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Chemistry 101 - SEAS

Net Dipole Moments & VSEPR:
Trigonal planar molecules & Tetrahedral molecules

As discussed in class, the VSEPR geometry of a molecule can be used in combination
with its bond dipole vectors to predict if the molecule will be polar or non-polar. It is a
matter of being able to picture the vector tug-of-war among the molecule!s bond
dipoles to see if there is cancellation (non-polar molecule) or not (polar molecule). It
was easy to demonstrate for the linear (Steric Number (SN) = 2) case. Herein we want
to demonstrate it for the less obvious trigonal planar (SN = 3) and tetrahedral (SN = 4)
cases. Hopefully, you will then believe what was stated:

Unless there are identical bonds to identical atoms, a trigonal planar (SN = 3)
molecule or a tetrahedral (SN = 4) molecule will still be polar (
net
! 0).

Since we are dealing with a vector quantity, we will address the two issues,
magnitude (length) and direction (geometry), separately.

Magnitude: Bond dipoles of equal length
Why: Identical bonds to identical atoms?

Recall, the length of the bond dipole vector (
bond
) depends on two (2) factors
for the polar A-B bond:

bond
= ! r = (amount of charge separated) (distance of separation)

The amount of charge separated (!) is proportional to the electronegativity
difference between A and B (i.e., "x
AB
= |x
A
- x
B
| ).

The distance of separation (r) is proportional to the A-B bond length.
[Recall that an A-B single bond, an A=B double bond, and an A"B triple
bond will have different lengths.]

Thus, unless you have the same B atoms bonded to the central A atom for each
bond dipole, ! won!t be the same. However, even if the same B atom is attached to
the A in each bond dipole, if bonding is not the same for each A-B bond, then r will
not be the same and ! r =
bond
will not have the same magnitude for each polar A-B
bond. Note that this is true for either (any) steric number, since this is a magnitude
issue, not a direction (geometry) issue.

Direction:
Demonstration that equal-length vectors will sum to zero for
a trigonal planar geometry and for a tetrahedral geometry.

For these demonstrations, we will exploit two equivalent ways that we can sum vectors:


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Resolve each input vector into its components - using the trigonometry of right
triangles - and then sum the individual x, y, and z components to obtain the
overall components.

If the input vectors are attached to a common (coordinate) origin, then the (x, y, z)
coordinates of the input vectors! tips are the components and can be
simply summed as before.

We will use the first approach in our trigonal planar example and the second approach
in the tetrahedral example. Here goes.

Trigonal planar: (Example: BF
3
, B is the central atom with the F-B-F bond
angle = 120)

As can be seen below, BF
3
is a planar molecule. Thus, we only have to determine two
components for each of the identical length bond dipole vectors (
B-F
). Recall that
fluorine (F) is more electronegative than B (or any other element). Thus, each bond
dipole vector is directed from B to F. We will choose the plane of the molecule to be the
plane of the page and denote it as the xy-plane. Note that the upper
B-F
bond dipole
vector is along the +y axis only whereas the two lower vectors have both x and y
components, the operative angle being 60 (half of 120). Also: cos(60) = 1/2.



Diagram summary:

B-F,x,net
= 0 -
B-F
sin(60) +
B-F
sin(60) = 0 and

B-F,y,net
=
B-F
-
B-F
cos(60) -
B-F
cos(60)
=
B-F
-
B-F
(1/2) -
B-F
(1/2) = 0

As anticipated, the molecule will be non-polar (
net
= 0) since all of the vector
components sum to zero. Note that if the lengths were not the same
(i.e., not identical bonds to identical atoms), all of the cancellations would not
occur and there would be a net , a polar molecule.
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Tetrahedral: (Example: CF
4
, C is the central atom with the F-C-F bond angle
= the tetrahedral angle = 109.5)

CF
4
is a not a planar molecule. Thus, although we could resolve each of the
C-F
bond
dipole vectors into its x, y, and z components using trigonometry, it is a bit messy. But,
we will make use of the relationship between a perfect tetrahedron and a cube. It is:
if we draw 2 vectors from the center of the cube to diagonal locations in the upper face
and then draw 2 vectors from the center to opposite diagonal locations in the lower face,
we will create 4 tetrahedrally situated vectors. Now, if we place our xyz-coordinate
system in the center of the cube, it is hopefully easy to see that the (x,y,z) coordinate of
any of the vertices will each have the same magnitude. That is, it is the same distance
from center to front as to back, from center to top as to bottom, and from center to left
as to right - since the origin is in the center of the cube. Then, as the diagram shows, if
we denote the magnitude of any of these coordinate distances as a, all we have to do
is to work out the signs. This is shown in the following diagram.


Diagram summary:
Summing the 4 x-coordinates, then the 4 y-coordinates, then the 4 z-coordinates:

C-F,x,net
= + a + a - a - a = 0

C-F,y,net
= + a - a + a - a = 0

C-F,z,net
= + a - a - a + a = 0

As anticipated, the molecule will be non-polar (
net
= 0) since all of the vector
components sum to zero. Note that if the lengths were not the same (i.e., not identical
bonds to identical atoms), all of the cancellations would not occur since the origin could
no longer be in the center of the cube. Thus, the x, y, and z coordinates would no
longer all have the same magnitude and there would be a net , a polar molecule.

You will never have to go through such a demonstration on any exam; but hopefully you
now understand/believe:
Unless there are identical bonds to identical atoms, a trigonal planar (SN = 3)
molecule or a tetrahedral (SN = 4) molecule will still be polar (
net
! 0).