Chapter 6 Chapter Overview

• Early atomic structure, light, & matter

– Planck’s equation, photoelectric effect, relativity
– Dual nature of light & matter
– Atomic spectrum of hydrogen

• Bohr model of hydrogen atom

• Quantum mechanics
– Orbitals, electron configurations (atoms and ions)
Electronic Structure and
• Periodic properties
Periodic Properties of – Atomic radius, ionization energy, electron affinity

Elements
1 2

Atomic Structure Atomic Structure

• Early view of atomic structure (Chapter 2) • Clues to electron arrangement  experiments
– Atom composed of protons, neutrons & electrons on how matter absorbs & emits light
– Small dense nucleus with electrons moving around it
• Example  flame emission
• Further questions
– Where are the electrons
relative to nucleus?
– How are they arranged
relative to each other
– Relationship of electron
arrangement to chemical
LiCl SrCl2 B(OH)3
behavior?

3 4
 Atomic Structure Electromagnetic Radiation
• Views on matter & light prior to 1900 • Light is generally classified as electromagnetic
radiation
Matter  particles whose mass & position could be
specified • Electromagnetic radiation  radiant energy
exhibiting wave-like behavior
Light  massless & delocalized energy waves
whose position could not be specified • Examples  visible light, X-rays,
microwaves, radiowaves
Matter and light did not intermingle
• Four primary characteristics of waves
• After 1900 some important experiments – Wavelength
challenged this view – Frequency
– Amplitude
– Velocity

5 6

Electromagnetic Radiation Electromagnetic Radiation

• Wavelength ()  distance between • Frequency ()  number of waves (cycles)
consecutive peaks, troughs, or midpoints that pass through a point in one second


1 s –1 or 1 Hz

 time
time

1 second 3 s –1 or 3 Hz


• Typical units  m (SI) & nm (10-9 m) • SI Units  s-1 or Hz (Hertz)

7 8
 Electromagnetic Radiation Electromagnetic Radiation
• Amplitude  vertical distance from midline of • Velocity (c)  distance wave travels in 1 s
c = ꞏ (mꞏs-1)   &  inversely related
wave to peak or trough

 = distance for 1 wave

time
time
 = waves per second

• Velocity is constant for electromagnetic

radiation  c = 2.9979 x 108 mꞏs-1

9 10

Candy Quiz Electromagnetic Radiation

• The wavelength of the green light
from a traffic signal is centered
around 522 nm
• Calculate the frequency (s-1) of this green light
• Answer 

m
𝜆 522 nm 5.22 𝑥 10 m
nm
Radiowaves Microwaves IR visible UV X-rays -rays
. m/s Increasing 
𝜈 5.74 𝑥 10 s
. m
 Increasing 

11 12
 Max Planck Planck’s Equation
• Max Planck (1900)  studied • Planck’s Equation
emission of radiation from
incandescent objects
E = nh = nhc/
• Physics of time predicted
increasing E with decreasing  E = change in energy (J)
n = integer
• Observation only explained if
– Energy absorbed and emitted in h (Planck’s constant) = 6.626  1034 J s
discrete amounts (quantized)
• The quantity h is called a quantum of energy
E  n (n = integer) – n gives the number of quanta

13 14

Planck’s Equation Photoelectric Effect

• Albert Einstein (1905)
• Sample exercise – Theoretical model for photoelectric effect

• A hospital X-ray machine emits X-ray • Photoelectric effect  ejection of e- from

radiation with  = 5.00 x 10-2 nm metals when exposed to ultraviolet light

• Calculate E for one quantum of this • Experimental observations

radiation – No e- unless  ≥ threshold value
– KE of e- increases linearly with 
• Compare this to one quantum of infrared – KE of e- independent of intensity of light
light with  = 5.00 x 104 nm
• Suggested light has particle character  photon
KE = h -  (h  photon E;   e- binding E)

15 16
 Special Theory of Relativity Characteristics of Light
• Special Theory of Relativity • From ideas of Planck & Einstein  view of light
(electromagnetic radiation) changed
E = mc2
• Dual nature of light
• Energy & mass are related – Wave properties →  & 
– Particle properties → quantized energy (nh) & mass
m = E/c2 & Ephoton = h = hc/

m = h/c

• Light has apparent mass related to wavelength

 also suggested particle character

17 18

Wave Character of Matter Wave Character of Matter

• Light has a dual nature  wave & particle • Davisson, Germer, & Thomson (1927)
– Bombarded nickel crystal with electrons
• Does matter behave as particle & wave? – Observed diffraction pattern → dark & light spots on
photographic film
• Louis de Broglie (1923) – Characteristic of wave behavior → constructive &
– Proposed matter does display wave properties destructive interference

m = h/c  m = h/v (v = velocity) • Confirmed wave nature of

matter
• de Broglie equation
•  only observable for very
 = h/mv = h/p (p = momentum) small objects
– electrons, protons, neutrons

19 20
 In Class Problem Character of Matter
• Calculate the wavelengths of
• After early 1900’s view of matter changed
p+ (m = 1.67 x 10-27 kg) with v = 3.0 x 105 m/s
bullet (m = 16.2 g) with v = 180 m/s – Matter and energy are not distinct

• Answers – All matter has both wave and particle properties

– Microscopic objects (electrons, proton, neutron)

exhibit predominately wave properties

– Macroscopic objects (baseball, etc.) exhibit

predominately particle properties

21 22

Atomic Spectrum of Hydrogen Atomic Spectrum of Hydrogen

• Key experiment for understanding atomic • Emission spectrum of H atoms
structure  emission spectrum of hydrogen – Electrical discharge in H2  excited H atoms
– Observe wavelengths emitted
• Spectrum  separation of light absorbed or
emitted into its component wavelengths – Light emitted at discrete wavelengths  line
spectrum

• Emission spectrum  wavelengths produced

when sample with excess energy (excited)
releases energy as light

23 24
 Atomic Spectrum of Hydrogen Atomic Spectrum of Hydrogen
• Compare to spectrum of white light (sun, electric • Conclusion  energies of H atom emission
discharge in vacuum)  continuous spectrum ( H atom) are quantized

E = nh = nhc/ (Planck’s equation)

Cause of emission?


Electrons

25 26

Bohr Model of H Atom Bohr Model of H Atom

• Niels Bohr (1913)
– Quantized model for e- structure of H atom
– e- moves @ nucleus in certain allowed
orbits (quantized)
– Emission  transition of e- between orbits

Orbits  n = 1, 2, 3,
• Electron can be in any orbit (n = 1, 2, 3, …) 
Energies  E1, E2, E3, not in between (rungs of ladder)

• n = 1  ground state or ground level

– Lowest possible orbit & energy

27 28
 Bohr Model of H Atom Bohr Model of H Atom
• Energy of electron in nth level • Energy expression can be used to calculate
difference in energy of orbits  emission E

Z = atomic number  model applies to any 1 e- species

• E  calculate  or  via Planck’s equation
• Negative sign  E of orbiting e- lower than
free e- (n = ∞  E = 0) E = h = hc/

H atom (Z=1) He+ ion (Z=2) • Note  n above (orbit) & n from earlier Planck
E1 = -2.178 x 10-18 J E1 = -8.712 x 10-18 J eq. (# photons) not same
E2 = -5.445 x 10-19 J E2 = -2.178 x 10-18 J

29 30

Bohr Model of H Atom Bohr Model of H Atom

• Sample exercise • Bohr model works well for H atom & 1 e- species
 reproduces spectral line wavelengths
• Calculate the energies and wavelengths for the
red, green, and blue emission lines of the H atom • Fails for anything with more than 1 e-  He, Li,
etc.

• Fundamental flaw  fixed circular orbits

• Concept of quantized e- energy levels important

step

• Needed new model  quantum mechanics

31 32
 Quantum Mechanics Quantum Mechanics
• Erwin Shrödinger (1925) • Standing wave equation  amplitude as
– Developed equation describing wave properties of e- function of position

• Thought of e- as standing wave

– Stationary, fixed endpoints
• 2nd order homogeneous differential equation
• Orbit must be integral multiple of   n
• For H atom
– E
– Include kinetic E & potential E (Coulomb’s Law)
– A   (3-D wave amplitude → wavefunction)

33 34

Quantum Mechanics Orbitals

• Schrödinger Equation • n  orbitals are mathematical functions (r,,)

• Solution to this equation  En’s & n’s

– n is 3-D wave function for e-  orbital
– En is energy of particular n
– n called principal quantum number

35 36
 Orbitals Principal QN
• Orbitals  related to 3-D region of space e-
resides in
• Principal QN (n)  integer values
• Characterized by 3 quantum numbers (QN)
n = 1, 2, 3, 4, …
1. n = principal QN  energy & size
• n related to energy & size of orbital
2. ℓ = angular momentum QN  shape – Distance from nucleus → shell
3. mℓ = magnetic QN  orientation
• As n increases  energy & size increase
• Orbitals are quantized
– Only certain QN’s  orbitals allowed

37 38

Angular Momentum QN Angular Momentum QN

• Angular Momentum QN (ℓ)  integer values n=1 ℓ=0 1s orbital
n=2 ℓ=0 2s orbital
ℓ = 0, 1, 2, 3, …, n  1 ℓ=1 2p orbital
• ℓ relates to 3-D shape of the orbital n=3 ℓ=0 3s orbital
– Subshell
ℓ=1 3p orbital
ℓ=2 3d orbital
• Value of ℓ assigned a letter n=4 ℓ=0 4s orbital
ℓ=1 4p orbital
ℓ 0 1 2 3 4 ℓ=2 4d orbital
s p d f g ℓ=3 4f orbital

39 40
 Magnetic QN Orbitals
1 orbital  n=1 ℓ=0 mℓ = 0 1s
• Magnetic QN (mℓ)  integer values n=2 ℓ=0 mℓ = 0 2s
ℓ=1 mℓ = -1 2p-1
4 orbitals
mℓ = -ℓ, …, 0, …, ℓ mℓ = 0 2p0
mℓ = +1 2p+1
• mℓ relates to orientation of the orbital in space n=3 ℓ=0 mℓ = 0 3s
ℓ=1 mℓ = -1 3p-1
• mℓ gives number of orbitals of given ℓ value mℓ = 0 3p0
mℓ = +1 3p+1
9 orbitals ℓ=2 mℓ = -2 3d-2
ℓ=0 (s) mℓ = 0 1 orbital
mℓ = -1 3d-1
ℓ=1 (p) mℓ = -1,0,1 3 orbitals
mℓ = 0 3d0
ℓ=2 (d) mℓ = -2,-1,0,1,2 5 orbitals
mℓ = +1 3d+1
ℓ=3 (f) mℓ = -3,-2,-1,0,1,2,3 7 orbitals mℓ = +2 3d+2

41 42

Physical Meaning of  Physical Meaning of 

•   3-D wave equation
– Has no true physical meaning • Use of probabilities rather than exact position
 Heisenberg Uncertainty Principle
• 2  has physical meaning
– Probability of finding an e- at point x, y, z • Uncertainty Principle  fundamental limit on
simultaneous precision of particle’s position and
• 2  expressed as probability distribution momentum
– Probability along a straight line from nucleus

1s
• Can not know exact movements & positions of
In 3-D 
e-  only probable locations & regions

e- density map

43 44
 Physical Meaning of  Physical Meaning of 
• Radial probability distribution  total probability 1s 2s 3s
of finding e- at given distance from nucleus

mpd

• Most probable distance  maximum in radial r (Å) r (Å) r (Å)

probability distribution
• As n increases
– Multiple maxima
• For H 1s  mpd = 5.29 x 10-2 nm or 0.529 Å
– Regions of zero probability → nodes

45 46

Physical Meaning of  Physical Meaning of 

2-D plots

3p

• Probability is asymptotic function px py pz

– Difficult to define orbital size

• Relative orbital size

– 3-D surface containing 90% of total e- probability
dxy dxz dyz dx2 – y2 dz2

47 48
 H Atom Orbital Energies Electron Spin QN
• In H atom  orbital energies depend only on n • Electron spin QN (ms)  4th QN (only 2 values)
ms = +½ or -½

• Interpreted as e- spinning on internal axis

• Spin up (↑)  +½

• Spin down (↓)  -½

• e- in atom  4 QN’s

• Orbitals with equal energy called degenerate n, ℓ, mℓ, ms

49 50

Pauli Exclusion Principle Pauli Exclusion Principle

• Pauli Exclusion Principle
– No two electrons can have same set of four quantum • Total number of electrons for each orbital type
numbers (n, ℓ, mℓ, ms)
s 1 orbital 2 electrons
• Electrons in same orbital
– Same n, ℓ, mℓ  ms must be different
p 3 orbitals 6 electrons
• Conclusion  any one orbital can hold only
d 5 orbitals 10 electrons
two e- & they must have opposite spins
n = 1 1 f 7 orbitals 14 electrons
= 0 0
1s m = 0 0
ms = +½ –½

51 52
 Multi-Electron Atoms Multi-Electron Atoms
• Schrödinger equation solved exactly for H • Approximation
– use H-orbitals as starting point
atom & agrees well with experimental data – consider average effect of electron repulsion (shielding)
– consider radial distribution of s, p, d, … orbitals
• Cannot be solved exactly for multi-electron
atoms • Shielding  inner e- cancel some + charge of
nucleus “felt” by outer e-
• 3 energy terms
– KE of electron motion
– PE of attraction between nucleus & electron
– PE of repulsion between electrons

• Difficulty due to electron repulsion

– Never know exact e- positions  H.U.P.

53 54

Multi-Electron Atoms Multi-Electron Atoms

• Result  same shape as H atom orbitals but 4f__ __ __ __ __ __ __
size & energy different  varies with n & ℓ 6s__
– hydrogen-like orbitals 5p__ __ __
4d__ __ __ __ __
• Orbital energies with given n are no longer 5s__
degenerate 4p__ __ __
Energy
Ens < Enp < End < Enf 3d__ __ __ __ __
4s__
• Orbitals with same ℓ but different mℓ are still 3p__ __ __
degenerate 3s__
2p__ __ __
E(2px) = E(2py) = E(2pz) 2s__
1s__

55 56
 Electron Configuration Electron Configuration
• Order of filling orbitals
• Can now describe electron arrangement for all
atoms & ions  filled orbitals

• Lowest energy arrangement  electron

configuration

• As e- fill orbitals  fill in order of increasing

energy (Aufbau principle)

• Completely fill degenerate set before filling next

energy orbital

57 58

Electron Configuration Electron Configuration

• Hunds rule  for degenerate orbitals
H 1e– 1s 1s1 – Most stable configuration = maximum number of
He 2e– 1s 1s2 unpaired electrons

Li 3e– 1s 2s 1s22s1 C 6e– 1s 2s 2p

Be 4e– 1s 2s 1s22s2 2p
B 5e– 1s 2s 2p 1s22s22p1 2p 1s22s22p2
C 6e– 1s 2s 2p 1s22s22p2
• Fill all degenerate orbitals with one spin up
2p
2p
? electron before filling with 2nd spin down electron

59 60
 H 1e– 1s 1s1 Electron Configuration
He 2e– 1s 1s2 • Valence electrons  electrons in the outermost
principle quantum level (n) of an atom or ion
Li 3e– 1s 2s 1s22s1
Be 4e– 1s 2s 1s22s2 Element e- configuration valence e-
N 1s2 2s2 2p3 5
B 5e– 1s 2s 2p 1s22s22p1
F 1s2 2s2 2p5 7
C 6e– 1s 2s 2p 1s22s22p2 Mg 1s2 2s2 2p6 3s2 2
N 7e– 1s 2s 2p 1s22s22p3
• Electrons below valence  core electrons
O 8e– 1s 2s 2p 1s22s22p4
• Elements in same column  same # valence
F 9e– 1s 2s 2p 1s22s22p5
electrons
Ne 10e– 1 s 2s 2p 1s22s22p6

61 62

Electron Configuration Periodic Table

• Elements in periodic table organized according
• Idea of core & valence electrons leads to
to valence e- configuration
shorthand for electron configuration
• Elements with same number & type of valence e-
Ne  1s2 2s2 2p6
grouped in same column
Mg  1s2 2s2 2p6 3s2 or [Ne]3s2
• Number & type of valence e-  chemical
properties & behavior
• Write core electron configuration as [NG]
– NG is name of noble gas
• Rows organized according filling subshells 
– Example  row 2 = filling 2s & 2p orbitals

63 64
 Electron Configuration Electron Configuration
• Several exceptions to e- filling rules
– Cr  [Ar]4s13d5 (should be [Ar]4s23d4)
– Cu  [Ar]4s13d10 (should be [Ar]4s23d9)
– several 2nd row transition metals  Nb – Ag
– Pt & Au

* *

• Main Group Elements  fill s and p

* *
• Transition Elements  filling d

• Lanthanide and Actinide Series  filling f

65 66

Electron Configuration Periodic Properties

• Electron configuration of ions (Chapter 7.1) • Periodic  property changes & repeats with
– Start with electron configuration of neutral atom
– Cation  remove e- in reverse order of filling
position
– Anion  add e- in correct filling order
• Element properties change with position in P.T.
Cl = [Ne]3s23p5
• Property variations  e- configuration
Cl- Add 1e- to 3p → Cl- = [Ne]3s23p6
Cl+  remove 1e- from 3p → Cl+ = [Ne]3s23p4 – Atomic radius
– Ionic radius
• Exception  cations of transition metals
– Remove s e- first, then d e- – Ionization energy

– Electron affinity
Mn = [Ar]4s23d5  Mn+ = [Ar]4s13d5 (not 4s23d4)

67 68
 Atomic Radius Atomic Radius
• Atomic Radius  size of atom Increases down a column
– Difficult to define precisely
– Inter-atomic distances in elements & compounds
d12 = r1 + r2

Radius (pm)
– Experimental technique → X-ray or e- diffraction

• Covalent radius  distances in molecules Decreases across a row

– H2  dH-H = 74 pm → rH = 37 pm
– HCl  dH-Cl = 136 pm → rCl = 99 pm

• Metallic radius  distances in metallic crystals

– Fe  dFe-Fe(Ave) = 248 pm → rFe = 124 pm
Atomic Number

69 70

Atomic Radius Ionic Radius

• Periodic trends in atomic radius • Ionic radius  size of cations and anions

1. Atomic radius decreases across a row

n same across row but increasing + charge

 stronger attraction  size decreases

2. Atomic radius increases down a column

n increases down column  e- farther

away from nucleus  size increases rcation < rneutral ranion > rneutral

71 72
 Ionic Radius
• Trends
1. Cations smaller than parent neutral atoms

Remaining e-’s experience full positive charge 

stronger attraction  radius decreases

2. Anions larger than parent neutral atoms

Additional e- experiences larger repulsions with

remaining e-  radius increases

73 74

Ionic Radius Ionization Energy

• Trends • Ionization energy (IE)  energy to remove an
3. Ion size increases down a column e- from ground state gaseous atom

n increases down column  e- farther away from X(g) → X+(g) + e-

nucleus  size increases
• IE always positive (endothermic)
4. Isoelectronic ions (same e- configuration)  Al(g) → Al+(g) + e- IE = 580 kJ/mol
size decreases as Z increases
• Multi-electron atoms  multiple ionizations
n same but increasing + charge  stronger
attraction  size decreases Al(g) → Al+(g) + e- IE1 = 580 kJ/mol
Al+(g) → Al2+(g) + e- IE2 = 1815 kJ/mol
O2> F > Na+ > Mg2+ > Al3+
largest size smallest size Al2+(g) → Al3+(g) + e- IE3 = 2740 kJ/mol
smallest Z largest Z Al3+(g) → Al4+(g) + e- IE4 = 11,600 kJ/mol

75 76
 Ionization Energy Ionization Energy
• Observed trends
Ionization Energies 1 - 8 for Sodium Through Argon (kJ/mol)
1. IE4 > IE3 > IE2 > IE1
Element IE1 IE2 IE3 IE4 IE5 IE6 IE7 IE8
IE increases with increasing positive charge Na 496 4562 6912 9544 13353 16610 20115 25490
Mg 738 1451 7733 10540 13628 17995 21704 25656
2. IE4 >>> IE3 > IE2 > IE1 Al 578 1817 2745 11578 14831 18378 23295 27459
IE1 Si 787 1577 3232 4356 16091 19785 23786 29252
Al = [Ne]3s23p1 Al+ = [Ne]3s2 P 1012 1903 2912 4957 6274 21269 25397 29854
IE2
IE3 Si 1000 2251 3361 4564 7013 8496 27106 31670
Al2+ = [Ne]3s1 Al3+ = [Ne] = [He]2s22p6
Cl 1251 2297 3822 5158 6540 9362 11018 33605
IE4
Ar 1521 2666 3931 5771 7238 8781 11995 13842
Al4+ = [He]2s22p5

IE core e- >>> IE valence e-

77 78

Ionization Energy Ionization Energy

• Periodic trends in IE1
Decreases down a column
1. IE1 increases across a row
IE1 (MJ/mole)

Increases across a row n same across row but increasing + charge

 stronger attraction  harder to remove

2. IE1 decreases down a column

n increases down column  e- farther away

from nucleus  easier to remove

Atomic Number Mirrors trend in atomic radius

79 80
 Electron Affinity Electron Affinity
• Electron Affinity (EA)  energy to add an e-
to ground state gaseous atom

X(g) + e- → X-(g)

EA (kJ/mole)
• EA can be positive (endothermic) or negative
(exothermic)

Ne(g) + e- → Ne-(g) EA = +120 kJ/mol

Cl(g) + e- → Cl-(g) EA = -350 kJ/mol

Less negative down a column
Related to filled vs unfilled shells More negative across a row
Atomic Number

81 82

Electron Affinity
• Periodic trends in EA

1. EA more negative across row

adding e-  closer to full valence shell

 harder to remove (more stable)

2. EA less negative down column

added e- farther away as n increases 

less tightly bound  easier to remove
(less stable)

83