Clays and Clay Minerals, Vol. 31, No. 4, 305-311, 1983.

ANI ON- EXCHANGE PROPERTI ES OF

HYDROTALCI TE- LI KE COMPOUNDS
SHIGEO MIYATA
Kyowa Chemical Industry Co., Ltd., 305 Yashimanishi-machi
Takamatsu, Kagawa, 761-01, Japan
Abstract--Ion-exchange isotherms between hydrotalcite-like compounds (HT) of the NO3-, CI-, and SO4-
forms and F , 0 % Br , I , OH-, SO42-, CO3 z-, and Naphthol Yellow S (NYS 2-) ions were determined,
and the spacing and the width of the 003 reflection were measured as a function of HT composition. The
ion-exchange equilibrium constant for HTs of monovalent anions are in the sequence OH- > F > Cl >
Br- > NO3- > I , those for divalent anions are in the sequence CO3 ~- > NYS z- > SO42-. The ion-exchange
equilibrium constants tend to increase as the diameters of the anions decrease, and the crystallite size in
the 001 direction tends to increase with anions having higher selectivity. The OH-form of HT has the
smallest basal spacing and the largest crystallite size in the 001 direction.
Key Words---Anion exchange, Anion selectivity, Crystallite size, Hydrotalcite, Naphthol Yellow S, X-ray
powder diffraction.
I NTRODUCTI ON
Hydr ot al ci t e- l i ke compounds ( HT) can be r epr e-
s ent ed by t he f ol l owi ng formul a: [Mgl_xAI x+
[Ax/n n-. mH20] x-, wher ei n 0 < x < 0. 33, and A n- is an
exchangeabl e ani on havi ng a val ence of n. Thes e com-
p o u n d s a r e s i mi l a r t o t he mi ne r a l h y d r o t a l c i t e ,
MgnAIz(OH)16CO3"4H20 ( Mi yat a and Kumur a , 1973;
Tayl or , 1973; Mi yat a, 1975). HT consi st s of pos i t i vel y
char ged br uci t e- l i ke l ayer s [Mg, xAI~(OH)2] ~+ al t er -
nat i ng wi t h di s or der ed, negat i vel y char ged i nt er l ayer s
[A mHzO] 9 Mg and AI ar e r andoml y di st r i but ed
among t he oct ahedr al posi t i ons, and t he OH l ayer se-
quence is - B C - C A- AB - B C - ( Al l mann, 1968).
HT is s t a b l e t o 400~ but t r a n s f o r ms i nt o a
MgO-AI203 sol i d sol ut i on (Mg,-3x/zAlxO) by heat i ng t o
500~176 Thi s sol i d sol ut i on r ehydr at es and com-
bi nes ani ons t o f or m HT in t he pr es ence of wat er and
ani on ( Mi yat a and Okada, 1977; Mi yat a, 1980). Con-
s equent l y, bot h HT and heat - t r eat ed HT ar e capabl e of
capt ur i ng ani ons and ar e t her ef or e useful as hal ogen
s cavenger s for pol yol ef i nes pr oduced by Zi egl er cat a-
l yst or Fr i del - Cr af t cat al ys t and t her mal st abi l i zer s for
pol yvi nyl chl or i de et c. ( Mi yat a and Kur oda, 1981a,
1981b). Accor di ngl y, t he i on- exchange pr oper t i es of
hydr ot al ci t e- l i ke compounds ar e i mpor t ant . The pr es-
ent ar t i cl e of hydr ot al ci t e r epor t s t he s ynt hes i s of t he
NO3-, CI-, and SO4-forms and t he i on- exchange iso-
t her ms and i on sel ect i vi t y f or t hese compounds and F - ,
CI - , Br - , I% OH , SO42-, CO3 z-, and Napht hol Yel l ow
S 2- ani ons.
EXPERI MENTAL
Hydr ot al ci t e- l i ke compounds cor r es pondi ng t o t he
a bove ment i oned f or mul a in whi ch x is about 0.3 and
A" - is NO3 , CI - , or SO42- wer e pr epar ed by t he met h-
Copyright 9 1983, The Clay Minerals Society
od des cr i bed by Mi yat a (1975) and Mi yat a et al. (1977).
At x = about 0.3, t he i on- exchange c a pa c i t y of t he
pr oduct s was hi gh, and by- pr oduct s di d not f or m. A
smal l amount of CO~ 2- was i ncor por at ed i nt o t he pr od-
uct s, but becaus e t he CO32- is hi ghl y s el ect ed by t hese
compounds as c ompa r e d wi t h ot her ani ons, t he i on- ex-
change r eact i on of CO32- was i gnored.
Determination of ion-exchange isotherm
An amount of each HT cal cul at ed t o gi ve an i on- ex-
change capaci t y of 2 t o 5 meq was pl aced in a fl ask wi t h
a gr ound gl ass s t opper and an appr opr i at e amount of a
0.1 N aqueous sol ut i on of each t he af or ement i oned an-
i ons was added. The fl ask was pl aced in a cons t ant t em-
per at ur e vessel (25~ and shaken over ni ght . The con-
t ent s of t he fl ask wer e t hen fi l t ered and t he ani on
concent r at i on in t he fi l t rat e det er mi ned. The ani on so-
l ut i ons used wer e pr epar ed by usi ng Na F, Na Br , KI ,
Na OH, Na2CO3, Na2SO4, and Napht hol Yel l ow S (an-
al yt i cal gr ade made by Wa ko Pur e Chemi cal Co. , Lt d. ,
chemi cal f or mul a C,0H4NzNazOsS" 3H20).
The i ndi vi dual ani ons wer e quant i t at i vel y det er -
mi ned by t he f ol l owi ng met hod: OH , by t i t r at i on wi t h
0.1 N HCI; F - by t i t r at i on wi t h 0.1 N t hor i um ni t r at e
usi ng Al i zar i n Red S as an i ndi cat or in a c c or da nc e wi t h
t he met hod of Japan St andar d As s oci at i on (1965a); CI - ,
Br - , and I - , by t he Vol har d met hod ( Ni ppon Bunseki
Kagakukai , 1961); CO32- by t he met hod of Japan St an-
dar d As s oci at i on (1965b); NO3 , by r educi ng NO3- of
t he s ampl e wi t h a mi xt ur e of Na OH sol ut i on and De-
ba l da al l oy t o f or m NH3 and backt i t r at i ng exces s sul-
furi c aci d havi ng NH3 a bs or be d in it wi t h aqueous
Na OH; SO42-, by t he gr avi met r i c anal ysi s of bar i um
sul fat e; and Napht hol Yel l ow S, phot omet r i cal l y by
measur i ng t he a bs or ba nc e at 430 nm usi ng a Hi t achi
Model 101 Spect r ophot omet er .
305
306 Miyata Clays and Clay Minerals
1 . 0 N03"CO 3 C I - N Y S N 0 3 - $ 0 4
1.0
OH
0 . 8
0 . 8
o.e
, . . , < o.e
0. 4
0. 2
O.
0 0 , 2 0 . 4 0 . 6 0 . 8 1.0 0
~ A 0 0 2 0 . 4 0 . 6 0 . 8 1.0
SA
Figure 1. Ion-exchange isotherms for the HT- NO3- OH- ((3),
HT-NO3-F- ( e) , HT-NO3-C1- (/k), HT-NO3-Br- (~), and HT-
NO3- I - (113) systems at 0.1 total normality and 25~
X-ray powder diffraction (XRD) analyses were car-
ried out using Ni-filtered CuKa radiation with a Philips
X-ray diffractometer after drying the products at 60~
for 20 hr.
RESULTS AND DISCUSSION
Three different HT exchangers (HT-NO3, HT-C1, HT-
SO4) were prepared. Their chemical compositions are
listed in Table 1.
Prior to measuring ion-exchange isotherms the sta-
bility of HT-NO3 in NaF and NaOH solutions was de-
termined by examining the molar ratio of Mg to AI in
the HT-NO3 using the lattice parameter a (Miyata, 1980)
before and after contact with the solution. The molar
ratio of Mg to A1 in HT-NO3 did not change, and AI was
virtually undetectable in the solution. Accordingly, AI
in HT does not react with F- or OH- anions.
Ion-exchange isotherms at 25~ in a total ion con-
centration of 0.1 N of HT-NO3-OH-, HT-NO3-F-, HT-
Table 1. Chemical analyses and formulae for hydrotalcite-
like compounds studied.
HT-NOa HT-CI HT-SO4
(wt. %) (wt. %) (wt. %)
A1203 17.5 18.4 17.6
MgO 32.5 36. I 34. I
CO2 1.05 0.77 0.77
NO3 17.0
C1 12.3
SO4 15.7
x 0.299 0.287 0.290
HT-NO3: Mgo.ro2Alo.2~(OH)2(NO3)o.268(CO3)o.61s" mH20.
HT-CI: Mg0.r13A10.2sr(OH)2C10.zrs(CO3)0.014" mHzO.
HT-SO4: Mg0.r10A10.zgo(OH)2(SO4)0.137(CO3)0.01~" mH20.
Figure 2. Ion-exchange isotherms for the HT-NO3-SO42- ( e) ,
HT-NO3-CO3 z ( 9 HT-C1-NYS 2- (A), and HT-SO4-CO32-
( ~) systems at 0.1 total normality and 25~
NO3-CI-, HT-NO3-Br-, HT-NO3-I-, HT-NO3-SO42-,
HT-NO3-CO32-, HT-C1-NYS 2-, and HT-SO4-CO32-
systems are shown in Figures 1 and 2. In the ion-ex-
change isotherms, St, for example, on the abscissa rep-
resents the equivalent fraction of a F- ion based on the
total anion concentration in an aqeous solution at equi-
librium, and (HT)v, for example, on the ordinate rep-
resents the equivalent fraction of the F- ion exchanged
onto HT.
The selectivity coefficients (K~o) of HT with re-
' . ' [
2 . 4
2 . 2
2 . 0
z ~ l . 8
Oz
w. e
- J 1.2
I.O
0. 8
0 . 6 ~ I i i
0 0 . 2 0 . 4 0 . 6 0 . 8
( H T ) o .
1.0
Figure 3. Selectivity coefficient for the HT- NO3- OH- sys-
tem as a function of HT composition.
Vol. 31, No. 4, 1983 Anion exchange of hydrotalcite-like compounds 307
0. 6
b
1.4
L~O0~I.O
0 . 8
- 0 . 8
- 1.0
I I I l
0 0. 2 0 . 4 0. 6 0 8 1.0
(HT)F
Fi gure 4. Sel ect i vi t y coefficient for t he HT- NO3- F- syst em
as a funct i on of HT composi t i on.
1.0
0. 8
0. 6
, . 0 m 0. 4
~ z 0. 2
...1 - o . a
- o . 4
- o . 6
i
I I I I
o 0. 2 0. 4 o. e o . ;.o
( H T ) a r
Fi gure 6. Selectivity coefficient for t he HT- NOa- Br - syst em
as a funct i on of HT composi t i on.
s pect t o NO3 wer e cal cul at ed from t he i on- exchange
i s ot her ms in Fi gur es 1 and 2 in accor dance wi t h t he fol-
l owi ng equat i ons.
When n = 1,
K A
No~ = (HT)ASNo3/(HT)~o, SA,
When n = 2,
KAos = (HT)O.SSNoj(HT)No3SO.L
NO3
Accor di ng to Fi gur es 1 and 2, i on- exchange i sot her ms
of HT- NO3 - OH- , HT- NO3 - F- , HT - NQ- S O4 z-, HT-
NO3-CO3 z-, HT- CI - NYS 2-, and HT-SO4-CO3 2- sys-
t ems ar e near l y of t he Langmui r t ype. The i on- ex-
change i sot her ms of t he HT- NO3- I s ys t em ar e not of
t he Langmui r t ype.
Fi gur es 3 t o 9 show t he l ogar i t hm of s el ect i vi t y coef-
fi ci ent s as a f unct i on of t he mol e f r act i on of ani on A on
t he HT. The equi l i br i um cons t ant (Ke) was cal cul at ed
by usi ng t he met hod of Gai nes and Thomas (1953) from
t he fol l owi ng equat i on
ft HT)A=I
l og Ke = l og K~o 3 d(HT)A,
(HT)A=0
in whi ch (HT)A is t he mol e f r act i on of ani on A on t he
HT. The i nt egral in t he a bove equat i on was gr aphi cal l y
1. 0
0. 8
0. 6
~ r 0 . 4
~," O . 2
- J - 0 . 2
- 0 . 4
- 0 . 8
- 0 . 8
- ! . 0
0
0 . 8
0. 4
0. 2
g o
- 0 . 2
- 0 . 4
--.l - 0 . ~
- 0 . 8
- I . 0
- I . 2
- I . 4
0 . 2 0. 4 0. 6 0. 8 1.0 0
( H T ) c t .
Fi gure 5, Selectivity coefficient for t he HT-NO3-CI- syst em
as a funct i on of HT composi t i on.
O 0 ~
0
I I I I
0.2 0. 4 o.e o. 8 i.o
( H T ) I
Figure 7. Selectivity coefficient for the HT-NO3-I- system
as a function of HT composition.
308 Miyata Clays and Clay Minerals
N
%
2 . 2
2 . 0
1 . 8
1.6
m 1 . 4
z o 1 . 2 0 0
x."
O~ 1.0
o % o
_ 1 o . e
0 . 6
0 . 4
0 . 2
0 I , I ,
o o. z 0 . 4 0. 6 , . o
(HT)mrs
Figure 8. Selectivity coefficient for the HT-CI-NYS 2- sys-
tem as a function of HT composition.
1.4
o ~ 1 . 2
O~ 1.0
0
_J
0. 8 -
0.6
I I I I
o 0. 2 0. 4 0. 6 o. o , . o
(HT)c%
Figure 9. Selectivity coefficient for the HT-SO4-COs 2- sys-
tem as a function of HT composition.
evaluated by calculating the area under the curve in
Figures 3 to 9. The calculated Gaines and Thomas equi-
librium constants are listed in Table 2.
These data show that the ion selectivities of mono-
valent anions are in the order of OH- > F- > CI- >
Br- > NO3- > 1-, and that divalent anions have higher
ion selectivities than monoval ent anions. Of the mono-
valent anions tested, OH- and F- have particularly high
ion selectivities, and CO3 z is the most selective of the
divalent anions. Figures 10 and 11 show the basal spac-
ing, d(003), and the width of the 003 reflection, B(003),
as a function of the mole fraction of anion A in the HT.
The basal spacing decreases almost continuously below
that of HT-NOs (d(003) = 8.79 ~,). In the HT-CI-NYS 2-
system, however, two basal spacings corresponding to
the HT-CI and HT-NYS were observed at HTNvs mole
fractions of 0.4 to 0.75. When the mole fraction of HTNvs
Table 2. The Gaines-Thomas equilibrium constant for hy-
drotalcite-like compounds and the selectivity coefficient for
Dowex 1 anion-exchange resins.
A n 1
log KNO~
Anion
(A") log Ke Dowex 1 Loading Dowex 2 Loading
OH- 1.42 - 1.62 0. 23 -0.70 0.6
F- I. 19 - 1.62 0.82 - 1.40 0.30
C1- 0.263 -0.58 - - -0.52 - -
Br- 0.082 -0.13 0. 60 -0.16 0.64
NOs- 0 0 0.62 0 - -
I- -0.60 0.36 0.73 0.35 0.73
CO32 1. 84 . . . .
NYS 2- 1. 46 . . . .
SO42- 1.39 - - - - -0.11 0.55
1 Peterson (1954).
is less than about 0.6, the diffraction intensity of the 003
reflection corresponding to HT-CI is stronger than that
corresponding to HT-Naphthol Yellow S, and con-
versely, the former is weaker than the latter when the
mole fraction of HTNys is more than about 0.7.
Thus, where no great difference in radius exists be-
tween two anions in question, the XRD patterns of the
003 reflection of the two HTs corresponding to the two
anions overlap and are seen as one diffraction pattern;
however, where the difference in radius bet ween two
anions is relatively large, as in the HT- NO3- OH- , HT-
NO3- F- , HT-NO3-CO32 systems, the XRD pattern of
the 006 reflection is split into two. This split of the 006
reflection is 4.44 A and 4.00 .~ for the HT- NO3- OH-
system, 4.44 ~ and 4.07 ~ for the HT- NOs - F- system,
and 4.44 ,~ and 4.04 ~ for the HT-NO3-COz z- system.
In each split, the former corresponds to HT-NOz and
the latter corresponds to HT-OH, HT-F, HT-CO3, re-
spectively.
On the other hand, the width of the 003 reflections,
B(003), which is nearly inversely proportional to the
Table 3. Basal spacing d(003) and the width of the 003 re-
flection at (HT)A = 0.9-1.0.
Anions Basal spacing (A) 003 width (~
OH- 7.55 0.64
F- 7.66 0.88
CI- 7.86 0.77
Br- 7.95 0.92
NOz- 8.79 1.13
I 8.16 1.45
CO32- 7.65 0.69
NYS 2 13.00 0.96
SO4 z- 8.58 1.40
Vol. 31, No. 4, 1983 Anion exchange of hydrotalcite-like compounds 309
1 . o ~
, ' ~ ' , ~ I t~ ~ I I *
o , , ' ~ , o k , . o s
O- - o . . _ O. O "
_ . . - . . . . .
" " " - " - . . . . - - - - I
~ s . o l - ~ - t o . 5 ~ ga o .8
~ 8
7 . 5 1 , i i , - . u O I i , , i I 0
0 . 4
o o ~ o . , o. ~ o. s , . o o o. 2 o. e o. o , . o
(HT)o. (HT)Nys
Figure 10. Basal spacing ( 9 and the width of the 003 reflec-
tion (~) for the HT-NO3-OH- system as a function of HT com-
position.
cr yst al l i t e si ze, i ncr eases when (HT)A is r el at i vel y smal l ,
and s ubs equent l y decr eas es pr ogr es s i vel y unt i l finally
it is smal l er t han t hat of t he ori gi nal mat er i al .
Tabl e 3 s ummar i zes t he basal spaci ng and t he wi dt hs
of t he 003 refl ect i on for var i ous HTs wi t h (HT)A of 0.9
t o 1.0. The r el at i onshi p bet ween t he basal spaci ng and
t he equi l i br i um cons t ant in an i on- exchange equi l i bri -
um of monoval ent ani ons is pl ot t ed in Fi gur e 12. Fi gur e
12 demons t r at es t hat except for HT- NO3, t he equi l i b-
r i um cons t ant of HT i ncr eases wi t h decr eas i ng basal
spaci ng, and t he r ank of t he basal spaci ng agr ees wi t h
t he r ank of t he i oni c r adi i , i . e. , F - (1.36 A) < CI - (1.81
A) < Br - ( 1.95 ~,) < I - (2.16 ~) . Thes e r esul t s al so agr ee
wi t h t he concl usi on of Mi yat a (1975) in t hat t he basal
spaci ng is subst ant i al l y det er mi ned by t he sum of t he
t hi ckness of t he bas i c l ayer (whi ch de c r e a s e s wi t h an
i ncr eas e in x but at a smal l er r at e t han t hat of t he in-
t er l ayer ) and t he si ze of t he ani on in t he i nt er l ayer .
Ther ef or e, a mai n f act or t hat det er mi nes t he sel ect i vi t y
of t he ani on- exchange of HT is t he di amet er of a bar e,
non- hydr at ed ani on.
The equi l i br i um cons t ant of HT is j us t oppos i t e t o
t hat of t he ani on- exchange r esi ns Dowex- 1 and Dowex-
2, al so l i st ed in Tabl e 2 ( Pet er son, 1954); i . e. , t he i on
s el ect i vi t y of t he l at t er depends upon t he di amt er of a
hydrated ani on.
The wi dt h of 003 r ef l ect i on, B(003), al so decr eas es
wi t h t he i on sel ect i vi t y. I n ot her wor ds, t he cr yst al l i t e
si ze of HT i ncr eases wi t h i ncr easi ng i on s el ect i vi t y (Ta-
bl es 2 and 3). I n vi ew of t he r el at i onshi p s hown in Fi g-
ur e 12, t he basal spaci ng of HT- NOa is une xpe c t e dl y
l arge. To find a cause of t hi s, t wo di f f er ent HT-NO3
pr oduct s in whi ch x was 0.250 and 0.280 wer e pr epar ed
and t he bas al spaci ngs det er mi ned t o be 8.34 ,~ and 8. 40
~., r es pect i vel y. I f t hese dat a ar e cons i der ed in con-
Figure 11. Basal spacing (9 and width of the 003 reflection
(~) for the HT-CI-NYS ~- system as a function of HT com-
position.
j unct i on wi t h t he f act t hat t he bas al spaci ng was 8.79
at x = 0.304, t he bas al spaci ng of HT- NO3 i ncr eas es
wi t h an i ncr eas e in x, at hi gher val ues of x. Thus, t he
r el at i onshi p is i nconsi st ent wi t h t he r el at i ons hi p gen-
er al l y obs er ved f or HT-CO3, et c. , i . e. , t hat x is i nver se-
ly pr opor t i onal t o t he basal spaci ng. The r eas on why
HT-NO3 has an unexpect edl y l arge basal spaci ng at
hi gher val ues of x is pr es umabl y due t o r epul s i on be-
2 . 0
1. 0
V
O
- , !
O
- I . 0 t t
7 . 5 8 . 0 8 . 5
Basal spacing ( X)
Figure 12. Relationship between the basal spacing and the
equilibrium constant log Ke.
310 Miyata Clays and Clay Minerals
tween NO3- ions. Because NOz- is monoval ent and oc-
cupies a space corresponding to three oxygens, the space
occupied by NO3- in the interlayer is greater than that
occupied by other anions such as CI- and Br-. When x
is small and the repulsion between NO.~ ions is small,
NO3- is oriented in the interlayer such that the bond
direction of N-O, i.e., the plane formed by NO3-, is
parallel to the basic layer. But as x increases, the re-
pulsion between NO3- ions becomes stronger, such that
the N- O bond direction of NOa- may be no longer par-
allel to the basic layer. This orientation change of NOa-
in the interlayer leads to the increase of interlayer thick-
ness. If the arrangement of NOa- ions in the interlayer
does not change as a result of the repulsion between
NOz- ions, the basal spacing at x = 0.304 will be close
to 8. I2 ~ which is anticipated from the relation shown
in Figure 12.
It is worth noting that HT-OH shows the smallest basal
spacing and the largest crystallite size of the mono- and
divalent anion forms studied (Table 3). This small spac-
ing is presumed to be due to the fact that the ionic di-
ameter of OH- is nearly equal to that of HzO in the in-
terlayer, and hydrogen bonding is great among OH-,
interlayer water, and OH of basic layers. Accordingly,
the crystal structure of l i T-OH consists of three oxygen
layers derived from two oxygen layers of the basic layer
and one oxygen layer of the interlayer. This structure
has the closest packing of atoms in the 001 direction.
Table 2 also shows that divalent anions generally have
higher ion selectivity than monovalent anions. In par-
ticular, NYS z- has high selectivity despite the fact that
its ionic diameter is about 189 times larger than SO42-.
This is due presumably to the difference in bonding
strength to Mg or AI in the basic layer bet ween NYS z-
and SO4 z-.
CONCLUSIONS
Hydrotalcite-like compounds are some of the few in-
organic anion exchangers that have relatively high ca-
pacities of about 3 meq/g. Anion-exchanger resins in-
duce an ion-exchange reaction with a hydrated anion,
whereas, HT-compounds induce ion-exchange reac-
tions with bare, non-hydrated anions. Accordingly, the
ion-exchange equilibrium constants for HTs are in the
sequence OH > F- > C1- > Br- > I - for monoval ent
anions, and in the sequence CO3 ~- > NYS 2- > SO4 ~-
for divalent anions. By utilizing their characteristic ion
selectivity, HTs are expected to find application in the
removal of acid dyes, HPO4 2-, CN-, CrO4 2-, AsO4 3-,
(Fe(CN)6) 4-, etc. from waste waters, as well as in the
neutralization and thermal stabilization of halogen-con-
taining polymers.
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Nippon Bunseki Kagakukai (1961) Bunseki kaga ku binvan:
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(Received 17 May 1982; accepted2 January 1983)
Pe31OMe---EbI~IH ollpe:leJ1eHbi HOHO-O6MeHHbIe H3oTepMbI Me:~jly FH~poTa,rlhKHTO-RO~[O6HblMH coe:IHHeHH-
aMn if' r) Tana NO3, CI H SO4 a aonaMH F-, CI-, Br-, I-, OH-, SO4 ~-, COs 2-, H
~e.TToro HaqbTo:la S (hKHS2-), a TaK~e 61,1rim n3mepenbi npoMen<yToK m~pnHa 003 oTpan~ennfi
KaK qbyHK~HH COCTaBa FT. ROCTOgHHble Hoao-o6Mennoro panHoaecng ~,n~ coe/InHeHnfi FT MOnO-
Ba.~eHTHhIX aHHOHOB 6bI.~n B c~e/ly~ouleM nopnJlre: OH- > F- > CI- > Br- > NO a- >I-, a JIJIfl
~IHBa.rleHTHbIX aHHOHOB----B caeJIymmeM nop~JlKe: CO3 z- > )KHS 2- > SO42-. I'[OCTOgHHble HOHO-O6MeH-
noro paBHoBecH~ yBeJInqHBa.nncb npH yMem, mennn ~lnaMeTpOB aHnOHO8, a pa3Mep KpHCTaJIJIHTOB B
001 nanpaanenHn yae~n,~Haa~c~ ~1~ aHHonoa C m,~coKofi ceJ1eKTHBHOCTbtO. OH THII FT nMe~
naHMenbulafi npoMe~yTor rl naa6oabmnfi paaMep KpHcTa.m'mTOa a 001 Hanpaaaeni~rl. [E.G.]
Vol. 31, No. 4, 1983 Anion exchange of hydrotalcite-like compounds 311
Resiimcc Die Ionenaustauschisotherme zwischen Hydrotalkit-fi.hnlichen Verbindungen (HT) der NO3-,
CI-, und SO4- Form und F-, CI-, Br-, I-, OH-, SO42-, CO3 z , sowie Naphtolgelb S (NYSZ-)-lonen wurden
bestimmt, und der Abstand und die Breite des 003 Reflexes wurde als Funktion der HT-Zusammensetzung
gemessen. Die Ionenaustauschgleichgewichtskonstanten ffir die HTs mit einwertigen Anionen haben die
Reihenfloge OH > F- > CI- > Br- > NO3- > I ; die mit zweiwertigen Anionen die Reihenfolge CO32-
> NYS z- > SO42 . Ihre lonenaustauschgleichgewichtskonstanten haben die Tendenz mit abnehmendem
Durchmesser des Anions zuzunehmen. Die Kristallitgr6ge in der 001 Richtung hat bei Anionen mit h6herer
Selektivit5t die Tendenz zuzunehmen. Die OH-Form von HT hat den kleinsten Basisabstand und die gr6gte
Kristallitgr6ge in der Richtung 001. [U.W.]
R6sum6-----Des isothermes d' 6change d' ions entre des compos6s semblables ft. l' hydrotalcite (HT) de forme
NQ- , CI-, et SO4-, et les ions F , CI-, Br-, I-, OH , SO42-, CO32-, et Naphthol Yellow S (NYS 2-) ont
6t6 d6termin6es, et l' espacement et la largeur de la r6flection 003 ont 6t6 mesur6s en fonction de la compo-
sition d' HT. La constante d'6quilibre d' 6change d' ions pour des HT d' anions monovalents sont dans la
s6quence OH- > F- > C1- > Br- > NO3- > I-, ceux pour des anions divalents sont dans la s6quence
CO3 ~- > NYS 2- > SO42-. Les constantes d'6quilibre d' 6change d' ions ont tendance & augmenter propor-
tionnellement a une diminution de diam/~tre des anions, et la taille du cristallite dans la direction 001 a
tendance ~ accroitre avec les anions ayant un plus grand selectionnement. La forme OH- d' HT a l' espa-
cement basal le plus petit et la taille de cristallite la plus grande dans la direction 001. [D.J.]