CHAPTER 4: THERMOCHEMISTRY ENERGY CHANGES IN CHEMICAL REACTION

b) Burning of magnesium ribbon

ENDOTHERMIC REACTION Endothermic reaction occurs when the reaction taken in (absorbs) heat from the surrounding. The temperature of the surroundings goes down because the surroundings lost heat to the reacting system. Although the reaction has gained heat, this gain in heat does not raise its temperature but goes to form new chemical bonds. Therefore, the temperature drop. Example of endothermic reaction: 1. Dissolving ammonium nitrate in water. Equation:

c) Burning of carbon The changes of energy show that a chemical reaction is taking place. When the heat energy is given out, the reaction gets hotter. This is called___________________ When the heat energy is taken in, the reaction gets colder. This is called___________________ EXOTHERMIC REACTION Exothermic reaction occur when the reaction given out (release) heat to the surrounding. Properties of exothermic reaction: a) Chemical energy is changed to heat energy. b) The temperature of the surrounding increases. c) Heat is liberated. Example of exothermic reaction: 1. Dissolving solid alkali in water, the temperature rises. Eg: dissolve solid sodium hydroxide in water. 2. Displacement reaction between zinc and copper sulphate. Equation: 8. Adding water to the oxides of very reactive metals such as sodium and potassium. Equation: 5. Diluting concentrated sulphuric acid. Equation:

4. Neutralisation reaction Eg:

6. Adding water to anhydrous copper sulphate. Equation: 2. Dissolving ammonium sulphate in water. Equation:

7. Reaction between active metal and dilute acids. Equation:

3. The dissociation of blue copper sulphate crystals into white powder and steam. Equation:

9. Reaction between acids and carbonates. Equation:

3. Combustion reaction. a) Burning of methane

10. Reaction between active metals and water. Equation:

4. Photosynthesis process. Leaves of the tree take in light energy from sun. This energy is used to combine carbon dioxide with water. This process absorbs energy.

ENERGY LEVEL DIAGRAM Exothermic reaction:

b) The reaction between sodium hydroxide and hydrochloric acid.

b) The dehydration of magnesium sulphate.

Endothermic reaction: The reactants high up have a lot of stored chemical energy. The product lower down has less energy. Heat energy is given off as the reactants reacts to give the products. The energy is release to form the bond of the product. The change in energy is negative. Example: a) The burning of magnesium

The reactants have lower energy content. The products have higher content. During the reaction, heat is absorbed by the reacting system. Therefore, the energy content of the system goes up. The energy is absorbs to break down the bond of the reactants to form the products. The change in energy is positive. Example: a) The breaking of hydrogen molecules into hydrogen atoms. - Hydrogen molecules have lower energy content than the hydrogen atoms.

Heat energy can be measured in units called joules (J) or kilojoules (kJ). The principle of endothermic and exothermic reaction used for cold and hot packs. They are used lo lessen pain for injuries in the field. Inside the cold pack a salt and water are packed separately by a membrane. Example of salt used: When the pack is needed, the membrane is broken and allows the salt to react with water to absorb heat from surroundings and the endothermic reaction is take place. A similar principle is used to make hot packs and the exothermic reaction will take place. The type of salt used will be different such as:

HEAT OF REACTION Example of thermochemical equation: The standard condition for heat of reaction: a) The pressure of reaction is 1 atmosphere b) The temperature of reaction is 25oC or 298K c) The reactants and products are in their usual physical state at 25oC d) The concentration should be at 1 mol dm-3 The equation is a thermochemical equation if all the conditions above are satisfied. Types of heat of reaction Different types of chemical reaction will give different values of heat of reaction. There are 4 types of heat of reaction: 1. Heat of precipitate 2. Heat of displacement 3. Heat of neutralization 4. Heat of combustion HEAT OF PRECIPITATION After a reaction, the solid appears in the solution is called a precipitate. Heat of precipitation is the heat change when one mole of precipitate is formed from the reacting solutions under standard conditions. Example: a) Formation of AgCl

Exercise: formation of barium sulphate Determine the heat of precipitation of barium sulphate and show the energy level diagram.

Step 4: calculate the heat of precipitate and draw energy level diagram

Step 1: construct the thermochemical equation

Step 2: calculate the number of moles of barium sulphate

Step 3: calculate the energy change Heat change = mc

b) Formation of lead (II) sulphate

HEAT OF DISPLACEMENT The more electropositive ions will displace the less electropositive ions form the solution. The heat of displacement is the heat change when 1 mole of a metal is displaced from its solution by another metal, under standard conditions. Example:

Exercise: In an experiment, 25 cm3 of silver nitrate 0.2 mol dm-3 was reacted with 0.7g copper powder. The copper powder used was more than what is required. The reaction produced a rise in temperature of 35oC. (a) Write down the equation for the reaction (b) Calculate: i. the number of moles of silver ions in the solution. ii. The total heat energy liberated. iii. The heat of displacement.

HEAT OF NEUTRALISATION Acid will react with alkali to form salt and water. This is called neutralization. Heat of neutralization is the heat energy produced when 1 mol of OH- ions combine with 1 mole of H+ ion to form 1 mole of H2O All heat of neutralization are always equal to -57oC kJ mol-1 which is an exothermic reaction. All neutralization reactions are exothermic reactions. Example:

Quantity of the acid and alkali A larger quantity of acid means that it has more moles of the acid in the solution. The higher the quantity of acid used, the higher will be the heat of neutralization. Example:

Their weak ionization causes them to have low heat of neutralization reacting with sodium hydroxide.

The basicity of the acid The basicity of acid measures the number of mole ions of H+ present in one mole of an acid. HCl is a monobasic acid that will produce one mole of H+ ions. 1 mole of H+ will combine with 1 mole of OHfrom alkali to form water.

Before the neutralization take place, energy is needed to break the bonds of the unionized weak acid molecules. This energy is taken from the heat of neutralization (57kJ) that is produced during neutralization. Exercise: 1. In an experiment, 500 cm3 of 2.0 mol dm-3 HCl was neutralized by 500 cm3 of 2.0 mol dm-3 NaOH. The initial temperature of both solutions was 29oC and the final temperature of the reacting mixture was 42oC. (a) Calculate the heat of neutralization (b) Why was the experimental value of the heat of neutralization lower than the theoretical value? Solution: (a) Rise in temperature:

Factors that effect the amount of heat produced during neutralization reactions: 1. The concentration of the acid or alkali 2. The quantity of the acid and alkali 3. The basicity of the acid The strength of acid or alkali Neutralization reaction between a strong acid and a strong alkali will produce more heat than reaction between a weak acid and a weak alkali. Example: a) Reaction of HCl with NaOH HCl is a strong acid, NaOH is a strong alkali. 1 mole of HCl will react with 1 mole of NaOH to produce 57 kJ of heat. b) Reaction of ethanoic acid with NaOH ethanoic acid is a weak acid, when react with NaOH will produce only 55 kJ of heat.

H2SO4 is a dibasic acid. It has 2 moles of H+ ions in 1 mole of acid. 2 moles of H+ ions from the acid will combine with 2 moles of OH- ions from an alkali to form 2 moles of water.

Thus for the same concentration, neutralization of a dibasic acid will produce more heat energy than a monobasic acid. Heat of neutralization for weak acid Example of weak acid: ethanoic acid and hydrocyanide acid. They ionize weakly in water.

Total mass of reacting mixture:

Total heat liberated: = mc

Number of moles of HCl:

Thus, the heat of neutralization is:

HEAT OF COMBUSTION Any substance of fuel that burns in oxygen to produce heat energy is called burning or combustion. Heat of combustion is the energy that given out when 1 mole of fuel burns. Example: The burning of 1 mole of methane in oxygen will produce 890 kJ of heat energy. Therefore, the heat of combustion of methane is 890 kJ mol-1.

(b) The experimental value of the heat of neutralization is less than the theoretical value because heat is lost to:

Exercise: 5 g of sulphur is burnt in a calorimeter. The heat generated increase the temperature of 500 g of water by 21oC. What is the heat of combustion for sulphur? [ Relative atomic mass: S = 32]

2. In an experiment 100 cm3 of 2.0 mol dm-3 KOH reacted with 100 cm3 of HNO3. If the heat of neutralization is -57 kJ mol-1, what is the rise in temperature?

Combustion reaction is always exothermic. Therefore, H is always negative. Example of heat of combustion for different fuels commonly used: Fuel Reacting equation Heat of combustion Hydrogen Ethanol Carbon Methane

During combustion, an excess supply of oxygen is required. If the supply of oxygen is restricted, the heat liberated will be lower.

EXERCISE 1. In an experiment, 4.6g of ethanol was burnt in oxygen. The heat given off was enough to raise the temperature of 1600 cm3 of water from 30 oC to 50 oC. What is the heat combustion for alcohol? [relative atomic mass: C:12 O:6 H:1] Solution: Step1 : amount of heat Heat given off =

2. 1.3 g of hydrocarbon was burnt in a rich supply of air. The heat energy from the combustion raised the temperature of 500 cm3 of water by 36oC. If the relative molecular mass of the hydrocarbon is 6, what is the heat of combustion for this hydrocarbon? Solution:

HEAT OF COMBUSTION FOR DIFFERENT FUELS All fuels can be burnt in air. They produce heat energy during combustion. Different types of fuel will give out different heat of combustion. In alcohol series, the heat combustion increases up the series. In alkane, the heat of combustion increases as the alkane rise in the series. This is because:

Step 2: molar mass and mole of ethanol

Step3: equation

________ mole of ethanol , liberated _______kJ of heat Step 4: heat for one mole

Fuel values Fuel values show the amount of heat given off by one kilogram (for solid) or one cubic meter (for gas). We choose fuels which are: 1. Easily available 2. High heat value 3. Cheap 4. Non polluting VARIOUS ENERGY SOURCE There are two main type of energy: 1. Non-renewable energy such as: coal, oil and gas, and nuclear fission 2. Renewable energy such as: wind, solar, biomass, geothermal, hydroelectric.

Therefore, heat of combustion is____________________