Beruflich Dokumente
Kultur Dokumente
Soundararajan
GGUu
LAY MiNERAL/organlcs re- der, In hazardous waste treatment (Wlchita. Kansas). Known amounts
C actions have been studied
extensively 1by way of in-
frared (IR) spectra, *' x-ray diffrac-
(the so-called "solidification" or
"encapsulation" technology).
Recently, U was shown thai there
of the orgaaics (trichloroethylene,
cbloroaniline, phenol, nitroben-
zene, and triethanolamioe) were
lion.4 and other physkochemkal U more than one type of bonding treated with Axed amounU of HWT-
methods. Many of the* ttudie* ex- between the clay mineral and the 22 and wen allowed to cure at room
plain Uw role of silicates, Including organic waste5 by Infrared TCLP temperature. The addition of ce-
their dehydration, which subse- (Toxtcity Characteristic Uachate ment, slag powder, and water waa
quently caialyzea the polymcrixa* Procedure), total extraction, and av9lded. since we did not want: 1)
tlon of compound* men at ityitne. thermognvimetric analysis. These water to mask the IR spectra, or 2)
Furthermore, then ha* been a con- studies clearly Indicate that there are the silicate hydration reaction to ui-
siderable amount of work done la all kinds of weak to strong bonding leifera with the clay mineral-organic
the arcaa of adaorptlon of organic*, between the organici and the clay reactions.
Lewis acU-bue reactions, and ad- minerals. After 48 hr. the samples were sub-
duct formation between the elay and In order to determine the practi- jected to FTTR analyses with a Per-
the organic compounds. A review cality of the containment technol- kin-Elmer model 1710 FTIR iastni-
of ell of these papers reveals the fol- ogy, we have continued our investi- ment scanning KBr pellets. The
lowing: gations using more powerful tools, FTIR spectra of the pure orgaaics
I) In genera), clays have alternat- such aa differential scanning calori- wen also run using this technique.
ing layers of alumina (hydrated) and metry (DSC) and gas chromatogra- The DSCs were rua using a
silica, with both tetrahedral and phy-maas spectroscopy (OC-MS), Pbrkin-Elmer DSC-2 Instrument in
octahedral sites available to retain in addition to Fourier transform in- nitrogen atmoaphere. The beating
organic*. 2) For charge balance, frared (FTIR) and thermogravimet- rate was KTC/mln.
Group I A elements, such as U*, ric analysis (TOA) techniques. In To determine the effluent*
Na * , and K * . as well as Grcrjp HA this paper, we present our conclu- evolved during DSC : canning, the
elements,
3
*uch as Ct1+ . M* * , *-nrf tiout drawn on the basis of FTIR, gases wen ibnoifrM :n ac&f'aicd
Fa *, are usually vtwrx &.JVXP. TQA, DSC, and OC-MS rtiulu, run.lgea. pt oved
th< c(llf a f nd turnip* ;*"<i * . Tj ' * ,c cc veraing the raikMiUv c* tnis *nd jun ;^i< 'U- > <
<'*th as 1.J1 , i*^*. ;A ' tfcvay etnergi&f ^ , L > . j h
IV ) cm ri. iciplr^cc by t-ir^rr *> txft'i to mirkfr "u: ^r^.
airrnoalun caiioni (*'*} oc <*** f kfltwa o*;^'., c:.-nr
organic catioric sr^cfci. Twif *. > g the v-~ : .'^-
ititutJon ctufci the *:lav tc or T^T the ;-aznk>ui s:b. . : . . -vtv tv T }S. and
In nature, 4} ,M.CT used in this itudy. ^ vet.
, me ciay can be used for a mere comotex organic
t long vrili cffnwnt hid tt'wr COIP- we believe thri Ui* r ^
citu, su-:h u T.y ash or --
Anaiyneai -f*r-
with HWT-22. are also ihowo in the Thete R shifti an exptaiaed on the
ume uble. The typec of pouibla batii of tar h indivKl^
bond* an predkied in f/fuiw 1-5. /:, Nitrobwtiu, Then U a thift
with the actual DSC curvet thown ><4ftom 1173 cm'1 to 1130 coT*
la Flgwt* 6-10. The recoutnicted which li one chancteriMic of mono-
loa chnKnttognnu of the effluent tubttitmed uomatic compoundi.
|uet from DSC ara ihown io Fit- Thit lowering U due to ihe rcttric-
MTM // tod 12. The DSC codother- Uoot impoied by Uuerealnion (i.e.,
mlc peak tempenturet, along with the of ganic compound U land*
AH of vaporization, an given in wiched between Uyen of alumina
TabU2. and liilca). Then U Mother reduc-
tion in ihe frequency at the CN
Infrared sptetra touching region, from 1349 cm~ '
to 1343 cm"', Indictling that the
A ciitful eitraioatkw of Table 1 motion of ihe nitro group U ie-
reveal* IR ihifU in both diitctiou. tuicied. A UUM of thU reatrictlon
Table 1
Infrared frequendee before mid Mar miment (cm'1)
tttenA^ndWeMftA ^
IVv^^WUn^lViV V
\
962 934 -26
WH EATON \
64f C-30 19 (
M*nuf*ctuf9f9 SJnc* 1 ^
1000 N. Tenth SlrMl 2286 -9,
Mitlvllle. NJ OS332. U.3.AI
Call Toll-Frw: 1-*XV225-1437. 2646 -S7
Ext. 2768 i 3067 -10
could ba the latenctloa between Al LAYER
outer oibital elecirona la the oxygen
and the matrix, which baa dw elec-
tron deflcfent aluminum. DuatoihU
hooding, the CN bond order It
decreased and hence thf reduction
In waveaumber. Then an four other
frequencies due to CH stretch
which an abo restricted. Thla. of
coune, can be explained la terra*
of feeble hydrogen bonding between
Iha five comer hydrogen* and the
silica and alumina oxygen*. SlOa LAYER
Phtnot, The 01 spectrum of flame 1 PoaaJbJa Maracitonf oefweefl flttobenieM art cty matte
phenol ii rather simple. The CO1
stretching U reduced by 28 cm'
from 962 cm"' to 934 cm"'. TWi f,*m
U again due to hydrogen bonding
between the -OH hydrogen and
oxygen la Iha lilica and alumina.
This cauaea a flow of electron dea-
ilry from carbon to oxygen, thereby
reducing the CO bond order.
Also, then Is evidence for a hydro-
gen bonded -OH group at 3640
cm"1 and 3632 cm"1.
Cktoroanilint. There It a poeltlva
ihift teen at the CO bond. Thia
U due to the decreased electron den-
sity on the benzene, which U caused
by the coordination of the ammo
group nitrogen with the aluminum
(a Uwia acid). Thii effect In turn SlOa LAYER
draws Ihe ring electron* toward the Ptaun 3 rt**W JrtfanceoM bflwMn pAenof tmi dty me**.
amino group. The electron-rich *
chlorine shifts Us electron density
closer to the ring carbon, which U ________Al AlaOa LAYER_____
indicated by the positive shift. Al.. H*
Then Is UK a sttong reduction
In the NH itretcUng frequency
which may be cMibutft to M HOCHSCH| H CHj CHa
HO bonding of the nuttrfc oxy-
gena.
TricHhrottfyhnt. There Is again
ptxltlve shift In the CO absorp- CHs
tion frequencies, as was mm In the
CA*e of chloroanilina. The charac-
teristic tthyleae frequency and the Chj
CH stretching frequencies are I
both lowered. It appean that interca-
e
lation causes the former, and re- HC
sidual hydrogen bonding causes the
latter.
Tritthanolamiiu. We have seen
several weak to moderate uterac- Figure 3 tou/bto.'- --*>.-*
CHEMICAL BONDINQ conttiuM*
'ft
KM 4lt 10. OB
cases. However, in the case of
uieihanolMnine, w* an able to es*
tebltoh {he pretenc of t coordhita
covhlcnt boRd between UM lone pair iat.n
of eiectrons on the ntoogea and the tM./f<Ur t.
matrU (altuiiinum). The CN
st!tch!ag frequency has 1drarottl-
flM *M* Mft t
cally shifted by 193 cm" toward CMttl. lit *4
CM./CMM .
the positive diitction, whkh Is very ir>. *ia
characteristic of amine salt forma-
tioo. ProtontUon of organic com*
IM.I*
6*i> U. 7
'111. JH. 4
Ml W4W 1C)
tnttnw* mMrtiL in
MMIHM 111.11 "**'
OHMfi !.
CM./CMM III
MAI/MIM IM.I1*
OK
1CNPWATUM <C)
CC
1IHPfATUHC tC)
tm WJM /****
1W Xm~~fm Am tTm"tm
TfNPMATuM (CI OSC
T/M/n III*. | II
116.46
Tabtot
Infrared data
Tables
Waete GC-M8 anatyala data on Identified priority poHutanU"
waste site! attract + Ira* hdvarad Cancan- Malhod
Waste Mndar ajueway tratton rtatacllcm
aitraat templet ahrtl asslgnrnmla No. Campaund
3384 3388-8 OHstttoOM-O 1 Bto(2-craoiolM
3382 3372 -10 NHstrfWiNH-O propy)a*ar U29 8-7
3373 3388 -18 2 NaphtMlana 18.000 1.8
3 20.184 8.4
1897 1880 -17 Kataorotp p^
4 Baruo(A) anthracene 30.460 7.8
1038 1008 -30 HydraganbondnoSl 1
o ' Avtnai wnotaM ncaotry * 91%.
and reiulu are described In thai wctlon. formed using 3-10 mg quantities In a DSC/TOA-2 unit
The PT1R studies of I) extracted waste, 2) pure bind- (Ptfkln-Elmer) Interfaced with a thermal analysis data
er, and 3) Sample I (binder + wane) were done by system (TADS).
mixing milligram quantities of the respective samples All the runs were carried out In sir and the heating
with dry KBr and peltetlilng them. These palletized rale was IO*Omin. Once the endothermlc peak temper-
samples were scanned In the range of 4000 to 40 cm ~' ature* were identified for Sample I (binder + waste),
In a model 1710 PT1R unit with a SEARCH-2 compu- the effluent gases at those temperatures wen collected
terized database (The PerkuvBlmer Corp., Norwalk, uilng an activated charcoal cartridge. The adsorbed
Connecticut). The TQA and DSC studies were per- gases were then extracted wilh CSa and analyzed lo the
TeWtZ
DtCdata
D80 mdotwnrtc paafc
TamoaraturarC}
Haw Jum a*e sn>. Waste imrad 13680 is.u
Haiardwa waste sHa:
Wndsr(8ampla 1) 121*07
4H.3BC
41
0.53
Hazardous wa^te sVr Watt) r*trad HaunkMN waste afta:
Wafeli; Mtrt t Uwlar (Sample 1)
TotalAHtvapoifeaaon) 10.63
Total 4 H (vapofttaaon) enrtcsed la 100%
Hurffcjue waate sMa;
wata extract t bkvte (dan> 1)
TOAi % w*5(otit lose at otvan
tamperatweranoa 38.48
% (notaataln 4 H (vsporfxitlon)
tor haiafdous waste sHa wista axtiaol
tblndaf
CHEMICAL BONDING oortfnueo*
FTIK
The FTIR absorption frequencies, their assignments,
and Ihe shifts In trie assigned frequencies in Sample I
are shown In Table I. Prom Ihe QC-MS data, it was
confirmed that the waste consists of large quantities of
long-chain hydrocarbons, alcohols, aldehydes, kctonea,
and amines, with trace quantities of four priority pollu-
tion. Due to low concentrations of these compounds,
their characteristic frequencies could MM be observed
In the PTIR studies.
Because of this problem, It wu decided to study Ihe
bonding between (he major components and Ihe binder.
There are three shifts In the regions assigned to N-H
and 0-H vibratlonal frequencies: from 3394 to 3383,
* from 3382 to 3372, and from 3373 to 3355, Indicating
weak to moderate perturbations. All these shifts toward
lower frequencies could be attributed to hydrogen bond-
ing between N-H and OH hydrogens and Ihe clay oxy-
gens. There are also weak Interactions in the C-H re-
' glon, which can be attributed to the C-H--O bonding.
The shift from 1597cm"1 to 1580 cro~' Is explained
by an amine sail formation, which Is the result of a
Lewis Acid-Base reaction. The most significant shift
Is seen In the region assigned to SI-O-S1, from 1035
cm "' to 1005 cnT'. This can be explained by Ihe fact
that Ihe oxygens of the silica strongly Interact with Ihe
hydrogens from alkyl groups, hydroxyl groups, and
amino groups, which result In reduction of the O-Si-O
bond order.
CSC
TIL4
The DSC data are thcva In Table 2. Tne extracted
weste shows an cndotfegnt?G peak maximum (Figure I)
at I36.9*C. Tbe energy required to volalHIu Ihe wute
at that temperetufc has been found to be 11.6 j cal/g.
However, the DSC of Sc*np4e I (waste + binder) stums
three cndothermi at I2I.2*C, 4I4.4T. and 4I4.5*C.
respectively. When the energies for these endothermlc
peaks were added together and canceled for 100% (the
weight loss In the sample from Ihe hazardous waste ill*
due to Ihe waste was found to be 36.48% by TOA),
the heat required to drive the waste out of Ihe syitern
turns out to be 28.86 cal/g. This Is considerably higher
(by 54.94%) than the energy required to evaporate ths
waste without the binder.
It is also Interesting to note In the DSC scans of our
synthetic binder that there are cndotherms In the region*
* ...1.1-1. III.. .!,,*
CHEMICAL BONDING eOftfwetf
the fact that the presence of similar compounds la the ..**..-. wall tti'Vi
clay structure favor belter binding characteristics. The
fact thai the waste requires an additional 54.94% energy
to leave the system Indicates that It Is bound rather
strongly lo the matrix.
Hne>Hla V-61.
bonding feMWMt ModUktf stay ptonti Md |k wuu &ait
riUt- Am, 14. 20 (7). H-46 (IMS).
2.