II. Orbital and Periodicity

Key focus of this chapter: periodic table with groups

This chapter focuses on periodic table with groups and gives concise summaries of the important things about orbital theory, shapes of orbitals, rules of filling up electrons in orbitals, quantum numbers, electron configuration, atomic radius, ionization, and electron affinitive in more detail.

A. Orbital theory

1. Bohr’s atomic model

Bohr’s model accurately describes the hydrogen atom and other one-electron species.

In Bohr’s model, electrons occupy quantized energy levels (shells) around the nucleus; they are not treated as classical particles moving in fixed circular paths in the modern model.

Each electron shell is identified by the principal quantum number (n). For hydrogen, energy increases as n increases: K (n=1) < L (n=2) < M (n=3) < N (n=4).

Fig. 1 Bohr’s atomic model

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Energy change when electrons move to other electron shells

         Fig. 2  Ground and excited state electron s Ground state electron Excited state electron Absorb energy Electron shell Nucleus Emit energy K (n=1) L (n=2)

2. Lyman, Balmer, and Paschen series

3. Modern atomic model

: Limitations of Bohrs model led to the modern quantum-mechanical model (orbital theory).

a. Orbital theory

Electrons do not move in fixed paths. An orbital describes a region of high probability for finding an electron.

Each principal shell contains one or more subshells (s, p, d, f as allowed by n).

b. Electron shells and orbitals

As n increases, more subshell types become available: n = 1 has s; n = 2 has s and p; n = 3 has s, p, and d; n = 4 has s, p, d, and f.

Fig. 3 Modern atomic model Authenticated embedded content preview

B. Shapes of orbitals

C. Rules of filling up electrons in orbitals

: Electrons are expressed by arrow (Source symbol Symbol F0AF,Source symbol Symbol F0AD) in the orbital filling diagram

D. Quantum numbers

: Quantum numbers describe an electrons shell, subshell, orbital orientation, and spin.

Combined quantum numbers (n, l, ml)

E. Electron configuration

1. Filling order of electrons in orbitals (from low to high energy)

1s Source symbol Wingdings F0E0 2s Source symbol Wingdings F0E0 2p Source symbol Wingdings F0E0 3s Source symbol Wingdings F0E0 3p Source symbol Wingdings F0E0 4s Source symbol Wingdings F0E0 3d Source symbol Wingdings F0E0 4p Source symbol Wingdings F0E0 5s Source symbol Wingdings F0E0 4d Source symbol Wingdings F0E0 5p Source symbol Wingdings F0E0 ….

Fig. 4 Position of orbitals in the periodic table

2. Electron configuration

: Electron configuration describes how electrons occupy atomic orbitals.

Ex/

Fig. 5 Ground state electron configuration in the periodic table

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** Exceptional atoms of electron configuration

Cr, Cu, Nb, Mo, Ru, Rh, Ag (Dark red color above)

Ex/ Cr: 1s22s22p63s23p64s23d4 (X)    Source symbol Wingdings F0E0  1s22s22p63s23p64s13d5 (O)

Cu: 1s22s22p63s23p64s23d9 (X)   Source symbol Wingdings F0E0  1s22s22p63s23p64s13d10 (O)

F. Application of electron configuration

1. Counting of unpaired electrons: half filling electrons in orbital

Si: 1s22s22p63s23p2 Source symbol Wingdings F0E0  Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD Source symbol Symbol F0AD   1s 2s 2p 3s 3p (2 unpaired electrons in 3p orbital)

P: 1s22s22p63s23p3  Source symbol Wingdings F0E0  Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD Source symbol Symbol F0AD Source symbol Symbol F0AD 1s 2s 2p 3s 3p (3 unpaired electrons in 3p orbital)

S: 1s22s22p63s23p4  Source symbol Wingdings F0E0  Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD Source symbol Symbol F0AD 1s 2s 2p 3s 3p (2 unpaired electrons in 3p orbital)

Cl: 1s22s22p63s23p5  Source symbol Wingdings F0E0  Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD 1s 2s 2p 3s 3p (1 unpaired electron in 3p orbital)

2. Ground state and excited state

Ground state: the lowest-energy electron configuration.

Si: 1s22s22p63s23p2 Source symbol Wingdings F0E0 Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD Source symbol Symbol F0AD   1s 2s 2p 3s 3p (low energy state electron in 3s orbital)

Excited state: one or more electrons are promoted to higher-energy orbitals.

Si: 1s22s22p63s13p3 Source symbol Wingdings F0E0 Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD Source symbol Symbol F0AD Source symbol Symbol F0AD Source symbol Symbol F0AD 1s 2s 2p 3s 3p (high energy state electron in 3p orbital)

G. Electromagnetic spectrum

1. Light

Classified by wavelength (Source symbol Symbol F06C)

Speed of light: c = 3.00 × 10⁸ m/s in vacuum.

Frequency (ν): number of wave cycles per second (Hz = s⁻¹).

** Photoelectric effect: electrons are ejected from a metal only when incident light has a frequency above the threshold frequency; photon energy is E = hν.

2. Energy (E)

Long wavelength Source symbol Wingdings F0E0 low frequency Source symbol Wingdings F0E0 low energy

Short wavelength Source symbol Wingdings F0E0 high frequency Source symbol Wingdings F0E0 high energy

Ex/ Gamma rays Source symbol Wingdings F0E0 short wavelength Source symbol Wingdings F0E0 high energy

3. Order of energy

H. Periodicity

1. Periods

Seven rows (n = 1, 2, 3, 4, 5, 6, 7)

The period number corresponds to the highest occupied principal energy level for main-group elements.

2. Groups

18 groups (columns). Modern numbering is Groups 118; older A/B notation may also appear in study materials.

Elements in the same group often have similar chemical properties because they have similar valence-electron configurations.

have the same outermost electrons)

Ex/ Be, Mg, and Ca are Group 2 elements and have two valence electrons.

electrons)

Fig. 6 Periods and groups

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a. Metal and nonmetal

b. Classification of groups

Fig. 7  Classification of groups in periodic table

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I. Atomic radius

: Atomic radius is a measure of atomic size; it generally decreases across a period and increases down a group.

1. Atomic radius in periodic table

In the same period, when the atomic number is increased, the atomic radius is decreased

because the attraction force between the protons (+) and outer electrons (-) is increased.

Li > Be > B > C > N > O > F

In the same group, when the atomic number is increased, the atomic radius is increased

because the electron shells are increased.

Li < Na < K < Rb < Cs < Fr

In an isoelectronic series, radius decreases as nuclear charge (Z) increases.

metallic) radius is greater than its neutral atom.

Ca2+ < K+ < Ar < Cl- < S2-

2. Cationic (metallic) and anionic (nonmetallic) radius

J. Ionization energy (Ei)

: Ionization energy is the energy required to remove an electron from a gaseous atom or ion.

Atom + energy  Source symbol Wingdings F0E0  Cationic atom + e-

Fig. 8 Ionization energy of Li

+ 520 kJ/mol energy   Li + Li e -

Li + energy of (+520 kJ/mol)  Source symbol Wingdings F0E0  Li+ + e-

Increasing ionization  energy Increasing  nonmetallic  character Increasing attraction force   b/w nucleus and electrons Decreasing atomic  radius

First ionization energy (IE): energy required to remove the first electron from a gaseous atom.

octet rule)

Ar > Be > Li

Second ionization energy (IE₂): energy required to remove a second electron from the gaseous +1 ion.

Li > Ar > Be

a. General trend

In the same period, with the increasing atomic number, the Ei is increased.

O < F < Ne

In the same group, with the increasing atomic number, the Ei is decreased.

He > Ne > Ar

The half-filled or fully-filled electrons in each orbital have a strong Ei to remove an

outermost electron.

Ex/ Be: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF1s 2s              (1/1 fully-filled in 2s orbital)

B: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0AD     1s 2s 2p   (1/3 half-filled in 2p orbital)

Therefore, ionization energy: Be > B

Ex/ C: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0AD Source symbol Symbol F0AD   1s 2s 2p    (2/3 half-filled in 2p orbitals)

N: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0AD Source symbol Symbol F0AD Source symbol Symbol F0AD 1s 2s 2p   (3/3 half-filled in 2p orbitals)

O: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD Source symbol Symbol F0AD 1s 2s 2p    (1/3 fully-filled in 2p orbitals)

Therefore, ionization energy: N > O > C

Fig. 9 Ionization energy of the atoms

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K. Electron affinity (EA)

: Electron affinity describes the energy change when a gaseous atom gains an electron. For many nonmetals the process is exothermic; sign conventions vary by textbook, so focus on relative favorability/trends for DAT questions.

Atom + e-  Source symbol Wingdings F0E0  anionic atom + energy

Fig. 10 Electron affinity of F

          e - - 340  kJ/mol energy F - F

F + e-   Source symbol Wingdings F0E0   F- + energy of (-340 kJ/mol)

Easily becoming anionic atom        Increasing electron affinitive Increasing  nonmetallic  character

a. General trends

Noble gases have very unfavorable electron affinities because an added electron must enter a higher-energy shell/subshell.

Across a period, electron affinity generally becomes more favorable (more energy released), but the trend is irregular.

N < O < F

Down a group, electron affinity generally becomes less favorable, with important exceptions (for example, Cl is more favorable than F).

Cl > Br > I        ** exception (F < Cl)

An atom that is 2/3 half-filled in orbitals has the stronger Eea than 3/3 half-filled in orbitals.

Ex/ C: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0AD Source symbol Symbol F0AD   1s 2s 2p (2/3 half-filled in 2p orbitals)

N: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0AD Source symbol Symbol F0AD Source symbol Symbol F0AD 1s 2s 2p (3/3 half-filled in 2p orbitals)

Therefore, electron affinity is more favorable for C than for N (N is relatively unfavorable because of its half-filled 2p subshell).

An atom that is 2/3 fully-filled in orbitals, has the stronger Eea than 3/3 fully-filled in

orbitals.

Ex/ F: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0AD 1s 2s 2p  (2/3 fully-filled in 2p orbitals)

Ne: Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF Source symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AFSource symbol Symbol F0ADSource symbol Symbol F0AF1s 2s 2p  (3/3 fully-filled in 2p orbitals)

Therefore, F has a much more favorable electron affinity than Ne; noble gases have very unfavorable electron addition.

Fig. 11 Electron affinity of the atoms

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L. Tendency of atoms in periodic table

Moving left and down the periodic table, metallic character and atomic radius generally increase. London dispersion forces generally increase with electron count/polarizability, but are not a simple universal periodic trend.

Moving right and up, electronegativity and first ionization energy generally increase. Electron affinity is less regular and has important exceptions.

Fig 12. Tendency of atoms in periodic table

     •   Metallic character       •   Atomic radius      •   Intermolecular forces         (=London dispersion) He He F F      •   Electronegativity      •   Ionization energy      •   Electro affinity

** He: Strongest ionization energy

F: Strongest electronegativity

Review list:    Orbital theory      Bohr ’ s atomic model       Ground and excited states       Lyman, Balmer, and Paschen series       Modern atomic model    Shapes of orbital s  (s, p, d, f)    Rules of filling up electrons in orbitals (Pauli exclusion principle, Hund ’ s rule, filling order)    Quantum numbers (n, l, M l )    Electron configuration       Ground state electron configuration       Orbital filling diagrams        Half filling electrons in orbital s       Ground and excite d  state s  in orbital s    Electromagnetic spectrum       Light:  C =        Energy: E = = h         Order of energy    Periodicity       Periods       Groups (metal and nonmetal)       Classification of groups (alkali metals, alkaline earth metals, transition metals, semi metals,         halogen s , noble gas es )    Atomic radius       Atomic radius in periodic table       Cationic and anionic radius    Ionization energy (E i )    Electron affinitive (E ea ) Tendency of atoms in periodic table ( metallic character,  atomic radius,  intermolecular  forces,   electronegativity, ionization energy, electro affinity)