163

Chapter 7
ULTW V IO L E T P N D V I S I B L E L I G H T SPECTROSCOPY

R o b e r t A . SCHOONHEYDT
K a t h o l i e k e U n i v e r s i t e i t Leuven, Centrum v o o r O p p e r v l a k t e s c h e i k u n d e
e n C o l l o i d a l e S c h e i k u n d e , D e C r o y l a a n 4 2 , B-3030 Leuven, Belgium.
7.1

INTRODUCTION

The d i c f e r e n t a s p e c t s o f c l a y m i n e r a l

p r o p e r t i e s which can b e

s t u d i e d by u l t r a v i o l e t ( u . v . )

and v i s i b l e ( v i s . ) l i g h t s p e c t r o s c o p y

a r e summarized i n T a b l e 7 . 1 .

I t i s c l e a r t h a t u s e f u l chemical

i n f o r m a t i o n i s a l s o found i n t h e n e a r i n f r a r e d ( n . i . r . )

and t h i s

region i s t h e r e f o r e included i n t h i s review.

TABLE 7 . 1

Clay m i n e r a l p r o p e r t i e s s t u d i e d by u . v . - v i s . - n . i . r .

spectroscopy

Lattice
p r o p e r t ies

Spectroscopic
domains

Surface
properties

Spectroscopic
domains

Absorption edge

U.V.

Surface
imrrobilized
transition
metal i o n s

u.v.,

vis.,

Pdsorbed
chrorophores

u'v'

vis'

Lattice
substituted
transition
metal ions

u.v., v i s .
n.i.r.

Vibrational
o v e r t o n e s and
combination
bands

n.i.r.

..

n i r.

A l t h o u g h a s t u d y o f t h e a d s o r p t i o n edge i n i t s e l f i s a n i n t e r e s t i n g
r e s e a r c h subject, one i s h i s t o r i c a l l y i n c l i n e d t o work w i t h " w h i t e "
s a m p l e s , t h a t i s , s a m p l e s w i t h a b s o r p t i o n e d g e s beyond t h e
s p e c t r a l r e g i o n o f i n t e r e s t (X<200nrr o r ~ > 5 0 , 0 0 O ~ r r - ~ F) .o r t h e

m o s t s t u d i e d c l a y rn-inerals, t h e smectites , t h e a b s o r p t i o n edge

b e g i n s below 5 0 , 0 0 O ~ m - ~and r e a c h e s i t s maximum above 5 0 , 0 0 O ~ r - ~ .
I n t h e s e cases s i g n i f i c a n t s p e c t r o s c o p i c i n f o r m a t i o n can s t i l l b e
g a t h e r e d from t h e

U.V.

region.

The change t r a n s f e r and d-d bands o f t r a n s i t i o n n e t a l i o n s c o n t a i n

information about t h e f i r s t coordination sphere.

They a r e t h e r e f o r e

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probes f o r isomorphic s u b s t i t u t i o n .

In t h e i n t e r l a m e l l a r space

t h e d i r e c t c o o r d i n a t i o n o f s u r f a c e oxygens t o t h e t r a n s i t i o n
m e t a l i o n and t h e s u r f a c e - t r a n s i t i o n m e t a l complex i n t e r a c t i o n
can be s t u d i e d .

I n t h e l a t t e r c a s e t h e s u r f a c e can be c o n s i d e r e d

a s a r i g i d a n i o n i c s o l v e n t i n t h e s e n s e t h a t t h e s u r f a c e oxyqens
a r e not coordinated t o t h e t r a n s i t i o n metal i o n .
The nn:: o r II+
77::
t r a n s i t i o n s of adsorbed chromophoric
m o l e c u l e s are s u b j e c t t o s u r f a c e i n t e r a c t i o n s .

A d s o r p t i o n on

t h e c l a y s u r f a c e may i n d u c e a g g r e g a t i o n , r e d o x r e a c t i o n s o r a c i d base r e a c t i o n s .
F i n a l l y , v i b r a t i o n a l o v e r t o n e s and c o m b i n a t i o n b a n d s n o t o n l y
c o n t a i n i n f o r m a t i o n on t h e n a t u r e of t h e a d s o r b e d s p e c i e s b u t a l s o
on i t s r o t a t i o n a l m o b i l i t y . The l a t t e r i n f o r m a t i o n h a s b e e n

e x t r a c t e d from t h e v + 6 band o f H 2 0 on s i l i c a b u t i t s e x t e n s i o n
t o c l a y m i n e r a l s p o s e s no problem i n p r i n c i p l e ( K l i e r , 1973; K l i e r ,
Shen and Z e t t l e m o y e r , 1 9 7 3 ) .

I t s h o u l d b e i n t e r e s t i n g t o compare

t h e r e s u l t s w i t h t h o s e o b t a i n e d by NMR o r n e u t r o n d i f f r a c t i o n .
U.v.-vis.-n.i.r.

s p e c t r o s c o p y i s a l s o complementary t o e p r ,

m a g n e t i c s u s c e p t i b i l i t y measurements, Mijssbauer s p e c t r o s c o p y and

ESCA, which a r e r e v i e w e d i n o t h e r c h a p t e r s o f t h i s book.
7.2

TECHNIQUES

With t h e d i m e n s i o n s of t h e c l a y p a r t i c l e s c o m p a r a b l e t o t h e
w a v e l e n g t h l i t i s i m p o s s i b l e t o d i s t i n g u i s h t h e phenomena o f
r e f l e c t i o n , r e f r a c t i o n and d i f f r a c t i o n .

The l i g h t i s s c a t t e r e d .

For c l o s e l y p a c k e d p a r t i c l e s ( d i s t a n c e between p a r t i c l e s l e s s t h a n
2 - 3 p a r t i c l e d i a m e t e r s ) i n t e r f e r e n c e s and p h a s e r e l a t i o n s a r i s e

among t h e s c a t t e r e d l i g h t beams.

Together with absorption of l i g h t

t h e s e s c a t t e r i n g phenomena s t r o n g l y i n h i b i t t r a n s m i s s i o n
spectroscopy.

N e v e r t h e l e s s , many q u a l i t a t i v e t r a n s m i s s i o n

measurements on o r i e n t e d f i l m s o r s h e e t s h a v e b e e n p e r f o r m e d .

All

t h e s e s t u d i e s i n v o l v e i n t e n s e b a n d s , e i t h e r due t o t h e i r l a r g e
absorption coefficients, or
absorbing centers.

to

large

concentration

of

For "forbidden" bands of absorbing

c e n t e r s i n r e l a t i v e l y s m a l l c o n c e n t r a t i o n ( t h i s i s m o s t l y t h e case
f o r t r a n s i t i o n metal ions)

one c a n u s e e i t h e r d i f f u s e r e f l e c t i o n

s p e c t r o s c o p y (DRS) or p h o t o a c o u s t i c s p e c t r o s c o p y (PAS)

Both

t e c h n i q u e s w i l l b e b r i e f l y compared. F o r a d e t a i l e d s t u d y t h e r e a d e r
s h o u l d c o n s u l t t h e b a s i c l i t e r a t u r e ( K o r t i i m , 1 9 6 9 ; K e l l e r m a n , 1979;
H a r s h b a r g e r and Robin, 1973; Monahan and N o l l e , 1 9 7 7 ) .

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7.2.1

Diffuse r e f l e c t a n c e spectroscopy

I n DRS t h e l i g h t i n t e n s i t y s c a t t e r e d a t a g i v e n w a v e l e n g t h
from an " i n f i n i t e l y t h i c k ' : c l o s e l y - p a c k e d c l a y l a y e r i s compared
w i t h t h a t s c a t t e r e d from an i n f i n i t e l y t h i c k l a y e r o f a
non-absorbing

(white) reference.

The r a t i o o f t h e l i g h t i n t e n s i t y

s c a t t e r e d from t h e c l a y t o t h a t from t h e r e f e r e n c e i s r e c o r d e d as
a f u n c t i o n o f t h e wavelength.
This c o n s t i t u t e s t h e d i f f u s e
r e f l e c t a n c e s p e c t r u m . T h e r e a r e 2 ways t o i l l u m i n a t e s a p p l e and
reference.

I n t h e f i r s t mode a d i r e c t , d i s p e r s e d l i g h t b e a r

impinges ' p e r p e n d i c u l a r l y on t h e sample and on t h e r e f e r e n c e .

The

f i r s t l a y e r o f randomly o r i e n t e d p a r t i c l e s s c a t t e r s t h e l i g h t i n a l l
d i r e c t i o n s , i n d e p e n d e n t l y o f t h e a n g l e of i n c i d e n c e ( L a m b e r t ' s l a w )
and e n s u r e s d i f f u s e i l l u m i n a t i o n o f t h e o t h e r p a r t i c l e s .

The

l i g h t s c a t t e r e d from sample and r e f e r e n c e i s c o l l e c t e d i n an

i n t e g r a t i o n s p h e r e and d e t e c t e d by a PbS c e l l ( n . i . r . 1
photomultiplier (vis.-u.v.)

or a

on t o p o f t h e i n t e g r a t i o n s p h e r e .

Because t h e i n t e g r a t i o n s p h e r e must s c a t t e r t h e l i g h t and n o t

absorb i t , i t is c o a t e d w i t h a p e r f e c t l y w h i t e c o a t i n g ( K o r t i h ,
1969; Kellerman, 1 9 7 9 ) .

I n t h i s way a n e g l i g i b l y s m a l l amount of

s p e c u l a r r e f l e c t i o n (on t h e f i r s t l a y e r o f p a r t i c l e s ) i s included.
I n t h e s e c o n d mode o f o p e r a t i o n sample and r e f e r e n c e a r e
illuminated with d i f f u s e , undispersed r a d i a t i o n , i t s d i f f u s e
c h a r a c t e r b e i n g e n s u r e d by t h e i n t e g r a t i o n s p h e r e .
Measurements on l u m i n e s c e n t samples p r e s e n t i n p r i n c i p l e no
I n mode 1 t h e a b s o r p t i o n s p e c t r u m i s o b t a i n e d ,

difficulties.

whereas i n mode 2 b o t h t h e a b s o r p t i o n and l u m i n e s c e n c e are

registered.

By s u b s t r a c t i o n t h e l u m i n e s c e n c e s p e c t r u m is o b t a i n e d .

The e x p e r i m e n t a l s p e c t r u m c o n t a i n s a n a b s o r p t i o n p a r t and a
scattering part.
A t p r e s e n t t h e r e i s no t h e o r y a b l e t o d e s c r i b e
q u a n t i t a t i v e l y t h e phenomenon of " d e p e n d e n t " m u l t i p l e s c a t t e r i n g ,

as it o c c u r s on c l a y powders.

T h e r e are 2 a p p r o a c h e s .

In the

continuum o r phenomenological approach - t h e m o s t p o p u l a r - t h e

c h a r a c t e r i s t i c s of t h e I n d i v i d u a l p a r t i c l e s , c o n s t i t u t i n g t h e
i n f i n i t e l y t h i c k l a y e r , are n e g l e c t e d .

In the statistical

approach t h e y a r e t a k e n i n t o a c c o u n t and t h e v a l i d i t y of t h e
r e s u l t s depends on t h e v a l i d i t y o f t h e model chosen t o d e s c r i b e
the particles.

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The b a s i c e q u a t i o n f o r t h e phenomenological t h e o r i e s i s t h e
r a d i a t i o n t r a n s f e r e q u a t i o n (Kortfim, 1 9 6 9 ) :

I i s t h e i n c i d e n t l i g h t i n t e n s i t y o f a g i v e n w a v e l e n g t h and

i t s change w i t h p a t h l e n g t h ;

dI

i s t h e d e n s i t y o f t h e medium;

K i s an a t t e n u a t i o n c o e f f i c i e n t c o r r e s p o n d i n g t o t o t a l r a d i a t i o n

l o s s due t o b o t h a b s o r p t i o n and s c a t t e r i n g .

j is a scattering function defined'as :

p ( @ , $ , ~ ' , $ ' ) t,h e p h a s e f u n c t i o n , i s a measure o f t h e i n t e n s i t y of

s c a t t e r e d r a d i a t i o n i n t h e s o l i d angle do' = sinO'd@'d$' i f a
beam i n t h e d i r e c t i o n ( @ , $ ) s t r i k e s a m a s s e l e m e n t of t h e medium.
The one p a r a m e t e r a p p r o x i m a t e s o l u t i o n of e q u a t i o n 1, known as
t h e Schuster-Kubelka-Munk o r t h e Kubelka-Munk e q u a t i o n , i s t h e
most p o p u l a r ( K o r t k n , 1969) :

Rm =

l i g h t i n t e n s i t y r e f l e c t e d from sample
l i g h t i n t e n s i t y r e f l e c t e d from r e f e r e n c e

K i s t h e a p p a r e n t a b s o r p t i o n c o e f f i c i e n t and S t h e a p p a r e n t

scattering coefficient.

E q u a t i o n 3 i s d e r i v e d f o r an i n f i n i t e l y

t h i c k l a y e r of randomly d i s t r i b u t e d p a r t i c l e s , s u b j e c t t o d i f f u s e
r a d i a t i o n and i s o t r o p i c s c a t t e r i n g .

I t i s a r e m a r k a b l y good

a p p r o x i m a t i o n i n t h e l i m i t of low c o n c e n t r a t i o n o f a b s o r p t i o n
c e n t e r s ( H e c h t , 1 9 7 6 ; K l i e r , 1 9 7 2 ) . F o r s t r o n g l y a b s o r b i n g media
s o l u t i o n s of t h e r a d i a t i o n t r a n s f e r e q u a t i o n b a s e d upon a n i s o t r o p i c

scatter g i v e a b e t t e r account of t h e e x p e r i m e n t a l r e f l e c t a n c e
(Hecht, 1 9 7 6 ) . For t h e s t a t i s t i c a l t h e o r i e s t h e o r i g i n a l l i t e r a t u r e
s h o u l d b e c o n s u l t e d ( K e l l e r m a n , 1 9 7 9 ; Melamed, 1 9 6 3 ) .

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7.2.2

Photoacoustic Spectroscopy

The e n e r g y o f t h e a b s o r b e d r a d i a t i o n , which i s r a d i a t i o n l e s s
r e l e a s e d , h e a t s up t h e g a s e o u s m o l e c u l e s i n t h e immediate environment
and a p r e s s u r e i n c r e a s e r e s u l t s .

When t h e i n c i d e n t r a d i a t i o n i s

chopped, p e r i o d i c p r e s s u r e changes o c c u r .

They p r o p a g a t e t h r o u g h t h e

g a s e o u s e n v i r o n m e n t and a r e d e t e c t e d by a microphone. The i n t e n s i t y

of t h e microphone r e s p o n s e i s p r o p o r t i o n a l t o t h e amount o f a b s o r b e d
radiation.

Thus , when a w a v e l e n g t h r a n g e i s scanned, a "spectrum"

i s o b t a i n e d . T h i s i s a power s p e c t r u m : t h e i n t e n s i t y o f t h e s i g n a l
i s n o t o n l y p r o p o r t i o n a l t o t h e number o f p h o t o n s a b s o r b e d b u t a l s o
t o t h e i r e n e r g y . The band p r o f i l e i n t h e p h o t o a c o u s t i c s p e c t r u m
a p p e a r s d i s t o r t e d due t o t h e f a c t t h a t t h e h i g h f r e q u e n c y s i d e
a b s o r b s more power t h a n t h e low f r e q u e n c y s i d e . F o r
g a s e o u s samples t h e m o l e c u l e s t h e m s e l v e s c o n s t i t u t e t h e medium f o r
t h e p r o p a g a t i o n of t h e p r e s s u r e p u l s e s .

F o r l i q u i d s and s o l i d s a

gaseous environment i s n e c e s s a r y .
P o t e n t i a l a d v a n t a g e s of PAS o v e r DRE a r e : ( i ) no problems w i t h
s c a t t e r e d and s p e c u l a r l y r e f l e c t e d l i g h t ;

( i i )e a s y measurements

o f l u m i n e s c e n t m a t e r i a l s and ( i i i ) t h e u s e o f s m a l l amounts o f
material.
The m o s t s e v e r e r e s t r i c t i o n f o r a q u a n t i t a t i v e
a p p l i c a t i o n of PAS a t p r e s e n t i s t h e l a c k of a f i r m t h e o r e t i c a l
foundation.

The t h e o r y of Rosencwaig and Gersho f o r n o n - s c a t t e r i n g

s o l i d s h a s been r e v i e w e d ( K e l l e r m a n , 1 9 7 9 ) .

F o r powders a

t h e o r y r e l a t i n g t h e PAS s i g n a l i n t e n s i t y t o t h e a b s o r p t i o n
c o e f f i c i e n t , i s p u b l i s h e d (Monahan and N o l l e , 1 9 7 7 ) .

It is clear

however t h a t more t h e o r e t i c a l and e x p e r i m e n t a l work i s n e c e s s a r y

(Adams, King and K i r k b r i g h t , 1 9 7 6 ) .

For i n s t a n c e , u n c e r t a i n t i e s

a r i s e due t o p a r t i c l e s h a p e s and d i s t r i b u t i o n o f p a r t i c l e s i z e s i n
t h e powdered s a m p l e s .

Also, i f t h e c h a r a c t e r i s t i c thermal d i s t a n c e

of t h e f i l l e r g a s i s much l a r g e r t h a n t h e p a r t i c l e d i a r r e t e r , t h e
p a r t i c l e s are thermally short-circuited with the r e s u l t t h a t the
PAS s i g n a l i n t e n s i t y i s smaller t h a n e x p e c t e d .

F i n a l l y , no a c c o u n t

i s g i v e n o f t h e e f f e c t o f s c a t t e r e d l i g h t . I t h a s b e e n shown
experimentally t h a t s c a t t e r e d l i g h t contributes s i g n i f i c a n t l y t o t h e
PAS s i g n a l a t l o w o p t i c a l d e n s i t i e s o r / a n d h i g h r e f l e c t i v i t i e s . P
f r a c t i o n o f t h e s c a t t e r e d l i g h t may r e a c h t h e c e l l w a l l s , b e
p a r t i a l l y a b s o r b e d t h e r e , t h u s p r o d u c i n g a background s i g n a l
d e p e n d e n t on t h e o p t i c a l p r o p e r t i e s o f sample and c e l l w a l l s . A
s u i t a b l e c e l l d e s i g n w i t h t r a n s p a r e n t windows e l i m i n a t e s t h i s e f f e c t
(McClelland and K n i s e l e y , 1 9 7 6 ) . About t h e e f f e c t o f i n t e r p a r t i c l e s c a t t e r i n g n o t h i n g i s known.

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Experimental c o n s i d e r a t i o n s
The c o n d i t i o n s o f i s o t r o p i c s c a t t e r i n g and d i f f u s e i l l u m i n a t i o n ,

7.2.3

r e q u i r e d b y e q u a t i o n 3 , are most c l o s e l y m e t when t h e medium

c o n s i s t s o f d e n s i l y p a c k e d , randomly shaped p a r t i c l e s whose s i z e s
a r e comparable o r smaller t h a n t h e w a v e l e n g t h o f t h e l i g h t .
Clay l a y e r s o f

5mm t h i c k a r e s u f f i c i e n t f o r t h e i n f i n i t e

thickness criterion.

For work i n vacuum, a d s o r p t i o n s t u d i e s

o r c a t a l y t i c e x p e r i m e n t s , s p e c i a l l y d e s i g n e d c e l l s are n e c e s s a r y
w i t h s i l i c a windows w i t h e x t r e m e l y low OH and H20 c o n t e n t s .
I t i s a d v i s a b l e t o s i e v e t h e c l a y and t o work w i t h i d e n t i c a l

fractions.

The s c a t t e r i n g p r o p e r t i e s a r e s t r o n g l y i n f l u e n c e d

by a d s o r b e d l a y e r s on t h e e x t e r n a l s u r f a c e s . Thus, t h e H20
c o m b i n a t i o n and o v e r t o n e b a n d s i n t e n s i t i e s are n o t l i n e a r l y
d e p e n d e n t on t h e amount a d s o r b e d from c o m p l e t e d e h y d r a t i o n up t o
f u l l s a t u r a t i o n b e c a u s e of a d s o r p t i o n on t h e e x t e r n a l s u r f a c e i n
t h e l a t t e r case.
The p h o t o a c o u s t i c S p e c t r o m e t e r r e p o n d s t o t h e t o t a l amount o f
l i g h t a d s o r b e d i n t h e sample w i t h i n a d e p t h r o u g h l y e q u a l t o t h e
thermal d i f f u s i o n length.

I f a l l t h e l i g h t i s absorbed within t h a t

d e p t h t h e sample i s p h o t o a c o u s t i c a l l y "opaque".
t h i s (EG

& G PAR

Pn example i l l u s t r a t e s

6001 Photoacoustic s p e c t r o m e t e r ) .

At a

m o d u l a t i o n f r e q u e n c y of 40Hz t h e t h e r m a l d i f f u s i o n l e n g t h i n an
aqueous s o l u t i o n i s of t h e o r d e r o f 30pm.

The p h o t o a c o u s t i c d e t e c t i o n

p r o c e s s w i l l o n l y y i e l d a measure o f t h e l i g h t a b s o r p t i o n w i t h i n t h e
30pm d i f f u s i o n l e n g t h . O p t i c a l a b s o r p t i o n c o e f f i c i e n t s g r e a t e r t h a n
I.

3 0 0 0 ~ m - c~a n n o t b e d i s t i n g u i s h e d i n t h a t s i t u a t i o n : t h e y w i l l

a p p e a r e q u a l l y opaque t o t h e p h o t o a c o u s t i c d e t e c t i o n p r o c e s s .
S o l u t i o n s t o t h i s problem a r e (i) t o work w i t h s a m p l e s t h i n n e r t h a n
t h e reciprocal absorption c o e f f i c i e n t o r (ii)to increase t h e
modulation frequency.

Both methods have t h e i r odds and optimum

c o n d i t i o n s have t o b e chosen d e p e n d e n t on t h e problem u n d e r i n v e s t i g a tion.

169

I n any c a s e f o r two-dimensional

s o l i d s o r m a t e r i a l s w i t h weak

surface adsorption p r o p e r t i e s , adsorbed gases (transparent i n t h e

s p e c t r a l r e g i o n o f i n t e r e s t ) do n o t p l a y a s i g n i f i c a n t r o l e i n t h e
p r o d u c t i o n o f t h e PAS s i g n a l .

A l s o , t h e r m a l e x p a n s i o n and c o n t r a c -

t i o n o f t h e s o l i d and any t h e r m a l l y i n d u c e d v i b r a t i o n a r e t o o s m a l l t o
p r o d u c e a d e t e c t a b l e PAS s i g n a l .
7.3

INTERLAMELLAR T R A N S I T I O N METAL I O N COMPLEXES

T h e r e a r e 3 t y p e s of t r a n s i t i o n s i n t h e s p e c t r a : d-d,

t r a n s f e r 'and i n t r a l i q a n d b a n d s .
molecules w i t h n

T::

or

charge

The l a t t e r a r e o n l y o b s e r v e d when

7 1 4 ~ : :

t r a n s i t i o n s a r e coordinated.

The

spectra w i l l be discussed with reference t o t h e solution spectra.

T h i s a l l o w s a d i s c u s s i o n of t h e e f f e c t s o f t h e b i d i r e n s i o n a l c l a y
s u r f a c e on t h e geometry and on t h e e l e c t r o n i c p r o p e r t i e s o f t h e
a d s o r b e d complexes. T h i s s e c t i o n w i l l b e d i v i d e d i n 3 p a r t s ,
depending on t h e n a t u r e o f t h e l i g a n d s : H 2 0 and l a t t i c e oxygens,
a l i p h a t i c p o l y a m i n e s and a r o m a t i c m o l e c u l e s .
7.3.1

Water and l a t t i c e oxygens

Cu (11)-, Co (11)- and N i (11)- c l a y s have t h e o c t a h e d r a l

H 0-saturated
2

[M(H20) 12+ complexes i n t h e i n t e r l a m e l l a r s p a c e .

The d-d band

s p e c t r u m o f t h e s e hexaquo-complexes i s - w i t h i n t h e l i m i t s o f experiment-

a l accuracy-similar tothe aqueous s o l u t i o n s p e c t r a (Kdnig, 1 9 7 1 ; L e v e r ,

1968; T a r a s e v i c h and S i v a l o v , 1975a, 197513, 1975c, 1 9 7 7 ) . I n a i r - d r y
2+
s y s t e m s [ C U ( ! ~ O ) ~ I *c+o l l a p s e s t o t h e p l a n a r [ C U ( H ~ O ) ~ ], t h e 2
o t h e r s remain o c t a h e d r a l ( T a r a s e v i c h and S i v a l o v , 1975a; Velghe ,
Schoonheydt and U y t t e r h o e v e n , 1 9 7 7 ) . T h e s e r e s u l t s a r e c o n f i r r e d by
e p r ( C l e m e n t z , P i n n a v a i a and M o r t l a n d , 1 9 7 3 ) .
That Cu(I1) p r e f e r s t h e t e t r a g o n a l l y d i s t o r t e d coordination
( D 4 h symmetry) i s well-known

i n i n o r g a n i c c h e m i s t r y (Hathaway and
B i l l i n g , 1 9 7 0 ) and a t t r i b u t e d t o t h e J a h n - T e l l e r e f f e c t .
For t h i s
p l a n a r complex t h e c o n t r i b u t i o n o f l a t t i c e oxygens t o t h e l i q a n d
f i e l d i s n e g l i g i b l y s m a l l ( V e l q h e , Schoonheydt and U y t t e r h o e v e n , 1 9 7 7 ) .
2+
I t i s t h e r e f o r e n o t e x a c t t o w r i t e [ C U ( H ~ O ) ~ ( O ~(OQ
) ~ ]= l a t t i c e
oxygen) as s u g g e s t e d i n t h e l i t e r a t u r e ( T a r a s e v i c h and S i v a l o v , 1 9 7 5 a ) .
I n s t r o n g l y d e h y d r a t i n g c o n d i t i o n s t h e s p e c t r a d r a s t i c a l l y change.
The s c a t t e r i n g power of t h e m a t e r i a l i s a l t e r e d and t h e background
h a s i n c r e a s e d s t r o n g l y : t h e s p e c t r a become i l l - r e s o l v e d .
a r e only determined approximately.
decide

on

Band maxima

I t i s i n most cases i m p o s s i b l e t o

t h e number of components u n d e r one band e n v e l o p e .

The

170

a s s i g n m e n t s p r o p o s e d a r e t h e r e f o r e i d e a l i z e d and t e n t a t i v e

( T a r a s e v i c h and S i v a l o v , 1975a, 1975b , 1 9 7 5 ~ ;Velghe, Schoonheydt

and U y t t e r h o e v e n , 1 9 7 7 ) . R e s u l t s a r e summarized i n T a b l e 2.
They c o r r e s p o n d t o t h e f o l l o w i n g i d e a l i z e d d e h y d r a t i o n s e q u e n c e s
( T a r a s e v i c h , 1975) :

Especially t h e intermediate 5-coordinate species a r e d i f f i c u l t

t o v i s u a l i z e i n terms o f t h e i d e a l i z e d CllV ( s q u a r e pyramid) or D
3h
( t r i g o n a l b i p y r a m i d ) s t r u c t u r e s . The i n t e r p r e t a t i o n i s a l s o made
d i f f i c u l t by t h e p o s s i b l e p r e s e n c e o f d-d bands i n t h e n . i . r .

o u t s i d e t h e s p e c t r o m e t e r r a n g e , e s p e c i a l l y f o r Co(11) ( T a r a s e v i c h

and S i v a l o v , 197533).
The o b s e r v a t i o n o f [Cu(O ) 12+ ( T a r a s e v i c h and S i v a l o v , 1975a)
w i t h a d-d band a t 14800cm- is i n t e r e s t i n g . I n d e h y d r a t e d
2+
s y n t h e t i c z e o l i t e s A , X o r Y [ C U ( O ~ ) ~ ]has i t s band maximum a t
1 0 8 0 0 ~ m -w
~ i t h a s h o u l d e r around 1 5 0 0 0 ~ m - ~ .The d i f f e r e n c e (1480010800) i n d i c a t e s t h a t C u ( I 1 ) i s more s t r o n g l y c o o r d i n a t e d t o t h e
s u r f a c e oxygens of c l a y s t h a n t h o s e o f z e o l i t e s .
I n t h e l a t t e r case
s p i n - o r b i t c o u p l i n g and J a h n - T e l l e r e f f e c t s must b e i n c l u d e d i n t h e
l i g a n d f i e l d c a l c u l a t i o n t o e x p l a i n t h e s p e c t r u m ( S t r o n e and K l i e r ,
1980).

Better resolved s p e c t r a a r e necessary f o r clays, before

m e a n i n g f u l l i g a n d f i e l d p a r a m e t e r s can b e d e r i v e d .

171
TABLE 7.2
S p e c t r a l c h a r a c t e r i s t i c s of t h e a q u o complexes
Band p o s i t i o n s ( c m - l )

P s s i gnn-en t s

8550
7800

13300

6320(1)7250(1)8130

8400 (

19400 21500sh
18050

22000

15750 17260 18760

i390

(Ok)

'+

25600
2 5000

14500
8770

15050

17000
24800 ( 2 )

14400(

1055 0 (

[Co ( H 2 0 )

[Co(OR)3H2012+

15150
154 50 ( 2 )

13 8 0 0 T 2

lOOOOsh

[CO(H~O)~]~+

[CU (H20) 1

12650
1 3$00
1 3100 (2

[cu (

15200 ( )

2+

~ ~ 12+
0 )

1 4 e00
(1) n o t o b s e r v e d
( 2 ) V e l g h e , S c h o o n h e y d t and U y t t e r h o e v e n ,

1977; t h e o t h e r s p e c t r a
a r e f r o m T a r a s e v i c h and Givalov, 1 9 7 5 a , 1 9 7 5 b , 1 9 7 5 c .

7.3.2

A l i p h a t i c polyamines

The complexes o f t r a n s i t i o n m e t a l i o n s w i t h p o l y a m i n e s on c l a y s
h a v e b e e n i n v e s t i g a t e d as m o l e c u l a r p r o p s (Knudsen and McPtee,

1972;

T h i e l m a n n and McFtee, 19751, as s o i l c o n d i t i o n e r s and as waste water

c l e a n e r s ( C r e m e r s , P e i g n e u r a n d Maes, 1979)

are

consequences of t h e e x t r a - s t a b i l i t y

The l a t t e r a p p l i c a t i o n s

g a i n e d b y t h e s e complexes

on t h e s u r f a c e w i t h r e s p e c t t o t h e i r s t a b i l i t y i n a q u e o u s s o l u t i o n

(Maes and C r e m e r s , 1979; S i l l e n a n d M a r t e l l , 1 9 6 4 ) .

( = e t h y l e n e d i a m i n e ) and C u ( I 1 ) t h e dOOl d i s t a n c e

For en

of 1.2751111-

( V e l g h e , S c h o o n h e y d t , U y t t e r h o e v e n , P e i g n e u r a n d L u n s f o r d , 1 9 7 7 , Maes
and C r e m e r s , 1979) i s i n d i c a t i v e f o r a p l a n a r complex C u ( e n )2+
2
( i d e a l i z e d symmetry = D 4 h )

i n t h e interlamellar space.

This suggests

t h e removal of t h e l o o s e l y bound a x i a l w a t e r m o l e c u l e s upon

adsorption :

172

[ C u ( e n ) (H20 2]2+

2 N a -clay

[Cu(en)2]-clay

2Na+

2H20

(7)

The d-d band s y s t e m o f [ C u ( e n ) 2 1 - c l a y i s i n t h e r a n g e 1 9 4 0 0

a s compared t o 1 8 2 0 0 ~ m - i~n a q u e o u s s o l u t i o n ( V e l a h e ,

20200cm-1

S c h o o n h e y d t , U y t t e r h o e v e n , P e i g n e u r and L u n s f o r d , 1 9 7 7 ) .
F i g . 7 . 1 shows how t h e i n c r e a s e d t e t r a g o n a l d i s t o r t i o n , due t o t h e
r e p l a c e m e n t o f t h e a x i a l w a t e r m o l e c u l e s by t h e s u r f a c e o x y g e n s ,
a c c o u n t s f o r t h e hypsochromic s h i f t .

The e x p e r i n e n t a l band p r o f i l e s

a r e s l i g h t l y a s y m m e t r i c t o w a r d s l o w e r wavenurrbers, b e c a u s e o f t h e
t r a n s i t i o n s 2B-2B

19

t h e main band
19'
(Maes, S c h o o n h e y d t , C r e m e r s and U y t t e r h o e v e n , 1980)
29

= lODq and

2B -2P
19

b e i n g 2B -2E
19
9
The c o m p l e t e r e s o l u t i o n o f t h e s e t r a n s i t i o n s by G a u s s i a n c u r v e

a n a l y s i s i s shown i n F i g . 7 . 2 t o g e t h e r w i t h t h e c o r r e s p c n d i n g
c r y s t a l f i e l d s t a b i l i z a t i o n e n e r g i e s (C.F.F.E.).

There is a

p o s i t i v e c o r r e l a t i o n between lODq, t h e i n - p l a n e l i g a n d f i e l d s t r e n g t h ,
t h e C.F.S.E.,

and

of t h e mineral.

the

average

negative

charge

density

P similar c o r r e l a t i o n w a s found between t h e a v e r a g e

n e g a t i v e c h a r g e d e n s i t y and t h e f r e e e n e r g y change o f e x c h a n g e ,
AGO (Maes and C r e m e r s ,

1979).

I n f a c t , t h e v a l u e s of A G O are

- w i t h i n e x p e r i m e n t a l e r r o r - e q u a l t o A(C.F.S.E.1
surface

C.F.S.E.

i n aqueous s o l u t i o n .

= C.F.F.E.

on

T h i s s u g g e s t s t h a t AGO i s

g o v e r n e d by e n e r g y terms.
The h e t e r o g e n e o u s c h a r g e d i s t r i b u t i o n o f t h e r r i n e r a l s ( F t u l and
M o r t i e r , 1 9 7 4 ) i s e x p e r i m e n t a l l y shown by t h e h y p s o c h r o m i c s h i f t of
t h e d-d band maximum w i t h d e c r e a s i n g e x c h a n g e l e v e l s (Maes,
f c h o o n h e y d t , C r e m e r s and U y t t e r h o e v e n , 1 9 8 0 ) .

Thus, m i c r o c r y s t a l s

w i t h t h e h i g h e s t c h a r g e d e n s i t y a r e p r e f e r e n t i a l l y exchanged i n
c o n d i t i o n s o f p a r t i a l exchange.

I n these crystals the strongest

e l e c t r o s t a t i c i n t e r a c t i o n surface-complex e x i s t s .

Both e f f e c t s ,

removal o f a x i a l H 2 0 and e l e c t r o s t a t i c i n t e r a c t i o n , are c o r r e l a t e d

a s t h e f o r m e r o c c u r s more e a s i l y on t h e m i n e r a l s w i t h t h e h i g h e s t
a v e r a g e n e g a t i v e c h a r g e d e n s i t y (Maes and Creners, 1 9 7 9 ) .

That t h e

a x i a l H 2 0 removal i s a c o n s e q u e n c e o f 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
i s a t p r e s e n t a u s e f u l w o r k i n g h y p o t h e s i s f o r which no d i r e c t

experimental evidence e x i s t s .

173

9
d :CU

Ni

*Oh

dxy : b2g

/ ~ D s -5Dt
increasing tetragonal

distortion

Fig. 7.1 d-orbital splitting under D4h symmetry

*
CI

0
-

214
21
20.1

217
24
17.4

In

207
14
14

198 193 CFSE(kJmoi')

12

A CFSE
A Go (kJrnol-')
2+

Fig. 7.2 d-d transitions, C.F.S.E. and AGO (exchange) of Cu(en)2

on hectorite (hect.), Otay and Camp Berteau montmorillonites
(Otay, Camp B.); 0.75 C.B. and 0.65 C.B. = Camp Berteau with
respectively 75 % and 6 5 % of the original C.E.C.
The Cu-N bonding of [Cu(en)2]2+ on the surface is essentially the
same as in solution (Schoonheydt, 1978). This and the surface
not being a ligand -or a weak one- suggests that the

174
c l a y s u r f a c e i s a r i g i d a n i o n i c s o l v e n t t o w a r d s [ C ~ ( e n ) ~ ] ~I n+d.e e d ,
t h e LMCT ( l i g a n d - t o - m e t a l
i n t h e range 40700
and 43860cm-1

c h a r g e t r a n s f e r ) band on t h e c l a y s i s
4 1 9 0 0 ~ m - ~ and a t a b o u t 4 0 0 5 0 ~ m - f~o r CF30F

i n water.

Fs a result the optical electroneuativity

o f e n i n C u ( e n ) ; + on c l a y s i s 1.32

0.04

a u a i n s t 1.18 i n aqueous

s o l u t i o n (Maes, S c h o o n h e y d t , C r e m e r s and U y t t e r h o e v e n , 1 9 8 0 ) .
P h y s i c a l l y , t h i s i n c r e a s e means t h a t e n on c l a y s i s s l i u h t l y more
b a s i c t h a n i n aqueous s o l u t i o n .

Such a b e h a v i o r r e r i n d s u s o f t h e

f a c t t h a t t h e f r e e e n e r g i e s of exchange of N a

f o r alkylammonium

i o n s f o l l o w t h e g a s p h a s e b a s i c i t y s e q u e n c e (Maes, Y a r i j n e n and
Cremers, 1977).

Thus, t h e " s c r e e n i n g " power o f t h e s o l v e n t

" h y d r a t e d c l a y " i s less t h a n t h a t o f t h e s o l v e n t "water", b o t h f o r

2+
alkylammonium i o n s and f o r C u ( e n ) 2

'2

A l l t h e s e r e s u l t s f o r Cu ( e n )

a p p l y t o N i (11)

The b i s - c o r r p l e x
i s exchanged w i t h removal o f t h e 2 a x i a l w a t e r m o l e c u l e s and
[Ni ( e n ) 2 ] 2 + on t h e c l a y i s d i a m a g n e t i c ( V e l g h e , S c h o o n h e y d t and

Uytterhoeven,

1979).

reference t o Fig. 7.2.

The d i a m a g n e t i s m c a n b e u n d e r s t o o d w i t h
The removal of 2 a x i a l F 2 0 m o l e c u l e s i n c r e a s e s

t h e t e t r a g o n a l d i s t o r t i o n t o s u c h an e x t e n t t h a t t h e e n e r g y d i f f e r e n c e
between d 2 2 and d Z 2 o r d
exceeds t h e s p i n p a i r i n g energy.
x -Y
XY
-1
contains the
c h a r a c t e r i s t i c band of N i ( e n ) 2 - c l a y a t 21500crr

The

f o l l o w i n g 3 t r a n s i t i o n s 'A- -1~
'A B'and 'A-lE
29'
19
1g
19
g
19
T h i s c a n b e s e e n from t h e e n e r g y d i a q r a r o f F i g . 7 . 3 , c o n s t r u c t e d
w i t h t h e e n e r g y matrices o f a p p e n d i x 7 . 7 .

Frorr a f i t o f t h e

observed spectrum w i t h t h i s l i g a n d f i e l d c a l c u l a t i o n , i t f o l l o w s t h a t
R a c a h ' s i n t e r e l e c t r o n i c r e p u l s i o n p a r a m e t e r i s B = 788
l O D q = 22800

1 1 2 00cm-I

-1

995~117 and

2 4 0 0 0 ~ m - ~ . The l a t t e r i s much l a r g e r t h a n t h e
2+
( L e v e r , 1968)

f o r t h e p a r a m a g n e t i c [ N i ( e n ) ( F 2 0 )2 1

Two e f f e c t s c o n t r i b u t e t o t h i s d i f f e r e n c e : t h e d i f f e r e n c e i n t h e
e f f e c t i v e n u c l e a r c h a r g e on N i and t h e d i f f e r e n c e i n t h e N i - N
distance.

bond

I f t h e f o r m e r i s s u p p o s e d t o b e c o n s t a n t , a maximurr v a l u e

f o r t h e l a t t e r c a n b e c a l c u l a t e d from ( L e v e r , 1968) :
10

zeff

lODq = where Z e f f
distance.

e2 r4

6a5

i s t h e e f f e c t i v e n u c l e a r c h a r g e and a t h e N i - N bond
= 0.2124nm f o r t h e p a r a m a g n e t i c complex

With N i - N

( M a r t i n , S p e r a t i and Busch, 1 9 7 7 ) o n e o b t a i n s f o r t h e d i a m a g n e t i c
complex a v a l u e of 0.183nm.

175
A,

A,

30B

A,

208

= 348

-EI
8C

60

40

_..--:

2 0 s2/
....
................. -.>-:
___.--............. _ic.
.........

---

/.
*+

Fig.7.3 Energy level diagrams for Ni(en)22+ on clays

Octahedral complexes do not undergo significant band shifts
on the surface. Mono-complexes such as [Cu(en) (H20)412+ and
[Ni(en)(H20) 12+ disproportionate on the surface into bis-corplexes
and aquo-complexes (Velghe, Schoonheydt, Lunsford, 1977; Velghe,
Schoonheydt, Uytterhoeven, Peigneur and Lunsford, 1977; Velghe,
Schoonheydt and Uytterhoeven, 1979). The stepwise adsorption
of gaseous en on hydrated clays proceeds over the bis-complex :
[M(H20)612+ + 2en

+ [M(en)2]2+ +

6H20

V(en),2+ (M=Ni, Cu) (9)

With ligands such as dien(diethy1enetriamine) and tetren(tetraethylenepentamine) an important amount of protonated 1igand.s is
exchanged together with the complexes (Schoonheydt, Velghe, Baerts
and Uytterhoeven, 1979). Dependkng on the water content the
following equilibria are observed :

176

tetrenH

2dienH +

-HZO'

+ [Ni(tetren)(H20) ] 2 + s 2 0 t e t r e n

[ N i ( d i e n I 2 l2 +

-+H20

2dien

-H20

[I

> t r e n H )13+(10)

Pla

diamagnetic

[ N i ( d i e n H ) 2 ]4+

(11)

p l a n a r , diamagne

S i m i l a r r e a c t i o n s can b e w r i t t e n f o r Cu.
P 1 1 t h e s e d a t a d e m o n s t r a t e t h e l a r g e a f f i n i t y of t h e b i d i

ion-

a 1 s u r f a c e o f c l a y s f o r " b i d i m e n s i o n a l " ( = p l a n a r ) .complexes.

7.3.3

Aromatic m o l e c u l e s

I n t h e e a r l y 7 0 ' s t h e most p o p u l a r s y s t e m w a s Cu2+

benzene,

forming on t h e s u r f a c e g r e e n , t y p e I , complexes and r e d , t y p e 11,

complexes : g r e e n r t y p e
1971, Mortland, 1973).

+H 0

r e d , t y p e I1 ( P i n n a v a i a and
-3
A u ( I I 1 ) i s a l s o able t o form t y p e s

+
2+
N a , Ca
, F13+,

3+

Mortland,
I and
2+
3+

I1 complexes (Vandepoel, 1 9 7 5 ) .
Cr
, Fe , Fe ,
2+
+
2+
Mn2+, Zn , Ag , N i 2 + and Co
o n l y form t y p e I complexes. A r o m a t i c
l i g a n d s c a n b e d i v i d e d i n 2 g r o u p s a c c o r d i n g t o t h e i r a b i l i t y t o form

2+

t y p e I o r b o t h t y p e s o f complexes w i t h Cu
The l a t t e r group c o n t a i n s
benzene, d i p h e n y l , n a p h t a l e n e , a n t h r a c e n e and a n i s o l e , t h e f o r m e r
t o l u e n e , x y l e n e s , p h e n o l , hexamethylbenzene and 1, 2 , 4 , 5
tetrachlorobenzene.
complex.
complexes.

Vandepoel e t a l . (1973) a l s o found a brown

T a b l e 7 . 3 summarizes 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 of t h e

The a s s i g n m e n t s g i v e n i n T a b l e 7.3 a r e t h o s e of Vande

P o e l e t a l . (1973) and must b e r e g a r d e d as working h y p o t h e s e s .

p r e s e n t t h e r e i s n o f i r m e x p l a n a t i o n of t h e s e s p e c t r a .
Complexes w i t h 2 ,2 ' - b i p y r i d i n e

( b i p ) and 1 , l o - p h e n a n t h r o l i n e

P t

(phen)

a r e exchanged w i t h e x t r e m e l y h i g h s e l e c t i v i t i e s and w i t h p r e c i p i t a t i o n
o f s a l t s i n t h e i n t e r l a m e l l a r s p a c e (Schoonheydt, P e l g r i m s , Heroes and
U y t t e r h o e v e n , 1 9 7 7 ; B e r k h e i s e r and M o r t l a n d , 1 9 7 7 ) .

Epacinns are

a b o u t 1.8nm and even a f t e r c a l c i n a t i o n i n t e r e s t i n g a d s o r p t i v e p r o p e r -

t i e s a r e e v i d e n t ( T r a y n o r , M o r t l a n d and P i n n a v a i a , 1978; L o e p p e r t ,
M o r t l a n d and P i n n a v a i a , 1 9 7 9 )
The s p e c t r u m of [ R u ( b i p ) 12+ i s

dominated by a ~ C band
T
a r o u n d 460nm and a n i n t r a l i w n d
band around 280nm ( F e r g i s o n and H a r r i s , 1966; L Y t l e and

~ + n "

177
1 9 6 9 ; Crosby and K l a s s e n , 1 9 6 5 ) .
TABLE 7 . 3

A b s o r p t i o n b a n d s and t e n t a t i v e a s s i g n m e n t s f o r Cu2+-benzene complexes

Species

assignment

benzene
255 (39200)

TI

-+

71

+TI::

comp1e x

iT::

physisorbed benzene
284 (35200)
type I (green)
390 (25640)
686 (14577)

charge t r a n s f e r
d-d

H2\
H20

t y p e I1 ( r e d )
510 (19608)

charge t r a n s f e r

900-5900

d-p

(11000-1700)

brown
355 (28169)
825 ( 1 2 1 2 1 )

charge t r a n s f e r

cu

;+/OH2
\

OH2

P H

d-d

On t h e c l a y t h e l a t t e r i s r e d u c e d i n i n t e n s i t y and a s h o u l d e r a p p e a r s
around 320nm ( K r e n s k e , Abdo, Van Damme, Cruz and F r i p i a t , 1 9 8 0 ) .
The f o l l o w i n g h y p o t h e t i c a l r e a c t i o n was p r o p o s e d t o a c c o u n t f o r
t h i s new band :

R e a c t i o n ( 1 2 ) r e s u l t s i n a l o s s of aromatic c h a r a c t e r o f t h e
ligand. A b l u e s h i f t o f t h e n+n:
band i s e x p e c t e d ( P l b e r t , 1 9 6 7 ) .
T h i s is o p p o s i t e t o t h e experimental o b s e r v a t i o n .
however, n o a l t e r n a t i v e i s a v a i l a b l e .

A t present,

178

The LMCT band i s a t 463nm on t h e h y d r a t e d h e c t o r i t e , a t 455nm on

t h e d e h y d r a t e d c l a y and a t 452nm i n aqueous s o l u t i o n ( K r e n s k e , ?&do
Van Damme, Cruz and F r i p i a t , 1 9 8 0 ) . Two e f f e c t s g o v e r n t h e s e
s h i f t s : ( i ) t h e change o f t h e s o l v e n t "H20" t o t h e s o l v e n t " c l a y "
and ( i i ) d i s t o r t i o n of t h e complex i n t h e i n t e r l a m e l l a r s p a c e .

The

l a t t e r i s e a s y t o imagine f o r 2 r e a s o n s : t h e " k e y i n u i n " phenomenon

and t h e i n t e r a c t i o n of a f l a t s u r f a c e w i t h a corrplex o f d i f f e r e n t
geometry.

The e x a c t n a t u r e o f t h e d i s t o r t i o n i s unknown a t p r e s e n t .

However d i s t o r t i o n s have b e e n invoked t o e x p l a i n s i r i l a r band s h i f t s

( F e l i x , F e r g u s o n , Giidel and L u d i , 1 9 8 0 ) .

'32

The l u m i n e s c e n c e p r o p e r t i e s o f R u ( b i p )
H 0-dependent.
2

t o c a . 15 %

on h e c t o r i t e a r e a l s o

The quantum y i e l d i n c r e a s e s by a b o u t 2 from ca. 3% H20

H20 ( 0 . 0 4 -+ 0 . 0 9 ) .
Cr(bip):+ on h e c t o r i t e , i r r a d i a t e d

i n i t s d-d band, h a s a quantum y i e l d d e c r e a s i n g from ca. 0.08 t o

c a . 0.002 w i t h i n c r e a s i n g w a t e r c o n t e n t ( K r e n s k e , Pbdo, Van Dame,
Cruz, and F r i p i a t , 1 9 8 0 ) . F o r b o t h complexes t h e l u m i n e s c e n c e i s
3+
3+
quenched i n a d i f f u s i o n - c o n t r o l l e d way by 02. Q u e n c h i n g by Eu , C r
o r Fe3+ i s more e f f e c t i v e w i t h t h e s e c a t i o n s s u b s t i t u t e d i n t h e
o c t a h e d r a l l a y e r s o f t h e l a t t i c e t h a n when t h e y a r e i n i o n exchange
positions.
These r e s u l t s open new r e s e a r c h a r e a s b u t many problems must
b e s o l v e d b e f o r e t h e s p e c t r a o f t h e s e complexes a r e u n d e r s t o o d and
r e l a t e d t o t h e i r p e c u l i a r i o n exchange b e h a v i o r .

The i m p o r t a n c e o f

a complete u n d e r s t a n d i n g of t h e s p e c t r o s c o p i c p r o p e r t i e s o f t h e s e
monolayer complexes r e a c h e s f u r t h e r t h a n t h a t .
I n d e e d , t h e photoc h e m i c a l s u b s t i t u t i o n o f 2H20 m o l e c u l e s on Cr(bip):+ on t h e s u r f a c e
i s i n c i s - p o s i t i o n s , whereas t h e r e a c t i o n i n s o l u t i o n g i v e s
trans-products

( C r u z , Pbdo, Van Damme and F r i p i a t , 1 9 8 0 ) .

This is

an example o f a s t e r e o s p e c i f i c , p h o t o c h e r r i c a l s u b s t i t u t i o n r e a c t i o n ,
t h e s t e r e o s p e c i f i c i t y b e i n g i n d u c e d by t h e s u r f a c e . Monolayer

'32

a r r a n g e m e n t s of Ru ( b i p )
d i s s o c i a t i o n of H 2 0 .

have been p r o p o s e d f o r p h o t o c a t a l y t i c

I t i s expected t h a t s t e r e o s p e c i f i c r e a c t i o n s

can b e performed on t h e c l a y s u r f a c e r o c c u p i e d by c a t i o n i c corrplexes

with c a t a l y t i c a c t i v i t y .
7.4

LATTICE TRFNSITION METAL IONS

U.v-vis.-n.i.r.
s p e c t r o s c o p y o f t r a n s i t i o n metal i o n s i n
l a t t i c e s i t e s i s mainly c o n c e r n e d w i t h Fe. The d-d bands o f Fe
a r e f o r b i d d e n and u s u a l l y n o t s e e n a t t h e low Fe c o n c e n t r a t i o n s
of k a o l i n i t e and smectite materials.

a t 240-5nm and a t 190-5nmr due t o an 0

They have 2 weak bands

+Fe(II1)

charae t r a n s f e r

179
transitions

( K a r i c h k o f f and B a i l e y , 1 9 7 3 ) , w i t h F e ( I I 1 ) i n o c t a h e d r a l

sites s u b s t i t u t i n g f o r A l ( I I 1 ) . For suspensions t h e i n t e n s i t y of

t h e b a n d a t 240nm i s d e p e n d e n t on t h e Fe c o n t e n t and on t h e t a c t o i d
s i z e of t h e m i n e r a l s (Chen, Shaked and B a n i n , 1 9 7 9 ) . I n n o n t r o n i t e
n e a r l y a l l F l ( I I 1 ) i s s u b s t i t u t e d by F e ( I I 1 ) and t h e 2 b a n d s a r e
f o u n d a t 260nm and a t 200nm. F e ( I I 1 ) s u b s t i t u t i n g f o r M g ( I 1 ) g i v e s
the c h a r g e t r a n s f e r b a n d i n t h e r e g i o n 245-250nm w h i l e i t i s a t 215nm
f o r t e t r a h e d r a l F e ( I I 1 ) ( K a r i c h k o f f and B a i l e y , 1 9 7 3 ) .
of t h e bands i s - p a r t i a l l y
bond l e n g t h s : FeIV-O

<

The p o s i t i o n

a t l e a s t - d e t e r p i n e d by t h e F e ( I I 1 ) - 0

FeV1(Al)-O

<

For nontrcrnite t h e

FeV1(Mg)-O.

s t r o n g l y i n t e r a c t i n g n e i g h b o u r i n g Fe i o n s may c r e a t e e x c i t o n s t a t e s ,
e x p l a i n i n g t h e r e d s h i f t t o 260nm ( K a r i c h k o f f a n d B a i l e y , 1 9 7 3 ) .

In

any case t h e b a n d s o f i m p u r i t y Fe o x i d e a r e r e p o r t e d a t 4 5 0 and 530nm,

d i a g n o s t i c a l l y d i f f e r e n t from t h e l a t t i c e b a n d s

(Bart, Furriesci,

C a r i a t i , Micene and Gessa, 1 9 8 0 ) .

The s p e c t r u m o f t h e F e - r i c h n o n t r o n i t e shows a l s o d-d t r a n s i t i o n s .
They a r e compared t o t h o s e o f V e r m i c u l i t e and m u s c o v i t e i n T a b l e 7.4
( K a r i c h k o f f and B a i l e y ,

1973)

TABLE 7.4
d-d

t r a n s i t i o n s (nm) o f F e ( I I 1 ) i n o c t a h e d r a l s i t e s i n c l a y s

transition

nontronite

vermiculite

muscovite

540

523 , 503

575 , 6 0 0

579

445

4 60

441

6Al (S)

+ 4T 2 ( G I

520

6Pl(S)

+4 T 1 ( G )

6 A 1 ( S ) -b 4 P l ,

4E ( G )

'A1(s)

+4 T2(D)

384

4 00

379

6Al(S)

+4 E ( D )

367

363

The e n e r g y i n c r e a s e of t h e 6Pl ( S )

+4 P1,

t r a n s i t i o n s i n t h e series v e r m i c u l i t e

<

4 E ( G ) a n d 6Pl ( S )

+4 E ( D )

n o n t r o n i t e < muscovite

f o l l o w s t h e decrease o f t h e F e ( I I 1 ) - 0 bond l e n g t h s .
When Fe3+ i n
2+
n o n t r o n i t e i s r e d u c e d t o Fe
t h e t y p i c a l d-d b a n d s d e c r e a s e and a
2+
Fe
Fe3+ charge t r a n s f e r t r a n s i t i o n a p p e a r s a r o u n d 760nr@, moving

t o 720nm w i t h h i g h r e d u c t i o n d e g r e e ( P n d e r s o n and F t u c k i , 1 9 7 8 ) .

180

The band splittings observed for vermiculite and muscovite are

ascribed to the Jahn-Teller effect (Karichkoff and Bailey, 1973).
The doublet at llOOnm and 400nm of Fe(II1) in micas is also
caused by the Jahn-Teller effect (Faye, 1968) , but there is some
discussion about the origin of the band intensity (Smith, 1977).
Indeed, for chlorite and biotite they increase with decreasing
temperature, a behavior not expected for symmetry allowed or
vibronically coupled transitions.
7.5 ORGANIC MOLECULES

Spectroscopy of adsorbed organic molecules allows surface acidity

measurements and -for coloured bases- identification of clays and
their application in the manufacture of pressure-sensitive,
carbon-free paper (Thompson, 1977; Lim, 1975). More recent
interest is found in the adsorption and degradation of pesticides
and in the luminescence, photochemical and photocatalytic properties
of surface-immobilized "monolayers" of these rrolecules.
The chemistry of these molecules on the surface is well understood
(Theng, 1974). The recent spectroscopic work is mainly concerned
with assignment of the observed bands. Thus, the usefulness of
spectroscopy for surface acidity measurements with H a m e t t dye
indicators has been demonstrated (Bailey and Karichkoff, 1973).
Tarasevich and coworkers studied the acidity of dehydrated H- and
P1-montmorillonites, cation-exchanged kaolinite and palygorskite
(Telichkun, Tarasevich and Goncharuk, 1976; Telichkun and Tarasevich,
1973; Tarasevich and Fedorova, 1979). The indicators used are
p-dimethylaminoazobenzene ( D W B , pKa = 3.3) , dicinnamalacetone
( D C P , pKa = -3.0) , benzo-acetophenone (BAPh, pKa = -5.61,
triphenylcarbinol (g3COH, pKa = -6.6) and diphenylcarbinol (d2CHOP,
pKa = -13.3).
Their characteristic bands are smmarized in Table 7.5.
Very strong Brijnsted and Lewis acidities are found on P- and P1-clays
Radicals Z 3 C o are thought to be generated through
(pKa = -6.6).
interaction with Fe3+. With the butylamine titration technique no
acidities stronger than pKa = -3.7 were found (Frenkel, 1974). This
is another illustration of the difficulties encountered by comparinu
different methods of surface acidity measurements (Jacobs, 1977).

181

TABLE 7.5
C h a r a c t e r i s t i c bands of i n d i c a t o r s on c l a y m i n e r a l s
DCF

DMPAB

X (nm)

a s signmen t

240-300

benzene r i n g

350

TI

4 00

chromophore

490-5
5 30

on e x c h a n g e a b l e P 1
p r o t o n a t ed

525
325

=yH-N='=>=NMe2

A (nm)

a N H = N e & H M e 2

450-480

chromophore on s u r f a c e

560

on A 1 3 + a t exchange s i t e s

6 50

on p13+ a t e x t e r n a l s u r f a c e

assignment

+ TI::

3+

BaPh
A

(nn)

assignment

+ 71::

305

TI

4 30

protonated

490-5

on e x c h a n g e a b l e P 1
3+
on l a t t i c e F 1

5 50
@,

3+

CHOH

(nm)

X (nm)

assignment

230, 285

p h y s i c a l l y adsorbed

415, 450

430, 445
460

g3 C+
g3 c+

310, 530

Co

assignment

g2

CH+

on A I ~ +

Dye m o l e c u l e s a r e exchanued on t h e s u r f a c e or s y n t h e s i z e d i n
s i t u ( S i f f e r t , 19-78).

On t h e s u r f a c e t h e y u n d e r a o a c i d - b a s e r e a c t i o n s ,

r e d o x r e a c t i o n s , c o m p l e x a t i o n w i t h t r a n s i t i o n m e t a l i o n s and
associations.

The b e s t known example i s b e n z i d i n e (Theng, 1 9 7 4 1 ,

which c a n undergo e l e c t r o n t r a n s f e r t o l a t t i c e Fe3+ by s h o r t r a n g e

i n t e r a c t i o n between r - e l e c t r o n s of b e n z i d i n e and s u r f a c e oxygens
( Y a r i v , 1 9 7 6 ) . These s t u d i e s have b e e n e x t e n d e d t o more
c o m p l i c a t e d m o l e c u l e s and a summary o f t h e s p e c t r o s c o p i c d a t a i s
g i v e n i n T a b l e 7.6.

182

TABLE 7 . 6
S p e c t r o s c o p y o f d y e s on c l a y s
solution

X (nm)
Na-V

Na-M

Ni-M

FeM

Safranine T
S+

528

504-10

504-510

SH2+

579

550

555

SHZ+

6 30

592

546 ( b r o a d )

methylene b l u e
BM+

665

665

(BM+)

595-615

570

N i l blue

BN+

640

640

(BN+)

5 8 0 - 6 10

560-590

625

640-5

4 30

445-50

435-55

435-60

b r i l l i a n t green
vB+

ChrysoIdine
CR+

V = vermiculite, M = Montmorillonite
I t i s shown t h a t d i m e r i z e d c a t i o n s a b s o r b a t s h o r t e r w a v e l e n g t h s

t h a n t h e c o r r e s p o n d i n g monomers and a f u r t h e r b l u e s h i f t o f

i s o b s e r v e d f o r t h e d i m e r s on t h e s u r f a c e .
found i n t h e l i t e r a t u r e f o r t h e monomers.

2.

20n~

N o such u n i f o r m i t y i s

Thus, t h e bands o f

rhodamine B and c h r y s o i d i n e do n o t undergo s i g n i f i c a n t f r e q u e n c y s h i f t s

a f t e r a d s o r p t i o n , w h i l e t h o s e of b r i l l i a n t g r e e n , t h e p e s t i c i d e
chloramben and t h e S o r e t band o f p o r p h y r i n s show r e d s h i f t s ( G h o s a l
and Mukherjee, 1 9 7 3 : B e r k h e i s e r and A h l r i c h s , 1 9 7 6 ; Van Dame, C r e s p i n ,
O b r e c h t , Cruz and F r i p i a t , 1 9 7 8 ; S a e h r , L e Dred and F o f f n e r , 1 9 7 8 ) . The
c h a r a c t e r i s t i c bands of s a f r a n i n e and j a n u s g r e e n are r e p o r t e d t o
undergo b l u e s h i f t s (Van D a m e , C r e s p i n , Cruz and F r i p i a t , 1 9 7 7 ;
Ghosal and Mukherjee, 1 9 7 3 ) .
for

+
S

on Na-M

An e x t r e m e case o f b l u e s h i f t was found

(Van D a m e , C r e s p i n , Cruz and F r i p i a t , 1 9 7 7 ) : t h e

183
band maximum of 528nm was a t 468nm i n s u s p e n s i o n .

T h i s was a s c r i b e d

t o t h e d e g r e e o f d i s p e r s i o n : i n o t h e r words t o l i a h t s c a t t e r i n g .
L i g h t s c a t t e r i n g i s w a v e l e n g t h d e p e n d e n t and f o r g r a i n s i z e s s i m i l a r
t o t h e w a v e l e n g t h t h e s c a t t e r i n g c o e f f i c i e n t i s - t o a f i r s t approximat i o n - p r o p o r t i o n a l t o t h e wavelength.
contrary t o the observation.

Calculation gives a red s h i f t ,

A l s o the reported red s h i f t s are

u s u a l l y l a r q e r t h a n e x p e c t e d on t h e b a s i s o f l i g h t s c a t t e r i n g a l o n e
(Kortfim, 1 9 6 9 ) .

Many o t h e r f a c t o r s can c o n t r i b u t e .

They a r e : ( i )

s t e r i c e f f e c t s i n d u c e d by t h e r i g i d b i d i m e n s i o n a l s u r f a c e : ( i i ) s o l v e n t
e f f e c t s , a s t h e h y d r a t e d c l a y h a s a p o l a r i t y d i f f e r e n t from t h e
s o l v e n t from which t h e dye i s a d s o r b e d , n+n::
t r a n s i t i o n s underao
b l u e s h i f t s , when t h e p o l a r i t y i n c r e a s e s : T + I T : :
t r a n s i t i o n s undergo
r e d s h i f t s (Rao, 1 9 7 5 ) . O t h e r f a c t o r s a r e P-bondina t o s u r f a c e
oxygens, r e d i s t r i b u t i o n o f p o s i t i v e c h a r g e o v e r t h e m o l e c u l e when
a d s o r b e d ( S a e h r , L e Dred and H o f f n e r , 1978) a n d , f o r p o r p h y r i n s ,
i n c r e a s e d r e s o n a n c e i n t e r a c t i o n between p h e n y l o r p y r i d y l s u b s t i t u e n t s
and t h e p o r p h y r i n n u c l e u s (Van Damme, C r e s p i n , O b r e c h t , Cruz, F r i p i a t ,
1978). I t w i l l be very d i f f i c u l t t o individualize t h e d i f f e r e n t
c o n t r i b u t i o n s b e c a u s e t h e y always a c t s i m u l t a n e o u s l y .
7.6

CONCLUSIONS
I n t h e a r e a of t r a n s i t i o n m e t a l i o n s i n t h e i n t e r l a r r e l l a r s p a c e

o n l y complexes o f h i g h o x i d a t i o n s t a t e metals ( h a r d a c i d s ) w i t h h a r d
b a s e s have been i n v e s t i g a t e d i n d e t a i l .

Three c o n c l u s i o n s can b e

drawn : ( i )p l a n a r complexes a r e p r e f e r e n t i a l l y a d s o r b e d on t h e
"bidimensional" surface.

T h i s a l l o w s t h e e a s y s y n t h e s i s of

complexes on t h e s u r f a c e , which are d i f f i c u l t t o s y n t h e s i z e i n

c l a s s i c a l inorganic chemistry:

( i i ) t h e s u r f a c e oxygens do n o t

e n t e r i n t o t h e f i r s t c o o r d i n a t i o n s p h e r e t o any s i g n i f i c a n t
extent,

( i i i ) a d e t a i l e d l i g a n d f i e l d a n a l y s i s of t h e s p e c t r a i s

necessary t o quantify t h e information leading to t h e 2 previous

conclusions.

How

f a r t h e s e conclusions can b e extended t o

complexes o f low o x i d a t i o n s t a t e m e t a l s ( s o f t a c i d s ) w i t h e l e c t r o n
r i c h l i g a n d ( s o f t b a s e s ) , remains t o be i n v e s t i u a t e d .
An e x c i t i n g new r e s e a r c h a r e a h a s been opened : p h o t o p h y s i c s and
p h o t o c h e m i s t r y o f monolayer complexes.

The p r e l i m i n a r y r e s u l t s look

v e r y p r o m i s i n g a s r e a c t i o n s can b e c o n t r o l l e d s t e r e o s p e c i f i c a l l y on
t h e s u r f a c e . An e x t e n s i o n t o p h o t o c a t a l y t i c work i s e x p e c t e d . The
e l e c t r o n i c i n t e r a c t i o n s o f o r g a n i c c a t i o n s w i t h t h e s u r f a c e are p o o r l y
understood.

T h e i r ( p h o t o ) c h e m i s t r y and ( p h o t o ) c a t a l y s i s on t h e

184

surface w i l l t h e r e f o r e be very d i f f i c u l t .

detailed spectroscopic

a n a l y s i s o f model s y s t e m s , e v e n t u a l l y s u p p o r t e d by quantum m e c h a n i c a l
calculations, is necessary t o i n i t i a t e t h e s e s t u d i e s .
F i n a l l y , t h e r e i s a l a c k of q u a n t i t a t i v e s p e c t r o s c o p i c s t u d i e s .
T h i s i s an e x t r e m e l y d i f f i c u l t t o p i c b e c a u s e of t h e h e t e r o p e n e o u s
n a t u r e of t h e s y s t e m s b u t some a t t e m p t s t o w a r d s s i m p l e model s y s t e m s
should be c a r r i e d out.

7.7
EPPENDIX
S t a t e f u n c t i o n s and e n e r g y m a t r i c e s f o r N i ( I 1 ) i n D q h symmetry
7.7.1
The 5 3d o r b i t a l s are r e p r e s e n t e d a s u = d,2, v = d X 2 - y2, I =
d
5 = d
and n = dxz. Only t h e u p p e r h a l f o f t h e symmetric
XY'
Y=
m a t r i c e s i s shown. F o r d e t a i l s of t h e c o n s t r u c t i o n o f s t a t e f u n c t i o n s
and c a l c u l a t i o n o f e n e r g y m a t r i c e s I r e f e r t o " M u l t i p l e t s o f t r a n s i t i o n - m e t a l i o n s i n c r y s t a l s " by S . Sugano, Y . Tanabe and H . Karrinmra,
Academic P r e s s , N e w York, 1970, 331 pp. A, B and C a r e R a c a h ' s
i n t e r e l e c t r o n i c r e p u l s i o n p a r a m e t e r s . E i s a common p a r a m e t e r and

C i s assumed e q u a l t o 4B. A l l A2 and A3 a r e

a r b i t r a r i l y t a k e n 0.
d e f i n e d i n f i g u r e 7.1.

1
--[I5
2

A+4B+3C-E

4B+C
2Al+A+4B
+3C-E

+ + 5 \+In n I1

C
4B+C

fi (3B+C)

2 A2+E+4B
+3C-E

E = A +F+4B+2C
2

A2+A+4B-E

-6B
2A3+A-5B-E

185

- 2 6 B
2A 3+A+B+2C-E

A1+A+2C-E

A 3+A+B+ZC-E

A3+A-5B-E

-G/2 B

-3/2 B
A 2+ A 3 +P+B+ZC-E

-5?/2

3B

-3fi

A 2+A 3+A-5B-E

- 3 0 B

2A3+A+B+2C-E

+A

B
+P+ B-E

2fl B
Al+A2+A+2C-E

186
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