Dpto.

Ciencia e Ingeniería de Materiales e Ingeniería Química

Chemical Basis of Engineering
Problem Set T5

Worked Examples

1. Thermal decomposition of potassium chlorate (KClO3) yields potassium chloride and

oxygen where H = -22.3 kJ/mol. Determine the value of the standard enthalpy of
formation of potassium chlorate from its elements in standard state if the standard
enthalpy of formation of potassium chloride is -436 kJ/mol.

Sol.:
Writing the thermal decomposition of potassium chlorate:
1 3
Cl 2 ( g )  O2 ( g )  K ( s )  KClO3 ( s )
2 2

Considering the following data:

3
KClO3 ( s )  KCl ( s )  O2 ( g ); H 1  22.3 kJ
2
1
Cl 2 ( g )  K ( s )  KCl ( s ); H 2  436kJ
2

Using the Hess’ Law

2. Considering the values of Kp for the chemical dissociation of molecular bromine in

brome as a function of temperature shown in Table 1, determine: a) Hº and Sº for
this reaction and b) Kc at 1400 K. Assume that Hº and Sº are constant throughout
this temperature range.

Table 1
Kp 0.05 0.12 0.25
T (K) 1400 1500 1600

Sol.:
a) ΔG 0   RT· ln K p ;
ΔG 0  H 0  TS 0

S 0 H 0 1
ln Kp   ·  Plotting ln Kp vs 1/T (K-1) it should yield a straight
R R T
line of which cero ordinate it is possible to calculate S0 and of its slope -H0/R.
Therefore:
1
ln K p  9.944  18074· ;
T

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 Then: S0 = 82.68 J·mol-1·K-1 and H0= 150.27 kJ·mol-1.

Kp
K p  K c ·(RT ) n  K c  n
 K p ( RT ) n ; Since n  1, therefore
( RT )
b)
Kp 0.05
Kc  1
 K p ( RT ) 1 ; K c   4.36 ·10 4
( RT ) (0.082 *1400)

3. How much heat is required to raise the temperature of 7.35 g of water from 21.0 to
98.0 ºC? (Assume the specific heat of water is 4.18 J·g-1·ºC-1 throughout this
temperature range).

4. Calculate H for the process in which 50.0 g of water is converted from liquid at 10.0
ºC to vapour at 25.0 ºC.

Sol.:

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Practice Exercises

5. How many kilograms of water initially at 30 ºC is it possible to heat up to its

transformation in water vapour at 100ºC by burning 1000 litres of C2H4 under STP
conditions?
Data:
Standard enthalpy of vaporization of water = 40.6 kJ/mol.
Standard enthalpy of formation of C2H4 = 52.3 kJ/mol
Standard enthalpy of formation of CO2 = -393.13 kJ/mol
Standard enthalpy of formation of H2O (l) = -285.85 kJ/mol
Specific heat of water = 4.18 kJ/kg K
Molar mass of water = 18 g/mol

Sol.: 24.70 kg

6. The molar enthalpies of fusion and vaporization of benzene are 0.9 kJ/mol and 31.0
kJ/mol, respectively. Calculate the entropy change associated with the following
phase transitions in benzene: solid  liquid and liquid  vapour. Benzene normal
melting and boiling points are 5.5 ºC and 80.1 ºC respectively.
Sol.: Sm = 3.2 J·mol-1·K-1; Sb = .2 J·mol-1·K-1

7. Determine the standard enthalpy of combustion for H2 at 200 ºC using the following
data: Hºcomb(H2)25ºC= -68320 cal mol-1, Hºvap(H2O)100ºC= 9720 cal mol-1, cp(H2) =
6.62 cal mol-1 K-1, cp(O2) = 6.76 cal mol-1 K-1, cp(H2O)l = 18 cal mol-1 K-1 cp(H2O)g =
8.22 cal mol-1 K-1.

Sol.: Hºcomb(H2) 200ºC = -58178 cal/mol.

8. Use the data presented in the following table to determine the values of Ho, So and
Go for the chemical synthesis of ammonia obtained at: i) 298 K and ii) 500 K.

Ho298(kcal/mol) So298K Cp
(cal/mol·K) (cal/mol·K)
N2 0.0 45.767 6.52 + 1.25·10-3 ·T

H2 0.0 31.211 6.94

NH3 -11.04 46.010 6.19 + 7.89·10-3 T

Sol.: i) 298 K Ho = -11040 cal/mol; Go = -3980,38 cal/mol;So = -23.69 cal/mol K
ii) 500 K  Ho = -12550 cal/mol. Go = 1228.5 cal/mol.; So = -27.56 cal/mol K

9. Determine the standard enthalpy of formation of water at 650 ºC using the heat of
formation of water H2O (l) at 25 oC and 1 atm (Hf0 = 68.3 kcal·mol-1) and given the
heat capacities at constant pressure of H2, O2 and H2O 6.9; 8.4 and 9.1 cal·mol-1 K-1
respectively in the range of temperature that follows 25 and 650 ºC as well as the
specific heat of water between 25 and 100 ºC, cp (H2O) 0.96 cal·g-1·C-1. Assume the
specific heats of H2, O2 and H2O are constant throughout this temperature range.

Sol.: Hf = -68.396 kcal/mol

10. Predict whether each of the following processes involves an increase or decrease in
entropy or whether the outcome is uncertain. Explain briefly your reasoning.
a) A solid melts
b) A liquid freezes
c) A liquid that boils
d) A vapour that condenses to solid

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 e) A vapour that condenses to liquid
f) One solid that sublimates

Sol.: a) S Increases; b) S decreases; c) S increases; d) S decreases; e) S decreases; f) S

increases.

11. Explain briefly in which of the following reactions the absorbed heat would be the same
than that corresponding to the standard enthalpy of formation of ethanol

a) 2C(graphite) + 6H (g) + O (g)  C2H5OH (l)

b) 2C(graphite) + 3H2 (g) + ½ O2 (g)  C2H5OH (l)
c) 2C(diamond) + 3H2 (g) + ½ O2 (g)  C2H5OH (l)
d) 4C(graphite) + 6H2 (g) + O2 (g)  2C2H5OH (l)

Sol.: b) (In (a) equation atomic H is being considered; in (d) two moles of ethanol are
formed while in (c) the allotrope less stable of carbon (diamond) instead of graphite was
considered.

12. The extraction of aluminium from aluminium oxide (Al2O3) takes place according to the
following reaction:

Al2O3 + 3C (s)  2Al (l) + 3CO (g)

Where Hº= 1340 kJ and Sº = 586 J/K at 1000 ºC, the temperature at which the
process is being considered. Calculate:
a) The free energy required per mole of aluminium
b) On the other hand, aluminium can also be obtained easily from recycling of
aluminium cans. The expense of energy involved in the recycling process of the
cans can be estimated from the caloric energy supply that is necessary to supply
to raise the temperature from 25 ºC to 660 ºC. Calculate the heat required to
recycle 1 mole of aluminium.
c) How much energy would be saved in the recycling process? Express it as
percentage.

Data:
Tmelting (Al) = 660 ºC; Hm(Al) =10.7 kJ/mol; Cp(Al) =0.90 J·g-1·ºC-1; M(Al)=27
g/mol.

Sol.: a) Gº = 297 kJ/mol; b) Energy = 26.1 kJ/mol; c) The recycling process
saves up to approximately the 91 % of the energy required to obtained aluminum
via electrolysis.

13. A 5-g sample of silver is added to an insulated vessel containing the stoichiometric
amount of chlorine to obtain quantitatively silver chloride. The heat liberated raises the
temperature of 250 cm3 of water in 5.6 ºC. What is the standard enthalpy of formation of
AgCl?
Data: M (Ag) = 107 g/mol; cp (H2O) = 4.18 kJ/kg K; Density (H2O) = 1 g/cm3.

Sol.: Hf (AgCl) = 125.2 kJ/mol

14. Standard enthalpy of formation of liquid water and carbon dioxide at 25 ºC are -68.32
and –94.03 kcal/mol respectively. If the enthalpy of combustion of acetylene to yield
liquid water and carbon dioxide is -310.61 kcal/mol, calculate the numerical value of the
standard enthalpy of formation of acetylene.

C2H2 (g) + 5/2 O2 (g)  2 CO2 (g) + H2O (l) H = -310.61 kcal/mol

Sol.: Hf (C2H2) = 54.23 kcal/mol

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15.Carry out the following operations related to the combustion of methane:
a) Write down the balanced equation for the combustion of methane.
b) Calculate the standard heat of combustion of methane, assuming the formation
of liquid water.
c) Calculate the standard heat of combustion of methane, assuming the formation
of water vapour.
DATA a 25 ºC y 1 atm: Hcombustion (C graphite) = -94.051 kcal/mol; Hvaporization
(H2O) = 9.72 kcal/mol; Hformation (CH4) = -17.895 kcal/mol; Hformation (H2O liquid)
= -68.317 kcal/mol

Sol.: b) Hc (CH4) = -212.79 kcal/mol; c) Hc (CH4) = -193.35 kcal/mol

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