Statistical Mechanics in

Biopolymers
 Statistical distribution End-to-End
dimensions
• A flexible chain in an isolated state assumes the shape of a
macromol. coil.
• End to end dist. of such a chain:h.
• If chain is maximally coiled, then h=0
• If chain is maximally straightened out, then h=L
• L =contour length of the chain
• Intermediate value of h between 0-L can be calculated by applying
laws of statistical physics to one chain.
• In freely jointed chain, there is no restriction either on free rotation at the
joints,or on the angle formed between any two segments.

• Here, the position of each unit doesn't depend on that of the other units.

• If such units are connected with lines, the direction of these lines are
independent of each other.
• i.e, a real chain containing n units, each of length l, can be divided into N
independent random sections of length d.

• The statistical element, d,whose position is independent of that of

adjacent units is called thermodynamic segment(Kuhn segment).

THERMODYNAMIC PROBABILITY OF CHAIN

• Every thermodynamic segment consists of m monomer units, hence
number of independent segment N is related to degree of polymerisation
P.
• N=P/m
• The length of segment d is related to hydrodynamic length L of the chain
by L= Nd
• The number of conformation that a chain may assume called
thermodynamic probability W of a chain expressed by Gauss formula W
 Hughes-Ingold rules
• Using a simple solvation model that considered only pure electrostatic
interactions between ions or dipolar molecules and solvents in initial and
transition states, all nucleophilic and elimination reactions were organized
into different charge types (neutral, positively charged, or negatively
charged.

• Hughes and Ingold then made certain assumptions that could be made
about the extent of solvation to be expected in these situations:
• increasing magnitude of charge will increase solvation
• increasing delocalization will decrease solvation
• loss of charge will decrease solvation more than the dispersal of charge
Eg,
• An increase in solvent polarity accelerates the rates of reactions where a
charge is developed in the activated complex from neutral or slightly
charged reactant.

• An increase in solvent polarity decreases the rates of reactions where

there is less charge in the activated complex in comparison to the starting
materials
 Solvent polarity scale
The Grunwald–Winstein equation is a linear free energy
relationship between relative rate constants and the ionizing power of
various solvent systems, describing the effect of solvent as nucleophile on
different substrates.

where the kx, sol and kx, 80% EtOH are the solvolysis rate constants
for a certain compound in different solvent systems and in the reference
solvent, 80% aqueous ethanol, respectively. The parameter m is a
parameter measuring the sensitivity of the solvolysis rate with respect to
Y, the measure of ionizing power of the solvent
 Solvent nucleophilicity and electrophilicity

• Moving horizontally across the second row of

the table, the trend in nucleophilicity parallels
the trend in basicity:
Polar aprotic solvent