Eurasi an Journal of Anal yt i cal Chemi st ry

Vol ume 3, N umber 1, 2008

Copyright 2008 by MOMENT
ISSN: 1306-3057
Adsorpti on Study of Cati oni c Surfactants i n Presence
of Dyes on the Cotton/Water I nterface
El ena Iri na Moater, Cri sti ana Rdul escu, Ioni ca Ioni , Ana-Mari a Hossu
U n i v e r s i t y V a l a h i a f r o m T r g o v i t e , F a c u l t y o f S c i e n c e s a n d A r t s , D e p a r t m e n t o f C h e m i s t r y , B l v d . U n i r i i ,
1 8 - 2 0 , T r g o v i t e , R o m a n i a , e - m a i l : i r i n a m o a t e r @ g m a i l . c o m
Abstract
T h e a d s o r p t i o n s t u d y o f s u r f a c t a n t / d y e m i x e d s y s t e m s o n n a t u r a l f i b r e s i s i m p o r t a n t
b e c a u s e t h e s e b i o a c t i v e s y s t e m s u s e d i n d y e i n g p r o c e s s e s m a y r e a c h s u r f a c e w a t e r s a n d h a v e
a c o n s i s t e n t i m p a c t u p o n h e a l t h . T h e c o n t a m i n a t i o n o f s o i l a n d s u r f a c e w a t e r w i t h t h e s t r o n g l y
a c t i v e o r g a n i c c o m p o u n d s ( s u r f a c t a n t s a n d d y e s ) w a s r e c o g n i z e d a s a n i m p o r t a n t p r o b l e m i n
t h e l a s t y e a r s .
B y U V - V I S s p e c t r o p h o t o m e t r y a n d s u r f a c e t e n s i o n m e a s u r e m e n t s t h e f o r m a t i o n o f
c o l l o i d a l a s s o c i a t e s b e t w e e n c a t i o n i c s u r f a c t a n t s a n d d y e s u s e d f o r d y e i n g o f f i b r e s w a s p u t i n
e v i d e n c e . A c l e a r d i f f e r e n c e b e t w e e n t h e a d s o r b e n t s y s t e m i n t h e c a s e o f m o n o m e r s u r f a c t a n t
a n d t h e a d s o r b e n t s y s t e m i n t h e p r e s e n c e o f t h e d y e i n s o l u t i o n w a s f o u n d b y c a l c u l a t i n g t h e
s u r f a c e o c c u p i e d b y s u r f a c t a n t m o l e c u l e s o n t h e c o t t o n / w a t e r i n t e r f a c e . T h e t y p e o f i n t e r a c t i o n
a n d t h e o r g a n i z a t i o n m o d e o f s u r f a c t a n t - d y e c o m p l e x e s o n t h e c o t t o n / w a t e r i n t e r f a c e w e r e
e s t a b l i s h e d b y t r e a t i n g t h e o r i g i n a l d a t a u s i n g c l a s s i c a l a n d r e c e n t e q u a t i o n s o f a d s o r p t i o n
i s o t h e r m s ( F o w l e r - G u g g e n h e i m , L a n g m u i r )
Keywords: A d s o r p t i o n , c o t t o n , d y e , c o m p l e x s u r f a c t a n t - d y e , c a t i o n i c s u r f a c t a n t
1 . Introducti on
T h e a d s o r p t i o n o f s u r f a c t a n t s i s a p r o c e s s w i t h c o n s i d e r a b l e a p p l i c a t i o n i n d e t e r g e n c e ,
f l o t a t i o n , p h a r m a c e u t i c a l i n d u s t r y , c o s m e t i c s , d y e s i n d u s t r y , f o r s t a b i l i z a t i o n o f c o l l o i d a l
s o l u t i o n s a n d d i s p e r s i o n s [ 1 ] .
I n g e n e r a l , t h e a d s o r p t i o n i s o t h e r m s o f i o n i c s u r f a c t a n t s a t a s o l i d / l i q u i d i n t e r f a c e a r e
c h a r a c t e r i z e d b y s e v e r a l r e g i o n s . T h e m o r p h o l o g y o f a d s o r b e d s t r u c t u r e s a s s o c i a t e d w i t h e v e r y
r e g i o n w a s d e s c r i b e d f o r t h e f i r s t t i m e i n [ 2 ] . S y s t e m s w i t h m o r e r e g i o n s o n t h e a d s o r p t i o n
i s o t h e r m s a r e : a n i o n i c s u r f a c t a n t s o n a l u m i n a [ 3 ] , c a t i o n i c s u r f a c t a n t s o n s i l i c a [ 4 ] , a n d c a t i o n i c
s u r f a c t a n t s o n m e t a l l i c o x i d e s [ 5 ] .
114 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
A l t h o u g h t h e r e a r e m a n y s t u d i e s o n t h e a d s o r p t i o n o f s u r f a c t a n t s o n s o l i d s f r o m s o l u t i o n ,
t h e i n t e r e s t f o r s u c h s t u d i e s s t i l l p e r s i s t s .
T h e a i m o f t h i s a r t i c l e i s t o d e t e r m i n e t h e s h a p e o f a d s o r p t i o n i s o t h e r m s f o r s o m e
c a t i o n i c s u r f a c t a n t s o f a l k y l p y r i d i n i u m c h l o r i d e t y p e i n a q u e o u s s o l u t i o n a n d i n p r e s e n c e o f d y e s
a t t h e c o t t o n / w a t e r i n t e r f a c e , a s w e l l a s t h e i n t e r a c t i o n t y p e a n d t h e o r g a n i z a t i o n m o d e o f
m o l e c u l e s i n t h e d i f f e r e n t a d s o r p t i o n s t e p s .
F o r q u a n t i t a t i v e m o d e l i n g o f t h e s u r f a c t a n t a d s o r p t i o n p r o c e s s i n a q u e o u s s o l u t i o n a n d
i n t h e p r e s e n c e o f a d y e a t t h e c o t t o n / w a t e r i n t e r f a c e , s p e c i f i c m o d e l s o f s u r f a c t a n t a d s o r p t i o n
o n s o l i d s w e r e v e r i f i e d ( F o w l e r - G u g g e n h e i m a n d L a n g m u i r ) . C a t i o n i c s u r f a c t a n t s u s e d w e r e
c h o s e n b e c a u s e o f t h e i r b a c t e r i o s t a t i c a n d b a c t e r i c i d e p r o p e r t i e s .
2. Experimental
2.1. Materials and methods
T h e u s e d c a t i o n i c s u r f a c t a n t s a r e a l k y l p y r i d i n i u m c h l o r i d e s d e n o t e d a s C
m
P
y
C l , w h e r e m
= 1 0 , 1 2 , 1 6 ; t h e s e c o m p o u n d s a r e o b t a i n e d f o r t h e f i r s t t i m e b y W i l l i a m s o n s y n t h e s i s [ 6 ] .
C r i t i c a l m i c e l l a r c o n c e n t r a t i o n v a l u e s a t t h e l i q u i d / g a s i n t e r f a c e f o r a c a t i o n i c s u r f a c t a n t
s e r i e s o f a l k y l p y r i d i n i u m c h l o r i d e t y p e a r e p r e s e n t e d i n T a b l e 1 .
Table 1. C r i t i c a l m i c e l l a r c o n c e n t r a t i o n v a l u e s ( C M C ) f o r c a t i o n i c s u r f a c t a n t s s t u d i e d i n
a q u e o u s s o l u t i o n a t 2 5
0
C
S u r f a c t a n t A b b r e v i a t i o n C M C 1 0
3
( m o l / L )
C
1 0
H
2 1
N C
5
H
5
C l C
1 0
P y C l 6 5 . 0 0
C
1 2
H
2 5
N C
5
H
5
C l C
1 2
P y C l 1 5 . 6 0
C
1 6
H
3 3
N C
5
H
5
C l C
1 6
P y C l 0 . 9 0
C a t i o n i c d y e ( R T ) , n e w l y s y n t h e s i z e d [ 7 ] , d e r i v a t i v e o f t h e c o m p a c t c o n d e n s e d s y s t e m 2 -
a m i n o t h i a z o l o O K [ 4 , 5 - b ] q u i n o x a l i n e - 6 - c a r b o x y l i c a c i d . T h e d y e w a s p u r i f i e d b y r e c r y s t a l l i z a t i o n
f r o m s o l v e n t s ; i t s p u r i t y w a s c h e c k e d b y t h i n l a y e r c h r o m a t o g r a p h y a n d H P L C . T h e s t r u c t u r e o f
t h i s c a t i o n i c d y e i s p r e s e n t e d i n F i g . 1 .
Eurasi an J. Anal . Chem. / Vol :3, N o:1, 2008 115
N
N C
H
C H
C
H
S
C
3
C
2
N
N = N
H O O C
C H
3
C
H
C
H
C - N ( C H
3
)
2
C
H
C
H
C
C
C
C C
C
1
4
5
6
7
8
9
1 0 1 1
1 2
1 3
1 4
+
J(ortho)
J(ortho)
J(ortho)
Fig.1. T h e s t r u c t u r e o f c a t i o n i c d y e R T
T h e s e l e c t i o n o f t h i s d y e f o r a d s o r p t i o n s t u d y o n c o t t o n i n t h e p r e s e n c e o f c a t i o n i c
s u r f a c t a n t s w a s b a s e d o n i t s a f f i n i t y t o n a t u r a l f i b r e s [ 7 ] a n d i t s s t a b i l i t y i n t i m e .
M e t h y l e n e B l u e ( A M ) w a s u s e d i n t h i s s t u d y o w i n g t o i t s s t r o n g a d s o r p t i o n o n n a t u r a l
f i b r e s a n d i t s b a c t e r i o s t a t i c a n d d i s i n f e c t i n g p r o p e r t i e s ; i t h a s M = 3 7 3 . 9 g / m o l , w h i c h
c o r r e s p o n d s t o m e t h y l e n e b l u e d i c h l o r i d e w i t h t h r e e w a t e r m o l e c u l e s .
H y d r o p h i l i c c o t t o n f i b r e o f t y p e B C f o r m e d i c i n a l u s e , p r o d u c e d b y R o m p e l S u r g i c a l
P r o d u c t s , S . T . 0 1 / 1 9 9 9 , S R E N I S O 9 0 0 2 ; t h i s c o t t o n h a s s p e c i f i c s u r f a c e S
s p
= 3 1 . 7 1 m
2
/ g ,
d e t e r m i n e d b y t h e m e t h y l e n e b l u e a d s o r p t i o n m e t h o d [ 8 ] , w h i c h c o r r e s p o n d s t o c o t t o n t y p e B
2 6
,
i n a c c o r d a n c e w i t h I n t e r n a t i o n a l S t a n d a r d s o f C o t t o n .
T h e a d s o r p t i o n d a t a w e r e o b t a i n e d b y U V - V I S s p e c t r o p h o t o m e t r y . T h e m e a s u r e m e n t s
w e r e p e r f o r m e d u s i n g t h e S E C O M A M S 7 5 0 s p e c t r o p h o t o m e t e r a n d t h e U N I C A M - H E L I O S -
s p e c t r o p h o t o m e t e r , c o u p l e d o n - l i n e t o P C s y s t e m s ;
T h e s u r f a c e t e n s i o n w a s d e t e r m i n e d b y t h e D u N o u y m e t h o d b y m e a s u r i n g t h e F f o r c e
n e c e s s a r y t o d e t a c h a P t - I r r i n g f r o m a l i q u i d s u r f a c e .
3. Results and discussions
3.1. Part I: Adsorption study of alkylpyridinium chlorides from aqueous solution on cotton
F o r t h e a d s o r p t i o n s t u d y o f a l k y l p y r i d i n i u m c h l o r i d e s o n c o t t o n , s o l u t i o n s o f t h e c a t i o n i c
s u r f a c t a n t a t d i f f e r e n t c o n c e n t r a t i o n s ( 0 . 5 1 0
- 4
1 . 0 0 1 0
- 3
m o l / L ) w e r e p r e p a r e d a n d p u t i n
c o n t a c t w i t h c o t t o n f i b r e s f o r 2 4 h a t 2 0
0
C . T h e a d s o r b e d q u a n t i t y w a s e v a l u a t e d b y t h e
e q u a t i o n :
116 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
a = [ ( c
i
c ) V ] / m ( m o l / g ) ( 1 )
w h e r e : a a d s o r b e d q u a n t i t y o n c o t t o n ; c
i
i n i t i a l s u r f a c t a n t c o n c e n t r a t i o n ; c e q u i l i b r i u m
c o n c e n t r a t i o n ; V v o l u m e o f s o l u t i o n ; m s o l i d m a s s .
T h e e q u i l i b r i u m c o n c e n t r a t i o n w a s d e t e r m i n e d f r o m a c a l i b r a t i o n c u r v e o f t h e s u r f a c t a n t . T h e
a d s o r p t i o n i s o t h e r m s f o r t h e c a t i o n i c s u r f a c t a n t s s t u d i e d a t t h e c o t t o n / w a t e r i n t e r f a c e a r e
p r e s e n t e d i n F i g . 2 .
0
1
2
3
4
5
6
0 0 . 0 2 0 . 0 4 0 . 0 6 0 . 0 8
[C
m
PyCl] mol/L
a
x
1
0
5
m
o
l
/
g
C 1 2 P y C
C 1 0 P y C
a)
I
II
III
IV
Fig. 2. a ) A d s o r p t i o n i s o t h e r m s o f C
1 0
P
y
C l a n d C
1 2
P
y
C l s u r f a c t a n t s o n c o t t o n a t 2 0
0
C ;
b ) A d s o r p t i o n i s o t h e r m o f C
1 6
P
y
C l s u r f a c t a n t o n c o t t o n a t 2 0
0
C .
A d s o r p t i o n i s o t h e r m s o f c a t i o n i c s u r f a c t a n t s o f C
m
P y C l t y p e o n c o t t o n b e l o n g t o t h e L
c l a s s , 4 u n d e r - c l a s s e s a c c o r d i n g t o t h e i s o t h e r m s c l a s s i f i c a t i o n [ 9 ] . T h e s u r f a c t a n t i s a d s o r b e d
b y e l e c t r o s t a t i c i n t e r a c t i o n w i t h t h e c o t t o n s u b s t r a t e l o a d e d w i t h n e g a t i v e c h a r g e s .
A n i n c r e a s e i n t h e a d s o r b e d q u a n t i t i e s o n t h e s u b s t r a t e i s o b s e r v e d a t s u r f a c t a n t
c o n c e n t r a t i o n s c l o s e t o C M C , w h e r e a m a x i m u m i s o b s e r v e d . T h e l a t t e r p o i n t s t o t h e f a c t t h a t
t h e f o r m a t i o n o f m i c e l l e s i n t h e s o l u t i o n p r e v a i l s o v e r t h e f o r m a t i o n o f a b i - l a y e r a t t h e
c o t t o n / w a t e r i n t e r f a c e ; m o r e o v e r , t h e m a x i m u m g i v e s a n e v i d e n c e f o r t h e e q u i l i b r a t e d b e h a v i o r
o f c a t i o n i c s u r f a c t a n t s o n a c e r t a i n c l a s s o f s u b s t r a t e s .
O n t h e b a s i s o f t h e a d s o r p t i o n r e s u l t s , w e c a l c u l a t e d t h e m o l e c u l a r s p e c i f i c s u r f a c e s (
*
A)
b y e q u a t i o n :
max
*
1
I
=
A
N
A ( n m
2
/ m o l e c u l e ) ( 2 )
w h e r e : N
A
- A v o g a d r o s n u m b e r , I
m a x
m a x i m u m a d s o r b e d q u a n t i t y a t t h e s o l i d / l i q u i d i n t e r f a c e .
HMC
0
1
2
3
4
5
6
0 0 , 0 0 0 5 0 , 0 0 1
a
x
1
0
5
m
o
l
/
g
[C
16
PyCl] mol/L
C 1 6 P y C
b)
C M C
I
II
III
IV
Eurasi an J. Anal . Chem. / Vol :3, N o:1, 2008 117
Table 2. O c c u p i e d s u r f a c e s o f c a t i o n i c s u r f a c t a n t m o l e c u l e s o n c o t t o n f i b r e a t 2 0
0
C .
S t u d i e d
s y s t e m
a 1 0
5
m o l / g N
A
a 1 0
5
m o l e c u l e s / g
*
A
n m
2
/ m o l e c u l e
1 0
6
m o l / m
2
C
1 0
P y C l 5 . 3 0 3 0 . 8 9 1 0
2 8
1 . 0 2 1 . 6 1 7
C
1 2
P y C l 5 . 2 5 3 1 . 6 2 1 0
2 8
1 . 0 0 1 . 6 5 5
C
1 6
P y C l 5 . 4 4 3 2 . 7 6 1 0
2 8
0 . 9 6 1 . 7 1 5
T h e m o l e c u l a r s p e c i f i c s u r f a c e d e c r e a s e s w i t h t h e i n c r e a s e i n h y d r o c a r b o n c h a i n l e n g t h
o f t h e s u r f a c t a n t .
3.1.2. Part II: Adsorption study of alkylpyridinium chlorides in the presence of dyes at the
cotton/water interface
F o r t h e a d s o r p t i o n s t u d y o f m i x e d a q u e o u s s o l u t i o n s o f c a t i o n i c s u r f a c t a n t C
1 6
P
y
C l d y e
o n c o t t o n , s a m p l e s w i t h d i f f e r e n t c o n c e n t r a t i o n s o f t h e d y e R T [ 0 . 5 1 0
- 4
1 1 0
- 3
m o l / l ] a n d t h e
s u r f a c t a n t C
1 6
P
y
C l , a s w e l l a s o f t h e m o n o m e r i c d y e A M [ 0 . 5 1 0
- 5
1 0 1 0
- 5
m o l / l ] a n d t h e
s u r f a c t a n t C
1 6
P
y
C l w e r e p r e p a r e d . T h e s a m p l e s w e r e p u t i n c o n t a c t w i t h c o t t o n f i b r e s f o r 2 4 h a t
2 0
0
C . T h e v o l u m e o f t h e m i x t u r e w a s 3 0 m L a n d t h e s o l i d m a s s w a s 0 . 3 g c o t t o n .
0
1 0
2 0
3 0
4 0
5 0
0 2 4 6 8
Ce x10
5
mol/l
a
x
1
0
6
m
o
l
/
l
A M - c o t t o n
A M - C 1 6 P C l - c o t t o n
C 1 6 P C l - c o t t o n
1
2
3
Fig. 3. A d s o r p t i o n i s o t h e r m s : 1 - a q u e o u s s o l u t i o n s o f m e t h y l e n e b l u e o n c o t t o n ; 2 - m i x e d s y s t e m
C
1 6
P
y
C l m e t h y l e n e b l u e o n c o t t o n ; 3 - a q u e o u s s o l u t i o n s o f s u r f a c t a n t C
1 6
P
y
C l a t 2 0
0
C .
T h e i s o t h e r m o f m o n o m e r i c m e t h y l e n e b l u e o n c o t t o n i s o f L c l a s s a c c o r d i n g t o G i l e s
c l a s s i f i c a t i o n a n d i t s h o w s a n i n c r e a s e i n t h e q u a n t i t y a d s o r b e d o n c o t t o n w i t h t h e i n c r e a s e i n
d y e c o n c e n t r a t i o n i n s o l u t i o n . T h e a f f i n i t y o f A M f o r c o t t o n f i b r e s i s d u e t o v a n d e r W a a l s f o r c e s ;
t h e a d s o r p t i o n i n c r e a s e s w i t h t h e i n c r e a s e i n d y e c o n c e n t r a t i o n , a n d w h e n t h e s i t e s o n t h e
s u r f a c e a r e o c c u p i e d , t h e f u r t h e r i n c r e a s e i n d y e c o n c e n t r a t i o n s u p p r e s s e s a d s o r p t i o n .
118 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
T h e i s o t h e r m o f m i x e d a q u e o u s s o l u t i o n s o f A M - C
1 6
P
y
C l p o i n t s t o a c o m p e t i t i v e
a d s o r p t i o n , t h e d y e b e i n g d i s s o l v e d i n t h e m i c e l l e s o f t h e c a t i o n i c s u r f a c t a n t . T h e s u r f a c t a n t
s t o p s t h e a d s o r p t i o n o f d y e a t t h e c o t t o n / w a t e r i n t e r f a c e . T h e m i n i m u m s u r f a c e o c c u p i e d b y a
m o l e c u l e a t t h e c o t t o n / w a t e r i n t e r f a c e f o r A M - C
1 6
P
y
C l s y s t e m s i s 2 . 5 9 n m
2
/ m o l e c u l e w h e r e a s
w i t h a q u e o u s s o l u t i o n s o f s u r f a c t a n t t h e s u r f a c e o c c u p i e d b y a m o l e c u l e i s 1 . 5 n m
2
/ m o l e c u l e .
T h e a d s o r p t i o n i s o t h e r m o f t h e c a t i o n i c d y e R T o n c o t t o n r e v e a l s t h e i n c r e a s e d
a d s o r p t i o n o n c o t t o n w i t h t h e i n c r e a s e i n d y e c o n c e n t r a t i o n i n t h e m i x t u r e . T h e a d s o r p t i o n
i s o t h e r m i s o f L a n g m u i r t y p e a n d i t i s a s s o c i a t e d w i t h m o n o - s t r a t u m f o r m a t i o n [ 1 0 ] . T h i s i s a n
i n d i c a t i o n f o r t h e a f f i n i t y o f t h e c a t i o n i c d y e t o t h e c o t t o n f i b r e l o a d e d w i t h n e g a t i v e c h a r g e s , t h e
a d s o r p t i o n t a k i n g p l a c e b y e l e c t r o s t a t i c i n t e r a c t i o n s . F o r c o n c e n t r a t e d s o l u t i o n s o f d y e t h e
a d s o r p t i o n m a x i m u m o n c o t t o n i s r e a c h e d a t = 3 . 6 8 9 1 0
- 7
m o l / m
2
, w h e r e a
m a x
= 1 1 . 7 1 0
- 5
m o l / g ;
i n t h i s w a y a n i n c r e a s e i n c o n c e n t r a t i o n w i l l n o t l e a d t o a n i n c r e a s e i n a d s o r p t i o n b e c a u s e t h e
s a t u r a t i o n p o i n t i s r e a c h e d .
T h i s b e h a v i o r i s s p e c i f i c f o r f i b r e s w i t h a l i m i t e d n u m b e r o f a c t i v e s i t e s . T h e a c c e s s i b l e
a c t i v e s i t e s l e a d t o i n c r e a s e d a d s o r p t i o n a c c o m p a n i e d b y i n c r e a s e d d y e c o n c e n t r a t i o n . I f t h e s e
s i t e s a r e o c c u p i e d , t h e i n c r e a s e i n d y e c o n c e n t r a t i o n d o e s n o t l e a d t o i n c r e a s e d a d s o r p t i o n .
0
1
2
3
4
5
6
7
0 2 4 6 8 1 0
[C
16
PyCl]ex10
4
mol/l
a
x
1
0
5
m
o
l
/
g
C 1 6 P y C l
C 1 6 P y C l - d y e
Fig 4. A d s o r p t i o n i s o t h e r m s f o r a q u e o u s s o l u t i o n s o f c a t i o n i c s u r f a c t a n t a n d m i x e d
s o l u t i o n s o f s u r f a c t a n t C
1 6
P
y
C l c a t i o n i c d y e R T a t 2 0
0
C .
T h e a d s o r p t i o n i s o t h e r m s o f C
1 6
P y C l m i c e l l e - c a t i o n i c d y e R T m i x e d s y s t e m s p o i n t t o a
p r e f e r e n t i a l a d s o r p t i o n o f t h e c a t i o n i c s u r f a c t a n t a t t h e c o t t o n / w a t e r i n t e r f a c e . B y u s i n g a
c a t i o n i c d y e t h e c a t i o n i c c h a n g e c a p a c i t y o f t h e s u b s t r a t e c a n b e m e a s u r e d .
Eurasi an J. Anal . Chem. / Vol :3, N o:1, 2008 1 1 9
T h e m o s t c o m p l e x b e h a v i o r w a s o b s e r v e d i n t h e c a s e o f n o n - i o n i c d y e s . M a n y o f t h e s e
d y e s a r e d i s s o l v e d a t c o n c e n t r a t i o n s a b o v e C M C [ 1 1 ] . T h e s t u d i e s s h o w t h a t i f t h e s u r f a c t a n t i s
c a t i o n i c , t h e d i s s o l v e d d y e c a n b e e a s i l y a d s o r b e d o n t h e f i b r e s , a n d t h e d e p t h o f c o l o r i n g i s
p r o p o r t i o n a l t o t h e c a t i o n i c c h a n g e c a p a c i t y o r t o t h e i n c r e a s e d i o n p a i r a d s o r p t i o n .
I f t h e s u r f a c t a n t i s a n i o n i c , l e s s d y e i s t r a n s f e r r e d t o t h e s u b s t r a t e . H o w e v e r , i f a
s u b s t r a t e i s d y e d w i t h a c a t i o n i c d y e s o l u t i o n , t h e n t h e a n i o n i c s u r f a c t a n t s o l u t i o n i s c o l o r e d a t
r o o m t e m p e r a t u r e ( t h e d y e i s t r a n s f e r r e d a g a i n i n s o l u t i o n ) . O n t h e b a s i s o f t h e o b t a i n e d r e s u l t s ,
w e c a n a f f i r m t h a t i o n p a i r a d s o r p t i o n n s u r e s d y e t r a n s f e r o n f i b r e o r i n s o l u t i o n .
F o r d e m o n s t r a t i n g t h e t y p e o f i n t e r a c t i o n a n d t h e m o d e o f o r i e n t a t i o n o f c a t i o n i c
s u r f a c t a n t s o f a l k y l p y r i d i n i u m c h l o r i d e t y p e f r o m a q u e o u s s o l u t i o n o n c o t t o n , c l a s s i c a l m e t h o d s
w e r e u s e d , d e v e l o p e d f o r i o n i c s u r f a c t a n t s a d s o r p t i o n o n s o l i d s u r f a c e s .
MODEL Fowler-Guggenheim [ 1 2 ] : a m o d e l w h i c h e x p l a i n s t h e l a t e r a l i n t e r a c t i o n s
b e t w e e n a d s o r b e d m o l e c u l e s o n s o l i d s u r f a c e .
I n t h i s m o d e l t h e e q u a t i o n o f a d s o r p t i o n i s :
m
m
303 . 2
2
K log 1 c log

=
|
|
.
|

\
|

( 3 )
w h e r e I - t h e a d s o r p t i o n c o e f f i c i e n t a t t h e e q u i l i b r i u m c o n c e n t r a t i o n o f t h e s u r f a c t a n t i n s o l u t i o n
c ; I
m
- t h e m a x i m u m a d s o r p t i o n c o e f f i c i e n t ; K - t h e c h a r a c t e r i s t i c c o n s t a n t o f t h e i n t e r a c t i o n
b e t w e e n t h e a d s o r b e d m o l e c u l e s a n d t h e s o l i d s u r f a c e s i t e s , e - a p a r a m e t e r d u e t o i n t e r a c t i o n
b e t w e e n a d s o r b e d m o l e c u l e s .
T h e e q u a t i o n ( 3 ) i s a l i n e a r e q u a t i o n ; t h e s l o p e i s d e n o t e d w i t h a l p h a ( ) w h i c h i s e q u a l t o
2 / 2 . 3 0 3 .
F r o m t h e F o w l e r - G u g g e n h e i m e q u a t i o n w e c a n o b t a i n t h e f r e e e n e r g y o f a d s o r p t i o n
A G
a d s
a n d t h e f r e e e n e r g y o f i n t e r a c t i o n A G
i n t
( T a b l e 3 ) .
Tabl e 3. A d s o r p t i o n a n d i n t e r a c t i o n e n e r g y v a l u e s b e t w e e n a d s o r b e d m o l e c u l e s a t
c o t t o n / w a t e r i n t e r f a c e a t 2 5
0
C ( F o w l e r - G u g g e n h e i m M o d e l ) .
Surfactant Ln K Kx1 0
3
al pha
ads
G A
kj /mol
int
G A
kj /mol
R
2
C
1 6
P
y
C l - 5 . 2 0 5 . 5 - 2 . 0 1 - 2 . 3 1 - 1 2 . 9 9 - 5 . 8 1 0 . 9 8 4
A M -
C
1 6
P
y
C l
- 8 . 3 3 0 . 2 3 - 1 . 3 2 - 1 . 5 2 - 2 0 . 9 - 3 . 8 0 0 . 9 8 7
R T - C
1 6
P
y
C l - 3 . 3 0 3 6 . 7 - 3 . 4 0 - 3 . 9 1 - 8 . 2 7 - 9 . 8 2 0 . 9 6 5
[ R T ] - 6 . 6 5 1 . 2 8 - 1 . 1 9 - 1 . 3 7 - 1 6 . 6 7 - 3 . 4 7 0 . 9 3 1
K ln RT G
ads
= ( k j / m o l ) , RT G
int
= ( k j / m o l ) , = 2 / 2 . 3 0 3 .
120 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
T h e m o d e l r e v e a l s t h e e x i s t e n c e o f e l e c t r o s t a t i c i n t e r a c t i o n s i n r e g i o n I . F o r t h e s y s t e m
A M - C
1 6
P
y
C l , a h i g h e r v a l u e o f G
a d s
w a s r e g i s t e r e d t h a n i n t h e c a s e o f a s i n g l e s u r f a c t a n t ,
w h i c h s h o w s t h e h i g h e r a d s o r p t i o n p o w e r o f t h e d y e . I n t h e c a s e o f t h e m i x e d s y s t e m s R T -
C
1 6
P
y
C l , a d e c r e a s e i n t h e a d s o r p t i o n e n e r g y a n d a n i n c r e a s e i n t h e i n t e r a c t i o n e n e r g y i n
c o m p a r i s o n w i t h a q u e o u s c a t i o n i c s u r f a c t a n t s o l u t i o n s i s o b s e r v e d .
M O D E L Langmuir: a m o d e l w h i c h e x p l a i n s t h e e l e c t r o s t a t i c i n t e r a c t i o n s b e t w e e n
s u r f a c t a n t , d y e m o l e c u l e s a n d c o t t o n s u r f a c e .
F o r d e t e r m i n a t i o n o f t h e m a x i m u m s u p e r f i c i a l e x c e s s I
m a x
, d e f i n e d a s t h e m a x i m u m m o l
n u m b e r o f t h e s u b s t a n c e t h a t c a n b e a d s o r b e d o n t h e i n t e r f a c e a n d t h e m i n i m u m s u r f a c e
o c c u p i e d b y a n a d s o r b e d m o l e c u l e o n l i q u i d - g a s a n d l i q u i d - l i q u i d i n t e r f a c e , t h e L a n g m u i r
i s o t h e r m i s u s e d :
2
2 ) 1 (
2
1 Kc
Kc
RT
B
+
= I ( 4 )
w h e r e K i s t h e a d s o r p t i o n c o n s t a n t .
T h i s e q u a t i o n c a n b e d e d u c e d f r o m t h e i n t e g r a l e q u a t i o n o f s u r f a c e t e n s i o n i s o t h e r m
c o m b i n e d w i t h G i b b s e q u a t i o n . T h e l i n e a r f o r m o f t h e a d s o r p t i o n e q u a t i o n p e r m i t s g r a p h i c
d e t e r m i n a t i o n ( F i g . 5 ) o f t h e m a x i m u m a d s o r p t i o n c o e f f i c i e n t a n d t h e c o n s t a n t k :
K
c c
I
+
I
=
I
max max
2
2
2
1
Fig. 5. L a n g m u i r a d s o r p t i o n i s o t h e r m
H a v i n g i n v i e w t h e d e f i n i t i o n o f s u p e r f i c i a l e x c e s s , t h e i n v e r s e o f t h i s v a l u e i s e q u a l t o t h e
s u r f a c e o c c u p i e d b y a m o l e c u l e i n t h e s u p e r f i c i a l l a y e r . I
m a x
b e i n g k n o w n , w e h a v e c a l c u l a t e d
2
2
I
c
c
2
( m o l / L )
max
1
I K
max
1
I
Eurasi an J. Anal . Chem. / Vol :3, N o:1, 2008 1 21
the minimum surface occupied by a molecule at the interface,
*
A by equation (2).
Tabl e 4. Evaluated values by Langmuir equation
Studi ed
system
a
max
1 0
5
mol/g

max
1 0
6
mol /m
2
kx1 0
5
nm
2
/
molec
Ln K F
ads
=-
RTl nK
kj /mol
R
2
C
16
P
y
Cl 3.35 1.056 2.58 1.57 -10.56 -26.45 0.998
AM 0.684 0.215 1.580 0.775 -11.05 -27.71 0.923
AM-
C
16
P
y
Cl
0.203 0.640 4.63 2.59 -9.97 -24.99 0.995
RT 5.708 1.800 37.40 0.926 -7.88 19.78 0.920
RT -
C
16
P
y
Cl
3.340 1.053 3.32 1.57 -10.31 -25.86 0.996
In the case of mixed aqueous solutions of AM - C
16
P
y
Cl, the specific molecular surface
was 2.5 nm
2
/molecule at the cotton/water interface, while for the aqueous surfactant solutions
the occupied surface is 1.57 nm
2
/ molecule.
For the cationic dye system RT - C
16
P
y
Cl, the minimum surface occupied by a molecule
at the interface is equal to the surface occupied by surfactant molecules, which confirms the
preferential adsorption of surfactant molecules at the cotton/water interface (Fig. 4).
4. Concl usi ons
The adsorption isotherms of cationic surfactants of alkylpyridinium chloride type at the
cotton/water interface belong to the L class, 4 under-classes of preferential adsorption
isotherms. In the first stage of adsorption, the cationic surfactant is adsorbed on the cotton
surface by electrostatic interaction. At surfactant concentrations close to CMC an increase in
the adsorbed quantity on the substrate is observed due to hydrophobic interactions between the
hydrocarbon chains of molecules adsorbed at the interface and those in solution; close to CMC
a maximum is observed which points to the fact that the formation of micelles in solution
prevails over the formation of a bi-layer at the interface.
It was found that the cationic change capacity of cotton fibres can be measured using
the cationic dyes AM and RT. The adsorption isotherms of aqueous mixed solutions of
alkylpyridinium chloride - methylene blue (C
16
P
y
Cl-AM) were obtained. These isotherms pointed
to a competitive adsorption between surfactant and dye. The studies revealed that the dye is
dissolved in the micelles of the cationic surfactant, which hampers its adsorption on the fibres;
the depth of dyeing is proportional to the cationic change capacity or to the increase in ion pair
adsorption.
122 Tyut yunni k, Chkhet i j a, Get si na, Badul i na, Gal uzi nskaya, L evi t an, K ubrakova
T h e t y p e o f i n t e r a c t i o n s a n d t h e o r i e n t a t i o n m o d e o f c a t i o n i c s u r f a c t a n t m o l e c u l e s i n
e a c h s t a g e o f a d s o r p t i o n a t t h e c o t t o n / w a t e r i n t e r f a c e a r e s t u d i e d b y v e r i f i c a t i o n o f o r i g i n a l d a t a
o n c l a s s i c m o d e l s ( F o w l e r - G u g g e n h e i m , L a n g m u i r ) c o n c e r n i n g t h e a d s o r p t i o n o f i o n i c
s u r f a c t a n t s o n s o l i d s . F o r d y e s u r f a c t a n t a q u e o u s s o l u t i o n s A M - C
1 6
P
y
C l , h i g h v a l u e s o f t h e
a d s o r p t i o n e n e r g y w e r e o b t a i n e d i n c o m p a r i s o n w i t h t h e v a l u e s o b t a i n e d f o r s u r f a c t a n t a q u e o u s
s o l u t i o n s . T h i s p o i n t s t o a h i g h e x t e n t o f d y e a d s o r p t i o n o n t h e c o t t o n / w a t e r i n t e r f a c e . F o r t h e
d y e s u r f a c t a n t R T - C
1 6
P
y
C l s y s t e m , t h e a d s o r p t i o n e n e r g y i s l o w e r , b u t t h e i n t e r a c t i o n e n e r g y
i s h i g h e r , w h i c h c o n f i r m s t h e p r e f e r e n t i a l a d s o r p t i o n o f s u r f a c t a n t m o l e c u l e s a t t h e c o t t o n / w a t e r
i n t e r f a c e .
References
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2 0 0 3 .
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6 . M n d r u I . , An. Univ. Bucharest, Ser. Chim. , X I X , 1 9 7 0 , p . 1 4 3 .
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8 . E l e n a I r i n a M o a t e r , M i h a e l a O l t e a n u , Bulletin of University Petrol-Gaze Ploiesti, v o l .
L V I I , 2 / 2 0 0 5 p . 1 7 6 - 1 7 9 , I S S N 1 2 2 1 - 9 3 7 1 .
9 . G i l e s G . H . , D . S m i t h a n d A . H u i t s o n , J. Colloid and Interface Sci. , 4 7 , n o . 3 , 1 9 7 4 , p . 7 5 5 .
1 0 . G i l e s , C . H . , T . H . M a c E w a n , S . N . N a k h v a , a n d D . S m i t h , J. Chem. Soc. 5 6 , 3 9 7 3 .
1 1 . E l e n a I r i n a M o a t e r , M i h a e l a O l t e a n u , C r i s t i a n a R d u l e s c u , I o n i c a I o n i , Review of
Chemistry, 5 6 ( 1 1 ) , 2 0 0 5 , p . 1 1 6 0 - 1 1 6 3
1 2 . F o w l e r R . , G u g g e n h e i m E . A , Statistical Thermodynamics, C a m b r i d g e U n i v e r s i t y P r e s s ,
1 9 5 6 , L o n d o n , 4 2 9 .
Corresponding author: E l e n a I r i n a M o a t e r
Address: U n i v e r s i t y V a l a h i a f r o m T r g o v i t e , F a c u l t y o f S c i e n c e s a n d A r t s , D e p a r t m e n t o f C h e m i s t r y ,
B l v d . U n i r i i , 1 8 - 2 0 , T r g o v i t e , R o m a n i a
Phone: ( + 4 0 ) - 2 4 5 2 2 2 1 7 5 ; 7 2 4 2 6 0 1 0 5
Fax: ( + 4 0 ) - 2 4 5 2 2 2 1 7 5
E-mail: i r i n a m o a t e r @ g m a i l . c o m