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STUDIES ON SOME ORGANIC COMPOUNDS

AS ANALYTICAL REAGENTS IN
COMPLEXOMETRIC TITRATIONS
AND SPECTROPHOTOMETRY

A THESIS SUBMITTED TO
MANGALORE UNIVERSITY
FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY
IN
CHEMISTRY

By
A. NITYANANDA SHETTY

DEPARTMENT OF CHEMISTRY
KARNATAKA REGIONAL ENGINEERING COLLEGE, SURATHKAL
P. O. SRINIVASNAGAR - 574 157
DECEMBER 1991
DEDICATED

TO

MY PARENTS
 CONTENTS

STATEMENT (1)

CERTIFICATE (ii)

ACKNOWLEDGEMENTS (i i i)

ABSTRACT (v)

PART ONE

ORGANIC COMPOUNDS AS ANALYTICAL REAGENTS IN

COMPLEXOMETRIC TITRATIONS
I INTRODUCTION TO MASKING AND DEMASKING TECHNIQUES 1

II COMPLEXOMETRIC DETERMINATION OF THALLIUMCIIID 28

4-Amino-5-mer capto-3-pr opyl-1,2,4-triazole,

hydrazine sulphate and 2-mercaptoethanol

as selective masking agents.

III COMPLEXOMETRIC DETERMINATION OF PALLADI UMC 11D 61

Hydroxyl amine hydrochloride, N-C2-pyridylD

thiourea and 3-acetyl-2-thiohydantoin

as selective masking agents.

IV COMPLEXOMETRIC DETERMINATIOIN OF MERCURYCII!) 95

Hydroxyl ami ne hydrochloride, 3-acetyl -

-2-thiohydantoin and 2-mercaptoethanol

as selective masking agents.

 PART TWO

ORGANIC COMPOUNDS AS ANALYTICAL REAGENTS

IN SPECTROPHOTOMETRY

V INTRODUCTION TO SPECTROPHOTOMETRY 129/~

VI 4-C DIMETHYLAMINOD BENZALDEHYDE THIOSEMICARBAZONE 155

AS A SPECTROPHOTOMETRIC REAGENT FOR PALLADIUMCIID

Estimation of Palladium in Complexes and

Mixture of Ions.

VII 4-CDI METHYLAMI NOD BENZALDEHYDE THI OSEMI CARBAZONE 187

AS AN EXTRACTIVE SPECTROPHOTOMETRIC REAGENT

FOR COPPERCII3

Analysis of Copper Alloys and Mixture of Ions 220

VIII 4-C DIMETHYLAMINOD BENZALDEHYDE THIOSEMICARBAZONE

AS AN EXTRACTIVE SPECTROPHOTOMETRIC REAGENT FOR

PLATT NUMCIVD

Estimation of Platinum in Mixture of Ions.

VITAE (xiii)

LIST OF PUBLICATIONS (xiv)

: -o-:
 (i)

STATEMENT

I hereby declare that the matter embodied in the

Thesis is the result of investigation Carried out by me in the

Department of Chemistry, Karnataka Regional Engineering

College, Surathkal, Srinivasnagar, under the supervision of

Prof.R.V.Gadag, Head, Department of Chemistry, Karnataka

Regional Engineering College, Surathkal.

In keeping with the general practice of reporting

scientific observations, due acknowledgement has been made

wherever the work described is based on the findings of other

investigators. However, errors and oversights, if any, are

unintentional and hence regretted.

Place : Srinivasnagar
Date : /9 -12-1991 (A. Nityananda Shetty)
 (ii)

CERTIFICATE

I hereby certify that the work presented in the Thesis

entitled, 'STUDIES ON SOME ORGANIC COMPOUNDS AS ANALYTICAL

REAGENTS IN COMPLEXOMETRIC TITRATIONS AND SPECTROPHOTOMETRY"

embodies the results of bonafide research work carried out by

Sri A. Nityananda Shetty, Lecturer, Department of Chemistry,

Karnataka Regional Engineering College, Surathkai, for the

degree of Doctor of Philosophy, under my guidance and direct

supervision. I further certify that this Thesis or part

thereof has not previously formed the basis for the award of

any degree or diploma.

Place: Sr inivasnagar
Date : -12-1991 Professor and Head,
Department of Chemistry,
Karnataka Regional Engineering College,
Surathkai, P.0. Srinivasnagar - 574 157.
 (Hi)

ACKNOWLEDGEMENT

I derive immense pleasure in placing on record my deep

sense of appreciation, gratitude and indebtedness to my Thesis

Supervisor, Prof. R.V.Gadag for suggesting the problem,

extending the facilities and providing valuable guidance for

the successful completion of my research work. His constant

encouragement, help and guidance during the course of the

investigation are invaluable.

I am highly grateful to Prof. M. R. Ga jendragad, Vice-

Chancellor, Kuvempu University, Shimoga, who has been a

constant source of help and inspiration.

1 am highly indebted to Prof. B.S. Basavara.jaiah,

Prof. T. Ramchandran, former Principals and Prof. N. R. Shelly,

present Principal of our College for providing me the

faci1ities.

1 am grateful to Prof. S.B.Akki, former Head of

Chemistry Department for his help and encouragement. 1

gratefully acknowledge the help and encouragement received from

Dr G.H. Kulk arid, Assistant Professor of Chemistry, during the

course of my work. 1 am thankful to my colleagues, Sri M.

Paridurangappa, Dr T. V. Venkatesha, Dr A. V. Adhikari and

Dr Shailaja Kumari for their cooperation. I express my sincere

thanks to our laboratory staff, Sri A. Bhavanishankar and

 (iv)

Sri V. Ganesh Rao for their help and assistance during the

course of my work.

1 have no words to express my sincere thanks to

Prof. B. Thimme Gowda, Dr B. S. Holla and Dr A. M. A. Khader,

Chemistry Department, Mangalore University, who have been

constant sources of inspiration. 1 am grateful to

Prof. G.Ranganna, former Head of Applied Mechanics Department,

Prof. H. V. Sudhak er Nayak, Metallurgical Engineering Department

and Prof. II. Hari das Bhat, former Head of Physics Department, for

their help at different stages of my work.

1 wish to express my sincere thanks to my friends,

Dr. G. Chandrakanth, Dr J. Ishwara Bhat, Sri R. Raghavendra Bhat,

Sri A. Jagannatha Nayak and Sri Subba Rao for their help and

moral support during my work.

1 am grateful to Sri Dinesh Hosadurga N. , who took

special interest and pains in doing a clean job of typing my

Thesis. 1 am also thankful to Sri Shreshta ICumar for the neat

drawings.

In conclusion, l thank all those who helped me

directly and indirectly in the completion of my work and

Thesis,

Place : Srinivasnagar

Date : ^-12-1991 A. Nityananda Shetty

 (v)

ABSTRACT

Recent years have witnessed a tremendous upsurge of

interest in the application of organic compounds as complexing

agents as well as analytical reagents. Considerable progress has

been made in the synthesis of metal complexes with sulphur,

nitrogen and oxygen donor ligands, in understanding the nature of

donor-acceptor relationship, stereochemistry of the complexes and

applications of the metal complexes in diverse fields such as

medicine, industries, etc., and analytical applications thereof.

Newly emerging fields like pollution, forensic science,

toxicology, food adulteration, hazards of chemical industries and

scores of others demand development of more and more simple,

rapid and accurate methods, tools and techniques of chemical

analysis.

Of late, the classical methods, gravimetry and

titrimetry have faced with severe competetion by the latest

sensitive and rapid ins trumenta1 techniques of analysis.

Titrimetry, however, has not been superseded by these techniques.

Titrimetric methods represent a lively and still growing area of

 (Vi)

analytical chemistry. The popularity of titrimetry is due to its

versatility, coupled with simplicity and speed. The technique

was given tremendous stimulus following the introduction of a new

titrant EDTA and metal 1ochromic indicators.

Among titrimetric methods, complexometric titrations

involving EDTA and related complexing agents are simple, rapid

and dependable. EDTA is a versatile reagent and forms highly

soluble and stable metal complexes with many divalent and

trivalent metal ions. Because of its high reactivity, EDTA is

not a selective reagent. There are some metal ions which can not

be estimated by direct EDTA titration methods particularly in

presence of associated diverse metal ions.

A great degree of selectivity in complexometric

titrations can be achieved by employing masking and demasking

techniques. The technique of masking provides a convenient means

to remove or temporarily suppress the effect of unwanted

constituents of a mixture of ions without resorting to elaborate

separation. This can be achieved by stable complex formation,

changing the oxidation state of the metal, kinetic masking or by

other types of mechanisms. A slight modification in the

procedure enables the estimation of a specific metal ion in the

presence of a large number of associated metal ions. The

procedure adopted is that all the metal ions present are first
 (vii)

complexed with EDTA and then the masking agent is added to

displace EDTA quantitatively and selectively from the desired

metal-EDTA complex. The released EDTA is then back titrated with

standard metal ion solution.

The present investigation aims at investigating the

masking behaviour of some sulphur and/or nitrogen containing

ligands in the complexometric estimation of thallium, palladium

and mercury. The great affinity of these metal ions for sulphur

and nitrogen donor atoms of the ligands, results in the formation

of stable complexes and enables precise analytical determination

of the metal ions in low concentrations, even in the presence of

several associated ions.

In the past forty years an extensive array of

instrumental techniques are reported which are extremely

sensitive and rapid, often with digital read out to a high degree

of accuracy. Spectrophotometry is one such technique which

enjoys a great deal of interest and provides an excellent

analytical area for research. Certain ligands form coloured

complexes with metal ions, showing strong absorbance in the uv

and/or visible region. The absorbance data can be used for the

estimation of metal ions in the suitable concentration ranges, in

accordance with Beer-Lambert*s law. Proper selectivity can be

achieved at by proper pH control, using masking agents, etc.

 (viii)

Spectrophotometric methods provide an excellent technique for the

estimation of metal ions in ppm levels.

The present work also aims at investigating the

application of 4-(dimethy1 ami no)benza1dehyde thiosemicarbazone as

spectrophotometric reagent for the estimation of palladium,

platinum and copper.

The work presented in the thesis is broadly divided

into two parts. The first part deals with the analytical

application of some of the organic reagents as selective masking

agents in the comp 1exometric determination of thallium, palladium

and mercury. The second part deals with the application of

4-(d imethy1 ami no)benza1dehyde thiosemicarbazone as a

spectrophotometric reagent in the determination of palladium,

platinum and copper.

Chapter 1 opens with an introduction to the first part

of the thesis, devoted to the analytical application of organic

ligands as selective masking agents in complexometric titrations.

It describes the techniques and mechanisms involved in masking

and demasking. The merits of organic compounds as analytical

reagents and their suitability for the determination of specific

metals are also highlighted.

Chapter II describes the complexometric determination

of tha11iurn( I 1 1 ) using 4-amino-5-mercapto-3-propy1 - 1,2,4

 (ix)

-triazole, hydrazine sulphate and 2-mercaptoethano 1 as selective

masking agents. The optimum conditions of the method, the effect

of diverse metal ions and anions on the determination of

thal1iumlI I I) and the mechanism involved are presented in this

chapter. The application of the proposed method for the

estimation of thallium in complexes and mixture of ions is also

included.

Chapter III describes the complexometric determination

of pa11 adiurn( 1 1 ) using hydroxy 1 amine hydrochloride,

N-(2-pyridy1)thiourea and 3-acety1-2-thiohydantoin as masking

agents. The optimum conditions of the method, the effect of

diverse metal ions on the determination of Pd ( 1 I) , the utility

of the method in the analysis of palladium present in complexes

and mixture of ions are also discussed in this chapter.

Chapter IV describes the analytical application of

hydroxy 1 amine hydrochloride, 3-acety1-2-thiohydanto i n and

2-mercaptoethano1 as selective masking agents in the

comp1exometric determination of mercury (II). The application of

the method in the estimation of Hg(ll) in complexes and in

mixture of ions are described.

The salient features of the methods proposed are

summarised below :

Kii.
 (x)

Masking Optimum Interfering

Metal agent conditions ions

1. T1(I I I) a.4-Amino-5- pH 5-6 Hg( I I), Pdi 1 i i

mercapto-3- (Hexamine) Bi(III),Cr(!il>
propy1 -1,2,4- and Sn(IV)
triazole

b. Hydrazine pH 5-6 Pd(II), Mni ! i )

su1phate ( Hexamine) and Sn(IV)

c.2-Mercapto pH 5-6 Hg ( I I ) , CuM '

ethanol (Hexamine) Pd( I I ) ,Cr( I 1 ! i
and Sn(IV)

a. Hydroxy 1 amine pH 5-6 Hg(II), Cd(!i)

hyd roch1 oride (Acetic acid- T1 ( I I I ) and
sodium acetate) Cr(III)

b. N-(2-pyridy1) pH 5-6 Hg(II), TIMM

thiourea (Acetic acid- and Cr(I1!)
sodium acetate)

c. 3-Ace ty1-2- pH 5-6 Hg(1I) and

thiohydantoin (Acetic acid- Cr ( ! 1 i i
sodium acetate)

a. Hydroxylamine pH 5-6 Pd(II), Cdiii)

hyd roch1 oride (Hexamine) T1(III) and
Cr( I I I )

b) 3-Acety1-2-thio pH 5-6 Pd(II) and

hydantoin (Hexamine) Cr(III)

c. 2-Mercapto pH 5-6 Pd(11), cuii;

ethano1 (Hexamine) Cr ( I I I ) , Tlii;
and Sn(IV)
 (xi)

Chapter V contains a brief introduction to the

spectrophotometric determination of metal ions. The chapter

highlights the technique of spectrophotometry, the

characteristics of the spectrophotometr ic reagents, the factors

governing the determinations and other relevant factors.

Chapter VI describes the spectrophotometric determina

tion of pal1 adiurn( 1 1 ) using 4-(dime thy 1 ami no)benza1dehyde

thiosemicarbazone. The optimum conditions for the determination,

the effect of diverse metal ions and anions, and the application

of the method in the analysis of palladium complexes and mixture

of ions, are also included in this chapter.

Chapter VI1 describes the spectrophotometric

determination of copperlll) using 4-(dimethy I ami no)benza1dehyde

thiosemicarbazone. The chapter discusses the optimum conditions

for the determination, the effect of diverse metal ions and

anions and the application of the method in the analysis of

copper based alloys and in mixtures of ions.

The last chapter includes the spectrophotometric

determination of platinum(lV) using 4~(dimethy1 ami no)benza! -

dehyde thiosemicarbazone. The chapter discusses the optimum

conditions for the estimation, the effect of diverse metal ions

and anions, and the application of the method in the analysis of

platinum in mixtures.
 (xii)

The salient features of the methods proposed are

summarised below :

Metal Range Molar Optimum Medium

max
ion ( nm) ( ppm) absor- pH
ptivity
< 1. mo 1 1cm 1)

Pd( I I) 405 0.5-1.75 4.59x10* 2.2-3.6 Aqueous

(HC1 + a 1 cohoi-
Potassiura acetone
ph tha1 ate)

Cu(II) 420 1.2-3. 6 1.72x10* *+.4-5.4 Ch1orof or m

(Acetic (Extract ion
ac id-Sodium
acetate)

P t < IV) 405 2.6-18.0 1.3x10* 4.4-5,6 Ch1orof orm

(Acet ic (Ex t rac tion
acid-Sodium
acetate >

: - o- :