Electrical dissociation of water. Dissociation of water. Hydrogen indicator. Electron clouds of orbitals with different values ​​of l have different configurations, and those with the same l have a similar configuration

Pure water, although poorly (compared to electrolyte solutions), can conduct electric current. This is caused by the ability of a water molecule to disintegrate (dissociate) into two ions, which are conductors of electric current in pure water (below, dissociation means electrolytic dissociation - disintegration into ions):

Hydrogen index (pH) is a value characterizing the activity or concentration of hydrogen ions in solutions. The hydrogen indicator is designated pH. The hydrogen index is numerically equal to the negative decimal logarithm of the activity or concentration of hydrogen ions, expressed in moles per liter: pH=-log[ H+ ] If [ H+ ]>10-7mol/l, [ OH-]<10-7моль/л -среда кислая; рН<7.Если [ H+ ]<10-7 моль/л, [ OH-]>10-7mol/l - alkaline environment; pH>7. Hydrolysis of salts- this is the chemical interaction of salt ions with water ions, leading to the formation of a weak electrolyte. 1). Hydrolysis is not possibleSalt formed by a strong base and a strong acid ( KBr, NaCl, NaNO3), will not undergo hydrolysis, since in this case a weak electrolyte is not formed. pH of such solutions = 7. The reaction of the medium remains neutral. 2). Hydrolysis by cation (only the cation reacts with water). In a salt formed by a weak base and a strong acid

(FeCl2,NH4Cl, Al2(SO4)3,MgSO4)

The cation undergoes hydrolysis:

FeCl2 + HOH<=>Fe(OH)Cl + HCl Fe2+ + 2Cl- + H+ + OH-<=>FeOH+ + 2Cl- + H+

As a result of hydrolysis, a weak electrolyte, H+ ion and other ions are formed. solution pH< 7 (раствор приобретает кислую реакцию). 3). Гидролиз по аниону (в реакцию с водой вступает только анион). Соль, образованная сильным основанием и слабой кислотой

(KClO, K2SiO3, Na2CO3,CH3COONa)

undergoes hydrolysis at the anion, resulting in the formation of a weak electrolyte, hydroxide ion OH- and other ions.

K2SiO3 + HOH<=>KHSiO3 + KOH 2K+ +SiO32- + H+ + OH-<=>НSiO3- + 2K+ + ОН-

The pH of such solutions is > 7 (the solution becomes alkaline). 4). Joint hydrolysis (both the cation and the anion react with water). Salt formed by a weak base and a weak acid

(CH 3COONH 4, (NН 4)2СО 3, Al2S3),

hydrolyzes both the cation and the anion. As a result, a slightly dissociating base and acid are formed. The pH of solutions of such salts depends on the relative strength of the acid and base. A measure of the strength of an acid and a base is the dissociation constant of the corresponding reagent. The reaction of the medium of these solutions can be neutral, slightly acidic or slightly alkaline:

Al2S3 + 6H2O =>2Al(OH)3v+ 3H2S^

Hydrolysis is a reversible process. Hydrolysis is irreversible if the reaction results in the formation of an insoluble base and (or) a volatile acid

The textbook is intended for students of non-chemical specialties of higher educational institutions. It can serve as a guide for individuals independently studying the basics of chemistry, and for students of chemical technical schools and senior high schools.

A legendary textbook, translated into many languages ​​of Europe, Asia, Africa and published in a total circulation of over 5 million copies.

When producing the file, the site http://alnam.ru/book_chem.php was used

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Pure water is a very poor conductor of electricity, but still has measurable electrical conductivity, which is explained by the slight dissociation of water into hydrogen ions and hydroxide ions:

Based on the electrical conductivity of pure water, the concentration of hydrogen and hydroxide ions in water can be calculated. At 25°C it is 10 -7 mol/l.

Let's write an expression for the water dissociation constant:

Let's rewrite this equation as follows:

Since the degree of dissociation of water is very small, the concentration of undissociated H 2 O molecules in water is almost equal to the total concentration of water, i.e. 55.55 mol/l (1 liter contains 1000 g of water, i.e. 1000:18.02 = 55.55 mol). In dilute aqueous solutions, the concentration of water can be considered the same. Therefore, replacing the product in the last equation with a new constant K H 2 O we will have:

The resulting equation shows that for water and dilute aqueous solutions at a constant temperature, the product of the concentrate of hydrogen ions and hydroxide ions is a constant value. This constant value is called the ionic product of water. Its numerical value can be easily obtained by substituting the concentrations of hydrogen and hydroxide ions into the last equation. In pure water at 25°C ==1·10 -7 mol/l. Therefore, for the specified temperature:

Solutions in which the concentrations of hydrogen ions and hydroxide ions are the same are called neutral solutions. At 25°C, as already mentioned, in neutral solutions the concentration of both hydrogen ions and hydroxide ions is 10 -7 mol/l. In acidic solutions the concentration of hydrogen ions is higher, in alkaline solutions the concentration of hydroxide ions is higher. But whatever the reaction of the solution, the product of the concentrations of hydrogen ions and hydroxide ions remains constant.

If, for example, enough acid is added to pure water so that the concentration of hydrogen ions increases to 10 -3 mol/l, then the concentration of hydroxide ions will decrease so that the product remains equal to 10 -14. Therefore, in this solution the concentration of hydroxide ions will be:

10 -14 /10 -3 =10 -11 mol/l

On the contrary, if you add alkali to water and thereby increase the concentration of hydroxide ions, for example, to 10 -5 mol/l, then the concentration of hydrogen ions will be:

10 -14 /10 -5 =10 -9 mol/l

These examples show that if the concentration of hydrogen ions in an aqueous solution is known, then the concentration of hydroxide ions is also determined. Therefore, both the degree of acidity and the degree of alkalinity of a solution can be quantitatively characterized by the concentration of hydrogen ions:

The acidity or alkalinity of a solution can be expressed in another, more convenient way: instead of the concentration of hydrogen ions, indicate its decimal logarithm, taken with the opposite sign. The last value is called the hydrogen index and is denoted by pH:

For example, if =10 -5 mol/l, then pH=5; if = 10 -9 mol/l, then pH = 9, etc. From here it is clear that in a neutral solution (= 10 -7 mol/l) pH = 7. In acidic solutions pH<7 и тем меньше, чем кислее раствор. Наоборот, в щелочных растворах pH>7 and the more, the greater the alkalinity of the solution.

There are various methods for measuring pH. The approximate reaction of a solution can be determined using special reagents called indicators, the color of which changes depending on the concentration of hydrogen ions. The most common indicators are methyl orange, methyl red, and phenolphthalein. In table 17 provides characteristics of some indicators.

For many processes, pH plays an important role. Thus, the pH of human and animal blood has a strictly constant value. Plants can grow normally only at pH values ​​of the soil solution that lie within a certain range characteristic of a given plant type. The properties of natural waters, in particular their corrosiveness, strongly depend on their pH.

Table 17. Key indicators

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Pure water, although poorly (compared to electrolyte solutions), can conduct electric current. This is caused by the ability of a water molecule to disintegrate (dissociate) into two ions, which are conductors of electric current in pure water (below, dissociation means electrolytic dissociation - disintegration into ions):

H 2 O ↔ H + + OH -

For approximately 556,000,000 non-dissociated water molecules, only 1 molecule dissociates, but this is 60,000,000,000 dissociated molecules in 1mm3. Dissociation is reversible, that is, the H + and OH - ions can form a water molecule again. Eventually it comes dynamic equilibrium in which the number of decayed molecules is equal to the number of H + and OH - ions formed. In other words, the speeds of both processes will be equal. For our case, the equation for the rate of a chemical reaction can be written as follows:

υ 1 = κ 1 (for water dissociation)

υ 2 = κ 2 (for the reverse process)

Where υ - speed reaction; κ - reaction rate constant (depending on the nature of the reactants and temperature); , And - concentration (mol/l).

In a state of balance υ 1 = υ 2, hence:

κ 1 = κ 2

Let's do some simple math and get:

κ 1 /κ 2 = /

κ 1 /κ 2 = K

K- equilibrium constant, and in our case, dissociation constant, which depends on the temperature and nature of the substances, and does not depend on concentrations (as well as κ 1 and κ 2). K for water 1.8 10 -16 at 25 °C (reference value).

Due to the very small number of dissociated molecules, the concentration can be taken to be equal to the total concentration of water, and the total concentration of water in dilute solutions as a constant value:

=1000(g/l)/18(g/mol)=55.6 mol/l.

Replacing κ 1 / κ 2 on K and using the magnitude , we determine what the product of concentrations is equal to And which is called - ionic product of water:

K = /55.6 mol/l
1.8 10 -16 55.6 mol/l =
10 -14 =

Since, at a certain temperature, the quantities used in calculating the ionic product of water ( K, ) are constant, the value of the ionic product of water just the same all the time. And since the dissociation of a water molecule produces the same number of ions And , it turns out that for pure water the concentration And will be equal 10 -7 mol/l. From the constancy of the ionic product of water, it follows that if the number of H + ions becomes larger, then the number of HO - ions becomes smaller. For example, if a strong acid HCl is added to pure water, it, as a strong electrolyte, will completely dissociate into H + and Cl -, as a result, the concentration of H + ions will increase sharply, and this will lead to an increase in the rate of the process opposite to dissociation, since it depends on the concentration of ions H+ and OH-:

υ 2 = κ 2

During the accelerated process opposite to dissociation, the concentration of HO - ions will decrease to a value corresponding to the new equilibrium, at which there will be so few of them that the rates of dissociation of water and the reverse process will again be equal. If the concentration of the resulting HCl solution is 0.1 mol/l, the equilibrium concentration will be equal to:

= 10 -14 /0.1 = 10 -13 mol/l

When adding the strong base NaOH, the shift will be towards a decrease in the H + concentration.

End of work -

This topic belongs to the section:

Electron clouds of orbitals with different values ​​of l have different configurations, and those with the same l have a similar configuration

Modern quantum mechanical theory states that an atom of any element has a complex structure; the positive part of the atom is a positive charge.. quantum theory implies that the energy of an electron can only be received.. so at l s, the orbital for an electron with any value of the principal quantum number n, the electron cloud is limited..

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The structure of atoms and the Pauli principle
The Pauli principle helps explain a variety of physical phenomena. A consequence of the principle is the presence of electron shells in the structure of the atom, from which, in turn, follows a variety of chemical

Basic types of chemical bonds. Covalent bond. Basic principles of the valence bond method. Sigma and Picovalent bonds
atoms can combine with each other to form both simple and complex substances. In this case, various types of chemical bonds are formed: ionic, covalent (non-polar and polar), metal

Sp hybridization
Occurs when one s- and one p-orbital mix. Two equivalent sp-atomic orbitals are formed, located linearly at an angle of 180 degrees and directed in different directions from the nucleus of the atom

Geometric shape and polarity of molecules
Hybridization Geometric shape Angle between bonds sp Linear 180° sp

Ionic bond as a limiting case of covalent bond polarization. Electrostatic interaction of ions
An ionic bond is a very strong chemical bond formed between atoms with a large difference (>1.5 on the Pauling scale) of electronegativity, at which the shared electron pair

Chemical properties of basic oxides
1. Water-soluble basic oxides react with water to form bases: Na2O + H2O → 2NaOH. 2. Interact with acid oxides, causing

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Chemical properties of amphoteric oxides
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Grounds. Chemical properties of bases. Amphoteric states, reactions of their interaction with acids and alkalis
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Acids. Anoxic and oxygenic acids. Properties of acids (sulfuric, hydrochloric, nitric)
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Nitrates
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An example of homogeneous catalysis is the decomposition of hydrogen peroxide in the presence of iodine ions. The reaction occurs in two stages: H2O2 + I → H2O + IO

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Rules for writing ion exchange reactions
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Types of redox reactions
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Mass fraction
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Pure water is a very poor conductor of electricity, but still has measurable electrical conductivity, which is explained by the slight dissociation of water into hydrogen ions and hydroxide ions:

Based on the electrical conductivity of pure water, the concentration of hydrogen and hydroxide ions in water can be calculated. At it is equal to mol/l.

Let's write an expression for the water dissociation constant:

Let's rewrite this equation as follows:

Since the degree of dissociation of water is very small, the concentration of undissociated molecules in water is almost equal to the total concentration of water, i.e. 55.55 mol/l (1 liter contains 1000 g of water, i.e. mol). In dilute aqueous solutions, the concentration of zoda can be considered the same. Therefore, replacing the product in the last equation with a new constant, we will have:

The resulting equation shows that for water and dilute aqueous solutions at a constant temperature, the product of the concentrate of hydrogen ions and hydroxide ions is a constant value. This constant value is called the ionic product of water. Its numerical value can be easily obtained by substituting the concentrations of hydrogen and hydroxide ions into the last equation. In pure water at mol/l. Therefore, for the specified temperature:

Solutions in which the concentrations of hydrogen ions and hydroxide ions are the same are called neutral solutions. At , as already mentioned, in neutral solutions the concentration of both hydrogen ions and hydroxide ions is equal to mol/l. In acidic solutions there is a higher concentration of hydrogen ions, in alkaline solutions there is a higher concentration of hydroxide ions. But whatever the reaction of the solution, the product of the concentrations of hydrogen ions and hydroxide ions remains constant.

If, for example, enough acid is added to pure water so that the concentration of hydrogen ions increases to mol/l, then the concentration of hydroxide ions will decrease so that the product remains equal. Therefore, in this solution the concentration of hydroxide ions will be:

On the contrary, if you add alkali to water and thereby increase the concentration of hydroxide ions, for example, to mol/l, then the concentration of hydrogen ions will be:

These examples show that if the concentration of hydrogen ions in an aqueous solution is known, then the concentration of hydroxide ions is also determined. Therefore, both the degree of acidity and the degree of alkalinity of a solution can be quantitatively characterized by the concentration of hydrogen ions:

The acidity or alkalinity of a solution can be expressed in another, more convenient way: instead of the concentration of hydrogen ions, indicate its decimal logarithm, taken with the opposite sign. The last value is called the hydrogen index and is denoted by:

For example, if mol/l, then ; if mol/l, then etc. From here it is clear that in a neutral solution (mol/l). In acidic solutions, the more acidic the solution, the less. On the contrary, in alkaline solutions the greater the alkalinity of the solution.

An extremely important role in biological processes is played by water, which is an essential component (from 58 to 97%) of all cells and tissues of humans, animals, plants and simple organisms. this is the environment in in which a wide variety of biochemical processes occur.

Water has good dissolving ability and causes electrolytic dissociation of many substances dissolved in it.

The process of water dissociation according to the Brønsted theory proceeds according to the equation:

N 2 0+H 2 0 N 3 ABOUT + + HE - ; ΔН dis = +56.5 KJ/mol

Those. one water molecule donates, and the other adds a proton, autoionization of water occurs:

N 2 0 N + + HE - - deprotonation reaction

N 2 0 + N + N 3 ABOUT + - protonation reaction

The dissociation constant of water at 298°K, determined by the electrical conductivity method, is equal to:

a(H +) - activity of H + ions (for brevity, instead of H3O + write H +);

a(OH -) - activity of OH - ions;

a(H 2 0) - water activity;

The degree of dissociation of water is very small, so the activity of hydrogen and hydroxide ions in pure water is almost equal to their concentrations. The concentration of water is constant and equal to 55.6 mol.

(1000g: 18g/mol= 55.6 mol)

Substituting this value into the expression for the dissociation constant Kd(H 2 0), and instead of the activities of hydrogen and hydroxide ions, their concentrations, a new expression is obtained:

K(H 2 0) = C (H +) × C (OH -) = 10 -14 mol 2 / l 2 at 298 K,

More precisely, K(H 2 0) = a(H +) × a(OH -) = 10 -14 mol 2 l 2 -

K(H 2 0) is called ionic product of water or autoionization constant.

In pure water or any aqueous solution at a constant temperature, the product of the concentrations (activities) of hydrogen and hydroxide ions is a constant value, called the ionic product of water.

The constant K(H 2 0) depends on temperature. As the temperature rises, it increases, because The process of water dissociation is endothermic. In pure water or aqueous solutions of various substances at 298K activity (concentration), hydrogen and hydroxide ions will be:

a(H +)=a(OH -)=K(H 2 0) = 10 -14 =10 -7 mol/l.

In acidic or alkaline solutions, these concentrations will no longer be equal to each other, but will change conjugately: as one of them increases, the other will correspondingly decrease and vice versa, for example,

a(H +)=10 -4, a(OH -)=10 -10, their product is always 10 -14

pH value

Qualitatively, the reaction of the medium is expressed through the activity of hydrogen ions. In practice, they do not use this value, but the hydrogen indicator pH - a value numerically equal to the negative decimal logarithm of the activity (concentration) of hydrogen ions, expressed in mol/l.

pH= -lga(H + ),

and for dilute solutions

pH= -lgC(H + ).

For pure water and neutral media at 298K pH=7; for acidic pH solutions<7, а для щелочных рН>7.

The reaction of the medium can also be characterized by the hydroxyl index:

pOH= -lga(OH - )

or approximately

pOH= -IgC(OH - ).

Accordingly, in a neutral environment pH = pH = 7; in an acidic environment pOH>7, and in an alkaline environment pOH<7.

If we take the negative decimal logarithm of the expression for the ionic product of water, we get:

pH + pH = 14.

Therefore, pH and pOH are also conjugate quantities. Their sum for dilute aqueous solutions is always equal to 14. Knowing the pH, it is easy to calculate pOH:

pH=14 – pH

and vice versa:

ROH= 14 - pH.

Solutions are distinguished between active, potential (reserve) and total acidity.

Active acidity measured by the activity (concentration) of hydrogen ions in a solution and determines the pH of the solution. In solutions of strong acids and bases, pH depends on the concentration of the acid or base, and the activity of H ions + and he - can be calculated using the formulas:

a(N + )= C(l/z acid)×α each; pH= - log a(H + )

a(OH - )=C(l/z base)×α each; pH= - log a(OH - )

pH= - logC(l/z acid) – for extremely dilute solutions of strong acids

pOH= - logC(l/z base) - for extremely dilute solutions of bases

Potential acidity measured by the number of hydrogen ions bound in acid molecules, i.e. represents a “reserve” of undissociated acid molecules.

Total acidity- the sum of active and potential acidity, which is determined by the analytical concentration of the acid and is established by titration

One of the amazing properties of living organisms is acid-base

homeostasis - constancy of pH of biological fluids, tissues and organisms. Table 1 presents the pH values ​​of some biological objects.

Table 1

From the table data it can be seen that the pH of various fluids in the human body varies over a fairly wide range depending on location. BLOOD, like other biological fluids, it strives to maintain a constant pH value, the values ​​of which are presented in Table 2

table 2

Changes in pH from the indicated values ​​by only 0.3 towards an increase or decrease leads to a change in the exchange of enzymatic processes, which causes a severe painful condition in humans. A pH change of just 0.4 is no longer compatible with life. Researchers have found that the following blood buffer systems are involved in the regulation of acid-base balance: hemoglobin, bicarbonate, protein and phosphate. The share of each system in the buffer capacity is presented in Table 3.

Table 3

All buffer systems of the body have the same mechanism of action, because They consist of a weak acid: carbonic, dihydrophosphoric (dihydrogen phosphate ion), protein, hemoglobin (oxohemoglobin) and salts of these acids, mainly sodium, which have the properties of weak bases. But since the bicarbonate system in the body has no equal in terms of speed of response, we will consider the ability to maintain a constant environment in the body using this system.