DoITPoMS

Polymer chain morphology

A single polymer chain can exist in any one of its possible conformations, from a tight coil to a straight chain. The probability of it having a particular end-to-end distance increases with the number of possible conformations that would achieve that size. There is only one possible conformation that will produce a straight chain, but as the molecule becomes more coiled the number of possibilities increases. A polymer chain will therefore tend to coil up to some extent.

The expected end-to-end distance of a chain can be estimated using a model in which a molecule is considered as being made up of a large number n of segments. Each segment is rigid, but is freely jointed at both ends, so that it can make any angle with the next segment. A model ‘molecule’ can then be built by adding each of the successive segments at a random angle, a procedure called a random walk.

How does the random walk model compare to reality?

Polymer Kuhn length / C-C bond lengths Notes
Poly(ethene) 3.5 PE is very flexible (due to low torsional barriers)
Poly(styrene) 5 PS has large side-groups which inhibit flexibility
DNA 300 DNA is very stiff due to its double helix structure

Calculating the root mean square end-to-end distance of a random walk ‘molecule’

In two dimensions, we can estimate the distance from end to end of a molecule modelled by a random walk, given the Kuhn length and the number of segments. Each segment is represented by a vector,

Note: This animation requires Adobe Flash Player 8 and later, which can be downloaded here.


You can now test this model using the simulation below.

Note: This animation requires Adobe Flash Player 8 and later, which can be downloaded here.

Although this is a two-dimensional model, extending it to three dimensions gives the same result.