International Journal of Advanced Science and Research

International Journal of Advanced Science and Research

ISSN: 2455-4227
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Volume 2; Issue 6; November 2017; Page No. 128-131

Effect of PH on the adsorption of copper (ii) ions from concentrated chloride solutions by the chelating
resin Dowex M-4195
RS Dave
Department of Chemistry, Arts, Science & Commerce College, Pilvai, Gujarat, India

Abstract
In the present study chelating anion exchange resin Dowex M-4195 was used for removing Cu (II) from electroplating waste
water. Adsorption was carried out in a batch process with different concentrations of Cu (II) ions by varying pH and agitation time.
The uptake of the metal ion was very fast initially, but gradually slowed down in dicating penetration in to the interior of the
adsorbent particles. The experimental data closely followed both Langmuir and Freundlich isotherms. A small amount of the
adsorbent (1.2 g/L) could remove maximum 87 % of Cu (II) in 300 min from a solution of concentration 100 mg/L at 300 K. The
highest adsorption was shown at pH 4.0 and then decreased.

Keywords: copper, adsorption, anion exchange resin, Dowex-M 4195

Introduction parameters like effect of adsorbate dose, effect of pH, effect of

Heavy metals like copper and nickel are widely used in contact time and effect of concentration have been studied
electroplating industry. The typical form of copper and nickel intensively [9]. In view of the uncertainty over the behavior of
which are used in plating is the toxic divalent copper and DowexM-4195 at high-chloride concentrations, the present
nickel. If wastewater contaminated with divalent copper and study was undertaken to examine the uptake of copper, at
nickel is discharged to water ways without adequate treatment, different pH values from chloride solutions more concentrated
soil and water resources become polluted. Electroplating than those studied hitherto. The study was made under
operations form part of large scale manufacturing plants (e.g. conditions that provide danexcess resin capacity for copper.
automobile, cycle, engineering and numerous other industries) The behavior of the resin is discussed in terms of the
or performed as job-work by small and tiny units They are chemistry of the bis (2-pyridylmethyl) amine functional
spread across the entire country with significant concentration group. DowexM-4195 was developed in theearly 1970 s and
in several states like Punjab, Haryana, part of U.P., has found some commercial applications, notably for
Maharashtra, Karnataka, Andhra Pradesh, Tamil Nadu and adsorption of heavy metals. Deniz et al. reported that the use
West Bengal. Electroplating is considered a major polluting of the chelating resin Dowex M-4195 in the adsorption of
industry because it discharges toxic materials and heavy selected heavy metal ions from manganese solutions10.
metals through wastewater (effluents), air emissions and solid Finally, the strong affinity of DowexM-4195 for many heavy
wastes into the recipient environment. It is harmful to humans metals, even in acidic solutions with high chloride
and other living organisms. Inhalation of divalent copper and concentrations, suggests that elution may not be
nickel causes an increase in the incidence of lung cancer. straightforward. The studies confirmed that M-4195 is capable
Moreover, soluble nickel compounds are carcinogenic, giving of removing arrange of heavy metal impurities from an acidic
rise to cancers of the nasal cavities, lungs and other organs copper chloride solution. Elution studies were also done, and
such as stomach and kidney [1, 3]. confirmed that elution would be the most challenging step in
Copper is also toxic to aquatic organisms even at very small developing a commercial process for separating heavy metals
concentrations [6]. It is found in sizeable amounts in the liquid from acidic copper chloridesolutions [11, 14].
effluent streams of printed circuit board plants [7] and other
effluents. It is desirable, therefore, to undertake investigations Material and Methods
on the removal of these metal ions from water. Among the All the chemicals used were of A.R. grade. A stock solution of
various cleanup methods available for metal ions removal copper chloride (1000 mg L-1) was prepared by dissolving
adsorption appears to have the least adverse effects. It 1.705 g. of copper chloride (s.d. fine Chemicals, Mumbai) in
includes a broad range of carbon aqueous materials at a high distilled water and it was diluted further as required for test
degree of porosity and large surface area [8] and finds use for samples containing 5 to 30 mg L-1of Cu (II). 5 ml of Cu (II)
the removal of toxic, biodegradable and non-biodegradable solution of a desired concentration and 2.5 ml of 0.1 M oxalic
substances from waste water. It is attractive as it can treat acid to prepare copper oxalate anion as a desired pH in test
waste water to acceptable quality suitable for reuse [4, 7]. The solutions containing fixed amount of resin. Dowex M-4195
removal efficiency of synthetically prepared resin towards resin was purchased from Supelco Sigma Aldrich Division.
copper (II) was carried out in the present study. Various The resin was rinsed with water several times to remove any

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leached materials. It was then underwent a wetting procedure Results and Discussion
to ensure that it was wet, without introducing extraneous The adsorption was carried out in 100 mL borosil glass bottle
water into the test solutions. The pH was then adjusted using by agitating a preweighed amount of the resin powder with 50
NaOH (certified, Fisher Chemicals) to a typical free acid mL of the aqueous Cu (II) solution in a constant temperature,
concentration of about 1.0 mol/L. The total chloride water bath shaker (NSW, Mumbai) for a predetermined time
concentration was 3.6 mol/L. Elution was done at 25 C using interval at a constant speed. After adsorption, the mixture was
1mol/L sulfuric acid (certified, Fisher Chemicals) and 4 mol/L centrifuged. Filtrate was separated out and unabsorbed Cu (II)
ammonium hydroxide (certified, Fisher Chemicals). was determined with uv-Vis spectrophotometer119. The
amount of Cu (II) adsorbed per unit mass of the adsorbent (q
Analysis in mg/g) was computed by using the following expression:
Metal concentrations were analyzed using a systronic uv-vis
spectrophotometer 119 with pc. All analysis were run at 25 C
in duplicate, except the samples from elution, where the low
sample volume dictated a single analysis. The pH of solution
and sample was measured using an Orion pH/ISE meter with
an Orion Ross combination pH electrode, calibrated by using Where C0and Ct are Cu (II) concentrations in mg/L before and
pH 1.0, 3.0 and 7.0 buffers (certified, Fisher Chemicals). after adsorption for time t, and m (g) is the amount of
adsorbent taken for 1 L of Cu (II) solution. The extent of
Table 1: Characteristics properties of the ion exchange resins used adsorption in percentage is found from.
Dowex M-4195 (weak basic anion exchange resin)
Physical form Spherical opaque beads
Ionic form as supplied free base
Moisture holding capacity 34%
Particle size 0.3 – 1.2 mm
Uniformity coefficient 1.7 max Effect of pH
Total exchange capacity 1.0 meq m L-1 The effects of initial pH on the removal of Cu (II) by ion
pH range 0–7
exchange resin Dowex - 4195 was investigated intensively.
The percentage of adsorption was gradually increased up to
Chemical formula of copper oxalate anion is as under, pH 4.0 and then it decreases rapidly with the increase in pH
which may be due to the formation of a copper hydroxide at
higher pH values. The results are graphically represented in
the figure 3. The pH value 6.0 was used for present
investigation. Result shows that the ion exchange resin Dowex
- 4195 is effective for the removal of Cu (II) in the pH range
4.0 to 7.0 for a solutioncontaining 5 mg L-1of copper.

Desorption and Regeneration

For carrying out desorption and regeneration studies, Dowex
M- 4195 resin as first saturated with Cu (II) by taking 4 g of
resin in apyrex glass column (1.5 cm internal diameter) and
continuously passing a solution of Cu (II) (60 mg/L) through
it For carrying out desorption and regeneration studies, while
keeping a constant head of 2 cm till the concentration at the
outlet equaled the initial concentration.
Fig 1
Table 2: Effect of pH on adsorption of Cu (II) on Dowex-M 4195
pH % Adsorption
2.0 64.59
3.0 75.50
4.0 87.67
5.0 80.00
6.0 71.31
7.0 63.50
Fig 2 8.0 60.05

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Fig 3: Effect of pH on adsorption of Cu (II) on Dowex-M 4195. Cu

(II) Concentration: mg/L, Adsorbent Dose: mg/L, Temp. 303 K

Desorption was carried out by passing successively (i) Fig 4: Freundlich adsorption isotherm for adsorption of Cu (II) on
deionised water (pH 7.0) and (ii) dilute nitric acid (pH 4.0) Dowex-M 4195
through the column till Cu (II) could not be detected in the
outlet in each case.
Equilibrium Modeling
It is important to establish the most appropriate correlation for
the equilibrium curves for the removal of metal from
industrial wastewater. Two isotherm equations have been
tested in the present study: Freundlich and Langmuir. These
plots were used to calculate the isotherm parameters given in
Table 3 for copper. Freundlich proposed that if the
concentration of solute in the solution at equilibrium, Ce, is
raised to the power n, the amount of solute adsorbed being qe,
then Ce n/ qe is a constant at a given temperature. The
Freundlich isotherm is derived by assuming a heterogeneous
surface with a non uniform distribution of heat of adsorption
over the surface. Hence the empirical equation can be written:
qe =K F C en (1)
Fig 5: Langmuir adsorption isotherm for adsorption of Cu (II) on
Where, KF is the Freundlich constant and in the Freundlich
Dowex-M
exponent. Therefore a plot of log qe vs. log Ce enables the
constant KF and exponent n to be determined [15, 18]. Table 3: The summary of isotherm parameters for Cu (II) on Dowex
Langmuir proposed a theory to describe the adsorption of gas - 4195 by ion exchange resin system.
molecules onto metal surfaces. The Langmuir adsorption
isotherm has been successfully applied to many other real Isotherm Resin Dowex - 4195
sorption processes and it has been used to explain the sorption
Freundlich isotherm Kf = 0.110 n = 0.490 R2 = 0.9825
of metal onto ion exchange resin. A basic assumption of the Langmuire isotherm Q = 1.60 b = 0.55 R2 = 0.9972
Langmuir theory is that sorption takes place at specific
homogeneous sites within the adsorbent. It is then assumed
Conclusion
that once a metal ion occupies a site, no further adsorption can
In this study, various parameters like effects of pH, resin dose
takes place at that site. Theoretically, therefore, a saturation
and initial concentration on removal of Cu (II) ions from
value is reached beyond which no further sorption can take
electroplating waste water have been reported. Two isotherm
place. The saturated monolayer curve can be represented by
models have been tested and the equilibrium data fits very
the expression [19, 21]:
well to Frundlich and Langmuir adsorption isotherms. In this
qe= QobCe (2) 1+ b Ce paper, it can be seen that ion exchange resins Dowex M- 4195
can be used for the removal of Cu (II) ions from electroplating
where b and Qo are the Langmuir constants. Therefore, a plot waste water and it is most efficient. Uptake capacity of Dowex
of 1/ qe vs. 1/Ce yields a linear plot of Langmuir isotherm. As M- 4195 is higher than other ion exchange resins.
shown in Table 2, maximum uptake of Dowex 50 x 4 is
greater than that of Dowex M - 4195. This may be due to the Acknowledgements
intrinsic characteristics such as exchange capacity of resins The author is thankful UGC New Delhi for providing financial
Table1. support to complete this project in form of Minor Research

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Project. The author gratefully acknowledge the Arts,

Commerce and Science College, Pilvai (North Gujarat), India.
For providing laboratory facilities during this project.

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