Chemical bonding and structure of molecules

1.1. Nature of the chemical bond

1.1.1. Covalent bonds
According to the Lewis theory of valence (1916), two atoms bind chemically only if the obtained particle
(molecule) has a greater stability (lower energy) than the parent atoms. Stable state of the outermost electron
layer is achieved in the so-called “electronic octet” or, more generally, when this layer is filled as in the inert
gases.

Heitler and London (1927) proposed the first quantum mechanical model for the formation of the hydrogen
molecule. Relative energy of a system of two hydrogen atoms (HA an HB below) at an infinite distance is
accepted to be zero. When approaching each other, electrostatic forces arise between them - attraction and
repulsion. The ratio between the two types of forces depends on the distance. The forces of attraction
increase (if the spins of the electrons are opposite). At a certain optimal distance, the system reaches a
minimum energy. This state corresponds to the length of the chemical bond formed between HA and HB. As
the distance decreases, the repulsive forces begin to predominate and the energy of the system increases.
 1.1.2. Atomic orbitals
The atomic orbital (AO) is a quantum mechanical concept, which is a one-electron solution of the
Schrödinger wave equation and is related to a certain combination of the three quantum numbers - n, l and
m. Formally, the term AO coincides to “electron cloud” – the space around the nucleus, where an electron
can be found with a probability close to 100%.

n – size of the AO
l - geometric form (shape) of AO
m - orientation in space of the AO
s - magnetic moment of the electron

s AO – sphere
p AO – dumbbell (spatial eight)
d AO – cloverleaf or elongated dumbbell with a
doughnut around its middle
Valence bond method (VBM)
During the formation of a chemical bond a partial overlap of the AO occurs and the two electrons form a
common electron pair. This pair is a joint possession of the two atoms and corresponds to the covalent bond.
Electron density is highest in the overlapping area, i.e. the
newly formed electron pair is most likely to be found
between the two nuclei.
Covalent bond: A region of relatively high electron density between nuclei arising from electron sharing
due to attraction forces at a characteristic internuclear distance.
The covalent bond can be single, when one pair of electrons if formed, double (two electron pairs) or triple
(three electron pairs). The number of electron pairs determines the multiplicity of the chemical bond.
According to the bond symmetry relative to the line connecting the two nuclei, the covalent bonds are sigma
(σ) and pi (π) bonds.
π-bonds (lateral overlap) – a
two part symmetry on both
sides of the axis, connecting
σ-bonds (frontal overlap) - cylindrical symmetry to the line the nuclei
connecting the nuclei

CH≡CH
CH2=CH2

1.1.3. Hybridization of atomic orbitals

The concept of AO hybridization is used to explain the spatial structure of molecules. Hybrid AOs are formed
by an overlap of original s- and p-orbitals. The number of hybrid AOs coincides with the number of
overlapping AOs and their shape is something between the shapes of parent orbitals, depending on the
proportions of s- and p-orbitals involved. Hybrid AOs are located at such angles that the repulsion
between electron pairs on them is minimal.
sp-Hybridization
Participants: one s- and one p-orbitals
Number: 2 sp-hybrid orbitals
Shape: asymmetric dumbbell.
Disposition: 180° (linear structure of the molecule)
sp2-Hybridization (trigonal hybridization)
Participants: one s- and two p-orbitals
Number: 3 sp2 -hybrid orbitals
Shape: asymmetric elongated dumbbell.
Disposition: 120° (planar structure of the molecule)

sp3-Hybridization
Participants: one s- and three p-orbitals
Number: 4 sp3 -hybrid orbitals
Shape: asymmetric elongated dumbbell.
Disposition: 109°28‘ (tetrahedral structure of the molecule)
Hybridization causes an additional decrease of the molecule energy (it is energetically efficient).
Hybrid orbitals can participate in σ-bonds, but for a π-bond, a non-hybridized p-orbital is needed.

1.1.4. Covalent bond with donor-acceptor mechanism of formation

This appears between a particle (atom, ion, molecule) having a free electron pair (not involved in a
chemical bond) (called a donor) and other particle (atom, ion, molecule) having a free AO in the outermost
electron layer (called an acceptor):

Once formed, the donor-acceptor bond cannot be distinguished from other covalent bonds.
Common donors: non-metals like O, N, F, Cl, S and their anions
Common acceptors: metal cations, non-metals of low electronegativity, H+
 Examples:
Formation of ammonium ion Coordination (complex) compounds

A typical example is the formation of tetrafluoroborate ion:

1.1.5. Delocalized chemical bond

Acyclic and cyclic conjugated systems
When the common electron pair belongs to only two atoms (involved in the covalent bond), the covalent bond
is called localized or bicentric. When the molecular electron orbitals cover the nuclei of more than two atoms
the bond is called delocalized. Such bonds are present in the so called conjugated systems - molecules in
which there is an alternation of single and double bonds.
Lets consider the molecule of 1,3-butadiene, as an example of an acyclic conjugated system:

All the carbon atoms are in sp2 hybrid state Actually, the bonds between the atoms are equal in length,
because the p-electrons in π-bonds move equally around all the four carbon atoms and the electron density is
equally distributed above and below the four nuclei.
 A typical example of a cyclic conjugate system is the benzene:

All the six carbon atoms are in sp2 hybrid state. They form six σ-bonds to obtain the so called σ-skeleton of
the molecule, which is planar. The p-orbitals involved in the formation of π-bonds are perpendicular to the
plane and their electrons move amongst all the six carbon atoms above and below the nuclei plane. All the six
bonds have one and the same length and energy.

Important definitions:
Aromaticity: A cyclic molecular formation is aromatic if
it has a significantly higher stability (due to
delocalization) than that of its corresponding hypothetical
localized structure. If the structure has a higher energy
(less stable) than its hypothetical classical structure, the
molecular formation is called "anti-aromatic".

Delocalized covalent bond: One or more electron pairs are common to three or more atoms in the structure
of a molecule.
Delocalization energy: The difference between the actual π-electron energy of a molecular formation and the
π-electron energy of its hypothetical non-conjugated compliance with a localized form of the π-electron
system.
 1.1.6. Non-polar and polar covalent bonds
Non-polar covalent bond - between the atoms of the same element at the same oxidation state - the electron
density is uniformly distributed around the two nuclei.
Polar covalent bond – between the atoms of different elements – the electron density is higher around the
nucleus of the atom of higher electronegativity.
Electronegativity: The ability of an atom of a given element to attract electron density compared to the
atoms of other elements in the compound. This ability depends on the ionization energy of the atom and its
electron affinity.
H
The electronegativity increases with increasing atomic number in the rows
2.1
of the Periodic Table: CH4 < NH3 < H2O < HF.
B C N O F It depends also on the hybridization and the oxidation state:
2.0 2.5 3.1 3.5 4.0
sp3-C sp2-C sp-C
Al Si P S Cl 2.5 2.75 3.1
1.5 1.8 2.1 2.5 3.0

1.1.7. Degree of ionicity and ionic bond

If the difference in electronegativities of the elements in a covalent bond is very large, the electron pair is
significantly shifted to the more electro-negative atom. This atom can acquire a negative charge and turn into
an anion, and the atom with the lower electronegativity - into a cation.
The two ions are hold together by the electrostatic forces
of attraction. The concept of ionic bond considers it as a
boundary state of covalent bond of a very high polarity.
Pure ionic bond does not exist as there is no complete transition of electrons from one atom to another.
Instead, the chemical bond is characterized by its degree of ionicity (DI) which depends on the deference
between the electro negativities of the two atoms (ΔEN) and is given in percentage.
For example: for HI DI is 6% and for HF DI is 41%.
Characteristics of the ionic bond:
• It is not directed in space, because the electrostatic field around each ion is spherical, i.e. the force field
is evenly distributed in all directions and can attract oppositely charged ions in every direction.
• It does not have the ability to saturate. Never mind the number of oppositely charged ions in the range
of an ion, they all are attracted and retained around it.
Substances with an ionic structure: salts, metal oxides, halides, sulfides etc.
Ionic substances are solids with high melting temperatures.
Ions form a crystal lattice in which they are closely located and surrounded with the maximum number of
oppositely charged ions. The ions arrangement is such as to achieve a minimal state of energy and so, a
maximum stability.

NaCl TiO2
 1.2. Basic characteristics of molecules
1.2.1. Geometry of molecules and valence angles
The basic spatial molecular structures are:

V-shaped linear triangular tetrahedral trigonal-bipyramidal octahedral

(tetragonal-bipyramidal)
Important characteristic of the molecule is the valence angle formed between two adjacent valent bonds. The
angles in the figure are true only if the two bond are formed by the same atoms: H-C-H. If the atoms are not
the same or the central atom has unshared electron pair(s) (UEP), the angle is different from that in the figure.
For example: water (H-O-H, 104.5º) and methane (H-C-H, 109.5º). In dichloromethane the valence angles
are H-C-H 112º, H-C-Cl 109º, Cl-C-Cl 111º.
Dihedral angle (torsion angle): The angle between two intersecting planes of a third plane perpendicular to
the intersection of the two planes.
Plane 1 – ABC
Plane 2 – BCD
Plane 3 – in red
The torsion angle varies from -180º through 0º to +180º.
The torsion angle between A and D is positive if the bond A-
B is rotated clockwise to reach the bond C-D; a negative
torsion angle requires reverse rotation.
 1.2.2. Length and energy of chemical bonds
Chemical bond length: the average distance between the nuclei of covalently bonded atoms, corresponding
to the minimum energy of the system.
The length of the bond depends on the nature of the atoms, their hybridization and the degree of oxidation. It
is usually measured in angstroms (Å).
Chemical bond energy: The minimum energy that must be expended to divide a mole of molecules into two
parts (atoms or atomic groups), by breaking a certain covalent bond, and to remove these parts from each
other at an infinite distance.
This energy is given for standard conditions - pressure 1 atm and temperature 25ºС and exceeds 150 kJ/mol,
e,g, for N2 it is 900 kJ/mol or more. Chemical bond energy is also called binding energy or dissociation
energy for diatom molecules.
Lengths and dissociation energies of some chemical bonds at 25° C.
Chemical E Bond’s length Chemical Bond’s E
bond (kJ/mol) (Å) bond length (Å) (kJ/mol)
C-H 415 1.10 C-C 1.54 344
C-F 443 1.38 C=C 1.35 615
C-Cl 328 1.77 C≡C 1.21 965
C-Br 279 1.94 C=N 1.22 615 sp3-C sp2-C sp-C
C-I 240 2,10 C≡N 1.16 890
C-N 300 1.47 C=O 1.22 725 sp3-C 1.54 1.51 1.46
C-P 264 1.87 C=S 1.60 573 sp2-C 1.48 1.43
C-O 350 1.43 N=N 1.25 418
C-S 272 1.81 N=O 1.17 607 sp-C 1.38
N-N 167 1.45 P=O 1.40 544
N-O 201 1.41 S=O 1.43 522
P-O 335 1.63
O-O 142 1.48
S-O 265 1.60
-10
1 Å = 1*10 m
 1.2.3. Dipole moment
Every molecule can be presented as a particle, in which positive (nucleus) and negative (electron clouds)
charges exist. The area in which positive charges prevail is called positive charges center, and this in which
negative charges prevail is called negative charges center. In symmetric molecules, the two centers coincide
and the molecule is non-polar. In asymmetric molecules, the two centers do not coincide - negative charge is
localized in one part of the molecule, and positive charge equal to it – in another part of molecule. In this
case, the part to which the electron cloud has shifted is negatively polarized, and the part from which the
cloud has shifted is positively polarized. Such molecules are called dipole (bipolar).
The size of the dipole is measured by the dipole moment (μ), which is
determined by the electric charge of the dipole multiplied by the distance
(l) between the two "electrical centers": μ = q.l
μ – dipole moment [C.m]; q – electric charge [C]; l – distance [m].
1 D = 3.335*10-30 C.m
The dipole moment is a vector variable. It has a direction indicated by an arrow, the tip of which points to
the negative charge (+ → -). When calculating the total dipole moment of a molecule, the vector nature of
the electric dipole moments of all bonds is taken into account, i.e, μ is a vector sum.
Dipole moment (μ) of some compounds in Debye (D)
compound μ (D) compound μ (D) compound μ (D)
HF 1.82 H2O 1.85 CH4 0.00
HCl 1.43 CO2 0.00 CH3Cl 1.01
HBr 1.08 H2C=O 2.33 CH2Cl2 1.60
HI 0.44 CHCl3 1.87

H2O CO2
CH2Cl2 CF4
 1.2.4. Hydrogen bond (HB)
Hydrogen bond: A form of association between an electronegative atom having at least one unshared
electron pair and a hydrogen atom covalently bonded to a second, relatively electronegative atom (Y).
The atom covalently bonded to the hydrogen atom is called the donor (Y), and
the atom with UEP (X) is called the acceptor .
The energy of HB is usually 10 to 30 kJ/mol, but can reach 160 kJ/mol. HBs with energies above 120 kJ/mol
have a covalent character and are called strong HBs (SHB).
SHBs are involved in the formation of some “unusual” compound like KHF2, containing the ion [FHF]-.
Strong HB is also present in the ion H5O2+ ([H2O-H-OH2]+), which is the actual form of hydrogen cations in
aqueous solutions.
Intermolecular hydrogen bonds: They occur between individual molecules of a substance/substances.

water 4-hydroxy benzoic acid acetone-water

Intramolecular hydrogen bonds: They occur

within a single molecule, i.e. the donor and the
acceptor groups are in the same molecule in
close proximity to each other. During the bond
formation, they converge even more. So, the
ethylene glycol salicylic acid 2-nitrophenol
HB can change the shape of the molecule.
 1.2.5. Significance of hydrogen bonds for life
Due to the HBs between water molecules around a hydrophobic molecule, specific intermolecular
interactions, called hydrophobic, occur which are crucial for the tertiary structure of biopolymers.
HBs are realized in the secondary as well as moderately in the tertiary structure of proteins and are
important for their stability.
HBs play an essential role in stabilizing the double-stranded structure of DNA, the spatial organization of
RNA and in the structures of polysaccharides.
The intermolecular HBs between the cellulose chains give the wood its characteristic properties. In plants,
water molecules bind not only to each other, but also to the cellulose chain in the walls of plant cells. This
creates a kind of capillary tube that allows capillary forces to occur. This mechanism allows the plants to
draw water into their roots.
Hbs can create a long chain of water molecules that can overcome the force of gravity and move to the
height of the leaves.
HBs are also important for the intermolecular recognition. For example, the binding of many enzymes to
their specific substrates or inhibitors, the formation of a complex between an antibody and its specific
antigen, the formation of a complex of a signaling molecule with the corresponding receptor.

HBs between adenine and cytosine in the structure of the DNA double helix.
 1.2.6. Nonvalent interactions (intramolecular and intermolecular)
The intermolecular interactions differ from the chemical bonding:
• they occur at significantly greater distances
• are characterized by a lack of saturation and specificity
• have low energies.
They are united under the common name of van der Waals forces.
Vanderwaals interactions
Dipole-dipole (orientational) interactions
Polar molecules (dipoles) orient to each other with their oppositely charged poles. The energy of these
interactions is in the range of 4 - 50 kJ/mol. With increasing temperature the thermal movement of
the molecules increases and the probability for orientation decreases.

Induction interactions

Those are between polar and nonpolar molecules. Polar

molecules deform the electron cloud of non-polar ones. As a
result, the nonpolar molecule acquires a temporary electric
dipole and then the two molecules interact as dipoles, i.e. as in
the orientational interactions. The energy of these interactions
is in the range 2 - 10 kJ /mol.
 Dispersion interactions (London’s forces)

Those appear between nonpolar molecules. In nonpolar particles, the electron density may concentrate in
one region due to the free movement of electron clouds. Such a state of the molecule lasts for a very short
time an so, the dipole is called instantaneous. Nevertheless, the time is sufficient to induce a dipole on
another molecule. Then, orientation interactions occur which distribute farther The energy of these
interactions is in the range ≤ 4 - 8 kJ/mol.

1.2.7. Biological significance of nonvalent interactions

• Nonvalent interactions are important for the tertiary structure of biopolymers.
• They are also important for intermolecular recognition, such as binding of enzymes to their specific
substrates or inhibitors, formation of the complex antibody-antigen, formation of a signal molecule
complex with the corresponding receptor.
• The attraction between two large molecules can be significant if they have certain complementary
forms, with many van der Waals contacts occurring in the vicinity. The specificity of the intermolecular
bonds between proteins or proteins and nucleic acids are also due to the nature of these non-covalent
forces.
 1.3. Electronic effects in molecules. Types of chemical reactions and reagents
1.3.1. Induction effect
Induction effect (I-effect): Redistribution of electron density in the original molecule under the action of a
substituent (polarization of other σ-bonds) along the axis of the sigma bonds, i.e. the polarization of one σ-
bond causes polarization of the adjacent σ-bond.
The inductive effect of the hydrogen atom is assumed to be zero.
The induction effect weakens along
the carbon chain.

Negative inductive effect (-I-effect): when the polarization of the bonds occurs toward the substituent.
Positive inductive effect (+I-effect): when the bonds are polarized from the substituent to the carbon atoms.
Substituents with -I effect Substituents with +I effect
F, Cl, Br, OH, OCH3, NH2, NHCOCH3, BH2, B(CH3)2, SiH3, Si(CH3)3, Li, MgCH3, CH3,
>C=O, COOH, COOCH3, >C=N, C≡N, NO2 CH2CH3, CH(CH3)2, C(CH3)3, Al(CH3)2

Alkyl substituents generally have a +I-effect due to the weak polarity of the
C-H bond, in which the more electronegative atom is carbon. For alkyl
radicals the +I-effect increases with increasing length of the carbon chain
and especially the degree of its branching.
1.3.2. Resonance method
Resonance: If two or more logical (acceptable) classical structures can be written for a given particle
(molecule, ion or radical), then the real distribution of the electron density does not correspond to any of
them, but is intermediate.
Classical structures are called boundary (resonant) structures. The resonant structures are connected with the
resonance sign - two-way arrow (↔) and are enclosed in middle brackets:
 For example, carboxylate ion has two resonant structures The true electron
density distribution corresponds to a hybrid structure in which each of the two
boundary structures contributes 50% and the length of the C-O bonds
corresponds to 1.5 orders of magnitude (between single and double).

The situation is similar with benzene, which is a resonant hybrid in

which all C-C bonds are equivalent:

In 1,3-butadiene the electron density distribution

corresponds to a resonant hybrid of two boundary
structures, represented to different degrees, because in one
of them formal (partial) electric charges are present.
Similar is the situation in propenoic acid:

Rules to be followed when writing resonant structures:

1) the atoms of the molecule do not change their position, only the position of UEP and π-electrons of
multiple bonds changes;
2) each resonant structure must have the same sum of π electrons (π bonds and UEP of heteroatoms).
Any delocalization of the electron density and any scattering of the electric charges leads to a
thermodynamic stabilization of the corresponding particle (molecule, ion or radical).
1.3.3. Mesomeric effect
Mesomeric (M-effect) or resonance effect (R-effect) is observed in conjugate molecular systems due to
delocalization of π- and/or p-electrons (formation of delocalized bonds in molecules).
Positive mesomeric (resonance) effect (+M-effect): when a substituent is a donor of electron density to the
conjugate system.
Positive mesomeric effect is realized by n, π-conjugation where n is UEP of a substituent.
Thus, the C-Cl bond in chloroethene (vinyl
chloride) or the C-O bond in methoxyethene
partially acquire the character of double
bonds and are shortened and strengthened.

The +M-effect can also be due to negatively charged ionic substituents

such as in enolate ions
The +M is also observed in longer chain systems and the resonant structures can be more than two:

Negative mesomeric (resonance) effect (-M-effect): when the substituent draws electron density from the
coupled system to itself.
Negative -M-effect represents a π,π conjugation caused by a substituent having a π-bond(s) in which
strongly electronegative atoms or atoms with a vacant orbital participate, i.e. are electron acceptors.
Examples are propenal (acrolein) and nitroethene:

Substituents with -М effect Substituents with +М effect

>C=O, COOH, COOCH3, >C=N, C≡N, -C≡C-, F, Cl, Br, OH, OCH3, NH2, N(CH3)2, SH,
NO, NO2, -N(CH3)3+, S(CH3)2+ NHCOCH3, О-, S-

The mesomeric and inductive effects act simultaneously and their influence is
superimposed.
 1.3.4. Types of chemical reactions
According to the way of breaking / forming the chemical bond
Homolytic: Homolytic destruction of bonds takes place, as a result of which radicals are formed - neutral
particles containing one unpaired electron. The opposite reaction is recombination.

Heterolytic: the common electron pair becomes the property of one atom or atomic group, resulting in the
formation of oppositely charged ions. The reverse process is the formation of a covalent bond by a donor-
acceptor mechanism.

According to the nature of the chemical conversion

Addition (coupling): A reaction in which two reagents form one product.
Most often this is a reaction in which a reagent binds to the substrate molecule at the expense of breaking the
π-bond (C=C, C≡C, C=O, C=N, C≡N, N=O, S=O and others.). The reaction is denoted by the Latin symbol
Ad (from "addition").

Elimination: A reaction in which a molecule or other particle (ion, radical) is released from a substrate.
This process usually produces two substances from one reagent. It is denoted by E (from "Elimination"). So,
E is the opposite of Ad.
Substitution: A reaction in which an atom or atomic group in the molecule is replaced by another atom or
atomic group (substituent).
Substitution reactions take place when two reagents exchange "parts" to give two new products. This
reaction is denoted by S (from "substitution").

Regrouping (Isomerization): A reaction in which a change occurs in the skeleton of a molecule, i.e. some
chemical bonds are formed at the expense of breaking other bonds within a molecule.

Oxidation-reduction (redox): Reactions in which reagents exchange electrons and in which the oxidation
states (oxidation numbers) change.

1.3.5. Types of reagents

Radical (free radical): A molecular object that has an unpaired electron.
Nucleophile (nucleophilic reagent): a reagent donating UEP. The nucleophile is a Lewis base.
Electrophile (electrophilic reagent): a reagent donating a free AO or, otherwise accepting UEP. The
electrophile is Lewis acid.

Nucleophiles react with electrophiles by donor-acceptor mechanism.

1.3.6. Activating energy. Activated complex and transition state
A chemical reaction occurs only between particles possessing energy higher than the average energy of the
whole system at a given temperature. The minimum energy that particles must have to react is called
"activating energy" - Ea. In the course of a reaction the system goes through a number of intermediate states,
in which the old connections are not completely broken, and the new ones are not completely formed.
Activated complex and transition state: The state corresponding to the highest potential energy of a
reaction is called “transition state”, and the configuration corresponding to this maximum is known as the
activated complex.
Reaction coordinate: Reflects the configurational changes in the elementary chemical act associated with
the change in the distances between the reacting particles. In the first approximation, it reflects the degree of
rupture of old bonds and the degree of formation of new bonds.
For example, lets consider the reaction between
chloromethane and iodide:

Intermediate (intermediate, I): Relatively unstable (short lifetime) and highly reactive molecular
formations occurring during the reaction course. Those are in low concentration during the reaction compared
to the amount of reagents or products.
 The scheme shows changes of energy during a chemical reaction.
Difference between the energy of the activated complex and the
energy of the starting materials (reactants) is the activating energy
of the reaction.

1.3.7. Complex reactions

Parallel (competitive) reactions
Reversible reactions

Sequential reactions

Chain reactions
 1.3.8. Thermal effect of chemical reactions
Energy changes in chemical processes can be expressed by the thermal effect of the chemical reaction.
Thermal effect of chemical reactions: The amount of heat that is released or absorbed during a chemical
reaction is called the thermal effect of the reaction. The thermal effect is denoted by Q and is measured in
joules (J) or kilojoules (kJ).
Since the thermal effect of the reaction depends on the physical state and the type of allotropic form of the
substances, in the thermochemical equations, after the formulas of the substances, the index is noted: (g) -
gas; (l) - liquid; (s) - solid; (aq) - aqueous solution, etc.
Chemical reactions that take place by releasing heat are called exothermic. They have a positive thermal
effect (+ Q). For example: C(s) + O (g) → CO (g) + 393.5 kJ
2 2
N2(g) + 3H2(g) → 2NH3(g) + 92.2 kJ
Chemical reactions that take place by absorbing heat are called endothermic. They have a negative thermal
effect (-Q). For example: N (g) + O (g)→ 2NO (g) - 180.4 kJ
2 2
CaCO3(s) → CaO(s) + CO2(g) - 178.3 kJ

Rules to be followed when calculating the thermal effect of a chemical reaction:

• The thermal effect of a chemical reaction is equal to the sum of the heats of formation of the reaction
products minus the sum of the heats of formation of the starting materials, taking into account the number
of moles with which they participate in the reaction.
• The heat of formation of simple substances is assumed to be zero. When a substance exists in several
allotropic forms, only its stable form under normal conditions has zero value of heat of formation.
• The thermal effect of a chemical reaction under certain conditions depends only on the initial and final
state, but not on the intermediate stages of the reaction.
 1.4. Isomerism
1.4.1. Constitutional (chain and positional) isomerism
The structural (constitutional) isomers have the same qualitative and quantitative composition, but differ in
chemical structure, i.e. the sequence of atoms in the molecule is not the same. Therefore, they exhibit
different properties.
Chain isomerism: Isomers have a different chain
structure - linear or branched.
pentane 2-methyl butane

Positional isomerism: These isomers differ in

the position of a functional group, substituent or
complex bond.
2-methyl pentane 3-methyl pentane
1.4.2. Stereoisomerism
1.4.3. Configuration isomerism
A configuration is the arrangement of atoms (atomic groups) in space, without taking into account the
rotation around simple bonds. The transition from one configuration to another can only be done by breaking
chemical bonds.
1.4.3.1. Enantiomerism in chiral center compounds
Enantiomers are stereoisomers that relate as an asymmetric object to its mirror image.
A chiral is any molecule that is not identical with its mirror image.
Typically, chiral molecules contain at least one saturated carbon atom (sp3-hybridized) attached to four
different substituents a, b, d, e. Such a carbon atom is commonly referred to as a chiral center, chiral
carbon atom or stereocenter and is denoted by an asterisk (*).
For example, lactic acid is a chiral molecule with two
stereoisomers. The substituents at the chiral carbon atom are
COOH, CH3, OH and H:

Optical activity: The phenomenon in which certain substances or their solutions rotate the plane of plane-
polarized light passing through them.
Light is electromagnetic radiation. The ray of ordinary light represents two oscillating fields - electric and
magnetic, which are in two mutually perpendicular planes. If we could look at the light beam from one end in
depth, and if we could see the oscillating electric field, we would notice that the electric field vector oscillates
in all possible planes. The same applies to the oscillation of the magnetic field.
After passing through a device called “polarizer”the electric field
of the beam oscillates only in one plane (also the magnetic one,
but in another, perpendicular plane). Such light is called plane-
polarized. Optical isomers (enantiomers) are a pair of isomers
with the same physicochemical characteristics that rotate the
plane of plane-polarized light at the same angle, but in opposite
directions.
For example, lactic acid has two optical isomers: right-rotating, denoted as (+) - lactic acid, which rotates the plane of
plane-polarized light at +3.8°, and left-rotating isomer, (-) - lactic acid, which rotates the plane at -3.8°. A mixture of
equal parts of (+) and (-) isomers is called a racemic mixture (racemate). Such a mixture is optically inactive ([α] =
0°) and is denoted by “±”, for example (±) -lactic acid.
The terms “enantiomers” and “optical activity” do not refer only to carbon. For example, tertiary amines in
which there are three different substituents (the fourth is UEP) can form two enantiomers, which can be
isolated at temperatures close to absolute zero because they pass rapidly into each other. On the other hand,
no such inversion is observed for their N-oxides and the corresponding enantiomers can be isolated under
normal conditions.

1.4.3.2. Fisher's projection and wedge-shaped formulas

Fisher projection formulas are constructed by transforming the
tetrahedron so that the front edge a-b (towards the observer)
becomes horizontal and the hind edge (d-e) is vertical. The
intersection of the projections of these two edges coincides with
the chiral center. In the projection formula thus derived, the main
group (or C1) is usually placed at the top.
Based on the projection formulas and the accepted structure of glyceraldehyde, Fischer introduced the concept of
relative configuration. If the substituents other than a hydrogen atom, in this case hydroxyl groups, are on the left
of the vertical line (carbon chain), they are denoted by L and those on the right by D. For example, in lactic acid the
isomer in which the hydroxyl group is on the left is denoted as L-lactic acid and the other as D-lactic acid:
Kahn, Ingold, and Prelog proposed other system for determining the absolute configuration, also known as the R, S-system.
It is adopted in the systematic nomenclature of IUPAC. A priority of the substituents around the stereocenter is introduced:
the atom that has the largest number in the periodic table is of highest priority. If the substituent is a group of atoms, the
atomic numbers in a substituent are summed. Other rules exist also. If the priority decreases clockwise, the configuration is
denoted as R (Latin rectus - right); if it decreases in a counterclockwise direction, it is marked by S (Latin sinister - left).
Through this system, the configuration of each chiral center can be determined, regardless of the nature of the substance. In
biochemistry the relative configuration (D, L-system) is used for natural compounds.

1.4.3.3. σ-Diastereoisomerism
This applies for molecules with more than one chiral
carbon atom. For example, the spatial structure of
monosaccharides with two chiral carbon atoms (C2 and
C3): erythrose and threose. Four combinations are
possible, expressed by Fisher projection formulas. There
are two pairs of enantiomers. D-erythrose and D-threose
have the same structures at C3 but their configuratiosn at
C2 are opposite. In general, the two molecules are spatial
isomers, but not enantiomers. They are diastereomers.
In the nomenclature, it is accepted that all diastereomers with two adjacent stereocenters, similar in
configuration to the erythrosis, are denoted by the prefix erythro, and those that are analogous to the threose
with the prefix threo. At n number of chiral centers, the maximum number of stereoisomers is equal to 2n.

An interesting case of diastereoizomerism is the structure of tartaric acids in which the substituents at each of
the two stereo centers C2 and C3 are the same: these are COOH, H, OH and CH (OH) COOH.
 The two formulas above correspond to the two optical antipodes of the
optically active tartaric acid (threo form). However, the other two
formulas are identical, because if we rotate one of them at 180° in the
plane of the drawing, we will get the other. This acid, called meso-
tartaric (ms-tartaric acid) has an achiral molecule (has the plane of
symmetry) and is therefore optically inactive. Meso-tartaric acid
(erythroform) is a diastereoisomer of each of the optically active
isomers.

1.4.3.4π-Diastereoisomerism (geometric isomerism)

The cases discussed so far are of the so-called σ-diastereoisomers, as they relate to compounds with σ-bonds.
The π-diastereoisomers are the cis-trans isomers known from alkenes, also called geometric. If we compare,
for example, the configuration of cis- and trans-2-butene or cis- and trans-cinnamic acids, it can be found that
these two pairs of isomers fully meet the definition of diastereoisomers, i.e. they are π-diastereoisomers.

It should be clear, however, that these are not chiral compounds, because the double bond and its
substituents lie in one plane, which is also a plane of symmetry for the molecule and are not optically active.
 1.4.4. Conformational isomerism
Conformation: different spatial states of a molecule with a given constitution (composition), which differ in
the magnitude of the angle of rotation around simple bonds (conformers). One conformer can be transformed
into another by rotating around a single bond.

1.4.5. Newman's projection formulas

The two carbon atoms are arranged one behind the other, with a small opaque disk placed between them.
Then only the part of the valent bonds at the more distant carbon atom, which is not covered by the disk, is
written. The energy of the conformations depends on the double-walled (dihedral) angle φ (fi) between the
plane of the bonds R1-C1-C2 and the plane of the bonds C1-C2-R2.

1.4.6. Basic types of conformations

Conformers (rotamers) are called the relatively stable (more stable) conformations.
Conformational isomers are called very stable conformers that exist independently and can be isolated as
individual substances.

Anti Eclipsed Eclipsed + Gauche - Gauche Totally

φ = ±180° φ = 120° φ = -120° φ = 60° φ = -60° eclipsed
(sin)
φ = 0°
 1.4.7. Conformations in butane
This is the energetic diagram of the conformations of butane:
The conformation with φ = 0 ° has the highest energy, when
the two methyl groups are closest to each other and the
greatest repulsive forces between them are realized.

The most stable is the conformer with φ = ± 180°, where the methyl groups are
located furthest from each other. This conformation is statistically the most
populated. The conformers with φ = ± 60° have a higher energy. Conformers with
φ = ± 120° (eclipsed) have a higher energy than gauche, due to the repulsion of
methyl groups with hydrogen atoms.

In cases other than repulsion, there may be favorable interactions between substituents. A typical example is ethylene glycol
(1,2-ethanediol). In this case, a hydrogen bond is formed between the two hydroxyl groups in a gaush conformation, which
stabilizes it and it becomes the conformation with the lowest energy.

1.4.6. Conformations of cyclohexane

It is possible to rotate around all six single C-C connections. There is a balance between the most stable
conformers "chair I" and "chair II". In them, the substituents on each of the six C-C bonds are in the gauche
conformation (see Newman's projections below). The "boat" conformation, through which the equilibrium
"chair I" - "chair II" passes, contains two opposite bonds with substituents in a shaded conformation
(eclipsed), and in addition, two of the hydrogen atoms (in position 1.4) are too close to each other in space.
All this leads to stresses (repulsive forces) in the "bath" conformation and it is a less stable conformer than
the "chair".
 chair I boat chair II

Energetic diagram

The "chair" conformers have 12 C-H connections, six of which are

parallel to the imaginary axis of the molecule and are called axial
(marked in red), and the other six are located close to the imaginary
equatorial plane of the molecule and are therefore called equatorial
(marked in blue)
 Disperse systems

2.1. Types of disperse systems. Properties of solutions

Disperse system: Systems of two or more substances in which the particles of one (disperse phase) are evenly distributed
between the particles of the other (disperse medium).
A disperse medium is usually a substance whose physical state coincides with the physical state of the system as a whole. In
case of the same physical state of the two substances, the substance that is in a larger quantity is considered to be a disperse
medium. Types of disperse systems according to the particle size of the disperse phase are:
Disperse system Particles’ size (nm) Coarse dispersions - Due to their significant size, the particles easily
Coarse dispersions > 100 precipitate or float depending on their relative weight. Coarse dispersions
Colloidal solutions 1 ÷ 100 include suspensions, emulsions and foams. They are unstable.
True solutions <1

Colloidal solutions - During prolonged residence or under the influence of external factors (heating, stirring, addition of
electrolytes) the dispersed phase precipitates or emerges on the surface and the system is destroyed - coagulation
True solutions - The dispersed phase is broken down into ions or molecules of low molecular weight compounds, which is
why these systems or solutions are also called molecular or ionic solutions. True solutions are stable systems.
2.1.1. Molecular and ionic solutions
Disperse medium of liquid solutions is called a solvent. The disperse phase is referred to as the solute. In solution, the
solute is in a state of individual molecules or ions. Depending on this, molecular or ionic solutions are distinguished.
Dissolution is a spontaneous process occuring when a substance comes into contact with a solvent, i.e. it is energetically
favorable process.
2.1.2. Mechanism of dissolution
Dissolution requires energy from outside to overcome the forces of attraction between building blocks of the solute and
those between the solvent molecules. Attraction forces also exist between the solvent molecules and the solute molecules or
ions. Solvent molecules surround the molecules or ions of the solute. As a result, groups called solvates are formed,
accompanied by the release of energy. Dissolution is a reversible process. The reverse process is precipitation.
 Dissolution of a solid with ionic
structure in water

Substances solubility depends on the Dissolution of a solid with

energy of the crystal lattice: polar molecular structure in
• Highly soluble (low energy) water
• Moderately soluble
• Slightly soluble or insoluble (high
energy)
Thermal effect of dissolution can be:
• Positive (exothermic - heat release): K2CO3, CaCl2, MgCl2, etc.
• Negative (endothermic - heat absorption): KNO3, NH4NO3, NH4Cl, etc.)
• Zero: NaCl, NaBr, LiNO3, etc.
Since dissolution is a spontaneous process, the thermal effect of the process
cannot serve as a criterion for its course.
2.1.3. Solubility and concentration of solutions
A certain amount of solvent can only dissolve a certain amount of the solute at a constant temperature (solubility). Solubility
is determined by a number of factors, primarily depending on the nature of the solute and the solvent. In many cases, the
empirical rule that similar dissolve into similar (in terms of polarity) can be used.
Solubility of a liquid in liquid: unlimited (ethanol, glycerol, etc. in water); limited (diethyl ether or chloroform in water –
two layers are formed).
Solubility of a gas in liquid: varies according to the Henry's law - the concentration of dissolved gas is proportional to its
pressure above the solution at a given temperature. Henry's law applies only when no chemical interaction (or insignificant,
as is the case in the CO2 / H2O system) occurs between the soluble gas and the solvent.
The solutions are classified into 3 groups:
Unsaturated solution is the one in which more of the substance can be dissolved.
Saturated solution cannot dissolve more amounts of the substance. Under certain conditions, a dynamic equilibrium occurs:
the more particles of the substance pass into solution, the more particles precipitate, and macroscopically the concentration of
the solute does not change. In order to obtain a saturated solution, the solute must be in excess and is in constant contact with
the solution.
Supersaturated solution contains a larger amount of solute than corresponds to a saturated solution at a given temperature.
Superaturated solutions are nonequilibrium systems and they cannot be obtained by directly dissolving the substance in the
solvent.
Concentration: the ratio of mass, amount in moles or relative volume of the solute to the volume of the whole system.
Molar concentration: The number of moles of solute contained in 1 dm3 (1 L) solution. This is the most used concentration
𝒏 𝒎
in chemistry: 𝑪𝑴 = =
𝑽 𝑴.𝑽
CM - molar concentration (mol / L ≡ mol / dm3 ≡ M), n - amount of substance in moles (mol), m - mass of dissolved
substance (g), M - molecular mass of dissolved substance (g / mol) and V - the volume of solution (L ≡ dm3).
Mass concentration: The amount of solute in units of mass contained in 1 dm3 (1 L) solution:
𝒎
𝑪𝒎 =
𝑽
Cm – mass concentration (g/L ≡ g/dm3), m – mass of the solute (g) and V – solution volume (L ≡ dm3).
Molal concentration: The number of moles of the solute in 1 kg of solvent. It is a temperature independent concentration:
𝒏 𝒎
𝑪𝒎𝒐𝒍 = =
𝒎(𝒔) 𝑴. 𝒎(𝒔)
Cmol – molal concentration (mol/kg), n – quantity of the solute in moles (mol), m – mass of the solute (g), M – molecular
mass of the solute (g/mol) and m(s) – mass of the solvent (kg).
Relative (percentage) concentration: It shows how many parts by mass or volume of the solute are contained in 100 parts
by mass or volume of the solution. It is usually expressed in percentages:
𝒎. 𝟏𝟎𝟎 𝑽. 𝟏𝟎𝟎
𝑪 % = 𝑪(%) =
𝒎 𝑽
C(%) – percentage concentration (%), m – mass of the solute (g), Σm – the mass of the solution (sum of the masses of the
solute and the solvent) (g); volume of the solute (L ≡ dm3) and S V – volume of the solution (L ≡ dm3).
Those concentrations are mostly used!
 2.1.4. Temperature dependence of solubility
The solubility of a substance in a solvent can be expressed also as grams solute in 100 grams solvent. This type of
expression is used to compare the saturated solutions of different substances in a given solvent at a given temperature.
The solubility of substances is strongly influenced by temperature. As the temperature rises, the solubility of the solids
usually increases. Some substances (e.g NaCl) almost do not change their solubility with increasing temperature. In rare
cases, a decrease in solubility has been observed with increasing temperature. For example, Ca(OH) 2, known as slack lime,
lowers its solubility with increasing temperature. CdSO4 is similar. There are other special cases. Thus, MnSO4 increases its
solubility in water up to 20°C and decreases it at higher temperatures. The solubility of the gases decreases with increasing
temperature. Some gases that react with water do not obey this dependence, as is the case with HCl.

2.1.5. Electrolyte solutions

Acids, bases and salts are called electrolytes, because their aqueous solutions conduct electricity. Upon dissolution, the ionic
substances release ions into the solution, which are solvated. Electrolyte molecules break down into ions under the action of
solvent molecules. As a result, the number of particles in the solution increases, and this leads to changes in some properties
of the solutions.
2.1.6. Dissociation constant and degree of electrolyte dissociation
Electrolyte dissociation is the process of breaking down an electrolyte into ions under the action of solvent molecules.
Upon dissolution, the molecule of the electrolyte KA decomposes into ions - cations K+ and anions A-:
Over time, the concentration of cations and anions increases, they become closer and can meet in the solution. Attraction
forces arise between them and they can bind into a molecule. This process is called molarization and is the opposite of
dissociation. After some time, the two processes equalize and equilibrium occurs. The equilibrium state is characterized by
the equilibrium constant KD which is called the dissociation constant:

Dissociation constant: the ratio of the multiplied equilibrium concentration of ions to the equilibrium concentration of the
undissociated compound. It depends on the nature of the solvent, the temperature, but does not depend on the concentration
of the substance in the solution.
Another important value from a practical point of view is the
degree of electrolyte dissociation (α):
where α is the ratio of the amount of electrolyte decomposed into ions to the total amount of electrolyte in solution; n d -
number of dissociated molecules; Nt - total number of dissolved molecules, NA - Avogadro's number (6.02214076×1023).
Otherwise: α is the ratio of the molar concentration of ionized (dissociated) molecules ([CM]i) to the molar concentration of
all dissolved molecules ([CM]o).
Degree of electrolyte dissociation: The part of molecules that decomposes into ions in solution. It depends on the
concentration, the nature of the substances, the temperature, the dielectric constant of the solvent, the presence of ions of the
same charge (positive, negative).
Instead as a fraction (1 ≥ α ≥ 0), ɑ can also be expressed as a percentage.
2.1.7. Strong and weak electrolytes
According to the degree of electrolyte dissociation, electrolytes are divided into strong (α is 30-100%), moderate (ɑ is 3-
30%) and weak (α is below 3%).
Strong electrolytes Medium electrolytes Weak electrolytes
HCl, HBr, HNO3, H2SO4, H2SO3, H3PO4, HF, HNO2, H2О, H2S, H2SiO3, HCN, HClO,
H2SeO4, H2Cr2O7, HMnO4, H2C2O4, HCOOH, LiOH, CH3COOH and other organic
HClO4, CF3COOH, CH3SO3H, Са(ОН)2, certain salts acids and bases, NH4OH,
NaOH, KOH, RbOH, CsOH, Al(OH)3, Fe(OH)2, CdCl2, ZnI2,
Ba(OH)2, Sr(OH)2, many CdI2, HgCl2, HgI2 and other salts
salts
 2.1.8. Ostwaldʹs law of dilution
For weak electrolytes, the constant and degree of dissociation are related by Ostwald's dilution law:
C - molar concentration of the electrolyte.
By substituting the concentrations [K+], [A-] and [KA] with their equal from
the above expressions in the equation of the dissociation constant we obtain:
For weak electrolytes α << 1 and accordingly 1- α ≈ 1. Then the
above expression takes the form:

The degree of electrolyte dissociation of a weak electrolyte increases with decreasing its concentration, respectively
with dilution of the solution. The physical reason for this is that when diluting the solution, it becomes less likely for two
opposite ions to encounter and to form a molecule, i.e. the probability for the molarization process is reduced.

2.2. Colloidal disperse systems. Colligative properties of dilute solutions

In colloidal solutions, the dispersed phase has a particle size of 10 -7 to 10-9 m (1-100 nm). The phase particles are separated
by a boundary surface from the disperse medium, but cannot be observed directly due to their small size. That is why they
are microheterogeneous systems that have more special properties.
2.2.1. Classification of colloidal disperse systems
А) According to the physical state of the dispersed medium B) According to the interaction between the disperse
Aerosols - gas. Lyosoles - liquid. Solid sols - solid. medium and the disperse phase
Disperse phase Disperse medium Examples
Lyophilic - dispersed particles strongly interact with the
Liquid Gas Aerosols - fog
solvent (adsorb a large number of molecules from the
Solid Gas Aerosols - smoke
disperse medium), e.g. hydrophilic - gelatin, Fe(OH)3,
Gas Liquid Foam
Al(OH)3, proteins or polysaccharides).
Liquid Liquid Emulsion
Lyophobic - dispersed particles interact weakly with the
Solid Liquid Suspension
solvent (adsorb a small number of molecules from the
Gas Solid Solid foams (foam plastics)
Liquid Solid Liquid inclusions in crystals
disperse medium), e.g. hydrophobic - sols of some
Solid Solid Some minerals and alloys
metals (silver, gold), slightly soluble metal sulfides.
Another feature by which colloidal systems can be classified is the structure of colloidal particles. Based on this feature,
they are subdivided into associative (micellar) and molecular.
The hydrosol (colloidal solution in water) of silver iodide (AgI) can be obtained by precipitation when mixing a solution of
silver nitrate with a solution of potassium iodide.

Lets consider the structure of the colloid particles: The nucleus center contains a microcrystal of the low soluble compound
AgI which has a considerable surface for ions adsorption. The other layers of the particle depend on whether potassium
iodide (left) or silver nitrate is in excess (right). One of the two ions that make up the precipitate is primarily adsorbed:
In the excess of iodide ions, they are primarily absorbed
on the nucleus (core) and are called potential
determining ions and the layer – potential determining
layer. They attract oppositely charged ions from the
solution (potassium ions) – secondary adsorption. Some
of the potassium ions are tightly attached to the potential
determining layer and form adsorption layer. The others
are loosely attracted and form the diffusion layer. The
core and the adsorption layer form the granule which in
this case is negatively charged. The core, the adsorption
and diffusion layer form the so-called micellar colloidal
particle (micelle), which is electroneutral.

In the excess of silver ions the primary layer is

composed of silver ions, the adsorption and the diffuse
Excess of KI layers are formed by nitrate ions. The granule is Excess of AgNO3
positively charged.

The granules of all the micellar colloidal particles are equally charged which is important for the properties of the micellar
colloid solutions.
 2.2.2. Kinetic and optical properties
Kinetic properties
Brownian motion. It is a chaotic movement along a broken line. This complex
course of the particles is the result of the continuous chaotic thermal motion of the
molecules of the disperse medium. Each colloidal particle experiences impacts from
all sides and moves in a direction determined by the vector sum of all forces acting
on it.
Diffusion. The particles of the solute are in constant chaotic motion. They are evenly
distributed throughout the volume of the solution. The movement of colloidal particles
takes place from places with higher concentration to places with lower. The rate of the
diffusion process decreases with increasing viscosity of the disperse medium and with
the increasing size of the colloidal particles.
Osmosis. This phenomenon will be discussed in detail in the following sections.
Sedimentation (coagulation). The phenomenon of visible precipitation of the dispersed phase, i.e. visible separation of the
dispersed phase from the dispersed medium.
Optical properties
In their optical properties, colloidal particles differ significantly from real solutions. The optical properties are manifested as
opalescence, coloring and Tyndall effect and are due to the absorption and scattering of light by colloidal particles.
Colloidal solutions appear cloudy in reflected light - they opalesce. For example, white ashes of silver chloride opalesce in
bluish color. This is due to the colloidal particles dimensions that are comparable to the wavelength of light in the visible part
of the spectrum, especially in the blue region. For example, the scattering of rays with a shorter wavelength explains the blue
color of the lake water, the sky blue and others.
 Their coloration is due to the selective absorption and diffraction (scattering) of light by colloidal
particles. Most colloidal solutions are brightly colored in a variety of colors. For example, the sol of
arsenic sulfide As2S3 is bright yellow, of iron hydroxide Fe(OH)3 is reddish brown. The figure shows a
colloidal solution of silver:

Some sols have the property of polychromy - depending on the method of obtaining the same
sols are colored differently. This is due to the different shape and size of the colloidal particles
and hence the differences in their adsorption capacity of light with different wavelengths. In
the figure colloidal silver in different stages of aggregation is shown:

The scattering of light by colloidal particles explains another

phenomenon characteristic of all colloidal solutions - the Tyndall effect
(visible path of light). It is observed when light is passed through a
solution, provided that the observer is perpendicular to the direction of
the light beam.

2.2.3. Electrical properties

The electrical properties of colloidal particles are explained by the presence of charges in
the colloidal particles, which are determined by the potential-determining ions of the
adsorption layer. Under the action of a direct electric current, all colloidal particles move
to the corresponding oppositely charged electrode. This phenomenon is called
electrophoresis.
2.2.4. Solutions of high molecular compounds
High molecular compounds (HMCs) are those with molecular weights higher than 5,000 - proteins, nucleic acids and
polysaccharides. Their solutions are referred to as molecular colloids since the molecules have the size of colloidal
particles. However, differencs exist between colloid solutions and solutions of biopolymers: the last are essentially
homogeneous systems. They do not have a separation surface, which is typical for colloidal solutions. Biopolymers
solutions are true solutions, although they have many properties similar to those of colloidal solutions. Unlike colloids, true
solutions are stable in terms of aggregation of the particles.
 2.2.5. Stability and coagulation of colloidal solutions
The stability of colloidal systems is much less than that of ordinary solutions. The adhesion and aggregation of colloidal
particles is counteracted by the same charges in hydrophobic colloids or solvate shells in hydrophilic ones. Regardless of
whether the colloid is lyophilic or lyophobic, the main factor for its stability is the adsorption capacity of the colloidal
particles. Therefore, all factors that favor desorption favor coagulation processes. Of these factors, the most important is
the high temperature - it always leads to coagulation of the colloidal system.

Coagulation in lyophobic colloids can be induced by:

1. Increase in temperature;
2. Mixing colloidal solutions with opposite charge;
3. In an electric field (electrophoresis);
4. Addition of electrolyte;
5. Addition of concentrated electrolyte solution.

2.2.6. Biological significance

The coagulation of lyophilic colloids is in many cases reversible. This is of great importance for the existence of living
organisms. Reversible lyophilic colloids have the property of forming a gel which contains a significant amount of molecules
from the disperse medium. Such a gel is formed, for example, by pectin. These gels can repeatedly change from a gel state to
a sol and vice versa only when the amount of dispersed medium and temperature change.
Blood, lymph and cerebrospinal fluid are colloids. Colloids in the various tissues of living organisms determine the diversity
of their functions and properties. Colloidal substances bind and retain a significant amount of water, which allows various
processes to take place in cells and tissues. They play a role in processes such as nutrition and the absorption of various
substances, including drugs.

2.2.7. Colligative properties of dilute solutions

Properties of the solution that do not depend on the type but on the concentration of the solute are called colligative. The
solute must be non-volatile and not affect the composition of the vapor phase, which is in equilibrium with the liquid phase.
2.2.8. Vapor pressure, change in boiling point and freezing point

Saturated vapor pressure

At any temperature, the solvent molecules from the surface may pass into the gaseous state - evaporation. Oppositely, the
solvent molecules from the gas state may pass into the liquid – condensation. If a liquid is placed in a closed vessel, a closed
system is formed in which a dynamic equilibrium is established between evaporation and condensation. The equilibrium
vapor pressure is called the saturated vapor pressure.
If a solution is placed in one vessel and pure solvent in another and the vessels are closed, upon reaching equilibrium both
systems will be characterized by their saturated vapor pressure. However, at the same temperature, the saturated vapor
pressure above the solution is always lower than that above the pure solvent.
The reason for this is the different intermolecular interaction in the solution and the solvent. In solution, solvent molecules
interact not only with each other but also with the particles of the solute. In order to enter the gas phase, the solvent
molecules must overcome these forces of attraction. It is obvious that in the pure solvent, its molecules have to overcome
only their inter-molecular interactions. In addition, the saturated vapor pressure above the pure solvent is higher than that
above the solution, because on the surface of the solutions, in addition to solvent molecules, there are also particles of the
solute. Therefore, there are fewer solvent molecules on the surface than in the pure solvent and, accordingly, a lower
probability of evaporation and hence lower vapor pressure is established.
As the concentration of the solution increases, the decrease in saturated vapor pressure becomes bigger. This dependence is
formulated in the Raoul's law: The decrease in the pressure of saturated vapor over the dilute solution compared to
that over the pure solvent is directly proportional to the mole fraction of the solute.

p0 – p = xs.p0 p0 – vapor pressure over the solvent at a given temperature; p - vapor pressure over the solution at the
same temperature; xs – mole fraction of the solute.
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑥=
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑎𝑛𝑑 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
Change in boiling point and freezing point
A liquid boils when the pressure of its saturated vapor equals atmospheric pressure. Solutions of non-volatile
substances have higher boiling points than those of pure solvent. At constant pressure, the increase in the boiling point of the
diluted solution is proportional to the concentration of the solution:
∆Tb – difference between the boiling point of the solution and that of the solvent; Ке – ebulioscopic
DTb = Ke.Cmol constant [K.kg/mol], which is specific for a given solvent and does not depend on the nature of the
solute and the temperature; Cmol – the molal concentration of the solute [mol/kg].
In the above equation, the solute concentration is expressed as molality, because it is temperature independent. When
dissolving 1 mol of substance (non-electrolyte) in 1 kg of solvent, the Tb of the solution increases by as many degrees as the
numerical value of the ebullioscopic constant. In order to reach atmospheric pressure and for the solution to boil, it must be
heated to a temperature higher than that of the pure solvent.
All pure solvents have a strictly defined and constant freezing point T f (solidification; crystallization). Liquids freeze at
temperatures at which their vapor pressure equals the vapor pressure over the solid phase. A change in the crystallization
temperature of the solutions compared to that of the solvent was observed. As the concentration of the solution increases, T f
decreases. The decrease in the freezing temperature of the solution is directly proportional to its molal concentration:

DTf = Kc.Cmol ∆Tf – difference between the freezing temperature of the solvent and that of the solution; Кc –
cryoscopic constant [K.kg/mol]; Cmol – the molal concentration of the solute [mol/kg].
The cryoscopic constant, like the ebulioscopic constant, is specific to the respective solvent and does not depend on the type
of solute and the temperature. When dissolving 1 mol of substance (non-electrolyte) in 1 kg of solvent, the Tf of the solution
decreases by as many degrees as the numerical value of the cryoscopic constant.
solvent Ке Кc
water 0.5 1.9
ethanol 1.2
acetone 1.7
benzene 2.6 5.1
acetic 3.1 3.9
acid
chloroform 3.9
nitrobenzene 5.2 7.0
 2.2.9. Diffusion, osmosis and the law of osmotic pressure
Diffusion: Transfer of particles, which leads to equalization of the concentration of substances at all points of the solution,
without external interference, due to the thermal movement of the particles. Diffusion is performed from places with higher
concentration to places with lower concentration.

As they move through the solution, the particles collide continuously. This leads to their chaotic motion, which causes the
particles to occupy the entire volume and the concentration of the solution is one in the same in the entire volume. This
applies both to the particles of the solute (or substances) and to those of the solvent. The diffusion rate is measured by the
amount of substance transferred per unit time through a unit area. It is proportional both to the difference in concentrations
between the two parts of the solution and to the temperature. The penetration of dissolved particles into the volume occupied
by a lower concentration solution or pure solvent occurs spontaneously.

Osmosis and osmotic pressure

If a semipermeable barrier (a membrane) is placed between two solutions of the same substance or between a pure solvent
and a solution, through which only solvent molecules can pass, one-way diffusion of the solvent particles takes place. The
reason is the desire to equalize the concentrations of the solutions.
Osmosis: The process of one-way passage (one-way diffusion) of solvent molecules through a semi-permeable barrier
between two solutions with different concentrations of the same substance or between solution and pure solvent.
The concentration of the solvent molecules in the solution is lower than in the pure solvent. Solvent molecules move to the
solution - they diffuse to the area with a lower concentration. They pass through the semipermeable membrane and enter the
solution. This leads to a gradual increase in the volume of the solution, as a result of which the elastic membrane swells
towards the solvent or the more dilute solution.
The impact of the dissolved particles on the membrane and the walls of the vessel causes an additional pressure, which is
called osmotic pressure. It occurs at the boundary between solution and solvent, separated by a semipermeable barrier. A
special device called an osmometer is used to measure the osmotic pressure of solutions. For example, to measure the
osmotic pressure of a glucose solution, the latter is placed in the osmometer, which in turn is immersed in a bath of pure
solvent (in this case water). As a result of osmosis, water molecules pass through the semipermeable barrier in the glucose
solution and dilute it, whereby the liquid level in the osmometer rises. The elevated level of the solution in the osmometer
resists the tendency of water molecules to pass through the semipermeable barrier. At a certain height of the column in the
capillary tube, the speed of passage of water molecules from the bath to the osmometer and from the osmometer to the bath is
equalized. Dynamic equilibrium is established and the level of the ladder remains constant. The hydrostatic pressure of the
solution column (Δh), which stops the osmosis, is called the osmotic pressure. It can also be represented as the additional
external pressure that needs to be applied to the solution to maintain the osmotic balance between the solution and the pure
solvent (or solution of another concentration), separated by a membrane permeable only to the solvent.

Vant Hoff’s laws of osmotic pressure: The osmotic pressure of a solution is equal to the pressure that the solute would
exert on the walls of the vessel if it were in a gaseous state and occupied the same volume as the solution at the same
temperature.
π – osmotic pressure [Pa]; R - the gas constant {8,314 [J/(mol.K)]}; T - the absolute temperature
p = R.T.CM [K] and C – the concentration of the solute [mol/L].
M

The osmotic pressure at a constant temperature is directly proportional to the molar concentration of the solute and does not
depend on its nature. Since an increase in temperature increases the kinetic energy of moving particles, the osmotic pressure
increases with increasing temperature.

It should be noted that the osmotic pressure is directly proportional to the molar concentration of the solute for dilute
molecular solutions of low molecular non-electrolytes. In electrolyte solutions, the experimentally measured osmotic
pressure is greater than theoretically calculated. For this reason, Vant Hoff introduces a correction factor:
 where i is the so called isotonic coefficient or Vant Hoff’s coefficient and is determined
p = i.R.T.CM experimentally.

πexp – the experimentally determined osmotic pressure; πne - the osmotic pressure of a non-
i = πexp/πne electrolyte solution of the same concentration.
The isotonic coefficient shows how many times the concentration of ions in the solution increases compared to the
concentration of the solute due to electrolytic dissociation. The determination of the osmotic pressure of an electrolyte
solution can be used to determine the degree of electrolyte dissociation. Solutions with equal osmotic pressure are called
isotonic. If the two solutions have different osmotic pressures, the solution with higher pressure is called hypertonic, and the
solution with lower pressure is called hypotonic.

2.2.10. Biological significance of osmosis

The cell membrane of each cell acts as a semipermeable barrier. The absorption of nutrients from the intestine, the
metabolism between the cell and the surrounding environment are directly dependent on osmosis. Blood, lymph, body fluids
in humans are aqueous solutions of molecules and ions of many substances. Their total osmotic pressure is about 7-8
atmospheres.

Saline solution - a solution of sodium chloride with a concentration of 0.15 mol/l or 0.9%. It creates the same osmotic
pressure as blood. It should be noted that the composition of the blood includes other salts and the actual saline solution has
the composition:
NaCl (0.85%), KCl (0.02%), CaCl2 (0.02%) and NaHCO3 (0.01%)

In the human body, fluids have a constant osmotic pressure due to the existence of an osmoregulatory mechanism. In the
osmoregulation a large burden falls on the liver and especially on the kidneys, through which excess water is expelled from
the body, as well as salts.
 3.1. Chemical kinetics
Chemical kinetics is a branch of chemistry that studies the rate and mechanism of chemical reactions, as well as the
influence of various factors on the rate of chemical reactions and developing research methods.
3.1.1. Rate of chemical reactions
The chemical reaction rate is the number of elementary acts that occur per unit time per unit volume (for homogeneous
reactions) or per unit surface area (for heterogeneous reactions). It is expressed as a change in the concentration of any of the
reactants or reaction products per unit time per unit volume (or per unit area) of the system.
For the reaction: A + X → D the reaction rate is: 𝑣 = ∆[𝐷] = − ∆[𝐴] = − ∆[𝑋]
∆𝑡 ∆𝑡 ∆𝑡
where v is the average reaction rate for the time interval ∆t [s] or [min]; ∆[…] – the change in molar concentration of any
substance [mol/L≡ mol/dm3].
∆[…] is positive when referring to the reaction products and negative when referring to the starting materials. It is especially
important to note that speed is always a positive quantity. Negative speed makes no physical sense. For this reason, to
express the rate by changes of concentration of any of the reaction products, the sign "+" is used, and the sign "-" respectively
∆𝐶𝑝 ∆𝐶𝑟
for the starting materials (reagents). 𝑣 = = −
∆𝑡 ∆𝑡

During the reactions, the concentrations of the starting materials decrease and the concentrations of the reaction products
increase:
The instantaneous or "true rate" of the reaction
refers to a very short period of time. And is
expressed by a differential - dt. Similarly, the
infinitesimal time interval dt corresponds to an
infinitesimal change in the concentration dС.
Thus, the instantaneous or true rate of a
chemical reaction is defined by the expression:

𝑑𝐶
𝑣=
𝑑𝑡
When one or more substances participate with two or more moles in the reaction equation, different results will be obtained
when determining the rate by one or another component. In this case, the rates obtained must be related to 1 mol of
substance.
∆𝐴 ∆𝐵 ∆𝑌 ∆𝑍
So, for the reaction: aA + bB → yY + zZ the reaction rate is: 𝑣=− = − = =
а. ∆𝑡 𝑏. ∆𝑡 𝑦. ∆𝑡 𝑧. ∆𝑡
As an example, lets consider the reaction: 2N2O5 → 4NO2 + O2 the rate of which is:
∆ 𝑁2𝑂5 ∆ 𝑁𝑂2 ∆ 𝑂2
𝑣=− = =
2. ∆𝑡 4. ∆𝑡 ∆𝑡

The reaction diagram

3.1.2. Dependence of the reaction rate on concentration

For simplicity, let us assume that a chemical reaction takes place in a homogeneous, system. In order for the reaction to take
place, it is necessary for the particles of the starting substances (atoms, radicals, molecules or ions) to collide with each other.
Some of these collisions do not lead to the formation of new substances, while in others - the so-called. effective impacts,
chemical interaction occurs. The effective impact in which a chemical interaction occurs is called an elementary act of the
reaction. From the graph it can be seen that the number of strokes is equal
to the product of the number of particles involved in the process.
Obviously, the higher the total number of impacts between the
particles of the reactants, the greater the probability of effective
impacts. Therefore, the number of strokes is proportional to
the product of the molar concentrations of the reactants.
 Kinetic equation. Rate constant
The influence of the concentrations of the reactants on the reaction rate :
aA + bB + … + nN →
is expressed by the basic law of chemical kinetics or the law v = k.[CA]a.[CB]b…[CN]n
of mass action:
The rate of a chemical reaction taking place at a constant temperature in a homogeneous medium is proportional to the
product of the molar concentrations of the reactants raised to degrees equal to the coefficients at the formulas of these
substances (number of moles) in the reaction equation.
The proportionality constant k is called the rate constant. It is a characteristic constant for a given chemical process and
depends primarily on the nature of the reactants, but also on some external factors: temperature, the presence of catalysts and
other factors, but not on the concentration. The physical meaning of the rate constant becomes clear if the concentrations of
all reactants are set equal to 1 mol / L: v = k The rate constant is the reaction rate under the given conditions when
all reagents have a concentration of 1 mol/L.
3.1.3. Reaction order. Reactions of different order
First order reaction Second order reaction
For the reaction A + B →
For the reaction A →
the kinetic equation is: v = k.[A].[B]
the kinetic equation is: v = k.[A]
For the reaction 2A →
v – the chemical reaction rate [mol/L.s; mol.L-1.s-1 ] or
the kinetic equation is: v = k.[A]2
[mol/L.min; mol.L-1.min-1];
v – the chemical reaction rate [mol.L-1.s-1] or [mol.L-1.min-1];
k – rate constant [s-1] or [min-1]; [A] – concentration of the
k - rate constant [L.mol-1.s-1] or [L.mol-1. min-1]; [A] and [B]
reagent [mol/L; mol.L-1; М].
- concentrations of the reagents [mol/L; mol.L-1; М].
Third order reaction
For the reaction A + B + D → For the reaction 2A + B → For the reaction 3A →
the kinetic equation is: v = k.[A].[B].[D] the kinetic equation is: v = k.[A]2.[B] the kinetic equation is: v = k.[A]3
v – the chemical reaction rate [mol.L-1.s-1] or [mol.L-1.min-1];
k - rate constant [L2.mol-2.s-1] or [L2.mol-2.min-1]; [A], [B]
and [D] - concentrations of the reagents [mol/L; mol.L-1; М].
The order of the reaction is the sum of all exponents of the concentrations in the equation of the law of mass action,
established experimentally.
 3.1.4. Molecularity of the reaction
The molecularity of a reaction is the number of particles involved in an elementary chemical act of the reaction.
Molecularity is determined by the number of molecules involved in the elementary chemical act of the process. For example,
if the elementary act is reduced to the destruction of a molecule, then the reaction is monomolecular. If two molecules must
be involved in the impact - the reaction is bimolecular, if three molecules are involved - trimolecular, etc. It should be noted
that in trimolecular reactions, three molecules should meet simultaneously at a given point in the reaction space and the impact
should be effective. It is obvious that the probability of such an event is very small, and an effective meeting between four
molecules is practically impossible.

3.1.5. Rate-determining step

The gross chemical equation shows the material balance of the system, its initial and final state. It is compiled on the basis of
the law of mass action and provides data on the quantitative ratio between the reactants, the possible yields and others. The
gross equation does not show the way in which starting materials are gradually transformed into products, i.e. it does not
show the mechanism of the reaction.
The mechanism of a chemical reaction is understood as the sequence of elementary processes affecting the destruction of
old and the formation of new chemical bonds, in which the starting materials are converted into the final products of the
reaction.
In successive reactions, one of all successive stages of the reaction mechanism is the slowest. It is called the rate-
determining or limiting step of the chemical interaction, and it determines the overall rate of the reaction. Therefore, the
mechanism of a reaction is not directly contained in its gross equation.
For example, the decomposition of N2O5 is expressed by the gross equation: 2N2O5 → 4NO2 + O2
The true mechanism of the reaction is a sequence of the 1. N2O5 → NO3* + NO2* slow
following steps (marked with * are molecular radicals): 2. NO3 + NO2 → NO + O2 + NO2 quick
* * * *

3. NO3* + NO* → 2NO2* quick

Thus, the decomposition of N2O5 is not subject to the
The actual equation of the rate is: v = k.[N2O5]
equation that would be reached in the formal application of
the mass action law (MAL): which applies to the first stage, since it is the slowest and is
v = k.[N2O5]2 therefore rate-determining.
The rate-determining step defines the kinetic equation. Other examples are given below. The rate determining steps are
marked in blue.

3.1.6. Influence of temperature on the rate of chemical reactions.

Arrhenius equation
Rising temperatures accelerate chemical reactions. According to the empirical rule of Vant Hoff, when the temperature
increases by 10°C, the reaction rate increases from 2 to 4 times. Increasing the temperature of a reaction system leads to an
increase in the number of impacts and hence to an increase in the reaction rate. Since not every impact leads to a chemical
interaction, the concept of "active impact" is introduced. It takes place on impact between particles that have an energy
greater than the average energy of all the molecules involved. The minimum energy that particles must have above the
average energy characteristic at a given temperature in order to participate in a chemical interaction is called "activation
energy" (Ea). In the course of chemical reactions it is necessary to break the bonds between the atoms in the molecules of the
reactants and to create new bonds between the atoms in the molecules of the reaction products. Accordingly, the difference
between the energy of the so called activated complex (transitional state) and the energy of the starting materials (reactants)
is the activation energy of the reaction.
The temperature dependence of the rate is calculated by the influence of temperature on the rate constant k. The quantitative
relationship between the rate constant and temperature is given by the Arrhenius equation:

k – rate constant; Ea – activation energy [J/mol]; T – absolute temperature [oK]; R – universal gas constant {8,314 [J/mol.K]};
A - preexponential factor. The factor A is in the range 0 <A <1; A - reflects the probability that the impact between particles
with sufficient energy is effective in terms of the course of the chemical reaction (the particles must also have a certain
orientation relative to each other - steric factor).
From the above equation it is seen that the rate constant, and the reaction rate are higher the higher the temperature and the
lower the activation energy of the process. The rate of the reaction directly depends on the number of molecules with energy
sufficient to form an activated complex, i.e. capable of chemical transformation. The more active molecules there are, the
faster the reaction. For the reaction to occur, the molecules in the collision must be oriented in a certain way and to have
enough energy. One way to increase the number of active molecules is by heating. The influence of temperature on the
reaction rate is visually represented by the so-called "Distribution curves". It is well known that a distribution of molecules
by kinetic energy and rate is established at each temperature. This distribution is maintained by the constant chaotic motion
of the molecules, during which they strike, redistribute their energies, change the direction of their motion. The figure shows
the dependence of a relative number of molecules as a function of their energy at two different temperatures:
Those curves are "normal distribution curves" or "Gaussian curves". A small
number of molecules have low energies and relatively the same proportion of
molecules have very high energies - the curves are symmetrical and have the
shape of a bell ("normal distribution curve"). In addition, at higher temperatures,
the bell-shaped curve has a lower maximum and is wider in its lower part. The
rate increases with increasing temperature, because the number of active impacts
between the molecules increases.
The rate constant, and therefore the reaction rate, are higher the higher the
temperature and the lower the activation energy of the process.

3.1.7. Influence of other factors on the rate of chemical reactions

The rate of a chemical reaction also depends on the nature of the reactants, the presence of a catalyst or an inhibitor. In some
cases, the reaction rate is influenced by the pressure (reactions in the gas phase), the nature of the solvent (reactions in
solution) and the type of electromagnetic radiation (photochemical processes). The rate of heterogeneous reactions depends
on the contact surface of the substances.
Biological significance
The course of biological processes largely depends on the rate characterized by the rate constant. The latter, together with the
diffusion coefficient, the osmotic pressure of the substances involved in the reactions, the magnitude of the electric charge,
the permeability of the cell membrane and others, form a system of physicochemical parameters characterizing the
functioning cell.
 3.2. Catalysis
Catalysis: A phenomenon in which the rate of a chemical reaction increases under the action of a substance called a catalyst.
3.2.1. Catalysts
Catalyst: A substance that increases the rate of a reaction, does not undergo qualitative and quantitative changes at the end of
the process and does not affect the change in the total standard Gibbs energy of the reaction.
3.2.2. Principle of operation of catalysts
In the presence of a catalyst, the reaction proceeds by a different mechanism, by carrying out intermediate steps, which are
more energetically favorable. A substance that accelerates a chemical reaction but is consumed during the reaction is called a
promoter. A substance that reduces the rate of a reaction is called an inhibitor.
Catalysis can be of different types: homogeneous (presence of only one phase), heterogeneous (the reaction takes place at or
near the phase boundary), autocatalysis (caused by one of the reaction products) and intramolecular (caused by a group in
the molecule of the reagent itself).
3.2.3. Homogeneous and heterogeneous catalysis. Mechanism of catalytic reactions
Homogeneous catalysis: The reactants and the catalyst form a homogeneous system, i.e. they are in the same phase.
In homogeneous catalysis, the reaction rate is proportional to the catalyst concentration. Some examples of homogeneous
catalysis are:

The most common case of homogeneous catalysis is acid-base catalysis. This type of catalysis is also widely used in
biocatalytic processes in living organisms.
In homogeneous catalysis, the catalyst leads the process through a different mechanism, including additional intermediate
stages, which have a lower activation energy than the uncatalyzed reaction:
 Catalyzed reaction
Non-catalyzed reaction
A + C → AC
A+ B→ D AC + B → D + C

Ea > Ea,1 > Ea,2; kc – catalytic constant

If in the catalytic reaction, the rate-

determining step is the second step:
v = k.[AC][B]
then the rate is directly proportional to
the concentration of the intermediate,
which in turn is proportional to the
concentration of the catalyst.

v = k.[A].[B] v = k.[C].[A] = kc.[A]

In homogeneous catalysis, the reaction rate is proportional to the catalyst concentration. The activation energies of the
intermediate stages are lower than the activating energy of the uncatalyzed reaction. Increasing the reaction rate is
achieved without importing energy from the outside.
For example, the oxidation reaction of sulfur dioxide to sulfur trioxide is catalyzed by nitric oxide:
The mechanism of the reaction is Nitrogen dioxide is obtained as an
intermediate, as a result of the reaction
of the catalyst with oxygen.
Heterogeneous catalysis: the reaction mixture and the catalyst are in different phases. When the catalyst is a solid and is in
contact with a gaseous or liquid reaction system, this catalysis is called contact, and the rate of the process is proportional to
the surface of the catalyst. The catalyst does not participate with its entire surface - this only happens in certain places, called
"active centers".

Examples:
In this type of catalysis, it is considered that intermediates are formed with a reagent on the catalyst surface. In some cases,
the intermediates are defined chemicals, but most often the intermediates do not have the character of defined chemicals, but
are surface adsorption compounds. In this case, the catalyst reduces the strength of the chemical bonds in the structure of the
reagents, which leads to a decrease in the activating energy of the reaction. An important process in industry is the oxidation
of alkenes to oxiranes, for example the oxidation of ethene to oxirane.:
The reaction proceeds with the formation on the surface of
silver oxide, which reacts with ethene:

Another example is the oxidation of sulfur dioxide to sulfur

trioxide catalyzed by V2O5.

Most often, in heterogeneous catalysis intermediates as defined chemical compounds do not form. Oppositely, surface
adsorption compounds are formed.
Non-catalyzed reaction
Catalyzed reaction
Such is the reaction of formation of alkanes from alkenes and
hydrogen at elevated temperature and pressure, in the
presence of platinum, palladium or nickel as catalysts. This
reaction is used not only in the chemical industry, but also in
the production of margarines (from liquid vegetable oils
containing predominantly unsaturated fats, solids in which
saturated fats predominate are formed).
The reaction between ethene and hydrogen, leading to the formation of ethane, goes through the following stages. The
covalent bond in the hydrogen molecule is broken down and adsorbed hydrogen atoms are formed on the surface of the metal
(or form a bond with the metal). The adsorbed H atoms on a metal surface are substantially more reactive than the hydrogen
molecule. Because the H-H bond (dissociation energy = 432 kJ/mol) is already broken, the energy barrier for most reactions
involving hydrogen is significantly lower at the catalyst surface.
Ethene is adsorbed on the surface of the catalyst, forming a
complex through the π-bond, as a result this bond is partially
ruptured. Hydrogen atoms can diffuse on the catalyst surface
and one hydrogen atom is added to the ethene:
Finally, another hydrogen
atom is attached, resulting in
the formation of ethane,
which is desorbed. The
reaction is reversible.
The platinum-rhodium catalyst is used in automobile 2CO + O2 ⟶ 2CO2
catalytic converters. Their aim is to reduce the amount of
toxic emissions from the combustion of petrol in internal 2NO ⟶ N2 + O2
combustion engines. They help to complete the combustion
of all carbon-containing compounds to carbon dioxide, and 2NO2 ⟶ N2 + 2O2
also aim to reduce the release of nitrogen oxides, which are
obtained at high temperatures in the combustion chamber.
A limitation of heterogeneous catalysis is related to the available catalyst surface. Once the surface of the catalyst is
completely saturated with reagent molecules, the reaction cannot continue until the products leave the surface and a small
space is opened for new adsorption or binding of a new reagent molecule. For this reason, the adsorption step in a
heterogeneously catalyzed reaction is often the rate-limiting step. However, the overall benefits of heterogeneous catalysis
often outweigh this disadvantage, as the catalyzed reaction is still much faster than the uncatalyzed reaction.
Catalysts are specific in their action. Only one group of catalysts is suitable for each process or group of processes. Catalysts do
not change the thermal effect of the reaction. Catalysts cannot cause impossible reactions. In reversible processes, catalysts
affect only the speed of the process, but not the chemical equilibrium, because they change the speed of both the forward and
the reverse reaction to the same extent. Therefore, the catalysts accelerate the time to reach equilibrium.
 3.2.4. Autocatalysis
Autocatalysis - A process in which one of the reaction products acts as a catalyst.
At the beginning of the autocatalytic process, the rate is relatively low, but increases rapidly over time as the amount of
catalytically active product increases. After a certain time, the reaction rate reaches a maximum value, after which it begins to
decrease due to depletion of starting materials. An example of such a process is the oxidation of oxalic acid with potassium
permanganate in an acidic medium:

In this case, the catalyst is Mn2+ ions. They react with

permanganate ions to form Mn3+ ions, which in turn oxidize
oxalic acid:
3.2.5. Influence of various factors on the catalytic process
Temperature. As the temperature rises, the catalyzed reaction rate also increases.
Pressure. In the processes the gas state, the rate significantly depends on the pressure.
Solvent. Rate of the catalytic process also depends on the nature of the solvent. The reason is different solvation and hence
the energy of the reacting particles.
Degree of catalyst dispersion. This is important for heterogeneous catalysis. The smaller the catalyst particles, the larger its
surface and that of the active centers, and the higher the rate of the catalyzed reaction.
The presence of different substances. The effectiveness of catalysts depends on the presence of certain substances. Some of
them stimulate their action and are called activators (promoters), while others reduce it and are called inhibitors. A third type
of substances also exists that irreversibly inactivate the catalyst and are called catalytic poisons.
3.2.6. General idea of biocatalysis
Biocatalyst - a biological substance that increases the rate of a chemical reaction in living organisms, while remaining
chemically unchanged.
Enzymes - these are proteins or glycoproteins, and they can function without or with coenzyme (non-protein part of different
nature: metal ions, organic compounds or complex compounds).
Abzymes (catalytic antibodies) - immunoglobulins (glycoproteins) that catalyze a certain type of reaction with a specific
substrate.
Ribozymes - RNA enzymes that work with coenzyme magnesium or manganese (2+) ions. They participate in the process of
"maturation" of RNA in many organisms, with the exception of higher eukaryotes, i.e. there are no such biocatalysts in the
human body.
Ribosome - Nucleic (RNA) / protein complex, including metal ions such as sodium, potassium, magnesium, zinc and others
which catalyzes protein synthesis.
Like all catalysts, biocatalysts do not change the chemical equilibrium (they increase the rate of the reaction and the reverse
reaction equally). The catalytic action takes place as a result of intermediate processes of the reagents and products with the
biocatalyst. These steps have a significantly lower activating energy than that of the uncatalyzed reaction. The intermediate
stages are presented below:

Biocatalysts (in particular enzymes: E) bind to the reactants, which in this case are called substrates (S). As a result, an
enzyme-substrate complex (ES) is formed, which is converted into several intermediate complexes due to chemical reactions.
As a consequence, an enzyme-product complex EP is formed, which dissociates thus releasing product(s) and the free
enzyme. Binding of the substrate takes place in the active center. The active site is relatively small in volume as compared
to the total enzyme. The active center is usually a depression: "cracks" or "pits" in the protein. It is filled with solvent - water.
Upon binding of the substrate, which is carried out on the basis of hydrophobic interactions, part of the water leaves the
active center. The active center is subdivided into a binding and a catalytic center. The catalytic center is composed of
amino acids or of amino acids and coenzyme(s) that are involved in the chemical transformation of the substrate. The binding
center is responsible for the intermolecular interactions that form the ES.
Enzymes have an extremely high efficiency - they accelerate the reaction rate most often from 109 to 1012 times. Enzymes,
like other catalysts, reduce the activation energy - they carry out the reaction in a different way but with lower activation
energies. The interactions between the enzyme and the substrate optimize and stabilize the enzyme-substrate transition state
(ES≠). The higher the absolute value of DGTS, the greater the stabilization of the transition state (ES≠) and the lower the
activation energy. The formation of ES also contributes to this. During its formation, a conformational changes in the two
molecules can be induced to varying degrees, which leads to a convergence and correct orientation of the reacting groups of
the two molecules. This increases the reactivity of the substrate.
 Non-catalyzed reaction

Catalyzed reaction

Biocatalysts, like chemical catalysts, have specificity (selectivity) with respect to the catalytic reaction. These are
chemoselectivity - selectivity with respect to the functional group; substrate selectivity - the ability to distinguish a
particular compound from a mixture of chemical compounds; regioselectivity - the ability to act in one place in a molecule
that contains the same functional groups and stereoselectivity - the ability to act on a substrate or to produce a product in one
enantiomeric or diastereomeric form.
Temperature affects the rate of enzymatic reactions. The temperature dependence of the enzyme activity (reaction rate) is
described by a bell-shaped curve, with a maximum corresponding to the optimal temperature of the given enzyme. According
to the principle of the influence of temperature on the rate, with increasing temperature, the rate of the catalytic reaction
increases. On the other hand, with increasing temperature, structural changes in the enzyme molecule take place leading to
the enzyme inactive forms - denaturation is observed. The graph shows the effect of temperature on cholesterol oxidase
activity at pH 7.5.
 3.3. Chemical thermodynamics
Chemical thermodynamics: Studies the conversion of energy during a chemical reaction and the ability of chemical systems
to do useful work. If a thermodynamic system does not exchange with the environment, it is called isolated system.
3.3.1. Thermodynamic quantities: enthalpy, entropy and free energy. Thermal effect of chemical reactions
Physical quantities characterizing the properties of a system are called thermodynamic parameters of the system. These
include: internal energy U, enthalpy H, entropy S and free Gibbs energy G.
Enthalpy (H) is a thermodynamic function of the state of the system which is used for isobaric (at constant pressure)
processes and characterizes the heat content of the system.
The enthalpy cannot be measured directly, it is only possible to measure the change in enthalpy ∆H (measured in [J]) as a
result of a chemical process:
∆Нreaction = Нfinal - Нinitial = Нproducts - Нreagents
The change of enthalpy in a chemical reaction is the thermal effect of this reaction (Q) at constant temperature and pressure.
In an exothermic process, heat is released into the environment (Q>0), while the change in enthalpy ∆H<0 (the energy of the
system decreases). In an endothermic process, heat is absorbed from the environment (Q<0) and the value of ∆H>0.
Examples of the thermal effect of some chemical reactions are presented:
C(s) + O2(g) → CO2(g) ΔH = - 393.5 kJ
N2(g) + 3H2(g) → 2NH3(g) ΔH = - 92.2 kJ
N2(g) + O2(g)→ 2NO(g) ΔH = + 180.4 kJ
CaCO3(s) → CaO(s) + CO2(g) ΔH = + 178.3 kJ
Entropy (S) reflects the probability one or another state of the system to be realized in the process of heat exchange; it is
proportional to the number of ways in which the system can perform its macro-state and is a measure of system disorder.
Entropy cannot be measured directly, it is only possible to measure its change ∆S (measured in [J / K]):
∆S = Q/T = Q.T-1 Q - heat released or absorbed [J]; T - the absolute temperature [K].
For a process occurring at a constant temperature (isothermal process), the change in entropy is equal to the heat that would
be transferred if the process was reversible divided by the absolute temperature. This means that the heat input to the system
increases the kinetic energy of the components (atoms, molecules or ions) and therefore increases their disorder.
The change in entropy of a chemical reaction is the difference between the final state
∆Sreaction = Sproducts - Sreagents
(entropy of the products) and the initial state (entropy of the reagents):
Gibbs' free energy (G), often referred to simply as free energy, is defined by three other functions of the state: enthalpy,
temperature, and entropy. It is the amount of energy released in the conversion of reactants to products under standard
conditions It, like other thermodynamic parameters, cannot be measured, but the difference ΔG is determined.
If a process (including a chemical reaction) takes place under isobaric-isothermal conditions, then ∆G = ∆H - T.∆S
the total driving force of the process is called the free Gibbs energy (ΔG) or isobaric-isothermal
potential:
The change in free energy (ΔG; measured in [J]) is the criterion for predicting the ∆Greaction = Gproducts - Greagents
spontaneity of chemical processes at constant temperature and pressure.
Examples of changes in the free Gibbs energy for some chemical reactions at 25°C and a pressure of 1 atm (101 kPa) are
presented:
C(s) + O2(g) → CO2(g) ΔG = - 394.4 kJ
N2(g) + 3H2(g) → 2NH3(g) ΔG = - 32.8 kJ
N2(g) + O2(g)→ 2NO(g) ΔG = + 175.2 kJ
CaCO3(s) → CaO(s) + CO2(g) ΔG = + 131.4 kJ
The functions of the state have a common property: a change in any of them depends only on the initial and final
states of the system and does not depend on the way this change is made. This allows the changes in each thermodynamic
function during the reaction to be calculated from the difference between the total values ​of the corresponding function for
the final substances and the total values ​of the same function for the starting substances. Calculations of thermodynamic
functions are usually reduced to standard conditions.
The generally accepted standard conditions in thermodynamics are temperature 298°K (25°C) and pressure 101.3 kPa
(1 atm). It is assumed that under these conditions each of the participants in the reaction is in its standard physical state -
stable under standard conditions.

3.3.2. Reversible and irreversible chemical reactions

Practically irreversible reactions are those in which products are unable to form back the starting materials.

Chemical reactions in which the starting materials are not completely converted into reaction products due to the interaction
between the products recovering the starting materials are called reversible reactions. The following are some examples of
reversible and irreversible chemical reactions:
 Reversible reactions Irreversible reactions

3.3.3. Chemical equilibrium. Law of Mass Action

Chemical equilibrium: This is a special state of reversible reactions in which the concentrations of all substances involved
remain constant indefinitely under certain conditions.
The main characteristics of chemical equilibrium are:
1. Reversibility of the chemical reaction;
2. Consistency of the composition of the system under given conditions.
In equilibrium state under given conditions, the ratio between reactants and products does not depend on the initial
concentrations of the components. If the conditions change, the system may react in the forward or reverse direction,
depending on the direction of the change in conditions. When the original conditions are restored, the system returns to its
original equilibrium state.
For example lets consider the reversible reaction N2O4 ⇋ 2NO2
Forward reaction Reverse reaction
 Let's consider the reversible reaction:
According to MAL, the rate of the forward reaction vf is: vf = kf.[A]а.[B]b for the opposite reaction: vr = kr.[C]c.[D]d
The chemical equilibrium is dynamic. the forward and the reverse reactions are constantly performed at the same rate.
In reversible reactions, the rate of the forward reaction initially has a maximum
value and then decreases due to the decrease of concentration of the starting
materials. Accordingly, the reverse reaction initially has a minimum rate, which
increases with increasing concentration of the reaction products. Finally, a state
occurs in which the rates of forward and reverse reactions become equal. Then:
vf = vr Using the MAL, we obtain: kf.[A]a.[B]b = kr.[C]c.[D]d
After conversion and keeping in mind the fact that the
rate constants are constants:

The ratio of the two rate constants (of the forward and the reverse reaction) is
a constant value for a given temperature and is called the equilibrium
constant.
The equilibrium constant is a quantitative characteristic of a given equilibrium system. With its help it is possible to
calculate the changes in the equilibrium state, which occur after a change of some external factors - temperature,
concentration, pressure and others. The equilibrium constant depends on the nature of the reactants, the nature of the
solvent if in solution, and the temperature.
When the reversible reaction goes in gaseous state, it is more convenient to use pressure instead of concentration in the above
equation, since the pressure is easily measured for gases.
The equilibrium constant does not depend on the concentrations of the substances involved, the pressure or the
presence of catalysts.
3.3.4. Equilibrium constant in homogeneous, heterogeneous and sequential reactions
In homogeneous reactions (all components are in one phase - solution or gas mixture), the expression includes the
concentrations or pressures of all components of the equilibrium system, for example:
When components of the equilibrium system form two or more phases, the ongoing reactions are in a heterogeneous
phase. Since the concentration of condensed phases (liquids and solids) does not change (their quantity can change), their
value is constant. For this reason, these concentrations are included in the value of the equilibrium constant, but do
not appear in the expression for it, defined by the MAL. Several such examples are given below:

Let's consider the reaction: which is characterized by an equilibrium constant Keq:

and proceeds in two stages, each of which is characterized by

the corresponding equilibrium constant:

If we express the concentration of [D] from the Comparing this expression

second equation as a function of [E] and K2 and with the expression for Keq, K1.K2 = Keq
replace it in the expression for K1, and after an we get:
elementary transformation, we obtain:
The total equilibrium constant of the process is the product of the equilibrium constants of the two stages. It can be
generalized for sequential reactions the total equilibrium constant of the process is a product of the equilibrium
constants at all stages:
K1.K2.....Кn = Keq
The following reaction can be given as an example:

3.3.5. Free energy and chemical equilibrium

There is the following relationship between the equilibrium constant and the change in the standard Gibbs free energy for a
chemical reaction: ∆G - change in the standard free energy of the reaction. It is customary to
∆G = - R.T.lnK
give in tabular form the change in the standard free energy ∆Gо of the
reaction:
∆Gо = - R.T.lnKeq
∆Gо - change of the standard free energy of the reaction (temperature 298 оК, pressure 101 kPa (1 atm = 101 kPa),
concentrations of the substances are 1 mol/L or activity is 1, the standard рН = 0 (for biochemical reactions the standard рН =
7); T – absolute temperature [оК], R – universal gas constant {8,314 [J/(mol.K]} and Кeq is the equilibrium constant under
standard conditions.
By experimentally determining the equilibrium constant of a chemical reaction under standard conditions or other conditions,
the change in the standard free energy of that reaction can be calculated. The large negative values of ∆G o correspond to the
large values of Keq, i.e. in an equilibrium mixture the products predominate. At large positive values of ∆G о, Keq << 1 and the
starting substances predominate in the equilibrium mixture. Кeq ΔG0 [kJ] Кeq ΔG0 [kJ]
1.105 -28.5 0.1 5.7
3.3.6. Criteria for determining the direction of spontaneous processes 1.104 -22.8 0.01 11.4
Two important principles are known about chemical processes occurring in nature: 1.103 -17.1 1.10-3 17.1
1. Tendency of the system to move into a state with the lowest possible energy, 100 -11.4 1.10-4 22.8
characterized by a change in enthalpy; 10 -5.7 1.10-5 28.5
2. Tendency of the system to achieve the most probable state, which is characterized 1 0
by the maximum number of independent particles, which is determined by the change
in temperature and entropy.
If the process takes place under isobaric-isothermal conditions, the Free Energy Change (ΔG), which is a function of the
above-mentioned parameters of the system, is the criterion for predicting the spontaneity and direction of chemical processes.
If ∆G<0, the process can occur spontaneously and it is called an exergonic process;
If ∆G>0, the process cannot proceed spontaneously and it is called an endergonic process;
If ∆G = 0 - an anergonic process.
It is very important to note that if the process is exergonic, it does not mean that the reaction proceeds to the end. Thus, the
hydrolysis of proteins to amino acids in the digestive system of mammals and humans is exergonic, but occurs in a yield of
99.9%, but not 100%. Accordingly, endergonic reactions can be said to occur to some extent. At very large absolute values of
∆G, the reactions become irreversible.
3.4. Influence of external factors on the processes in an equilibrium system
3.4.1. Vant Hoff reaction isotherm
Let’s consider the reversible reaction:
If the system is not in equilibrium yet and at a certain moment a sample of the reaction
mixture is taken and the concentrations of the components are determined, we can express the
instantaneous (pseudo) equilibrium constant by means of MAL Кapp (app from apparent):
If the system is left for a sufficient time under standard conditions, an
equilibrium will occur, which is characterized by an equilibrium constant ∆Greaction = ∆Gproducts - ∆Greagents = ∆G° - ∆Gapp
Keq. The change in free energy of the reaction will be:
Using the relationship between the change in free energy ∆Greaction = ∆G° + R.T.lnK
and the equilibrium constant, we obtain:
∆G - change of the free energy of the reaction; ∆Gо - change in the standard free energy of the reaction; [A], [B], [C] and [D]
- the instantaneous concentrations of the components [mol/L]. Depending on the values of ∆G° and ∆Gapp, the difference ∆G
can be negative or positive. Depending on this, it is possible to predict in which direction and to what extent the reaction will
proceed until equilibrium is reached.
3.4.2. Influence of external factors on the processes in an equilibrium system
The state of chemical equilibrium is maintained under the same conditions indefinitely. When conditions change the
forward and the reverse reaction are influenced differently and the system goes out of equilibrium. Processes take place in
the system that lead to the restoration of equilibrium or the establishment of a new one
 3.4.3. Le Chatelier-Brown principle
If an external influence is exerted on an equilibrium system, then changes occur in it and processes are carried out
that lead to a reduction of the effect of the external influence – i.e. such reactions occur spontaneously in the system as to
compensate for the external influence.
3.4.4. Influence of temperature on chemical equilibrium
To assess the effect of temperature on chemical equilibrium, it is necessary to know the thermal effect (change in enthalpy) of
the reaction. Increasing the temperature will favor the process leading to a decrease of the temperature of the system. This is
the reaction that is associated with heat absorption, i.e. the endothermic reaction for which ∆H>0. On the contrary, lowering
the temperature will favor the reaction in which heat is released, i.e. the exothermic reaction for which ∆H<0. Some
examples are given below:

The change in temperature, unlike other external influences discussed below, affects the value of the equilibrium constant.
The equilibrium at the new temperature is characterized by a different equilibrium constant. Another equilibrium is
realized.
3.4.5. Influence of concentration on the direction of the chemical reaction in an equilibrium system
Esterification is a reversible process. As an example, lets consider the reaction between acetic acid and ethanol, which results
in the formation of ethyl acetate and water:

Under certain conditions, it is characterized by the

equilibrium constant:
If acetic acid is added to the system (at constant temperature), then according to LMA, the rate of the forward reaction (vf =
kf.[CH3COOH].[C2H5OH]) increases and the system goes out of equilibrium. This treatment favors the forward reaction.
Over time, the concentration of the reagents decreases and at a moment the two reaction rates equalize again. The balance is
restored. Although the concentrations of the components are different from the baseline, the equilibrium constant retains its
value. Equilibrium is preserved because it is characterized by the same equilibrium constant.
If in the system in its initial equilibrium state, a dryer is introduced to connect part of the water, then its concentration will
decrease. According to the MAL, the rate of the reverse reaction (hydrolysis reaction; v r = kr.[CH3COOC2H5].[H2O])
decreases and the system goes out of equilibrium. After some time, the balance is restored. In cases where, for example, the
concentration of acetic acid is reduced or the concentration of water is increased, the course of the reverse reaction will be
favored, i.e. hydrolysis will occur.
Introduction of an additional amount of any of the reactants into the equilibrium system accelerates the reaction in which it is
consumed.
We can summarize the effect of concentrations on the direction of the chemical reaction, as follows:
Influence Effect
Increasing concentration of a reagent Forward reaction is favored
Increasing concentration of a product Reverse reaction is favored
Decreasing concentration of a reagent Reverse reaction is favored
Decreasing concentration of a product Forward reaction is favored акция
3.4.6. Influence of pressure on the direction of the chemical reaction in an equilibrium system
Similar considerations can be made when the reaction happens in a gas phase (in a gas mixture) or in a heterogeneous
medium where at least one of the components is a gas. Given the fact that at constant temperature the pressure p is
proportional to the molar concentration (p = R.T.CM), we can draw the same conclusions as for the effect of concentration.
The molar concentration is equal to the number of moles (n) per unit volume (V), so the equation can be written in the form:
This means that if the volume is constant, the pressure will increase in direct proportion to the number of
p.V = R.T.n moles of the gas and, respectively, at constant pressure with increasing number of moles of gas, the
volume will increase in direct proportion.
When gas(s) participate in a chemical reaction, there is one peculiarity concerning the influence of pressure. The reaction of
synthesis (1) of ammonia from nitrogen and hydrogen is characterized by an equilibrium constant:
If we increase the total pressure, according to the principle of mobile equilibrium, then a process will take place in the system
to oppose this external influence, i.e. there will be a reaction associated with a reduction in the volume (respectively pressure
reduction) of the system. This in the above case is the right reaction, i.e. the formation of ammonia. The pressure of each gas
(gas partial pressure) in a gas mixture is proportional to the number of moles of that gas in the mixture. According to reaction
equation (1), the number of moles of reagents in total is 4 (respectively 4 relative volumes) and of products is 2 (respectively
2 relative volumes), the process leading to pressure reduction (in a closed system this means the volume) will be the
formation of ammonia, i.e. the forward reaction will be favored. A corresponding reduction in pressure will favor the reverse
reaction.
According to the principle of mobile equilibrium, if the pressure increases, the equilibrium system must counteract
this external influence by spontaneously reducing its own volume.
The reaction of synthesis (2) of hydrogen iodide from iodine and hydrogen is
characterized by an equilibrium constant:
According to the reaction equation (2), the number of moles of reagents in total is 2 (respectively 2 relative volumes) and of
products is also 2 (respectively 2 relative volumes). In this case there are no changes in the number of moles, respectively the
volume and pressure will not affect the system. In this case, the increase in pressure (this means an increase in
concentrations) will only accelerate the achievement of equilibrium.
The pressure affects the equilibrium only in those cases when the reversible reaction takes place with a change in the
total volume of the system, i.e. with a change in the total number of moles of starting materials compared to that of
the products.
The latter also applies to heterogeneous systems involving gas(s). For example, for the decomposition reaction (3) of
calcium carbonate to calcium oxide and carbon dioxide, it is characterized by an equilibrium constant:

In this case, the number of moles of reagents in the gaseous state is 0 in total, and of the products is 1. In the case of the
forward reaction, an increase in volume will be observed, while in the case of the reverse reaction - a decrease in volume.
Decreasing the pressure will favor the forward reaction, and increasing the pressure will favor the reverse reaction.
Based on the above, we can summarize the three reactions considered:
 Influence Reaction Effect

Increasing pressure 1 Forward reaction is favored

2 No effect
3 Reverse reaction is favored
Decreasing pressure 1 Reverse reaction is favored
2 No effect
3 Forward reaction is favored

3.4.6. Conjugation (coupled) reactions in biochemistry

Coupled reactions are those in which one reaction promotes the course of the other. In these processes, the substance(s)
obtained from one reaction serve as the reagent(s) for the next reaction. These are successive reactions.
Biochemical processes take place in very limited temperature ranges and therefore it is impossible to change the direction of
a chemical reaction by changing the temperature, especially in warm-blooded organisms where the temperature is maintained
in a very narrow range.
Thermodynamic analysis shows that in living nature the processes of biosynthesis of biopolymers, as well as a number of
other substances are impossible without the introduction of energy from outside. Therefore, the maintenance of organisms is
done through the consumption of external energy. Living organisms are open systems that exchange energy and substances
with the environment. In biochemical terms, the realization of processes that require energy (endergonic reactions, ΔG > 0) is
done by combining them with other reactions in which energy is released (exergonic reactions ΔG < 0).
As shown in Section 3.3., The total equilibrium constant of a process that consists of successive reactions, is the product of
the equilibrium constants of all stages. Given the mathematical relationship between the equilibrium constant and the change
in free energy, we can write:
DG = DG1 + DG2 + ... + DGn
For conjugation reactions, the change in the total free energy of the process is generally the sum of the changes in the free
energy of all stages. For the process to proceed as a whole, the sum of ΔGi must be less than zero, i.e. the reaction is
generally exergonic. The way to realize the reaction as a whole in this case is not important. In biochemical thermodynamics,
there is often a misconception that in conjugation reactions, the exergonic process must proceed first and then the endergonic
process. It is based on thermodynamic formalism, without taking into account the microscopic characteristics of the system.
If ΔG> 0, this does not mean that the reaction will not proceed at all.
Let us consider two successive reactions, the first of which is endergonic:
From the table on slide 6 it is seen that К1 is 0.01, which means that В is
0.1% (molar) in the system. Substance B participates in the second reaction
as a reagent. According to the principle of Le Chatelier - Brown, the system
will react to compensate for the decrease in the concentration of B. This
means that a certain amount of A will be transformed into products (B and
C). This will favor the reaction as a whole: DG = -5.7 kJ and respectively К
= 10. In this way, metabolic pathways are formed by combining
enzymatically catalyzed reactions so that the total free energy of the pathway
is negative.
3.4.7. Compounds with "macroergic" bonds
Compounds with the so-called "macroergic" bonds are used as energy carriers. This notion is misleading because the bonds
in these compounds are not of high energy (in which case, they would be relatively chemically inert). Their hydrolysis
releases a significant amount of energy. Macroergic or energy-rich are those bonds which hydrolysis releases a significant
amount of energy - from 30 to 70 kJ/mol. The pH of the medium is essential, as for biochemical processes, the standard pH is
7. For example, the hydrolysis of ATP:

or of creatine phosphate:
These compounds can react not only with water but also with alcohols, phenols and amines, releasing a significant amount of
energy. For this reason, it is more accurate to speak not of energy-rich "macroergic bonds" but of "high potential of groups
transfer", a term recommended for use.

Endergonic processes in organisms occur at the expense of energy released during exergonic processes and stored in
macroergic bonds. The coupling between exergonic and endergonic processes takes place through "macroergic"
compounds.
 4.1. Protolysis processes
Despite the fact that terms "acid" and "base" are widely used in chemistry, there is no single approach to classifying
substances as acids or bases. There are currently three main theories.

4.1.1. Classical theory of Arrhenius

Acids are electrolytes that dissociate in aqueous solution into
only one type of cations - hydrogen H + ions and acid anions.
Bases are electrolytes, which in aqueous solution dissociate
into metal cations and a type of anions - hydroxide anions HO-.
Ampholytes are electrolytes that dissociate in solution
to form both H+ ions and HO- ions.
Salts are substances obtained during the neutralization of an acid
with a base and in aqueous solution do not give H+ and HO- ions
and in the solid state form an ionic crystal lattice.
Neutralization is a process in which an acid and a base react in water,
resulting in the formation of salt and water. In general, this interaction is
reduced to a reaction between hydrogen cations and hydroxide anions,
leading to the formation of water:
Arrhenius theory is very limited and cannot explain a number of phenomena, incl. in non-aqueous solutions.
4.1.2. Broensted and Lowry theory of acids and bases
Acid is a compound (molecule or ion) that donates a proton (proton donor) and
becomes a base, which is called the conjugate base of the acid.
Base is a compound (molecule or ion) that accepts a proton (proton acceptor) and is
converted to an acid, which is called the conjugate acid of the base.
The acid and the base are in an interdependent equilibrium and form the so-called
coupled (conjugate) system. From the acid its conjugate base is formed, and from
the base - its conjugate acid.
The equilibria between acids and their conjugate bases are called acid-base half-reactions. A real acid-base interaction can
take place only in the simultaneous presence of two systems, of two acid-base pairs. The real acid-base process is called
protolysis or protolysis equilibrium:

The interaction between acid and base does not lead to mutual
neutralization, but to the formation of a new acid and base.

Examples of acids (a) and bases (b) are given below:

a) b)

Ampholites are substances that can exhibit both acid and

base properties. For example, water acts as an amphoteric
compound (ampholyte):
Another example of an ampholyte is the bicarbonate ion:
The protolytic theory considers the terms "acid" and "base" not as a property but as a function that the compound in question
performs in a protolytic reaction. The same compound may react as an acid under some conditions and as a base under
others. Thus, in aqueous solution, CH3COOH exhibits the properties of an acid, and in H 2SO4 – as a base.

A significant difference between the theory of Broensted and Lowry from that of Arrhenius is that acid-base reactions can
take place in non-aqueous solutions. In some of them ions with opposite charges can be formed - lyonium (positively
charged) and lyate (negatively charged) ions. These solvents include alcohols, carboxylic acids, ammonia, amines and other
classes of compounds.
 Solvent Lyonium ion Lyate
CH3OH CH3OH2+ CH3O-
CH3COOH CH3COOH2+ CH3COO-
NH3 NH4+ NH2-
CH3NH2 CH3NH3+ CH3NH-

In order for a solvent to act as a base, it must have a certain affinity for the proton (to have basic properties), and in order to
act as an acid - in its molecule a hydrogen atom should exist that is capable of being released as a proton. The solvents shown
as examples in the table meet these requirements. They are called proton solvents. Solvents that do not meet the
requirements cannot participate in acid-base processes and they are inert in this respect. Such are hydrocarbons, their
halogenated derivatives and some other groups of substances. Although these solvents are inert to protolythic reactions,
protolysis processes between an acid pair and a base can be performed in them.
Acid-base reaction is essentially the interaction of two competing bases with a proton.
However, despite its advantages, the protolytic theory, like Arrhenius's theory, is not applicable to substances that do not
contain hydrogen atoms, but at the same time exhibit acidic properties in some processes. Such are some compounds of
boron, aluminum, silicon and others.
4.1.3. Strength of the protolytes. Protolysis constants (pKa and pKb)
Like any reversible process, electrolytic dissociation reaches equilibrium between two opposing processes, and this
equilibrium is dynamic. For the reaction below, an equilibrium constant can be introduced, called in this case a protolysis
constant (dissociation constant), which is a quantitative characteristic of the process. The relative strength of acids can be
determined by measuring their equilibrium constants in solution, for example in aqueous. For the acid reaction:
the equilibrium constant is:

Although water is a reagent, it is also the solvent, so its concentration for relatively dilute
acid solutions is a constant value and therefore we include [H 2O] in the value of the
constant:
The equilibrium constant Ka for a given acid is called the acid dissociation constant. It determines the strength of the acids.
In solutions of the same concentration, the stronger acids dissociate to a greater extent than the weaker acids. In water
solvent, stronger acids give a higher concentration of hydronium (oxonium) ions (H 3O+). The values of Ka are very small and
it is preferable to use pKa, which is a negative decimal logarithm of Ka : 𝑝𝐾𝑎 = −𝑙𝑔𝐾𝑎
Acids that can donate two or more protons (polyprotic acids)
dissociate in stages. For example, sulfuric acid dissociates
step-wisely:

The table shows the pKa values of some inorganic and organic acids (stronger acids have a lower pK a value):
Acid pKa,1 pKa,2 pKa,3 Acid pKa,1 pKa,2
HClO4 -10.0 CF3COOH 0.2
HCl -7.0 HOOC-COOH 1.2 4.2
H2SO4 -3.0 1.9 HCOOH 3.7
HNO3 -1.6 C6H5COOH 4.2
H3PO4 2.1 7.2 12.4 CH3COOH 4.7
H2S 7.0 12.6 C6H5OH 10.0
Stronger acids form weaker conjugate bases, and weaker acids form stronger conjugate bases. Strong acids are
practically completely ionized in aqueous solution because their conjugate bases are weaker than water. Weak acids are only
partially ionized, as their conjugate bases compete successfully with water for proton possession.
The relative strength of bases can be determined by measuring their equilibrium constants in solution, for example in
aqueous solution. For the base reaction:
the equilibrium constant is called the basic dissociation constant Kb:
This constant determines the strength of the bases. In this case it is accepted to use pK : 𝑝𝐾𝑏 = −𝑙𝑔𝐾𝑏
b
Stronger bases have a lower pKb value. Stronger bases form weaker conjugate acids, and weaker bases form stronger
conjugate acids. In the chemical literature, it is not the pKb of the bases that is used, but the pKa of their conjugate acids. The
higher the pKa of the conjugate acid, the stronger the base and vice versa. The table shows the pK a values of the conjugate
acids of some inorganic and organic bases:
Base pKa Base pKa
NH3 9.2 NH2OH 6.0
CH3NH2 10.6 NH2NH2 8.1
C6H5NH2 4.6 PO43- 12.3
C6H5CH2NH2 9.4 SO32- 7.0
(C2H5)2NH 11.0 S2- 12.9
 For an acid and its conjugate base, according to the reactions:

and using the expressions for pKa and pKb, it can be shown
that the product of the two constants in the same solvent, for
example water, is a constant at constant temperature:
This equation proves the statement that the stronger the acid, the weaker the conjugate base and vice versa.
The strength of an acid or a base cannot be determined independently, but must be compared with another acid-base
pair, such as water.
4.1.4. Factors on which the strength of protolytes depends
The strength of protolytes depends on the nature of the substances (intramolecular factors), the nature of the solvent and to a
lesser extent on the temperature (external factors).
A) Intramolecular factors:
● The polarity of the H-X bond in the structure of the acid: it depends on the electro-negativity of X, which in turn depends
on its nature and on the oxidation state of X; the polarity of the bond also depends on the electronic effects in the acid
structure;
● The dissociation energy of the H-X bond in the acid structure;
● Electronic effects in the conjugate acid or base: if the conjugate acid or base is an ion, the more delocalized the charge, the
more stable the ion, which leads to an increase in the strength of the acid or base;
● Intramolecular hydrogen bonds: their formation stabilizes the ionic form, especially if it is an anion, and this leads to an
increase in the strength of the acid or base.
B) External factors:
● The solvation energy of a conjugate base or acid: if the conjugate base or acid is an ion, their solvation energy is much
higher than that of neutral molecules and, accordingly, the higher the solvation energy of these ions, the stronger the base or
acid;
● Temperature: For most acids, as the temperature increases, Ka rises slightly, reaches a maximum value, and then begins to
decrease.
To compare the strength of acids or bases, data should be used for the same solvent at the same temperature. On the other
hand, the effect of the solvent can also be studied for different classes of compounds.
The pKa values ​of the oxoacids of chlorine, sulfur and phosphorus, in which these elements are in the maximum degree of
oxidation were presented on the previous slide. Chlorine is the most electronegative element of the three and perchloric acid
is the strongest of the three acids. On the other hand, phosphorus has the lowest electronegativity of the three elements and,
accordingly, phosphoric acid is the weakest of the three. In these cases, the higher the electronegativity of the element X, the
more polar the O-H bond. Also, in the anion, the negative charge is distributed not only on the oxygen atoms but also on the
central atom (the X-O bond is less polar in the anion than in the molecule of the corresponding acid, i.e. the positive charge
of the central atom in the anion is less than in the acid). This leads to a stabilization of the anion, which in this case is greatest
in the perchlorate (ClO4-) ion. Both factors discussed act in concert in this case, but this also applies in principle.
As an example of the influence of the electronic effects of substituents in the molecule, we will consider acetic acid and its
chloro-substituted derivatives. The pKa values ​of these compounds are given in the table, as well as the energies (ΔE aq) of
solvation of the anions (conjugate bases) in water.
Acid CH3COOH ClCH2COOH Cl2CHCOOH Cl3CCOOH
pKa 4.7 2.9 1.5 0.7
ΔEaq (RCOO-) [kJ/mol] -343.5 -335.6 -328.2 -324.6

Replacement of a hydrogen atom in the acetic acid molecule with an electronegative atom (possibly an atomic group), in this
case chlorine (with an -I-effect), leads to a redistribution of the electron density in the molecule and its conjugate base (anion).
In chloroacetic acid, chlorine leads to further polarization of the O-H bond compared to acetic acid and stabilization of the
chloroacetic ion relative to the acetic ion, respectively. As in the previous example, these effects act in concert, i.e. increase
the strength of the acid.

Increasing the number of chlorine atoms enhances these effects and, accordingly, the strength of acids. The energy of
solvation decreases linearly during the transition from acetic acid to trichloroacetic acid. This effect acts in contrast to the two
effects discussed above. The fact that trichloroacetic acid is 4 orders of magnitude stronger than acetic acid shows that the
electronic effect of the substituent(s) is decisive for the strength of the acids, and solvation is a secondary factor.
We can summarize that electron aceptor substituents (negative induction and/or mesomeric effect) increase the
strength of the acid, and electron donors (positive induction and/or mesomeric effect) decrease it. For bases, the effects
are reversed - electron donor substituents increase basicity and electron-acceptor substituents decrease it.
The strength of acids is explained by the polarity of the X-H bond and, accordingly, the stabilization of the anion. These two
factors are not always decisive. A classic example is the power of hydrogen halides. The table below gives data on their pK a
values ​in water, as well as other data on various factors influencing the strength of acids.
НХ HF HCl HBr HI These data show that the strength of the acids increases in the order HF <
pKa 3.2 -7.0 -9.0 -10.0 HCl < HBr < HI. Conversely, the degree of ionicity (polarity) of the H-X
Degree of ionicity 41 18 12 6 bond decreases with the transition from HF to HI, in accordance with the
(%) electronegativity of the halogens. The solvation energy of the anion
ΔEaq (X-) [kJ/mol] -524 -378 -348 -308 (conjugate base) also decreases in this order. Obviously, another factor
ΔEdis H-X [kJ/mol] 570 431 366 298 determines the order of acidity of hydrogen halides.
The data in the table show that the hydrogen-fluorine bond is significantly stronger than that of the other compounds and is
difficult to break. The weaker the bond, the stronger the acid, because it is easier to brake it. This is illustrated in the table
where it is seen that the weakest H-X bond is in the strongest acid. Looking vertically downwards at the halogen group from
F to I, the charge of the anion becomes more diffuse, i.e. the negative charge is distributed over a significantly larger volume,
which makes the conjugate base (anion) more stable and less electrostatic attraction between the X and proton.
The situation is similar with the hydrogen compounds of the elements of Н2Y H2O H2S H2Se H2Te
the oxygen group (H2Y). Thus, water is the weakest acid, although the H-
O bond is 33% ionic, while hydrogen telluride is the strongest acid and pKa 15.7 7.0 3.9 2.4
the H-Te bond is the least polar.
The presence of a hydrogen bond between a group determining the acidic properties and another substituent in the structure
of the molecule can significantly change its strength. The hydroxyl group as a substituent in the aromatic compounds has the
-I effect and the +M effect, the latter being stronger. In general, the HO group is an electron donor substituent. Based on the
effects of the substituents discussed above, it should be expected that 4-hydroxy- and 2-hydroxybenzoic acids are weaker
than benzoic acids. The data in the table show that this is true for 4-hydroxybenzoic acid, but 2-hydroxybenzoic (salicylic)
acid is more than an order of magnitude stronger than benzoic acid.
Acid C6H5COOH 4-HO-C6H4-COOH 2-HO-C6H4-COOH
pKa 4.2 4.6 3.0
The reason for this irregularity is the presence of an intramolecular hydrogen bond between the HO group and the COOH
group in its molecule. Its formation leads to an increase in the polarization of the OH bond in the carboxyl group. Much more
significant is the fact that there is an intramolecular hydrogen bond between the HO group and the carboxylate anion. This
leads to a significant stabilization of the anion due to the delocalization of the charge and the hydrogen bond in the anion has
a significantly higher energy than that in the neutral molecule.

The strength of acids and bases depends on the nature of the solvent. Apart from the acid-base properties of the solvent (when
it is protic), the polarity of the solvent (its dielectric constant) is important and the specific solvation that is realized (for
example the formation of hydrogen bonds) is especially important. When ions are formed as a result of the protolytic process,
the strength of the acid increases as the dielectric constant of the solvent increases.
The table shows the pKa values ​of some acids and of the conjugate acids of some bases in water (dielectric constant ε = 78.5),
methanol (ε = 36) and dimethyl sulfoxide (ε = 46.4). In the transition from water to methanol, the strength of the acids
weakens. Both solvents are proton, but methanol has a lower polarity. The same is observed in the transition from water to
dimethyl sulfoxide, in which case the fact that dimethyl sulfoxide is an aprotic solvent is also important. On the other hand,
in dimethyl sulfoxide (DMSO) the strength of acids is lower than in methanol, despite the greater polarity of DMSO. This
shows the importance of hydrogen bonds formation in methanol with the conjugate bases of acids.
Acid H2O (CH3)2SO Base H2O CH3OH (CH3)2SO In the case of ammonia and amines, the
CH3OH effect of the solvent is weak. In this
case the process takes place:
pKa pKa
HBr -9.0 1.0 0.9 (CH3CH2)2NH 11.1 11.3 12.2
HCl -7.0 1.2 2.0 CH3CH2NH2 10.9 11.0 10.5 The conjugate acid is positively
C6H5COOH 4.2 9.3 11.0 NH3 9.2 10.0 10.5 charged and the reaction also results
CH3COOH 4.7 9.6 12.6 C6H5NH2 4.6 6.0 3.8 in a positively charged particle. In this
C6H5OH 10.0 14.3 18.0 case, the polarity and the specific
solvation in the solvent have little
effect.
 4.1.5. Lewis's theory of acids and bases
Lewis acids are molecules or ions that have unoccupied (vacant) electron orbitals capable of accepting electron pairs
(electron pair acceptors).
Those are for example hydrogen cations Н+, a number of metal ions (Ag+, Cu2+, Zn2+, Fe3+, Al3+, etc.), non-metal oxides
(SO3, P2O5, SiO2 , etc.) an other compounds of non-metals (BF3, SiCl4, PF5, SbF5, etc.). Protic acids are considered a special
case of the acid class.
Lewis bases are molecules or ions that can donate electron pairs (electron pair donors).
These are, for example, almost all anions, water, alcohols, ammonia, amines and many other compounds.
Examples of chemical reactions between Lewis acids and bases: Schematically, these interactions can be
illustrated by the example of the formation of
Lewis acid + Lewis base → Product
tetrafluoroborate ion (BF4-) from boron
trifluoride and fluoride ion:

The product of such an interaction can be considered as a salt or a coordination (complex) compound. In this sense, these
reactions are not neutralization, but complex-forming processes. Lewis's ideas are the most general, because in this theory the
acid-base properties are associated with a certain electronic structure, and not with reference to certain chemical classes of
compounds. For this reason, the number of Lewis acids and bases is much higher than that of Broensted and Lowry.
In essence, this theory shows that acids are actually electrophiles, and bases are nucleophiles.
4.2. Autoprotolysis
Autoprotolysis: An equilibrium chemical reaction in which two molecules of an amphiprotic solvent interact
by exchanging a proton.
If we have a solvent with the general formula SH, we can express the
autoprotolysis as:
As a result, lyonium (SH2+) and liate (S-) ions of the solvent are formed. For this
equilibrium we can write the expression for the equilibrium constant:

In general, the concentrations of ions formed as a result of autoprotolysis are much

lower than the concentration of the solvent in molecular (neutral) form. For this
reason, we can include [SH]2 in the value of the constant:

This expression is the so-called ionic product (product of ion concentrations) of

𝑝𝐾𝑠 = −𝑙𝑔𝐾𝑠
the solvent. Since the values of KS are generally very small, it is preferable to
use pKS, which is a negative decimal logarithm of KS:
4.2.1. Ionic product of water
The autoprotolysis of water and the ionic product of
proceeds by the reaction: water (Kw) is:
It is the product of concentration of H3О+ and НO-. This value is constant only at a given temperature. Thus, at 25°С, [H3O+]
= [HO-] = 1.10-7 mol/L and Kw = 1.10-14 mol2/L2, and рKs ≡ рKw = 14.

The presence of ions in pure water is proved by measuring its electrical conductivity. Using the relationship between
electrical conductivity and the degree of electrolyte dissociation, it is easy to determine the amount of dissociated water
molecules. Since the value of Kw is constant in pure water, the concentrations of oxonium and hydroxide ions are
interdependent.

Many solvents, in addition to water, are involved in the process of autoproteolysis. The table below gives some examples:
 Solvent/Reaction pKs
16.9
19.5
6.2
14.5
17.3
5.0

(for liquid ammonia) 32.5

4.2.2. Hydrogen ion indicator (hydrogen ion exponent)

If an acid dissolves in water, the concentration of hydrogen ions increases and according to the principle of Le Chatelier-
Brown the reaction is drawn to form whole molecules. Some of the hydrogen ions bind to the hydroxide ions and cause a
decrease in their concentration. Equilibrium is established in the solution when the concentration of hydroxide ions reaches
such a value that their product with the concentration of oxonium (hydrogen) ions is equal to the ionic product of water at this
temperature. In an acid solution, the concentration of hydrogen ions is higher than the concentration of hydroxide ions. When
the base is dissolved in water, the reaction is also carried out to form whole water molecules, the concentration of hydrogen
ions being less than the concentration of hydroxide ions. The ionic product of water shows that in an aqueous solution,
regardless of what the solute is (acid, base or salt), the product of the concentration of hydrogen and hydroxide ions remains
constant (at 25°C - 10-14).
In order to quantify the acidity and alkalinity of a solution, the term hydrogen index or
hydrogen exponent has been introduced. The hydrogen index is defined as the negative pH = -lg[H+] = -lg[H3O+]
decimal logarithm of the concentration of hydrogen (oxonium) ions in the solution:
In pure water, the concentration of oxonium (hydrogen) ions at 25°C is 10-7 mol/dm3 (mol/L). The negative decimal
logarithm, pH = 7. Thus, increasing the concentration of H+ (H3O+) ions decreases the pH, and decreasing the concentration
of H+(H3O+) ions increases the pH. When comparing the pH values of different solutions, these values should be related to
the same temperature.
It is convenient to express the nature of the medium using the pH value:
 • neutral medium: pH = 7 (at 25°C);
• acidic medium: pH<7;
• alkaline medium pH>7.

If the expression KW  [Н3О+][НО] is taken a logarithm

-lgKW  - lg[Н3О+] - lg[НО] → pKw = pH + pOH
and multiplied by -1, then we obtain:
Since at 25°С: pKw = 14, then pH = pOH = 7.

It is important to note that pH can also be defined in non-aqueous solvents: pH = -lg[H+] = -lg[SolvH+]

So, pH value of the solvent is the negative decimal logarithm of the concentration of lyonium ions. The table on previous
slide shows that the pH scale in some solvents is narrow, for example formic acid, in others it is medium (acetic acid,
methanol), while in liquid ammonia it is wide.
4.2.3. Temperature dependence of the ionic product of water
Neutralization is an exothermic process, which means that the reverse reaction, the autoprotolysis of water is an endothermic
reaction (ΔH = 57.3 kJ/mol). Raising the temperature will favor dissociation. This is illustrated by the data in the table
Temperature (ºС) 0 15 25 35 50 70 100
pKw 14.94 14.34 14.00 13.68 13.26 12.80 12.26
pH neutral 7.47 7.17 7.00 6.84 6.63 6.40 6.13
From the data it becomes clear that with the transition from 0ºС to 100ºС, the degree of dissociation of water increases
almost 500 times. In addition, the neutral pH varies from 7.47 to 6.13. It should be noted that when talking about an acidic or
alkaline environment, temperature must also be taken into account.
4.2.4. Significance of pH of biological fluids

The concentration of H+ (i.e. pH) is one of the essential constants in the body. Examples of normal intervals in which the pH
varies in different fluids in the human body are given in the table below.
 pH (in pH (in
Biological fluid Biological fluid
norm) norm)
Gastric digestion fluid 0.9  1.2 Erytrocytes 7.25
Urine 4.8  7.5 Blood plasma 7.40  0.05
Bile in the gallbladder 5.4  6.9 Spinal fluid 7.40  0.05
Saliva 6.35  6.85 Inntestinal fluid 7.0  8.0
Skin 6.2 – 7.5 Pancreatic juce 7.5  8.5

The increase in the concentration of hydrogen ions (decrease in pH) leads to an increase in acidity (acidosis), which can
occur as a result of impaired excretion (excretion) of acid, loss of significant amounts of bases from the body, in the presence
of high concentrations of CO2 in the inhaled air, in case of diarrhea, vomiting of intestinal contents and other causes. An
increase in pH (alkalosis) can develop as a result of the loss of acid anions or the retention of alkaline cations, intestinal
obstruction, impaired excretion of sodium by the kidneys, when significant amounts of alkaline substances enter the body
with food or drugs, poisoning and for other reasons. Both forms of acid-base imbalance in the human body are harmful to the
body and can cause serious damage. For example, if the pH of the blood plasma is below 6.8 or above 7.8, hemoglobin
denaturation occurs, which leads to a reduction in the supply of oxygen to the cells and ultimately leads to death.
4.2.5. Methods for determining pH
Indicators are used for approximate determination of pH, which are widely used in the acid-base volumetric quantitative
analysis.
Indicators - complex organic acids or bases that have different colors depending on the concentration of hydrogen ions, i.e.
at different pH.
These substances, also known
as pH indicators, are weak or bases: or ampholytes:
acids:

The neutral form and the ionic forms of the indicators have different colors due to the different distribution of the electron
density in the respective particle. The transition from one form to another takes place smoothly, in a certain pH range in
which both forms of the indicator exist. The table below shows some of the most used indicators, their pK a, conversion
interval and color transitions.
 Indicator рКа рН-interval of transition Color change
thymol blue 1.5 1.2 - 2.8 red-yellow
8.9 8.0 - 9.6 yellow-blue
methyl orange 3.7 3.2 - 4.5 red - orange
bromophenol 4.0 3.0 – 4.6 yellow - blue
blue
methylroth 5.1 4.4 - 6.2 red-yellow
litmus 5.0 - 8.0 red - blue
bromothymolbl 7.0 6.0 – 7.6 yellow - blue
au
phenolphthalei 9.4 8.7 - 10.0 colorless - red
n
thymolphthalei 9.6 9.4 - 10.6 colorless - blue
n
As an example, let’s consider the bromophenol blue indicator:
At pH <3 the color of the solution is yellow. If we
add a base and the pH rises to 3, there is a sufficient
concentration of the conjugated base in the medium,
which is blue. As the overlap of yellow and blue
forms a green color, the solvent turns yellow-green.
As the pH increases, the concentration of the blue
form increases and the color of the solution turns
green. Upon further addition of base, the conjugate
base begins to predominate, the color becomes blue-
green and above 4.6 becomes blue.
A pH-meter is used to accurately measure pH, and the measuring element is a glass electrode that is selective for hydrogen
cations and changes its potential depending on the concentration of hydrogen cations (oxonium ions in water). The potential
of any electrode cannot be measured, but the potential difference between two electrodes can be measured, one of which has
a constant potential, called a reference electrode. One such electrode that is widely used as a reference electrode is the
silver/silver chloride electrode. As AgCl is slightly soluble in water, a concentrated aqueous solution of KCl is used to form
complex ions [AgCl2]-, which increases the solubility of AgCl. This electrode has a very stable potential and is weakly
temperature dependent. When the glass electrode is immersed in a solution of some pH, its potential changes, as the pH-
meter reads the potential difference between it and the reference electrode and this difference is read as pH. There are also so-
called combined electrodes in which the two electrodes - measuring (in this case glass) and reference electrode are built in
one body. Reference Glass
electrode electrode

4.2.6. Biological significance of pH

Acid-base processes play an important role in the human body. Thus, the rate of enzymatic reactions in the human body
depends on the pH of the medium. Each enzyme has a specific pH, which is optimal for its action. The acidity of the medium
is important to maintain the biologically active conformation of the protein molecule. Therefore, metabolic processes and
physiological functions largely depend on the acidity of the environment. Thus, a necessary condition for the normal course
of life processes is the steadiness of the pH of biological fluids (acid-base homeostasis). Disturbance of the acid-base
balance (homeostasis) in the body leads to a change in the pH of biological fluids, which in turn disrupts the normal course of
metabolic processes.
 4.3. Hydrolysis processes
Hydrolysis: This is a process of solvolysis in which substances (molecular or ionic) interact with water, leading to their
destruction and new substances formation.
Solvolysis: the interaction between a solvent and a solute.
The dissolution of substances in water is often accompanied by chemical interactions with it, and in principle a substitution
reaction takes place. In general, this interaction proceeds according to the scheme:
Hydrolysis occurs only if at least one weak electrolyte is obtained.
4.3.1. Quantitative characteristics of hydrolysis
The hydrolysis constant (Kh) can be used to quantify the hydrolysis, which is similar to the
dissociation process. The expression for the hydrolysis constant is composed according to the
general rules for reversible processes (there are also cases when the hydrolysis process is
irreversible):
Since water is the solvent, its concentration can enter the constant value. Then the expression
for the hydrolysis constant (Kh [mol/L]) becomes:
Kh is a constant at a given temperature that characterizes the ability of a substance to hydrolyze. The value of Kh depends on
the nature of the substance, the temperature (increases with increasing temperature), but does not depend on the concentration
of the solute.
Degree of hydrolysis (h): is the ratio of the amount of hydrolyzed substance to the total amount of
solute.
Ch – concentration of hydrolyzed molecules; Cо – total concentration of dissolved molecules.
The degree of hydrolysis h increases with increasing amount of water and
with increasing temperature. For example, the hydrolysis of a 0.1 M CrCl 3
solution follows the equation:
 4.3.2. Hydrolysis of salts of weak electrolytes
Hydrolysis of salts is a process of exchange interaction of salt ions with water, which leads to the formation of weakly
dissociating compounds or ions, which causes a change in the pH of the solution. The salts that are hydrolyzed are only those
that as a result of hydrolysis form a weak electrolyte or gas that is released from the system. Salts of strong acids and strong
bases are not hydrolyzed.
The hydrolysis can be carried out both by the ions of water and by its molecules:
Since the concentrations of oxonium and hydroxide ions (at
25ºC it is 10-7 M) is much lower than the concentration of water
(55.5 M), the amount of salt hydrolyzed by water ions is
negligible in comparison to the amount hydrolyzed by water
molecules. Thus, the hydrolysis takes place with a water
molecule from the solvate shell of the ion.
Hydrolysis of the salts of strong acids and weak bases
Examples are the hydrolysis of ammonium chloride and silver nitrate, presented by the complete and abbreviated reaction
equations:

Solutions of such salts have an acidic reaction due to an increase in the concentration of oxonium ions.
Hydrolysis the salts of a weak acid and a strong base
Examples are the hydrolysis of potassium cyanide and sodium acetate, presented by the complete and abbreviated reaction
equations:

Solutions of such salts have an alkaline reaction due to an increase in the concentration of hydroxide ions.
By changing the concentration of H+ or OH- ions, it is possible to control the hydrolysis process. By adding an acid, the
hydrolysis of a weak base salt and a strong acid can be reduced, and by adding a base, the hydrolysis of a strong base salt
and a weak acid can be reduced.
 Hydrolysis of the salts of a weak acid and a weak base
Examples are the hydrolysis of ammonium cyanide and ammonium formate:
It can be seen from the presented
abbreviated equations that the reaction
between the salt ions also leads to the
hydrolysis products. This type of reaction
takes place substantially in concentrated
solutions of these salts.

4.3.3. Relationship between hydrolysis and protolysis constants

Hydrolysis constant of the ammonium chloride hydrolysis is:

Dissociation constant of the ammonium ion (the conjugate acid of

ammonia) is the same. If we multiply the numerator and denominator by
the concentration of hydroxide ions, we get:

Hydrolysis constant (Kh) is the ratio of the water ionic product (KW) to the dissociation constant of the weak base in the salt
structure. The weaker the base, the more hydrolyzed the salt formed by it.
Hydrolysis constant of the potassium cyanide hydrolysis is:

Dissociation constant of the cyanide ion (conjugate base of hydrogen

cyanide) is the same. If we multiply the numerator and denominator
by the concentration of oxonium ions, we get: HCN + H2O ↔ CN- + H3O+

Hydrolysis constant (Kh) is the ratio of the water ionic product (KW) to the dissociation constant of the weak acid in the salt
structure. The weaker the acid, the more hydrolyzed the salt formed by it.
The weaker the electrolyte from which the salt is formed, the higher the hydrolysis
constant, i.e. greater degree of hydrolysis.
For the hydrolysis of weak acid and weak base salts, the expression for Kh is:
In this case, pH of the medium is determined by the relative strength of the two
weak electrolytes from which the salt is derived:
Ка(cation) > Kb(anion) acid medium (HCOONH4)
Ка(cation) = Kb(anion) neutral medium (CH3COONH4)
Ка(cation) < Kb(anion) alkaline medium (NH4CN)
Since in this case both salt ions undergo hydrolysis, under the same other conditions this type of salts is hydrolyzed to a
greater extent than the salts obtained from a weak and strong electrolyte.
In the hydrolysis reaction: Concentrations of ROH and HX are equal ([ROH] = [HX]).
According to the equation for the degree of hydrolysis, the
concentration of hydrolyzed substance is:
Ch = Co.h
The reaction results in two substances whose molar concentration is equal to the molar
concentration of the hydrolysed substance.: [ROH] = [HX] = Co.h
On the other hand, the concentration of the non-hydrolyzed substance will be the difference [RX] = Co - Co.h = Co.(1-h)
between the concentration of the solute (total Co concentration) and that of the hydrolysed
substance:
Then the expression for the hydrolysis constant takes form:
For diluted solutions h << 1 and so 1 - h ≈ 1. Then, the above
expression will be: Kh = Co.h2

For h we obtain:
The more dilute the
The degree of hydrolysis depends on the total
solution, the greater
concentration of the solute, and the lower the
the degree of
concentration of the solution, the greater the degree
hydrolysis.
of hydrolysis. This can be illustrated by the
hydrolysis of sodium carbonate at 25ºC following
the equation:
The reason for this is that in order for the reverse reaction to take place, two particles of hydrolysis products must meet in the
solution, which becomes less probable with dilution. On the other hand, upon dilution, the amount of water relative to the
hydrolyzable substance increases and, accordingly, the probability of a chemical process taking place between them also
increases.
4.3.4. Hydrolysis of organic compounds
Various groups of organic compounds can participate in hydrolysis reactions such as esters, amides, ethers, acetals and others.
Some organic compounds can be hydrolyzed in a biological medium with the help of enzymes. Hydrolysis of proteins,
polysaccharides, nucleic acids, fats and other organic substances is present in living organisms. The enzymes involved in
their hydrolysis are called hydrolases.
Hydrolysis of proteins and peptides Hydrolysis of nucleic acids Hydrolysis of polysaccharides

Fat hydrolysis
 4.3.5. Biological significance of hydrolysis processes
Enzymatically catalyzed hydrolysis processes play an essential role in the digestion and tissue metabolism of all living
organisms. Thus, macromolecular compounds are hydrolyzed to low molecular weight products (amino acids,
monosaccharides, fatty acids, etc.), which are then absorbed from the intestine and transported to various tissues, where they
undergo further transformations.
Hydrolysis is of the greatest practical importance for:
(a) Biopolymers (proteins, polysaccharides and nucleic acids) which take place in the presence of an appropriate
biological catalyst. Most of the amino acids derived from proteins are used to synthesize their own proteins.
Monosaccharides are a major energy source;
b) Esters, in particular fats. The resulting fatty acids are an energy source, and on the other hand are precursors for the
synthesis of other biologically active substances.
Spontaneous hydrolysis undergoes a number of salts in the body, which is essential for regulating the acidity of the
environment and in maintaining acid-base homeostasis in the body.
 4.4. Buffer solutions
Buffer solution (buffer): A solution of a conjugated acid and base that slightly changes its pH when a moderate amount of
strong acid or base is added or when the solution is diluted. One of the components of the buffer should be a weak
electrolyte.
4.4.1 Nature and properties
Most often, buffers are solutions of weak acid and its salt (acid buffers) or weak base and its salt (basic buffers). In biological
systems, buffer solutions can also be formed from ions and ampholytic molecules, for example amino acid and protein buffer
systems. The buffering action is due to the established acid-base balance in the solution. This ability of buffers is called
buffer action. The range of pH values ​in which the system exhibits buffering properties is called the buffer zone (region).
Buffer solutions are used to maintain the pH of the medium at a certain level if a certain process (e.g. enzymatic reaction) has
to be carried out at a constant pH value.
Mechanism of the buffer action
From the point of view of the protolithic theory, the buffering
effect of the solutions is due to the presence of acid-base balance.
Consider, for example, acetate buffer, which is a solution
containing acetic acid and a salt thereof, for example sodium or
potassium acetate. The following processes are performed in the
solution.
Sodium acetate is a strong electrolyte that completely dissociates into
ions:
Acetic acid is a weak electrolyte that partially dissociates into ions:

When a strong acid is added, the acetate ions (CH3COO-) bind H3O+
ions into molecules of the weak electrolyte acetic acid:

Thus, the concentration of free H3O+ ions in the solution and, accordingly, the pH value practically does not change or there
is a small change in pH due to a decrease in the concentration of acetate ions at the expense of increasing the concentration of
acetic acid. Significant deviations in pH values ​(by more than a unit) are observed under conditions of significant (up to 90%)
consumption of CH3COO- anions.
 When a strong base (e.g. NaOH) is added, the dissociation of acetic acid increases as the free H3O+ ions react with HO- ions
to form water, and on the other hand the CH3COOH molecules react with the hydroxide ions to acetate ions and water:

In this case, also there is no significant change in the concentration of H3O+ ions in the solution, as the added HO- ions are
found to be bound in the molecules of a weak electrolyte - water. A slight change in pH may result due to a decrease in the
concentration of CH3COOH and an increase in the concentration of CH3COO-, and a slight increase in pH may be observed.
Significant deviations in pH values (more than a unit) are observed if almost complete (up to 90%) consumption of acid
molecules ocurres.
The cases above show that each component of the buffer solution performs a strictly defined function: the salt anions are
responsible for neutralizing the added acid, and the acid molecules are responsible for neutralizing the added base. Thus, the
following conclusions are valid for acid buffers:
The higher the salt concentration, the more acid can be added to the buffer without significantly lowering the pH.
The higher the acid concentration, the more bases can be added to the buffer without significantly raising the pH.
Let’s consider in brief the action of an alkaline buffer, such as ammonia, consisting of ammonia and ammonium chloride. In
aqueous solution, the hydrated form of ammonia exhibits the properties of a weak base, which is partially decomposed into
ions, while ammonium chloride is a strong electrolyte that completely decomposes into ions.:

When a strong acid is added, its H+ ions react with HO- ions to form water. In addition, NH3 is a base that also reacts with the
added acid to form ammonium ions: Thus, no significant change in the pH of the
solution was observed.
When a strong base is added, the hydroxide ions added to the solution react with the
ammonium ions in the ammonia molecules (weak electrolyte) and no significant deviation in
pH will be observed.:
A significant change in the pH of the buffer solution will only occur The higher the weak base concentration, the more acid
when most of one or the other component of the solution (more than can be added without significantly lowering the pH.
90%) is used to bind the added ions into molecules. The following The higher the salt concentration, the more base can be
conclusions are valid for alkaline buffers: added without significantly raising the pH
 4.4.2. Henderson-Hasselbalch equation for pH of buffer solutions
For the reaction: the equilibrium constant (acid dissociation constant Ka) is
After conversion and logarithmization, it is obtained:

Since -lg[H3O+] = pH and conversion of the

logarithmic equation the Henderson- or summarized:
Hasselbalch equation is obtained:
This is essentially the same equation.
The equation for alkaline buffers, e.g. The difference pKw - pKb = pKa. Thus, in
ammonia, can be derived in a similar way. this case, the pKa of the conjugate acid
can be used.
It follows from the Henderson-Hasselbach equation that:
• The pH value of the buffer solutions depends on the dissociation • The dissociation constant of the weak electrolyte
constant of the acid or base and on the ratio of the amounts of determines the area of ​the buffer action of the solution,
components (weak electrolyte and its salt), but in practice does not i.e. this range of pH values ​in which the buffer
depend on the dilution or concentration of the solutions. In fact, in properties of the system are exhibited. As the buffering
these processes, the concentrations of the components of the buffer action continues until 90% of the component is
solution change proportionally, so that their ratio, which determines consumed (i.e. its concentration has not decreased by
the pH of the buffer solution, remains unchanged. If the an order of magnitude), the buffering action zone
concentrations of the components of the buffer solutions exceed 0.1 differs by 1 unit from pKa (pH = pKa ± 1). In the case
mol/L, then the calculations must take into account the activity of an alkaline buffer, pKa of the conjugate acid is used.
coefficients of the ions in the system.
The Henderson-Hasselbach equation can be used to calculate the pH of the buffer by adding a strong electrolyte. To account
for the dilution of the system when adding a strong electrolyte solution to the buffer solution, multiply the concentrations of
the conjugated base and acid by the volume of the buffer solution :
where VБ is the buffer solution volume, and nb and na are the mols
of conjugate base and conjugate acid respectively.
As an example to illustrate the application of this equation, we will use acetate buffer. If we add a specific volume of strong
acid (Vk) with a concentration of Ck to a certain volume of buffer (VB) with a given concentration, the reaction will take
place:
In the presence of the second component of the buffer solution (acetate ions), obtained mainly from a strong electrolyte, the
degree of dissociation of the weak acetic acid, according to the principle of Le Chatelier-Brown, will be reduced. Therefore,
we can assume that the concentration of neutral acetic acid molecules is practically equal to the concentration of acid in the
buffer solution, and the concentration of acetate ions is equal to the concentration of salt. This means that the reaction written
above will proceed to the end. This assumption leads to a negligible error in the calculations compared to the actually
measured pH change. The number of moles of the added strong electrolyte is:
nk = Vк.Ск.
Then using the alternative form of the Henderson-Hasselbach
equation, we obtain:
Using this equation we can calculate the change in pH of the buffer with the addition of a strong acid.
In the case of adding a strong base, the reaction will proceed:
In this case, the change in pH is given by the equation: where nо are mols of the added strong
base.
If the concentrations of the conjugated base and acid are equal, the Henderson- pH = pKa
Hasselbach equation takes the form:
Therefore, pKa is the pH at which the acid is dissociated in half (50%).
4.4.3. Buffer capacity
It is possible to add an acid or base without significantly changing the pH of the buffer solution, only in relatively small
amounts, as the ability of the buffer solutions to maintain a constant pH is limited.
The ability of the buffer to maintain its pH when acid or base is added or when the solution is diluted is called buffer
capacity.
The buffer capacity (β, dimension - [mol/L]) of the solution is expressed by the amount (number of moles - n) of strong acid
or base, which is added to 1 liter of buffer solution to change the pH by one unit:
𝑛 where ∆pH is the change of the buffer’s pH where CM is the molar concentration of the
𝛽= 𝐶м. 𝑉
after the addition of acid or base (the absolute 𝛽 = Δ𝑝𝐻 strong acid or base, and V is the volume of
Δ𝑝𝐻
value of ∆pH is used). This equation can be the added strong electrolyte solution.
written as:
If the acid that is added is polyprotic or the base is polyvalent and the volume of the buffer is
different from 1 L, the formula is:
where z is the molar equivalent of H+ which the acid releases, respectively taking up by the base. For example, for H2SO4 z =
2, which also applies to Ba(OH)2.

The buffer capacity depends on the following factors:

1. The higher the absolute content of the components of the conjugate base/acid pair, the greater the buffer capacity of the
buffer solution.
2. The capacity of the buffer depends on the ratio of the amounts of the components of the buffer solution and therefore on
the pH of the buffer. The capacity of the buffer is maximum at equal amounts of the components of the buffer system (at pH
= pKa of the weak electrolyte - acid or of the conjugate acid of a given base) and decreases with deviation from this ratio.
The graph shows the change in the buffer capacity of the acetate buffer.

4.4.3. Preparation of buffers with predefined properties

Various chemical compounds can be used to prepare aqueous buffer solutions, following the general principle - the solution
must contain a conjugated acid-base pair (proton donor and proton acceptor) which concentrations are sufficiently high and
comparable. Only then will the buffer be able to effectively maintain a constant pH of the medium at the addition of small
amounts of acid or base, by a chemical or biochemical reaction accompanied by the release/uptake of protons or by dilution.
First, the appropriate pair of conjugated protolites should be selected based on the dissociation constant (pKa ≈ pH). It is then
necessary to select sufficiently high concentrations of the components to determine the concentration of the buffer solution
(e.g. 10-3 M or higher) and to determine the ratio between them required to maintain the desired pH according to the
Henderson-Hasselbach equation.
The following pairs of conjugated protolytes are often used in practice: CH3COONa / CH3COOH, H2PO4- / HPO42-, HPO42- /
PO43-, borate anion / boric acid and others.
 4.4.4. Biological significance of buffers. Blood buffers
The functional state of living organisms is inseparably linked to the stability of the environment in cells, tissues, organs and a
number of biological fluids (blood, saliva, gastric juice, etc.), determined by pH. The state of acid-base balance
corresponding to the norm is called protolytic homeostasis. The appearance of deviations can be caused by various reasons.
The acidity of the medium is important to maintain the biologically active conformation of protein molecules. Therefore,
metabolic processes and physiological functions largely depend on the acidity of the environment. Many substances are
involved in protolytic processes, and in many cases their biological function depends on whether they are neutral molecules
or ions, which is determined by the pH of the medium.
In the process of metabolic transformations in cells, acids are formed (carbon, sulfur, phosphorus, lactic, etc.) as well as bases
(ammonia, amines, etc.). The excess release of these substances over the permissible level may lead to acidosis or alkalosis.
In the process of respiration (oxidation of organic molecules with oxygen) a large amount of carbon dioxide is emitted. The
transport of CO2 is carried out through the blood, which is characterized by a certain range of pH fluctuations - from 7.35 to
7.45. Even small deviations in blood pH from the norm indicate metabolic disorders. Blood pH values ​below 6.8 and above
7.8 are incompatible with life. Blood buffering is crucial. Electrolytes present in the blood (НСО3–, Н2СО3, Н2РО4–, НРО42–
and proteins are involved in maintaining the pH in the normal range.
In blood plasma, the most important buffer system for
maintaining a constant pH is the hydrogen carbonate
H2CO3/HCO3-. The peculiarity of this buffer system is that
one of its components - carbonic acid is formed by the
interaction of CO2 dissolved in water with water:

In normal blood plasma, the ratio of the concentrations of

the system components conjugate base HCO3- / carbonic acid
H2CO3 is approximately 20:1. Since concentration of
NaHCO3 in the blood significantly exceeds the one of
H2CO3, the buffer capacity of this system is very high.
Hydrogen carbonate buffer is the most important buffer in blood plasma, as it works together with two open organs - the
lungs and the kidneys. As a result, the bicarbonate buffer provides a decrease in proton concentration in the body (when CO 2
is exhaled through the lungs) or an increase in proton concentration (when HCO 3 is released through the kidneys). When CO2
is exhaled through the lungs, the body releases carbonic acid, due to which the concentration of hydrogen ions in it decreases.
The rate at which CO2 is released is determined by the rate of respiration.
The protein buffer system is a combination of proteins - albumin (human serum albumin is more than 50% of all blood
proteins), globulins and transferrins (mainly hemoglobin), which make up the majority of blood plasma (~ 90%). The
isoelectric points of most proteins are in the range of pH = 4.9 - 6.3, i.e. - a weakly acidic environment. Therefore, under
physiological conditions (at pH = 7.4), proteins are predominantly in the form of anions. Hemoglobin buffer forms 80% of
the blood's buffering capacity. Blood buffering is due to the reaction (pK a = 8.2):
The system HHb/Hb- can actively neutralize acidic and basic metabolic products, but has a greater capacity for alkaline
substances (at pH = 7.4, conjugated acid predominates) than for acids.
In the lungs, hemoglobin reacts with which is transported with the arterial blood to the capillaries,
HHb + O2 ⇄ HHbO2 from where oxygen enters the tissues
oxygen. Oxyhemoglobin is formed
HHbO2: HHbО2 + H2О ⇄ H3O+ + HbО2

Oxyhemoglobin is a weak acid (pKa = 6.9), but stronger than hemoglobin (pKa 8.2).
At physiological pH 7.4, the conjugate base predominates and the buffer capacity is greater toward acids.
The great importance of hemoglobin is also due to the fact that in addition to its buffering action, after transferring oxygen
from the lungs to the tissues, it returns in the opposite direction associated with CO2. This is done in two ways - by a
complex with the iron ion in the composition of heme, and through a non-enzymatic binding of carbon dioxide to the
terminal amino groups of lysine in the hemoglobin structure, forming carbaminohemoglobin:

Hydrogenphosphate buffer (НРО42-/Н2РО4-), is also involved in maintaining the constant plasma pH. The phosphate
buffer system is able to maintain a constant pH in the range of 6.2 - 8.2 and provides part of the buffer capacity of the
blood. It is essential that, if necessary, its ingredients can be excreted in the urine. Hydrogen phosphate buffer is the most
important intracellular buffer. Its maximum buffer capacity is at pH 6.7.
Due to the above processes, the pH of the blood hardly changes. The strength of the plasma buffer systems decreases in the
order: bicarbonate> protein> hydrogen phosphate. As a summary, the processes of oxygen and carbon dioxide transport are
given in the scheme below.
 5.1 Chemical redox processes
Тhe redox processes (ROP) were first explained by Pisarzewski (1914): An element or ion that loses (donates) electrons is
oxidized, and when electrons are received, a reduction takes place. The two processes take place simultaneously.
Redox processes (ROP): Processes in which electrons are transferred from one type of atoms, ions or molecules to another
type of atoms, ions or molecules, as a result of which their oxidation states change.
5.1.1. Electronic exchange. Semi-reactions
Oxidation is a process in which electrons are donated, and the substance that donates them is called a reducer.
Reduction is a process in which electrons are taken in, and the substance that takes them in is called an oxidant.
Oxidation and reduction can be represented using general electronic
equations:
The above processes take place due to the differences in atoms' electronegativity:
• The atom of a higher electronegativity accepts the valence electrons from the other atom and becomes a negative ion or
more generally: its oxidation state reduces.
• The atom that has lost electrons becomes a positively charged ion or, more generally, its oxidation state increases.
Oxidation number (state): Conditional charge of the atoms in the composition of compounds, if all bonds are considered
ionic (the more electronegative element will be negatively charged, and the one with less electronegativity, positively
charged). Oxidizers reduce their oxidation state (the oxidation number becomes negative) and reducers increase their
oxidation state (the oxidation number becomes positive).
For example, for the reaction: The half-reactions that take place are presented below:
Oxidation Cu - reducer
Reduction О – oxidant
The oxidation state of copper in CuO is 2+ and that of oxygen 2-. These half-reactions are useful for equalizing the reaction
equation based on the electronic and material balance, but do not take into account the real process.
Actually, the two processes are The real process is the process of exchanging
coupled and take place simultaneously, electrons between the two redox systems (or
which is realized by at least two redox pairs).
systems or two redox pairs:
The main rule when writing ROP is: the total number of electrons donated by the reducing agents and the total number
of electrons received by the oxidants in a given reaction system must be the same. The rules for compiling and equalizing
the equations of redox reactions are based on this fact.
Some examples of redox reactions are given below:

Redox processes also take place between organic compounds, but examples of them will be presented when considering
chemical reactions for a given group of organic compounds in the second part of the course.
It is important to note that the term oxidation state (oxidation number) is also used in organic compounds, for example:
It should be kept in mind that valence and oxidation state are
different concepts and do not always coincide, for example in nitric
acid:
Nitrogen is in oxidation state + V, while its valence
is four.

5.1.2. Electrochemical redox potential. Standard redox potential

If we put zinc in a solution of copper sulphate, a red precipitate is observed from the metal copper,
and the solution which is blue is discolored.
The reaction takes place:

Similarly, if copper is placed in a solution of silver nitrate, a gray-silvery

precipitate is observed from the metal silver, and the solution which is colorless
turns blue. The reaction is going on:

On the other hand, between silver and a solution of copper dinitrate, no reaction takes place.

To explain these phenomena and many other facts, we‘ll consider the processes occurring when a metal plate is placed in
water or in an aqueous salt solution containing the ions of the same metal. The metal crystal lattice is composed exclusively
of ions, and in the metal body the electrons move relatively freely - the metal bond is a delocalized chemical bond, without
limitation of the atoms involved. Contact of metal with water or an aqueous solution of electrolyte leads to an interaction
between the polar water molecules and metal cations located in the nodes of the crystal lattice.

When a metal is immersed in water, the polar water molecules

attract the metal cations from its surface and some of them pass
into the aqueous phase, where they are solvated, i.e. form an
aquacomplex:
Thus, the solution near the metal surface is positively charged, and the metal surface is negatively charged due to excess
electrons. The charged surface of the metal attracts ions with the opposite charge, so the process is reversible - the reverse
transition of cations from the solution to the crystal lattice of the metal takes place. A type of capacitor is formed - a double
electric layer on the surface of the metal and the water around it. There is a potential difference, which value depends only on
the nature of the metal.
 These processes also take place when the metal is in a solution of its salt. If the
concentration of metal ions in the solution is low, the process of separation of ions
into the solution prevails until equilibrium is reached. In this case, the metal is
negatively charged and the solution is positively charged. In the case when the
concentration of metal ions in the solution is high, the process of deposition of metal
ions on the surface of the crystal lattice of the metal prevails until equilibrium is
reached. In this case, the metal is positively charged and the solution is negatively
charged, as the anions prevail.
As a result of the above processes between the metal surface and the electrolyte, a double electric layer appears. The potential
difference is called the electrode potential between the metal in the solid phase (reduced form) and the metal cations in
solution (oxidized form). The absolute value of the electrode potential cannot be measured or calculated, but it is possible to
determine only its relative value. When the temperature is 25°C and the concentration of metal ions is 1 M, the potential
difference between the metal and the solution is called the standard electrode potential (E0).
A system of chemically inert electrode, for example a platinum in electrolyte solution containing ions of one and the same
chemical element but in different oxidation state, is also called an electrode. A double electric layer also occurs on the inert
electrode as a result of oxidation-reduction reactions at the interface, i.e. an electric potential arises on the surface of the
electrode.
Redox potential: The potential that arises in a system consisting of an inert electrode and a solution containing a conjugated
redox pair.
5.1.3. Hydrogen electrode
Since the oxidant is such only in the presence of a reducer and vice versa, it is impossible for an oxidant to exist without a
reducer and vice versa. For this reason, it is impossible to measure the potential of an isolated redox pair without combining
it with another for electronic exchange. The presence of two redox pairs leads to a potential difference that can be measured.
This requires the use of a certain standard. In the electrochemistry of aqueous solutions, a standard hydrogen electrode
consisting of an aqueous solution of sulfuric acid ([H3O+] = 1 mol/L ≡ 1 M; pH = 0) is used as such a standard, in which a
platinum plate is immersed at a temperature 25ºC (298º K). The surface of the plate is covered with a layer of "spongy"
(porous) platinum, thus increasing its adsorption capacity. Pure hydrogen is passed through the solution at a pressure of 1
atmosphere (101 kPa).
 Platinum has the ability to adsorb hydrogen, and adsorbed H2 molecules break down
into atoms that are ionized. For the half-reaction:

the standard electrode potential is assumed to be 0 (EºH = 0).

If a standard hydrogen electrode is connected to any other electrode with an
electrolyte concentration relative to the metal ion of 1 mol/L and the potential
difference is measured under standard conditions (at a temperature of 25ºC and a
pressure of 1 atmosphere (101 kPa)), then the value of the standard potential of the test
electrode is determined.
The values of the standard electrode potentials Eº (V) for a number of
electrodes are given in the table.
Li+ + e-  Li –3.05 2H+ + 2e-  H2 0.00 Fe3+ + e-  Fe2+ 0.77
K+ + e-  K –2.92 Cu2+ + 2e-  Cu 0.34 Co3+ + e-  Co2+ 1.85
Ca2+ + 2e-  Ca –2.76 Ag+ + e-  Ag 0.80 H2O2 + 2e-  2HO- 1.80
Na+ + e-  Na –2.71 Hg2+ + 2e-  Hg 0.85 Fe(CN)63-+e-Fe(CN)64+ 0.36
Mg2+ + 2e-  Mg –2.37 Cl2 + 2e-  2Cl¯ 1.36 Co(NH3)63++e-Co(NH3)62+ 0.10
Al3+ + 3e-  Al –1.76 Au3+ + 3e-  Au 1.68 Au(CN)2-+e-Au + 2CN- -
Zn2+ + 2e-  Zn –0.76 Au+ + e-  Au 1.69 0.50
Fe2+ + 2e-  Fe –0.41 F2 + 2e-  2F¯ 2.87

On the basis of the electrode potentials (electrochemical redox potentials) thus obtained, the so-called electroaffinity order
or the order of relative activity (ORA) of metals can be compiled.

Increasing the oxidation ability

All metals to the left of hydrogen dissolve in non-oxidizing acids, and those to the right of it do not dissolve in them. Each
metal of the ORA can displace from the corresponding compound the metals that are to the right of it in the row. This line
applies only to ORA between metals and electrolyte solutions (soluble metal salts)!
By comparing the potential values, it is possible to determine whether a metal is capable of displacing hydrogen from acidic
solutions in which H+ is an oxidant or displacing another metal from a solution of its salt. In the first case it is necessary to
compare a given electrode potential with the potential of the hydrogen electrode, in the second case - two electrode potentials
should be compared with each other - the reducing agent must be characterized by a lower potential than the oxidant.
The more negative the value of the standard electrode potential of the metal, the higher its reducing ability and the
lower the oxidizing ability of its cations.
It is impressive that lithium is the strongest reducer of all metals, although other alkali metals are much more reactive than it.
The reason for this "anomaly" is the fact that the enthalpy of solvation (ΔH<0) of Li + is significantly higher in absolute value
than that of other alkali metals and in general the most energy is released during the transition from lithium metal to hydrated
lithium ion relative to other alkali metals. The same is the reason for calcium to be before sodium in ORA. It is very
important to note that this order applies only to aqueous solutions and in the absence of substances capable of forming stable
complexes with the corresponding metal ion.
In aqueous solution, copper does not react with hydrochloric acid, but with dry
hydrogen chloride it reacts reversibly by the reaction:
If substances are present in the system that can form a stable complex with any of the components of the redox pair, this
leads to a change in the redox potential of this redox pair. For example, for the reaction:
the potential is 1.69 V. However, in the presence of
cyanide ions:
The potential is -0.50 V, i.e. the difference is as high as 2.19 V.
5.1.4. Chemical sources of electric energy. Galvanic cell
Electrochemistry is an experimental science. Its origins date back to the early 19th century. This science owes its
development to three exceptional events related to the practice: in 1800 the Italian Alessandro Volta created the first chemical
source of direct current - an electric battery. The author named it a "galvanic cell" after his colleague Luigi Galvani, the
author of the theory of "animal electricity."
The galvanic cell consists of two electrodes of different metals in the form of plates, rods and others, and solutions of
electrolytes, that are connected. Solutions of salts of these metals, solutions of acids or bases can be used as electrolytes.
 We will consider a model of a galvanic cell Daniel - Jacobi. It was
invented in England by John Daniel and in Russia by Boris Jacobi
at the same time. The cell consists of zinc and copper plates
immersed in solutions of zinc and copper sulphates, respectively,
and its device is shown in the figure to the left
(Zn | Zn2+ || Cu2+ | Cu).
To separate electrolyte solutions in such a cell, porous barriers or
isolated solutions are used which are connected to with a salt bridge.
If the metal plates are connected to a wire, electrons will move along
it from the electrode with a lower (more negative) potential to the
electrode with a higher (more positive) potential according to the
reaction:

The oxidation process is performed on the zinc electrode and the reduction on the copper electrode. In the process of redox
reactions, a directed movement of electrons from the reducing agent to the oxidant occurs. This process will result in a
positive charge of the ZnSO4 solution and a negative charge of the CuSO4 solution. This creates a reverse voltage, which
proceeds until the potential between the two cells equalizes. Then, the process stops. A salt bridge is used to continue the
reaction until one of the components is exhausted. It allows the movement of ions from both solutions from one side of the
cell to the other. This closes the electrical circuit. Such systems is a source of electrical energy based on the transformation of
the energy of a chemical reaction. In turn, the flowing electric current can do a job.
Galvanic cell: A device for the direct conversion of the energy of chemical processes into electrical energy. It consists of two
electrodes immersed in electrolyte. It works at the expense of a spontaneous redox process - on the surface of one electrode
an oxidation process takes place and electrons are released, and on the other - a reduction process occurs and electrons are
accepted. Thus ,the chemical energy is converted into electric energy.
5.1.5. Electrolysis
Let’s consider a galvanic cell composed of Cd | Cd2+ || Cu2+ | Cu. A chemical reaction
takes place:
If we apply a reverse voltage greater than the potential difference between the two
electrodes, the reverse process will take place.:
In this case, cadmium is an oxidant and copper is a reducer. The process is forced – it cannot happen spontaneously, but
under the action of the electric current the chemical reaction takes place. This process is called electrolysis.

Electrolysis: the set of processes that take place when a

direct electric current passes through an electrochemical
system consisting of two electrodes (cathode (-) and
anode (+)) and a solution or a melt of electrolyte. A
reduction process takes place at the cathode and an
oxidation process at the anode.
In the process of electrolysis (in an electrolyte cell) there
is a conversion of electrical energy into chemical
energy.

Electrolysis is a process that finds great application in the production of metals and other substances. For example,
electrolysis of a melt of NaCl produces Na and Cl2. Electrolysis of an aqueous NaCl solution gave NaOH and Cl 2.
Electrolysis also takes place when charging the batteries. Today, the so-called lithium-ion batteries are widely used. They
consist of lithium cobalt (III) (LiCoO2) or lithium nickel (III) (LiNiO2) as positive electrodes and graphite as negative
electrode. There is a barrier between them that has pores through which only lithium ions can pass. When charging the
battery, the following anode process takes place (usually made of aluminum):

Some of the lithium ions, under the action of the electric field, pass through the barrier and fall into the graphite. Graphite is
made up of layers between which Li+ can be embedded. Through the wire, the electrons move to the cathode (usually made
of copper). That's where the reaction takes place:

At the cathode, lithium ions accept electrons and are converted into lithium atoms, which remain embedded in the crystal
lattice of graphite. In case of discharge, the reverse processes take place.
 5.2. Dependence of the potential on various factors
The value of each electrochemical redox potential or only redox potential (E, V]) depends on the nature of the redox pair, the
concentration of its components in the solution and the temperature.
5.2.1. Dependence of the potential on the concentration. Nernst-Peters equation
The potential difference (voltage) between two redox pairs can be used in the galvanic cell to convert chemical to electrical
energy, and the latter can be used to perform work. The converted electrical energy is equal to the work done Wel ([J]) and is
expressed by the equation:
where n is the number of mols of electrons, F is a Faraday number, which represents the charge of
Wel = - n.F.E 1 mole of electrons (96 485 C/mol) and Е is the potential of the cell ([V] = [J/C]).
The performed electrical work Wel is related to the change of free Gibbs energy ([J]) by means
of the equation: Wel = DG = - n.F.E
If the reaction is carried out under standard conditions (temperature 298 oK, pressure 101 kPa (1 atm), the concentration
of the substances is 1 mol/L), the change in the standard free energy ∆G° is given by the expression:
where E° is the standard redox potential ([V]). As mentioned above, the standard redox potential
∆G° = - n.F.E° of each redox pair was measured at 25°C and monomolar concentrations of its reduced and
oxidized form. When the concentrations of the oxidized and reduced forms are not the same, the
redox system has a different redox potential.
For the reversible reaction: we can use the Vant Hoff equation for the change of free
energy

If in this equation we replace ∆G and ∆G° with their equals

by the redox potential, we get:
where T is the absolute temperature ([оК]), R is the universal
gas constant (8,314 [J/(mol.K]), and [A], [B], [C] and [D] are
the concentrations of components ([mol/L]).
Dividing both sides of the equation by - n.F, we get:
 where DE is the difference in the redox potentials of the products and reagents, and
ΔE° is the difference in the redox potentials of the products and reagents under
standard conditions.
For a redox pair, it is accepted that the reversible chemical half-reaction to be
expressed as:
i.e. the forward reaction is the reduction of the oxidized form. The dependence of the redox potential of a half-reaction on the
concentrations of its oxidized and reduced form is expressed by the equation:

If we take the inverse ratio of the two forms (which also

changes the sign) we get the Nernst-Peters equation:

If solids are involved in the reaction, their concentrations are taken to be 1 and are not taken into account in the Nernst-Peters
equation. Since it is more convenient to use a decimal logarithm, the equation takes form:

At a temperature 25°C (298 оК), we obtain:

According to the Nernst-Peters equation, the values ​of such redox potentials depend on the three factors mentioned at the
beginning. The nature of the redox pair is characterized by E°. As the temperature rises, the potential increases. The potential
also depends on the concentrations of the two forms of the redox pair. As the concentration of the oxidized form increases,
the potential of the redox pair increases and vice versa. The higher the value of the redox potential, the more pronounced
the oxidizing properties of the system and vice versa.
As an example of the importance of concentrations, let’s consider a galvanic cell with two nickel electrodes immersed in a
solution of nickel sulfate (NiSO4), with different concentrations - 0.001 M and 1 M.
 A potential difference is obtained between the two electrodes,
despite the same chemical composition of electrodes and
electrolyte solutions. This is due to the difference in the
concentrations of the oxidized form (Ni2+), according to the
Nernst-Peters equation for the two half-elements of the galvanic
cell.
[Ni2+] (M) E(Ni2+/Ni) (V)
1.10-6 -0.43
1.10-5 -0.40
The table shows the potentials of the semi-element depending on the 1.10-4 -0.37
concentration of nickel ions at temperature 25C (298K). 1.10-3 -0.34
1.10-2 -0.31
1.10-1 -0.28
1 -0.25

5.2.2. Conditional electrode potential (Eh)

A number of redox reactions, especially biochemical ones, in which in addition to electron transfer a proton transfer also
takes place. When the redox process is accompanied by the transfer of H+ (or oxonium ions in water), the potential of the
redox pairs is pH-dependent.
If the half-reaction proceeds according to the equation:
then for the redox potential the expression is obtained: where m is the number of
exchanged moles of
protons.

After a conversion, use of the decimal logarithm and taking into account
the dependence that рН = - lg[H+], it is obtained:
At a temperature 25C (298K), the equation has the form:
The expression which includes pH is called the conditional electrode
potential or the conditional redox potential (Eh):

In the case of redox processes accompanied by proton exchange, the standard pH = 0. In the biochemical literature, in
contrast to chemistry, the standard pH = 7.
Reaction Е [V]
H2O2 + 2H+ + 2e-  2H2O 1.78
The table gives examples of some such reactions: MnO4- + 8H+ + 5e-  Mn2+ + 4H2O 1.51
Cr2O72- + 14H+ + 6e-  2Cr3+ + 7H2O 1.33
О2 + 4H+ + 4e-  2H2O 1.23
SO42 + 2H+ + 2е-  SO32- + H2O 0.17

Graphically, the dependence of some of these potentials on pH is

shown in the figure:

At pH = 7, the potential of the hydrogen electrode ЕH = -0.41 V.

All metals that have a potential less than -0.41 V react with
water.

5.2.3. Criterion for the direction of the redox processes

For two redox pairs half-reactions are:

accordingly the sum reaction is:

The change in the redox potential of the reaction (DE = DE1 - DE2)
as a whole is
The values of the redox potentials allow to predict the direction of the redox reactions. In this case, the oxidant function is
taken over by a system with a higher potential, and the role of a reducer is taken over by a system with a lower potential. The
reaction proceeds spontaneously in the direction that provides a positive value of E.
The redox pair with a higher potential is an oxidant, and the one with a lower redox potential is a reducing agent.

5.2.4. Biological oxidation

Redox processes are crucial for living organisms. Typical paradoxes are performed during cellular respiration. Through them
the body is supplied with the energy necessary for life processes. Cells that require oxygen as an oxidant (electron acceptor)
have aerobic metabolism, and those that use other oxidants have anaerobic metabolism.
In the cell, energy is released gradually as electrons pass through chains of biological redox systems called respiratory chains.
These redox systems are arranged according to their standard redox potential, with each successive redox system having a
higher redox potential. Usually the last is the oxygen redox system.

The energy released during the transfer of electrons (oxidation, respiration) through the respiratory circuits is most often used
to phosphorylate ADP to ATP. This process, which is essentially the association of electron transfer with phosphorylation, is
called oxidative phosphorylation. Both electron transfer along the respiratory chain and oxidative phosphorylation take place
in the inner mitochondrial membrane. The transfer of electrons along the respiratory chain is accompanied by the transfer of
protons outside the inner mitochondrial membrane.
Photosynthesis is an oxidation-reduction process at the heart of plant life processes. It takes place under the action of light
and with the participation of chlorophyll: 6CO + 6H O → C H O + 6O
2 2 6 12 6 2

Carbon dioxide is absorbed and glucose is formed, which is a key energy source (glucose is oxidized with the release of
energy) for plants (during the dark part of the day) and for animal organisms and humans that feed on plants. Photosynthesis
is the natural process leading to the formation of oxygen.
 6.1. Complex (coordination) compounds
6.1.1. Complex (coordination) compounds - introduction
In the broadest sense, a complex is a particle obtained by association of two or more simpler particles, when each of them is
capable of existing independently.
For example, in the association process expressed by the equation below, the particle AB represents a complex:

The most important for chemistry are complex compounds which are called coordination complexes or coordination
compounds.
The existence of complex compounds took shape in the late 19th century, when it was found that some compounds in which
the constituent atoms had exhausted their valence to enter into chemical reactions, could still accept other compounds or
ions. For example, PtCl4 reacts with ammonia to form a number of compounds: PtCl 4.2NH3, PtCl4.4NH3 and PtCl4.6NH3.
In 1893, Werner proposed his coordination theory. According to it, many metal ions tend to coordinate particles called
ligands around them to form stable complexes. To explain the formation and structure of these compounds, Werner
formulated the following postulate:
1) Metal ions have two types of valences - primary and secondary (coordination);
2) Metal ions tend to use both primary and secondary valence;
3) The secondary valences are directed in the space around the central metal ion.
Werner's theory does not explain why secondary valences occur. Lewis & Sedgewick later explained that metal ions sought
to obtain the electronic structure of the noble gas closest to them or to obtain an electronic structure with a semi-filled
electronic layer that was relatively stable. But even these theories do not explain all the observed facts.
6.1.2. Complex former, ligands and coordination number
Coordination compounds always contain a central atom or ion, which is called a complex former (or coordination center).
The complex former may be metal atoms or metal ions, as well as atoms and ions of non-metallic elements.
The complex former is surrounded by ligands, which can be negatively charged ions or neutral molecules.
The ligands located around the central ion or atom form the internal coordination sphere of the complex compound. It is
customary to enclose the internal coordination sphere in middle brackets.
Other ions make up the outer coordination sphere and they are not directly connected to the coordination center.
Thus, complexes of PtCl4 with ammonia can be written as: [Pt(NH3)2Cl4.], [Pt(NH3)4Cl2]Cl2 и [Pt(NH3)6]Cl4.
Coordination compounds: Complex substances composed of a central atom or ion (complex former) around which simple
or complex ions or neutral molecules (ligands) are coordinated (by chemical bonding).
6.1.3. Coordinate covalent bond - a covalent bond with a donor-acceptor mechanism of formation
The formation of coordination compounds in many cases can be observed visually. For example, if we add an aqueous
solution of ammonia to an aqueous solution of copper sulphate, the color of the solution changes from pale blue to dark blue:

Addition of potassium thiocyanate (potassium rhodanide) to an aqueous solution of iron trichloride (colorless or pale yellow
in color) results in an intense blood red color:

A mechanism of formation of a two-electron bond (covalent bond) is the donor-acceptor mechanism. The bond formed in that
way are called coordination bonds and are denoted by an arrow beginning with the donor (ligand) and ending with the
acceptor (complex former), e.g.:
Complex compounds that have covalent
bonds formed by a donor-acceptor
mechanism are called coordination
compounds.
6.1.4. Types of ligands - dentation
An important characteristic of the ligand is their dentation - the number of bonds that the ligand can form with the complex
former.
Ligands that can form only one bond with the complex former are called monodentate. Monodentate ligands, for example,
are: H2O, NH3, CO, F-, I-, Cl-, HO-, NO2-, CN-
Ligands are called bidentate if they can form two bonds with the complex former, for example: С 2О42-, S2О32-
Ethylene diamin glycinate 2,2‘-bipyridine acetyl acetonate

Ligands capable of forming several bonds with the complexing agent are called polydentate. These include, for example,
EDTA (ethylenediaminetetraacetic acid) and other organic compounds:

N1, N1-bis(2-amino ethyl)-

ethane-1,2-diamine

ethylenediaminetetraacetic acid (EDTA)

6.1.5. Chelate complexes
Polydentate ligands are known as chelating agents because they form more than one bond with the complex former to form
chelate complexes.
The figure shows examples of chelate complexes of Cu 2+ and Co3+:

In this type of complex formation cyclic complexes are

obtained. Intra-complex compounds can exist as neutral
complexes and charged complexes.

In the cobalt (III) ion complex with EDTA, the two nitrogen atoms are donor, as well as the
four oxygen atoms of the carboxylate ions. Because EDTA binds to the metal ion through six
donor atoms, it forms a particularly stable complex (in order to destroy the complex, it is
necessary to break six chemical bonds). The structure of the complex obtained by X-ray
diffraction analysis is shown in the figure:
 6.1.5. Cationic, neutral and anionic complexes
Depending on the charge of the complex former and the charge of the ligands, the coordination compounds are cationic,
neutral and anionic. The table gives some examples of the three types of complexes:
cationic neutral anionic
[Ag(NH3)2]+ [Fe(CO)5] [AlF6]3-
[Cu(NH3)4]2+ [Ni(CO)4] [BF4]-
[Mg(H2O)6]2+ [Pt(NH3)2Cl2] [Fe(CN)6]3-
[XeF5]+ [Pt(NH3)2Cl4] [Ni(CN)4]2-

6.1.6. Nomenclature and spatial structure of coordination compounds

According to the rules adopted by IUPAC for the names of complex compounds:
1. The name of the complex is formed as always the name of the cation is placed before the name of the anion;
2. In the complex ion, the name of the ligands is placed before the name of the metal. In the case of different ligands, their
arrangement is in alphabetical order, and the prefix showing their number is not taken into account in the arrangement;
3. The ending -o is added to the name of the anionic ligands. 2+
[Mg(H2O)6] hexaaquamagnesium (II)
Ligand Name Ligand Name
[Cu(NH3)4]2+ tetraaminocopper (II)
H- hydro NO2 - nitro
[Pt(NH3)2Cl2] diaminodichloroplatine (II)
Cl- chloro H2O aqua
[Fe(CO)5] pentacarbonyliron (0)
HO- hydroxo NH3 amine [Fe(CN)6]3- Hexacyanoferate (III)
CN- cyano CO carbonyl [Co(NO2)6]3- hexacyanocobaltate (III)

The nature and coordination number of the complex former determines the spatial structure of the coordination compound.
Some examples of spatial structure are given below:
Coordination Examples Structure
number
2 [Ag(NH3)2]+ linear
[Ag(CN)2]-
3 [Cu(CN)3]2- triangle
[HgI3]-

4 [BF4]- tetrahedron
[Cu(NH3)4]2+
[Ni(CO)4]
[Zn(OH)4]2-
[Pt(NH3)2Cl2] planar
[AuBr4]-
[PtCl4]2-
[NiCl4]2-
5 [Fe(CO)5] triangular
[CuCl5]3- bipyramid
[FeCl5]2-

[Ni(CN)5]3- square
pyramid

6 [Cr(H2O)6]3+ octahedron
[Fe(CN)6]2- (square
[SbF6]- bipyramid)
[PF6]-
7 [ZrF7]3- pentagonal
[TaF7]2- bipyramid
8 [TaF8]3- square
[W(CN)8]2- antiprism
[ReF8]2−
[Mo(CN)8]4− dodecahedron
Geometric isomerism can occur in complex compounds. The geometric isomerism is due to the different arrangement of the
ligands relative to each other and is a common case of complex compounds with planar structure and coordination number 4.
Mixed complexes with the composition [MA2X2], which have a flat square configuration, may have two isomers. If the same
ligands are on one side of the complexing agent, then this isomer is cis, and if they are on different sides, a trans-isomer is
formed, e.g. diaminodichloroplatinum (II) - [Pt(NH3)2Cl2]. Such compounds are also found in coordination number 6 and
composition [MA4X2]. цис- транс-
cis- trans-

Geometric isomers exhibit different

properties, including their biological activity.

Violet Green
Optical isomerism occurs in complex compounds, the structures of the inner
spheres of which do not coincide in three-dimensional space and are a mirror
image of each other. The optical isomerism of complex compounds is possible
only when the inner sphere does not have a single plane of symmetry, i. a
plane that would divide it into two equal parts.

Another type of isomerism occurs when a ligand can bind to

a metal through any of two different donor atoms (ambient
ligands). For example, the nitrite ion forms two different
pentaaminecobalt (III) complexes: a yellow nitro complex
that contains a Co-N bond, and a red nitrite complex that
contains a Co-O bond:
 6.1.7. Stability of coordination compounds
The formation and decomposition of a complex ion or compound
[ in solution
is an equilibrium process:
This reaction takes place in stages, which are presented in the scheme (in this case
the ligand L is neutral, but this also applies to ligands which are ions):

According to the law of mass action, the equilibrium constant

for the formation of the complex Kf has the form:

The value of the equilibrium constant indicates how stable the resulting complex compound is. Therefore, it is also called the
stability constant and is denoted by β. Since this is a constant of complex formation, the larger it is, the more stable the
resulting complex compound. Different complex compounds have different stability. For example, K4[Fe(CN)6] does not
produce many of the reactions inherent in Fe2+ or CN- and is therefore practically non-toxic. On the other hand, K3[Fe(CN)6]
gives reactions typical of the CN ion and is toxic. In addition to the stability constant, stability of the coordination
compounds is characterized by the dissociation constant Kd which value is reciprocal of β:

The higher the value of the stability constant β or the smaller the value
of the dissociation constant, the greater the stability of the complex ion
and vice versa. Ligands from the internal coordination sphere of
complex compounds can be replaced by other molecules or ions. Thus,
the destruction of the complex ion can be achieved by binding the
dissociation products either in more stable complexes or in sparingly
soluble compounds, according to Le Chatelier-Brown's principle of
chemical equilibrium. For example, the reaction between zinc sulfate
and ammonia in water. In the aqueous solution of zinc sulphate, zinc
ions exist in the form of an aqua complex [Zn(H2O)4]2+. As a result of
the reaction, the water molecules are gradually replaced by ammonia
molecules, as the tetraaminozinc ion is significantly more stable than
the tetraaquazinc ion.
 6.1.8. Biological significance
Complex compounds are widespread in nature, e.g. hemoglobin, chlorophyll, vitamin B12, various enzymes etc. are complex
compounds. Rare elements that are found in the tissues of plants and animals are part of complex compounds.
Metalloproteins include biopolymers which, in addition to the protein, contain a prosthetic group (non-protein component)
that includes metal ions.
A separate group of metalloproteins is composed of hemoproteins containing iron compounds as a prosthetic group. One of
the most important hemoproteins is hemoglobin. It consists of protein (globin) and a complex of iron with porphyrin (heme).
In heme, the Fe2+ ion (complex former) binds to two nitrogen atoms belonging to the porphyrin ring through a covalent bond
and two more "coordination" bonds. The coordination number of Fe 2+ is six. In the porphyrin complex, the fifth coordination
position is occupied by the imidazole nucleus of histidine from the protein, forming a coordination bond through the nitrogen
atom with Fe2+. In the absence of oxygen, the sixth ligand is water. When water is replaced by oxygen, oxyhemoglobin is
formed.
In hemoglobin, the Fe2+ ion can bind other ligands, for
example CO, CN- and nitrogen oxides. These complexes are
much more stable than the oxy-complex, which leads to a
blockage of oxygen transport and therefore CO, CN- are
highly toxic.

heme В heme + oxigen forms oxyhemoglobin

Enzymes provide the realization of genetic information, as well as metabolism and energy. Enzymes differ from chemical
catalysts in much higher activity and high specificity of action: an enzyme usually catalyzes only one chemical reaction.
Many metal ions play a role as coenzymes (Fe2+, Cu2+, Mn2+ and others) in enzymes that catalyze redox reactions. Others are
coenzymes in hydrolytic enzymes (Zn2+, Mg2+ and others), such as coenzymes (Mg2+) in enzymes involved in the
biosynthesis of nucleic acids or those in the biosynthesis of polysaccharides (Mg2+, Mn2+). Coordination compounds also
perform many other functions, for example, chlorophyll, which is a porphyrin-type complex of Mg2+, vitamin B12
(cobalamin), a porphyrin-like complex with Co3+.
 6.1.9. Application in medicine
The toxic effect of most heavy metals (mercury, lead, thallium, etc.) is explained by the ability of the ions of these metals to
form stable complexes with proteins (including enzymes). As a result, the biological activity of proteins is suppressed
because they are denatured.
Some agents capable of forming stable complexes with metal ions are used as antidotes in domestic and occupational
poisoning with heavy metal compounds. In case of poisoning with compounds of mercury, lead, antimony and arsenic,
dimercaprol (2,3-dithiopropan-1-ol) is used for their binding and removal from the body, which is administered
intravenously. It removes from the body in the form of complexes, for example:

Intravenous administration of EDTA is used to remove excess Ca2+ ions from the body in the form of a stable complex that
reduces the likelihood of kidney and gallbladder stones.
Under the name cisplatin, the cis-isomer of diaminodichloroplatin (II) ([Pt(NH3)2Cl2]) is used as an effective anticancer
agent. The trans isomer has no curative effect and can cause deafness. Thus, the cis-isomer has a therapeutic effect in cancer,
while the trans-isomer has no antitumor effect, but both compounds are highly toxic.
6.2. Corrosion
Corrosion: a process of gradual physico-chemical destruction of the material under the influence of the environment.
Destruction always starts from the surface and spreads to the inside.
6.2.1. Nature and mechanism of corrosion
Corrosion of metals is the spontaneous destruction of the metal due to chemical or electrochemical effects of the
environment. It is accompanied by a change in the surface of the metal, on which there are destroyed areas and corrosion
products. The environment in which corrosion takes place (corrosive environment) is usually a gas or liquid.
The corrosive medium can be non-electrolyte (gases such as O2, SO2, NO2, CO2, H2S, etc. or liquids such as oil and its
derivatives, etc.) or electrolyte (aqueous solutions of acids, salts, bases, sea, river or tap water). and others. Corrosion of
metals in a non-electrolytic medium occurs by a chemical mechanism. Chemical corrosion consists of a direct chemical
reaction between a metal and a medium, whether liquid or gas. In an electrolytic environment, corrosion occurs by an
electrochemical mechanism. Electrochemical corrosion in general has the character of anodic oxidation, which can be based
on spontaneously generated galvanic cell, the so-called galvanic corrosion or a kind of electrical system caused by an
electric current from an external source - the so-called electrocorrosion. The presence of substances capable of forming
complexes with metal ions also favors the corrosion.

In corrosion, the electroneutral atoms of the metal pass into positively charged ions due to the release of electrons. Corrosion
is caused by a number of factors known as corrosive factors - primarily oxygen (air) and water vapor. The content of SO2,
CO2, H2S and others accelerates corrosion. This should include the particularly high corrosive capacity of aqueous salt
solutions - sea water. In addition, the pH of the solution in which the metal is located has a significant effect on the corrosion
rate. The susceptibility of metals to corrosion is closely related to their places in the electroaffinity order. The metals that are
strong electron donors are much more prone to corrosion. These are the metals to the left of hydrogen.
Chemical corrosion: a spontaneous redox process in a non-conductive medium in which there is a direct heterogeneous
interaction of the metal with an oxidant from the aggressive medium.
An example is the oxidation of metals under the action of atmospheric oxygen, which 2nM + mO2 → 2MnOm
takes place according to the equation:
Schematically, the process is presented in the figure:
Oxygen molecules are adsorbed on the metal surface. There they can
accept electrons from the crystal lattice of the metal, forming oxide ions
(O2-). By reacting with the positively charged metal ions, the corresponding
metal oxides are formed. Thus, an oxide layer is formed on the surface of
the metal. Through the oxide layers thus obtained, oxide ions can diffuse
inside the metal, and many oxides have semiconductor properties, which
facilitates the transfer of electrons to the surface, where they are transferred
to the oxygen atoms of O2.
Electrochemical corrosion: a spontaneous redox process in electrolyte solutions in which oxidation of a metal and reduction
of the oxidizing component in a corrosive medium take place on different parts of the metal surface.
A typical example is the rusting of carbon steels (pure iron also corrodes, but does not form rust!). Depressions caused by
corrosion can be seen on the surface of the steel, but rust (Fe(OH)3 + FeO(OH) + Fe2O3.nH2O) is deposited in a place
physically separated from the pits. This suggests that rust is not formed by a direct reaction of iron and oxygen, but by an
electrochemical process in which iron is oxidized in one area of ​the surface and oxygen is reduced in another region.
The surface of the iron and a droplet of surface water represent a small galvanic cell in which different areas of the surface
act as an anode and a cathode, while the aqueous phase serves as an electrolyte. Some of the iron in carbon steels exists in the
form of a compound with carbon Fe3C (cementite), which is more easily oxidized than iron.
In some places, areas called anodes are formed, and in other places, cathodic areas are formed where different processes take
place.
Anode process: the metal passes into the solution in the form of ions (most often hydrated), and an equivalent amount of
electrons remain in the metal.
On the anode: 2Fe → 2Fe2+ + 4e- (E° = 0.45 V)
Cathode process: acceptance of the uncompensated electrons of the metal by some oxidant (atoms, molecules or ions) from
the solution, which are reduced.
On the cathode: O2 + 2H2O + 4e- → 4HO- (E° = 0.40 V)

The iron and hydroxide ions formed react to iron dihydroxide: 2Fe2+ + 4HO- → 2Fe(OH)2
In turn, Fe(OH)2 is easily oxidized by oxygen from the air: 4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
The resulting iron trihydroxide is gradually dehydrated Fe(OH)3 → FeO(OH) + H2O
according to the equations:
4Fe(OH)3 → 2Fe2O3.H2O + 5H2O
The considered rusting mechanism, in accordance with the
known facts, is illustrated in the figure:
The corrosion of metals in electrolyte solutions is due to the formation and
action of numerous microgalvanic cells located on the metal surface.
The corrosion products usually remain on the surface of the metal and the
further performance of the corrosion process is determined by the structure,
chemical and mechanical properties of the resulting layer.
• If the corrosion products do not bond tightly to the metal surface, the corrosion process continues until the metal product
is completely destroyed (for example, the formation of rust in steels).
• If the corrosion products bind tightly to the metal surface, the oxidant's access to the metal becomes difficult, leading to a
delay in the corrosion process or passivation. For example, the formation of Al 2O3 on aluminum or Fe3(PO4)2 or FePO4
on iron or steel products.
Biochemical corrosion: occurs under the action of various living organisms, most often microorganisms. In their vital
activity, they usually emit various types of organic acids, which cause corrosion of metals, which is often accompanied by
electrochemical corrosion.
6.2.3. Corrosion protection
There are several methods to protect metals against corrosion. The most widely used are:
Coating the metal with a layer of another metal that is more active (better reducer).
Steel, for example, can be coated with zinc (galvanized steel). As the electrode potentials show, zinc is more easily oxidized
than iron, and therefore, when the metal is oxidized, zinc is oxidized instead of iron. Any initial oxidation of iron will be
accompanied by a reduction of its oxide or hydroxide from Zn to Fe. While zinc and iron are in contact, zinc protects iron
from oxidation (see figure), even if the zinc layer is damaged. Zn is the anode and Fe is the cathode.

 Covering the metal with a layer of another metal that is less active.
Such are nickel-plated steels. Nickel is less active than iron and is also passivated. Thus, the Ni layer protects the steel from
rusting. Unlike the previous case, the violation of the nickel layer will lead to corrosion of the iron. In this case, Fe is the
anode and Ni is the cathode.
 Passivation of the metal surface
Treatment with organic and inorganic substances to obtain a thick layer of oxide or other chemical composition.
Protection by alloying
Other metals (alloys) or non-metals are "introduced" into the parent metal to give corrosion-resistant products. Some of the
most commonly used stainless steels are chromium-nickel, vanadium and chromium-vanadium.
Insulation of the metal from the corrosive environment.
Creating protective coatings on the metal surface consisting of high molecular organic compounds or creating a coating of
inorganic substances (ceramics).
Stainless steels or other alloys are widely used in the manufacture of dental instruments. These include stainless steels, other
iron alloys for dental purposes, chromium-nickel, chromium-cobalt and cobalt-chromium-molybdenum alloys. Chromium
and molybdenum improve corrosion resistance.
Metal-ceramic tooth crowns are the most commonly used in practice fixed dental coatings (crowns and bridges). They are
made of metal alloys and ceramic masses, which are chemically and mechanically connected. They are made of a metal
skeleton (core) produced of a special alloy. This alloy can be made of precious metals such as gold and platinum. These
alloys are not often used in modern dentistry, as they can cause allergies, although rarely. For this reason, silver-tin-platinum
alloys are more commonly used. The base of metal ceramics can also be made of base alloy. They are used quite often in
practice due to their lower cost. A special highly aesthetic ceramic (porcelain) is applied on the metal skeleton. The most
commonly used base alloys are chromium-nickel and chromium-cobalt alloys. In recent years, the use of bioinert titanium
alloys has begun, with the demand for titanium-containing denture alloys increasing in line with the increasing rate of use of
dental implants.
5.2.4. Corrosion of hydroxyapatite

Caries is the destruction of the hard tissues of the tooth - enamel and dentin. The formation of caries is due to acidic
dissolution of tooth enamel and decomposition of the protein content of the underlying tooth structure. Bacteria from dental
plaque, carbohydrates from food and saliva are actively involved in this process. In general, the bacteria in the plaque
process the carbohydrates from the food, forming acids that come in contact with the tooth enamel. As a result of the acidic
environment in which it is located, the tooth begins to release calcium ions. As a result, the tooth structure becomes brittle,
microcavities appear, into which bacteria enter and the process continues deeper and deeper into the tooth. The role of saliva
is also to neutralize the acidity around the tooth through various mechanisms, but when the amount of dental plaque is large,
it is difficult to deal with it and at some stage caries develops.
Enamel is a white-yellow cell-free tissue that covers the surface of a tooth. It consists mainly of inorganic substances, 97% of
which are hydroxyapatite and a small amount of chemical components such as fluoroapatite. Enamel is important for the
function of the teeth and when damaged, it can cause further destruction of the teeth. Our bones consist of 50%
hydroxyapatite, and its high resistance to physiological conditions gives the bones their characteristic hardness.
Hydroxyapatite performs its function in the bones, accompanied by collagen, a fibrous connective tissue protein.
The chemical formulae of hydroxyapatite and fluoroapatite, as well as their structure are presented below:
hydroxyapatite Ca10(PO4)6(OH)2
respectively
3Ca3(PO4)2.Ca(OH)2 As mentioned, dental caries is the destruction of
tooth enamel under the action of acidic agents.
Among the main destroyers of tooth enamel is
lactic acid, which is produced by the breakdown
of sucrose by bacteria in the oral cavity. In the
fluoroapatite Ca10(PO4)6(F)2 case of acid destruction of the enamel, the
respectively following processes take place:
3Ca3(PO4)2.CaF2
Ca10(PO4)6(OH)2 + 8H+ → 6CaHPO4 + 4Ca2+ + 2H2O
CaHPO4 + H+ → Ca2+ + H2PO4-

As a result of these processes, there is a gradual destruction (in this case dissolution) of tooth enamel. This can be illustrated
by the data in the table regarding the solubility of these compounds.
The structure of hydroxyapatite includes hydroxide ions, which are
Compound Solubility a strong base because their conjugate acid - water is very weak
(mol/L)
(pKa(H2O) = 15.7). On the other hand, fluoroapatite contains
Ca10(PO4)6(OH)2 9,1.10-6
fluoride ions instead of hydroxide ions. They are much weaker
CaHPO4 5,2.10-4
bases than hydroxide ions because the pKa of the conjugate acid
Ca(H2PO4)2 1,2.10-1
HF is 3.1. Fluoroapatite is more stable and resistant to acid than
hydroxyapatite - the main component of enamel, and the reaction
with acids shown below is much less common.
 Ca10(PO4)6(F)2 + 8H+ → 6CaHPO4 + 4Ca2+ + 2HF

The destruction of tooth enamel under the action of acids is called demineralization. When
these acids, such as citric acid (pKa,1 = 3.1; pKa,2 = 4.7; pKa,3 = 6.4), can give anions
capable of forming relatively stable complexes with calcium ions, they facilitate the
demineralization process:

The reverse process, mineralization can take place in the

presence of fluoride ions. They help to form fluoroapatite.

Use of fluorides - their introduction into toothpastes, intake of fluoride-rich waters, and their local application plays an
important role in the prevention of caries. They protect the enamel from the demineralizing action of acidic bacterial products
by embedding in the enamel in the form of fluoroapatite. The crystals of hydroxyapatite that predominate in the enamel
interact with fluoride ions, whereby the hydroxide ions are replaced by fluoride:

Ca10(PO4)6(OH)2 + 2F-  Ca10(PO4)6(F)2 + 2OH-

The more fluoroapatite it contains, the more stable the enamel. For a long time, NaF was used as the main source of fluoride
ions in toothpastes. It is very soluble in water, which creates a problem due to the high toxicity of F-. Fluoride ions form
strong hydrogen bonds with proteins, leading to their denaturation. To overcome this problem, CaF2, which has a very low
solubility in water, is increasingly used in toothpastes. Calcium difluoride crystals are incorporated into the enamel
(fluoroapatite can be considered as 3Ca3(PO4)2.CaF2).
In recent years, the use of fluoride-free toothpastes has begun. They contain hydroxyapatite as the main ingredient.