Gupta 2012 WORKSHEET: KINETICS PROBLEMS SORTED BY TYPES OF PROBLEMS RATES OF REACTION 1.

Give the relative rates of disappearance of reactants and formation of products for each of the following reactions. a. 2 O3 (g) 3 O2 (g) b. 2 HOF (g) 2HF (g) + O2 (g) 2. !perimental data are listed here for the reaction " 2 #. $ime (s) ).)) 1).) 2).) 3).) -).) %#& (mol'() ).))) ).32* ).+,2 ).,+) )../)

a. 0repare a graph from these data1 connect the points with a smooth line1 and calculate the rate of change of %#& for each 1) second interval from ).) to -).) s. 2oes the rate of change decrease from one time interval to the ne!t3 4uggest a reason for this result. 5. How is the rate of change of %"& related to the rate of change %#& in each time interval3 6alculate the rate of change of %"& for the time interval from 1).) to 2).)s. c. 7hat is the instantaneous rate when %#& 8 ).,+) mol'(3 3. For the reaction 6(g) 2(g)1 %6& vs. time is plotted9

How do :ou determine each of the following3 a. $he average rate over the entire e!periment 5. $he reaction rate at time ! c. $he initial reaction rate d. 7ould the values in parts a1 51 and c 5e different if :ou plotted %2& vs. time3 !plain. 4. $he 6ompound ";2 decomposes according to the e<uation 2";2(g) 2";(g) + ;2(g). =n one e!periment1 %";2& was measured at various times and these data were o5tained9 Time (s) ) [AX2] (m !"L) ).)+))

Gupta 2012 2.) *.) ..) 1).) 2).) ).)--. ).)3)) ).)2-/ ).)2)/ ).))..

a. Find the average rate over the entire e!periment. 5. =s the initial rate higher or lower than the rate in part a3 >se graphical methods to estimate the initial rate. +. ?ust as the depletion of stratospheric o@one toda: threatens life on arth1 its accumulation was one of the crucial processes that allowed life to develop in prehistoric times9 3O2 (g) 2O3 (g) a. !press the reaction rate in terms of %O2& and %O3&. 5. "t a given instant1 the reaction rate in terms of %O 2& is 2.1, ! 1)A+ mol'((Bs). 7hat is it in terms of %O3&3 *. " reaction has the following e!perimental rate e<uation9 Cate 8 D%"& 2%#&. =f the concentration of " is dou5led and the concentration of # is halved1 what happens to the reaction rate3 INITIAL RATES METHOD PROBLEMS 1. $he reaction 5etween o@one and nitrogen dio!ide at 231 E is first order in 5oth %FO 2& and %O3&9 2FO2 (g) + O3 (g) F2O+ (s) + O2 (g) a. 7rite the rate e<uation for the reaction. 5. =f the concentration of FO2 is tripled1 what is the change in the reaction rate3 c. 7hat is the effect on reaction rate if the concentration of O 3 is halved3 2. $he data in the ta5le are for the reaction of FO and O 2 at **) E. 2 FO (g) + O2 (g) 2 FO2 (g) %FO& (mol'() ).)1) ).)2) ).)1) %O2& (mol'() ).)1) ).)1) ).)2) Cate of "ppearance of FO (mol'( B s) 2.+ ! 1)GA+ 1.) ! 1)GA+.) ! 1)GA+

a. 2etermine the order of the reaction for each reactant. 5.7rite the rate e<uation for the reaction. c. 6alculate the rate constant. d.6alculate the rate (in mol'( B s) at the instant when %FO& 8 ).)1+ mol'( and %O 2& 8 ).))+) mol'(.

Gupta 2012 e. "t the instant when FO is reacting at the rate 1.) ! 1)GA- mol'( B s1 what is the rate at which O2 is reacting and FO2 is forming3 3. 2ata for the reaction 2 FO (g) + O2 (g) 2FO2 (g) are given in the ta5le. !periment 1 2 3 %FO& (mol'() 3.* ! 1)GH3.* ! 1)GA1.. ! 1)GA1.. ! 1)GA%O2& (mol'() +.2 ! 1)GA3 1.)- ! 1)GA2 1.)- ! 1)GA2 +.2 ! 1)GA3 =nitial Cate (mol'(Bh) 3.- ! 1)GA. *.. ! 1)GA. 1., ! 1)GA. 3

a. 7hat is the rate law for this reaction3 5. 7hat is the rate constant for the reaction3 c. 7hat is the initial rate of the reaction in e!periment -3 -. For the reaction9 -"(g) + 3#(g) 26(g) $he following data were o5tained at constant temperature9 E#$e%ime&' 1 2 3 I&i'i(! [A] (m !"L) ).1)) ).3)) ).1)) ).3)) I&i'i(! [B] (m !"L) ).1)) ).1)) ).2)) ).2)) I&i'i(! R('e (m !"(L)mi&) +.)) -+.) 1).) /).)

a. 7hat is the order with respect to each reactant3 5. 7rite the rate law. c. 6alculate k (using1 for e!ample1 the data from e!periment 1). +. $he decomposition of ammonia is first order with respect to FH 3. 2FH3 (g) F2 (g) + 3H2 (g) a. 7hat is the rate e<uation for this reaction3 5. 6alculate the rate constant1 k1 given the following data9 %FH3& (mol'() $ime ).*, ) ).2* 1/ c. 2etermine the halfAlife of FH3. PROBLEMS BASED ON INTEGRATION (*si&+ ',e I&'e+%('e- R('e L(.s F %m*!() 1. "mmonium c:anate1 FH-F6O1 rearranges in water to give urea1 (FH2) 26O9

Gupta 2012 FH-F6O (a<) (FH2)26O (a<) $he rate e<uation for this process is Cate 8 D%FH-F6O&21 where D 8 ).)113 ( ' mol B min. =f the original concentration of FH-F6O in solution is ).22/ mol'(1 how long will it taDe for the concentration to decrease to ).1.) mol'(3 2. $he rate e<uation for the decomposition of F2O+ (giving FO2 and O2) is A%F2O+& ' t 8 D %F2O+&. $he value of D is +.) ! 1)A- sA1 for the reaction at a particular temperature. a. 6alculate the halfAlife of F2O+. 5. How long does it taDe for F2O+ concentration to drop to one tenth of its original value3 3. For the simple decomposition reaction "#(g) "(g) + #(g)1 rate 8 k%"#&2 and k 8 ).2 ('(molBs) How long will it taDe for %"#& to reach oneAthird of its initial concentration of 1.+) M3 PROBLEMS BASED ON INTEGRATION (*si&+ /%($,i0(! Me', -s) 1. 6ommon sugar1 sucrose1 5reaDs down in dilute acid solution to form glucose and fructose1 as shown 5elow. #oth products have the same formula1 6*H12O*. 612H22O11 (a<) + H2O (l) 2 6*H12O* (a<) $he rate of this reaction has 5een studied in acid solution1 and the data in the ta5le were o5tained. $ime (min) %612H22O11& (mol'() ) ).31* 3/ ).2,.) ).23. 1-) ).1/) 21) ).1-* a. Graph =n %sucrose& versus time and 1'%sucrose& versus time. 7hat is the order of the reaction3 5. 7rite the rate e<uation for the reaction1 and calculate the rate constant1 D. c. stimate the concentration of sucrose after 1,+ min. 2. Gaseous %FO2& decomposes at +,3 E according to the following reaction9 2 FO2 (g) 2 FO (g) + O2 (g) $he concentration of FO2 was measured as a function of time. " graph of 1'%FO 2& versus time gives a straight line with a slope of 1.1 ('mol B s. 7hat is the rate law for this reaction3 7hat is the rate constant3 3. 7hen heated1 tetraflouroeth:lene dimeri@es to form octaflouroc:clo5utane9 2 62F- (g) 6-F. (g) $o determine the rate of this reaction at -.. E1 the data in the ta5le were collected. "nal:sis was done graphicall:1 as shown 5elow9

Gupta 2012

%62F-& (M) ).1)) ).).) ).)*) ).)-) ).)3)

$ime (s) ) +* 1+) 33+ +2)

>sing the data in the ta5le9 a. 2ecide whether the reaction is first order or second order. 5. 6alculate k for this reaction. PROBLEMS ON ACTIVATION ENERGY 1. 7hen heated to a high temperature1 c:clo5utane1 6-H. decomposes to eth:lene9 6-H. (g) 262H- (g) $he activation energ:1 a1 for this reaction is 3*) D?'mol. "t .)) E1 the rate constant D8).)31+ s A1. 2etermine the value of D at /+) E. 2. $he rate constant of a reaction is -.+) ! 1)A+ ('(molBs) at 1/+o6 and 3.2) ! 1)A3 ('(molBs) at 2+.o6. 7hat is the activation energ: of the reaction3 PROBLEMS ON REACTION MECHANISMS 1. " proposed mechanism for the reaction of FO 2 and 6O is 4tep 1 (4low1 endothermic) 2FO2 (g) FO (g) + FO3 (g) 4tep 2 (Fast1 e!othermic) FO3 (g) + 6O (g) FO (g) + 6O2 (g) Overall Ceaction ( !othermic) FO2 (g) + 6O (g) FO (g) + 6O2 (g) a. =dentif: each of the following as a reactant1 product1 or intermediate9 FO 2 (g)1 6O (g)1 FO3 (g)1 6O2 (g)1 FO(g). 5. 2raw a reaction coordinate diagram for this reaction. =ndicate on this drawing the activation energ: for each step and the overall reaction enthalp:. 2. $hree mechanisms are proposed for the gasAphase reaction of FO with #r 2 to give #rFO9 Iechanism 1 FO (g) + FO (g) + #r2 (g) 2#rFO (g) Iechanism 2

Gupta 2012 4tep 1 (4low) 4tep 2 (Fast) Iechanism 3 4tep 1 (4low) 4tep 2 (Fast) FO (g) + #r2 (g) #r2FO (g) #r2FO (g) + FO (g) 2#rFO (g) FO (g) + FO (g) F2O2 (g) F2O2 (g) + #r2 (g) 2#rFO (g)

a. 7rite the 5alanced e<uation for the net reaction. 5. 7hat is the molecularit: for each step in each mechanism3 c. 7hat are the intermediates formed in mechanisms 2 and 33 d. 6ompare the rate laws that are derived from these three mechanisms. How could :ou differentiate them e!perimentall:3

"nswers9 Cates of Ceaction

1.

a.

5. 2. a. T,e +%($, 1 [B] ($% -*0' 0 &0e&'%('i &) 2e%s*s 'ime s, .s [B] i&0%e(si&+ 1% m 3e% 4 T,e !i&e is 0*%2e-5 i&-i0('i&+ ',e %('e 0,(&+es .i', 'ime6 ',*s ',(' ',e %('e -e$e&-s & 0 &0e&'%('i &4 R('es 1 % ',e 1 *% 789s i&'e%2(!s (%e (s 1 !! .s: 1% m 8978s5 848:2 m !"L)s6 1% m 78928s5 8482;< m !"L)s6 1% m 289:8s5 8487=> m !"L)s6 1% m :89;8s5 8487;8 m !"L)s 5. ',% *+, *' ',e %e(0'i &4

I& ',e i&'e%2(! 78928s5

? 984872:

c. I&s'(&'(&e *s %('e .,e& [B] ? 84=@8 m !"L ? 3. a. 6alculate the slope of the line connecting ()1 %6&o) and (tf1 %6&f)A the negative of this slope is the average rate. 5. 6alculate the negative of the slope of the tangent line at t 8 ! c. 6alculate the negative of the slope of the tangent line at t 8 ) d. =f :ou plotted %2& vs. time1 :ou would not need to taDe the negative of the slopes in a. H c.

Gupta 2012

-.

a. 1.)

789:

A4 $he initial rate is determined 5: the slope of the tangent to the curve at the point t 8 ).
$he initial rate is higher than the rate in part a. =nitial rate 8 789:

+.

a.

A4 74;@
*.

789@

T,e %e(0'i & %('e - *A!es4

=nitial Cates Iethod 1. a. R('e ? k[NO2][O2] 5. I1 [NO2] is '%i$!e-5 ',e %('e '%i$!es4 c. I1 [O:] is ,(!2e-5 ',e %('e is ,(!2e-4 a. T,e %e(0'i & is se0 &- %-e% i& [NO] (&- 1i%s' %-e% i& [O 2] 5. ? k[NO]2[O2]

2.

c. 2@48 M92s97 d. 24>7 X 789@ M"s e. W,e& ? 748 789; 5

? @48

789@

5 (&-

? 748
3.

789;

a. R('e ? k[NO]2[O2] 5. k ? @84 L2 " m !2 , c. I&i'i(! %('e ? >4;2 789B

-.

a. Fi%s' %-e% i& [A]5 se0 &- %-e% i& [B]4 5. R('e ? k[A]2[B] c. k ? @488 78:

Gupta 2012 +. a. R('e ? k[NH:] 5. k ? 848@8 s97 c. H(!19!i1e ? 7:4> s =ntegration 1. 1)+.2 min 2. a. 13.*.3 s 5. -*)+ s 3. *.*, s =ntegration (GraphA5ased 0ro5lems) 1. a. A +%($, 1 7"[s*0% se] 2e%s*s 'ime $% -*0es ( s'%(i+,' !i&e5 i&-i0('i & ',(' ',e %e(0'i & is se0 &- %-e% 1 % [s*0% se]4 5. k ? 8487=@ mi&97 c. A' 7=@ mi&5 [s*0% se] ? 847<7M 2. T,e +%($, 1 7"[NO2] 2e%s*s 'ime +i2es ( s'%(i+,' !i&e5 i&-i0('i&+ ',e %e(0'i & is se0 &%-e% .i', %es$e0' ' [NO2]4 T,e s! $e 1 ',e !i&e is k5 s k ? 747 3. a. A $! ' 1 7"[0 &0] 2e%s*s 'ime is !i&e(%5 s ',e %e(0'i & is se0 &- %-e%4 5. S! $e ? k ? 848;;<

"ctivation nerg: 1. 2. k ? 7<2 s97 a8 1-). D?'mol

Ceaction Iechanisms 1. 2. a. FO2 (g) reactant1 6O (g) reactant1 FO3 (g) intermediate1 6O2 (g) product1 FO (g) intermediate 5. (draw the diagram) a. 2FO(g) + #r2 (g) 2 #rFO(g) 5. Iechanism 1 is termolecular1 Iechanism 2 and 3 each have two 5imolecular steps. c. #r2FO is the intermediate in mechanism 2 and F2O2 is the intermediate in mechanism 3. d. "ssuming step 1 in each mechanism is the slow step1 the rate e<uations will all differ. Iechanism 1 would 5e second order in FO and first order in #r 2. Iechanism 2 would 5e first order in 5oth FO and #r2. Iechanism 3 would 5e second order in FO and @ero order in #r 2. $o find the right one1 :ou could time the reaction at various reactant concentrations.