Journal of Dispersion Science and Technology

ISSN: 0193-2691 (Print) 1532-2351 (Online) Journal homepage: http://www.tandfonline.com/loi/ldis20

Adsorption of Malachite Green by Diatomite:

Equilibrium Isotherms and Kinetics Studies

Lijie Tian, Jian Zhang, Haiqiang Shi, Na Li & Qingwei Ping

To cite this article: Lijie Tian, Jian Zhang, Haiqiang Shi, Na Li & Qingwei Ping (2015): Adsorption
of Malachite Green by Diatomite: Equilibrium Isotherms and Kinetics Studies, Journal of
Dispersion Science and Technology, DOI: 10.1080/01932691.2015.1080610

To link to this article: http://dx.doi.org/10.1080/01932691.2015.1080610

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Aug 2015.

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 Adsorption of malachite green by diatomite: equilibrium isotherms and kinetics
studies

Lijie Tian1, Jian Zhang1, Haiqiang Shi1, Na Li1, Qingwei Ping1

1
Liaoning Key Laboratory of Pulp and Paper Engineering, School of Light industry and
Chemical Engineering, Dalian Polytechnic University, Dalian, China

Corresponding author: Dr. Jian Zhang Mailing address: School of Light industry and
Chemical Engineering, Dalian Polytechnic University, 1# Qinggongyuan, Dalian, China
116034 E-mail: zhangjian@dlpu.edu.cn
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Abstract

The utilization of diatomite as potential adsorbent to remove malachite green (MG) from

aqueous solution was developed. The characterization of the diatomite was evaluated by

SEM and BET. The operating variables of pH, diatomite mass, initial MG concentration

and adsorption reaction time were studied. The equilibrium, kinetics and thermodynamic

parameters were investigated as well. It was found that the diatomite was composed of

integral and almost circle sieve tray with lots of small pores on it, which afforded the

diatomite high specific surface area of 46.09 m2g-1. The optimum pH and reaction time

were 7 and 90 min respectively. The MG removal increased accordingly as the diatomite

mass increased. The isotherms results showed that the equilibrium data was fitted to

Langmuir model better, indicating the MG adsorption was better characterized by

monolayer. The maximum monolayer capacity obtained from Langmuir was 23.64mgg-1

at 25℃. The kinetics studies indicated that experiment data followed

1
 pseudo-second-order model better. It also revealed that intra-particle diffusion was not

the only rate controlling step. The thermodynamic concluded that the adsorption was

endothermic and more favorable at high temperature. Researches confirmed the

applicability of diatomite as an efficient adsorbent and low-cost process to remove

hazardous materials.
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KEYWORDS: Diatomite, Malachite green, Adsorption, Kinetic, Thermodynamic

1. INTRODUCTION

Environmental problems have become a global concern for their impact on public

health[1, 2]. Industrial effluents are one of the major causes of environment pollution,

particularly the waste aqueous effluent from dye industry[3]. Malachite green (MG) is a

basic dye and important water-soluble dye belonging to triphenylmethane family[4]. It is

widely used to dye wool, silk, cotton, leather, jute, paper as well as fungicide and

ectoparasiticide in aquaculture and fisheries. Due to the considerable resistance of MG,

2
 physical, chemical and biological methods[5] for MG removal have been widely studied,

such as advance oxidation[6], photocatalysis [7], adsorption[8], membrane filtration[9]

and electrochemical techniques[10]. Among these methods, the adsorption technique is

especially attractive for its high efficiency, low cost and easy operation. Many adsorbents

have been investigated on the possibility to lower dye concentrations from aqueous

solutions, such as activate carbon[11], bentonite[12], chicken feathers[13], sugar cane

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dust[14], sludge[15] and agroindustry waste[16].

Diatomite, also known as diatomaceous earth, is a fine sedimentary rock of biogenetic

origin, which mainly consists of amorphous hydrous silica (SiO2·nH2O) that derives from

the skeletons of aquatic plants called diatoms[17]. It consists a wide variety of shapes and

characterized by a high porosity up to 80%, low density and high surface area [18]. These

properties suggest that diatomite is a potential adsorbent for pollutants found in industrial

wastewater including dyes [19]. Previous studies indicated that a kind of commercial

diatomite come from USA after treated was an effective adsorbent to remove methylene

blue from contaminated solution[20]. Diatomite is abundant in many parts of China and

the price is lower than other country, is about 500 RMB per ton for the raw diatomite.

However the physical characters of different areas sample were very different. It is

reported that the diatomite produced from Baishan in Jilin province showed excellent

physical characters in China.

3
 This research focused on developing the feasibility of the diatomite from Baishan area,

China, as low-cost and environmental friendly adsorbent for malachite green removal

from aqueous solution. The adsorption of MG onto diatomite was studied under several

different experimental conditions, such as initial MG concentration, reaction temperature

and pH. The equilibrium, kinetics and thermodynamic parameters were also evaluated
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and investigated.

2. EXPERIMENTAL

2.1 Materials

The diatomite samples were supplied by Jilin Lulin novel materials Co.,Ltd., Baishan,

Jilin province, China. The morphology features and surface characteristics of the

diatomite samples were observed from a scanning electron microscopy (JEOL,

JSM-6460LV, Japan). The specific surface area was obtained by Surface Area & Pore

Size analysis (Quantachrome NOVA, USA). Malachite green (MG) and other chemical

agents were of analytical grade and were purchased from commercial sources in China.

2.2 Adsorption Studies

The dye solution of MG was prepared by dissolving accurately measured amounts of MG

in distilled water to obtain a concentration of 500 mgL-1 and further diluted to the various

4
 required concentrations before used. Batch adsorption experiments were performed by

adding 0.05g diatomite in a set of 30mL vials containing 20mL of MG solution with

various initial concentrations. The mixtures were processed under constant stirring at

different temperature in a temperature-controlled water bath shaker to reach equilibrium.

The MG concentration in the aqueous solutions was determined by UV

spectrophotometer (Varian CARY 300 Conc, USA) at 618nm. The adsorbed capacity ( Qe )
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and removal efficiency (R) of MG onto diatomite were calculated according to Eq. (1)

and Eq. (2).

C0 - Ce V
Qe (1)
M

C0 - Ce 100
R (2)
C0

Where Qe is the adsorption capacity at equilibrium (mgg-1), R is the removal efficiency

(%), C0 and Ce are the initial and equilibrium concentration of MG in solution (mgL-1), V

is the volume of solution (L), M is the mass of the diatomite (g).

2.3 Adsorption Isotherm

The relationship between the amount of a substance adsorbed at constant temperature and

its concentration in the equilibrium solution is called the adsorption isotherm[2]. The

adsorption isotherm is important from both a theoretical and a practical point of view.

Adsorption coverage over the surface of diatomite was studied using the two well-known

5
 isotherm models, Langmuir and Freundlich[21]. The parameters obtained from the

different models provide important information for the sorption mechanisms and the

surface properties and affinities of the adsorbents. The Langmuir model[22] and

Freundlish model[23] were as Eq. (3) and Eq. (4), respectively.

Ce Ce 1
(3)
Qe Qmax Qmax K L
1
ln Qe ln K F ln Ce (4)
n
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Where Qmax is the maximum adsorption capacity (mgg-1), KL is a Langmuir constant relate

to the affinity of the binding sites and energy of adsorption (Lg-1), K F is a Freundlish

1
constant related to adsorption capacity (Lg-1), is an empirical parameter related to
n
adsorption intensity.

Adsorption isotherm studies were carried out in vials where fixed diatomite of 0.05g was

introduced into 20mL of MG solution with different concentration at 25℃, 35℃ and

45℃.

2.4 Adsorption Kinetics

The kinetic parameters provided important information for designing and modeling the

adsorption processes[2]. The research of adsorption kinetics describes the dye uptake rate

and evidently this rate controls the residence time of adsorbent uptake at the

solid-solution interface[24]. In order to determine the best kinetic model and find out

6
 adsorption mechanism, the pseudo-first-order[25], pseudo-second-order [26] and

intraparticle diffusion[27] models were used to understand the adsorption dynamics in

relation to time for the MG and diatomite system. These models can be described as

follows:

ln Qe - Qt ln Qe - K1t (5)

t 1 1
t (6)
Qt K 2Qe2 Qe
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1
Qt Kit 2 C (7)

Where Qt is the amount of adsorbed MG onto diatomite at t moment (mgg-1), C (mgg-1)

is the intercept which provide information about the thickness of the boundary

layer, K1 (min-1), K2 (gmg-1min-1), Ki (mgg-1min-1/2) are the rate constants of the adsorption

in pseudo-first-order (Eq.(5)), pseudo-second-order (Eq.(6)) and intraparticle diffusion

(Eq.(7)) respectively.

Kinetic studies were carried out in vials where a fixed mass of diatomite of 0.05g was

introduced into 20mL different initial MG concentration solution for different reaction

time at room temperature.

2.5 Adsorption Thermodynamic

Both enthalpy and entropy are the key factors to be considered in any process design[28].

It is essential to clarify the change of thermodynamic parameters to evaluate the

7
 feasibility and endothermic nature of the adsorption process[1]. The thermodynamic

parameters for the adsorption process, the standard free energy, standard enthalpy and

standard entropy were calculated using the following equations [29]:

ΔG -RT ln KC (8)

Ce adsorbent
KC (9)
Ce solution
ΔS ΔH
ln K C - (10)
R RT
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where K C is the equilibrium constant of the adsorption[3], G is the standard free energy

(kJmol-1), R is the universal gas constant, 8.314Jmol-1K-1, T is the absolute solution

temperature (K), H is the standard enthalpy (kJmol-1), S is the standard entropy

(JK-1mol-1). The standard enthalpy and standard entropy values can be calculated from
1
the slope and intercept of the plot of ln KC versus .
T

The activation energy (Ea) was calculated from the Arrhenius equation which expressed

as Eq.(11)[5]:
Ea
ln K 2 ln A - (11)
RT
Where K2 is the rate constant of pseudo-second-order adsorption (gmg-1min-1), A is the

Arrhenius factor, R is the gas constant, 8.314Jmol-1K-1, T is the absolute temperature (K).

3. RESULTS AND DISCUSSION

3.1 Characterization Of Diatomite

8
 The morphological structure of the Baishan diatomite is shown in Fig. 1.

The diameter of the sieve tray unit is approximately 36 μm, which was roughly estimated

based on scale bar. There were a few column units in the diatomite sample. There many

small pores on each surface of the sieve tray unit and column unit. The pore size in the

center of sieve tray is about 250 nm while the pores on the edge of sieve tray are smaller,
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round 80 nm. Based on the SEM images, it confirmed that the Baishan diatomite sample

has high surface area which is potential to be an excellent adsorbent. In order to verify its

high surface area, the specific surface area was obtained by Surface Area & Pore Size

analysis. The specific surface area of the diatomite was 46.09 m2g-1. The surface areas of

15.87 m2g-1 and 31.35 m2g-1 for a kind of commercial diatomite and its modified sample

respectively, were previously studied by our research group[20]. The surface area of the

Baishan diatomite has tripled compared with the commercial diatomite mentioned above.

These results revealed that the Baishan diatomite was a potential adsorbent with excellent

surface structure and high specific surface area.

3.2 Effect Of Ph And Diatomite Mass

The pH of initial solution plays an important role in the adsorption process. The effect of

different pH and diatomite mass on the MG removal by diatomite was investigated while

9
 the MG concentration and reaction time were fixed at 20mgL-1 and 120min. Results

showed in Fig. 2

The MG removal increased with the increase of diatomite mass. The MG removal

increased from 72.06% to 93.72% as the diatomite mass increased from 0.01g to 0.5g at

pH 7. The paper chooses 0.05g diatomite mass for the following studies based on the cost
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and MG removal performance consideration. With the increase of the diatomite mass, the

surface area and active sites of adsorbent led to an increase in MG removal from aqueous

solution. However when the diatomite reached a certain mass, the MG removal increased

slightly. It is due to the almost saturation adsorption. From Fig. 2, it is clear that the

maximum MG removal obtained at pH 7. As pH<7, the MG removal was poor, since the

interaction between diatomite and MG was reduced which may be due to the protonate

function and competing reaction of the excess hydrogen ion. At higher pH, weak

electrostatic attraction appeared between diatomite and MG for the deprotonate function

which made the MG removal decrease at high pH condition. Similar trend of pH effect

was reported for the adsorption of MG on active carbon prepared by fly ash[30]. Hence

the pH 7 and diatomite mass 0.05g were chosen for further adsorption experiments.

3.3 Effect Of Reaction Time And Initial MG Concentration

10
 The MG removal was measured at varying reaction time with different initial MG

concentration at pH 7 and diatomite mass 0.05g, the results are presented in Fig. 3.

The rate of MG removal increased considerably as the reaction time increased. Initial

portion of the curve increased gradually in nature and thereafter a plateau was reached in

all case. The equilibrium was attained at 90 min when the maximum MG removal on
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diatomite was reached. Fig. 3 showed that the MG removal decreased with the increase of

initial MG concentration. However the actual amount of MG adsorbed per unit mass of

diatomite increased. The adsorption capacity for diatomite was increased from 5.34 mgg-1

to 35.53 mgg-1 (not showed in Fig. 3) as the MG concentration increased from 20 mgL-1

to 200 mgL-1. Therefore the optimum reaction time was selected for 90 min for further

study.

3.4 Adsorption Isotherms

The significance of the adsorption isotherms is that they show how the adsorbent molecules

are distributed between the solution and the adsorbent at the equilibrium conditions and the

effect of equilibrium concentration on the loading capacity at different temperature[31].

The effect of MG equilibrium concentration on the adsorption capacity of diatomite was

carried out at 25℃, 35℃ and 45℃ as shown in Fig. 4.

11
 Fig. 4 showed the MG adsorption isotherms at different temperature. The results indicated

that the MG adsorption on diatomite increased with the increase of MG concentration. And

the amount of MG adsorbed on diatomite was raised by increasing temperature, while the

increase was not so obviously. This may be caused by the increase of the intraparticle

diffusion of MG as the temperature increased. Moreover the desorption phenomena

impeded totally as the temperature increasing[32]. The MG adsorption on diatomite

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increased with increase in temperature, suggesting that the adsorption was endothermic.

A fundamental equilibrium isotherm study is important to considering MG removal by

diatomite. To quantity the MG adsorption capacity by diatomite, Langmuir and Freundlich

isotherms have been adopted. The calculated results of Langmuir and Freundlich

isothermal adsorption parameters were achieved according to the equations by the plot of

Ce
versus Ce and the plot ln Qe versus ln Ce at different temperature and were summarized
Qe

in Table 1.

The Langmuir isotherm model had the best fit with the experimental data due to the high

correlation coefficients R2 >0.99. This suggested that the adsorption of MG on diatomite

was characterized by monolayer coverage. The Qmax value provided the approximate

evaluation of the MG adsorption on diatomite. The maximum monolayer capacity

obtained from Langmuir was 23.64mgg-1 at 25℃. It revealed that diatomite exhibited

12
 better ability to remove MG from aqueous solution. However, the correlation coefficient

( R2 around 0.95) of the Freundlich model was much lower than that of the Langmuir

model, indicating that the MG adsorption was better modeled by monolayer than by
1
multilayer. The Freundlich constant ( ) is related to the adsorption intensity of the
n
1 1
adsorbent. When, 0.1 < ≤0.5, adsorption is wonderful, 0.5 < ≤1, it is easy to adsorb;
n n
1 1
> 1, there is difficult to adsorb[33]. The obtained in this work was between 0.4451
n n
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and 0.4626, lied in the range from 0.1 to 0.5, indicating that MG could adsorb on

diatomite excellently. Moreover, it was clear that the values of K F increased as the

temperature increased, indicating that the adsorption was favorable at high

temperature[34].

3.5 Adsorption Kinetics

Kinetic studies are important to understand the dynamic of the reaction in terms of order

of the rate constant [35]. Moreover the adsorption kinetics provided valuable information

regarding the mechanism of the adsorption process. Three kinetics models were applied

to analyze the results and to determine the adsorption mechanism. The Qe exp , K1 , K2 , Qe

and R2 of MG under different initial concentration were calculated by the plot of

t
ln Qe Qt versus t and the plot versus t and were given in Table 2.
Qt

13
 As showed in Table 2, the correlation coefficients of R2 for the pseudo-second-order

models were between 0.9958 and 0.9995, all more than 0.99. While the R2 for

pseudo-first-order model and intraparticle diffusion model were all less than 0.99 for

different diatomite. This suggested that the rate of the adsorption process was preferably

controlled by chemisorption. Similar results have been reported by Gholamereza Kiani et

al [36]. In addition, the values of Qe (from 7.07 mgg-1 to 39.22 mgg-1) calculated from the
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pseudo-second-order kinetic equation are more close to the values observed

experimentally Qe exp (from 6.69 mgg-1 to 35.34 mgg-1). Thus it is evident that the MG

adsorption on diatomite was best described by the pseudo-second order kinetic model.

The MG is most probably transported from its aqueous solution to the external surface of

the diatomite through intraparticle diffusion, which is often the rate limiting step in many

adsorption processes. Hence, the intraparticle diffusion is another kinetic model should be

used to study the rate of MG adsorption on diatomite. The values of Qt were found to be

1
linearly correlated with values of t 2 showed in Fig. 5.

The linearity of the plots demonstrated that intraparticle diffusion played a significant

role in the uptake of the adsorbate by adsorbent[2]. It has shown that if the intraparticle
1
diffusion is the sole rate-limiting step, it is essential for the Qt versus t 2 plots to pass

through the origin[37]. The plots for the MG adsorption did not pass through the origin

14
 (Fig. 5), which implied that intraparticle diffusion was not the sole rate-limiting step. In

addition, the C values increased from 4.6712 mgg-1 to 18.642 mgg-1 (Table 2) as the

initial MG concentration increased from 20 mgL-1 to 200 mgL-1, which indicating the

increase of the thickness of the boundary layer and the chance of internal mass transfer. It

revealed that the MG adsorption process may have involved many kinds of diffusion of

MG, such as the diffusion from solution to boundary layer, the diffusion from external to
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diatomite surface, the diffusion from surface to pore of diatomite. Furthermore the

correlation coefficients ( R 2 ) for the intraparticle diffusion model given in Table 2 were

between 0.7858 and 0.8880, indicated that the intraparticle diffusion was not the only rate

controlling step, other process could control the rate of adsorption. In sum, it concluded

that the surface adsorption and intraparticle diffusion were occurred during the adsorption

process of MG on diatomite simultaneously.

3.6 Adsorption Thermodynamic

The thermodynamic parameters were evaluated to investigate the nature of the adsorption.

The standard entropy and standard enthalpy were obtained from the slope of the plot

ln KC versus 1/T. The linear regression equation was achieved as y=-1488.9x+6.5876

which indicating the slope was -1488.9. The coefficient in the linear regression achieved

above was 0.995.

15
 The values of these thermodynamic parameters were determined at three different

temperatures and were calculated using Eq. (8), Eq. (9) and Eq. (10) (Table 3).

As shown in Table 3, the H and S values were 12.38 KJmol-1 and 54.77 JK-1mol-1,

respectively. The positive value of H indicated that the adsorption process was

endothermic. The positive of S suggested the good affinity of diatomite for MG as a

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result of the increased randomness at the interface between the solid-liquid phases. The

overall G during the adsorption was negative for the range of temperature investigated,

indicating that the adsorption of MG on diatomite would follow a spontaneous and

favorable trend. The increase in G absolute value with increasing temperature

revealed that adsorption of MG on diatomite became more favorable at higher

temperature. However the increase of G absolute value was not so obviously. This

fact was previously confirmed by the isotherm experiments mention above.

The activation energy (Ea) was calculated from the linear Arrhenius equation(Eq.(11)).

The linear Arrhenius equation was obtained as y=-2751.2x+5.1165 by the plot of lnK2

versus 1/T which revealing the slope was -2751.2. The coefficient in the linear Arrhenius

equation was 0.989. The slope of the lnK2 versus 1/T resulted in a value for the Ea that

was 22.87KJmol-1. Generally, low activation energies (5-40 kJmol-1) are characteristic of

physical adsorption, while high ones (40-800 kJmol-1) suggest chemisorptions[38].

16
 Therefore the physical adsorption mechanism occurred in MG adsorption process on

diatomite.

4. CONCLUSION

It was shown in the present investigation that the diatomite exhibited its performance as

adsorbent for malachite green. The specific surface area of the diatomite reached 46.09

m2g-1. The well-develop porous structure was confirmed by SEM analysis as well. The
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adsorption potential of the diatomite for the removal of malachite green was investigated.

The MG adsorption was dependent on diatomite mass, pH, reaction time and initial MG

concentration. The MG removal increased with the increase of diatomite mass and the

decrease of initial MG concentration. The optimum pH and reaction time were 7 and 90

min, respectively. The adsorption equilibrium was described by Langmuir model well.

The monolayer adsorption capacity based on Langmuir isotherm was found to be

23.64mgg-1 at 25℃. The kinetics results showed that experiment data followed

pseudo-second-order model better, suggesting that the rate of the adsorption process was

preferably controlled by chemisorption. Moreover intraparticle diffusion studies revealed

that the surface adsorption and particle diffusion were occurred in adsorption

simultaneously. The thermodynamic concluded that the adsorption was endothermic,

spontaneous and favorable at high temperature. The activation energy was also calculated

and was found the adsorption confirmed to be physical process. Consequently, both the

17
 physical adsorption and the chemisorption occurred in MG adsorption process on

diatomite. Researches confirmed the applicability of diatomite as an efficient adsorbent

and provided an attractive and low-cost process to remove hazardous materials from

aqueous solution.

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 TABLE 1 Langmuir and Freundlich parameters for MG adsorption on diatomite

Langmuir Freundlich

T(℃) Qmax (mgg-1) KL R2 KF 1/n R2

25 23.64 0.1704 0.9926 4.4393 0.4451 0.9535

35 24.88 0.1767 0.9946 4.6385 0.4550 0.9570

45 27.10 0.1800 0.9939 5.0374 0.4626 0.9657

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 TABLE 2 Kinetic parameters for MG adsorption on diatomite

Pseudo-first-order Pseudo-second-order Intraparticle diffusion

C0 Qe exp K1 Qe R2 K2 Qe R2 Ki C R2

(mgL- (mgg- (min-1) (mgg- (gmg-1 (mgg-1) (mgg-1 (mgg-1

1 1 1
) ) ) min-1) min1/2) )

20 6.69 0.0409 4.06 0.9475 0.0167 7.07 0.9988 0.1715 4.6712 0.7858
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40 13.10 0.0552 15.02 0.9432 0.0065 14.04 0.9974 0.3963 8.4183 0.7938

60 17.84 0.0551 29.20 0.9481 0.0036 19.57 0.9958 0.6653 9.9998 0.7894

80 20.69 0.0506 36.55 0.9285 0.0055 21.74 0.9995 0.4589 15.081 0.888

100 21.53 0.0505 48.74 0.9732 0.0029 23.53 0.9978 0.7733 12.235 0.848

200 35.54 0.0486 92.97 0.9379 0.0015 39.22 0.9977 1.3887 18.642 0.8698

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 TABLE 3 thermodynamic parameters for MG adsorption

-1 -1 -1 -1
T/℃ ΔH(KJmol ) ΔS(JK mol ) ΔG(KJmol )

25 12.38 54.77 -3.96

35 -4.49

45 -5.05
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 Downloaded by [University of Otago] at 01:10 28 October 2015

Figure 1. SEM image of diatomite

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 Downloaded by [University of Otago] at 01:10 28 October 2015

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Figure 2. Effect of pH and diatomite mass on MG removal
 Figure 3. Effect of reaction time and initial MG concentration on MG removal
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 Downloaded by [University of Otago] at 01:10 28 October 2015

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Figure 4. Adsorption isotherms of MG on diatomite
 Figure 5. Intraparticle diffusion model plot for MG adsorption on diatomite
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