Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 1 of 50

Philip DuttonUniversity of Windsor, Canada

Prentice-Hall © 2002

General ChemistryPrinciples and Modern Applications

Petrucci • Harwood • Herring

8th Edition

Chapter 9: Electrons in Atoms

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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

9-6 Wave Mechanics

9-7 Quantum Numbers and Electron Orbitals

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Contents

9-8 Quantum Numbers

9-9 Interpreting and Representing Orbitals of the Hydrogen Atom

9-9 Electron Spin

9-10 Multi-electron Atoms

9-11 Electron Configurations

9-12 Electron Configurations and the Periodic Table

Focus on Helium-Neon Lasers

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9-1 Electromagnetic Radiation

• Electric and magnetic fields propagate as waves through empty space or through a medium.

• A wave transmits energy.

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EM Radiation

Low

High

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Frequency, Wavelength and Velocity

• Frequency () in Hertz—Hz or s-1.• Wavelength (λ) in meters—m.

• cm m nm 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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Electromagnetic Spectrum

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RedOrange

Yellow

Green

Blue

Indigo

Violet

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ROYGBIV

700 nm 450 nm

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Constructive and Destructive Interference

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Refraction of Light

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9-2 Atomic Spectra

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Atomic Spectra

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9-3 Quantum Theory

Blackbody Radiation:

Max Planck, 1900:

Energy, like matter, is discontinuous.

є = h

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The Photoelectric Effect

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

> o threshold frequency

• e- I• ek

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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.

mu2 = eVs12

• At frequencies greater than o:

Vs = k ( - o)

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The Photoelectric Effect

Eo = hoEk = eVs o = eVo

h

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

Conservation of energy requires that:

h = mu2 + eVo2

1

mu2 = h - eVo eVs = 2

1

Ephoton = Ek + Ebinding

Ek = Ephoton - Ebinding

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9-4 The Bohr Atom

E = -RH

n2

RH = 2.179 10-18 J

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Energy-Level Diagram

ΔE = Ef – Ei = -RH

nf2

-RH

ni2

–

= RH ( ni2

1

nf2

–1

) = h = hc/λ

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Ionization Energy of Hydrogen

ΔE = RH ( ni2

1

nf2

–1

) = h

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

h = RH ( ni2

1) = RH

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

h = -Z2 RH

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Emission and Absorption Spectroscopy

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9-5 Two Ideas Leading to a New Quantum Mechanics

• Wave-Particle Duality.– Einstein suggested particle-like properties of

light could explain the photoelectric effect.– But diffraction patterns suggest photons are

wave-like.

• deBroglie, 1924– Small particles of matter may at times display

wavelike properties.

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deBroglie and Matter Waves

E = mc2

h = mc2

h/c = mc = p

p = h/λ

λ = h/p = h/mu

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X-Ray Diffraction

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The Uncertainty Principle

Δx Δp ≥ h

4π

• Werner Heisenberg

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9-6 Wave Mechanics

2Ln

• Standing waves.– Nodes do not undergo displacement.

λ = , n = 1, 2, 3…

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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.

L

xnsin

L

2ψ

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Probability of Finding an Electron

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Wave Functions for Hydrogen

• 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.

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Principle Shells and Subshells

• Principle electronic shell, n = 1, 2, 3…• Angular momentum quantum number,

l = 0, 1, 2…(n-1)

l = 0, sl = 1, pl = 2, dl = 3, f

• Magnetic quantum number, ml= - l …-2, -1, 0, 1, 2…+l

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Orbital Energies

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9-8 Interpreting and Representing the Orbitals of the Hydrogen Atom.

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s orbitals

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p Orbitals

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p Orbitals

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d Orbitals

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9-9 Electron Spin: A Fourth Quantum Number

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9-10 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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Penetration and Shielding

Zeff is the effective nuclear charge.

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9-11 Electron Configurations

• Aufbau process.– Build up and minimize energy.

• Pauli exclusion principle.– No two electrons can have all four quantum

numbers alike.

• Hund’s rule.– Degenerate orbitals are occupied singly first.

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Orbital Energies

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Orbital Filling

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Aufbau Process and Hunds Rule

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Filling p Orbitals

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Filling the d Orbitals

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Electon Configurations of Some Groups of Elements

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9-12 Electron Configurations and the Periodic Table

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Focus on He-Ne Lasers

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Chapter 9 Questions

1, 2, 3, 4, 12, 15, 17, 19, 22, 25, 34, 35, 41, 67, 69, 71, 83, 85, 93, 98