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Biot3109 Unit2 Part I

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25 views19 pages

Biot3109 Unit2 Part I

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dawit.mekonnen
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COLLEGE OF NATURAL AND APPLIED SCIENCES

DEPARTMENT OF MPS

UNIT 2: MACROMOLECULES AND RANDOM WALK

MESAY TILAHUN (PHD)


NOV 2023
UNIT 2: MACROMOLECULES AND RANDOM WALKS
Macromolecules:
are very large polymer molecules
Polymer:
a large molecule consisting of (at least five) repeated chemical units joined together
• A repeat unit in a polymer chain (unit cell) is a mer (is called a monomer)
• When all the mers are the same, the molecule is called a homopolymer,
while when there is more than one type of mer present, the molecule is a copolymer.
• Most polymers consist of long and flexible chains with a string of C atoms as a back-bone.
2.1 POLYMER STRUCTURE
2.1.1. Hydrocarbon molecules (I)
• Most polymers are organic, and formed from hydrocarbon molecules.
• Examples of saturated (all bonds are single ones) hydrocarbon molecules:
2.1.2 HYDROCARBON MOLECULES (II)

• Double and triple bonds can exist between C atoms.


• These bonds are called unsaturated bonds.
• Unsaturated molecules are more reactive.
2.1.3 HYDROCARBON MOLECULES (III)
• Many other organic groups can be involved in polymer molecules.
2.1.4 POLYMERIZATION
Polymerization is the process of joining small molecules called monomers to form large
molecules called polymers, which have unique properties and structures

Polymers:
may be natural, such as cellulose or DNA, or synthetic, such as nylon or polyethylene.
# Living organisms are mainly composed of polymerized
@ amino acids (proteins),
@ nucleic acids (RNA and DNA), and
@ other biopolymers
2.1.5 MOLECULAR WEIGHT
• Formation of macromolecules during polymerization results in distribution of chain
lengths and molecular weights
• The average molecular weight can be obtained by:
[a] number-average molecular weight or
[b] weight-average molecular weight.
[a] Number average molecular weight:
is the total weight of the sample divided by the number of molecules in the sample.
The number average molecular weight (𝑴𝒏 ) for this sample is:
σ 𝒊 𝑵𝒊 𝑴 𝒊
𝑴𝒏 =
σ𝒊 𝑵𝒊
where σ𝒊 𝑵𝒊 𝑴𝒊 = the total weight of the sample
σ𝒊 𝑵𝒊 = the number of molecules in the smaple
EXAMPLE
Calculating the number average molecular weight for the sample where the distribution
obtained from Size Exclusion Chromatography.

σ𝒊 𝑵𝒊 = 𝟏𝟎𝟎 σ𝒊 𝑵𝒊 𝑴𝒊 = 𝟓𝟎, 𝟎𝟎𝟎, 𝟎𝟎𝟎


WEIGHT-AVERAGE MOLECULAR WEIGHT
[b] The calculation of the weight average molecular weight:
requires the Weight Fraction, Wi, of each type of molecule
So, what is the weight fraction?
it is the weight of that type of molecule divided by the total weight of the sample.
Mathematically, the weight fraction can be written as:
𝑵𝒊 𝑴𝒊
𝑾𝒊 = σ𝒊 𝑵𝒊 𝑴𝒊

The weight average molecular weight is then calculated by:

Example:
Calculating the weigth average molecular weight for the sample where the distribution
obtained from Size Exclusion Chromatography.
SOLUTION
CONT.…
Note: The number average and the weight average molecular are not the same.
The distribution of molecular weights in a polymer sample is often described by the ratio of
the weight average molecular weight to the number average molecular weight.
In the above example, the ratio is: 531,600/500,000 = 1.063
This ratio is called the Polydispersity Index (or PDI).
Polydispersity index (PDI) is used as a measure of broadness
of molecular weight distribution.
@ The larger the PDI, the broader the molecular weight.
@ The polydispersity index (PDI) is a measure of the heterogeneity of a sample based on size.
# The PDI has a value always greater than 1, but as the polymer chains approach uniform chain
length, the PDI approaches unity (1).
# A polymer material is denoted by the term polydisperse if its chain lengths vary over a wide
range of molecular masses; this is characteristic of man-made polymers.
CONT.…

On the otherhand, the average molecular weight can be obtained by averaging the masses
with:
[1] the fraction of times they appear (number-average molecular weight) or
[2] with the mass fraction of the molecules (weight-average molecular weight).
Mathematically,

where,
Mi is the mean molecular weight of range i,
 wi is weight fraction of chains of length i and
 xi is number fraction of chains of length i
CONT.…

• Note: Melting / softening temperatures increase molecular weight (up to 100, 000 g/mol).
At room temperature,
# short chain polymers (molar weight ∼ 100 g/mol) are liquids or gases,
# intermediate length polymers (∼ 1000 g/mol) are waxy solids,
# solid polymers (sometimes called high polymers) have molecular weights of 104 - 107
g/mol
Alternative way to express average polymer chain size is degree of polymerization (DP)
- the average number of mer units in a chain:

where
EXAMPLE

Find:
(a) The number-average
molecular weight
(b) The weight-average
molecular weight
(c) PDI
(d) The degree of
polymerization for the
given polypropylene
material (C3 H6)
[MC = 12 g/mol and
MH2 = 1 g/mol]
SOLUTION
SOLUTION
SOLUTION
(c) PDI

= 36, 240 g/mol = 1.10


33, 040 g/mol

(d) Degree of polymerization:


DEGREE OF POLYMERIZATION

The degree of polymerization (DP):


is defined as the number of monomer units in the polymer.
It is calculated as the ratio of molecular weight of a
polymer and molecular weight of the repeat unit.
The degree of polymerization has a dramatic effect on the
mechanical properties of a polymer.
As chain length increases, mechanical properties such as
ductility,
tensile strength, and
hardness rise sharply and eventually level off.

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