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# Rates of reaction

Some reactions happen very quickly. Others are so slow it appears that nothing much is happening. It is useful to understand why the rates of reactions vary so much, and what makes reactions go faster or slower. Put simply, the rate of a reaction tells us how rapidly the products are made from the reactants. Rate of reaction = amount of reactants used time or amount of product made time

Fast reactions:

Slow reactions:

## Measuring the rate of a reaction:

We need to measure some change at regular time intervals, as the reactants are used up and the products are formed. We can do that in a variety of ways: 1) Measuring the volume of gas produced in a reaction, at regular time intervals

gas syringe

zinc + acid

2) Measuring the decrease in mass of the reactants, at regular time intervals, as a gas is produced and lost into the atmosphere

3) Measuring the time taken for a certain mass of solid product to be formed, resulting in a certain degree of colour change, or the solution becoming opaque.

The results: In an experiment where we measure the amount of product formed, e.g. the volume of a gas being collected, at regular time intervals the results will appear as below: Note how the gradient shows the rate of reaction. It is initially steep where the reaction is fast. The rate slows down as reactants are used up. Eventually the curve becomes flat as the reaction finishes, when one of the reactant has been completely used up.
mass of reactants (g)

## volume of gas (cm3)

time (s)

For a reaction where we measure the amount of reactants used at regular time intervals, the results will look like this: Note how the initial gradient is again steep, and the curve becomes flat when the reaction stops because a reactant has been completely used up.

time (s)

We can use graphs like this to compare the rates of different reactions. There are several points to note: The blue reaction has a faster rate than the green reaction. We can tell because the initial gradient is steeper. The blue reaction finishes before the green reaction. We can tell because the blue line becomes flat at an earlier time than the green line.
time (s)

## volume of gas (cm3)

Both the blue and green reactions produce exactly the same amount of product. We can tell because the final volume of gas is the same in each case. These results are typical of an experiment where the same quantities of reactants are used, but the reaction is done e.g. at different temperatures. (Blue = hotter) The red reaction is slower than the green reaction, and produces less product. This is typical of an experiment where the concentration of a reactant is changed, and the reaction finishes when this reactant is completely used up. (Red = more dilute)

To understand how rates of reaction differ, we need a model of how reactions work. Collision Theory provides an effective model to help us explain how different factors affect the rate of a reaction. In collision theory we imagine our reactants to be particles which can move around and collide with one another. Collision Theory states that:

1) For a reaction to take place, the reactant particles have to collide with one another. In this example our reaction is:
2) The collision has to take place with sufficient energy for the reaction to be successful too little energy and the reactants just bounce off one another. We say that the particles must collide with energy greater than the ACTIVATION ENERGY for the reaction in order for a collision to be successful.

The picture above shows the reactants, before any reactions have happened. Two particles collide with sufficient energy Product particle, from a previous successful collision.

Collision theory allows us to explain how the rate of a reaction can be altered:

For example, if there are more particles per cm3 of one of the reactants, then there will be more frequent collisions the rate of reaction will increase.
SOLIDS: We cant increase the number of particles per cm3 of a solid reactant. SOLUTIONS: Increasing the concentration of a solution means having more solute particles per cm3 of the solvent. Increasing the concentration of a solution increases the rate of reaction, as explained above. The concentration of a solution is measured in moles per dm3 (1 dm3 = 1000cm3 = 1 litre) Adding more solvent to a solution means there are the same number of solute particles in a larger volume of solution the solution is more dilute. This means there are fewer solute particles per cm3. GASES: Increasing the pressure in a gas means forcing the particles closer together so there are more particles per cm3. This has a similar effect on the rate to increasing the concentration of a solution.

## volume of gas (cm3)

Reaction between acid and marble chips excess marble chips present.

time (s)

The initial rate of reaction is high because there are lots of particles of acid per cm3 to collide with the marble chips. As the acid is used up, there are fewer acid particles per cm3 so collisions are less frequent, and the rate slows down. When all the acid particles have reacted, there are no more successful collisions, so the reaction stops the rate becomes zero.

## volume of gas (cm3)

Reaction between 50cm3 of different concentrations of acid, and marble chips excess marble chips present. Blue: acid conc. = 2 moles per dm3 Red: acid conc. = 1 mole per dm3
time (s)

In the more concentrated acid there are twice as many acid particles in the same volume of acid. The rate of the blue experiment is faster than the red experiment because there are more acid particles per cm3 to collide with the marble chips, so successful collisions occur more frequently. Because there are twice as many acid particles per cm3 in the blue reaction, wed expect the rate of reaction to be twice as fast. In the blue experiment there were twice as many acid particles in total (in the same volume of acid) to react with the marble chips, so wed expect twice as much gas to be produced when the acid particles were all used up and the reaction finished.

Using collision theory to explain the shapes of graphs - temperature Increasing the temperature of a reaction has two effects: i) The particles move around more quickly, so collisions between the reactant particles occur more frequently. ii) The particles are also moving around and therefore colliding with more energy so more of the collisions which take place will be successful because the particles will have collided with more energy than the activation energy for the reaction.

These two factors work together, so that increasing the temperature has a dramatic effect in speeding up reactions.
(This is why food left out in the kitchen spoils much more quickly than food kept cold in the fridge !).

## volume of gas (cm3)

Reaction between same volume and concentration of acid, and same amount of marble chips at different temperatures.
Blue: acid temp. = 30C Green: acid temp. = 20C
time (s)

In the blue experiment the acid particles are moving faster and with more energy because they are at a higher temperature. This means successful collisions will occur more frequently, and the rate of reaction will be faster than in the green experiment. The same quantities of acid and marble chips are used in both blue and green experiments, so the same amount of gas will be produced in each case once the reaction is complete.

## Using collision theory to explain the shapes of graphs surface area

Reaction between same volume and concentration of acid, and same amount of marble chips
Blue: powdered marble chips Green: small pieces of marble While we dont change the pressure or concentration for solids, we can do something to affect the rate with which they react. When we put a lump of solid into a reaction it is only the particles on the outside of the lump which are exposed to collisions with the other reactant particles. We can increase the rate of reaction by exposing more of the solid to collisions with the other reactants. This is done by crushing the solid, or using smaller pieces. This increases the surface area available for successful collisions. When we increase the surface area of a solid reactant, we increase the frequency of collisions between the reactants, and therefore successful collisions take place more often, increasing the rate of reaction.

A catalyst is a substance which can be added to alter the rate of reaction. Usually a catalyst has the effect of speeding up the reaction. (Occasionally catalysts called inhibitors are used to slow down the rate of a reaction) The special thing about a catalyst, unlike a reactant, is that it is all still there at the end of the reaction.

We therefore define a catalyst as: A substance which alters (speeds up) the rate of a reaction, but is not used up.

e.g. hydrogen peroxide decomposes to form water and oxygen. The reaction goes much faster if a manganese IV oxide catalyst is added. We show this as:
manganese IV oxide

2 H2O2

2 H2O + O2

Note how the catalyst is not shown as a reactant, but may be written over the arrow, where the reaction conditions are shown. Once the bubbles of oxygen has finished being produced, we can filter off, dry and weigh the manganese IV oxide to show that it is all still there. We could add it to more hydrogen peroxide and use it again.

Examples of catalysts you should be aware of: Nickel is used as a catalyst for the hydrogenation of vegetable oils, where hydrogen is added to the unsaturated oils in order to make them saturated, so more solid. Iron is used the catalyst in the Haber process for the manufacture of ammonia from nitrogen and hydrogen Cars have a catalytic converter containing platinum and rhodium in the exhaust system, which helps pollutant gases such as carbon monoxide and nitrogen oxide react to form less harmful gases such as carbon dioxide and nitrogen

A catalyst (often alumina) is used in cracking of crude oil fractions. In the laboratory, pieces of broken ceramic pot can be used as the catalyst.

Enzymes are biological catalysts which are used e.g. in reactions such as fermentation (the yeast organism manufactures the enzyme in this case)

So how does a catalyst actually work ? It is best to think of a solid catalyst as a place where reactant molecules can come together. On the surface of the catalyst the bonds in the reactants are weakened. With weakened bonds, it takes less energy for a collision to be successful, so the effect of a catalyst is to lower the Activation Energy for the reaction.

By lowering the activation energy for a reaction, a catalyst causes more of the collisions between reactant particles to be successful, thereby increasing the rate of reaction.

The more places there are on the catalyst surface for reactant molecules to stick on and have their bonds weakened, the faster the rate of reaction will become. This is why many catalysts are designed to have very high surface areas.
close-up of the surface of a platinum rhodium catalyst showing the rough surface, which provides a high surface area