A C T A U N I V E R S I T A T I S L O D Z I E N S I S
FOLIA CHIMICA 1, 1982 * ____
S t e f a n i a T a n le w s k a -O s liis k a , M aria n W oldan
VISCOSIMETRIC INVESTIGATIONS OF H20-AcNH2-N a I TERNARY
SYSTEM WITHIN THE TEMPERATURE RANGE 25 -8 5 °C *
The v i s c o s i t y o f N al s o l u t i o n s i n m ix ed w a te r - a c e t a m i d e s o l v e n t s o v e r t h e te m p e r a t u r e r a n g e 2 5 -8 5 °C h a s b een mea s u r e d . The d e p e n d e n c e o f v i s c o s i t y , r e l a t i v e v i s c o s i t y an d t h e th erm o d y n a m ic f u n c t i o n s o f a c t i v a t i o n f o r f l u i d flo w o f I n v e s t i g a t e d s o l u t i o n s on t h e c o n c e n t r a t i o n and te m p e r a t u r e h a s b ee n d i s c u s s e d . The c o n c l u s i o n s a b o u t t h e e f f e c t o f N al an d a c e ta m id e on th e s t r u c t u r e o f i n v e s t i g a t e d s y s te m s h a v e b ee n d ra w n . The l i t e r a t u r e d a t a on v i s c o s i t y o f e l e c t r o l y t e s o l u t i o n s i n d i c a t e t h a t i o n s c a n i n c r e a s e o r d e c r e a s e t h e v i s c o s i t y o f s o l v e n t r e l a t i v e l y t o t h e i r s o l v a t i o n an d I n f l u e n c e on t h e s o l v e n t s t r u c t u r e . W eakly s o l v a t e d i o n s d e c r e a s e t h e v i s c o s i t y o f s o l v e n t , w h ile s t r o n g l y s o l v a t e d o n e s i n c r e a s e t h e ab o v e men t i o n e d q u a n t i t y . The c o n c lu s i o n a b o u t t h e e f f e c t o f e l e c t r o l y t e on s o l v e n t i n c a s e o f d i l u t e d s o l u t i o n s c a n b e draw n fro m t h e a n a l y s i s o f v a l u e o f B c o e f f i c i e n t fro m J o n e s -D o le * 3 e q u a t i o n an d i t s c h a n g e w ith t e m p e r a t u r e [1 , 2 ] . As f o r t h e more c o n c e n t r a t e d s o l u t i o n t h e c o n c l u s i o n a b o u t t h e e f f e c t o f e l e c t r o l y t e on s o l v e n t ca n b e draw n fro m t h e d e p e n d e n c e o f r e l a t i v e v i s c o s i t y o f th e s o l u t i o n on i t s c o n c e n t r a t i o n an d te m p e r a t u r e [ 3 ] .
* The p r e s e n t w ork h a s b ee n c a r r i e d o u t a n d s u p p o r te d w ith i n t h e fram ew o rk o f r e s e a r c h on I n t e r d e p a r t m e n t P ro b lem M R-I-
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1 1.
F i g . 1 . D ependence o f v i s c o s i t y o f N a l - s o l u t i o n s i n w a t e r - a c e t - am id e s o l v e n t s v s . c o n c e n t r a t i o n s o f e l e c t r o l y t e a t 25°C • ( w t % AcNH2 ) From r e c e n t w o r k s ^ A , 5 ] i t f o l l o w s t h a t s t r u c t u r a l c h a n g e s t a k i n g p l a c e i n t h e s o l u t i o n i l l u s t r a t e t h e t e m p e r a t u r e c o e f f i c i e n t Atj^ /A T o f r e l a t i v e v i s c o s i t y b e t t e r t h a n r e l a t i v e v i s c o s i t y . I n c a s e o f e l e c t r o l y t e o r d e r i n g s o l v e n t s t r u c t u r e A î}r / A Î c o e f f i c i e n t i s n e g a t i v e and p o s i t i v e f o r s t r u c t u r e b r e a k i n g e l e c t r o l y t e s . The a n a l y s i s o f th e rm o d y n a m ic a l p r o p e r t i e s o f e l e c t r o l y t e
s o l u t i o n s i n m o lte n a c e ta m id e [ 6 ] a llo w e d t o o b s e r v e a c e r t i n s i m i l a r i t y o f t h e ab o v e m e n tio n e d s o l u t i o n s t o a q u e o u s s o l u t i o n s . T hus i t seem ed i n t e r e s t i n g t o c a r r y o u t t h e v i s c o s i - m e t r i c i n v e s t i g a t i o n s o f N al s o l u t i o n s i n m ixed w a t e r - a c e t - am id e s o l v e n t s . Such i n v e s t i g a t i o n s c o u ld s u p p ly c e r t a i n i n f o r m a ti o n on i n t e r a c t i o n among w a te r an d a c e ta m id e m o lecu l e s . F i g . 2 . D ep endence o f v i s c o s i t y o f N al s o l u t i o n s i n w a t e r - a c e t - araide s o l v e n t s v s . c o n c e n t r a t i o n s o f e l e c t r o l y t e **0 C (w t % AcNH2 )
E x p e r im e n ta l
The m ixed w a te r - a c e t a m id e s o l v e n t s w e re p r e p a r e d fro m tw ic e d i s t i l l e d w a te r a n d a c e ta m id e p . a . b y "Xenon" - Ł ó d ź . The way o f p u r i f y i n g a c e ta m id e an d N al w as d e s c r i b e d e a r l i e r [ 7 ] . F o r t h e m e a su re m e n ts o f v i s c o s i t y o f N al s o l u t i o n s I n w a te r
a c e ta m id e s o l v e n t s t h e U b b e lo h d e ’ s v i s c o m e t e r by S c h o t t - Cen M ainz (J e n a G l a s s ) w as u s e d . ,
The v i s c o m e t e r was p l a c e d i n l i q u i d t h e r m o s t a t e a l l o w i n g t o k e e p t h e r e q u i r e d te m p e r a t u r e w ith t h e p r e c i s i o n t o +0.05°C . The e r r o r o f v i s c o s i t y m e a su re m e n ts was ,+ 0 .5 # . The r e s u l t s o f v i s c o s i t y m e a su re m e n ts o f N al s o l u t i o n s i n w a te r - a c e t a m i d e s o l v e n t s a t t h e te m p , 2 5 ° , 4 0 ° , 6 0 ° , 7 5 ° an d 85°C a r e p r e s e n t e d on F i g . 1-5« F i g . A. D ep endence o f v i s c o s i t y o f N al s o l u t i o n s i n v * ^ t e r - a c e t - am ide s o l v e n t s v s . c o n c e n t r a t i o n o f e l e c t r o l y t e a t 75 C 'vw t % A c N H 2 ) The d i s c u s s i o n o f r e s u l t s As i t s e e n fro m F i g . 1 - 5 ’ t h e v i s c o s i t y o f t h e i n v e s t i g a t e d H20-AcNH2-Na I t e r n a r y s y s t e m grow s w i t h t h e i n c r e a s e o f e l e c
-t r o l y -t e c o n c e n t r a t i o n i n t h e s o l u t i o n . The i n c r e a s e o f v i s c o s i t y o f t h e s o l u t i o n i s th e l e a s t i n s o l v e n t s w i t h s m a ll a c e t - a m id e c o n t e n t s an d i t g ro w s g r a d u a l l y w ith t h e i n c r e a s e o f n o n e l e c t r o l y t e c o n t e n t s i n t h e s o l u t i o n . I t seem s p r o b a b le t h a t t h e o b s e r v e d i n c r e a s e o f v i s c o s i t y o f t h e i n v e s t i g a t e d t e r n a r y s y s te m w ith t h e i n c r e a s i n g a c e ta m id e c o n t e n t s i n t h e s o l u t i o n
F i g . 6 . D ependence o f r e l a t i v e v i s c o s i t y o f N al s o l u t i o n s i n wa- t e r - a c e t a m i d e s o l v e n t s v s . c o n c e n t r a t i o n and a c e ta m id e c o n t e n t s a t 25°C ( v t * AcNH2 ) F i g . 7 . D ependence o f r e l a t i v e v i s c o s i t y . ^ ^ i S ^ d ? 38 c o i - v a t e r - a c e t a m i d e s o l v e n t s v s . a c e ta i6 id e t e n t s a t 40°C (w t % AcNH2 )
i s c a u s e d by t h e p r e s e n c e o f g r e a t e r a c e ta m id e m o le c u le s an d by t h e f o r m a tio n o f m ixed a s s o c i a t e s com posed o f w a te r an d a c e t - am id e m o le c u le s w ith t h e c o n t r i b u t i o n o f h y d ro g e n b o n d s .
From t h e d i e l e c t r i c i n v e s t i g a t i o n s [ 8 - 1 0 ] i t f o l l o w s t h a t h y d ro g e n b o n d s among w a te r an d a c e ta m id e m o le c u le s a r e s l i g h t l y ? e a k e r th a n h y d ro g e n b o n d s i n p u re w a t e r . I t c a n b e t h u s e x
-p o c te d t h a t th e o b s e r v e d g r e a t e r e f f e c t o f t e m p e r a t u r e c h a n g e s on t h e v i s c o s i t y o f HgO-AcNHg-Nal sy ste m i n c o m p a riso n w ith HgO-Nal b i n a r y s y s te m i s c a u s e d by a p a r t i a l d i s i n t e g r a t i o n o f m ixed w a t e r - a c e ta m id e a a o c i a t e s p r e s e n t i n t h e s o l u t i o n .
[mole/dm3]
0,9 CN o I
F i g . 1 v a t e r -Imole/dm3 ] 0 . D ep endence o f r e l a t i v e v i s c o s i t y o f Nal s o l u t i o n s i n a c a ta m id e s o l v e n t s v s . c o n c e n t r a t i o n an d a c e ta m id e c o n t e n t s a t 85°C (vrt % AcNH2 ) 85 °C
The d i s c u s s e d a b o v e c h a n g e s o f v i s c o s i t y o f H20-Ac.NH2-N a I t e r n a r y a y s te m a s a f u n c t i o n o f c o n c e n t r a t i o n a n d t e m p e r a t u r e a r e more v i s i b l e i n c a s e o f r e l a t i v e v i s c o s i t y o f t h e i n v e s t i g a t e d s y s t e m s . The d e p e n d e n c e o f r e l a t i v e v i s c o s i t y r)r o f Nal s o l u t i o n s i n w a t e r a c e t a m i d e s o l v e n t s on t h e s a l t c o n c e n t r a t i o n , n o n e l e c t r o l y t e c o n t e n t s and t e m p e r a t u r e i s p r e s e n t e d on F i g . 6
-
10.
I t c a n be e a s i l y n o t i c e d t h a t r e l a t i v e v i s c o s i t y o f t h e i n v e s t i g a t e d s o l u t i o n s grow s w i t h t h e I n c r e a s e o f e l e c t r o l y t e con c e n t r a t i o n and a c e t a m i d e c o n t e n t s i n t h e m ixed s o l v e n t s . I t ca n b e s u p p o s e d t h a t t h e i n c r e a s e o f r e l a t i v e v i s c o s i t y o f t h e d i s c u s s e d s y s t e m s i s c a u s e d by g ro w in g volum e o f s o l v a t i o n s sh ells a r o u n d i o n s . I n o r d e r t o v e r i f y t h i s h y p o t h e s i s t h e v a l u e s o f l i m i t i n g e f f e c t i v e f l o w i n g volum e o f Nal i n w a t e r - a c e t a m i d e s o l v e n t s w ere c a l c u l a t e d o v e r t h e t e m p e r a t u r e r a n g e 25-85°C ( T a b l e 1).
" T a b 1 e 1 The v a l u e s o f t h e l i m i t i n g e f f e c t i v e f l o w i n g volum e ( c m V m o l e ) o f N al i n w a t e r a c e t a m i d e s o l v e n t s w i t h i n t h e t e m p e r a t u r e r a n g e 25-85°C T (°C ) 5 w t % AcNH2 1 5 w t % AcNH2 3 0 w t % AcNH2 5 0 w t % AcNH2 7 0 w t % a c n h 2 8 5 w t % a c n h2 9 5 w t % AcNH2 2 5 16 2 4 3 2 3 6 - •* -4 0 2 4 2 8 4 0 4 4 - - -60 2 8 3 6 4 8 5 6 7 6 - w 7 5 3 6 4 4 5 6 6 4 8 4 - -8 5 4 0 4 8 6 0 6 8 9 2 1 3 2 168 The l i m i t i n g e f f e c t i v e f l o w i n g volum e o f N al i n th e i n v e s t i g a t e d s o l u t i o n s w a s o b t a i n e d b y e x t r a p o l a t i o n t o c * 0 o f a f f e c t i v e f l o w i n g v o l u m e s c a l c u l a t e d f r o m E i n s t e i n ’ s e q u a t i o n s c o n c e r n i n g r e l a t i v e v i s c o s i t y o f t h e s o l u t i o n s i) / t)0 - 1 ♦ 2.5cV e ( 1 )« to a re : c - m o la r c o n c e n t r a t i o n o f t h e s o l u t i o n V# - e f f e c t i v e f lo w in g v o lum e o f e l e c t r o l y t e 1 . e . t h e volum e o f 1 m ole o f i o n s t o g e t h e r w ith s o l v a t i o n a s h e l l s . As i t I s s e e n from T a b le 1 t h e l i m i t i n g e f f e c t i v e f lo w in g v o lu m e V® o f N al i n w a te r - a c e t a m i d e s o l u t i o n s i n c r e a s e s w i t h J O t h e g ro w th o f a c e ta m id e c o n t e n t s an d t e m p e r a t u r e . G r e a t e r V" v a l u e s o f Nal i n s o l u t i o n s w i th g r e a t e r a c e t a o i d e c o n t e n t s c a n b e e x p l a i n e d by g ro w in g c o n t r i b u t i o n o f a c e ta m id e a o l e o u l e s I n s o l v a t i o n o f i o n s a n d t h e d e c r e a s e o f V° v a l u e o f N al w i t h g ro w in g t e m p e r a t u r e c a n be c a u s e d by b r e a k i n g e f f e c t o f th e r m a l m o tio n s o f m o le c u le s on m ixed s o l v e n t s t r u c t u r e . I n h i g h e r t e m p e r a t u r e t h e m ixed w a te r - a c e t a m i d e a s s o c i a t e s w i t h w e a k e r h y d ro g e n b o n d s a r e m ore s u s c e p t i b l e t o d i s r u p t i o n t h a n w a te r a s s o c i a t e s . M oré f r e e m o le c u le s w h ic h ca n t a k e p a r t i n i o n i c s o l v a t i o n a p p e a r th e n i n t h e s o l u t i o n . U s in g t h e F i g . 6 -1 0 t h e v a l u e s o f te m p e r a t u r e c o e f f i c i e n t o f r e l a t i v e v i s c o s i t y At)r /A T o f t h e i n v e s t i g a t e d s o l u t i o n s w e re d e t e r m in e d . The o b t a i n e d v a l u e s a r e g iv e n i n T a b le 2 . T a b l e 2 The v a l u e s o f te m p e r a t u r e c o e f f i c i e n t o f r e l a t i v e v i s c o s i t y Ai)r / A T o f N al s o l u t i o n s i n w a te r - a c e t a m i d e s o l v e n t s w i t h i n t h e t e m p e r a t u r e r a n g e 25-85 °C a <m o le / k g ) 2 5-40°C 4 0-60 °C 6 0 -7 5 °C 7 5 -8 5 °C 1 2 3 4 5-5 w t # AcNH2 ( 1 . 58 m ole % AcNH2 ) 0 . 1 0 .1 0 .1 0 .1 0 .1 0 . 2 0 . 3 0 . 2 0 . 2 0 .1 0 . 3 0 . 4 0 . 3 0 . 4 0 .1 0 . 4 0 . 5 0 . 5 0 . 5 . 0 .1 0 . 5 0 . 7 0 . 6 0 . 6 0 . 2 0 . 6 0 . 8 0 . 7 0 . 8 0 . 3
T a b le 2 ( c o n t d . )
1 2 3 4 5
15 v t 5i AcNH2 ( 5 .1 m ole % AcNH2 )
0 . 1 0 .1 i 0 .1 0 ,1 0 .1 0 . 2 0 . 2 0 . 2 0 . 2 0 . 2 0 . 3 0 . 3 0 . 3 . 0 . 3 0 . 3 0 . 4 0 . 5 0 . 4 0 . 4 0 . 3 0 . 5 0 . 6 0 . 6 0 . 5 0 . 4 0 . 6 0 . 7 0 . 7 0 . 7 0 . 5
. / 30 v t % AcNH2 (1 1 .5 5 m ole % AcNHg)
0 .1 0 .1 0 .1 0 .1 0 .1 0 . 2 0 . 2 0 . 2 0 . 2 0 . 2 0 . 3 0 . 4 0 . 4 0 . 3 0 . 3 0 . 4 0 . 6 0 . 5 0 . 5 0 . 3 0 . 5 0 . 7 0 . 6 0 . 6 0 . 2 0 . 6 1 .0 0 . 7 0 . 7 0 . 3
50 w t JÉ AcNH2 ( 2 3 .3 6 m ole % AcNH2 )
0 .1 0 . 2 0 .1 0 .1 0 . 1 _ 0 . 2 0 . 3 0 . 3 0 . 2 0 . 2 0 . 3 0 . 5 0 . 4 _ 0 . 2 0 . 4 0 . 4 0 . 7 0 . 6 0 . 3 0 . 5 * 0 . 5 0 . 9 0 . 8 0 . 4 0 . 7 0 . 6 1 .1 1 .0 0 . 6 1 .0
70 w t % AcNH2 (41 m ole # AcNH,>>
0 .1 mm 0 .1 0 . 2 0 . 2 « - 0 . 3 0 . 4 0 . 3 • - 0 . 6 0 . 5 0 . 4 mm - 0 . 9 0 . 7 0 . 5 mm - 1 .1 0 . 9 0 . 6 - - 1 .3 1 .1
The t e m p e r a t u r e c o e f f i c i e n t At^ A T o f w a te r - a c a t a m i d e Nal a o l u t i o n a i 3 p o s i t i v e an d i t I n c r e a s e s w ith t h e g ro w in g s a l t c o n c e n t r a t i o n i n th e s o l u t i o n a l i k e i n w a t e r . A c c o rd in g t o l i t e r a t u r e [ 4 , 11] I t ca n s u b s t a n t i a t e th e b r e a k i n g a f f e c t o f d i s s o lv e d N al on t h e s t r u c t u r e o f w a te r - a c e t a m l d e s o l v e n t s .
I n o r d e r t o com pare a c e ta m id e w ith o t h e r s o l v e n t s t h e d e p e n d e n c e s o f A rjr /A T c o e f f i c i e n t ' o f 0 . 5 m N al s o l u t i o n s i n s e v e r a l w a t e r - o r g a n i c s o l v e n t s on t h e m ix tu r e c o m p o s itio n a r e p r e s e n t e d on F i g , 1 1 . F i g . 1 1 . D ependence o f A t]x /A T c o e f f i c i e n t o f 0 . 5 m N al s o l u t i o n s i s s e v e r a l w a te r - o r g a n i c s o l v e n t s on t h e m ix tu r e co m p o si t i o n w i t h i n t h e te m p e r a tu r e ra n g e 2 5 -3 5 ° C . 1 - w a t e r - i s o p r o p a - n o l [ 1 2 ] ; 2 - w ater-EM F [1315 3 « w a te r - a c a t a m i d e ; 4 w a te r --fo rm a m id e [ 1 3 ] From t h e e n c l o s e d d a t a i t f o l l o w s t h a t A î] r /A T c o e f f i c i e n t o f a q u e o u s N al s o l u t i o n s c o n t a i n i n g s m a ll am o u n ts o f DMF (u p t o ~ 5 m ole % ) an d ls o p r o p a n o l ( u p t o ~ 10 m ole %) g ro w s w i t h th e v i n c r e a c i n g o r g a n i c com ponent c o n t e n t s . I t s u b s t a n t i a t e s th e g ro w in g b r e a k i n g e f f e c t o f N al on t h e s t r u c t u r e o f t h e s e m ix t u r e s . T hus a c o n c l u s i o n can be draw n t h a t t h e m i x tu r e s a r e m ore o r d e r e d th a n p u r e w a t e r . T h is c o n c l u s i o n i s i n a g re e m e n t w ith th e r e s u l t s o f w orks o f K e s s l e r e t . a l . [1 4 , 1 5 ] . The g r e a t e r c o n t e n t s o f DMF an d l s o p r o p a n o l In t h e m ix tu r e c a u s e s t h e d e c r e a s e o f v a l u e o f t h e d i s c u s s e d c o e f f i c i e n t w h ic h c h a n g e s I t s s i g n i n t o n e g a t i v e . S i m i l a r l y , i n w a te r-fo r m a m ld e sy ste m t h e v a l u e o f A t ] r /A T c o e f f i c i e n t d e c r e a s e s w i t h g ro w in g am ide
c o n t e n t s . The n e g a t i v e s i g n o f t h e c o e f f i c i e n t Ar]r /A T o f N al s o l u t i o n s s u b s t a n t i a t e s t h e o r d e r i n g e f f e c t o f t h e d i s s o l v e d e l e c t r o l y t e on t h e s t r u c t u r e o f t h e d is c u s s e d m i x t u r e s . I t c a n b e e a s i l y o b s e r v e d t h a t fro m a l l t h e d i s c u s s e d s u b s t a n c e s f o r - mamide b r e a k s w a te r s t r u c t u r e m o s t. I n c a s e o f w a te r - a c e t a m i d e s y s te m t h e c o e f f i c i e n t AT)r /A T p o i n t s w e ak ly t o t h e d i s t u r b in g e f f e c t o f N al on t h e s t r u c t u r e o f w a te r - a c e t a m i d e m i x tu r e s a l i k e I n c a s e o f p u r e w a te r n ad m o lte n a c e ta m id e [ 4 ] , The b re ak -, ln g e f f e c t o f N al s l i g h t l y i n c r e a s e s w ith t h e g ro w in g c o n t e n t s o f a c e ta m id e i n t h e s o l u t i o n . From t h e c a r r i e d o u t c o m p a riso n i t f o l l o w s t h a t a c e ta m id e w ith t h r e e d im e n t lo n a l h y d ro g e n bond l a t t i c e I n s o l i d s t a t e [ 1 6 - 1 8 ] p r o b a b ly fo rm s w ith w a te r t h e a s s o c i a t e s w ith s p a c i a l s t r u c t u r e w h i l e f l a t form am ide m o le c u l e s [ 1 9 3 form c h a in a s s o c i a t e s w ith w a te r [ 2 0 , 2 1 ] . U sin g J o n e s - D o le ’ s e q u a ti o n we h av e d e te r m in e d t h e v a l u e s o f A and B c o e f f i c i e n t s o f N al s o l u t i o n s i n w a te r - a c e t a m i d e m i x t u r e s . The c o e f f i c i e n t A s u b s t a n t i a t i n g t n 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 among i o n s i n t h e s o l u t i o n s i s c l o s e t o z e r o an d a lm o s t d o e s n ' t c h a n g e w ith th e g ro w in g t e m p e r a t u r e . The v a l u e s o f B c o e f f i c i e n t ( T a b le 3) b e in g th e m e a su re o f i n t e r a c t i o n s T a b l e 3 The v a l u e s o f B ( 1 /m o l e ) c o e f f i c i e n t o f J o n e s - D o l e ’ s e q u a ti o n o f N al i n w a te r - a c e t a m i d e s o l v e n t s - — \---T (°C ) 5 w t 54 AcNH2 15 w t % :30 w t % AcNH0 i AcNH, 2 , • 2 50 wt % AcNr^ 70 wV % AcNH2 85 w t % AcNH2 95 w t # AcNH2 25 ---0 .---0 4 . 0 .0 6 0 .0 8 0 .0 9 - - -40 0 .0 6 0 .0 7 0 .1 0 0 .1 1 - -60 C .0 7 . 0 .0 9 0 .1 2 0 .1 4 0 .1 9 - -75 0 .0 9 0 .1 1 0 .1 4 0 . 16' 0 .2 1 - -85 0 .1 0 0 .1 2 0 .1 5 0 .1 7 0 .2 3 0 .3 3 0 .4 2 among i o n s and m o le c u le s o f t h e s o l v e n t a r e p o s i t i v e i n c a s e o f t h e s o l u t i o n s i n v e s t i g a t e d by u s . The v a l u e s o f t h i s c o e f f i c i e n t i n c r e a s e w ith t h e g ro w in g c o n t e n t s o f a c e ta m id e i n t h e m ixed
s o l v e n t and w ith t h e te m p e r a tu r e g r o w th . From t h l a I t f o l l o w s t h a t t h e e f f e c t o f th e a d d i t i o n o f a c e ta m id e on e l e c t r o l y t e - - w a t e r i n t e r a c t i o n s i s s i m i l a r t o th e e f f e c t o f t e m p e r a t u r e . I t i s known t h a t te m p e r a tu r e g ro w th h a s b r e a k i n g e f f e c t on t h e s o l v e n t s t r u c t u r e , so a c e ta m id e m o le c u le s a l s o c a u s e t h e d i s tu r b a n c e o f s t r u c t u r e o f a q u e o u s N al s o l u t i o n s . I t seem s p r o b a b l e t h a t t h i s f a c t i s c o n n e c te d . w i t h t h e a f f i n i t y o f - a c a t - am ide m o le c u le s ( h y d r o p h i l i c c h a r a c t e r ) t o w a t e r . The f o r m a tio n o f m ixed a s s o c i a t e s from w a te r an d a c e ta m id e m o le c u le s bound by h y d ro g e n b o n d s d i s t u r b s t h e s t r u c t u r e o f a q u e o u s N al s o l u t i o n . A s i m i l a r c o u r s e o f r e l a t i o n o f B c o e f f i c i e n t o f NagSO^ an d MgSO^ t o a c e ta m id e c o n t e n t s i n m ixed H?0-AcNH2 s o l v e n t was o b s e r v e d by D. S in g h , N, P . S in g h an d L. B a h a d u r [ 2 2 ] . The i n v e s t i g a t i o n s o f v i s c o s i t y o f H gO -A cN t^-N al s y s te m i n f i v e te m p e r a t u r e s c a r r i e d o u t by u s a llo w e d t o c a l c u l a t e th e v a l u e s o f th erm o d y n a m ic f u n c t i o n s o f a c t i v a t i o n f o r f l u i d flo w from E y r i n g ’s e q u a ti o n : i , Vv w AG ^ m AH ao* . Tj ■ - y - ex p —j>£rj5 ■ ~y~ exp — e xp —g ( 2 ) w h e re : h - P la n c k ’ s c o n s t a n t N - A v o g a rd o 's num ber V - m o la r volum e o f s o l v e n t R - g a s s c o n s t a n t
AG*, AH* an d AS* - f r e e e n e r g y , e n t h a l p y an d e n t r o p y o f a c t i v a t i o n f o r f l u i d f l o w .
I t f o l l o w s from t h e l i t e r a t u r e [ 2 3 - 2 5 ] t h a t i n c a s e o f w a te r s t r u c t u r e o r d e r i n g e l e c t r o l y t e s b o th AH* and AS* i n c r e a s e w ith t h e g ro w in g s a l t c o n c e n t r a t i o n , w h i l e s o l v e n t s t r u c t u r e b r e a k i n g e l e c t r o l y t e c a u s e s t h e d e c r e a s e o f t h e v a l u e s o f t h e s e f u n c t i o n s . D i s c u s s i n g th e v a l u e s fro m T a b le s 4 - 7 i t can be n o - t i v e d t h a t e n t h a l p y o f a c t i v a t i o n f o r f l u i d f l o w o f Nal s o l u t i o n i n w a t e r - a c e ta m id e m i x tu r e s d e c r e a s e s w ith t h e g ro w th o f s a l t c o n c e n t r a t i o n and t e m p e r a t u r e , s i m i l a r l y t o w a te r [ 2 4 ] , Tne g ro w th o f a c e ta m id e c o n t e n t s i n m ixed s o l v e n t on th e o t h e r h a n d , c a u s e s t h e i n c r e a s e o f t h e v a l u e e n t h a l p y o f a c t i v a t i o n .
T a b l e 4
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m o le kJ kJ J kJ kJ J kJ kJ J kJ kJ J kJ kJ J
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0 .0 2 1 7 .3 8 1 0 .1 2 2 4 .4 1 6 .6 3 9 ,7 7 2 1 .9 1 5 .7 3 9 .4 2 1 8 .9 1 5 .1 2 9 .1 6 1 7 .1 1 4 .7 4 9 .0 1 ----1 6 ,0 0 .0 5 1 7 .3 5 1 0 .1 2 2 4 .3 1 6 .6 0 9 . 7 8 2 1 .8 1 5 .7 0 9 .4 3 1 8 .8 1 5 .0 9 9 .1 7 1 7 .0 1 4 .7 2 9 .0 2 1 5 .9 0 . 0 8 1 7 .3 2 1 0 .1 3 2 4 .2 1 6 .5 7 9 .7 8 2 1 .7 1 5 .6 7 9 . 4 3 1 8 .7 1 5 .0 6 9 .1 8 1 6 .9 1 4 .6 9 9 . 0 3 1 5 .8 0 . 1 0 1 7 .3 0 1 0 .1 3 . 2 4 .1 1 6 .5 5 9 .7 9 2 1 .6 1 5 .6 5 9 . 4 4 1 8 .6 1 5 .0 5 9 .1 8 1 6 .8 1 4 .6 7 9 .0 4 1 5 .7 0 .1 5 1 7 .2 5 1 0 .1 4 2 3 .9 1 6 .5 0 9 .7 9 2 1 .4 1 5 .6 1 9 . 4 5 1 8 .5 1 5 .0 0 9 .2 0 1 6 .7 1 4 .6 3 9 . 0 6 1 5 .6 0 . 2 0 1 7 .2 1 1 0 .1 4 2 3 .7 1 6 .4 6 9 .8 0 2 1 .3 1 5 .5 6 9 .4 7 1 8 .3 1 4 .9 5 9 .2 1 1 6 .5 1 4 .5 8 9 .0 7 1 5 .4 0 .3 0 1 7 .1 4 1 0 .1 6 2 3 .4 1 6 .3 7 9 .8 2 2 0 .9 1 5 .4 6 9 . 4 9 1 7 .9 1 4 .8 5 9 .2 5 16 .1 1 4 .4 7 9 .1 1 1 5 .0 0 . 4 0 1 7 .0 8 1 0 .1 7 2 3 .2 1 6 .3 0 9 .8 4 2 0 .6 1 5 .3 6 9 .5 1 1 7 .6 1 4 .7 3 9 .2 8 1 5 .7 1 4 .3 4 9 .1 4 1 4 .5 0 .5 0 1 7 .0 4 1 0 .1 8 2 3 .0 1 6 .2 3 9 .8 5 2 0 .4 1 5 .2 6 9 .5 4 1 7 .2 1 4 .6 0 9 .3 1 1 5 .2 1 4 .2 0 9 .1 8 1 4 .0 0 . 6 0 1 7 .0 2 1 0 .2 0 2 2 .9 1 6 .1 7 9 .8 7 2 0 .1 1 5 .1 5 9 .5 6 1 6 .8 1 4 .4 7 9 .3 4 1 4 .7 1 4 .0 4 9 .2 1 1 3 .5
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0 .0 2 1 9 .0 0 1 1 .1 6 2 6 .3 1 8 .0 3 1 0 .8 0 2 3 .1 1 6 .8 7 1 0 .4 4 1 9 .3 1 6 .0 9 1 0 .1 6 1 7 .0 1 5 .6 1 1 0 .0 4 1 5 .6 0 . 0 5 1 8 .9 6 1 1 .1 7 2 6 .1 1 8 .0 0 10 .8 1 2 3 .0 1 6 .8 4 1 0 .4 5 1 9 .2 1 6 .0 6 1 0 .1 7 1 6 .9 1 5 .5 8 1 0 .0 5 1 5 .4 0 .0 8 1 8 .9 3 1 1 .1 7 2 6 .0 17.96 10.31 2 2 .8 16.8 1 1 0 .4 6 19 .1 1 6 .0 3 1 0 .1 8 1 6 .8 1 5 .5 5 1 0 .0 7 1 5 .3 0 .1 0 18 .9 1 1 1 .1 8 2 5 .9 17 .9 4 1 0 .8 2 2 2 .7 1 6 .7 9 1 0 .4 7 1 9 .0 16.01 1 0 .1 9 1 6 .7 1 5 .5 3 1 0 .0 7 1 5 .2 0 .1 5 1 8 .8 5 1 1 .1 9 2 5 .7 1 7 .8 9 1 0 .8 3 2 2 .5 1 6 .7 4 1 0 .4 8 1 8 .8 1 5 .9 6 1 0 .2 1 1 6 .5 1 5 .4 8 1 0 .1 0 1 5 .0 0 .2 0 1 8 .7 9 1 1 .2 0 2 5 .5 1 7 .8 3 1 0 .8 4 2 2 .3 1 6 .6 8 1 0 .5 0 1 8 .6 15.91 1 0 .2 3 1 6 .3 1 5 .4 3 1 0 .1 2 1 4 .8 0 .2 0 1 8 .6 8 1 1 .2 2 2 5 .1 1 7 .7 2 1 0 .8 7 2 1 .9 1 6 .5 8 1 0 .5 3 1 8 .2 15.81 1 0 .2 7 1 5 .9 1 5 .3 3 1 0 .1 6 1 4 .4 0 .4 0 1 8 . 5 e 1 1 .2 4 2 4 .6 1 7 .6 2 1 0 .8 9 2 1 .5 1 6 .4 8 1 0 .5 7 1 7 .8 15.71 1 0 .3 1 1 5 .4 1 5 .2 4 1 0 .2 0 1 4 .1 j 0 . 5 0 1 8 . 4 7 1 1 .2 6 2 4 .2 1 7 .5 2 10 .9 1 2 1 .1 1 6 .3 9 1 0 .6 0 1 7 .4 1 5 .6 2 1 0 .3 6 15 .1 1 5 .1 5 1 0 .2 4 1 3 .7 }0.6Q 1 8 .3 7 1 1 .2 8 2 3 .8 1 7 .4 2 1 0 .9 3 2 0 .7 1 6 .2 9 1 0 .6 ? 1 7 .0 1 5 .5 3 1 0 .4 0 1 4 .7 1 5 .0 5 1 0 .2 8 1 3 .3
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From t h i s I t f o l l o w s t h a t Nal I n t r o d u c e d t o w a t e r - a c e t a m i d e s o l v e n t a c t s s i m i l a r l y t o t h e g ro w th o f t e m p e r a t u r e i . e . b r e a k s s o l v e n t s t r u c t u r e . F l u i d f l o w o f t h e s o l v e n t w i t h d i s t u r b e d s t r u c t u r e r e q u i r e s s m a l l e r i n p u t o f e n e r g y . The a d d i t i o n o f a c e t - am id e c a u s e s o p p o s i t e e f f e c t . The i n c r e a s e o f a c e t a m i d e c o n t e n t s i n a q u e o u s N al s o l u t i o n c a u s e , a s i t was m e n t i o n e d a b o v e , t h e f o r m a t i o n o f g r e a t e r an d g r e a t e r ammounts o f mixed a s s o c i a t e s , w h ic h makes t h e f l u i d f l o w o f t h e s o l u t i o n more d i f f i c u l t . Thus t h e e n t h a l p y o f a c t i v a t i o n f o r f l u i d f l o w grow s w i t h t h e i n c r e a s i n g a c e t a n i d e c o n t e n t s i n t h e s o l u t i o n . S i m i l a r c o n c l u s i o n s a b o u t t h e e f f e c t o f Nal a n d a c e t a m i d e on t h e s t r u c t u r e o f i n v e s t i g a t e d s y s t e m s c a n be drawn fro m t h e a n a l y s i s t h e d e p e n d e n c e o f a c t i v a t i o n e n t r o p y f o r f l u i d f l o w o f t h e d i s c u s s e d s y s t e m s on t h e s o l u t i o n c o n c e n t r a t i o n , a c e t a m i d e c o n t e n t s i n t h e m ixed s o l v e n t an d on t e m p e r a t u r e . REFERENCES [ 1 ] K a m i n s k y M ., 2 . P n y s . C hem ., 5 , 154 (1 9 5 5 ); § . 173 ( 1 9 5 6 ) ; 12, 206 (1 9 5 7 ) . [ 2 ] K a m i n s k y M ., D i s c . F a ra d a y S o c ., 24, 171 (1 9 5 7 ) . [ 3 ] P i e n k i n a N. W., Z h u r. F i z . K hiœ . ( " V i n i t i " No 2Ô12, 2Ó13, 2 6 1 4 , 2 6 1 5 ) ( 1 9 7 1 ) , [ 4 ] W o 1 d a n M ., D o c to r a l D i s s e r t a t i o n , U n i v e r s i t y Ł ód ź,
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[ 5 ] T a n i e w s k a - O s i ń s k a S . , W o 1 d a n M ., A c ta U n iv . L o d z . ZNUŁ, S . IX , 2 4 , 33 (1 9 7 0 ) . [ 6 ] T a n i e w s k a - 0 s i ń s k a S . , V o 1 d a n M., R o c z . C hem ., 4 8 , 1753 (1 9 7 4 ) . [ 7 ] T a n i e w s k a - 0 s i ń s k a S . , W o 1 d a n M., R o cz. C hem ., 5 j , 1933 (1 9 7 7 ). [ 8 ] R O h d e w a 1 d P . , M o 1 d n e r M ., J . P h y s . Cham ., 7 7 , 373 (1 9 7 3 ) . [ 9 ] r, o n c z a r o w W. S . , L J a s z c z e n k o J a s t r e m s k i j P . S . , Z h u r. S t r u k t . K h i n .. - , •*,[10] G o n c z a r o w W. S . , J a s t r e m s k i J P . S . t I z v . V y s s h . U c h e b . Z a v o d . Khim. Khim. T e k h n ., A, 6 0 2 (1 9 7 6 ). [ 11] S t o k e s R. H. , M i l l s R . , V i s c o s i t y o f E l e c t r o - l y t e s and R e l a t e d P r o p e r t i e s , N«w Y ork ( 1 9 6 5 ) . [12] T a n i e w s k a - 0 s i ń s k a S. , K a c p e r s k a A ., P o l . J . C hem ., 5 3 , 1351 (1 9 7 9 ) . [ 13] P i e k a r s k a A ., D o c to r a l D i s s e r t a t i o n , U n i v e r s i t y Ł ó d i (1 9 7 5 ) . [14] M 1 s h u s t i n A. J . , K e s s l e r Y u . M ., Z h u r . S t r u k t . K h im ., 1 5 , 205 (1 9 7 A ). [15] V e r s t a k o v E. S. , Y a s t r e a s k i J P. S. , K e s s l e r Yu . M. , M i s h u s t 1 n A. J . , E m a i l n V , P . , Z h u r. F i z . K h im ., 4 9 , 160A ( 1 9 7 5 ) . [16] S e n t i F. , H a r k e r , D ., J . Am. Chem. S o c . , 6 2 , 2008 (1 9,40). [17] H a m i l t o n W. C ., A c ta C r y s t , , 18, 866 ( 1 9 6 5 ) . [18] D e n n e W. A. , S m a l l R . W. H ., A c ta C r y s t . , B27, 109A ( 1 9 7 1 ) . f l 9 ] L a d t l 1 J . , P o s t B . , A c ta C r y s t . , 7 , 559 (195A). [20] K e s s l e r Yu. M. , E m e l i n V. P. , T o l u l e e v Yu. S. , T r u s k o v 0 . V. , L a p s h i n R . M ., Z h u r. S t r u k t . K h im ., l_3 , 2 , 210 (1 9 7 2 )* [21] Y a s t r e o s k i J P. S . , V e r s t a k o v E. S. , K e s s l e r Yu. M. , M i s h u s t i n A. J . , E m e - 1 i u V. P . , B o b r i n e r Y u. M ., Z h u r . F i z . K h im ., 4 9 , 2950 (1 9 7 5 ) . [2 2 ] S i n g h D ., S i n g h K . P . , B a h a d u r L . , I n d i a n J . C hem ., 1 3 , 1177 (1 9 7 5 ) . [2 3 ] G o o d W., E l e c t r o c h i m i c a A c ta , 1 0 , 1 (1 9 6 5 )5 11« .7 5 9 , 7 6 7 , (1 9 6 6 )} 12, 1031 ( 1 9 6 7 ) . [2 4 ] G o o d W., E l e c tr o c h i m i c a A c ta , 9 , 203 (1 9 6 4 ) . [2 5 ] N i g h t i n g -a 1 e E . R ., B e n o k R . F . , J . ' P h y s . C hem ., 63,, 1777 (1 9 5 9 ) . D e p a rtm e n t o f P h y s i c a l C h e m is try U n i v e r s i t y o f Ł ódź
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