t i v e l y .  be s e e n t h a t  ions  VI.  conductivity i n that  constants  the  in table  [coCCO)^^  the d i e l e c t r i c  higher w i l l  of  [ C o ( C 0 ) ^ 2 [ C o ( p h t h ) ^ ] c a n be  a value  molar c o n d u c t i v i t y The  a solution  the The  and b e n z It  can  f o r the molar  conductivity  i n benzaldehyde,  and 212  conductivity  i n acetophenone,  agree w i t h i n experimental  e r r o r w i t h the  value  for  o b t a i n e d by H i e b e r  the m o l a r  in  acetone.  Transference Measurements. A transference (28)  of  cell  of the  was u s e d i n a n a t t e m p t  [co(C0)^j [ c o ( p h t h ) ^ j 2  phenone. and were  The c e l l  a distance  t y p e d e s i g n e d b y Washburn  t o measure  in solutions  of  transference acetone  and  numbers aceto-  h a d a volume o f a p p r o x i m a t e l y l O O m l s .  between  electrodes  o f p l a t i n u m and were  set  o f 45cms.  The  electrodes  i n h o r i z o n t a l l y through  Figure  III  (32)  ground  glass  s t o p p e r s so t h a t  t h e y c o u l d be removed f o r  counting. It a cell  was  found  of t h i s  In  an a c e t o n e  c u r r e n t had  results. dropped end  an  prepared.  The  resulting  so t h a t  and  l o n g enough t o s e c u r e the  in practically  compound was  resistance  c u r r e n t at  c u r r e n t flowed through the  to  so  cell,  also  high  even  set i n . a eell  o f the  the r e s i s t a n c e  With  o f the s o l u t i o n  Hittorf 25ml.  a cell  of  i s much  and measurements c a n be made i n a s h o r t e r t i m e  the s o l u t i o n has cell  t h a t was  time used  t o decompose a p p r e c i a b l y . i s shown i n f i g .  e l e c t r o d e s were o f p l a t i n u m and were s e t i n glass  the  s o l u t i o n s c o u l d be  d e s i g n e d , h a v i n g a volume o f a p p r o x i m a t e l y  these dimensions  The  cell  more s t a b l e , b u t  a d i s t a n c e b e t w e e n e l e c t r o d e s o f 8cm.  before  no  the  o f t h e s e s o l u t i o n s was  overcome t h e s e d i f f i c u l t i e s  reduced,  accurate  current through  only very d i l u t e  b e f o r e d e c o m p o s i t i o n had  t y p e was  before  hour.  that very l i t t l e  To  difficultiesI  the f o r m a t i o n o f a p r e c i p i t a t e ,  a c e t o p h e n o n e the  soluble,  o f the f o l l o w i n g  with  t h e compound showed s i g n s o f  With decomposition  o f about  less  solution  been p a s s e d  rapidly,  In  impossible to obtain r e s u l t s  t y p e , because  d e c o m p o s i t i o n by the  t o be  j o i n t s , w i t h the cathode  prevent mixing,  since  m i g r a t e s t o the cathode,  the  3«  through  at the bottom.  [Go(phth) ] 3  ground  This helps  which  i s h e a v i e r than the  The  presumably  [00(00)4]  ion.  « o ^  o o Potentiometer  G  s/wv  To  S t a n d a r d 100  transference "cell.  Figure  IV.  K  X  Resistance.  K  2  (33)  The  cathode  that  was  set i n through  i t c o u l d be  formed  removed e a s i l y  on i t , and was  t h e p r e c i p i t a t e more The  and  the  t o count  shaped  so t h a t  some o f the  any  so  precipitate  i t would h o l d  the  f o r the p u r p o s e  cell,  but  r e m o v e d i n t h i s way  cathode  i t was mixing  portion remaining  r u n n i n g o u t w i t h t h e anode p o r t i o n .  middle  o f the c e l l ,  easily.  s o l u t i o n from  t h e s o l u t i o n was  from  side  s t o p c o c k a t t h e b o t t o m was  removing if  cup  the  found  side  anode  p o r t i o n s were t h e r e f o r e r e m o v e d w i t h a  suction  and  t h e n r u n out from the bottom.  t e s t w h e t h e r o r not  m i x i n g r e s u l t e d when t h e manner a few in  crystals  the cathode  of potassium  p o r t i o n and  giving  a colored  of  the  solution  in  t h e manner d e s c r i b e d . The  found  s o l u t i o n was  circuit  solution c o u l d be  used  arm  and  p i p e t t e from the top o f the c e l l , To  that  resulted  i n the  The  of  the cathode  portion  removed i n t h i s  permanganate were p l a c e d  the c e l l  f i l l e d with  around  the cathode.  observed  when i t was  water, No  mixing  removed  i s shown i n the d i a g r a m .  It  was  t h a t f o r t h e s m a l l number o f coulombs p a s s e d d u r i n g  a measurement  a silver  tly  accurate r e s u l t s .  the  v o l t a g e drop  connected  circuit  coulometer  w o u l d not g i v e  A p o t e n t i o m e t e r was  a c r o s s a s t a n d a r d hundred  used ohm  i n s e r i e s w i t h the t r a n s f e r e n c e c e l l .  used  standardized  i s shown i n f i g . A .  The  sufficient o measure  resistance The  potentiometer  a g a i n s t a s t a n d a r d Weston c e l l  before  was the  (34 )  run  and s e v e r a l t i m e s d u r i n g m e a s u r e m e n t s .  d r o p a c r o s s t h e s t a n d a r d r e s i s t a n c e was  The v o l t a g e  measured e v e r y  few m i n u t e s  d u r i n g a r u n , and f r o m t h e c a l c u l a t e d  a g r a p h was  plotted  the  of current  v s . time.  The  c u r v e r e p r e s e n t e d t h e number o f coulombs  current  area  under  passed.  Procedure; T r a n s f e r e n c e measurements were made i n s o l u t i o n s acetone.  The  a c e t o n e was  C.P.  s e v e r a l times over a c t i v a t e d The  [ C o ( G 0 ) j 2 [ C o ( p h t h ) J was  and  any  4  insoluble residue  i t i o n was  filtered  a c c u r a t e l y and the  3  after  redistilled  a l u m i n a t o remove any dissolved  that The  and was  i n the  remained  cathode  due  and  water.  acetone,  t o decompos-  anode were  weighed  t h e s o l u t i o n had b e e n i n t r o d u c e d  were s e a l e d  the  current  had b e e n p a s s e d f o r t h e d e s i r e d l e n g t h o f t i m e  the  anode  carefully  cribed  i n with paraffin.  into  After  was  cell,  off.  grade  of  removed, and t h e s o l u t i o n d r a w n o u t as  i n t o weighed  glass  t h r e e p o r t i o n s weighed.  stoppered b o t t l e s , The  and  des-  the  s o l u t i o n s were k e p t  tightly  stoppered to prevent e v a p o r a t i o n of acetone. The  s o l u t i o n was  drawn o u t  anode p o r t i o n e x t e n d i n g to a b o u t the  m i d d l e p o r t i o n t o about  remaining  s o l u t i o n b e i n g r u n out  During e l e c t r o l y s i s was  formed  two  a heavy  on the c a t h o d e .  a c e t o n e , and w e i g h e d . each run, but  The  i n three portions, two cm.  cm.  below the  d a r k brown  anode was  anode,  above t h e c a t h o d e ,  as t h e c a t h o d e  T h i s was  the  the  portion.  precipitate  removed, washed w i t h a l s o weighed  no w e i g h t d i f f e r e n c e was  found.  A  after gas  (35) a p p e a r e d t o be f o r m e d a t b o t h t h e anode and c a t h o d e , b u t was n o t c o l l e c t e d The  i n sufficient  quantities  c o n c e n t r a t i o n o f the o r i g i n a l  t o be i d e n t i f i e d  s o l u t i o n was  a i n e d b y e v a p o r a t i n g known v o l u m e s t o d r y n e s s , the weight and  obt-  obtaining  [co(G0)^]2 [oo(phth) "] i n t h i s volume,  of the  3  then c o u n t i n g the samples.  three portions a f t e r  The c o n c e n t r a t i o n o f t h e  electrolysis  c o u l d t h e n be  b y e v a p o r a t i n g known volumes t o d r y n e s s  obtained  and c o u n t i n g  them  u n d e r t h e same c o n d i t i o n s .  and  The  precipitate  from  i t s weight  on t h e c a t h o d e the percent  was a l s o  active  prom t h e w e i g h t o f t h e p r e c i p i t a t e number o f coulombs p a s s e d  counted,  cobalt  calculated,  on t h e c a t h o d e  i t s h o u l d be p o s s i b l e t o c a l c -  u l a t e t h e e q u i v a l e n t weight o f the p r e c i p i t a t e . tent results the f a c t  Results  No c o n s i s -  c o u l d be o b t a i n e d however, p r o b a b l y due t o  that the p r e c i p i t a t e  very w e l l ,  and t h e  and was p r o b a b l y  d i d not adhere t o the cathode  not a l l removed f o r w e i g h i n g .  and C a l c u l a t i o n s ;  Transference  numbers were c a l c u l a t e d ,  f o l l o w i n g r e a c t i o n s t o take  anode: cathode:  2JCo(C0)J"  [Co(phth)3] + ++  at  2  + 2E  OH"  2  2H* +  place:  > Co(CO)^  . E 0^±E*+  20H"—>[Co(phth) ](OH)  2E-—»H  3  2  anode: g a i n t_ e q u i v .  [00(00)4]  lose t  [Co (phth) oJ  +4+  assuming the  equiv.  2  .  (36)  at  cathode: l o s e t _ e q u i v . [co((iCO)^J g a i n t+ e q u i v . deposit  net  [Go(phth)^j[  1 equiv.  ^(phth).^  (GH)  2  result: lose  (1 - t ) e q u i v . - t - e q u i v .  The  c o b a l t atom i n [bo(phth)-^j was made a c t i v e .  end  o f the r u n the middle  ion.  Since  its final  o f t h e cathode  r  +  p o r t i o n had changed  -H-  (Co(phth) J 3  A t the  concentrat-  c o n c e n t r a t i o n was t h e samB a s t h a t  p o r t i o n , t h e two were t a k e n  together.  Table V I I I . cts./min.* 10.2ml.  cone. equiv./l.  volume i n mis.  equiv. transferred  original  2398 t 28  0.0117  cathode  2291  t30  0.0113  10.005  middle  2288 ? 3 8  0.0113  2.02  0.81x10  anode  2151  0.0106  2.05  2.20*10  3.8  coulombs p a s s e d * 0.83 -8.6x10 * Background Transference  faradays  subtracted.  numbers  (1) f r o m  -6  calculated:  change i n c o n e , o f anode p o r t i o n : t =0.256 + t_ = 0.74.4  (2) f r o m  change i n c o n e , o f c a t h o d e t-'0.465 •? t - 0.535  portion:  *10 -6 -6  (37)  The  precipitate  on t h e c a t h o d e  was d a r k brown i n  c o l o u r , w i t h a s m a l l amount o f l i g h t e r brown m a t e r i a l on the  surface.  solution*  I t was s o l u b l e i n w a t e r , f o r m i n g  C a l c u l a t i o n o f i t s e q u i v a l e n t weight,  weight of p r e c i p i t a t e passed,  a yellow  d e p o s i t e d a n d t h e number o f coulombs  gave t h e f o l l o w i n g r e s u l t s ,  obtained i n previous  from the  including  values  runs:  Table IX. Wt. o f p p t .  Coulombs.  Equiv.  0.0036 gms.  0.83  420  0.0176  5.18  293  0.0176  5.45  312  0.0026  1.167  216  A radiochemical a n a l y s i s of the p r e c i p i t a t e following Table  gave t h e  results:  X. Wt. p p t .  Counts/min.  Gms. Co  % Co  0.0067gms.  4533 ^ 33  0.00025  3.76  0.0118  7241 ± 4 1  0.00040  3.41  0.0103  6549 * 3 9  0.00036  3.53 Ave.  If  Wt.^ni)  the p r e c i p i t a t e  s h o u l d be  - 3.57$  Is [Cotphth^J ( 0 H ) the f o l l o w i n g values 2  obtained: M o l e c u l a r weight E q u i v a l e n t weight  -  616.2 -  308.1  Percent a c t i v e cobalt ( a s s u m i n g no e x c h a n g e )  9.58$  ( 3 8 )  Measurements were [00(00)4!""  a l s o made w i t h  iona ctive.  inaccurate  The r e s u l t s o b t a i n e d  to calculate transference  erence i n c o n c e n t r a t i o n the  original  were t o o  numbers,  as t h e d i f f -  between t h e c a t h o d e p o r t i o n a n d  s o l u t i o n was t o o s m a l l  The anode p o r t i o n showed which agrees w i t h  the cobalt I n the  t o be  a definite  the equations  significant.  increase  postulated.  i n activity, The p r e c i p i t a t e  on t h e c a t h o d e ' h o w e v e r was f o u n d t o be a c t i v e . precipitgte it had  should  I s ^ C o C p h t h ) ^ ( O H ) as h a s b e e n  occured  precipitate  postulated,  2  n o t have b e e n a c t i v e i n t h i s b e t w e e n t h e two c o b a l t showed  that  case,  atoms.  i t contained  6.7$  I f this  unless  Analysis  exchange of the  active cobalt,  a much l a r g e r p e r c e n t a g e t h a n was f o u n d when t h e c o b a l t i n the phenanthroline  complex was a c t i v e .  An a t t e m p t was made t o a n a l y s e t o t a l c o b a l t content method.  However  using  the  i t was f o u n d  the p r e c i p i t a t e f o r  - nitrosoy9  that only  a very  naphthol small  o f t h e c o b a l t c o u l d be p r e c i p i t a t e d i n t h i s manner, the o r t h o - p h e n a n t h r o l i n e of cobalt  I n the u s u a l  complex p r e v e n t s manner.  amount since  the p r e c i p i t a t i o n  (39)  S t u d y o f E x c h a n g e b e t w e e n t h e Two C o b a l t  Atoms I n  [cofcoj^fcofphth)^ Because o f the r e s u l t s  obtained  m e a s u r e m e n t s , w h i c h seem t o i n d i c a t e type,  an experiment  was c a r r i e d  or not exchange o c c u r s  i n the t r a n s f e r e n c e exchange  o f some  out t o d e t e r m i n e  whether  b e t w e e n t h e two c o b a l t atoms i n  [Co(C0) J (co(phth)3]. 4  2  B e c a u s e o f t h e weak a c i d should  nature  be p o s s i b l e t o l i b e r a t e  o f Co(CO)^H, i t  Co(CO)^H f r o m  |co(phth)3] by the a d d i t i o n o f a s t r o n g a c i d and  this  was f o u n d  w i l l be a measure roline  t o be t h e c a s e .  such  prepared  of this  the phenanth-  as p r e v i o u s l y ,  w i t h t h e c o b a l t atom i n ' t h e p h e n a n t h r o l i n e  complex  active.  p r e c i p i t a t e was washed w e l l w i t h w a t e r , b u t no a t t e m p t  was made  to dry i t . A small d i s t i l l i n g  ected through  f l a s k was  t h e s i d e arm t o a d r y i n g t r a i n ,  cooled  to -79*C.  The p r e c i p i t a t e  drying  flask with  a s m a l l amount o f d i s t i l l e d  s y s t e m was a t t a c h e d concentrated completely  t o the carbon  hydrochloric acid  dissolved, giving  t h e time  carbon  that  and a t r a p  water, the  monoxide g e n e r a t o r and  a bright blue  the p r e c i p i t a t e solution.  About  t h e compound was made,  i t was a c i d i f i e d .  monoxide was a l l o w e d  conn-  was washed i n t o t h e  added u n t i l  an h o u r e l a p s e d b e t w e e n t h e t i m e and  as H C l ,  initially.  (po(C0)^2(Cofphth)^was  The  2  The a c t i v i t y  o f the exchange i f o n l y  Co was a c t i v e  (Co(CO)^l ~  A slow stream  t o pass f o r about  of  t e n hours  (40)  at  t h e e n d o f w h i c h t i m e a s m a l l amount o f 0 0 ( 0 0 ) 4 6 : h a d  collected  i n the trap.  The t r a p was e v a c u a t e d a t - 7 9 ° C .  and a l l o w e d t o come t o room  temperature, g i v i n g  o c t a c a r b o n y l . - T h i s was d i s s o l v e d  i n benzene,  dicobalt  evaporated  t o d r y n e s s , and c o u n t e d . b a c k g r o u n d - 61*3  00(00)4 This  indicates  t h e two c o b a l t  that  t h e r e was no exchange  atoms, under t h e c o n d i t i o n s  Study o f t h e Exchange Since  - 60*3  2  Between  i t appears that  t h e two c o b a l t  atoms  of the experiment.  and Q c o ( p h t h ) j  Co  there  between  •  3  i s no exchange  between  i n [ 0 0 ( 0 0 ) 4 ] 2 [po(phth) ], some  other  3  e x p l a n a t i o n must be s o u g h t t o a c c o u n t f o r t h e r e s u l t s I f t h e £co(C0)^l  o b t a i n e d i n t r a n s f e r e n c e measurements. i o n were t o decompose ions,  i n acetone s o l u t i o n ,  i t m i g h t be p o s s i b l e  .exchange w i t h t h e © b a i t  f o r these c o b a l t  i n [_Co(phth) J . *-»  has b e e n o b s e r v e d b e t w e e n Pe A standard radioactive i n t h e f o l l o w i n g manner. were d i s s o l v e d  giving  cobalt  Ions t o  S u c h an e x c h a n g e  i  r  +  i o n s and [ F e f p h t h ) ^ ] ( 2 9 ) .  cobalt  s o l u t i o n was p r e p a r e d  A p p r o x i m a t e l y 0.2gms. Co^ 0^  i n HCI and a l i t t l e  HNO^•  The s o l u t i o n  was made up t o a p p r o x i m a t e l y 100ml. and C o C L 2 » 6 H 0 2  to o b t a i n the d e s i r e d  specific  s a m p l e s were measured  out, evaporated nearly  t o g e t r i d o f t h e W0^, for  cobalt  +  diluted  activity.  t o 10ml.,  using«<.-nitroso/4-naphthol.  Three  added  2.0ml.  to dryness  and a n a l y s e d  (41)  Table X I . Wt. o f C o ( C  1 0  H 0 N) .2H2O. 6  Wt. Co.  3  1.  0.1252 gms.  0.0121 gms.  2.  0.1170  0.0118  3.  0.1299  0.0120  Ave.-  1  2  0.0120 gms. C o / 2 m i s .  Solution.  0.0060 gms. C o / 1 m l .  Solution.  p o r t i o n s o f t h e s o l u t i o n were e v a p o r a t e d  and c o u n t e d :  2400*57  counts/min.  1 gm. c o b a l t -4*10** In  t o dryness  counts/min.  o r d e r t o s t u d y t h e exchange b e t w e e n Co  and  [ b o ( p h t h ) J * * a s o l u t i o n was p r e p a r e d b y a d d i n g t o a known 3  weight  of ortho-phenanthroline s u f f i c i e n t  complex  o f a p p r o x i m a t e l y 0.02M.  t o 50mls.  5 mis.  To t h i s was a d d e d  and t h e s o l u t i o n was  A t t h e end o f t h e d e s i r e d  length of  o f s o l u t i o n were w i t h d r a w n and t h e \ C o ( p h t h ) " 3  p r e c i p i t a t e d w i t h an ammoniacal s o l u t i o n  {c°(C0)4]2 f P ^ P k t * ^ • 1  which the p r e c i p i t a t e ered througha a little  2  1  5 m l s . o f s t a n d a r d Co C l g s o l u t i o n ,  time  6  t h e o r t h o - p h e n a n t h r o l i n e and p r o v i d e a Co"*" i o n  concentration  diluted  CoCl2» H 0 to  t i m e was t a k e n a s t h e t i m e a t formed.  The p r e c i p i t a t e  G-ooch c r u c i b l e , washed w e l l  alcohol,  and d r i e d  i n a vacuum.  p r e c i p i t a t e was w e i g h e d  i n the c r u c i b l e ,  ved  leaving  i n acetone, u s u a l l y  uble r e s i d u e .  After  o f C o C C O ^ H , as  was  filt-  w i t h water and When d r y t h e and t h e n  dissol-  a s m a l l amount o f I n s o l -  d r y i n g i n a vacuum t h e c r u c i b l e was  (42)  reweighed, g i v i n g the weight e f [Co(G0)^J fcotphth)^] i n 2  solution,  The s o l u t i o n was d i l u t e d t o 50mls. and 0.4 m l ,  samples c o u n t e d .  From the w e i g h t o f p r e c i p i t a t e i n t h e  a c e t o n e s o l u t i o n and I t s a c t i v i t y ,  the a c t i v i t y  £co(phth) J  was c a l c u l a t e d ,  the p e r c e n t  exchange b e i n g t a k e n as t h e p e r c e n t  3  which had been t r a n s f e r r e d phenanthroline  complex.  and hence t h e p e r c e n t  from the c o b a l t  exchange a t e q u i l i b r i u m  using the f a c t that to inactive cobalt for  exchange,  of cobalt  i o n t o the  From t h e c o n c e n t r a t i o n s o f Co ,  Co*"**, a n d [ C o ( p h t h ) ^ J ^ i n t h e o r i g i n a l e t i c a l percent  o f the  atequilibrium atoms w i l l  s o l u t i o n , the theorwas c a l c u l a t e d ,  the r a t i o  of active  be t h e same f o r Co a n d  [co(phth) ]*T 3  The f o l l o w i n g r e s u l t s were  obtained:  1.  Wt. o - p h t h . H 0  -  0.594-0 gms,  :  Wt. C o C l . 6 H 0  -  0.3000 gms.  2  2  2  5 m i s . Co CI2 s o l n . Wt. o f c o b a l t  - 0.0300 gms. C o = 1 . 2 1 0  a s Co* -  Wt. Co i n Complex  +  -  7  c/m.  0.0454 gins. 0.0589 gms.  Table X I I . Time.  ^Exchange.  1 hr.  44.4 %  2 hrs.  43.2 %  4 hrs.  44.9 %.  Theoretical  percent  exchange a t e q u i l i b r i u m  - 56.5$  (43) 2.  Wt. o-pb.th.H2O  -  0.5943 gms.  Wt. C o C l . 6 H 0  -  0.3459 gms.  2  2  5 mis. Co*Cl  2  s d n . =.  0 . 0 3 0 0 gms. Co  1.2 1 0 c/m. 7  Table  Wt. c o b a l t  as Co"**  0.0568 gms.  Wt. c o b a l t  I n complex  0.0589 gms.  XIII. jo E x c h a n g e .  Time.  2.5 m i n .  31.5  10  30.9  20  36.9  30  34.5  40  35.4  „  T h e o r e t i c a l percent  exchange a t e q u i l i b r i u m  - 50.95$ Prom t h e s e r e s u l t s i t c a n be s e e n t h a t seems t o exchange v e r y value  i n a few m i n u t e s .  considerably expected. precipitate it  r a p i d l y reaching This  an e q u i l i b r i u m  e q u i l i b r i u m value  lower than the t h e o r e t i c a l value  that the  o f [Co(C0)^l 2 £c°(phth)3| m i g h t c a r r y down w i t h  a c e r t a i n amount o f a d s o r b e d Co cl 2 »  Then i f t h e r a t e  X  2  e x p e c t e d t o be a c o n s t a n t ,  w h i c h w o u l d be  w o u l d c o v e r up any change i n  p e r c e n t a g e e x c h a n g e , and make I t a p p e a r a s t h o u g h a n  e q u i l i b r i u m had b e e n a t t a i n e d . the  i s however,  which Is  The method u s e d h a s t h e d i s a d v a n t a g e  o f exchange i s s l o w , t h e a d s o r b e d C o C l ,  the  the cobalt  f i g u r e s i n t h e second  The s l i g h t  upward t r e n d i n  s e t o f measurements make i t a p p e a r  (44)  as t h o u g h t h i s may  be  the  case.  In order t o a s c e r t a i n whether the  observed  a r e due  to a very r a p i d  and  c o b a l t i n [ c o ( p h t h ) 3 ] ^ or whether the  the  i s merely  the r e s u l t  c h l o r i d e by arating  and  Since  Co(0H) » 2  insoluble  and  of three with  00(011)3.  o f two,  Co(OH)2 suoh  an  oxidizing  hydroxide than  agent  c a n be  cobaltous  i n water o f 0.00032  3  cobaltic  by  oxidized as  precipitated,  hydroxide,  gms./lOO  mis. from  t h e p r e c i p i t a t i o n o f t h e c o b a l t Ions  hydroxide,  p r o v i d e d t h a t t h i s method d o e s  also precipitate  some o f t h e  roline  After f i l t e r i n g  complex.  C o ( 0 H ) , d e t e r m i n a t i o n of the 3  cobalt from  a i n i n g c o b a l t i o n s o n l y , the u n p r e c i p i t a t e d by  the  activity  o f the  By r u n n i n g activity  the hydroxide  the  as not  phenanth-  o f f the p r e c i p i t a t e  activity  t h e amount o f e x c h a n g e .  s u b t r a c t e d from  as  such  s h o u l d t h u s be p o s s i b l e t o s e p a r a t e Co  LCo(phth) j  gives  cobaltous  a d d i t i o n o f a base  cobaltic  a solubility  It  hydroxide,  the v a l e n c e  sep-  devised.  hydroxides,  cobaltic  i s much more i n s o l u b l e  having  method o f  I f however t h e c o b a l t Is f i r s t  hydrogen peroxide, and  i o n s was  3  I s g e n e r a l l y f o r m e d on t h e  to a valence  a different  LCo(phth) J  c o b a l t n o r m a l l y has  sodium h y d r o x i d e .  activity  of adsorption of active cobalt  C o b a l t f o r m s two hydroxide,  exchange b e t w e e n c o b a l t i o n s  the p r e c i p i t a t e ,  t h e Co  results  c a n be  of- the  due  of  solution  a blank  cont-  to c o b a l t ions  determined  solution.  and  (45)  To  determine  c a n be p r e c i p i t a t e d was  as c o b a l t i c  made up c o n t a i n i n g  to form  the cobalt  very s l i g h t 30$  excess  hydrogen  made b a s i c  be  hydroxide, a  enough C o C l g  and # o - p h e n a n t h r o l i n e  p h e n a n t h r o l i n e c o m p l e x and p r o v i d e a of o-phenanthroline.  no p r e c i p i t a t e  2  cobalt  of cobaltic  (II) c h l o r i d e .  a f t e r the d e s i r e d  length  were added, a n d 10 d r o p s  2  about  Under  hydroxide  [po(phth)3j  10.  bringing  The p r e c i p i t a t e  o f time  had e l a p s e d , 5 m l .  6NaOH t o b r i n g  a double  t h e P.H. t o  and w a s . f i l t -  thickness of f i l t e r  p r e c i p i t a t e was washed w i t h about  paper.  45. m l . d i s t i l l e d  to b r i n g  t h e volume o f t h e f i l t r a t e  t o 50 m i s .  portions  were e v a p o r a t e d  and c o u n t e d .  was  prepared containing  (II) c h l o r i d e , Co(OH)  0  3  described  to dryness  phenanthroline  s u b t r a c t e d from measurements.  the a c t i v i t y  found  water  A blank cobalt  complex.  u n d e r t h e same c o n d i t i o n s  above a n d t h e a c t i v i t y  The  0.3 ml.  t h e same amount o f a c t i v e  b u t no c o b a l t  was p r e c i p i t a t e d  o f 30$  o f C o ( 0 H ) 3 was c o a g u l a t e d b y  the s o l u t i o n to the b o i l i n g point,  ered o f f through  ions  To s e p a r a t e t h e two  o f t h e s o l u t i o n were w i t h d r a w n , 3 d r o p s  portions H 0  10.  observed.  active  ions  A few d r o p s o f  w i t h 6N NaOH t o a P.H. o f about  A s o l u t i o n was p r e p a r e d c o n t a i n i n g and  solution  p e r o x i d e were t h e n added, a n d t h e s o l u t i o n  these c o n d i t i o n s could  i n ^CofphtbO^J  whether or not the c o b a l t  as  i n the f i l t r a t e  o b t a i n e d i n t h e exchange  (46) The  f o l l o w i n g r e s u l t s were  obtained;  Wt. o f o - p h t h . H 0  -  0.5897  gms.  o  -  0.3457  gms.  2  Wt. o f C o C l  .6H  5 mis. active CoCl^  soln.  0.0211gms. Co  containing  8.425  »  10  cts/min.  S o l u t i o n d i l u t e d t o 50 m i s . Wt. o f c o b a l t  i n complex  - 0.0586  gms.  Wt. o f c o b a l t  as C o *  - O.O48O  gms.  Blank  -  +  16*5  cts./min./0.3mls.  T a b l e XIV. Time  cts./min./0.3 m i s . of f i l t r a t e  5 min.  3659 ± 5 1  72.2$  1 day  3788 2 46  74.6  2 days  3681 &26  72.5  3 days  3830 2 34  75.4  8 days  3693 £ 60  72.6  T h e o r e t i c a l percent  -  exchange a t e q u i l i b r i u m  55.04  These f i g u r e s c o n f i r m t h a t Co * i o n s -  reaching The  4  exchange v e r y  e q u i l i b r i u m value  entrations fact  the r e s u l t  that  00(011)3,  previously,  [cofphth^**  i n a few m i n u t e s .  found experimentally  than the value  of the various  found  rapidly with  an e q u i l i b r i u m v a l u e  I s much h i g h e r  the  % Exchange  howeveB,  c a l c u l a t e d from the conc-  ions.  This  i n the presence  i s p r o b a b l y due t o of  too  (phth)  3  1 * t  tends t o form a c o l l o i d a l " s o l u t i o n , which i s hard to f i l t e r .  (47)  Co(OH) the  3  left  activity  In the f i l t r a t e o f the f i l t r a t e ,  exchange v a l u e  too high.  i n this  manner w o u l d  making the  increase  experimental  (48)  S t u d y o f the  E x c h a n g e Between C o b a l t  M e t a l and  Dicobalt  Octacarbonyl* The  exchange b e t w e e n a c t i v e  octacarbonyl  m e t a l and c o b a l t  i n a s o l u t i o n o f b e n z e n e , was s t u d i e d a t  room t e m p e r a t u r e .  The a c t i v e  f o l l o w i n g manner:  0.0508 gms.  i n H2SO4, 10 gms. a d d e d , and  cobalt  the  c o b a l t was p r e p a r e d o f Co 0 2  3  were  40 m i s .  o f (NH^) S04 and 2  e l e c t r o l y s e d between p l a t i n u m e l e c t r o d e s  at  5 volts.  water, d r i e d  and Wt.  This  o f Co  1.1*10  and  a l l o w e d t o s t a n d f o r 18 h r s .  cobalt  end o f t h i s  itate and  and L  C o  c  o f the  evacuated,  c a r b o n y l had The a c t i v e  s o l u t i o n , the  precip-  o f f , the. s o l u t i o n e v a p o r a t e d t o d r y n e s s , counted.  Background  - 5 0 1 1 cts./min©  Solution  - 50 i 1  Precipitate  - &Z t 2  Indicates  ( °)4]2*  solution.  temperature.  precipitate.  b o t h p r e c i p i t a t e and s o l u t i o n  This  a t room  time a good d e a l  m e t a l was removed f r o m the filtered  with  c/m.\.0.0445 gms.("Co(C0)  was added, t h e s y s t e m  decomposed, f o r m i n g a p i n k i s h cobalt  was washed w e l l  i n b e n z e n e , g i v i n g a 0.00325M  radioactive  the  1 amp.  d e p o s i t - 0.0191 gms.  The  At  using  weighed.  would c o n t a i n  were d i s s o l v e d  dissolved  The s o l u t i o n  was  of cobalt  the  c o n e . NH^OH  s o l u t i o n d i l u t e d t o 150 m i s .  The d e p o s i t  in  no exchange b e t w e e n c o b a l t  metal  (49) IV.  Discussion  The  of  Results,  compound £ Co ( C O ) ^ ^ C  f o u n d t o be  unstable  ution i n various  b o t h i n the  organic  of a strong salt  dry  solvents.  ments i n a c e t o p h e n o n e and compound has  (P^ith.)was prepared  Co  state  and  Conductivity  e l e c t r o l y t e , i n d i c a t i n g that carbonyl  hydride.  The  previous  i t is a  results  ference  number of  o f the  |C°(P th)3j  the  n  ion.  6.7$  o f an  active cobalt.  should  be  I f the  9»58$  the  be  active cobalt  i n a c t i v e In the  p r e c i p i t a t e c o u l d be  both  [co(phth)3]*and[co(C0)^j  hence w o u l d  \po(CO)  the  j\ 2 (p°(phth)  postulated  i n the  a compound  [co(C0) l2 jco(phth)^ .  first  are  case  which and  It is possible containing  i n some manner. the  the  contained  [Co(phth)3l(OH)2>  seem p r o b a b l e however b e c a u s e of 4  that  since  cathode d u r i n g  second case.  the  form of  expected,  l a r g e r , and  reactions  that  not  i s t o be  transthan  active ihe p r e c i p i t a t e  p r e c i p i t a t e should  would c o n t a i n  the  3*5$ a c t i v e c o b a l t , whereas w i t h  atom i n £ . 0 0 ( 0 0 ) ^  the  true  obtained  ion i s greater  acetone s o l u t i o n of  found to c o n t a i n  correct  that  mobility.  p r e c i p i t a t e f o r m e d on  electrolysis  cobalt  This  i o n i s p r o b a b l y the  have a l o w e r i o n i c  was  ^Co(CO)^")  the  workers.  T r a n s f e r e n c e measurements i n d i c a t e t h a t  The  measure-  a molar c o n d u c t i v i t y c o r r e s p o n d i n g to  of cobalt  latter  sol-  benzaldehyde i n d i c a t e that  a g r e e w i t h t h o s e q u o t e d by  the  in  and  This  highly  I t seems l i k e l y ,  does  ionized there-  (50)  the p r e c i p i t a t e c o n t a i n s  only  t h e [bo(phth)^J*"*"  fore  that  ion,  and t h e r e s u l t s c a n o n l y be e x p l a i n e d  o f some s o r t b e t w e e n t h e two c o b a l t shown t h a t  t h e two c o b a l t  do n o t exchange over a p e r i o d their  a t room  atoms  o f a few h o u r s .  exchange  This  is  very  I t has b e e n  ( C 0 ) ^ (jP°(P^th) ^"J 2  i n an a c i d does not  the r e s u l t s  has b e e n o b s e r v e d however [bo^rith^J^ions  r a p i d and r e a c h e s  Instantaneously.  preclude  obtained.  between  i n solution.  If, t h e r e f o r e ,  Co  i o n s were  almost present  1 **  t h e y w o u l d e x c h a n g e w i t h t h e [Co(phth)-^j i o n s ,  the  Assuming t h i s  g i v i n g the  t o be t h e c a s e , and  p r e c i p i t a t e on t h e c a t h o d e i s ( b o ( p h t h ) ] ( O H ) 3  amount o f c o b a l t percent  exchanged at e q u i l i b r i u m ,  active cobalt  exchange  t o d e c o m p o s i t i o n o f £co(C0)^\ ,  r  obtained.  cobalt  This  an e q u i l i b r i u m v a l u e  i n t h e a c e t o n e s o l u t i o n , due  results  solution  i f s u c h a n exchange d i d o c c u r i t  w o u l d be r a p i d enough t o g i v e  ( I I ) I o n s and  G o  exchange  i n an a c e t o n e s o l u t i o n , b u t i t i s h a r d l y  t o be e x p e c t e d t h a t  Exchange  atoms.  in C  temperature  by  2  that  the  and hence t h e  i n t h e p r e c i p i t a t e c a n be  calcul-  ated. Por  [co(C0)^ fco 2  I n one mole  (phth) ]:  o f t h e compound,  118 gms.COoXln 59  gms.  Co i n  Then at e q u i l i b r i u m , atoms w i l l  3  [Co(C0)^J  2  [Co(phth)^ the r a t i o  of active to inactive  be t h e same i n b o t h c a s e s so  that:  (51)  x  5 9  x  -  -  w h e r e  1 1 8  5 9  x  c o b a l t  *  w  t  .  e  3 9  { C o ( p h t h ) 3 J  T h e  5 9  -  x • = 2 0  a c t i v e  a c t i v e  t o  f r o m  C o C C O ) ^  g m s .  t h e r e f o r e  g m s .  in  c o b a l t  f  t r a n s f e r r e d  C o ( p h t h ) 3  x  o  a c t i v e  n o w  c o n t a i n s  c o b a l t .  ( c o t p h t h ^ ] ( 0 H )  2 0  1 0 0 $  ^  .  T h e  Is  2  .  p e r c e n t  t h e r e f o r e ,  3 . 2 5 $  6 1 6 . 2  S i m i l i a r  f o r  t h e  i b r i u m  c a l c u l a t i o n s  w e i g h t  a  v a l u e  o  f  o f  o f  6 . 5 $ .  T h e s e  in  a  in  w h i c h  v a l u e s  a g r e e  f o r m  t h e s e  a c t i v e  3 9  f  o  ,  c a n  v e r y  I n  a n d  c a l c u l a t i o n s  t  [co(C0)^j  c o b a l t  g m s .  i  r  a  ^ C o ( p h t h ) ^  p e r c e n t  a s s u m e  e x c h a n g e .  c l o s e l y  ^ 0 ( p h t h ) 3 J g i v e  2  w i t h  t h a t  I  t  e q u i l -  a c t i v e  a  t  a  l  lt h e  c a n  t h o s e  b e  c o b a l t  c o b a l t  s e e n  o b t a i n e d  i  t h a t  .  e x p e r i m e n t a l l y .  P e r c e n t  [ c o ( C 0 )  4  ]  [ c o ( C 0 ) ^  In  c o u r s e  n u m b e r s  t h e  A c t i v e  2  [ c o ( p h t h )  2  ( C o ( p h t h )  p r e s e n c e  i m p o s s i b l e  b y  C o b a l t  t h e  t o  m e t h o d  3  3  o  i  ( c o ( p h t h )  n  3  j ( 0 H )  2  .  E x p e r i m e n t a l .  C a l c u l a t e d .  3 . 5 7 $  3 . 2 5 $  ] j  6 . 7 $  f  a n  o b t a i n  e x c h a n g e  t h e  d e s c r i b e d .  6.5$  s u c h  c o r r e c t  a s  t h i s  i  t  t r a n s f e r e n c e  i  s  o  f  s  (52) V.  Suggestions f o r Further An  during  analysis the  o f the  electrolysis  Work*  p r e c i p i t a t e f o r m e d on  of 100(00)^2£co(phth) J not  that postulated.  presence  this  can  HIeber ysing  the  not  (15) the  Because the  normal I o n i c r e a c t i o n s  be  done by  however has  cobalt  substance  i t s formula  any  o f the  devised  of  agrees  with  two  cobalt,  a n a l y t i c a l methods.  a s u i t a b l e method f o r  i n [cotCOj^^fcotphth)^]  be  o-phenanthroline  of valence  usual  cathode  should  3  made, t o d e t e r m i n e w h e t h e r o r  eliminates  the  by  heating  i n a p l a t i n u m c r u c i b l e , decomposing the  anal-  the residue  w i t h KHSO^, d i s s o l v i n g i t i n w a t e r , and p r e c i p i t a t i n g the  cobalt The  in  as t h e  anthranilate.  possibility  o f exchange b e t w e e n the  £00(00)4]2 (0°(Phth)2]  ecially  i n solutions  but  not  may  time t h a t  should  of acetone.  have b e e n s u f f i c i e n t  the  compound was  in  be  studied  existence.  atoms  further,  E x c h a n g e may to detect  cobalt  be  i n the  esp-  present, short  (53)  Bibliography.  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