Electronic Structure & Covalent Bonding

Roldan M. de Guia
Department of Biochemistry Faculty of Pharmacy University of Santo Tomas 2009

ORGANIC CHEMISTRY
compounds

the study of compounds of carbon there are over 10 million organic

(S)-((S)-1-((2S,3S)-3-hexyl-4-oxooxetan-2-yl)tridecan-2-yl) 2-formamido4-methylpentanoate

ATOMIC STRUCTURE

ELECTRON CONFIGURATION
Pauli Exclusion Principle
 Orbitals can contain a maximum of two electrons which

must be of opposite spin

ms = +½ ms = -½

ELECTRON CONFIGURATION
Aufbau Principle
 Atomic orbitals are filled with electrons from lowest

potential energy to highest.

ELECTRON CONFIGURATION
Madelung’s Rule
 Orbitals fill with

electrons as n + l, where n is the principle quantum number and l is the angular momentum quantum number  explains why the 4s orbital has a lower energy than the 3d orbital  gives the periodic table its characteristic appearance

“Fill up” electrons in lowest energy orbitals (Aufbau principle)

? ? Be6 electrons Li 54electrons B 3 C BBe 1s222s12 1 Li 1s 2s 1s22s22p

H 12 electrons He electron He 1s12 H 1s

The most stable arrangement of electrons in subshells is the one with the greatest number of parallel spins (Hund’s rule).

F 9 10 electrons Ne O 7 electrons N 6 electrons C 8
3 4 Ne 1s22s22p5 6 N 1s 2s2 2p2 C 1s222s22p O F

CHEMICAL BONDING
Atom Electronic Structure Electronic Configuration
3p 3s

Lewis Dot Structure

Boron

1s 2s 2p

2

2

1

2p 2s

B

1s

3p 3s

Phosphorus

[Ne] 3s23p3

2p 2s

P

1s

CHEMICAL BONDING – Octet Rule

Li+ +

F

-

Li+ F -

IONIC BONDING
Na Cl + 1 e Na + 1e Cl

COVALENT BONDING
σ* Eσ*
1s 1s

Eσ σ

COVALENT BONDING
 F2

F

F

A nonpolar covalent bond

 HF

H F
δ+ δ−

A polar covalent bond

CLASSIFICATION OF CHEMICAL BONDS

CLASSIFICATION OF CHEMICAL BONDS
Difference in Electronegativity between Bonded Atoms <0.5 0.5 – 1.9 >1.9 Type of Bond Non-polar covalent Polar covalent Ionic Most Likely Formed Between 2 non-metals or a non-metal & a metalloid A metal & a nonmetal

 Care must be taken to distinguish between polar bonds and polar molecules!!

MOLECULAR GEOMETRY VSEPR

POLARITY OF BONDS

H

Cl

O H H

O C

H C CH 3 3  Care must be taken to distinguish between polar bonds and polar molecules!! Carbon dioxide:

O C O

LEWIS STRUCTURE
F N F F O C O O

H

C

O

H

H H

C

O

total formal charge on = number of valence an atom in a electrons in Lewis the free structure atom

-

total number of nonbonding electrons

-

1 2

(

total number of bonding electrons

)

one of two or more Lewis structures for a single molecule that cannot be represented accurately by only one Lewis structure. + O O O O + O O

RESONANCE STRUCTURE

FORMAL CHARGE = 0

 Diazomethane, CH2N2

H C N N H
• Nitromethane, CH3NO2

H or C N N H

H O H C N O H or

H O H C N O H

STRUCTURES & FORMULAE

MOLECULAR MODELS

HYBRIDIZATION OF ORBITALS

CH4

HYBRIDIZATION OF ORBITALS

sp2 HYBRID ORBITALS
H H C C H
H C H C H H

Ethene

H

sp2 HYBRID ORBITALS

sp2 HYBRID ORBITALS

sp2 HYBRID ORBITALS

sp HYBRID ORBITALS

Acetylen e

sp HYBRID ORBITALS

sp HYBRID ORBITALS: CO2

O C O

O
O

C
C

O
O

Lengths of Covalent Bonds
Bond Type Bond Length (pm)

C-C C= C C≡ C C-N C= N C≡ N
Bond Lengths Triple bond < Double Bond < Single Bond

154 133 120 143 138 116

BOND LENGTH & STRENGTH

Effect of Hybridization on Bond Length & Strength BOND TYPE C –C sp3 – sp3 sp3 – sp2 sp3 – sp sp2 – sp2 sp2 – sp sp – sp # of π BONDS 0 0 0 1 0 2 BOND LENGTH, pm 154 153 146 147 142 138 BOND ENERGY, kcal/mole 82.76 85.48 91.58 91.42 96.48 103.60

↑ s character = ↓ bond length = ↑ bond strength

Comparison of Bond Length of C to C Bonds involving Hybrid Orbitals BOND TYPE BOND LENGTH, pm

Ethane Propylene Methylacetylene Ethylene Acetylene

CH3 – CH3 CH3 – CH = CH2 CH3 – C ≡ CH CH2 = CH2 CH ≡ CH

sp3 – sp3 sp3 – sp2 sp3 – sp sp2 – sp2 sp – sp

153.8 150.1 145.9 133.9 120.7

FUNCTIONAL GROUPS

FUNCTIONAL GROUPS

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