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Chapter 13

Form 5 Chapter 13 : THERMOCHEMISTRY

Thermochemistry is the study of changes in heat energy during chemical reaction. Two types of chemical reactions : 1. Exothermic reaction 2. Endothermic reaction 13.1 : ENERGY CHANGES IN CHEMICAL REACTIONS 1. Chemical energy is stored within the chemical bonds. During a chemical reaction, chemical bonds of the reactants are broken and new bonds in the products are formed. When bonds are broken, heat energy is . When bonds are formed, heat energy is . 2. Energy that is released or absorbed is in the form of energy. 3. The energy change (the difference between the energy of reactants and the products) in a chemical reaction is called heat of reaction, H. 4. Heat of reaction, H is the energy change when one mole of reactant reacts or when one mole of product is formed. H = Total energy content of products total energy content of reactants = Hproducts Hreactants

5. Two types of reactions that occur are : Exothermic reaction Endothermic reaction 13.1.1 Exothermic Reaction Example :

2H2 + O2

2H2O ,

H = - 486 kJ

Bonds are broken in the reactants : ( +1370 kJ heat energy absorbed)

New bonds are formed in the products: (-1856 kJ heat energy released ) :
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Energy change in the reaction :

Energy

Interpretation :

The quantity of energy absorbed for bonds breaking between

lower hydrogen atoms and oxygen atoms are .. than

Energy absorbed +1370 kJ 2H2 + O2
H = - 486 kJ 2H2O

energy released for the formation of bonds between hydrogen

Energy released -1856 kJ

and oxygen atoms.

strong Weak . bonds are broken and .. bonds are formed.

Heat is released to the surrounding temperature increases.

negative The sign of H is .

Energy change : Chemical energy Heat energy

Total energy content are decreased. Total energy content of the Energy change : H = 1370 - 1856 = - 486 kJ product is lower/less than total energy of the reactants.
The value of H is -486 kJ The heat released from bond formation is greater than heat absorbed for bond breaking. A negative sign for H shows that heat is released.

Energy Level Diagram

Energy level diagram shows the total energy content of the reactants compared to the products. Energy level diagram for exothermic reactions :
Energy

Reactants t/b
H negative (heat is released)

Products

Total energy content of the products is less than total energy of the reactants. Example of exothermic reactions : Chemical equation Neutralisation Reaction between acids and metals Reaction between acids and carbonate Combustion of alcohol Dissolving sodium hydroxide in water Adding water to concentrated acid.
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2KOH

+ H2SO4 K2SO4 + 2 H2O

Mg + 2HCl MgCl2 + H2 Na2CO3 + H2SO4 Na2SO4 + H2O + CO2 C2H5OH + 3O2 2CO2 + 3H2O NaOH(s) H2SO4(aq) Na+ (aq) + OH- (aq) 2H+ (aq) + SO42-(aq)
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13.1.2 Endothermic Reaction Energy Change in Endothermic Reaction:

Energy Energy released ( -ve)
Energy absorbed (+ve)

Interpretation :

higher The quantity of energy absorbed for bonds breaking is

than energy released from the formation of bonds.

Strong weak ... bonds are broken and ... bonds are formed.
Heat is absorbed from the surrounding temperature decreases

Products
H positive

positive The sign of H is .

Energy change : Heat energy Chemical energy Total energy content are increased. Total energy content of the product is more than total energy of the reactants.

Reactants

Energy Level Diagram

Energy level diagram shows the total energy content of the reactants compared to the products . Energy level diagram for exothermic reactions :
Energy

Products b
H positive (heat is absorbed)

Reactants
Total energy content of the products is greater/more than total energy of the reactants. Example of endothermic reactions : Chemical equation Decomposition of nitrate and carbonate salt when heated Decomposition of hydrated salt to anhydrous salt and water when heated

CaCO3

CaO + CO2 CuSO4(s) + 5H2O(l) (white)

CuSO4.5H2O(s) (blue)

Dissolving ammonium salts/nitrate salts in water

H2O

NH4Cl(s)

NH4+ (aq) + Cl- (aq)

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Activity 1:1 Complete the following table to compare and contrast between Exothermic and Endothermic reactions.

Exothermic
Absorb /release heat Temperature of surrounding change Total energy content Release heat Increase

Endothermic
Absorb heat Decrease Products reactants

Reactants

products

Energy Reactants

Energy Products

Energy level diagram H = -ve

Products Reactants

H = +ve

Value of H

Negative

Positive

Construct energy level diagram for the following thermochemical equations : (i) (ii)
Energy

HCl

+ NaOH

NaCl

+ H2O

H = -57 kJ H = +26 kJ

NH4NO3(s)

NH4+(aq) + NO3 -(aq)

Energy

HCl + NaOH H = - 57 kJ mol-1 NaCl + H2O NH4NO3

NH4+ + NO3H = + 26 kJ mol-1

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13.2 : APPLICATION OF KNOWLEDGE OF EXOTHERMIC AND ENDOTHERMIC REACTIONS IN EVERYDAY LIFE (a) Hot packs Contain chemicals that released heat [exothermic reaction] It is a plastic bag containing separate compartments of water and anhydrous calcium chloride. The anhydrous calcium chloride dissolve in water to release heat; the temperature increase.

CaCl2(s)

H2O

Ca2+(aq) + 2Cl-(aq)

H = - 83 kJ

Other substances that can be used in a hot pack are anhydrous magnesium sulphate, anhydrous copper(II) sulphate and calcium oxide. A reusable hot pack uses supersaturated solution of sodium ethanoate crystallization and resolution. (b) Cold packs Contain chemicals that absorbed heat [endothermic reaction] It is a plastic bag containing separate compartments of water and solid ammonium nitrate. The solid ammonium nitrate dissolve in water and absorbed heat from surrounding;the temperature decrease.
H2O

NH4NO3(s)

NH4+(aq) + NO3 - (aq)

H = + 83 kJ

Other substances that can be used in a cold pack are ammonium chloride, potassium nitrate and sodium thiosulphate.

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4.3 : DETERMIINE THE HEAT OF REACTION (H) 1. Heat of Reaction, H the energy change when one mole of reactant reacts or the energy change when one mole of product is formed. 2. Four types of heat of reaction discussed in this chapter are : Heat of reaction Definition Example Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(s) + 2NaNO3(aq), H = -50.4 kJ 1 Heat of Precipitation Heat change/ Heat energy released when 1 mol of precipitate is formed. Ionic equation : Pb2+ + SO42- PbSO4 50.4 kJ heat energy is released when 1 mol of lead(II) ions reacted with 1 mol of sulphate ions to form 1 mol of lead (II) sulphate. Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s), H = -217 kJ 2 Heat of Displacement Heat change/ Heat energy released when 1 mol of metal is displaced from its salt solution. Ionic equation : Cu2+ + Zn Zn2+ + Cu 217 kJ heat energy is released when 1 mol of copper is displaced from copper(II) sulphate solution by zinc. KOH(aq) + HNO3 (aq) KNO3(aq) + H2O(l), H = -57 kJ Heat of Neutralisation Heat change / Heat energy released when 1 mol of water is formed from neutralisation of acid with an alkali. Ionic equation : H+ + OH H2O 57 kJ heat energy is released when 1 mol of water formed from neutralization of potassium hydroxide with nitric acid.

Heat of Combustion

Heat change / Heat energy released when 1 mol of fuel is burnt completely in excess oxygen.

C2H5OH + 3O2 2CO2 + 3H2O, H = -1366 kJ 1366 kJ heat energy is released when 1 mol of ethanol is burnt completely in excess oxygen.

3. Method of calculating H
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Quantity of heat change in a substance depends on : Mass of substance, m (g) Specific heat capacity of a substance, c ( J g-1 oC-1 ) Temperature change, (oC)

Heat change, H = mc (J)

As the chemical reaction occurs in an aqueous solution, these assumptions are made during the calculation of heat of reaction : Density of aqueous solution = Density of water = 1 g cm-3 1 cm3 of aqueous solution has a mass of 1 g 250 cm3 of aqueous solution has a mass of 250 g x cm3 of aqueous solution has a mass of x g
o

Specific heat capacity of solution, c = Specific heat capacity of water = 4.2 J g-1 C-1

No heat lost to the surroundings during reaction, all heat released in an exothermic reaction is absorbed into the reaction mixture.

Heat change, H The heat change in a reaction can be calculated the following formula :

Heat change = mc

m = mass of the solution in gram c = specific heat capacity of solution in J g-1 oC-1 = temperature change in C

Heat of reaction , H Heat of reaction ( H) is the energy change when one mole of reactant reacts or one mole of product is formed. Calculation : If n mol of reactant/product absorbs/releases H J of heat energy, 1 mol of reactant/product absorbs/releases H (heat of reaction) = +/-

H n

J mol -1

H n

x = number of moles of reactant/product

Note : i. The sign of H is negative for exothermic reaction ( temperature increases) ii. The sign of H is positive for endothermic reaction (temperature decreases) iii. The unit for heat of reaction is kJ mol-1. iv. When the amount of heat is presented in H, it is written H = +/- kJ mol-1. Example 1 : (Heat of Precipitation)
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60 cm3 of 0.025 mol dm-3 silver nitrate solution reacts with 60 cm3 of 0.025 mol dm -3 potassium bromide solution at a temperature of 29 oC. A yellow precipitate was formed and the highest temperature reached is 32 oC. Determine the heat of reaction, H and draw the energy level diagram for this reaction. Solution : Steps S1: Determine the mass of the solution, m (Density of aqueous solution = 1 g cm-3) S2 : Determine the temperature change, S3 : Determine the energy change/ heat released, H (Specific heat capacity of solution = 4.2 J g-1 oC-1) S4 : Determine the number of moles of silver bromide precipitated, n Calculation Mass of the solution, m = ( 60 cm3 + 60 cm3 ) 1 g cm-3 m = 120 g Temperature change, = 32 29 = 3 oC Heat released, H = mc = 120 4.2 3 = 1512 J = 0.025 60 1000 = 0.0015 mol Number of moles of Br= 0.025 60 1000 = 0.0015 mol

Number of moles of Ag+

AgNO3 + KBr AgBr Ag+ + Br- AgBr

or

+ KNO3

From the ionic equation : 1 mol of Ag+ ions reacts with 1 mol of Br- ions to form 1 mol of AgBr 0.0015 mol of Ag+ ions reacts with 0.0015 mol Br- ions to form 0.0015 mol of AgBr. Number of mole of AgBr, n = 0.0015 mol S5 : Determine the heat of reaction, H H

= -

H n

= - 1512 0.0015

= - 100800 J mol-1
= - 1008 kJ mol-1

H is negative because temperature increased / heat is released to the surrounding (Exothermic reaction).

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Energy Level Diagram : From chemical equation

Energy AgNO3 + KBr

H =

- 100.8 kJ mol-1

AgBr + KNO3

or From ionic equation

Energy Ag+ + BrH =

- 100.8 kJ mol-1

AgBr

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Example 2 : (Heat of Displacement) Excess zinc, Zn powder is added to 50 cm3 of 0.05 mol dm-3 copper(II) nitrate, Cu(NO3)2 solution. The temperature of the reaction mixture rises by 2.62 oC. Calculate the heat of displacement, H of copper, Cu from its salt solution and draw the energy level diagram for this reaction. Solution : Steps S1: Determine the mass of the solution, m (Density of aqueous solution = 1 g cm-3) S2 : Determine the temperature change, S3 : Determine the heat released, H (Specific heat capacity of solution = 4.2 J g-1 oC-1) S4 : Determine the number of moles of copper(II) nitrate, n Calculation Mass of the solution, m = 50 cm3 1 g cm-3 m = 50 g Temperature change, = 2.62 oC Heat released, H = mc = 50 4.2 2.62 = 550.2 J

Num. of moles of Cu(NO3)2 / Cu2+ = 0.05 50

1000

= 0.0025 mol

Cu(NO3)2 + Zn

Cu

+ Zn(NO3)2

From the equation : 1 mol of Cu(NO3)2 form 1 mol of Cu 0.0025 mol of Cu(NO3)2 form 0.0025 mol of Cu Number of mole of Cu displaced, n = 0.0025 mol S5 : Determine the heat of reaction, H H

= -

H n

= - 550.2 0.0025

= - 220080 J mol-1
= - 220.08 kJ mol-1

H is negative because temperature increased/rised. Heat is released to the surrounding (Exothermic reaction)

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Energy Level Diagram : From chemical equation

Energy Cu(NO3)2 + Zn
H =

- 220.08 kJ mol-1

Cu + Zn(NO3)2

or From ionic equation

Energy Cu2+ + Zn
H =

- 220.08 kJ mol-1

Cu + Zn2+

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Example 3 : (Heat of Combustion) Diagram below shows the set-up of apparatus for an experiment to determine the heat of combustion of butanol.

Thermometer Wind shield Copper can 250 cm3 of water

Butanol Wooden block

Result : Volume of water in copper can, m Initial temperature of water, T1 The highest temperature of water, T2 Initial mass of spirit lamp contains butanol Final mass of spirit lamp = 250 cm3 = 28.0 0C = 59.5 0C = 175.20 g = 174.10 g

Calculate the heat of combustion, H of butanol, C4H9OH and draw the energy level diagram for this reaction. Solution : Steps S1: Determine the mass of the water, m (Density of aqueous solution = 1 g cm-3) S2 : Determine the temperature change, S3 : Determine the heat released, H (Specific heat capacity of solution = 4.2 J g-1 oC-1) S4 : Determine the number of moles of butanol is burnt, n
Mr of C4H9OH = 4(12) + 10(1) +16 = 74

Calculation Mass of the solution, m = 250 cm3 1 g cm-3 m = 250 g Temperature change, = 59.5 28.0 = 11.5 oC Heat released, H = mc = 250 4.2 11.5 = 12075 J = 175.20 174.10 = 1.10 g =
1.10 74

Mass of C4H9OH

Num. of moles of C4H9OH

= 0.015 mol
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S5 : Determine the heat of reaction, H

= -

H n

= - 12075 0.015

= - 805000 J mol-1
= - 805 kJ mol-1

H is negative because temperature increased/rised. Heat is released to the surrounding (Exothermic reaction)

Chemical equation :

C4H9OH + 6O2
Energy Level Diagram :

4CO2 + 5H2O

Energy C4H9OH + 6O2

H =

- 805 kJ

4CO2 + 5H2O

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13.4

ACTIVITY / EXPERIMENT TO DETERMINE HEAT OF REACTION Procedure Set up of apparatus :

Thermometer Metal powder Polystyrene cup Salt solution

Heat of Reaction

Heat of displacement

Procedure : 1. Measure the volume of salt* solution using a measuring cylinder. 2. Pour the salt solution into a polystyrene cup. 3. Determine the initial temperature (T1). 4. Quickly and carefully, excess metal** powder is added into the solution. 5. The mixture is stirred with a thermometer and the highest temperature reached is recorded (T2). Set up of apparatus :

Volume of salt solution

Specific heat = T2 T1 capacity of water

Number of moles of metal displaced [calculated from balanced equation of displacement reaction]

Acid Acid Alkali Alkali

Heat of neutralisation

Procedure : 1. Measure the volume of acid* and alkali** using measuring cylinders. 2. Pour the solutions into different polystyrene cups. 3. Record the initial temperature of acid & alkali (Ta and Tb). 4. Quickly and carefully, acid is poured into the alkali. 5. The mixture is stirred with a thermometer and the highest temperature reached is recorded (T2).

Total volume of acid and alkali

Specific T1 = Ta + Tb heat 2 capacity of water

Number of moles of water formed. [calculated from balanced equation of neutralisation reaction]

= T2 T1

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Set up of apparatus :

Heat of precipitation

Solution B Solution A

Total volume of both aqueous salt solutions

Specific heat = T2 T1 capacity of water

Number of moles of

precipitate
[calculated from balanced equation of reaction]

Procedure : [Use two aqueous solutions that contain the cation and the anion of the insoluble salt]. Procedure is the same as above. Set up of apparatus :
Thermometer Copper can Water

Heat of combustion

Fuel /alcohol

Volume of water in the copper can

Specific heat = T2 T1 capacity of water

m1 m2 RMM of fuel

Procedure : 1. Determine the mass of fuel used by measuring the weight of the lamp with the fuel before burning, m1 and after burning, m2. 2. The heat released during burning is used to raise the temperature of water in the copper can [determine the initial temperature of water, T1 and the highest temperature, T2]

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13.4.1 Comparison of Heat of Neutralisation (a) Strong acid and strong alkali : All neutralisation process can be represented by the following equation :

H+ + OH- H2O,

H = - 57 kJ mol1

1 mol of hydrogen ions react with 1 mol of hydroxide ions to form 1mol of water to release 57 kJ of heat energy. Heat of neutralisation for KOH/ NaOH with HCl and HNO3 is the same because all these reactions form 1 mol of H2O. HCl HCl HNO3 HNO3 + + + + KOH NaOH KOH NaOH

KCl + H2O NaCl + H2O KNO3 + H2O NaNO3 + H2O

H+ + OH- H2O H = - 57 kJ mol-1

Neutralisation of NaOH with H2SO4 (diprotic acid) 2NaOH + H2SO4 Na2SO4 + 2H2O 2 mol of OH- reacts with 2 mol of H+ to form 2 mol of H2O. Heat released is 2 57 kJ, that is, 114 kJ, not 57 kJ. Heat of neutralisation of sulphuric acid with sodium hydroxide remains at -57 kJ mol-1 because the definition for heat of neutralisation is in terms of formation of 1 mol of water, not 2 mol of water.

(b) Weak acid and strong alkali : Magnitude of heat of neutralisation for a weak acid with a strong alkali is less than 57 kJ mol-1. NaOH + CH3COOH CH3COONa
ethanoic acid

+ H2O,

H = -55 kJ mol-1 H = -12 kJ mol-1

NaOH + HCN
hydrocyanic acid

NaCN + H2O,

Explanation : Weak acids ionise partially in water to produce hydrogen ions in low concentration. CH3COOH CH3COO- + H
+

Some of the acid particles still remain in the form of molecules. Heat energy is absorbed to break the bonds in the molecules of the weak acid that have not been ionised, so that they ionise completely. Part of the heat that is released is used to break the bonds in the molecules of the weak acid that has not been ionised.

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Calculation guide : (i) If the experiment is repeated by changing the volume without changing the concentration, change in temperature is the same. (ii) If the experiment is repeated by changing the concentration of the solution by x times without changing the volume, the temperature change is x times.

Example 1 : Experiment I Reactants 50 cm3 of 2.0 mol dm-3 hydrochloric acid is added to 50 cm3 of 2.0 mol dm-3 potassium hydroxide solution. 300 cm3 of 2.0 mol dm -3 hydrochloric is added to 300 cm3 of 2.0 mol dm -3 potassium hydroxide solution. Temperature change rises by 13 oC

II

What is the temperature change in Experiment II?

Solution :
Experiment I : Heat released, H = mc = (50 + 50) 4.2 13 = 5460 J MV 1000 = 2.0 50 1000 = 0.1 mol = 5460 0 .1 = 54600 J

Number of mole of HCl / H+ =

Number of mole of HCl = Number of mole of H + Number of mole of KOH = Number of mole of OH -

KOH + HCl KCl + H2O

Number of mole of HCl = Number of mole of KOH Number of mole of H2O = Number of mole of HCl Number of mole of H2O = Number of mole of KOH

Heat of neutralisation, H

Heat of neutralisation, H for Exp. I = Heat of neutralisation, H for Exp. II Experiment II : Heat of neutralisation, H = 54600 J Number of mole of HCl / H+ = MV 1000 = 2.0 300 1000 = 0.6 mol

Heat released, H

= 54600 0.6 = 32760 J

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Heat released, H

mc
(300 + 300) 4.2

= mc = 32760

= 32760 = 32760
2520

= 13 0C

Example 2 : Experiment
3

Reactants 50 cm of 0.2 mol dm lead(II) nitrate solution is added to 50 cm3 of 0.2 mol dm-3 sodium carbonate solution. 50 cm3 of 0.6 mol dm-3 lead(II) nitrate solution is added to 50 cm3 of 0.6 mol dm-3 sodium carbonate solution.
-3

Temperature change rises by 2.4 oC

What is the temperature change in Experiment Q? Solution :

H = Heat of precipitation of lead(II) carbonate H = Heat change = mc n

= Number of moles of lead(II) carbonate

H = H n

Ionic equation for both experiments :

Pb2+

+ CO32-

PbCO3

Experiment P : H = 100 4.2 2.4 0.01 = 100800 J Experiment Q : 100800 = 100 4.2 0.03 = 7.2 oC [ The temperature changes 3 times more than Exp. P! ] .

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13.4.2 Comparison between Heat of Combustion of Various Fuel 1. The higher the number of carbon and hydrogen atoms per molecule, the higher the heat energy released by the combustion of 1 mol of fuel.
Heat of combustion of alcohol (kJ mol -1)

4000 3000 2000 1000

Number of carbon atoms per molecule

The heat of combustion of alcohols increase with the increasing of number of carbon atoms and hydrogen atoms in the molecules. More heat released when more carbon atoms become carbon dioxide molecules and hydrogen atoms become water molecules. Example : Diagram below shows the set-up of apparatus for an experiment to compare the heat of combustion of methanol and ethanol. 200 cm3 of water is poured into copper container in this experiment.
Thermometer

Wind shield Copper container

Water Tripod stand Spirit lamp Alcohol* Wooden block

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Table below shows the results obtained from Experiment I; to determine the heat of combustion of methanol and Experiment II; to determine the heat of combustion of ethanol. Experiment I Experiment II

25 20 15
Initial temperature of water :

25 20 15
Initial temperature of water : .........................

65 60 55
Highest temperature of water : ...........................

65 60 55
Highest temperature of water : ..........................

Experiment I

Experiment II

150.50

151.35

Initial mass of spirit lamp and methanol : ......... g

Initial mass of spirit lamp and ethanol : ......... g

149.37

150.50

Final mass of spirit lamp and methanol : ... g

Final mass of spirit lamp and ethanol : .............. g

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(a)

Write the readings of the temperature and the mass of spirit lamp and alcohol in the spaces provided. Based on the experiment above, complete the table below. Name of variables Action to be taken (i) ............ ............ ............ (ii) What to observe in the responding variable : ............ ............ ............ (iii) The way to maintain the controlled variable : ............ ............ ............

(b)

(i) Manipulated variable : ............ ............ ............ (ii) Responding variable : ............ ............ ............ (iii) Fixed variable : ............ ............ ............

(c)

(i) Calculate the energy change, H in the Experiment I and II. [ Energy change = mc, specific heat capacity of water, c = 4.2 J g-1 oC-1 ] Experiment I Experiment II

(ii) Calculate the number of moles of methanol and ethanol burnt in this experiment. [ Molar mass of methanol = 32 g mol-1 ; Molar mass of ethanol = 46 g mol-1 ] Methanol Ethanol

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(iii) Calculate the heat of combustion of methanol in this experiment. Heat of combustion of methanol Heat of combustion of ethanol

(d)

Compare to the heat combustion of methanol and ethanol. Explain why.

2. Fuel Value Fuel value is the amount of heat released when 1 g of fuel burns completely, -1 the unit is kJ g A fuel with high fuel value can supply more energy. Example : Type of Fuel Methanol Charcoal Crude oil Kerosene Petrol Natural gas Fuel Value / kJ g-1 23 35 45 37 34 50

Aspects to be considered when choosing a fuel in industry : (a) Fuel value of the fuel. (b) Cost of energy / cost of fuel. (c) Availability and sources of the fuel. (d) Effect of the fuel to the environment. 4.4 OTHER SOURCES OF ENERGY Worlds major sources of energy are fossil fuels such as coal, petroleum and natural gas are non-renewable source of energy, eventually they will be used up. Other sources of energy are the sun, biomass, water and radioactive substances. END OF CHAPTER 4

Chapter 13

Thermochemistry