420 S. Iftekhar et al.
/ Chemosphere 204 (2018) 413e430
Scheme 3. Proposed structure of ammonium citrate modified biochar.
2017b). In other studies, La adsorption on tangerine peel (Torab-
Mostaedi, 2013) and Plantanus orientalis leaf (Sert et al., 2008)
was explored as a function of contact time. It was observed that La
removal increased up to 60 min, and no further increase was noted
afterward. Qing (2010) observed that La adsorption by modified
bamboo charcoal increased linearly by increasing the contact time
from 0 to 480 min (Qing, 2010). Among all the adsorbents, it can be
seen from Table 1 that CL-Zn/Al LDH nanocomposites displayed 99%
removal of La within 10 min (Iftekhar et al., 2017d). In another
study, it was reported that the hybridized silica-chitosan beads
exhibited instant La adsorption within 1e5 min, while the hybrid-
ized silica-chitosan flakes of similar modifications demanded a
longer contact time of more than 2 h due to the diffusion re-
strictions in the flake form with its increased particle size
(Ramasamy et al., 2017d). The statistical analysis of the data pre-
sented in Table 1 indicates that optimum contact time for La
removal by different adsorption materials is highly variable with a
mean contact time of 329 min (Fig. 3c).
4.4. Effect of temperature
The temperature of the solution mainly affects the enlargement
nature of adsorbents, mobility of La ions and solid/liquid interface
(Iftekhar et al., 2017c). It can be seen from Fig. 2d that 298 K has the
highest frequency of occurrence, indicating that majority of studies
(Table 1) were conducted at room temperature.
Along with temperature, thermodynamic parameters were used
to determine the nature of adsorption process viz exothermic or
endothermic, spontaneity and randomness and also to determine
whether the temperature is favorable for the process or not. The
important thermodynamic parameters are DG0, DH0 and DS0 rep-
resenting the change in Gibbs free energy, enthalpy and entropy.
The negative values of DG0 are associated with the adsorption
process being spontaneous. Similarly, the positive values of DH0
indicate that the process is endothermic. Also, the magnitude of
DH0 seems to be related with the type of sorption viz. physisorption
(DH0 < 50 kJ/mol) and chemisorption (DH0 > 50 kJ/mol) (Iftekhar
et al., 2017c; d). Moreover, the positive values of DS0 could be
explained as that increase in entropy occurred due to the exchange
of metal ions by more mobile ions during adsorption process
(Iftekhar et al., 2017c). Therefore, many researchers studied the
effect of temperature on La adsorption by various adsorbents and
related works are summarized in Table 2.
From Table 2, it can be concluded that La adsorption on most of
the adsorbents reported was endothermic with few exceptions. The
adsorption process of La on SnO2eTiO2 nanocomposite (Rahman
et al., 2014), MWCNTs (Koochaki-Mohammadpour et al., 2014),
Fe3O4@Alg-CHI (Wu et al., 2011) and Fe3O4@Ca-Alg beads (Wu
et al., 2010) was observed to be exothermic as suggested by the
negative value of DH0. In addition, adsorption process seems to be
spontaneous and favorable due to negative DG0 along with positive
DS0. In a study carried out by Rahman et al. (2014) on SnO2eTiO2
nanocomposite; the negative values of DG0 increased (27.7
to 30.62 kJ/mol) with temperature from 278 to 338 K indicating
adsorption was favorable at a higher temperature (Rahman et al.,
2014). The same was observed by Mohammadpour et al. (2014) in