PROCEEDINGS
OF THE TOMSK ORDER OF THE OCTOBER REVOLUTION
AND ORDER OF THE RED BANNER OF LABOR
POLYTECHNIC INSTITUTE named after S. M. KIROV

Volume 253　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　1976

ENERGY TRANSFORMATION IN THE EARTH’S CRUST

AND HYDROCARBON FORMATION

A. A. VOROB'EV

§ 1. Introduction

The formation of oil and combustible natural gases is explained by means of hypotheses of the organic origin of these minerals, or of inorganic origin.

According to hypotheses of the organic origin of oil and gas, these minerals are obtained from organic matter under the conditions of its occurrence in the earth’s interior. The transformation of the initial substance may take place under the simultaneous action of heat, pressure, aqueous solutions, radiation, microorganisms, the catalytic influence of rocks, or some of the factors listed.

According to some hypotheses of inorganic origin, the chemical compounds that make up oil and gas were formed as early as the protoplanet, perhaps when the materials from which the planets were formed were in a plasma state. The hydrocarbons formed in the protoplanet then entered into the composition of the planet’s materials. During compression of the planet and its heating, the hydrocarbons were released and rose closer to its daytime surface, forming deposits.

According to other hypotheses, methane and more complex hydrocarbons are formed as a result of inorganic synthesis from carbon and hydrogen, under the action of the heat of magma and the catalytic influence of minerals [1] in the earth’s crust or upper mantle.

Earlier, hypotheses were proposed for the formation of petroleum hydrocarbons under the action of radioactive radiation. According to V. A. Sokolov, the initial product for the formation of petroleum hydrocarbons is organic matter. Under the action of radioactive radiation, decomposition of organic matter occurs and H₂, CO₂, CO, CH₄, C, O₂ are released. In the radiation field, a synthesis reaction also occurs, with the formation of carbon compounds which, by polymerizing, may turn into heavy hydrocarbons that enter into the composition of oil [2].

In some existing hypotheses, processes of obtaining oil from natural combustible gas are considered. In other hypotheses, the process of obtaining gas from oil is considered.

According to data [3], the process of gas formation is much more widespread in nature than the process of oil formation. Polymerization, complication, and weighting of hydrocarbon molecules under the influence of radioactive radiation, and also in the presence of certain catalysts and, in particular, clays, have been proven experimentally.

Oil is a complex mixture of various hydrocarbon and nonhydrocarbon...

hydrocarbon compounds that arise undergo changes and, ultimately, are destroyed in the lithosphere while interacting with the enclosing rocks, with underground waters, and with gases. Therefore it is necessary to carry out comprehensive geological–chemical studies of the entire coupled natural system: oil—rocks—waters—gases [4].

A particularly difficult problem in the geochemistry of oil is explaining the formation of oxygen- and sulfur-containing compounds in the composition of the asphalt–resin fraction of oils and bitumens.

Some proponents of the organic hypothesis point out that a satisfactory mechanism for the transformation of the original organic material into hydrocarbon mixtures has not yet been proposed, and that there are still no experimental data illuminating this process with sufficient completeness and clarity and with due consideration of geological data [1]. The results of astrophysical observations and the study of the chemical composition of meteorites indicate that in various regions of the Galaxy there occurs an abiogenic—that is, not connected with the vital activity of any organisms—synthesis of certain organic compounds of varying complexity. Molecules of water, methane, and ammonia have been detected in interstellar space. As a result of the subsequent abiogenic synthesis from these simple chemical compounds containing carbon, nitrogen, hydrogen, and oxygen, more complex organic compounds, including some biologically important ones, can also be formed.

Recently, with the aid of radio-astronomical observations, molecules of hydrogen cyanide and formaldehyde have been detected in space. From these compounds complex molecules of organic compounds can be formed, including the bases of nucleic acids and amino acids.

Of scientific interest is the problem of searching for and studying organic compounds in lunar rocks, closely connected with the problem of the origin of life in the Solar System and, in particular, the possibility of abiogenic synthesis of organic compounds on the Moon. There is practically no atmosphere on the Moon; therefore organic synthesis there may occur as a result of the interaction of the “solar wind” with inorganic compounds of lunar rocks in the surface layer.

The formation of organic compounds is also possible when meteorites fall on the Moon, under the action of ultraviolet radiation, in the plasma of electrical discharges.

Under the action of these same factors and of large temperature gradients, not only addition reactions but also decomposition reactions of organic compounds may occur in the surface layer of the Moon. Analysis of samples of lunar rock delivered by American astronauts showed an extremely low carbon content in them. Rock samples taken by the Soviet station “Luna-16” down to a depth of 350 mm may give qualitatively different results. According to some hypotheses, abiogenic synthesis of organic compounds could have occurred at an early stage of the Moon’s development. If this hypothesis is correct, then in the deep layers of the lunar crust organic compounds may be preserved at a higher concentration than on the surface. In the study of meteorites, especially the so-called carbonaceous chondrites, hydrocarbons, sugars, fatty acids, and amino acids have been isolated from them. It is assumed that at least some of the listed organic compounds formed in space by an abiogenic radiochemical pathway, under the action of energy sources in the form of cosmic rays, ultraviolet radiation, and high temperatures [5].

The hydrocarbons that form oil and combustible gases have a high calorific value. Considerable energy is stored during

formation of hydrocarbons. The origin of this energy, contactless methods of supplying it to the volume where reactions occur and energy is stored, had not previously been developed in hypotheses on the origin of gas and oil.

From the content of the organic hypotheses one may suppose that the energy stored in oil owes its origin to the vital activity of organisms, from whose remains, under the catalytic action of solid, liquid, and gaseous minerals, as well as certain microorganisms, oil was formed at relatively low temperature and pressure in sedimentary rocks.

According to hypotheses of inorganic origin, it must be thought that the source of the energy expended on the formation of the molecules of compounds that make up oil is the heat of magma.

According to other hypotheses, methane and more complex hydrocarbons that go into the formation of gas and oil were formed already in the protoplanet. Then, from these compounds, under the action of heat in the depths of the planet, natural combustible gases and oil are formed \[1,4\].

The extraction of combustible gases and oil from the Earth and their combustion is a way of pumping out and consuming the planet’s energy reserves.

In the cycle under consideration there is no external source for replenishing the planet’s energy reserves from cosmic space. Taking into account the well-known difficulties in using hypotheses of the organic and inorganic origin of oil to solve many of the most important stages of this problem, we have proposed a hypothesis of the formation of carbon compounds that are components of oil and gas in plasma, which can form in the Earth’s interior.

Many difficult questions in describing the processes of formation of natural gases and oil can be solved if one proceeds from the hypothesis of their formation as a result of the synthesis of organic compounds in the plasma of electric discharges.

§ 2. Chemical reactions of synthesis and decomposition of hydrocarbons in electric discharges

The conditions for the course of various reactions in a discharge have been studied qualitatively. Quantitative relations for calculating the course of chemical reactions have not yet been investigated.

At the very high temperatures that develop in a spark electric discharge, molecules decompose into atoms and radicals. In the discharge plasma the temperature of the ionic, and especially of the electronic, gas may considerably exceed the molecular temperature. Various types of electric discharges in gases, liquids, solids, and plasma have been studied. In an electric discharge it is possible to obtain a high temperature of the ionic and electronic gas, a high concentration of energy, and to carry out chemical and nuclear reactions.

Then, entering a region of the discharge with a lower temperature and interacting with the initial and newly formed molecules of chemical compounds, the active particles may enter into new chemical reactions. Therefore there arises the complex task not only of initiating the beginning of reactions in the discharge, but also of creating conditions for obtaining the desired product, eliminating reactions between intermediate products. For hydrocarbon synthesis reactions, the production of atomic hydrogen in a glow discharge is probably essential. Chemical reactions proceeding at constant pressure and sufficiently high temperature, as is known, are accompanied by a decrease in the isobaric potential—

(G) and proceed to a state of equilibrium characterized by the minimum value of \(G\). To achieve a degree of dissociation of molecular hydrogen into atoms equal to 0.5 at a pressure of 0.001 atm, the hydrogen must be heated to approximately 2600°K. At a temperature of 800°K, the equilibrium mixture contains only about \(10^{-8}\%\) atoms.

In a glow discharge, at gas temperatures substantially below 800°K, it is already possible to obtain practically complete dissociation of hydrogen, i.e., concentrations of atoms that are superequilibrium for the given temperature. The cited possibility of obtaining superequilibrium concentrations of products is connected with the nonisothermality of the discharge plasma and with the existence, alongside the relatively low temperature of the molecular gas, of a very high temperature of the electron gas. It is this temperature difference within the gas that makes it possible to realize a nonequilibrium state.

In an arc electric discharge, which is characterized by a higher current density than a glow discharge, the molecular temperature increases, while the temperature of the electron gas decreases. In an arc discharge, reactions of synthesis of nitrogen oxides occur, as well as the electrocracking of methane to acetylene according to the equation: \(2\mathrm{CH}_4 = \mathrm{C}_2\mathrm{H}_2 + 3\mathrm{H}_2\). For this endothermic reaction, the energy consumption in the arc is about 10 kW·h per 1 kg of acetylene [7].

Plasma burning in the voids of a layered or porous dielectric has a polymerizing effect. In it, liquid and solid products are formed from low-molecular-weight hydrocarbons.

As is known, oil and natural gases often occur in porous sedimentary rocks, in which the indicated chemical reactions may proceed in a barrier discharge [9, 10].

For chemical kinetics in a gas discharge, the basic proposition is that the rate of a chemical reaction in a given type of electric discharge is proportional to the power of the discharge [6].

A change in power in the discharge circuit should not be accompanied by a change in the type of discharge, since the proportionality coefficients indicated in the cited rule for one and the same reaction, but in different types of discharge, may have different values. For example, a glow discharge at low pressure is very ineffective with respect to the reaction of converting methane into acetylene, whereas an arc at medium pressures is very effective. Therefore, the transition of a glow discharge into an arc is accompanied by a sharp increase in the effectiveness of the process.

The main difficulty in studying the kinetics of reactions in a discharge is that it is practically impossible to determine precisely the time during which the reaction proceeds, because the reaction volume is not defined. This difficulty is overcome by including the volume \(V\) of the reaction zone in the rate constant, i.e., by replacing, in the kinetic equations, the reaction time by a quantity proportional to it—the reciprocal volumetric velocity of gas passage through the reaction vessel \(\left(\dfrac{1}{V}\right)\) [6].

In the Earth’s interior, it is possible for various physical processes to occur in which various kinds of energy are transformed into electrical energy, with the formation of high voltages and the occurrence of electric discharges in rocks. Classical electrical engineering, based on the macroscopic electrodynamics of Faraday–Maxwell, studies electromagnetic interactions in isotropic media and does not take into account the atomic structure of bodies and electricity, interatomic interactions, or defects in the structure of solids. The production, transmission, distribution, and use of electric power are based on the laws of the classical macroscopic theory of electricity.

Great prospects for the generation of electric charges under various conditions are presented by the electronic and ionic properties of anisotropic media and defective structures. The magnetic, electrical, and semiconductor properties of solid and liquid bodies and of plasma receive their explanation when the microscopic properties of the medium and structural disturbances are taken into account. In semiconductor energy technology, phenomena of electronic interactions in a solid body, occurring at the boundary between a metal and a dielectric, are beginning to be used—in thin semiconductor films on metals, in finely dispersed metal–dielectric mixtures, and in semiconductor–dielectric systems.

The electronic and ionic properties of solids determine their photoelectric and thermoelectric properties, which find applied uses. Previously known phenomena of contact electrification, the appearance of charges during the passage of elastic waves and plastic deformation of solids, etc., are being intensively studied. Such systems and contacts are also possible in the Earth’s interior.

Interesting research is being conducted on the electronic and ionic properties of the liquid and gaseous states of matter and of phenomena at phase boundaries. Studies of electrical double layers at the boundary surfaces of contact between solid, liquid, and gaseous states lead to practically interesting consequences: the direct conversion of the energy of chemical fuel into electricity, the development of electrochemical current sources, and new methods of electrochemical synthesis. Such phenomena are also possible in the Earth’s interior.

In the USSR, the USA, and other countries, models of electrochemical current sources have been created that operate on gaseous hydrogen and oxygen, with an efficiency of direct conversion of the chemical energy of fuel into electricity reaching 80%.

It is assumed that electric spark discharges at high voltage, or arc and glow discharges at low voltage (up to 20 V), are formed in the Earth’s interior as a result of various physical phenomena observed in laboratories, or in the same way as thunderstorm phenomena in the atmosphere.

Under atmospheric conditions, in a spark discharge in a gas, the concentration of energy in the plasma may prove to be only one order of magnitude lower than in a nuclear explosion. In a spark discharge in a liquid, the power released in the plasma sphere reaches hundreds of megawatts. The plasma formed in the discharge has a temperature of \(10^4—3\cdot10^4\ ^\circ\mathrm{K}\). The particle concentration is \(10^{20}—10^{21}\ \mathrm{cm}^{-3}\); the pressure in the plasma reaches \(10^2—10^4\ \mathrm{kg}/\mathrm{cm}^2\), and the energy density is \(10^2—10^3\ \mathrm{J}/\mathrm{cm}^3\).

Electric currents flow in the Earth’s interior. A break in an electric-current line will be accompanied by the emergence of an electric arc; the existence of plasma in the arc is determined by the conditions in the circuit. The flight of a high-energy particle is also accompanied by the formation of plasma in the particle’s track. Each individual one of the indicated phenomena of plasma formation lasts only a short time, but, taking into account the duration of the Earth’s geological history and its volume, it may be considered that the total time of plasma existence and the possibility of plasma processes occurring are large. The transfer to underground conditions of the phenomena of electrification and plasma formation observed in the atmosphere, on the Earth’s surface in nature, and in production is still a hypothesis. Discharges in the Earth’s interior have not yet been observed. However, there are no physical grounds for prohibiting such a hypothesis [7, 8].

With the formation of high-temperature plasma and poor heat removal in the Earth’s interior, thermonuclear processes may possibly occur.

§ 3. Formation of Oil and Gas in Plasmochemical Reactions in the Earth's Interior

The origin of oil and gas according to the organic hypothesis is explained by the action of various external factors on organic matter in the process of petroleum formation. Among such factors determining the process of petroleum formation, high temperature, pressure, microflora, the catalytic action of a mineral or biological medium, radioactivity, salinity, the action of water, and so forth are advanced.

Hypotheses of petroleum formation differ from one another by the hypertrophied role of some single feature: for example, temperature, the action of radioactive radiation or microflora, and so forth [1]. In the plasmochemical hypothesis, the geochemical setting of the formation of oil and gas is preserved. The quantity of energy necessary for a chemical reaction to proceed is introduced into the natural reaction volume and into the discharge plasma that is formed. The energy is introduced in a clean, contactless way, from the electric field, by means of an electric discharge. In this, the natural conditions of the geochemical reactor are preserved. According to our hypothesis, to the previously considered factors ensuring the progress of the process of transformation of organic matter into oil or gas, it is proposed to add the chemical processes occurring in reactions of organic synthesis in the plasma of electric discharges. The reaction is sustained by the supply of energy from external sources. The absence of energy sources was a weak point in the preceding hypotheses. The plasmochemical reaction itself may proceed in the organic matter itself and with its participation. According to the organic hypothesis of petroleum formation, petroleum hydrocarbons are reduced carbon compounds [1].

The mandatory conditions of petroleum formation are considered to include the presence of a geochemical reducing environment in sedimentary rocks. The opinion has been expressed that, for the formation of oil, the main factor is the oxidative transformation of organic matter in sedimentary rocks. According to the plasmochemical hypothesis, the formation of hydrocarbons is possible by way of dehydrogenation and subsequent polymerization of the hydrocarbons formed in the plasma of an electric discharge [7]. The initial substance in such a plasmochemical cycle may be the organic matter present in sedimentary rocks. At deeper stages of metamorphism of this substance, gaseous products are formed and, in particular, methane. Methane in the discharge plasma may undergo partial dehydrogenation, leading to the formation of free radicals, which, combining with one another, form acetylene, ethylene, and various gaseous and liquid hydrocarbons. Reactions for the formation of acetylene from methane in a discharge plasma as a result of polymerization are widely used for the industrial production of acetylene [7]. Thus, plasmochemical processes in gases can supplement the hypothesis of the organic origin of oil in the Earth's interior, removing part of the difficulties encountered by these hypotheses in explaining the formation of liquid oil and especially its compounds containing sulfur, nitrogen, oxygen, and also metals: vanadium, molybdenum, and others.

Plasmochemical processes permit the corresponding reactions to occur and compounds with carbon of the above-listed and other elements to be obtained [7].

From experience with high-voltage electrical oil-filled apparatus, for example transformers and oil circuit breakers, it is known that an accumulation of sludges is observed in their tanks. These products are formed as a result of the polymerization and oxidation of oil in the plasma of a silent discharge.

The process of sludge formation in oil-filled high-voltage oil apparatus proceeds rather rapidly. Over several years of being under voltage, in the presence of corona discharge, a considerable amount of sludge accumulates.

Under the action of electrical discharges in solid polymers at elevated temperatures of 100–200°C, electrothermal destruction occurs. Under the action of fast electrons from the discharge, destruction of the polymer macromolecules is also probable, with the formation of excited paramagnetic molecules—free radicals. At high temperatures free radicals intensively recombine with one another or chemically interact with the surrounding unsaturated molecules of polymers and dissolved gases. Consequently, the formation in the discharge of new chemical bonds may also occur simultaneously, leading to a change in the mobility of polymer macromolecules in thermal motion [11].

In [12] the stability of liquid dielectrics in an electric field of 25 kV/mm was investigated. In such a comparatively high field, gas evolution was observed in a layer 0.1 mm thick. Aromatic hydrocarbons proved to be more stable than hydrocarbons of the methane or naphthene series [13].

According to experimental data, spark electrical discharges cause predominantly destruction, decomposition of polymers, while glow discharges cause cross-linking of hydrocarbons, their polymerization.

Known laboratory and practical data lead to the conclusion that during the movement of loose bodies—coal dust, flour, sugar, cement, and others—glow discharges and, rarely, spark discharges are observed. It may be assumed that in sedimentary finely dispersed rocks, for example in sandy-clayey strata of sedimentary rocks at low moisture content and high temperature, when the particles do not coalesce but may detach from one another, their charging and a glow discharge between them occur. In the plasma of a glow discharge, a reaction of hydrocarbon formation, their cracking or dehydrogenation, and then cross-linking of molecular residues and formation of molecules of heavy hydrocarbons take place.

In this case, electrification of particles in sediments will occur as a result of their displacement by gravitational forces or during tectonic phenomena. Indicating the cause of plasmochemical reactions in sedimentary rocks supplements the hypotheses of the organic origin of oil. The hypothesis gives a mechanism for the processes by which chemical reactions proceed and a source of energy input for such a reaction from the plasma of a glow electrical discharge. According to this hypothesis, in finely dispersed sedimentary rocks containing organic matter or carbon and hydrogen in compounds, lying under conditions in which small displacements of particles relative to one another and low moisture content are possible, discharges may arise. In the discharge plasma a reaction of synthesis of molecules of hydrocarbon compounds may occur.

The German volcanologist F. Wolff earlier suggested that oil specialists pay attention to the possibility of the synthetic occurrence of petroleum hydrocarbons from gases ordinary for volcanoes, for example carbon monoxide and hydrogen, according to the schemes:

\[ 2\mathrm{CO}+2\mathrm{H}_2=\mathrm{CH}_4+\mathrm{CO}_2+q, \]

\[ \mathrm{CO}+3\mathrm{H}_2=\mathrm{CH}_4+\mathrm{H}_2\mathrm{O}+q, \]

where \(q\) is the thermal equivalent [14].

Berthelot, as early as 1863, carried out reactions in a spark discharge with oxygen compounds of carbon and hydrogen in mixtures of \(\mathrm{CO}+\mathrm{H}_2\). As a result of plasmochemical reactions, various gaseous and liquid hydrocarbons were obtained [7].

According to the plasmochemical hypothesis, the formation of methane from hydrogen and carbon can proceed by the same reactions as under thermochemical action. Hydrogen may be formed during the decomposition of a number of hydrocarbons or of water, or of other hydrogen-containing compounds.

In the field of geochemical study of petroleum gases and combustible dry gases, a difficult task is to explain the presence in their composition of admixtures of metamorphic and juvenile components, CH₄, CO₂, and admixtures of heavy hydrocarbons, organometallic compounds, compounds containing sulfur, oxygen, etc.

Plasmochemistry explains the appearance of these carbon compounds both by inorganic synthesis and by the destruction of organic matter to the gaseous state, the decomposition of these gases, and the polymerization of the products of decomposition of organic substances in the plasma of an electric discharge [7].

Supporters of the organic and inorganic hypotheses of petroleum formation alike do not allow for the possibility of oil and gas formation in crystalline rocks. According to the plasmochemical hypothesis, plasma can also arise in the crystalline phase, and, consequently, hydrocarbons included, for example, in crystalline carbonate rocks or other minerals and dielectric rocks may also be formed.

In minerals and rocks a metamict state is observed. In the thickness of good dielectrics, for example mica, residual tracks from the passage of high-energy nuclear particles are observed [15].

In the plasma formed in the track of a high-energy particle, chemical reactions are also possible. In the past geological history of the Earth, when greater fluxes of cosmic rays reached its surface than at present, the total volume of plasma obtained in this way could have been considerable. In this case it is necessary to take into account chemical reactions not only in the plasma, but also radiation-chemical processes.

In the process of formation of hydrocarbons and oils in plasma, the geological conditions of occurrence may have a substantial influence. The presence of zones of reduced or elevated pressure in an oil-and-gas-productive bed creates conditions for the migration of gaseous and liquid hydrocarbons.

A. I. Kravtsov points to the confinement of gas and oil fields, in particular in Azerbaijan, to zones of deep faults, and to their role in the formation of these fields [1]. The formation of faults in rocks must be accompanied by electrification of the edges of the fault walls. On the large new surfaces formed during a fault, an electric charge of great magnitude appears and enormous energy is released in the discharge. The subsequent destruction and crushing of pieces of rock is also accompanied by electrification of the surfaces, with the release of energy and the formation of plasma in an electric discharge and by luminescence. These considerations show that products of plasmochemical reactions may form in the fault zone, and, during the formation of the fault, large electric discharges in this region could cause earthquakes and seismic phenomena. It is often observed that a bed of bituminous rock is cut by veins of quartz, now milky-white in color, now colored brownish tones. The coloration of quartz is the result of the formation in the quartz of color centers under the action of radioactive radiation. When colored quartz is heated to a temperature above 100°C, the color centers disintegrate and the quartz becomes decolorized [16]. The presence of color centers in quartz or other minerals indicates that the temperature of these minerals after their coloration remained low for a long time, and that the electrical resistance of the dielectrics was

high. Under such conditions, the accumulation of charges in quartz [16] and an electrical discharge are possible. Veinlets of bitumen are sometimes observed between rock layers, and calcite, as a rule, is not colored by bitumen. In deposits containing a small amount of bituminous substances, the latter color various formations in calcite: veinlets, concretions, etc. Calcite is a material of high resistance. In it a volume charge of high concentration is formed, and electric fields of up to \(10^8\) V/cm arise. Such a field in the surrounding medium can cause the occurrence of electrical discharges.

Rocks are encountered that contain pointlike scattered inclusions of oil. These include bituminous limestones, bituminous siliceous rocks, etc.

Proponents of the organic theory assume that droplets of oil formed in such strongly consolidated rocks could not have been squeezed out through capillary channels. Therefore, after their oxidation, the oil droplets turned into bitumen [17].

The regularities of formation of dispersed oil and bitumen in the rocks listed also agree with the hypothesis of the formation of hydrocarbons and oil droplets in electrodeless discharges that arose in rocks located in a dielectric.

According to the plasmochemical hypothesis, it is assumed that the formation of hydrocarbons occurs in an electrical discharge as a result of inorganic or organic synthesis, which can also arise in crystalline rocks. Discharges can pass in the earth’s crust to a depth of 15 km. Accumulations of charges and electrical discharges in the earth’s crust are most probable to a depth of 5 km. Accumulation of charges in the earth’s crust can also occur as a result of the action of tectonic processes, atmospheric discharges, and phenomena in near-Earth space.

Discharges may be of different power. Discharges in soft rocks are characterized by a small amount of energy; discharges in hard rocks, by a large energy release, of the order of the energy of a nuclear-bomb explosion. In such a case earthquakes may also occur. In the hypothesis under consideration it is assumed that oil-and-gas formation, having begun in plasma in the distant times of the planet’s formation, continues at the present time, since in the schemes considered it is assumed that electrical discharges in the earth’s crust may take place even in our time.

The proposed hypothesis of oil-and-gas formation explains the origin of energy sources ensuring the course of energy-intensive reactions of hydrocarbon synthesis and their subsequent dehydrogenation and polymerization, i.e., it considers the question of the plasmochemistry of the origin of gas and oil. This hypothesis does not concern questions of petroleum geology. In the presence of electrical discharges with the release of a large total amount of energy and the explosive action of the discharge, changes are possible in the structure of the surrounding geological setting and changes in the conditions of migration and accumulation of oil and gas in this region. Thus, electrical discharges may be the cause of plasmochemical reactions, seismic processes in some region, and the migration of oil or gas. It is noted that the main resources of oil and gas calculated up to the present time are confined to deposits lying to a depth of 5 km. To these same depths extend the foci of small earthquakes. At these same depths the occurrence of electrical discharges in the earth’s crust is probable.

Diagram 1 presents a possible sequence of formation of oil or gas during inorganic or organic synthesis in an electrical discharge in the earth’s interior.

The plasmochemical hypothesis of oil-and-gas formation allows the cre—

inorganic

[Inorganic substances
(inorganic compounds
of the Earth’s crust)]

↓

[Inorganic synthesis in
plasma.
Formation of organic
compounds containing
in their molecules atoms of
hydrogen, carbon, oxygen,
nitrogen, sulfur, phosphorus,
and metals]

↘

[Natural gas
(methane and other light
hydrocarbons)]

↓

[Plasmochemical transformations
of natural gas in plasma
(dehydrogenation of methane and
synthesis of more complex
compounds)]

↓

[Oil:
hydrocarbons of various classes,
oxygen-, sulfur- and nitrogen-containing
compounds, resins,
asphaltenes, carbenes, carboids,
metal-organic
compounds]

↓

[Secondary plasmochemical
transformations of oils
(changes in the ratio
between the components of oil).
Formation of oils
of various types]

organic

[Primary organic
substances (remains
of living organisms)]

↓

[Microbiological processes
and transformation of buried
matter at various stages
of evolution of sedimentary rock.
Plasmochemical transformations
of organic substances
(formation of methane,
higher hydrocarbons and
non-hydrocarbon compounds)]

↙

[Natural gas
(methane and other light
hydrocarbons)]

↓

[Plasmochemical transformations
of natural gas in plasma
(dehydrogenation of methane and
synthesis of more complex
compounds)]

↓

[Oil:
hydrocarbons of various classes,
oxygen-, sulfur- and nitrogen-containing
compounds, resins,
asphaltenes, carbenes, carboids,
metal-organic
compounds]

↓

[Secondary plasmochemical
transformations of oils
(changes in the ratio
between the components of oil).
Formation of oils
of various types]

Diagram 1. Plasmochemical hypotheses of the formation of oil and natural gas in the Earth’s crust.

creating artificial conditions in the earth’s crust, when, in the plasma of a gas discharge in the Earth’s interior, caused, for example, by pulsed discharges from a pulsed-voltage generator, hydrocarbons and petroleum may be formed.

The previously proposed hypotheses for the formation of hydrocarbons and petroleum did not propose creating conditions for the artificial synthesis of hydrocarbons and petroleum in the earth’s crust.

Modern technology has the capability of forming, in the Earth’s interior, high-intensity electric fields in which electrical discharges and plasma will arise.

Thus, there are possibilities for modeling the conditions of petroleum formation in the Earth’s interior.

§ 4. Conclusion

Under laboratory, natural, and production conditions, the phenomenon of surface and volume charging of dielectrics and of the surfaces of conductors situated in a nonconducting medium, and the formation of electric fields, is observed. When the intensity of the electric field reaches the value of the electric strength of the medium, its breakdown and the neutralization of charges occur. The energy of the electric field is expended on the mechanical destruction of bodies, the heating and melting of matter, the kinetic energy of flying fragments, the emission of light and heat, acoustic phenomena, etc. In the discharge channel a plasma is formed, in which numerous physical and chemical processes, including nuclear reactions, may take place.

The phenomenon of charging of a dielectric under known conditions constitutes a concentration of energy in an electric field.

The formation of plasma is also observed at the point where an electric-current circuit is broken.

It is assumed that the phenomena of charge accumulation and the occurrence of discharges may also take place in the Earth’s interior during tectonic processes in dielectric rocks and cavities. In the Earth’s interior there may also be specific conditions of electrification other than those known from laboratory practice. Spark discharges in the Earth’s interior, when much energy is released in the spark channel, may initiate earthquakes and seismic processes.

Glow and arc discharges in the pores of rocks may cause plasma-chemical reactions to proceed. Sections of the earth’s crust in which such phenomena occur may be regarded as a plasma-chemical reactor. Comparative estimates make it possible to assume a high integral productivity of such a generator over the geological history of the Earth.

It is of interest to establish the geological and physical conditions under which the processes of the appearance of free charges, their accumulation, the passage of an electric discharge in a dielectric, and processes in the discharge plasma are possible.

The plasma-chemical hypothesis proposes that the formation of hydrocarbons should occur in places where discharge plasma arises, or plasma in tracks of high-energy particles. In the earth’s crust such regions may be fault zones and areas where various tectonic phenomena occur, causing the displacement of rock masses, their destruction, and the formation of new surfaces on which free charges arise, leading to electrical discharges. In regions where deposits of finely dispersed materials are present, charging of surfaces occurs at the point of contact between particles.

particles and the formation of double layers. Under such conditions, the formation of high-intensity electric fields, microdischarges, and the occurrence of plasma-chemical reactions with the formation, for example, of hydrocarbons or other organic or inorganic compounds is possible. This idea is not contradicted, for example, by the existence of oil and gas deposits in sandy deserts or by the presence of deposits of asphalt sands on the Athabasca River in western Canada. It is known that the latter case presents considerable difficulties of explanation in petroleum geology [18].

Among the regions in which a large number of thunderstorm discharges from clouds to the Earth’s surface are observed are mountainous and piedmont regions and the surfaces of large bodies of water [19]. Large currents, measured in millions of amperes, flowing in near-Earth space under the action of the Earth’s magnetic field, are displaced into the regions of the magnetic poles [19]. The possible induction currents in the Earth and the high potentials caused by them must also, probably, be concentrated mainly in the polar regions and may participate in oil-and-gas formation in the Arctic and Antarctic and in northern regions according to one of the schemes mentioned above.

The formation of electric charges upon irradiation of dielectric rocks and minerals by radioactive radiation, and discharges in them upon the accumulation of free charges, suggest that these processes occur in places near the occurrence of radioactive ores. The converse conclusion is also valid: that near oil and gas deposits it is possible to find radioactive ores, the radiation of which has caused the processes of formation of hydrocarbons, oil, and gas.

Finally, the formation of tracks along the paths of high-energy particles will occur in rocks containing radioactive ores and will be confined to the places of their deposits. The formation of radioactive nuclei in the Earth’s crust is also possible during the passage of fluxes of neutrinos, protons, neutrons, and gamma quanta coming from space. These processes may occur throughout the Earth, but the number of such nuclei will be relatively small and cannot explain the formation of the known oil reserves [20].

In the plasma of an electric discharge, various reactions may proceed: cracking of hydrocarbons, hydrogenation and dehydrogenation, polymerization of hydrocarbons in gaseous, vapor, liquid, and solid phases, synthesis and various transformations of oxygen-containing, nitrogen-containing, halogen-containing compounds, and other reactions of synthesis and decomposition of compounds. This makes it possible to describe, by means of plasma chemistry, the formation of the chemical compounds that make up natural combustible gases, oil, minerals, and rocks.

All organic compounds, including saturated hydrocarbons—for example, methane—polymerize in an electric discharge. Methane decomposes in the discharge as a result of rupture of the C—H bond, i.e., the occurrence of a dehydrogenation reaction.

With partial rupture of C—H bonds, methane is dehydrogenated and free radicals are formed; these, combining with one another, form acetylene, ethylene, and other gaseous and liquid products. Polymerization of saturated hydrocarbons in a discharge occurs as a result of the combination of free radicals [7].

In the plasma of a stationary electric discharge, reactions of synthesis of organic compounds and reactions of their decomposition may occur. Subsequently, among the products of the decomposition reaction in the plasma, synthesis reactions and formation of other chemical products, different from the products of the first-order synthesis reaction, may again take place. In plasma-chemical technology, during the burning of a stationary discharge, an essentially important operation is the timely remo-

the removal of the necessary product from the volume where the reaction occurs and the lowering of its temperature to the value at which the product is in a stable or metastable state. In a pulsed, short-duration electrical discharge in the Earth’s crust, the need for the indicated technological operation may disappear. With the extinction of the pulsed discharge, the chemical reactions cease and the formed product is preserved—for example, methane or the products of its subsequent transformations in the electrical discharge. Repeated action of electrical discharges will be accompanied by the formation of new chemical compounds of carbon with other elements, depending on the conditions under which the reaction proceeds.

In the plasma of an electrical discharge, or in the plasma in the track of a high-energy particle, many reactions can be carried out, and many compounds of carbon with metals and metalloids can be formed, including those that cannot be obtained by thermochemical reactions and the use of catalytic action.

In the scheme under consideration, the formation in plasma of molecules of chemical compounds that are constituents of natural gases and petroleum is assumed, as well as their residence in the gaseous phase. During subsequent discharges, condensation occurs from the gaseous stage into a droplet-liquid state, followed by migration and accumulation of the liquid in traps in the Earth’s crust.

Plasmochemical reactions for the formation of chemical compounds that are constituents of petroleum may begin with the synthesis of carbon and hydrogen in their free state. They may also begin first with the decomposition, in an electrical discharge, of carbon- or hydrogen-containing organic or inorganic compounds, and only then with the synthesis of the elements that have formed, free radicals, or products of destruction of the molecules of the initial compounds [20].

The proposed plasmochemical hypothesis for the formation in the Earth’s crust of molecules of compounds that are constituents of combustible gases and petroleum does not exclude other methods and pathways of gas and petroleum formation, including the pathways indicated by organic or inorganic hypotheses. Plasmochemical reactions may come into effect at some stage of the processes also described by organic hypotheses of petroleum formation—for example, from the stage at which, in the process of decomposition of organic matter, methane, or carbon dioxide and hydrogen, etc., has been obtained. Subsequently, when hydrogenation, polymerization, cyclization, and other reactions for obtaining complex organic compounds occur in the plasma. According to the inorganic hypothesis of the formation of petroleum or gas [8]:

a) hydrocarbons are released from magma.
b) hydrocarbons are synthesized from C and H₂ under the catalytic action of rocks.

In the discharge plasma, the synthesis of methane according to Berthelot and the subsequent possible dehydrogenation of methane are possible.

According to the organic hypothesis of petroleum formation, pathways of destruction from solid organic matter to methane have been described, but the pathways and sources of energy for the polarization of methane into petroleum and asphalts have not been indicated. Plasmochemistry indicates pathways for obtaining a liquid product from solid or gaseous organic matter.

According to organic theories, the process of transformation of the organic residue of seas is stimulated by: temperature, pressure, microflora, the catalytic action of minerals (clays) and microflora, radioactivity, and water salinity. In the proposed plasmochemical hypothesis, to this list of factors, on equal grounds, is added plas-

in an electrical discharge. The author is grateful to Doctor of Geological and Mineralogical Sciences G. L. Pospelov, Prof. A. V. Aksarin, Doctor of Physical and Mathematical Sciences I. A. Tikhomirov, Prof., Doctor of Technical Sciences S. I. Smolyaninov, Docent V. S. Dmitrievsky, and others, who familiarized themselves with the manuscript and, by their advice, objections, and comments, contributed to the development of the problem under consideration.

REFERENCES

1. A. I. Kravtsov. Fundamentals of the Geology of Combustible Minerals. Vysshaya Shkola Publishing House, Moscow, 1968.

2. V. A. Sokolov. In: The Origin of Petroleum. Publishing House of the Academy of Sciences of the USSR, Moscow, 1951.

3. N. O. Prod, N. A. Eremenko. Fundamentals of the Geology of Oil and Gas. Moscow State University Publishing House, 1960.

4. M. F. Dvali, N. A. Eremenko. In: The Origin of Oil and Gas. Gostoptekhizdat, Moscow, 1960.

5. A. Mukhin. Newspaper Pravda, 24 September (1970).

6. Course of Physical Chemistry. Edited by Corresponding Member of the Academy of Sciences of the USSR, Prof. Ya. I. Gerasimov, Vol. II, “Chemistry,” Moscow, 1966.

7. D. N. Andreev. Organic Synthesis in Electrical Discharges. Publishing House of the Academy of Sciences of the USSR, Moscow–Leningrad, 1953.

8. A. A. Vorob'ev. On the question of the initiation of earthquakes by underground thunderstorm phenomena. In: Electrophysical Apparatus and Electrical Insulation. Energiya, Moscow, 1970.

9. A. A. Vorob'ev. On the possibility of electrical discharges in the depths of the Earth. Geology and Geophysics, No. 12 (1970).

10. A. A. Vorob'ev. The Possibility of Plasmochemical Reactions in the Earth's Depths and the Formation of Oil and Combustible Gases. Tomsk, Tomsk State University Publishing House, 1970.

11. M. P. Voitikov, V. L. Makemov, R. N. Kharichkina. In: Ionization Aging, Corona Resistance... Moscow, TsNITI, 1963.

12. V. T. Renne, P. N. Bondarenko. In: Ionization Aging, Corona Resistance... Moscow, TsNITI, 1963.

13. V. T. Renne, Tsui Si-Sing. ZhTF, 26, issue 5, 1070 (1956); 27, issue 7, 1462.

14. S. A. Kovalevsky. In: The Origin of Oil and Gas. Gostoptekhizdat, Moscow, 1960.

15. B. V. Budylin, A. A. Vorob'ev. The Action of Radiation on Ionic Structures. Moscow, Gosatomizdat, 1962.

16. A. A. Vorob'ev. Color Centers in Alkali-Halide Crystals. Tomsk, Tomsk State University Publishing House, 1968.

17. In: The Origin of Oil and Gas. Moscow, Gostoptekhizdat, 1960.

18. I. M. Imyanitov, K. S. Shifrin. UFN, 76, No. 4, 593 (1962).

19. N. B. Vassoevich, Yu. N. Korchagina, N. V. Lopatin, V. A. Chernyshev. Vestnik MGU, No. 6, 3 (1969).

20. S. N. Raizer, D. G. Mel'nik, V. D. Parkhomenko. Plasma in Chemical Technology. Tekhnika, Kiev, 1969.