Copper and Cadmium removal by Bagasse Fly Ash: Kinetic and Isotherm Study

Abstract

Herein, the current study presents a batch adsorption experiments to remove two different toxic

metal ions, copper (Cu) and cadmium (Cd), as model synthetic pollutants in the aqueous phase

by using the bagasse fly ash (BFA) as an adsorbent. The various operating parameters of

adsorption process including pH, adsorbent dose, contact time, initial metal ion concentration is

optimized. Experimental results confirmed the pH 6.0 was found to be optimum for the removal

of both model metal ions. Approximately 90 minutes of contact time is required to achieve the

adsorption equilibrium, at 4g/L of adsorbent dose for Cu and at 5 g/L of adsorbent dose for

cadmium, respectively. The maximum removal efficiency achieved for Cu and Cd were found to

be 98.3% and 98.6% respectively at the optimized condition of batch adsorption process.

Langmuir, Redlich-Peterson and Hill isotherm for Cu; Freundlich, Langmuir, Redlich-Peterson

and Hill isotherm for Cd removal are best fitted with experimental adsorption isotherm data and

pseudo first kinetics is best fitted for both Cu and Cd ions, respectively. The thermodynamic

property Enthalpy, ΔH0 = -16.52, -26.78 kJ/mole; Entropy, ΔS0 = -0.041, -0.084 kJ/mole/K are

calculated for Cu and Cd metal respectively at initial metal load of 100 mg/L.

Keywords: bagasse fly ash (BFA), heavy metals, adsorption, surface area, porosity

INTRODUCTION

The occurrence of highly toxic pollutants like heavy metal ions in the drinking water and river

water due to different anthropological activities caused serious ill impacts on both environment

and human health. Despite the leaching of heavy metals ions in water system from natural

minerals and ores are quite common but secretions of different pollutants from industrial waste

1
have become a serious concern these days. Metal plating industry is one of the most common

industry, used for coating an anti-corrosion layer on the surface example, which contributes

significantly leaching of different heavy metals including Zn, Cu, Ag, Pb, etc in the aqueous

environment (Álvarez-Ayuso et al. 2003; Fu and Wang 2011; Da̧browski et al. 2004; Kadirvelu

et al. 2001). Metals like nickel, cadmium, platinum, gold, silver, chromium are least corrosive

and costly which are used frequently in the electroplating industry. The wastewater discharged

from such industry carried a large amount of metal ions which are hazardous in nature. The

toxicological studies and World Health Organization (WHO) reports set the lowest permissible

limit of different heavy metals in drinking water and wastewater below parts per millions (Izah et

al. 2016; Jaishankar et al. 2014; Organization 2004; Reza and Singh 20110). The presence of the

heavy metals beyond lowest certain limits is causing cancer, kidney damage, and even death in

some cases (Kar et al. 2008).

The treatment of various water impurities including organic, biological impurities (microbes and

bacteria) and heavy metals can be completely destroy or decomposed to non-toxic form except

metal ions which are rigid in the aqueous environment, and remains for hundreds of years or

more in the environment (Kurniawan et al. 2006), therefore, a separation technique is required.

Although, different technologies have been developed to reduce the heavy metal to some relative

toxic forms like Cr(VI) to Cr(III), As(V) to As(III) which are relatively lesser toxic (Verma et al.

2015; Khare et al. 2016; Gupta and Chen 1978; Baral et al. 2006; Al-Othman et al. 2012).

Among other metal ions, copper ion is frequently found in the industrial wastewater from

associated industrial plants like plating, dyeing, mining, metal cleaning, and petroleum and

electroplating industries (Bailey et al. 1999). Moreover, at this concentration level, copper (Cu)

is toxic heavy metal and its presence causes serious ill effect on humans like stomach-ache and

2
intestinal distress, kidney damage and anemia (Järup 2003; Raikwaret al. 2008; Yu et al. 2000).

Cadmium from heavy metal family is another toxic pollutant in the environment, and causes

harmful effects, like renal damage, testicular problems, hypertension and emphysema. The prime

sources of cadmium metal ions discharges are found in the industrial wastewater from battery

and electroplating industries (Singh et al. 2005; Deveci and Kar 2013; Panda et al. 2011).

Various commercial methods for separation of heavy metals from aqueous phase are being

continuously in use, including chemical precipitation, ion exchange, flotation and membrane

filtration etc. However, in view of materials and operating energy requirements, adsorption

process is relatively inexpensive, efficient process and easy to scale up, therefore, still applied at

industrial scale (Martín-Lara et al. 2010; Sočo and Kalembkiewicz 2013; Dehghani et al. 2019;

Sahu et al. 2015). In general, an efficient adsorbent decides the efficiency of adsorption process.

The desired general properties of an adsorbent are such as large surface area with high porosity,

free flowing for easy handling and its compatibility with an adsorbate, keeping all this in regards,

so far, many adsorbents have been investigated. Among which few of them are classified as

activated carbon (Kobya et al. 2005; Bishnoi et al. 2004), activated alumina (Naiya et al. 2009),

bone char (Ko et al. 2000; Inyang et al. 2016), activated clays (Bhattacharyya and Gupta 2008;

Uddin 2017; Eloussaief and Benzina 2010), silica gel (Najafi et al. 2012; Gao et al. 2006),

fuller’s earth (Oubagaranadin et al. 2007), zeolite (Motsi et al. 2009). In recent years, different

types of agriculturally based wastes like saw dust, sugarcane dust, peanut, rice husk, orange peel,

banana peel and their bio resources derived fly ash have been applied for removing heavy metals

from aqueous phase (Annadurai et al. 2003; Anwar et al. 2010; Chuah et al. 2005; Cho et al.

2005; Alinnor 2007).

3
The objective of the present work is to study the removal of copper and cadmium ions from

synthetic wastewater using Bagasse Fly Ash (BFA) as an adsorbent. It includes Characterization

of BFA, optimization of various parameters like pH, adsorbent dose and selection of suitable

kinetic model (among the pseudo first order, pseudo second order model) for adsorption process

based on regression analysis. Also study of adsorption isotherm model e.g. Langmuir, Freundlich

etc. for the adsorption process by regression analysis is done.

MATERIAL AND METHODS

All the chemicals of analytical grade were used in the study of SD fine chemicals Mumbai, India.

Deionised water (DI) with conductivity 5.3 μS/m used for the preparation of solution. A standard

stock solution prepared from the salt of cadmium, copper and different aliquots were prepared by

progressively diluting, stock solution as Eq 1 with DI water.

m1V1=m2V2 (1)

Bagasse fly ash (BFA) was collected from Uttam Sugar Mill, Manglaur, Haridwar, Uttarakhand,

India. It was washed, dried and characterize before used as an adsorbent. Table 1 present the

proximate and nitrogen physio-sorption analyses of BFA sample. Table 1 is showing moisture,

volatile, fixed carbon and ash contents as measured from proximate analysis. The Brunauer–

Emmett-Teller (BET) method was used to determine the BET surface area, total pore volume.

The structural properties like spatial plane of carbon, and to determine impurities were analysed

by X-ray diffraction (XRD) for BFA. XRD analysis of BFA carried out in Bruker X-ray

diffractometer (model D8 advance) instrument, in which copper target was used with nickel as

filter media (Kα radiation ~ 1.542 oA). Thermal stability of BFA sample in a controlled

atmosphere, analysed at heating rate of 10oC/min in oxygen rich environment, started from room

4
temperature, using thermo gravity analysis (TGA), instruments (model: SII 6300 EXSTAR,

USA). Differential thermogravity analysis (DTA) determines the temperature range at which

maximum weight loss takes place.

Fourier transform infrared (FTIR, detail- Thermo Scientific Nicollet 6700-FTIR-spectrometer)

was used to identify as composition functional groups of the sample. Scanning electron

microscope (SEM), used for analysing the morphology of metal loaded and unloaded BFA. Prior

to SEM analysis, sample were prepared by coating with gold to improve the conductivity for

electron microscopic analysis. Concentrations of metallic solutions were determined by atomic

absorption spectrophotometer (AAS, Avanta, Australia). The high accurate concentration of

different unknown aliquots was analysed after standardizing the AAS instrument over the

different linear concentration ranges for Cu (1- 5 ppm) and Cd (0.2-1.8 ppm) with standard

samples.

Adsorption process for Cu and Cd metal ions removal, batch experiments were conducted at the

temperature of 30±1oC. To conduct each experiment 100 ml of synthetic solution was taken in

250 ml conical flask with known amount of adsorbent. Then these samples were kept in shaker

with speed of 150 rpm for specific time. After finishing the experiments, sample were

centrifuged at 6400 rpm for 5 min then concentration of samples was determined by atomic

absorption spectroscopy (AAS, Make: Avanta M, GBC, Australia).

The pH of samples was adjusted by using 1 N HCl and 1 N NaOH solution. In each experiment a

blank sample with adsorbent was also conducted. Then the percentage of metal removal and

equilibrium adsorption uptake qe (mg/g) was calculated by Eq 2 and Eq 3.

Percentage removal 
 C0  Ce  100
C0 (2)

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 Adsorbed amount, q e 
 C0  Ce  V 100
m (3)

where, Ce is the equilibrium adsorbate concentration (mg/l); C o is the initial adsorbate

concentration (mg/l); m is the mass of adsorbent taken

Isotherm Model

Freundlich, Langmuir, Redlich-Peterson, Hill, Temkin, Elovich and Jossens isotherm were used

to describe the adsorption of copper and cadmium by BFA. The Freundlich expression is an

empirical equation-based sorption on a heterogeneous surface (Al-Anber and Matouq 2008).

This isotherm corelates heterogeneity of active surface with the active site distribution and their

energies. Freundlich equation is defined as,

1
log (q e )  log(K F )  log(C e )
n (4)

where, Ce is the equilibrium concentration of metal ion in the solution (mg/l) , n and KF are the

Freundlich model constants, related to the intensity and adsorption capacity, respectively. The

Freundlich constants n and KF can be determined by plotting (linear plot) between log(qe) versus

log(Ce). qe is the amount of metal ion adsorbed at equilibrium per gram of adsorbent (mg/g).

The Langmuir model stats that the uptake of metal ions on a homogeneous surface by monolayer

adsorption without any interaction between adsorbed ions within the adsorbent (Chen et al.

2009; Ayawei et al. 2017), which is defined as Equation 5.

bCe
q e  q max
(1  bCe ) (5)

Where, qmax is the maximum metal uptake per unit mass of adsorbent (mg/g)

6
Equation (5) can be rearranged to plat the graph between Ce/qe versus Ce as equation 6,

Ce 1 C
  e
q e bq max q max (6)

Temkin isotherm states that heat of adsorption decreases linearly due to interactions between

adsorbate. The characterization of adsorption can be done with help of distribution of binding

energy and related expression is given as equation 7,

q e  B1 ln(K T )  B1 ln(Ce ) (7)

RT
B1 
Where, b ; b is the Temkin energy constant (j/mole), K T is the explicitly which considers

interaction between adsorbate and adsorbent.

The Redlich-Peterson isotherm is the combine form of Freundlich and Langmuir isotherms. The

numerator of Redlich-Peterson isotherm is from the Langmuir isotherm and has the benefit of

approaching the Henry region at infinite dilution and mechanism of adsorption is a mix and does

not follow ideal monolayer adsorption (Farouq & Yousef 2015). Equation is expressed as,

K R Ce
qe 
1  a R Cge (8)

Where, KR and aR are the parameters for Redlich-Peterson isotherm.

Equation 8 can be expressed as,

Ce 1 aR g
  Ce
qe K r Kr (9)

by plotting the graph between Ce/qe vs Ce value of Redlich-Peterson isotherm constant can be

calculated by the slope and intercept of the straight line.

7
Hill isotherm is expressed as equation 10, Hill isotherm equation defines the binding of diverse

species on homogeneous materials. This expression states that adsorption is a supportive

phenomenon with adsorbates at the adsorbent surface (Rania and Yousef 2015).

Q H Cen H
qe 
K D  Cen H

(10)

Where, KD and nH are the parameters for Hill isotherm.

Equation 10 can be expressed in linearized form as, presented below in equation 11,

 qe 
log    n H log(C e )  log(K D )
 QH  qe  (11)

 qe 
log  
by plotting the graph between  Q H  q e  vs log(Ce) value of Hill isotherm constant can be

calculated from the slope and intercept of the straight line.

Elovich isotherm is based on a kinetic principle, which corelates the absorption sites with the

multilayer adsorption process. The equation was first developed to describe the kinetics of

chemisorption of gas onto solids (Hamdaoui and Naffrechoux 2007). The Elovich Isotherm

expression is expressed as equation 12

q
qe e

 K e Ce e q m
qm (12)

Where Ke and qm are the Elovich Isotherm constant and equation 12 can be linearized by taking

ln both side and linear expression can be expressed as equation 13.

qe q
ln  ln K e q m  e
Ce qm (13)

8
by plotting the graph between ln(qe/Ce) vs qe value of Elovich isotherm constant can be

calculated from the slope and intercept of the straight line.

The energy distribution of metals(adsorbate)-fly ash(adsorbent) interactions at adsorption sites

for heterogeneous surface of adsorbent with respect to interaction with adsorbate is expressed as

Jossens isotherm and it is represented as equation 14 (Syafiuddin et al 2018).

qe
Ce  exp(Fq ep )
H (14)

Where, (similar to Henry’s constant), p, F are represented as Jossens isotherm constant. By

taking log both side, equation 14 can be rearranged as equation 15.

Ce
ln   ln H  Fq ep
qe (15)

From equation 15 the values of 𝐻 and 𝐹 can be calculated by plotting the graph between ln(C𝑒/q𝑒)

versus 𝑞𝑒.

Kinetic Model

The kinetic study of Cu and Cd is done to determine the order of the reaction byusing pseudo-

first order and pseudo second order absorption equations. Pseudo first order can be expressed as

equation (16) (Chen et al. 2009).

dq t
 K f (qe  q t )
dt (16)

Where, qt(mg/g) is the adsorbed amount at time 't'; qe is the equilibrium adsorption capacity

(mg/g), Kf is the pseudo first order rate constant (min-1).

By solving equation 12 at boundary condition qt = 0 at t = 0 we get,

kf t
log  q e  q t   log  q e  
2.303 (17)

9
 log  q e  q t 
Further, by plotting graph between versus t we get value of adsorption rate

constant kf.

Equation of second order can be given as equation 18 (Pérez-Marín et al. 2007).

dq t
 KS  qe  q t 
2

dt (18)

Where, KS is the pseudo second order rate constant (g/mg min).

By solving equation 18 at boundary condition qt = o at t = o we get,

K Sq e2 t
qt 
1  K Sq e t (19)

Gibbs free energy determination

distribution coefficient (K0) with temperature can be used to determine the thermodynamic

constraints associated with the adsorption process. K0 can be defined by equation 20

K0=Ca/Ce (20)

Where, Ca is the metal ions concentration remaining, and Ce is the equilibrium concentration of

metal ions (Borhade et al., 2014).

The energetic values of enthalpy and entropy in addition to free energy (adsorption) must be

taken in considerations to determine the adsorption process.

The adsorption standard free energy changes (ΔG0) can be corelated with distribution coefficient

(K0) as Equation 21 (vant Hoff equation)

G 0  RT ln K 0 (21)

where R: universal gas constant and T is temperature in kelvin

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 G 0 q 
  ln  e 
RT  Ce  (22)

The standard Gibbs free energy change (ΔG0), standard enthalpy change (ΔH0) and standard

entropy change (ΔS0) were determined by using the following equations:

ΔG0= ΔH0 - TΔS0 (23)

The numerical value of ΔH° and ΔS° can be determined from slope and the intercept by plotting

the graph between ln K0 versus 1/T obtained from the slope and the intercept of each plot (ln K c

versus 1/T)

RESULTS AND DISCUSSION

Physio-chemical properties of BFA

Ultimate Analysis of BFA

The ultimate analysis measured the quantity of carbon, hydrogen, nitrogen, oxygen and sulphur

components present in sample. Result of ultimate analysis of bagasse fly ash is presented in table

2. It is observed that carbon, hydrogen, nitrogen composition of BFA increases after metal

absorption. Since, BFA contain 28-29 % ash which is mainly the mixture of SiO 2, Al2O3, Fe2O3,

CaO, K2O, Na2O, P2O5, MgO, MnO, etc. out of these components some components are soluble

or slightly soluble in the water (Cordeiro et al. 2004). So, high operating time (time: 90 minute)

for adsorption responsible for the reduction of ash content of the used BFA due to dissolution of

soluble component in the water.

11
X-ray diffraction analysis (XRD)

The XRD spectrum of unloaded BFA (blank), Cu-loaded and Cd-loaded BFA samples are

presented in the Fig 1. It is cleared that the presence of two small intensity broad peaks in the all

samples confirming the amorphous nature of carbon plane between 200 and 400 corresponding to

2 θ peak at 26 and 44 οC. However, the presence of adsorbed metals which is present in small

amounts are not able to map by this analysis.

Surface morphology of the adsorbent

The surface morphology of the blank, Cu and Cd loaded BFA as shown in Fig 2 (a-c) were

analysed by SEM at magnification of 100 X resolution scale. Fig. 2 show, BFA were resembles

like small broken piece of rectangular straw cut down symmetrically along axis. The Blank BFA

(Fig. 2a) is clean and no evidence of other impurity in the sample. However, the presence of thin

white layers in patches on surface were appeared in the Cu and Cd loaded BFA after adsorption.

Moreover, it is noticeably seen that relatively a little thick layer in patches (Fig. 2b) was found

for Cu loaded samples as compare with Cd loaded BFA (Fig. 2c) sample. The white layers may

be due to the presence of metals ions impurity which is bound with BFA surface via weak

hydrogen bonding (Shankar et al. 2014).

TGA/DTA/DTG curve of blank and loaded BFA

Fig. 3(a), 3(b) and 3(c) represent the TGA, DTA and DTG analysis of blank BFA, Cu and Cd

loaded BFA samples, respectively. Heating rate was kept constant at 10 oC/min over the 15–500
o
C temperature range, for the degradation of adsorbent sample in the air atmosphere. Total

weight loss in blank BFA over the temperature range from 15–500oC was found to be 17.75 %,

in copper loaded BFA between 25-450 oC was found to be 25 % and in Cd loaded from 27 – 470
o
C was found to be 21.4 %. At lower temperature (25-200 oC) the BFA weight loss is mainly due

12
to loss of moisture and light volatile matter [Shankar et al., 2014]. However, when the BFA is

heated at higher temperature, the surface groups decompose, producing CO in the temperature

range 200-600 oC, CO2 in the temperature range of 450-1000 oC and element-based water vapour

and free hydrogen in the temperature range of 500-1000 oC [Sahu et al., 2015, Mall et al. 2006,

Puri and Walker 1966]. Also, in case of blank BFA maximum weight loss of around 83.7 % took

place between 500-630 oC, in copper loaded it was 69.8% between 450-550 oC and in case of

cadmium loaded 72% between 470-560 oC. The weight loss in case of metal absorbed BFA is

less it is probably due to non-combustible nature of Cu and Cd.

DTA curve of all samples, confirming the degradation of samples with temperature are following

exothermic reaction. Energy of reaction (degradation) for blank, copper and cadmium loaded

BFA samples are -25, -5.67 and -4.79 J/mg respectively. DTG graph gives us the information

about rate of weight loss with respect to time. Maximum weight loss is taking place around 570
o
C for blank BFA, around 480 oC for copper loaded BFA and 500 oC for cadmium loaded BFA.

Rate of weight loss is found to be 1.01 mg/min for blank BFA, 3 mg/min for copper loaded BFA

and 3.15 mg/min for cadmium loaded BFA [Shankar et al. 2014; Sahu et al. 2015]. Rate of

weight loss of BFA with both metals is high in comparison with blank BFA. It is because

presence of metal ions act as a catalyst which help in the rate of decomposition (Wang et al.

2018).

FTIR analysis of blank and loaded BFA

Fig. 4 (a) & 4 (b) show FTIR analysis of blank/copper loaded BFA and blank/cadmium loaded

BFA, respectively. From both curves, a molecular absorption vibration present at 3429 cm -1

shows the alkyne C-H stretch as well as O-H stretch, a peak at 2916 cm -1 webnumber shows the

methylene C-H stretch, and peak at 2358 cm-1 shows the alkyne group stretch, in the both sample.

13
The peaks between 1400-1800 cm-1 is mainly due to C=C present in aromatic ring and C-H

stretching (shankar et al. 2016). The skeletal alkane vibrations are shown at 1235 cm -1.

Wavenumber 1055 cm-1 is characterized by skeletal C-H vibrations. Peaks around webnumbers

610 cm-1 is shown by aliphatic compound (Srivastava et al. 2007; Ren et al. 2008).

In figure 4(a) variation in the peaks are noted between the webnumbers 1100 cm -1 to 1600 cm-1

and in figure 4(b) variations in peak are noted between the webnumbers 900-1900 cm -1 which

indicates the accumulation of Cu and Cd metals with aromatic ring and C-H bond-based

compounds.

Adsorption study of Cu and Cd ions on BFA

Effect of pH

Fig 5 present the effect of pH on adsorption of copper and cadmium using BFA as an adsorbent.

To study the effect of pH, experiments were conducted with pH range from 2-10. It is found that

as pH increases up to 6, removal efficiency also increases then decreases thereafter for both Cd

and Cu metals. In highly acidic condition (pH<4) hydrogen cations are present bulk in the

solution which compete with Cu and Cd for adsorption with the negatively charge adsorbent

surface or active sites. With increase in pH, hydrogen cations concentration is reduced, so

removal is increased (Hamdaoui and Naffrechoux 2007). It was also observed at higher pH

precipitation takes place, but metal removal due to hydrogen cations reduced, Overall the

removal of metal ions increases (Suresh et al., 2010). From Fig 5, the optimum pH for the

removal is 6.0 for both metal ions and pH 6.0 were used for further study.

Effect of adsorbent dose

14
Effect of adsorbent dose on removal of Cu and Cd are presented in Fig 6. The adsorption test

was performed by keeping the different parameters of testing solution constant (adsorbate

concentration 100 mg/L, pH 6.0, and temperature at 30 oC). From Fig 6, Cu and Cd removal

efficiency increases with increase in adsorbent dose upto 4 g/L and 5 g/L respectively and above

this dose, metal removal efficiency becomes constant.

Figures shows the adsorption increases with the adsorbent dose, due to availability of

more vacant sites with high dose of the adsorbent. Hence, adsorption efficiency is increased with

adsorbent dose (Dilekoglu 2016). Optimum dose of BFA for Cu and Cd removal, 4 g/l and 5g/l,

respectively, are used for further study.

Effect of adsorbate concentration and contact time

Fig 7(a) and 7(b) represents the effect of initial metal (adsorbate) concentration with time on Cu

and Cd ion reduction.

Fig 7(a) and 7(b) show, at low concentration, equilibrium contact time is achieved within 90

minutes for Cu and Cd after that removal efficiency become constant. Generally, the contact time

for adsorption is a crucial step to understand the approach of metal ions (adsorbate) to the

adsorbent surface and it is very well evident from the study that for lower concentration of

adsorbate, approximately 70 % removal was observed within 50 min contact time, however at

higher concentration of adsorbate, the increase in equilibrium adsorption time (contact time)

were observed for both cases. Generally lower contact time refers to the physical adsorption.

Adsorption kinetic study

Experiments for the removal of Cu and Cd using BFA as an adsorbent were conducted at

optimized conditions which include optimum pH, adsorbent dose, at the room temperature (30

15
o
C) etc. Value of adsorption kinetic parameters for Cu and Cd removal are presented in Tables 3.

The experimental data are fitted with pseudo first and second order kinetic equation for both Cu

and Cd metals, and correlation coefficient values obtained are much closer to 1 for first order

kinetics as compare to the second order kinetics data, hence overall removal of Cu and Cd follow

first order kinetics.

Adsorption isotherm modelling

Adsorption isotherm modelling for Cu and Cd removal experiments from aqueous phase were

conducted at different temperatures i.e. 15, 30and 45 oC. Other conditions which were kept

constant (pH =6.0, adsorbent dose = 4 g/l for Cu and pH = 6.0, adsorbent dose = 5 g/l for Cd).

Analysis of equilibrium data for Cu and Cd removal was done by regression analysis using

Microsoft Office Excel (Srivastava et al. 2007). A curve was plotted between extent of

adsorption and equilibrium concentration in aqueous phase. Fig. 9(a) and 9(b) show adsorption

isotherms of Cu and Cd removal. Tables4 show different values of isotherm parameters obtained

by fitting experimental data with different models like Freundlich, Langmuir etc. Experimental

and theoretical values are denoted by points and line, respectively.

Thermodynamic Study

All the thermodynamic parameters (change in Gibbs free energy (ΔG), change in enthalpy (ΔH)

and change in entropy (ΔS)) for variable metal load are represented in Table 5 and

thermodynamic plots for different initial organic load are shown in Fig 10. From the table it is

noted that adsorption of both the metals Cu and Cd are in exothermic in nature because of

calculated value of ΔH are negative in nature. Enthalpy change from negative to positive states

that adsorption is exothermic in nature. Endothermic adsorption of Cu(II) and Cd(II) ions with

16
various adsorbents has been reported by (Ren et al. 2008). However, value of ΔG° increased

with the temperature which suggest that spontaneous tendency of adsorption is inversely

proportional to temperature. the negative value of decreased with an increase in temperature,

indicating that the spontaneous nature of adsorption is inversely proportional to temperature

(Sharma et al. 2010; Surchi 2011). It is also observed that value of ΔG° is increased with the

initial metal loading it is obvious because availability of higher metals decreases the spontaneous

nature because of fixed available active site of adsorbent. The structural change at active sites

and in BFA is evidenced by entropy change (ΔS°) at elevated temperature during the adsorption

process (Bao et al. 2013). The negative and small numerical value of ΔS° shows enhanced

randomness at solid/liquid interface during the adsorption process.

It is also noted that value of ΔS increases with the initial metal load. Change in ΔS indicates that

randomness of metal molecules increases on the solid surface (Ren et al. 2008). So, it can

understand that metal adsorption on solid surface increases with initial organic load and it has

maximum value at temperature 318 K for initial metal load of 600 mg/L for both metals.

CONCLUSIONS

Present study states that bagasse fly ash (BFA) is an efficient low-cost adsorbent for the heavy

metal removal from the contaminated wastewater. Effectiveness of BFA depends upon the multi

parameters i.e. initial metal load, operating time, types of pollutants etc. Removal of metal was

found to be higher when initial metal concentration was lower. Optimum pH of the removal was

found to be around 6.0 for both copper and cadmium metals. Optimum dose of maximum

removal is found to be 4 g/l for Cu and 5 g/l for Cd ions. Contact time of maximum removal was

found to be 90 min for Cu and 60 min for Cd. Maximum reduction of 98.3% and 98.6% were

17
found for Cu and Cd respectively at optimum condition. Overall bagasse based adsorbent can

play an alternative role of conventional available adsorbent.

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