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Chemistry 40S Supplementary Problems Electronic Structure, etc… page 1

Electronic Structure, Bonding & The Periodic Table


1. What are the definitions of “wavelength” and “frequency” of waves?

2. List the regions of the electromagnetic spectrum in order of increasing wavelength.

3. List the colours of the rainbow in order of increasing frequency.

4. What is the “speed of light”? What symbol is used to represent this quantity?

5. A recent news report stated that scientists had succeeded in slowing down the speed
of light. How is this possible if the speed of light is supposed to be “constant”?

6. CJOB radio emits a signal at a frequency of 680 kHz. Calculate the wavelength of
these radio waves.

7. A cordless telephone operates at 900 MHz. What is the wavelength of this signal?

8. Visible light falls between 400 nm and 700 nm. What is the range of frequencies for
visible light?

9. A sodium lamp emits yellow light at a frequency of 5.1 x 1014 s-1. Calculate the
wavelength of this light.

10. Which color of light is at the 400 nm end of the visible spectrum?

11. What is a “quantum”? What is a “photon”?

12. Calculate the minimum and maximum energies of light in the visible spectrum (see
question 6).

13. How is the energy of electromagnetic radiation related to its wavelength? How is it
related to the frequency of the radiation?

14. Calculate the energy and frequency of light where λ = 6.56 x 10-5 cm.

15. Microwave radiation may have ν = 3.2 x 1011 s-1. Calculate the energy and
wavelength of this radiation.

16. Green light has an energy of 3.84 x 10-19 J/photon. Calculate λ and ν for this green
light.

17. Calculate the energy of an electron in the 3rd energy level of a hydrogen atom.

18. Calculate the energy of an electron in the 2nd energy level of a lithium cation, Li2+.

19. An electron falls from n = 5 to n = 2 in a hydrogen atom.


a) Is energy released or absorbed? Explain.
b) Calculate the wavelength of light emitted during this electron transition.

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Chemistry 40S Supplementary Problems Electronic Structure, etc… page 2

20. An electron falls from n = 6 to n = 3 in a helium cation, He+. Calculate the


wavelength of the light emitted during this transition. Would this light be visible to the
naked eye?

21. Calculate the frequency of light that would allow an electron to jump from the 2nd to
the 3rd energy level in a hydrogen atom.

22. What does it mean to say that an atom is in the “ground state”? What is the term
applied when the atom is not in the ground state?

23. When an atom is “ionized”, it loses an electron. The electron can be thought to jump
from to an energy level where n = ∞. Calculate the maximum wavelength of
radiation that would ionize a ground-state hydrogen atom.

24. What does the “Heisenberg Uncertainty Principle” state?

25. How did Bohr’s model of the atom violate the Heisenberg Uncertainty Principle?

26. Is an electron a particle? or is it a wave? Explain.

27. What is an “orbital”? What is the probability of finding an electron in an orbital as it


is pictured in your text?

28. What are the four “quantum numbers” that are used to describe an electron within
an atom? What does each quantum number determine?

29. What does the Pauli Exclusion Principle state?

30. How many electrons can be held in any given orbital? This is a direct result of the
Pauli Exclusion Principle.

31. How many electrons (in total) can be held on the 3rd energy level of an atom? Show
how you calculated the answer.

32. Why is the electron configuration, 1s2 2s2 2p4 3s1, called an “excited state”?

33. Why is the electron configuration, 1s2 2s2 2p7 3s1, an impossible configuration?

34. Draw orbital diagrams for: a) silicon b) fluorine c) copper

35. Write electron configurations for: a) nitrogen b) argon c) chromium

36. Write abbreviated electron configurations for: a) calcium b) chlorine

37. Identify the element whose valence electron configuration is “5s2 5p2”.

38. Write the valence electron configurations for: a) bromine b) barium

39. Identify the element whose electron configuration is 1s2 2s2 2p6 3s2 3p6 4s2 3d2.

40. Identify the element whose abbreviated electron configuration is [Ar] 4s2 3d10 4p3.

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Chemistry 40S Supplementary Problems Electronic Structure, etc… page 3

41. Identify the element whose valence configuration is 5s2 5p5.

42. How many unpaired electrons are there in ground state atoms of…
a) carbon b) sulfur c) iron d) nickel

43. Which element(s) in period 4 have two unpaired electrons in their ground states?

44. Which two families of elements comprise the “s-block” on the periodic table?

45. Which family of elements comprises the “d-block” on the periodic table?

46. Which families of elements comprise the “f-block” on the periodic table?

47. Give the symbol of the atom whose ground state electron configuration is…
a) 1s2 2s2 2p3
b) 1s2 2s2 2p6 3s1
c) 1s2 2s2 2p6 3s2 3p6 4s2
d) [Xe] 6s2 4f14 5d10 6p2

48. Which family of elements has electron configurations ending in “p5”?

49. Describe the trend in atomic radii of elements within a period on the periodic table.
Explain why the trend exists.

50. Describe the trend in atomic radii of elements within a group on the periodic table.
Explain why the trend exists.

51. Lithium (Z = 3) has the following successive ionization energies:

IE 1: 520 kJ/mol IE 2: 7 300 kJ/mol IE 3: 11 810 kJ/mol

Explain why there is such a large increase between IE 1 and IE 2.

52. An element in period 3 has the following successive ionization energies:

IE 1: 787 kJ/mol IE 2: 1577 IE 3: 3232 IE 4: 4356 IE 5: 21 270

How many valence electrons does the element have? Identify the element.

53. What is the trend in first ionization energies within a period on the periodic table?
Explain the trend.

54. Explain the following trend in first ionization energies:

Li: 520 kJ/mol Na: 496 K: 419 Rb: 403 Cs: 376

55. Arrange the following in order of increasing first I.E.: As, Sn, Br, Sr

56. Arrange the following in order of increasing atomic radius: Rb, As, Sb, Br, Sr

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Chemistry 40S Supplementary Problems Electronic Structure, etc… page 4

57. An element is considered to be paramagnetic if it has unpaired electrons. Which


elements in the third period on the periodic table are paramagnetic?

58. Write the symbols of the four most electronegative elements, in order of increasing
electronegativity.

59. What is a “polar covalent bond”? Discuss “electronegativity” and “sharing of


electrons” in your answer.

60. Classify the following bonds as “non-polar covalent”, “polar covalent”, or “ionic”.
Include calculations as part of your answers.
a) Li-F b) C-Br c) Zn-Cl d) Cu-S

61. Classify the following bonds as “non-polar covalent”, “polar covalent”, or “ionic”.
Include calculations as part of your answers.
a) Na-O b) Al-I c) Si-O d) N-N

62. Arrange the following in expected order of increasing radius: K+, Cl-, S2-, Ca2+, Ar.
Explain your answer.

63. Arrange the following in expected order of increasing radius: F-, O2-, Na+, Ne.

64. Draw the Lewis electron dot diagrams for: a) Mg b) O c) Br

65. Draw the Lewis electron dot diagrams for: a) Na b) P c) Ar

66. Draw the Lewis electron dot diagrams for: a) Ca2+ b) O2- c) F-

67. Draw the Lewis electron dot diagrams for: a) NH4+ b) H3O+ c) OH-

68. Draw the Lewis electron dot diagrams for: a) C2H6 b) C2H4 c) CO2

69. Draw the Lewis electron dot diagrams for: a) N2 b) O2 c) Br2

70. Draw the Lewis electron dot diagrams for: a) NaCl b) K2O c) NH4Br

71. Draw the Lewis electron dot diagrams for: a) NH3 b) CN- c) NaBr

72. What is a coordinate covalent bond? Draw the Lewis dot diagram for the
hydronium ion and label a coordinate covalent bond.

73. Use the periodic table and concepts in this unit to answer the following:
a) What is the electron dot formula for the element with Z = 51.
b) Which of the following elements has the smallest radius? (Li, C, O, Br)
c) What type of bonding would you expect between carbon and sulfur?
d) Which element has the lowest first ionization energy – Ca, Sr, or Mg?
e) Which of the following elements is most metallic – Si, S, N, or Cl?
f) Which is larger – P3- or P, Ca2+ or Ca?

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AP Chemistry 42S Supplementary Problems Chemical Kinetics… page 5

Chemical Kinetics – Rates of Chemical Reactions


1. Describe the collision theory of reactions. What is a “successful” collision? What
factors determine if a collision is successful?

2. List the factors that affect the rates of chemical reactions.

3. Which of the following units would NOT be used to measure the rate of a reaction?
Explain why. a) cm/s b) mL/min c) mol/L

4. Refrigerated food stays fresh for long periods. The same food stored at room
temperature spoils quickly. Why?

5. Use collision theory to explain how “temperature” affects the rate of a reaction.

6. What is the “activation energy” of a reaction? How is this related to the rate of the
reaction?

7. When the gas to a Bunsen burner is turned on, the gas does not begin to burn (react
with the oxygen in the air) until a flame lights it. Once lit, however, it burns
completely until the gas is turned off. Explain these observations.

8. A charcoal grill has air vents that can be adjusted. As the air vents are made
smaller, explain what happens to the rate of burning of the charcoal. Will the
temperature become higher or lower?

9. In your body, sugar is oxidized at 37°C (body temperature). Outside the body, sugar
will burn only at a temperature of over 600°C. What accounts for this difference?

10. What is a “catalyst”? How does the catalyst affect the rate of a reaction?

11. What is an “inhibitor”? How does the inhibitor affect the rate of a reaction?

12. Explain the difference between a homogeneous and a heterogeneous catalyst.

13. What is the “mechanism” of a reaction?

14. What is an “elementary step”? What is the “rate determining step” of a mechanism?

15. Use collision theory to explain why most reactions probably occur through a multi-
step reaction mechanism.

16. Define the term “reaction intermediate”. Why are intermediates important for
studying reaction mechanisms?

17. For each reaction below, explain how the rate of disappearance of each reactant is
related to the rate of appearance of each product:
a) H2O2 → H2O + ½O2 b) CO + 2 H2 → CH3OH

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AP Chemistry 42S Supplementary Problems Chemical Kinetics… page 6

18. What is an “endothermic” reaction? What is the sign of ∆H for this reaction?

19. Construct and label a potential energy diagram from the information below.
Calculate ∆H for the reaction and include it on your diagram.

P.E. of reactants = 300 kJ P.E. of products = 500 kJ Ea = 400 kJ

20. Construct and label a potential energy diagram for the two-step reaction, using the
information below. Calculate ∆H for step 1 and ∆H for the overall reaction.

P.E. of reactants = 400 kJ ∆H for step 2 = -100 kJ


P.E. of intermediates = 250 kJ Ea for step 2 = 300 kJ
Ea for step 1 = 200 kJ

21. Which step in the reaction in the previous question is more likely the “rate
determining step”? Explain your choice.

22. Use the P.E. diagram below to answer the questions that follow:

800 kJ
Energy

700 kJ

600 kJ

500 kJ
Potential

400 kJ

300 kJ

200 kJ

100 kJ
Reaction Coordinate

a) What is the P.E. of the reactants?


b) What is the P.E. of the products?
c) What is the P.E. of the intermediates?
d) What is the activation energy of step 1?
e) What is the activation energy of step 2?
f) Which step is more likely the rate-determining step? Explain.
g) What is ∆H for the overall reaction?
h) What is ∆H for step 2?
i) Is step 1 endothermic or exothermic? Explain.
j) What is the P.E. of the second Transition State (activated complex)?

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AP Chemistry 42S Supplementary Problems Chemical Kinetics… page 7

23. Define the term “activated complex”. Why is it a “complex”? Why is it “activated”?
Why is it sometimes called the “Transition State”?

24. What is a “rate law”?

25. The rate law for the reaction between bromine and nitrogen monoxide is given
below:
Br2 + 2 NO → 2 NOBr

rate = k [Br2] [NO]

Indicate whether the following statements are true or false. Explain your reasoning.

a) The reaction is 1st order with respect to bromine.


b) The reaction is 2nd order with respect to nitrogen monoxide.
c) The reaction is 2nd order overall.
d) The reaction rate will double if the concentration of bromine is doubled.
e) The reaction rate will double if the concentration of nitrogen monoxide is doubled.
f) The reaction rate will double if the concentrations of both reactants are doubled
at the same time.
g) The reaction cannot involve a single-step reaction mechanism. (This is not an
elementary reaction)

26. Based on the rate law given in the previous question, propose two simple two-step
reaction mechanisms for the reaction. Identify any “intermediates” in your
mechanisms. Identify the rate-determining step in each mechanism.

27. The rate law for the decomposition of ozone into oxygen gas is given below:

2 O3 → 3 O2

rate = k [O3]

Indicate whether the following statements are true or false. Explain your reasoning.

a) The reaction is 2nd order with respect to the ozone.


b) The reaction involves a single collision between two ozone molecules.
c) If the concentration of ozone is tripled, the rate of decomposition will increase 9x.

28. Based on the rate law given in the previous question, propose a simple two-step
reaction mechanism for the reaction. Identify any “intermediates” in your
mechanism. Identify the rate-determining step in the mechanism.

29. A reaction has the experimental rate law, rate = k[A]2[B].

a) What is the overall order of the reaction?


b) What would be the effect on the rate if [A] were tripled?
c) What would be the effect on the rate if [B] were halved?
d) What would be the effect on the rate if [A] were doubled while [B] was tripled?

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AP Chemistry 42S Supplementary Problems Chemical Kinetics… page 8

30. The hypochlorite ion, ClO-, undergoes a decomposition into the chlorate and chloride
ions. A two-step reaction mechanism has been proposed for the decomposition:
step 1: (slow) ClO- + ClO- → ClO2- + Cl-
step 2: (fast) ClO2- + ClO- → ClO3- + Cl-

a) What is the net (overall) reaction for the decomposition reaction?


b) What intermediate is formed in this reaction mechanism?
c) Which step is the rate-determining step? Explain.

31. The reaction, 2 NO + 2 H2 → N2 + 2 H2O, has been studied at 904°C:

Reactant Concentrations (mol/L) Rate of Appearance of N2


[NO] [H2] (mol/L·s)
0.420 0.122 0.136
0.210 0.122 0.0339
0.210 0.244 0.0678
0.105 0.488 ?

a) Determine the rate law for the reaction.


b) What is the overall order of the reaction?
c) Calculate the value of the rate constant for the reaction at 904°C.
d) Calculate the rate of the reaction in trial 4 in the data table.
e) Notice that the rates are measured for the “appearance of N2”. What would be
the rate of appearance of “H2O” in trial 1? Explain.

32. The reaction, 2 NO + O2 → 2 NO2, has been studied at 940°C:

Reactant Concentrations (mol/L) Rate of Disappearance of NO


[NO] [O2] (mol/L·s)
0.020 0.010 1.0 x 10-4
0.040 0.010 4.0 x 10-4
0.020 0.040 4.0 x 10-4
0.010 0.020 ?

a) Determine the rate law for the reaction.


b) What is the overall order of the reaction?
c) Calculate the value of the rate constant for the reaction at 940°C.
d) Calculate the rate of the reaction in trial 4 in the data table.
e) Notice that the rates are measured for the “disappearance of NO”. What would
be the rate of appearance of “NO2” in trial 1? Explain.

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AP Chemistry 42S Supplementary Problems Chemical Kinetics… page 9

33. The reaction, O3 + NO → O2 + 2 NO2, has been studied at 750°C:

Reactant Concentrations (mol/L) Rate of Appearance of NO2


[O3] [NO] (mol/L·s)
0.21 0.21 0.016
0.42 0.21 0.032
0.63 0.63 0.144

a) Determine the rate law for the reaction.


b) What is the overall order of the reaction?
c) Calculate the value of the rate constant for the reaction at 904°C.
d) Calculate the rate of the reaction if the concentrations in trial 1 were both
doubled.
e) Notice that the rates are measured for the “appearance of NO2”. What would be
the rate of disappearance of ozone in trial 1? Explain.

34. A chemist collected data for the reaction: CH3Cl + H2O → CH3OH + HCl

Reactant Concentrations (mol/L) Rate of Appearance of CH3OH


[CH3Cl] [H2O] (mol/L·s)
0.50 0.50 22.700
0.75 0.50 34.050
0.50 0.75 51.075
? 0.125 2.128

a) Determine the rate law for this reaction.


b) What is the overall order of the reaction?
c) Calculate the rate constant for the reaction at this temperature.
d) What was the concentration of chloromethane in trial 4?

35. Explain why the rate of a chemical reaction such as: 2 NO + O2 → 2 NO2 , is likely to
be most rapid at the beginning of the reaction. In other words, why does the reaction
slow down as it progresses?

36. In an experiment, a student reacts magnesium with excess hydrochloric acid:

trial 1: 1.0 g Magnesium Ribbon is added to 1.0-M HCl at 20°C


trial 2: 1.0 g Magnesium Ribbon is added to 0.50-M HCl at 20°C
trial 3: 1.0 g Magnesium powder is added to 1.0-M HCl at 20°C
trial 4: 1.0 g Magnesium powder is added to 1.0-M HCl at 40°C

a) Rank the four trials in the expected order of increasing reaction rates.
b) Which trial would require the least time for the magnesium to dissolve?
c) If the student collected the hydrogen gas produced in the reactions in 4 identical
balloons, which balloon would have the largest volume. Explain your answer.
(Assume the balloons have been tied and cooled to room temperature).
d) If the student performed the four trials simultaneously, collecting the hydrogen
gas in balloons, what would an observer notice about the rate of filling of the
balloons?

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AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 10

37. Explain the effect of a catalyst on the activation energy of a reaction. Does the
catalyst affect the heat of reaction? Sketch a P.E. diagram to help explain your
answer.

38. Explain why a mixture of methane gas and oxygen can stand quietly for years if kept
away from sparks or flame, but will explode violently if a spark is passed through the
container.

Chemical Equilibrium
1. What is a “reversible” reaction? Give an example of a reaction that is NOT
reversible.

2. What is the definition of chemical equilibrium?

3. Why is equilibrium sometimes referred to as “dynamic” equilibrium?

4. Water in an open glass will evaporate completely. If the glass is sealed, the water
appears to stop evaporating. Does evaporation still occur in the sealed glass? How
is this an example of a physical equilibrium?

5. Dry ice, solid carbon dioxide, sublimes at room temperature. One piece of dry ice is
placed in a sealed container and another is placed in an open beaker. The next day,
the dry ice in the sealed container is seen to have decreased in mass only slightly,
whereas there is no more dry ice in the open beaker. Explain these observations.

6. Write equilibrium expressions for each reaction below:


a) S (s) + O2 (g) ' SO2 (g)
b) C6H12O6 (s) + 6 O2 (g) ' 6 CO2 (g) + 6 H2O (l)
c) 2 NO2 (g) ' 2 NO (g) + O2 (g)
d) 2 BrCl (g) ' Br2 (g) + Cl2 (g)
e) H2O (l) ' H2 (g) + ½ O2 (g)

7. Write equilibrium expressions for each reaction below:


a) 2 H2O (l) ' H3O+ (aq) + OH- (aq)
b) Fe3+ (aq) + SCN- (aq) ' FeSCN2+ (aq)
c) C (s) + H2O (g) ' CO (g) + H2 (g)
d) CaO (s) + CO2 (g) ' CaCO3 (s)
e) NH3 (g) + HCl (g) ' NH4Cl (s)

8. Consider the reaction, 2 HCl (g) ' H2 (g) + Cl2 (g)

a) Write the equilibrium expression for the reaction.


b) Write the new equilibrium expression for the reaction if the coefficients are all
doubled: 4 HCl (g) ' 2 H2 (g) + 2 Cl2 (g).
c) Write the new equilibrium expression for the reaction if the reaction is written in
reverse: H2 (g) + Cl2 (g) ' 2 HCl (g).
d) Write the new equilibrium expression for the reaction if the coefficients are all
halved: HCl (g) ' ½ H2 (g) + ½ Cl2 (g).

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AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 11

9. The equilibrium constant (K) for the reaction, A ' 2 B, is “9” at 20°C. Calculate the
value of the equilibrium constant at the same temperature for the reaction as
balanced below:

a) 2 A ' 4 B b) 2 B ' A c) ½ A ' B

10. Consider the reaction, H2 (g) + I2 (g) ' 2 HI (g) K = 45.9

a) What is K for the reverse reaction?


b) What is K for the reaction, ½ H2 (g) + ½ I2 (g) ' HI (g) ?

11. Describe the significance of the size of an equilibrium constant on the extent of a
chemical reaction.

12. What does it mean to say “reactants are favored” in a chemical reaction? What is
the size of the equilibrium constant for this type of reaction?

13. Silver chloride is almost completely ISOLUBLE in water. The equation for the
dissolving of silver chloride is : AgCl (s) ' Ag+ (aq) + Cl- (aq). Predict whether the
equilibrium constant

14. State whether the following statements are true or false. Explain your answers.

a) Only gases are included in equilibrium expressions.


b) When a reaction reaches equilibrium, it appears to “stop”.
c) Equilibrium requires a “closed” system.
d) The value of an equilibrium constant depends on how a reaction is balanced.
e) The value of an equilibrium constant depends on temperature.
f) Reactions with very small equilibrium constants are considered to be “complete”
reactions.
g) Reactions with large equilibrium constants favor the formation of products.
h) A large equilibrium constant means a reaction will be very fast.

15. How does a catalyst affect the value of an equilibrium constant? Explain.

16. For the reaction, 2 H2S (g) ' 2 H2 (g) + S2 (g), the equilibrium concentrations at
1130°C are: [H2S] = 0.15 M, [H2] = 0.010 M, and [S2] = 0.051 M. Write the
equilibrium expression for the reaction and calculate K.

17. At a high temperature, the following reaction reaches equilibrium:

N2 (g) + O2 (g) ' 2 NO (g)

An analysis of the equilibrium mixture in a 2.0-L flask shows 0.80 mol NO, 0.64 mol
N2 and 0.42 mol O2. What is the value of the equilibrium constant for the reaction at
this temperature?

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AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 12

18. A chemist studying the reaction, H2 (g) + I2 (g) ' 2 HI (g) placed hydrogen and
iodine into a 10.0-L vessel. At equilibrium, she found 0.222 mol H2, 0.222 mol I2 and
1.56 mol HI.

a) What is the value of the equilibrium constant for the reaction as written above?
b) What is the value of the equilibrium constant for the reverse reaction?

19. While studying the Haber process for the production of ammonia gas from its
elements, a chemist performed three different experiments at the same temperature:

Initial Concentration Equilibrium Concentration


N2 1.00 M 0.921 M
Experiment 1 H2 1.00 M 0.763 M
NH3 - 0.157 M
N2 - 0.399 M
Experiment 2 H2 - 1.197 M
NH3 1.00 M 0.203 M
N2 2.00 M 2.59 M
Experiment 3 H2 1.00 M 2.77 M
NH3 3.00 M 1.82 M

a) Write a balanced chemical equation for the Haber Process (all reactants &
products are gases).
b) Write the equilibrium expression for the reaction.
c) For each of the three experiments, calculate the value of the equilibrium
constant.
d) Does the value of K for a reaction appear to depend on the initial concentrations?

20. A student placed 4.00 mol of HI into a 10.0-L vessel and allowed the HI to
decompose into H2 and I2. Use your answer to question 18 to calculate the number
of moles of H2 and I2 that will be present when the system reaches equilibrium.

21. At 80°C, the gas BrNO will decompose slightly according to the equation:

2 BrNO (g) ' Br2 (g) + 2 NO (g)

When 2.0 mol of BrNO are placed into a 5.0-L vessel at 80°C, 5.0% of the molecules
are found to decompose. Calculate the value of the equilibrium constant.

22. 4.00 mol of SO2 gas and 1.50 mol of O2 gas are placed in a 2.00-L flask and allowed
to reach equilibrium in the reaction:

2 SO2 (g) + O2 (g) ' 2 SO3 (g)

At equilibrium, there is 0.80 mol of O2 remaining in the flask. Calculate K at this


temperature.

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AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 13

23. A substance (CD) decomposes into C and D: CD (g) ' C (g) + D (g). At a certain
temperature, 15% of the CD is decomposed when equilibrium is reached. If the
initial concentration of the CD is 0.20 M, what is K for the reaction?

24. A reaction may be represented by: A (g) + B (g) ' AB (g). At a given
temperature, 1.0 mol of A and 1.0 mol of B are placed into a 2.0-L container and
allowed to reach equilibrium. Analysis showed that the equilibrium concentration of
AB was 0.40 M.

a) What percent of “A” was converted to AB?


b) What is the value of K for the reaction at this temperature?

25. F2 reacts with H2 according to: H2 (g) + F2 (g) ' 2 HF (g). A student placed 0.50
mol each of the two reactants into a 1.0-L vessel and allowed the system to reach
equilibrium. The equilibrium concentration of H2 was 0.10 M. What is the equilibrium
constant for the reaction at this temperature?

26. Consider the equilibrium reaction, A (g) ' 2 B (g) + C (g). When 1.00 mol of A is
placed into a 4.00-L vessel at a given temperature, the concentration of C at
equilibrium is found to be 0.050 M. What is the value of K for the reaction?

27. Students were studying the reaction: PCl3 (g) + Cl2 (g) ' PCl5 (g). An equilibrium
mixture of the three gases in a 4.0-L flask was found to contain 2.40 mol PCl3, 2.00
mol Cl2 and 1.20 mol PCl5. Calculate the value of the equilibrium constant for the
reaction.

28. A chemist was studying the reaction: SO2 (g) + SCl2 (g) ' 2 SOCl K = 22.4.
An equilibrium mixture of the three gases was found to contain 0.20 M SO2 and 0.40
M SCl2. Calculate the concentration of SOCl in the mixture of gases.

29. A researcher placed 2.0 mol of HBr (g) into a 5.0-L tank and allowed it to
decompose: 2 HBr (g) ' H2 (g) + Br2 (g). When equilibrium was reached, 15% of
the HBr had decomposed. What is the value of the equilibrium constant for the
reaction?

30. If the same researcher repeated his experiment from the previous question, starting
with 5.0 mol of HBr, what percent of the HBr would decompose? Use the value of K
to calculate the answer!

31. In a sealed container, nitrogen dioxide is in equilibrium with dinitrogen tetraoxide:


2 NO2 (g) ' N2O4 (g). The equilibrium constant for the reaction is 1.15 at 55°C. If
the equilibrium concentration of NO2 at 55°C is found to be 0.050-M, what is the
concentration of N2O4 in the vessel?

32. A student placed 0.20-mol of phosphorus pentachloride gas into a 20.0-L flask and
allowed it to decompose into phosphorus trichloride gas and chlorine gas. At
equilibrium, she found 0.040 mol of the PCl5 left in the flask. Calculate K for the
reaction at this temperature: PCl5 (g) ' PCl3 (g) + Cl2 (g)

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AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 14

33. 5.00 g of HBr (g) was placed into a 15.0-L flask and allowed to decompose into H2
and Br2. At equilibrium, 2.21 g of Br2 was discovered. Calculate K for the reaction at
this temperature: 2 HBr (g) ' H2 (g) + Br2 (g)

34. When studying the reaction, 2 CO2 (g) ' 2 CO (g) + O2 (g), a chemist placed 10.0 g
of carbon dioxide gas into a 2.00-L vessel. She found that 8.0% of the CO2
decomposed in reaching equilibrium. Calculate K for the reaction at this
temperature.

35. A student placed 10.00 g of solid magnesium carbonate into a 5.00-L container and
heated the system to 80°C. The MgCO3 decomposed slightly and at equilibrium
there was only 9.15 g of the MgCO3 left in the container. Calculate K for the reaction
at this temperature: MgCO3 (s) ' MgO (s) + CO2 (g).

36. When 0.250 mol of CO2 is placed into a container, some of it decomposed according
to the reaction: 2 CO2 (g) ' 2 CO (g) + O2 (g). At equilibrium, 0.040 mol of CO are
found in the container. Calculate K for the reaction.

37. A chemist is studying the reaction, 2 BrCl (g) ' Br2 (g) + Cl2 (g) K = 0.11.
What will be the equilibrium concentrations of all three species if 0.20 mol of BrCl is
placed into a 2.00-L flask and allowed to decompose?

38. At very high temperatures, Cl2 molecules decompose slightly: Cl2 (g) ' 2 Cl (g).
The equilibrium constant for the reaction is small (K = 1.2 x 10-6 at 1000°C). What
will be the concentration of Cl atoms in a flask where the initial concentration of Cl2
molecules is 0.20 M?

39. A chemist was studying the reaction, 2 NO2 (g) ' NO (g) + NO3 (g) K = 0.085.
If 5.0 mol of NO2 are placed into a 10.0-L vessel, what mass of NO will be in the
container when the system reaches equilibrium?

40. 3.00 mol of H2 gas is placed in a 10.0-L flask along with 3.00 mol of F2 gas and
allowed to react until equilibrium was reached: H2 (g) + F2 (g) ' 2 HF (g) If
K = 115 at this temperature, calculate the concentration of HF gas in the container at
equilibrium.

41. How is the reaction quotient, Q, calculated? How is it different from K? What is it
used for?

42. The equilibrium constant for the Haber process, N2 (g) + 3 H2 (g) ' 2 NH3 (g) is
0.060 at a given temperature. A reaction vessel contains 2.00 M nitrogen, 2.00 M
hydrogen and 2.00 M ammonia.

a) Use calculations to show that the system is NOT at equilibrium.


b) Which direction will the reaction shift to reach equilibrium?

43. Carbon monoxide gas reacts with steam to produce carbon dioxide and hydrogen (all
species are gases). At 700 K, the equilibrium constant for this reaction is 5.10.
Calculate the equilibrium concentrations of all species if 1.00 mol of each gas is
placed into a 2.00-L vessel and allowed to reach equilibrium.

GPHS Science Department


AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 15

44. While studying the reaction, 2 HI (g) ' H2 (g) + I2 (g), a chemist placed 1.0 mol of
each gas into a 5.00-L flask. If the equilibrium constant for the reaction at this
temperature is 22.0, calculate the concentrations of all three gases when the system
reaches equilibrium.

45. Consider the equilibrium where ammonia decomposes into its elements:
2 NH3 (g) ' N2 (g) + 3 H2 (g)

Suppose the original concentrations of the three species are all 1.0 M. Which of the
following are possible values for the concentrations at equilibrium?

[NH3] [N2] [H2]

a) 0.8 M 1.1 M 1.4 M


b) 1.2 M 0.9 M 0.7 M
c) 1.2 M 1.2 M 1.2 M
d) 0.6 M 1.2 M 1.6 M
e) 0.2 M 1.4 M 2.2 M

46. Given: 2 SO2 (g) + O2 (g) ' 2 SO3 (g) ∆H = -192 kJ/mol. For this reaction,
describe how the following should be adjusted to give a high equilibrium
concentration of SO3 (g).

a) Temperature
b) Pressure
c) Concentration of SO2
d) Concentration of O2

47. Hydrogen peroxide decomposes according to: H2O2 (aq) ' H2O (l) + ½O2 (g).
The reaction is endothermic. After equilibrium has been reached, predict what would
happen to the amount of hydrogen peroxide in the system if…

a) the system was placed in an ice bath


b) a catalyst is added
c) more water is added

48. Consider this reaction which is at equilibrium in a closed vessel:


Heat + 2 SO3 (g) ' 2 SO2 (g) + O2 (g)

Explain what would happen to the amount of O2 in the vessel if the following stresses
were applied:

a) more SO3 is added c) the system is heated e) SO2 is removed


b) a catalyst is added d) the volume is doubled f) pressure increases

GPHS Science Department


AP Chemistry 42S Supplementary Problems Chemical Equilibrium… page 16

49. Consider the reaction which is at equilibrium in a closed flask:

Fe3O4 (s) + 4 H2 (g) ' 3 Fe (s) + 4 H2O (g) ∆H = -52 kJ/mol

Explain what would happen to the mass of iron oxide in the container if the following
stresses were applied:

a) hydrogen gas is removed from the flask


b) water vapor is added to the flask
c) the temperature is raised
d) iron metal is added to the flask
e) the total pressure in the flask is increased
f) hydrogen gas is added to the flask

50. Consider the endothermic reaction at 456 °C:


2 NOBr (g) ' 2 NO (g) + Br2 (g)

The reaction is at equilibrium in a closed flask. Explain what would happen to the
amount of Br2 in the flask if the following stresses were applied:

a) the volume of the flask is doubled


b) the flask is cooled down
c) NO is removed from the flask
d) NOBr is added to the flask
e) an inert gas (Argon) is added to the flask, increasing the total pressure
f) a catalyst is added to the flask

51. State LeChatelier’s Principle.

52. Explain how changing the volume of a flask affects the equilibrium position of the
system in the flask. Do volume changes always affect the equilibrium position of a
system? Explain your answer.

53. For the reaction in question 50, decide whether the following statements are true or
false.

a) ∆H for the reaction is positive


b) At equilibrium, increasing [NO] will cause an increase in [NOBr]
c) At equilibrium, removing Br2 causes the system to shift left
d) Adding more Br2 will change the value of K
e) Increasing temperature will change the value of K
f) Adding a catalyst will increase the yield of product

GPHS Science Department


AP Chemistry 42S Supplementary Problems Acids & Bases… page 17

Acids & Bases


1. List several properties of acids and bases.

2. Give three examples of commonly encountered acids and three of bases.

3. What does it mean to say that an acid is “strong”? Is this the same as saying the
acid is “concentrated”? Explain.

4. What is a monoprotic acid? a diprotic acid? Give an example of each.

5. Write balanced equations showing the dissociation of the following acids in water. If
the acid is polyprotic, write the equations showing the step-wise dissociation of the
acid.
a) nitric acid d) carbonic acid
b) hydrochloric acid e) phosphoric acid
c) acetic acid f) sulfuric acid

6. Write the Ka expressions for the acid dissociations in the previous question.

7. Identify the following acids as strong or weak. Explain.


a) nitric acid d) hydrofluoric acid
b) carbonic acid e) hydrochloric acid
c) acetic acid f) phosphoric acid

8. What is an “amphoteric” substance? Decide which of the following species are


amphoteric. If the substance is amphoteric, write balanced equations to show the
substance acting as an acid and as a base.

a) H2O b) PO43- c) HCO3- d) H2PO4- e) S2-

9. What equation is used to calculate “pH”?

10. A solution whose pH is 4.00 has _____ times the concentration of hydronium ion as
a solution whose pH is 7.00.

11. A solution whose pH is 3.50 has 1% the concentration of hydronium ions as a


solution whose pH is _____.

12. Calculate the hydronium ion concentration, [H3O+], in a solution whose pH is…
a) 1.00 d) 3.52
b) 2.00 e) 4.91
c) 8.00 f) 11.22

13. Pure water has a pH of 7.00. What is the [H3O+] in pure water? Write a balanced
chemical equation that shows how the hydronium ions are formed in water.

14. The Kw for water at 50°C is 5.47 x 10-14. What is the pH of pure water at 50°C?

GPHS Science Department


AP Chemistry 42S Supplementary Problems Acids & Bases… page 18

15. Make the following inter-conversions. In each case, tell whether the solution is acidic
or basic.
pH [H3O+] [OH-]

a) 1.00 ? ?
b) 10.50 ? ?
c) ? 1.3 x 10-5 ?
d) ? ? 2.3 x 10-4

16. Describe an acidic solution at 25°C in terms of a) [H3O+] and [OH-] and b) pH.

17. Write the formula for the conjugate base for each of the following Bronsted-Lowry
acids:
a) H2O b) HNO2 c) NH4+ d) H3PO4

18. In the following equations, identify the Bronsted-Lowry acids (A) and bases (B):
a) HSO4- + H2O ' SO42- + H3O+
b) CH3COO- + HCl ' Cl- + CH3COOH
c) NH3 + H2O ' NH4+ + OH-
d) HCO3- + HSO4- ' SO42- + H2CO3

19. Write equations for the following acting as Bronsted-Lowry bases in aqueous
solutions:
a) fluoride ion, F- b) methylamine, CH3NH2 c) sulfate, SO42-

20. Recall that the products of an acid-base neutralization reaction are a salt and water.
Write balanced equations for the following neutralization reactions. In each case, the
neutralization reaction is complete.
a) magnesium hydroxide, Mg(OH)2, and hydrobromic acid, HBr
b) sulfuric acid, H2SO4, and sodium hydroxide, NaOH
c) phosphoric acid, H3PO4, and potassium hydroxide, KOH
d) ammonium hydroxide, NH4OH, and hydrogen carbonate, HCO3-

21. What will be the concentration of sulfuric acid solution, if 25.0 mL of 0.260-M solution
is diluted to 35.0 mL?

22. How much water must be added to 25.0 mL of 6.0-M H2SO4 to make a 1.0-M
solution?

23. Rank the following acids in order of increasing strength: HClO4, HNO2, CH3COOH,
HF

24. Use Le Chatelier’s principle to explain what happens to [OH-] when NH4Cl is added
to a solution of ammonia, NH3. What happens to [H3O+] at the same time?

25. Calculate the pH of 0.020-mol/L HCl. The Ka for hydrochloric acid is large.

26. Calculate the pH of 0.00050-M HNO3. Nitric acid is a strong acid.

27. Calculate the pH of 0.0035-M HBr. Hydrobromic acid is a strong acid.

GPHS Science Department


AP Chemistry 42S Supplementary Problems Acids & Bases… page 19

28. Calculate the pH of 0.0025-M HF. The Ka for hydrofluoric acid is 6.8x 10-4.

29. Calculate the pH of 0.0052-M CH3COOH. The Ka for acetic acid is 1.8 x 10-5.

30. Calculate the pH of 0.042-M benzoic acid, C6H5COOH. The Ka is 6.5 x 10-5.

31. Calculate the pH of a solution of formic acid, HCOOH, made by dissolving 1.00 g of
the acid in enough water to make 500.0 mL of solution. The Ka of formic acid at
25 °C is 1.8 x 10-4.

32. Calculate the pH of a solution of benzoic acid, C6H5COOH, made by dissolving 2.50
g of the acid in enough water to make 100.0 mL of solution. The Ka for benzoic acid
is 6.5 x 10-5 at 25°C.

33. Calculate the pH of a 0.00105-M solution of sulfuric acid, H2SO4. Ka1 is large, and
Ka2 is 0.012. Consider each step in the dissociation separately!

34. Calculate the pH of 0.125-M sulfuric acid solution. Ka1 is large, and Ka2 is 0.012.

35. What was the %-dissociation for the second step of the dissociation of sulfuric acid in
the previous question?

36. What assumption can be made in calculating the pH of phosphoric acid solutions?
Why is the assumption valid?

37. Calculate the pH of 0.012-M phosphoric acid. Ka1 is 7.5 x 10-3, Ka2 is 6.2 x 10-8 and
Ka3 is 4.8 x 10-13.

38. Calculate the pH of 0.0025-M H3PO4. Use the Ka values from the previous question.

39. Calculate the percent ionization (dissociation) in each of the following solutions. The
Ka for hydrofluoric acid is 6.8 x 10-4.
a) 0.50-M HF b) 0.050-M HF c) 0.0050-M HF

40. Based on your answers to the previous question, describe what happens to the
fraction of acid molecules that have dissociated as an acid solution becomes more
dilute.

41. The percent ionization of a 0.10-M solution of a weak monoprotic acid, HA, is found
to be 3.42%. What is the Ka for the acid?

42. The pH of a 0.063-M solution of hypobromous acid, HBrO, is measured to be 4.95.


Calculate the Ka for the acid.

43. The pH of a 0.050-M solution of trichloroacetic acid, CCl3COOH, is 1.40. Calculate


the Ka for the acid. Is this a stronger acid than acetic acid (Ka = 1.8 x 10-5)?

44. A typical sample of vinegar has a pH of 3.0. Assuming that the vinegar is only a
dilute solution of acetic acid (Ka = 1.8 x 10-5), calculate the concentration of
CH3COOH in the vinegar.

GPHS Science Department


AP Chemistry 42S Supplementary Problems Acids & Bases… page 20

45. A 0.015-M solution of the weak acid, HOCN, has a pH of 2.67. Calculate the Ka of
this acid. What is the percent dissociation of the acid?

46. Calculate the pH of the following solutions of strong bases:


a) 0.015 M NaOH b) 0.0020-M Ba(OH)2

47. What is the pH of a saturated solution of calcium hydroxide, Ca(OH)2? This salt is
only sparingly soluble and has a Ksp = 7.9 x 10-6.

48. Calculate the pH of 0.10-M ammonia solution, NH3 (aq). The Kb of ammonia is
1.8 x 10-5 at 25°C.

49. Calculate the pH of 0.015-M ammonia solution. The Kb for ammonia is 1.8 x 10-5.

50. Methylamine is a weak base (Kb = 5.0 x 10-4). What % of CH3NH2 molecules are
ionized in a 0.060-M solution of methylamine? What is the pH of the solution?

51. Pyridine is a weak base (Kb = 1.5 x 10-9). What % of C5H5N molecules are ionized in
a 0.110-M solution of pyridine? What is the pH of the solution?

52. What equation relates the Ka of an acid with the Kb of its conjugate base?

53. Given the following acids and their Ka’s, write the formula of the conjugate bases and
calculate their base dissociation constants, Kb.
a) HCN, Ka = 4.0 x 10-10 b) H3PO4, Ka = 0.0075

54. Calculate the pH of a solution made by dissolving 5.00 g of sodium fluoride, NaF, in
50.0 mL water. Is the solution acidic, basic, or neutral? The Ka of HF is 7.2 x 10-4.

55. Calculate the pH of a solution made by dissolving 1.50 g of NaHCO3 in 200.0 mL of


water. Use the Ka values in your text or on the class wall-chart to help answer this.

56. Predict whether the following 0.10-M solutions will be acidic, basic, or neutral. (Do
not actually calculate the pH of the solutions!)
a) NaCl b) NH4Br c) K2SO4 d) NH4F

57. Predict whether the following 0.10-M solutions will be acidic, basic, or neutral. (Do
not actually calculate the pH of the solutions!)
a) CaI2 b) NaCH3COO c) NH4CH3COO d) Na2CO3

58. What is an acid-base indicator? Describe the color changes involved in Litmus and
in phenolphthalein indicators.

59. In a titration experiment, a 0.925-g sample of potassium hydrogen phthalate (KHP,


molar mass 204.22 g/mol) required 22.35 mL of sodium hydroxide solution for
neutralization. Calculate the concentration of the NaOH solution. Recall that KHP is
a weak monoprotic acid that can be represented as “HA” in an equation.

GPHS Science Department


AP Chemistry 42S Supplementary Problems Acids & Bases… page 21

60. In another experiment, the NaOH solution from the previous question was used to
titrate a sample of acetic acid, CH3COOH. If a 25.00-mL sample of the acetic acid
required 16.93 mL of the NaOH solution to reach the endpoint of the titration, what
was the concentration of the acetic acid?

61. What is the endpoint of a titration? How is it different from the equivalence point of
the titration?

62. How should an indicator be chosen in an acid-base titration? In other words, what
factor(s) must be considered when selecting an acid-base indicator for a titration?

63. A 1.023-g sample of KHP (molar mass, 204.22 g/mol), required 17.33 mL of KOH
solution to reach the endpoint of a titration. Calculate the concentration of the KOH
solution. Recall that KHP is a weak monoprotic acid.

64. A 10.00-mL sample of phosphoric acid, H3PO4, required 42.08 mL of the KOH
solution from the previous question to reach the third equivalence point. Calculate
the concentration of the phosphoric acid solution.

65. A 25.00-mL sample of ammonia (NH3) required 22.84 mL of 0.0875-M sulfuric acid
(H2SO4) for complete neutralization. Calculate the concentration of the ammonia
solution.

66. What is a “standard” solution? What does it mean to “standardize” a solution?

67. You require 36.78 mL of 0.0105-M HCl solution to reach the equivalence point in a
titration of a 0.525-g sample of a weak base. Calculate the molar mass of the base.
Assume that the base reacts with the HCl in a 1:1 ratio (the base can be represented
as “B” in a chemical equation).

68. Assume that you dissolve 0.235 g of the weak acid benzoic acid (C6H5COOH) in
exactly 100.0 mL of water and then titrate a 10.00-mL sample of the solution with
0.108-M ammonia (NH3). What volume of the ammonia will be required to neutralize
the benzoic acid sample?

GPHS Science Department


AP Chemistry 42S Supplementary Problems Solubility Equilibrium… page 22

Solubility Equilibrium
1. For equilibrium to exist, two opposing processes must be occurring at the same rate.
Use this definition to explain how a “saturated solution” is an example of equilibrium.

2. Write balanced equations for the dissociation of the following salts. Include the
solubility product expressions for each salt, also.

a) silver phosphate, Ag3PO4 d) lead iodide, PbI2


b) magnesium fluoride, MgF2 e) cerium(III) hydroxide, Ce(OH)3
c) calcium carbonate, CaCO3 f) aluminum chromate, Al2(CrO4)3

3. What mass of sodium hydroxide, NaOH, must be dissolved to prepare 2.00 L of


0.0500-M solution?

4. What mass of iron(III) nitrate, Fe(NO3)3 , must be dissolved to prepare 500.0 mL of


0.120-M solution?

5. A student used a pipette to transfer 25.00 mL of 0.50-M sulfuric acid to a clean 500-
mL volumetric flask. She then filled the flask with distilled water and shook to mix.
What is the concentration of the new solution?

6. A chemistry student mixed 20.0 mL of 0.010-M NaOH with 25.0 mL of 0.025-M


KNO3. What is the concentration of each ion in the mixed solution? No reaction
occurs during the mixing.

7. Indicate whether the following statements are true or false.

a) Sodium salts are generally very soluble in water.


b) The solubility of salts is generally higher in cold water than in hot water.
c) The solubility of gases is generally higher in cold water than in hot water.
d) Salts containing the chloride ion are soluble, except silver chloride and lead
chloride.
e) Salts containing the nitrate ion are insoluble.
f) “Sparingly soluble” is a more accurate description for salts considered to be
“insoluble” in water.
g) A salt with a small Ksp is generally very soluble in water.
h) To compare solubilities of two salts in water, one can simply compare the sizes
of their solubility product constants.

8. A student mixed 1.0-M solutions of the following salts. In which case(s) will a
precipitate likely form? Identify any precipitates that form.

a) NaI is mixed with KNO3 e) KF is mixed with AgNO3


b) Pb(NO3)2 is mixed with KNO3 f) ZnCl2 is mixed with Pb(NO3)2
c) FeCl3 is mixed with KOH g) CaCl2 is mixed with NaOH
d) CuSO4 is mixed with CaCl2 h) KOH is mixed with NaCl

GPHS Science Department


AP Chemistry 42S Supplementary Problems Solubility Equilibrium… page 23

9. At 25°C, the solubility product constant for silver bromide, AgBr, is 5.0 x 10-13.
Calculate the molar solubility of silver bromide at this temperature.

10. Calculate the mass of AgBr that can be dissolved in 2.00 L of water at 25°C.

11. As temperature increases, does Ksp for a salt increase or does it decrease? Justify
your answer.

12. At 25°C, the Ksp of calcium fluoride (CaF2) is 3.9 x 10-11. What is the molar solubility
of calcium fluoride in water at 25°C?

13. The Ksp of magnesium hydroxide, Mg(OH)2, is 7.1 x 10-12 at 25°C. Calculate the
solubility of this salt, expressed in “grams per liter”.

14. Lead sulfate, PbSO4, has a solubility product constant, Ksp, of 6.3 x 10-7 at 25°C.
The Ksp of lead fluoride, PbF2, is smaller, 3.6 x 10-8 at 25°C. Calculate the molar
solubility of each salt. Which salt is more soluble in water?

15. The Ksp of aluminum hydroxide, Al(OH)3, is very small (3.0 x 10-34). How much
water is required to dissolve 1.0 g of this salt?

16. Calculate the volume of water needed to dissolve 0.50g of silver chromate. The Ksp
of Ag2CrO4 is 1.2 x 10-12 at 25°C.

17. What mass of lead iodide, PbI2, is needed to make 1.00 L of saturated solution at
25°C? The Ksp of lead iodide is 7.9 x 10-9 at 25°C.

18. What mass of iron(II) hydroxide, Fe(OH)2, is needed to prepare 500.0 mL of


saturated solution? The Ksp of Fe(OH)2 is 7.9 x 10-16 at 25°C.

19. A student added a teaspoon of barium sulfate, BaSO4, to a glass of water and stirred
for several minutes. Use calculations to predict whether the salt will appear to
dissolve in the water. The Ksp of barium sulfate is 1.1 x 10-10.

20. Lead iodide, PbI2, is a bright yellow precipitate that makes a colorful demonstration.
The Ksp of lead iodide is 7.9 x 10-9. A chemist added 1.00 g of sodium iodide, NaI,
to 2.00 L of 0.100-M lead nitrate, Pb(NO3)2. Will the chemist observe a precipitate?

21. What mass of potassium hydroxide, KOH, can be dissolved in 500.0 mL of 0.20-M
magnesium nitrate, Mg(NO3)2, without causing a precipitate to form? The Ksp of
Mg(OH)2 is 7.1 x 10-12.

22. Calculate the mass of Na2CO3 that must be dissolved in 2.00 L of 0.050-M AgNO3 to
make a saturated solution of silver carbonate, Ag2CO3. The Ksp of silver carbonate is
8.1 x 10-12.

23. The solubility of strontium carbonate, SrCO3, is 0.0059 g per 250 mL of water. What
is the Ksp for strontium carbonate?

24. The molar solubility of barium phosphate, Ba3(PO4)2, is 0.0041 mol/L. Calculate the
Ksp for this salt.

GPHS Science Department


AP Chemistry 42S Supplementary Problems Solubility Equilibrium… page 24

25. The solubility of calcium hydroxide, Ca(OH)2, is measured to be 0.93 g/L at some
temperature. What is the Ksp of the salt at this temperature?

26. You place 2.75 g of BaF2 in 1.00 L of pure water at 25°C. After equilibrium has been
established, the fluoride ion concentration is 0.0150 M. What is the Ksp of the salt?

27. Describe the common ion effect on the solubility of a salt.

28. Compare the solubility of AgCl (Ksp = 1.0 x 10-10) in water to that in 0.10-M NaCl.

29. The Ksp of silver iodide is 8.3 x 10-17. What is the iodide ion concentration of a 1.00-
L saturated solution of AgI, to which 0.020 mol of AgNO3 is added?

30. Calculate the molar solubility of silver thiocyanate, AgSCN, in pure water and in a
solution containing 0.010-M NaSCN. The Ksp of silver thiocyanate is 1.0 x 10-12.

31. What is the solubility, in “grams per milliliter”, of barium fluoride in a solution
containing 1.5 g/L potassium fluoride, KF. The Ksp of BaF2 is 1.7 x 10-6.

32. Calculate the molar solubility of calcium hydroxide, Ca(OH)2, in 0.100-M NaOH. The
Ksp of Ca(OH)2 is 6.5 x 10-6 at 25°C.

33. Rank the following compounds in order of increasing solubility in pure water:
Na2CO3, BaF2, PbCl2, and Ag2CrO4. Refer to the Ksp table in ch. 17 of your text.

34. Rank the following compounds in order of increasing solubility in pure water: CaSO4,
NiCO3, AgOH, and ZnS. Refer to the Ksp table in ch. 17 of your text.

35. Which has a greater solubility in pure water – Ag2SO4 or CaSO4? Refer to the Ksp
table in ch. 17 of your text.

36. Will a precipitate form if 100.0 mL of 0.0030-M NaCl is added to 200.0 mL of 0.0.012-
M AgNO3? The Ksp of silver chloride, AgCl, is 1.0 x 10-10.

37. Will a precipitate form if 10.0 mL of 0.050-M NaOH is added to 500 mL of 0.050-M
Pb(NO3)2? The Ksp of Pb(OH)2 is 1.2 x 10-15.

38. Will a precipitate form if 2.0 g of solid Pb(NO)3 is added to 250 mL of 0.020-M NaI?
The Ksp of PbI2 is 1.4 x 10-8. Assume that no volume change occurs.

39. Will a precipitate form if 50.0 mL of 0.10-M AgNO3 is added to 1.0-L of 0.10-M KCl?
The Ksp of AgCl is 1.0 x 10-10.

40. Will a precipitate form if 25.0 mL of 0.0040-M NaF is added to 75.0 mL of 0.0160-M
Mg(NO3)2? The Ksp of MgF2 is 6.4 x 10-9.

41. Define a “supersaturated solution” in terms of the reaction quotient.

42. A solution is prepared by dissolving 1.40 g of Ag2SO4 in 100.0 mL of hot water. Will
a precipitate form if the solution is cooled to 25°C? At 25°C, the Ksp of Ag2SO4 is
1.2 x 10-5.

GPHS Science Department


AP Chemistry 42S Problem Booklet Electrochemistry… page 25

Oxidation, Reduction & Electrochemistry


1. In each of the following reactions, identify the substance being oxidized and the
substance being reduced. Identify the oxidizing agent and the reducing agent.

a) 2 Al + 3 Cl2 → 2 AlCl3
b) FeS + 3 NO3- + 4 H3O+ → 3 NO + SO42- + Fe3+ + 6 H2O
c) Zn + HCl → ZnCl2 + H2

2. In each of the following reactions, identify the substance being oxidized and the
substance being reduced. Identify the oxidizing agent and the reducing agent.

a) 4 NH3 + 3 O2 → 2 N2 + 6 H2O
b) PbO2 + Pb + 2 H2SO4 → 2 PbSO4 + 2 H2O
c) Cl2 + 2 I- → 2 Cl- + I2

3. Assign oxidation numbers (states) to each atom in the following species:

a) ClO4- b) NaOCl c) KNO3 d) CH4

4. Assign oxidation states to each atom in the following species:

a) MnO4- b) CrO42- c) Cr2O72- d) O3

5. Assign oxidation numbers to the nitrogen atoms below:

a) NO b) N2 c) N3- d) NO2-

e) NO2 f) NH3 g) N2O5 h) N2O3

6. Identify each of the following changes as “oxidation” or “reduction”:

a) MnO4- → MnO2 b) P4O10 → P4O6 c) Fe3+ → Fe2+

7. Identify each of the following changes as “oxidation” or “reduction”.

a) Cr2O72- → Cr3+ b) SO42- → SO32- c) Zn → Zn2+

8. Balance the following, using oxidation numbers.

a) HBrO3 + SO2 + H2O → Br2 + H2SO4


b) K2Cr2O7 + H2O + S → KOH + Cr2O3 + SO2
c) PH3 + I2 + H2O → H3PO2 + HI
d) Cl2 + KOH → KClO3 + KCl + H2O
e) KIO4 + KI + HCl → KCl + I2 + H2O
f) HNO2 + HI → NO + I2 + H2O
g) As2O3 + Cl2 + H2O → H3AsO4 + HCl
h) MnO2 + H2SO4 + H2C2O4 → MnSO4 + CO2 + H2O

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AP Chemistry 42S Problem Booklet Electrochemistry… page 26

9. Identify which reactions below represent redox reactions. If the reaction is redox,
identify what is being reduced & what is being oxidized. Also identify the reducing &
oxidizing agents.

a) Li + H2O → LiOH + H2
b) Al + HCl → AlCl3 + H2
c) H2O + SO3 → H2SO4
d) 2 NaOH + H2CO3 → 2 H2O + Na2CO3
e) 2 NaBr + Cl2 → 2 NaCl + Br2
f) BaCl2 + 2 KIO3 → Ba(IO3)2 + 2 KCl

10. Balance the following equations using the half-reactions method, in acidic solution:
a) Cr2O72- + I- → Cr3+ + I2
b) Fe2+ + MnO4- → Fe3+ + Mn2+
c) H2O2 + Br- → H2O + Br2
d) C2H5OH + Cr2O72- → CH3COOH + Cr3+
e) Cu + NO3- → Cu2+ + NO2

11. Balance the following equations using the half-reactions method, in basic solution:
a) ClO- + CrO2- → Cl- + CrO42-
b) CrO42- + S2- → Cr(OH)3 + S
c) MnO4- + SO32- → MnO2 + SO42-
d) MnO2 + ClO3- → MnO4- + Cl-
e) Fe(OH)3 + ClO- → FeO42- + Cl-

12. A KMnO4 solution was standardized by titration against As2O3. A 0.1156-g sample of
As2O3 requires 27.08 mL of the KMnO4 for its titration. What is the concentration of
the potassium permanganate solution? Assume the reaction occurs in acidic
solution.
MnO4- + As2O3 → Mn2+ + H3AsO4

13. The titration of 50.0 mL of saturated solution of sodium oxalate, Na2C2O4, requires
25.8 mL of 0.0214-M K2Cr2O7. Calculate the concentration of the sodium oxalate
solution. Assume the reaction occurs in acidic solution.

Cr2O72- + C2O42- → Cr3+ + CO2

14. A 1.026-g sample of an iron-containing ore was dissolved in an acid solution and the
iron converted to Fe2+. This solution required 24.35 mL of 0.0195-M KMnO4 to reach
the equivalence point of a titration. Calculate the percentage of iron in the sample (by
mass).
MnO4- + Fe2+ → Mn2+ + Fe3+

15. A 25.1-mL sample of NaBr requires 24.9 mL of 0.129-M KMnO4 solution to reach the
equivalence point for its oxidation to BrO- in a basic solution. The KMnO4 is reduced
to MnO2. Find the concentration of the NaBr solution.

MnO4- + Br- → MnO2 + BrO-

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AP Chemistry 42S Problem Booklet Electrochemistry… page 27

16. Sketch the electrochemical cells below in your notebook.

i) Label the anode and cathode


ii) Label the half-cells as “oxidation” or “reduction”
iii) Indicate the direction of electron flow
iv) Write the half-reaction occurring in each beaker
v) Record E° for each half-cell
vi) Calculate E°cell

a)

Na2SO4
S
Z
I
I
L
N
V
C
Zn2+(aq) , Ag+(aq), E
1M 1M R

b)

Na2SO4
C
I
O
R
P
O
P
N
Fe2+(aq) , Cu2+(aq), E
1M 1M R

17. What does “standard” refer to in the phrase, “standard electrochemical cell”?

18. What are two common salts used in salt bridges? Describe an alternative device
that could be used in place of a salt bridge in an electrochemical cell.

19. How is the standard reduction potential for a species related to its standard oxidation
potential?

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AP Chemistry 42S Problem Booklet Electrochemistry… page 28

20. Which of the species below is most likely to be reduced?


a) Ag, I2 or Zn2+ b) Cl2, Li, or F- c) Cu2+, Cl-, or MnO4-

21. Which of the species below is most likely to get oxidized?


a) K+, F- or K b) Fe, Zn, or Mg c) H2, Ag, or Na+

22. Draw and completely label each of the electrochemical cells below. Calculate E° for
each cell.
a) Al | Al3+ (1 M) || Ag+ (1M) | Ag
b) Zn | Zn2+ (1M) || Cl2 (1 atm) | Pt
c) Cu | Cu2+ (1M) || Au3+ (1 M) | Au

23. Draw and completely label each of the electrochemical cells below. Calculate E° for
each cell.
a) Mg | Mg2+ (1M) || Sn2+ (1M) | Sn
b) Al | Al3+ (1M) || Sn2+ (1M) | Sn
c) Ni | Ni2+ (1M) || Ag+ (1M) | Ag

24. In each case below, decide if a redox reaction will spontaneously occur. Show
calculations of E° to support your answers.
a) A copper wire is placed into a solution of zinc nitrate (contains Zn2+)
b) A lead strip is dipped into a solution of copper(II) sulfate (contains Cu2+)
c) A silver coin is washed with a solution containing Cl2(aq)
d) A nickel coin is dipped into a solution containing Mg2+
e) Sodium iodide (contains I-) is mixed with aqueous bromine, Br2(aq)
f) An iron nail is dipped into a solution of nickel(II) sulfate (contains Ni2+)

25. A student dissolved some potassium permanganate in a beaker of water to make a


relatively concentrated solution. She then dipped a piece of magnesium metal into
the solution. To her surprise, there was no reaction!
a) Calculate E° for the reaction and state whether the reaction should be
spontaneous or non-spontaneous.
b) Suggest a reason for the student’s observation.

26. Which of the following metals would be practical ones to use in an experiment to
prepare hydrogen gas from dilute hydrochloric acid solution: iron, sodium, zinc,
copper, magnesium. For the metals that you deem to be impractical, explain why.

27. If the Ag/Ag+ half-cell was chosen as the standard reference cell (instead of
hydrogen), what would be the standard reduction potentials of the …

a) Cu2+/Cu half-cell b) H+/H2 half-cell c) Mg2+/Mg half-cell

28. Which is the best reducing agent? the best oxidizing agent? I2, I-, Au, Au3+, Mg, Mg2+

29. Can a 1.0-M solution of Fe2(SO4)3 be stored in a nickel container? Explain.

30. Which is the best oxidizing agent? the best reducing agent? Sn2+, Sn, K+, K, Cl2, Cl-

GPHS Science Department


AP Chemistry 42S Problem Booklet Electrochemistry… page 29

31. The following observations were made, and equations for the reactions are given.
Using these observations, list the ions with their reduction half-reactions, in order of
decreasing ability to gain electrons. (do NOT refer to a table of reduction potentials!)

a) Mn + Zn2+ → Zn + Mn2+
b) Fe + Co2+ → Fe2+ + Co
c) Fe + Zn2+ → no reaction

32. In an experiment, strips of gold, silver and tin were placed in solutions containing
solutions of Au3+, Ag+ and Sn2+ ions. The following results were observed:

a) Sn + Au3+ → metallic gold was deposited


b) Au + Ag+ → no reaction
c) Sn + Ag+ → metallic silver was deposited

Arrange the three metal ions as reduction half-reactions, in decreasing ability to gain
electrons.

33. Given: H2O, Ni, Cl2, K+, Cl-, Cu+, H2O2

a) Which is most easily oxidized?


b) Which is the strongest oxidizing agent?
c) Which could reduce Fe3+ to Fe2+?
d) Which could oxidize Br- to Br2?

34. Write net ionic equations for these reactions (all aqueous). If no reaction occurs,
write “no reaction”.

a) chlorine + tin(II) nitrate


b) iron(II) nitrate + potassium iodide
c) silver + hydrochloric acid
d) tin + sulfuric acid
e) iron(II) nitrate + aluminum nitrate

35. Draw a diagram showing how a copper spoon could be plated with silver metal.
Identify the anode and cathode. Calculate the mass of silver that could be plated by
a 1.0-A current flowing for 27 h.

36. How long must an electrolytic cell operate to produce 3.55 g of Cl2(g) with a current
of 6.50 A (from a solution of Cl-).

37. A current of 1.50 A is passed through 250 mL of 0.10-M Cu2+(aq). How long will it
take for all off the copper in the solution to precipitate as copper metal?

38. If you use a current of 2.50 A to deposit nickel from a solution of Ni(NO3)2 for 2.00 h,
how many grams of nickel will be deposited?

39. If you wish to convert 1.00 g of Au3+(aq) to Au(s) in 30 min, what current should you
use?

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AP Chemistry 42S Problem Booklet Electrochemistry… page 30

40. A current of 1.00 A is applied to 1.0 L of 1.0-M HCl solution for 24 h, producing
hydrogen gas.
a) Calculate the number of moles of hydrogen ions that would have been consumed
in the 24 h period.
b) What would be the pH of the solution at the end of the 24 h period?
c) If the hydrogen gas was collected at 25°C and 100.0 kPa, what volume of gas
would there be? (R = 8.314 kPa·L·mol-1·K-1)

41. A metal forms the chloride compound, MCl4. Electrolysis of the molten metal
chloride by a current of 1.81 A for 25.6 min produced 1.09 g of the metal. Find the
molar mass of the metal. Identify the metal from the periodic table.

42. The electrolysis of molten potassium chloride is carried out with a current of 9.78 A.
How long will it take to deposit 17.5 g of potassium metal?

43. What mass of tin can be deposited during the electrolysis of molten SnI2 by a 5.00-A
current for 2 h 30 min?

44. Predict the products at the anode and cathode from the electrolysis of…
a) molten sodium chloride
b) molten zinc bromide
c) aqueous potassium bromide
d) aqueous copper(II) chloride

45. Predict the products at the anode and cathode from the electrolysis of…
a) water
b) molten aluminum iodide
c) molten silver chloride
d) aqueous hydrochloric acid

46. Draw and label the standard electrochemical cell: Mg | Mg2+ (1M) || Ag+ (1M) | Ag

a) Calculate the standard cell potential for the cell.


b) Write a balanced equation for the overall reaction occurring in this cell.
c) Would the voltage increase, decrease, or stay the same if a bigger magnesium
electrode was used? (hint: LeChatelier’s Principle!)
d) Would the voltage increase, decrease, or stay the same if water was added to
the magnesium half-cell?
e) Would the voltage increase, decrease, or stay the same if AgNO3 was added to
the silver half-cell?

47. Describe what is meant by “cathodic protection”. Give an example.

48. What processes occur at the anode and cathode in an electrochemical cell. in an
electrolytic cell?

49. What is a battery?

50. What material is the anode in a dry cell (e.g. Duracell)? the cathode?

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