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Transcript of Prentice-Hall © 2002General Chemistry: Chapter 9Slide 1 of 50 General Chemistry Principles and...
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 1 of 50
General ChemistryPrinciples and Modern Applications
Petrucci • Harwood • Herring
10th Edition
Chapter 8: Electrons in Atoms
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 2 of 50
Contents
8-1 Electromagnetic Radiation
8-2 Atomic Spectra
8-3 Quantum Theory
8-4 The Bohr Atom
8-5 Two Ideas Leading to a New Quantum Mechanics
8-6 Wave Mechanics
8-7 Quantum Numbers and Electron Orbitals
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 3 of 50
Contents
8-8 Interpreting and Representing Orbitals of the Hydrogen Atom
8-9 Electron Spin: A Fourth Quantum Number
8-10 Multi-electron Atoms
8-11 Electron Configurations
8-12 Electron Configurations and the Periodic Table
Focus on Helium-Neon Lasers
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 4 of 50
8-1 Electromagnetic Radiation
• Electric and magnetic fields propagate as waves through empty space or through a medium.
• A wave transmits energy.
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 5 of 50
EM Radiation
Low
High
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 6 of 50
Frequency, Wavelength and Velocity
• 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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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 7 of 50
Electromagnetic Spectrum
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 8 of 50
RedOrange
Yellow
Green
Blue
Indigo
Violet
Prentice-Hall ©2002 General Chemistry: Chapter 9 Slide 8
ROYGBIV
700 nm 450 nm
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 9 of 50
Constructive and Destructive Interference
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 10 of 50
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 11 of 50
Refraction of Light
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 12 of 50
8-2 Atomic Spectra
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 13 of 50
Atomic Spectra
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 14 of 50
8-3 Quantum Theory
Blackbody Radiation:
Max Planck, 1900:
Energy, like matter, is discontinuous.
Energy quantum: є = h E = n h ν
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 15 of 50
The Photoelectric Effect
• Light striking the surface of certain metals causes ejection of electrons.
• > o threshold frequency
• e- ~ I• ek ~
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 16 of 50
The Photoelectric Effect
Vs stop voltage
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 17 of 50
The Photoelectric Effect
• At the stopping voltage the kinetic energy of the ejected electron has been converted to potential.
mv2 = eVs12
• At frequencies greater than o:
Vs = k ( - o)
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 18 of 50
The Photoelectric Effect
Eo = hoEk = eVs o = eVo
h
eVo, and therefore o, are characteristic of the metal.
Conservation of energy requires that:
h = mv2 + eVo2
1
mv2 = h - eVo eVs = 2
1
Ephoton = Ek + Ebinding
Ek = Ephoton - Ebinding
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The Photoelectric Effect
General Chemistry: Chapter 9 Slide 19 of 50
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 20 of 50
8-4 The Bohr Atom (1913)
E = -RH
n2
RH = 2.179.10-18 J
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General Chemistry: Chapter 9 Slide 21 of 50
Energy-Level Diagram
ΔE = Ef – Ei = -RH
nf2
-RH
ni2
–
= RH ( ni2
1
nf2
–1
) = h = hc/λ
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H atom spectral series
General Chemistry: Chapter 9 Slide 22 of 50
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 23 of 50
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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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 24 of 50
Emission and Absorption Spectroscopy
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General Chemistry: Chapter 9 Slide 25 of 50
Visible atomic emission spectra
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 26 of 50
8-5 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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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 27 of 50
deBroglie and Matter Waves
E = mc2
h = mc2
h/c = mc = p
p = h/λ
λ = h/p = h/mu
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 28 of 50
X-Ray Diffraction
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 29 of 50
The Uncertainty Principle
Δx Δp ≥ h
4π
• Werner Heisenberg 1927
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 30 of 50
8-6 Wave Mechanics
2Ln
• Standing waves.– Nodes do not undergo displacement.
λ = , n = 1, 2, 3…
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 31 of 50
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
2ψn
En = (n π /L)2 /2
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 32 of 50
Probability of Finding an Electron
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Quantum physics and chemistry
33
E. Schrödinger
EH
The fundamental idea of wave mechanics
Theory of electrons and positrons
P. A. M. Dirac
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Operators
• In quantum mechanics operator acts on a function and it transfers the function into another function.
• Typical example: derivation– x2 is transformed to 2x – sin(x) is transformed to cos(x)– ex is transformed to ex
– exk is transformed to k exk
Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 34 of 50
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Hamilton operator• Total energy = kinetic + potential
Slide 35 of 60
VTHVTH operátor ˆˆˆ
mp
Tm
pmvT operátor
2ˆˆ
221 22
2
zyxiip ˆ
dxd
ixp ˆ
2
2
2
2
2
222
22
222ˆˆ
zyxmmm
pT
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Hamilton operator 2.
• The operator of potential energy, atomic unit
• Nuclear charge:• Electron charge: • rZ is the position of the nucleus: rZ = 0,0,0
Slide 36 of 60
eZ
eZeZ
rrqq
rqq
Vˆˆˆ
ˆ
1Zq
1eq
erVTH
ˆ
12
ˆˆˆ2
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 37 of 50
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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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 38 of 50
8-7 Quantum Numbers and Electron Orbitals
• 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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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 39 of 50
Orbital Energies
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 40 of 50
8-8 Interpreting and Representing the Orbitals of the Hydrogen Atom.
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Simplified wave functions (Z=1, a0=1)
Slide 41 of 60
n l m Rnl(r) Y( ,f )real
Complex
1 0 0 1s 2e-r -
2 0 0 2s -
2 1 0 2pz-
2 1 (±1) 2px,yYes
e±if
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Rn,0(r) for s orbitals for Z=1
Slide 42 of 60
Radial part of the 3s orbital Radial part of the 4s orbital
Radial part of the 1s orbital Radial part of the 2s orbital
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Rn,1(r) for p orbitals for Z=1
Slide 43 of 60
Radial part of the 2p orbital
Radial part of the 3p orbital
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Slide 44 of 60
8-8 Interpreting and Representing Orbitals of the Hydrogen Atom
0 in the yz plane 0 in the xz plane 0 in the xy plane
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Slide 45 of 60
d orbitals
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The shape of the atomic orbitals
Slide 46 of 60
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Slide 47/61
The electron density of s orbitals
s orbitals
22s 2
3sπ
e 221
r
s
r (distance)
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Slide 48 of 60
The electron density of p orbitals
22 xp
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Slide 49 of 60
Radial electron density r(r) = 4p r2 y2(r)
The probability of finding electrons on the surface of a sphere with radius r. The surface area = 4p r2
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 50 of 50
8-8 Electron Spin: A Fourth Quantum Number
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 51 of 50
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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Általános Kémia, Periódikus tulajdonságok
Slide 52 of 60
Shielding
Zeff = Z – S
En = - RH n2
Zeff2
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 53 of 50
Shielding
Slater rules: For a 1s electron, S = 0.3.
For electrons in an s or p orbital with n > 1, the screening constant is given by
S = 1.00·N2 + 0.85·N1 + 0.35·N0N0 represents the number of other electrons in the same shell, N1 represents the number of electrons in the next smaller shell (n-1), and N2 is the number of electrons in other smaller shells
(n-2 and smaller).
The effective nuclear charge is
Zeff = Z - S
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 54 of 50
8-11 Electron Configurations
• Aufbau principle.– Build up and minimize energy.
• Pauli exclusion principle.– No two electrons can have all four quantum
numbers alike (n, l, ml, s).
• Hund’s rule.– Degenerate orbitals are occupied singly first,
and the spins of the electrons are parallel.
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Prentice-Hall © 2002 General Chemistry: Chapter 9 Slide 55 of 50
Orbital Energies
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Orbital Filling
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Dia 57/61
Aufbau Process and Hunds Rule
C
E(1s) < E(2s) < E(2p)
B
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Filling p Orbitals
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Electron configuration
• Short notation. For example:• B: 1s2 2s2 2p1
• C: 1s2 2s2 2p2
• N: 1s2 2s2 2p3
• O: 1s2 2s2 2p4
• F: 1s2 2s2 2p5
• Ne: 1s2 2s2 2p6 is: [Ne] (10 electrons)
Dia 59/61
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Filling the d Orbitals
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Electon Configurations of Some Groups of Elements
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8-12 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