Thermal mass spectroscopy

Thermal electrocyclizations of perhalogenated 1,3-butadienes yield perhalogenated cyclobutenes which can be solvolysed to 3,4-dihydroxy-3-cydobutene-l,2-dione ( squaric acid") and its derivatives (G. Maahs, 1966 H. Knorr, 1978 A.H. Schmidt, 1978). Double CO extrusion from fused cyclobutenediones has been used to produce cycloalkynes, e.g., benzyne from benzocyclobutenedione by irradiation in an argon matrix (O.L. Chapman, 1973) and cyc/o-Ci8, cyclo-Cn, etc. by laser desorption mass spectroscopy of appropriate precursors (see section 4.9.8). 

The principal techniques for determining the microstmcture of phenoHc resins include mass spectroscopy, proton, and C-nmr spectroscopy, as well as gc, Ic, and gpc. The softening and curing processes of phenoHc resins are effectively studied by using thermal and mechanical techniques, such as tga, dsc, and dynamic mechanical analysis (dma). Infrared (ir) and electron spectroscopy are also employed. 

An intensely colored by-product of the photolysis reaction of methyl-2-azidobenzoate has been identified as the first known derivative of 3,3 -diazaheptafulvalene 70 (94LA1165). Its molecular mass was established by elemental analysis and mass spectroscopy as that of a formal nitrene dimer, whereas and NMR studies demonstrated the twofold symmetry as well as the existence of a cross-conjugated 14 7r-electron system in 70. Involving l-azido-2,3-dimethoxy-5,6-dimethoxycarbonylbenzene in thermal decomposition reactions, the azaheptafulvalene 71 could be isolated and characterized spectroscopically and by means of X-ray diffraction. Tliis unusual fulvalene can be regarded as a vinylogous derivative of azafulvalenes (96JHC1333) (Scheme 28). 

The conversion of 70 to the final PPV 60 is then carried out thermally at relatively low processing temperatures (about 100-150 °C) with elimination of (unstable) alkylsulfinic acid. TGA-mass spectroscopy, FT-IR, UV/Vis and CP/MAS NMR spectroscopy are all consistent with quantitative elimination and formation of PPV 60. 

We have undertaken a series of experiments Involving thin film models of such powdered transition metal catalysts (13,14). In this paper we present a brief review of the results we have obtained to date Involving platinum and rhodium deposited on thin films of tltanla, the latter prepared by oxidation of a tltanliua single crystal. These systems are prepared and characterized under well-controlled conditions. We have used thermal desorption spectroscopy (TDS), Auger electron spectroscopy (AES) and static secondary Ion mass spectrometry (SSIMS). Our results Illustrate the power of SSIMS In understanding the processes that take place during thermal treatment of these thin films. Thermal desorption spectroscopy Is used to characterize the adsorption and desorption of small molecules, In particular, carbon monoxide. AES confirms the SSIMS results and was used to verify the surface cleanliness of the films as they were prepared. 

The apparatuses used for the studies of both ammonia synthesis emd hydrodesulfurization were almost identical, consisting of a UHV chamber pumped by both ion and oil diffusion pumps to base pressures of 1 x10 " Torr. Each chamber was equipped with Low Energy Electron Diffraction optics used to determine the orientation of the surfaces and to ascertain that the surfaces were indeed well-ordered. The LEED optics doubled as retarding field analyzers used for Auger Electron Spectroscopy. In addition, each chamber was equipped with a UTI 100C quadrupole mass spectrometer used for analysis of background gases and for Thermal Desorption Spectroscopy studies. 

Thermal desorption spectroscopy and temperature programmed reaction experiments have provided significant insight into the chemistry of a wide variety of reactions on well characterized surfaces. In such experiments, characterized, adsorbate covered, surfaces are heated at rates of 10-100 K/sec and molecular species which desorb are monitored by mass spectrometry. Typically, several masses are monitored in each experiment by computer multiplexing techniques. Often, in such experiments, the species desorbed are the result of a surface reaction during the temperature ramp. 

Structural characterization was based on solubility, thermal and elemental analyses, and infrared and mass spectroscopies. Charac-... 

Electrochemical Thermal Desorption Mass Spectroscopy (ECTDMS). 132... 

The recently developed ex situ analysis of electrode ad-layers by thermal desorption mass spectroscopy has been demonstrated to be a powerful tool for the study of adsorbates [13, 14],... 

Fig. 1.3. Experimental setup for electrochemical thermal desorption mass spectroscopy (ECTDMS). C = electrochemical cell, W = working electrode, El = electrolyte inlet, EO = electrolyte outlet, EH = electrode holder, V = valve, TP = turbo pump, VC = vacuum chamber, L = light source, W = window, P = protective jacket, A = aperture to analysis chamber, GI = grid ion source, S = SEM detector.

Different experimental approaches were applied in the past [6, 45] and in recent years [23, 46] to study the nature of the organic residue. But the results or their interpretation have been contradictory. Even at present, the application of modem analytical techniques and optimized electrochemical instruments have led to different results and all three particles given above, namely HCO, COH and CO, have been recently discussed as possible methanol intermediates [14,15,23,46,47]. We shall present here the results of recent investigations on the electrochemical oxidation of methanol by application of electrochemical thermal desorption mass spectroscopy (ECTDMS) on-line mass spectroscopy, and Fourier Transform IR-reflection-absorption spectroscopy (SNIFTIRS). 

Carbon dioxide chemisorptions were carried out on a pulse-flow microreactor system with on-line gas chromatography using a thermal conductivity detector. The catalyst (0.4 g) was heated in flowing helium (40 cm3min ) to 723 K at 10 Kmin"1. The samples were held at this temperature for 2 hours before being cooled to room temperature and maintained in a helium flow. Pulses of gas (—1.53 x 10"5 moles) were introduced to the carrier gas from the sample loop. After passage through the catalyst bed the total contents of the pulse were analysed by GC and mass spectroscopy (ESS MS). 

An initial experiment involved determination of Arapahoe Smoke Chamber results for samples with and without the zinc coating present. Data are presented in Table II. Depending upon orientation of the sample, an increase in char occurred for some samples with zinc present, while no change in smoke formation was seen. Initial pyrolysis GC/mass spectroscopy results at 90CPC in helium showed no difference in volatiles formed with or without zinc. These results suggested enhanced char formation as the origin of the Radiant Panel results for zinc on modified-polyphenylene oxide (m-PPO). Zinc oxide is a known, effective thermal stabilizer in the alloy. The next work then focused on DSC/TGA studies. 

Figure 5.3. TDS of solution-processed a-Si films. Three samples were prepared by the thermal decomposition of polysilane under the following conditions sample a, 300 °C for 10 min sample b, 300 °C for 120 min and sample c, 540 °C for 120 min. Desorbed gases from the samples were analyzed using mass spectroscopy while the samples were heated in a vacuum. [Reproduced with permission from Ref. 10. Copyright 2006 Nature Publishing Group.]...

The presence of a fragment corresponding to the loss of selenium in mass spectroscopy under electronic impact of germaneselone 179 points to a thermal instability of the Ge = Se bond.132 Heating a solution of 179 in benzene at 80°C in the presence of sulfur leads to a chalcogen exchange, likely via the divalent species (ArO)2Ge 141 [Eq. (38)]. 

Iwasita et used the similar techniques and confirmed that the adsorbate contains a proton atom but concluded that the adsorbate is C-OHad ie same group executed electrochemical thermal desorption mass spectroscopy, in which the methanol absorbing electrode was washed by the supporting electrolyte, transferred to the UHV environment, heated to desorb the adsorbates to analyze them by mass spectroscopy. They found hydrogen molecules in the desorbed gas as well as CO and the ratio of hydrogen to CO decreased as the concentration of methanol increased. 

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