HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY

SCHOOL OF CHEMISTRY AND LIFE SCIENCE Socialist Republic of Vietnam

Department of Chemistry
----***------ Independence – Liberty – Happiness
-------------------------------------

Home exercises
Part 1

1.The wavelength of the green light from a traffic signal is centered at 522 nm. What is the
frequency of this radiation?
2. Calculate the energy (in joules) of
a) a photon with a wavelength of 5.00x104 nm (Infrared region)
b) a photon with a wavelength of 5.00x10-2 nm.
3. The energy of a photon is 5.87x10-20 J. What is the wavelength (in nanometers)?
4. What is the wavelength of a photon emitted during a transition from the ni=5 state to the nf
= 2 in the hydrogen atom?
5. Calculate the wavelength in the following two cases:
* The wavelength of an electron traveling at 1.24x107 m/s. me = 9.1x10-31 kg
* The wavelength of a baseball of mass 149g traveling at 41.3m/s.
6. Calculate the wavelength of the “particle” in the following two cases:
a) The fastest serve in tennis is about 62 m/s. Calculate the wavelength associated with a
6.0x10-2 kg tennis ball traveling at this velocity
b) Calculate the wavelength associated with an electron moving at 62 m/s.

7. How many individual orbitals are there in the third shell? Write out n, l, ml quantum
numbers for each one and label each set by the s, p, d, f designations.
8. Describe the characteristics of an s orbital, a p orbital, and a d orbital. Which of the
following orbitals do not exist: 1p, 2s, 2d, 3p, 3d, 3f, 4g?
9. What is the maximum number of electrons in an atom that can have the following
quantum numbers? Specify the orbitals in which the electrons would be found. (a) n = 2,
ms = +1/2; (b) n=4, ml = +1; (c) n=3, l =2; (d) n=2, l=0, ms = +1/2; (e) n=4, l =3, ml =-2
10. An electron in a certain atom is in the n=2 quantum level. List the possible values of l and
ml that it can have.
11. List all the possible subshells and orbitals associated with the principle quantum number n,
if n=5.
12. Indicate which of the following sets of quantum numbers in an atom are unacceptable and
explain why:
(a) (1,0,1/2,1/2) (b) (3,0,0,+1/2) (c) (2,2,1,+1/2)
(d) (4,3,-2,+1/2) (e) (3,2,1,1,)
13. Indicate the number of unpaired electrons present in each of the following atoms: B (Z=5),
Ne (Z=10), P (Z=15), Sc (Z=21), Mn (Z=25), Se (Z=34), Kr (Z=36), Fe (Z=26), I (Z=53),
Pb (Z=82), Cd (Z=48).
14. Draw the shapes (boundary surfaces) of the following orbitals: a) 2py; b) 3 d Z 2 ; c) 3d x 2 - y 2
15. Draw orbital diagrams for atoms with the following configuration:
a) 1s22s22p5 b) 1s22s22p63s23p3 c) 1s22s22p63s23p64s23d7
16. The ground-state electron configurations listed here are incorrect. Explain what mistakes
have been made in each and write the correct electron configurations
Al: 1s22s22p43s23p3
B: 1s22s22p5
F: 1s22s22p6
17. Without referring to a periodic table, write the electron configuration of the elements with
the following atomic numbers: a) 9; b) 20; c) 26; d) 33. Classify the elements.
18. Specify the group of the periodic table in which each of the following elements is found:
a) [Ne] 3s1, b) [Ne]3s23p3, c) [Ne]3s23p6, d) [Ar]4s23d8
19. A M2+ ion derived from a metal in the 1st transition metal series has four electrons in the
3d subshell. What element might M be?
20. In general, ionization energy increases from left to right across a given period. Aluminum,
however, has a lower ionization energy than magnesium. Explain.
21. Two atoms has the electron configurations 1s22s22p6 and 1s22s22p63s1. The first ionization
energy of one is 2080 KJ/mol, and that of the other is 496 KJ/mol. Match each ionization
energy with one of the given electron configurations. Justify your choice ?
22. A hydrogenlike ion is an ion containing only one electron. The energies of the electron in
a hydrogenlike ion are given by
æ 1 ö
En = -(2.18 x10 -18 J ) Z 2 ç 2 ÷
èn ø
Where n is the principle quantum number and Z is the atomic number of the element.
Calculate the ionization energy of the He+ ion.
23. From the following data, calculate the average bond energy for the N-H bond:
NH3(g) ® NH2(g) + H(g) DHo = 435KJ
NH2(g) ® NH(g) + H(g) DHo = 381 KJ
NH(g) ® N(g) + H(g) DHo = 360 KJ
24. The energy needed for the following process is 1.96x104KJ.mol-1:
Li(g) ® Li3+ (g) + 3e-
If the first ionization energy for lithium is 520 kJ/mol-1, calculate the second ionization
energy of lithium, that is, the energy required for the process
Li+(g) ® Li2+(g) + e-
æ 1 ö
(Use the equation: En = -(2.18 x10 -18 J ) Z 2 ç 2 ÷ )
èn ø
25. According to VB theory, explain, why the nitrogen atom cannot have pentavalence, while
the phosphorus has.
26. Determine and explain all possible valences of the following atoms: S, Cl, C.
27. Draw a Lewis formula for the following species: H2O, H3O+, NF3, OF2, BF3, [BF4]-, SF4,
SF6.
28. What is the hybridization of the central atom in each of the following: NCl3, CF4, SF6, NH3,
NH4+.
29. What hybridizations are predicted for the central atoms in the following molecules:
H2 O H2 S H2Se H2Te
o o
104.5 92.2 91o 89.5o
 Why the bond angles decrease by the above order?
30. Predict geometry of the following molecules: H2O, H3O+, CH4, CO2, SO2, BF3.
31. Describe the hybridization of N in each of these species:
i) NH3; ii) NH4+; iii) H𝑁̈ = 𝑁̈H; iv) HC º N : ; v) H2𝑁̈ - 𝑁̈H2
32. What change in hybridization occurs in the following reaction?
:NH3 + BF3 →H3N: BF3
31. Briefly discuss the bond angles in the hydroxylamine molecule in terms of the ideal
geometry and the small changes caused by electron-pair repulsions.
32. Use the appropriate milecular orbital energy diagram to write the electron configuration for
each of the following; calculate the bond order of each, and predict which would exist (a)
H2+; (b) H2; (c) H2-; (d) H22-.
33. Repeat exercise 32 for (a) He2+; (b) He2; (c) He22+
34. Repeat exercise 32 for (a) N2; (b) Ne2; (c)C22-
35. Repeat exercise 32 for (a) Li2; (b) Li2+; (c) O22-
36. Use the appropriate molecular orbital energy diagram to write electron configurations of
the following molecules and ions: (a) Be2, Be2+, Be2-; (b) B2, B2+, B2-.
37. Use the preceding diagram to fill in an MO diagram for NO-, what is the bond order of NO-
? It is paramagnetic? How would you assess its stability?
38. Repeat exercise 37 for NO+
39. Repeat exercise 37 for CN+. Refer to the preceding diagram but assume that the P2px P2py
MOs are lower in energy than the 2σp MO.
40. Explain why ionization energies of molecules H2, N2, C2, CO higher than those of the
corresponding atoms ?
H C N O F
I1 (KJ.mol-1) 1308 1083 1396 1312 1675
H2 C2 N2 O2 F2
-1
I1 (KJ.mol ) 1488 1154 1507 1173 1526

41. Compare dipole moment of the following molecules: NH3 and NF3 and explain?
42. Do the following molecules have dipole moment ? Explain?
F2; BeF2; BF3; CF4; CO2; SO2

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:

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

8. Calculate the standard enthalpy of formation of

(1) DHo= -726 kJ/mol
(2) DHco(Cgr) = -393 kJ/mol
(3) DHfo(H2O(l)= -286 kJ/mol

9. Calculate the enthalpy change for the process

(*)

And calculate bond energy of C-Cl in CCl4

Given that:
DHo(1)=30.5 kJ/mol
DHo(2)=715.0 kJ/mol
DHo(3)=242 kJ/mol
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
2 2
H2(g) + F2(g) → HF(l) DHo2 = -600.0 kJ/mol

DHo3 = -285.8 kJ/mol

1
H2(g) + 2 O2(g) → 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.
Chapter II

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)
DH = -393 kJ/mol and DS = 2.86 J/mol K at 25 C. (a) Does this reaction becom more or less
o o . o

favorable as the temperature increases? (b) For the reaction:

C(s) + 12 O2(g) → CO (g) (111)
DH = -110.52 kJ/mol and DS = 89.36 J/mol K at 25oC. Does this reaction becom more or less
o o .

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 25 C. What is the equilibrium constant for the reaction H2(g) + Cl2(g) ⇄2HCl(g) at the same
o

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
o
at 1650 C. 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=
-11
4.8x10 . 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).