Topic 6 Kinetics EO Homework Booklet B 6.

Reaction Mechanism
( .. Nitrogen dioxide can react with carbon monoxide in the exhaust gases of car engines:

N0 2 (g) + CO(g) -t NO (g) + CO 2 (g)

The following mechanism has been proposed:

N0 2 (g) + N0 2 (g) -t N 2 0 4(g) slow

N 2 0 4 (g) + CO (g) -t N0 2 (g) + CO 2 (g) + NO (g) fast

What is the rate equation for this mechanism?

A. Rate=k [N02(g)] [CO(g)] ==H Sfep c/..sLp e1"vdo

® Rate = k [N02(g)]2 env ~~ NO:).. .
.::::::: e

C. Rate =k [N204(g)] [CO(g)]

...."
D. Rate = k [N(\(g)]2 [CO (g)]

Some reactions occur in a series of steps. Which is the best description of the rate-determining step
in a reaction mechanism?

A. The step involving the greatest number of reactant particles

B. The step involving the smallest number of reactant particles

c. The step releasing the most energy h~5 fv E,A ~ sCOW

The step with the highest activation energy ~ IfCli;e- <J} ~L~
3.... For the reaction 2N0 2 (g) + F2 (g) -t 2N0 2 F(g) the accepted mechanism is

N0 2(g)+F2 (g)-tN0 2 F(g)+F(g) slow

N0 2(g) + F(g) -t N02F(g) fast

What is the rate expression for this reaction?

A. rate = k[N0 2]2[F2]

SloN
@ rate k [NOJ [FJ

C. rate = k[N0 2][F]

13.
 4" A reaction occurs in four steps. The steps and their rates are shown in the table

Step Rate
1 I 0.01 mol dm-3s­ 1

1
2 0.10 mol dm-3s­
3 0.01 mol dm-3 mi~~ L----->
4 0.10 mol dm-3 min-I

Which is the rate-determining step?

A. Step 1
V, d IS , <;; {O/t-..{ Wr
.:::=:::::;;
,S'kp,
B. Step 2

~ Step 3

D. Step 4

.5 _
(~ Consider the following reaction.

NO} (g) + CO (g) --? NO (g) + CO 2 (g)

Possible reaction mechanisms are:

Above 775 K: N0 2 + CO --? NO + CO 2 slow

Below 775 K: 2N0 2 --? NO + N0 3 slow

N0 3 + CO <~ N0 2 + CO 2 fast

Based on the mechanisms, deduce the rate expressions above and below 775 K. [2J

Above 775 J( ::

BeioN '77:5 t< :

(h) State two situations when the rate of a chemical reaction is equal to the rate constant. [2J

41 .z.era 0 Vc'\ ex- V'ea c..t I 0 f\.A

• all co "",c,e Y'\. t vuX-1 ~V\S a.v-e.. I.. 0 Vv'\C \ cl r'V'-

3
b, The following reaction
is described as first order with respect to N 20 5 •

(a) Write the rate expression for the reaction. [l}

... .v:.0t~.:=~ .. ~. r ~.~~ 5 J...........................................

(b) One possible mech;mism for this reaction is given below.

Step 1
N 20 5 (g) + N0 3 (g) ~ 2N0 2(g) + 02(g) Step 2

C;scrl;)he rate expression that would result if the rate determining step in the mechanism is

(i) Step 1. [l}

.r~~.:~ .~. r.~~?5J ... ?10~~...1. ~~~I~~.~~.~ ~.f .. ~~.~~~ ... ••

(ii) Step 2. • v-o..te d € p en..-d.D <:) n.. [ /'..., ~0 .s1 a.n...d L NO.3 J [2]
........... q~ ..":--!~.3 ..CP.~. .~t:0.. . N.cJ..q!5 .I~ ..~1~. .1. ....
Sa vnJ:~ ==- k L N~Clsl~
7. 1!)

Nitrogen(II) oxide reacts with Iiyarogen according to the Tollowing equation:

The table shows how the rate of reaction varies as the concentrations of the reactants are
changed.

Initial [NO] I Initial [H 2 ] I Initial rate I

Experimlm t
mol dm-3 mol dm-3 mol (N 2) dm- 3 s-\

1 0.100 0.100 2.53 x 10-6

2 0.100 0.200 5.05 x 10-6

3 0.200 0.100 1.01x10-5

4 0.300 0.100 2.28 x 10-5

(a) Determine the order of reaction with respect to H2 and with respect to NO. [2]
I
H2 .................................................................... .
2
NO .................................................................... .

(b) Write the rate expression for the reaction. [l}

...~.. ~ ..~~.. {.~.~.J ..c ~~~.~ ........ C~l>\9~.. F-~ .C:F...fi~.r:!. (0))
IS' I
(Question! continued)

(d) A suggested mechanism for this reaction is as follows.

H2 + NO.,;-X fast step

X+N0---7Y+H 20 slow step
Y + H2 ---7 N2 + H 20 fast step

State and explain whether this mechanism agrees with the experimental rate expression
~ [4J
cO Agrees I yes; OR
VI Slow step depends on X and NO; ..... '* Agrees I yes;
l> (so) NO is involved twice and Hz once; [X].
~ Overall equation matches the stoichiometric' .. ". and - - - =constant,
[H2][NO]
equation I OWTTE; ........................~ rate of slow step = k [X] [NO];
Award [1J each for any three ofthe four above • but X depends on Hz and NO;
ECFfor "no ", depending on answer for (b). • rate of slow step = k [Hz] [NO]z;
ECFfor "no ", depending on an.swer for (b).
" - -.... ~.~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . "'.

(e) Explain why a single step mechanism is unlikely for a reaction of this kind. [21

.. ~ .. ~I.?~ .. 1.0.Y9.[~0.. _. j9.'A,("....1r:0.9.\Q-(.,Y'A~ ..... .

.:". _..s.t:.9A::~-'>:t; ~~.l.~. - B~~4~.<7-.0.\.~ .. ~(! ~{~:~;\j. -I·

B_The rate expression for the reaction between nitrogen monoxide gas, NO(g), with
oxygen gas to form nitrogen dioxide gas, NO z (g), was found to be rate [NO]z[Oz]

CO), Explain why the following mechanism is not consistent with the rate expression. 12l
NO (g) + O2 (g) 4- N0 2 (g) + 0 (g); slow step
NO (g) + 0 (g) 4- N0 2 (g); fast step

e S{OhJ 5tep/r.d.~. Involves Or'\~ ()A(!. NO CA..r\d

On e.. C);t

Ill> hOC t""'a No Q..F\. d ot'"\e 0.:1 0-~ V--eq,\.A\ve,d b~

voJ: e.. -e. Xpvf>_ SS let') )
(6) Explain why lhe following mechanism is consistent with the rate expressioI4 but is unlikely. [21
2NO (g) + O 2 (g) 4- 2N0 2 (g)

~ S((\Ce. tw-o NO CAtJ.d One. 0,2 ,'nvolv-e.A t('\

-th e (or"\e cSte....p) VV\e..cho..n; 5 ..'<"\) Cc we.....J vv-J:'e.

ex.pre.--S SlOr) pOS5d:~1 e
C» but- u.~(d:_-e-~ ~ g po.ytlcJe..s Nlll GO {ltd-€ . .. o...t
tr...e. so. rY\ e t -e. . j'"""
CCVULS-hon.. ~ (J:J,..J::; I')1...\.e d )
(iJz) Explain why the following mechanism is consistent with thc rate expression. [3]
NO (g) + 02 (g) -t N0 3 (g); fast
N0 3 (g) + NO (g) -t 2N0 2 (g); slow

• ro..te. dep-e~ On [Nol and [NO.3]

• Fch"l 'f\vst sie..f [N0 3 ] d€40~ en [NO] (Afld [0.,l]

• thu.:5 ~e.- m~$. t de-pen d Or'") [Na].l. [O::l.1

(c:b Suggest, giving a reason, one other mechanism that would be consistent with the rate
expression. [3]
~

o NO(g) + NO(g) -t N 20 2(g) fast;

<f N 2 0 2 (g) + 02 (g) -t 2N0 2 (g) slow',

• similar reasoning to above / rate depends on [N 20 2] and [°2]' and
[N202] depends on [NO] and [NO] (thus consistent with the overall third
order reaction);

17.