General Chemistry

Chem. 102 for Engineering

Tutorial 6
1

1A

Valence Electrons
Lewis Dot Symbols

18

8A

12

13

14

15

16

17

2A

3A

4A

5A

6A

7A

Number of valence electrons is equal to the Group number

Sulfite ion, SO32Step 1. Central atom = S Step 2. Count valence electrons S= 6 3 x O = 3 x 6 = 18 Negative charge = 2 TOTAL = 6 + 18 + 2 = 26 eStep 3. Form sigma bonds 10 pairs of electrons are left.

O O S O
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Sulfite ion, SO32- (2)

Remaining pairs become lone pairs, first on outside atoms then on central atom.

O S

2-

Each atom is surrounded by an octet of electrons.

Example: Write the Lewis structure for CN- ion and calculate the formal charge for both atoms Number of valence electrons = 10 For C: There are 4 valence electrons (from periodic table). In the Lewis structure there are 2 nonbonding electrons and 3 from the triple bond. There are 5 electrons from the Lewis structure. Formal charge: 4 - 5 = -1. For N: There are 5 valence electrons. In the Lewis structure there are 2 nonbonding electrons and 3 from the triple bond. There are 5 electrons from the Lewis structure. Formal charge = 5 - 5 = 0. We write:
0

C N

C N

Some additional structures and observations Isoelectronic molecules have the same number of valence electrons and thus the same Lewis Dot Structures
NO+, N2, CO, CN- all have 10 electrons [ N O ]+ N N C O [ C N ] H3O+, NH3: 8 valence electrons

H N H H

H O H + H
+

CO2, OCN-, SCN-, N2O, NO2+, COS, CS2: 16 valence electrons

O C O N C O N C S O N O O C S S C S

CO32-, NO3-: 26 valence electrons

O N O O O N O O
2-

O N O O

PO43-, SO42-, ClO4-: 32 valence electrons

O O P O O 3etc.
O O S O O etc.
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Lewis Structures: Examples a) CH2ClF

Cl H C H F

A resonance structure is one of two or more Lewis structures for a single molecule that cannot be represented accurately by only one Lewis structure.
When one LS cannot represent the molecule and we have to use a set of equally good LS, this set is called the resonance structures.

Ozone O3

1O

1+ O

1+ O

1O

What are the resonance structures of the C 4 ecarbonate (CO32-) ion?

3O 3x 6 e-ve charge 2 e24 e-

C O

C
O

O 1

C
O

O 1
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If you have more than one possible Lewis structures, how do you tell which one is better? Formal charge principle
Example: Write the possible Lewis structures for the sulfate ion (SO42-), and decide which is more possible Possible structure No. I The number of valence electrons = 32eEach O atom has 6 unshared e- (3 lone pairs) and shared 2 electrons with S atom Calculate formal charges for S and O
-1 -1 +2 -1

-1

Possible structure No. II

0 -1 0 -1

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There are two fundamental assumptions about using formal charges to evaluate Lewis structure: 1. Atoms in molecules try to achieve formal charge as close to zero as possible. 2. Any negative formal charges are expected to reside on the most electronegative atoms. 3.Adjacent atoms should not carry formal cahrges of the same sign. Notice that, In the structure with only single bonds each oxygen has a formal charge of 1, while the sulfur has a formal charge of +2.

In contrast, in the structure with two double bonds and two single
bonds, the sulfur and the 2 oxygen atoms have a formal charge of zero. So this structure is preferred as it has lower formal charges.

Resonance structures

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Resonance structures
SO2 Sometimes we can have two or more equivalent Lewis structures for a molecule. OS=O O=SO

- Satisfy the octet rule - have the same number of bonds - have the same types of bonds - Have the same formal charges . Which is right?
9 - 12

Resonance structures
No one of them is correct!
-1 +1

OS=O

O =SO

The correct structure

Hybrid structure

This results in an average of 1.5 bonds between each S and O.

9 - 13

Alternate Lewis structure for SO2 uses 2 double bonds

Sulfur does not obey OCTET rule BUT the formal charge = 0

O=S=O
This is better structure than O=S+-Osince it reduces formal charge. 3rd row S atom can have 5 or 6 electron pairs

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Carbon Dioxide, CO2

1. Central atom = __C____ 2. Valence electrons = _16_ or _8_ pairs 3. Form sigma bonds.

This leaves __6__ pairs (12 e-). 4. Place lone pairs on outer atoms.

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Carbon Dioxide, CO2

4. Place lone pairs on outer atoms.

5. To give C an octet, form DOUBLE BONDS between C and O.

The second bonding pair forms a pi

(p) bond.
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Carbon Dioxide
At OXYGEN

6 - (1/ 2)(4) - 4

O
=

At CARBON

4 - (1/ 2)(8) - 0

0
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Carbon Dioxide
An alternate Lewis structure is: 6 - (1/ 2)(2) - 6 =

-1

C atom charge is 0.

6 - (1/ 2)(6) - 2

= +1

AND the corresponding resonance form

O
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Carbon Dioxide, CO2

Which is the predominant resonance structure?

C
C

OR

Answer ? Form with zero formal charges is BETTER [no +ve charge on O]
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Thiocyanate ion, (SCN)-

A.

S=C=N S=C - N S-C N

Which of three possible structures is most important? B.

C.

ANSWER: A

Exercise: Write the three possible resonance structures for cyanate ion, NCO- and decide which form is most important?
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Exceptions to the Octet Rule (electron deficient atoms)

Boron Trichloride, BCl3

Cl
B

Cl

Cl

What if we form a BCl double bond to satisfy the B atom octet?

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Boron Trifluoride BF3, BCl3 (2)

Cl +1
B -1

fc = 7 - 2 - 4 = +1 Chlorine fc = 3 - 4 - 0 = -1 Boron

Cl

Cl

To have +1 charge on Cl, with its very high electron affinity is not good. -ve charges best placed on atoms with high EA. Similarly -1 charge on B is bad Ignore octet rule and consider 22 boron as exception.

Exceptions to the Octet Rule (Expanded valence shells)

Molecules having atoms with more than 8 electrons This can occur for molecules in which the central atom is in the third or later periods

Group 4A F F Si F

Group 5A F F F P F F F F F P F F F -

Group 6A F F S F F F F F S F F F

Group 7A F F Cl F F F F Br F F

Group 8A F Xe F F F Xe F F

F F 2-

F F F Si F F F

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The total number of lone pairs in NCl3 is A. 6 B. 8 C. 9 D. 10 E. 13 The Lewis structure for CS2 is:

None of the above

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The best Lewis structure for a chlorate ion, ClO 3, should show ____single bond(s), ____ double bond(s), and ____ lone pair(s).
A. B. C. D. E. 2, 1, 10 3, 2, 10 1, 2, 8 3, 0, 10 2, 1, 9

The number of resonance structures for the sulfur dioxide molecule that satisfy the octet rule is (see previous) A. 1. B. 2. C. 3. D. 4. E. None of these. What is the formal charge on sulfur in the best Lewis structure for the SCN (thiocyanate) ion? (see previous) A. +2 B. 2 C. +1 D. 1 E. 0
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Which of these statements is a useful guideline for the application of formal charges in neutral molecules? A. Lewis structure in which there are zero formal charges is preferred. B. Lewis structures with large formal charges (e.g., +2,+3 and/or 2,3) are preferred. C. The preferred Lewis structure is one in which positive formal charges are on the most electronegative atoms. D. The preferred Lewis structure is one in which negative formal charge is on the central atom. E. (A) and (D).

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Consider the following molecules. BF3 CHBr3 (C is the central atom) Br2 XeCl2 CO SF4 Select the molecule(s) that fits the statement "these molecules violate the octet rule"
A. B. C. D. E. I, II, IV I, III, IV, VI III, V, IV I, IV, VI I, II, IV, VI

In the Lewis structure of ICl2, how many nonbonding pairs of electrons are around the central iodine atom? A. 0 B. 1 C. 2 D. 3 E. 4
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