John E. McMurry ‡ Robert C.

Fay

General Chemistry: Atoms First Chapter 3 Periodicity and the Electronic Structure of Atoms
Lecture Notes
Alan D. Earhart Southeast Community College ‡ Lincoln, NE

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Chapter 3/2

Light and the Electromagnetic Spectrum
Electromagnetic energy (³light´) is characterized by wavelength, frequency, and amplitude.

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Chapter 3/3

Light and the Electromagnetic Spectrum
Wavelength x Frequency = Speed 

m

x 

1 s

=

c
m s

c is defined to be the rate of travel of all electromagnetic energy in a vacuum and is a constant value²speed of light. c = 3.00 x 108 m s

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Chapter 3/6

Light and the Electromagnetic Spectrum
The light blue glow given off by mercury streetlamps has a wavelength of 436 nm. What is the frequency in hertz? 3.00 x 108 c m s 

= 

=
436 nm 1m 1 x 109 nm

= 6.88 x 1014 s-1 = 6.88 x 1014 Hz

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Chapter 3/7

Electromagnetic Energy and Atomic Line Spectra
Line Spectrum: A series of discrete lines on an otherwise dark background as a result of light emitted by an excited atom.

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Chapter 3/8

Chapter 3/9

Chapter 3/10

Electromagnetic Energy and Atomic Line Spectra
Johann Balmer in 1885 discovered a mathematical relationship for the four visible lines in the atomic line spectra for hydrogen. 1 1 1 = R’ 2 - 2 n 2  Johannes Rydberg later modified the equation to fit every line in the entire spectrum of hydrogen. 1 

= R’

1 m2

-

1 n2

R (Rydberg Constant) = 1.097 x 10-2 nm-1
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Particlelike Properties of Electromagnetic Energy
Photoelectric Effect: Irradiation of clean metal surface with light causes electrons to be ejected from the metal. Furthermore, the frequency of the light used for the irradiation must be above some threshold value, which is different for every metal.

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Chapter 3/12

Particlelike Properties of Electromagnetic Energy

Chapter 3/13

Particlelike Properties of Electromagnetic Energy
Photoelectric Effect: Irradiation of clean metal surface with light causes electrons to be ejected from the metal. Furthermore, the frequency of the light used for the irradiation must be above some threshold value, which is different for every metal.

Einstein explained the effect by assuming that a beam of light behaves as if it were a stream of particles called photons.

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Chapter 3/14

Particlelike Properties of Electromagnetic Energy
E = h E 

h (Planck¶s constant) = 6.626 x 10-34 J s Electromagnetic energy (light) is quantized. Quantum: The amount of energy corresponding to one photon of light.
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Particlelike Properties of Electromagnetic Energy
Niels Bohr proposed in 1914 a model of the hydrogen atom as a nucleus with an electron circling around it. In this model, the energy levels of the orbits are quantized so that only certain specific orbits corresponding to certain specific energies for the electron are available.

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Chapter 3/16

Particlelike Properties of Electromagnetic Energy

Chapter 3/17

Wavelike Properties of Matter
Louis de Broglie in 1924 suggested that, if light can behave in some respects like matter, then perhaps matter can behave in some respects like light. In other words, perhaps matter is wavelike as well as particlelike. h 

=

mv

The de Broglie equation allows the calculation of a ³wavelength´ of an electron or of any particle or object of mass m and velocity v.
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Quantum Mechanics and the Heisenberg Uncertainty Principle
In 1926 Erwin Schrödinger proposed the quantum mechanical model of the atom which focuses on the wavelike properties of the electron. In 1927 Werner Heisenberg stated that it is impossible to know precisely where an electron is and what path it follows²a statement called the Heisenberg uncertainty principle.

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Chapter 3/19

Wave Functions and Quantum Numbers
Wave solve Wave function equation or orbital ( ) Probability of finding electron in a region of space ( 2)

A wave function is characterized by three parameters called quantum numbers, n, l, ml.

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Chapter 3/20

Wave Functions and Quantum Numbers
Principal Quantum Number (n) ‡ Describes the size and energy level of the orbital ‡ Commonly called shell ‡ Positive integer (n = 1, 2, 3, 4, «) ‡ As the value of n increases: ‡ The energy of the electron increases ‡ The average distance of the electron from the nucleus increases

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Chapter 3/21

Wave Functions and Quantum Numbers
Angular-Momentum Quantum Number (l) ‡ Defines the three-dimensional shape of the orbital ‡ Commonly called subshell ‡ There are n different shapes for orbitals ‡ If n = 1 then l = 0 ‡ If n = 2 then l = 0 or 1 ‡ If n = 3 then l = 0, 1, or 2 ‡ etc. ‡ Commonly referred to by letter (subshell notation) ‡ l=0 s (sharp) ‡ l=1 p (principal) ‡ l=2 d (diffuse) ‡ l=3 f (fundamental) ‡ etc.
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Chapter 3/22

Wave Functions and Quantum Numbers
Magnetic Quantum Number (ml ) ‡ Defines the spatial orientation of the orbital ‡ There are 2l + 1 values of ml and they can have any integral value from -l to +l ‡ If l = 0 then ml = 0 ‡ If l = 1 then ml = -1, 0, or 1 ‡ If l = 2 then ml = -2, -1, 0, 1, or 2 ‡ etc.

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Chapter 3/23

Wave Functions and Quantum Numbers

Chapter 3/25

The Shapes of Orbitals

Node: A surface of zero probability for finding the electron.

Chapter 3/26

The Shapes of Orbitals

Chapter 3/27

The Shapes of Orbitals

Quantum Mechanics and Atomic Line Spectra

Quantum Mechanics and Atomic Line Spectra

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Chapter 3/31

Electron Spin and the Pauli Exclusion Principle
Electrons have spin which gives rise to a tiny magnetic field and to a spin quantum number (ms).

Pauli Exclusion Principle: No two electrons in an atom can have the same four quantum numbers.

Orbital Energy Levels in Multielectron Atoms
Effective Nuclear Charge (Zeff): The nuclear charge actually felt by an electron. Zeff = Zactual - Electron shielding

Electron Configurations of Multielectron Atoms
Electron Configuration: A description of which orbitals are occupied by electrons. Degenerate Orbitals: Orbitals that have the same energy level. For example, the three p orbitals in a given subshell. Ground-State Electron Configuration: The lowestenergy configuration. Aufbau Principle (³building up´): A guide for determining the filling order of orbitals.
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Electron Configurations of Multielectron Atoms
Rules of the aufbau principle: 1. Lower-energy orbitals fill before higher-energy orbitals. 2. An orbital can only hold two electrons, which must have opposite spins (Pauli exclusion principle). 3. If two or more degenerate orbitals are available, follow Hund¶s rule. Hund¶s Rule: If two or more orbitals with the same energy are available, one electron goes into each until all are half-full. The electrons in the half-filled orbitals all have the same value of their spin quantum number.
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Electron Configurations of Multielectron Atoms
Electron Configuration H: 1s1 1 electron s orbital (l = 0) n=1

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Chapter 3/36

Electron Configurations of Multielectron Atoms
Electron Configuration H: He: 1s1 1s2

2 electrons s orbital (l = 0) n=1

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Chapter 3/37

Electron Configurations of Multielectron Atoms
Electron Configuration H: He: Li: 1s1 1s2 Lowest energy to highest energy 1s2 2s1 1 electrons s orbital (l = 0) n=2

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Chapter 3/38

Electron Configurations of Multielectron Atoms
Electron Configuration H: He: Li: N: 1s1 1s2 1s2 2s1 1s2 2s2 2p3 3 electrons p orbital (l = 1) n=2
Chapter 3/39

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Electron Configurations of Multielectron Atoms
Electron Configuration H: He: Li: N: 1s1 1s 1s2 1s2 2s1 1s2 2s2 2p3 Orbital-Filling Diagram

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Chapter 3/40

Electron Configurations of Multielectron Atoms
Electron Configuration H: He: Li: N: 1s1 1s 1s2 1s 1s2 2s1 1s2 2s2 2p3 Orbital-Filling Diagram

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Chapter 3/41

Electron Configurations of Multielectron Atoms
Electron Configuration H: He: Li: N: 1s1 1s 1s2 1s 1s2 2s1 1s2 2s2 2p3 1s 2s Orbital-Filling Diagram

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Chapter 3/42

Electron Configurations of Multielectron Atoms
Electron Configuration H: He: Li: N: 1s1 1s 1s2 1s 1s2 2s1 1s2 2s2 2p3 1s 2s 1s 2s 2p
Chapter 3/43

Orbital-Filling Diagram

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Electron Configurations of Multielectron Atoms
Electron Configuration Na: 1s2 2s2 2p6 3s1 Ne configuration Shorthand Configuration [Ne] 3s1

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Chapter 3/44

Electron Configurations of Multielectron Atoms
Electron Configuration Na: P: 1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p3 Shorthand Configuration [Ne] 3s1 [Ne] 3s2 3p3

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Chapter 3/45

Electron Configurations of Multielectron Atoms
Electron Configuration Na: P: K: 1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p3 1s2 2s2 2p6 3s2 3p6 4s1 Ar configuration Shorthand Configuration [Ne] 3s1 [Ne] 3s2 3p3 [Ar] 4s1

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Chapter 3/46

Electron Configurations of Multielectron Atoms
Electron Configuration Na: P: K: Sc: 1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p3 1s2 2s2 2p6 3s2 3p6 4s1 1s2 2s2 2p6 3s2 3p6 4s2 3d1 Shorthand Configuration [Ne] 3s1 [Ne] 3s2 3p3 [Ar] 4s1 [Ar] 4s1 3d1

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Chapter 3/47

Chapter 3/48

Some Anomalous Electron Configurations
Expected Configuration Cr: [Ar] 4s2 3d4 Actual Configuration [Ar] 4s1 3d5

Cu:

[Ar] 4s2 3d9

[Ar] 4s1 3d10

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Chapter 3/49

Electron Configurations and the Periodic Table
Valence Shell: Outermost shell.

Li: 2s1 Na: 3s1

Cl: 3s2 3p5 Br: 4s2 4p5

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Chapter 3/50

Electron Configurations and Periodic Properties: Atomic Radii

Chapter 3/52

Electron Configurations and Periodic Properties: Atomic Radii

Chapter 3/53

Electron Configurations and Periodic Properties: Atomic Radii
column radius

row

radius

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Chapter 3/54

Chapter 3/55

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