Class Note for CHEM 112 at UMass(10)
Class Note for CHEM 112 at UMass(10)
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Date Created: 02/06/15
S u mma N of Rate Laws Table 151 Characteristic Properties of Reactions ofthe Type quotR gt Productsquot Rate Integrated Rate StraightLine Order Equatlun Equation Plot Slope k Units 0 rRTkR mu 7 Rkt mm r 7r motL time 1 awntramp Ln gamma in m itt vst 4 timequot 2 7ARTkRZ 1Rtr1Rukr 1Rt vst r Lmnt time What is the rate order for a reaction where the data look like A Ze ro I P 39 Q First 5 CSecond Tm D Fourth E What is the rate order for a reaction where the data look like ero ll 4 k B First CSecond le DFourth What is the rate order for a reaction where the data look like What did you think of the Oscars Did your favorite film win Did you have a drink after to celebrate Ethanol Oxidation Rates In Massachusetts legal intoxication is 008 by volume Adults average 40 L of uids At intoxication 40 Lx 008 32 ml ethanol in the bloodstream 0533 moles ethanol I 0015 0533 moles40 L 00133M b 39 1 008 ethanol by vo Uptake The small intestine takes up ethanol with a rst order reaction with t12 4 minutes 25 in different individuals Breakdown The liver oxidizes ethanol with a zero ogggr rate constant of000425 moleL hour using an enzyme called Liver Alcohol Dehydrogenase LAD LAD Ethanol NAD gt Acetaldehyde NADH H Ethanol Oxidation Rates One mole of ethanol CH3CH2OH 46 g by mass 60 ml by volume X beers 64 ethanol by volume X x 355 ml x 0064 Y ml ethanol Z mole ethanol X cocktails with 45 ml 15 02 each of 80 proof 40 ethanol Xx45 mx040 Y ml ethanol Z mole ethanol X bottles of wine 750 ml at 14 ethanol Xx 750 ml x 014 Y ml ethanol Z mole ethanol Ethanol Oxidation Rates One mole of ethanol CH3CH2OH 46 g by mass 60 ml by volume 3 beers with 355 mL 64 ethanol by volume E ml ethanol Ll mole ethanol 3 cocktails with 45 ml 15 02 each of 80 proof 40 ethaEnqobl l 14 q39glmL39 OJSZ 3gt MLquot 0439 9i ml ethanol mole ethanol 12 bottle ofwine 750 ml at 14 eth nol 9 any x1Sb l39 57 ml ethanol W mole ethanol Hwm h J wiuh Don t worry this is TOTALLY anonymous But relevant 125 lbs or less 57 kg 126150 lbs 5768 kg 150175 lbs 6880 kg 175200 lbs 8091 kg 200225 lbs 91102 kg More than 225 lbs 102 kg 95915905 L 10 Ethanol Oxidation Rates Calculate the ethanol oxidation of 3 people 50 70 and 90 kg 110 154 and 198 lbs Assumptions 70 of a person s weight is fluid typically 6575 An average liver is 16 kg typical is 1418 kg a An LAD enzyme rate c n tant of 000425 6 my a Sabiston s Textbook of Surgery 15th ed 1997 b Umlis et al 2005 Alcohol 35 312 11 Ethanol Oxidation Rates Ethanol oxidation by weight 1 mole ingested 008 l al drunk O 1 2 3 4 S 6 Time hours 12 Ethanol Oxidation Rates Now calculate what happens when a 57 kg 125 lb person ingests 1 2 and 3 moles of ethanol 13 Ethanol Oxidation Rates Ethanol Oxidation by 57 kg person quotm 99Dfu9flte e t7 1 mole ingested N houtS 7 15 hours u r 5 0 08 N3ENS egaHv drunk I s u 5 1n 5 2n Time hours 14 What controls how drunk ou yet A How much you drink vs your weight B How fast you drink vs your blood volume C Kinetics of alcohol absorption D Kinetics of alcohol metabolism EAl ofthe above AA 15 In my lab we work with an enzyme that cuts proteins leading to cell death Which ofthe following are true The cutting reaction is faster in the presence of the enzyme The cutting reaction is slower in the presence of the enzyme The same reaction is thermod namical mor favorabl the presence of the enzyme M 23 In The same reaction is thermodynamically less favorable in the presence of the enzyme The reaction is thermodynamically equally favorable in the presence of the enzyme m 16 Collisions leads to reactions To react molecules must collide with one another They must collide in an orientation that is favorable for reaction Rate of reaction is MOSTLY related to the concentration of reactions a 1 Mods 03 e 2 hitssecond b 2 quot015 03 e 4 hitssecond it 1ND 32 o e 4 hitssecond 1 IV Activation Energy and Temperature Reactions are faster at higher T because a larger fraction of reactant molecules have enough energy to convert to product molecules Lower tent parature In general Mm WWW differences in required m m activation I E energy cause reactions to vary from fast to slow Higher temperature Number of molecules with a given energy Kinetic energy 18 Reactants Transition state Products a 132 ltJmol Reacta nts E 352 kJmol Energy AE 7226 ltJmol Products N0 co2 gt Reaction progress 19 Cars amp Activation Energy Chemicals amp Activation Energy 15m09an1 15m09an2 15m09an3 15m10an1 20 Which of the following are true A If two molecules have enough energy they will react no matter the orientation B The activation is proportional to the molecular weight of the reactants C The activation energy is how much energy it takes to get over the barrier to form products D If the activation energy is high a large number of w molecules with react 21 A Closer Look Reaction Coordinate Diagrams Reaction coordinate diagrams Figure 1513 can convey a great deal ofinforma tion Another reaction that would have an energy diagram like that in Figure 1513 is the substitution of a halogen atom of CHgCl by an ion such as F39 Here the F39 ion attacks the molecule from the side oppo site the Cl substituent AS F39 begins to form a bond to carbon the C Cl bond weakens and the CH portion of the mole cute changes shape As time progresses the producb CHgF and 139 are formed F cngcl 3 8 4 Length J o Qa O J H Cl Energy at intermediate F5 for step 2 Energy Reactants Reaction progress Figure A A reach39on coordinate diagram for a twostep reaction a process involving an intere mediate The diagram in Figure A shows a differ ent type of reaction a twostep reaction that involves a martian intermediate An example would be the substitution of the 70H group on methanol by a halide ion in the presence of acid In the rst step an H ion attaches to the o oi the c 70 group in a rapid reversible reaction Acti vation energy is required to reach this state The energy ot this protonated species CH30H2 a reaction intermediate is higher than the energies of the reactants and is represented by the dip in the curve shown in Figure A In the second step a halide ion say or attacks the intermedie ate in a process that requires further actir vation energy The nal resutt is methyl bromide HgBT and water I W J r J CHXDH H J O J J cHgohzt 39 a 15quot o CH30H1 or J y 2 J J CH3Br H20 Notice in Figure A as in Figure 1513 that the energy of the products is lower than the energy of the reactants The reaction is exothermic 22 More About Activation Energy Arrhenius equation Frequency factor related to frequency of collisions with correct geometry 23 More About Activation Energy Arrhenius equation k Ae EaRT Take natural log of both sides Ea 1 Ink T lnA 24 MECHANISMS amp Activation Energy Hzc CH H H cc g gt cc g H H H CH3 derrbiitene Tianxitiun state transvzbutene 4 J x V band break Conversion of cis to transZbutene requires twisting around the 00 bond Rate ktrans2 butene 25 IodineCatalyzed Isomerization of cis 2 Butene 1 a H steps Step 1 J V 34 J J Step 2 5m 1 J a J J Figure 1516 Step 2 25 IodineCatalyzed Isomerization of cis 300 Uncatalyzed veactv39un E 251 Klmnl znu Camtyzed A reat un S 5 mu 3 n R d t mam ea an 3 f 4 k mm mm IZ nanycmx IZ 7mm Reac nn pmgvess 27
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