Chem 3053

Organic Chemistry I Klein 1st Ed. Chapter 1 Structure and Bonding

R.L. Halterman

Learning Strategy: Preview the sections before the lecture covering those sections. Even a light reading will introduce new vocabulary and graphical depictions. With some prior familiarity the conceptual connections can be better made in lecture without as many huh?! moments. In lecture, use the provided notes, but keep your mind active by emphasizing sections or adding your own notes/comments to the preprinted version. Studies show that adding motor functions (aka writing) while listening/reading greatly improves retention. After lecture, reread the lecture notes and mark any additional items you recall, but did not put down during lecture. At this point you can carefully read the text and work the in chapter problems especially the Skillbuilder problems suggested in these study guides (do these in a spiral bound notebook for permanent record keeping). These problems are the backbone and strength of this text. You can master the material by working the problems. Check your answers against those in the study guide. Mark those problems you were weak on and review notes/textbook sections before reworking those problems. Do not fail to rework your weaker answers. By writing correct, complete answers with conceptual context you are more likely to retain and be able to use the information. At end of unit, work, check and rework end-of-chapter problems as assigned in these sheets. Prior to the Sapling homework windows for each chapter, you should complete the reading and text problems above. During the Sapling homework window, you should set aside time to work through the problems. You are able to rework the problems 5 times with a 5% penalty per additional attempt. Thus, you will score higher if you have good understanding prior to starting the Sapling set. You will not be penalized too much for typographical input errors or incorrect responses and should rework the problems until correct or you run out of attempts. It is very important that you learn to not only recognize the correct answers, but be able to produce and justify them. Attend Action Centers for additional problems in a group setting. The worksheets are graduated from simple access-or-process-the-information problems through more connected apply-the-concepts problems. By discussing and working the problems in small groups you should be able to hone your understanding and ability to work with the conceptsrather than just sitting home and memorizing. Since these are worksheets and the process is more stressed than the the answers, no keys will be posted. The quizzes on the days following action centers will emphasize material developed in these worksheets. Prior to exams, go back and rework quizzes, Action Center worksheets and textbook problems you had prior difficulty with. Review notes and text to patch rough spots as indicated by difficulties with these problems. Focused problem solving and reviewing sticking points are more effective than--but not as easy as uniform reviewing notes and readingsdo the writing! After this review work, work the problems posted from prior exams to check your level of familiarity. There will be review sessions the morning of exam days in which you can check your answers in small groups or ask the instructor. By the time of the exam, you should have a clear picture of which concepts are being stressed and whether you have a good handle on those key topics. After getting the graded exams back, you should rework all weak answers. Late mastery is better than none as the material builds on what should be as strong a foundation as possible.

The main part of this chapter introduces bonding. We will develop some views of Lewis structures, valence bond models and molecular orbital models, then look at hybridization, molecular geometry and intermolecular forces. Key concept--1st Law of Organic Chemistry: Negative charges like to be near plus charges and the more plus, the betterelectrostatic attraction is the basis of electronegativity. In assigned problems, SB stands for Skillbuilder exercises. Important Concepts, Topics and Reactions: Section Topic 1.1-2 Introduction and constitutional isomers. Start to recognize typical number of groups attached to various organically important atoms (H, C, N, O, X), aka valence. Problems SB1.1, 1.1, 1.3 Lecture notes: Additional emphasis placed on Coloumbic electron-electron repulsion and electronnucleus attraction (dependent on distance to nucleus and effective nuclear charge) 1.3-4 Lewis structures and closed shell configuration. Use two dots to symbolize the 2 electrons in bonds or non-bonded lone pairs on atoms (or bond line to represent 2 electrons). Double bonds have 4 dots. Atoms have formal charges if the electrons assigned to the atom has more or less than the number of protons its nucleus. Valid Lewis structures may not exceed the octet rule and must have the proper formal charge. Problems: SB1.2, 1.5, 1.6, SB-1.3, 1.10, 1.12, SB-1.4, 1.13, 1.14 1.5 Polar covalent bonds are directional with shared electronsbut since electrons are unequally shared one atom has partial negative charge (moderate difference in electronegativity). Know qualitative effect of partial charges given rise to dipole moments and that more charge separation corresponds to higher dipole moments. Not responsible for quantitative treatment. Problems: SB1.5, 1.15, 1.16. Atomic Orbitals. In atoms, electrons are placed into atomic orbitals which have set sizes and shapes. For O-chem, the 1s, 2s and 2p-orbitals are the most important. Electrons in larger orbitals, further from the nucleus are less stable (plus and minus charges attract less strongly). Only 2 electrons per orbital. Know how to fill in electrons into atomic orbitals using the Aufbau princple based on Hunds rule and the Pauli exclusion principle. Be able to draw electronic configuration of B, C, N, O, F as in Figure 1.10. Problems. SB1.6, 1.18

1.6

1.7-8 Valence Bonds and Molecular Orbitals form from the addition or subtraction of atomic orbitals. The constructive combination (bonding orbitals) allows two electrons to be nearer two nuclei and are more stable than the atomic orbitals. Destructive combination places a node between the nuclei and the electrons in these orbitals are less stable (antibonding). Overlap along the bonding axis is a sigma bond. Overlap above and below bonding axis (side to side overlap) is a pi-bond. 1.9 Hybridization--Single Bondshow do the most electrons get some benefit from the more stable s-orbital. Methanesp3 hybridization. Methane has four equal sigma bonds at corners of tetrahedron. They cannot be generated directly from electron configuration in atomic C. 1 2s and 3 2p-orbitals recombine to provide 4 sp3 orbitals of equal energy for bonding with H. sp3 orbitals are 25%s and 75% p character. When carbon uses two 2p-orbitals and one 2s orbitals it forms 3 equal trigonal planar sp2 orbitals (in one plane 120 bond angles). The remaining porbitals overlap to form a -bond. The double bond is one sigma and one pi-bond. Ethyne is sp hybridized and has two linear orbitals (180) in the sigma framework and two p-orbitals for forming pi-bonds. Problems. 1.20, SB1.7, 1.22 Methyl cation and anion (lecture only). The cation prefers sp2 hybridization with the empty orbital being a pure p-orbital (leaving all of the desirable s-character for orbitals with electrons).

The methyl anion has a non-bonded lone pair that prefers to be in an sp3 orbital rather than being stuck in a less desirable p-orbital if the anion were sp2 hybridized. 1.10 VSPER and Geometry and Water and ammonia. These are sp3 hybridized in order to keep the lone pair in an orbital with s-character (as opposed to being stuck in a p-orbital if atom is sp2 hybridized). HOH and HNH bond angles are compressed due to relatively large non-bonded lone pair. Problems: SB1.8, 1.25, 1.26, 1.27. Bond Dipoles, molecular polarity. Be able to use differences in atomic electronegativity (EN) to qualitatively predict polarized bonds (bond dipole). Although H is less EN than C treat C-H bonds as unpolarized and emphasize bonds with greater electronegativity differences. More charge separation = higher bond dipole. Be able to vector sum bond dipoles to sketch an overall qualitative molecular dipole. While it is good to do some quantitative problems as homework to build skills, we will only use resulting qualitative take-away message in quizzes/exams. Problems: SB1.9, 1.29.

1.11

1.12-13 Intermolecular attraction and physical (macroscopic) properties. Note that intramolecular stabilization of electrons within bonds and as non-bonded lone pairs account for heat of formation, bond strengths, overall molecular energy etc. Intermolecular attractions of electrons on one molecule for nuclei on adjacent molecules account for many physical properties such as boiling point and water solubility. Know how to justify van der Waal (London) attraction via induced dipoles, permanent dipolar attraction and hydrogen bonding (all are essentially flavors of intermolecular dipolar attractions). Problems SB1.10, 1.32, 1.33 Review concepts and terminology p. 42-43 and SkillBuilder concepts p. 43-45. Assigned Problems for End of Unit Do these problems when you have finished the chapter (or as indicated in lecture). 1.36, 1.38., 1/39, 1.43, 1.46, 1.48, 1.50, 1.52, 1.53, 1.58, 1.59, 1.61.

When you work the problems, you should copy enough of the question to enable your answer sheet to be understandabledont just write the answers. You should in most cases include a short key word phrase to explain the reason behind your answer (even when such comments are not included in the solutions manual. Use the FIFER-I approach of framing the question in terms that you can address, identifying factors, evaluating them and reaching a supported conclusionthen reevaluate the completeness of your answer and iterate method as needed. You should work all of the problems (on paper in your notebook). Read the solutions and correct any inaccuracies in a different color of ink. If you merely think your answers, then read the correct answer, you will perhaps fill in missing details in your answer and misjudge your level of understanding. You must be intellectually honest with yourself and know what you know and what you need to review.