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:

𝑁! + 3𝐻!(#) → 2𝑁𝐻% (#) DHo(1)=-92.4 kJ/mol

What is the standard enthalpy of 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 is the enthalpy change 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 -258.8 kJ/mol, respectively. Calculate enthalpy of formation of CH4 from the
following equations
𝐶𝐻4(𝑔) + 2𝑂2(𝑔) → 𝐶𝑂2(𝑔) + 2𝐻2 𝑂 (𝑔)
𝐶(𝑠) + 𝑂2(𝑔) → 𝐶𝑂2(𝑔)
2𝐻! + 𝑂!(#) → 𝐻! 𝑂(#)
8. Calculate the standard enthalpy of formation of 𝐶𝐻# 𝑂𝐻 (𝑙) 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑓𝑜𝑙𝑙𝑜𝑤𝑖𝑛𝑔 𝑑𝑎𝑡𝑎
3
(1) 𝐶𝐻3 𝑂𝐻(𝑙) + 𝑂2(𝑔) → 𝐶𝑂2(𝑔) + 2𝐻2 𝑂 (𝑙5
2
DHo= -726 kJ/mol
(2) 𝐶(𝑠) + 𝑂2(𝑔) → 𝐶𝑂2(𝑔) DHco(𝐶(𝑔) )= -393 kJ/mol
1
(3) 𝐻2 + 𝑂2(𝑔) → 𝐻2 𝑂(𝑙)
2
DHfo(𝐻2 𝑂(𝑙) )= -286 kJ/mol
9. Calculate the enthalpy change for the process
𝐶𝐶𝑙-(#) → 𝐶(𝑔) + 4𝐶𝑙(𝑔) (*)
And calculate bond energy of C-Cl in CCl4
Given that:
𝐶𝐶𝑙-(.) → 𝐶𝐶𝑙-(#) DHo(1)=30.5 kJ/mol
𝐶(/) → 𝐶(#) DHo(2)=715.0 kJ/mol
𝐶𝑙!(#) → 2𝐶𝑙(#) DHo(3)=242 kJ/mol

𝐶(𝑔) + 4𝐶𝑙(𝑔) → 𝐶𝐶𝑙-(.) DHo(4)=-135.5 kJ/mol

10. Given that

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

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

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

11. Determine the heat of formation of liquid hydrogen peroxide at 25oC from the following
thermochemical equations.
 1
H2(g) + O22(g) → H2O(g) DH1o = -241.82 kJ/mol
2H(g) + O(g) → H2O(g) DH2o = -926.92 kJ/mol
2H(g) + 2O(g) → H2O2(g) DH3o = -1070.60 kJ/mol
2O(g) → O2(g) DH4o = -498.34 kJ/mol
H2O2(l) → H2O2(g) DH5o = 51.46 kJ/mol

12. From the following enthalpies of reaction,

4HCl(g) + O2(g) → 2H2O(l) + 2Cl2(g) DHo1 = -202.4 kJ/mol

1 1
H2(g)
2 + F2(g)
2 → HF(l) DHo2 = -600.0 kJ/mol

DHo3 = -285.8 kJ/mol

1
H2(g) + O2(g)
2 → H2O(l)

Find DHo 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

C¾C 346 C=C 602 CºC 835
N¾N 163 N=N 418 NºN 945
O¾O 146 O=O 498
 C¾N 305 C=N 615 CºN 887
C¾O 358 C=O 732* CºO 1072
*
Except in CO2, where it is 799 kJ/mol.

13. Use tabulated bond energies to estimate the enthalpy of reaction for each of the following
gas phase reaction.
(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 ¾ C ¾F(g) + F ¾ F(g) → F ¾ C ¾ F(g) + Cl ¾ 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 DSo298 for each the following reactions.
Compare the signs and magnitudes for these DSo298 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 DGo for the reaction
H2O
NaI(s) → Na+(aq) + I-(aq)

19. For the reaction

C(s) + O2(g) → CO2 (g) (110)

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

C(s) + 12 O2(g) → CO (g) (111)

DHo = -110.52 kJ/mol and DSo = 89.36 J/mol.K at 25oC. Does this reaction becom more or less
favorable as the temperature increases? (c) Compare the temperature dependencies of these
reaction.
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. Calculate the concentration of OH- ions in a 1.4x10-3 M HCl solution

27. Classify each of the following species as a Bronsted acid or base, or both: a) H2O, b) OH-, c)
H3O+, d) NH3, e) NH4+, g) NO3-, h) CO32-, i) HBr, j) HCN
28. What are the concentrations of HSO4-, SO42-, and H+ in a 0.2M KHSO4 solution? (H2SO4 ís a
strong acid; Ka for HSO4- = 1.3x10-2)
29. 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
30. 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.
31. H2CO3 is diprotic and therefore 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
32. Calculate the pH of the buffer system made up of 0.15M NH3/0.35M NH4Cl. Ka for NH4+ =
5.6 x 10-10.
33. Calculate the pH of a 0.36M CH3COONa solution, knowing Ka(CH3COOH) = 1.8x10-5
34. Predict the pH of a NaHCO3 solution. Ka1(H2CO3) = 4.2x10-7 and Ka2(H2CO3) = 4.8x10-11
35. What is the solubility of silver chloride in g/L? (Ksp for AgCl(s) = 1.6 x 10-10).
36. If 2.00 mL of 0.200 M NaOH are added to 1.00 L of 0.100 M CaCl2, will a precipitate form?
(Ksp for Ca(OH)2 = 8.0 x 10-6).
37. 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).