Arab J Sci Eng (2017) 42:1545–1557

DOI 10.1007/s13369-017-2416-3

RESEARCH ARTICLE - CHEMICAL ENGINEERING

Equilibrium and Kinetic Studies of Hexavalent Chromium

Removal Using A Novel Biosorbent: Ruellia Patula Jacq
N. Saranya1 · E. Nakkeeran1 · S. Shrihari2 · N. Selvaraju1

Received: 12 August 2016 / Accepted: 14 December 2016 / Published online: 1 February 2017
© King Fahd University of Petroleum & Minerals 2017

Abstract The present work utilized Ruellia patula Jacq List of Symbols
leaves as biosorbent for hexavalent chromium removal. Sul-
furic acid modification was done and checked for enhanced G ◦ Gibbs free energy (kJ/mol)
biosorption capacity. Electron microscopy–energy-dispersive H ◦ Enthalpy (kJ/mol)
X-ray spectroscopy, Fourier transform infrared spectrome- S ◦ Entropy (kJ/mol K)
try, elemental analysis were performed for characterization Co Initial Cr(VI) concentration (mg/L)
of biosorbents. Batch experiments were conducted to opti- Ce Cr(VI) concentration in solution at equilibrium
mize contact time, solution pH, initial Cr(VI) concentration, (mg/L)
biosorbent dose, agitation speed and temperature for max- KL Langmuir isotherm constant (L/mg)
imum Cr(VI) removal. Also, the study attempted to show C Intraparticle diffusion model intercept
polyphenols present in the biosorbent reduce Cr(VI) through E Mean adsorption energy (kJ/mol)
adsorption. Equilibrium data were analyzed using Langmuir, ε Polanyi potential
Freundlich and Dubinin–Radushkevich isotherms. Mono- k1 pseudo-first-order constant (min−1 )
layer adsorption capacities of raw and acid-modified biosor- k2 pseudo-second-order constant (g/mg/min)
bents were found to be 37.03 and 62.50 mg/g, respectively. kc Distribution coefficient
Pseudo-second-order kinetic model suited well than other kF Freundlich constant (mg/g)/(mg/L)1/n
models like pseudo-first-order and intraparticle diffusion kid Intraparticle diffusion rate constant (mg/g/min1/2 )
models examined. Determination of H ◦ , S ◦ and G ◦ m Amount of biosorbent (g)
from thermodynamic studies showed that the biosorption n Adsorption intensity
is exothermic, stable and thermodynamically feasible. Des- q Amount of Cr(VI) adsorbed at time t(mg/g)
orption studies using NaOH as desorbing agent showed Q0 Monolayer adsorption capacity (mg/g)
considerable performances up to three cycles. These findings qe Amount of Cr(VI) ions adsorbed per unit mass of
revealed that Ruellia patula leaves serve as potent biosorbent biosorbent (mg/g)
for the removal of hexavalent chromium from aqueous solu- Qm Maximum adsorption capacity (mg/g) in D–R model
tions. R Atmospheric gas constant (8.314 J/mol K)
R2 Coefficient of determination of regression
Keywords Biosorption · Cr(VI) · Desorption · Kinetics · RL Separation factor
Polyphenols · Ruellia patula Jacq T Temperature (K)
V Volume of the solution (L)
B N. Selvaraju
selvaraju@nitc.ac.in
1 Department of Chemical Engineering, National Institute of 1 Introduction
Technology Calicut, Kozhikode, Kerala 673601, India
2 Department of Civil Engineering, National Institute of Industrial effluents release many pollutants among which
Technology Karnataka, Surathkal, Karnataka 575025, India heavy metals are considered as one of the major hazards to

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ecosystem. Heavy metals impose deleterious effects to flora
and fauna when exceeds permissible limit. Since chromium
appears to be peculiar due to its electronic configuration and
different oxidation states at different Eh-pH environments,
it is found to be highly reactive and hence toxic [1,2].
According to Bureau of Indian standards (2013), the max-
imum allowable limit of Cr is 0.05 mg/L. Plants and their
parts are being used as zero cost adsorbents for heavy metal
acquisition for the past decades owing to their abundant
availability, inbound lignocelluloses and phytochemicals,
which bear heavy metal capturing functional groups. Leaves
from several plant species like Mangifera indica [3], Nico-
tiana tabacum [4], Polyalthia longifolia [5], Tradescantia
pallida [6] and Caryota urens [7] were used as biosor-
bents for the removal of hexavalent chromium. Plant leaves
are structurally being composed of polysaccharide residues
such as celluloses, hemicelluloses and lignins collectively
called as lignocelluloses. These constituents have sugar moi-
eties along with certain functional groups like methoxyl
(–OCH3 ), phenolic hydroxyl (–C6 H5 –OH), aliphatic
hydroxyl (–CH3 –OH), carbonyl (–C=O–) that would pref-
erentially make interactions with cationic and anionic heavy
metal ions under suitable conditions of pH, temperature,
etc. Phytochemicals are plants’ secondary metabolites which
provide defense to plants against invading microbes. This
includes alkaloids, terpenoids, phytosterols, polyphenols and
saponins. These metabolites naturally contain certain inter-
active groups such as hydroxyl, carboxyl, sulfonate, thiol,
phosphate, amino, amido and imidazole groups that also
serve as sorption sites for heavy metal species in solutions
[8]. Polyphenols have 12–16 hydroxyl groups bounded upon
5–7 phenol groups out of 1000 daltons. Natural polyphenols
have been studied in water treatment as flocculants and as
biosorbents for the removal of heavy metals and dyes. They
may coagulate and decolorize water contaminated with the
synthetic dyes [9], chelate heavy metals and promote in situ
inactivation of heavy metal ions in waters [10,11]. Lignocel-
lulosic biosorbents in its native form are modified by either
physical or chemical means to increase removal capacity
through chemical functional groups [12,13]. Hence, the pres-
ence of lignocelluloses and enormous polyphenols in plants,
especially in leaves, made them suitable for the sequestra-
tion of heavy metals from aqueous solutions. Ruellia patula
Jacquin (synonym—Dipteracanthus patulus JACQ. NEES)
is a small hairy under shrub, distributed in Arabia, Africa,
Sri Lanka, India and Myanmar. R. patula is being used in the
treatment of gonorrhea, syphilis, eye sores, renal infection,
cough, wounds, toothache, stomach ulcers [14–16]. Studies
on Ruellia patula jacq revealed that it is naturally composed
of several cellulosic constituents like lyoniresinol-9’-o-β-
d-glucoside, 5,5-dimethoxy-lariciresinol-9-o-β glucopyra-
noside, β-sitosterol, lupeol, α-ethyl galactose, apiginin-7-o-
rutinoside, α-d-glucose, β-d-glucose and β-Dfructose [17]
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Arab J Sci Eng (2017) 42:1545–1557
and phytochemicals like ascorbic acid, phenolic compounds,
tannin, lycopene, carotenoid and α-tocopherol [18]. Fur-
thermore, the leaves have been demonstrated to contain
antioxidant and reducing properties [19] which can be
exploited for the removal of toxic heavy metals from aqueous
solutions. The focus of the present study is to investigate, for
the first time, Cr(VI) biosorption from aqueous solution using
untreated and chemically treated Ruellia patula leaves. The
influence of different parameters on adsorption of chromium
was determined by performing batch experiments. It has
to be highlighted that the role of polyphenols upon Cr(VI)
detoxification was also analyzed using gallic acid and pyro-
gallic acids as standards. Kinetic and equilibrium parameters
were determined to study the biosorption mechanisms and
rate-limiting steps. Attempts were also made to check the
regeneration capacity of the biosorbent by desorption exper-
iments.
2 Materials and Methods
2.1 Biosorbent Preparation Through Modification
Dried leaves of Ruellia patula Jacq collected from Tamil
Nadu, India, were used as biosorbent. The leaves were
cleaned up with deionized water, shade dried for 4 days,
oven dried at 80 ◦ C for 6 h and pulverized using a blender
and sieved through different meshes using a sieve shaker.
Four different sized microparticles ranges from 0.075 to 0.08,
0.08 to 0.09, 0.09 to 0.106 and 0.106 to 0.125 mm were
obtained in a bulk quantity and kept in airtight plastic con-
tainers, called as RPJL. Pretreatment modifies the functional
groups on the biosorbent surface by removing impurities or
introducing new binding sites on them. Microparticles of
different sizes were allowed to contact with 50 mL of 10%
H2 SO4 solution at 35 ◦ C rotated at 100 rpm in a rotary shaker
(model GeNei, SLM-INC-OS-250, India) for 12 h. Then, the
acid-modified leaf microparticles (AML) were washed with
deionized water, dried and analyzed for removal of hexava-
lent chromium.
2.2 Stock Solution
A stock chromate solution of 1000 mg/L is prepared by dis-
solving potassium dichromate salt (AR grade) in deionized
water. Working solutions of 50, 100, 150, 200 and 250 mg/L
were prepared by appropriately diluting the stock solution.
2.3 Characterization of Biosorbent
Elemental composition of RPJL and AML was done using
CHNS Analyzer (Vario EL III, Elementar, Germany). Data
regarding porosity and surface area of raw and acid-
Arab J Sci Eng (2017) 42:1545–1557
modified biosorbent were determined using mercury intru-
sion porosimeter (Quantachrome ASAP 2200, Micromerit-
ics, USA). Surface morphologies of RPJL and AML were
analyzed using scanning electron microscope (SEM) (JSM—
6390LV, JEOL, USA) before and after chromium loading.
Cr(VI) binding on the surface active groups of RPJL and
AML was predicted by EDX (JED2300-JEOL, USA). Func-
tional groups involved in biosorption with both the samples
before and after adsorption were predicted using FTIR spec-
trophotometer (Jasco 1033, FT/IR-4700 type A, India) in the
range of 400–4000 cm−1 . Zero point charge of the biosorbent
was determined as per [7] to evaluate the point at which the
sorbent would participate in anion exchange reactions. Total
polyphenols present in RPJL and AML were estimated by
standard Folin–Ciocalteu method with gallic acid as a stan-
dard using UV–visible spectrophotometer at 765 nm [20].
2.4 Biosorption Studies
Batch studies were allowed to take place in 250-mL stoppered
conical flasks with 50 mL working solutions. The contents of
the flasks were uniformly mixed by rotating in the rotary
shaker at 100 rpm and at ambient temperature. Effect of
biosorbent size, biosorbent dose, pH, temperature, time of
contact, agitation speed and initial chromium concentration
on biosorption were evaluated for both RPJL and AML. pH
adjustments were done using 0.1 mol/L HCl and 0.1 mol/L
NaOH solutions with the aid of digital pH meter. Filtrate was
collected using Whatman filter paper (No. 1) after equilib-
rium. Unadsorbed chromium in the filtrate was measured in
terms of purple color formed when the solution was allowed
to react with 1,5-diphenyl carbazide in an acidic environment
using a UV–visible spectrophotometer (model PerkinElmer,
Lambda 650, USA) at 540 nm. Analytical grade chemicals
and reagents were used throughout the study.
The amount of Cr(VI) adsorbed at time ‘t’ and percentage
removal of chromium were computed [21] according to the
following equations:
(C0 − Ct ) V
qt = (1)
m
where qt is the adsorption capacity at time ‘t’ (mg/g), C0
is the initial Cr(VI) concentration (mg/L), Ct is the Cr(VI)
concentration (mg/L) at time t, ‘m’ is the adsorbent weight
(g) and V is the volume of the Cr(VI) solution (L). Percentage
removal of Cr(VI) was calculated as:
 
Co − Ce
%Removal = × 100 (2)
Co
1547
2.5 Effect of Polyphenols
To study the influence of polyphenols upon reduction of
chromium ions, the biosorbent was extracted with 98%
methanol at an elevated temperature of 70 ◦ C in a stoppered
conical flask with mild shaking. It is ultrasonicated at 15 KHz.
The mixture is centrifuged (model REMI R-8C, India) at
2000 rpm for 20 min, supernatant was discarded and the
biosorbent was collected as pellets. It was then washed with
deionized water several times to remove excess methanol,
oven dried to remove excess moisture and batch studies were
carried out for the hexavalent chromium removal [22].
2.6 Desorption-Regeneration Capacity
The extent of efficiency of a biosorbent lies in its regen-
eration capacity which is vital for the commercialization
of biosorption in industrial scale in removing heavy metals
from complex wastewater. Successive adsorption-desorption
experiments were carried out to examine the reutility of RPJL
and AML, up to three runs. 0.1 N NaOH is used as a des-
orbing agent and checked for expulsion of chromium ions up
to 24 h. More over the desorption percentage was computed
from the following equation [23],
Cdes
%Desorption = × 100 (3)
Cads
where Cdes and Cads are the concentration of chromium ions
during desorption and adsorption at time ‘t’ (mg/L), respec-
tively.
3 Results and Discussion
3.1 Physicochemical Characterization
Zero point charge was calculated for the raw biosorbent to
determine how easily the biosorbent can adsorb Cr(VI) ions.
The zero point charge was determined as pH 2.0 showed that
the surface charge of RPJL will be positively charged at pH
value of less than 2.0 [24], thus attracting chromium anions
below this pH.
The results of elemental analysis for both RPJL and AML
using CHNS analyzer are shown in Table 1.
Percentage of carbon after acid modification was increased
from 35.37 to 39.12 and percentage of sulfur increased from
0.32 to 4.77, whereas there is a slight increase in the hydro-
gen and nitrogen content after acid modification. Increase
in C and S thought to preferentially involves in the biosorp-
tion process in the form of carbonyl, carboxyl, sulfhydryl,
sulfate or sulfonate group which are major biosorption sites
for anionic HCrO− 4 ions. The increase in intruded volume
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Table 1 Physicochemical characterization of RPJL and AML (a) 125

RPJL before adsorption
Parameters RPJL AML RPJL after adsorption

C% 35.27 39.12 100

H% 5.35 7.27

% Transmittance
N% 3.36 3.32
S% 0.32 4.77
75
Total intruded pore volume (cc/g) 0.6097 0.9533
Total surface area (m2 /g) 0.3028 0.5247
pHZPC 2.0 2.0
50
Total polyphenols (μg/mL) 323 324.11

25
0 500 1000 1500 2000 2500 3000 3500 4000
from 0.6097 to 0.9533 cc/g and increase in total surface area
Wavenumber (Cm-1)
from 0.3028 m2 /g to 0.5247 m2 /g describe that H2 SO4 treat-
ment modified the biosorbent considerably which enhance
the rate of biosorption (Table 1). Total polyphenols of RPJL (b) 125 AML before adsorption
were found to be 323 μg/mL of extract. Same results were AML after adsorption
obtained by [25] in his work on evaluation of antimicro-
100
bial and antioxidant activity study on Ruellia patula Jacq.
AML has a polyphenol content of 324.11 μg/mL of extract
% Transmittance

that denotes the acid modification (10%) did not altered the 75
polyphenol content of the biosorbent. These findings rep-
resents that the biosorbent is polyphenol rich constituting
several OH− groups that readily binds and reduce Cr(VI) 50

ions.
FTIR spectrum reveals the functional groups involved in
the chromium binding. The complex spectra of RPJL in
Fig. 1a show several strong absorption bands.
The presence of broad peak at 3420.31 cm−1 depicts the
presence of O–H stretch of H– bonded alcohols or phenols.
The shift of the peak at this point after adsorption revealed
the involvement of –OH groups of alcohols or phenols [26].
Disappearance of peak at 2994.52 after adsorption clearly
confirms the involvement of C–H stretch of alkanes. Peak
at 2323.52 corresponds to O–H stretch of carboxylic acids
and the absence of the peak after adsorption shows that car-
boxylic acids involved strongly in Cr(VI) binding. A sharp
peak at 1391 cm−1 before adsorption corresponds to S=O,
sulfate or sulfhydryl groups, and disappearance after adsorp-
tion shows the involvement of those groups in biosorption or
reduction. Peak at 1348.83 cm−1 before adsorption shifted to
1357.045 cm−1 directly represented the participation of N–O
symmetric stretch of nitro compounds present in RPJL. Peak
at 931.25 cm−1 is the indication of O–H bend of carboxylic
acids, and it is shifted to 882.69 cm−1 after adsorption. Peak
at 882 cm−1 corresponding to Cr(VI) of potassium dichro-
mate [27] clearly reveals that adsorption of Cr(VI) took place
with hydroxyl bends of carboxylic acids. Hence, the predom-
inant functional groups of RPJL that involved in biosorption
are found to be hydroxyl, sulfhydryl, nitro and C–H stretches
of alkanes. FTIR spectrum of AML is shown in Fig. 1b.
25
0
0 500 1000 1500 2000 2500 3000 3500 4000
-1
Wavenumber (Cm )
Fig. 1 a FTIR peaks of RPJL before and after chromium adsorption.
b FTIR spectra of AML before and after chromium adsorption
Appearance of sharp peaks at 1070.67 and 2711.35 cm−1
indicated the existence of –OH stretch of carboxylic acids.
Involvement of =C–H stretch of alkenes is clearly depicted
by the disappearance of medium peak at 3183.76 cm−1 .
Hence, it is clear that hydroxyl groups impregnated on the
surface of the AML were involved in chromium ion binding.
SEM images of RPJL and AML are shown in Fig. 2.
Porous and striated structure of RPJL showed that the sur-
face is complex and prone to metal binding (Fig. 2a). After
acid modification, the surface is shown to be heterogeneous
and more complex with several ups and downs compared to
RPJL (Fig. 2c). Hence, it is clear that H2 SO4 modification of
RPJL introduced many functional groups upon the surface
of biosorbent suitable for metal binding [28]. Figure 2b, d
depicts the impregnation of Cr ions over the striated and hol-
low surface of AML. So, the morphological study of RPJL

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Arab J Sci Eng (2017) 42:1545–1557 1549

Fig. 2 SEM–EDX images of a RPJL before adsorption, b RPJL after adsorption, c AML before adsorption, d AML after adsorption

confirms that it is suitable for sequestration of Cr(VI) ions by
adsorption process. EDX analysis did not show any distinct
peaks of Cr loaded in RPJL and AML before adsorption
(Fig. 2a, c), whereas after adsorption the spectrum clearly
showed incidence of Cr upon both the sorbent surfaces (Fig.
2b, d).
3.2 Effect of Biosorbent Size and Dose
Different sized biosorbents were analyzed for the removal
of Cr(VI) at 180 min contact time, 303 K temperature, pH
1.0, 100 rpm agitation speed and 0.1 g biosorbent. The results
indicated that the adsorption capacity increased rapidly when

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1550
110
100
% Removal of Cr(VI)
90
80
70
60
50
0.00 0.05 0.10 0.15 0.20
Biosorbent dose(g)
Fig. 3 Effect of biosorbent dose on Cr(VI) removal percentage
the biosorbent size decreases. Surface area increases when
the biosorbent size decreases [29]. Functional groups present
upon the biosorbent surface expose more with increase in sur-
face area, thus prone to sorbate binding. Therefore, smaller
sized biosorbent particles with their greater surface area
were found to be reliable for increased biosorption capacity.
Hence, 0.075- to 0.08-mm-sized RPJL and AML parti-
cles were selected for further studies because of their high
removal efficiency.
Removal of Cr(VI) was studied by varying the biosorbent
dosage from 0.05 to 0.3 g in 50 mL of 50 mg/L initial Cr(VI)
concentration with 303 K, pH 1.0 and 100 rpm for 180 min.
The optimum dose of biosorbent for RPJL was found to be
0.2 g with a maximum removal of 96.76%, whereas for AML
it was 0.15 g with 99.6% removal. This is an evident that
the acid modification had introduced more functional groups
upon the biosorbent. The percentage biosorption increased in
a gradual manner and attained its maximum at 0.3 g for both
unmodified and acid-modified forms of biosorbent (Fig. 3).
3.3 Effect of Contact Time on Biosorption
Contact time between sorbent and ligand plays a vital role
in driving the biosorption process [30]. The biosorption effi-
ciency of Cr(VI) increased gradually at a slower rate until
160 min is reached and attained saturation after that. This
may be attributed to coverage of free sites of adsorbents by
Cr(VI) ions and made them unavailable for further adsorp-
tion. So, the optimum contact time for the experiments was
selected as 160 min.
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Arab J Sci Eng (2017) 42:1545–1557
30
AML
RPJL AML
RPJL
Adsorption capacity (mg/g)
20
10
0
0 1 2 3 4 5 6 7 8
0.25 0.30 0.35 pH
Fig. 4 Influence of pH on adsorption capacity of RPJL and AML
3.4 Effect of pH
pH tends to be a typical parameter in adsorption studies as it
influences the speciation of pollutants.
As shown in Fig. 4, maximum adsorption capacity was
obtained at pH 1.0, then slowly decreased up to pH 4.0 and
attained minimum at a pH above 4.0. Similar kind of results
and the reason pertaining to such behavior were reported by
many researchers in this context [31,32]. At high pH, electro
negativity prevails on the surface of the biosorbents. But the
predominant form of Cr(VI) species in solution is of Cr2 O2−7
and HCrO− 4 ions which tend to repel off from the sorbent
surface. Hence, reduction in Cr(VI) is not possible at high pH
as observed. On the other hand, low pH environment makes
the biosorbent get protonated, which preferentially attract
Cr(VI) anions. Therefore, pH 1.0 was found to be suitable
for the experiments.
3.5 Effect of Initial Concentration
Figure 5a, b shows the effect of initial Cr(VI) concentration
(50–250 mg/L) on the adsorption capacity of the biosorbents
at various time. The biosorption capacity gradually rose up
and attained equilibrium exactly at 120 min as shown in
Fig. 5. After that, no considerable increment was found for
each concentration. When the concentration of Cr is high, a
gradient develops between sorbent and Cr ions which serves
as potential driving force for exchange of ions, whereas the
removal percentage of Cr(VI) decreased with an increase
in Cr(VI) concentration from 50 to 250 mg/L owing to a
quick exhaustion of the adsorption sites and a charge balance
between the active functional groups and Cr(VI) ions [33].
Arab J Sci Eng (2017) 42:1545–1557 1551

(a) 30
40 AML
50 mg/L
25
RPJL
35 100 mg/L
150 mg/L

Adsorption capacity (mg/g )

200 mg/L
Adsorption Capacity (mg/g)

30
250 mg/L 20

25
15
20

15 10

10
5

5
0
0 300 305 310 315 320
0 20 40 60 80 100 120 140 160 180 Temperature (K)
Contact time (mins)
Fig. 6 Effect of temperature on chromium adsorption by AML and
RPJL
(b) 70
50 mg/L
60 100 mg/L
150 mg/L
adsorption sites accessible for the metal ions. Higher agita-
200 mg/L tion speed lowered the biosorption capacity due to occupation
Adsorption capacity (mg/g)

50 250 mg/L
or utilization of all biosorption sites of RPJL and AML [34].
Also there is the higher chance of desorption that could take
40
place at high speed. Based on the study results, 100 rpm was
selected as optimum speed for better Cr(VI) removal.
30

20 3.7 Reducing Effect of Polyphenols

10 Experiments were done with methanol-extracted biosorbent

0 acid at 50 mg/L chromium concentration, 100 rpm, pH 1.0
0 20 40 60 80 100 120
Contact time (mins)
Fig. 5 Effect of initial concentration on Cr(VI) removal at various con-
tact time for a RPJL and b AML (at 303 K, 100 rpm, pH 1.0)
3.6 Effect of Temperature and Agitation Speed
The effect of temperature on the biosorption of Cr(VI)
was studied at optimal conditions with a rotation speed of
100 rpm, and the results are shown in Fig. 6.
At 303 K, the biosorption was found to attain equilibrium
and the extent of increase above 303 K was significantly small
and not appreciable. Even a slight decrease above 315 K may
be due to the excitation of ions which made them to bounce
out of the adsorption site. Hence, 303 K was fixed as optimum
temperature for both RPJL and AML biosorption studies.
Percentage of Cr(VI) biosorbed at different agitation speed
from 50 to 250 rpm was determined. It is clear that at 100 rpm,
99% of Cr(VI) showed the speed is optimal enough to make
and pure polyphenols, namely gallic acid and pyrogallic
140 160 180
and 303 K temperature, in order to understand the effect of
polyphenols in heavy metal removal. The polyphenol con-
tent in the methanol-extracted RPJL is estimated by Folin’s
method and found to be 2.34 μg/mL of extract which is
comparatively lower than that of the raw and acid-modified
biosorbent.
Figure 7 clearly shows that gallic acid and pyrogallic acid
produced 90% Cr(VI) removal as soon as they contacted with
the hexavalent chromium solution and reached almost 100%
within 20 min. This is due to the fact that gallic acid and pyro-
gallic acid contain several hydroxyl groups in their structure
which readily bind with the anionic Cr(VI) ions and reduce
them. Raw biosorbent removed only 40% of the Cr(VI) ions
at 20 min and 95% removal was achieved only at the end
of 120 min. However, the polyphenol-extracted biosorbent
showed mere 1.61% removal even after 160 min owing to the
non-availability or transformation of hydroxyl and metal cap-
turing functional groups present over the biosorbent. These
observations are consistent with results observed in the study
of hexavalent chromium removal using tobacco leaves by [4]

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1552 Arab J Sci Eng (2017) 42:1545–1557

100 it is unfavorable and the process is irreversible if RL = 0.

Linearization of equilibrium data was performed by plotting
Ce /qe versus Ce .
80
From Table 2, the coefficient of determination of RPJL
Gallic acid and AML was found to be very high, depicted that monolayer
Pyrogallic acid coverage of Cr(VI) ions over the biosorbent surface.
% Cr(VI) removal

60
40
20
0 tion process takes place on heterogeneous surface [39].
0 20 40 60 80 100
Contact time (mins)
Fig. 7 Effect of polyphenols on biosorption of Cr(VI)
and [35] in their studies on gallic acid as agents for hexavalent
chromium removal. Hence, polyphenols in the biosorbent
have good reducing properties that readily detoxify hexava-
lent chromium within a short span of time. The sequential
steps of polyphenol and metal ion interaction can be stud-
ied by GCMS, LCMS, XRD or high throughput molecular
techniques.
3.8 Biosorption Isotherms
Insights of the biosorption process were analyzed with
the equilibrium data obtained, using the following two
parameter models like Langmuir, Freundlich and Dubinin–
Radushkevich models.
The Langmuir isotherm is meant for monolayer adsorp-
tion taking place over a even homogeneous adsorbent surface
[36].
Q 0 K L Ce
qe =
1 + K L Ce
where Ce is equilibrium concentration of the ionic species
(mg/L), qe is the equilibrium adsorption capacity (mg/g), Q0
represents the monolayer adsorption capacity (mg/g), and KL
is the Langmuir isotherm constant (L/mg).
Separation factor, RL , is defined by the following equa-
tion:
1 constants were calculated and are shown in Table 2. However,
RL =
1 + kL C 0
where C0 is the initial Cr(VI) concentration (mg/L) [37]. If
0 < RL < 1, the adsorption may be favorable, while RL = 1
Raw biosorbent
Sorbent without
The monolayer adsorption capacity for Cr(VI) removal
polyphenol by RPJL and AML was 37.03 and 62.50 mg/g, respectively.
Low value of K L , viz. 0.168 and 0.113 L/mg indicated the
high affinity of Cr(VI) ions toward RPJL and AML. The RL
values indicated that the biosorption process is favorable by
both unmodified and acid-modified biosorbents, and process
is found to be reversible [38].
The Freundlich model describes that multilayer adsorp-
120 140 160 180
Freundlich isotherm model can be written as
1
qe = K F Cen (6)
where K F is the Freundlich constant (mg/g)(L/mg)1/n and
n is the Freundlich exponent (dimensionless) which defines
extent of linearity of the adsorption. Eq. (5) was linearized,
and constants K F and n were determined. From Table 2, K F
values are found to be 10.715 and 22.54 and n F values were
3.745 and 5.208, respectively, for RPJL and AML. R 2 values
indicated that Freundlich isotherm represents a least fit to the
equilibrium data which represents multilayer adsorption is
not the predominant process taken place.
The Dubinin–Radushkevich (D–R) isotherm model is
given by [40]
qe = Q m exp−K ε
2
(7)
where Q m is the maximum adsorption capacity (mg/g), and
K is the activity coefficient (mol/J). ε is the Polanyi poten-
tial, equal to RT (ln(1 + (1/Ce )), R (J/mol K) is the universal
gas constant and T is the absolute temperature (K). The sig-
nificance of applying D–R model is to determine apparent
adsorption energy, E (kJ/mol) which is given by
(4)
1
E=√ (8)
2k
Plot of log (qe ) versus ε2 gives Q m and K values. If 1 < E <
16 kJ/mol, the process is said to be physical adsorption, and
if the value is greater than 16 kJ/mol, it may be a chemisorp-
tion. If E lies between 8 and 16, then ion exchange may be the
predominant mechanism [41]. The Dubinin–Radushkevich
(5)
the value of E for RPJL and AML was found to be 2.236 and
40.824 KJ/mol, respectively. This clearly showed that chemi-
cal modification had intensified the biosorption process from
physisorption to chemisorption. Regression analysis showed

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Table 2 Isotherm parameters

Models Parameters RPJL AML
for Cr(VI) removal by RJPL and
AML at various Cr(VI) Langmuir Q 0 (mg/g) 37.03 62.50
concentrations
K L (L/mg) 0.168 0.113
RL for various C0 (mg/L)
50 0.106 0.150
100 0.056 0.081
150 0.038 0.055
200 0.028 0.042
250 0.023 0.034
R2 0.999 0.932
Freundlich K F (mg/g)(L/mg)1/n 10.715 22.540
nF 3.745 5.208
R2 0.927 0.911
Dubinin–Radushkevich model Q m (mg/g) 9.817 16.33
K (mol2 /J 2 ) 1 × 10−7 3 × 10−10
E(kJ/mol) 2.236 40.824
R2 0.739 0.769

Table 3 Kinetic parameters of RPJL and AML

C0 (mg/g) Pseudo-first-order Pseudo-second-order Intraparticle diffusion
k1 (min) qe (mg/g) R2 k2 (g/mg/ min) qe (mg/g) R2 kid (mg/g/min1/2 ) C (mg/g) R2

RPJL
50 0.0092 4.207 0.797 0.00154 15.62 0.96 1.002 0.676 0.96
100 0.0092 3.837 0.858 0.00015 45.45 0.967 1.988 −1.643 0.935
150 0.0092 3.435 0.829 0.00017 47.61 0.964 2.499 −2.845 0.941
200 0.0069 3.235 0.877 0.00007 76.92 0.977 2.901 −3.095 0.901
250 0.0046 2.09 0.763 0.00004 100 0.961 3.156 −3.599 0.731
AML
50 0.005 2.032 0.942 0.001 20.83 0.993 1.101 3.069 0.983
100 0.005 2.133 0.919 0.0005 40 0.994 2.163 2.77 0.982
150 0.007 3.083 0.911 0.0002 62.5 0.991 3.377 −0.951 0.967
200 0.009 3.689 0.922 0.0001 83.33 0.992 4.36 −4.224 0.987
250 0.009 4.518 0.919 0.0001 125 0.994 5.884 −10.85 0.99

a low value for this model since multi-linearity resulted. k1

Therefore, the Dubinin–Radushkevich equation represents
the least fit to the experimental data.
3.9 Adsorption Kinetics
Adsorption kinetic studies are important to determine the effi-
cacy of adsorption. Pseudo-first-order, pseudo-second-order
and intraparticle diffusion models have been widely used to
study the rate-limiting step of the adsorption process.
The pseudo-first-order kinetic model in its linearized form
is given in the following form as
log(qe − q = logqe − t (9)
2.303
where adsorption capacity (mg/g) at time t (s), qe , is
the equilibrium adsorption capacity (mg/g) and K 1 is the
pseudo-first-order equilibrium rate constant (min−1 ). Table 3
presents the kinetic parameters of all the three kinetic models
examined.
Due to boundary layer limitations, pseudo-first-order
model had a least fit to the equilibrium data. Calculated qe
values did not match with the experimental values. R 2 val-
ues of RPJL and AML were found in the range from 0.974 to
0.763, which seem to be comparatively lower than the other
kinetic models, representing the unsuitability of this model.

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1554 Arab J Sci Eng (2017) 42:1545–1557

16 ilar behavior was observed by [42] in his kinetics studies

(a)
on Uncaria gambir for copper removal. The R 2 values
14 50 mg/L
100 mg/L for pseudo-second-order model were comparatively higher,
12
150 mg/L for all the experimental conditions examined. Hence, the
200 mg/L
250 mg/L adsorption process of Cr(VI) by RPJL and AML followed
10 chemisorption involving valence forces through exchange or
t/q t (min.g/mg)

sharing of electrons.
8
Intraparticle diffusion model is given by the following
equation
6

4 qt = K id t 1/2 + C (11)

2 where kid is the intraparticle diffusion rate constant

(mg/g/min1/2 ), C is the intercept. The qe values were not
0 well correlated with those of the calculated values. R 2 values
0 20 40 60 80 100 120 140 160 180
are comparatively low with respect to first order and second
Time (mins)
order kinetic models. For the process to be completely con-
(b) trolled by the intraparticle diffusion model, the plot between
10 ‘t 1/2 ’ and ‘qt ’ has to fit and pass through the origin. But the
50 mg/L plot did not passed through origin and showed a multi-linear
100 mg/L
150 mg/L curve which clearly depicts that intraparticle diffusion is only
8 200 mg/L a part of the adsorption, proceeding with multiple steps, and
250 mg/L
thus could not be considered as a sole rate-limiting step [43].
t/q t (min.g/mg)

Pseudo-second-order model represents a best fit than the

6
other models examined with a higher R 2 values; hence, it
is clear that the adsorption process followed chemisorption
rather than diffusion.
4

3.10 Thermodynamics of the Biosorption Process

2
Calculation of change in Gibbs free energy (G ◦ ), enthalpy
0 20 40 60 80 100 120 140 160 180
(H ◦ ) and entropy (S ◦ ) predicts about spontaneity of the
Time (mins) reaction, heat of reaction and degree of randomness at the
interface between the contacting species. The equations for
Fig. 8 a Pseudo-second-order plot for RPJL. b Pseudo-second-order calculating those parameters are as follows:
plot for AML
G o = −RT ln K C (12)
The pseudo-second-order kinetic model expression is as
where ‘T ’ is absolute temperature (K) and ‘R’ is universal
follows:
gas constant (8.314 J/mol/K), and Kc is the distribution coef-
t 1 t ficient given by
= 2
+ (10)
qt K 2 qe qe H o S o
ln KC = − + (13)
RT R
where k2 (g/mg/min) is the pseudo-second-order constant. qe
Figure 8a, b represents the linear form of the pseudo-second- KC = (14)
Ce
order kinetic model at Cr(VI) concentrations of 50, 100, 150,
200 and 250 mg/L, respectively. The thermodynamic parameters calculated from the anal-
The experimental and calculated qe values were well ysis are given in Table 4.
correlated and the kinetic rate constant decreased with the Increase in the G ◦ values with the consequent increase
increase in the concentration of Cr(VI) for both RPJL and in temperature for both the biosorbents clearly shows that
AML, which are given in Table 3. This behavior is mainly the reactions are spontaneous and energetically favorable at
attributed to the decrease in the adsorption sites on the lower or optimum temperatures. Above 308 k, the adsorp-
biosorbent with the increase in Cr ion concentration. Sim- tion upon RPJL is not spontaneous and less favorable due

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Arab J Sci Eng (2017) 42:1545–1557 1555

Table 4 Thermodynamic parameters of RPJL and AML for the removal of Cr(VI)
Co (mg/L) T (K) RJPL AML
G ◦ (kJ/mol) S ◦ (kJ/molK) H ◦ (kJ/mol) G ◦ (kJ/mol) S ◦ (kJ/molK) H ◦ (kJ/mol)

50 303 −4.107 −0.335 −105.521 −11.983 −0.304 −103.62

308 −2.1864 −8.832
313 0.076 −8.267
318 0.699 −7.138

Table 5 Comparison of
Leaf biosorbents pH Qe (mg/g) References
adsorption capacities of various
leaf biosorbents with RPJL and Azadirachta Indica 5.5 8.812 (45)
AML for Cr(VI) removal
Euclea schimperi 2.0 3.94 (46)
Erythrina Variegata Orientalis 3.0 1.72 (47)
Polyalthia longifolia (acid treated) 3.0 5.128 (34)
Pineapple leaves 2.0 18.77 (48)
Leersia hexandra Swartz 2.0 28.64 (49)
Ficus carica 3.0 13.41 (50)
Ficus auriculata 2.0 13.33 (51)
Ruellia patula jacq 1.0 37.03 (RPJL) This study
62.50 (AML)

to the increased randomness, while adsorption upon AML 4 Conclusions

is found to be favorable. The negative H ◦ values of RPJL
and AML indicated that the process is exothermic favorably.
Negative S ◦ value represents decrease in the randomness at
the interface between sorbent and sorbate during the adsorp-
tion process clearly implies process of Cr(VI) upon sorbent
surface is associative and stable [44]. Similar results were
reported by [45] on neem leaves.
3.11 Desorption Studies
Repeated adsorption–desorption experiments were performed
to examine the regeneration capability of RPJL and AML.
Biosorption–desorption cycles of Cr(VI) repeated up to three
runs for 24 h at 100 rpm and 303 K. Maximum desorption and
equilibrium attained at about 12 h. Adsorption experiments
were done with 50 mg/L Cr(VI) solution at 1.0 pH, 303 K and
100 rpm. The percentage of desorption of Cr(VI) from AML
was 42.12, 39.05 and 29.47, whereas from RPJL was 33.81,
19.15 and 14.73 for the 1st, 2nd and 3rd cycles, respectively.
The decrease in the desorption percentages of Cr(VI) ions
from the biosorbents might be due to the heterogeneity of the
surface after being repeatedly encountered by Cr ions. The
adsorption percentages after regeneration of the biosorbent
were found to be 87.04, 59.14, 48.85 for AML and 80.67,
49.33, 39.80 for RPJL, respectively. There was no consider-
able desorption and adsorption performances after third cycle
for both AML and RPJL owing to unavailability of binding
sites.
Adsorption of hexavalent chromium onto raw and acid-
modified leaves of Ruellia patula Jacq has been studied
in detail. Total polyphenol content in the leaves found to
be 325 μg/g of biosorbent showed that the sorbent has
rich reducing property naturally. It was found that max-
imum adsorption had taken place at pH 1.0, adsorbent
dose 0.15–0.20 g for 50 mL of 50 mg/L chromium solution
at a contact time of 120 min and agitation speed 100 rpm
for unmodified and acid-modified sorbents. Langmuir, Fre-
undlich and Dubinin–Radushkevich isotherm models were
used to explain the biosorption phenomenon. The order of
fit in relation to coefficient of correlation was Langmuir >
Dubinin–Radushkevich >Freundlich. Monolayer adsorption
capacity was calculated as 62.50 and 37.07 mg/g for AML
and RPJL leaves, respectively. Effect of polyphenols upon
biosorption was experimentally depicted using pure polyphe-
nols as standards. The process was found to be exothermic,
spontaneous and favorable. Interaction between adsorbate
and adsorbent followed chemisorption and followed pseudo-
second-order kinetics. Desorption experiments using NaOH
as desorbing agent produced considerable results up to three
cycles depicted that the biosorbent is reusable. Compar-
ing the adsorbent with previously used materials for Cr(VI)
removal (Table 5, [46–51]), it was concluded that the Ruellia
patula leaves can be an excellent ecofriendly biosorbent with
regeneration capacity for removing toxic Cr(VI) from aque-
ous solutions. Being a inexpensive and abundantly available

123
1556
material, the leaf particles can be used for industrial applica-
tions in removing Cr(VI) from various real effluents released
from chrome plating, textile dyeing, leather tanning and pho-
tolithographic industries.
Acknowledgements The authors heartfully thank the Editor and
anonymous reviewers for their valuable comments and suggestions
which improved the quality of the paper. We greatly acknowledge Kerala
State Council for Science, Technology and Environment, India (Grant
No. ETP/02/2014/KSCSTE), for their financial support to perform this
study.
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