Chem 16 General Chemistry 1

03 Electron Configuration and Chemical Periodicity

Dr. Gil C. Claudio

First Semester 2019-2020

Table of Contents 1 Development of the Periodic Table

Lothar Meyer
Contents In 1869, Dmitri Mendeleev and Lothar Meyer independently proposed the
periodic law:
1 Development of the Periodic Table 1 • When the elements are arranged in order of increasing atomic mass, certain sets
of properties recur periodically.
2 Quantum Mechanical Model of the Periodic Table 2
Meyer based his periodic law on the property called atomic volume.
3 Electron Configurations 4

4 Periodic Law and the Periodic Table 4 Dmitri Mendeleev

Dmitri Mendeleev was a Russian chemist and inventor. He is credited as being
5 Periodic Properties of the Elements 6 the creator of the first version of the periodic table of elements.
5.1 Atomic and Ionic Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.2 Ionization Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5.3 Electron Affinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.4 Electronegativity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.5 Magnetic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

6 Metals, Nonmetals, and Metalloids 8

References
References of these notes

• General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring, Jeffry

D. Madura, and Carey Bisonnette. en.wikipedia.org/wiki/File:Medeleeff by repin.jpg

1
2 QUANTUM MECHANICAL MODEL OF THE PERIODIC TABLE 2

Predicted Observed • An additional electron raises the orbital energy due to electron-electron
Property Eka-silicon Germanium repulsions.
Atomic mass 72 72.6
Density, g/cm3 5.5 5.47 • Electrons in outer orbitals (higher n) are higher in energy because inner
Molar volume, cm3 /mol 13 13.22 electrons shield them from nuclear charge (effective nuclear charge, Zeff ).
Specific heat capacity, J/g-K 0.31 0.32 • Electrons that have a finite probability distribution near the nucleus
Color dirty gray grayish white (penetration) have lower energy. Thus, an energy level (shell) is split into
Density of oxide, g/cm3 EsO2 , 4.7 GeO2 , 4.703 sublevel (subshell) energies: s < p < d < f .
Boiling point of chloride EsCl4 , below 1000 C GeCl4 , 860 C
Chloride density, g/cm3 EsCl4 , 1.9 GeCl4 , 1.887 Summary
Hydrogen atom A typical multielectron atom
Mendeleev’s Periodic System
. . . (4p, 4d, 4f)
4s
4p
3s 3p 3d 3d
4s
3p
2s 2p
3s

Energy

Energy
1s
2p
2s

1s
en.wikipedia.org/wiki/File:Mendelejevs periodiska system 1871.png

Properties of Germanium Rules for Electron Assignment

Three elements predicted by Mendeleev were discovered shortly after the The electron configuration of an atom is a designation of how electrons are
appearance of his 1871 periodic table–gallium (1875), scandium (1879), and distributed among various orbitals in principal shells and subshells. The rules for
germanium (1886). this distribution are:
• Electrons occupy orbitals in a way that minimizes the energy of the atom.

2 Quantum Mechanical Model of the Periodic Table • 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
Splitting of Energy Levels electrons, and they must have opposite spins.
• The higher the nuclear charge Z lowers orbital energy by increasing • Hund’s rule. For orbitals of identical energy (degenerate orbitals), electrons
nucleus-electron attractions. initially occupy these orbitals singly.
2 QUANTUM MECHANICAL MODEL OF THE PERIODIC TABLE 3

Pauli Exclusion Principle • also called Hund’s Rule of Maximum Multiplicity.

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.
• Since electrons repel each other, the electrons attain the lowest energy level by
Aufbau Principle staying as far apart from each other by staying in different sub-orbitals.
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 Orbital Energy Diagram
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.

Hydrogen atom A typical multielectron atom

Klechkowski Rule 4s
. . . (4p, 4d, 4f)

4p
3s 3p 3d 3d
4s
3p
2s 2p
3s

Energy

Energy
1s
2p
2s

1s

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

Hund’s Rule
Hund’s Rule states that for degenerate orbitals, the lowest energy is attained Summary: Hund’s Rule
when the number of electrons with the same spin is maximized.
3 ELECTRON CONFIGURATIONS 4

a. correct The periodic table is an arrangement of the elements, by atomic number, in

which elements with similar physical and chemical properties are grouped together
1s 2s 2p in vertical columns.

b. correct
(since this is the 1 electron in the p sublevel
Modern Periodic Table
it can be either "spin-up" or "spin-down")
Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
1s 2s 2p Period
1 2
1
H He
c. incorrect 3 4 5 6 7 8 9 10
2
(the spin of the 2nd electron depends on the spin of the Li Be B C N O F Ne
1st electron, even though they aren't in the same orbital) 11 12 13 14 15 16 17 18
1s 2s 2p 3
Na Mg Al Si P S Cl Ar

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
d. correct 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5
(as long as you draw the first electron in each orbital as Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
"spin-up", you will draw a correct orbital diagram) 55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
1s 2s 2p 6
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
7
Fr Ra Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
commons.wikimedia.org/wiki/File:Hund%27s Rule.svg

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanides La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

3 Electron Configurations 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

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

Symbol # e− Electron configuration Group and Period

Li 3 1s2 2s1 A group is a vertical column of elements in the periodic table. Members of a group
Be 4 1s2 2s2 have similar properties.
B 5 1s2 2s2 2p1
C 6 1s2 2s2 2p2 • Group numbers at the top
N 7 1s2 2s2 2p3
A period is a horizontal row of the periodic table. All members of a period have
O 8 1s2 2s2 2p4
atoms with the same highest principal quantum number.
F 9 1s2 2s2 2p5
Ne 10 1s2 2s2 2p6 • arranged in order of increasing atomic number from left to right
Ge 32 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2
Au 79 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4 f 14 5d9 • numbered at the extreme left

Groups
4 Periodic Law and the Periodic Table
• The first two groups–the s block–and the last six groups–the p block–together
The Periodic Law constitute the main-group elements.
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. • Because they come between the s block and the p block, the d block elements
are known as the transition elements.
4 PERIODIC LAW AND THE PERIODIC TABLE 5

• The f block elements, sometimes called the inner transition elements, would P 1s2 2s2 2p6 3s2 3p3 → [Ne]3s2 3p3
extend the table to a width of 32 members if incorporated in the main body of Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d8 → [Ar]4s2 3d8
the table.

ns2np 1
ns2np 2
ns2np 3
ns2np 4
ns2np 5
ns2np 6
– The table would generally be too wide to fit on a printed page, and so the

ns1
ns2
f block elements are extracted from the table and placed at the bottom.
main group main group
1A 8A

1s 1s
• The 15 elements following barium (Z = 56) are called the lanthanides, and the 2A 3A 4A 5A 6A 7A

15 following radon (Z = 88) are called the actinides. 2s 2p

transition elements

Alkali earth metals

Noble gases
3s 3B 4B 5B 6B 7B 8B 1B 2B 3p

Halogens
Alkalai metals
4s 3d 4p
5s 4d 5p
Periodic Table and Electronic Configuration
6s 5d 6p
7s 6d

inner transition elements

s-block
1A
p-block 8A Lanthanide series 4f
1s 1s Actinide series 5f
2A 3A 4A 5A 6A 7A

2s 2p
d-block
3s 3B 4B 5B 6B 7B 8B 1B 2B 3p
4s 3d 4p Noble Gas Notation
5s 4d 5p
6s 5d 6p
1A 8A

7s 6d 2A 3A 4A 5A 6A 7A

Ne
f-block 3B 4B 5B 6B 7B 8B 1B 2B P Ar
4f Ni
5f

en.wikipedia.org/wiki/File:Periodic Table structure.svg

Periodic Table and Electronic Configuration

5 PERIODIC PROPERTIES OF THE ELEMENTS 6

5 Periodic Properties of the Elements Trend in Atomic Radius

5.1 Atomic and Ionic Size decreasing atomic radius

Atomic Radius He
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).
Fr increasing atomic radius
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
Ionic Radius
covalent compounds.
Cations are smaller than the atoms from which they are formed.
Ionic radius is the radius of a spherical ion. It is the atomic radius associated • For isoelectronic cations, the more positive the ionic charge, the smaller the ionic
with an element in its ionic compounds. radius.
Metallic radius is one-half the distance between the centers of adjacent atoms Anions are larger than the atoms from which they are formed.
in a solid metal.
• For isoelectronic anions, the more negative the charge, the larger the ionic
The van der Waals radii are strictly hard sphere radii measured using atomic radius.
distances in closest packed crystals.
• solid sample of a noble gas 5.2 Ionization Energy
Ionization Energy
Trend of Atomic Radius The ionization energy, I, is the quantity of energy a gaseous atom must absorb to
The atomic radius tends to decrease as one progresses across a period from left to be able to expel an electron.
right
• because the effective nuclear charge (Zeff ) increases, thereby attracting the • The first ionization energy I1 is the energy required to remove the most loosely
orbiting electrons and lessening the radius held electron from a gaseous atom.

The atomic radius usually increases while going down a group • The second ionization energy I2 is the energy required to remove an electron
from a gaseous unipositive ion.
• 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 Mg(g) → Mg+ (g) + e – I1 = 738 kJ/mol
with a few unusual peaks. Mg+ (g) → Mg2+ (g) + e – I2 = 1451 kJ/mol
5 PERIODIC PROPERTIES OF THE ELEMENTS 7

Trend in Ionization Energy 5.4 Electronegativity

Ionization energies decrease as atomic radii increase.
Electronegativity
• IE decreases down a group. Electronegativity (EN) is a measure of the ability of an atom to attract electrons
towards itself in the context of a chemical bond.
• IE increases across a period.
EN is related to IE and EA. In 1934, Robert S. Mulliken developed an approach
• I < I1 < I2 < · · · where
EN = IE − EA2
• reflects the effect of n on Zeff

An equation for ionization energy is

Trend in Electronegativity
Z2
I = RH × eff As one moves from left to right across a period in the periodic table, the
n2 electronegativity increases

• due to the stronger attraction that the atoms obtain as the nuclear charge
increases
5.3 Electron Affinity
Moving bf down a group, the electronegativity decreases
Electron Affinity
Electron affinity is the energy change associated with the gain of an electron by a • due to the longer distance between the nucleus and the valence electron shell,
neutral gaseous atom. thereby decreasing the attraction.

In general, EN is inversely related to atomic size.

F(g) + e – → F – (g) ∆Hea = −328 kJ/mol

Some EAs are endothermic, others are exothermic. Trend in Electronegativity

Trends in Electron Affinity increasing electronegativity

It is more difficult to make generalizations about EAs than about IEs.
F
• 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 Fr decreasing electronegativity
have to enter an empty p subshell, etc.
6 METALS, NONMETALS, AND METALLOIDS 8

Electronegativity: Pauling Scale ↑ ↑ ↑ ↑ ↑

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
en.wikipedia.org/wiki/Electronegativity
able to conduct heat and electricity.

5.5 Magnetic Properties Nonmetals

Magnetic Properties A nonmetal is an element whose atoms tend to gain small numbers of electrons
An important property related to the electron configurations of atoms and ions to form negative ions (anions) with the electron configuration of a noble gas.
is their behavior in a magnetic field. A spinning electron is an electric charge in
motion, which induces a magnetic field. • Nonmetal atoms may also alter their electron configurations by sharing
electrons.
• A diamagnetic substance has all its electrons paired and the individual
magnetic effects cancel out. It is slightly repelled by a magnetic field. • Nonmetals are mostly gases, liquid (bromine), or low melting point solids and
are very poor conductors of heat and electricity.
• 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.
Metalloids
A metalloid is an element that may display both metallic and nonmetallic
Paramagnetism in Manganese properties under the appropriate conditions.
The Mn atom ([Ar] 3d5 4s2 ) has a paramagnetism corresponding to 5 unpaired
electrons

↑ ↑ ↑ ↑ ↑ ↑↓ Trend in Metallic Character

Metallic property decreases across a period with increase in number of valence
When it loses 2 electrons to become Mn2+ , the strength of its paramagnetism electrons, as well as decrease in atomic radius, and it increases down the group
corresponds to 5 unpaired electrons. with increase in the number of shells and atomic radius.
6 METALS, NONMETALS, AND METALLOIDS 9

Trend in Metallic Character

decreasing metallic character

metalloids
F
nonmetals

metals
Fr
most increasing metallic character
metallic