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Notes - THERMOCHEMISTRY
Notes - THERMOCHEMISTRY
1 Exothermic reaction
- Is a chemical reaction that gives out heat to the surroundings.
- Chemical energy is converted to heat energy.
- The surroundings gain heat and as a result, the temperature of the surroundings
increases.
- Others examples of exothermic reactions are shown below:
(a) Respiration
(b) Rusting of iron
(c) Reaction between Group 1 elements with water
Example: 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)
(d) Neutralisation reaction between acid and alkali
Example: HCl(aq) + NaCl(aq) NaCl(aq) + H2O(l)
(e) Reaction of a dilute acid with metal carbonate
Example: 2HCl(aq) + CaCO3(aq) CaCl(aq) + H2O(l) + CO2(g)
(g) Displacement reaction of metals
Example: Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)
- Some physical processes also release heat as shown below:
(a) Dissolving of alkali in water
Example: NaOH(s) Na+(aq) + OH-(aq)
(b) Dilution of concentrated acids
Example: H2SO4(l) 2H+(aq) + SO42-(aq)
(c) Condensation and freezing process
2 Endothermic reaction
- Is a chemical reaction that absorbs heat from the surroundings.
- Heat energy is converted to chemical energy and store it in the products.
- The surroundings lose heat energy and as a result the temperature of the surrounding
decreases.
- Others examples of endothermic reactions are shown below:
(a) Photosynthesis
(b) Reaction between sodium hydrogen carbonate and dilute acid
Example: NaHCO3(s) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
(c) Decomposition of carbonate salts
Example: PbCO3(s) PbO(s) + CO2(g)
(d) Decomposition of nitrate salts
Example: 2Zn(NO3)(s) 2ZnO(s) + 4NO2(g) + O2(g)
(e) Decomposition of hydrated salt, such as hydrated copper(II) sulphate
Example: CuSO4.5H2O(s) CuSO4(s) + 5H2O(l)
- Some physicals processes also absorb heat as shown below:
(a) Dissolving of ammonium salts such as ammonium chloride, ammonium
nitrate and ammonium sulphate in water
Example: NH4Cl(s) NH+(aq) + Cl-(aq)
(b) Melting and boiling process
3 Heat of Reaction and Energy Level Diagrams
- The total energy stored in a chemical substance is known as energy content.
- It is impossible to measure the energy content for a particular substance but the
changes in energy content that occurs when the reactants are converted to the
products can be determined and is given the symbol, ΔH.
- The amount of heat change in a specific reaction, however, depends on how much
of each reactant is present.
- The more reactants are used, the more heat energy is given out/absorbed in the
reaction. Thus, it is necessary to clearly states the amounts of reactants involved for
the definition of the heat of reaction.
The heat of reaction (ΔH): is defined as the heat change which occurs when the
numbers of moles of reactants indicated by the equation react together.
H reactants H products
Reactants
ΔH = negative
Products
For example, the energy level for the reaction between sodium hydroxide solution and
hydrochloric acid is shown in Figure 2.
Energy
NaOH(aq) + HCl(aq)
ΔH = -57.3 kJ
NaCl(aq) + H2O(l)
Figure 2: Energy level diagram for the reaction between sodium hydroxide
solution and hydrochloric acid
When an endothermic reaction occurs, heat energy is absorbed from the surroundings.
Thus, the total energy content of the products is higher than the reactants.
Energy
Products
ΔH = positive
Reactants
For example, the energy level for the reaction between sodium hydrogen carbonate
solution and hydrochloric acid is shown in Figure 4.
Energy
ΔH = +11.8 kJ
NaHCO3(aq) + HCl(aq)
Figure 4: Energy level diagram for the reaction between sodium hydrogen
carbonate solution and hydrochloric acid
(a) Heat of precipitation Defined as the heat change when 1 mole of reactant reacts or one
(b) Heat of displacement mole of product is formed. Therefore, the unit of ΔH for these
(c) Heat of neutralization reactions is kJmol-1.
(d) Heat of combustion
Heat of precipitation
- Precipitation reaction occurs when we add two solutions together to form a
precipitate.
- For example, when lead(II) nitrate solution and potassium sulphate solution are added
together, a white precipitate, lead(II) sulphate is formed.
- The heat of precipitate is the heat change when 1 mole of a precipitate is
formed from their ions in aqueous solution.
o For example, 50.4 kJ of heat energy is given out when 1 mole of lead(II)
sulphate, PbSO4 is formed. Thus, the heat of precipitation of lead(II) sulphate,
PbSO4 is -50.4 kJ mol-1.
o Thermochemical equation:
Pb2+(aq) + SO42-(aq) PbSO4(s)
ΔH = -50.4 kJ mol-1
o The energy level diagram is shown below:
Energy
Pb2+(aq) + SO42-
(aq)
ΔH = -50.4 kJ mol-1
PbSO4(s)
Figure 5: Energy level diagram for the precipitation of lead(II) sulphate
(b) Using the heat of reaction, ΔH if the value of ΔH and the number of moles (n) of
the reactant are given.
Thus, the heat change in a reaction = n x ΔH kJ
Energy
Zn(s) + Pb2+(aq)
ΔH = -112 kJ mol-1
Pb(s) + Zn2+
(aq)
Figure 6: Energy level diagram for the displacement of lead by zinc
Energy
H+(aq) + OH-
(aq)
ΔH = -57.3 kJ mol-1
H2O(l)
2) Therefore, the heat of neutralization between a strong monoprotic acid and a strong
alkali is always equal to -57.3 kJ mol-1. For example,
5) However, the heat given out by 1 mole of water formed is still 57.3 kJ as shown
below:
2 moles of H2O formed give out 114.6 kJ
114.6 kJ
1 mole of H2O formed gives out =57.3 kJ
2
Therefore, the thermochemical equation can be written as:
3) This is because most of the weak acids exist as molecules when they dissolve in
water. They only ionize partially in water to produce low concentration of H+.
4) Some of the heat given out during neutralization reaction is used to ionize the acid
molecules completely to produce H+. As the result, the value of ΔH is always less
than -57.3 kJ mol-1.
5) The heat of neutralization between a weak acid and a weak alkali is even much lower
because more energy is required to ionize both the weak acid and weak alkali
molecules.
6) For example, the heat of neutralization between ethanoic acid and ammonia solution
is -51.5 kJ mol-1.
Solve problems involving to heat of neutralization
Example 1:
40 cm3 of 0.5 mol dm-3 sodium hydroxide, NaOH solution is added to 25 cm 3 of 1.0 mol dm-3 nitric acid,
HNO3 in a plastic cup. The results are shown below:
Initial temperature of NaOH solution = 28.0 °C
Initial temperature of HNO3 = 28.0 °C
Highest temperature of the mixture = 32.0 °C
(a) Which solution is in excess?
(b) Calculate the heat of neutralization between NaOH solution and HNO3?
[Specific heat capacity of solution = 4.2 J g-1°C-1; density of solution = 1 g cm-3]
Example 2:
When 50 cm3 of 1.0 mol dm-3 sodium hydroxide, NaOH is added to 50 cm3 of 1.0 mol dm-3 nitric acid, HNO3
the temperature rise of the mixture is 7 °C. Predict the temperature rise in each of the following cases.
(a) 100 cm3 of 1.0 mol dm-3 sodium hydroxide, NaOH is added to 100 cm3 of 1.0 mol dm-3 nitric acid,
HNO3
(b) 50 cm3 of 2.0 mol dm-3 sodium hydroxide, NaOH is added to 50 cm3 of 2.0 mol dm-3 nitric acid, HNO3
Heat of combustion
- Heat change when 1 mole of a substance is completely burnt in O 2 under standard
condition.
At standard condition, the temperature is 25 °C and
atmospheric pressure is 1 atm
- Alcohol is a good fuel. The complete combustion of alcohol produces CO2, H2O and
releases a lot of heat.
- For example, the heat of combustion of ethanol is shown by the thermochemical
equation and the energy level diagram below:
C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(l) ΔH = -1376 kJ mol-1
Energy
C2H5OH(l) + 3O2(g)
ΔH = -1376 kJ mol-1
2CO2(g) + 3H2O(l)
- The heat of combustion of alcohol increases from 1 member to the following member
as shown in Table 1.