Electron Configurations  Chemical Periodicity (Ch 8)

• Electron spin & Pauli exclusion principle

• configurations
• spectroscopic, orbital box notation
• Hund’s rule - electron filling rules
• configurations of ATOMS:
Na + Cl  NaCl
• the basis for chemical valence
• configurations and properties of IONS
• periodic trends in :
• size
• ionization energies
• electron affinities
Mg + O2  MgO

6 Oct 1997 Chemical Periodicity 1

 Arrangement of Electrons in Atoms
Electrons in atoms are arranged as

SHELLS (n)

SUBSHELLS ()
Each orbital can be assigned
ORBITALS (m) up to 2 electrons!

WHY ? . . . Because there is a 4th quantum number,

the electron spin quantum number, ms.

6 Oct 1997 Chemical Periodicity 2

 Electron Spin
Quantum Number, ms

• It can be proved experimentally that the

electron has a spin. This is QUANTIZED.
• The two allowed spin directions are defined by
the magnetic spin quantum number, ms
ms = +1/2 and -1/2 ONLY.

6 Oct 1997 Chemical Periodicity 3

 Electron Spin Quantum Number
MAGNETISM is a macroscopic
result of quantized electron spin
5_magnet.mov

Diamagnetic: NOT attracted to a magnetic field

All electrons are paired N2

Paramagnetic: attracted to a magnetic field.

Substance has unpaired electrons O2

6 Oct 1997 Chemical Periodicity 4

 Pauli Exclusion Principle
• electrons with the same spin keep as far apart as possible
• electrons of opposite spin may occupy the same
“region of space” (= orbital)
• Consequences:
• No orbital can have more than 2
electrons
• No two electrons in the same atom can
have the same set of 4 quantum
numbers (n, l, ml, ms)
OR
• “Each electron has a unique address.”
6 Oct 1997 Chemical Periodicity 5
 QUANTUM
NUMBERS

n (shell) 1, 2, 3, 4, ...
 (subshell) 0, 1, 2, ... n - 1
m (orbital) -  ... 0 ... + 
ms (electron spin) +1/2, -1/2

6 Oct 1997 Chemical Periodicity 6

Shells, Subshells, Orbitals
n  #orbitals #e- Total PERIOD
1 0 s 1 2 2 1 (H, He)
2 0 s 1 2
1 p 3 6 8 2 (Li…Ne)
3 0 s 1 2
1 p 3 6 3 (Na .. Ar)
2 d 5 10 18
4 0 s 1 2 =0 s
1 p 3 6 =1 p
2 d 5 10 =2 d
3 f 7 14 32 =3 f
n 0..(n-1) (2 +1) 2*(2 +1) 2n2 etc, for n = 5, 6

6 Oct 1997 Chemical Periodicity 7

 Element Mnemonic Competition

Hey! Here Lies Ben Brown. Could Not Order Fire. Near
Nancy Margaret Alice Sits Peggy Sucking Clorets. Are
Kids Capable ?

6 Oct 1997 Chemical Periodicity 8

 Assigning Electrons to Atoms
• Electrons are assigned to orbitals successively in order
of the energy.
• For H atoms, E = - R(1/n2). E depends only on n.
• For many-electron atoms, orbital energy depends on
both n and .
• E(ns) < E(np) < E(nd) ...

6 Oct 1997 Chemical Periodicity 9

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 + )
increases.
b) for subshells of same (n +), (n + )=
subshell with lower n is 5
lower in energy. (n + )= 4

5_manyelE.mov

6 Oct 1997 Chemical Periodicity 10

Effective Nuclear Charge
• The difference in SUBSHELL energy
e.g. 2s and 2p subshells
is due to effective nuclear charge, Z*.

Charge felt by 2s 2s e- spends

e- of Li atom more time
close to Li3+
nucleus than
the 2p e-
Therefore
2s is
lower in E
than 3s
6 Oct 1997 Chemical Periodicity 11
 Effective Nuclear Charge, Z*
• Z* is the nuclear charge experienced by an electron.
• Z* increases across a period owing to incomplete
shielding by inner electrons.
• For VALENCE electrons we estimate Z* as:
Z* = [ Z - (no. of 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!

6 Oct 1997 Chemical Periodicity 12

Photoelectron Spectroscopy - Measuring IE
Photoelectric effect: h + A  A+ + e-
forms basis for DIRECT determination of IE
Kinetic energy of electron = h - IE
- VALENCE
therefore: IE = h - KE(e ) ELECTRONS

1s Ne Inner shell or
2s 2p
CORE ELECTRONS
Signal

Ar
1s 2s 2p 3s 3p

309 100 50 0
IE (MJ/mol)
6 Oct 1997 Chemical Periodicity 13
 Electron Filling Order (Figure 8.7)

6 Oct 1997 Chemical Periodicity 14

Writing Atomic Electron Configurations
Two ways of writing configurations.
One is called the spectroscopic notation:
SPECTROSCOPIC NOTATION
for H, atomic number = 1
1 no. of
1s electrons

value of l
value of n

6 Oct 1997 Chemical Periodicity 15

Writing Atomic Electron Configurations (2)

A second way is called the orbital box notation.

ORBITAL BOX NOTATION
for He, atomic number = 2
Arrows
2
1s
depict
electron
1s spin

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

Other electron has n = 1,  = 0, ml = 0, ms = - 1/2

6 Oct 1997 Chemical Periodicity 16

Electron Configuration tool - see “toolbox”.

6 Oct 1997 Chemical Periodicity 17

 Lithium Beryllium
Group 1A Group 2A
Z=3 Z=4
1s22s1 1s22s2

3p
3p 3s
3s
2p
2p 2s
2s

1s
1s
6 Oct 1997 Chemical Periodicity 18
 Boron Carbon
Z=5 Z=6
1s2 2s2 2p1 1s2 2s2 2p2

3p 3p
3s 3s

2p 2p
2s 2s
Why not  ?
1s 1s
6 Oct 1997 Chemical Periodicity 19
 Carbon The configuration of C is an
Z=6 example of HUND’S RULE:
1s2 2s2 2p2
the lowest energy
arrangement of electrons in
a subshell is that with the
3p MAXIMUM no. of unpaired
3s electrons

2p
Electrons in a set of orbitals
2s
having the same energy,
are placed singly as long as possible.
1s
6 Oct 1997 Chemical Periodicity 20
 Nitrogen Oxygen
Z=7 Z=8
1s2 2s2 2p3 1s2 2s2 2p4

3p
3p
3s
3s
2p
2p
2s
2s

1s
1s
6 Oct 1997 Chemical Periodicity 21
 Fluorine Neon
Z=9 Z = 10
1s2 2s2 2p5 1s2 2s2 2p6

3p 3p
3s 3s

2p 2p
2s 2s
Note that we have reached
the end of the 2nd period,
1s 1s . . . and the 2nd shell is full!

6 Oct 1997 Chemical Periodicity 22

 GROUPS and
PERIODS
Sodium
Z = 11
1s2 2s2 2p6 3s1
or “neon core” + 3s1
[Ne] 3s1 (uses rare gas notation)
Na begins a new period.
All Group 1A elements: Li Na K Rb Cs
have [core] ns1 configurations. (n = period #)

6 Oct 1997 Chemical Periodicity 23

Periodic Chemical Properties
REACTIVITY SIZE IE (Ionization Energy)
Li Be
5_Li.mov
Na Mg

K Ca
5_Na.mov
Rb Sr

Cs Ba
5_K.mov
Alkalis Alkaline Earths
6 Oct 1997 Chemical Periodicity 24
 Metals (ns2) - easily oxidized to M2+ Alkaline Earths
- less reactive than alkalis of same period
reactivity: Be < Mg < Ca < Sr < Ba
WHY? - • Size INCREASES as  group
• VALENCE e- are farther from nucleus
• same Z* - Valence e- less tightly held
• Therefore valence e- are easier to remove
Typical reactions / compounds
Oxides: M +1/2O2 (g)  MO (s) CaO (lime) - #5 Ind. Chem
Halides: M + X2 (g)  MX
Carbonates: CaCO3 (limestone)  CaO + CO2
Sulfates:
CaSO4.2H2O (gypsum)  CaSO4. 0.5H2O (plaster-of-paris) + 3/2H2O
RECALL: Solubility rules and PRECIPITATION REACTIONS
6 Oct 1997 Chemical Periodicity 25
 Relationship of Electron Configuration
and Regions of the Periodic Table

s block d block p block

f block

6 Oct 1997 Chemical Periodicity 26

 Transition Metals Table 8.4
• Transition metals (e.g. Sc .. Zn in the 4th period)
have the configuration [argon] nsx (n - 1)dy
• also called “d-block” elements.

3d orbitals used for Sc - Zn

Chromium Iron Copper

6 Oct 1997 Chemical Periodicity 27
Ion Configurations
To form cations from elements : remove 1 e- (or more)
from subshell of highest n [or highest (n + )].

P [Ne] 3s2 3p3 - 3e-  P3+ [Ne] 3s2 3p0

3p 3p
3s 3s

2p 2p
2s 2s

1s 1s
6 Oct 1997 Chemical Periodicity 28
Ion Configurations (2)

Transition metals ions:

remove ns electrons and then (n - 1)d electrons.

Fe [Ar] 4s2 3d6 loses 2 electrons  Fe2+ [Ar] 4s0 3d6

Fe Fe2+

4s 4s
3d 3d

E4s ~ E3d - exact energy Fe3+

of orbitals depend on
whole configuration 4s
3d
6 Oct 1997 Chemical Periodicity 29
 Ion Configurations (3)

How do we know the configurations of ions?

From the magnetic properties of ions.

Ions (or atoms) with UNPAIRED ELECTRONS are:

PARAMAGNETIC.
Ions (or atoms) without unpaired electrons are:
DIAMAGNETIC.

6 Oct 1997 Chemical Periodicity 30

 General Periodic Trends
• Atomic and ionic radii : SIZE
• Ionization energy : E(A+) - E(A)
• Electron affinity : E(A-) - E(A)
Higher Z*.
Electrons held
more tightly.
Larger orbitals.
Electrons held less
tightly.

6 Oct 1997 Chemical Periodicity 31

Atomic Size INCREASES
down a Group

• Size goes UP on going down a GROUP

• Because electrons are added further from the
nucleus, there is less attraction.

6 Oct 1997 Chemical Periodicity 32

Atomic Size DECREASES across a period

Size goes DOWN on going across a PERIOD.

Size decreases due to increase in Z*.
Each added electron feels a greater and greater
+ve charge.

6 Oct 1997 Chemical Periodicity 33

 Atomic Radii

6 Oct 1997 Chemical Periodicity 34

 Trends in Atomic Size
(Figure 8.10)
Radius (pm)
250
K

3rd period 1st transition

200
Na series
2nd period
Li
150

Kr
100
Ar
Ne
50

He
0
0 5 10 15 20 25 30 35 40

Atomic Number

6 Oct 1997 Chemical Periodicity 35

Sizes of Transition Elements(Figure 8.11)

• 3d subshell is inside the 4s subshell.

• 4s electrons feel a more or less constant Z*.
• Sizes stay about the same and chemistries are similar!
6 Oct 1997 Chemical Periodicity 36
Ion Sizes - CATIONS
Does the size go up or down when an atom loses an
electron to form a cation?

+ Forming
a cation
Li, 152 pm Li+, 60 pm
3 e-, 3 p 2 e-, 3 p

• CATIONS are SMALLER than the parent atoms.

• The electron/proton attraction goes UP so size DECREASES.

6 Oct 1997 Chemical Periodicity 37

 Ion Sizes - ANIONS
Does the size go up or down when gaining an
electron to form an anion?

Forming
- an anion

F, 64 pm F-, 136 pm
9 e-, 9 p 10 e-, 9 p

• ANIONS are LARGER than the parent atoms.

• electron/proton attraction goes DOWN so size INCREASES.

6 Oct 1997 Chemical Periodicity 38

 Trends in Ion Sizes
CATIONS ANIONS

(59 pm)

(207 pm)
Trends in relative ion sizes are the same as atom sizes.

6 Oct 1997 Chemical Periodicity 39

 Oxidation-Reduction Reactions
• Why do metals lose electrons in
their reactions?
• Why does Mg form Mg2+ ions
and not Mg3+?
• Why do nonmetals take on
electrons?

- related to IE and EA

6 Oct 1997 Chemical Periodicity 40

 Ionization Energy (IE)
Mg (g) atom [Ne]2s Mg3+

Mg (g) + 735 kJ  Mg+ (g) + e- [Ne]2s1

Mg+ (g) + 1451 kJ  Mg2+ (g) + e- [Ne]2s0

Mg2+ (g) + 7733 kJ  Mg3+ (g) + e- [He]2s22p5

Mg2+
• Energy ‘cost’ is very high to remove an
INNER SHELL e- (shell of n < nVALENCE). Mg+
• This is why oxidation. no. = Group no. Mg

6 Oct 1997 Chemical Periodicity 41

Trends in First 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
6 Oct 1997 Chemical Periodicity 42
 Trends in Ionization Energy (2)

• 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.

• IE decreases down a group

• Because size increases, reducing
ability generally increases down the
periodic table.
• E.g. reactions of Li, Na, K

6 Oct 1997 Chemical Periodicity 43

2nd IE / 1st IE 2nd IE: A+  A++ + e-

Li
Na
K

6 Oct 1997 Chemical Periodicity 44

Electron Affinity (EA)

• A few elements GAIN electrons to form anions.

• Electron affinity is the energy released when an
atom gains an electron.
A(g) + e-  A-(g) E.A. = DE = E(A-) - E(A)
• If E(A-) < E(A) then the anion is more stable
and there is an exothermic reaction
6 Oct 1997 Chemical Periodicity 45
Trends in Electron Affinity (Table 8.5, Figure 8.14)
Atom EA (kJ)
• Affinity for electron increases B -27
across a period C -122
(EA becomes more negative). N 0
O -141
F -328

• Affinity decreases down a F -328

group Cl -349
(EA becomes less negative). Br -325
I -295
6 Oct 1997 Chemical Periodicity 46
SUMMARY
• Electron spin: diamagnetism vs. paramagnetism
• Pauli exclusion principle - allowable quantum numbers
• configurations
• spectroscopic notation
• orbital box notation
• Hund’s rule - electron filling rules
• configurations of ATOMS: the basis for chemical valence
• period 2 ; groups
• transition metals
• configurations and properties of IONS
• periodic trends in :
• size
• ionization energies
• electron affinities
6 Oct 1997 Chemical Periodicity 47