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Ans. True Q4. Define the following terms and give three examples of each i) System ii) Surroundings iii) State function iv) Units of energy v) Exothermic reaction vi) Endothermic reaction vii) Internal energy of the system viii)Enthalpy of the system. Q5. (a) Differentiate between the following: (i) Internal energy and enthalpy (ii) Internal energy change and enthalpy change (iii) Exothermic and endothermic reactions (b) Define the following (i) Standard enthalpy of reaction (ii) Standard enthalpy of combustion (iii) Standard enthalpy of atomization (iv) Standard enthalpy of solution
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(a)
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C(s ) O2(g) +CO2 (g) CO(g ) C(s) + O2 (g) H2 (g) + 12 (s) H1(g) H1(g) H2 (g) + 12 (s)
Second Thermaochemical law (Hesss Law-1840) The amount of heat evolved or absorbed in a chemical reaction is the same whether the reaction takes place in one step or in several steps. Mathematically: 2.
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+NaOH (aq)
1mole
1mole
NaC1(aq) + H2 O(l)
0.05mole
Now, 0.1 mole of formation of H2 O liberates heat =-2.717 KJ 1 mole of formation of H2 O liberates heat = =- 54.34 kJ Enthalpy of neutralization, Hn = -54.34 kJ Answer Q14. Hyrazine N2 H4 is a rocket fuel. It burns in o2 to N2 and H2O. N2H4(l) +O2(g) N2(g) + 2H2 O(g) 1.00 g of N2H4 is burned in a bomb calorimeter. An increase of temperature 3.51oC is recorded. The heat capacity of calorimeter is 5.5 kJK-1 . Calculate the quantity of heat evolved. Also calculate the heat of combustion of 1 mole of N2 H4. Solution:
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=-
x1g
= - 86.52 kJ Heat of combustion of 1 mole of octane = -86.52 kJ No, of moles of octane =1 mole Molar mass of octane, C8 H18 =96+18=114 g mol-1 Mass of octane = moles of octane x molar mass of octane = 1 mol x 114 g mol-1 =114 g Now, heat of combustion of 1 g of octane = -86.52 kJ Heat of combustion of 114 g of octane = x 114 g Hence, 1 Answer Q16. By applying Hesss law calculate the enthalpy change for the formation of an aqueous solution of NH4 C1 from NH3 gas and HC1. The results for the various reactions and pressure are as follows. (i) NH3(s) +aq NH3(aq) H= -35.16kJ mol-1 (ii) HC1(g) +aq HC1(aq) H= -72.41kJ mol-1 (iii) NH3(s) +HC1(aq) NH4 C1(aq) H= -35.16kJ mol-1 Solution: NH3(g) +HC1(g)+ aq NH4C1(aq) H= ? (i) NH3(g) +aq NH3(aq) H= -35.16kJ mol-1 (ii) NH3(g) +aq HC1(aq) H= -72.41kJ mol-1 (iii) NH3(aq) +HC1(aq) NH4 C1(aq) H= -51.48kJ mol-1 Add Eq (i), Eq (ii) (i) NH3(g) +aq NH3(aq) H= -35.16kJ mol-1 (ii) NH3(g) +aq HC1(aq) H= -72.41kJ mol-1 __________________________________________________________ __ (iv) NH3(g) +HC1(g)+2aq NH3(aq)+HC1(aq) H= -107.57kJ mol-1
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(i)
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(vi)
(i) C2H5OH(l) 3O2(g 2CO2(g) 3H2 O(l) H= 1367 kJ __________________________________________________________ __ 2C(s)+ 3H2(g) + O2(g) C2H5 OH(l) 0 H= -277.8 kJ 2C(s)+ 3H2(g) + O2(g) or C2H5 OH(l) H= -277.8 kJ
Hence, the heat of formation of ethyl alcohol is - 277.8 kJ Answer Q18. If the heats of combustion of C2H2, H2 and C2 H6 are 337.2 , 68.3 and 372.8 k calories respectively , then calculate the heat of the following reaction. C2H2(g)+ 2H2(g) C2H6 (g) Solution: C2H2(g)+ 2H2(g) C2H6 (g) H= ? (i) C2H2(s)+ O2(g) 2CO2(g)+ C2H6(g) H= -337.2 kJ (ii) (iii) (iv) (i) (ii) (v) (v) (iii) H2(s)+ C2 H6(s)+ O2(g) O2(g) H2 O(l) 2CO2(g) +3H2O(l) H= -68.3 kJ H= -372.8 kJ H= -136.3kJ H= -337.2 kJ
Multiply Eq (ii) by2 2H2(g)+ O2(g) 2H2O(l) Add Eq (i) , Eq (iv) C2H2(s)+ O2(g) 2CO2(g)+ H2O(l)
2H2(g)+ O2(g) 2H2O(l) H= -136.3kJ C2 H2(s)+ 2H2(g) + O2(g) 2CO2(g) +3H2O(l) H= -473.8 kJ From Eq(v) subtract Eq(iii) C2 H2(s)+ 2H2(g) + O2(g) 2CO2(g) +3H2O(l) C2H6(g) O2(g) 2CO2(g) 3H2 O(l)
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H= -473.8 kJ H= 372.8 kJ
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H= -101.0 k cal
C2H2(g)+ 2H2(g)
(ii)CH3COOH(l) + Na+(aq) +OH-(aq) CH3COO (aq) + Na+(aq)+H2O(l) H=55.2kJ mol-1 Now, from Eq(ii), Subtract Eq(i) (ii) CH3COOH(l) + Na+(aq) +OH-(aq) CH3COO (aq) + Na+(aq)+H2O(l) H=55.2kJ mol-1
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H=2.1 kJ mol-1 H=2.1 kJ mol-1 H=2.1 kJ mol-1Answer Q21. (a) Explain what is meant by the following terms. (i) Atomization energy (ii) Lattice energy (b) Draw a complete, fully labeled Born-Haber Cycle for the formation of potassium bromide. (c) Using the information given in the table below , calculate the lattice energy of potassium bromide. Reactions: H / kJ mol-1 K(s) + Br2(l) -392 K(s) K(g) +90 K(g) +420 Br2(l) +112 Br(g) + -342 Solution: Hf(KBr)=-392 kJ mol-1 Hat (K) =90kJ mol-1 Hi(K)=420 kJ mol-1 HD/2 (Br2)=112 kJ mol-1 He (Br) = -342 kJ mol-1 Hl =? According to Born-Haber cycle Hf(KBr) = Hf + Hat(k) + Hi(k) + HD/2 (Br2 ) + He(Br) On putting the values, -1 -392 kJ mol = Hl + 90 kJ mol-1 + 420 kJ mol-1 + 112 kJ mol-1 342 kJ mol-1 -392 kJ mol-1 = Hl + 280 kJ mol-1
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