Looking Back at Chemical Bonding

Bonding must be electric nature.

1852, E. Frankland proposed the valence concept, using for valence.
1857, F.A. Kekule figured out the structure of benzene C6H6.
1874 J.H. van't Hoff and le Bel postulated the tetrahedral arrangement of 4
bonds around carbon.
1916 G.N. Lewis propsed the dot symbol for valence electrons
1923 G.N. Lewis wrote Valence and the structure of atoms and molecules.
1939 L. Pauling wrote The nature of chemical bond
1940 N.V. Sidgwick and H.E. Powell studied the lone pairs of valence
electrons.
Basic Chemical Bonding 1
 Lewis Theory

G.N. Lewis (1875-1946) recognized

valence (outmost) electrons fundamental to bonding
electron transfer resulting in ionic bonds
sharing electrons resulting in covalent bonds
atoms tend to acquire a noble-gas electronic
configurations

The attraction between electrons of one atom to the nucleus of another

atom contribute to what is known as chemical bonds.

Basic Chemical Bonding 2

 Lewis Dot
Structure
Lewis wrote in a
memorandum
dated March 28,
1902

Basic Chemical Bonding 3

 Lewis Dot Structure 2
Lewis' Paper of 1916
In this paper, Lewis begins by using cubes, but he moves away from
them by the end of the paper. Here is how he visualized the elements
lithium through fluorine:

Please illustrate modern Lewis dot structures of periods

2 and 3 elements. Chieh does that during lecture.

Basic Chemical Bonding 4

 Lewis Dot in Covalent Bond
Write the Lewis dot structures for these molecules:
HH, HCl, HOH, NH3, H, He, Cl, Ne
H3O+, NH4+, OH , (coordinate covalent)
Cl2,
O2, (multiple bonds)
N2 ,
CO2
Explain the types in each line and write the dot structures.
Define: bond pair, lone pair, single bond, double bond, triple bond

Basic Chemical Bonding 5

Polar Covalent Bond & Electronegativity
Discuss the nature of these bonds:
HF, HCl
HOH (including lone pairs)
Electronegativity: the ability of an
element competing for bonding
electrons.

The variation as a function of atomic number and

its trends on the Periodic Table has been
discussed previously, and the Periodic Table
showing electronegativity is shown next.

Basic Chemical Bonding 6

Periodic Table of Electronegativity

Basic Chemical Bonding 7

 Covalent and Ionic Bonds
The ionicity of a bond depends on the difference in electronegativity.
A difference of 1.7 is given as 50% ionic, and usually considered ionic.

Analyze these

Basic Chemical Bonding 8

 Electron Density of a Polar Bond LiH

Li H
dipole moment

Basic Chemical Bonding 9

 Writing Lewis Dot Structures
Show all valence electrons.
Each bond represents two electrons.
All electrons are paired, usually (exceptions).
Each atom acquires 8 valence electrons, usually (exceptions).
Multiple bonds are needed sometimes.

Show class how to write Lewis structure for

CF4, (CX4, SiX4), NH3, H2O, HF
C2H5OH, HCN, H3PO4, O=N=O

Basic Chemical Bonding 10

 Formal Charge
The formal charge on any atom in a Lewis structure is a number
assigned to it according to the number of valence electrons of the
atom and the number of electrons around it.
The formal charge of an atom is equal to the number of valence
electrons, Nv.e. subtract the number of unshared electrons, N us.e. and
subtract half of the bonding electrons, Nb.e..

Formal charge = Nv.e. - Nus.e. - Nb.e.

Stability rules:
Formulas with the lowest magnitude of formal charges are more stable.
More electonegative atoms should have negative formal charges.
Adjacent atoms should have opposite formal charges.
Find Formal Charge

Confirm these FCs

 Resonance
When several structures with different electron distributions among the
bonds are possible, all structures contribute to the electronic structure
of the molecule. These structures are called resonance structures.
When two or more plausible Lewis structures can be written but the
correct structure cannot be written is called resonance. For example:

.. .. ..
O O O
:O: :O : :O: :O: :O: :O :

Please complete the dot structure and find the formal charge for the
above structures.
Basic Chemical Bonding 13
 Exceptions to the Octet Rule
Molecules with odd number of valence electrons, N=O
(compare to CO), CH3, OH, H, NO2 etc.
:Cl: :Cl: :Cl:
/ \ / \ / \
M M M M
Molecules with incomplete octets,
\ / \ / \ /
BeCl2 AlCl3, (gas and polymeric for both),
:Cl: :Cl: :Cl:
BF3, compare with NH3BF3, BF4 ,

M = Al or Be

Expanded valence shells, PCl3, PCl5, SF6, H2SO4, H3PO4

 Bond Properties
Bond length distance between the nuclei of bonded atoms
bond angle angles for any two bonds around an atom
bond energy energy required to break the bond
bond-dissociation energy
length energy
Bond Length Energy
Compound Bond (pm) (kJ/mol)
C C 154 348
H2 HH 74 436
C = C 134 614
C C 120 839 HF FH 92 565
H2O OH 96 464
O O 148 145 NH3 NH 101 389
O = O 121 498
CH4 CH 109 414
Basic Chemical Bonding 15
 VSEPR Theory
Valence-Shell Electron Repulsion Theory: The VSEPR model counts
both bonding and nonbonding (lone) electron pairs (E), and call the
total number of pairs number of electron groups (Neg). If the element A
has m atoms bonded to it and n nonbonding pairs (E), then
Neg = m + n
Discuss the electronic and molecular structures of CH 4, ENH3, &
E2OH2. All have Neg = 4.
Bond angles in these structure indicates that E E repulsion is stronger
than that of bonding electrons.
CH4 ENH3 H2OE2 HFE3

Basic Chemical Bonding 16

 Shape of Molecules
During the lecture, we will discuss structures of the following:
AX2 linear Make sure you can draw and name the
BeCl geometrical shape of these structures.
2

AX3, AX2E triangular planar, bent

BF3, SO2E
AX4, AX3E AX2E2 tetrahedral, pyramidal, bent
AX5, AX4E, AX3E2, AX2E3 triangular pyramidal, butterfly
PCl5, SF4E, ClF3E2, XeF2E3 T-shape, linear
AX6, AX5E, AX4E2 octahedral, square pyramidal, square planar
SF6, BrF5E, XeF4E2, ICl4E2 AX4E, whats my shape?
Basic Chemical Bonding 17
 Chemistry and Molecular Shapes
Neg Example Descriptor
2 BeCl2, CO2 Linear

3 BF3, SO3 Trigonal planar

SO2E, OO2E Bent

4 CH4 Tetrahedral
NH3E pyramidal Neg Example Descriptor
H2OE2 Bent
6 SF6, OIF5 Octahedral
5 PF5 Trigonal BrF5E Pyramidal
bypyramidal XeF4E2 Square planar
SF4E Seesaw, butterfly
Basic Chemical Bonding 18
ClF3E2 T-shape
 Structures with Multiple Covalent Bonds
We will talk about pi () bonding later.
At this stage, you may consider all electrons in a multiple bond are
confined around the lines connecting the two atoms. Thus the number
of electron groups Neg for a multiple bond is 1.
For example, Neg = 3 for H
.. \
S C=O
/ \\ /
::O: :O: H

What is the Neg for

SO42, COS, N2O? Basic Chemical Bonding 19
 Molecules with more than one central atom
Describe the structure of methyl isocyanate, CH 3NCO.
Draw the skeleton and add all valence electrons
H3C N C O
Draw the Lewis dot structure that satisfy the octet rule.
180o

109o N=C=O
120o
H-C
H H

What are the formal charges of all atoms in both structures?

Describe the structures of C2H5OH, CH3CO2H, and
H2NCH2CH2(OH)COOH. Basic Chemical Bonding 20
 Dipole Moment
The product of magnitude of charge on a molecule and the distance
between two charges of equal magnitude with opposite sign is equal to
dipole moment; D (unit is debye, 1 D = 3.34E30 C m (coulumb.metre);
representation Cl+H, a vector )
Dipole moment = charge x distance
Symbol: = e x d = q * dbond

For Cl+H, = 1.03 D, dHCl = 127.4 pm

Two ways of lookint at H+Cl,
q = 1.03*3.34e30 C m / 1.274e-12 m
= 2.70e-20 C (charge separation by HCl ) HCl = 1.03 D
Ionic character = q / e = 0.17 = 17% HF = 1.9 D, find d and %
d = 3.44e-30 C m / 1.60e 19 C (e charge) ionic character for them.
= 2.15E11 m = 0.215 pm (+eBasic

byChemical
0.215 pm)
Bonding 21
Dipole moment and Molecular Shape
Dipole moments are vectors. The net dipole moment of a molecule is
the resultant (vector sum) of all bond-dipole-moment.
Answer & explain these:
HH = ____
O=C=O = _____
CH4 = _____
CCl4 = _____
BF3 = _____
H2O = 1.84 D
O3 = 0.534 D (implication of long pair)
Which are polar and non-polar, SF6, H2O2, C2H4, Cl3CCH3, PCl5, I-Cl,
NO, SO2, CH2Cl2, NH3, (put your skill to tell molecular shape at work)
Basic Chemical Bonding 22
 Review 1
Predict the molecular geometry of the polyatomic anion ICl 4
Hint:
Draw the Lewis dot structure for Cl and I (figure out the valence e s)
Drew the Lewis dot structure for ICl4
What is the number of unshared e of the above?
Drew the ion, and describe this shape in proper term.

Do the same for NCl3, POCl3, COS, H2CO,

Basic Chemical Bonding 23

 Review 2
Apply bond energy for thermochemistry calculation
In a chemical reaction, add (ve) energy released from bonds
formed and (+ve) energy required to break the bonds is the energy
of the reaction Hrxno. Data:
D(O=O) = 498 kJ mol1
D(HH) = 436;
What is the heat of reaction for D(HO) = 464;
2 H2 (g) + O2 (g) 2 H2O (g), 2 H (g) H2 (g),
Hrxno = 2 * D (HH) + D(O=O) 4 * D(HO) H = D (HH)
H2 (g) H (g),
= 2 * 436 + 489 4*464
= 495 kJ compare to Hfo = 248 kJ mol1 of H2O H = D (HH)

Basic Chemical Bonding 24

Work on example 11-14 on page 423
 Review 3 Data:
D(C-H) = 414 kJ mol1
What is the energy of reaction for D(ClCl) = 243
CH4 (g) + Cl2 (g) CH3Cl (g) + HCl (g)? D(C-Cl) = 339
D(HCl) = 431
Solution:
H3C H + Cl Cl H3C Cl + H Cl
+ 414 + 243 339 431 kJ
Hrxno = + 414 + 243 339 431 kJ
= 113 kJ
Answer: 113 kJ is released in this reaction.

Basic Chemical Bonding 25