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University of Southern California Dissertations and Theses
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A study of the relation between the concentration of a dye and the transmission of an image produced by dye adsorption on a suitable mordant.
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A study of the relation between the concentration of a dye and the transmission of an image produced by dye adsorption on a suitable mordant.
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A STUDY OF THE RELATION BETWEEN THE CONCENTRATION OF A DYE AND THE TRANSMISSION OF AN IMAGE PRODUCED BY DYE ADSORPTION ON A SUITABLE MORDANT A T h e s is P r e s e n t e d t o t h e F a c u l t y o f t h e G r a d u a te S c h o o l The U n i v e r s i t y o f S o u th e r n C a l i f o r n i a In. P a r t i a l F u l f i l l m e n t o f t h e R e q u ir e m e n ts f o r t h e D e g re e M a s te r o f S c ie n c e i n .C h e m i s t r y b y L . S . T rim b le J u l y 1940 UMI Number: EP41531 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI' P w o iftB tofl PablislJrtg UMI EP41531 Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 C h- i T z m This thesis, written by .......................... under the direction of hLa.. Faculty Committee, and approved by all its members, has been presented to and accepted by the Council on Graduate Study and Research in partial fulfill ment of the requirements for the degree of ( f t - MASTER OF SCIENCE o w e . ...... Secretary D ate A u g u s t ...1 9 . 4 0 .............. Dean Faculty Com m ittee Chair mi C o l l e c t i o n o f d a t a w as f a c i l i t a t e d t h e u s e o f t h e m a t e r i a l a n d e q u ip m e n t o f C i n e c o l o r M o tio n P i c t u r e L a b o r a to r y . TABLE OP CONTENTS CHAPTER PAGE I . THE PROBLEM AND DEFINITIONS OF TERMS USED . . . . 1 The p ro b le m ............................................... 1 D e f i n i t i o n s o f te r m s u s e d .......................... 2 I I . BACKGROUND OF THE A R T .......................................................... 4 P r a c t i c e i n t h e a r t ................................................... 4 T h e o r e t i c a l c o n s i d e r a t i o n s . ................................................ 5 I I I . METHODS OF STUDY ............................................................... 7 E x p e r im e n ta l t e c h n iq u e . . . . . . 7 Type o f i m a g e ............................................................. 7 The p r e p a r a t i o n o f u n if o r m s i l v e r d e n s i t i e s . 8 The p r e p a r a t i o n o f t h e d y e i m a g e .................................. 9 The t r a n s m i s s i o n o f t h e d y e i m a g e ................................... 11 T r e a tm e n t o f d a t a o b t a i n e d .......................................................... 13 R e l a t i o n f o r a s i n g l e d y e .............................. 13 R e l a t i o n f o r t h e d y e m i x t u r e ................................................15 V i s u a l i n t e n s i f i c a t i o n ......................................................... 16 IV . SUMMARY AND C O N C L U SIO N S......................................................... . 19 Sum m ary ................................................................... . . . ' 19 C o n c l u s i o n s .........................................................................................20 BIBLIOGRAPHY.................... ....................................................................................... 2 1 TABLE LIST OF TABLES FOLLOWING PAGE 1 . E v a l u a t i o n o f t h e C o n s t a n t s m a n d b a s a F u n c t io n o f S i l v e r D e n s i t y ..................................... 14 2 . E q u a t io n s r e l a t i n g t r a n s m i s s i o n , Dye C o n c en t r a t i o n , a n d S i l v e r D e n s i t y f o r T h io n i n e , A u ro m in e , a n d t h e Dye M i x t u r e ......................... 14 3 . F i n a l E q u a t io n s D e r iv e d fro m E x p e r im e n ta l D a t a ......................... 15 4 . D a ta f o r I n t e n s i f i c a t i o n C u r v e s ......................... 17 LIST OF FIGURES FIGURE FOLLOWING . PAGE 1 . T r a n s m is s io n C h a r a c t e r i s t i c s o f a S u r f a c e S i l v e r I o d i d e Im age . . . . . . . 7 2 . T y p i c a l S e n s i t o m e t r i e s t r i p P l o t t e d a s a n H u r t e r a n d D r i f f i e l d C u rv e . . . . 9 3 . - 9 . T r a n s m is s io n V e rs u s W a v e le n g th D a ta f o r T h i o n i n e .............................. 13 1 0 .- 1 6 . T r a n s m is s io n V e rs u s W a v e le n g th D a ta f o r A urom ine- ......................................................... 13 1 7 .- 2 3 . T r a n s m is s io n V e rs u s W a v e le n g th D a ta f o r t h e M ix tu r e o f T h io n in e a n d A u ro m in e . 13 2 4 .- 3 7 . Dye C o n c e n t r a t i o n p l o t t e d a s a F u n c t io n o f t h e T r a n s m is s io n o f t h e R e s u l t i n g Im ag e ........................................................ 13 3 8 .- 4 0 . S i l v e r D e n s i t y P l o t t e d a s a F u n c t io n o f t h e C o n s t a n t s m a n d b ........................... 13 4 1 . - 4 3 . C o n s t a n t s o f t h e C o n c e n t r a t i o n , T ra n s m is s i o n , a n d S i l v e r D e n s i t y R e l a t i o n P l o t t e d a s a f u n c t i o n o f w a v e le n g th . . . 14 4 4 . - 4 5 . T r a n s m is s io n v e r s u s W a v e le n g th a s F o u n d fro m t h e Dye M ix tu re a n d a s C a l c u l a t e d fro m I n d i v i d u a l Dye D a t a ...................... 15 4 6 . A v e ra g e v i s i b i l i t y C u rv e f o r E q u a l E n e rg y D i s t r i b u t i o n .............................................................. 17 FIGURE FOLLOWING - PAGE 4 7 . - 5 3 . L u m in o s ity C u rv e s fro m E x p e r im e n ta l D a ta . 17 5 4 . C u rv e s S h o w in g t h e R a te - o f C hange o f V i s u a l D e n s i t y w ith Dye C o n c e n t r a t i o n . . 18 5 5 . C u rv e s S h o w in g t h e R a te o f C hange o f V i s u a l D e n s i t y w i t h S i l v e r D e n s i t y . . . 18 5 6 . V i s u a l I n t e n s i f i c a t i o n o f t h e Dye Im a g e s a s a F u n c t io n o f Dye C o n c e n t r a t i o n a n d S i l v e r D e n s i t y . ........................................................... 18 CHAPTER I THE PROBLEM AND DEFINITION'S OF TERMS USED The p r o b le m . C o lo r p h o t o g r a p h i c r e p r o d u c t i o n i s . b a s e d u p o n t h e a c c e p t e d p r i n c i p l e t h a t a n y c o l o r i n t h e v i s i b l e s p e c tr u m c a n b e r e p r o d u c e d b y s u i t a b l e c o m b in a tio n o f t h r e e p r i m a r y c o l o r s . To o b t a i n t h e s e so c a l l e d p r im a r i e s , c o l o r e d p ig m e n ts o r d y e s a r e u s e d . In a sm u c h a s t h e r e a r e a g r e a t n u m b er o f d y e s a v a i l a b l e , e a c h h a v in g som ew hat d i f f e r e n t s p e c t r a l c h a r a c t e r i s t i c s , t h e p r i m a r y c o l o r s a r e o f t e n m ade up o f a s i n g l e d y e , o r a m ix tu r e o f s e v e r a l d y e s . A s lo n g a s no c h e m ic a l r e a c t i o n o r p h y s i c a l a s s o c i a t i o n o c c u r s , t h e t r a n s m i s s i o n c h a r a c t e r i s t i c s o f a. s i n g l e d y e i n s o l u t i o n , o r a m ix tu r e o f d y e s , a r e e x p r e s s e d i n te r m s o f t h e w e l l known L a m b e rt- B e e r la w o f a b s o rp tio n ,-* - w h ic h s t a t e s I = - k c 1 w h e re k « a b s o r p t i o n c o e f f i c i e n t I„ c = c o n c e n t r a t i o n o f m a t e r i a l 1 * l e n g t h o f l i q u i d t r a v e r s e d I = t r a n s m i t t e d e n e r g y 1^ = i n c i d e n t e n e r g y The u s e o f d y e s o r d y e m i x t u r e s i n c o l o r p h o t o g r a p h i c p r e p r o d u c t i o n i s o l d i n t h e a r t . The s t u d y a n d a n a l y s i s o f ^ T he S v e d b e rg , C o l l o i d C h e m is tr y . 1 9 2 8 , p . 2 0 5 ; A r t h u r C. H a rd y a n d F r e d H. P e r r i n , P r i n c i p l e s o f O p t i c s . 1 9 3 2 , C h. 1 4 ; F . H. G etm an a n d F . D a n i e l s , O u t l i n e o f T h e o r e t i c a l C h e m is tr y . 1 9 3 1 , p . 5 4 3 . 2 E . J . W a ll, The H i s t o r y o f T h re e C o lo r P h o to g r a p h y . 1 9 2 5 , p . 3 7 8 . d y e m i x t u r e s b y m eans o f t h e s p e c t r o p h o t o m e t e r i s n o t new *^ T he s t u d y , h o w e v e r, o f t h e s p e c t r a l c h a r a c t e r i s t i c s o f t h e r e s u l t i n g d y e im a g e s o b t a i n e d w hen a s i n g l e o r m u l t i p l e d y e s o l u t i o n i s a llo w e d t o a d s o r b u p o n a s u i t a b l e s u b s ta n c e t o p r o d u c e a c o l o r t r a n s p a r e n c y o r p r im a r y i s n o t r e c o r d e d i n t h e l i t e r a t u r e . I f a s u b s t a n c e w e re a v a i l a b l e h a v in g no c o l o r c h a r a c t e r i s t i c s , a n d h a v in g t h e a b i l i t y t o a d s o r b t h e d y e i n d i r e c t p r o p o r t i o n t o t h e q u a n t i t y o f m a t e r i a l p r e s e n t , t h e n a la w o f t h e L a m b e r t-B e e r fo rm m ig h t a p p ly . I t i s t h e p u r p o s e o f t h i s i n v e s t i g a t i o n t o p r e p a r e s u c h a s u b s t a n c e , a n d s t u d y t h e r e s u l t i n g im a g e c h a r a c t e r i s t i c s f o r s i n g l e d y e s a n d f o r d y e m i x t u r e s . D e f i n i t i o n s o f t e r m s u s e d . ( 1 ) The s u b s ta n c e o r m a t e r i a l s u i t a b l e f o r d y e a d s o r p t i o n i s te r m e d a m o r d a n t. I t i s o f s u c h a n e l e c t r o s t a t i c n a t u r e t h a t c e r t a i n d y e s i n s o l u t i o n h a v e t h e a b i l i t y t o becom e i n t i m a t e l y a t t a c h e d o r a d s o r b e d t o t h e m a t e r i a l w i t h o u t e x h i b i t i n g a n y a f f i n i t y f o r t h e s u r r o u n d i n g m edium i n w h ic h t h e m o rd a n t i s s u s p e n d e d . ^ A s h le y , S p e c tr o p h o tom e t r i e M eth o d s i n M odem A n a l y t i c a l C h e m is tr y ; J o u r n a l o f I n d u s t r i a l a n d E n g in e e r i n g C h e m is tr y , A n a l y t i c a l E d i t i o n , F e b r u a r y 1 5 , 1 9 3 9 . (2) Opacity = incident energy 4- transmitted energy = Io . I ( 3 ) T r a n s p a r e n c y = X Io ( 4 ) D e n s i t y = l o g 1Q ( O p a c ity ) = l o g 10{° = l o g 1 0 ^ ( 5 ) A n e g a t i v e s e p a r a t i o n i s a p h o n o g r a p h ic r e c o r d o f . a l l p o r t i o n s o f a s u b j e c t r e f l e c t i n g e n e r g y b e tw e e n g i v e n w a v e le n g th l i m i t s . ( 6 ) A p o s i t i v e im a g e i s t h e r e s u l t i n g p h o t o g r a p h i c r e c o r d m ade b y e x p o s u r e a n d d e v e lo p m e n t o f a p r i n t fro m a n e g a t i v e s e p a r a t i o n . S u ch a p o s i t i v e im a g e , r e g a r d l e s s o f i t s c o n t r a s t , w i l l h a v e a d e n s i t y r a n g e o f fro m z e r o t o a b o u t 0 .8 0 . ( 7 ) C o n t r a s t . i s a m e a s u re o f t h e r a t e o f c h a n g e o f d e n s i t y w i t h e x p o s u r e . CHAPTER IX BACKGROUND OP THE ART P r a c t i c e i n t h e a r t . E x p e r ie n c e i n c o l o r p h o to g r a p h i c r e p r o d u c t i o n f o r t h e m o tio n p i c t u r e s c r e e n h a s show n t h a t a d y e im a g e m u s t b e s h a r p , p e r f e c t l y t r a n s p a r e n t , a n d g r a i n l e s s . T h is r e q u i r e s a m o rd a n t h a v in g no g r a i n s t r u c t u r e , a h i g h t r a n s p a r e n c y , a n d a g r e a t a f f i n i t y f o r t h e d y e o r d y e s u s e d . S e v e r a l s u c h m o r d a n ts a r e a v a i l a b l e ; a n d t h e p r o c e d u r e i n s e c u r i n g a d y e im a g e i s a s f o l l o w s . A p o s i t i v e im a g e , i n s i l v e r , i s p r o d u c e d b y e x p o s u r e o f t h e p o s i t i v e th r o u g h a s u i t a b l e n e g a t i v e s e p a r a t i o n , r e d u c t i o n o f t h e e x p o s e d s i l v e r b ro m id e b y a s t a n d a r d d e v e l o p in g o r r e d u c i n g s o l u t i o n , w a s h in g o u t t h e d e v e l o p in g s o l u t i o n a n d t h e n r e m o v in g t h e u n e x p o s e d s i l v e r h a l i d e i n a s o l u t i o n o f so d iu m t h i o s u l f a t e . A f t e r w a s h in g t h e r e s i d u a l H h y p o n fro m t h e p r i n t , t h e r e m a in in g s i l v e r im a g e r e p r e s e n t s t h e a r e a t o be c o l o r e d . T h is p o s i t i v e s i l v e r im a g e i s c o n v e r t e d b y s u i t a b l e c h e m ic a l t r e a t m e n t t o a m o rd a n t h a v in g a n e l e c t r o s t a t i c c h a r g e o f s u c h a m a g n itu d e a s t o a t t r a c t a n d h o l d , f i r m l y c e r t a i n t y p e s o f d y e s . The c o n v e r s i o n i s g e n e r a l l y a s t r a i g h t f o r w a r d c h e m ic a l r e a c t i o n i n v o l v i n g t h e o x i d a t i o n o f t h e s i l v e r im a g e w i t h t h e r e s u l t i n g c o n v e r s i o n , th r o u g h m a s s a c t i o n a n d s o l u b i l i t y p r o d u c t p r i n c i p l e s , o f t h e s i l v e r s a l t i n t o t h e d e s i r e d s u b s t a n c e . N o t o n l y i s t h e s u b s t a n c e i m p o r t a n t , b u t a l s o t h e e x a c t fo rm i n t h e g e l a t i n e l a y e r d e te r m i n e s t h e m o r d a n tin g a b i l i t y . S e v e r a l s u c h m or d a n t s a r e c o p p e r f e r r o c y a n i d e , v a n a d iu m f e r r o c y a n i d e a n d s i l v e r i o d i d e . T he m o rd a n t a n d g e l a t i n e a r e w e l l w a s h e d , t h e n im m e rse d i n t h e d y e s o l u t i o n f o r a p e r i o d -o f tim e lo n g e n o u g h t o i n s u r e th o r o u g h s a t u r a t i o n o f t h e m o r d a n t. T h is - i s f o l lo w e d b y a w ash t o rem o v e t h e e x c e s s d y e w h ic h d o e s n o t a d h e r e t o t h e g e l a t i n e o r b a s e . T he r e s u l t i s a c l e a r , s h a r p im a g e , i n c o l o r , o f t h e o r i g i n a l s i l v e r r e c o r d . Dye a d s o r p t i o n b y t h e m o rd a n t i s a n e l e c t r o s t a t i c p h e n o m e n o n . The g e l a t i n e c o a t i n g , i n w h ic h a l l p h o to g r a p h i c im a g e s a r e s u s p e n d e d , h a s , i n g e n e r a l , a n e l e c t r o s t a t i c a l l y p o s i t i v e c h a r g e . I f t h e m o r d a n t i s t o b e c o l o r e d a n d n o t t h e g e l a t i n e , t h e a d s o r b i n g s u b s ta n c e m u s t h a v e a n e g a t i v e c h a r g e a n d t h e d y e s u s e d a p o s i t i v e c h a r g e . T h is l i m i t s t h e a v a i l a b l e d y e s t o t h e so c a l l e d b a s i c t y p e i n w h ic h t h e c o l o r e d i o n i n s o l u t i o n c a r r i e s a p o s i t i v e c h a r g e . The r a n g e o f u s a b l e d y e s , t h e n , i s l i m i t e d b y , f i r s t , t h e g e l a t i n e c h a r g e , f o r a s t h e d y e b e co m es l e s s b a s i c a n d m ore a c i d i c , t h a t i s t h e c o l o r e d i o n b e co m es m ore n e g a t i v e , t h e t e n d e n c y t o s t a i n i n c r e a s e s ; a n d s e c o n d , b y t h e e x t e n t o f . t h e n e g a t i v e c h a r g e u p o n t h e m o rd a n t i n d e t e r m i n i n g how t i g h t l y t h e d y e m ay b e h e l d . T h e o r e t i c a l c o n s i d e r a t i o n s . I f d i f f e r e n t s i l v e r d e n s i t i e s a r e c o n v e r t e d t o t h e m o rd a n t i n a m an n e r g i v i n g t h e sam e p a r t i c l e s i z e t h r o u g h o u t , a n d i f b u t a s m a ll f r a c t i o n o f d y e i s w a sh e d aw ay fro m t h e m o rd a n t i n c l e a r i n g t h e g e l a t i n e s t a i n , t h e n fro m t h e o r e t i c a l c o n s i d e r a t i o n s t h e L a m b e rt B e e r la w w o u ld a p p ly t o t h e r e s u l t i n g im a g e w h e re c ■ c o n c e n t r a t i o n o f d y e i n s o l u t i o n 1 = s i l v e r d e n s i t y w h ic h i s t r a n s f e r r e d c h e m i c a l l y i n a l i n e a r m a n n e r t o t h e m o r d a n t. I t w o u ld b e e x p e c te d * t h e n , t h a t t h e r a t e o f d e c r e a s e o f i n i t i a l l i g h t i n t e n s i t y w i t h m o r d a n t t h i c k n e s s w o u ld b e p r o p o r t i o n a l t o t h e i n t e n s i t y o f l i g h t . S e v e r a l f a c t o r s a p p e a r , fro m e x p e r i e n c e , t o i n f l u e n c e t h i s t h e o r e t i c a l r e a s o n i n g . F i r s t , d i a l y s i s i n d i c a t e s t h a t t h e d y e s o l u t i o n i s p a r t i a l l y c o l l o i d a l . T h is c o l l o i d a l c o n d i t i o n c h a n g e s w i t h m e th o d s o f m ix in g , a c i d c o n c e n t r a t i o n , tim e o f s t a n d i n g , t e m p e r a t u r e a n d t y p e o f d y e . S e c o n d t h e q u a l i t y o f m o rd a n t v a r i e s a s a f u n c t i o n o f t e m p e r a t u r e , r a t e o f f o r m a t i o n , w a s h in g t im e , e n d d e p th o f im a g e i n t h e g e l a t i n e l a y e r . T h i r d , t h e t y p e , a g e a n d c o n d i t i o n o f t h e g e l a t i n e h a s a m a rk e d e f f e c t u p o n t h e k i n d a n d q u a l i t y o f im a g e o b t a i n e d . CHAPTER III METHODS OP STUDY I . EXPERIMENTAL TECHNIQUE Type o f im a g e . To e l i m i n a t e a s m any tr o u b le s o m e f a c t o r s a s p o s s i b l e t h e s i l v e r i o d i d e m o rd a n t w as c h o s e n f o r s t u d y . I t i s p r a c t i c a l l y c o l o r l e s s ( s e e F i g u r e 1 ) , h ay i n g , b u t a s l i g h t p e a k i n t h e y e llo w . I t i s p r e p a r e d b y im m e r s in g t h e s i l v e r im a g e i n a s o l u t i o n o f i o d i n e a n d i o d i d e s u c h t h a t a s t h e s i l v e r i s o x i d i z e d b y t h e i o d i n e t h e r e i s s u f f i c i e n t i o d i d e p r e s e n t so t h a t a c o m p le x s i l v e r i o d i d e i s fo rm e d . I t i s p r o b a b l y a c o m b in a tio n o f g e l a t i n e , a c i d , a n d p o t a s s i u m s i l v e r i o d i d e . A f t e r t h i s b l e a c h i n g a c t i o n , t h e i o d i n e i s rem o v e d i n a b i - s u l f i t e s o l u t i o n a n d t h e m or d a n t i s w a sh e d f o r a s h o r t p e r i o d o f t i m e . The im a g e a t t h i s p o i n t i s v e r y t r a n s p a r e n t , b u t p r o l o n g e d w a s h in g r e s u l t s i n t h e c o m p le x d i s s o c i a t i o n t o y e ll o w , c o a r s e g r a i n e d o p a q u e s i l v e r i o d i d e . I t w as fo u n d t h a t a s u r f a c e s i l v e r im a g e c o u ld n o t b e t r a n s f o r m e d i n t o a s a t i s f a c t o r i l y t r a n s p a r e n t i o d i d e im a g e . A s a r e s u l t , c o r r e c t i o n s m u s t b e a p p l i e d t o e a c h d y e d e n s i t y t o e l i m i n a t e t h e m o rd a n t c h a r a c t e r i s t i c s show n i n F i g u r e 1 . H o w ev er, b y p r o d u c i n g t h e s i l v e r im a g e a d j a c e n t t o t h e b a s e , t h a t i s b y e x p o s in g t h r o u g h t h e c e l l u l o i d s u p p o r t r a t h e r t h a n o n t h e e m u ls io n s u r f a c e , t h e b l e a c h i n g a c t i o n p r o d u c e s a p e r f e c t l y t r a n s - 54 I t .tn r . 55 Tiir. rrifts s s r i w f w e e jd r r r : 5 - L i:.:} ?-5 L _ i ----- ni p a r e n t im ag e h a v in g no s p e c t r a l c h a r a c t e r i s t i c s i n t h e d e n s i t y r a n g e d e s i r e d . P r o b a b l y t h e g e l a t i n e l a y e r i n ' f r o n t o f t h e im a g e p r e v e n t s r a p i d d i s s o c i a t i o n o f t h e p o t a s s i u m s i l v e r i o d i d e c o m p le x . W ith t h i s ty p e o f im a g e , t h e n , no c o r r e c t i o n n e e d b e m ade f o r s i l v e r i o d i d e t r a n s m i s s i o n , a n d t h e r e s u l t i n g d y e im a g e s m ay b e s t u d i e d a s s u c h . The p r e p a r a t i o n o f u n if o r m s i l v e r d e n s i t i e s . An E a s tm a n t y p e 2 b S e n s i t o m e t e r c o n s i s t s o f a s t a n d a r d l i g h t s o u r c e , o p e r a t e d a t a p r e d e t e r m in e d a m p e ra g e a n d v o l t a g e , p l a c e d a t a f i x e d d i s t a n c e fro m t h e f i l m p l a n e . 4 T he l i g h t p a t h i s i n t e r r u p t e d b y a r o t a t i n g drum w h ic h h a s i t s c irc u m f e r e n c e c u t i n s u c h a m a n n e r t h a t tw e n ty - o n e d i f f e r e n t tim e s c a l e e x p o s u r e s a r e g i v e n t o t h e f i l m b y a s i n g l e drum r o t a t i o n . The r e s u l t i s t h a t a s t r i p o f f i l m e i g h t a n d o n e h a l f / i n c h e s lo n g i s g i v e n tw e n ty - o n e e x p o s u r e s , e a c h d i f f e r i n g fro m t h e p r e c e e d i n g b y t h e f a c t o r s q u a r e r o o t o f tw o . A b o u t t h i r t y s u c h e x p o s u r e s w e re m ade th r o u g h t h e b a s e o f p o s i t i v e m o tio n p i c t u r e f i l m . The t h i r t y f o o t l e n g t h o f f i l m w as t h e n d e v e lo p e d i n a c o n t i n o u s t y p e m a c h in e , w a s h e d , f i x e d , w a sh e d a n d d r i e d . The d i f f u s e d e n s i t y o f e a c h s t e p o n e a c h s t r i p w as 4 C . " b . I f e b l e t t e , P h o to g r a p h y , I t s p r i n c i p l e s a n d P r a c t i c e . S e c o n d E d i t i o n , , p . 2 1 1 c h e c k e d o n a C a p s t a f f d e n s i t o m e t e r5 a n d a n y sh o w in g s l i g h t v a r i a t i o n s w e re d i s c a r d e d . A s a m p le o f t h e t y p e o f s t r i p o b t a i n e d i s show n i n F i g u r e 2 . The d i f f u s e d e n s i t y , D * lo g lO ( o p a c i t y ) , i s p l o t t e d a g a i n s t t h e log-^Q e :x p o su re v a l u e s g i v e n t h e f i l m s t r i p . T h is i s a s t a n d a r d H u r t e r a n d D r i f f i e l d c u r v e . 5 The - p r e p a r a t i o n o f t h e d y e im a g e . E a c h s t r i p o f f i l m w as t r e a t e d a s f o l l o w s : ( a ) W ash - - - - - - - - - - - - - 5 m in u te s ( b ) B le a c h - - - - - - - - - - - - 5 m in u te s g ra m s K I - - - - - - - 5 0 .0 g ra m s A lp (S04 )q *18Ho0 - 1 0 .0 g ra m s CH3CO0H - - - - - 5 .0 m l CHgCOpNa - - - - - 5 .0 g ra m s 'S o l u t i o n - - - - - 1 .0 l i t e r ( c ) C l e a r - - - - - - - - - - - - 0 .5 m in u te s NaH S0 3 - - - - 1 0 . 0 g ra m s S o l u t i o n - - - - - 1 .0 l i t e r ( a ) W ash - - - - - - - - - - - - 0 . 5 m in u te s ( e ) Dye - - - - - - - - - - - - 5 m in u te s ( f ) W ash - - - - - - - - - - - - 1 5 m in u te s ( g ) D ry - - - - - - - - - - - - 20 m in u te s 5 E a stm a n K odak C om pany, M o tio n P i c t u r e L a b o r a t o r y P r a c t i c e . 5 C . B . K e b l e t t e , P h o to g r a p h y . I t s P r i n c i p l e s a n d P r a c t i c e . S e c o n d E d i t i o n , p . 2 1 1 . .. V CM: o il 7 IRE 10 U n ifo rm f l o w , a g i t a t i o n a n d t e m p e r a t u r e (6 5 * P ) w e re m a in t a i n e d . The d y e s o l u t i o n s w e re m ade up i n c o n c e n t r a t e d f o rm , im m e d ia te ly d i l u t e d t o t h e d e s i r e d s t r e n g t h s a n d t h e s t r i p s d y e d . Two d y e s w e re u s e d , a u ro m in e 0 , a n d t h i o n i n e b l u e . T h ey w e re c h o s e n fro m t h e s t a n d p o i n t o f f o r m in g _ s t r o n g im a g e s w i t h b u t s l i g h t s t a i n , a n d b e c a u s e t h e i r s e p a r a t e a n d c o m b in e d t r a n s m i s s i o n s c o v e r t h e v i s i b l e s p e c tr u m . h3cm A r r H > H N /y S y 'V M x w A u ro m in e O T h io n in e B lu e The d y e c o n c e n t r a t i o n i s g i v e n below. ( 1 ) S t a n d a r d S o l u t i o n s ( a ) A c id CHoCOoH 10 m l S o l u t i o n - - - 1 .0 l i t e r (b) Dye CHoOH----------------------3 3 m l CH3 CO2H -------------- 10 m l Dye - - - - - - 5 g ra m s . S o l u t i o n - - - - 1 . 0 l i t e r ( 2 ) M eth o d o f d i l u t i o n D e s i r e d Dye C o n e .( g / 1 ) m l o f s o l u t i o n s r e q u i r e d T h io m in e A u ro m in e T h io m in e A u ro m in e A c id S o In ( a ) 4 . 0 0 2 0 0 m m 50 ( b ) 2 . 0 0 - 1 0 0 — 150 ( c ) i . 0 0 50 - 2 0 0 ( d ) 0 .5 0 25 — 225 ( e ) 0 .2 5 0 1 2 .5 - 2 3 7 .5 ( 2 ) M ethod o f d i l u t i o n ( c o n t i n u e d ) D e s i r e d Dye C o n e .( g / 1 ) m l o f s o l u t i o n s r e q u i r e d T h io n in e A u ro m in e T h io n in e A u ro m in e A c id S o ln ( f ) 0 . 0 4 . 0 — 2 0 0 50 ( g ) 0 . 0 2 . 0 - 1 0 0 150 ( h ) 0 . 0 1 . 0 - 50 2 0 0 ( i ) 0 . 0 0 .5 — 25 2 2 5 C j) 0 . 0 0 .2 5 - 1 2 .5 2 3 7 .5 0 0 4 . 0 4 . 0 2 0 0 0 . 4 g 50 ( 1 ) 2 . 0 2 . 0 1 0 0 1 0 0 50 (m) 1 . 0 - 1 . 0 50 50 150 ( n ) 0 . 5 0 .5 25 25 2 0 0 Co) 0 .2 5 0 .2 5 1 2 .5 1 2 .5 2 25 The t r a n s m i s s i o n o f t h e d y e im a g e s . The a v e r a g e p i c t u r e r a n g e e x p r e s s e d a s s i l v e r d e n s i t y o f a c o l o r s e p a r a t i o n p o s i t i v e i s fro m z e r o t o 0 .8 0 . The d y e im a g e s w e re o f s a t i s f a c t o r y t r a n s p a r e n c y t h r o u g h o u t t h i s r a n g e . S e v e n d e n s i t i e s w e re c h o s e n f o r s t u d y . The t r a n s m i s s i o n a t e a c h w a v e le n g th o f s e v e n d e n s i t i e s on f i f t e e n d i f f e r e n t f i l m s t r i p s w as d e t e r m in e d b y m ean s o f ' t h e H a s s l e r s p e c t r o g r a p h . ? A r a n g e o f fro m 4 2 5 t o 6 7 5 mu w as s t u d i e d s i n c e t h i s i s t h e m a in s e c t i o n o f t h e v i s i b l e s p e c tr u m . The s p e c t o g r a p h f u n c t i o n s a s f o l l o w s . L i g h t fro m a n i n c a n d e s c e n t t u n g s t e n s o u r c e a t 3000* K p a s s e s th r o u g h a c o l l i m a t i n g l e n s a n d f a l l s on a s e t o f p r i s m s so a r r a n g e d t h a t h a l f o f t h e beam t r a v e l s th r o u g h t h e s a m p le a n d r e t u r n s th r o u g h a f i x e d r o t a t i n g s e c t o r t o t h e V P u b l i c a t i o n s o f T he A p p lie d R e s e a r c h L a b o r a t o r i e s o f L o s A n g e le s . i n i t i a l p l a n e , w h ile t h e o t h e r h a l f p a s s e s t h r o u g h t h e c l e a r f i l m b a s e , t o e l i m i n a t e t h e e f f e c t s o f s u r f a c e r e f l e c t i o n a n d s t a i n , a n d r e t u r n s th r o u g h a v a r i a b l e r o t a t i n g s e c t o r t o t h e o r i g i n a l p l a n e . T h is v a r i a b l e s e c t o r c a n b e a d j u s t e d t o a llo w t r a n s m i s s i o n s o f fro m z e r o t o o n e h u n d r e d p e r c e n t o f t h e i n c i d e n t l i g h t . The tw o a d j a c e n t b eam s now p a s s t h r o u g h t h e s l i t a n d o n to t h e g r a t i n g . T he r u l e d c o n c a v e g r a t i n g h a s t w e n t y - f o u r t h o u s a n d l i n e s p e r i n c h , a n d th r o u g h t h e p h en o m en a o f i n t e r f e r e n c e r e f l e c t s t h e t r a n s m i t t e d l i g h t b a c k to . t h e c a m e ra p l a n e a s a s p e c tr u m w i t h a l i n e a r d i s p e r s i o n o f 6 A n g s tro m s p e r m i l l i m e t e r . O r d i n a r y p a n c h r o m a tic m o tio n p i c t u r e f i l m i s u s e d i n t h e c a m e ra . T he tw o b eam s r e c o r d i n t h e s p a c e o f a b o u t o n e e i g h t o f a n i n c h , t h u s l e a v i n g room f o r t e n s u c h r e c o r d i n g s a c r o s s t h e f i l m w i d t h . The e x p o s u r e r e q u i r e d i s a b o u t f i v e s e c o n d s , a n d .a s h u t t e r i s p r o v i d e d i n f r o n t o f t h e s l i t f o r t h i s p u r p o s e . The p a n c h r o m a tic s t o c k c a n b e d e v e lo p e d i n a c o n ti n u o u s t y p e d e v e l o p in g m a c h in e . The tw o beam s o f l i g h t h a v e p r o d u c e d tw o im a g e s o f d i f f e r i n g d e n s i t y f o r e a c h s i n g l e e x p o s u r e . The w a v e le n g th a t w h ic h t h e d e n s i t i e s a r e e q u a l r e p r e s e n t s t h e p o i n t a t w h ic h t h e s a m p le h a s t h e t r a n s m i s s i o n s e t on t h e v a r i a b l e r o t a t i n g s e c t o r . By s u i t a b l y m a rk in g t h e s e e q u a l d e n s i t y p o i n t s , w h ic h a r e e a s i l y d e te r m in e d v i s u a l l y , a t r a n s m i s s i o n c u r v e o f t h e s a m p le i s e v i d e n t o n t h e p a n c h r o m a tic n e g a t i v e s t o c k . The w a v e le n g th s c a l e m ay b e 13 p h o to g r a p h e d b y t h e i n i t i a l e x p o s u r e o r d e te r m in e d l a t e r b y r e f e r e n c e t o a c a l i b r a t e d s c a l e . I I . . TREATMENT OF BATA OBTAINED F i g u r e s 3 t o 2 3 show t h e r e s u l t s o f o n e h u n d re d f i v e d e t e r m i n a t i o n s o f t e n s p e c tr o g r a m s e a c h . F i g u r e s 3 t o 9 r e p r e s e n t t h i o n i n e , F i g u r e s 10 t o 16 r e p r e s e n t a u ro m in e , a n d F i g u r e s 17 t o 2 3 r e p r e s e n t t h e d y e m i x t u r e . T h ey a r e p l o t t e d f o r e a c h o f t h e s e v e n d e n s i t i e s , a s t r a n s m i s s i o n v e r s u s w a v e le n g th f o r s e v e r a l d y e c o n c e n t r a t i o n s . The c h a r a c t e r i s t i c s o f t h e b l u e , y e ll o w a n d g r e e n c o l o r s a r e e v i d e n t . R e l a t i o n f o r a s i n g l e d y e . To d e te r m in e t h e v a l i d i t y o f a r e l a t i o n s h i p s u c h a s t h e L a m b e r t- B e e r la w t h e v a l u e s o f t r a n s m i s s i o n a t a g i v e n w a v e le n g th w e re p l o t t e d a g a i n s t c o n c e n t r a t i o n o f t h i o n i n e . The r e l a t i o n f o u n d , F i g u r e s 24 t o 3 7 , i s lo g |0c - - m T + b . T h is r e l a t i o n s h i p b e tw e e n d y e c o n c e n t r a t i o n a n d t r a n s m i s s i o n o f t h e r e s u l t i n g im a g e i s v a l i d a t e a c h w a v e le n g th c o n s i d e r e d . I t w i l l b e n o t i c e d t h a t t h e s l o p e c h a n g e s i n a r e g u l a r m a n n e r w i t h s i l v e r d e n s i t y . ' T h is i n d i c a t e s t h a t t h e tw o c o n s t a n t s m a n d b m ay b e a f u n c t i o n o f s i l v e r d e n s i t y . The c o n s t a n t s w e re e v a l u a t e d fro m t h e c u r v e s , a n d a r e l i s t e d a s s u c h o n e a c h s h e e t ( F i g u r e s 24 t o 3 7 ) . F i g u r e s 38 t o 4 0 show t h a t l o g D = m, K + b ,. The v a l u e s o f m, a n d b, w e re d e te r m in e d fro m t h e c u r v e s , a n d t h e c o r r e s p o n d i n g v a l u e s o f m a n d b r e p l a c e d i n t h e i n i t i a l i • u*. n firtl -it! /: : ini in: in a;.: ,;i:r rt i_LL T irr ao &O l jra M 20 ill iiii n ill T .l :.qr i.rr MADt IN U. S. A. i m MtZM ;! " i : : :U i : u .XL w ■ - a& on F j ■vypzi. ^ -jfZ - ^ ^ - c &w pz 172 OF 0 8 W W O T t t : > fir: < T i er> w j / ^ s w r / v o not ssfOTsni& c u J i i nyvapasejr car e as 1 T H E IT HfWMTOjrabi *¥ •£ -o S '' 3 -V W o r> r r -O ’ : it WO'fS sr £ : v/siwatt tJ&.L jLti3?a.W. : j r z n r.:i t w o * te : T T T T <3/ H W 3 tffi Q'l *% l& \os~o, v " . 1-::: • _ __ .:** :. rs^. rc'y ss i i N 3 o & s r < i rater V (N r T S 7. W S N b f$ Z ;U i3rD ,9f:m VO Jn o TH tO N tN V E B L U E . . 6-5T Ox 0, \ t '■ £ o w s o so 60 70 60 % 7 '^ f l N S M I S'S. I O N 90 zo to i ir e » cr i*oc T H /O N iW £ B L U E . , 6 W ^ I s 90 90 1 0 JO 70 V o r & a M S M t s s i o n *r/auRE zs L.OG- T H /O N iN E K > c 9 0 eo /oo eo 3 0 fO / o /v ri«t> A c 1 0 t m j l a & e /J M e - L 8 i i V O 3 ~ 0 ~ 60 A#/S 3 /© /V to 3 0 90 eo 9 O too m ^ a 1 < ~J I— • 1 0 TM'ONINA* \ BL 6 0 VO too ao to Vo r / ? « A /J M /5 S /O W n fiD R E 28 4,OG C. i o f icj/sjo a n hi'eu ? o\ 90 zo jTO 60 to 80 bOt5 o. 1 o euu5> vmmje. ..a Q 90 fO too VoT/mMStVHsS/Ofi/ /rse.uMFC st i.O& 10 * U f* O A 7l M E C o IQ S O 3 0 60 90 S O t a 7 ’ „ M/SS/Orj * - / G U t * £ 3 ' *c 10 T.HJOt W/ViS": 3c RLfAfOMLtilU: o : \* ■ \ p. v Ci ' N A 8 0 JO 6 0 90 /O V O 70 ^ TR&MSMISS, t O fj jr/QC/MMI S3 o* o o K IK > < ■ * Vi~<r < 0 0 0 0 0 9 o e o t o . i n o o 0 ! f f i i- 1 0 « in (°J +x3 )$07 % T& giN 3 MtSS I ON 10 4 k f t - i .9 .© k o u 9 80 oo lO so so 90 % r / y w A / J ' W ^ s /o < v s n tt. i ! K n tr »«r t,O G T M U A ; o o W • “ I * 0 £ -0 6 O % T/?e=tNS M t s s i ot / &o 9 0 < r-/ C U/r fi ! TH!/ M S T Q //B O 8.33 8.00 fBZO s & 8 a: 70 •S'. S 3 3.158 2. O /.V / ic p.sv VO -* - 0 T/P&/VS/S7/SSSOA/ LO G DENSITY 0 9 t P q 1 $ s s C O A t S T G N T HCOPE 38 p i c o e e s s L O Q D E N S I T Y to Jy 600B T 6Q 0 Q ■JrbSO*- O t ^© < 5 D BM S ITV 1 0 C Q > • s » > 05 03 CONSTANT 14 e q u a t i o n ( T a b l e s 1 a n d 2 ) . T h is r e s u l t s i n a n e q u a t i o n a t a g i v e n w a v e le n g th i n t e r m s o f t r a n s m i s s i o n , d y e c o n c e n t r a t i o n , s i l v e r d e n s i t y , a n d c o n s t a n t s . By c o m p a ris o n w i t h t h e Lam b e r t - B e e r fo rm : T - e - k c D s t a n d a r d T - lo g ^ c + K q lo g l^ K g D e r iv e d KgltogD* K 4 T h is i n d i c a t e s t h a t t h e p o s t u l a t e d e q u i v a l e n c e o f m or d a n t c o n c e n t r a t i o n a n d s o l u t i o n c o n c e n t r a t i o n d o e s n o t h o l d . A p p a r e n t l y t h e s i l v e r i o d i d e m o r d a n t, w h ile t r a n s p a r e n t , m ay c o n s i s t o f a n o n - u n if o r m p a r t i c l e s i z e a g g r e g a t i o n s u c h t h a t t h e s i l v e r d e n s i t y i s n o t t r a n s f o r m e d l i n e a r l y i n t o t h e m or d a n t . T he w a s h in g t i m e , o f c o u r s e , m ay p e r m i t som e o f t h e d y e p a r t i c l e s t o l e a v e t h e m o rd a n t? h o w e v e r, t h e tim e c h o s e n w as s u c h t h a t t h e s t a i n w o u ld w a sh o u t w i t h o u t a p p r e c i a b l e c h a n g e i n im a g e c o l o r . D o u b le t h i s w a s h in g tim e w o u ld s t i l l g i v e a f a i r c o l o r im a g e , h e n c e n o t to o m uch e r r o r w as i n t r o d u c e d t h e r e . I t w i l l b e n o t i c e d t h a t t h e c o n s t a n t s o f t h e e q u a t i o n s , T a b le 2 , v a r y i n a r e g u l a r o r d e r . F i g u r e s 4 1 t o 4 3 show t h e s e c o n s t a n t s p l o t t e d a s a f u n c t i o n o f w a v e le n g th . In a s m u c h a s a l l c a l c u l a t i o n s a r e b a s e d u p o n e x p e r i m e n t a l d a t a , a n d a n y s l i g h t e x p e r i m e n t a l e r r o r c o u ld b e som ew hat m a g n i f ie d b y c a l c u l a t i o n s a d v a n c e d t o t h i s p o i n t , t h e f a c t t h a t o n e o r tw o p o i n t s f a i l e d t o f a l l u p o n t h e c o n s t r u c t e d c u r v e w as d i s r e - l EVALUATION OF m OND b OS A FUNCTION OF D /< 0 & c " T -rt> I o'" LOG,0D = ^ H S O s w M . : B L U E t-EO syrt M! YELLOW y s O s m M - : GREEN 5 0 0 r-r^M. - . BLUE 50 0 ^ X M . y e l l o w 5 0 0 smM.'. GREEhJ 5 2 S sy~ vl. YELLOW S S Q srriM*: BLUE 550 s m YELLOW 5 5 0 smM.: GREEN bOOsrr^M: B L U E 600 srr\M*i YELLOW 6 0 0 sv*.m.: GREEN 650smM- ' ■ BLiUE 6>50/yr*M,: YELLOW 6 5 D / v > ^ ^ c : g r e e n , ( OR b ) t b t J H E N C E (sr r v OR b ) = L 0 £iaRZ-k<.. L O G 0 - / 7 5 0.34% LOG 0-2.52 7^3 ^yn .- LOGD-0.732 0.177 L C G 0 - 0 . 9 0 4 0 . 4 7 6 L O O P - 0.732 0.462 L0&D~ L it 0.18 / L O G O - LOO 0 .5 5 5 L 0 6 0-1.29 0.7/4 LOO 0 -2 .5 9 0.58% LO G O -2.20 1.H9 LOG D - 2 .ll I.2 B LOG P - eO LOGO- 1.82 1.22 L0GD-J.78 1.22 ^ L0G0-<*=> o o - L O G O - 3 . 1 2 1 . 82 k - LOGO-2 .8 2 1 -0.513 b= LQ(y D'° b d 5 5 -Z.3J L = LO G O - 0,0/47 1 -0 .3 3 4 LOGO- 0 .5 7 7 ~ - 0.449 LOG Q - 0 .3 0 * - 0 . 4 3 5 LOG D - 0.734 -0.690 LOGO- 0 .6 7 5 -0 .4 3 5 LOGO-0 .6 3 0 -0.7 66 LOG D - 2.60 -0 .6 0 6 L O G O - 0.805 -A 09 LOO P - 0 . 4 2 8 7/ , v l LOOP- _ _ 6 = f c > = 6 = 6 = 6 = t> = 6 = /> = b - b = b = b - L O O P - 0 . 2 7 7 -A20 LOOP-0 .0 8 4 - A /6 LOOP- < * « LOG P - 0.075 - 0 .4 3 5 T / 9 & L E / H 50 s w a C : SOO /mil; 600 Cq-) G O ( c ) ( c t) t o o C ~ - f ^ 0 3 t f 8 7 5 ) T ^ C ^O ^sf-Z 2 ) = -2.7?,'T'L,0<o D + S O ^ T - / . 9 5 LOG D+ 5 .5 L O G c * —/ L°6 P -fl.9 Q 5 \ / l o (j p-n.57\ ( 0X76 } T + (- ’ ) = -ZtO-T-LOG-D +I.3T - 2.25 LOCrD + J.3 LOG C » - ) T + ^ i i g f r P ^ ' 6 3 - ) = — IMO'T' L O G O + 7 , 8 / T - f.Z7 LOG D -+ O .8 0 LOG C » ? ’' 7 . ) T ~ > - / l*POO~QH3 \ _ a •78-T-hOG- D + J .7 0 T -0 .7 0 LOG O + 0 . 3 0 ' ® ' - / . ¥ 3 ' LOG r » J r ^ /LOGV-OMSl ) - _ n . * 7 .T LOG D + ). 6 2 T - 0.86 L O G D+0.07 v IZ2 i V r/^g - / - 6 SV -/¥ 02 ¥68 (c> = ' * " “ ' - 1 9 8 5 780 ( d ) — — 620 8 9 EQUATIONS RELATiM& T * t O Y E CONCENTRATION. ANO D FOR THlONlNE (*.) ( b . ) C c.) ( d , ) LOO C = T + ( ^ ~ | ^ ) = -ftW-TMS D + /-76T - 0.7*r OOOD +0.50 5 0 ^ * : 0 0 & c ~ e ° t^ 2 ) T + = - * '8 - T - t 0 6 0+ /.37T - 2.3 -606 D + 0 .7 0 S Z S ^ m . . L# 6 C = -/106D -/.00 \ y / 606P-A675 \ _ _ ; 0 .7 ; /,^G P f- /0 O r - 2-3 p + /.«*• v 0.555 / ' I - 0 H S 5 I ° SSO /rx-M . i.d f'.c - —A jO frP -2 .5 9 'j -- / 6 0 6 P - 2 . 6 O 1 _ _ / 7 0 7 : 6 0 6 P -f H .dT ~ 1.& 5 L iO G > D + V .2 8 ^ 0.588 / \ - O.60b / (a ,) — 7 /0 (b,) = too - ///V -372 (c ,) = ^ ^ - 7 0 6 83 (di) = ■ - 3 8 9 / a s HQUATfONS PELflTlMG Tx , DYE COh/CEh/TRBT/ON, a n d D FOR AVROMINE TRBLE 2 CcOKO-'e) (aa ) (bj C c J U J / L 0 6 t > - 0 . 7 3 2 \ / L O C P - 0 , 0 l & \ _ _ _ ^ ^50/rruM ^: L O G { ^ ~ j ~ - ' t — ------/ T + ( : ^ 3 3 ^ — / = ~ & .6 T LOGO +H.10T - 3 . 0 LOG D + 0 . 4 8 S O O ^ m.: i Z t e ( - S i ^ j = ~ ( ~ ° | y B/ -— j T + " - I - 2 6 T L 0 G P + I M Z T - IHS LOG D + O .l* S S O ^ LO G ^Y- - (W f^ ? SL)7 + = -O MT LOGOtLSr -0.92 L O G 0+0.9* 600s~,M .: wg( ^ s)= - ( M ? ^ H ) T + ( - 0 ^ U 6 2 7 7 ' ) = “ o e 2 'T - L O l i D + , 5 T -°-83LOGD. az3 \ 2 , / ••fcfc 6 5 - 0 ^ ^ ; lC o (‘^ < ) , ( L0C? g ? K ) T + ( - -ri.3 9 ~ ) = ^ • 5 5 ',T' 4 0 6 D +I.7/T - 0 - 7 ? LOGO + 0.10 s ~ \ * -y » “ 6 * 7 {ax)~ /2 7 ( W ^y~OMs+ 210 so o (<’ 0 « •838 * 6 0 (.60 = 700 - 6 0 8 SQOATiONS RELATING- } D Y E CONCENTRATION, AND 0 #r0£ THIONINE- AUROMINE M IX T U R E T8BLE Z(C0NTP) — ■ r: T ? Sj:n bj.^k o : 15 g a r d e d . The e v a l u a t i o n o f t h e c o n s t a n t s fro m t h e c u r v e s r e s u l t s i n o n e s i n g l e e q u a t i o n ( T a b le 3 ) f o r t h e a d s o r p t i o n o f t h i o n i n e b l u e o n to a s i l v e r i o d i d e m o rd a n t i n t e r m s o f d y e c o n c e n t r a t i o n , s i l v e r d e n s i t y , w a v e le n g th a n d t r a n s m i s s i o n . A r b i t r a r i l y c h o s e n v a l u e s o f c , A , a n d D r e s u l t i n a c a l c u l a t e d t r a n s m i s s i o n w i t h i n tw o a n d o n e h a l f p e r c e n t o f t h e e x p e r i m e n t a l l y d e te r m i n e d v a l u e . R e l a t i o n f o r t h e d y e m i x t u r e . F i g u r e s 4 4 a n d 4 5 show , a s a d o t t e d l i n e , t h e c a l c u l a t e d su m m a tio n e f f e c t o f t h e i n d i v i d u a l y e llo w a n d b l u e d y e im a g e s a s w e l l a s t h e a c t u a l c u r v e o f t h e tw o d y e s a d s o r b e d o n t h e m o r d a n t. T h e re i s a d e f i n i t e d i s c r e p a n c y a t lo w w a v e l e n g th s . To b e t t e r s t u d y t h i s e f f e c t , t h e y e ll o w a n d g r e e n d y e c u r v e s w e re i n v e s t i g a t e d t o o b t a i n r e l a t i o n s a s a o o v e . T he sam e fo rm o f e q u a t i o n w as f o u n d t o e x i s t . S in c e t h e a u ro m in e t r a n s m i s s i o n r e a c h e s 1 . 0 a n d r e m a in s t h e r e a t a l l c o n c e n t r a t i o n s f o r some s p e c t r a l r a n g e , t h e d e r i v e d r e l a t i o n f a i l s a t t h i s p o i n t ; t r a n s m i s s i o n i s i n d e p e n d e n t o f c o n c e n t r a t i o n . T he f i n a l c o n s t a n t s do n o t show a s g o o d l i n e a r r e l a t i o n a s f o r t h e t h i o n i n e , h e n c e t h e r e s u l t i n g e q u a t i o n f o r w a v e le n g th s u n d e r 550 mu i s n o t e x a c t . T he e q u a t i o n r e p r e s e n t i n g t h e c o m b in a tio n o f t h e tw o d y e s i s s u b j e c t t o t h e a b o v e p l u s a n a d d i t i o n a l e r r o r . The p r o b le m h e r e i s o n e o f p a r t i t i o n . The tw o m u s t r e a c h a c o n c e n t r a t i o n e q u i l i b r i u m d e p e n d in g u p o n t h e a f f i n i t y o f e a c h T H I O N I N E : LOG* lO m i r o m i n e : log c MIXTURE i LOG^— 1 F t N f ) l E Q U A T I O N S CT = 7 o o o (j- 3<r* T‘t 0 ^ D 4' ? -<3T^ l z 8 Ll0^ o D + , l ^ ) + < ?.0 8 -T U 0 6 D + 3 . 0 T + 2 . 5 5 LO G O -»6.9 7 r lo § o " ( ,0,1:1*O G r . D 42.€»9T+/2.O6L06D-7.¥/j + 7W8 T lJ0G! ) D +3.G T+9.52 LOGO-2.B8 j = jtfo{7.88-TLO C JO -2.0T+ 335LO O O +I.b^+5.I7<U 0G D+0.H2J +3.22 LOGO +1.15 WHME; C = • D Y E CONCENTRATION IN GRAMS PER. LITER X - WAVELENGTH I N /rv n ja . T- TRANSMISSION AT A t> = INITIAL SILVER DENSITY T A B L E 3 c « 4 c c u » * y r / 0 / \ / o f t f r o m the t h /o n /ive eqo&tion C O f r f t 0 0 I I 1 £ II 0 Q M 0 ft o o f t I * V •v 0 0 f t ft \ c r S ! < 0 < II 0 5 : V ii t v u z 0 k 5 u K > v *-v v l 1 . <0 U l U l * > k U l 5 0 0 £ • * U i £ 3 I A 1 4 c IS. I l t o 7 > V I 'N , « 0 c k * 0 K « Z S © ■ u i u i Q 1 k IK Z k V I M l ■ J <t > U l n U J 5 s i- k k V ) ft 3 ft tv < 9 - v j O f *• d i? H * t v « n tv m < S o? n > O i t s ft € X « v C O tt ft I k Is »• ft ♦ V » *v 0 s 1 K ft + t v 0- s « v ft f t* I < v rv i0 I m .0 C l ft « v k ft ft ft « < 3 ! • ^5 CL v > 0 o ♦ k < 0 O s j k ct ft ft C M < M ft < 3 0* § 2 M I I f l o or f V si * s » 0 ft o' 1 < 0 ‘ n + O v ft Pi 1 4 0 f4 ■ * < t rt m ft k \ V tn o it U i > 1 C \t 3 u ft £ $ w * i s s o { <v o 0 + I f q; o O f fc Ul y ft w M Q a TftBLE 3(CO*/r'a) p fit ■ rr< rfs&tvst p is Tjrr-.j iv.rzvsaf PWICT. Cl'M£ 1M • 3 0 JH : WBMGLK** 16 f o r t h e s i l v e r i o d i d e im a g e . U n le s s t h e y h a v e e q u a l m or d a n t i n g p o w e r o n e w i l l p r e d o m i n a t e . When t h e d y e d s t r i p i s p u t i n t o t h e w a s h , i f o n e d y e i s m o re s o l u b l e , o r m o re mo b i l e t h a n t h e o t h e r , i t w i l l w ash o u t f i r s t ; t h u s a l t e r i n g t h e c o n c e n t r a t i o n s a ro u n d t h e im a g e w h ic h m ay p r o d u c e a d i s p l a c e m e n t o f o n e d y e . T h is e f f e c t w o u ld b e som ew hat a f u n c t i o n o f d e n s i t y s i n c e t h e f i r s t .d y e t o l e a v e w o u ld h a v e t o p a s s t h r o u g h a g r e a t d e a l o f t h e e q u i l i b r i u m m ix t u r e i n a h i g h d e n s i t y c o m p a re d t o p r a c t i c a l l y n o n e i n a lo w d e n s i t y . A s s e e n b y t h e i n i t i a l c u r v e s t h e r e i s a te n d e n c y f o r t h e lo w d e n s i t i e s t o s h i f t to w a r d t h e b l u e w h ile t h e h i g h d e n s i t i e s r e m a in g r e e n . A p p a r e n t l y t h e y e ll o w i s w a s h in g o u t m o re r a p i d l y t h a n t h e b l u e , p a r t i c u l a r l y a t h i g h d y e c o n c e n t r a t i o n s . T h is p h en o m en o n c a n n o t b e a c c u r a t e l y r e p r e s e n t e d b y a s i n g l e m a t h e m a t i c a l e q u a t i o n ; a n d a lt h o u g h t h e tw o e q u a t i o n s show t h e sam e g e n e r a l f o r m , a n d i n t h a t t h e y a r e p r o b a b l y c o r r e c t , t h e y a r e n o t r e l i a b l e f o r a l l c o n d i t i o n s o f t h e f o u r v a r i a b l e s . I f tw o d y e s o f e q u a l a f f i n i t y f o r t h e s i l v e r i o d i d e c o u ld b e f o u n d , a m uch m ore r e l i a b l e r e l a t i o n m ig h t b e d e d u c e d . V i s u a l i n t e n s i f i c a t i o n . So f a r , t h e s p e c t r o p h o t o - m e t r i c r e s u l t s h a v e b e e n c o n s i d e r e d fro m t h e s t a n d p o i n t o f a g r o u p o f i n d i v i d u a l w a v e l e n g th s . T he v i s u a l i n t e n s i f i c a t i o n , d e te r m i n e d a s f o l l o w s , c o n s i d e r s t h e n e t e f f e c t o f t h e v a r i o u s c h a n g e s i n d e n s i t y a n d d y e c o n c e n t r a t i o n . F i g u r e 4 6 17 sh o w s t h e a v e r a g e v i s i b i l i t y f u n c t i o n f o r a n e q u a l e n e r g y d i s t r i b u t i o n . ® The p l o t o f p e r c e n t t r a n s m i s s i o n o r r e l a t i v e r e s p o n s e a g a i n s t w a v e le n g th r e p r e s e n t s t h e s e n s i t i v i t y o f t h e hum an e y e w hen v ie w in g a s p e c tr u m h a v i n g a n e q u a l e n e r g y e m i s s io n f o r e a c h w a v e le n g th . As c a n b e s e e n , t h e r e i s a d e f i n i t e p e a k i n t h e g r e e n . The o r d i n a t e s o f t h i s c u r v e w e re m u l t i p l i e d b y t h e c o r r e s p o n d i n g o r d i n a t e s o f s e v e r a l o f t h e o r i g i n a l d y e t r a n s m i s s i o n c u r v e s . T h e s e r e s u l t i n g v a l u e s a r e t h e o r d i n a t e s o f new c u r v e s , e a c h o f w h ic h r e p r e s e n t s t h e e f f e c t s e e n b y t h e e y e v ie w in g t h e g i v e n d y e d e n s i t y . T h e s e l u m i n o s i t y c u r v e s w e re p l o t t e d , F i g u r e s 47 t o 5 3 , a n d t h e a r e a s u n d e r e a c h d e te r m in e d w i t h a p l a n i - m e t e r . ^ T he su m m a tio n o f t h e s e o r d i n a t e s f o r a n y o n e c u r v e , o r t h e a r e a u n d e r t h e c u r v e , r e p r e s e n t s t h e t o t a l o r i n t e g r a t e d p h y s i o l o g i c a l e f f e c t o n t h e hum an e y e . T h is v a l u e d i v i d e d i n t o t h e a r e a u n d e r t h e a v e r a g e v i s i b i l i t y f u n c t i o n i s a n i n v e r s e m e a s u re o f t h e i n t e n s i t y o f t h e d y e im a g e . I n f a c t , t h i s v a l u e i s t h e r a t i o o f r e l a t i v e a m o u n ts o f v i s i b l e e n e r g y . I f t h e log-^Q o f t h i s r a t i o b e c o n s i d e r e d , t h e n b y v i r t u e o f t h e d e f i n i t i o n o n p a g e 3 , t h e r e s u l t i n g v a l u e i s t h e v i s u a l d e n s i t y o f t h e d y e im a g e ( s e e T a b le 4 ) . S j 7~w7 T . W a ls h , P h o to m e tr y . 1 9 2 6 , p . 2 9 5 . 9 J o u r n a l o f t h e F r a n k l i n I n s t i t u t e , V o l. 2 1 7 , N o. 4 , A p r i l 1 9 3 4 ; A. M. G u n d e l f i n g e r , S o e c t r o p h o t o m e t r i c D e te r m in a t i o n o f T one I n t e n s i f i c a t i o n i n C o lo r M o tio n P i c t u r e F ilm . I not s < r v<3/ sT/e*SN&&u. 1 1 - ; : u :i n i. : i.r; 2 L / V O / S B / W f f XN3 >3 * 3 4 I I i TABLE 4 DATA FOR INTENSIFICATION CURVES D e n s i t y = 0 .6 6 A r e a i n s q u a r e i n c h e s A r e a of* a v e r a g e v i s i b i l i t y c u r v e s Q u o t i e n t I T D e n s i t y I 1 0 g lo rji 0 .2 5 g / 1 T . 8 .8 9 1 2 .7 2 1 .4 3 • 0 .1 5 5 0 .5 0 g / 1 T . 7 .0 4 1 2 .7 2 1 .8 0 5 0 .2 6 1 . 0 g / 1 T . 6 . 1 2 1 2 .7 2 2 .0 8 0 .3 2 2 . 0 g / 1 T . 3 .8 7 1 2 .7 2 3 .2 9 0 .5 2 4 . 0 g / 1 T . 1 .9 1 1 2 .7 2 6 .6 7 0 .8 2 D e n s i t y * 0 .1 2 0 .2 5 g / 1 T . 1 0 .0 6 1 2 .7 2 1 .2 6 8 0 . 1 0 0 .5 0 g / 1 T , 8 .7 2 1 2 .7 2 1 .4 6 0 .1 6 1 . 0 g / 1 T . 7 .8 7 1 2 .7 2 1 .6 2 0 . 2 1 2 . 0 g / 1 T . 6 .3 5 1 2 .7 2 2 . 0 1 0 .3 0 4 . 0 g / 1 T . 4 .3 0 1 2 .7 2 2 .9 6 0 .4 7 D e n s i t y * 0 .6 6 0 .2 5 g / 1 A . 1 2 .0 7 1 2 .7 2 1 .0 5 5 0 . 0 2 0 .5 0 g / 1 A. 1 1 .6 9 1 2 .7 2 1 .0 9 0 .0 4 1 . 0 g / 1 A. 1 1 .2 8 1 2 .7 2 1 .1 2 7 0 . 0 5 2 . 0 g / 1 A. 1 0 .3 0 1 2 .7 2 1 .2 3 0 .0 9 4 . 0 g / 1 A. 9 .3 7 1 2 .7 2 1 .3 6 0 .1 3 D e n s i t y « 0 .1 2 0 .2 5 g / 1 A. 1 2 .3 1 1 2 .7 2 1 .0 3 0 . 0 1 0 .5 0 g / 1 A. 1 2 .0 0 1 2 .7 2 1 .0 6 0 .0 3 1 . 0 g / 1 A. 1 1 .5 2 1 2 .7 2 1 .1 0 0 .0 4 2 . 0 g / 1 A . 1 1 .2 9 1 2 .7 2 -. 1 .1 3 0 .0 5 4 . 0 g / 1 A . • 1 0 .8 2 1 2 .7 2 1 .1 7 4 0 .0 7 D e n s i t y » 0 .6 6 0 .2 5 g / 1 e a c h 8 .4 7 1 2 .7 2 1 .5 0 0 .0 6 0 .5 0 g / 1 e a c h 5 .3 7 1 2 .7 2 2 .3 7 0 .3 7 1 . 0 g / 1 e a c h 4 .7 2 1 2 .7 2 2 .7 0 0 .4 3 2 . 0 g / 1 e a c h 2 .5 4 1 2 .7 2 5 .0 0 0 .7 0 4 . 0 g / 1 e a c h 0 .5 0 1 2 .7 2 2 5 .4 2 1 .4 1 D e n s i t y » 0 .1 2 0 .2 5 g / 1 e a c h 1 1 .5 5 1 2 .7 2 1 .1 0 0 .0 4 0 .5 0 g / 1 e a c h 9 .2 1 1 2 .7 2 1 .0 8 7 0 .0 4 1 . 0 g / 1 e a c h 7 .3 6 1 2 .7 2 1 .3 6 0 .1 3 2 . 0 g / 1 e a c h 5 .3 1 1 2 .7 2 2 • 39 0 .3 8 4 . 0 g / 1 e a c h 3 .3 1 1 2 .7 2 . 3 .0 2 0 .4 8 18 F i g u r e 54 sh o w s t h e s e v i s u a l d e n s i t y v a l u e s p l o t t e d a g a i n s t d y e c o n c e n t r a t i o n f o r s e v e r a l i n i t i a l s i l v e r d e n s i t i e s . The s l o p e s r e p r e s e n t t h e r e l a t i v e i n t e n s i f i c a t i o n s o f t h e d y e im a g e s , a n d s i n c e t h e s e v a r y w i t h s i l v e r d e n s i t y , i t i s e v i d e n t t h a t a s im p le e x p o n e n t i a l f u n c t i o n s i m i l a r t o t h e L a m b e r t- B e e r la w c a n n o t h o l d . F i g u r e 5 5 show s t h e v i s u a l d e n s i t y i n c r e a s e w i t h s i l v e r d e n s i t y f o r s e v e r a l d y e c o n c e n t r a t i o n s , w h i l e F i g u r e 56 s u m m e riz e s t h e s e r e s u l t s b y show i n g t h e r a t e s o f c h a n g e o f t h e s e s e v e r a l f a c t o r s . e t X o cdTm, Hl d - 1 - 6 . S c f = ° - 13 - 0 .3 3 0 .0 3 o t D c c t- o I t c a n b e s e e n t h a t f o r i n d i v i d u a l d y e s , t h e ( g fis u a l i n t e n s i f i c a t i o n i s i n c r e a s e d m uch m ore b y i n c r e a s i n g s i l v e r d e n s i t y t h a n b y c h a n g in g d y e c o n c e n t r a t i o n . T he d y e m ix - fc ^ t u r e d a t a a r e g i v e n , b u t t h e p o i n t s f a i l t o i n d i c a t e a n y l i n e a r v i s u a l d e n s i t y c h a n g e . T h is i s p r o b a b l y d u e t o t h e d i f f e r e n c e i n m o r d a n tin g p o w e r e x h i b i t e d b y t h e tw o d y e s s t u d i e d . V i 5 Hi n S7SO rrsTw CHAPTER IV SUMMARY AND CONCLUSIONS Sum m ary. I t h a s b e e n p o s s i b l e t o d e r i v e a g e n e r a l e q u a t i o n f o r t h e t r a n s m i s s i o n a n d c o n c e n t r a t i o n c h a r a c t e r i s t i c s o f s i n g l e d y e s a d s o r b e d o n to a s i l v e r i o d i d e m o rd a n t, a s w e l l a s t o show t h e .ty p e a n d r e l a t i v e im p o r ta n c e o f t h e f a c t o r s c o n t r o l l i n g v i s u a l i n t e n s i f i c a t i o n . Due t o d i f f e r e n c e s i n m o r d a n tin g a b i l i t y b e tw e e n t h e a u ro m in e a n d t h i o - n i n e , a g e n e r a l e q u a t i o n i n v o l v i n g i n d i v i d u a l d y e c o n c e n t r a t i o n s a n d r e s u l t i n g im a g e t r a n s m i s s i o n w as f o u n d u n r e l i a b l e . B e f o r e c o n t i n u i n g s u c h a n i n v e s t i g a t i o n a k n o w le d g e o f r e l a t i v e m o r d a n tin g p o w e r s h o u ld b e a c q u i r e d . I t m ay b e p o s s i b l e t o d e te r m i n e r e l a t i v e v a l u e s f o r a p a r t i c u l a r m o rd a n t b y s t a n d a r d i z i n g a l l f a c t o r s b u t w a s h in g t i m e . T he c o n c e n t r a t i o n l o s s b e tw e e n tw o d i f f e r e n t w a s h in g t im e s s h o u l d b e a n i n v e r s e m e a s u re o f t h e t e n d e n c y o f t h e m o rd a n t t o h o l d t h e d y e . M e th o d s o f m e a s u r in g t h e e l e c t r o s t a t i c c h a r g e o n t h e d y e a r e a p t t o b e m i s l e a d i n g in a s m u c h a s a su m m a tio n o f c h a r g e s a n d p a r t i c l e s i z e s m u s t b e a v e r a g e d , w h e re t h e m or d a n t m ay s e l e c t o n e c h a r g e a n d o n e s i z e p a r t i c l e fro m a l l t h o s e p r e s e n t . To e x te n d t h i s a b i t f u r t h e r , i t m ay b e p o s s i b l e t o d e te r m i n e t h e m o l e c u l a r w e ig h t o f t h e a d s o r b e d p a r t i c l e b y s t u d y i n g m o l e c u l a r l a y e r s o f t h e m o r d a n t. The m a ss o f t h e m o rd a n t a n d a d s o r b e d d y e c o u ld b e d e te r m i n e d 20. a n a l y t i c a l l y * W ith a th o r o u g h u n d e r s t a n d i n g o f t h e s e s e v e r a l f a c t o r s a f u r t h e r a t t e m p t a t su m m a tio n e f f e c t s s h o u ld y i e l d a m ore r e l i a b l e g e n e r a l e q u a t i o n f o r d y e m i x t u r e s . C o n c l u s i o n s . ( 1 ) A s i l v e r i o d i d e m o rd a n t w as p r e p a r e d a n d a d s o r p t i o n s t u d i e s m ade w i t h tw o d y e s , a u ro m in e 0 a n d t h i o n i n e . T he a d s o r p t i o n o f e i t h e r d y e a lo n e w as fo u n d t o f o l l o w t h e g e n e r a l fo rm T * lo g ,wc ♦ Kq lo g ;,D + % 1 0g|t> D - K4 r a t h e r t h a n t h e L a m b e r t- B e e r t y p e f o r m u la . ( 2 ) F o r s i n g l e d y e s i t w as f o u n d t h a t l o g C ■ A C k .TLOG10D ^ K 2T + K ,L O G |0 D *K J-*-K 5 LOG10D *K fc T«- K , 1 0 w h e re c « d y e c o n c e n t r a t i o n i n g r a m s / l i t e r T * t r a n s m i s s i o n a t w a v e le n g th A D = s i l v e r d e n s i t y X * w a v e le n g th i n mu ( 3 ) The sam e g e n e r a l fo rm w as f o u n d t o a p p l y t o a m i x t u r e o f a u ro m in e a n d t h i o n i n e , b u t o n l y w i t h f a i r a c c u r a c y d u e t o v a r i a t i o n s i n r e l a t i v e d y e a d s o r p t i o n ; h e n c e i t w as n o t p o s s i b l e t o e x p a n d t h e g e n e r a l f o u r v a r i a b l e e q u a t i o n t o s a t i s f a c t o r i l y f i t t h e m ix t u r e o f d y e s u s e d . ( 4 ) T he v i s u a l i n t e n s i f i c a t i o n o f t h e s e v e r a l d y e s w as d e te r m i n e d . I t w as f o u n d t h a t t h e t h i o n i n e h a d a n i n t e n s i f i c a t i o n f i v e t i m e s t h a t o f t h e a u ro m in e , a n d t h a t a g r e a t e r c h a n g e i n i n t e n s i f i c a t i o n c o u ld b e p r o d u c e d b y a l t e r i n g s i l v e r d e n s i t y t h a n b y v a r y i n g d y e c o n c e n t r a t i o n . BIBLIOGRAPHY A . BOOKS G etm an , F . H . a n d F . D a n i e l s , O u t l i n e o f T h e o r e t i c a l Chem i s t r y , 1 9 3 1 . H a r d y , A r t h u r C . a n d F r e d H . P e r r i n , P r i n c i p l e s o f O p t i c s , 1 9 3 2 . N e b l e t t e , C . B . , P h o to g r a p h y , I t s P r i n c i p l e s a n d P r a c t i c e , S e c o n d E d i t i o n . S v e d b e r g , T h e , C o l l o i d C h e m i s t r y , 1 9 2 8 . W a ll, E . J . , T he H I s t o r y o f T h re e C o l o r P h o to g r a p h y , 1 9 2 5 . W a ls h , J . W. T . , P h o to m e tr y . 1 9 2 6 . B . PERIODICAL ARTICLES A s h le y , " S p e c tr o p h o t o m e t r i c M e th o d s i n M o d e m A n a l y t i c a l C h e m i s t r y , 1 1 T he J o u r n a l o f I n d u s t r i a l a n d E n g i n e e r i n g C h e m i s t r y . A n a l y t i c a l E d i t i o n , F e b r u a r y 1 5 , 1 9 3 9 . G u n d e l f i n g e r , A . M ., " S p e c t r o p h o t o m e t r i e D e t e r m i n a t i o n o f T one I n t e n s i f i c a t i o n i n C o lo r M o tio n P i c t u r e F i l m , 1 1 T he J o u r n a l o f t h e F r a n k l i n I n s t i t u t e , V olum e 2 1 7 , N o. 4 , A p r i l 1 9 3 4 . C . PUBLICATIONS OF LEARNED ORGANIZATIONS M o tio n P i c t u r e L a b o r a t o r y P r a c t i c e , E a s tm a n K odak C om pany. P u b l i c a t i o n s o f T he A p p l i e d R e s e a r c h L a b o r a t o r i e s o f L o s A n g e l e s .
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Trimble, L. S. (author)
Core Title
A study of the relation between the concentration of a dye and the transmission of an image produced by dye adsorption on a suitable mordant.
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Digitized by ProQuest
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Master of Science
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University of Southern California
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Chemistry (Physical Chemistry),OAI-PMH Harvest
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English
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[illegible] (
committee chair
), [illegible] (
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), Copeland, C.S. (
committee member
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https://doi.org/10.25549/usctheses-c17-789115
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UC11347888
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EP41531.pdf (filename),usctheses-c17-789115 (legacy record id)
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EP41531.pdf
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Trimble, L. S.
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University of Southern California Dissertations and Theses
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University of Southern California Dissertations and Theses