Chapter 6 Electronic Structure of atoms

6.1 Electromagnetic radiation

l =c -frequency, hertz, s
-1
, l-wavelength, meter, nm
c=3.0x10
8
m/s) 1m=10
9
nm

Sample Exercise 6.1 Concepts of Wavelength and
Frequency
Two electromagnetic waves are represented below.
(a) Which wave has the higher frequency? (b) If one wave
represents visible light and the other represents infrared
radiation, which wave is which?

Two electromagnetic waves are represented below.








(a) Which wave has the higher frequency? (b) If one wave represents visible light and the other represents
infrared radiation, which wave is which?

C= l c=2.9979x10
8
m/s, l -nm,
-1/s, s
-1
, hertz(hz), 1m=10
9
nm
Sample Exercise 7.1
The brilliant red colors seen in fireworks are due to the
emission of light with wavelengths around 650 nm when
strontium salts such as Sr(NO
3
)
2
and SrCO
3
are heated.
(This can be easily demonstrated in the lab by dissolving
one of these salts in methanol that contains a little water
and igniting the mixture in an evaporating dish.) Calculate
the frequency of red light of wavelength 6.50 X 10
2
nm.
(4.61x10
14
s
-1
)
Practice Exercise
(a) A laser used in eye surgery to fuse detached retinas
produces radiation with a wavelength of 640.0 nm.
Calculate the frequency of this radiation. (b) An FM radio
station broadcasts electromagnetic radiation at a frequency
of 103.4 MHz (megahertz; MHz = 106 s
1
). Calculate the
wavelength of this radiation. The speed of light is 2.998
10
8
m/s to four significant digits.
Answers: (a) 4.688 1014 s
1
, (b) 2.901 m

6.2 Quantized energy and photons
E=h
h-Planks constant=6.626x10
-34
J-s
E
photon
=hv
Sample Exercise 6.3 Energy of a Photon
Calculate the energy of one photon of yellow light with a
wavelength of 589 nm.
Practice Exercise
(a) A laser emits light with a frequency of 4.69 10
14
s
1
.
What is the energy of one photon of the radiation from this
laser? (b) If the laser emits a pulse of energy containing
5.0 10
17
photons of this radiation, what is the total
energy of that pulse? (c) If the laser emits 1.3 10
2
J of
energy during a pulse, how many photons are emitted
during the pulse?
Answers: (a) 3.11 10
19
J, (b) 0.16 J, (c) 4.2 10
16

photons
Atomic Spectra and Bohr
If e-s are in quantized energy
states, then E of states can
have only certain values.
This explain sharp line
spectra.
PLAY MOVIE
Energy
Adsorption/Emission
See Active Figure 6.9
Origin of Line Spectra
Balmer series
See Active Figure 6.10
E=(-2.178x10
-18
J)(Z
2
/n
2
) Z=nuclear charge=1 (hydrogen)
=(-2.178x10
-18
J)(1/n
2
)
DE=(-2.178x10
-18
J)(1/n
2
f
- 1/n
2
i
)
l=hC/DE
1/l=R
H
(1/n
2
f
- 1/n
2
i
) R
H
=Rydberg
constant=1.096776x10
7
m
-1

Sample Exercise 7.4 Energy Quantization in Hydrogen
Calculate the energy required to excite the hydrogen
electron from level n = 1 to level n = 2. Also calculate the
wavelength of light that must be absorbed by a hydrogen
atom in its ground state to reach this excited state.
(1.633x10
-18
)
Sample Exercise 6.4 Electronic Transitions in the Hydrogen
Atom
Using Figure 6.14, predict which of the following electronic
transitions produces the spectral line having the longest
wavelength: n = 2 to n = 1, n = 3 to n = 2, or n = 4 to n = 3.
Practice Exercise
Indicate whether each of the following electronic
transitions emits energy or requires the absorption of
energy: (a) n = 3 to n = 1; (b) n = 2 to n = 4.
Answers: (a) emits energy, (b) requires absorption of
energy.

DE=energy of level n
final
-energy of level n
initial
=-2.178x10
-18
J(1/n
final2
-1/ n
initial2
)
Sample Exercise 7.5 Electron Energies
Calculate the energy required to remove electron from a hydrogen
atom in its ground state.
6.3 The wave behavior of matter
E=mc
2
h=6.626x10
-34
J s or 6.626x10
-34
kg m
2
/s
1 J= 1 kg m
2
/s
2

m=h/l, or vinal=h/m (de Brolie's equation)
-velocity
m -momentum
Sample Exercise 7.3 Calculations of Wavelength
Compare the wavelength for an electron (mass = 9.11
X 10
-31
kg) traveling at a speed of 1.0 X 10
7
m/s with that
for a ball (mass = 0.10 kg) traveling at 35 m/s.
(7.27x10
-11
)
Sample Exercise 6.5 Matter Waves
What is the wavelength of an electron moving with a speed of
5.97 10
6
m/s? The mass of the electron is 9.11 10
31
kg.
Practice Exercise
Calculate the velocity of a neutron whose de Broglie
wavelength is 500 pm. The mass of a neutron is given in the
table inside the back cover of the text.
Answer: 7.92 10
2
m/s

Symbol Values Description
n (principal) 1, 2, 3, .. Orbital size
(shell) and energy
where E = -R(1/n
2
)
(angular 0, 1, 2, .. n-1 Orbital shape or
Azimuthal) or type
(subshell)

m
l
(magnetic) -..0..+ Orbital
orientation
#orbitals in shell = n
2
# of orbitals in subshell = 2 + 1
QUANTUM NUMBERS
QUANTUM NUMBERS
The shape, size, and energy of each orbital
is a function of 3 quantum numbers:
n (principal) f shell
(angular or azimuthal) f subshell
m

(magnetic) f designates an orbital
within a subshell

Subshells &
Shells
n = 1
n = 2
n = 3
n = 4
Types of
Atomic
Orbitals
See Active Figure 6.14

s- SPHERICAL in shape-1 orbital
p-dumbbell shaped-3 orbital
d-5 orbital
f-7 orbital

The angular momentum quantum number (l) indicates the shape of
the orbital (subshell). (l value is from 0 to n-1)
For specific main energy level, the number of orbital shapes
possible is equal to n, number of orbitals is n
2
, the number of
electrons is 2 n
2

Depending on its value of l, an orbital is assigned a letter
(s,p,d,f).
Value of l 0 1 2 3 4
letter used s p d f g
Sublevels in the atom
Principal sublevel sublevel
Level number, l letter
1 0 s
2 0, 1 s, p
3 0,1, 2 s, p, d
4 0,1,2,3 s, p, d, f
Orbitals in the atom
orbital number of number of
n l Designation m
l
orbitals, electrons
per sublevel
1 0 1s 0 1 2
2 0 2s 0 1 2
1 2p -1, 0, +1 3 6
3 0 3s 0 1 2
1 3p -1, 0, +1 3 6
2 3d -2, -1, 0, +1, +2 5 10
4 0 4s 0 1 2
1 4p -1, 0, +1 3 6
2 4d -2, -1, 0, +1, +2 5 10
3 4f -3, -2, -1, 0, +1, +2, +3 7 14

Sample Exercise 6.6 Subshells of the Hydrogen Atom
(a) Without referring to Table 6.2, predict the number of
subshells in the fourth shell, that is, for n = 4.
(b) Give the label for each of these subshells. (c) How
many orbitals are in each of these subshells?
Practice Exercise
(a) What is the designation for the subshell with n = 5 and
l = 1? (b) How many orbitals are in this subshell? (c)
Indicate the values of ml for each of these orbitals.
Answers: (a) 5p; (b) 3; (c) 1, 0, 1


Exercise 6.7 Using Quantum Numbers
Complete following Statements
(A) when n = 2, the values of l can be _____ and
_____.
(B) When l = 1, the values of ml can be_____,____,
and _____, and the subshell has the letter label ____.
(C) The subshell with l=2 is called a ______subshell
(D) when a subshell is labeled s, the value of l is
_____, and ml has the value_____.
(E) There are _______ orbitals in the p subshell
(F) When a subshell is labeled f, there are ___ values
of ml, corresponding to ___ orbitals
Practice: 1. An electron with the following four quantum
numbers may be an electron in an unfilled (outermost)
sublevel of S, N, Ag, Ca, Eu, I, or Cu
a. 3, 2, -1,+1/2
b. 4, 3, +2, -1/2
c. 2, 1, 0, +1/2
2. . All of the following sets of quantum numbers are
allowed EXCEPT
a. n = 1, = 0, m

= 0
b. n = 3, = 2, m

= +2
c. n = 4, = 3, m

= 1
d. n = 5, = 1, m

= 0
e. n = 6, = 2, m

= +3

Sample Exercise 7.6 Electron Subshells
For principal quantum level n = 5, determine the
number of allowed subshells (different values of ), and give
the designation of each.
1. Electron configuration-the arrangement of electrons in
an atom.
Rules governing electron configurations
a. Aufbau principle: an electron occupies the lowest-
energy orbital that can receive it.



b. Pauli exclusion principle: no two electrons in the same atom can
have the same set of four quantum numbers.
c. Hundis rule: orbitals of equal energy are each occupied by one
electron before any orbital is occupied by a second electron, and all
electrons in singly occupied orbitals must have the same spin.
Representing electron configurations: orbital notation, electron-
configuration notation and noble gas electron configuration.
Core electrons (inner shell) and valence electrons (outer shell)
Sample Exercise 6.7 Orbital Diagrams and Electron
Configurations
Draw the orbital diagram for the electron configuration of
oxygen, atomic number 8. How many unpaired electrons
does an oxygen atom possess?
Practice Exercise
(a) Write the electron configuration for phosphorus,
element 15. (b) How many unpaired electrons does a
phosphorus atom possess?
Answers: (a) 1s
2
2s
2
2p
6
3s
2
3p
3
, (b) three

Anomalous electron configuration (due to the closeness of
the 3d and 4s orbitals)
Chromium (Cr): [Ar]4s
1
3d
5
(Mo)

Copper (Cu): [Ar]4s
1
3d
10
(Ag, Au)
Palladium (Pd): [Kr]5s
0
4d
10
Nb(Niobium) [Kr]5s
1
4d
4
-----Rh(Rhodium) [Kr]5s
1
4d
8

Sample Exercise 7.7 Electron Configurations
Give the electron configurations for sulfur (s),
cadmium (Cd), hafnium (Hf), chromium (Cr), copper (Cu),
and radium (Ra) using the periodic table inside the front
cover of this book.
Sample Exercise 6.9 Electron Configurations from the
Periodic Table
(a) Write the electron configuration for bismuth, element
number 83. (b) Write the condensed electron configuration
for this element. (c) How many unpaired electrons does
each atom of bismuth possess?
Practice Exercise
Use the periodic table to write the condensed electron
configurations for (a) Co (atomic number 27)
(b) Te (atomic number 52).
Answers: (a) [Ar]4s
2
3d
7
or [Ar]3d
7
4s
2
, (b) [Kr]5s
2
4d
10
5p
4

or [Kr]4d
10
5s
2
5p
4

The p block element together with the s block element are
called the main group elements (or representative elements)
The d- block element are metals with typical metallic
properties and are often referred to as transition elements.
Diamagnetism: no unpaired electrons, repelled from a
magnetic field
Paramagnetism: unpaired electrons, attracted to
Sample exercise 7-7:an element has the electron configuration
[kr]4d
5
5s
1
. without looking at the periodic table, identify the
period, block, and group inn which element is located. Then
consult the periodic table to identify this element and the
others in its group.
Exercise: An electron with four quantum numbers 3, 2, -1, -1/2
may be an electron in an unfilled sublevel of Ca, Fe, Al, Ar,
Ag?
Sample Exercise 6.8 Electron Configurations for a Group
What is the characteristic valence electron configuration of the
group 7A elements, the halogens?
Practice Exercise
Which family of elements is characterized by an ns
2
np
2

electron configuration in the outermost occupied shell?
Answer: group 4A

Sample Integrative Exercise Putting Concepts Together
Boron, atomic number 5, occurs naturally as two isotopes,
10B and 11B, with natural abundances of 19.9% and
80.1%, respectively. (a) In what ways do the two isotopes
differ from each other? Does the electronic configuration of
10B differ from that of 11B? (b) Draw the orbital diagram
for an atom of 11B. Which electrons are the valence
electrons? (c) Indicate three major ways in which the 1s
electrons in boron differ from its 2s electrons. (d)
Elemental boron reacts with fluorine to form BF
3
, a gas.
Write a balanced chemical equation for the reaction of solid
boron with fluorine gas. (e) H
f
for BF
3
(g) is 1135.6 kJ
mol
1
. Calculate the standard enthalpy change in the
reaction of boron with fluorine. (f) When BCl
3
, also a gas at
room temperature, comes into contact with water, the two
react to form hydrochloric acid and boric acid, H
3
BO
3
, a
very weak acid in water. Write a balanced net ionic
equation for this reaction.