Chemical Equilibria

Chemical Change
Occurs when the atoms that make up one or more substances rearrange themselves in such a way that new substances are formed.

These substances are the components of the chemical reaction system; those components which decrease in quantity are called reactants, while those that increase are products.

A given chemical reaction system is defined by a balanced net chemical equation which is conventionally written as reactants ? products The first thing we need to know about a chemical reaction represented by a balanced equation is whether it can actually take place. If the reactants and products are all substances capable of an independent existence, then the answer is always "yes.

This answer must always be qualified by the following two considerations: the reaction take place to a sufficient extent to produce useful (or even detectable) quantities of products the mechanism of the reaction What happens, at the atomic or molecular level, when reactants are transformed into products? What intermediate species are involved?

A reaction that is thermodynamically possible but for which no reasonably rapid mechanism is available is said to be kinetically limited. One that occurs rapidly but only to a small extent is thermodynamically limited.

What is equilibrium? Basically, the term refers to what we might call a "balance of forces". A book sitting on a table top remains at rest because the downward force exerted by the earth's gravity acting on the book's mass is exactly balanced by the repulsive force between atoms that prevents two objects from simultaneously occupying the same space. mechanical equilibrium

If we pick up the book and raise it above the table top, the additional upward force exerted by our arm destroys the state of equilibrium as the book moves upward. If we wish to hold the book at rest above the table, we adjust the upward force to exactly balance the weight of the book, thus restoring equilibrium.

Another kind of equilibrium we all experience is thermal equilibrium. When two objects are brought into contact, heat will flow from the warmer object to the cooler one until their temperatures become identical. Thermal equilibrium is a "balance of forces" in the sense that temperature is a measure of the tendency of an object to lose thermal energy.

Thermal equilibrium is something we often want to avoid; this is why people insulate buildings, perspire in the hot and wear heavier clothing in the winter.

Chemical equilibrium When a chemical reaction takes place in a container which prevents the entry or escape of any of the substances involved in the reaction, the quantities of these components change as some are consumed and others are formed. Eventually this change will come to an end, after which the composition will remain unchanged as long as the system remains undisturbed.

The system is then said to be in its equilibrium state, or more simply, "at equilibrium". A chemical reaction is in equilibrium when there is no tendency for the quantities of reactants and products to change. The direction in which we write a chemical reaction (and thus which components are considered reactants and which are products) is arbitrary.

Thus the two equations H2 + I2 2 HI "synthesis of hydrogen iodide"

2 HI H2 + I2 "dissociation of hydrogen iodide" represent the same chemical reaction system in which the roles of the components are reversed, and both yield the same mixture of components when the change is completed.

This is central to the concept of chemical equilibrium. It makes no difference whether we start with two moles of HI or one mole each of H2 and I2; once the reaction has run to completion, the quantities of these two components will be the same. In general, then, we can say that the composition of a chemical reaction system will tend to change in a direction that brings it closer to its equilibrium composition.

Once this equilibrium composition has been attained, no further change in the quantities of the components will occur as long as the system remains undisturbed.

Reversible reactions A reversible reaction is one which can be made to go in either direction depending on the conditions. If we pass steam over hot iron the steam reacts with the iron to produce a black, magnetic oxide of iron called triiron tetroxide, Fe3O4.

The hydrogen produced in the reaction is swept away by the stream of steam.

Under different conditions, the products of this reaction will also react together. Hydrogen passed over hot triiron tetroxide reduces it to iron. Steam is also produced.

This time the steam produced in the reaction is swept away by the stream of hydrogen.

These reactions are reversible, but under the conditions normally used, they become oneway reactions. The products aren't left in contact with each other, so the reverse reaction can't happen.

Reversible reactions happening in a closed system A closed system is one in which no substances are either added to the system or lost from it. Energy can, however, be transferred in or out at will. In the example we've been looking at, we would have to imagine iron being heated in steam in a closed container. Heat is being added to the system, but none of the substances in the reaction can escape. The system is closed.

As the triiron tetroxide and hydrogen start to be formed, they will also react again to give the original iron and steam. So, if we analysed the mixture after a while, what would we find? We would find that we had established what is known as a dynamic equilibrium.

Thinking about reaction rates

This is the equation for a general reaction which has reached dynamic equilibrium How did it get to that state? Let's assume that we started with A and B.

At the beginning of the reaction, the concentrations of A and B were at their maximum. That means that the rate of the reaction was at its fastest. As A and B react, their concentrations fall. That means that they are less likely to collide and react, and so the rate of the forward reaction falls as time goes on.

In the beginning, there isn't any C and D, so there can't be any reaction between them. As time goes on, though, their concentrations in the mixture increase and they are more likely to collide and react. With time, the rate of the reaction between C and D increases.

Eventually, the rates of the two reactions will become equal. A and B will be converting into C and D at exactly the same rate as C and D convert back into A and B again.

At this point there won't be any further change in the amounts of A, B, C and D in the mixture. As fast as something is being removed, it is being replaced again by the reverse reaction. We have reached a position of dynamic equilibrium.

Summary
A dynamic equilibrium occurs when we have a reversible reaction in a closed system. Nothing can be added to the system or taken away from it apart from energy. At equilibrium, the quantities of everything present in the mixture remain constant, although the reactions are still continuing. This is because the rates of the forward and the back reactions are equal.

 If we change the conditions in a way which changes the relative rates of the forward and back reactions we will change the position of equilibrium in other words, change the proportions of the various substances present in the equilibrium mixture.

Equilibrium Constant
Writing Equilibrium Constant Expressions Concept of equilibrium constants is important in chemistry Equilibrium constants are the key to solving a wide variety of stoichiometry problems involving equilibrium systems

q an industrial chemist who wants to maximize the yield of sulfuric acid must have clear understanding of equilibrium constants for all steps in the process, starting from the oxidation of sulfur and ending with the formation of acid q a physician specializing in clinical cases of acid-base imbalance needs to know the equilibrium constants of weak acids and bases q an environmental chemist must has a knowledge of equilibrium constants of pertinent gas-phase reactions, will help him better understand the process of ozone destruction in the stratosphere

To use equilibrium constants, we must express them in terms of the reactant(s) and product(s) concentrations Our only guide is the law of mass action which is the general formula for finding equilibrium concentrations

Law of Mass Action

States that for a reversible reaction at equilibrium and a constant temperature, a certain ratio of reactant and product concentrations has a constant value K (the equilibrium constant). In general, a reversible reaction is written as: aA + bB cC + dD

where a, b, c, and d are the stoichiometric coefficients for the reacting species A, B, C, and D

For the reaction at a particular temperature, the equilibrium constant is K= [C]c[D]d [A]a[B]b

The above equation was formulated by two Norwegian chemists, Cato Guldberg and Peter Waage in 1864. Note that although the concentrations may vary, as long as a given reaction is at equilibrium and the temperature does not change, according to the law of mass action, the value of K remains constant.