Part II- Fundamental laws of chemical processes

1. In a certain process, 678 J of heat is absorbed by a system while 294 J of work is done on the
system. What is the change in internal energy for the process?
2. In a process, 394J of work is done by the system and 307J is the change in internal energy for
the given process. What is the heat absorbed/ released by the system?
3. Given that:

Ho(1)=-92.4 kJ/mol
What is the standard enthalpy of the formation of NH3 gas?
4. The heat of combustion of carbon to CO2 is -393.5 KJ/mol. Calculate the heat upon formation
of 35.2 g of CO2 from carbon and oxygen gas
5. What enthalpy changes when 1.0 g of water is frozen at 0oC? (ΔHmel= 1.435 kcal/mol)
6. Calculate the enthalpy of sublimation of 100 g of carbon dioxide at 183 K, if ΔHsub = 3.87
kcal/mol)
7. The enthalpy of combustion of methane, graphite, and hydrogen at 298K are -890.3 kJ/mol, -
395 kJ/mol and -285.8 kJ/mol, respectively. Calculate the enthalpy of the formation of CH4 from
the following equations
(1)

8. Calculate the standard enthalpy of formation of

(1) Ho= -726 kJ/mol

(2) Hco( = -393 kJ/mol

(3) Hfo( )= -286 kJ/mol

9. Calculate the enthalpy change for the process

(*)

And calculate the bond energy of C-Cl in CCl4

Given that:
Ho(1)=30.5 kJ/mol

Ho(2)=715.0 kJ/mol

Ho(3)=242 kJ/mol

Ho(4)=-135.5 kJ/mol
 10. Given that

S(s) + O2(g) → SO2(g) H = -296.8 kJ/mol

S(s) + 23 O2(g) → SO3(g) H = -395.6 kJ/mol

Determine the enthalpy change for the decomposition reaction 2SO3(g) → 2SO2(g) + O2(g)

11. Determine the heat of the formation of liquid hydrogen peroxide at 25oC from the following
thermochemical equations.

H1o = -241.82 kJ/mol

1
H2(g) + 2 O2(g) → H2O(g)
2H(g) + O(g) → H2O(g) H2o = -926.92 kJ/mol
2H(g) + 2O(g) → H2O2(g) H3o = -1070.60 kJ/mol
2O(g) → O2(g) H4o = -498.34 kJ/mol
H2O2(l) → H2O2(g) H5o = 51.46 kJ/mol

12. From the following enthalpies of reaction,

4HCl(g) + O2(g) → 2H2O(l) + 2Cl2(g) Ho1 = -202.4 kJ/mol

Ho2 = -600.0 kJ/mol

1 1
2 H2(g) +2 F2(g) → HF(l)

H2(g) + 2 O2(g) → H2O(l) Ho3 = -285.8 kJ/mol

1

Find Ho for 2HCl(g) + F2(g) → 2HF(l) + Cl2(g).

TABLE 15-2 Some Average Single Bond Energies (kJ/mol of bonds)

H C N O F Si P S Cl Br I
436 413 391 463 565 318 322 347 432 366 299 H
346 305 358 485 272 339 285 213 C
163 201 283 192 N
146 452 335 218 201 201 O
155 565 490 284 253 249 278 F
222 293 381 310 234 Si
201 326 184 P
226 255 S
242 216 208 Cl
193 175 Br
151 I
 TABLE 15 -3 Comparison of Some Average
Single and Multiple Bond
Energies (kJ/mol of bonds)

Single Bonds Double Bonds Triple Bonds

C⎯C 346 C=C 602 CC 835
N⎯N 163 N=N 418 NN 945
O⎯O 146 O=O 498
C⎯N 305 C=N 615 CN 887
C⎯O 358 C=O 732* CO 1072
*Except in CO , where it is 799 kJ/mol.
2

13. Use tabulated bond energies to estimate the enthalpy of the reaction for each of the following
gas phase reactions.
(a) N2 + 3H2 → 2NH3
(b) CH4 + Cl2 → CH3Cl + HCl
(c) CO + H2O → CO2 + H2

14. Use the bond energies listed in Table 15-2 to estimate the heat of reaction for
Cl F

Cl ⎯ C ⎯F(g) + F ⎯ F(g) → F ⎯ C ⎯ F(g) + Cl ⎯ Cl(g)

F F

15. (a) Use the bond energies listed in Table 15-2 to estimate the heats of formation of HCl(g)
and HF(g). (b) Compare your answers to the standard heats of formation in Appendix K.

16. When solid sodium chloride is cooled from 25oC to 0oC, the entropy change is -4.4 J/mol. K.
Is this an increase or decrease in randomness? Explain this entropy change in terms of what
happens in the solid at the molecular level.

17. Use So data from Appendix K to calculate the value of So298 for each the following
reactions. Compare the signs and magnitudes for these So298 values and explain your
observation.
(a) 2NO(g) + H2(g) → N2O(g) + H2O(g)
(b) 2N2O5(g) → 4NO2(g) + O2(g)
(c) 2NH4NO3(s) → 2N2(g) + 4H2O(g) + O2(g)

18. The standard Gibbs free energy of formation is -286.06 kJ/mol for NaI(s), -261.90 kJ/mol for
Na+(aq), and -51.57 kJ/mol for I-(aq) at 25oC. Calculate Go for the reaction
H2O
NaI(s) → Na+(aq) + I-(aq)

19. For the reaction

C(s) + O2(g) → CO2 (g) (110)

Ho = -393 kJ/mol and So = 2.86 J/mol. K at 25oC. (a) Does this reaction become more or less
favorable as the temperature increases? (b) For the reaction:

C(s) + 12 O2(g) → CO (g) (111)

Ho = -110.52 kJ/mol and So = 89.36 J/mol.K at 25oC. Does this reaction become more or less
favorable as the temperature increases? (c) Compare the temperature dependencies of these
reactions.
20. The equilibrium constant (Kc) for the reaction: 2HCl(g) ⇄H2(g) + Cl2(g) is 4.17x10-34 at
25oC. What is the equilibrium constant for the reaction H2(g) + Cl2(g) ⇄2HCl(g) at the same
temperature?
21. Consider the following equilibrium process at 700oC: 2H2(g) + S2(g) ⇄ 2H2S(g)
Analysis shows that there are 2.50 moles of H2, 1.35x10-5 mole of S2 and 8.70 moles of H2S
present in a 12.0 L flask. Calculate the equilibrium constant Kc for the reaction.
22. At equilibrium, the pressure of the reacting mixture CaCO3(s) ⇄ CaO(s) + CO2(g) is 0.105
atm at 350oC. Calculate Kp and Kc?
23. For the synthesis of ammonia N2(g) + 3H2(g) ⇄ 2NH3(g) the equilibrium constant Kc at
375oC is 1.2. Starting with [H2]o = 0.76M, [N2]o= 0.6M, [NH3]o= 0.48M, which gas will have
increased in concentration and which will have decreased in concentration when the mixture
comes to the equilibrium?
24. The equilibrium constant Kc for the reaction H2(g) + CO2(g) ⇄ H2O(g) + CO(g) is 4.2 at
1650oC. Initially, 0.80 mol H2 and 0.80 mol CO2 are injected into a 5.0 L flask. Calculate the
concentration of each species at equilibrium.
25. Consider the following equilibrium process at 686oC:
H2(g) + CO2(g) ⇄ H2O(g) + CO(g)
The equilibrium concentrations of the reacting species are [CO] = 0.05M, [H2] = 0.045M,
[CO2]= 0.086M, and [H2O] = 0.04M a) Calculate Kc at 686oC. b) If we add CO2 to increase its
concentration to 0.50 mol/L what will the concentrations of all the gases be when equilibrium is
restablished?
26. PCl5 was decomposed by the reaction:
PCl5(g) ⇋ PCl3(g) + Cl2(g)
- Calculate Kp for the reaction, knowing that the decomposition percent of PCl5 is 0.485 at
200oC and the total pressure at equilibrium is 1 atm.
- Calculate the system's pressure at equilibrium if adding 2.085 g PCl5 to a vacuum flash of
200 cm3 at 200oC.
27. H2(g) + I2(g) 2HI (g).
a. When 46.0 g of I2 and 1.00 g of H2 are heated to equilibrium at 470oC, the equilibrium mixture
contains 1.9g I2. How many mol of each gas are present in the equilibrium mixture. Calculate the
equilibrium constant.
b. 1 mol each of H2 and I2 are heated in a 30-L chamber to 470oC. Determine (a) how many mol of
I2 remain unreacted when equilibrium is established. (b) the total pressure in the chamber.
 28. A solution is prepared by mixing 1.00 g ethanol (C2H5OH) with 100.0 g water to give a final
volume of 101 mL. Calculate the molarity, mass percent, mole fraction, and molality of
ethanol in this solution.
29. A certain soft drink is bottled so that a bottle at 25oC contains CO2 gas at a pressure of 5.0
atm over the liquid. Assuming that the partial pressure of CO2 in the atmosphere is 4.0* 10-4
atm, calculate the equilibrium concentrations of CO2 in the soda both before and after the
bottle is opened. The Henry’s law constant for CO2 in aqueous solution is 3.1* 10-2 mol.L-1.
atm-1 at 25oC.
30. A solution was prepared by dissolving 18.00 g glucose in 150.0 g water. The resulting
solution was found to have a boiling point of 100.34oC. Calculate the molar mass of
glucose. Glucose is a molecular solid that is present as individual molecules in solution.
31. What mass of ethylene glycol (C2H6O2, molar mass 62.1 g/mol), the main component of
antifreeze, must be added to 10.0 L water to produce a solution for use in a car’s radiator
that freezes at -23.3oC)? Assume the density of water is exactly 1 g/mL
32. A chemist is trying to identify a human hormone that controls metabolism by determining
its molar mass. A sample weighing 0.546 g was dissolved in 15.0 g benzene, and the
freezing-point depression was determined to be 0.24oC. Calculate the molar mass of the
hormone.
33. Arrange the following species according to their strengths as bases: H2O, F-, Cl-, NO2-, and
CN-.
Ka (HF) = 7.2x10-4; Ka (HNO2) = 4.10-4; Ka (HCN) = 6.2x10-10; Ka (HClO) = 3.5x10-8
34. Calculate the concentration of OH- ions in a 1.4x10-3 M HCl solution
35. Classify each of the following species as a Bronsted acid or base, or both: a) H 2O, b) OH-, c)
H3O+, d) NH3, e) NH4+, g) NO3-, h) CO32-, i) HBr, j) HCN
36. What are the concentrations of HSO4-, SO42-, and H+ in a 0.2M KHSO4 solution? (H2SO4 is a
strong acid; Ka for HSO4- = 1.3x10-2)
37. A solution of nitrous acid HNO2 is 0.2M a) Calculate pH, b) What is the concentration of the
nitrite ion NO2-? Ka(HNO2) = 4.5x10-4
38. The ionization constant, Ka, for propanoic acid C2H5COOH is 1.3x10-5. What is the
ionization percent in 0.65M solution of propanoic acid? Propanoic acid is monoprotic acid.
39. H2CO3 is diprotic and has two ionization constants, Ka1= 4.2x10-7 and Ka2= 4.8x10-11. The
pH of a carbonic acid solution can be calculated without using Ka2. Explain using a 0.10 M
solution.
40. Calculate the pH of a solution that contains 1.00 M HCN (Ka= 6.2x10-10) and 5.00 M HNO2
(Ka= 4.0x10-4). Also, calculate the concentration of cyanide ion (CN-) in this solution at
equilibrium. (Results: pH=1.35; [CN-] =1.4x10-8M)
41. Calculate the pH of the buffer system made up of 0.15M NH3/0.35M NH4Cl. Ka for NH4+ =
5.6 x 10-10.
42. Calculate the pH of a 0.36M CH3COONa solution, knowing Ka(CH3COOH) = 1.8x10-5
43. Predict the pH of a NaHCO3 solution. Ka1(H2CO3) = 4.2x10-7 and Ka2(H2CO3) = 4.8x10-11
44. What is the solubility of silver chloride in g/L? (Ksp for AgCl(s) = 1.6 x 10-10).
45. If 2.00 mL of 0.200 M NaOH is added to 1.00 L of 0.100 M CaCl2, will a precipitate form?
(Ksp for Ca(OH)2 = 8.0 x 10-6).
46. What is the molar solubility of AgBr in (a) pure water and (b) 0.0010 M NaBr? (Ksp for
AgBr = 7.7 x 10-13).