Química

Física IV QU0928 Artur Clement /Ester Bochons

S6. DETERMINATION OF AVERAGE

MOLECULAR WEIGHT BY
POLYMER END-GROUP ANALYSIS.
1. Theorical introduction
Polymers are compounds of high molecular weight formed by combining a large
number of small molecules, called monomers. whenever a synthetic polymer is made,
chains of varying length are produced, and the product has a molecular weight
distribution. Therefore the “molecular weight” is really an average for the sample and
there are several types of averages, depending on how the molecular weight is
measured.

The number average molecular weight is the simplest of the molecular weights, because
it corresponds to the usual notion of an average.

Where Mi is the molecular weight of the polymer i, and xi

represents its corresponding molar fraction.

This equation can be lightly modified. In this way, if Ni is the number of moles of each
polymer i, and wi is the weight of each polymer in the sample, then:

where wT and NT are related with the total mass of the sample and the total number of
moles of the polymer, respectively. Therefore, the Mn may be determined
experimentally by measuring the total number of moles of polymer in a known weight
of sample.

This is the reaction used for the experiment:

We made a titration after this

reaction was completed and also
titrated a blank experiment.

The difference between the NaOH
consumed in the blank solution
and the experiments with PEG will
indicate the number of acid groups
esterified, and therefore the final
number of hydroxyl groups
present. The number average
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Química Física IV QU0928 Artur Clement /Ester Bochons


molecular weight of PEG can be obtained taking into account that each molecule of
PEG contains two hydroxyl groups.

𝑛(𝑂𝐻) 𝑛(𝑁𝑎𝑂𝐻)!"#$%& − 𝑛(𝑁𝑎𝑂𝐻)!"#
𝑁! = =
2 2

2. Data

- Solutions prepared:

• 100 mL of 0,2 M solution of PMDA in DMF

1𝐿 0,2 𝑚𝑜𝑙 218,12 𝑔
100𝑚𝐿 ∗ ∗ ∗ = 4,362 𝑔
1000 𝑚𝐿 1𝐿 1 𝑚𝑜𝑙

• 500 mL of 0,2 solution of NaOH in wáter

1𝐿 0,2 𝑚𝑜𝑙 40 𝑔
500𝑚𝐿 ∗ ∗ ∗ =4𝑔
1000 𝑚𝐿 1𝐿 1 𝑚𝑜𝑙

- Standardization:

1) mphthalate=0,823 g VNaOH=20,2 mL

2) mphthalate=0,836 g VNaOH= 20,7 mL

- PEG Samples :


1) mPEG=200 mg VNaOH=29,9 mL

2) mPEG=228 mg VNaOH=29,1 mL

3) mPEG=240 mg VNaOH=28,6 mL


- Blank Experiment:

1) VNaOH= 39,4 mL

2) VNaOH= 39,6 mL

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Química Física IV QU0928 Artur Clement /Ester Bochons


3. Results and discussions

1) Synhtesis and applications of polyethylene glicol

- Synthesis:

Polyethylene glycol is produced by the interaction of ethylene oxide with
water, ethylene glycol, or ethylene glycol oligomers. The reaction is
catalyzed by acidic or basic catalysts. Polymer chain length depends on the
ratio of reactants.

Depending on the catalyst type, the mechanism of polymerization can be
cationic or anionic. The anionic mechanism is preferable because it allows
one to obtain PEG with a low polydispersity.

- Applications:

The high quality polyethylene glycols are utilized in the form of dispersing
agents, solvents, ointments, in suppository bases, and as laxatives in
medical, pharmaceuticals and cosmetics industries. They can prevent
foaming and therefore used in preparations where foaming is not required
in food industry. The low molecular weight polyethylene glycols are
preferred products for formation of ink solvents and lubricants for printing.
These are also important for cosmetics and preferred in preparation of skin
creams, lubricants and ointment bases because of their friendliness to the
skin. Polyethylene glycols do not cause any irritation to the skin and can
even be removed easily by water because of their excellent water solubility.

2) Methods of end group analysis in determining molecular weight:
applications and limitations

Because of the importance of end groups, there have been many analytical
techniques developed for the identification of the groups. The three main
methods for analyzing the identity of the end group are by NMR, mass
spectrometry (MS) or vibrational spectroscopy (IR or Raman). Each
technique has its advantages and disadvantages.

o NMR Spectroscopy

The advantage of NMR for end groups is that it allows for not only
the identification of the end group units, but also allows for the
quantification of the number-average length of the polymer. End-
group analysis with NMR requires that the polymer be soluble in
organic or aqueous solvents. Additionally, the signal on the end-
group must be visible as a distinct spectral frequency. As molecular

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Química Física IV QU0928 Artur Clement /Ester Bochons


weigh increases, the width of the spectral peaks also increase. As a
result of this, methods which rely on resolution of the end-group
signal are mostly used for polymers of low molecular weight. By
using the information obtained from the integration of a 1H NMR
spectrum, the degree of polymerization can be calculated.

o Mass Spectrometry

Mass Spectrometry is helpful for the determination of the molecular
weight of the polymer, structure of the polymer etc. Although
chemists utilize many kinds of MS, the two that are used most
typically are matrix-assisted laser desorption ionization/time of
flight (MALDI-TOF) and electrospray ionization-mass spectroscopy
(ESI-MS). One of the biggest disadvantages of this technique is that
much like NMR spectroscopy the polymers have to be soluble in
some organic solvent. A limitation of using MALDI is that the
ionization can be rather hard and as a result some end groups do not
remain intact for analysis. The limitation of using ESI is that the data
obtained an be very complex due to the mechanism of the ionization
and thus can be difficult to interpret.

o Vibrational Spectroscopy

The vibrational spectroscopy methods used to analyze the end
groups of a polymer are Infrared (IR) and Raman spectroscopy.
These methods are useful in fact that the polymers do not need to be
soluble in a solvent and spectra can be obtained simply from solid
material. A disadvantage of the technique is that only qualitative
data is typically obtained on the identification end groups.

3) Final results obtained


- Standardization:

𝑚!!!!!"!#$
𝑀!"#$ =
𝑀𝑟!!!!!"!#$ ∗ 𝑉!"#$

1) MNaOH= 0,199 M
2) MNaOH= 0,197 M

MNaOH= 0,198 M

- Blank:

1) n(NaOH)blank=0,00787 mol
2) n(NaOH)blank=0,00784 mol

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Química Física IV QU0928 Artur Clement /Ester Bochons


n(NaOH)blank= 0,00782 mol

- Experiment:

𝑛(𝑃𝑀𝐷𝐴)!"#$% = 𝑛(𝑁𝑎𝑂𝐻)!"#$%

𝑛(𝑃𝑀𝐷𝐴)!" !"#$%"& = 𝑛(𝑁𝑎𝑂𝐻)!"#

𝑛(𝑁𝑎𝑂𝐻)!"#$% − 𝑛 𝑁𝑎𝑂𝐻 !"# = 𝑛 𝑃𝑀𝐷𝐴 !"#$% − 𝑛(𝑃𝑀𝐷𝐴)!" !"#$%"&
= 𝑛(𝑃𝑀𝐷𝐴)!"#$%"&

𝑛(𝑃𝑀𝐷𝐴)!"#$%"& 𝑛(𝑁𝑎𝑂𝐻)!"#$% − 𝑛 𝑁𝑎𝑂𝐻 !"#
𝑁! = 𝑛 𝑃𝐸𝐺 = =
2 2

wT VNaOH NT Mn
200 mg 29,9 mL 0,00095 mol 210,52 g/mol
228 mg 29,1 mL 0,00103 mol 221,36 g/mol
240 mg 28,6 mL 0,00108 mol 222,22 g/mol