DYNAMICAL PROPERTIES OF THE Li+, 3H2O HYDRATE IN THE INTERLAMELLAR SPACE OF A SWELLING CLAY

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DYNAMICAL PROPERTIES OF THE Li+, 3H2O HYDRATE IN THE INTERLAMELLAR SPACE OF A

SWELLING CLAY

J. Conard, H. Hestrade-Szwarkopf, C. Poinsignon, A. Dianoux

To cite this version:

J. Conard, H. Hestrade-Szwarkopf, C. Poinsignon, A. Dianoux. DYNAMICAL PROPERTIES OF

THE Li+, 3H2O HYDRATE IN THE INTERLAMELLAR SPACE OF A SWELLING CLAY. Journal

de Physique Colloques, 1984, 45 (C7), pp.C7-169-C7-172. �10.1051/jphyscol:1984718�. �jpa-00224283�

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JOURNAL DE PHYSIQUE

Colloque C7, suppl6ment au n09, Tome 45, septembre 1984 page C7-169

DYNAMICAL PROPERTIES OF THE L i

+

, 3 H 2 0 HYDRATE I N THE INTERLAMELLAR SPACE OF A SWELLING CLAY

J. Conard, H. Hestrade-Szwarkopf, C . ~ o i n s i ~ n o n * and A . J . ~ i a n o u x * C.N.R.S., C.R.S.O.C.I., 4 5 0 4 5 OrZ&ans, France

*I. L. L., 38042 GrenobZe, France

RQsumQ

-

~ i ' 3 ~ ~ 0 e s t l ' b t a t d ' h y d r a t a t i o n s t a b l e l e p l u s f a i b l e de l ' h e c t o r i t e l i t h i u m . Les grandeurs gouvernant l ' a b s o r p t i o n du rayonnement infra-rouge (frsquences de v i b r a t i o n s , c o e f f i c i e n t d ' a b s o r p t i o n i n t Q g r 6 ) montrent que l ' e a u de l ' h y d r a t e du l i t h i u m dans l ' e s p a c e i n t e r l a m e l l a i r e e s t dans un Q t a t i n t e r m e d i a i r e e n t r e l e gaz e t l e l i q u i d e , pratiquement s a n s l i a i s o n hydrogsne (Fig. 1 , t a b l e a u I ) . Le modsle dynamique Q t a b l i B p a r t i r des donnCes de R.M.N. du 1 ~ e t de 7 ~ i e s t d Q c r i t p a r deux mouvements de r e o r i e n t a t i o n

(Fig. 2) :

.

une r o t a t i o n r a p i d e de l a mol6cule d ' e a u a u t o u r de son axe C2 ;

.

une r o t a t i o n l e n t e de l'ensemble de l ' h y d r a t e p a r r a p p o r t 2 l ' a x e c du f e u i l l e t

.

P a r d i f f u s i o n q u a s i - S l a s t i q u e des n e u t r o n s , on a :

.

p r Q c i s C l e s temps de c o r r Q l a t i o n des 2 mouvements de l ' h y d r a t e p l a t (Tableau 11) _;

.

montrP l a s t r u c t u r e bidimensionnelle e t l ' a n i s o t r o a i e du mouvement l e n t ,

.

montrQ l ' a b s e n c e d ' a c t i v a t i o n thermique des deux mouvements e n t r e 240 e t 300 K (Fig. 3)

.

A b s t r a c t

-

L i ' 3 ~ ~ 0 i s t h e lowest s t a b l e h y d r a t i o n s t a t e of t h e l i t h i u m

h e c t o r i t e . From t h e I R spectroscopy d a t a (bending and s t r e t c h i n g f r e q u e n c i e s , i n t e g r a t e d i n t e n s i t i e s ) t h e w a t e r i n t h e c l a y i n t e r l a m e l l a r space appears i n a s t a t e i n t e r m e d i a t e between gaz and l i q u i d , n o t involved i n any hydrogen bond.

From IH and 7 ~ i NMR d a t a , t h e dynamical model e s t a b l i s h e d i s e x p l a i n e d by two r e o r i e n t a t i o n a l motions :

.

a f a s t motion of t h e water molecule around C2 a x i s ;

.

a slow r o t a t i o n of t h e whole h y d r a t e w i t h r e s p e c t t o t h e c a x i s of t h e c l a y p l a t e l e t .

By q u a s i - e l a s t i c n e u t r o n s c a t t e r i n g ,

.

t h e c o r r e l a t i o n times of t h e both motions a r e determined,

.

t h e a n i s o t r o p y of t h e motions i s proved,

.

t h e absence of thermal a c t i v a t i o n f o r t h e both motions between 240 and 300 K i s shown.

I

-

XNFRA-RED DATA

The i n f r a - r e d spectrum of t h e l i t h i u m h e c t o r i t e between 1200 and 4000 cm -1 shows t h e well-resolved b e n d i n g b a n d s o f t h e water molecule ( v l and v3) a t r e s p e c t i v e l y 3580 and 3643 cm-l, and t h e s h a r p b u t i n t e n s e s t r e t c h i n g band V2 a t 1630 cm-l.

The sharpness and t h e good r e s o l u t i o n of t h e t h r e e fundamental v i b r a t i o n a l modes of t h e w a t e r molecule, t h e high i n t e n s i t y of v2 w i t h r e s p e c t t o v1 and v2 a r e a proof of t h e low a s s o c i a t i o n s t a t e of H20 [ I ] .

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1984718

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JOURNAL DE PHYSIQUE

F i g . 1

-

I . R . s p e c t r u m o f Li-3H20 h e c t o r i t e 6 - I

T a b l e I

-

A b s o r p t i o n c o e f f i c i e n t (A x 10 M cm) of t h e w a t e r s t r e t c h i n g band i n d i f f e r e n t environment.

R e f e r e n c e s f o r T a b l e I

M. Baverez and C . J . P o i n s i g n o n , C.R. Acad. S c i . , P a r i s , S e r . D , 2423-2426 (1967)

J. White, A. J e l l i , J. AndrG, and J.J. F r i u i a t , T r a n s . Faraday Soc. 63,

461-475 (1967)

E. G r e i n a c h e r , W . L u t t k e , and R. Mecke, Z . E l l e k t r o c h e m .

59,

23-31 (1955) C.N. Svenson, Spectrochim. Acta

g,

987-993 (1965)

R e f e r e n c e s

G r e i n a c h e r e t a l . idem

Swenson/ferruso-Ludwig Poinsignon e t a l . G r e i n a c h e r e t a l . Baverez

S i t u a t i o n

. 0 0 7 5 ~ / 1 - ' i n cc14

.

⁰²⁸~ / 1 - ' i n benzene H20 v a p o r

~ i + 3 ~ ~ 0 H20 l i q u i d

H20 adsorbed on s i l i c a g e l

C.C. F e r r u s o and C.G. Ludwig, J. Quantum S p e c t r o s c . R a d i a t . T r a n s f e r

5 ,

215-227 (1964)

A

2.9 2.2 2.12 5.68 23.6 25

M. Baverez, ThSse de D o c t o r a t d l E t a t , Nancy, 1966 E. Bauer and M. Magat, J . Phys.

2,

318-330 (1938)

C. P o i n s i g n o n , J . M . Cases and J.J. F r i p i a t , J . Chem. Phys.

82,

1855-1860 (1978).

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Table I (2) - V i b r a t i o n a l f r e q u e n c i e s

I1 - N.M.R. DATA

F i g u r e 2 shows t h e ~ i + 3 ~ 2 0 h y d r a t e between two l a y e r s of h e c t o r i t e . a ) and c) a r e t h e b a s a l p l a n s of t h e c l a y l a y e r s ,

b) t h e L i + 3 ~ ~ 0

0 1 , 02.

..

^O6 oxygens of t h e c l a y l a t t i c e ,

oC1, og, OY w a t e r oxygens

.

Front view o

-

¹ 2~ 0 . i . I Top view

F i g . 2

-

R o t a t i n g h y d r a t e model.

The water molecules a r e involved i n two u n i a x i a l r e o r i e n t a t i o n a l motions :

1 . The r o t a t i o n of t h e whole h y d r a t e around t h e A-axis ( f r o n t view) g i v i n g 12 s i t e s f o r t h e protons on t h e l a t t i c e oxygens ( b l a c k d o t s on t h e top view).

2. The proper r o t a t i o n of t h e H20 molecule around i t s C 2 a x i s ( I a x i s on t h e t o p view), on 6 s i t e s . AA',BB' a r e t h e protons s i t e s when t h e l i t h i u m o s c i l l a t e s from one s h e e t t o t h e o t h e r 121.

This model f o r t h e f l a t h y d r a t e i s only an average a t t h e N.M.R. time s c a l e ( 1 0 - ~ s ) .

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C7-172 JOURNAL DE PHYSIQUE

I11

-

NEUTRON SCATTERING RESULTS

A t t h e n e u t r o n time s c a l e (10-1°s, 10-:~s), t h e slow motion o f t h e whole h y d r a t e i n v o l v e s 12 s i t e s o n a c i r c l e o f 2.18 A o f r a d i u s and a c o r r e l a t i o n t i m e of 2 . 1 2

1 0 - l l s (Table 1 1 ) .

T a b l e I1

-

The p a r a m e t e r s f o r t h e two r o t a t i o n s .

0

The p r o t o n s of t h e w a t e r molecules r o t a t e on a c i r c l e of 1.23 A on 6 p o s i t i o n s w i t h a c o r r e l a t i o n t i m e of 2.7 10-12s.

The a b s e n c e of t h e r m a l a c t i v a t i o n of t h e two motions i s shown t h r o u g h t h e t h e r m a l dependence of t h e c o r r e l a t i o n t i m e s ( F i g . 3 ) .

slow motion

f a s t motion

F i g . 3

-

Thermal dependence o f t h e c o r r e l a t i o n t i m e s . g y r a t i o

r a d i u s 2.18 A

0

1.23 A

REFERENCES

T l

2 . 1 2 1 0 ~ ~ ~ s

2 . 7 10-12s jump s i t e s

number 12

6

[ I J P o i n s i g n o n C . , Cases J.M., B u l l . Soc. F r . M i n e r a l . C r i s t a l l .

101

(1978) 469-477.

1 / y 1 31 peV

240 yeV

1.21 Conard J . , Magn. Res. i n C o l l . I n t e r f . S c i e n c e s (1976) ACS Symp. S e r i e s T, 34-85.

[ 3 1 Conard J . , Estrade-Szwarckopf H . , Dianoux A. J . , ~ o i n s i ~ n o n C. (1984) J. de P h y s i q u e , i n p r i n t .