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 AgHg 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, 3propyl- I,2,4-tri azo le" thiocyanate(" 2-imidazo lidinethione 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 (

Fax: 9 1-08252 -257 107 1 )

-~

prakash.shclt Y@ l1lit.manipa l.cdu:

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

di still ed wate r. Xylenol orange indicator (0.5%) was
prepared in disti lied water.

during titration s under the experimental cond ition s .

This helps in the detection of sharp end-point.

Determination of mercury

The addition of sodium metabi suJphite in the

molar ratio of 1:5 (Meta l :Reagent) was found to be
sufficient for the in stantaneolls and qu a ntitati ve re lease
of EDTA from Hg-EDTA co mplex. However, no
adverse effects were noticed on addin g large excess of
the reagent.

To a so lution containing 4-100 mg of mercury(II)

and vary in g amounts of foreign ion s, 1-25 mL of 0 .04
M EDTA was added and the mixture was diluted to
about 100 mL with distilled water. The pH of the
so luti on was adjusted to 5-6 by adding solid hexamine.
The surplus EDTA was backtitrated against stand ard
zin c su lphate so lution to a sharp colour change of
xy leno l oran ge from yellow to red . To this, an excess
of 2% sod ium metabi sulphite so lution ( I mL for each
4 mg of Hg) was added and th e contents were mixed
well. Th e liberated EDTA was the n titrated against the
same standard zinc su lph ate so luti on as before. The
seco nd titre value is equivalent to th e mercury content
in th e ali quot.
Analysis of alloy samples

A known weight (0.2-0.3 g) of alloy sample was

di sso lved in minimum amount of concentrated nitric
acid by slow heat ing. Tin present, if any, precipitated
as metastann ic acid and was fi ltered off. The solution
or filtrate was diluted with distilled water and made up
to 100 mL in a standard nask. Aliquots of 10 mL were
used for th e determination o f me rcury by the procedure
desc ribed.
Ana lys is of mercury complexes

M e rcur y (Il) complexes with thiourea ,

thi ocarbohyd razide, I ,2,4-triazole-3(5)-thiol, thionalide,
4-ami no-5-mercapto-3-methyl-I ,2,4-triazole we re
prepared and purified as in the reported-procedures I4' 17
A known we ight of the complex (0. 1-0.2 g) was
carefully decomposed with aqua-regia by evaporation
to nea r dryness. The residue was cooled, dissolved in
distilled water and made up to 100 mL in a standard
fla sk. Aliquots of 10 mL were used for titration by the
recommended procedure.
Results and Discussion
Sodium metabi sulphite selecti vely decomposes HgEDTA comple x and re lease EDTA quantitatively. The
mercury(ll) th e n forms a stable so lubl e complex with
the reagent. Mercury(JI) be ing a soft metal ion, prefers
to bond stron g ly with su lphu r containing ligands'K. , ~ . It
is, th erefore, reasonabl e to expect that Hg-reage nt
co mpl ex formed is apparently more stable than HgEDTA complex . The in stantaneous release of EDTA
from Hg-EDTA complex at room temperature itself
supports thi s view. Further, no prec ipitates are formed

Effect of excess reagent

Reliability of the method

To assess the accuracy and precIS Ion of th e

proposed method , detel111inati ons of mercury at diffe re nt
concentration leve ls were ca rri ed out as pe r the
recommended procedure. It is ev ident from th e results
(Table I) that the observed relati ve error of the me th od
is less th an 0 .26 % and the coefficient of variati o n not
more than 0.40 %. Th us the method is acc urate bes ides
being precise.
Effect of foreign ions

The effect of the p rese nce of va ri ous fore ig n io ns

on the quantitat ive determin at ion of me rc ury we re
s tudied with aliquots co nt a inin g 19.30 m g o f
mercury(II). Of th e vari ous cations and anion s tes ted
individually in th e de te rminati o n of me rcury (II), no
interference was observed in the presence of 200 mg of
Zn(II), Pb(Il), acetate , borate, c itrate, tl uoride, nitrate,
oxalate, su lphate; 150 mg of c hloride; 100 mg o f
Tablel-DeterminUlion of mercury in mercury( lI ) nil rule SO IUlioll
Mercury, mg
Taken

CoelTicieJ1l of
variatioll (%)

Relati ve
error ( % )

FOllnd *

3.86

3.87

0.40

+0.26

7. 72

7.71

0 .28

-0. 13

11 .58

11 .61

0.37

+0.26

19.30

19.28

0.26

-0. 10

38.60

38.50

0 . 11

-0.26

57.90

58 .00

0.07

+0 . 17

77.20

77 .26

0 .1 1

+O . O~

100.52

0. 11

+0. 16

100.36

* Average of six determinations

SHETTY & SHETTY e! al. : COMPLEXOMETR IC METHOD FOR THE DETERMINATION OF MERCURY

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

AI(III), FeWI), Mo(VI), Ti(lV) ; 20 mg of Mn(II) ; 15
mg of Ru(III ), Rh(III) , Pt(IV), Ir(III), Au(III), As(V) .
The metal ions such as TI (III), Pd(II) and Sn(IV) show
severe intelference. Thi s is due to the simu ltaneous
release of EDTA from their respective EDTA complexes
by the reagent. However, the interference of TI(III) (up
to 40 mg) , Pd(II) (20 mg) and Sn(IV) (40 mg) can be
eliminated by premaskin g these ions with hydrazine
sulph ate, L-histidine and sodium fluoride respectively.
Analytical applicatio ns

The prese nt method was app li ed to the

determination of mercury in alloy samples. The results
(Tab le 2) are in reasonably good agreement with those
obtai ned gravime trically by periodate methodl.l. The
method developed was also applied to the determination
of mercury in its comp lexes (Tab le 3). From the
experimental results, it can be concluded that the
method can be convenient ly employed for the rap id
analysis of such samples with a fair degree of accuracy.

Conclusions
To conclude, the proposed method is simpl e and
rapid besides be ing accurate. It does not require any
heating for the qu antitative re lease of EDTA from the
Hg-EDTA comp lex. Sodium metabi sulphite is read il y
avai lab le, cheap and water so lubl e reagent , so that it
can be used convenie ntly. The reagent form s no
precipitate either with me rcury (II ) or the titrant under
the experimental conditions. This facilitates the detection
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
mercury in its comp lexes and alloy samp les.
Acknowledgement
Sincere thank s are due to MAHE [Deemed
University], Manipal for the financial assistance to one
of the authors (PS) and De ntal Materia ls Departme nt ,
College of Dental Surgery, Manipal for the
complementary alloy sampl es .

References
Herber R F M & Stoeppler M (eds), Tra ce elelllel/! ol/olysis

Table 2-Determination of mercury in alloy samples

Alloy sample

Mercury*

Mercury**

Rel ative

prese/ll (% )

found (%)

error (%)

Dental amalga m
(Hg-Ag-Sn-Cu)

4 1.80

41 .68

-0.29

Hg-Zn all oy

25.08

25. 14

+0.24

Hg-Cu all oy

50.16

50.04

-0.24

2
3
4

Mercury
present (o/r )

Mercury*
found (%)

6
7
8

Table 3-Determin ati on of mercury in complexes

Complex

il/ biolog ical specilllel/s (Elsevier, New York), 1994, 405 .

* Estimated gravimetrically by periodate method .

** Average of lhree determinations.

Relative
error ( % )

10
II

Hg(C H,N 2S)C1 2V2Hp'

56. 18

56.08

-0.18

H g(CH,N ~ S ) 2 C1 !h

47.28

47. 18

-0.2 1

Hg(C I-I"N,S)P !'

4 1.46

41 .56

+0.24

Il g(C} 12N,S)/

49 .55

49.42

-0.26

Hg(C,/I,,,ONS\ '

31.70

3 1.62

-0.25

Hg(C,H, . S)2'

43.7 1

43.60

-0.25

IClI(en) ~ 11

HgI,!

22.49

22.54

+0. 22

Hg[Zn (eN S).,

40 .26

40 .34

+0.20

" Ave rage of lhree determinations.

Mercury compl ex with thiourea,,&h, lhi ocarbohydrazide', 1,2,4lriazolc-3( 5 )-t hi ol", thional ide", 4-amino-5-mercapto-3-mcth yl1.2.4- lri azo lc'.

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