,tlttl*I -. '

I -fI ,.--:,.;I'I

ii

I. .

I.

I.

?,. PROBLEM SEl'l

CI.IEMICAL KINETICS

Reaction Rates

Meanlng of reaction rate

rraitorsiftecting rates of reac[ion

?.1. Nature'ofreactants;..i.. concenl'ratioti o[reactants

2.2.1. Rate equation or ra[e law

Z.Z':. Law of 'Mass

AcLiott

2'2.3' Rate constant

12 q' order of reaction

i,z-,s. Half-tife of a reaclron

2.3. TemPera[ureZ.:,f

" Arrhenius Equation

i':'z' EnergY of activa[ion

7.q. CatalYst - ^. .^ -=t.trrciq

2'4'1' HomogetteouttuflT:::.

1qi Heterogeneouscatal\'sls

e Theones on reaction rates ' :3.1. Coltision Theory.1:''' 3.1.1. . Ac$vation energY

3'I'2.' S[eric factor - 'ir'-:^^' 3'1'3' FrequencY of colltston '

3.7' tli"ansition State Theory

Reaction Meclranism

1' :t5:H::;fiti?l'..0 rare-deternrinins step

' :Hil:i.'il":f'lon' o'oounation' termination steps

NUCLTAR CHEMISTRY

iJr

i' RadiOactivttY^-r ,eactiofis versus nuclear reactions

chemtcat t

rT 'd ,Radioactive DecaYrr' r. nuoiouttltt ff::: 3p6 g6ificially Induced RadioactrvitY

2. Nuclear Rea

l'nii.r"utTransmutailon4:,. Electron CaPlure

;. Transuranium Elemenu

r\r Mass Dgfect and nuclear Bindinq Energy

'"' 1' Nut["ar StabililY

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I

fiuclear fitiian ;:nd I luclear Fusion

El{eclof l).arjiatir:n on 14atter- lJnif; r"rsr:d foi mcasuring radiation'

t,pplicaii ans of Ba d i oi soto Pes

Each of the follovring nurnbers con5ists of the follovring quantitiesr one in coltrrnn I and

another in colurnn il, 'i;; ;;; it cornPare the tvro quarrtities and choose

A iF the quantity.ln Column I is greater

B if the quantibl in Column II is greater

C if the tvlo quantities a're equal -:..^^ ,^6^.marie

D if the relationship *;;;iil;;*termined from the given information

" Colu6nn ii

Slnat is/are the catalYft/s?LV.i,'m.HI

P, ---*i P is a first order reaction -t:: of reaction al25'C

. trtz 0f reaction at 50'C

l*i[;'j',,,,,, ..

Er- c,i P.xn I 'v, I .-i ''

Ea of P;n II

e ':lf-iife 0i the :crcrd

qrder t.,r'i5'''r?.. ' .

P,at= canstant v,'he'n lA1, = 514 Reie'constant vilhen [A]: = ]0 l'1

Rate Constant = 50 s-r ior'the reaction

Eawhenlxl' ='io tt' Ea v'rhen lxlo = z0 a[ir'I

7g + Bz -'-"-+ Z

Rate of disappearance of c ,, , ,t( { .- r r,l-r t ilt

* formation of Z

-7

Fscfi afthe questions orlncomplete statements belout is followed by suggested answers'

*tte**eanswer vrhich is best in each'case'

tre harf _.rife ofa first order reacti.n is 5 sei. How rong vl,r it take to reduce the reactant to

1/c, of itsoriginal value?

A) 5.sec 'Ll 10 sec c).i5 sec : D) 20 sec E) 25'sec

The,ioJrovring sequenre-of rea$ion has been-proposed for the -cataryzed

production of Hzo:

"- -Z HrO + S9-) + i''--+ H2SO4 + 2 HI

Z Hi ---t Iz 'i Hz

HrSO. ---+ HzO + t50) + tPAt

,..\

Colurnn I

ta

(

fi

L,

-)

I. SOz

A) 1, iI. II:H,sO{

B) Ii, m, w c) I, iv D) Il,IIIA) L' tr

rresponds to the follorrying mechanism?

3. v/hickof the foltovring'enbrgy prbfiles coirrry v"-''' 'A * g ----+ AB (slow)'

AB + C -== ABC (fast)

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Progress of reactionProgress of reaction

iLt

ta

A) i B) IIi c) iI' N D) Il E) I' II

4. \'Jhich of the foilorvin$ cquses a candle Y*Jo burn'faster in an atmosphere of oz than in air?

1. an int'"u="]ilil;;;;tttration-of the wax

11. ln increase in the concentr-ation of O2

III' nn int"ut* in thc sLrrl'acc arca of [ltt'w;t:':

o;,* ul,l'$0"'"';,',lTll" D) Ir ' E)r' 1I' ,r' Iv

5.Inthereaction:A+ZB-P,itis.foundthaldoublingtheConcentrationofbo|hAandBincreases the rate bv rour EI!'- YL'l^' 'i' oo"io ' "'$:;r?:ii?J::fi'"il""""d order i'r B-

I' first order in A' hrst oroel rlr Ir

II- "'onO'Jra"r

in A' zero'o(er in g V' second ordt' in A' f,rist order in B

III. ze'o order in A' Second order in B

A) I, II. V B) l', iI', lll o I', llD) I1l' N E) 11' lll' v

o wrrv d oes T[ :fiiffi l,li:,fi:'':il..}f ff:fff. ::Tp::t:: "

is i':creased

, ; ll; *."+1,$;'fl.:1.,1 ru:.fx"*TT::flI"-:i;tr#!:il'ffersv to cross rhe

barrier E) I, IV

A) 1, lI, ill u1t'' "'' " .,c)u'

ttt D) 1l' iv

T.Whichofthefollowingeeuatiolsj,]'aPRlicautgforthenelreaction:A+B'_l2C,whichoroceeds uy a srnir*Jep' ni*oruc;iur mechanism?

"4fi;r-'"1" = o 69* o nr A = k tAllBlA) hatr _.*E -. "."-_,n.*

of A = k [A][B]

:i :E:iffi5n'if ii ['= *t' er oi"pp*"unce or A

;i ffii;ili-* t2303)t + rosrAl"

fj att of the above

\\\*._

/'\i\I \/ \l ,'., t

Progress of reacttonProgress of reaction

Hf of $tf e!cz!Dbn Tdboof dryn ljort jh/dpn

;r-r'. t.r rii::i:i

A and B, both of which are gat.,:, *:t:,T,l:d_I a rigid container. No rcaclion w'rs oi"'sttvctl'

9.

i"i.t.*ra possibly aciount for the observation?

I.TheenergYofatlreactingmoleculesisfarbelowtlteenergybarricr,ii. ' ,lu i"..ting molecules are are nor properly oriented'

IiI. I!0 catalys[ was added'

N. flot "nougll

amounts of A and B were added'

A) I, N ei i,-il'cl iII, iv ' D) I' II' IIi E) l' II' lil' iv

\ryhich of ihe following statements is GORRECT about the second order"reaction: 2A *r t] + c ?

' I. rhe rate tiint it"t'on decreasps ".*o::,8- ill :::::::ll':t * A wirr be rerrrtcerl; f:rl'l:,?:,i['J;l;;,?X,ffiffi,t;i;, ffi;il concPntration or A wirr be rerl ctd

to % of its original value after 20 ntin.' , . ,. -

"t"r'".

. ili. A plot of 1nl uutt" time yields a stiaighr line'

iV. The rate of iormation of C is on*fluffin. rate of disappearance of A"

v. -the rate } cf,niumption or n quaUiup'* -Tt-lol.rs doubled'

A) I, Ii, IiI B)1, IV c) i', iv', v n; it'. ttt E) III' lv' v

10.Aflrst'order rezjction: A,--_+ P, has a half-life of 100 s' Whiclr of ttre foilowing is TRUE for

:^'r orr:riiifv of subsia:r':e invoived in the reactiott?

;i'il; t;;ition eoes:o completion in 200 s'

ai ine quanti\ "i"i ":#;i;q iftt' 200 sl; half of what ren';'irs ;ner 100's

g', rhe ,u*" o,unil*ir'; i;;;;;.,t-d.'q' tuu,-v 100 s ror th: rea:iion

L i 100 s elapses befcre r=action begtns' iE) i'lone of ihe abo'^'e

11,lr Is found tha[ the d:composition reaction:'^'

oi i:i rin when the iniliai pressure of HI is

;'c*t ,t the order of the reattion?

;;;;; -

B) rirst c) second

t) insuificient data

2 HI ----r Hr * Ii, at StrS K har a lratf*lifc

6.r'ut,,;# zi ,nln t"'hen the pressure ls 0'5 atnt'

D) third

lz. Ii--ntifu the process described by the reaction: s3214Bi

A) alPha decaY B) beta decaY

oi-'positton d.tuY 'E) fission

t:. fnis reaction describes electron capture by tungsten-181'

A) zrrs'v\1 1 -,',a'-J--- llu'ru ' -01'

"tu'w -l- -toc

-1 T5rurRe

c) ,o'BrW ---* ,r"'TB '+ -,oe ;i

'lsrW --; 75ru'Re t +t,e

t

14. V/hich nuclear reaction will prod.uce-{8j'',1^'-'ei" potu*ti"*-l: decay by proton emissron

BJ' Dorasslum-ro decay by positron'emission

;i ffi*" caPture bY Potassium-3o '6i i'.utton capture by potassium-3a

15. What type of emissiont'vill produce U-238'lrom Pu-242V

C) positron emtssion D) proton emlsston-

t-

--3 ,."*Po + -roe

C). gamma decaY

Hf of drd elcz!Dbn Tdboof dgpn ljotl jh/dpn

@'Pt:&l *:t"Y/ Y Ib'iY/ a' .<-r/ 0,/5 tr8g

!)(/t 5a

" ifi:?.$:trfi.i#4ffi,,,.,r#'u' o"'Z'

u,,n.A) beta PaI

15.2. mercury-t88 decays to gold-1BB-'

A) beta Partroe . B) Positron

5.3. radon-222 decays to polonium-218 -

A) be[a-Particle B) Posi".-ron

5.4 thorium-Z30 decays lo a radium isotope

''' '"";;';.i, prttial B) Positrr'rn

Lt , StrnPIY the missing Particle'.

17.1. st"'Cf + 5"6 4A)

'oiuolr

17.2. iH + zrHe'A) ,lH

r7.3 :i':l 'u"'Xg -"- "ni ,tg q ;!

LJ.4 zesete --,---> -'ot oA) zceFe

rl-rJ o tr

B) ,*u'Frn

2a{e * -B) zaHe

+

C) otn

'C) oinD') -t'z

. C) alPha

CJ alPhe

C) alSit;:

D) neur.rcil

D'1 r;eut-rorr

D") neu?'on ?=

D) neutro:i

D") ,f'io

l^'r ,.r,i""ili, D1 ':'lzi?3

D) -,'e

IV, Solve tlre following prol;lints' :,ncentration of D is 0.150 14.

' ff,',i'j:.,|tji,',:'flli';3,il I;'lf'l1i#'il1;l'J/i[] [ii;;;;'; er' t,)ftrst c'rcier; (C)

s.ionO order; (D) third order'

Z. The follov,ring data obfaine d * ?5:.? !::tfre

reaction'- 7 h + A + Z C'--'- 3 D'

Exneriment ,n,r,uiiot, il- -

ini'itt tBl' ; -

lnitial [c]' 14 lnitial R'ate (t'4 min ')

i o'l;'' ''' ^" ''q'ii" o'10 4'o x 10"

z a;'io o':q o'zo 1'7 t'10-r

'3 ofi o 19 o'30 4'o Y' 10"

'h o;o o3o, o'40 3'6 x 1o-r

A) What is the rate uq'"'ilonZ B) Whai is the value of the rate c'nstant?

S.t4anybiologicalreactionsareacid_catalyzed'AQpicalmechanismconsistentyaiftthe.-p.iri*..ii rate equation

. Rate = k LXI [HR1v,

'

In which HA'is the acid and X is the ieactant is given as follovrs:"" -

'.- Io *=il [=.. *fr' liili]XH, --; ? (slow)

HA is Ure onlY source of H' and A-'

Hf of sbd e!cz!Dbn Tdboof dgpn ljott jh/dpn

oliCt,

$O'

'/o-o:

hYjsl

A) Show lhatthe nrechanism is consistentlvith the rate lur* uuing, a) Equilibrium aF)proacl\;

b) steady-state prinfiple.B) Sketch the reaction profile.

For rhe frrsr order reaction: A -+ p, aH = -.20 kl' Ir the activallttft:#t H ';;:i'il''',P"

P

For the frrst order reaction: A .-+ p, AH = - 20 KJ' II Lrru ou''""";-C i, e.iS min, what is

* A. is 60 kl and the half*life of the reaction' A -

P' at l':

lihlf-life of the reaction: A -.-+ P, at 50'C?

\

s'r:--' A -? B' is 35 min' enougltAls'placed itt

-1

the half-life of rhe first order gas-phase r:acLio^n:j .=i;;i oi.$rr. aiter 1'10 mirr?The half-life of the first order gas-phase isactlon: A < ! "r -

ssure aiter 1'10 min.r

a container so that ib';;";';;;z1s mm Hs' what is the toral pre

i 'vith the observed ra[e latt'

6 Propose a plausible mechanlsm tgn:i:tTt t'Tr''*;,"*'l+,

Rare = [Nozcl] tt'lt'nl"itlttion'"; ils-61---* 2 No2 + c+2

7- The rate constant at several temperatur:s have been reported for trre reaction of acelanlide

-t'rt 'iil'=

acid in aqueous solution: I n rcq

O'f SZ 0'1S2 0'233 0'26J v'1" r

k (L mol- r) :-':' ;;; 30.0 32.0 ir'0'. ('C) 2i'0 7l '5

Detei'nrine tlre activai':c*tnptgy graphica\\y''

:tionstepsintheorderoichain-iniii;tion'an''ir-hain-r: Rear,ange and label r:re iollorruing rear:r'

prnpagation steps: CIO + O .--,-----+ CL 1. O,

^crit' + uu -_+ gF'zcl : cl

""Lr'" oe + Clo + oz

rr -^_arinnT

Suggest a possible chain-ternrinatfon stlp' What is the over-all reaction?

9' Al temperatures belor"'l 50g"c' tl" -'::- dimerization of:" czH+ + c-rHs follows second

order kinerics. At 1400c, the rate.".*;i'fJ;hir r.iirion ir:.qz x 10-r M-I s-'. Suppose we

start with 0'20 n4 ;rLtH" what fractiJil iht original concenlration would remain after one

hour? )-5 g' what is the half-life of recl?

10.It takes 165 min for a- 1'000-9 sample of reCl to decay to 0'1i

i , . ^n is accidentally exposed for 95 s to a 28-mG source of beta radiation coming

11-A 65-kg Perso- -'n'o* u iampte of ssr'

egrations per second (dps)?

11.1' Wnat is tiri activity of the radiaflon source in disint

, l',i Hil'..;.'ri*IJ[ny:rm""'ffi;:ii?i!]''l'o 50% or the m*i:l:'{}$ is

' au,oqj;-uy the person, .nii,,ii.g tr",tt tl.q ui,,ojlJ.|-udiation is spread $". the

11 4 ?r[,T ;,'ffT#;'JJ'., icel's*: *sa? !: lfl i :?': L#T': : 1 ; ]?H'i n o'n s i p ve rts?

Hf of $d elcz!Dbn Tdboof dgpn ljorl jh/dpn