Ch08 - Electrons in Atoms

General Chemistry
Principles and Modern Applications Petrucci Harwood Herring 9th Edition
Chapter 8: Electrons in Atoms

Dr. Chris Kozak Memorial University of Newfoundland, Canada
General Chemistry: Chapter 8
Slide 1
What is Quantum Theory?

Quantum Theorys Explanation of Chemistry in 60 seconds
Electron Earth
Classical Mechanics Quantum Mechanics

Nucleus Sun
Slide 2
Quantum Numbers
In classical physics, all orientations are possible In quantum physics, only certain orientations are possible. They are quantized y q
with quantum number j with j = 0, 1, 2, 3, 4,
Slide 3
Quantum Numbers
For j = 1, There are three orientations
Y
Slide 4
Quantum Numbers
In general, 2j + 1 Orientations j 0 1 2 etc.
General Chemistry: Chapter 8 Slide 5
2j + 1 1 3 5
Quantum Numbers
1 3 5
Slide 6
Quantum Numbers
Slide 7
Quantum Numbers
Slide 8
Quantum Numbers
The Periodic Table! It explains all of chemistry chemistry, all of biology and biochemistry, and all the interesting parts of physics mostly.
Slide 9
Contents
8-1 8-2 82 8-3 8-4 8-5 8-6 8-7 Electromagnetic Radiation Atomic S At i Spectra t Quantum Theory The Bohr Atom Two Ideas Leading to a New Quantum Mechanics M h i Wave Mechanics Quantum Numbers and Electron Orbitals
Slide 10
Contents
8-8 8-9 89 Quantum Numbers Interpreting and Representing Orbitals of the Hydrogen Atom 8-9 8 9 Electron Spin 8-10 Multi-electron Atoms 8-11 8 11 Electron Configurations 8-12 Electron Configurations and the Periodic Table
Slide 11
8-1 Electromagnetic Radiation
Electric and magnetic fields propagate as waves through empty space or th h t through a medium. A wave transmits energ a e energy.
Slide 12
EM Radiation
Low
High
Slide 13
Frequency, Wavelength and Velocity

Frequency ( ) in HertzHz or s-1. q y () Wavelength () in metersm. m nm cm
pm (10-2 m) (10-6 m) (10-9 m) (10-10 m) (10-12 m)
Velocity (c)2.997925 x 108 m s-1.
c =
= c/
= c/
Slide 14
Electromagnetic Spectrum
Slide 15
ROYGBIV
Orange Yellow 700 nm Green Blue
Red
450 nm Indigo Violet
Slide 16
Constructive and Destructive Interference
Slide 17
Water and Light Wave Interference
Slide 18
Refraction of Light
Slide 19
8-2 Atomic Spectra
Slide 20
Atomic Spectra
Slide 21
Blackbody Radiation
1000 K Embers in a fire
1500 K Stove heating Element
2000 K Lightbulb Filament
Slide 22
8-3 Quantum Theory

Blackbody Radiation:
Max Pl M Planck, 1900 k 1900: Energy, like matter, is discontinuous.
E = nh
The Photoelectric Effect

Light striking the surface of certain metals causes ejection of electrons Wave properties of light is unable to explain some observations
> o ne- I Ek threshold frequency # of e- depends on intensity kinetic energy depends on frequency
Slide 24
Slide 25

At the stopping voltage the kinetic energy of the ejected electron has been converted to potential.
1 mu2 = e-Vs 2
At frequencies greater than o:

Vs = k ( - o)
Slide 26

Ek = eVs Eo = ho o = eVo h
eVo, and therefore o, are characteristic of the metal. Conservation of energy requires that: Ephoton = Ek + Ebinding Ek = Ephoton - Ebinding 1 mu2 + eVo 2 1 eVs = mu2 = h - eVo 2 h =
Slide 27
Photoelectron Spectroscopy
Slide 28
8-4 The Bohr Atom

E= -RH n2
RH = 2.179 x 10-18 J
Slide 29
Energy-Level Diagram
E = Ef Ei = = RH (
-RH -RH nf2 ni2
1 1 ) = h = hc/ ni2 nf2
Slide 30
Ionization Energy of Hydrogen

E = RH ( 1 1 ) = h ni2 nf2
As nf goes to infinity for hydrogen starting in the ground state: h = RH ( 1 ) = RH ni2
This also works for hydrogen-like species such as He+ and Li2+. h = -Z2 RH
Great, but what do we really need to know? k ?

Calculate the energy, frequency and wavelength for any hydrogen atom transition Id tif th wavelengths of the electromagnetic spectrum Identify the l th f th l t ti t as being in the UV, visible or IR regions. You should be able to do Examples 8 1 to 8 4 (and the 8-1 8-4 practice examples)
Slide 32
Summary of Bohrs Atomic Theory

Electrons are in motion around the nucleus (orbits) But, for circular orbits, electrons would possess angular momentum (acceleration) and therefore radiate energy! So, using Plancks quantum hypothesis, 1) El t Electrons move i fi d orbits around th nucleus in fixed bit d the l 2) Fixed orbits (stationary states) mean properties of individual electrons will have unique values for example values, example, the angular momentum is quantized based on the orbit in which the electron resides. 3) Electrons only pass between allowed orbits. This means that fixed quanta of energy are involved. QUANTUM NUMBERS!
What is Bohrs Theory Good For?

Approximations of the energy associated with transitions (movement) of electrons ONLY in ions with one electron!
Slide 34
8-5 Two Ideas Leading to a New Quantum Mechanics Q t M h i

Wave-Particle Duality Heisenberg s Heisenbergs Uncertainty Principle
Slide 35
Fire Photon Torpedoes!

Wave Particle Duality Wave-Particle Duality.
Einstein suggested particle-like properties of light cou d explain e photoelectric effect. could e p a the p o oe ec c e ec But diffraction patterns suggest photons are wavelike.
de Broglie, 1924
Small particles of matter may at times display wavelike properties a elike properties. The concept of the photon! photon !
de Broglie and Matter Waves

E = mc2 h = mc2 h/c = mc = p p = h/ = h/p = h/mu
The wavelength is related to the mass of the particle (particle property) If matter waves exist for small particles, then beams of particles should exhibit th characteristic properties of waves: diffraction. hibit the h t i ti ti f diff ti
Einsteins Relativity Equation Plancks Equation for Energy Rearrange to g g give momentum, p , Momentum carried by a photon in relation to its wavelength!
X-Ray Diffraction
Structure 1
Structure 2
Slide 38
The Uncertainty Principle

Werner Heisenberg
x p h 4
x is uncertainty in position p is uncertainty in momentum We cannot measure the exact position or exact momentum of a subatomic particle t t f b t i ti l simultaneously WHY?!
Sample Problems
1. Some Diamonds appear yellow because they contain nitrogen compounds that absorb purple light with a frequency of 7.23 x 1014 Hz. Calculate the wavelength in nm of absorbed light. g g Calculate the E of one photon of UV ( = 1 x 10-8 m), visible ( = 5 x 10-7 m) and IR ( = 1 x 10-4 m) light. What do the answers indicate about the relationship between and E? p Calculate the Energy required to remove an electron from a hydrogen atom in its ground state. Calculate the wavelength of the transition from n = 4 to n = 1 in Hydrogen (one of the Lyman series of transitions). Calculate the de Broglie wavelengths of a 50 kg mass travelling at the speed of light and for a proton (m = 1 673 x 10-27 kg) travelling at this speed What do 1.673 speed. these wavelengths say about the wave properties of matter in relation to their size?
2.
3. 4. 4 5.
Slide 40
8-6 Wave Mechanics

Standing waves.
Nodes do not undergo displacement. displacement
2L , n = 1, 2, 3 n
Slide 41
Wave Functions
, psi, the wave function. p ,
Should correspond to a standing wave within the boundary bo ndar of the s stem system being described.
Particle in a box box.

= 2 n x sin L L
Slide 42
Probability of Finding an Electron
Slide 43
Wave Functions for Hydrogen

Schrdinger, 1927
H (x,y,z) or H (r,,)
E = H
(r,,) = R(r) Y(,)

R(r) is the radial wave function. Y(,) is the Y( ) i th angular wave l function.
Principle Shells and Subshells

Principle electronic shell, n = 1, 2, 3 A Angular momentum quantum number, l t t b l = 0, 1, 2(n-1)
I = 0, s l=1 p 1, l = 2, d l=3 f 3,
Magnetic quantum number, ml= - l 2 -1, 0 1 2 +l l-2, 1 0, 1, 2+l
Slide 45
Orbital Energies
Slide 46
9-8 Interpreting and Representing the Orbitals of the Hydrogen Atom.
Slide 47
s orbitals
Slide 48
p Orbitals
Slide 49
p Orbitals
Slide 50
d Orbitals
Slide 51
8-9 Electron Spin: A Fourth Quantum Number N b
Slide 52
Electronic Structure of the H atom

We have 3 quantum numbers for H n=1 l=0 ml = 0 ms
Only one type of orbital orientation/symmetry Only one electron (can be either +1/2 or -1/2) 1s orbital
Ground State Configuration:

1s1
Slide 53
8-10 Multi-electron Atoms

Schrdinger equation was for only one e-. Electron-electron repulsion in multi-electron atoms. atoms Assume they have Hydrogen-like orbitals (by approximation). approximation)
Slide 54
8-11 Electron Configurations Three Main Principles

A fb process. Aufbau
Build up and minimize energy.
Pauli exclusion principle.

No two electrons can have all four quantum numbers alike. t b lik
Hunds rule.
D Degenerate orbitals are occupied singly t bit l i d i l first.
Orbital Energies
Slide 56
Orbital Filling for Atoms Only
Slide 57
Aufbau Process and Hunds Rule

spdf notation: C (carbon) 1s22s22p2 Expanded notation: 1s22s22px1py1
Slide 58
Filling p Orbitals (Electrons in Boxes)
Slide 59
Filling the d Orbitals
Slide 60
8-12 Electron Configurations and the Periodic Table
Slide 61

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General Chemistry

Principles and Modern Applications Petrucci Harwood Herring 9th Edition

Chapter 8: Electrons in Atoms

General Chemistry: Chapter 8

What is Quantum Theory?

Classical Mechanics Quantum Mechanics

General Chemistry: Chapter 8

with quantum number j with j = 0, 1, 2, 3, 4,

General Chemistry: Chapter 8

General Chemistry: Chapter 8

General Chemistry: Chapter 8

General Chemistry: Chapter 8

General Chemistry: Chapter 8

General Chemistry: Chapter 8

General Chemistry: Chapter 8

General Chemistry: Chapter 8

8-1 Electromagnetic Radiation

General Chemistry: Chapter 8

General Chemistry: Chapter 8

Frequency, Wavelength and Velocity

pm (10-2 m) (10-6 m) (10-9 m) (10-10 m) (10-12 m)

Velocity (c)2.997925 x 108 m s-1.

General Chemistry: Chapter 8

Orange Yellow 700 nm Green Blue

450 nm Indigo Violet

General Chemistry: Chapter 8

Constructive and Destructive Interference

General Chemistry: Chapter 8

Water and Light Wave Interference

General Chemistry: Chapter 8

General Chemistry: Chapter 8

8-2 Atomic Spectra

General Chemistry: Chapter 8

General Chemistry: Chapter 8

1000 K Embers in a fire

1500 K Stove heating Element

2000 K Lightbulb Filament

General Chemistry: Chapter 8

8-3 Quantum Theory

Max Pl M Planck, 1900 k 1900: Energy, like matter, is discontinuous.

The Photoelectric Effect

General Chemistry: Chapter 8

The Photoelectric Effect

General Chemistry: Chapter 8

The Photoelectric Effect

At frequencies greater than o:

General Chemistry: Chapter 8

The Photoelectric Effect

General Chemistry: Chapter 8

General Chemistry: Chapter 8

8-4 The Bohr Atom

General Chemistry: Chapter 8

-RH -RH nf2 ni2

1 1 ) = h = hc/ ni2 nf2

General Chemistry: Chapter 8

Ionization Energy of Hydrogen

As nf goes to infinity for hydrogen starting in the ground state: h = RH ( 1 ) = RH ni2

Great, but what do we really need to know? k ?

General Chemistry: Chapter 8

Summary of Bohrs Atomic Theory

What is Bohrs Theory Good For?

General Chemistry: Chapter 8

8-5 Two Ideas Leading to a New Quantum Mechanics Q t M h i