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Igor I. Kondrashin
Dialectics of Matter
Dialectical Genesis of Material Systems
The following organisational level of systemic formations of Matter unites all the qualitative variety of inorganic elements. To proceed from requirements of the law of augmentation of increase of functions per a unit of time owing to the limitation of spatial displacement, the appearance of systemic formations of the present sublevel was taking place mainly on the planetary bodies of the Universe.
The chemical compound of the elements of Matter, but more precisely, the chemical connection between functioning units of the sublevel C (that is atoms) serves as a forming base of structures of the level D. As a result of that fng. units of the new level (molecules) are being formed, each of them has its strictly definite fnl. features, most of which have been studied well by nowadays.
Let us consider briefly the mechanism of the functioning of the chemical connection.
All numerous chemical processes are going on as a result of the mutual re-grouping of atoms being accompanied by breaks of old fnl. links between them and the generation of new ones within the limits of structures of fnl. cells of elements of the present sublevel. There are no chemical reactions during which the links between fnl. cells, occupied by different atoms, would not modify. The electronic covers of atoms, having entered into contacts with each other, are responsible outwardly for this. Therefore we can safely affirm that it is their principal fnl. characteristic, their function.
A contiguity of interacting atoms being accompanied by partial recovering of their electronic covers is the necessary condition for the beginning of a chemical connection between them. As an example, let us examine the mechanism of the organisation of the simplest by structure formation of the present level - a molecule of hydrogen.
The electron in an atom of hydrogen occupies a definite power level, which is the lowest if the atom is not excited and is situated in an isolated condition. During the closing in of two atoms their electrons experience attraction from the sides of both atoms, which is increasing with the decrease in the distance between them. However, at a certain phase the closing in of the atoms can be suspended owing to the influence of repulsion forces between the electrons, as each of them has the negative charge. Therefore a further interaction of the two atoms will be taking place depending on the characteristic of the spins of their electrons. Electrons with parallel (equally directed) spins
( )are pushing off from each other, and electrons with antiparallel spins ( )are closing in, tightening into an electronic couple. This principle was already mentioned by us during the description of the construction of atomic orbitals of electronic covers of atoms.
Consequently, during the closing in of the two atoms of hydrogen, two electrons, the spins of which are antiparallel, can enter into the space between the atomic nuclei. As a result a stable diatomic systemic formation appears - a molecule of hydrogen H2, fnl.cells of which are filled in by fng. units of the sublevel C - atoms of hydrogen. The total kinetic energy of the system of two atoms is decreasing owing to its absorption during the generation of the system itself in the way of transformation of a part of the kinetic energy of separate atoms into the potential energy of connection of the molecule. The nuclei of connected atoms remain at a strictly definite distance and are performing oscillations relative to each other. The balanced internuclear distance, having the name 'a length of chemical connection', for a molecule H2 is equal 0,74 at radii of hydrogen atoms 0,53 . A field of space between atomic nuclei, where the probability of finding an electronic couple is at maximum, constitutes a molecular orbital. As we have elucidated, two electrons with parallel spins cannot be situated there simultaneously. Therefore during the closing in of two atoms, the electrons of which have parallel spins, a molecule of hydrogen cannot be formed.
A chemical connection can arise both between separate atoms of the periodical system of the sublevel C and between more complex fng. units - molecules, ions, radicals... But in any case at its foundation a method of valency links is used, the principle postulate of which is that the valency of any given unit is equal to the number of its uncoupled electrons. If in an atom there are vacant orbitals (fnl. cells of the level AA), which differ very little in the level of energy from orbitals, having a couple of electrons, then a transition of one of the electrons is possible to a vacant orbital of a neighbouring sublayer. As a result, the electrons 'uncouple' and become valency. However, to actualise such a transition of an electron to another orbital, that is to excite the atom, one should expend a definite quantity of extrasystemic energy. The number of generalised electronic couples defines the covalency of an element.
Each fng. unit (an atom, an ion or a molecule) having in an orbital an uncoupled electron, following the laws of motion of Matter in quality
(), is striving to establish an atomic connection with partners and therefore has high reactional ability, revealing itself first of all in reactions of substitution (Na + H2O = NaOH + H) and joining (H + H = H2 or H + Cl = HCl).
The connection between atoms, being realised by the common electronic couple, can arise in another way as well. If in an atomic orbital of one atom (D) there are two electrons, and the other atom (A) has a vacant atomic orbital, then the connection between them is being formed on the account of the couple of electrons of the first atom
(D: А). The atom D, giving the electronic couple for forming the connection, is a donor, and the atom A, having a vacant orbital, an acceptor.
The formation of a donor-acceptoral connection is taking place quite differently from the mechanism of a covalency link, but brings the same result. During it a complication of composition and structure of substances with formation of complicated "complex" compounds is happening, bearing their strictly definite functional load. As a rule, one of the atoms (usually the acceptor) taking up the position in the centre is coordinating units around it, which are entering with it into the donor-acceptoral connection, also having therefore the name of a coordinative link. Owing to the coordinative link a chemical saturation of atom is taking place, as a result of which the internal energy of the system of interacting atoms is going down. Because of this the total valency of an atom (as a sum of all its links) can be high enough.
Thus during the establishment of a chemical connection, the atom gives a partner either an atomic orbital with two vacant fnl. cells (an acceptor), or an atomic orbital with one electron and one vacant fnl. cell, or an atomic orbital with a couple of electrons - fng. units (a donor). Therefore the valency of an element is equal to a total number of orbitals of its atom participating in the formation of chemical connections. During the filling in by electrons fnl. cells of all possible atomic orbitals an atom is becoming chemically saturated and incapable of establishing additional chemical connections.
In a general case, an establishment of each additional valency link leads to a further stabilisation of a molecule, and so the most steady molecules are such, in atoms of which all stable atomic orbitals either are used for establishment of connections or occupied by not divided couples of electrons.
A covalency, like a donor-acceptoral chemical connection, is being established between atoms disposed in space relative to each other in a certain manner - directionally. And so the more completely in space one is covered with the other two atomic orbitals participating in a chemical connection, the less reserve of energy electrons, being situated in the field of covering and actualising the connection, have, and the more stable the chemical connection between these atoms is. The direction of chemical connections in space gives all multiatomic particles (molecules, ions, radicals) a definite configuration. An internal structure of a substance as well as its fnl. features depend on it.
Parallel with the development of the structure of fng. units of the level D, a further division of their fnl. features was going on. As an example of this the division of units to diamagnetic and paramagnetic can serve. The first ones put up resistance to the passage of the magnetic lines of force more than 'vacuum', and the second are passing them better than 'vacuum'. Therefore an external magnetic field is forcing out diamagnetic substances and pulling in paramagnetic. Such a difference in their behaviour is explained by peculiarities of their structural construction, dictated by laws of lower organisational levels, the influence of which defines the character of internal magnetic fields of a substance forming from its own magnetic moments of nucleons and electrons. A magnetic moment of any atom is determined mainly by the total spinal magnetic moment of electrons, as magnetic moments of protons and neutrons are approximately by three grades less than moments of electrons. If two electrons are in one orbital, then their magnetic fields are locking, as both of them can have antiparallel spins. Thus, if in a substance, representing a sum of similar units, magnetic moments of all electrons are mutually compensated, that is all electrons are coupled, then this substance is diamagnetic. On the contrary, if in orbitals there are idle electrons, then the substance reveals paramagnetics. Molecular hydrogen, nitrogen, fluorine, carbon and lithium (in a gaseous state) can serve as examples of diamagnetic substances. Molecular boron, oxygen, nitric oxide relate to paramagnetic.
Substances with anomalously high magnetic receptivity (for example, ferrum) relate to ferromagnetic. However, ferromagnetism is revealing by them only in a solid state.
Here we should also note, that one of the important types of chemical connection, originated within the period of motion of Matter in her evolution along the level D, are oxidizing-restorative reactions. Those are the reactions, as a result of which the grades of elements' oxidation are being changed, that is mutual relative displacement of electrons of substances, that have entered the reaction, is taking place, at the same time an output of electrons by some molecules is going on (oxidation) and joining them by the others (reduction). Oxidizing-restorative reactions are playing a big part in biological systems' activity, and such processes as photosynthesis, breathing, digestion, etc. can happen only because of them.
Thus, during the evolution of Matter along the organisational level D, the functional differentiation of atoms became a cause of their structural integration into molecules.
All around us bodies and substances constitute combinations of a big number of fng. units of the level D - molecules, ions, radicals with strictly definite fnl. features - this or that way located in space and united into corresponding systemic formations of the level E. Their relative location in space is not fortuitous, but obeys objective laws of the general theory of systems, according to which they fill in destined for them fnl. cells in structures of systemic formations of a higher order. Depending on the character of the interactions of fng. units, being regulated by algorithms of corresponding fnl. cells, the substance uniting them is in one of phase states, the features of which predetermine a structure of the fixation of fnl. cells and a behaviour of fng. units filling them in.
One can distinguish three principal types of phase states of substance - gaseous, liquid and solid. In addition, there are also such phase states as plasmas and superconductive. The difference between states is in the systemic organisation of fng. units entering them, their relative location in space and the level of their energy. During the transition of a substance from one phase state into another, first of all a structural reorganisation of the system of fnl. cells takes place, reflecting the reserve of internal energy of the substance, its heat capacity, density, etc. Besides, any system of units of the level D has a certain number of grades of freedom, equal to the number of conditions, that can be changed arbitrarily (within definite limits) without inspiring in the system phase transitions.
It is quite natural to assume, that in the initial stage of the motion of Matter along the level E small associations of D-formations later were acquiring more and more complex structural composition, including primary microsystems as fng. units and uniting them into bigger macrosystems. The phase state of every macrosystem of the level E first of all depends on states of all microsystems entering it and is characterised by its thermodynamic probability. Thus, obeying statistics, a system is striving to turn into such a macrostate, to which most of the variants of microstates correspond.
With the growth of the number of variants a probability of transition of a system into a given state is rising and at the same time an order in location of particles is decreasing, that is a 'disorder' in the system is increasing. Implied by this is an expansion of the set of both velocities and directions of movement (forward, vibratory, rotary) in space of fng. units of all levels forming a system (of molecules, atoms, electrons, etc.). The above is reflecting the aspiration of Matter through systemic states to balance her motion in quality-space-time in accordance with the laws of her Evolution. Therefore systems, obeying the regularities of development in the three categories, are striving to turn into states, ensuring their most stability, however, during that the extent of isolation (or locking) of a given system, defining its ability to participate in formation of fng. units of a higher order in accordance with the requirements of , is playing more and more a part.
Besides, it is necessary to bear in mind, that every system of the level E has already a substantial quantity (by comparison with lower levels) of reserve of internal energy, being formed from the energy of movement, vibration and rotation of all molecules, the energy of movement of electrons and nuclei in atoms, the energy of nucleons, that is from a total energy of all kind of the motion of all the fng. units of lower levels, included in the structure of a given system. A location or displacement of the system in space as a fng. unit of an organisational level of the next order do not affect the reserve of internal energy, therefore the kinetic and, in certain cases, the potential energy of the system as a whole are not the components of its internal energy, which depends only on the organisational level of the system as well as on the extent of its isolation.
In the case of a lack of locking of a systemic formation
(), only those processes can go on in the system that lead to the decreasing of internal energy, to the perfection of systemic organisation, to free motion of Matter in space-time-quality. In the locked, to a certain extent, systems (not exchanging with external surroundings by fng. units and energy) only such processes can go on, during which the entropy of the system is growing.
Much of the above is confirmed by the formula , which has already been considered by us and which after the permutation of meanings is transforming into . In systems not isolated the development of material substance is going on relatively equivalently in , however at higher levels of organisation, including level E, owing to the reduction of velocities of spreading in space, is substantially decreasing in comparison with the dynamics of this parameter at lower levels, the energy of the combined Matter is declining for each significant volume of space and motion in quality strives to more and more spatial localisation (but not to isolation). In closed systems (, ) the above formula transforms, as it is known, into , that is a system strives to get over into a state with a maximum number of variants, owing to that the process can go on always until such a state, the entropy of which has the maximum value for existing conditions. Thus, a state, in which a system can be under unchanging conditions, is a result of competition of the two active factors - entropic and energetic. (The accumulative factor has always a passive character.)
During the conversion of a substance into this or that phase state depending on the conditions the two opposite tendencies come into collision: the first - the striving to declining of internal energy, leading to a loss of mobility by particles and to increasing of order in the system, and the second - the striving to an augmentation of the entropy, leading to decreasing of the systemic order. Any process at any organisational level, including even as high as social, is a reflection of the struggle of these opposite factors, and it is necessary always to bear in mind this fact. In systemic processes at the level E a predominance of one of the factors leads to a gradual conversion of a system into a more thermodynamically stable state.
While a predominance of the energetic factor a process is going toward declining of internal energy of a system as a result of intensification of interaction of particles of a substance occurring with emitting of energy. To such processes we can attribute mainly those processes, that complicate the structure of a substance, raise its aggregation: formation of a molecule from atoms, association of molecules, straightening and mutual relative orientation of macromolecules, compression of gases, condensation of steam, crystallisation of a substance.
In the case of the prevailing of the entropic factor a process is going towards augmentation of the entropy of a system as a result of separation of particles of a substance and their mutual moving away from each other. Those are mainly the processes, linked with the disaggregation of a substance: the melting of a substance, its evaporation, expansion and mixture of gases, solution of substances, disassociation of molecules, etc.
Let us consider briefly the peculiarities of the behaviour of fng. units in structures of a substance in systemic formations of the organisational level E during different phase states.
A gaseous state of a substance - more probable at high temperatures - is characterised by high meanings of entropy. It reflects an entire disorder in a system of fng. units, performing individual forward movements with different velocities and practically not interacting one with others. The less energy of interaction between the two fng. units, being in contact (weak connections), the bigger reserve of internal energy a system has, and then even at lower temperatures a substance is able to be in a gaseous state. To such substances are attributed first of all inert gases, atoms of which experience a very weak attraction one to another.
During the complication of structural construction of fng. units (owing to ), their ability for mutual attraction is growing. It reveals itself in the rise of the temperatures of boiling of substances with growth of fnl. mass of elements composing them. At a set temperature an average velocity
()of molecules of a gas depends on their functional mass: the higher its meaning, the more energy is required to increase its velocity ().Velocities of molecules are linked with parameters of a system's state (with a temperature, a pressure) and therefore are an important characteristic of their behaviour.
A thermal motion of molecules in a substance makes conditional its ability to diffusion, that is to a spontaneous transition of a substance to those fields of space
(), where its concentration is less or equal to zero. This feature reveals itself in quite different natural processes - evaporation, dissolution, osmosis, glueing, etc.
During the cooling of substances being in a gaseous state (or while strong pressing them), the forces of interaction between particles begin to predominate over the energy of their thermal motion, and at a certain temperature (individual for each substance) it turns into a liquid state. An essential condition of such a transition is the establishment of connections between separate fng. units (molecules or atoms), as a result of which the internal energy of a system is becoming less. A liquid state of a substance gives a more 'organised' structure, than its gaseous state, but it is less stable, that is susceptible to more frequent changes during different periods of time
(), than a solid substance. Therefore a liquid state is intermediate between gaseous and solid. Molecules of a liquid, having the possibility of displacements, keep the definite order in mutual relative location. By the structure and the character of interactions between particles a liquid is more similar to crystals, than to gases. As well as solid bodies, liquids have a certain volume, that also distinguishes them from gases. The principle distinction of a liquid from a solid body is the lack of its own form.
Thus, each fng. unit of the sublevel E depending on a fnl. cell, it occupies, can be in a structure of a substance in any phase state: 1) gaseous, 2) liquid, 3) solid.
Through the analysis of the structural peculiarities of the phase states of substances it is obvious that fng. units in a gaseous state do not interact with each other, therefore their structure is uncertain and changeable. In a liquid state one can observe more interaction in the behaviour of fng. units, they are united into a more combined structure, having more definite features than a gaseous state of a substance. Fng. units in the structure of a liquid perform 1012 - 1013 vibrations per second, staying in a certain fnl. cell during 10-11 - 10-10 seconds. Hence, until a jump to a new position or until a reorganisation of the structure of fnl. cells around it, a fng. unit manages to complete from 10 to 100 vibrations. In other words, only from 1 to 10% of vibratory moves of a fng. unit end by its displacement in space. By this the features of similarity of a liquid with a solid body are revealing themselves, as in a solid body almost no one vibration of a molecule (or an atom) occurs with its transition to another place. But if a solid body is characterised by practically invariable relative location of fng. units, then in a liquid as a result of the relative displacements of units the compression of the structure of fnl. cells is irregular, and local alterations of short duration in separate parts of the structure are being observed constantly. Under the action of external forces (for example, of force of gravity) displacements of separate concentrations of particles in a liquid, that is fluctuations of its density, become directional. As a result a liquid is flowing that is moving with an alteration of its form, but with preservation of the entire volume (if there is no evaporation), in the direction of an application of force. Thus, the fluidity is a specific feature of a liquid body, caused by a limited mobility of its structural units.
The structure of a liquid is very sensitive to alterations of temperature. At temperatures close to T-melting the structure of a liquid is approximating to a solid body as it has elements of a crystal structure, and vice versa, at temperatures close to T-boiling the order in locations of fng. units is reducing to a minimum and an intensive evaporation starts, that means, that a substance is turning into a gaseous state. Therefore the temperature is a conceptual index of vibrations of fng. units relatively each other in a given system within the limits allowed by fnl. cells, they occupy. In their turn the frequency and the amplitude of vibrations of fng. units, that is the velocity of their displacement in space per a unit of time, depend on the quantity of kinetic energy, coming to this group of fng. units at the given moment of time. During a rise of T, that is while receiving by the given group of fng. units some additional quantity of kinetic energy, the amplitude and the frequency of vibrations are increasing until a certain significance, exceeding which fng. units leave the fnl. cells of a given structure, getting over into fnl. cells of another phase state with other permissible significances of amplitudes and frequencies of vibration. The opposite process is going during a decline of temperature, that is while the decreasing of the quantity of kinetic energy, coming to the given group of fng. units of a substance. From the point of view of a substance's formation a liquid state is the most changeable and varied.
While hardening substances acquire the structure, that has a distant order in the location of fng. units forming them (molecules, atoms or ions). Therefore it is enough to know a part of the structure of fnl. cells in order to get a conception about their location in the entire volume of the given solid body. As a rule, the cells form in it the strictly definite crystals, while according to the principles of the general theory of systems all fnl. cells should be filled in by fng. units corresponding to them.
The crystal structure of a substance thermodynamically is more steady, then amorphous. This can be explained in the way that the regular location of fng. units in the cells of crystals allows them to establish the maximum number of connections between themselves, and this assists to a further reduction of the reserve of internal energy in a substance. A tightly-filled packing of fng. units one can imagine as a piling of balls of the same size. In every row balls come into contact with each other, and a ball of the next row is situated between two balls of the previous row. A distinctive feature of the most compact piling of balls is a big number of the nearest neighbours of each ball: six in one layer and by three from below and from above. Thus, during the most compact piling of balls a so-called coordinational number of each ball equals 12.
The construction of crystals one can imagine usually with the help of their abstract illustrations - crystal lattices, representing a three-dimensional figure, received by conjunction with straight lines of centres of fnl. cells. It is necessary to underline, that a crystal lattice, as well as all elements forming it, are only a mathematical abstraction being used for the description of the structure of a crystal and, in the first place, for the description of a symmetry in the location of its fnl. cells.
The atoms of a solid substance as fng. units take up positions in accordance with the given structure of fnl. cells, while during an augmentation of total interaction between them the internal energy of the system is declining at the simultaneous growth of its steadiness. In the case of a reorganisation by this or that reason of the structure of fnl. cells of a substance the number of connections between its atoms is changing, that in a moment is revealing itself in a modification of the entire complex of fnl. features of the substance and is an evidence of its transformation into a new substance. Allotropic modifications of carbon - graphite and diamond - can serve as examples of that, as they differ not only by mechanical (hardness) and physical (electrical conductivity, light passing) fnl. features of these substances, but also by their chemical behaviour: if graphite is an analogue of organic compounds of the benzol group, then diamond has more in common with compounds of the saturated group. As other examples we can designate the molecular oxygen O2 and ozone O3.
All crystal bodies, as stated above, are desmical (linked) systems, which by uniformity of connections, acting between atoms forming them, are usually divided into two groups: homodesmical (equally linked) and heterodesmical (differently linked). The crystals, having all connections of one type, can be attributed to homodesmical systems. It is impossible to pick out some isolated portions in such crystals as all the connections in the entire volume of the substance are adequate in between. These are atomic and metallic crystals as well as crystals consisting of ordinary ions.
The crystals, having between fnl. cells connections of different types, are attributed to heterodesmical systems. We should take here ionic crystals, in the junctions of the lattice of which complex ions are situated, and molecular crystals.
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