Solution Manual for Organic Chemistry 7th

Edition Brown Iverson Anslyn Foote

1133952844 9781133952848
Full download link at:
Solution manual: https://testbankpack.com/p/solution-manual-for-
chemistry-7th-edition-by-mcmurry-isbn-0321940873-9780321940872/
Test bank: https://testbankpack.com/p/test-bank-for-chemistry-7th-
edition-by-mcmurry-isbn-0321940873-9780321940872/
CHAPTER 5
PERIODICITY AND THE ELECTRONIC STRUCTURE OF ATOMS

Chapter Learning Goals for Students

Section 5.1 Label the wavelength, frequency, and amplitude in an electromagnetic wave and
understand their meaning.

Interconvert between wavelength and frequency of electromagnetic radiation.

Section 5.2 Calculate the energy of electromagnetic radiation in units of J/photon or kJ/mol,
when given the frequency or wavelength.

Describe the photoelectric effect and explain how it supports the theory of
particlelike properties of light. (Figures 5.4 and 5.5)

Calculate the frequency or wavelength of radiation needed to produce the

photoelectric effect given the work function of a metal.

Section 5.3 Describe the difference between a continuous and line spectrum. (Figure 5.7)

Section 5.4 Compare the wavelength and frequency of different electron transitions in the Bohr
model of the atom.

Relate wavelengths calculated using the Balmer–Rydberg equation to energy levels

in the Bohr model of the atom.

Section 5.5 Calculate the wavelength of a moving object using the de Broglie equation.

Explain why the wavelength of macroscopic objects is not observed.

Section 5.6 Calculate the uncertainty in the position of the moving object if the velocity is
known.

Section 5.7 Identify and write valid sets of quantum numbers that describe electrons in different
types of orbitals.

Section 5.8 Identify an orbital based on its shape and describe it using a set of quantum
numbers.

Visualize the nodal planes in different types of orbitals and different shells.

41
 Chapter 5—Periodicity and the Electronic Structure of Atoms

Section 5.9 Assign a set of four quantum numbers for electrons in an atom.

Section 5.10 Explain how electron shielding gives the order of subshells from lowest to highest in
energy. (Figure 5.9)

Predict the order of filling of subshells based upon energy.

Section 5.11
and
Section 5.12 Assign the electron configuration to atoms in the ground state.

Section 5.13 Draw orbital filling diagrams for the ground state of an atom and determine the
number of unpaired electrons.

Identify atoms from orbital filling diagrams or electron configurations.

Section 5.14 Explain the periodic trend in atomic radii.

Predict the relative size of atoms based upon their position in the periodic table.

42
 Chapter 5—Periodicity and the Electronic Structure of Atoms

Lecture Outline
5.1. The Nature of Radiant Energy and the Electromagnetic Spectrum1
A. Electromagnetic radiation – forms of radiant energy (light in all its varied forms)
B. Electromagnetic spectrum – a continuous range of wavelengths and frequencies of all forms of
electromagnetic radiation
C. Radiant energy – has wavelike properties
1. Frequency () – the number of peaks (maxima) that pass by a fixed point per unit time (s –1
or Hz)
2. Wavelength () – the length from one wave maximum to the next
3. Amplitude – the height measured from the middle point between peak and trough
(maximum and minimum)
4. Intensity of radiant energy is proportional to amplitude 2
D. Speed of light (c) – rate of travel of all electromagnetic radiation in a vacuum
1. c = 3.00  108 m/s
2. Wavelength  Frequency = Speed
(m)   (s–1) = c (m/s)
3. Frequency and wavelength inversely related:
c c
  or ν 
ν 
a. long ; low ν
b. short ; high ν
5.2. Particlelike Properties of Radiant Energy: The Photoelectric Effect and Planck’s Postulate2
A. The photoelectric effect can be seen when light of a minimum frequency strikes some metal
surfaces resulting in electron emission.
B. Einstein postulated that light behaves like a stream of particles called photons.
1. Based on Planck’s Postulate, the energy of a photon is quantized—occurs in a discrete
quantity.
hc
a. E  h ; E  ; h = 6.626 x 10–34 Js (Planck’s constant)

b. High-energy radiation – higher , shorter 
c. Low-energy radiation – lower , longer 
C. The work function, , is the minimum amount of energy required to cause electron emission.
1. Low intensity, high frequency light results in few electrons emitted.
2. High intensity, high frequency light results in many electrons emitted.
D. Einstein concluded that the nature of light is more complex than previously believed.
1. Light can behave as waves.
2. Light can behave as small particles—photons with a quantized or discrete amount of energy.
5.3. The Interaction of Radiant Energy with Atoms: Line Spectra3
A. Individual energetically-excited atoms emit light
1. Provides clue to atomic makeup
2. Consists of only a few 
3. Line spectrum – series of discrete lines (or wavelengths) separated by blank areas
4. Each element has its own unique line spectrum
B. Balmer – pattern in atomic line spectra for the hydrogen atom
1. All four lines in the hydrogen spectrum expressed by
1 æ1 1ö
= Rç 2 - 2 ÷
l è2 n ø

1
Test Item File Questions: Multiple Choice 1 – 6, Algorithmic 1, Short Answer 1 – 6
2
Test Item File Questions: Multiple Choice 7 – 10, Algorithmic 2, Short Answer 7 – 9
3
Test Item File Questions: Multiple Choice 11 – 14, Algorithmic 3, Short Answer 10 – 11
 Chapter 5—Periodicity and the Electronic Structure of Atoms

2. R (Rydberg constant) = 1.097 10–2 nm–1

3. Rydberg – every line in the entire hydrogen spectrum fits the generalized Balmer-Rydberg
equation
1 æ1 1ö
= R ç 2 - 2 ÷ where n > m
l è2 n ø
5.4. The Bohr Model of the Atom: Quantized Energy 4
A. The hydrogen atom has a small, highly charged nucleus with electrons in specific orbitals, like
planets.
1. Each orbital has a specific energy.
2. Electron energies are quantized – have only specific energy values associated with the
orbital.
B. Addition of energy to an atom causes an electron to transition from a lower to a higher energy
orbital.
1. Absorption of energy results in an excited atom.
2. Excited atom is unstable.
a. Electron returns to a lower energy level by emission of an amount of energy equal to
the energy difference between the higher and lower energy levels.
b. Since energy levels are quantized, the energy of the emitted light is of only certain
frequencies
3. Calculate the energy differences between levels by measuring the frequencies or wavelengths
emitted.
C. The Bohr model failed to predict line spectra of other atoms.
D. The model does not provide an accurate depiction of the electron’s location.
5.5. Wavelike Properties of Matter: deBroglie’s Hypothesis5
A. Einstein – relationship between mass and 
E hc / l h
m= 2 = 2 =
c c lc
B. de Broglie – matter can behave in some respects like light
1. Both light and matter wavelike as well as particlelike
2. Relationship between  of an electron or of any other particle or object of mass m moving
at velocity v
h h
m= ; l=
lv mv
C. Dual wave/particle description of light and matter
1. Wave properties of macroscopic objects have not been observed.
2. On the atomic scale, matter behaves differently. Diffraction (wave characteristic) of
electrons has been observed.
5.6. The Quantum Mechanical Model of the Atom: Heisenberg Uncertainty Principle6
A. Schrödinger
1. Quantum mechanical model of the atom
2. Abandoned idea of an electron as a small particle moving around the nucleus in a defined
path
3. Concentrated on the electron’s wavelike properties
B. Heisenberg Uncertainty Principle – both position (x) and momentum (mv) of an electron
cannot be known beyond a certain level of precision
h
(Dx)(Dmv) ³
4p
1. Cannot know both the position and the momentum of an electron with a high degree of
certainty

4
Test Item File Questions: Multiple Choice 15 – 22, Algorithmic 4
5
Test Item File Questions: Multiple Choice 23 – 26, Algorithmic 5 – 6, Short Answer 12
6
Test Item File Questions: Multiple Choice 27 – 30,
44
 Chapter 5—Periodicity and the Electronic Structure of Atoms

2. If momentum is known with a high degree of certainty,

a. mv is small
b.  x (position of the electron) is large
3. If the exact position of the electron is known,
a. x is small
b. mv is large
5.7. The Quantum Mechanical Model of the Atom: Orbitals and Quantum Numbers7
A. Quantum mechanical model of atomic structure
1. Mathematical form is a wave equation
2. Wave function () or orbital – solution to wave equation
a. Has a specific energy
b. Contains information about an electron’s position in 3-D space
c. 2 – gives the probability of finding an electron within a given region in space
d. Defines a volume of space around the nucleus where there is a high probability of
finding an electron
e. Says nothing about the electron’s path or movement
B. Wave function – contains a set of three variables, quantum numbers
1. Describes the energy level of an orbital
2. Defines the shape and orientation of the region in space where the electron is most likely to
be found
C. Principal quantum number (n) – describes the size and energy level of the orbital
1. A positive integer (n = 1,2,3,4,…)
2. As the value of n increases,
a. number of allowed orbitals increases
b. size of the orbitals increases
c. energy of the electron in the orbital increases
3. Shell – grouping of orbitals according to the principal quantum number
D. Angular-momentum quantum number (l) – defines the 3-D shape of the orbital
1. Integral value from 0 to n – 1
2. Within each shell, n different shapes for orbitals
3. Subshells – grouping of orbitals according to the angular-momentum quantum number
4. Referred to by letter rather than by number
a. quantum number l: 0 1 2 3 4 ...
b. subshell notation: s p d f g ...
E. Magnetic quantum number (ml) – defines the spatial orientation of the orbital along a standard
set of coordinate axes
1. Integral values from – l to +l
2. Within each subshell (same n and same l), 2 l + 1 different spatial orientations
F. Energy level of various orbitals – textbook Figure 5.10
1. Hydrogen – energy levels depend only on n
2. Multielectron atoms – energy levels depend on both n and l
5.8. The Shapes of Orbitals8
A. s orbitals – textbook Figure 5.11
1. Spherical
2. Probability of finding an electron – depends only on electron from the nucleus
3. Differences among s orbitals in different shells
a. Size increases in successively higher shells
b. Electron distribution in outer s orbitals – several different regions of maximum
probability separated by a node
4. Node – a surface of zero probability
a. Intrinsic property of a wave – zero amplitude at node (textbook Figure 5.12)

7
Test Item File Questions: Multiple Choice 31 – 41, Algorithmic 7 – 12, Short Answer 13 – 18
8
Test Item File Questions: Multiple Choice 42 – 44, Algorithmic 13 – 15, Short Answer 19 – 21
 Chapter 5—Periodicity and the Electronic Structure of Atoms

B. p orbitals – textbook Figure 5.13

1. Dumbbell shaped
2. Electron distribution concentrated in identical lobes on either side of the nucleus
3. Nodal plane cuts through the nucleus
4. Probability of finding a p electron near the nucleus is zero
5. Have different phases (mathematical signs)
a. Crucial for bonding
b. Only lobes with same phase interact to form covalent bonds
6. Three p orbitals oriented along the x-, y-, and z-axes. (px, py, pz)
C. d and f orbitals
1. d orbitals – textbook Figure 5.14
a. Four (dxy , dxz, dyz, dx2– y2) – cloverleaf shaped
i. Four lobes of maximum electron probability separated by two nodal planes through
the nucleus
b. dz2 – similar in shape to a pz orbital with additional donut-shaped region of electron
probability in the xy plane
c. Alternating lobes have different phases
2. f orbitals – eight lobes of maximum electron probability
a. Three nodal planes through the nucleus
5. 9. Electron Spin and the Pauli Exclusion Principle 9
A. Fourth quantum number – ms
1. Related to property called electron spin
2. Electron behaves as if spinning around an axis
a. Gives rise to a tiny magnetic field
3. Has two values: +1/2 (  ) or –1/2 (  )
4. Independent of other quantum numbers
B. Pauli Exclusion Principle
1. No two electrons in an atom can have same four quantum numbers
2. Only two electrons with opposite spins per orbital
5.10. Orbital Energy Levels in Multielectron Atoms10
A. Energy level of an orbital in multielectron – depends on both n and l.
1. Energy difference due to electron-electron repulsions
2. Outer-shell electrons
a. Pushed farther from nucleus
b. Held less tightly
3. Partially cancels electron-nucleus attractions
4. Electrons shielded from nucleus by the other electrons.
B. Effective nuclear charge, Zeff – net nuclear charge actually felt by an electron
1. Zeff = Z – electron shielding
2. Lower than the actual nuclear charge
3. For the same shell
a. Lower value of l corresponds to higher value of Zeff
b. Corresponds to lower energy for the orbital
4. Useful for explaining various chemical phenomena
5.11. Electron Configurations of Multielectron Atoms11
A. Electron configuration – describes the orbitals occupied by electrons in an atom
B. Aufbau principle
1. Fill lowest-energy orbitals first
2. Only two electrons with opposite spin per orbital
3. Follow Hund’s rule: if two or more orbitals with same energy available, one electron with
parallel spin in each until all are half full

9
Test Item File Questions: Multiple Choice 45, Algorithmic 16 – 19
10
Test Item File Questions: Multiple Choice 46 – 49, Algorithmic 20
11
Test Item File Questions: Multiple Choice 50 – 51, Algorithmic 21
46
 Chapter 5—Periodicity and the Electronic Structure of Atoms

C. Ground-state configuration – lowest-energy electron configuration

D. Degenerate orbitals – orbitals with the same energy level
E. Orbital-filling diagrams – electrons are represented by arrows
5.12. Anomalous Electron Configurations12
A. Unusual stability when subshells half-filled or filled – leads to anomalies in electron
configurations
B. Anomalies
1. Occur when energy differences between subshells small
2. Transfer of an electron from one subshell to another
a. Lowers total energy of the atom
b. Due to decrease in electron-electron repulsions
c. More than 40 anomalies
5.13. Electron Configurations and the Periodic Table 13
A. Valence-shell electrons – outermost shell of electrons
1. Elements in each group of the periodic table have similar valence-shell electron
configurations.
2. Most loosely held
3. Determine an element’s properties
B. Similar electron configurations explain why the elements in a given group have similar
chemical behavior.
C. Blocks of elements in the periodic table – depends upon the valence orbitals being filled
1. s-block elements – Groups 1A and 2A (filling of an s orbital)
2. p-block elements – Groups 3A through 8A (filling of p orbitals; ns orbitals are filled)
3. d-block elements – transition metals (filling of (n – 1)d orbitals)
4. f-block elements – lanthanide and actinide elements (filling of (n – 2) f orbitals)
5.14. Electron Configurations and Periodic Properties: Atomic Radii 14
A. Radius of an atom – half the distance between nuclei of two identical atoms when covalently
bonded together
B. Atomic radius
1. Increases down a group
2. Successively larger valence-shell orbitals occupied
C. Atomic radius
1. Decreases across a period
2. Due to increase in Zeff for valence-shell electrons across a period
a. Value of Zeff – dependent upon the amount of shielding felt by an electron
b. Amount of shielding – depends on both the shell and subshell of other electrons
c. Valence-shell electrons
i. Strongly shielded by electrons in inner shells
ii. Less strongly shielded by electrons in same shell – order: s > p > d > f
iii. Weakly shielded by electrons in same subshell
Inquiry – How Does Knowledge of Atomic Emission Spectra Help Us Build More Efficient Light
Bulbs?

12
Test Item File Questions: Multiple Choice 52, Algorithmic 22 – 23, Short Answer 22
13
Test Item File Questions: Multiple Choice 53 – 57, Algorithmic 24 – 35, Short Answer 23 – 24
14
Test Item File Questions: Multiple Choice 58, Algorithmic 36 – 41, Short Answer 25
 Chapter 5—Periodicity and the Electronic Structure of Atoms

CHAPTER 5
PERIODICITY AND THE ELECTRONIC STRUCTURE OF ATOMS

Teaching Tips, Points of Emphasis, and Common Misconceptions

Section 5.1 Radiation refers to any form of energy that travels in all directions from a single
source, such as light from the sun.

Section 5.1 Many students associate radiation only with nuclear decay processes and their
negative connotations. This form of radiation represents only a small segment of the
electromagnetic radiation spectrum.

Section 5.1 Wavelength can be related to colors of the spectrum ranging from 400 nm (violet) to
700 nm (red) using the acronym ROY G BIV (Red, Orange, Yellow, Green, Blue,
Indigo, Violet).

Section 5.1 Students best relate some wave properties to radio waves: the frequency of a favorite
radio station and loudness (amplitude).

Section 5.2 Wave-particle duality does not mean that energy is sometimes a wave and other
times a particle; it means we must use both wave and particle theories to describe
energy.

Section 5.2 A photon is a quantum of light energy.

Section 5.4 The Bohr model does not fit with the current understanding of atomic structure.

Section 5.4 For a single atom, transition of an electron from a higher to a lower energy level
results in the emission of one photon of light with an energy that corresponds to the
difference in energy of the two levels.

Section 5.7 Quantum number n is related to the size and energy of an orbital. The larger the
value of n, the larger the orbital and the higher the energy of an electron occupying
the orbital.

Section 5.7 Quantum number l defines orbital shape. Some students believe that the shape of an
orbital shows how the electron moves about the atom. An orbital defines the region
in which the electron moves with an indeterminable motion.

Section 5.7 Quantum number ml defines the different orientations an orbital of a given shape
may assume. This gives the number of orbitals of a given type: s orbital (one), p
orbital (three), d orbital (five), f orbital (seven).

Section 5.7 For neutral atoms 4s < 3d but for cations 3d < 4s in energy.

Section 5.8 An electron’s orbital is a wave theory concept. Since a wave exists simultaneously
on both sides of a node, an electron does not “move” from one lobe of an orbital to
another according to this mathematical model.

Section 5.8 The closer an electron is brought to the nucleus of an atom, the greater the energy of
the photon emitted and the lower the energy of the electron.

48
 Chapter 5—Periodicity and the Electronic Structure of Atoms

Section 5.8 The Planck equation is for a single photon or single electron energy. On a
macroscopic scale it is useful to convert to energy per mole of photons or electrons
by multiplying by Avogadro’s number.

Section 5.9 If a beam of atoms having one unpaired electron (such as atoms of silver) pass
through a magnetic field, half are attracted to one pole and half to the other pole of
the magnetic field.

Section 5.9 Electrons are said to be paired on an atom or ion if there are the same number of
electrons with ms = + 1/2 as with ms = – 1/2; any electron with ms = + 1/2 without a
corresponding electron with ms = – 1/2 is said to be unpaired. Experimentally, atoms
and ions that have only paired electrons are repelled from a magnetic field and are
called diamagnetic; atoms and ions with one or more unpaired electrons are attracted
to a magnetic field and are called paramagnetic.

Section 5.11 Electron orbital-filling diagrams explicitly show the number of unpaired electrons;
electron configurations do not. Students who ignore the use of orbital-filling
diagrams are prone to say that all electrons are paired on an atom with an electron
configuration such as 1s22s22p2.

Section 5.14 Core electron configuration does have some effect on the chemistry of an element.
Due to filling of the d orbitals , p-block elements in period 4 have an additional 10
core electrons relative to elements in period 3. This influences some properties, such
as atomic radius. A similar and more dramatic effect, called the lanthanide
contraction, caused by f orbital filling, occurs for period 6 d-block and p-block
elements.

Lecture/Laboratory Demonstration References

Section 5.3 N. C. Thomas and R. Brown, “A Spectacular Demonstration of Flame Tests,” J.
Chem. Educ., Vol. 69, 1992, 326. Brightly-colored flashes of light resulting from the
ignition of cellulose nitrate impregnated with salts of sodium, potassium, strontium,
and barium ions demonstrate light emission from these energetically excited ions.

Literature References
Section 5.2 Robert R. Perkins, “Put Body to Them,” J. Chem. Educ., Vol. 72, 1995, 151-152.
Analogies for quantized states.

Section 5.6 Bianca L. Haendler, “Presenting the Bohr Atom,” J. Chem. Educ., Vol. 59, 1982,
372-376.

Section 5.6 Oliver G. Ludwig, “On a Relation Between the Heisenberg and de Broglie
Principles,” J. Chem. Educ., Vol. 70, 1993, 28.

Section 5.6 Pedro L. Muino, “Introducing the Uncertainty Principle Using Diffraction of Light
Waves,” J. Chem. Educ., Vol. 77, 2000, 1025-1027.

Section 5.6 Lawrence S. Bartell, “Perspectives on the Uncertainty Principle and Quantum
Reality,” J. Chem. Educ., Vol. 62, 1985, 192-196.
 Chapter 5—Periodicity and the Electronic Structure of Atoms

Section 5.7 Ngai Ling Ma, “Quantum Analogies on Campus,” J. Chem. Educ., Vol. 73, 1996,
1016-1017.

Section 5.7 Mali Yin and Raymond S. Ochs, “The Mole, The Periodic Table, and Quantum
Numbers: An Introductory Trio,” J. Chem. Educ., Vol. 78, 2001, 1345-1347.

Section 5.7 Geoff Raynner-Canham, “A Student's Travels, Close Dancing, Bathtubs, and the
Shopping Mall: More Analogies in Teaching Introductory Chemistry,” J. Chem.
Educ., Vol. 71, 1994, 943-944.

Section 5.7 John J. Fortman, “Pictorial Analogies VII: Quantum Numbers and Orbitals,” J.
Chem. Educ., Vol. 70, 1993, 649-650.

Section 5.8 Elvin Hughes, Jr., and Arnold George, “Suitable Light Sources and Spectroscopes
for Student Observation of Emission Spectra in Lecture Halls,” J. Chem. Educ., Vol.
61, 1984, 908-909.

Section 5.11 Robert D. Freeman, “New Schemes for Applying the Aufbau Principle,” J. Chem.
Educ., Vol. 67, 1990, 576.

Section 5.11 James R. Hanley, III, and James R. Hanley, Jr., “A Low-Cost Classroom
Demonstration of the Aufbau Principle,” J. Chem. Educ., Vol. 56, 1979, 747.

Section 5.11 Ronald J. Gillespie, James N. Spencer, and Richard S. Moog, “Demystifying
Introductory Chemistry; Part 1. Electron Configurations from Experiment,” J.
Chem. Educ., Vol. 73, 1996, 617-622.

Section 5.11 Anthony Garofalo, “Housing Electrons: Relating Quantum Numbers, Energy Levels,
and Electron Configurations,” J. Chem. Educ., Vol. 74, 1997, 709-719.

Section 5.11 M. Bonneau, “The Quantum Shoe Store and Electron Structure,” J. Chem. Educ.,
Vol. 68, 1991, 837.

Section 5.12 Peter Cann, “Ionization Energies, Parallel Spins, and the Stability of Half-Filled
Shells,” J. Chem. Educ., Vol. 77, 2000, 1056-1061.

Section 5.13 Judith A. Strong, “The Periodic Table and Electron Configurations,” J. Chem. Educ.,
Vol. 63, 1986, 834.

Media References
Section 5.2 The Photoelectric Effect movie from the Instructor Resource DVD

Section 5.3 Flame Tests for Metals movie from the Instructor Resource DVD

Section 5.8 Shapes of Orbitals activity from the Instructor Resource DVD

Section 5.8 Radial Electron Distribution movie from the Instructor Resource DVD

Section 5.10 Line Spectrum of Sodium activity from the Instructor Resource DVD

Section 5.10 Effective Nuclear Charge movie from the Instructor Resource DVD

Section 5.11 Electron Configuration movie from the Instructor Resource DVD
50
 Chapter 5—Periodicity and the Electronic Structure of Atoms

Section 5.14 Periodic Trends: Atomic Radii movie from the Instructor Resource DVD