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Example of a complex reaction: Reaction of hydrogen and nitric



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Example of a complex reaction: Reaction of hydrogen and nitric

oxide[edit]
For the reaction
2 H2(g) + 2 NO(g) → N2(g) + 2 H2O(g) the observed rate equation (or rate expression) is:
As for many reactions, the experimental rate equation does not simply reflect the stoichiometric coefficients in the overall reaction: It is third order overall: first order in H2 and second order in NO, even though the stoichiometric coefficients of both reactants are equal to 2.[2]
In chemical kinetics, the overall reaction rate is often explained using a mechanism consisting of a number of elementary steps. Not all of these steps affect the rate of reaction; normally the slowest elementary step controls the reaction rate. For this example, a possible mechanism is:

  1. 2 NO(g) ⇌ N2O2(g) (fast equilibrium)




  1. N2O2 + H2 → N2O + H2O (slow)

  2. N2O + H2 → N2 + H2O (fast)

Reactions 1 and 3 are very rapid compared to the second, so the slow reaction 2 is the rate determining step. This is a bimolecular elementary reaction whose rate is given by the second order equation:

where k2 is the rate constant for the second step.
However N2O2 is an unstable intermediate whose concentration is determined by the fact that the first step is in equilibrium, so that [N2O2] = K1[NO]2 , where K1 is the equilibrium constant of the first step. Substitution of this equation in the previous equation leads to a rate equation expressed in terms of the original reactants
This agrees with the form of the observed rate equation if it is assumed that k = k2K1. In practice the rate equation is used to suggest possible mechanisms which predict a rate equation in agreement with experiment.
The second molecule of H2 does not appear in the rate equation because it reacts in the third step, which is a rapid step after the rate-determining step, so that it does not affect the overall reaction rate.
Temperature dependence
Main article: Arrhenius equation

Each reaction rate coefficient k has a temperature dependency, which is usually given by the Arrhenius equation:


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Ea is the activation energy and R is the gas constant. Since at temperature T the molecules have energies given by a Boltzmann distribution, one can expect the number of collisions with energy greater than Ea to be proportional to eE aRT. A is the pre-exponential factor or frequency factor.
The values for A and Ea are dependent on the reaction. There are also more complex equations possible, which describe temperature dependence of other rate constants that do not follow this pattern.
A chemical reaction takes place only when the reacting particles collide. However, not all collisions are effective in causing the reaction. Products are formed only when the colliding particles possess a certain minimum energy called threshold energy. As a rule of thumb, reaction rates for many reactions double for every 10 degrees Celsius increase in temperature,[3] For a given reaction, the ratio of its rate constant at a higher temperature to its rate constant at a lower temperature is known as its temperature coefficient (Q).Q10 is commonly used as the ratio of rate constants that are 10 °C apart.
Pressure dependence
The pressure dependence of the rate constant for condensed-phase reactions (i.e., when reactants and products are solids or liquid) is usually sufficiently weak in the range of pressures normally encountered in industry that it is neglected in practice.

The pressure dependence of the rate constant is associated with the activation

volume. For the reaction proceeding through an activation-state complex:

A + B ⇌ |A⋯B| → P

the activation volume, V, is:
where denotes the partial molar volumes of the reactants and products and ‡ indicates the activation-state complex.
For the above reaction, one can expect the change of the reaction rate constant (based either on mole-fraction or on molar-concentration) with pressure at constant temperature to be:
In practice, the matter can be complicated because the partial molar volumes and the activation volume can themselves be a function of pressure.
Reactions can increase or decrease their rates with pressure, depending on the value of V. As an example of the possible magnitude of the pressure effect, some organic reactions were shown to double the reaction rate when the pressure was increased from atmospheric (0.1 MPa) to 50 MPa (which gives V = −0.025 L/mol).[10]
A chemical equation

A chemical equation is the symbolic representation of a chemical reaction in the form of symbols and formulae, wherein the reactant entities are given on the left-hand side and the product entities on the right-hand side.[1] The coefficients next to the symbols and formulae of entities are the absolute values of the stoichiometric numbers. The first chemical equation was diagrammed by Jean Beguin in 1615.[2]


A chemical equation consists of the chemical formulas of the reactants (the starting substances) and the chemical formula of the products (substances formed in

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the chemical reaction). The two are separated by an arrow symbol ( , usually read as "yields") and each individual substance's chemical formula is separated from others by a plus sign.
As an example, the equation for the reaction of hydrochloric acid with sodium can be denoted:
2 HCl + 2 Na → 2 NaCl + H

2

This equation would be read as "two HCl plus two Na yields two NaCl and H two." But, for equations involving complex chemicals, rather than reading the letter and its subscript, the chemical formulas are read using IUPAC nomenclature. Using IUPAC nomenclature, this equation would be read as "hydrochloric acid plus sodium yields sodium chloride andhydrogen gas."


This equation indicates that sodium and HCl react to form NaCl and H2. It also indicates that two sodium molecules are required for every two hydrochloric acid molecules and the reaction will form two sodium chloride molecules and one diatomic molecule of hydrogen gas molecule for every two hydrochloric acid and two sodium molecules that react. Thestoichiometric coefficients (the numbers in front of the chemical formulas) result from the law of conservation of mass and the law of conservation of charge (see "Balancing Chemical Equation" section below for more information).
Common symbols[edit]
Symbols are used to differentiate between different types of reactions. To denote the type of reaction:[1]


  • "=" symbol is used to denote a stoichiometric relation.

  • "→" symbol is used to denote a net forward reaction.




  • "" symbol is used to denote a reaction in both directions.

  • "" symbol is used to denote an equilibrium.

The physical state of chemicals is also very commonly stated in parentheses after the chemical symbol, especially for ionic reactions. When stating physical state,




  1. denotes a solid, (l) denotes a liquid, (g) denotes a gas and (aq) denotes an aqueous solution.

If the reaction requires energy, it is indicated above the arrow. A capital Greek letter delta () is put on the reaction arrow to show that energy in the form of heat is


added to the reaction. is used if the energy is added in the form of light. Other symbols are used for other specific types of energy or radiation.
Balancing chemical equations


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