ENGINEERING TASK ENGLISH

Name : Harris Nur Hidayat

NIM : 2010440009

Chapter 2
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Molecular weight and polymer solution

2.1 Weight average molecular weight and number average molecular weight
Molecular weight is a variable that is particularly important because direct contact with the physical
properties of polymers. In general, polymers with higher molecular weight are more powerful, but (as
will be shown in the next chapter) that is too high molecular weight bias causes difficulties in
processing. How to define a molecular weight of the polymer in question and the expected
application. In this chapter will be presented the definitions of molecular weight and molecular weight
distribution determination method in a polymer sample. We will provide a discussion of the molecular
structure of the polymer, because the solubility is a prerequisite for the determination of molecular
weight.
Mentioned that the polymers are compounds with high molecular weight, but we must start with the
question, how do we interpret the high molecular weight? Until that limit rendan molecular weight
and molecular weight ranging how high? Not easy to answer, because what constitute the molecular
weight of the "low", for example, for a sample of polyethylene, may be ideal for polyamide samples.
Moreover, some polymers deliberately made with a low molecular weight (even as oligomers) to
facilitate the initial process, the molecular weight increases the level of the next process. But in
general, the polymers are considered as having a molecular weight ranging from thousands to
millions, with the optimum molecular weight depends on the chemical structure and its application.
Vinyl polymers that have commercial value usually has a molecular weight between 105 to 106.
Polymers having functional groups are very polar, such as polyamides, may have a low molecular
weight ranging from 15,000 to 20,000.
To define the molecular weight compounds are simple (nonpolimerik), we use the techniques
commonly known as mass spectrometry, the freezing point depression (krioskop), the boiling point
elevation (ebulliometri) and when present functional groups are suitable, titration (for example,
neutralization, or saponification). However, the determination of the molecular weight of the
polymers is much more complex by the following two basic reasons. First, in a polymerization
process, in fact it would not be possible if all of the growing polymer chain ends (berterminasi) with
vesar or similar chain length; therefore one needs to treat the average molecular weight. (Some natural
polymer having a molecular weight typically have a legal exception to this). Second, the techniques of
krioskopi, ebulliometri, and titration only effectively applied to polymers with relatively low
molecular weight; methods must be more sophisticated to polymers with higher molecular weight of
40,000. Conventional techniques of mass spectrometry is not much more used in the field beyond the
characterization of polymer-related products of polymer degradation products because of the
requirements for sample measurement is volatile. Lately it has been found ebberapa exciting new
developments in the

field desorption mass spectrometry has expanded into the area of macromolecules. However, such
developments are still in the early phase (growth) and do not have regular use of the methods in a
more traditional molecular weight determination.

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The techniques are more commonly used for polymer molecular weight determination is osmometri,
light scattering (light scattering), and ultracentrifugation, although titration (end group analysis),
krioskopi, and ebulliometri also used in some applications. 1.2 The most convenient method for
routine determination of molecular weight measurement involves viskopsitas solution, but this is not
an absolute method and can only be used in conjunction with any of the techniques of measurement of
absolute molecular weight.
Molecular weight values obtained depend on the magnitude of the size of the measurement method.
The method relies on the analysis of end groups or colligative properties (freezing point depression,
the boiling point elevation, osmotic pressure) results in what is known as the average molecular
weight of numbers or a number because the number of molecules of each of the respective weight of
the sample is calculated. The total weight of a polymer sample, w , is the total weight of each species
of molecules that exist:

where N and M, respectively show the number of moles and molecular weight of each species i.
Average molecular weight number, Mn, is the sample weight per mole:

For example, suppose we have a sample of a polymer consisting of 9 mol molecular weight of 30,000
and 5 mol molecular weight of 50,000, then

Other examples, such as the sample consisted of 9 grams with a molecular weight of 30,000
and a 5 gram molecular weight of 50,000, then:

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On the other hand, light scattering and ultracentrifugation method for establishing a molecular weight
based on the mass and polarizability polymer species are present. Polymers with a larger mass then its
contribution to the measurement becomes larger. In contrast to the average molecular weight number
(which merupaakn number of mole fraction of each species multiplied by molecular weight), these
methods summing the weight fraction of each species multiplied by its molecular weight. Thus the
value obtained is called the weight average molecular weight, Mw , and systematically expressed as
follows:

Consider the same two samples just described above. Nine mole with a molecular weight of 30,000
and 5 mol molecular weight of 50,000:

If the mole is replaced grams:

In each case, it can be seen that the Mw , Mn greater than

In the measurement of colligative properties, each molecule has the same contribution, regardless of
weight, while the light scattering method, the molecules have a greater contribution over for having
light more effectively. For this reason the weight average molecular weight is always greater than the
average molecular weight number except, of course, when all molecules have the same magnitude;
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the Mw = Mn. Narrower molecular area values Mw and Mn his closer, and thus the ratio Mw /Mn can be
used as an indication of the width of the molecular weight of a polymer sample. This ratio is called
the index polidispersiias and systems that have a region depends on the molecular weight of the
polymer solubility and interaction - solvent.

2.2 Solution polimer3

Dissolving a polymer is not the same as dissolving compound having a low molecular weight because
of the dimensions are very different between the solvent and the polymer molecules. Dissolution of
the polymer occurs in two stages. At first solvent molecules diffuse across the polymer matrix to form
a mass called a bulging and solvated gel. (A student who closes a flask containing organic solvents
with a rubber cap surely see for yourself the effects of development coupled with gel formation ). In
the second stage, the gel breaks (divorce-divorce) and the molecules are dispersed into a true solution.
Dissolution is often a slow process. While some types of polymers can be dissolved rapidly in certain
solvents, other polymers may require long periods of heating near the melting point of the polymer.
Network polymers can not be dissolved, but usually swollen (ballooned) in the presence of solvent.
Even some linear polymers can not be dissolved in any manner whatsoever, hence the lack of
solubility of the polymer does not necessarily mean that the person concerned is a type of polymer
network.
How does one choose a solvent? The easiest way is to check on a polymer handbook, in which
accumulated abundant list of solvents and nonpelarut for various types of polymers. 4a detailed study
of the solubility of the polymer using the principles of thermodynamics have melhirkan semiempiris
relationships to predict solubility. A dissolution process is governed by the free energy relationship.
G=

H- T

When a soluble polymer with a spontaneous, free energy solution,

G, is negative. Entropy solution,

S, always has a positive value that occurs as a result of the increase in conformational mobility of
the polymer chains. Therefore, the magnitude of the enthalpy of solution,

H, will determine the sign

of G. It has been proposed that the hot mixture Hmix 'for a binary system parameters related to the
concentration and energy through the equation where Vmix is the total volume of the mixture, V1 and V2
is the molar volume (molecular weight /

49

density) of the two components,

is the volume fraction, and
E1 and E2 and are the
energy evaporation. Scale
meeting called cohesive energy (rapat energi kohesif). If
replaced with a symbol, then the above equation is written more simply:

symbol called the solubility parameter. Clear that, in order to dissolve the polymer (
negative),
the mix should be small. In other words,
, must have a value that is
approximately the same. When
, solubility at all only influenced by the effects of entropy.
Therefore, predictions based on the discovery of the solubility of the solvent and the polymer
solubility parameters were comparable, who need a way (tool) to establish a cohesive energy meeting.
Meeting cohesive energy is the energy required to move a molecule from its nearest neighbors, thus
analogous to the heat of vaporization per volume for a compound that is volatile (easily evaporated).
For the solvent,
can be calculated directly from the latent heat of vaporization (
) using the
relationship

Where R is the ideal gas constant, and T is the absolute temperature in Kelvin. Thus

Because polymers have negligible vapor pressure, the easiest method is to use to determine the molar
attraction constant of the cluster. The constants derived from the results of a study of compounds with
low molecular weight that gave birth to numeric values for the various groups of molecules based on
the consideration of intermolecular forces. Two sets of these numeric values (denoted by G) have been
proposed, one by Small, 5 which is derived from the heat of vaporization, and the other by Hoy,6
which is based on the vapor pressure measurements. G values are given in Table 2.1 is typical. It is
clear that there is a significant difference between the values proposed by Small and Hoy. Sets which
are used are usually determined by the method used to determine the value of the solvent.
The values of G is in addition to a certain truktur, and linked to

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by the equation

Where d is the type of M is the molecular weight. As an example for polystyrene has a density
(obtained from handhbook4b) 1.05; and re-104 mass units, as well as the structure

Calculated, using the values of G Small, as

Or by using the data Hoy

We note that , the solvent can be calculated in the same way. The main problem with respect to the
solubility parameter as discussed above that we did not include dipolar forces such strong hydrogen
bonds. But the proposals have made to separate the solubility parameters into components that reflect
the dispersion forces. The pull (attraction) dipole-dipole, and hydrogen bonding. Compile for the
solvent and the polymer contained in the literature:.4c
After establishing a polymer solvent system, other considerations are how the polymer molecules
behave dala solvent. Which is especially important in terms of molecular weight determination is
large or the resultant hydrodynamic volume, of the polymer molecules in solution. Assuming that the
polymer molecules with a specific weight to each other separated by a perfectly solvent, the volume
hidrodinamiknya will depend on various factors, including the interaction between solvent molecules
and polymer chain branching, conformation effects arising from steric hindrances polarity and
substituent groups, and limited rotation resonasi posed by, for example, which is common in
polyamide.

By the presence of Brownian motion, the molecules have a continuously changing shape. Therefore,
methods that try to predict the magnitude of the molecule must be based on statistical considerations
and the average dimensions. If a molecule is stretched to the maximum, then the amount can be
calculated from knowledge of the bond angles and bond lengths. But not so with most of the common
polymers; therefore the size is generally expressed in terms of the average squared distance between
the ends of the chain, r, for linear polymers, or turning radius mean square of the center of gravity. s
2
, for branched polymers. Figure 2.1 illustrates the meaning of r and s from the perspective of a
cauliflower structure of polymer molecules having a center gravitasnya padatitik early. Average shape
of a molecule coil is bentul ball. The greater affinity of the polymer solvent, then the ball will be a
tendency to increase, ie, will form a hydrodynamic volume. When the polymer solvent interaction is
51

reduced, it becomes more important intramolecular interactions, which cause shrinkage of the
hydrodynamic volume.
It is easy to express r and s by the following two factors:
Fixed dimensions (r0 atau s0) and the expansion factor (). Thus,

Fixed dimension refers to the size of the macromolecule exclusive solvent effects. He arose from the
combination of free rotation and intramolecular steric interactions and polar interactions. On the other
hand, the expansion factor arises from the interaction between the solvent and the polymer. For a
linear polymer, r 2 = 6 s 2 . because

Then will be greater than unity in a solvent that is "good", and the actual dimensions (blurred) will
exceed the dimensions remain. Value of depends on the temperature. For a given type of polymer in
a particular solvent, the lowest temperature where = 1 is called the theta temperature (0). In
addition, the polymer is said to be in a theta state. It is easy to think of the theta state as a polymer
becomes insoluble in the limit; in other words, the solvent has minimal solvation effects

Against bersolvasi molecules. Further diminution of this effect causes the attractive force between
polymer molecules become dominant, and the polymer becomes settles. And compile a lot of theta
solvent and temperature are available in the literature. . 4d

From the principle of the determination of molecular weight, the significance of these parameters is
that they can be linked to the viscosity of the solution according to the Flory-Fox equation.
Where [n] is the intrinsic viscosity (to be defined later), M is the average molecular weight, and is a
constant of proportionality, which is comparable to approximately 3 x1024 mol-1 (the so-called Flory
constant). Replacement r 2

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With r022 obtained

Which can be rearranged into

Because r0 and M is constant, with regard
Then

At the theta temperature, = 1 and

For conditions other than the theta temperature, the equation has the form

Where a is a constant which changes depending on the polymer, solvent, and temperature. Known as
the Mark-Houwink equation-Sakurada, this equation is important that, as we will see later in Section
2.5, is used to connect the viscosity of the aqueous solution with molecular weight.
In addition to the determination of molecular weight, practical considerations are important to muncil
of solubility effects. When someone moves in the direction of solvent "good" to "bad", and
intramolecular forces become more important, the polymer molecules shrink in volume. This
compactness rising birth reduced "shrinkage" and therefore the solution viscosity becomes lower. The
chemists in the field of paints especially once associated with solvent effects due to viscosity is a
basic requirement in the application of spray or brush-application of paint or solvent-based lacquer.
The manufacturer of fiber can also reduce the cost of energy used in spinning fibers from solution (see
Chapter 4) by reducing the viscosity of the solution.

2.3 Measurement of the molecular weight of the average number of

2.3. 1 Analysis of end groups 8a, 9a, 10a
Average molecular weight of the amount of a linear polymer having end groups that can be Measured
by the methods of chemistry or physics could theoretically determined if the method of measurement
is quite sensitive. But it must be remembered that the end groups are present in very low
concentration of. The techniques available today Allows the upper limit of the measurement of
molecular weight to about 50,000. Several methods in the determination of end groups mutakir
include (1) titration, using either an indicator or Potentiometric techniques;(2) analysis of end groups
elements containing certain elements, (3) measurement of end groups which are radioactive; and (4)

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UV spectroscopic determination of end groups that have a chromophore nuclear magnetic (NMR) has
a more limited use.
The things that must be considered in the application of analysis of end groups are as follows:
1 This method can not be applied to branched polymers except if the number of branches is known
with certainty; thus this method in practice is limited to linear polymers.
2 In a linear polymer end groups are sebanbyak two linear molecules.
3 If the polymer contains different groups at each end of the chain and the measurement is only
carried out on one of the end groups that can dikarakterisasai, the number of types of end groups is
equal to the number of polymer molecules.
4. measurement molecular weight by end group analysis only has meaning if the initiation and
termination mechanism is well understood.
As a typical example, let us consider the unsaturated polyester (Chapter 12). Polyester is a linear
polymer with a relatively low molecular weight that they provide cross (crosslinking), carboxyl
groups and hydroxyl end groups can diditrasi with standard methods. 9a In case karboksl, the polymer
sample was weighed, dissolved in a suitable solvent such as acetone and titrated with standard base to
the end point fenolfatelin. For hydroxyl, samples acetylated with excess acetic anhydride and acetic
acid release, along with the carboxy end groups diditrasi the same way. Of both the sample titration.
The number of moles of polymer per gram is then given by equation (Item 2nd in the denominator.
Considering that the two end groups per molecule).
Molecular weight =

1
Moles of polymer per gram

In the processing of polyester, acid number, which is defined as the number of milligrams of base
required to neutralize 1 gram polyester, are often used to monitor the advancement of the reaction.
Other end groups that can be titrated is an amino group in the polyamide, polyamide acetyl group in
acetyl lead, isocyanates in polyurethane and epoxide in epoxy polymers. A number of factors can
complicate the analysis of end groups, for example: hilanya solubility, high biskositas solution, a large
steric barrier. But when the trouble for these difficulties could be overcome, end group analysis can be
done for polymer-polymer having a molecular weight region of 5,000 to 10,000.

2.3. 2 Osmometri membrane 8b, 9b, 10b

Among the various methods of molecular weight determination of the average amount based on
colligative properties, osmometri membrane is the most useful method. When the pure solvent is
separated from the solution by a barrier (barrier) which allows a solvent (but solute molecules can not
pass), then the solvent will pass through the barrier to continued upward pressure hidrostatiknya
prevent the continuation of the solvent through, or in other words, to balance is achieved. This
pressure is the osmotic pressure. Barriers of this kind is called a semi-permeable membrane.

54

Schematic representation of an osmometer shown in Figure 2.2 Memberam semipermeable usually

constructed of polymeric materials such as rubber, nitrocellulose, cellulose acetate, and poly (vinyl
alcohol). The osmotic pressure can be determined by making
system reaches ksetimbangan and measure hydrostatic pressure arising. This way is classified as a
static equilibrium method. Alternatively, one can apply back pressure to the first measuring tube
usually requires a long period of time to reach equilibrium, the dynamic method is preferred.
Various dynamic membrane osmometer has been produced, which usually includes a horizontal
membrane separator solution and solvent cells. The type is shown schematically in Figure 2.3
measures the osmotic pressure directly through the strain gauge transducer connected to a flexible
diaphragm in the solvent cell.

Osmotic pressure attributed to the molecular weight by the van't Hoff equation were calculated
according to the concentration of zero:

Where

is the osmotic

pressure, is given by the equation:

55

Where R is the ideal gas teatpan 0.082 mol L-1 atm K1 (CGS) or 8.314 J mol-1 K-1 (SI); T is the
temperature in Kelvin; C is the concentration, in grams per liter; p is the solvent density, in grams per
cubic centimeter; g is the acceleration of gravity 0,981 m / s2; is the height difference
between the
solvent and the solution, in centimeters; and A2 is the second virial coefficient (a measure of the
interaction between the solvent and polymer).
Plot reduction osmotic pressure, / C, versus concentration (Figure 2.4) with a linear shaped cut point
is equal to RT / Mn and the gradient is equal to A2 . [Unit for / C is dyne L g-1 cm-1 (CGS) or J kg-1
(SI).] Because is a measure of the solvent-polymer interaction, the gradient becomes zero at theta
temperature. Thus the osmotic pressure measurements can be used to determine the theta conditions.
The main causes of errors in osmometri membrane arising from species with low molecular weight
diffuses across the membrane. This explains why the molecular weight obtained is usually lower than
the value obtained through measurement pengukurang-other colligative properties in which all species
are present calculated. Ososmetri membrane

usually beneficial to the molecular weight above about 50,000 to 2 million, the limiting factors such
as the permeability of the membrane to the lower limit of the measurement and the smallest osmotic
pressure can be measured at the upper limit of the measurement. Since most polymers have value
commercial has a molecular weight in this area, osmometri membram is the most widely used method
to assign an average molecular weight of absolute numbers.
2.3.3 Krioskopi and ebulliometri 8c, 9c, 10c, 11a
The techniques used in the freezing point depression (krioskopi) and the boiling point elevation
(ebulliometri) analogous to techniques for low molecular weight compounds, and thermodynamic
relations, derived for dilute solutions is infinite also like:

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In these equations C is the concentration in grams per cubic centimeter; T is the freezing point or
boiling point of the solvent in Kelvin; R is the gas constant; p is the density of the solvent;
successive latent heat of fusion and evaporation of solvent per gram; M is the average
molecular weight and the number of A is the second virial coefficient. The molecular weight
determined from plots
versus concentration, as in the case of analog osmometri.
The main limitation of krioskopi and ebulliometri lies in the sensitivity of the methods of measuring
the freezing point
or elevation of boiling point,
when the molecular weight increases
more and
more small such that even with the most sensitive thermistor (of which is sensitive
to 1 x 10-4 C, upper limit of measurable molecular weight range of 40,000. would but this method,
together with the vapor pressure osmometri method (discussed below), it is better to use if the
molecular weight below 20,000.
2.3.4 Osmometri vapor pressure 5c, 8c, 9c
This method is usually helpful to set a molecular weight below 25,000. Although the vapor pressure
osmometri not involve membrane, thermodynamic principles analogous to the principles included
osmometri membrane. A drop of solvent and a drop of solution is placed on top of the spray using a
thermistor which has been adapted in an isolated room that is saturated with solvent vapor.
Condensation heating thermistor solution to the vapor pressure rose to pure solvent vapor pressure.
Changes in temperature, which is measured from the change in resistance of the thermistor, connected
with the molality of the solution, and thus the molecular weight, through the equation

Where

is the heat of vaporization per gram of solvent and m is the molality

2.3.5 refraksi12 index measurement

It has been shown that, for some types of polymers, there is a linear relationship between the
refractive index and the average molecular weight of the inverse number. Besides, this may be the
most suitable method is applied to the polymer-polymer having a low molecular weight, it also has the
advantage of the simplicity of how it works.
2.4 Measurement of weight average molecular weight
2.4.1 Light scattering 8d, 9d
Aside from osmometri, light scattering (light scattering) is the most widely used method to obtain
absolute molecular weight. This method is based on the fact that light, when passed through a solvent
or solution, releasing energy that is caused by absorption, conversion into heat, and scattering.
Scattering of light to a pure solution arising from irregularities in the limited distribution of solvent
molecules. Amplitude or intensity of the scattered light depends on several factors, the most important
is konsentrasim size, and polaribilitas scattering molecules. Refractive index also depends on the
concentration and the amplitude of vibration. To evaluate the turbidity caused by the scattering, one
must combine equations derived from pengukurang scattering and refractive index. Turbidity, T ,
associated with concentration, c, by the equation

57

and no is the solvent refractive

index, is the wavelength of
light that occurred, and no is Avogadro's number. Tribe dn / dc referenced as a specific increase in
refraction, obtained by measuring the refractive index gradient as a function of concentration, and its
value but for the polymer, solvent, and temperature. Ketike large molecular size approaches the
wavelength achaya, corrections must be made for the interference between the scattered light that
comes from the parts of different molecules.
To define the molecular weight, the equation for turbidity rewritten as

Where P (0) is a function of the angle 0 at time T is measured, this function depends on the shape of
the molecule in solution. A2 is the second virial coefficient. Then, turbidity was measured at different
concentrations as well as the different angles, the latter is to compensate for variations in molecular
shape,
Then the experimental data extrapolated to zero concentration and zero angle, where P (0) be equal to
1 double Extrapolation Thus, as shown in Figure 2.5, is called Zimm plot (from
Bruno Zimm, who pioneered this method) factor k oada jiirdubat flat (coordinate x) is any constant.
The point of intersection with the y-axis according to 1 Mw..
The main problem in the light scattering method is to get the solutions that really clear and free of
dust. This is usually done by ultracentrifugation or filtration caution. Despite such difficulties arise,
the light scattering method is widely used to obtain the weight average molecular weight of between
10,000 and 10,000,000. Light scattering photometer-photometer longer use high pressure mercury
lamp and filters to obtain monochromatic light beam. This photometer has been replaced with a laser
light source. Laser light scattering photometer scheme is given in Figure 2.6
2.4.2 ultracentrifugation 8c, 13, 14a
Ultrasentrifug so far is the instrument of the most complicated and expensive for molecular weight
determination. This method is not used as much as or osmometri ray scattering method in determining
the molecular weight synthetic polymers, but it is widely used for natural polymers, especially
proteins. The technique is based on the principle that molecules, under the influence of strong
centrifugal field, distribute themselves according to the magnitude of the perpendicular to the axis
putarm a process called sedimentation, and its speed is proportional to the mass of the molecule.
Centrifugation carried out in an open hole in a cell in the rotor circuit, given both windows so that
optical methods, such as measurement of refractive index or interferometry, can be used to observe
changes in the concentration of the polymer solution is concerned. The basic components of a
ultrasentrifug shown in Figure 2.7

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There are two approaches to obtain the molecular weight with ultrasentrifug. One of them,
sedimentation equilibrium method, involves the screening of a polymer solution with a low speed for
a long time to achieve equilibrium between sedimentation and diffusion. Changes in refractive index
between two points within the cell (the meniscus and cell base for heterogeneous samples, to include
all species) associated with a change in concentration, and a weight average molecular weight is given
by the statement

Where C1 and C2 are the concentrations, respectively, at distances r1 and r2 from the center of rotation
to the point of observation in the cell; v is the specific volume of the polymer; p is the density of the
solution, and is the angular velocity of rotation.
Another approach is the ultrasentrifug operate at high speed (up to 70.00 rpm) and connect to the
sedimentation rate of the average molecular weight. This is called the sedimentation velocity method.

Figure 2.6 Schematic of laser light scattering photometer. [From Rabek, xj copyright 1980 Rewritten
by permission of John Wiley & Sons, Ltd.]
Sedimentation rate is defined by the sedimentation constant, s, which is connected to the mass of the
particle by the equation:

59

Figure 2.7 Schematic of

Rabek, 8c copyright
permission of John

a ultrasentrifug. [From
1980
Rewritten
by
Wiley & Sons, Ltd.]

Where dr / dt is the sedimentation velocity, m is mass, and f is the friction coefficient. For random coil
polymers, f associated with the diffusion coefficient, D at infinite dilution by the equation

The average molecular weight can then be obtained from equation

This type of measurement is most effective on monodispersi systems such as proteins, and synthetic
polymers for polidispersi can be obtained only approximate.
2.4.3 The field desorption mass spectrometry (FDMS)
Field desorption is a method of separating molecular ions directly from a solid to a gaseous state
without dekomposisi.15 For example, the sample plimer superimposed upon filament-filament
Carbon anodes are tied to the sharpened tip (sharp-edged) at the entrance of a mass spectrometer.
These samples were then subjected to an electric field is very strong (with the 105 volt level
persentimeter). When the anode is heated, molecular ions out of the sample and analyzed by the
spectrometer. Thus the mass spectrum gives the calculation of various molecular masses are present in
a sample polidispersi. Good usability of the FDMS (Field Desorption Mass Spectrometry) lies in its
ability to measure M and Mw as well in addition to molecular weight distribution. 16 FDMS can
almost be sure will have a better advantage if the instrumentation developed for uses more routine.
2.5 viscometry
Viscosity measurements of dilute solutions provide the simplest techniques and most widely used for
determination of molecular weight on a regular basis. 8f, 9e 14b. Viscometry method is not absolute; each
polymer system must first be calibrated with the determination of absolute molecular weight (usually
with a light scattering method) were run on samples fractionated polymer. Viscosity measured at a
concentration of about 0.5 g / 100 ml solvent flow by setting the length of a volume of solution
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through the capillary length is fixed. Lamanbya flow in seconds is recorded as the time for the
meniscus passed between two boundary signs on the viscometer. Viscosity-viscosity set at a constant
temperature, usually 30.0 + 0.01 0C.
Two typical viscometer is shown in Figure 2.8. Between them, the type Ubbelohde easier to use
because it does not need to have the exact volume to obtain results that can be proven again.
Moreover, additional solvent can be added (assuming that the reservoir is large enough);
concentration can thus be reduced without having to empty and refill the viscometer. Whichever type
is used, the polymer solution needs to be filtered into the viscometer because dirt particles affect the
length of the flow. Filtration easily solved with micro filter units that replace hypodermic needle on a
syringe.

Gambar 2.8 Viskometer kapiler: (A) Ubbelohde; (B) Cannon-Fenske

The modules are controlled by a computer viscometer is now available commercially. This tool
measures the time in the capillary flow of the photoelectric and held dilution and mixing
automatically in addition to the viscosity value calculation and planning.
Viscosity can be, expressed in several ways (Table 2.2). Now these common names are more widely
used than the names recommended by IUPAC .17 (The names of the more recently appointed by
IUPAC to avoid inconsistencies arising from the designation of "viscosity" that there is no unit).
Relative viscosity (viscosity ratio) (nre) is the ratio (ratio) solution viscosity is proportional to the
viscosity of the solvent with the first approach for dilute solutions of time-time to the ratio of the
corresponding flow. Unit viscosity (usually expressed with poise) or flow time divided into various
expressions of viscosity. Specific viscosity (NSP) is an increase in the fraction (part) in the viscosity.
Both nrel and nsp both dimensionless. When the concentration increases, the viscosity was increased.
Therefore, to eliminate the effect of the concentration, the specific viscosity divided by the
concentration and extrapolated to zero concentration to give intrinsic viscosity, [n]. Sometimes the
viscosity determined at a single concentration and inherent viscosity (ninh) is used as an indication of
the approach of molecular weight. Inherent viscosity mengektrapolasi to [n] are the same.
Concentration, C, in the above expression is expressed in grams per 100 ml of solvent or in grams per
cubic centimeter, and the initial unit more commonly used. Thus the inherent viscosity and intrinsic
viscosity-have units of grams per deciliter or, which is the take gumum, cubic centimeters per gram.
Clear that the units of concentration must be specified when reporting data viskoitas.
Table 2.2 Distribution of solution viscosity encer0

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Among the various types of viscosity, intrinsic viscosity is the most helpful and easy to use because it
can be linked to the molecular weight by the Mark-Houwink equation-Sakurada:

Where Mv is the weight average molecular viscosity, which is defined as:

Set K and A, respectively, the intersection and the gradient of the plot of log [n] versus log Mw or Mn
log of a series of polymer samples were fractionated. Such plots be linear (except at the low molecular
weight) for the linear polymers, thus
Log [n] = log K + a log M

Weight average molecular viscosity lies between the polymer Mw and Mn are concerned, but closer to
Mw. will therefore obtained results are better if the K and A are determined by
fractionated samples with Mw values are known. To evaluate K and a require considerable
manipulation, but now it has published a wide area that shows the value of a wide spectrum of the
polymer, solvent and temperature 4e. For most plimer general, the value of a varies between 0.5 (for
random coil polymers in a theta solvent) and 0.8; whereas for long-chain polymers that more
resembles the stem where hidrodinamikanya relatively large volume, the value of a may be 1.0, a state
where Mv = Mw. K values generally vary between 10-3 and 0.5. Some peresentatif values of a and K
are given in Table 2.3.
The factors that can disrupt the application of equation Mark-Houwink_Sakurada is chain branching,
molecular weight distribution is too wide in the samples used to determine the value of a and K,
solvation of polymer molecules, and the presence of a series of alternations or blocks in the polymer

62

backbone . The state of the polymer chain that wraps usually not a problem on solutions highly
diluted such that, unless very large molecular weight.
Types of other viscosity measurements were based on the principles of shifting mekanik14b also
performed, the most common is the polemic solutions of concentrated or insoluble polymer; however
these methods can be applied to the flow properties of polymers (Chapter 3), not for the determination
of molecular weight. Another Moetode to assign based on the molecular weight of the polymer
fractionation and will be discussed in the following pasa.

2.6 The molecular weight distribution

A molecular weight distribution of the polymer characteristics are important because, as well
molekulm weight can greatly affect the properties of the polymer. As low molecular weight
polystyrene shows the different properties of high molecular weight polystyrene, a polystyrene sample
that has a narrow molecular weight area will show the different properties of polystyrene which has a
broad molecular weight region, although the mean molecular weight the average of the two samples
are the same.

63

In general, the techniques for the determination of the molecular weight distribution of polymer
samples involving fractionation and comparison of fractions obtained with samples having an
absolute molecular weight is already known through some calibration procedures. In this regard,
various methods have been developed.
2.6.1 gel permeation chromatography (GPC) 8g, 18, 14c, 19a
Until now, GPC (Gel Permeation Chromatography) is the most widely used method for determination
of molecular weight distribution. As a column chromatographic technique. GPC may be used as a first
step to obtain fractions of narrow molecular weight. Separation is done in a column filled with a
material very axis that separates polymer molecules according to size, a phenomenon that is often
expressed as molecular sieving (molecular sleving). (A common technique is sometimes called size
exclusion chromatography). Thought to later stated that the separation was based on the
hydrodynamic volume of the molecule rather than the molecular weight per se.20 molecules able to
diffuse into the axes (small holes) column filled (packed) more efficiently, and therefore they pass
through the column more slowly. Thus the first to be eluted are fractions with higher molecular
weight.
The basic form of gel permeation chromatography are shown in Figure 2.9. Filler materials (packing)
column included in a variety of forms, but most commonly they consist of small grains and a half of
soft bonded polystyrene cross-linked with divinylbenzene and bulging with solvent, or from grains
dank shaft eras of glass or silica. Detection of polymer fractions in the elution, most commonly done
with a refractive index detector or spectroscopic (ultraviolet and infrared). Instruments-instruments
that are commercially available do sample injection and fraction collection automatically, by the rapid
flow of high-pressure pumps, and treatment data with computer aided. Which is closely related to
GPC gel filtration chromatography (GPC), a technique that in principle be used to characterize the
natural polymers in aqueous solution. GFC columns packed with hydrophilic gels, which are usually
in the form of dextran-dextran crosslinked or crosslinked polyacrylamide. As in the case of GPC,
GFC column separation also occurs via molecular filtration, however, adsorption, ion of exchange and
ion exclusion also play a role.

64

A
typical
gel
permeation
chromatogram
(Figure
2.10)
will
plot
the
detector response
to the volume of dilute polymer solution is passed through the column (elution volume, Vr). To obtain
molecular weights at a particular retention volume, the chromatogram may be compared to a reference
chromatogram obtained with fractions with average molecular weight is known in the same solvent
and at the same temperature. to objectives benchmarking purposes, ribbon (band) elution divided into
"columns" with height above the baseline is proportional to the amount of polymer (N1M1) were
eluted.
A major problem in calibrating the GPC column for a typical polymer is that the standard samples are
slightly narrower molecular weight distribution available commercially. Polystyrene standards have
polydispersity index close to one available with a broad molecular weight region (600-2,5juta) and is
often used; but when someone treats polymers other than polystyrene, molecular weight obtained at
best are approximate and may, in some cases, a wrong value. To avoid this difficulty, use the universal
calibration method.
Universal calibration based on the observation that obervasi21-viscosity product (bilanganviskositas
barrier) and the molecular weight does not depend on the type of polymer. This product, [n] M, called
the universal calibration parameters. As shown in Figure 2.11, the plot of log ([n] M) versus elution
volume and the solvent tetrahydrofuran (THF) produces a single curve, shaped almost linear, for
groups of polymers are manifold. Thus log ([n] M) can be considered as a constant for all polymers
for columns, temperature and elution volume is concerned. If it is considered that the reference
polymer (eg, polystyrene) are polymer 1 and polymer is a polymer difraksikan 2, then apply
([n] 1M1) = ([n] 2M2)
from the equation Mark-Houwink-Sakurada,
[n]1 = K1M1a
[n]2 = K2M2a
Combining these equations and solve for the log M2, obtained

65

To define the molecular weight (M2) at a certain retention bolume,

At first column must be calibrated with standard polystyrene fractions (same solvent, and the same
temperature). It will provide a link with the type as shown in Figure 2.12. Semilogarithmic calibration
plots thus usually be linear over a wide molecular weight region, with deviations due to the linearity
which occurs in a high molecular weight low, especially at high molecular weight. Constants K and a
can usually be obtained from a polymer handbook. 4e substitution M1 values for specific retention
volume of the calibration plots and the values of K and a in the above equation, will soon be able to
66

determine the value of M2. GPC thereby providing a rapid and practical method to obtain the
molecular weight distribution if a suitable calibration-calibration can be arranged.
2.6.2 Leaching fraction 8h, 22
In its simplest form, it may involve extraction fraction dissolving the polymer in a Soxlhet type tool to
dissolve the fractions of molecular weight increased with the passage extraction. To be practical, this
method has been adapted to krematografi procedure. Chromatography column filled with an inert
material such as glass or grains of fine sand coated with polymer. A nonpelarut fluid flowed through
the column, followed by increasing the amount of solvent that is mixed with the liquid nonpelarut. At
first, a low molecular weight polymer will dissolve, followed by fractions with higher molecular
weight. This is in contrast with

Figure 2.12 Plot of typical semilogarithmic calibration of molecular weight versus retention volume
GPC, therefore, the first to be eluted fractions are low molecular weight. Typical combination
between solvent and nonpelarut are consecutive 2-butanone to polystyrene; and xylene (xylene) and
1-propanol for politetilena. Ternal applications gradient along the column chromatography method
called gradient solvent - is a variation of the dissolution fractions.
2.6.3 deposition fraction 8h 22
Essentially this is the opposite of dissolving fraction. The procedure is umu is by adding a small
amount nonpelarut to dilute homogeneous solution of polymer polidispersi to materials with high
molecular weight settles. The precipitate was taken by filtration or decantation and then add the
remaining solubility nonpelarut once again. This procedure is repeated many times as long as
necessary to get the desired fractionation and all polymers have been retrieved.
One variation of the deposition fraction is turbidimetri.4h, 20b. when the polymer solution is added
into a nonpelarut, turbidity occurs, which is recorded as the light scattered in a photocell, in correlated
with molecular weight. If the temperature change is used to hold the mengendapan turbidimetry
technique called thermal gradient.
2.6.4 thin layer chromatography (TLC) 17c, 23-25
TLC at the top of the pieces are coated silica gel or alumina have been studied, not only as a method
specifies the molecular weight distribution, but also to separate and characterize the types of
polymers, such as block copolymers and cangkok.26 there are two main mechanisms of separation of
polymers above pieces TLC: absorption and deposition. (screening molecules may also occur if the
67

used type of coating that macroporos). The absorption based on the competition between solvent and
solute for penyerapnya materials; primarily a function of the chemical structure of the deposition
involves fractionation by molecular weight; he is the main mechanism in determining the molecular
weight distribution.
There are 3 ways to hold while keeping TLC fractionation have been attached to the polymer; (1)
solvent mixture and homogeneous nonpelarut used as an elution medium. When the solvent limit goes
above the chip, komposisisnya changed due to a combination of different absorption and evaporation.
When the solvent limit be filled with non-solvent, fractions with high molecular weight began to
settle. (2) nonpelarut first used, and the solvent is added to the amount of the increase during elution.
Fractions with low molecular weight initially moves will increase move, followed by fractions with
higher molecular weight. (3) the solvent initially used to move the entire patch (dot) polymer, then
added nonpelarut with increasing amounts; which causes the fractions with high molecular weight
will settle first.
Definite advantage of TLC is its low cost and simplicity. Also, he has the ability as a routine method
for the initial screening of polymer samples or to monitor polymerization processes paper
chromatography has also been studied as a method to establish the molecular weight distribution, 27
but its users are less extensive.
2.6.5 ultracentrifugation 13
This method involves observations of the boundary during sedimentation velocity experiments
performed sedimentation (centrifugation at high speed). Sedimentation boundary is moving boundary
caused by the movement of solvent penetrating the polymer during centrifugation. The limit is
widened, partly due defusi and partly due to the polydispersity, and this widening can be attributed to
the molecular weight distribution. This technique provides the advantage with the ability to decipher
fractions with very narrow area, but the drawback is the high cost of equipment and complexity.

68

References
1 S.G. Weissberg, S.Roothman, and M. Wales. In Analytical Chemistry of polymers, Part 2 (GM
Kline, ed.), Wiley-Interscience, New York, 1962 Chap.1
2 N. C. Billingham, Molar Mass Measuraements in Polymer Science, Halsted Press, New York, 1977.
3 H. Morawetz, Polymers in Solution, 2nd ed., Wiley-Interscience, New York, 1975
4 J. Brandrup and EH Immergut (eds.) Polymer Handbookm 2nd ed., Wiley-Interscience, New York,
1975: (a) O. Fuch-H and H. Suhr, pp IV-241ff; (b) JF Rudd , p. V-59; (c) H. Burrell, pp. IV-337ff; (d)
H.-G. Elias and H.G Burher, pp. IV-157ff; (e) M. Kurata, Y Tsunashima, M. Iwarna, and K.Kamada,
pp. IV-1ff.
5. P.M. Small, J. Appl. Chem., 3.71 (1953).
6. K.L. Hoy, J.Paint Tech., 42, 76 (1970).
7 C.M. Hansen, J.Paint. Tech., 39, 104, 505, 511 (1967).
8 J. F, Rabek. Experimental Methods in Polymer Chemistry, Wiley Interscience, New York, 1980: (a)
Chap.7; (b) Chap.5; (c) Chap.6. (d) Chap.13; (e) Cgao. 8; (f) Chap 9; (g) Chap.25; (h) Chap. 4.
9. P.W. allen (ed.), Techniques of Polymer characterization, Butterworth, London 1959: (a) GF Price,
Chap. 7; (b) H.T Hookway, Chap. 3; (c) D.F. Rushman, Chap 4; (d) F.W. Peaker, Chap.5; (e) P.F.
Onyan, Chap 6.
10 P.E. Slade Jr. (ed), Polymer Molecular Weights, Part 1, Dekker, New York, 1975: (a) RC Garmon,
chap. 5; (b) R.D. Ulrich, Chap.2 (c) C. A. Glover, Chap. 4; (d) E.P. Cassassa and G.C. Berry, Chap.5.
11. LS Bark and NSAllen (eds.), Analysis of polymer systems, Applied Science, London, 1982: (a)
G.Davidson, Chap.7; (b) A. R. Cooper, Chap, 8.
12. R.A. Rhein and D.D.Lawson, CHEMTECH, 122 (Feb.1971).
13. JWWilliams, Ultracentrifugation of Macromeolecules, Academic Press, New York, 1972.
14. PE Slade Jr. (ed.), Polymer Molecular Weight, Part 2, Dekker, New York, 1975: (a) Th. G.
Scholte, Chap. 8; (b) D.K Carpenter and L. Westerman, Chap. 7; (c) A.C Ouanc, E. M. Barrall II, and
J.F. Johnson, Chap, 6.
15. W.D.Reynolds, Anal, Chem., 51, 283a (1979).
16. R.P Lattimer, D.J. Hrmon, and GE Hansen, Anal, Chem, 52, 1808 (1980).
17th International Union of Pure and Applied Chemistry, J.Polym. Sci., 8.257 (1952).
18. K.H Altgelt and L.E. Segal (eds), Gel Permeation Chromatography, Dekker, New York, 1971.
19. L.H. Tung (ed), Fractionation of Synthetic Polymers, Dekker, New York, 1977: (a) LH Tung and
J.C. Moore, Chap.6; (b) H.-G Elias Chap. 4; (c) H. Inagaki, Chap, 7.

69

20. J.C. Moore, in Liquid Chromatography of Polymers and Related Materials, Part 3 (J. Cazes, ed),
Dekker, New York, 1981, p. 1ff.
21. Z, Grubisic, P. Rempp, and H. Benoit, J. Polymer. Sci., B5, 753 (1967).
22. R.M. Secreaton, in Newer Methods of Polymer characterization (B. Ke, ed), Wiley-Interscience,
New York, 1964, Chap. 11
23. EP Otocka, Weiht Methods in Molecular Polymer, Adv. Chem. Ser. 125, American Chemical
Society. Washington, D.C., 1973, P55.
24. B.G. Benenkii and E.S. Gankina, J. chromatog. Rev., 141, 13, (1977).
25 DW Armstrong and K.H. Bul, Anal, Chem., 54, 706 (1981).
26. H. Inagaki, T. Kotoka, and T.-I. min, Pure Appl. Chem., 46.61 (1976).
27. Siling M. I., V. Ya. Kovner, Yu. Pvyrsky, and O.F. Alkayeva, J. chromatog., 101 83 (1974).

Exercises
1 Imagine that you want to make something "model" linear polyethylene having a molecular weight
of about 170,000 (a number that makes sense for a commercial product) using paper clips to show
their repetitive units. How many paper clips there must be the chain (flops) together?
2 In general, the increase in temperature will reduce the viscosity of the polymer solution. How does
the magnitude of the strength of this effect than in a solvent "bad" and solvent "good"? (asked by a
matter of principle that this is the basis for the motor oil multiviskositas)
3 An experimental method to establish the parameters of polymer leaching involves sampling a little
concerned polymer crosslinked (network structure) and putting it in different solvents which have a
dissolution parameters are known. Explain the theory behind this method contained.
4 Specify the parameters for the dissolution polypropilena and poly (methylmethacrylate) amorphous.
(The density of both the polymer respectively 0.905 and 1.18 g / ml). check a handbook polymer and
propose suitable solvents for both polymers are based on the parameters of dissolution.
5. Based on practical thinking, when measuring the molecular weight of the polymer, which is better
between solvent wear a "good" or solvent "bad"? explain.
6 What is the weight average molecular weight and the average amount of a propylene oligomer
sample consisting of 10 mol 5mol pentamer and hexamer?
7 Compute Mn, Mw and Polydispersitas index for a hypothetical polymer sample containing the same
number of moles of polymer having a molecular weight of 30,000, 60,000, and 90,000?
8 At about 7, change the word "the same number of moles" to "equal weight" and count back.
9 A total of 0.5000 grams of unsaturated polyester resins samples reacted with excess anhydride
assetat. Titration of the reaction mixture with 0.0102 ml of 8.17 M KOH need to reach the end point

70

of the titration. What is the molecular weight of the average number of the polyester? Is this method
suitable for the determination of any polyester? Explain.
10 What is the DP (degree of polymerization) of a sample of polyester made from 4-hydroxybenzoic
acid if the acid number, which is determined by a standard KOH solution, was 11.2?
11. Calculate the freezing point depression, raising the boiling point, and osmotic pressure (in
millimeters of water at 250 C) to 1.00% by weight per volume of water solution of 3 samples of
polymer molecular weight has an average number of 5,000, 50,000 and 100,000. based on your
answers, What conclusions can be drawn about the effectiveness realitif of each method in
determining the molecular weight?
12. Explain how one set of experiments the constants K and a common-Sakurada Mark-Howink for a
particular type of polymer.
13 How the average molecular weight of a polymer viscosity hypothesis if the intrinsic viscosity of
2.3 dl / g under Theta conditions? consider the value of K of 3.6 x 10 -3.
14. What is the value for a polymiida DP approach with structure

If 0.50 g / l solution in 1 cm cells showed uptake (absorbance) anthracene is 0.28 in 360 mm?
Suppose that the molar absorpsivitas for 7800 for the anthracene units. (MP Stevens, J.Polym. Sci.
Polymer. Lett. Ed., 22,467, 1984).

71