WRITING ASSIGNMENT 10

Ishani Jain
2013CH10082
Group 5

The catalyst has to necessarily stabilise the transition state. It may or may
not stabilise the ground state, but stabilising the Transition State is a must.
A species that stabilises the ground state but doesnt stabilise the Transition
state is known as a Promoter.
There is another class of substances who bind to the substrate and stabilise
it, however, unlike catalysts they get bound too strongly and hence are unable
to break free. This doesnt regenerate the catalyst, hence there is no turnover.
Concept of binding is very important for the process of catalysis.
N aCl doesnt dissolve in Benzene at all whereas it is highly soluble in water.
This is because, water, being a polar solvent itself solvates the N a+ and Cl
ions hence the ions remain in the solution.
Similarly, even number carbon containing chains of alkanes have higher melting
point than those containing odd number. This is because in case of even numbered chains, every C atom finds somebody to pair with while in case of odd
numbered chain, one is left alone, hence less binding energy and easy to melt
the alkane.
What effect does chemical bond have on the rate of a reaction?
What I mean is: If instead of reacting 2 species to get a class of products,
we could adjust the structure of one reactant to exhibit thr properties of both
the reactants, how would the rate differ?
A quantitative measure of this is Effective Molarity, which is the ratio of rate
constants of 1st order and 2nd order reactions. Very high experimentally observed and physically unattainable values of effective molarity suggest that rate
of a reaction increases manifold if its mechanism changes from 2nd order to 1st
order.
Ground State Stabilisation The concept of Rotamer freezing suggests
that as we increase the constraint on the ring whose substituent is undergoing
reaction - the rate of the reaction increases.
This concept is relevant to the context since we are trying to figure out the
factors which control the rate of the reaction and it has been seen that rate
of reaction shoots up for some particular conformation of the reaction species.
This has a lot to do with thermodynamics of the reaction, since the entropy
factor now controls the value of G which in turn controls Keqb. or the rate of
the reaction indirectly.
For example, all chelating ligands react in their eclipsed conformation.
There would be certain reactions of double bonds that can occur only in the
trans conformation., anhydride formation being one such example.
Acid and Base Catalysis These species are indispensable to the concept of
the catalysts- given that the best catalyst in industry is an acid- H2 SO4 .
There are 2 kinds of Catalysis:
1. Specific Acid Catalysis
2. General Acid Catalysis
Specific Acid Catalysis(SAC)

In most of the compounds containing an Oxygen- Carbon bond, H + from

the acid serves to increase the polarisation of the Oxygen- Carbon bond, hence
making it easier for the nucleophile to attack the highle electron density deficient Carbon.
In SAC, the rate of the reaction doesnt depend on the proton density that
actually exists in the solution and has come from the acidic source. Rather, we
need the concentration of all the species that can possibly act as the source of
H + . The proton might have come from anywhere, but as long as it has the
potential to protonate a species, it is counted in the conc. of H + expression in
the rate law.
RateLaw:
Rate = k2 K[S][H + ]
where, k2 is the rate constant of the slow step and
[H + is the concentration of the species available for reaction( NOT NECESSARILY THE CONC OF THE ACID).
This unexpected behaviour is because of the fact that transfer of H + is the preRate Determining step, hence, the interactions during bond breaking between
the species releasing H + and H + is insignificant.
Theory of Acids
1. Arrhenius: Valid only for solutions.
2. Bronsted : The attention changes from acids to conjugate bases.
3. Lewis: Lone-pair donor/Lone-pair acceptor concept. No ionization is needed.
Pearsons HSAB Principle The interactions between acids and bases are
decided on the basis of their polarizability.
Those species that get polarised easily are called soft. In other words,the species
having lower charge density are called soft and vice-versa, the species with higher
charge density are called hard.
By the Pearsons principle, soft acids react with soft bases and hard acids react
with hard bases.
Strong Vs. Weak Electrolytes
As is seen from the figure, conductance is almost constant for strong electrolytes with concentration while it decreases rapidly for weak electrolyte. For
weak electrolytes like CH3 COOH as concentration increases, the interaction
between, molecules themselves start getting stronger, hence concentration of
mobile ions decreases leading to a decrease in conductivity.
General Acid Catalysis(SAC)
In this case, rate depends on [H + as well as the undissociated source of H + .
Here, a weaker acid than that used in SAC is used and hence the H + is removed
by the lone-pair rich species. In SAC, the H + was relatively free and would
attach at the solevnt and then be removed by the substrate.
In other words, it can be said that in GAC the attack of a nucleophile for H +
is the slow step, unlike SAC, where slow step is the next step in the sequence.