Clay Minerals (1994) 29, 297-300
NOTE
DETERMINATION OF HYDRATION (H20-) AND STRUCTURAL (H2 O+)
WATER FOR CHEMICAL ANALYSIS OF SMECTITES. APPLICATION
TO LOS TRANCOS SMECTITES, SPAIN
Typically, the m e t h o d e m p l o y e d for d e t e r m i -
n a t i o n of h y d r a t i o n w a t e r in clays is the heating of
t h e sample at 110~ overnight. T h e c o n s e q u e n t
h e a t i n g at 1000~ is t h o u g h t to p r o d u c e the loss of
structural water, i.e. of hydroxyls. Nevertheless,
some a u t h o r s h a v e r e p o r t e d t h a t n o t all h y d r a t i o n
w a t e r evolves u p o n heating at l l 0 ~ F o r ex-
a m p l e , Fripiat et al. (1960) p r o v e d , by i n f r a r e d
spectroscopy, t h e p r e s e n c e of h y d r a t i o n w a t e r
after h e a t i n g at such a t e m p e r a t u r e , a n d Savin &
E p s t e i n (1970) used t e m p e r a t u r e s up to 250~ to
e n s u r e the loss of all h y d r a t i o n w a t e r for t h e i r
isotopic studies.
O b s e r v a t i o n of chemical data on smectites f r o m
a great n u m b e r of publications shows t h a t the
a m o u n t of structural w a t e r ranges b e t w e e n 6 a n d
12 w t % with respect to the sample weight after
drying at 110~ ( W e a v e r & Pollard, 1973; New-
m a n & B r o w n , 1987). O n the basis of the
structural f o r m u l a e of smectites the ideal a m o u n t
of structural w a t e r is a r o u n d 5 % . T h e r e is a clear
d i s a g r e e m e n t b e t w e e n chemical a n d structural
data.
Structural water
In o r d e r to d e t e r m i n e quantitatively the causes
of d i s a g r e e m e n t b e t w e e n ideal a n d chemical data,
a g r o u p of 20 samples from Los T r a n c o s deposit
( A l m e r f a , s o u t h e a s t e r n Spain) have b e e n studied
thermally. A description of the samples can b e
f o u n d in Reyes et al. (1979) a n d in Linares et al.
(1993). E a c h sample h a d a particle size < 2 ~tm.
S o m e c o n t a i n some interstratified kaolinite, as
could b e d e t e c t e d by m e a n s of X-ray diffraction of
o r i e n t e d m o u n t s t r e a t e d with e t h y l e n e glycol.
T h e smectites were studied by m e a n s of differ-
ential t h e r m a l analysis ( D T A ) a n d t h e r m o g r a v i -
m e t r y ( T G ) in a N E T Z S C H S i m u l t a n e o u s
T h e r m a l Analysis S T A 409 E P with a T e m p e r a -
ture P r o g r a m m e r 410 controlled by c o m p u t e r .
Differential t h e r m a l analysis a n d T G curves were
9 1994 The Mineralogical Society
o b t a i n e d simultaneously for all samples using 3 0 -
35 mg, r u n at 10~ with an a t m o s p h e r e of air.
Figure 1 shows the D T A a n d T G curves of o n e
of the samples. T h e i r features are the same as for
any smectite. T h e first is a n e n d o t h e r m i c r e a c t i o n
c o r r e s p o n d i n g to a quick loss of mass up to
--200~ This stage c o r r e s p o n d s to loss of hyd-
ration water. T h e s e c o n d step is o n e in which T G
shows a c o n s t a n t mass loss t h a t is not reflected in
D T A . T h e r e is n o generally a c c e p t e d e x p l a n a t i o n
for this process, a l t h o u g h it is related to h y d r a t i o n
w a t e r loss ( M a c k e n z i e , 1964; G r i m , 1968). A
third step is a new e n d o t h e r m i c reaction that can
be multiple (i.e. one, two or, rarely, t h r e e D T A
peaks) reflected clearly in T G curves as new,
quick mass losses. This step can begin in a r a n g e
of t e m p e r a t u r e s b e t w e e n 500 and 700~ What-
ever the t e m p e r a t u r e at which it begins, it always
intercepts the f o r m e r zone of c o n t i n u o u s , slow
mass loss s h o w n by T G . This stage c o r r e s p o n d s to
evolution of structural water. Finally, a b o v e
750~ an e x o t h e r m i c r e a c t i o n occurs, which m a y
b e p r e c e d e d by a n e d o t h e r m i c o n e a n d in which
t h e r e are n o mass changes. T h e s e reactions are
related to structural b r e a k d o w n a n d reorganiza-
tion of ions in n e w stable p h a s e s at those
temperatures.
T a b l e i shows t h e p e r c e n t a g e of mass loss in the
TA
T
I ~ I f I J I , I r I
0 200 400 600 800 1000
TEMPERATURE (~
FIG. 1. TG and DTA curves of a smectite from Los Trancos
deposit.
298 Note
TABLE I. Values of smectite mass loss in the 200-800~ (1964) a n d E1-Baraway et aL (1986) f o u n d a
range and in the true dehydroxylation region as shown by definite link b e t w e e n the slope of T G curves at
DTA and TG. They are measured by TG on the basis of this stage of t h e r m a l analysis of smectites a n d the
sample weight after drying at 110~
interlayer cation, b u t it is strange t h a t the w a t e r
molecules p r e s e n t such different s o r p t i o n ener-
Sample % mass loss % mass loss in gies. It is also possible t h a t t h e r e is some k i n d of
200-800~ dehydroxylation physical h i n d r a n c e to w a t e r evolution, such as
t r a p p i n g in closed p o r e s p r o d u c e d by layer
LT 10/3 8.3 5.0 collapse, or the fact t h a t t h e w a t e r molecules
LT 10/6 8.7 5.6
which h a v e already b r o k e n loose within the
LT 11 9.3 5.9
interlayers n e e d s u p p l e m e n t a r y energy to m a k e
LT 11/2 9.2 6.0
TR 3 6.9 4.1 t h e i r way to the smectite surface. Such effects
TR 4 7.5 4.4 would explain t h e n e e d for h i g h e r t e m p e r a t u r e s
T4 8.0 5.1 or m o r e h e a t i n g time for the c o m p l e t e evolution
T 15 7.9 4.8 of the water.
T 18 7.8 5.0 It is i m p o r t a n t to notice t h a t the t e m p e r a t u r e s
T.19 7.9 4.6 at which the reactions take place d e p e n d largely
T 20 9.5 6.6 o n the h e a t i n g rate. L o w rates give rise to an
T 22 7.1 4.6 earlier b e g i n n i n g a n d c o m p l e t i o n of reactions.
TR 110 6.9 3.0
Also, the reactions can b e c o m p l e t e d by p r e v e n t -
TR 115 7.7 5.1
ing the t e m p e r a t u r e f r o m increasing a n d by
TR 117 9.6 6.3
TR 119 7.7 4.8 m a i n t a i n i n g it for a sufficient a m o u n t of time.
TR 123 8.7 5.2 D e h y d r a t i o n a n d d e h y d r o x y l a t i o n are driven by
TR 125 7.9 5.4 b o t h t h e r m o d y n a m i c ( t e m p e r a t u r e ) a n d kinetic
TR 128 7.2 3.1 (time) conditions. T h e f o r m e r description corres-
TR 146 6.5 3.4 p o n d s to the s t a n d a r d h e a t i n g rate of 10~

r a n g e of 200-800~ c o r r e s p o n d i n g to mass loss in M e t h o d f o r true structural water determination

the second a n d third steps of D T A / T G , a n d the
p e r c e n t a g e of mass loss in the true dehydroxyla-
tion process c o r r e s p o n d i n g to t h e t h i r d D T A / T G
step. Study of this table shows t h a t h y d r a t i o n
w a t e r is n o t completely e v o l v e d during the first
step, b u t goes o n evolving t h r o u g h o u t the second.
T h e mass loss in the t h i r d stage is - - 5 % , in general
a g r e e m e n t with the ideal a m o u n t of structural
water. V a r i a t i o n s of the mass loss a r o u n d 5%
h a v e already b e e n r e p o r t e d (Schultz, 1969). T h e
sum of mass lffss in the s e c o n d a n d t h i r d stages is
b e t w e e n 6 and~,10%, a g r e e i n g with the a m o u n t s of
'structural w a t e r ' o b t a i n e d in most chemical
analyses. / each run, the samples were p l a c e d in a desiccator
T h e way in which a p a r t of h y d r a t i o n w a t e r is
r e t a i n e d by smectites, avoiding its c o m p l e t e
evolution a b o v e 200~ is u n k n o w n . T h e fact t h a t
t h e c o r r e s p o n d i n g weight loss displayed b y T G is
n o t o b s e r v e d by D T A can b e due to a lack of
t h e r m a l reaction, i.e. n o chemical b o n d s are
b r o k e n , or to the fact t h a t slow e n e r g y changes
m a y n o t b e resolved by D T A , showing only a
p e a k a s y m m e t r y like t h a t in Fig. 1. M a c k e n z i e
T h e following t h e r m a l study was d e v e l o p e d in
o r d e r to decide the conditions of t e m p e r a t u r e a n d
time in which h y d r a t i o n w a t e r is completely
evolved from smectites, t h e r e b y p e r m i t t i n g the
d e t e r m i n a t i o n of the real a m o u n t of structural
water. It was carried out u n d e r the same con-
ditions and with the i n s t r u m e n t s n o r m a l l y used in
r o u t i n e chemical analysis.
T h e same 20 smectitic samples were h e a t e d at
different increasing t e m p e r a t u r e s for different
times. T h e samples were placed in ceramic
crucibles a n d they were all t r e a t e d t o g e t h e r . A f t e r
with CaC12, allowed to cool, a n d t h e n weighed.
T a b l e 2 shows t h e study t e m p e r a t u r e a n d times,
t h e p e r c e n t a g e s of mass loss with respect to the
u n t r e a t e d s a m p l e weight, a n d t h e differences of
p e r c e n t a g e of mass loss in each t r e a t m e n t with
respect to the former.
T h e r e is n o t a single ideal p o i n t of t e m p e r a t u r e
a n d time at which all h y d r a t i o n w a t e r is evolved
a n d all structural w a t e r remains. This is a logical
 Note 299

TABLE2. Percentage of mass loss of smectites after each thermal treatment and their corresponding differences with respect
to the previous heat treatment.

% Wt % Wt % Wt % Wt % Wt % Wt
% Wt loss loss loss loss loss loss % Wt
loss 200~ Loss 200~ Loss 300~ Loss 300~ Loss 400~ Loss 400~ Loss loss Loss
Sample 110~ 4h dif. ov dif. 4h dif. ov dif. 4h dif. ov dif. 1000~ dif.

LT 10/3 14.0 13.8 -0.2 15.4 1.6 15.4 0.0 17.1 1.7 17.1 0.0 19.2 2.1 22.4 3.2
LT 10/6 12.4 12.4 0.0 13.9 1.5 14.0 0.1 15.6 1.6 15.6 0.0 17.9 2.3 21.1 3.2
LT 11 11.2 11.1 -0.1 12.2 1.1 12.5 0.3 14.2 1.7 14.4 0.2 17.5 3.1 20.5 3.0
LT 11/2 10.9 10.7 -0.2 12.2 1.5 12.6 0.4 14.2 1.6 14.1 -0.1 17.5 3.4 20.3 2.8
TR 3 15.3 15.7 0.4 17.0 1.3 17.4 0.4 18.4 1.0 18.3 -0.1 19.9 1.6 23.0 3.1
TR 4 15.9 16.3 0.4 17.6 1.3 18.0 0.4 18.8 0.8 18.8 0.0 20.1 1.3 23.4 3.3
T4 14.3 15.5 1.2 16.4 0.9 16.8 0.4 17.7 0.9 17.9 0.2 19.3 1.4 22.9 3.6
T 15 15.2 16.6 1.4 17.5 0.9 18.1 0.6 18.7 0.6 18.8 0.1 20.5 1.7 24.1 3.6
T 18 15.1 16.6 1.5 17.3 0.7 18.0 0.7 18.6 0.6 18.6 0.0 20.3 1.7 24.0 3.7
T 19 15.8 17.7 1.9 18.1 0.4 18.6 0.5 19.3 0.7 19.4 0.01 20.7 1.3 24.5 3.8
T 20 13.2 14.6 1.4 15.2 0.6 15.5 0.3 16.2 0.7 18.7 2.5 19.4 0.7 22.8 3.4
T 22 14.0 15.8 1.8 16.1 0.3 16.4 0.3 17.1 0.7 18.5 1.4 19.1 0.6 22.7 3.6
TR 110 11.9 14.1 2.2 14.3 0.2 14.9 0.6 15.5 0.6 16.8 1.3 17.5 0.7 20.6 3.1
TR 115 11.3 12.1 0.8 13.4 1.3 13.8 0.4 14.5 0.7 16.4 1.9 17.1 0.7 20.5 3.4
TR 117 10.9 11.6 0.7 12.7 1.1 13.1 0.4 13.8 0.7 16.9 3.1 17.6 0.7 20.7 3.1
TR 119 7.3 8.4 1.1 9.4 1.0 9.9 0.5 10.3 0.4 12.2 1.9 13.0 0.8 16.5 3.5
TR 123 12.4 13.2 0.8 14.3 1.1 14.7 0.4 15.1 0.4 17.4 2.3 18.2 0.8 21.6 3.4
TR 125 8.2 8.9 0.7 10.3 1.4 10.8 0.5 11.3 0.5 13.3 2.0 14.1 0.8 17.8 3.7
TR 128 11.6 12.5 0.9 13.7 1.2 14.2 0.5 14.5 0.3 15.4 0.9 16.1 0.7 19.8 3.7
TR 146 7.8 9.1 1.3 10.2 1.1 11.0 0.8 11.2 0.2 12.3 1.1 13.3 1.0 17.0 3.7

ov: overnight

c o n s e q u e n c e o f t w o facts: (1) t h e loss o f h y d r a t i o n t h a t t h e t e m p e r a t u r e w a s r a i s e d to 1000~ in t h e

w a t e r is c o n s t a n t a n d o v e r l a p s w i t h d e h y d r o x y l a -
t i o n ; a n d (2) t h e d e h y d r o x y l a t i o n t e m p e r a t u r e o f
s m e c t i t e s is v a r i a b l e . T h u s , at 4 0 0 ~ f o r 4 h , t h e
first t e n s a m p l e s h a v e n o m a s s l o s s , b u t t h e o t h e r
t e n h a v e a g r e a t loss. T h i s s h o w s t h a t t h e first t e n
lost all t h e i r h y d r a t i o n w a t e r in t h e p r e v i o u s
t r e a t m e n t a n d d i d n o t b e g i n to d e h y d r o x l y l a t e ,
a n d t h a t t h e o t h e r s b e g a n to l o s e s t r u c t u r a l w a t e r .
It is i m p o s s i b l e to d e t e r m i n e w h e t h e r o r n o t all
h y d r a t i o n w a t e r w a s lost in t h e p r e v i o u s s t e p f o r
the second ten samples. However, the hydration
w a t e r d o e s n o t s e e m to h a v e b e e n lost b e c a u s e t h e
s u m s o f loss d i f f e r e n c e s d u r i n g t h i s s t e p a n d t h e
following ones are higher than the percentages of
d e h y d r o x y l a t i o n m a s s loss s h o w n in T a b l e 1.
T h e v a l u e s o f m a s s loss p e r c e n t a g e s d u r i n g t h e
a c t u a l d e h y d r o x y l a t i o n a r e s o m e w h a t h i g h e r in
T a b l e 2 t h a n in T a b l e 1. S i n c e T G is t h e m o r e
a c c u r a t e t e c h n i q u e , its m e a s u r e m e n t s a r e m o r e
r e l i a b l e . A p o s s i b l e c a u s e o f t h o s e d i f f e r e n c e s is
conventional study and the TG calculations were
c a r r i e d o u t o n l y u p to 8 0 0 ~ in o r d e r to a v o i d
m a s s c h a n g e s d u e to p r o c e s s e s o t h e r t h a n
dehydroxylation.
I n s p i t e o f all t h e s e difficulties, it c a n b e
concluded that the best treatment for assuring
evolution of the greatest amount of hydration
w a t e r w i t h o u t r e a c h i n g d e h y d r o x y l a t i o n is h e a t -
i n g at 3 0 0 ~ o v e r n i g h t . T h i s t r e a t m e n t s h o u l d b e
e m p l o y e d in p l a c e o f t h e c u r r e n t l y m o r e u s u a l o n e
o f h e a t i n g at l l 0 ~ o v e r n i g h t . It w o u l d h e l p to
o b t a i n m o r e r e a l i s t i c s t r u c t u r a l f o r m u l a e : real
amounts of hydroxyls could be determined, (not
a l w a y s t h e i d e a l o n e s s u p p o s e d in s t r u c t u r a l
formulae determinations), and together with F
content might offer information about 0 2- for
O H s u b s t i t u t i o n . T h e s e last t w o f a c t o r s m a y p l a y
a n i m p o r t a n t role in b o t h t h e c o m p o s i t i o n o f t h e
octahedral sheet and the spatial distribution of
c a t i o n s w i t h i n it.
300 Note
GRIM R.E. (1968) Dehydration, rehydration, and the
ACKNOWLEDGMENTS changes taking place on heating. Pp. 278-352 in: Clay
Mineralogy. McGraw-Hill, New York.
We thank Mrs M a Jesfis Civantos and Mrs M a Teresa LINARESJ., HUERTASF., REYESE., CABALLEROE., BARA-
Martin-Vivaldi for their co-operation in the laboratory HONA E., GUARDIOEAJ.L., YAIqEZ J., ROMERO E. &
work and the typing of the paper, respectively. This work DELGADO A. (1993) Investigaci6n de las betonitas como
was carried out with the financial support of the Junta de materiales de sellado para almacenamiento de residuos
Andalucia (group 4049) and the DG1CYT project radiactivos de alta actividad. Pp. 85-126. ENRESA
PB91-0112. Technical Publication 01/93.
MACKENZIE R.C. (1964) Hydration characteristics of
E s t a c f o n E x p e r i m e n t a l del Z a i d i n J. CUADROS
montmorillonite. Ber. Deut. Keram. Ges. 41, 696-707.
(CSIC), F. HUERTAS
NEWMAN A.C.D. & B~OWN G. (1987) The chemical
P r o f e s o r A l b a r e d a 1, A . DEL~ADO constitution of clays. Pp. 1-128 in: Chemistry of Clays
18008 G r a n a d a , J. LINARES and Clay Minerals (A.C.D. Newman, editor). Mineral-
Spain. ogical Society, London.
R e c e i v e d 4 M a r c h 1993; r e v i s e d 29 O c t o b e r 1993 REYES E., HUERTASF. & LINARESJ. (1979) Mineralogia y
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Gata (Alrneria). V. Area de Los Trancos. Estudios Geol.
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