THERMOCHEMISTRY

Thermochemistry: The Law of Conservation of Energy energy can neither be created nor destroyed but it can be changed from one form to the other form Exothermic reaction a chemical reaction that gives out heat to the surrounding Endothermic reaction a chemical reaction that absorbs heat from the surrounding. Surroundings do not involve in the reactions. Example: water, container, the air, solvent and thermometer

Heat of reaction the heat change when the number of moles of reactants in the chemical equation reacts to form products in standard conditions. Standard conditions: temperature (25C / 298 K), pressure (1 atm), concentration of solution (1.0 mol dm-3), reactants and products are at their normal physical states. 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 neutralisation the heat change when one mole of water is formed from the reaction between an acid and an alkali Heat of combustion the heat change when one mole of a substance is completely burnt in oxygen under standard conditions.

Exothermic reaction

Chemical energy > Heat energy

The heat energy is transferred to the surrounding. Temperature of the surrounding increases

Example of Chemical Reactions:

Respiration
Burning of metal Reaction of an alkaline metals (Group 1) with water Reaction of a reactive metal with acid Neutralisation reaction between acid and alkali

Reaction of a carbonate with acid

Combustion of carbon compound Displacement reaction of metals Rusting of iron

Example of Physical Processes:

Freezing process
Condensation process Dissolving an alkali in water Dissolving an concentrated acid in water

ENDOTHERMIC REACTION

Endothermic reaction Heat energy > Chemical energy

The heat is absorbed from the surrounding.

Temperature of the surrounding decreases Example of Chemical Reactions: Photosynthesis Decomposition of nitrate salts Decompositon of carbonates salts Reaction between acid with hydrogen carbonates

Example of Physical Processes:

Melting process
Boiling process Sublimation process Dissolving of ammonium salts in water Dissolving of potassium salts in water

Dissolving of thiosulphate in water

Heat of Reaction Enthalpy (H) absolute energy content of a substance. Change in energy content (H) absolute energy content cannot be determined, but H can be determined when the reactants are converted to the products.

1 kJ (kilojoule) = 1000 J The unit H is kJ

ENERGY DIAGRAM

Energy Level Diagram

H = H product H reactant = negative value.

Example: CH4(g) + 2O2(g) > CO2(g) + 2H2O(l) H = -890 Kj The value of H is negative = exothermic reaction H = H product H reactant = positive value. Example: N2(g) + 3H2(g) > 2NH3(g) H = +91.8kJ

The value of H is positive = endothermic reaction

Energy Change during Formation and Breaking of Bonds Bond breaking Usually chemical bonds of the reactant. Heat energy is absorbed

Bond forming
Usually new chemical bonds of the product. Heat energy is given out. Relationship between energy change and the formation and breaking of bonds In a chemical reaction, if the heat energy absorbed in bond breaking is lower than the

heat energy given out in bond forming, the reaction is an exothermic reaction
Example: H (bond breaking) = +600 kJ, H (bond forming) = -800 kJ, H (heat of reaction) = [(+600) + (-800)] kJ= -200 kJ

In a chemical reaction, if the heat energy absorbed in bond breaking is higher than the heat energy given out in bond forming, the reaction is an endothermic reaction.

Example: H (bond breaking) = +800 kJ, H (bond forming) = -600 kJ, H (heat of reaction) = [(+800) + (-600)] kJ= +200 kJ

Applications of Exothermic and Endothermic Reaction in Everyday Life

Hot pack Contains of anhydrous calcium chloride / anhydrous magnesium sulphate / wet iron powder and sodium chloride / calcium oxide.
Uses: reduce swelling and muscles or joint sprain. Cold pack or Ice pack Contains of ammonium nitrate / potassium nitrate / sodium thiosulphate.

Uses: reduce swelling, muscles or joint sprain and reduce fever.

You must be able to 1. Calculate the number of moles of salt precipitated / metal displaced / water produced / fuel used; 2. Calculate the heat energy released (H); and 3. Calculate the heat of precipitation / heat of displacement / heat of neutralization / heat of combustion.

Heat of Precipitation (Form 4, Chapter 8 Salts) Heat of precipitation the heat change when one mole of a precipitate is formed fromtheir ions in aqueous solution. Precipitation reaction = double decomposition which is used to prepare insoluble salts

Heat change of a solution = mc Joule [m = mass of the solution (g), c = specific heat capacity of the solution (J g-1C-1), = temperature change in the solution (C)]
Heat change in a reaction, mc = n x H

Heat of reaction / Heat of precipitation, H = mc / n

Example 1: Chemical reaction: Pb(NO3)2(aq) + 2KI(aq) > PbI2(s) + 2KNO3(aq) Ionic reaction: Pb2+(aq) + 2I-(aq) > PbI2(s) Heat of precipitation of PbI2 = Heat change / Number of moles of PbI2

Example 2: Chemical reaction: BaCl2(aq) + Na2SO4(aq) > BaSO4(s) + 2NaCl(aq)

Ionic reaction: Ba2+(aq) + SO42-(aq) > BaSO4(s)

Heat of precipitation of BaSO4 = Heat change / Number of moles of BaSO4

Heat of Displacement (Form 4, Chapter 6 Electrochemistry & Form 5, Chapter 3 Oxidation and Reduction) Heat of displacement the heat change when one mole of a metal is displaced from its salt solution by a more electropositive metal. Heat change of the reaction mixture / Heat energy released / Heat given out in the reaction = mc Joule

Heat change in a reaction, mc = n x H

Heat of reaction / Heat of displacement, H = mc / n

Example 1:

Chemical equation: Mg(s) + FeCl2(aq) > MgCl2(aq) + Fe(s)

Ionic equation: Mg(s) + Fe2+(aq) > Mg2+(aq) + Fe(s) Example 2: Chemical equation: Zn(s) + CuSO4(aq) > ZnSO4(aq) + Cu(s) Ionic equation: Zn(s) + Cu2+(aq) > Zn2+ (aq) + Cu(s)

Heat of Neutralisation (Form 4, Chapter 7 Acids and Bases) Heat of neutralisation the heat change when one mole of water is formed from the reaction between an acid and an alkali. Neutralisation a reaction between an acid reacts with a base (alkali) to form a salt andwater. Hydrogen ion from acid reacts with hydroxide ions from alkali to form water. H+(aq) + OH(aq) > H2O(l) Neutralisation reaction gives out heat and always an exothermic reaction.

Example 1: (Strong acids monoprotic acid and strong alkalis) Chemical equation: HCl(aq) + NaOH(aq) > NaCl(aq) + H2O(l)
Ionic equation: H+(aq) + OH-(aq) > H2O(l) Heat of neutralisation of strong acids and strong alkalis are the same (H = -57.3 kJ mol-1) Example 2: (Strong acids diprotic acid and strong alkalis) Chemical equation: H2SO4(aq) + NaOH(aq) > Na2SO4(aq) + 2H2O(l) Ionic equation: 2H+(aq) + 2OH-(aq) > 2H2O(l) Heat of neutralisation of strong acids and strong alkalis are the same (H = -57.3 kJ mol-1)

Example 3: (Weak acids and strong alkalis)

Chemical equation: CH3COOH(aq) + NaOH(aq) > CH3COONa(aq) + H2O(l) Ionic equation: H+(aq) + OH-(aq) > H2O(l) Heat of neutralisation of weak acids and strong alkalis are lower (H = -55.0 kJ mol-1) than heat of neutralisation of strong acids and strong alkalis (H = -57.3 kJ mol-1). Example 4: (Strong acids and weak alkalis) Chemical equation: HCl(aq) + NH4OH(aq) > NH4Cl(aq) + H2O(l) Ionic equation: H+(aq) + OH-(aq) > H2O(l)

Heat of neutralisation of strong acids and weak alkalis are lower (H = -51.5 kJ mol-1) than heat of neutralisation of strong acids and strong alkalis (H = -57.3 kJ mol-1).

Example 5: (Weak acids and weak alkalis)

Chemical equation: CH3COOH(aq) + NH4OH(aq) > NH4Cl(aq) + H2O(l) Ionic equation: H+(aq) + OH-(aq) > H2O(l) Heat of neutralisation of strong acids and weak alkalis are lower (H = -50.4 kJ mol-1) than heat of neutralisation of strong acids and strong alkalis (H = -57.3 kJ mol-1).

Heat of Combustion (Form 5, Chapter 2 Carbon Compounds) Heat of combustion the heat change when one mole of a substance is completely burnt in oxygen under standard conditions. Combustion redox reaction between substance (fuel) reacts rapidly with oxygen with the production of heat energy. Combustion reaction gives out heat and always an exothermic reaction. Heat evolved in combustion of fuel = Heat absorbed by water.

Bomb calorimeter is used to determine the heat of combustion.

The more carbon and hydrogen atoms per molecules in a fuel, the more heat that is releasedwhen 1 mol of fuel combusts.

There are differences in heats of combustion: The selection of suitable fuel:

Chemical equation

H (kJ mol-1)

H2(g) + O2(g) > H2O(l)

C(s) + O2(g) > CO2(g)

-286
-392

CH4(g) + 2O2(g) > CO2(g) + 2H2O(l)

CH3OH(l) + 3/2 O2(g) > CO2(g) + 2H2O(l) C2H5OH(l) + 3O2(g) > 2CO2(g) + 3H2O(l) C3H7OH(l) + 9/2 O2(g) > 3CO2(g) + 4H2O(l)

-890
-728 -1376 -2016

Fuel value (the amount of heat energy given out when one gram of the fuel is completely burnt in excess of oxygen): The higher the fuel value, the more energy is released.

Effect on the environment: Production of soot which caused air pollution. Hydrogen fuel is known as clean fuels (no soot or poisonous gases).

Qualities of a fuel are based on the following: Easily available

Cheap in cost
High fuel value Do not pollute the environment Less storage space The Existence of Various Energy Sources

The Sun: solar cell (still expensive and inefficient)

Fossil Fuels: relatively high fuel value and convenient to use (non-renewable and cause greenhouse effect and acid rain) Water: hydroelectric power. It is clean, renewable, convenient and economical to use (high cost of construction and destruction of the surrounding environment) Biomass: plants and droppings of animals biodiesel (large areas of land to grow plants) Radioactive substances: uranium and plutonium (non-renewable and very destructive if an accident occurs)