GENERAL CHEMISTRY

Principles and Modern Applications TENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

8
Electrons in
Atoms

PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND
BIOCHEMISTRY

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Chemical Compounds

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Chemical Compounds

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Vocabulary to know..

Wavelength- shortest distance between equivalent

points on a continuous wave
Symbol- λ (lambda)
Unit- meters, centimeters, or nanometers (1 nm=
1x10-9m)
Frequency- the number of waves that pass a give
point per second
Symbol- ν (nu)
Unit- Hertz (SI Unit)= (1/s)= (s-1)
Amplitude- the wave’s height from the origin to a
crest, or from the origin to a trough
 8-1 Electromagnetic Radiation

Electric and magnetic

fields propagate as waves
through empty space or
through a medium.
A wave transmits energy.

FIGURE 8-1
The simplest wave motion – traveling wave in a rope
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Low 

High 

This sketch of two different electromagnetic waves shows the propagation of mutually perpendicular
oscillating electric and magnetic fields. For a given wave, the wavelengths, frequencies, and amplitudes
of the electric and magnetic field components are identical. If these views are of the same instant of
time, we would say that (a) has the longer wavelength and lower frequency, and (b) has the shorter
wavelength and higher frequency.

FIGURE 8-2
Electromagnetic waves
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 Frequency, Wavelength and Speed of
Electromagnetic Radiation

Frequency () in Hertz—Hz or s-1.

Wavelength (λ) in meters—m.
cm m nm Å pm
(10-2 m) (10-6 m) (10-9 m) (10-10 m) (10-12 m)

Velocity (c)—2.997925  108 m s-1.

c = λ λ = c/  = c/λ

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 FIGURE 8-3
The electromagnetic spectrum

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a) In constructive interference, the troughs and crests are in step
(in phase), leading to addition of the two waves. (b) In destructive
interference, the troughs and crests are out of step (out of phase),
leading to cancellation of the two waves.
FIGURE 8-5
Interference in two overlapping light waves

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 FIGURE 8-4
Examples of interference

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 FIGURE 8-6
Refraction of light

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 (a) (b) (c) (d) (e)
Light emitted by an electric discharge through
(a)hydrogen gas and (b) neon gas.
(b)Light emitted when compounds of the alkali metals are
excited in the gas flames: (c) lithium, (d) sodium, and (e)
potassium.
FIGURE 8-8
Sources for light emission

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 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 by
other than visual or
photographic means, the term
generally used is spectrometer.

FIGURE 8-9
The atomic, or line, spectrum of helium

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 FIGURE 8-10
The Balmer series for hydrogen atoms – a line spectrum

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 8-3 Quantum Theory

Max Planck, 1900

Energy, like matter,
is discontinuous.
є = h
FIGURE 8-11
Spectrum of radiation given off by a heated body
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 Light emission by molten iron

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 The Photoelectric Effect

Heinrich Hertz, 1888

Light striking the surface of
certain metals causes
ejection of electrons.
 > o
threshold frequency

#e-  I
ek  
Albert Einstein 1905

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Schematic diagram of the apparatus for photoelectric effect measurements. (b) The
photoelectric current Ip, appears only if the frequency (n) is greater than the threshold
value. For (n > n0) the current (Ip) increases as the intensity of the light is increased. (c)
Stopping voltage of photoelectrons as a function of frequency of incident radiation. The
stopping voltage (ns) is plotted against the frequency of the incident radiation. The
threshold frequency (n0) of the metal is found by extrapolation.
FIGURE 8-12
The Photoelectric Effect

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 The Photoelectric Effect

At the stopping voltage the kinetic energy of the

ejected electron has been converted to potential.

The potential difference at this

point is called the stopping
1
mu2 = eVs voltage, At the stopping
2 voltage, the kinetic energy of
the photoelectrons has been
converted to potential energy,
At frequencies greater than o: expressed through the
following equation (in which m,
u and e are the mass, speed, and
Vs = k ( - o) charge of an electron,
respectively).

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 The Photoelectric Effect

eVo
Ek = eVs Eo = ho o =
h

eVo, and therefore o, are characteristic of the metal.

Conservation of energy requires that:

1
Ephoton = Ek + Ebinding h = mu2 + eVo
2
1
Ek = Ephoton - Ebinding eVs = mu2 = h - eVo
2

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 8-4 The Bohr Atom
-RH
E= 2
n

RH = 2.179  10-18 J

FIGURE 8-13
Bohr model of he hydrogen atom
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 -RH -RH
ΔE = Ef – Ei = – 2
nf 2
ni
1 1
= RH ( 2 – ) = h = hc/λ
ni nf2

FIGURE 8-14
Energy-level diagram for the hydrogen atom

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 Emission Absorption

FIGURE 8-15
Emission and absorption spectroscopy

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 Bohr Theory and the
Ionization Energy of Hydrogen

1 1
ΔE = RH ( 2 – 2 ) = h
ni nf

As nf goes to infinity for hydrogen starting in the ground state:

1
h = RH ( 2 ) = RH
ni

This also works for hydrogen-like species such as He+ and Li2+.

-Z2
En = RH ( 2 ) = -Z2RH
ni
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8-5 Two Ideas Leading to a New Quantum
Mechanics
Wave-Particle Duality To explain the photoelectric
Einstein suggested particle-like
properties of light could explain the effect, Einstein suggested that
photoelectric effect. light has particle-like properties,
Diffraction patterns suggest photons which are displayed through
are wave-like.
deBroglie, 1924
photons. Other phenomena,
Small particles of matter may at times however, such as the dispersion
display wavelike properties. of light into a spectrum by a
prism, are best understood in
terms of the wave theory of
light. Light, then, appears to
have a dual nature.

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 Wave-Particle Duality In order to use this equation for a material
particle, such as an electron, de Broglie
substituted for the momentum, p, its equivalent
E = mc2 —the product of the mass of the particle, m,
and its velocity, u. When this is done, we arrive
h = mc2 at de Broglie’s famous relationship.

h/c = mc = p De Broglie called the waves associated with

material particles “matter waves.” If matter
waves exist for small particles, then beams of
p = h/λ particles, such as electrons, should exhibit the
characteristic properties of waves, namely
diffraction.

λ = h/p = h/mu

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 FIGURE 8-16
Wave properties of electrons demonstrated

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 The Uncertainty Principle
h
Δx Δp ≥
4π

Heisenberg and Bohr

FIGURE 8-17
The uncertainty principle interpreted graphically
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 8-6 Wave Mechanics

Standing waves.
Nodes do not undergo
displacement.

λ = 2L, n = 1, 2, 3…
n

FIGURE 8-18
Standing waves in a string
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 FIGURE 8-19
The electron as a matter wave

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Particle in Box: Standing Waves, Quantum Particles,
and Wave Functions

ψ, psi, the wave function.

Should correspond to a standing
wave within the boundary of
the system being described.
Particle in a box.
2  n 
 sin  x
L  L 

FIGURE 8-20
The standing waves of a particle in a one-dimensional box
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 FIGURE 8-21
The probabilities of a particle in a one-dimensional box

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 Wave Functions of the Hydrogen Atom

Schrödinger, 1927 Eψ = H ψ

H (x,y,z) or H (r,θ,φ)
ψ(r,θ,φ) = R(r) Y(θ,φ)

R(r) is the radial wave function.

Y(θ,φ) is the angular wave function.

FIGURE 8-22
The relationship between spehrical polar coordinates and Cartesian coordinates

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 8-7 Quantum Numbers and Electron Orbitals

Principle quantum number, n = 1, 2, 3…

Angular momentum quantum number,

l = 0, 1, 2…(n-1)

l = 0, s
l = 1, p Magnetic quantum number,
l = 2, d ml= - l …-2, -1, 0, 1, 2…+l
l = 3, f

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 Principal Shells and Subshells

FIGURE 8-23
Shells and subshells of a hydrogen atom
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 9-8 Interpreting and Representing the Orbitals
of the Hydrogen Atom.

Represent the probability densities of the

orbitals of the hydrogen atom as three
dimensional surfaces.

Each orbital has a distinctive shape.

Acquire a broad qualitative understanding.

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 s orbitals

FIGURE 8-24
Three representations of the electron probability density for the 1s orbital
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 2s orbitals

FIGURE 8-24
Three-dimensional representations of the 95% electron probability density for the 1s, 2s and 3s orbitals

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 FIGURE 8-27
Three representations of electron probability for a 2p orbital

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 FIGURE 8-28
The three 2p orbitals

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 FIGURE 8-30
Representations of the five d orbitals

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 8-9 Electron Spin: A Fourth Quantum Number

FIGURE 8-32
Electron spin visualized
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 FIGURE 8-33
The Stern-Gerlach Experiment

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 8-10 Multi-electron Atoms

Schrödinger equation was for only one e-.

Electron-electron repulsion in multi-electron
atoms.
Hydrogen-like orbitals (by approximation).

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 Zeff is the effective nuclear charge.

FIGURE 8-35
Radial probability distributions

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 FIGURE 8-36
Orbital energy-level diagram for the first three electronic shells

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 8-11 Electron Configurations

Aufbau process
Electrons occupy orbitals in a way that minimizes
the energy of the atom.
Pauli exclusion principle
No two electrons can have all four quantum
numbers alike.
Hund’s rule
When orbitals of identical energy (degenerate orbitals)
are available, electrons initially occupy these orbitals
singly.
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 FIGURE 8-37
The order of filling of electronic subshells

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 Representing Electron Configurations

spdf notation (condensed) 1s22s22p2

spdf notation (expanded) 1s22s22px12py1

spdf notation

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 The Aufbau process

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 The Aufbau Process – Sc through Zn

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8-12 Electron Configurations and the Periodic Table

FIGURE 8-38

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 End of Chapter Questions

Test your decisions that you make while

solving a problem by continuing on a path
and seeing if they turn out to be:

a) sensible and b) useful.

You must validate your assumptions at some

point in your solution.

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