chapter 4 thermochemistry

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Chapter 4 Thermochemistry

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Chapter 4

Thermochemistry

A. Energy Changes in Chemical Reactions

Thermochemistry

The study of changes in heat energy which take place during chemical reactions

Classify into:

• Exothermic reaction

• Endothermic reaction

TIPS: EX mean to go out/exit EN mean to come in/enter

EXOTHERMIC REACTION

ENDOTHERMIC REACTION

Energy level diagram

The energy of the products is lower than

the total energy of the reactants

The energy of the products is higher than

the energy of the reactants

Energy

Reactants

Products

∆H = negative

Energy

Reactants

Products

∆H = positive

Exothermic reaction Endothermic reaction

Definition A chemical reaction that gives out heat to

the surroundings

A chemical reaction that absorbs heat

from the surroundings

What happen?

During exothermic reaction,

temperature of the surrounding

increases.

This is because heat given out from

the reaction is transferred to the

surroundings.

During endothermic reaction,

temperature of the surrounding

decreases.

This is because the reactants absorb

heat energy from the surroundings.

Heat of reaction, ∆H

The change in the amount

of heat in a chemical

reaction.

∆H negative: heat is given out ∆H positive: heat is absorbed

Step to construct energy level diagrams

Step 6 Label ∆H as positive or negative

Step 1 Identify whether the reaction is exothermic or

endothermic

Step 2 Draw and label the energy axis

Step 3 Draw the energy level for reactants and

products

Step 4 Draw an arrow from reactants level to the

products level

Step 5 Write the reactants and products based on the

balanced chemical equations

Construct energy level diagrams for the following thermochemical equations

• Zn + 2HCl → ZnCl2 + H2 ∆H = -152 kJ

• N2 + 2O2 → 2NO2 ∆H = +220 kJ

• KOH + HNO3 → KNO3 + H2O ∆H = -57 kJ

• C + 2S → CS2 ∆H = +220 kJ

• Ca(NO3)2 + K2CO3 → CaCO3 + 2KNO3 ∆H = +12 kJ

Energy change during formation and breaking of bonds

Usually a chemical reaction involves bond breaking and bond formation.

• Bond breaking : always requires energy

• Bond formation : always releases energy

Endothermic

Energy absorb for bond breaking is

more than energy released from bond

formation

∆H positive

Type of Reaction Energy Change Sign of ∆H

Exothermic

Energy absorb for bond breaking is

less than energy released from bond

formation

∆H negative

Application of exothermic and endothermic reaction

Cold packs

Contain chemicals (water & solid ammonium nitrate, NH4NO3) that react to absorb heat from surroundings.

• Help to reduce high temperature

• Help to reduced swelling

Application of exothermic and endothermic reaction

Hot packs

Contain chemicals (calcium chloride, CaCl2

or magnesium sulphate, MgSO4 and water)that react to release heat.

• Help to warm up something

• Help to lessen the pain of aching muscles

Application of exothermic and endothermic reaction

Reusable heat pack

Contain sodium acetate crystallization and re-solution system

Lye (drain cleaner)

Contain sodium hydroxide, NaOH

Heat of Reaction

• The change in the amount of heat in a chemical reaction.

• Symbol: ∆H

Different types of reactions

Combustion Heat of Combustion

Types of Reaction Heat of Reaction

Precipitation Heat of Precipitation

Displacement Heat of Displacement

Neutralization Heat of Neutralization

Heat of Combustion

The heat change when one mole of a substance is

completely burnt in oxygen under standard

conditions

Heat of reaction Definition

Heat of Precipitation The heat change when one mole of a precipitate is

formed from their ions in aqueous solution

Heat of Displacement

The heat change when one mole of a metal is

displaced from its salt solution by a more

electropositive metal

Heat of Neutralization The heat change when one mole of water is formed

from reaction between an acid and an alkali

The Ways to Calculate Heat of Reaction

Heat of Precipitation

Experiment to investigate the heat of precipitation between

silver nitrate solution and sodium chloride solution

Heat of Precipitation

Procedure:

1. Measure 25 cm3 of 0.5 mol dm-3 sodium chloride, NaCl solution using

a measuring cylinder and pour the solution into a polystyrene cup.

2. Measure and record the initial temperature of sodium chloride

solution.

3. Measure 25 cm3 of 0.5 mol dm-3 silver nitrate, AgNO3 solution using a

measuring cylinder and pour the solution into another polystyrene

cup.

4. Measure and record the initial temperature of silver nitrate solution.

5. Pour silver nitrate, AgNO3 solution into the polystyrene containing

sodium chloride, NaCl solution.

6. Stir the mixture and record the highest temperature, θ3

Tabulation of data:

Initial temperature silver nitrate solution :

Initial temperature sodium chloride solution :

Highest temperature :

Heat of Displacement

Experiment to investigate the heat of displacement of copper

by zinc

Copper(II) nitrate

0.5 g zinc powder

Polystyrene cup

Heat of Displacement

Procedure:

1. Measure 25 cm3 of 0.2 mol dm-3 copper(II) nitrate solution

using a measuring cylinder.

2. Pour the solution into a polystyrene cup.

3. Measure and record the initial temperature, θ1 of

copper(II) nitrate solution.

4. Measure 0.5 g of zinc powder and added into the

polystyrene quickly.

5. Stir the mixture and the highest temperature is recorded,

θ2

Tabulation of data:

Initial temperature copper(II) nitrate solution :

Highest temperature :

Heat of Neutralization

Describe an experiment to determine the heat of neutralization between dilute hydrochloric acid and sodium hydroxide solution.

100cm3 of 2 mol dm-3 dilute hydrochloric acid

100 cm3 of 2 mol dm-3 aqueous sodium hydroxide Plastic cup

Procedure:

1. 50 cm3 of 2.0 mol dm-3 sodium hydroxide solution is

measured using a measuring cylinder and poured into a

plastic cup.

2. The initial temperature of sodium hydroxide solution is

measured after a few minutes.

3. 50 cm3 of 2.0 mol dm-3 hydrochloric acid is measured using

another measuring cylinder and poured into a plastic cup.

4. The initial temperature of hydrochloric acid solution is

measured after a few minutes.

5. The hydrochloric acid is then poured quickly and carefully

into the sodium hydroxide solution.

6. The mixture is stirred using thermometer and the highest

temperature reached is recorded.

Heat of Neutralization

All neutralization process can be presented by the following ionic equation

H+ + OH- → H2O ∆H = -57 kJ mol-1

• Heat of neutralization for strong acid and strong alkali is same, that is -57 kJ mol-1

• Heat of neutralization for weak acid and strong alkali is less than -57 kJ mol-1

• Heat of neutralization for weak acid and weak alkali is much lesser

Strong acid & strong alkali

Explanation:

Strong acid ionise completely in water to produce high concentration of hydrogen ions

HCl → H+ + Cl-

1 mol of hydrogen ions reacts with 1 mol of hydroxide ions to form I mol of water to release 57 kJ of heat energy

KOH/NaOH with HCl/HNO3

Weak acid & strong alkali

Explanation:

Weak acid ionise partially in water to produce low concentration of hydrogen ions

CH3COOH + CH3COO- + H+

Most of the ethanoic acid still remains in the form of molecule

Thus the heat release is always less than 57 kJ

Weak acid & weak alkali

Explanation:

More heat energy is needed to dissociate both the weak acid and weak alkali completely to produce hydrogen ions.

Monoprotic acid & Diprotic acid

H2SO4 + 2NaOH → Na2SO4 + 2H2O ∆H = - 114.6 kJ HCl + NaOH → NaCl + H2O ∆H = - 57.3 kJ

Explain the differences of heat of reaction.

1. H2SO4 is a diprotic acid while HCl is monoprotic acid.

2. H2SO4 will produce 2 mole of H+ ions and HCl produce 1 mole of H+ ion

3. Neutralization of a diprotic acid will produce twice heat energy than monoprotic acid

Heat of Combustion

Describe an experiment to determine the heat of combustion of butanol in the laboratory.

In your description include a labelled diagram, procedure and tabulation of data

Heat of Combustion

Procedure:

1. 100 cm3 of water is measured using a measuring cylinder.

2. Poured into a copper tin.

3. The initial temperature of water is measured and

recorded, θ1 .

4. The spirit lamp is filled with butanol and weighed, x g

5. A spirit lamp is light and put under the copper tin.

Heat of Combustion

Procedure:

6. The water is stirred continuously with a thermometer

7. When the temperature of water increased by 30 °C, the

flame is put off

8. The spirit lamp is weighed again, y g

9. The highest temperature is recorded, θ2

Heat of Combustion

Results:

Mass of weight of spirit lamp + butanol / g x

Final mass of spirit lamp + butanol / g y

Mass of butanol used / g x-y = z

Highest temperature of water / °C θ2

Initial temperature of water / °C θ1

Increased in temperature / °C θ2 - θ1 = θ3

Heat of Combustion

When 2.7 g of glucose (C6H12O6) is burnt completely in excess oxygen, the heat released increases the temperature of 600 g of water by 12.5 °C. Calculate the heat of combustion of glucose.

[Specific heat capacity of water = 4.2 J g-1 °C-1, density of water = 1.0 g cm-3, RAM: H = 1, C = 12, O = 16]

When 1 mole of butanol is burnt in excess of oxygen, 2600 kJ of heat is produced. Calculate the mass of butanol needed to burn completely in oxygen in order to raise the temperature of 250 cm3 of water by 30 °C.

[Specific heat capacity of water = 4.2 J g-1 °C-1, density of water = 1.0 g cm-3, RAM: H = 1, C = 12, O = 16]

Comparing & contrasting heats of combustion

Draw a graph of the number of carbon atoms in alcohol

againts the magnitude of the heat of combustion.

Alcohol Molecular formula

Heat of combustion (kJ/mol)

Methanol -728

Ethanol -1376

Propanol -2016

Butanol -2678

Pentanol - 3332

Hexanol

From the graph:

1. State the relationship between the number of

carbon atoms in an alcohol and the heat of

combustion

2. Predict the heat of combustion of hexanol

Compare the heat of combustion between ethanol and butanol. Explain why there is a difference in the heat of combustion between ethanol and butanol.

1. The heat of combustion of butanol is higher than ethanol.

2. Butanol has higher number of carbons per molecules than ethanol

3. Butanol will produced more carbon dioxide and water than ethanol

4. The combustion of butanol produced more heat than ethanol.