General Chemistry II - Worksheet 3: Kinetics and Mechanisms

Model 1: Elementary Steps

The rate law shows us how the rate of a reaction is affected by the concentration of the reactants and you worked
out the rate law from experimental measurements.
Most reactions occur at the molecular level through a sequence of one of more events called elementary steps.
Only two types of elementary step are important:
• a unimolecular step: a bond breaks in a molecule
CHEM1612 Worksheet 12 – Answers to Critical Thinking Questions
• a bimolecular step: two molecules collide leading to one or more bonds being broken or made.
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Because each step in a mechanism is either a unimolecular or bimolecular step, you can write the rate law down
as you did in Model 1:
• a unimolecular step involves only one molecule so the rate is proportional to its concentration:
rate = k1[Br2(g)]
• a bimolecular step involves two molecules colliding so the rate is proportional to the concentration of
each: CHEM1612 Worksheet 12 – Answers to Critical Thinking Questions

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.
1Model (a)
2: A The
Multi-Step
(d) first[O] step= Mechanism is the rate determining "#$ %"#% step. 2
e.will double. ..
12. (a)
(b)
(c) The
It will first double. step is"# the rate determining step.
$ %the
12. (a)
(a) equilibrium
The
The number
first
second 2.step constant
ofis
step collisions
(a)the is = KThe
rate =determining
rate will double.
determining
number ofstep. step. will double.
collisions
(b) rate ! [NO ][O ] or rate "#
= k& %[NO ][O ]
)] !or[Brrate 1 . = k[Br (a)
(c) (g)] rateThe
rate ! first [Br step 2 is 3 the rate determining 1 2 step. 3
ate 2(g)] or (b)
(b)
(b) 2rate =rate
The k[Br ! !
number (g)]2(g)]
[NO
2[NO
[O][O ][O
2][O of ] 3]]or or
collisions
(b) or
or rate rate
rate
rate
The
=will
k[Br
== kkkdouble.
=
number '"#
12[NO (g)]2][O
2[NO
[O][O of ][O
% ] 3]]
collisions (will
$ '"#
$
& %to obtain
double. ( ) "#a&rate
%$ law that does not involve
sm (e) Substitute '"#your &
2 % answer to (d) into your
3 3 1 & rate law from
2 3 3 (b)
of
hecollisions
2. will(a)
2. (a)
(b)
(d)double. The
(e) =
rate
[O]
The ! [NO
second
number rate2step =
][O ]is
ofk2collisions
3[O][O the
or 3rate = kdetermining
]rate 2×
= kdouble.
1[NO2][O ×step.3[O
] 3] = = where k′ = k2K
number
determining 2. of collisions
step. (a)
(c) any
Thewill
rate second
intermediates.
! double.
second "#$2(g)][H(g)]
[Br step
%step (c)is is the the or will
rate
rate "#!determining
%"#%
determining
rate $[Br ="# 2k[Br
(g)][H(g)] step.
$ % 2(g)][H(g)]
step. or rate "#$=% k[Br2(g)][H(g)] "#$ %
of 2. will(b) (c)
(b)
(a) rate
The
The !
equilibrium
!second
number [O][O constant
3]] collisions
step
of is or the = Krate = will = k2[O][O
determining
"#kk%double. 3]] step.
hecollisions
number (b)
of collisions
(b) double. rate
will!
(f)
rate [O][O
double. The rates
[O][O 3] (a) ofor or theThe rate
forward
rate
'"# == & % andofbackward
[O][O
22[O][O ] by ($a'"# reactions
%$of increase
4:(it are
) "# the same.
$quadruple.
3.
te = k1[NO2][O3(b) (a)
] The number 3. of
3 collisions will & increase
number 33collisions factor &will & % by
will a factor of 4: it will quadruple.
(e)
(c) rate
rate ! !
= k[O][O
[Br [O][O (g)][H(g)] ] ] = or
k × rate
or "#
"# =
rate %"#%
k
%"#% ×
= [O][O
[O
k[Br ] =]
(g)][H(g)] = where k′ = k2K
ate)][H(g)] or rate = k[Br
! [Br2(g)][H(g)] (b)
(c) (g)
orrate (g)][H(g)]
2rate
equilibrium! ='"# 2
rate
k[Br
[NO(g)]
2 &of %2(g)][H(g)]
3
constant
3
forward
2
(b)or=
2
rate
K rate
= "#
reaction
"# =!
$
$
$$ %%"#%
2
k[NO(g)]
[NO(g)] = k1[O 3 3
22 3]
or "# $ % = k[NO(g)]
rate "#$2%
te determining step.
(d)
(c) [O]
equilibrium = constant = K
K = "#= "# %%
'"#of $
& % 3. (ofwill
) "#(c)(a) $
%increase
equilibrium
The bynumber "# constant
$ %constant
ofof collisions it== will "#
will $ %"#%
&
&increase by ][O] a factor of 4: it will quadruple.
hecollisions
number &(f)
collisions
(c) will
The
equilibrium a factor
increase
rates rate of ofthe by 4:a factor
backward
forward K =and quadruple.
of "#
reaction %it
4:backward
& = k-1quadruple.
will [O reactions are the same.
te 2= k2[O][O = 3] (b) where 2 ! '"#
k′ = k
%
K
2 2 "# &%
2
$ ( ) "#& %$
2
# %
)] $!or "# %
$(g)
rate = k[NO(g)]
2 rate '"#
'"#[NO(g)]
As & %
% reaction
&these2 or
rates rate
are '"# =
equal & %
k[NO(g)] at equilibrium: ( $ '"# & %
ate [NO(g)]
"#$ %"#%Model(f)
or
(d)
2: A If
(e) rate =
rate
[O] k[NO(g)]
Multi-Step
rate =of forward
Model & 2:
Mechanism A =
Multi-Step k [O ] Mechanism =rates of the forward
the==first k2[O][O ] = k2 × × [O3] = where k′ = kbackward
2K
1 3
tions are the same.
(d) [O] '"#"#$step
"# % % is3 at equilibrium,
&
% "#$ % what are the "#relative
$ % "# %"#% "#$ % and reaction?
"#& % 1.
(d) [O]
rate =of backward $ reaction = k [O ][O] ( * $
'"#,
(a) The first"#step 1 . % iskthe (a) [Orate The first
determining -1 step2 is
step. the rate determining step.
The rates $of the 3] ='"# kand
-1[O%backward
2][O] or reactions (($$+* $ the (%)) "# =K $ so K = k1 / k-1 or k′ = k2k1/k-1
Model (f) & %%$are "# & %%$
2: A Multi-Step Mechanism1forward same.
Mechanism '"# &
& % ( '"# & "#&( &
ulti-Step Mechanism (e)
(e)
(b) As
rate
rate = these
=
! k
k[NO22[O][O
rates
[O][O 2][O
are
]
(b) =
33]3]= kor
equal
k × rate
22 × rate
at
'"#
equilibrium:
! =&%[O[NO ×
%k1×[NO [O
[O ][O]
2 332]][O = ]
=3 ( or
3]$ '"#& %
rate $= = k [NO
1 ( "# ) 2 & %$3] where
][O where k′ k′ == kk22K
K
1. (g)
(a)
(g)
3.
(e) rate
The
ByFor
rate of
first
first
the
= k forward
step
2writing3 down
rate
[O][O is
determining]reaction
the = k rate
2 the rate
× "#
"#
= k
step,
$ 1%
determining
$ ]
laws
×
3 [O step.
3for the
] = "#
"# $ %
%
forward
$ = and "#
"# $ %
%
backward
$ reactions
where k′ = kin
2Kthe first step, find a
is the
he first steprate determining step. ( "# %"#%
2. is the (a)rate relationship
determining
The second 2. step.
k1of [O step
between
(a)is the The
3] =3forward kreaction[Othe rate
2][O]
"#second
rate $ %constants
determining
or
*
step
, isstep.the
kreactions
"#
13]and k-1 and
$ % are
$rate determining
Ktheso
= the "#$ %K step.
equilibrium= k1 / kconstant
-1 or k′ =K. k2k1/k-1
(f)
(b)
(f) The
rate
rate
The !
rates
of
rates
$ 3] ( ) "# %$ 2 2 2
backward
[NO rate of 2 the
][O
the
= k forward
]
[N -1or
O rate
][O and
and =] = kbackward
k
backward
-1 1 [O
[NO (+*2][O]
2 ][O reactions
"#& % are the same.
same.
[O
ate "#3!&] % [NO
or 2rate ][O3=( k1'"#
] (b)
$
(f) [NOrate
or &2%The
][O = k
rates [NO of& ][O
the (b)]
forward rate 2
and ! [O][O
backward ] or
reactions rate =
are k [O][O
the same. ]
× [O 3] = (g) (g) rate
rate !
=these
of
1 [O][O
forward
2
3] are
3
where
reaction or rate
=k′ =[Okk223K
atkk=equilibrium: [O][O 3 3] 2 3
#tep $ %"#%
# %
is the
2.3.rate
(a)
For "#
determining the%
As
The
rate
This
rate second
of forward
involves"#
determining
step.
rates
%
step [N is
reaction
2 O equal
step, the 2 ] rate
which = determining
11[Ois 3an]] intermediate step. and cannot be controlled experimentally. However, if the
he$second = Kstep so is(g) Kthe =$krate / kdetermining
1 rate -1 of k′ =$ k2k1step.
or forward reaction
/k -1 ="# k1[O %"#% 3] "#$ %"#%
"#& % (b) first
rate
rate !
of
ofstep backward
[O][O
backward is at3]equilibrium:
(c) reaction
or
reaction rate =
equilibrium
= = $
k
k k [O
[O [O][O (
][O]
2constant
][O]
* ] "#
= K
$ %"#%
=
[O2][O], "# % "#
-1 2 3
and
3] !backwardor rate (c)[O][O
reactions rate
equilibrium
are
3]= the k=2[O][Ok2same.
k[N 2O
constant 2][O-1 2][O= K2][O] = = k-1 -1 2
2 = &K% so K = k1 / k-1 or k′ = k2k1/k-1
ate [O][O 3] = k2or raterate of backward1[O 33] = kreaction or
"#%"#% &% (
As these rates "-
are $ # equal$ % at"# -1
equilibrium:
$ +* &
= k1[O3] "#$(c) This
%"#% involves As"#
these
equilibrium %"#% [N Krates 2eqO =2] are
constant which equal=$ is K= an
orat [Nequilibrium:
intermediate
'"#
2O2]&= % Keq[NO] and cannot 2 be controlled experimentally. However, if the
3. For the As
rate $these '"#
determining rates & % are step,
"-#% equal at equilibrium:
"# %
onstant = Kconstant = first
= Kstep is = at equilibrium: (d) [O] = & (*
nquilibrium
= k-1[O2][O] "#(d) &%
=[O]
"#& %"# "#$( %(** , "# "#
"#
$%"#%
$$%"#%
$
%"#% =
cannot be controlled rate ='"#
Substituting
experimentally. "-
k 1[O
kkk211$[N
1 $#
[O[O
%
&2%$33O
3
3 ]
this = k -1
kkinto
]]% 2However,
==][O -1
-1
[O
2[O]
[O
2
2
2the][O]
][O]
][O] rate
if the
or
or
orequation ( +*
+*
* ,, gives: "# &
& %
= K so K = k11 / k-1
= KK so
so KK == kk1 // k
k
-1 or k′ = k22k11/k-1
-1 or
or k′k′==)kk22kk11/k/k$-1-1-1
'"#& %
t equilibrium: (d) [O] =
Keq = "# % $ or [N2O'"#
-1 2
2] = K%eq[NO]
((+* 2 "#
"#
2 &&
%
'"#
% $ & % ( ) "# %$($2'"#& %
1 -1 $
( 2"#& %
O] = 3. Thisthe
For involves
rate "-#%
[N
determiningrate $2O= 2] kwhich 2[N
(e) step, 2Ois 2][O an
rate 2]intermediate
=&=k2k[O][O 2 × Keq
+* [NO]
3] =
(and k2'"#
$ × [O
cannot
× & % 2] be=×kcontrolled
Keq3]&[NO]
2[O [O2] = k[NO]
= experimentally. = [OHowever,
2] where whereifk the
=k′k2=Kkeq2K
"#$3. 3.%*
( (e)
"#
For
For %"#%
$the
the rate
rate
rate =determining
k2[O][O3] =step,
determining step,k2 × × [O3] = "#$$ %= ) $
"# $ % k′ = k"#
where 2K $ %
O] or , Substituting
first step The is at
= K=proposed
equilibrium: mechanism '"#"# $=
k′is &%consistent
%k2gives: k1/k-1 with ($ '"# "#the $ %& %experimental
( "# "#$&%% rate law, and warrants further investigation
rate kso
this [N
22[O][O
into K$22=the
22O ][Ok1 rate /])k-1 equation
22k
or $ rates)× =
(+* '"#&(e) % "#& %'"# rate ( = k
'"#
%=$ k"- % ]
(f) =(
(forward "# × The %$ of[O the]
$ = forward and backward whereare
reactions k′ the
= k2same.
K
rate&rates 22[N &22O %22][O $ '"# 22] &&%"# ( "#& %2 reactions
2 3 2 3
(f) The $ of # the
$ = and $ %backward "# $ % are the "# 2 $%
same. 2
O3]==kk22[O][O
ate × The
3. ] =This
"#3$ %This
k×2 [O
reaction 3]rate
×involvesK= eq = ×
between = [N
"#
k2[O [N 2O 32]22O
%NO
][O
]=2which
and or2[N ] =2is2gives
O kan
O =
=of Keqwhere
22]×intermediate
KNO [NO]
eq[NO]
k′×=[O
2
2. By varying and kwhere
2K]cannot
=[NO]k2k′Keq=be[NO] K[O[O
k2controlled
and ] = k[NO]
2],2 the experimentally.
rate law [Ohas
2] been
where found
However, k = kto
2Kifbe:
eqthe
(f) "#
involves
The $ %rates [N"-#% $222ofO $] which
the (g)
forward"#"# $is %an
%$rate
an andintermediate
intermediate
backward"#
forward $ % reaction and
and
reactions cannot
cannot = kare1[O
be
be ]controlled
3controlled
the same. experimentally.
experimentally. However,
However, if
if the
the
(g)
first
The step rate
proposed is at of equilibrium:
forward
mechanism
22 reaction
2
is consistent = k1[O3]with the experimental rate law, and warrants further investigation.
forward and first
backward steprate is =
at
andreactions k[NO]
equilibrium: [O 2
arereactions ]
therate same. rate
he= krates of the
2Keq[NO] [O
2 forward
Substituting
(g)
2] = k[NO] rate
rate of
backward
2 this
of[O "- forward
2]$#where
backward
into
$%
thereactionk = kequation
reaction 2K =eq=kof
are 1k
the
[O backward
-1[O
gives: reaction = k-1[O2][O]
same.
3] 2][O]
It is proposed that$#
"- #the %% 2reaction proceeds through 22are equal 2 ifsteps:
3"-
nrdteintermediate
reaction
of forward = k1and [O 3]cannot Krate 1be
=of=controlled $ or [N
experimentally. 2O Ask22]]×these
= K [NO]However,
rates theat equilibrium: 2 2
ratereaction
law, and=rate keq [O ]k2$[N
eq $O eq[NO]
perimental K warrants= backward
"-#% 2$
further ][O
or reaction
2[N]=
investigation. O =
= KkK eq[O [NO] ][O] 22× [O2] = k2Keq[NO] [O2] = k[NO] [O2] where k = k2Keq
As
K eq these
= "-#% rates $$
areor equal
[N 2O 2at
] =equilibrium:
K -1 eq [NO] 2
NO(g) eq +
"-#% NO(g) 2 N 2 O eq fast equilibrium (
* law, "# $ %"#%
ardofreaction = kreaction
[O2proposed
][O] 2 2
te backward The = these
k-1this[O ][O]
mechanism is consistent with the experimental rate and warrants further investigation.
-1
Substituting As 2rates
into the are rate equal at equilibrium:
equation k gives:
[O ( *] = k "#
[O $ %"#%
][O] or , = K so K = k1 / k-1 or k′ = k2k1/
2 , "# %"#% = K so
1 3 -1 2
s]s=are equal at2 are Substituting
Substituting
equilibrium: N O
2 2 this (g)
this +
k1into O
into
[O32] the àthe
= k-1 2NO
rate
rate [O22equation(g)
equation
][O] or gives: gives: k 2 ; slow (2+* K = k1"# / k
& %
-12or k′ = k2k1/k-1
these
Keq rates
[NO] equal atrate equilibrium:
= kk2[N 2O 2][O 2] = k 2 × K eq[NO] (
(+* *2 × [O 2]"# = &k%2K eq=[NO]
$ 2[O 2] = = k[NO] 2[Ok′2] where k = k2Keq
Is this( mechanismrate = k
"#k$2[N 21[N
3. %"#%
[O 23O ] 2=][O
consistent For k-12[O ]
the = 2][O]
withk 2 ×the
rate K or
eqexperimental
determining[NO] 2 × , [O
step, 2] rate
= k 2Klaw? K so
eq[NO] 2 [OK 2] = kk[NO]
1 / k-12or [O ]= where
k2k1/k-1k = k2Keq
* rate = ( *2O2][O "#2is ]$ %"#%
=consistent
k2 × Keq[NO] (+* × [O2]"# = &k%2Keq[NO] [O 2] =andk[NO] [O22] further
where investigation.
k = k2Keq
] = k-1[O
uation 3.
2][O]
kgives:
1[O 3] = kor
The
For the][O],or mechanism
proposed
-1[O2proposed
The
rate mechanism
determining , = K is step, soconsistent K == K k1 /so with
kwith
-1 orK the
= experimental
k′ k=1experimental
the
rate
k/ 2kk-11/kor-1 k′ = k2rate k /klaw,
law, and
warrants
warrants further investigation.
3. 2 For
Thethe
For (the rate determining
+*rate
proposed "#
determining (2 &+*
mechanism % "#
step,
step, is %2rate = k2[N
&consistent with 2O2][O2]
the experimental rate
1 -1
law, and warrants further investigation.
× Keq[NO] × [O2] = k2Krate eq[NO] = k2[N [O22O ] 2=][O k[NO]
This
2]
involves[O2] [N where k = k2Keq
ning step,
ate determining step,involves rate = [N k2[N 2O ][O 2] is an intermediate 2O2] which is an intermediate and cannot be controlled experimentally. H
This O ] 2which and cannot be controlled experimentally.
sistent with the experimental This involvesrate [N22O 2
law, 2] which first
and warrants step is an is intermediate
at further
equilibrium: and cannot be controlled experimentally. However, if the
investigation.
Oate 2][O= 2k]2[N2O2][OHowever, This
2] step
first involves [Nfirst
isifattheequilibrium: 2O2]step which is atisequilibrium:an intermediate and cannot be controlled experimentally. However, if the
first step is at equilibrium: "-$ #$ %
] which
olves [N2isOan intermediate
2] which and"-
is an intermediate cannot # % be
and controlled
cannot Keq be = experimentally.
controlled $ 2 orexperimentally.
[N2O However,
2] = Keq[NO] the2
ifHowever, if the
rium: "- $ $
# % "-#%
is at equilibrium: Keq = $ $$ or [N2O2] = Keq[NO]2
Keq = "-#%$ or [N2O2] = Keq[NO]
% "-$ #$ % "-#% Substituting this into the rate equation gives:
2 2 the rate equation gives:
eq = or [N2O$2] =or Substituting
KSubstituting
[N [NO]
2O2] = Kthis this[NO] into
into the
the rate rate equation rate = k2gives: [N 2 2 2
"-#%
eq
Substituting this
eq into equation gives: 2O2][O2] = k2 × Keq[NO] × [O2] = k2Keq[NO] [O2] = k[NO] [O2] wher
rate =
rate = kk2[N [N2O O2][O ][O
The 2]]proposed
= kk2 ×
= ×K [NO]22 ×
Keqmechanism
[NO] × [O [Ois 2]] consistent
= kk2K
= Keq[NO]
[NO] with
2 2
2[O2] = k[NO]2[O2] where k = k2Keq
[O the] =experimental
k[NO] [O2] ratewhere law,k and = k2Kwarrants furthe
ingthethis
rateinto equationthe rate gives:
equation gives: 2 2 2 2 2 eq 2 2 eq 2 eq
The proposed
proposed mechanism is2 consistent
consistent 2with with the experimental
experimental rate law, and and warrants further investigation.
Oate][O
2 = k] [N
22 = kO×][O
22 2 K The [NO]
eq2
2
] = k ×× K[O [NO]
2 eq2 ]mechanism
= k2K× [O
2 eq 2 [NO] ] is
2 2 eq = [O k K] =[NO] 2 k[NO]
2 [O[O
2 the
] =] k[NO]
2 2 eq where 2
[O k =] kwhere
2 eqKrate law, k = k K warrants further investigation.
nism mechanism
osed is consistent
iswith
The the experimental
consistent
proposed mechanism rate law, andrate
with the experimental
is consistent warrants
law,
with further
theand investigation.
warrants
experimental further investigation.
rate law