Weakly Assignment 10

Lecture 36 - Lecture 39
November 18, 2014

Contents
1 Catalyst vs Promoter

2 Forms of Catalysis

3 Confirmational Analysis
3.1 Case 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 Case 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2
2
2

4 Conditions for Catalysis

4.1 Necessary Condition . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Sufficient Condition . . . . . . . . . . . . . . . . . . . . . . . . .

2
2
2

5 Acid - Base Catalysis

5.1 Specific Acid Catalysis . . . . . . . . . . . . . . . . . . . . . . . .
5.2 Theories of Acids and Bases . . . . . . . . . . . . . . . . . . . . .
5.3 General Acid Catalysis . . . . . . . . . . . . . . . . . . . . . . . .

2
2
3
3

Catalyst vs Promoter

Both stabilize the ground state as well as the transition state. but the catalyst
is one which stabilises the t.s. more than the g.s. That way it actually decreases
the activation energy of the reaction. while the promoter can only stabilise the
g.s. well enough.
Also the binding to the catalyst should not be very strong to separate the
catalyst.

Forms of Catalysis

Binding is very important for catalysis. Binding is similar to to solvation(how?).

Just like water dissolves NaCl, is due to binding of polar molecules. Also,
relative rates of intra molecular reaction depends upon the no of carbon atoms
in between and the presence of conjugation.
1

Confirmational Analysis

3.1

Case 1

C2 H6 molecule All confirmations of each kind(staggered and eclipse) are equivalent to their
kinds.

3.2

Case 2

C4 H10 molecule Not all are equivalent but the completely anti confirmation has the lowest energy. And the energy plot is symmetric again.
If we replace one of C(2) hydrogen with -X, then the molecule will become
chiral. And due to no mirror images now, the plot remains no symmetric.

Conditions for Catalysis

4.1

Necessary Condition

Catalyst has to bind the ground state.

4.2

Sufficient Condition

It has to bind the Transition state.(better)

Acid - Base Catalysis

Two kinds of Acid/base catalysis are there 1. Specific Acid/base Catalysis

2. General Acid/base Catalysis.

5.1

Specific Acid Catalysis

Reaction of substituted epoxide with methanol. The protonation happens before the RDS. methanol attacks the neutral epoxide very slowly while quickly to the protonated epoxide. This catalysis depends
upon the protonating power of the solution only.
S + H + < > SH + K1 andK1
SH + > P K2
Rate =

d[P ]
dt

= K2 [SH + ]

K=
d[P ]
dt

[SH + ]
[S][H + ]

= K2 K[S][H + ]

SAC - Rapid protonation follwed by slow step.

5.2

Theories of Acids and Bases

1. Arrhenius Theory - H + donating species are acids and OH donating species

are bases.
2. Brownstate - Lowry Theory - H + donating species are acids and H +
accepting species are bases.
3. Lewis Theory - Lone pair donating species are bases and accepting one
are acids.
4. Pearsons HSAB principle - It talks about the polarising power and polarisability. Hard means more positive charge density and soft means less electron
density.

here the upper line is strong electrolyte and the other curve is for weak
electrolytes.
]
+
in the equation for SAC - d[P
dt = K2 K[S][H ]
+
the conc. of H means the conc. of protonated solvent like H3 O+ and not H +
itself.

5.3

General Acid Catalysis

Catalysis depends not on pH but also on the conc. of undissolved acids.

The proton transfer is the RDS here. We use a weaker acid than the one in
SAC, so the H + is not completely dissociated and makes it the RDS.
Basic difference bw SAC and GAC is that there rds are not the same steps.

SAC only depends on the protnated solvent but the GAC depends on H + conc.
as well as undissolved acids.