MPOC Ch8. Forthe aboveelimination 1 7. Dissociation. than C D. If C HID bond is breaking in the RDS Kitshouldbe than KD

Similar documents
A L A BA M A L A W R E V IE W

2) Of the following questions, which ones are thermodynamic, rather than kinetic concepts?

P a g e 5 1 of R e p o r t P B 4 / 0 9

CHEMICAL KINETICS: 1. Rate Order Rate law Rate constant Half-life Temperature Dependence

T h e C S E T I P r o j e c t

AP Chemistry--Chapter 12: Chemical Kinetics

Trade Patterns, Production networks, and Trade and employment in the Asia-US region

176 5 t h Fl oo r. 337 P o ly me r Ma te ri al s

Advanced Organic Chemistry

OH BOY! Story. N a r r a t iv e a n d o bj e c t s th ea t e r Fo r a l l a g e s, fr o m th e a ge of 9

2 tel

Chapter 12. Chemical Kinetics

Chapter 15: Phenomena. Chapter 15 Chemical Kinetics. Reaction Rates. Reaction Rates R P. Reaction Rates. Rate Laws

Executive Committee and Officers ( )

Chapter 13 Homework Answers

Second order reactions. Second order, class I reactions 2A P A + B P. class I. class II. Nov 17, 2010!

1. (18 points) The reaction given below is performed in water at a ph above the pka of ethane thiol, thus making ethane thiolate:

I M P O R T A N T S A F E T Y I N S T R U C T I O N S W h e n u s i n g t h i s e l e c t r o n i c d e v i c e, b a s i c p r e c a u t i o n s s h o

Name. CHM 115 EXAM #2 Practice KEY. a. N Cl b. N F c. F F d. I I e. N Br. a. K b. Be c. O d. Al e. S

Chapter 14 Chemical Kinetics

Beechwood Music Department Staff

Northern Arizona University Exam #1. Section 2, Spring 2006 February 17, 2006

KIE = k H. k D SM H SM! D PDT H PDT D. Kine%c Isotope Effects. Ques%ons: What is the mechanism of a reac%on?

HIGGS&AT&HADRON&COLLIDER

Chapter 15: Reactions of Substituted Benzenes

C is very reactive, difficult to control and stabilize

CHM 115 EXAM #2 Practice

V;Y. i\ l-' / Student ID: Recitation day and time:

Math 2214 Solution Test 1B Fall 2017

Relaxation in Glass. Transition

KEY. Math 334 Midterm I Fall 2008 sections 001 and 003 Instructor: Scott Glasgow

Module 3: The Damped Oscillator-II Lecture 3: The Damped Oscillator-II

I n t e r n a t i o n a l E l e c t r o n i c J o u r n a l o f E l e m e n t a r y E.7 d u, c ai ts is ou n e, 1 V3 1o-2 l6, I n t h i s a r t

( ) is the stretch factor, and x the

PET467E-Analysis of Well Pressure Tests/2008 Spring Semester/İTÜ Midterm Examination (Duration 3:00 hours) Solutions

Today in Physics 218: radiation reaction

Two Coupled Oscillators / Normal Modes

Electrical Circuits. 1. Circuit Laws. Tools Used in Lab 13 Series Circuits Damped Vibrations: Energy Van der Pol Circuit

An recursive analytical technique to estimate time dependent physical parameters in the presence of noise processes

INVERSION IN THE PLANE BERKELEY MATH CIRCLE

Physics 235 Chapter 2. Chapter 2 Newtonian Mechanics Single Particle

Problem Set on Differential Equations

Let us start with a two dimensional case. We consider a vector ( x,

Assignment 6. Tyler Shendruk December 6, 2010

Chapter 14 Chemical Kinetics

1 Nuclear particles and nuclear radiation may cause ionisation as they pass through matter.

Multi-Frequency Sheath Dynamics

L1, L2, N1 N2. + Vout. C out. Figure 2.1.1: Flyback converter

MIT Amorphous Materials

Introduction to AC Power, RMS RMS. ECE 2210 AC Power p1. Use RMS in power calculations. AC Power P =? DC Power P =. V I = R =. I 2 R. V p.

ACE 564 Spring Lecture 7. Extensions of The Multiple Regression Model: Dummy Independent Variables. by Professor Scott H.

Ranking accounting, banking and finance journals: A note

Using the Rational Root Theorem to Find Real and Imaginary Roots Real roots can be one of two types: ra...-\; 0 or - l (- - ONLl --

Suggested Problem Solutions Associated with Homework #5

NAME (please print) MIDTERM EXAM FIRST LAST JULY 13, 2011

Chapter Q1. We need to understand Classical wave first. 3/28/2004 H133 Spring

A) Arrhenius Acids produce H+ and bases produce OH not always used because it only IDs X OH as basic species

h : sh +i F J a n W i m +i F D eh, 1 ; 5 i A cl m i n i sh» si N «q a : 1? ek ser P t r \. e a & im a n alaa p ( M Scanned by CamScanner

Chapter 14 Homework Answers

Formulas and Constants (you may remove this page)

EXCHANGE RATE ECONOMICS LECTURE 3 ASYMMETRIC INFORMATION AND EXCHANGE RATES. A. Portfolio Shifts Model and the Role of Order Flow

Module 4: Time Response of discrete time systems Lecture Note 2

Chem. 1B Final Practice Test 2 Solutions

NMR Spectroscopy: Principles and Applications. Nagarajan Murali 1D - Methods Lecture 5

A Dynamic Model of Economic Fluctuations

Substitution and Elimination reactions

Nuclear Decay kinetics : Transient and Secular Equilibrium. What can we say about the plot to the right?

CHAPTER 13: ACIDS & BASES. Section Arrhenius Acid & Bases Svante Arrhenius, Swedish chemist ( ).

M10/4/CHEMI/SPM/ENG/TZ2/XX+ CHEMISTRY. Wednesday 12 May 2010 (afternoon) 45 minutes INSTRUCTIONS TO CANDIDATES

CHBE320 LECTURE IV MATHEMATICAL MODELING OF CHEMICAL PROCESS. Professor Dae Ryook Yang

Chapter 5: Discontinuous conduction mode. Introduction to Discontinuous Conduction Mode (DCM)

Elimination reactions

A First Course on Kinetics and Reaction Engineering. Class 19 on Unit 18

EQUATIONS REVIEW I Lesson Notes. Example 1. Example 2. Equations Review. 5 2 x = 1 6. Simple Equations

Ecological Archives E A1. Meghan A. Duffy, Spencer R. Hall, Carla E. Cáceres, and Anthony R. Ives.

Some Basic Information about M-S-D Systems

CATAVASII LA NAȘTEREA DOMNULUI DUMNEZEU ȘI MÂNTUITORULUI NOSTRU, IISUS HRISTOS. CÂNTAREA I-A. Ήχος Πα. to os se e e na aș te e e slă ă ă vi i i i i

( ) Thermodynamic selectivity (reversible reactions)

Created by T. Madas MIXED SURD QUESTIONS. Created by T. Madas

Chap. 8 Substitution Reactions

Math 333 Problem Set #2 Solution 14 February 2003

A single crystal investigation of L-tryptophan with Z = 16

ψ ( t) = c n ( t) t n ( )ψ( ) t ku t,t 0 ψ I V kn

P a g e 3 6 of R e p o r t P B 4 / 0 9

Position, Velocity, and Acceleration

EE 330 Lecture 41. Digital Circuits. Propagation Delay With Multiple Levels of Logic Optimally driving large capacitive loads

Presentation Overview

Activity 4 Solutions: Transfer of Thermal Energy

USP. Surplus-Production Models

Biol. 356 Lab 8. Mortality, Recruitment, and Migration Rates

Nature of superconducting fluctuation in photo-excited systems

Lesson Ten. What role does energy play in chemical reactions? Grade 8. Science. 90 minutes ENGLISH LANGUAGE ARTS

The general Solow model

Faculty of Natural and Agricultural Sciences Chemistry Department. Semester Test 1 MEMO. Analytical Chemistry CMY 283

EE 435. Lecture 31. Absolute and Relative Accuracy DAC Design. The String DAC

Organic Chemistry CHM 314 Dr. Laurie S. Starkey, Cal Poly Pomona Alkyl Halides: Substitution Reactions - Chapter 6 (Wade)

Welcome to the Public Meeting Red Bluff Road from Kirby Boulevard to State Highway 146 Harris County, Texas CSJ No.: December 15, 2016

Chem 209 Final Booklet Solutions

SUPPLEMENTARY INFORMATION

Numerical Dispersion

Transcription:

MPOC Ch8 KineicisoopeEffec soopeshave he same chemical properies Labeling will no changehemechanism H o Ph Br v ph H D D O D Ph rbr ph u soopes can minimally perurb he rim leadingo a change in An rae KE KD ligh isoope heavyisoope Forhe aboveeliminaion 1 7 Origin Vibraional saes are quanized The lowes energy vibraional sae Zero poin energy 2PE H X D V forceconsan Mr mx.m.noew1e 1 2.186g reduced mass Mx Mmolecule 184 21186 UH Loser1Hisher E vibraion VD Smaller Lower E vibraion Lower 2 PE 0.995 1.99 MorsePoenial Dissociaion µzpe Breaking C H requires less C D 2PE energy han C D f C HD bond is breaking in he RDS Kishouldbe han KD is issues sa EEance

Experimens o Sudy Rin Mechanisms Z Z Z Z T N0z N Oz KD pka 8 S 2 H or D pka 5.6 This is a primary LGOy Oxidaion i TO iz Cg lo kbrag Ki 7.2 kineic isoope effec C H C D bond breaks in he RDS Maximum of 8 Lower for early or lae ransiion saes o o H o c i 11 0 11 P.T S Hol 1 Ho Cr H o Cri f orange Wih C D he colorchase b bo is much slower 09 0 120 M Primark k E Horas l o CT KHA 5.9 green R NMR GL HPLC can all be Used o deermine produc raios o measure KE Secondary Kineicsoope Effec C HC D bonds are close o he reacive sie bu do no break in he RDS Sp's Sp2 in RDS dissociaive Ph i fpn ifiii.us PhfEjf H D H has CP smaller Normal Secondary KE 1 1,4 L KE barrier

Sp Sp's in RDS associaive 0 H RDS 11 HCN 11 Ar HD Ar HD ART HD CN CN 0.73 nverse Secondary KE commonly 0.800.9 D Fi The ou of plane bending dominaes he secondary ki Hy Hb Dhassmaller us 5 barrier 800cm 1350cm weaker forceconsan Smaller C HC D Gap Bc 8 FCTETS Fbc Oas 8Ts k 0.96 W w Grea LG more Sp3 like X inverse S of OTS Secondary KE BC w more sp2 like T.i Ef c io B normal secondary KE

Experimens o Sudy Rin Mechanisms LinearFreeaionships LEER Goal Sudy how subsiuens influence he rae or equilibrium of a rim HammePlos Scale o measure he abiliy of subsiuens o influence he acidiy of benzoic acid x 7 0 ho 7 he 8 13010 X mea or para f 7 0 o o pka 4.21 g HE y me EDG o N 4 TW6 pka 4.48 Y pka 3.44 0 0.27 0 0.77 Subsiuen parameer o for eachsubsiuen For Ph CO of O ox log K PKa H pka KH when 0 0 X EDG Lessacidichan PhCO when 0 X EWG More acidichan PhCO For PhCO opera ome.la induciveeffec inducive e resonance effec y Ho 0 7 K 0 0.13 0 0.38 Rho P Nin KO Using Ph as a reference rxn ha creaes a 0 Chase Compare oher rxn o see if i involves a or 0

O Ar fele Ph Y Ar q B RDS Near Ar p 3 Builds up in RDS o_o puff Ar NK Ph o g A Hl H s pu Nk Ar Ar go Ph O_O Near Ar Ar 101 p 1 S Builds up in RDS NL Ph Ex 6 Esimae K when X NO 0 0.71 me o im log 1k Po 1 popo Kx 1000 KH 1012.38 071 2 10 4 M s 9.8 10 3 MS A non linear plo can indicae change in mechanism or RDS lien Bo Bo 7710

i OheroosformechorismDeerminaif Wih EWG he eliminaion becomes he RDS 1 denify all producs 2 nermediaetrapping SEE f 7 rapwih furan Nk 3 Crossover Experimen Use o see if a reacan breaksapar before recombining o give a produc Claisen Rearrangemen Pan.n

5 Pah B F oo Experimen a is OT 7 e Xx 6 Mus operae via a CrossoverProducs Concered Mechanism No Formed 4 Sereochemical Analysis Cl be a c Oc by Odb s 0 13 Experimen yes go f en Consisen wih mechanism C Cl Oas S soope Tracing p o Ph p which subsiuen migraed

Benzyne n me 6 Radical Clocks e Traps Used o rap a suspecedradical inermediae j j y K 108 s l Newcomb Terahedron 19931151 l K 109 S i in Ph Ph Ph K 10 s Example Tk z Eo r Ta r r EQyR Naure 2018 1972 L Na EOzC R Eoze ri carbene coffee P R 74 R f RMR R

Experimens o Sudy Rin Mechanisms 100 Used cyclopropane as a radical rap.o.e T T T T r ou Ph CozE Ph RadicalCaion Trap Newcomb JACS 19949753 XJR g R g R r 9 Phl home phl home phl me H R H Phl Once p me R