1. (a)Given the following standard enthalpies of combustion (298K, 1 atmos.): C(s) -393 kJ mol-1; H2(g) -285.

6 kJ mol-1; C2H6(g) -1560 kJ mol-1 (note: the first two enthalpies correspond to the enthalpy of formation of carbon dioxide and water respectively) Calculate the standard enthalpy of formation of ethane, C2H6(g) Solution: We will use the enthalpy of combustion of ethane to find its enthalpy of formation: 7 2 6 + 2 2 2 + 3 2 2

The enthalpy of combustion is then given by,

We note that (2 ) = 0 according to the definition of standard enthalpy. Therefore, unknown (2 6 ) can be solved for (2 6 ) = 2 (2 ) + 3 (2 )

= 2 (2 ) + 3 (2 ) (2 6 )

(2 6 ) = 2(393) + 3(285) (1560) = 81 / (b) Given the following bond enthalpies (bond energies) in kJ mol-1; C-H 412; C-C 347; O-H 464; O=O 498; C=O 805 (for CO2); C-O 358 calculate the enthalpy of combustion of ethane. You will not get -1560 kJ mol-1. The bond enthalpy method is much less accurate than tabulated enthalpies of formation. Solution: Construct a reaction scheme that shows the individual bonds

H H C H

H C H H + 3 1/2 O O 2 O C O + 3 H O H

Count the bonds broken :

6 C-H bonds + 1 C-C 3.5 O=O double bonds = 6(412)+347+3.5(498) = 4562 kJ/mol Count the bonds formed : 4 C=O + 6 O-H = 4(804) + 6(464) = -6004 kJ/mol The total is 4562 6004 kJ/mol = -1442 kJ/mol

2. Given the following standard enthalpies of combustion (298K, 1 atmos.): C(s) -393 kJ mol-1; H2(g) -285.6 kJ mol-1; C8H18(l) -5512 kJ mol-1; Calculate the enthalpy of formation of octane, C8H18(l) Solution: Use Hess law. The enthalpy of formation of octane can be written as 8 () + 9 2 () 8 18 () (8 18 )

The enthalpies of combustion are 8 18 () +

(8 18 ) = 8 (393) + 9(285.6) (5512) = 202.4 / 3. Given the following standard enthalpies of combustion (298K, 1 atmos.): C(s) -393 kJ mol-1; H2(g) -285.6 kJ mol-1; and the enthalpy of formation of cyclohexane, C6H12(l) -156 kJ mol-1; Calculate the enthalpy of combustion of cyclohexane, C6H12(l) Solution: Use Hess law. The enthalpy of combustion of cyclohexane can be written as 6 12 () + 15 2 () 6 2 () + 6 2 () (6 12 )

(8 18 ) = 8 (2 ) + 9 (2 ) (8 18 )

1 2 () + 2 () 2 () 2

() + 2 () 2 ()

25 () 8 2 () + 9 2 () (8 18 ) 2 2 (2 ) (2 )

To obtain this we use the known enthalpies of formation 6 () + 6 2 () 6 12 () 1 2 () + 2 () 2 () 2 () + 2 () 2 () (6 12 )

(2 )

(6 12 ) = 6(393) + 6(285.6) (156) = 3915.6 / 4. (a) Given the following standard enthalpies of combustion (298K, 1 atmos.): C(s) -393 kJ mol-1; H2(g) -285.6 kJ mol-1; and the enthalpy of formation of ethanoic acid, CH3COOH(l) -487 kJ mol-1 Calculate the enthalpy of combustion of ethanoic acid, CH3COOH(l)

(6 12 ) = 6 (2 ) + 6 (2 ) (6 12 )

(2 )

Solution: Use Hess law. The enthalpy of combustion of ethanoic acid (acetic acid) can be written as 3 () + 2 2 () 2 2 () + 2 2 () (3 ) 2 () + 2 2 () + 2 () 3 () 1 2 () + 2 () 2 () 2 () + 2 () 2 () (3 )

To obtain this we use the known enthalpies of formation

(2 ) = 393

(6 12 ) = 2 (2 ) + 2 (2 ) (3 )

(2 ) = 286

 (3 ) = 2(393) + 2(286) (487) = 871 / 5. Given the following standard Enthalpies of Formation (298K, 1 atmos.): NH3(g) -46.2 kJ mol-1; HCl(g) -92.3 kJ mol-1; NH4Cl(s) -315.0 kJ mol-1; Calculate the enthalpy change for the reaction: NH4Cl(s) NH3(g) + HCl(g) Solution: = (3 ) + () (4 )

= (46.2) + (92.3) (315) = +218.5 /