Question

The enthalpy of reaction changes somewhat with temperature. Suppose we wish to calculate ΔH for a reaction at a temperature T that is different from 298 K. To do this, we can replace the direct reaction at T with a three-step process. In the first step, the temperature of the reactants is changed from T to 298 K. ΔH for this step can be calculated from the molar heat capacities of the reactants, which are assumed to be independent of temperature. In the second step, the reaction is conducted at 298 K with an enthalpy change ΔH°. In the third step, the temperature of the products is changed from 298 K to T. The sum of these three enthalpy changes is ΔH for the reaction at temperature T.
An important process contributing to air pollution is the following chemical reaction:
SO2(g) + ½O2(g) → SO3(g)
For SO2(g), the heat capacity cp is 39.9, for O2(g) it is 29.4, and for SO3(g) it is 50.7 J K⁻¹ mol⁻¹.
Calculate ΔH for the preceding reaction at 500 K, using the enthalpies of formation at 298.15 K from Appendix D.

Answer 1

Answer:

-99.8 kJ

Explanation:

We are given the methodology to answer this question, which is basically  Kirchhoff law . We just need to find the heats of formation for the reactants and products and perform the calculations.

The standard heat of reaction is

ΔrHº = ∑ ν x ΔfHº products - ∑ ν x ΔfHº reactants

where ν are the stoichiometric coefficients in the balanced equation, and ΔfHº are the heats of formation at their  standard states.

  Compound                 ΔfHº (kJmol⁻¹)

        SO₂                             -296.8

         O₂                                    0

         SO₃                            -395.8

The balanced chemical equation is

SO₂(g) + ½O₂(g) → SO₃(g)

Thus

Δr, 298K Hº( kJmol⁻¹ ) =  1 x (-395.8) - 1 x (-296.8) = -99.0 kJmol⁻¹

Now the heat capacity of reaction  will be be given in a similar fashion:

Cp rxn = ∑ ν x Cp of products - ∑ ν x Cp of reactants

where ν is as above the stoichiometric coefficient in the balanced chemical equation.

Cprxn ( JK⁻¹mol⁻¹) = 50.7 - ( 39.9 + 1/2 x 29.4 ) = - 3.90

                         = -3.90 JK⁻¹mol⁻¹

Finally Δr,500 K Hº = Δr, 298K Hº +  CprxnΔT

Δr,500 K Hº = - 99 x 10³ J + (-3.90) JK⁻¹ ( 500 - 298 ) K = -99,787.8

                     = -99,787.8 J x 1 kJ/1000 J  = -99.8 kJ

Notice thie difference is relatively small that is why in some problems it is o.k to assume the change in enthalpy is constant over a temperature range, especially if it is a small range of temperatures.