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4. Mass Spectrom. See. Jpn. Regular Paper Vol. 48, No. 4, 1998 Thermal Decomposition of Urea and Urea Derivatives by Simultaneous TG/(DTA)/MS Jian Ping Cu (Received December 16, 19 *’ and Kimio Isa*” ; Accepted June 9, 1998) ‘Simultaneous TG-MS (TG: thermogravimetry, MS: mass spectrometry) measurement, a mass spectrometer ‘connected with a thermogravimetry by a transfer li investigate decomposition of urea, ‘and an interface or by the skimmer coupling, was used to ‘A simple decomposition reaction of urea to form ammonia and eyanic acid (or isocyanic acid) was determined, The low intensity ratio of m/z 43 to m/z 17 was attributed (o that the eyanic acid react with water to form carbon dioxide, Polymerization and decomposition ofthe polymers were more predominant later than the simple decomposi- tion ater tne first stage. Introdu Thermogravimetry (TG) is used to investigate weight loss during thermal decomposition of solid ma- terials, However it is necessary to analyze the evolved ‘gases in order to surmise the reaction mechanism. Mass spectrometry (MS) can distinguish gaseous products of the reaction with high sensitivity. There- fore, a simultaneous TG-MS measurement, £e., a mass spectrometer connected to a thermogravimetry by a transfer line and an interface, is an effective approach to investigate decomposition of materials, TG-MS has been applied to many fields,” and has been developing. ‘The activation energy for thermal decomposition of urea was determined by TG.” Ozawa et al. reported that urea was thermally unstable” The following de- composition reactions were reported.” ‘The decomposition of urea by means of TG-(DTAY MS has not been studied until now. In this paper, thermal decomposition of urea was investigated by the simultaneous TG-DTA-MS to understand its decompo- sition mechanisms. Systematic reaction pathways were chicidated using the mass spectra of a series of urea derivatives. Experimental ‘The simultaneous TG-MS is shown in Fig. 1. The TG (Sinku Riko Co, Ltd.) consists of thermobalance (TGD- 7000 RH model) and the control system (TA-7000 model), The MS (Denshi Kagaku Co, Ltd) consists of a small double focussing mass spectrometer (EMD-050 model) and the data system (MD-DP300 model). The TG is combined with the MS via both a transfer line and an a e @ 2 200 g ee w "Natural Science Education Laboratory, Faculty of Education, Fucui University Wunkyo 3-9-1, Fukui 910~ 8507, Japan) =8NHL,~ 3H homemade interface. Intermediates of thermal decomposition of urea were also investigated with an EIMS (EIMS: electron —299— JAP. Chen and K. Isa Fig. 1. Apparatus of simultaneous TG-MS. Table IA Tynieal Pxperimental Condition ‘Atmospheric He Sensitivity of DTA ‘Temperature of transfer line Temperature of interface “Temperature of ion source chamber | lonie eneray Electric emission current (MS scanning time 805 + fullsean: Fig. 2 1G-IA of urea. =| : MS system vacuum 2X10 Torr ‘Weight of samale (222) mg ionization mass spectrometry) apparatus (JMS DX 303, JEOL)®. Urea and urea derivatives were also measured with a skimmer coupled TG-DSC-MS (STA409/QMS, NETZSCH Geratebau GmbH)". Urea, N-methylurea, N,N-dimethylurea, and 1,3- dimethylurea (GR grade, Kanto Chemical Co.) were used without further purification, Alumina was used as a standard material for differential thermal analysis (TA), ‘A typical experimental condition was shown in Table 1. After flowing helium for 2-3 hours, the MS apparatus was run for 10 minutes for measuring mass spectral base lines of background. Then the TG was heated at a constant heating rate until 500°C, when the MS spectrometer was stopped and then the TG was quickly heated to 1,000°C. The TG was maintained 10 minutes at 1,0C0'C for cleaning. Results and Diseussion ‘The TG-DTA of urea measured with the heating rate 4°C-min“', is shown in Fig. 2, The decomposition initiated before the melting point (mp, 132.5°C). The weight losses were about 66 %, 13.96, 18 9, and 3% (total 100 94) for each stage, respectively. The mass spectra corresponding to the first and second stages were shown in Figs. 3a and 3b, respectively. The mass spectra of the third and fourth stages were similar to those of the second stage. The m/z 60 (molecular ion M*" of urea) was not detected. The m/z 14, 28, 16, and 32 observed in both figures were considered as residual nitrogen and oxygen, respectively. The m/z 18 and ‘m/z 40 in both figures were considered as water and gee s sR ee 5 Mass Nomtor {ina Fig. a. Mass spectrum ofthe second stage in Fig 2 0-4 4 4 zo) | wd, | 414) ott ik Lt 0 eather een eesgeesee eee g Mase Number [on/2] Fig. 3b. Mass spectrum of the second stage in Fig. 2 argon in the ambience, respectively. The m/z 44 were attributed (0 carbon dioxide evolved during decompo- sition of urea as will be explained later (the reaction formula (10). The mass chromatograms of m/z 17, 18, 43, and 44 are shown in Fig. 4. The background was too high to recognize the signal. In order to obtain more definitive information, the urea was heated up to 180 at 4°C+ min“! and maintained at 180°C for 2 hours. Then the residual was cooled to ambient temperature with helium and was subjected to EIMS measurement. Its ‘mass spectrum is shown in Fig. 5. The m/z 60 and 180 are assigned to a single molecule and the trimer of urea, respectively. The m/z 103 and 129 coincide with the polymeric reactions (1) and (2), respectively. The m/z 17 (considered to be ammonia gas) can be understood —a00— Mate Chromatogram Maw Numer (21 1 Decomposition of Urea and Urea Derivatives by Simultansous TG/(DTA)/MS 6 Mate Chromatogram ; eames @ Fig. 4 Fig. 5. El mass spectrum of the residual in terms of both the polymeric reactions and the simple decomposition reaction (reaction formula (5)) The detection of m/z 43 (considered to be cyanic acid) supports the simple decomposition (). These results suggested that several polymeric reactions and the simple decomposition reaction occur simultaneously in the same stage. Fig. 6, 7, and 8 show the TG-MS spectra of urea derivatives, N-mathylurea, N.N-dimethylurea, and 1,3 dimethylurea, respectively. N-methylurea (molecular weight 74) resulted in the formation of m/z 17, 87, 31, and 44 jons (Fig. 6). N.N-Dimethylurea (molecular weight 88) showed ions of m/z 43, 44, and 45 (Fig. 7). ‘The 1,3-dimethylurea, which molecular weight is identical with that of N.V-dimethylurea, showed ions of m/z 31 and 87 (Fig. 8). ‘These results can be ex- plained by the following simple decomposition reac- tions accompanying the equilibrium intermedium (the reaction formula(6),(7), and (8)). From these reactions ‘a model for the thermal decomposition of urea deriva tives is generally expressed by the reaction formula (9). Decomposition of urea (reaction formula (5) can be Metention time min} GD) 30 300 40080 o Mass chromatograms of ures. g latensiey ob8888 Mase Number (m1 Mass Chrom Maws Number {m2 time {mio} Fig. 6. Mass spectrum and mass chromatogram of N-methylurea, derived by substituting Ri, Re, and Ry by hydrogen in the reaction formula (8). The presence of m/z 17 ion (ammonia) and m/z 43 ion (cyanic acid or isocyanic acid) can be interpreted by the decomposition reactions —301—