23/09/2017 KINETIC OF THE CHEMICAL REACTION

KINETIC OF THE CHEMICAL REACTION

Rate of a chemical reaction

Chemical equilibrium

RATE OF A CHEMICAL REACTION

The rate of a reaction is the rate at which products are formed or the rate at which reactants are used up in the reaction. The rate of a reaction is
defined by change of molar concentrations of one of the reacting substances:

С2 - С1 DС
V=± ––––– =± –––
t2 - t1 Dt

where C1 and C2 - are molar concentrations of substance at moments of the time t1 and t2 respectively. Symbol (+) if the rate is defined on the
product of reactions, symbol (-) if the rate is defined on the initial substance.
Reaction occurs at the colliding of molecules of reacting substances. Its rate is determined by quantity of collisions and by probability that this
process bring about the conversion. The number of collisions is determined by concentrations of reacting substances, but probability of reactions
is determined by energy of colliding molecules.

Numbers of factors influencing on the rate of any particular reaction

The most important of these are:
the nature of reactants;
concentration of reactants;
temperature;
presence of catalysts.
Below, the influence of each factor on the rate of chemical reactions is described.
1. Dependence of reaction rate on the nature of reactants. The character of chemical bonds and structure of reactant molecules has a great
importance. Reactions run toward destroying of less strong bonds and stronger substances are formed. Thus, for a bonds breakup in
molecules H2 and N2 high energies are required; such molecules have small reaction ability. For a bonds breakup in strong polarized
molecules (HCl, H2O) less energy is required and the rate of reactions well above. Reactions between ions in solutions of electrolytes run
practically instantly.
examples
1) Fluorine react with hydrogen with explosion at the room temperature, bromine slowly interact with hydrogen under the heating.
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2) Calcium oxide energetically reacts with water with extracting of heat; cooper oxide - does not react.
2. Dependence of reaction rate on the reactant concentrations. The rate of a reaction is proportional to the number of collisions experienced by
the molecules of the reactant. The number of collision grows with the concentration of each of the reactant (the number of particles in the unit
of volume are growing), thus the rate of a reaction is increasing.

Low of mass action

(C. Guldberg and P. Waage in 1867)

At a constant temperature, the rate of a chemical reaction is directly proportional to the product of the concentrations of the reactants.

aA + bB + . . . ® . . .

V = k * [A]a * [B]b * . . .

The value of the rate constant k depends on the nature of the reactant, on the temperature, and on the presence of catalysts, but does not
depend on the concentration of the substances.
The physical meaning of the rate constant is: its equal to the rate of a reaction at the singles concentrations of the reactants.
For heterogeneous reactions the concentration of solid phase does not include in the expression of the rate of a reaction.
3. Dependence of reaction rate on the temperature. When the temperature of the system increases by each 10°C the rate of a reaction
increases in 2-4 times (Vant-Hoff rule). In the time of a temperature increases from till the change of reaction rate is possible to calculate:

Vt2 (t2 - t1)/10

–– = g
Vt1

(Vt2 and Vt1 - is a reactions rate at temperatures t2 and t1 correspondingly, g- is a temperature coefficient of reaction).
Vant-Hoff rule is applicable in the narrow interval of temperatures only. More exact is Arrhenius equation:

k = A * e -Ea/RT

A - is a constant for the reaction depends on the nature of reactant;

R - is the gas constant {8.314 J/mol * K)=0.082 liters * atm/(mol * K);
Ea - is the activation energy, i.e. the excess energy that molecules must have for their collision been effective.

Energy diagram of chemical reaction

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Reaction coordinate Reaction coordinate

Endothermic reaction Exothermic reaction

A - reagents, B- activated complex (transition state), C - products.

Than energy of activation Ea higher that more strong increases of the rate of a reaction when increasing a temperature is observed.
4. Dependence of reaction rate on the surface of reactants. For heterogeneous systems (when reactants stand in the different aggregation
condition) the greater contact surface the reaction runs faster. The surface of solid substances can be increase by means of shallower, but for
soluble substances by means of dissolution.
5. Catalysis. Substances that are not consumed in a reaction, but affect its rate, are called catalysts. The phenomenon of the change in the rate
of a reaction under the action of such substances is known as catalysis. Reactions proceeding under the action of catalysts are called
catalytic. The action of a catalyst in the majority of cases is explained by the fact that it lowers the activation energy of a reaction. In
homogeneous catalysis, the catalyst and the reactant form a single phase (stand in one the same aggregation condition), in heterogeneous
catalysis, the catalyst forms an independent phase (stand in the different aggregation condition). In number of events sharply slow down the
undesirable chemical reactions by means of adding in the reactionary ambience inhibitors is possible (phenomena of «negative catalysis»).

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Reversible reactions - chemical reactions, simultaneously running in two opposite directions.

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Chemical equilibrium - is a system condition, in which the rate of direct reaction (V1) is equal to the rate of inverse reactions (V2). At chemical
equilibrium concentrations of substances stay unchangeable. Chemical equilibrium is called dynamic equilibrium. This stresses the fact that both
the forward and reverse reactions proceed in equilibrium, but their rates are the same, and as a result no changes are noticeable in the system.
Chemical equilibrium is characterized quantitatively by a quantity known as the chemical equilibrium constant. Equilibrium constant is a relation of
constants of forward (K1) and reverse (K2) reactions.
For reaction mA + nB « pC + dD equilibrium constant is

K1 [C]p * [D]d
K = –– = –––––––
K2 [A]m [B]n
*

The magnitude of the equilibrium constant depends on the nature of the reacting substances and on the temperature. It does not depend on the
presence of catalyst. Since a catalyst changes the activation energy of both the forward and reverse reactions by the same amount, it does not
affect the ratio of their rate constant.

Displacement of chemical equilibrium

Le Chatelier’s principle. Any system in stable chemical equilibrium, when subjected to the influence of an external cause which tends to change
either temperature or condensation (pressure, concentration, number of molecules in unit volume), throughout or in only some of its part, can
undergo only such internal modifications which, if they occurred on their own, would bring about a change of temperature or of condensation of a
sign contrary to that resulting from the external cause.

V1
A+Б « В
V2

1. Pressure. When the pressure is increased by compressing a system, equilibrium shifts in the direction of a reduction in the number of
molecules of the gases (i.e. in the direction of lowering pressure).

V1
A + Б « В ; increasing P brings about V1 > V2
123 V2 {
2 1

2. Temperature. Upon elevation of the temperature, equilibrium shifts in the direction of the endothermic reaction (i.e. aside reaction, running
with absorbing a heat).
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V1
A + Б « В + Q, increasing t°C brings about V2 > V1
V2

V1
A + Б « В - Q, increasing t°C brings about V1 > V2
V2

3. Increasing a concentration of source substances and removing the products from the reaction sphere shift equilibrium in the direction of
forward reaction. Increasing the concentrations of source substances [A] or [Б] or [A] and [Б]: V1 > V2
4. Catalyst has no influence on the position of equilibrium.

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