Journal of Polymer and Biopolymer Physics Chemistry, 2018, Vol. 6, No.

1, 13-25
Available online at http://pubs.sciepub.com/jpbpc/6/1/2
©Science and Education Publishing
DOI:10.12691/jpbpc-6-1-2

Intrinsic Viscosity Determination of High Molecular

Weight Biopolymers by Different Plot Methods.
Chia Gum Case
Martin A. Masuelli*

Laboratorio de Investigación y Servicios de Química Física (LISeQF-UNSL). Instituto de Física Aplicada-CONICET y FQByF-
Universidad Nacional de San Luis, Ejercito de los Andes 950, ZC: 5700, San Luis, Argentina
*Corresponding author: [email protected]
Received August 17, 2018; Revised September 28, 2018; Accepted October 08, 2018
Abstract The chia (Salvia hispanica) generates an abundant and viscous mucilage, this is purified with periods of
heating-cooling and finally precipitated with ethanol, obtaining chia gum, CG. In this work the intrinsic viscosity is
determined by different methods being Huggins taken as standard. The different methods are compared and
evaluated with their respective percentage relative errors. By means of intrinsic viscosity is determined the
molecular weight with a value of 3846000g/mol. This polysaccharide acquires a rod-like conformation with an "a"
value, Mark-Houwink parameter, of 0.803 according to Int. J. Biological Macromol. 81 (2015) 991–999. This
macromolecule is very promising and has a potential in several industrial applications such as film forming, gel,
thickener, and coemulsifier.
Keywords: chia gum, intrinsic viscosity, molecular weight
Cite This Article: Martin A. Masuelli, “Intrinsic Viscosity Determination of High Molecular Weight
Biopolymers by Different Plot Methods. Chia Gum Case.” Journal of Polymer and Biopolymer Physics
Chemistry, vol. 6, no. 1 (2018): 13-25. doi: 10.12691/jpbpc-6-1-2.

Campos et al. [4], studied extraction of mucilage of

chia seed varied temperature (30-80 C), extraction time
1. Introduction (2-4 h) and water: seed ratio (10:1-30:1) on the yield.
Salgado-Cruz et al. [5], released microstructural
Chia (Salvia hispanica) is an herbaceous plant of the characterization of chia seed mucilage. Results showed
family Lamiaceae, is of Mesoamerican origin; it is one of that the mucilage is excreted from the polygonal cells
the plant species with the highest concentration of omega of the epidermis coat, being composed mainly by
3 (alpha-linolenic fatty acid). It is therefore cultivated to carbohydrates fibres (18–45 nm width).
take advantage of its seeds, which are used as ground food Capitani et al. [6], evaluated the viscoelasticity and
[1]. The seeds soaked in water release the mucilage, flow behavior of aqueous dispersions with different
producing a gelatinous liquid; in Mexico it is flavored concentrations of chia mucilage (Salvia hispanica L.) from
with vegetable juices or essences and it is consumed as a Argentina seeds. The mucilage obtained by two methods:
refreshing drink. The seeds can also be dried and ground (I) soaking–freezing–freeze drying–sieving, and (II)
to prepare a fine flour with an intense flavor, called pinole, soaking–filtration–concentration–freezing–freeze drying.
which is consumed mainly as a sweet. Tender shoots are The effect of mucilage concentration, temperature, pH,
eaten as raw or cooked vegetables and can be used in ionic strength and presence of sucrose on the rheological
salads. The nutritional composition of chia seed is: 20% properties of the aqueous dispersions with the addition of
protein, 40% dietary fiber (5% soluble fiber of very high NaCl or CaCl2 is also evaluated.
molecular weight) and 34% oil; over 64% of the oil are Timilsena et al. [7,8], extracted chia seed gum, and its
omega 3 and fatty acids. It does not contain gluten, so it is rheological and microstructural properties in aqueous
suitable for celiacs. Non toxic components are known in it solutions are studied. The intrinsic viscosity is high
[2]. (∼1600 cm3/g) Controlled acid hydrolysis of purified
Lin et al [3], reported a tentative structural linear unit CSP yielded various low molecular fractions with
of chia seed gum, this is a tetrasaccharide with 4-O- fairly uniform polydispersity giving a Mark–Houwink
methyl-a-D-glucoronopyranosyl residues occurring as relationship of intrinsic viscosity equaling to 0.0152
branches at 0-2 of some b-D-xylopyranosyl residues in the (molecular weight) 0.803 (cm3/g).
main chain consisting of (1->4)-b-D-xylopyranosyl-(1- Capitani et al. [9], characterized the physicochemical
>4)-a-D-glucopyranosyl-(1->4)-b-D-xylopyranosyl units. and functional properties of meals (M) and fibrous
The molecular weight varies from 0.8 to 2.0 x 10 6 daltons. fractions (FRF) of chia seeds (Salvia hispanica L.), and to
14 Journal of Polymer and Biopolymer Physics Chemistry

compare the effect of oil extraction methods (pressing -p- In this work we will study the mucilage obtained from
and solvent extraction -s-) and sieving process on these the chia, which we purified for obtained of chia gum (CG).
properties. At CG we will perform physicochemical studies in aqueous
Muñoz et al. [10], researched the effect of temperature solution using viscosity and density determinations. In this
(4–80 C), pH (4–8) and seed:water ratio (1:20 and 1:40) work the intrinsic viscosity is determined by different
on extraction of the mucilage of chia seeds and the effect methods being Huggins taken as standard. The different
of temperature (20–80 C), pH (3–9) and ionic strength (0– methods are compared and evaluated with their respective
1%) on hydration of the extracted mucilage. The mucilage percentage relative errors. Also, we will obtain Mark-Houwink
is localized in cellular structures in the first three layers of parameters from intrinsic viscosity measurements and
the seed coat and upon full hydration filaments (mucilage with which we will determine the molecular weight and
fibers) became apparent and conformed to a transparent the hydrodynamic parameters of CG.
‘‘capsule’’ attached to the seed. During extraction, temperature
and seed:water ratio were found to have a significant 1.1. Intrinsic Viscosity and Hydrodynamic
effect on yield. Hydration of the extracted mucilage is
significantly increased at high pH values, and was higher
Parameters
when salt concentration decreased, being maximal when The viscosity of a capillary viscometer can be
the temperature reached values close to 80 C. calculated from the following equation:
Segura-Campos et al. [11], extracted Chia Gum from its
dietary fiber fractions for use as an additive to control η r = Aρ t (1)
viscosity, stability, texture, and consistency in food It should also be remembered that:
systems. They reported that gums dispersion exhibited a
non-Newtonian fluid behavior, specifically shear thinning η s ρ s .ts
η=
r = (2)
or pseudoplastic type. η0 ρ0 .t0
Goh et al. [12], obtained hydrated chia seeds using
water and isolated by ethanol precipitation. They reported where the subindex “s” indicates “solution” and “0”
that chia gum from freeze-dried consisted of ∼95% non- indicates “solvent” viscosity.
starch polysaccharides (35% w/w neutral soluble fraction IUPAC recommends the term “increment of relative
and 65% w/w negatively charged insoluble fraction). The viscosity (ηi)”, instead of “specific viscosity”, because it
soluble polysaccharide fraction has molar mass, root-mean has no attributions of specific quantity, meaning:
square radius and intrinsic viscosity of ∼5 × 105 g/mol, 39 η= (3)
i η sp
= ηr − 1
nm and 719 cm3/g, respectively. The viscosity of the
dispersion is fairly resistant to variations in temperatures when high concentrations are used it is better to start with
(20–80◦C), pH (4–12), ionic strengths (0.01–0.5 M NaCl) the first term of the Huggins equation “ηsp/c = ηred”.
and cation types (MgCl2, CaCl2, NaCl and KCl). The In Huggins’ method [15], intrinsic viscosity [η] is defined
swollen microgel particles dispersed in soluble as the ratio of the increase in relative viscosity (ηsp) to
polysaccharide continuous phase provided complex and concentration (c in g/cm3) when the latter tends towards zero.
potentially useful rheological properties in food systems.
Coorey et al. [13], studied the characteristics of chia gel η sp 2
and compared to guar gum and gelatin which are = [η ] + K H [η ] c (4)
c
commonly used in the food industry. The extracted chia
gels from seeds and flour are analyzed for moisture, where KH is Huggins constant.
ash, protein, crude fiber, oil, and fatty acid profile. The Kraemer [16] propose the following equation:
Water-holding capacity, oil-holding capacity, viscosity, ln ηr 2
emulsion activity, and freeze–thaw stability of the = [η ] + K K [η ] c (5)
extracted chia seed gel are similar to guar gum, and c
gelatin. Chia gel is a polysaccharide based gel mainly where KK is Huggins constant.
consists of crude fiber (58%) and carbohydrate (34%). The Martin [17] propose the following equation:
Extracted chia seed gel has a great potential in food
formulations as thickening agent, emulsifying agent, and η sp
ln= ln [η ] + k M [η ] c (6)
as a stabilizer. c
Dick et al. [14], investigated the physicochemical and
mechanical properties of a novel edible film based on chia where KM is Martin’s constant.
mucilage (CM) hydrocolloid. CM (1% w/v) films were Fuoss [18] propose the following equation:
prepared by incorporation of three concentrations of c 1 1
glycerol (25%, 50%, and 75% w/w, based on CM weight). = + k Fs c1/2 (7)
As glycerol concentration increased, water vapor
η sp [η ] [η ]
permeability (WVP), elongation at break, and water where KFs is Fuoss constant.
solubility of CM films increased while their tensile Fedors [20] propose the following equation:
strength, and Young’s modulus decreased significantly.
CM films exhibited excellent absorption of ultraviolet 1 1 1
= − (8)
light, and good thermal stability. This study demonstrated
that the chia mucilage hydrocolloid has important
2 (
η1/2
r −1 ) [η ] c [η ] Cmax
properties and potential as an edible film, or coating. where Cmax is polymer parameter concentration.
 Journal of Polymer and Biopolymer Physics Chemistry 15

Heller [21] propose the following equation: Maron & Reznik [38] propose the following equation:

1  1 1  1
(9)
η sp − ln ηr [η ]2 +  k 1 3
c +
2  η sp ln ηr
 = − K He c
 [η ] 2
=  H −  [η ] c (21)
 c 2  3

where KHe is Heller’s constant. Maron-Reznik Modified equation

Lyons & Tobolsky [22,23] propose the following equation:
 η sp − ln ηr   [η ]2 
η sp K [η ] c  ln  =  ln   +  k H − 1  [η ]3 ln c. (22)
ln= ln [η ] +  L −T  (10)  c 2
  2   3
c 1 − bc  
 
where KL-T and b are constant. In this work two alternatives are proposed that serve to
Baker [24,25] propose the following equation: calculate the intrinsic viscosity and are models that take
into account the average between two values obtained by
c different methods that we will detail next.
ηr1/ n = 1 + [η ] (11)
n The first is a plot method where the figures of the
equations are made 23 and 24. Finally, from the ordinate
1 to the origin, the intrinsic viscosity is obtained and the
n= (12)
1 − 2K H average is obtained from them.
with 0.25<KH<1, and KH = 0.9204. 2
 η sp 
Tager [26] propose the following equation:  =  [η ]2 + k p 2 c 2 (23)
 c 

[η ] ( )
c 1
= KT 1 + KT 2C 2 (13) The relative percentage error (RE%) with respect to
η sp
Huggins of this equation is by excess.
where KT1 and KT2 are Tager’s constant. 1/2
Budtov [27] propose the following equation:  η sp 
 c =  [η ]1/2 + k p1/2 c1/2 . (24)
ηr KB
= 1 + K B [η ] c (14)  
The percentage relative error (RE%) with respect to
K B = 1 − 2K M (15) Huggins of this equation is by default.
Where KM is Martin's constant. This method is not Therefore, an average of both plot solutions gives a
applicable to intrinsic viscosity and molecular weights as value of less than 5% regarding the Huggins method.
high and KM>0.5. In the second case, an empirical equation is proposed, which
Solomon & Gotesman [28,29,30] propose the following is a combination of both, from the realization of the figure
equation: and from the ordinate to the origin, the intrinsic viscosity
is obtained. This work proposes the following empiric equation:
1 η
[η ] sp .
1 + η sp = (16) 
1  η sp
2
  η sp 
1/2 
3 c 
2  c
 + 
  c 



2 1
 =2.5 [η ] + k p c + c
2
2
(
1/2
)
(25)
Arrhenius-Rother-Hoffmann [31,32,33,34] propose the 
following equation:
where kp2, kp1/2 and kp are constants which contain the
ln ηr intrinsic viscosity function.
= [η ] + K A ln ηr (17) The Mark-Houwink [39,40] equation (26) describes the
c
relationship between intrinsic viscosity and molecular
where KA is constant. weight. Since molecular weight is related to the size of the
Kreisa [35] propose the following equation: polymer chain [41]. The calculation of Mark-Houwink
2 (M-H) parameters is carried out by the plot representation
η sp η sp
= [η ] + K Kr (18) of the following equation:
c c
ln [=
η ] ln k + a ln M w (26)
where KKr is Kreisa’s constant.
Staudinger & Heuer [35] propose the following equation: where k and a are M-H constants, depending upon the type of
polymer, the solvent, and the temperature of viscometric
η sp determinations. The exponent a is a function of polymer
ln= ln [η ] + K S − H [η ] c (19)
c geometry and varies from 0.5 to 2.0. These constants can
be determined experimentally by measuring the intrinsic
where KS-H is a constant.
viscosity of several polymer samples for which the
Schramek [37] propose the following equation:
molecular weight has been determined by an independent
 η sp 
1/ n method (e.g., osmotic pressure or light scattering) [42].
 =  [η ]1/ n + kSch c (20) Using the polymer standards, a plot of ln [η] versus ln
 c  Mw usually gives a straight line. The slope of this line is
the value of a and its intercept is equal to ln k. The M-H
where KSch is Schramek’s constant.
exponent bears the signature of a polymer chain's three-
16 Journal of Polymer and Biopolymer Physics Chemistry

dimensional conformation in the solvent environment: a 2.2. Viscosity and Density

values from 0.0−0.5 reflect a rigid sphere in an ideal
solvent; those from 0.5−0.8 a random coil in a good Measurements were taken from fresh MCG in aqueous
solvent; and from 0.8−2.0 a rigid or rod like configuration solutions of 0.001-0.1 % wt. Solutions and dissolutions
(stiff chain). The polymer molecule assumes a tighter were prepared with deionised water. The different
configuration, and the solution has a lower intrinsic temperatures were maintained using a HAAKE C thermostatic
viscosity. The M-H “a” constant is close to 0.5 in “poor” bath (±0.1°C). Determinations were done using an
solvents, whereas for a rigid or rod-like polymer molecule Ubbelohde “suspended level” viscometer (IVA 1), with a
that is greatly extended in solution the “a” constant water draining time of 35.97s. The density of each
approaches a value of 2.0 [43,44]. solution was measured using an Anton Paar DMA35N
The hydrodynamic radius (RH) is given by the Einstein densimeter.
relation [45],
3
M [η ] = ν a / b N A π ( RH )3 . (27) 3. Results and Discussion
4
A common practice to express the intrinsic viscosity The extraction of chia mucilage is a procedure carried
and specific volume [46], as: out in this work and with it diluted solutions of this
gum were prepared and the intrinsic viscosity was
[η ] determined by different methods. The intrinsic viscosity
ν a /b = (28)
Vs data calculated in this work differ from those reported by
Timalsena et al. [7] mainly due to differences in the
ν(a/b) is called Einstein viscosity increment, and Vs is way of extracting and purifying chia gum; our intrinsic
specific volume (cm3/g) [47,48]. viscosity is double that reported by these authors. In this
work, the following Mark-Houwink parameters were
used to calculate the molecular weight: [η] = 1.52 ×
2. Experimental 10-2M0.803 cm3/g [7], and with intrinsic viscosity greater
than of 1600 cm3/g. From the data using the Huggins
2.1. Mucilage Chia Gum (MCG) method the intrinsic viscosity was calculated with a
value of 2498.20 cm3/g, and from this the molecular
The mucilage was collected with a syringe from the seeds weight was calculated with a value of 3845000 g/mol.
of chia, Salvia hispanica. To dissolve this seeds, heating-cooling This macromolecule acquires in aqueous solution is
periods were carried out in agitation during 8hs at 90°C. rod-like form with the characteristic of being very
Once dissolved, it was pressure-filtration and precipitated branched [7].
with ethanol several times. Finally, it was dried at 60°C for Figure 2 shows the data obtained from the Huggins
24hs, and redissolved in distilled water at a concentration and Kraemer methods, in this figure we can see the
of 0.1% wt. difficulty that both methods converge for the calculation
of the intrinsic viscosity, being the Huggins method
normally taken as standard and with which The rest
of the methods are compared. The intrinsic viscosity
data can be compared in Table 1. In Figure 3 the
application of Martin's method is observed, the calculation
of the intrinsic viscosity accounts for an ER% of
1.55%, but R2=0.9326; in similar works such as
Roven'kova et al. [49,50] comparative and detailed
studies were made of different graphical methods for the
calculation of the intrinsic viscosity in which they
conclude that the Martin and Budtov methods are suitable
for synthetic polymers used. One of the problems that
normally involves the Kraemer method is its slope and
also its R2 approximately equal to zero, which is why
it is not taken as a reference to compare against other
methods.
In Figure 4 and Figure 5 are the methods of Fuoss and
Fedors, both methods have become more relevant in the
last 20 years, in the first RE% is close to 10%, and second
less than 1%. Both methods have 30 years of separation
from each other, but with outstanding news. The method
https://viaorganica.org/como-cosechar-semillas-de-chia-en-tu-huerto/
of Heller, developed in the 1950s, is another method that
https://www.frutoseco.com/es/semillas-legumbres/11-comprar-semillas- has jumped to be used today, this method acquires a
de-chia-online.html RE% close to 10% which makes it unsuitable for this
https://mejorconsalud.com/semillas-chia-remedio-natural-estrenimiento/ type of macromolecules with high molecular weight
Figure 1. Salvia hispanica flower, seed and mucilage (see Figure 6).
 Journal of Polymer and Biopolymer Physics Chemistry 17

Table 1. Intrinsic viscosity by different methods

Methods Huggins Kraemer Martin Fuoss Fedors

3
[η] (cm /g) 2948.20 3217.20 2993.80 2673.79 2932.55
R2 0.9902 - 0.9326 0.9592 0.9948
RE% - 9.12 1.54 9.73 0.53
Methods Heller Lions-Tobolsky Baker Tager Solomon-Gotesman
[η] (cm3/g) 3184.89 2851.50 2605.20 3431.27 2955.90
2
R 0.9542 0.9927 0.9885 0.8906 0.9912
RE% 8.37 3.28 11.63 16.38 0.26
Methods Arrhenius-Rother-Hoffmann Kreisa Staudinger-Heuer Schramek Maron-Reznik
[η] (cm3/g) 2911.10 3298.50 3202.22 3098.26 3262.51
2
R 0.8619 0.9210 0.9572 0.9780 0.9773
RE% 1.26 11.88 8.62 5.09 10.66
Methods Budtov Square Square Root Mean New Method
3
[η] (cm /g) 2498.40 3674.23 2042.04 2858.14 2851.75
R2 0.9863 0.9740 0.9714 - 0.9986
RE% 15.26 24.62 30.73 3.05 3.27

8000
y = 8E+06x + 2948.2
7000 R² = 0.9902
6000
ηsp/c or (lnηr)/c (cm3/g)

5000

4000

3000
y = -195197x + 3217.2
2000 R² = 0.0381

1000

0
0.000000 0.000100 0.000200 0.000300 0.000400 0.000500 0.000600
c (cm3/g)
Huggins Kraemer

Figure 2. Huggins and Kraemer methods

9.2
y = 2212x + 8.0043
9 R² = 0.9326

8.8
ln ηsp/c

8.6

8.4

8.2

8
0.0000 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006

c (g/cm3)

Figure 3. Martin method

18 Journal of Polymer and Biopolymer Physics Chemistry

0.00035

0.0003
y = -0.010791x + 0.000374
0.00025 R² = 0.959213
c/ηsp (g/cm3)
0.0002

0.00015

0.0001

0.00005

0
0 0.005 0.01 0.015 0.02 0.025

c1/2

Figure 4. Fuoss method

7
y = 0.000341x - 0.406502
6 R² = 0.994779

5
1/2(ηr1/2-1

0
0 5000 10000 15000 20000 25000
c (cm3/g)

Figure 5. Fedors equation

0.00035

0.0003
0.5 c (1/ηsp+1/ln ηr)

0.00025

0.0002

0.00015 y = -0.253931x + 0.000313

R² = 0.954231
0.0001

0.00005

0
0.000000 0.000100 0.000200 0.000300 0.000400 0.000500 0.000600

c (cm3/g)

Figure 6. Heller equation

 Journal of Polymer and Biopolymer Physics Chemistry 19

9.4

9.2 y = 2384x + 7.9556

R² = 0.9927
9
ln ηsp/c
8.8

8.6

8.4

8.2

8
0 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006
c (cm3/g)

Figure 7. Lyons-Tobolsky equation

y = 2,605.2005x + 0.9862
0.8
R² = 0.9885

0.6

(ηr)1/n
0.4

0.2

0
-0.00045 -0.0004 -0.00035 -0.0003 -0.00025 -0.0002 -0.00015 -0.0001 -0.00005 0
-0.2
c/n

Figure 8. Baker equation

12000
y = 28,099,365,950.04x + 3,431.27
10000 R² = 0.89

8000

6000
c/ηsp

4000

2000

0
0 5E-08 0.0000001 1.5E-07 0.0000002 2.5E-07 0.0000003
c2

Figure 9. Tager equation

20 Journal of Polymer and Biopolymer Physics Chemistry

8000
y = 2955.9x + 701.18
7000 R² = 0.9912

6000

5000
1/(1+3ηsp)

4000

3000

2000

1000

0
0 0.5 1 1.5 2 2.5
c/ηsp

Figure 10. Solomon-Gotesman Equation

4000

3500

3000
y = 514.18x + 2911.1
2500 R² = 0.8619
(ln ηr)/c

2000

1500

1000

500

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

ln ηr

Figure 11. Arrhenius-Rother-Hoffmann Equation

12000
y = 0.2905x + 3298.5
10000 R² = 0.921

8000
ηsp/c

6000

4000

2000

0
0 5000 10000 15000 20000 25000 30000

ηsp2/c

Figure 12. Kreisa method

 Journal of Polymer and Biopolymer Physics Chemistry 21

Figure 7 shows a method that stands out for its RE% with a RE% greater than 10%, which makes it unsuitable
less than 5% that can be useful at the time of using an for the present study.
appropriate plot method of calculating the intrinsic viscosity. One of the methods of the early 20th century is that of
Figure 8 shows the Baker method, this method is Staudinger-Heuer with a RE% less than 10%, as can be
dependent on the Huggins method since in this case n seen in Figure 13.
contains the Huggins constant, KH, and not only carries The Schramek power method with n = 2, is a method
the errors of Huggins method but adds its own, which with RE% close to 5% which makes it attractive for this
leads to RE% greater than 10%. Therefore, Baker's type of calculation, the difficulty lies in the selection of
method is inadequate if one wants to determine the the value of n, which represents a source of error to the
intrinsic viscosity. method.
Figure 9 shows the Tager method, which has a RE% The Maron-Reznik method, Figure 15, is an inadequate
greater than 15%. model for the calculation of intrinsic viscosity; therefore,
The Solomon-Gotesman method, Figure 10, is an it is essential to modify it in order to calculate it, this
empirical equation that provides intrinsic viscosity data situation causes it to be unsuitable for its use (RE%> 10).
with RE% less than 0.5%, which makes it a very suitable Budtov's method, Figure 16, is a slope model of
method for this type of macromolecules. Martin's constant, KM, similar case of Baker's model,
The Arrhenius-Rother-Hoffmann equation, observed in makes it inappropriate and impractical at the time of being
figure 11, is one of the oldest and most accurate methods able to calculate the intrinsic viscosity with an RE%> 10.
of plot calculation of the intrinsic viscosity with RE% less The Budtov method is inadequate to calculate the intrinsic
than 2%. This classic method is universal and applicable to viscosity since it is dependent on the method applied by
macromolecules of all types, although it is not widely used. Martin, which leads to an error in the most pronounced
In Figure 12 we observe the application of the Kreisa calculation due to this dependence. Therefore, both
method for the plot calculation of the intrinsic viscosity unsuitable to be applied for this type of biopolymers.

9
8.9 y = 1662.5x + 8.0716
R² = 0.9572
8.8
8.7
8.6
8.5
ln ηsp/c

8.4
8.3
8.2
8.1
8
0 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006

c (g/cm3)

Figure 13. Staudinger-Heuer equation

90
y = 58812x + 55.662
80 R² = 0.978
70
60
(ηsp/c)1/n

50
40
30
20
10
0
0 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006

c (cm3/g)

Figure 14. Schramek equation, with n=2

22 Journal of Polymer and Biopolymer Physics Chemistry

25
y = -1.5374x + 4.3917
R² = 0.9773 20

15

ln(ηsp-ln ηr)/c2
10

0
-12 -10 -8 -6 -4 -2 0

ln c

Figure 15. Maron-Reznik modified equation

2
y = 2498.4x + 0.63
1.8 R² = 0.9863
1.6
1.4
((ηrkB-1)-1)/kB

1.2
1
0.8
0.6
0.4
0.2
0
0 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006
c (g/cm3)

Figure 16. Budtov Method

Square Method
60000000
y = 1.52E+14x + 1.35E+07
50000000 R² = 9.74E-01
(ηsp/c)2

40000000

30000000

20000000

10000000

0
0 5E-08 0.0000001 1.5E-07 0.0000002 2.5E-07 0.0000003
c2

Figure 17. Square Method

 Journal of Polymer and Biopolymer Physics Chemistry 23

Square Root Method

90
y = 1661.2x + 45.189
80
R² = 0.9714
70
60
(ηsp/c)1/2

50
40
30
20
10
0
0 0.005 0.01 0.015 0.02 0.025
c1/2

Figure 18. Square root method

New Method
25000000

20000000 y = 1.8263E+09x - 1.3012E+06

0.5{(ηsp/c)2+(ηsp/c)1/2}

R² = 9.9857E-01

15000000

10000000

5000000

0
0 0.002 0.004 0.006 0.008 0.01 0.012

0.5(c2+c1/2)

Figure 19. New equation proposed

In this paper two ways to calculate are proposed that from the intercept, the intrinsic viscosity is obtained. The
serve to determine the intrinsic viscosity and are plot intrinsic viscosity obtained is with a value of 2851.75
methods that take into account the average between two cm3/g and RE%=3.27%.
values obtained by different methods that we will detail next. The Mark-Houwink parameters observed in Table 2 are
The first plot method is based the equations 23 and 24, reference from Timalsena et al. [7]. The hydrodynamic
plotted Figure 17 and Figure 18. Finally, from the ordinate radius of the macromolecules changes with the type
to the origin, the intrinsic viscosity is obtained and the solution and with temperature via changes in their chain
average is obtained from them. flexibility. The molecular weight determined for this work
The relative percentage error with respect to Huggins of is 3845000 g/mol, with an intrinsic viscosity by Huggins
this equation 23 is by excess (RE%=24.62%); and plot of method of 2498.20 cm3/g. What is very clear is that it is a
equation 24 obtained error respect to Huggins is by default molecule that acquires a rod-like shape, that is
(RE%=30.73%). Therefore, an average of both plot hyperbranched and that water is not an ideal solvent;
solutions gives a value of 3.05% regarding the Huggins clarifying that it is only valid for the treatment carried out
method. in the extraction and purification performed in this work.
In the second case, an empirical equation 25 is Mark-Houwink value of “a” confirm that for these
proposed, which is a combination of the previous plot conditions. Empiric functions can be used to facilitate the
method (an empirical combination of equations 23 and 24). calculation of these parameters in an acceptable way, as
Figure 19 is the realization of the plot of this equation, proposed in this work.
24 Journal of Polymer and Biopolymer Physics Chemistry

Table 2. Mark-Houwink and hydrodynamic Parameters

KH KM RH (nm) M (g/mol) νa/b k (cm3/g) a

0.9204 0.7388 182.68 3845000 2.80 0.00152 0.803

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