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Determination of the Cation Exchange Capacity (CEC) of Clay Minerals

Using the Complexes of Copper(II) Ion with Triethylenetetramine and
Tetraethylenepentamine

Article  in  Clays and Clay Minerals · January 1999

DOI: 10.1346/CCMN.1999.0470315

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Lorenz P Meier
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Clays and Clay Minerals, Vol. 47, No. 3, 38(~388. 1999.

NOTE

D E T E R M I N A T I O N OF THE C A T I O N E X C H A N G E C A P A C I T Y (CEC) OF
C L A Y M I N E R A L S U S I N G THE C O M P L E X E S OF COPPER(II) ION W I T H
TRIETHYLENETETRAMINE AND TETRAETHYLENEPENTAMINE

LORENZ P. MEIER1 AND GUENTER KAHR2

Department of Materials, Institute of Polymers, ETH, CH-8092 Ztifich, Switzerland
2 Laboratory for Clay Mineralogy IGT, ETH, CH-8093 Ztirich, Switzerland

Key Words--Cation Exchange Capacity of Clays, CEC, Copper Complex, Triethylenetetramine, Tetrae-
thyenepentamine.

INTRODUCTION centrations is not appropriate, due to the small relative

differences at these high concentrations.
The ion-exchange capability of clay minerals, in
Methylene blue can be used in a rapid qualitative
particular, smectites, influences their unique physical
procedure, but results are not reliable in comparison
properties, such as the cation retention and diffusion
to other methods (Kahr and Madsen, 1995; Yariv et
processes of charged and uncharged molecules. These
al., 1990). Recent investigations of CEC methods use
processes influence cation and molecule migration
an Ag thiourea complex (Dohrmann and Echle, 1994;
through clay-rich barriers in nature. The numerical
Chabra et al., 1975), Co(III) hexamine complex
value of this property is described by the cation ex-
(R6my and Orsini, 1976), and Cu(II) ethylenediamine
change capacity (CEC). Methods for determining CEC
complex (Bergaya and Vayer, 1997). Clay minerals
involve the complete exchange of the naturally-occur-
have a high affinity for these ions. This affinity allows
ring cations by a cationic species, such as ammonium,
CEC determination directly, via the ion concentration
K, Na, methylene blue, Co(III) hexamine complex
(Rdmy and Orsini, 1976), Ba, Ag thiourea complex, decrease in the exchanging solution.
and Cu(II) ethylendiamine complex. Exchange with The Cu in the blue Cu(II) ethylenediamine complex
organic cations, such as alkylammonium, provides an has a high affinity for clay minerals. Thus, atomic ab-
indirect method for the determination of CEC. This sorption spectroscopy (Bergaya and Vayer, 1997)
procedure involves determination of the expansion of would allow for an easy photometrical determination.
the layers and calculations involve charge density However, the photometrical extinction in these solu-
(Olis et al., 1990; Lagaly, 1981). Depending on the tions is too low.
method utilized, the excess of the exchanged cations The Cu(II) ion forms stable complexes with the oli-
is removed in a subsequent step and the amount re- goamines triethylenetetramine (trien), tetraethyle-
tained on the clay is determined. However, the deter- neamine (tetren), and pentaethylenehexamine (penten),
mined CEC values are dependent on the method used. which are bound over four and five N atoms to Cu.
Although time consuming, the exchange with ammo- They form violet-blue complexes. The stability con-
nium acetate is the standard method for CEC deter- stants are 20.4 for Cu(II)-trien, 22.8 for Cu(II)-tetren,
mination (Mackenzie, 1951). and 22.4 for Cu(II)-penten, respectively (Gmelin,
To obtain complete ion exchange and to obtain re- 1966). The maximum light extinction for these com-
liable values of C E C , either a high surplus of an ex- plexes varies slightly in the pH range of 5-10. The
changing cation or a cation with a high affinity for the maximum absorption is not affected by other cations
clay mineral must be employed. In the former, because or anions at low salt concentration (Cheng, 1962).
of the excess of cations, (usually in 1 M salt solutions) Compared to other methods the Cu(II) complexes with
clay suspensions must be washed until salt free. A de- triethylenetetramine and tetraethylenepentamine allow
termination of concentration before and after the cat- an easy and rapid CEC determination by photometric
ion exchange to assess differences at such high con- analysis.

Copyright 9 1999, The Clay MineralsSociety 386

Vol. 47, No. 3, 1999 CEC of clay minerals 387

Table 1. Characteristic values of the investigated materials.

Clay Intedayer
content cations
Sample Origin % exchange

Bentonite SAz-1 ("Cheto") Arizona (USA) 90 Ca 2+

Bentonite Volclay Wyoming (USA) 89 Na §
Bentonite MX-80 Wyoming (USA) 75 Na +
Bentonite Montigel Bayern (Germany) 62 Ca 2+
K-Bentonite B39 Kinnekulle (Sweden) 76 Ca 2+
K-Bentonite B31/32 Kinnekulle (Sweden) 87 Ca 2+
K-Bentonite M40 Montana (USA) 39 Cae+/Mg 2+
Illite MC Massif Central (France) 88 Ca 2+
Illite S Sarospatac (Hungary) 86 Ca 2+
China Clay (Kaolinite) St. Austell (UK) 99 Ca 2+
Clinoptilolite Slowakia 160 Ca 2+

M A T E R I A L S AND M E T H O D S d e t e r m i n e d at 6 2 0 n m b y a L a n g e L P 1 W F i l t e r p h o -
S e v e r a l clay m i n e r a l s a n d a zeolite (Table 1) o f tometer. T h e e x t i n c t i o n m a x i m a w a s 5 8 0 n m for
k n o w n C E C w e r e used. Table 2 s h o w s e a c h C E C as C u ( I I ) - t r e n a n d 6 3 0 n m for C u ( I I ) - t e t r e n a n d Cu(II)-
d e t e r m i n e d b y the a m m o n i u m acetate m e t h o d a n d the p e n t e n u s i n g a Dr. L a n g e C A D A S 100 p h o t o m e t e r .
r e s p e c t i v e m e t h y l e n e - b l u e v a l u e (not c o r r e c t e d w i t h L i n e a r i t y in the a b s o r p t i o n was o b s e r v e d in the r a n g e
o f 10 -4 a n d 10 2 M in the Cu c o m p l e x e s .
the C E C o f a r e f e r e n c e clay) m e a s u r e d w i t h N a h e x a
m e t a p h o s p h a t e as a d i s p e r s i o n a g e n t ( K a h r a n d M a d - T h e p H o f the C u c o m p l e x s o l u t i o n was --7 a n d the
sen, 1995). s o l u t i o n w a s n o t b u f f e r e d for the e x c h a n g e reactions.
Cu(II) sulfate (purum, free o f water), t r i e t h y l e n e t e - H o w e v e r , m e a s u r e m e n t s in p h o s p h a t e b u f f e r s at p H o f
7 g a v e similar results.
t r a m i n e (purum), t e t r a e t h y l e n e p e n t a m i n e (techn.), a n d
p e n t a e t h y l e n e h e x a m i n e (techn.) w e r e o b t a i n e d f r o m
Experimental procedure for the photometric
FLUKA AG, CH-9471 Buchs. Cu(II)-trien complex
measurement with the Copper(lI)-tren complex
was u s e d for the d e t e r m i n a t i o n b e c a u s e o f its h i g h pu-
rity. E x c h a n g e w i t h the C u ( I I ) - p e n t e n c o m p l e x solu- 2 0 0 m g (-+0.5 m g ) o f clay s a m p l e w i t h a C E C o f
tion s h o w e d n o significant d i f f e r e n c e to the tetren < 1 0 0 m M o l / 1 0 0 g w e r e a d d e d to 35 m l o f distilled
c o m p l e x a n d thus, was not i n v e s t i g a t e d further. w a t e r a n d d i s p e r s e d b y u l t r a s o n i c t r e a t m e n t (20 kHz,
4 0 0 W, 5 min). A n y r e m a i n i n g s a m p l e w a s w a s h e d o f f
Preparation of the 0.01 M copper(lI)-trien sulfate the u l t r a s o n i c rod. T h e s u s p e n s i o n w a s diluted in a 50
solution m l v o l u m e t r i c flask to 5 0 ml, t h e n c o m p l e t e l y trans-
1.463 g o f t r i e t h y l e n e t e t r a m i n e were d i s s o l v e d in ferred into a 100 m l beaker. W h i l e stirring the s u s p e n -
100 m l o f distilled water. A n o t h e r s o l u t i o n was pre- sion, 10 m l o f the s o l u t i o n o f the C u c o m p l e x w a s
p a r e d b y m i x i n g 1.596 g o f d r y Cu(II) sulfate w i t h added. A f t e r 3 m i n r e a c t i o n time, the s u s p e n s i o n w a s
distilled w a t e r to give 1 1 o f solution. T h e s e solutions c e n t r i f u g e d w i t h a m i c r o c e n t r i f u g e at 13,000 r p m (a
w e r e t h e n m i x e d together. A series o f dilute Cu(II) force o f 11,000 ' g ' ) for 3 min. T h e s u p e r n a t a n t solu-
c o m p l e x s o l u t i o n s was p r e p a r e d a n d the e x t i n c t i o n w a s tion was c a r e f u l l y r e m o v e d a n d the e x t i n c t i o n w a s

Table 2. Measured CEC with the ammonium acetate method and with the copper(II) complexes and the methylene blue
value (not corrected with the CEC of a reference clay).
CEC Methylene CEC CEC
NH4OAc pH 7 blue value Cu-trien Cu-tetren
Material (mmol/100 g) (mmol/100 g) (mmol/100 g) (mmol/100 g)

Bentonite SAz-1 120 145 122.0 122.0

Bentonite Volclay 81.9 106 84.5 83.7
Bentonite MX-80 71.5 92 75.5 78.9
Bentonite Montigel 62 78 63.9 65.2
K-Bentonite B39 53 75 60.1 59.9
K-Bentonite B31/32 42 63 46.1 48.7
K-Bentonite M40 29 40 31.4 32.6
Illite MC 19 29 20.0 21.9
Illite S 16 25 19.0 20.0
China Clay (Kaolinite) 3.8 12 6.4 4.0
Clinoptilolite 160 10 5.0 4.0
388 Meier and Kahr Clays and Clay Minerals

140 , , , = , , i , , = , , , = , , , i , , , i , , ,
s u m m a r y , the C E C m e a s u r e m e n t u s i n g the C u c o m -
- - y = 2 . 9 7 + 1 . 0 0 2 - x R = 0 . 9 9 8 9 p l e x e s o f trien, tetren, a n d p e n t e n is a r a p i d a n d reli-
1
120 able m e t h o d . T h e C E C results u s i n g this m e t h o d are
in g o o d a g r e e m e n t w i t h the s t a n d a r d a m m o n i u m ace-
8 tate m e t h o d . H o w e v e r , this m e t h o d s h o u l d n o t r e p l a c e
,~ 100
the a m m o n i u m acetate m e t h o d for c e r t a i n m a t e r i a l s ,
such as zeolites. N o n e t h e l e s s , the m e t h o d g i v e s reli-
E 80 3 2
able v a l u e s o f C E C q u i c k l y a n d w i t h o u t the o f e x p e n -
E
sive e q u i p m e n t . Values o f the C E C are m u c h c l o s e r to
"-~ 5 4
60 t h o s e o b t a i n e d u s i n g a m m o n i u m acetate c o m p a r e d to
/ 2 Volclay t h o s e o b t a i n e d u s i n g the m e t h y l e n e - b l u e m e t h o d ( K a h r
U 6 <j~ 3 Bento~lite MX-80
40 - /- 4 Bentonite Montigel a n d M a d s e n , 1995). In addition, the C E C d e t e r m i n a -
7 ,~ 5 K - B e n t o n i t e B39 tion u s i n g the C u ( I I ) - t r i e n c o m p l e x is suitable for N a
9 f.) 6 K-Bentonite B31/32
8 / ~ 7 K-Bentonite M40 a n d C a - r i c h clay,
20 - 9,~ 8 tllite M C
9 lllite S
~'/ 10 Ch-i-na C l a y ( K a o l i n i t e ) REFERENCES
0 , , ,
2 /0 ' ' ' i ' ' ' i ' ' ' i ' ' ' i ' ' ' I ' ' '
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