Journal of Organometallic Chemistry xxx (2017) 1e7

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Journal of Organometallic Chemistry

journal homepage: www.elsevier.com/locate/jorganchem

Adsorption of Cobalt (II) on Layered Double Hydroxides (Mg/Al and Ca/Al) in

Aqueous Medium : Kinetic and Thermodynamic Aspect
Hensen1
1
Department of Chemistry, Faculty of Mathematics and Natural Science, Sriwijaya University
*Corresponding Author E-mail: Hensenkimia@gmail.com

ABSTRACT
The synthesis of layered double hydroxides has been conducted using M2+/M3+ metal cation in aqueous medium on high
bacisity, where M2+: Mg2+, Ca2+ and M3+: Al3+. The materials Mg/Al and Ca/Al layered double hydroxides were
characterized using FTIR and X-Ray powder analyses. Layered double hydroxides (Mg/Al and Ca/Al) materials then
were applied as adsorbent of cobalt (II) in aqueous medium. Kinetics and thermodynamic adsorption of cobalt (II) were
studied. The results of FTIR spectrum of layered double hydroxide Mg/Al and Ca/Al were showed by unique vibration
of layered material at wavenumber 500-1600 cm-1. The results of X-Ray powder analysis was showed high crystallinity.
Kinetically, Mg/Al layered double hydroxides is more reactive than Ca/Al to adsorb cobalt (II) in aqueous medium.
Thermodynamically, adsorption of cobalt (II) on Mg/Al layered double hydroxides is larger than Ca/Al layered double
hydroxide.
Keywords: layered double hydroxides, cobalt (II), adsorption.

INTRODUCTION waste water is important to public health. The

Layered material are classified into two groups,
cationic clays and anionic clays. Cationic clays are
found in nature and anionic clays are easily
synthesized. Layered double hydroxides (LDH) belong
to the anionic clay minerals was consist of sheets of
the hydroxides of two metals different valence. The
metals hydroxides layeres are positively charged, so
neutrality charged requires must be anion
intercalated into interlayer. Usually, hydroxil ions was
present as anion and this anion can be readily
exchanged by others such as carbonate ions
(Rosenberg and Armstrong, 2013).
Layered double hydroxides has general formula
[M2+(1-x)M3+x(OH)2](An-)x/nH2O, where M2+and M3+
are di-valent and tri-valent cations such as Mg2+, Fe2+,
2+ 2+ 2+ 2+ 3+ 3+ 3+ 3+ 3+
Co , Cu , Ni or Ca and Al , Cr , Ga , Mn or Fe
(Hongo et al, 2017). This layer materials have high
flexibility cation exchange and easily synthesized in
laboratory (Zhao et.al, 2011). Layered double
hydroxide has many potential aplications for layered
double hydroxides including catalysis, adsorption and
flame retardant composite (Clark et al, 2017).
There have been many studies were focusing on
the aplication of layered double hydroxides as
adsorbent (Ahmed and Gasser, 2012). Layered double
hydroxides was used to adsorpted heavy metals (Zhao
et al, 2011) and stable at pH >5 up to 12 (Costantino
et al, 2013). As known, the presence of heavy metals
in the environment can be harmful to variety of living
species. Therefor, the removal of heavy metals from
industrial waste water usually containing cobalt (II) is
common. The adsorption of heavy metals in solution
can be removed using several technique such as
adsorption, precipitation, coagulation, chemical
precipitation, ion-exchange, ozonation and membran
filtration (Shou et al, 2015). The adsorption is
recognized as an easy, economic and effective to
removed heavy metals from the waste water (Sayed et
al, 2016).
In this research, synthesis and characterization of
layered double hydroxides was conducted using
Frourier Transform Infra Red (FT-IR) and X-Ray
Difractometer (XRD). The adsorption process of
layered double hydroxides is intended to determine
the kinetic and thermodynamic parameters by
measuring residual concentration and adsorbed using
Atomic Adsorption Spectrophotometer.
EXPERIMENTAL SECTION
Materials
The chemicals used are analytical grade such as
magnesium nitrate, alumunium nitrate, calsium
nitrate, sodium carbonate, sodium hydroxide and
cobalt nitrate. Water was supplied from Integrated
Research Lab Graduated School, Sriwijaya University.
Analysis instrument were used FT-IR Shimadzu
Prestige-21, XRD Shimadzu Lab X-Type 6000 and
Atomic Adsorption Spectrophotometer NovAA 350
Analytic Jena.
1
Synthesis of Layered Double Hydroxides
Synthesis of layered double hydroxides Mg/Al was
conducted according to Palapa and Said (2016).
Synthesis of layered double hydroxides Ca/Al was
conducting using 100 mL of a solution containing 0.3
mol Ca(NO3)2.H2O and 0.1 mol Al(NO3).9H2O under
vigorous stirring, while was added dropwise 2 mol L-1
of NaOH at pH 11 then stirring until 24 h to form
white solid material and dried at room temperature
to obtain Ca/Al layered double hydroxides (Rojas,
2014).

Adsorption of Cobalt (II) on Layered Double

Hydroxides
Kinetic Parameter
0.0l g layered double hydroxides Mg/Al and Ca/Al
Fig 1. FT-IR spectrum of layered double hydroxides
each added into 25 mL of cobalt (II) 50 mg/L shaker
Mg/Al (a) and layered double hydroxides Ca/Al (b)
with variations in absorption time varied start from
10, 20, 30, 40 and 50 minutes using a horizontal
shaker. The solution of the adsorbed cobalt (II)
substance was separated by filtration and then
measured its concentration by using Atomic
Adsorption Spectrophotometer.
Thermodynamic Parameter
Thermodynamic adsorption of cobalt (II) using
adsorbent 0.01 g layered double hydroxides Mg/Al
and Ca/Al each added into 25 mL cobalt (II) by
variying the concentration to adsorbent layered
double hydoxides Mg/Al 25, 30, 35, 40, 45 mg/L and
to absorbent layered double hydroxides Ca/Al 10, 15,
20, 25, 30 mg/L with each adsorption temperature is
30 0C, 35 0C, 40 0C, 45 0C, 50 0C. The solution of the
adsorbed cobalt (II) substance was separated by
filtration and then measured its concentration by
using Atomic Adsorption Spectrophotometer. Fig. 2 XRD patterns of layered double hydroxides Mg/Al (a)
and layered double hydroxides Ca/Al (b)

RESULTS AND DISCUSSION

Characterization
Characterization of layered double hydroxide was
carried out using the FT-IR. The FT-IR of the layered
double hydroxides Mg/Al and Ca/Al is shown in Fig.1.
The vibration at wavenumber 3300-3800 cm-1 is
assigned as streching of O-H and the bending of O-H at
1635 cm-1. The bending of nitrate is appeared at
wavenumber 1381-1388 cm-1. These vibration was
Kinetic Adsorption of Cobalt (II) on Mg/Al and Ca/Al
Layered Double Hydorxides
Kinetic adsorption of cobalt (II) on layered double
hydroxides both Mg/Al and Ca/Al was studied by
investigated adsorption time as shown in Fig. 3.
25
ads.conc (mg/L)

unique vibration for layered double hydroxides. The 20

vibrations of Al-O, Ca-O and Mg-O were appreated at 15 Mg/Al
563 cm-1 , 424 cm-1 and 416 cm-1 respectively. 10 Ca/Al
The XRD patterns of Mg/Al and Ca/Al material
were shown in Fig 2. The unique structure of layered 5
double hydroxides was identified at diffraction angle. 0
This difraction 100 and 600 indicated that presence of 0 20 40 60
layered materials and the anion on the interlayered.
XRD pattern of Ca/Al in Fig.2b was shown semiliar to adsorption time (min)
that reported by Hongo et al, 2017 when synthesis of Fig. 3. The adsorption time to each adsorbent
material was carried out at temperature was 270C
Fig. 3 showed layered double hydroxides Mg/Al can
(room temperature), the peak intensity of calcite was
adsorp cobalt (II) from aqueous solution higher than
stong, its because layered double hydroxides
layered double hydroxides Ca/Al. The amount of
contained calcite.
cobalt (II) was adsorbed 22.5 mg/L at min using
Mg/Al material and 7.3 mg/L using Ca/Al material at
the same adsortion material. The kinetic data was
obtained from data in Fig. 3. To identify the rate

2
kinetics of the adsorption process, two kinetics
models, namely the pseudo-first-order (PFO) and
seudo-second-order (PSO) have been employed to fit
the experimental data. The pseudo-first-order kinetics
model desribes the adsorption of liquid/solid system
based on solid capacity. The model can be written as:
𝑑𝑞𝑡
= k1 (qe – qt)
𝑑𝑡
𝑘1
log (qe – qt) = log 𝑞𝑒 − 𝑡 (2)
2.303
where qe and qt are t he capacity of metal ions
adsorbed (mg g1) at equilibrium and time t (h),
respectively, and K1 is the PFO rate constant (h1).
Thus the value of qe and k1 can be determined
experimentally by plotting log(qe-qt) versus t and
extracting information from the least squares
analysis of slope and intersept into eq (2).
The seudo-second-order adsorption kinetic is
expressed as following formulation:
𝑑𝑞𝑡
= 𝑘2 (𝑞𝑒 − 𝑞𝑡)2
𝑑𝑡
𝑡 1 1
= + 𝑞𝑒 𝑡
𝑞𝑡 𝑘2𝑞𝑒2
the effect of adsorption temperature and
concentration on the cobalt (II) adsorbate amount of
layered double hydroxides Mg/Al and Fig. 5 show that
the effects of of adsorption temperature and
concentration on the cobalt (II) adsorbate amount of
layered double hydroxides Ca/Al. Fig. 4 and Fig. 5
show that the larger temperature is the greater the
(1)
amount of adsorbed cobalt (II).
The Thermodinamics parameters was studied by
varied of concentration and temperature. Adsorption
capacity and adsorption energy calculated using
Langmuir eq:
𝑐 1 𝐶
= +𝑏 (5)
𝑚 𝑏𝐾
𝐸 = − 𝑅𝑇 𝑙𝑛 𝐾 (6)
Where :
C The cobalt (II) concentration after adsorption
reaches equilibrium, m is Mol of cobalt (II)
adsorption, K is Equilibrium constant, b is Adsorption
capacity , E is Adsorption Energy, R is Boltzmann
constant and T is Temperature
(3) Whereas to find the coefficient value of
adsorbat ditribution is used the equation:
(4) ln 𝐾𝑑 = ∆𝑆 − ∆𝐻 (7)
𝑅 𝑅𝑇

Where k2 (g mg-1 h-1) is the PSO rate constant for the
adsorption process. Thus values of k2 and qe can be
calculated from intercept and the slope of the linear
relationship eq (4) between t/qt and t.
The calculated values of k 1 , k2 , and coefficient
correlation (R2) obtain in Table 1. The result indicated
that linear of PFO model did not give reasonable
values with regard to the experimentals of Co(II).
However, the R2 values are low for linear PFO
comparing with R2 values obtain from PSO. These
result suggest that theb second order mechanism is
predominant, in which the adsorption mechanism
depends on the adsorbate and adsorbent.
Table 1. Kinetics models for the adsorption of Co (II)
PSO kinetic models
T (K) adsorbent K2
R2
(mg/g L min)
Layered double
hydroxides 0.165 0.956
Ca/Al
303
Layered double
hydroxides 0.018 0.962
Mg/Al
The data obtained in Table 1 also showed that the
layered double hydroxides Mg/Al has a more reactive
than Ca/Al because layered double hydroxides Mg/Al
has the adsorption rate a lower than layered double
hydroxides Ca/Al.
Thermodynamic Adsorption of Cobalt (II) on Mg/Al
and Ca/Al Layered Double Hydroxides
Thermodynamic adsorption of cobalt (II) on
layered double hydroxides Mg/Al and Ca/Al was
studied by variying concentration and temperature.
Adsorption data by layered double hydroxides Mg/Al
and Ca/Al in Fig. 4 and Fig.5. Fig.4 show the result of
Where :
Kd Coefficient ditribution adsorption find the
coefficient value of adsorbat ditribution (qe/Ce), ΔH is
Enthalpy, ΔS is Entropy, R is Boltzmann constant and
T is Temperature
The adsorption capacity and adsorption energy of
cobalt (II) adsorption process by layered double
hydroxides Mg/Al and Ca/Al. Table 2 explains that the
adsorption energy value (E) of cobalt (II) adsorbed by
layered double hydroxides Mg/Al and Ca/Al. the
energy value (E) of layered double hydroxides Mg/Al
in the higher temperature the more increasing the
adsorption energy (E). This indicates that the
adsorption process occuring at the varied
temperature undergoes the isothermic condition
which means the process sugests for fisical states
(fisisorpsi) (Vimoses et al, 2009) the determination of
the adsorption capacity (b) is determined by eq 5. In
table 2 shows adsorption capacity layered double
hydroxides Mg/Al has the higher state in 313 K and
layered double hydroxides Ca/Al incline increases in
high temperature.
The subsequent thermodynamic parameters of
enthalpy (ΔH) and entropy (ΔS) of the cobalt (II)
adsorption process by the layered double hydroxides
Mg/Al and Ca/Al are presented in Table 3. The table
shows the entropy (ΔS) of cobalt (II) adsorption by
layered double hydroxides Ca/Al indicates the degree
of irregularity that occurs where large entropy values
indicate that the smaller the concentration the degree
of irregularity or greater entropy. In addition to the
enthalpy value (ΔH) of cobalt (II) adsorption by the
layered double hydroxides Mg/Al and Ca/Al
presented in Table 3 indicates a decreases as
concentration increases and negative of enthalpy

3
 means this process exothermic reaction. 30 -79.86 22.66
30 25 -36.81 140.42
29 layered 30 -21.59 85.05
28 double
35 -19.52 75.16
27 30 hydroxide
Absorbed (mg/L)

26 s Mg/Al 40 -91.70 38.83

35
25 45 -87.04 36.92
24 40
23
45 CONCLUSION
22 Adsorption process of cobalt (II) on layered double
21 50 hydroxides Mg/Al and Ca/Al showed the adsorption
20 rate 0.018 and 0.165, resectively. Layered double
0 20 40 60 hydroxides Mg/Al more reactive than layered double
hydroxides Ca/Al. Thermodynamics adsorption
Concentration (mg/L)
layered double hydroxides Mg/Al has higher
Fig. 4. Adsorption of cobalt (II) varied concentration and adsorption capacity than layered double hydroxides
temperature by layered double hydroxides Mg/Al
Ca/Al. Other thermodynamic parameters such as
entalphy is decreases with increasing concentration
9 and entrophy decreases with increasing of cobalt (II)
8 concentration.
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