普化Ch06 Lecture

Chapter 6
Electronic
Structure of Atoms
© 2022 Pearson Education Ltd.

Electronic Structure
• This chapter is all about electronic structure—the
arrangement and energy of electrons.
• It may seem odd to start by talking about waves.
However, extremely small particles have properties that
can only be explained in this manner!

Waves
• To understand the electronic structure of atoms, one
must understand the nature of electromagnetic
radiation.
• Electromagnetic radiation moves as waves through
space at the speed of light. (2.998  108 m/s)
• The distance between corresponding points on
adjacent waves is the wavelength (λ).
Figure 6.1 Water waves.

© 2022 Pearson Education Ltd. Figure 6.2 Water waves.
Waves
• The number of waves passing
a given point per unit of time is
the frequency (ν).
• For waves traveling at the
same velocity, the longer the
wavelength, the smaller the
frequency.
• If the time associated with the
lines to the left is one second,
then the frequencies would be
Figure 6.3 Electromagnetic waves.
2 s–1 and 4 s–1, respectively.

Electromagnetic Radiation
• All electromagnetic radiation travels at the same
velocity: The speed of light (c) is 2.998 × 108 m/s.
• Different types of electromagnetic radiation have

different properties. Their differences are due to their
different wavelengths.
• The various types of electromagnetic radiation
arranged in order of increasing wavelength, a display
called the electromagnetic spectrum.

Electromagnetic Spectrum
Figure 6.4 The electromagnetic spectrum.

Electromagnetic Radiation
• There are many types of electromagnetic radiation.
• They have different wavelengths and energies from
each other.
• The typical wavelength unit used vary based on
the lengths.

Sample Exercise 6.1 Concepts of Wavelength and Frequency
Two electromagnetic waves are represented in the
margin. (a) Which wave has the higher frequency? (b) If
one wave represents visible light and the other represents
infrared radiation, which wave is which?
Solution
(a) Wave 1 has a longer wavelength
(greater distance between peaks). The
longer the wavelength, the lower the
frequency ( = c/). Thus, Wave 1
has the lower frequency, and Wave 2
has the higher frequency.
(b) The electromagnetic spectrum
(Figure 6.4) indicates that infrared
radiation has a longer wavelength
than visible light. Thus, Wave 1 is
infrared radiation.

Sample Exercise 6.1 Concepts of Wavelength and Frequency
Continued
Practice Exercise
A source of electromagnetic radiation produces infrared light. Which of the following could be the wavelength of
the light?
(a) 3.0 nm (b) 4.7 cm (c) 66.8 m (d) 34.5 µm (e) 16.5 Å

Sample Exercise 6.2 Calculating Frequency from Wavelength
The yellow light given off by a sodium vapor lamp used for public lighting has a wavelength of 589 nm. What is the
frequency of this radiation?
Solution
Analyze We are given the wavelength, , of the radiation and asked to calculate its frequency, .
Plan The relationship between the wavelength and the frequency is given by Equation 6.1. We can solve for  and
use the values of  and c to obtain a numerical answer. (The speed of light, c, is 3.00 × 108 m/s to three significant
figures.)
Solve Solving Equation 6.1 for frequency gives  = c/. When we insert the values for c and , we note that the
units of length in these two quantities are different. We use a conversion factor to convert the wavelength from
nanometers to meters, so the units cancel:
Check The high frequency is reasonable because of the short wavelength. The units are proper because frequency
has units of “per second,” or s –1.

Sample Exercise 6.2 Calculating Frequency from Wavelength
Continued
Practice Exercise
(a) A laser used in orthopedic spine surgery produces radiation with a wavelength of 2.10 µm. Calculate the frequency
of this radiation. (b) An FM radio station broadcasts electromagnetic radiation at a frequency of 103.4 MHz
(megahertz; 1 MHz = 106 s–1). Calculate the wavelength of this radiation. The speed of light is 2.998 × 10 8 m/s to four
significant figures.

Electronic Properties NOT
Explained by Waves
• Three observed properties associated with how atoms
interact with electromagnetic radiation can NOT be
explained by waves:
1) the emission of light from hot objects (blackbody
radiation)
2) the emission of electrons from metal surfaces on
which light is shone (the photoelectric effect)
3) emission of light from electronically excited gas
atoms (emission spectra)

The Nature of Energy
• The wave nature of light does not explain how an
object can glow when its temperature increases.
Figure 6.5 Color and temperature.

The Nature of Energy—Quanta
• Max Planck explained it by
assuming that energy comes in
packets called quanta (singular:
quantum).
• According to Planck’s theory, matter
can emit and absorb energy only in
whole number multiples of hv.
• Because the energy can be
released only in specific amounts,
we say that the allowed energies
are quantized
Figure 6.6 Quantized versus

continuous change in energy.
The Photoelectric Effect
• Einstein used quanta to explain
the photoelectric effect.
• Each metal has a different
energy at which it ejects
electrons. At lower energy,
electrons are not emitted.
• He concluded that energy is
proportional to frequency:
Energy of photon = E = hν
Figure 6.7 The photoelectric effect.
where h is Planck’s constant,
6.626 × 10−34 J∙s.

Sample Exercise 6.3 Energy of a Photon
Calculate the energy of one photon of yellow light that has a wavelength of 589 nm.
Solution
Analyze Our task is to calculate the energy, E, of a photon, given its wavelength,  = 589 nm.
Plan We can use Equation 6.1 to convert the wavelength to frequency:  = c/. We can then use Equation 6.3 to
calculate energy: E = h
Solve The frequency, , is calculated from the given wavelength, as shown in Sample Exercise 6.2:
The value of the Planck constant, h, is given both in the text and in the table of physical constants on the inside
back cover of the text; thus we can easily calculate E:
Comment If one photon of radiant energy supplies 3.37 × 10 –19 J, we calculate that one mole of these photons
will supply:

Sample Exercise 6.3 Energy of a Photon
Calculate the energy of one photon of yellow light that has a wavelength of 589 nm.
Practice Exercise
Which of the following expressions correctly gives the energy of a mole of photons with wavelength ?
(a) E = (b) E = (c) E = (d) E = (e) E =

Atomic Emissions
• Another mystery in the early twentieth century involved
the emission spectra observed from energy emitted by
atoms and molecules.
• Niels Bohr offered a theoretical explanation of line
spectra.

Continuous vs. Line Spectra
• For atoms and molecules, one does not observe a
continuous spectrum (the “rainbow”), as one gets
from a white light source.
• A continuous visible spectrum is produced when a
narrow beam of white light is passed through a prism.
Figure 6.8 Creating a spectrum.

• When a high voltage is applied to tubes that contain
different gases under reduced pressure, the gases
emit different colors of light.
Figure 6.9 Atomic emission of hydrogen and neon.

• When light coming from such tubes is passed through
a prism, only a few wavelengths are present in the
resultant spectra.
• Only a line spectrum of discrete wavelengths is
observed. Each element has a unique line spectrum.
Figure 6.10 Line spectra of hydrogen and neon.

The Hydrogen Spectrum
• Johann Balmer (1885) discovered a simple formula
relating the four lines to integers.
• Johannes Rydberg advanced this formula. (RH is called
the Rydberg constant.)
• Neils Bohr explained why this mathematical relationship

works.

The Bohr Model
• Niels Bohr adopted Planck’s assumption and explained
these phenomena in this way:
1. Only orbits of certain radii, corresponding to specific
energies, are permitted for the electron in a hydrogen atom.
2. An electron in a permitted orbit is in an “allowed” energy
state. An electron in an allowed energy state does not
radiate energy, and, therefore, does not spiral into the
nucleus.
3. Energy is emitted or absorbed by the electron only as the
electron changes from one energy state to another. This
energy is is emitter of absorbed as a photon that has
energy E = h.
The Bohr Model
• Electrons in the lowest energy
state are in the ground state.
• Any energy higher is called an
excited state.
• Since each orbit has a specific
value compared to RH, transitions
from one energy level to another
can be calculated:
Figure 6.11 Energy levels in

the hydrogen atom from
the Bohr model.
Values of Transitions
• What do the values mean
using the Bohr Model?
• A positive ΔE means energy
is absorbed. A photon is
absorbed in this instance.
This happens if nf > ni.
• A negative ΔE means energy
is released. A photon is
emitted in this instance. This
happens if nf < ni.
Figure 6.12 Change in energy states
for absorption and emission of a
photon in a hydrogen atom.

Sample Exercise 6.4 Electronic Transitions in the Hydrogen Atom
In the Bohr model of the hydrogen atom, electrons are confined to orbits with fixed radii, and those radii can be
calculated. The radii of the first four orbits are 0.53, 2.12, 4.76, and 8.46 Å, respectively, as depicted below.
(a) If an electron makes a transition from the ni = 4 level to a lower-energy level, nf = 3, 2, or 1, which transition
would produce a photon with the shortest wavelength?
(b) What are the energy and wavelength of such a photon, and in which region of the electromagnetic spectrum
does it lie?
(c) The image on the right shows the output of a detector that measures the intensity of light emitted from a
sample of hydrogen atoms that have been excited so that each atom begins with an electron in the n = 4 state.
What is the final state, nf, of the transition being detected?

Continued
Solution
Analyze We are asked to determine the energy and wavelength associated with various transitions involving an
electron relaxing from the n = 4 state of the hydrogen atom to one of three lower-energy states.
Plan Given the integers representing the initial and final states of the electron, we can use Equation 6.6 to
calculate the energy of the photon emitted and then use the relationships E = h and c =  to convert energy to
wavelength. The photon with the highest energy will have the shortest wavelength because photon energy is
inversely proportional to wavelength.
Solve
(a) The wavelength of a photon is related to its energy through the relationship E = h = hc/. Hence, the photon
with the smallest wavelength will have the largest energy. The energy levels of the electron orbits decrease as n
decreases.
The electron loses the most energy on transitioning from the ni = 4 state to the nf = 1 state, and the photon
emitted in that transition has the highest energy and the smallest wavelength.
(b) We first calculate the energy of the photon using Equation 6.6 with ni = 4 and nf = 1:

Continued
Next we rearrange Planck’s relationship to calculate the frequency of the emitted photon.
Finally, we use the frequency to determine the wavelength.
Light with this wavelength falls in the ultraviolet region of the electromagnetic spectrum.
(c) From the graph, we estimate the wavelength of the photon to be approximately 480 nm. Starting from the
wavelength, it is easiest to estimate nf using Equation 6.4:
Rearranging:
So nf = 2, and the photons seen by the detector are those emitted when an electron transitions from the nf = 4 to
the nf = 2 state.

Continued
Check Referring back to Figure 6.12, we confirm that the n = 4 to n = 1 transition should have the largest energy of
the three possible transitions.
Practice Exercise
In the top part of Figure 6.10, the four lines in the H atom spectrum are due to transitions from a level for which ni > 2
to the nf = 2 level. What is the value of ni for the red line in the spectrum? (a) 3 (b) 4 (c) 5 (d) 6 (e) 7

Limitations of the Bohr Model
• It only works for hydrogen!
• Classical physics would result in an electron falling
into the positively charged nucleus. Bohr simply
assumed it would not!
• Circular motion is not wave-like in nature.

Important Ideas from the
Bohr Model
• Points that are incorporated into the current atomic
model include the following:
1) Electrons exist only in certain discrete energy
levels, which are described by quantum numbers.
2) Energy is involved in the transition of an electron
from one level to another.

The Wave Nature of Matter
• Louis de Broglie theorized
that if light can have material
properties, matter should
exhibit wave properties.
• He demonstrated that the
relationship between mass
and wavelength was:
Figure 6.13 Electrons as waves.
The wave nature of light

is used to produce this
electron micrograph of
graphene.

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.
Solution
Analyze We are given the mass, m, and velocity, , of the electron, and we must calculate its de Broglie
wavelength, .
Plan The wavelength of a moving particle is given by Equation 6.8, so  is calculated by inserting the known
quantities h, m, and . In doing so, however, we must pay attention to units.
Solve
Using the value of the Planck constant: h = 6.626 × 10–34 J-s
we have the following:
Comment By comparing this value with the wavelengths of electromagnetic radiation shown in Figure 6.4, we see
that the wavelength of this electron is about the same as that of X rays.

Sample Exercise 6.5 Matter Waves
Continued
Practice Exercise
Consider the following three moving objects: (i) a golf ball with a mass of 45.9 g moving at a speed of 50.0 m/s,
(ii) An electron moving at a speed of 3.50 × 10 5 m/s, (iii) A neutron moving at a speed of 2.3 × 10 2 m/s. List the three
objects in order from shortest to longest de Broglie wavelength.
(a) i < iii < ii (b) ii < iii < i (c) iii < ii < i (d) i < ii < iii (e) iii < i < ii

The Uncertainty Principle
• Heisenberg showed that the
more precisely the momentum
of a particle is known, the less
precisely its position is known:
uncertainty principle
It is impossible for us to know Figure 6.14 Werner Heisenberg
simultaneously both the exact (1901–1976).
momentum of the electron
and its exact location in
space.
Quantum Mechanics
• Austrian physicist Erwin Schrödinger reated the electron in a
hydrogen atom like the wave on a plucked guitar string.
• Because such waves do not travel in space, they are called
standing waves.
Figure 6.15 Standing waves

in a vibrating string.
Quantum Mechanics
• Erwin Schrödinger developed a
mathematical treatment into
which both the wave and particle
nature of matter could be
incorporated.
• This is known as quantum
mechanics.
Figure 6.16 Electron-density

distribution.
Quantum Mechanics
• The solution of Schrödinger’s
wave equation for hydrogen
yields wave functions for the
electron.
• The square of the wave
function gives the electron
density, or probability of
where an electron is likely to
be at any given time.
Figure 6.16 Electron-density

distribution.
Quantum Numbers
• Solving the wave equation gives a set of wave
functions, or orbitals, and their corresponding
energies.
• Each orbital describes a spatial distribution of electron
density.
• An orbital is described by a set of three quantum
numbers.

Principal Quantum Number (n)
• The principal quantum number, n, describes the
energy level on which the orbital resides.
• The values of n are integers ≥ 1.
• These correspond to the values in the Bohr model.

Angular Momentum Quantum Number (l)
• This quantum number defines the shape of the orbital.
• Allowed values of l are integers ranging from 0 to n − 1.
• Letter designate the different values of l. This defines
the shape of the orbitals.

Magnetic Quantum Number (ml)
• The magnetic quantum number describes the three-
dimensional orientation of the orbital.
• Allowed values of ml are integers ranging from −l to l
including 0:
−l ≤ ml ≤ l
• Therefore, on any given energy level, there can be up

to 1 s orbital, 3 p orbitals, 5 d orbitals, 7 f orbitals, and
so forth.

Magnetic Quantum Number (ml)
• Orbitals with the same value of n form an electron shell.
• Different orbital types within a shell are subshells.

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?
Solution
Analyze and Plan We are given the value of the principal quantum number, n. We need to determine the allowed values
of l and ml for this given value of n and then count the number of orbitals in each subshell.
Solve There are four subshells in the fourth shell, corresponding to the four possible values of l (0, 1, 2, and 3).
These subshells are labeled 4s, 4p, 4d, and 4f. The number given in the designation of a subshell is the principal
quantum number, n; the letter designates the value of the angular momentum quantum number, l: for l = 0, s; for l = 1, p;
for l = 2, d; for l = 3, f.

Sample Exercise 6.6 Subshells of the Hydrogen Atom
Continued
There is one 4s orbital (when l = 0, there is only one possible value of ml: 0). There are three 4p orbitals (when l = 1,
there are three possible values of ml: 1, 0, –1). There are five 4d orbitals (when l = 2, there are five allowed values of
ml: 2, 1, 0, –1, –2). There are seven 4f orbitals (when l = 3, there are seven permitted values of ml: 3, 2, 1, 0, –1, –2, –3).
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.

s Orbitals
• The value of l for s orbitals is 0.
• They are spherical in shape.
• The radius of the sphere increases with the value of n.
Figure 6.19 Comparison of the 1s, 2s, and 3s orbitals.

s Orbitals
• For an ns orbital, the number of peaks is n.
• For an ns orbital, the number of nodes (where there is zero
probability of finding an electron) is n – 1.
• As n increases, the electron density is more spread out and
there is a greater probability of finding an electron further from
the nucleus.
Figure 6.18 Radial probability functions for the 1s, 2s, and 3s
orbitals of hydrogen.
Probability Density and
Radial Probability Function
Figure 6.20 Comparing probability density [ψ(r)]2 and radial probability

function 4πr 2[ψ(r)]2.

Probability Density and
Radial Probability Function
Figure 6.21 Probability density [ψ(r)]2 in the 1s, 2s, and 3s orbitals of hydrogen.

p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node between them.
Figure 6.22 The p orbitals.

d Orbitals
• The value of l for a d orbital is 2.
• Four of the five d orbitals have four lobes; the other
resembles a p orbital with a doughnut around the center.
Figure 6.23 Contour representations

of the five d orbitals.

f Orbitals
• Very complicated shapes (not shown in text)
• Seven equivalent orbitals in a sublevel
• l=3

Energies of Orbitals—Hydrogen
• For a one-electron
hydrogen atom, orbitals
on the same energy level
have the same energy.
• Chemists call them
degenerate orbitals.
Figure 6.17 Energy levels

in the hydrogen atom.
Energies of Orbitals—
Many-electron Atoms
• As the number of electrons
increases, so does the
repulsion between them.
• Therefore, in atoms with more
than one electron, not all
orbitals on the same energy
level are degenerate.
• Orbital sets in the same
sublevel are still degenerate.
• Energy levels start to overlap
in energy (e.g., 4s is lower
in energy than 3d.) Figure 6.24 General energy ordering
of orbitals for a many-electron atom.

Spin Quantum Number, ms
• In the 1920s, it was discovered that two electrons in
the same orbital do not have exactly the same energy.
• The “spin” of an electron describes its magnetic field,
which affects its energy.
• This led to the spin quantum number, ms.
• The spin quantum number has only two allowed
values, +½ and –½.
Figure 6.25 Electron spin.

Pauli Exclusion Principle
• No two electrons in the same atom can have the
same set of four quantum numbers.
• Therefore, no two electrons in the same atom can
have the exact same energy.
• This means that every electron in an atom must differ
by at least one of the four quantum number values: n,
l, ml, and ms.

Nuclear Spin and MRI Image
Figure 6.26 Nuclear spin. Figure 6.27 MRI image.

Electron Configurations
• The way electrons are distributed in an atom is called
its electron configuration.
• The most stable organization is the lowest possible
energy, called the ground state.
• Each component consists of
– a number denoting the energy level;
– a letter denoting the type of orbital;
– a superscript denoting the number of electrons in those
orbitals.
4p 5
4p 5
4p 5
Orbital Diagrams
• Each box in the diagram represents one orbital.
• Half-arrows represent the electrons.
• The direction of the arrow represents the relative spin
of the electron.

Hund’s Rule
“When filling degenerate orbitals the lowest
energy is attained when the number of electrons
having the same spin is maximized.”
• This means that, for a set of orbitals in the same

sublevel, there must be one electron in each
orbital before pairing and the electrons have the
same spin, as much as possible.

Hund’s Rule

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?
Solution
Analyze and Plan Because oxygen has an atomic number of 8, each
oxygen atom has eight electrons. Figure 6.25 shows the ordering of
orbitals. The electrons (represented as half arrows) are placed in the
orbitals (represented as boxes) beginning with the lowest-energy
orbital, the 1s. Each orbital can hold a maximum of two electrons
(the Pauli exclusion principle). Because the 2p orbitals are
degenerate, we place one electron in each of these orbitals (spin-up)
before pairing any electrons (Hund’s rule).
Solve Two electrons each go into the 1s and 2s orbitals with their
spins paired. This leaves four electrons for the three degenerate
2p orbitals. Following Hund’s rule, we put one electron into each
2p orbital until all three orbitals have one electron each. The fourth
electron is then paired up with one of the three electrons already in a
2p orbital, so that the orbital diagram is

Sample Exercise 6.7 Orbital Diagrams and Electron Configurations
Continued
The corresponding electron configuration is written 1s22s22p4. The atom has two unpaired electrons.
Practice Exercise
How many of the elements in the second row of the periodic table (Li through Ne) will have at least one unpaired
electron in their electron configurations?
(a) 3 (b) 4 (c) 5 (d) 6 (e) 7

Condensed Electron Configurations
• Elements in the same group of the periodic
table have the same number of electrons in
the outer most shell. These are the valence
electrons.
• The filled inner shell electrons are called core
electrons. These include completely filled d or
f sublevels.
• We write a shortened version of an electron
configuration using brackets around a noble
gas symbol and listing only valence electrons.
Figure 6.28 The condensed

electron configurations of the
alkali metals (group 1A in the
periodic table).
Transition Metals
• Argon (atomic number 18)
ends period 3. Its electron
configuration is
1s22s22p63s23p6.
• Potassium (atomic number
19) might be expected to
have electrons in 3d. BUT 4s
fills next.
• Transition metals follow the
filling of 4s by filling 3d in the
4th period. Figure 6.24 General energy ordering of
orbitals for a many-electron atom.

Lanthanides and Actinides
• The elements which fill the f orbitals have special
names as a portion of a period, not as a group.
• The lanthanide elements (atomic numbers
57 to 70) have electrons entering the 4f sublevel.
• The actinide elements (including Uranium, at. no. 92,
and Plutonium, at. no. 94) have electrons entering the
5f sublevel.

Electron Configurations
• All group 2 elements have an
ns2 outer configuration
• All group 3 elements have an
ns2np1 outer configuration

Periodic Table
• We fill orbitals in increasing order of energy.
• Different blocks on the periodic table correspond to different
types of orbitals: s = blue, p = pink (s and p are
representative elements); d = orange (transition elements); f
= tan (lanthanides and actinides, or inner transition elements)
• The s and p blocks are called the main-group elements.
Figure 6.29 Regions of the periodic table.

Periodic Table and
Electron Configuration
• The periodic table is followed directly when determining
the electron configuration for MOST elements.

Sample Exercise 6.8 Electron Configurations for a Group
What is the characteristic valence electron configuration of the group 17 elements, the halogens?
Solution
Analyze and Plan We first locate the halogens in the periodic table, write the electron configurations for the first two
elements, and then determine the general similarity between the configurations.
Solve The first member of the halogen group is fluorine (F, element 9). Moving backward from F, we find that the
noble-gas core is [He]. Moving from He to the element of next higher atomic number brings us to Li, element 3.
Because Li is in the second period of the s block, we add electrons to the 2s subshell. Moving across this block gives
2s2. Continuing to move to the right, we enter the p block. Counting the squares to F gives 2p5. Thus, the condensed
electron configuration for fluorine is
The electron configuration for chlorine, the second halogen, is
From these two examples, we see that the characteristic valence electron configuration of a halogen is ns2np5, where n
ranges from 2 in the case of fluorine to 6 in the case of astatine.

Sample Exercise 6.8 Electron Configurations for a Group
Continued
Practice Exercise
Which group of elements is characterized by an ns2np2 electron configuration in the outermost occupied shell?

Sample Exercise 6.9 Electron Configurations from the Periodic Table
(a) Based on its position in the periodic table, write the condensed electron configuration for bismuth, element 83.
(b) How many unpaired electrons does a bismuth atom have?
Solution
(a) Our first step is to write the noble-gas core. We do this by locating bismuth, element 83, in the periodic table. We
then move backward to the nearest noble gas, which is Xe, element 54. Thus, the noble-gas core is [Xe].
Next, we trace the path in order of increasing atomic numbers from Xe to Bi. Moving from Xe to Cs, element 55,
we find ourselves in period 6 of the s block. Knowing the block and the period identifies the subshell in which we
begin placing outer electrons, 6s. As we move through the s block, we add two electrons: 6s2.
As we move beyond the s block, from element 56 to element 57, the curved arrow below the periodic table
reminds us that we are entering the f block. The first row of the f block corresponds to the 4f subshell. As we move
across this block, we add 14 electrons: 4f 14.
With element 71, we move into the third row of the d block. Because the first row of the d block is 3d, the second
row is 4d and the third row is 5d. Thus, as we move through the ten elements of the d block, from element 71 to
element 80, we fill the 5d subshell with ten electrons: 5d10.
Moving from element 80 to element 81 puts us into the p block in the 6p subshell. (Remember that the principal
quantum number in the p block is the same as that in the s block.) Moving across to Bi requires three electrons:
6p3. The path we have taken is Putting the parts together, we obtain the condensed electron configuration:
[Xe]6s24f 145d106p3. This configuration can also be written with the subshells arranged in order of increasing
principal quantum number: [Xe]4f 145d106s26p3.

Continued
Finally, we check our result to see if the number of electrons equals the atomic number of Bi, 83: Because Xe has
54 electrons (its atomic number), we have 54 + 2 + 14 + 10 + 3 = 83. (If we had 14 electrons too few, we would
realize that we have missed the f block.)
(b) We see from the condensed electron configuration that the only partially occupied subshell is 6p. The orbital
diagram representation for this subshell is
In accordance with Hund’s rule, the three 6p electrons occupy the three 6p orbitals singly, with their spins parallel.
Thus, there are three unpaired electrons in the bismuth atom.

Continued
Practice Exercise
A certain atom has a [noble gas]5s24d105p4 electron configuration. Which element is it?
(a) Cd (b) Te (c) Sm (d) Hg (e) More information is needed

Some Anomalies
• Some irregularities occur when there are enough
electrons to half-fill s and d orbitals on a given row.
Figure 6.30 Outer-shell

electron configurations
of the elements.

Chromium as an Anomaly
• For instance, the electron configuration for chromium
is
[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4.
• This occurs because the 4s and 3d orbitals are very
close in energy.
• These anomalies occur in f-block atoms with f and d
orbitals, as well.

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 ways in which the 1s electrons in boron differ from its 2s electrons. (d) Elemental boron reacts with
fluorine to form BF3, a gas. Write a balanced chemical equation for the reaction of solid boron with fluorine gas. (e)
for BF3(g) is –1135.6 kJ/mol. Calculate the standard enthalpy change in the reaction of boron with fluorine. (f) Will
the mass percentage of F be the same in 10BF3 and 11BF3? If not, why is that the case?
Solution
(a) The two isotopes of boron differ in the number of neutrons in the nucleus. (Sections 2.3 and 2.4) Each of
the isotopes contains five protons, but B contains five neutrons, whereas B contains six neutrons. The two
10 11
isotopes of boron have identical electron configurations, 1s22s22p1, because each has five electrons.
(b) The complete orbital diagram is
The valence electrons are the ones in the outermost occupied shell, the 2s2 and 2p1 electrons. The 1s2 electrons
constitute the core electrons, which we represent as [He] when we write the condensed electron configuration,
[He]2s22p1.

Continued
(c) The 1s and 2s orbitals are both spherical, but they differ in three important respects: First, the 1s orbital is lower
in energy than the 2s orbital. Second, the average distance of the 2s electrons from the nucleus is greater than
that of the 1s electrons, so the 1s orbital is smaller than the 2s. Third, the 2s orbital has one node, whereas the 1s
orbital has no nodes (Figure 6.19).

Continued
(d) The balanced chemical equation is
2 B(s) + 3 F2(g) 2 BF3(g)
(e) ΔH ° = 2(−1135.6) − [0 + 0] = −2271.2 kJ. The reaction is strongly exothermic.

(f) As we saw in Equation 3.10 (Section 3.3), the mass percentage of an element in a substance depends on the
formula weight of the substance. The formula weights of 10BF3 and 11BF3 are different because of the difference in
the masses of the two isotopes (the isotope masses of 10B and 11B are 10.01294 and 11.00931 u, respectively). The
denominators in Equation 3.10 would therefore be different for the two isotopes, whereas the numerators would
remain the same.

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Chapter 6

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Figure 6.1 Water waves.

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• Different types of electromagnetic radiation have

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Figure 6.4 The electromagnetic spectrum.

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Figure 6.5 Color and temperature.

Figure 6.6 Quantized versus

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(a) E = (b) E = (c) E = (d) E = (e) E =

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Figure 6.8 Creating a spectrum.

Figure 6.9 Atomic emission of hydrogen and neon.

Figure 6.10 Line spectra of hydrogen and neon.

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• Neils Bohr explained why this mathematical relationship

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Figure 6.11 Energy levels in

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Finally, we use the frequency to determine the wavelength.

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Figure 6.13 Electrons as waves.

The wave nature of light

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we have the following:

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Figure 6.15 Standing waves

Figure 6.16 Electron-density

Figure 6.16 Electron-density

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• Therefore, on any given energy level, there can be up

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Figure 6.19 Comparison of the 1s, 2s, and 3s orbitals.

Figure 6.20 Comparing probability density [ψ(r)]2 and radial probability

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Figure 6.22 The p orbitals.

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Figure 6.23 Contour representations

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