Petrucci’s General Chemistry
P R I N C I P L E S A N D M O D E R N A P P L I C AT I O N S
Twelfth Edition
PETRUCCI HERRING MADURA BISSONNETTE
Electrons in Atoms 8
Electrons in Atoms
CONTENTS
8-1 Electromagnetic Radiation
8-2 Prelude to Quantum Theory
8-3 Energy Levels, Spectrum, and
Ionization Energy of the Hydrogen
Atom
8-4 Two Ideas Leading to a New
Quantum Mechanics
8-5 Wave Mechanics
8-6 Quantum Theory of the Hydrogen
Atom
8-7 Interpreting and Representing the
Orbitals of the Hydrogen Atom
Electrons in Atoms
CONTENTS
8-8 Electron Spin: A Fourth Quantum
Number
8-9 Multielectron Atoms
8-10 Electron Configurations
8-11 Electron Configurations and the
Periodic Table
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
FIGURE 8-2
Electromagnetic waves
Frequency, Wavelength and Speed of
Electromagnetic Radiation
Frequency (ν) in Hertz—Hz or s −1.
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)
Velocity (c) 2.99792458 × 108 m s −1.
c=ν×λ
FIGURE 8-3
The electromagnetic spectrum
FIGURE 8-4
Examples of interference
FIGURE 8-5
Interference in two overlapping light waves
FIGURE 8-6
Refraction of light
The Visible Spectrum
FIGURE 8-7
The spectrum of “white” light
8-2 Prelude to Quantum Theory
Light emission by molten iron
Blackbody Radiation
FIGURE 8-8
Spectrum of radiation given off by a heated body
Max Planck, 1900
Energy, like matter,
is discontinuous.
E = hν
Max Planck (1858-1947)
The Photoelectric Effect
Heinrich Hertz, 1888
Light striking the surface of certain metals causes ejection of electrons
when ν > νo , the threshold frequency
• number of e– depends on intensity of incident light
• kinetic energies of e– depend on the frequency of
the light
Einstein proposed electromagnetic
radiation has particle-like properties
Ephoton = hν
Albert Einstein (1879-1955)
FIGURE 8-9
The Photoelectric Effect
At the stopping voltage the kinetic energy of the ejected
electron has been converted to potential.
1
mu2 = eVs
2
At frequencies greater than νo:
Vs = k (ν - νo)
The threshold frequency is given by
By conservation of energy we have
Since Ephoton=hν and Φ = eV0
which gives
Atomic Emission Spectra
FIGURE 8-10
Sources for light emission
FIGURE 8-11
The atomic, or line, spectrum of helium
1885 Johan Balmer
1888 Johannes Rydberg
FIGURE 8-12
The Balmer series for hydrogen atoms – a line spectrum
An Early Attempt to Understand Atomic
Emission Spectra: The Bohr Model
1. The electron moves about the nucleus with speed u in one
of a fixed set of circular orbits; as long as the electron
remains in a given orbit, its energy is constant and no
energy is emitted. Thus, each orbit is characterized by a
fixed radius, r, and a fixed energy, E.
2. The electron’s angular momentum, l = mur , is an integer
multiple of, (h/2π) that is l = n (h/2π), with n = 1, 2, 3, and
so on.
3. An atom emits energy as a photon when the electron falls
from an orbit of higher energy and larger radius to an orbit
of lower energy and smaller radius.
–RH
E= n = 1, 2, 3 …
n2
RH = 2.179 × 10 −18 J
Neils Bohr (1885-1962)
8-3 Energy levels, Spectrum, and Ionization
Energy of the Hydrogen Atom
Spectroscopy and Atomic Line Spectra
Ground state: electron in lowest energy level (n = 1)
Excited state: an electron that gains a quantum of energy, it
moves to a higher level (n=2, 3, and so on)
−R −R
H H
ΔE = Ef – Ei = –
nf2 ni2
1 1
= RH ( – ) = hν = hc/λ
ni2 nf2
FIGURE 8-13
Energy-level diagram for the hydrogen atom
FIGURE 8-14
Emission and absorption spectroscopy
Ionization Energy of Hydrogen
and Hydrogen-Like Ions
Ephoton = hv = Ef –Ei = 0–E1 = E1
define the ionization energy of the hydrogen atom as
RH
Ei(H) = –E1= –(– ) = RH
12
The corresponding energy level expression for
hydrogen like species such as He+ and Li2+ is
–Z2 RH
En =
n2
8-4 Two Ideas Leading to a
New Quantum Mechanics
Wave-Particle Duality
Einstein suggested particle-like
properties of light could explain the
photoelectric effect.
Diffraction patterns suggest photons
are wave-like.
deBroglie, 1924
Small particles of matter may at times
display wavelike properties.
Louis de Broglie (1892-1987)
Wave-Particle Duality
E = mc2
hν = mc2
hν/c = mc = p
p = h/λ
λ = h/p = h/mu
FIGURE 8-15
Wave properties of electrons demonstrated
The Uncertainty Principle
h
Δx Δp ≥
4π
Werner Heisenberg (1901-1976)
FIGURE 8-16
The uncertainty principle interpreted graphically
8-5 Wave Mechanics
Standing waves.
Nodes do not undergo displacement.
λ = 2L , n = 1, 2, 3…
n
Total nodes = n + 1
FIGURE 8-17
Standing waves in a string
FIGURE 8-18
The electron as a matter wave
The standing waves of a particle in a
one-dimensional box
ψ, psi, the wave function.
Should correspond to a standing wave
within the boundary of the system
being described.
FIGURE 8-19
The standing waves of a particle in a one-dimensional box
The Born Interpretation of the Wave Function
The total probability of finding a
particle in a small volume of
space is the product of the square
of the wave function, ψ2, and the
volume of interest. The factor ψ2
is called the probability density.
FIGURE 8-20
The probabilities of a particle in a one-dimensional box
8-6 Quantum Theory of the Hydrogen Atom
The Schrödinger Equation
Schrödinger, 1927
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 8-21
The relationship between spherical polar coordinates and Cartesian coordinates
Assigning Quantum Numbers
Principle quantum number, n = 1, 2, 3…
Angular momentum quantum number,
l = 0, 1, 2…(n −1)
l = 0, s
Magnetic quantum number,
l = 1, p
ml= −l … −2, −1, 0, 1, 2…+l
l = 2, d
l = 3, f
Principal Shells and Subshells
The Energies of Principal Shells and
Subshells in One-Electron Species
FIGURE 8-22
Shells and subshells of a hydrogen atom
8-7 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.
The Radial Functions
FIGURE 8-23
Radial functions of hydrogen orbitals
The Angular Functions
FIGURE 8-24
Angular functions of the s, p, and d orbitals
The Wave Functions and Shapes of the Orbitals
radial function
angular function
FIGURE 8-25
Representations of the wave function and electron probability density of the 1s orbital
FIGURE 8-24
Three-dimensional representations of the 95% electron probability density for the
1s, 2s and 3s orbitals
FIGURE 8-27
Representations of the wave function and electron probability
density for a 2p orbital
FIGURE 8-28
Simplified representations of the three 2p orbitals
FIGURE 8-29
Representations of the 3dxy and 3dz2 orbitals of the hydrogen atom
FIGURE 8-30
Representations of the five d orbitals
8-8 Electron Spin: A Fourth Quantum Number
FIGURE 8-32
Electron spin visualized
FIGURE 8-33
The Stern-Gerlach Experiment
8-9 Multi-electron Atoms
1. The electronic charge cloud of a multielectron atom can
be approximated as a superposition of one-electron charge
clouds called orbitals.
2. The total energy of an atom with N electrons is
Eatom=F–G, where F represents orbital energies and G
accounts for electron-electron repulsion.
The orbital energy is the energy of electron 1 in a
particular orbital interacting with the nucleus under the
average influence of all the other electrons.
3. The order in which we assign electrons to specific orbitals
is based on minimizing Eatom. Be careful not to place too
much emphasis on the energies of the orbitals themselves.
FIGURE 8-34
Orbital energy-level diagrams for the hydrogen atom and a multielectron atom
Penetration and Shielding
FIGURE 8-36
Radial distribution functions
8-10 Electron Configurations
1. Electrons occupy orbitals in a way that minimizes the
energy of the atom.
2. Only two electrons may occupy the same orbital, and these
electrons must have opposite spin: the Pauli exclusion
principle.
3. When orbitals of identical energy (degenerate orbitals) are
available, electrons initially occupy these orbitals singly
with parallel spins: Hund’s rule
Representing Electron Configurations
The Aufbau process
8-12 Electron Configurations and the Periodic Table
FIGURE 8-38
Electron configurations of the periodic table