t14.1 Further Aspects of Covalent Bonding and Structure

Chemical Bonding &
Structure
Further aspects of covalent bonding and structure
Hybridization
Ms. Thompson - HL Chemistry

Wooster High School
Saturday, August 1, 15
Topic 14.1
Further aspect of covalent bonding and
structure
• Covalent bonds result from the overlap of atomic orbitals. A sigma
bond (σ) is formed by the direct head-on/end-to-end overlap of
atomic orbitals, resulting in electron density concentrated between
the nuclei of the bonding atoms. A pi (π) bond is formed by the
sideways overlap of atomic orbitals, resulting in electronic density
above and below the plane of the nuclei of the bonding atoms.
• Formal charge (FC) can be used to decide which Lewis (electron
dot) structure it Is preferred from several. The FC is the charge an
atom would have if all atoms in the molecule had the same
electronegativity. FC =(Number of valence electrons) -
1/2(Number of bonding electrons) - (Number of non-bonding
electrons). The Lewis (electron dot) structure with the atoms
having FC values closest to zero is preferred.
Topic 14.1
structure
• Exceptions to the octet rule include some species having
incomplete octets and expanded octets.
• Delocalization involves electrons that are shared by more than
two at times in a molecule or ion as opposed to being localized
between a pair of atoms.
• Resonance involves two or more Lewis (electron dot)
structures to represent a particular molecule or ion. A
resonance structure is one of two or more alternative Lewis
(electron dot) structures for a molecule or ion that cannot be
described fully with one Lewis(electron dot) structure alone.
structure
Nature of science
• Principle of Occam’s razor — bonding theories have been
modified overtime. Newer theories need to remain as simple as
possible while maximizing explanatory power, for example the
idea of formal charge.
structure
Formal charge
• Sometimes different Lewis dot structures can be drawn for the a
molecular species or polyatomic ion that obey the octet rule
• To determine which Lewis structure to use - must rely on formal
charge (FC) of the atoms present in the molecule or ion.
FC = (# of valence electrons) - 1/2 (# of bonding
electrons) - (# of non-bonding electrons)
• If there are more than one Lewis structures available, the most
reasonable one will be:
• the one with FC difference (∆FC=FCmax-FCmin)
closest to zero
• the one that has negative charges located on most
electronegative atom
structure
Formal charge
• For example, tetrachloromethane, CCl4:
FC (C) = 4 - 1/2(8) - 0 = 0
FC (Cl) = 7 - 1/2(2) - 6 = 0
• For example, carbonate anion, CO32-:

A FC (C) = 4 - 1/2(8) - 0 = 0
FC (OA) = 6 - 1/2(4) - 4 = 0
B B FC (OB) = 6 - 1/2(2) - 6 = -1
structure
Formal charge
• For example, boron trifluoride, BF3:
For structure a: For structure b:
FC (B) = 3 - 1/2(6) - 0 = 0 FC (B) = 3 - 1/2(8) - 0 = -1
FC (F) = 7 - 1/2(2) - 6 = 0 FC (FA) = 7 - 1/2(2) - 6 = 0
∆FC = 0 FC (FB) = 7 - 1/2(4) - 4 = +1
a b
∆FC = FCmax - FCmin
A ∆FC = (+1) - (-1) = +2
B A
structure
Different interpretations of charge
• Oxidation state, formal charge, ionic charge, partial charge, total
charge, etc... Let’s examine HF molecule
• Oxidation state: H: +1 F: -1
• Formal Charges: FC(H)=0, FC(F)=0, ∆FC=0
• Partial Charges: Electronegativity for H = 2.2 and F = 4.0
so partial charge on F due to the pulling of electrons
• Total (Net) Charges: Would be 0 as it is a neutral
molecule
structure
Molecular geometries based on five and six
electron domains
• Use same method to deduce molecular geometry for 5 & 6
electron domains as you would 2, 3, & 4 electron domains
(topic 4)
• For five electron domains, lone pairs (non-bonding pairs)
occupy the equatorial positions.
• Based on terms of repulsion, order of interactions:
• LP|LP > LP|BP > BP|BP
Number of electron Electron domain
Molecular geometry Notes
domains geometry
AB5
5 trigonal bipyramidal 5 BP’s
example: PF5
tetrahedral (AB4)
AB4E
5 trigonal bipyramidal 4 BP’s and 1 LP
example: SF4
see-saw
AB3E2
5 trigonal bipyramidalurl 3 BP’s and 2 LP’s
example: ClF3
T-shaped
Number of electron Electron domain
Molecular geometry Notes
domains geometry
AB2E3
5 trigonal bipyramidal 2 BP’s and 3 LP’s
example: I3-
linear
AB6
6 octahedral 6 BP’s
example: SF6
octahedral
AB5E
6 octahedral 5 BP’s and 1 LP
example: BrF5
square-based pyramidal
AB4E2
6 octahedral 4 BP’s and 2 LP’s
example: XeF4
square planar
structure
Overlap of atomic orbitals: Sigma and pi bonding
• A single covalent bond consists of two electrons shared between two atoms A
and B
• A single bond is a sigma bond (σ)
• A double covalent bond consists of four electrons, two pairs, shared between
two atoms A and B.
• A double bond is a sigma bond (σ) plus a pi bond (π)
• A triple covalent bond consists of six electrons, two pairs, shared between two
atoms A and B.
• A triple bond is a sigma bond (σ) plus two pi bonds (π)
σ σ+π σ + 2π
A –– B A ––
–– B ––
A ––
–– B
•• •
••
A••B A•B A•B
• ••
structure
Overlap of atomic orbitals: Sigma and pi bonding
• Lewis structure is a simple model showing how the valence electrons
are distributed in a molecule or polyatomic ion.
• We will learn a more in depth theory based on quantum
mechanics molecular orbital theory (MOT)
• Helps to better visualize sigma and pi bonds and see the difference
• For atomic orbitals to overlap, must be close in energy and have
identical symmetry. Three possible outcomes:
• bonding orbital: sigma (σ) or pi (π) bond
• anti-bonding orbital: sigma star (σ*) or pi star (π*) orbital
• non-bonding situation
• Order of bond lengths: A–B > A=B > A-B --
• Order of bond strength: A-B -- > A=B > A–B
structure
Description of a sigma and pi bond
• In the formation of a sigma bond there is a direct head-on
overlap of the atomic orbitals along the internuclear axis and
the electron density is located along this axis.
• In the formation of a pi bond there is a sideways overlap of
the atomic orbitals and the electron density is located above
and below the internuclear axis
Combination of
Molecular orbitals formed Type
atomic orbitals
σ
+ bonding
s+s
σ*
+ anti-bonding
σ
+ bonding
s + px
σ*
+ anti-bonding
s + py + NB non-bonding
s + pz + NB non-bonding
σ
+ bonding
px + px
σ*
+ anti-bonding
Combination of
Molecular orbitals formed Type
atomic orbitals
π
+ bonding
py + py
π*
+ anti-bonding
π
+ bonding
pz + pz
π*
+ anti-bonding
px + py + NB non-bonding
px + pz + NB non-bonding
py + pz + NB non-bonding
structure
Delocalization and resonance
• A molecule or polyatomic ion can have multiple Lewis
structures - identical arrangement of atoms but different
arrangement of electrons.
• These are known as resonance forms as they contribute to
the electronic structure called a resonance hybrid.
structure
Delocalization and resonance
• Can also be represented with a dashed curve or two dashed lines
as below
• This shows delocalization which is a quantum mechanical
concept used to describe the pi bonding in a conjugated system
• A conjugated system is a molecular entity whose structure
can be represented as a system of alternating single and multiple
bonds. Not localized between two atoms but instead each link has
a fractional double bond character or bond order.
• It is the interaction between:
• One p orbital with another across an intervening sigma
bond.
• A double bond and a p orbital containing a lone pair of
electrons
Practice Problem
... I Do ...
Consider the following species:
a) BrF3
b) IF5
For each species, deduce:

(i) the electron domain geometry
(ii) the molecular geometry
(iii) the approximate bond angle(s)
(iv) a valid Lewis (electron dot) structure
Practice Problem
BrF3
For Br:
number of valence electrons = 7 F
number of sigma bonds = 3
total number of valence electrons = 10 Br
Number of electron domains = 5 F F
From table 1, electron domain geometry:

trigonal bypyramidal
Practice Problem
BrF3
This is an example of a AB3E2 system, so the two lone
pairs are located in the equatorial positions:
molecular geometry: t-shaped
Practice Problem
BrF3
Bond angles: less than 90º The Br-F-Br

experimental value is 86.2º but this
cannot be predicted from the VSEPR
theory
Practice Problem
BrF3
To draw the Lewis (electron dot) structure, complete the octets

of fluorine atoms:
Practice Problem
IF5
For I:
number of valence electrons = 7 F
number of sigma bonds = 5 F F
total number of valence electrons = 12 I
number of electron domains = 6 F F
From table 1, electron domain geometry:

trigonal bypyramidal
Practice Problem
IF5
This is an example of a AB5E system, so the one lone
pair is located in any of the six equivalent positions:
molecular geometry: square-based

pyramidal
Practice Problem
IF5
Bond angles: six F-I-F bond angles are

less than 90º. Each one of these F-I-F
bond angles is 80.9º
Practice Problem
IF5
To draw the Lewis (electron dot) structure, complete the octets

of fluorine atoms:
Practice Problem
... We Do ...
a) [ICl2]-
b) SOF4

Practice Problem
... You Do ...
a) [ICl4]-

structure
An environmental perspective: Catalysis of ozone
depletion
• Ozone, O3, is a v-shaped (bent) molecule with a
bond angle of 116.8º and its two O-O bond lengths
are equal (128pm). Two contributing resonance
forms are below:
structure
depletion
• Calculate bond order:
total number of O-O bonding pairs = 3 = 1.5
total number of O-O positions 2
• A high bond order indicates more attraction between electrons. A
higher bond order also means that the atoms are held together more
tightly.With a lower bond order, there is less attraction between
electrons and this causes the atoms to be held together more loosely.
Bond order also indicates the stability of the bond.The higher the bond
order, the more electrons holding the atoms together, and therefore the
greater the stability.
structure
depletion
• In topic 6 you learned about how the ozone layer (located in
stratosphere) absorbs over 95% of harmful UV radiation
hv
O3(g) --> O2(g) + O•(g)
O2(g) + O•(g) --> O3(g) + heat
There is a net energy conversion from UV radiation to heat

energy.
Ozone depletion leads to increased skin cancer (melanoma) and
cataracts from more UV radiation hitting Earth’s surface.
structure
depletion
• The bonds in ozone can be broken by UV radiation (hv). THe
bond order for ozone is 1.5 and for the O=O bond it’s 2 - which
is much stronger and harder to break and requires higher energy
(shorter wavelength) to break.
• Energy, E, of a photon of light is inversely proportional to the
wavelength, λ, so the greater the energy, the shorter the
wavelength and vice versa.
E = hv = hc/λ
Where;
h = Planck’s constant 6.63 x 10-34 J s v = frequency of the radiation
c = speed of light = 3.00 x 108 m s-1 λ = wavelength of radiation
Practice Problem
depletion
With a partner, work on the following problem:
The average bond enthalpy in ozone is 362 kJ mol-1. Using the

relationships given in section 1 and the bond enthalpy data given in
section 11 of the data booklet, calculate the maximum wavelength,
in nm, of the UV radiation required to break the O=O double
bond in oxygen and the O–O bond in ozone.
Practice Problem
... You Do ...
Work within a group of 3-4 and answer the
following question:
Deduce the molecular polarities of the following:
• SF6
• cisplatin, Pt(NH3)2Cl2
• transplatin, Pt(NH3)2Cl2
Topic 14.1
structure
➡Covalent bonds result from the overlap of atomic orbitals. A sigma
bond (σ) is formed by the direct head-on/end-to-end overlap of
atomic orbitals, resulting in electron density concentrated between
the nuclei of the bonding atoms. A pi (π) bond is formed by the
sideways overlap of atomic orbitals, resulting in electronic density
above and below the plane of the nuclei of the bonding atoms.
➡Formal charge (FC) can be used to decide which Lewis (electron
dot) structure it Is preferred from several. The FC is the charge an
atom would have if all atoms in the molecule had the same
electronegativity. FC =(Number of valence electrons) -
1/2(Number of bonding electrons) - (Number of non-bonding
electrons). The Lewis (electron dot) structure with the atoms
having FC values closest to zero is preferred.
Topic 14.1
structure
➡Exceptions to the octet rule include some species having
incomplete octets and expanded octets.
➡Delocalization involves electrons that are shared by more than
two at times in a molecule or ion as opposed to being localized
between a pair of atoms.
➡Resonance involves two or more Lewis (electron dot)
structures to represent a particular molecule or ion. A
resonance structure is one of two or more alternative Lewis
(electron dot) structures for a molecule or ion that cannot be
described fully with one Lewis(electron dot) structure alone.

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Chemical Bonding &

Ms. Thompson - HL Chemistry

• For example, carbonate anion, CO32-:

For each species, deduce:

From table 1, electron domain geometry:

molecular geometry: t-shaped

(iii) the approximate bond angle(s)

Bond angles: less than 90º The Br-F-Br

To draw the Lewis (electron dot) structure, complete the octets

From table 1, electron domain geometry:

molecular geometry: square-based

(iii) the approximate bond angle(s)

Bond angles: six F-I-F bond angles are

To draw the Lewis (electron dot) structure, complete the octets

For each species, deduce:

For each species, deduce:

There is a net energy conversion from UV radiation to heat

The average bond enthalpy in ozone is 362 kJ mol-1. Using the

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