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SYSTEMATIC METHOD FOR DETERMINING LEWIS DOT

STRUCTURES

Do the following steps in order.

1. Sum the number of valence electrons from all atoms in the molecule.
2. Add or subtract appropriate number of electrons, if molecule is charged.
(Polyatomic ion)
3. Identify the central atom and decide how other atoms are bonded to it.
- least electronegative atom is usually central atom
- hydrogen is never central atom
4. Draw bonds between atoms. (Subtract 2 e- for each bond from total number
of valence e-)
5. Complete octets of peripheral atoms. (Subtract 1 e- for each electron used
from total number of valence e-)
6. Put remaining electrons in pairs on central atom. (if possible)
7. If central atom has too few electrons to complete octet, change lone pairs on
peripheral atoms to bonds between central atom and peripheral atom.
8. Write Lewis structure as to minimize formal charges. (More about formal
charges in a bit.)
- Most correct Lewis structure will have negative formal charge on most
electronegative atom. (Also, any positive charge must be on least
electronegative atom.)

Examples
Draw the Lewis structure for PCl3 .

1. # of e- = 5 + 3(7) = 26 e-
3. Central atom is P.

Draw the Lewis Structure of SO3 .

1. # of e- = 6 + 3(6) = 24 e-
3. Central atom is S.

7. Central atom has too few electrons, use multiple bond.

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Draw the Lewis Structure of NH4 +.
1. # of e- = 5 + 4(1) – 1 = 8 e-
2. Note: one electron is subtracted.
3. Central atom is N.

Draw the Lewis Structure of SF4 .

1. # of e- = 6 + 4(7) = 34 e-
3. Central atom is S.

6. Put remaining electrons on central atom.

- more about exceptions to octet rule later

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Lewis Structures With More Than One Central Atom.

Recall the reminders given previously concerning polyatomic bonding.

1. Carbon will form 4 covalent bonds per atom.

2. Oxygen will form 2 covalent bonds per atom.
3. Nitrogen will form 3 covalent bonds per atom.
4. Hydrogen will form 1 covalent bond per atom.
5. Halogens will form 1 covalent bond per atom.

Also keep in mind that hydrogen will never be a central atom and the halogens will be
a central atom generally in oxyacid anions such BrO3 -.

Most difficult detail of constructing Lewis structures is deciding how central atoms
are connected.

Often the chemical formula gives hints as how to make structure.

Example: Draw the Lewis dot structure for methanol, CH3 OH.

Note the chemical formula implies that three hydrogens are bonded to carbon and
one hydrogen is bonded to oxygen.

⇒ Carbon and oxygen must be bonded to each other.

# of e- = 4 + 6 + 4(1) = 14 e-

Example: Draw the Lewis dot structure for formaldehyde, CH2 O.

Example: Draw the Lewis dot structure for propane, CH3 CH2 CH3 .
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Example: Draw the Lewis dot structure for acetamide, CH3 C(O)NH2 .

We look to the chemical formula for help in deciding how to arrange atoms. The
O atom is put in parenthesis to clue us that the oxygen atom is above the chain of
central atoms.

Thus central atom skeleton looks like

Putting in the rest of the hydrogens and the electrons yields the structure:

Note that one carbon is deficient of electrons. Multiple bond must be used.
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Formal Charge
Each atom within a Lewis structure can be assigned a charge based on the number
of valence electrons it normally has versus the number of valence electrons
actually has.

Rules for Determining Formal Charge

1. Start with normal # of valence e- for atom.
2. Subtract number of nonbonding e- surrounding atom.
3. Subtract ½ number of bonding electrons surrounding atom.

Example: Which atom is assigned the 1+ charge in the ammonium ion?

+
H

H N H

Therefore, the N atom has positive charge in NH4 + ion.

Example: What are the formal charges of the atoms within a water molecule?
H

H O

Example: What are the formal charges of the atoms in the thiocyanate ion given the
Lewis structure below?

S C N

Formal Charge of S: 6 – 4 – ½(2) = 0

Formal Charge of C: 4 – 0 – ½(8) = 0
Formal Charge of N: 5 – 4 – ½(4) = -1

The negative charge of the thiocyanate ion lies on the nitrogen atom.
- Note: This is sensible, since the nitrogen atom is the most electronegative of
the three atoms.
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Using Formal Charge to Determine Lewis Structures
Recall rule 8 of our procedure to construct Lewis structures.
8. Write Lewis structure as to minimize formal charges.
- Most correct Lewis structure will have negative formal charge on most
electronegative atom. (Also, any positive charge on least electronegative
atom.)

Example: Which of the following Lewis structures is correct for carbon dioxide?

O C O O C O

Note both Lewis structures satisfy octet rule. But the correct one has
minimized formal charge.

O C O O C O

+1 0 -1 0 0 0
correct Lewis structure

Using multiple bonds in Lewis structures also minimizes formal charge.

Consider NO3 -

Use double bond to satisfy octet rule as well as minimize formal charges.

0 +1 -1

O N O

O
-1
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RESONANCE
- Sometimes more than one correct Lewis structure can be drawn.
- In that case, actual structure is a blend of correct structures.

Consider the nitrate ion again

O O O N O
N

O O

O N O

- Double-headed arrows indicate resonance structures.

Resonance structure implies the following:

- Double bond is not confined to a single O – N pair.
- Double bond is distributed over all three O – N pairs.

Consider oxalate ion, C2 O4 2-

O O O O

C C C C

O O O O

O O O O

C C C C

O O O O

- resonance adds to the stability of a compound or polyatomic ion.

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O O
-
C C -

O O

Double bond is distributed over both oxygen

atoms.

BENZENE
An important application of the idea of resonance is the molecule benzene, C6 H6 .

H H
H C H H C H
C C C C
C C C C
H C H H C H
H H
To illustrate that the double bonds form an uninterrupted circle, often benzene is
written as
H
H C H
C C
C C
H C H
H

The resonance in benzene makes it an exceptionally stable molecule. It is extremely

important in the chemistry of carbon (organic chemistry).
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EXCEPTIONS TO OCTET RULE
Three usual exceptions to Octet Rule
1. Molecules with odd number of e- (rare)
Example: ClO 2

Cl O

- note chlorine atom has 7 e-, not 8 e-

2. Molecules where atom has less than octet

- common in beryllium and boron compounds
Example: BF3

F B F

- Hmm! Why don’t we create double bond to satisfy octet rule. Look at
formal charge.
+1 -1 0
F B F

F
0

3. Molecules where atom has more than octet

- relatively common
- only atom in third row or below can “expand its octet”.
- valence shell is larger, more electrons can fit around the central atom

Recall previous example of SF4

F S F

- note sulfur has ten electrons

- sulfur has “expanded its octet”
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Example: I3 -

BOND ENTHALPIES
When two atoms bond together, the chemical energy of the system decreases.

Consider an energy level diagram of before bonding and after bonding.

H H

H–H

before after

The energy of the bonded system is lower than the unbonded system.

The energy released when two unbonded atoms become bonded is called the
bond enthalpy.

Aside: Enthalpy is another word for heat. We learn more about heat
and enthalpy in Chapter 6.

The bond enthalpy increases as atoms are more strongly bonded together. As the
strength of the bond increases, the distance between the atoms decrease.
Bond enthalpies are an experimentally found quantity; i. e., we can’t predict bond
enthalpies from periodic table.

Bond Enthalpies and Chemical Changes

**All chemical changes involve the breaking and creation of bonds.**

If we can understand what bonds are breaking and what bonds are forming, then we
can use bond enthalpies to estimate the energy (technically, enthalpy) change of the
reaction.

To break a bond, we input (add) the bond enthalpy.

When a bond is formed, the bond enthalpy is released (subtracted).
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Example: Given the table of bond enthalpies below, calculate the energy change,
when two molecules of hydrogen and one molecule of oxygen change into
two molecules of water.
H–H → O H O H
+ O –
– O
H–H
H H

TABLE OF BOND ENTHALPIES

Bond E (kJ/mol) Bond E (kJ/mol)

C–H 413 H–H 436
C–C 348 N–N 163
C–O 358 N=N 418
C=C 614 N≡N 941
C≡C 839 O–H 463
C=O 1072 O=O 495

Breaking two H – H bonds means inputting 2 x 436 kJ/mol.

Breaking one O = O bond means inputting 495 kJ/mol.
Forming four O – H bonds means releasing 4 x 463 kJ/mol.

Overall the energy change is

2 (436 kJ/mol) + 495 kJ/mol – 4 (463 kJ/mol) = – 485 kJ/mol

SHAPES OF MOLECULES (VSEPR MODEL)

Valence Shell Electron-Pair Repulsion model
- Electron domains surrounding atom spread out as to minimize repulsion.
- Electron domains can be bonding pairs (including multiple bonds) or
nonbonding pairs.
- Arrangement of all the atoms surrounding central atom depends on electron
domains surrounding central atom.

Two similar, but different geometries

1. Electron domain geometry
- arrangement of e- domain around central atom
- remember: multiple bonds count as a single e- domain

2. Molecular geometry
- arrangement of atoms around central atom

**A molecular geometry is decided only after an electron domain geometry has been
determined.**

*- need to write Lewis structure to determine number of electron domains.*

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Geometries with two e- domains about central atom.
1. electron domain geometry – linear
A A – generic atom
- angle between e domains is 180 °
-

2. possible molecular geometries

a) Linear
- only linear geometry is possible with two electron domains

Example: BeCl2

Cl Be Cl

Example: CO2

O C O

- Note: Only two electron domains around central atom since multiple bonds
count as a single domain.

Example: CO O C

Geometries with three e- domains about central atom.

1. electron domain geometry – trigonal planar

A – generic atom
A

- angle between e- domains is 120 °

2. possible molecular geometries

a) Trigonal Planar
- all three electron domains are bonding pairs

Examples: BF3 and NO3 -

F F O
B
N O
F O
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b) Bent (V-shaped)
- two bonding pairs and one nonbonding pair

Example: dichlorocarbene

C
Cl Cl

*Nonbonding e- pairs take up more room than bonding pairs. Therefore bond angle
between chlorine atoms is slightly less than 120°.*

Geometries with four e- domains about central atom.

1. electron domain geometry – tetrahedral
- tetrahedron is three dimensional object
- angle between electron domains is 109.4°

Caution! Representation is 2-D,

A not 3-D, bond angle between e-
pairs is not 90°

2. possible molecular geometries

a) Tetrahedral
- all four electron domains are bonding pairs

Example: CH4
H
H H
C H C H

HH H

2-D picture 3-D picture

Example: PO4 3-

O
O O
O P O P
O OO
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b) Trigonal Pyramidal
- 3 bonding pairs and 1 nonbonding pair

Example: NH3
H N H
N
H H H
H

- Bond angle is 107°. (specifically for NH3 )

- Bond angle is less than 109.4° because nonbonding pair takes more room
than bonding pair.

Example: ClO 3 -

O Cl O
Cl
O O O
O

c) Bent (V-shaped)
- two bonding pairs and two nonbonding pairs

Example: H2 O
H

H O

- Bond angle is 104.5°.

Redraw H2 O to show tetrahedral angle.

H H
O

Example: SF2

S
F F
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Geometries with five e- domains about central atom.
1. electron domain geometry – trigonal bipyramidal
- two different positions in a trigonal bipyramid
- axial – two position along axis
- equatorial – three positions along equator
- angle between equatorial positions is 120°
- axial positions are 90° from equator
* - nonbonding pairs prefer equatorial position*

2. possible molecular geometries

a. Trigonal Bipyramidal
- all five electron domains are bonding pairs

Example: PF5
F
F
F F F
P F P F
F F F

Note: axial bond lengths usually longer than equatorial bond lengths

b. Seesaw
- four electron domains are bonding pairs and one nonbonding pair

Example: SF4

F F
F
F S F S F
F F
- remember lone pairs prefer equatorial position
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c. T-shaped
- three electron domains are bonding pairs and two are nonbonding pairs

Example: ClF 3

F Cl F F
F Cl
F
F
- both lone pairs occupy an equatorial position

d. Linear
- two electron domains are bonding pairs and three are nonbonding pairs

Example: I3 - (triiodide ion)

I I I

- all three lone pairs occupy equatorial positions

Geometries with six e- domains about central atom.

1. electron domain geometry – octahedral
- angle between electron domains is 90°

2. possible molecular geometries

a.) Octahedral
- all six electrons domains are bonding pairs

Example: SF6
F
F F
S
F F
F
b.) Square pyramidal
- five electrons domains are bonding pairs with one lone pair

Example: BrF5
F
F F
Br
F F
- note angles will be slightly less than 90°
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c.) Square planar
- four electrons domains are bonding pairs with two lone pairs

Example: XeF4
F F
Xe
F F
- What are angles between fluorine atoms?

POLAR MOLECULES
A polar molecule has one side slightly positive and the other slightly negative.

Two conditions must be met in a polar molecule.

1.) Polar covalent bonds
2.) Correct geometry

To emphasize necessity of correct geometry, compare two examples.

BeCl2 H2 O
χBe = 1.5 χH = 2.1
χCl = 3.0 χO = 3.5
|χBe – χCl| = 1.5 |χH – χO| = 1.4

δ+ δ- δ+ δ-
Be – Cl H–O

indicates positive
end of bond

Be – Cl bond is more polar than H – O bond; however, BeCl2 is nonpolar molecule

and H2 O is a polar molecule.
Question: How can this be?
Answer: BeCl2 has a linear geometry and H2 O has a bent geometry.

δ+ H
H

O
Cl Be Cl
δ-
total polarity adds total polarity is nonzero
to zero
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Example: Is either ammonia or methane a polar molecule?
δ-
H H
N C
H H H
HH
δ+

Answer: Ammonia is a polar molecule, but methane is a nonpolar molecule.

Nonequivalent polar bonds can affect overall polarity.

CF4 is a nonpolar molecule. CF3 Cl is a polar molecule.

F Cl
C C
F FF F FF

Dipole Moment - µ
When equal and opposite charges, ±Q, are separated by a distance, d; the dipole
moment is defined as
µ=Q×d

Since a polar molecule has a separation of charge, it has a dipole moment.

Polarity of molecule is usually considered via its dipole moment.