Kinetic isotope effect not theory

Chain reaction identify the steps

Recombination reaction most efficacious third body M
Determine the rate law
What does the rate of a reaction depend on?
Which of the following is not true about termolecular recombination reactions?
Which of the following refinements of Lindemann-Christiansen mechanism is false?
What is not true about an activated complex?
Who first proposed the idea of collisional activation to form a short lived intermediate, A*?
The diffusion-controlled rate constant does not depend on which of the following?
Which of the following statements is false regarding branching in chain reactions?]
Which of the following is not true regarding explosions?
Which of the following is wrong regarding chain reactions?
Which statement on the Kinetic Salt Effect is NOT true?
Who first proposed that an excited molecule requires enough energy in the critical vibrational energy level (=activated
molecule) so that it can react?


















What statement regarding the Stopped Flow technique is FALSE?
A. Its applications include the measurement of enzyme kinetics, study of drug-binding processes, or
determination of protein structures.
B. The reactants are mixed completely very quickly.
C. The reaction is monitored as a function of time
D. It is suitable for slow reactions.
E. The method makes use of UV/Vis spectroscopy.

The Stopped Flow technique is used in the case of enzymatic reactions, because they are very fast and
they involve short-lived intermediates. Moreover, the method is very helpful since the reactants the
substrate and the enzyme are mixed completely in only 1 ms. Consequently, the method is
appropriate for the processes mentioned in A.
Which of the following statements is an improvement that Marcus contributed to the RRK, and
thus to the previous Simple Collision Theory?

A. A molecule has several vibrational modes
B. Energy flows randomly between vibrational modes
C. The energy distribution in normal modes of vibration is treated statistically
D. The reaction of an excited molecule occurs when enough energy accumulates in one critical
vibrational mode
E. The rotational energy is included

The contribution of Rudolph A. Marcus to the RRK is even a greater refinement of the model of
collisional excitation. Thus, by contrast with the Hinshelwood and RRK theories, it involves that
each vibrational mode is treated explicitly, zero point energies of reactants and activated
complex are taken into account and the rotational energy is included, so E is the correct answer.
Moreover, another important fact is that these features are in good quantitative agreement
with the experiment, while in the RRK, the value of the number of vib. modes had to be adjusted
in order to give the best fit to experimental data.












Why does the C=O bond in the -lactam ring appear on an IR spectrum at a stretching frequency of
~1780 cm
-1
, instead of ~1675 cm
-1
, as in the case of a normal acyclic amide?
A. The N atom is trigonal planar, and thus it has more sp
2
character
B. The C=O bond is longer than in a normal amide
C. The N atom is more pyrimidal, leading to a shorter C=O bond than in a normal amide
D. -lactams are particularly stable carbonyl functional groups due to the resonance structure

Explanation:

It can be noticed from the picture of the amide that the nitrogen atom is trigonal planar,
with sp
2
character, causing the C-N bond to be shorter and the C=O bond to be longer
and appear at a lower IR frequency, so A and B are both incorrect answers.


By contrast, in the case of the -lactams, the N atom is more pyrimidal and has a
more pronounced sp
3
character, instead of sp
2
. As a result, the C-N bond is longer
than in a normal amide, while the C=O bond is shorter and stronger. Consequently, it
appears at a higher frequency, so C is the right answer.

D is also an incorrect answer, since
the resonance structure in the -
lactams, represented above, does
not contribute to its true structure,
as it does in amides. Hence, the
amides are particularly stable
carbonyl functional groups, while
the -lactams are not.








What component from penicillin G, makes it prone to acid hydrolysis?
A. The free carboxylic acid
B. The sulfur atom
C. The -lactam ring
D. The N-acyl group


The reason why penicillin G is prone to acid hydrolysis is the fact that it contains the -lactam
ring, which is highly reactive. However, if the radical R from the N-acyl chain is bulky or is an
EWG, the amide carbonyl oxygen is less nucleophilic, and hence the rate of hydrolysis is greatly
reduced. This can be noticed from the mechanism below.

What is the product of the following reaction?





Which is the correct order of the steps of the auto-oxidation mechanism?