3 Physical chemistry

3:01 know that chemical reactions in which heat energy is given out are described as exothermic, and those in which heat energy is taken in are described as endothermic

Exothermic: chemical reaction in which heat energy is given out.

Endothermic: chemical reaction in which heat energy is taken in.

 

(So, in an exothermic reaction the heat exits from the chemicals so temperature rises)

 

3:02 describe simple calorimetry experiments for reactions such as combustion, displacement, dissolving and neutralisation

Calorimetry allows for the measurement of the amount of energy transferred in a chemical reaction to be calculated.

 

EXPERIMENT1: Displacement, dissolving and neutralisation reactions

Example: magnesium displacing copper from copper(II) sulfate

Method:

  1. 50 cm3 of copper(II) sulfate is measured and transferred into a polystyrene cup.
  2. The initial temperature of the copper sulfate solution is measured and recorded.
  3. Magnesium is added and the maximum temperature is measured and recorded.
  4. The temperature rise is then calculated. For example:
Initial temp. of solution (oC)Maximium temp. of solution (oC)Temperature rise (oC)
24.256.732.5

Note:  mass of 50 cm3 of solution is 50 g

 

The cup used is polystyrene because:

polystyrene is an insulator which reduces heats loss

 

EXPERIMENT2: Combustion reactions

To measure the amount of energy produced when a fuel is burnt, the fuel is burnt and the flame is used to heat up some water in a copper container

Example: ethanol is burnt in a small spirit burner

Method:

  1. The initial mass of the ethanol and spirit burner is measured and recorded.
  2. 100cm3 of water is transferred into a copper container and the initial temperature is measured and recorded.
  3. The burner is placed under of copper container and then lit.
  4. The water is stirred constantly with the thermometer until the temperature rises by, say, 30 oC
  5. The flame is extinguished and the maximum temperature of the water is measured and recorded.
  6. The burner and the remaining ethanol is reweighed. For example:
Mass of water (g)Initial temp of water (oC)Maximum temp of water (oC)Temperature rise (oC)Initial mass of spirit burner + ethanol (g)Final mass of spirit burner + ethanol (g)Mass of ethanol burnt (g)
10024.254.230.034.4633.680.78

The amount of energy produced per gram of ethanol burnt can also be calculated:

3:03 calculate the heat energy change from a measured temperature change using the expression Q = mcΔT

Calorimetry allows for the measurement of the amount of energy transferred in a chemical reaction to be calculated.

 

EXPERIMENT1: Displacement, dissolving and neutralisation reactions

Example: magnesium displacing copper from copper(II) sulfate

Method:

  1. 50 cm3 of copper(II) sulfate is measured and transferred into a polystyrene cup.
  2. The initial temperature of the copper sulfate solution is measured and recorded.
  3. Magnesium is added and the maximum temperature is measured and recorded.
  4. The temperature rise is then calculated. For example:
Initial temp. of solution (oC)Maximium temp. of solution (oC)Temperature rise (oC)
24.256.732.5

Note:  mass of 50 cm3 of solution is 50 g

 

EXPERIMENT2: Combustion reactions

To measure the amount of energy produced when a fuel is burnt, the fuel is burnt and the flame is used to heat up some water in a copper container

Example: ethanol is burnt in a small spirit burner

Method:

  1. The initial mass of the ethanol and spirit burner is measured and recorded.
  2. 100cm3 of water is transferred into a copper container and the initial temperature is measured and recorded.
  3. The burner is placed under of copper container and then lit.
  4. The water is stirred constantly with the thermometer until the temperature rises by, say, 30 oC
  5. The flame is extinguished and the maximum temperature of the water is measured and recorded.
  6. The burner and the remaining ethanol is reweighed. For example:
Mass of water (g)Initial temp of water (oC)Maximum temp of water (oC)Temperature rise (oC)Initial mass of spirit burner + ethanol (g)Final mass of spirit burner + ethanol (g)Mass of ethanol burnt (g)
10024.254.230.034.4633.680.78

The amount of energy produced per gram of ethanol burnt can also be calculated:

3:05 (Triple only) draw and explain energy level diagrams to represent exothermic and endothermic reactions

The symbol ΔH is used to represent the change in heat (or enthalpy change) of a reaction.

ΔH is measured in kJ/mol (kilojoules per mole).

The change in heat (enthalpy change) can be represented on an energy level diagram. ΔH must also labelled.

 

In an exothermic reaction, the reactants have more energy than the products.

Energy is given out in the form of heat which warms the surroundings.

ΔH is given a negative sign, because the reactants are losing energy as heat, e.g  ΔH = -211 kJ/mol.

 

 

 

 

In an endothermic reaction, the reactants have less energy than the products.

Energy is taken in which cools the surroundings.

ΔH is given a positive sign, because the reactants are gaining energy, e.g  ΔH = +211 kJ/mol.

 

 

 

3:06 (Triple only) know that bond-breaking is an endothermic process and that bond-making is an exothermic process

During chemical reactions, the bonds in the reactants must be broken, and new ones formed to make the products.

Breaking bonds need energy and therefore is described as endothermic.

Energy is released when new bonds are made and therefore is described as exothermic.

 

If bonds are both broken and made during chemical reactions, why can a reaction overall be describe as either exothermic or endothermic?

Example: hydrogen reacts with oxygen producing water. Overall energy is released and therefore the reaction is exothermic.

         

The reaction is exothermic because the energy needed to break the bonds is less than the energy released in making new bonds.

If a reaction is endothermic then the energy needed to break the bonds is more than the energy released in making new bonds.

3:07 (Triple only) use bond energies to calculate the enthalpy change during a chemical reaction

Each type of chemical bond has a particular bond energy. The bond energy can vary slightly depending what compound the bond is in, therefore average bond energies are used to calculate the change in heat (enthalpy change, ΔH) of a reaction.

Example: dehydration of ethanol

Note: bond energy tables will always be given in the exam, e.g:

BondAverage bond energy in kJ/mol
H-C412
C-C348
O-H463
C-O360
C=C612

So the enthalpy change in this example can be calculated as follows:

Breaking bondsMaking bonds
BondsEnergy (kJ/mol)BondsEnergy (kJ/mol)
H-C x 5(412 x 5) = 2060C-H x 4(412 x 4) = 1648
C-C348C=C612
C-O360O-H x 2(463 x 2) = 926
O-H463
Energy needed to break all the bonds3231Energy released to make all the new bonds3186

Enthalpy change, ΔH = Energy needed to break all the bonds - Energy released to make all the new bonds

ΔH = 3231 – 3186 = +45 kJ/mol (ΔH is positive so the reaction is endothermic)

3:08 practical: investigate temperature changes accompanying some of the following types of change: salts dissolving in water, neutralisation reactions, displacement reactions and combustion reactions

Calorimetry allows for the measurement of the amount of energy transferred in a chemical reaction to be calculated.

 

EXPERIMENT1: Displacement, dissolving and neutralisation reactions

Example: magnesium displacing copper from copper(II) sulfate

Method:

  1. 50 cm3 of copper(II) sulfate is measured and transferred into a polystyrene cup.
  2. The initial temperature of the copper sulfate solution is measured and recorded.
  3. Magnesium is added and the maximum temperature is measured and recorded.
  4. The temperature rise is then calculated. For example:
Initial temp. of solution (oC)Maximium temp. of solution (oC)Temperature rise (oC)
24.256.732.5

Note:  mass of 50 cm3 of solution is 50 g

 

EXPERIMENT2: Combustion reactions

To measure the amount of energy produced when a fuel is burnt, the fuel is burnt and the flame is used to heat up some water in a copper container

Example: ethanol is burnt in a small spirit burner

Method:

  1. The initial mass of the ethanol and spirit burner is measured and recorded.
  2. 100cm3 of water is transferred into a copper container and the initial temperature is measured and recorded.
  3. The burner is placed under of copper container and then lit.
  4. The water is stirred constantly with the thermometer until the temperature rises by, say, 30 oC
  5. The flame is extinguished and the maximum temperature of the water is measured and recorded.
  6. The burner and the remaining ethanol is reweighed. For example:
Mass of water (g)Initial temp of water (oC)Maximum temp of water (oC)Temperature rise (oC)Initial mass of spirit burner + ethanol (g)Final mass of spirit burner + ethanol (g)Mass of ethanol burnt (g)
10024.254.230.034.4633.680.78

The amount of energy produced per gram of ethanol burnt can also be calculated:

3:09 describe experiments to investigate the effects of changes in surface area of a solid, concentration of a solution, temperature and the use of a catalyst on the rate of a reaction

The rate of a chemical reaction can be measured either by how quickly reactants are used up or how quickly the products are formed.

The rate of reaction can be calculated using the following equation:

The units for rate of reaction will usually be grams per min (g/min)

 

An investigation of the reaction between marble chips and hydrochloric acid:

Marble chips, calcium carbonate (CaCO3) react with hydrochloric acid (HCl) to produce carbon dioxide gas. Calcium chloride solution is also formed.

Using the apparatus shown the change in mass of carbon dioxide can be measure with time.

As the marble chips react with the acid, carbon dioxide is given off.

The purpose of the cotton wool is to allow carbon dioxide to escape, but to stop any acid from spraying out.

The mass of carbon dioxide lost is measured at intervals, and a graph is plotted:

 

Experiment to investigate the effects of changes in surface area of solid on the rate of a reaction:

The experiment is repeated using the same mass of chips, but this time the chips are larger, i.e. have a smaller surface area.

Since the surface area is smaller, the rate of reaction is less.

Both sets of results are plotted on the same graph.

If instead the chips were smashed into powder (and again same mass of chips used) the surface area would be much larger and so the rate of reaction higher (steeper line on graph).

 

Experiment to investigate the effects of changes in concentration of solutions on the rate of a reaction:

The experiment is again repeated using the exact same quantities of everything but this time with half the concentration of acid. The marble chips must however be in excess. The reaction with the half the concentration of acid happens slower and produces half the amount of carbon dioxide.

 

Experiment to investigate the effects of changes in temperature on the rate of a reaction:

The experiment is once again repeated using the exact same quantities of everything but this time at a higher temperature. The reaction with the higher temperature happens faster.

 

Experiment to investigate the effects of the use of a catalyst on the rate of a reaction:

Hydrogen peroxide naturally decomposes slowly producing water and oxygen gas.

Manganese (IV) oxide can be used as a catalyst to speed up the rate of reaction.

The rate of reaction can be measured by measuring the volume of oxygen produced at regular intervals using a gas syringe.

Both sets of results are plotted on the same graph.

 

 

 

 

 

 

 

Experiment to investigate the reaction between varying concentrations of sodium thiosulfate and hydrochloric acid

Sodium thiosulfate (Na2S2O3) and hydrochloric acid (HCl) are both colourless solutions. They react to form a yellow precipitate of sulfur.

     sodium thiosulfate   +   hydrochloric acid    →     sodium chloride   +   sulfur dioxide   +   sulfur   +   water

    Na2S2O3(aq)         +         2HCl(aq)           →           2NaCl(aq)         +         SO2(g)         +         S(s)         +         H2O(l)

 

To investigate the effects of changes in concentration of sodium thiosulfate on the rate of a reaction, the conical flask is placed above a cross. The reaction mixture is observed from directly above and the time for a cross to disappear is measured. The cross disappears because a precipitate of sulfur is formed.

In order to change the concentration of sodium thiosulfate, the volumes of sodium thiosulfate and water are varied (see results table). However the total volume of solution must always be kept the same as to ensure that the depth of the solution remains constant.

In this reaction, sulfur dioxide gas (SO2), which is poisonous is produced therefore the experiment must be carried out in a well ventilated room.

The results are recorded in the table below and then plotted onto a graph.

Volume of Na2S2O3(aq) (cm3)Volume of water (cm3)Concentration of Na2S2O3(aq) (mol/dm3)Time taken for cross to disappear (s)Rate of reaction (s-1) (1/time)
5000.10450.0222
40100.08600.0167
30200.06800.0125
20300.04130.0769
10400.022550.0039

The graph shows that the rate of reaction is directly proportional to the concentration.

The experiment can also be repeated to show how temperature affects the rate of reaction.

In this experiment the concentration of sodium thiosulfate is kept constant but heated to range of different temperatures.

As a rough approximation, the rate of reaction doubles for every 10oC temperature rise.

 

3:10 describe the effects of changes in surface area of a solid, concentration of a solution, pressure of a gas, temperature and the use of a catalyst on the rate of a reaction

Increasing the surface area of a solid increases the rate of a reaction.

Increasing the concentration of a solution increases the rate of a reaction.

Increasing the pressure of a gas increases the rate of a reaction.

Increasing the temperature increases the rate of a reaction.

Using a catalyst increases the rate of a reaction.

3:11 explain the effects of changes in surface area of a solid, concentration of a solution, pressure of a gas and temperature on the rate of a reaction in terms of particle collision theory

Increasing the surface area of a solid:

  • more particles exposed
  • more frequent collisions
  • increase the rate of a reaction

 

Increasing the concentration of a solution or pressure of a gas:

  • more particles in same space
  • more frequent collisions
  • increase rate of reaction

 

Increasing the temperature:

  • particles have more kinetic energy
  • more frequent collisions
  • and a higher proportion of those collisions are successful because the collision energy is greater or equal to the activation energy
  • increase rate of reaction

 

3:12 know that a catalyst is a substance that increases the rate of a reaction, but is chemically unchanged at the end of the reaction

A catalyst is a substance that increases the rate of a reaction, but is chemically unchanged at the end of the reaction.

3:13 know that a catalyst works by providing an alternative pathway with lower activation energy

Catalyst: A substance that speeds up a chemical reaction while remaining chemically unchanged at the end of
the reaction.

A catalyst is not used up in a reaction.

A catalyst speeds up a reaction by providing an alternative pathway with lower activation energy.

3:14 (Triple only) draw and explain reaction profile diagrams showing ΔH and activation energy

Below is a diagram showing the reaction profile for the reaction of hydrogen with oxygen, which is EXOTHERMIC:

The activation energy is the minimum amount of energy required to start the reaction.

For an exothermic reaction, the products have less energy than the reactants. The difference between these energy levels is ΔH.

For an exothermic reaction, more energy is released when bonds are formed than taken in when bonds are broken.

 

Below is a diagram showing the reaction profile for the thermal decomposition of calcium carbonate, which is ENDOTHERMIC:

The activation energy is the minimum amount of energy required to start the reaction.

For an endothermic reaction, the products have more energy than the reactants. The difference between these energy levels is ΔH.

For an endothermic reaction, more energy is taken in to break bonds than is released when new bonds are formed.

3:15 practical: investigate the effect of changing the surface area of marble chips and of changing the concentration of hydrochloric acid on the rate of reaction between marble chips and dilute hydrochloric acid

The rate of a chemical reaction can be measured either by how quickly reactants are used up or how quickly the products are formed.

The rate of reaction can be calculated using the following equation:

The units for rate of reaction will usually be grams per min (g/min)

 

An investigation of the reaction between marble chips and hydrochloric acid:

Marble chips, calcium carbonate (CaCO3) react with hydrochloric acid (HCl) to produce carbon dioxide gas. Calcium chloride solution is also formed.

Using the apparatus shown the change in mass of carbon dioxide can be measure with time.

As the marble chips react with the acid, carbon dioxide is given off.

The purpose of the cotton wool is to allow carbon dioxide to escape, but to stop any acid from spraying out.

The mass of carbon dioxide lost is measured at intervals, and a graph is plotted:

 

Experiment to investigate the effects of changes in surface area of solid on the rate of a reaction:

The experiment is repeated using the exact same quantities of everything but using larger chips. For a given quantity, if the chips are larger then the surface area is lesson. So reaction with the larger chips happens more slowly.

Both sets of results are plotted on the same graph.

 

Experiment to investigate the effects of changes in concentration of solutions on the rate of a reaction:

The experiment is again repeated using the exact same quantities of everything but this time with half the concentration of acid. The marble chips must however be in excess. The reaction with the half the concentration of acid happens slower and produces half the amount of carbon dioxide.

 

3:16 practical: investigate the effect of different solids on the catalytic decomposition of hydrogen peroxide solution

Oxygen (O2) is made in the lab from hydrogen peroxide (H2O2) using manganese(IV) oxide (MnO2) as a catalyst.

 

 

Different catalysts could be used to investigate which is the most effective in decomposing hydrogen peroxide. Examples of other substances which could be tested are:

  • Manganese dioxide
  • Liver
  • Potato
  • Potassium iodide
  • Copper oxide
  • Sodium chloride

Only some of these are effective catalysts when used with hydrogen peroxide. If a substance is not a catalyst, there will be no bubbles of oxygen produced. For other substances, such as liver which is a very effective catalyst in the decomposition of hydrogen peroxide, bubbles of oxygen will be produced quickly.

 

 

 

3:18 describe reversible reactions such as the dehydration of hydrated copper(II) sulfate and the effect of heat on ammonium chloride

Dehydration of copper(II) sulfate

 

Heating ammonium chloride

On heating, white solid ammonium chloride decomposes forming ammonia and hydrogen chloride gas. On cooling, ammonia and hydrogen chloride react to form a white solid of ammonium chloride:

 

3:20 (Triple only) know that the characteristics of a reaction at dynamic equilibrium are: the forward and reverse reactions occur at the same rate, and the concentrations of reactants and products remain constant

Features of a reaction mixture that is in dynamic equilibrium:

  1.   the concentrations of reactants and products remain constant
  2.   rate of forward reaction = rate of backward reaction

3:21 (Triple only) understand why a catalyst does not affect the position of equilibrium in a reversible reaction

A catalyst is a substance which increases the rate of reaction without being chemically changed at the end of the reaction.

A reversible reaction is one where the forward reaction and the backward reaction happen simultaneously. For example:

3H₂ + N₂ ⇋ 2NH₃

In such a reaction a catalyst speeds up both the forward and the backward reactions. Hence, although the system will reach dynamic equilibrium more quickly, the addition of a catalyst will not affect the position of equilibrium.

3:22 (Triple only) predict, with reasons, the effect of changing either pressure or temperature on the position of equilibrium in a reversible reaction (references to Le Chatelier’s principle are not required)

In a reversible reaction the position of the equilibrium (the relative amounts of reactants and products) is dependent on the temperature and pressure of the reactants.

If the conditions of an equilibrium reaction are changed, the reaction moves to counteract that change.

Therefore by altering the temperature or pressure the position of the equilibrium will change to give more or less products.

Adding a catalyst does not affect the position of the equilibrium.

 

If a change in conditions moves equilibrium to the right, the yield of the substances on the right is increased.

 

Changing the temperature:

All reactions are exothermic in one direction and endothermic in the other way.

For this reaction the enthalpy change, ΔH is negative therefore the forward reaction is exothermic:

     CO(g)     +             2H2(g)                    ⇌            CH3OH(g)              ΔH = –91 kJ/mol

If temperature is decreased the position of the equilibrium will shift to the right because it is an exothermic reaction.

For this reaction the enthalpy change, ΔH is positive therefore the forward reaction is endothermic:

     CH4(g)                     +              H2O(g)                    ⇌            CO(g)      +              3H2(g)                     ΔH = +210 kJ mol–1

If temperature is increased the position of the equilibrium will shift to the right because it is an endothermic reaction.

Key point: an increase (or decrease) in temperature shifts the position of equilibrium in the direction of the endothermic (or exothermic) reaction

 

Changing the pressure:

Reactions may have more molecules of gas on one side than on the other.

For this reaction there are 2 molecules on the left and 4 molecules on the right:

     CH4(g)                     +              H2O(g)                    ⇌            CO(g)      +              3H2(g)                     ΔH = +210 kJ mol–1

If the pressure is increased the position of the equilibrium will shift to the left because there are fewer molecules on the left-hand side.

For this reaction there are 3 molecules on the left and 1 molecule on the right

     CO(g)     +             2H2(g)                    ⇌            CH3OH(g)              ΔH = –91 kJ/mol

If the pressure is decreased the position of the equilibrium will shift to the left because there are more molecules on the left-hand side.

Key point: an increase (or decrease) in pressure shifts the position of equilibrium in the direction that produces fewer (or more) moles of gas

Select a set of flashcards to study:

     Terminology

     Skills and equipment

     Remove Flashcards

Section 1: Principles of chemistry

      a) States of matter

      b) Atoms

      c) Atomic structure

     d) Relative formula masses and molar volumes of gases

     e) Chemical formulae and chemical equations

     f) Ionic compounds

     g) Covalent substances

     h) Metallic crystals

     i) Electrolysis

 Section 2: Chemistry of the elements

     a) The Periodic Table

     b) Group 1 elements: lithium, sodium and potassium

     c) Group 7 elements: chlorine, bromine and iodine

     d) Oxygen and oxides

     e) Hydrogen and water

     f) Reactivity series

     g) Tests for ions and gases

Section 3: Organic chemistry

     a) Introduction

     b) Alkanes

     c) Alkenes

     d) Ethanol

Section 4: Physical chemistry

     a) Acids, alkalis and salts

     b) Energetics

     c) Rates of reaction

     d) Equilibria

Section 5: Chemistry in industry

     a) Extraction and uses of metals

     b) Crude oil

     c) Synthetic polymers

     d) The industrial manufacture of chemicals

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