(2) Experiment 19: Models of Molecular Shapes, VSEPR

Theory and Orbital Hybridization

Experiment 19: Models of Molecular Shapes, VSEPR Theory and Orbital Hybridization

Source: James Postma, Julian Roberts et al. Chemistry in the Laboratory, 7th ed. W.H.
Freeman, 2010.

Prelab Experiment 19: Models of Molecular Shapes, VSEPR Theory and Orbital
Hybridization

Hemoglobin carries
oxygen from the lung
or gills of most
vertebrates and
invertebrates, to tissue
via blood. Red and blue ribbons are
globin which hold the four (4) “Heme”
groups in place.

Question 1: is this a chaotic mess or

is there order in heme?

Answer Q1:

Question 2: what is ultimately

responsible for the shape of
molecules?

Answer Q2:

If you go to wiki, to Heme and under the section called “Cooperativity” animates the “oxygen”
and “deoxygenation” process, that is the Fe3+ to Fe2+ reduction oxidation step.

Below is a Lewis diagram (b) of the Heme group, with Fe2+ at the center; once oxygen attaches
the iron 2+ cation (Fe2+) is oxidized to Fe3+.
 Question 3: looking at the Heme group, picture (b) below, do you think the shape of the
Heme molecules (Lewis structure) resembles an atomic picture where the atoms (1) exist in a
chaotic, spaghetti, twisting structure or (2) do you think the atoms in heme follow a scheme
where atoms have less freedom of motion, their bonds follow a stricter more orderly fashion of
lining up.

Answer Q3:

Go to Canvas, under this prelab is a video “Chem 202 Hybrid Orbitals_1.mp4” open the video to
see the 3 different points.
1. Aromatic rings create planar structures;
2. Randomly moved atoms, readopt or reposition themselves after a steric energy
minimization calculation;
3. The dynamic movement of every atom inside a molecule.

Question 4: Did this video change your previous answer, if so why or maybe why not?

Answer Q4:

Question 5: how would you explain “steric energy” after looking at the video?
 Answer Q5:

Question 6: describe both the orderly as well as a chaotic behavior of atoms in a molecule.

Answer Q6:

All bonds in a molecule originate from atomic orbitals.

Making bonds between 2 hydrogen atoms to make H2, using 2@s orbits would look like:

Other possible combinations would be an [s-orbit] + [p-orbit], and also 2 p-orbits.

Question 7: Draw how a d-orbit (dx2-y2 for example) with a px-orbit might look.

Answer Q7:

Beyond binary

In the diagram below, compare the central atom bond angles of the atomic
orbitals to the actual bond angles seen in molecules
 Question 8: Why can we not use atomic orbitals to describe the type of orbitals used to
construct Boron Trifluoride or Methane?

Answer Q8:

Valence Bond Theory

Valence bond theory or VB theory describes what a bonding orbital, between

two or more atoms, looks like.

What happened to the Atomic orbitals with bond angles of spheres, 90 or 180
shaped orbitals? The answer is we have to remember that atomic orbitals are
waves, they are calculated as a wave-particle to describe where we will find an
electron. What results from these quantum mechanics calculations are atomic
orbitals where we find electrons in “shells” and “subshells” with a shape like s, p, d, f, etc. Those
shapes are calculated as the “lowest energy” or most stable energy for any electron to exist as it
orbits the nucleus. Now, when atomic orbitals from different atoms “approach” each other, a
NEW lower, Energy level exists for those electrons, meaning a new or different type of
bonding/molecular orbital is “recalculated.”

It might be helpful think of how we derive gas laws, or any equation for that matter. We take
experimental, or observed data and determine an equation that best describes what we see. That
is what we did in Valance Bond Theory (VBT). We can not use Atomic Orbital theory to
describe Molecular Bonds in molecules.

Question 9: how do you define the word “Hybrid” in your everyday life; the term is used to
describe cars, crops, animals, what do you think of when you see the word Hybrid?

Answer Q9:

VBT is a hybrid theory. Hybrid in this case is a “mixing” process, crossing two different, yet
similar ideas. An example in automobiles is putting batteries in a gasoline powered car, or cross-
pollinating two different breeds of corn to get new species of corn with characteristics of the two
parent corn species. In VBT theory we “mix” the original (parent) atomic orbitals to produce a
new hybrid bonding orbital.
Carbon will, 100% of the time form four bonds; rare exceptions exist where carbon makes 3 or 5
bonds, but these compounds cannot be isolated, meaning you cannot bottle them up and sell that
type of carbon molecules. When carbon does form 3 or 5 bonds, those types of compounds
exists in a “transition states” (see kinetics chapter) but will only last until carbon can go back to
forming its regular four bonds.

When carbon makes 4 bounds, it needs 4 atomic orbits. What must happen for carbon is it takes
all for atomic orbitals the 1@s-orbit and the 3@p-orbits [px, py, pz] and “mixes” them together, in
a quantum-mechanic-blender to produce 4 new orbits. These 4 new bonding or molecular orbits
have a new name, after mixing, called sp3, sp3, sp3, sp3, so we start with 4 orbits and produce 4
new bonding orbits.

Question 10: How many bonds does carbon typically like to make?

Answer Q10:

Question 11: Why do we call the new “mixed” or hybrid orbitals for carbons new four
bonding/molecular orbitals “sp3”?

Answer Q11:

Question 12: if a molecule needs to form 3 bonds than how many atomic orbitals would it
need?

Answer Q12:
Boron typical makes 3 bonds, if boron makes 4 bonds, BH4+ or B(OH)4- it does so as an ion. For
three bonds, boron uses 1@s and 2@p leaving

Question 13: why do we call each of boron’s 3 new hybrid orbits “sp2”?

Answer Q13:

Question 14: which orbit of boron is not hybridized?

Answer Q14:

Bond Names: Sigma (σ) & Pi (p or π)

Single bonds form when two hybrid orbitals overlap.

• These are called sigma (σ) bonds; σ-bond.
• The first bond formed is Always called the sigma bond
Second or third bonds form by a “side-on” interaction between two p-orbits.
 • These are called pi (p) bonds; π-bond.
• The first π-bond is often called π1
• The second π-bond is often called π2

Question 15: How many sigma and pi bonds in the first molecule NH3?

Answer Q15:

Question 16: in NCO-, how many sigma and pi bonds are on each “N”, “C” and “O”?

Answer Q16:

N:

C:

O:

Question 17: How many total sigma and pi bonds are in compound with the C=C bond,
assume the molecule is H2C=CH2, hydrogens were omitted for clarity.

Answer Q17:
 Steps in Valance Bond Theory

1. Find the Lewis Structure

2. Formal charge is important, you will have to either add (anions) or subtract (cations)
electrons from the central atom
3. Write the Grounds State electron configuration for the central atom
4. Count the number of sigma bonds first
a. Each σ-bond will get a Hybridized orbit
5. Each double bond will be a π-bond which is an Unhybridized orbit
a. Meaning the original atomic orbital is not hybridized
6. Always match your Lewis Structure to your Valence Hybrid picture
a. If your Lewis structure has 6 sigma-bonds than you must have 6 hybrid orbits
b. If you Lewis structure has a pi-bond, then each pi-bond is just an atomic orbital

Example of IF32-

1. Lewis structure shows 3-lone pairs and 3 sigma-bonds or 6 bonds total

a. Hybridize 6 orbits
b. 4 orbits from the original ground state
c. Add 2 more orbits from the empty d-orbits
2. Show the iodine with its 7-valance electrons
3. Hybrid orbits have 6, don’t forget to include the unused d orbits
4. The formal charge on Iodine is 2-, so add 2 more electrons in the hybrid diagram.
 Experiment 19: Models of Molecular Shapes, VSEPR
Theory and Orbital Hybridization

Include the following in your lab notebook.

1. BeCl2
2. BF3
3. SnCl2
4. CH4
5. NH3
6. H2O
7. PCl5
8. SF4
9. BrF3
10. XeF2
11. SF6
12. IF5
13. XeF4
14. PO43-
15. ClO3-
16. ClF4-
17. NO2-
18. NO3-
19. CO2
20. SF42-
21. SO42-
22. SO32-
23. AsO43-

Work Across Both Pages of your lab notebook.

Arrange your data into columns, see below. Do not put lines in your lab notebook.

Lewis Orbital Atomic # Hybrid VSEPR VSEPR Draw

Structure box for orbitals hybrid orbital Geometry molecular Dipole,
1. GS & hybridized name name shape is it
2.Hybrid name polar?
BeCl2
BF3
Example:

1. Lewis Structure Cl Be Cl
2. An orbital box diagram for: Remember that Z = atomic number = protons = electrons.
The examples shown in the lab book are sufficient diagrams.
a. Ground State
b. Hybrid State
Z=4

p p p p p
sp sp
s

AO or GS Hybrid

3. The atomic orbitals that are hybridized…..One s and one p

4. Number of hybridized orbitals…..2

5. sp
6. Geometry of the hybrid orbitals, this is the VSEPR Class…..Linear
7. The VSEPR molecular shape…..Linear

Cl Be Cl

8. Dipole, show dipole moment using a Lewis structure…… no dipole