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GC-MS Characterization Of Radiolytic Degradation Products Of Tri-isoamyl Phosphate

C. Banerjee , M. Bindu, M. Lokhande, S.C. Tripathi ,* P.M. Gandhi and P. Janardan Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400085, India.
*Email add.: sct@barc.gov.in Received on:

Introduction
Despite the overall success of TBP, it has some demerits, which result in process problems [1,2]. Most of its process disadvantages stem from the radiation-chemical degradation of the solvent resulting in the formation of harmful species like Di-n-Butyl phosphoric acid (HDBP) and Mono Butyl Phosphoric acid (H2MBP) [3]. Presence of these species in the solvent not only reduces the quality of the product (decontamination factor) but also leads to their significant losses in waste streams. A new and indigenous extractant, tri-iso-amyl phosphate (TiAP) is proposed for the spent fuel reprocessing of the Fast Breeder Test Reactor (FBTR). TiAP being a higher homologue with branched alkyl chain, has an edge over TBP, that helps to prevent the third phase formation [4-6]. The degradation species of the extractant are normally identified by their characteristic retention times under standardized condition by Gas chromatographic analysis. Due to the presence of large number of degradation species of the diluent and solvent, resolution of sample components on capillary column followed by library search provides the identification of the species for unknown compounds. Present study was aimed at generating the mass spectral data of Pure TiAP as well its degradation products generated by gamma radiolysis using 60Co source.

Experimental Details
Tri-iso-amyl Phosphate (TiAP) manufactured by Heavy Water Board was used for the preparation of 30 % TiAP. AR grade n-dodecane supplied by Orion Chemicals Pvt. Ltd., Navi Mumbai was used as diluent. 30 % TiAP was equilibrated with 2M nitric acid in 1:1 (v/v) ratio. The acid equilibrated samples were subjected to gamma radiolysis for absorbed dose of 0, 6, 12, 18 and 24 M Rads. Correspondingly, a blank sample (30% TiAP-n-dodecane) was also analyzed with the aforesaid samples through electron impact ionization using a Shimadzu model QP2010 plus GC-MS system having Rxi- 5MS column (30m 0.25 mm;0.25 m) under temperature programmed condition (with a split ratio of 57) from 90 oC to 230 oC at a program rate of 10 oC . The sample aliquots were treated with diazomethane (in ether) for methylation of the acidic phosphates.

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Results TABLE 1. Major mass fragment pattern of TiAP

Peak (m/ z) 309 239 169 125 99 71 Major TiAP Fragments Remarks Molecular ion peak of TiAP Loss of an iso-amyl group (mass 71) Loss of two iso-amyl group (mass 141) Loss of two iso-amyl group and an isopropyl group (mass 43) Loss of three iso-amyl group (H3PO4 ,M.W. 98) Iso-amyl fragment Nature of peak (m+1) (m+1) (m+1) (m+1) (m+1) Base peak (m)

TABLE 2. Major mass fragment pattern of MeDiAP

Major MeDiAP Fragments
Peak (m/z) Remarks Nature of peak

183 139 113 71 57 43

Loss of a methyl group (mass 15) Loss of a methyl group and a propyl group (mass 43) Molecular ion peak of MeDiAP (methyl ester of DiAP) Iso-amyl fragment Loss of a butyl group (mass 57) Loss of a propyl group (mass 43)

(m+1) (m+1) (m+1) Base peak (m) (m) (m)

Fig. 1. Total Ion Chromatogram of TiAP as such, Retention Time: 13.27 minutes

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Fig. 2. Mass spectra of MeTiAP as such, Retention Time: 13.27 minutes

Fig. 3. Mass spectra of TiAP (12MRad), Retention Time: 10.18 minutes

Fig. 4. Mass spectra of TiAP (24MRad), Retention Time: 17.12 minutes

Conclusions
Present investigation has led to the mass spectral characterization of tri-iso-amyl phosphate (TiAP), a novel solvent proposed to be used for the reprocessing of FBTR spent fuel. Its degradation products Di-iso-amyl phosphoric acid (HDiAP) has also been eluted as methyl ester on capillary column and has been characterized due to the presence of the base peak at m/z = 113 along with a small fragment of iso-amyl group at m/z = 71. It is interesting to note that the highly intense base peak (Fig. 3.) corresponding to m/z =113 identified as the marker of the methyl ester of DiAP resembling the corresponding ester of Dibutyl phosphoric acid (HDBP) also studied earlier [7,8]. However, the discriminating feature between the two acidic phosphates is the next intense peak at lower mass number with m/z = 71 reflecting the loss of the iso-amyl group (m/z = 71) in case of MeDiAP (methyl ester of di-iso-amyl phosphate) and m/z = 57, reflecting the loss of the butyl group from MeDBP (methyl ester of dibutyl phosphate). In addition, the present investigation has also revealed the radiolytic formation of High Molecular weight organoPhosphate (HMP) corresponding to addition of .OH radical/ group to one of the alkyl chain of TiAP (Fig. 4.) identified by the (m+1) peak at m/z = 327, at retention time higher than that of the TiAP. This species is similar to a High Molecular Phosphate (hydroxyl TBP) formed in case of radiolytic degradation of TBP in our earlier studies [7, 8]. These are the tentative assignments to the observed mass fragments under experimental conditions. The existing NIST library of Shimadzu GC-MS system does not

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contain the mass spectral data of DiAP molecule under study. The methyl ester of DiAP is identified as an ester of phosphoric acid; its exact atomic composition is not reflected by the library search engine of the GC-MS system. Hence, present investigation has enabled us to add these assignments to the existing library of mass spectra stored in NIST library.

Acknowledgment
The authors wish to acknowledge their sincere thanks to Shri S. D. Misra, Director, Nuclear Recycle Group for his constant encouragement during the course of the present investigation. Thanks are also due to the Dr. Arun Sharma, Head, Food Irradiation and Processing Laboratory (FIPLY) for providing us their gamma irradiation facility and Dr. Lalit Varshney, Head, Radiation Technology Development Division for providing the GC-MS facility, used in the present investigation.

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3. S. H. Hasan, J. P. Shukla, Journal of Radioanalytical and Nuclear Chemistry. Vol. 4. 5.

258, No. 3 (2003) 563. W. W. Shulz, J. D. Navratil, Science and Technology of Tributyl Phosphates, Vol. 1 , Chapter III , p. 60,CRC Press Inc. . S.C.Tripathi, P.Bindu, , A. Ramanujam, Studies on the identification of harmful radiolytic products of 30%TBPn-dodecaneHNO3 by gas liquid chromatography. Part I: formation of diluent degradation products and their role in Pu retention behaviour. Sep. Sci. Technol.36 (07), 1463,2001. S.C.Tripathi, A. Ramanujam ,K.K. Gupta, P. Bindu, Studies on the identification of harmful radiolytic products of 30% TBP-n-Dodecane-HNO3 by gas-liquid chromatography. II. Formation and characterization of high molecular weight organophosphates. Sep. Sci. Technol. 36(13), 28632883,2001. U. Jambunathan,M. Bindu,S.C. Tripathi and A. Ramanujam, Proceedings of ISMAS Silver Jubilee Symposium on Mass Spectrometry (ISMAS-SJS-2003),859. Manisha R. Lokhande and S.C. Tripathi, Proceedings of 11th ISMAS Triennial International Conference on Mass Spectrometry (11th ISMAS-TRICON 2009), 539.

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