Clays and Clay Minerals, Vol. 26, No. 4, pp. 273-278, 1978.

THE I.R. SPECTRA OF DIMETHYL SULFOXIDE ADSORBED

ON SEVERAL CATION-SUBSTITUTED
MONTMORILLONITES*
G. A. GAR WOOD, J R. AND R . A. CONDRAT E , SR.
Di vi si on of Engi neer i ng and Sci ence, New Yor k St at e Col l ege of Cer ami cs
Al f r ed Uni ver si t y, Al fred, New Yor k 14802
(Received 21 December 1977)
Abst ract - - The i.r. spect r a (4000-1200 cm 1) ar e obt ai ned for sever al homoi oni c mont mor i l l oni t e films on whi ch var i ous
amount s of di met hyl sul foxi de (DMSO) wer e adsor bed. Anal ys es of t hese spect r a i ndi cat e t hat H- and nat ur al - mont mo-
ri l l oni t e-DMSO compl exes cont ai n an i nt er cal at ed l ayer of phys i s or bed DMSO whi l e t r ansi t i on met al cat i on subst i t ut ed-
mont mor i l l oni t e- DMSO compl exes possess bot h physi - and chemi sor bed DMSO in t hei r i nt er l amel l ar spaces. The l at t er
speci es i nvol ve coor di nat i on of DMSO mol ecul es wi t h t he exchangeabl e cat i ons by t hei r oxygen at oms. Most of t he
i nt er l amel l ar wat er i s r epl aced by DMSO as t he l at t er mol ecul es penet r at e t he i nt erl ameUar spaces. Heat - t r eat i ng t r ansi t i on
met al cat i on subst i t ut ed- mont mor i l l oni t e- DMSO compl exes at 120~ for 48 hr r esul t s in bot h t he desor pt i on of physi sor bed
DMSO and t he r et ent i on of i nt er cal at ed monol ayer s i nvol vi ng DMSO- t r ansi t i on met al cat i on coor di nat i on. A wat er-sen-
si t i ve, r ever si bl e col or change (tan t o l i ght purpl e) i s pr oduced by ei t her desi ccat i ng over P~O.~ or heat - t r eat i ng at 120~
t he cobal t - mont mor i l l oni t e- DMSO compl ex. I nt er pr et at i on of t he vi si bl e spect r a suggest s t hat Co2+-cations under go
changes from oct ahedr al t o t et r ahedr al coor di nat i on dur i ng desi ccat i on or heat i ng. Band as s i gnment s ar e made for t he
cl ay compl exes usi ng t he as s i gnment s for r el at ed gases, l i qui ds, and cr yst al s.
Key Wordr~---Chemisorption, Di met hyl sul f oxi de, Mont mor i l l oni t e, Physi sor pt i on.
I NTRODUCTI ON
Ver y little wor k has been report ed in the literature
regarding the adsorpt i on of di met hyl sulfoxide (DMSO)
on cl ays and cl ay minerals. Gonzal ez Gar ci a and San-
chez Camazano (1968a,b) applied DMSO in t he identifi-
cat i on of cl ay minerals present in mi xt ures. For in-
st ance, kaolinite coul d be differentiated f r om chlorite
by X- r ay analysis because the monol ayer compl ex
f or med bet ween DMSO and kaolinite possessed a char-
acteristic distinguishable basal spaci ng of 11.18 ]k. Hor-
t on (1970) has descri bed a kaol i ni t e-DMSO intercala-
tio n compl ex which can be used f or the gradual rel ease
of sulfoxide in a moist at mospher e for drug t herapy.
Olejnik et al. (1968) exami ned t he infrared spect ra of
DMSO compl exes with the kaolin minerals and f ound
t hat DMSO bonds via its oxygen at om t o t he cl ay hy-
droxyl surface. Gonzal ez Garci a and Sanchez Cama-
zano (1965, 1966) and Gonzal ez Garci a et al. (1%7)
have report ed st ruct ural studies of DMSO- mont mor i l -
lonite compl exes using instrumental t echni ques such as
X- r ay diffraction, TGA, and DTA anal yses. Al t hough
infrared spect r oscopy was cited in the latter st udy, no
spect r a were illustrated f or any DMSO- cl ay com-
plexes. Berkhei ser and Mort l and (1975) studied the
variability in t he exchange posi t i on in smect i t e using
vari ous mont mori l l oni t es swelled by a series of sol-
vent s including DMSO. I n this st udy, we will r epor t t he
infrared spect ra of several homoi oni c mont mori l l oni t e-
* Pr esent ed at t he 49th Nat i onal Col l oi d Symposi um, Pot s dam,
N. Y. June 1975.
Based on a t hesi s submi t t ed by G. A. Gar wood, Jr. for t he Ph. D.
degr ee in Cer ami c Sci ence.
Copyright ~) 1978, The Clay Minerals Society
DMSO compl exes, and i nt erpret t hem in t erms of t he
species present in t he cl ay films.
EXPERI MENTAL
The mont mori l l oni t e used in this st udy originated
f r om Wyomi ng. Cl ay films were pr epar ed f r om cl ay
particles whose equi val ent di amet ers were less t han 2
mi crons. The fract i on containing these cl ay particles
was col l ect ed by sedi ment at i on f r om a 5% cl ay suspen-
sion in distilled wat er. Transition metal subst i t ut ed
mont mori l l oni t e was prepared by saturating natural
cl ay with a 1 N aqueous solution of t he appropri at e
metal chloride. The cl ay had t o be washed several times
with distilled wat er t o eliminate free metal ions. H-
mont mori l l oni t e was prepared i mmedi at el y pri or t o use
f r om a 1% suspensi on of natural cl ay by passing it
t hrough a col umn of Amberl i t e I. R. -120 (H-form). The
concent r at i ons of the resulting cl ay suspensi ons were
adj ust ed so t hat t he cl ay made up approxi mat el y 2.4%
of t he weight of the aqueous suspensi ons. Self-sup-
port i ng thin films (approxi mat el y 3.2 cm di amet er, 20
/~m thick) were prepared by evaporat i ng 2-ml aliquots
of the cl ay suspensi ons on an al umi num foil suppor t ed
by a flat glass plate. Since most exchangeabl e cat i ons
react with al umi num foil, t he foil had t o be lined with
a thin film of col l odi on t o prot ect t he cl ay f r om chemi cal
react i ons. The resulting air-dried film speci mens were
easily stripped f r om t he foil by drawi ng t he foil over a
sharp edge.
The films of t he vari ous cat i on-subst i t ut ed mont -
morillonites were t reat ed by qui ckl y deposi t i ng con-
trolled vol umes of DMSO ont o their cent ers, and t hen
placing t hem in a large empt y glass desi ccat or for 4 hr.
273
274 Garwood and Condrate Clays and Clay Minerals
I i 9 i i i
Cu Mont
4000 3600 5200 2800 [800 1600 1400 1200
WAVENUMBER (cm -I]
Fi g. 1. The i nf r ar ed spect ra o f a DMSO- Cu- mont mor i ] ] oni t e compl ex
af t er s ever al di f f er ent t r e a t me nt s : A) bl ank cl ay film wi t h no DMSO
a ds or be d, B) bot h 4 hr e x p o s u r e t o DMSO a nd 20 hr de s i c c a t i on ove r
P~O,~, C) 48 hr he a t - t r e a t me nt at 120~
DMSO- s at ur at ed Co- mont mor i l l oni t e films wer e al so
pr epar ed by i mmer si ng t he unt r eat ed cl ay films com-
pl et el y in l i qui d DMSO, or by exposi ng t he unt r eat ed
films t o a vapor at mos pher e of DMSO. Some t r eat ed
film sampl es wer e des i ccat ed for 28 t o 48 hr over P20.5
and/ or heat - t r eat ed for 48 hr at 120~ in ai r. Wet chem- .
i cal , t r ace emi ssi on s pect r ogr aphi c, SEM and X- r ay
anal ys es wer e used t o char act er i ze t he films.
The i . r. abs or pt i on s pect r a (4000-1200 cm -1) wer e
obt ai ned for t he cl ay speci mens by pl aci ng t hei r cor -
r es pondi ng sel f - suppor t i ng t hi n films in t he s ampl e bean
of a Per ki n- El mer Model 621 doubl e be a m gr at i ng spec-
t r ophot omet er . An ai r purgi ng uni t was e mpl oye d t o
el i mi nat e abs or pt i on bands due t o at mos pher i c wat er
and car bon di oxi de. Cal i br at i on of t he s pect r ophot om-
et er was car r i ed out usi ng pol ys t yr ene bands , and a
wave number accur acy of -+2 cm -1 was obt ai ned.
RESULTS AND DI SCUSSI ON
I . R. s pect r a wer e meas ur ed f or var i ous homoi oni c
mont mor i l l oni t e films cont ai ni ng DMSO. Fi gur e 1 il-
l ust r at es t he i . r. s pect r a obt ai ned for a Cu- mont mor i l -
l oni t e- DMSO compl ex af t er var i ous t r eat ment s . The
ver y st r ong band at 3625 cm -1 is assi gned t o t he OH-
st r et chi ng mode of t he hydr oxyl i ons in t he al umi na
sheet of t he cl ay l amel l ae. Thi s band r emai ns unaf f ect -
ed by t he var i ous t r eat ment s . The 2600-1800 cm -~ r e -
Tabl e 1. Wa ve numbe r s of b a n d ma xi ma a nd ba nd a s s i gnme nt s f or
Cu- a nd Co- mont mor i l l oni t e - DMSO c ompl e xe s .
C u C o A s s i g n m e n t s
3 0 1 7 3 0 2 4
3 0 0 1 3 0 0 3 } A s y m . C - H s t r .
2 9 2 0 2 9 2 0 Sym. C - H str.
2 8 2 7 2 8 1 7 C o m b . o r o v e r t o n e
1 6 3 6 1 6 3 0 H - O - H b e n d
1 4 3 1 1 4 3 3 ~
1 4 1 5 1 4 1 7
1 4 0 3 1 4 0 4 j D e g e n e r a t e C - H d e f .
1 3 4 0 1 3 5 0 c o m b .
1 3 2 0 1 3 1 8 } S y m . C - H def.
1 2 9 7 1 2 9 7
gi on is omi t t ed f r om t he i . r. s pect r a be c a us e t hi s r egi on
cont ai ns no si gni fi cant spect r al f eat ur es for any of t he
i nves t i gat ed c l a y- a ds or ba t e s ys t e ms . Band assi gn-
ment s ar e l i st ed in Tabl e 1 for Cu- and Co- mont mor i l -
l oni t e- DMSO compl exes . As may be not ed, t hese as-
si gnment s ar e cons i s t ent with t hos e made f or DMSO
in r el at ed phas es ( For el and Tr anqui l l e, 1970; Cot t on
et al . , 1960). The obs e r ve d band l ocat i ons for one of t he
s ymmet r i c C- H def or mat i on modes of Co- and Cu- cl ay-
DMSO compl exes ar e 1318 and 1320 cm -1, r es pect i ve-
l y. These bands ar e shi ft ed 8 t o 17 cm -1 hi gher t han
t hose obs e r ve d f or DMSO ei t her in t he gas (1310 cm -1)
and l i qui d (1310 cm -1) st at es or in var i ous sol ut i ons
(1303 cm-1). A si mi l ar shi ft in band l ocat i on was not ed
for t he r el at ed band of cr yst al s cont ai ni ng a Co- DMSO
compl ex (1314 c m- l ) , i n t he l at t er compl ex, DMSO
mol ecul es ar e coor di nat ed t o cobal t cat i ons vi a t hei r
oxygen at oms. The obs e r ve d spect r al dat a s eem t o sug-
gest t hat t he t r ansi t i on met al - mont mor i l l oni t e- DMSO
compl exes cont ai n cbemi s or bed s peci es i nvol vi ng t he
di r ect coor di nat i on of DMSO mol ecul es t o met al cat -
i ons. Thi s speci es is pr es ent al ong wi t h phys i s or be d
DMSO. Spect r al changes due t o t he heat t r eat ment of
t he t r ansi t i on met al - cl ay- DMSO films ar e cons i s t ent
wi t h t he pr es ence of bot h chemi s or bed and phys i s or be d
speci es in t he i nt er l amel l ar spaces. Bands r el at ed to t he
nor mal vi br at i ons of DMSO shar pen and ar e mor e
cl ear l y r es ol ved af t er t he heat t r eat ment . Each band is
t he r esul t ant of t he bands for t he r el at ed modes of bot h
t he phys i s or be d and t he chemi s or bed DMSO ( Fi gur e
1B). Heat t r eat ment dr i ves off phys i s or be d DMSO, in-
cr easi ng t he r el at i ve concent r at i on of chemi s or bed
DMSO in t he cl ay film. Thi s change in r el at i ve concen-
t r at i ons causes t he obs e r ve d bands t o s har pen ( Fi gur e
1C). Si mi l ar r esul t s ar e al so obs e r ve d for DMSO- t r eat -
ed mont mor i l l oni t es cont ai ni ng Zn, Ni , and Cd. The
r el at ed bands for t he DMSO compl exes wi t h nat ur al
and H- mont mor i l l oni t es decr eas e in i nt ensi t y wi t hout
shar peni ng af t er heat i ng, i ndi cat i ng t he pr es ence of
onl y phys i s or bed DMSO.
Di r ect DMSO- met al i on coor di nat i on in t he cl ay in-
Vol_ 26, No. 4, 1978 Dimethyl sulfoxide on montmorillonite 275
I1:
t,-
380
' I ' 7 I
Co Mont J
D Z O 1.000 m l
O.l OOml
I
L
Y
L I , _ _ 1
5400 3000
I 9
2600 1800
WAVENUMBER (crn-,)
1600 1400 1200
Fig. 2. The i nfrared spect r a of compl exes f or med af t er deposi t i ng var-
i ous amount s of DMSO On t hi n cl ay films of Co- mont mor i l l oni t e.
t er l ayer s r equi r es t he concomi t ant r emoval of some
wat er of hydr at i on f r om t he coor di nat i on s pher es of t he
exchangeabl e cat i ons. One may r eas onabl y expect t hat
a st r ongl y pol ar s ol vent such as DMSO (4.3 Debye)
shoul d c ompe t e wi t h ads or bed wat er mol ecul es (1.85
Debye) for bi ndi ng si t es in t he i nt er l ayer s paces of a
cl ay. Ol ej ni k et al . (1968) det er mi ned by i nf r ar ed spec-
t r os c opy t hat i nt er cal at i on of DMSO i nt o hydr at ed hal-
l oysi t e di s pl aces t he i nt er l amel l ar wat er . I n t he pr es ent
case, a band is obs e r ve d at 1612 cm -1 for unt r eat ed Cu-
mont mor i l l oni t e ( Fi gur e 1A). Thi s band r esul t s f r om an
over l ap of bands at 1598 and 1632 cm -1. Dowdy and
Mor t l and (1967) have assi gned t he f or mer band t o t he
bendi ng mode of wat er coor di nat ed t o Cu- cat i ons,
whi l e t hey have assi gned t he l at t er band to t he bendi ng
mode of wat er l oos el y a ds or be d on t he cl ay. The ob-
s er ved band shifts t o ca. 1630 cm -~ and dr amat i cal l y
decr eas es in i nt ensi t y af t er t he film is t r eat ed wi t h
DMSO. Si mi l ar t r ends in spect r al changes ar e not ed for
Co-, Ni - , Zn- , and Cd- mont mor i l l oni t e films. The shi ft
can be expl ai ned by assumi ng t hat t he maj or i t y of wat er
mol ecul es coor di nat ed t o t he met al cat i ons ar e r epl aced
by DMSO mol ecul es. Thi s i nt er pr et at i on is cons i s t ent
wi t h t he r esul t s obt ai ned by Ber khei s er and Mor t l and
(1975) f or Cu- mont mor i l l oni t e t r eat ed wi t h DMSO.
Thei r ESR st udi es i ndi cat ed t hat t he Cu~+-ions ar e sol -
vat ed by t he DMSO mol ecul es and ar e l ocat ed a wa y
f r om t he cl ay sur f ace. I nt er est i ngl y, t hei r X- r ay basal
i i ~ i
CO Mont
+
DMSO
r ~ i I
004/ " ' ,
/ "', ~ ~ Blonk
004
0 0 l Or n l
0 0 4 ['~ ~ ]
I / ~ , , I Z ' , , / O , O O m , / , ,
00,
32 2 8 2 4 2 0 16 12 8 q
- - DEGREES 2 0
Fig. 3. The X- r ay powder di ffract i on pat t er ns of compl exes f or med
af t er deposi t i ng var i ous amount s of DMSO on t hi n cl ay films of Co-
mont mor i l l oni t e.
spaci ngs wer e 18.4 ]k wher eas t he spaci ngs in t hi s s t udy
wer e onl y 14. I ] k. Thi s di f f er ence can be expl ai ned by
t he di f f er ences in bot h t he amount of DMSO added t o
t he cl ay film and t he l engt h of t i me of expos ur e. Thei r
pr epar at i on pr ocedur e was t o submer ge a cl ay film in
a bat h of DMSO f or 10 days whi l e in t hi s s t udy onl y 26
/~1 of DMSO was al l owed t o i nt er act wi t h t he cl ay film
f or 4 hr. Two i mpor t ant poi nt s may be made wi t h re-
s pect t o t hese cont r ast i ng pr ocedur es and X- r ay re-
sul t s. Fi r s t , sol vat i on of Cu- mont mor i l l oni t e by DMSO
appear s t o be a s t epwi s e pr oces s . A st abl e monol ayer
compl ex (d001 = 14.1 ]k) f or ms at l ow DMSO l oadi ngs,
and t hen a doubl e l ayer compl ex (d00~ = 18.4 ]~) is
f or med when t he DMSO l oadi ng is suffi ci ent l y in-
cr eas ed. Thi s s t epwi s e sol vat i on of mont mor i l l oni t e
was st udi ed in gr eat er det ai l for t he Co- c l a y- DMSO
s ys t em and will be di s cus s ed l at er . Second, t he st er eo-
chemi s t r y of t he Cu2+-ions in t he monol ayer compl ex
ought t o be qui t e di f f er ent f r om t hat obs e r ve d by Ber k-
hei s er and Mor t l and (1975). Thei r r esul t s f r om i so-
t r opi c ESR s pect r a t oget her wi t h t hei r l arge bas al spac-
ings i ndi cat ed t hat t he Cu- DMSO compl ex i ons r api dl y
t umbl e in t he i nt er l ayer . One may r eas on t hat t he mon-
ol ayer compl ex, occupyi ng a l ess e xpa nde d i nt er l ayer ,
woul d be mor e r es t r i ct ed and l ess l i kel y t o t umbl e.
276 Garwood and Condrate Clays and Clay Minerals
Anal ys i s of t he ESR s pect r a for our Cu- DMSO- c l a y
compl ex shoul d show an or i ent at i on de pe nde nc e of t he
g I and g I I component s of t he g- t ensor .
The ef f ect of t he i ni t i al concent r at i on of t he ads or -
bat e on t he ads or pt i on pr oces s es was i nves t i gat ed usi ng
Co- mont mor i l l oni t e as a model syst em. A ser i es of
compl exes was pr epar ed by var yi ng t he amount of
DMSO depos i t ed on Co- cl ay films. The DMSO- t r e a t e d
films wer e kept in des i ccat or s for 48 hr at ambi ent t em-
per at ur e. The des i ccat or s wer e t hen opened, and t he
speci mens wer e e xpos e d t o ai r at ambi ent t e mpe r a t ur e
f or a ppr oxi ma t e l y 20 hr in or der t o e va por a t e exces s
DMSO f r om some of t he cl ays. The i nf r ar ed s pect r a
( Fi gur e 2) show concl us i vel y t hat each of t he com-
pl exes cont ai ned a c he mi s or be d s peci es i nvol vi ng
DMSO- Co coor di nat i on. As e xpe c t e d, t he DMSO
bands gr ow and t he wat er band weakens in i nt ensi t y
and shifts as t he i ni t i al concent r at i on of t he ads or bat e is
i ncr eas ed. Howe ve r , a bove an a dde d DMSO vol ume
of 0.100 ml , no i ncr eas e in DMSO band i nt ensi t i es is
obs er ved. Thi s r esul t suggest s t hat t he Co- cl ay film is
compl et el y s at ur at ed wi t h DMSO when t he vol ume of
t he al i quot is t he a bove ment i oned amount . X- r ay dif-
f r act i on pat t er ns wer e al so obt ai ned f or s ever al mem-
ber s in t hi s ser i es and ar e shown in Fi gur e 3. Anal ys i s
of t he X- r ay dat a ( Tabl e 2) cl ear l y r eveal s t he s t epwi s e
sol vat i on pr oces s i nvol ved as t he bas al spaci ngs in-
cr eas e f r om 12. 6/~ t o 14.5 A and t hen t o 18.3 A for t he
bl ank Co- cl ay film, 0.010 ml- and 0.100 ml - DMSO- Co-
cl ay s peci mens , r es pect i vel y. X- r ay pat t er ns for com-
pl exes cont ai ni ng i nt er medi a! e amount s of DMSO pos-
s es s ed br oa de r bands i ndi cat i ng s ome degr ee of i nt er-
st r at i f i cat i on. Thes e r esul t s ar e cons i s t ent wi t h t he i . r.
dat a and i ndi cat e t hat a doubl e l ayer is ful l y de ve l ope d
when t he film is sat ur at ed. I nf r ar ed band f eat ur es f or
DMSO- s at ur at ed cl ay films ar e ent i r el y i ndependent of
t he t echni que of sat ur at i ng t he films. The s at ur at ed
films may be pr e pa r e d by i mmer si ng t he film in a bat h
of t he abs or bat e, expos i ng i t t o a va por of t he abs or bat e
or by deposi t i ng a cont r ol l ed amount of abs or bat e on
it al l owi ng t he l i qui d t o penet r at e t he film. I n each case,
t he i . r. s pect r a ar e i dent i cal .
An i nt er est i ng r ever s i bl e col or change was obs e r ve d
in t he cas e of t he Co- mont mor i l l oni t e- DMSO compl ex
af t er i t was des i ccat ed f or 20 hr over P~O5. I ni t i al l y,
bef or e des i ccat i on, t he Co- cl ay- DMSO compl ex pos-
s es s ed a l i ght t an col or si mi l ar t o t hat for a Co- cl ay film
t hat was not t r eat ed wi t h DMSO. Howe ve r , af t er des-
i ccat i on, t he t r eat ed f i l m' s col or changed t o l i ght pur -
pl e. Upon r emoval of t he compl ex f r om t he des i ccat or ,
t he s peci men gr adual l y r e ve r t e d t o t he or i gi nal t an col or
wi t hi n sever al mi nut es. The pur pl e col or change coul d
be achi eved agai n ei t her by desi ccat i ng t he compl ex or
by heat i ng i t at 120~ f or a few mi nut es. We yl (1959)
not ed si mi l ar col or changes f or var i ous gl as s es con-
t ai ni ng cobal t . For i nst ance, most cobal t gl as s es whi ch
ar e pi nk at r oom t emper at ur e t ur n bl ue on heat i ng. The
Table 2. X-ray basal spacings and interlamellar spaces for complexes
formed after depositing various amounts of DMSO on thin Co-mont-
morillonite films.
DMSO v o l u m e d 0 0 1 ( X ) Interlamellar
(ml) space (A)
0.0 (blank) 12.6 3.0
0.010 14.5 4.9
0.i00 18.3 8.7
0.500 18.4 8.8
cobal t cat i ons in t hese gl asses under go a coor di nat i on
change f r om oct ahedr al t o t et r ahedr al upon heat i ng.
Appar ent l y, cobal t cat i ons in t he DMSO- t r e a t e d cl ay
films under go si mi l ar coor di nat i on changes upon des-
i ccat i on or heat i ng. Thi s change in coor di nat i on can be
achi eved by t he l oss of t wo wat er mol ecul es f r om t he
cobal t compl ex dur i ng des i ccat i on or heat i ng, l eavi ng
t he Co2+-ion t et r ahedr al l y coor di nat ed t o f our DMSO
mol ecul es. The r ever s e change can occur by t he r ead-
sor pt i on of t wo wat er mol ecul es per cat i on dur i ng ex-
posur e to wat er vapor , r esul t i ng in oct ahedr al coor di -
nat i on of t he Co~+-ion t o f our DMSO and t wo H20
mol ecul es. A di st ant possi bi l i t y exi st s t hat DMSO may
f or m a f our - coor di nat ed s quar e- pl anar compl ex wi t h
Co2+-ions upon des i ccat i on or heat t r eat ment . How-
ever , t hi s pos s i bi l i t y seems unl i kel y be c a us e mos t li-
gands will not nor mal l y f or m such compl exes wi t h
Co2+-ions ( Cot t on and Wi l ki nson, 1966).
REF ERENCES
Berkheiser, V. and Mortland, M. M. (1975) Variability in exchange
ion position in smectite: dependence on interlayer solvent: Clays &
Clay Minerals 23, 404-410.
Cotton, F. A., Francis, R. and Horrocks, W. D. (1960) Sulfoxides as
ligands. I: infrared spectra of some dimethyl sulfoxide complexes:
J. Phys. Chem. 64, 1534-1536.
Cotton, F. A. and Wilkinson, G, (1966) Advancedlnorganie Chem-
istry: A Comprehensive Text: Interscience Publishers, New York.
Dowdy, R. H. and Mortland, M. M. (1967) Alcohol-water interactions
on montmorillonite surfaces. I: ethanol: Clays & Clay Minerals 15,
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Forel, M. T. and Tranquille, M. (1970) Spectres de vibration du di-
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Olejnik, S., Alymore, L. A. G., Posner, A. M. and Quirk, J. P. Weyl, W. A. (1959) ColouredGlasses, pp. 168-196. Society of Glass
Technology, Sheffield.
P e 3 m M e - H H ~ p a K p a c H ~ e c n e K T p ~ --/4000-1200CM-I/ 6hUlH n o n y q e H ~ ~ n ~ H e c K o n ~ K H X
FOMOHOHHbIX M O H T M O p H n n O H H T O B h I X iUJIH~OB C pa3nHqHb~4 K O n H q e C T B O M a ~ C O p 6 H p O B a H - -
H O ~ O ~ H M e T H n O B O F O C y n b ~ O K C H ~ a / ~ v I C O / . A H a n H 3 ~ 9 T H X c H e K T p O B y K a 3 ~ B a m T r q T O
H- H H a T y p a n b H ~ e MOHTMOpHIInOHHT--~24C0 K O M H n e K C ~ c o ~ e p ~ a T H H T e p K a 2 H p o B a H H ~
C ~ O 2 ~ H B H q e C K H c O p 6 H p O B a H H O F O ~ M C 0 r B T O B p e M ~ K a K K O M H n e E c ~ O6MeHHhL~ M e -
Ta/I~HqecKH~ K a T H O H n e p e x o ~ H O 2 F P y H H ~ - - M O H T M O p H ~ O H H T - - ~ M C 0 c o ~ e p ~ a T K a K ~H--
3 H ~ e c K H T a K H X H M H ~ e C K H c O p 6 H p O B a H H ~ e ~ M C 0 B C B O H X M e ~ c n O 2 H ~ X H p o M e ~ y T K a X .
B ~ o c n e ~ H H X p a B H O B H ~ H O C T H X H a 6 n ~ a m T c ~ K O O P ~ H H a ~ H O H H ~ e C B H B H M O n e K y n ~ 4 C 0
C O6MeHHbIMH K a T H O H a M H , o 6 p a 3 y e M ~ e H X K H C ~ O p O ~ H B ~ 4 H a T O M a M H . B o n b m a H q a C T b
M e ~ c n O A H O 2 B O ~ 3 a M e ~ a e T c ~ ~]~4COrKoF~a e F o M O n e E y n ~ npOHHKa/0T B M e m c 2 o ~ H ~ e
n p o M e ~ y T K H . 0 6 p a 6 o T K a TerI~OM n p H T e M n e p a T y p e 1 2 0 o c B T e ~ e H H e 48 q a C O B
K O M H n e K c o B M e T a n n H q e C K H ~ O 6 M e H H ~ K a T H O H H e p e x o ~ H O ~ FpyHH~--MOHTMOpHnnOHHT--
~ M C 0 H p H B O ~ H T K ~ e c o p 6 ~ H H ~ H 3 H q e c K H C O p 6 H p O B a H H O F O ~ M C 0 , H O y ~ e p ~ H B a e T HH--
T e p K a ~ H p O B a H H ~ e M O H O C ~ O H ~ B K S m q a D ~ H e K o o p ~ H H a ~ H O H H ~ e C B H 3 H ~ C 0 - M e T a n n M q e c -
K H ~ K a T H O H H e p e x o ~ H O 2 P p y H H ~ . H S M e H e H H e B O ~ O q y B C T B H T e n B H O F O , O 6 p a T H M O F O
~ B e T a /OT pbDKeBaTO--KOpHqHeBOrO ~ O C B e T n O - - H y p H y p H O F O / H p O H C X O ~ H T H n H H p H
B~CyB/HBaHHH H a ~ P 2 0 5 H n H n p H O 6 p a 6 O T K e T e n n o M n p H 1 2 0 ~ K o M n n e K c a Ko6anBT--
M O H T M O p H 2 n O H H T - - ~ C 0 . H H T e p H p e T a ~ H H B H ~ H M O F O c n e K T p a n p e ~ n o n a F a e T , q T O K a T M -
H C 2+
O ~ O H 3 M e H ~ D T C B O H o ~ T a g ~ p H q e c K H e ~ O O p ~ M H a ~ M O H H ~ e C B H 3 H Ha TeTpa9~pH--
q e c K H e B T e ~ e H ~ e B~cBr~/MBaHH~ H n M H a ~ p e B a H M ~ . 0 n p e ~ e n e H H e C B ~ 3 e ~ ~ F~H--
HHCTbIX KOMJIneKCOB 6huIO c ~ e n a H o n o a H a n o F H H c p O ~ C T B e H H b ~ 4 H P a 3 a M H , ~ H ~ K O C T ~ - -
M H H K p H c T a n n a M H .
K u r z r e f e r a t - Die I n f r a r o t s p e k t r a ( 4 0 0 0 - 1 2 0 0 c m -I) v o n v e r s c h i e d e n e n h o m o -
i o n i s c h e n M o n t m o r i l l o n i t e n , a u f d i e u n t e r s c h i e d l i c h e M e n g e n v o n D i m e t h y l -
s u l f o x y d ( D M S 0 ) a d s o r b i e r t w a r e n , w u r d e n a u f g e n o m m e n . A n a l y s e d i e s e r S p e k t r a
d e u t e n d a r a u f h i n , d a B H - u n d n a t U r l i c h e M o n t m o r i l l o n i t - D M S 0 - K o m p l e x e e i n e
e i n g e b e t t e t e S c h i c h t v o n p h y s i k a l i s c h a d s o r b i e r t e m D M S 0 e n t h a l t e n , w o h i n -
g e g e n m i t U b e r g a n g s m e t a l l k a t i o n e n s u b s t i t u i e r t e M o n t m o r i l l o n i t - D M S 0 - K o m -
p l e x e s o w o h l p h y s i k a l i s c h w i e a u c h c h e m i s c h a d s o r b i e r t e s D M S 0 in i h r e n in-
t e r l a m i n a r e n R ~ u m e n b e s i t z e n . D i e l e t z t e r e S o r t e i s t m i t K o o r d i n a t i o n d e r
S a u e r s t o f f a t o m e d e r D M S 0 - M o l e k U I e m i t d e n a u s t a u s c h b a r e n K a t i o n e n v e r b u n d e n .
D a s m e i s t e i n t e r l a m i n a r e W a s s e r w i r d d u r c h D M S 0 e r s e t z t , s o b a l d d i e D M S 0
M o l e k ~ l e d i e i n t e r l a m i n a r e n R ~ u m e p e n e t r i e r e n . W ~ r m e b e h a n d l u n g d e r m i t U b e r -
g a n g s m e t a l l k a t i o n e n s u b s t i t u i e r t e n M o n t m o r i l l o n i t - D M S 0 K o m p l e x e , b e i 1 2 0 |
fur 48 S t d . , r e s u l t i e r t e in d e r D e s o r p t i o n y o n p h y s i k a l i s c h a d s o r b i e r t e m D M S 0
w i e a u c h in d e r B e i b e h a l t u n g d e r e i n g e b e t t e t e n E i n z e l s c h i c h t e n , w e l c h e m i t
D M S 0 - M e t a l l k a t i o n k o o r d i n a t i o n v e r b u n d e n s i n d . E i n w a s s e r e m p f i n d l i c h e r , r e -
v e r s i b l e r F a r b u m s c h l a g ( v o n b e i g e zu h e l l v i o l e t ) w i r d e n t w e d e r d u r c h E n t w ~ s -
s e r n d e s K o b a l t - M o n t m o r i l l o n i t - D M S O - K o m p l e x e s H b e r P 2 0 s o d e r W ~ r m e b e h a n d -
l u n g bei 1 2 0 ~ e r h a l t e n . I n t e r p r e t a t i o n d e r s i c h t b a r e n S p e k t r e n , s c h l a g e n v o r
d a b C o ( I I ) K a t i o n e n , w ~ h r e n d d e s E n t w ~ s s e r n o d e r d e r W ~ r m e b e h a n d l u n g , v o n ok-
t a h e d r i s c h e r zu t e t r a h e d r i s c h e r K o o r d i n a t i o n H b e r w e c h s e l t . D i e B e s t i m m u n g
d e r B ~ n d e r fur d i e T o n k o m p l e x e w i r d d u r c h V e r g l e i c h m i t ~ h n l i c h e n G a s e n ,
F i U s s i g k e i t e n u n d K r i s t a l l e n g e m a c h t .
R~sum~-Les spectres i n f r a - r o u g e s (4000-1200 cm -I) ont ~t~ obtenus p o u r plu-
sieurs films de m o n t m o r i l l o n i t e h o m o i o n i q u e sur lesquels diverses q u a n t i t ~ s
de sulfoxide d i m ~ t h y l ont ~t~ adsorb~es (DMS0).Les analyses de ces spectres
i n d i q u e n t que les complexes H - m o n t m o r i l l o n i t e - D M S 0 et m o n t m o r i l l o n i t e na-
t u r e l l e - DMS0 c o n t i e n n e n t un feuillet i n t e r c a l a i r e de DMS0 p h y s i s o r b ~ , t a n -
dis que les complexes de m o n t m o r i l l o n i t e s u b s t i t u t e par des cations de m~tal
de t r a n s i t i o n - DMSO ont ~ la fois du D M S O p h y s i s o r b ~ et c h e m i s o r b ~ dans les
espaces i n t e r l a m e l l a i r e s . Cette d e r n i ~ r e e s p ~ c e implique la c o o r d i n a t i o n de
278 Gar wood and Condr at e Clays and Clay Minerals
m o l ~ c u l e s de D M S O avec les cations ~ c h a n g e a b l e s p a r l ' i n t e r m ~ d i a i r e de leurs
atomes d'oxyg~ne. La p l u p a r t de l'eau i n t e r l a m e l l a i r e est r e m p l a c ~ e par du
D M S O , p u i s q u e les m o l ~ c u l e s de ce d e r n i e r p ~ n ~ t r e n t les espaces i n t e r l a m e l -
laires. Le t r a i t e m e n t ~ la c h a l e u r de c o m p l e x e s m o n t m o r i l l o n i t e s u b s t i t u t e
par des cations de m~tal de t r a n s i t i o n - D M S O ~ 120~ p e n d a n t 48 h e u r e s don-
ne les r ~ s u ! t a t s s u i v a n t s : ~ la fois la d ~ s o r p t i o n de D M S O p h i s i s o r b ~ , e t la
r ~ t e n t i o n de m o n o - f e u i l l e t s i n t e r c a l a i r e s i m p l i q u a n t la c o o r d i n a t i o n des mo-
l~cules de DMSO avec les cations du m ~ t a l de transition. Un c h a n g e m e n t de cou-
leur (de b r u n ~ m a u v e p ~ l e ) , s e n s i b l e ~ l ' e a u , e s t p r o d u i t soit par la dessica-
tion sur P 2 0 ~ , s o i t par t r a i t e m e n t ~ la c h a l e u r ~ 120~ du complexe cobalt-
m o n t m o r i l l o n I t e - D M S O . L ' i n t e r p r ~ t a t i o n des spectres v i s i b l e s sugg~re que les
2+
cations CO s u b i s s e n t des c h a n g e m e n t s de c o o r d i n a t i o n de m o d e o c t a ~ d r a l e
t @ t r a ~ d r a l e p e n d a n t la d e s s i c a t i o n ou l'~chauffement. Des bandes sont attri-
butes aux complexes argileux e m p l o y a n t les a t t r i b u t i o n s faites p o u r les gaz,
liquides et c r i s t a u x apparent~s.