PART ONE

ORGANIC REAGENTS AS MASKING AGENTS IN

COMPLEXOMETRIC DETERMINATION OF METALS

 CHAPTER I

INTRODUCTION TO MASKING AND DEMASKING TECHNIQUES IN

COMPLEXOMETRIC TITRATION

1.1 TITRIMETRY

1.3 COMPLEXOMETRIC TITRATIONS

1.3 SCOPE OF COMPLEXOMETRIC TITRATIONS

1.4 SELECTIVITY IN EDTA TITRATIONS

1.5 MASKING TECHNIQUE

1.6 TYPES OF MASKING REACTIONS

1.7 DEMASKING TECHNIQUE

1.8 CHOICE OF MASKING AGENTS

1.9 INDUSTRIAL APPLICTTONS OF MASKING AGENTS

1.10 ORGANIC REAGENTS IN CHEMICAL ANALYSIS

1.11 PRESENT WORK

1.1 TITRIMETRY

The last four decades have witnessed a tremendous

change in the field of Analytical Chemistry. - An array of

instrumental methods of analysis have been developed. These

are naturally rapid and extremely sensitive with a high degree

of accuracy, but are expensive. The classical methods of

gravimetry and titrimetry have therefore faced a strong

challenge from these methods. Gravimetric methods, which are

inevitably rather slow and also involve many steps, have been

superseded by new techniques. Yet, the gravimetric methods are

often used to confirm the reliability of new instrumental

methods. On the otherhand, titrimetric methods continue to be

of prime importance. Titrimetry, far from being replaced,

stands firm as an analytical technique of value in teaching,

research and practice. These methods are widely used for

routine analysis because they are rapid, convenient, accurate

and above all they need simple equipments. Titrimetric

methods, therefore provide a lively and still growing area of

Analytical Chemistry.

During the past few decades some new techniques

have been introduced in the field of titrimetry to keep pace

with modern developments in industry and research. " Among

titrimetric methods, the complexometry enjoys a great deal of

interest as a prominent analytical tool.

 2

1.2 COMPLEXOMETRIC TITRATIONS

All those titrimetric methods, which involve

complex-formation reactions, fall under complexometric

titrations. A complexation reaction of a ligand with a metal

ion in homogeneous liquid phase involves replacement of one or

more co-ordinated solvent molecules by other nucleophiles or

ligands!!.!. In aqueous phase, the reaction can be represented

by the equation,

rw-
MCH C» M CH2O) n-1 L H 2O
2 n

where L represents a monodentate neutral ligand. The charge on

M in the complex, however, depends on the nature of the ligand.

The replacement of water molecules by other ligands can

continue till the final complex ML Ti is formed, where "n" is the

co-ordination number of the metal ion.

The molecule or an ion containing the donor atoms

is called a ligand. Ligands may be classified according to the

number of donor atoms per ligand molecule. Ligands such as

halide ions, CN\ SCN", NO- , NH , HO, C H N, etc. , which have
9 9 2 S 5

only one donor site per molecule are called unidentate ligands.

If a ligand has two donor atoms both forming co-ordinate bonds

with the same metal ion, then it is termed as bidentate one.

Ligands containing more than two donor atoms per molecule are

commonly known as poly-dentates. EDTA is one such polydentate

ligand since it has six donor sites in two nitrogen and four
 3

oxygen atoms. A chelate is formed when a metal ion forms a

complex with a bi- or multi-dentate ligand. The process of

chelate formation is known as chelation and the ligand involved

is called a chelating agent or chelon. Chelation offers

stability to the metal complexes. Titrations involving chelons

are called chelatometric titrations. EDTA is a powerful

chelating titrant.

The technique of complexometric titrations was

given a great stimulus in 1950, following the introduction of

EDTA and metallochromic indicators. Once the potential of EDTA

in the determination of ions was appreciated by chemists,

subsequent developments were very rapid.

For convenience, EDTA is often abbreviated as H^Y

and its disodium salt is therefore, Ha H Y. It affords the

2 2

complex forming ion H^Y2- in aqueous soluton, which forms

stable 1:1 mol ar complexes with many di- and ter a-valent metal
2—
ions. The reaction of H^Y with metal ions can be represented

as :

♦
M™- + H Y2- .----> CMY^"-** + 2H*
2 <----

It is obvious from the above equation that the ionisation of

the complex is pH dependent. Lowering of the pH decreases the

stability of the metal-EDTA complex. However, if a metal-EDTA

complex is highly stable, then the titration of metal ion with

EDTA may be carried out at lower pH.

 4

1.3 SCOPE OF COMPLEXOMETRIC TITRATIONS

Complexometric titrations with EDTA and its

related compounds have been extensively used for the

determination of virtually every metal ion with the exception

of alkali metal ions. EDTA being stable, water soluble and

having a definite composition, it is preferable to other

titrants. Since the stability constants of the various

metal-EDTA complexes vary widely, some selectivity in the

titration of different metal ions may be achieved by

controlling the pH. In acid solutions CpH 1 -3D ter- and

tetra-valent cations can be titrated without interference from

divalent cations. At pH 5 all divalent cations except those of

the alkaline earths are titrated, and the alkaline earths are

included if the titration is carried out at pH 10 *2*.

Majority of metal-EDTA complexes being water

soluble, the equivalence point is readily reached in such

titratons. Besides, it is possible to employ complexometric

titration for the determination of several metal ions in semi-

micro levels I3J. The introduction of metal-ion indicators has

greatly enhanced the utility of EDTA in complexometry'4! . The

majority of complexometric titrations are performed with these

indicators which themselves are chelating agents and. whose

metal-complexes have different colors. Most commonly used

indicators are eriochrome black-T, pyrocatechol violet,

xylenol orange, calmagite, 1 -C2-pyridylazonaphthoiZ>, zincon,

methyl-thymol blue, and calceium blue. Each of these indicator

 5

is effective over a limited pH range, but together, they cover

a wide range of pH.

Finally, interference from a particular cation can

sometimes be eliminated by using a suitable secondary masking

agent, that preferentially forms highly stable and soluble

complex with the potential interference. Cyanide ion is often

employed as a masking agent to permit the titration of magnesium

and calcium ions in the presence of cadmium, cobalt, copper,

nickel, zinc and palladium!21 .

All these factors coupled with the inherent

potential of EDTA to form stable and soluble 1:1 molar

complexes with metal ions have made it a versatile chelating

agent.

1.4 SELECTIVITY IN EDTA TITRATIONS

EDTA is a highly unselective titrant because it

complexes with numerous di-, ter- and tetra-valent metal ions.

Improved selectivity must therefore be sought for in applying

it to the resolution of multicomponent metal systems!4!. When

a solution containing two metal ions, which can form complexes

with EDTA, is titrated without the addition of a complex

forming indicator and if a titration error of 0. lPi is

permissible, then the ratio of the stability constants of the

two metal-EDTA complexes must be K /K i > lO4, if m* is not to
MM —

interfere with the titration of u. Strictly speaking, the

constants and should be apparent stability constants of

the complexes. If a complex forming indicator is used, then

 6

0
for at similar titration error, the ratio must be K /K 1 > 10 .
U M ~

Since there are very few cases where the ratio

of stability constants in a particular mixture is above 10**,

complications may often arise when one wishes to determine a

desired metal in a mixture. In such a solution, it is often

necessary to carry out the actual titration by time consuming

separation techniques. However, some degree of selectivity can

be achieved by appropriate adjustment of pH. Metal ions

forming more stable EDTA complexes can be titrated at lower pH

values. Some times, the addition of a secondary masking agent

can yield the desired effect. In a mixture of metal ions,

specific ions are masked by secondary masking agents so that

they can no longer react with either EDTA or with the

indicator. In somes cases, demasking agents can also be used

in order to achieve the desired selectivity. Thus, the use of

masking and selective demasking agents permits the

determination of desired metal ion in a mixture.

1.5 MASKING TECHNIQUE

The technique of masking is an elegant means

available for conditioning the system in the enhancement of

selectivity. It is one of the versatile and useful adjuncts in

Analytical Chemistry.

The masking technique in analysis was first

introduced by Professor Fritz Feigl.BI to describe a process by

which an ion or a molecule could be so transformed, usually by

complex formation, that it no longer exhibits its
 7

characteristic chemical reactions. This technique found wide

spread applications in many fields of chemistry because it

offers a convenient means to remove or temporarily supress the

effect of an unwanted constituents of - a system without

resorting to elaborate separation. The substance used for

masking is commonly known as "masking agent".

In Analytical Chemistry, the technique of masking

is mainly used to improve selectivity in a wide variety of

methods such as complexometric titrations, spectrophotometry,

gravimetry, polarography, solvent extraction, ion-exchange,

chromatography, etc. Apart from this, the technique possesses

extensive industrial applications.

The conventional methods of analysis have been

suplemented by certain newly developed analytical techniques

such as atomic absorption spectrometry. The extent of this

erosion will depend largely on how much can be achieved in

simplifying and speeding up the existing titrimetric, spectro-

photometric and gravimetric procedures without sacrificing

accuracy and reliability. It is in this direction that much

can be expected from simple and elegant masking and demasking

techniques. These are designed to enhance the selectivity of

chemical reactions and in many cases to make possible the rapid

analysis of mixtures that would otherwise take unduly long time

by the conventional methods of analysis.

 8

1.6 TYPES OF MASKING REACTIONS

The important types of masking reactions are

masking by precipitation, soluble complex formation, oxidation

or redcution, mixed masking, kinetic masking and indirect

masking. The essence of these masking reactions are described

bel ow.

1.6.1 Masking by Precipitation

Masking by precipitation is a method in which the

interfering species is precipitated by a masking agent and

there by it is prevented from entering into reactions.

The added masking agent forms an insoluble

precipitate with the species to be masked. This process is

different from the actual separation in the sense that the

precipitate formed is not removed before titration. It is

obvious that the concentration of the metal ions masked by a

precipitation reaction must be made so low that no reaction can

take place.

This technique was employed in the determination

of calcium in presence of magnesium CpH 12D, wherein Mg is

precipitated as its hydroxide. Similarly metal ions such as

FeCIII}, TiCIV3, SnCIVD can also be masked by precipitating as

their hydroxides. Pribil ! 6! described the use of fluoride ion

as a masking agent for Ca, Mg and A1 in the titration of Zn.

Sulfate ions can be used to mask Pb when Bi is to be

titratedJ7i.
 9

However, this type of masking is of less

importance because of its inherent limitations and limited

applications. The precipitation is often accompanied by

co-precipitation of the species to be determined and hence low

result is obtained. Moreover, the adsorption of the indicator

on the precipitate produces a trailing end point. Even when no

adsorption takes place, the presence of a precipitate makes it

harder to detect the color change.

1.6.2 Masking by Oxidation or Reduction

In this masking technique, the interfering metal

ion is either reduced or oxidised by a suitable masking agent

to a state in which it is non-interfering.

The metals existing in two different oxidation

states show entirely different reaction tendencies.

Consequently the oxidation or reduction of a species may be

conveniently employed in achieving the desired masking. But

care should be taken to see that excess of the oxidant or

reductant does not interfere with the principal reaction.

Some metals in their higher oxidation states

generally form more stable complexes with EDTA than in their

lower oxidation states. In the case of FeCIIID, masking can be

effected by reduction to FeCII} using hydroxylamine or ascorbic

acid*8! . Nevertheless, masking by oxidation is often a

possibility, provided the metal to be masked is transformed by

oxidation into a stable oxyanion. This technique can be

applied to avoid the interference of Cr, Mo, W and V in their

 10

lower oxidation states which form stable complexes with EDTA.

The above metal ions can be masked by their oxidation into

2"* 2— 2* 3—
stable oxyanions such as CrO^ » MoO^ , WO^ and VO^

r espectively.

However, masking by oxidation or reduction has

limited applications since only a few of the common elements

can exist in different oxidation states in aqueous solution.

Moreover, some of the possible oxidation states are so unstable

that they can not be readily obtained and maintained. One such

example is CoCHID which is highly unstable in aqueous phase

unless suitably complexed.

1.6.3 Masking by Soluble Complex Formation

In this technique, the masking agent selectively

forms a stable soluble complex with the interfering metal ion

and thereby renders it inactive.

The overwhelming majority of masking methods

involve the formation of stable and soluble complexes. The

masking agent must therefore be a highly selective complexing

agent. It should not react with the metal to be titrated but

should form a stable complex with the interfering metal, so

that the ratio of the effective stability constants is

increased as much as possible by its presence.

The most valuable masking agents are those that

form very stable complexes with interfering metals. However,

there are cases where even weak complexing agents sometimes can
 11

produce good results, as in the case of masking bismuth by-

large amount of chloride in the tiration of FeCIIID !9!.

Masking by complexation has long been employed in

inorganic analysis using reagents such as cyanide, iodide,

citrate and tartarate ions. Flaschka and HuditzSlO! used

cyanide ions for masking Cu, Cd, Zn, Ni , Co and Hg in the

titration of Pb. Iodide is used in low concentrations for

masking HgCIIDSllS. In iron alloys, Zn has been titrated with

EDTA at pH 8 in the presence of citrate ion to mask iron! 12. .

Tartarate has been used as an auxiliary complexing agent to

hold magnesium in a solution when calcium is titrated at

pH 12 ! 13!.

Sulfosalicylic acid is a masking agent for A1 in

the t i tati on of FeC HID ! 14!. Tri ethanol ami ne is used for

masking A1, Fe, Mn in the titration of Hi and Ca!15!.

Compounds that co-ordinate through sulfur are selective masking

agents for those metals that form sulfides. Thiourea has often

been used to mask copper! 16!. 3-mercaptopropionic acid can be

used to mask Pb!17! and thiosemicarbazide to mask Hg!18! in the

titration of Zn or Cd.

1.6.4 Mixed Masking

In mixed masking more than one of the above types

of masking reactions take place simultaneously.

Depending on the situation, the above three types

of masking reactions may be applied either simultaneously or

 12

concurrently in order to achieve the desired results. In the

determination of bismuth!19*, mercuryCIID can be masked by

reduction to the metal precipitate using ascorbic acid or

formic acid. Masking may sometimes involve both reduction and

complexation. In the titration of Zn!20, or Ni!21i, CuCII5 can

be masked with thiosulfate, where by reduction to a

thiosulfato-complex of CuCID takes place. In the titration of

cadmium and zinc*22!, FeCIIID is masked by adding ascorbic acid

and cyanide since hexacyano-ferrateCII} ion interferes less

than hexacyano-ferrateCIII} ion.

1.6.5 Kinetic Masking

In certain cases, a principal masking agent

reacts at a significantly different rates with different

species of interest. These kinetic differences sometimes can

be used in securing the desired selectivity. This kind of

approach used in securing selectivity is termed as "kinetic

masking".

The reaction of CrCIIID with EDTA is very slow at

room temperature and requires boiling to attain complete

complexation. This kind of kinetic behaviour of CrCIIID is

used in the titration of a number of metal ions5 23* in cold

solution with EDTA without interference from CrCIIID.

Kinetic masking may sometimes be secured by

lowering the temperature. Nickel is displaced only slowly from

its EDTA complex by BiCIIID in ice-cold solution. Whereas

 13

other cations like CdCII3, CoCIID, CuCIID, PbCIID and ZnCIID

are replaced rapidly. This kinetic masking is used in the

determination of NiCIID in a mixture of above metal ions!34* by

complex!ng all metal ions with EDTA and titrating an ice-cold

solution with BiCIII}.

1.6.6 Indirect Masking

Masking agents. especially those operating

through the formation of soluble complexes may be added after

the metal ions mixture has been reacted with the principal

masking agent. This approach is called "indirect masking".

This technique is particularly useful when the ion Cor ionsD to

be determined is present in a substantially smaller amount than

the interfering ions.

Raoot et al! 25! used thioglycolic acid as a

selective indirect masking agent for CuCIID in presence of

other metal ions. Aluminium can be determined in the presence

of certain other metal ions by using fluoride ion as indirect

masking agent*S6'. UenoSll! proposed potassium iodide as a

selective indirect masking agent for HgC11D.

The indirect masking some times allows the

determination of several species with a single aliquot of the

sample. Sajo!27J has described determination df Pb and Hg. In

a mixture, the sum of Pb and Hg is first measured by back-

titrating excess EDTA with zinc, then by adding NaCl the

mercury is displaced from its EDTA complex, and the amount of

EDTA released is determined by titrating with zinc.
 14

1.7 DEMASKING TECHNIQUE

Demasking is a reverse of masking reaction in

which a masked species regains its ability to enter into normal

reactions. Demasking is thus used to offset the effect of

masking. Demasking is especially important for successive

determinations. In general, demasking is less easily

accomplished than masking and often elaborate measures are

required to achieve complete demasking. The different types of

demasking are discussed in the following sections.

1.7.1 Demasking through Displacement Reactions

In this method, the added demasking agent

selectively displaces the metal ion of interest from its

complex.

Many methods have been developed on the basis of

the demasking of NiCIII> from NiCCN52~. In ammoniacal solution,

nickel is demasked by silver ion,

NiCChD2" + 2Ag+ —> 2AgC CND ~ + Ni2*

The displaced nickel ions can be determined complexometrically

by EDTA. This forms the basis for the complexometric

determination of silver !28!. Similarly palladium and gold can

be determined based on their demasking reaction ter. displace

nickel from NiCCND2_S29!.
4

Snail amounts of silver ion can be determined by

its ability to demask CuCIID from copper diethyldithiocarbamate

dissolved in chloroform or carbon tetrachloride.

 15

CuCDDO + 2Ag+ ----> 2Ag DDC + Cu*2

2

The liberated CuCIID is then titrated with EDTA in a weakly

acid solution! 30! .

BismuthCIII} can be titrated with EDTA in the

presence of HgCII} if the latter is masked by adding a slight

2—
excess of potassium thiocyanate to form soluble [HgCSCND^J

After the titration at pH 1, the HgCIID is demasked by adding a

slight excess of silver nitrate and the HgCIID is titrated with

EDTA!31S.

1.7.2 Conversion of Masking Agent to Non-reacting Species

This is a method in which the demasking agent

reacts with the masking agent, converts it into a nonreacting

species and makes the masked metal ion free to show its

characteristic reactions.

The demasking of Cd and Zn from their cyanide

complexes by formaldehyde have been extensively used for their

determinations. The addition of formaldehyde! 32! converts

masking agent cyanide into nitrile of glycolic acid and demasks

Cd.

CdC CND 2~ + 4H+ + 4CH O —> Cd+2 + 4HO. CH . CN

4 2 2

Chloral hydrate! 33! can also be used in place of CH^O. The

metals Co, Ni, Cu and Hg remain completely masked by cyanide

during this process.

 16

A typical application of this demasking technique

is proposed for the analysis of a Mg-Zn-Cu mixture!34!.

Addition of known excess of standard EDTA followed by back

titration with standard Mg, gives the total metal content.

Then KCN is added to mask Zn and Cu, and again titrated. The

amount of Mg present is obtained by difference. After the end

point formaldehyde or chloral hydrate is added to demask Zn

from ZnCCKD*- complex and liberated Zn is then titrated. The

amount of copper present is found by difference.

Kinnunen and Merikanto,35! determined Zn in brass

by EDTA titration after masking Zn and Cu as their cyanides and

then selectively demasking Zn by formaldehyde.

1.7.3 Demasking by pH Adjustment

The stability of a metal complex is normally pH

dependant. Therefore either by lowering or increasing pH, the

desired demasking can be achieved.

Barium can be masked at pH 7 by EDTA against

precipitation as its sulfate, but at pH 5 it is no longer

masked. In a complexometric method for Zn, other metals are

2-
titrated while Zn is masked with cyanide ion. Then ZnCCNZ)^ is

demasked with hydrochloric acid. The freed Zn is then titrated

with EDTA using acetate buffer and xylenol orange as

indicator•36 ! .
 17

Often the desired demasking can also be achieved

by increasing pH. In the selective determination of A1 and Ga

by EDTA-titration, all metal ions are titrated with EDTA at

pH 3.7, but when the pH is raised above 10.5, A1 and Ga are

demasked and masked as aluminates and galliumates. The

released EDTA is titrated with a suitable metal ion*375. In a

pyridine buffer, ammonium borofluoride masks Ca and Mg whereas

Mn can be titrated directly with EDTA using methyl thymol blue

indicator. By adding concentrated ammonia Ca and Mg can be

demasked and titrated with EDTA.

1.7.4 Demasking by Change in Oxidation State of the Metal Ion

The stability of a metal complex is greatly

influenced by the oxidation state of the metal. It is often

found that a masking agent can form a very strong complex with

a metal at one oxidation state but not at other oxidation

state. This property of the metal, sometimes, can be used in

achieving desired demasking.

When a metal ion can exist in more than one

valence state, there will be differences in the stability of

the corresponding complexes with a given ligand. A change in

oxidation state of a metal ion may so decrease the stability of

a complex that the metal ion may no longer remain masked.

Thiosulfate ion forms a very stable complex with CuCI> in

slightly acid soluton but a weak one with CuCIID in slightly

alkaline solution. This property can be used in demasking

copper from CuC13>-thiosulfate complex. If the solution is made
 18

alkaline, CuC I -thiosulfate is readily oxidised to

CuCI 13-thiosulfate, which is a weak complex. The demask ed

copper can be titrated with EDTA.

1.7.5 Deamsking by Distruction of Masking Agent

In some cases, demasking can be achieved through

destruction of the masking agent by heat, chemical reaction, or

both.

Thiocyanate ion used for masking can be abolished

by heating with alkaline hydrogen peroxide. Ami nocarboxyl ic

acids such as EDTA are distroyed in acid solutions by

permanganate or other strong oxidising agents.

However, distruction of masking agent is not a

significant demasking technique in complexometric titrations

because of its limited applications.

1.8 CHOICE OF MASKING AGENTS

Most of the common masking agents used in

Analytical Chemistry are not very selective in their action

since they mask related cations rather than individual species.

The main factors that determine the suitability of masking

agents are :

Ci} the kind of donor atoms through which they bond metal

ions.

Cii3 the pK value of the ionisable groups.

 19

Apart from these, stereochemical factors can also

play a significant role in their choice. Whether a given

process will indeed serve for masking, depends on factors such

as the nature of the species to be masked, principal reagent,

the type of reaction involved, the concentration and the

solution conditions.

Some of the desired characteristics of a masking

agent used in complexometry are :

CiD the complex formed by the reaction of masking agent with

the metal ion should have high stability,

CiiD the masking agent should form a soluble and almost

colorless metal complex, so that the accurate detection

of end point becomes easy,

Ciii> the masking agent should be readily soluble in the

medium,

Civ3 the release of EDTA should occur instantaneously and

quantitatively at room temperature,

CvD the masking agent should not react with the titrant metal

ion.

1.9 INDUSTRIAL APPLICATIONS OF MASKING AGENTS

The applications of masking agents in industry

are numerous and varied. They include a wide range of

industrial and manufacturing processes. The important

industrial applicatons of masking agents are summarised in

Table 1.1.
 20

TABLE 1.1

INDUSTRIAL APPLICATIONS OF MASKING AGENTS

SI. Metal i ons Masking

No. Industry to be masked agent Effect of masking

1. Laundries Ca, Mg and EDTA and Prevents the

other heavy Nitrilo- wastage of cleansing
metal ions. acetic agent and staining
Fe and Mn acid of fabrics

2. Texti1es Fe and Mn. EDTA Avoids variation of

Ca and Mg and colors and shades,
ions in related and the precipita­
dye bath compoum tion of the basic
dyes

3. Pulp and Fe, Mn,etc. EDTA and Prevents the dis-

Paper calgon coloration of
unbleached pulp
and paper

4. Preservation FeCIIID, EDTA Controls rancidity

of fish VCII!> and in blended fish
CuCII3 muscle, and thereby
increases the
storage life of
the fish

5. Food stuff Heavy EDTA and Prevents the ranci-

and metal ions r el a ted dity, turbidity,
Bever ages compounds disagreeable taste
and odour in oils
and fats. Prevents
discoloration in
canned sea foods.
Prevents turbidities
in wines and beers

5. Steam Ca, Mg, Fe, EDTA Prevents scale

boilers Mn formation
 21

1.10 ORGANIC REAGENTS IN CHEMICAL ANALYSIS

Organic reagents have been used for a long time

in inorganic analytical work. They are selective and sensitive

in their reactions with metal ions. Much of the early

empherical work was confined to the search of specific and

selective reagents for particular constituents. Recently, the

study of organic reagents is based on a quantitative study of

the various equilibria involved and the structural factors that

led to selectivity of the organic reagents. Thus the approach

is more fundamental in nature. By careful control of pH and

reagent concentration followed by the use of suitable masking

agents, a fair degree of selectivity can be achieved.

Majority of organic reagents used in quantitative

analytical work generally form stable metal chelates. Many

quantitative studies have confirmed that metal chelates are

more stable than those of related unidentate ligands. Further,

five or six membered chelates are by far the most common and

are in general most stable*38!.

Organic ligands showing dual character, viz., of

possessing both acidic and basic functional groups are capable

of forming a neutral metal chelate. The acidic group usually

contains a replaceable proton and basic group contains a lone

pair of electrons which takes part in co-ordination and

chelation.
 22

Another important condition for chelation is that

the functional groups must be so positioned as to facilitate

the formation of a strainless ring. Chelates involving five or

six memebred rings are found to be the most stable.

1.11 PRESENT WORK

In the present work, an attempt has been made to

investigate the masking and demasking behaviour of some sulfur

and/or nitrogen containing organic reagents such as 3-mercapto-

propane-1,2-diol, thioglycolic acid, mercaptoethane.

2-mercaptopropionyl glycine, 2-mercaptoethylamine in complexo-

metric determination of thallium, mercury and palladium. The

above reagents are found to be quite effective and selective

demasking agents, forming soluble and stable complexes with

demasked metal ions. After optimising the experimental

conditions, suitable methods have been proposed for the

determination of above metal ions. Moreover, the proposed

methods find extensive applications in the analysis of metal

complexes and alloys.

A brief account of these methods is given in

Table 1.2.
 23

TABLE - 1.2

ORGANIC REAGENTS FOR COMPLEXOMETRIC DETERMINATION OF

THALLIUM, MERCURY AND PALLADIUM

Si.No. Hetal Hacking agent pH Recovery, I Application Hasking technique

Thai 1iua Thioglycoiic acid 5-6 99.71-100.17 Analysis of Hixed tasking

(Hexaiine) coaplexes, and (reduction followed
synthetic by coaplexation)
3-Hercaptopropane-l,2-diol 5-6 99.72-100.19 ■ixtures or
(Hexaiine) alloys

Hercaptoethane 5-6 99.72-100.19

(Hexaiine)

Hercury 3-Hercaptopropane-l,2-dio1 5-6 99.59-100.20 Analysis of indirect

(Hexaiine) complexes, ■asking
and synthetic
Thipglycolic acid 5-6 99.79-100.21 ■ixtures or
(Hexaiine) alloys

2-Hercaptopropionylglycine 5-6 99.74-100.26

(Hexaiine)

Pal ladim 3-Hercaptopropane-l,2-diol 5-5.5 99.75-100.29 Analysis of Indirect

(Acetate complexes, ■asking
buffer) and
synthetic
2-Hercaptopropiony1glycine 5-5.5 99.74-100.36 ■ixtures or
(Acetate alloys
buffer)

2-Hercaptoethylaiine 5-5.5 99.71-100.38

(Acetate
buffer)
 24

REFERENCE

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