CHEMICAL BONDING

Cocaine Water

Chapter 9 Outline
Ionic -vs- Covalent Bonding in molecules Valance electrons Lewis Structures
Oxidation Numbers Formal Charges

VESPR

Chemical Bonding
Problems and questions How is a molecule or polyatomic ion held together? Why are atoms distributed at strange angles? Why are molecules not flat? Can we predict the structure? How is structure related to chemical and physical properties.

Forms of Chemical Bonds

There are 2 extreme forms of connecting or bonding atoms:

Ioniccomplete transfer of
electrons from one atom to another

Covalentelectrons shared
between atoms Most bonds are somewhere in between.

Complete electron Ionic transfer from an element of low IE (metal) to an element of high EA (nonmetal)

Bonds

2 Na(s) + Cl2(g) ---> 2 Na+ + 2 Clresults in a metal/nonmetal or ionic compound.

Covalent Bonding
Covalent bond forms by the sharing of

VALENCE ELECTRONS, between

two nonmetals.

Valence Electrons
Electrons are divided between core and valence electrons.

Na 1s2 2s2 2p6 3s1 Core = [Ne] and valence = 3s1

Br

[Ar] 3d10 4s2 4p5

35

Core = [Ar] 3d10 and valence = 4s2 4p5

: Br:
[Ar] 3d10 4s24p5

Valence Electrons

Covalent Bonding
The bond arises from the mutual attraction of 2 nuclei for the same electrons.

A Bond is a balance of attractive and repulsive forces.

Chemical Bonding Objectives

Objectives are to understand:
1. e - distribution in molecules and ions.

2. molecular structures.
3. bond properties and their effect on molecular properties.

Electron Distribution in Molecules

Electron distribution is depicted with

Lewis electron dot structures

Electrons are distributed as shared or BOND PAIRS and unshared or LONE

PAIRS.
G. N. Lewis 1875 - 1946

Bond and Lone Pairs

Electrons are distributed as shared or

BOND PAIRS and unshared or LONE PAIRS.

Cl

shared or bond pair

lone pair (LP)

This is called a LEWIS ELECTRON DOT structure.

13

Lewis Dot Electron Configs

Bond Formation
A bond can result from a head-to-head overlap of atomic orbitals on neighboring atoms.

Cl

Cl

Overlap of H (1s) and Cl (3p)

This type of overlap places bonding electrons in a MOLECULAR ORBITAL along the line between the two atoms and forms a SIGMA BOND ().

Rules of the Game

Observation that atoms want to obtain a filled noble gas electron configuration is called the OCTET RULE There are exceptions to these rules!!!

Building a Dot Structure

3. Form a sigma bond between the central atom and surrounding atoms.

N H

4. Remaining electrons go to the central atom to form LONE PAIRS to complete octet as H N needed. 3 BOND PAIRS and 1 LONE H PAIR. Note that N has a share in 4 pairs (8 electrons), while H shares 1 pair.

Building a Dot Structure

Ammonia, NH3 1. Decide on the central atom; never H.

Central atom is atom of lowest affinity for electrons. Therefore, N is the central atom. 2. Count valence electrons
H = 1 and N = 5 Total = (3 x 1) + 5 = 8 electrons / 4 pairs

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 = 26 e- or 13 pairs Step 3. Form sigma bonds

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 = 26 e- or 13 pairs Step 3. Form sigma bonds O 10 pairs of electrons are now left.

Sulfite ion, SO32Remaining pairs become lone pairs, first on outside atoms and then remaining pairs on central atom.

O S

-2

Each atom is surrounded by an octet of electrons.

Carbon Dioxide, CO2

C 1. Central atom = _______ 2. Valence electrons = __ 16 or __ 8 pairs 3. Form sigma bonds.

This leaves 6 pairs. 4. Place lone pairs on outer atoms.

Carbon Dioxide, CO2

4. Place lone pairs on outer atoms.

5. So that C has an octet, we form DOUBLE BONDS between C and O.

The second bonding pair forms a pi bond.

(p )

Double and even triple bonds are commonly observed for C, N, P, O, and S

H2CO

C2F4

SO3

Sulfur Dioxide, SO2

1. Central atom = S 2. Valence electrons = 18 or 9 pairs

3. Form pi (p) bond so that S has an octet but note that there are two ways of doing this.
bring in left pair

OR bring in right pair

Sulfur Dioxide, SO2

bring in left pair

OR bring in right pair

This leads to the following structures.

These equivalent structures are called

RESONANCE STRUCTURES. The true

electronic structure is a HYBRID of the two.

Urea, (NH2)2CO
1. Arrangement, is C or O the central atom? 2. Number of valence electrons = 24 e3. Draw sigma bonds.

O
C O

H N H

N H

Urea, (NH2)2CO
4. Place remaining electron pairs in the molecule.

O
C

H N H

N H H

5. Carbon needs an Octet, take from the Oxygen

Urea, (NH2)2CO

Exceptions to the Octet Rule

Occurs with B (the only 2nd period exception) and elements of 3rd - 7th periods.

BF3

SF4

Boron Trifluoride
Central atom = Valence electrons = or electron pairs = Assemble dot structure

The B atom has a share in only 6 electrons (or 3 pairs). The B atom in many molecules is electron deficient.

Sulfur Tetrafluoride, SF4

Central atom = Valence electrons = ___ or ___ pairs. Form sigma bonds and distribute electron pairs.

5 pairs around the S atom. A common occurrence outside the 2nd period.

Draw Lewis Structures for:

N2

CH4
I2CO

HCOOH
NO2-

XeF4

Oxidation Number
Oxidation Number is assigned based on a set of rules.

These rules are based on the Lewis Structures of the compounds or ions.

Oxidation Number = Group no. - (no. assigned electrons) - (no. of LP electrons)

Sample Problem

Formal Atom Charges

Atoms in molecules often bear a charge (+ or -).

The predominant resonance structure of a molecule is the one with charges as close to 0 as possible.

Formal charge = Group no. - 1/2 (no. bond electrons) - (no. of LP electrons)

Carbon Dioxide, CO2

Formal charge calculations

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

O
=

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

Carbon Dioxide, CO2

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

-1

C atom charge is 0.

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

= +1

Which is the predominant resonance structure?

Carbon Dioxide, CO2

-0.73
+1.46

-0.73

Actual partial charges.

Boron Trifluoride, BF3

F B

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

Boron Trifluoride, BF3

F fc = 7 - 2 - 4 = +1 B fc = 3 - 4 - 0 = -1

To have +1 charge on F, with its very high affinity for electrons, is not good. Negative charges are best placed on atoms with high affinity for electrons.

Thiocyanate ion, SCNWhich of three possible resonance structures is the most important?

Calculate the formal charge for each element.

Thiocyanate ion,

SCN

-0.16

-0.52

-0.32

Calculated partial charges

PRACTICE PROBLEM
Ox # = group # - lone pair electrons assigned electrons F.C. = group # - lone pair electrons - 1/2 bonding electrons
Practice Problem

Determine oxidation numbers and formal charges for the atoms in SO3-2.

MOLECULAR GEOMETRY

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.

Figure 9.11

Figure 9.12

No. of e- Pairs Around Central Atom 2

Example FBeF 180 F

Geometry linear

B
120

planar trigonal F
109 tetrahedral

4 H

H C

H H

Notice where the central atom is

4 electron pair groups

Electron pair geometry

48

Molecular Shape name

Electron pair geometry

Molecular name

Figure 9.14

Brief Summary of VESPR

Electron Pair Geometry 2 electron pairs 3 electron pairs 4 electron pairs Linear Trigonal Planar Trigonal Planar Tetrahedral Tetrahedral Tetrahedral Trigonal Bipyramidal Octahedral Molecular Geometry Linear Trigonal Planar V Bent

50

5 electron pairs 6 electron pairs

Tetrahedral Trigonal Pyramidal V Bent look all 4 of them up look all 4 of them up

14 possible combinations.learn them all!

Structure Determination by VSEPR

Ammonia, NH3 1. Draw electron dot structure

H N H H
2. Count BPs and LPs around central N atom = 4 (Called the number of structural pairs.)

Structure Determination by VSEPR

Ammonia, NH3 H 1. Draw electron dot structure 2. Count BPs and LPs = 4 3. The 4 electron pairs are at the corners of a tetrahedron.

N H H

N H H H

lone pair of electrons in tetrahedral position

Structure Determination by VSEPR

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

H N H H
H

N H H

lone pair of electrons in tetrahedral position

The ELECTRON PAIR GEOMETRY is tetrahedral.

Structure Determination by VSEPR

Ammonia, NH3 The electron pair geometry is tetrahedral.
N H H H lone pair of electrons in tetrahedral position

The MOLECULAR GEOMETRY or SHAPE the positions of the atoms is Trigonal PYRAMIDAL.

55

VESPR Step-by-step Determination

Structure Determination by VSEPR

Water, H2O
1. Draw electron dot structure

H O H
2. Count BPs and LPs = 4

Structure Determination by VSEPR

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

H O H

The electron pair geometry is TETRAHEDRAL.

Structure Determination by VSEPR

Water, H2O

H O H

O H H

The electron pair geometry is TETRAHEDRAL.

The molecular geometry is bent 109.5

Structure Determination by VSEPR

Formaldehyde, CH2O
1. Draw electron dot structure

O
C H

Structure Determination by VSEPR

Formaldehyde, CH2O
1. Draw electron dot structure 2. Count BPs and LPs = 3

O C H

(the double bond is treated as a lump of electrons or one pair)

Structure Determination by VSEPR

Formaldehyde, CH2O

1. Draw electron dot structure H C 2. Count BPs and LPs = 3 3. There are 3 electron pairs are at the corners of a planar triangle.

O C

The electron pair geometry is TRIGONAL PLANAR with 120o bond angles.

Structure Determination by VSEPR

Formaldehyde, CH2O

C
H H

The electron pair geometry is TRIGONAL PLANAR

The molecular geometry is also TRIGONAL PLANAR.

Structure Determination by VSEPR

Methanol, CH3OH
1. Draw electron dot structure
H

HCOH 1 H 2

2. Define bond angles 1 and 2

Structure Determination by VSEPR

Methanol, CH3OH
Define bond angles 1 and 2
H

1
H

In both cases the atom is surrounded by 4 electron pairs.

Structure Determination by VSEPR

Acetonitrile, CH3CN
Define bond angles 1 and 2 Angle 1 = 109o Angle 2 = 180o

One C is surrounded by 4 electron lumps and the other by 2 lumps

Phenylalanine, an amino acid

Determine the bond angles.

120o
109o

109o

:
120o

109o

Compounds with 5 or 6 Pairs Around the Central Atom

Compounds with 5 or 6 Pairs Around the Central Atom

90 F F P F 90
6 electron pairs

Trigonal bipyramid F F F S F Octahedral F F 90 120 5 electron pairs

F F

69

STRUCTURES WITH CENTRAL ATOMS THAT DO NOT OBEY THE OCTET RULE

70

Deviations from the Octet Rule

Usually occurs with Group 3A elements and with those of 3rd period and higher. Consider boron trifluoride, BF3

F
B

71

Deviations from the Octet Rule

Consider boron trifluoride, BF3 The B atom is surrounded by only 3 electron pairs.

F B

Bond angles are

120o

Geometry described as planar trigonal

Sulfur Tetrafluoride, SF4

Number of valence electrons =

Central atom =
Dot structure

Sulfur Tetrafluoride, SF4

Number of valence electrons = 34

Central atom = S
Dot structure
F F F S F

Sulfur Tetrafluoride, SF4

Number of valence electrons = 34 Central atom = S F Dot structure
F S F F

Electron pair geometry = ?

Sulfur Tetrafluoride, SF4

Number of valence electrons = 34 Central atom = S Dot structure Electron pair geometry = trigonal bipyramid (because there are 5 pairs around the S)

F F F S F

What is the Molecular Geometry?

Sulfur Tetrafluoride, SF4

Not all repulsions are equivalent. L.P. - L.P. > L.P. - B.P. > B.P. - B.P. Minimize lone pair bond pair repulsions at the 90o angle.
90
F

F F

120

Structural Determination
Determine the geometries for PF3, NO2-, NO2+, ICl2-, ClF3, ClF5, and IBr4-, giving VSEPR class, shape name, 3-D diagram, and bond angles.

Solutions

Bond Properties
What is the effect of bonding and structure on molecular properties?

Buckyball in HIV-protease

Bond Order
The number of bonds between a pair of atoms.
H H triple, BO = 3 1 and 2 p C N

H
single BO = 1 1

double, BO = 2 1 and 1 p

Bond Order
Fractional bond orders occur in molecules with resonance structures. Consider NO2

The NO bond order = 1.5

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 = 2 N O bonds

Bond Order
Bond order is proportional to two important bond properties:

(a) bond strength (b) bond length

110 pm

745 kJ
414 kJ 123 pm

Bond Length
Bond length is the distance between the nuclei of two bonded atoms.

Bond Length
Bond length depends on size of bonded atoms.

HF

HCl
Bond distances measured in Angstroms or pm where 1 A = 100 pm.

HI

Bond Length
Bond length depends on bond order.

Different C-O Bond Lengths

C-C bond lengths C-N bond lengths

Bond Strength
Bond strength is measured by the energy required to break a bond. See Table 9.9

C-C bond strengths

Bond Strength
BOND HH CC C=C CC NN STRENGTH (kJ/mol) 436 346 602 835 945

The GREATER the number of bonds (bond order) the HIGHER the bond strength and the SHORTER the bond.

Bond Strengths for O-O

Bond HOOH Order 1 Length 147 pm Strength 210 kJ/mol

1.5 O

128

394 ?

O=O

121

498

Using Bond Energies

DHorxn = S H (bonds broken) S H (bonds formed) or DHorxn = energy input (+) + energy output (-).
Net energy = DHrxn, bond = energy required to break bond energy evolved when bonds are formed.

Using Bond Energies

Estimate the energy of the reaction HH + ClCl ----> 2 HCl
HH = 436 kJ/mol ClCl = 242 kJ/mol HCl = 432 kJ/mol

Sum of H-H + Cl-Cl bond energies = 436 kJ + 242 kJ = +678 kJ 2 mol H-Cl bond energies = 864 kJ Net = DH = +678 kJ - 864 kJ = -186 kJ

Using Bond Energies

Estimate the energy of the reaction 2 HOOH ----> O=O + 2 HOH

Is the reaction exo- or endothermic?

Which is larger: energy reqd to break bonds or energy evolved on making bonds?

Using Bond Energies

2 HOOH ----> O=O + 2 HOH

Energy required to break bonds:

break 4 mol of OH bonds = 4 (463 kJ)

break 2 mol OO bonds = 2 (146 kJ)

TOTAL ENERGY to break bonds = 2144 kJ

Using Bond Energies

2 HOOH ----> O=O + 2 HOH

Energy evolved on making bonds:

make 1 mol of O=O bonds = 498 kJ make 4 mol OH bonds = 4 (463 kJ) TOTAL ENERGY evolved on making bonds = 2350 kJ

Using Bond Energies

2 HOOH ----> O=O + 2 HOH Net energy = +2144 kJ - 2350 kJ = - 206 kJ

The reaction is exothermic!

More energy is evolved on making bonds than is expended in breaking bonds.

Calculate DHorxn for the reaction below using bond energies.

CH4 (g) + 2 O2 (g) ______> 2 H2O (g) + CO2 (g)
DH = [4(C-H) + 2(O=O)] - [4(H-O) + 2(C=O)] DH = [4(413kJ) + 2(498kJ)] - [4(463kJ) + 2(732kJ)] DH = -1166 kJ More Sample Problems!

Molecular Polarity

Why are water molecules attracted to a balloon that has a static electric charge?

Bond Polarity
+

Cl

HCl is POLAR because it has a positive end and a negative end. Polarity arises because Cl has a greater share in bonding electrons than does H.

Bond Polarity
This model, calcd using CAChe software, shows that H is + (red) and Cl is - (yellow). Calcd charge is + or - 0.20.

This model shows that the electron density is greater around Cl than around H.

Cl

Bond Polarity
Due to the bond polarity, the HCl bond energy is GREATER than expected for a pure covalent bond. ENERGY 339 kJ/mol calcd 432 kJ/mol measured

BOND pure bond real bond

Difference = 92 kJ. This difference is proportional to the difference in

ELECTRONEGATIVITY,
Dont confuse with mole fraction from Ch 12

Cl

Bond Polarity
-

Partial charge on atom A =

Group Number of A

# lone pair electrons

A/(A+ B)( # bonding e- shared by A )

Electronegativity,
is a measure of the ability of
an atom in a molecule to attract electrons to itself.
Concept proposed by Linus Pauling 1901-1994

Linus Pauling, 1901-1994

The only person to receive two unshared Nobel prizes (for Peace and Chemistry). Chemistry areas: bonding, electronegativity, protein structure

Electronegativity,
See Figure 9.10
F has maximum . Atom with lowest is the center atom in most molecules. Relative values of determine BOND POLARITY (and point of attack on a molecule).

Electronegativity,

Figure 9.9

Basic Trend =

Bond Polarity
Which bond is more polar (or DIPOLAR)? OH OF 3.5 - 2.1 3.5 - 4.0 D 1.4 0.5 OH is more polar than OF

OH - +

OF + -

and polarity is reversed.

Bond Polarity
Relative polarity in a bond is determined by D , where the approximate % ionic character is give by:

D = 1.0, 20%; D = 2.0, 60%;

D = 1.5, 40%; D = 2.5, 80%.

Molecular Polarity
Moleculessuch as HCl and H2O can be POLAR (or dipolar).
They have a DIPOLE MOMENT. The polar HCl molecule will turn to align with an electric field.

Molecular Polarity
The magnitude of the dipole is given in Debye units. Named for Peter Debye (1884 - 1966). Received the 1936 Nobel prize for work on x-ray diffraction and dipole moments.

Molecular Polarity
Molecules will be polar if 1. bonds are polar AND 2. the molecule is NOT symmetric Symmetric molecules

Molecular Polarity

Unsymmetrical

Carbon Dioxide
CO2 is NOT polar even though the CO bonds are polar. CO2 is symmetrical.

Positive C atom is reason CO2 + H2O gives H2CO3

Microwave oven

Consequences of H2O Polarity

Molecular Polarity More Examples

F B F F
BF bonds in BF3 are polar. But molecule is symmetrical and NOT polar

B atom is positive and F atoms are negative.

Molecular Polarity

H B F F
BF and BH bonds in HBF2 are polar. But molecule is NOT symmetrical and is polar

B atom is positive but H & F atoms are negative.

Polarity of Methane, CH4

H C

H H

Methane is symmetrical and is NOT polar.

Polarity of CH3F

F C H H H

CF bond is very polar. Molecule is not symmetrical and so is polar.

Substituted Ethylene

CF bonds are MUCH more polar than CH bonds. Because both CF bonds are on same side of molecule, molecule is POLAR.

Substituted Ethylene

CF bonds are MUCH more polar than CH bonds. Because both CF bonds are on opposing ends of molecule, molecule is NOT POLAR.

Practice Problems
1. Give the VSEPR class, bond angle, shape, and polarity of KrF2, CO, and NO2-. 2. Calculate the heat of reaction for C2H4 (g) + 3 O2 (g) --> 2 CO2 (g) + 2 H2O (g) 3. Calculate the carbon-carbon triple bond energy in C2H2(g). Heat of formation of C2H2 = 226 kJ/mole) 4. Determine the number of p and bonds in acetic acid. 5. Arrange in order of increasing polarity: Sr-Br, P-F, S-F, Al-O

Practice Problems Answers

1. AX2E3, 1800, linear, nonpolar AXE, 1800, linear, polar

AX2E, 1200, bent, polar

2. -1032 kJ

3. 818 kJ
4. 7 and 1 p

5. S-F, P-F, Al-O, Sr-Br,

Ionic Bonding
Ionic bonds form by the transferring of

VALENCE ELECTRONS, the

electrons at the outer edge of the atom.

Ionic Bonding
Na and F Na 1s22s22p63s1
F 1s22s22p5

Na1+ 1s22s22p6

F1- 1s22s22p6

NaF

Ionic Bonding
Mg and O Mg 1s22s22p63s2
O 1s22s22p4

Mg2+ 1s22s22p6

O2- 1s22s22p6

MgO

Ionic Bonding
Mg and F Mg 1s22s22p63s2
F 1s22s22p5

F 1s22s22p5 Mg2+ 1s22s22p6 F1- 1s22s22p6 F1- 1s22s22p6

MgF2

Ionic Bonding
Na and O Na 1s22s22p63s1

O 1s22s22p4

Na 1s22s22p63s1

Na1+ 1s22s22p63s1
Na1+ 1s22s22p63s1

O2- 1s22s22p6

Na2O

Covalent Bonding
Cl and F

Cl

. . Cl . F

.F

Covalent Bonding
S and F

.S.
F

.F . . .S. F

Covalent Bonding
O and O

. . O .. O

Sample Problems
Draw dot structures for the following: H2O CO NO21-1

-O- H
C O

-O
-1

O- N

Draw Lewis Structures for:

N2 N N

CH4
I2CO

HCOOH
NO2-

XeF4

Draw Lewis Structures for:

N2 H

CH4
I2CO

C H

HCOOH
NO2-

XeF4

Draw Lewis Structures for:

N2

CH4
I2CO

O I

HCOOH
NO2-

XeF4

Draw Lewis Structures for:

N2

CH4
I2CO O H C O H

HCOOH
NO2-

XeF4

Draw Lewis Structures for:

N2

CH4
I2CO O N O

HCOOH
NO2O O

XeF4

Draw Lewis Structures for:

N2

CH4
I2CO

HCOOH
NO2
-

XeF4

.. Xe ..

Sample Problems
Determine the oxidation number for each atom in the following: CO2 SO32O = -2 O = -2

C=4

S=4

Sample Problems
Determine the formal charge for each atom in the following: CO NO21O=1 single bond O = -1

C = -1

double bond O = 0
N=0

Structural Determination

PF3
PF3 AX3E trigonal pyramidal

..

Structural Determination

NO2+
NO2+ linear AX2

Structural Determination

ICl2
ICl2AX2E3

linear

180o 120o

. .

Structural Determination

ClF3
ClF3 AX3E2 T - shaped

120o

Structural Determination

ClF5
ClF5 AX5E square pyramidal

..

Structural Determination

IBr4
IBr4AX4E2

square planar

..

..

Calculate DHorxn for the reaction below using bond energies.

C (g) + 2 Cl2 (g)
______>

CCl4 (g)

DH = [2(Cl-Cl)] - [4(C-Cl)]

DH = [2(242 kJ)] - [4(339 kJ)]

DH = - 872 kJ

Calculate DHorxn for the reaction below using bond energies.

C (s) + 2 Cl2 (g)
______>

CCl4 (g)

DH = [ DHsubC + 2(Cl-Cl)] - [4(C-Cl)]

DH = [ 717 kJ + 2(242 kJ)] - [4(339 kJ)]

DH = -155 kJ

Calculate DHof for CH4 using bond energies.

C (s) + 2 H2 (g) --> CH4 (g)
DHf = [DHsub C + 2(H-H)] - [4(C-H)] DHf = [ 717 kJ + 2(436 kJ)] - [4(413kJ)] DHf = - 63 kJ

Given DHof for C2H4 (g) is 52 kJ/mole. Using bond energies, calculate the carbon carbon bond energy in C2H4 (g).
2 C (s) + 2 H2 (g) -- > C2H4 (g)

DHf = [ 2(DHsubC) + 2(H-H) ] - [ 4(C-H) + 1(C=C) ]

52kJ = [ 2(717kJ) + 2(436kJ)] - [4(413kJ) + 1(C=C)] (C=C) = 602 kJ

Bond Polarity
Ionic Polar Nonpolar Covalent Covalent <--------------------------------------------------------------> :F Li C : F F : F