You are on page 1of 58

CHEMICAL BONDING

CHM 474
2/11/2014 1

Able to draw a Lewis structure for

Outlines.
dimolecule
based on VSEPR

Able to predict the shape/geometry

2/11/2014

2/11/2014

Chemical Bonds, Lewis Symbols, and the Octet Rule


Chemical bond: attractive force holding two or more atoms together. Covalent bond results from sharing electrons between the atoms. Usually found between nonmetals. Ionic bond results from the transfer of electrons from a metal to a nonmetal.
2/11/2014 4

Valence electrons are the outer shell electrons of an atom. The valence electrons are the electrons that participate in chemical bonding.
Group 1A 2A e- configuration ns1 ns2 ns2np1 ns2np2 ns2np3 ns2np4 # of valence e1 2 3 4 5 6

3A
4A 5A 6A 7A
2/11/2014

ns2np5

7
5

9.1

2/11/2014

Chemical Bonds, Lewis Symbols, and the Octet Rule

The Octet Rule


All noble gases except He has an s2p6 configuration. Octet rule: atoms tend to gain, lose, or share electrons until they are surrounded by 8 valence electrons (4 electron pairs). Caution: there are many exceptions to the octet rule.
2/11/2014 7

Li + F Li+ F 1s22s11s22s22p5 1s22s22p6 [He][Ne] Li Li+ + F e- + F Li+ + eF-

Li+ F -

2/11/2014

2/11/2014

Covalent Bonding

10

2/11/2014

A covalent bond is a chemical bond in which two or


more electrons are shared by two atoms.

Why should two atoms share electrons?


F + F F F

7e7e8e- 8eLewis structure of F2


lone pairs single covalent bond lone pairs
2/11/2014

lone pairs

single covalent bond

F F

lone pairs
11

Continued

2/11/2014

12

Lewis structure of water


single covalent bonds

O +

H O H 2e8e-2e-

or

Double bond two atoms share two pairs of electrons O C O 8e- 8e- 8edouble bonds

or

double bonds

Triple bond two atoms share three pairs of electrons N N 8e-8e2/11/2014

or

N
13

triple bond

triple bond

9.4

Lengths of Covalent Bonds


Bond Type

Bond Length (pm)

C-C C C C C C-N C N

154 133 120 143 138

C N
Bond Lengths Triple bond < Double Bond < Single Bond
2/11/2014

116

14

9.4

Chemical Bonds
Bond Type # of es Notation Bond order Bond strength Bond length
2/11/2014

Single 2 1

Double 4 = 2

Triple 6 3

Increases from Single to Triple Decreases from Single to Triple


15

2/11/2014

16

Writing Lewis Structures


1. Draw skeletal structure of compound showing what atoms are bonded to each other. Put least electronegative element in the center. 2. Count total number of valence e-. Add 1 for each negative charge. Subtract 1 for each positive charge. 3. Complete an octet for all atoms except hydrogen 4. If structure contains too many electrons, form double and triple bonds on central atom as needed.
2/11/2014 17

Write the Lewis structure of nitrogen trifluoride (NF3).


Step 1 N is less electronegative than F, put N in center Step 2 Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5) 5 + (3 x 7) = 26 valence electrons Step 3 Draw single bonds between N and F atoms and complete octets on N and F atoms. Step 4 - Check, are # of e- in structure equal to number of valence e- ?

3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

N F

2/11/2014

18

Write the Lewis structure of the carbonate ion (CO32-).


Step 1 C is less electronegative than O, put C in center Step 2 Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4) -2 charge 2e4 + (3 x 6) + 2 = 24 valence electrons Step 3 Draw single bonds between C and O atoms and complete octet on C and O atoms. Step 4 - Check, are # of e- in structure equal to number of valence e- ? 3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons Step 5 - Too many electrons, form double bond and re-check # of e2 single bonds (2x2) = 4 1 double bond = 4 O C O 8 lone pairs (8x2) = 16 Total = 24

O
2/11/2014

19

Lewis structure H3PO4


Skeleton is:

Count total valence electrons:


1P= 5 3H= 3 4 O = 24 Total = 32 e- or 16 valence e- pairs.

2/11/2014

7 e- pairs needed to form s skeleton.


20

Lewis structure H3PO4


Add remaining e- pairs:

Left has a formal charge of +1 on P and -1 on one O,

right has 5 e- pairs around P (hypervalence) Analysis of phosphoric acid shows purely Td phosphate groups, which requires something beyond either simple Lewis model.

2/11/2014

21

Two possible skeletal structures of formaldehyde (CH2O) H C O H C O H H


An atoms formal charge is the difference between the number of valence electrons in an isolated atom and the number of electrons assigned to that atom in a Lewis structure.
formal charge on an atom in a Lewis structure

total number total number of valence of nonbonding electrons in electrons the free atom

1 2

total number of bonding electrons

)
22

The sum of the formal charges of the atoms in a molecule or ion must equal the charge on the molecule or ion.
2/11/2014

-1 H C

+1 O H

C 4 eO 6 e2H 2x1 e12 e-

2 single bonds (2x2) = 4 1 double bond = 4 2 lone pairs (2x2) = 4 Total = 12

formal charge on an atom in a Lewis structure

total number total number of valence of nonbonding electrons in electrons the free atom

1 2

total number of bonding electrons

formal charge = 4 - 2 - x 6 = -1 on C

formal charge = 6 - 2 - x 6 = +1 on O

2/11/2014

23

Formal Charge and Lewis Structures


1. For neutral molecules, a Lewis structure in which there are no formal charges is preferable to one in which formal charges are present.

2. Lewis structures with large formal charges are less plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of formal charges, the most plausible structure is the one in which negative formal charges are placed on the more electronegative atoms. Which is the most likely Lewis structure for CH2O? -1 H
2/11/2014

+1 O H

H H

0 C

0 O
24

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. + + O O O O O O

What are the resonance structures of the carbonate (CO32-) ion?

C
O

C
O -

C
O -

25

2/11/2014

2/11/2014

26

2/11/2014

27

2/11/2014

28

2/11/2014

29

2/11/2014

30

Exceptions to the Octet Rule


The Incomplete Octet H BeH2 Be 2e2H 2x1e4eB 3e3F 3x7e24e3 single bonds (3x2) = 6 9 lone pairs (9x2) = 18 Total = 24

Be

BF3

B F

31

2/11/2014

Exceptions to the Octet Rule


Odd-Electron Molecules NO N 5eO 6e11eN O

The Expanded Octet (central atom with principal quantum number n > 2)

SF6

S 6F 42e48e6e-

F S

6 single bonds (6x2) = 12 18 lone pairs (18x2) = 36 Total = 48


32

F
2/11/2014

VSEPR - Valence Shell Electron Pair Repulsion Theory


Electron-group repulsions and the five basic molecular shapes.

linear

trigonal planar

tetrahedral

trigonal bipyramidal

octahedral

2/11/2014

33

Valence shell electron pair repulsion (VSEPR) model:


Predict the geometry of the molecule from the electrostatic repulsions between the electron (bonding and nonbonding) pairs.
# of atoms bonded to central atom # lone pairs on central atom

Class

Arrangement of electron pairs

Molecular Geometry

AB2

linear
B

linear
B

2/11/2014

34

The single molecular shape of the linear electron-group arrangement.

Examples: CS2, HCN, BeF2

2/11/2014

35

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2
AB3

2
3

0
0

linear
trigonal planar

linear
trigonal planar

2/11/2014

36

VSEPR
Class
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB3 AB2E

3 2

0 1

trigonal planar trigonal planar

trigonal planar
bent

2/11/2014

37

The two molecular shapes of the trigonal planar electrongroup arrangement.


Class

Examples: SO2, O3, PbCl2, SnBr2 Examples:

Shape

SO3, BF3, NO3-, CO32-

2/11/2014

38

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2
AB3 AB4

2
3 4

0
0 0

linear
trigonal planar

linear
trigonal planar

tetrahedral

tetrahedral

2/11/2014

39

VSEPR
Class
# of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB4 AB3E

4 3

0 1

tetrahedral tetrahedral

tetrahedral trigonal pyramidal

2/11/2014

40

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB4 AB3E AB2E2

4 3 2

0 1 2

tetrahedral tetrahedral tetrahedral

tetrahedral trigonal pyramidal bent O H H

2/11/2014

41

The three molecular shapes of the tetrahedral electron-group arrangement.


Examples: CH4, SiCl4, SO42-, ClO4-

NH3 PF3 ClO3 H3O+

H2O OF2 SCl2

2/11/2014

42

lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding > > repulsion pair repulsion pair repulsion
2/11/2014 43

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2
AB3 AB4 AB5

2
3 4 5

0
0 0 0

linear
trigonal planar

linear
trigonal planar

tetrahedral
trigonal bipyramidal

tetrahedral
trigonal bipyramidal

2/11/2014

44

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB5
AB4E

5
4

0
1

trigonal bipyramidal
trigonal bipyramidal

trigonal bipyramidal
distorted tetrahedron

2/11/2014

45

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB5
AB4E AB3E2

5
4 3

0
1 2

trigonal bipyramidal
trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal
distorted tetrahedron T-shaped F

Cl F

2/11/2014

46

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB5
AB4E AB3E2 AB2E3

5
4 3 2

0
1 2 3

trigonal bipyramidal
trigonal bipyramidal trigonal bipyramidal trigonal bipyramidal

trigonal bipyramidal
distorted tetrahedron T-shaped linear I I

2/11/2014

47

The four molecular shapes of the trigonal bipyramidal electrongroup arrangement.


SF4 XeO2F2 IF4+ IO2F2-

PF5

AsF5
SOF4

ClF3 BrF3

XeF2 I3IF2-

2/11/2014

48

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB2
AB3 AB4 AB5 AB6

2
3 4 5 6

0
0 0 0 0

linear
trigonal planar

linear
trigonal planar

tetrahedral
trigonal bipyramidal octahedral

tetrahedral
trigonal bipyramidal octahedral

2/11/2014

49

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB6 AB5E

6 5

0 1

octahedral
octahedral

octahedral
square pyramidal F F F Br F F

2/11/2014

50

VSEPR
Class # of atoms bonded to central atom # lone pairs on central atom Arrangement of electron pairs Molecular Geometry

AB6 AB5E AB4E2

6 5 4

0 1 2

octahedral
octahedral octahedral

octahedral
square pyramidal square planar F Xe F F F

2/11/2014

51

The three molecular shapes of the octahedral electron-group arrangement.


SF6 IOF5

XeF4 ICl4BrF5 TeF5XeOF4


2/11/2014 52

53

2/11/2014

2/11/2014

54

1. Draw Lewis structure for molecule.

Predicting Molecular Geometry

2. Count number of lone pairs on the central atom and number of atoms bonded to the central atom. 3. Use VSEPR to predict the geometry of the molecule.

What are the molecular geometries of SO2 and SF4? O S AB2E


bent
2/11/2014

O F

F S F F

AB4E distorted tetrahedron


55

2/11/2014

56

2/11/2014

57

2/11/2014

58