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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 re s e n te d to
t h e F a c u l t y o f th e G ra d u a te S c h o o l
T he U n i v e r s i t y o f S o u t h 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 ire 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 in .C h e m is tr y
by
L . S . T r im b l e
J u l y 1940
UMI Number: EP41531
All rights reserved
INFORMATION TO ALL USERS
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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 oiftBtofl PablislJrtg
UMI EP41531
Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author.
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C
h- i
Tz m
This thesis, written by
..........................
under the direction of hLa.. Faculty Committee,
a n d a p p r o v e d by a l l its m e m b e r s , has been
presented to and accepted by the Council on
Graduate Study and Research in partial fulfillн
m e n t of the r e q u ir e m e n t s f o r the d e g r e e of
MASTER OF SCIENCE
D ean
o w
e . ......
Secretary
D a te
A u g u s t ...1 9 .4 0 ..............
F aculty C om m ittee
Chair mi
(ft-
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 t o r y .
TABLE OP CONTENTS
CHAPTER
I.
PAGE
THE PROBLEM AND DEFINITIONS OF TERMS USED
1
..........................
2
BACKGROUND OF THE A R T ..........................................................
4
D e f in i t io n s o f te rm s u se d
P ra c tic e
i n t h e a r t ...................................................
METHODS OF STUDY
E x p e rim e n ta l te c h n iq u e
4
. ................................................
5
...............................................................
7
T h e o re tic a l c o n s id e ra tio n s
III.
1
...............................................
T he p r o b l e m
II.
. . . .
. . .
. . .
7
T y p e o f i m a g e .............................................................
7
T he p r e p a r a t i o n o f u n i f o r m s i l v e r d e n s i t i e s
.
8
T he 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
T he 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 ................................... 1 1
T r e a t m 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 is u a l i n t e n s i f i c a t i o n
IV .
.........................................................
SUMMARY AND C O N C L U S IO N S .........................................................
Sum m ary
.................................................................. .
.
.
16
.
.
19
' 19
C o n c l u s i o n s .........................................................................................2 0
BIBLIOGRA PHY.................... ....................................................................................... 2 1
LIST OF TABLES
FOLLOWING
PAGE
TABLE
1.
E v a lu a tio n o f th e C o n s ta n ts m and b a s a
F u n c t i o n o f S i l v e r D e n s i t y .....................................
2.
E q u a tio n s r e l a t i n g
tra tio n ,
tra n s m is s io n ,
Dye C o n c e n н
and S i l v e r D e n s ity f o r T h io n in e ,
A u r o m in e , a n d t h e Dye M i x t u r e .........................
3.
14
F i n a l E q u a tio n s D e riv e d fro m E x p e r im e n ta l
D a t a .........................
4.
14
D a t a f o r I n t e n s i f i c a t i o n C u r v e s .........................
15
17
LIST OF FIGURES
FIGURE
1.
FOLLOWING
. PAGE
T ra 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 rн
f a c e S i l v e r I o d i d e Im a g e . . . . . . .
2.
T y p ic a l S e n s ito m e tr ie
s trip
P lo tte d as
a n H u r t e r a n d D r i f f i e l d C u rv e
3 .- 9 .
7
. . . .
9
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 D a t a f o r
T h i o n i n e ..............................
13
1 0 . - 1 6 . 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 D a t a f o r
A u ro m in e1 7 .- 2 3 .
.........................................................
13
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 D a t a f o r
t h e M i x t u r e o f T h i o n i n 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 i o n
o f th e T ra n s m is s io n o f th e R e s u ltin g
Im a g e
3 8 .- 4 0 .
........................................................
13
S i l v e r D e n s ity P l o t t e d a s a F u n c tio n o f
th e C o n s ta n ts m and b
...........................
4 1 .- 4 3 . C o n s ta n ts o f th e C o n c e n tra tio n ,
s io n ,
13
T ra n s m is н
and S i l v e r D e n s ity R e la tio n P l o t н
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 i s s i o n v e r s u s W a v e le n g th a s F o u n d
f r o m t h e Dye M i x t u r e a n d a s C a l c u l a t e d
f r o m I n d i v i d u a l Dye D a t a ......................
46.
A v e rag e v i s i b i l i t y
D is trib u tio n
15
C u rv e f o r E q u a l E n e r g y
..............................................................
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 .
54.
C u r v e s S h o w in g t h e R a te - o f C h a n g e o f
V i s u a l D e n s i t y w i t h Dye C o n c e n t r a t i o n .
55.
.
18
C u r v e s S h o w in g t h e R a t e o f C h a n g e o f
V is u a l D e n s ity w ith S i l v e r D e n s ity . . .
56.
17
18
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 I m a g e s
a s a F u n c t i o n o f Dye C o n c e n t r a t i o n a n d
S ilv e r D e n s ity .
...........................................................
18
CHAPTER I
THE PROBLEM AND DEFINITION'S OF TERMS USED
T he p r o b l e m .
C o lo r p h o to g ra p h ic r e p r o d u c tio n i s .
b a se d upon th e a c c e p te d p r i n c i p le
v is ib le
s p e c tru m c an be r e p ro d u c e d b y s u i t a b l e
o f th r e e p rim a ry c o lo r s .
a rie s ,
t h a t any c o lo r in th e
To o b t a i n t h e s e
c o m b in a tio n
so c a l l e d p r i m н
c o lo r e d p ig m e n ts o r d y e s a r e u s e d .
In asm u ch a s
t h e r e a r e a g r e a t num ber o f d y e s a v a i l a b l e ,
e ac h h a v in g
so m e w h a t 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 ,
th e p rim a ry
c o l o r s a r e o f t e n m ad e u p o f a s i n g l e d y e , o r a m i x t u r e o f
s e v e ra l d y es.
As 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 in g le dye in
s o lu tio n ,
o r a m ix tu re o f d y e s ,
a re e x p re sse d
i n t e r m s o f t h e w e l l know n L a m b e r t - B e e r la w o f a b s o r p t io n ,- * w h ic h s t a t e s
I = - k c 1
I?
w h e re k л a b s o r p t i o n c o e f f i c i e n t
c = c o n c e n tra tio n o f m a te r ia l
1 * le n g th o f liq u id tr a v н
e rse d
I = tr a n s m itte d e n e rg y
1^ = i n c i d e n t e n e r g y
T he 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
re p ro d u c tio n i s o ld in th e a r t .
T he s t u d y a n d a n a l y s i s o f
^ The S v e d b e rg , C o l lo i d C h e m is tr y . 1 9 2 8 , p . 2 0 5 ; A rн
t h u r C . H a r d 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 e tm a n 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 try . 1 9 3 1 , p . 543.
2 E . J . W a l l , T he H i s t o r y o f T h r e e C o l o r P h o t o g r a p h y .
1925, p . 378.
d y e m ix tu 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 n ew * ^
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 lu tio n i s
a llo w e d t o
a d so rb upon a s u ita b le
s u b s ta n c e to
p ro d u c e a c o lo r tr a n s p a r e n c y o r p rim a ry i s n o t r e c o r d e d i n
th 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 i n g n o
c o lo r c h a r a c t e r i s t i c s ,
an d h a v in g th e a b i l i t y
dye i n d i r e c t p r o p o r tio n to
s e n t,
is
to
a d so rb th e
th e q u a n tity o f m a te r ia l p r e н
t h e n a la w o f t h e L a m b e r t - B e e r f o r m m i g h t a p p l y .
th e p u rp o se o f t h i s
s ta n c e ,
in v e s tig a tio n to p re p a re
It
su ch a su b н
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 in g le d y es and f o r dye m ix tu re s .
D e f in itio n s o f te rm s u s e d .
(1 )
m a te r ia l s u ita b le f o r dye a d s o rp tio n i s
I t is
o f such an e l e c t r o s t a t i c
s o lu tio n have th e a b i l i t y
a d so rb ed to
f o r th e
T he s u b s t a n c e o r
te rm e d a m o rd a n t.
n a tu re th a t c e r ta in dyes in
t o b eco m e i n t i m a t e l y a t t a c h e d o r
th e m a te r ia l w ith o u t e x h ib itin g an y a f f i n i t y
s u r r o u n d i n g m ed iu m i n w h ic h t h e m o r d a n t i s
susн
pended.
^ A s h l e y , S p e c t r o p h o to m e t r i e 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 ; 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 н
e e r in g C h e m is try , A n a l y ti c a l E d it i o n , F e b ru a ry 1 5 , 19 3 9 .
(2)
Io
I
Opacity = incident energy
4-
transmitted energy =
.
(3 ) T ra n sp a re n c y = X
Io
( 4 ) D e n s i t y = l o g 1Q ( O p a c i t y ) = l o g 1 0 { ░ = l o g 1 0 ^
(5 ) A n e g a tiv e
s e p a ra tio n i s
a p h o n o g ra p h ic r e c o r d
o f . a l l p o rtio n s o f a s u b je c t r e f le c tin 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 l o p m e n t o f a p r i n t f r o m a
n e g a tiv e
its
s e p a ra tio 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
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 to
a b o u t 0 .8 0 .
(7 ) C o n t r a s t . i s a m e a su re o f th e r a t e
d e n s ity w ith e x p o su re .
o f change o f
CHAPTER IX
BACKGROUND OP THE ART
P r a c tic e in th e a r t .
E x p e rie n c e i n
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
c o lo r p h o to g ra p h н
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 ,
g ra in le s s .
tu re ,
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
a h ig h tr a n s p a r e n c y ,
o r dyes u sed .
p ro c e d u re in
im a g e , i n
s tru c н
and a g r e a t a f f i n i t y f o r th e dye
S e v e r a l su c h m o rd a n ts a r e a v a i l a b l e ;
s e c u r i n g a d y e im a g e i s
s ilv e r,
and
a s fo llo w s .
and th e
A p o s itiv e
i s p ro d u c e d b y e x p o su re o f th e p o s i t iv e
th ro u g h a s u i t a b l e n e g a tiv e
s e p a ra tio n ,
re d u c tio n o f th e exн
p o s e d s i l v e r b r o m id e b y a s t a n d a r d d e v e l o p i n 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 lo p in g s o l u t i o n a n d t h e n r e н
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
th io s u lfa te .
i n a s o l u t i o n o f s o d iu m
A f t e r w a s h i n g t h e r e s i d u a l Hh y p o n f r o m t h e
p r in t,th e
r e m a i n i n 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 b e
c o lo re d .
T h is p o s i t i v e
s i l v e r im a g e i s
a b le c h e m ic a l tr e a tm e n t to
s ta tic
a m o rd a n t h a v in g an e l e c t r o н
c h a rg e o f su c h a m a g n itu d e a s t o
, firm ly c e r ta in
c o n v e rte d b y s u i t н
ty p e s o f d y e s.
a t t r a c t and h o ld
T he 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 in v o lv i n g t h e o x i d a t i o n
o f th 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 io n , th ro u g h
m ass a c tio n and s o l u b i l i t y p ro d u c t p r i n c i p l e s ,
v e r s a l t in to
th e d e s ir e d s u b s ta n c e .
o f th e
N ot o n ly i s
s ilн
th e subн
s ta n c e im p o rta n t, b u t a ls o
th e e x a c t fo rm i n
l a y e r d e te r m in e s t h e m o rd a n tin g a b i l i t y .
th e g e la tin e
S e v e r a l s u c h m o rн
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 io d id e .
The m o rd a n t an d g e l a t i n e
a re w e ll w ashed ,
t h e n im m e rs e 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 t i m e l o n g
en o u g h t o i n s u r e th o ro u g h s a t u r a t i o n o f t h e m o rd a n t.
is
f o l l o w e d b y a w a s h t o re m 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 ere to
th e g e la tin e
s h a r p im a g e , i n c o l o r ,
o r base.
The r e s u l t i s
phenom enon.
T he g e l a t i n e
an e le c t r o s t a t i c
c o a t i n g , i n w h ic h a l l p h o t o g r a p h н
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 lly p o s itiv e
c h a rg e .
n o t th e g e la tin e ,
tiv e
th e
I f th e m o rd a n t i s
l im i ts th e a v a ila b le d y es to th e
a c id ic ,
to be c o lo re d and
c o lo re d io n i n
c h a rg e .
T h is
so c a l l e d b a s i c t y p e i n
s o lu tio n c a r r ie s a p o s itiv e
T he r a n g e o f u s a b l e d y e s , t h e n , i s
g e la tin e
an e le c tr o s ta tic н
a d s o rb in g s u b s ta n c e m u st h a v e a n e g a н
c h arg e and th e d y e s u se d a p o s itiv e
w h ic h t h e
a c le a r,
o f th e o r i g in a l s i l v e r re c o rd .
Dye a d s o r p t i o n b y t h e m o r d a n t i s
ic
T h is -
lim ite d by, f i r s t ,
c h a rg e .
th e
c h a r g e , f o r a s t h e d y e b e c o m e s l e s s b a s i c a n d m o re
th a t i s th e
te n d e n c y to
. th e n e g a tiv e
c o l o r e d i o n b e c o m e s m o re n e g a t i v e , t h e
s ta in in c re a s e s ;
and se c o n d , b y th e
e x te n t o f
c h a r g e u p o n t h e m o r d 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 re tic a l c o n s id e ra tio n s .
I f d i f f e r e n t s i l v e r denн
s itie s
a re
c o n v e rte d to
sam e p a r t i c l e
th e m o rd an t i n a m anner g iv in g th e
s i z e th ro u g h o u t,
an 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
tin e
s ta in ,
c le a r in g th e g e la н
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 l y t o t h e r e s u l t i n g im a g e w h e r e
c ? c o n c e n tra tio n o f dye i n s o lu tio 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
i n a l i n e a r m an n er t o t h e m o rd a n t.
I t w o u ld b e e x p e c te d *
th e n , t h a t th e r a t e
c h e m ic a lly
o f d e crea se 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 н
p o r tio n a l to th e in te n s ity o f l ig 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 ie n c e ,
ence t h i s t h e o r e t i c a l re a s o n in g .
F irs t,
t h a t th e dye s o lu tio n i s p a r t i a l l y
to
in flu н
d ia ly s is in d ic a te s
c o llo id a l.
T h is c o l l o i d н
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 i x i n g , a c i d c o n c e n t r a н
tio n ,
tim e o f s ta n d in g ,
te m p e ra tu re and ty p e o f d y e .
Second
th e q u a l i t y o f m o rd an t v a r i e s a s a f u n c tio n o f te m p e r a tu r e ,
ra te
o f f o r m a t io n , w a s h in g tim e ,
g e la tin e
la y e r.
T h ird , th e ty p e ,
e n d d e p t h o f im a g e i n
th e
age and c o n d itio n o f th e
g e l a t i n e h a s a m ark e d e f f e c t u p o n t h e k in d an 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
T ype o f i m a g e .
To e l i m i n a t e
f a c to r s a s p o s s ib le th e
f o r s tu d y .
a s m an y t r o u b l e s o m e
s i l v e r io d id e m o rd a n t w as c h o s e n
I t is p ra c tic a lly
c o lo rle s s
i n g , b u t a s l i g h t p e a k i n th e y e llo w .
m e rs in g t h e
( s e e F ig u r e 1 ) , hayн
I t i s p r e p a r e d b y im н
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
such t h a t a s th e
s ilv e r is
and io d id e
o x id iz e d by th e io d in e th e r e
is
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
is
fo rm e d .
I t i s p r o b a b ly a c o m b in a tio n o f g e l a t i n e ,
and p o ta s s iu m
s i l v e r io d id e .
th e io d in e i s
re m o v e d i n
a c id ,
A f te r t h i s b le a c h in g a c tio n ,
a b i-s u lfite
s o l u t i o n a n d t h e m o rн
d a n t i s w ashed f o r a s h o r t p e r i o d o f tim e .
T he 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 lo n g e d w a s h in g r e н
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 l l o w ,
opaque s i l v e r io d id e .
I t w as fo u n d t h a t a s u r f a c e
im a g e c o u l d n o t b e t r a n s f o r m e d i n t o
p a r e n t i o d i d e im a g e .
p lie d to
te ris tic s
As a r e s u l t ,
each dye d e n s ity to
show n i n F i g u r e 1 .
s i l v e r im a g e a d j a c e n t t o
th ro u g h th e c e l l u l o i d
su rfa c e ,
c o a rse g ra in e d
s ilv e r
a s a tis f a c to r ily tra n s н
c o r r e c tio n s m u st be ap н
e lim in a te th e m o rd an t c h a ra c н
H o w e v e r, b y p r o d u c i n g t h e
th e b a s e ,
th a t is
b y e x p o s in g
s u p p o r t r a t h e r th a n on t h e e m u ls io n
th e b le a c h in g a c tio n p ro d u c e s a p e r f e c t l y tr a n s -
54
I t
.tn
r.
55
Tiir. rrifts s s r iw f w e e jd r
rr: 5
- L i:.:} ? - 5
L _ i -----
ni
p a r e n t im a g e h a v i n 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
s ity
ra n g e d e s ir e d .
P ro b a b ly th e g e la t i n e
in th e denн
la 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
v e r io d id 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 ,
s ilн
no c o r н
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 ,
and th 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 .
T he p r e p a r a t i o n o f u n i f 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 te r m in e d a m p e rag 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 th e f i l m p l a n e . 4
The l i g h t
p a th i s
i n t e r r u p t e d b y a r o t a t i n g d ru m w h ic h h a s i t s
fe re n c e
c u t in
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 le e x p o su re s a re g iv e n to
tio n .
T he r e s u l t i s
th e film
th a t a s tr ip
b y a s i n g l e d ru m r o t a н
o f film
/in c h e s lo n g i s g iv e n tw e n ty -o n e e x p o s u r e s ,
e ig h t and one h a l f
each d iffe rin g
f r o 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 .
th irty
c ir c u m н
A bout
s u c h e x p o s u r e s w e r e m ade t h 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
film .
T he t h i r t y
fo o t le n g th o f film
w as t h e n
d e v e l o 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 s h e d
and d rie d .
T he d i f f u s e
d e n s ity o f each s te p on each s t r i p
4 C. " b . I f e b l e t t e , P h o to g ra p h y , I t s p r i n c i p l e s
P r a c t i c e . S econd E d itio n ,, p . 211
w as
and
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 r 5 a n d a n y s h 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 .
o b ta in e d i s
lo g lO
sh o w n i n F i g u r e 2 .
(o p a c ity ),
T he d i f f u s e
s trip .
T h is i s
a s ta n d a rd H u rte r and
c u rv e . 5
T he - p r e p a r a t i o n o f t h e d y e i m a g e .
film
d e n s ity , D *
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 s u re
v a lu e s g iv e n th e f ilm
D riffie ld
A s a m p le o f t h e t y p e o f s t r i p
E ach s t r i p
of
w as t r e a t e d a s f o l lo w s :
(a )
W ash - - - - - - - - - - - - - 5
m in u te s
(b )
B le a c h - - - - - - - - - - - - 5
m in u te s
KI - - - - - - 5 0 .0
A l p ( S 0 4 ) q * 1 8 Ho 0 - 1 0 . 0
CH3 CO0 H - - - - 5 .0
CHgCOpNa - - - - 5 .0
'S o l u t i o n - - - - 1 .0
(c)
C le a r- - - - - - - - - - - -
g ra m s
g ram s
g ra m s
ml
g ra m s
lite r
0 .5 m in u te s
NaH S 0 3 - - - 1 0 . 0 g ra m s
S o lu tio n - - - - 1 .0 l i t e r
(a)
W ash - - - - - - - - - - - - 0 . 5
(e)
Dye
- - - - - - - - - - - -
5 m in u te s
(f)
W ash - - - - - - - - - - - -
15 m in u te s
(g )
D ry
20 m in u te s
- - - - - - - - - - - -
m in u te s
5 E a s tm 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 ra c tic e .
5 C. B. K e b l e t te , P h o to g ra p h y . I t s P r i n c i p l e s an d
P r a c ti c e . Second E d itio n , p . 211.
..
IRE
V
CM:
o il 7
10
U n if o r m f l o w , a g i t a t i o n
ta in e d .
and te m p e ra tu re
T he d y e s o l u t i o n s w e r e m ade u p i n
fo rm , im m e d ia te ly d i l u t e d to
s tr ip s dyed.
b lu e .
c o n c e n tra te d
th e d e s ir e d s tr e n g th s and th e
Two d y e s w e re u s e d , a u r o m in e 0 , a n d t h i o n i n e
T h e y w e re c h o s e n f r o m t h e
s t a n d p o i n t o f fo rm 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 ra te
( 6 5 * P ) w e r e m a in н
and b ecau se t h e i r sepн
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
h3cmA
w
r
r
H>
s p e c tru m .
H N /y S y 'V M x
A u ro m in e O
T h i o n i n e B lu e
T he 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 ta n d a rd S o lu tio n s
( a ) A c id
CH oC O oH
S o lu tio n
10 m l
- - - 1 .0 l i t e r
(b) Dye
CHoOH----------------------3 3 m l
CH3 CO2 H -------------- 1 0 m l
Dye - - - - - 5 g ram s .
S o lu tio n - - - - 1 .0 l i t e r
(2 )
M e th 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 )
T h io m in e
(a)
(b )
(c )
(d )
(e)
4 .0
2 .0
i .0
0 .5
0 .2 5
A u ro m in e
0
0 0
0
0
m l o f s o lu tio n s re q u ire d
T h io m in e
200
100
50 25
1 2 .5
A u ro m in e A c i d S o In
mm
?
?
-
50
150
200
225
2 3 7 .5
( 2 ) M e th o d o f d i l u t i o n
(c o n tin u e d )
D e s i r e d Dye C o n e . ( g / 1 )
T h io n in e
A u ro m in e
(f)
(g )
(h )
(i)
C j)
0 .0
0 .0
0 .0
0 .0
0 .0
4 .0
2 .0
1 .0
0 .5
0 .2 5
00
(1 )
(m)
(n )
Co)
4 .0
2 .0
1.0 0 .5
0 .2 5
4 .0
2 .0
1 .0
0 .5
0 .2 5
m l o f s o lu tio n s re q u ire d
T h io n in e
?
?
200
100
50
25
1 2 .5
T he 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 s .
A u ro m in e A c i d S o l n
200
100
50
25
1 2 .5
50
150
200
225
2 3 7 .5
0 .4 g
100
50
25
1 2 .5
50
50
150
200
225
T he a v e r a g e p i c н
t u r e ra n g e e x p re ss e d a s s i l v e r d e n s ity o f a c o lo r s e p a r a tio n
p o s itiv e
is
fro m z e ro t o 0 .8 0 .
T he d y e im a g e s w e re o f s a t i s н
f a c t o r y tr a n s p a r e n c y th ro u g h o u t t h i s ra n g e .
w e re c h o s e n f o r s tu d y .
Seven d e n s i ti e s
T he t r a n s m i s s i o n a t e a c h w a v e l e n g t h
o f se v e n d e n s i t i e s on f i f t e e n
d if f e r e n t film
s t r i p s w as d e н
te r m in e d b y m eans o f ' th e H a s s le r s p e c tr o g r a p h .?
f r o m 4 2 5 t o 6 7 5 mu w a s s t u d i e d s i n c e t h i s i s
tio n o f th e v i s i b l e
f o llo w s .
s p e c tru m .
A ra n g e o f
t h e m a in s e c н
T he s p e c t o g r a p h f u n c t i o n s a s
L ig h t fro m a n in c a n d e s c e n t t u n g s t e n s o u rc e a t
3000* K p a s s e s t h 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 b eam t r a v e l s t h r o u g h
t h e s a m p le a n d r e t u r n s t h r o u g h a f i x e d r o t a t i n g
s e c to r to
th e
V P u b l i c a t i o n s o f The 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 os A n g e le s .
i n i t i a l p la n e , w h ile th e o t h e r h a l f p a s s e s th ro u g h th e
c le a r film
tio n
base,
and s ta in ,
t o r to
to
e lim in a te th e e f f e c t s o f s u rfa c e r e f l e c н
and r e t u r n s th ro u g h a v a r i a b le r o t a t i n g
th e o r ig in a l p la n e .
a d ju s te d to
T h is v a r i a b l e
s e c to r can be
a llo w t r a n s m i s s io n s o f fro m z e ro to
p e r c e n t o f th e in c id e n t l i g h t .
p a s s th ro u g h th e s l i t
one h u n d re d
T he tw o a d j a c e n t b e a m s now
an d o n to t h e g r a t i n g .
The r u l e d co n н
cav e g r a t i n g h a s tw e n ty - f o u r th o u s a n d l i n e s p e r in c h ,
th ro u g h th e phenom ena o f i n t e r f e r e n c e r e f l e c t s
m i t t e d l i g h t b a c k to . t h e
secн
and
th e t r a n s н
c am era p la n e a s a s p e c tru m w ith a
l i n e a r d i s p e r s i o n o f 6 A n g s tr o m s p e r m i l l i m e t e r .
p a n c h r o m a tic m o tio n p i c t u r e
film
is
u se d in th e
O rd in a ry
c am era .
The
tw o b e a m 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 ro o m f o r t e n
w id th .
such re c o rd in g s a c r o s s th e f ilm
T he e x p o s u r e r e q u i r e d i s
about fiv e
s h u t t e r i s p ro v id e d i n f r o n t o f th e
seco n d s,
a n d .a
s l i t f o r t h i s p u rp o se .
T he p a n c h r o m a t i c s t o c k c a n b e d e v e l o p e d i n a c o n t i n u o u s
t y p e d e v e l o p i n g m a c h in e .
T he tw o b e a m s o f l i g h t h a v e p r o н
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
su re .
expoн
T he w a v e l e n g t h 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 н
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 th e v a r i a b l e r o t a t i n g
s e c to r.
By s u i t a b l y m a r k i n 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 t e r m i n e d v i s u н
a lly ,
a tr a n s m is s io n c u rv e o f th e
p a n c h ro m a tic n e g a tiv e s to c k .
s a m p le i s
e v id e n t on th e
T he w a v e l e n g t h s c a l e m ay b e
13
p h o to g ra p h e d b y th e i n i t i a l e x p o su re o r d e te rm in e d l a t e r b y
re fe re n c e to
a c a lib ra te d
I I ..
s c a le .
TREATMENT OF BATA OBTAINED
F i g u r e s 3 t o 2 3 sh o w t h e r e s u l t s o f o n e h u n d r e d f i v e
d e te rm in a tio n s o f te n
s p e c tro g ra m s e a c h .
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
F ig u re s 3 to 9
16 r e p r e s e n t a u r o m i n 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 .
te d f o r each o f th e
seven d e n s itie s ,
as tra n s m is s io n v e rs 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 .
is tic s
T hey a r e p l o t н
T he c h a r a c t e r н
o f th e b lu e , y e llo w and g r e e n c o lo r s a re e v id e n t.
R e la tio n f o r a s in g le d y e.
o f a re la tio n s h ip
To d e t e r m i n e t h e v a l i d i t y
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 iv 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 tra tio n o f th io n in e .
to
37, is
T he r e l a t i o n
l o g |0c - - m T + b .
f o u n d , F i g u r e s 24
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 lid
a t e a c h w a v e le n g th c o n s id e r e d .
t h a t th e s lo p e ch an g es i n
I t w ill be n o tic e d
a r e g u l a r m anner w ith s i l v e r d e n s iн
t y . ' T h i s 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
fu n c tio n o f s i lv e r d e n s ity .
fro m th e
c u rv e s,
u r e s 24 to
3 7 ).
T he c o n s t a n t s w e re e v a l u a t e d
and a re l i s t e d
a s su ch on each s h e e t (F ig н
F i g u r e s 3 8 t o 4 0 show t h a t l o g D = m, K + b , .
T he v a l u e s o f m, a n d b, w e re d e t e r m i n e d f r o m t h e c u r v e s ,
th e
c o rre s p o n d in g v a lu e s o f m and b r e p la c e d i n
and
th e i n i t i a l
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╗лr
TM U
A ;
o
o
t,O G
W
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*0
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6O
&o
90
% T/?e= tN S M t s s i o t /
<r-/ CU /r fi
MSTQ
! TH!/
//B O
3 .158
8 .33
8.00
fBZO
2. O
s& 8
/.V /
?S'. S 3
icp.sv
a: 70
VO
-*-0
T/P&/VS/S7/SSSOA/
1$ss
LO G DENSITY
0 9t P q
COAtS T G N T
HCOPE 38
to
DENSITY
Ot
LO Q
p icoee
Jy 6 0 0 B
T 6 Q0 Q
?JrbSO*-
s s
10
^й<5
DBMS ITV
CQ>?
s ╗>
05
03
CONSTANT
14
e q u a tio n
(T a b le s 1 an d 2 ) .
g iv e n w a v e le n g th i n
s i l v e r d e n s ity ,
T h is r e s u l t s i n
te rm s o f tr a n s m is s io n ,
and c o n s ta n ts .
an e q u a tio n a t a
dye c o n c e n tr a tio n ,
B y c o m p a r i s o n w i t h t h e Lamн
b e r t - B e e r fo rm :
T
-
T
-
e
- k c D
s ta n d a rd
l o g ^ c + K q lo g l^ K g D e r i v e d
K gltogD * K4
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
d a n t c o n c e n tra tio n and s o lu tio n
A p p a re n tly th e
c o n c e n tra tio n d o es n o t h o ld .
s i l v e r i o d i d e m o r d a n t , w h i l e 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 ifo rm p a r t i c l e
th e
s i l v e r d e n s ity i s
d a n t.
to
w as su c h t h a t th e
a g g re g a tio n
such t h a t
t h e m o rн
o f c o u r s e , m ay p e r m i t som e o f t h e
l e a v e t h e m o r d a n t? h o w e v e r , t h e t i m e c h o s e n
s t a i n w o u ld w a s h 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 .
g iv e a f a i r
s iz e
n o t tra n s fo rm e d l i n e a r l y in to
T he w a s h in g t im e ,
dye p a r t i c l e s
e q u i v a l e n c e o f m o rн
D o u b le t h i s w a s h i n g t i m e w o u ld s t i l l
c o l o r i m a g e , h e n c e n o t t o o m uch e r r o r w a s i n t r o н
duced th e re .
I t w i l l be n o tic e d th a t th e
T a b le 2 , v a r y i n
a re g u la r o rd e r.
c o n s ta n ts o f th e
e q u a tio n s ,
F i g u r e s 4 1 t o 4 3 sh o w 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 asm u ch a s
a l l c a lc u l a t i o n s a re b a se d upon e x p e rim e n ta l d a ta ,
and any
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 l d b e so m e w h a t m a g n i f i e d b y c a l н
c u la tio n s advanced to
p o in ts f a ile d
l
to
t h is p o in t,
f a l l upon th e
t h e f a c t t h a t o n e o r tw o
c o n s tr u c te d c u rv e w as d i s r e -
EVALUATION
/<0 &Io'"c "
T -rt>
LOG,0D = ^
H SO s w M .:
BLUE
t-EO syrt M! YELLOW
ysO sm M -:
GREEN
5 0 0 r-r^M. -. BLUE
500 ^ X M .
yello w
5 0 0 smM.'. GREEhJ
5 2 S sy~
OF m O N D b O S A FUNCTION OF D
vl.
YELLOW
SSQ
srriM*: BLUE
550
sm
,(
OR b )
t
bt
J
H E N C E ( s r r v OR b ) =
LOG0-/75
0.34%
0-2.52
7 ^3
^ y n .- LO G D -0.732
0.177
LCG
0
-0
.9
0
4
0.476
LQ(y D ' ░ b d 5
-Z.3J
L=
L O G O - 0 , 0 /4 7
- 0 .3 3 4
1
6=
LOGO- 0 . 5 7 7
0.449
~
-
LOG Q - 0 . 3 0 *
-0 .4 3 5
L0 & D ~ L it
0. 18 /
6=
LOG D - 0 . 7 3 4
-0.690
L O G O - LOO
0 .5 5 5
6=
LOGO- 0 .6 7 5
-0 .4 3 5
L 0 6 0 -1 .2 9
0.7 /4
6 =
LOGO-0 .6 3 0
-0.7 6 6
t> =
LOG D - 2 . 6 0
-0 .6 0 6
LOO 0 - 2 . 5 9
0.58%
L O G O -2.20
1.H9
LOG D - 2 . l l
I.2 B
bOOsrr^M: B L U E
600 srr\M*i YELLOW
LOG P
-
eO
LO G O - 1.82
6 0 0 sv*.m.: GREEN
1.22
6 =
/> =
b b =
L O G O - 0.805
-A 0 9
LOO P - 0 . 4 2 8
7/ , v l
LOOP-
__
LOOP-0.277
-A20
L0G D -J.7 8
1.22
b=
LOOP- 0 . 0 8 4
-A /6
^ L0G0-<*=>
b -
LOOP-
650smM- '? BLiUE
oo
green
b=
5
fc>=
0.732
0.462
5 5 0 smM.: GREEN
6 5 D /v > ^ ^ c :
LOGO-2 .8 2
-0.513
LOOP-
YELLOW
6>50/yr*M,: YELLOW
k1
LOG
L 0 г iaR Z -k<..
-
LOGO-3.12
1. 8 2
T/9&LE/
<*л
LOG P - 0.075
-0 .4 3 5
Cq-)
H 50
sw aC
:
SOO /m il;
L O G c * ?/ L░6P -fl.9Q 5 \
(
LOG
600
) T ^ C ^ O ^s f - Z 2 )
to o C ~ - f ^0 3 tf8 75
0X76
LOG C ╗
'
LOG r ╗
v
о
(c t)
-2.7?,'T'L,0<o D + S O ^ T - / . 9 5 LOG D + 5 . 5
?) = -ZtO-T-LOG-D +I.3T - 2.25 LOCrD + J.3
=
? ?' 7 . ) T ~>- / l*POO~QH3 \
'
- /.е 3
'
IZ 2
(c)
/ lo(j p-n.57\
} T + (-
-) T + ^i i g f r P ^ ' 6 3 - )
C╗
=
GO
J r ^ /LOGV-OMSl ) i
V r/^ g /
? IMO'T' L O G O + 7 , 8 / T - f.Z 7 LOG D - + O . 8 0
_ a ?78-T-hOG- D + J .7 0 T -0 .7 0 LO G O + 0 . 3 0
_ n . * 7 .T LOG D + ). 6 2 T - 0.86 LOG D+ 0.07
- 6 SV
-/е 0 2
е68
(c> =
' * " ?'-1 9 8 5
780
(d) ?
?
620
89
EQUATIONS
RELATiM&
T* t OYE CONCENTRATION. ANO D
FOR THlONlNE
(* .)
LOO C =
50^ * :
00& c
S Z S ^ m . . L#
S S O /rx-M .
6
C =
T + ( ^ ~
~
|^ )
e ░ t^ 2)T
i.d f '.c - ? A j O f r P - 2 . 5 9 'j --
^
0.588
/
/
I
/6 0 6 P -2 .6 O 1 _
- O.60b
(a ,) ?
too
(d ,)
- 2.3 -606 D + 0 .7 0
6 0 6 P-A 675 \ _ _ ; 0 .7 ; /,^G P f- / 0 O r - 2-3
-0 H S 5
I
░
\
_
/70
7:
p
^
7 /0
^ -7 0 6
83
( d i ) =?
- 389
/a s
HQ UA TfONS
P E L flT lM G
Tx , DYE C O h/C Eh/TRBT /O N , a n d
TRBLE 2 CcOKO-'e)
+ /.л*?
6 0 6 P -f H .d T ~ 1 .& 5 LiOG> D + V . 2 8
/
- ///V
-372
(b,) =
(c ,) =
Cc.)
= -ftW -TM S D + /-76T - 0.7*r OOOD + 0 .5 0
= - * '8 - T - t 0 6 0 + /.37T
+
- /1 0 6 D - /.0 0 \ y
v 0.555 / '
(b .)
D
FO R AVROMI NE
/L 0 6 t> -0 .7 3 2 \
^50/rruM ^: L O G { ^ ~ j ~ - ' t ?
S O O ^ m .: i Z t e ( - S i ^ j =
------ / T
(aa )
_
/ L O C P - 0 ,0 l& \
+ (
(bj
_
C cJ
_
^
UJ
: ^ 3 3 ^ ? / = ~ & .6 T LO G O + H. 1 0 T - 3 . 0 LOG D + 0 . 4 8
~ ( ~ ░ | y B/ -? j T +
"
S S O ^ L O G ^ Y - - (W f^ ? SL)7 +
- I - 2 6 T L 0 G P + I M Z T - I HS LOG D + O .l*
= -O MT LOGOtLSr -0.92 LOG 0+0.9*
600s~,M.: wg(\ ^2, s)=
- ( M ??fcfc
? ^ H ) T + ( - 0 ^ U 6 2 7 7 ' ) = ? o e 2 'T - L O l i D + , 5 T -░-83LOGD. az3
/
6 5 - 0 ^ ^ ; lC o (?^ < ) ,
( L0C? g ? K
) T+(
- -ri.3 9 ~
*-y╗?
(W
^y~OMs+ 210
soo
(.60 =
S Q O A T i O N S RELATING-
= ^ ? 5 5 ',T' 4 0 6 D + I . 7 / T - 0 - 7 ? LOGO + 0.10
6*7
s~\
{ax)~
(<?0 л
)
/2 7
?838
*60
700
-608
} DYE CONCENTRATION, AND 0 #r0г THIONINE- AUROMINE MIXTURE
T8BLE Z ( C 0 N T P )
?
?r:
T?
Sj : n b j .^ k o :
15
g a rd e d .
T he e v a l u a t i o n o f t h e c o n s t a n t s f r o m t h e
s u lts in
one s in g le
e q u a tio 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 lu e o n to a s i l v e r io d id e m o rd a n t i n
c o n c e n tra tio n ,
A rb itra rily
c u rv e s r e н
te rm s o f dye
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 .
ch o sen v a lu e s o f c , A , and D r e s u l t i n
a c a lc u н
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 im e n ta lly d e te rm in e d v a lu e .
R e la tio n f o r th e dye m ix tu re .
a s a d o tte d lin e ,
d i v i d u a l y e llo w
th e
F i g u r e s 4 4 a n d 4 5 sh o w ,
c a l c u l a t e d s u m m a tio n e f f e c t o f t h e i n н
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 .
d e fin ite
th is
d i s c r e p a n c y a t lo w w a v e l e n g t h s .
e ffe c t,
g a te d to
th e y e llo w
re a c h e s 1 .0
a
To b e t t e r s t u d y
an d g r e e n dye c u rv e s w e re i n v e s t i н
o b ta in r e la tio n s
t i o n w as fo u n d to
T h ere i s
e x is t.
as aoove.
T h e sam e f o r m o f e q u a н
S i n c e t h e a u r o m in e t r a n s m i s s i o n
a n d re 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 som e
s p e c tra l ra n g e ,
th e d e riv e d r e l a t i o n
fa ils
tra n s m is s io n i s
in d e p e n d e n t o f c o n c e n tr a tio n .
s t a n t s do n o t sh o w a s g o o d l i n e a r r e l a t i o n
n in e , hence th e r e s u ltin g
a t t h i s p o in t;
The f i n a l c o n н
a s f o r th e th io н
e q u a tio 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 io n r e p r e s e n t i n g t h e
dyes i s
s u b je c t to
p ro b le m h e r e i s
c e n tra tio n
c o m b i n a t i o n o f t h e tw o
th e above p lu s an a d d itio n a l e r r o r .
one o f p a r t i t i o n .
e q u ilib riu m
T he
T he tw o m u s t r e a c h a c o n н
d e p e n d in g upon th e a f f i n i t y
o f each
FtN f)l
T H IO N IN E :
m ir o m in e :
EQ U ATIO N S
LOG*lOCT = 7 o o o (j-3<r*T?t 0 ^ D 4' ? -<3T^ l z 8 Ll0^ oD + , l ^ ) + <?.08-T U 06D + 3 .0 T + 2 .5 5 LO G O -╗6.9 7
log c r
MIXTURE i LOG^?
lo з o " (,0,1:1*OGr.D 42.?╗9T +/2.O 6L06D -7.е/j + 7W8 T lJ0G!)D +3.G T +9. 52 L O G O - 2 . B 8
1
j = jtfo {7 .8 8 -T L O C JO -2 .0 T + 3 3 5 L O O O + I.b^+ 5.I7< U 0G D+0.H2J +3.22 LOGO +1.15
WHME; C=? DYE CONCENTRATION IN GRAMS PER. LITER
X - WAVELENGTH I N /rv n j a .
T- T R A N S M I S S I O N AT A
t>= INITIAL SILVER DENSITY
TABLE
3
tv
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O
f
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CM
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of
t
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16
f o r th e
s i l v e r i o d i d e im a g e .
U n l e s s t h e y h a v e e q u a l m o rн
d a n tin g pow er one w i l l p re d o m in a te .
p u t in to
b ile
th e w ash ,
if
th a n th e o th e r ,
th e
W hen t h e d y e d s t r i p
o n e d y e i s m o re s o l u b l e ,
i t w i l l w ash o u t f i r s t ;
is
o r m o re moн
th u s a l t e r i n g
c o n c e n t r a t i o n s a r o 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 is p la c e m e n t o f one d y e .
fu n c tio n o f d e n s ity
T h i s e f f e c t w o u ld b e s o m e w h a t a
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
to p a s s th ro u g h a g r e a t d e a l o f th e e q u ilib r iu m m ix tu re 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 .
As se en by th e i n i t i a l c u rv e s th e r e
lo w d e n s i t i e s t o
tie s
is
a te n d e n c y f o r th e
s h i f t to w a rd t h e b lu e w h ile th e h ig h d e n s i н
re m a in g r e e n .
A p p a r e n tly t h e y e llo 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 н
tra tio n s .
T h is phenom enon 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 te d
b y a s in g le m a th e m a tic a l e q u a tio n ;
e q u a t i o n s sh o w t h e
p ro b a b ly c o r r e c t,
sam e g e n e r a l f o r m ,
s i l v e r io d id e
and in t h a t th e y a re
th e y a re n o t r e l i a b l e
o f th e fo u r v a r ia b le s .
th e
a n d a l t h o u g h t h e tw o
fo r a ll
c o n d itio n s
I f tw o d y e s o f e q u a l a f f i n i t y
c o u ld b e fo u n d ,
a m uch m o re r e l i a b l e
fo r
re la н
t i o n m ig h t b e d e d u c e d .
V is u a l i n t e n s i f i c a t i o n .
So f a r ,
th e
m e t r ic r e s u l t s h a v e b e e n c o n s id e r e d fro m th e
a g ro u p o f i n d i v i d u a l w a v e le n g th s .
tio n ,
d e te rm in e d a s f o llo w s ,
s p e c tro p h o to s ta n d p o in t o f
The v i s u a l i n t e n s i f i c a н
c o n s id e rs th e n e t e f f e c t o f th e
v a rio u s ch an g es in d e n s ity and dye c o n c e n tr a tio n .
F ig u re 46
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
d is tr ib u tio n .о
t iv e re sp o n se
fu n c tio n f o r an e q u a l e n e rg y
T he 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 н
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 itiv ity
o f t h e h u m an e y e w h en v i e w i n g a s p e c t r u m h a v i n g a n e q u a l
e n e rg y e m is s io n f o r e a c h w a v e le n g th .
is
a d e f in ite peak in th e g re e n .
c u rv e w e re m u l t i p l i e d b y t h e
As c a n b e s e e n ,
T he o r d i n a t e s o f t h i s
c o rre s p o n d in g o r d in a te s o f se v н
e r a l o f th e o r ig in a l dye tra n s m is s io n
c u rv e s.
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 ,
r e p r e s e n ts th e
d e n s ity .
to
53,
m e te r .^
e f f e c t se en b y th e
T hese r e s u l t н
e a c h o f w h ic h
ey e v ie w in g t h e g iv e n dye
T h e se 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 ,
and th e
F ig u r e s 47
a r e a s u n d e r e a c h d e te rm in e d w ith a p l a n i -
T h e s u 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 th e a re a u n d e r th e
c u rv e ,
r e p r e s e n ts th e t o t a l o r i n t e н
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 h u m an e y e .
d iv id e d in to
is
th e re
th e a re a u n d e r th e
T h is v a lu e
a v e ra g e v i s i b i l i t y
fu n c tio n
an 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 .
In f a c t,
ib le
t h i s v a lu e i s
e n erg y .
by v irtu e
I f th e
th e r a t i o
o f re la tiv e
log-^Q o f t h i s r a t i o
o f th e d e f in itio n on page 3,
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
j
a m o u n ts o f v i s н
be c o n s id e re d ,
th e n
th e r e s u l t i n g v a lu e i s
( s e e T a b le 4 ) .
7~ w7 T . W a ls h , P h o t o m e t r y . 1 9 2 6 , p .
295.
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 ril 1934;
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 t e r m i n a н
t i o n o f T o n e I n t e n s i f i c a t i o n i n C o l o r M o tio n P i c t u r e F i l m .
In o t s <r
v<3/ sT/e*SN&&u.
- ;:u
1 1
:i n
i. :
2L
i.r;
/V O /S B / W f f
X N 3 >3*34
I
I
i
TABLE 4
DATA FOR IN TEN SIFICA TIO N CURVES
D e n s ity = 0 .6 6
0 .2 5
0 .5 0
1 .0
2 .0
4 .0
g /1
g /1
g /1
g /1
g /1
T.
T.
T.
T.
T.
A re a i n
sq u a re
in c h e s
A r e a of*
a v e ra g e
v is ib ility
c u rv e s
Q u o tie n t
I
T
D e n s ity
I
1 0 g lo rji
8 .8 9
7 .0 4
6 .1 2
3 .8 7
1 .9 1
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 .4 3
1 .8 0 5
2 .0 8
3 .2 9
6 .6 7
? 0 .1 5 5
0 .2 6
0 .3 2
0 .5 2
0 .8 2
1 0 .0 6
8 .7 2
7 .8 7
6 .3 5
4 .3 0
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 .2 6 8
1 .4 6
1 .6 2
2 .0 1
2 .9 6
0 .1 0
0 .1 6
0 .2 1
0 .3 0
0 .4 7
1 2 .0 7
1 1 .6 9
1 1 .2 8
1 0 .3 0
9 .3 7
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 .0 5 5
1 .0 9
1 .1 2 7
1 .2 3
1 .3 6
0 .0 2
0 .0 4
0 . 05
0 .0 9
0 .1 3
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2 -.
1 2 .7 2
1 .0 3
1 .0 6
1 .1 0
1 .1 3
1 .1 7 4
0 .0 1
0 .0 3
0 .0 4
0 .0 5
0 .0 7
D e n s ity * 0 .1 2
0 .2 5
0 .5 0
1 .0
2 .0
4 .0
g /1
g /1
g /1
g /1
g /1
T.
T,
T.
T.
T.
D e n s ity * 0 .6 6
0 .2 5
0 .5 0
1 .0
2 .0
4 .0
g /1
g /1
g /1
g /1
g /1
A.
A.
A.
A.
A.
D e n s ity л 0 .1 2
0 .2 5
0 .5 0
1 .0
2 .0
4 .0
g /1
g /1
g /1
g /1
g /1
A.
A.
A.
A.
A.
1 2 .3 1
1 2 .0 0
1 1 .5 2
1 1 .2 9
? 1 0 .8 2
D e n s ity ╗ 0 .6 6
0 .2 5 g / 1 eac h
0 .5 0 g /1 e a c h
1 .0
g/1 each
2 .0
g/1 each
4 .0
g /1 each
D e n s ity ╗ 0 .1 2
0 .2 5 g /1
0 .5 0 g / 1
1 .0
g/1
2 .0
g/1
4 .0 g /1
each
each
each
each
each
8 .4 7
5 .3 7
4 .7 2
2 .5 4
0 .5 0
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 .5 0
2 .3 7
2 .7 0
5 .0 0
2 5 .4 2
0 .0 6
0 .3 7
0 .4 3
0 .7 0
1 .4 1
1 1 .5 5
9 .2 1
7 .3 6
5 .3 1
3 .3 1
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 2 .7 2
1 .1 0
1 .0 8 7
1 .3 6
2 ? 39
. 3 .0 2
0 .0 4
0 .0 4
0 .1 3
0 .3 8
0 .4 8
18
F i g u r e 5 4 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 in s t dye c o n c e n tra tio n f o r s e v e ra l i n i t i a l
tie s .
T he 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
t h e d y e im a g e s ,
is
and s in c e
s i l v e r d e n s iн
in te n s ific a tio n s o f
th e s e v a ry w ith s i l v e r d e n s ity ,
e v id e n t t h a t a s im p le e x p o n e n tia l f u n c t i o n
L a m b e r t - B e e r la w c a n n o t h o l d .
s im ila r to
it
th e
F i g u r e 5 5 sh o w s t h e v i s u a l
d e n s ity in c r e a s e w ith s i l v e r d e n s ity f o r s e v e r a l dye c o n cen н
tra tio n s ,
w h ile F ig u re
56 s u m m e r iz e s t h e s e r e s u l t s b y sh o w н
in g th e r a t e s o f change o f th e s e
e tX o
Hl d
cdTm,
-
1 -6 .
o t D - 0 .3 3
It
se v e ra l fa c to rs .
S c f = ░ - 13
c c t- o
can be seen th a t f o r in d iv id u a l d y es,
in te n s ific a tio n
is
t h e (g fis u a l
i n c r e a s e d m uch m o re 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 th a n b y c h a n g in g d y e c o n c e n tr a ti o n .
tu re
0 .0 3
d a ta a re g iv e n , b u t th e p o in ts f a i l to
lin e a r v is u a l d e n s ity change.
T h e d y e m ix fc ^
in d ic a te any
T h is i s p r o b a b ly due to
th e
d i f f e r e n c e i n m o r d a n t i n 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 tu d ie d .
Vi5
Hi
n
S7SO
rrsTw
CHAPTER IV
SUMMARY AND CONCLUSIONS
S um m ary.
I t h a s b een p o s s ib le to
d e riv e
a g e n e ra l
e q u a tio n f o r th e tr a n s m is s io n an d c o n c e n tr a tio n c h a r a c te r н
is tic s
o f s i n g l e d y e s a d s o r b e d o n t o a s i l v e r i o d i d e m o r d a n t,
a s w e ll a s to
fa c to rs
sh o w t h e .t y p e a n d r e l a t i v e
im p o rta n c e o f th e
c o n tro llin g v is u a l in te n s if ic a tio n .
Due t o
d iffe rн
e n c e s i n m o r d a n t i n g a b i l i t y b e t w e e n t h e a u r o m in e a n d t h i o n in e ,
a g e n e r a l e q u a tio n in v o lv in g in d iv id u a l dye c o n c e n tra н
tio n s and r e s u ltin g
B e fo re
im a g e t r a n s m i s s i o n w a s f o u n d u n r e l i a b l 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 н
t i v e m o rd a n tin g p o w er s h o u ld b e a c q u ir e d .
b le to
d e te rm in e r e l a t i v e
I t m ay b e p o s s i н
v a lu 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 im e .
tio n
The c o n c e n tr a н
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 i n g t i m e s s h o u l d b e a n
i n v e r s e m e a su re o f th e te n d e n c y o f th e m o rd a n t to h o ld th e
dye.
M e th o d s o f m e a s u r i n g t h e
dye a re
a p t to
e le c tro s ta tic
c h a rg e on th e
b e m i s l e a d i n g in a s m u c h a s a s u m m a tio n o f
c h a rg e s and 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 r e t h e m o rн
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
th o s e p r e s e n t.
s ib le
to
p a rtic le
To e x t e n d t h i s
a b it fu rth e r,
fro m a l l
i t m ay b e p o s н
d e te rm in e t h e m o le c u la r w e ig h t o f th e a d s o rb e d
b y s tu d y in g m o le c u la r l a y e r s o f th e m o rd a n t.
T he
m ass o f th e m o rd a n t an d a d s o rb e d dye c o u ld b e d e te rm in e d
20.
a n a ly tic a lly *
e ra l fa c to rs
W ith a t h 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
a f u r t h e r a t t e m p t a t s u m m a tio n e f f e c t s
y i e l d a m o re r e l i a b l e
(1 )
A s i l v e r io d id e m o rd a n t w as p r e н
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 ,
to
fo llo w
s h o u ld
g e n e r a l e q u a tio n f o r dye m ix tu re s .
C o n c lu s io n s .
and th io n in e .
sevн
a u r o m in e 0
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 h e g e n e r a l fo rm
T
* lo g ,wc ? Kq lo g ;,D +
% 1 0 g|t>D - K4
r a t h e r th a n t h e L a m b e rt-B e e r ty p e fo r m u la .
(2 )
F o r s in g le
lo g
C
10
(3 )
d y e s i t w as fo u n d t h a t
? A C k .TLOG 10D ^ K 2T + K ,L O G |0 D * K J-* -K 5 LOG10D *K fcTл- K ,
w h e re c л d y e c o n c e n t r a t i o n i n
g ra m s /lite r
T * t r a n s m i s s io n a t w a v e le n g th A
D = s ilv e r d e n s ity
X * w a v e l e n g t h i n mu
T he sam e g e n e r a l f o r m w a s f o u n d t o
a p p ly to
a
m i x t u r e o f a u r o 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 н
ra c y due to
it
v a ria tio n s in r e la tiv e
w as n o t p o s s i b l e
e q u a tio n to
expand th e g e n e r a l f o u r v a r ia b le
s a tis fa c to rily f i t
(4 )
th e m ix tu re o f d y e s u s e d .
The v i s u a l i n t e n s i f i c a t i o n
w as d e te r m in e d .
s ific a tio n
to
dye a d s o rp tio n ; hence
fiv e
e r change in
o f th e
s e v e ra l dyes
I t w as fo 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 н
tim e s t h a t o f th e
in te n s ific a tio n
a u ro m in e ,
and t h a t a g r e a t н
c o u ld b e p ro 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 ity th a n b y v a ry in g dye c o n c e n tr a tio n .
BIBLIOGRAPHY
A.
BOOKS
G e tm a n , 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 Chemн
i s t r y , 1931.
H a rd y , A rth u r C. and F re d H. P e r r i n , P r i n c i p l e s o f O p tic s ,
1932.
N e b l e t te , C. B ., P h o to g ra p h y ,
Second E d itio n .
Its
P r in c ip le s and P r a c tic e ,
S v e d b e rg , T h e, C o llo id C h e m is try , 1928.
W a ll, E . J . , 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 .
W a ls h , J . W. T . , P h o t o m e t r y . 1 9 2 6 .
B.
PERIODICAL ARTICLES
A s h l e y , " S p e c t r 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 , 11 T h e 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 is try . A n a ly ti c a l E d iti o n , F e b ru a ry 1 5 , 1939.
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 o n e I n t e n s i f i c a t i o n i n C o l o r M o tio n P i c t u r e F i l m , 11
T h e 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 t i o 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 o d ak C o m p an y .
P u b l i c a t i o n s o f The 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 .
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