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Bonding & Molecular ShapesBonding & Molecular Shapes
Dr. Ron RusayDr. Ron Rusay
Fall 2007Fall 2007
© Copyright 2002-2007 R.J. Rusay© Copyright 2002-2007 R.J. Rusay
Bond EnergyBond Energy
It is the energy required to break a It is the energy required to break a bond, i.e. overcome the force of bond, i.e. overcome the force of attraction.attraction.
The quantitative value provides The quantitative value provides information about the strength and information about the strength and nature of the bond.nature of the bond.
Bond EnergiesBond Energies
Bond Bond breakingbreaking requires energy requires energy (endothermic).(endothermic).
Bond Bond formationformation releases energy releases energy (exothermic).(exothermic).
HHrxnrxn = = H(bonds broken) H(bonds broken) H(bonds H(bonds
formed)formed)
Lattice EnergyLattice EnergyImportant for ionic crystalline solidsImportant for ionic crystalline solids
The change in energy when The change in energy when gaseous gaseous ions ions pack together to form an pack together to form an ionic solidionic solid..
MM++(g) + X(g) + X(g) (g) MX(s) MX(s)
Lattice energy is a Lattice energy is a negativenegative value value (exothermic).(exothermic).
How can the Lattice energy be calculated?How can the Lattice energy be calculated?
Determining Bond Polarity from Electronegativity Values
Solutions:
a) the EN of O = 3.5 and of H = 2.1: O - H the EN of O = 3.5 and of Cl = 3.0: O - Cl the EN of C = 2.5 and of P = 2.1: C - P the EN of P = 2.1 and of N = 3.0: P - N the EN of N = 3.0 and of S = 2.1: N - S the EN of C = 2.5 and of Br = 2.8: C - Br the EN of As = 2.0 and of O = 3.5: As - O
b) C - Br < C - P < O - Cl < P - N < N - S < O - H < As - O 0.3 < 0.4 < 0.5 < 0.9 < 0.9 < 1.4 < 1.5
Lewis StructureLewis Structure
Shows how valence electrons are Shows how valence electrons are arranged among atoms in a molecule.arranged among atoms in a molecule.
Reflects central idea that stability of a Reflects central idea that stability of a compound relates to noble gas electron compound relates to noble gas electron configuration.configuration.
G.N. LewisPhoto Bancroft Library, University of California/LBNL Image Library
Notes from Lewis’s notebook and his “Lewis” structure.Notes from Lewis’s notebook and his “Lewis” structure.
Footnote:G.N. Lewis, despite his insight and contributions to chemistry, was never awarded the Nobel prize.
Octet Rule: General CommentsOctet Rule: General Comments 2nd row elements C, N, O, F 2nd row elements C, N, O, F observe the octet observe the octet
rulerule..
2nd row elements B and Be often have fewer 2nd row elements B and Be often have fewer than 8 electrons around themselves - they are than 8 electrons around themselves - they are very reactive.very reactive.
3rd row and heavier elements 3rd row and heavier elements CANCAN exceed the exceed the octet rule using empty valence d orbitals.octet rule using empty valence d orbitals.
When writing Lewis structures, When writing Lewis structures, satisfy octets satisfy octets firstfirst,, then place electrons around elements then place electrons around elements having having available d orbitalsavailable d orbitals..
Three Ways of Showing the Formation ofLi+ and F - through Electron Transfer
Lewis Electron-Dot Symbols for Elements in Periods 2 & 3
Depicting ion formation with orbitaldiagrams and electron dot symbols
Problem: Use orbital diagrams and Lewis structures to show the formation of magnesium chloride from its ions starting with the respective atoms.
Step 1: Draw the orbital diagrams for Mg and Cl atoms.
To reach completely filled, stable electronic configurations each Mg atom loses 2 electrons, and each Cl atom gains 1 electron.
Therefore there are two Cl - ions for every one Mg 2+ ion.
Step 2: Draw the orbital diagrams for the Mg 2+ cation and 2 Cl-
anions.
2 Cl
Mg+2 + 2 Cl-
Mg
+
Mg + Cl
Cl
......
....
..Mg+2 + 2 Cl.. ....
Depicting Ion Formation with OrbitalDiagrams and Electron Dot Symbols
Remember chlorine is diatomic.Remember chlorine is diatomic.
..
....
Lewis Structures of Simple Lewis Structures of Simple Covalently Bonded MoleculesCovalently Bonded Molecules
KClO3
CF4
CH3CH2OH Ethyl alcohol (Ethanol)
Potassium Chlorate
Carbon Tetrafluoride
CH4 Methane
Draw Lewis Structures for the following: Draw Lewis Structures for the following:
Lewis Structures of Simple Lewis Structures of Simple MoleculesMolecules
C
H
H H
H
Cl
O
O O
K+
KClO3
CF4
..
..H C O H
H
H
H
H
C
Ethyl Alcohol (Ethanol)
Potassium Chlorate Carbon Tetrafluoride
......
..
..
..
.. ...... ..
.... C
F
FF
F
......
..
.. ..
..
....
CH4
Methane
Lewis Structures of Simple Lewis Structures of Simple MoleculesMolecules
N
H
H H. .
N
H
H H
H
+
Ammonia
Ammonium Ion
C
NN
O
H H
HH
. .
. .
. .
. .
Urea
Formal ChargeFormal Charge
Equals the number of Equals the number of valence valence electrons electrons of the free atom minus [the of the free atom minus [the number of unshared valence electrons number of unshared valence electrons in the molecule + 1/2 the number of in the molecule + 1/2 the number of shared valence electrons in the shared valence electrons in the molecule].molecule].
http://www2.gasou.edu/chemdept/general/molecule/fc.htm
Oxidation NumberOxidation Number
Formal Charge Formal Charge
Charge Density Charge Density
ResonanceResonance Occurs when more than one valid Occurs when more than one valid
Lewis structure can be written for a Lewis structure can be written for a particular molecule.particular molecule.
These are These are resonance structuresresonance structures. . The actual structure is an average of the The actual structure is an average of the resonance structures.resonance structures.
Resonance: Delocalized Electron-Pairs
Ozone : O3 ......
..
O O
O ........ ..OOO..
I II
O
O
O
..
........
Resonance Hybrid Structure
One pair of electron’s resonates between the two locations!!
....
Resonance and Formal ChargeResonance and Formal Charge
Not as goodNot as good Better Better
COO(-1)(0)(+1)COO(0)(0)(0)
Acetic acid Acetic acid
Complete the Lewis Structure.Complete the Lewis Structure.
Acetic acidAcetic acid
The nitrogen atom in theammonium ion has a formalcharge of +1, but the actualpositive charge of the ion isdistributed around the hydrogen atoms and the nitrogen atom has a partial negative charge.
Localized Electron ModelLocalized Electron Model
1.1. Description of valence electron Description of valence electron arrangement (Lewis structure).arrangement (Lewis structure).
2.2. Prediction of geometry (VSEPR model).Prediction of geometry (VSEPR model). 3.3. Description of atomic orbital types used Description of atomic orbital types used
to share electrons or for lone pairs.to share electrons or for lone pairs.
Coupled with molecular orbital theory, highly Coupled with molecular orbital theory, highly reliable conceptual images of molecular reliable conceptual images of molecular shape can be obtained.shape can be obtained.
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