To the equilibrium that is established in a solution of a weak electrolyte between molecules and ions, we can apply the laws of chemical equilibrium and write down the expression for the equilibrium constant. For example, for the electrolytic dissociation (protolysis) of acetic acid occurring under the action of water molecules,
CH 3 COOH + H 2 O ↔ H 3 O + + CH 3 COO –
the equilibrium constant has the form
Two methods are used to record the values of the acidity and basicity constants. In the first method, the values of the constant and temperature are indicated on the same line after the reaction equation and a comma, for example,
HF + H 2 O ↔ H 3 O + + F – , K k = 6.67·10 –4 mol·l –1 (25°С).
In the second method, the value of the constant is first written down, and then the acid and base forms of the electrolyte, the solvent (usually water) and the temperature are given in parentheses:
Kk = 6.67·10 –4 (HF, F – , H 2 O, 25°C) mol L –1.
The acidity and basicity constants depend on the nature of the electrolyte, solvent, and temperature, but do not depend on the concentration of the solution. They characterize the ability of a given acid or a given base to dissociate into ions: the higher the value of the constant, the easier the electrolyte dissociates.
Polybasic acids, as well as bases of two or more valent metals, dissociate stepwise. In solutions of these substances, complex equilibria are established in which ions of different charges participate. For example, the dissociation of carbonic acid occurs in two stages:
H 2 CO 3 + H 2 O ↔ H 3 O + + HCO 3 – ;
HCO 3 – + H 2 O ↔ H 3 O – + CO 3 2–.
The first equilibrium is first stage of protolysis- characterized by an acidity constant, denoted K k1:
Overall balance
H 2 CO 3 + 2H 2 O ↔ 2H 3 O + + CO 3 2 –
The total acidity constant K to corresponds to:
| K k = |
The quantities K k, K k1, and K k2 are related to each other by the relation:
K k = K k1 K k2.
With the stepwise dissociation of substances, the decomposition in the next step always occurs to a lesser extent than in the previous one (in the second less than in the first, etc.) In other words, the following inequalities are observed:
K k > K k2 > K k3 and K 01 > K 02 > K 03. . .
This is explained by the fact that the energy that must be expended to remove an ion is minimal when it is separated from a neutral molecule and becomes greater during dissociation in each subsequent step.
If we denote the concentration of an electrolyte breaking up into two ions by c in, and the degree of its dissociation in a given solution by α, then the concentration of each ion will be c in α, and the concentration of undissociated molecules will be c in (1 – α). Then the equation for the protolysis constant K k,ω (either the acidity constant or the basicity constant) takes the form:
This equation expresses Ostwald's dilution law. It makes it possible to calculate the degree of dissociation at various electrolyte concentrations if its dissociation constant is known. Using this equation, you can also calculate the dissociation constant of an electrolyte, knowing its degree of dissociation at a particular concentration.
For solutions in which the dissociation of the electrolyte is very small, the Ostwald law equation is simplified. Since in such cases α<<, то величиной α в знаменателе уравнения для К к,ω можно пренебречь. При этом уравнение принимает вид.
where: K a – acidity constant; K p – equilibrium constant.
The acid there is stronger, the higher the acidity constant. pK a values are often used. The lower the pKa value, the stronger the acid.
pK a = -logK a
For example, pK a of phenol = 10, pK a of ethanol = 16. This means that phenol is six orders of magnitude (million times) a stronger acid than ethyl alcohol.
Basicity can be expressed in terms of pK b.
rKb = 14 - pKa
It is important to remember that pKa of water = 15.7. All substances that have a pKa greater than water are not able to exhibit acidic properties in aqueous solutions. Water, as a stronger acid, suppresses the dissociation of weaker acids. Since most organic compounds have acidic properties that are many times weaker than those of water, a polarographic approach to assessing their acidity has been developed (I.P. Beletskaya et al.). It allows you to evaluate acidity up to pK a = 50, although for very weak acids pK a values can only be estimated very approximately.
Qualitative assessment of acidity both in the series of substances with similar structures and for compounds of different classes is extremely important. The ability of an acid to donate a proton is related to the stability of the resulting anion. The more stable the resulting anion, the less its tendency to capture the proton back and turn into a neutral molecule. Several factors must be taken into account when assessing the relative stability of an anion.
The nature of the atom donating a proton. The more easily an atom loses a proton, the higher its electronegativity and polarizability. Therefore, in the series of acids, the ability to dissociate decreases as follows:
S-H>O-H>-N-H>C-H
This series corresponds perfectly to the properties of atoms known from the periodic table.
The influence of the environment. If substances that are similar in structure are compared, the assessment is carried out by comparing the electron density on the atom that donated the proton. All structural factors that contribute to a decrease in charge stabilize the anion, and an increase in charge destabilize it. Thus, all acceptors increase acidity, all donors decrease it.
This occurs regardless of what effect of electron transfer (inductive or mesomeric) is responsible for the redistribution of electron density.
Solvation effect. Solvation (interaction with solvent molecules) increases the stability of the anion due to the redistribution of excess electron density between the anion and solvent molecules. In general, the pattern is as follows:
· the more polar the solvent, the stronger the solvation;
· the smaller the ion, the better it is solvated.
Basicity according to Brønsted is the ability of a substance to provide its pair of electrons for interaction with a proton. As a rule, these are substances containing atoms of nitrogen, oxygen and sulfur in the molecule.
The weaker the basic center holds a pair of electrons, the higher the basicity. In a row
R 3 -N>R 2O>R 2S
basicity decreases. This sequence is easy to remember using the mnemonic rule “NOS”.
There is a relationship among Brønsted bases: anions are stronger bases than the corresponding neutral molecules. For example, the hydroxide anion (–OH) is a stronger base than water (H2O). When a base interacts with a proton, onium cations can be formed:
· R 3 O + - oxonium cation;
· NR 4 + - ammonium cation;
· R 3 S + - sulfonium cation.
Qualitative assessment of the basicity of substances with similar structures is carried out using the same logic as the assessment of acidity, but with the opposite sign.
Therefore, all acceptor substituents reduce their basicity, and all donor substituents increase their basicity.
Lewis acids and bases
Lewis bases are electron pair donors, just like Brønsted bases.
Lewis's definition for acids differs markedly from the usual one (according to Brønsted). A Lewis acid is any molecule or ion that has a vacant orbital that can be filled with an electron pair as a result of interaction. If, according to Brønsted, an acid is a proton donor, then according to Lewis, the proton itself (H +) is an acid, since its orbital is empty. There are a lot of Lewis acids: Na +, Mg 2+, SnCl 4, SbCl 5, AlCl 3, BF 3, FeBr 3, etc. Lewis theory allows many reactions to be described as acid-base interactions. For example:
Often, in reactions with Lewis acids, organic compounds that donor a pair of p-electrons participate as bases:
In organic chemistry the following is accepted:
· if the term “acid” is used, it means Brønsted acid;
· if the term “acid” is used in the Lewis sense, they say “Lewis acid”.
Lecture No. 5
Hydrocarbons
Alkanes
· Homologous series, nomenclature, isomerism, alkyl radicals. Electronic structure of alkane molecules, sp 3 -hybridization, s-bond. Lengths of C-C and C-H bonds, bond angles, bond energies. Spatial isomerism of organic substances. Methods for depicting the spatial structure of molecules with sp 3 -hybridized carbon atoms. Spectral characteristics of alkanes. Physical properties of alkanes and patterns of their changes in the homologous series.
Alkanes (saturated acyclic compounds, paraffins)
Alkanes are hydrocarbons with an open chain of atoms, corresponding to the formula C n H 2 n+2, where the carbon atoms are connected to each other only by σ bonds.
The term “saturated” means that each carbon in the molecule of such a substance is bonded to the maximum possible number of atoms (four atoms).
The structure of methane is described in detail in lecture No. 2.
Isomerism, nomenclature
The first three members of the homologous series (methane, ethane and propane) exist as one structural isomer. Starting with butane, the number of isomers is growing rapidly: pentane has three isomers, and decane (C 10 H 22) already has 75.
Using pH-metry method
Measurements are carried out in dilute solutions, taking the activity coefficient equal to unity.
If we do not take into account the reaction of autoprotolysis of water, then the equation of ionic equilibria in an aqueous solution of a weak monobasic acid will have the following form:
HA + H 2 O = H 3 O + + A - x
The acidity constant will be expressed as:
Moreover, [c] = 1 mol/l
If the acid is weak, then 
From here we get
Solutions with different initial acid concentrations are prepared and their pH is measured.
Build a graph of pH versus lg c H.A. From the above equation it follows that the segment cut off by the straight line on the ordinate axis is equal to 1/2рK kis.
Determination of acidity constant by potentiometric method
For monobasic acid
.
To determine it, it is necessary to measure the concentration of hydronium ions in a solution with a known acid concentration. A glass or quinhydrone electrode, such as Ag | AgCl | KCl || H 3 O + , sat.x.g |Pt
To obtain more accurate results, titrate a weak acid solution with a NaOH solution; during titration, measure the EMF of the element and calculate the pH.
The following reactions occur in the system:
H 2 O + H 2 O = H 3 O + + OH - x 1
HA + H 2 O = H 3 O + + A - x 2
H 3 O + + NaOH = 2 H 2 O + Na x 3
It can be assumed that x 1<< x 2 и x 1 << x 3 .
The balance equations have the form: 
.
As shown earlier
SECTION 3. KINETIC REGULARITIES OF SIMPLE REACTIONS
Chemical kinetics is a science that studies the course of a chemical reaction or physical and chemical processes over time; it is a section of physical chemistry that studies the dependence of the rate of a chemical reaction on the concentration of reagents, temperature, properties of the medium, radiation and other factors.
Classification of chemical reactions
From a kinetics point of view, there are several principles for classifying chemical reactions:
1) according to the state of aggregation of the reaction participants, all reactions are divided into homogeneous and heterogeneous.
Homogeneous reactions when all reactants are in the same phase. They are:
a) gas-phase
b) liquid phase
c) solid phase
Heterogeneous reactions, when the participants in the reaction are in different phases; the reaction occurs at the interface
2) according to the specifics of the elementary act
a) catalytic
b) non-catalytic
c) photochemical
d) electrochemical
e) chain
3) by number of stages
a) simple (stage 1)
b) complex
4) according to the reversibility of reactions
a) reversible (bilateral)
b) irreversible
A reaction is considered irreversible if:
a) as a result of the reaction a gas is formed
HCOOH → H2O + CO2
b) a sparingly soluble compound is formed
AgNO 3 + KJ → AgJ↓ + KNO 3
c) a slightly dissociable compound is formed
HNO 3 + NaOH → NaNO 3 + H 2 O
d) a large amount of heat is released
3Fe 3 O 4 + 8Al → 4Al 2 O 3 + 9Fe + ∆H
3.2. Elementary chemical reactions
The rate of chemical reactions depends on the path of the reaction. This path can be represented as a sum of elementary chemical reactions.
An elementary reaction is a one-way process of converting one component into another. It is a set of similar elementary acts of chemical transformation. Most chemical reactions are not elementary; they include several elementary stages - complex reactions.
The reaction mechanism is a set of elementary stages.
A reactant is a participant in a chemical reaction.
d ρ n k– infinitesimal change in the number of moles of a component k in an elementary reaction ρ
If d ρ n k > 0 – reaction product
d ρ n k< 0 – starting material
d ρ n k = 0 – indifferent substance
3.3. Chemical reaction rate
The rate of a chemical reaction is the number of similar elementary acts of chemical transformation occurring per unit time per unit volume or per unit surface.
Consider the reaction:
t = 0 - original mole numbers
t ≠ 0 n A n B n C n D - current numbers of moles ξ =
(xi) ξ – reaction depth
1. Protolysis (ionization) reactions.
These include reactions between an acid or base and water:
Kit 1 main 2 kit 2 main 1
Set 1 main. 2 set 2 main. 1
2. Autoprotolysis reactions, associated with the transfer of a proton from one water molecule to another.
Hydrolysis reactions
CH 3 COONa+ H 2 O ←→ CH 3 COOH + NaOH
CH 3 COO - + H 2 O ←→ CH 3 COOH + OH -
main 2 set 1 set 2 main 1
Acid-base reactions
NH 3 + HCl → NH 4 + + Cl -
main 2 set 1 set 2 main 1
From an analytical point of view, the following types of reactions are distinguished:
1) with proton transfer – acid-base;
2) with electron transfer – OB reaction;
3) with the transfer of electron pairs with the formation of bonds according to the donor-acceptor mechanism - complexation reactions.
2.2.2 Constant of acidity and basicity. pH calculations
The ability of an acid to donate a proton, and a base to accept it (i.e., the strength of acids and bases) can be characterized by equilibrium constants,
HS – solvent
which are called acidity constants (K A ) and basicity (K b ).
Solvent activity is a constant value (tabular data)
Positions of acid-base equilibria
and the values of the corresponding acidity and basicity constants depend on the nature of the solvent.
If the solvent is a stronger proton acceptor than water (for example, ammonia), then the strength of the acids in it increases. So acids that are weak in aqueous solutions can be strong in ammonia.
The stronger the basic properties of the solvent, the more acids are leveled in it.
Likewise, the stronger the acidic properties of the solvent, the more bases it neutralizes.
When moving from a more to a less basic solvent, strong acids can become weak (for example, HCl and HClO 4 in water are strong acids, but in glacial acetic acid they become weak).
pH calculation
Acid-base equilibrium calculations are used for:
1) finding the pH of the solution using known equilibrium concentrations;
2) determination of equilibrium concentrations based on a known pH value
pH is an important assessment for biological fluids.
Living organisms are characterized by maintaining the acid-base state at a certain level. This is expressed in fairly constant pH values of biological media and the ability to restore normal pH values when exposed to protoliths.
The system that maintains protolytic homeostasis includes not only physiological mechanisms (pulmonary and renal compensation), but also physicochemical action, ion exchange, and diffusion.
In analytical chemistry, it is important to know the concentrations of all particles in a solution of an acid or base after equilibrium has been established, in particular the concentration of H + ions (pH).
- weak electrolyte
- strong electrolyte
Pure water
There is no such thing as clean water. Sea water contains almost all chemical elements.
Solutions of weak acids
Because 
, That
Solutions of weak bases
Solutions of strong acids
To take into account the influence of electrostatic interaction of ions, the concept ionic strength of solution. It depends on the concentration of the ion and its charge.
For strong electrolytes, the law of mass action is satisfied if activities are used. Activity takes into account the concentration of reagents, inter-ion interaction (ion-ion, ion-dipole, dipole-dipole, hydrogen bonds).
According to the theory of Debye and Hückel
- dependence of the mobility coefficient on ionic strength
A depends on the dielectric constant of the solvent and the temperature of the system. At t=25°C A=0.512 and for a binary electrolyte
Solutions of strong bases
3.3Protolytic equilibrium in buffer solutions
In a broad sense, buffer systems are systems that maintain a certain value of a parameter when the composition changes.
Buffer solutions can be acid-base - they maintain a constant pH value when introducing acids or bases; redox - keep the potential of the system constant when oxidizing or reducing agents are introduced; metal buffer solutions are known.
The buffer solution is a conjugate pair; in particular, an acid-base buffer is a conjugate acid-base pair:
Types of protolytic reactions.
MU "Solutions" pp. 52-55
Autoprotolysis of water. Ionic product of water.MU "Solutions"» page 56
A small proportion of water molecules are always in an ionic state, although it is a very weak electrolyte. Ionization and further dissociation of water, as already mentioned, is described by the equation of the protolytic reaction of acid-base disproportionation or autoprotolysis.
Water is a very weak electrolyte, therefore the conjugate acid and conjugate base formed are strong. Therefore, the equilibrium of this protolytic reaction is shifted to the left.
The constant of this equilibrium K equals =
The quantitative value of the product of water ion concentration × is ionic product of water.
It is equal to: × = K equal. × 2 = 1×10 – 14
Therefore: KH 2O = × = 10 – 14 or simplified KH 2O = × = 10 – 14
KH2O is the ionic product of water, the autoprotolysis constant of water, or simply the constant of water. KH2O depends on temperature. It increases with increasing temperature.
In chemically pure water = = = 1×10 – 7. This is a neutral environment.
The solution may contain > – the medium is acidic or< – среда щелочная
= ; =
pH value
To quantitatively express the acidity of solutions, use hydrogen ion concentration indicator pH.
The hydrogen index is a value equal to the negative decimal logarithm of the concentration of free hydrogen ions in a solution.
pH = – log ⇒ = 10 – pH
In a neutral environment pH = 7
At acidic pH< 7
In alkaline pH > 7
To characterize the basicity of the medium, the hydroxyl indicator pOH is used
рОН = – log [ОH - ] ⇒ [ОH - ] = 10 – рОН
pH + pOH = 14 Þ pH = 14 – pOH and pOH = 14 – pH
Formulas for calculating pH for solutions of acids and bases.
pH = – log
- Strong acids: = C(1/z acid)
Calculate the pH of a HCl solution with C(HCl) = 0.1 mol/l under the condition of its complete dissociation.
C(HCl) = 0.1 mol/l; pH = – log 0.1 = 1
2. Strong bases: [ОH - ] = С(1/z base)
Calculate the pH of the NaOH solution under the same conditions.
C(NaOH) = 0.1 mol/l; = = 10 – 13 ; pH = – log 10 – 13 = 13
3. Weak acids
Calculate the pH of a solution of acetic acid with a molar concentration of 0.5 mol/L. K CH 3COOH = 1.8×10 – 5.
3×10 – 3
pH = – log 3×10 – 3 = 2.5
4. Weak foundations
Calculate the pH of an ammonia solution with a molar concentration of 0.2 mol/L.
K NН 3 = 1.76×10 – 5
1.88×10 – 3
0.53×10 – 11; pH = – log 0.53×10 – 11 = 11.3
5. C(H +) = [H + ] = 10 – pH
At pH = 7, [H + ] = 10 – 7
There are various methods for determining pH: using indicators and ionomer devices.
The value of pH for chemical reactions and biochemical processes in the body.
Many reactions require a strictly defined pH value to proceed in a certain direction.
Normally, in a healthy body, the reaction of the environment of most biological fluids is close to neutral.
Blood – 7.4
Saliva – 6.6
Intestinal juice – 6.4
Bile – 6.9
Urine – 5.6
Gastric juice: a) at rest – 7.3
b) in a state of digestion – 1.5-2
Deviation of pH from the norm has diagnostic (definition of the disease) and prognostic (course of the disease) significance.
Acidosis is a shift in pH to the acidic side, the pH decreases, the concentration of hydrogen ions increases.
Alkalosis is a shift in pH to the alkaline region, the pH increases, and the concentration of hydrogen ions decreases.
A temporary deviation of blood pH from the norm by tenths leads to serious disturbances in the body. Long-term deviations in blood pH can be fatal. Deviations in blood pH can be 6.8 - 8; changes outside this range in any direction are incompatible with life.
Combined and isolated protolytic equilibria.
Protolytic processes are reversible reactions. Protolytic equilibria are shifted towards the formation of weaker acids and bases. They can be considered as competition between bases of different strengths for the possession of a proton. They talk about isolated and combined equilibria.
If several simultaneously existing equilibria are independent of each other, they are called isolated. A shift in equilibrium in one of them does not entail a change in the equilibrium position in the other.
If a change in equilibrium in one of them leads to a change in equilibrium in the other, then we speak of combined (conjugate, competing) equilibria. The predominant process in systems with combined equilibrium is the one characterized by a larger value of the equilibrium constant.
The second process will be predominant, because its equilibrium constant is greater than the equilibrium constant of the first process. The equilibrium in the second process is shifted to the right to a greater extent, because methylamine is a stronger base than ammonia, NH 4 + is a stronger acid than CH 3 NH 3 +.
Conclusion: A stronger base suppresses the ionization of a weaker base. Therefore, when a small amount of hydrochloric acid is added to a mixture of ammonia and methylamine, it will be mainly the methylamine that undergoes protonation.
And also: the strongest acid suppresses the ionization of weak acids. Thus, hydrochloric acid found in gastric juice suppresses the ionization of acetic acid (coming from food) or acetylsalicylic acid (medicinal substance).
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