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Examples
Draw the Lewis structure for PCl3 .
1. # of e- = 5 + 3(7) = 26 e-
3. Central atom is P.
1. # of e- = 6 + 3(6) = 24 e-
3. Central atom is S.
1. # of e- = 6 + 4(7) = 34 e-
3. Central atom is S.
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.
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.
# of e- = 4 + 6 + 4(1) = 14 e-
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.
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.
H N H
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
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
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.
O O O N O
N
O O
O N O
O O O O
C C C C
O O O O
O O O O
C C C C
O O O O
O O
-
C C -
O O
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
Cl O
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
F S F
BOND ENTHALPIES
When two atoms bond together, the chemical energy of the system decreases.
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.
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.
2. Molecular geometry
- arrangement of atoms around central atom
**A molecular geometry is decided only after an electron domain geometry has been
determined.**
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
A – generic atom
A
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°.*
Example: CH4
H
H H
C H C H
HH H
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
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
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*
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
I I I
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.
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
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+
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