George Mason University General Chemistry 211 Chapter 11 Theories of Covalent Bonding

Acknowledgements
Course Text: Chemistry: the Molecular Nature of Matter and Change, 6th edition, 2011, Martin S. Silberberg, McGraw-Hill The Chemistry 211/212 General Chemistry courses taught at George Mason are intended for those students enrolled in a science /engineering oriented curricula, with particular emphasis on chemistry, biochemistry, and biology The material on these slides is taken primarily from the course text but the instructor has modified, condensed, or otherwise reorganized selected material. Additional material from other sources may also be included. Interpretation of course material to clarify concepts and solutions to problems is the sole responsibility of this instructor.
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Molecular Structure - Summary

Atomic theory Molecular Weight (MW) Neutrons + Protons Mass, Atomic Mass units, Law of Definite Proportions Moles, Chemical Equations, Stoichiometry Gas Laws, Thermodynamics (reaction energy) Quantum Theory waves vs particles, electronic structure of atoms energy absorption, emission electronic energy levels quantum numbers, electron shells Periodicity orbital diagrams Pauli exclusion principle Aufbau Principle for populating subshells
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Molecular Structure - Summary

Bonding Valence electrons Periodic table Ionic Bonds Covalent Bonds Electronic Configuration Lattice Energy, Born-Haber cycle, Bond energy Geometry Lewis diagrams Resonance, Octet Rule Formal Charge (valence electrons unbonded electrons bonded electrons) Valence-Shell Electron Pair Repulsion Model (VSEPR) Molecular Notation AXaEb Xa Bonding pairs Eb Nonbonding pairs sum(a + b) determines geometry (linear, tetrahedral) if b > 0 molecule may form dipole (polar)
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Bond Theories

Quantum Numbers & Electron Configuration

In Chapters 8 & 9 an electron was defined as a unique set of 4 quantum numbers The first 3 quantum numbers (n, l, ml) defined an atomic orbital, which could contain a maximum of 2 electrons (+1/2 & -1/2 spin (ms)) Each orbital (s, p, d) has a unique shape: spherical (s), dumbell(p), pear shaped(d)

All of the orbitals defined by a unique set of n, l, ml quantum numbers, have the same energy

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p orbitals s orbital

d orbitals

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Bonding Theories

Valence Bond (VB) theory is one of two basic theories, along with Molecular Orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding Valence Bond Theory is a chemical bonding theory that explains the bonding between two atoms caused by the overlap of the half-filled atomic orbital from each atom It focuses on how the atomic orbitals of the dissociated atoms combine to give individual chemical bonds when a molecule is formed The two atoms from the bonding atoms share each other's unpaired electron to form a filled orbital to form a hybrid orbital and bond together.
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Bonding Theories

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Molecular Orbital (MO) theory is a method for determining molecular structure in which electrons are not assigned to individual bonds between atoms, but are treated as moving under the influence of the nuclei in the whole molecule In this theory, each molecule has a set of molecular orbitals, in which it is assumed that the molecular orbital wave function j may be written as a simple weighted sum of the n constituent atomic orbitals A given Atomic Orbital (s, p, d) takes the form of a subset of Molecular Orbitals bonding & antibonding bonds and bonding & antibonding bonds Each has its own energy Molecular Orbital orbitals cover the whole molecule
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Valence Bond Theory

Valence Bond Theory is an attempt to explain the Covalent bond from a Quantum Mechanical view

All orbitals of the same type (s, p, d, f) have the same energy According to this theory, a bond forms when two atomic orbitals (s/s s/p p/p) overlap

The space formed by the overlapping orbitals has a capacity for two electrons that have opposite spins, +1/2 & -1/2 (exclusion principle)
Note: Each orbital forming the bond has at least one unfilled slot to accommodate the electron being shared from the other bonding orbital

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The bond strength depends on the attraction of the nuclei for the shared electrons
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Valence Bond Theory

Valence bond theory (cont)

The greater the orbital overlap, the stronger (more stable) the bond The extent of the overlap depends on the shapes and directions of the orbitals An s orbital is spherical, but p and d orbitals have more electron density in one direction than in another Whenever possible, a bond involving p or d electrons will be oriented in the direction that maximizes overlap

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Valence Bond Theory

Hydrogen, H2 1s1

Hydrogen Fluoride, HF [He]2s22p5 To maximize overlap, half-filled H 1s and F 2p orbitals overlap along the long axis of the 2p orbital

Fluorine, F2

[He] 2s22p5

In F2, the half-filled 2 px orbital on one F atom points end to end toward the half-filled 2px of the other F to maximize overlap
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Hybrid Orbitals

One might expect the number of bonds formed by an atom would equal its unpaired electrons Chlorine, for example, generally forms one bond as it has one unpaired electron - 1s22s22p5 Oxygen, with two unpaired electrons, usually forms two bonds - 1s22s22p4

However, Carbon, with only two unpaired electrons, generally forms four (4) bonds
C (1s22s22p2) [He] 2s22p2

The four bonds come from the 2 (2s) paired electrons and the 2 (2p) unpaired electrons
For example, Methane, CH4, is well known The uniqueness of these bonds is described next
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Hybrid Orbitals

Linus Pauling proposed that the valence atomic orbitals in a molecule are different from those of the isolated atoms forming the molecule

Quantum mechanical computations show that if specific combinations of orbitals are mixed mathematically, new atomic orbitals are obtained
The spatial orientation of these new orbitals lead to more stable bonds and are consistent with observed molecular shapes These new orbitals are called:

Hybrid Orbitals
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Hybrid Orbitals

Types of Hybrid Orbitals

Each type a unique geometric arrangement The hybrid type is derived from the number of s, p, d atomic orbitals used to form the Hybrid
Geometric Arrangements Number of Hybrid Orbitals Formed by Central Atom Example

Hybrid Orbitals (Hybridization)

sp sp2 sp3 sp3d sp3d2

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Linear Trigonal planar Tetrahedral Trigonal bipyramidal Octahedral

2 3 4 5 6

Be in BeF2 B in BF3 C in CH4 P in PCl5 S in SF6

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SP Hybrid Orbitals

SP Hybridization 2 electron groups surround central atom Linear shape, 180o apart VB theory proposes the mixing of two nonequivalent orbitals, one s and one p, to form two equivalent sp hybrid orbitals Orientation of hybrid orbitals extend electron density in the bonding direction Minimizes repulsions between electrons Both shape and orientation maximize overlap between the atoms

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sp Hybrid Orbitals

hybrid orbitals Ex: BeCl2 The Be-Cl bonds in BeCl2 are neither spherical (s orbitals) nor dumbell (p orbitals) The Be-Cl bonds have a hybrid shape

Beryllium Hybrid Orbital Diagram

In the Beryllium atom the 2s orbital and one of the 2p orbitals mix to form 2 sp hybrid orbitals
Each Be Hybrid sp orbital overlaps a Chlorine 3p orbital in BeCl2
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orbital box diagrams

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sp2 Hybridization

sp2 - Trigonal Planar geometry (Central atom bonded to three ligands)

The three bonds have equivalent hybridized shapes The sp2 hybridized orbitals are formed from:

1 s orbital and 2 p orbitals

Note: Of the 4 orbitals available (1 s & 3 p) only the s orbital and 2 of the p orbitals are used to form hybrid orbitals Note: Unlike electron configuration notation, hybrid orbital notation uses superscripts for the number of atomic orbitals of a given type that are mixed, NOT for the number of electrons in the orbital, thus, sp2 (3 orbitals), sp3 (4 orbitals), sp3d (5 orbitals)
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sp2 Hybridization BF3

The 3 B-F bonds are neither spherical nor dumbell shaped They are all of identical shape In Boron, the 2s orbital and two of the 2p orbitals mix to form 3 sp2 hybrid orbitals, each containing one the 3 total valence electrons Each of the Boron hybrid sp2 orbitals overlaps with a 2p orbital of a Fluorine atom Boron (B) 1s22p1 Forms 3 sp2 hybrid orbitals

Hybrid Orbital Diagram

BF3
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sp3 Hybrid Orbitals

sp3 (4 bonds, thus, Tetrahedral geometry) The sp3 hybridized orbitals are formed from:

1 s orbital and 3 p orbitals

Example Carbon is the basis for Organic Chemistry Carbon is in group 4 of the Periodic Chart and has 4 valence electrons 2s22p2 The hybridization of these 4 electrons is critical in the formation of the many millions of organic compounds and as the basis of life as we know it The following slides show 3 different forms of the electronic structure and explains why the hybridized form reflects the observed structure of organic compounds
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SP3 Hybrid Orbitals

2p 2p
This structure implies different shapes and energies for the s and p bonds in carbon compounds. Observations indicate that all fours bonds are equivalent

2s Energy

2s

1s

1s C atom (promoted)
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C atom (ground state)

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SP3 Hybrid Orbitals

One bond on Carbon would form using the 2s orbital while the other three bonds would use 3

2p orbitals

This does not explain the fact that the four bonds in CH4 appear to be identical
Valence bond theory assumes that the four available atomic orbitals (2s22p2) in carbon combine to make four equivalent hybrid orbitals

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Hybrid Orbitals

Hybrid orbitals are orbitals used to describe bonding that is obtained by taking combinations of atomic orbitals of an isolated atom

In the case of Carbon, one s orbital and three p orbitals, are combined to form 4 sp3 hybrid orbitals The carbon atom in a typical sp3 hybrid structure has 4 bonded pairs and zero unshared electrons, therefore, Tetrahedral structure AXaEb (a + b) 4 + 0 = AX4 The four sp3 hybrid orbitals take the shape of a tetrahedron

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Hybridization of Carbon in CH4

4 sp3 orbitals formed

2p
Energy

sp3

sp3
C-H bonds

2s 1s
C atom (ground state)

1s
C atom (hybridized state)

1s
C atom (in CH4)
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Spatial Arrangement of sp3 Hybrid Orbitals

Shape of sp3 hybrid orbital different than either s or p

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sp3d Hybrid Orbitals

sp3d (5 molecules, thus, Trigonal Bypyramidal geometry) Molecules with central atoms from Period 3 or higher, can utilize d orbitals in the formation of hybrid orbitals The sp3d hybridized orbitals are formed from: 1 s orbital, 3 p orbitals, 1 d orbital
:

PCl5 AXaEb AX5E0

:

:F: : :F : : F : : P F: F: : : :

hybrid orbitals 5 (sp3d)

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SP3d Hybrid Orbitals

Hybridized Orbital Diagram for PCl5

5 equivalent (hybrid) orbitals are required The one 3s orbital, the 3 3p orbitals and one of the unused 3d orbitals of the Phosphorus atom mix to form the 5 sp3d hybrid orbitals

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The remaining 4 empty 3d orbitals (unhybridized) are not used

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Diagrams of Hybrid Orbitals Showing their Spatial Arrangements

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Hybrid Orbitals

To obtain the bonding description of any atom in a molecule, you proceed as follows:

Write the Lewis electron-dot formula for the molecule From the Lewis formula, use the VSEPR theory to determine the arrangement of electron pairs around the central atom, i.e., the geometry From the geometric arrangement (AXaEb) of the electron pairs, obtain the hybridization type Assign valence electrons to the hybrid orbitals of this atom one at a time, pairing only when necessary Form bonds to the central atom by overlapping singly occupied orbitals of other atoms with the singly occupied hybrid orbitals of the central atom
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Oxygen Atom Bonding in H2O

4 sp3 Hybridized Orbitals

2p
H

sp3
Tetrahedral

sp3
lone pairs O-H bonds

2s
Energy

a+b 2+2=4 Tetrahedral AX2E2 bent

1s
O Central Atom (ground state)

1s
O atom (hybridized state)

1s
O atom (in H2O)
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Practice Problem
What hybrid orbitals of Sulfur are involved in the bonding in Sulfur Trioxide (SO3)? a. sp b. sp2 c. sp3 d. sp2d e. sp3d2 Ans: b
A

O S

O S

O S

O S

fcS = +3

fcS = +2

fcS = +1

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Total Valence e- - 3 x 6 + 6 = 24 Bonded Pairs 3 x2= 6 Distribute e- about O atoms = 3 x 6 = 18 Unshared e- about S atom = 24 - 6 -18 = 0 Move e- pairs from Cl to S to form alternative forms of SO3 Compute formal charge on S; select form with least formal charge (D) AXaEb = 3 + 0 = 3 = AX3 (trigonal Planar) 3 O-S hybridized orbitals are required: one s orbital blended with 2 p orbitals (sp2)

fcS = 6-0-1/2(12) fcS = 0 (preferred form)

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Sulfur Trioxide Hybrid Orbitals

3p 3p
VSEPR AX3 Trigonal Planar

3p

3s

3 sp2 orbitals required

sp2
S atom (ground state)
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sp2
S atom (in SO3)
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S atom (hybridized state)

Nitrogen Atom Bonding in NH3

4 sp3 orbitals required

2p
H

sp3
Tetrahedral

sp3
lone pair N-H bonds

2s
Energy

1s

a+b 3+1=4 Tetrahedral AX3E1 trigonal pyramidal

1s
N atom (hybridized state)

1s
N atom (in NH3)
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N atom (ground state)

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Multiple Bonds

Types of Covalent Bond & Orbital Overlap Orbitals can overlap two ways Side to Side or End to End

Two types of Covalent Bonds: Sigma Bonds (C-C) pi () Bonds (C=C) Multiple Bonds
Ethane Tetrahedral (both carbons)
109.5o

Ethylene Trigonal planar (both carbons)

120o

Acetylene Linear (both carbons)

180o

sp3

sp2

sp

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double bond acts as single electron group

triple bond acts as single electron group

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Multiple Bonds

End-to-End overlap & Sigma Bonds

The C C bond in Ethane (C2H6) involves overlap of 1 sp3 orbital from each carbon

Each of the six (6) C H bonds involves the overlap of a Carbon sp3 and a Hydrogen 1 s orbital
All bonds involve overlap of one end of orbital with the end of the other orbital The bond formed from end-to-end overlap is called a sigma bond (symbol - )

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Multiple Bonding

According to Valence Bond theory, one hybrid orbital is needed for each bond (whether a single or multiple) and for each lone pair

For example, consider the molecule:

Ethene (or Ethylene)

H C C H
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H H
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Multiple Bonding

Each Carbon atom is bonded to three other atoms and no lone pairs, which indicates the need for three hybrid orbitals

This implies AX3E0 (Trigonal) sp2 hybridization

1 2s & 2 2p orbitals

The third 2p orbital is left unhybridized and lies perpendicular to the plane of the trigonal sp2 hybrids The following slide represents the sp2 hybridization of the Carbon atoms

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Multiple Bonding
(unhybridized)

2p

2p sp2

2s Energy

1s 1s C atom (hybridized)
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C atom (ground state)

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Multiple Bonding

Each carbon atom is sp2 hybridized Each of the carbon atoms 4 valence electrons fill its 3 sp2 orbitals and its unhybridized 2p orbital, which lies perpendicular to sp2 plane Two sp2 orbitals of each carbon form C H sigma () bonds by overlapping the 1 s orbitals of the two H atoms The 3rd sp2 orbital of one carbon forms a C C () bond with the sp2 orbital of the other carbon with end-to-end overlap A pi () bond is formed when the two unhybridized 2p orbitals (one from each carbon) overlap side-to-side, forming two regions of electron density, one above and one below the -bond axis A double bond always consists of:

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one -bond and one

bond

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Multiple Bonding

Two of the sp2 hybrid orbitals of each carbon overlap end-to-end with the 1s orbitals of the 2 hydrogen atoms forming a sigma bond

The remaining sp2 hybrid orbital, one on each carbon, overlap end-to-end to form a sigma bond

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Multiple Bonding

The remaining unhybridized 2p orbitals, one on each of the carbon atoms, overlap side-to-side, one on top of the sigma bond and one on the bottom of the sigma bond, forming a bond

The carbon-carbon double bond is described as one s bond and one bond
The two electron pairs in a double bond act as a single electron group
The electron pairs do not repulse each other because each electron pair occupies a distinct orbital, a specific region of electron density, thus repulsions are reduced
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Practice Problem
Use valence bond theory to describe the bonding in CO2 Ans: 1. Draw Lewis structure 2. Determine hybridization 3. Draw diagram of hybrid atomic orbitals 4. Pair electrons (O) with hybrid C orbitals forming sigma bonds 5. Pair electrons (O) with unpaired p electrons in C atom to form pi () bonds

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Practice Problem (Cont)

Use valence bond theory to describe the bonding in CO2

O C O

O C O

2 bonding pairs

O C O

0 non-bonding pairs AXaEb = a + b = 2 + 0 = 2 (Linear)

Hybridization sp (2 hybrid orbitals required

2p 2s 1s
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p sp

C-O p () (unhybridized)

2p 2s

Carbon atom 2s22p2

Hybridized Carbon

C-O sp ()

Oxygen atom 2s22p4

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Molecular Orbital (MO) Theory

Molecular Orbital (MO) theory is a theory of the electronic structure of molecules in terms of molecular orbitals, which may spread over several atoms or the entire molecule

MO theory explains the observed and computed energy differences among orbitals, which Valence Bond theory does not
As atoms approach each other and their atomic orbitals overlap, molecular orbitals (MO) are formed

Note: Only outer (valence) Atomic orbitals (AO) interact enough to form Molecular Orbitals (MO)

Electron motions are complex making solutions to the Schroedinger equation approximations Mathematically, the combination of atomic orbitals to form molecular orbitals involves adding or subtracting atomic wave functions
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Molecular Orbital (MO) Theory

Adding Wave Functions

Forms a Bonding () molecular orbital (MO)

Region of high electron density between nuclei

Electron charge between nuclei is dispersed over a larger area than in atomic orbitals (AO) MO orbital energy is lower than in the AO because of the reduction in electron repulsion Bonding MO is more stable than AO
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Molecular Orbital (MO) Theory

Subtracting Wave Functions Forms a Nonbonding (*) molecular orbital The node between the nuclei has most of the electron density outside the node with very little density (zero) between the nuclei Thus, the electrons do not shield one nuclei from the other resulting in increased nucleus-nucleus repulsion Therefore, the antibonding MO has a higher energy than the corresponding atom orbitals (AO) When the antibonding orbital is occupied, the molecule is less stable than when the orbital is not occupied
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Molecular Orbital Theory

Example: The bonding of two Hydrogen atoms

1s

(bonding) molecular orbital is formed

1s * (antibonding) molecular orbital is formed

The following slide illustrates the relative energies of the molecular orbitals (MO) compared to the original atomic orbitals (AO) Because the energy of the two electrons in the bonding orbital is lower than the energy of the individual atoms, the molecule is stable

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Molecular Orbital Theory

Atomic orbital Molecular Orbital Atomic orbital

H atom

H2 molecule 1s*

H atom

1s

1s

1s
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More Stable
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Bonding and Antibonding Orbitals from 1s Hydrogen Atom Orbitals

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Bond Order

The term bond order refers to the number of electron pairs shared between two atoms

The bond order of a diatomic molecule is defined as one-half the difference between the number of electrons in bonding orbitals, nb, and the number of electrons in antibonding orbitals, na

Bond

Order

1 (nb - na ) 2

For example, try H2 and He2. Determine bond orders

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Bond Order H2
Atom Molecule Atom

H 1s1
Bond Order
Energy
1s*
1s 1s

BO = [(2) (0)] = [2] =1

1s

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Bond Order He2

Atom Molecule Atom

He 1s2
Bond Order
Energy

BO = [(2) (2)] = [0] =0

1s*
1s 1s

1s

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Diatomic Homonuclear Substances in 2p period

The 2p orbitals can overlap in two ways

End-to-End gives 2p and *2p molecular orbitals (MO) Side-to-Side gives a pair of 2p and *2p MOs

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Diatomic Homonuclear Substances in 2p period

The order of MO energy levels, whether bonding or nonbonding, is based on the AO (atomic orbital) energy levels and on the mode of the p orbital combination

MOs formed from 2s orbitals are lower in energy than 2p orbitals because 2s AOs are lower in energy than 2p AOs Bonding MOs are lower in energy than antibonding MOs

2p is lower in energy than *2p 2p is lower in energy than *2p

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Diatomic Homonuclear Substances in 2p period

Atomic p orbitals (AO) can interact more extensively End-to-End than Side-to-Side

Thus, 2p MO is lower in energy than 2p

The destabilizing effect of the *2p MO is greater than that of the *2p MO The energy order for MOs derived from 2p orbitals is:

2p < 2p < *2p < *2p

Most Stable Least Stable

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Diatomic Homonuclear Substances in 2p period

Several factors are involved in the relative energies of the various molecular orbitals (MO)

Bond length Bond energy Bond order Magnetic properties

Electron valence shell configuration

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Diatomic Homonuclear Substances in 2p period

Factors that affect the MO energy level order There are three (3) mutually perpendicular 2p orbitals in each atom of a diatomic molecule (2px 2py 2pz) When the 6 p orbitals (3 from each element) combine, only one orbital from each element can interact end-to-end forming a (bond) and a * (antibonding) Molecular Orbital (MO) The other two pairs of orbitals interact side to side to form two MOs and two * MOs of the same energy giving the expected MO diagrams for the p-block Period 2 homonuclear diatomic molecules
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Diatomic Homonuclear Substances in 2p period

End to end

Side to side

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Diatomic Homonuclear Substances in 2p period

Other factors influence the MO energy level order

s" and p AOs can be similar in energy or differ considerably in energy, which determines whether the orbitals mix or dont mix O, F, Ne atoms are relatively small and electron repulsions raise the energy of 2p orbitals high enough above 2s orbitals to minimize orbital mixing

Atoms, such as B, C, N, are larger in size and the s and p AOs have less electron repulsion and the energy difference between 2s & 2p is less, resulting in mixing of the s & p orbitals
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Diatomic Homonuclear Substances in 2p period

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This smaller difference in energy of the 2p & 2s orbitals in the P, C, N atoms permits some mixing of the orbitals between the 2s orbital of one atom and the endon of the 2p orbital of the other atom This orbital mixing: lowers the energy of the 2s and *2s MOs and raises the energy of the 2p and *2p MOs The MOs are not affected The effect of the mixing is the reversal of the 2s and 2p MOs 2p < 2p < *2p < *2p The next slide illustrates these differences
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Diatomic Homonuclear Substances in 2p period

Without 2s -2p mixing
Effect of Mixing

The MOs are not affected Reversal of the 2s and 2p MOs

With 2s -2p mixing

MO energy levels O2, F2, Ne2

MO energy levels B2, C2, N2

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Diatomic Homonuclear Substances in 2p period

MO occupancy and molecular properties for B2 through Ne2 Bond energy and bond order are inversely related to bond length

Orbitals with unpaired electrons are:

paramagnetic
and are attracted to an external magnetic field Note reversal of 2p & 2p energy levels
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Diatomic Homonuclear substances in 2p period

The arrows show the occupation of molecular orbitals by the valence electrons in N2 Bond Order BO = (Nb - Na) BO = [(2+4+2) - (2)]

= [8-2]
=3
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Sample Problem
Which of the following species has a bond order of 2.5? a. b. c. d. e. O2 O 2 O 22 O 2+ NO
Energy

2p*
2p*

2p
2p

2p

Ans: d or e for NO

Nitrogen 1s22s22p3

2p

Oxygen 1s22s22p4

2s*

BO = [(2+4+2)-(2+1)] = (8-3) = 2.5

2s
2s

2s

Cont on next slide

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Sample Problem
Which of the following species has a bond order of 2.5? a. O2 b. O2 c. O22 d. O2+ e. NO Ans: d or e for O2+
BO = [(2+4+2)-(2+1)] = (8-3) = 2.5
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2p*

2p

2p*
2p

2p

Energy

Oxygen 1s22s22p4

2p 2s*

Oxygen+ 1s22s22p3

2s 2s

2s

Diatomic Heteronuclear Substances in 2p period

Heteronuclear diatomic molecules are composed of two different atoms HF NO , etc.

Heteronuclear molecules have Asymmetric MO diagrams

Atoms with greater effective nuclear charge (Zeff) draw their electrons closer to the nucleus, thus, they have higher electronegativity

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Diatomic Heteronuclear Substances in 2p period

Example: Hydrogen Fluoride(HF) Higher effective nuclear charge of Fluorine nucleus holds electrons more tightly than H (proton nucleus) All occupied atomic orbitals of F have lower energy than the 1s orbital of Hydrogen The Hydrogen 1s orbital reacts with the F 2p orbitals Only one of the 3 F 2p orbitals, 2pz leads to end-to-end overlap with Hydrogen 1s orbital producing a MO The other two p orbitals (2px & 2py) are not involved in the bonding and are called nonbonding MOs) 5/29/2013
Hydrogen Fluorine

2s AO of F is not shown 65

Diatomic Heteronuclear Substances in 2p period

Example Bonding in Heteronuclear Nitrogen Monoxide, NO Highly reactive compound because it has a lone electron Two possible Lewis Structures
Formal charge I II Formal charge

Not clear where lone electron resides (N or O) Lower Formal charge on N suggests structure I MO theory predicts electron resides closer to the Nitrogen atom Measured bond energy suggests bond order higher than 2

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Diatomic Heteronuclear Substances in 2p period

Example: Nitrogen Monoxide The 11 valence electrons of NO fill MOs in order of increasing energy, leaving the lone electron in one of the *2p orbitals Atomic orbitals of O have lower energy than those of N Oxygen is more electronegative Nitrogen The 8 bonding electrons and the 3 nonbonding electrons give a bond order of (8-3) = 2.5 The bonding electrons lie in MOs closer in energy to the AOs of the Oxygen atom The lone unshared electron occupies an anti-bonding orbital (*2p) Because this orbital receives a greater contribution from the 2p orbitals of the N atom, it resides closer to the Nitrogen atom
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Nitrogen

Oxygen

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Molecular Orbital Template (without 2s 2p mixing)

Atom (AO) Molecule (MO)
2p* 2p* 2p 2p 2p 2s* 2s 2s 2s

Atom (AO)

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Energy

2p

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Molecular Orbital Template (with 2s 2p mixing)

Atom (AO) Molecule (MO)
2p* 2p*

Atom (AO)

Energy

2p 2p 2p 2s* 2s 2s 2s

2p

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Equation Summary
1 Bond Order = (n - n ) a 2 b n - number of electrons in bonding orbitals b n - number of electrons in anti - bonding orbitals a

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Equation Summary

VESPR Model Molecular Notation:

AXaEb
A The Central Atom (Least Electronegative atom) X The Ligands (Bonding Pairs) a The Number of Ligands E Non-Bonding Electron Pairs b The Number of Non-Bonding Electron Pairs

Double & Triple Bonds count as a single electron pair The Geometric arrangement is determined by: sum (a + b)

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