General Chemistry Review Chapters 1 & 2 General Chemistry Review Electronic Structure and Bonding Molecular Representations

Molecular Representations Klein: 2.1, 2.2, 2.6 5

Molecular Representations Empirical Formula, Molecular Formula, Structure: (Lewis, Kekule, Condensed, Line), Visual Model: wireframe, stick, ball & stick, space filling, electrostatic, energy surface

Draw bond-line structures for each of the four molecules. ketone 1. aldehyde 2. carboxylic acid 3. ester (carboxylic acid ester) Figure Number: 01-01-31T05UN Title: Table 1.5 An oxygen doubly bonded to a carbon. Caption: Condensed structures can be written in different forms Notes: The condensed structures are simplified by omitting some or all of the covalent bonds (lines and dots) and listing atoms bonded to a particular carbon (or nitrogen, or oxygen) next to it with a subscript to indicate the number of such atoms. 4.

Introduction to Organic Functions (Functional Groups) (Klein 2.3) ketone 1. aldehyde 2. carboxylic acid 3. ester (carboxylic acid ester) Figure Number: 01-01-31T05UN Title: Table 1.5 An oxygen doubly bonded to a carbon. Caption: Condensed structures can be written in different forms Notes: The condensed structures are simplified by omitting some or all of the covalent bonds (lines and dots) and listing atoms bonded to a particular carbon (or nitrogen, or oxygen) next to it with a subscript to indicate the number of such atoms. 4. Worksheet 3: Organic Functional Groups (2 Sudoku) http://chemconnections.org/organic/chem226/226assign-12.html#Worksheets Worksheet 4: Functions, Polarity, Formal Charge http://chemconnections.org/organic/chem226/226assign-12.html#Worksheets 6

Question 2.1 The molecular formula of morpholine is: A) C2HNO B) C4HNO C) C4H4NO D) C4H5NO E) C4H9NO

Question 2.2 The respective number of bonded pairs of electrons and of unshared pairs of electrons in morpholine is: A) 7, 0 B) 7, 1 C) 15, 0 D) 15, 1 E) 15, 3

Formulas & Kekulé / Condensed / Bond-Line Structures / Drawings Molecular formula? Empirical Formula? C7H16O C7H16O Bond-Line Structure? Figure Number: 01-01-29T05UN Title: Table 1.5 Groups bonded to the far right carbon. Caption: Notes:

Question 2.3 The bond-line representation for (CH3)2CHCH2CH2CHBrCH3 is A) B) C) D)

Question 2.4 Select the best condensed structural formula for the following bond-line structure: (CH3)2CHCH2COHOHCOH CH3CH3CHCH2C(OH)2CHO (CH3)2CHCH2C(OH)2CHO (CH3)2CHCH2C(OH)2COH CH3CHCH3CH2C(OH)2CHO

Line Drawing and Ball & Stick 8.16 Å (0.816 nm) http://chemconnections.org/COT/chemical-communication/ChemComm.html

Question 2.5 While on-line, examine the jmol-structure on the left. Which one of the formulas or structural renderings that follow is correct? http://chemconnections.org/organic/chem226/Labs/VSEPR/acetic-acid.html 13

Worksheet 2: Structures, Formulas & Orbitals http://chemconnections.org/organic/chem226/226assign-12.html#Worksheets

Question 2.6 How many constitutional alcohol isomers have the molecular formula C4H10O? A) two B) three C) four D) five E) six SEE: http://m.wolframalpha.com/examples/Chemistry.html

Worksheet: Organic Molecules 1 More Molecular Representations Empirical Formula, Molecular Formula, Structure: (Lewis, Kekule, Condensed, Line), Visual Model: wireframe, stick, ball & stick, space filling, electrostatic, energy surface Worksheet: Organic Molecules 1 http://chemconnections.org/COT/organic1/VSEPR/

Very Large Molecules:DNA http://www.umass.edu/microbio/chime/beta/pe_alpha/atlas/atlas.htm Views & Algorithms 10.85 Å 10.85 Å 15-23 Title: Base Pairs Caption: Representation of the base pairings of thymine and adenine, and cytosine and guanine, in line as well as ball-and-stick models. Notes: Base pairs occur through hydrogen bonding. Several formats are commonly used but all rely on plotting atoms in 3 dimensional space; .pdb is one of the most popular.

B-DNA: Size, Shape & Self Assembly Very Large Molecules http://info.bio.cmu.edu/courses/03231/ProtStruc/ProtStruc.htm B-DNA: Size, Shape & Self Assembly 46 Å Rosalind Franklin’s Photo 12 base sequence (1953-2003) http://molvis.sdsc.edu/pdb/dna_b_form.pdb

Atomic Orbitals Valence Bond theory Molecular Orbital Theory Klein: 1.6 – 1.9 5

Atomic Orbitals Experimental data shows that electrons, like light and photons, behave as BOTH particles and waves. Orbital theory that was developed from this observation offers the ability to make fairly accurate predictions. Like a lake’s wave, an electron’s wavefunction can be (+), (-), or ZERO.

Atomic Orbitals Orbitals are mathematically derived from wavefunctions. (Solutions for values of ℓ.) Remember the four q.n.: n (principal), ℓ (orbital), mℓ (magnetic), ms (spin) Orbital regions can be (-), (+), or ZERO based on mℓ . In the example on the right of a p-orbital, ℓ = 1, there are three possible values for mℓ . The point where mℓ = 0 is referred to as a Node or nodal plane. The sign of mℓ is important in considering orbital overlap and bond formation.

Atomic Orbitals s and p orbitals

Atomic Orbitals Molecular Orbital (MO) Atomic orbitals mix to form molecular orbitals The total number of molecular orbitals (bonding + non- and anti bonding orbitals) equal the total number of atomic orbitals s bond is formed by overlapping of two s orbitals

MO & Valence Bond Theories A bond occurs when certain atomic orbitals overlap. These overlapping orbitals are like waves. Only constructive interference results in a bond.

In-phase overlap of s atomic orbitals form a bonding MO (no node); Out-of-phase overlap forms an antibonding MO (has node) A single bond is a s bond with a bond order of 1.

A sigma bond (s) is also formed by end-on overlap of two p orbitals Double bonds have 1 s and 1 p bond with a bond order of 2. A p bond is weaker than a s bond. A double bond is shorter and stronger than a single bond.

Molecular Orbital Theory Consider the MOs for CHBr3: There are many areas of atomic orbital overlap. Notice how the MOs extend over the entire molecule. Each image represents ONE orbital, which depending on its energy can be bonding (lowest) or non-bonding (higher) or anti-bonding (highest).

Pi bond (p) is formed by sideways overlap of two parallel p orbitals

Mixing Atomic Orbitals Hybridization of s and p orbitals 30

Single Bonds (Methane) Hybridization of s and p atomic orbitals:

The atomic orbitals used in bond formation determine the bond angles Tetrahedral bond angle: 109.5° Electron pairs spread themselves into space as far from each other as possible

Hybrid Orbitals of Ethane Practice: CONCEPTUAL CHECKPOINT 1.19

Bonding in Ethene: A Double Bond Double bonds have 1 p and 1 s bond. A double bond is shorter and stronger than a single bond. Practice: CONCEPTUAL CHECKPOINT 1.20

Ethene: Molecular Orbitals MO theory provides a similar theoretical picture: NOTE: the red and blue regions are part of the same orbital.

An sp2-Hybridized Carbon The bond angle in the sp2 carbon is 120° The sp2 carbon is the trigonal planar carbon http://chemconnections.org/organic/Movies%20Org%20Flash/HybridizationofCarbon.swf

Ethyne: A Triple Bond sp-Hybridized Carbon A triple bond consists of one s bond and two p bonds with a bond order of 3. Triple bonds are shorter and stronger than double bonds There is a bond angle of the sp carbon: 180°

Question 2.7 What is the molecular shape of each of the carbons of tetrachloro ethene (Cl2CCCl2)? A) tetrahedral B) bent C) trigonal planar D) linear E) trigonal pyramidal

http://chemconnections.org//organic/Movies Org Flash/hybridization.swf

Summary A p bond is weaker than a s bond The greater the electron density in the region of orbital overlap, the stronger is the bond The more s character, the shorter and stronger is the bond The more s character, the larger is the bond angle

Hybridization & Bond Strength Being able to explain the different strengths and lengths: CONCEPTUAL CHECKPOINT 1.24.

Reactive Carbon Atoms Klein: 2.4 5

Reactive Intermediates Carbocation

Reactive Intermediates Radical

Reactive Intermediates Carbanion