You are on page 1of 9

CHEM 636 -Fall 2006 -Exam 1

1. Short Answers (5 Pts each)


(a) What is the Principle of Microscopic Reversibility?

(b) Which complex would be expected t o undergo more rapid CO substitution? Why?
Fe(CO)5

(c) It took 150 sec for 50% of a particular reagent to decompose. If the initial concentration is 0.050 M and the decomposition reaction follows second-order kinetics, what is the value of the r a t e constant?

CHEM 636 - Fall 2006 - Exam I

Pg. 2

(d) For a reaction which obeys first-order kinetics and has a kl value o f 1.OO x 10-~sec-' at 2s0C, what is the value of the half-life at 25"C?

(e) A typical diffusion controlled bimolecular rate constant (include units) at ambient I x lo% lo10 ~ - i - ~1 temperature in an organic solvent is:

(f) AS one proceeds from a D(dissociative) mechanism to an A(associative) mechanism

what are the trends in AH', AS', and AV'. At this point do not worry abour Z processes.

CHEM 636 - Full 2006 - Exam 1

Pg. 3

2. Derive the rate law for the equilibrium process below which involves the intramolecular isomerization of an octahedral metal carbonyl derivative.

Given the kinetic data for the forward reaction (cis + trans) at various temperatures, i-e., kobsd= kl+ k-1 , and if the equilibrium constant I ( , measured at 64.8"C of 5.3 is not very temperature dependent between 60 and 80C, calculate AH' and AS' for the cis + trans process. Draw an energy vs reaction coordinate profile and clearly indicate which isomer is thermodynamically more stable. Would you expect the value of & to be greater or less than 5.3 if n-Bu3P is replaced by the smaller PMe3 ligand? Explain. Temp. ("C)

bbsd x 104sec-'

-14.8

-14.6

-14.4 y = -12091x + 21.254 R2 = 0.9983 -14.2

-14 ln (k/T)

-13.8

-13.6

-13.4

-13.2

-13

-12.8 0.00282

0.00284

0.00286

0.00288

0.0029 1/T

0.00292

0.00294

0.00296

0.00298

CHEM 636 -Fall 2006 - Exum 1

3. For the ligand substitution processes described below, Lbsd is a composite of two reaction path ways

Mo(CO)G+ PPh3
kobsd

-+

Mo(CO)~PP +~CO ~

(1)

= {kl + k2 [PPh3]}

Pt(dien)CI'

Br-

-+

Pt(dien)Br'

CI-

(dien = a tridentate amine ligand)


kobsd

= {kl + k2[Bf]}

(a) Compare and contrast the significance of and the relative importance of the two terms in the rate-laws for each process.

Mo-c~ d i s s O ~ - & ~ ~ L MO(CO)' t ->, Mo(0)5 + C Q ) W has~di4~lpm4,~f'~hd v s + . -4-L k'k&on5c bk, usi.%TA. S ~ ~ Wo ( w ) is ~ \ ~ c l &S hF I ~ T3vi%,.Hu. b, isw& S h L 4 - L , & . , ~ ~ ~ h ~
I '
a

L,+te*

%I

~ S ~

koLv-3a j c - i h L k i ~ U ~ ~ \ / c

l b ~ ~ < + , , & ~ ~ .
'D~SL

m d lay-r +&& . (b) Assuming both reactions are spontaneous as written (i) For reaction (1) draw the reaction profile for the process proceeding via ki. Account for the fact that the intermediate in this process does not discriminate between incoming ligands.

4 , u 5 ; 2

a,

CHEM 636 - Fall 2006 - Exum I

Pg. 6

(ii) For reaction (2) draw the reaction profile for the process proceeding via k2 where bond-breaking is the rate-determining step.

& & L h o(c) Is AV' for the kl pathway in reaction (1) negative or positive? Explain. Would an increase in pressure retard or enhance the process?

(d) Is AV' for the k2 pathway in reaction (2) negative or positive? Explain. Would an increase in pressure retard or enhance the process?

CHEM 636 -Fall 2006 - Exam 1

Pg. 7

4.

(a) The ligand substitution reaction below was shown to occur via a dissociative (D) process.

The kinetic data in the table contains the observed rate constants as a function of [NHCsHlo] and [CO] for reactions run at 28C. Derive the rate law for this process. From the data in the table calculate the competition ratio of the five coordinate intermediates for piperidine (NHC5Hlo) vs CO.

a[CO] is in large excess

45000

40000 y = 3668x + 1567.6 R2 = 0.9987 35000

30000

1 / kobsd

25000

20000

15000

10000

5000

0 0 2 4 6 [NHC5H10] / [CO] 8 10 12

CHEM 636 - Fall 2006 - Exam I

Pg. 9

(b) What is known about the reactivity of five-coordinate intermediates of this type with incoming ligands in hydrocarbon and in perfluorohydrocarbon solvents?