1 Y O R K U N IV E R S I T Y W 2 0 1 0 S C /C H E M 1 0 01.03 N Q u iz N o. 1 J a n u a r y 28, 2010 NAM E: S T U D E N T NO.

_ 50 m in u te s 30 M a rk s

R = 8.315 J K - ^ o r 1 = 0.08206 L atm K - 1 m o r 1 ; 0C = 273.15 K [A\t = [A]0 - akt ; [A}t = [A]0 e~akt ; [A ]t 1 = [A]^1 + akt ; k (T ) = Ae~Eal RT _ N o te : alw ay s w r ite n u m e r ic a l a n sw e rs w ith c o rre c t n u m b e r o f sig n ific a n t figures A ll fin al a n sw e rs a n d s ig n ific a n t in te r m e d ia te r e s u lts m u s t b e w r itt e n in in k . [m arks] [5] 1. Fill in the blanks with the appropriate missing words, symbols, or numbers. ( 1- 1 ) If ^4 Products is a unimolecular elementary reaction, its rate law is R >

= KCAl _

( 1- 2 ) If A - Products is a second order reaction with a rate constant of 0.50 M -1 s -1 , the rate of reaction when the concentration of the reactant A is 0.20 M is _/

Q . Q 20 MS

(give a numerical answer) (1-3) In an elem entary reaction A-\-B Prod uc ts, the number of A-B collisions is proportional > to [A][B], and the fraction of those collisions having sufficient energy to generate products is proportional to * & __________ ~________________________ . (give a m athem atical expression)

(1-4) Consider: 2 N H 3(aq) + OCl~{aq) >N 2H A{aq) + H 20() + Cl~(aq). If [NH3] is l.OOM a t time t = 0 and 0.900 M a t t = 80s, the average rate of reaction in the time interval from 30 s to 50 s is roughly _ i v 10 M ^ _______ (give a numerical answer) e O ^ A u i (1-5) Circle the correct answer. Consider the Arrhenius law, k = Ae Ea/RT; for a bimolecular elementary reaction where the products have a lower energy th an the reactants. Which of the following is certainly true? (a) E a < 0 (b) 0 < E a < R T (c) E a > R T (d) k > A

2 [2] 2. Chlorine and fluorine are introduced in an empty vessel and react at constant tem perature according to Cl2(g) + 3 F 2(g) If C1F3 is produced at a rate of O.lO M /s, then: (2- 1 ) at what rate is F 2(g) being consumed? 2 C lF 3(g)

(2-2) what is the rate of the reaction?

0-050
[4] 3. The decomposition of N2O5 into NO3 and NO2 is a first-order reaction and it is taking place a t constant tem perature and constant volume. If the p artial pressure of N2O5 is 400mmHg at time t = 0, and lOOmmHg at tim e t = 100 s, w hat will th e p artial pressure of N2O5 be at time t = 250 s?

1 S '* S

<v\kv\H

0.005 - 0 .0 0 4 ,0.003

0.04 g 0 .0 3

0.002
* 0.001 0.2 0.4 0.6 0.8 [A] (M) (a) 1.0

0 .02'

a! 0.01

10

20 30 tim e (s) (b)

40

50

(c)

(d)

[6] 4. Each of the three graphs above is for a different reaction, but each reaction is of the general type A y Products. Indicate the order of reaction in each case, and explain briefly (one sentence) your choice in each case. (a) the order is 1 b e c a u s e ...^ fo \* . Cml ^

(b ) the order is

0 _____

because . . . H'C.

*5

C-a/'vSfhv^ VS "V )

(c) the order is

b e c a u s e ... f a

VtfUQrty

(d ) the order is

because . . . iJ r^

half - l i j ^

is

c e ^ s W f-

4 [7] 5. The data shown below were collected for the first-order reaction: N 20 (g ) Tem perature (K) 800 1000 R ate C onstant (1/s) 3.24 x 10~5 0.0614 > N 2(g) + 0 ( g )

Determine the activation barrier E a and the Arrhenius constant A (A is also called th e preexponentional factor) for this reaction.

.
1 l X IO

it
s

5 [6] 6 . Consider this overall reaction which is experimentally observed to be second order in X and first order in Y. x + y >x y (6-1) Is it likely th a t the reaction occurs in a single step in which X and Y collide? Explain. k) 0 I f it* be. OCClAHLtfi k iA a sfe p /otv\>

w w aM

L x l tV ^

(6- 2 ) Is the following two-step mechanism valid? Explain. 1. 2. 2X ^ X 2 X 2 + Y >X Y + X (fast equilibrium)

T h is

ft a l< W

V70/UW (v ^ c K q ^ i^ r^ of\4 (\\S o n 3pR>c|uc 5

Hr NLfc

-(+c ^X p ^ O n rc rc fa l KCtc^!( 3r \ -

THE

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