Scribd
Upload
6 views

AnswersOttoChapter3 2023

Uploaded by

baggie.baggie.bags
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
6 views

AnswersOttoChapter3 2023

Uploaded by

baggie.baggie.bags
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

1.

a) Explain why noncovalent interactions are normally under thermodynamic control while
covalent bond formation is most often under kinetic control.
b) Which interaction will be stronger: that between a dipole and a quadrupole (such as
benzene) or that between the same dipole and an ion. Explain your answer.
c) The interaction between a benzene ring and tetramethylammonium iodide is stronger in
water than in chloroform. Explain why.

a) In noncovalent interactions, the ΔG0 values (Gibbs free energy change) as well as the Ea values
)activation energies’ are small, so that the sum of the both, which is the activation energy of
the back reaction, is small as well. Thus, there is place for “error correction”: if the system has
not found the absolute thermodynamical minimum, just a local one, it can go back to the initial
state (back reaction, disruption of thermodynamically not optimal covalent bonds) and reform
the bonds in such a way so that the system corresponds to the absolute free energy minimum.
not In contrast, in covalent reactions both ΔG0 and Ea are considerably larger, so that the
activation energy of the back reaction is large as well. This means that here, once a covalent
bond is formed, the system is retained in this state, even if the this does not correspond to
the thermodynamic minimum, because the back-reaction would be too costly energetically.

b) The dipole-ion interaction has an r-2 dependency, while the dipole-quadrupole interaction has
an r-6 dependency (r is the distance of the dipole from the other chemical entity), thus the
latter is weaker (and decreases more rapidly with increasing r.)

c) C6H6…….CHCl3 + NMe4+ …….CHCl3 → C6H6……. NMe4+ + CHCl3…….CHCl3


Medium Weak Medium Medium

ΔG0= Medium+ Medium- (Medium+ Weak)= Medium

C6H6…….H2O + NMe4+ ……. H2O → C6H6……. NMe4+ + H2O ……. H2O


Weak Medium Medium Strong

ΔG0= Medium+ Strong - (Medium+ Weak)= Strong


The main driving force in the latter case is the reformation of the H-bond network of water.
2.
a) What would the approximate equilibrium constant be for the H-bonded complex formed
between 1 and 2 in a solvent that cannot participate at all in hydrogen bonding?
b) What is the approximate equilibrium constant for the complex formed between 1 and 2 in
DMSO at room temperature? (α and β for DMSO are 0.8 and +8.9 kJ1/2 mol-1/2 respectively)
c)Construct a graph of ΔG0for hydrogen bond interactions in DMSO as a function of α and β

a) ΔΔG0= -αdonor βacceptor. The α value for phenols is ca. 4 kJ1/2 mol-1/2 and the β value for acetone
(aliphatic ketones) is ca. 6 kJ1/2 mol-1/2, so ΔΔG0= - 24 kJ mol-1. However, upon binding of the 2
molecules their thermal motion is restricted, which results in a free energy loss (mainly of
enthropic origin ) of ca. +6 kJ mol-1, so the overall free energy change is ΔG0=-18 kJ mol-1, which
corresponds to K =𝑒−∆𝐺/𝑅𝑇 = 1.4×103 M-1. (for the α and β values see p. 22-23 of the script.)

b) In this case, the following process takes place: A…….S + B …….S → A……. B + S…….S

ΔΔG0= -αdonor βacceptor-αsolvent βsolvent+αdonor βsolvent+αsolvent βacceptor = -(αdonor-αsolvent)( βacceptor- βsolvent)= 9.28
kJ mol-1, so ΔG0= 15.28 kJ mol-1, which means that K = 2.0×10-3 M-1.

Take-home message: DMSO is such a good H-bond acceptor that it renders unfavourable any
H-bonding, because this results in the disruption of DMSO-donor H-bonds.

c) ΔΔG0=-(αdonor-αsolvent)( βacceptor- βsolvent), so: α= −∆∆𝐺 /(𝛽−𝛽𝑆) +α𝑆


Let us depict α as a function of β (with αs=0.8kJ1/2 mol-1/2 and βs=8.9kJ1/2 mol-1/2 as parameters)

by various ΔΔG0 values:


The areas where ΔΔG0 values are negative (favourable binding) are colored blue, areas of
unfavorable binding are colored red. Take-home message: for the same reason as in the
previous parts , just in a very few cases (very good donors and/or acceptors) is H-bonding
favorable in DMSO thermodynamically.

3. Draw the structures of the complexes formed between A1 and A2; B1 and B2; C1 and C2;
D1 and D2 and E1 and E2. In each case identify the main noncovalent interaction that drives
complexation in hexane as a solvent.

4. Receptor 1 binds guest 2 with an equilibrium constant of 1 × 104 M-1 and guest 3 with an
equilibrium constant of 4 × 104 M-1.
a) Explain this difference in affinity by referring to the most important noncovalent
interactions involved in complex formation in each case.
b) What would you predict for the enthalpy, the entropy and the heat capacity of the binding
of 2 to 1.
c) How could the heat capacity of the binding of 2 to 1 be determined?

a)The difference in binding affinities can be explained by the presence of a positive charge in 3, which
results in a more electron-deficient pi-system, and finally in a more reinforced pi-pi binding with the
electron-rich host (the host has an electron-rich pi-system, originating from the presence of the ether
groups, while both guests has an electron-poor pi-system due to the presence of nitrogen atoms in the
ring) . Moreover, in the case of 3 , additional cation-pi interactions can emerge.

b) The enthalpy change is negative, because both guests are hydrophobic, so that guest binding
results in the re-formation of the H-bonded network of water molecules, previously disrupted by the
presence of the organic molecules. Additionally, the pi-pi interactions contribute to the enthalpy but
to a lower extent.

For the same reasons, the binding is enthropically unfavourable, as the flexibility of the system
decreases upon binding : the H-bonded network of water molecules is more ordered than the disrupted
one, and the motion of the guests is restricted in the small cavity of the host compared to the situation
where the guest was loosely bound in the hydration shell of water molecules.
Regarding the heat capacity, the hydration of 1, 2, or the 1-2 complex will have a positive heat capacity
(as it is characteristic for hydrophobic hydrations), because a higher temperature leads to more
interactions of the solute with the water molecules and more disrupted H-bonds. However, when they
form the 1-2 complex this effect is lower than when they are separated, so the heat capacity of the
binding will be negative (as in the Figure 3.23 of the reader).

c) The heat capacity can be determined by performing ITC measurements at different


temperatures. From 1 measurement one can directly determine ΔG0 and ΔS0 values, and thus
determine ΔH0 . by plotting ΔH0 as a function of temperature and calculating the slope of the plot , one
can determine the heat capacity.

You might also like