MENO""NE. RD A± 57V TURI COLLOIDAL PSENLIZE CH SECT 5I R/D57CTI -U) i/ SP 5 /-507CH6 AD ~~AA C -6623RSEBISEFETO HRIR ECIOSU / UNCLAS

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1 RD A± 57V TURI COLLOIDAL PSENLIZE CH SECT 5I R/D57CTI -U) i/ TRINUNV -PLIZTT ITL) SP 5 /-507CH6 AD ~~AA C -6623RSEBISEFETO HRIR ECIOSU / UNCLAS MENO""NE SIFIED F/O 7/3 NL

2 111j=2A 1 j.2 mu 11111L--. MICROCOPY RESOLUTION TEST CHA~tl.JRFAU - TAfn*JW-1963-A - dpre - - w IMF--

3 DJTIC FILE COPY COLLOIDAL ASSEMBLIES EFFECT ON CHEMICAL REACTIONS E. Pelizzetti Universita di Torino Contract no. DAJA C-0023 "First Periodic Report" August September 1985 "The research reported in this document has been made possible trough the support and sponsorship of the U.S. Government trough its European Research Office of the U.S. Army. h,-g.pq*4 DT k - SELE CT SAPR Apnovsd for pubiac n~mg Dlurlutont'dljtcj

4 T~r~rbJA~~r1r% VWrU % FUI W VM i. u- U'F L-R vvn' vvm~m U vv ~ WI / (1) In the period August-September 1985 the research carried out Gar-'bt divided into the following parts 1) PHOTODEGRADATION OF ORGANIC COMPOUNDS BY VISIBLE LIGHT. Chloroaromatic derivatives ( compounds of relevant concern because some of them are bioaccumulative and persistent in the enviroment and also extremely toxic) were investigated. Microbial degradation and naturally occurring hydrolysis require long periods; direct photodegradation requires high energy photons often leading to incomplete decomposition and, in some cases, to the formation of dangerous products. Heterogeneous photo-assisted catalytic degradation by mn nq.ofsemiconductor particles has been applied to a variety of haloaromatic compounds ( see Table 1). Various semiconductor slurries have been used and Figure 1 shows the results of light exposure of aerated acqueous solutions of 3,4-dichlorophenol. Inasmuch as naked Ti9, exhibited the highest efficency in the photodegradation reaction, we have chosen TiO 2 to investigate the decomposition of DCP and the series of haloaromatic compounds listed in Table 1. The presence of catalyst and light is essential for a rapid degradation. As well, oxygen and water are crucial ingredients for the reaction progress. As for the final products, analysis after long experiments (3 hours for DCP ) showed quantitative formation of C and HCI. Since substitution of TiO 2 with A 2 0 3, or irradiation with light of wavelenght greater than the bandgap excitation. of the semiconductor, leads to inefficient degradation, it is possible that organic radicals ( primary intermediates) are formed concomitant with the displacement of chlorine and formation of chloride ion. These radicals species can subsequently and rapidly produce hydroxy or dihydroxy aromatic intermediates which can be degraded further but at slower rates. It is evident from the data of Table 1 that this semiconductor catalyst assisted photodegradation process can be applied to a wide variety of compounds even when present at very low concentrations. The degradation half life (tvl/2a) is only slightly affected by the increase in the halogen content as well as by the solubility of the compounds. Of interest, experiments n For have demonstrated that photodegradation proceeds at a significant A&I rate also under direct sunlight. 0 Particular attention has been devoted to 2,4,5-T degradation. e The identification of the intermediates has been accomplished through GC-MS technique (1). ilitt Codes C"2 _AA 2 /or p00 lal.. i... I i I i ' I I I "''l " l *' r ' - fr.i ',. -

5 2) KINETIC INVESTIGATIONS OF THE EFFECT OF COLLOIDAL ASSEMBLIES AND SOLVENT COMPOSITION ON THE ELECTRON TRANSFER REACTIONS. I The electron tranfer kinetics between inorganic complexes (e.g. IrCl 2 -, Mo(CN) 3 - ) and benzenediols ( catechol and substituitej catechols) has been investigated in the presence of O/W microemulsions ( water,naci 1% / toluene/ 1-butanol/ SDS). The rates of reactions are affected by the microemulsion concentration and composition. This effect is also dependent on the substituent ( e.g. hydrophobicity) present on the aromatic ring (2). The same reactions are gr.tually investigated also in the presence of water/orgaje -solvent mixtures (acetone, t-butanol, methanol). Anothei- -investigation has concerned the degradation of chlo enols by means of B0 2 in the presence of Fet The final ppducts, the parameters influencing the reactions have been jassessed (3). 3) PROPERTIES OF AGGREGATES. The formation of the ground state charge transfer complex between durene and chloranil has been investigated in CH C1 and in oil-in-water (O/W) microemulsions. The CH 2C12 or 2 C 2 2 C1 2 /hexadecane microemulsion systems are stabilized by a cationic surfactant ( hexadecyltrimethylammonium bromide) and 1-butanol as a cosurfactant. If the effective concentration in the oil phase (CH 2C1 2 /hexadecane) is accounted for, the equilibrium constant is not significantly changed with respect to the homogeneous CH C1 solution. The equilibrium of formation or dissociation of?he 2 complex is reached in less then 1*l073 sec. (4). 3

6 LIST OF PUBLICATIONS 1) M.Barbeni, E.Pramauro, E.Pelizzetti, M.Vincenti, E.Borgarello and N.Serpone - manuscript in preparation 2) C.Minero, E.Pramauro and E.Pelizzetti - manuscript in preparation, -V - 3) M.Barbeni; C.Minero, E.Pramauro, E.Pelizzetti, E.Borgarello and N.Serpone - manuscript in preparation 4) P.Infelta, R.Graglia and E.Pelizzetti - manuscript in preparation 4I 4"

7 (2) RESEARCH PLANS - Photodegradation of organic compounds by visible light. Other haloaromatic compounds, such as PBC and dioxins, will be considered. Particular attention will be devoted in the investigation of the details of the reaction mechanism (adsorption-desorption process, kinetics, inhibition, nature of the semiconductor and its surface, detection of intermediates). - Catalysis effects of transition metal ions complexes on reactions in homogeneous and heterogeneous media and in the presence of organised systems like micelles and microemulsions, will be explored, with particular attention to peroxide/metal ions degradative effect on organic compounds. - The effect of organised assemblies and solvent composition on the electron transfer reaction between organic molecules and inorganic complexes will be examined. - The physico-chemical properties of colloidal aggregates will be investigated. (3) No significative administrative actions occurred during the period reported. (4) (5) Annex ( see attached sheets) (6) No founds have have been received until now. I I ' I ' I '"'I I '

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Second Interim Report NTIS GRA&I. 0 Michael Grttzel, Ph.D. By. Professor of Chemistry. June 20, United States Army

D FILE COPY CATALYTIC AGENT DEGRADATION ON OXIDE LI 8 AND IN MCROHETEROGENEOUS SOLU'ION SYSTEMS cj Accession For Second Interim Report NTIS GRA&I by DTIC TAB Unannounced Justification 0 Michael Grttzel,