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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 C 4 H 10 O isomeric alcohols?

10

Section 5.3. Sigma molecular orbitals

13

Learning Objectives for Section 5.3:

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 σ n orbitals??

14

Section 5.4. Sigma Molecular Orbitals and Molecular Geometry

15

Learning Objectives for Section 5.4:

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

Learning Objectives for Section 5.5:

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 C 6 H 14 and C 6 H 12 ?

21

Consider This 5.27.

What is the geometry of double bonded molecules?

24

Section 5.6. Pi Molecular Orbitals

25

Learning Objectives for Section 5.6:

25

Section 5.7. Delocalized orbitals

25

Learning Objectives for Section 5.7:

25

Consider This 5.37. Do Lewis structures give correct geometries for CO 3 2 and NO 3 ?

25

Consider This 5.38. What are the bonding and structure of the CO 2 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

Structure of Molecules

Chapter 5

Section 5.8. Representations of Molecular Geometry

29

Learning Objectives for Section 5.8:

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

Learning Objectives for Section 5.9:

32

Investigate This 5.55. How many C 4 H 8 molecular structures are possible?

32

Consider This 5.56. What are the line (condensed) formulas for the C 4 H 8 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 C 3 H 8 O 2 isomers are there?

41

Sample Worksheet for Investigate This 5.65

42

Consider This 5.66. What are the functional groups in C 3 H 8 O 2 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 O 2 and N 2 affected by a magnet?

47

Consider This 5.74. How are O 2 and N 2 gas affected by a magnet?

48

Solutions for Chapter 5 Check This Activities

50

Check This 5.4. Comparison of the C 5 H 12 and C 4 H 10 O isomers

50

Check This 5.5. Lewis structures of the C 2 H 7 N isomers

50

Check This 5.7. Lewis structures and molecular models for C 3 H 9 N isomers

51

Check This 5.9.

More on the C 5 H 12 isomers

52

Check This 5.11.

Boiling points of the C 4 H 8 O 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 SF 6

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

Chapter 5

Structure of Molecules

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 C 5 H 12 isomers

59

Check This 5.52. Skeletal structures for the C 5 H 12 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

Structure of Molecules

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 shouldn’t 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.

Chapter 5

Structure of Molecules

Materials for Chapter 5 Activities

Activity

Material

Total Quantity

5.1, 5.22

Small test tubes

6

5.1, 5.22

Glass droppers

6

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

1

5.41

Sharp knife

1

5.59

Overhead projector

1

5.59

Sheet of cardboard to cover projector stage

1

5.59

Petri dishes (see activity)

2

5.59

10 × 10-cm squares of polarizing filters

2

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, KmnO 4

1.58 g per 100 mL of H 2 O

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

Structure of Molecules

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 Breathalyzertest. 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

Breathalyzerreagent is also known as Jones reagent. This preparation is adapted from The Systemic Identification of Organic Compounds, 7 th 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, Na 2 Cr 2 O 7 or K 2 Cr 2 O 7 . These preparations work equally well. Place 25 g of chromic anhydride, CrO 3 , 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 Breathalyzerreagent 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, KMnO 4 , 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 K 2 Cr 2 O 7 ) in 2-3 M sulfuric acid will work. Addition of a tiny amount of silver ion (50-100 mg/L of AgNO 3 ) 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.

Chapter 5

Structure of Molecules

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 Breathalyzerreagent 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 Breathalyzerreagent 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 Cr 3+ .

The overall reaction can be represented as:

3

OH R C
OH
R
C

R

H

+

Cr 2 O 7 2 + 8H +

Pictures of the results are shown here:

– + 8H + • Pictures of the results are shown here: Reagents before alcohol is

Reagents before alcohol is added

O 3 C O O
O
3 C
O
O

+ 2Cr 3+ + 7H 2 O

alcohol is adde d O 3 C O O + 2Cr 3 + + 7H 2

Mixtures after alcohol is added

The order of alcohols from left to right is ethanol, n-butyl alcohol, sec-butyl alcohol, iso- butyl alcohol, tert-butyl alcohol, and control (no alcohol). Clean-up:

Pour the six solutions together in a flask or beaker and add sodium bicarbonate, NaHOCO 2 , in small amounts until all the acid has reacted (no more CO 2 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.

Structure of Molecules

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 don’t. 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. Instructor’s 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, Cr 3+ .

(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, Cr 3+ .

(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.] Follow-up activities:

Consider This 5.3. How do the properties of the butyl alcohols isomers differ?

Check This 5.4. Comparison of C 5 H 12 and C 4 H 10 O

End of chapter problems 5.1 and 5.2.

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.

Chapter 5

Structure of Molecules

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.

This activity could also be assigned as a homework problem and then discussed at the next 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. Students should reason and conclude:

(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 200°C, 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 H 2 O, 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.

Follow-up activities:

Check This 5.4. Comparison of C 5 H 12 and C 4 H 10 O isomers

End of chapter problems 5.1 and 5.2.

Structure of Molecules

Chapter 5

Section 5.2. Lewis Structures and Molecular Models of Isomers

Learning Objectives for Section 5.2:

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.

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.

Consider This 5.10. What are the Lewis structures and molecular models for the C 4 H 10 O isomeric alcohols? Goal:

Students determine the Lewis structures and construct molecular models for the C 4 H 10 O 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 another’s 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. Students should reason and conclude:

(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 O–H group at one end:

H H H H H H C C C C O H H H H
H
H
H H
H
H
C
C
C
C
O
H
H
H H
possible chain with the O–H group at one end: H H H H H H C

Chapter 5

Structure of Molecules

[2-butanol] Construct the Lewis structure for a second isomer by moving the O–H group to one of the middle carbons:

H H H O H H C C C C H H H H
H
H
H O
H
H
C
C
C
C
H
H H
H

H

The structure of the enantiomer of 2-butanol is:

H H H H H The structure of the enantiomer of 2-butanol is: [2-methyl-1-propanol] Construct a
H H H H H The structure of the enantiomer of 2-butanol is: [2-methyl-1-propanol] Construct a

[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 O–H group bonded to one of the end carbons:

H H H H C H H H C C C O H H H
H
H
H
H
C
H
H
H
C
C
C
O
H H
H
ith the O–H group bonded to one of the end carbons: H H H H C

Structure of Molecules

Chapter 5

[2-methyl-2-propanol] In the previous structure, move the O–H group to the second carbon atom to form a fourth isomer:

H H H H C H H C C C H O H H
H
H
H
H
C
H
H
C
C
C
H
O
H
H

H

a fourth isomer: H H H H C H H C C C H O 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 O–H group is bonded to an end carbon of the chain, it makes sense call this 1-butanol, because the O–H

is at the first position on the chain. When the O–H 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 O–H 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 O–H is attached at the end of three-carbon chain and 2-methyl-2-propanol when the O–H 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

Chapter 5

Structure of Molecules

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. Follow-up discussion:

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. Follow-up activities:

Check This 5.11. Boiling points of the C 4 H 10 O alcohols.

End of chapter problem 5.1 through 5.9.

Section 5.3. Sigma molecular orbitals

Learning Objectives for Section 5.3:

Describe the similarities and differences between the formation and energetics of atomic and molecular orbitals.

Draw and/or describe σ and σ n orbitals for simple molecules containing elemental atoms from periods one, two, and three.

Predict molecular geometries for molecules containing σ and/or σ 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-two- proton 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 don’t 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:

Students should reason and conclude:

(a) The potential energy of attraction between proton A and the electron PE A becomes more

negative (more stable) as the protons are brought closer together.

(b) The potential energy of attraction between proton B and the electron PE B 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.

Structure of Molecules

Chapter 5

(d) The kinetic energy of the electron wave increases because the wave becomes more

constrained (smaller) as the protons move closer together. Follow-up discussion:

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 σ molecular orbitals. Follow-up activities:

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.

This activity can be conducted as an open class discussion. Time for activity:

Approximately 10 minutes. 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, σ, molecular orbitals. Students should reason and conclude:

(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. Follow-up discussion:

Discuss how σ 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 σ nonbonding molecular orbitals. Follow-up activities:

Consider This 5.14. What are the characteristics of σ n orbitals?

End of chapter problems 5.10 through 5.17.

Consider This 5.15. What is the symmetry of σ n orbitals?? Goal:

Define the symmetry axis of σ n orbitals so it is consistent with the cylindrical symmetry of σ orbitals.

Chapter 5

Structure of Molecules

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.

This activity can be conducted as an open class discussion. 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 σ bonding and nonbonding orbitals. Students should reason and conclude:

The axis of symmetry for a σ 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 σ orbital is smaller than a σ n orbital on the same atom. This is because two atomic cores attract the σ orbital electrons, while only one attracts the σ n orbital electrons. Follow-up activities:

End of chapter problems 5.10 through 5.17.

Section 5.4. Sigma Molecular Orbitals and Molecular Geometry

Learning Objectives for Section 5.4:

Draw and/or describe the σ and σ 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.

Structure of Molecules

Chapter 5

Procedure:

(a) Compounds of second period elements with hydrogen are often called hydrides. Write Lewis

structures for the hydrides of carbon (CH 4 ), nitrogen (NH 3 ), and oxygen (H 2 O).

(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.

Anticipated Results:

(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

C H H N H H
C
H H
N
H
H

H

HOH

(b) carbon hydride (methane)

H H C H H N H H H HOH (b) carbon hydride (methane) nitrogen hydri

nitrogen hydride (ammonia)

(b) carbon hydride (methane) nitrogen hydri de (ammonia) oxygen hydride (water) The geometry of the electron

oxygen hydride (water)

(methane) nitrogen hydri de (ammonia) oxygen hydride (water) The geometry of the electron pairs around the

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 CH 4 are usually described as having a tetrahedral geometry of four H atom centers arranged around the central C atom. The four atom centers in NH 3 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 H 2 O are described as having a bent geometry with the O atom at the center of the angular structure.

Chapter 5

Structure of Molecules

(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. Follow-up discussion:

Show or refer students to Figure 5.10 during the discussion of their answers.

Discuss the σ 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. Follow-up activities:

Check This 5.17. A fourth combination of sigma orbitals.

Worked Example 5.18. The structures of PF 3 and PF 5 .

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 SF 6 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. Students should reason and conclude:

(a) Another view of an octahedral array of balls is shown here to compare with Figure

5.12(b).

Structure of Molecules

Chapter 5

Structure of Molecules Chapter 5 (b) The octahedral array of balls is the same as the

(b) The octahedral array of balls is the same as the arrangement of σ bonding orbitals (sticks representing the bonding electron pairs) in the SF 6 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. Follow-up discussion:

Discuss the energetic reasons why the second period atoms do not accommodate more than four σ orbitals while third period atoms can accommodate more than four orbitals.

Summarize the points in the "Reflection and Projection" section. Follow-up activities:

Check This 5.21. Sigma orbitals around third and higher period atoms in molecules.

End of chapter problems 5.18 through 5.22.

Section 5.5. Multiple Bonds

Learning Objectives for Section 5.5:

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.

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 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 KMnO 4 (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:

Chapter 5

Structure of Molecules

0.1M potassium permanganate solutions, KMnO 4 (aq). Dissolve 1.58 g of KMnO 4 (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 MnO 2 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 KMnO 4 to each test tube.

The

reaction should be instantaneous.

Alternative suggestions:

Use one tube as a control with just ethanol and KMnO 4 in it.

Anticipated results:

Pictured from left to right in this photograph are the results of the test on hexane, hexene, pinene, limonene, blank

of the test on hexane, hexene, pinene, limonene, blank Clean-up: • Dispose of solutions in properl

Clean-up:

Dispose of solutions in properly labeled waste containers in accord with local ordinances. Follow-up discussion:

Use

Consider This 5.23 to initiate discussion of this activity.

Introduce and discuss the properties of double bonds.

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Chapter 5

Follow-up activities:

Worked Example 5.24. The Lewis structure and molecular model for ethene.

Consider This 5.25. What are the Lewis structure and molecular model for methanal (formaldehyde)?

Consider This 5.26. What are the structures and reactivity of C 6 H 14 and C 6 H 12 ?

Consider This 5.27. What is the geometry of double bonded molecules?

Check This 5.28. Other bond angles in ethene and methanal.

End of chapter problems 5.23 through 5.25.

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. Students should reason and conclude:

(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".

Follow-up activities:

Worked Example 5.24. The Lewis structure and molecular model for ethene.

Consider This 5.25. What are the Lewis structure and molecular model for methanal (formaldehyde)?

Consider This 5.26. What are the structures and reactivity of C 6 H 14 and C 6 H 12 ?

Consider This 5.27. What is the geometry of double bonded molecules?

Check This 5.28. Other bond angles in ethene and methanal.

End of chapter problems 5.23 through 5.25.

Consider This 5.25. What are the Lewis structure and molecular model for methanal (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. Students should reason and conclude:

Chapter 5

Structure of Molecules

H C O H
H
C
O
H

(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:

the nonbonding as well as bonding electron pairs is: In patterning this model after Figure 5.13,

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. Follow-up discussion:

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. Follow-up activities:

Consider This 5.26. What are the structures and reactivity of C 6 H 14 and C 6 H 12 ?

Consider This 5.27. What is the geometry of double bonded molecules?

Check This 5.28. Other bond angles in ethene and methanol.

End of chapter problems 5.23 through 5.25.

Consider This 5.26. What are the structures and reactivity of C 6 H 14 and C 6 H 12 ? Goal:

Writing Lewis structures and construct molecular models of the straight chain C 6 H 14 and C 6 H 12 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 C 6 H 14 and C 6 H 12 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.

Structure of Molecules

Chapter 5

Instructor notes:

Keep students focused on constructing straight chain isomers with no branches. In this case, there is one isomer for C 6 H 14 and three isomers for C 6 H 12 . Two of the C 6 H 12 isomers have cis- trans isomers (for a total of five isomers), but don’t 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 C 6 H 14 and C 6 H 12 . Students should reason and conclude:

(a) The Lewis structures for six-carbon-chain C 6 H 14 and C 6 H 12 isomers are:

H H H HHH H C C C C C C H H H H
H
H
H
HHH
H
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
C
C
C
CCC
H
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H

H

Although there is only one way to write a Lewis structure for C 6 H 14 with all the carbons connected in a chain, there are three ways to write a Lewis structure for C 6 H 12 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 C 6 H 12 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

these names. (b) Photographs of molecular models fo r these molecules are shown here. hexane 22

Chapter 5

Structure of Molecules

1-hexene:

Chapter 5 Structure of Molecules 1-hexene: 2-hexene ( cis and trans ): 3-hexene ( cis and

2-hexene (cis and trans):

5 Structure of Molecules 1-hexene: 2-hexene ( cis and trans ): 3-hexene ( cis and trans

3-hexene (cis and trans):

5 Structure of Molecules 1-hexene: 2-hexene ( cis and trans ): 3-hexene ( cis and trans
5 Structure of Molecules 1-hexene: 2-hexene ( cis and trans ): 3-hexene ( cis and trans
5 Structure of Molecules 1-hexene: 2-hexene ( cis and trans ): 3-hexene ( cis and trans

Structure of Molecules

Chapter 5

The C 6 H 12 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. Follow-up discussion:

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. Follow-up activities:

Consider This 5.27. What is the geometry of double bonded molecules?

Check This 5.28. Other bond angles in ethene and methanal.

End of chapter problem 5.25.

Consider This 5.27. What is the geometry of double bonded molecules? 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 classroom- size 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.

Chapter 5

Structure of Molecules

(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 σ bonding orbital between the cores is smaller so the atomic cores are brought closer together in a C–O bond compared to a C–C 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 C–C double bond, presumably for the same reason that the C–O single bond is shorter than a C–C single bond. Follow-up discussion:

Discuss the planar geometry of doubly bonded atoms, as found in these two examples, and go on to the geometry of triply bonded atoms. Follow-up activities:

Check This 5.28. Other bond angles of ethene and methanol.

End of chapter problem 5.25.

Section 5.6. Pi Molecular Orbitals

Learning Objectives for Section 5.6:

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 σ, σ n , and π 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

Learning Objectives for Section 5.7:

Draw and/or describe the σ, σ n , and localized and delocalized π 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 π orbitals and sketch what they might look like.

Consider This 5.37. Do Lewis structures give correct geometries for CO 3 2 and NO 3 ? Goal:

Determine if Lewis structures predict the correct geometries for CO 3 2 and NO 3 .

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Chapter 5

Classroom options:

Allow 3-5 minutes for students, working in small groups, to complete this activity. Then you can lead the discussion, summarizing answers on the chalkboard or an overhead transparency, or have the students do so.

This activity could also be assigned as a homework problem and then discussed at the next 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. Students should reason and conclude:

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. Follow-up discussion:

Discuss delocalized π molecular orbitals.

Introduce and discuss bond order. Follow-up activities:

Consider This 5.38. What are the bonding and structure of the CO 2 molecule?

Check This 5.39. Bond order in carbon dioxide.

Check This 5.40. Structure of the cyanate ion and the ozone molecule.

End of chapter problems 5.30 through 5.34.

Consider This 5.38. What are the bonding and structure of the CO 2 molecule? Goal:

From the Lewis structure and our sigma-pi bonding model predict the geometry of the CO 2 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.

This activity can be conducted as an open class discussion. Instructor notes:

Bring a classroom-size molecular model of CO 2 to class. Students should reason and conclude:

 
OCO

OCO

OCO
OCO
  OCO

(a)

The Lewis structure of CO 2 is:

(b)

In the sigma-pi structure derived from this Lewis structure, there are two σ orbitals on the

carbon atom, which predicts linear geometry about the carbon atom.

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Structure of Molecules

(c) A molecular model based on the Lewis structure, with paddles used to represent the nonbonding electrons is:

with paddles used to represent the nonbonding electrons is: The molecular model confirms the linear geometry

The molecular model confirms the linear geometry predicted in part (b). Follow-up discussion:

Discuss the σ framework and delocalized π molecular orbitals in the CO

2

molecule.

Lead into discussing why molecules with delocalized π orbitals have a lower total energy

than a molecule with localized π orbitals. Follow-up activities:

Check This 5.39. Bond order in carbon dioxide.

Check This 5.40. Structure of the cyanate ion and the ozone molecule.

End of chapter problems 5.30 through 5.34.

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:

Approximately 10 minutes. Time for activity:

Approximately 10 minutes. 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 screw- capped 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

Structure of Molecules

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.

and after cutting in two and then each piece in two again. These are photos of
and after cutting in two and then each piece in two again. These are photos of

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.

The hamme r shattered the crystals into smaller pieces. Clean-up: • Return the sodium metal pieces

Clean-up:

Return the sodium metal pieces to the container with mineral oil. Dispose of the rock salt, according to local ordinances. Follow-up discussion:

Use Consider This 5.42 to initiate discussion of the results of this activity.

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. Follow-up activities:

Check This 5.43. Three-dimensional packing of spheres.

Chapter 5

Structure of Molecules

Check This 5.44. More properties of metals.

End of chapter problems 5.35 and 5.36.

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:

Allow 3-5 minutes for students, working in small groups, to complete this activity. 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. 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. Students should reason and conclude:

(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. Follow-up activities:

Check This 5.43. Three-dimensional packing of spheres.

Check This 5.44. More properties of metals.

End of chapter problems 5.35 and 5.36.

Section 5.8. Representations of Molecular Geometry

Learning Objectives for Section 5.8:

Build molecular models based on the connectivities shown in Lewis structures of the 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.

Structure of Molecules

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. Students should reason and conclude:

(a) The Lewis structure and 3-D drawing for propene are:

H H H C C C
H
H
H
C
C
C

H H

H

H H H C H C C H H
H
H
H C
H
C
C
H 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, –CH 3 , 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 60º 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 C–C 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 C C C H H H
H
H
H
H
C
C
C
C
H
H H

H

H H H H C C H H C C H H
H
H
H
H
C
C
H
H C
C
H
H
H H H H C C C H H C H H
H H
H
H C
C
C
H
H
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 180º 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. Follow-up discussion:

Use the discussion of these structures as a lead in to condensed structures as a “shorthand” to represent complex structures. Follow-up activities:

Worked Example 5.48. 3-D and condensed structures for 2-propanol.

Check This 5.49. 3-D and condensed structures for the C 5 H 12 isomers.

Consider This 5.50. How many hydrogen atoms are bonded to a carbon?

Check This 5.52. Skeletal structures for the C 5 H 12 isomers.

Chapter 5

Structure of Molecules

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 carbon- containing 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 5–10 minutes. Instructor notes:

Use this activity to introduce and discuss skeletal structures. Students should reason and conclude that:

Carbon atoms do not have σ nonbonding electrons.

If necessary, sufficient H atoms are σ bonded to each carbon atom in a molecule to give it four σ and π bonding orbitals. Or stated another way, if the carbon atoms are bonded to non- hydrogen atoms, the remaining bonds that make up four bonding orbitals will be with hydrogen atoms. Follow-up activities:

Check This 5.52. Skeletal structures for the C 5 H 12 isomers.

Consider This 5.53. Can different skeletal structures represent the same molecule?

Check This 5.54. Interpreting skeletal representations.

End of chapter problems 5.38 and 5.39.

Consider This 5.53. Can different skeletal structures represent the same molecule? 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. Students should reason and conclude that:

Structure of Molecules

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 C 5 H 12 isomers, pentane and

2-methylbutane, can be made by rotating one part of the molecule with respect to another (that is, by rotating about C–C bonds). Here are just two possibilities for each isomer:

bonds). Here ar e just two possibilities for each isomer: Only one skeletal structure is possible

Only one skeletal structure is possible for 2,2-dimethylpropane because rotation about any of the C–C bonds leaves all five carbons in exactly the same relationship to one another.

carbons in exac tly the same relationship to one another. Follow-up discussion: • Use the discussion

Follow-up discussion:

Use the discussion to help summarize the points in the Reflection and Projection section. Follow-up activities:

Check This 5.54. Interpreting skeletal representations.

End of chapter problems 5.37 through 5.42.

Section 5.9. Stereoisomerism

Learning Objectives for Section 5.9:

Build molecular models based on the connectivities shown in Lewis structures of the molecules.

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).

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 C 4 H 8 molecular structures are possible? Goal:

Construct molecular models and draw their corresponding skeletal structures to determine how many C 4 H 8 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.

Chapter 5

Structure of Molecules

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. Anticipated results:

(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 C–C 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

methylcyclopropane

1-butene

them.   cyclobutane methylcyclopropane 1-butene 2-methylpropene trans -2-butene cis -2-butene •
them.   cyclobutane methylcyclopropane 1-butene 2-methylpropene trans -2-butene cis -2-butene •
them.   cyclobutane methylcyclopropane 1-butene 2-methylpropene trans -2-butene cis -2-butene •

2-methylpropene

trans-2-butene

cis-2-butene

(b)

The skeletal structures corresponding to the models for the six C 4 H 8 isomers in part (a)

are:

Structure of Molecules

Chapter 5

Structure of Molecules Chapter 5 Follow-up discussion: • Use Consider This 5.56 to initiate discu ssion

Follow-up discussion:

Use Consider This 5.56 to initiate discussion of the results of this activity. Follow-up activities:

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 C 4 H 8 isomers? Goal:

Write line formulas for the C 4 H 8 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.