John W.

Moore
Conrad L. Stanitski

http://academic.cengage.com/chemistry/moore

Chapter 5
Electron Configurations and the
Periodic Table
Stephen C. Foster • Mississippi State University
Electromagnetic Radiation
Oscillating traveling waves Magnetic field

• like ripples on a pond Electric field

(vacuum) speed
c = 2.997.. x 108 m s-1

wavelength

+
# of crests λ
Frequency (n) =
time

Amplitude
In hertz (Hz) or s-1 (1 Hz = 1 s-1) distance
0

n = c
“top-bottom”
distance -
Electromagnetic Radiation & Matter
EM Radiation Magnetic field
• Oscillating electric and Electric field
magnetic fields.

• Traveling wave.
 moves through space like the ripples on a pond.

All types (“colors”) have the same velocity (through a

vacuum).
• c = speed of light = 2.99792458 x 108 ms-1 (exact)
Electromagnetic Radiation & Matter
Wavelength, λ λ
+
Distance between crests.
Length units (m, cm, nm).

Amplitude
distance
Amplitude 0
Top to bottom distance.

Frequency, n = number of crests passing a fixed point

per unit time. Inverse time units (s-1).
1 hertz (1 Hz) = 1 s-1
nλ = c
Electromagnetic Radiation & Matter
E increasing,  increasing,  decreasing
Planck’s Quantum Theory
Hot solid objects emit visible light
• Continuous spectrum

Increasing T
• Intensity and colors depend on T:

Higher T = shorter λmax (higher E) Heated wire

• Physics couldn’t explain this...

Planck’s Quantum Theory
Classical theory:
• no restriction on the E emitted by hot atoms.
• didn’t fit experimental data.

Planck:
• When an atom (or molecule) vibrates its E can only
equal an integer multiple of some minimum E.
• Energy is quantized.
• The smallest packet is a quantum
• Equantum = hnradiation = hc/λradiation
(h = Planck’s constant = 6.626 x 10-34 J s)
Planck’s Quantum Theory
Calculate the energy of 1 quantum of green light
emitted by a green laser pointer ( = 532 nm).

Equantum = hradiation

hc
= radiation

(6.626 x 10-34 Js)(2.998 x 108 ms-1)

=
632 x 10-9 m
= 3.14 x 10-19 J
The Photoelectric Effect
“Light” can cause ejection of e- from
a metal surface.

Metal cathode (-)

An anode (+) attracts e .
-

Current is measured.
vacuum

window
Anode (+)
The Photoelectric Effect
If λ > threshold (E too low), no e- emission.
• Higher intensity does NOT cause e- emission when
E < threshold !
threshold
High I
(# of ejected e-)
current

low I

increasing E

Einstein proposed that these results arose because of

the quantization of radiation.
The Photoelectric Effect
Einstein: Electromagnetic radiation
• is quantized.
• behaves like a stream of massless particles.
• G. N. Lewis later named them photons.

Imagine photons as particles, hitting electrons

embedded in glue. If the E of the photon (particle):
• is low, it can’t overcome the force holding in the e -.
• exceeds the strength of the glue, an e- is released

Higher intensity = more photons.

If Ephoton > threshold, more photons eject more e-.
Planck’s Quantum Theory
Photons with λ = 452 nm are blue.
(a) What’s the frequency of this radiation?
(b) What’s the energy of 1 of these photons?
(c) What’s the energy of 1 mol of 452-nm photons?
a) n = c
c 2.9979 x 108 ms-1
n= = = 6.63 x 10 s
16 -1
 4.52 x 10 m
-9

b) E = hn
E = 6.626 x 10-34 Js (6.63 x 1016 s-1) = 4.39 x 10-17 J
c) E/mol = 4.39 x 10-17 J (6.022 x 1023 mol-1)
= 2.6 x 107 J mol-1
The Photoelectric Effect
BUT light also acts like a wave:

EM radiation exhibits wave and particle properties. It:

• Doesn’t oscillate between wave and particle.
• Exhibits Wave-Particle Duality.
Hydrogen Atom
Excited gases emit line spectra.
• Heated solids emit continuous spectra.

Each element has a unique pattern.

Hydrogen, H
Slit
400 500 600 700
wavelength (nm)

Mercury, Hg

400 500 600 700

wavelength (nm)
Gas discharge
tube
Bohr Model of the Hydrogen Atom
Neils Bohr (1913):
• The single e- orbit the nucleus.
• Different orbits are possible with different radii
• Each has a fixed E (quantized).
• E-levels are identified with integers, n (n = 1…).
 Larger n = higher E
 Larger n = e- further from nucleus
Bohr Model of the Hydrogen Atom
The quantized E values are given by:

1
E = −RH n = 1, 2, 3. . . 
n2

Rydberg constant
2.179 x 10-18 J

Lowest E Niels Bohr

If:
• n = 1, atom is the ground state.
• n = , atom is ionized (E = 0).
Bohr Model of the Hydrogen Atom
infrared
n 1
0
emission
∞ E = −RH
-¹⁄9RH 3 n2

-¼RH 2
visible
emission absorption: ΔE > 0, n ↑
emission: ΔE < 0, n ↓
Energy

400 500 600 700

wavelength (nm)

1
-RH
ultraviolet ultraviolet
Bohr’s model exactly predicts
emission absorption the H-atom spectrum.
Bohr Model of the Hydrogen Atom
For an H-atom transition: ΔE = −RH 1 – 1
nf 2 ni2

Calculate E, n and λ (in nm) for an H-atom n = 4 → 2 transition.

ΔE = −RH [(½)2 − (¼)2 ] = -³⁄16RH = 4.086 x 10-19 J

(negative sign omitted; losing E = emission)
1 s-1 = 1 Hz

n= ΔE = 4.086 x 10 -19
= -34 J x 1014 Hz
6.166
h 6.626 x 10 Js

= c = 2.9979 x 10 8
ms -1
= 4.862 x 10-7 m = 486.2 nm
n 6.166 x 1014 s-1
Beyond Bohr: Quantum Mechanics
Bohr’s model predicts the H-atom:
• emission and absorption spectrum.
• ionization energy.

The model does not work for any other atom.

e- do not move in fixed orbits.

Beyond Bohr: Quantum Mechanics
De Broglie (1924): all moving objects act as waves:
h
λ =
mv
λ = wavelength (m) h = Planck’s constant (J s)
m = mass (kg) v = velocity (m s-1)

Davidson and Germer (1927) observed

e- diffraction by metal foils.
• e- exhibit wave-like behavior!
Beyond Bohr: Quantum Mechanics
Heisenberg Uncertainty Principle
It is impossible to know both the exact position and
exact momentum of an e-.

Why?
• Objects only seen by “light” with λ ≤ object size.
• Electrons are very small. Short λ is required.
• Short λ = high n = high E.
• Energetic collisions alter the speed and direction of
the e-.
Beyond Bohr: Quantum Mechanics
Schrödinger equation (1926):
• Treats e- as standing waves (not particles).
• Developed by analogy to classical equations for
the motion of a guitar string.
• Called “wave mechanics” or “quantum
mechanics”
 Explains the structure of all atoms and molecules.
 Complicated math; important results.

The solutions are energies and mathematical functions

(wave functions, ).
Beyond Bohr: Quantum Mechanics
2 = probability of finding an e- at a point in space.

An electron density (probability) map plots 2 for each

point in space.

Bigger value = darker shade.

Beyond Bohr: Quantum Mechanics
Each  describes a different energy level.
• H-atom wavefunction () = an orbital.
• e- do not follow fixed orbits around the nucleus.

Probability maps are hard to draw.

• Boundary surfaces are used
 contain the e- 90% of the time.
 Why not 100%? – it would include the
entire universe!
The H-atom
ground-state
orbital
Quantum Numbers
Each orbital () includes three quantum numbers:
n, ℓ, and mℓ

Principal quantum number, n (n = 1, 2, 3, … )

• Most important in determining the orbital energy.

• Defines the orbital size (larger n = larger average
radius).
• Orbitals with equal n are in the same shell.
Quantum Numbers
Azimuthal quantum number, ℓ (ℓ = 0 to n −1)
• Defines the shape of an orbital. ℓ code
• Orbitals with equal ℓ (and equal n) 0 s
are in the same subshell. 1 p
• Code letters identify ℓ 2 d
3 f
4 g

Magnetic quantum number, mℓ (mℓ = -ℓ to +ℓ )

Defines the orientation of the orbital.
Quantum Numbers
Example
List all sets of quantum numbers for an n = 3 e-.

ℓ = 0, or 1, or 2

if n = 3 and ℓ = 2 (3d), mℓ can equal -2, -1, 0, 1 or 2.

if n = 3 and ℓ = 1 (3p), mℓ can equal -1, 0, or 1.

if n = 3 and ℓ = 0 (3s), mℓ must be 0.

Note: every (n, ℓ, mℓ) set has a different shape and/or

orientation.
Electron Spin
Experiments showed a 4th quantum no. was needed
spin quantum number, ms
• +½ or −½ only.

View an e- as a spinning sphere.

Spinning charges act as magnets.

• Pauli: every e- in an atom must have a unique set of

(n, ℓ, mℓ, ms).
 Maximum of 2e- per orbital (opposite spins).
 known as the Pauli exclusion principle.
Atoms with More than 1 Electron
1
H-atom only: E = −RH n = 1, 2, 3. . . 
n2
E only depends on n
 H-atom: E3s = E3p = E3d etc.

All other atoms: E3d > E4s

4s
4p
3d
(but very close)
3p
E3s ≠ E3p ≠ E3d 3s
2p
2s

Energy
But, E3px = E3py = E3pz

1s
Atoms with More than 1 Electron
number of entries = n = 2ℓ +1 = n2 = 2/orbital = 2n2

Shell (n) Subshell (ℓ) # orbitals Orbitals in shell Max. e- Max. e- in shell

1 s 1 1 2 2

s 1 2
2 p 3 6 8
4

s 1 2
3 p 3 9 6 18
d 5 10

s 1 2
p 3 6
4 16 32
d 5 10
f 7 14
s Orbitals
One s orbital in every shell (n level).
ℓ =0

Spherical.
• Larger n = larger sphere

Probability of finding e- at
distance r from nucleus
1s 2s 3s

Distance from nucleus, r (pm)

p Orbitals

Three p orbitals (ℓ = 1): px, py and pz

Related to mℓ = -1, 0, +1.

d Orbitals

ℓ =2
Five d orbitals:

3dxz 3dxy 3dyz 3dx -2 y 3dz

2 2
Electron Configuration of Main-Group Elements
In multielectron atoms subshell energies depend on
n and ℓ.

4p
3d
Note:
4s
3p
E3s ≠ E3p ≠ E3d.
3s

2s
2p But,
Energy

E3px = E3py = E3pz

Also:
1s
3d is above 4s (but E4s≈ E3d)
Electron Configuration of Main-Group Elements
Add e- to orbitals in increasing E order
• If sets of orbitals have equal E (degenerate) use
Hund’s rule.

“The most stable arrangement of e- in the same

subshell has the max. number of unpaired e-, all with
the same spin”.

Paired e-: +½ and -½ ; ↑↓

Unpaired e-: all +½ or -½ ; ↑↑… or ↓↓…
Electron Configuration of Main-Group Elements

Electron configurations
1s 2s 2p Expanded Condensed
H 1s1 1s1
He 1s2 1s2
3p
Li 3s
1s22s1 1s22s1
2p
Be 1s 2s
2 2
1s 2s
2 2 2s

Energy
B 1s22s22p1 1s22s22p1
C 1s22s22p12p1 1s22s22p2
N 1s22s22p12p12p1 1s22s22p3
O 1s22s22p22p12p1 1s22s22p4 1s
F 1s22s22p22p22p1 1s22s22p5
Ne 1s22s22p22p22p2 1s22s22p6
Electron Configuration of Main-Group Elements

The first 20 elements have only s and p e-:

Full Configuration Noble Gas Notation

N 1s2 2s2 2p3 [He] 2s2 2p3

P 1s2 2s2 2p6 3s2 3p3 [Ne] 3s2 3p3

Ca 1s2 2s2 2p6 3s2 3p6 4s2 [Ar] 4s2

Ca
1s2 2s2 2p6 3s2 3p6 4s2
Electron Configurations of Transition Elements
4th period and heavier elements
• Pick the noble-gas core.
• Add ns
• Add (n – 1)d (d “steps down”)
• Add np

Sn (5th period, group 4A). Noble-gas core: [Kr]

Complete 5s and 4d. 2 e- into 5p:
[Kr] 4d10 5s2 5p2
Electron Configurations of Transition Elements
1s 1s

2 s 2 p

3 s 3 p

4 s 3d 3 d 4 p

5 s 4d 4 d 5 p

6 s 5d 4 f 5 d 6 p

7 s 6d 5 f 6 d 7 p

Main group Lanthanides and actinides Transition elements Main group

s block f block d block p block

Block identities show where successive e- add.

Note: d “steps down”, f “steps down” again.
Electron Configurations of Transition Elements
Increasing (n + ℓ ), then increasing n
ℓ value
n value
0 1 2 3
8 8s

7 7s 7p

6s 6p
6 6d

5s 5p 5d 5f
5
n+ℓ=8
4s 4p 4d 4f
4
n+ℓ=6 n+ℓ=7
3
3s 3p 3d
n+ℓ=4 n+ℓ=5
2s 2p
2
n+ℓ=2 n+ℓ=3
1s
1 n+ℓ=1
Electron Configurations of Transition Metals

Tc (5 ; 7B; 5 e into 4d)

th - [Kr] 4d5 5s2

Ni (4th; 8B; 8 e- into 3d) [Ar] 3d8 4s2

Cu (4th; 1B; 9 e- into 3d) [Ar] 3d9 4s2

Cu has lower E with
filled d-block and half-
filled s-block
[Ar] 3d10 4s1
Electron Configurations of Transition Metals

Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d1 4s2 3d2 4s2 3d3 4s2 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4d1 5s2 4d2 5s2 4d4 5s1 4d5 5s1 4d5 5s2 4d7 5s1 4d8 5s1 4d10 4d10 5s1 4d10 5s2

La Hf Ta W Re Os Ir Pt Au Hg
5d1 6s2 5d2 6s2 5d3 6s2 5d4 6s2 5d5 6s2 5d6 6s2 5d7 6s2 5d9 6s1 5d10 6s1 5d10 6s2

Note: ½ filled and filled shells have extra stability

Elements with Incomplete f Atomic Orbitals
Inner transition metals (Lanthanides & Actinides) have
partially filled f orbitals.
• Configurations can be read from the periodic table
block identities.

1s Pr is: [Xe] 4f2 5d1 6s2 1s

2 s 2 p

3 s 3 p

4 s 3d 3 d 4 p
Pr
5 s 4d 4 d 5 p

6 s 5d 4 f 5 d 6 p

7 s 6d 5 f 6 d 7 p
Valence Electrons
Gilbert N. Lewis: e- are arranged in shells.

Periodicity: similar elements have equal numbers of

e- in their outer shell.

Outer-shell e- = valence electrons =

• e- in incomplete shells, and
• partially-filled d and f orbitals

Inner e- = core electrons

• Noble gas core
• complete d and f orbitals
Valence Electrons

atom configuration core valence

N 1s2 2s2 2p3 [He] 2s2 2p3
Si 1s2 2s2 2p6 3s2 3p2 [Ne] 3s2 3p2

Se 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p4 [Ar] 3d10 4s2 4p4

Mn 1s2 2s2 2p6 3s2 3p6 3d 5 4s2 [Ar] 3d 5 4s2

Note: # of valence e- = A group #

Valence Electrons
Lewis dot symbols:
• Dots represent valence e-.
• Usually only used for s- and p-block elements.

N
Example nitrogen
5 valence e- (group 5A)
Ion Electron Configurations
Similar approach.
Positive ion: remove one e- for each “+”
Negative ion: add one e- for each “-”
S2- (16 + 2) = 18 e-
S [Ne] 3s2 3p4
S2- [Ne] 3s2 3p6 or [Ar]

Rb+ (37 - 1) = 36 e-
Rb[Kr] 5s1
Rb+ [Kr] or [Ar] 3d10 4s2 4p6
Ion Electron Configurations
Isoelectronic = equal number of e-.

“A-group” ions usually adopt the nearest noble-gas

configuration…
… many ions are isoelectronic.
Valence shell 5A
(15)
6A
(16)
7A
(17)
8A
(18)
1A
(1)
2A
(2)
3B
(3)

1s2 H+ He Li+ Be2+

2s2 2p6 N3- O2- F- Ne Na+ Mg2+ Al3+

3s2 3p6 P3- S2- Cl- Ar K+ Ca2+ Sc3+

4s2 4p6 Se2- Br- Kr Rb+ Sr2+ Y3+

5s2 5p6 Te2- I- Xe Cs+ Ba2+ La3+

Transition-Metal Ions
When filled, Ens > E(n -1)d .
ns e- are lost first.
Fe [Ar] 3d6 4s2 → Fe2+ [Ar] 3d6
→ Fe3+ [Ar] 3d5

Mn [Ar] 3d5 4s2 → Mn2+ [Ar] 3d5

→ Mn4+ [Ar] 3d3
→ Mn7+ [Ar]
Paramagnetism & Unpaired Electrons
Spinning e- = tiny magnet. If all e- are paired:
• The magnets cancel.
• The atom is diamagnetic
Paramagnet
 pushed weakly away from magnetic fields.

With unpaired e-:

• Spins point in the same direction (Hund’s rule).
• Magnets add.
• The atom is paramagnetic.
Ferromagnet
 attracted to magnetic fields.

Bulk aligned atom-magnets produce a

ferromagnet - a permanent magnet.
Periodic Trends: Atomic Radii
An estimate of atomic size
½(homonuclear bond length)
Cl = 99 pm
• Cl2 bond = 198 pm.
C = 77 pm
• diamond bond =154 pm.

Radii are additive.

• C-Cl in CCl4 is 176 pm long.
• From radii: (77 + 99) = 176 pm.
Periodic Trends: Atomic Radii
Periodic Trends: Atomic Radii
Atoms grow in size down a group.
Larger shell (larger n) added in each new row.

Atoms shrink across a period

• e- add to the same shell. Size stays ~constant? No,
• p+ add to the nucleus.
• Larger charge pulls all e- in, shrinking the atom.

Big Jump in size from noble gas to alkali metal

• A new shell (with larger n) is added.
Atomic Radii of Transition Metals
Outermost orbital (ns) determines atom size.
• Competing forces on this orbital:

add p+ = contract
Sc Ti V Cr Mn Fe Co Ni Cu Zn
164 147 135 129 137 126 125 125 126 137

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
182 160 147 140 135 134 134 137 144 152

La Hf Ta W Re Os Ir Pt Au Hg
188 159 147 141 137 135 136 139 144 155
radius
add e- add to inner (n -1)d in pm

Slightly inflate the outer shell

Overall: ~ constant radius in each period.

Periodic Trends: Ionic Radii
Grp 1A Grp 2A Grp 3A
Li Li+ Be Be2+ B B3+
157 90 112 59 86 41
Na Na+ Mg Mg2+ Al Al3+
191 116 160 86 143 68
K K+ Ca Ca2+ Ga Ga3+
235 152 197 114 153 76
Rb Rb+ Sr Sr+ In In3+
250 166 215 132 167 94

A cation is smaller than its neutral atom.

Main block: outer shell completely removed.
• e-/e- repulsion reduced (fewer e- ).
Periodic Trends: Ionic Radii
Group 6A Group 7A
O O2- F F-
74 126 72 119
S S2- Cl Cl-
104 170 99 167
Se Se2- Br Br-
117 170 114 182
Te Te2- I I-
137 207 133 206

An anion is larger than its neutral atom.

• More e-/e- repulsion (more e-). The shell swells.
Ionic Radii

Ne configuration

Isoelectronic Ions O2- F- Na+ Mg2+

Ionic radius (pm) 126 119 116 86
Number of p+ 8 9 11 12
Number of e- 10 10 10 10
More p+
Smaller size
Periodic Trends: Ionization Energies
Ionization energy (IE)
E to remove an e- from a gas-phase atom.

Mg(g) Mg+(g) + e- ΔE  Ionization Energy

Also called IE1

Periodic Trends: Ionization Energies

Down a group: IE ↓. Larger atom = less tightly held e-

Across a period: IE ↑. Smaller atom = more tightly held e-
Periodic Trends: Ionization Energies
Higher ionization energies (IEn)
IEn is the E required to remove a nth e-.

Mg(g)  Mg+ (g) + e- ΔE  IE1

Mg+(g)  Mg2+(g) + e- ΔE  IE2
Mg2+(g)  Mg3+(g) + e- ΔE  IE3

• IE2 > IE1 etc.

• Mg+ holds the 2nd e- more tightly.
• Huge increase if e- removal breaks a complete
shell (the core).
Periodic Trends: Ionization Energies
Table 5.6 Successive Ionization Energies for Second-Period Atoms (MJ/mol)

Li Be B C N O F Ne
1s22s1 1s22s2 1s22s22p1 1s22s22p2 1s22s22p3 1s22s22p4 1s22s22p5 1s22s22p6
IE1 0.52 0.90 0.80 1.09 1.40 1.31 1.68 2.08
IE2 7.30 1.76 2.43 2.35 2.86 3.39 3.37 3.95
IE3 11.81 14.85 3.66 4.62 4.58 5.30 6.05 6.12
IE4 21.01 25.02 6.22 7.48 7.47 8.41 9.37
IE5 32.82 37.83 9.44 10.98 11.02 12.18
IE6 47.28 53.27 13.33 15.16 15.24
IE7 64.37 71.33 17.87 20.00
IE8 Core electrons 84.08 92.04 23.07
IE9 106.43 115.38
IE10 131.43
Periodic Trends: Electron Affinities
Electron Affinity (EA)
E released when an e- adds to a gas-phase atom.

F(g) + e- F-(g) ΔE = Electron Affinity

• Usually exothermic (EA is negative)

• EA increases from left to right.
• Metals have low EA; nonmetals have high EA.
• Some tables list positive numbers.
 a sign-convention choice.
Periodic Trends: Electron Affinities
F(g) + e- F-(g) ΔE = Electron Affinity
Usually exothermic.
• Metal = low EA; nonmetals = high EA
EA > 0
X- less stable than X
1A 2A 3A 4A 5A 6A 7A 8A
(1) (2) (13) (14) (15) (16) (17) (18)

H He
-73 +50
Li Be B C N O F Ne
-60 +50 -27 -122 +70 -141 -328 +120
Na Mg Al Si P S Cl Ar
Table 5.7 -53 +40 -43 -134 -72 -200 -349 +96
K Ca Ga Ge As Se Br Kr
-48 +96 -30 -120 -78 -195 -325 +96
Rb Sr In Sn Sb Te I Xe
-47 -5 -30 -120 -103 -190 -295 +80
Energy, Ions & Ionic Compounds
Ionic compound formation is very exothermic:

K(s) + ½ F2(g) → KF(s) ΔHf° = -567.3 kJ

Two, of several, steps are:

K → K+ + e- IE = 419 kJ
[Ne] 4s1 [Ne]

F + e- → F- EA = -328 kJ
[He] 2s2 2p5 [He] 2s2 2p6 = [Ne]
Energy in Ionic Compound Formation
A Born-Haber cycle is useful:

K(g) ΔH3 = IE K+(g)

+
F(g) F (g)
ΔH4 = EA -

ΔH1 = ΔsubH

ΔH5 =
ΔH2 = ½ Bond E Lattice E

K(s) + ½ F2(g) KF(s)

ΔfH°

ΔfH° = ΔH1 + ΔH2 + ΔH3 + ΔH4 + ΔH5

(H is a state function)
Ionic Compound Formation

ΔH5 K(s) → K(g) F2 → 2F K →K+ F → F-

Elattice = ΔHf° – ΔH1 – ΔH2 – ΔH3 – ΔH4

= -567.3 – (+89) – (+79) – (+419) – (-328)
= -826 kJ/mol
Table 5.8 Effect of Ion Size & Charge on Lattice E & Melting Point
Compound Ion Charges r+ + r- Lattice E (kJ/mol) Melting Pt. (°C)

NaCl +1 -1 102 + 181 = 283 pm -786 800

BaO +2 -2 135 + 140 = 275 pm -3054 1920
MgO +2 -2 66 + 140 = 206 pm -3791 2800