Kinetics: Rates and Mechanisms of Chemical Reactions Chapter 16

Multiple Choice Questions 1. E The compound RX3 decomposes according to the equation 3RX3 R R!X3 3X!

"n an e#periment the follo$ing data $ere collected for the decomposition at 1%%C. &hat is the a'erage rate of reaction o'er the entire e#periment( t)s* % ! 6 / 1! 12 a. 3. c. d. e. !. M +RX3,)mol -.1* %./0 %.61 %.21 %.33 %.!% %.16

%.%11 mol -.1s.1 %.%14 mol -.1s.1 %.%22 mol -.1s.1 %.%24 mol -.1s.1 %.%64 mol -.1s.1

Consider the follo$ing reaction /5)g* 06)g* /C)g* 67)g*

"f +C, is increasing at the rate of 2.% mol -.1s.18 at $hat rate is +6, changing( a. 3. c. d. e. 3. M .%.2% mol -.1s.1 .!.0 mol -.1s.1 .2.% mol -.1s.1 .6.2 mol -.1s.1 none of the a3o'e8 since its rate of change must 3e positi'e

Consider the general reaction 06r.)aq* 6r93.)aq* 6: )aq* 36r!)aq* 3:!9)aq*

;or this reaction8 the rate $hen e#pressed as +6r!,<t is the same as a. b. c. d. e. .+:!9,<t 3+6r93.,<t .0+6r.,<t .%.6+6r.,<t none of the a3o'e

242

2. M

Consider the reaction !=:3)g* =!)g* 3:!)g*

"f the rate +:!,<t is %.%3% mol -.1 s.18 then +=:3,<t is a. 3. c. d. e. 0. M .%.%20 mol -.1 s.1 .%.%3% mol -.1 s.1 .%.%!% mol -.1 s.1 .%.%1% mol -.1 s.1 none of the a3o'e

;or the reaction 35)g* !6)g* !C)g* !7)g*

the follo$ing data $ere collected at constant temperature. 7etermine the correct rate la$ for this reaction. Trial 1 ! 3 2 a. 3. c. d. e. 6. M "nitial +5, )mol<-* %.!%% %.1%% %.!%% %.3%% "nitial +6, )mol<-* %.1%% %.1%% %.!%% %.!%% "nitial Rate )mol<)->min** 6.%% 1%.! 1.0% 1%.! 1.!% 1%.1 !.1% 1%.1

Rate ? k+5,+6, Rate ? k+5,+6,! Rate ? k+5,3+6,! Rate ? k+5,1.0+6, Rate ? k+5,!+6,

;or the reaction 5)g* !6)g* !C)g* !7)g*

the follo$ing data $ere collected at constant temperature. 7etermine the correct rate la$ for this reaction. Trial 1 ! 3 2 a. 3. c. d. e. "nitial +5, )mol<-* %.1!0 %.310 %.!0% %.310 "nitial +6, )mol<-* %.!%% %.!%% %.2%% %.2%% "nitial Rate )mol<)->min** 1.!0 !1.10 12.0% !1.10

Rate ? k+5, +6, Rate ? k+5,! +6, Rate ? k+5, +6,! Rate ? k+5, Rate ? k+5,3

243

1. :

;or the reaction !5 6 !C 7 E

the follo$ing initial rate data $ere collected at constant temperature. 7etermine the correct rate la$ for this reaction. 5ll units are ar3itrar@. Trial 1 ! 3 2 a. 3. c. d. e. /. M +5, %.!!0 %.3!% %.!!0 %.!!0 +6, %.10% %.10% %.!0% %.10% +C, %.30% %.30% %.30% %.6%% Rate %.%!11 %.%234 %.%36! %.%1!1%

Rate ? k+5,+6,+C, Rate ? k +5,!+6,+C, Rate ? k +5,!+6,+C,.1 Rate ? k +5,+6,!+C, .1 none of the a3o'e

The rate constant for a reaction is 2.60 - mol.1s.1. &hat is the o'erall order of the reaction( a. 3. c. d. e. Aero first second third More information is needed to determine the o'erall order.

4. M

Bulfur@l chloride8 B9!Cl!)g*8 decomposes at high temperature to form B9!)g* and Cl!)g*. The rate constant at a certain temperature is 2.6/ 1%.0s.1. &hat is the order of the reaction( a. 3. c. d. e. Aero first second third More information is needed to determine the order.

1%. E

&hen the reaction 5 6 C is studied8 a plot of ln+5,t 's. time gi'es a straight line $ith a negati'e slope. &hat is the order of the reaction( a. 3. c. d. e. Aero first second third More information is needed to determine the order.

11. E

&hen the reaction 5 6 C is studied8 a plot 1<+5,t 's. time gi'es a straight line $ith a positi'e slope. &hat is the order of the reaction( a. 3. c. d. e. Aero first second third More information is needed to determine the order.

244

1!. M

&hich of the follo$ing sets of units could 3e appropriate for a AeroCorder rate constant( a. 3. c. d. e. s.1 - mol.1 s.1 -! mol.! s.1 -3 mol.3 s.1 mol -.1 s.1

13. M

&hich one of the follo$ing sets of units is appropriate for a secondCorder rate constant( a. 3. c. d. e. s.1 mol -.1 s.1 - mol.1 s.1 mol! -.! s.1 -! mol.! s.1

12. M

&hich one of the follo$ing sets of units is appropriate for a thirdCorder rate constant( a. 3. c. d. e. s.1 mol -.1 s.1 - mol.1 s.1 -! mol.! s.1 -3 mol.3 s.1

10. M

5 reaction has the follo$ing rate la$: Rate ? k+5,+6,! "n e#periment 18 the concentrations of 5 and 6 are 3oth %.1% mol -.1D in e#periment !8 the concentrations are 3oth %.3% mol -.1. "f the temperature sta@s constant8 $hat is the 'alue of the ratio8 Rate)!*<Rate)1*( a. 3. c. d. e. 3.% 6.% 4.% 1/ !1

16. M

5mmonium c@anate )=:2C=9* reacts to form urea )=:!C9=:!*. 5t 60C the rate constant8 k8 is 3.6% - mol.1s.1. &hat is the rate la$ for this reaction( a. 3. c. d. e. Rate ? 3.6% - mol.1s.1+=:2C=9, Rate ? 3.6% - mol.1s.1+=:2C=9,! Rate ? %.!/ mol -.1 s.1+=:2C=9, Rate ? %.!/ mol -.1 s.1+=:2C=9,! Rate ? 3.6% - mol.1s.1+=:!C9=:!,.1

245

11. :

!=96r)g* !=9)g* +=96r,)mol -.1* %.%20% %.%31% %.%%40

6r!)g* Rate )mol -.1s.1* 1.6! 1%.3 1.64 1%.2 1.!! 1%.0

6ased on the initial rate data a3o'e8 $hat is the 'alue of the rate constant( a. 3. c. d. e. 1/. : %.%36% - mol.1s.1 %./%% - mol.1s.1 1.!0 - mol.1s.1 !1./ - mol.1s.1 %.%36% s.1 6B @ields the follo$ing initial rate data

5 stud@ of the decomposition reaction 3RB! 3R +RB!,)mol -.1* %.10% %.!0% %.30% %.0%% Rate )mol<)->s** %.%342 %.1%4 %.!12 %.23/

&hat is the rate constant for the reaction( a. 3. c. d. e. 14. M %.%1%3 - mol.1s.1 %.!63 - mol.1s.1 %.011 - mol.1s.1 1.11 - mol.1s.1 1.10 - mol.1s.1

Bucrose decomposes to fructose and glucose in acid solution. &hen ln +sucrose, is plotted 's. time8 a straight line $ith slope of .%.!%/ hr.1 results. &hat is the rate la$ for the reaction( a. 3. c. d. e. Rate ? %.!%/ hr.1 +sucrose,! Rate ? %.!%/ hr.1 +sucrose, Rate ? %.%233 hr +sucrose,! Rate ? %.%233 hr +sucrose, Rate ? %.!%/ mol -.1hr.1 +sucrose,%

!%. M

Tetrafluoroeth@lene8 C!;28 can 3e con'erted to octafluoroc@clo3utane $hich can 3e used as a refrigerant or an aerosol propellant. 5 plot of 1<+C!;2, 's. time gi'es a straight line $ith a slope of %.%22/ - mol.1s.1. &hat is the rate la$ for this reaction( a. 3. c. d. e. Rate ? %.%22/ )- mol.1s.1*+C!;2, Rate ? !!.3 )mol -.1s*+C!;2, Rate ? %.%22/ )- mol.1s.1*+C!;2,! Rate ? !!.3 )mol -.1s*+C!;2,! Rate ? %.%22/ s.1 +C!;2,

246

!1. M

The reaction 5 6 is firstCorder o'erall and firstCorder $ith respect to the reactant 5. The result of dou3ling the initial concentration of 5 $ill 3e to a. 3. c. d. e. shorten the halfClife of the reaction. increase the rate constant of the reaction. decrease the rate constant of the reaction. shorten the time taEen to reach equili3rium. dou3le the initial rate.

!!. :

The decomposition of h@drogen pero#ide is a firstCorder process $ith a rate constant of 1.%6 1%.3 min.1. :o$ long $ill it taEe for the concentration of :!9! to drop from %.%!%% M to %.%1!% M( a. 3. c. d. e. F 1 min 1.00 min 2/1 min 200% min 3182%% min

!3. :

C@clopropane is con'erted to propene in a firstCorder process. The rate constant is 0.2 1%.! hr.1. "f the initial concentration of c@clopropane is %.10% M8 $hat $ill its concentration 3e after !!.% hours( a. 3. c. d. e. %.%201 M %.1%0 M %.1!1 M %.24! M none of the a3o'e

!2. M

The rate la$ for the reaction 35 !6 is rate ? E+5, $ith a rate constant of %.%221 hr.1. &hat is the halfC life of the reaction( a. 3. c. d. e. %.%!!2 hr %.%620 hr 10.0 hr !!.2 hr 22.1 hr

!0. M

The rate la$ for the rearrangement of C:3=C to C:3C= at /%% K is rate ? )13%% s.1*+C:3=C,. &hat is the halfClife for this reaction( a. b. c. d. e. 1.64 1%.2 s 0.3 1%.2 s 1.4 1%.3 s 0!% s 14!% s

!6. M

The rate constant for the reaction 35 26 is 6.%% 1%.3 - mol.1min.1. :o$ long $ill it taEe the concentration of 5 to drop from %.10 M to %.!0 M? a. b. c. d. e. !.! 1%.3 min 0.0 1%.3 min 1/% min 22% min 0.% 1%! min

247

!1. M

6utadiene8 C2:6 )used to maEe s@nthetic ru33er and late# paints* dimeriAes to C/:1! $ith a rate la$ of rate ? %.%12 -<)mol>s* +C2:6,!. &hat $ill 3e the concentration of C2:6 after 3.% hours if the initial concentration is %.%!0 M( a. 3. c. d. e. %.%%0! M %.%!2 M 23 M 14% M %.%%%% M

!/. :

The rate la$ for the reaction 35 C is Rate ? 2.36 1%.! - mol.1 hr.1+5,! &hat is the halfClife for the reaction if the initial concentration of 5 is %.!0% M( a. 3. c. d. e. %.%1%4 hr %.%6!4 hr 10.4 hr !3.4 hr 41.1 hr

!4. :

The decomposition of B9Cl! is firstCorder in B9Cl!. "f the halfClife for the reaction is 2.1 hr8 ho$ long $ould it taEe for the concentration of B9Cl! to drop from %.36 M to %.%20 M? a. 3. c. d. e. %.0! hr 1.2 hr 1! hr 33 hr G 2% hr

3%. :

The reaction C:3=C)g* C:3C=)g* is firstCorder $ith respect to meth@l isoc@anide8 C:3=C. "f it taEes 1%.3 minutes for e#actl@ one quarter of the initial amount of meth@l isoc@anide to react8 $hat is the rate constant in units of min.1( a. 3. c. d. e. .%.130 min.1 %.%!14 min.1 %.%/4 min.1 %.130 min.1 30./ min.1

31. M

5 reactant R is 3eing consumed in a firstCorder reaction. &hat fraction of the initial R is consumed in 2.% halfCli'es( a. 3. c. d. e. %.42 %./1 %.10 %.13 %.%63

248

3!. M

5 firstCorder reaction has a halfClife of !%.% minutes. Btarting $ith 1.%% 1%!% molecules of reactant at time t ? %8 ho$ man@ molecules remain unreacted after 1%%.% minutes( a. b. c. d. e. 1.%% 1%2 molecules !.%% 1%14 molecules 3.!% 1%16 molecules 0.%% 1%!% molecules none of the a3o'e

33. M

Car3onC12 is a radioacti'e isotope $hich deca@s $ith a halfClife of 013% @ears. &hat is the firstCorder rate constant for its deca@8 in units of @ears .1( a. b. c. d. e. 0.!0 1%.0 @ears .1 1.!1 1%.2 @ears .1 1.10 1%.2 @ears.1 3.24 1%.2 @ears.1 3.41 1%3 @ears.1

32. :

The radioacti'e isotope tritium deca@s $ith a firstCorder rate constant k of %.%06 @ear.1. &hat fraction of the tritium initiall@ in a sample is still present 3% @ears later( a. 3. c. d. e. %.14 %.6% %.10 !./ 1%.3/ none of the a3o'e

30. :

7initrogen tetrao#ide8 =!928 decomposes to nitrogen dio#ide8 =9!8 in a firstCorder process. "f k ? !.0 1%3 s.1 at 0C and k ? 3.0 1%2 s.1 at !0C8 $hat is the acti'ation energ@ for the decomposition( a. 3. c. d. e. %.13 EH<mol 0/ EH<mol 12% EH<mol 0/% EH<mol G 1%%% EH<mol

36. :

5mmonia $ill react $ith o#@gen in the presence of a copper catal@st to form nitrogen and $ater. ;rom 162.0ICto 114.%IC8 the rate constant increases 3@ a factor of 2.!1. &hat is the acti'ation energ@ of this o#idation reaction( a. 3. c. d. e. !2.0 EH<mol 160 EH<mol !2! EH<mol 163% EH<mol G 1%2 EH<mol

31. M

"f the acti'ation energ@ of a reaction decreases 3@ 1%.% EH<mol8 from 1%%.% to 4%.% EH<mol8 $hat effect $ill this ha'e on the rate of reaction at !4/K( a. 3. c. d. e. The rate $ill increase8 3@ a factor of more than 0%. The rate $ill decrease8 3@ a factor of more than 0%. The rate $ill increase8 3@ a factor of less than 0%. The rate $ill decrease8 3@ a factor of less than 0%. The rate $ill not change unless temperature changes.

249

250

3/. M

5 rate constant o3e@s the 5rrhenius equation8 the factor A 3eing !.! 1%13 s.1 and the acti'ation energ@ 3eing 10%. EH mol.1. &hat is the 'alue of the rate constant at !!1C8 in s.1( a. b. c. d. e. !.1 1%13 s.1 6.1 1%.!! s.1 1.0 1%11 s.1 2.1 1%.3 s.1 none of the a3o'e

34. :

5 reaction has an acti'ation energ@ of 140.% EH<mol. &hen the temperature is increased from !%%. C to !!%.C8 the rate constant $ill increase 3@ a factor of a. b. c. d. e. 1.1 2.3 1%2 3.! 1.0 none of the a3o'e

2%. :

The decomposition of dinitrogen pentao#ide to nitrogen dio#ide and o#@gen follo$s firstCorder Einetics and has an acti'ation energ@ of 1%! EH<mol. 6@ $hat factor $ill the fraction of collisions $ith energ@ greater than or equal to the acti'ation energ@ increase if the reaction temperature goes from 3%C to 6%C( a. 3. c. d. e. 1.%% 1.1% !.%% 2.%% 3/.2

21. E

The decomposition of dinitrogen pentao#ide has an acti'ation energ@ of 1%! EH<mol and Hr#n ? 00 EH<mol. &hat is the acti'ation energ@ for the re'erse reaction( a. 3. c. d. e. !1 EH<mol 21 EH<mol 00 EH<mol 1%! EH<mol More information is needed8 since this is a :essJs la$ calculation.

2!. E

The Einetics of the decomposition of dinitrogen pentao#ide is studied at 0%C and at 10C. &hich of the follo$ing statements concerning the studies is correct( a. b. c. d. e. The rate at 10C $ill 3e greater than the rate at 0%C 3ecause the acti'ation energ@ $ill 3e lo$er at 10C than at 0%C. The rate at 10C $ill 3e greater than the rate at 0%C 3ecause the acti'ation energ@ $ill 3e higher at 10C than at 0%C. The rate at 10C $ill 3e less than the rate at 0%C 3ecause the molecules at higher speeds do not interact as $ell as those at lo$er speeds. The rate at 10C $ill 3e greater than at 0%C 3ecause the concentration of a gas increases $ith increasing temperature. The rate at 10C $ill 3e greater than the rate at 0%C 3ecause the num3er of molecules $ith enough energ@ to react increases $ith increasing temperature.

251

23. M

Reaction intermediates differ from acti'ated comple#es in that a. 3. c. d. e. the@ are sta3le molecules $ith normal 3onds and are frequentl@ isolated. the@ are molecules $ith normal 3onds rather than partial 3onds and can occasionall@ 3e isolated. the@ are intermediate structures $hich ha'e characteristics of 3oth reactants and products. the@ are unsta3le and can ne'er 3e isolated. all reactions in'ol'e reaction intermediates8 3ut not all ha'e acti'ated comple#es.

22. :

Consider the follo$ing mechanism for the o#idation of 3romide ions 3@ h@drogen pero#ide in aqueous acid solution. : :!9! :!9 .9: )rapid equili3rium* :!9 .9: 6r. :96r :!9 )slo$* :96r : 6r. 6r! :!9 )fast* &hat is the o'erall reaction equation for this process( a. b. c. d. e. !:!9 .9: !6r. :!9! 6r! !:!9 . !: !6r :!9! 6r! !:!9 !: :!9! 6r. :96r :!9 .9: :!9 .9: 6r. : 6r! :!9 none of the a3o'e

6r!

:!9

20. E

&hat is the molecularit@ of the follo$ing elementar@ reaction( =:!Cl)aq* a. 3. c. d. e. 9:.)aq* =:Cl.)aq* :!9)l*

unimolecular 3imolecular termolecular tetramolecular =eed to Eno$ the reaction order 3efore molecularit@ can 3e determined.

26. M

Consider the follo$ing mechanism for the o#idation of 3romide ions 3@ h@drogen pero#ide in aqueous acid solution. : :!9! :!9 .9: )rapid equili3rium* . :!9 .9: 6r :96r :!9 )slo$* :96r : 6r. 6r! :!9 )fast* &hich of the follo$ing rate la$s is consistent $ith the mechanism( a. 3. c. d. e. Rate ? k+:!9!,+: ,!+6r., Rate ? k +:!9 .9:,+6r., Rate ? k+:!9!,+: ,+6r., Rate ? k+:96r,+: ,+6r.,+:!9!, Rate ? k+6r.,

21. E

&hich of the follo$ing affects the acti'ation energ@ of a reaction( a. 3. c. d. e. temperature of the reactants concentrations of reactants presence of a catal@st surface area of reactants reaction progress

252

2/. E

5 catal@st accelerates a reaction 3ecause a. 3. c. d. e. it increases the num3er of molecules $ith energ@ equal to or greater than the acti'ation energ@. it lo$ers the acti'ation energ@ for the reaction. it increases the num3er of collisions 3et$een molecules. it increases the temperature of the molecules in the reaction. it supplies energ@ to reactant molecules.

24. E

&hen a catal@st is added to a reaction mi#ture8 it a. 3. c. d. e. increases the rate of collisions 3et$een reactant molecules. pro'ides reactant molecules $ith more energ@. slo$s do$n the rate of the 3acE reaction. pro'ides a ne$ path$a@ )mechanism* for the reaction. does none of the a3o'e.

0%. M

The gasCphase reaction C:3=C C:3C= has 3een studied in a closed 'essel8 and the rate equation $as found to 3e: rate ? .+C:3=C,<t ? k+C:3=C,. &hich one of the follo$ing actions is least liEel@ to cause a change in the rate of the reaction( a. 3. c. d. e. lo$ering the temperature adding a catal@st using a larger initial amount of C:3=C in the same 'essel using a 3igger 'essel8 3ut the same initial amount of C:3=C continuousl@ remo'ing C:3C= as it is formed

Short Answer Questions 01. E "n the gas phase at 0%%.C8 c@clopropane reacts to form propene in a firstCorder reaction. The figure alongside sho$s the concentration of c@clopropane plotted 'ersus time. Kse the graph to calculate appro#imate 'alues of a. the rate of the reaction8 6%%. seconds after the start. 3. the halfClife of the reaction8 t1<!.

0!. :

Lou are stud@ing the rate of the reaction !5 6 and ha'e o3tained measurements of the concentration of 5 at times t ? 1%%8 !%%8 3%%8 ......8 1%%% seconds from the start of the reaction. Carefull@ descri3e ho$ @ou $ould plot a graph and use it to: a. pro'e that the reaction is secondCorder $ith respect to 5. 3. determine the secondCorder rate constant k.

253

03. M

"n the gas phase at 0%%.C8 c@clopropane reacts to form propene in a firstCorder reaction. The figure sho$s the natural logarithm of the concentration of c@clopropane )in mol<-* plotted 'ersus time. a. E#plain ho$ this plot confirms that the reaction is first order. 3. Calculate the firstCorder rate constant8 k. c. 7etermine the initial concentration of c@clopropane in this e#periment.

02. :

5 chemical reaction of the general t@pe 5 !6 is firstCorder8 $ith a rate constant of 1.0! 1%.2 s.1. a. Calculate the halfClife of 5. 3. 5ssuming the initial concentration of 5 is %.%61 mol -.18 calculate the time needed for the concentration to fall to %.%1% mol -.1. The gasCphase con'ersion of 183C 3utadiene to 180Cc@clooctadiene8 !C2:6 C/:1! $as studied8 pro'iding data for the plot sho$n alongside8 of 1<+3utadiene, 'ersus time. a. E#plain ho$ this plot confirms that the reaction is second order. 3. Calculate the secondCorder rate constant8 k. c. 7etermine the initial concentration of 183C3utadiene in this e#periment.

00. M

06. : 01. M 0/. :

Lou are required to determine the energ@ of acti'ation )Ea* of a reaction. 6riefl@ descri3e the e#perimental measurements @ou $ould maEe and ho$ @ou $ould o3tain the acti'ation energ@ from a suita3le linear plot of the e#perimental data. 5t !0.%C8 a rate constant has the 'alue 0.!1 1%./ - mol.1 s.1. "f the acti'ation energ@ is 10.! EH<mol8 calculate the rate constant $hen the temperature is 0%.%C. C@clo3utane decomposes to ethene in a firstCorder reaction. ;rom measurements of the rate constant )k* at 'arious a3solute temperatures )T*8 the accompan@ing 5rrhenius plot $as o3tained )ln k 'ersus 1<T*. a. Calculate the energ@ of acti'ation8 Ea. 3. 7etermine the 'alue of the rate constant at 12%. K. )"n the plot8 the units of k are s.1.* 5ccording to the collision theor@ of reaction rates8 $hat are the three requirements $hich must 3e met 3efore an elementar@ reaction 3et$een t$o molecules can occur(

04. E

254

6%. : 61. M

6riefl@ outline the Ee@ arguments in the collision theor@ of reaction rates for the elementar@ reaction C 7 products. Bho$ that this theor@ predicts a secondCorder rate la$8 and ho$ it predicts the form of the rate constant k. "n the collision theor@ of reaction rates8 the rate constant for a 3imolecular reaction can 3e $ritten as k ? zpe#p).Ea<RT* "n one sentence each8 clearl@ e#plain the ph@sical meaning )interpretation* of the follo$ing three factors $hich appear in the a3o'e e#pression: a. z 3. p c. e#p).Ea<RT*

6!. :

The elementar@ reaction :6r)g* a. 3.

6r)g* :)g*

6r!)g* is endothermic.

&ould @ou e#pect the rate constant for the 3acE reaction to 3e smaller or larger than that for the for$ard reaction( E#plain8 3riefl@. 7ra$ a full@Cla3eled reaction energ@ diagram for this reaction8 sho$ing the locations of the reactants8 products and transition state.

63. : 62. M

"s a 3imolecular reaction necessaril@ secondCorder( "s a secondCorder reaction necessaril@ 3imolecular( 5ns$er8 $ith e#planations and clarifications. ;or each of the follo$ing terms<concepts8 gi'e a 3rief e#planation or definition. &here possi3le8 use e#amples. a. 3. c. order of a reaction elementar@ reaction reaction intermediate

60. M 66. :

6riefl@ list the features<properties common to all catal@sts and ho$ the@ $orE. 7ra$ a la3eled reaction energ@ diagram as part of @our ans$er. Consider the general gasCphase reaction of a molecular su3stance8 5 1. 56

5t 'er@ lo$ pressures man@ such reactions occur 3@ the follo$ing mechanism: !. 5 5 5M 5 )slo$* 3. 5M 6 )fast* )5M represents a molecule $ith sufficient energ@ to o'ercome the acti'ation energ@ 3arrier.* a. 3. c. d. &hich of the three reactions a3o'e is<are elementar@( &here appropriate8 identif@ the molecularit@ of the reactions. Bho$ that the proposed mechanism is consistent $ith reaction 18 the o3ser'ed reaction. Ni'en the mechanism a3o'e8 suggest a liEel@ rate la$ for reaction )1*.

255

True/False Questions 61. M 6/. E 64. M 1%. E 11. M 1!. E 13. E 12. : 10. M 16. E 11. M 1/. M The rate la$ cannot 3e predicted from the stoichiometr@ of a reaction. The units of the rate constant depend on the order of the reaction. The units of the rate of reaction depend on the order of the reaction. The halfClife of a firstCorder reaction does not depend on the initial concentration of reactant. The halfClife of a secondCorder reaction does not depend on the initial concentration of reactant. The greater the energ@ of acti'ation8 Ea8 the faster $ill 3e the reaction. 5n elementar@ reaction is a simple8 oneCstep process. 5ll secondCorder reactions are 3imolecular reactions. 5ll 3imolecular reactions are secondCorder reactions. The rate of a reaction is determined 3@ the rate of the fastest step in the mechanism. 5 transition state is a species )or state* corresponding to an energ@ ma#imum on a reaction energ@ diagram. 5 reaction intermediate is a species corresponding to a local energ@ ma#imum on a reaction energ@ diagram.

256

Kinetics: Rates and Mechanisms of Chemical Reactions Chapter 16 5ns$er Ke@

1. !. 3. 2. 0. 6. 1. /. 4. 1%. 11. 1!. 13. 12. 10. 16. 11. 01. d 3 d c e d c c 3 3 c e c d e 3 3 1/. 14. !%. !1. !!. !3. !2. !0. !6. !1. !/. !4. 3%. 31. 3!. 33. 32. e 3 c e c a c 3 d a e c 3 a e 3 a 30. 36. 31. 3/. 34. 2%. 21. 2!. 23. 22. 20. 26. 21. 2/. 24. 0%. 3 3 a d d e 3 e 3 3 3 c c 3 d e

a. Rate ? . slope ? 6 1 1%.0 mol -.1 s.1 3. 34% !% s a. 3. a. 3. c. Olot 1<+5, 'ersus time. "f a straight line results8 the reaction is secondCorder. The rate constant k is the slope of the plot in )a*. The fact that a plot of ln +c@clopropane, )i.e.8 ln +reactant,* 'ersus t gi'es a straight line pro'es that it is firstCorder. k ? . slope ? 1./ 1%.0 s.1 %.1% mol -.1

0!. 03.

02.

a. tP ? 2.06 1%3 s 3. 1.!0 1%2 s a. 3. c. The fact that a plot of 1<+3utadiene, 'ersus t gi'es a straight line pro'es that it is secondCorder. k ? slope ? /.! 1%.! - mol.1 s.1 %.%!0 mol -.1

00.

06. 01. 0/.

93tain rate constants k o'er a suita3le range of a3solute temperatures T. 5 plot of ln k 'ersus 1<T should 3e linear8 and its slope is . Ea<R. 0.22 1%.1 s.1 a. !6% !% EH<mol 3. 1.6 1%.3 s.1 Molecules must collide $ith each otherD the molecules must ha'e sufficient energ@ to o'ercome the acti'ation energ@ 3arrierD the molecules must ha'e the correct orientation.

04.

257

6%.

;or reaction to occur8 the molecules must collide. Collision rate ? z+C,+7, ;or a collision to lead to reaction8 the molecules must ha'e an energ@ at least equal to the energ@ of acti'ation8 Ea. The fraction of molecules $ith sufficient energ@ is e#p).Ea<RT*. E'en if a collision has sufficient energ@8 reaction $ill not occur unless the molecules are correctl@ oriented $.r.t. each other. The steric factor8 p8 gi'es the fraction of collisions $ith correct orientation. Thus8 the total rate of successful collisions 3et$een C and 7 is gi'en 3@ z+C,+7,pe#p).Ea<RT*. This is a secondCorder rate la$8 3eing firstC order in 3oth C and 7. 5ccording to the rate equation8 the rate of reaction is k+C,+7,. Comparison of the t$o e#pressions for the rate sho$s that k is equal to zpe#p).Ea<RT*. a. 3. c. z is a collision rate constant8 such that the rate of collision 3et$een C and 7 ? z+C,+7,. p is the steric factor8 $hich is the fraction of collisions 3et$een C and 7 in $hich the molecules are suita3l@ oriented for reaction. e#p).Ea<RT* is the fraction of collisions $hich ha'e sufficient energ@ to o'ercome the acti'ation energ@ 3arrier. The 3acE reaction is e#othermic. Bince 3. the reactions share a common transition state8 the acti'ation energ@ for the 3acE reaction must 3e smaller than that for the for$ard reaction. 9ther things 3eing equal8 the rate constant for the 3acE reaction $ill 3e larger.

61.

6!.

a.

63.

;or elementar@ reactions8 the order follo$s from the molecularit@. Therefore a 3imolecular reaction is necessaril@ secondCorder. 5 secondCorder reaction ma@ result from a comple# mechanism in'ol'ing steps of different orders8 and it is thus meaningless to attempt to deduce molecularit@ from reaction order. a. 3. c. 9rder refers to the po$er to $hich the concentration of a reactant is raised in the rate equation. 5n elementar@ reaction is one occurring in a single step on the molecular le'el. 5 reaction intermediate is an unsta3le species $hich appears in a reaction mechanism8 3ut is neither a reactant nor a product.

62.

60.

Catal@sts speed up a reaction 3@ pro'iding an alternati'e route of lo$er acti'ation energ@. The@ do not alter the equili3rium position of a reaction.

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66.

a. 3. c. d. T T ; T ; ; T ; T ; T ;

Reactions ! and 3 are elementar@. Reaction ! is 3imolecularD reaction 3 is unimolecular. &hen reactions ! and 3 are added8 the result is 5 68 i.e.8 the same as reaction 1. Reaction !8 3eing slo$8 is the rateCdetermining step of the mechanism. The o'erall rate $ill 3e the rate of this reaction8 i.e.8 rate ? k!+5,!.

61. 6/. 64. 1%. 11. 1!. 13. 12. 10. 16. 11. 1/.

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