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Chem 16 General Chemistry 1

03 Electron Configuration and Chemical Periodicity

Dr. Gil C. Claudio


Second Semester 2014-2015
Table of Contents

Contents
1 Development of the Periodic Table

2 Quantum Mechanical Model of the Periodic Table

3 Electron Configurations

4 Periodic Law and the Periodic Table

5 Periodic Properties of the Elements


5.1 Atomic and Ionic Size . . . . .
5.2 Ionization Energy . . . . . . . .
5.3 Electron Affinity . . . . . . . . .
5.4 Electronegativity . . . . . . . .
5.5 Magnetic Properties . . . . . . .

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6 Metals, Nonmetals, and Metalloids

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References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffry D. Madura, and Carey Bisonnette.

1 Development of the Periodic Table


Lothar Meyer
In 1869, Dmitri Mendeleev and Lothar Meyer independently proposed the
periodic law:
When the elements are arranged in order of increasing atomic mass,
certain sets of properties recur periodically.
Meyer based his periodic law on the property called atomic volume.
Dmitri Mendeleev
Dmitri Mendeleev was a Russian chemist and inventor. He is credited as
being the creator of the first version of the periodic table of elements.

Property
Atomic mass
Density, g/cm3
Molar volume, cm3 /mol
Specific heat capacity, J/g-K
Color
Density of oxide, g/cm3
Boiling point of chloride
Chloride density, g/cm3

Predicted
Eka-silicon
72
5.5
13
0.31
dirty gray
EsO2 , 4.7
EsCl4 , below 1000 C
EsCl4 , 1.9

Observed
Germanium
72.6
5.47
13.22
0.32
grayish white
GeO2 , 4.703
GeCl4 , 860 C
GeCl4 , 1.887

en.wikipedia.org/wiki/File:Medeleeff by repin.jpg

Mendeleevs Periodic System

en.wikipedia.org/wiki/File:Mendelejevs periodiska system 1871.png

Properties of Germanium
Three elements predicted by Mendeleev were discovered shortly after the
appearance of his 1871 periodic tablegallium (1875), scandium (1879), and
germanium (1886).

2 Quantum Mechanical Model of the Periodic


Table
Splitting of Energy Levels
The higher the nuclear charge Z lowers orbital energy by increasing
nucleus-electron attractions.
2

An additional electron raises the orbital energy due to electron-electron


repulsions.
Electrons in outer orbitals (higher n) are higher in energy because inner
electrons shield them from nuclear charge (effective nuclear charge, Zeff ).
Electrons that have a finite probability distribution near the nucleus
(penetration) have lower energy. Thus, an energy level (shell) is split
into sublevel (subshell) energies: s < p < d < f .
Summary
Hydrogen atom
4s

A typical multielectron atom

. . . (4p, 4d, 4f)


4p

3s

3p

3d

3d
4s
3p

2s

2p

Energy

Energy

3s

1s

2p
2s

1s

Rules for Electron Assignment


The electron configuration of an atom is a designation of how electrons are
distributed among various orbitals in principal shells and subshells. The rules
for this distribution are:
Electrons occupy orbitals in a way that minimizes the energy of the atom.
Pauli exclusion principle. No two electrons can have the same set of
four quantum numbers (n, l, ml , ms ). An orbital can hold a maximum of
two electrons, and they must have opposite spins.
Hunds rule. For orbitals of identical energy (degenerate orbitals),
electrons initially occupy these orbitals singly.
Pauli Exclusion Principle
The Pauli exclusion principle states that no two electrons can have the
same set of four quantum numbers (n, l, ml , ms ). An orbital can hold a
maximum of two electrons, and they must have opposite spins.
Aufbau Principle
The Aufbau Principle electrons fill orbitals starting at the lowest available
(possible) energy states before filling higher states (e.g. 1s before 2s).
Also called the Building-Up Principle
The order in which these orbitals are filled is given by the (n + l ) rule, which
states that given two orbitals, the one which has a higher n value but a lower
(n + l ) value is considered to be of a lower energy level.
Also called the Madelung rule or the Klechkowski rule.
3d is higher energy than 4s since the (n + l ) of 3d is 5 while the (n + l ) of
4s is 4.
3

Klechkovski Rule

en.wikipedia.org/wiki/File:Klechkovski rule.svg

Hunds Rule
Hunds Rule states that for degenerate orbitals, the lowest energy is
attained when the number of electrons with the same spin is maximized.
also called Hunds Rule of Maximum Multiplicity.
Since electrons repel each other, the electrons attain the lowest energy
level by staying as far apart from each other by staying in different
sub-orbitals.
Orbital Energy Diagram
Hydrogen atom
4s

A typical multielectron atom

. . . (4p, 4d, 4f)


4p

3s

3p

3d

3d
4s
3p

2s

2p

Energy

Energy

3s

1s

2p
2s

1s

Summary: Hunds Rule

correct

a.
1s

2s

2p
correct

b.
1s

2s

2p

c.

(since this is the 1 electron in the p sublevel


it can be either "spin-up" or "spin-down")

incorrect

1s

2s

2p

(the spin of the 2nd electron depends on the spin of the


1st electron, even though they aren't in the same orbital)

correct

d.
1s

2s

2p

(as long as you draw the first electron in each orbital as


"spin-up", you will draw a correct orbital diagram)

commons.wikimedia.org/wiki/File:Hund%27s Rule.svg

3 Electron Configurations
Examples
Symbol
Li
Be
B
C
N
O
F
Ne
Ge
Au

# e
3
4
5
6
7
8
9
10
32
79

Electron configuration
1s2 2s1
1s2 2s2
1s2 2s2 2p1
1s2 2s2 2p2
1s2 2s2 2p3
1s2 2s2 2p4
1s2 2s2 2p5
1s2 2s2 2p6
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4 f 14 5d9

4 Periodic Law and the Periodic Table


The Periodic Law
The periodic law refers to the periodic recurrence of certain physical and
chemical properties when the elements are considered in terms of increasing
atomic number.
The periodic table is an arrangement of the elements, by atomic number, in
which elements with similar physical and chemical properties are grouped
together in vertical columns.
Modern Periodic Table

Group
Period

10

11

12

13

14

15

16

17

18

1
H

2
He

3
Li

4
Be

5
B

6
C

7
N

8
O

9
F

10
Ne

11
Na

12
Mg

13
Al

14
Si

15
P

16
S

17
Cl

18
Ar

19
K

20
Ca

21
Sc

22
Ti

23
V

24
Cr

25
Mn

26
Fe

27
Co

28
Ni

29
Cu

30
Zn

31
Ga

32
Ge

33
As

34
Se

35
Br

36
Kr

37
Rb

38
Sr

39
Y

40
Zr

41
Nb

42
Mo

43
Tc

44
Ru

45
Rh

46
Pd

47
Ag

48
Cd

49
In

50
Sn

51
Sb

52
Te

53
I

54
Xe

55
Cs

56
Ba

72
Hf

73
Ta

74
W

75
Re

76
Os

77
Ir

78
Pt

79
Au

80
Hg

81
Tl

82
Pb

83
Bi

84
Po

85
At

86
Rn

87
Fr

88
Ra

104
Rf

105
Db

106
Sg

107
Bh

108
Hs

109
Mt

110
Ds

111
Rg

112
Cn

113
Uut

114
Uuq

115
Uup

116
Uuh

117
Uus

118
Uuo

Lanthanides

57
La

58
Ce

59
Pr

60
Nd

61
Pm

62
Sm

63
Eu

64
Gd

65
Tb

66
Dy

67
Ho

68
Er

69
Tm

70
Yb

71
Lu

Actinides

89
Ac

90
Th

91
Pa

92
U

93
Np

94
Pu

95
Am

96
Cm

97
Bk

98
Cf

99
Es

100
Fm

101
Md

102
No

103
Lr

en.wikipedia.org/wiki/File:Periodic table.svg

Group and Period


A group is a vertical column of elements in the periodic table. Members of
a group have similar properties.
Group numbers at the top
A period is a horizontal row of the periodic table. All members of a period
have atoms with the same highest principal quantum number.
arranged in order of increasing atomic number from left to right
numbered at the extreme left
Groups
The first two groupsthe s blockand the last six groupsthe p
blocktogether constitute the main-group elements.
Because they come between the s block and the p block, the d block
elements are known as the transition elements.
The f block elements, sometimes called the inner transition elements,
would extend the table to a width of 32 members if incorporated in the
main body of the table.
The table would generally be too wide to fit on a printed page, and
so the f block elements are extracted from the table and placed at
the bottom.
The 15 elements following barium (Z = 56) are called the lanthanides,
and the 15 following radon (Z = 88) are called the actinides.
Periodic Table and Electronic Configuration

P
Ni

1s2 2s2 2p6 3s2 3p3


1s2 2s2 2p6 3s2 3p6 4s2 3d8

[Ne]3s2 3p3
[Ar]4s2 3d8

s-block

p-block

1A

1s

2A

3A

2s

4A

5A

3B

4B

5B

6B

7B

7A

2p

d-block

3s

6A

8A

1s

8B

1B

3p

2B

4s

3d

4p

5s

4d

5p

6s

5d

6p

7s

6d

f-block
4f
5f
en.wikipedia.org/wiki/File:Periodic Table structure.svg

main group

1A

8A

1s

7A

1s

Noble gases

ns2np 1
ns2np 2
ns2np 3
ns2np 4
ns2np 5
ns2np 6

main group

Halogens

ns1
ns2

Periodic Table and Electronic Configuration

2A

3A

4A

5A

4s
5s
6s

Alkali earth metals

Alkalai metals

3s

6A

2p

2s
transition elements
3B

4B

5B

6B

7s

7B

8B

1B

3p

2B

3d

4p

4d

5p

5d

6p

6d
inner transition elements

Lanthanide series

4f

Actinide series

5f

Noble Gas Notation


8A

1A
2A

3A

3B

4B

5B

6B

7B

8B

1B

Ni

2B

4A

5A

6A

7A

Ne
Ar

5 Periodic Properties of the Elements


5.1

Atomic and Ionic Size

Atomic Radius
The atomic radius of an element is a measure of the size of the atom, usually
the distance from the nucleus to the boundary of the surrounding cloud of
electrons.
There is no precise outer boundary to an atom.
Thus we can describe an effective atomic radius as, the distance from the
nucleus within which 95% of all the electron charge density is found.
In fact, all that we can measure is the distance between the nuclei of
adjacent atoms (internuclear distance).
Definitions of Radii
Covalent radius is one-half the distance between the centers of two atoms
that are bonded covalently. It is the atomic radius associated with an element
in its covalent compounds.
Ionic radius is the radius of a spherical ion. It is the atomic radius associated
with an element in its ionic compounds.
Metallic radius is one-half the distance between the centers of adjacent
atoms in a solid metal.
The van der Waals radii are strictly hard sphere radii measured using
atomic distances in closest packed crystals.
solid sample of a noble gas
Trend of Atomic Radius
The atomic radius tends to decrease as one progresses across a period from
left to right
because the effective nuclear charge (Zeff ) increases, thereby attracting
the orbiting electrons and lessening the radius
The atomic radius usually increases while going down a group
due to the addition of a new energy level (shell).
The atomic radii of transition elements tend to be about the same across a
period but with a few unusual peaks.
Trend in Atomic Radius

decreasing atomic radius

Fr

He

increasing atomic radius


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Ionic Radius
Cations are smaller than the atoms from which they are formed.
For isoelectronic cations, the more positive the ionic charge, the smaller
the ionic radius.
Anions are larger than the atoms from which they are formed.
For isoelectronic anions, the more negative the charge, the larger the ionic
radius.

5.2

Ionization Energy

Ionization Energy
The ionization energy, I, is the quantity of energy a gaseous atom must
absorb to be able to expel an electron.
The first ionization energy I1 is the energy required to remove the most
loosely held electron from a gaseous atom.
The second ionization energy I2 is the energy required to remove an
electron from a gaseous unipositive ion.
Mg(g)
Mg+ (g)

Mg+ (g) + e
Mg2+ (g) + e

I1 = 738 kJ/mol
I2 = 1451 kJ/mol

Trend in Ionization Energy


Ionization energies decrease as atomic radii increase.
IE decreases down a group.
IE increases across a period.
I < I1 < I2 <
reflects the effect of n on Zeff
An equation for ionization energy is
I = RH

5.3

2
Zeff
n2

Electron Affinity

Electron Affinity
Electron affinity is the energy change associated with the gain of an
electron by a neutral gaseous atom.
F(g) + e F (g)

Hea = 328 kJ/mol

Some EAs are endothermic, others are exothermic.


Trends in Electron Affinity
It is more difficult to make generalizations about EAs than about IEs.
The smaller atoms to the right of the periodic table (e.g., group 17) tend
to have large, negative electron affinities.
EAs tend to become less negative in progressing toward the bottom of
a group, with the notable exception of the second-period members of
groups 15, 16, and 17 (namely, N, O, and F).
Some atoms have no tendency to gain an electron, such as the noble gases
where electrons have to enter the next shell, and groups 2 and 12 where
the electrons have to enter an empty p subshell, etc.
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5.4

Electronegativity

Electronegativity
Electronegativity (EN) is a measure of the ability of an atom to attract
electrons towards itself in the context of a chemical bond.
EN is related to IE and EA. In 1934, Robert S. Mulliken developed an
approach where
EN = IE EA2

Trend in Electronegativity
As one moves from left to right across a period in the periodic table, the
electronegativity increases
due to the stronger attraction that the atoms obtain as the nuclear charge
increases
Moving down a group, the electronegativity decreases
due to the longer distance between the nucleus and the valence electron
shell, thereby decreasing the attraction.
In general, EN is inversely related to atomic size.
Trend in Electronegativity

increasing electronegativity

Fr

decreasing electronegativity

Electronegativity: Pauling Scale

en.wikipedia.org/wiki/Electronegativity

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5.5

Magnetic Properties

Magnetic Properties
An important property related to the electron configurations of atoms and
ions is their behavior in a magnetic field. A spinning electron is an electric
charge in motion, which induces a magnetic field.
A diamagnetic substance has all its electrons paired and the individual
magnetic effects cancel out. It is slightly repelled by a magnetic field.
A paramagnetic substance has one or more unpaired electrons in its
atoms or molecules and the individual magnetic effects do not cancel
out. It is attracted into a magnetic field.
Paramagnetism in Manganese
The Mn atom ([Ar] 3d5 4s2 ) has a paramagnetism corresponding to 5
unpaired electrons

When it loses 2 electrons to become Mn2+ , the strength of its paramagnetism


corresponds to 5 unpaired electrons.

When a third electron is lost to produce Mn3+ , the ion has a paramagnetism
corresponding to 4 unpaired electrons.

6 Metals, Nonmetals, and Metalloids


Metals
A metal is an element whose atoms have small numbers of electrons in the
outermost electronic shell. Removal of an electron(s) from a metal atom occurs
without great difficulty, producing a positive ion (cation).
Metals generally have a lustrous appearance, are malleable and ductile,
and are able to conduct heat and electricity.
Nonmetals
A nonmetal is an element whose atoms tend to gain small numbers of
electrons to form negative ions (anions) with the electron configuration of a
noble gas.
Nonmetal atoms may also alter their electron configurations by sharing
electrons.
Nonmetals are mostly gases, liquid (bromine), or low melting point
solids and are very poor conductors of heat and electricity.
Metalloids
A metalloid is an element that may display both metallic and nonmetallic
properties under the appropriate conditions.
Trend in Metallic Character
Metallic property decreases across a period with increase in number of
valence electrons, as well as decrease in atomic radius, and it increases down
the group with increase in the number of shells and atomic radius.

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Trend in Metallic Character

decreasing metallic character


metalloids

F
nonmetals

metals

Fr
most

increasing metallic character

metallic

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