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Chapter 8: ATOMIC ELECTRON

CONFIGURATIONS AND
PERIODICITY
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Arrangement of
Electrons in Atoms
Electrons in atoms are arranged as

SHELLS (n)

SUBSHELLS (l)

ORBITALS (ml)
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Arrangement of
Electrons in Atoms
Each orbital can be assigned no
more than 2 electrons!
This is tied to the existence of a 4th
quantum number, the electron
spin quantum number, ms.
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Electron
Spin
Quantum
Number,
ms

Can be proved experimentally that electron

has a spin. Two spin directions are given by
ms where ms = +1/2 and -1/2.
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Electron Spin Quantum Number

Diamagnetic: NOT attracted to a magnetic

field
Paramagnetic: substance is attracted to a
magnetic field. Substance has unpaired
electrons.
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QUANTUM
NUMBERS

n ---> shell 1, 2, 3, 4, ...

l ---> subshell 0, 1, 2, ... n - 1
ml ---> orbital -l ... 0 ... +l

ms ---> electron spin +1/2 and -1/2

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Pauli Exclusion Principle

No two electrons in the
same atom can have the
same set of 4 quantum
numbers.
That is, each electron in an
atom has a unique address
of quantum numbers.
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Electrons in Atoms
When n = 1, then l = 0
this shell has a single orbital (1s) to
which 2e- can be assigned.
When n = 2, then l = 0, 1
2s orbital 2e-
three 2p orbitals 6e-
TOTAL = 8e-
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Electrons in Atoms
When n = 3, then l = 0, 1, 2
3s orbital 2e-
three 3p orbitals 6e-
five 3d orbitals 10e-
TOTAL = 18e-
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Electrons in Atoms
When n = 4, then l = 0, 1, 2, 3
4s orbital 2e- And many more!

three 4p orbitals 6e-

five 4d orbitals 10e-
seven 4f orbitals 14e-
TOTAL = 32e-
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Assigning Electrons to Atoms

• Electrons generally assigned to orbitals of
successively higher energy.
• For H atoms, E = - C(1/n2). E depends only
on n.
• For many-electron atoms, energy depends
on both n and l.
• See Figure 8.5, page 295 and Screen 8. 7.
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Assigning Electrons to Subshells

• In H atom all subshells of
same n have same
energy.
• In many-electron atom:
a) subshells increase in
energy as value of (n + l)
increases.
b) for subshells of same
(n + l), the subshell with
lower n is lower in
energy.
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Electron
Filling
Order
Figure 8.5
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Effective Nuclear Charge, Z*

• Z* is the nuclear charge experienced by 
the outermost electrons. 
• Explains why E(2s) < E(2p)
• Z* increases across a period owing to 
incomplete shielding by inner electrons.
• Estimate Z* by ­­>  [ Z ­ (no. inner electrons) ]
• Charge felt by 2s e­ in Li        Z* = 3 ­ 2 = 1
• Be  Z* = 4 ­ 2 = 2
• B  Z* = 5 ­ 2 = 3 and so on!
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Effective
Nuclear
Charge
Figure 8.6

Electron cloud
for 1s electrons
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Writing Atomic Electron

Configurations
Two ways of 
writing configs. 
One is called  spdf notation
the spdf  for H, atomic number = 1
notation.
1 no. of
1s electrons

value of l
value of n
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Writing Atomic Electron
Configurations
Two ways of
writing ORBITAL BOX NOTATION
configs. Other for He, atomic number = 2
Arrows
is called the
2
1s
orbital box depict
electron
notation. spin
1s

One electron has n = 1, l = 0, ml = 0, ms = + 1/2

Other electron has n = 1, l = 0, ml = 0, ms = - 1/2
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See “Toolbox” for Electron Configuration tool.

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Effective Nuclear Charge, Z*
• Atom Z* Experienced by Electrons in
Valence Orbitals
• Li +1.28
• Be -------
• B +2.58 Increase in
• C +3.22 Z* across a
• N +3.85 period
• O +4.49
• F +5.13
 General Periodic Trends
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• Atomic and ionic size

• Ionization energy
• Electron affinity

Higher effective nuclear charge.

Electrons held more tightly

Smaller orbitals.
Electrons held more
tightly.
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Atomic Size

• Size goes UP on going

down a group.
• Because electrons are
added farther from the
nucleus, there is less
attraction.
• Size goes DOWN on going
across a period.
Atomic Radii 24

Figure 8.9
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Trends in Atomic Size

See Figures 8.9 & 8.10
Radius (pm)
250
K

3rd period 1st transition

200
series
2nd period Na
Li
150

Kr
100

Ar
Ne
50

He
0

0 5 10 15 20 25 30 35 40

Atomic Number
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Ion Sizes
Does+the size
go+
Li,152 pm Li , 60 pm
3e and 3p up or down
2e and 3p
when losing an
 
electron to form
a cation?
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Ion Sizes
+
Forming
Li,152 pm Li +
, 78 pm a cation.
3e and 3p 2e and 3 p

• CATIONS are SMALLER than the

atoms from which they come.
• The electron/proton attraction
has gone UP and so size
DECREASES.
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Ion Sizes
Does the size go up or
-
down when gaining an
F,64 pm F-electron
, 136 pmto form an
9e and 9p 10anion?
e and 9 p
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Ion Sizes
-
Forming
F, 71 pm F-, 133 pm an anion.
9e and 9p 10 e and 9 p

• ANIONS are LARGER than the atoms

from which they come.
• The electron/proton attraction has
gone DOWN and so size INCREASES.
• Trends in ion sizes are the same as
atom sizes.
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Trends in Ion Sizes

Figure 8.13
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Redox Reactions

Why do metals lose

electrons in their
reactions?
Why does Mg form Mg2+
ions and not Mg3+?
Why do nonmetals take
on electrons?
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Ionization Energy
See Screen 8.12

IE = energy required to remove an electron

from an atom in the gas phase.

Mg (g) + 738 kJ ---> Mg+ (g) + e-

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Ionization Energy
See Screen 8.12

Mg (g) + 735 kJ ---> Mg+ (g) + e-

Mg+ (g) + 1451 kJ ---> Mg2+ (g) + e-

Mg2+ (g) + 7733 kJ ---> Mg3+ (g) + e-

Energy cost is very high to dip into a
shell of lower n.
This is why ox. no. = Group no.
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Trends in Ionization Energy

1st Ionization energy (kJ/mol)
2500
He
Ne
2000

Ar
1500 Kr

1000

500

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35
H Li Na K
Atomic Number
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Trends in Ionization Energy

• IE increases across a period

because Z* increases.

• Metals lose electrons more

easily than nonmetals.
• Metals are good reducing
agents.
• Nonmetals lose electrons with
difficulty.
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Trends in Ionization Energy

• IE decreases down a group

• Because size increases.

• Reducing ability generally

increases down the periodic
table.
• See reactions of Li, Na, K
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Electron Affinity
A few elements GAIN electrons to
form anions.
Electron affinity is the energy
change when an electron is added:

A(g) + e- ---> A-(g) E.A. = ∆E

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Electron Affinity of Oxygen

O atom [He] ↑↓ ↑↓ ↑ ↑ ∆E is EXOthermic

because O has
+  electron an affinity for an
e-.
O­ ion [He] ↑↓ ↑↓ ↑ ↑

EA  =   ­  141 kJ
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Electron Affinity of Nitrogen

N atom [He] ↑↓ ↑ ↑ ↑ ∆E is zero for N-
due to electron-
+  electron electron
repulsions.
N­ ion [He] ↑↓ ↑ ↑ ↑

EA  =  0  kJ
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Trends in Electron Affinity

Atom EA
• Affinity for electron
increases across a F -328 kJ
period (EA becomes Cl -349 kJ
more negative). Br -325 kJ
• Affinity decreases down
a group (EA becomes I -295 kJ
less negative).
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Trends in Electron Affinity