Physical chemistry as a fundamental chemical science. Sections of physical chemistry. The structure of molecules and spectroscopy
1. Physical chemistry: purpose, tasks, research methods. Basic concepts physical chemistry.
Phys. chemistry - Science of laws of Chem.Processes and Him. phenomena.
The subject of fiz. Chemical explanation. phenomena based on more general laws of physics. Phys.Chimiya considers two main groups of issues:
1. Studying the structure and properties of the substance and components of its particles;
2. Study of substance interaction processes.
Fiz. Chemistry aims to study the links M / in Him Mi and Physi Phenomena. Knowledge of such connections is necessary in order to learn chemical deeper in nature and used in the technologist. Processes, control the depth and direction of the reaction. The main goal of the discipline of the physical school study of general relations and the laws of Him. Processes based on fundamental principles of physics. Phys.Chemy applies Piz. Theories and methods for chemical.
She explains why and how the transformations of substances occur: Chem. Reactions and phase transitions. Why - Chem.Termodynamics. Query kinetics.
The basic concepts of fiz. Chemistry
The main object Chem. Thermodynamics is a thermodynamic system. Thermodynamic. system - Any body or a set of bodies that can exchange M / act and other bodies of energy and in-B. Systems are divided into open, closed and isolated. Open and I - the thermodynamic system exchanges with an external environment and in-B and energy. Closed and I - System, in which there is no exchange in-in with the environment, but it can exchange energy with it. Isolated and I -System volume remains constant and deprived of the ability to exchange with the environment and energy and in-B.
The system can be homogeneous (homogeneous) or heterogeneous (inhomogeneous ). Phase - This is part of the system, which in the absence of an external field of forces has the same composition in all its points and the same thermodynamic. You are also separated from other parts of the section of the section. Phase is always homogeneous, i.e. Homogenna, so one-phase system is called homogeneous. A system consisting of several phases is called heterogeneous.
The properties of the system are divided into two groups: extensive and intense.
In thermodynamics, the concepts of equilibrium and reversible processes are used. Equilibrium - This is the process passing through a continuous number of equilibrium states. Reversible thermodynamic process - This is a process that can be carried out in the opposite direction without any changes to the system and the environment.
2. Itho law of thermodynamics. Inner energy, heat, work.
The first top of thermodynamicsdirectly associated with the law of energy conservation. Based on this law, it follows that in any isolated system, energy remains constant. Another formulation of the first start of thermodynamics follows from the laws of energy - the impossibility of creating the perpetual engine (Perpetuum Mobile) of the first kind, which would produce work without spending on it. Especially important for chemical thermodynamics wording
the first start is the expression of it through the concept of internal energy: internal energy is a function function, i.e. Its change does not depend on the path of the process, but depends on the initial and end state of the system. Change internal energy system U.may occur due to the exchange of warmth Q.and work W.with the environment. Then, out of the law of energy conservation, it follows that the heat obtained by the heat system q is spent on the increment of internal energy ΔU and the work W, a perfect system, i.e. Q \u003dΔ U + W.. This w.equality is
mathematical expression of the first start of thermodynamics.
I. Beginning of thermodynamics His wording:
in any isolated system, the energy supply remains constant;
different forms of energy go to each other in strictly equivalent quantities;
eternal Engine (perpetuum mobile) the first kind is impossible;
Internal energy is a function function, i.e. Its change does not depend on the path of the process, but depends only on the initial and end state of the system.
analytical expression: Q. = D. U. + W. ; For infinitely small changes in magnitude d. Q. = du + d. W. .
1st The beginning of thermodynamics sets a relationship. m / in warm q, work A and change in ext. Energy system ΔU. Change internal. The energy of the system is equal to the number of reported heat system minus the amount of work performed by the system against external forces.
Equation (I.1) is the mathematical record of the 1st beginning of the thermodynamics, equation (I.2) - for infinitely small changes in Sost. Systems.
Internal Energy - FUNCTION COST; This means that change is internal. The energy ΔU does not depend on the path of transition of the system from state 1 to state 2 and equal to the difference in extras. Energy U2 and U1 in these states: (I.3)
Internal The energy of the system is the amount of potential energy interaction. all body particles m / act and kinetic energy Their movements (excluding kinetich. and potential. Energy system as a whole). Inside. The energy of the system depends on the nature of the BA, its masses and from the parameters of the system of the system. She is age. With an increase in the mass of the system, since it is an extensive bond system. Internal The energy is denoted by the Litera U and express in Joules (J). In general, for the system with the number of 1 mol. Internal Energy, like any thermodynamic. SV-in system, it is a function of the Sost. Directly in the experiment, only changes are manifested. Energy. That is why, in calculations, it is always operated with its change U2 -U1 \u003d U.
All changes internal. Energy is divided into two groups. In the 1st group, the group includes only 1 - and the movement of the movement by chaotic collisions of the molecules of two contacting bodies, i.e. By thermal conductivity (and at the same time by radiation). The measure of the movement transmitted in this way is heat. Concept warmassociated with the behavior of a huge number of particles - atoms, molecules, ions. They are in constant chaotic (thermal) movement. Heat - energy transfer form. The second way of exchanging energy - work.This energy exchange is due to the action performed by the system, or the action committed on it. Usually work indicate a symbol W.. Work, as well as heat, is not a function of the state of the system, so the value corresponding to infinitely small work is denoted by a special derivative symbol - W..
The classification of sciences is based on the classification of forms of motion of matter and their relationship and difference. Therefore, in order to outline the borders of physical chemistry with a number of sections of physics and chemistry, the connection should be considered and the difference between the chemical and physical forms of movement.
For the chemical form of motion, i.e., for a chemical process, a change in the number and arrangement of atoms in the molecule of reacting substances is characteristic. Among many physical forms of movement (electromagnetic field, movement and conversion of elementary particles, physics of atomic nuclei, etc.), especially close relationship with chemical processes has intramolecular form of motion (oscillations in the molecule of its electronic excitation and ionization). The simplest chemical process is an elementary act of thermal dissociation of the molecule takes place when the intensity of the intensity (amplitude and energy) of oscillations in the molecule, especially the oscillations of the nuclei along the valence between them. The achievement of the known critical amount of oscillation energy in the direction of a certain connection in the molecule leads to the rupture of this connection and the dissociation of the molecule into two parts.
More complex reactions involving several (usually two) molecules can be viewed as a compound of two molecules when they collide in a continuing and short-lived complex (the so-called active complex) and the rapidly coming destruction of this complex for new molecules, since this complex with internal oscillations is unstable. According to certain relations.
Thus, an elementary chemical act is a special, critical point of the oscillatory movement of molecules. The latter can not be considered a chemical movement, but it is the basis for primary chemical processes.
For the chemical conversion of significant mass substances, i.e. the set of molecules, the collision of molecules and the exchange of energies between them (the transfer of the motion of the molecules of the reaction products to the source molecules by collisions). Thus, the real chemical process is closely connected with the second physical Motion Form - Chaotic movement of molecules of macroscopic bodies, which is often called thermal motion.
Above markedly, the mutual relationship of the chemical form of movement with two physical forms of movement in the most common features. Obviously, there are the same links of the chemical process with the emission of the movement of the electromagnetic field, with the ionization of atoms and molecules (electrochemistry), etc.
Structure of matter . This section includes the structure of atoms, the structure of molecules and the doctrine of aggregate states.
The doctrine of the structure of atoms has a greater attitude to physics than to physical chemistry. This teaching is the basis for studying the structure of molecules.
In the teaching on the structure of molecules, geometry of molecules, intramolecular movements and forces that bind atoms in the molecule are investigated. In experimental studies of the structure of molecules, the method of molecular spectroscopy (including radio spectroscopy) was obtained, electrical, radiographic, magnetic, and other methods are also widely used.
In the teaching on aggregate states, the interactions of molecules in gases, liquids and crystals, as well as the properties of substances in various aggregate states are considered. This very important section of science can be considered part of physics (molecular physics) for physical chemistry.
The entire section on the structure of the substance can also be considered as part of physics.
Chemical thermodynamics . In this section, based on the laws of general thermodynamics, the laws of chemical equilibrium and the doctrine of phase equilibriums are presented, which is commonly called the phase rule. Part of chemical thermodynamics is thermochemistry,in which thermal effects are considered chemical reactions.
The doctrine of solutions aims to explain and predict the properties of solutions (homogeneous mixtures of several substances) based on the properties of the substances constituting the solution.
The solution to this problem requires the construction of a general theory of interaction of heterogeneous molecules, i.e. solutions to the main task, molecular physics. For the development of general theory and private generalizations, the molecular structure of solutions is being studied and their various properties depending on the composition.
The doctrine of surface phenomena . The various properties of surface layers of solid bodies and liquids are being studied (separation boundaries between phases); one of the main studied phenomena in surface layers is adsorption(accumulation of substances in the surface layer).
In systems, where the surfaces of the section between liquid, solid and gaseous phases are highly developed (colloidal solutions, emulsions, fogs, smokes), the properties of the surface layers acquire the basic value and determine many peculiar properties of the entire system as a whole. Such microheterogenicsystems are studied colloid chemistry,which is a major independent section of physical chemistry and independent educational discipline in chemical higher educational institutions.
Electrochemistry. The interaction of electrical phenomena and chemical reactions is studied (electrolysis, chemical sources of electric current, electrosynthesis theory). In an electrochemistry, usually the doctrine on the properties of electrolyte solutions, which can be attributed to equal rights to the teachings on solutions.
Chemical kinetics and catalysis . The rate of chemical reactions is studied, the dependence of the reaction rate from external conditions (pressure, temperature, electrical discharge, etc.), the connection of the reaction rate with the structure and energy states of molecules, an effect on the reaction rate of substances that are not involved in the stoichiometric reaction equation (catalysis).
Photochemistry. The interaction of radiation and substances involved in chemical transformations (reactions occurring under the influence of radiation, such as photographic processes and photosynthesis, luminescence). Photochemistry is closely related to chemical kinetics and teaching about the structure of molecules.
The above list of the main sections of physical chemistry does not cover some recent areas and smaller sections of this science, which can be viewed as part of larger sections or as independent sections of physical chemistry. Such, for example, radiation chemistry, physicochemistry of high molecular substances, magnetochemistry, gas electrochemistry and other sections of physical chemistry. The value of some of them is currently growing rapidly.
Physico-chemical research methods
The main methods of physical chemistry, naturally, are methods of physics and chemistry. This is primarily an experimental method - a study of the dependence of the properties of substances from external conditions and the experimental study of the laws of the flow of chemical reactions in time and laws of chemical equilibrium.
Theoretical comprehension of the experimental material and the creation of a slender system of knowledge of the properties of substances and the laws of chemical reactions is based on the following methods of theoretical physics.
Quantum-mechanical method (in particular, the wave mechanic method) underlying the teachings on the structure and properties of individual atoms and molecules and the interaction of them among themselves. Facts belonging to the properties of individual molecules are obtained mainly using experimental optical methods.
Method of statistical physics giving the ability to calculate the properties of the substance; consisting of multiple molecules ("macroscopic" properties), on the basis of information on the properties of individual molecules.
Thermodynamic method , allowing you to quantify the various properties of the substance ("macroscopic" properties) and calculate some of these properties on the basis of the experimental values \u200b\u200bof other properties.
Modern physico-chemical studies in any particular area are characterized by the use of various experimental and theoretical methods for studying the various properties of substances and clarify their connection with the structure of molecules. The entire set of data and the above theoretical methods are used to achieve the main goal - to determine the dependence of the direction, speed and limits of the flow of chemical transformations from external conditions and on the structure of molecules - participants in chemical reactions.
PHYSICAL CHEMISTRY
§ 1. Subject of physical chemistry. Its value
The relationship of chemical and physical phenomena studies physical chemistry.This chemistry industry is border between chemistry and physics. Using the theoretical and experimental methods of both sciences, as well as its own methods, physical chemistry is engaged in a multilateral study of chemical reactions and physical processes associated with it. Since, however, even a multilateral study is never complete and does not cover the phenomenon of an exhaustive way, so far the laws and patterns of physical chemistry, as well as other natural sciences, always simplify the phenomenon and do not reflect it completely.
Fast development and growing importance of physical chemistry are associated with its border position between physics and chemistry. The main overall task of physical chemistry is the prediction of the time process of the process and the final result (equilibrium state) in various conditions on the basis of the data on the structure and properties of the substances that are studied by the system.
§ 2. A brief essay of the history of the development of physical chemistry
The term "physical chemistry" and the definition of this science was first given by M.V. Lomonosov, which in 1752-1754. I read the students of the Academy of Sciences Course of physical chemistry and left the manuscript of this course "Introduction to True Physical Chemistry" (1752). Lomonosov performed many studies whose topics correspond to the "plan to the course of physical chemistry" (1752) and the program of experimental work "Experience of physical chemistry" (1754). Under his leadership, student workshop on physical chemistry was also conducted.
Lomonosov gave the following definition of physical chemistry: "Physical chemistry is a science explaining on the basis of the provisions and experiments of physics what is happening in mixed bodies in chemical operations." This definition is close to modern.
For the development of physical chemistry, the discovery of two thermodynamics laws in the middle of the XIX century (S. Carno, Yu.R. Maer, Gelmgolts, DP Jowle, R. Kulausius, V. Thomson) was of great importance.
The number and variety of studies lying in the field, border between physics and chemistry, constantly increased in the XIX century. The thermodynamic doctrine of chemical equilibrium was developed (K.M.Guldberg, P.Vaage, D.U. Bakebs). Research L.F.Vilgelmi marked the beginning of the study of the rates of chemical reactions (chemical kinetics). The transfer of electricity in solutions (I.V.Gittorf, F.V.G. Kolraush) was investigated, the laws of equilibrium of solutions with ferry (DPKovalov) were studied and the theory of solutions was developed (D. I. Mendeleev).
Recognition of physical chemistry as independent science and educational discipline It was expressed in the institution at the University of Leipzig (Germany) in 1887 the first department of physical chemistry led by V. Super and at the base of the first scientific journal in physical chemistry. At the end of the 19th century, the University of Leipzig was the center for the development of physical chemistry, and the leading physico-chemists were V. Suvald, Ya.H.Vant-Hoff, S.Arrenius and V.Nestst. By this time, three main sections of physical chemistry were determined - chemical thermodynamics, chemical kinetics and electrochemistry.
The most important areas of science, the development of which is a prerequisite for technical progress, refers to the study of chemical processes; Physical chemistry belongs to the leading role in the development of this problem.
§ 3. Sections of physical chemistry. Research methods
Chemical thermodynamics. In this section, on the basis of laws of general thermodynamics, the laws of chemical equilibrium and the doctrine of phase equilibrium are set.
The doctrine of solutions aims to explain and predict the properties of solutions (homogeneous mixtures of several substances) based on the properties of the substances constituting the solution.
The doctrine of surface phenomena. A variety of properties of surface layers of solid bodies and liquids are being studied (separation boundaries between phases); one of the main studied phenomena in surface layers is adsorption(accumulation of substance in the surface layer).
In systems, where the surfaces of the section between liquid, solid and gaseous phases are highly developed (emulsions, fogs, smoke, etc.), the properties of the surface layers acquire the basic value and determine many peculiar properties of the entire system as a whole. Such dispersed (microheterogenic)systems are studied colloid chemistry,which is a major independent section of physical chemistry.
The above list of the main sections of physical chemistry does not cover some areas and smaller sections of this science, which can be viewed as part of larger sections or as independent sections of physical chemistry. It should once again emphasize the close relationship of various sections of physical chemistry. In the study of any phenomenon, it is necessary to use the arsenal of representations, theories and methods for studying many sections of chemistry (and often from other sciences). Only at the initial acquaintance with physical chemistry it is possible in academic purposes Distribute the material at the specified sections.
Physico-chemical research methods. The main methods of physical chemistry, naturally, are methods of physics and chemistry. This is primarily an experimental method - a study of the dependence of the properties of substances from external conditions, the experimental study of the laws of the flow of various processes and the laws of chemical equilibrium.
Theoretical understanding of experimental data and the creation of a slender system of knowledge is based on the methods of theoretical physics.
The thermodynamic method, which is one of them, allows you to quantify the various properties of the substance ("macroscopic" properties) and calculate some of these properties on the basis of the experimental values \u200b\u200bof other properties.
Chapter I.
The first law of thermodynamics
§ 1. Energy. The law of conservation and turning energy
An integral property (attribute) of matter is movement; It is unable, like the matter itself. Movement of matter is manifested in different forms that can move one to another. Measure of motion of matter is energy.Quantitatively energy is expressed in a certain way through the parameters characteristic of each specific form of movement, and in the units specific for this form.
In the system of units of the system of energy (heat and work) is Joule ( J)equal work of force in 1 N. On the way to 1 m.1 J \u003d 1 N · m.
A widespread energy unit (heat) of calorie is currently an incident unit allowed for use. Current currently used by definition is equated with a certain number of Jowle: 1 cal.equal to 4,1868 joule. This unit is used in heat engineering and may be called heat engineering caloria.In the chemical thermodynamics, a somewhat excellent one is equivalent to 4,1840 joule and called thermochemical calorie.The expediency of its application is related to the convenience of using an extensive experimental thermochemical material collected in reference editions expressed in these units.
In converting one form of movement to another energy of the disappeared and motion, expressed in various units, is equivalent to each other, i.e. the energy of the disappeared movement is in constant quantitative attitude to the energy of the emergence of the movement (the law of equivalent energy transformations). This attitude does not depend on the values \u200b\u200bof the energies of two forms of movements and on the specific conditions under which the transition of one form of movement to another occurred. So, when the electric current energy turns into the energy of the chaotic molecular movement is always one joele of electrical energy turns into 0.239 cal.molecular motion energy.
Thus, the energy as a measure of the movement of matter is always manifested in a qualitatively peculiar form corresponding to this form of movement, and is expressed in the corresponding units of measurement. On the other hand, it quantitatively reflects the unity of all forms of movement, their mutual transformation and non-profitability of the movement.
The above law of equivalent energy transformations is a physical experienced law. The law of equivalent energy transformationsmay be expressed differently, namely in the form the law of conservation and transformation of energy:energy is not created and does not destroy; With all processes and phenomena, the total energy of all parts of the insulated material system involved in this process does not increase and does not decrease, while remaining constant.
The law of conservation and conversion of energy is universal in the sense that it is applicable to phenomena flowing at an arbitrarily large bodies representing a set of a huge number of molecules, and to phenomena taking place with the participation of one or few molecules.
For various forms of mechanical movement, the law of conservation of energy has long been expressed in high-quality form (Deskarte - 1640) and quantitative form (leibhers - 1697).
For mutual transformations of heat and work (see below), the law of conservation of energy was proven as a natural science law of research by Yu. R. Mayer, Gelmgolts and D.P.Joule, held in the fortieth years of the XIX century.
Using the law of equivalent transformations, it is possible that the energy of various forms of movement can be expressed in units characteristic of one type of energy (one form of motion), and then produce operations of addition, subtraction, etc.
§ 2. The subject, method and boundaries of thermodynamics
Thermodynamics is one of the main sections of theoretical physics. Thermodynamics studies the laws of mutual transformations of various types of energy associated with the transitions of energy between the bodies in the form of heat and work. Focusing its attention on heat and work, as the forms of energy transition for a wide variety of processes, the thermodynamics involves the numerous energy bonds in its circle of consideration and the dependences between the various properties of the substance and gives very widely applicable generalizations wearing name the laws of thermodynamics.
When establishing major thermodynamic patterns, energy transformations are usually not detailed (often very complex) occurring inside the body. The types of energy peculiar to the body in this state are not differentiated; The combination of all these types of energy is considered as a single internal energy system .
The subject of thermodynamics, outlined above, determines the method and boundaries of this science. The difference between the warmth and work received by thermodynamics as the starting position and the opposition of heat of work makes sense only for bodies consisting of a plurality of molecules, since for one molecule or for a set of a small number of molecules, the concept of heat and work lose meaning. Therefore, thermodynamics considers only the bodies consisting of a large number of molecules, the so-called macroscopic systemsmoreover, thermodynamics in its classic form does not take into account the behavior and properties of individual molecules.
The thermodynamic method is also characterized by the fact that the object of the study is the body or group of bodies allocated from the material world in thermodynamic system (hereinafter referred to as system).
The system has certain boundaries separating it from the outside world (environment).
The system is homogenic , if each parameter has each parameter in all parts of the system, the same value or continuously changes from the point to the point.
The system is heterogeneous , if it consists of several macroscopic (in turn, from many molecules) parts separated by one from the other visible surfaces of the section. On these surfaces, some parameters vary jump-like. Such is, for example, the system "solid salt is a saturated aqueous salt solution - a saturated water vapor". Here at the borders of the salt - the solution and the solution - steam jumps about the composition and density.
Homogeneous parts of the system separated from the rest of the visible surfaces of the section are called phases . At the same time, the combination of individual homogeneous parts of the system with the same physical and thermodynamic properties is considered to be a single phase (for example, a set of crystals of a single substance or a set of droplets of fluid suspended in gas and the components of the fog). Each system phase is characterized by its own status equation.
A system that cannot communicate with the environment with the substance and energy (in the form of heat or work) is called isolated .
A system that can exchange with the environment substance and energy (in the form of heat or work) is called open.
A system that cannot communicate with the environment, but can exchange energy (in the form of warmth or work), is called closed .
Thermodynamics examines the mutual relationship of such measurable properties of the material system as a whole and its macroscopic parts (phases), as temperature, pressure, mass, density and chemical composition of the phases that are logged in, and some other properties, as well as the relationship between changes in these properties.
The combination of thermodynamics of properties (so-called thermodynamic parameters of the system) Determines thermodynamic state of the system.Changing any thermodynamic properties (at least one) leads to a change in the thermodynamic state of the system.
All processes found in nature can be divided into spontaneous (natural) and non-prospecting.
Spontaneous processes - These are such processes that do not require energy costs from the outside. For example, the transition of heat from the body with a higher temperature to the body with a lower temperature, dissolving the salt in water, etc. proceeds by itself.
Nonseparate processes Require for its flow energy costs from outside, for example, the separation of air on nitrogen and oxygen.
In thermodynamics, mainly such states of the system are considered, in which its parameters (temperature, pressure, electrostatic potential, etc.) do not change spontaneously in time and have the same value at all points of the volume of individual phases. Such states are called equilibrium.
One of the main postulates of thermodynamics is the statement that the flow of any spontaneous process ultimately leads an isolated system into an equilibrium state when its properties are no longer able to change, i.e. the equilibrium will be established.
Conditions characterized by uneven and variable in time by the distribution of temperature, pressure and composition inside the phases are nonequilibrium. They are considered thermodynamics of nonequilibrium (irreversible) processes in which, in addition to major thermodynamic laws, additional assumptions are used.
Thermodynamics, built on the basis of the basic laws of thermodynamics, which are considered as a summary of experience, is called often classicor Phenomenological thermodynamics.Thermodynamics gives theoretical foundations for the teachings on heat machines; This section is called technical thermodynamics.Study chemical processes From a thermodynamic point of view chemical thermodynamics,being one of the main sections of physical chemistry.
§ 3. Heat and work
Changing the forms of movement during the transition from one body to another and the corresponding energy transformations are very diverse. The forms of the transition of the movement and related energy transitions can be broken into two groups.
The first group includes only one form of the transition of the movement by chaotic collisions of the molecules of two contacting bodies, i.e. By thermal conductivity (and at the same time by radiation). Measure transmitted in this way of movement is heat .
The second group includes various forms of movement of the movement, which is the movement of macroscopic mass under the action of any external forces that are directed. Such are the lifting of bodies in the field of gravity, the transition of a certain amount of electricity from greater electrostatic potential to a smaller, expansion of gas under pressure, etc. The general measure of traffic transmitted by such methods is work .
Heat and work characterize qualitatively and quantitatively two different forms of transmission of motion from one part of the material world to another.
Movement transmission is a kind of complex movement of matter, the two main forms of which we differ. Heat and work are measures of these two complex forms of motion of matter, and they should be considered as types of energy.
The common property of heat and work is that they matter only during periods of time in which these processes occur. During such processes, the movement in certain forms decreases in some bodies and decreases the corresponding energy, simultaneously in other bodies, movement increases in the same or other forms and increase the corresponding energy.
We are not talking about the reserve of warmth or work in any body, but only about the warmth and work of the famous process. After his ending about the presence of warmth or work in bodies, it is not necessary to speak.
§ 4. Equivalence of heat and work
The constant equivalent relationship between the warmth and work in their mutual transitions is established in the classical experiments of DP JOULE (1842-1867). A typical Joule experiment is as follows.
Joule device to determine the mechanical equivalent of heat.
Falling S. famous height Loads rotate a stirrer immersed in water in a calorimeter (cargo and water calorimeter constitute the thermodynamic system.) The rotation of the blades of the stirrer in water causes water heating in the calorimeter; The appropriate increase in temperature is quantified.
After the process is completed, the system must be given in its original state. This can be done by mental experience. Loads rise to the original height, while the work is spent from outside, which increases the energy of the system. In addition, the calorimeter is torn (transmitted to the environment) of heat by cooling it to the starting temperature. These operations return the system to the initial state, i.e., all measurable properties of the system acquire the same values \u200b\u200bthat they had in the initial state. The process during which the properties of the system changed, and at the end of which it returned to the initial state is called circular (cyclic) process or cycle .
The only result of the described cycle is the extension of work on the environment surrounding the system, and the transition to this warmth environment taken from the calorimeter.
A comparison of these two values \u200b\u200bmeasured in the respective units shows a constant relationship between them, independent of the magnitude of the cargo, the size of the calorimeter and the specific amounts of heat and work in different experiments.
Warm and work in the cyclic process, it is advisable to write down as an amount (integral) of infinitely small (elementary) heat Q. and infinitely small (elementary) works W., and the initial and end-limits of integration coincide (cycle).
Then the equivalence of heat and work in the cyclic process can be written as follows:
(I, 1)
In equation (I, 1) sign 
Indicates integration by cycle. Constancy of the coefficient k.
reflects the equivalence of heat and work ( k. - Mechanical equivalent of heat). Equation (I, 1) expresses the law of conservation of energy for a private, very important case turning work in heat.
In Joule's research, Rowland (1880), Mikulesk (1892) and others. Friction methods in metals, impact, direct transformation of electric current operation in warmth, tensile solid bodies, and other coefficient k. always constant within the error of experience.
Further presentation always assumes that work and heat using the coefficient k. expressed in one units (no matter what) and coefficient k. Soots.
§ 5. Internal energy
For the necrow process, equality (I, 1) is not respected, since the system is not returned to its original state. Instead, equality for the necrow process can be written (lowering the coefficient k.):
≠
Since integration limits are generally arbitrary, then for elementary values W. and Q.:
Q. W.,
hence:
Q. – W. 0
Denote by difference Q. – W. For any elementary thermodynamic process through du:
du Q. – W. (I, 2)
or for the final process:
–
(I, 2a)
Returning to the circular process, we obtain (from equation i, 1):
=
–
\u003d 0 (i, 3)
Thus, the value du it is a complete differential of some system status function. When the system is returned to the initial state (after cyclic change), the value of this function acquires the initial value.
System status functionU. , equal decisions (I., 2) or (I., 2a) is calledinternal energy systems .
Obviously, the expression (I, 2a) can be recorded as follows:
= U. 2 – U. 1 = ∆ U. = – (I, 2B)
U. 2 – U. 1 \u003d ΔU \u003d Q - W
This reasoning justifies the experimental way by the presence of a certain function of the system of a system that has the meaning of the total measure of all movements that the system has.
In other words, the internal energy includes the progressive and rotational energy of molecules, the oscillatory energy of atoms and groups of atoms in the molecule, the energy of the electron movement, internaloretical and other types of energy, i.e., the set of all types of particles in the system with the exception of the potential and kinetic energy of the system itself .
Suppose that the cyclic process was able to hold so that after the system returned to the initial state, the internal energy of the system did not accept the initial value, but increased. In this case, the repetition of circular processes would cause the accumulation of energy in the system. It would be possible to transform this energy into operation and obtaining this way of work without at the expense of heat, and "from nothing", since in a circular process, work and heat is equivalent to each other, which is shown by direct experiments.
The impossibility of implementing the specified construct cycle perpetual motion (perpetuum mobile) of the first kind,giving work without the cost of an equivalent amount of another type of energy, proved by a negative result of a thousand-year experience of mankind. This result leads to the same conclusion that in private, but more strict form we received, analyzing Joule's experiments.
We formulate the result again. The total supply of the energy of the system (its internal energy) as a result of the cyclic process is returned to the initial value, i.e. the internal energy of the system in this state has one particular value and does not depend on how the changes the system has undergone before reaching to this state.
In other words, the internal energy of the system there is a unambiguous, continuous and end function of the system status.
The change in the internal energy of the system is determined by the expression (I, 2B); For a circular process, expression (I, 3) is true. With an infinitely small change in some properties (parameters) of the system internal energy of the system, there is also infinitely little. This is the property of a continuous function.
Within the limits of thermodynamics there is no need to use general definition The concepts of internal energy. The formal quantitative determination through expressions (I, 2) or (I, 2a) is sufficient for all further thermodynamic reasoning and conclusions.
Since the internal energy of the system is the function of its condition, then, as already mentioned, the increase in internal energy with infinitely small changes in the parameters of the system full differential Status functions. Breaking the integral in equation (i, 3) to two integrals in the portions of the way 1 to state 2 (path "A") (see Fig. I) and back - from the state 2
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ProgramEquilibrium // M.: Metallurgy.-1988.-560s. Course physical chemistry / ME AND. Gerasimov, V.P. Tree, E.I. Ermin and others: under ....- 1980.- 180С. Gorshkov B.I., Kuznetsov I.A. / Basics physical chemistry. 2nd ed. // M.: Publishing House of Moscow University ...
Thermodynamic system - body or group of bodies in collaboration, mentally or actually separated from the environment.
Homogeneous system - The system, inside which there are no surfaces that are separated by the properties of the system (phase).
Heterogeneous system - The system inside which is present surfaces that are separated by the properties of the system part.
Phase - A combination of homogeneous parts of the heterogeneous system, the same in physical and chemical properties, separated from other parts of the system visible section surfaces.
Isolated system - a system that is not exchanged with the environment or a substance nor energy.
Closed system - A system that communicates with the environment, but not exchanged substance.
Open system - A system that communicates with the environment and substance and energy.
Status parameters - The values \u200b\u200bcharacterizing any macroscopic property of the system under consideration.
Thermodynamic process - Any change in the thermodynamic state of the system (changes of at least one parameter of the status).
Reversible process - A process that allows the ability to return the system to its original state without any changes in the environment.
Equal process - The process in which the system passes through a continuous series of states, infinitely close to the state of equilibrium. Characteristics equilibrium process:
1) Infinitely small difference in existing and counteractive forces: F EX - F IN > 0;
2) the system in the literal process of maximum work | W.| = max;
3) infinitely slow flow of the process associated with an infinitely small difference in the current forces and infinitely large numbers intermediate states t. > ?.
Spontaneous process - A process that can occur without external costs, and as a result, work can be obtained in an amount proportional to the change in the status of the system. Spontaneous process can flow reversibleor irreversible.
Non-promotional process - The process, for which the cost of work is required from outside in an amount proportional to the change in the state of the system.
Energy - measure of the ability of the system to work; General qualitative measure of motion and interaction of matter. Energy is an integral property of matter. Distinguish potential energydue to the position of the body in the field of some forces, and kinetic energyconducted by changing body position in space.
Internal energy system U. - The sum of the kinetic and potential energy of all particles constituting the system. You can also determine the internal energy of the system as its complete energy minus the kinetic and potential energy of the system as a whole. [ U.] \u003d J.
Heat Q. - The form of energy transmission by disordered movement of molecules by chaotic collisions of the molecules of two contacting bodies, i.e. by heat conduction (and at the same time by radiation). Q\u003e0 if the system gets warmth of the environment. [ Q.] \u003d J.
Work W. - The form of energy transmission by an ordered movement of particles (macroscopic mass) under the action of any forces. W\u003e0, if environment Makes work on the system. [W] \u003d J.
All work is divided into mechanical work of expansion (or compression)and other types of work (useful work) :? W \u003d -pdv +? W?.
Standard condition of solid and liquid substances - Sustainable state of pure substance at a given pressure under pressure p \u003d.1ATM.
Standard condition of pure gas - The state of the gas, subordinate to the equation of the state of the ideal gas at a pressure of 1 atm.
Standard values - The values \u200b\u200bdefined for substances in standard condition (are denoted by an additive index 0).
1.1. The first top of thermodynamics
Energy of non-futile and irrelevant; It can only move from one form to another in equivalent ratios.
The first top of the thermodynamics is the postulate - it cannot be proven by a logical way or derived from any more general provisions.
The first top of thermodynamics establishes the ratio between heat Q,work W.and changing the internal energy of the system? U..
Isolated system
Internal energy of an isolated system remains constant.
U \u003d.const or du \u003d.0Closed system
The change in the internal energy of the closed system is performed due to the heat, reported by the system, and / or work performed over the system.
? U \u003d Q + Wor du \u003d?Q +? W.Open system
The change in the internal energy of the open system is performed due to the heat, reported by the system, and / or work performed over the system, as well as due to changes in the mass system.
?U \u003d Q + W +? U Mor du \u003d?Q +? W +. i. U. i. DN. i.Internal energy is a function function; Does this mean that the change in internal energy? U. does not depend on the path of transition of the system from state 1 to state 2 and equal to the difference in the internal energy values U 2.and U 1. In these states:
? U \u003d u 2 - u 1For some process:
? U \u003d? (V i u i) NPOd -? (V I U i) Ex1.2. The use of the first start of thermodynamics to homogeneous one-component closed systems
Isochhore process (V. = const; ? V. = 0)In the simplest case, useful work is not performed.
du \u003d?Q +? W \u003d?Q - pDV du \u003d? q v \u003d c v dt \u003d nc v dtAll the amount of heat obtained by the system is on the change in internal energy.
– heat capacity at a constant volumei.e. the amount of heat required to increase the temperature of the system by one degree at a constant volume. [ With V.] = J / Grad.
C V. - Moldable heat capacity at a constant volume, J / (mol? Grad). For perfect gases:
C v \u003d 2/3 R - single andomic gas;
C v \u003d 5/2 R - Double gas.
Isobaric process (R = const) du \u003d?Q +? W \u003d? Q - PDV ? Q p \u003d du + pdv \u003d d (u + pv) \u003d DHH \u003d u + pv - enthalpy - system status function.
? N \u003d? (? I u i) Prod - ? (? I u i) ISX? Q p \u003d du + pdv \u003d dh \u003d c p dt -the thermal effect of the isobaric process is equal to the change in the enthalpy of the system.
– heat capacity at constant pressure. [FROM] \u003d J / Grad.
C R. - Mole heat capacity at constant pressure, J / (mol? Grad).
For perfect gases: C p \u003d C V + R; C p, C V \u003d[J / (Mol K)].
Thermal effect (heat) chemical reaction - The amount of heat released either absorbed during the reaction at a constant temperature.
Q v \u003d? U v Q p \u003d? U p The dependence of the thermal effect of the reaction on temperature. Kirchhoff lawThe temperature coefficient of thermal effect of the chemical reaction is equal to the change in the heat capacity of the system during the reaction.
Kirchhoff law:
For the chemical process, the change in heat capacity is set by changing the composition of the system:
? With r\u003d? (? i c p, i) Prod -? (? i C p, I) Execution or? C v \u003d? (? I C V, I) Prod -? (? I C V, I) ExThe integral form of the Law of Kirchhoff:
? N T2 \u003d? N T1 +? With P (T 2 - T 1) or? U t2 \u003d? U ti +? With V (T 2 - T 1)1.3. The second beginning of thermodynamics. Entropy
1) The heat cannot spontaneously move from the less heated body to the more heated.
2) The process is impossible, the only result of which is the transformation of heat to work.
3) There is some system status function called entropythe change of which is as follows associated with the heat absorbed and temperature:
in a non-equilibrium process
in equilibrium process
S - entropy,J / Grad,
- Limited heat.
Statistical interpretation of entropyEach state of the system is attributed to thermodynamic probability(Defined as the number of microstasters that make up this system of system), the largest, the more disordered or uncertain is this condition. Entropy is a function of a state describing the degree of unforgettable system.
S \u003d K.lN. W. - Boltzmann formula.
The system seeks to spontaneously switch to a state with a maximum thermodynamic probability.
Calculation of absolute entropy
The change in entropy during the chemical process is determined only by the type and state of the initial substances and the reaction products and does not depend on the path of the reaction:
? S \u003d? (? I S i) Prod - ? (? I S i) ISXThe magnitudes of absolute entropy under standard conditions are given in reference books.
1.4. Thermodynamic potentials
Potential - The value of which decreases the system produced.
Only those processes that lead to a decrease in the free energy of the system can spontaneously. The system comes to equilibrium state when free energy reaches the minimum value.
F \u003d U - TS - Helmholt's free energy - isochloro-isothermal potential(J) - determines the direction and limit of the spontaneous flow of the process in a closed system in isochloro-isothermal conditions.
df \u003d du - TDSor? F \u003d? U - t? SG \u003d H - TS \u003d U + PV - TS - free energy of Gibbs - isobaro-isothermal potential(J) - determines the direction and limit of spontaneous flow of the process in a closed system in the isobaro-isothermal conditions.
dG \u003d DH - TDSor? G \u003d? N - T? S ? G \u003d. ? (? I g i) Prod - ? (? I g i) ISX ? G 0. = ? (? i? G arr 0) Prod - ? (? i? G arr 0) ISX Conditions of spontaneous flow processes in closed systemsIsobaro isothermal (p \u003dconst T \u003d.const):
G.< 0, dG < 0Isochorean isothermal (V \u003dconst T \u003d.const):
? F.< 0, df.< 0Thermodynamic equilibriumit is called such a thermodynamic state of the system with minimal free energy, which under constancy of external conditions does not change over time, and this immutability is not due to any external process.
Terms of thermodynamic equilibriumin a closed systemIsobaro isothermal (p \u003dconst T \u003d.const):
? G \u003d 0, dG \u003d.0, d 2 G\u003e0Isochorean isothermal (V \u003dconst T \u003d.const):
? F \u003d.0, df \u003d. 0, d 2 F\u003e0 Chemical reaction isotherm equations:For reaction v 1 A 1 + V 2 A 2+ … = v? 1 b 1 + v? 2 B 2 + ...
Here C i, p i - Concentration, pressure of reacting substances at any time, other than the state of equilibrium.
Effect of external conditions for chemical equilibriumThe principle of the balance of equilibrium le chateel-brown
If there is an external impact on the system in a state of true equilibrium, then the system has a spontaneous process that compensates for this impact.
Effect of equilibrium position
Exothermic reactions :? H °< 0 (? U ° < 0). Повышение температуры уменьшает величину константы равновесия, т. е. смещает равновесие влево.
Endothermic reactions:? H °\u003e0 (? U ° \u003e 0). Increasing the temperature increases the value of the equilibrium constant (displays the balance to the right).
2. Phase equilibrium
Component - Chemically homogeneous component of the system that can be highlighted from the system and exist outside it. The number of independent system components is equal to the number of components minus the number of possible chemical reactions between them.
The number of degrees of freedom - The number of system status parameters that can be simultaneously modified in some limits without changing the number and nature of the phases in the system.
Phase ruleJ. Gibbs:
The number of degrees of freedom of the equilibrium thermodynamic system is equal to the number of independent components of the system to minus the number of phases F plus the number of external factors affecting the equilibrium: C \u003d K - F + N.
For the system to which from external factors affect only temperature and pressure,you can write: C \u003d K - F+ 2.
Principle of continuity - with a continuous change in the status parameters, all properties of individual phases are also changed continuously; The properties of the system as a whole are changed continuously until the number or nature of the phases in the system will change, which leads to an accelerated change in the properties of the system.
According to the principle of conformityon the system status diagram of each phase corresponds to part of the plane - the phase field. The line intersection of the planes correspond to the equilibrium between the two phases. Every point on the state diagram (T.N. point)respects some system status with certain values \u200b\u200bof status parameters.
2.1. Water status diagram
K \u003d.1. In the system there are three phase equilibriums: between liquid and gas (OA line), solid and gas (line s), solid and liquid (OC line). Three curves have an intersection point about called triple water point - correspond to equilibrium between the three phases and C \u003d 0; Three phases can be equilibrium only with strictly defined values \u200b\u200bof temperature and pressure (for water a triple point corresponds to a state with P \u003d.6.1 kPa I. T \u003d.273.16 K).
Inside each of the areas of diagrams (AOs, Boc, AOC), the system is single-feed; C \u003d 2 (Bariviant system).
On each of the lines, the number of phases in the system is two, and, according to the phase rule, the system of monovariant: C \u003d 1 - 2 + 2 \u003d 1, i.e., for each temperature value, there is only one pressure value.
The effect of pressure on the temperature of the phase transition describes klasa Uzius equation - Klapaireron:
V 2, V 1 - change in the molar volume of the substance at the phase transition.
The equilibrium curve "solid - liquid" on the water condition diagram is tilted to the left, and on the status diagrams of the remaining substances - right, since the density of water is greater than the density of ice, i.e. melting is accompanied by a decrease in volume (AV.< 0). In this case, the increase in pressure will be reduced the temperature of the phase transition "Solid Body - Liquid" (water - anomalous substance).For all other substances (t. N normal substances)? V pl\u003e 0 and, according to the Clausius-Klapairone equation, the increase in pressure leads to an increase in melting point.
3. Properties of solutions
3.1. Thermodynamics of solutions
Solution - a homogeneous system consisting of two or more components, the composition of which can be continuously changed in some limits without a jump-like change of its properties.
Diffusion in solutions
Diffusion - Spontaneous process of equalizing the concentration of the substance in solution due to thermal motion of its molecules or atoms.
Fiki law:the amount of substance diffuseing per unit of time through the unit area of \u200b\u200bthe surface is proportional to the gradient of its concentration:
where j. - diffusion stream; D. - Diffusion coefficient.
Einstein-Smolukhovsky equation:
where? - viscosity of the medium; R. - Radius of diffusory particles.
Gas solubility in gasesThe Act of Dalton:the total pressure of the gas mixture is equal to the amount of partial pressures of all gases included in it:
R total \u003d? p I.and PI \u003d XI.P sharesThe Law of Henry Dalton:the solubility of gas in the liquid is directly proportional to its pressure above the liquid: C i \u003d kp i,where C I. - concentration of gas solution in liquid; k. - Proportionality coefficient depending on the nature of the gas.
As a rule, when the gas dissolved in the liquid is highlighted by heat (to< 0), therefore with an increase in temperature, solubility decreases.
Formula Sechenov:
X \u003d x 0 e -kswhere X.and X 0 - Gas solubility in a pure solvent and electrolyte solution with concentration FROM.
3.2. Convigative properties of non-electrolyte solutions
Configative (collective)the properties of solutions are called relative to the properties of the solvent, depending mainly on the number of dissolved particles.
Pressure of a saturated pair of dilute solutionsPar, located in equilibrium with liquid, is called saturated.Pressure of such a para p 0.called pressure or elasticity of saturated pairpure solvent.
The first law of Raul.The partial pressure of a saturated pair of the component of the solution is directly proportional to its molar fraction in the solution, and the proportionality coefficient is equal to the pressure of saturated steam above the clean component:
p i \u003d p i 0 x iFor a binary solution consisting of components A and B: a relative decrease in the pressure of the solvent steam above the solution is equal to the molar fraction of the dissolved substance and does not depend on the nature of the dissolved substance:
The solutions for which the Raoul's law is performed are called ideal solutions.
Pressure of a pair of ideal and real solutions
If the components of the binary (consisting of two components) of the volatile solution, then the solution of the solution will contain both components. General composition, they say. Shares in (x c) Pressure Couple:
p \u003d p a 0 x. A + P B 0 x. B \u003d P a 0 (1 - X. B) + p b 0 x.B \u003d p a 0 - X. B (p a 0 - p b 0)
If the molecules of this component interact with each other more than with the molecules of another component, then the true partial pressure of the vapor over the mixture will be greater than calculated according to the first law of Raoul (positive deviations ,? n TV\u003e 0). If homogeneous particles interact with each other weaker than heterogeneous, partial pressure of the vapors of components will be less than calculated (Negative deviations ,? H solitary< 0).
Crystallization temperature of dilute solutionsThe second law of Raul.Reducing the temperature of the freezing of the solution? T deputy directly proportional to the molaous concentration of the solution :? T deputy \u003d T 0 - T \u003d ks m,where T 0 -freezing temperature of a pure solvent; T. - the freezing temperature of the solution; TO - cryoscopic constant solvent, hail / kg mole,
T 0 2. - the freezing temperature of the solvent; M. - Molecular weight of the solvent ,? H pl - mole heat of melting solvent.
Boiling temperature of diluted solutionsBoiling temperature - The temperature at which the saturated pair pressure becomes equal to external pressure.
Increase the boiling temperature of solutions of non-volatile substances? T K \u003d T K - T to 0in proportion to the decrease in the pressure of saturated steam and directly proportional to the molaous concentration of the solution:? T kip \u003d EU M,where E - Eculicopic constantsolvent, hail / kg mole,
Osmotic pressure of dilute solutions
Osmosis - Preferably one-sided passage of solvent molecules through a semipermeable membrane into a solution or solvent molecules from a solution with a smaller concentration into a solution with a greater concentration.
The pressure that needs to be applied to the solution to prevent the solvent movement into the solution through the membrane separating the solution and the pure solvent is numerically osmotic pressure?(PA).
Principle of Vant-Gooff:the osmotic pressure of the ideal solution is equal to the pressure that had a dissolved substance if it were, while in a gaseous state at the same temperature, would occupy the same amount that the solution occupies :? \u003d CRT.
Isotonic solutions - Two solutions with equal osmotic pressure (? 1 \u003d? 2).
Hypertensive solution - Solution, the osmotic pressure of which is greater than that of another (? 1\u003e? 2).
Hypotonic solution - solution, the osmotic pressure of which is less than that of another (? 1< ? 2).
3.3. Solutions of electrolyte
Divociation degree? - the ratio of the number of molecules n,blooming on ions to the total number of molecules N:
Isotonic coefficient I Van-Gooff - The ratio of the actual number of particles in the electrolyte solution to the number of particles of this solution is excluding dissociation.
If because N.molecules predissated n,and every molecule broke up on? ions, T.
For non-electrolytee i \u003d.1.
For electrolytes 1.< i.? ?.
3.4. Configative properties of electrolyte solutions:
Arrhenius electrolytic dissociation theory
1. Electrolytes in solutions are disintegrated by ions - dissociate.
2. Dissociation is a reversible equilibrium process.
3. The forces of the interaction of ions with solvent molecules and small with each other (i.e., solutions are ideal).
The dissociation of electrolytes in the solution occurs under the action of polar solvent molecules; The presence of ions in the solution predetermines its electrical conductivity.
By magnitude of the dissociation, electrolytes are divided into three groups: strong(? ? 0,7), middle power(0,3 < ? < 0,7) и weak(? ? 0,3).
Weak electrolytes. Dissociation constantFor some electrolyte, disintegrating in the solution on ions in accordance with equation:
A in B - AA X- + BB y +.
For binary electrolyte:
- The law of the ostel dilution: the degree of dissociation of weak electrolyte increases with the dilution of the solution.
The activity of the dissolved substance - empirical value replacing concentration - activity (effective concentration) but,associated with concentration through the activity coefficient f.which is a measure of the deviation of the properties of the real solution from the perfect:
a \u003d fc; A + \u003d F + C +; a_ \u003d F_C_.For binary electrolyte:
- average electrolyte activity;
- average activity coefficient.
Debai Hyukkelfor binary electrolyte: LG f. = -0.51Z 2 i?,where z. - the charge of the ion for which the activity coefficient is calculated;
I - ion power of solution I \u003d0.5? (C i R i 2).
4. Electrical conductivity of electrolyte solutions
Conductors I kind - Metals and their melts in which electricity is transferred by electrons.
Conductors II - solutions and melts of electrolytes with ionic conduction type.
Electricitythere is an ordered movement of charged particles.
Every conductor through which the current flows is defined for him resistance r,which, according to the law of Ohm, is directly proportional to the length of the conductor l.and inversely proportional to the cross section S;the proportionality coefficient is resistivitymaterial? - resistance of the conductor having a length of 1 cm and the section 1 cm 2:
Value W,reverse resistance is called electrical conductivity - Quantitative measure of the power of the electrolyte solution to carry out an electric current.
Specific electrical conductivity? (k) - conductor conductor I sort 1 m Long with an area cross section 1 m 2 or electrical conductivity of 1 m 3 (1 cm 3) of the electrolyte solution (conductor II) at a distance between the electrodes 1 m (1 cm) and the electrode area 1 m 2 (1 cm 2).
Molar electrical conductivity of the solution)? - electrical conductivity of a solution containing 1 mol of the dissolved substance and placed between the electrodes located at a distance of 1 cm from each other.
The molar electrical conductivity of both strong and weak electrolytes increases with a decrease in the concentration (i.e. with increasing dilution of the solution V \u003d 1 / C), reaching some limit value? 0 (?), called molar electrical conductivity with infinite dilution.
For binary electrolyte with single-charged ions at a constant temperature and field strength 1 V M -1:
? = ?F (u + + and?),where F. - the number of Faraday; and +, and? - Absolute mobility (m 2 V -1 s -1)cation and anion - the speed of movement of these ions under standard conditions, with the difference in potentials in 1B per 1 m of the length of the solution.
? + \u003d FU +; ?? \u003d FU?,where? +, ?? - Mobilitycation and anion, M 2 mol -1 (OM 2 mol -1).
? = ?(? + + ??)For strong electrolytes? ? 1 I. ? = ? + + ??
With infinite dilution of the solution (V. > ?, ? + > ? ? + , ?? > ? ? ?, ? \u003e 1) for strong and weak electrolytes? ? \u003d? ? + – ? ? ? - The Law of Kolrauša:the molar conduit with infinite breeding is equal to the amount of electrolytic mobility? ? + , ? ? ? Cation and anion of this electrolyte.
H + and OH ions? have abnormally high mobility, which is associated with a special charge transfer mechanism by these ions - relay mechanism.Between the hydroxony ions H 3 O + and water molecules, as well as between water molecules and OH ions? Continuously exchanged protons across equations:
H 3 O + + H 2 O\u003e H 2 O + H 3 O +
H 2 O + OH? \u003e Oh? + H 2 O
5. Electrochemical processes
5.1. Electrode potentials. Galvanic elements. EMF.
In contact with two chemically or physically heterogeneous materials (Metal 1 (Conductor I) - Metal 2 (Conductor i of genus), Metal (Conductor I) - Metal Salt Solution (Conductor II), Electrolyte Solution 1 (Conductor II) - The electrolyte solution 2 (conductor II of the genus), etc.) between them occurs double electric layer (DES).DES is the result of an ordered distribution of oppositely charged particles on the border of the phase partition.
DES formation leads to a potential jump?, Which in conditions of equilibrium metal (genus conductor) - a solution of metal salt (Conductor II) is called galivani potential.
System: Metal (ME) - aqueous salt of this ME - called electrodeor semi-elementand schematically depicted as follows:
The electrode (P / E) is written so that all substances in the solution are placed on the left, and the electrode material is to the right of the vertical feature.
? \u003e 0, if the reaction of the reduction of N + + is proceeding on the electrode noney? -Me 0
? < 0, если на электроде протекает реакция окисления Ме 0 - Ме n+ + nE?.
Electrode potential E. N + / me is called the equilibrium potential difference arising at the border of the phases conductor I type I / conductor II of the genus and measured relative to the standard hydrogen electrode.
nernsta equation,where n. - the number of electrons involved in the electrode reaction; FROM N + is the concentration of cations; E. Me n + / - Standard electrode potential.
Contact potential? ? - equilibrium horse racing, occurring on the border of the section of two conductors of the I genus.
Diffusion potential? Diff is an equilibrium potential difference arising at the phase border of the genus II / conductor II of the genus.
Galvanic element (E.) – electrical circuitconsisting of two or more P.E. and producing electrical energy due to the chemical reaction occurring in it, and the stage of oxidation and the reduction of the chemical reaction is spatially separated.
The electrode in which the oxidation process proceeds when the galvanic element is called anode,the electrode on which the recovery process is underway - cathode.
Rules of Jew for recording galvanic elements and reactions flowing into them1. In E. The work is done, so the EMF of the element is considered to be positive.
2. The magnitude of the Galvanic Chain EMS E.the algebraic amount of potential jumps on the boundaries of the partition of all phases is determined, but since oxidation occurs on the anode, the EMF is calculated, the value of the potential of the anode (left electrode) is determined from the numerical value of the cathode potential (left electrode). right Pole rule.Therefore, the element scheme is written so that the left electrode is negative (oxidation flows), and the right - positive (recovery process flows).
3. The boundary of the section between the conductor I of the genus and the conductor II of the genus is indicated by one feature.
4. The boundary between the two guides of the genus is depicted by a dotted feature.
5. The electrolyte bridge on the border of two conductors II of the genus is denoted by two dotted features.
6. The components of the same phase are recorded through the comma.
7. The equation of the electrode reaction is recorded so that the substances in the oxidized form be left (OH), and on the right - in the restored (Red).
Galvanic element of Daniel-Jacobiit consists of zinc and copper plates immersed in the corresponding solutions of ZNSO 4 and CUSO 4, which are separated by a saline bridge with a solution of KCl: the electrolytic bridge provides electrical conductivity between solutions, but prevents their mutual diffusion.
(-) Zn | Zn 2+ :: Cu 2+ | Cu (+)Reactions on the electrodes:
Zn 0\u003e zn 2+ + 2e? Cu 2+ + 2e? \u003e Cu 0.Summary redox process:
Cu 2+ + Zn 0\u003e Cu 0 + Zn 2+The operation of the current electroplating element (and, consequently, the potential difference) will be maximal when it is reversible when the processes on the electrodes flow infinitely slowly and the current of the current in the chain is infinitely small.
The maximum potential difference arising when the electroplating element is reversible electrical power (EMF) galvanic element E.
EMF element E. Zn / cu \u003d? Cu 2+ / Cu +? Zn 2+ / Zn + ? K +? Differ.
Excluding? Diff and? to: E. Zn / Cu. = ? Cu 2+ / Cu +? Zn 2+ / Zn = E. Cu 2+ / Cu + E. Zn 2+ / Zn is galvanic elements consisting of two identical metal electrodes, lowered into solutions of salt of this metal with different concentrations with 1\u003e C 2. The cathode in this case will be an electrode with a greater concentration, since the standard electrode potentials of both electrodes are equal.
Concentration chains
The only result of the operation of the concentration element is the transfer of metal ions from a more concentrated solution into less concentrated.
The operation of the electric current in the concentration galvanic element is the operation of the diffusion process, which is carried out reversible as a result of its spatial separation by two opposite in the direction of reversible electrode process.
5.2. Classification of electrodes
Electrodes of the first kind. Metal plate immersed in solid salt of the same metal. When the element is reversible, which includes an electrode, on a metal plate, the process of transition of cations from metal into the solution is a solution or from a solution into a metal.
Second-sort electrodes.The metal is coated with a low-soluble salt of this metal and is in solution containing another soluble salt with the same anion. The electrodes of this type are reversible relative to the anion.
Electrodes comparison - Electrodes with precisely known and reproducible potentials.
Hydrogen electrodeit is a platinum plate washed by gaseous hydrogen, immersed in a solution containing hydrogen ions. Adsorbed hydrogen platinum is in equilibrium with hydrogen gaseous.
PT, H 2 / H +Electrochemical equilibrium on the electrode:
2N + +. 2e? - H 2.The potential of a standard hydrogen electrode (with the activity of H + 1 mol / l ions and hydrogen pressure 101.3 kPa) is taken equal to zero.
Electrode potential of a non-standard hydrogen electrode:
Calulose electrodeit consists of a mercury electrode placed in a KCL solution, a certain concentration and a saturated Calometra Hg 2 Cl 2:
HG / HG 2 Cl 2, KCLCalulose electrode Reverse relative to chlorine anions
Chlorinebry electrode - We turn relative to chlorine anions:
{!LANG-98f77c1083b1c10b17e0a7111c83f3e4!}
{!LANG-075c0295df378c56a91d89ed05b537eb!}
{!LANG-e4c1029f37d170981f1fd491c5c19021!}{!LANG-9fa356b612c4c1b8e1071293bd3caa53!}
{!LANG-11559c32b6668d5777c25fb3a6c74020!}{!LANG-79e8d9c2edea887176986c25792e07c4!}
{!LANG-00d813f3843c0543eb3e568890dd6070!}{!LANG-369fd6a31c4c30d9763621afa52b60b9!} {!LANG-f982b3b4532b49023a1bda3e31ef4995!}{!LANG-43e713a288154863cfdc7d83969ce2bd!}
{!LANG-48981fc2135ce25ff188301ae1cc8e3b!} E.{!LANG-122244ae106a0561a1fa7607969de9d9!} {!LANG-3d94e9f7e307d8c12e29a6ee3ac28fc0!}{!LANG-0206c7057d75e003889e61f913ff642e!}
{!LANG-7cda523e7a8886ff2be9d759c584d83a!}{!LANG-b771d10335b432a77410cbb98df0592e!} {!LANG-0e94a210a558fb511f67b4ccc16d8ae1!}or {!LANG-b93f58b7fffb05588b2371f12d472b2e!}
{!LANG-308363728868ffeb310d3392325240f7!} noney? -{!LANG-06f22caeba98cb28f60c4adaaa856f9b!}
{!LANG-56fa74a7d37ce1675b6f1c5fdd9b8223!} {!LANG-4d856564823395567cf99db6e2046a19!}{!LANG-0822b10d6e019aa702e47a56c9417b80!}
{!LANG-ae81dde9c832fadbd603ed2da5ca9246!}
{!LANG-84c918ce1960fc7762d508793e9718f9!}
{!LANG-9888d7404289ecc5368201134281510f!}{!LANG-6cd75ff070f46c28204ab13b329f7ab6!}
{!LANG-1e3e0bc15723e9eeebde5608ca29400a!}where {!LANG-d6749b6407ef9874c0e6063037239ae9!}{!LANG-a1cfc13fe6646224b05936ba3ad5dcda!}
{!LANG-4f5932551fdab7106bce8f1f095cf4f8!}{!LANG-300ba1936318ad66721bc59c26e6454e!}{!LANG-ae663020b53ec4cdebb4783905cd9d16!}
{!LANG-72dd990d86de8de3ca151d905181f55a!} {!LANG-a4b81aeb09089582e18a9c4ba75917cc!}{!LANG-e785f1a000fc1509ca7e9faae7850ad9!}
{!LANG-882795147eea1ac87976ee622b9ad31f!} {!LANG-a9edcba9448d16f8a376b306f113dfb2!}
{!LANG-92d26f161163af5bef569d4220ed6ffa!}1. {!LANG-efaf9e549681abf9d92a8e89573f4c4a!}{!LANG-28ae1dfde6317fd262ea914e27325cb0!}< ? 0) g >{!LANG-f923e48070cb45c7ca28eaf7926202c4!}
2. {!LANG-26bdcefa93c4a7dda2f9fb27cf3a84c0!}{!LANG-da008aa84f965fd23ddaea61cbaa4a8f!}< 0 (неорганические кислоты, основания, соли, глицерин, ?-аминокислоты и др).
3. {!LANG-2e12fdbd772e64890796b8d76ff163f8!}{!LANG-3498bca0d1672abb9ab60d66abf48798!}
{!LANG-a49f9ccb4234d233a63e7603c6efdbf3!}{!LANG-34ec8e32d3e778b98a50e5aef397321f!}
{!LANG-e77f74ebb2654d4652b6cf5311c24b2a!}
where {!LANG-3b5d5c3712955042212316173ccf37be!}and TO{!LANG-2cdcc7402c8133983868485164f2cb56!} {!LANG-3b5d5c3712955042212316173ccf37be!}{!LANG-1975331f4856031431468b579ae054c5!}
{!LANG-01cec236b8df128ccee552005ac9dd80!} {!LANG-459dc3de4a81b3208a27c8961a34e10f!}{!LANG-a4690346250335f0c086361300f51242!} {!LANG-72b3165329c611e764c5c84f2d82927f!}
{!LANG-e3c47139e8c6e2aaddc7ea871be8ea92!}
{!LANG-f7775c7b45fa36db75fbfa6fd26742f4!} {!LANG-5689e1671763bf873274497b11c330c7!}{!LANG-a556eedf2d1921e0e8ef0e524cd2920a!} {!LANG-e6dd2682202b5ce7729ee8471ba3b098!}{!LANG-a01ee27938d82b1c1b861dc4a84f1c5c!}
{!LANG-cb1c3ca1e331ca816a918c91bff3bbef!}
{!LANG-55ffe307367e1dca34af153e9f468734!}{!LANG-766106c84cfaf09bbf373820d141e593!}
{!LANG-6ffc66adadad2eddb0f3d9f8acf168b6!}{!LANG-36c82b7d37be0baa7db5c1724c3b04d6!} {!LANG-d2e4952cbe95035723ae76bd276b1030!}{!LANG-a0a4d3b8f2c69ac2abb6a2007de49146!}
{!LANG-c30a874aeaea1134ffb2be7c9e201def!}{!LANG-6f3ef0050d73655529b142b1744f2375!}
{!LANG-87e7d616dfeadaf1b565e86fdce2ba11!}or {!LANG-fbbb714b943db490661ed53454902a7f!}TO{!LANG-540ed81ed9112cb824ab15647a1d9a16!} {!LANG-1d41a2b62d027a7ce72a44a7784a2972!}{!LANG-6ae67e501ef6f58e1b1ac4ae2ab2afd6!}
{!LANG-67835e5749595b8269572006c6bfe1f5!}
{!LANG-7b80a7098259a95e5eef5f2c14c9073f!}
{!LANG-8be96e4693b0a25ca549512bde9c9f2d!}
{!LANG-72be0a34ddd3065f614f43df5b92b356!}
{!LANG-dc0cf399727b732027f92fdc5cfb4123!}
{!LANG-157df003041272c541d590c56136a93c!}
where {!LANG-842cba4eabd778b511ffbc8f91efcf4c!}{!LANG-1d49d92d174750d1949d7d87f11a43a9!} {!LANG-3b5d5c3712955042212316173ccf37be!}{!LANG-638fa7019526f9a80bea009172cc1f77!}
{!LANG-eff4eaa408ea519bc26a8ad9c69321af!}{!LANG-b936e36eef97b606ae6c0ab501c2edc2!} {!LANG-3274d61cce9942e397f23a47b58f1f25!}{!LANG-00a3d4f200595056fd8396207474dfd1!} {!LANG-9da221b5004b2c31658f6d8cb6f424bd!}{!LANG-61fb9d9f4f20ee7d689093b01e3c433c!} n.{!LANG-ac0c595453e4aca59a6cf36e6ca8f4c8!} {!LANG-f08266997a30e663afa614b3ebe3c772!}= 0,1–0,6).
{!LANG-aa9922e20896563a2ee0ddfb62e5da86!}
{!LANG-21dd40a49ff5d64d99751ed9921c3542!} FROM{!LANG-c25d1ff4279255e8b6676ecd4d395e29!} {!LANG-425a3e9d228952d6bf6ae19e67d8ade4!}{!LANG-de9b38eb7d969ed0acfa236cdf2047e8!} {!LANG-69b64623f86def16ce17d454b8be41ae!}{!LANG-7e1405068de89ec0fc7b767a1941a7e5!}
{!LANG-477958be8e6e463f63adf284f9a1283e!} {!LANG-adbf9439d818faccc8ea2e718792b097!}{!LANG-070e7a35a2562516d2f15e9f455e8f0a!} {!LANG-152d6ae770d40337c23530f7752ba55b!}
{!LANG-a93ece71546aa1ae1337e5539587f076!}
{!LANG-9709e04dbf3d36e459c70b8daee3d6b4!}
where M.{!LANG-f5e81eb95a9ffde375669c57c3eecd7c!}
{!LANG-e6af97f987cbf480b365a2b71be406f2!}{!LANG-000bf868449725ac88758e38a0796ba9!}
{!LANG-57d8111ad3f08cd53f3d0340482f5948!}
{!LANG-a6af6d25f9cc3af3e60d9f1b4e75a790!}
{!LANG-116026926459e26936719fc6c051d3c3!}{!LANG-5efc115f1a26b76f68ebe8e435b66420!} {!LANG-8d14b2f0de3812609562918db3a7d87d!}{!LANG-8ad70946fcc5c50aecf8fcaba69219ec!}
{!LANG-3d790f46bd89b8769c7d0463ad4b5b4f!}{!LANG-1e4082e6a902f2399865425295d7a96c!}
{!LANG-80de26ff84e2dc08724507162f4ba882!}
{!LANG-bcb480a6c94d2a570a5d8b720f002fc1!}{!LANG-41c9d9427dab275d5a3c4c1a4889b638!} {!LANG-95219cf9e8b79a28aa896ce35ef7be76!}{!LANG-654cc69cd2b126ab10ca02f21907871e!} {!LANG-511188ed0fe471a103e60af1eecc3c15!}{!LANG-705ba358464556a69dc1a56d89111f05!}
{!LANG-bd06d864d68949e1738f26acd4901d11!} {!LANG-4dace983a18b3e53cf5df670f9758bfb!}
{!LANG-d8867f7b2fa53d37d550521a84a9ae0c!}{!LANG-3d230ee229c039798695b55efefb0847!} d.{!LANG-5e96e35faf9880a37661a8fa602093e1!}
{!LANG-07c2339581b4e0b29ca2ae1e33f2fad1!}{!LANG-70a833f7f8148dc4fae1ab2038c693c4!}
{!LANG-55c62ec8469911a81404435b6338559b!}
{!LANG-202d6d2e9bf5928d0e7a7bf3ee0d3947!} {!LANG-20884cf8f7358780ade7d4689ed75f32!}{!LANG-111c72a2811ef9b1c38b6987e1fe238b!}
{!LANG-8d2bb24f79f6392e9b97cbdd1aeb66d3!}
{!LANG-25de302e12ff647bf42d1bf9cd38b51a!}
{!LANG-ab4dda4410238dab6d6725efe336a5ca!}
{!LANG-4d5223b5c1cc5d5b94a712772494d698!}
{!LANG-33b09bba3e129bf5f8a28561a195d389!}
{!LANG-13021790b63137c9a490ac3fcd29effe!} {!LANG-30837f9f676f3057b474944fc7efec18!}{!LANG-37ccaf24d318c07d96d4e8050ef46294!}{!LANG-3b278a9092e196ba86f732f3d2759e90!} {!LANG-42b464f6f45590436006830353ccc10b!}{!LANG-50490560531af16333684ff66c51ec93!}
{!LANG-cc044c3136ecf5cf5d7f759d0e52f4f4!}{!LANG-ee509a1b79ceccc63f30609bb3d0abff!}
{!LANG-c7371b34e7070ecfb85c91c3130d73ca!}{!LANG-fad19be33cd4db2549aa789c09c6fb97!}{!LANG-687ae12a1e83543a48045af25e9fd935!}
{!LANG-7bb3bade46fcc70975f06ce06feb54f4!}{!LANG-01c540338040386564b6e3e57eb57709!}
{!LANG-a2e927bac856b535d503a57f48b48af4!}
{!LANG-9490d5ee33888ef45227cae63af1bfba!}
{!LANG-228837bb66385934f64dc90d2b5d616c!}{!LANG-c0aa0b9451cb139e8154a484ab26b4e4!}<< ?);
{!LANG-434499d9d48e3db6be3bc691424c99cb!}{!LANG-b31f839f079bca68489587a9b2020f71!}
{!LANG-99afc039b63ce0ffa866b5d45191177e!}{!LANG-4ad8e2d598ad848e72cf6188a55f91ad!}
{!LANG-3891c864d81dcb6cef82327666423eb1!}{!LANG-f4844962e259d54a8aa647ae812835ac!}
{!LANG-5598caedeea6750f64ffc84a8e074167!}{!LANG-5cc1356b7146ab371f938bc05cf8e41d!} {!LANG-86752d3d1bebbe6015f69bb61f0d8151!}{!LANG-d2639bdbddcef7eac60e44aa6d6444a9!}
adsorption{!LANG-604202767d60129b9013eec50a25cdb0!}
{!LANG-09eef97645db763b1484f45a76058575!}
{!LANG-d8fb1f973481591bda2abb3935c244e0!} {!LANG-425a3e9d228952d6bf6ae19e67d8ade4!}{!LANG-15d25ab1772a1692ad4387211e7d2500!} {!LANG-600af2af26a1846f6abe3c7c2650ab66!}{!LANG-d2145352031c783d75e1e85e7ef0a0a5!}
{!LANG-6cc5213e9c67ad8224440506c301551b!} {!LANG-19099c81163e6298d3deb3d557e802a0!}{!LANG-076cc1e893581bdb55f3d0709b3fedae!} {!LANG-d254c08e47e6495bb44786b0569c288e!}
{!LANG-8efd40e6bd624ccd87e15880827974bd!}
{!LANG-79ed2b77db1faf0f7bf2efce866e107a!} {!LANG-c5d9f5736345398c4adfb6471355927e!}{!LANG-117f5f57c9fb1de7eeeb42b2b9687575!}
Diffusion{!LANG-acf433d1330bf22db9feba452256bded!}
Fiki law:
{!LANG-544bb5ff7b6679b92e30d6742b8ade4b!} {!LANG-7dc99e85d04c2632103a00d397b28bab!}.
{!LANG-f57f4cd87716b62134b2983727fecfe7!}
{!LANG-c09876421f9ebe29eb39c7131fe5ece2!} {!LANG-69b64623f86def16ce17d454b8be41ae!}{!LANG-70c4cd5020a4c6be99a2f73e24bf09e1!} {!LANG-425a3e9d228952d6bf6ae19e67d8ade4!}{!LANG-eaa6c0c240ef65179ca56e31defef391!} {!LANG-2a7e2da05cd6b8e575eed343d5d20caf!}{!LANG-3fc04160a604eb1845a83a9713bfe541!} T.{!LANG-4b1ce9bb40fef266fa4298db3cd0c3b9!} k.{!LANG-9c49b04724bf20f2112a48318411dd63!}
{!LANG-aec52a9d79e513f743e9583229ddde4d!}
{!LANG-6fcc1eb73b9f2f5541081107efcc3ddb!}
{!LANG-6efc24089aeb0a8b79ae7fac66ed277c!}
{!LANG-d6aa6c9a020bdc8a3ebcc38e4510824d!}{!LANG-2d0cac9e5b5b95f48e62f940239ada09!}
{!LANG-a13fdc7920f6a2750bde8e3ffaff5832!}{!LANG-22db0cd01e7e58f387c0bd2cf82d9f33!} {!LANG-7748f1faef5166c693d99024a444c2dd!}{!LANG-a1a2305227d3776074a61cb0a99f9342!} {!LANG-aab13bb19f8ba905e5a254f0c24775c4!}
{!LANG-a3fc0fa4415735889acab24a4ee58b6a!}{!LANG-c197a2b2f69ce2cf97e28d771c2a9c51!}
{!LANG-1539362506c0ba21e073fee3bd48d419!} {!LANG-090bbc5ec56af1309dce45b5f35c5646!}
{!LANG-34945f1906adc1a408fae3c2d675c0e3!} {!LANG-99d5da2d4b8b19c079d3a6b41ef32fca!}{!LANG-a6e91406dc2235d62c0bf3659356d1b0!} {!LANG-2c8dbb2a01c874e5f3a84eab6ef840e2!}
{!LANG-e2d1456356c42ccaf4043c0044128fea!} {!LANG-9ecd05b8b7ba22937273a74f4aea8394!}{!LANG-895b4fa16700d5c5723d896a6fc886bc!}
{!LANG-0655c1f5ec0f93959d005bb1fb27b578!} {!LANG-239b00fcd976501e947b0070ec1a6b87!}{!LANG-c2dafd8f87005d67d49a599df58bc8b9!}
{!LANG-f0ad2eac8bf00fb8baf34cb76c97bfc6!} {!LANG-ec51fe285659368af6702e936913208c!}{!LANG-024dddde335501b144d8e003050e6287!} {!LANG-44663bb8e6af64b14b300f56fcf724b0!}{!LANG-807252d8ea87315506370406dc3b2253!}
{!LANG-23c634534311021addfb5967b74e5273!} {!LANG-f473670c5b1289cd2a7d8d3a985f3bef!}{!LANG-8073cdbc39fd72d9dff295763b7b9744!} {!LANG-4879b767d0451cfc865ba5b0817d3f22!}
{!LANG-6fb68ce745d5d4cc37f3e71a613b1f8c!} {!LANG-f8be99379b3bcba0ae2c3b537dd77162!}{!LANG-e680419de42d01d5c4f7263b8916926a!} {!LANG-febce118b5334ae76dcb6c7e635ac180!}
{!LANG-fd8d1b6c43fc38a8993a116761970132!}
{!LANG-f731da6863ab8eeb5b8793c7a3d2b75b!}{!LANG-6d6fd8197be1cd0ccbcff428378f89bb!}
{!LANG-4f9e33050fcf7c379c202a1e79ca59c4!} {!LANG-a188bc8d4c5b436504c118a1749b6588!}
{!LANG-e6b1ccbc5656f848f8a87bce9aa8b321!}{!LANG-965e619234eda8b51e59c935ed8b5108!}
{!LANG-96b05dc3e08fc2b61b6b30015d05285b!} {!LANG-81185896d6259da9421bde180b5c6b55!}{!LANG-db8cac9db33cc49b8f1734b325e17a9b!} {!LANG-02c7f91365f7d5ada409ff1fcf991da3!}{!LANG-9ecb0cab0cac98dec005dceff2e320df!}
{!LANG-cb771aaf5eb5f667165bc8f2a64fcd54!}{!LANG-a931c24269a87b963322792d12761ad8!}{!LANG-7effae545acff28077a124927b5b2ba6!}
{!LANG-6909bfbd91957111253efd08b7c475c1!}{!LANG-49b3b427e38296146b8791081d0ca8c7!}
{!LANG-0533dc2cf9c64f38379fab01455b5079!} {!LANG-b90383d160fbe33942cab9bdff87a32b!}{!LANG-8be5447c7547b0857569457937f932c0!}
{!LANG-58c9d80b635b751bbd4742d38ee56db8!}
{!LANG-1e17962922d42e112cc1c208bdb15b55!}
{!LANG-01177c902c75e41fef92b5c7984e185c!}
{!LANG-95b688a25b38155d7768dd68981d50c7!}
{!LANG-30ce81d78438df82b1332092d822a9e3!}
{!LANG-8fcd142647f09e1753ddaa8e54d17c1f!}
{!LANG-a29275a8be8658774696a3b0cf1ae95c!}
{!LANG-19e152248bb76821973983546bfec0a9!}
{!LANG-ec7c7645985a30ccb8db3be1d35d6ccb!}{!LANG-3a396732afcaffb40c57ed8f85f30914!}{!LANG-7fda7ef1fec5c0fca2e1c1f0f58a76b6!} {!LANG-579a8df9041d12cfdbe251483f549a0b!}{!LANG-a9d86424205bfa125ec94de7878ffc72!} {!LANG-717526b12333ddc0cb18338a7b5e2cb2!}{!LANG-3a90ef70ec0eb47e3520a4f8c82edc9d!}<р не изменяется. Данный электролит не содержит таких ионов, которые были бы способны к специфической адсорбции на частицах по правилу Па-нета-Фаянса, т. е. не способны достраивать кристаллическую решетку агрегата:
{!LANG-7f801c818d26e959555b1332b0338477!} {!LANG-f9d79a4709b34d475b74596e72e4f237!}{!LANG-c87bbad6abf33556f6b4516974889f6b!}
{!LANG-b466265cff1f488897d389ba3559de62!}{!LANG-337536ba3df3e0faa0d555f692328e1f!} {!LANG-6014f847cf71824b4a758a52311e1588!}{!LANG-a64fc0a9bed818b0ee6730d6df2e439b!} {!LANG-86ec28033a3c6ad420c4db8e80ff2c63!}{!LANG-c020fadc7168ff27089fa4fb7edd496e!}
{!LANG-1cc610bbb49e599396791545a3a387ef!} {!LANG-99abffd9aa414afa4170493f32088db9!}
{!LANG-4adbd3e0dbed782ef819dbb50b0ff12f!}{!LANG-cc2348ae7f7026fbbe73d39c6f6728ce!} {!LANG-929fc94f29380f93d5afcf785b9e55d9!}
{!LANG-a749bbd79965ed7d9a692e89fc6aabcb!} {!LANG-425a3e9d228952d6bf6ae19e67d8ade4!}{!LANG-3bd8ceb8cce8976325f9fddbebae424b!} {!LANG-425a3e9d228952d6bf6ae19e67d8ade4!}{!LANG-9491f2672ee3bb306902d2729bb80c4d!}
{!LANG-f70348189248a8974a66e0f3d8fabbab!} {!LANG-d5730489a0a3cefd77dd7c9b4034dc10!}
{!LANG-0f4c717ae4e21c2faa5be50274ab8cbf!}
{!LANG-4d786de0dee35bb5c1fb3d3d53f938c7!}
? 1: ? 2: ? 3 = 1/1 6: 1/2 6: 1/3 6 = 729: 11: 1{!LANG-acf3165514d10ee245b485bc9bfc0b91!} {!LANG-f94ba701bbfce0ea0969d109bf42ad34!}
{!LANG-4362fc00825d4b284d232fdac88f27b6!}{!LANG-99b45371a710655742d02307b01f258b!}
{!LANG-9d35a5b2a32bcb6f051e2cf8670ce45d!}{!LANG-f02b1cee7e9f921a9202fa1fc9605478!}
{!LANG-32b03684069951f210813db71ce8f65e!}
{!LANG-cc3037c0b6144d633c0b39ac57a2ea4c!}{!LANG-730a6af081fa5c3ae3802919453bbc2c!} {!LANG-82d7f5a33d308d5a63bdd12ebfd05c15!}{!LANG-4d402d01a5c209161dc5f4b9bfaf2f73!} {!LANG-2dc9d3469d3eb5c1ffdab82a2c0acbdf!}{!LANG-8c524a4d95133e9e759f6b2ccf709ae9!}
{!LANG-ab64bcee5e2fd3e10b2b82734e817814!}
{!LANG-8d87d76dee4c61ad757c3028bc1b8faa!}
{!LANG-970cbe42ffd63553900ae150afcb19dc!}
{!LANG-ca9c34d9981657b231dc763a74852431!}
{!LANG-871e51cdbecd4cdfedf3c406bccfdf42!}
{!LANG-0bb4c14cc2d1168593978e233a79ec88!}
{!LANG-d3ac446b899ed5fada12d9286df08595!}
{!LANG-85ecb5e1a51679aa560f23d139790a05!}
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