FROG Chapter05 PDF

Chapter 5.
Structure of Molecules
Faculty Resource and Organizational Guide (FROG)
Table of Contents
Notes to Instructors regarding this chapter: ...............................................................................4
Materials for Chapter 5 Activities................................................................................................5
Reagents for Chapter 5 Activities.................................................................................................5
Section 5.1. Isomers.......................................................................................................................6
Learning Objectives for Section 5.1: ...........................................................................................6
Investigate This 5.1. How do different alcohols react in a Breathalyzer test? ........................6
Consider This 5.2. Are all alcohols detected by the Breathalyzer test?...................................8
Consider This 5.3. How do the properties of the butyl alcohol isomers differ? .........................8
Section 5.2. Lewis Structures and Molecular Models of Isomers...........................................10
Learning Objectives for Section 5.2: .........................................................................................10
Consider This 5.10. What are the Lewis structures and molecular models for the C4H10O
isomeric alcohols?......................................................................................................................10
Section 5.3. Sigma molecular orbitals .......................................................................................13
Consider This 5.12. How do the PEs and KE vary with the proton-proton distance?..............13
Consider This 5.14. What are the relative sizes of atomic and molecular orbitals? .................14
Consider This 5.15. What is the symmetry of n orbitals?? .....................................................14
Section 5.4. Sigma Molecular Orbitals and Molecular Geometry..........................................15
Consider This 5.16. What are the geometries of second period hydrides?...............................15
Consider This 5.20. How are all six octahedral positions equivalent? .....................................17
Section 5.5. Multiple Bonds........................................................................................................18
Investigate This 5.22. Do carbon-hydrogen compounds react with permanganate? ................18
Consider This 5.23. What compounds react with permanganate?............................................20
Consider This 5.25. What are the Lewis structure and molecular model for methanal
(formaldehyde)?.........................................................................................................................20
Consider This 5.26. What are the structures and reactivity of C6H14 and C6H12? ....................21
Consider This 5.27. What is the geometry of double bonded molecules?................................24
Section 5.6. Pi Molecular Orbitals.............................................................................................25
Section 5.7. Delocalized orbitals ................................................................................................25
Consider This 5.37. Do Lewis structures give correct geometries for CO32 and NO3? .........25
Consider This 5.38. What are the bonding and structure of the CO2 molecule? ......................26
Investigate This 5.41. What happens when substances are cut?...............................................27
Consider This 5.42. What substances can be cut in two? .........................................................29
ACS Chemistry FROG
Chapter 5
Section 5.8. Representations of Molecular Geometry..............................................................29

Consider This 5.47. How do you draw 3-D structures for larger molecules? ..........................29
Consider This 5.50. How many hydrogen atoms are bonded to a carbon? ..............................31
Consider This 5.53. Can different skeletal structures represent the same molecule?...............31
Section 5.9. Stereoisomerism......................................................................................................32
Investigate This 5.55. How many C4H8 molecular structures are possible?.............................32
Consider This 5.56. What are the line (condensed) formulas for the C4H8 isomers?...............34
Investigate This 5.59. Do solutions affect polarized light? ......................................................35
Consider This 5.60. What solutions affect polarized light?......................................................37
Investigate This 5.62. Are there stereoisomers for lactic acid? ................................................38
Consider This 5.63. Can you identify optical isomers? ............................................................39
Section 5.10. Functional Groups Making Life Interesting.................................................40
Learning Objectives for Section 5.10: .......................................................................................40
Investigate This 5.65. How many C3H8O2 isomers are there?..................................................41
Sample Worksheet for Investigate This 5.65.............................................................................42
Consider This 5.66. What are the functional groups in C3H8O2 isomers?................................43
Sample Worksheet for Consider This 5.66 ................................................................................44
Consider This 5.68. What are the interactions between an alcohol and an aldehyde? .............44
Section 5.11. Molecular Recognition .........................................................................................45
Learning Objectives for Section 5.11: .......................................................................................45
Consider This 5.71. Can you construct a molecule-to-order? ..................................................45
Sample Worksheet for Consider This 5.71 ................................................................................47
Section 5.13. Extension Antibonding Orbitals: The Oxygen Story ...................................47
Investigate This 5.73. Are O2 and N2 affected by a magnet? ...................................................47
Consider This 5.74. How are O2 and N2 gas affected by a magnet?.........................................48
Solutions for Chapter 5 Check This Activities...........................................................................50
Check This 5.4. Comparison of the C5H12 and C4H10O isomers ..............................................50
Check This 5.5. Lewis structures of the C2H7N isomers ..........................................................50
Check This 5.7. Lewis structures and molecular models for C3H9N isomers ..........................51
Check This 5.9. More on the C5H12 isomers.............................................................................52
Check This 5.11. Boiling points of the C4H8O alcohols...........................................................52
Check This 5.13. Potential and kinetic energy combinations...................................................52
Check This 5.17. A fourth combination of sigma orbitals........................................................53
Check This 5.19. The structure of SF6 ......................................................................................53
Check This 5.21. Sigma orbitals around third- and higher-period atoms in molecules............54
Check This 5.28. Other bond angles in ethene and methanal...................................................54
Check This 5.30. Lewis structure for the ethyne (acetylene) molecule....................................54
Check This 5.31. Representations of the bonding in ethene.....................................................55
Check This 5.32. The sigma-pi representation for methanal ....................................................55
Check This 5.33. The sigma framework and pi molecular orbital in methanal........................56
Check This 5.34. The sigma-pi representation for ethyne ........................................................56
Check This 5.36. Lewis structure for the nitrate ion.................................................................56
ACS Chemistry FROG
Chapter 5
Check This 5.39. Bond order in carbon dioxide .......................................................................56

Check This 5.40. Structure of the ozone molecule ...................................................................57
Check This 5.43. Three-dimensional packing of spheres .........................................................57
Check This 5.44. More properties of metals.............................................................................58
Check This 5.45. Interpreting 3-D structures............................................................................58
Check This 5.46. 3-D structures ...............................................................................................59
Check This 5.49. 3-D and condensed structures for the C5H12 isomers ...................................59
Check This 5.52. Skeletal structures for the C5H12 isomers .....................................................59
Check This 5.54. Interpreting skeletal representations.............................................................60
Check This 5.57. Cis-trans isomers..........................................................................................60
Check This 5.58. Identifying isomers .......................................................................................61
Check This 5.61. Direction of optical rotation .........................................................................61
Check This 5.64. Properties of optical isomers ........................................................................61
Check This 5.67. Retinol and retinal ........................................................................................62
Check This 5.69. Identifying functional groups .......................................................................63
Sample Worksheet for Check This 5.67 and 5.69 .....................................................................63
Check This 5.70. Information from different representations of molecules.............................64
Check This 5.72. One form of molecular recognition ..............................................................65
Check This 5.75. Molecular orbitals in nitrogen ......................................................................65
Sample from the Classroom: Chapter 5 Quiz ...........................................................................66
Chapter 5, Quiz Section Exercise ..............................................................................................66
Sample from the Classroom: Chapter 5 Exam .........................................................................66
Sample Chapter 5 Exam.............................................................................................................66
ACS Chemistry FROG
Chapter 5
Notes to Instructors regarding this chapter:

In chapter 4, we discussed the interactions of atoms with nuclei and focused on the energy
associated with the interaction (potential energy and kinetic energy with respect to the
stability of the atom). In chapter 5, we make the transition to molecules. Here, electrons are
interacting with more than one nucleus. The electron is still a matter wave, but the outcome is
more complicated. To mathematically derive these waves, we could use density functional
theory (DFT), linear combination of atomic orbital theory (LCAO), valence bond theory,
and/or absolute molecular orbital theory (Mulliken approach). In the true molecular orbital
approach, there are no atomic orbitals, but just electron density from the electron waves
interacting with nuclei. Since the mathematics is complex, we do not provide information on
how the shapes of the molecular orbitals are obtained, but simply give the results. This allows
students to focus on the structure of the molecules.
Although the terms, resonance and resonance hybrid are used commonly in the chemistry
curriculum, especially in organic chemistry texts, a conscious decision was made by the
Chemistry writing team not to introduce these terms. The team had observed that students
often visualize resonance as an actual exchange among the Lewis structures. Thus, we
agreed on using the delocalization terminology. This is consistent with the lowering of
electronic energies when the electron waves are more spread out, and is the basis for the lower
energy of the resonance hybrids. If you feel comfortable introducing the resonance
terminology, you may, but the book does not.
Note an error in the presentation of the chapter opening illustration. The all-trans retinal
molecule represented by the ball-and-stick model at the lower right has been rotated 180
from the way it is supposed to be shown. The aldehyde group should be on the left for easy
comparison with the structure of the 11-cis isomer at the upper left.
The chapter opening illustration highlights the structure of a protein, opsin, in a hybrid
representation. Cylinders show the positions of the alpha helices that span the membrane
where these molecules are found and are a sort of foundation for the structure. Most of the rest
of the protein is shown in a space-filling representation. Refer students who are interested in
this structure back to Figure 1.31 (page 35) where the structure of the alpha helix and its
relationship to cylindrical parts of proteins is illustrated. You probably shouldnt spend a great
deal of time, if any, discussing this structure, as it is too complex for most students at this
stage really to appreciate. It is worth noting the size of the protein compared to the retinal.
You might ask students to estimate how large a model of the protein would be, if constructed
from their model kits.
ACS Chemistry FROG
Chapter 5
Materials for Chapter 5 Activities

Activity
Material
Total Quantity
5.1, 5.22
Small test tubes
5.1, 5.22
Glass droppers
5.10, 5.16, 5.25, 5.26, 5.27,

5.38, 5.47, 5.53, 5.55, 5.62,
5.63, 5.65, 5.71
Modeling kits
1/student
5.41
Shallow dish
5.41
Sharp knife
5.59
Overhead projector
5.59
Sheet of cardboard to cover

projector stage
5.59
Petri dishes (see activity)
5.59
10 10-cm squares of
polarizing filters
Reagents for Chapter 5 Activities

Activity
Reagent
Total Quantity
5.1
Breathalyzer reagent
See activity
5.1
Acetone
See activity
5.1
Various alcohols
See activity
5.22
0.1 M potassium permanganate,

KmnO4
1.58 g per 100 mL

of H2O
5.22
Hexane
One drop
5.22
Hexene
One drop
5.22
Turpentine or pinene
One drop
5.41
Sodium metal, Na.
Small piece
5.41
Rock salt, sodium chloride, NaCl
Small crystal
5.59
Light corn syrup
See activity
ACS Chemistry FROG
Chapter 5
Section 5.1. Isomers

Learning Objectives for Section 5.1:
For a series of compounds, correlate patterns of chemical behavior with their Lewis structures
and molecular models and, based on these patterns, predict the behavior of other compounds.
Use appropriate molecular representations to show whether a pair of structures are unrelated
to one another, are identical to one another, are structural isomers, or are stereoisomers
(cis/trans and/or optical isomers).
Investigate This 5.1. How do different alcohols react in a Breathalyzer test?
Goal:
Students observe how different alcohols react in a Breathalyzer test.
Set-up time:
Ranged from 20-40 minutes (including preparation of the Breathalyzer reagent).
Time for activity:
Approximately 15-20 minutes (including follow-up discussion).
Materials:
Six small test tubes.
Plastic transfer pipets or glass droppers for the reagents.
Reagents:
SAFETY NOTES
Wear safety goggles
Wear protective plastic gloves when handling
Breathalyzer reagent
Sulfuric acid solutions are corrosive to skin and other
materials
Dichromate is a suspect carcinogen
Acetone and alcohols are flammable--no flames
Breathalyzer reagent is also known as Jones reagent. This preparation is adapted from The
Systemic Identification of Organic Compounds, 7th edition, R. L. Shriner, C. K. F. Hermann,

T. C. Morrill, D. L. Curtin, R. C. Fuson, (Wiley, New York, 1998). Other preparations of the
Jones reagent may use sodium or potassium dichromate, Na2Cr2O7 or K2Cr2O7. These
preparations work equally well. Place 25 g of chromic anhydride, CrO3, in 25 mL of
concentrated sulfuric acid. Pour the resulting solution, while stirring, into 75 mL of water.
Cool the orange-red solution to room temperature before use.
Acetone. Test the acetone with the Breathalyzer reagent to be sure it does not contain any
contaminants that would interfere with the alcohol reactions. It the acetone is contaminated,
add some potassium permanganate, KMnO4, and distill the acetone from this mixture.
Alcohols: ethanol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, and tert-butyl alcohol.
NOTE: Many different chromic acid formulations are used to test alcohols. Most call for rather
concentrated sulfuric acid solutions, but these are unnecessary, if waiting a few minutes to see
the results is OK. A solution that is about 0.004 M in dichromate (about 1.2 g/L of K2Cr2O7) in
2-3 M sulfuric acid will work. Addition of a tiny amount of silver ion (50-100 mg/L of AgNO3)
speeds up the reaction. Differences in the speed of reaction, as well as the lack of reaction with
the tertiary alcohol, might be noted with less acidic solutions.
ACS Chemistry FROG
Chapter 5
Procedure:
This activity is conducted as a class investigation with students working in small groups to
discuss and analyze the results. Due to the reagents involved, the instructor, wearing
appropriate protective apron/lab coat, gloves, and goggles should add the reagents to the test
tubes.
Record the appearance of the contents of the test tubes after the addition of each reagent.
Add about 1.0 mL of acetone to each of the six small test tubes.
Add 1 drop of the Breathalyzer reagent to each test tube.
Leave one of the test tubes as a control.
Add 1 drop or 1 tiny crystal of the following five compounds to separate test tubes containing
the reagent: ethanol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, and tert-butyl
alcohol.
Alternate Procedure:
This activity can be combined with Consider This 5.2 as a laboratory activity.
Anticipated Results:
The Breathalyzer reagent reacts with primary and secondary alcohols. It should react with
ethanol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, but not tert-butyl alcohol. A
blue-green color indicates a positive reaction and is due to the presence of the Cr3+.
The overall reaction can be represented as:
OH
3 R
O
H + Cr2O72 + 8H+
C
O
+ 2Cr3+ + 7H 2O
Pictures of the results are shown here:
Reagents before alcohol is added

Mixtures after alcohol is added
The order of alcohols from left to right is ethanol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, and control (no alcohol).
Clean-up:
Pour the six solutions together in a flask or beaker and add sodium bicarbonate, NaHOCO2, in
small amounts until all the acid has reacted (no more CO2 bubbles produced). Dispose of the
solution in an appropriate waste container consistent with your local ordinances. Perhaps you
can evaporate off the acetone and dispose of the tiny residue as solid heavy metal waste.
Follow-up activities:
Use Consider This 5.2 to initiate discussion of the results of this activity.
End of chapter problems 5.1 and 5.2.
ACS Chemistry FROG
Chapter 5
Consider This 5.2. Are all alcohols detected by the Breathalyzer test?
Goal:
Determine which alcohols are detected by the Breathalyzer reagent and speculate on why
some react and others dont.
Classroom options:
Allow 3-5 minutes for students, working in small groups, to interpret the data and answer the
questions. Then you can lead the discussion, summarizing answers on the chalkboard or an
overhead transparency or have the students do so.
This activity can be conducted as an open class discussion.
This activity could also be assigned as a homework problem and then discussed at the next
class session.
Time for activity:
Approximately 10 minutes.
Instructors notes:
Begin this activity by having the class agree on what was observed in Investigate This 5.1.
With the exception of ethanol, all of the other alcohols have the same molecular formulas, but
different structures.
Some instructors have students use their model kits to build models of the alcohols and then
discuss their structure and properties. Consider This 5.3 could be part of this extended
discussion. This is a way to begin to integrate the content and concepts from Sections 5.1 and
5.2.
Students should reason and conclude:
(a) The orange reagent solution to which a drop of ethanol was added turned a murky green,
indicating that ethanol reacts with the dichromate ion to produce the green chromic ion, Cr3+.
(b) The orange reagent solution also changed color to the murky green when n-butyl alcohol,
sec-butyl alcohol, and iso-butyl alcohol were added, so they also react with the dichromate
ion to produce the green chromic ion, Cr3+.
(c) The orange reagent solution did not change color when tert-butyl alcohol was added, so it
does not react with the Breathalyzer reagent.
(d) Although all the butyl alcohols have the same molecular formula, their structures must be
different or they would not have different names and properties (which we see in Table 5.1).
Because all the alcohols except the tert-butyl alcohol reacted with the Breathalyzer reagent,
the other structures, including ethanol, must have a feature that tert-butyl alcohol does not
have. [The reaction equation shown above with Investigate This 5.1, shows that the alcohols
that react have a hydrogen atom bonded to the alcohol carbon. t-butanol does not have a
hydrogen atom to be lost from this carbon.]
Consider This 5.3. How do the properties of the butyl alcohols isomers differ?
Check This 5.4. Comparison of C5H12 and C4H10O
Consider This 5.3. How do the properties of the butyl alcohol isomers differ?
Goal:
Based on observations from Investigate This 5.1 and the data presented in Table 5.1, discern
patterns in the properties of the butyl alcohols that differentiate tert-butyl alcohol from the
others.
8
ACS Chemistry FROG
Chapter 5
Classroom options:
Allow about 5 minutes for students, working in small groups, to answer the questions. Then
you can lead the discussion, summarizing answers on the chalkboard or an overhead
transparency, or have the students do so.
The discussion of this activity could be an extension of the discussion begun with Consider
This 5.1.
class session.
Instructor notes:
Show or refer students to Table 5.1 as this activity is carried out. If necessary, review and/or
display the results from Investigate This 5.1.
(a) The properties of three of the butyl alcohol isomers (n-butyl, sec-butyl, and iso-butyl) are
similar. The properties of tert-butyl alcohol are quite different from the other alcohols. The
melting points of the three similar isomers are all around 100 C, their boiling points are
around 100 C, and they have relatively limited solubility in water, about 10 g per 100 mL.
In contrast, tert-butyl alcohol has a melting point about room temperature, a boiling point
well below 100 C, and it is miscible with water.
(b) A striking property of ethanol and the three similar isomers is that their liquid range is
about 200C, while tert-butyl alcohol has a liquid range of only 57 C. Ethanol is a small
polar molecule, so its miscibility with water is not surprising. The butyl alcohols have
nonpolar parts that are likely to limit their solubility in water, as observed for the similar
isomers; the miscibility of tert-butyl alcohol is surprising. The larger butyl alcohols have
more electrons than ethanol and we expect their boiling points to be higher than ethanol
because they have greater attractive dispersion forces to overcome (as well as hydrogen
bonding). This expectation is borne out for the three similar isomers, but, once again,
tert-butyl alcohol is the surprising exception; its boiling point is only a few degrees higher
than for ethanol. The properties of the three similar isomers, relative to ethanol, make sense
in terms of the models of molecular interactions discussed in Chapter 1 and 2, but those of
tert-butyl alcohol do not seem to fit.
(c) If the results of the Breathalyzer test are added to Table 5.1, the results would fit the
patterns found in parts (a) and (b). Ethanol and the three similar isomers all react, but
tert-butyl alcohol does not, which fits the pattern that tert-butyl alcohol does not behave as
might be expected from the behavior of the other alcohols.
Follow-up discussion:
Discuss the comparisons between t-butyl alcohol and the other alcohols, especially the boiling
point and solubility in H2O, which are similar to ethanol, a lower molecular mass alcohol.
Review the differences in properties between ethanol and dimethyl ether from Table 1.2 in
Chapter 1, Section 1.11, page 48.
Show or refer students to Table 5.2 and point out that they can extend their analysis from this
discussion to Check This 5.4.
Check This 5.4. Comparison of C5H12 and C4H10O isomers
ACS Chemistry FROG
Chapter 5
Section 5.2. Lewis Structures and Molecular Models of Isomers

Write appropriate Lewis structures for molecules whose atomic composition you know,
including multiple Lewis structures representing possible isomers.
Build molecular models based on the connectivities shown in Lewis structures of the
molecules.
Consider This 5.10. What are the Lewis structures and molecular models for the C4H10O
isomeric alcohols?
Goal:
Students determine the Lewis structures and construct molecular models for the C4H10O
isomeric alcohols.
Classroom options:
This would be a long classroom activity, if some of it were not completed prior to classroom
discussion. For homework, assign students to complete both the Lewis structures and the
molecular models for the alcohols. The model kits have enough hydrogen atom centers (30) to
make three isomers, so it is probably better to suggest that groups of students work together,
each making perhaps two of the models. This provides some redundancy and a check on one
anothers work. Then, at the next class session, students can continue their work in small
groups or you can complete this activity as an open class discussion.
The activity could also be done, probably along with other modeling activities, as a laboratory
exercise.
Instructor notes:
Show or refer students to Table 5.1 as this activity is carried out.
You should make a set of molecular models for these isomers, preferably from a model kit
with larger components, so the models are relatively easy to see in the classroom. This makes
it easier for students to follow the discussion with their own models, if you wish to point out
particular features.
We are not pointing out that two different, nonsuperimposable structures (enantiomers) are
possible for 2-butanol. If your students notice this, congratulate them and indicate that we will
discuss this important form of isomerism in Section 5.9.
(a) Construction of the Lewis structures and molecular models are given here with their
names. The rationale for the assignment of names is in part (b).
[1-butanol] Begin by connecting the carbon atoms to form the longest possible chain with the
OH group at one end:
10
H
O
ACS Chemistry FROG
Chapter 5
[2-butanol] Construct the Lewis structure for a second isomer by moving the OH group to
one of the middle carbons:
H
H
The structure of the enantiomer of 2-butanol is:
[2-methyl-1-propanol] Construct a three-carbon atom chain and bond the fourth carbon atom
to the middle carbon atom of the chain with the OH group bonded to one of the end
carbons:
H H
H
H C H
H
H
O
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Chapter 5
[2-methyl-2-propanol] In the previous structure, move the OH group to the second carbon
atom to form a fourth isomer:
H H
H
H C H
H
H
H
(b) The names are listed above. The base name for an alcohol with a four-carbon chain is
butanol (derived from butane--see marginal table on page 282 of the text). If the OH group
is bonded to an end carbon of the chain, it makes sense call this 1-butanol, because the OH
is at the first position on the chain. When the OH group is bonded to the second carbon of
the chain, the name 2-butanol makes sense. When we go to a three-carbon chain, the base
name of the alcohol is propanol. Now we have to name the fourth carbon (and its associated
hydrogen atoms) bonded to the middle carbon of the chain. This one-carbon group is named
methyl and, because it is bonded to the second carbon in the chain, it is 2-methyl. The
position of the OH group on the three-carbon chain is designated in the same way it was for
the four-carbon chain, so our names are 2-methyl-1-propanol when the OH is attached at the
end of three-carbon chain and 2-methyl-2-propanol when the OH is bonded to the second
carbon in the chain.
(c) The 2-methyl-2-propanol (or tert-butyl alcohol) structure is very compact, almost
spherical, instead of a chain. You can almost see this compactness in the Lewis structure.
These compact, almost spherical molecules pack more efficiently in the solid and also have
less surface area exposed to their neighbors, so the nonpolar attractive dispersion forces
between them are not as strong as in the elongated chain-like structures. The low boiling
point due to this compactness is the subject of Check This 5.11. The high freezing point is a
result of the packing of the spherical molecules and the relatively low energy required to go
from solid to liquid (because of the low attractive forces among the molecules). [In terms of
entropy arguments that we will meet in Chapter 8, the positional entropy change is smaller
going from solid to liquid for the almost spherical molecules with little attraction for one
another compared to the more elongated isomers. Consequently, the thermal entropy change
for the process is also relatively small. The thermal entropy change is the energy (enthalpy)
input required for the melting divided by the melting temperature. To make the thermal
entropy change low, the temperature is higher than for the other isomers, which helps to
explain the high melting temperature of 2-methyl-2-propanol compared to its isomeric
alcohols.]
(d) Since vitamin A has its alcohol group at the end of its carbon chain similar to ethanol and
1-butanol, we would predict that if vitamin A was mixed with chromic acid, the resulting
reaction would be positive and the solution would turn blue-green. The similarity or retinol to
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Chapter 5
retinal is the long chain of carbons with a ring at one end and an oxygen atom at the other.
Double bonds are introduced later in the chapter.
NOTE: The objective here is not to have the students understand the structure of retinol at this
point, but to see that it contains an alcohol group that is like the one in 1-butanol and therefore
to predict that it will undergo similar reaction. One of the aims of the chapter is to have students
begin to recognize functional groups and this is a beginning toward that end. This item is part of
a Consider This so that it is likely to be part of a class discussion that can be led beyond the
complexity of the structure to see the simple alcohol group.
Reiterate the point in the Reflection and Projection on page 290 that the Lewis model is a
simple and useful model that describes connectivity without taking more complex electron
wave models into consideration.
Check This 5.11. Boiling points of the C4H10O alcohols.
End of chapter problem 5.1 through 5.9.
Section 5.3. Sigma molecular orbitals

Describe the similarities and differences between the formation and energetics of atomic and
molecular orbitals.
Draw and/or describe and n orbitals for simple molecules containing elemental atoms from
periods one, two, and three.
Predict molecular geometries for molecules containing and/or n orbitals.
Consider This 5.12. How do the PEs and KE vary with the proton-proton distance?
Goal:
Using the animation in the Web Companion, Chapter 5, Sect 5.3, page 1, determine the effect of
change in proton-proton distance on the potential and kinetic energies of the one-electron-twoproton system.
Classroom options:
This activity can be done in the classroom, in about 10 minutes, if you have facilities for
projecting the Web Companion. Have a student group control the dragging of the proton with
input from the other student groups. Then you can lead the discussion as the questions are
answered and discussed.
If you dont have facilities for using the Companion in class, this activity can be assigned as a
homework problem, but it is essential that the results are discussed in class to reinforce the
ideas in the animation and shown in the static Figure 5.3.
Instructor notes:
(a) The potential energy of attraction between proton A and the electron PEA becomes more
negative (more stable) as the protons are brought closer together.
(b) The potential energy of attraction between proton B and the electron PEB becomes more
negative (more stable) as the protons are brought closer together.
(c) The two protons repel each other, so the potential energy becomes more positive (less
stable) as the protons are brought closer together.
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Chapter 5
(d) The kinetic energy of the electron wave increases because the wave becomes more
constrained (smaller) as the protons move closer together.
The discussion should lead on to Figure 5.4, which is also shown in the Web Companion,
Chapter 5, Section 5.3, page 2.
The activity and discussion is designed to introduce molecular orbitals.
Check This 5.13. Potential and kinetic energy combinations.
End of chapter problems 5.10 through 5.17.
Consider This 5.14. What are the relative sizes of atomic and molecular orbitals?
Goal:
Students discuss the relative sizes of atomic and molecular orbitals.
Classroom options:
Allow 3-5 minutes for students, working in small groups, to complete this activity. Then you
can lead the discussion, summarizing their answers on the chalkboard or an overhead
transparency, or have the students do so.
Time for activity:
Instructor notes:
Show or refer students to Figure 5.4 and, if possible, display the Web Companion, Chapter 5,
Sect 5.3, page 1. Draw attention to the distance between the electron and the protons as the
protons are brought closer in the animation. Point out that this effect is also represented by the
decreasing size of the electron wave.
Show or refer students to Figure 5.5 and introduce sigma bonding, , molecular orbitals.
(a) The kinetic energy of an orbital (electron wave) increases as it is constrained to occupy a
smaller volume. Therefore, the sigma bonding molecular orbital has the higher (less
favorable) kinetic energy.
(b) In a molecular orbital, the electron is attracted by two positive density is constrained
between the two atomic cores, making it more stable than an individual atomic orbital.
Discuss how bonding orbitals form the strongest bonds because they are the most favorable
arrangement for coulombic attraction between the electron orbital and the nuclei.
Show or refer to students to Figure 5.6 as part of the discussion of the overall energetics of
bonding in molecules.
Lead into a discussion of nonbonding molecular orbitals.
Consider This 5.14. What are the characteristics of n orbitals?
Consider This 5.15. What is the symmetry of n orbitals??
Goal:
Define the symmetry axis of n orbitals so it is consistent with the cylindrical symmetry of
orbitals.
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Classroom options:
Allow about 3 minutes for students, working in small groups, to complete their responses.
Then you can lead the discussion, summarizing their descriptions on the chalkboard or an
overhead transparency, or have the students do so.
Time for activity:
Less than 10 minutes.
Instructor notes:
Show or refer students to Figure 5.9 as this activity is done and they discuss the differences
between bonding and nonbonding orbitals.
The axis of symmetry for a n orbital is an imaginary line passing through the nucleus to
which the orbital is attracted and through the region of highest electron density of the orbital.
If you look down this axis and rotate the orbital about the axis, the orbital will appear exactly
the same no matter how far you rotate it. This is what we mean by cylindrical symmetry.
Note that a orbital is smaller than a n orbital on the same atom. This is because two
atomic cores attract the orbital electrons, while only one attracts the n orbital electrons.
Section 5.4. Sigma Molecular Orbitals and Molecular Geometry

Draw and/or describe the and n orbitals for simple molecules containing elemental atoms
from periods one, two, and three.
Draw and/or describe the sigma framework of a molecule and predict the shape of the
molecule.
Consider This 5.16. What are the geometries of second period hydrides?
Goal:
Using both Lewis structures and molecular models, students determine the geometries of second
period hydrides.
NOTE: This activity combines aspects of both the Investigate This (manipulation of materials)
and Consider This (conceptual questions) features. In this case (and several others), the
distinction makes little difference pedagogically, since both features are designed to drive and
stimulate instructor-student and student-student interactions in the classroom.
Set-Up Time:
5 minutes to make lecture-size molecular models of methane, ammonia, and water.
Time for Activity:
10 minutes, if students bring the models to class and previously complete the corresponding
Lewis structures. Students can discuss their answers while working in small groups and then
can discuss their conclusions with the entire class. Otherwise, this activity will take
approximately 15-20 minutes.
Equipment:
Molecular modeling kits.
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Procedure:
(a) Compounds of second period elements with hydrogen are often called hydrides. Write Lewis
structures for the hydrides of carbon (CH4), nitrogen (NH3), and oxygen (H2O).
(b) Make molecular models of the hydrides in part (a). Use the paddles in your model kit to
represent any nonbonding electrons in the Lewis structures. How would you describe the
geometry (shape) of the electron pairs around the second period atom center in each of your
models? Explain your responses.
(c) How would you describe the geometry of the atom centers with respect to one another in the
model of each molecule? Explain your responses.
Alternative Procedure:
Some instructors have students use CAChe software to construct models and measure the
bond angles for ideal tetrahedral geometry.
Then they do a geometry optimization calculation (MM-AM1) and remeasure the bond angle
to discover that the bond angle in molecules with nonbonding pairs of electrons is slightly
compressed.
(a) Lewis structures for the three hydrides will probably look something like this. The oxygen
hydride, water, structure might be shown bent, since we have made a big point of the bent
structure in the first two chapters.
H
H
(b) carbon hydride (methane)
nitrogen hydride (ammonia)
oxygen hydride (water)
The geometry of the electron pairs around the second period atom in each model is tetrahedral.
Each second period atom has four pairs of electrons that give a total of four sigma molecular
orbitals, both bonding and nonbonding. The most stable arrangement of these four pairs of
electrons around these atom cores is the tetrahedral arrangement.
(c) The atom centers in CH4 are usually described as having a tetrahedral geometry of four H
atom centers arranged around the central C atom. The four atom centers in NH3 are usually
described as having trigonal pyramidal geometry with the N atom center at the apex of a
triangular pyramid with the H atom centers at the corners of the base of the pyramid. The three
atom centers in H2O are described as having a bent geometry with the O atom at the center of the
angular structure.
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(d) The answers to parts (b) and (c) are not the same, because the nonbonding electrons are taken
into account in describing the orientation of the electron pairs but not in describing the molecular
geometry. See Figure 5.10.
Show or refer students to Figure 5.10 during the discussion of their answers.
Discuss the bonding framework, pointing out that the number of bonding orbitals plus the
number of nonbonding orbitals always adds up to four for the second-row elements C, N, O,
and F in their molecules. Relate this to the octet rule that was introduced as an empirical rule
in Chapter 1, Section 1.4, and that we have been using ever since to help construct Lewis
structures.
Reiterate the distinction between molecular shape and the arrangement of orbitals.
Check This 5.17. A fourth combination of sigma orbitals.
Worked Example 5.18. The structures of PF3 and PF5.
End of chapter problem 5.18 through 5.22.
Consider This 5.20. How are all six octahedral positions equivalent?
Goal:
Show how all six balls in an octahedral array of balls are at equivalent positions.
Classroom options:
Allow about 5 minutes for students, working in small groups, to complete this activity.
Provide each group with six Styrofoam balls and toothpicks. Then you can lead the
discussion, summarizing their structures on the chalkboard or an overhead transparency, or
have the students do so.
Have two student volunteers construct the octahedral array of balls and then discuss the
questions with the entire class.
Time for activity:
From 10 minutes to more than 20 minutes, depending upon how much you want to go into the
octahedral geometry and the difference between second and third period elements in their
ability to accommodate more than four sigma orbitals.
Instructor notes:
Show or refer students to Figure 5.12(b), which shows an octahedral array of six balls for
students to compare with the one they constructed. To construct the octahedral array, use
toothpicks that have been cut or broken in half.
Show a ball-and-stick model of a molecule with a regular octahedral array of identical balls
around a central ball (or have students use their SF6 model from Check This 5.19) as part of
the discussion of the equivalence of all six positions about the central atomic core. Some
students see the equivalence better with the ball-and-stick and others with the array.
(a) Another view of an octahedral array of balls is shown here to compare with Figure
5.12(b).
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(b) The octahedral array of balls is the same as the arrangement of bonding orbitals (sticks
representing the bonding electron pairs) in the SF6 model in Check This 5.19. The octahedral
array of Styrofoam balls puts them all at the same distance from the central point of the
array. This is the most efficient packing of six spheres and represents the closest approach
that six sigma orbitals can make to a central atomic core. This is the most stable arrangement
for the six bonding electron pairs.
Discuss the energetic reasons why the second period atoms do not accommodate more than
four orbitals while third period atoms can accommodate more than four orbitals.
Summarize the points in the "Reflection and Projection" section.
Check This 5.21. Sigma orbitals around third and higher period atoms in molecules.
Section 5.5. Multiple Bonds

Write appropriate Lewis structures for molecules whose atomic composition you know,
including multiple Lewis structures representing possible isomers.
molecules.
Use Lewis structures to predict multiple bonding in the molecules of a compound.
Investigate This 5.22. Do carbon-hydrogen compounds react with permanganate?
Goal:
Determine which carbon-hydrogen compounds react with permanganate.
Set-up time:
Ranges from 10 minutes to longer than 20 minutes, depending upon whether the KMnO4(aq)
reagent solution is readily available.
Time for activity:
Ranges from less than 10 minutes to 20 minutes, depending on the depth of the discussion you
wish to have as a lead in to multiple bonding.
Materials:
Small test tubes.
Plastic or glass pipets/droppers.
Reagents:
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0.1M potassium permanganate solutions, KMnO4(aq). Dissolve 1.58 g of KMnO4(s) in 100
mL of water.
NOTE: This is the Baeyer Test for unsaturation in hydrocarbons. The beautiful reddish purple
color of the permanganate ion turns a muddy brown as MnO2 is formed by reduction of the
permanganate by the double bonds.
Ethanol (about 6 mL of 95%)
Hexane (a drop).
Hexene (a drop).
Turpentine or pinene (a drop).
NOTE: Turpentine is a mixture. Its predominant component is pinene, which is responsible
for its "pine" odor. Any available liquid alkane and alkene can be used in place of hexane and
hexene, respectively, for this test.
Limonene (optional). Probably twisting or pressing a bit of lemon peel in a few milliliters of
ethanol and removing the peel will produce a solution that will give a positive test.
SAFETY NOTES
Wear safety goggles
Ethanol, hexane, hexene, and turpentine are flammable-no flames and good ventilation
Procedure:
NOTE: This is a class activity that can be carried out by student volunteers while the class
observes and discusses the results in small groups.
Dissolve one drop of each sample in 2 ml of 95% ethanol in small test tubes.
Add one drop of 0.1M KMnO4 to each test tube.
The reaction should be instantaneous.
Alternative suggestions:
Use one tube as a control with just ethanol and KMnO4 in it.
Anticipated results:
Pictured from left to right in this photograph are the results of the test on hexane, hexene,
pinene, limonene, blank
Clean-up:
Dispose of solutions in properly labeled waste containers in accord with local ordinances.
Use Consider This 5.23 to initiate discussion of this activity.
Introduce and discuss the properties of double bonds.
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Worked Example 5.24. The Lewis structure and molecular model for ethene.
(formaldehyde)?
Consider This 5.26. What are the structures and reactivity of C6H14 and C6H12?
Consider This 5.27. What is the geometry of double bonded molecules?
Check This 5.28. Other bond angles in ethene and methanal.
Consider This 5.23. What compounds react with permanganate?
Goal:
Try to find similarities among the compounds that reacted with permanganate in Investigate
This 5.22.
Classroom options:
This activity can be conducted as an open class discussion in connection with the
investigation.
Time for activity:
Approximately 10-15 minutes.
Instructor notes:
Make sure there is class agreement on the observations from Investigate This 5.22.
(a) Yes, the permanganate reacted with all the samples except for hexane. The evidence was
the appearance of brown precipitate and the disappearance of the purple permanganate color.
(b) Not all the samples reacted. The names of the compounds that reacted all ended in "ene".
Worked Example 5.24. The Lewis structure and molecular model for ethene.
(formaldehyde)?
(formaldehyde)?
Goal:
Write the Lewis structure and construct the molecular model for methanal.
Classroom options:
Have students work for 3-5 minutes in small groups writing the Lewis structure and
constructing their models and then have groups share their results with the class.
For homework, assign students to complete both the Lewis structure and the molecular model
for the methanal. Make a classroom molecular model for class demonstration. Then, at the
next class session, you can complete this activity as an open class discussion.
Instructor notes:
Discuss Worked Example 5.24, which introduces the way multiple bonds are formulated in
Lewis structures, before completing this activity.
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H
C
(a) The Lewis structure for methanal is:

The Lewis structure for methanal is different than ethene because one carbon atom of ethene
is replaced in methanal with an oxygen atom (and two nonbonding sigma molecular orbitals
in place of two hydrogen atoms). Both atoms are second period atomic cores. Both molecules
contain two pairs of bonding electrons between their second period atomic cores.
(b) A molecular model for methanal that represents the nonbonding as well as bonding
electron pairs is:
H
In patterning this model after Figure 5.13, one oxygen atom replaced a carbon atom and two
paddles, each representing a pair of nonbonding electrons, replaced the hydrogen atoms that
were bonded to the replaced carbon atom. [It is not incorrect at this point to omit the paddles
in the molecular models, but they do help to understand the geometry discussed later in the
section.
Discuss the bent bond representation of double bonds with a stress on the idea that this is a
model that retains the octet rule for these second period elements.
Check This 5.28. Other bond angles in ethene and methanol.
Goal:
Writing Lewis structures and construct molecular models of the straight chain C6H14 and C6H12
isomers and correlate the structures with the reactivities of these molecules and others
containing double bonds.
Classroom options:
To save class time, you could assign students to complete both the Lewis structures and the
molecular models for C6H14 and C6H12 before coming to class. They probably should work in
groups because there are only sufficient hydrogen atom centers (30) to construct two of these
molecules or isomers. Make a set of classroom size molecular models of the molecules or
isomers for class demonstration. Then, at the next class session, students can work in small
groups to answer the questions or you can complete this activity as an open class discussion.
Time for activity:
Ranges from 10-15 minutes to more than 20 minutes, depending on the depth to which your
want to take the discussion of the isomers and the reactivity of the double bond.
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Instructor notes:
Keep students focused on constructing straight chain isomers with no branches. In this case,
there is one isomer for C6H14 and three isomers for C6H12. Two of the C6H12 isomers have cistrans isomers (for a total of five isomers), but dont dwell on this observation at this time. If
students observe and ask about this, briefly explain why there are two isomers and note that
this is a topic that is taken up in Section 5.9. If branching is included, there are more isomers
of both C6H14 and C6H12.
(a) The Lewis structures for six-carbon-chain C6H14 and C6H12 isomers are:
H
H
H
H
C
Although there is only one way to write a Lewis structure for C6H14 with all the carbons
connected in a chain, there are three ways to write a Lewis structure for C6H12 with the
carbon atoms connected in a chain, because there are three different positions along the chain
where the double bond can go. All three isomers have a double bond.
NOTE: From left to right, the C6H12 isomers are named 1-hexene, 2-hexene, and 3-hexene.
Think about why they have these names.
(b) Photographs of molecular models for these molecules are shown here.
hexane
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1-hexene:
2-hexene (cis and trans):
3-hexene (cis and trans):
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Chapter 5
The C6H12 isomers contain double bonds (represented by the pair of curved blue connectors
in each of the models. The representation makes it look like the electrons in double bonds are
more exposed to the surroundings than those in sigma bonds and perhaps more reactive.
Hexene reacted with permanganate ion, but hexane did not. We postulate that compounds
containing double bonds are more reactive than compounds containing all sigma bonds.
(c) If the postulate we made in part (b) is correct, then it is likely that pinene contains a
double bond because it reacted with the permanganate ion.
(d) If the postulate we made in part (b) is correct and, since retinol contains several double
bonds, it will probably react with the permanganate ion.
NOTE: Focus again on the parts of the retinol molecule, the double bonds, that are similar to the
other alkenes investigated. These are the basis of the prediction that retinol will react like a
molecule with double bonds. Now that the students have seen a few more molecules, they may
be more comfortable with the larger structure, even though not understanding it completely.
Reiterate that compounds containing carbon-carbon double bonds react with permanganate.
Stress that the electron density in double bonds is not all concentrated between atomic cores
as observed in sigma bonds. This means that these electrons in the double bonds can better
interact with other molecules than can electrons in sigma bonds.
End of chapter problem 5.25.
Goal:
Compare the geometry of molecular models for double-bonded molecules with their
experimental geometry and try to explain the geometries based on our bonding model.
Classroom options:
Allow about 5 minutes for students, working in small groups, to build the models and work on
the questions. Then you can lead the discussion, showing the models and summarizing
answers on the chalkboard or an overhead transparency, or have the students do so.
This activity can be conducted as an open class discussion, if you have constructed classroomsize molecular models of ethane, ethene, and methanal.
Together with several other of the molecular model building activities in this chapter, this
activity could be done as part or all of a laboratory experiment in model building and
interpretation.
Time for activity:
Approximately 10-15 minutes, depending on he depth you wish to go in interpreting the
patterns in bond lengths and angles for different molecular bonding.
Instructor notes:
Students need to examine molecular models of ethane, ethene, and methanal. These can be
either ones they have constructed or a classroom set you have made.
Students should reason and conclude that:
(a) All the atomic centers in both ethene and methanal lie in a plane. This is shown also in
Figure 5.14.
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(b) The bond angles are approximately 109 because the models were made from tetrahedral
atom centers. Experimentally, the bond angles are closer to 120, as shown in Figure 5.14.
(c) The carbon atom centers are further apart in a molecular model of ethane (using a white
connector between the carbon atom centers) than in a model of ethene made with the curved
blue connectors. This is consistent with the experimental data. Perhaps, because there are
more bonding electrons in the double bond, compared to the single bond, the atomic cores
are held more tightly and the increased attraction by the larger number of electrons draws the
nuclei closer together.
(d) An oxygen atomic core has a higher charge than the carbon atomic core, so the attraction
felt by the bonding electrons is larger. The bonding orbital between the cores is smaller so
the atomic cores are brought closer together in a CO bond compared to a CC bond. The
double bond in methanal, like the double bond in ethene, is shorter than the corresponding
single bond. The explanation in part (c) would be valid in this case as well. Note that the C
O double bond is shorter than a CC double bond, presumably for the same reason that the
CO single bond is shorter than a CC single bond.
Discuss the planar geometry of doubly bonded atoms, as found in these two examples, and go
on to the geometry of triply bonded atoms.
Check This 5.28. Other bond angles of ethene and methanol.
End of chapter problem 5.25.
Section 5.6. Pi Molecular Orbitals

Describe the formation of pi bonding molecular orbitals in terms of wave reinforcement.
Explain in words or with drawings how both lobes of a pi bonding orbital are parts of the
same electron wave.
Draw and/or describe the , n, and orbitals for simple molecules containing elemental
atoms from periods one, two, and three.
Draw and/or describe the sigma framework of a molecule containing both sigma and pi bonds
and predict the shape of the molecule.
Section 5.7. Delocalized orbitals

Draw and/or describe the , n, and localized and delocalized orbitals for simple molecules
containing elemental atoms from periods one, two, and three.
Use Lewis structures to predict whether a molecule is likely to have delocalized orbitals and
sketch what they might look like.
Consider This 5.37. Do Lewis structures give correct geometries for CO32 and NO3?
Goal:
Determine if Lewis structures predict the correct geometries for CO32 and NO3.
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Chapter 5
Classroom options:
can lead the discussion, summarizing answers on the chalkboard or an overhead transparency,
or have the students do so.
class session.
This activity could be conducted as an open class discussion.
Time for activity:
From 5 to 20 minutes, depending on how well students interpret the Lewis structures in terms
of the sigma frameworks introduced in the previous sections.
Instructor notes:
Show or refer students to the sigma orbital geometries in Table 5.3, and review the Lewis
structures from Worked Example 5.35 and Check This 5.36 as this activity is carried out.
For both ions, all the Lewis structures show two single and one double bond about the central
atom center. In the sigma-pi model derived from these Lewis structures, there are three sigma
orbitals (and a pi orbital) on the central atom center, which predicts the correct planar
geometry. What is not predicted, as was commented on in Worked Example 5.35, is the
equivalence of the three oxygen atoms in each ion.
Discuss delocalized molecular orbitals.
Introduce and discuss bond order.
Consider This 5.38. What are the bonding and structure of the CO2 molecule?
Check This 5.39. Bond order in carbon dioxide.
Check This 5.40. Structure of the cyanate ion and the ozone molecule.
Consider This 5.38. What are the bonding and structure of the CO2 molecule?
Goal:
From the Lewis structure and our sigma-pi bonding model predict the geometry of the CO2
molecule and build a molecular model to test the prediction.
Classroom options:
Allow about 5 minutes for students, working in small groups, to complete this activity. Then
you can lead the discussion, showing the molecular models and summarizing answers on the
chalkboard or an overhead transparency, or have the students do so.
Instructor notes:
Bring a classroom-size molecular model of CO2 to class.
O
(a) The Lewis structure of CO2 is:

(b) In the sigma-pi structure derived from this Lewis structure, there are two orbitals on the
carbon atom, which predicts linear geometry about the carbon atom.
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(c) A molecular model based on the Lewis structure, with paddles used to represent the
nonbonding electrons is:
The molecular model confirms the linear geometry predicted in part (b).
Discuss the framework and delocalized molecular orbitals in the CO2 molecule.
Lead into discussing why molecules with delocalized orbitals have a lower total energy
than a molecule with localized orbitals.
Check This 5.39. Bond order in carbon dioxide.
Check This 5.40. Structure of the cyanate ion and the ozone molecule.
Investigate This 5.41. What happens when substances are cut?
Goal:
Discover the great difference between cutting a piece of Na(s) and a rock salt crystal, NaCl(s).
Set-up time:
Time for activity:
Materials:
Shallow dish.
Sharp knife.
Small hammer.
Reagents:
Small piece of sodium metal, Na(s), large enough to be easy to see being cut.
A crystal of rock salt, sodium chloride, NaCl(s), large enough to see as you try cutting it.
SAFETY NOTES
Wear safety goggles
Sodium metal can cause severe burns by reacting with the
moisture on your skin--handle with metal tongs
NOTE: For this activity, use about a one cubic centimeter piece of sodium metal. To minimize
any hazard in the classroom, prepare this beforehand and bring it to class in a small screwcapped glass container filled with enough mineral oil to cover the sodium and protect it from air
and water. If handled with tongs and kept away from water, the metal is safe in air. (It does not
spontaneously ignite.) In a large class, a video camera and some form of projection should be
used to show what happens when the metal is cut. When the student volunteer cuts it, s/he can
report the small amount of effort required and everyone can observe that the piece of metal is
ACS Chemistry FROG
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Chapter 5
cut cleanly in two. Be sure to focus on the shiny surfaces of the freshly exposed metal, as they
will be mentioned later in the text. As soon as all observations are complete, return the metal
pieces to the container with mineral oil. For the rock salt activity, choose a large enough piece
to be easily visible with the camera and again have the student volunteer report the amount of
effort required to cut the crystal, which will probably shatter into several pieces.
Procedure:
Do this activity as a class investigation and work in small groups to discuss and analyze the
results.
Place a small piece of sodium metal in a shallow dish and try cutting it in two with a sharp
knife. Record the observations, including the ease of cutting, and then return the pieces of
sodium to their storage container.
Place a crystal of rock salt, sodium chloride, in a shallow dish and try cutting it in two with a
sharp knife. Record the observations, including the ease of cutting.
NOTE: Cutting this crystal may be impossible without the use of a great deal of force that will
cause it to shatter. Take care not to break the dish. You may have to use a hammer to smash the
crystal.
Anticipated results:.
These are photos of a piece of sodium metal before cutting and after cutting in two and then
each piece in two again.
These are photos of pieces of rock salt before attempting to cut with a knife and after hitting
with a hammer when that proved futile. The hammer shattered the crystals into smaller pieces.
Clean-up:
Return the sodium metal pieces to the container with mineral oil. Dispose of the rock salt,
according to local ordinances.
Use this activity as a lead in to a discussion of Figure 5.26 and how the model represented by
the figure helps to explain the results for the sodium metal.
Check This 5.43. Three-dimensional packing of spheres.
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Check This 5.44. More properties of metals.

Consider This 5.42. What substances can be cut in two?

Goal:
Consider what molecular level model might explain the difference between the ease of cutting a
metal compared to the difficulty of cutting a crystal.
Classroom options:
Instructor notes:
Be sure the class agrees on the observations from Investigate This 5.41 as you begin this
activity.
Show or refer students to Figure 5.26. Use this activity to lead in to a discussion of metallic
bonding and delocalized molecular orbitals in metals.
(a) Sodium metal was easy to cut. It sliced nicely with a knife. A knife would not cut
NaCl(s). Instead, a hammer shattered the big crystals into many smaller pieces.
(b) The sodium atoms in the metal pack closely together, but there are no highly directional
interactions among the atoms, as there are among the ions in a crystal. The salt crystal has
strong coulombic attractions between the positively charged sodium ions and the negatively
charged chloride ions. These interactions tightly hold the ions together resulting in a lot of
effort to cut the crystal. The sodium atoms sort of slide apart as the sharp edge of the knife
pushes them aside.
Check This 5.43. Three-dimensional packing of spheres.
Check This 5.44. More properties of metals.
Section 5.8. Representations of Molecular Geometry

molecules.
Beginning with any one of the following representations of relatively simple molecules, write,
draw, or build all the other representations: condensed formula, Lewis structure, 3-d structure,
condensed structure, skeletal structure, molecular model.
Consider This 5.47. How do you draw 3-D structures for larger molecules?
Goal:
Draw 3-D structures for three- and four-carbon molecules to visualize their geometries and
discover the difficulty of drawing these structures for even modest size molecules.
Classroom options:
Allow about 5 minutes for students, working in small groups, to complete this activity. Then
have the groups share their drawings and models with the class.
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Chapter 5
This activity could also be assigned as a homework problem (to draw the Lewis and 3-D and
build the molecular models) and then discussed at the next class session, either in small
groups initially or open class discussion.
Time for activity:
From 10 to 20 minutes, depending on how adept the students have become at visualizing the
structures in three dimensions.
Instructor notes:
Before discussing this activity, make your own models to help guide students in answering the
questions, if they need help.
(a) The Lewis structure and 3-D drawing for propene are:
H
H
H
C
C
H
All the carbons in the molecule must lie in a plane. (They must lie in a plane because three
points not in a straight line define a plane.) Notice that three of the six hydrogen atoms also
must lie in the plane because they are part of the trigonal planar geometry about the carbon
atoms at the ends of the double bond. A fourth hydrogen atom may lie in the plane, as shown,
if the methyl group, CH3, is rotated into the appropriate orientation with respect to the rest
of the molecule. Either of the other two hydrogen atoms could lie in the plane if the methyl
group is rotated 60 into or out of the plane of the paper. The hydrogen atom that lies in the
plane does not have to be down, as drawn, but could be up at an angle complementary to the
CC bond on the carbon atom. Draw this 3-D structure.
(b) The Lewis structure and two 3-D drawings for 1-butene are:
H
H
H
H
C
H
C
C
H
H
All the carbons in the molecule can lie in a plane. There are two ways for them to lie in a
plane. In the first 3-D drawing, the carbons are stretched out to be in as straight a line as
possible. In the second drawing, the third carbon is rotated 180 so that the fourth carbon is
up and the carbon chain is curled back on itself instead of straight. Prove for yourself that
these are the only two ways for all the carbons to lie in a plane. Again, as with propene, three
of the hydrogen atoms must lie in the plane and other can also lie in the plane, if the methyl
group is appropriately rotated.
Use the discussion of these structures as a lead in to condensed structures as a shorthand to
represent complex structures.
Worked Example 5.48. 3-D and condensed structures for 2-propanol.
Check This 5.49. 3-D and condensed structures for the C5H12 isomers.
Consider This 5.50. How many hydrogen atoms are bonded to a carbon?
Check This 5.52. Skeletal structures for the C5H12 isomers.
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Consider This 5.53. Can different skeletal structures represent the same molecule?
Check This 5.54. Interpreting skeletal representations.
End of chapter problems 5.37, 5.41, and 5.42.
Consider This 5.50. How many hydrogen atoms are bonded to a carbon?
Goal:
Conclude that enough Hs are bonded to C to give four bonds to carbon in essentially all carboncontaining molecules.
Classroom options:
Allow about 3 minutes for students working in small groups to answer these questions and
then share their conclusions with the class.
This activity could be assigned as a homework problem and then discussed at the next class
session.
Time for activity:
About 510 minutes.
Instructor notes:
Use this activity to introduce and discuss skeletal structures.
Carbon atoms do not have nonbonding electrons.
If necessary, sufficient H atoms are bonded to each carbon atom in a molecule to give it
four and bonding orbitals. Or stated another way, if the carbon atoms are bonded to nonhydrogen atoms, the remaining bonds that make up four bonding orbitals will be with
hydrogen atoms.
Check This 5.52. Skeletal structures for the C5H12 isomers.
Goal:
Identify different skeletal structures that represent the same molecule.
Classroom options:
This activity could be assigned as a homework problem (to make the molecular models and
skeletal structure) and then discussed at the next class session, either in small groups initially
or open class discussion.
And again, this activity, perhaps together with others in the chapter can be done in the
laboratory.
Time for activity:
From 15 to longer than 20 minutes, depending on whether you want to use this activity (as
well as Check This 5.52 and 5.54 as a way of assessing your students understanding of
molecular geometry and its representations.
Instructor notes:
Before discussing this activity, make your own models to guide students in completing this
activity, if necessary.
Computerized molecular graphics can be used as well, as an alternative for this activity.
ACS Chemistry FROG
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Chapter 5
(a) The structures shown for 1-butanol in this activity and in Figure 5.32 can be
interconverted.
(b) Different skeletal structures for two of the three C5H12 isomers, pentane and
2-methylbutane, can be made by rotating one part of the molecule with respect to another
(that is, by rotating about CC bonds). Here are just two possibilities for each isomer:
Only one skeletal structure is possible for 2,2-dimethylpropane because rotation about any of
the CC bonds leaves all five carbons in exactly the same relationship to one another.
Use the discussion to help summarize the points in the Reflection and Projection section.
Section 5.9. Stereoisomerism

molecules.
Use appropriate molecular representations to show whether a pair of structures are unrelated
to one another, are identical to one another, are structural isomers, or are stereoisomers
(cis/trans and/or optical isomers).
Use appropriate molecular representations to show whether structural isomers and/or
stereoisomers (cis/trans and/or optical isomers) are possible for a given molecular formula.
Investigate This 5.55. How many C4H8 molecular structures are possible?
Goal:
Construct molecular models and draw their corresponding skeletal structures to determine how
many C4H8 isomers are possible.
Set-up time:
5-10 minutes to make classroom-size molecular models.
Time for activity:
From 15 minutes to longer than 30 minutes, depending on the amount of discussion you want
students to have about how to tell whether structures are isomers or identical and whether all
isomers have been found. These are important discussions to have.
Materials:
Molecular model kits.
32
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Procedure:
For part (a), have student groups construct molecular models of as many isomers as they can
find.
For part (b), students should draw skeletal structures for the isomers whose models they have
made. Then the groups can share their models and skeletal structures with the class and the
class can come to a consensus about the number of isomers and their structures.
To save some class time, it might be useful to assign this activity as a homework assignment
(in groups) and then have students bring their models and skeletal structures to class for
discussion.
Could be conducted as a molecular modeling mini-lab, if software is available.
(a) Models of some of the isomers are a little difficult to make because the bond angles in the
rings are more acute than the atom centers are designed for. Students might use the longer
connectors for the CC bonds in these rings to make bending them a bit easier. The names of
the isomers are given here with the structures for reference, but students are not expected to
name them.
cyclobutane
2-methylpropene
methylcyclopropane
1-butene
trans-2-butene
cis-2-butene
(b) The skeletal structures corresponding to the models for the six C4H8 isomers in part (a)
are:
ACS Chemistry FROG
33
Chapter 5
Check This 5.57. Cis-trans isomers.
Check This 5.58. Identifying isomers.
End of chapter problems 5.34, 5.43, and 5.45.
Consider This 5.56. What are the line (condensed) formulas for the C4H8 isomers?
Goal:
Write line formulas for the C4H8 isomers and find that some cannot be distinguished by their
line formulas (because their connectivity is the same).
Classroom options:
This activity can be conducted as an open class discussion integrated with Investigate This
5.55.
Time for activity:
15-20 minutes.
Instructor notes:
The molecular models from Investigate This 5.55 will be very useful in this activity.
(a) Line formulas for the double bonded isomers (in the order presented above in Investigate
This 5.55) are: CH2CHCH2CH3, CH2CH(CH3)2, CH3CHCHCH3, and CH3CHCHCH3.
NOTE: Line formulas for the cyclic isomers are tricky. Their structures should not be belabored
in this discussion, since they will not be used again. One way to show the cyclic structures is:
CH 2CH 2CH 2CH 2 for
cyclobutane and CH2CH2CH(CH3 ) for methylcyclopropane. Another, more

compact way to write these line formulas, is (CH2)4 for cyclobutane and (CH2)2CHCH3 for
methylcyclopropane, but these are more abstract and even harder for students who are just
beginning to learn about molecular structure and geometry.
(b) Two structures, the ones with the double bond between the second and third carbon atoms
in a four-carbon chain, have the same line formula. They are isomers because their atoms are
arranged differently with respect to the double bond when their models and structural or
skeletal formulas are examined. The two molecular structures cannot be superimposed on
one another.
Lead into an extension of the discussion of structural isomers and on to cis-trans isomers.
Check This 5.57. Cis-trans isomers.
Check This 5.58. Identifying isomers.
34
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Chapter 5
Investigate This 5.59. Do solutions affect polarized light?

Goal:
Students determine if solutions of water and light corn syrup affect polarized light.
Set-up time:
Time for activity:
Ranged from less than 10 minutes to 15-20 minutes.
Materials:
Overhead projector.
Sheet of cardboard with an 8-cm diameter hole in the center.
Petri dishes about 6-cm in diameter or 80 40 crystallizing dishes.
Two 10-cm square sheets of polarizing filters. One source of these filters is Educational
Innovations, Inc., 362 Main Ave. Norwalk, CT 06851, phone: (203) 229-0730; website:
www.teachersource.com.
Reagents:
Water.
Light corn syrup (as nearly colorless as possible).
Procedure:
This activity is conducted as a class investigation. Student volunteers can carry out the activity
while the rest of the class work in small groups to discuss and analyze the results.
Place the cardboard on the projector and put one of the squares of polarizing filter over the
hole. Turn on the projector and make a mark (or place a sticky dot) near the edge of the
projected image.
Place the second polarizing filter on top of the first and rotate the second filter until the image
on the screen is as dark as possible. Show the difference between parallel and crossed filters,
so students see how dramatic the change is.
Make a mark on the second filter directly over the mark on the first filter.
Fill one of the Petri dishes about half full of water and sandwich the dish between the two
polarizing filters. Make sure the mark on the top filter is directly over the mark on the bottom
filter and check to see whether the image on the screen is still as dark as possible. If not, rotate
the top filter until the image is as dark as possible and make another mark on the top filter to
indicate the new alignment of the filters.
NOTE: With just water in the light path, no rotation of the light should occur, so no rotation of
the top filter should be necessary. If, for some reason, the containers themselves affect the
polarized light, you should probably use a different container. It will be confusing for students
to consider the possibility that water affects the polarization of the light.
Repeat the procedure with the second Petri dish about half full of light corn syrup from the
grocery store.
Alternate Procedure:
Demonstrate polarized light, using the lenses from a pair of polarizing sunglasses to illustrate
parallel and crossed polarizers.
Then demonstrate how a polarimeter works using a solution of glucose (dextrose). Cross the
two polarizing filters to eliminate light. Place a solution of glucose in a large vial between the
two polarizing filters. Rotate the top polarizing filter until the light is once again blocked. This
is fundamentally the same procedure as above, but modified for smaller polarizing filters.
ACS Chemistry FROG
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Chapter 5
If you use glucose (dextrose) as a sample, you can extend the investigation by using fructose
(levulose) as a second sample to show that different sugars rotate the polarized light
differently. The marginal note on page 329 indicates that the names dextrose and levulose for
glucose and fructose refer to the fact glucose is dextrorotatory and fructose is levorotatory.
Showing this experimentally is interesting.
The polarizing filters sandwiching the water sample should align directly with the marks made
in the absence of water. However, with the corn syrup sample, the top polarizing filter will
need to rotated slightly to the right to fully darken the inner circle.
Photographs (i) and (ii) below show the set up with a water sample between the polarizing
filters. In photograph (i) you see the result when the top filter is rotated so that the maximum
amount of light is transmitted. Note that the filters are aligned squarely with one another. The
grayish ring is due to the walls of the glass dish, which do not transmit all the light (whether
polarized or not). Its important to note that there is an annulus of light outside the gray ring
that is light that has not passed through either glass or water. The inner circle of light has
passed through both the bottom of the container and the water. In photograph (ii) you see the
result when the top filter is rotated so that the minimum amount of light is transmitted. Note
that the filters are aligned squarely with one another, but the top filter has been rotated 90, so
that the polarizers are now crossed. No light is transmitted and projected. (The camera
observing from the side senses some light, but this is an artifact of the photography. Note that
the top filter appears more gray when rotated to this position.
(i)
36
(ii)
ACS Chemistry FROG
Chapter 5
(iii)
(iv)
Photographs (iii) and (iv) show what occurs when a sample of light corn syrup is substituted
for the water in the container between the polarizing filters. Compare (iii) with photograph
(ii). You can see that the top filter has been rotated clockwise a bit to again minimize the
amount of light transmitted through the solution and filters. There is a dim annulus of light
around the sample container [compare to photograph (i)] where the light does not pass
through the container or the sample and a small amount is transmitted because the filters are
no longer exactly crossed. Photograph (iv) is an attempt to show that the pink dots that
denoted the crossed alignment of the polarizers are no longer aligned, but the dots (to the right
of the container) are very difficult to discern. It is easier to see that the filter has been rotated
somewhat because the corners of the top and bottom filters are no longer aligned.
Discuss optical rotation and the fact that substances that rotate a plan of polarized light are
called optically active.
Introduce the concept of mirror images and discuss the mirror image crystals represented in
Figure 5.31.
Check This 5.61. Direction of optical rotation.
Investigate This 5.62. Are there stereoisomers of lactic acid?
Consider This 5.63. Can you identify optical isomers?
Check This 5.64. Properties of optical isomers.
Consider This 5.60. What solutions affect polarized light?
Goal:
Determine that a beam of polarized light is not affected by water but has its angle of
polarization changed by a sugar solution (light corn syrup).
ACS Chemistry FROG
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Chapter 5
Classroom options:
This activity can also be conducted as an open class discussion while Investigate This 5.59 is
being carried out.
Instructor notes:
Be sure the class agrees on the results from Investigate This 5.59.
(a) Water does not change the direction of polarization of the light beam. The evidence is
that the crossed polarizing filters do not have to be rotated with respect to one another when
the water sample is sandwiched between them.
(b) The solution of sugars changes the direction of polarization of the light beam. To observe
the darkest part of the inner circle, the top polarizing filter had to be rotated slightly
clockwise (to the right). The corn syrup rotated the plane of polarized light produced by the
lower filter. Further experiments might include using different types/concentrations of sugars
or drinks containing a lot of sugar. Perhaps a regular and diet version of such a drink could
be tried. Plastic wrap or plastic zip-closure bags could be tried to see if the polymer is
optically active. Stretching such a plastic often shows interesting polarization effects as the
polymer molecules become more aligned.
Discuss optical rotation.
Introduce mirror images and optical isomers.
Check This 5.61. Direction of optical rotation.
Investigate This 5.62. Are there stereoisomers of lactic acid?
Investigate This 5.62. Are there stereoisomers for lactic acid?
Goal:
By building molecular models of lactic acid, discover that there are two nonsuperimposable
structures with the same connectivity.
Set-up time:
5-10 minutes (to construct classroom-size molecular models of the optical isomers of lactic
acid).
Time for activity:
10-15 minutes (including discussion).
Materials:
Molecular modeling kits.
Procedure:
Students need to work in small groups on this activity, because they need to construct a few
models to test whether two or more nonsuperimposable structures are possible.
Alternately, they could construct the models as a homework assignment and bring them to the
next class session for comparison and discussion.
This activity could be done as part of a model building laboratory experiment.
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Chapter 5
Two structures that cannot be superimposed are possible for lactic acid. The structures are
mirror images of one another, as shown in this photograph:
Goal:
Identify optical isomers as structures that are nonsuperimposable mirror images of one another.
Classroom options:
This activity provides a pattern students can use to compare their models of lactic acid from
Investigate This 5.62 and an alternative model that does not produce nonsuperimposable
structures.
The activity, together with Investigate This 5.62, could be conducted at a recitation session or
be integrated into a laboratory.
If available, molecular graphics can be used to extend this activity.
Time for activity:
About 15 minutes (beginning with the structures of lactic acid from Investigate This 5.62)
Instructor notes:
(a) Drawings of the mirror image structures (looking down the CH axis) should look
something like this:
C(O)OH
H3C
HO(O)C
OH
HO
CH3
mirror plane
Both structures put the OH and C(O)OH groups next to each other, but in one isomer the
OH group is at the 8-oclock position and in the other isomer the OH group is at the
4-oclock position. Some student models will fit one of these patterns and the rest will fit the
ACS Chemistry FROG
39
Chapter 5
other. The two, nonsuperimposable structures of lactic acid from Investigate This 5.62 are
mirror images of one another.
(b) Mirror image drawings of a square planar structure for lactic acid look like this:
H 3C
C(O)OH
HO(O)C
HO
OH
CH 3
H
mirror plane
One square planar structure of lactic acid can be flipped over and superimposed onto its
mirror image structure. These mirror image structures are identical to one another. They are
not isomers. Mirror image structures of square planar molecules like this are not different
from one another, but we know that two isomers of lactic acid exist that differ only in that
one rotates the plane of plane polarized light clockwise and the other isomer rotates it
counterclockwise.
NOTE: Some students might suggest that these three planar structures are not superimposable
on one another and could be isomers of a square planar structure for lactic acid:
C(O)OH
H3C
C
H
OH
C(O)OH
H
OH
C(O)OH
H3C
CH3
OH
There are two arguments against this hypothesis. First, only two isomers, the optical isomers, of
lactic acid have ever been discovered. If there were actually three isomers, the third would
probably have been discovered by now. Second, the groups in these three molecules are not in
the same geometric position with respect to one another in these molecules. In the first two, the
C(O)OH and OH groups are next to one another, but, in the third, they are opposite one
another. It is quite likely that these three different structures would have different chemical and
physical properties, but the two isomers of lactic acid that we know have identical chemical and
physical properties, except for their interaction with polarized light (and with other molecules
that are also optical isomers, have chiral centers.) These are very much like the arguments vant
Hoff and Le Bel made when developing the tetrahedral model for the geometry around carbon
atoms in molecules.
Follow-up Discussion:
Help students come to understand that the central carbon atom in lactic acid has four different
atoms or groups attached and that there will be two nonsuperimposable, mirror image
isomeric structures for any molecule that has such a carbon atom. These two structures are
optical isomers.
Review key points in the Reflection and Projection section.
Follow-up Activities:
Section 5.10. Functional Groups Making Life Interesting

Identify the functional group(s) present in a molecular structure.
40
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Chapter 5
Use the polarities of functional groups (from electronegativities and bond polarities and/or
calculated electron distributions) to predict where molecules will be likely to interact with one
another.
Investigate This 5.65. How many C3H8O2 isomers are there?
Goal:
Build molecular models of as many C3H8O2 isomers as possible. [This activity provides practice
in model building, distinguishing isomers from identical structures, and insight into the large
number of connectivities (isomers) possible for a small number of second period atoms that can
be chained together.]
Set-up time:
You might want to make classroom-size models of the structures, but it is probably more
useful simply to have the model set available to build models on the spot, if students need
hints about connectivities they havent thought of.
Time for activity:
10-15 minutes (including discussion).
Materials:
Molecular models.
Procedure:
To save time in class, it might be useful to assign this activity as a homework assignment to
be done in groups (since the molecular model kits do not have enough atom centers to
construct all the isomers). Students will then bring their models to class to share and discuss.
This activity could be done in the laboratory and, if modeling software is available, enhanced
by seeing the structures in space-filling form.
The functional groups in the isomers can be alcohols, ethers, and peroxides (which students
have not previously encountered). Two of the structures have a carbon with four different
groups attached, thus adding optical isomers to the mix. Some of the possible structures are
unstable, such as gem-diols (hydrates of carbonyl compounds) and hemiacetals, but this is of
no concern for this activity or this text. This is not the stage of the students learning to make
such distinctions or to consider introducing nomenclature, such as acetal. If the students see
an acetal as two ether groups sharing a common carbon, that is just fine.
These isomers are possible:
Structures containing two alcohol, OH, groups
H
H
(1)
H
O
(2, 3)
O H
*
C C
(4)
H
H
(5)
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Chapter 5
Structure (2, 3) represents two isomers, the optical isomers of 1,2-propanediol. The starred
carbon (*) is bonded to four different groups, CH2OH, OH, H, and CH3. There are five
C3H8O2 isomers containing two alcohol groups.
Structures containing an alcohol group and an ether, COC, group
H
H
H
H
O
H
*
H
H H
H H
H
H
H H
(6)
(7)
(8, 9)
Structure (8, 9) represents two isomers, the optical isomers of 1-methoxyethanol or
1 hydroxy-1-methoxyethane. The starred carbon (*) is bonded to four different groups,
OCH3, OH, H, and CH3. There are four C3H8O2 isomers containing an alcohol and an
ether group.
Structure containing two ether groups
H
H
H
O
H
O
H
H
H
(10)
There is one C3H8O2 isomer containing two ether groups.
Structures containing a peroxide, OO, group
O
H
H
H H H
H
H H
H H H
(11)
(12)
(13)
There are three C3H8O2 isomers containing a peroxide group.
The total number of C3H8O2 isomers (including optical isomers as two isomers) is 13.
Use Consider This 5.66 to initiate further discussion of this activity that focuses on the
functional groups rather than finding different structures.
Check This 5.67. Retinol and retinal
Consider This 5.68. What are the interactions between an alcohol and an aldehyde?
Check This 5.69. Identifying functional groups
Sample Worksheet for Investigate This 5.65

The following is a worksheet used by Dr. Jonathan Mitschele, Saint Josephs College, Standish,
ME, to help his students focus on their tasks in this activity. Some editing has been done to
tighten up spacing (leaving out the spaces for answers), but no content has been changed.
Investigate This 5.65. How many C3H8O2 isomers are there?
Information: Table 5.4 on page 334.
You will be using your model kits to make molecular models today. Keep each model intact
until you have reported your results to the class.
42
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Chapter 5
1. Work in small groups (three in a group is ideal for this exercise, but two or four in a
group works well too; appoint one Manager, one Reporter, one Recorder, and one Modeler).
Modelers should assemble as many different skeletal structures (omit all hydrogens except
those attached to oxygen) for C3H8O2 as the group can think of. Be sure to look for
stereoisomeric pairs (for help with this see Tetrahedral arrangements around carbon on p.
5-62).
2. You should make skeletal drawings (again omitting all hydrogens except for those
attached to oxygen) that show the connections for each of the structures the group builds; the
Recorder should verify that each of your drawings is correct. Use the space below for your
drawings.
When all groups have completed this part of the activity, the Reporter should share your
groups results and models with the class.
Consider This 5.66. What are the functional groups in C3H8O2 isomers?
Goal:
Identify the functional groups and stereoisomers (optical isomers) in the C3H8O2 isomers
modeled in Investigate This 5.65.
Classroom options:
This activity can be conducted as an open class discussion as an extension of the discussion of
the isomeric structures in Investigate This 5.65.
class session, either in small groups initially or open class discussion.
Instructor notes:
Make sure students have their models and drawings from Investigate This 5.65 as this activity
is carried out.
Show or refer students to Table 5.4 as a reminder of some functional groups that contain
oxygen and/or nitrogen.
(a) Structures (1) through (9) shown above in Investigate This 5.65 have either one or two
alcohol groups.
(b) The peroxide functional group in structures (11) through (13) is not shown in Table 5.4
and we have not previously met this group. The peroxide group can be represented as:
O
The atoms bonded to the oxygens can be either H or C, as you see in the structures you made
for Investigate This 5.65.
(c) Two of the structures in Investigate This 5.65 are stereoisomeric pairs, structures (2,3)
and (8, 9). Each pair has a carbon atom with four different groups attached, so each is a pair
of optical isomers. The structures are:
ACS Chemistry FROG
43
Chapter 5
H
H
H
(2, 3)
O H
*
C C
H
H
(8, 9)
C
H
O
O
C
H
H
*
Discuss alcohol and ether functional groups, leading the class to see the similarities and
differences and the relationship to water.
Use this discussion to lead on to a discussion of the carbonyl and carboxyl functional groups.
Check This 5.67. Retinol and retinal.
Sample Worksheet for Consider This 5.66
Consider This 5.65. What are the functional groups in C3H8O2 isomers?
1. How many different functional groups are there in your set of C3H8O2 isomers?
2. How many structures contain a functional group or groups that are not included in Table
5.4?
3. Are any of your structures stereoisomeric pairs? How can you tell when two structures
are stereoisomers? Draw the structures for each pair of stereoisomers below.
groups results with the class.
Goal:
Identify the interactions between the positive and negative charge centers in an alcohol and an
aldehyde.
Classroom options:
class session, either in small groups initially or open class discussion.
Time for activity:
Instructor notes:
The concept of hydrogen bonding may need to be reviewed as this activity is begun.
44
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Chapter 5
(a) A hydrogen atom bonded to a highly electronegative atom is required for hydrogen
bonding to a pair of nonbonding electrons on a highly electronegative atom in the other
molecule. The hydrogen atom in the alcohol group of ethanol and the nonbonding electron
pairs on oxygen atom of the carbonyl group in methanal fit these criteria. The hydrogen
bonding interaction (hydrogen bond shown in red) can be represented as:
O CH 2CH3
+ H
H
+ C
(b) The positive center of methanal, the C atom, interacts (is attracted by) one of the
nonbonding electron pairs on the negative center of ethanol, the O atom. The attractive
interaction is shown as a dashed red line in this representation, which also tries to represent
the geometry of the interaction as the nonbonding pair of electrons approaches from one face
of the planar geometry around the positive carbon center in the methanal.
O
+ C
HH
CH CH
2
3
O
H+
If a reaction were to occur, a bond would be likely to form between the carbonyl carbon atom
and the alcohol oxygen atom.
Discuss how interactions of positive and negative charge centers can lead to chemical
reactions and the formation of new molecules, but do not dwell on the possible reactions here,
since they are subject of Chapter 6, Sections 6.7 and 6.8.
Check This 5.70. Information from different representations of molecules.
Section 5.11. Molecular Recognition

Use the polarities of functional groups (from electronegativities and bond polarities and/or
calculated electron distributions) to predict where molecules will be likely to attract or repel
one another.
Consider This 5.71. Can you construct a molecule-to-order?
Goal:
Construct molecular models of C4H8O isomers that have specified properties.
Set-up time:
You might want to make classroom-size models of the structures, but it is probably more
useful simply to have the model set available to build models on the spot, if students need
hints about connectivities they havent thought of.
ACS Chemistry FROG
45
Chapter 5
Time for activity:

Allow about 5 minutes for students working in small groups to build their models and then
share them with the class. The discussion of the desired isomers and numbers of structural
isomers prepared by the class can be brief or take longer, if you wish to suggest looking
further at structures that are not the obvious ones most students will find.
This activity and follow-up discussion may be more easily accommodated in a recitation
session or as part of a laboratory activity.
Materials:
Molecular model kits.
Procedure:
Using their molecular model kits, students work in small groups to construct C4H8O cis-trans
stereoisomers.
Using their molecular model kits, students work in small groups to construct C4H8O optical
stereoisomers.
Comparing structures created by the groups, the class determines the number of structural
isomers represented by the cis-trans, and optical isomers constructed.
(a) There are four possible acyclic and two cyclic cis-trans isomers of C4H8O, for a total of six
structural isomers. The first and third pair of acyclic isomers are enols that would exist almost
entirely in their carbonyl forms, but the students do not know about this, so these structures are
OK. It is unlikely that most students will think about the cyclic isomers. You have to use your
judgment about whether to introduce them, since they will not appear again in the text.
HO
HO
HO
HO
HO
O
HO
HO
HO
(b) There is only one possible acyclic pair of optical stereoisomers, but there are five cyclic
pairs. Again, you have to use your judgment whether to introduce the cyclic structures, if
students do not find them for themselves. Three of the cyclic cis-trans isomers shown in part (a)
exist as pairs of optical stereoisomers and these are shown here as pairs of mirror images. For
the other structures, the chiral carbon is starred (*). If you do introduce the cyclic isomers, it is
probably imperative to build models of the mirror images to show that they are not
superimposable or to use the method outlined for cyclic molecules in Check This 5.64(c).
OH
HO
46
OH
ACS Chemistry FROG
HO
OH
Chapter 5
Sample Worksheet for Consider This 5.71
Consider This 5.71. Can you construct a molecule-to-order?
1. Each of you should construct a pair of C4H8O cis-trans stereoisomers. Compare your
models with those of others in the group.
2. Draw skeletal structures for each of your models. How many different structural isomers
are there?
3. Each of you should construct a pair of C4H8O optical stereoisomers. Compare your
models with those of others in the group.
4. Draw skeletal structures for each of your models.
Section 5.13. Extension Antibonding Orbitals: The Oxygen Story

Investigate This 5.73. Are O2 and N2 affected by a magnet?
To get this activity to work well is not trivial. Detailed instructions are given by H. Shimada,
T. Yasuoka, and S. Mitsuzawa, Observation of Paramagnetic Property of Oxygen by Simple
MethodA Simple Experiment for College Chemistry and Physics Courses, J. Chem. Educ.
1990, 67, 63. The major factors affecting the ability to observe the effect of a magnet on a
bubble of gas on the surface of a dilute soap solution are: the size of the bubble, the curvature
of the surface, and the strength of the magnet. The bubble should be 3-10 mm in diameter on a
convex liquid surface. To create the convex surface, the level of the soap solution must be
higher than the edge of the Petri dish used to contain it, that is, the liquid has to pile up
toward the middle of the dish. A bubble on this surface will move to the center of the surface,
the highest point. As strong a magnet as possible (consistent with being able to hold and
maneuver it near the bubble) should be used. Ceramic magnets are probably the best bet for
this purpose. The authors used a syringe to contain the gas, blew their bubbles on the tip of
the syringe needle (like using a bubble pipe) and then brought them into contact with the
surface. You need to practice this technique to make sure you can carry it out consistently
before using it in class. If you are successful, this is surely the easiest and safest way actually
to show the attraction of oxygen to a magnet.
A more spectacular, albeit more dangerous, technique is to pour liquid nitrogen and liquid
oxygen between the pole pieces of a strong magnet. Liquid nitrogen simply runs through with
no evidence of interaction, but liquid oxygen is held between the poles by the magnet and
does not pour through. Seeing the pale blue liquid suspended between the pole pieces is very
convincing evidence of its attraction to the magnet. With appropriate protection for the stage,
this activity can be projected (although the color of the oxygen will not be visible) or a video
camera and projection device can display it for the entire class.
ACS Chemistry FROG
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Chapter 5
The properties of nitrogen and oxygen in a magnetic field are the subject of one of the
demonstrations on Volume 2 of the Chemistry Comes Alive! CD-ROMs available from JCE
Software (the Journal of Chemical Education). QuickTime movies of liquid nitrogen and
liquid oxygen being poured between the poles of a powerful permanent magnet are included
on this CD. Although less exocharmic [R. W. Ramette, J. Chem. Educ. 1980, 57, 68; reprinted
in B. Z. Shakhashiri, Chemical Demonstrations, Volume 1, pp. xiii-xvi (University of
Wisconsin Press, Madison, 1983)] than the actual experiment or the movies, still pictures
from the movies are available free at the Journal of Chemical Education website:
http://jchemed.chem.wisc.edu. Navigate to the appropriate page via JCE Software > Video >
Chemistry Comes Alive! > Contents > Volume 2 > Electronic Structure/Periodic Table >
Paramagnetism: Nitrogen and Oxygen > Slides. Several jpeg stills are available in large
enough format to display in a lecture hall, if you can access this website. The QuickTime
movies are not available on the website.
Use Consider This 5.74 to initiate discussion about the observations while this activity is
carried out.
Consider This 5.74. How are O2 and N2 gas affected by a magnet?
Goal:
Conclude from the Investigate This 5.73 results that O2 has magnetic properties and N2 does not.
Classroom options:
Instructor notes:
O2(g) bubbles are attracted to a magnet, while N2(g) bubbles are not.
O2(g) molecules must have magnetic properties that N2(g) molecules do not.
Discuss the paramagnetism of oxygen, leading into determining the molecular orbital model
for oxygen and the lower reactivity of oxygen with unpaired electron spins compared to
oxygen with paired electron spins.
Check This 5.67. Molecular orbitals in nitrogen.
Although the chemistry of O2 is very different from what one might expect, it is not unique,
and students might find other examples, especially those with a biochemical flavor, of interest
as well. Another reaction that is affected by unpaired electron spins is the acid dissociation
equilibrium for HNO(aq):
HNO(aq) + H2O(l) H3O+(aq) + NO(aq)
The reactant, HNO, has all electrons paired, but the product NO has the same number of
electrons as O2 (they are isoelectronic) and is calculated also to have two unpaired electrons in
its lowest energy state (ground state). We pointed out that reactions of O2 are slow because of
its unpaired spins. In the acid dissociation reaction above, the formation of a product with
unpaired spins is also inhibited and the equilibrium constant is calculated to be about 3 10
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11
, which is much smaller than would be expected without this electronic effect. This
phenomenon and a good deal more about NO and HNO in biological systems are discussed in
an article by E. K. Wilson, New NO Directions, Chem. & Eng. News 2004, 82, 39 (March
8, 2004 issue).
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Chapter 5
Solutions for Chapter 5 Check This Activities

Check This 5.4. Comparison of the C5H12 and C4H10O isomers
(a) Just as the properties of the 2-methyl-2-propanol (tert-butyl alcohol) are not similar to the
other C4H10O alcohols, so the melting and boiling points of 2,2-dimethyl propane are not similar
to the other C5H12 isomers. Both 2-methyl-2-propanol and 2,2-dimethyl propane have higher
melting points, but lower boiling points than their isomers.
(b) Both 2-methyl-2-propanol and 2,2-dimethyl propane have two groups in the 2 position of
their molecular structures.
(c) The molar mass of C4H10O is 74 gmol1 and the molar mass of C5H12 is 72 gmol1. There
are 42 (= 4 6 + 10 1 + 1 8) electrons in a C4H10O molecule and 42 (= 5 6 + 12 1)
electrons in a C5H12 molecule. Since the number of electrons is the same in each molecule, you
would expect the attractive dispersion forces between the molecules in their pure liquids to be
about the same. This would suggest that the boiling points of the two sets of isomers would be
about the same. However, the boiling points of the corresponding isomers (1-butanol and
pentane, 2-methyl-1-propanol and 2-methylbutane, and 2-methyl-2-propanol and 2,2-dimethyl
propane) differ by 70-80 C, with the alcohols all having the higher boiling points. The
difference between the two sets of isomers is that the alcohol molecules can form hydrogen
bonds and the hydrocarbon molecules cannot. Hydrogen bonding is likely to be the main factor
responsible for the great difference in boiling points.
Check This 5.5. Lewis structures of the C2H7N isomers
(a) The Lewis structures for ethyl amine and dimethyl amine are:
H
(b) A photo of the molecular models is shown here. The structure on the left is ethyl amine,
CH3CH2NH2, and the structure on the right is dimethyl amine, CH3NHCH3. Both structures are
bent, but dimethyl amine is symmetrical, that is, the molecule is the same on both sides of the
center nitrogen atom.
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Check This 5.7. Lewis structures and molecular models for C3H9N isomers
Use the same approach as in Worked Example 5.6, by starting with the longest possible carbon
chain, adding an NH2 group (amino) to positions along the chain and then begin inserting the
nitrogen atom between carbon atoms to produce further isomers. The Lewis structures are:
H
H
H N H
H
H
H
H
H
C
N
C
H
H
C
The four isomers (in the order shown) are 1-aminopropane (propylamine), 2-aminopropane
(isopropylamine); ethylmethylamine, and trimethylamine. You are not responsible for knowing
or using these names, although you should study the names and structures to see how the names
are derived. Photographs of the molecular models in the same order are shown here.
1-aminopropane
2-aminopropane
ethylmethylamine
trimethylamine
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Chapter 5
Check This 5.9. More on the C5H12 isomers

(a) All three structures should be the same and look like this model:
(b) Names are always a clue for identifying isomers, because every isomer has a different name.
The base name is the name of the longest carbon chain and is chosen first using the nomenclature
given in the marginal note on page 282. Then the branches that split off from the main carbon
chain are identified and named using nomenclature also derived from the names in the note.
Structure (a) is a five-carbon chain and we see that the base name is pentane. Since there are no
branches, this is the name of the compound. Structure (b) is the one shown in part (a) here; its
longest chain is four carbon atoms, so the base name is butane. A methyl group, CH3, is bonded
at the second carbon atom, and this position of attachment is designated by 2 in the name, 2methylbutane. The longest carbon atom chain in structure (e) is three carbons, so the base name
is propane. Two methyl groups are attached at the middle or second carbon atom in the chain and
this position is again denoted by a 2 (one for each methyl) in the name, 2,2-dimethylpropane.
Check This 5.11. Boiling points of the C4H8O alcohols
Two factors may help explain the lower boiling point for 2-methyl-2-propanol compared to the
other isomers. Attractive dispersion forces depend on the number of electrons that interact with
one another on adjacent molecules. When the structure is more stretched out, there are more
opportunities for such interactions. A sphere has the lowest surface to volume ratio of any solid.
The rather compact structure of 2-methyl-2-propanol molecules reduces the amount of surface
that can interact, so there is less attraction among the molecules. The compact structure also
inhibits the amount of hydrogen bonding somewhat, because not as many molecules can get
together in the appropriate geometry to hydrogen bond. They get in one anothers way.
Check This 5.13. Potential and kinetic energy combinations
No numbers are shown on the scales in Figure 5.4, because the numbers are different for
different orbitals and nuclei, but the shape of the curves remains the same. For ease in carrying
out this activity, imagine that each major division on the energy scale represents one energy unit
(unspecified size). Likewise imagine that the internuclear distance axis begins at 0 on the left
and that each major division is one unit. Thus, at three units of the distance axis, the energies
are: PE = 2.5 unit; KE = 1.0 unit; E = 1.5 unit. Equation (5.2), E = PE + KE, is satisfied. At
four units on the distance axis we have PE = 2.0 unit, KE = 0.7 unit, and E = 1.3 unit, and
equation (5.2) is satisfied. At five units on the distance axis we have PE = 1.7 unit, KE = 0.5
unit, and E = 1.2 unit, and, once again, equation (5.2) is satisfied
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Check This 5.17. A fourth combination of sigma orbitals

(a) The Lewis structure for HF is H F . HF has 1 orbital and 3 n orbitals and it is linear.
The shape must be linear because there are only two atomic cores involved and two points
always determine a line, so this shape is predictable without reference to the orbitals or any
bonding model. Based on the progression of HX bond lengths for the three preceding second
row hydrides, which decease by 8 pm from CH4 to NH3 and then 7 pm from NH3 to H2O, we
would expect the HF bond length to be less than 94 pm, perhaps by a few pm to 90 pm. The
bond length should continue to decrease, because the atomic core charge is +7 for F and its
orbitals are even smaller than for O atoms. The experimentally determined bond length is 92
pm. A sketch of the molecular orbitals and a ball-and-stick model to show the geometry are:
(b) Again, in the Web Companion, Chapter 5, Section 5.4, page 2, as in Figure 5.10, we see that
each second row central atomic core is surrounded by four tetrahedrally arranged sigma
molecular orbitals. Bonding to H atoms is via these molecular orbitals, but not all the molecular
orbitals are used for bonding in these three molecules. The geometries of the hydrides are
determined by the arrangement of the orbitals that bond the H atoms. For example, only three
orbitals are used for bonding in ammonia, NH3, and the resulting geometry is a triangular
pyramid (trigonal pyramidal) with the N at the apex and the Hs at each of the corners of the base.
The remaining nonbonding sigma molecular orbital occupies somewhat more space and distorts
the tetrahedral geometry with the result that the H-N-H bond angles are a bit smaller than the
tetrahedral angle.
Check This 5.19. The structure of SF6
The Lewis structure for SF6 has a total of 48 valence electrons. The Lewis structure requires six
pairs of electrons (total of 12) for the SF sigma bonds and the rest are arrayed around the Fs to
give octets on each one. The most symmetrical distribution of the sextet of sigma bonding
orbitals on the central S atom is an octahedral array with the orbitals directed toward the
vertices of a regular octahedron.
F
F
S
F
F
F
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Chapter 5
Check This 5.21. Sigma orbitals around third- and higher-period atoms in molecules
The Lewis structures and geometries for ClF3, BrF5, and IF7 (with nonbonding electrons on F
not shown) are:
F
F
Cl
F
F
F
Br
F
F
I
F
F
F
T-shaped
Square pyramidal
Pentagonal bipyramidal
ClF3 has 5 electron pairs around the central Cl atom, BrF5 has 6 electron pairs around the central
Br atom, and IF7 has 7 electron pairs around the central I atom. The Cl and Br atoms cannot
form compounds with more F atoms due to the smaller size of their cores, which permit five and
six sigma orbitals, respectively, to be accommodated, but no more. The larger core of the I atom
allows more sigma orbitals to pack closely. Thus, it can accommodate more F atoms.
Check This 5.28. Other bond angles in ethene and methanal
(a) The experimental H-C-C bond angle in ethene must be 121.5. The sum of all the bond
angles around the planar C atom geometry in ethene must be 360. Since the observed H-C-H
bond angle in ethene is 117, each H-C-C bond angle must be (360 117)/2 = 121.5. By the
same reasoning, the experimental H-C-O bond angle in methanal must be 122.
(b) Using our molecular models of ethene and methanal, we know that the H-C-H bond angles
are 109.5 each. Therefore, the H-C-C bond angle in ethene and the H-C-O bond angle in
methanal are both 125.3 [= (360 109.5)/2 = 125.3]. The same calculation strategy that was
used in part (a) is used here. These calculated bond angles are close to those calculated in part
(a), but somewhat larger, as is expected because the H-C-H bond angle in the models is smaller
than the experimental value.
Check This 5.30. Lewis structure for the ethyne (acetylene) molecule
(a) The Lewis structure for ethyne is H C C H . Use bent bonds in the molecular model kit
to construct a model structure corresponding to the Lewis structure.
This model predicts that ethyne is a linear molecule (all four atomic centers on a line).
(b) The carbon atomic centers in the bent bond molecular model of a triple bond are somewhat
closer together than for a double bond, which is shorter than a single bond (constructed with the
white connector in the model kit). Thus the models are consistent with the experimentally
determined decreasing bond lengths with increasing number of bonds between the carbon atoms.
We suggested that more bonding electrons between the carbon atom cores would hold them more
tightly and the increased attraction by the larger number of electrons would draw the nuclei
closer together. This explanation continues to work for the triple bond, as the number of bonding
electrons between the carbon atomic cores is now six, compared to two or four.
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Check This 5.31. Representations of the bonding in ethene

In order to view the movie and exercise Molecular representations of ethene in the Web
Companion, Chapter 5, Section 5.6, page 1, as intended, you may have to click on the Lewis
structure of ethene instead of the hand. Sometimes, only a portion of the window appears when
just the hand is clicked. At the lower left of the window is a movie that consists of four
frames with four different representations of the ethene molecule, each of which can be rotated
about its vertical axis. To navigate between the representations, you can drag the cursor hand
vertically or you can position the cursor at the top or bottom of the movie panel until it turns
into an arrow and then hold down the mouse button. The four representations are shown here
left to right: transparent charge density surface with internal ball-and-stick structure to locate
nuclei; charge density surface with colors as in the text; electron surface of the molecule without
charge density coding; and, space filling model:
Drag the cursor horizontally across the representations to rotate them. They can also be rotated
by moving the cursor to the left or right margin of the movie screen until it becomes a curved
arrow and then hold down the mouse button.
This activity is a Check This to encourage students to explore these representations on their
own, to think about what they can learn from each one, and to consider which is the most useful
to them (or which parts of more than one are the most useful for their understanding). If
facilities are available for using the Companion in the classroom, it would probably be
worthwhile to follow up a homework assignment that includes this activity with a classroom
discussion while it is available to be explored.
Check This 5.32. The sigma-pi representation for methanal
To modify the illustrations in Figure 5.19 to represent methanal, we let one of the second period
atomic cores (dots) represent the oxygen atomic core and the other the carbon core. Instead of
two bonding sigma orbitals to hydrogen on the oxygen atomic core, there will be two
nonbonding sigma orbitals. The sigma framework is the same, but not all the sigma orbitals are
bonding. The pi orbital will be essentially identical (although probably modified in size by the
larger attraction of the more positive oxygen core). The combination simply brings together the
sigma framework and pi orbital as viewed side on to the molecule.
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Chapter 5
Check This 5.33. The sigma framework and pi molecular orbital in methanal
(a)/(b) The model is similar to ethene, but one atom, the oxygen atom, has two pairs of
electrons in nonbonding sigma orbitals instead of two bonding sigma orbitals with hydrogen
atoms. The light blue, trigonal atom center is used for the oxygen atom, with the two blue
paddles designating the two nonbonding electron pairs that are part of the sigma framework.
Check This 5.34. The sigma-pi representation for ethyne

(a) The sketch would look similar to Figure 5.22 except the nitrogen atom (blue) would be
replaced by a carbon atom bonded to a second hydrogen atom extending in a straight line along
the axis of the molecule.
(b) Ethyne has a - and two -bonding orbitals. Thus, in addition to the two bonding electrons
directly between the two carbon atomic cores, there are four other electrons just outside the line
of centers that add to the attractive forces on the carbon cores. These carbon cores are drawn
even closer than the carbon cores in a double bond with two -bonding electrons and only two
-bonding electrons.
Check This 5.36. Lewis structure for the nitrate ion
Lewis structures for the nitrate ion are easy to write, but they have the same problem as for
carbonate: none of them show the equivalence of the oxygen atoms.
O
N
O
Check This 5.39. Bond order in carbon dioxide

(a) Each of the two delocalized pi orbitals in CO2 interacts with all three atomic centers. Thus,
the pair of electrons in each orbital is shared between two pairs of atomic cores and the pi bond
order is 1/2 for each orbital in each bond. Since there are two of these delocalized pi orbitals, the
total pi bond order for each bond is one. Together with the sigma bond, therefore, the bond
order for each bond in CO2 is two. The Lewis structure shows the same bond order.
(b) Both the Lewis model and the delocalized -electron model of CO2, suggest that the bond
order is two for the bonding between the carbon atomic core and each oxygen atomic core.
Thus, the 115 pm bond length, which is shorter than the usual 120 pm CO double-bond length,
might seem puzzling. But these are not normal CO double bonds, because they are the result of
electron delocalization. Delocalization lowers the kinetic energy of the electrons, so the
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Chapter 5
minimum in total energy of the negative potential energies of attraction and the positive
contribution from the kinetic energy occurs at a slightly shorter internuclear distance (bond
length). It is like moving the kinetic energy curve in Figure 5.4 a bit to the left, thus moving the
energy minimum to a smaller internuclear distance. This explanation is also consistent with the
overall greater stability of the molecule compared to what would be predicted for localized
orbitals. [The greater stability of the CO2 molecule lowers the energy of the molecule compared
to two isolated CO double bonds, as we will see in Chapter 7, Section 7.7, especially in the
footnote to Table 7.3.]
Check This 5.40. Structure of the ozone molecule
(a) Two equivalent Lewis structures can be written for ozone:
O
The central oxygen atomic core in these structures is surrounded by three sigma orbitals, two
bonding and one nonbonding. Figure 5.18 shows that the orbital geometry about the central
oxygen atom will be trigonal planar, so the molecule will be bent. Either of these structures
alone is not consistent with the equivalence of the end oxygen atoms in the chain; they have
different electron arrangements. The two equivalent Lewis structures signal that we need to use
delocalized pi orbitals to describe the pi bonding in ozone. The two pi electrons are shared
across two OO bonds, so the pi bond order is 1/2 for each bond. Thus, the sigma and pi bonds
together give a bond order of 1-1/2, for each OO bond in ozone.
(b) Since the bond order for each O-O bond in ozone is 1-1/2, we expect the bond length to be
intermediate between a single and double bond, and, indeed, it is. Note that intermediate does
not mean exactly half way. Bond lengths depend on several factors that do not vary linearly
with internuclear distance, so we cant accurately predict numerical values for unknown bond
lengths based on known lengths for other bond orders. (In this particular case, the OO single
bond length is longer than expected, compared to what we might predict by comparison with
other molecules. The CC and NN single bond lengths are 154 and 147 pm, respectively. On
the basis of the decrease in orbital size with increasing core charge, we might expect the OO
single bond to be about 140 pm, instead of the same as for the NN single.)
Check This 5.43. Three-dimensional packing of spheres
This photograph shows the packing of the plastic balls representing hydrogen atomic centers in
your molecular model kit.
The packing of the top and bottom layers looks similar to the packing shown in Figure 5.26. The
layers are shifted with respect to one another so the spheres can fit into depressions in the other
layer. Packing would be more efficient (for an array of spheres not constrained by a box) if each
spheres in one layer fit into the triangular depression between three spheres in the next layer, as
shown in Figure 5.8 for the packing of four spheres.
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Chapter 5
Check This 5.44. More properties of metals

The bonding in the metal is not very directional. The sea of electrons essentially surrounds each
atomic center so it is not attracted strongly in any particular direction. Thus, when a force is
applied that pushes atomic centers away from one position, they can relatively easily move past
one another as the electron sea shifts continuously to accommodate the new shape of the metal.
Forcing the atomic centers into new positions does not cause a great deal of difference in the
bonding properties, so the metal is much the same after as before it was reshaped. The bonding
in ionic crystals, on the other hand, is quite directional. Each ion is attracted by oppositely
charged ions that are at specific locations with respect to one another. If a force is applied to
move charge centers from one location to another many of these directed interactions have to be
broken and the crystal cannot easily accommodate such an upheaval. When the force is strong
enough, the attractions are broken, but the result is that the crystal structure is disrupted and the
crystal usually shatters. These are the results you observed in Investigate This 5.41 and
illustrated in the photograph accompanying this activity on page 317.
Check This 5.45. Interpreting 3-D structures
(a) Most students find Figure 5.29(a) easiest to interpret because it is more apparent that the
hydrogen atoms are all on the side of the nitrogen atom opposite the nonbonding electron pair.
In the other representations the location of the Hs relative to the nonbonding pair is difficult to
discern. (Some students may find one of the other representations easier to interpret and they
might explain to the class why this is the case.)
(b) The comments on Check This 5.31 concerning navigation in the movie window apply here
as well. Share with the class what you found most useful about the various representations of
the methane molecule in the Web Companion, Chapter 5, Section 5.8, page 1. The
representations, from left to right are ball-and-stick, 3-D, space-filling, and electron surface.
(c) The 3-D structures for chloromethane shown here should be compared with the similarly
labeled structures in Figure 5.29. In each case, the Hs are in the same position and the Cl in
CH3Cl takes the place of the nonbonding electron pair in NH3. The three dimensional structure
is much easier to see for all three of these structures.
C
H
H
H
(a)
Cl
H
Cl
(b)
C
H
Cl
H
(c)
Correlations with a molecular model of CH3Cl help to see that all three of these representations
are the same molecule simply rotated in space.
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Check This 5.46. 3-D structures

(a) The Lewis structure for methanol shows that there are four sigma orbitals around each
second period element: four on C and two and two n on O. The orbital geometry around
each atom is tetrahedral. We can rotate the groups so that two Hs are coplanar with the C and O,
as shown in the 3-D structure.
H
H
H
O
H
(b) The Lewis structure for methanoic acid shows that there are three orbitals on C and two
and two n on O. The geometry around the C must be trigonal planar, so the C, both Os, and the
H bonded to C must lie in a plane. The OH group can be rotated so the alcohol H can also lie in
this plane, as shown in the 3-D structure.
O
O
H
(c) All four atoms in ethyne lie on a line, which, of course, must also lie in a plane.
H
Check This 5.49. 3-D and condensed structures for the C5H12 isomers
The 3-D and condensed structures for the 12 isomers are:
H H H H
C
C
C
H
C
C
H
H
pentane
H H
H H
H H HH
H
H
2,2-dimethylpropane
C
C
H H
C
H2
H HH
H H C H
C
C
H
H
C
C
2-methylbutane
H 3C
C
C
H
H2
C
C
H2
CH 3
CH 3
H 3C
H
H
H
C
H2
CH
CH3
H3 C CH3
H3 C
CH3
Check This 5.52. Skeletal structures for the C5H12 isomers

[Two proofreading errors appear in this Check This. In (a), the reference should be to Figure
5.32 and in (b) the reference should be to Check This 5.49. Although the errors might cause
confusion, it should be obvious what the correct references should be.]
(a) The line means a methyl group, CH3, is attached at this position or is the end of a carbon
atom chain.
(b) The skeletal structures for the C5H12 isomers are:
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Chapter 5
pentane
2-methylbutane
2,2-dimethylpropane
Check This 5.54. Interpreting skeletal representations

(a) At the end of each line (bond) and at each intersection, we know there is a carbon atom.
Enough Hs are bonded to each C to give it four bonds.
H3 C
CH
H 3C
CH3
H 3C
CH2
H 3C
2-methylpropane
2-methylpropene
(b) This is the skeletal structure for retinol (based on the condensed structure in Consider This
5.10 with the six-membered ring rotated to more clearly show the relationship to retinal in the
chapter opening illustration):
HO
The model of retinal shown at the lower right in the chapter opening illustration has this same
sequence of four double bonds in a carbon chain bonded to a six-membered ring. The
attachment to the ring is to a carbon at one end of a double bond and there is a methyl group
bonded to the carbon at its other end. Two methyl groups are bonded to the carbon that is one
away from the chain attachment in the other direction. The difference between these structures
is that the alcohol, OH, group at the end of the chain in retinol has become a carbonyl carbon
(loss of the alcohol H and a second H from the C to which the O is bonded) in retinal.
Check This 5.57. Cis-trans isomers
(a) There are three C2H2Cl2 isomers:
Cl
Cl
Cl
Cl
Cl
cis
Cl
trans
The cis isomer has two chlorine atoms on the same side of the C=C double bond, while the
trans isomer has the chlorine atoms on opposite sides.
(b) The skeletal structure for all-trans-retinol is given above in Check This 5.54(b). Look at the
four double bonds in the carbon chain. The carbon atoms that continue the chain at either end of
each double bond are trans to one another. This is why the structure is called all-trans.
(c) These two structures show the change from the cis (upper left structure in the chapter opening
illustration) to trans (lower right structure) forms of retinal, with the relevant double bond
indicated.
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O
O
cis
trans
[If you would like to introduce a more complex light-induced cis-trans (or E-Z) isomerization
that also has biological relevance, consider the case of bilirubin, which is responsible for
jaundice in some newborn infants and is treated by phototherapy (exposing the infant to bright
visible light). The chemistry and structures involved in the treatment are included in an
interesting case study by F. J. Dinan, Bilirubins chemical formula, J. Coll. Sci. Teach. 2004,
XXXIII, 18-22.]
Check This 5.58. Identifying isomers
The elemental composition for all the structures is C5H10O, so they are all isomers of one
another. Structures (ii) and (v) are identical. (Identical structures can superimposed after
rotating their parts with respect to one another without breaking any bonds. Making molecular
models can help identify identical structures.) The pairs of structural isomers [not including
structure (v), which is identical to (ii)] are: (i)/(ii); (i)/(iv); (ii)/(iii); (ii)/(iv); and, (iii)/(iv). The
stereoisomers are (i) and (iii).
Check This 5.61. Direction of optical rotation
(a) In Figure 5.30(b), the polarizer has been rotated clockwise (as seen by the observer at the
head of the arrow), so this is right or dextrorotatory rotation.
(b) From the observer's perspective in the Web Companion, Chapter 5, Section 5.9, page 2, the
rotation is counterclockwise, so this is left or levorotatory rotation.
(c) The top polarizing filter had to be rotated clockwise (see the photos accompanying
Investigate This 5.59 above), so this is right or dextrorotatory rotation.
Check This 5.64. Properties of optical isomers
(a) The structures from the Web Companion, Chapter 5, Section 5.9, page 5 are shown here with
3-D structures (stereochemistry shown only around the carbon with four different groups
attached) for comparison:
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Chapter 5
CH2
+
H3N
COO
CH2
H
NH3 +
COO
If you slide the 3-D structures on top of one another the COO and CH2C6H5 groups, both of
which are behind the plane of the paper, will be superimposed, but the NH3+ and H groups
will not be. There is no way to rotate the structures to make them superimposable. They are
optical stereoisomers, because they are nonsuperimposable mirror image isomer.
(b) The phenylalanine isomer shown in the beam of plane polarized light in the Companion,
Chapter 5, Section 5.9, page 6, is the one on the left in the model and 3-D structure in part (a).
If the other isomer was placed in the light path, the resultant arrow (representing the light after it
has passed through the sample) would be oriented along a line from about 11 oclock to 5
oclock (instead of the 1 oclock to 7 oclock shown above and in the animation). This is
because the other isomer would rotate the light by the same amount, but in the opposite
(counterclockwise) direction.
(c) [The directions should state that the position of the CH2OH group must be marked as well;
here we use a blue dot.] The marked hexagon and its mirror image are:
The mirror-image hexagons are not superimposable. The stereoisomers of glucose are optically
active. This finding is consistent with the results in Investigate This 5.51, where we found that
the sugars in corn syrup rotate the plane of polarized light passing through the syrup.
Check This 5.67. Retinol and retinal
Both molecules contain oxygen functional groups as well as CC double bonds (alkene groups).
Retinol has an alcohol group at the end of the carbon chain, while the retinal functional group in
the same location is an aldehyde (a carbonyl) group. The carbon skeletons of the molecules are
identical.
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Chapter 5

(a) Retinol contains one alcohol functional group and five alkenes while retinal contains one
aldehyde functional group and the same five alkenes.
(b) The functional groups in each molecule are outlined.
HO
NH2
(i)
C2H7NO
alcohol amine
O
(ii)
C7H12O2
both ketones
OH
HO
C
O
(iii)
alcohol
C7H12O3
carboxylic acid
OH
HO
(iv)
C
O
C7H12O3
alcohol carboxylic acid
(c) Structures (iii) and (iv) are nonsuperimposable stereoisomers (not mirror images of one
another). Imagine that the six-membered ring is simply a double bond and you see that the
structures are related to one another like cis-trans isomers. In (iii) the alcohol and acid group are
on the same side of the ring (like cis) and in (iv) they are on opposite sides (like trans).
Sample Worksheet for Check This 5.67 and 5.69
Check This 5.67 and 5.69 Functional groups
1. Draw skeletal structures for retinol (Consider This 5.10) and retinal (Check This 5.67 and
the chapter opening illustration).
2. What functional groups are present in retinol and retinal?
3. Each member of your group should make a model of each of the following molecules;
show each completed model to the group.
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63
Chapter 5
O
O
CH 3
NH2
HO
OH
CH 3
HO
O
3
OH
HO
O
4. Do the two ring structures (3 and 4) represent the same molecule? How can you verify
your answer? Are 3 and 4 stereoisomers? If so, what kind of stereoisomers are they?
Check This 5.70. Information from different representations of molecules
The comments on Check This 5.31 concerning navigation in the movie window apply here as
well. Share with the class what you found most useful about the various representations of the
acetone (propanone) and methyl ethanoate molecules in the Web Companion, Chapter 5,
Section 5.10, page 1. The representations, from left to right are ball-and-stick, space-filling,
electron surface and charge density (and, for acetone, transparent charge density enclosing a
ball-and-stick model to show the locations of the atom centers).
The charge density representations look quite similar for the two compounds. There is a high
density of negative charge at the carbonyl oxygen end of the molecules and quite a high density
of positive charge (low electron density) at the carbonyl carbon (to right of the carbonyl oxygen
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Chapter 5
in these views). Reactants that have positive charge (or the positive end of a highly polarized
molecule) will be attracted to the negative end of these molecules and might form bonds with
the carbonyl oxygen. Reactants that are negatively charged (or the negative end of a highly
polarized molecule) will be attracted to the positive region and might form bonds with the
carbonyl carbon. [Reactions like these are introduced in Chapter 6, Section 6.7.]
Check This 5.72. One form of molecular recognition
Before checking which isomer fits the receptor molecular surface, check to see which
phenylalanine structure each represents:
CH2
H
N H 3+
COO
CH2
+
H 3N
COO
Isomer 2 fits the receptor molecule surface. The positively charged functional group (the
protonated amine) on isomer 2 is attracted to the electron rich site (labeled with a negative sign)
on the receptor and the negatively charged functional group (the carboxylate anion) is attracted
to the electron deficient site (labeled with a positive sign) on the receptor. The nonpolar group
on the isomer interacts with the nonpolar site on the receptor.
Check This 5.75. Molecular orbitals in nitrogen
The energy level diagram for N2, assuming that the relative energy levels from Figure 5.42 are
applicable, is:
There are three pairs of bonding electrons in the and bonding orbitals, so the bond order is
three, that is, a triple bond. The Lewis structure for N3 is on page 342 and shows a triple bond,
so the molecular orbital and Lewis descriptions are compatible.
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Chapter 5
Sample from the Classroom: Chapter 5 Quiz

Chapter 5, Quiz Section Exercise
This Quiz Section Exercise was contributed by Dr. Priscilla Bell, Whittier College, Whittier,
CA. It has been edited to conserve space.
Name____________________________
1. Do Check this 5.7 from your text. For each isomer
a) write the full structural formula
b) write the condensed formula
c) write the skeletal structure
d) identify the character of each bond ( or ).
e) List the intermolecular forces the molecule might exhibit
f) the relative boiling point (highest, lowest, intermediate)
2. Do consider this 5.10 from your text. For each isomer
b) write the condensed formula
c) write the skeletal structure
d) identify the character of each bond ( or ).
e) List the intermolecular forces the molecule might exhibit
f) Assign the correct name from table 5.1
3. Consider the isomers of C3H7N
b) identify the character of each bond ( or ).
c) List the intermolecular forces the molecule might exhibit
Sample from the Classroom: Chapter 5 Exam

Sample Chapter 5 Exam
This examination was contributed by Dr. Jonathan Mitschele, Saint Josephs College, Standish,
ME. It has been edited to conserve space.
Name: ___________________
For this examination you may use only the periodic table provided! I recommend using your
model kit where appropriate. Write all of your answers on this examination, but be sure to
include all work with your examination if you wish to have partial credit. Staple any additional
sheets to this examination.
1. (a) Draw a Lewis structure for the acetate ion CH3C(O)O; if appropriate, include resonance
structures.
(b) Predict the OCO bond angle in the acetate ion.
(c) Predict the HCC bond angle in the acetate ion.
2. The molecule N2O has the skeletal structure NNO.
(a) Which Lewis structure(s) below is(are) acceptable? (Nitrogen and oxygen may have more
than the usual number of bonds in an acceptable structure.)
(i)
N
66
(ii)
O
(iii)
O
(iv)
O
(v)
O
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(vi)
O
(vii)
O
(viii)
O
Chapter 5
(b) If there are structures that are not acceptable explain why.
3. Which of the following isomers has the lower boiling point?
OH
OH
4. Which electrons, core or valence, are generally responsible for chemical bonding? Explain
why.
5. Consider the nitrate ion, NO3-, the nitrite ion, NO2-, and the nitronium ion, NO2+.
(a) What is the total number of valence electrons in each ion?
(b) Draw the Lewis structure for each ion.
(c) How many sigma bonding orbitals are there around the central atom in each ion?
(d) What geometry is predicted for each ion?
(e) How many pi bonding orbitals are there around the central atom in each ion?
(f) How many localized and how many delocalized pi orbitals are there in each ion? Explain
how you arrive at your answer.
(g) What is the bond order for nitrogen-to-oxygen in each ion? Use sketches of the
delocalized orbitals, if any, to illustrate your answer.
6. (a) Write a Lewis structure for each of the following molecules, including all non-bonding
electron pairs.
(i) I3(ii) BF4- (iii) SF4 (iv) XeF4 (v) PF6(b) What is the shape of each of these molecules?
(i)
(ii)
(iii)
(iv)
(v)
8. Stereoisomers (isomers that share the same connectivity of their bonds, but differ in their 3-d
shapes) can be subcategorized as optical isomers (those stereoisomers that bear a mirror image
relationship to one another) and those that are not optical isomers. Identify which of the
following pairs of structures are identical, which are optical isomers, and which are other types
of stereoisomers. Building models could be very helpful. NOTE: Bonds in bold come out of the
paper; dashed bonds go behind the paper.
(a)
(b)
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
(e)
Br
Br
Br
Br
(f)
(d)
OH
OH
OH
OH
OH
OH
OH
OH
(g)
(c)
OH
OH
(h)
OH
OH
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Useful Constants and Relationships:

speed of light, c = 3.0 108 ms-1
1 u = 1.66 10-24 g
h = 6.63 10-34 Js
c = (electromagnetic radiation) Ephoton = h
NA =6.02 1023
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67

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Chapter 5.

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Section 5.8. Representations of Molecular Geometry..............................................................29

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Check This 5.39. Bond order in carbon dioxide .......................................................................56

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Notes to Instructors regarding this chapter:

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Materials for Chapter 5 Activities

Small test tubes

5.10, 5.16, 5.25, 5.26, 5.27,

Sheet of cardboard to cover

Petri dishes (see activity)

Reagents for Chapter 5 Activities

0.1 M potassium permanganate,

1.58 g per 100 mL

Sodium metal, Na.

Rock salt, sodium chloride, NaCl

Light corn syrup

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Section 5.1. Isomers

Systemic Identification of Organic Compounds, 7th edition, R. L. Shriner, C. K. F. Hermann,

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Pictures of the results are shown here:

Reagents before alcohol is added

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Section 5.2. Lewis Structures and Molecular Models of Isomers

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The structure of the enantiomer of 2-butanol is:

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Section 5.3. Sigma molecular orbitals

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Section 5.4. Sigma Molecular Orbitals and Molecular Geometry

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(b) carbon hydride (methane)

nitrogen hydride (ammonia)

oxygen hydride (water)

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Section 5.5. Multiple Bonds

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0.1M potassium permanganate solutions, KMnO4(aq). Dissolve 1.58 g of KMnO4(s) in 100

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(a) The Lewis structure for methanal is:

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2-hexene (cis and trans):

3-hexene (cis and trans):

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Section 5.6. Pi Molecular Orbitals

Section 5.7. Delocalized orbitals

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(a) The Lewis structure of CO2 is:

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Check This 5.44. More properties of metals.

Consider This 5.42. What substances can be cut in two?