GENERAL CHEMISTRY

Principles and Modern Applications 8 th EDITION

Petrucci • Harwood • Herring

Chapter 8: Electrons in Atoms

Electrons in Atoms 8
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Electrons in Atoms CONTENTS

9-1 Electromagnetic Radiation

9-2 Atomic Spectra

9-3 Quantum Theory
9-4 The Bohr Atom
9-5 Two Ideas Leading to a New Quantum
Mechanics
9-7 Quantum Numbers and Electron Orbitals
9-8 Interpreting and Representing the Orbitals of
the Hydrogen Atom
9-9 Electron Spin: A Fourth Quantum Number
9-10 Multielectron Atoms
9-11 Electron Configurations
9-12 Electron Configurations and the Periodic Table

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8-1 Electromagnetic Radiation
• We can learn about electrons in atoms by studying the interactions of
electromagnetic radiation and matter.

• We will begin with background information about electromagnetic radiation and

then consider connections between electromagnetic radiation and atomic structure .

• Electromagnetic Radiation is a form of energy propagated as mutually

perpendicular electric and magnetic fields through a vacuum or through a medium,
such as glass.

• It includes visible light, infrared, ultraviolet, X-ray, and radiowaves.

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8-1 Electromagnetic Radiation

• Wave: a disturbance that transmits energy through a medium.

Example: Traveling wave in a rope.

• As a result of up-and-down hand motion, waves

pass along the rope from left to right.

• Electric and magnetic fields propagate as waves

through empty space or through a medium.
• A wave transmits energy.

The simplest wave motion –

traveling wave in a rope

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Wave

§ Trough: low points, where the rope is at its greatest depth below the centre line.

§ Crest: high points, where the rope is at its greatest height above the centre line.

§ Amplitude: the height of a crest of a wave above the centre line of the wave.

§ Wavelength (λ): the distance between successive crests or troughs of a wave

motion.

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Frequency, Wavelength and Speed of
Electromagnetic Radiation

§ Frequency (n): in wave motion, this is the number of wave crests or

troughs that pass through a given point in a unit of time. It is expressed by
the unit (time-1).

§ Hertz (Hz): the SI unit of frequency, equal to s-1.

§ Velocity: if the wavelength of the wave is 0.5 m and the frequency is 3 s-1,
the speed of the wave would be:

0.5 m x 3 s-1 = 1.5 m/s

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Frequency, Wavelength and Speed of
Electromagnetic Radiation

§ Wavelength (λ) in meters—m.

cm µm nm Å pm
(10-2 m) (10-6 m) (10-9 m) (10-10 m) (10-12 m)

§ Electromagnetic waves cannot be seen, but can be represented by a magnetic

field component in a plane perpendicular to the electric field component.

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Low n

Longer wavelength; lower frequency

High n

Shorter wavelength; higher frequency

Electromagnetic waves

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§ Electromagnetic radiation has a constant speed in a vacuum, referred to as
the speed of light (c).

§ The relationship between the speed of light, frequency and wavelength of

electromagnetic radiation is given by:

§ Velocity (c) c =n ×l = 2.997925 ´ 108 m s-1

c = λn λ = c/n n = c/λ

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The Electromagnetic Spectrum

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An Important Characteristic of Electromagnetic Waves

• Constructive interference: two sets of

waves intersect in phase and their crests
and troughs are additive

• Destructive interference: two sets of

waves intersect out of phase and lead to
cancellation

FIGURE 8-5
Interference in two overlapping light waves

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Examples of Interference

(a) Stones and ripples. (b) CD reflection-diffraction pattern

The dispersion of different wavelength components of a light beam through

the interference produced by reflection from a grooved surface is called
diffraction.
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The Visible Spectrum
• The speed of light is lower in any medium than it is in a vacuum. Also, the speed is
different in different media. As a consequence, light is refracted, or bent, when it passes
from one medium to another.

Refraction of Light

• Light is refracted (bent) as it passes from air into the glass prism, and again as it emerges
from the prism into air.
• Red light is refracted the least and blue light the most. The blue light strikes the prism at
such an angle that the beam undergoes an internal reflection before it emerges from the
prism.
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The spectrum of “white” light

• When a beam of white light is passed through a transparent medium, the wavelength
components are refracted differently.
• The light is dispersed into a band of colors, a spectrum.

a) Dispersion of light through a prism. Red light is refracted the least and violet light the
most when “white” light is passed through a glass prism. The other colors of the visible
spectrum are found between red and violet.
b) Rainbow near a waterfall. Water droplets are the dispersion medium.
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9-2 Atomic Spectra
• The visible spectrum is a continuous spectrum because the light being diffracted
consists of many wavelength components.
• If the source of a spectrum produces light having only a relatively small number of
wavelength components, then a discontinuous spectrum (line) is observed.

• Sources for Light Emission

Light emitted by an electric discharge through

(a) hydrogen gas and (b) neon gas.

Light emitted when compounds of the alkali metals are excited in the gas flames:
(c) lithium, (d) sodium, and (e) potassium.
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Atomic Spectra

• The Atomic (Line) Spectrum of Helium

The light passes

through a narrow
slit.

Electric discharge; Each wavelength

Atoms absorb component appears as an
energy and re-emit image of the slit.
Light is then
it as light.
dispersed by
a prism.
Helium There are five
lines in the
spectrum of
Components of light
helium
are detected on
Photographic film.

• The apparatus pictured here, in which the spectral lines are photographed, is called a
spectrograph.
• If the observations are made by visual sighting alone, the device is called a spectroscope.
• If the positions and brightness of the lines are measured and recorded, the device is
called a spectrometer. 17
• Each element has its own distinctive line spectrum—a kind of atomic fingerprint.

• Robert Bunsen (1811–1899) and Gustav Kirchhoff (1824–1887) developed the first
spectroscope and used it to identify elements.

• In 1860, they discovered a new element and named it cesium (Latin, caesius, sky
blue) because of the distinctive blue lines in its spectrum.

• They discovered rubidium in 1861 in a similar way (Latin, rubidius, deepest red).

• Still another element characterized by its unique spectrum is helium (Greek, helios, the
sun).

• Among the most extensively studied atomic spectra has been the hydrogen spectrum.
Light from a hydrogen lamp appears to the eye as a reddish purple color (Fig. 8-8a).

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The Balmer Series for Hydrogen Atoms – A Line Spectrum

• Light from a hydrogen lamp appears to the eye as a reddish purple color. The principal wavelength
component of this light is red light of wavelength 656.3 nm.
• Three other lines appear in the visible spectrum of atomic hydrogen, a greenish blue line at 486.1
nm, a violet line at 434.0 nm, and another violet line at 410.1 nm.

• The visible atomic spectrum of hydrogen

• In 1885, Johann Balmer, deduced a formula for the wavelengths of hydrogen spectral lines.
Balmer’s equation based on frequency, is

• In this equation, n is the frequency of the spectral line, and n must be an integer (whole number)
greater than 2.
• If n=3 is substituted into the equation, the frequency of the red line is obtained. If n = 4 is used in
equation, the frequency of the greenish blue line is obtained, and so on.
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• The fact that atomic spectra consist of only limited numbers of well-
defined wavelength lines provides a great opportunity to learn about the
structures of atoms.

• Atomic spectra suggests that only a limited number of energy values are
available to excited gaseous atoms.

• Classical (nineteenth-century) physics, however, was not able to provide

an explanation of atomic spectra.

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8-3 Quantum Theory
Blackbody Radiation
• Black body is an idealized object that absorbs all electromagnetic radiation that falls on it.
Because no light is reflected or transmitted, the object appears black when it is cold.
– However, a black body emits a temperature-dependent spectrum of light. This thermal
radiation from a black body is termed black-body radiation

We are aware that hot objects emit light of different colors, from the dull red of an
electric-stove heating element to the bright white of a light bulb filament
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Light emission by molten iron

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• Red hot objects have a spectral peak at ~ 675 nm.

• The sun has a blackbody temperature of ~ 5750 K.

• White hot objects have spectral properties that are comparable at all wavelengths.

• Objects emit radiation at all temperatures, not just at high temperature.

Max Planck, 1900

Spectrum of radiation given off by a heated body

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• Light emitted by a hot radiating object can be dispersed by a prism to produce a continuous
color spectrum.
• In Blackbody Radiation, Intensity (I) is inversely proportional to wavelength (λ), or,
Intensity (I) increases with increasing frequency (υ) (I proportional to 1/λ).
• Classical theory predicts continuous increase of intensity with frequency. However, in
reality the intensity drops off after specific wavelengths.
• Classical physics could not explain the emission of light by heated solids.
• It predicted that the intensity of the radiation emitted would increase indefinitely at higher
energy (lower wavelength).
• In 1900, Max Planck developed a formula that fit the data perfectly. However, he had to
make a radical assumption which led to a new view of energy and a new physics.
• Energy, like matter, is discontinuous.

Spectrum of radiation
given off by a heated body

Max Planck, 1900

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• Classical physics places no limitations on the amount of energy a system may possess,
whereas quantum theory limits this energy to a discrete set of specific values.

• The difference between any two allowed energies of a system also has a specific value, called
a quantum of energy.

• This means that when the energy increases from one allowed value to another, it increases by
a tiny jump, or quantum (Energy increases in only stepwise increments).

• Plank introduced the concept of QUANTA of energy.

E = nhυ,
E is energy, n is a positive integer, h = 6.62607 x 10-34 J.s (Planck’s constant) and υ is
requency in hertz (s-1).

• If the object’s radiation is emitted by the atoms, then the atoms themselves can emit only
certain quantities of energy.

Changes in Energy are given by

ΔE = Δnhυ

Between two adjacent energy levels, or absorption of one “quantum” of energy, Δn = 1, so,

ΔE = hυ
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The Photoelectric Effect

• Heinrich Hertz, 1888

Light striking the surface of certain metals causes
ejection of electrons.

• Light may cause electrons to be emitted from an electrode in a photocell.

• Long wavelength light (lower energy) does not have enough energy to cause the
electron to escape, regardless of its intensity.
• When light of a shorter wavelength (higher energy) light strikes the electrode,
electrons are released.
• The amount of current produced depends on the intensity of the light and
the energy of the escaping electrons depends on the wavelength of the light.

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§ Electron emission only occurs when the frequency of the incident light exceeds a
particular threshold value (no).

Ø n > no

§ The number of electrons emitted depends on the intensity of the incident light.
Ø #e- µ I

§ The kinetic energies of the emitted electrons depend on the frequency of the light.
Ø ek µ n

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• Electrons emitted through the photoelectric effect can be referred to as photoelectrons.

• The Wave model of light could not explain the photoelectron effect.

• Light must therefore have the properties of a particle as well. Light transfers energy
through photons.

• Photons: a “particle” of light. The energy of a beam of light is concentrated into these
photons. They have characteristic energy given by Planck’s equation:

E = hn

Albert Einstein 1905

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• At the stopping voltage (Vs) the kinetic energy of the ejected electron has been
converted to potential.
1
mu2 = eVs
2
• At frequencies greater than no:

Vs = k (n - no)
eVo
Ek = eVs Eo = hno Eo = eVo no =
h

eVo, and therefore no, are characteristic of the metal.

Conservation of energy requires that:
1
Ephoton = Ek + Ebinding hn = mu2 + eVo
2
1
Ek = Ephoton - Ebinding eVs = mu2 = hn - eVo eVo= hno
2
[Link] = hn photon - hno
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Photons of Light and Chemical Reactions

• Photochemical reactions: a chemical reaction that is induced by light.

Ø Photons can be thought of as reactants.

• Example: The production of ozone (O3) from oxygen (O2) molecules:

O 2 + hn → O + O

O2 + O + M → O3 + M

• Where the radiation is UV (λ = 242.4 nm) and M is some other entity (like N2(g))
that carries away excess energy and prevents the immediate dissociation of ozone.

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 8-4 The Bohr Atom

• In 1913 Niels Bohr postulated that for a hydrogen atom:

1. The electron moves in circular orbits about the nucleus with the motion
described by classical physics.

• The H atom has only certain allowable energy levels or stationary states.
• Each state is associated with a fixed circular orbit of the electron around the
nucleus.

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 8-4 The Bohr Atom

• In 1913 Niels Bohr postulated that for a hydrogen atom:

2. The electron has only a fixed set of allowed orbits, called stationary states.
The allowed orbits are those in which certain properties of the electron have
unique values.
As long as an electron remains in a given orbit, its energy is constant and no
energy is emitted.

The atom does not change energy while

the electron moves within an orbit.

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 8-4 The Bohr Atom

• In 1913 Niels Bohr postulated that for a hydrogen atom:

3. An electron can pass only from one allowed orbit to another. In such
transitions, fixed, discrete quantities of energy (quanta) are involved; either
emitted or absorbed.

The atom changes from one stationary state to another by absorbing or

emitting a photon whose energy equals the difference in energy between the
two stationary states.

Ephoton = Estate B − Estate A

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• Radii of allowed orbits in hydrogen: Bohr theory predicts

rn = n2 ao

where n = 1,2,3,… and ao = 53 pm (0.53 A). (8.5)

With expression (8.5), the energies of the allowed energy states, or

energy levels, of the hydrogen atom can be calculated.

Bohr model of the hydrogen atom

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• Energy level diagrams: when a free electron is attracted to the
nucleus and confined to the orbit, n, the electron energy is negative,
and given by:

-RH
E= 2
n
where RH = Rydberg constant for hydrogen RH = 2.179 ´ 10-18 J

Bohr model of the hydrogen atom

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• Energy level diagrams: a representation of the allowed energy states for
the electrons in an atoms. For hydrogen:

Energy-level diagram for the hydrogen atom

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• Ground state (n=1): the lowest energy state for the electrons in an atom or
molecule.

• Excited state (n=2, 3,..): when one or more electrons are promoted to a higher
energy level than in the ground state.

• When an electron drops from a higher to a lower numbered orbit, a unique

quantity of energy is emitted:

• The energy of the photon, either absorbed or emitted, is calculated in

accordance with Planck’s equation,
ΔE=hν

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