DOCTORAL D ISSE R T A TIO N SERIES t itle The E /e d n c d C o n d u c ta n c e O f A lk a lin e E & rth H s lid e s I n E t h a n o l - V a t e r a u th o r fichard Louis Bole man DEGREE d a te 19 W MichicjZin S i d e College m U N IV E R S IT Y ^ S y ste m s ________ _ PUBLICATION N O .. \i> £> 68 UNIVERSITY MICROFILMS ANN ARBOR • MICHIGAN T l'il’J h ij h O l'ilX CALi. O j h l.'IJ C i j ..hi 0 A 01' T i i ; f f ; LLL!JL»'v.'Vi f t : A.-Lu\ A-L>i j.vi A _'_..A.jhihi iii 1-0 .1. J. i- ? lX' ihXb i ..LL1 :1 : :1 -l.yj Oh A )■: h . 1A- J.'i A T iih b lb S u b m i t t 3d to t h e UjAAiuoto S c h o o l o f h i e h i A 0 .n S t a t e C o l l to ’8 Of A g r i c u l t u r e siiid A p p l i e d S c i e n c e i n t - e r i i a l f u l f i l m e n t o f t h e rceTiirejaents f o r h ie deuroe o f DOCTOR OF IMIhOsUihil L 'o ja.rtm e n t of On eini a t r y M i c h i g a n o t p . t e G u i l e ao - 1 9 44~ a:.-LilDDiiT Trls v / r i t e r v.;: l s u e s t o e x o r o z ? U i s a p p r e c i a t i o n t o Dr. I;, T c t v l n g f o r h i s h e l p f u l aurliu: t h e cou r o e of t h i s s u g g e s t i o n s oho in v esti^ atio n * o.v\Ji\i1 aLU i. li'iT ItO111 Oil ir-i 1 . I n t t o di i c t o r y L t a t an ent, . . . . . . 2. Review o f t h e L i t o r a l u r e . ., PURI jX CAT1 0 a O f rLnTARJr.itl 1. Con cm c t am ee h a t o r . . . . . . . . . . . T.v E t h y l A l c o h o l . ............. 5, P o t a s s i u m C h l o r i d e . . . . . . . . . . 4. S t r o n t i u m C h l o r i t e . . . . . . . . . . o . LL,rout it uu n ro m i'-ie . . . . . . . . . . . 6. b a r i u m and MinfiepiUm C h l o r i c PLLPhj liTlOa 01’ LULU i t uw h 1» L e i a n t e ano B a l a n c e s . . . . . . . . 2. G r a d u a t e * 1 G l a s s w a r e . ............... 5. A 1 c o h o l - W a t e r S o l v e n t s . . . » . 4-. S o l u t i o n s i n A l c o h o l - V . ' s t e r L L x t u r e s id?PAK/Aii l-M ii] PiVJ CELLKL 1. T em perature C o n tro l. 2 . Cond u o tG iic e C e l l s . . . . . . . . . . 3. L e t e r r a i n a t i o n o f C e l l C o n s t uh T tg e 1 1 y Q 10 10 11 11 II 11 I£ > 4. Aricine Assembly. . . . . . . 5 P r o e e uu r e . . . . . . . . . . . . . . . . . . LAP 1IRIMT1 mT a_L AERIJa T t ; 1. C a l c u l a t i o n o f R e s u l t s . . . y . I a t s ( T a o l e s j .. ; . ... 3. G r a p h s . . . . .................... 13 13 14 .x 6 18 19 36 LUMM/ucY. . . . . . . . . . . . . . . . . . . . . . . LITIRLAU RI CITED. .......... M ltOLUC TIOh A l a r g e amount o f e x p e r i m e n t a l w o rk r e l a t i n g t o t h e e le ctrica l co n d u ctan c e i n aqueous so lx rtio n s h as been r e ­ p o r t e d d u rin g t h e p a s t . f i f t y o r sixtj^ y e a r s . However, t h e a m o u n t o f work t h a t h a s b e e n d o n e o n t h e e l e c t r i c a l a n c e i n m i x e d s o l v e n t s n e s beexi r a t h e r l i m i t e d . work wa.s u m , e r t ; ' k e i : i n o r d e r to d e t e r m i n e t n e behsvior of c e rta in w ater m ix tu re s. aiw aJino e a rth h a lite s conuuot- The p r e s e n t conductance in eth y l alc o h o l- I n o r u e r to g i v e a g e n e r a l v iew of t h e s t a t u s o f e l e c t r i c a l c o n d u c ta n c e i n v e s t i g a t i o n s i n m ixed so lv en ts, th e fo llo w in g l i t e r a t u r e Lenz (1) w o rk e d w i t h is c i t cd. potassium io d id e , b r o m i d e and c h l o r i d e and sodium c h l o r i d e i n m e th y l c l c o h o l - v v a t e r end e t h y l alcohol-w rit e r m ixtures,. iyt e p h e n ( S) wo rk e d w i t h d ilu te l i t h i u m and p o t a s s i u m c h l o r i d e s , s o l u t i one o f sodium , and sodium an a p o t a s s i u m io d id e s in eth y l alco iiol-vw ter m ix tu res. K n b l u k o f f ( o) w o r k e d w i t h a lco h o l c o n ta in in g varying A r r h e n iu s {4}, H o llan d th e h y d ro c h lo ric aciu in eth y l am ounts of w a t e r . {5} and h t r i n o b e r g {6} studied changes i n conductance o f aqueous s o l u t io n s r e s u l t i n g from t h e a d d i t i o n to them o f s m a ll q u a n t i t i e s o f non­ e le c tro ly te s, a ceto n e, such as m ethyl o r e t h y l a l c o h o l , cane sugar, etc. Yvakemen ( 7 ) w o r k e d w i t h s o d iu m arid p o t a s s i u m h y d rochloric acid , ch lo rid es, and numerous o r g a n i c a c i u s i n e t h y l a 1 c o h o 1 - w at e r mi x t u r o s . o c h a l l (8) worked. w i l l ; p i c r i c a c id in ocueous e th y l a l ­ cohol . 2 e l i n s k y and X r a p i w in ( 9) w o r k e d vd t h n i u m i o d i d e s an a 'uiojaid.es i n w a t e r , t u r e o f t h e s e two s o l v e n t s s o d i u m unci annao- m e t h y l a l c o h o l e nd a m i x ­ c o n t a i n i n g 50 p e r c e n t w a t e r by vvriiyht * C ohen ( 10} w o r k e d ;i ' h ; u o r a s s i uia i.odi de i n e t h y l ■ W e l k e r and Ilsiiibly (1 1 ) women w its d islh ylax w m ium h y d r o c h l o r i d e i n e t h y l n I c o h o I - - v ; ; x te r m i x t u r e s , T i'.jm stru ( IS) ;vorK-id. i d t h m i x t u r e s o f m e t h y l or eth y l a l c o h o l .ana w a t e r o n r o d i u m . Roth (15) e Gup x o .i worked w ith c ti L■.)— l . a.! \ ‘i: , I ")j. T h e work o f I k potassium c h lo r id e in m ix tu re s o f , C, J o n e s a n d h i s c o - w o r k e r s (CO) o n c o n ­ d u c t a n c e i n m ix e d s o l v e n t s was u n d e r t a k e n a s an e x t e n s i on o f i n a o l u e r vvoru o 1 ■r o l x n s n y . Kim \ r a p i ’f i ; .1 d) , suid . {.mien 1 i d ) on t h e c o n d u c t a n c e o f e t h y l a l c o h o l s witn e l e c t r o l y t e s i n m i x t u r e s o f m e t h y l and water,. J o n e s and L i n d s a y (14) tem s: potassium io d id e , in w ater, of th ese worked w ith t h e f o l l o w i n g s y s ­ ammonium u r o m i d e and l i t h i u m n itra te e t h y l a l c o h o l „ m e t h y l a l c o h o l and b i n a r y n u r t u r e s so lv en ts; stro n tiu m io a id e in w ater, m e th y l, atiiy l, a n d p r o o y l a l c o h o l s and m i x t u r e s o f t a e s e t h r e e a l c o h o l s w i t h w ater; cadmium i o a i d e a n a f e r r i c ch lo rid e a l c o h o l and m i x t u r e ? o f t h e s e s o l v e n t s , . in w a te r, m ethyl J o n o s alia C g r r o . l l (15} v / o r k e a vd t n t h e tem s: cadmium, fo llo w in g sys­ s o d i u m and p o t a s s i u m i o d i d e s i n w a t e r , m e t h y l a l c o h o l end m i x t u r e s o f t h e s e s o l v e n t s ; calcium n i t r a t e i n w a t e r , m e t h y l and e t h y l a l c o h o l s sad b i n a r y m i x t u r e s o f t h e s e so lv en ts; h y d r o c h l o r i c a c i d i n m e t h y l a l c o h o l and i n m i x t u r e s o f m e t h y l a l c o h o l ana w a t e r ; W rie r ana a c e t i c sodium a c e t a t e i n m i x t u r e s o f acrci. t o n e s slid .Lto s .oe e a 0 ; m nnao. >.Ln 0 l.Ly e r U.Lt m e e i n v ^ i t e r , m e t h y l a n d e t h y l , a l c o h o l s ana. b i n a r y m i x t u r e s o f t h e s e a l c o h o l s w i t I i wat e r , J o n e s aid bingnnm (17) worhoa w ith t a s s i u m i o d i d e and c a l c i u m n i t r a t e eth y l a lc o h o ls, w ater, lith iu m n i tr a te , po­ i n a c e t o n e ; m e t h y l and and m i x t u r e s o f a c e t o n e v / it h o n e o f t h e o t h e r s o l v e n t s.. J o n e s and. Eon i l l o r ( l b ) w ater, a o r k c o \vi tn silv er n itra te in a c e t o n e , m e t h y l anu e t h y l a 3 . o o h o i s 3 a c e t o n e and. o n e o f t h e o t h e r s o l v e n t s ana. i n m i x t u r e s o f m e t h y l and e t h y l a lc o h o l s. J o n e s and ivicblaster ( 19) worked w ith lith iu m c o b a l t c h l o r i d e i n m e t h y l and e t h y l a l c o h o l s , b r o m i d e and v e/ter, acetone and b i n a r y m i x t u r e s o f t h e s e s s o l v e n t s . . . J o n e s and V e a z e y { £0) worked w i t h t h e fo llo w in g system s: c o p p e r c h l o r i d e i n w a t e r , m e t h y l end e t h y l a l c o h o l s a n d b i ­ nary m ix tu res of those s o l v e n t s; p o t a s s iu ia s u l f o c y e n a t e i n w a t e r , m e t h y l said e t h y l , a l c o h o l s , b in ary m ix tu res of th e se s o l v e n t s a nd i n b i n a r y m i x t u r e s o f a c e t o n e v / i t h e t h y l and m ethyl a le o n o ls . K r e i d e r a n d o o n e s { 21) n:onium i o a i d e , worked with p o t a s s i u m i o d i d e , oiamonium b r o m i d e , lith iu m n itr a te , podii.ua i o d i d e , am- potassium th io c y a n a te , caLcium n i t r a t e , e o b e l t c h l o r i d e and oo piper e l i l o r i u e i n m e t h y l e.i c o h o ! - 1,vat e r ana e t h y l a l o o n o l - ' . v n t e r i;:iIxtur ep., J o n e s d a l M a h i n ( 21) w o r k e d v. i t n lith iu m n itr a te aixd c c dmirm i o t i be i n b i n a r y aria t o m a r y m i x t a r es ; o f a c e t o n e w i t h m ethyl alcohol,, e t h y l alcohol k eiim idt ana l o n e a ( l b ) b ait and. a c t o r . , vorxced with lith iu m brom ide, co- c h l o r i d e a ud u o t a . u s l u m i o d i d e I n b i n a r y m i x t u r e s o f o l p e s r o i l/.'jLoil etny.i_ a l c o h o l i c o a h y x a r co !\o ..l ar* w atem Guy aim J o n e s ( ‘51) w o r k e d wl ti;. p o t a a n i r ii i c h l o r i c : e s a riium n i t r a t e , ammonium, promj de cud o t r o i i t l u i r . c l i l o r i c l e i n nary m irtu ro o o f y ly c o ro i -'I t l v aier, ij I — e t h y l a l a o h o i and m ethyl, a l c o h o l l l a v i s a n d <3) ru.L*iieu vvi. tie a.riuoniuiii L . a l C t a n d f.hhuonium b r o m i d e i n t e r n a r y niutnv'-ec; L._{ rubidium ‘ \j ... 3 ; f ,..w, a w i , a a.. „• Carmona k l ) u m ;;;; i l l . ; u h i n i h . ! .. rd i n meTli.yl a b ' - l .■'i.-a-ha- - l a c to r e s . socluia c a l o r l / ’ei'Kuv { 51) worker! vxith l i t h i u m n i ’ o. m il h r] iun ch lo rid e, io d id e, -lithium n i t r a t e , diun oolioy u t c i n b i n a r y ;■11 x t n r r:'i c o d o l , lith io n nro- tamuoniuiu t l i i o c y a n t h e 03 o f we t e i y diethyl e t h y l a l c o h o l and a c e t o n e . CtOletsciiYiicit { o o n i ' u o u n l . " : ) c a l l o y i 1. ■'. a n,\ o m nn.o_:/y • . v i . t n x; ’ r). ] o i a bn. f y r i o , I . ‘ -i. ’;■n ' .L ’’ ” i a t robjivco-lc.. a r i c h I o r e b u t y r i c cue, - ‘i ' 2 . ^cj.u i n 0 0 a u lfo salie y iic ay colce in m eth y l-. .&1cohoi ond i n raet h yl- ■s l e o l i o l - v n t e r x a i x t u r e s . , B i u i t e r 126) work or; m i x t u r e s oi‘ a c e to n e F i c o h l e r l b' / ) 01 t h mono- an ci u l ~ n i t r o s o r c i n i n nxd w a t e r , worked w ith pot L F s i e n i o a i e e brom ide i n b i n a r y td n tv - r e s o f terrene Den n o n e , m e t h y l a l c o h o l j, n i t r o and a c e t o n e . Do 10 Oi l eo a l l : i o d i c e, an d l i t i i i u m n r- c o t a s shu,: i o a i o e , Yxio uciylu.!!' n i t r a t e lii x n icJ iih { 26) Yvorheu. v / i t t 00 01 Lrrrium ciu o rid e,. ', end i n m i x t u r e a o f t h e s e t h re alc o h o l, sodium h u r l uni c i i l o r i d e e th v i alco h o l -6 ~ man'll a n c v a n d P r 7 , h e i ) o r o v £ k i I (6 9 ) trate in a n ilin e , ace to n itrile, p y ric ine, worked w i t h s i l v e r n i ­ o u in o lin e, m ~ ch lo ro an ilin e „ v e t e r end t i i e i r v a r i o u s m i x t u r e s . Ghosh ( 40} w o r k e d w i t h s o d iu m c h l o r i d e , potassium c h lo ­ r i d e and b a r i u m c h l o r i d e i n m i x t u r e s o f w a t e r and. p y r i d i n e . . K r a u s anti G r e e r ( 41) w o r k e d w i t h t r i m e t h y l s t u n n y l c h l o ­ r i d e i n ill t ro b o n . o n e - p y r i d i n e B ro w n son and C r a y (4 1 ) a c e t o n e ~ p y r i d i n e tuid a c e t o n e - worked, w ith h y d r o c h l o . r i c a c i d and p o ta s s iu m chloric; e in a c e t o n e - v a t e r m i x t u r e s . G o l d s c i u t i i u l and / . r f l o t fid) worked w ith h y d r o c h l o r i c a c i d and s o d i u m b r o m i d e i n m i x t u r e s o f m e t h y l a l c o h o l end w ater. Vdp.it man a nd Bp on c o r ane ntU rua. ( 41) w orked p ith lith iu m n i t r a t e in m etn v x mi. oeI■o ' I e t i ..y k m.coiiOj.. ei.np 1 *'..i.coha*i v.’;;t e r and m e t h y l e l c o l i o l - w a texa Y,h i t m a n and K u r t { 4-5) ro r k e d w i t h m ixtures: w eter--n~propyl a lc o h o l, e th y l alc u h o i-u -p iG p y i a lc o h o l, lith iu m n itr a te in the w x .ter-iso -p ro p y l a l c o h o l , e t h y l a l c o h o l - - i s o - p i ’o p y l a lc o h o l, a-prop yl alcoh ol-1 so-propyl a lco h o l. d i e s {46} w o r k e d w i t h a l k a l i n e h a l i d e s i n m i x t u r e s o f ethyl, .a lc o h o l-a c e to n e . R a k s h . i t {17) w o r k e d w ith h y d r o eh ."Lori a eo j :C m o r p h i n e , c o d e i n e , n a r c o t i n e and co t e r n i n e i n e t h y l e 1 coho 1-v/e.t e r m i x ­ tu res. F u s e y e an d M u r a t a ( 46} w orked w i t n c u p r i c , cobalt., c h r o m i c arid f e r r i c su lfa te s, silv er, zin c, n ick el, 1 ead mid. c u o r i c -7- n i t r a t e s end o u o r i c c h l o r i d e i n m i x t u r e s o f g l y c o c o l l end w ater. P r z e b o r o v ;-.k LI 5 G e o r g i e w s k i and F i l i p iowa ( 40) with s u lfu ric acid i ji ethyl K r e u s r-nd i ' u o s s ( 5 0 ) wo r k e d alcohol-w ater m ixtures. w o r k e d w i t h t e t r e i s o u m v l imimon.iiun n i t r a t e i n t n o x m i e ( Cl i ...CH,.UChi CR ,,0) , w et e r ond e t h y l e n e clic n i o i ' i d e and v a r i o u s m i x t u r e s o f e t h y l e n e d : i c h l o r i n e .unci o f w ater w its d i o x s r e ; t o b r s i s o n u y i s nmonium e y e u s t o i n d i o x s n e , bensene era in m ix tu res of th e s e tvo s o l v e n t s ond t r i - i s o b.my 1 tu.iiiioi i i urn p i crux, e i n e x n y r e n e a i c n l o r i d e , o e n s e n e a nd i n m i x t u r e s of t he oe two s o l v on c t . b rfo inI.u a ( 51) worned w i t h s u l f u r i c uciu in m ix tu re s o f v a t or m b {-lyccrol. C onnell c h l o r i d e sun ( ;3f) w orno! w ith l i t i i i u m w i l o r i c e , nine c h lo r i d e p o t a s slum ini m i x t u r e s o f e t h y l a i c o h o l .mid v'i t e r , A g a r w o l n an d 1.1 uni o r v i l l e ( 55) worksu w i t h p o t a s s i u m ch lo rid e in the m ix tu res: alco h o l, w a t e r - e t h y l a l c o h o l mo. - w a t e r - i s o p r o p y l a l c o h o l . H a t c h e r anu Ah'son ( 54 ) m ter-x m eto iie, v;oter-m ethyl wcrxea w ith s o d iu m h y u r o x i c i e i n m ix ­ t u r e s o f w a t e r unci a c o t on eThomas m b i-ho.tG.eviiie ( 5 5 ) wormed w i t h p o t a s s i u m ch lo ­ ric) s i n m e t h y l - u 1 c o l i o x . x t e r mi x t u r e s . C h i x t u m .‘uiU a n m n r ( 56) e o o iu m c h l o r i d e , t u r e s of ilrJ *vorkeu w i t h l i t h i u m potassium a c e t a t e and D*0. c h lo rid e, end n o e t i c a c i d i n m i x ­ Owen nncL '>«<ers ( 57} w o rk e d vvi t h h y d r o c a l o r i c a c i d i n d i o x a n e - w a t e r mi x t u r e s * hard (56, &£} w o r k e d wi t h a o d e c y l s o d i u m s u l f a t e i n e t h y l alc<>lio 1 - wet e r m i x t iir e n .. L o n g s w o r t k and am c l l i n e s ( 59} wo rked w i t h s o d i u m and lith iu m c h l o r i d e s i n a e t h y l alcohol-■'.•vat e r m i x t u r e s . Zrii kov a nd D n e o r o v (60) tue m ixtures; uorrec; w i t h hydrochloric acid in \v.i-.,r—e t n y i <• i c o n o i s v a t , e r —e t i i y r e n e e l y c o l and r t er-glycerol. Indovina m ix tu res. ( fil ! v n i f v n w> i-> h y d r o c h l o r i c a c i d i n —9 — P U K li'I Cjva'IOIm 01'* ivL'iL'EKlALfc) C o n d u c ta n ce i f e t e r , -The c o n riu c ta ij.e e w o t e r u s e d i n t h i s i n v e s t i g a t i o n had a s p e c i f i c r e c i p r o c a l ohms a t £ 5 ° . tillin g (63), flask c o n d u c t a n c e o f i <-00-1-0 ‘ixi0~*tJ f h i s w a t e r was o b t a i n e d by r e d i s ­ u i s t i l l e e l wet e r f r o m a l k a l i n e p o ta ssiu m p erm ang an ate T he a i s t i l l a t i o n was c a r r i e d o u t and conoen s e d by means o r a b >ut f i f t y The f i r s t a bioon in a fiv e l i t e r P yrex tin conuenser. o o r c e n t of th o s t e a m v,.£-c a l l o w e d t o 500 m l, u sed during th e of d i s t i l l a t e were d i s c a r d e d . O nly condense. ill sto p p ers d i s t i l l a t i o n , were c a r e f u l l y w rap p ed v-ith t i n f o i l , . T h e c o n d u c t a n o e w at e r w a s p r e p s - r e d o n l y a s h o r t t i m e before i t was u s e d . Et n y l a ! c q h o 1 - T 11 e a b s o l u t e p u rified and d e h y d r a t e d by t h e (a) To f r e e t h e i n g £0 m l . a l c o h o l t h a t v/as u s e d was fo llo w in g step s: a l c o h o l o f a m i n e s * e. s o l u t i o n o f w a t e r a n d SO m l . o f s u l f u r i c each l i t e r o f 95 p e r c e n t a l c o h o l , , c.cid wer. a acted t o The a l c o h o l was fcnen d i s ­ t i l l e d , o n a w a t e r b a t h and con den seci i n a b i o clc t i n denser. The f i r s t ( b) To f r e e t h e p r e c e d u r e ( 64) A so lu tio n and l a s t was u s e d f o r w a s s l o w l y a dried t o t h e s o l u t i o n was t h e n stirrin g , in to o f lead alco h o l, 25 n il, a cetate Then 5 g . in 5 m l. o f w ater o f p otassium o f warm a l c o h o l f r o m ( a ) . ooured slo w ly , the a lc o h o lic about one h o u r the th e fallo w in g each l i t e r of a l c o h o l from ( a } . h y d r o x id e were d i s s o l v e d i n T his con­ 50 m l «. p o r t i o n s w e r e d i s c o r d e d a lc o h o l of ald e h y d es, c o n t a i n i n g 3 g. c o n tain ­ w ith o u t m ixing o r so lu tio n of lead a e s ta te . A fter r a i x t u r e w a s a n a k e n t h o r o u g h l y and a l l o w e d -10- to .stand o v e r n i g h t . T h i s v'oe t h e n f i l t e r e d d i s c a r din#.-, 'd i e f i r s t ( c) ond l a s t 50 m l . Two h u n d r e d g r a n t s o f each l i t e r of d istilla te shaken th o ro u g h ly , f 3uxea f o r a llo w e d to about eig h t p o rtio n s. tienydroted from ( b ) . o v ern ig ht tio n A l l flask .. v -V . y.' -w ^ -v . . . a block tin Trie f i r s t o o x O X T 'I u c -i- - u j , \V X ...................... : r:. jy su ctio n flask . 11 coho 1 p r e p a r e d 99,. 9> a b s o l u t e o f 0„ £ 0 - 0 « 1 4 x 1 0 . u V V 1 \ J r^-Kd c h l o r i d e t u b e was n t t a c b e a about o 1 j. ! - l - - - •• b i l l to th e colum n, were d i s c a r d e d . J . U sid e arid h o d a S p e c i f i c P o t a s s ium C h l o r i d e . - T h e p otassium c ell S ' X X L liiU . IX arm o f h i e conductance 55°. c h lo rid e used in p re ­ c o n s t tint d e t e r m i n a t i o n s was r e c r y s t a l l i z i n g j . T„ B r i e r C o . o btained by t w i c e ,fs p e c i a l c r y s t a l s ” from c o n d u c ta n c e w a te r . heated re- i n t is is m a n n e r w a s o r d i ­ b r e c i p r o c a l ohms a t p a r i n g tti o s o l u t i o n s f o r an d t h e n a d istillin g d istilla te calcium n arily then e o n c e n s e r and. c o l l e c t i n t , i n a s u c ­ 50 ml., o f t K, ; J added to T h e a l c o h o l war th en rem oved f r o m t u e l i m e b y d . i s t i.Li. o t i o n t h r o u g h condensing in liiae v e re The m i x t u r e was stan d iiourm an d d i s t i l l e d , i n a- c r u c i b l e u n t i l p a r t i a l . l y Cb p . The s a l t was t h e n fu se d and p la c e d i n a d essicato r. fctro n tim s C h lo r id e . -The B a k e r Co. C. P . was p u r i f i e d fifty (co n tain in g in th e G.O Py BaO a n a 0.01%- CsO) f o llo w in g m anner ( 65) . g r a m s o f S r C l <-,* 5Ho0 w e r e c o d e d t o a n c e w a t e r „ h e a t eo t o at th is salt s t r o n t i u i a c h l o r i d e was 1 . T. u s tem p eratu re, w hich P our hundred 100 m l. of condu ct- ico i l i n g , c o o l e d t o 6 5 ° a n d f i l t e r e a , ft u s in g a B uchner fu n n e l (65 g . ) . The th en d isso lv e d in conductance w a te r a t 58° and -11- filtere cl. T h e f i i t r : : t e was t h e n cooled to q° ^nd f i l t ero d »T a B u c h n e r f u n n e l ( P-6 g . ) . using f 1 r o n t i urn B r o m l d e . - T h e s t r o n t i u m B a k e r Co* 0., p« k alies) b r o m i d e was J * T . ( c o n t a i n i n g 0.005/'> Ba r n d 0 . Mg a n d A l ­ w h i c h v.-us p u r i f i e d b y t v / i c e r o c r y c t a l l i z i n g fro m con- du. c t en c e v;at e r a t 0 . . B o r i u r s and B a k e r Co. -A 1 , B h lo r ia e s .-T hese sa lts were J . .>i-o uu c fc i n e a c h c a s e sue. w e r e p u r i f i e d T. by r e c r y a t u l l i u i n g once from c o n d u ctan c e w a te r . i n d J k U d . f l O n 01 l O i b l l O u l W elg n ts and i a . l r m c e s . -The w e ig h t a t h a t w ere u s e d were c alib rated by t h e K I c h o r d s s u b s t i t u t i o n m e t h o d ( 6 6 ) r e f e r e n c e t o w e i g h t s (1 0 g. brated by t h e B u r e a u o f AtaiKn. r d s ( T . b a l a n c e s were u s e d i n t h i s Bros., and 100 g . ) t h a t h a d iry e s t i m a t i o n . b a l a n c e ,, w i t h a c a p a c i t y s e n s i t i v i t y o f 1 . 0 may,, cohol fo r th e balan ce, so lu tio n s. h . k. a n d by seen c a l i ­ 01005), Two A ia r p e Becker o f 10 k i l o g r a m s and a n a v e r a g e was u s e d i n w e i g h i n g w a t e r a n d a l ­ A km, A i n s w o r t h a n d Bone a n a l y t i c a l v&th a s e n s i t i v i t y of 0 , 1. mg. , w a s u s e d f o r 'w e i g h i n g sm all q u a n t i t i e s of ele ctro ly te and f o r a n a l y t i c a l p u r p o s e s . G r a d u a te d G l a s s w a r e . -The v o l u m e t r i c f l a s k s and b u r e t t e s were c a l i b r a t e d tille d by d e t e r m i n i n g t h e w e i g h t o f b o i l e d d i s ­ writer t h a t c a l i b r a t i o n mark. was n e c e s s a r y t o b rin g th e m eniscus to t h e The c a l i b r a t i o n s were made a t t h e t e m ­ p e r a t u r e a t which t h e calib rated f l a s k w a s to be u s e d . A l c o h o l - Wa t e r S o l v e n t s „ - T h e a l c o h o l - v / a t e r e o l a t i o n s ’.'-■ere u s e d e s s o l v e n t s w e r e p r e p a r e d that from c o n d u c ta n c e w a te r a n d a b s o l u t e a l c o h o l b y weigh.i ng e a c h o f t h e s e s u b s t a n c e s ( co rrected to vacuum ). c o h o l V:a s d e t e r m i n e s . The w a te r c o n te n t o f the by d on s i ty ab so lu te a l ­ d e t e r m i n u t I on s a t £ 5 ° r n d then re fe rrin g to d e n s ity -c o m p o s itio n t a b l e s co n ten t o f th e a l c o h o l was u s e u i n c e t o r m i n i u g t h e i u a n t i t i u s o f alco h o l ana w a te r f u r each (67) . The w a t e r exact solution,. ho l u t i o n s- f o r C o n d u c t a a c e D e t e n n l n a t i on s »- 1 n a 11 c a. s s s except th e so lu tio n s in ab so lu te a lc o h o l. i t a d v i s a b l e to prop or o t h e e o l a t i o n s of t h e " ' m a s t e r s o l u t i o n ” r a t ) : o r t h a n f r o in t h e cord in g ly , G .£5 y, was c o n s i d e r e d sa lts from a anhydrous sa lt. Ac­ tw o ’’m a s t e r s o l u t i o n s ” ( e a c h c o n t a i n i n g a b o u t o f S r 0 1 o pel" £ . 0 0 g,. o f s o l u t i o n ) th e salt th e ch lo rid e as uere p re p fired enu c o n t e n t c s e t e r m i n e d by a g r a v i m e t r i c c o t e r m i n a t i o n o f silv er ch lo rid e. In t h i s weyy t h e amount o f m a s t e r s o i u t i o n r e p a i r e d t o s u p p l y a .given q u a n t i t y o f s t r o n ­ tium . c h l o r i d e in g c o u l d bo c a l c u l a t e s a s w e l l u s t h e q u a n ti t y o f w a te r a s s o c i a t e d w ith i t . T h is correspond­ q u an tity o f m a s t e r s o l u t i o n w a s t h e n w e i g h e d an d q u a n t i t a t i v e l y t r a n s ­ f e r r e d to flask ten t. a c a l i b r a t e d 100-ial. and a l c o h o l w a s a d d e d t o volum etric corny eu s a t e f o r t h e vast o r c o n ­ T h en t h e p r o p e r a l c o h o l - w n t e r s o l u t i o n was u u u e u , so lu tio n brought to £ 5 ° ( o r 50°} s i f t e r a b o u t 45 m i n u t e s t h e in so lu tio n b r a t e d mark w i t h no r e o f t h e d ilu te {g l a s s - s t o p p e r e d ) a th erm o stat the o a t h and. was b r o u g h t t o al uuhol-w ot e r s o l v e n t. th e c ali­ T h e more a l e o h o l - w a t e r s o l u t i o n s were p r e p a r e d by d i l u t i n g t h e more c o n c e n t r a t e d so lu tio n s. c en trate d so lu tio n in to The p r o p e r q u a n tity wos w i t h d r a w n f r o m a c a l i b r a t e d a c a l i b r a t e d 100-m l. v o lu m e tric f l e s h flash b u rette the The so lu ­ t i o n s i n a b s o l u t e a l c o h o l w e r e p r e p ; r e d by p l a c i n g q u a n tity of anhydrous s a l t con­ and b r o u g h t t o marie w i t h t h e p r o p e r s o l v e n t a s d e s c r i b e d a b o v e . rect of th e th e cor­ in a c a lib ra te d v o lu m etric and d i l u t i n g t o t h e marie w itri a b s o l u t e a l c o h o l . AdhlR/.TUh AuL hi-: jClbU in] Teinpera tu re C o n t r o l , -T em per at u r e p re p a ra tio n o f so lu tio n s and d e t e m i n a t i o n o f was a c c o m p l i s h e d b y m e a n s o f (g lass) co n d u ctiv ities e th e rm o sta tic a lly co n tro lled w a t e r - b a t h o f 28 l i t e r s du c ed by t w o , 125 w a tt* c o n tro l d u rin g the capacilj' . h eatin g u n its H e a t i n g was p r o ­ end c o o l i n g by w a t e r running' t h r o u g h a c o p p e r c o o l i n g u n i t . In o rd e r to av o id th e i n t r o d u c t i o n o f .any u n d e s i r a b l e e f f e c t s from an e l e c t r i c m o to rs a sm all t u r b i n e , d r i v e n by a for s tirrin g T he t e m p e r a t u r e was r e a d f r o m a 0 . 0 1 ° th e b a th . w a te r m otor, was u s e d Be ckm ann t h e r m o m e t e r t h a t h a d b e e n c h e c k e d a g a i n s t a 0 . 1 ° A n s c h u t 2 . t h e r m o m e t e r (13. 8., B o . m in atio n s, t h e tem p eratu re 49571). During th e d e te r­ d i n n o t v a r y m o re t h a n 0 . 0 1 ° f r o m the d e sire d tem p eratu re. C ond.uctance c e l 1 5 . ~Tliree d i f f e r e n t t y p e s o f c o n d u c t a n c e c e l l s were u se d ; t h e 0 s t w u l d , W ashburn* B o llin g e r types. In general* th e doterniunation o f th e o th e r ty p es f o r th e and J o n e s and tn e O s t w a i n t y p e was u s e d f o r conuu c t a n c e s o f t h e s o l v e n t s e n d t h e conductances o f th e so lu tio n s. The -14- le sh b u rn type more d i l u t e c e l l wu s u s e d f o r o n l y a s m a l l n u m b e r o f t h e so lu tio n s,. A v a r ia tio n of r e s i s t a n c e h a s been o b se rv e d the e ffe c t to how ever, effeet" in the stray a d so rp tio n . by P a r k e r ( 6 8 ) d i s a p p e a r s when t h e are constant a t higli who a t t r i b u t e d J o n e s and B o l l i n g e r (69) d e f i n i t e l y proved t h a t t h i s cell cell have, so -called "Perker- f i l l i n g t u b e s an d e l e c t r o d e l e a d s sp a c e d i n a m anner w hich a v o i d s a o p r e c i a b le C urrents. The J o n e s ona B o l l i n g o r t y p e c ells s i g n e e so a s t o a v o i d c l o s e p r o x i m i t y o f p a r t s o f o f opp o site p o la r ity ( see F ig, 1). a re de­ the ceil Two J o n e s a n d B o l l i n g e r c e l l s w e r e made b y t h e w r i t e r a n d u s e d f o r m o s t o f t h e d u ctan ce d e te rm in a tio n s in e.lcohol~ w nter m ix tu r e s . c e l l s w e r e m ad e o f J e n a 1 6 ' o x id atio n in th e a lc o h o lic Ll 1 glo ss. so lu tio n s con­ These I n o r d e r to i p r e v e n t (70), th e e le c tro d e s were n o t c o a te d w ith p la tin u m b la c k . D e t e r m i n a t i o n o f C e l l Co n s t a n t s , - A l 1 c e 1 1 s e x c e p t t h e JVoshburn t y p e w ere c a li brated a t s o lu tio n o f potassium c h lo rid e, 2 5 ° -u s i n g a 0 , 0 1 " d e n i a l " c o n t a i n i n g 0A745S6 g , p o t a s s i u m c h l o r i d e mud 9 9 9 . 255 g . to vacuum ). The s p e c i f i c o f w ater ( both c o lle c te d c o n d u c t a n c e of c o r d i n g t o J o n e s a n d B r a d s h a w ( 71) Th i s v alu e ch lo rid e w ater. is the after sp ecific su b tractin g of is th i s so lu tio n ac­ 0 ,0 0 1 4 - 0 8 7 7 a t 2 5 ° , conductance of the p o tassiu m th e sp ecific T h e re fo re „ in using th is conductance o f th e v alu e, th e sp ecific con­ d u c t a n c e o f th e w a t e r u s e d i n p r e p a r i n g t h e 0 . 0 1 "denial" s o l u t i o n w as added to 0.0014087 7 t o g iv e t h e s p e c i f i c d u ctan ce o f th e so lu tio n . con­ T h is v a lu e has been ta k e n as th e be s i s fo r e ll th e m ation. c o n d u c ta n c e m easurem ent s in The W ashburn c e l l p re p a rin g a s o lu tio n of p otassium i n t h e J o n e s and B o l l i n g e r T his c ell. sp ecific T h is t h e VVachburu c e l l . c o n d u c t an ce v a l u e s o b t a i n e d conductance s o l u t i o n was In com puting .in t r e c e l l s , , v i i i c h w e r e c a l i ­ b r a t e d e.t f r e q u e n t i n t e r v a l s , , t h e m o s t r e c e n t •vans a l w a y s u s e d . wns d o n e b y c h l o r i d e v / h i c h was a n u r o x i - m a t e l y 0 . 0 0 1 " d e n ia l” and d e t e r m i n i n g t h e th e n used i n c a .li'o ratin g inv e s t i ­ was c a l i b r a t e d b y i n t e r - c o m p a r i s o n w ith one o f t h e J o n e s and B o l l i n g e r c e l l s . of it th is The c e l l c o n s t a n t s a t calib ra tio n *’.0° and 5 0 ° wene c a l ­ c u l a t e d from t h e v a l u e s a t 15° u s i n g t h e m ethod o f c a l c u l a ­ tio n d e s c r i b e d by W a s h b u r n ( 7 £ } . o f 5° r e s u l t e d i n An i n c r e a s e i n t e m p e r a t u r e a decrease in th e ceil c o n s t a n t o f 0.0050% f o r t h e J o n e s and B o l l i n g e r c e l l and 0.0055% f o r t h e W ashburn cell. co n stan t i s le s s T h is sm all change in experim ental e r r o r in t h i s cell work w i t h v ent s . than th e s o l u t i o n s i n m ixed s o l . . . . . . . . . . B r i d g e A s s e r a b l ; ; . - A Ko3m.ra.usch. b r i d g e a s s e m b l y w a s em­ ployed in t h e conductance d e te r m in e tio n s ( se e llig . g) . The assem bly c o n s is te d o f th e fo llo w in g p a r t s ; { o) L e e d s and L o r t h r u p h o u r rausc.h s l i d e w i r e b r i d g e w ith e x te n s io n co ils (1000 d i v i s i o n s , read ab le to 0 .1 d iv i­ sion) . ( b) T u n a b l e t e l e p h o n e ( c) r e c e i v e r ( R e s i s t f n e e 12 0 o h m s ) . T y p e E V r e e l a n d o s c i l l a t o r { 500 a n d 1 0 0 0 c y c l e s p e r s e c . ;, ( d) V a r i a b l e a ir c o n d e n s e r ( 0 - 0 ,>0005 m i c r o f a r a d s ) -18- ( e) C u r t i s c o i l r e s i s t a n c e bo 2: ( 1 0 0 0 - 2 0 0 0 0 ohms)* (f) 3 - D i a l R e s i s t a n c e box ( 1 - 1 0 0 0 o h m s ) . The l e a d w i r e s t o t h e v a r i o u s p a r t s o f t h e b r i d g e a s s e m b l y an d t o t h e c o n d u c t a n c e c e l l s w ere h e a v y , wire* in su lated , copper T he w i r e l e a d s f r o m t h e b r i d g e w e r e c o n n e c t e d t o t h e c o n d u c t a n c e c e l l by m ea ns o f tw o s m a l l c u p s c o n t a i n i n g m e r ­ cury. A ll p a r ts o f th e b r i d g e a s s e m b l y wore p r o t e c t e d by p r o p e r l y grounded s h i e l d s , P r o c e d u r e . - T h e s o l u t i o n s whi ch w ere t o be u s e d i n c o n ­ d u c t a n c e d e t e r m i n a t i o n s w ere p r e p a r e d o n l y f o r e t h e i r c o n d u c t a n c e s were d e t e r m i n e d . s h o r t t i n e be­ 0 C a r e was t a k e n t o make a l l t r a n s f e r s o f l i q u i d away f r o m c o n t a m i n a t i n g a i r and to p rev e n t e v a p o ra tio n d uring preps r a t i o n , The c o n d u c t a n c e c e l l wes r i n s e d s e v e r a l t i m e s v.-itn t h e s o l u t i o n , f i l l e d w ith t h e s o l u t i o n and p l a c e d i n t h e t h e r m o s t a t b a t h f o r a t l e a s t t h i r t y m inutes. A fte r t h i s tim e, the c o n d u c t a n c e was d e t e r ­ m i n e d by m ea ns o f t h e K o h l r e u s c i i b r i d g e a s s e m b l y * The r e ­ s i s t a n c e box was s e t a t a v a l u e w h ich would g i v e a b r i d g e re a d in g n e a r tne center* The v a r i a b l e a i r c o n d e n s e r was a d ­ j u s t e d so t h a t t h e m o s t s a t i s f a c t o r y n u l l - p o i n t was o b t a i n e d . , ft i t h t n e SMiiie b r i d g e s e t t i n g , s e v e r a l b r i d g e r e a d i n g s were mode a n a t h e a v e r a g e v a l u e was r e p o r t e d * p o larisa tio n , I n o r d e r to p r e v e n t e l e c t r o l y s i s end h e a t i n g o f t h e c o n ta c t key ( com pleting t h e c i r c u i t ) so lu tio n , the was t o p p e d o n l y enough to perm it th e p roper lo c a tio n of th e n u l l - p o i n t , n d eter­ m i n a t i o n was now made 011 a s e c o n d s o l u t i o n o f t h e same com­ p o s i t io n as the f i r s t b u t which h e a been p r e p a r e d c o m p le te ly - 19- i n depend, e n t of t l i e f i r s t so lu tio n . I f t n e co n d u ct'an ees o f t h e two s o l u t i o n s did. n o t a g r e e w i t h i n a b o u t 0.1^,** t h e d e ­ t e r m i n a t i o n was r e p e a t e d . R e p e t i t i o n s were n e c e s s a r y o n l y i n a v e r y l i m i t e d number o f cases.. The c o n d u c t a n c e o f e a c h s o l v e n t was d e t e r m i n e d a s h o r t t i m e b e f o r e t h e p r e p a r a t i o n o f th e corresponding solutions,, The s p e c i f i c s o l v e n t was s u b t r a c t e d f r o m t h e s p e c i f i c s o lu tio n to give th e s p e c if ic conductance of t h e c o n d u ctan c e o f the corduo f e n c e due t o t h e s o l u t e a lo n e (75), j U v f . 'h i 1 i v i i - 'j i 'i j . / I i P 1 .1 C a l c u l a t i o n o f Re su i t s . - T h e so lu tio n is sistan ce, dofined I j i— , 1 i .i1 sp ecific conuu.co&nce o f e as t n e r e c i p r o c a l o f i t s sp ecific re­ The r e s i s t a n c e o f f e r e d , by a s o l u t i o n t h a t t a i n e d i n o c e l l w ith e l e c t r o d e s 1 sq. xiowever, so lu tio n . i s n o t c o n v e n i e n t n o r a d v i s a b l e to h a v e a c o n ­ d u c t a n c e c e l l w i t h tli e s e d i m e n s i o n s . ance, con­ cm. i n a r e a a n d 1 cm. a p a r t i s Known a s t h e s p e c i f i c r e s i s t a n c e o f t h e O rdin arily i t is T he s p e c i f i c conduct- . i s r e l a t e d t o t h e " m e a s u r e d " c o n d u c t a n c e by a c o n s t a n t f a c t o r K., d e p e n d i n g u p o n t h e d i m e n s i o n s of t h e cell, which I s known a s t h e " c e l l coup t e n t . n The c e l l c o n ­ s t a n t may be d e t e r m i n e d fO r a c e l l by m e a e u r i up t h e ance o f a s o l u t i o n whose s p e c i f i c t h i s wo r k t h e c a l l o r a t i n g conduct­ c o n d u c t a n c e i s known. In s o l u t i o n was 0 . 0 1 " a e m e l " p o t a s s i u m c h l o r i n e v/hich h a s a s p e c i f i c c o n d u c t a n c e o f 0 . 0 0 1 4 0 0 7 7 r e c i p r o c a l ohns ( p l u s th e s p e c i f i c conductance of th e w ater) irt 25°. I f t h e o o t ' c r v e d r e s i s t a n c e , K s fox' t h i s s o l u t i o n i s m u l t i p l i e d by i t s so e c i f i c c o n d u c t o r c e s t h e c e l l c o n s t a n t i s obtained. .if - LK P.y u s i n g t h i s ealibr;: t e d c e l l th e s p e c i f i c s o l u t i o n may now be o b t a i n e d c o n d u c t a n c e o f xny ey uci ng The s p e c i f i c c o n d u c t a n c e r h u s a s t o i v i i - c s , nopreoonts the bo t s i t r u e d .l i. o o'■-':’■'i o x ' ■i! ' X‘ o [ t ■l . so x. 1.1 x x o fi , co n d u ctan ce o f tbs p u r e s o l v e n t i s s u b t r a c t e d from t h i s v a l u e the d iffe re n c e re p re se n ts th e s p e c ific e le ctro ly te X..l o!le Sir) 3 c x 11 e (in tn is solu tio n ) . conductance o f t h e The e q u i v a l e n t c o n d u c t a n c e i s t h e co n d u ctan c e- I n r e c i p r o c a l ohms o f a s o l u t i o n c o n t a i n ­ i n g one gra m e q u i v a l e n t p l a c e d o e t v e e n e l e c t r o d e s o f i n d e f i ­ n i t e h e i g i lt p l a c e d i cm, apart. e v e r , may oo uo.re c o n v e n i e n t l y ik u i v a l e n t c o n d u c t a n c e , how­ c a l c u l a t e d from tn e r e l a t i o n A ~ LV wiLere V i s t h e \o lu m e o f t h e s o l u t i o n i n cubic c e n t im e te r s , w h i c h c o n t a i n s o n e g r a m e q u i v a l e n t w e i g h t o f t :;e e l e c t r o l y t e . D a t a T a b l e s.. -T hu d a t a f o r t h e v a r i o u s s y s t e m s i n v e s t i ­ g a te d a re in c lu d e d in tn e f a b l e s of t h e fo llo w in g p a g es, nn a t t e m p t h a s b een made to laaice t h e s e t a b l e s p r a c t i c a l l y s e l f explanatory, However, a few rem a rk s a t t h i s tim e w i l l u n ­ d o u b t e d l y c l e a r c e r t a i n p o i n t s which m ig h t o t h e r w i s e be do ubtful. The c o n d u c t i v i t i e s by a .1.1 s y s t e m s e x c e p t 0 , 0 1 1! s t r o n t i u m c h l o r i d e were d e t e r m i n e d on s o l u t i o n s w h i c h h a d b e e n p r e p a r e d by t l i e s u c c e s s i v e d i l u t i o n s o f t h e more Conductance of S t r o n t i u m Chlorine in 4 0 ;,? Sthc.no 1 m u 60 5 Wat e r at S5 ° r-i -p 05 1o60 Oi) i■ : 60 av- -ic u :j a va *. o V Oo a Vi’ 8. S p e c i f i c C onductance C o r r e c t e d . i n r e c i p r o c a l ohms end i s ( uncorrected) m inus t h e t h a t was u s e d 111 S. eq u al to t h e sp ecific T h is i s sp ecific expressed conductance conductance of th e solvent t h e p r e p a r a tio n o f the s o lv e n t. E q u iv a le n t C onductance. T his i s expressed in r e c i p r o c a l ohms a nd i s o b t a i n e d b y m u l t i p l y i n g t h e conductance ( c o rre c te d ) by t h e n u m b er o f m i l l i l i t e r s quired to c o n t a i n o n e g r a m e- u i v a l e x i t w e i g h t trolyte-.. The r e s u l t s of the for d u p licate d ele rn in atio n s in the ta b le s as t r i a l s sp ecific (a) re­ e le c­ a re given a n d ( b) t o g e t h e r w i t h t h e a v e r a g e e q u i v a l e n t c o n d u c t a n c e f o r t h e s e tw o t r i a l s - O o O C; 01 --y ry' f--' c fr­ ee cc H* ■ ■■ y Ci << * i- ;—' h ' r- J ft © 0 = CD O CD r— rt— o k- co ;) OS GI C.s C C ft « i i O' fie CS CD) O <0 - ') "TO h~’ CO OS os cs :0 O m co cn > T-‘ if'-* c0 iO O' n , £"~ y w. liu C Ol rh-; L~* f- OS iO- rn OS O r ?; ■ O OS ’ .i CO .I'-* -0 < Tc ■co r. :• DO C"! o c;i 4 » i„-^ os ros CD * * Cl c ; o'* 1 0 ; > Ol •;'i CO Co tl:- : 1 f - i~- •_.. o c »• ,f;> r '; <0 CD1 OS C.(S CD U<-i y. > n;\ >* O'" r— CO y> y. • y. CO *"•*• O'C j-'. ;") * 0 > ( . O ': O C> Ol i (— O': OS ro co ;o - y o {— ■1) o c- ; i s t n r c e Sou Reno.inf 'o ' i n s ■ ’ o; j-■ ’ * •» CO SO < ’.T to' o 0 o h- ■;r i n 0 "S otio” ;/lo ( Cl1 is :*O Or, ] l rnC5 e.! 0) f-e Cel 'y - « * * CD O Cl C oncentration o f S olution (rio rnelity ) O' c ; 0; r .■ « V O 1 1 O oO f-o O C; 0 3 o S CD I-- ;yt •- ( \ -•r\ <( j C 0 ■t ' Is 0.T) f .j '\ *r •J ft c ) C) ("; < '• r i >; ' ; < Cv) c p ecific ( .icorrect- ? C, : c^ ; ro e .. CO S"S j. S p e c i f i c Ce Corrected. Cohn; uC b .. CO CO O'! Ol Co CO 00 i c o o -o n ;o h" C> CO cO t.. . (O J . . . } a ■ 0 — 00 OS ^ u c u i v e l e n t Conductance (ohms"~) o o o o o C oncentration o f S olution (norm ality) Cr O M >v O r L 0, r- ■ c o .. ! "j i- ~ o n O' O' -o !— p ,11-. ^ j - -r * e O .O■'“> tu c . c . c. c. -o -r -,3 1... J»■ O f- ;v U' r c cy .& ■ c r*' o -o C: c. r-J C- * ® o •c o. o -'.jr- c o d- C- *.j •i. O rr o r► ■ . o OO o cr O' O O: ■- o c- ^ cr < i r*J o CJ D ON ; MJiiA] o * E q u i v a l e n t Conductance (x ^ • :■■O'. 01 O cm'£- (ohms” - ) cr ry o■ o o A * o cr r* ♦ r; '>-• y- f ’ 0> C'<_ ■ Cf__ r-' • o G.1 G . J. h--‘ O' v:; G. o ► O'1 j'.1 e=J •-;' j' 05 C . j ; ■O r>-< c :: e ■ o J. j: o 'J « • • I 4 o o >— * J. CC f— ‘ re r' c % O o o rr 0 C* A’ C " CJ •• f' —r~ < r*• r .■ C ‘- i—’ y~ rr- CL- GJ O 'T- i—1 I— c JCj •G r' ‘ C J o Or rj *—■ r: J: r“ »4 k F . e s i s t a n c e Box R e a d i n g (ohms) r- C B ridge Reading * - R a t i o ?? • O O' o O' 00 C~r D’ c* o f c-' 1—' A J. •»!'■• j— J rr- v C oncentration o f S olution (norm ality) n r j i r ^ v i n ’K i o o CO o h™ < ao r't»■> « '. g o rr cr* r--' '-S vo o1—• o C.j (C o O' Cj o h- ■”o J) o —’ -.2 o C’ nini. i' m cr' O O o o o o rr CJ rc CJ — — ^ r-' -G C- O' .. :■ ■.J O ' J j A/ 10 0 0“ A : ' O' cc J r.xo i q - ) "4 “ — c i CO o Or-‘ cc O CC 0-: G fr ^- j rr •P= •-». 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O —33— Conauctc:nee oi Strontium in u 0 /0 E t n a n o l Onloriue on 1 0 ;5 W a t e r to o 06 0 0 0 5 1 6 i t 1 o ♦4 4 6 J 0 0 5 8 5 c c. .Lo , 4 5 4 lo .4 4 0 O4 06 19 ,.396 19.369 19.377 ./ 96 7 0 10 0 14 10 14 1 0 00011173 0 0011176 0 04 6 avg 6 0 0 1 £ Vg iso 185 165 175 90 6 4 O 'i O ■ . 0 0 1 at 00607 0 005 005 anu 5c 0 1 560 1 9 99 6 ■ j 00006507 0 0 0 1 1 1 1 1 C- C. . ! ,! r-J V •’■I \ Cc ^ Vi - p [ ; p ■ ' • 4- > *.-t f/. PP P-l S o lv e n t ; y 4j 4-1- »._■. i v b0 (..■ L.‘ ».■■ i •i :\v v \r> ‘. . o i o . C * • ) ;/ E t h a n o l .• . J •■ -0- i- ■ i. *, J X. i c .1’■ Ob o C .' 4 : j ■') ~r Cc: . -j j ■' c 1 in t t Z- .4 i J K .I 0 , J J 06 0 . j ' ! o 'h u c .'J x. or ^ ; ' ) s; ,.« 0 < o c-7'c ‘ J ;•. \ ., 1 L, 1:0 7 0 . 3 SO 0 *’2 C■C7 ( ;'l ; ' 0 7; ) t. i ' ■ ‘ ■ ■' 1 a » * -J: ‘C^c’b j 7 7.7 ri - . • r o J p.11 0 1 o O' 10:1 . 0 5 . O O l o l o O ; 1 .0 1 . Ob 1 , "i Ky ,0 1; * :0 7 4 Pi n x. I P. .' 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O r .1 u t k t 0 per cent oC etnano 1 m Pifc.4 . - - E q u i v a l e n t conductance e t h a n o l “ Water m i x t u r e s a t 05°. * of oo solvent barium 100 chloride O'" .-3> ; ■C r -O t) • Y>U - 40- 160 eight per cent ethanol in solvent: 140 C onductance r\ 100 Equivalent 80 40 20 o 0 0.04 0.06 Con c e n t r a t i o n , g r a i n e q u i v a l e n t s F i g . 6,-- E q u i v a l e n t c o n d u c t a n c e in e t h a n o l - w a t e r m i x t u r e s at 25°. of 0.08 per lite r 0.1 strontium chloride -■17- 160 eight per cent ethanol in s o l v e n t : 1 - - 9 9, 897' 2 ^ 9 0 /:■' 140 3~ - 80 Equivalent C onductance 120 100 80 60 40 20 —o 0 0.05 0.10 Square F i g , 7.-- E q u i v a l e n t ethanol-water mixtures 0.15 root of conductance at 25°, 0.20 concentration of 0.25 strontium chloride 0.30 in 160 i-'Ci' c e n t e t h a n e xu a o l v e u L e Equivalent C onductance 140 cU 0 .) V o l u me , l i t. e r s in 60 r% p e r ^ram e q u i v a l e n t F i g . S . E q u i v a l e n t oonauctance e t h a n o l - w a t e r m i x t u r e s at 1 5 u , . / weight of s t r o n t i u m chloride 160 eigh t per cent ethanol in solvent: 1-- 99.39 100 SO Equivalent Conductance 140 40 O- 20 24 26 Te m p e r a t u r e , ° 0 . 28 30 F i g . 9 . - - E q u iv a le n t conductance of 0.01 N s t r o n t iu m c h l o r i d e in e t h a n o l - w a t e r m i x t u r e s as a f u n c t i o n of t h e t emperature. 160 Tempera t u r e : 140 100 80 Ecuivalent Conductance i 1!0 7 40 n 0 40 20 Weight p e r c en t 60 ethanol 80 in s o l v e n t 100 E i g . l O . -- E q u i v a l e n t c o n d u c t a n c e of 0,01 K s t r o n t i u m c h l o r i d e in e t h a n o l - w a t e r m i x t u r e s at 2 0 ° , 2 5 ° and 30°, 160 o n c en tra .tio n of s o l u t i o n : ( no x'inali t y ) 140 0.05 0.025 0.01 0 .005 0,0025 100 80 mivalent Conductance 120 40 20 20 Weight p e r A 'J cent 60 ethanol F i g , 11.-- E q u i v a l e n t c o n d u c t a n c e in e t h a n o l - w a t e r m i x t u r e s at 25°, 100 in s o l v e n t of strontium bromide 160 140 eight per cent ethanol in s o l v e n t ; U'/O Co nduc t a i 120 ruivalent 80 60 40 -Q 20 0 0,02 0,04 0,06 0.08 C o nncceennt trr a t i o n , g r a m e q u i v a l e n t s p e r l i t e r F i g . 12,-- Equivalent conductance in e t h a n o l - w a t e r m i x t u r e s at 25°. of strontium bromide Equivalent Conductance o Pi ' r i 4 'fi O ’V O •J ;-r w u B o o 160 ip:n p e r c e n t ethane n solven t: 1.00 80 Ecuivalent Conductance 40 40 °0 0 400 800 200 1000 V o l u m e , l i t e r s p e r g r ?m e q u i v a l e n t weight P i g , 14.-- E q u i v a l e n t c o n d u c t a n c e of s t r o n t i u m ‘bromide in eth? n o 1-w a t e r m i x t u res at 2 5 0 , ■J'./• , C v.-;r r ci of F i . t : , 1 5 . ■■■ '-'h- n i ty 1■- v r. i x t u r 1--; +-v. V.’^L~ r v. ~l:e e o i t i: e t r e e tv.:; -"hfcr'te'. ■ % cr. the ^c. r.v .. r: < r c t . v t c v'i Ti; j \ • e - or. e t e r . t - c r/’ u ■' 5e r:~ e —s o ­ i l L1OU i -P i 0 lm systems in v e s tig s te a For the dependence o f e q u iv a le n t electrolyte, In t n i s wor:c, t h e g e n e r a l c o n d u c t o n c e on: the nature of the t h e coiapositi on o f t h e s o l v e n t , tio n o f the electrolyte, and t h e may b e i n f e r r e d f r o m F i g u r e s s i d e r how e q u i v a l e n t the tem perature of 5-Id, At t h i s conduct; mee i s cone out r a ­ the solution, fci .se, l e t u s con­ I n f l u e n c e d by each o f t h e s o 1'ou r f a c t o r s , ( rh f!' - p-fi ii-p j_v~i f-. h o T) Q-f-nv-n o f f'n ° feet of th is F i g u r e s 3, 4, figures that the change i s 3 and 11. illustrated It r e l a t i v e l y sm all trend. 1 f A~ r"V | 1 *rf C g iv es conductance I n oaon c a s e , curves with the addition of a q u a n tity of ethanol to th e aqueous s o lu - equivalent d u c t a n c e t h on by t h e . a d d i t i o n o f t h i m s a n e 1’h e e f f e c t o f i n c r e a s i n g l y l a r g e r p e r c e n t a g e s o f e t h a n o l to increasingly same e l e c t r o l y t e sm aller percentage conductance. certain value, concentration) decreases in the When t n e p e r c e n t a g e o f very l i t t l e , if any., con­ q u a n t i t y o f ■■ any of t h e e t h a n o l - w a t e r s o l u t i o n s , s o lu tio n ( fo r the of— by i n t e r c o m p a r i s o n o f t io n s produces o la r g e r d ecrease in the e t h a n o l to ^ ln 0 may b e o b s e r v e d f r o m t h e s e each e l e c t r o l y t e same g e n e r a l 0 a given causes equivalent ethanol reaches a effect is p r o d u c e d by t h e f u r t h e r a d d i t i o n o f a sm all q u a n tity of ethanol, corresponds to conduct ancc a point of i n f l e c t i o n i n the c u r v e a nd o c c u r s a t d i f f e r e n t positions for d ifferen t This . electrolytes this ( sa me c o n c e n t r a t i o n ) . a given e le c tr o ly te p o i n t o f mi ni mum e f f e c t f o r d e p e n d e n t on t h e e l e c t r o l y t e j-.F. i l i u s t r a t i o n s , the s o lu tio n s of d i f f e r e n t ing p e rc e n ta g e s of r i d e SO1;? ( F i r , Also, th e p o s itio n of concentration* points of in fle c tio n so lu tio n s occur at ethanol in the 5); solvent: f o r t h e cii f f e ^ e n f e~ie c t r o l ■ ’.rt.r 3 equivalent 11) a re compared, As e t h a n o l i s served, th a t ancG i s ( F i g . 5) strontium chloride a a d e d to the ( 1 2 0 solvent, same curves fo r and s t r o n t i u m o h ms “ J') it Li;at t h e w ill th is point, the decreases lo ss (b) of solvent th e De o b ­ of t h e e a u iv f ile n t - c o n d u c t- ethanol. p e r c e n t age i s i n c r e a s e d eouivalent does for strontium CJinnge i n c o m p o s i t i o n o f t h e s o l v e n t . c o m p o s i t i o n on e q u i v a l e n t by c o n s i d e r i n g ( s e p a r a t e l y ) sm aller percentage tne above, the p e rc en t ages of ethanol w ■ about beyond conductance o f s t r o n t iu m bromide rap id ly than i t As. wa s s t a t e d is in pure a b o u t t h e sa me f o r t l i e s e t w o e l e c t r o l y t e s up t o as ). .^n +■ + >*<:.+■ i t v/i 11 be o b s e r v e d r a t e .of d e c r e a s e th e 4:0% e t h a n o l , 11. i f the 1 1 c o n d u c t a n c e o f s t r o n t i u m b r o m i d e (11.3 ohras~~) g r e a t e r t i i a n t h a t of water. 4) ; s t r o n t i u m curves i s th e F or example, OoOl I>i s o l u t i o n s o f s t r o n t i u m c h l o r i d e bromide ( F ig . magnesium c h l o ­ i t p,hivi 1 n ho nf\ >n +■ do e x i s t . 14 follow ­ unci s t r o n t i u m b r o m i d e 63> ( P i g * Svon th o u g h t h e g e n e r r 1 t r e n d o f t h e s e certain differences f o r 0.01 about th e 3} ; b a r i u m c h l o r i d e 65)6 ( F i g . c h l o r i d e 73% F i g . is The a f f e c t c o n d u c t a n c e may b e r i o t e d curves o f F ig u re s e ffe c t of a given chloride. 3, 4, 5 and. i n c r e a s in g l y larger- so lu tio n causes in cre asin g ly decreases in the equivalent c o n d u c t a n c e up to n certain ^oint. b e y o n d ti: I s p o i n t a d d i t i o n o f moro e t n a n o l d e c re a se in the subs tan t i a l l r t h e effect of orange 01 coiuti unroof a n e l e c t so -Lyt e i n Iona m u ( 7 6-78) that in (It conform ance with p r o b a b l y - as m i d tne A rrhenius theory the is v e l o c i t y o f the Lire i n u l v i u u a l t n e number o f io n result of increased assumes t h a t tho ionic velocity is due o n l y t o W i t h ’’ s t r o n g ” e l e c t r o l y t e s iiinivim ai A ccording to ions v a rie s tile v e l o c i t y the ihtorrjnro first at*— e-, n a t i o n o f f e by-: a n d d u e h i e . , t u e u e n d • upon. t o e fric tio n offered by f ’t o r t f o l a w ) to the and . h e n c e of r t i c l e . ail.L be d e p e n d e n t uoon t h e v i s c o s i t y md c o n s ta n t o f trie s o l v e n t , Iron the solvent the in accordance w ith \ . ,' ■■■■.. , ( u i ( w h i c h v 111 be g o v e r n e d d ielectric i an i n c r e a w i l l b e d e p e n d e n t u >on t l f a i i r n i u me a ; cl nit. s s o f t h e Also, point ■wssssji.n.oc bo r e ma mi urceiissuyou ■■■,. a ch e ionic v elo city w ill particle i s u.ei >enu e n t os . m e n t i o n e d at, b u l r t n e 1., e b y e-eim c.a e i — w n a- a y e .a a,. , s :' . traction- of chlorine- th o o r y o f i . r h i o n i u s c o n s t o u t ami i n or e ; me. c o n d u c t a n c e i n t h e mr.iber o f i o n s , . ) i.et us l i m i t sum m on c a s e o f ‘" n e s i h e Le c t r o l y t m , n u m b e r o.* i o n s eoniposition i s strontium 'the v e l o c i t y w i l l u n d o u b t e d l y be l u c r e a s e a s o t h e ionisation in mme f o r ea c h e l s e t r o l y t e . u. ;on t h e : i u : n e r o f in the the c a u s e s ttn i n c r e a s i n g l y m o r e r a p i d discus;.-ion to T n e c o u n i i c t i v iiiv ions- inflection, confuct.-uice. oinee th e general our p re sent of aoove cat s t e r n e r t s . i t follow s t h a t changes the v i s c o s i t y or d i e l e c t r i c solvent or if the ’' s i n e " o f the if a s o cone constant of a iuaivioual ion is altered, the i o n i c v c l o c i t y , r.nd h e n c e t h e e< u i v s l e n t ductcUi cG, o f t h e e l e c t r o l y t e v / i i i b e a r t u r e a , . hue u e u i ti.u 11 o f e. s e c o n d so-Lveiit a I.f i -jr o o ; ijt j simultaneour> change I n each o f 'these f a c t o r s . Obviously* CdUoG s Thus, c o n d u c t a n c e i n m i x e d n o t e e n t e b e c o me s &. more o r l e s s f u n c t i o n o f trie r e l a t i v e c o mp o n e n t s * viscosity) complex T h e d e p e u o e n c e o f f l u i d i t y ( r e c i p roc e l o f arm d i e l e c t r i c be s e e n f r o m t h i s c o n s t a n t on i r e composition of - ■, . etuauoi . Is cun f i g u r e t h a t t h e i n f l u e n c e of v i s c o s i t y c h a n g e i s l u m n t l v e i y t h e u a ■a i m p o r t a n t i m l v i e u c e up lover, the c o n c e n t r a t i o n s o f t h e tv/o s o l v e n t o t h ‘.ooj x.-" a a . r n mr xi mr e s ' l o r . 1■s u i u S'u Jui f i g u r e a c u n t v: a ; oou- x s i/no u i u i o c t r i c c o n s t a n t v e s h o u l d e ; r >e c t ( o f ) go becomes the in flu en ce of d i e l e c t r i c c o n s t a n t on t h e c o n d u c t a n c e c u r v e t o be mor e p r o u o u n c e u t u r n before. Tni s i s i l l u s t r a t e d ( 7’I r , 15) bv comoc r.i ng t h e c u r v e v / i t h t h e b -• c u r v e * ( K e e p i n g .in ,\ - mi Aid t h a t t h e v i s ­ c o s i t y e f f e c t I s \ v o ru ing mow. i n o p p o s i t i o n t o t h e d i o l e o t r i e constant. ) It cm tout tne extent the also bo s e e n or r e f e r e n c e ‘to F i g u r e 5 t o -which a o n r i i / e i n comp o s i t ! on i n f l u e n c e s c o n d u c t a n c e c u rv e I s d e p e n d e n t upon trie c o n c e n t r a t i o n the electrolyte. T n e :-:i, s r p n e e c o f t h e i n f l o c t i o n o f t i e c u r v e s a nd t h e p o s i t i o n of t h e i n f l e c t i o n pronounced in th e d i l u t e fo r strontium -joint a r e most s o l u t i o n a a nd g r n t i u a i l / b e c o me s bus.; proaoiuiced v.ith i n c r e a s i n g c o n c e n t r a t i o n . . points, of chlorine, occur at f o l lo w in g p e r c e n t a g e s o f wtnsnol in the The i n f l e c t i o n c-.plj r o r r i i a a t e l y t n e solvent: 0 ,, J 2 5 b a t e 0 > ; ' G , 0 1 L n t 78>1; 0 . 00b 14 a t 7 f h ; 0 . 0 0 7 5 li a t 6rj->-; 0 . 0 0 1 ip a t 65y ana z e r o c o n e e n t r a t i o n a t H i e f a c t t h a t y.-altien* r. ( 0 9 ) to apply in th ese s o lu tio n s c a r v e o f F I r u r e 15, rule o lio ,. ( Ayn = c o n s t a n t ) fails i s i l l u s t r a t e d by t h e a 0 n - Th e f a c t t n s t this c a b l e t o t h e s e s y s t e m s m i d s t be a t l e a s t rule is not u p p ii- p a r t i •■illy e x p l a i n e d by t h e f o l l o w i n ' " n c o p o s n l o r t h e i v r x t o r o f tux.; r e p o r t . us resume i t a t th o a t r o n t i ura nub ( o r ) strontium chloriue lav e the slid w i t h e t h a n o l i f cnIori.be io n s of c a p a c i t y of s o l v a t i n g v.-itii m a t e r i>r e s e n t i n e i t h e r of t h e b e p u r e s o l v e n t s , and w i t h u o t ii ' ' / a t o r and e t h a n o l i f these solvents. Let . a ct u s a . i s o /resent a sumo t n o t in mixture of thc o o u p o sitio n o f t l i e ’’s o l v a t e d l a y e r ” i s a f u n c t i o n uj1‘ t h e c o m p o s i t i o n o f t h e solvent v from t n i s proposal,. we. c o u l d have,, f o r e x a m p l e , a s t r o n t i u m i o n s o l v a t e d ui t h " r ” m o l e c u l e s o f r a t e r and " y " molecu!eu o f e th a n o l - Lot, u s f u r t h e r a s s ume t n s t t h e v a r i e s .oi . x .ana y o r e \ on x a o uy; xi'ciye) i-m.u . u e m j t u u r i i y i i i t B y e r s imu e a c h may v a r y u s a fun nut on o f t a x c o m p o s i i i on of t h e s o l v e n t .. from t h i s i c e u , s a o ostia In ie u h a v e a c o n t i n u o u s l y v s r y i u y s o L v n I a i a . y c r , ; t ri ot i s c a r r i e d , s i t s : t h e i o n and t h e r e b y t h e v e x e d to oi' b e a t l o r w o n i a oe i n f l u e n c e d i n t c - CGrauuee w i t h t h e a a t sure of t h e s o l v a t e d we m l y u t assume that this Furthermore, s u i r t i c u l s r t y p e o r s o l v a t i o n c«ould be c ompa r ed ( i n a v e r y 11ml t e d s e n s e ) s o r p t i o n ” f r o m ci mlived s o l v e n t . to ”p r e f e r e n t i a l un- ( m s e r i e s os' e i a u u i - . O u t s t o e s t a b l i s n t h e compos L t i o n o f t h i s o f c o n s i d e rs ole soi Laye r . n u i v s b o n l a y e r woul d ue -G . Loriue c o u l d be c o m p a r e a t o t r i e n a r t i a l nio.La 1 vol ume o f ethanol in t h e co r r e o o o i i u 1 no e t h on o i --a a t o r m i m v t r o , c ovt elri Lau no s t r o n t i u m , J.f z\\ a e t u m i o i e u a t l a i . mo J.al vol ume cnlorrm . io ui a .towo r j_u L:i e el e o t x ' o l y t i.o r o i U u i o u i. ul'or.i;.; L'.i.oa Uot’ t h e ;ouj . ci cee;i on '.corn nr: t h e >aive e vt . i u u t i ojl o f t h e dorr:-!; o f s o l v e t i o n o f JOiri’iO Ox Gj. Olifc! . j. o r name m a n n e r , t ,a c a r r e a ;J ■;eoi n. in an at irrnwr n o , t a c t . iiii, I t h . o a;.a u i n. a o ,roee ■.f e f t h e w a t e r niiprnt be d e t e r m i n e d .} ( c) Cn an pe i n t r i e c o n c e n t r a t i on of t h e o f m ' t r 1 h. e. >■I1a ■■a ■root o f t h e la: iui)1 t ;, OU a ,0 T e (: a ; , 6 1 0 C “ t ‘-.Ji L . 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( -) re i l l u l u , , t f . j i.xTjieiiinr, \ u; i.* (xim ) lob 0 li.'Yb■. .: c (7i . lu ro : (11) , u. :X ( 1 6 9 6 }. ;■!;(: ben. j. iu i .n , ,. , jiii. • u.'OO i v i~o i >.iiouj 1:01.0,,]% J - 2 1 oi ( i u±u o . ( 1 8 ; T i j bib IE. Lb b. (lb] !;Oth I '! A\ J on or X 88 ; ::i: o o r r u u . . -J o;. liu'. „:.o> J o e e , ( 17) one;-.,- i: o ny (18) donor ( 1006) omim. 10id (1007). -'O* ‘zC f —6 6 - i » 0. r. £0 ) CiiuKi; j Ii (loo?); 90 / / f zC‘7 ,57, ,4.0, 5 8.0 ( 1 9 U6 ) : l i d V e o b e1,7 y ,3 ^ v.' t* -1- = ’ y j :!Lr 0 i ;,4 ‘1*> J , jj 07, 0. J o n u s , j 1. Ibid- Miu ; lei';.: . " t o r , 1 0 Cbeiii. , 6 1 , Gli (1906); 405 GO. i 1908). (81) dreic :r 5 4 4 0 OH' <'110. JO! .. i ui (i... 40 . i ol C . r 3 . piivc.ik. \ 40/ ■ (1 9 lj * Ujier. 1 , , 81, orf ( J. 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COei.u !’, oo. s 40, Hii'.ijt.rof;, 'i', ( a-ol.4.} Kiolutrcic , T, u, , I b i d « , 20 , 1 4 4 ( 1 9 0 u ) «, ( 67) 1-0 t oi MK-t i ari u l C r i t i e o l I ' c b l a f . ( 63) t5:-rk-jr, j i . 0* , 8 - Ain» Ciiein , ;: o c . s J_5, 118 (1988), 1566, 8017 f\ "t 9 551 WA • ( 09) I m i o n „ 8, e n d a;) 11 1 m y e r , 18 . 4,* (70; 8: - t i l l ; :1c,; , d , k „ , (71) d o II0 8 . 18 ruiu 1 Omm, I u l d , 3 5_53 i l l -mm, idj.T'-iIoiiov;, 11♦ £0 , 3.957 (1951)„ (1511), 3 J „ /.!!!-. C UvsIIlo^ OC. 5, _0b? 1.7. ' 0 I 1 9 55} . V i . 1 o i a . t b e , 74.81 ( 7 8) Vnmrmuru, (78) I. on cl o i l , J 8 1 8 1 ,8 . (71) i k e r l o f f , 0 , s JO j ;.ui,. Olicm. (75) I n t e r ; ir t l o r i a l C r j U i o u r . n r O l e v p 5 , 58 (76) / . i T i i O i i i i U ' ,7.. 851 (7 7) r i m i e r , 78 , ,.ru;. P . , y s i 5 ;t 8 2 ; 168 (18737), (■78) OoOJ r a u s ' c l i , 10,' ,' Varfn I b h - a n a l , 88, v;,v/:vi5j K e i e h f d n.Mt f.at , 8. 1180, m+6 0 loc. , Ciioin. , 519 (loi6)„ 1.. ( 15X6) ; 51. 89, 1185 7 (1917) ( 19 88) » (1980), (Id a?) . mm - t e c h ■■ (1900), / 01 (.>i O18\ * { (80) ;Vi.lli5;uo3 J , 517 8, r . , a jOriOv.nii i-.; * o n , . I , , 1'c l 5 on 1 : o n , 78. , 5>v. fviodov i l 9 ftyo l e v y (85) Onm.yer, L P-vysik, (68) Onci.yer, L, (81) Fuor.n, iOrvm j3 ( 1 5 89),. (51) cbo;* Cii enu „ cu t; l u o s r . , (5, R, 2 7 , 5c 8 wl, s 1 , 5, 115 (1 5 5 1 ) , (1986); pays. V i.AJ C.57 j ,8. .vi. , P h y s i n . I . , 55, 59 ( 1 9 5 1 .) „ 58 5 7 7 ( 1 5 8 7 ) Ch e m. , 5 b „ - 70 - r , y J" - \^ J f w f-. \ u. u . , ( o7) 071'.; T , 0. Chom. S o o . , 5 4 , I - I I I ( 19 58) . J . .;n, C;i oi.u LOG, , _5GS 1H97 ( 1 9 SO) « U i.'U.LO , iv: i j •-!" . i’.m. Uii6M . bOO . , fcMj, d ? . r::o), inio i ■. !mj C, . _g 5 , i. iG:,, 1 0 1 9 ( 1 ‘J;5S) ::>.)7.GGo ( 190G)