CHEMICAL EQUILIBRIUM

Contents for this page Reversible reactions Dynamic equilibrium The equilibrium constant Additional questions Related topics Reaction rates Catalysis Le Chatelier's principle Learning Outcomes After studying this section, you will (a) understand what is meant by a dynamic equilibrium, (b) understand the meaning of the equilibrium constant, Kc, and (c) know how to formulate the expressions by means of which it may be calculated, and (d), be able to perform calculations involving the equilibrium constant.

Data Glossary

Reversible reactions:
Many chemical reactions give rise to products which are capable of reacting in such a way as to give back the original reactants:

For example, at 20 C, two molecules of the gas NO2 can react to form one molecule of another gas, N2O4. But this gas in turn is not very stable, and can dissociate at 20 C into two molecules of NO2.

We say that this reaction is REVERSIBLE, and indicate this by the symbol

Dynamic equilibrium:
Reversible reactions give rise to a state of DYNAMIC EQUILIBRIUM, where the products of the reaction are converted back into the reactants from which they were derived as fast as they are formed. In other words, at equilibrium, the rates of the forward and reverse reactions are exactly the same:

When a reversible reaction has established a dynamic equilibrium, things just don't stand still! There are countless numbers of A and B molecules being converted to C and D, and vice versa. The MOST IMPORTANT thing to bear in mind is that when equilibrium has been reached, the CONCENTRATIONS of A, B, C and D do not change with time - they have reached a CONSTANT value. In the animation you are about to see here on the right, watch how the concentrations of A and B change with time. Initially, we start with A at some fixed concentration [A]0, while the concentration of B, [B]0 = 0. As time progresses, the concentration of A decreases, while that of B increases by the same amount. At some time, the concentrations of both A and B remain unchanged. Equilibrium has been reached! (Start the animation.)

The equilibrium constant:

Consider a general case of a reversible reaction

It is a fact that when equilibrium has been established, the concentrations of A, B, C and D are constant. (We write [A] for the concentration of A, [B] for the concentration of B, and so on). Under a given set of conditions, such as a constant temperature, the concentrations of the reactants and products are linked by the expression

where Kc is the EQUILIBRIUM CONSTANT. The equilibrium constant Kc has a value which will be fixed for each reversible reaction, under a particular set of conditions (notably temperature).

It is most important to note that the expression

describing the equilibrium constant Kc is valid only at equilibrium. The concentrations in the expression for Kc must be those concentrations actually found at equilibrium. The implication of the equilibrium constant is that no matter what the initial concentrations of reactants and/or products might be, the reaction will take place in such a manner that at equilibrium, the concentration values will have adjusted so that [C][D]/[A][B] will equal the appropriate value of Kc. For the generally stated reversible reaction

the equilibrium constant is given by

where a is the number of molecules of A taking part in the reaction, b the number of molecules of B, and so on.

As an example take the reaction

The equilibrium constant is

(Easy) (More difficult)

Additional questions

The reaction between hydrogen and iodine at 700K is described by the equilibrium

In a certain experiment at 700 K, the various concentrations at equilibrium were found to be [H2] = 1.84 x 10-3 mol.dm-3 [I2] = 3.13 x 10-3 mol.dm-3 [HI] = 17.7 x 10-3 mol.dm-3 Calculate Kc for this equilibrium at 700K. Solution: Apply the appropriate equation for the equilibrium constant

I2 (3.0 x 10-2 moles) and H2 (2.0 x 10-2 moles) were mixed in a closed container and heated to 700K. The equilibrium constant Kc for the reaction is 55. How many moles of HI will be present at equilibrium?

Solution: This requires a number of steps. Step 1: Set up a "balance sheet" using symbols for the amounts of the reactants and products: I2 Amount (moles) at the start Amount (moles) used up Amount (moles) formed Amount at equilibrium Concentration at equilibrium (mol.dm ) where V is the unknown volume of the container. Step 2: Write down the equation linking the equilibrium constant Kc with the equilibrium concentrations:
-3

H2 n x 0 n-x (n - x)/V

HI 0 0 2x 2x 2x/V

m x 0 m-x (m - x)/V

Note that the volume V cancels out, so its value is irrelevant. This may not always be true for other reactions! Step 3: Rearrange the equation to give a quadratic equation in the standard form ax2 + bx + c = 0:

Step 4: Solve for x, using the formula used to solve quadratic equations:

Therefore, x = 3.6 x 10-2 or x = 1.8 x 10-2. The first value must be rejected, since it is greater than the starting amount of either H2 or I2. The amount of HI formed is 2x, i.e. 3.6 x 10-2 mol. NOTE: By approaching the problem in an algebraic manner, one can easily keep track of the various steps, and the arithmetic can be done right at the end. This makes it easy to go over the calculations in order to check the answer.

Solving quadratic equations: For a general quadratic equation y = x2 + bx + c, the roots of the equation (i.e., the values of x when the equation is zero, y = 0), are given by