Received date: March 16, 2012; Accepted date: April 24, 2012; Published date: May 23, 2012
Citation: Dhote SS, Deshmukh L, Paliwal L (2012) Heavy Metal Ions Separation on Thin Layer of Impregnated Carbamide-Formaldehyde Polymer. J Chromat Separation Techniq 3:124. doi:10.4172/2157-7064.1000124
Copyright: © 2012 Dhote SS, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.
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Various heavy metal ions such as Pb2+, Hg2+, Cd2+, Zn2+, Co2+, Ni2+, Cu2+, Fe3+, UO2 2+, VO2+ and Bi3+ have been chromatographed on thin layer of carbamide-formaldehyde polymer impregnated with sodium diethyl- dithiocarbamate and its admixture with Na2 CO3 , NaCl, EDTA, H3 PO4 and NaOH. Common solvent namely acetone, benzene, carbon tetrachloride, methanol and ethanol have been used as mobile phases. Semiquantitative determination of Hg2+, Bi3+ and Ni2+ by visual comparison of color intensities on the TLC plates as well as by measurement of spot area was attempted.
Carbamide; EDTA; TLC; Cu2+; Dithiocarbamate
Thin layer chromatography (TLC) is a very convenient and rapid method for the separation and identification of inorganic ions. Therefore, any attempts to improve TLC for this application seen to be of interest for chromatographers. There are several ways to improve the TLC method. One of them is use of support possessing different characteristics than those commonly used in TLC. For that reason a number of metal ions were systematically chromatogrphed on thin layer of a synthesized carbamide-formaldehyde polymer, and already used for the separation of amino acid  and various metal ions were also chromatographed  using various organic solvents as a mobile phases. Sodium diethyl-dithiocarbamate [(C2H5)2NCS2]?Na+, (NaDDC) is an effective extraction reagent for over twenty metal ions into various organic solvents such as chloroform, carbon tetrachloride, methanol and ethanol . Espinola et al.  have used immobilized dithiocarbamate on silica gel for extraction of cobalt, nickel, copper and zinc cations in ethanolic solution. Web et al.  have reported the simultaneous preconcentration of beryllium, bismuth, cobalt, gallium, silver, lead, cadmium, copper, manganese and indium in sea water by using poly(acrylaminophosphonic dithiocarbamte), chelating fibre, as an adsorbent. Various heavy metal ions and several binary mixtures were separated on thin layer cellulose plates and paper chromatographic strips impregnated with sodium diethyldithiocarbamate , and chromatographic behavior of various dithiocarbamate fungicides  were studied on cellulose plates. The aim of our work was to obtain a general feeling on the chromatographic behavior of a number of heavy metal cations on impregnated carbamide-formaldehyde polymer layer.
Glass jars (25 × 5cm), glass capillary, watch glass and temperature controlled electric oven were used.
Reagents and chemicals
Urea, formalin solution, was obtained from Merk, dimethylglyoxime, dithizone, potassium ferrocyanide, carbon tetrachloride, NaCl, EDTA, NaOH, Na2CO3, H3PO4 methanol and ethanol were obtained from SD Fine India. Sodium diethyldithiocarbamate was obtained from CDH, India. All other chemicals were of analytical reagent grade.
Preparation of Solutions
Solutions (1%) of metal salts, sodium sulphide and diethyldithiocarbamate (NaDDC) (0.01M) was prepared in distilled water. Aqueous solutions of metal salts were stabilized by adding the corresponding mineral acids (0.5ml of 4M) and ethanol (0.5ml).
Metal ions studied
Pb2+, Hg2+, Cd2+, Zn2+, Cu2+, Fe3+, UO22+, VO2+ , Ni2+, Co2+ and Bi3+.
i. 1% aqueous potassium ferrocyanide- Fe3+, Cu2+, UO22+ and VO2+
ii. 0.5% Dithiozone in CCl4 – Pb2+, Hg2+, Cd2+, Zn2+and Bi3+
iii. 1% alcoholic solution of DMG – Ni2+ and Co2+
Thin layer chromatography
Preparations of Carbamide-formaldehyde polymer plates: The carbamide- formaldehyde thin layer were prepared by suspending 10 gram of carbamide formaldehyde powder  in 60ml of distilled water, and the suspension was then coated onto glass plate using by dipping method. The plates were allowed to dry over night at room temperature and were used to next day for TLC.
Preparation of Carbamide- formaldehyde plates: Solutions with desired concentration of impregnants with various additives [(ICF1)- NaDDC(20%), (ICF2)- NaDDC (20%) + Na2CO3 (4%), (ICF3)- NaDDC (20%) + NaCl (4%), (ICF4)- NaDDC (20%) + EDTA (4%), (ICF5)- NaDDC (20%) + NaOH (4%) and (ICF6)- NaDDC (20%) + H3PO4 (4%) ] were prepared in distilled water. After that plain carbamide – formaldehyde plates are dipped in above prepared solutions. The developed plates were then activated by heating at 60±1°C for 1hr. (ICF- Impregnated carbamide- formaldehyde)
Spotting of test solution: Thin layer chromatography was performed on impregnated carbamide-formaldehyde layer plates. Test solutions (1 μl) were applied on plates with the help of micropipettes at about 2cm above the lower edge of the plates. The solvent ascent was fixed to 10cm in all cases for the determination of RF values of all individual metal ions. Linear ascending development was carried out in a TLC chamber.
Limit of detection: The limits of detection of the metal cations were determined by spotting different amounts of metal ion onto the TLC plates, developing the plates using the method describe above, and then detecting the spots. This method was repeated with a successive decrease in the amount of metal ion used until spots were not detected. The minimum detectable amount on the TLC plates was taken as the limit of detection.
Semiquantitative determination of Hg2+, Bi3+ and Ni2+: To determine recovery of Hg2+, Bi3+ and Ni2+ by spot area measurement method, 0.01mL from series of standard solution of Hg2+, Bi3+ and Ni2+ were spotted on ICF5 plates. The plates were developed with carbon tetrachloride mobile phase. After detection, the spots were copied onto tracing paper from the chromatoplates and then the area of each spot was calculated. The recovery of Hg2+, Bi3+ and Ni2+ were studied by analyzing various samples. For this purpose, experiments were performed by spotting 0.01mL of sample of solution containing 100 μg Hg2+, Bi3+ and Ni2+. The recovery of Hg2+was 28± 3%.
This study includes chromatography of eleven metal ions (Pb2+, Hg2+, Cd2+, Zn2+, Cu2+, Fe3+, UO2 2+, VO2+ , Ni2+, Co2+ and Bi3+) on thin layer of carbamide-formaldehyde polymer impregnated with six adsorbent and six mobile phase (water, acetone, benzene, carbon tetrachloride, ethanol and methanol). The practically achieved separations of metal ions are given in the Table 1.
|Stationary phase||Separations RF or (RL-RT)|
|Mobile phase – Acetone|
|ICF1||Cd2+ (0.80) from Co2+ (0 - 7.0 cm) or Fe3+ (0 - 3.0 cm)|
|ICF2||Zn2+ (0.87) from Co2+ (0 - 6.9 cm) or Fe3+ (0 - 6.2 cm) or Hg2+ (0-5.0 cm)|
|ICF3||Hg2+ (0.90) from Fe3+ (0.00)|
|ICF5||Hg2+ (0.90) from Pb2+ (0.75)|
|Mobile phase – Methanol|
|ICF1||Hg2+ (0.95) from Cd2+ (0.00), Hg2+ (0.93) from Cd2+ (0.00)|
|ICF3||Fe3+ (0.98) from Pb2+ (6.6 - 8.8 cm)|
|ICF4||Hg2+ (0.95) from Cd2+ (0.00)|
|Mobile phase – Ethanol|
|ICF1||Cu2+ (0.00) from Cd2+ (4.4 - 9.0 cm), Fe3+ (0.00) from Cd2+ (3.1 - 8.8 cm)|
|ICF2||Fe3+ (0.13) from Cd2+ (4.8 - 8.1 cm), Ni2+ (0.19) from Zn2+ (5. 9- 9.8 cm)|
|ICF3||Hg2+ (0.00) from Cd2+ (6.1 – 9.4 cm) , Co2+(0.00) from Cd2+ (6.5 - 9.4 cm)|
|ICF4||Hg2+ (0.00) from Cd2+ (6.5 – 8.6 cm) , Pb2+(0.00) from Cd2+ (6.5 – 9.7 cm)|
|ICF5||Pb2+(0.00) from Cd2+ (8.0 – 9.8 cm)|
|Mobile phase – Carbon tetrachloride|
|ICF1||Hg2+ (0.96) from Co2+ (0 – 7.5 cm)|
|ICF2||Hg2+ (0.98) from Cd2+ (0.00), Cd2+ (0.00) from Bi3+ (5.7 – 10.0 cm)|
|ICF3||Cd2+ (0.00) from Hg2+ (5.7 – 10.0 cm), Cd2+ (0.00) from Zn2+ (4.6 – 10.0cm)|
|ICF4||Hg2+ (0.95) from Ni2+ (0.00), Hg2+ (0.94) from Cd2+ (0.00)|
|ICF5||Ni2+ (0.00) from Hg2+ (7.5 – 10.0 cm), Ni2+ (0.00) from Zn2+ (3.5 - 10.0 cm)|
|Mobile phase – Benzene|
|ICF1||Cd2+ (0.00) from Bi3+ (7 – 9.8 cm), Cd2+ (0.00) from Pb2+ (2.1 – 9.6 cm)|
|ICF2||Hg2+ (0.86) from Cd2+ (0.00)|
|ICF4||Hg2+ (0.97) from Cd2+ (0.00)|
ICF (Impregnated carbamide- formaldehyde) - Impregnations materials listed in experimental section.
RL(tailing) = distance (cm) travelled by the lower edge of a tailing spot.
RT (tailing) = distance (cm) travelled by the upper edge of a tailing spot.
Table 1: Separation achieved
The effect of impregnation material
The RF values of all the metal ions were found to be zero on carbamide- formaldehyde layer impregnated with acidic admixture, ICF6 [NaDDC (20%) + H3PO4 (4%)], in the mobile phases. These observations support the fact that metal dithiocarbamate complexes are unstable in acidic mixtures. The alkaline impregnation material, ICF5 [NaDDC (20%) + NaOH (4%)] was found to be the best as it gives compact spots for all the metal ions. Hence, it seems that NaDDC act as a complexing agent as well as adsorbent. The role of water soluble salts is suppressed due to the excess of NaDDC (20%).
The effect of mobile phase
The RF values were found to be zero for the metal ions on thin layer of carbamide – formaldehyde impregnated with any of the six impregnation materials in the mobile phase of highest dielectric constant (ε = 78.54) such as water. It is on line with the fact that the dithiocarbamates of metal ions of atomic number more than 20 are water insoluble. The differential RF values have been obtained for the metal ions in low dielectric constant mobile phase such as carbon tetrachloride (ε = 2.24), benzene (ε = 2.27), acetone (ε = 20.7), ethanol (ε = 24.5) and methanol (ε = 32.7). Hence it is clear that the RF values of metal dithiocarbamates depend on its solubility in the mobile phase, the adsorption affinity and pH of the impregnation materials. Therefore, the maximum numbers of separations have been achieved in lowest dielectric constant mobile phase that is carbon tetrachloride. Hence carbon tetrachloride seems to be better mobile phases for metal ions chromatography on NaDDC using carbamide- formaldehyde polymer layer.
Quantitative analysis by spot area measurement method
An attempt has been made to determine the recovery of Hg2+, Bi3+ and Ni2+ spiked into water using spot area measurement method by using ICF5 plates and carbon tetrachloride as a mobile phase. A linear relationship obtained when the amount of sample spotted was plotted against area of the spot follows the empirical equation ζ=km, where ζ is the area of the spot, m is the amount of solute and k is a constant. Representative plot for Hg2+ has been shown in Figure 1 and 2. The linearity is maintained up to 250 μg/spot. At higher concentration a positive deviation from linear law was observed. The accuracy and precision was around Hg2+ = ±28%.
Sodium diethyldithiocarbamte and carbamide - formaldehyde polymer is a promising chromatographic material for the separation of metal ions in organic mobile phases such as acetone, ethanol, methanol, carbon tetrachloride. However aqueous solutions and acidic solutions may not be useful as mobile phase in chromatography on sodium dithiethyldithiocarbamate. The thin layer plate of carbamide – formaldehyde with NaOH and carbon tetrachloride contains mobile phase was identified as the most useful for the analysis of heavy metal ions.
The authors would like to thank the principal and head of the Department of Chemistry, Hislop College Nagpur, and M.S. India for the provision of the research facilities used in our study.
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