7. How far? How fast?

7.1 Energy changes in chemical reactions

Chemical reactions are capable of releasing vast amounts of energy.

The reaction between methane and oxygen

Hydrocarbon molecules contain only the elements carbon and hydrogen.

Methane + oxygen carbon dioxide + water CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

During this reaction, as with all others, bond are first broken and then new bonds are made.

In methane molecules, carbon atoms are covalently bonded to hydrogen atoms. In oxygen gas, the atoms are held together in diatomic molecules.

During the reaction, all these bonds must be broken. Chemical bonds are forces of attraction between atoms or ions.

To break these bonds requires energy; Energy must be taken in to pull the atoms apart.

Breaking chemical bonds takes energy from the surroundings. This is an endothermic process.

in

New bonds are then formed: between carbon and oxygen to make carbon dioxide, and between hydrogen and oxygen to form water. Forming these bonds gives out energy.

Making chemical bonds gives energy to the surroundings. This is an exothermic process.

out

When methane reacts with oxygen, the total energy given out is greater than the total energy taken in. So, overall, this reaction gives out energy it is an exothermic reaction. The energy is released as heat.

The overall change in energy for this exothermic reaction can be shown in an energy level diagram.

Exothermic Reaction
Reactants Products + Energy
Energy of reactants Energy of products

Energy

Reactants

-DH
Products

Reaction Progress

Energy / kJ

CH4 (g) + 2O2 (g)

Heat given out

CO2 (g) + 2H2O (g)

Progress of reaction

In this reaction, energy is given out because the bonds in the products (CO2 and H2O) are stronger than those in the reactants (CH4 and O2) This means that the products are more stable than the reactants.

Some bonds are stronger than others. They require more energy to break them, but they give out more energy when they are formed.

The combustion reactions of fossil fuels such as oil and gas are exothermic.

The major characteristics that make these fuels so useful are that: they are easy to ignite and burn They are capable of releasing large amounts of energy as heat.

The reaction between nitrogen and oxygen

Endothermic reactions are far common than exothermic ones. less

Here, energy is absorbed from the surroundings.

The reaction between nitrogen and oxygen is endothermic.

It is one of the reaction that take place when fuel is burnt in car engines.

Nitrogen + monoxide

oxygen

nitrogen

Here the bonding in the products is weaker than in the reactants. Overall, energy is taken in by the reaction.

N2 (g) + O2 (g) NO (g)

Heat of reaction
The energy change in going from reactants to products in a chemical reaction is known as the heat of reaction. It is given the symbol H ( the symbol means change in

Heat of reaction
The energy given out or taken in is measured in kilojoules (kJ); 1 kJ = 1000 J.

It is usually calculated per mole of a specific reactant or product (kJ / mol)

Exothermic reaction
The starting point for the calculation is the reacting mixture. If a reaction gives out heat to the surroundings, the mixture has lost energy. It is an exothermic reaction.

Exothermic reaction In EXothermic reaction, heat EXits the reaction mixture. An exothermic reaction has a negative value of H.

Exothermic Reaction
Reactants Products + Energy
Energy of reactants Energy of products

Energy

Reactants

-DH
Products

Reaction Progress

Endothermic reaction
If a reaction takes in heat from the surroundings, the mixture has gained energy. It is an endothermic reaction.

Exothermic reaction In ENdothermic reaction, heat ENters the reaction mixture. An endothermic reaction has a positive value of H.

Endothermic Reaction
Energy + Reactants Products

Energy

Activation Energy

Products

Reactants

+DH

Reaction progress

Heat of reaction: for exothermic reactions, heat energy is given out (exits) and H is negative for endothermic reactions, heat energy is taken in (enters) and H is positive

These ideas fit with the direction of the arrows shown in the energy diagrams.

Exothermic reaction
Energy / kJ

CH4 (g) + 2O2 (g)

Heat given out (728kJ/mol)

CO2 (g) + 2H2O (g)

Progress of reaction

Making and breaking bonds

Experiments have been carried out to find out how much energy is needed to break various covalent bonds in compounds. The average value obtained for a particular bond is known as the bond energy. It is a measure of the strength of the bond.

Energy / kJ

2NO2 (g)

Heat taken in
N2 (g) + O2 (g)

Progress of reaction

ENERGY LEVEL DIAGRAMS

We can show the energy transfers in reactions on an energy level diagram. These show us the energy stored in the reactants compared to the energy stored in the products.

Exothermic energy level diagram

Exothermic energy level diagram

H (delta H) is the symbol for the change in energy. In an exothermic reaction the products have less energy than the reactants. H is negative for an exothermic reaction.

Endothermic energy level diagram

Endoothermic energy level diagram

In an endothermic reaction the products have more energy than the reactants. H is positive for an endothermic reaction.

Making and breaking bonds

We have seen how bonds are formed (both ionic and covalent) Do you think energy is needed to break bonds?

 Breaking bonds requires energy. It is endothermic.

 Breaking bonds requires energy. It is endothermic. Making new bonds gives out energy. It is exothermic.

Heat of combustion

The energy change of a reaction when a substance is burnt.

Heat of neutralisation

The energy change of a reaction when an acid react with an alkali to form water.

Activation energy

the amount of energy that is required to start a chemical reaction. Once activation energy is reached the reaction continues until you run out of material to react.

Activation energy

More usually, energy is required to start the reaction. When fuels are burnt, for example, energy is needed to ignite them.

Activation energy

This energy may come from a spark, a match or sunlight. It is called the activation energy (given the symbol EA) It is required because initially some bonds must be broken before any reaction can take place.

Activation energy

Sufficient atoms or fragments of molecules must be freed for the new bonds to begin forming.

Once started, the energy released as new bonds are formed causes the reaction to continue.

Activation energy

All reactions require some activation energy.

For the reaction of sodium or potassium with water the activation energy is low, and there is enough energy available from the surroundings at room temperature for the reaction to begin spontaneously.

Activation energy

Reactions can be thought of as the result of collisions between atoms, molecules or ions. In many of these collisions, the colliding particles do not have enough energy to react, and just bounce apart, rather like dodgem cars.

Activation energy

A chemical reaction will only happen of the total energy of the colliding particles is greater than the required activation energy of the reaction.

7.2 Rate of reaction

A chemical reaction will only happen of the total energy of the colliding particles is greater than the required activation energy of the reaction.

What does rate of reaction mean?

The speed of different chemical reactions varies hugely. Some reactions are very fast and others are very slow. The speed of a reaction is called the rate of the reaction.

What is the rate of these reactions?

rusting baking explosion

slow

fast

very fast

Rates of reaction
Why are some reactions faster than others?

Reactions, particles and collisions

Reactions take place when particles collide with a certain amount of energy.

The minimum amount of energy needed for the particles to react is called the activation energy, and is different for each reaction. The rate of a reaction depends on two things:
the frequency of collisions between particles the energy with which particles collide.

If particles collide with less energy than the activation energy, they will not react. The particles will just bounce off each other.

Changing the rate of reactions

Anything that increases the number of successful collisions between reactant particles will speed up a reaction. What factors affect the rate of reactions?

increased temperature increased concentration of dissolved reactants, and increased pressure of gaseous reactants increased surface area of solid reactants use of a catalyst.

Slower and slower!

Reactions do not proceed at a steady rate. They start off at a certain speed, then get slower and slower until they stop. As the reaction progresses, the concentration of reactants decreases. This reduces the frequency of collisions between particles and so the reaction slows down.

0%

25% reactants product

50%

75%

100%

percentage completion of reaction

Graphing rates of reaction

Reactantproduct mix

How can rate of reaction be measured?

Measuring the rate of a reaction means measuring the change in the amount of a reactant or the amount of a product. What can be measured to calculate the rate of reaction between magnesium and hydrochloric acid?
magnesium + hydrochloric magnesium + hydrogen acid chloride

The amount of hydrochloric acid used up (cm3/min). The amount of magnesium chloride produced (g/min). The amount of hydrogen product (cm3/min).

Setting up rate experiments

What equipment is needed to investigate the rate of hydrogen production?
glass tube rubber connecter gas syringe

conical flask

rubber bung

hydrochloric acid

magnesium

Calculating rate of reaction from graphs

How can the rate of reaction be calculated from a graph?
70
hydrogen produced (cm3)

60 50 40 x
rate of reaction = y x

30
20 10 0

10

time (seconds)

20

30

40

50

The gradient of the graph is equal to the initial rate of reaction at that time
rate of reaction = 45 cm3 20 s rate of reaction = 2.25 cm3/s

The reactant/product mix

Collisions and reactions: summary

Temperature and collisions

How does temperature affect the rate of particle collision?

Effect of temperature on rate

The higher the temperature, the faster the rate of a reaction. In many reactions, a rise in temperature of 10 C causes the rate of reaction to approximately double. Why does increased temperature increase the rate of reaction?

At a higher temperature, particles have more energy. This means they move faster and are more likely to collide with other particles.
When the particles collide, they do so with more energy, and so the number of successful collisions increases.

Temperature and particle collisions

Temperature and batteries

Why are batteries more likely to rundown more quickly in cold weather? At low temperatures the reaction that generates the electric current proceeds more slowly than at higher temperatures.

This means batteries are less likely to deliver enough current to meet demand.

How does temperature affect rate?

The reaction between sodium thiosulfate and hydrochloric acid produces sulfur.

sodium hydrochlor sodiu m thiosulfa + ic chlorid te acid e

sulfur sulfu dioxid + r e

+ wate
r

Na2S2 O3 (aq)

2HC l (aq)

2NaC l (aq)

SO

(g)

S (s )

H2 O (l)

Sulfur is solid and so it turns the solution cloudy. How can this fact be used to measure the effect of temperature on rate of reaction?

The effect of temperature on rate

The higher the concentration of a dissolved reactant, the faster the Effect of concentration on rate of reaction rate of a reaction. Why does increased concentration increase the rate of reaction?

At a higher concentration, there are more particles in the same amount of space. This means that the particles are more likely to collide and therefore more likely to react.

lower concentration

higher concentration

Concentration and particle collisions

The effect of concentration on rate

Effect of pressure on rate of Why does increasing the pressure of gaseous reactants increase reaction the rate of reaction?
As the pressure increases, the space in which the gas particles are moving becomes smaller. The gas particles become closer together, increasing the frequency of collisions. This means that the particles are more likely to react.

lower pressure

higher pressure

Effect of surface area on Any reaction involving a solid can only take place at the surface rate of reaction of the solid.
If the solid is split into several pieces, the surface area increases. What effect will this have on rate of reaction?

low surface area

high surface area

This means that there is an increased area for the reactant particles to collide with. The smaller the pieces, the larger the surface area. This means more collisions and a greater chance of reaction.

Surface area and particle collisions

Reaction between a Marble chips are made of calcium carbonate. They react with carbonate and acid hydrochloric acid to produce carbon dioxide.
calcium hydrochlor carbonat + ic e acid
CaCO3 (aq)

2HCl (aq)

calciu + wat m er chlorid CaCl2 H2O e (aq) + (aq)

carbo + n dioxid CO2 e + (g)

The effect of increasing surface area on the rate of reaction can be measured by comparing how quickly the mass of the reactants decreases using marble chips of different sizes.

The effect of surface area on rate

Catalysts are substances that change the rate of a reaction without being used up in the reaction. Catalysts never produce more product they just produce the same amount more quickly. Ea without catalyst energy (kJ)

What are catalysts?

Different catalysts work in different ways, but most lower the reactions activation energy (Ea).

Ea with catalyst

reaction (time)

Many catalysts are transition metals or their compounds. For example: Nickel is a catalyst in the production of margarine (hydrogenation of vegetable oils). Iron is a catalyst in the production of ammonia from nitrogen and hydrogen (the Haber process). Platinum is a catalyst in the catalytic converters of car exhausts. It catalyzes the conversion of carbon monoxide and nitrogen oxide into the less polluting carbon dioxide and nitrogen.

Everyday catalysts

Why are catalysts so important for industry?

Catalysts in industry

Products can be made more quickly, saving time and money.

Catalysts reduce the need for high temperatures, saving fuel and reducing pollution.

Catalysts are also essential for living cells. Biological catalysts are special types of protein called enzymes.

 activation energy The amount of energy needed to Glossary

start a reaction.

catalyst A substance that increases the rate of a chemical

reaction without being used up.

concentration The number of molecules of a substance in

a given volume.

enzyme A biological catalyst. rate of reaction The change in the concentration over a
certain period of time.

Anagrams

Rates of reaction: summary

Multiple-choice quiz

Surface area
If we make the pieces of the reactants smaller we increase the number of particles on the surface which can react. This makes the reaction faster.
The particles on the surface can react

When cut into smaller pieces the particles on the inside can react

How do we make the reaction go faster?

There are four things that we can change to make the reaction go faster. They are Temperature Surface area Concentration Using a catalyst

Temperature
When we increase the temperature we give the particles energy This makes them move faster This means they collide with other particles more often So the reaction goes faster.

Concentration
If we make one reactant more concentrated (like making a
drink of orange squash more concentrated)

There are more particles in the same volume to react So the reaction goes faster.
Click here to complete exercise

There are less red particles in the same volume so there is less chance of a collision There are more red particles in the same volume so there is more chance of a collision so the reaction goes faster

Using a catalyst
A catalyst is a chemical which is added to a reaction. It makes the reaction go faster. The catalyst does not get used up in the reaction. It gives the reaction the energy to get started

Endothermic Reaction:
- system absorbs E

- more energy needed to break bonds than released by creating bonds - change in enthalpy is positive

Exothermic Reaction: - system releases E - more energy released by creating bonds than needed to break bonds - change in enthalpy is negative

Cold and hot packs

How do instant hot and cold packs work?

100

Hot pack
Pressing the bottom , the diaphragm breaks. Calcium chloride dissolves in water and warms it. The beverage gets warm.

101

Exothermic process
Heat flows into the surroundings from the system in an exothermic process.
Surroundings

Energy

Hot pack
Temperature rises
102

Hot pack
We will repeat the process in a beaker with calcium chloride ( 25 g CaCl2) + water (25 ml) and a thermometer. We will record the initial temperature of the water and the temperature after the dissolution of the salt. Observation: 103 a temperature rise of.

Cold pack
Water and ammonium nitrate are kept in separate compartments. Pressing the wrapper, the ammonium nitrate dissolves in water and absorbs heat. The pack becomes cold.

It is used to treat sports injuries.

104

Endothermic process
Heat flows into the system from the surroundings in an endothermic Surroundings process.
Cold pack
Energy

Temperature falls
105

Cold pack
We will repeat the process in a beaker with ammonium nitrate ( 25 g NH4NO3) + water (25 ml) and a thermometer. We will record the initial temperature of the water and the temperature after the dissolution of the salt. Observation: a temperature drop of.
106

Exothermic Reaction
Reactants Products + Energy
10 energy = 8 energy + 2 energy
Energy of reactants Energy of products

Energy

Reactants

-DH
Products

Reaction Progress

Endothermic Reaction
Energy + Reactants Products

Energy

Activation Energy

Products

Reactants

+DH Endothermic

Reaction progress

Effect of Catalyst on Reaction Rate

What is a catalyst? What does it do during a the chemical reaction? Catalyst lowers the activation energy for reaction.
No catalyst activation energy for catalyzed reaction

Energy

reactants

products

Reaction Progress

Basic Revision
For a chemical reaction to occur, bonds must be both formed and broken Fe + CuSO4 Cu + FeSO4

Basic Revision
Chemical reactions always involve energy changes. Making and breaking bonds involves energy changes

ENERGY AND CHEMICAL REACTIONS

Exothermic reactions These reactions give out heat energy. Combustion is an exothermic reaction.

ENERGY AND CHEMICAL REACTIONS

Endothermic reactions These reactions take in heat energy from their surroundings. These cause temperatures to fall.

ENERGY AND CHEMICAL REACTIONS

Use the apparatus as shown. Work with 20ml of each substance in turn. Copy the results table before you start

ENERGY AND CHEMICAL REACTIONS

Reaction temp. before mixing (0C) temp. after mixing (0C) Exothermic or Endothermic?

sodium hydroxide soln + hydrochloric acid sodium hydrogen carbonate soln + citric acid

copper sulphate soln + magnesium powder sulphuric acid + magnesium ribbon

barium chloride + sodium sulphate

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The Energy of Physical, Chemical and Nuclear Reactions

Thermodynamics - the study of energy and energy transfer Thermochemistry - the study of energy involved in chemical reactions

Energy (symbol: E unit: J joules) Law of Conservation of Energy

- total energy of the universe is constant

- energy can neither be created nor destroyed universe=0

- energy can be transferred from one substance to another - energy can be converted into various forms

System - part of the universe that is being studied and

observed (reactants & products)

Surroundings - everything else in the universe - part of the universe that is likely to be affected by energy changes in the system

Universe = System + Surroundings univeres= system+surrounding = 0

Any change in the system is accompanied by an equal and opposite change in the surroundings. system =surrounding

Heat (symbol: Q unit: J joules) - transfer of kinetic

energy (Ek) spontaneously from warmer to cooler

objects

Temperature (symbol: T unit: K Kelvin, C

Celsius degrees) TK = TC + 273.15 - measure of the average kinetic energy of the particles that make up a substance or system Celsius scale relative to water (0C water melting point, 100C water boiling point) Kelvin scale absolute scale (O K is temp. when a substance has no kinetic energy)

Enthalpy (symbol: H unit: J joules)

- total internal energy of a substance at a constant pressure - hard to measure; includes (1) energy of physical state, (2)

energy in bonds, (3) energy in nucleus; includes:

- moving electrons within atoms - vibration of atoms connected by chemical bonds - rotation and translation of molecules - nuclear potential energy of protons and neutrons in atomic

nuclei
- electronic potential energy of atoms connected by chemical bonds

- easily measure and study change in enthalpy (H) in a

reaction - enthalpy change of a process is equivalent to its heat change at constant pressure - chemical bonds are sources of stored energy

- breaking a bond is a process that requires energy

- creating a bond is a process that releases energy

Representing Enthalpy Changes

Hrxn enthalpy of reaction (depends on

temperature and pressure)

Hrxn standard enthalpy of reaction at

SATP (25C, 100 kPa)

(1) Thermochemical Equation balanced equation that indicates enthalpy change

(2) Separate Expression

(3) Enthalpy Diagram

1. Physical changes - Small change in enthalpy (tens of kJ/mol) - Change in intermolecular bonds between molecules as they change phase o Hvap enthalpy of vaporization (liquid gas) o Hcond enthalpy of condensation (gas liquid) o Hmelt enthalpy of melting (solid liquid) o Hfre enthalpy of freezing (liquid solid)

o Hsoln enthalpy of solution (solid

2. Chemical changes - Moderate change in enthalpy (hundreds of kJ/mol) - Change in intramolecular bonds within molecules as reactants break apart to form products o Hcomb enthalpy of combustion o Hneut enthalpy of neutralization o Hf enthalpy of formation

3. Nuclear changes - Enormous change in enthalpy (billions of kJ/mol) - Change in nuclear binding energy holding together the nucleus of an atom o A significant amount of mass of the reactants is actually converted to energy o Einstein: E=mc2, where m=mass and c=speed of light (3.0x108m/s) so a tiny mass is equivalent to a significant amount of energy

Mass Defect o difference in mass between a nucleus and its nucleons (particles found in the nucleus) o caused by the energy associated with the strong force that holds a nucleus together

o the higher the nuclear binding energy, the more stable the nucleus
Nucleus + Nuclear binding energy Nucleons

References McGraw-Hill Ryerson Chemistry 12 Nelson Chemistry 12

Rates of Reactions and Enzymes

Rates of Reaction
Chemical reactions occur when different atoms or molecules collide: For the reaction to happen the particles must have a certain amount of energy this is called the ACTIVATION ENERGY.
The rate at which the reaction happens depends on four things: 1) The temperature of the reactants, 2) Their concentration 3) Their surface area 4) Whether or not a catalyst is used

Measuring rate of reaction

Two common ways:
1) Measure how fast the products are formed

2) Measure how fast the reactants are used up

Rate of reaction graph

Amount of product formed
Slower rate of reaction here due to reactants being used up

Fast rate of reaction here

Slower reaction

Time

Enzymes
Enzymes are biological catalysts. They help the reactions that occur in our bodies by controlling the rate of reaction. Yeast is an example of an enzyme. It is used to help a process called fermentation: Sugar Alcohol + carbon dioxide

The alcohol from this process is used in making drinks and the carbon dioxide can be used to make bread rise.

Enzymes work best in certain conditions:

Enzyme activity

Enzymes are denatured beyond 40OC

Could be protease (found in the stomach)

Could be amylase (found in the intestine)

400C

Temp

pH

pH

Uses of enzymes
1) Enzymes are used in washing powders to help digest food stains. Biological washing powders will only work on 400C or lower.
2) Enzymes are used in baby foods to pre-digest the proteins. 3) Enzymes are used to convert starch into sugar which can then be used in food. 4) Conversion of glucose into fructose glucose and fructose are isomers (they have the same chemical formula), but fructose is sweeter.