CHAPTER 7 CHEMICAL ENERGETICS CHEMICAL ENERGETICS

ENTHALPY CHANGE OF REACTION HESS' LAW BORN - HABER CYCLE SOLUBILITY OF SOLID IN LIQUIDS

7.1 ENTHALPY CHANGE OF REACTION

7.11 Define the terms exothermic reaction, endothermic reaction and standard enthalpy change of reaction (H). 7.12 Calculate the enthalpy change for a reaction using experimental data 7.13 Evaluate the results of experiments to determine enthalpy changes. 1. Thermochemistry is the study of energy changes associated with chemical reactions. Most chemical reactions absorb or evolve energy, usually in the form of heat. Thermochemistry studies the amounts of energy (measured in joules, J) associated with these changes. 2. Temperature is the degree of hotness. 3. Molar heat capacity: energy required to raise the temperature of one mole of the substance by one kelvin or (1oC). Specific heat capacity (c): energy required to raise the temperature of one g of the substance by one kelvin or (1oC). 4. The specific heat capacity for water 4.18 J g-1K-1 H = m c T H = heat absorbed or released 5. Enthalpy (H, also known as heat content) is the total energy of a system, some of which is stored as chemical potential energy in the chemical bonds. Enthalpy Change, H = The total enthalpy of products - The total enthalpy of reactants 6. Enthalpy changes during the chemical reaction may represented by energy level diagrams. In an exothermic reaction the products are more stable than the reactants , H is negative. In an endothermic reaction the opposite is true. This is shown in Figure below for both an exothermic and an endothermic reaction. 7. Exothermic process: heat given out to surrounding. The value has a negative sign as the heat content of product is less than that of the reactant. 8. Endothermic process: heat absorbs from the surrounding. The value has a positive sign as the heat content of product is more than that of the reactant.

9. 2 Mg(s) + O2 (g)

2 MgO(s)

H = 1200 kJ mol1

means that 1200 kJ of heat are evolved (as H is negative) when 2 moles of magnesium react completely with 1 mole of oxygen molecules. Thus if 0.600 g of magnesium (= 0.600/24.3 moles) is burnt, then the amount of heat produced is:

0.600/24.3 1200 = 14.8 kJ

Exercise 7a 1. When 25 cm3 of 2 mol dm3 aqueous sodium hydroxide is added to an equal volume of hydrochloric acid of the same concentration, the temperature increases by 15 C. What is the enthalpy change for the neutralisation of sodium hydroxide by hydrochloric acid?

2. How much heat energy is required to increase the temperature of 10 g of nickel (specific heat capacity 440 J kg1 K1) from 50 C to 70 C? 3. Copper has a specific heat capacity of 400 J kg1 K1. If a 50 g cylinder of copper absorbs 800 J of energy, by how much will its temperature rise? 4. When 8.00 g of ammonium nitrate completely dissolved in 100 cm3 of water, the temperature fell from 19.0C to 14.5C. Calculate the enthalpy of solution of ammonium nitrate.

10. The standard heat of formation, or standard enthalpy of formation (represented as H), for a substance is the enthalpy change in the formation of 1 mole of that substance from its individual elements at 1 atmosphere (1 atm) and 25o C (unless otherwise noted). 11. The more negative the value, the more energetically stable the compound.

Example 1 Which of the following equations represents a reaction that provides the heat of formation of ethanol (CH3CH2OH)? A) CH2 = CH2(g) + H2O(l) B) 2C(s) + 6 H(g) + O(g) C) 2 CO2(g) + 6 H2(g) CH3CH2OH(l) CH3CH2OH(l) CH3CH2OH(l) + 3H2O(l) CH3CH2OH(l)

D) 2 C(s) + 3H2(g) + 1/2 O2(g) E) 2 CO(g) + 3 H2(g) Answer

CH3CH2OH(l) + 1/2 O2(g)

Equation A: CH2 = CH2(g) is not the most stable form of C, and H2O(l) is not the most stable form of H or O (C(s), H2(g) and O2(g) are). Equation B: H(g) is not the most stable form of H (H2(g) is). Equation C: CO2(g) is not the most stable form of C or O (C(s) and O2(g) are). Equation D: Correct. Equation E: CO is not the most stable form of C (C(s) is).

Example 2: The heat of formation of CO2(g) is -394 kJ/mole and that of H2O(l) is -286 kJ/mole. The heat of combustion of C5H12 is -3534 kJ/mole. What is the heat of formation of C5H12? C5H12(l) + 8 O2(g) 5 CO2(g) + 6 H2O(l)

Answer

12. The heat of combustion, or enthalpy of combustion (represented as Hoc), is the amount of energy released in the combustion of one mole of a substance. Example 3

CalculateHf(C2H4 (g)), given: Hf(CO2(g))=395kJmol1, Hf (H2O (l)) = 287 kJ mol1 and Hcomb (C2H4 (g)) = 1416 kJ mol1.

Example 4 The combustion of 0.625 g of benzoic acid causes the temperature of the water in the bomb calorimeter to increase by 1.572 K while the combustion of 0.712 g of an organic compound causes an increase of 1.54 K. Calculate the standard enthalpy change of combustion of the organic compound. [ HC benzoic acid is -3230 kJmol-1. The RMM for benzoic acid and organic compound is 122 and 60.] Answer Heat released of burning of acid: 0.625/122 x 3230 = 16.55 kJ 1.572 K 16.55 kJ 1.54 K ? kJ (16.2 kJ) released by burning of organic compound. Standard enthalpy change of combustion of the organic compound: 16.2 kJ/ no. of mol organic compound = 16.2 /(0.712/60) = 1361 kJmol-1 13. Standard molar enthalpy change of neutralization is enthalpy change when one mole of acid reacts with one mole of alkali to form one mole of water under standard condition. 14. When strong acid is neutralized by strong base, heat of neutralization is constant at -57.2 kJmol-1.. Hneut for diprotic strong acid > -57.1 kJ/mol due to dilution of acid when alkali is added. H2SO4 + NaOH NaHSO4 + H2O NaHSO4 + NaOH Na2SO4 + H2O Hneut = -62.0 kJ/mol Hneut = -71.0 kJ/mol

Average = -66.5 kJ/mol 15. When weak acid or weak alkali is used, further heat change is involved in ionizing the weak acid. Thus, heat of neutralization is less exothermic (less negative) than -57 kJ/mol. 16. Standard molar enthalpy change of atomization is enthalpy change when one mole of gaseous atoms is formed from the element in its standard condition. This process requires energy (endothermic) Na (s) Na (g) Cl2(g) Cl (g) Hat = +107 kJmol-1 Hat = +242 kJmol-1

17. The first electron affinity: enthalpy change when one electron is added to each gaseous atom in one mole to form one mole of x-1.. 18. The second electron affinity: enthalpy change when one electron is added to each gaseous anion in one mole to form one mole of x-2. O (g) + e O- (g) + e O- (g) O2- (g) HEA1 = -144 kJmol-1 HEA2 = + 791 kJmol-1

The second electron affinity is endothermic because energy is required to overcome the repulsive force between the electron and the x-.

19. The lattice energy: energy given out when one mole of an ionic crystalline solid formed from its ions. K+ (g) + Cl- (g) KCl (s) KCl (s) K+ (g) + Cl- (g) Hlattice = -701 kJmol-1 Hlattice dissociation = +701 kJmol-1

20. Factors that affecting the magnitude of lattice energy: a) The attractive forces between the positive and negative ions b) The distance between the ions/ ionic radius. c) The larger the charge of the ions, the more exothermic is the lattice energy d) The smaller the ionic radius, the more exothermic is the lattice energy

7.2

HESS LAW

7.2.1 State Hess law 7.2.2 Construct energy level diagrams relating the enthalpy to reaction path and activation energy. 1. Hesss Law states that the total enthalpy change for the two stage reaction must be equal
to the single stage process.

2. If a reaction is carried out in a series of steps, H for the reaction will be equal to the sum of the enthalpy changes for the individual steps. The overall enthalpy change for the process is independent of the number of steps or the particular nature of the path by which the reaction is carried out. 3. Consider the combustion reaction of methane to form CO2 and liquid H2O CH4(g) + 2O2(g) -> CO2(g) + 2H2O(l) This reaction can be thought of as occurring in two steps: In the first step methane is combusted to produce water vapor: CH4(g) + 2O2(g) -> CO2(g) + 2H2O(g) H = -802 kJ In the second step water vapor condenses from the gas phase to the liquid phase: 2H2O(g) -> 2H2O(l) H = -88 kJ Combining these equations yields the following: CH4(g)+2O2(g)+2H2O(g) CO2(g)+2H2O(g)+2H2O(l) H = (-802) kJ + (-88) kJ= -890 kJ

Example 1

Answer

Exercise 7b
1.

Given the enthalpy changes of the reactions below

2 H2O2 (aq) 2 H2 (g) + O2 (g)

2 H2O (l) + O2 (g) 2H2O (l)

H = 200 kJ mol1 H = 600 kJ mol1

what will be the enthalpy change for H2 (g) + O2 (g)H2O2 (aq)?

2.

The reaction of 1.00 mol of phosphorus with chlorine gas to form PCl3 (g) releases 287.0 kJ. The reaction of 1 mol of phosphorus to form PCl5 (g) releases 374.9 kJ. Calculate the enthapy change for the reaction. PCl3 (g) + Cl2 (g) PCl5 (g) under these conditions.

3.

cHo298 for methane, CH4, is 890.3 kJ mol1. Calculate fHo298 for methane.

4.

CH4(g) + 2 O2(g) --> CO2(g) + 2 H2O(l) HfCH4 = 889.1 kJ HfH2O(l) = 285.8 kJ/mol HfCO2(g) = 393.3 kJ/mol What is the standard heat of formation of methane, HfCH4(g), as calculated from the data above? H2(g) + 1/2 O2(g) --> H2O(l) H = 286 kJ 2 Na(s) + 1/2 O2(g) --> Na2O(s) H= 414 kJ Na(s) + 1/2 O2(g) + 1/2 H2(g) --> NaOH(s) H= 425 kJ Based on the information above, what is the standard enthalpy change for the following reaction? Na2O(s) + H2O(l) --> 2 NaOH(s)

5.

STPM Tral Question 6. Chlorine dioxide gas, ClO2, which is a reddish yellow gas. It is used for the disinfection and the principal agent used in the decontamination of buildings in the United states after the 2001 anthrax attack. Chlorine dioxide gas can be prepared in the laboratory by the following reactions: 2AgClO3 (s) + Cl2 (g) 2AgCl (s) + 2ClO2 (g) + O2 (g); H = zero

[ Hf (AgClO2) = -25kJ mol-1; Hf (AgCl) = -127 kJ mol-1] (i) (ii) Calculate the value of Hf (ClO2) From the value obtained in a (i) above; comment on the relative stability of chlorine dioxide. [ 3 marks ]