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PHYSICAL CHEMISTRY FOR TEXTILE

9. Chemical Equilibrium L16: chemical equilibrium, reversible reactions, law of mass action, law of chemical equilibrium

CHEMICAL EQUILIBRIUM
In

general equilibrium is a state where all the forces acting on anything are equal and opposite or the equilibrium is a balance of forces. For example a book lying on a table is in equilibrium since all the forces acting downward and upward are balanced and there is no motion. When we consider such an equilibrium state in chemical reactions, it is called chemical equilibrium.
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CHEMICAL EQUILIBRIUM

Not all the chemical reactions that occur go to completion.


Some reactions go to completion where all the reactants are converted into products, for e.g. sodium bicarbonate reacts with hydrochloric acid to produce sodium chloride, water and carbon dioxide. In this reaction the reactants are completely converted into products. However some reactions stop when a certain amount of reactants has converted into products under certain fixed conditions. These reactions are said to be in a state of equilibrium.

For example CO2 dissolves in water under high pressure according to the equation: CO2 (aq) + H2O (l) HCO3- (aq)+ H+ (aq)
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If high pressure is maintained the equilibrium lies to the right, but on releasing pressure the equilibrium shifts to the left.

CHEMICAL EQUILIBRIUM

The equilibrium can be of two types:


Static equilibrium: is that in which every type of change has stopped when the system is in equilibrium. For instance if we consider again the example of book lying on table on which all the forces are balanced and absolutely no change is occurring. Dynamic equilibrium: is that in which although the reaction as a whole has stopped and there is no more change in the quantities of reactants and products but the reaction in fact has not stopped. In these reactions a reverse reaction is also occurring and at equilibrium the rate of reverse reaction becomes equal to the forward reaction. Hence although no net change is occurring but reactants and products are continuously converting into one another.

The position of equilibrium is defined as if at equilibrium the reactants are more than the products, the equilibrium is said to lye to the left. However, if the products are more than the reactants, the equilibrium is said to lye to the right. 4

REVERSIBLE REACTIONS
In organic chemistry most of the reactions are bidirectional i.e. they can proceed in both directions, from reactants to products or from products to reactants. However the amount of product formed depends on the relative speed of both forward and reverse reactions before the equilibrium is established. The position of equilibrium, however depends also on the reaction conditions like temperature, pressure, concentration etc. On the other hand if there is no reverse reaction, the reaction will go to completion and no reactants will remain at the end of reaction. In organic chemistry such reactions are usually found in polymerizations. 5

KINETICALLY AND THERMODYNAMICALLY CONTROLLED REACTIONS


If

a reaction is thermodynamically possible but it does not proceed reasonably rapidly (i.e. the rate of reaction is very slow), it is called a kinetically controlled reaction. If on the other hand the reaction is reasonably rapid but proceeds to only a small extent, it is called thermodynamically controlled reaction.
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LAW OF MASS ACTION


For a homogenous system the rate of a chemical reaction is proportional to the active masses of the reacting substances. The molecular concentration of a substance in solution or in the gas phase is taken as a measure of its active mass. If two substances A and B take part in a reversible reaction in which the products are C and D, and a, b, c and d are their molar concentrations, the reaction may be written as follows:

aA + bB

cC + dD
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LAW OF MASS ACTION


Then

according to the law of mass action the rate of either of the forward or reverse reaction is proportional to the product of active masses of the various components involved in reaction, therefore: rate of forward reaction = kf [A]a[B]b rate of reverse reaction = kr [C]c[D]d In these equations k represents the rate constant and the square brackets represent molar concentrations of reactants and products.

LAW OF MASS ACTION


When we combine the reactants A and B, the forward reaction starts immediately, but due to formation of products, reverse reaction also gets underway. As the reaction proceeds the rate of forward reaction diminishes, and the rate of reverse reaction increases. Eventually both the forward and reverse reactions fall to the same reaction rate, and the reaction is said to be in equilibrium. Hence: rate of forward reaction = rate of reverse reaction kf [A]a[B]b = kr [C]c[D]d

LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT

If we consider a homogenous reversible reaction, aA + bB cC + dD the rates of which are kf [A]a[B]b and kr [C]c[D]d respectively, then at equilibrium the rates of both the forward and reverse reactions are the same, and hence: kf [A]a[B]b = kr [C]c[D]d Or kf /kr = [C]c[D]d /[A]a[B]b = Kc

The constant Kc is called the equilibrium constant of the reaction. This equation, derived from the law of mass action, is referred to as the law of chemical equilibrium which states that whatever are the initial concentrations of reactants and products, the concentrations at equilibrium are related to each other in such a way that the value of Kc remains constant.

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LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT


Initial concentration (mol/L) CH3COOH 1.00 1.00 1.00 1.00
C2H5OH

S. No 1 2 3 4

Concentration at equilibrium (mol/L) Reactants Products


CH3COOH C2H5OH CH3COOC2H5

Equilibr ium

H2O 0.171 0.667 0.888 0.966

Constant

0.18 1.0 2.0 3.0

0.829 0.333 0.142 0.034

0.009 0.333 1.142 2.034

0.171 0.667 0.888 0.966

3.9 4.0 4.5 3.9


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LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT


When

chemical reactions are carried out in solution, the equilibrium constant is given by the following equation: Kc = [C]c[D]d /[A]a[B]b It follows from this equation that if more product is formed and less reactants are left at equilibrium, Kc will have a larger value. While if less product is formed and more reactants are left at equilibrium, the value of Kc will be smaller.

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LAW OF CHEMICAL EQUILIBRIUM


We

can draw the following important conclusions from the above discussion:
When

Kc is large the equilibrium mixture will contain a high proportion of products, i.e. the reaction will go nearly to completion. When Kc is small the reaction does not proceed very far under the given reaction conditions and the concentration of product formed is low. The value of Kc does not change by the addition of more reactants or products to the equilibrium mixture if the reaction conditions are kept 13 constant.

LAW OF CHEMICAL EQUILIBRIUM

Considering the following equation, aA + bB cC + dD Kc = [C]c[D]d /[A]a[B]b

if some additional B is added the value of expression will not stay equal to Kc, however, some of the B will react with A to produce more C and D until the proportion of reactants and products again become equal to equilibrium value of Kc. If on the other hand some of the product is added to equilibrium mixture, it will convert to the reactants to establish equilibrium Although there is no rule but for most practical purposes the value of K within the rage from 0.01 to 100 is considered significant, which indicates that chemically significant amount of all the components of the reaction 14 system will be present in an equilibrium mixture and that the reaction will be incomplete or reversible.

SIGNIFICANCE OF KC

When Kc for a reaction is known, the relative proportions of the reactants and products at equilibrium can be calculated for any mixture of reactants used initially. For the previously considered esterification reaction, the reaction equation will be as follows:

CH3COOH(l) + C2H5OH(l) H2O(l)


Equation for Kc will be as follows:

CH3COOC2H5(l) +

Kc=[CH3COOC2H5(l)] [H2O(l)] /[CH3COOH(l)] [C2H5OH(l)]

If considering one mole each of acetic acid and alcohol at start of reaction and Kc=4, the ratio of products and reactants will be: Kc = 4 = 4/1 = 2/1 Ratio of products to reactants will be = [0.666] [0.666] / [0.333] [0.333]
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UNCHANGING CONCENTRATION IN EQUILIBRIUM EXPRESSIONS

Substances whose concentration do not undergo significant change in a chemical reaction do not appear in equilibrium constant expressions. There two such general cases which are considerable:
The

substance is also a solvent The substance is a solid or a pure liquid phase.

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ONE OF REACTION COMPONENTS IS SOLVENT OF REACTION MIXTURE


Considering

an acid base reaction,


NaCl (aq)+ H2O

HCl (aq) + NaOH (aq)

we know that in acid base reactions, one of the products is water, therefore, if the reaction is carried out in aqueous medium, the concentration of water will not change appreciably. Hence concentration of water will not appear in the expression of equilibrium constant.
Kc = [NaCl(aq)] / [HCl(aq)] [NaOH(aq)]
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ONE OF REACTION COMPONENTS IS SOLVENT OF REACTION MIXTURE


In

organic reactions if a condensation reaction is carried out in aqueous medium, the concentration of condensate brings negligible change and is therefore not considered in equation for Kc. An example is the formation of water soluble amides from organic acids and amines. Amide formation is a condensation reaction in which water is produced as byproduct.

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SOLID REACTION COMPONENT OR PURE LIQUID PHASE

When one or more of the components of a reaction are solid, their concentration cannot be defined and cannot be included in the expression of equilibrium constant. For example the decomposition reaction of CaCO3 to give CaO and CO2 the reaction is as follows: CaCO3 CaO + CO2 The equilibrium constant for this equation does not include the solid components and hence the equation is: Kc = [CO2(g)]
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