Covalent Bonding: Sharing Electrons

Mass ratio proton : electron = ~ 1800

Ionic Bonding: No Sharing of Electrons

Who donates and who accepts?

Partial Periodic Table

Duet

Octets Valence electrons

Why Do Elements React?

Noble Gas Configuration 1. Ionic Bonds Na2,8,1 F2,7 Therefore: 2 Na + F2
+ 2 Na F -1e +1e

[Na2,8]+ [F2,8]-

Transfer of Valence Electrons

2. Covalent Bonds
Elements in the middle of the periodic table have a problem with electron affinity (EA) and ionization potential (IP):
Cov ale 4C nt Bon ds

(He)

4+

-4e

+4e

Shows only valence e (Ne)

Compromise: electron-sharing
C 2 H2 + 4H + O2

H .. H C .. H H

.. HO .. H .. ..

.. ..

3. Most Bonds Are Between Covalent and Ionic:

Polar Covalent
H : F:
:
!+ !!+

!+

A:B
!+

!-

I : Cl :
:

!-

H3C : F :
:

!-

Pauling electronegativity scale

1901-1994 Nobel prizes for chemistry and peace

push

pull

Increase

Decrease

":

0.3
Covalent

<

0.3 2.0
Polar Covalent

<

2.0
Ionic

The Shape of Molecules

Controlled by valence electron repulsion
: :

Diatomics: linear (of course), e.g. H : H Triatomics: either linear (i.e. not bent), e.g. e.g
: : F: Be : F: : : : : :

Li : H : F: F:
: :

not

: F: Be:

H :O H : Cl: Tetraatomics: either trigonal, e.g. : Cl : B : Cl:

or bent, when there are lone e-pairs, e.g. :
:

F:

:
:
:

Or pyramidal, when there are lone e-pairs, e.g. N H : H H H C H H H

Pentaatomics: tetrahedral, e.g.

But other shapes are possible, when there are more electrons, e.g. in transition metals (octahedral etc.).

How to distribute valence electrons: Lewis Structures

Rule 1: Draw molecular skeleton (given) CO2 OCO CH4 H HC H H

Rule 2: Count total number of valence electrons .. . . : .C. :Br . H. O . . Rule 3: Octet (Duet) Rule
: : : : Provide octets (duets for H) around all atoms : : F: F : :O H: H

Rule 4:

Take care of charges, if any. Charges occur when the formal effective electron count around the nucleus differs from valence electron count.

Effective electron count: Each bond with two

shared electrons counts as 1e; lone pairs count as 2e.

Valence electron count: Rule 2 (# of valence electrons). + H + .. :H : N:::O : H:O .. + + H3O NO : C:::O: CO +

Example: CO2 C O 2. Valence electrons: O 6e, C 4e

3. Octet rule 1. Atom arrangement: O

16e total

Shortcut:

1. Connect all bonded atoms with 2e line.

O C O .. ..

2. If there are e left, add them as lone pairs .. to any .. :O C O: atom to give it an octet until no e left. 3. If some atoms lack octet, move lone pairs into shared positions. .. .. .. ..

:O C O: .. ..

O .. .. C O

Resonance
Often several octet structures are possible for a molecule: Resonance forms Molecule is a superposition of these forms

Form A .. :O:

move electrons (pairs)

form B .. : O:
..

.. ..

Carbonate, CO32-. All forms are equivalent

.. .. ..

..

..

..

..

.. ..

- C O O

..

.. ..

..
..

..

Resonance Forms
The carbonate ion is delocalized:

symmetrical!

.. :O :

Electrostatic Potential Map: Red = relatively electron rich Blue = relatively electron poor

.. .. ..

..

..

Nonequivalent Resonance Forms

Rules

which ones are better?

1. Octet rule (wins over all other) N + O + N O

major

6e

O C
major

O C+

6e

2. When there are two or more forms with complete octets: electronegativity rules.
Example: enolate ion

charge on more e-negative element

H H

C C
major

H H

C C

H O

But:

N
major

+ O

6e

+ N O

When in doubt, rule 1 wins !

3. Minimum charge separation O H C O H H O C + O

major

Formic acid

Note:

-: ::: + C O:

Rule 1 wins !

1927 Schrdinger: Wave equations for an electron moving around the nucleus

Orbitals: Solutions to wave equations (wavefunctions) Born: Square of a value of the wavefunction = probability of finding the electron there

Orbitals
Spherical (three-dimensional) shape. Contrast to mechanical waves (guitar string, rubber band) Two-dimensional wave:
amplitude 0

+
node

+/- = signs, not charges

Most important orbitals (for us):

node

s Orbital ball

p Orbital spherical eight

+ -

Actual solutions: 1s, 2s, 2px, 2py, 2pz, 3s, 3px, 3py, 3pz, etc.
#s are related to classical shells

(increasing energy)

The 1s Orbital

The 2s Orbital

The Three 3p Orbitals

Aufbau Principle
or: where the electrons go Energy diagram depicting solutions as energy levels:

2s 1s

px

py pz electrons (He)

There are rules for filling up levels with e

1. Lower energy orbitals filled first (closed shell) 2. Pauli: Exclusion principle: 2e max 3. Hunds rule: Equal energy orbital (i.e. px,y,z) filled with one e each first

Energies of Orbitals Calculated for H Atom

Bonding Bonding occurs by overlap of atomic orbitals to give molecular orbitals

In phase overlap ! bonding molecular orbital Out of phase overlap ! antibonding molecular orb.

Energy E diagrams

antibonding (node) 1s 1s bonding 1s

2p

no e

bad

e go down
-Orbitals split energy levels when entering into overlap. -The better the overlap [e.g. same type of orbital, same energy (shell)], the larger the splitting. -For orbitals of unequal energy, the higher orbital goes up, the lower down.

good

1s

2p

The Types of Orbital Overlap

Hybridization and Shape

++ -H : Be : H is linear; but Be atom has

filled shells (1s)2(2s)2!

Li : H 2s + 1s no shape issues

How does it bond? Use an empty p orbital:

This allows for bonds, but gives wrong structure:

Better: Hybridization of Orbitals

Intraatomic overlap of 2s and one 2p orbitals generates two new hybrid molecular orbitals: s + p ! two sp hybrids, with linear arrangement:

sp-Hybrid

We shall see next that other combinations of intraatomic overlap (hybridization) are possible:

s + p + p ! 3 sp2 with trigonal shape s + p + p + p ! 4 sp3 with tetrahedral shape

Note: n atomic orbitals ! n new orbitals

Example: Bonding in BH3. Hybridization to Trigonal

sp2-Hybrid

Bonding in Methane: Hybridization to Tetrahedral

sp3-Hybrid

Bonding in Ethane: Overlap of Two sp3 Hybrid Orbitals

More sp3 Hybrids: NH3 and H2O

Double and Triple Bonds: A Preview

Molecular Models: Use Them!!!

The Dashed-Wedged Line Notation