36 Chapter 1 Matter, Measurement, and Problem Solving

Key Equations and Relationships

Relationship between Kelvin (K) and Celsius (C) Temperature Scales (1.6) Relationship between Density (d), Mass (m), and Volume (V) (1.6)
K = C + 273.15 m
d =
V
Relationship between Celsius (C) and Fahrenheit (F) Temperature
Scales (1.6)
(F - 32)
C =
1.8

Key Learning Outcomes

Chapter Objectives Assessment

Determining Physical and Chemical Example 1.1 For Practice 1.1 Exercises 4350
Changes and Properties (1.4)

Converting between the Temperature Scales: Fahrenheit, Example 1.2 For Practice 1.2 Exercises 5154
Celsius, and Kelvin (1.6)
Calculating the Density of a Example 1.3 For Practice 1.3 For More Practice 1.3
Substance (1.6) Exercises 6568

Reporting Scientific Measurements to the Correct Digit Example 1.4 For Practice 1.4 Exercises 73, 74
of Uncertainty (1.7)
Working with Significant Figures (1.7) Examples 1.5, 1.6 For Practice 1.5, 1.6
Exercises 77, 78, 80, 8388
Using Conversion Factors (1.8) Examples 1.7, 1.8, 1.9, 1.10 For Practice 1.7, 1.8, 1.9, 1.10
For More Practice 1.9, 1.10 Exercises 91, 92, 9699, 101, 102
in cm
2.54 cm
1 in

Solving Problems Involving Equations (1.8) Examples 1.11, 1.12 For Practice 1.11, 1.12
Exercises 117, 118

EXERCISES
Review Questions
1. Explain this statement in your own words and give an example. 3. Describe the scientific approach to knowledge. How does it
The properties of the substances around us depend on the atoms differ from other approaches?
and molecules that compose them. 4. Explain the differences between a hypothesis, a law, and a theory.
2. Explain the main goal of chemistry. 5. What observations did Antoine Lavoisier make? What law did
he formulate?

6. What theory did John Dalton formulate?
7. What is wrong with the expression That is just a theory, if by
theory the speaker is referring to a scientific theory?
8. What are two different ways to classify matter?
9. How do solids, liquids, and gases differ?
10. What is the difference between a crystalline solid and an amor-
phous solid?
11. Explain the difference between a pure substance and a mixture.
12. Explain the difference between an element and a compound.
13. Explain the difference between a homogeneous and a heteroge-
neous mixture.
14. What kind of mixtures can be separated by filtration?
15. Explain how distillation is used to separate mixtures.
16. What is the difference between a physical property and a chem-
ical property?
17. What is the difference between a physical change and a chemi-
cal change? List some examples of each.
18. Explain the significance of the law of conservation of energy.
19. What kind of energy is chemical energy? In what way is an
elevated weight similar to a tank of gasoline?
Problems by Topic
Note: Answers to all odd-numbered Problems, numbered in blue, can
be found in Appendix III. Exercises in the Problems by Topic section
are paired, with each odd-numbered problem followed by a similar
even-numbered problem. Exercises in the Cumulative Problems
section are also paired, but more loosely. Challenge Problems and
Conceptual Problems, because of their nature, are unpaired.
The Scientific Approach to Knowledge
33. Classify each statement as an observation, a law, or a theory.
a. All matter is made of tiny, indestructible particles called atoms.
b. When iron rusts in a closed container, the mass of the con-
tainer and its contents does not change.
c. In chemical reactions, matter is neither created nor destroyed.
d. When a match burns, heat is released.
34. Classify each statement as an observation, a law, or a theory.
a. Chlorine is a highly reactive gas.
b. If elements are listed in order of increasing mass of their
atoms, their chemical reactivity follows a repeating pattern.
c. Neon is an inert (or nonreactive) gas.
d. The reactivity of elements depends on the arrangement of
their electrons.
35. A chemist decomposes several samples of carbon monoxide
into carbon and oxygen and weighs the resultant elements. The
results are shown in the table.
Sample Mass of Carbon (g) Mass of Oxygen (g)
1 6 8 c. aluminum
2 12 16
3 18 24
Exercises 37
20. What are the standard SI base units of length, mass, time, and
temperature?
21. What are the three common temperature scales? Does the size
of a degree differ among them?
22. What are prefix multipliers? List some examples.
23. What is a derived unit? List an example.
24. Explain the difference between density and mass.
25. Explain the difference between intensive and extensive properties.
26. What is the meaning of the number of digits reported in a mea-
sured quantity?
27. When multiplying or dividing measured quantities, what deter-
mines the number of significant figures in the result?
28. When adding or subtracting measured quantities, what deter-
mines the number of significant figures in the result?
29. What are the rules for rounding off the results of calculations?
30. Explain the difference between precision and accuracy.
31. Explain the difference between random error and systematic error.
32. What is dimensional analysis?
a. Do you notice a pattern in these results?
Next, the chemist decomposes several samples of hydrogen
peroxide into hydrogen and oxygen. The results are shown
in the table:
Sample Mass of Hydrogen (g) Mass of Oxygen (g)
1 0.5 8
2 1 16
3 1.5 24
b. Do you notice a similarity between these results and those
for carbon monoxide in part a?
c. Can you formulate a law from the observations in a and b?
d. Can you formulate a hypothesis that might explain your
lawin c?
36. When astronomers observe distant galaxies, they can tell that
most of them are moving away from one another. In addition,
the more distant the galaxies, the more rapidly they are likely to
be moving away from each other. Can you devise a hypothesis
to explain these observations?
The Classification and Properties of Matter
37. Classify each substance as a pure substance or a mixture. If it is
a pure substance, classify it as an element or a compound. If it
is a mixture, classify it as homogeneous or heterogeneous.
a. sweat b. carbon dioxide
d. vegetable soup
38 Chapter 1 Matter, Measurement, and Problem Solving

38. Classify each substance as a pure substance or a mixture. If it is 43. Classify each of the listed properties of isopropyl alcohol (also
a pure substance, classify it as an element or a compound. If it known as rubbing alcohol) as physical or chemical.
is a mixture, classify it as homogeneous or heterogeneous. a. colorless b. flammable
a. wine b. beef stew c. liquid at room temperature d. density = 0.79 g>mL
c. iron d. carbon monoxide e. mixes with water
39. Complete the table. 44. Classify each of the listed properties of ozone (a pollutant in the
lower atmosphere but part of a protective shield against UV
Substance Pure or mixture Type
light in the upper atmosphere) as physical or chemical.
aluminum pure element a. bluish color b. pungent odor
apple juice ___________ ___________ c. very reactive
d. decomposes on exposure to ultraviolet light
hydrogen peroxide ___________ ___________ e. gas at room temperature
chicken soup ___________ ___________ 45. Classify each property as physical or chemical.
a. the tendency of ethyl alcohol to burn
40. Complete the table. b. the shine on silver
c. the odor of paint thinner
Substance Pure or mixture Type
d. the flammability of propane gas
water pure compound 46. Classify each property as physical or chemical.
coffee ___________ ___________ a. the boiling point of ethyl alcohol
b. the temperature at which dry ice evaporates
ice ___________ ___________ c. the tendency of iron to rust
carbon ___________ ___________ d. the color of gold
47. Classify each change as physical or chemical.
41. Determine whether each molecular diagram represents a puresub- a. Natural gas burns in a stove.
stance or a mixture. If it represents a pure substance, classify the b. The liquid propane in a gas grill evaporates because the
substance as an element or a compound. If it represents amixture, valve was left open.
classify the mixture as homogeneous or heterogeneous. c. The liquid propane in a gas grill burns in a flame.
d. A bicycle frame rusts on repeated exposure to air and water.
48. Classify each change as physical or chemical.
a. Sugar burns when heated in a skillet.
b. Sugar dissolves in water.
c. A platinum ring becomes dull because of continued abrasion.
d. A silver surface becomes tarnished after exposure to air for a
long period of time.
49. Based on the molecular diagram, classify each change as
physical or chemical.
(a) (b)

(c) (d)
(a)
42. Determine whether each molecular diagram represents a pure
substance or a mixture. If it represents a pure substance, classify
the substance as an element or a compound. If it represents a
mixture, classify the mixture as homogeneous or heterogeneous.

(b)

(a) (b)

(c) (d) (c)

 Exercises 39

50. Based on the molecular diagram, classify each change as physi- 58. Use scientific notation to express each quantity with only the
cal or chemical. base units (no prefix multipliers).
a. 35 mL b. 225 Mm c. 133 Tg d. 1.5 cg
59. Complete the table.

a. 1245 kg 1.245 * 106g 1.245 * 109 mg

b. 515 km _______dm _______cm
c. 122.355 s _______ms _______ks
d. 3.345 kJ _______J _______mJ
60. Complete the table.

a. 355 km>s _______cm>s _______m>ms

b. 1228 g>L _______g>mL _______kg>ML
c. 554 mK>s _______K>s _______K>ms
(a) (b) d. 2.554 mg>mL _______g>L _______g>mL
61. Express the quantity 254,998 m in each unit.
a. km b. Mm c. mm d. cm
- 12
62. Express the quantity 556.2 * 10 s in each unit.
a. ms b. ns c. ps d. fs
63. How many 1 cm squares would it take to construct a square that
is 1 m on each side?
64. How many 1 cm cubes would it take to construct a cube that is
4 cm on edge?
(c)
Density
Units in Measurement
65. A new penny has a mass of 2.49 g and a volume of 0.349 cm3.
51. Convert each temperature. Is the penny made of pure copper? Explain.
a. 32 F to C (temperature at which water freezes) 66. A titanium bicycle frame displaces 0.314 L of water and has a
b. 77 K to F (temperature of liquid nitrogen) mass of 1.41 kg. What is the density of the titanium in g>cm3?
c. 109 F to C (temperature of dry ice)
67. Glycerol is a syrupy liquid often used in cosmetics and soaps. A
d. 98.6 F to K (body temperature)
3.25 L sample of pure glycerol has a mass of 4.10 * 103 g.
52. Convert each temperature. What is the density of glycerol in g>cm3?
a. 212 F to C (temperature of boiling water at sea level)
68. A supposedly gold nugget is tested to determine its density. It is
b. 22 C to K (approximate room temperature)
found to displace 19.3 mL of water and has a mass of 371
c. 0.00 K to F (coldest temperature possible, also known as
grams. Could the nugget be made of gold?
absolute zero)
d. 2.735 K to C (average temperature of the universe as mea- 69. Ethylene glycol (antifreeze) has a density of 1.11 g>cm3.
sured from background black body radiation) a. What is the mass in g of 417 mL of this liquid?
b. What is the volume in L of 4.1 kg of this liquid?
53. The coldest temperature ever measured in the United States is
80 F on January 23, 1971, in Prospect Creek, Alaska. Convert 70. Acetone (nail polish remover) has a density of 0.7857 g>cm3.
that temperature to C and K. (Assume that 80 F is precise to a. What is the mass, in g, of 28.56 mL of acetone?
two significant figures.) b. What is the volume, in mL, of 6.54 g of acetone?
54. The warmest temperature ever measured in the United States is 71. A small airplane takes on 245 L of fuel. If the density of the fuel
134 F on July 10, 1913, in Death Valley, California. Convert is 0.821 g>mL, what mass of fuel has the airplane taken on?
that temperature to C and K. 72. Human fat has a density of 0.918 g>cm3. How much volume
55. Use the prefix multipliers to express each measurement without (incm3) is gained by a person who gains 10.0 lb of pure fat?
any exponents.
a. 1.2 * 10 - 9 m b. 22 * 10 - 15 s
The Reliability of a Measurement and Significant Figures
c. 1.5 * 10 g9
d. 3.5 * 106 L 73. Read each measurement to the correct number of significant
56. Use prefix multipliers to express each measurement without figures. Laboratory glassware should always be read from the
any exponents. bottom of the meniscus.
a. 38.8 * 105 g b. 55.2 * 10 - 10 s
c. 23.4 * 1011 m d. 87.9 * 10 - 7 L
57. Use scientific notation to express each quantity with only the
base units (no prefix multipliers).
a. 4.5 ns
b. 18 fs
c. 128 pm
d. 35 mm
(a) (b) (c)
40 Chapter 1 Matter, Measurement, and Problem Solving

74. Read each measurement to the correct number of significant 85. Calculate to the correct number of significant figures.
figures. Laboratory glassware should always be read from a. 43.7 - 2.341
thebottom of the meniscus. Digital balances normally display b. 17.6 + 2.838 + 2.3 + 110.77
mass to the correct number of significant figures for that c. 19.6 + 58.33 - 4.974
particular balance. d. 5.99 - 5.572
86. Calculate to the correct number of significant figures.
a. 0.004 + 0.09879 b. 1239.3 + 9.73 + 3.42
c. 2.4 - 1.777 d. 532 + 7.3 - 48.523
87. Calculate to the correct number of significant figures.
a. (24.6681 * 2.38) + 332.58
b. (85.3 - 21.489) , 0.0059
c. (512 , 986.7) + 5.44
d. 3 (28.7 * 105) , 48.533 4 + 144.99
(a) (b) (c)
88. Calculate to the correct number of significant figures.
75. For each number, underline the zeroes that are significant and a. 3 (1.7 * 106) , (2.63 * 105) 4 + 7.33
draw an x through the zeroes that are not. b. (568.99 - 232.1) , 5.3
a. 1,050,501 km b. 0.0020 m c. (9443 + 45 - 9.9) * 8.1 * 106
c. 0.000000000000002 s d. 0.001090 cm d. (3.14 * 2.4367) - 2.34
76. For each number, underline the zeroes that are significant and
draw an x through the zeroes that are not. Unit Conversions
a. 180,701 mi b. 0.001040 m
c. 0.005710 km d. 90,201 m 89. Perform each unit conversion.
a. 27.8 L to cm3 b. 1898 mg to kg
77. How many significant figures are in each number?
c. 198 km to cm
a. 0.000312 m b. 312,000 s
c. 3.12 * 105 km d. 13,127 s 90. Perform each unit conversion.
e. 2000 a. 28.9 nm to m b. 1432 cm3 to L
c. 1211 Tm to Gm
78. How many significant figures are in each number?
a. 0.1111 s b. 0.007 m 91. Perform each unit conversion.
c. 108,700 km d. 1.563300 * 1011 m a. 154 cm to in b. 3.14 kg to g
e. 30,800 c. 3.5 L to qt d. 109 mm to in
79. Which numbers are exact (and therefore have an unlimited 92. Perform each unit conversion.
number of significant figures)? a. 1.4 in to mm b. 116 ft to cm
a. p = 3.14 c. 1845 kg to lb d. 815 yd to km
b. 12 inches = 1 foot 93. A runner wants to run 10.0 km. She knows that her running
c. EPA gas mileage rating of 26 miles per gallon pace is 7.5 miles per hour. How many minutes must she run?
d. 1 gross = 144 94. A cyclist rides at an average speed of 18 miles per hour. If she
80. Indicate the number of significant figures in each number. If the wants to bike 212 km, how long (in hours) must she ride?
number is an exact number, indicate an unlimited number of 95. A European automobile has a gas mileage of 17 km/L. What is
significant figures. the gas mileage in miles per gallon?
a. 305,435,087 (2008 U.S. population) 96. A gas can holds 5.0 gallons of gasoline. Express this quantity
b. 2.54 cm = 1 in incm3.
c. 11.4 g>cm3 (density of lead)
97. A house has an area of 195 m2. What is its area in each unit?
d. 12 = 1 dozen
a. km2 b. dm2 c. cm2
81. Round each number to four significant figures.
98. A bedroom has a volume of 115 m3. What is its volume in each
a. 156.852 b. 156.842
unit?
c. 156.849 d. 156.899
a. km3 b. dm3 c. cm3
82. Round each number to three significant figures.
99. The average U.S. farm occupies 435 acres. How many square
a. 79,845.82 b. 1.548937 * 107
miles is this? (1 acre = 43,560 ft2, 1 mile = 5280 ft)
c. 2.3499999995 d. 0.000045389
100. Total U.S. farmland occupies 954 million acres. How many
square miles is this? (1 acre = 43,560 ft2, 1 mile = 5280 ft).
Significant Figures in Calculations
Total U.S. land area is 3.537 million square miles. What per-
83. Calculate to the correct number of significant figures. centage of U.S. land is farmland?
a. 9.15 , 4.970 101. An acetaminophen suspension for infants contains 80 mg>
b. 1.54 * 0.03060 * 0.69 0.80 mL suspension. The recommended dose is 15 mg>kg body
c. 27.5 * 1.82 , 100.04 weight. How many mL of this suspension should be given to an
d. (2.290 * 106) , (6.7 * 104) infant weighing 14 lb? (Assume two significant figures.)
84. Calculate to the correct number of significant figures. 102. An ibuprofen suspension for infants contains 100 mg>5.0 mL
a. 89.3 * 77.0 * 0.08 suspension. The recommended dose is 10 mg>kg body weight.
b. (5.01 * 105) , (7.8 * 10 2) How many mL of this suspension should be given to an infant
c. 4.005 * 74 * 0.007 weighing 18 lb? (Assume two significant figures.)
d. 453 , 2.031

10. Describe Rutherfords gold foil experiment. How did the
experiment prove that the plum-pudding model of the atom was
wrong?
11. Describe Rutherfords nuclear model of the atom. What was
revolutionary about his model?
12. If matter is mostly empty space, as suggested by Rutherford,
then why does it appear so solid?
13. List the three subatomic particles that compose atoms and give
the basic properties (mass and charge) of each.
14. What defines an element?
15. Explain the difference between Z (the atomic number) and
A(the mass number).
16. Where do elements get their names?
17. What are isotopes? What is percent natural abundance of isotopes?
18. Describe the two different notations used to specify isotopes
and give an example of each.
19. What is an ion? A cation? An anion?
20. State the periodic law. How did the periodic law lead to the
periodic table?
Problems by Topic
Note: Answers to all odd-numbered Problems, numbered in blue, can
be found in Appendix III. Exercises in the Problems by Topic section
are paired, with each odd-numbered problem followed by a similar
even-numbered problem. Exercises in the Cumulative Problems section
are also paired, but somewhat more loosely. (Challenge Problems and
Conceptual Problems, because of their nature, are unpaired.)
The Laws of Conservation of Mass, Definite Proportions, and
Multiple Proportions
29. A hydrogen-filled balloon was ignited and 1.50 g of hydrogen
reacted with 12.0 g of oxygen. How many grams of water vapor
formed? (Assume that water vapor is the only product.)
30. An automobile gasoline tank holds 21 kg of gasoline. When the
gasoline burns, 84 kg of oxygen is consumed, and carbon
dioxide and water are produced. What is the total combined
mass of carbon dioxide and water that is produced?
31. Two samples of carbon tetrachloride were decomposed into
their constituent elements. One sample produced 38.9 g of
carbon and 448 g of chlorine, and the other sample produced
14.8 g of carbon and 134 g of chlorine. Are these results consis-
tent with the law of definite proportions? Show why or why not.
32. Two samples of sodium chloride were decomposed into their
constituent elements. One sample produced 6.98 g of sodium
and 10.7 g of chlorine, and the other sample produced 11.2 g of
sodium and 17.3 g of chlorine. Are these results consistent with
the law of definite proportions? Explain your answer.
33. The mass ratio of sodium to fluorine in sodium fluoride is
1.21:1. A sample of sodium fluoride produces 28.8 g of sodium
upon decomposition. How much fluorine (in grams) is formed?
34. Upon decomposition, one sample of magnesium fluoride pro-
duced 1.65 kg of magnesium and 2.57 kg of fluorine. A second
sample produced 1.32 kg of magnesium. How much fluorine (in
grams) did the second sample produce?
35. Two different compounds containing osmium and oxygen have
the following masses of oxygen per gram of osmium: 0.168 and
0.3369 g. Show that these amounts are consistent with the law
of multiple proportions.
Exercises 79
21. What are the characteristic properties of metals, nonmetals, and
metalloids?
22. What are the characteristic properties of each group?
a. noble gases
b. alkali metals
c. alkaline earth metals
d. halogens
23. How do you predict the charges of ions formed by main-group
elements?
24. What is atomic mass? How is it calculated?
25. Explain how a mass spectrometer works.
26. What kind of information can be determined from a mass
spectrum?
27. What is a mole? How is the mole concept useful in chemical
calculations?
28. Why is the mass corresponding to a mole of one element
different from the mass corresponding to a mole of another
element?
36. Palladium forms three different compounds with sulfur. The mass
of sulfur per gram of palladium in each compound is listed below.
Show that these masses are consistent with the law of multi-
pleproportions.
Compound Grams S per Gram Pd
A 0.603
B 0.301
C 0.151
37. Sulfur and oxygen form both sulfur dioxide and sulfur trioxide.
When samples of these were decomposed the sulfur dioxide
produced 3.49 g oxygen and 3.50 g sulfur, while the sulfur
trioxide produced 6.75 g oxygen and 4.50 g sulfur. Calculate
the mass of oxygen per gram of sulfur for each sample and
show that these results are consistent with the law of multi-
pleproportions.
38. Sulfur and fluorine form several different compounds including
sulfur hexafluoride and sulfur tetrafluoride. Decomposition of a
sample of sulfur hexafluoride produces 4.45 g of fluorine and
1.25 g of sulfur, while decomposition of a sample of sulfur tet-
rafluoride produces 4.43 g of fluorine and 1.87 g of sulfur.
Calculate the mass of fluorine per gram of sulfur for each
sample and show that these results are consistent with the law
of multiple proportions.
Atomic Theory, Nuclear Theory, and Subatomic Particles
39. Which statements are consistent with Daltons atomic theory as
it was originally stated? Why?
a. Sulfur and oxygen atoms have the same mass.
b. All cobalt atoms are identical.
c. Potassium and chlorine atoms combine in a 1:1 ratio to form
potassium chloride.
d. Lead atoms can be converted into gold.
80 Chapter 2 Atoms and Elements

40. Which statements are inconsistent with Daltons atomic theory
as it was originally stated? Why?
a. All carbon atoms are identical.
b. An oxygen atom combines with 1.5 hydrogen atoms to form
a water molecule.
c. Two oxygen atoms combine with a carbon atom to form a
carbon dioxide molecule.
d. The formation of a compound often involves the destruction
of one or more atoms.
41. Which statements are consistent with Rutherfords nuclear
theory as it was originally stated? Why?
a. The volume of an atom is mostly empty space.
b. The nucleus of an atom is small compared to the size of the
atom.
c. Neutral lithium atoms contain more neutrons than protons.
d. Neutral lithium atoms contain more protons than electrons.
42. Which statements are inconsistent with Rutherfords nuclear
theory as it was originally stated? Why?
a. Since electrons are smaller than protons, and since a hydrogen
atom contains only 1 proton and 1 electron, it must follow that
the volume of a hydrogen atom is mostly due to the proton.
b. A nitrogen atom has 7 protons in its nucleus and 7 electrons
outside of its nucleus.
c. A phosphorus atom has 15 protons in its nucleus and
150electrons outside of its nucleus.
d. The majority of the mass of a fluorine atom is due to its
9electrons.
43. A chemist in an imaginary universe, where electrons have a
different charge than they do in our universe, performs the
Millikan oil drop experiment to measure the electrons charge.
The charges of several drops are recorded here. What is the
charge of the electron in this imaginary universe?
Drop # Charge
A - 6.9 * 10 - 19 C
47. Which statements about subatomic particles are true?
a. If an atom has an equal number of protons and electrons, it
will be charge-neutral.
b. Electrons are attracted to protons.
c. Electrons are much lighter than neutrons.
d. Protons have twice the mass of neutrons.
48. Which statements about subatomic particles are false?
a. Protons and electrons have charges ofthe same magnitude
but opposite signs.
b. Protons have about the same mass as neutrons.
c. Some atoms dont have any protons.
d. Protons and neutrons have charges of the same magnitude
but opposite signs.
49. How many electrons would it take to equal the mass of a proton?
50. A helium nucleus has two protons and two neutrons. How many
electrons would it take to equal the mass of a helium nucleus?
Isotopes and Ions
51. Write isotopic symbols in the form X-A (e.g., C-13) for each
isotope.
a. the silver isotope with 60 neutrons
b. the silver isotope with 62 neutrons
c. the uranium isotope with 146 neutrons
d. the hydrogen isotope with 1 neutron
52. Write isotopic symbols in the form AZ X for each isotope.
a. the copper isotope with 34 neutrons
b. the copper isotope with 36 neutrons
c. the potassium isotope with 21 neutrons
d. the argon isotope with 22 neutrons
53. Determine the number of protons and the number of neutrons in
each isotope.
a. 14
7 N
b. 23
11Na
c. 222
86 Rn

- 9.2 * 10 - 19 C d. 208
82 Pb
B
54. Determine the number of protons and the number of neutrons in
C - 11.5 * 10 - 19 C each isotope.
D - 4.6 * 10 - 19 C a. 40
19K
b. 226
88 Ra
44. Imagine a unit of charge called the zorg. A chemist performs the c. 99
43Tc
oil drop experiment and measures the charge of each drop in d. 33
15P
zorgs. Based on the results shown here, what is the charge of the 55. The amount of carbon-14 in ancient artifacts and fossils is often
electron in zorgs (z)? How many electrons are in each drop? used to establish their age. Determine the number of protons
and the number of neutrons in a carbon-14 isotope and write its
Drop # Charge symbol in the form AZ X.
A - 4.8 * 10 - 9 z 56. Uranium-235 is used in nuclear fission. Determine the number
of protons and the number of neutrons in uranium-235 and
B - 9.6 * 10 - 9 z
write its symbol in the form AZ X.
C - 6.4 * 10 - 9 z 57. Determine the number of protons and the number of electrons
D -12.8 * 10 - 9 z in each ion.
a. Ni2 + b. S2 - c. Br - d. Cr3 +
45. On a dry day, your body can accumulate static charge from 58. Determine the number of protons and the number of electrons
walking across a carpetor from brushing your hair. If your body in each ion.
develops a charge of - 15 mC (microcoulombs), how many a. Al3 + b. Se2 - c. Ga3 + d. Sr2 +
excess electrons has it acquired? What is their collective mass? 59. Predict the charge of the ion formed by each element.
46. How many electrons are necessary to produce a charge of -1.0 C? a. O b. K c. Al d. Rb
What is the mass of this many electrons? 60. Predict the charge of the ion formed by each element.
a. Mg b. N c. F d. Na
 Exercises 81

61. Fill in the blanks to complete the table. 72. Magnesium has three naturally occurring isotopes with the
following masses and natural abundances:
Number of Number of
Electrons in Protons in Isotope Mass (amu) Abundance (%)
Symbol Ion Formed Ion Ion Mg-24 23.9850 78.99
Ca Ca2 + _____ _____ Mg-25 24.9858 10.00
_____ 2+ 2 _____
Be Mg-26 25.9826 11.01
Se _____ _____ 34
Sketch the mass spectrum of magnesium.
In _____ _____ 49
73. The atomic mass of fluorine is 18.998 amu and its mass spec-
62. Fill in the blanks to complete the table. trum shows a large peak at this mass. The atomic mass of
chlorine is 35.45 amu, yet the mass spectrum of chlorine does
Number of Number of not show a peak at this mass. Explain the difference.
Electrons in Protons in
Symbol Ion Formed Ion Ion 74. The atomic mass of copper is 63.546 amu. Do any copper
isotopes have a mass of 63.546 amu? Explain.
Cl _____ _____ 17
75. An element has two naturally occurring isotopes. Isotope 1 has
Te _____ 54 _____ a mass of 120.9038 amu and a relative abundance of 57.4%, and
Br Br - _____ _____ isotope 2 has a mass of 122.9042 amu. Find the atomic mass of
this element and identify it.
_____ Sr2 + _____ 38
76. An element has four naturally occurring isotopes with the
masses and natural abundances given here. Find the atomic
mass of the element and identify it.
The Periodic Table and Atomic Mass
Isotope Mass (amu) Abundance (%)
63. Write the name of each element and classify it as a metal, non-
metal, or metalloid. 1 135.90714 0.19
a. K b. Ba c. I d. O e. Sb 2 137.90599 0.25
64. Write the symbol for each element and classify it as a metal, 3 139.90543 88.43
nonmetal, or metalloid. 4 141.90924 11.13
a. gold b. fluorine c. sodium
d. tin e. argon
77. Bromine has two naturally occurring isotopes (Br-79 and
65. Determine whether or not each element is a main-group element. Br-81) and has an atomic mass of 79.904 amu. The mass of
a. tellurium b. potassium Br-81 is 80.9163 amu, and its natural abundance is 49.31%.
c. vanadium d. manganese Calculate the mass and natural abundance of Br-79.
66. Determine whether or not each element is a transition element. 78. Silicon has three naturally occurring isotopes (Si-28, Si-29, and
a. Cr b. Br c. Mo d. Cs Si-30). The mass and natural abundance of Si-28 are 27.9769
67. Classify each element as an alkali metal, alkaline earth metal, amu and 92.2%, respectively. The mass and natural abundance
halogen, or noble gas. of Si-29 are 28.9765 amu and 4.67%, respectively. Find the
a. sodium b. iodine c. calcium mass and natural abundance of Si-30.
d. barium e. krypton 79. Use the mass spectrum of europium to determine the atomic
68. Classify each element as an alkali metal, alkaline earth metal, mass of europium.
halogen, or noble gas. 100%
a. F b. Sr c. K d. Ne e. At
Intensity %

69. Which pair of elements do you expect to be most similar? Why?

a. N and Ni b. Mo and Sn 50%
c. Na and Mg d. Cl and F
e. Si and P
70. Which pair of elements do you expect to be most similar? Why? 151 153
a. nitrogen and oxygen b. titanium and gallium Mass (amu)
c. lithium and sodium d. germanium and arsenic
e. argon and bromine 80. Use the mass spectrum of rubidium to determine the atomic
71. Gallium has two naturally occurring isotopes with the following mass of rubidium.
masses and natural abundances: 100%
Intensity %

Isotope Mass (amu) Abundance (%)

50%
Ga-69 68.92558 60.108
Ga-71 70.92470 39.892
85 87
Sketch the mass spectrum of Gallium. Mass (amu)
330 Chapter 7 The Quantum-Mechanical Model of the Atom
8. Explain the wave behavior known as interference. Explain the
difference between constructive and destructive interference.
9. Explain the wave behavior known as diffraction. Draw the
diffraction pattern that occurs when light travels through twoslits
comparable in size and separation to the lights wavelength.
10. Describe the photoelectric effect. How did experimental
observations of this phenomenon differ from the predictions of
classical electromagnetic theory?
11. How did the photoelectric effect lead Einstein to propose that
light is quantized?
12. What is a photon? How is the energy of a photon related to its
wavelength? Its frequency?
13. What is an emission spectrum? How does an emission spectrum
of a gas in a discharge tube differ from a white light spectrum?
14. Describe the Bohr model for the atom. How did the Bohr model
account for the emission spectra of atoms?
15. Explain electron diffraction.
16. What is the de Broglie wavelength of an electron? What deter-
mines the value of the de Broglie wavelength for an electron?
17. What are complementary properties? How does electron
diffraction demonstrate the complementarity of the wave nature
and particle nature of the electron?
18. Explain Heisenbergs uncertainty principle. What paradox is at
least partially solved by the uncertainty principle?
19. What is a trajectory? What kind of information do you need to
predict the trajectory of a particle?
20. Why does the uncertainty principle make it impossible to
predict a trajectory for the electron?
21. Newtons laws of motion are deterministic. Explain this statement.
Problems by Topic
Electromagnetic Radiation
35. The distance from the sun to Earth is 1.496 * 108 km.
Howlong does it take light to travel from the sun to Earth?
36. The nearest star to our sun is Proxima Centauri, at a distance of
4.3 light-years from the sun. A light-year is the distance that
light travels in one year (365 days). How far away, in km, is
Proxima Centauri from the sun?
37. List these types of electromagnetic radiation in order of (i)
increasing wavelength and (ii) increasing energy per photon:
a. radio waves b. microwaves
c. infrared radiation d. ultraviolet radiation
38. List these types of electromagnetic radiation in order of
(i)increasing frequency and (ii) decreasing energy per photon:
a. gamma rays b. radio waves
c. microwaves d. visible light
39. Calculate the frequency of each wavelength of electromagnetic
radiation:
a. 632.8 nm (wavelength of red light from heliumneon laser)
b. 503 nm (wavelength of maximum solar radiation)
c. 0.052 nm (a wavelength contained in medical X-rays)
40. Calculate the wavelength of each frequency of electromagnetic
radiation:
a. 100.2 MHz (typical frequency for FM radio broadcasting)
b. 1070 kHz (typical frequency for AM radio broadcasting)
(assume four significant figures)
c. 835.6 MHz (common frequency used for cell phone
communication)
22. An electron behaves in ways that are at least partially
indeterminate. Explain this statement.
23. What is a probability distribution map?
24. For each solution to the Schrdinger equation, what can be pre-
cisely specified: the electrons energy or its position? Explain.
25. What is a quantum-mechanical orbital?
26. What is the Schrdinger equation? What is a wave function?
How is a wave function related to an orbital?
27. What are the possible values of the principal quantum number
n? What does the principal quantum number determine?
28. What are the possible values of the angular momentum quan-
tum number l? What does the angular momentum quantum
number determine?
29. What are the possible values of the magnetic quantum number
ml? What does the magnetic quantum number determine?
30. List all the orbitals in each principal level. Specify the three
quantum numbers for each orbital.
a. n = 1 b. n = 2
c. n = 3 d. n = 4
31. Explain the difference between a plot showing the probability
density for an orbital and one showing the radial distribution
function.
32. Make sketches of the general shapes of the s, p, and d orbitals.
33. List the four different sublevels. Given that only a maximum of
two electrons can occupy an orbital, determine the maximum
number of electrons that can exist in each sublevel.
34. Why are atoms usually portrayed as spheres when most orbitals
are not spherically shaped?
41. Calculate the energy of a photon of electromagnetic radiation at
each of the wavelengths indicated in Problem 39.
42. Calculate the energy of a photon of electromagnetic radiation at
each of the frequencies indicated in Problem 40.
43. A laser pulse with wavelength 532 nm contains 3.85 mJ of
energy. How many photons are in the laser pulse?
44. A heat lamp produces 32.8 watts of power at a wavelength
of 6.5 mm. How many photons are emitted per second?
11 watt = 1 J>s2
45. Determine the energy of 1 mol of photons for each kind of light.
(Assume three significant figures.)
a. infrared radiation (1500 nm)
b. visible light (500 nm)
c. ultraviolet radiation (150 nm)
46. How much energy is contained in 1 mol of each?
a. X-ray photons with a wavelength of 0.135 nm
b. g-ray photons with a wavelength of 2.15 * 10-5 nm.
The Wave Nature of Matter and the Uncertainty Principle
47. Sketch the interference pattern that results from the diffraction
of electrons passing through two closely spaced slits.
48. What happens to the interference pattern described in
Problem 47 if the rate of electrons going through the slits is
decreased to one electron per hour? What happens to the pattern
if we try to determine which slit the electron goes through by
using a laser placed directly behind the slits?

49. The resolution limit of a microscope is roughly equal to the wave-
length of light used in producing the image. Electron microscopes
use an electron beam (in place of photons) to produce much higher
resolution images, about 0.20 nm in modern instruments. Assum-
ing that the resolution of an electron microscope is equal to the de
Broglie wavelength of the electrons used, to what speed must the
electrons be accelerated to obtain a resolution of 0.20 nm?
50. The smallest atoms can themselves exhibit quantum-mechanical
behavior. Calculate the de Broglie wavelength (in pm) of a
hydrogen atom traveling at 475 m>s.
51. What is the de Broglie wavelength of an electron traveling at
1.35 * 105 m>s?
52. A proton in a linear accelerator has a de Broglie wavelength of
122 pm. What is the speed of the proton?
53. Calculate the de Broglie wavelength of a 143 g baseball travel-
ing at 95 mph. Why is the wave nature of matter not important
for a baseball?
54. A 0.22-caliber handgun fires a 27 g bullet at a velocity of
765m>s. Calculate the de Broglie wavelength of the bullet. Is
the wave nature of matter significant for bullets?
55. An electron has an uncertainty in its position of 552 pm. What
is the uncertainty in its velocity?
56. An electron traveling at 3.7 * 105 m>s has an uncertainty in
its velocity of 1.88 * 105 m>s. What is the uncertainty in
itsposition?
Orbitals and Quantum Numbers
57. Which electron is, on average, closer to the nucleus: an electron
in a 2s orbital or an electron in a 3s orbital?
58. Which electron is, on average, further from the nucleus: an
electron in a 3p orbital or an electron in a 4p orbital?
59. What are the possible values of l for each value of n?
a. 1 b. 2 c. 3 d. 4
60. What are the possible values of ml for each value of l?
a. 0 b. 1 c. 2 d. 3
61. Which set of quantum numbers cannot occur together to specify
an orbital?
a. n = 2, l = 1, m l = - 1
b. n = 3, l = 2, ml = 0
c. n = 3, l = 3, m l = 2
d. n = 4, l = 3, m l = 0
Cumulative Problems
73. Ultraviolet radiation and radiation of shorter wavelengths can
damage biological molecules because they carry enough energy to
break bonds within the molecules. A typical carboncarbon bond
requires 348 kJ>mol to break. What is the longest wavelength of
radiation with enough energy to break carboncarbon bonds?
74. The human eye contains a molecule called 11-cis-retinal that
changes shape when struck with light of sufficient energy. The
change in shape triggers a series of events that results in an
electrical signal being sent to the brain. The minimum energy
required to change the conformation of 11-cis-retinal within the
eye is about 164 kJ>mol. Calculate the longest wavelength
visible to the human eye.
75. An argon ion laser puts out 5.0 W of continuous power at a
wavelength of 532 nm. The diameter of the laser beam is
5.5mm. If the laser is pointed toward a pinhole with a diameter
Exercises 331
62. Which combinations of n and l represent real orbitals and which
do not exist?
a. 1s b. 2p c. 4s d. 2d
63. Sketch the 1s and 2p orbitals. How would the 2s and 3p orbitals
differ from the 1s and 2p orbitals?
64. Sketch the 3d orbitals. How would the 4d orbitals differ from
the 3d orbitals?
Atomic Spectroscopy
65. An electron in a hydrogen atom is excited with electrical energy
to an excited state with n = 2. The atom then emits a photon.
What is the value of n for the electron following the emission?
66. Determine whether each transition in the hydrogen atom
corresponds to absorption or emission of energy.
a. n = 3 h n = 1
b. n = 2 h n = 4
c. n = 4 h n = 3
67. According to the quantum-mechanical model for the hydrogen
atom, which electron transitions would produce light with the
longer wavelength: 2p h 1s or 3p h 1s?
68. According to the quantum-mechanical model for the hydrogen
atom, which electron transition would produce light with the
longer wavelength: 3p h 2s or 4p h 3p?
69. Calculate the wavelength of the light emitted when an electron
in a hydrogen atom makes each transition and indicate the
region of the electromagnetic spectrum (infrared, visible,
ultraviolet, etc.) where the light is found.
a. n = 2 h n = 1 b. n = 3 h n = 1
c. n = 4 h n = 2 d. n = 5 h n = 2
70. Calculate the frequency of the light emitted when an electron in
a hydrogen atom makes each transition:
a. n = 4 h n = 3 b. n = 5 h n = 1
c. n = 5 h n = 4 d. n = 6 h n = 5
71. An electron in the n = 7 level of the hydrogen atom relaxes to
a lower energy level, emitting light of 397 nm. What is the value
of n for the level to which the electron relaxed?
72. An electron in a hydrogen atom relaxes to the n = 4 level,
emitting light of 114 THz. What is the value of n for the level in
which the electron originated?
of 1.2 mm, how many photons will travel through the pinhole
per second? Assume that the light intensity is equally distrib-
uted throughout the entire cross-sectional area of the beam.
(1 W = 1 J>s)
76. A green leaf has a surface area of 2.50 cm2. If solar radiation is
1000 W>m2, how many photons strike the leaf every second?
Assume three significant figures and an average wavelength of
504 nm for solar radiation.
77. In a technique used for surface analysis called Auger electron
spectroscopy (AES), electrons are accelerated toward a metal sur-
face. These electrons cause the emissions of secondary electrons
called auger electronsfrom the metal surface. The kinetic
energy of the auger electrons depends on the composition of the
surface. The presence of oxygen atoms on the surface results in
374 Chapter 8 Periodic Properties of the Elements

Key Learning Outcomes, continued

Br Br
Using Periodic Trends to Example 8.5For Practice 8.5For More Practice 8.5
Predict Atomic Size (8.6) Exercises 6164
228 pm

Writing Electron Configurations for Ions (8.7) Example 8.6For Practice 8.6Exercises 65, 66

Using Periodic Trends to Predict Ion Size (8.7) Example 8.7For Practice 8.7For More Practice 8.7
Exercises 6972

Using Periodic Trends to Predict Relative Ionization Energies (8.7) Example 8.8For Practice 8.8For More Practice 8.8
Exercises 7376

Predicting Metallic Character Based on Example 8.9For Practice 8.9For More Practice 8.9
Periodic Trends (8.8) Exercises 8184

Writing Reactions for Alkali Metal and Halogen Reactions (8.9) Example 8.10For Practice 8.10Exercises 8590

EXERCISES
Review Questions
1. What are periodic properties? 16. What are valence electrons? Why are they important?
2. Which periodic property is particularly important to nerve 17. Copy this blank periodic table onto a sheet of paper and label
signal transmission? Why? each of the blocks within the table: s block, p block, d block,
3. Explain the contributions of Johann Dbereiner and John Newlands and f block.
to the organization of elements according to their properties.
1A 8A
4. Who is credited with arranging the periodic table? How were 1 2A 3A 4A 5A 6A 7A 18
elements arranged in this table? 1 2 13 14 15 16 17
2 3B 4B 5B 6B 7B 8B 1B 2B
5. Explain the contributions of Meyer and Moseley to the periodic 3 3 4 5 6 7 8 9 10 11 12
Periods

table.
6. The periodic table is a result of the periodic law. What observa-
tions led to the periodic law? What theory explains the underly-
ing reasons for the periodic law?
7. What is an electron configuration? Give an example.
8. What is Coulombs law? Explain how the potential energy of
two charged particles depends on the distance between the
charged particles and on the magnitude and sign of their charges.
9. What is shielding? In an atom, which electrons tend to do the
most shielding (core electrons or valence electrons)?
10. What is penetration? How does the penetration of an orbital into
the region occupied by core electrons affect the energy of an
electron in that orbital?
11. Why are the sublevels within a principal level split into different
energies for multielectron atoms but not for the hydrogen atom?
12. What is an orbital diagram? Provide an example.
13. Why is electron spin important when writing electron configu-
rations? Explain in terms of the Pauli exclusion principle.
14. What are degenerate orbitals? According to Hunds rule, how
are degenerate orbitals occupied?
15. List all orbitals from 1s through 5s according to increasing
energy for multielectron atoms.
4
5
6
7
Lanthanides
Actinides
18. Explain why the s block in the periodic table has only two
columns while the p block has six.
19. Why do the rows in the periodic table get progressively longer
as you move down the table? For example, the first row
contains 2 elements, the second and third rows each contain 8
elements, and the fourth and fifth rows each contain 18
elements. Explain.
20. Explain the relationship between a main-group elements let-
tered group number (the number of the elements column) and
its valence electrons.
21. Explain the relationship between an elements row number in
the periodic table and the highest principal quantum number in
the elements electron configuration. How does this relationship
differ for main-group elements, transition elements, and inner
transition elements?
 Exercises 375

22. Which of the transition elements in the first transition series
have anomalous electron configurations?
23. Explain how to write the electron configuration for an element
based on its position in the periodic table.
24. Explain the relationship between the properties of an element
and the number of valence electrons that it contains.
25. List the number of valence electrons for each family in the
periodic table, and explain the relationship between the number
of valence electrons and the resulting chemistry of the elements
in the family.
a. alkali metals b. alkaline earth metals
c. halogens d. oxygen family
26. Define atomic radius. For main-group elements, give the
observed trends in atomic radius as you
a. move across a period in the periodic table.
b. move down a column in the periodic table.
27. What is effective nuclear charge? What is shielding?
28. Use the concepts of effective nuclear charge, shielding, and n
value of the valence orbital to explain the trend in atomic radius
as you move across a period in the periodic table.
29. For transition elements, give the trends in atomic radius as you
a. move across a period in the periodic table.
b. move down a column in the periodic table.
Explain the reasons for the trends described in parts a and b.
30. How is the electron configuration of an anion different from
that of the corresponding neutral atom? How is the electron
configuration of a cation different?
31. Explain how to write an electron configuration for a transition
metal cation. Is the order of electron removal upon ionization sim-
ply the reverse of electron addition upon filling? Why or why not?
32. Describe the relationship between
a. the radius of a cation and that of the atom from which it is
formed.
b. the radius of an anion and that of the atom from which it is
formed.
33. What is ionization energy? What is the difference between first
ionization energy and second ionization energy?
34. What is the general trend in ionization energy as you
move down a column in the periodic table? As you move
across a row?
35. What are the exceptions to the periodic trends in ionization
energy? Why do they occur?
36. Examination of the first few successive ionization energies for a
given element usually reveals a large jump between two ioniza-
tion energies. For example, the successive ionization energies
of magnesium show a large jump between IE2 and IE3. The
successive ionization energies of aluminum show a large jump
between IE3 and IE4. Explain why these jumps occur and how
you might predict them.
37. What is electron affinity? What are the observed periodic trends
in electron affinity?
38. What is metallic character? What are the observed periodic
trends in metallic character?
39. Write a general equation for the reaction of an alkali metal with
a. a halogen.
b. water.
40. Write a general equation for the reaction of a halogen with
a. a metal.
b. hydrogen.
c. another halogen.

Problems by Topic
Electron Configurations 48. Use the periodic table to determine each quantity.
a. The number of 3s electrons in Mg
41. Write the full electron configuration for each element. b. The number of 3d electrons in Cr
a. Si b. O c. K d. Ne c. The number of 4d electrons in Y
42. Write the full electron configuration for each element. d. The number of 6p electrons in Pb
a. C b. P c. Ar d. Na 49. Name an element in the fourth period (row) of the periodic table
43. Write the full orbital diagram for each element. with
a. N b. F c. Mg d. Al a. five valence electrons. b. four 4p electrons.
44. Write the full orbital diagram for each element. c. three 3d electrons. d. a complete outer shell.
a. S b. Ca c. Ne d. He 50. Name an element in the third period (row) of the periodic table with
45. Use the periodic table to write an electron configuration for a. three valence electrons.
each element. Represent core electrons with the symbol of the b. four 3p electrons.
previous noble gas in brackets. c. six 3p electrons.
a. P b. Ge c. Zr d. I d. two 3s electrons and no 3p electrons.
46. Use the periodic table to determine the element corresponding
to each electron configuration.
Valence Electrons and Simple Chemical Behavior from the
a. [Ar] 4s 2 3d 10 4p 6 b. [Ar] 4s 2 3d 2 Periodic Table
2 10 2
c. [Kr] 5s 4d 5p d. [Kr] 5s 2 51. Determine the number of valence electrons in each element.
47. Use the periodic table to determine each quantity. a. Ba b. Cs c. Ni d. S
a. The number of 2s electrons in Li 52. Determine the number of valence electrons in each element.
b. The number of 3d electrons in Cu Which elements do you expect to lose electrons in their chemi-
c. The number of 4p electrons in Br cal reactions? Which do you expect to gain electrons?
d. The number of 4d electrons in Zr a. Al b. Sn c. Br d. Se
376 Chapter 8 Periodic Properties of the Elements

53. Which outer electron configuration would you expect to belong 66. Write the electron configuration for each ion.
to a reactive metal? To a reactive nonmetal? a. Cl- b. P3- c. K+
a. ns2 b. ns2 np6 d. Mo 3+
e. V 3+
2 5
c. ns np d. ns2 np2 67. Write orbital diagrams for each ion and determine if the ion is
54. Which outer electron configurations would you expect to diamagnetic or paramagnetic.
belong to a noble gas? To a metalloid? a. V5+ b. Cr3+ c. Ni2+ d. Fe3+
a. ns2 b. ns2 np6 68. Write orbital diagrams for each ion and determine if the ion is
2 5
c. ns np d. ns2 np2 diamagnetic or paramagnetic.
a. Cd2 + b. Au + c. Mo3 + d. Zr2 +
Coulombs Law and Effective Nuclear Charge
69. Which is the larger species in each pair?
55. According to Coulombs Law, which pair of charged particles a. Li or Li + b. I - or Cs +
has the lowest potential energy? c. Cr or Cr3 + d. O or O2 -
a. a particle with a 1- charge separated by 150 pm from a 70. Which is the larger species in each pair?
particle with a 2+ charge a. Sr or Sr2 + b. N or N3 -
2+
b. a particle with a 1- charge separated by 150 pm from a c. Ni or Ni d. S2 - or Ca2 +
particle with a 1+ charge 71. Arrange this isoelectronic series in order of decreasing radius:
c. a particle with a 1- charge separated by 100 pm from a F - , Ne, O2 - , Mg2 + , Na + .
particle with a 3+ charge 72. Arrange this isoelectronic series in order of increasing atomic
56. According to Coulombs law, rank the interactions between charged radius: Se2 - , Kr, Sr2 + , Rb + , Br - .
particles from lowest potential energy to highest potential energy. 73. Choose the element with the higher first ionization energy from
a. a 1+ charge and a 1- charge separated by 100 pm each pair.
b. a 2+ charge and a 1- charge separated by 100 pm a. Br or Bi b. Na or Rb
c. a 1+ charge and a 1+ charge separated by 100 pm c. As or At d. P or Sn
d. a 1+ charge and a 1- charge separated by 200 pm
74. Choose the element with the higher first ionization energy from
57. Which electrons experience a greater effective nuclear charge: each pair.
the valence electrons in beryllium or the valence electrons in a. P or I b. Si or Cl
nitrogen? Why? c. P or Sb d. Ga or Ge
58. Arrange the atoms according to decreasing effective nuclear 75. Arrange these elements in order of increasing first ionization
charge experienced by their valence electrons: S, Mg, Al, Si. energy: Si, F, In, N.
59. If core electrons completely shielded valence electrons from 76. Arrange these elements in order of decreasing first ionization
nuclear charge (i.e., if each core electron reduced nuclear charge energy: Cl, S, Sn, Pb.
by 1 unit) and if valence electrons did not shield one another
77. For each element, predict where the jump occurs for succes-
from nuclear charge at all, what would be the effective nuclear
sive ionization energies. (For example, does the jump occur
charge experienced by the valence electrons of each atom?
between the first and second ionization energies, the second and
a. K b. Ca c. O d. C
third, or the third and fourth?)
60. In Section 8.6, we estimated the effective nuclear charge on a. Be b. N c. O d. Li
berylliums valence electrons to be slightly greater than 2 + .
78. Consider this set of successive ionization energies:
What would a similar treatment predict for the effective nuclear
charge on borons valence electrons? Would you expect the IE 1 = 578 kJ>mol
effective nuclear charge to be different for borons 2s electrons IE 2 = 1820 kJ>mol
compared to its 2p electron? In what way? (Hint: Consider the IE 3 = 2750 kJ>mol
shape of the 2p orbital compared to that of the 2s orbital.) IE 4 = 11,600 kJ>mol

Atomic Radius To which third-period element do these ionization values belong?

61. Choose the larger atom from each pair. Electron Affinities and Metallic Character
a. Al or In b. Si or N c. P or Pb d. C or F
79. Choose the element with the more negative (more exothermic)
62. Choose the larger atom from each pair.
electron affinity from each pair.
a. Sn or Si b. Br or Ga
a. Na or Rb b. B or S
c. Sn or Bi d. Se or Sn
c. C or N d. Li or F
63. Arrange these elements in order of increasing atomic radius:
80. Choose the element with the more negative (more exothermic)
Ca, Rb, S, Si, Ge, F.
electron affinity from each pair.
64. Arrange these elements in order of decreasing atomic radius: a. Mg or S b. K or Cs
Cs, Sb, S, Pb, Se. c. Si or P d. Ga or Br
81. Choose the more metallic element from each pair.
Ionic Electron Configurations, Ionic Radii, Magnetic Properties,
a. Sr or Sb b. As or Bi
and Ionization Energy c. Cl or O d. S or As
65. Write the electron configuration for each ion. 82. Choose the more metallic element from each pair.
a. O2- b. Br- c. Sr2+ a. Sb or Pb b. K or Ge
d. Co3+ e. Cu2+ c. Ge or Sb d. As or Sn
 Exercises 419

15. Within a covalent Lewis structure, what is the difference
between lone pair and bonding pair electrons?
16. In what ways are double and triple covalent bonds different
from single covalent bonds?
17. How does the Lewis model for covalent bonding account for why
certain combinations of atoms are stable while others are not?
18. How does the Lewis model for covalent bonding account for the
relatively low melting and boiling points of molecular
compounds (compared to ionic compounds)?
19. What is electronegativity? What are the periodic trends in
electronegativity?
20. Explain the difference between a pure covalent bond, a polar
covalent bond, and an ionic bond.
21. Explain what is meant by the percent ionic character of a bond.
Do any bonds have 100% ionic character?
22. What is a dipole moment?
23. What is the magnitude of the dipole moment formed by separat-
ing a proton and an electron by 100 pm? 200 pm?
24. What is the basic procedure for writing a covalent Lewis structure?
25. How do you determine the number of electrons that go into the
Lewis structure of a molecule? A polyatomic ion?
26. What are resonance structures? What is a resonance hybrid?
27. Do resonance structures always contribute equally to the overall
structure of a molecule? Explain.
28. What is formal charge? How is formal charge calculated? How
is it helpful?
29. Why does the octet rule have exceptions? Give the three major
categories of exceptions and an example of each.
30. What elements can have expanded octets? What elements
should never have expanded octets?
31. What is bond energy? How can you use average bond energies
to calculate enthalpies of reaction?
32. Explain the difference between endothermic reactions and exo-
thermic reactions with respect to the bond energies of the bonds
broken and formed.
33. What is the electron sea model for bonding in metals?
34. How does the electron sea model explain the conductivity of
metals? The malleability and ductility of metals?

Problems by Topic
Valence Electrons and Dot Structures 44. Rubidium iodide has a lattice energy of - 617 kJ/mol, while
potassium bromide has a lattice energy of - 671 kJ/mol. Why
35. Write an electron configuration for N. Then write a Lewis sym- is the lattice energy of potassium bromide more exothermic
bol for N and show which electrons from the electron configu- than the lattice energy of rubidium iodide?
ration are included in the Lewis symbol. 45. The lattice energy of CsF is - 744 kJ/mol, whereas that of BaO
36. Write an electron configuration for Ne. Then write a Lewis is - 3029 kJ/mol. Explain this large difference in lattice energy.
symbol for Ne and show which electrons from the electron con- 46. Arrange these compounds in order of increasing magnitude of
figuration are included in the Lewis symbol. lattice energy: KCl, SrO, RbBr, CaO.
37. Write a Lewis symbol for each atom or ion. 47. Use the BornHaber cycle and data from Appendix IIB, and
a. Al b. Na+ c. Cl d. Cl- Chapter 8 and this chapter to calculate the lattice energy of KCl.
38. Write a Lewis symbol for each atom or ion. (Hsub for potassium is 89.0 kJ/mol.)
a. S2 - b. Mg c. Mg2 + d. P 48. Use the BornHaber cycle and data from Appendix IIB and
Table 9.3 to calculate the lattice energy of CaO. (Hsub for
Ionic Lewis Symbols and Lattice Energy calcium is 178 kJ/mol; IE1 and IE2 for calcium are 590 kJ/mol
and 1145 kJ/mol, respectively; EA1 and EA2 for O are
39. Write the Lewis symbols that represent the ions in each ionic
141 kJ/mol and 744 kJ/mol, respectively.)
compound.
a. NaF b. CaO c. SrBr2 d. K2O
40. Write the Lewis symbols that represent the ions in each ionic Simple Covalent Lewis Structures, Electronegativity,
compound. and Bond Polarity
a. SrO b. Li2S c. CaI2 d. RbF
41. Use Lewis symbols to determine the formula for the compound 49. Use covalent Lewis structures to explain why each element (or
that forms between each pair of elements. family of elements) occurs as diatomic molecules.
a. Sr and Se b. Ba and Cl a. hydrogen b. the halogens
c. Na and S d. Al and O c. oxygen d. nitrogen
42. Use Lewis symbols to determine the formula for the compound 50. Use covalent Lewis structures to explain why the compound
that forms between each pair of elements: that forms between nitrogen and hydrogen has the formula
a. Ca and N b. Mg and I NH3. Show why NH2 and NH4 are not stable.
c. Ca and S d. Cs and F 51. Write the Lewis structure for each molecule.
43. Explain the trend in the lattice energies of the alkaline earth a. PH3 b. SCl2 c. HI d. CH4
metal oxides. 52. Write the Lewis structure for each molecule.
a. NF3 b. HBr c. SBr2 d. CCl4
Metal Oxide Lattice Energy (kJ/mol) 53. Write the Lewis structure for each molecule.
MgO -3795 a. SF2
CaO -3414 b. SiH4
SrO -3217 c. HCOOH (both O bonded to C)
d. CH3SH (C and S central)
BaO -3029
420 Chapter 9 Chemical Bonding I: The Lewis Model

54. Write the Lewis structure for each molecule. 70. Draw the Lewis structure (including resonance structures) for
a. CH2O b. C2Cl4 methyl azide (CH3N3). For each resonance structure, assign
c. CH3NH2 d. CFCl3 (C central) formal charges to all atoms that have formal charge.
55. Determine whether a bond between each pair of atoms would 71. What are the formal charges of the atoms shown in red?
be pure covalent, polar covalent, or ionic.
a. Br and Br b. C and Cl CH3
c. C and S d. Sr and O
CH3 N O
56. Determine whether a bond between each pair of atoms would
be pure covalent, polar covalent, or ionic. CH3
a. C and N b. N and S
c. K and F d. N and N 72. What are the formal charges of the atoms shown in red?
57. Draw the Lewis structure for CO with an arrow representing the
dipole moment. Use Figure 9.10 to estimate the percent ionic O
character of the CO bond.
CH3 S CH3
58. Draw the Lewis structure for BrF with an arrow representing
the dipole moment. Use Figure 9.10 to estimate the percent
ionic character of the BrF bond. Odd-Electron Species, Incomplete Octets, and Expanded Octets

Covalent Lewis Structures, Resonance, and Formal Charge 73. Write the Lewis structure for each molecule (octet rule not
followed).
59. Write the Lewis structure for each molecule or ion. a. BCl3 b. NO2 c. BH3
a. CI4 b. N2O c. SiH4 d. Cl2CO 74. Write the Lewis structure for each molecule (octet rule not
60. Write the Lewis structure for each molecule or ion. followed).
a. H3COH b. OH- c. BrO- d. O22- a. BBr3 b. NO c. ClO2
75. Write the Lewis structure for each ion. Include resonance struc-
61. Write the Lewis structure for each molecule or ion. tures if necessary and assign formal charges to all atoms. If
a. N2H2 b. N2H4 c. C2H2 d. C2H4 necessary, expand the octet on the central atom to lower formal
62. Write the Lewis structure for each molecule or ion. charge.
a. H3COCH3 b. CN- a. PO43 - b. CN- c. SO32 - d. ClO2-
-
c. NO2 d. ClO-
63. Write a Lewis structure that obeys the octet rule for each mole- 76. Write Lewis structures for each molecule or ion. Include reso-
cule or ion. Include resonance structures if necessary and assign nance structures if necessary and assign formal charges to all
formal charges to each atom. atoms. If necessary, expand the octet on the central atom to
a. SeO2 b. CO32 - c. ClO- d. NO2- lower formal charge.
a. SO42 - b. HSO4- c. SO3 d. BrO2-
64. Write a Lewis structure that obeys the octet rule for each ion.
Include resonance structures if necessary and assign formal 77. Write Lewis structures for each molecule or ion. Use expanded
charges to each atom. octets as necessary.
a. ClO3- b. ClO4- c. NO3- d. NH4+ a. PF5 b. I3- c. SF4 d. GeF4
65. Use formal charge to determine which Lewis structure is better: 78. Write Lewis structures for each molecule or ion. Use expanded
octets as necessary.
H H a. ClF5 b. AsF6- c. Cl3PO d. IF5

H C S H S C Bond Energies and Bond Lengths

66. Use formal charge to determine which Lewis structure is better:
79. Order these compounds in order of increasing carboncarbon
H H bond strength and in order of decreasing carboncarbon bond
length: HCCH, H2CCH2, H3CCH3.
H S C H H C S H
80. Which of these compounds has the stronger nitrogennitrogen
H H bond? The shorter nitrogennitrogen bond?
67. How important is this resonance structure to the overall struc- H2NNH2, HNNH
ture of carbon dioxide? Explain.
## O C i O# # ##
81. Hydrogenation reactions are used to add hydrogen across dou-
## ble bonds in hydrocarbons and other organic compounds. Use
average bond energies to calculate Hrxn for the hydrogenation
68. In N2O, nitrogen is the central atom and the oxygen atom is reaction.
terminal. In OF2, however, oxygen is the central atom. Use
formal charges to explain why. H2C CH2(g) + H2(g) h H3C i CH3(g)
69. Draw the Lewis structure (including resonance structures) for 82. Ethanol is a possible fuel. Use average bond energies to calcu-
the acetate ion (CH3COO-). For each resonance structure, late Hrxn for the combustion of ethanol.
assign formal charges to all atoms that have formal charge.
CH3CH2OH(g) + 3 O2(g) h 2 CO2(g) + 3 H2O(g)

83. Hydrogen, a potential future fuel, can be produced from carbon
(from coal) and steam by this reaction:
C(s) + 2 H2O(g) h 2 H2(g) + CO2(g)
Use average bond energies to calculate Hrxn for the reaction.
84. In the Chemistry and the Environment box on free radicals in this
chapter, we discussed the importance of the hydroxyl radical
in reacting with and eliminating many atmospheric pollutants.
Cumulative Problems
85. Write an appropriate Lewis structure for each compound. Make
certain to distinguish between ionic and molecular compounds.
a. BI3 b. K2S c. HCFO d. PBr3
86. Write an appropriate Lewis structure for each compound. Make
certain to distinguish between ionic and molecular compounds.
a. Al2O3 b. ClF5 c. MgI2 d. XeO4
87. Each compound contains both ionic and covalent bonds. Write
ionic Lewis structures for each of them, including the covalent
structure for the ion in brackets. Write resonance structures if
necessary.
a. BaCO3 b. Ca(OH)2
c. KNO3 d. LiIO
88. Each compound contains both ionic and covalent bonds. Write
ionic Lewis structures for each of them, including the covalent
structure for the ion in brackets. Write resonance structures if
necessary.
a. RbIO2 b. NH4Cl c. KOH d. Sr(CN)2
89. Carbon ring structures are common in organic chemistry. Draw
a Lewis structure for each carbon ring structure, including any
necessary resonance structures.
a. C4H8 b. C4H4 c. C6H12 d. C6H6
90. Amino acids are the building blocks of proteins. The simplest
amino acid is glycine (H2NCH2COOH). Draw a Lewis struc-
ture for glycine. (Hint: the central atoms in the skeletal structure
are nitrogen bonded to carbon, which is bonded to another car-
bon. The two oxygen atoms are bonded directly to the right-
most carbon atom.)
91. Formic acid is responsible for the sting of ant bites. By mass,
formic acid is 26.10% C, 4.38% H, and 69.52% O. The molar
mass of formic acid is 46.02 g/mol. Find the molecular formula
of formic acid and draw its Lewis structure.
92. Diazomethane is a highly poisonous, explosive compound because
it readily evolves N2. Diazomethane has the following composi-
tion by mass: 28.57% C; 4.80% H; and 66.64% N. The molar mass
of diazomethane is 42.04 g/mol. Find the molecular formula of
diazomethane, draw its Lewis structure, and assign formal charges
to each atom. Why is diazomethane not very stable? Explain.
93. The reaction of Fe2O3(s) with Al(s) to form Al2O3(s) and Fe(s)
is called the thermite reaction and is highly exothermic. What
role does lattice energy play in the exothermicity of the
reaction?
94. NaCl has a lattice energy of - 787 kJ/mol. Consider a
hypothetical salt XY. X3 + has the same radius of Na+ and Y3 -
has the same radius as Cl-. Estimate the lattice energy of XY.
95. Draw the Lewis structure for nitric acid (the hydrogen atom
is attached to one of the oxygen atoms). Include all three
resonance structures by alternating the double bond among the
Exercises 421
However, the hydroxyl radical does not clean up everything. For
example, chlorofluorocarbonswhich destroy stratospheric
ozoneare not attacked by the hydroxyl radical. Consider the
hypothetical reaction by which the hydroxyl radical might react
with a chlorofluorocarbon:
OH(g) + CF2Cl2(g) h HOF(g) + CFCl2(g)
Use bond energies to explain why this reaction is improbable.
three oxygen atoms. Use formal charge to determine which of
the resonance structures is most important to the structure of
nitric acid.
96. Phosgene (Cl2CO) is a poisonous gas used as a chemical
weapon during World War I. It is a potential agent for chemical
terrorism today. Draw the Lewis structure of phosgene. Include
all three resonance forms by alternating the double bond
among the three terminal atoms. Which resonance structure is
the best?
97. The cyanate ion (OCN-) and the fulminate ion (CNO-) share
the same three atoms but have vastly different properties. The
cyanate ion is stable, while the fulminate ion is unstable and
forms explosive compounds. The resonance structures of the
cyanate ion were explored in Example 9.8. Draw Lewis struc-
tures for the fulminate ionincluding possible resonance
formsand use formal charge to explain why the fulminate ion
is less stable (and therefore more reactive) than the cyanate ion.
98. Draw the Lewis structure for each organic compound from its
condensed structural formula.
a. C3H8 b. CH3OCH3
c. CH3COCH3 d. CH3COOH
e. CH3CHO
99. Draw the Lewis structure for each organic compound from its
condensed structural formula.
a. C2H4 b. CH3NH2
c. HCHO d. CH3CH2OH
e. HCOOH
100. Use Lewis structures to explain why Br3- and I3- are stable,
while F3- is not.
101. Draw the Lewis structure for HCSNH2. (The carbon and nitro-
gen atoms are bonded together and the sulfur atom is bonded to
the carbon atom.) Label each bond in the molecule as polar or
nonpolar.
102. Draw the Lewis structure for urea, H2NCONH2, one of the
compounds responsible for the smell of urine. (The central
carbon atom is bonded to both nitrogen atoms and to the oxygen
atom.) Does urea contain polar bonds? Which bond in urea is
most polar?
103. Some theories of aging suggest that free radicals cause certain
diseases and perhaps aging in general. As you know from the
Lewis model, such molecules are not chemically stable and will
quickly react with other molecules. According to certain theo-
ries, free radicals may attack molecules within the cell, such as
DNA, changing them and causing cancer or other diseases. Free
radicals may also attack molecules on the surfaces of cells,
making them appear foreign to the bodys immune system. The
immune system then attacks the cells and destroys them, weak-
474 Chapter 10 Chemical Bonding II: Molecular Shapes, Valence Bond Theory, and Molecular Orbital Theory
EXERCISES
Review Questions
1. Why is molecular geometry important? Cite some examples.
2. According to VSEPR theory, what determines the geometry of a
molecule?
3. Name and sketch the five basic electron geometries, and state
the number of electron groups corresponding to each. What
constitutes an electron group?
4. Explain the difference between electron geometry and molecu-
lar geometry. Under what circumstances are they not the same?
5. Give the correct electron and molecular geometries that corre-
spond to each set of electron groups around the central atom of
a molecule.
a. four electron groups overall; three bonding groups and one
lone pair
b. four electron groups overall; two bonding groups and two
lone pairs
c. five electron groups overall; four bonding groups and one
lone pair
d. five electron groups overall; three bonding groups and two
lone pairs
e. five electron groups overall; two bonding groups and three
lone pairs
f. six electron groups overall; five bonding groups and one
lone pair
g. six electron groups overall; four bonding groups and two
lone pairs
6. How do you apply VSEPR theory to predict the shape of a
molecule with more than one interior atom?
7. How do you determine if a molecule is polar? Why is polarity
important?
8. What is a chemical bond according to valence bond theory?
9. In valence bond theory, what determines the geometry of a
molecule?
10. In valence bond theory, the interaction energy between the
electrons and nucleus of one atom with the electrons and
nucleus of another atom is usually negative (stabilizing) when
______________.
11. What is hybridization? Why is hybridization necessary in
valence bond theory?
12. How does hybridization of the atomic orbitals in the central
atom of a molecule help lower the overall energy of the
molecule?
13. How is the number of hybrid orbitals related to the number of
standard atomic orbitals that are hybridized?
14. Sketch each hybrid orbital:
a. sp b. sp2
3
c. sp d. sp3d
3 2
e. sp d
Problems by Topic
VSEPR Theory and Molecular Geometry
31. A molecule with the formula AB3 has a trigonal pyramidal geom-
etry. How many electron groups are on the central atom (A)?
15. In the Lewis model, the two bonds in a double bond look identi-
cal. However, valence bond theory shows that they are not.
Describe a double bond according to valence bond theory.
Explain why rotation is restricted about a double bond, but not
about a single bond.
16. Name the hybridization scheme that corresponds to each elec-
tron geometry:
a. linear b. trigonal planar
c. tetrahedral d. trigonal bipyramidal
e. octahedral
17. What is a chemical bond according to molecular orbital theory?
18. Explain the difference between hybrid atomic orbitals in
valence bond theory and LCAO molecular orbitals in molecular
orbital theory.
19. What is a bonding molecular orbital?
20. What is an antibonding molecular orbital?
21. What is the role of wave interference in determining whether a
molecular orbital is bonding or antibonding?
22. In molecular orbital theory, what is bond order? Why is it
important?
23. How is the number of molecular orbitals approximated by a lin-
ear combination of atomic orbitals related to the number of
atomic orbitals used in the approximation?
24. Sketch each molecular orbital.
a. s2s b. s*2s
c. s2p d. s*2p
e. p2p f. p*2p
25. Draw an energy diagram for the molecular orbitals of period 2
diatomic molecules. Show the difference in ordering for B2, C2,
and N2 compared to O2, F2, and Ne2.
26. Why does the energy ordering of the molecular orbitals of the
period 2 diatomic molecules change in going from N2 to O2?
27. Explain the difference between a paramagnetic species and a
diamagnetic one.
28. When applying molecular orbital theory to heteronuclear
diatomic molecules, the atomic orbitals used may be of differ-
ent energies. If two atomic orbitals of different energies make
two molecular orbitals, how are the energies of the molecular
orbitals related to the energies of the atomic orbitals? How is
the shape of the resultant molecular orbitals related to the
shapes of the atomic orbitals?
29. In molecular orbital theory, what is a nonbonding orbital?
30. Write a short paragraph describing chemical bonding according
to the Lewis model, valence bond theory, and molecular orbital
theory. Indicate how the theories differ in their description of a
chemical bond and indicate the strengths and weaknesses of
each theory. Which theory is correct?
32. A molecule with the formula AB3 has a trigonal planar geome-
try. How many electron groups are on the central atom?
 Exercises 475

33. For each molecular geometry, list the number of total electron geometry, given the number of lone pairs and bonding groups
groups, the number of bonding groups, and the number of lone on the central atom.
pairs on the central atom.

(a) (b) (c)

(a) (b) (c)
44. Each ball-and-stick model shows the electron and molecular
34. For each molecular geometry, list the number of total electron geometry of a generic molecule. Explain what is wrong with
groups, the number of bonding groups, and the number of lone each molecular geometry and provide the correct molecular
pairs on the central atom. geometry, given the number of lone pairs and bonding groups
on the central atom.

(a) (b) (c)

(a) (b) (c)
35. Determine the electron geometry, molecular geometry, and
45. Determine the geometry about each interior atom in each mol-
idealized bond angles for each molecule. In which cases do you
ecule and sketch the molecule. (Skeletal structure is indicated in
expect deviations from the idealized bond angle?
parentheses.)
a. PF3 b. SBr2
a. CH3OH (H3COH) b. CH3OCH3 (H3COCH3)
c. CHCl3 d. CS2
c. H2O2 (HOOH)
36. Determine the electron geometry, molecular geometry, and
46. Determine the geometry about each interior atom in each mol-
idealized bond angles for each molecule. In which cases do you
ecule and sketch the molecule. (Skeletal structure is indicated in
expect deviations from the idealized bond angle?
parentheses.)
a. CF4 b. NF3
a. CH3NH2 (H3CNH2)
c. OF2 d. H2S
b. CH3CO2CH3 (H3CCOOCH3 both O atoms attached to
37. Which species has the smaller bond angle, H3O + or H2O? second C)
Explain. c. NH2CO2H (H2NCOOH both O atoms attached to C)
38. Which species has the smaller bond angle, ClO4- or ClO3- ?
Explain. Molecular Shape and Polarity
39. Determine the molecular geometry and sketch each molecule or
ion using the bond conventions shown in the Representing 47. Explain why CO2 and CCl4 are both nonpolar even though they
Molecular Geometries on Paper box in Section 10.4. contain polar bonds.
a. SF4 b. CIF3 48. CH3F is a polar molecule, even though the tetrahedral geometry
c. IF2- d. IBr4- often leads to nonpolar molecules. Explain.
40. Determine the molecular geometry and sketch each molecule or 49. Determine whether each molecule in Exercise 35 is polar or
ion, using the bond conventions shown in the "Representing nonpolar.
Molecular Geometries on Paper" Box in Section 10.4. 50. Determine whether each molecule in Exercise 36 is polar or
a. BrF5 b. SCl6 nonpolar.
c. PF5 d. IF4+ 51. Determine whether each molecule is polar or nonpolar.
41. Determine the molecular geometry about each interior atom a. ClO3- b. SCl2 c. SCl4 d. BrCl5
and sketch each molecule. 52. Determine whether each molecule is polar or nonpolar.
a. C2H2 (skeletal structure HCCH) a. SiCl4 b. CF2Cl2 c. SeF6 d. IF5
b. C2H4 (skeletal structure H2CCH2)
c. C2H6 (skeletal structure H3CCH3)
Valence Bond Theory
42. Determine the molecular geometry about each interior atom
and sketch each molecule. 53. The valence electron configurations of several atoms are shown
a. N2 next. How many bonds can each atom make without hybridization?
b. N2H2 (skeletal structure HNNH) a. Be 2s2 b. P 3s23p3 c. F 2s22p5
c. N2H4 (skeletal structure H2NNH2) 54. The valence electron configurations of several atoms are shown
43. Each ball-and-stick model shows the electron and molecular next. How many bonds can each atom make without
geometry of a generic molecule. Explain what is wrong with hybridization?
each molecular geometry and provide the correct molecular a. B 2s22p1 b. N 2s22p3 c. O 2s22p4
476 Chapter 10 Chemical Bonding II: Molecular Shapes, Valence Bond Theory, and Molecular Orbital Theory

55. Write orbital diagrams (boxes with arrows in them) to represent overlapping orbitals, and label all bonds using the notation
the electron configurationswithout hybridizationfor all the shown in Examples 10.6 and 10.7.
atoms in PH3. Circle the electrons involved in bonding. Draw a a. C2H2 (skeletal structure HCCH)
three-dimensional sketch of the molecule and show orbital b. C2H4 (skeletal structure H2CCH2)
overlap. What bond angle do you expect from the unhybridized c. C2H6 (skeletal structure H3CCH3)
orbitals? How well does valence bond theory agree with the 67. Consider the structure of the amino acid alanine. Indicate the
experimentally measured bond angle of 93.3? hybridization about each interior atom.
56. Write orbital diagrams (boxes with arrows in them) to represent
the electron configurationswithout hybridizationfor all the H
atoms in SF2. Circle the electrons involved in bonding. Draw a
O
three-dimensional sketch of the molecule and show orbital
overlap. What bond angle do you expect from the unhybridized
orbitals? How well does valence bond theory agree with the O C H
experimentally measured bond angle of 98.2?
57. Write orbital diagrams (boxes with arrows in them) to represent C
the electron configuration of carbon before and after sp3 H
H
hybridization.
C N
58. Write orbital diagrams (boxes with arrows in them) to represent
the electron configurations of carbon before and after sp H
hybridization. H H
59. Which hybridization scheme allows the formation of at least
one p bond? 68. Consider the structure of the amino acid aspartic acid. Indicate
the hybridization about each interior atom.
sp3, sp2, sp3d2
60. Which hybridization scheme allows the central atom to form O
more than four bonds? H H
3 3 2
sp , sp d, sp
C C O
61. Write a hybridization and bonding scheme for each molecule.
Sketch the molecule, including overlapping orbitals, and label H
O C C
all bonds using the notation shown in Examples 10.6 and 10.7.
a. CCl4 b. NH3
H
H
c. OF2 d. CO2 H
N O
62. Write a hybridization and bonding scheme for each molecule. H
Sketch the molecule, including overlapping orbitals, and label
all bonds using the notation shown in Examples 10.6 and 10.7.
a. CH2Br2 b. SO2 Molecular Orbital Theory
c. NF3 d. BF3
63. Write a hybridization and bonding scheme for each molecule or 69. Sketch the bonding molecular orbital that results from the linear
ion. Sketch the structure, including overlapping orbitals, and combination of two 1s orbitals. Indicate the region where inter-
label all bonds using the notation shown in Examples 10.6 ference occurs and state the kind of interference (constructive
and10.7. or destructive).
a. COCl2 (carbon is the central atom) 70. Sketch the antibonding molecular orbital that results from the
b. BrF5 linear combination of two 1s orbitals. Indicate the region where
c. XeF2 interference occurs and state the kind of interference (construc-
d. I3- . tive or destructive).
64. Write a hybridization and bonding scheme for each molecule 71. Draw an MO energy diagram and predict the bond order of Be2+
or ion. Sketch the structure, including overlapping orbitals, and Be2- . Do you expect these molecules to exist in the gas phase?
and label all bonds using the notation shown in Examples 10.6 72. Draw an MO energy diagram and predict the bond order of Li2+
and 10.7. and Li2- . Do you expect these molecules to exist in the gasphase?
a. SO32- b. PF6- c. BrF3 d. HCN 73. Sketch the bonding and antibonding molecular orbitals that
65. Write a hybridization and bonding scheme for each molecule result from linear combinations of the 2px atomic orbitals in a
that contains more than one interior atom. Indicate the hybrid- homonuclear diatomic molecule. (The 2px orbitals are those
ization about each interior atom. Sketch the structure, including whose lobes are oriented along the bonding axis.)
overlapping orbitals, and label all bonds using the notation 74. Sketch the bonding and antibonding molecular orbitals that
shown in Examples 10.6 and 10.7. result from linear combinations of the 2pz atomic orbitals in a
a. N2H2 (skeletal structure HNNH) homonuclear diatomic molecule. (The 2pz orbitals are those
b. N2H4 (skeletal structure H2NNH2) whose lobes are oriented perpendicular to the bonding axis.)
c. CH3NH2 (skeletal structure H3CNH2) How do these molecular orbitals differ from those obtained
66. Write a hybridization and bonding scheme for each molecule from linear combinations of the 2py atomic orbitals? (The 2py
that contains more than one interior atom. Indicate the hybrid- orbitals are also oriented perpendicular to the bonding axis, but
ization about each interior atom. Sketch the structure, including also perpendicular to the 2pz orbitals.)

Key Learning Outcomes, continued
Determining Whether a Molecule Displays
Hydrogen Bonding (11.3)
Using the Heat of Vaporization in Calculations (11.5)
Using the ClausiusClapeyron Equation (11.5)
Using Braggs Law in X-Ray
Diffraction Calculations (11.10)
Relating Density to Crystal Structure (11.11)
EXERCISES
Review Questions
1. Explain how a gecko is able to walk on a polished glass surface.
2. Why are intermolecular forces important?
3. What are the main properties of liquids (in contrast to gases and
solids)?
4. What are the main properties of solids (in contrast to liquids
and gases)?
5. What is the fundamental difference between an amorphous
solid and a crystalline solid?
6. What factors cause transitions between the solid and liquid
state? The liquid and gas state?
7. Describe the relationship between the state of a substance, its
temperature, and the strength of its intermolecular forces.
8. From what kinds of interactions do intermolecular forces
originate?
9. Why are intermolecular forces generally much weaker than
bonding forces?
10. What is the dispersion force? What does the magnitude of the
dispersion force depend on? How can you predict the magni-
tude of the dispersion force for closely related elements or
compounds?
11. What is the dipoledipole force? How can you predict the
presence of dipoledipole forces in a compound?
12. How is the miscibility of two liquids related to their polarity?
13. What is hydrogen bonding? How can you predict the presence
of hydrogen bonding in a compound?
14. What is the iondipole force? Why is it important?
15. What is surface tension? How does surface tension result from
intermolecular forces? How is it related to the strength of inter-
molecular forces?
Exercises 535
Example 11.2 For Practice 11.2 Exercises 4960
Example 11.3 For Practice 11.3
For More Practice 11.3 Exercises 7174
Examples 11.4, 11.5 For Practice 11.4, 11.5 Exercises 7578
Example 11.6 For Practice 11.6 Exercises 95, 96
Example 11.7 For Practice 11.7 Exercises 99102
16. What is viscosity? How does viscosity depend on intermolecu-
lar forces? What other factors affect viscosity?
17. What is capillary action? How does it depend on the relative
strengths of adhesive and cohesive forces?
18. Explain what happens in the processes of vaporization and con-
densation. Why does the rate of vaporization increase with
increasing temperature and surface area?
19. Why is vaporization endothermic? Why is condensation exo-
thermic?
20. How is the volatility of a substance related to the intermolecular
forces present within the substance?
21. What is the heat of vaporization for a liquid and why is it
useful?
22. Explain the process of dynamic equilibrium. How is dynamic
equilibrium related to vapor pressure?
23. What happens to a system in dynamic equilibrium when it is
disturbed in some way?
24. How is vapor pressure related to temperature? What happens to
the vapor pressure of a substance when the temperature is
increased? Decreased?
25. Define the terms boiling point and normal boiling point.
26. What is the ClausiusClapeyron equation and why is it
important?
27. Explain what happens to a substance when it is heated in a
closed container to its critical temperature.
28. What is sublimation? Give a common example of sublimation.
29. What is fusion? Is fusion exothermic or endothermic? Why?
30. What is the heat of fusion and why is it important?
536 Chapter 11 Liquids, Solids, and Intermolecular Forces

31. Examine the heating curve for water in Section 11.7
(Figure11.36). Explain why the curve has two segments in which
heat is added to the water but the temperature does not rise.
32. Examine the heating curve for water in Section 11.7
(Figure11.36). Explain the significance of the slopes of each of
the three rising segments. Why are the slopes different?
33. What is a phase diagram? Draw a generic phase diagram and
label its important features.
34. What is the significance of crossing a line in a phase diagram?
35. How do the properties of water differ from those of most other
substances?
36. Explain the basic principles involved in X-ray crystallography.
Include Braggs law in your explanation.
37. What is a crystalline lattice? How is the lattice represented with
the unit cell?
38. Make a drawing of each unit cell: simple cubic, body-centered
cubic, and face-centered cubic.
39. For each of the cubic cells in the previous problem, give the
coordination number, edge length in terms of r, and number of
atoms per unit cell.
40. What is the difference between hexagonal closest packing and
cubic closest packing? What are the unit cells for each of these
structures?
41. What are the three basic types of solids and the composite units
of each? What types of forces hold each type of solid together?
42. In an ionic compound, how are the relative sizes of the cation
and anion related to the coordination number of the crystal
structure?
43. Show how the cesium chloride, sodium chloride, and zinc
blende unit cells each contain a cation-to-anion ratio of 1:1.
44. Show how the fluorite structure accommodates a cation-to-
anion ratio of 1:2.
45. What are the three basic subtypes of atomic solids? What kinds
of forces hold each of these subtypes together?
46. In band theory of bonding for solids, what is a band? What is
the difference between the valence band and the conduction
band?
47. In band theory of bonding for solids, what is a band gap?
How does the band gap differ in metals, semiconductors, and
insulators?
48. Explain how doping can increase the conductivity of a semicon-
ductor. What is the difference between an n-type semiconductor
and a p-type semiconductor?

Problems by Topic
Intermolecular Forces 54. Arrange these compounds in order of increasing boiling point.
Explain your reasoning.
49. Determine the kinds of intermolecular forces that are present in a. H2S
each element or compound. b. H2Se
a. N2 c. H2O
b. NH3 55. In each pair of compounds, pick the one with the highest boil-
c. CO ing point. Explain your reasoning.
d. CCl4 a. CH3OH or CH3SH
50. Determine the kinds of intermolecular forces that are present in b. CH3OCH3 or CH3CH2OH
each element or compound. c. CH4 or CH3CH3
a. Kr 56. In each pair of compounds, pick the one with the higher boiling
b. NCl3 point. Explain your reasoning.
c. SiH4 a. NH3 or CH4
d. HF b. CS2 or CO2
51. Determine the kinds of intermolecular forces that are present in c. CO2 or NO2
each element or compound. 57. In each pair of compounds, pick the one with the higher vapor
a. HCl pressure at a given temperature. Explain your reasoning.
b. H2O a. Br2 or I2
c. Br 2 b. H2S or H2O
d. He c. NH3 or PH3
52. Determine the kinds of intermolecular forces that are present in 58. In each pair of compounds, pick the one with the higher vapor
each element or compound. pressure at a given temperature. Explain your reasoning.
a. PH3 a. CH4 or CH3Cl
b. HBr b. CH3CH2CH2OH or CH3OH
c. CH3OH c. CH3OH or H2CO
d. I2
59. Determine if each pair of compounds forms a homogeneous
53. Arrange these compounds in order of increasing boiling point. solution when combined. For those that form homogeneous
Explain your reasoning. solutions, indicate the type of forces that are involved.
a. CH4 a. CCl4 and H2O
b. CH3CH3 b. KCl and H2O
c. CH3CH2Cl c. Br2 and CCl4
d. CH3CH2OH d. CH3CH2OH and H2O

60. Determine if each pair of compounds forms a homogeneous
solution when combined. For those that form homogeneous
solutions, indicate the type of forces that are involved.
a. CH3CH2CH2CH2CH3 and CH3CH2CH2CH2CH2CH3
b. CBr4 and H2O
c. LiNO3 and H2O
d. CH3OH and CH3CH2CH2CH2CH3
Surface Tension, Viscosity, and Capillary Action
61. Which compound would you expect to have greater surface
tension: acetone [(CH3)2CO] or water (H2O)? Explain.
62. Water (a) wets some surfaces and beads up on others.
Mercury (b), in contrast, beads up on almost all surfaces.
Explain this difference.
(a) (b)
63. The structures of two isomers of heptane are shown below.
Which of these two compounds would you expect to have the
greater viscosity?
Compound A
Compound B
64. Explain why the viscosity of multigrade motor oils is less
temperature-dependent than that of single-grade motor oils.
65. Water in a glass tube that contains grease or oil residue displays a
flat meniscus (left), whereas water in a clean glass tube displays a
concave meniscus (right). Explain this observation.
Exercises 537
66. When a thin glass tube is put into water, the water rises 1.4 cm.
When the same tube is put into hexane, the hexane rises only
0.4 cm. Explain.
Vaporization and Vapor Pressure
67. Which evaporates more quickly: 55 mL of water in a beaker
with a diameter of 4.5 cm, or 55 mL of water in a dish with a
diameter of 12 cm? Is the vapor pressure of the water different
in the two containers? Explain.
68. Which evaporates more quickly: 55 mL of water 1H2O2 in a
beaker or 55 mL of acetone [(CH3)2CO] in an identical beaker
under identical conditions? Is the vapor pressure of the two sub-
stances different? Explain.
69. Spilling room-temperature water over your skin on a hot day
cools you down. Spilling room-temperature vegetable oil over
your skin on a hot day does not. Explain the difference.
70. Why is the heat of vaporization of water greater at room
temperature than it is at its boiling point?
71. The human body obtains 915 kJ of energy from a candy bar. If
this energy were used to vaporize water at 100.0 C, how much
water (in liters) could be vaporized? (Assume the density of
water is 1.00 g>mL.)
72. A 100.0 mL sample of water is heated to its boiling point. How
much heat (in kJ) is required to vaporize it? (Assume a density
of 1.00 g>mL.)
73. Suppose that 0.95 g of water condenses on a 75.0 g block of
iron that is initially at 22 C. If the heat released during
condensation goes only to warming the iron block, what is the
final temperature (in C) of the iron block? (Assume a constant
enthalpy of vaporization for water of 44.0 kJ>mol.)
74. Suppose that 1.15 g of rubbing alcohol (C3H8O) evaporates
from a 65.0 g aluminum block. If the aluminum block is initially
at 25 C, what is the final temperature of the block after the
evaporation of the alcohol? Assume that the heat required for
the vaporization of the alcohol comes only from the aluminum
block and that the alcohol vaporizes at 25 C.
75. This table displays the vapor pressure of ammonia at several
different temperatures. Use the data to determine the heat of
vaporization and normal boiling point of ammonia.
Temperature (K) Pressure (torr)
200 65.3
210 134.3
220 255.7
230 456.0
235 597.0
76. This table displays the vapor pressure of nitrogen at several
different temperatures. Use the data to determine the heat of
vaporization and normal boiling point of nitrogen.
Temperature (K) Pressure (torr)
65 130.5
70 289.5
75 570.8
80 1028
85 1718
538 Chapter 11 Liquids, Solids, and Intermolecular Forces

77. Ethanol has a heat of vaporization of 38.56 kJ>mol and a normal
boiling point of 78.4 C. What is the vapor pressure of ethanol
at 15 C?
78. Benzene has a heat of vaporization of 30.72 kJ>mol and a
normal boiling point of 80.1 C. At what temperature does
benzene boil when the external pressure is 445 torr?
Sublimation and Fusion
79. How much energy is released when 65.8 g of water freezes?
80. Calculate the amount of heat required to completely sublime
50.0 g of solid dry ice (CO2) at its sublimation temperature.
Theheat of sublimation for carbon dioxide is 32.3 kJ>mol.
81. An 8.5 g ice cube is placed into 255 g of water. Calculate the
temperature change in the water upon the complete melting of
the ice. Assume that all of the energy required to melt the ice
comes from the water.
82. How much ice (in grams) would have to melt to lower the
temperature of 352 mL of water from 25 C to 5 C? (Assume
the density of water is 1.0 g>ml.)
83. How much heat (in kJ) is required to warm 10.0 g of ice,
87. Nitrogen has a normal boiling point of 77.3 K and a melting
point (at 1 atm) of 63.1 K. Its critical temperature is 126.2 K
and critical pressure is 2.55 * 104 torr. It has a triple point at
63.1 K and 94.0 torr. Sketch the phase diagram for nitrogen.
Does nitrogen have a stable liquid state at 1 atm?
88. Argon has a normal boiling point of 87.2 K and a melting point
(at 1 atm) of 84.1 K. Its critical temperature is 150.8 K and
critical pressure is 48.3 atm. It has a triple point at 83.7 K and
0.68 atm. Sketch the phase diagram for argon. Which has the
greater density, solid argon or liquid argon?
89. The phase diagram for sulfur is shown here. The rhombic and
monoclinic states are two solid states with different structures.
a. Below what pressure does solid sulfur sublime?
b. Which of the two solid states of sulfur is most dense?
Liquid
Rhombic

Pressure
initially at - 10.0 C, to steam at 110.0 C? The heat capacity of Monoclinic
ice is 2.09 J>g # C, and that of steam is 2.01 J>g # C.
84. How much heat (in kJ) is evolved in converting 1.00 mol of 119 C, 0.027 mmHg
steam at 145 C to ice at - 50 C? The heat capacity of steam is
2.01 J>g # C, and that of ice is 2.09 J>g # C. 96 C, 0.0043 mmHg
Vapor
Phase Diagrams
85. Consider the phase diagram shown here. Identify the states Temperature
present at points a through g.
d 90. The high-pressure phase diagram of ice is shown here. Notice
that, under high pressure, ice can exist in several different solid
Pressure (not to scale)

Pc
e forms. What three forms of ice are present at the triple point
b
marked O? What is the density of ice II compared to ice I (the
a f familiar form of ice)? Would ice III sink or float in liquid water?

g
c Ice VII
Ice VI
Pressure (not to scale)

Ice V
O
Tc Ice II Ice
III
Temperature (not to scale)

86. Consider the phase diagram for iodine shown here. 1 atm
a. What is the normal boiling point for iodine? Ice I Liquid water
b. What is the melting point for iodine at 1 atm?
c. What state is present at room temperature and normal Gaseous
atmospheric pressure? water
d. What state is present at 186 C and 1.0 atm? Temperature (not to scale)
Pressure (not to scale)

Pc
The Uniqueness of Water
1 atm
91. Water has a high boiling point given its relatively low molar
mass. Why?
92. Water is a good solvent for many substances. What is the
molecular basis for this property and why is it significant?
93. Explain the role of water in moderating Earths climate.
113.6 C 184.4 C Tc 94. How is the density of solid water compared to that of liquid
Temperature (not to scale) water atypical among substances? Why is this significant?
 Exercises 539

Types of Solids and Their Structures

95. An X-ray beam with l = 154 incident on the surface of a crystal
produced a maximum reflection at an angle of u = 28.3.
Assuming n = 1, calculate the separation between layers of
atoms in the crystal.
96. An X-ray beam of unknown wavelength is diffracted from a
NaCl surface. If the interplanar distance in the crystal is 286pm,
and the angle of maximum reflection is found to be 7.23, what (c) Chromium
is the wavelength of the X-ray beam? (Assume n = 1.)
97. Determine the number of atoms per unit cell for each metal. 99. Platinum crystallizes with the face-centered cubic unit cell.
The radius of a platinum atom is 139 pm. Calculate the edge
length of the unit cell and the density of platinum in g>cm3.
100. Molybdenum crystallizes with the body-centered unit cell.
The radius of a molybdenum atom is 136 pm. Calculate the
edge length of the unit cell and the density of molybdenum.
101. Rhodium has a density of 12.41 g>cm3 and crystallizes with the
face-centered cubic unit cell. Calculate the radius of a rhodium
(a) Polonium atom.
(b) Tungsten
102. Barium has a density of 3.59 g>cm3 and crystallizes with the body-
centered cubic unit cell. Calculate the radius of a barium atom.
103. Polonium crystallizes with a simple cubic structure. It has a
density of 9.3 g>cm3, a radius of 167 pm, and a molar mass of
209 g>mol. Use this data to estimate Avogadros number (the
number of atoms in one mole).
104. Palladium crystallizes with a face-centered cubic structure. It has a
density of 12 .0 g>cm3, a radius of 138 pm, and a molar mass of
106 .42 g>mol. Use this data to estimate Avogadros number.
(c) Nickel
105. Identify each solid as molecular, ionic, or atomic.
a. Ar(s) b. H2O(s)
98. Determine the coordination number for each structure. c. K2O(s) d. Fe(s)
106. Identify each solid as molecular, ionic, or atomic.
a. CaCl2(s) b. CO2(s)
c. Ni(s) d. I2(s)
107. Which solid has the highest melting point? Why?
Ar(s), CCl4(s), LiCl(s), CH3OH(s)

108. Which solid has the highest melting point? Why?

C(s, diamond), Kr(s), NaCl(s), H2O(s)
(a) Gold
109. Which solid in each pair has the higher melting point and why?
a. TiO2(s) or HOOH(s) b. CCl4(s) or SiCl4(s)
c. Kr(s) or Xe(s) d. NaCl(s) or CaO(s)
110. Which solid in each pair has the higher melting point and why?
a. Fe(s) or CCl4(s) b. KCl(s) or HCl(s)
c. Ti(s) or Ne(s) d. H2O(s) or H2S(s)
111. An oxide of titanium crystallizes with the unit cell shown here
(titanium = gray; oxygen = red) What is the formula of
theoxide?

(b) Ruthenium