Chem 125

Winter 2010 More Kinetics Problems

Dr. Neff

12. The conversion of t-butyl bromide to t-butyl alcohol is achieved in the first order reaction (CH3)3CBr + H2 (CH3)3C H + HBr (loo! familiar at all") The half-life of this reaction is 1#.1 hours at 2$%C and #&.& min at $'.%C. Ho( lon) (ill it ta!e for this conversion to )o to *'+ com,letion at -$%C" 13. n the basis of the fre.uency factors and activation ener)y values of the follo(in) t(o reactions/ determine (hich one (ill have the lar)er rate constant at 2*& 0. ()) 2 ()) + 2 ()) 3 ()) + 1 2 &.' 3 1'-12 cm34molecule 5s 6a 2 17.1 !84mol ()) + 3 ()) + Cl ()) Cl 1 2 2.* 3 1'-11 cm34molecule 5s
2

()) 6a 2 2.1- !84mol

1#. 1 rule of thumb in chemical !inetics states that for many reactions/ the rate of reaction a,,ro3imately doubles for a tem,erature rise of 1'.'%C. 9hat must be the activation ener)y for a reaction if the rate is indeed found to double bet(een 2$%C and 3$%C" 1$. :ra( a rou)h s!etch of the reaction ener)y dia)ram (,otential ener)y ,rofile) for each of the follo(in) cases/ labelin) H/ 6a/ reactants/ transition state/ and ,roducts. (a) H 2 +1' !84mol/ 6a 2 2$ !84mol (b) H 2 -2' !84mol/ 6a 2 $' !84mol (c) 1dd to the dia)ram in ,art (a) a cataly;ed reaction ,ath. 16. The reaction 1 + 2 B C + 2 : is found to be first order in 1 and first order in B. ,ro,osed mechanism for the reaction involves the follo(in) first ste,< 1 + B = + : (slo( ste,) a) 9rite a ,lausible second ste, to )o (ith this first ste,/ to ma!e a t(o-ste, mechanism. b) =s the second ste, fast of slo(" 63,lain" ne

17. 1t tem,eratures belo( -'' 0/ the follo(in) reaction e3hibits the rate la(< >ate 2 !?@ @
2

A2.

()) + C

()) @

()) + C

())

Bro,ose a t(o-ste, mechanism involvin) one fast ste, and one slo( ste, that is consistent (ith the net e.uation and the observed rate la(.

Chem 125

Winter 2010

Dr. Neff

1&. 63,lain (hy the follo(in) mechanism is not ,lausible for the reaction in ,roblem 1- above< Cast 2@ 2 @2 # Dlo( @2
#

+2C

2@

+2C

1*. The rate la(s for the thermal and ,hotochemical decom,ositions of @ 2 are different. 9hich of the follo(in) mechanisms are ,ossible for the thermal decom,osition of @ 2 and (hich are ,ossible for the ,hotochemical decom,osition of @ 2" The rate of thermal decom,osition 2 !?@ 2A2 and the rate of ,hotochemical decom,osition 2 !?@ 2A. a. b. @ ()) + @ @
2 2

()) @ ()) + ()) + 2 ()) @

()) 2 ())

slo( fast

()) + @ 2 ()) @2 # ()) fast/ reversible @2 # ()) @ ()) + 2 ()) slo( @ 3 ()) @ ()) + 2 ()) fast
2

c. .

()) + @ 2 ()) @ ()) + @ 3 ()) slo( @ 3 ()) 2 @ ()) fast

2'. The rate la( for the reaction

2@ Step 1 Step 2 Step 3

()) + 2 H2 ())

@2 ()) + 2 H2

())

is rate 2 ! ?@ A2 ?H2A. The mechanism that has been ,ro,osed for this reaction is

2 @ ()) @2 @2 2 ()) + H2 ()) @2 ()) + H2 ())

()) fast, reversible @2 ()) + H2 ()) slow @2 ()) + H2 ())

a) Dho( that this mechanism is valid. b) D!etch a reaction ener)y dia)ram for this e3othermic reaction. Eabel the activation ener)ies of each ste, and the overall reaction enthal,y.