CHEMICAL BONDING

Cocaine

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
1 or more electrons from one atom to another

Covalentsome valence
electrons shared between atoms

Most bonds are somewhere in between.

Essentially complete electron transfer from an element of low IE (metal) to an element of high affinity for electrons (nonmetal) 2 Na(s) + Cl2(g) ---> 2 Na+ + 2 ClTherefore, ionic compds. exist primarily between metals at left of periodic table (Grps 1A and 2A and transition metals) and nonmetals at right (O and halogens).

Ionic Bonds

Covalent Bonding
The bond arises from the mutual attraction of 2 nuclei for the same electrons. Electron sharing results. (Screen 9.5)

HA + H B

HA

HB

Bond is a balance of attractive and repulsive forces.

Chemical Bonding: Objectives

Objectives are to understand: 1. valence 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

Valence electrons are distributed as shared or BOND PAIRS and unshared or LONE

PAIRS.
G. N. Lewis 1875 - 1946

Bond and Lone Pairs

Valence 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.

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 (2p)

Note that each atom has a single, unpaired electron.

Valence Electrons
Electrons are divided between core and

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valence electrons
B 1s2 2s2 2p1 Core = [He] , valence = 2s2 2p1

Br [Ar] 3d10 4s2 4p5 Core = [Ar] 3d10 , valence = 4s2 4p5

Rules of the Game

No. of valence electrons of a main group atom = Group number For Groups 1A-4A (14), no. of bond pairs = group number. For Groups 5A (15)-7A (17), BPs = 8 - Grp. No.

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Rules of the Game

No. of valence electrons of an atom = Group number For Groups 1A-4A (14), no. of bond pairs = group number For Groups 5A (15)-7A (17), BPs = 8 - Grp. No.

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Except for H (and sometimes atoms of 3rd and higher periods),

BPs + LPs = 4
This observation is called the

OCTET RULE

Building a Dot Structure

Ammonia, NH3
1. Decide on the central atom (the atom with lowest electron affinity); never H. Hydrogen atoms are always terminal. Therefore, N is central 2. Count valence electrons H = 1 and N = 5 Total = (3 x 1) + 5 = 8 electrons; 4 pairs

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Building a Dot Structure

3. Form a single bond between the central atom and each surrounding atom

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H N H
H

4. Remaining electrons form LONE PAIRS to complete octet as needed. 3 BOND PAIRS and 1 LONE PAIR.

H N H H

Note that N has a share in 4 pairs (8 electrons), while H shares 1 pair.

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 bonds 10 pairs of electrons are now left.

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O S O

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

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Each atom is surrounded by an octet of electrons.

Carbon Dioxide, CO2

1. Central atom = _______ 2. Valence electrons = __ or __ pairs 3. Form bonds. This leaves 6 pairs. 4. Place lone pairs on outer atoms.

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Carbon Dioxide, CO2

4. Place lone pairs on outer atoms.

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

The second bonding pair forms a pi

() bond.

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

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H2CO

SO3

C2F4

Sulfur Dioxide, SO2

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

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3. Form double 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

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This leads to the following structures.

These equivalent structures are called RESONANCE STRUCTURES. The true electronic structure is a HYBRID of the two.

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Urea, (NH2)2CO

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Urea, (NH2)2CO
1. Number of valence electrons = 24 e2. Draw sigma bonds.

O H N H C N H H

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

O C

H N H

N H

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Urea, (NH2)2CO
4. Complete C atom octet with double bond.

H N H

N H

Violations of the Octet Rule

Boron Trifluoride

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Central atom = _____________ Valence electrons = __________ or electron pairs = __________ Assemble dot structure

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

Violations of the Octet Rule

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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.

Violations of the Octet Rule

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Odd # of electrons, NO2

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

N O

Formal Atomic Charges

Definition of Formal Charge:

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Formal charge= Group no. 1/2 BEs - LPEs

Carbon Dioxide, CO2

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

O
=

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

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Calculated Partial Charges in CO2

Yellow = negative & red = positive Relative size = relative charge

Thiocyanate Ion,

SCN-

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

5 - (1/2)(6) - 2 = 0

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

Thiocyanate Ion, SCN-

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N
S

C
N

Which is the most important resonance form?

Calculated Partial Charges in SCN-

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All atoms negative, but most on the S

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Boron Trifluoride, BF3

+1
-1

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

MOLECULAR GEOMETRY

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MOLECULAR GEOMETRY

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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.

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Electron Pair Geometries

Figure 9.12

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No. of e- Pairs Around Central Atom 2

Example FBeF 180 F

Geometry linear

3 F

B 120

planar trigonal F

4 H

H C

109 tetrahedral H H

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Electron Pair Geometries

Figure 9.12

Structure Determination by VSEPR

Ammonia, NH3 There are 4 electron pairs at the corners of a tetrahedron.
N H H H lone pair of electrons in tetrahedral position

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The ELECTRON PAIR GEOMETRY is tetrahedral.

Bond Properties

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bond order, bond length, bond energy, bond polarity

Buckyball in HIV-protease

# of bonds between a pair of atoms

Bond Order

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Double bond

Single bond

Acrylonitrile Triple bond

Bond Order
Fractional bond orders in resonance structures.
Consider NO2-

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O O O O 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 NO bonds Bond order = 2 N O bonds

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

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(a) (b)

bond strength bond length

414 kJ 123 pm 110 pm 745 kJ

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

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Bond Length
Bond length depends on bond order.

Bond distances measured using CAChe software. In Angstrom units where 1 A = 10-2 pm.

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Using Bond Energies

Estimate the energy of the reaction HH + ClCl ----> 2 HCl Net energy = Hrxn = = energy required to break bonds - energy evolved when bonds are made

HH = 436 kJ/mol ClCl = 242 kJ/mol HCl = 432 kJ/mol

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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 = H = +678 kJ - 864 kJ = -186 kJ

Molecular Polarity
Boiling point = 100 C Boiling point = -161 C Why do water and methane differ so much in their boiling points?

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Why do ionic compounds dissolve in water?

Bond Polarity
HCl is POLAR because it has a positive end and a negative end.
+d -d
H Cl

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Cl has a greater share in bonding electrons than does H.

Cl has slight negative charge (-d) and H has slight positive charge (+ d)

+d

-d

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

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BOND pure bond real bond

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

ELECTRONEGATIVITY, .

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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

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

Electronegativity
Figure 9.9

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Electronegativity,
See Figure 9.9

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).

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

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-d O

+d H

+d O

-d F

and polarity is reversed.

Molecular Polarity
Moleculessuch as HCl and H2O can be POLAR (or dipolar).

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They have a DIPOLE MOMENT. The polar HCl molecule will turn to align with an electric field.

Figure 9.15

Molecular Polarity
The magnitude of the

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dipole is given in
Debye units. Named for Peter Debye (1884 -

1966). Recd 1936

Nobel prize for work on x-ray diffraction and

dipole moments.

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Dipole Moments

Why are some molecules polar but others are not?

Molecular Polarity
Molecules will be polar if a) bonds are polar AND b) the molecule is NOT symmetric

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All above are NOT polar

Polar or Nonpolar?
Compare CO2 and H2O. Which one is polar?

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

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Positive C atom is reason CO2 + H2O gives H2CO3

-0.75

+1.5

-0.75

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Microwave oven

Consequences of H2O Polarity

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Polar or Nonpolar?
Consider AB3 molecules: BF3, Cl2CO, and NH3.

Molecular Polarity, BF3

F B F F
B atom is positive and F atoms are negative.

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BF bonds in BF3 are polar.

But molecule is symmetrical and NOT polar

Molecular Polarity, HBF2

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

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

Is Methane, CH4, Polar?

H C H H H

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Methane is symmetrical and is NOT polar.

Is CH3F Polar?
F C H H H

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

Substituted Ethylene

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

Substituted Ethylene

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