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Sorption of Water Vapor, Hydration, and Viscosity of

Carboxymethylhydroxypropyl Guar, Diutan, and Xanthan Gums,
and Their Molecular Association with and without Salts (NaCl, CaCl2,
HCOOK, CH3COONa, (NH4)2SO4 and MgSO4) in Aqueous
Solution
Paltu Banerjee, Indrajyoti Mukherjee, Subhash Bhattacharya, Sidhhartha Datta, and
Satya P. Moulik*
Centre for Surface Science, Department of Chemistry, Jadavpur University, Kolkata 700032, India

Diptabhas Sarkar
Halliburton, 10200 Bellaire Boulevard, Houston, Texas 77072

Received April 9, 2009. Revised Manuscript Received August 10, 2009

Gums are routinely used in food industry, pharmacy and oil recovery process. In these uses, the hydrocolloids
very often encounter interactions with salts at moderate to high temperature. Since they are normally employed in
the form of solution and gel, their viscous or fluidity properties need detailed investigation. In the present work,
properties such as water vapor adsorption of finely powdered carboxymethylhydroxypropyl derivatized guar
(CMHPG) as well as xanthan (Xn) and diutan (Dn) gums, their hydration in solution, their viscosity behaviors, and
salt effects on fluidity have been studied. The concentration domains for the existence of free and associated molecules in
the studied solutions have been assessed from the viscosity results. The gums have been found to bind a fair amount of
water from the vapor phase with them. In solution, they can interact and arrest a large amount of water in their folded
configuration. Intrinsic viscosities of the gums in aqueous medium declined in the presence of salts. The activation
energies for their viscous flow were moderate and comparable, and were dependent on their concentrations. From the
power law relation and viscosity master curve behavior mostly two critical association states of the macromolecular
dispersions were envisaged.

Introduction
Biopolymers such as gums, carboxymethylcellulose, pectin,
and other carbohydrate-based materials are liberally used in the
preparation of flow controlling solutions, in pharmacy,1,2 in food
industries, in textiles,3 in mineral processing,4 in cementing,5 in
oil-field operations,6 and in many other industrial processes.7-11
The gums, derivatized carboxymethyl and hydroxypropyl
guar (CMHPG), diutan (Dn), and xanthan (Xn) are used or
*Corresponding author. E-mail: cssju@yahoo.co.uk. Fax: 91-33-2414-
6266.
(1) Gebert, M. S.; Friend, D. R. Pharm. Dev. Technol. 1998, 3, 315–323.
(2) Misra, A. N.; Baweja, J. M. Indian Drugs 1997, 34, 216–223.
(3) Kokol, V. Carbohydr. Polym. 2002, 50, 237–247.
(4) Liu, Q.; Zhang, Y.; Laskowski, J. S. Intl. J. Miner. Proc. 2000, 60, 229–245.
Wang, J.; Somasundaran, P.; Nagaraj, D. R. Miner. Eng. 2005, 18, 77–81. Ma, X.;
Pawlik, M. J. Colloid Interface Sci. 2006, 298, 609–614.
(5) Sakata, N.; Yanai, S.; Yokoziki, K.; Maruyama, K. J. Adv. Concrete
Technol. 2003, 1, 37–41.
(6) Prud’homme, R. K.; Constien, V.; Knoll, S. Adv. Chem. Ser. 1989, 89, 223–
236.
(7) Brode, G. L.; Harris, E. D.; Salensky, G. A. In Cosmetic and Pharmaceutical
Applications of Polymers; Gebelein, C. G., Cheng, T. C., Yang, V. C., Eds.; Plenum:
New York, 1991; p 117.
(8) Tsaur, L. S.; Shen, S.; Jobling, M.; Aronson, M. P.; Lever Brothers Co. U.S.
Patent 6,066,613, 2000.
(9) Goldstein, A. M.; Alter, E. N. In Industrial Gums, Polysaccharides and their
Derivatives; Whistler, R. L., Ed.; Academic Press: New York, 1959; p 321.
(10) Goel, N.; Shah, S. N.; Yuan, W. L.; O’Rear, E. A. J. Appl. Polym. Sci. 2001,
82, 2978–2990.
(11) Rayment, P.; Ross-Murphy, S. B.; Ellis, P. R. Carbohydr. Polym. 2000, 43,
1–9.
(12) Nayak, B. R.; Singh, R. P. Polym. Int. 2001, 50, 875–884.
have prospects for use in the oil field, particularly as fracturing
fluids.12,13 “Fracturing” as related to oil field services, is a process
in which a “fluid” laden with “propping agents” is pumped into
an underground rock formation at a very high pressure and flow
rate. The idea is to fracture the subterranean hydrocarbon bearing
formation to create lateral fractures or to enhance existing
fractures make recovery of oil and gas faster. The propping
agents (compression resistant materials like ground walnut shells,
sand, and ceramic beads, etc.) are used to hold the newly for-
med “fracture” open. The base fluids used are solutions of the
biopolymers, which aid in suspending the propping agents;
frequently, the solutions are cross-linked.
Most of the carbohydrate-based polymers (macromolecules)
hydrate and swell in the presence of water forming solutions of
increasing viscosity depending on their concentration. A funda-
mental understanding of the behavior of these biopolymers in
solution is essential in optimizing their use in various industrial
processes. In addition, the possibility of interaction of these
biopolymers with salts has significance with reference to food
formulations and fluidity controlling formulations and especially
in oil-field applications.
Investigations on the interaction of different salts with simple
carbohydrates have been done in the past.14 For example, it is
(13) Etemadi, O.; Petrisor, I. G.; Kim, D.; Wan, M. W.; Yen, T. F. Soil
Sedimentation Contamination 2003, 12, 647–661.
(14) Moulik, S. P.; Khan, D. P. Carbohyd. Res. 1974, 36, 147–157. Moulik, S. P.;
Mitra, A. K. Carbohyd. Res. 1973, 29, 509–512. Moulik, S. P.; Khan, D. P. Carbohyd.
Res. 1975, 41, 93–104.

Langmuir 2009, 25(19), 11647–11656 Published on Web 08/28/2009 DOI: 10.1021/la901259e 11647
Article Banerjee et al.

known that the carbohydrates form adducts with alkali and Scheme 1. Molecular Structures of (a) the Gum Carboxymethylhy-
alkaline earth metal salts.14 Interactions of salts with gums and droxypropylguar, (b) the Gum Diutan, and (c) the Gum Xanthan
polysaccharides have been also studied by different workers.15-18
In addition, the rheological properties of pure and modified
gums and carbohydrate polymers have been explored in details
in view of their field applications and flow controlling and
pharmaceutical and agricultural uses and applications.19-23
It is thus imperative that there will be physicochemical interac-
tions between the carbohydrate-based polymer (gums) and
salts, which constitute a major part of the objective of the present
study.
Guar gum is a galactomannan, a polysaccharide consisting
of (1-4)-linked β-D-mannopyranose backbone with a 1-6-
linked R-D-galactopyranose as a branch point. It is harvested
mainly from the endosperms of the seeds of the legume Cyamopsis
tetragonolobus, an annual plant found in arid regions of India.
In the derivatized guar (CMHPG) the amount of carboxymethyl
and hydroxypropyl groups in the backbone is characterized by a
molar substitution (MS) value and a degree of substitution (DS)
value, respectively. It is expected that derivatization of gums
should produce property changes.24 Thus, gums like carboxy-
methyl guar, hydroxypropyl guar; CMHPG, etc have evidenced
changes in soluibilities and rheological properties without and
with salts.25,26 Diutan is a natural high molecular weight gum
produced by controlled aerobic fermentation of the bacterial-
strain Sphingomonas sp. ATCC 53159. Diutan consists of a repeat
unit with L-rhamnose, D-glucose, D-glucuronic acid, D-glucose
backbone, and two-sugar L-rhamnose side-chain attached to the
(1 f 4) linked glucose residue. Two O-acetyl groups are attached
per repeat unit to the 20 and 60 positions of the (1 f 3) linked
glucose. Xanthan gum is a microbial desiccation-resistant poly-
mer prepared commercially by aerobic submerged fermentation
from Xanthomonas campestris. It is an anionic polyelectrolyte
with a β-(1f4)-D-glucopyranose glucan (as cellulose) backbone
with side chains of (3f1)-R-linked D-mannopyranose-(2 f1)-β-
D-glucuronic acid-(4f1)-β-D-mannopyranose on alternating re-
sidues. The molecular architectures of the three gums used in this
study are presented in Scheme 1a-c.
Here, we report the water absorption capacity and hydration
behavior of the above-mentioned gums, using conductance and
isopiestic methods. Their viscosity behaviors and effects of varia-
tion in temperature and presence of salts have been investigated in
detail. Results have provided information on native configuration
and molecular association in solution along with the activation threshold concentration above which dimers and multimers are
energy for the flow process. It is well-known that the gums show a formed.27-29 This aspect was investigated for the three gums
through viscometric studies, with particular focus on the effect of
(15) Whitfield, D. M.; Stojkovski, S.; Sarkar, B. Coord. Chem. Rev. 1993, 122, salts and temperature. It may be mentioned that of the three gums
171–225. herein experimented upon, CMHPG has been fairly studied from
(16) Lynn, J. D.; Nasr-El-Din, H. A. J. Pet. Sci. Eng. 1998, 21, 179–201.
(17) Yadira, I.; Cantu, V.; Hauge, R. H.; Norman, L. R.; Powell, R. J.; Billups, the standpoint of rheology and interaction with salts, xanthan has
W. E. Biomacromolecules 2006, 7, 441–445. been moderately studied, but diutan has been rarely investigated.
(18) Gittings, M. R.; Cipelletti, L.; Trappe, V.; Weitz, D. A.; In, M.; Lal, J. In addition, the hydration behaviors of all the three gums have
J. Phys. Chem. A 2001, 105, 9310–9315.
(19) Mahammad, S.; Comfort, D. A.; Kelly, R. M.; Khan, S. A. Biomacromo- been so far remaining unexplored. In the present work, a
lecules 2007, 8, 949–956. comparative physicochemical assessment of the solution behav-
(20) Kok, M. S.; Hill, S. E.; Mitchell, J. R. Food Hydrocolloids 1999, 13, 535– iors of the three gums in the absence and presence of salts has been
542.
(21) Lai, L. S.; Chiang, H. F. Food Hydrocolloids 2002, 16, 427–440. attempted.
(22) (a) Higiro, J.; Herald, T. J.; Alavi, S.; Bean, S. Food Res. Int. 2007, 40, 435–
440. (b) Higiro, J.; Herald, T. J.; Alavi, S. Food Res. Intl. 2006, 39, 165–175.
(23) Lai, L. S.; Tung, J.; Lin, P. S. Food Hydrocolloids 2000, 14, 287–294. Experimental Section
(24) Rinaudo, M. Biomacromolecules 2004, 5, 1155–1165. Materials. The gums CMHPG (carboxymethylhydroxypro-
(25) (a) Zhang, L.-M.; Zhou, J.-F.; Hui, P. S. J. Sci. Food. Agric. 2005, 85, 2638–
2647. (b) Pasha, Mazhar; Swami, N. G. N. Pak. J. Pharm. Sci. 2008, 21, 40–44. pylguar), diutan and xanthan used in this study were provided by
(c) Cheng, Y.; Brown, K. M.; Prud'homme, K. Biomacromolecules 2002, 3, 456–461. Halliburton Energy Services, Inc. (USA), and were used as
(d) Zhang, L.-M.; Jhou, J.-F. Colloids Surf. A: Physicochem. Eng. Aspects 2006, 279,
34–39.
(26) Cordova, A. US Patent 6,387,169, May 14, 2002. (28) de Gennes, P. G. Nature (London) 1979, 282, 367–370.
(27) Robinson, G.; Ross-Murphy, S. B.; Morris, E. R. Carbohyd. Res. 1982, 107, (29) Launay, B.; Cuvelier, G.; Martinez-Reyes, S. Carbohydr. Polym. 1997, 34,
17–32. 385-390 and references therein.

11648 DOI: 10.1021/la901259e Langmuir 2009, 25(19), 11647–11656

Banerjee et al.
received. CMHPG had MS range 0.15-0.35 and DS range
0.05-0.20. Both diutan and xanthan gums had high purity. The
gum diutan was isolated from the bacterial broth using enzymes to
break down the bacterial cells that were removed by filtration and
the biopolymer collected by precipitation. Xanthan was a food
grade material collected by drying after removing salts and
protein fragments at the lowest possible temperature to preserve
the native structure. When not in use, the gums were stored in a
desiccator to prevent sorption of moisture. Prepared solutions
were not used consecutively for more than 3 days. The salts
used were NaCl, CaCl2, HCOOK, CH3COONa, (NH4)2SO4
and MgSO4 obtained from either Merck (India) or SRL (India).
They were Pro Analysis grade, and were used without further
purification.
Water, doubly distilled over alkaline permanganate and ex-
hibiting conductance of 2-4 μS cm-1, was used in the experi-
ments.
Methods. Three methods, conductometry, isopiestic, and
viscometry, were employed in the study. A brief description of
each is presented below.
Conductometry. The conductometry method used here was
followed by Moulik et al.30 for the determination of hydration of
polyvinylpyrrolidone (PVP) system. In brief, measurements were
done with a Jenway (UK) (Model No. PCM-3) conductivity
bridge. The measurements were taken in a constant temperature
water bath with an accuracy of (0.1 °C using a dip type cell of
cell constant K = 1.0 cm-1 under constant stirring condition.
In the actual experiment, 10 mL of a 0.1% gum solution contain-
ing 0.01 M NaCl was taken in a container into which the cell
was dipped. The initial conductance of the solution was measured.
The 0.01 M NaCl solution was progressively added in small
installments into the gum solution. After each addition, it was
stirred well and allowed sufficient time to reach temperature
equilibrium and then the conductivity of the solution was deter-
mined and noted. The procedure was followed until the bio-
polymer solution was diluted to 0.05%. A control study was
performed for an aqueous solution of 0.1% gum in the absence
of NaCl, which was diluted by water following the same proto-
col as with NaCl solution. The conductances of the control
solutions were subtracted from the experimented solutions for
processing the data as per the physicochemical requirement to be
discussed later. Each experiment was duplicated to check repro-
ducibility.
Isopiestic Method. In this method, solid dried sample of a
powdered gum of definite weight was taken in several accurately
weighed sample bottles of special design. The bottles without lid
were then kept enclosed in several specially designed desiccators
containing concentrated sulfuric acid of varied strengths. The
desiccators were then evacuated, and the sulfuric acid solutions
were frequently stirred with magnetic stirrers for a week. It was
considered that by this time the vapor pressure equilibrium
between the hydrated samples present in the bottles and the
sulfuric acid solutions in the desiccators was established. The
sample bottles were then quickly taken outside the desiccators,
closed with the lids, and weighed. From the difference between the
final and the initial weights, the masses (mw) of the water vapor
associated per gram of the gum in the samples were known. The
concentrations of sulfuric acid in the desiccators were determined
by the NaOH titration method. The corresponding values of
the relative humidities (p/p0) at these acid concentrations were
obtained from the standard table. By Raoult’s law, these p/p0
values were the water activities. The measurements were per-
formed at a constant temperature of 303 ( 0.2 K. The standard
deviation of the mw values were within 3%. Further details on the
isopiestic method can be found elsewhere.30 The plot between mw
(30) Bull, H. B. J. Am. Chem. Soc. 1944, 66, 1499–1507. Ghosh, N.; Datta, P.;
Mahapatra, P.; Das, K. P.; Chattoraj, D. K. Biophys. Chem. 2001, 89, 201–217. Dan, A.;
Ghosh, S.; Moulik, S. P. J. Phys. Chem B. 2008, 112, 3617–3624.
Langmuir 2009, 25(19), 11647–11656
Article
and (p/p0) at a constant temperature then constitutes the sorption
isotherm of water with gum.
Viscometry. The viscosity measurements were also taken in a
water bath with an accuracy of 0.1 K. A three-armed calibrated
(with sucrose solution) Ubbelohde viscometer, used earlier by us30
was employed in the study. The flow time of 3 mL water through
the bulb was 160 s at 303 K. As per an earlier report of Norman
et al.,17 guar gum solutions of concentration e0.3% show New-
tonian flow behavior, which is e0.1% according to Ma and
Pawlik.31 The gum solutions herein used did satisfy this condition.
The measurements were taken in the concentration range
0.01-0.2% at several dilutions, and the time of flow was noted
at each concentration after proper temperature equilibration.
Averages of three repeat experiments were considered for data
analysis.
Results and Discussion
Water Content. The gum samples used in this study were
initially desiccated for removing the sorbed water in them.
Desiccation to constant weight of definite amounts of the gums
has shown the presence of water to the extents of 0.0786, 0.0994,
and 0.0708 g/g for CMHPG, diutan, and xanthan, respec-
tively. All through the study, the gum samples were kept in
desiccating condition, and were only taken out during solution
preparation.
Sorption of Water Vapor by the Gums. The water vapor
sorption property of the gums was studied by the isopies-
tic method as described above. The results are presented in
Figure 1.The g/g adsorption of water vapor are plotted against
water activity or p/p0 where p is the equilibrium vapor pressure,
and p0 is the aqueous tension at 303 K. Although the curves have a
Bruner-Emmet-Teller (BET, type III) isotherm like look, the
results did not fit the BET plots. Exponential growth fitting
procedure has yielded the maximum water adsorption extents of
CMHPG, diutan, and xanthan as 0.826, 0.673, and 0.816 g/g,
respectively, at p/p0 = 1. It may be mentioned here that isopiestic
method applied to the water vapor sorption on the polymer
polyvinylpyrrolidone (PVP) has evidenced formation of type III
multilayer adsorption isotherm which has responded to BET
treatment producing monolayer capacity of 0.40 g/g, and for-
mation of trilayer on the PVP binding centers,30 at p/p0 = 1. The
results have suggested that water molecules from the vapor phase
formed three stacked layers on the binding centers (N centers)
on the PVP at the maximum binding state. The total capacity
of binding was thus 1.2 g/g of PVP. In the case of gums, there
were plenty of oxygen centers in the molecules where water
molecules from the vapor can get attached by hydrogen bonding.
Formation of stacks (as in the case of PVP) was doubtful since
the multilayer rationale of BET did not fit to the data. Calculation
of water molecules bound per oxygen center on the gum could not
be performed for want of accurate knowledge on the molar
masses of the gums. It may be mentioned that water vapor
sorption studies with carbohydrate polymers were also reported
in the past.30
Hydration of Gums. In aqueous solution, the gums slowly get
hydrated. Their dilute solutions look transparent. We have herein
used low concentration (∼0.05-0.1 g dL-1) of the gums to study
their hydration characteristics by the method of conductance.
The eq 1 to be used to process the data has been found to obey in
low concentration of the obstructant (here the gums) to ion
conductance. The procedure has been described in the Method
section.
(31) Ma, X.; Pawlik, M. Carbohydr. Polym. 2007, 70, 15–24.
DOI: 10.1021/la901259e 11649
Article Banerjee et al.

Figure 1. Representations of Isopiestic plots for water vapor

adsorption by gums. Here n represents moles of water/kilograms Figure 2. Conductivity plots for the determination of hydration
of gum, and a is water activity. of gums.

The following equation (a rearranged form of the equation

used in earlier references)30,32,33 was used to monitor the hydra- Table 1. Slope (S), Vh and Hydration Values (mg)a,b of the Gums
tion properties of the gums at 303K

k gum S Vh, mL . g -1 mg, g g-1

¼ 1þ1:93V h c ð1Þ
k0
0 diutan
where k is the specific conductance of 0.01 M NaCl, k is the
conductance of the same electrolyte solution and c is the con-
centration of the gum expressed in g mL-1 at a constant
temperature, and Vh is its hydrated specific volume in solution.
The measurements were taken at different concentrations, and
the Vh was determined from the slope of the least-squares linear
plot between k/k0 and c. The nature of the observed plots is
illustrated in Figure 2, where fairly good linear dependences were
observed. The anhydrous specific volume of the gum (reciprocal
of the anhydrous density) was subtracted from the Vh to evaluate
mg, the g/g hydration of the gum. The slope, Vh, and the mg values
for the three studied gums are presented in Table 1.
The isopiestic and conductivity methods have produced data,
which are quite interesting. The former method has yielded results
∼20-30 fold lower than the latter. This type of nonequivalence
was not observed34 for the interaction of PVP with water
molecules in the vapor form as well as in the associated form in
solution when experimented following the same procedure herein
followed. This difference can be reasoned out in the following
way. In the isopiestic method, water vapor became adsorbed on
the gum particles, penetration into the interior was minor. The
extent of hydration was thus much lower than that in solution,
where the individual gum molecules got the full share of hydration
since all the hydrophilic centers were exposed to water. The Vh
values were thus greater. The trapping of water molecules into the
segmental folds/overlaps of the biopolymers increased Vh, and
hence the hydration (Scheme 2). In the PVP molecule, the
nitrogen centers were only solvated by the water molecules; there
were no other potential water interacting centers in the molecule.
Hence, at equal concentrations, PVP produced less interaction
than the gums. It is accepted that on the average in solution 2-3
water molecules get bound to one oxygen center.35 The carbohy-
drate polymer (gums) have such centers in plenty, and hence, it is
not unreal that they would show large hydration when measured
using the method of conductance in solution where the bio-
polymer molecules have free access to organize their mole-
(32) Moulik, S. P. Electrochim. Acta 1972, 17, 1491 - 1496; 1973, 18, 981 - 986.
(33) Mandal, A. B.; Biswas, A. M.; Ray, S.; Moulik, S. P. J. Phys. Chem. 1980,
84, 856–859.
(34) Dan, A.; Ghosh, S.; Moulik, S. P. Langmuir 2007, 23, 7531–7538.
(35) Moulik, S. P.; Gupta, S.; Das, A. R. Can. J. Chem. 1989, 67, 356–364.
CMHPG 38.50 19.9 19.2
35.64 18.5 17.9
xanthan 46.14 23.9 23.3
a
The measured anhydrous densities of the gums were 1.376, 1.500,
and 1.596 for CMHPG, diutan, and xanthan, respectively. Their reci-
procals, 0.727, 0.667, and 0.627 were their respective anhydrous specific
volumes. At 303K, the density of water was taken to be unity to evaluate
mg (g/g hydration of the gums). b Errors in mg were within (7%.
Scheme 2. Schematic Configurations of Gum in Aqueous and Salt
Environments
cular configurations to maximize their interaction with water
molecules.
Viscosity of Gum Solutions. The relative viscosities of the
aqueous gum solutions at different concentrations were deter-
mined at different temperatures, and the specific viscosity (ηsp)
values were obtained from the relation ηsp = ηr - 1. The ηsp per
unit concentration i.e., ηsp/C or reduced viscosity was then plotted
against C to obtain the intrinsic viscosity according to the
Huggins equation,
ηsp
¼ ½ηþk½η2 C ð2Þ
C
where, [η] is the intrinsic viscosity, C is the gum concentration
expressed in g dL -1, and k is the Huggins constant. A repre-
sentative plot for the gums is exemplified in Figure 3. The derived
[η] and k values are presented in Table 2.
The plots in Figure 3 are fairly linear with good correlations
except for diutan at 338 K. It is generally considered that 1/[η] is
the highest polymer concentration to be used in the Huggins
equation to evaluate [η]. Thus, in the studied range of temperature

11650 DOI: 10.1021/la901259e Langmuir 2009, 25(19), 11647–11656

Banerjee et al. Article

Figure 3. Trends of reduced viscosities in different concentrations

of gum solutions (aqueous) in different temperatures: 1, CMHPG, Figure 4. Plot of log[η] vs T-1 for the estimation of A and Ea of the
318 K; 2, CMHPG, 328 K; 3, Dn, 303 K; 4, Dn, 338 K; 5, Xn, gums.
298 K; 6, Xn, 303 K.
k =0.50-0.70. For uncharged solid spheres, the k value should be
∼1.0, and 2.0 in good and poor solvent, the constant for flexible
Table 2. Intrinsic Viscosity Values and Huggins Constants for Gums
coils is greater than 0.50. In a Θ solvent, k = 0.50-0.70 The
at Different Temperatures
constant k is also sensitive to molecular aggregation. At 298 K
[η]CMHPG, [η]Dn, [η]Xn, CMHPG, diutan and xanthan have shown k values of 0.15, 0.13,
temp, K dL g-1 kCMHPG dL g-1 kDn dL g-1 kXn and 0.19 respectively. The k values have increased with tempera-
298 68.40 0.15 41.65 0.13 55.16 0.19
ture. Solvation of the biopolymers has lessened with increasing
303 53.60 0.34 40.27 0.20 50.33 0.37 temperature-causing increase in k, which has even exceeded the
308 48.29 0.39 34.74 0.38 46.73 0.66 value of 2.0 (expected for sphere) for diutan at 338 K. At 318 K,
318 45.93 0.56 29.90 0.55 37.66 0.76 the criterion of the Θ solvent was applicable to the aqueous
328 36.15 1.04 22.04 1.33 31.13 1.05 solution of the gums for the values of k were 0.56, 0.55, and
338 14.44 3.74 27.20 1.29
0.76 for CMHPG, diutan, and xanthan, respectively.
(Table 2), the upper limits of concentration of the gums required The [η] can be related through the shape factor of the solute
to be used should range between 0.02-0.10 g dL -1. We have used species in solution and the partial specific volumes of the solute
C = 0.05 g dL -1 uniformly at all the temperatures used in the and the solvent,33,37 in the following way
study. We considered that on the overall basis, the uniform range
of experimented concentration, 0.05 g dL -1 would not incur ½η ¼ υðvg þδvw Þ ð3Þ
serious errors in the reported [η]. We may mention that higher
polymer concentrations than the required upper limit according where vg and vw are the partial specific volumes (for dilute
to the above rationale have been used by others.22,23 Ma and solutions, partial specific volumes have been considered  specific
Pawlik31 have shown a nice linear course in the concentration volumes)of the solute (gum) and the solvent (water), respectively,
range of 0-0.08 g dL -1 for guar of [η] = 22 dL.g -1 in saturated δ is the g/g hydration of the solute, and ν is the shape factor of the
LiCl solution solute in solution. For spherical geometry of the solute, ν = 2.5;
The Huggins equation is meant for neutral polymers. The gums for spheroids (prolates and oblates), ν > 2.5, and it depends on
herein studied were polyelectrolyte type with weakly acidic the axial ratio of the entity in solution.
(-COOH) groups. We have assumed that the Huggins equation Considering the specific volumes of the gums equal to the
was applicable to these weak polyelectrolytes. In the salt environ- reciprocal of their densities (see footnote a, Table 1), and the
ment manifestation of their charge effect was restricted by way of knowledge of their hydration in solution (determined by the
electrostatic screening. In the studied concentration range, their ηr conductance method and given in the table), their shape factors,
values were within 1.5 in salt solution so that Kraemer’s equation ν have been estimated. The magnitudes obtained at 298 K were
(subsequently described) was applicable. 3.3, 2.2, and 2.3 for CMHPG, diutan and xanthan, respectively.
In the aqueous medium, the [η] of all the three gums has The shape factors were close to that of spheres (2.5) except
decreased with increasing temperature. For a 30 K increase, the CMHPG, which has shown spheroidal characteristic at 298 K.
percent decreases were 50, 53, and 65% for CMHPG, xanthan, This has been an interesting observation found from the estimated
and diutan, respectively. On a comparative basis, [η] followed overall hydration of the gums and the use of eq 3. Similar analysis
the order CMHPG > xanthan > diutan; this was the effective on gums was not done in the past. According to reports27-29
sequence of the gums to obstruct the laminar flow of the solvent polysaccharides are semiflexible random coils in solution. Their
medium (water) in their solution. The decline in the reported [η] overall geometry can thus be modeled as sphere-like in line with
with temperature followed overall smooth trends. The [η] values the depiction of Robinson et al.27 In the illustration (Scheme 2),
obtained by the linear extrapolation method (Table 2) were thus we have pictorially shown the possible states of water (free,
reasonable. trapped, and hydrated) associated with the random coil biopoly-
The configuration of the polymers in solution can also be mer entity. Similar experimental results at higher temperatures
assessed,36 on an overall basis, from the Huggins constant values. would add more insight into the molecular geometry of the gums
For flexible polymers in a good solvent, the values range between which is contemplated to be examined in a future study.
0.20-0.40, the value is greater in poor solvent; in Θ solvent The temperature dependence of the [η] for the gums studied in
the temperature range 298-338 K were processed in terms of
(36) (a) Tanford, C. Physical Chemistry of Macromolecules; John Wiley: New
York. 1961; Chapter 6, p 392 ; (b) Pamies, R.; Cifre, J. G. H.; Martinez, M. d. C. L.; de la (37) Tanford, C. Physical Chemistry of Macromolecules; John Wiley: New York,
Torre, J. G. Colloid Polym. Sci. 2008, 286, 1223–1231. 1961; Chapter 6, p 391.

Langmuir 2009, 25(19), 11647–11656 DOI: 10.1021/la901259e 11651

Article
Table 3. The Arrhenius Constant A and Ea Values of the Studied
Gums
gum A, dL g-1 Ea, kJ mol-1
CMHPG 14.8 15.0
diutan 15.8 13.8
xanthan 11.8 15.3
Arrhenius type equation (eq 4 shown below) to obtain the
activation energy and the pre exponent coefficient A for the
viscous flow according to the plots shown in Figure 4. The results
are presented in Table 3. Thus,
½η ¼ AeðEa =RTÞ
where A is a constant and Ea is the activation energy for the
viscous flow of the gum solution expressed in kilojoules per mole
(the average molar mass of the entire chain).
The gums are fairly polydisperse but that does not bar them to
be physicochemically characterized in terms of molar mass, Ea,
etc. The comparison of their physical properties in terms of their
structural/compositional variations is not a simple proposition,
and such studies are scarce in literature. This has not been the
main focus of the present study. It has been observed that the Ea
values for CMHPG and xanthan were comparable but the value
for diutan was smaller. The barrier for the viscous flow of diutan
was less than that for CMHPG and xanthan. Zhang et al.25 have
reported Ea for CMHPG to be 22.1 and 30.1 kJ mol -1; the results
were fairly higher than the present findings. The reports on Guar
and xanthan by Launay et al.29 were 13.2 and 17.2, respectively,
which fairly agreed with this work. The past workers seldom used
[η] in the evaluation of Ea (which conceptually accounts for the
flow activation process of nonassociated gum molecules). The Ea
values derived from processing [η] dependence on T are herein
reported. They, we consider, have correctly represented the
activation process.
In the overall consideration, the activation process was mod-
erate for the gum solutions. Dilute solutions of small carbo-
hydrate and polyhydroxy compounds viz., glucose, sucrose,
glycerol, mannitol, sorbitol, etc. have been reported38 to produce
activation energies or enthalpies in the range 15-17 kJ mol -1. In
comparison, the flow of dilute solutions of (high molecular
weight) gum was energetically not appreciably different from
the small carbohydrate molecules. The activation enthalpy for
water has been reported to be 16.4 kJ mol -1 The comparable
order of magnitude of the activation energy for the viscous flow of
water with both small polyhdroxy molecules and the very large
molecules of gums in dilute solutions has suggested that the
activation for the flow of water molecules controlled the transport
energetics of the studied biopolymer solutions determined from
their [η] values. How the concentration of the solutes in solution
could affect the energetic parameter should be an important and
interesting aspect of analysis. For glucose, sucrose, and poly-
hydroxy compounds, the activation parameters for the viscous
flow have been found to increase with concentration, initially
linearly up to a concentration of 0.5 M and nonlinearly there-
after.38 We have, therefore, estimated the Ea values for the gums,
at several concentrations: the results are presented in Table 4.
Instead of ln[η] vs T-1, a plot of ln [ηsp] vs T-1 was used in the
calculation of Ea. The concentration dependence of Ea has been
found to be comparable among the studied gums. However, the
activation energy for each gum has been found to decrease with
concentration in contrast to what has been observed for solu-
(38) Moulik, S. P.; Khan, D. P. Indian J. Chem. 1978, 16A, 16–19.
11652 DOI: 10.1021/la901259e
Banerjee et al.
Table 4. Concentration Dependent Activation Energy (Ea) Values of
the Gums
Ea, kJ mol-1
-1
[gum], g dL CMHPG Dn Xn
0.010 10.2 14.4 15.0
0.020 6.88 9.35 7.87
0.035 4.12 5.36 5.69
0.050 0.97 1.72 3.98
tions of small carbohydrate molecules discussed above. The flow
mechanisms for solutions of small molecules and large (polymer)
molecules in moderate concentrations have been considered to be
ð4Þ different. With increasing concentration, the biopolymers have
formed associated entities with voids through which the solvent
molecules have flown relatively easily and the requirement for
activation was lower. It is thus recommended that, for a macro-
molecular solution, Ea should be measured from the temperature
dependence of [η] and compared among different systems for a
better understanding. It will be shown subsequently that, at C ∼
0.02 g dL-1 (Table 6 and 7 below), the gum molecules start
forming molecular association. The results in Table 4 have
revealed that the Ea values started declining fairly also at C g
0.02 g dL -1. This aspect of viscosity dependence on simple
carbohydrates, and macromolecules of carbohydrate origin re-
quire a detailed investigation.
The intrinsic viscosity, Huggins constant, and the activation
energy values are vital information on the nature of the gums in
solution, which will be further discussed in a subsequent section.
We have also studied the viscosity behaviors of the gums in salt
solutions. It has been found that Huggins equation (eq 2) does not
hold in salt solutions. Therefore, as done by others,22,39 we tried to
use Kraemer’s equation,40 in the following form (eq 5) for the
determination of the intrinsic viscosity. but without success.
ln ηr
¼ ½ηþk 00 ½η2 C ð5Þ
C
k00 is Kraemer’s constant
Of the other forms of equation tried, the following ln ηr - C
form41 has been found to obey the present results on the studied
gums in electrolyte solutions.
ln ηr ¼ ½ηC ð6Þ
Equation 6 is equivalent to the Kraemer equation for dilute
solution where the second term on the right side is neglected.
Figure 5 is a representative plot that shows the validity of eq 6.
The intrinsic viscosities realized in the salt solutions of the gums
are presented in Table 5. The results have evidenced that in the salt
environments, the [η] of all the gums have followed similar trends
as in aqueous solution but its magnitudes were significantly lower
(cf. Scheme 2). However, (NH4)2SO4 strikingly reduced the
viscosity of diutan at both the temperatures. The [η] values for
each gum depended on the types of salts used. The monovalent
electrolytes produced comparable viscosity reduction. The biva-
lent salts reduced the viscosity more but their effects were nearly
comparable. Ma and Pawlik31 reported [η] of guar to be inde-
pendent of the salt type and concentration <4.1 M. In saturated
salt solutions the values differed. The presently studied gums were
polyelctrolyte in nature with weak -COOH groups, which were
(39) Mc Millan, D. E. Biopolymers 1974, 13, 1367–1376.
(40) Kraemer, E. O. Ind. Eng, Chem. 1938, 30, 1200–1203.
(41) Sornsrivichani, T. Ph.D. thesis, Cornell University: Ithaca, NY, 1986.Cited
by Higiro, J.; Herald, T. J.; Alavi, S.; Bean, S. Food Res. Int. 2007, 40, 435-440.
Langmuir 2009, 25(19), 11647–11656
Banerjee et al. Article

Table 5. The [η] of Gums in 1 M Aqueous Solution of NaCl, HCOOK, The initial slope with values greater than unity has been
CH3COONa, (NH4)2SO4, and MgSO4 at 308 and 338 K Obtained considered as evidence for random coil conformation of the
Using Eq 6 biopolymers in solution.42 Slope values lower than unity stand
[η]308, dL g -1 [η]338, dL g-1 for rod-like conformation of the polymer molecules.21 Our
values of the intercept, Pp on the whole were large with small
additives CMHPG Dn Xn CMHPG Dn Xn
values here and there. The slopes in aqueous medium for all the
none 45.90 33.31 44.75 33.06 30.61 43.30 three gums have been found to be greater than unity. In salt
NaCl 12.09 22.92 16.80 10.86 23.13 15.44 environments, the values have become smaller; much reduced
HCOOK 11.03 19.51 14.97 10.10 19.50 13.44 values have been obtained in CaCl2 solution. Increasing tem-
CH3COONa 11.50 19.05 15.65 10.09 19.16 14.52
CaCl2 10.34 19.59 15.57 9.46 19.75 13.70 perature has a lowering effect on all the parameters involved
(NH4)2SO4 10.95 7.733 14.89 9.40 8.26 13.63 with the power law equation. According to Whistler and
MgSO4 10.88 16.16 14.24 8.14 15.95 12.92 BeMiller,43 xanthan has been hypothesized as a rod-like
molecule; its qp value has been reported by Higiro et al.22 to
only partially ionized. The cations of the monovalent salts be 0.786 (temperature has not been mentioned in the report).
produced a screening effect reducing segmental repulsions to The xanthan used by us has shown qp values moderately greater
yield relatively compact configuration and hence reduction than one. In salt, environment the values of the first slope were
in [η]. Bivalent cations at the same concentration (1 M) pro- appreciably lower than unity. We consider fair conformational
duced greater effect with greater reduction in [η]. The large effect changes from nearly random coil to compact configuration for
of (NH4)2SO4 on diutan and xanthan could not be directly the gums in solution. The three studied gums have shown
fitted to this rationale. It may be added that the “chaotropic” parallel features as revealed from the observed slope values.
and “cosmotropic” nature of the ions had only a small effect The effect of CaCl2 was the strongest among the salts herein
on the configurational changes of the gums at the studied studied. The xanthan molecules in solution assume shapes
concentration of 1 M. The 1 M CH3COONa solution was depending on its molar mass: lower mass produces molecules
although alkaline (pH 8.7) produced [η] comparable with other with less flexibility than those with higher mass.44,45 The helical
monovalent nonhydrolyzable electrolytes. The pH values of xanthan molecules change to rod-like species with salt addi-
other non hydrolyzable salt solutions at 1 M were in the range tion.46 The [η] and k values in salt -free solution have been
5.4-6.8. reported by Higiro et al.22 to be 214.2 dL g -1 and 0.78,
Validity of the Power Law Relation. A power law equa- respectively. The sample we have used has shown [η] ≈ 50 at
tion,21,23 of the following form, can be used to derive information lower temperatures with k ≈ 0.35. The molecular size and hence
on the internal consistency of the biopolymer solution. Thus the molar mass of our sample of xanthan was much lower than
that of Higiro et al.,22 and consequently, its conformation
ηsp ¼ Pp C p qp ð7Þ was less flexible. Reasonably high concentration of the salts
(1 M each) was used in the present study. Ma and Pawlik,31
where, “Pp” is a constant and “qp” is an exponent that has been have used moderate to high salt concentration (4.1 M) in their
known to be capable of demarcating between low and high study with guar gum and alkali metal salts.
concentration regimes where association of polymer molecules Validity of Master Plots. It has been established that gum solu-
in solution may result. tions in the Newtonian fluidity range obey “master curves”;27,46-49
From the logarithmic plots of eq 7, the values of “Pp” and “qp” i.e., log ηsp vs log (C[η]) plots display straight lines either with a
can be obtained. It has been found that for a number of systems single break (Cm*) or double breaks Cm* and Cm**. In the
the plots have produced either two or three straight lines with concentration range < Cm*, polymer molecules remain isolated;
increasing slopes. This has been considered as one or two at Cm* and beyond, molecules start association (probably form-
molecular-association stages of the biopolymers in solution. At ing dimers) which continues up to Cm**, and beyond that point
very dilute solution, the macromolecules are individually dis- further molecular association arises. In the dilute regime <Cm*,
persed in solution. After a critical concentration (Cp*), they come polymer coils have infinite dilution dimensions; in the regime
closer for association, and at a further higher concentration Cm* < Cm**, polymer coils are in contact and shrink, and in the
(Cp**), molecules assemble with overlaps. This is considered as semidilute region C > Cm**, polymer strands overlap more and
the reason for getting one or two breaks in the plots. It may be more, and reach Θ dimensions. It has been also reported,50 that a
mentioned here that from a master plot of log [ηsp] vs log (C[η]), third critical concentration Ce (Cm* < Ce < Cm**) may exist in a
Robinson et al.27 have also reported the point of existence of Cm*, good solvent; between Cm* and Cm**, the molecules do not attain
a critical concentration for guar gum solutions. Later, two breaks their Θ dimensions although they remain overlapped. The master
in such plots have been reported in support of the existence of curve has been observed to be obeyed by random coil polymers,
two critical concentrations for molecular association in solution.
This point will be subsequently presented in some details on (42) Lapasin, R.; Pricl, S. In Rheology of Industrial polysaccharides: theory and
our results. In Figure 6, the power law plots are illustrated applications; Lapasin, R., Pricl, S., Eds.; Blackie Academic and Professional: Glasgow,
Scotland, 1995; p 250.
with demonstration for the occurrence of one or two breaks at (43) Whistler, R. L.; BeMiller, J. N. Carbohydrate chemistry for food scientists;
Cp* and Cp**. Eagan Press: St. Paul, MN, 1997.
In Table 6, the values of the constant, “Pp”, and the slopes (44) Morris, E. R. In Food polysaccharides and their applications; Stephen, A. M.,
Ed.; Marcel Dekker: New York, 1995; p 341.
“qp1”, “qp2” and “qp3” are presented for the gums at two (45) Sato, N.; Fujita Macromolecules 1984, 17, 2696–2700.
temperatures 308 and 338 K in aqueous and salt solutions, where (46) Rochafert, W. E.; Middleman, S. J. Rheol. 1987, 31, 337–369.
qp1, qp2, and qp3 are the slopes of the first second and third straight (47) Launay, B.; Cuvelier, G.; Martinez-Reyes, S. In gums and stabilizers for
Food Industry-2; Philips, G. O., Wedlock, D. J., Williams, P. A., Eds.; Pergamon:
lines in the plots, respectively. Oxford, U.K., 1984; p 79.
In most of the previous reports, only a single break in the (48) Launay, B.; Doublier, J. L.; Cuvelier, G., In The functional properties of
food macromolecules; Ledward, D., Mitchell, J. R., Eds.; Elsevier: London, 1986; p 1.
plot with a single slope have been reported; in some reports (49) Cuvelier, G.; Launay, B. Carbohydr. Polym. 1986, 6, 321–333.
a second slope of greater magnitude has been also observed. (50) Graessley, W. W. Polymer 1980, 21, 258–262.

Langmuir 2009, 25(19), 11647–11656 DOI: 10.1021/la901259e 11653

Article Banerjee et al.

Table 6. The Constant Pp and the Slopes qp1, qp2, and qp3 Obtained for the Gums along with Cp* and Cp** Values at Different Temperatures in
Aqueous and Salt Solutions
Pp, g dL-1 (qp1/qp2/qp3) [Cp*/Cp**]
temp, K CMHPG Dn Xn

Aqueous
308 61.52 (1.03/1.31/-) [0.007/-] 56.43 (1.13/1.29/-) [0.005/-] 178.89 (1.26/1.61/-) [0.002/-]
338 11.36 (0.79/1.04/1.56) [0.003/0.014] 34.71 (1.05/1.36/2.17) [0.006/0.036] 69.74 (1.16/1.38/1.57) [0.002/0.06]
NaCl
308 14.65 (1.0/1.31/2.05) [0.021/0.1] 8.54 (0.89/1.29/2.12) [0.01/0.05] 28.64 (1.05/1.74/-) [0.02/-]
338 12.86 (1.01/1.32/2.03) [0.02/0.1] 23.21 (1.0 /1.34 /2.21) [0.01/0.05] 0.54 (0.16/0.83/1.94) [0.01/-]
CaCl2
308 1.39 (0.19/0.78 /1.63) [0.013 /0.048] 1.72 (0.43/1.03/1.52) [0.006/0.03] 4.34 (0.63/0.97/2.09) [0.008/0.054]
338 0.79 (0.14 /0.94/1.74) [0.015/0.066] 3.48 (0.58/1.09/1.83) [0.007/0.046] 0.54 (0.16/0.87/1.94) [0.005/0.05]
(NH4)2SO4
308 3.02 (0.86/1.13/1.81) [0.012/0.07] 5.77 (0.919/1.40/-) [0.03/-] 15.8 (0.982/2.08/-) [0.045/-]
338 9.25 (0.98/1.50/-) [0.03/-] 1.89 (0.69/1.03/1.35) [0.006/0.02] 0.153 (0.066/0.394/1.77) [0.013/0.067]
CH3COONa
308 25.40 (1.07/1.73/-) [0.037/-] 40.04 (1.096/1.57/-) [0.03/-] 14.34 (0.955/1.40/-) [0.012/-]
338 61 (0.68/1.10/1.62) [0.01/0.05] 19.09 (0.99/1.19/1.62) [0.005/0.04] 1.94 (0.626/0.942/1.472) [0.005/0.016]
HCOOK
308 68.36 (1.19/1.68/-) [0.051/-] 25.47 (1.002/1.52/-) [0.02/-] 29.78 (1.11/1.49/-) [0.04/-]
338 12.49 (1.0/1.51/-) [0.035/-] 12.78 (0.908/1.13/1.68) [0.004/0.03] 11.64 (0.95/1.10/1.46) [0.008/0.04]
MgSO4
308 18.8 (0.80/1.15/1.71) [0.01/0.051] 23.95 (1.04/1.51/-) [0.03/-] 20.94 (1.04/1.45/-) [0.03/-]
338 16.03 (1.04/1.24/-) [0.015/-] 12.45 (0.93/1.07/1.53) [0.006/0.03] 6.38 (0.83/1.06/1.43) [0.008/0.03]

Table 7. Master Plot Results of Cm* and Cm** Values for CMHPG, Diutan, and Xanthan Gums in Aqueous and in Salt Solutions, and the Constant
Pm, and the Slopes qm1, qm2, and qm3 at 303 K
Pm, g dL-1 (qm1/qm2/qm3) [Cm*/Cm**]
temp, K CMHPG Dn Xn

Aqueous
308 0.12 (1.07/1.37/-) [0.018/-] 1.24 (1.19/1.29/-) [0.006/-] 0.17 (1.25/1.67/-) [0.029/-]
338 0.06 (0.96/1.63/-) [0.017/-] 0.047 (1.10/1.24/-) [0.015/-] 0.18 (1.36/1.50/-) [0.021/-]
NaCl
308 0.08 (1.0/1.31/2.05) [0.02/0.10] -0.04(0.89/1.29/2.12) [0.011/0.049] 0.17 (1.17/2.24/-) [0.049/-]
338 0.03 (1.01/1.32/2.03) [0.021/0.10] 0.002 (1.0/1.34/2.21) [0.011/0.051] -0.79 (0.16/0.83/1.94) [0.004/0.045]
CaCl2
308 -0.43 (0.19/0.92/1.81) [0.014/0.072] -0.33 (0.43/1.03/1.52) [0.006/0.029] -0.38 (0.36/0.99/2.10) [0.01/0.051]
338 -0.52 (0.14/0.95/1.79) [0.015/0.07] -0.12 (0.64/1.16/1.83) [0.01/0.051] -0.78 (0.16/0.87/1.94) [0.005/0.047]
(NH4)2SO4
308 -0.02 (0.96/1.19/1.81) [0.01/0.07] 0.952 (0.946/1.52/-) [0.043/-] 1.11 (0.981/2.08/-) [0.045/-]
338 0.034 (0.99/1.51/-) [0.022/-] 0.412 (0.688/1.03/1.39) [0.006/0.024] 0.129 (0.066/0.40/1.77) [0.013/0.068]
CH3COONa
308 0.11 (1.06/1.58/-) [0.034/-] 1.405 (1.096/1.57/-) [0.03/-] 1.0 (0.955/1.40/-) [0.018/-]
338 -0.25 (0.68/1.09/1.62) [0.011/0.055] 1.06 (0.99/1.18/1.62) [0.005/0.04] 0.377 (0.626/0.902/1.43) [0.004/0.014]
HCOOK
308 0.21 (1.19/1.54/-) [0.029/-] 1.215 (1.01/1.66/-) [0.03/-] 1.45 (1.11/1.49) [0.04/-]
338 0.042 (0.99/1.51/-) [0.033/-] 0.91 (0.91/1.13/1.68) [0.005/0.03] 0.93 (0.95/1.08/1.46) [0.007/0.04]
MgSO4
308 -0.11 (0.85/1.21/1.81) [0.017/0.071] 1.25 (1.04/1.51/-) [0.03/-] 1.2 (1.04/1.45/-) [0.03/-]
338 0.17 (1.06/1.33/-) [0.024/-] 0.931 (0.93/1.07/1.53) [0.006/0.03] 0.73 (0.85/1.06/1.43) [0.008/0.03]

11654 DOI: 10.1021/la901259e Langmuir 2009, 25(19), 11647–11656

Banerjee et al.
Figure 5. Plot of ln ηr vs C for gums at various temperatures: 1,
CMHPG in HCOOK at 308 K; 2, CMHPG in (NH4)2SO4 at
338 K; 3, Dn in CaCl2 at 308 K; 4, Xn in NaCl at 338 K.
Figure 6. (A) Power law plots (ln ηsp vs ln C) for gums in aqueous
solution. 35 and 65 refer to temperatures in °C. (B) Power law plots
(ln ηsp vs ln C) for gums in salt solutions. 35 and 65 refer to
temperatures in °C.
but at low pH and high ionic strength locust bean gums, guar
gum, hyaluronate have produced specific interaction creating
hyperentanglements between chains.42,51 Nonsuperimposed re-
sults have been also reported for carboxymethylcellulose (CMC),
and hydroxyethylcellulose (HEC) in NaCl solution. The master
curve plots for the CMHPG, diutan and xanthan gums, and the
results are presented in Figure 7 and Table 7, respectively. The
slopes of the plots have been assessed region-wise. The results are
discussed below in relation to the previous findings from the
power law plots.
The findings from the power law and the master plots (Table 6
and 7) revealed a two stage molecular association process for the
gum molecules in solution. When examined, the Cp* and Cp**
values by power law plots have been observed to be fairly
comparable with the Cm* and Cm** values by the master plots
for the gums of the studied environmental conditions (aqueous
and salt solutions) with only a few exceptions. Thus, any one of
(51) Castelain, C. J.; Doublier, L.; Lefebvre Carbohydr. Polym. 1987, 7, 1–16.
Langmuir 2009, 25(19), 11647–11656
Article
Figure 7. (A) Master curve plots ln ηsp vs ln (C[η]) for gums in
aqueous solution. 35 and 65 refer to temperatures in °C. (B) Master
curve plots ln ηsp vs ln (C[η]) for gums in salt solutions. 35 and 65
refer to temperatures in °C.
the two procedures is useful to understand the molecular inter-
action states of the gums in solution. However, a generalization of
the salt effects on Cp* (or Cm*) and Cp** (or Cm**) is not
apparently visible from the tabulations. But temperature has a
declining effect on the threshold values. Both salt and temperature
have no radical effect on the magnitudes of the slopes derived
from either power plot or master plot, i.e., qp (or qm), rp (or rm),
and sp (or sm). How these values correlate requires to be examined
for a general understanding of the salt effects on the flow
properties of the gum solutions. This may be undertaken in a
future study.
Conclusions
Under isopiestic condition, water molecules essentially get
bound to the oxygen centers on the gums by hydrogen bonding.
The type III isotherms obtained do not fit to the BET equation. In
solution, conductometry has registered the obstructed mobility of
the ions to probe also the trapped water molecules in the folded
configurations of the biopolymers in addition to the molecules
arrested by way of hydrogen bonding. The gums have exhibited
quite high values of intrinsic viscosity which have followed the
trend CMHPG < diutan < xanthan. On the basis of the water
binding capacities of the gums, and their intrinsic viscosity values
in aqueous medium, the shape factor υ for the gums have been
found to be close to 2.5 for diutan and xanthan; they were thus
nearly spherical shapes, but the value for CMHPG was 3.3, which
has meant spheroidal geometry for the latter. This was an
interesting finding showing that the flexible polymers by generous
folding assumed nearly spherical assemblies in solution. The tem-
perature effect on the intrinsic viscosity has yielded the activation
energy for viscous flow which has been observed to compare well
with small carbohydrate molecules (glucose, sucrose, glycerol,
mannitol, sorbitol), but with increasing concentration the activa-
tion energies for the flow have declined, and in this respect they
have differed in behavior from small carbohydrate molecules
DOI: 10.1021/la901259e 11655
Article
mentioned above. This has been attributed to the differences in
the modes of transport of the two classes of compounds in
solutions when not dilute. The salts NaCl, CH3COONa,
(NH4)2SO4, CaCl2, and MgSO4 at 1 M concentration have fairly
decreased the viscosity of the gum solutions. The differences
among the monovalent salts used have been only moderate, which
for the bivalent salts have been lower but comparable among
themselves except for (NH4)2SO4 which has produced a greater
effect on diutan. The viscosity values of the gums have followed
the power law equation, and have as well shown master plot
manifestation. The plots have revealed the presence of two critical
11656 DOI: 10.1021/la901259e
Banerjee et al.
concentrations (designated as C* and C**) that have suggested
the phenomenon of two stage association of the macromolecules
in solution. The critical values realized from both power law
and master plots have shown fair degree of agreement between
them.
Acknowledgment. P.B and I.M. thank Halliburton Energy
services for financial support. S.P.M. thanks the Indian National
Science Academy for an Honorary Scientist position. We appreci-
ate the critique of one of the reviewers which has improved the
quality of the presentation.
Langmuir 2009, 25(19), 11647–11656