In addition, as the extraction and stripping process proceeded, the hydroxide ions were

released into the external phase through Reaction 6 and pH of external phase increased [16].
As the pH changed, amount of CrO42 ionsincreased and consequently reacted slowly with
NR4+Cl and NR4+OH as shown in Reactions 10 and 11. The stripping reactions of
CrO42 ions are depicted in Reactions 12 and 13.
Overall, the mechanisms of chromium extraction and stripping process involving the
HCrO4 ion TOMAC and NaOH are illustrated in Figure 1.
3.2 Emulsion Stability and Chromium Extraction Performance
3.2.1 Effect of Carrier (TOMAC) Concentration
In this present work, TOMAC has been selected as the carrier in an organic phase that
consisted of 30 % by volume from kerosene and 70 % from palm oil. Figure 2 depicts the
experimental results of chromium extraction. Apparently, with an increasing carrier
concentration from 0.01 M to 0.1M, there is more Cr-carrier complex that can be formed and,
hence, the percentage of chromium extracted from feed phase increases gradually. As shown
in Figure 2, 0.1 M TOMAC and above provide better extraction performance because they
are able to extract almost 100% of chromium. This result is in line with Chakraborty et al.,
[19] who also used high concentration of TOMAC of around 0.18 M.
However, instead of 0.1 M TOMAC, 0.2 M TOMAC had been chosen as the optimum
concentration of carrier in this case because it could increase the viscosity of the ELM as
shown in Figure 3. According to Karimi and Bjrkegren (2012), high viscosity of ELM can
help to enhance the stability of the ELM so that it would not swell or break easily during the
extraction stage. Low TOMAC concentration such as 0.01 M and 0.05 M did not increase
much of the ELM viscosity. Hence, the ELM is quite unstable and breakage of ELM occurred
as shown in Figure 2. In addition to that, at the end of extraction, ELM with the presence of
0.2 M TOMAC did undergo swelling but the extent of ELM swelling in the presence of 0.1
M TOMAC was more obvious.
Besides that, increasing the concentration of TOMAC over a certain limit can cause the
osmotic pressure to become higher in ELM than in the external phase [18, 21] and, thus, a
very obvious swelling phenomena occurred as water entered the ELM for the case of 0.4 M
and 0.6 M of TOMAC. Too high amount of carrier present in the ELM could also bring about
the increment in mass transport resistance [17] and the Cr (VI) extraction percentage
decreased consequently for 0.4 M and 0.6 M TOMAC. Therefore, 0.2 M TOMAC was
chosen as a better carrier concentration to proceed to the extraction study.
Fig 2 Chromium extraction percentage and ELM swelling percentage (TOMAC
concentration) [Experiment conditions: agitation time = 2 min, agitation speed = 600 rpm,
ratio of kerosene: palm oil = 3:7, [NaOH] = 0.1 M, [Span 80] = 3 % w/v, ratio of organic:
NaOH = 3:1 and treat ratio = 2:1]
Fig 3 Effect of carrier concentration on viscosity of liquid membrane (Experimental
conditions: ratio of kerosene: palm oil = 3:7)

3.2.2 Effect of Agitation Speed

In order to find out the optimal agitation speed that allows emulsion stability and
effectiveness chromium (VI) extraction, the effect of agitation speed was investigated in the
range of 200 till 800 rpm and the results obtained are analyzed as shown in Figure 4. The
results show that agitation speed of 200 rpm provided a higher extraction percentage with less
swelling (3 %) than 400 rpm. However, due to the low agitation speed of 200 rpm, the ELM
globules cannot be well-dispersed in the external solution and formations of large globules
were observed during the experiment. This result is in agreement with Kumbasar [21], who
attempted the extraction of chromium (VI) using kerosene-based ELM at agitation speed of
350 rpm instead of 275 rpm. Hence, 200 rpm should not be chosen as the suitable agitation
speed.
Next, when the agitation speed was increased from 400 rpm to 800 rpm, there was a gradual
increment in the chromium extraction percentage from 92 % to 97 % as shown in Figure 4.
Higher stirring rate can facilitate the formation of smaller sized ELM globules, thereby
increasing the interfacial area between the feed solution and the emulsion liquid membrane
solution, which leads to an increase in the mass transfer rates as well as the chromium
(VI) extraction efficiency [17, 22, 23].
Comparing between two high agitation speeds of 600 rpm and 800 rpm, both sets of the
experiment achieved considerably high chromium extraction percentage of about 97 %.
However, in this case, 600 rpm is more preferable than 800 rpm as the agitation speed. This
result is in line with Karimi and Bjrkegren [16], who claimed that 600 rpm is the minimum
agitation speed for a pure palm oilbased ELM to be dispersed in small sizes when contacting
the external phase with ELM due to the high viscosity of ELM. As shown in Figure 4, when
agitation speed of 800 rpm was applied in the experiment, swelling percentage also became
larger than that of 600 rpm. This indicates that agitation speeds that exceed a certain limit
could also bring about the swelling of ELM due to the increasing rate of co-transport of water
and this might cause the ELM to become highly unstable [21, 24]. Hence, 600 rpm was
considered to be the optimal agitation speed to provide a good dispersion of ELM globules
along with the least possibility of breakage. To further the study of ELM extraction and
Chromium recovery, selected conditions of stable emulsions of 0.2 M TOMAC and 600rpm
agitation speeds were used.
Fig 4 Chromium extraction percentage and ELM swelling percentage (Agitation speed)
[Experiment conditions: agitation time = 2 min, ratio of kerosene: palm oil = 3:7, [NaOH] =
0.1 M, [TOMAC] = 0.2 M, [Span 80] = 3 % w/v, ratio of organic: NaOH = 3:1 and treat ratio
= 2:1]
3.2.3 Effect of NaOH Concentration on Chromium Recovery
In this experiment, the sodium hydroxide solution acted as the stripping phase and its
concentration was considered as one of the parameters that could affect the recovery
efficiency of ELM. Figure 5 shows the effect of NaOH concentration on the chromium
extraction performance. The highest chromium extraction percentage can be achieved using
0.1 M NaOH but it provides the lowest chromium recovery percentage. It is due to the
insufficiency of stripping agent to strip out the chromium into the internal phase. Further
increment of NaOH concentration to 0.5 M enhances the recovery of chromium but the
extraction percentage decreases. With an increase of NaOH concentration from 0.5 M to 1.0
M, there is a great improvement in the chromium (VI) removal efficiency from 75 % to 93 %.
This is due to the fact that higher concentration of NaOH can provide more OH- and, hence,

more Cr ions in the form of Cr-carrier complex are able to be stripped on the inner (W/O)
interface of ELM. The more the chromium being stripped, the more carrier molecules can be
free from the Cr-carrier complexes and continue to facilitate the removal of chromium from
external solution.
From the aspect of recovery percentage, the stripping effect of NaOH increased gradually as
shown in Figure 5, 1 M of NaOH acted as the most effective stripping agent in extracting as
well as concentrating the chromium (VI) transported through the organic phase. When the Crcarrier formation rate is constant for each set of experiment due to the usage of the same
amount of surfactant and carrier, the enhanced stripping rate at higher concentration of NaOH
can be achieved by providing sufficient OH- in the stripping phase to extract the Cr (VI) from
the Cr-carrier complexes. Hence, at low concentration of NaOH, many Cr-carrier complexes
still remain unstripped in the membrane phase. This will cause low recovery percentage of
chromium.
Nevertheless, with the increase of NaOH concentration up to 2.0 M, the chromium removal
efficiency and recovery rate dropped significantly. According to Goyal et al.,[17] the
surfactant, Span 80 reacts with high concentration NaOH and thus, the effective number of
surfactant molecules reduces and then the emulsion liqui membrane destabilizes. Breakage of
ELM due to the ELM instability releases the stripped chromium back into the stripping
phase. At the same time, high concentration of NaOH induces large difference in osmotic and
pH pressure as compared to the external phase [16, 18, and 24]. This consequently results in
the swelling of the ELM, which also reduces the recovery efficiency. Hence, when the rate of
swelling is equal to the rate of breakage, there will be no observable increase or decrease in
the volume of external solution as in the case of 2 M of NaOH. Therefore, 1 M is the suitable
concentration of NaOH as it possesses the greatest ability to strip and concentrate the
chromium from the feed solution.
Fig 5 Chromium extraction percentage, chromium recovery percentage and ELM swelling
percentage (NaOH concentration) [Experiment conditions: agitation time = 2 min, agitation
speed = 600 rpm, ratio of kerosene: palm oil = 3:7, [TOMAC] = 0.2 M, [Span 80] = 3 % w/v,
[1-octanol] = 2 % w/v, ratio of organic: NaOH = 3:1 and treat ratio = 2:1]
3.2.4 Effect of Treat Ratio on Chromium Recovery
Figure 6 shows the effect of treat ratio on chromium removal and recovery. The results
present that emulsion liquid membrane (ELM) possesses greater ability to remove chromium
(VI) ion from the feed phase when the lower treat ratios was applied (2:1). This is due to the
fact that when the treat ratio is decreasing, the volume of ELM is comparatively increasing in
the system and there will be more possible active sites on the membrane phase available for
the chromium permeation process [23].
Furthermore, the ELM globules underwent swelling when treat ratio of 3:1 was applied and it
might due to the osmotic pressure difference between the ELM and external phase. The
increasing osmotic pressure difference could also bring about the rupture of ELM globule
since breakage had occurred for the treat ratio of 5:1 and 10:1. The larger osmotic pressure
difference between external and ELM phase when treat ratio increased was incurred by the
presence of larger amount of water molecules in the external phase [17]. Hence, the
percentage of chromium removal from the external phase and the percentage of chromium
recovery decrease as compared to treat ratio of 2:1. Besides, Goyal et al. [17] also claimed
that it is plausible that there is no sufficient free internal reagent, NaOH, to strip the
chromium (VI) ion from the Cr-carrier complex in membrane phase. Meanwhile, the

available carrier molecules at the O/W interface decreases and, thus, the percentage of
chromium extracted also decreases.
Fig 6 Chromium extraction percentage, chromium recovery percentage and ELM swelling
percentage (Treat ratio) [Experiment conditions: agitation time = 2 min, agitation speed = 600
rpm, ratio of kerosene: palm oil = 3:7, [TOMAC] = 0.2 M, [NaOH] = 1 M, [Span 80] = 3 %
w/v, [1-octanol] = 2 % w/v and ratio of organic: NaOH = 3:1]
In this study, the similar chromium removal percentages achieved using treat ratios of 2:1 and
3:1 implied that treat ratio of 3:1 would be the more economically effective choice in
chromium extraction as less ELM is needed to treat the same amount of external phase.
However, when the chromium recovery efficiency is considered, the higher chromium
recovery percentage of 97 % can be achieved using treat ratio of 2:1 as compared to that of
treat ratio of 3:1, which is only 69 %. Besides, when treat ratio of 2:1 was applied in the
experiment, the ELM phase did not undergo such swelling or breakage problem as other treat
ratios used in the extraction. Hence, it can be concluded that treat ratio of 2:1 is the best to be
applied in the chromium extraction and recovery process.
4.0 CONCLUSION
In this work, the extraction and recovery of Cr by ELM using palm oilbased liquid
membrane were investigated. Diluent containing kerosene-palm oil mixture with the ratio of
3:7 was selected and used. The influence of various parameters on the Cr extraction and
recovery has been accepted and the results show that the optimum conditions were identified,
such as 0.2 M for carrier (TOMAC) concentration, 600 rpm for agitation speed, 1.0 M for
internal phase (NaOH) concentration, 2:1 for treat ratio and 3 minutes for agitation time in
order to enhance the recovery of chromium in ELM process.
Acknowledgements
The authors would like to acknowledge the ministry of science technology and innovation
(Vot 4F450), Centre of Lipids Engineering and Applied Research (CLEAR), and Universiti
Teknologi Malaysia (UTM) for facilities support to make this research possible.