Chemistry 101 for eng students

Dr. Rasha El-Nashar 7th lecture

Objectives.

Apply the Valence-Shell Electron Pair Model (VSPER). Predict the effect of unshared pairs on geometry. Predict the effect of multiple bonds on geometry. Predict the polarity of molecules.

Writing Lewis structure

1. Count the number of valence electrons.

For a molecule, simply sum up the valence electrons of the atoms present. For a polyatomic anion, one electron is added for each unit of negative charge. For a polyatomic cation, a number of electrons equal to the positive charge must be subtracted.
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Writing Lewis structure (cont.)

2. Draw a skeleton structure for the species, joining atoms by single bonds.
In some cases, only one arrangement of atoms is possible, in others, there are two or more alternative structures.
Most of the molecules and polyatomic ions dealt with, consist of a central atom bonded to two or more terminal atoms , located at the outer edges of the molecule or ion. For such species (e.g. NH4+, SO2, CCl4), it is relatively easy to derive the skeleton structure. The central atom is usually the one written first in the formula, put this in the center of the molecule or ion. Terminal atoms are most often hydrogen, oxygen or a 4 halogen, bond these atoms to the central atom.

Writing Lewis structure (cont.)

3. Determine the number of valence electrons still available for distribution.

To do this deduct two valence electrons for each single bond written in step 2.

4. Determine the number of valence electrons still required to fill out an octet for each atom (except H) in the skeleton. Remember that shared electrons are counted for both atoms.
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IF
Both are equal No. of es needed > No. of es available by 2
No. of es needed > No. of es available by 4

No. of Electrons available is higher than No. Of electrons needed

Draw the structure without any multiple bonds

You have to have One Double bond

You have to have a triple bond or two Double bonds

NCl3

HCO2- and NO3-

Put the extra es on the central atom, which will exceed the octet rule

H2C2 and OCS

ClF2-, IF4-

Molecular geometry

The geometry of a diatomic molecule such as Cl2 or HCl can be described very simply. Because two points can define a straight line, the molecule must be linear. Cl-Cl, H-Cl With molecules containing three or more atoms, the geometry is not obvious. Here the angles between bonds, called bond angles, must be considered. For example, a molecule of the type YX2, where Y represents the central atom and X an atom bonded to it, can be Linear, with a bond angle of 180: X-Y-X Bent, with a bond angle less than 180 : Y X X
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The Valence-Shell Electron Pair Model (VSPER)

The model sates that, The valence electron pairs surrounding an atom repel one another, consequently, the orbitals containing those electron pairs are oriented to be as far apart as possible. This helps in predicting the geometry of some simple molecules and polyatomic ions in which a central atom is surrounded by from two to six pairs of electrons.

Ideal geometries with 2 to 6 electron pairs on the central atom

Linear

Triagonal Planar

Tetrahedral

Bent

Pyramidal

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Ideal geometries with 2 to 6 electron pairs on the central atom ( cont.)

possible when they are directed at 180 to one another. So it is a linear structure. For a 3e pairs AX3 (BF3), the three electron pairs around the boron atom are directed towards the corners of an equilateral triangle, the bond angles120. We describe this geometry as triangular planner. Molecules of the type AX4 ,(obey the octet rule), the four bonds are directed towards the corners of a regular tetrahedron. All the bonds are 109.5, the tetrahedral angle. This geometry is found in the ammonium ion and 11 sulphate ion.

The geometries for two and three electron pairs are those associated with species in which the central atom has less than an octet of electrons. For 2 e pairs AX2 (BF2), the two pairs are as far apart as

Ideal geometries with 2 to 6 electron pairs on the central atom ( cont.)

In AX5 molecules, as PF5, the five bonding pairs are directed towards the corners of a triangular bipyramid,
which a combination of two triangular pyramids fused together base to base. Three of the fluorine atoms are located at the corners of an equilateral triangle with the phosphorus atom at the center, the other two fluorine atoms are directly above and below the P atom.

In AX6 molecules, SF6, the six bonds are directed towards the corners of a regular octahedron, a figure with eight
sides but six vertices. An octahedron can be formed by fusing two square pyramids base to base. Four of the fluorine atoms in SF6 are located at the corners of a square with the S atom at the center, one fluorine atom is directly above the S atom, another directly below it.
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Effect of unshared pairs on Molecular geometry

In many molecules and polyatomic ions, one or more of the electron pairs around the central atom are unshared. The VSPER model is readily extended to predict the geometries of these species.

In general, The electron-pair geometry, is approximately the same as that observed when only single bonds are involved. The bond angles are ordinarily a little smaller than the ideal values listed. The molecular geometry, is quite different when one or more unshared pairs are present.

In describing molecular geometry, we refer only to the positions of the bonded atoms. These positions can be determined experimentally, positions of unshared pairs cannot be established by experiment. Hence the locations of unshared pairs are not specified in describing molecular geometry.13

Consider the NH3 molecule

The apparent orientation of the four electron pairs around the N atom in NH3 is shown at the left side of the above figure.
The diagram at the right shows the positions of the atoms in NH3. The nitrogen atom is located above the center of an equilateral triangle formed by the three hydrogen atoms. The molecular geometry of the NH3 molecule is described as a triangular pyramid. The bond angle is 107.
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Consider the water molecule,

The Lewis structure shows that the central oxygen atom is surrounded by two single bonds and two unshared pairs. The diagram at left emphasizes that four electron pairs are oriented tetradehrally. At the right, the positions of the atoms are shown. Clearly they are not in a straight line , the water molecule is bent. The bond angle is about 105.
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These effects can be explained in a rather simple way:

An unshared pair is attracted by one nucleus, that of the atom to which it belongs. In contrast, a bonding pair is attracted by two nuclei, those of the two atoms it joins.
Hence the electron cloud of an unshared pair is expected to spread out over a larger volume than that of a bonding pair. In NH3, this tends to force the bonding pairs closer to one another there by reducing the bond angle. In H2O, this effect is more pronounced due to the presence of two unshared pairs.
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Example 7.8.1. Predict the geometry of NH4+, GeF2, PF3

The Lewis structure for NH4+, this is an AX4 species, it is tetrahedral with 109.5 bond angle. The Lewis structure for GeF2 this is an AX2E, it is bent shape. The bond angle less than 120. The Lewis structure of PF3 this is AX3E, it should be triangular pyramid like (NH3) with a bond angle less than 109.5

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In many expanded-octet molecules, one or more of electron pairs around the central atom are shared. Geometries of these molecules are given in the following tables.

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Multiple bonds

The VSEPR model can be extended to species in which double or triple bonds are present. The four electrons in a double bond, or the six electrons in a triple bond, must be located between the two atoms, as are the two electrons in a single bond. This means that the electron pairs in a multiple bond must occupy the same region of space as those in a single bond. Hence, the extra electron pairs in a multiple bond has no effect on the geometry.
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Consider the CO2 molecule,

The central carbon has two double bonds and no shared electrons

The double bond is counted as single bond, ignoring extra bonding pairs. The bonds are directed to be as far apart as possible, giving a 180O-C-O .

The CO2 and BeF2 are linear.

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Example Predict the geometries of the ClO3ion, NO3 and N2O molecule, which have the Lewis structures. 1. The central atom, chlorine, is bonded to 3 oxygen atoms, it has one unshared pair. The ClO3- ion is of the type AX3E. This a triangular pyramid, ideal bond 109.5. 2. The central atom, nitrogen, is bonded to 3 oxygen atoms, it has no unshared pairs. The NO3 ion is of the type AX3. It has a triangular planner structure with bond angle of 120. 3. The central nitrogen atom is bonded to two other atoms with no unshared pairs. The molecule, Type 23 AX2, is linear with a bond angle of 180.

Polarity of molecules
Covalent bonds and molecules held together by such bonds may be: Polar, as a result of an unsymmetrical distribution of electrons, the bond or molecule contains a positive and a negative pole and therefore a dipole. Nonpolar, A symmetrical distribution of electrons lead to a bond or molecule with no positive or negative poles.

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Examples
The two electrons in the H2 molecule are shared equally by the two nuclei thus a bonding electron is as likely to be found in the vicinity of one nucleus as another. Bonds of this type are described as nonpolar. In the HF molecule, the distribution of the bonding electrons is somewhat different, where there is a higher electron density about the fluorine atom. Bond in this case is asymmetric this a polar bond.

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Polarity of molecules (cont.)

Polar molecules such as HF, align their positive and negative ends toward the negative and positive poles of an electric field, respectively If a molecule contains more than two atoms, it is not so easy to decide whether it is polar or nonpolar. In this case, not only bond polarity but molecular geometry determines the polarity of the molecule.

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Consider the following molecules:

All bonds in these molecules are polar as shown by the symbol , in which the arrow points to the more negative end of the bond and the + indicates the more positive end.
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 In BeF2, there are two polar BeF bonds, in both bonds, the electron density is concentrated around the more negative fluorine atom. However, because BeF2 molecule is linear, the two Be F dipoles are in opposite directions and cancel one another.

The molecule has no net dipole and hence is nonpolar.

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For the H2O, an O-H bond is polar as oxygen is more electronegative than hydrogen, thus of more electron density. In the bent H2O molecule, the two H O dipoles do not cancel each other. Instead, they add to give the H2O molecule a net dipole. The center of negative charge is located at the O atom, this is the negative pole of the molecule. The center of positive charge is located midway between the two H atoms. The H2O molecule is polar and it tends to liner up in an electric field with the oxygen atom oriented towards the positive.
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Carbon tetrachloride, CCl4, is another molecule that is nonpolar despite the presence of polar bonds. Each of its four bonds is a dipole, However, because the four bonds are arranged symmetrically around the carbon atom they cancel. As a the molecule has no net dipole. It is nonpolar.

If one of the Cl atoms in CCl4 is replaced by hydrogen, the situation changes. In the CHCl3 molecule, the H C dipole does not cancel with the three C Cl dipoles. Hence the CHCl3 is polar.
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There are two criteria for determining the polarity of a molecule:

bond polarity and molecular geometry.

If the polar A-X bonds in a molecule AXmEn are arranged symmetrically around the central atom A, the molecule is nonpolar. Molecules of the type AX2 (linear), AX3 (triangular planar) and AX4 (tetrahedral) are nonpolar. Examples: CO2, BF3, CCl4. Molecules of the type AX2E (bent), Ax2E2 (bent) and AX3E (triangular pyramid) are polar. Examples: SO2, H2O, NH3
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Predict whether the following molecules are polar or nonpolar. (a) BrCl (b) SO2 (c) SF6 (d) PF5

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