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This course will be team taughtwe will manage the entire course as a team, including lectures, quizzes and exams
Understanding
Time Many of life's failures are people who did not realize how close they were to success when they gave up. ~ Thomas Edison
You may attend more than one discussion per week, if space You may earn up to 10 bonus points over the semester for 4 attending office hours (max 1 per week)
OFFICE HOURS
We will hold 12 office hours weekly beginning next week Professor Oakley will hold office hours this week from 3:00-4:00 on Tuesday and from 4:00 to 5:05 on Thursday, Simon Hall (across from Jordan), Room 320B. Professor Brown will hold office hours this week on Monday 9-10 am and Wednesday from 12:20-1:20 in Chemistry A112 Regular office hours begin next week.
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Grading
Quizzes (see syllabus for dates) best 3 out of 4 (100 pts) Early quizzes available only for university sanctioned events, etc. Exams 3 x 2 hr exams; Tues evenings (150 pts each) Final Exam (300 pts) Drop lowest exam or of final grade, whichever is lowest YOU ARE RESPONSIBLE FOR READING THE SYLLABUS
Grading Cutoffs
The instructors do not grade on a curve (A) understands the material well and can apply it creatively to new situations. Cutoff for an A- no higher than 90%. (B) Good, solid understanding of the material Cutoff for a B- no higher than 75% (C) Major gaps in understanding Cutoff for a C- no higher than 60%. (D or F) Still larger gaps
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Active Learning
You should be thinking during class We will do lots of problem-solving in class We will call on students to help us work problems You should be trying to work the problem at the same time as the student who has been called on You get a bonus point every time you participate right or wrong There are no other ways to earn bonus points, except for discussion attendance
Courtesy in Class
This is a large room and there are a lot of people in it. Whispering in class makes it difficult for others to hear the lectures This class costs a lot of money! Lecture attendance is optional in this course Should you choose to attend lecture, we expect you to be courteous to us and to your classmates If we are slowed or cannot continue because of noise, you are responsible for all the material we would have covered without the noise.
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B. Write a Lewis structure for diazomethane (CH2N2) and assign each atom a formal charge (connectivity as shown)
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B. Move from electron source to electron sink source: sink: ________ __________ charge or _____________ _____________
charge or partial
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III. Resonance
A. Provide appropriate curved arrows to show how to generate additional resonance structures (if possible)
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B. How many resonance structures can you draw for the benzyllic cation (5 possible)? Show the electron flow between each one.
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continued
O S
-O
CH3 S
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A.
B.
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Provide Arrows
Provide mechanistic arrows, indicating the direction of electron flow, for the following one-step transformation. Hint:number your carbons. Where are bonds broken or formed?
O H
H O
O H O N H O H H H N
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Which of these groups of mechanistic arrows is correct? Why? Electron source? Sink?
H N
+HN
CO2H N H O CH3
H H N
CO2H O CH3
N+ H
N H
H N
+HN
CO2H N H O CH3
H H N
CO2H O CH3
N+ H
N H
VI. Nomenclature
You should be able to write structures from IUPAC or common names Examples: 1. isopropanol (2 propanol) 2. cis 3-hexene (Z-hexene)
3. tert-butanol (2,2-dimethylethanol)
4. trans-2-butene (E-butene)
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(1) Gravitational
(2) Electrical
(3) Chemical 24
Free Energy is a Combination of Enthalpy and Entropy G = H TH If G < 0, reaction is product-favored If G >0, reaction is reactant-favored In other words: If G < 0, reaction is thermodynamically favorable (higher to lower energy) If G >0, reaction is is thermodynamically unfavorable (lower to higher energy)
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Example of an Exothermic Reaction. Where does the energy come from? Consider the reaction H2(g) + Cl2 (g) --> 2 HCl
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O
Keto tautomer
These molecules are a special kind of isomer of one another called tautomers (molecules that differ by the placement of a double bond and a proton).
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OH
Bonds broken:
Bonds formed:
Enthalpy of reaction:
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+ H2
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Chemical Equilibrium
Concentrations of products and reactants at equilibrium are CONSTANT. Equilibrium is DYNAMIC; the rates of the forward and reverse reactions are equal. Equilibrium concentrations are independent of the direction of approach (same reaction, same temp). 32
At equilbrium, add a tiny amount of radioactive sodium acetate: C*H3COOGet labeled acetic acid: C*H3COOH How can this happen?
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Figure 14.1
2NH3(g) 34
Rateforward = kforward [cis-butene] Ratereverse = kreverse [trans-butene] What happens to the concentrations of cis and trans butene as we approach equilibrium?
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[trans-butene] eq [cis-butene]eq
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Only consider substances whose concentrations change as the reaction occurs. Should we consider: A) B) C) D) E) Pure solids Pure liquids Gases Solutes in dilute solutions (the stuff thats dissolved) Solvents in dilute solutions
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Figure 14.6
Can drive a reaction to completion by removing one of the products. Acid-Catalyzed Esterification of Carboxylic Acids
O OH OH H2SO4 O O
The concentrations of reactants and products at equilibrium are dictated by the difference in free energy between them:
At room temperature, For example calculate Keq for following reaction: N2(g) + 3H2 (g) G =-32.90 kJ 2NH3(g)
Or to estimate, Keq =
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O
+ CO2 (g)
OH OH
NH3
OH
NH4
Keq ~ 1016
init. 1 mmol 1 mmol 0 mmol 0mmol Note: your book uses .33 mmol arrows only when the reaction is actually at eq. .33 mmol equilibrium .67 mmol .67mmol
equilibrium. This is technically correct but not very useful pedagogically. We will use reversible arrows to indicate that both forward and reverse reactions are occurring.
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H-A+
H+ + A
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So, the higher the pKa, the stronger or weaker the acid?
Acid-Base Equilibria
In which direction does the equilibrium lie? Is Keq < 1 or > 1? Keq=
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Where K = Ka
Ka =
OH acetic acid H O H
NH3+
Note:
NH4+ NH2 O
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H 2O
HF
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H C C H
Conj base? pKa?
H C N:
name?
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OH OH O O
OH
O OH
v.
OH
OH
OH
4.8
15.9
10
15
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H3C CH3
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name? pKa 4.8 3.2 2.9 2.6 As halogen electronegativity increases, pKa _____________
O OH Cl Cl Cl OH Cl
O OH Cl
O OH Cl
pKa 4.8
2.9
1.5
0.7
v.
O OH
name?
OH
OH
OH
NO2
NO2
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Explain:
8.4
7.2
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When the acid is neutral, consider the stability of the conjugate base. The more stable (less reactive) the conjugate base, the more reactive the acid, lower pKa. 58
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acid O OCH3 H
pKa
-6.5
Why is the protonated ester more acidic than the protonated amide? Hint: think about resonance structures.
H O NH2
O NH2 -0.5
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List the five structural factors important for determining the pKa of an acid:
1) 2) 3) 4) 5)
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