The decomposition of Bicyclo[3,3,1]nonan-9-ylidene

1970 ◽  
Vol 23 (8) ◽  
pp. 1625 ◽  
Author(s):  
RD Allan ◽  
RJ Wells
Keyword(s):  
Thermal Decomposition ◽  
Sodium Salt ◽  
Aprotic Solvents ◽  
Protic Solvent ◽  
Product Analysis ◽  
Decomposition Products ◽  
Product Composition ◽  
Excess Base

The intramolecular decomposition products of bicyclo[3,3,1]nonan-9-ylidene, generated by thermal decomposition of the sodium salt of bicyclo[3,3,1]nonan-9-one-tosylhydrazone, have been investigated in protic and aprotic solvents and also without solvent. When bicyclo[3,3,1]nonan-9-ylidene is generated in the presence of excess base in aprotic solvents product analysis indicates that 1,3 insertion is predominant with some carbene rearrangement. When a protic solvent is used the product composition indicates a predominantly cationic intermediate. Decomposition of the carbene in the presence of a limited amount of base, even under aprotic conditions, gives rise to products resulting from both cationic and carbenoid intermediates.

scholarly journals Thermal decomposition of tris(O-ethyldithiocarbonato)-antimony(III)—a single-source precursor for antimony sulfide thin films

2021 ◽  
Author(s):  
Jako S. Eensalu ◽  
Kaia Tõnsuaadu ◽  
Jasper Adamson ◽  
Ilona Oja Acik ◽  
Malle Krunks
Keyword(s):  
Thin Films ◽  
Thermal Decomposition ◽  
Mass Loss ◽  
Solid Phase ◽  
Evolved Gas Analysis ◽  
Gas Analysis ◽  
Thermal Decomposition Mechanism ◽  
Product Analysis ◽  
Gaseous Species ◽  
Single Source Precursor

AbstractThermal decomposition of tris(O-ethyldithiocarbonato)-antimony(III) (1), a precursor for Sb2S3 thin films synthesized from an acidified aqueous solution of SbCl3 and KS2COCH2CH3, was monitored by simultaneous thermogravimetry, differential thermal analysis and evolved gas analysis via mass spectroscopy (TG/DTA-EGA-MS) measurements in dynamic Ar, and synthetic air atmospheres. 1 was identified by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) measurements, and quantified by NMR and elemental analysis. Solid intermediates and final decomposition products of 1 prepared in both atmospheres were determined by X-ray diffraction (XRD), Raman spectroscopy, and FTIR. 1 is a complex compound, where Sb is coordinated by three ethyldithiocarbonate ligands via the S atoms. The thermal degradation of 1 in Ar consists of three mass loss steps, and four mass loss steps in synthetic air. The total mass losses are 100% at 800 °C in Ar, and 66.8% at 600 °C in synthetic air, where the final product is Sb2O4. 1 melts at 85 °C, and decomposes at 90–170 °C into mainly Sb2S3, as confirmed by Raman, and an impurity phase consisting mostly of CSO 2 2− ligands. The solid-phase mineralizes fully at ≈240 °C, which permits Sb2S3 to crystallize at around 250 °C in both atmospheres. The gaseous species evolved include CS2, C2H5OH, CO, CO2, COS, H2O, SO2, and minor quantities of C2H5SH, (C2H5)2S, (C2H5)2O, and (S2COCH2CH3)2. The thermal decomposition mechanism of 1 is described with chemical reactions based on EGA-MS and solid intermediate decomposition product analysis.

Theoretical study on the formation of carbon disulfide and ammonia from thermal decomposition products of thiourea

2014 ◽  
Vol 13 (04) ◽  
pp. 1450022 ◽  
Author(s):  
Zerong Daniel Wang ◽  
Meagan Hysmith ◽  
Perla Cristina Quintana
Keyword(s):  
Thermal Decomposition ◽  
Carbon Disulfide ◽  
Density Functional ◽  
Basis Sets ◽  
Structural Isomer ◽  
Consecutive Reaction ◽  
Functional Theory ◽  
Decomposition Products ◽  
Thermal Decomposition Products ◽  
Hybrid Module

The formation of carbon disulfide ( CS 2) and ammonia ( NH 3) from the thermal decomposition products of thiourea has been studied with MP2, and hybrid module-based density functional theory methods (B3LYP, MPW1PW91 and PBE1PBE), each in conjunction with five different basis sets (6-31+G(2d,2p), 6-311++G(2d,2p), DGDZVP, DGDZVP2 and DGTZVP). The free energy changes and activation energies for all the five primitive reactions involved in the formation of CS 2 and NH 3 have been compared and discussed. The results indicate that CS 2 is most likely formed in a consecutive reaction path that consists of the addition of hydrogen sulfide ( H 2 S ) to isothiocyanic acid (HNCS) to generate carbamodithioic acid and subsequent decomposition of carbamodithioic acid. By contrast, thiocyanic acid (HSCN) as the structural isomer of isothiocyanic acid is not likely the source of CS 2.

Pyrolysis of ethane in the presence of hydrogen sulfide. Rates of formation of ethylene, hydrogen, and methane

1970 ◽  
Vol 48 (11) ◽  
pp. 1782-1785 ◽  
Author(s):  
P. R. McLean ◽  
D. J. McKenney
Keyword(s):  
Thermal Decomposition ◽  
Hydrogen Sulfide ◽  
Quantitative Data ◽  
Methane Formation ◽  
Partial Product ◽  
Complex Mechanism ◽  
Product Analysis ◽  
Hydrogen Formation

Rates of formation of ethylene, hydrogen, and methane have been measured at 630 °C for the thermal decomposition of ethane at pressures between 100 and 620 Torr, with various pressures (approximately 1 to 100 Torr) of added hydrogen sulfide. The effect of the H2S was to increase the rate of methane formation and to decrease the rate of ethylene and hydrogen formation. Rates of formation of all three of these gases decreased with increasing hydrogen sulfide pressures. The quantitative data obtained and the partial product analysis indicate that a complex mechanism is operative. Possible qualitative explanations for the observations are discussed.

Transport and condensation of soft a-C:H film thermal decomposition products

2003 ◽  
Vol 313-316 ◽  
pp. 460-464 ◽  
Author(s):  
A.E. Gorodetsky ◽  
R.Kh. Zalavutdinov ◽  
I.I. Arkhipov ◽  
V.Kh. Alimov ◽  
A.P. Zakharov ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Decomposition Products ◽  
Thermal Decomposition Products
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