Detection of mercury in trace amoumnts in the environment through its catalytic effect on ligand substitution reaction between hexa

cyanoferrate(II) and phenanthroline Amarika Singha* and Anupma Singhb

a

Department of Chemistry, Institute of Engineering and Technology, Sitapur Road, Lucknow-226021,U. P. Department of Chemistry, Institute of Engineering and Technology, Sitapur Road, Lucknow-226021,U. P. a* Corresponding author : E-mail : amarikasingh@rediffmail.com b anupma121_121@rediffmail.com

Detection of mercury in trace amoumnts in the environment through its catalytic effect on ligand substitution reaction between hexa cyanoferrate(II) and phenanthroline Abstract The Mercury is known to catalyse the reaction between hexcyano ferrate (II) and phenanthroline in the concentration range 3.0 x 10 -7-3.0 10-8 M. The phenanthroline is substituted in hexacyanoferrate (II) by replacing two of the cyanide co-ordinated in the coordination sphere to Iron (II) in hexacyanoferrate (II) ion. A catalytic Kinetic Method based on fixed time procedure has been developed for estimation of mercury by following the progress of the reaction spectrophotometrically at 528 nm. The reaction conditions chosen for the progress of the reaction were: Ionic strength I = 0.1 M (KNO3), Temp= 25.0 0.1oC and pH = 3.0 0.02. On the basis of experimental results for the catalyzed reaction the following rate expressions was derived:= In this equation k' is the rate constant for uncatalysed path when a non rate limiting concentration of phenanthroline was taken and k is composite rate constant. The absorbance changes were recorded at every fifteen minutes for the reaction under experimental condition [Fe(CN)6]4
-

=5.5x10-3 M and [Phen] = 2.5x10-4M at each

Mercury concentration in the range (3.0x10-7 to 3.0x10-8M).The plot of absorbance versus[Hg+2] concentration yields a straight line following equation A15 = 3.3x105[Hg+2]+0.09. The detection limit is evaluated by standard procedure and is found to be 2.5x10-7M in [Hg+2]. The concentration of [Hg+2] was also estimated in presence of several other interfering and non interfering cations and anions. Keywords- detection; mercury; phenanthroline;hexacyanoferrate(II); environment

1. Introduction Many transition metal ions are know to be essential for life and are involved in specific biological functions. There was a certain stage in chemical evolution when availability of these metal complexes up to minimum concentration level was a necessary requirement for further promotion of life. However, if these metals are present beyond a threshold concentration the same metal ions become toxic. The concentration of many metals of industrial importance is increasing in environment as they are being released in increasing amounts causing grievous pollution of the precious gifts of nature, namely air, water and land. Mercury is an unusual metal having unique properties and wide ranging industrial applications Mercury is present as a pollutant in air, water and soil. Since it is toxic, it ought to be regularly monitored in a wide variety of samples of air, water, food, human blood and urine. During the past decade, many new and improved methods for determination of Mercury (II),1-6 and other metals like Ruthenium,7 cobalt (II), Nickel (II), 8 copper ,9have been developed. Most of these methods lack sufficient sensitivity for determination of Mercury at Sub nanogram per milliter levels. In many case extractive separation techniques,10,11 are required before analysis and therefore a large volume of sample is required. Thus, the use of Hg+2 catalysed ligand substitution reaction on hexacyano ferrate (II) can be exploited for its trace determination using kinetic catalytic Method (KCM) because of its several advantage over conventional method,9,12 .Most of these involve oxidation Reactions,13-21 while References of ligand substitution reactions are scanty,22-26. In many cases catalytic action of mercury (II) on slow redox processes [18-21] have been used to develop KCMs for determination of Mercury (II). However, these methods are costly and less sensitive. The advantage of KCM lies in the fact that only a simple spectrophotometer is required as a main instrument. In this paper, we report a new sensitive Kinetic method for estimiation of Mercury (II) based on its catalytic activity on the ligand substitution reaction between phenanthroline and hexacyanoferrate (II), under optimum reaction conditions. This method may achieve wide spread acceptance because of its higher sensitivity greater precision and improved selectivity.

2. Experimental 2.1 Chemicals, solvents and solutions All reagents used were of analytical grade. Double distilled water was used to prepare all solutions. Stock solutions of 2x10-2M Mercury (II) chloride, 2x10-2 M Phenanthroline and 2x10-2M potassium hexacyanoferrate(II) were prepared by weighing their calculated amounts from their analytical grade samples in water. Solution of hexacyanoferrate(II) were stored in dark amber coloured bottles to prevent photodecomposition of the complex. The mercury(II) and hxacyanoferrate (II) solutions were diluted as per requirement just before use everyday. The pH of the reaction mixture was maintained at 3.0+ 0.02 with the help of a phthalate sodium hydroxide buffer, as reported in literature 27 potassium nitrate was used to maintain the ionic strength at 0.1 M each time. 2.2 Instrumental The pH measurement were made on a digital pH meter of Sio-global. All the reactant solutions were equilibrated at 25oC by keeping them inside environmental chamber in order to maintain the desired temperature.Genesis Model No. 10UV was used to record the spectra of the reaction. All glassware were steamed before use. Certified A grade volumetric apparatus were used throughout the study. Quartz cuvettes were cleanced by imersion in 1:1 nitric acid for 15 minutes to remove traces of impurities. The standard BDH buffers were used for standardization of pH meter. 2.3 Kinetic measurements All the reactant solutions were placed in a the environmental chamber at 25.0 0.1 oC for 30 minutes to attain thermal equilibrium. Then, 2ml of 2.5x10-4 mol L-1 of phenanthroline solution, 2ml of phthalate buffer solution (pH=3.0+0.02) and 2ml of 3.0x10-7 3.0x10-8M solutions of mercuric chloride were pipette in sequence into a 25 ml glass Stoppered graduated flask and the above mixture was finally mixed with 2 ml of 2.5X10-2 M hexacyanoferrate (II) with the help of syringe to initiate the reaction. The solution was shaken and transferred to a 10mm pathway quartz cuvette to measure the absorbance. After 15, 20, and 25 min of the reaction, the absorbance was measured. The data obtained were used to plot the calibration curves and the subsequent determinations of Mercury(II).

3. Results and discussion In the fixed time procedure, the Absorbance At (t=15,20 and 25min, after mixing of the reagents) were recorded . A Plot of the At values versus the concentration of Hg +2, where hexacyanoferrate (II) was present in sufficient excess and phenanthroline in non-rate-limiting excess, were found to be linear. The plot of A t versus (Hg+2) is given in figure 1. The linear regression co-relating the A t values to the Hg+2 concentration between 3.0x10-73.0x10-8M are given table (1), and is represented by Equations (13) A15 A20 A25 = = = 3.3x105[Hg+2]+0.09 3.9x105[Hg+2]+0.105 3.0x105[Hg+2]+0.126 (1) (2) (3)

Figure 1: Calibration Curve for determination of [Hg+2] The chosen reaction conditions are - [Fe(CN) 6]4 - = 5.5x10-3 M, [phen] = 2.5x104

M,pH 3.0+0.02, I = 0.1M(KNO3), Temp = 25.0 + 0.1oC.

TABLE 1. Absorbance at fixed time (At) as a Function of [Hg+2 ] [Hg+2]x10-7 0.30 0.60 0.90 1.20 1.50 1.80 2.10 2.40 2.70 3.00 Conditions: [Fe(CN)6]4
-

A15 0.090 0.100 0.110 0.120 0.130 0.140 0.150 0.160 0.170 0.180

A20 0.110 0.120 0.125 0.135 0.140 0.150 0.160 0.170 0.175 0.185

A25 0.135 0.140 0.150 0.155 0.165 0.175 0.180 0.190 0.200 0.210

= 5.5x10-3 M, [phen] = 2.5x 10-4M, pH=3.0+0.02,I =

0.1M(KNO3) and temp = 25.0+0.1oC The relationship at higher [Hg+2] is more complicated. The rate equation for ligand substitution reaction on [Fe(CN)6]4 - with [Phen] in presence of a non-rate limiting excess of [Phen] and a trace amount of mercury (II) is expressed as in Equation(4) Rate = = (4)

The first term corresponds to the rate of the uncatalysed path, the second term of the catalysed path, which shows the trend towards a leveling of the rate at higher (Fe(CN)6]4 - and a variable order dependence. At a relatively large excess of hexacyanoferrate (II), rate can be written as

(5)

In this equation k' is an experimental rate constant for an uncatalysed reaction and k 2 is made up of many terms derived from the mechanistic scheme. Equation (5) predicts a linear relationship between the initial rate and the concentration of Mercury(II) catalyst, and has been found to be true in the present investigation (Figure1) It must

be kept in mind, the ratio of the rate of the catalysed reaction to that of the uncatalysed reaction must be high. Therefore, [Fe(CN)6]4 - should be high enough for the catalysed reaction to be fast, but not so high so as to make the rate of the uncatalysed path considerable when compared to the catalysed path. Absorbance changes for lesser or slightly more reaction duration also give a linear relationship having higher errors. The error associated with calibration curves for A 20 and A25 are higher than that of A15 as shown in Table 2. This is because A15 is a close measure of the initial rate in comparision to A20 or A25. Although smaller fixed time of 10 minutes or less can also be chosen but the absorbance changes are smaller and their measurements, would cause larger errors. The chosen time of 15 minutes gives sufficient and convinent absorbance changes. The first calibration curve (A15) versus [Hg]+2 is therefore, re-commended for determination of Mercury in trace amounts in the present study. This fixed time (A15) allows 30 determination per hour. Table 2 shows that the Mercury (II) determined from all the analytes are quite satisfactory for environmental monitoring applications. TABLE 2. Computation of error for the determination of Hg+2
[Hg+2]x107 M taken
+2 7

A15 [Hg ]x10 M Found % Error

+2 7

A20 [Hg ]x10 M Found %Error

+2 7

A25 [Hg ]x10 M Found %Error

0.30 0.60 0.90 1.20 1.50 1.80 2.10 2.40 2.70 3.00

0.31 0.59 0.85 1.22 1.47 1.76 2.12 2.41 2.69 2.98

+3.3 -1.6 -5.5 +1.6 -2.0 -2.2 +0.9 +0.4 -0.3 -0.6

0.32 0.58 0.91 1.17 1.53 1.78 2.11 2.44 2.72 2.97

+6.6 -3.3 +1.1 -2.5 +2.0 -1.1 +0.4 +1.6 +0.7 -1.0

0.27 0.61 0.88 1.25 1.52 1.83 2.12 2.42 2.64 3.03

-10.0 +1.6 -2.2 +4.1 +1.3 +1.6 +0.9 +0.8 -2.2 +1.0

Conditions: [Fe(CN)6]4 - = 5.5x10-3 M, [phen] = 5.0x10-4 M, pH = 3.0+ 0.02, I = 0.1M (KNO3) and Temp = 25.0+0.1oC. An instantaneous but not significant change in absorbance is noticed immediately after mixing the reaction followed by a slow absorbance change. The first change is

attributed to fast reaction between [Fe(CN)5H2O]-3 (already present in the reaction medium due to thermal and photodecomposition of [Fe(CN)6]4 -) and Phenanthroline. Thus, it is recommended to prepare fresh solution of K 4[Fe(CN)6] before every kinetic run by proper dilutions from the stock solution in order to minimize this back ground reaction. Application of the Arrhenius equations to the rate constants of the uncatalysed and catalysed reactions gives the expression.

(6)

(7) In the above equation, au and ac are quotient of the pre-exponential factors for catalysed and uncatalysed reactions respectively and Eau and Eac are the corresponding activations energies (Eau = 69.48 KJ mol-1 and Eac= 60.25 KJ mol-1). The ratio Kcexp / Kuexp decreases slightly with rise in temperature. Thus 25 0C is found to be the most suitable temperature. Consequently, the increase in temperature does not alter the sensitivity to any appreciable extent. Thus, any convenient temperature may be selected for a complete set of kinetic runs but it is possible to work at room temperature in absence of a precision thermostatic compartment without sacrificing the appreciable accuracy of the result. The detection limit was calculated according to Tanakss method, 28 from the expression D= B+t 2SB D is the statistical detection limit B is the average blank value SB = R/d2 where R= blank max-blank min. And 1/d2 is a factor for obtaining SB from the range R of n replicates. It is advisable to take 1/d2 = 0.5908 for use of three blank measurements and t=3 [28]. The detection limit estimated for the method under specified conditions using the A 15 calibration equation corresponds to 2.5x10-7M concentration of Hg+2. The sensitivity expressed by the slope of calibration function (A15) is 3.3x103 Lmol-1 which is quite high. Further improvement in sensitivity can be achieved by increasing

the time interval to 20 or 25 minutes or more (Table1) but this would correspondingly increase the total analysis time and also introduce higher errors. Percentage errors for the determination of various mercury concentrations in the ramge 3x10 -7 to 3x10-8 M are cited in Table 2. The general precision and accuracy for the determination of mercury was tested in presence of diverse ions at a fixed mercury (II) concentration and results are given in Table 3, along with percentage errors. Thiosulphate, cyanide and thiocyanate ions complex strongly with Hg+2 and thus mask its catalytic activity. The interference by Cu+2 , Cd+2 , Pb+2 ,and Ni+2 at low mercury concentration can be explained due to their salt formation with [Fe(CN)6] 4 - 29. TABLE 3. Effect of Various interfering and non-interfering Cations and anions on determination of [Hg+2] using A15 Calibration Curves Ion Cd+2 Pb+2 Ni+2 Cu+2 EDTA Oxalic Acid Condition: Ion Conc.taken x107 M 2.5 2.5 2.5 2.5 2.5 2.5 x107M 2.51 2.50 2.52 2.49 2.53 2.50 0.4 0.0 0.8 0.4 1.2 0.0 [Hg+2] found %Error

[Fe(CN)6]4- =5.5x10-3 M,[phen] = 2.5x 10-4M [Hg+2] =2.5x10-7M,

pH=3.0+0.02,I = 0.1M(kNO3) and temp = 25+ 0.1oC. 3.1 Application to Determination of Mercury (II) To establish reliability and applicability i. e. in order to validate the analytical capability of the proposed method, recovery experiments were carried out on synthetic mixtures (SMs) containing other metals that are commonly found alongside mercury. This had to be done because authentic samples containing trace amounts of mercury (II) were not available. The results are shown in Table 4. The higher recovery can in most cases can be attributed to a synergistic effect from other ions,

which is not uncommon. The recovery in each case is well within the acceptable error limit for envirommental monitoring applications. TABLE 4. Application of the proposed method for the determination of mercury (II) in the synthetic Mixtures under the conditions specified before for A 15 Curve. Synthetic Mixture (SM) 1 2 3 Compsition of SM * Conc. X107 M Hg0.30 +Cu 0.55 Co 1.75+ Cd 0.80 Hg0.30+Zn2.25 Cd 0.80+Ag0.85 Hg 0.30+Pb 0.87 Ni 0.40+Cr 0.55 0.32 0.29 0.33 101.2 99.0 101.7 Hg+2 Found ** % Recovery 7 conc. x10 M

Condition: * All are in +2 state Except Cr+3 and Ag+ ** Mean of three analysis 4. Conclusion Finally it has been eslablished that Hg+2 can be determined in trace amounts from 3.0x10-7 to 3x10-8 M by a Kinetic method in presence of a number of metal ions present in about 10-100 folds excess of mercury. The proposed analytical method can be adopted for determination of mercury present as an envirommental pollutant in various unknown saniples. Among the various sophisticated procedures employed in the envirommental analytical work, the method described in the present investigation, involving the use of simple spectrophotometric technique, still ranks popular on account of its simplicity, adaptibility, economy and above all more accuracy.

5. Acknoledgement

I am extremely thankful to Prof.R.M.Naik for guiding me throughout this work. References [1]Morita,M.; Yoshinaga,J.;.Edmonds, L.S.; Pure Appl. Chem. 1998,70, 1585. [2]Chen,N.;.Lai,E.P.C.; Talanta. 1989,36, 479. [3] Mottola,H.A.;.Perez-Bebdito,D.; Anal.Chem. 1996 ,68, 257R. [4] Crouch,S.R.; Cullen,T.F.; Scheeline,A.; Kirkor,E.S.; Anal. Chem. 1998,70,53R. [5] Richardson,S.D.;Anal. Chem. 2001,73, 2719. [6] Clement,R.E.; Yang,P.W.; Anal Chem. 2001,73, 2761. [7] Naik,Rahey,M..; Srivastava, A.;Prasad,S.; Spectrochim. Acta. Part A. 2008,69 (1), 193. [8] Agarwal, Ram K.;Prasad,S.; Bioinorg. Chem. Appln. 2005, 3, 271. [9] Prasad, S.; Halafihi, T.; Mikrochim.Acta. 2003,142, 237. [10] Raman,B.;Shinde,V.M.; Analyst.1990, 115, 93. [11] Ma,W.X.; Liu,F.;Li,K.A.; Anal.Chim.Acta2000,.416, 191. [12] Kawashima,T.;Nakano,S.;Tabata,M.;Tanaka,M.; Trends Anal.Chem. 1997, 16,132 . [13] Parra, M.J.A.; Mateos,A.A.; De Maria,G.G.;Rozas,L.G.; Analyst,1992 ,117, 921. [14] Igov, R.P.; Mitic,G.;Miletic,S.; Mitic,S.; J.Serb.Chem.Soc. 1997,62, 375.. [15] Pirvutoiu, S. .;Surugiu,I.;Dey,E.S.; Ciucu,A.V.; Magearu; Danielson,B.; Analyst,2001, 126, 1612. [16] Sanchez-Pedreno,C.; Albero,M.I.; Garcia,M.S.; Talanta. 1988 ,35, 397. [17] Shi,R.; Stein,K.;.Schwedt,G.; Fresenius;J.Anal.Chem. 1997,357, 752. [18] Ye, C.; Fan,J.;Feng,S.; Huang,X.; Huaxue, Fenxi .; 2000,28, 1155, (CA133:3289 1s). [19] Safavi, A. ; Baezzat,M.R.; Anal.Lett. 1996,29, 807. [20] Lazaro, F. ;. Castro, M.D; Valcarcel,M.;Fresenius,Z.; Anal. Chem. 1985, 320,128. [21] Grases, F. ; March,J.G.; Foreza,R.; Microchem.J. 1985,32, 367. [22] Ramesh, A.; Analyst.1993,118, 945. [23] Jlang, H.;Yuan,D.; Xuebao, Huaxue;1991, 45, 757.(CA 115:214398s). [24] Sicilia,D.; Rubio,S.; Perez-Bendito,D.; Talanta.1991,38, 1147. [25] Feng,Y.L.; Narasaki,H.; Tian,L.C.; Wu,S.M.; Chen II,Y.; Anal.Sci.1999,15,915.

[26] Phull,M.; Bajaj,H.C.; Nigam,P.C.; Talanta.1981,28, 610. [27] Weast,R.C.; CRC Handbook of Chemistry and Physics,49th ed. ;Ohio,Chemical Rubber Co.,1969. [28] Tanaka,N.; Kyoto, Fu Eisci; Nemp. Kenkyusho;1977, 22, 121 (CA.1979:90: 11440lv). [29] Sharpe,A.G.; The Chemistry of Cyanocomplexes of the Transition Metals ,London. Academic Press,1976.