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Physicochemical Studies on an All-Purpose Pesticide Spray Adjuvant-(APSA-

80)
Indrajyoti Mukherjee a; Dipankar Haldar b; Soumen Ghosh a; Satya P. Moulik a
a
Centre for Surface Science, Department of Chemistry, Jadavpur University, Kolkata, India b Department of
Food Technology and BioChemical Engineering, Jadavpur University, Kolkata, India

Online Publication Date: 01 November 2009

To cite this Article Mukherjee, Indrajyoti, Haldar, Dipankar, Ghosh, Soumen and Moulik, Satya P.(2009)'Physicochemical Studies on
an All-Purpose Pesticide Spray Adjuvant-(APSA-80)',Journal of Dispersion Science and Technology,30:10,1430 — 1441
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 Journal of Dispersion Science and Technology, 30:1430–1441, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690903107182

Physicochemical Studies on an All-Purpose Pesticide

Spray Adjuvant-(APSA-80)
Indrajyoti Mukherjee,1 Dipankar Haldar,2 Soumen Ghosh,1 and
Satya P. Moulik1
1
Centre for Surface Science, Department of Chemistry, Jadavpur University, Kolkata, India
2
Department of Food Technology and BioChemical Engineering, Jadavpur University, Kolkata, India

APSA-80, an useful pesticide spray adjuvant is a mixture of 2-[2-(4-nonylphenoxy) ethoxy]

ethanol, 1-butanol and tall oil fatty acids. It is strongly surface active and can decrease the sur-
face tension of water to
20 mNm1 at its critical micelle concentration (CMC) of 0.006 g%.
APSA-80 itself and its binary mixtures, (APSA-80 þ water) and (APSA-80 þ isopropylmyristate
[IPM]) and ternary mixtures (APSA-80 þ water þIPM) can undergo a number of physical
changes with rise in temperature; the main changes are in color, turbidity and phases. The ternary
mixtures of APSA-80/water/IPM with changing compositions can form mono-, bi-, and triphasic
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solutions as well as gels and viscous solutions. The gel and viscous phases show characteristic
rheological properties of both shear thinning and thickening types. They also show permeation
of hydrophilic and oleophilic dyes through them. SEM and optical microscopic measurements
have shown interesting surface morphologies of the gels and their vertical projections in
three-dimensional pictorial mode. Salts like LiCl, NaCl, KCl, CsCl, MgSO4, and Al2(SO4)3
can have both minor and major effects on the gel consistencies. The alkanols like ethanol, propa-
nol, and isopropanol are also mild to fairly large gel influencing co solvents. The antibacterial
properties of APSA-80 have been studied with two Gram positive bacteria and a yeast; the
activities found were moderate.
Keywords Antibacterial property, APSA-80, gels, miscibility with IPM and water, morphol-
ogy, phase behaviors

INTRODUCTION greenness of the environment where they are used. The

Pesticides are essentially water insoluble toxic organic
compounds.[1–3] They are dispersed in water with the help
of dispersants that are surface-active compounds that can
form aggregated assemblies[9–12] like micelles, reverse
micelles or microemulsions, emulsions, etc., when mixed
either with water or oil or with both. The type of disper-
sions required to vehicling pesticides in the field applica-
tions depends on the practical needs keeping in mind the
Received 25 July 2008; accepted 6 September 2008.
I.M. thanks Jadavpur University for laboratory facilities of the
Centre for Surface Science, Department of Chemistry, to carry
out the work. S.P.M. thanks JU for an emeritus professor ship
and Indian National Science Academy for an Honorary Scientist
position. The authors thank Mr. Pallab Dasgupta of Department
of Instrumentation Science, Jadavpur University for SEM
measurements and Mr. A. Garai of Polymer Science Unit of
Indian Association for the Cultivation of Science for rheological
experiments.
Address correspondence to Satya P. Moulik, Centre for Sur-
face Science, Department of Chemistry, Jadavpur University,
Kolkata 700032, India. E-mail: spmcss@yahoo.com
choice of the pesticide, the dispersant, and other vehicling
additives is, therefore, crucial in this respect.
In recent years, the commercial dispersant APSA-80 has
been shown to be an effective all-purpose spray adjuvant in
agricultural uses as a vehicle for various fungicides, herbi-
cides, and insecticides.[4–8] It is a good activator, spreader
that improves the coverage of the pesticides. It appreciably
increases the effectivity of Limonine[13,14] (a Citrus fruit
extract) to control Mealybugs, scale insects, white
flies, and aphides. Compared with water and other compe-
titors, APSA-80 is less corrosive to mild steel, stainless
steel, brass, copper bronze, etc. The amount of 0.5%
aqueous solution is a better fire extinguisher.[15,16]
Although APSA-80 has been showing promises as
pesticide spray adjuvant, its physicochemical properties in
solution in varied conditions have not been adequately stu-
died. Although this commercial product has the main
ingredient 2-[2-(4-nonylphenoxy) ethoxy] ethanol (a non-
ionic surfactant), it also contains 1-butanol and tall oil
fatty acids (discussed in the materials and method section),
which add toward the solubilization and dispersion of the
pesticides by the adjuvant.[37–39] Therefore, information

1430
 PHYSICOCHEMICAL STUDIES ON AN ALL-PURPOSE PESTICIDE SPRAY
on the dispersions of either water-in-oil or oil-in-water type
in the form of emulsions and microemulsions using
APSA-80 as the stabilizer would be interesting and impor-
tant for housing pesticides in the compartmentalized
liquids for preparing effective spraying formulations useful
in practical applications. This prospect has prompted us to
study the basic physicochemical and surface chemical pro-
perties of APSA-80 in aqueous solution and in ternary
mixtures with isopropylmyristate (IPM). The IPM is a
biofriendly material; it is, thus, expected that APSA-80 for-
mulations with water and IPM would help in the formation
of a better and stable vehicle for the field application of the
pesticides with a better green environment maintaining
effect.
In this work, we have made detailed studies on the solu-
tion properties of APSA-80 with special focus on the phase
behaviors of its binary mixtures with water and with IPM
and ternary mixtures with water and IPM. It has been
found that the compound has a remarkable surface tension
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lowering property in comparison with a number of other
nonionic surfactants, and the phase behaviors are fascinat-
ing and conspicuous. A number of varied combinations
can form gels (both hard and soft), which are structurally
and rheologically interesting. Salts and alkanols have spe-
cific effects on the gels. The antibacterial effects of
APSA-80 on two Gram positive bacteria and a yeast have
been also studied. The adjuvant has shown moderate
activities towards them. The study has emerged with new
findings qualifying the effort to be original.
MATERIALS AND METHODS
Materials
IPM used, was 98% pure product of Fluka (Buchs,
Switzerland). APSA-80 (all-purpose spray adjuvant) was
obtained from AMWAY (Mumbai, India.). Mg(SO4) and
Al2(SO4)3.18H2O were obtained from Loba Chemie. Pvt.
Ltd. (Mumbai, India). NaCl, KCl and propanol were
products of Merck (Mumbai, India). LiCl was a product
of Sigma (St. Louis, MO, USA.) CsCl and isopropanol
(IP) were products of SRL (New Delhi, India) and ethanol
was that of Bengal Chemical (Kolkata, India). Tween-20,
Triton-X-100 and Brij-35 obtained from Sigma, BDH
(West Sussex, UK), and Merck (Darmstadt, Germany)
respectively. The dyes Crystal Violet and Oil Red were
the products of Sigma-Aldrich (St. Louis, MO, USA).
The chemicals used were either pure or AR grade products
and they were used as received.
Peptone (5 g=L) was obtained from S.D. Fine Chem.
Ltd. (Mumbai, India), used as nutrient in microbiological
experiment. Beef extract powder (3 g=L) obtained from
Loba Chemie. Pvt. Ltd.
APSA-80 (the product under detailed study) was a com-
bination of 2-[2-(4-nonylphenoxy) ethoxy] ethanol
80%,
1431
1-butanol
15% and tall oil fatty acids
5%. The first
ingredient is a nonionic surfactant, which is expected to
be fairly surface active; the presence of 1-butanol and tall
oil fatty acids should also add to the overall surface activity
of APSA-80. Tall oil fatty acid[44] comprising oleic acid
(35%), linoleic acid=conjugated C18 fatty acid (50%), poly-
unsaturated fatty acid (7%), and saturated fatty acid (2%).
From the compositions of the ingredients, an average
molar mass of APSA-80 has been estimated to be 209.
The product is stable but its contacts with strong acids or
bases, and oxidizing or reducing agents should be avoided.
Contact of APSA-80 with eye, skin, and its inhalation and
ingestion should also be avoided.
Doubly distilled water of specific conductance, 0. 2–0. 4
lS cm1 at 298 K was used in all experiments.
Methods
Tensiometry
Tensiometric measurements were taken with a calibrated
du Noüy tensiometer (Krüss, Hamburg, Germany) by the pla-
tinum ring detachment technique. The solutions of
surface-active compounds were successively added in
aqueous medium by a Hamilton (Bonaduz, Switzerland)
microsyringe in a double walled glass container. Water at a
fixed temperature (fluctuation 0.1 C) was circulated
through the space between the walls to maintain constant
temperature of the experimented solution. After thorough
mixing, the solutions were given 10 minutes time for equilibra-
tion prior to taking measurements. Accuracy of the measured
surface tension (c) values was 0.1 mNm1. The detailed
procedure of measurement can be found elsewhere.[17–20]
Phase Behavior
A fixed amount of the surface-active material
(APSA-80) was taken in different amounts of oil (IPM)
in a set of dry test tubes with a microsyringe (Hamilton)
to have solutions of different strength in them. Water in
increasing quantities was added to these solutions under
a constant stirring condition. The test tubes were then
placed into the thermostated water bath (accuracy
0.1 K) to note the phases obtained in them. The solutions
were allowed to stand for several days to study their stabi-
lities with time and temperature. The solutions were then
disturbed by cyclomixing and allowed to reequilibrate for
examining the reversibility of the phase forming behaviors.
The experiments were found to be reproducible within an
error limit of  1%. The results were used to construct
ternary phase diagrams.
Dilution Experiment
A known amount of the solubilizer (APSA-80) was
taken in a dry stopppered test tube. Known amounts of
isopropylmyristate and water were also added. The mixture
was then cyclomixed and kept into the thermostated water
 1432 I. MUKHERJEE ET AL.

bath (accuracy 0.1 K) at a fixed temperature. Appearance
of the solution was noted after allowing a considerable per-
iod of time to reach equilibration. Water was added to the
solution stepwise by a microsyringe under constant stirring
condition allowing time for stabilization. In different stages
of addition, different types of phases were observed to
appear. At each stage of appearance of a new phase, the
system was destabilized by agitation and was allowed to
reequilibrate for observations. The whole procedure was
also repeated once, if required twice. The behaviors were
found to be fairly reproducible.
Microcalorimetry
An isothermal titration calorimeter (ITC) of OMEGA
MicroCal Inc. (Piscataway, NJ, USA) was used for mea-
surements. A solution of APSA-80 of 0.0616 g% (about
10 times more than its critical micellar concentration
[CMC]) was stepwise-added (10 ml at each step) with 240
seconds time interval into 1.325 ml water taken in the
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like bacteria) and one yeast Saccharomyces cerevisiae.
The effects were quantified based on the dimension of inhi-
bition zone[40] developed in plates, and determining the
minimum inhibitory concentration (MIC)[41] of the sprea-
der in the liquid batch culture.
RESULTS AND DISCUSSION
Surface Activity and Critical Micelle Concentration
(CMC) of APSA-80
APSA-80 is an excellent surface-active material. A large
reduction in surface tension of water has been observed by
its presence. A linear fall in c occurred up to a concentra-
tion of 0.006 g% and after wards, the decrease practically
halted. The tensiometric behavior of APSA-80 has been
compared with several other nonionic surfactants viz.,
polyoxy ethylene (20) sorbitan monolaurate (Tween-20)[27],
p-tertiary octyl phenoxy polyoxy (9.5) ether (TritonX-
100),[28] polyoxyethylene (23) lauryl ether (Brij-35),[29] and

calorimeter cell under constant stirring (350 rpm) condi- N-methyl-N-decanoyl glucamide (MEGA-10)[30] (Figure 1,
tions at 303  0.01 K. The reference cell had 1.65 ml water inset). Equi g% ternary combination of Tween-20,
in it. The associated heat during titration were calculated Triton-X-100, Brij-35 and quaternary combination of
using a MicroCal origin ITC software. The experiment Tween-20, Triton-X-100, Brij-35, and APSA-80[31] are also
was repeated to check the reproducibility. For further presented in Figure 1 (main), for a comparison with
experimental details, we refer to our earlier works.[21–23] APSA-80. APSA-80 has lowered c the most (20 mNm1)
and its CMC has been also found to be the lowest. The
Rheometry quaternary combination has shown a slightly better surface
The observed phases of the ternary system (APSA-80= activity than the ternary. Efficient surface activity of
water=IPM) were thin, thick (viscous) and gels. The viscous APSA-80 has also been reported by Hollingsworth[13] for
and gel like products were studied in a shear viscometer
(Advance Rheometer AR 2000 TA Instruments, New
Castle, DE, USA). The rheological[24–26] experiments were
done with the sample in a parallel plate confinement in an
environmental testing chamber (ETC). The plate diameter
was 25 mm and the gap between them was 500 mm.To
maintain the constancy of temperature in ETC, air was
passed at a flow rate of 10 L=m. Several characteristic phe-
nomena have been observed in the experiments.

UV-VIS Spectrophotometry
The spectroscopic properties of APSA-80 were studied
in a dual beam Shimadzu 1601 UV-visible (Tokyo, Japan)
Spectrophotometer using a matched pair of quartz cuvettes
of 1 cm path length. Spectra were taken in the range of 200
to 700 nm. Experiments were done with and without pyrene
in APSA-80 solution for verifying the characteristic fea-
tures of the compound and its solution. The spectra of
an oil soluble dye oil red in IPM were also examined in
the scanned range of 200 to 1100 nm.
FIG. 1. Tensiometric profiles of APSA-80 and other nonionic surfac-
Antimicrobial Study tants and their mixtures at 294 K except MEGA-10 at 303 K. (1)
APSA-80, (2) Triton-X-100, (3) Tween-20, (4) Brij-35, (5) MEGA-10, (6)
The antimicrobial properties of APSA-80 with two APSA-80, (7) Triton-X-100 þ Tween-20 þ Brij-35 þ APSA-80 (1:1:1:1
Gram positive mesophilic bacterial strains, Bacillus subtilis mass ratio), (8) Triton-X-100 þ Tween-20 þ Brij-35 (1:1:1 mass ratio).
and Streptomyces fradiae (an antibiotic producing fungus The CMC points are indicated on the curves by arrowheads.
 PHYSICOCHEMICAL STUDIES ON AN ALL-PURPOSE PESTICIDE SPRAY
verification, the CMC of APSA-80 was also determined
from UV-spectra following pyrene absorption spectra in
APSA-80 solution. In a series of APSA-80 solution with
varying concentration, 2.3 mM pyrene was dissolved as
described earlier.[32,33] Their spectra were measured
(Figure 2, main) and the sum of absorbances of the main
peaks of pyrene (283, 276, 263, 243 nm.) have been plotted
against the concentration of APSA-80 (Figure 2, inset) to
get CMC from the intersection of two linear curves marked
on the plot. The tensiometric and spectrophotometric
CMC values were in full agreement at 0.006 g%.
Calorimetric Observations
Enthalpy of dilution of APSA-80 at 0.0616 g% (10 times
CMC) was calorimetrically studied. The enthalpograms
(three repeat experiments) were shallow in their variation
with [APSA-80]. However, there was a sigmoidal trend in
the plots (illustration not shown) like other studied
surfactants[21] with transition at [APSA-80] ¼ 0.0069 g%
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that closely agreed with the CMCs by tensiometry and
spectrophotometry discussed above. The enthalpy of
micelle formation (DH0m ) obtained from the differences
between the asymptotes of the sigmoid was 1.6 kJ=mol.
at 303 K. It may be mentioned that nonionic surfactants
viz. Tweens, Brijs, etc. have evidenced indeterminable
DH0m by ITC because of their low CMC values of
10 mM.
Triton-X-100 has been found to produce DH0m ¼21.7 (kJ=
mol.) at 303 K. On the other hand, surfactants like
MEGA-10 and Octylglycoside have evidenced larger
DH0m of 2.86 kJ=mol at 303 K and 7.01 kJ=mol at 300 K,
respectively. In that comparison, APSA-80 has produced
a lower DH0m value. It is to be noted that nonionic
FIG. 2. Main plot: Spectra of pyrene in aqueous solution of APSA-80
at 303 K. 1–20: 1. pyrene in water (2.35 mM); 2–20 increasing concentra-
tion of APSA solution from 6.972  104 g% to 0.0114 g%, pyrene concen-
tration remains same. Inset: Summation of peak absorbance versus
[APSA-80] break point is CMC.
1433
micellization processes are all endothermic process and
APSA-80 has been in that line.
Phase Behavioral Study
APSA-80 with IPM and water at different proportions
has exhibited interesting multiple phase behavior, which
has shown fair temperature dependence. The results are
clubbed in Figures 3a through 3d for temperatures 299,
303, 307, and 311 K, respectively. At 299 K (Figure 3a)
there appeared twelve different phase variations; they were
1, clear monophasic solution (CM); 2, clear biphasic solu-
tion (CB); 3, smoky gel (SG); 4, clear viscous solution
(CV); 5, transparent gel (TG); 6, biphasic, lower gel upper
clear solution (BGC); 7, milky gel (MG); 8, lower smoky
solution and upper milky thin ring (BSM); 9, triphasic;
lower gel, middle gel, and upper solution (TGS); 10, tripha-
sic; lower clear solution, middle creamy-milky layer and
upper clear solution (TCMC); 11, biphasic, lower clear
and upper smoky solution (BCS), and 12 tiny clear gel
(CG). At 303 K, (Figure 3b) number 8 and number 12 were
absent. At 307 K (Figure 3c) numbers 5, 7, 8, and 12 did
not appear and at 311 K (Figure 3d) the phase number 5,
7, 9, and12 were absent. Thus, with rise in temperature
several phases did not form. Thus, phase behavior of
FIG. 3. Ternary phase diagrams of water=APSA-80=IPM. regions: 1,
clear monophasic solution (CM); 2, clear biphasic solution (CB); 3, smoky
gel (SG); 4, clear viscous solution (CV); 5, transparent gel (TG); 6, bipha-
sic, lower gel upper clear solution (BGC); 7, milky gel (MG); 8, lower
smoky solution and upper milky thin ring (BSM); 9, triphasic; lower
gel, middle gel, and upper solution (TGS); 10, triphasic; lower clear solu-
tion, middle creamy-milky layer and upper clear solution (TCMC); 11,
biphasic, lower clear and upper smoky solution (BCS); and 12. tiny clear
gel (CG). 3a: 299 K; 3b: 303 K; 3c: 307 K; 3d: 311.
 1434 I. MUKHERJEE ET AL.

water=APSA-80=IPM system has been found to be
complex and conspicuous. Several phases disappeared with
rise in temperature while the areas and shapes of the exist-
ing phases in the ternary diagram changed. Detailed studies
on the physicochemical properties of the individuals would
be interesting. This requires prolonged planning for mea-
surements, which has remained undone, and it was not
our immediate objective of study. However, we have exam-
ined properties of several of these preparations, which are
described in subsequent sections.
Behavior of the Produced Gels
With reference to Figure 3, the areas identified by the
numbers 3, 5, and 7 were smoky gel (SG), transparent gel
(TG) and milky gel (MG) respectively. Their mass%
compositions were, SG (water ¼ 32.6 g, APSA-80 ¼ 56.4 g,
IPM ¼ 11.0 g); MG (water ¼ 21.7 g, APSA-80 ¼ 22.6 g,
IPM ¼ 55.7 g); TG (water ¼ 46.6 g, APSA-80 ¼ 35.1 g, IPM ¼
18.3 g). The different properties of these gels studied were
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of desiccation effect has also been observed for the tight
gel appeared after using 0.1 (M) Al2(SO4)3.18 H2O solution
in the smoky gel composition. Here, after desiccation the
gel converted to a clear liquid with a separation of a small
white precipitation at the bottom. On cyclomixing, the
whole clear solution converted to a turbid solution. The
loss of water on desiccation was 4.49%, which was only
higher than the TG but lower than the SG and MG.
Salt Effect
Effects of salts on the consistencies of the gels between
the temperature range from 20 C to 30 C were studied;
the concentrations of the salts used were all at 0.1 M (see
Table 2). They have suggested that the salts produced
greater effect on MG; the effect on SG was not observed
for LiCl, KCl, CsCl, and MgSO4. NaCl had some loosen-
ing effect whereas Al2(SO4)3 had tightening effect on SG.
CsCl and MgSO4 made MG nonsticky (on glass) viscous
solution.

dessicating effect, salt effect, solvent effect, rheology and

structural features by scanning electron microscopy (SEM). Solvent Effect
The results are presented below. We have studied the effects of ethanol, propanol and
isopropanol on the MG and SG in the temperature range
Desiccation Effect of 25 C to 30 C. Transitions of different types were
The water ratios of the gels were studied by prolonged observed by the presence of alkanols (see Table 3). Solvents
desiccation of known quantities of the gels in a desiccator produced different effect on MG and SG. Their effects on
over silica gel. The results are presented in Table 1. By pre- MG were same so also on SG. MG broke by the presence
paration, MG and SG had 21.7 and 32.6% water in them, of the alkanols whereas SG did not loose its consistency
respectively. They have lost fair percentages (7.71% and but turned to transparency. The effect on it was thus
11.73%, respectively) of water on desiccation and turned minor. The alkanols could not affect the developed internal
into solution. The removal of water destroyed the gel struc- structure of the SG.
ture. Thus, 13.99% and 20.87% of water for MG and SG,
respectively, were strongly associated with APSA-80 of Structural Features
which on an average
10% water built the gel architecture. The structural features of the gels were studied by scan-
It may be mentioned that since the transparent gel (TG) ning electron microscope (SEM) and optical microscopy
was nonthixotropic, it was formed in a small wide mouth (OM). SEM measurements were taken with a scanning
container, and as such kept in the desiccator to estimate electron microscope-JEOL-JSM-5200, Tokyo (Japan) at
the loss in mass and it was found as 1.49%. Another kind accelerating potentials of 15 and 20 KV. The images of
the gels (SG and TG) were taken in different magnifica-
tions and scale bar after the gold coating of the samples
TABLE 1 for making them conducting. Gold coating was done by
Desiccating effect on APSA-80 and gels formed with the sputtering method in a temperature range of 50 C to
water and IPM 60 C. Optical microscopic images were taken using a Motic
Trinocular Phase Contrast Microscope-AE-31 (Hong
Constant Mass Kong). Power of the lense used was 40X. The whole study
Initial desiccated reduction done through a compatible software named Motic Images
System mass=g. mass=g. (%) Advanced – 3.2. The SEM results are on SG and TG and
OM results are on MG and TG. For MG, SEM could
APSA-80 4.41 4.23 4.08 not be performed for the material melted and did not
Milky gel (MG) 5.71 5.27 7.71 become dry during gold quoting at higher temperature;
Smoky viscous gel (SG) 4.69 4.14 11.73 moreover, it could not be dried which was needed for
Transparent gel (TG) 9.41 9.27 1.49 taking SEM images. This might have occurred due to the
Aluminium sulfate 9.58 9.15 4.49 presence of higher percentage of oil (of higher boiling
induced gel point, 193 C) in MG as compared with the other two gels.
 PHYSICOCHEMICAL STUDIES ON AN ALL-PURPOSE PESTICIDE SPRAY 1435

TABLE 2
Effects of 0.1 M salts on the gel consistencies in the temperature range of 20 C to 30 C
Salts Milky gel (MG) Time=days Smoky viscous gel (SVG) Time=days

LiCl Upper clear lower gel 7 No change 7

Upper clear, middle milky soft layer, 30 No change 30
bottom milky solution
NaCl Tight milky gel 7 Viscous solution 7
Upper clear soln, middle milky layer, 30 Less viscous solution 30
bottom clear solution
KCl Upper clear part with lower milky gel 7 No change 7
Upper clear solution, middle soft milky 30 No change 30
layer, lower clear solution
CsCl Tight milky gel 7 No change 7
Non sticky loose gel 30 No change 30
MgSO4 Non sticky milky viscous solution with 7 No change 7
lower clear solution
Upper and lower clear solution with 60 No change 60
middle soft milky layer
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Al2(SO4)318H2O Same as Mg(SO4) 7 Tight Milky gel 7

Upper and lower clear solution with a tiny 60 No change 60
separation at the bottom

The Figures 4a and 4b constituted the SEM pictures of TG
and SG, respectively. Both horizontal and vertical layers of
materials were observed in distinct mixed domains for SG.
The TG produced rose petal like domains. The SG and TG
had distinct but different morphologies. On the other
hand, Figure 4g depicted the internal morphology of the
aluminium-incorporated gel as described above. It also
exhibited a patterned nature of the internal structure. The
OM pictures of TG at much lower magnification evidenced
multi colored spotted and irregular shaped domain that lin-
early propagated (Figure 4c); its 3D picture (Figure 4d)
revealed fairly populated spike like projections. OM pre-
sentation of MG (Figure 4e) offered interlinked noodle like
structures dispersed with tiny nearly spherical bodies
revealing a mosaic pattern. Its 3D picture (Figure 4f) has
produced densely populated spikes of larger size than that
observed for TG. It is mentionable that OM pictures of the
gels were taken under ambient condition. Drastic tempera-
ture related drying up of the samples as in SEM was not
required for this measurement. Significant differences
between OM and SEM pictures as observed were thus
not very unusual.
Rheology
For rheological studies the gels MG and SG were used
along with a viscous solution (VS) of composition in g%
(water ¼ 59.1, APSA-80 ¼ 37.4 and IPM ¼ 3.4) falling in
the zone 4 in Figure 3. Both MG and SG have evidenced
shear thinning with mild to moderate transitions
(Figure 5a) indicated in the figures. The VS has witnessed
(Figure 5b) an initial small shear thinning up to shear rate ¼
0.01995 s1, and beyond that the system has undergone

TABLE 3
Solvent effect on the behaviors of MG and SVG in the temperature range of 25 C to 30 C
Appearances for MG Appearances for SG

Initial Final Initial Final

Ethanol (34.5) Upper-(smoky loose gel) Upper clear solution and Smoky viscous gel Transparent gel
Ethanol (9.5) and lower clear solution lower clear solution
Propanol (25.5) Upper-(smoky loose gel) Upper clear solution and Smoky viscous gel Transparent gel
Propanol (9.5) and lower clear solution lower clear solution
Isopropanol (29.5) Upper-(smoky loose gel) Upper clear solution and Smoky viscous gel Transparent gel
Isopropanol (9.5) and lower clear solution lower clear solution
 1436 I. MUKHERJEE ET AL.
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FIG. 4. (a) SEM image of the transparent gel, TG of mass% composition (water ¼ 46.6 g, APSA-80 ¼ 35.1 g, IPM ¼ 18.3 g) region 5 in Figure 3.
Accelerating potential 15 KV, scale bar 50 mm, and magnification 500 pa. (b) SEM image of the smoky gel, SG of mass% composition (water ¼ 32.6 g,
g, APSA-80 ¼ 56.4 g, IPM ¼ 11.0 g) region 3 in Figure 3. Accelerating potential 15 KV, scale bar 50 mm, and magnification 500 pa. (c) Optical micro-
scopic results of transparent gel, TG of mass% composition (water ¼ 46.6 g, APSA-80 ¼ 35.1 g, IPM ¼ 18.3 g) region 5 in Figure 3. Magnification
40. (d) Three-dimensional optical microscopy image of transparent gel, TG of mass% composition (water ¼ 46.6 g, APSA-80 ¼ 35.1 g, IPM ¼ 18.3 g)
region 5 in Figure 3. (e) Optical microscopy image of milky gel, MG of mass% composition (water ¼ 21.7 g, APSA-80 ¼ 22.6 g, IPM ¼ 55.7 g) region
7 in Figure 3. Magnification 40. (f) Three-dimensional optical microscopy image of milky gel, MG of mass% composition (water ¼ 21.7 g,
APSA-80 ¼ 22.6 g, IPM ¼ 55.7 g) region 7 in Figure 3. (g) SEM image of the aluminium sulfate incorporated smoky gel, SG of mass% composition
(water ¼ 32.6 g, APSA-80 ¼ 56.4 g, IPM ¼ 11.0 g) region-3 in Figure 3. Accelerating potential 20 KV, scale bar 50 mm, and magnification 350 pa.

remarkable shear thickening up to the shear rate of unity the form of a small peak) at s1 ¼ 3.981. The observations
with a small shouldering at 0.1995 s1. Beyond s1 ¼ 1, of both thinning and thickening of the same system is
sharp shear thinning has occurred with an inflection (in not commonly found. The constituted system internally
 PHYSICOCHEMICAL STUDIES ON AN ALL-PURPOSE PESTICIDE SPRAY
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FIG. 5. (a) Viscosity versus shear rate of milky gel, MG - (2) of mass%
composition (water ¼ 21.7 g, APSA-80 ¼ 22.6 g, IPM ¼ 55.7 g), region 7 in
Figure 3 and smoky gel, SG – (1) of mass% composition (water ¼ 32.6 g,
APSA-80 ¼ 56.4 g, IPM ¼ 11.0 g) region 3 in Figure 3 at 303 K. Transition
points are indicated by arrowheads on the curves. (b) Viscosity versus
shear rate of clear viscous solution (region-4 in Figure 3) of composition
in g% (water ¼ 59.1, APSA-80 ¼ 37.4 and IPM ¼ 3.4).
organized up to s1 ¼ 1 and then disorganized by the
application of shear stress. The observed results were fitted
to a four-degree polynomial equation. In the figure, the
fitted curve is shown with the experimental points; the
equations with the related coefficients are also presented
along with the figure. The fitting was fair. The results in
Figure 5a and b were fitted to three- and four-degree poly-
nomials, respectively, and the experimental points with the
1437
fitted curves are presented in the figures along with the fit-
ting relations and coefficients. MG had produced more
inflections (five) than SG, which have shown only two.
The polynomial fittings for them were much better than
the viscous solution (VS).
Dye Penetration in Gels
The polarity and nonpolarity of the gels has been tested
by way of dye solubilization and penetration. (The beha-
vior has been discussed with reference to the Figures 6a
through 6e.) Two dyes crystal violet and oil red have been
used they are water and oil soluble, respectively. The
biphasic liquid system of g% composition (water=
APSA-80=IPM as 2.8=13.6=83.6), Figure 6a has shown
solubility of oil red in the top layer and crystal violet in
the bottom layer. In the biphasic system of mass% compo-
sition (water=APSA-80=IPM as 11.2=21.8=66.9), the top
red layer was oil and consumed Oil-Red and the bottom
gel layer was polar and consumed crystal violet
(Figure 6b). In the biphasic system, the addition of the dyes
to their unfriendly region transferred them to the friendly
region, that is, oil red was transferred from aqueous envir-
onment to oil environment and vice-versa. In three-phase
systems where a milky-creamy viscous gel layer was the
middle phase and top and bottom were nonpolar and
polar, respectively, the added dye penetrated through the
middle viscous gel layer to reach its destination either top
or bottom depending on its nature and the favored envir-
onment. The viscous middle milky layer has acted like a
diaphragm or membrane in Figure 6c. In Figures 6d and
6e, the photographs of the inverted container with gels
represent a combined system of lower clear gel and upper
milky gel, SG and MG (shown in Figure 6d) and transpar-
ent gel in which both water and oil soluble dyes penetrated
(Figure 6e). We are in the process of studying the rate of
penetration of dyes through the gel. Special designing of
experimental setup is required. At present, we do not have
sufficient results at hand for presentation in this article;
they will presented in a future publication.
Temperature Effect on IPM, APSA-80, IPM þ Water,
APSA-80 þ Water and Water þ APSA-80 þ IPM Systems
In connection with phase studies of the ternary formula-
tions of water=APSA-80=IPM, we have also examined the
temperature effect on the stability of the pure, binary, and
ternary mixtures of the studied components. The results are
presented in Table 4. In general, application of temperature
on IPM studied up to 250 C and did not show any change,
the system remained transparent throughout. Application
of heat produced turbidity and clouding to the other mixed
compositions; the details of which are discussed with refer-
ence to the data in the table. Like many nonionic surfac-
tants and water-soluble polymers,[34–36] APSA-80 started
clouding at high temperature in the range of 180 C to
 1438 I. MUKHERJEE ET AL.
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FIG. 6. Dye penetration to biphasic and triphasic systems of water=APSA-80=IPM. (a) Biphasic composition in g% (water=APSA-80=IPM as
2.8=13.6=83.6), liquid=liquid (CV in the bottom phase, OR in the top phase). (b) Biphasic composition in g% (water=APSA-80=IPM as 11.2=21.8=
66.9), liquid=gel (CV in the bottom gel phase, OR in the top oil phase). (c) Triphasic composition in g% (water=APSA-80=IPM as 49.9=16.2=33.9),
liquid=gel=liquid system with and without dye. OR in the top oil and CV in the bottom water phase. (d) Inverted presentation with mass% composition
of milky gel, MG (water ¼ 21.7 g, APSA-80 ¼ 22.6 g, IPM ¼ 55.7 g), smoky gel, SG (water ¼ 32.6 g, APSA-80 ¼ 56.4 g, IPM ¼ 11.0 g), and combined
transparent and milky gel system (water ¼ 34.1 g, APSA-80 ¼ 25.1 g, IPM ¼ 40.8 g). (e) Transparent gel composition in g% (water ¼ 46.6 g,
APSA-80 ¼ 35.1 g, IPM ¼ 18.3 g), Middle, without dye; left, with OR; right, with CV.

220 C and continued to cloud more with rise in tempera-
ture studied up to 250 C. In the temperature range of
220 C to 250 C the product turned to be a biphasic solu-
tion. Mixed with 50% v=v water, the binary system
(APSA-80 þ water) also became turbid at 60 C, and the
clouding process continuously increased up to 102 C. On
cooling to room temperature (
28  0.1 C), a biphasic
solution (upper turbid and lower clear) was realized.
Irreversible formation of emulsion was envisaged at
temperature beyond 70 C; a part of it did not revert to
its original state of single-phase solution. The APSA-80=
IPM (1:1 v=v) solution was more complex toward tempera-
ture. It started with smoky appearance at 76 C that became
strongly turbid at 84 C which changed into a clear solution
at 104–118 C then the solution became highly turbid in the
range of 118 C to 140 C. The ternary mixture of water=
APSA-80=IPM of g% composition (1.9=37.4=60.6) falling
in the region 1 in the phase diagram (Figure 3) has evi-
denced turbidity at 70 C which became intensely turbid
at 76 C and became clear solution at 110 C. On cooling,
the state of the solution did not change, it remained as a
clear monophasic solution. Another clear viscous solution.
Water=APSA-80=IPM of g% composition (59.1=37.4=3.4)
falling in the region 4 in the phase diagram (Figure 3)
showed appearance of clouding from 52 C. The solution
got completely clouded at 62 C. At temperature >100 C,
it formed a heterogeneous turbid solution was formed
which on cooling to room temperature resulted in a lower
 PHYSICOCHEMICAL STUDIES ON AN ALL-PURPOSE PESTICIDE SPRAY 1439

TABLE 4
Temperature effect on the stabilities of IPM, APSA-80, APSA-80 þ IPM, APSA-80 þ Water and Water
þAPSA-80 þ IPM
Transition
System temperature= C Visual appearances

IPM Till 250 Transparent

APSA-80 180–220 Faintly yellow turbid solution
220–250 Intense wine color appeared and a phase separation was occurred
APSA-80 þ water 1:1(V=V) 60–62 Start of Turbidity
70–102 Complete clouding that persisted beyond 102 C. On cooling
biphasic solution with upper turbid and lower clear part observed
APSA-80 þ IPM 76–78 Smoky appearance
84–86 Intense clouding
104–118 Clear solution
118–140 Reappearance of intense clouding
Water=APSA-80=IPM-w= 70–72 Start of turbidity
w%(1.9=37.4=60.6) – 76–78 Intense clouding
region-1 in phase diagram 108–110 Clear solution (remained clear and monophasic on cooling to room
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temperature)
Water=APSA-80=IPM-w= 52–54 Start of turbidity
w%(59.1=37.4=3.4)-
region-4 in phase diagram
62–64 Intense clouding
100–102 Heterogeneous solution appeared on cooling to room temperature
upper, lower clear biphasic solution appeared

and upper clear biphasic solution that remained stable for a

long period of time.

Antibacterial Activities of APSA-80

The study has shown that APSA-80 produced moderate
antibacterial activities against the studied strains Bacillus
subtilis, Streptomyces fradiae, and the yeast Saccharomyces
cerevisiae. An inhibition zone of diameter 20 mm developed
on an average in the original form of APSA-80 as
compared to around 35 mm developed by an antibiotic,
Erythromycin (2.5 mg=ml; Figure 7). MIC study has shown
that Streptomyces fradiae has a higher sensitivity to
APSA-80 since the MIC has been found to be 0.075% with
APSA-80 for both the Gram positive bacteria Bacillus
subtilis and yeast in comparison with 0.05% APSA-80 for
Streptomyces fradiae. Because of limited of reports on anti-
bacterial properties of APSA-80, further studies are
required to understand the mechanism of antibacterial
and antifungal effects of the adjuvant.[42] It can be added
that APSA-80 may offer some synergistic effect[43] to the
spray formulations to be used for agricultural purposes.
FIG. 7. Antibacterial activity of APSA-80 compared with the antibio-
This spray adjuvant has the prospect for specific applica- tic erythromycin on Gram positive bacteria Bacillus subtilis, A) pure ery-
tions. Since mesophiles are the most frequent pathogens thromycin, B) 100% APSA-80, C) 0.025% APSA-80; plaque size indicates
to the agricultural surface and other infections in tropical degree of effectivity.
 1440 I. MUKHERJEE ET AL.
and subtropical developing countries, the above response
warrants scaling-up for practical purposes.
CONCLUSIONS
APSA-80 efficiently gets adsorbed at the air water inter-
face and self assemble in aqueous medium to form micelle
at 0.006 g%. In terms of surface tension lowering it is more
effective than the other nonionic surfactants (Tween-20,
TritonX-100, Brij-35, and MEGA-10) and their binary
and ternary combinations. This physical property makes
the formulations very effective dispersant for pesticides in
agricultural applications. Normally, it has a very good
miscibility with both water and IPM but at temperature
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