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Rates of reaction

The rate of a reaction tells us how rapidly the products are made from the reactants. Rate of reaction = amount of reactant used time
or

amount of product made time

Fast reactions:

combustion, explosions

Slow reactions:

baking, corrosion/rusting, fermentation

Measuring the rate of a reaction:


e.g. 1) Measure the volume of gas produced in a reaction, at regular time intervals

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

3) Measure the time taken for a colour change to occur, or the solution becoming opaque.

Rate Graphs: If we measure the amount of product formed vs. time the results will look like this:
volume of gas (cm3)

time (s)

The gradient shows the rate of reaction: It is initially steep because the reactions is fastest at the start. The rate slows down as reactants are used up the gradient gets less steep. Eventually the curve becomes flat as the reaction finishes, when one of the reactants has been completely used up.

Rate Graphs: If we measure the amount of reactants used up vs. time, the results will look like this:
mass of reactants (g)

time (s)

The initial gradient is still steepest, the reaction is fastest at the start The curve becomes flat when the reaction stops because a reactant has been completely used up.

Comparing rates:

volume of gas (cm3)

time (s)

Practice questions: (answers at the end of the topic) Which is faster, blue or green reaction ? Which reaction finishes first, blue or green ? Which two curves could be the same reaction happening at two different temperatures ? Which is hotter ?

The reaction: methane + oxygen carbon dioxide + water


Our model: = methane = oxygen
The particles in a liquid or gas are moving around they have kinetic energy. In order for a chemical reaction to occur the reactant particles must collide with each other. There is an amount of energy called the Activation Energy for each reaction it is actually the amount of energy needed to break the necessary bonds in the reactants.

If the particles are moving quickly and collide with more than the activation energy, then they will react a successful collision a reaction occurs.
If the particles collide with less than the activation energy, then they will simply bounce off one another and not react an unsuccessful collision.

Reactions with a solid:

e.g. zinc + hydrochloric acid

Imagine the particles in this reaction. A reaction can only take place when the acid particles (blue) collide with the surface of the solid zinc particles. A collision cannot take place with the zinc particles inside a solid piece.
Factors which affect the rate of reaction: - temperature of reactants - pressure (only applies to gases) - concentration of reactants (applies to solutions) - surface area (applies to solid reactants) - use of a catalyst

Concentration
The concentration of a solution means the number of particles in a given volume of the solvent (usually water). We measure concentration in moles per dm3. (1dm3 = 1 litre) If we increase the concentration of a reactant, we have more particles per cm3. This means that collisions will take place more frequently. Therefore there will be more frequent successful collisions, and the rate of reaction will increase. Prediction: If we double the concentration of the acid, we double the number of acid particles per cm3,we double frequency of successful collisions, therefore we double the rate of the reaction. We can test this prediction experimentally.

Pressure

The same volume of different gases contain the same number of particles of gas (when the gases are at the same pressure and temperature).

Increasing the pressure of a gas makes the particles closer together. So we have more particles per cm3. This means that collisions will take place more frequently. Therefore there will be more frequent successful collisions, and the rate of reaction will increase.

Temperature
If we increase the temperature of a gas or solution: The particles will move more quickly (i.e. having more kinetic energy). This means that the particles will collide more frequently. Also the particles will collide with more energy. This means that more of the collisions will be successful, because more often the colliding particles have more energy than the activation energy for the reaction.\ Both of these factors will increase the rate of reaction. Prediction: Because the particles are colliding more frequently AND they are colliding with more energy, doubling the temperature should more than double the rate of reaction.

Surface Area
Collision can only take place at the surface of a solid, so the larger the surface area, the faster the rate of reaction. For the same mass of solid reactant: large lumps slow reaction; low surface area small lumps faster reaction; more surface area powder fast reaction; high surface area

Catalysts
A catalyst affects the rate of a reaction but is not used up during the reaction. It therefore remains behind when the reaction is complete, ready to be used to catalyse further reactions. Manganese(IV) oxide (MnO2) is an example of a catalyst. It speeds up the breakdown (decomposition) of hydrogen peroxide. 2 H2O2(aq)

MnO2

2 H2O(l) + O2(g)

Notice how the catalysts formula doesnt show up in the equation, because its not a reactant or a product. We write it over the arrow, showing that it is one of the conditions for the reaction.

How does a catalyst work ? Reactions require successful collisions between the reactant particles. The reactant particles must collide with enough energy to break the bonds in the reactants. This is called the Activation Energy for the reaction. When a catalyst is added to a reaction it provides an alternative reaction pathway - a place for the reaction to happen where the Activation Energy is lower, so more of the collisions between the reactants are successful so the rate is faster. Catalysts need a high surface area so that there are lots of places for the reactants to bind onto the catalyst surface ready to react. A powdered catalyst, or a rough gauze provides a high surface area.

Close-up of a Pt-Rh catalyst used in industry

Is being a catalyst different from being a reactant ? A reactant is used up during the reaction as it is turned into the products. A catalyst is not used up. We could remove it after the reaction (e.g. by filtering it then washing and drying it) and weigh it to show it is all still there. We could use it again and again.

Examples of catalysts: The catalytic converter in the exhaust system of cars contains a catalyst made from platinum, rhodium and palladium. This catalyst removes toxic carbon monoxide and nitrogen oxides (which cause acid rain) from the exhaust gases from the car.

Catalytic converter

The Haber process is used to make ammonia. An iron catalyst is used to speed up the reaction so a lower temperature can be used in the reactor, (lower energy costs). It also means less fuel is burnt, conserving finite fossil fuel resources and minimising greenhouse gas emissions. Ammonia reactor

Reversible reactions
Some reactions do not go to completion we dont get 100% yield because not all of the reactants react to form products.
One of the reasons for this is that some reactions are reversible the products can react to form the reactants !

e.g.
but also

3 H2 + N2 2 NH3 2 NH3 N2 + 3 H2

We use a special symbol to denote a reaction which is reversible:

3 H2 + N2 2 NH3
A single arrow in an equation means that the reactants form the products but the products cant react to form the original reactants again.

e.g.

CaCO3 CaO + CO2 (thermal decomposition of calcium carbonate)

The double-headed arrow means the reaction can go in either direction e.g. NH4Cl NH3 + HCl (ammonium chloride reacts to form ammonia and hydrogen chloride and also ammonia and hydrogen chloride react to form ammonium chloride)

thermal decomposition NH4Cl NH3 + HCl

NH3 + HCl NH4Cl neutralisation

Heat

The forward reaction is a thermal decompostition ammonium chloride breaks up when heated into two simpler substances: ammonia and hydrogen chloride.

The reverse reaction is a neutralisation the hydrogen chloride is acting as an acid (H+ donor) and the ammonia as a base (H+ acceptor).

A reversible reaction the test for water:

White, anhydrous copper sulphate forms blue hydrated copper sulphate if water is added. The reaction is reversible. If the crystals are heated they turn white as anhydrous copper sulphate is formed.
CuSO4.5H2O(s) hydrated copper sulphate

CuSO4(s) anhydrous copper sulphate

+ 5H2O(l) + water

An alternative test for water: Blue, anhydrous cobalt chloride is also used as a test for water it turns to pink hydrated cobalt chloride if water is added. If the crystals are heated they turn blue again. CoCl2.6H2O(s) hydrated cobalt chloride

CoCl2(s) anhydrous cobalt chloride

+ 6H2O(l) + water

Equilibrium When reactants are turning into products, and products are turning into reactants, a dynamic equilibrium can be set up. (Think of this as being like a balance-point the forward and reverse reactions becoming balanced. Running up an escalator which is going down at a rate causing you to stay in the same place would be one example of a dynamic equilibrium. Adjusting the flow into and out of the pot so that the volume of liquid remains the same even though the actual liquid is constantly changing, would be another example) At equilibrium: There will be both products and reactants present in a mixture. The rate of products turning into reactants will be the same as the rate of reactants turning into products. To get an equilibrium, none of the reactants or products must escape you need a closed system.

How it works: The reactants begin to react forming products. The initial rate of forward reaction will be fast.
The forward reaction slows down as reactants are used up. Products have now been formed, so they begin to react to form reactants. The initial rate of the reverse reaction is very slow as only a few product particles are present. As more products are formed, the rate of the reverse reaction increases. Eventually the rates of forward reaction and backward reactions become the same. THE REACTIONS HAVENT FINISHED BUT AN EQUILIBRIUM IS SET UP.

How much is there at equilibrium ? The amounts of the products and the reactants at equilibrium depends on the conditions (e.g. temperature, pressure). Changing the conditions will change the amounts of reactants and products present in the mixture - a new equilibrium gets set up. We call this changing the POSITION of the equilibrium. - if changing the conditions causes the position of equilibrium to move in the forward direction (to the right) we get more products, less reactants in the equilibrium mixture

N2

3H2

2NH3

- if changing the conditions causes the position of equilibrium to move in the backwards direction (to the left) we get less products, more reactants in the equilibrium mixture

N2

3H2

2NH3

Making more product at equilibrium


Whenever we change the conditions, the position of the equilibrium will shift to try and oppose the change.

N.B. The effect of pressure only applies to GASES in the balanced equation !

Example:

CH3OH (g) + H2O(g) CO2(g) + 3H2(g)

endothermic in the forward direction

This reaction is called steam reforming of methanol. It is used to produce hydrogen, a valuable fuel, from an alcohol.
What would be the best conditions of temperature and pressure to get the best yield of hydrogen? Temperature: A high temperature would move the position of equilibrium in the endothermic direction, which is the forward direction, so more products would be made. There are four moles of gases on the right side of the equation and only two moles of gases on the left side. A low pressure would move the position of equilibrium in the forward direction, making more product. A catalyst would speed up the reaction (in both directions) so products would be made sooner. It would have no effect on the position of equilibrium, and hence the yield, only how quickly the product is made.

Pressure:

Catalyst:

True or False ? (answers at the end of the topic)


All chemical reactions are reversible. The mass can change if a solid product is formed in a closed system. Equilibrium can only happen in closed systems.

In a reversible reaction, reactants can form products and products can form reactants.
A symbol shows that an equilibrium has been set up. Once at equilibrium no more products are formed. Once at equilibrium, the forward and backward reactions stop.

Answers:
volume of gas (cm3)

time (s)

Which is faster, blue or green reaction ? BLUE steeper gradient. Which reaction finishes first, blue or green ? BLUE flat after shortest time. Which two curves could be the same reaction happening at two different temperatures ? Which is hotter ? BLUE (HOTTER) , GREEN because both produce the same volume of gas, just at different rates.

True or False ?
All chemical reactions are reversible. FALSE burning, and rusting, for example, cant be reversed The mass can change if a solid product is formed in a closed system FALSE all the same atoms are still there, mass is conserved Equilibrium can only happen in closed systems. TRUE a closed system is a requirement for an equilibrium In a reversible reaction, reactants can form products and products can form reactants. TRUE this is exactly what does happen A symbol shows that an equilibrium has been set up. FALSE it only shows that the reaction is reversible Once at equilibrium no more products are formed. FALSE the reactions happen continuously, so product is still being made, but it is being used up by the reverse reaction at the same rate. Once at equilibrium, the forward and backward reactions stop. FALSE these reactions continue, but at the same rate

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