Chang, 8th Edition, Chapter 6, Worksheet #2

S. B. Piepho, Fall 2005

The Enthalpy of Chemical Change: Calculations using Hess's Law and Heats of Formation Enthalpy of reaction values have been determined experimentally for numerous reactions, and these H values may be used to calculate H values for other reactions involving the same chemical species. The reason this is possible is that enthalpy H is a state property so H is independent of path. (Similarly, the height of a mountain above sea level is independent of the path you follow to climb the mountain.) Because H is independent of path, we can determine the enthalpy of foods by burning them in a bomb calorimeter in the laboratory to produce the same products that are obtained by the complicated metabolic pathways in our body! There are two principle methods used to calculate H values for a reaction, both of which are based on the idea that H for a reaction is independent of the path used to go from reactants to products. The first makes use of Hess's Law while the second employs tabulated heats of o formation H f (kJ/mol). Use of Hess's Law to Calculate H Hess's Law states that H for a reaction can be found indirectly by summing H values for any set of reactions which sum to the desired reaction. Usually before reactions are added together, some of them must be reversed and/or multiplied by a factor n in order that they sum to the desired reaction. In this process the rules are: Whenever you multiply a reaction by n, H for the reaction is also multiplied by n. If you reverse a reaction, H changes sign. Problem (1) below is an example of how this procedure is used. Use of Tabulated Heats of Formation to Calculate H o The Standard Heat of Formation H f (kJ/mol) for a compound is the heat absorbed (or released) in forming one mole of the compound from its elements in their standard states at 1 bar o ( 1 atm) pressure and the specified temperature (usually 25oC). Thus H f (kJ/mol) for acetone CH3COCH3 is the heat of the reaction 3 C(s) + 3 H2(g) + 1/2 O2(g) CH3COCH3(l)

H = 246.8 kJ

(1)

o o and so H f (CH3COCH3(l)) = 246.8 kJ/mol). By definition, H f (kJ/mol) = 0 for any element in its standard state at 25oC and 1 bar. o Tabulated heats of formation H f (kJ/mol) are given in Table 6.4, p. 238, and Appendix 3,

pp. A-8 to A-12, in Chang. These may be used to calculate the standard enthalpy change, Hrxn , for any reaction for which the heats of formation of all reactants and products are known:
o o Hrxn =

products

prod

Ho f ( prod)

reactants

react

H o f (react)

(2)

This equation tells us to sum the enthalpies of formation of each product multiplied by its stoichiometric coefficient in the reaction equation and then to subtract the enthalpy of formation of each reactant multiplied by its stoichiometric coefficient. We use this equation to work
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Chang, 8th Edition, Chapter 6, Worksheet #2

S. B. Piepho, Fall 2005

problem (2). o Hrxn applies for a balanced equation with specific stoichiometric amounts. If a different number of moles reacts, the heat absorbed or evolved will change proportionately (problem 3).

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Chang, 8th Edition, Chapter 6, Worksheet #2

S. B. Piepho, Fall 2005

_____________________________________________________________________________ _ 1. From the following heats of reaction 2 SO2(g) + O2(g) 2 SO3(g) H = 196 kJ (a) 2 S(s) + 3 O2(g) 2 SO3 (g) H = 790 kJ (b) calculate the heat of reaction for S(s) + O2(g) SO2(g) H = ? kJ (c)

Method: Use Hesss Law to solve this problem: Identify a species in the target equation (c) which is on the correct side in only one of the listed equations, (a) or (b). Multiply the entire equation, and its H value by the factor n necessary to make the stoichiometric coefficient for the species identical to that in equation (c). Reverse a listed equation, (a) or (b), and change the sign of its H value if it contains a species which is on the wrong side of the target equation (c); next multiply the entire reversed equation by the factor n necessary to make the stoichiometric coefficient for the species identical to that in equation (c). The H value for the rewritten equation is ( - n) times that of the original equation. (Ignore any species present in both equations (a) and (b).) Test to see if your rewritten equations now sum to the desired equation (c). If they do, the H value for equation (c) is the sum of the H values of the rewritten equations. Answer: (1/2) Eq(b) + ( - 1/2) Eq(a) = Eq(c); Thus, (1/2)H (b) + ( 1/2)H (a) = H (c) so H(c) =(1/2)( 790 kJ) + ( 1/2)( 196 kJ) = 297 kJ

_____________________________________________________________________________ _ 2. Calculate the standard reaction enthalpy for the photosynthesis reaction, o Hrxn 6 CO2(g) + 6 H2O(l) C6H12O6(s) + 6 O2(g) = ? kJ
Note: The heat of formation of glucose, C6H12O6(s), is given in Appendix 3 on pg A-12.

Answer: Use Eq (2) with 1274.5 kJ/mol, and

o o Ho f (CO2(g)) = 393.5 kJ/mol, H f (H2O(l)) = 285.8 kJ/mol, H f (C6H12O6(s)) =

o Ho f (O2(g)) = 0 kJ/mol. Thus H = 2801.3 kJ 2801 kJ for the photosynthesis reaction. _____________________________________________________________________________ _ 3. Is the photosynthesis reaction above endothermic or exothermic? How much heat is absorbed or evolved if 11.0 g of CO2(g) reacts completely with excess water to form glucose and oxygen

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Chang, 8th Edition, Chapter 6, Worksheet #2 gas?

S. B. Piepho, Fall 2005

Answers: Endothermic. For second part, see last paragraph on page 1. 117 kJ of heat is absorbed.

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