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Kariim Ishaq Ahmed Aliyu

Federal University of Technology Minna Federal University Wukari


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American Journal of Innovative Research and Applied Sciences. ISSN 2429-5396 I




| Kariim Ishaq1 | Aliyu Ahmed2 |Abdulkareem Ambali Saka1,3|Abubakre Oladiran Kamardeen1,4|Mohammed Ishaq

Federal University of Technology | Center for Genetic Engineering and Biotechnology (CGEB) | Minna| Nigeria |
Federal University | Department of Chemical Engineering | Wukari, Taraba State | Nigeria |
Federal University of Technology| Department of Chemical Engineering | Minna, Niger State | Nigeria |
Federal University of Technology| Department of Mechanical Engineering | Minna, Niger State | Nigeria |

|Received | 14 March 2016| |Accepted | 20 March 2016| | Published 31 March 2016 |


Background: The dependence of adsorption rate on the particulate behavior of adsorbents can be effectively studied using the
concept of Brownian motion. Variation in settling time of particles at different temperatures could have effect on adsorption process.
The dynamic light scattering (DLS) technique is based on the principle of Brownian motion, and thus is suitable for investigating the
behavior of particles under different conditions. Objectives: In the present research, particulate behavior of modified kaolin was
studied at varied temperature using DLS technique in Zetasizer Nano-S equipment. Methods: Local kaolin was characterized for its
thermal stability, surface morphology, and crystallinity using Thermogravimetric analysis (TGA), high resolution scanning electron
microscopy (HRSEM) and X-ray diffractometry (XRD) respectively. For adsorbent development purpose, the local kaolin was modified
by acid activation process, and its properties were studied by DLS and XRD techniques. The DLS was also used to investigate the effect
of temperature on the viscosity, refractive index, polydispersity index, and particle size of the adsorbent. Results: It was found that
the intensities and sizes of particles increased with increase in temperature during the DLS experiment by the Zetasizer Nano-S
equipment. Conclusion: The study therefore suggests that for effective adsorption process at varied temperature, there should be a
stirring medium to increase the relaxation time of the adsorbent in a batch reactor.

Keywords: Kaolin, Zetasizer Nano-S, DLS, Particulate behavior, Adsorbent, Characterization


Effective methods for the removal of highly poisonous organic compounds from water have attracted significant interest.
This is due to challenges combating most developing countries resulting from problems imposed by contamination of
drinking water by pollutants. A number of methods such as adsorption, membrane separation, precipitation, ion
exchange, reverse osmosis and advanced oxidation processes have been used for the removal of organic pollutants from
polluted water and wastewater [1,2]. Adsorption is one of the most used processes for toxic material removal. It is a
surface phenomenon whose mechanism is similar for both organic and inorganic toxic contaminants. During this process,
a liquid-solid intermolecular forces is established when a solution containing solute comes in contact with a solid with a
highly porous surface structure, therefore, a deposited at the solid exist at the adsorbent surface [3,4]. Petroleum
distillation, Mining, plating, dyeing, automobile manufacturing and metal processing are major processes by which toxic
materials are released into the environment. Wastewater with organic pollutants contains large quantities of suspended
solids which reduce the light available to photosynthetic organisms and, on settling out, alter the characteristics of the
river bed, rendering it an unsuitable habitat for many invertebrates. Organic pollutants include pesticides, fertilizers,
hydrocarbons, phenols, plasticizers, biphenyls, detergents, oils, greases, pharmaceuticals, proteins and carbohydrates
[5,6]. The behaviors of an adsorbents particles at varied temperature in a batch reactor system are an important factor
that affects the rate of adsorption due to varied settling time. Therefore, the best study system that best fit such
behavior is Brownian motion.


2.1 Materials: Raw kaolin was sourced from Lagos state of Nigeria. Other chemicals such as hydrochloric acid (HCl),
sodium hydroxide (NaOH), and hydrogen peroxide (H2O2) were of analytical grade with a high purity of 99.99% and
supplied by Aldrich without any further purification. Distilled water was used for all experimental investigations.

All articles published in The American Journal of Innovative Research and Applied Sciences are the property of Atlantic Center Research Sciences, and is protected by copyright 113
laws. See: Copyright 2014, Atlantic Center for Research Sciences. All Rights Reserved.
American Journal of Innovative Research and Applied Sciences. ISSN 2429-5396 I

2.2 Methods: Raw kaolin was screened through a 212 m sieve. A known weight of 100 g of the sieved kaolin was fed
in a beaker and agitated with 30% hydrogen peroxide to remove organic particles from the sieved kaolin. At the
completion of effervescence as a result of addition of hydrogen peroxide, the top layer was decanted immediately and
later washed in distilled water for the removal of hydrogen peroxide remnant. The left over kaolin sample was then oven
dried at 110oC for 5 hours.
The oven dried pretreated kaolin sample was then activated using hydrochloric acid of 0.5 mol/dm3 and the mixture was
continuously stirred for 2 hours on a magnetic stirrer. The resulting slurry was then neutralized using 0.02 mol/dm3 of
sodium hydroxide. Subsequently the solution was filtered and washed with distilled water to ensure a pH of 7. Finally, the
resulted activated kaolin was then dried in a static air oven at 110oC for 5 hours and stored.

2.3 Characterization of kaolin samples

The chemical compositions of the kaolin were characterized by X-ray fluorescence (XRF) using Philips PW2400 and
Powder XRD patterns were recorded in the range of 10 to 80 degrees on a Phillips (PW 1800), X-ray diffractometer with
Cu K radiation (1.542 ). HRSEM images of the kaolin was taken using Joel JEM 100S. TGA/DTG graphs was recorded
on Perkin Elmer (TGA 4000), in the temperature range 40 to 1000C with a heating rate of 10 C/min in the presence of
nitrogen. The particle size and hydrodynamic diameter were determined using Zetasizer Nano-S at scattering angle of
173o operating at 25oC, 50oC and 75oC with equilibrating time of 10 sec per runs. 1 mg of the samples were dispersed in
10 mL of water by means of a sonication (Misonix 3000; power: 1 W/mL, pulse on: 3 sec, pulse off: 3 sec, time: 1 min)
and a centrifugation (5 min @ 3000 rpm). The supernatant (free of larger aggregates) then transferred into a polystyrene
quartz cuvette using a syringe with 0.23 m filter and placed in the Zetasizer Nano S cuvette holder immediately for
analysis. Each DLS measurement was averaged over 20 runs (10 sec per run).


Figure 1: The figure 1 presents the Thermo-gravimetric and

derivative thermal analysis of raw kaolin between 73oC and 769oC
showing the percentage weight loss as function of temperature

Figure 2: The figure 2 presents the X-ray diffraction patterns for (a) raw kaolin (b) activated
kaolin with HCl, recorded in the range of 10o to 80o with Cu K radiation (1.542 )

American Journal of Innovative Research and Applied Sciences. ISSN 2429-5396 I

Figure 3: The figure 3 presents the High resolution scanning electron microscope images (a) raw
kaolin (b) activated kaolin with HCl, showing pore distribution on the surface

Figure 4: The figure 4 presents the Zetasizer Nano-S results of activated kaolin with HCl at
25oC operating Condition.

American Journal of Innovative Research and Applied Sciences. ISSN 2429-5396 I

Figure 5: The figure 5 presents the Zetasizer Nano-S results of activated kaolin with HCl at
50oC operating Condition.

Figure 6: The figure 6 presents the Zetasizer Nano-S results of activated kaolin with HCl at
75oC operating Condition.

American Journal of Innovative Research and Applied Sciences. ISSN 2429-5396 I

Figure 7: The figure 7 presents the particle size representation from

Zetasizer Nano-S results of activated kaolin with HCl at different

Table 1: Table 1 presents the chemical composition of raw Lasgos state kaolin.
Sample Fe2O3 MnO TiO2 CaO K2O SiO2 Al2O3 MgO Na2O LOI Total
KAOLIN 0.73 0.02 0.26 0.19 1.26 52.27 33.80 0.11 0.00 11.44 100.07

Table 2: Table 2 presents the extracted data from the Zetasizer Nano-S results of activated kaolin with HCl at
different temperature.
S/N Temperature Count Viscosity Material Z-average Intercept pdI
(oC) rate(kcps) (cP) RI (d.nm)
1 25 682.00 0.8872 1.59 338.50 0.112 0.325
2 50 376.60 0.5482 1.59 421.40 0.437 0.380
3 75 34.30 0.3784 1.59 2093.00 1.090 0.755


Table 1 shows the oxides constituents of kaolin using XRF analyzer. The kaolin sample contains alumina (33.80%) and
silica (52.27%) which was in major quantities, whereas other oxides such as iron oxide, magnesium oxide, calcium oxide,
potassium oxide, manganese oxide, and titanium oxide are present in trace amounts. There is general agreement
between the current obtained values and results previously obtained for Nigeria kaolin by Kovo (2011) [7,12].

The thermal analysis curves of kaolin, (TGA/DTA), are present in Figure 1. The total weight loss reached at 768.9 oC is
13.94% which is in agreement with literature value of 14% [8]. Only One transition was observed, i.e., the kaolin thermal
decomposition curves show one endothermic effect at 546.52C which is attributed to the liberation of water caused by
dehydroxylation of coordinated and structural water molecule [9]. However, XRD pattern for the investigated raw and
activated kaolin are presented in Figure 2 which shows an increase in the quartz content with a notable decrease in both
kaolinite contents after activation using hydrochloric acid [10,13].

The HRSEM images in Figure 3 revealed the flakes morphological structure of kaolin sample. After acidic activation, the
pores in the flakes structure increased as shown in Figure 3(b). These confirmed that acidic activation of kaolin increases
the pores which favor adsorbent performance during adsorption process [13].

The particulate nature of the developed adsorbent was characterized Using Zetasizer Equipment. The equipment operates
using the mechanism of Brownian motion coupled with Stokes-Einstein equation in the determination of the important
parameters. Using Nanosizer, particle size was analyzed using a Dynamic Light Scattering Technique (DLS). In all cases,
particles are hypothetically analyzed as a spherical object. Thus, hydrodynamic diameters are generated; size of a sphere
that has the same diameter as the particle being analyzed (dH). In DLS experiment, temperature, refractive index and

American Journal of Innovative Research and Applied Sciences. ISSN 2429-5396 I

viscosity are the main important parameter of interest. Therefore, the average particle sizes were determined using
Stokes-Einstein equation. Generally, the most important and frequently reported parameter is the d H [11].

The particulate behavior of the developed adsorbent was monitored at varied temperature. During the analysis process,
collision occurs both on the sides of the spherical materials being analyzed, while the front size is more pronounced. This
resulted to an increment in the rate of collision as a function of the systematic induced velocity (V). The systematic
induced velocity is inversely proportional to the velocity of the particles been analyzed [11]. At this point, the average
induced velocity gained by the material is a function of the experienced stochastic force at any microseconds which is
detectable by the Zetasizer equipment.

Figure 4-6 shows the effects of temperature on the diffusion coefficient of the adsorbent at varied temperature. From
Table 2, temperature has no effect on the refractive index of the developed adsorbent. This implies that the color of the
material is not affected with temperature variation. Also, the intercept, polydispersity index (pdI) which indicate that the
particles in the developed adsorbent are polydispersed in the aqueous medium. Molecules in suspension undergo
Brownian motion. This is as a result of bombardment of particles by the laser rays generated from the equipment. Hence,
particles behave differently as temperature increases due to variation in viscosity and velocity hence, the settling time are
affected as shown in Figure 4-6. As particles are illuminated in laser, particles gain more kinetic energy at higher
temperature and therefore, smaller particles are kick down. This phenomenon is highly pronounced at higher
temperature due to reduction in viscosity which leads to high velocity of the particles in the medium been examined.
Therefore, the particle sizes are of important consideration as illustrated in Figure 4-6. These particles movement
depends on the translational velocity of the material which is calculated by the equipment using Stoke-Einstein equation.
Therefore, for effective adsorption of the developed adsorbent, a stirring medium is desired so as to increase the setting
time of the particles as temperature has effect of the settling time.


The industrial applications of adsorbents in batch processes cannot be over-emphasized, especially in wastewater
treatment. Brownian motion forms an important phenomenon in investigating the principles of adsorption rate vis--vis
its dependence on particulate behavior of adsorbents at various temperatures and settling time. The DLS technique is
suitable for studying behavior of particles in batch systems because it works based on the principle of Brownian motion.
Particles of local kaolin material were shown to exhibit high thermal stability and flakes-like morphological structure. Its
pores were improved by modification using chemical activation process, which is favorable for the adsorbent properties.
Temperature was found to have significant influence on viscosity, Z-average and polydispersity index (PdI) of the
particles. From the temperature effect on the particulate behavior, an effective application of the developed adsorbent
would require a stirring medium to increase the settling time of the material so as to favor adsorption process.


Authors are grateful to Centre for Genetic Engineering and Biotechnology (CGEB), FUT Minna, Nigeria for given us access
to centers facilities.

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Cite this article: Kariim Ishaq, Aliyu Ahmed, Abdulkareem Ambali Saka, Abubakre Oladiran Kamardeen, Mohammed Ishaq Alhassan.
S. American Journal of Innovative Research and Applied Sciences. 2015; 2(3): 113-119.

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