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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, ΔV, is:

{\displaystyle \Delta V^{\ddagger }={\bar {V}}_{\ddagger }-{\bar {V}}_{\mathrm {A} }-{\bar {V}}_{\mathrm {B} }}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:

{\displaystyle -RT\left({\frac {\partial \ln k_{x}}{\partial P}}\right)_{T}=\Delta V^{\ddagger }}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 ΔV. 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 ΔV = −0.025 L/mol).[10]

chemical equation 

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 the chemical reaction). The two are separated by an arrow symbol ({\displaystyle \rightarrow }, 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]

  • "{\displaystyle =}=" symbol is used to denote a stoichiometric relation.

  • "{\displaystyle \rightarrow }→" symbol is used to denote a net forward reaction.

  • "{\displaystyle \rightleftarrows }" symbol is used to denote a reaction in both directions.

  • "{\displaystyle \rightleftharpoons }" 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, (s) 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 ({\displaystyle \Delta }) is put on the reaction arrow to show that energy in the form of heat is added to the reaction. {\displaystyle h\nu } 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


As seen from the equation CH

4 + 2 O

2 → CO


2 + 2 H

2O, a coefficient of 2 must be placed before the oxygen gas on the reactants side and before the water on the products side in order for, as per the law of conservation of mass, the quantity of each element does not change during the reaction





P4O10 + 6 H2O → 4 H3PO4

This chemical equation is being balanced by first multiplying H3PO4 by four to match the number of P atoms, and then multiplying H2O by six to match the numbers of H and O atoms.

The law of conservation of mass dictates that the quantity of each element does not change in a chemical reaction. Thus, each side of the chemical equation must represent the same quantity of any particular element. Likewise, the charge is conserved in a chemical reaction. Therefore, the same charge must be present on both sides of the balanced equation.

One balances a chemical equation by changing the scalar number for each chemical formula. Simple chemical equations can be balanced by inspection, that is, by trial and error. Another technique involves solving a system of linear equations.

Balanced equations are written with smallest whole-number coefficients. If there is no coefficient before a chemical formula, the coefficient 1 is understood.

The method of inspection can be outlined as putting a coefficient of 1 in front of the most complex chemical formula and putting the other coefficients before everything else such that both sides of the arrows have the same number of each atom. If any fractional coefficient exists, multiply every coefficient with the smallest number required to make them whole, typically the denominator of the fractional coefficient for a reaction with a single fractional coefficient.

As an example, seen in the above image, the burning of methane would be balanced by putting a coefficient of 1 before the CH4:

1 CH4 + O2 → CO2 + H2O

Since there is one carbon on each side of the arrow, the first atom (carbon) is balanced.

Looking at the next atom (hydrogen), the right-hand side has two atoms, while the left-hand side has four. To balance the hydrogens, 2 goes in front of the H2O, which yields:

1 CH4 + O2 → CO2 + 2 H2O

Inspection of the last atom to be balanced (oxygen) shows that the right-hand side has four atoms, while the left-hand side has two. It can be balanced by putting a 2 before O2, giving the balanced equation:

CH4 + 2 O2 → CO2 + 2 H2O

This equation does not have any coefficients in front of CH4 and CO2, since a coefficient of 1 is dropped.



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