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    shapesandhybridization

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    shapesandhybridization

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    Shapes of Molecules and Hybridization

    A. Molecular Geometry
    • Lewis structures provide us with the number and types of
    bonds around a central atom, as well as any NB electron
    pairs. They do not tell us the 3-D structure of the molecule.
    H
    H C H CH 4 as drawn conveys no 3-D information
    (bonds appear like they are 90° apart)
    H
    • The Valence Shell Electron Pair Repulsion Theory (VSEPR),
    developed in part by Ron Gillespie at McMaster in 1957,
    allows us to predict 3-D shape. This important Canadian
    innovation is found worldwide in any intro chem course.
    • VSEPR theory has four assumptions
    1. Electrons, in pairs, are placed in the valence shell of the
    central atom
    2. Both bonding and non-bonding (NB) pairs are included
    3. Electron pairs repel each other Æ maximum separation.
    4. NB pairs repel more strongly than bonding pairs,
    because the NB pairs are attracted to only one nucleus
    • To be able to use VSEPR theory to predict shapes, the
    molecule first needs to be drawn in its Lewis structure.
    Shapes of Molecules and Hybridization 2

    • VSEPR theory uses the AXE notation (m and n are integers),


    where m + n = number of regions of electron density
    (sometimes also called number of charge clouds).

    AX m E n

    1. Molecules with no NB pairs and only single bonds


    • We will first consider molecules that do not have multiple
    bonds nor NB pairs around the central atom (n = 0).
    • Example: BeCl2

    o Molecule is linear (180°)


    • Example: BF3

    o Molecule is trigonal (or triangular) planar (120°)


    Shapes of Molecules and Hybridization 3

    • Example: CH4

    o Molecule is tetrahedral (109.5°)


    • Example: PF5

    o Molecule is trigonal bipyramidal (90° and 120°). There


    are three X atoms in a planar triangle and two axial
    atoms, one above and one below the central atom.
    • Example: SF6

    o Molecule is octahedral (all 90°)


    Shapes of Molecules and Hybridization 4

    2. Molecules with ≥ 1 NB pairs and only single bonds


    • The geometry of the regions of electron density is roughly the
    same as what we see when no NB pairs are involved.
    • However, the shape of the molecule is determined by looking
    at only the bonding pairs, NOT the non-bonding pairs.
    • Example: NH3

    o There are four regions of electron density (m + n = 4),


    and the electronic arrangement is still tetrahedral.
    o Yet, the shape of the molecule (look at bonding pairs
    only) is trigonal pyramidal. Angles < 109.5° (why?)

    • Example: H2O

    o Electronic arrangement is tetrahedral.


    Shape of molecule = bent
    Shapes of Molecules and Hybridization 5

    • Example: NF

    o Electronic arrangement is trigonal planar.


    Shape of molecule = linear

    • Example: SF4

    o Electronic arrangement is trigonal bipyramidal.


    Shape of molecule = see saw

    • Example: XeF3+

    o Electronic arrangement is trigonal bipyramidal.


    Shape of molecule = T-shaped
    Shapes of Molecules and Hybridization 6

    • Example: XeF5+

    o Electronic arrangement is octahedral.


    Shape of molecule = Square pyramidal

    • Example: ICl4−

    o Electronic arrangement is octahedral.


    Shape of molecule = Square planar

    • Example: the amino acid alanine


    o There can be more than one “central atom”
    Shapes of Molecules and Hybridization 7

    3. Molecules with double or triple bonds


    • These are quite simple: treat them as single bonds, and the
    AXE system still works. i.e. a multiple bond is still considered
    to be one region of electron density.
    • Examples: predict the shapes of CO2, C2H4, and NO2−
    Shapes of Molecules and Hybridization 8

    B. Molecular Polarity
    • Recall that electronegativity is a relative measurement of an
    atom’s ability to attract a bonding electron pair to itself.

    • Differences in electronegativity between two covalently


    bonded atoms result in a polar covalent bond, and atoms
    have a partial negative or partial positive charge.

    • These bonds are said to have dipole moments, which can be


    experimentally quantified. If placed in an electric field, the
    molecule will rotate and line up to the field.

    • The greater the bond polarity, the greater the dipole moment.
    However, can we say that a molecule with a polar bond must
    also be a polar molecule? Not necessarily!
    Shapes of Molecules and Hybridization 9

    • Note: The overall polarity of a molecule depends on its


    geometry and the presence of polar bonds.
    o The presence of polar bonds does not necessarily imply
    that the molecule is polar. This is because the bond
    dipole moments can cancel out (no net dipole moment).
    o Think of the bond dipoles as vectors, and if the sum of all
    of the vectors is zero, the molecule is not polar.

    • Examples:

    CO2 H 2O

    BF3 NH3

    CCl4 CFCl3
    Shapes of Molecules and Hybridization 10

    SF4 SF6

    • Notice that non-polar molecules are highly symmetrical,


    allowing the bond dipole moments to cancel out.

    • In a set of resonance structures, the overall polarity is


    averaged out over the resonance structures. For example,
    CO32− and SO42− are non-polar (no net dipole moment).
    Shapes of Molecules and Hybridization 11

    C. Hybridization (Compounds with Single Bonds)


    • How does molecular shape relate to the orbitals in the
    valence shell?
    • Consider methane, CH4, which uses the valence electrons in
    the 2s, 2px, 2py, and 2pz orbitals. These electrons must
    become unpaired prior to making bonds with H.

    • Recall the shapes of the s and p orbitals.

    • If we used these orbitals to bond


    with the H atoms, we would get this
    structure. Yet, we know that the
    proper structure from VSEPR theory
    is tetrahedral. This structure shown
    is clearly incorrect!
    • How do we explain this?
    Shapes of Molecules and Hybridization 12

    • Before bonding to H atoms, the one 2s and three 2p atomic


    orbitals are mixed and rearranged to give a new set of four
    equivalent (same energy) “hybrid” atomic orbitals (sp3)
    arranged at tetrahedral angles of 109.5°.

    • Each new hybrid orbital


    around the C contains one
    electron.
    • After each pairs up with one
    electron from H, the orbitals
    contain an electron pair.

    • The single bond formed by the direct, head-on overlap of


    orbitals is a sigma bond (σ).
    Shapes of Molecules and Hybridization 13

    • Note: hybrid orbitals can also contain NB pairs, for example,


    in ammonia and water. These also have tetrahedral electronic
    arrangements and are sp3.

    • NH3, which has a tetrahedral


    electronic arrangement,
    contains three σ bonds. Its
    shape is trigonal pyramidal.

    • sp3 hybridization is just one possibility. Five major


    hybridization types form the VSEPR structures, and these
    types are summarized in this table (details follow).

    Regions of Atomic Hybrid Electronic


    e− density orbitals orbitals arrangement
    2 one s, one p two sp linear
    3 one s, two p three sp2 trigonal planar
    4 one s, three p four sp3 tetrahedral
    5 one s, three p, one d five sp3d trigonal bipyramidal
    6 one s, three p, one d six sp3d2 octahedral

    o Regions of electron density: an NB pair, a single bond, or


    a multiple bond each constitute one region.
    o Electronic arrangement may not equate to molecular
    shape if there is at least an NB pair present.
    Shapes of Molecules and Hybridization 14

    1. sp hybridization
    • The combination of one s and one p results in the formation
    of two sp orbitals. These two hybrid orbitals are 180° apart.

    • Where we have used only one of the p orbitals, there must be


    two p orbitals remaining. (Recall there are three p orbitals).
    We’ll see later on that these leftover orbitals are used when
    there is multiple bonding.
    • The two leftover p are 90° to each other and the sp hybrids.
    Shapes of Molecules and Hybridization 15

    2. sp2 hybridization
    • One s + two p = three sp2 orbitals 120° apart.

    • There is one leftover p orbital remaining, since we started


    with three p orbitals and used two of them for hybridization.
    Shapes of Molecules and Hybridization 16

    3. sp3 hybridization
    • One s + three p = four sp3 orbitals 109.5° apart.
    • There are no leftover p orbitals. Also see diagram on p. 12.

    4. Others: sp3d and sp3d2 hybridization


    • One s + three p + one d = five sp3d orbitals
    • One s + three p + two d = six sp3d2 orbitals

    IF5 (sq. pyramidal)


    Shapes of Molecules and Hybridization 17

    D. Hybridization (Compounds with Multiple Bonds)


    • How do we assign hybridization to compounds containing
    multiple bonds? The same way! We still examine the number
    of regions of electron density (table on page 13).
    • Consider ethene. Each carbon has an AX3 H H
    configuration (sp2-hybridized). Remember to C C
    count double bonds as one region. Each C also H H
    has a remaining p orbital (see p. 15).

    • Recall that σ bonds are formed by the direct overlap of


    orbitals, which result in single bonds. Where do double
    bonds come from?
    o The first bond in the double bond comes from a regular
    single bond caused by direct overlap (i.e. a σ bond)
    Shapes of Molecules and Hybridization 18

    o The second bond comes from the sideways overlap of


    the leftover p orbitals to give a pi (π) bond. This is 90° to
    the plane defined by the trigonal-planar σ bonds. The π
    bond is both above and below the plane (2 lobes).

    • The structure therefore appears like this… note that π bonds


    involve a sideways overlap, so bond rotation is not possible.
    Shapes of Molecules and Hybridization 19

    • How about a triple bond? Example: acetylene H C C H


    o Carbon atoms are sp-hybridized, and each has two
    remaining p orbitals 90° to each other (see p. 14)
    o The first bond in the triple bond originates from the direct
    overlap of sp orbitals (σ bond)
    o Both the second and the third bonds in the triple bond
    are π bonds originating from the sideways overlap of the
    remaining p orbitals. These two π bonds are 90° apart.

    • Example: assign the hybridizations and the number of π


    bonds present in the molecule acetone

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