Solution Manual for Organic Chemistry 7th Edition

Brown Iverson Anslyn Foote 1133952844

9781133952848
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CHAPTER 6
IONIC COMPOUNDS: PERIODIC TRENDS AND BONDING THEORY

Chapter Learning Goals for Students

Section 6.1 Predict the ground-state electron configuration for main group and transition metal ions.

Determine the number of unpaired electrons in a transition metal ion.

Section 6.2 Predict the relative size of anions, cations, and atoms.

Predict the relative size of isoelectronic ions.

Section 6.3 Order elements from lowest to highest ionization energy.

Explain the periodic trend in ionization energy.

Section 6.4 Compare successive ionization energies (higher second, third, fourth, etc.) for different
elements.

Identify elements based on values of successive ionization energies.

Section 6.5 Compare the value of the electron affinity for different elements.

Explain the periodic trend in electron affinity.

Section 6.6 Use the octet rule to predict charges on main group ions, electron configurations of main
group ions and formulas for ionic compounds.

Section 6.7 Visualize ionic compounds on the molecular level.

Draw a Born-Haber cycle, identifying the energies involved in the calculation of lattice
energy for an ionic compound formed from its elements.

Use the Born-Haber cycle to solve for the energy change associated with one of the
steps.

Section 6.8 Predict the relative magnitude of lattice energy given the formula or molecular
representation of an ionic compound.

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 Chapter 6 — Ionic Compounds: Periodic Trends and Bonding
Theory

Lecture Outline
6.1. Electron Configurations of Ions1
A. Main-group elements
1. Electrons lost by a metal come from the highest-energy occupied orbital
2. Electrons gained by a nonmetal go into lowest-energy unoccupied orbital
B. Transition metals – lose valence-shell s electrons first, then d electrons
6.2. Ionic Radii2
A. Cations have smaller radii than neutral atoms
1. Electrons removed from larger valence-shell orbitals
2. Increase in Zeff when electrons removed
B. Anions have larger radii than neutral atoms
1. Decrease in Zeff when electrons added
2. Increase in electron-electron repulsions
6.3. Ionization Energy3
A. Ionization energy (Ei) – amount of energy required to remove the outermost electron from an
isolated neutral atom in the gaseous state
B. Periodic trends in ionization energy
1. Minimum Ei – group 1A alkali metals
2. Maximum Ei – group 8A noble gases
3. Ei increases across a period
4. Ei decreases down a group
C. Periodicity due to electron configurations
1. Single s electron in valence-shell of alkali metals feels low Zeff
a. Single valence electron well shielded by the core (inner shell) electrons
b. Electron loosely held
c. Low energy needed to remove electron
2. Electrons in filled valence-subshell of noble gas elements feel high Zeff
a. Electrons tightly held
b. Radius of atom shrinks
c. High energy needed to remove electron
3. Increase in atomic number down a group
a. Average distance of the electron from the nucleus increases as the value of n increases
b. Valence-shell electrons less tightly held than core electrons
c. Ei decreases
D. Minor irregularities occur from left to right across a row of the periodic table
1. Group 2A elements – Ei (Be) > Ei (B) (due to electron configuration)
a. 2p electron of boron shielded somewhat by 2s electrons
b. Feels a smaller Zeff
c. More easily removed
2. Group 6 A elements – Ei (N) > Ei (O) (due to electron configuration)
a. 2p electron removed from nitrogen removed from a half-filled orbital (stable configuration)
b. 2p electron removed from oxygen removed from a filled orbital
i. Electrons in filled orbitals forced together and have slightly higher energy
ii. Easier to remove electrons from filled orbitals
6.4. Higher Ionization Energies4
A. Energy involved with the removal of two, three, or even more electrons sequentially from an atom
B. Successively larger amounts of energy required for each ionization step – more difficult to remove
a negatively charged electron from a positively charged ion
C. Large jumps in successive ionization energies of the elements – textbook Table 6.2

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Test Item File Questions: Multiple Choice 1 – 6, Algorithmic 4 – 9, Short Answer 1 – 12
2
Test Item File Questions: Multiple Choice 7 – 12, Algorithmic 10, Short Answer 13
3
Test Item File Questions: Multiple Choice 13 – 21, Algorithmic 11 – 15, Short Answer 14
4
Test Item File Questions: Multiple Choice 22 – 28, Algorithmic 16 – 21, Short Answer 15 – 16
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 Chapter 6—Ionic Compounds: Periodic Trends and
Bonding Theory

1. Valence-shell electrons easily lost during ionization

2. Core electrons relatively difficult to remove
D. Valence-shell electron configuration of an atom controls its chemistry.
6.5. Electron Affinity5
A. Electron affinity (Eea) – energy change when electron added to an isolated gaseous atom
B. Eea usually has a negative value
1. Energy usually released when an atom adds an electron
2. More negative the value,
a. greater the tendency of the atom to accept an electron
b. more stable the anion
C. Eea > 0 for atoms that form an unstable anion on addition of an electron
D. No experimental measurements can be made.
E. Periodic trends of Eea related to electron configurations
1. Sign and magnitude of Eea due to offsetting factors
a. Negative Eea due to attraction between the additional electron and the atomic nucleus
b. Positive Eea due to repulsions between the additional electron and the electrons in the atom
2. Halogens have large, negative Eea
a. High Zeff
b. Room in valence-shell for an additional electron
c. High attraction between additional electron and atomic nucleus
3. Noble-gas elements have positive Eea
a. Filled s and p sublevels
b. Additional electron goes into the next higher shell – feels a low Zeff
c. Small attraction between the additional electron and the atomic nucleus
d. High electron-electron repulsions
4. Alkaline earth metals have Eea  0
a. Filled s subshell
b. Added electron goes into p subshell of higher energy
c. Relatively low Zeff
6.6. The Octet Rule6
A. Octet rule – main-group elements tend to undergo reactions that leave them with eight valence
electrons
1. Useful for making predictions; provides insights about chemical bonds
2. “Magic number” = 8
a. Filled octet – s and p subshells both filled
b. Can’t take electrons away – electrons tightly held by high Zeff
c. No low-energy orbitals available to accept electrons
3. Failure of rule
a. Elements on right side of periodic table in third or lower period
b. More than eight electrons sometimes accommodated by larger atoms
B. Factors that determine cation or anion formation
1. Cations
a. Electrons highly shielded from nucleus by core electrons
i. Feel low Zeff
ii. Easily lost
b. Charge based on electronic configuration – energy required unavailable to lose another
electron once next-lower noble gas configuration achieved
2. Anions
a. Electrons poorly shielded from nucleus by core electrons
i. Feel high Zeff
ii. Can gain electrons because of Zeff

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Test Item File Questions: Multiple Choice 29 – 35, Algorithmic 22 – 23, Short Answer 17 – 18
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Test Item File Questions: Multiple Choice 36, Algorithmic 24 – 31, Short Answer 19
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 Chapter 6 — Ionic Compounds: Periodic Trends and Bonding
Theory

b. Charge based on electronic configuration – low-energy orbitals required for additional

electrons unavailable once next-higher noble gas configuration achieved
6.7. Ionic Bonds and the Formation of Ionic Solids 7
A. Element with low Ei can transfer an electron to an element with negative Eea
1. Produces a cation and an anion
2. Cation and anion mutually attracted by electrostatic forces
3. Ionic bond created
4. Three-dimensional network of ions (ionic solid) formed
a. Each cation surrounded by and attracted to many anions
b. Each anion surrounded by and attracted to many cations
B. Ionic bond formation leads to large gain in stability
1. Overcomes unfavorable energy change of electron transfer
C. Born-Haber cycle – series of hypothetical steps each of which contributes to the overall energy
change during the formation of an ionic compound
1. Net process is the sum of individual steps
2. Typical individual steps
a. Sublimation of a metal atom to a gaseous atom
b. Dissociation of nonmetal molecules
c. Ionization of isolated metal atoms
d. Formation of nonmetal anions
e. Formation of solid ionic compound
6.8. Lattice Energies in Ionic Solids8
A. Lattice energy (U) – sum of electrostatic interaction energies between ions in a solid
1. Refers to the breakup of a crystal into individual ions
a. Positive value
b. When using the lattice energy in a Born-Haber cycle must change the sign because last step
is the reverse of the breakup of the crystal
2. Lattice energy mostly coulombic
zz
Coulomb's law: F = k ´ 1 22
d
3. Effect of ion charge – compounds of ions with higher charges have greater lattice energies than
compounds of ions with lower charges
4. Effect of ion size – compounds of ions with smaller sizes have greater lattice energies than
compounds of ions with larger sizes
2. Anions
a. Electrons poorly shielded from nucleus by core electrons
i. Feel high Zeff
ii. Can gain electrons because of Zeff
b. Charge based on electronic configuration – low-energy orbitals required for additional
electrons unavailable once next-higher noble gas configuration achieved
Inquiry – How Has an Understanding of Ionic Compounds Led to the Production of Safer Solvents?

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Test Item File Questions: Multiple Choice 37 – 45, Algorithmic 32
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Test Item File Questions: Multiple Choice 46 – 47, Algorithmic 33 – 39, Short Answer 20
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 Chapter 6—Ionic Compounds: Periodic Trends and
Bonding Theory

CHAPTER 6
IONIC COMPOUNDS: PERIODIC TRENDS AND BONDING THEORY

Teaching Tips, Points of Emphasis, and Common Misconceptions

Section 6.1 Electrons are always lost from orbitals having the highest value of the principal quantum
number, n, before they are lost from orbitals with lower values of n.

Section 6.2 The larger the proton-to-electron ratio, the greater the attraction of the nucleus for the
valence electrons and the smaller the size of the ion.

Section 6.3 Ionization energy is defined for isolated, gaseous-state atoms. Other factors, such as
lattice energy or solvation energy, must be considered when forming ions in a condensed
state.

Section 6.3 Core electrons shield valence electrons effectively; electrons in the same shell shield one
another ineffectively.

Section 6.3 The closer an electron is to the nucleus, the higher its ionization energy. Hence, small
atoms have high ionization energies. Due to its small size, the first element in every
group tends to differ significantly from the other elements in the same group.

Section 6.4 A large change in two successive ionization energies signifies that a core electron is
being ionized. In ordinary chemical reactions there is not enough energy available to
ionize core electrons. Hence, only valence electrons are involved in chemical reactions.

Section 6.5 Electron affinity is defined for isolated, gaseous-state atoms. Other factors, such as
lattice energy or solvation energy, must be considered when forming ions in a condensed
state.

Section 6.5 Just as there are successive ionization energies: Ei1, Ei2, Ei3,..., there are successive
electron affinities: Eea1, Eea2, Eea3,....While energy is generally released on addition of one
electron, energy is always required to add two or more electrons to a neutral gaseous
atom.

Section 6.7 An ionic compound will form when an element from the far left-hand side combines with
an element from the far right-hand side of the periodic table (a notable exception being
BeCl2). Compounds encountered in a general chemistry course are usually ionic if
formed from reaction of a metal with a nonmetal.

Section 6.7 Formulas for ionic compounds are empirical formulas giving the relative number of
cations and anions. Although the formula for sodium chloride is NaCl, molecules of
NaCl do not exist under ordinary laboratory conditions.

Section 6.7 Because the sum of ionization energy and electron affinity is always positive, obtaining
noble gas electron configurations upon formation of ions is not the driving force behind
the formation of an ionic compound. The ions must be stabilized by strong forces arising
from electrostatic attraction.

Section 6.7 The Born-Haber cycle is an example of Hess’s law, which will be introduced in Chapter
9. It is used to calculate properties that are impossible to measure directly.

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 Chapter 6 — Ionic Compounds: Periodic Trends and Bonding
Theory

Section 6.8 When an actual lattice energy is more negative than that calculated on the basis of an
ionic model, some covalent bonding between ions is occurring. This typically happens
when the electronegativity of the metal is high (approximately > 1.5).

Lecture/Laboratory Demonstration References

Section 6.5 Lee R. Summerlin, Christie L. Borgford, and Julie B. Ealy, “Halogens Compete for
Electrons,” Chemical Demonstrations, A Sourcebook for Teachers, Vol. 2 (American
Chemical Society, Washington, DC, 1988), pp. 60-61. The relative tendency of halogens
to gain or lose electrons is demonstrated.

Section 6.7 Kristin A. Johnson, Rodney Schreiner, and Jon Loring, “A Dramatic Flame Test
Demonstration,” J. Chem. Educ., Vol. 78, 2001, 640-641.

Section 6.7 M.D. Alexander, “Reactions of the Alkali Metals with Water: A Novel Demonstration,”
J. Chem. Educ., Vol. 69, 1992, 418. The reaction of sodium metal with water to produce
an aqueous solution of sodium hydroxide and hydrogen gas is performed at the interface
between paint thinner and the more dense water. Periodically, bubbles of hydrogen gas
carry the sodium metal into the organic layer, temporarily stopping the reaction. The
presence of the aqueous layer is shown by a phenolphthalein indicator color change.

Section 6.8 Lee R. Summerlin, Christie L. Borgford, and Julie B. Ealy, “Producing Hydrogen Gas
from Calcium Metal,” Chemical Demonstrations, A Sourcebook for Teachers, Vol. 2
(American Chemical Society, Washington, DC, 1988), pp. 51-52.

Literature References
Section 6. None

Media References
Section 6.1 Ion Electron Configuration activity from the Instructor Resource DVD

Section 6.2 Gain and Loss of Electrons movie from the Instructor Resource DVD

Section 6.3 Effective Nuclear Charge movie from the Instructor Resource DVD

Section 6.3 Periodic Trends: Ionization Energies movie from the Instructor Resource DVD

Section 6.5 Electron Affinity movie from the Instructor Resource DVD

Section 6.5 Periodic Trends: Electron Affinity movie from the Instructor Resource DVD

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