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Chapter 6
And 5.2
Representing
Molecules
Homework
Chapter 5: 3, 5, 7 and 9
Chapter 6: 23, 25, 29, 31, 35, 37, 39
41, 53, 57, 59, 73 and 79
Kent L. McCorkle
Cosumnes River College
Sacramento, CA
Copyright (c) The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
5.2
Boron 1s22s22p1
3 valence electrons
Na: 1s22s22p63s1
Na+: 1s22s22p6
10 electrons total,
isoelectronic with Ne
Cl: 1s22s22p63s23p5
Cl: 1s22s22p63s23p6
18 electrons total,
isoelectronic with Ar
B
1s22s22p1
1s22s22p2
1s22s22p3
5 valence electrons; first pair formed
in the Lewis dot symbol
Na
Na
Na 1s22s22p63s1
Valence electron lost in the formation
of the Na+ ion.
O 1s22s22p4
Na+
Na+ 1s22s22p6
Core electrons not represented in the
Lewis dot symbol
O2 1s22s22p6
Write Lewis dot symbols for (a) fluoride ion (F-), (b) potassium ion (K+), and
(c) sulfide ion (S2-).
Strategy Starting with the Lewis dot symbols for each element, add dots (for
anions) or remove dots (for cations) as needed to achieve the correct charge on
each ion. Dont forget to include the appropriate charge on the Lewis dot symbol.
Solution (a)
(b) K+
(c)
Think About It For ions that are isoelectronic with noble gases, cations should
have no dots remaining around the element symbol, whereas anions should have
eight dots around the element symbol. Note, too, that for anions, we put square
brackets around the Lewis dot symbol and place the negative charge outside the
brackets. Because the symbol for a common cation such as the potassium ion
has no remaining dots, square brackets are not necessary.
6.
3
Follow these steps when drawing Lewis structure for molecules and polyatomic
ions.
1)Draw the skeletal structure of the compound. The least electronegative atom is
usually the central atom. Draw a single covalent bond between the central atom and
each of the surrounding atoms.
2)Count the total number of valence electrons present; add electrons for negative
charges and subtract electrons for positive charges.
3)For each bond in the skeletal structure, subtract two electrons from the total
valence electrons.
4)Use the remaining electrons to complete octets of the terminal atoms by placing
pairs of electrons on each atom. Complete the octets of the most electronegative
atom first.
5)Place any remaining electrons in pairs on the central atom.
6)If the central atom has fewer than eight electrons, move one or more pairs from
the terminal atoms to form multiple bonds between the central atom and terminal
N
F
H with 2 e
H OH
O with 8 e
H O H
O C O
O= C= O
H O H
H OH
O with 8 e
O with 8 e
C with 8 e
A triple bond occurs when atoms are held together by three electron
pairs.
each N has 8 e
N N
<
N=N
124 pm
<
NN
147 pm
The shorter multiple bonds are also stronger than single bonds.
We quantify bond strength by measuring the quantity of energy
required to break it.
H2(g) H(g) + H(g)
Formal Charges
Sometimes, while drawing Lewis structures, you don't have observational data to use.
Formal charges can be used to find out what to choose.
Formal charge = (# of Valence shell e- of an atom) - (# Bond pair e-) - (# of unshared e-)
For example, lets take the first incorrect drawing of sulfuric acid.
Formal charge on S = 6 - 4 - 0 = 2
Formal charge on H = 1 - 1 - 0 = 0
Formal charge on O = 6 - 2 - 4 = 0 (on the ones bonded to H)
Formal charge on O = 6 - 1 - 6 = -1 (on the isolated ones)
We can disregard the ones with 0 formal charge.
The ones that do have formal charge are the sulfur and the isolated oxygens.
Since the 2 oxygens are -1 and sulfur is 2, another bond goes from each oxygen
to the sulfur to cancel the formal charge. (2 + 2(-1) = 0)
When several Lewis structures are possible, those with the smallest formal
charges are the most stable and are preferred.
total number
of valence
electrons in
the free atom
total number
of nonbonding
electrons
1
2
total number
of bonding
electrons
-1
+1
formal charge
on an atom in
a Lewis
structure
total number
of valence
electrons in
the free atom
total number
of nonbonding
electrons
formal charge
on C
= 4 -2 - x 6 = -1
formal charge
on O
= 6 -2 - x 6 = +1
1
2
total number
of bonding
electrons
H
H
0
C
formal charge
on an atom in
a Lewis
structure
0
O
total number
of nonbonding
electrons
formal charge
on C
= 4 - 0 - x 8 = 0
formal charge
on O
= 6 -4 - x 4 = 0
1
2
total number
of bonding
electrons
-1
+1
H
H
0
C
0
O
6.
4
Formal charge can be used to determine the most plausible Lewis
Structure when more than one possibility exists for a compound.
Formal charge = valence electrons associated electrons
To determine associated electrons:
1) All the atoms nonbonding electrons are associated with the
atom.
2) Half the atoms bonding electrons are associated with the atom.
O = O O
4 unshared + 4 shared = 6 e
2
+1
The N atom has five valence electrons and four associated electrons (one from
each single bond and two from the double bond). Each singly bonded O atom has
six valence electrons and seven associated electrons (six in three lone pairs and
one from the single bond). The doubly bonded O atom has six valence electrons
and six associated electrons (four in two lone pairs and two from the double
bond.)
Solution
The formal charges are as follows: +1 (N atom), -1 (singly bonded O atoms), and
0 (doubly bonded O atom).
Think About It The sum of formal charges (+1) + (-1) + (-1) + (0) = -1 is equal
to the overall charge on the nitrate ion.
Formal
charge
O= C= O
O C O
+1
Based on formal charge, identify the best and the worst structures
for the isocyanate ion below:
Solution:
Step 1 Assign formal charges on each atom using the formula
Formal charge = valence electrons associated electrons
Ve
Ae
FC
4
6
2
5
4
+1
6
6
0
4
5
1
5
4
+1
6
7
1
4
7
3
5
4
+1
6
5
+1
Based on formal charge, identify the best and the worst structures
for the isocyanate ion below:
Solution:
Step 2 Determine the best and worst structure
FC
+1
+1
+1
+1
Best structure:
Worst structure:
Formal charges
inconsistent with
electronegativities
Strategy The complete Lewis structures for the skeletons shown are:
Strategy The complete Lewis structures for the skeletons shown are:
-1
+1
Strategy The complete Lewis structures for the skeletons shown are:
Solution Of the two possible arrangements, the structure on the left has an O
atom with a positive formal charge, which is inconsistent with oxygens high
electronegativity. Therefore, the structure on the right, in which both H atoms are
attached directly to the C atoms and all atoms have a formal charge of zero, is the
better choice for the Lewis structure of CH 2O.
Think About It For a molecule, formal charges of zero are preferred. When
there are nonzero formal charges, they should be consistent with the
electronegativities of the atoms in the molecules. A positive formal charge on
oxygen, for example, is inconsistent with oxygens high electronegativity.
C
O
Resonance Structures
Sometimes, a single Lewis structure does not adequately
represent the true structure of a molecule.
Consider the carbonate ion, CO32-
carbon (C) has four valence electrons x 1 carbon = 4 eoxygen (O) has six valence electrons x 3 oxygens = 18 eThe ion has an overall negative two charge so we add 2 e- to
give a total of 24 e- to be placed in the Lewis structure.
Carbon is the central atom, the three oxygens are bound to it and
electrons are added to fulfill the octets of the outer atoms.
All the available electrons have been used but carbon is electron
deficient - it only has six electrons around it.
So
becomes
or
becomes
or
becomes
6.
5
A resonance structure is one of two or more Lewis structures for a
single molecule that cannot by represented accurately by only one
Lewis structure.
O = O O
O O= O
High oil and gasoline prices have renewed interest in alternative methods of
producing energy, including the clean burning of coal. Part of what makes
dirty coal dirty is its high sulfur content. Burning dirty coal produces sulfur
dioxide (SO2), among other pollutants. Sulfur dioxide is oxidized in the
atmosphere to form sulfur trioxide (SO3), which subsequently combines with
water to produce sulfuric acid a major component of acid rain. Draw all
possible resonance structures of sulfur trioxide.
Strategy Following the steps for drawing Lewis structures, we determine that a
correct Lewis structure for SO3 contains two sulfur-oxygen single bonds and one
sulfur-oxygen double bond.
But the double bond can be put in any one of three positions in the molecule.
Solution
Think About It Always make sure that resonance structures differ only in the
position of the electrons, not in the positions of the atoms.
Atoms in and beyond the third period can have more than eight
valence electrons.
In addition to the 3s and 3p orbitals, elements in the third period
also have 3d orbitals that can be used in bonding.
There are a total of 24 valence electrons (3 from the B and 7 from each of the
three I atoms). We subtract 6 electrons to account for the three bonds in the
skeleton, leaving 18 electrons to distribute in lone pairs on each I atom.
Solution
Think About It Boron is one of the elements that does not always follow the
octet rule. Like BF3, however, BI3 can be drawn with a double bond in order to
satisfy the octet of boron. This gives rise to a total of four resonance structures.
Draw two resonance structures for sulfurous acid (H 2SO3): one that obeys the
octet rule for the central atom, and one that minimizes the formal charges.
Determine the formal charges on each atom in both structures.
Strategy Begin by drawing the skeletal structure and counting the total number
of valence electrons. Use the steps outlined in Section 6.4 to draw the first
structure and reposition one or more lone pairs to adjust the formal charges for
the second structure.
Note that each hydrogen in an oxoacid is attached to an oxygen atom, and not
directly to the central atom. The total number of valence electrons is 26 (6 from
S, 6 from each O, and 1 from each H).
From the
top O
atom, Itwhich
has three
lone
pairs,
we reposition
Think
About
In some
species,
such
as the
sulfate ion,one
it islone pair to
create possible
a double to
bond
between too
O and
S todouble
get thebonds.
second
structure.with
incorporate
many
Structures
three and four double bonds to sulfur would give formal charges on
S and O that are inconsistent with the electronegativities of these
elements. In general, if you are trying to minimize formal charges by
expanding the central atoms octet, only add enough double bonds to
Incorporating
theformal
doublecharge
bond on
results
in every
atom
having a formal charge of
make the
the central
atom
zero.
zero.
6.
6
Exceptions to the octet rule fall into three categories:
1) The central atom has fewer than eight electrons due to a
shortage of electrons.
H Be H
2) The central atom has fewer than eight electrons due to an odd
number of electrons.
O= N O
17 valence electrons in
the system
6.
2
There are two extremes in the spectrum of bonding:
covalent bonds occur between atoms that share electrons
ionic bonds occur between a metal and a nonmetal and involve
ions
Bonds that fall between these extremes are polar.
In polar covalent bonds, electrons are shared but not shared
equally.
M:X
M+X
M+X
Pure covalent bond
Neutral atoms held
together by equally
shared electrons
Ionic bond
Polar covalent bond
Oppositely charged
Partially charged
atoms held together by ions held together by
unequally shared
electrostatic attraction
electrons
polar covalent
HF
HF
1 D = 3.3361030 Cm