Chapter 1: Chemical Bonding

Aspartame (Nutrasweet)

I. Electronic Configurations of the Elements

Periodic Table Review: periods; principle quantum numbers s-block, p-block, d-block; groups s and p atomic orbitals rules for filling atomic orbitals core and valence electrons Question 1-1. From a periodic table, give the electron configuration and Lewis structure for the following atoms. Then click on the arrow to check your answers. C N O F Cl

Check Answer

I. Electronic Configurations of the Elements

Answer 1-1: Electron Configuration C [He]2s22p2 Lewis Symbol

C
N
O

[He]2s22p3

[He]2s22p4

[He]2s22p5

F Cl
3

Cl

[Ne]2s22p5

II. Bonding and Molecular Structure

A. Ionic, covalent, and polar bonds: electronegativity
ionic bonds: transfer of electrons

Na + Cl

Na

+ Cl

covalent bonds: sharing of electrons

H + Cl

H Cl

electronegativity, ': relative attraction for electrons in a bond - increases going up and to the right in the periodic table - Pauling electronegativity scale (arbitrary): Table 1.2

II. Bonding and Molecular Structure

A. Ionic, covalent, and polar bonds: electronegativity
HH ' = 2.1 2.1 ClCl ' = 3.0 3.0 H+ H HCl ' = 2.1 3.0 (' = 0 equal sharing of electrons = nonpolar covalent bond nonmetal + nonmetal (' = 0.9 unequal sharing of electrons = polar covalent bond metal + nonmetal

Na+Cl ' = 0.9 3.0 generally:

(' = 2.1 transfer of electrons = ionic bond when (' < 1.9 covalent > 1.9 ionic

Question 1-2. Use a periodic table or use the Pauling electronegativity values to classify each of the following compounds as non-polar covalent, polar covalent, or ionic. Click on the arrow to check your answers. F2

H2

HF

NaF
Check Answer

Answer 1-2. Compare your answers:

F2

Non-polar covalent

H2

H H
H H


Non-polar covalent

HF

H F

Polar covalent

NaF

Na+ F-

Ionic

II. Bonding and Molecular Structure

B. Drawing Lewis structures
1. Count all the valence electrons; add one for each charge subtract one for each + charge 2. Draw single bonds between the atoms (the connectivity of the atoms is determined experimentally and is usually given in the problem). 3. Using the remaining valence electrons, place octets on all atoms (exception H), in order of decreasing electronegativity. 4. If atoms do not have octets, use lone pair electrons on adjacent atoms to form double or triple bonds to complete the octets. 5. Determine formal charges. 6. The better Lewis structure is the one: -with fewer formal charges -with more octets -with a charge on a more electronegative atom, and vice versa
8

II. Bonding and Molecular Structure

B. Drawing Lewis structures Question 1-3. Draw Lewis structures of the following.
CCl4 CH2O C 2H 2 CH3OH CH3CHCH2
Check Answer

HCN
9

II. Bonding and Molecular Structure

B. Drawing Lewis structures Answer 1-3. Draw Lewis structures of the following.
Cl Cl C Cl Cl
O H C H
H C C H

CCl4
H H C H O H

CH2O

C2H2

H H H H C C C H H

H C N
HCN
10

CH3OH

CH3CHCH2

II. Bonding and Molecular Structure

C. Formal charges
(Use the silly, complex formula in the textbook, or use this easier method.) 1. Divide the electrons in each bond equally between the two atoms sharing them. 2. Count the number of electrons each atom now has and compare this number to its normal valence. -more electrons than normal valence negative formal charge -fewer electrons than normal valence positive formal charge Question 1-4. Draw the Lewis structures, then determine the formal charge on each atom in the following molecules or ions. Check your answer by clicking on the arrow. H3O+ CH3O CH3+ CO N 3
Check Answer

11

II. Bonding and Molecular Structure

C. Formal charges
Answer 1-4. Compare your answers.

H H O H O: 6 - 5 = +1

H H C O H C: 4 - 4 = 0 O: 6 - 7 = -1
1 2 3

H H C H C: 4 - 3 = +1
1 2 3

C O C: 4 - 5 = -1 O: 6 - 5 = +1

N N N N1: 5 - 5 = 0 N2: 5 - 4 = +1 N3: 5 - 7 = -2

or

N N N N1: 5 - 6 = -1 N2: 5 - 4 = +1 N3: 5 - 6 = -1

12

II. Bonding and Molecular Structure

C. Formal charges
When two or more nonequivalent Lewis structures are possible, the better (more stable) one is the one with: 1. fewer formal charges 2. more octets 3. a charge on a more electronegative atom, or a + charge on a more electropositive atom In decreasing order of importance

Question 1-5. Draw the most stable Lewis structure for each of the following compounds. Check your answers by clicking on the arrow. COCl2 BF3 (CH3)2SO HOCN
Check Answer

13

II. Bonding and Molecular Structure

C. Formal charges
Answer 1-4. The preferred Lewis structures are shown here. Note that formal charges for all atoms in the preferred Lewis structure are 0.
O Cl C Cl

F F B F

F +1

not

B -1

H O H H C H S C H H

H O C N

14

II. Bonding and Molecular Structure

D. Structural formulas of organic compounds
structural formula
H H H H H H C C C C C H CH3CH2CH2CH2CH3 H H H H H H H OH H H C C C C H H H H H H O H H C C H C H H CH3CH2CHCH3 OH CH3CH2CH(OH)CH3 O CH3CCH3 CH3COCH3 (CH3)2CO
15

condensed formula

bond-line formula

OH

II. Bonding and Molecular Structure

D. Structural formulas of organic compounds
Question 1-6. Draw the first two compounds in a bond-line formula. Draw the second two compounds in a condensed formula. Click on the arrow to check your answer.
(CH3)3CCH2CH2CH(CH3)2
CH3CH2C(CH3)2CH(OH)CH2CH2CH2Cl

OH

OH Br

Check Answer

16

II. Bonding and Molecular Structure

D. Structural formulas of organic compounds
Answer 1-6. Draw the first two compounds in a bond-line formula. Draw the second two compounds in a condensed formula. Click on the arrow to check your answer.
Cl OH
(CH3)3CCH2CH2CH(CH3)2
CH3CH2C(CH3)2CH(OH)CH2CH2CH2Cl

OH
OH

(CH3)2CHCH2C(CH3)2CH(OH)CH(Br)CH3
OH Br

H2C H2C

CH CH2

CH2 CH2

17

II. Bonding and Molecular Structure

E. Constitutional isomers -different atoms bonded to one another; different connectivity
C4H10 H H H H H C C C C H H H H H H H H H C C C H H H H C H H C3H8O C C C O O C C C C O C C CH3CH2CH2OH OH CH3CH(OH)CH3 CH3CH2OCH3 O
18

CH3CH2CH2CH3

CH3CHCH3 CH3 CH3CH(CH3)CH3 OH

II. Bonding and Molecular Structure

E. Constitutional isomers
Question 1-8. Draw all of the constitutional isomers for the following. Check your answer by clicking on the arrow. C4H9Cl

C3H6O

Check Answer

19

II. Bonding and Molecular Structure

E. Constitutional isomers
Answer 1-8. There are four constitutional isomers and five constitutional isomers, respectively. C4H9Cl
Cl Cl Cl Cl

C3H6O
O O H O O O

20

II. Bonding and Molecular Structure

F. Resonance structures -atomic positions (connectivity) the same, but different arrangement of electrons

delocalized electrons

HCO2

O H C O H C

O = H C O

O O -

neither of these accurately describes the formate ion actual species is an average of the two

1.5 bond order

greater number of equivalent resonance structures greater stability = resonance stabilization

21

II. Bonding and Molecular Structure

F. Resonance structures Question 1-8. Draw resonance forms for the following. Indicate whether the resonance forms are equivalent in energy. If not, indicate the major resonance contributor (most stable). Click on the arrow to check your answers.
SCNCH2N2 CH3CO2-

Check Answer

22

II. Bonding and Molecular Structure

F. Resonance structures Answer 1-8. The major resonance forms are marked. Formal charge is indicated above the structure.
0 0 -1 S C N -1 S 0 0 C N +1 0 -2 S C N

SCN-

More electronegative atom has negative charge.

H H H C N N
0 +1 -1

CH2N2

H C N N
-1 +1 0

More electronegative atom has negative charge. CH3CO2

-

H O H C H C O

H O H C H C O

equal in stability
23

II. Bonding and Molecular Structure

G. Molecular geometry: Question 1-9. Draw Lewis structures and determine molecular geometry for each of the molecules. Click on the arrow to check.
formula C2H2 CH2O CH4 HCN NH3 H2O
Check Answer

e pair geometry

molecular geometry (angle)

24

II. Bonding and Molecular Structure

G. Molecular geometry: Answer 1-9. Draw Lewis structures and determine molecular geometry for each of the molecules. Click on the arrow to check.
formula C2H2 CH2O CH4 HCN NH3 H2O Lewis
H C
O H C
H C H H H

e pair geometry
H linear
H

molecular geometry (angle) linear (180) trigonal planar (120) tetrahedral (109.5)

trigonal planar tetrahedral

H C N

linear tetrahedral tetrahedral

linear (180) trigonal pyramidal (107) bent (104.5)

25

N H H H

O H H

II. Bonding and Molecular Structure

H. Molecular polarity Question 1-10. Draw the Lewis structures, give the molecular geometry, and determine whether the following will be polar or non-polar. Click on the arrow to check your answers.

CCl4

CHCl3

CH2O

CO2

Check Answer

26

II. Bonding and Molecular Structure

H. Molecular polarity Answer 1-10. Draw the Lewis structures, give the molecular geometry, and determine whether the following will be polar or non-polar. Click on the arrow to check your answers.
CCl4
Cl Cl C Cl Cl

CHCl3
Cl

H C Cl Cl

no net dipole: non-polar CH2O

H O C H

net dipole: polar CO2

O C O

net dipole: polar

no net dipole: non-polar

27

III. Other Bonding Theories

A. Molecular orbital theory: H2
H + H p HH

Two electrons in W1s are lower energy than in the separate atoms covalent bond
28

III. Other Bonding Theories

B. Valence bond theory
1. sp3 hybridization CH4 facts:
H C H H H

tetrahedral, 4 equivalent bonds

2p 2s
hybrid a.o.s:

promote electron

hybridize

2p 2s H
4H sp3 hybrid a.o.s

sp3

C(sp3) tetrahedral

C H H H
W(sp3C + 1sH)

29

III. Other Bonding Theories

B. Valence bond theory
1. sp3 hybridization

C H H C C H H H W(sp3C + sp3C) H

N lone pairs in sp3 a.o.s H C N H H H W(sp3C + sp3N) H

H C O H H W(sp3C + sp3O)

30

III. Other Bonding Theories

B. Valence bond theory
2. sp2 hybridization trigonal planar = sp2 C2H4 facts: H
C C H H
1s

all six atoms lie in same plane

1s

1s 2p sp
2

H C
sp

H
2p

1s

C
2p

T bond

H H

C C

H H

overlap p orbitals

H H

C C

H H
=

H C H C

H H double bond = 1 T bond + 1 W bond

W(sp2C + 1sH) W(sp2C + sp2C)

all atoms coplanar for p orbital overlap

31

III. Other Bonding Theories

B. Valence bond theory
2. sp2 hybridization

C H H C C H H W(sp2C + sp2C) + T H H

O lone pairs in sp2 a.o.s

C O

W(sp2C + sp2O) + T

32

III. Other Bonding Theories

B. Valence bond theory
3. sp hybridization C2H2 facts: H

C C H

linear = sp

1s

H
2p sp

1s

C
2p H

2p sp 2 T bonds

C C

H W(spC + 1sH)

C C

H = H

W(spC + spC)

triple bond = 2 T bonds + 1 W bond

33

III. Other Bonding Theories

B. Valence bond theory
3. sp hybridization

N lone pair in sp a.o. H C N

W(spC + spN) + 2T

34

III. Other Bonding Theories

B. Valence bond theory
Question 1-11. What is the hybridization of each indicated atom in the following compound? Click on the arrow to check your answers.

CH3 OH C CH

HO
17-ethynylestradiol (The Pill) Check Answer
35

III. Other Bonding Theories

B. Valence bond theory
Answer 1-11. What is the hybridization of each indicated atom in the following compound? Click on the arrow to check your answers. sp3 sp3

CH3 OH C CH
sp

HO
sp3 sp2 17-ethynylestradiol (The Pill)
36