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Chemical Bonding and Molecular Structure

(Chapter 9)

Ionic vs. covalent bonding Molecular orbitals and the covalent bond (Ch. 10) Valence electron Lewis dot structures octet vs. non-octet resonance structures formal charges VSEPR - predicting shapes of molecules Bond properties electronegativity polarity, bond order, bond strength
20 Oct 97 Bonding and structure (2) 1

Rules for making Lewis dot structures


1. Count no. of valence electrons
(- dont forget to include the charge on molecular ions!)

2 for # of PAIRS 2. Place a bond pair (BP) between connected atoms 3. Complete octets by using rest of e- as lone pairs (LP) 4. For atoms with <8 e-, make multiple bonds to complete octets 5. Assign formal charges : fc = Z - (#BP/2) - (#LP) Indicate equivalent (RESONANCE) structures 6. Structures with smaller formal charges are preferred - consider non-octet alternatives (esp. for 3rd, 4th row) OCTET RULE: #Bond Pairs + #Lone Pairs = 4
(except for H and atoms of 3rd and higher periods)

#lone pairs at central atom in AXn = {(#e-) - 8*n}/2


20 Oct 97 Bonding and structure (2) 2

Sulfur Dioxide, SO2


Rules 1-3
bring in left pair

OS O
OR bring in right pair

O S +

These equivalent structures are called:

The proper Lewis structure is a HYBRID of the two.

RESONANCE STRUCTURES.

Each atom has OCTET . . . . . BUT there is a +1 and -1 formal charge


20 Oct 97 Bonding and structure (2) 3

SO2 (2) Alternate Lewis structure for SO2 uses 2 double bonds

O=S=O

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

This is better structure than O=S+-Osince it reduces formal charge (rule 6). 3rd row S atom can have 5 or 6 electron pairs NB: # of central atom lone pairs = (3*6 -8*2)/2 = 1 in both O=S+-O- and O=S=O structures
20 Oct 97 Bonding and structure (2) 4

Thiocyanate ion, (SCN)

Which of three possible resonance structures is most important?

A.

S=C=N

B.
C. Calculated partial charges

S=C - N
S-C N

20-0.52 Oct 97

-0.16

ANSWER: C>A>B

-0.32
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Bonding and structure (2)

MOLECULAR GEOMETRY

VSEPR
Valence Shell Electron Pair Repulsion theory.
Most important factor in determining geometry is relative repulsion between electron pairs.

Molecule adopts the shape that minimizes the electron pair repulsions.
6_VSEPR.mov

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Bonding and structure (2)

No. of e- Pairs Around Central Atom 2

Example FBeF 180o F

Geometry
linear

CAChe image

3
F

B 120o

planar trigonal

4 H
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H C

109o tetrahedral H H
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Bonding and structure (2)

Structure Determination by VSEPR


Ammonia, NH3 There are 4 electron pairs at the corners of a tetrahedron.

N H

H
H

N H H

lone pair of electrons in tetrahedral position

The ELECTRON PAIR GEOMETRY is tetrahedral.


20 Oct 97 Bonding and structure (2) 8

VSEPR - ammonia
Ammonia, NH3
N lone pair of electrons in tetrahedral position H H

Although the electron pair geometry is tetrahedral . . .


. . . the MOLECULAR GEOMETRY the positions of the atoms is PYRAMIDAL.
20 Oct 97 Bonding and structure (2) 9

AXnEm notation
a good way to distinguish between electron pair and molecular geometries is the AXnEm notation where: A - atom whose local geometry is of interest (typically the CENTRAL ATOM) Xn - n atoms bonded to A Em - m lone pair electrons at A NH3 is AX3E system pyramidal
(NB this notation not used by Kotz)
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VSEPR - water Water, H2O


1. Draw electron dot structure 2. Count BPs and LPs = 4 3. The 4 electron pairs are at the corners of a tetrahedron.
O H H
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H-O-H

The electron pair geometry is TETRAHEDRAL.


Bonding and structure (2) 11

VSEPR - water (2)

H-O-H

O H

Although the electron pair geometry is H TETRAHEDRAL . . .

. . . the molecular geometry is bent.

H2O - AX2E2 system - angular geometry

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Bonding and structure (2)

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VSEPR - formaldehyde

Formaldehyde, CH2O

1. Draw electron dot structure O 2. Count BPs and LPs: H C H At Carbon there are 4 BP but . . . 3. These are distributed in ONLY 3 regions. Double bond electron pairs are in same region. There are 3 regions of electron density Electron repulsion places them at the corners of a planar triangle. Both the electron pair geometry and the O molecular geometry are PLANAR TRIGONAL o bond angles. 120 C

H
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H2CO at the C atom is an AX3 species


Bonding and structure (2) 13

VSEPR - Bond Angles


Methanol, CH3OH
H

Define bond angles 1 and 2 Angle 1 = H-C-H = ? Angle 2 = H-O-C = ? Answer: 109o because both the C and O atoms are surrounded by 4 electron pairs.
6_CH3OH.mov

HCOH H Angle 1 Angle 2

AXnEm designation ? at C at O AX4 = tetrahedral AX2E2 = bent


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20 Oct 97

Bonding and structure (2)

VSEPR - bond angles (2)


Define bond angles 1 and 2

Acetonitrile, CH3CN
H HCC 1 H 2

109o Angle 1 = ?
Angle 2 = 180 ? o Why ? :

The CH3 carbon is surrounded by 4 bond charges The CN carbon is surrounded by 2 bond charges

AXnEm designation ? at CH3 carbon AX4 = tetrahedral


at CN carbon
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AX2 = linear
Bonding and structure (2) 15

What about: STRUCTURES WITH CENTRAL ATOMS THAT DO NOT OBEY THE OCTET RULE ?

PF5

BF3
SF4
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Geometry for non-octet species also obey VSEPR rules

Consider boron trifluoride, BF3 The B atom is surrounded by only 3 electron pairs. Bond angles are 120o

F B

Molecular Geometry is planar trigonal BF3 is an AX3 species


20 Oct 97 Bonding and structure (2) 17

Compounds with 5 or 6 Pairs Around the Central Atom

6_VSEPR.mov

90 F

F P

Trigonal bipyramid F F 120 5 electron pairs

F
90
6 electron pairs

AX5 system
F S F F F Octahedron 90

F F

AX6 system
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Bonding and structure (2)

Sulfur Tetrafluoride, SF4


Number of valence e- = 34 No. of S lone pairs = {17 - 4 b.p. - 3x4 l.p.(F)} = 1 lone pair on S There are 5 (BP + LP) e- pairs around the S THEREFORE: electron pair geometry ? = trigonal bipyramid
F

F F F S F
S F
OR

F F
F

S
F
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F F

AX4E system. Molecular geometry ?


20 Oct 97 Bonding and structure (2)

Sulfur Tetrafluoride, SF4 (2) axial


equatorial
90 F S F F F

120

Lone pair is in the equatorial position because it requires more room than a bond pair.
Molecular geometry of SF4 is see-saw

Q: What is molecular geometry of SO2 ?


20 Oct 97 Bonding and structure (2) 20

Bonding with Hybrid Atomic Orbitals


- Carbon prefers to make 4 bonds as in CH4 But atomic carbon has an s2p2 configuration Why can it make more than 2 bonds ?

6_CH4.mov

4 C atom orbitals hybridize to form four equivalent sp3 hybrid atomic orbitals.

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Bonding and structure (2)

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Orbital Hybridization
BONDS SHAPE HYBRID REMAIN s2p2 2 3 4 linear trigonal planar {2 x sp & 2 ps} {3 x sp2 & 1 p} C2H2 C2H4 CH4
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e.g.

tetrahedral {4 xsp3 }

20 Oct 97

Bonding and structure (2)

s and p Bonding in C2H4


2p C atom orbitals are COMBINED (= re-hybridized) to form orbitals better suited for BONDING The 3 sp2 hybrid orbitals are used to make the C-C and two C-H s bonds
6_C2H4-sg.mov 6_C2H4-pi.mov

Multiple Bonds

2s

3 sp2 hybrid orbitals

p orbital

The extra p orbital electron on each C atom overlaps the p orbital on the neighboring atom to form the p bond.

120
Bonding and structure (2)

H H

H
H

sp2
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6_C2H4.mov
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Consequences of Multiple Bonding


Restricted rotation around C=C bond in 1-butene = CH2=CH-CH2-CH3.
See Butene.Map in ENER_MAP in CAChe models.
E (kJ/mol) 233

27 -180

0 180 C-C=C angle (o)

P. 475 - Photo-rotation about double bonds lets us see !!


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20 Oct 97

Bonding and structure (2)

Bond Properties
What is the effect of bonding and structure on molecular properties ?
- bond order - bond length - bond strength - bond polarity - MOLECULAR polarity

Buckyball in HIV-protease, see page 107

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Bonding and structure (2)

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Bond Order
the number of bonds between a pair of atoms.
H H C H C C

triple, BO = 3 1 s and 2 p
N

CH2CHCN Acrylonitrile

single BO = 1 1 s

double, BO = 2 1 s and 1 p

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Bonding and structure (2)

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Bond Order (2)


Fractional bond orders occur in molecules with resonance structures.

Consider NO2-

Total # of e - pairs used for a type of bond Bond order = Total # of bonds of that type

3 (e pairs in N-O bonds) Bond order in NO2 = 2 (N - O bonds) N-O bond order in NO2- = 1.5
20 Oct 97 Bonding and structure (2) 27

Bond Order and Bond Length


Bond order is related to two important bond properties:

(a) bond strength


as given by DE

110 pm 745 kJ

(b) Bond length


- the distance between the nuclei of two bonded atoms.
20 Oct 97 Bonding and structure (2)

414 kJ 123 pm
Formaldehye
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Bond Length
- depends on size of bonded atoms: Molecule H- F H- Cl H- I - depends on bond order. Molecule CH3C- OH O=C=O C O
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R(H-X) 104 pm 131 pm 165 pm

R(C-O) 141 pm 132 pm 119 pm


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Bonding and structure (2)

Bond Strength
Bond Dissociation energy (DE) - energy required to break a bond in gas phase. See Table 9.5 BOND STRENGTH (kJ/mol) LENGTH (pm) HH 436 74 CC C=C CC NN 347 611 837 946 154 134 121 110

The GREATER the number of bonds (bond order) the HIGHER the bond strength and the SHORTER the bond.
20 Oct 97 Bonding and structure (2) 30

Bond Strength (2)


Bond HOOH O=O
O O O

Order 1 2 1.5

Length 149 pm 121 128

Strength 210 kJ/mol 498 kJ/mol ? kJ/mol 303

HOW TO CALCULATE ?

O3 (g) 3 O(g)

Hrxn = {3xHf(O) - Hf(O3)} = {3x249.2 - 142.7} = 605 kJ/mol 2 O-O bonds in O3 DE (O3) = 605/2 = 302.5 kJ/mol
20 Oct 97 Bonding and structure (2) 31

Bond Polarity
+

Cl

HCl is POLAR because it has a positive end and a negative end (partly ionic). Polarity arises because Cl has a greater share of the bonding electrons than H. Calculated charge by CAChe: H (red) is +ve (+0.20 e-) Cl (yellow) is -ve (-0.20 e-).
(See PARTCHRG folder in MODELS.)

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Bonding and structure (2)

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Bond Polarity (2)

Due to the bond polarity, the HCl bond energy is GREATER than expected for a pure covalent bond. BOND ENERGY pure bond 339 kJ/mol calculated real bond 432 kJ/mol measured Difference 92 kJ/mol. This difference is the contribution of IONIC bonding It is proportional to the difference in

Cl

ELECTRONEGATIVITY, c.
20 Oct 97 Bonding and structure (2) 33

Electronegativity, c

c is a measure of the ability of an atom in a


molecule to attract electrons to itself. Concept proposed by Linus Pauling (1901-94) Nobel prizes: Chemistry (54), Peace (63)
See p. 425; 008vd3.mov (CD)

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Bonding and structure (2)

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4 3.5 3 2.5 2 1.5 1 0.5 0


1 2 3 4 5 6 7

N C H

F P S

Cl Si

Electronegativity, c Figure 9.7

10

11

12

13

14 15

16

17

18

F has maximum c.
Atom with lowest c is the center atom in most molecules.

Relative values of c determines BOND POLARITY (and point of attack on a molecule).


20 Oct 97 Bonding and structure (2) 35

Bond Polarity
Which bond is more polar ? (has larger bond DIPOLE) OH OF c H
c(A) - c(B) 3.5 - 2.1 3.5 - 4.0 0.5 c 1.4 c(O-H) > c(O-F) Therefore OH is more polar than OF

2.1 O F 3.5 4.0

Also note that polarity is reversed.

OH - +
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OF + -
Bonding and structure (2) 36

Molecular Polarity
Moleculessuch as HCl and H2O can be POLAR (or dipolar). They have a DIPOLE MOMENT. Polar molecules turn to align their dipole with an electric field.
POSITIVE HCl
Bonding and structure (2)

NEGATIVE
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20 Oct 97

Predicting molecular polarity


A molecule will be polar ONLY if a) it contains polar bonds AND b) the molecule is NOT symmetric
Symmetric molecules

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Bonding and structure (2)

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O H polar H

Molecular Polarity: H2O


O H + H

Water is polar because: a) O-H bond is polar b) water is non-symmetric

The dipole associated with polar H2O is the basis for absorption of microwaves used in cooking with a microwave oven

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Bonding and structure (2)

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Carbon Dioxide
CO2 is NOT polar even though the CO bonds are polar. Because CO2 is symmetrical the BOND polarity cancels

-0.73 +1.46 -0.73

The positive C atom is why water attaches to CO2 CO2 + H2O H2CO3
20 Oct 97 Bonding and structure (2) 40

Molecular Polarity in NON-symmetric molecules

F B F F

B +ve F -ve

H B F F

Atom Chg. c

B H F

+ve +ve -ve

2.0 2.1 4.0

BF bonds are polar molecule is symmetric BF3 is NOT polar

BF, BH bonds polar molecule is NOT symmetric HBF2 is polar

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Bonding and structure (2)

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Fluorine-substituted Ethylene: C2H2F2


CF bonds are MUCH more polar than CH bonds. c(C-F) = 1.5, c(C-H) = 0.4 CIS isomer both CF bonds on same side molecule is POLAR.

TRANS isomer both CF bonds on opposite side molecule is NOT POLAR.


20 Oct 97 Bonding and structure (2) 42

Chemical Bonding and Molecular Structure


(Chapter 9)

Ionic vs. covalent bonding Molecular orbitals and the covalent bond (Ch. 10) Valence electron Lewis dot structures octet vs. non-octet resonance structures formal charges VSEPR - predicting shapes of molecules Bond properties electronegativity polarity, bond order, bond strength
20 Oct 97 Bonding and structure (2) 43