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Thermodynamics. More solved problems.

Problem 1

Calculate the standard molar enthalpy of oxidation of sulfur dioxide to sulfur trioxide (one of most
common processes in inorganic industry) on the basis of the standard molar enthalpies of formation of
the reactants and products (to be found in Tables in Appendix A). Decide, whether the process is
exothermic or endothermic.

SO 2 (g) + 21 O 2 (g) 
→ SO 3 (g)

Solution:

One can find the answer in a single step utilizing equation (1.2):

∆H0 = - 395.72 - (-296.83) = -98.89[kJ / mol]


1 mole SO3 1 mole SO2
product reactant

Oxygen is neglected, as its enthalpy of formation is equal to zero. The reaction is exothermic, heat is
released, the ∆H0 is negative.

Problem 2

Calculate the standard molar enthalpy of absorption of sulfur trioxide in water (another step in sulfuric
acid manufacturing) on the basis of the standard molar enthalpies of formation of the reactants and
products (to be found in Tables in Appendix A). Make a statement on the energetic effect of the
reaction:

SO 3 (g) + H2 O(l) 
→ H2 SO 4 (aq)

Solution:

Again, one can utilize equation (1.2). One should notice, however, that the product is not pure sulfuric
acid, but its aqueous solution. Remember, standard state of aqueous solution corresponds to the
activity equal to 1 mole/dm3.

∆H0 = - 909.27 - (-395.72 + (-285.83)) = -227.72[kJ / mol]


1 mole H2SO4 1 mole SO3 1 mole H2O
product reactants

This absorption is exothermic, heat is released, the ∆H0 is negative.

Problem 3

Calculate the change in enthalpy occurring when 500 grams of pure sulfuric acid (also called
monohydrate) are diluted to 1 mole/dm3 concentration. Assume the temperature of concentrated
sulfuric acid and water used, as well as that of the final solution, was 25°C.

Solution:

H2 SO 4 (l) 
→ H2 SO 4 (aq, 1M)

Here goes equation (1.2) once more. The reaction does not include water, as it is chemically
unchanged (if we decided to put it into equation, it would be at both sides of it). We make additional
assumption (or simplification) by using concentration instead of activity.
Step A. Calculating the number of moles of monohydrate used:
m 500[g]
n= = = 5.102 [mol]
M 98[g / mol]

Step B. Calculating the standard molar enthalpy of dilution:

∆H0 = - 909.27 - (-813.99) = -95.28[kJ / mol]

Step C. Calculating the actual change in enthalpy:

∆H = 5.102 [mol] ⋅ - 95.28[kJ / mol] = -486.122[kJ]

Diluting sulfuric acid is an exothermic process (the ∆H is negative). Heat is released, as is known to
anybody who has performed it (with adequate care and suitable precautions!).

Problem 4

Calculate the change in enthalpy occurring when green parts of the sugar beet produce sugar
(sucrose) contained in its root from gaseous carbon dioxide and liquid water. Assume the
temperature of reactants and product was 25°C and that, on the average, sugar beet-root amounts to
1.5 kg and its sugar content is 20.0 % (w/w). Another simplification involved is treating the main
product as being in standard state. The overall reaction is:

12CO 2 (g) + 11H2 O(l) light,chlorophyll


 → C12H22 O11 (s) + 12O 2 (g)

Solution:

In solving this problem we make full use of the fact that enthalpy is a state property. No matter how
many stages there are between the left side and the right side of the overall reaction (and there are
quite a few in the photosynthesis), we can calculate the change from the difference between the final
state and the initial state of the system.
Step A. Calculating the number of moles of sucrose produced:
m 1500[g] ⋅ 0.20
n= = = 0.877 [mol]
M 342[g / mol]

Step B. Calculating the standard molar (per one mole of sucrose) enthalpy of reaction on the basis of
the enthalpies of formation of the product and reactants:

∆H0 = - 2222 - (12(-393.51) + 11(-285.83)) = 5644.25[kJ / mol]


1 mole sucrose 12 moles CO2 11 moles H2O
product reactants

Step C. Calculating the actual change in enthalpy:

∆H = 0.877 [mol] ⋅ 5644.25[kJ / mol] = 4950.0[kJ]

Synthesis of carbohydrates is an endothermic process (the ∆H is positive). Heat (energy) is


consumed in the process, actually being delivered in the form of photons.

Problem 5

Calculate the change in enthalpy occurring when 1 kg of sucrose is being hydrolysed (inverted) into its
component simple sugars, i.e., glucose and frustose. Assume the temperature of reactant and
products was 25°C. The reaction is:
C12H22 O11 (s) + H2 O(l) invertase
→ C 6H12 O 6 (s, glucose ) + C 6 H12 O 6 (s, fructose )

Solution:

Step A. Calculating the number of moles of sucrose hydrolysed:


m 1000[g]
n= = = 2.924[mol]
M 342[g / mol]

Step B. Calculating the standard molar enthalpy of reaction on the basis of the enthalpies of formation
of the products and reactants:

∆H0 = - 1268 + (-1266) - (-2222 + (-285.83)) = -26.17[kJ / mol]


glucose fructose sucrose H2O
products reactants

Step C. Calculating the total change in enthalpy:

∆H = 2.924[mol] ⋅ -26.17[kJ / mol] = - 76.5[kJ]

Reaction of inversion of sucrose is exothermic (heat is released, the ∆H is negative).

Problem 6

Calculate the change in enthalpy occurring when 152 g of propene (propylene) are converted into
cyclopropane in an isomerization reaction. Assume the temperature of both the reactant and product
was 25°C. The overall (O) target reaction is:
C 3H6 (g, propylene ) 
→ C 3H6 (g, cyclopropane ) (O)
Use only the data given below and apply the Hess's law. (After solving the problem in the desired
way, you can check the final result using standard enthalpies of formation from the tables).

3C(s) + 3H2 (g) 


→ C 3H6 (g, propylene ); ∆H0 = +20.42[kJ / mol] (A)
C(s) + O 2 (g) 
→ CO 2 (g);
∆H0 = -393.51[kJ / mol] (B)
H2 (g) + 21 O 2 (g) 
→ H2 O(l); ∆H0 = -285.83[kJ / mol] (C)
→ 3CO 2 (g) + 3H2 O(l) ∆H0 = -2091[kJ / mol] (D)
C 3H6 (g, cyclopropane ) + 4 21 O 2 (g) 
Solution:

Utilizing Hess's law is useful when the necessary data (enthalpies of formation) are not available for
all the substances involved. In the case we have at our disposal the standard molar enthalpies of
formation of propylene (A), carbon dioxide (B) and water (C), as well as standard molar enthalpy of
combustion of cyclohexane (D).

Step A. We can prepare a new set of reactions (A' through D') rearranging the original set (A through
D) and utilizing the rules given in Example 1.5.

C 3H6 (g, propylene ) 


→ 3C(s) + 3H2 (g); ∆H0 = -20.42[kJ / mol] (A')
3C(s) + 3O 2 (g) 
→ 3CO 2 (g);
∆H0 = -1180.53[kJ / mol] (B')
3H2 (g) + 1 21 O 2 (g) 
→ 3H2 O(l); ∆H0 = -857.49[kJ / mol] (C')
→ C 3H6 (g, cyclopropane ) + 4 21 O 2 (g); ∆H0 = +2091[kJ / mol]
3CO 2 (g) + 3H2 O(l)  (D')
Note: Reactions (A) and (D) were simply written backward and signs of their enthalpies changed.
Reactions (B) and (C) were tripled along with the corresponding enthalpies. Adding
reactions (A') through (D') leads to reaction (O) as the same amounts of C, H2, O2, and H2O
at both sides may be cancelled. Also, adding enthalpies (A') through (D') leads to the
change in enthalpy for reaction (O). Therefore:

∆H0O = ∆H0A' + ∆HB'


0
+ ∆H0C' + ∆HD'
0
= -20.42 - 1180.5 - 857.7 + 2091 = 32.56[kJ / mol]

Step B. Calculating the total change in enthalpy:

152[g]
∆H = ⋅ 32.56[kJ / mol] = 117.84[kJ]
42[g / mol]

Conclusion: this isomerization reaction requires heat supply (at constant pressure).

Check (calculating ∆H0 as a difference between the two enthalpies of formation):

∆H0O = ∆H0f,cyclopropane + ∆H0f,propylene = 53.30 - 20.42 = 32.88[kJ / mol]

The agreement is fairly good. The difference may be ascribed to the fact that enthalpy of combustion
of cyclopropane (D) is known with much less accuracy than the enthalpies of formation.

Unsolved problems.

Problem 7 Calculate the standard enthalpy and standard Gibbs free energy of combustion of
propane using data from thermochemical tables.

Problem 8 Calculate standard enthalpy, standard entropy and standard Gibbs free energy for the
following reactions:
C2H4(g) + H2(g) = C2H6(g)
Fe2O3(s) + 3CO(g) = 2Fe(s) + 3CO2(g)
NO(g) + O3(g) = NO2(g) + O2(g)
C6H6(l) + 3H2(g) = C6H12(l)
Are these reaction spontaneous under standard conditions?

Problem 9 Calculate the amount of heat released (under standard conditions) when

a) 50 g of acetylene,
b) 100 g of benzene,
c) 10 dm3 of methane are burned.

© W. Chrzanowski, 2002

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