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 3 , 1984___________________
S t e f a n l a T an iew sk a-O sirisk a, M a lg o rz a ta J<5iwiak CALOKIMETRIC INVESTIGATION OF ANILINE SOLUTIONS
IN HMPT-HgO MIXTURES AT 2 9 8 .1 5 K
E n th a lp ie s o f s o l u t i o n o f a n i l i n e , KI and KCI in HMPT-water m ix tu re s c o n ta in in g up t o 3 mole % o f IIMPT w ere m easu red . S ta n d a rd e n t h a l p i e s o f s o l u t i o n AH ana e n t h a l p i e s o f t r a n s f e r o f th e compounds under s tu d y from w a te r t o th e m ixed s o lv e n t AH?r were c a l c u l a t e d . The r e s u l t s o b ta in e d e x p e r im e n ta lly a r e e x t e n s i v e l y d iscu ss ed a g a i n s t th e background o f th e r e l e v a n t l i t e r a t u r e d a t a .
I n t r o d u c ti o n
I n v iew o f th e f a c t t h a t hexam eth y lph osphoram id e (HMPT) i s an a p r o t i c s o l v e n t w ith good d i s s o l v i n g p r o p e r t i e s 1 r e l a t i v e to a w ide ra n g e o f b o th e l e c t r o l y t e s an d o r g a n ic s u b s ta n c e s th e compound h a s r e c e iv e d a l o t o f a t t e n t i o n o f i n v e s t i g a t o r s . Mi x t u r e s o f HMPT w ith w a te r have been s t u d i e d by s p e c t r o s c o p i c
[1 -3 ] a3 w e ll a s by d e n s im e tr ic , v i s c o s i a e t r i c , and c o n d u c to - m e tr ic [4 -8 ] m ethod s. S i m i l a r l y , th re e -c o m p o n e n t HMPT-HgO-elec- t r o l y t e m ix tu re s have been s t u d i e d by d e n s im e tric -, v i s c o s i m e t- r i c , and c o n d u c to m e tric m ethods [4 -8 ] a s w e ll a s c a l o r i m e t r i c - a l l y [ 9 ] .
An a n a l y s i s o f th e r e s u l t s o b ta in e d l e d K e s s le r to th e c o n c lu s io n t h a t HMPT form s c l a t r a t e s w ith w a te r [ 1 - 3 ] . M e rlin e t a t . [10] i n v e s t i g a t e d th re e -c o m p o n e n t H H PT-H pC -nonelectroIy- t e m ix tu re s a n d , on th e b a s is o f s t u d i e s o f AG°r , A n ^ ,, ana AS°r , th e y s u g g e s te d t h a t HHPT m ig h t be r e g a r d e d a s a h y d ro - p h o b ic compound w ith s t r u c t u r e making p r o p e r t i e s r e l a t i v e to
w a te r in w a t e r - r i c h m ix tu r e s . Between h y d ro p h o b ic compounds on th e one h an d , and HMPT on th e o t h e r , t h e r e may p la c e i n - t e r m i a c i b i l i t y o r i n te r g g r e g a ti o n . The aim o f th e r e s e a r c h r e p o r t e d h e re was to o b ta in more in fo r m a tio n a b o u t HMPT-h^O sy ste m by way o f c a l o r i m e t r i c m easurem ents o f th e h e a t o f s o l u t i o n o f a t h i r d s u b s ta n c e i n i t . A n ilin e was s e l e c t e d a s th e s o l u t e and i t s h e a t o f d i s s o l u t i o n was d e te rm in e d i n th e ra n g e o f sm a ll HMPT c o n t e n t s , t h e ra n g e t h a t seems p a r t i c u l a r l y i n t e r e s t i n g in l i g h t o f th e r e s e a r c h r e f e r r e d t o abo v e . E x p e rim e n ta l P u re HMPT m a n u fa c tu re d by FTuka AC w ith w a te r c o n te n t o f / ,
l e s s th a n 0 .0 5 p e r c e n t and nd o f 1 .4 5 9 was em ployed. A ni l i n e , d r ie d o v e r KOH, was d i s t i l l e d p r i o r t o e a c h measurem e n t} i t s p u r i t y was t e s t e d by UV a n d IR s p e c tr o s c o p y . The m easurem ents were made i n an " " i s o p e r i b o l " ty p e c a l o r i m e t e r a t 298 .15 - 0 .0 0 5 K. The h e a t o f a n i l i n e s o l u t i o n was m easured in th e ra n g e o f 0 .0 0 4 3 -0 .0 2 2 1 m ole/kg i n th e m ixed • s o lv e n t w hich c o n ta in e d from 0 t o 3 mole p e r c e n t o f HMPT i n wa t e r .
R e s u lts and d i s c u s s io n
The h e a ts o f a n i l i n e s o l u t i o n i n w a te r and i n th e mixed s o l v e n t HMPT + HL,0, and th e h e a t o f a n i l i n e t r a n s f e r t o th e m ixed s o lv e n t a r e p r e s e n te d i n Tab. 1 .
S ta n d a r d e n t h a l p i e s o f s o l u t i o n i n i n f i n i t e l y d i l u t e s o l u t i o n s AH° fe>Nr a n i l i n e d i s s o l v e d in w a te r and i n th e mix ed s o l v e n t HMPT +■ ^ 0 have been d e te rm in e d g r a p h i c a l l y . The h e a ts o f a n i l i n e t r a n s f e r from w a te r t o th e m ixed s o l v e n t a r e p l o t t e d i n F ig . 1f t o g e t h e r w ith th e c o rr e s p o n d in g fu n c t io n o b ta in e d f o r p - n i t r o a n i l i n e by M e r l i n e t a l . [10] who c a l c u l a t e d th e e n th a lp y o f t r a n s f e r ta k in g a d v a n t age o f s o l u b i l i t y m easurem ents and u s in g th e fo rm u la :
H eat o f s o l u t i o n o f C-H^NHg i n water-HMPT m ix tu re s a t 2 98 .1 5 K XHMPT mc6H5NH2 [m o l/k g j AH [j/m o l] iH ? r [J /mol] XHMPT ° W H2 [ra o l/k g ] AH [J /m o l] “ t r [J/m ol] XHMPT [m ol/kg] AH [J/m ol] AH?t r [ J/m o l] 0 .0 0 0 0 0 .0 0 6 2 1816 ' 0 610051 0 .0 0 4 7 3628 -1791 0.0201 0 .0 0 4 8 8460 -6640 0 .0 0 6 9 1807 0 .0 0 4 8 3607 0 .0 0 5 0 8443-0 .8443-0 8443-0 7 2 1820. ,0.0080 3586 0 .0 0 9 7 8439 0 .0 0 7 2 1812 0 .0 0 8 8 3586 0 .0 1 0 0 8439 0 .0 0 7 3 1833 0 ,0 1 8 5 .. 3565 0 .0 1 8 2 8414 0 .0 0 7 3 1833 • 0 .0 2 0 3 3569 0 .0 1 9 0 8418 0 .0 0 9 7 1803 0 .0 1 5 9 1795 0 .0 1 5 9 1795 0 .0 0 3 6 0 .0 0 4 3 2912 -1 0 9 6 0 .0 1 3 4 0 .0 0 4 4 6452 -4 6 5 7 0 .0 3 0 0 0.00 45 10774 -3 9 5 0 0 .0 0 5 3 2891 0 .0 0 4 9 6489 0 .0 0 5 2 10732 0 .0 0 8 4 2916 0 .0 0 6 9 6456 0 .0 0 9 7 10736 0 .0 0 8 3 2891 0 .0 0 8 3 6477 0.0111 10745 0 .0 0 8 9 2916 0 .0 1 6 9 6435 0 .0 2 2 0 10719 / 0 .0 1 6 8 2900 0.0173 6439 0.0221 10678 C al o r im ot r ic in v e e tle & tlo n of a n il in e s o lu ti o n s .
w h ere:
F i < 1.
AH?*. - AO? + TASt r
AG? . - R T l n ! a o ^ ertt
t r w a te r
A Hjr t J-mol'1 • 10* ]
30
H eat o f t r a n s f e r o f p-NOa-CfcHsNHj, C6 Hs NHo from w a te r to KMPT-water m ix tu re s a t 2 9 8 .1 5 1C -I--- ► 3 mol% HMPT x - p-no2 -c6h5nh2 • - C6 H5NH2 As c ■ d- s e e n , th e p l o t s have d i f f e r e n t s h a p e s . A p o s s i b l e rc-.23on is th e p re s e n c e o f th e -N02 g ro u p i n C^H^NHgNOg o r a
b e t t e r a c c u ra c y o f c a l o r i m e t r i c m easurem ent o f r e l a t i v e t o th e c o rre s p o n d in g v a lu e d e te rm in e d i n d i r e c t l y . The d i f f e r ence in th e sh a p e s o f th e p l o t s f o r a n i l i n e and p - n l t r o a n i l l n e a ro u s e d o u r i n t e r e s t i n th e c o u rs e o f e n th a lp y in th e f u n c tio n o f th e c o m p o s itio n o f t h e m ixed s o lv e n t In th e c a s e o f e l e c t r o - ■'* l y t e s o l u t i o n s . In th e l i t e r a t u r e a v a i l a b l e t o us we have found a s tu d y o f V o r o b e v e t a l . [ 9 ] c o n c e rn in g th e m easurem ent o f KCi and KI s o l u t i o n e n th a lp y in HMPT-HgO and th e p l o t s o b ta in e d by th o s e a u th o r s a r e p r e s e n te d in F ig . 2 .
AH* [ kJ • mot*1 ]
F ig . 2 . H eat o f s o l u t i o n o f KCI, KI in water-HMPT m ix tu re s a t 2 90 .1 5 K
I t i s p o s s i b l e t h a t t h e AH0 d a ta f o r KI and KCI i n w a te r , p r e s e n t e d h e re in F ig . 2 and a d o p te d from th e p a p e r o f _ V o r o b e v e t a l . [ 9 ] , w ere n o t d e te rm in e d by th o s e a u th o r '
th e m s e lv e s b u t were ta k e n from some l i t e r a t u r e t o w hich no r e f e r e n c e i s made. Such a c o n c lu s io n i 3 s u g g e s te d by th e f a c t t h a t , u n l ik e o t h e r d a ta g iv e n in th e o r i g i n a l p a p e r , th e s e a r e n o t c o l l e c t e d in th e r e l e v a n t t a b l e b u t o n ly p l o t t e d i n a f i g u r e .
I n v iew o f th e d i f f e r e n t c o u rs e o f AH° p l o t s f o r KC1 and KI i n th e f u n c t i o n o f s o l v e n t c o m p o s itio n i n co m p ariso n w ith th e p l o t s f o r a n i l i n e and p - n i t r o a n i l i n e , we d e c id e d t o a n a ly z e V o ro b e v 's d a t a . To t h i s end we d e te rm in e d AH° f o r KI i n wa t e r and t h e f in d i n g s o b ta in e d a r e c o l l e c t e d i n T ab. 2 , T a b l e 2 H eat o f s o l u t i o n o f KI in w a te r a t 2 9 8 .1 5 K XUMPT mKI [m ol/k g] AH [j/m o l] AH0 [J/m o l] 0.0 0 1 8 20029 0.0 0 2 6 20056 0 .0 0 2 9 20016 0.0 0 3 2 20010 0 .0 0 3 8 20011 0 .0 0 4 4 20001 0 .0 0 4 5 20020 0 .0 0 0 0.00<+8 20028 20040 - 200a ) 0 .0 0 5 0 20059 19934 Î 200b 0.0Q50 20048 0.005 3 20020 0.C057 20026 0 .0 0 6 7 20067 0,0071 20074 ('.0 0 7 8 20022 C.0034 20059 0 .0 0 8 4 20086
4 V alue c a l c u l a t e d a3 a mean o f a l l m easu rem en ts. b Value o b ta in e d by th e m ethod o f Guggenheim and P ru e .
The s ta n d a r d h e a t o f KI s o l u t i o n i n w a te r was c a l c u l a t e d by t h e m ethod o f C uggenhein and Prue and compared w ith th e l i t e r a t u r e 'd a t a (T a b , 3 ) . T a b l e 3 H eat o f s o l u t i o n o f KI in w a te r a t 29 3 ,1 5 K A u th o rs , Year and R e fe re n c e Number o f measu rem e n ts 5 O M 9 y-i AH0 [J/m o l] WUst, Lange 1925 [11] 24 7 .9 5 - 0 .2 9 20490 + 250 Lange, M arbin 1937 [12] 1 0.11 20390 + 250 K a p u s t in s k i i, D rak in 1952 113] 1 0 .0 0 0 8 20210 + 300 P a r k e r ’ s " 3 e s t " v a lu e 1965 [14] _ • 20330 + 130 T sv e tk o v , R ab in o v ich 1969 [1^] 1 0 . f l 1 20150 + 250 J o ] y , T ljourney, P ^rachon m ■ 0 ,0 1 8 4 20580 ♦ 210
Efim ov, K le v a ic h u k ond a l .
1979 [17] 11 0 .0 0 6 -0 .0 7 20145 ♦ 24
Our d a ta 17 0 .0 0 1 8 -0 .0 0 8 4 20040 + 200a
19934 + 200b ,
a Value c a l c u l a t e d a s a mean o f a l l m easurem ents. b Value o b ta in e d by th e m ethod o f Guggenheim and P ru e .
A3 can be s e e n , o u r r e s u l t i s in good ag re e m e n t w ith m ost o f th e l i t e r a t u r e d a ta a s w e ll a s w ith th o s e recommended by NBÜ ( 2 0 .1 5 +• 0 .2 k J/m o le) [ 1 7 ] , w h ile th e v a lu e e x t r a c t e d from Vo- ro b e v ’ s p l o t a g re e s w ith t h a t o b ta in e d by . ii s t and L a n g e [11]« Assuming t h a t Vorobev a d o p te d th e r e s u l t i n q u e s t i o n from th e s tu d y o f Wiist and Lange, i t h as to be p o in te d o u t t h a t t h e l a t t e r a u th o r s c a l c u l a t e d i t from m easurem ents r. uie f o r s o l u t e c o n c e n t r a t io n s o f 7 .9 5 + 0 .2 9 m ole/tcg. i t th u s seems t h a t th e r e s u l t s o b ta in e d by i f i m o v [17] and us ,;re more a c c u r a te b e c au se th e m easurem ents were made f o r c o n s id e r a b ly more d i l u t e s o l u t i o n s . To e s t a b l i s h th e d e g re e o; agréée1
.-e n t b.-etw .-e.-en Vorobev’ s d a ta and o u rs we m easured th e h e a t o f KI s o l u t i o n in th e mixed s o lv e n t c o n ta in in g 0 .0 0 5 mol % HMPT. Thj v a lu e o f th e s ta n d a r d h e a t o f s o l u t i o n was c a l c u l a t e d by th ^ method o f Guggenheim and P ru e . The f in d i n g s c a l l e c t e d i n Tab. 4 a g re e - w ith in th e l i m i t e r r o r - w ith th o s e o f V o ro b e v 's . T a b l e 4 H eat o f s o l u t i o n o f KI in water-HMPT m ix tu re s a t 2 9 0 .1 5 K XHMPT mKI [raol/kg] AH [j/m o lJ AH0 [j/m o l] 0 .0 0 3 0 20200 0.0035 20194 0.0043 20165 0.0043 20201 O.OOpO 0 .0 0 4 5 20208 20076 ♦ 200 0.00t>b 20180 0 .0 0 5 9 20216 0 .0 0 6 0 20219 0 .0 0 7 8 20236 0 .0 0 8 9 20246 By c o n t r a s t t o th e mechod u s e d by us Vorobev c a l c u l a t e d th e s ta n d a r d h e a t o f s o l u t i o n u s in g a fo rm u la - tra n s fo r m e d by him s e l f and h i s a s s o c i a t e s - d e s c r i b in g th e se co n d a p p ro x im a tio n o f D e b y e an d H li c k e 1 [1 8 ). I n th e c a s e o f t h e KC1 p l o t we r e p e a te d th e m easurem ents o f th e h e a t o f s o l u t i o n i n w a te r , and th e r e s u l t s o b ta in e d a g re e - w ith in 0 .5 p e r c e n t - w ith th o s e e x t r a c t e d from V o r o - b e v* s p l o t [ 9 ] . F u rth e rm o re , u s in g th e e x o e rim e n ta l d a ta o b ta in e d by Vorobev f o r HMPT-water s y s te m s , we c a l c u l a t e d th e s ta n d a r d h e a t o f s o l u t i o n by th e l i m i t i n g law Debye and Hiickel th e c e th o d o f Guggenheim an d Prue c o u ld n o t be u s e d i n view o f th e s m a ll number o f m easurem ents ( t h r e e f o r e a ch b in a r y d r ,p o s it i o n o f th e s o l v e n t ) . As c an be s e e n i n Tab. 5 and *. 3 , th e two s e t s o f v a lu e s ( o u rs and V orobev’ s ) d i f f e r s l i g h t l y . '
T a b l e 5 H eat o f s o l u t i o n o f KC1, KI in th e water-HMPT m ix tu re s a t 2 9 8 .1 5 K AM0 [j/m o l] XHMPT KC1 KI 0 .0 0 0 172J8a 17163° 20500a 19934° 0 .00 5 17590 + 30b 17186d 19980 + 150b 20076° 0 .0 1 0 17530 + 40b 17336d 19900 + 50b 19792d 0 .0 3 0 19070 + 40b 18693d 19090 + 90b 18763d a D ata e x t r a c t e d from V o ro b ev 's p l o t . b Data c i t e d by Vorobev.
0 D ata m easured and c a l c u l a t e d by u s .
d D ata c a l c u l a t e d by u s from Vorobev’ s m easu rem ents.
T a b 1 o 6 H eat o f t r a n s f e r o f th e e l e c t r o l y t e s from w a te r t j HMPT-water
m ix tu re s a t 2 9 8 .1 5 K XHMPT AH°r [J/m o l] KC1 KI 0 .0 0 0 0 0 0*005 -2 3 -142 0 .0 1 0 -173 +142 0 .0 3 0 -15 3 0 + 1171 T ak in g a d v a n ta g e o f t h e new ly c a l c u l a t e d d a ta we d e t e r m ined th e h e a t o f e l e c t r o l y t e t r a n s f e r from w a te r i n to th e m ixed s o lv e n t and th e r e s u l t s a re p r e s e n te d in Tab. 6 ¿aid F ig . 4 .
S te fa n la Tftnlewska-Oslriak«, MalRorzata J6iwiale
3 mot % HMPT
F i r . 3. H eat o f s o l u t i o n o f
K c l, r f in th e water-HMPT F ig . 4 . H eat o f t r a n s f e r o f f i x t u r e s a t ? .j 3 .15 K. 1, 3 th e e l e c t r o l y t e s from w a te r - ' a lc u ltite d by us from to HMPT-water m ix tu re s a t
V o ro b ev 'a m easurem ents; 2 , 2 9 8 .1 5 K
4 - d a ta c i t e d by Vorobey
A H * [ U J • m o l* 1]
AH r [ J-m ol1 *10*] 12
In e v e ry c a s e , in th e ra n g e o f s m a ll HMPT c o n te n t in w a te r (u p to 0 .5 mol Si), t h e e n th a lp y o f t r a n s f e r d e c r e a s e s . More o v e r* th e p l o t s o f s o l u t i o n e n t h a l p i e s i n th e f u n c tio n o f s o l - ..vent c o m p o s itio n show a d i s t i n c t dependence on th e k in d o
d i s s o l v e d s u b s ta n c e .
^ The p r e s e n t f in d i n g s i n d i c a t e t h a t i t i s n e c e s s a ry to p e r form th e r e l e v a n t m easurem ents e v e ry 0 . 2 - 0 .3 mole A o f th e o r g a n ic c o s o lv e n t . O th e rw ise one may o v e rlo o k changes in th e
shape o f th e f u n c t i o n u n d e r s tu d y d e s c r i b in g th e change o f p r o p e r t i e s o f th e s y ste m . F u r th e r work on th e s o l u t i o n e n th a lp y i n HMPT - HgO m ix tu re s i s in p r o g r e s s . R e fe re n c e s [ 1] Y. M. K e s s 1 e r , V. P. E m e 1 i n , A. J . M i s h u - s t i n , P. S . J a s t r e m s k i j , E. S . V e r s t a - k o v , N, M. A 1 p a t o v a , M. C. F o m i c h e v u , K. V. K i r e e v , V. D. G r u b a , K. H. B r a t i s h - k o , Z hu r. S t r u c t . K hlm ., 16, 797 (1975). [ 2 ] V. S . G o n c h a r o v , P. S* J a s t r e rn s k i j , Y. M. K e s s 1 e r , R. H. B r a t i s, h k o , A . I . M i - s h u s t l n , V. P. E m e l i n , Z hu r. F iz . K him ., -51, 789 (1 9 7 7 ). [ 3 ] Y. M„ K e s s 1 e r , V. D. G r u b a , R. H. B r a t i - s h k o , I z v . VUZ Khim. i Khim . T e k h n o l., 24, 13o8 (1 9 8 1 ). [ 4 ] J . C. B o 1 1 i n g e r , G. Y v e r n a u 1 t , T. Y v e r - n a u 1 t , J . S o l . Chem., 7 , 317 (1 9 7 8 ). [ 5 ] J . C, B o l l i n g e r , T. Y v e r n a u l t , J .- Y . G a l , F. P e r s i n , Canad. J . Chem., 5 4 , 3060 (1 9 7 6 ). [ 6 ] J . - Y . G a l , Ch. L a v i l l e , F. P e r s i n , M. P e r a i n , J . - C . B o l l i n g e r , T. ' Y v e r n a u l t , Cana'd. J . Chem., .57, 11 2 7 ( 1 9 7 9 ) . [ 7 ] J . - C . B o l l i n g e r , T. Y v e r n a u l t , G a l , F. P e r s i n , C. R. A cad. S c . P a r i s , £ 3 7 , i ’i (1 9 7 8 ).
[ 8 ] E. M. H a n n a , N. J . A 1-S a 1 1 h i , J , S o l . Chem,, 8 , 539 (1 9 7 9 ). [ 9 ] A. F. V o r o b e v , L. S . , S a r k i 8 o v , Y. M. K e s s l e r , N. A. A b a k u m o v a , Z h u r. F iz. Khim., 5 5 , 1937 (1 9 8 1 ). ' [10J H. C h e b 1 b , C. J a m b o n , J - C . M e r l i n , J . Chlm. P h y s ., 78, 607 (1981) and C h e b 1 b H ., The s i s , U n iv e r s ite C laude B ern ard - Lyon 1981.
[11] J . W U s t , E. L a n g e , Z. P h y s ik . Chem,, 116. 161 (1 9 2 5 ). [12] E. L a n g e , W. Z. M a r t i n , Z. P h y s ik . Chem., A180. 233 (1 9 3 7 ). [13] A. F. K a p u s t i n s k i , S. I . D r a k i n , Z hur. F i z . K him ., 2 6 , 581 (1 9 5 2 ). [14] V. B. P a r k e r . Thermal P r o p e r t i e s o f U n i- u n iv a le n t E l e c t r o l y t e s N a t. S ta n d . R ef. D ata s e r , N a t. B ur. S ta n d , (U S ), Zj 66 (1 9 6 5 ). [15] V. G. T s v e t k o v , I . B. R a b 1 n o v i c h , , Z hur. F i z . K him ., 4,3, 1213 (1 9 6 9 ). [16] R .-D . J o l y , J . T h o u r e y , G. P e r a c h o n , C. R. Acad. S c . P a r i s , S e r . C, 2 27, 1179 (1 9 7 3 ). [17] M. E. E f i m o v , G. M. K 1 e v a 1 c h u k , V. A. M e d v e d e v , ^ M. V. K 1 1 d a y , J . R es. N a t. B ur. S t a n d . , 8 4 , 273 ( 1 9 7 9 ). / [18] S . M. S o 1 o v e v , N. M. P r i v a 1 o v a , A. F. V 0 r o b e v , Z hu r. F i z . K him ., 50 2719 (1 9 7 6 ),
D epartm ent o f P h y s ic a l C h a m istry U n i v e r s i ty o f L6dz
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S t e f a n i a T an iew sk a-O sitfsk a, M a łg o rz a ta Jóźw iak 9
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-D la po rów nan ia otrzym anych wyników zm ierzono e n t a l p i ę r o z p u s z c z a n ia XI w m ie s z a n in ie HMPT-H^O. S tę ż e n ie KI w y:iosito 0 ,0 0 1 8 -0 ,0 0 8 9 m ola/kg r o z p u s z c z a ln ik a . Na p o d sta w ie uzyskanyci. danych AHm a n i l i n y i KI o b lic z o n o stan d ard o w ą e n t a l p i ę r o z p u s z c z a n ia ( AH ) i e n t a l p i ę p r z e n i e s i e n i a (Alit,).
Ve w s z y s tk ic h p rzyp ad k ach w p r z e d z ia l e 0 - 0 , molowych HM?!' o b se rw u je s i ę o b n iż e n ie e n t a l p i i p r z e n i e s i e n i a .
v . K s z t a ł t krzyw ych AH - f (i* molowych HuMPT) z a le ż y w sp o só b w yraźny od r o d z a ju s u b s t a n c j i ro z p u s z c z o n e j. v
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