Molecular structure and covalent bonding
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Molecular structure and covalent bonding. Chapter 8. Key concepts. Understand the difference between Lewis structures and molecular geometries. Know the basic shapes of several molecule types. Know how to predict molecular shapes using valence-shell electron repulsion (VSEPR) model.

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Key concepts l.jpg
Key concepts

  • Understand the difference between Lewis structures and molecular geometries.

  • Know the basic shapes of several molecule types.

  • Know how to predict molecular shapes using valence-shell electron repulsion (VSEPR) model.

  • Understand how overall molecular shape can affect the dipole moment of the molecule.

  • Understand the use of valence-bond theory as an explanation for the VSEPR model.

  • Know different hybrid orbitals that function in molecular geometries.


Molecular geometries l.jpg
Molecular geometries

  • Lewis structures help us understand the type of bonds between atoms in a molecule

  • But, they do NOT indicate the geometry in 3-D space.

  • VSEPR theory helps describe the actual geometry of molecules based on their covalent bonding.


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Molecular geometries

  • two main parameters to know for molecular geometry:

    • bond length(s) –

    • bond angle(s) –

    • (there is a third parameter, the dihedral angle, important in molecules with more than one central atom, which we will occasionally encounter)


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Fundamental geometry

  • five fundamental geometries behind all ABn molecular shapes

    • Linear

    • Trigonal planar

    • Tetrahedral

    • Trigonal bipyramidal

    • Octahedral

  • Table 8.1 (p. 305) illustrates fundamental geometries


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valence-shell electron repulsion (VSEPR) model

  • used to predict geometries of ABn molecules where A is a p-block element.

  • Electron domains (“regions of high electron density”): areas where electrons are most likely found in a molecule.

  • two types of electron domains:

  • bonding domain -

  • non-bonding domain –


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Basic principles of VSEPR

  • Electron domains repel each other; will force as far away from each other as possible.

  •  the best electronic geometry is the one that minimizes all electron repulsions in the molecule.


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The electronic geometry is NOT the molecular geometry.

  • Electronic geometry –

  • molecular geometry –



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Steps for predicting molecular geometries

  • Write Lewis formula and identify a central atom.

    • Examples: H2O, NH3, CH4, CO2, SO2, SO32-, COCl2, SF6, XeF4

  • Count regions of high electron density (electron domains) on that central atom.

    • Single bonds, multiple bonds, lone pairs all count as ONE region.


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Steps for predicting molecular geometries

  • Determine electronic geometry around central atom.

  • Determine molecular geometry around central atom.

    • If there is ≥ 1 non-bonding electron pair in the molecule, the electronic geometry is never the same as the molecular geometry.


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Non-bonding pairs and multiple bonds affect the ideal molecular geometry.

  • Adjust molecular geometry for any lone pairs (or multiple bonds).

  • Non-bonding domains take up more space than bonding domains, and have a greater repulsive force that will compress bond angles in the molecule.

  • Multiple bonds have higher electron density than single bonds.

  •  multiple bonds compress bond angles between single bonds.

  • the amount of compression is

    Lone pair >> multiple bonds > single bonds


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Steps for predicting molecular geometries molecular geometry.

  • Determine hybrid orbitals, describe bonding.

  • Hybrid orbitals: How to explain both bonding between atoms and molecular geometries. Atomic orbitals cannot explain this.

  • Different atomic orbitals of the central atom mix to form hybrid orbitals that have proper shapes to produce observed molecular geometries.


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Types of hybrids molecular geometry.

  • What atomic orbitals combine to form the hybrid orbitals on the central atom?

  • sp –

  • sp2 –

  • sp3 –

  • sp3d –

  • sp3d2 –

  • The number of hybrid orbitals ________ the number of atomic orbitals


Sp hybrids l.jpg
sp molecular geometry. hybrids


Sp 2 hybrids l.jpg
sp molecular geometry.2 hybrids


Sp 3 hybrids l.jpg
sp molecular geometry.3hybrids


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sp molecular geometry.3d hybrids

suppose I had SF4 instead of

PF5. Where would the lone pair

be located?

Lone pairs of trig. bipyrimidal

electronic geometries first occupy

____________ positions.


Sp 3 d 2 hybrids l.jpg
sp molecular geometry.3d2hybrids

What if we had XeF4 instead

of SF6? Where would the lone

pairs be located?


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Steps for predicting molecular geometries molecular geometry.

  • Can another central atom be identified?

    • Not in current examples, but how about C2H6?


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Multiple bonds in the molecule molecular geometry.

  • consider C2H4, which has a double bond (H2C=CH2).

  • What is the electronic geometry on each C? molecular geometry? What hybrid orbitals are used?

  • of the 2 bonds between C and C, one is between sp2 orbitals on each C. Where is the other bond?


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 and  bonds molecular geometry.

  • Bond between sp2 orbitals of carbons called a  (sigma) bond. Orbitals overlap head-to-head.

  • other bond forms between unhybridized 2p orbitals of carbons. This is called a  (pi) bond. Orbitals overlap side-by-side.

  •  bond extends above and below the plane of the  bond.


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Triple bonds molecular geometry.

  • Let’s use our molecular geometry process on acetylene (HCCH). What do we get for the molecular geometry?

  • What hybrid orbitals are used?

  • How are the multiple bonds formed?


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Steps for predicting molecular geometries molecular geometry.

  • Determine if molecule is polar or non- polar

    • We must examine the dipole moment along each bond in context of the molecular geometry

    • Dipoles are vectors, so they add like vectors.


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To be or not to be…polar… molecular geometry.

Two conditions for polarity:

  • There must be at least one polar bond (or lone pair) on the central atom.

  • a. the polar bonds (if more than one) must not cancel each other out, or

    b. lone pairs (if more than one) must not have a geometry that cancels out.

    of our examples, which are polar? which are non-polar?


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