reversible reactions and equilibrium

Reversible reactions and equilibrium

Consider the following reaction:
reversible reaction equations

combustion reaction In this topic we are not concerned with the reacting chemical or the products of the reaction but with the arrow → , in the above equation. This arrow tells us that the reaction goes to completion. This means that all (100%) of the reactants are turned into products. Most of the equations you have seen in science will probably have used this type of arrow. However very few reactions occur where all the reactants are turned into products. Neutralisation, metal acid reactions and combustion are a few examples of reactions that you will have met that go to completion.

Reversible reactions

Most chemical equations are written with a different arrow:
reversible reaction This equation might look very similar to the one above except for the arrow, which is obviously different. However this reaction is very different from the one mentioned above. You can think of it as two separate reactions that are happening at the same time reversible reactions

The important fact is that these two reactions are happening at the same time. The equation below basically shows two reactions in one!

A + B C + D
As A and B react and turn into C and D, C and D are reacting and turning back into A and B. The reaction is reversible. Both these reactions happen at the same time. reversible reaction We can use the symbols Rf and Rb to represent the rates of the forward and reverse reactions. It is a common error to assume that these two rates are equal, but this is rarely the case. It is important to realise that during this reversible reaction you will end up with a mixture of A, B, C and D once the reaction gets going. The proportions of A, B, C and D will depend to a large extend on the rate of the forward and reverse reactions.

The simple diagram below may help to give you a mental picture of what is happening during a reversible reaction. Here the large glass troughs are filled with water, the water in each trough represents the reactants and products in a reaction. The amount of water in each beaker will give an indication of the speed or rate of reaction for the forward and reverse reactions. What you have to imagine is pouring the contents of the two beakers backwards and forwards at the SAME TIME into the two troughs.

reversible reactions

Dynamic equilibrium

Study the diagram below, it explains what is meant by dynamic equilibrium. dynamic equilibrium At equilibrium:

These changes at equilibrium are summarised in the graph shown below. Here the green line represents the amount of reactant and the red line the amount product. To begin with there is 100% reactant present and 0% of the product since the reaction has not started. However both lines for the reactants and products level out at a constant amount, this is the point at which the forward and reverse reactions are proceeding at the same rate. The reaction has achieved dynamic equilibrium and the amount of reactant and product does not change despite the fact that both the forward and reverse reactions are still proceeding..

graphs to show reactant and product concentrations at equilibrium

Examples of reversible reactions

Copper sulfate is a colourless (white) ionic crystalline solid. However most of the time you will have seen or used it in the lab it is blue not white. The reason for this is that it absorbs water from the air and this turns it blue. The dry or anhydrous copper sulfate has the formula CuS04, it is an ionic compounds with a giant ionic lattice structure. The water it absorbs from the air fits into this lattice structure and is held weakly in place. The wet or hydrated copper sulfate has the formula: CuS04.5H2O (the .5H2O just means that it has 5 moles of water associated with it crystal structure). This water can be easily evaporated from the lattice by heating. This is shown below, once it has evaporated it loses its blue colour and turns white or colourless to form anhydrous copper sulfate. Addition of water again forms the hydrated blue form of copper sulfate.

heating hydrated copper sulfate

We can show this reversible reaction in an equation as:

hydrated copper sulfateanhydrous copper sulfate + water
CuS04.5H2O CuS04 + 5H20

The thermal decomposition of ammonium chloride

decomposition of ammnonium chloride

Ammonium chloride is a colourless solid which will decompose when heated to form a mixture of two gases, ammonia and hydrogen chloride gas. This reaction is reversible and when cooled the mixture of the basic ammonia and the acidic hydrogen chloride gases will reform solid crystals of ammonia chloride. This reaction can be shown as:

ammonia chloride(s) ammonia(g) + hydrogen chloride(g)
NH4(s) NH3(g) + HCl(s)
The diagram opposite shows the reaction. On heating the solid crystals of ammonium chloride decompose to form the basic gas ammonia and the acidic gas hydrogen chloride. These two gases quickly rise up the boiling tube, and if they meet a cool surface they will immediate react and reform crystals of ammonium chloride. During the experiment shown if the boiling tube is gently heated then the middle and top will remain sufficiently cool for crystals of ammonium chloride to reform on the sides of the boiling tube. Once the two gases leave the boiling tube they will also cool down enough for a cloud of white solid ammonium chloride to form.

Dynamic equilibrium

The examples above all show reversible reactions, however none of these reactions will ever achieve dymanic equilibrium. The reason for this is simple - equilibrium can only be achieved in closed systems. That is a system where there is no transfer or movement of matter (solids, liquids or gases) in or out of the system. As a simple example consider two conical flasks filled with a little water. One flask is left open to the surrounding while the other represents a closed system, simply by placing a rubber bung in the flask.

example of open and closed system

If left evaporation of water will start in both flasks. In the open flask given enough time the water (the system) will simply evaporate and enter the surroundings- the atmopshere. However in the closed flask the water molecules will begin to evaporate and leave the liquid phase to enter the gas phase in the conical flask. The amount of water molecules in the gas phase will increased with time and eventually some will start to re-enter the liquid phase. When the rate of evaporation and the rate of condensation are the same then the amounts of water vapour and liquid water will remain constant despite the fact that evaporation and condensation are still going on. The key point is that a balance has been achieved, the rates of condenation and evaporation are equal - we say they are in equilibrium or balance. The word dymanic implies movement and since the two processes of evaporation and condensation are in balance but still continuing we say dynamic equilibrium has been reached,

What would happen if we set up three conicals flasks, each fitted with a stopper to ensure a closed systen and with:

The three flasks were then placed in a warm room for 1 week. What do you think you could say about the contents of the flasks after 1 week?

After 1 week the contents of the flasks would be the same, each flask would contain the same amount of water vapour and liquid water. This simple experiment demonstrates an important point regarding equilibrium, that is it can be approached from either 100% reactants or products or some mixture of the two. Equilibrium is a low energy point in a reacting system and the reaction will always end up at this low energy point at any given temperature no matter from where you start.

Key Points