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CHAPTER 4
Removal of Bi (III) with adsorption technique using coconut shell activated
carbon as a low cost adsorbent
*This work has been communicated to “Chinese Journal of
Chemical Engineering” (Revised)
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4.1 INTRODUCTION
The level of natural resources of bismuth is about 2 X 10-5 %. The world
production is about 5000 tones per year. Much of the bismuth produced in the U.S.
is obtained as by-product in refining lead, copper, tin, silver and gold ores.
Bismuth and its compounds are used in semiconductor, cosmetics preparation,
alloys and metallurgical additives also in the preparation and recycling of uranium
nuclear fuels [1, 2]. The inorganic bismuth salts are used for medical treatment.
The patients suffering from gastric disorder leaves 0.5 to 1 g pure bismuth per day.
Bismuth contamination is becoming an environmental problem [3]. Bismuth
containing compounds have been used for different medicinal purposes, especially
for the treatment of syphilis, gastritis, and ulcer. As the use of bismuth in
medicines is increasing, it has spread in the environment, and the exposure of
organisms to bismuth has increased. However, a number of toxic effects in
humans have been attributed to bismuth compounds such as nephropathy,
osteoarthropathy, hepatitis, and neuropathology [4]. Therefore the removal of
bismuth is essential for the elimination of bismuth contamination.
The methods available for the removal of heavy metals from aqueous
solution are electrochemical precipitation, ion exchange, ultrafiltration, reverse
osmosis, adsorption. Amongst all, adsorption technique is feasible option, both
technically and economically [5]. Especially, if the adsorbent is inexpensive and
readily available then adsorption process provides an attractive alternative.
Activated carbons are effective adsorbents for many pollutant compounds
(organic, inorganic, and biological) of concern in water and waste water treatment.
The major use of activated carbon is in solution purification and for the removal of
taste, color, odors and other objectionable impurities from liquids, water supplies
and vegetables and animal oils [6]. Activated charcoal derived from coconut shell
was found to be a good non-conventional adsorbent used for the removal of heavy
metals like, Cd(II) [7], Pb(II) [8] as well as cationic dye [9] etc. from aqueous
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solution. The green coconut shell was used without treatment for separation of
Cr(III), Cr(VI), As(V) and Cd(II) [10]. Coconut shell as well as coconut husk was
reported for removal of Cr(VI), Zn(II) and Ni(II) [11].
4.2 LITERATURE SURVEY OF METHODS FOR REMOVAL OF Bi(III)
Now a days it is well known, that the abundance increment in the world
population as well as the use of amenities with various technology which gave rise
to need of more production of required things is responsible to expanded pollution
by various pollutants. Amongst the various pollutants, pollution due to bismuth is
getting increased due to enhanced applications of bismuth. The several techniques
reported for removing Bi(III) from water include liquid-liquid extraction [12],
solid phase extraction [13], flotation [14] and adsorption [15]. The experimental
studies on Bi(III) adsorption by using resins [16] and the electrodes surface of
metals, such as Pt [17, 18], Au [19] and Si [20] had been reported. There are very
few reports on bismuth removal using adsorption [15].
The liquid-liquid extraction and recovery of Bi(III) from succinate solution
using 2-octylaminopyridine (2-OAP) as an extractant was reported. The
quantitative extraction of Bi(III) occurs from 0.004 to 0.007M sodium succinate
solution at pH 2.5-10 using 0.036 M 2-OAP in chloroform [1]. The N-n-
hexylaniline in xylene was used for the extraction separation of Bi(III) from
thiocyanate and sulphuric acid media. Bi(III) was extracted quantitatively with 10
mL 1.5% N-n-hexylaniline in xylene. It was stripped from the organic phase with
sodium acetate buffer [12]. In liquid-liquid extraction, required reagent is not
economical as well as the systems are not ecofriendly with respect to use of the
solvent.
The solid phase extraction was performed with 6 mL syringe cartridges
containing 500 mg octadecyl bonded silica (40 µm particles) modified with
cyanex 301 from Varian. The modified cartridge was preconditioned by passing a
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10 mL portion of 0.1M HCl solution, then 25 mL of the sample solution
containing 1 g of Bi(III) ions and 0.1M HCl, was passed through the cartridge by
applying a slight vacuum. The cartridge was dried completely by passing an air
through it. The extracted Bi(III) was stripped from the cartridge using appropriate
amounts of suitable mineral acids [21]. In the other report, the syringe was filled
with 0.5 g of silica gel modified with 3-aminopropyltriethoxysilane and in order to
retain the analyte elements, 5 mL of sample solution (pH 5) was drawn into the
syringe to 15s and discharged again in 15s. Then, 2.0 M HCl, as the eluent, was
drawn into the syringe and ejected back to desorb the analyte elements [22]. In
another case sample solution treated with and without ammonium pyrolidine
dithiocarbamate was drawn into the syringe filled with chromosorb-107. Analyte
elements adsorbed on the resin were quantitatively eluted with 3.0 M of HNO3
[13].
Ion flotation involves the removal of surface-inactive ions (colligend) from
aqueous solutions by adding surfactants which act as collectors. Precipitate
flotation is a foam separation process used to remove surface inactive substances
from aqueous dispersions. The component to be removed is precipitated before the
addition of a surfactant (collector). Flotation is a simple and quantitative technique
for the separation of Cd(II), Hg(II), Bi(III) and Sb(III). It depends on the formation
of metal iodide anion [MI4] (n-4)-, the combination with Fe(II)tris(1,10-
phenanthroline) reagent (I), and flotation of the resulting chemical associate with
oleic acid surfactant. The parameters influencing the flotation process were pH of
solution, iodide, Fe(II)tris(1,10-phenanthroline) and surfactant concentrations,
temperature and foreign ions [14]. In another case Bi(III) could be removed from a
water insoluble ternary association complex BiI4-·TBAB+ with tetrabutyl
ammonium bromide (TBAB) and KI in water solution. When the concentrations of
tetrabutyl ammonium bromide and KI in solution were 5.0×10-4 mol/dm3 and
3.0×10-3 mol/dm3 at pH 3.0, Bi(III) could be quantitatively separated from
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Mo(VI), Ga(III), Co(II), Mn(II), Zn(II), Rh(II), Al(III), Cr(III), V(V), Ni(II),
Sn(IV), W(VI) and Fe(II) [23].
Separations with the anion exchange resin Deacidite FF have proved
exceedingly useful for the separation of macro amounts of bismuth from small
amounts of thorium and uranium, without any significant losses of these latter
constituents. The use of ion-exchange resins, however, introduces problems in the
subsequent determination of the separated elements and the frequent need for the
removal of organic matter taken into solution from the resin, since the introduction
of a wet oxidation step considerably extends the time needed for the analysis [24].
Traces and larger amounts of bismuth (up to 50 mg) can be separated from gram
amounts of thallium, mercury, gold and platinum (up to 5 g) by sorption from a
mixture of 0.1 M hydrochloric acid and 0.4 M nitric acid on a column containing
3 g (8.1 mL) of AGMP-50, a macroporous cation-exchange resin. This resin
retains bismuth (III) much more strongly than does the usual microporous resin
(styrene-DVB with 8% cross-linkage) [25]. A method for the determination of
trace bismuth in lead using a high-performance chelating ion chromatography
system is described where chelating column was prepared from a neutral
hypercrosslinked polystyrene resin, MN200 (Purolite) [26].
Anodic stripping differential pulse polarographic method has been
developed for the determination of trace amount of bismuth in various samples
after adsorption of its 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex
on amberlite XAD-2 resin in the pH range of 2.0–3.0. The retained analyte on the
resin recovered with 10.0 mL of 2 M hydrochloric acid and bismuth is determined
by anodic stripping differential pulse polarography [27]. The determination of
trace bismuth is based on the adsorption of bismuth–bromopyrogallol red at a
carbon paste electrode. The overall analysis involved a three-step procedure:
accumulation, reduction, and anodic stripping [28].
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Impregnated resins prepared by the immobilization of an ionic liquid (IL,
Cyphos IL-101, tetradecyl(trihexyl)phosphonium chloride) into a composite
biopolymer matrix (made of gelatin and alginate) have been tested for recovery of
Bi(III) from acidic solutions. Maximum sorption capacity reached to 110–130
mg/g in 1 M HCl solutions [29]. An epoxy-group containing vinyl monomer was
appended uniformly across the porous sheet. Subsequently, a 1-octadecyl group
(C18H37) was introduced into the polymer chain grafted on the porous sheet. Tri-n-
octylphosphine oxide (TOPO), which contains octyl groups, was deposited on the
1-octadecyl group. The resultant TOPO-modified porous sheet had a higher
binding rate and a higher equilibrium binding capacity for bismuth than
conventional TOPO-modified beads [30].
The extraction chromatographic separation of Bi(III) was reported with
Versatic 10 coated on silanized silica gel. The result showed that the pH of
solution, influent volume, flow-rate and solution temperature would affect the
sorption of Bi(III). The extraction system has got good values of exchange
capacity (1.42 meq. of H+/g of dry exchanger at 298 K), breakthrough capacity
(19.75 mg/g at pH 5.5) and column efficiencies (300) with respect to Bi(III) [31].
Bismuth is extracted from 0.0l M citric acid at pH 3.0 with aliquat 3363 coated on
a silica gel column, by extraction chromatography. It was then stripped with 0.l M
sulphuric acid and determined spectrophotometrically [32].
A cloud point extraction method was used for separation and
electrothermal atomic absorption spectrometric method was used for determining
bismuth. The aqueous analyte was acidified with sulfuric acid (pH 3.0–3.5). Triton
X-114 was added as a surfactant and dithizone was used as a complexing agent.
[33]. A cloud point extraction method was used for the preconcentration of ultra-
trace bismuth in human serum prior to its determination by inductively coupled
plasma optical emission spectrometry. The method was based on the complex of
Bi(III) with 8-hydroxyquinoline and Triton X-114 used as non-ionic surfactant.
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The main factors affecting cloud point extraction efficiency were pH of solution,
concentration of complexing agent, concentration of non-ionic surfactant,
equilibration temperature and time [34].
The reversed-phase chromatography combines the selectivity of liquid-
liquid extraction and the advantages of chromatographic operation. In general, the
efficiency of reversed phase chromatographic separation depends on many
interrelated parameters including the particle size of the support, surface area, flow
characteristics and stationary phase. Polyurethane foam was used in a column
technique, where separation of Pd(II), Bi(III) and Ni(II) in the tributyl
phosphatethiourea-perchloric acid was achieved [35]. Trans-l,2-cyclohexane
diaminetetra-acetic acid (DCTA) chelates of bismuth(III), iron(III) and copper(II)
have been separated by two techniques using reversed-phase paired-ion
chromatography. The chelates in aqueous solution were separated within 20 min
on a 6.0 x 300 mm ERC-ODS column with 10-2 M tetrabutylammonium ion
(TBA+) in methanol-water mixture (45:55 v/v) as eluent. In the other, the metal
ions in aqueous solution were separated within 10 min by direct injection into an
ERGODS column with 10-2 M TBA+/10-3 M DCTA in methanol-water mixture
(40:60 v/v) as eluent [36].
A supported liquid membrane (SLM) using neutral extractants such as tri-n
octylphosphine oxide (Cyanex 921) is able to recover Bi(III) contained in highly
acidic solutions (from H2SO4/HCl media) [37]. The seperaration and recovery of
bismuth from a bismuth glance through leaching, purification and electro winning
from chloride solution is reported. A maximum current efficiency of >97% was
attained with an composition of 70 g/dm3 Bi, 25 g/dm3 NaCl, 4.5mol/dm3 HCl and
an analyte composition of 20 g/dm3 NaOH at 328 K and a cathode current density
of 200 A/m2 [38].
The metal surface electrodes were reported in last decade for adsorption of
bismuth. The growth of bismuth single crystals was studied when bismuth was
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deposited with a rate of about 6 monolayers per minute on the tungsten substrate
and kept at 470 K [39]. Co-adsorption of bismuth and hydrogen on the Si surface
was investigated. The formation of the morphology and electronic structure of the
Bi/H/Si interface at co-adsorption of bismuth and hydrogen on the Si surface was
investigated by scanning tunneling microscopy (STM), ultraviolet photoelectron
spectroscopy (UPS), low energy electron diffraction (LEED) and Auger electron
spectroscopy (AES) [40].
Some reports give information regarding the use of single crystal surface of
bismuth to adsorb the various organic compounds as well as halides like 2-methyl-
2-butanol [41], dodecyl sulfate anions on bismuth (011¯) [42], uracil [43], C1¯
and Br¯ ions on the (111) plane of a bismuth single crystal from solutions in 2-
propanol [44]. The adsorption of D-ribose [45] and the adsorption of I¯ ions on the
(111), (001) and (011) planes of a bismuth single crystal electrode from solutions
in ethanol has been investigated by means of differential capacity and electrode
charge measurements [46].
In present work, the adsorption study of bismuth on activated carbon
developed from coconut shell was carried out. The influence of adsorption time,
adsorbent dosage, shaking speed etc. has been studied. From experimental data the
isotherm models, kinetic model as well as the thermodynamic parameters has been
investigated for adsorption of Bi(III) on low cost, easily and abundantly available
adsorbent. The coconut shell activated carbon (CSAC) has good adsorption
capacity within a short period so it would be a good adsorbent.
4.3 EXPERIMENTAL
4.3.1 Preparation of materials
All chemicals were purchased from S. D. Fine Chem. Ltd. India. The
standard solution of 1 mg/mL Bi(III) was prepared from bismuth nitrate. The
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required solutions were prepared with dilutions from stock solution as per
necessity.
The adsorbent was prepared from dry coconut shell. The coconut was
collected from local market. To develop the activated carbon, the preparation
method was followed as given in the chapter 2 (2.3.1) using H2SO4 as
impregnating agent and sieved through BSS-25.
4.3.2 Characterization of adsorbent
The developed adsorbent was characterized with Fourier Transform Infra
Red Spectroscopy (FTIR) (Perkin Elmer Spectrum 100), Scanning Electron
Microscopy (SEM) (JEOL – JSM 6360 unit, Japan) and C, H, N, S analyzer (Euro
EA, Elemental Analyzer). The FTIR spectrum shows the peaks for functional
groups such as, O-H stretch, C-H, C=O stretch, C=C, SO2 and C-O stretch
respectively 3310.05, 2899.46, 1703.10, 1608.48, 1167.01, 1034.86 cm-1 values
(Fig. 4.1). For the better adsorption porous nature was required and it was
confirmed with SEM (Fig. 4.2). The elemental analysis reveals the presence of
carbon as the major quantitative element. The percentage amount of elements and
physical properties have also been investigated which are given in Table 4.1.
4.3.3 Batch adsorption experiment
The batch adsorption experiments were carried out by using orbital shaker
with Erlenmeyer flasks. The agitations were conducted at constant temperature of
299 ± 2 K for predetermined period. Adsorption study had been done with varying
the variables like initial concentration of metal ion, agitation period and speed etc.
The metal ion solution was maintained acidic through out the study with pH 2,
considering the fact that Bi(III) precipitates at pH values higher than 2.5 in
aqueous solution [8], the initial pH of each solution was adjusted to 2.0 with dilute
HNO3 or NaOH. The concentrations of Bi(III) in residual solutions were analyzed
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spectrophotometrically with xylenol orange as chromogenic reagent ( λmax =545
nm) (Elico SL 171) [47] and confirmed by Atomic Absorption Spectroscopy
(Perkin Elmer, AAnalyzer 300). The initial concentration of Bi(III) was varied
from 250 to 1000 mg/dm3 at constant adsorbent dose of 700 mg and adsorbent
mass was varied from 100 to 700 mg at constant 250 mg/dm3 of Bi(III). The
shaking period was varied from 15 to 300 min and the kinetic study was carried
out. For the thermodynamic study temperature was varied from 303 to 323 K. The
equilibrium adsorption capacity was evaluated using the formula given in chapter
2 (2.3.3).
4.4 RESULT AND DISCUSSION
4.4.1 Effect of time
From the study of effect of agitation time on the adsorption of Bi(III), it is
evident that time has a significant influence. The amount of adsorption of Bi(III)
was measured at different time intervals (Table 4.2). At the equilibrium time of
240 min, the Bi(III) adsorption was investigated to be 98.72% with initial
concentration of Bi(III) 250 mg/dm3 and other conditions like temperature,
agitation speed etc. were kept constant. Initially the rate of adsorption was very
fast, in 15 min the adsorption was 38.88% and in 90 min adsorption increases up
to 72.26%. Then after 240 min the adsorption of Bi(III) was found to be 98.72%
which remains constant thereafter. This may be due to availability of the all active
sites of adsorbent at the initial stage so rapid adsorption was observed and as the
time increased the repulsive forces increased due to adsorbed adsorbate. The
significant amount of 17.62 mg/g was adsorbed at 240 min which remained steady
for further increase in time (Fig. 4.3), so for further study 240 min time was kept
as fixed time.
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4.4.2 Effect of initial concentration of Bi(III)
Removal of Bi(III) was investigated with 250 mg/dm3 of Bi(III) for 240 min
agitation. As the initial concentration of Bi(III) was increased from 250 to 1000
mg/dm3 and the amount adsorbed was increased from 17.62 to 53.47 mg/g (Fig.
4.4, Table 4.3). The pH, temperatures as well as other conditions were kept
constant through out the study.
The removal of Bi(III) was found to be dependent on the initial
concentration, the amount adsorbed increased with increase in initial
concentration. Further, the adsorption was rapid in the early stages and then attains
an asymptotic value for larger adsorption time. The percentage removal of Bi(III)
decreases from 98.72 to 72.77% with an increase in initial Bi(III) concentration. It
may be due to an increase in the number of Bi(III) ions for the fixed amount of
CSAC. The amount of Bi(III) adsorbed per unit mass of activated carbon increases
with increase in Bi(III) concentration, this is due to the complete utilization of
adsorbent surface and active sites available which was not possible in low
concentration.
4.4.3 Effect of adsorbent dosage
The effect of adsorbent dosage was presented in Fig. 4.5 (Table 4.4) which
clearly indicates that the adsorption was quantitative with 700 mg CSAC dosage.
The study was carried out with 100 to 700 mg amount of adsorbent dosage with
250 mg/dm3 Bi(III) concentration and agitated for 240 min while other conditions
were kept constant. At the equilibrium 17.62 mg/g amount of Bi(III) was adsorbed
with 98.72 % maximum adsorption. As illustrated in Fig. 4.5, as the adsorbent
dose was increased from 100 to 700 mg the amount adsorbed and percentage
removal of Bi(III) was increased; this is due to increase in contact surface of
adsorbent particles and adsorption sites.
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4.4.4 Effect of agitation speed
The study was carried out by using orbital shaker under the controlled
temperature at 299 ± 2 K. The agitation speed for the Bi(III) was optimized by
varying rpm from 50 rpm to 200 rpm (Fig. 4.6, Table 4.5) when the concentration
of Bi(III) was 250 mg/dm3 and other conditions were constant. The removal of
Bi(III) became more quantitative with increase in rpm from 50 to 160 rpm with
98.72 % removal and it remained steady further, so 160 rpm was used throughout
study. At 50 rpm, the adsorption capacity was 12.81 mg/g and at 160 rpm it was
17.62 mg/g which was significant and remained constant further. The results show
that the speed of interaction played vital role and the contact between adsorbent
and adsorbate was significant at higher speed.
4.4.5 Adsorption isotherm
An adsorption isotherm, which describes the relation between the activity
of the adsorbent and the quantity of adsorbate on the surface at constant
temperature, is usually employed to describe adsorption. The L-shaped isotherm is
characterized by decreasing slope, as concentration of adsorbate increases since
vacant adsorption sites were decreased as the adsorbent gets covered. Such
adsorption behavior could be explained by the high affinity of the adsorbent for
the adsorbate at low concentrations, which then decreases as concentration
increases [48].
A variety of isotherm equations have been in use, some of which have a
theoretical foundation and some being of mere empirical nature. The adsorption
isotherm of Bi(III) adsorption on CSAC adsorbent is given in Fig. 4.7 (Table 4.6).
The Langmuir and Freundlich isotherm models were used for further study.
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4.4.6 Langmuir isotherm
The Langmuir model is probably the best known and most widely applied
adsorption isotherm. This model supposes a monolayer adsorption with a
homogeneous distribution of adsorption sites and adsorption energies, without
interactions between the adsorbed molecules. It has produced good agreement
with a wide variety of experimental data as discussed in chapter 2.
Further, the essential characteristics of the Langmuir isotherm can be
described by a separation factor or also called as dimensionless equilibrium
parameter, RL. In the present study, the computed values of RL are found to be
fraction as in the range of 0 to 1, indicating that the adsorption process is favorable
for the removal of Bi(III) ion by using CSAC adsorbent.
The adsorption of Bi(III) on CSAC follows the Langmuir isotherm model
for metal adsorption. For the experiment, the adsorbent dose was maintained 700
mg while the other conditions were kept constant. The plot of Langmuir isotherm
is shown in Fig. 4.8 (Table 4.7). The values of qm and KL have been evaluated
from the plot and results are given in Table 4.8. There was more correlation
between qm calculated value 53.47 mg/g and qm experimental value 54.35 mg/g.
The dimensionless parameter RL between 0.0305 to 0.7118 is consistent with the
favorable adsorption. The high value of correlation coefficient R2 indicates a good
agreement between the parameters and confirms the monolayer adsorption of
Bi(III) on the CSAC surface.
4.4.7 Freundlich isotherm
The Freundlich empirical model can be applied to non-ideal sorption on
heterogeneous surfaces as well as multilayer sorption which is discussed in
chapter 2 (2.4.8).
The values of Kf and n can be calculated from the intercept and slope (Fig.
4.9, Table 4.9) and presented in Table 4.10. The results showed that the adsorption
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fits better in the Langmuir equation. The equilibrium adsorption capacity
investigated from this isotherm which was found to be 17.62 mg/g while
experimental value was 13.41 mg/g, which was not good agreed.
4.4.8 Adsorption kinetics
Kinetics of sorption describes the solute uptake rate, which in turn governs
the residence time of sorption reaction. It is one of the important characteristics in
defining the efficiency of adsorption. The pseudo-first order equation (Lagergren
Equation) as given in chapter 2 (2.4.9) is applied here also. The rate constant k1 is
for the pseudo-first order adsorption process. The plot of log (qe - qt) vs. t (Fig.
4.10, Table 4.11) gives a linear relationship, from which k1 and qe can be
determined by using the slope and intercept of the plot, respectively.
Lagergren plot was studied with the adsorption of Bi(III) by CSAC dosage
of 700 mg with 250 mg/dm3 concentration of Bi(III) ion. At constant temperature
the Bi(III) was agitated with fixed 50 mL quantity and 160 rpm. The study was
made from 0 min to 240 min and removal was observed. The k1 and qe value for
the initial concentration of 250 mg/dm3 are found to be 0.66x10−3 min−1 and 16.17
mg/g. The true value of qe obtained from experiments was 17.78 mg/g. The
correlation coefficients for the pseudo first order kinetic model obtained at all the
studied concentrations were low.
The pseudo-second order adsorption kinetic rate equation was applied as
discussed in chapter 2 (2.4.9). The rate constant k2 (g mg-1min-1) of pseudo
second-order adsorption was determined from the plot of t/qt vs. t (Fig. 4.11, Table
4.12). The values obtained from graph for pseudo-first and pseudo-second order
models are given in Table 4.13. The results found that pseudo-second order was
more followed than the pseudo first order.
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4.4.9 Intraparticle diffusion study
The most commonly used technique for identifying the mechanism
involved in the sorption process is by fitting the experimental data in an
intraparticle diffusion plot. In intraparticle diffusion model, a good fit to the
experimental data reveals that the sorption rate is governed by intraparticle
diffusion and the intraparticle diffusion process is the rate-limiting step.
The kid (mg/g min1/2) value can be obtained from the slope of the plot of qt
(mg/g) versus t1/2 for bismuth ion from Fig. 4.12 (Table 4.14). The slope of the
linear portion of the plot has been defined as the intraparticle diffusion parameter
kid (mg/g min1/2). On the other hand, the intercept of the plot reflects the boundary
layer effect. The larger the intercept, greater is the contribution of the surface
adsorption in the rate limiting step. Higher values of the intraparticle parameters
illustrate an enhancement in the rate of adsorption [49]. However, these plots
indicated that the intraparticle diffusion was not the only rate controlling step
because it did not pass through the origin. The rate constant of intraparticle
diffusion is shown in Table 4.15. The intraparticle diffusion process is controlled
by the diffusion of ions within the adsorbent.
4.4.10 Effect of temperature
The adsorption of Bi(III) on CSAC at different temperatures from 303 to
323 K is shown in Fig. 4.13 (Table 4.16), the adsorption capacity increased when
the temperature was increased. The adsorption capacity increased from 54.90 to
59.09 mg/g for the initial concentration of 1000 mg/dm3 at pH 2.0. The increase in
adsorption capacity was due to the creation of active sites at higher temperature.
The thermodynamic parameters such as free energy (ΔG°) (kJ/mol),
enthalpy (ΔH°) (kJ/mol) and entropy (ΔS°) (J/k /mol) for adsorption of Bi(III) on
CSAC were determined. The ∆H○ and ∆S○ were obtained from the slope and
intercept of the Van’t Hoff’s plot of ln Kc vs. 1/T as shown in Fig. 4.14, Table
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4.17. Positive value of ΔH○ indicates that the adsorption process is endothermic.
The negative values of ΔG○ (Table 4.18) reflect the feasibility of the process and
the values become more negative with increase in temperature as well as it shows
that, the adsorption is highly favorable and spontaneous. The positive values of
standard ΔS° entropy (Table 4.18) show the increased disorder and randomness at
the solid solution interface of bismuth ion with CSAC. The enhancement of
adsorption capacity of the activated carbon at higher temperatures was attributed
to the enlargement of pore size and activation of the adsorbent surface. The
enrichment in the adsorption capacity may be due to the chemical interaction
between adsorbates and adsorbent, creation of some new adsorption sites or the
increased rate of intraparticle diffusion of Bi(III) ions into the pores of the
adsorbent at higher temperatures [50].
4.5 CONCLUSION
1) The adsorbent could be easily prepared from dry coconut shell which is
abundantly available as waste all over. It has developed as porous, effective
and economically affordable activated carbon which showed the maximum
percentage removal of Bi(III) i.e. 98.72 %.
2) The formation was confirmed with various characterizations like C, H, N, S
analyzer, SEM, FTIR and other properties.
3) This developed activated carbon is having the high capacity to adsorb Bi(III)
ions from aqueous solution with amount adsorbed from 17.62 mg/g to 53.47
mg/g with increase in the initial concentration up to 1000 mg/dm3 and the
required period was only 240 min.
4) The adsorption isotherm was followed with L shaped curve which indicate
the competition between adsorbent and adsorbate was less, so that the
adsorption was good.
Chapter 4
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194
5) The isotherm models such as Langmuir and Freundlich were also studied,
amongst them Langmuir equation shows more applicability to the
experimental data than Freundlich isotherm; as Langmuir isotherm gives
maximum adsorption capacity 54.35 mg/g.
6) The rate of adsorption was also investigated with kinetic study and it was
found that the experimental data fits better in pseudo second order than
pseudo first order with 0.978 as regression factor.
7) The adsorption was feasible, spontaneous and endothermic, which was
confirmed by the evaluation of thermodynamic parameters viz. ∆H○, ΔG○ and
∆S○.
Chapter 4
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ADSORBENTS
195
Table 4.1
Elemental analysis and properties of CSAC
Property Result
Ash content 12.62%
Bulk density 0.7685 gm/ cm3
Moisture content 6.75%
Carbon 59.23%
Hydrogen 3.41%
Sulphur 3.84%
Chapter 4
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ADSORBENTS
196
Table 4.2
Effect of time on removal, % and amount adsorbed mg/g of adsorption of Bi(III),
on CSAC.
Bi(III) =250 mg/g, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
Time, min Amount adsorbed, qt mg/g Removal of Bi(III), %
15 6.94 38.88
30 10.41 58.21
60 11.48 64.32
90 12.90 72.26
120 13.81 77.32
150 15.18 85.01
180 16.60 92.96
210 17.45 97.76
240 17.62 98.72
270 17.62 98.72
300 17.62 98.72
Chapter 4
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ADSORBENTS
197
Table 4.3
Effect of initial concentration of Bi(III) on amount adsorbed mg/g and removal, %
on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Initial conc. Bi(III)
mg/dm3
Amount adsorbed,
q mg/g
Removal of Bi(III), %
250 17.62 98.72
300 20.95 97.73
400 27.77 97.21
500 33.72 94.42
600 39.33 91.79
700 45.72 91.44
800 49.68 86.95
900 52.90 82.29
1000 53.47 74.86
Chapter 4
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ADSORBENTS
198
Table 4.4
Effect of adsorbent dosage on removal, % and amount adsorbed, mg/g of Bi(III)
Bi(III) = 250 mg/dm3, Time= 240 min, T= 299 ± 2 K, agitation speed= 160 rpm,
pH=2
CSAC mg Amount adsorbed,
q mg/g
Removal of Bi(III), %
100 13.86 11.09
200 14.32 22.91
300 14.57 34.97
400 15.72 50.29
500 16.69 66.52
600 17.31 83.09
650 17.56 92.34
700 17.62 98.72
Chapter 4
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ADSORBENTS
199
Table 4.5
Effect of agitation speed on removal, % and amount adsorbed, mg/g of Bi(III)
Bi(III)= 250 mg/g, Time= 240 min, T= 299 ± 2 K, CSAC =700 mg, pH=2
Agitation speed, rpm Amount adsorbed, q mg/g Removal of Bi(III), %
50 12.81 71.72
70 13.45 75.32
100 14.41 80.68
120 16.68 94.40
140 17.50 98.00
160 17.62 98.72
180 17.62 98.72
200 17.62 98.72
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
200
Table 4.6
Adsorption isotherm of Bi(III) adsorption on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Ce q
3.20 17.62
6.80 20.95
11.15 27.77
27.92 33.72
49.27 39.33
59.89 45.72
104.42 49.68
159.44 52.90
251.42 53.47
Chapter 4
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201
Table 4.7
Langmuir isotherm for adsorption of Bi(III) on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Ce Ce/q
3.20 0.1816
6.80 0.3246
11.15 0.4015
27.92 0.8280
49.27 1.2527
59.89 1.3099
104.42 2.1019
159.44 3.0140
251.42 4.7021
Table 4.8
Langmuir isotherm constant for adsorption of Bi(III) on CSAC
qm (mg/g)
KL(1/mg)
R2
54.350
0.1265
0.995
Chapter 4
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202
Table 4.9
Freundlich adsorption isotherm for adsorption of Bi(III) on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
log Ce log qe
0.5052 1.2461
0.8325 1.3212
1.0473 1.4436
1.4460 1.5279
1.6926 1.5947
1.7774 1.6601
2.0188 1.6962
2.2026 1.7235
2.4004 1.7282
Table 4.10
Freundlich constant for adsorption of Bi(III) on CSAC
Kf
n
R2
13.41
3.669
0.969
Chapter 4
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203
Table 4.11
Pseudo first order model for adsorption of Bi(III) on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
t min log (qe-qt)
0 1.2500
15 1.0350
30 0.08675
60 0.7994
90 0.6889
120 0.6628
150 0.4150
180 0.0719
210 -0.4815
Chapter 4
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ADSORBENTS
204
Table 4.12
Pseudo second order model for adsorption of Bi(III) on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
t t/qt
0 0
15 2.16
30 2.88
60 5.23
90 6.98
120 8.69
150 9.69
180 10.85
210 12.04
240 13.62
Table 4.13
Kinetic parameters for the adsorption of Bi(III) on CSAC
Pseudo first order Pseudo second order
qe exp.
(mg/g)
k1x10–3
(min–1)
qe calc.
(mg/g)
R2 k2 x10–3 qe calc.
(mg/g)
R2
17.62
0.66
16.17
0.869
2.159
18.62
0.978
Chapter 4
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ADSORBENTS
205
Table 4.14
Intraparticle diffusion for the adsorption of Bi(III) on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
t1/2 qt
3.873 6.94
5.477 10.41
7.746 11.48
9.487 12.90
10.955 13.81
12.248 15.18
13.417 16.60
14.491 17.45
15.492 17.62
Table 4.15
Study of intraparticle diffusion for adsorption of Bi(III) on CSAC
kid
(mg g−1min−1)
R2
0.880
0.976
Chapter 4
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ADSORBENTS
206
Table 4.16
Effect of temperature on amount of Bi(III) adsorbed on CSAC
Bi(III) = 1000 mg/dm3, Time= 240 min, CSAC=700 mg, agitation speed = 160 rpm, pH=2
T K Amount adsorbed, q mg/g
303 54.90
308 56.74
313 57.83
318 58.62
323 59.09
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
207
Table 4.17
Van't Hoff plot for removal of Bi(III) on WASAC
Bi(III) = 1000 mg/dm3, Time= 240 min, CSAC=700 mg, agitation speed= 160 rpm, pH=2
1/T lnKc
0.00330 1.1232
0.00324 1.1560
0.00319 1.1751
0.00314 1.1886
0.00309 1.1967
Table 4.18
Thermodynamic parameters for adsorption of Bi(III) on CSAC
T K ΔG○ kJ/mol ∆H○ kJ/mol ∆S○ J/mol k
303 -2.830
0.348
2.279
308 -2.960
313 -3.058
318 -3.143
323 -3.214
Chapter 4
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ADSORBENTS
208
Fig. 4.1
FTIR spectrum of CSAC
4000 3500 3000 2500 2000 1500 1000 50080
90
100
110
120
130
140
150
1034.86
1167.01
1608.48
1703.10
2899.463310.05
Tra
nsm
issi
on (
%)
Wavenumber (cm-1)
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
209
Fig. 4.2(a)
SEM image of CSAC
Fig. 4.2 (b)
SEM image of CSAC
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
210
0
20
40
60
80
100
0 100 200 300
Time, min
Re
mo
va
l of
Bi(
III),
%
0
4
8
12
16
20
Am
ou
nt
ad
so
rbe
d o
f B
i(III
), m
g/g
Fig. 4.3
Effect of time on removal, % and amount adsorbed, mg/g of Bi(III), on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
211
0
20
40
60
80
100
200 400 600 800 1000
Initial Conc. of Bi(III), mg/dm3
Rem
oval o
f B
i (III
),%
0
10
20
30
40
50
60
Am
ou
nt ad
so
rbed
of B
i(III
), m
g/g
Fig. 4.4
Effect of initial concentration of Bi(III) on amount adsorbed, mg/g and removal, %
of Bi(III)
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
212
0
20
40
60
80
100
0 200 400 600 800
Adsorbent dose, mg
Re
mo
va
l of
Bi(I
II), %
0
4
8
12
16
20
Am
ou
nt
ad
so
rbe
nt
of
Bi(
III),
mg
/g
Fig. 4.5
Effect of adsorbent dosage on removal, % and amount adsorbed, mg/g of Bi(III)
on CSAC
Bi(III) = 250 mg/dm3, Time= 240 min, T= 299 ± 2 K, agitation speed= 160 rpm,
pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
213
0
20
40
60
80
100
0 50 100 150 200 250
rpm
Re
mo
va
l of
Bi(
III),
%0
4
8
12
16
20
Am
ou
nt a
ds
orb
ed
of B
i(III)
, mg
/g
Fig. 4.6
Effect of agitation speed on removal, % and amount adsorbed, mg/g of Bi(III) on
CSAC
Bi(III) = 250 mg/g, Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
214
0
10
20
30
40
50
60
0 50 100 150 200 250 300
Ce mg/dm3
qe m
g/g
Fig. 4.7 Adsorption isotherm for Bi(III) adsorption on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
215
0
1
2
3
4
5
0 50 100 150 200 250 300
Ce
Ce/q
Fig. 4.8 Langmuir isotherm for adsorption of Bi(III) on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
216
1
1.2
1.4
1.6
1.8
2
0 0.5 1 1.5 2 2.5 3
log Ce
log
qe
Fig. 4.9 Freundlich isotherm for adsorption of Bi(III) on CSAC
Time= 240 min, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
217
-0.6
-0.3
0
0.3
0.6
0.9
1.2
1.5
0 50 100 150 200 250
t min
log
(q
e-q
t)
Fig. 4.10 Pseudo-first order plot for adsorption of Bi(III) on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
218
0
4
8
12
16
0 50 100 150 200 250 300
t min
t/q
t
Fig. 4.11 Pseudo-second order plot for adsorption of Bi(III) on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
219
0
5
10
15
20
0 5 10 15 20
t1/2
qt
Fig. 4.12 Intraparticle diffusion for adsorption of Bi(III) on CSAC
Bi(III) =250 mg/dm3, T= 299 ± 2 K, CSAC=700 mg, agitation speed= 160 rpm,
pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
220
50
52
54
56
58
60
300 305 310 315 320 325
T K
qe
Fig. 4.13 Effect of temperature on amount of Bi (IIII) adsorbed, mg/g on CSAC Bi(III) = 1000 mg/dm3, time= 240 min, CSAC=700 mg, agitation speed= 160 rpm, pH=2
Chapter 4
REMOVAL OF DYES AND HEAVY TOXIC METALS WITH ADSORPTION TECHNIQUE USING LOW COST
ADSORBENTS
221
1.1
1.12
1.14
1.16
1.18
1.2
1.22
0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335
1/T K
lnK
c
Fig. 4.14
Vant Hoff’s plot for adsorption of Bi(III) on CSAC
Bi(III) = 1000 mg/dm3, time= 240 min, CSAC=700 mg, agitation speed= 160 rpm, H=2
Chapter 4
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ADSORBENTS
222
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