Indi an Journal of Chemical Technology

Vol. II. March 2004. pp. 163-165

Complexometric method . for the determination of mercury usmg

- .
sodium metabisulphite as selective masking reagent
Prakash Shetty"* & A Nity ananda Shetty"
"Department of Chemistry, Manipal Institute of Technology, Manipal 576 11 9, India
"Department of Chemi stry, Nati onal Institute of Technology, Karn ataka. Suratkal,
Srinivasnagar 575 025, Indi a .

.., Received 12 Jllll e 2003; revised received 25 Septelllher 2003; accep ted 4 Fe!JI'//(f rv 2004

A selecti ve comp lexometri c method is described for the determinati on of mercury(lI) using sud ium metabisulphite
as a masking reagent. An excess of EDTA is added to mercury(lI ) soluti on containing assoc iated dive rse metal ions
and the surplus EDTA is back titrated at pH 5-6 (hexamine buffer) with standard zinc sulphate solut io n using xy lenol
orange as indicator. An aqueous soluti on of sodium metabi sulphite is then added to di splace EDTA selectively from
Hg-EDTA complex and the released EDTA is then titrated aga inst th e same stand ard zinc sul phate soluti on.
Reproducible and accurate results are obtained in the range 4-100 mg of mercury with a relati ve error:::; 0.26% and
coeffici ent of variati on :::;0.40%. The method is usefu l fo r the analysis of mercury in co mplexes and all oy samples.
IPC Code: GOIN33/20, 3 111 6
Keywords: Complexometry. Mercury, Sodium metabisu lphite. Masking agent

Mercury(Il) is a protoplasmi c poison, toxic e ven at
sub-trace levels and causes many di seases ' . Compounds
of mercury are used widely as fun gic ides and pesticides.
Mercury forms amalgams with many me tal s, which
find various applications in di verse fie lds such as Ag-
Hg in dental fillings, Zn-Hg as redu c ing agent in
chemical synthesis, and Cd-Hg in weston-cadmium
cell. In most of these application s, often a simple,
rapid and accurate ana lytical method for dete rmining
th e me rcury co nte nt in the sampl es is essential.
Mercury(II) is usua ll y de te rmin ed in the presence of
associated metal ions by the selective decomposition of
Hg -EDTA compl ex with maskin g age nts . Wh e n
thi ose micarb az id e~ and thi ourea' are used as masking
agents , many metal ions show interference. The method
usin g N-all ylthi ourea-l as masking agent requires heating
to deco mpose th e Hg-EDTA comp lex and al so
prec ipitati on of HgS occurs. 4-Amino-S-mercapto, 3-
propyl- I,2,4-tri azo le" thiocyanate(" 2-imidazo lidine-
thione 7 , hexa h y dr o p y rimidin e-2 -thion e x and
acety l aceto n e~ are a lso used as mask ing reagents for
* For C,)lTCspolldc ncc ( -~ prakash.shclt Y@ l1lit.manipa l.cdu:
Fax: 9 1-08252 -257 107 1 )
mercury (II). Some of the re age nts, 7X require tedi ous
and time-con suming pre paration methods . 3-Mercapto
propane-I ,2-di o l lO , thiog lyco ll ic acid II and 2-me rcapto
propionyl g l ycine'~, have bee n re ported ea rli er as
selecti~e maskin g reagents for merc ury .
This pape r desc ribes the applicati on of sodium
metabi sulphite (Na 2S 20 ,) as a selective masking reage nt
for the complexo me tric dete rmin ation of merc ury(If).
Copper(1I) does not inte rfe re and th e decompos iti on of
Hg-EDTA compl ex takes place in stantaneously at room
temperature.
Experimental Procedure
Materials
An alytica l g rade chemicals were used. A stoc k
soluti o n containing 3.86 Ill g/mL of me rcury(Il) was
prepared by di sso lvin g 6.83 g of me rcury(II) nitrate
(Me rck) in one litre distill ed wate r and stand ardi sed
gravimetrica ll y by ethy len edi a min e me thod 13 . EDTA
so luti on (0.04 M ) was prepared by di sso lvin g 14.89 g
of di sod ium sa lt of EDTA (Merc k) in distill ed water
and dilutin g to o ne litre. Zi nc sulphate so luti on (0 .02
M) was st anda rdi sed by ox in ate method ". Sodium
 164 INDIAN J. CHEM. TECHNOL. , MARCH 2004

metabisulphi te (Merck) was used as 2% solution in during titration s under the experimental cond ition s .
di still ed wate r. Xylenol orange indicator (0.5%) was This helps in the detection of sharp end-point.
prepared in disti lied water. Effect of excess reagent
Determination of mercury The addition of sodium metabi suJphite in the
To a so lution containing 4-100 mg of mercury(II) molar ratio of 1:5 (Meta l :Reagent) was found to be
and vary in g amounts of foreign ion s, 1-25 mL of 0 .04 sufficient for the in stantaneolls and qu a ntitati ve re lease
M EDTA was added and the mixture was diluted to of EDTA from Hg-EDTA co mplex. However, no
about 100 mL with distilled water. The pH of the adverse effects were noticed on addin g large excess of
so luti on was adjusted to 5-6 by adding solid hexamine. the reagent.
The surplus EDTA was backtitrated against stand ard Reliability of the method
zin c su lphate so lution to a sharp colour change of To assess the accuracy and precIS Ion of th e
xy leno l oran ge from yellow to red . To this, an excess proposed method , detel111inati ons of mercury at diffe re nt
of 2% sod ium metabi sulphite so lution ( I mL for each concentration leve ls were ca rri ed out as pe r the
4 mg of Hg) was added and th e contents were mixed recommended procedure. It is ev ident from th e results
well. Th e liberated EDTA was the n titrated against the (Table I) that the observed relati ve error of the me th od
same standard zinc su lph ate so luti on as before. The is less th an 0 .26 % and the coefficient of variati o n not
seco nd titre value is equivalent to th e mercury content more than 0.40 %. Th us the method is acc urate bes ides
in th e ali quot. being precise.
Analysis of alloy samples
Effect of foreign ions
A known weight (0.2-0.3 g) of alloy sample was
The effect of the p rese nce of va ri ous fore ig n io ns
di sso lved in minimum amount of concentrated nitric
on the quantitat ive determin at ion of me rc ury we re
acid by slow heat ing. Tin present, if any, precipitated
s tudied with aliquots co nt a inin g 19.30 m g o f
as metastann ic acid and was fi ltered off. The solution
mercury(II). Of th e vari ous cations and anion s tes ted
or filtrate was diluted with distilled water and made up
individually in th e de te rminati o n of me rcury (II), no
to 100 mL in a standard nask. Aliquots of 10 mL were
interference was observed in the presence of 200 mg of
used for th e determination o f me rcury by the procedure
Zn(II), Pb(Il), acetate , borate, c itrate, tl uoride, nitrate,
desc ribed.
oxalate, su lphate; 150 mg of c hloride; 100 mg o f
Ana lys is of mercury complexes
M e rcur y (Il) complexes with thiourea , Tablel-DeterminUlion of mercury in mercury( lI ) nil rule SO IUlioll
thi ocarbohyd razide, I ,2,4-triazole-3(5)-thiol, thionalide,
Mercury, mg CoelTicieJ1l of Relati ve
4-ami no-5-mercapto-3-methyl-I ,2,4-triazole we re
variatioll (%) error ( % )
prepared and purified as in the reported-procedures I4' 17 • Taken FOllnd *
A known we ight of the complex (0. 1-0.2 g) was
3.86 3.87 0.40 +0.26
carefully decomposed with aqua-regia by evaporation
to nea r dryness. The residue was cooled, dissolved in
7. 72 7.71 0 .28 -0. 13
distilled water and made up to 100 mL in a standard
fla sk. Aliquots of 10 mL were used for titration by the
11 .58 11 .61 0.37 +0.26
recommended procedure.
Results and Discussion
19.30 19.28 0.26 -0. 10
Sodium metabi sulphite selecti vely decomposes Hg-
EDTA comple x and re lease EDTA quantitatively. The
38.60 38.50 0 . 11 -0.26
mercury(ll) th e n forms a stable so lubl e complex with
the reagent. Mercury(JI) be ing a soft metal ion, prefers
57.90 58 .00 0.07 +0 . 17
to bond stron g ly with su lphu r containing ligands'K. , ~ . It
is, th erefore, reasonabl e to expect that Hg-reage nt 0 .1 1 +O . O~
77.20 77 .26
co mpl ex formed is apparently more stable than Hg-
EDTA complex . The in stantaneous release of EDTA 100.36 100.52 0. 11 +0. 16
from Hg-EDTA complex at room temperature itself
* Average of six determinations
supports thi s view. Further, no prec ipitates are formed
 SHETTY & SHETTY e! al. : COMPLEXOMETR IC METHOD FOR THE DETERMINATION OF MERCURY 165

Cu(ll), CdeII), Ni(Il), Co(II), Bi(lIl); 40 mg of Ag(I) , Conclusions

AI(III), FeWI), Mo(VI), Ti(lV) ; 20 mg of Mn(II) ; 15 To conclude, the proposed method is simpl e and
mg of Ru(III ), Rh(III) , Pt(IV), Ir(III), Au(III), As(V) . rapid besides be ing accurate. It does not require any
The metal ions such as TI (III), Pd(II) and Sn(IV) show heating for the qu antitative re lease of EDTA from the
severe intelference. Thi s is due to the simu ltaneous Hg-EDTA comp lex. Sodium metabi sulphite is read il y
release of EDTA from their respective EDTA complexes avai lab le, cheap and water so lubl e reagent , so that it
by the reagent. However, the interference of TI(III) (up can be used convenie ntly. The reagent form s no
to 40 mg) , Pd(II) (20 mg) and Sn(IV) (40 mg) can be precipitate either with me rcury (II ) or the titrant under
eliminated by premaskin g these ions with hydrazine the experimental conditions. This facilitates the detection
sulph ate, L-histidine and sodium fluoride respectively. of a sharp end-point. The method is fairly se lective, so
it can be used successfu ll y for the rapid analy sis of
Analytical applicatio ns
mercury in its comp lexes and alloy samp les.
The prese nt method was app li ed to the
Acknowledgement
determination of mercury in alloy samples. The results
(Tab le 2) are in reasonably good agreement with those Sincere thank s are due to MAHE [Deemed
obtai ned gravime trically by periodate methodl.l. The University], Manipal for the financial assistance to one
method developed was also applied to the determination of the authors (PS) and De ntal Materia ls Departme nt ,
of mercury in its comp lexes (Tab le 3). From the College of Dental Surgery, Manipal for the
experimental results, it can be concluded that the complementary alloy sampl es .
method can be convenient ly employed for the rap id
analysis of such samples with a fair degree of accuracy. References
Table 2-Determination of mercury in alloy samples Herber R F M & Stoeppler M (eds), Tra ce elelllel/! ol/olysis
il/ biolog ical specilllel/s (Elsevier, New York), 1994, 405 .
Alloy sample Mercury* Mercury** Rel ative
2 Korbl J & Pribil R, Chelll List\', 51 ( 1957) 667.
prese/ll (% ) found (%) error (%) 3 Singh R P, Talall/a, 16 (1969) 1447.
4 Vasilikioti s G S & Apostolopoulou C D, Microchelll J. 20
Dental amalga m 4 1.80 41 .68 -0.29
(Hg-Ag-Sn-Cu) ( 1975) 66.
5 Gadiyar H R A, Gadag R V & Gajendragad M R, Talol//a.
Hg-Zn all oy 25.08 25. 14 +0.24 29 ( 1982) 94 1.
Hg-Cu all oy 50.16 50.04 -0.24 6 Raoot K N, Sarala Raoot & Lalitha Kumari V, Tolalllo , 30
( 1983) 611.
* Estimated gravimetrically by periodate method .
7 Narayana B & Gajendragad M R, Talal/!o, 35 (1988) 719.
** Average of lhree determinations. 8 Narayana B, Kuchinad G T & Gajendragad M R, Chil/ ese J
Chelll, 10 ( 1992) 394.
Table 3-Determin ati on of mercury in complexes 9 Bije Mathew, Rao B M & Narayana B, AI/a lys!, 120 ( 1995)
1097.
Complex Mercury Mercury* Relative
10 Shetty Prakash , Kh ade r A M A, Shelly Nityananda A &
present (o/r ) found (%) error ( % )
Gadag R V, ReI' ROIIIII Cllilll , 40 ( 1995) 35 1.
Hg(C H,N 2S)C1 2·V2Hp' 56. 18 56.08 -0.18 II Shelly Prakas h, Shelly Nit ya nanda A & Gadag R Y. Re"
H g(CH,N ~ S ) 2 C1 !h 47.28 47. 18 -0.2 1 ROIIIII Chill/, 45 (2000) 841.
Hg(C I-I"N,S)P !' 4 1.46 41 .56 +0.24 12 Shelly Prakas h, Shell y Nityananda A & Gadag R V.
Il g(C} 12N,S)/ 49 .55 49.42 -0.26 Mikrochilll AC/a. 137 (200 1) 7 1.
13 Vogel A I, A Tn! Book of Qllal/!ilarive II/orgal/ic Al/oll'Sis.
Hg(C,/I,,,ONS\ ' 31.70 3 1.62 -0.25
3rd edn (Longman, London), 1964, 488 & 288.
Hg(C,H, . S)2' 43.7 1 43.60 -0.25 14 Rosenheim R & Meyer V J , Z A IlUlg Cirelli. 49 (1906) 13.
IClI(en) ~ 11 HgI,! 22.49 22.54 +0. 22 15 Burns G R, II/o rg Cir elli. 7 ( 1968) 277.
Hg[Zn (eN S)., 40 .26 40 .34 +0.20 16 Gupta B K, Gupta D S. Dikshit S K & Agarwala U, II/dial/
J Chelll , 15A ( 1977) 624.
" Ave rage of lhree determinations.
Mercury compl ex with thiourea,,&h, lhi ocarbohydrazide', 1,2,4- 17 Gadag R V & Gagendragad M R, Illdioll J Cheill. 16A
lriazolc-3( 5 )-t hi ol", thional ide", 4-amino-5-mercapto-3-mcth yl- ( 1978) 703.
1.2.4- lri azo lc'. 18 Pearson R G, Cll elll £I/g g Nell·s. 43 ( 1965 ) 90.
19 Pearso n R G. Cllelll Brir . 3 ( 1967) 103 .