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Hydrogen argonide {H2Ar}: artifact or an objective reality?

For less than a year, our experimental studies at SKTB Catalyst LLC continued. The main objective of this stage was to confirm the results on decomposition of hydrogen sulfide at room temperature on metal catalysts previously obtained at the Institute of Catalysis with the production of hydrogen and diatomic gaseous sulfur. For a very short time, the experimental setup was put into operation, on which previously obtained results on the decomposition of hydrogen sulfide were reproduced. Moreover, a fundamentally new catalytic system was developed, which later received the conventional name “Start-1”, which in its characteristics significantly surpasses all our known catalytic systems.

However, the main obstacle to the continuation of the research was an incredible experimental fact that we discovered: hydrogen, as the target product of the decomposition of hydrogen sulfide, was detected on the “Test-1” hydrogen analyzer in very small quantities, significantly less than what the reaction stoichiometry required. To the best of our ability, we tried to convince the management of SKTB of the need for scientific research requiring additional funding, but in vain. Since SKTB is a commercial structure, the unforeseen costs for conducting basic research have become an overwhelming and risky financial burden for SKTB, therefore, further continuation of work in this direction was considered inappropriate.

Due to the fact that the prospect of the revival of experimental studies on the low-temperature decomposition of hydrogen sulfide in the Siberian region is very illusive (recall that the chairman of the Siberian Branch of the Russian Academy of Sciences is Parmon), it was decided to publish in the public domain a hypothesis about the possibility of interaction of atomic hydrogen generated at the moment of decomposition of hydrogen sulfide on solid catalysts, with chemically very inert molecules – argon, nitrogen and carbon dioxide. To prove (or refute) this hypothesis, fundamental research is required involving the most modern experimental instruments and theoretical calculation methods. Therefore, I appeal to the progressive leaders of the scientific community, free from the corrupting influence of the conservative leadership of Russian science, and I really hope for help and support from commercial structures.

H2Ar-HydrogenArgonide-Startsev  DOI: 10.13140/RG.2.2.10096.81920

I am ready to share all my knowledge and accumulated experience to solve the tasks.

Low-temperature catalytic decomposition of hydrogen sulfide on metal catalysts under layer of solvent.

A. N. Startsev, O. V. Kruglyakova, Yu. A. Chesalov, E. A. Paukshtis, V. I. Avdeev, S. Ph. Ruzankin, A. A. Zhdanov, I. Yu. Molina & L. M. Plyasova

Boreskov Institute of Catalysis, Novosibirsk, Russia

Journal of Sulfur Chemistry. Published online: 24 Feb 2016.

ABSTRACT
When hydrogen sulfide decomposition {2 H2S ↔ 2 H2 +S2(gas)} is carried out in the flow regime at room temperature on metal catalysts placed in a liquid capable of dissolving H2S and sulfur, the reaction equilibrium can be significantly (up to 100%) shifted to the right yielding the desired product – hydrogen. The process efficiency was demonstrated using aqueous solutions of monoethanolamine (MEA), sodium carbonate, which is widely used in industry for H2S absorption from tail gases, and aqueous hydrazine as examples. IR and Raman spectroscopy data demonstrated that sulfur obtained in the solutions is in the form of diatomic molecules. DFT calculations showed that diatomic sulfur forms weakly bound coordinative
complexes with solvent molecules. Some problems related to sulfur accumulation and recovery from the solvents are discussed.

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Purification of Hydrogen Sulfide from Oxygen.

O. V. Kruglyakova and A. N. Startsev
Boreskov Institute of Catalysis, Russian Academy of Sciences, Novosibirsk, 630090 Russia
Received October 11, 2014

Abstract

A technique for determining the concentration of oxygen in hydrogen sulfide is developed on passing the tested hydrogen sulfide through the stainless steel chips and determining the amount of solid sulfur formed over the catalyst’s surface as a result of hydrogen sulfide oxidation by impurities of oxygen. A method for the deep purification of hydrogen sulfide of oxygen is developed. It is shown that under certain conditions, two chemical reactions for the conversion of hydrogen sulfide into two different modifications of sulfur (solid and gaseous) can proceed independently and simultaneously on the catalyst’s surface.

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Aqueous Solutions of Sulfur Produced via Low-Temperature Hydrogen Sulfide Catalytic Decomposition.

A. N. Startsev, O. V. Kruglyakova, Yu. A. Chesalov, A. N. Serkova, E. A. Suprun, A. N. Salanov, and V. I. Zaikovskii
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
Received January 23, 2014

Abstract:

White globules of solid sulfur modification are obtained from saturated aqueous solutions. The chemical composition, morphology, and structure of the white sediment are investigated by means of X-ray fluorescence analysis, scanning electron microscopy, and high resolution transmission electron microscopy. It is shown that the white sediment contains an unknown modification of globular hexagonal sulfur with globule sizes of 5–10 μm and interplanar distances of 0.45, 0.29, and 0.15 nm. A single absorption band at 880 cm–1 is found in the Raman scattering spectra of the saturated solutions above the sediment. It is suggested that the white sediment consists of condensed S2 phase.

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The key role of catalysts in H2S decomposition: non-equilibrium thermodynamics of open system

The stumbling block of all our research has been and remains the thermodynamics of the reaction of low-temperature decomposition of hydrogen sulfide into constituent elements, as well as the unusual state and properties of the resulting diatomic gaseous sulfur. Since sulfur and hydrogen sulfide have been known since ancient times and an incredible amount of research has been devoted to the study of their properties, the discovery of some fundamentally new states of sulfur caused a categorical rejection of all the experimental evidence we obtained, and we ourselves were labeled as illiterate charlatans and crooks who strive to surprise the world with “outstanding discovery “(quote from Parmon)

Indeed, classical equilibrium thermodynamics considers only isolated systems that do not exchange either matter or energy with the environment. In these systems, chemical processes are carried out by supplying energy from outside, so the rate and direction of the process depends only on external conditions, and the catalyst does not change the thermodynamics of the process.

At the same time, all processes occurring in Nature are carried out at ambient temperature and pressure without supplying energy from outside (in this case, we consider only dark processes without the participation of sunlight). All biological processes are far from equilibrium and are irreversible, therefore, to describe them, nonequilibrium thermodynamics, or thermodynamics of irreversible processes, was created, which was formed as an independent scientific discipline in the middle of the last century and one of its creators is I.R. Prigogine. Distinctive features of biological thermodynamics is that the systems it considers are open to flows of matter and energy. The inevitability of the appearance of this science was due to the understanding that the vast majority of processes occurring in nature and with the participation of humans are irreversible and cannot be described within the framework of the existing “classical” equilibrium thermodynamics, which does not take into account the time factor.

In terms of nonequilibrium thermodynamics for an open system, the role of catalysts becomes clear, on the surface of which chemical reactions are carried out which are impossible in the gas phase. This material was sent on 04.16.2018 for publication in the journal Kinetics and Catalysis, however a negative review was received. The corrected version of the manuscript was sent on July 16, 2018 to the Journal of Physical Chemistry, where after six months of review and replacement of 4 (four !!!) reviewers, on February 23, 2019, Startsev’s review was rejected.

Due to the lack of prospects for publication in Russian journals, it was decided to publish this review in the public domain on our website.

KeyRole-Startsev-2019  DOI: 10.13140/RG.2.2.28119.21921

Ready to answer all questions and comments.

 

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Diatomic Gaseous Sulfur: a misterious molecule

The completely unexpected and unpredictable experimental fact of the formation of diatomic gaseous sulfur in the reaction of low-temperature catalytic decomposition of hydrogen sulfide made us very carefully and comprehensively analyze the very extensive experimental material on the study of the properties of elemental sulfur in all three aggregate states. As a result, a review was prepared with the same name, which was submitted for publication to the Russian Journal of General Chemistry, Vestnik of the Russian Academy of Sciences, the Russian Journal of Structural Chemistry, but publication refusals were received. Finally, the English version of the review was submitted to a specialized Journal of Sulfur Chemistry where it was published JSulfChem-2019-40-4-435-450-Startsev .

It was shown that the diatomic gaseous sulfur obtained by us for the first time is in the ground triplet state, as is its isoelectronic analog, oxygen. In the thermal processes of the  dissociation of elemental sulfur and decomposition of hydrogen sulfide, diatomic sulfur is formed in a metastable singlet state, the thermodynamic parameters of which are given in the handbooks. Therefore, based on the analogy with molecular oxygen, we have to conclude that the standard enthalpy of formation of triplet sulfur should also be equal to zero

ΔfHо298 (S2 X 3S–g ) = 0.

The gaseous diatomic sulfur S2 is stable at temperatures up to 200 ° C and higher, has a sharp nauseating smell, crystallizes at the temperature of liquid nitrogen in the form of delicate white snowflakes, and sublimates after heating to room temperature. It is well dissolved in water (over 5 g / liter). The aqueous sulfur solution is colorless, has a neutral pH like that of the original water, has no absorption bands in the IR and Raman spectra, and the refractive index corresponds to the refractive index of water. This is characteristic of many dissolved diatomic gases that do not interact with water.

From saturated aqueous solutions of diatomic sulfur, a previously unknown white globular modification of solid sulfur was obtained. The size of white globules of almost regular spherical shape reaches 5 – 10 microns, while the smallest particles are transparent and colorless. Electron diffraction on an individual sulfur globule indicates its hexagonal structure with interplanar spacings of 0.45, 0.29 and 0.15 nm.

When dissolved in polar solvents or when adsorbed onto carriers, the colorless triplet sulfur acquires a yellow color, while maintaining a diatomic state.

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Low Temperature Catalytic Decomposition of Hydrogen Sulfide into Hydrogen and Diatomic Gaseous Sulfur.

A. N. Startsev, O. V. Kruglyakova, Yu. A. Chesalov, S. Ph. Ruzankin, E. A. Kravtsov, T. V. Larina, E. A. Paukshtis.
Published online: 24 May 2013.
©Springer Science+Business Media New York 2013.

Abstract

A new catalytic reaction of hydrogen sulfide decomposition is discovered, the reaction occurs on metal catalysts in gas phase according to equation
2H2S ↔ 2H2 + S2(gas)
to produce hydrogen and gaseous diatomic sulfur, conversion of hydrogen sulfide at room temperature is close to 15 %. The thermodynamic driving force of the reaction is the formation of the chemical sulfur–sulfur bond between two hydrogen sulfide molecules adsorbed on two adjacent metal atoms in the key surface intermediate and elimination of hydrogen into gas phase. ‘‘Fingerprints’’ of diatomic sulfur adsorbed on the solid surfaces and dissolved in different solvents are studied. In closed vessels in adsorbed or dissolved states, this molecule is stable for a long period of time (weeks). A possible electronic structure of diatomic gaseous sulfur in the singlet state is considered. According to DFT/CASSCF calculations, energy of the singlet state of S2 molecule is over the triplet ground state energy for 10.4/14.4 kcal/mol. Some properties of gaseous diatomic sulfur are also investigated. Catalytic solid systems, both bulk and supported on porous carriers, are developed. When hydrogen sulfide is passing through the solid catalyst immersed in liquid solvent which is capable of dissolving sulfur generated, conversion of hydrogen sulfide at room temperature achieves 100 %, producing hydrogen in gas phase. This gives grounds to consider hydrogen sulfide as inexhaustible potential source of hydrogen—a very valuable chemical reagent and environmentally friendly energy product.

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The Molecular Mechanism of Low-Temperature Decomposition of Hydrogen Sulfide under Conjugated Chemisorption–Catalysis Conditions.

I. I. Zakharov, A. N. Startsev, O. V. Voroshina, A. V. Pashigreva, N. A. Chashkova, and V. N. Parmon

Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences.

Abstract

The molecular mechanism of interaction of two hydrogen sulfide molecules with the (CoIII−Ho)2S2(SH2)4 model active center containing occluded hydrogen was studied by the density functional theory method with the B3P86 hybrid exchange-correlation functional. The reaction was found to occur in the following elementary steps: molecular adsorption of hydrogen sulfide ⇒ dissociative chemisorption ⇒ S–S bond formation in the surface intermediate {2CoIII – (µ-S2) + 2H(ads)} with the release of the first hydrogen molecule into the gas phase H2(g) ⇒ the release of the second hydrogen molecule into the gas phase H2(g) ⇒ the formation of cyclooctasulfur in the reaction 4S2(ads) → S8(ads).

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