CHAPTER 1

INTRODUCTION

Industrial activity is major environmental issue for heavy metals

contamination. Rapid industrialization has contributed the release of toxic metals
in the water streams. World health organization states that water must be free from
organisms. According to WHO the toxic heavy metals are aluminium, chromium,
copper, mercury, nickel, iron, lead, zinc [1].

Chromium (VI) is one of the world‘s most major strategic and critical
materials. It is having a wide range of uses in the several industries, such as
leather, textile, pigment and metal plating industries. Being chromium is a
carcinogen it also irritates eyes, causes chromosome abnormalities, liver and
kidney damage [2]. Cr exists in several oxidation states, but it is in 2 oxidation
states in the environment, Cr (III) & Cr (VI). Cr (VI) is highly soluble and more
toxic to the environment like soil, aquatic systems and chromium is a strong
oxidant so they are easily absorbed by skin [3]. Cr (VI) is a primary contaminant
because of its toxicity to humans, animals, plants and microorganisms [4, 5].
Trivalent chromium is relatively insoluble and it should be nutrient for living
organisms [6].

Discharge concentration of chromium (VI) in metal plating industry is 127

mg/l per day. Cr (VI) discharge in textile industry is 2.38±0.005 mg/l, but the

1
acceptance level for Cr (VI) into the surface water is 0.1 mg/l and in drinking
water is 0.05 mg/l [7]. So the removal of Cr (VI) is most important one.

Removal of Cr (VI) ions from wastewater is usually achieved by physical

and chemical processes [8] which include precipitation [9], coagulation, ion
exchange [10] reverse osmosis [11], membrane separation [12], solvent extraction
[13] and adsorption [14]. However precipitation produces large amount of sludge,
and disposal of sludge also difficult, it requires maintenance. Coagulation is high
cost and large consumption of chemicals. Ion exchange is highly expensive,
requires careful design and it removes less number of metal ions. Reverse osmosis
plants occupies more place [15]. Membrane separation has disadvantages like
fouling, removal efficiency decreases with the presence of other metal ions, high
initial and running cost. In adsorption mostly activated carbon is used. It requires
huge amount of activated carbon and it‘s difficult to regenerate and reuse [16].
Among these methods solvent extraction is chosen for this present work, because
it is cost effective process with simple design, the recovered and recycled of
solvent is very well possible. Chromium (VI) ions by liquid–liquid extraction
(LLE) can be analyzed by various analytical methods including High Performance
Liquid Chromatography [HPLC] [17], UV-Spectrophotometer [18], Flame Atomic
Absorption Spectroscopy [19, 20] and Emission Spectroscopy.

Solvent extraction, an effective separation method is employed to separate

compounds based on their relative solubility in two different immiscible liquids
[21, 22]. There are various parameters which affect the extraction efficiency such
as pH, agitation speed, feed concentration, treat ratio and temperature. The
maximum percentage removal of Cr is obtained when all these parameters have
optimized values. These values can be estimated either by experiments involving
the variation in the value of one parameter at a time while keeping other
parameters at constant values or by using response surface methodology [23]. IL is

2
a molten salt in the form of liquid at ambient conditions. It consists of bulky
organic cations and inorganic anions. Melting point is below the arbitrary
temperature. IL‘s are negligible vapor pressure and are non-flammable [24].
Application of ILs in extraction and removal of organic compounds, like metal
ions [25], phenols, [26, 27, 28], biofuels [29], sulfur compounds in diesel oil [30].
Therefore, ILs can be regarded as clean and green solvents for separation. IL is
non-corrosive and thermally stable, and they possess excellent solubility for both
organic and inorganic compounds. Ammonium pyrrolidine dithiocarbamate
(APDC) is one of the effective solvent [17, 31].

Optimization methods determine a single factor at a time while fixing all

other variables at one level. Response surface methodology (RSM) is a statistical
tool, effective for responses that are influenced by many factors and their
interactions. RSM not only provides the optimum level for each variables it also
estimates interactions [32, 33]. This methodology cuts down the number of
experiments without affecting the interactions among the parameters. RSM has
been used to optimize the parameters such as fermentation, biosorption of metals,
oxidation and catalyzed reaction conditions [34]. It has also been a useful tool to
optimize the parameters such as temperature, pH, stirring speed, concentration,
treat ratio [35–37].

The aim of the present work was to investigate the batch extraction of
chromium (VI) using ammonium pyrrolidinedithiocarbamate and 1-butyl 3-
methyimidazolium hexafluorophasphate. Factors affecting the extraction system
were investigated.

1.1 CHROMIUM

Chromium is an important industrial metal used in diverse products and

processes. It is widely used in many industrial processes such as stainless steel,

3
chrome plating in metal ceramics, leather tanning, textile manufacturing, wood
preserving, pigmenting, chromium chemical production, pulp and paper industrial.
Chromium plating was once widely used to give steel with a polished silvery
mirror coating. It is used in metallurgy to impart corrosion resistance and a shiny
finish; as dyes and paints and it is used to produce synthetic rubies; as a catalyst in
dyeing and in the tanning of leather; to make moulds for the firing of bricks.
Chromium exists in several oxidation states, but mainly 2 common oxidation
states of chromium are present in the environment Cr (III) and Cr (VI). These
applications will mainly increase concentrations of chromium in water.

1.1.1 CHEMICAL AND PHYSICAL PROPERTIES OF CHROMIUM

The name, Chromium is derived from Greek word Chroma (Colour) as all
compounds of chromium are colored. Some important properties of chromium are
shown in Table 1:

Table 1: Properties of chromium

Atomic Symbol Cr
Atomic number 24
Atomic mass 51.996 [Link] -1
Electro negativity 1.6
Density 7.19 [Link]-3 at 20°C
Melting point 1907 °C
boiling point 2672
Vanderwaals radius 0.127nm
Ionic radius 0.061 nm (+3) ; 0.044 nm
(+6)

4
1.1.2 HEALTH IMPLICATIONS OF CHROMIUM

Trivalent chromium occurs naturally in many fresh vegetables, fruits,

meats, grains and yeast. But the uptake of too much chromium(III) can cause
health effects as well, for instance skin rashes. It is mineral nutrient essential to the
cell membrane receptor sites stimulated by insulin. In the absences of Cr(III),
tissues resist insulin‘s influence. Blood sugar can‘t enter the cells to be
metabolized and signs of type II diabetes may appear. Cr(III) is more stable, less
toxic, and listed as an essential element (in trace concentrations) to provide good
health . Most of the chromium that we swallow leaves our body within a few days
through the feces and never enters our blood stream, if it is in very small quantity
(an intake of 50–200 μg of Cr(III) per day is recommended for adults daily from
food).

In general, human being can be exposed to chromium by breathing air,

drinking water, eating food-containing chromium or through skin contact with
chromium or chromium compounds.

The International Agency for Research on Cancer (IARC) has determined

that Cr (VI) is carcinogenic to human beings, based on sufficient evidence in
humans for the carcinogenicity of Cr (VI) compounds as found in chromate
production, chromate pigment production and chromium planting industries. Lung
cancer may occur due to long term exposure to Cr (VI) (Washington State
Department of Health, 1995). Breathing high level of Cr (VI) can cause irritation
to the nose, such as runny nose, nosebleeds and ulcers and holes in the nasal
septum. Ingesting large amount of Cr (VI) can cause stomach upsets and ulcers,
convulsions, kidney and liver damage and even death. Skin contact with certain Cr
(VI) compounds can cause skin ulcer. Cr (VI) compounds can penetrate the skin
more readily than the trivalent compounds. The most commonly affected areas are
wrists, fingers and the back and sides of hands (ATSDR, 2000). Chromium is not
5
known to accumulate in the bodies of fish, but high concentrations of chromium,
due to the disposal of metal products in surface waters, can damage the gills of
fish that swim near the point of disposal.

1.1.3 STANDARDS AND GUIDELINES

The following agencies have set the guidelines and standard values, and the
maximum permissible limit of total chromium in drinking water shown in Table 2:

Table 2: Guidelines and standard values of total

Agencies Maximum level, (mg/l)

European Community (EC) 0.05

World Health Organization (WHO) 0.05

Environment Protection Agency, United State of 0.10

America (USEPA)

1.2 LIQUID-LIQUID EXTRACTION

1.2.1 LLE PRINCIPLE

LLE or solvent extraction is a useful technique for separation of both

organic and inorganic compounds from interferences based on the partitioning
between two immiscible liquid phases. This technique can separate substance in
the concentration range of trace to macro level. One phase in LLE is usually
aqueous and the other is an organic solvent.

Solvent extraction is a chemical term that means the separation process of

compounds using solvents by dissolving the mixture in another solvent. The
product of the extraction is called distribution ratio.

6
1.2.2 DISTRIBUTION CO-EFFICIENT AND DISTRIBUTION RATIO

Nernst Distribution Law is the fundamental law of quantitative basis

governing of a solute between two immiscible solvents. This can be stated that at
equilibrium, constant temperature and pressure, any solute will distribute between
two essential immiscible solvents with the constant ratio of the concentration of
solute in the two phases. For a solute X distributing between aqueous and organic
solvent, the distribution coefficient, KD is defined as follows:

Xaq ↔ Xorg

KD

Where [X]org is the concentration of solute in organic phase

[X]aq is the concentration of solute in aqueous phase

It is important to realize that the distribution coefficient refers to only

one specific species. The distribution coefficient is roughly a measure of the
relative solubility of the particular species, and it not a total actual concentration in
each phase. When more than one species are involved in the distribution, each
species will distribute independently of all other, the distribution ratio, D is
evaluated.

The distribution ratio is defined as the ratio of concentration of all the

species of the solute in each phase. The distribution of a solute X with numerous
forms in solution between aqueous and organic solvents is

KD

Where, │ [ Xorg]│— Concentration of solute in Organic solvent

7
 │ [Xaq] │— Concentration of solute in aqueous solution

1.2.3 PERCENTAGE EXTRACTION (%E)

Extraction Efficiency is the ratio of difference in the concentration of a solute in

aqueous phase to the initial concentration of solute in the aqueous phase. The
equation is given by

%E

Where, (Ci)aq – Initial concentration of solute in aqueous phase

(Cf)aq – Final concentration of solute in aqueous

1.3. IONIC LIQUIDS

Ionic Liquids (ILs) are simply molten salts, which are made up of cations
and anions. Inorganic salts such as sodium halides are solids with melting points
well above [Link] be a part of the IL family, a given salt must have a melting
point fixed at or below [Link] the salt melting point is below room temperature
(~250C), the IL is called room temperature ionic liquid (RTIL).The term ionic
liquids covers inorganic as well as organic molten salts.

The RTIL‘s are made up of bulky nitrogen or phosphorous containing

organic cation such as alkyl-imidazolium, pyridinium or pyrollidinium,
ammonium or phosphonium cations and the anion part is a chloride,nitrate,
perchlorate, chloraluminate, tetrafluoroborate, or hexafluorophosphate anions.

RTIL‘s generally exhibit good solvent properties and can often facilitate
and influence most chemical reactions without being transformed in the process.
Most RTIL‘s have negligible vapor pressure and very little flammability and they
also exhibit high thermal stability and wide working temperature ranges. Research
has shown that RTIL‘s can be effective substitutes for common organic solvents
8
like benzene, toluene, kerosene etc. where control of volatile organic carbons
(VOC) emissions is critical. The extremely low vapor pressure of most IL‘s is the
main reason that renders them useful in green chemistry. In chemical processes,
they are easily recyclable and produce minimum pollution by volatile organic
compounds if no organic solvents are used to recycle them.

1.3.1. HISTORY OF IONIC LIQUIDS

The discovery date of the ―first‖ ionic liquid is disputed, along with
the identity of the discoverer. Ethanol ammonium nitrate was first reported in
1888 by [Link] and [Link]. One of the earliest truly room temperature ionic
liquids was ethyl ammonium nitrate, synthesized in 1914 by paul walden. In the
1970‘s and 1980‘s ionic liquids based on alkyl-substituted imidazolium and
pyridinum cations, with halide or tetrahalogenaluminate anions, were initially
developed for use as electrolytes in battery applications.

In 1992, Wilkes and Zawarotko obtained ionic liquids with ‗neutral‘

weakly coordinating anions such as hexafluorophosphate [PF6]- and
tetrafluoroborate(BF4)-, allowing a much wider range of applications.

1.3.2. LOW TEMPERATURE IONIC LIQUIDS

Low temperature ionic liquids (130K) have been proposed as the fluid
base for an extremely large diameter spinning liquid mirror telescope to be based
on the Earth‘s moon. Low temperature is advantageous in imaging long wave
infrared light which is the form of light that arrives from the most distant parts of
the visible universe. Such a liquid base would be covered by a thin metallic film
that forms the reflective surface. Low volatility is important for use in lunar
vacuum conditions.

9
1.3.3. SAFETY OF IONIC LIQUIDS

Ionic liquid‘s non-volatility effectively eliminates a major pathway for

environmental release and contamination. However, this property is distinct from
toxicity. Ionic Liquid‘s aquatic toxicity is as severe as or more so than many
current solvents. Mortality isn‘t necessarily the most important metric for
measuring impacts in aquatic environments, as sub-lethal concentrations change
organisms‘ life histories in meaningful ways. Despite low vapor pressure many
ionic liquids are combustible and therefore require careful handling. Brief
exposure (5 to 7 seconds) to a flame torch can ignite some ILs .Complete
combustion is possible for some ILs.

1.3.4. APPLICATIONS OF IONIC LIQUIDS

1. Chemical Industry: The first major IL application was the BASIL

(Biphasic Acid Scavenging utilizing Ionic Liquids) process by BASF, in
which 1-alkylimidazole scavenged the acid from an existing process. This
then results in the formation of an IL, which can be easily be removed from
the reaction mixture. This increased the space time/yield time of the
reaction by a factor of 80,000.
2. Pharmaceuticals: It is known that approximately 50% of the commercial
pharmaceuticals are organic salts, ionic liquid forms a number of
pharmaceuticals have been investigated.
3. Algae Processing: Algae is perhaps the most widespread organism on
earth, occupying most niches on the planet. Algae perform photosynthesis
and produce high-energy molecules such as lipids and sugars, that can be
converted to useful chemicals such as biodiesel, ethanol and other biofuels.
To accomplish this, however, algae must be harvested and its constituents
extracted from within the cell in an economically viable industrial process.
ILs have been shown to be effective at destroying the cell wall and
10
 releasing cell contents using a fraction of the energy, and potentially the
cost, of current harvesting and extraction process.
4. Food and bioproducts: The ionic liquid 1-butyl-3-methylimidazolium
chloride completely dissolves freeze dried banana pulp and with an
additional 15% Dimethylsulfoxide, lends itself to Carbon-13 Nuclear
Magnetic Resonance analysis. In this way the entire banana complex of
starch, sucrose, glucose and fructose can be monitored as a function of
banana ripening. ILs can extract specific compounds from plants for
pharmaceutical, nutritional and cosmetic applications, such as the
antimalarial drug artemisinin from the plant Artemisia annua.
5. Waste recycling: ILs can aid the recycling of synthetic goods, plastics and
metals. They offer the specificity required to separate similar compounds
from each other, such as separating polymers in plastic waste streams. This
has been achieved lower temperature extraction processes than current
approaches and could help avoiding incinerating plastics.
6. Batteries: Researchers have identified ILs that can replace water as the
electrolyte in metal-air batteries. ILs has great appeal because they
evaporate at much lower rates than water, increasing battery life by drying
slower. Further, ILs have an electrochemical window of upto 6 volts (Vs
1.23 for water) supporting more energy-dense metals. Energy densities
from 900-1600 watt-hours per kilogram appear possible. A metal- air
battery draws oxygen through a porous ambient ―air‖ electrode (-cathode)
and produces water, hydrogen peroxide, or hydroxide anions depending on
the nature oxygen reduction catalyst and electrolyte. These compounds
store the electrons released by the oxidation of the anode.

11
1.4 OBJECTIVE
 To extract the chromium (VI) ions from aqueous solutions.
 To analyse the extracted chromium (VI) ion.
 To study the influence of various parameters that affecting the extraction
performance like
 pH
 Speed
 Feed concentration
 Temperature
 Treat ratio
 Optimization of extraction parameters

12
 CHAPTER 2

REVIEW OF LITERATURE

BertaGala.n et al 2005., The focus of this work has been the study of Cr(VI)
removal from ground waters and the simultaneous concentration for its reuse
using three different technological alternatives: anion-exchange resins, liquid–
liquid extraction assisted by hollow fibre membranes and emulsion pertraction.
The viability of the considered objectives, i.e., Cr(VI) separation(0.5 g/m3) and
concentration for reuse (420,000 g/m3) has been checked and a comparative
analysis of the three technologies has been performed. Although the flexibility
and ease of operation of non-dispersive solvent extraction, anion-exchange
resins and emulsion pertraction lead to higher velocities of chromium removal,
yet still maintaining similar concentration efficiencies.

Mohammad Abul Hossain et al 2005., A simple and rapid method was

developed for the simultaneous determination of Cr(VI) and Cr(III) based on
the formation of their different complexes with ammonium
pyrrolidinedithiocarbamate (APDC). Separation was performed using
reversed-phase high-performance liquid chromatography coupled with UV
detection. The conditions for complex formation and speciation were
determined, such as solution pH, amount of APDC, temperature, and type of
mobile phase. In order to substantially reduce the analysis time, the separation
was carried out without extraction of chromium-APDC complexes from the
mother liquor. Under the optimum analysis conditions, the chromatograms
obtained show good peak separation.
13
Berta Gala et al 2005., The focus of this work has been the studied of Cr(VI)
removal from ground waters and the simultaneous concentration for its reuse
using three different technological alternatives: anion-exchange resins, liquid–
liquid extraction assisted by hollow fibre membranes and emulsion pertraction.
The viability of the considered objectives, i.e., Cr(VI) separation (0.5 g/m3)
and concentration for reuse (420,000 g/m3) has been checked and a
comparative analysis of the three technologies has been performed.

Mahdi Chiha et al 2006., The membrane phase consists of hexane as diluent,

tributyl phosphate as extractant, and sorbiton monooleate as surfactant. A
NaOH solution is the internal aqueous phase. Results show that with proper
adjustment of experimental conditions the stability of the membrane can be
enhanced to a great extent. This study also examined the effects of the
concentrations of feed phase acid, metal ions, and carrier on the extraction of
Cr(VI) ions. Further, the extraction kinetics of the metal ions by LSMs was
examined. The results also showed that by appropriate selection of the
extraction and stability conditions, nearly all of the Cr(VI) ions present in the
continuous phase were extracted within a few minutes. The influence of the
NaOH concentration on stripping efficiency was investigated. Efficiency of
Cr(VI) was 95%.

Weidong Zhang et al 2007., Extraction % of Cr (VI) from different inorganic

acid solutions follows the order: HCL > H2SO4 >H3PO4. At the lowest pH
value of 0 and highest TBP concentration, the maximum distribution
coefficient 1359 and an extraction efficiency of 99.9% were achieved. More
than 70% of the Cr(VI) could be recovered with 0.3 mol.L-1 of NaOH
solution.

14
Aniruddha Pisal 2007., Chromium can occur as Cr(III) or Cr(VI) in dissolved
form in different concentrations in all kinds of waters. Cr(VI) is more toxic
than Cr(III) and is of specific interest. Chromium was determined
colorimetrically by reaction with diphenylcarbazide in acid solution. A red-
violet colour of unknown composition is produced which is measured at 540
nm. Estimated total chromium, digest the sample with a sulphuric-nitric acid
mixture and then reacting with the diphenylcarbazide.

Shan Haixia et al 2007., The present work was described for the
preconcentration of ultratrace amounts of lead in water. Dithizone was
employed as a chelator forming a neutral lead-dithizone complex to extract
lead ions from aqueous solution into the ionic liquid 1-octyl- 3-
methylimidazolium hexafluorophosphate. The extraction efficiency was 99.9
and 99.8%. The determination of lead was free from interference from almost
all cations and anions, and from humic acid in water from plant rot. Lead
recoveries between 97.8 and 100.8% for spiked samples prove the accuracy of
the method.

R.S. Karale et al 2007., The aim of this project is to adopt appropriate

methods and to develop suitable techniques either to prevent metal pollution or
to reduce it to very low levels with due consideration to cost optimization.
Extensive chemical analysis was done to detoxify Cr (VI) by reducing it to Cr
(III) by using reducing agents such as ferrous sulphate and sodium
metabisulphite, and the precipitation of chromium hydroxide by addition of
base. Also experiments were conducted to study the effect of reduction time
and pH on the reduction of chromium for various doses of reducing agents. In
this paper, efforts have been made to highlight the cost economics of removal
and recovery of chromium.

15
M. Rajasimman et al 2009., The characteristics of raw waste sodium
dichromate sludge recovered from pharmaceutical industry were studied and
found that it is highly acidic and contains high dichromate ions. Statistical
experimental design was applied for the optimization of process parameters for
the extraction of chromium by emulsion liquid membrane. The effects of
process parameters, agitation speed, membrane to emulsion (M/E) ratio and
carrier concentration on the extraction of chromium were optimized using a
response surface method. RSM was used to find the optimum process
conditions for the extraction of chromium. The values predicted by RSM were
found to vary with R2 value of 0.9614 and 0.9124 for Trioctyl amine and
Aliquat-336. The optimized condition the maximum chromium extraction was
found to be 89.2% and 96.15% using Trioctylamine and Aliquat-336.

[Link] et al 2010., The Cr(VI) is held by electrostatic attraction as an

ion-association complex of HCrO4 with tricaprylmethylammonium chloride
and extracted into the organic phase using isoamylalcohol (IAA) as the diluent.
The effects of various experimental parameters that affect the extraction
process have been examined. Chromium can be determined UV-visible
spectrophotometer. Extraction percentage of chromium was- 96%.

Yinghui Liu et al 2010., A series of silica-based organic–inorganic hybrid

materials were prepared by the sol–gel process for Cr(III) and Cr(VI)
adsorption. Trialkylmethyl ammonium bis 2,4,4 trimethylpentylphosphinate
and trihexyl(tetradecyl) phosphonium bis 2,4,4-trimethylpentylphosphinate
(Cyphos IL) were explored as porogens to prepare porous silica and as
extractants to extract chromium ions. Cyphos IL and [A336][C272]
functionalized silica sorbents (SG-2, SG-5) can be effectively used for the

16
removal of Cr(III) and Cr(VI) from aqueous solutions by adjusting pH values,
whereas trialkylmethyl ammonium chloride and bis(2,4,4-trimethylpentyl)
phosphinic acid (Cyanex 272) functionalized silica sorbents (SG-3, SG-4) can
only be used for the removal Cr(VI) or Cr(III). The maximum adsorption
amounts of Cr(III,VI) were 2.14 and 19.31mgg−1 for SG-2 and 2.32 and
15.29mgg−1 for SG-5.

Rahul Kumar Goyal et al 2010., A new type of emulsion liquid membrane

(ELM) has been prepared to separate and concentrate chromium (Cr) from
waste water. A hydrophobic ionic liquid 1-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ([BMIM]+[NTf2]−) is used in the membrane
phase as a stabilizer to provide sufficient stability and a second ionic liquid
Tri-n-octylmethylammonium chloride (TOMAC) as a carrier. kerosene as
[Link] effects of various parameters such as homogenization speed,
carrier concentration, internal phase concentration, agitation speed, treat ratio,
internal to membrane phase ratio,surfactant concentration, pH of the feed phase
and ([BMIM]+[NTf2]− concentration was investigated. 97% percentage of Cr
could be extracted.

[Link] 2010., proved that The task specific ionic liquid tricaprylmethyl
ammonium thiosalicylate to be an excellent extraction agent for chromium
from aqueous solution. Chromium was removed from tannery effluents to a
greater extent than the conventional methods using the water insoluble, thiol
containing task specific ionic liquid. It was found to remove more than 90% of
Chromium from tannery effluents.

Behrooz Majidi et al 2011., This report on the salt-assisted liquid-liquid

microextraction of cationic complexes of Cr(VI) ion using the hydrophilic

17
ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoraborate and potassium
hydrogen phosphate. This is a novel, simple, non-toxic and effective technique
for sample pretreatment technique that displays large extraction efficiency and
represents a new platform where Cr(VI) is complexed with 1,5-
diphenylcarbazide (DPC) in sulfuric acid medium. It was applied to the
extraction of Cr(VI) in the form of the Cr(VI)- DPC complex prior to its
determination by flame atomic absorption spectrometry. Extraction is mainly
affected by the amount of water-soluble IL, the kind and quantity of inorganic
salts, by pH and the concentration of DPC.

Li-Yan Ying et al 2011., A simple method has been proposed for the
determination of chromium species by high-performance liquid
chromatography (HPLC) after preconcentration by the ionic liquid, 1-butyl-3-
methyimidazolium hexafluorophosphate ([C4MIM][PF6]). The simultaneous
preconcentration of Cr(VI) and Cr(III) in wastewater was achieved with
ammonium pyrrolidinedithiocarbamate (APDC) as the chelating agent and the
ionic liquid [C4MIM][PF6] as the extractant. Baseline separation of the APDC
chelates of Cr(III) and Cr(VI) was realised on a RP-C18 column using a
mixture of methanol–acetonitrile–water (53:14:33, v/v) as the mobile phase at
a flow rate of 1.0 mLmin−1. Recoveries ranged from 91.8% to95.8%.

Kuppusamy Ranganathan et al 2011., In this studies tanneries reusing

wastewater by combination of conventional and advanced Reverse Osmosis
(RO) treatment technologies were assessed for technical and economic
viabilities. The effluents of tanneries are segregated as high TDS soaking
wastewater, toxic chromium wastewater and other wastewaters channels. After
chromium recovery the wastewater are mixed with other wastewater and
provided advanced treatment for water recycling. The studied tanneries show

18
that the removal of total dissolved solids, sodium and chloride are in the range
of 91-99%.

Rahul Kumar Goyal et al 2011., Emulsion ionic liquid membrane (EILM)

was prepared using ionic liquids, i.e. TOMAC as an extractant and
[BMIM]+[NTf2]− as a stabilizer for the separation of Cr. The parameters such
as carrier concentration, internal phase concentration, agitation speed, treat
ratio, internal to membrane phase ratio, surfactant concentration and pH of the
feed phase were optimized separately by response surface methodology.
Interaction between two parameters suggested their inter-dependence on each
other and their effect on the final percentage removal of Cr. a good stability
could be obtained by the combination of [BMIM]+[NTf2]−.

Ignacio López-García et al 2012., A new procedure for the determination of

very low levels of Cr(III) and Cr(VI) using ionic liquid dispersive liquid–liquid
microextraction(IL-DLLME) followed by electrothermal atomic absorption
spectrometry (ETAAS) is presented. The ionic liquid, 1-octyl-3-
methylimidazolium bis(trifluoromethanesulfonyl)imide([C8MIm][NTf2]), is
formed in situ by mixing 1-octyl-3-methylimidazolium chloride([C8MIm]Cl)
and lithium bis(trifluoromethanesulfonyl)imide ([NTf2]Li) aqueous solutions,
and is used to extract Cr(III) and Cr(VI) with ammonium
pyrrolidinedithiocarbamate (APDC). The recoveries of spiked samples are in
the 95–104% range.

A. Brinda Lakshmi et al 2012., Ionic liquid [Bmim]þ[BF4]_ in TBP was

found to be an effective solvent that enables high extraction of phenol and
chlorophenols. The parameters which affect extraction and stripping were
carefully studied and optimized. The optimum conditions for maximum
19
stripping of phenols were found to be as strip phase pH 10 and NaOH
concentration in strip phase of 0.007 N. The extraction is not much influenced
by an increase in temperature, so room temperature conditions were found to
be suitable for performing extraction. The solvent TBP and ionic liquid
[Bmim]þ[BF4]_ were recovered using stripping agent and reused.

Mohamed E et al 2013., The present work describes a continuation of our

efforts to establish the novel static step-by-step deposition and extraction
technique (SbS-DET) as an efficient and low cost methodology for treatment
of chromium. Cr(III) and Cr(VI) were efficiently removed from aqueous
solutins by using the static (SbS-DET) technique. The extraction process was
initiated by an initial deposition step of 8-hydroxyquinoline (8HQ) from
ethanolic solution on the surface of a glass substrate. Several experimental
parameters were found to exhibit significant contributions to the static (SbS-
DET) such as solution pH, deposition area, reaction temperature, dipping
cycles, dipping time and metal ion concentration were investigated. Cr (III)
was highly extracted in pH ≥ 5.0, while Cr(VI) was efficiently extracted in
lower pH ≤ 2.0.

20
 CHAPTER 3

MATERIALS AND METHODOLOGY

3.1. SELECTION OF IONIC LIQUID

The Ionic Liquid (IL) 1- butyl 3- methyimidazolium hexafluorophosphate
[C4MIM][PF6] was selected for the extraction process. Because imidazolium based
IL shows higher extraction efficiencies than pyridinum based IL‘s [31]. From the
Literature survey APDC gives higher efficiency.

3.2. EXPERIMENTAL SETUP

3.2.1 CHEMICALS AND REAGENTS
 Potassium dichromate ( K2Cr2O7)
 Diphenylcarbazide (DPC)
 Sodium hydroxide (NaOH)
 Conc. Sulfuric acid (H2SO4)
 Distilled water
 APDC
 Ionic Liquid
3.2.2 MATERIALS REQUIRED
 Beaker
 PH Meter
 Pipette
 Measuring jar
 Magnetic Stirrer
 Volumetric Flask
 Uv- Spectroscopy

21
3.2.3 PROCEDURE
[Link] CALIBRATION PROCEDURE
Chromium (VI) stock solution: 0.566g of potassium dichromate (K2Cr2O7)
was diluted to 100 ml of water.(1ml=100ppm of chromium)
Chromium (VI) standard solution: Stock solution was added to varying
concentration (10-100ppm) of stock solution and made to 100 ml by adding
distilled water. 0.2N of Sulfuric Acid was prepared.
200 of diphenylcarbazide were dissolved in 50 ml of acetone. 10 ppm of
chromium (VI) was prepared by adding 1 ml of stock chromium solution to a 100
ml beaker and 5 drops of concentrated phosphoric acid was added to that beaker
then the solution was made up to 100 ml and sulfuric acid was added for P H
adjustment. PH was measured by using PH meter. 2 ml of diphenylcarbazide was
added to the same beaker, then the mixture was stirred with a magnetic stirrer and
settling time of 5 – 10 mins was given for full colour development. Appropriate
portion was transferred to a 1 cm absorption cell and measured the absorbance at
540nm with the blank solution as a reference. This procedure was repeated for
other concentrations.

[Link] DETERMINATION OF EQUILIBRIUM TIME

10ppm standard solution was prepared by adding 1ml of K2Cr2O7 stock
solution and made to 100 ml by adding distilled water.15ml of the above solution
was taken for extraction. Exactly 100µl of ionic liquid (1-butyl 3-
methyimidazolium hexafluorophasphate) and 2ml of APDC (Ammonium
pyrrolidine dithiocarbamate) was also taken. Stirring was done for 30mins and
sampling was taken for every 5mins interval. The sample was centrifuged and
aqueous and organic phase was separated and aqueous phase was taken for UV
analysis. The sample was analysed using Uv-vis spectrophotometry and the

22
absorbances for various samples were noted. % Extraction was calculated from the
calibration chart. Percentage extraction Versus Extraction time was plotted.

[Link] STUDY ON EFFECT OF pH

15ml of the stock solution was taken for extraction. Exactly 100µl of ionic
liquid (1-butyl 3-methyimidazolium hexafluorophasphate) and 2ml of APDC
(Ammonium pyrrolidine dithiocarbamate) was also taken. The extraction was
carried out for 35mins and the pH was determined using pH meter. The Extraction
was carried out for various pH. The sample was centrifuged and aqueous and
organic phase was separated and aqueous phase was taken for UV analysis. The
sample was analysed using Uv-vis spectrophotometry and the absorbances for
various samples were noted. % Extraction was calculated from the calibration
chart. Percentage Extraction Versus pH was plotted.

[Link] STUDY ON EFFECT OF AGITATION SPEED

15ml of the K2Cr2O7 stock solution was taken in a beaker. Exactly 100µl of
ionic liquid (1-butyl 3-methyimidazolium hexafluorophasphate) and 2ml of APDC
(Ammonium pyrrolidine dithiocarbamate) was added. The extraction was carried
out for 35mins and at the pH value of 6 by varying the agitation speed from 100 -
500 rpm at the interval of 100 rpm. The sample was centrifuged and aqueous
phase was separated from organic phase taken for analysis. The sample was
centrifuged and aqueous and organic phase was separated and aqueous phase was
taken for UV analysis. % Extraction was calculated from the calibration chart. %
Extraction Verus Agitation speed was plotted.

[Link] DETERMINATION OF FEED CONCENTRATION

15ml of the K2Cr2O7 stock solution was taken for extraction. Exactly 100µl
of ionic liquid (1-butyl 3-methyimidazolium hexafluorophasphate) and 2ml of

23
APDC (Ammonium pyrrolidine dithiocarbamate) was also taken. The extraction
was carried out for 35mins and at the pH value of 6 by varying the feed
concentration from 10-60 ppm at the interval of 10ppm. The sample was
centrifuged and aqueous and organic phase was separated and aqueous phase was
taken for UV analysis. The sample was analysed using Uv-vis spectrophotometry
and the absorbances for various samples were noted. % Extraction was calculated
from the calibration chart % Extraction Versus Feed ratio was plotted.

[Link] PROCEDURE FOR EFFECT OF TEMPERATURE

15 ml of K2Cr2O7 stock solution was taken in a beaker and 2 ml of APDC
and 100µl of IL was added. The above mixture was taken for stirring at 35 mins
and pH value of 6. Then the temperature was increased at 35 oC – 55 oC. The
sample was centrifuged and aqueous and organic phase was separated. Aqueous
phase was taken for UV analysis.

[Link] PROCEDURE FOR TREAT RATIO

10 ml of K2Cr2O7 stock solution was taken in a beaker and IL , APDC was
added in the varies ratio of 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 . The mixture was taken
for stirring at 35 mins in the pH value of 6 and 50 oC . The sample was
centrifuged and aqueous and organic phase was separated. Aqueous phase was
taken for UV analysis.

[Link] PROCEDURE FOR EFFECT OF VOLUME % OF IL IN APDC

10 ml of K2Cr2O7 stock solution was taken in a beaker and IL concentration
was varied at 50-300µL. The mixture was taken for stirring at 35 mins in the pH
value of 6 and 50 oC. The sample was centrifuged and aqueous and organic phase
was separated. Aqueous phase was taken for UV analysis

24
 CHAPTER 4

RESULT AND DISCUSSION

4.1. RESULTS OF CALIBRATION

Fig 4.1: Calibration Curve for Cr ions.

The calibration data showed that the value of R2 (Regression Coefficient) was
found to be 0.991.

4.2 EQUILIBRIUM TIME

To determine the equilibrium time extraction of Chromium (VI) ions
using [C4MIM][PF6] and ammonium pyrrolidine dithiocarbamate (APDC) has
been carried out for a time interval of 5mins till 40 mins. It was found that
equilibrium was achieved at 30 mins and the future experiments on extraction are
planned to carry out for 35 mins to ensure equilibrium.
Table 4.2 Determination of Equilibrium Time
Time (min) 5 10 15 20 25 30 35 40
% Extraction 33 35 52 66 78 86 86 86

25
Fig 4.2: Efficiency Vs Time

From graph, Optimum Time = 30 mins

4.3 EFFECT OF pH
pH plays a critical role on the formation of complex between the APDC
and Cr(VI). pH is one the most important parameter affecting the extraction of
Cr(VI) ions. The effect of pH was investigated in the pH range of 2-9. The results
of pH experiments are shown in Fig.2. As can be seen from Fig. 2, % Extraction
gradually increases from pH value of 2-6. NaOH and sulfuric acid was chosen for
pH adjustment. The maximum extraction % of 92.27% was achieved at pH 6. The
reason for the decreasing pH may be the presence of oxygen atom (14) and
inability of chromium to form complex with APDC (37). Therefore, pH 6 was
selected for further studies.

Table 4.3: Effect of pH

pH 2 3 4 5 6 7 8 9
% Extraction 61 72 86 90 92 82 39 13

26
 From Graph the Optimum pH = 6
Fig 4.3: Effect of pH on extraction percentage of Cr (VI) (feed concentration: 10
mg/L, agitation speed: 600 rpm, T: 323 K, treat ratio: 2, volume percentage of
ionic liquid in APDC 1.5%).

4.4 EFFECT OF AGITATION SPEED

The effect of stirring speed on the extraction of chromium(vi) ions were
investigated at various speed (100-800 rpm) under the conditions of pH value of 6
and equilibrium time 35 mins. The result is illustrated in Fig. .It can been seen that
the stirring speed has some impact on the reaction in the extraction process and the
optimum value is 600rpm. Lower agitation speed (100 rpm), the extraction
percentage was low because of lower mass transfer rate. Increasing the agitation
speed from 100 to 800 rpm, extraction of chromium ions was increased because of
mass transfer rate increases. The extraction percentage was found to be >92%.
From the results, an agitation speed of 600rpm was chosen for further studies.
Table 4.4 Agitation speed

Speed (rpm) 100 200 300 400 500 600 700 800
% Extraction 24 37 58 66 79 93 93 93

27
 From this graph the optimum speed 400 rpm
Fig 4.4: Effect of Speed on extraction percentage of Cr (VI) (pH: 6, feed
concentration: 10 mg/L, T: 323 K, treat ratio: 2, volume percentage of ionic liquid
in APDC 1.5%).

4.5 DETERMINATION OF FEED CONCENTRATION

To determine the feed concentration on the extraction efficiency of

chromium (VI) ions were investigated under the conditions of pH value of 6 and
contact time 35 mins. Feed concentration was varied from 10 to 50 mg/L and its
effect on extraction percentage was studied and shown in Fig. The results shows
that >90% of Cr (VI) ions were extracted when the feed concentration was
maintained <15 mg/L. As feed concentration increases extraction %
simultaneously decreases. Because of ionic liquid saturated with solute i.e ionic
liquid cannot extract anymore solute from the mixture.

Table 4.5 Determination of feed concentration

Feed
10 12 14 16 18 20 30 40 50
Concentration
% Extraction 96 94 93 92 86 81 75 69 61

28
Fig 4.5: Effect of Feed Concentration on extraction percentage of Cr (VI) (pH:6,
agitation speed: 600 rpm, T: 323 K, treat ratio: 2, volume percentage of ionic
liquid in APDC 1.5%)

4.6 EFFECT OF TEMPERATURE

The influence of temperature on the extraction of Chromium (VI) ions was

investigated at pH 6. The extraction studies were carried out at various
temperature range of 35 – 55 oC. When temperature increases extraction % also
slightly increases from 35-45oC. At the temperature range 50.-55oC extraction was
constant, because of solubility of the solute in the solvent increases with
temperature then its gets optimized. [because of solubility, futher extraction
efficiency should be constant because it is saturated].

Table 4.6 Effect of Temperature

Temperature 35 40 45 50 55

% Extraction 92 93 94 94 94

29
Fig 4.6: Effect of heating temperature on extraction percentage of Cr (VI) ( pH: 6,
feed concentration: 10 mg/L, agitation speed: 600 rpm, treat ratio: 2, volume
percentage of ionic liquid in APDC 1.5%)

4.7 EFFECT OF TREAT RATIO (Aqueous to Solvent)

The % extraction of Cr (VI) ions was investigated by varying the amount of

aqueous phase to solvent phase. Fig shows the % removal of Cr (VI) was found to
be maximum at the treat ratio of 2, the treat ratio further increased , extraction %
was decreased, this is due to the lack of solvent.

Table 4.7 Effect of treat ratio on extraction percentage

Treat ratio (v/v) 1 2 3 4 5 6 7

% Extraction 98 97 93 90 77 61 61

30
Fig 4.7: Effect of treat ratio on extraction percentage of Cr (VI) (pH: 6,
Temperature: 50oC, feed concentration: 10 mg/L, agitation speed: 600 rpm,
volume percentage of ionic liquid in APDC 1.5%)

4.8 EFFECT OF VOLUME % OF IL IN APDC

The effect of volume % of IL in APDC on the extraction of Cr (VI) ions

was investigated. The extraction of chromium ions was low at volume % of 0.5
(50µl of IL in10ml APDC) because of insufficient of IL in APDC. When the
volume % of IL in APDC increases from 0.5 – 2, % extraction also increases after
it was constant it means that volume % of 2 is sufficient for removal of chromium
ions. Extraction of chromium ions was found to be 96%.

Table 4.8: Effect of Volume % of IL in APDC

IL (v/v) 0.5 1.2 1.5 2.0 2.5 3.0

% Extraction 64.89 93.11 94.67 96.22 96.22 96.22

31
Fig 4.8: Effect of volume % of IL in APDC on extraction percentage of Cr (VI)
(pH: 6, Temperature: 50oC, feed concentration: 10 mg/L, agitation speed: 600
rpm, treat ratio: 2)

4.9 RSM- MODEL DEVELOPEMENT

Table 1 Shows the extraction of Chromium ions were determined

using RSM with CCD. Percentage of chromium removal model equation was
expressed as equation (2). Where Y is the Extraction of chromium ions, A is the
Agitation Speed, B- is the pH, C- is the treat ratio, D- is the feed concentration.
The predicted values calculated from Eq. (2) were in very good agreement with
the experimental values, as shown in Fig.7. Hence, this quadratic model is well
suited for this experimental set up. The significance of the quadratic model were
tested using ANOVA. The results are shown in table2.

___________(2)

32
Fig 4.9: Predicted Versus Actual values for percentage removal of Chromium (VI)

The value of regression coefficient (R2= 0.992) is closer to one and

indicates that the correlation is well-matched in predicting the values for the
extraction system and the predicted values are found to be closer to the
experimental results. As shown in Table 2, the Model F-value of 145.56 implies
the model is significant. There is only a 0.01% possibility that a ―Model F-Value‖
this large can occur due to noise. Values of ―Prob > F‖ less than 0.0500 shows the
model conditions are significant. In this case A, B, C, AB, AD, BC, BD, CD, A2,
B2, C2 and D2 are significant model terms. The model terms indicates greater than
0.1000 are not significant. The "Lack of Fit F-value" of 14.92 implies the Lack of
Fit is significant. There is only a 0.75% chance that a "Lack of Fit F-value" this
large could occur due to noise. The ―Pred R-Squared‖ of 0.9579 is in logical
conformity with the ―Adj R-Squared‖ value of 0.9858. ―Adeq Precision‖ measures
the signal to noise ratio. A ratio of 48.749 indicates an adequate signal which is
greater than 4 is desirable (38).

33
 The response surface curves indicate the interaction of the variables and
also determine the optimum level of variables for maximum response. The
response surface plots for significant interaction between two variables against %
removal efficiency of Cr are, as shown in Figs. 1-6.

4.9.1 RESPONSE SURFACE PLOTS or (INTERACTIONS AND

OPTIMIZATION OF THE VARIABLES

Fig 1: The 3D plot showing the effects of speed, pH and their mutual interaction
on extraction of chromium (VI).

The contour plot in Fig.1 illustrates the interaction between speed and pH.
In the figure, the parabolic nature of contours implies that the interaction between
both the variables is significant. The speed and pH, both cause the increase in the
extraction % when their values were increased from lower level to up to a certain
point. After this point, extraction % was decreases, as shown in Fig 1. Maximum
percentage extraction of 92 was obtained at pH value of 6 and 650rpm.

34
Fig 2: The 3D plot showing the effects of speed, feed concentration and their
mutual interaction on extraction of chromium (VI).

Fig 2 shows the interaction between speed and feed concentration. Circular
Contours of the figure implies that the interaction between the parameters is not
significant. Hence, the optimum values of the variables are not easy to find.
However, increasing the feed concentration and pH, increases the % extraction up
to certain values. After that, the % extraction decreases upon further increment in
both the values. Maximum percentage extraction of 92 was obtained at 650rpm
and treat ratio.

Fig 3: The 3D plot showing the effects of speed, treat ratio and their mutual
interaction on extraction of chromium (VI).

35
 Fig 3 demonstrates the interaction between speed and treat ratio. %
extraction of Cr (VI) increases up to a certain value. However, it decreases with
further increment. Since contours are parabolic, the interaction between them is
significant. Maximum percentage extraction of 92 was obtained at 650rpm and
feed concentration of 14 ppm.

Fig 4: The 3D plot showing the effects of pH, feed concentration and their mutual
interaction on extraction of chromium (VI).

The interaction between pH and feed concentration is, as shown in Fig 4. A

parabolic contour signifies that the interaction between them is significant. The
curve illustrates that both the values increase the extraction % upon increment
from lower level, but after certain values, the extraction % tend to decline until the
higher level. The optimum values can be found out easily since the contours are
parabolic. Maximum percentage extraction of 95 was obtained at
pH value of 6 and Treat ratio of 3 (v/v %).

36
Fig 5: The 3D plot showing the effects of pH, treat ratio and their mutual
interaction on extraction of chromium (VI).

The contour plot in Fig 5 shows that interaction between pH and treat ratio.
In the figure, the parabolic nature of contours implies that the interaction between
both the variables is significant. The pH and treat ratio, both cause the increase in
the extraction % when their values were increased from lower level to up to a
certain point. After this point, extraction % was decreases. Maximum percentage
extraction of 95 was obtained at pH 6 and feed concentration of 15 ppm.

Fig 6: The 3D plot showing the effects of feed concentration, treat ratio and their
mutual interaction on extraction of chromium (VI).

Fig 6 demonstrates the interaction between feed concentration and treat

ratio. % extraction of Cr (VI) increases up to a certain value. However, it

37
decreases with further increment. Since contours are parabolic, the interaction
between them is significant. Maximum percentage extraction of 92 was obtained
at 3(v/v%) and feed concentration of 14 ppm.

The plotted response surface curves were used to understand the interaction
of the variables and to determine the optimum level of each variable for a
maximum response. The circular nature of the contour signifies that the interactive
effects between the variables are not significant and the optimum values of the test
variables cannot be easily obtained. The response surface curves for % Extraction
of chromium (VI) are shown in Figs.1-6. Each 3D plot represents the number of
combinations of the two-test variable. The maximum percentage extraction of
chromium (VI) is indicated by the surface confined in the smallest curve of the
plot with the other variable maintained at zero levels. It is evident to the elliptical
nature of the contours that the interaction between the individual variables is
significant. Under the optimal condition the maximum predicted efficiency was
93 %.

38
Table 4.9.1: CCD matrix along with experimental values of % extraction of Cr(VI)
ions
Speed (A) % Extraction of Chromium (%)
Feed Concentration (C)
Run pH (B) Treat ratio (D)
ppm
rpm Experimental Predicted

1 -1 -1 -1 -1 76 75.58

2 -1 1 1 1 73 73.62

3 -1 1 1 -1 78 77.42

4 1 1 -1 -1 83 82.08

5 0 0 0 0 93 93.00

6 -1 -1 1 1 78 79.08

7 0 0 0 2 86 84.79

8 1 -1 1 -1 83 84.08

9 0 1 -2 0 88 88.79

10 0 1 0 0 93 93.00

11 0 -2 0 0 65 64.79

12 0 0 0 0 93 93.00

13 1 1 1 1 72 72.58

14 0 0 0 0 93 93.00

15 0 0 0 -2 83 84.63

16 0 0 0 0 93 93.00

17 -1 -1 -1 1 84 84.29

18 2 0 0 0 90 90.29

19 1 -1 -1 1 86 86.75

20 1 -1 1 1 84 83.29

21 0 2 0 0 58 58.62

22 1 -1 -1 -1 84 82.79

23 0 0 2 0 83 82.63

24 1 1 -1 1 78 78.29

25 -2 0 0 0 84 84.13

26 -1 1 -1 1 82 81.08

27 -1 -1 1 -1 76 75.13

28 0 0 0 0 93 93.00

39
 29 -1 1 -1 -1 80 80.12

30 1 1 1 -1 82 81.13

Table 4.9.2. ANOVA for response surface quadratic model for % extraction of
Cr(VI) ions

Mean F p-value

Source Sum of Squares df Square Value Prob > F

Model 2026.55 14 144.75 145.56 < 0.0001 Significant

A-Speed 57.04 1 57.042 57.36 < 0.0001

B-pH 57.042 1 57.042 57.36 < 0.0001

C-Feed
Concentration 57.042 1 57.042 57.36 < 0.0001

D-Treat ratio 0.042 1 0.042 0.041 0.8406

AB 27.56 1 27.56 27.71 < 0.0001

AC 3.06 1 3.06 3.08 0.0997

AD 22.56 1 22.56 22.69 0.0003

BC 5.06 1 5.06 5.09 0.0394

BD 60.06 1 60.06 60.39 < 0.0001

CD 22.56 1 22.56 22.68 0.0003

A^2 57.50 1 57.50 57.82 < 0.0001

B^2 1678.57 1 1678.57 1687.95 < 0.0001

C^2 91.14 1 91.145 91.65 < 0.0001

D^2 117.86 1 117.86 118.52 < 0.0001

Residual 14.92 15 0.99

Lack of Fit 14.92 10 1.497

Pure Error 0 5 0

Cor Total 2041.46 29

SD = 0.9975, mean = 82.46, Coefficient of variation % = 1.209, R squared = 0.993,

Adjusted R squared =0.9858 , Predicted R squared =0.9579, Adequate Precision = 48.749

40
 CHAPTER 5

CONCLUSION

Extraction studies were performed for the removal of Chromium (VI)

ions using 1-butyl-3-methyimidazolium hexafluorophosphate ([C4MIM][PF6]) and
ammonium pyrrolidine dithiocarbamate (APDC). Equilibrium studies were carried
out to determine extraction equilibrium time it was found to be 35 mins. The
Various parameters affecting extraction performance like pH, agitation speed,
Feed concentration, temperature, treat ratio and volume % of IL in APDC were
studied. Statistical optimum conditions and interaction between the parameters
were determined by Response surface methodology.

% Extraction of Cr (VI) experimentally = 96%

% Extraction of Cr (VI) statiscally = 93%
This shows that the experimentally optimized results were found to be
compatible with statistical results.

41
 CHAPTER 6

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