4.1 INTRODUCTION - Shodhganga : a reservoir of Indian...

Chapter 4– Nickel(II)

Analytical Chemistry Laboratory, Shivaji University, Kolhapur (MS) India.

82

4.1 INTRODUCTION

Nickel was identified as a separate element by the Swedish chemist Axel

Cronsedt is 1751, but for thousands of years it had been incorporated in alloys

used for making swords, ornaments, cooking utensils and coins. Meteoritic

iron-nickel was raw material for the swords of many an ancient warrior [1].

Nickel is present in certain rocks found in many parts of the world, e. g. in

peridotite, 0.20%, gabbro, 0.016%, diorite, 0.004%, and granite, 0.0002%, but

the content is too low to make mining and extraction worth-while. Nickel is

moderately abundant (99 ppm) and is produced in large quantities. It is used in

large quantities in wide varieties of alloys both ferrous and nonferrous. Mine

production of ore contained 8.5 X 105 tonnes of nickel in 1992 [2].

Nickel improves both the strength of steel and its resistance to chemical

attack. In 1991, 569000 tonnes of ferronickel were produced. Stainless steel

may contain 12-15% nickel and steel for cutlery contains 20% Cr and 10% Ni.

Very strong permanent magnets are made from ‘Alnico’ steel. Monel metal is

very resistant to corrosion and is used in apparatus to handle F2 and other

corrosive fluorides. It contains 68% Ni, 32% Cu and traces of Fe and Mn. The

Nimonic series of alloys (75% Ni with Cr, Co, Al and Ti) are used in gas

turbine and jet engines where they are subjected to high stresses and high

temperatures. Other such as Hastelloy C are used for their corrosion resistance.

Nichrome contains 60% Ni and 40% Cr and is used to make the wire which

gets red hot in electric rediators. Cupro-nickel (80% Cu and 20% Ni) is used to

make silver coins. The so called ‘nickel-silver’ contains roughly 60% Cu, 20%

Ni, and 20% Zn. This is used to make imitation silver articles and can be

electroplated on other metals to give EPNS (electroplated nickel-silver). The

name nickel-silver is confusing as it contains no silver. Often steel is

electroplated with Ni before electroplating with Cr. Some Ni is used in Ni/Fe

storage batteries, which have the advantage that they can be charged at very

fast rates without of very finely divided Ni (Raney Ni) are used for many

reduction processes. Examples include the manufacture of



83

hexamethylenediamine, the production of H2 from NH3, and the reduction of

antraquinone to anthraquinol in the production of H2O2.

Nickel is present in small amount in soils, plants and animal tissues. The

main source comes from the hydrogenation of oils, irons factories, from the

combustion of coal, diesel and residual oils, tobacco smoke, chemicals and

catalysts [3]. However, nickel is toxic and the primary route for nickel toxicity

is mainly due to its exposure through inhalation and contaminated food and

water. The soluble nickel complexes are more toxic than insoluble complexes.

Nickel in human body [4] causes dermatitis, pneumonia, lung and nose cancer.

The formation of toxic Ni(CO)4 causes giddiness, headache, nausea and

vomiting. Considering the toxic effects of nickel, it has become necessary to

determine the nickel; content in soil and industrial effluent samples.

The acidic dyes such as 2-(2-thiazolylazo)-5-(sulfomethylamino)benzoic

acid (TAMSMB) [5]. 2-(2-Thiazolylazo)- and 2-(2-benzothiazolylazo)-5-

dimethylaminobenzoic acid [6] benzoic acid type-2-[2-(6-methylbenzothia-

zolyl)azo]-5-(N-methyl-N-sulphomethyl)aminobenzoic acid (6-Me-BTAMSB),

2-[2-(6-methylbenzothiazolyl)azo]-5-(N-ethyl-N-sulphomethyl) aminobenzoic

acid (6-Me-BTAESB), and 2-[2-(6-methylbenzothiazolyl)azo]-5-(N-ethyl-N-

carboxymethyl)aminobenzoic acid (6-Me-BTAMCB) [7], 2-[2-(3,5-

dibromopyridyl)azo]-5-dimethylaminobenzoic acid (3,5-diBr-PAMB) [8], 4-(2-

benzo-thiazolylazo) salicylic acid (BTAS) [9], [o-carboxy phenylazo] moiety

of barbituric acid, thiobarbituric acid, thiouracil, citrazic acid, and disodium

chromotoropate [10] were used for complexation with nickel(II). These

spectrophotometric methods are highly sensitive but suffers from pH sensitive

range and large number of diverse ions interfered in determination of nickel(II).

A simple, sensitive and rapid spectrophotometric determination of nickel(II)

has been developed by using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

[11-13]. The methods are applied for determination of nickel(II) from real

samples [12] and development of an optical chemical sensor in Nafion [13].

2-[2-(4-Methylquinolyl)azo]-5-diethylnophenol [14] was used for extractive

spectrophotometric determination of nickel(II) in chloroform. A



84

spectrophotometric method for determination of nickel(II) in copper bronze

alloy with 2-(2-thiazolylazo)-p-cresol [15] is described. The interference of

foreign ions can be eliminated by masking with mixture of sodium tartarate and

Na-thiosulphate.

(2-Pyridylazo)-2-naphthol (PAN) [16] has been used with adsorbed

resin phase spectrophotometry, its sulphonated form [17] and in miceller media

[18] for determination of nickel(II). 1-(1,2,4-Triazolyl-3-azo)-2-naphthol [19]

in aqueous 40% ethanol at pH 5 to form a red 1:2 complex with nickel(II)

having an absorption peak 523 nm. By spectrophotometric determination of

nickel(II) using 1-(2-thiazolyl azo)-2-naphthol [20] chemometric method has

been reported. A spectrophotometric method for determination of trace amount

of nickel(II) with p-acetyl aresenazo [21] was described. The proposed method

was sensitive as consider to pH. A simple, rapid, sensitive procedure for

spectrophotometric determination of nickel(II) has been developed at pH 9.4 in

presence of emulsifier p-octyl polyethylene glycol phenyl ether [22]. A novel

azocalyx[4]arene [23] was prepared and used for spectrophotometric method

for determination of nickel(II), method is highly sensitive. Complex formation

of the new reagent 5-(6-methoxy-2-benzothiazole azo)-8-aminoquinolene [24]

for its sensitive spectrophotometric method for determination of nickel(II) was

described. Method requires 20 min waiting period for full colour development.

Determination of nickel(II) was carried out as diethyldithiocarbamate

complex in presence of aqueous solution of cationic surfactants of

hexadecyltrimethylammonium bromide, chloride and hydroxide [25] and

sodium dodecylsulfate [26] in presence of miceller system avoids the previous

step of solvent extraction. A partial least square molding based on singular

value decomposition was applied for spectrophotometric determination of

nickel(II) as its ammonium 2-amino-l-cyclohexene-l-dithiocarboate complexes

[27, 28].

Oxime and thiosemicarbazones are two important classes of reagents

widely employed for spectrophotometric determination of nickel(II). The

oxime-thiosemicarbazone may be considered as novel reagents because they



85

contain mixed functional groups (2 in 1) viz. oxime and thiosemicarbazones.

Survey of literature reveals that oximes such as 4-methyl 2,3-pentanedion

dioxime [29], 2-hydroxy-1-naphthaldoxime [30] and dimethylglyoxime

[31, 32] have been used for spectrophotometric determination of nickel(II).

However, Cu(II), Co(II), Pd(II), Fe(III) interfered [29, 30] and number of steps

are involved in determination procedure [32], while thiosemicarbazones such

as N-ethyl-3-carbazolecaroxyaldehyde-3-thiosemicarbazone [33], 1-phenyl-

1,2-propanedione-2-oxime thiosemicarbazone [34], 2,2’-dihydroxybenzo-

phenon thiosemicarzone [35], bis(4-phenyl-3-thiosemicarzone) [36] and

pyridoxal-4-phenyl-3-thiosemicarzone [37]. These methods have narrow pH

range [33, 34, 36], required higher reagent concentration; use of salting out

reagent [37]. The study of adduct formation of nickel(II)-di(6-chloro-2-

methylphenyl)carbazone [38] has been undertaken by spectrophotometric

method in a monophase chloroform. The results are discussed in the form of

steric factor of bases.

The coordination chemistry of hydrazones is an intensive area of study

and numerous transition metal complexes with their ligands have been

investigated. Hydrazone compounds obtained by reaction of aromatic and

heterocyclic hydrazones with mono and dialdehyde and ketones have reveals

very versatile behavior in metal coordination. Heterocyclic hydrazones are

highly sensitive and selective for the determination of nickel(II). The most

sensitive reagents have reported for nickel(II) are 2,2’-dipyridyl

ketone-2-pyridylhydrazone [39], 3-(picolydene)benzenesulphonic acid 2-

hydroxybenzoylhydrazone [40], 2-pyridinecarbaldehyde 3,5-dinitro-2-

pyridylhydrazone [41], isatin-3,2’-quinolylhydrazones [42], 2-pyridine

carboxaldehyde isonicotinyl hydrazone [43], 2-benzoylpyridine-2-

pyridylhydrazone [44] and picolinealdehyde salicyloylhydrazone [45].

Aqueous solution of non-ionic surfactants becomes turbid when they are

heated above the temperature known as cloud point. This solution is then

separated into two isotropic phases i.e. a surfactant rich phase and a bulk

aqueous phase. The hydrophilic solutes and metal ions, after the formation of



86

sparingly water soluble complex can be enriched into the surfactant-rich phase.

A small volume of surfactant-rich phase obtained with this methodology. The

micelles mediated extraction/preconcentration practically expressed in the form

of cloud point extraction has been applied under batch condition to the

spectrophotometric analysis of trace nickel ions in various samples after

complexation with some chelating agents. These reagents are 2-amino-

cyclopentene-1-dithio-carboxylic acid [46], with Triton X-114, 2-(5-bromo-2-

pyridylaxo)-5-diethylaminophenol [47], 1-(2-pyridylazo)-2-naphthol [48] with

Triton X-100, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol [49] tergitol

NPX surfactant, 1-(2-pyridylazo)-2-naphtol [50] with Tween-80 and α-benzyl

dioxime [51] with sodium dodecyl sulfate.

The flow analysis process was first proposed in 1957 by Skeggs [52]

who developed continue flow methodology based on multisegmentation of the

sample, the research area underwent its greatest development after the

introduction of the flow injection analysis process in 1975 [53]. The flow

injection systems are excellent tools for solution management allowing the easy

implementation of different steps are required for selectivity and sensitive

enhancement. Ion exchange, precipitation, filteration-desolution and addition of

chelating agents were exploited to improve the flow injection determination of

nickel(II) [54-58].

The solid phase spectrophotometry was paid great intention recently,

since, it was introduced in 1976. The reason is that, this technique can provide

various important advantages: The sensitivity is much higher than

corresponding spectrophotometry in solution, it does not require an expensive

instrumentation and the species interfering in spectrophotometry in solution

can be excluded from the resin in adequate conditions. The solid phase

spectrophotometry combines the use of solid support such as, 3M Empore

SDB-XC47 mm extraction membrane [59], styrene-divinyl benzene-type resin

Amberlite XAD-4 [60], polyurethane foam [61].

A method for spectrophotometric determination of divalent nickel based

on formation of its complex with 1,5-bis(di-2-pyridylmethylene)



87

thiocarbonohydrazide [62] was proposed. A first and second derivative was

also presented. The equilibrium between 3-(l-naphthyl)-2-mercaptopropenoic

acid [63] and nickel(II) in presence of hydrogen ions at 25 oC in aqueous 0.1 M

NaClO4 solution containing 1-2% ethanol have been studied

spectrophotometrically. Protonation constant for ligand and formation of

constant for complex were reported. The effects of surfactant on the extraction

and atomic absorption spectrophotometric determination of nickel(II) was

extracted into 10 mL of MIBK as ammonium pyrrolidine dithiocarbamate

chelate [64], EDTA interferes in this determination of nickel(II). The derivative

spectrophotometric determination of nickel(II) by dithizone [65] without

extraction has been reported, method requires 30 min equilibrium time at

higher alkalinity. A novel sensitive chromogenic reagent N,N-bis(3-

methylsalicylidene)-ortho-phenylenediamine [66] has been used in

spectrophotometric determination of nickel(II). Method has successfully been

applied to determination of trace amount of nickel(II) in some food samples.

The method was proposed for determination of nickel(II) by third derivative

spectrophotometrically based on the absorption spectra of its complex with

cyanide in ultraviolet range. The method has been applied for direct

determination of nickel(II) in iron alloys and in aluminum alloys without any

separation [67]. Derivative UV-visible spectrophotometric determination of

nickel(II) in alloys and biological samples after preconcentration with the ion-

pair of 2-nitroso-1-naphthol-4-sulfonic acid and tetradecyl-dimethylbenzyl-

ammonium chloride [68] on to microcrystalline naphthalene or by column

method has been investigated. A study of the adduct formation of nickel(II)-

di(2,4-dimethylphenyl)carbazonate [69] with heterocyclic nitrogen based, has

been undertaken for spectrophotometric determination of nickel(II). Partial

least square modeling as a powerful multivariate statistical tool applied to

spectrophotometric determination of nickel(II) in aqueous solution using

nitroso-R-salt [70] has been described. A method for spectrophotometric

determination of nickel(II) based on the formation of its complex with

pyrrolidine and CS2 was proposed [71]. A new method for spectrophotometric



88

determination of nickel-naphthalene in gasoline in a micro emulsion was

developed. PAN reacts with nickel(II) forming a red complex with an

absorption 568 nm. Interferences of Cu(II), Fe(III), Mn(II), Zn(II) can be

eliminated by adding mixed masking agents [72]. A partial least square applied

to the determination of divalent nickel base on its form of complex with zincon

[73] has been investigated. The effect of pH, sensitivity, and selectivity was

studied. At pH 8.5 nickel(II) treat with purpurin (1,2,4-trihydroxy

antharaquinone) [74] to form a 1:1 red complex, extracted into MIBK with an

absorption maxima at 525 nm. The extraction of nickel(II) with bis(4-

hydroxypent-2-ylidene)diaminoethane [75] from various acids and buffer

solutions has been studied and yellow green nickel chelate shows two maxima

at 373 and 563 nm. Nickel(II) was separated from iron and vanadium. A

spectrophotometric method for determination of nickel(II) using a new reagent

sodium ethylthioxanthate [76] has been described. Some ions are interfered in

this procedure. The spectrophotometric study of dipodal ligand N,N’-bis{2-[(2-

hydroxybenzylidine)amino]ethyl}malonamide [77] with nickel(II) was

proposed by spectrophotometric method. Extraction and spectrophotometric

determination of nickel(II) in steel and aluminum metal with 3-(2-pyridyl)-5,6-

diphenyl-1,2,4-triazine and ethyl tetrabromophenolphthalein [78] at pH 6.8 has

been reported at 610 nm. 8-Hydroxyquinoline [79] has been used as a

photometric reagent for spectrophotometric determination of nickel(II) after

extracting its complex in chloroform. The use of first derivative spectra allows

better resolution of samples and corrects for errors arising from incomplete

phase separation.

In the present investigation, 1-(2’,4’-Dinitro aminophenyl)-4, 4, 6-

trimethyl-1,4-dihydropyrimidine-2-thiol, [2’,4’-dinitro APTPT] has been

employed for the extraction and subsequent spectrophotometric determination

of nickel(II) in chloroform. The colour of extract complex was stable for > 48

h. The method is rapid and selective and sensitive for the amounts of nickel(II)

can be determined in the presence of foreign ions by the use of the 1-(2’,4’-

dinitro aminophenyl)-4, 4, 6-trimethyl-1,4-dihydro-pyrimidine-2-thiol. The



89

sensitivity of the method was increased by the use of masking agents. The

method is applicable for analysis of synthetic mixture of associated metal ions

and alloys.

Various methods are summarized in Table 4.1 for spectrophotometric

determination of nickel(II) with respect to reagent, absorption maximum, molar

extinction coefficient, Sandell’s sensitivity and special features.



90

Table 4.1. Summary of spectrophotometric methods for determination of

nickel(II)

Name of Reagent Aq.

Phase

Solvent λmax,

nm

Beer’s

range

µg

ε = lit

mol-1

cm-

1

s = µg

cm-2

Special Features Ref.

No.

1 2 3 4 5 6 7 8

2-(2-Thiazo-lylazo)-

and 2-(2-benzo

thiazolylazo)-5-

dimethylamino

benzoic acid

pH 8.5 Methanol 640 0.05-0.5 ε = 0.95

x 105 and

1.2 x 105

• Stoichiometry

1:2

• Cu(II), Cr(VI),

Co(II), Fe(III)

interfered

seriously

6

i) 2-[2-(6-Methyl

benzothiazolyl)azo]-

5-(N-methyl-N-

sulphomethyl)amino-

benzoic acid

ii) 2-[2-(6-Methyl


5-(N-ethyl-N-

sulphomethyl)

aminobenzoic acid

iii) 2-[2-(6-Methyl


5-(N-ethyl-N-

carboxymethyl)amino

benzoic acid

pH 5.6 Methanol 642

620

625

0-7

0-6

0-12

ε = 8.81

x 104

s = 0.6 x

10-3

ε = 8.82

x 104

s = 0.7 x

10-3

ε = 1.03

x 105

s = 0.5 x

10-3

• Stoichiometry

1:2

• Three reagents

are sensitive

• Most foreign

ions do not

interfere

• Good selectivity

• Absorbance was

measured after 5

min

7

2-[2-(3,5-Dibromo-

pyridyl)azo]-5-

dimethylamino

benzoic acid

pH 6.0 Chloroform 618 0.04-0.4 ε = 1.50

x 105

• Stoichiometry

1:2

• Cu(II), Co(II),

Fe(III), Pd(II),

V(III) seriously

interfered

• Absorbance was

stable for 24 h

8

4-(2-Benzo-

thiazolylazo)

salicylic acid

pH 7.0 Ethanol 525 0.59-

7.08

ε = 0.6 x

104

s = 2.824

x 10-9

• Stoichiometry

1:1

• Fe(III), F-,

HPO42-

interfered

seriously

9



91

1 2 3 4 5 6 7 8

i) [o-Carboxy-

phenylazo] barbituric

acid

ii) [o-Carboxy

phenylazo]

thiobarbituric acid

iii) [o-Carboxy

phenylazo] thiouracil

iv) [o-Carboxy

phenylazo] citrazic

acid

v) [o-Carboxy

phenylazo] disodium

chromotoropate

pH 6.3

pH 6.1

pH 7.4

pH

13.2

pH 8.4

Water 473,

504.7

267.4

276.1

424,

590

398.3

466.6

310,

472,

580

- - • Stoichiometry

1:1

• Stoichiometry

1:2

• Stoichiometry

1:3

• Stoichiometry

2:1

• Stoichiometry

3:2

10

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH 5.5

Water-

ethanol

520

and

560

0-15 ε = 1.26

x 105

• Stoichiometry

1:2

• Absorbance was

measured after

30 min

• Absorbance was

stable for 24 h

11

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH 7.0

Methanol 555 - ε = 8.2 x

105

• Stoichiometry

1:2

• Absorbance was

stable for 24 h

12

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH 6.5

Water 520,

558

0.1-16 - • Absorbance

measured at

both maxima

• Successfully

applied to

Vegetable oil

and Chocolate

13

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH 2.5 Chloroform 547 0.4-72 ε = 1.0 x

105

• Equilibrium

time 20 min

• Absorbance

measured at 457

and 526 nm

14

2-(2-Thiazolylazo)-p-

cresol

pH 5.7 Ethanol 580 20-70 ε = 2.6 x

104

• Equilibrium

time 10 min

• Absorbance was

stable for 24 h

• Interfered ions

are removed by

using masking

agent

15



92

1 2 3 4 5 6 7 8

1-(2-Pyridylazo)-2-

naphthol

pH 8.0 Ethanol 563 - - • β-Cyclodextrin

polymer used

for adsorption

• Stoichiometry

1:2

• Equilibrium

time 40 min

16

1-(2- Pyridylazo)-2-

naphthol

10 mL of

2 M

Ammo-

nia-

ammo-

nium

chloride

Chloroform 570 1-10 ε = 5.6 x

103

• Heating

required

• Equilibrium

time 5 min

17


naphthol

pH 9.2 Water 621 0.5-1.5 - • Triton X-100

was used as a

surfactant

18

1-(1,2,4-Triazolyl-3-

azo)-2 naphthol

pH 5.0 Chloroform 523 0.2-2.8 ε = 3.7 x

104

• Cd(II), Co(II),

Cu(II), Fe(III),

Hg(II), La(III),

V(IV) were

interfered

19

1-(2-Thiazolylazo) 2-

naphthol

pH 8.0 Methanol 621 0.05-

1.05

s = 0.012 • Simultaneously

determined

Co(II) and

Cu(II) with

Nickel(II)

• Highly sensitive

20

p-Acetyl aresenazo pH 6.0 Water 630 0-0.8 ε = 6.5 x

104

• Stoichiometry

1:2

• Absorbance was

stable for 48 h

• Maximum

absorbance

measured after 1

min

21

Benzothiaxolyldiazoa

minoazobenzene

pH 9.4 Water 550 0-0.7 ε = 1.96

x 105

• p-Octyl

polyethylene

glycol phenyl

ether was used

as a emulsifier

• Equilibrium

time 50 min

22

5,17-Bis(quinolyl-8-

azo)-25,26,27,28-

tetrahydroxycalix

[4]arene

pH

10.7

N,N-

Dimethyl-

formamide

580 1.7 x

10-7

–

5.1 x

10-6

ε = 1.28

x 105


• Stoichiometry

1:1

• Absorbance was

stable for 3 h

23



93

1 2 3 4 5 6 7 8

5-(6-methoxy-2-

benzothiazole azo)-8-

aminoquinolene

pH 10 Ethanol 623 0-0.32 ε = 1.28

x 105

• CTAB was used

as a surfactant

• Stoichiometry

1:3

• Absorbance was

measured after

20 min

24

Diethyldithio

carbamate

pH 9 Carbon

tetra-

chloride

325 - - • CTAB was used

as a surfactant

• Equilibrium

time 15 min

• Sensitivity was

enhanced by

using surfactant

25

Diethyldithio

carbamate

pH 8 Water 320 0-619 - • Simultaneously

determined

Cu(II)

• SDS was used

as a surfactant

• No extraction

step was

involved

• Stoichiometry

1:2

26

Ammonium 2-amino-

l-cyclohexene-l-

dithiocarboate

pH 3.0-

9.0

Water:

acetone

535 0.005-

3.5

- • Higher pH

range

• Absorbance was

stable for 8 min

• Simultaneously

determined

Cu(II) and

Co(II) with

nickel(II)

27

Ammonium 2-amino-

l-cyclohexene-l-

dithiocarboate

pH 3.0-

8.0

Acetone 535 0-4.0 ε = 2.8 x

104

• Higher pH

range

• Stoichiometry

1:2

• Low

interference of

ions

28

4-Methyl 2,3-

pentanedion dioxime

pH 9 Chloroform 370 0.5-10 ε = 3.039

x 103

s =

0.0192

• Stoichiometry

1:2


• Cu(II), Co(II),

Pd(II) and

Fe(III)

interfered

seriously

29



94

1 2 3 4 5 6 7 8

2-Hydroxy-1-

naphthaldoxime

pH 5.8 Chloroform 410 5-50 ε = 8.1 x

103

• Equilibrium

time 10 min

• Stoichiometry

1:2

30

Dimethylglyoxime pH 8 Water 485 0.15-1.5 - • Cu(II), Co(II),

Fe(III) were

interfered

seriously

• Complex was

exposed to atm.

oxygen

31

Dimethylglyoxime pH 12 Water 470 2.5-40 - • The mixture

was allowed to

stand for 10 min

• Equilibrium

time 1 min

• Polyethylene

glycol was used

for extraction

32

N-ethyl-3-

carbazolecarboxy-

aldehyde-3-

thiosemicarbazone

pH 6 n-Butanol 400 1.2-5.6 ε = 1.114

x 104

s = 5.29

x 10-3

• Absorbance was

stable for 72 h

• Less interfered

33

1-Phenyl-1,2-

propanedione-2-

oxime thiosemi-

carbazone

pH 3-4 DMF 395 0.42-

3.76

ε = 1.01

x 104

s = 5.0 x

10-3

• Simultaneously

determined

Cu(II)

• Absorbance was

stable for 12 h

• Stoichiometry

1:2

34

2,2’-Dihydroxy-

benzophenone

thiosemicarzone

pH 7.8 Ethanol 385 5-40 ε = 15.4

x 103

• Absorbance was

stable for 24 h

35

Bis(4-phenyl-3-

thiosemicarzone)

pH 2.5 DMF 460 2-20 ε = 2.28

x 104

s = 2.5 x

10-3

• Ringbom’s

conc. Range is

0.5-2.0 µg mL-1


method

• Stoichiometry

1:1

36

Pyridoxal-4-phenyl-

3-thiosemicarzone

pH 5.0 n-Butanol 430 0.5-5.0 ε = 1.92

x 104

s = 3.05

x 10-3

• Equilibrium

time 1 min

• Magnesium

nitrate was used

as salting out

agent

37



95

1 2 3 4 5 6 7 8

Di(6-chloro-2-methy-

phenyl)carbazone

pH 6.2 Chloroform 634 - - • Stoichiometry

1:2

• Equilibrium

time 30 min

38

2,2’-Dipyridyl

ketone-2-pyridyl-

hydrazone

pH 3.5 Ethanol 438 6-60 - • Interfered ions

was removed by

EDTA masking

agent

• Simultaneously

determined

Fe(III)

39

3-(Picolydene)

benzenesulphonic

acid 2-hydroxy

benzoylhydrazone

pH 4.0-

5.3

Ethanol 375,

385

0.05-2.0 ε = 3.6 x

104

• Absorbance was

stable for 2 h

• Simultaneously

determined

Co(II),V(IV)

40

2-Pyridinecarbal

dehyde 3,5-dinitro-2-

pyridylhydrazone

pH 4.5 1,4-

Dioxane

484 0-6 ε = 1.0 x

105

• Equilibrium

time 7 min

• Stoichiometry

1:2

41

Isatin-3,2’-quinolyl-

hydrazones

- - - - - • Spectroscopic

and physico-

chemical studies

of nickel(II)

with reagent

42

2-Pyridine

carboxaldehyde

isonicotinyl

hydrazone

pH 7 Ethanol 363 0.01-1.4 ε = 8.4 x

104

s = 6.9 x

10-3

• Stoichiometry

1:2

43

2-Benzoyl pyridine-

2-pyridyl hydrazone

pH 8.3 MIBK 495 0-1.5 ε = 5.04

x 104

• Extraction

method was free

from

interference

ions

• Synergistic

effect caused by

thiocyanate ion

44

Picolinealdehyde

salicyloylhydrazone

pH 5.0-

6.3

Ethanol 375,

385

0.25-1.0 ε = 3.9 x

104

• Absorbance was

stable for 24 h

• Stoichiometry

1:2

• Ringbom’s

optimum conc.

was 0.55-0.85

µg mL-1

45



96

1 2 3 4 5 6 7 8

2-Amino-

cyclopentene-1-

dithiocarboxylic acid

pH 5.0 Water 534 20-500 - • Triton X-114

was used as a

surfactant

• Simultaneously

determined the

Co(II) with

nickel(II)

• NaNO3 was

used as a salting

out agent

• Equilibrium

temp. and time

is 40 oC and 15

min,

respectively

46

2-(5-Bromo-2-

pyridylaxo)-5-

diethylaminophenol

pH

5.25

Water 530

and

562

10-200 ε = 1.10

x 105

• Triton X-100

was used as a

surfactant

• Absorbance was

measured after

50 min

• Stoichiometry

1:2

• Absorbance was

stable for 24 h

47


naphthol

pH 9.2 Water 552 0.1-1.5 - • Triton X-100

was used as a

surfactant

• Stoichiometry

2:1

• Simultaneously

determined the

Co(II) and

Zn(II) with

nickel(II)

48

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH 4.5 Water 530

and

560

0-0.40 ε = 1.22

x 104

at

530 and

ε = 8.20

x 104 at

560 nm

• Tergitol NPX

was used as a

surfactant

• Absorbance was

measured after

50 min

• Absorbance was

stable for 6 h

49



97

1 2 3 4 5 6 7 8

1-(2-Pyridylazo)-2-

naphthol

pH 5 Water 570

and

530

0.050-

0.50

- • Solution was

heated to

boiling for full

complexation

• Simultaneously

determined the

Co(II) and

Pd(II) with

Nickel(II)

• Tween-80 was

used as a

surfactant

50

α -Benzyl dioxime pH 12 Water 555 0.1-25.0 - • SDS was used

as a surfactant

• Stoichiometry

1:1:2

51

Dimethylglyoxime 0.25 M

NaOH

Water - - - • Flow injection

system was used


• Avoid loss of

solvent

54

Dimethylglyoxime 0.5 M

NaOH

Water - 5-50 - • Stoichiometry

2:2

• Very low

reagent conc. is

required

55

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH 4.7 Water - 0.025-

0.50

- • Detection limit

was 17 µg L-1

• Flow injection

system was used

• Heating

required to 50 oC

56

Bis(acetylacetone)-

ethylenediimine

pH 7.0 Chloroform 370 0-25 - • Sampling rate

was 18 h-1

• Reaction stream

was heated to

60 oC

57

2-(5-Bromo-2-

pyridylazo)-5-

diethylaminophenol

pH

4.75

Ethanol - - - • Multi-site

detection was

involved

• Heating

required to 55 oC

58

Dimethylglyoxime pH 9 Methanol - 0.5-5.0 - • Stoichiometry

1:2

• Equilibrium

time 40 s

59



98

o-Carboxyl

phenyldiazoaminoazo

benzene

pH 9 Acetyl-

acetone

588 1.2-41 ε = 2.95

x 107

• Amberlite

XAD-4 reisn

was used

• Equilibrium

time 20 min

60

4-(2-Pyridylazo)-

resorcinol

pH 10 Water 498 0.25-5.0 - • Polyurethane

foam was used


61

1,5-Bis(di-2-

pyridylmethylene)

thiocarbonohydrazide

pH 4 DMF 400 0.1-1.2 - • Absorbance was

measured after

30 min

• Less

interference of

foreign ions

62

3-(l-Naphthyl)-2-

mercaptopropenoic

acid

0.1 M

HClO4

Ethanol 315 - - • Highly sensitive 63

Ammonium

pyrrolidine

dithiocarbamate

pH 2.4 MIBK - - - • 9 Surfactants

are used for

increase the

sensitivity

• Less

interference of

foreign ions

64

Dithizone pH 12 Tetrahy-

drofurane

740 0-3.5 - • Coloured

complex was

stable for 2 h

• Successfully

applied to real

samples

65

N,N-bis(3-methyl

salicylidene)-ortho-

phenylene diamine

pH 8 Methanol 430 0-1.0 x

10-5

ε = 9.5 x

107

• Stoichiometry

1:1

• Tetradentate

Schiff base

having N2O2

donor group

was used as a

chromogenic

reagent


66

Ammonical sodiun

cyanide

5 mL

of

conc.

HNO3

Water 268 0.55-6.8 - • Simultaneously

determined the

Cu(II) and

Fe(III) with

nickel(II)

• Less

interference of

foreign ions

• Successfully

applied to real

sample analysis

67



99

1 2 3 4 5 6 7 8

Tetradecyldimethyl

benzylammonium

chloride

pH

10.5

DMF 551 0.9-120 - • Nickel(II)

determined by

first derivative

and using

adsorbent

• Detection limit

was 0.3 µ mL-1

• Equilibrium

time 5 min

68

Di(2,4-dimethyl-

phenyl)carbazonate

pH 6.5 Chloroform 640 - ε = 4.5 x

104

• Stoichiometry

1:1

• The

monodentate

pyridine bases

form 1:1 penta-

coordinated

adduct

69

Disodium-1-nitroso-

2-naphthol-3,6-

disulfonate

pH 7.8 Water 490 0-55 - • Highly sensitive

• Simultaneously

determined the

Cu(II) and

Co(II) with

nickel(II)

70

Pyrrolidine and CS2 pH 8 p-Xylene 340 0.005-

0.500

- • Equilibrium

time 6 min

• Simultaneously

determined the

Co(II)

71

4-(2- Pyridylazo)-

naphthol

pH 4.3 n-Butanol 568 0-0.8 ε = 4.8 x

104

• Cu(II), Fe(III),

Mn(II), Pb(II),

Zn(II) strongly

interfered

• Stoichiometry

1:2

• Equilibrium

time 1 min

72

Zincon pH 8 Water 665 0-4.6 - • After 30 min

absorbance was

measured

• Simultaneously

determined the

Co(II), Cu(II),

Zn(II)

73

Purpurin (1,2 4-

trihydoxy

antharaquinone

pH 8.5 MIBK 550 0-25 ε = 17.2

x 103

• Equilibrium

time 2 min

• Stoichiometry

1:1

74



100

1 2 3 4 5 6 7 8

Bis(4-hydroxypent-2-

ylidene)diamino

ethane

pH 13 Chloroform 375 - - • Equilibrium

time 20 min

• Stoichiometry

1:2

75

Sodium

ethylthioxanthate

pH

5.25

Carbon

tetra-

chloride

495 0-7 ε = 8.35

x 103

s = 7.0 x

10-3

• Equilibrium

time 7 min

• Coloured

complex stable

for 7 days

• Stoichiometry

1:3

76

N,N’-bis{2-[(2-

hydroxybenzylidine)

amino]ethyl}

malonamide

pH 6 Ethanol 255 - - • Potentiometric

studied the

complexes of

metals

77

3-(2-pyridyl)-5,6-

diphenyl-1,2,4-

triazine and ethyl

tetrabromophenolpht

halein

pH 6.3 1,2-

Dichloro-

ethane

610 0-0.05 ε = 2.21

x 105

s = 0.27

• Equilibrium

time 5 min

• The method is

very sensitive

78

8-Hydroxyquinoline pH 5.5 Chloroform 395 - - • Equilibrium

time 30 min

• Simultaneously

determined the

Al(III), Fe(III),

Cu(II), Ti(IV)

with nickel(II)

79



101

4.2 EXPERIMENTAL

4.2.1 Apparatus:

Absorption measurements were carried out with digital

spectrophotometer model Systronic 106 using 1 cm quartz cell. The pH values

were determined with an Elico digital pH meter model LI-120.

Glass vessels were cleaned by soaking in acidified solutions of K2Cr2O7,

followed by washing with soap water and rinsed two times with water.

4.2.2 Standard nickel(II) solution:

A stock solution of nickel (1 mg mL−1

) was prepared by dissolving an

accurately weighed amount of Merck nickel sulphate (4.7835 g) in 1000 mL of

double-distilled water with a few drops of concentrated sulphuric acid and

standardized by a known method [80].

4.2.3 Preparation of 1-(2’,4’-dinitro aminophenyl)-4,4,6-trimethyl-1,4-

dihydropyrimidine-2-thiol solution:

1-(2’,4’-Dinitro aminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2-

thiol, [2’,4’-dinitro APTPT] was synthesized and recrystallised as reported by

R. A. Mathes [81]. A 0.02 M stock solution was prepared by dissolving 0.324 g

of 2’,4’-dinitro APTPT in a 50 cm3 of chloroform.

Other standard solutions of different cations and anions were prepared

by dissolving weighed quantities of their salts in water or dilute HCl [82].

Different synthetic mixtures containing nickel(II) were prepared by combining

with commonly associated metal ions in definite composition [83].

All of the chemicals used were of AR grade. Double distilled water was

used throughout the work.

4.2.4 Recommended procedure:

An aliquot of the sample solution containing 300 µg nickel(II) solution

was taken in 25.0 mL of calibrated flask and pH was adjusted to 9.5 with dilute

hydrochloric acid and sodium hydroxide. The solution was transferred into a



102

125 mL separatory funnel and thoroughly mixed with 5.0 mL of a 0.02 mol L-1

2’,4’-dinitro APTPT and 5.0 mL of 0.5 mol L-1

pyridine in chloroform and

equilibrated for 10 min. The two phases were allowed to separate and dried

over anhydrous sodium sulphate. The organic layer having green colour was

transferred to a 10.0 mL of standard volumetric flask and made upto the mark

with chloroform. The absorbance of the coloured complex was measured at 660

nm against reagent blank prepared in similar manner. Percentage extraction

(% E) and metal distribution ratio (D) were calculated according to Eqs. (1) and

(2), respectively.

%E = [M] org. / [M] aq., init. X 100 ........… (1)

D = [M] org. / [M] aq., init .............(2)

where, [M]aq., init. are represents the initial concentration of metal ion in

the aqueous phase. [M]aq. and [M]org. are the total concentrations of metal ion in

the aqueous and organic phases after equilibrium, respectively.

4.3 RESULTS AND DISCUSSION

4.3.1 Spectral characteristics:

Nickel(II) forms a green 1:2:2 (M:L:Sy) ternary complex with 2’,4’-

dinitro APTPT, in presence of pyridine as an auxiliary ligand, which was

extracted into chloroform at pH 9.2. The colored complex in chloroform

showed maxima at 660 nm, and was stable for a more than 48 h. The optimum

conditions for the effective extraction of nickel(II) were established by

studying the effect of pH, reagent concentration, pyridine concentration, choice

of solvent, equilibrium time and interference of various diverse ions. It offers

advantages such as reliability and reproducibility in addition to its simplicity,

instant color development and lower levels of interference. The spectral

characteristic properties are shown in Table 4.2.



103

4.3.2 Absorption spectra:

The absorption spectra of green colored complex of nickel(II) with

2’,4’-dinitro APTPT in presence of pyridine showed maxima at 660 nm against

reagent blank. The absorption spectra of complex in chloroform were studied

over the wavelength range 300-800 nm. The λmax of reagent was recorded at

415 nm against the solvent as a blank (Fig. 4.1).

4.3.3 Effect of pH:

The effect of pH on the formation of the nickel(II)-2’,4’-dinitro

APTPT-pyridine complex was investigated by varying the pH of nickel(II)

solution in the range from 1 to 14 before the addition of the organic phase. The

result in Fig. 2 showed that the optimal pH for the reaction of nickel(II) with

2’,4’-dinitro APTPT is 8.7-9.8 in the presence and absence of pyridine.

However, in the presence of 5.0 mL of 0.5 mol L-1

pyridine, there was

enhancement of absorbance but in absence of pyridine absorbance was

decreased in the same pH range. Hence pH 9.2 was recommended for further

studies (Fig. 4.2).

4.3.4 Effect of solvent:

Various organic solvents were examined for the extraction of nickel(II)

(Table 4.3) with 2’,4’-dinitro APTPT complex in presence of 5 cm3 of 0.5

mol L-1

pyridine. It was observed that, the percentage extraction (%E) values

increased in the order of kerosene (6.14), < n-butanol (7.48) < amyl acatate

(9.59) < amyl alcohol (22.07) < toluene (26.48) < xylene (58.15) < methyl-iso-

butylketone (62.57) < 1,2-dichloroethane (84.26) < carbon tetrachloride (93.28)

< chloroform (99.9). Among these, chloroform was used for further extraction.

4.3.5 Effect of a chromogenic ligand concentration (2’,4’-dinitro APTPT):

Different molar concentrations of 2’, 4’-dinitro APTPT in chloroform in

the range of 0.01 to 0.04 mol L-1

added to a fixed nickel(II) ion concentration

(300 µg mL-1

) and absorbances were measured according to the standard



104

procedure. It was observed that, 3.5 mL of 0.02 mol L-1

reagent was used for

full color development in the presence of 5.0 mL of 0.5 mol L-1

pyridine. The

absorbance of the organic phase was measured at 660 nm and against reagent

blank. In absence of pyridine, absorbance was lowered. However, in order to

ensure the complete complexation 5.0 mL of 0.02 mol L-1

reagent was

recommended. A further excess of 2’,4’-dinitro APTPT has no adverse effect

on absorbance of nickel(II)- 2’,4’-dinitro APTPT-pyridine complex (Fig. 4.3).

4.3.6 Effect of equilibrium time:

The optimum shaking time of 4 min was determined by varying the

shaking time from 0.5-20 min in absence and presence of pyridine. Prolonged

shaking has no adverse effect on the extraction of nickel(II) in presence of

pyridine. Hence, a shaking time of 10 min was selected for subsequent

experiment (Fig. 4.4).

4.3.7 Effect of pyridine concentration:

The effect of pyridine concentration was studied from 0 to 5.0 mL of

0.5 mol L-1

to obtain the maximum and constant color development. It was

observed that color of nickel(II) complex into organic phase increases with the

pyridine concentration and remains constant from 3.0 mL of 0.5 mol L-1

pyridine. Therefore 5.0 mL of 0.5 mol L-1

pyridine was used for further

extraction (Fig. 4.5). Thus pyridine shows synergistic effects by the formation

of adduct.

4.3.8 Effect of color stability of complex:

The color stability was studied at room temp by measuring the

absorbance at regular time intervals. The absorbance of the nickel(II)-2’,4’-

dinitro APTPT-pyridine complex in chloroform was stable for more than 20 h.

But in absence of pyridine complex was stable for 10 h. Hence the time of

measurement of absorbance of complex in presence of pyridine was not critical

(Fig. 4.6).



105

4.3.9 Validity of Beer’s law and sensitivity:

The system obeyed Beer’s law over the concentration range of 5 to 50

µg mL-1

of nickel(II) (Fig. 4.7) as evaluated by Ringbom’s plot method [84]

was 10 to 40 µg mL-1

(Fig. 4.8). The sensitivity of the method defined by

Sandell was 0.0585 µg cm-2

and molar absorptivity was 1.64 x 103 dm

3 mol

-1

cm-1

. The standard deviation calculated from ten determinations on a solution

containing 30 µg mL-1

of nickel(II) is 0.018 and relative standard deviation of

the method is 0.16%.

4.3.10 Determination of the stoichiometry of the complex:

The synergistic extraction of precious metals by mixtures of an acidic

chelating extractant and an organic amine has been investigated. In order to

apply this kind of extraction system to the separation of nickel(II) and to

evaluate its extraction properties, the synergistic extraction with 2’,4’-dinitro

APTPT and a pyridine (py) was studied at pH 9.2.

The probable composition of extracted species was ascertained by

plotting graphs of log D[Ni(II)] against log C[2’,4’-dinitro APTPT] at fixed pyridine

concentration (0.5 mol L-1

) (Fig. 4.9). The plots were linear having the slopes

1.9 and 2.0 at pH 8.0 and 10.2, respectively. Also plots of log D[Ni(II)] against

log C[pyridine] at fixed 2’,4’-dinitro APTPT concentration (0.02 mol L-1

)

(Fig. 4.10) were linear with slopes of 1.7 and 1.8 at pH 8.0 and 10.2,

respectively. The probable composition of extracted species was calculated to

be 1:2:2 (Metal:Thiol:Pyridine). The composition was also verified by Mole

ratio (Fig. 4.11) and Job’s method of continuous variation (Fig. 4.12).

Nickel(II) reacts with 2’,4’-dinitro APTPT in the presence of auxiliary

ligand pyridine, giving an uncharged chelate which is distributed between two

phases according to the following probable equations,

[Ni(H2O)6]2+

+ 2R – S H [Ni(R-S)2 (H2O)2] + 4H2O ....(1)

[Ni(R-S)2 (H2O)2] + 2Py [Ni(R-S)2 (Py)2] + 2H2O ....(2)



106

Based on this investigation the structure is recommended for the

complex is

N

N

N

O2N

NO2

S

Ni/2

H . 2Py

4.3.11 Study of diverse ions:

The effect of foreign ions on the determination of nickel(II) was

investigated by adding the known amount of test ion to a standard nickel(II)

solution and by comparing the final absorbance with the standard. The

tolerance limits of other ions which do not cause a deviation of more than ± 2%

in the absorbance in the determination of nickel(II) is given in Table 4.4. The

result shows that most common ions do not interfere with the determination.

Selectivity of this method is increased by the use of suitable masking agent.

4.4 APPLICATIONS

4.4.1 Separation of nickel(II) from associated metals:

The method permits separation and determination of nickel(II) from

associated metals containing Au(III), Bi(II), Cu(II), Co(II), Sb(III), Ru(III),

Ir(III), Pd(II), Hg(II), Zn(II), Cd(II) and Fe(III).

Nickel(II) separated from Au(III), Bi(II), Sb(III), Ru(III), Ir(III), Fe(III)

by its extraction with 5 cm3 of 0.02 mol L

-1 2’,4’-dinitro APTPT and 5 cm

3 of

0.5 mol L-1

pyridine in chloroform at pH 9.2. Under these conditions the added

metal ions remain quantitatively in the aqueous phase. The aqueous phase was

evaporated to moist dryness by treating with 5 cm3 conc. HNO3 followed by



107

HCl. The residue was dissolved in water and diluted to appropriate volume.

The metal ions from were determined by standard methods [83, 85, 87, 88].

The organic phase containing nickel(II)-2’,4’-dinitro APTPT-pyridine

complex was estimated spectrophotometrically at 660 nm against reagent

blank.

Copper(II), Hg(II), Co(II), were co-extracted and affect the colour

stability of nickel(II) complex. Therefore, separation of these metal ions can be

achieved by use of masking agent. Copper(II), Co(II) and Cd(II) masked by

each of 1 mg of thiosulphate while Hg(II) was masked by 50 mg of sulphate,

under these conditions the added metal ions remained in the aqueous phase

quantitatively and were subsequently demasked by evaporation to moist

dryness by treating with 2 cm3 of conc. HClO4 The residue was dissolved in

water, diluted to appropriate volume and metal ions were determined by

standard methods [83, 86, 89] (Table 4.5). The absorbance of nickel(II)-2’,4’-

dinitro APTPT-pyridine complex from organic phase was measured at 660 nm

against reagent blank.

4.4.2 Determination of nickel(II) in a synthetic mixtures:

A solution containing 30 µg mL-1

of Nickel(II) was taken and known

amount of different composition of metal ions were added followed by suitable

masking agents. The results were obtained in good agreement with the amount

added (Table 4.6).

4.4.3 Determination of nickel(II) from alloys:

In order to assess the analytical applicability of proposed method,

nickel(II) was determined in standard alloys such as Monel metal (Shubh

Chemi Incorporate, Mumbai), Gun metal (Kamini Industries, India), Brass

(Shubh Chemi Incorporate, Mumbai), Nickel-Silver (ITA Laboratory,

Mumbai), Cast iron (33b) and Nickel-Base alloy (Nimonic 901). About 0.1 g of

each alloy was dissolved in 5.0 mL of aqua-regia. The alloys solutions were

heated to almost dryness and the nitrate was expelled from the residue using



108

3.0 mL of concentrated HCl. Each residue was filtered to remove silica and

metastannic acid if present. The filtrate was made up to 100 mL volume with

water separately. Suitable aliquots of these solutions are taken and

determination Nickel(II) was determined by recommended general procedure.

The results confirmed by using atomic absorption spectrophotometer

(Table 4.7).

4.5 CONCLUSION

2’,4’-Dinitro APTPT has been proved to be a sensitive and selective

spectrophotometric reagent for the determination of Nickel(II). The developed

method is simple, reproducible and rapid; requires less time for separation and

determination of Nickel(II). The important features of the proposed method’s

are (i) low 2’,4’-dinitro APTPT concentration is required for quantitative

extraction determination of nickel(II); (ii) the recommended extraction

procedure is a single stage; (iii) 2’,4’-dinitro APTPT forms complex with

Nickel(II) in weakly acidic medium in presence of pyridine used as a synergent

with probable stoichiometry at extracted species is 1:2:2 (M:L:Py); (iv) the

green colored ternary complex is stable for more than 48 h; (v) it is free from

interference of a large number of foreign ions which are commonly associated

with nickel(II). The selectivity was enhanced by the use of suitable masking

agents; (vi) the developed method is simple, reproducible, rapid and used for

separation and determination of nickel(II) from real samples.



109

Table 4.2. Spectral characteristics and precision data of nickel(II)-2’,4’-

dinitro APTPT-pyridine complex

Optical characteristics and precision

Parameters

Solvent Chloroform

λmax (nm) 660

pH range 8.7–9.7

2’,4’-dinitro APTPT concentration 5 mL (0.02 mol L-1

)

Pyridine concentration 5 mL (0.5 mol L-1

)

Equilibrium time (min) 10

Stability (h) > 48

Beer’s law range (µg mL-1

) 5-50

Ringbom optimum conc. range (µg mL-1

) 10-40

With pyridine

Molar absorptivity (lit mol-1

cm-1

) 1.67 x 103

Sandell’s sensitivity (µg cm-2

) 0.058

Without pyridine

Molar absorptivity (lit mol-1

cm-1

) 7.4 x 102

Sandell’s sensitivity (µg cm-2

) 0.78

Relative standard deviation*, (%) 0.16

Range of error ± 0.2

Mean recovery 99.8 ± 0.06

Stoichiometry of the extracted complex 1:2:2

* Average of five determinations



110

Table 4.3. Effect of solvent on extractability of nickel(II)-2’,4’-dinitro

APTPT-pyridine complex

Ni(II) = 30 µg mL-1

pH = 9.2

2’,4’-Dinitro APTPT = 5 cm3 of 0.02 mol L

-1 Pyridine = 5 cm

3 of 0.5 mol L

-1

Equilibrium time = 10 min

Solvent Dielectric

constant

λmax,

nm

Absorbance %

Extraction

Kerosene 1.80 460 0.032 6.2

n-Butanol 11.20 465 0.039 7.6

Amyl acetate 17.10 460 0.050 9.8

Amyl alcohol 2.30 450 0.115 22.5

Toluene 2.38 415 0.138 26.9

Xylene 5.00 425 0.303 59.2

Methyl

isobutylketone

13.11 445 0.326 63.7

1,2-

Dichloroethane

2.24 425 0.439 85.7

Carbon

tetrachloride

4.40 435 0.486 94.9

Chloroform 10.50 445 0.512 100.0



111

Table 4.4. Study of diverse ions for the determination of 30 µg mL-1

nickel(II) with 2’,4’-dinitro APTPT at 660 nm (relative error ±2%)


pH = 9.2


-1 Pyridine = 5 cm

3 of 0.5 mol L

-1

Solvent = Chloroform Equilibrium time = 10 min

Ions added as

Tolerance limit,

mg

Fluoride, bromide, nitrate, nitrite, tartarate, malonate, oxalate, 100

Mg(II), Ca(II), Te(IV), sulphate, thiourea, salicylate 50

Ir(III), Tl(III), Se(IV), acetate, succinate 25

Mo(IV), Al(III), Zn(II), Ga(III), Sr(II), Nb(V) 15

Mn(II), Bi(III), W(VI), Sn(II), Cd(II)a, Hg(II)

b, Pd(II), citrate 10

In(III), Cr(VI), Cr(III), Sn(IV), Co(II)a, Mn(VII)

a, ascorbate 5

Y(III), Th(IV), Fe(II), Pb(II), Pt(IV), Gd(III), Cu(II)a 3

Sb(III), Au(III), Ru(III), Fe(III), thiocynate, thiosulphate 1

U(VI), Zr(IV),Os(VIII), Rh(III) 0.500

iodide, EDTA None

a =

Masked by 1mg Thiosulphate

b = Masked by 50 mg Sulphate



112

Table 4.5. Separation of nickel(II) from associated metal ions

Metal ion

Amount

taken, µg

Average %

Recovery*

R.S.D.

%

Chromogenic

ligand

Reference

number

Ni(II) 100 99.8 0.09

Au(III) 1000 99.9 0.17 2’,4’-Dinitro

APTPT 85

Ni(II) 100 99.9 0.10

Cu(II)a 500 99.8 0.05 2’,4’-Dinitro

APTPT 86

Ni(II) 100 99.9 0.24

Co(II)a 500 99.8 0.15 Thiocyanate 83

Ni(II) 100 99.9 0.27

Bi(III) 100 99.7 0.11 Ascorbic acid +

KI

83

Ni(II) 100 99.8 0.20

Sb(III) 250 98.8 1.32 Ascorbic acid +

KI

83

Ni(II) 100 99.9 0.06

Fe(III) 50 98.6 1.39 Thiocyanate 83

Ni(II) 100 99.7 0.23

Ir(III) 150 99.6 0.41 HBr + SnCl2 83

Ni(II) 100 99.7 0.30

Ru(III) 200 99.6 0.42 Thiourea 87

Ni(II) 100 99.9 0.15

Pd(II) 100 99.7 0.26 4’-chloro PTPT 88

Ni(II) 100 99.8 0.15

Hg(II)b 100 99.9 0.07 PAR 82

Ni(II) 100 99.5 0.49

Zn(II) 100 98.4 1.11 PAR 82

Ni(II) 100 99.8 0.22

Cd(II)a 100 99.5 1.23 PAR 82

* = Average of five determinations a = Masked by 1mg Thiosulphate a = Masked by 50mg Sulphate



113

Table 4.6. Determination of nickel(II) from ternary synthetic mixtures

Composition (µg)

Average Recovery*,

%

R.S.D., %

Ni(II), 300; Cu(II)a, 300; Co(II)

a , 100 99.9 0.09

Ni(II), 300; Fe(III), 50; Mn(II), 100 99.9 0.12

Ni(II), 300; Cu(II)a, 300; Zn(II), 100 99.8 0.09

Ni(II), 300; Ag(I), 50; Au(III), 100 99.7 0.18

Ni(II), 300; Pd(II), 100; Au(III), 100 99.8 0.13

Ni(II), 300; Pd(II), 100; Ir(III), 200 99.9 0.15

Ni(II), 300; Mn(II), 100; Mo(VI), 100 99.8 0.09

Ni(II), 300; Cd(II)a, 100; Pb(II), 100 99.8 0.09

Ni(II), 300; Hg(II)b, 100; Bi(III), 100 99.9 0.09

Ni(II), 300; Sn(II), 300; Pb(II), 100 99.9 0.17

Ni(II), 300; Ag(I), 100; Cd(II)a, 100 99.9 0.10

Ni(II), 300; Au(III), 100; Hg(II)b, 100 99.9 0.09

* Average of five determinations

a = Masked by 1mg Thiosulphate

b = Masked by 50 mg Sulphate



114

Table 4.7. Determination of nickel(II) from alloys

Composition of Alloy,

%

Certified

values

of

Ni(II),

%

Amount of Ni(II)

found*,

%

Confidence

limit

α = 0.95

R.S.D.,

%

AAS

method

Proposed

method

Monel Metal

(Shubh Chemi Incorporate,

Mumbai)

Cua, 80.1; Mn

b, 13.50; Fe, 0.68

4.65 4.64 4.63 0.04 0.22

Gun Metal

(Kamini Industries supplied

standards, India)

Cua, 65; Fe, 0.5; Sn, 1; Pb,

20, Zn, 30

0.3 0.3 0.29 0.13 0.08

Brass

(Shubh Chemi Incorporate,

Mumbai)

Zn, 41.90; Fe, 0.78; Mnb,

0.55; Al, 0.51

0.3 0.3 0.28 0.21 0.15

Nickel-Silver

(ITA, Laboratory, India)

Cua, 54.6; Pb, 0.13; Sn, 0.05;

Mnb, 0.21

17.4 17.2 17.2 0.08 0.03

Cast Iron alloy 33b

Si, 2; Mnb, 0.5; Cr, 0.5; Mo,

0.5

2.0 2.0 1.92 0.06 0.15

Nickel-Base alloy 387 BCS

(Nimonic 901)

Crc, 12.46; Co

a, 21; Ti, 2.95;

Al, 0.24; Mo, 5.83; Mnb,

0.08; Fe, 36; Cu, 0.032

41.9 41.8 41.76 0.11 0.09

* = Average of five determinations

a = Masked by 1mg Thiosulphate

b = Masked by 100 mg Fluoride

c = Masked by 10 mg Citrate



115

0

0.2

0.4

0.6

0.8

1

1.2

300 400 500 600 700 800 900

Wavelength, nm

Abso

rbance

Reagent

Coloured complex

A

B

Fig. 4.1. (A) Absorption spectra of 2’,4’-dinitro APTPT vs. Chloroform blank

(B) Absorption spectra of Ni(II)-2’,4’-dinitro APTPT-pyridine

complex Vs. 2’,4’-dinitro APTPT blank


pH = 9.2


-1 Pyridine = 5 cm

3 of 0.5 mol L

-1

Solvent = Chloroform Equilibrium Time = 10 min

Wavelength = 300 to 800 nm



116

0

0.1

0.2

0.3

0.4

0.5

0.6

0 2 4 6 8 10 12 14 16

pH

Abso

rbance

With pyridine

Without pyridine

A

B

Fig. 4.2. Effect of pH on the extraction of

(A) Ni(II)-2’,4’-dinitro APTPT-pyridine complex

(B) Ni(II)-2’,4’-dinitro APTPT cpmplex


pH = 1-14


-1 Pyridine = 5 cm

3 of 0.5 mol L

-1


λmax = 660 nm



117

0

0.1

0.2

0.3

0.4

0.5

0.6

0 5 10 15 20

Reagent conc. X 10-3

mol L-1

Ab

sorb

an

ce

With pyridine

Without pyridine

Fig.4.3. Effect of reagent concentration


pH = 9.2

2’,4’-Dinitro APTPT = 0.5 to 15 x 10-3

mol L-1

Pyridine = 5 cm3 of 0.5 mol L

-1


λmax = 660 nm



118

0

0.1

0.2

0.3

0.4

0.5

0.6

0 5 10 15 20 25

Time, min

Ab

sorb

an

ceWith pyridine

Without pyridine

Fig. 4.4. Effect of equilibrium time

Ni(II) = 30 µg mL

-1 pH = 9.2


-1 Pyridine = 5 cm

3 of 0.5 mol L

-1

Solvent = Chloroform Equilibrium Time = 10 s to 20 min

λmax = 660 nm



119

0

0.1

0.2

0.3

0.4

0.5

0.6

0 10 20 30 40 50 60

Pyridine conc. X 10-2

mol L-1

Ab

sorb

an

ce

At 660 nm

Fig. 4.5. Effect of pyridine concentration


pH = 9.2

2’,4’-Dinitro APTPT = 5 cm3

of 0.02 mol L-1

Pyridine = 0 to 50 x 10-2

mol L-1


λmax = 660 nm



120

0

0.1

0.2

0.3

0.4

0.5

0.6

0 5 10 15 20 25 30

Time, h

Ab

sorb

ance

With pyridine

Without pyridine

Fig. 4.6. Effect of colour stability

Ni(II) = 30 µg mL

-1 pH = 9.2


-1 Pyridine = 5 cm

3 of 0.5 mol L

-1


λmax = 660 nm Colour stability range = 0 to 20 h



121

0

0.2

0.4

0.6

0.8

1

1.2

0 200 400 600 800 1000

Ni(II), µg

Abso

rbance

With pyridine

Without pyridine

Fig. 4.7. Validity of Beer’s law for nickel(II))2’,4-dinitro APTPT-pyridine

complex in chloroform

Ni(II) = 50 to 800 µg pH = 9.2

2’,4’-Dinitro APTPT = 5 cm3

of 0.02 mol L-1


-1


λmax = 660 nm



122

0

10

20

30

40

50

60

70

80

90

100

0 0.5 1 1.5 2 2.5 3 3.5

Log µg, Ni(II)

%T

With pyridine

Without pyridine

Fig. 4.8. Ringbom’s plot for determination optimum nickel(II) concentration

Ni(II) = 50 to 800 µg pH = 9.2


-1 Pyridine = 5 cm

3 of 0.5 mol L

-1


λmax = 660 nm



123

-1.5

-1

-0.5

0

0.5

1

1.5

2

2.5

-6.5 -5.5 -4.5 -3.5 -2.5 -1.5 -0.5 0.5

Log C [2’,4’-dinitro APTPT]

Log D

[N

i(II

)]

At pH = 8.0

A pH = 10.2

Slope = 1.9

Slope = 2.0

Fig. 4.9. Slope ratio method: With fixed pyridine concentration

Log D [Ni(II)] – Log C [2’,4’-dinitro APTPT] plot for determination of composition

of extracted species in chloroform


pH = 8.0 and 10.2

2’,4’-Dinitro APTPT = 0.1 to 3.5 cm3

of 0.02 mol L-1


-1


λmax = 660 nm



124

-1.5

-1

-0.5

0

0.5

1

1.5

2

2.5

-3.5 -3 -2.5 -2 -1.5 -1 -0.5 0 0.5

Log C [Pyridine]

Log D

[N

i(II

)]At pH = 8.0

At pH = 10.2

Slope = 1.7

Slope = 1.8

Fig. 4.10. Slope ratio method: With fixed 2’,4’-dinitro APTPT concentration: 4

Log D [Ni(II)] – Log C [Pyirdine] plot for determination of composition of

extracted species in chloroform


pH = 8.0 and 10.2


-1 Pyridine = 0.1 to 3.5 cm

3 of 0.5 mol L

-1


λmax = 660 nm



125

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0 0.5 1 1.5 2

M / L

Abso

rbance

With pyridine

Without pyridine

Fig. 4.11. Mole ratio method for determination of composition of complex

Ni(II)-2’,4’-dinitro APTPT-pyridine complex

Ni(II) = 0.2 to1.8 cm3 of 50 µg mL

-1 pH = 9.2

2’,4’-Dinitro APTPT = 1.0 cm3

of 8.518 x 10-3

mol L-1

Equilibrium Time = 10 min

Pyridine = 5.0 cm3 of 8.518 x 10

-3 mol L

-1 Solvent = Chloroform

λmax = 660 nm



126

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0 0.2 0.4 0.6 0.8 1

M / M + L

Abso

rbance

With pyridine

With pyridine

Fig. 4.12. Job’s plot for continuous variation method for Ni(II)-2’,4’-dinitro

APTPT-pyridine complex

Ni(II) = 0.2 to1.8 cm3 of 50 µg mL

-1 pH = 9.2

Pyridine = 5.0 cm3 of 8.518 x 10

-3 mol L

-1 Equilibrium Time = 10 min

2’,4’-Dinitro APTPT = 0.2 to 1.8 cm3

of 8.518 x 10-3

mol L-1

Solvent = Chloroform λmax = 660 nm



127

References:

[1] J. H. De Bussy, Materials and Technology, Vol. 3, Longman Group Ltd.

Londan, 1970.

[2] J. D. Lee, Concise Inorganic Chemistry, 5th

Ed., ELBS with Chapman

and Hall, London, 1996.

[3] B. K. Sharma, Environmental Chemistry, Goel Publishing House;

Meerut, 1997.

[4] T. Z. Judith, T. Peter, T. Thomas, Immunotoxicology of Environmental

Occupational Metals, School of Medicine, New York, 1998.

[5] H. Wada, T. Ishizuki, G. Nakagawa, 2-(2-Thiazolylazo)-4-methyl-5-

(sulfomethylamino)benzoic acid as a reagent for the spectrophotometric

determination of cobalt, Anal. Chim. Acta 135 (1982) 333-341.

[6] M. Furukawa, Synthesis and spectrophotometric studies of 2-(2-

thiazolylazo)-5-(sulfomethylamino)benzoic acid a as an analytical

reagents:determination of nickel, Anal. Chim. Acta 140 (1982) 281-289.

[7] X. Fan, C. Zhu, Synthesis of three new benzoic acid-type thiazolylazo

reagents and their application to spectrophotometric determination of

microamounts of nickel, Microchem. J. 59 (1998) 284-293.

[8] M. Furukawa, S. Shibata, Synthesis and spectrophotometric studies of

2-[2-(3,5-dibromopyridyl)azo]-5-dimethylaminobenzoic acid as an

analytical reagents:determination of nickel, Anal. Chim. Acta 140

(1982) 301-307.

[9] E. Y. Hashem, M. S. Abu-Bakr, S. M. Hussain, Interaction of nickel

with 4-(2’-benzothiazolylazo) salicylic acid (BTAS) and simultaneous

first-derivative spectrophotometric determination of nickel(II) and

iron(III), Spectrochim. Acta Part A 59 (2003) 761-769.

[10] M. S. Masouda, E. A. Khalil, A. M. Hindawya, A. E. Ali, E. F.

Mohamed, Spectroscopic studies on some azo compounds and their

cobalt, copper and nickel complexes, Spectrochim. Acta Part A 60

(2004) 2807–2817.



128

[11] W. Fu-Sheng, Q. Pei-Hua, S. Nai-Kui, Y. Fang, Sensitive

spectrophotometric determination of nickel(II) with 2-(5-bromo-2-

pyridylazo)-5-diethylaminophenol, Talanta 28 (1980) 189-191.

[12] K. Sözgen, E. Tütem, Second derivative spectrophotometric method for

simultaneous determination of cobalt, nickel and iron using 2-(5-bromo-

2-pyridylazo)-5-diethylaminophenol, Talanta 62 (2004) 971–976.

[13] M. K. Amini, T. Momeni-Isfahani, J. H. Khorasani, M. Pourhossein,

Development of an optical chemical sensor based on 2-(5-bromo-2-

pyridylazo)-5-(diethylamino)phenol in Nafion for determination of

nickel ion, Talanta 63 (2004) 713–720.

[14] T. Ishizuki, M. Tsuzuki, A. Yuchi, Y. Ozawa, H. Wada, Synthesis of

2-[2-(4-methylquinolyl)azo]-5-diethylnophenol and its use for the

spectrophotometric determination of nickel, Anal. Chim. Acta 272

(1993) 161-167.

[15] S. L. C. Ferreira, Spectrophotometric determination of nickel in

copper-base alloy with 2-(2-thiazolylazo)-p-cresol, Talanta 35 (6)

(1988) 485-486.

[16] R. Li, Zi-Tao Jiang, Lu-Yuan Mao, Han-Xi Shen, Adsorbed resin

spectrophotometric determination of nickel, Anal. Chim. Acta 363

(1998) 295-299.

[17] K. Ohshita, H. Wada, G. Nakagawa, Sulfonated 1-(2-pyridylazo)-2-

naththol and 2-(2-pyridylazo)-1-naththols as spectrophotometric

reagents:determination of nickel, Anal. Chim. Acta 140 (1982) 291-300.

[18] A. Affhami, M. Bahram, H-point standard addition method for

simultaneous spectrophotometric determination of Co(II) and Ni(II) by

1-(2-pyridylazo)-2-naththol in miceller media, Spectrochim. Acta Part A

60 (2004) 181-186.

[19] J. Cacho, C. Nerin, Spectrophotometric determination of nickel with

l-(1,2,4-triazolyl-3-azo)-2-naphthol with application to steel, Anal.

Chim. Acta, 131 (1981) 277-280.



129

[20] A. Niazi, A. Yazdanipour, Simultaneous spectrophotometric

determination cobalt, copper and nickel using 1-(2-thiazolylazo)-2-

naththol, by chemometrics methods, Chinese Chem. Lett. 19 (2008)

860-864.

[21] Shu-Lin Zhao, Xin-Quan Xia, Hou-Rong Ma, Hong-Jie Xi,

Spectrophotometric determination of nickel with p-acetylarsenazo,

Talanta 41 (8) (1994) 1353-1356.

[22] S. Zhao, X. Xia, X. Kong, T. Liu, Highly sensitive colour-reaction of

nickel with a new chromogenic reagent benzothiaxolyldiazoaminoazo-

benzene and its application, Talanta 45 (1997) 13-17.

[23] Q. Ma, H. Ma, M. Su, Z. Wang, L. Nie, S. Liang, Determination of

nickel by a new chromogenic azocalix[4]arene, Anal. Chim. Acta 439

(2001) 73–79.

[24] S. Zhao, X. Xia, Q. Hu, Complex formation of the new reagent

5-(6-methoxy-2-benzothiazoleazo)-8-aminoquinoline with cobalt and

nickel for their sensitive spectrophotometric detection, Anal. Chim. Acta

391 (1999) 365-371.

[25] M. P. S. Ndrfs, M. L. Marina, S. Vera, Spectrophotometric

determination of copper(II), nickel(II) and cobalt(II) as complexes with

sodium diethyldithiocarbamate in cationic micellar medium of

hexadecyltrimethylammonium salts, Talanta 41 (2) (1994) 179-185.

[26] M. Kompany-Zareh, A. Massoumi, H. Tavallali, Simultaneous

spectrophotometric determination of copper(II) and nickel(II) as

complexes with sodium diethyldithiocarbamate in an anionic miceller

medium using partial least-square regression, Microchem. J. 63 (1999)

257-265.

[27] T. Khayamian, A. A. Ensafi, B. Hemmateenejad, Simultaneous

spectrophotometric determinations of cobalt, nickel and copper using

partial least squares based on singular value decomposition, Talanta 49

(1999) 587–596.



130

[28] A. Safavi, A. A. Ensafi, A. Massoumi, Spectrophotometric

determination of nickel in vegetable oil with ammonium 2-amino-l-

cyclohexene-l-dithiocarboate, Talanta 38 (2) (1991) 229-231.

[29] D. J. Garole, A. D. Sawant, Extractive spectrophotometric determination

of nickel(II) using 4-methyl 2,3-pentanedion dioxime (H2MPDDO),

J. Sci. Ind. Res. 64 (2005) 581-584.

[30] K. Uesugi, S. Yamaguchi, Extraction-spectrophotometric determination

of nickel with 2-hydroxy-1-naphthaldoxime, Microchem. J. 27 (1982)

71-76.

[31] C. S. De Sousa, M. Korn, Effects of ultrasonic irradiation on the

spectrophotometric determination of nickel with dimethylglyoxime,

Anal. Chim. Acta 444 (2001) 309–315.

[32] N. Yoshikuni, T. Baba, N. Tsunoda, K. Oguma, Aqueous two-phase

extraction of nickel dimethylglyoximato complex and its application to

spectrophotometric determination of nickel in stainless steel, Talanta 66

(2005) 40–44.

[33] C. Ramachandraiah, J. R. Kumar, K. J. Reddy, S. L. Narayana, A. V.

Reddy, Development of a highly sensitive extractive spectophotometric

method for the determination of nickel(II) from environmental

matrices using N-ethyl-3-carbazolecaroxyaldehyde-3-thiosemi-

carbazone, J. Environ. Manage. 88 (2008) 729-736.

[34] K. H. Reddy, N. B. L. Prasad, T. S. Reddy, Analytical properties of

1-phenyl-1,2-propanedione-2-oxime thiosemicarbazone: simultaneous

spectrophotometric determination of copper(II) and nickel(II) in edible

oils and seeds, Talanta 59 (2003) 425-433.

[35] F. Toribio, J. M. L. Frenandez, D. P. Bendito, M. Valcarcel,

2,2’-Dihydroxybenzophenone thiosemicarzone as a spectrophotometric

reagent for the determination of copper, cobalt, nickel, and iron trace

amounts in mixture without previous separations, Microchem. J. 25

(1980) 338-347.



131

[36] A. G. Asuero, Spectrophotometric determination of nickel with biacetyl

bis(4-phenyl-3-thiosemicarzone), Microchem. J. 28 (1983) 198-202.

[37] L. S. Sarma, J. R. Kumar, K. J. Reddy, T. Thriveni, A. V. Reddy,

Development of highly sensitive extractive spectrophotometric

determiantion of nickel(II) in medicinal leaves, soil, industrial effulents

and standard alloy samples using pyridoxal-4-phenyl-3-thiosemicarzone,

J. Trace Ele. Med. Bio. 22 (2008) 285-295.

[38] A. H. M. Siddalingaiah, A. F. Dodamani, P. S. Kanavi, A study of

adduct formation of heterocyclic nitrogen bases with nickel(II) chelate

of di(6-chloro-2-methylphenyl)carbazone, Spectrochim. Acta Part A 56

(2000) 2627–2635.

[39] M. R. Ditusa, A. A. Schilt, Simaltaneous spectrophotometric

determination of cobalt, nickel, and iron, Microchem. J. 32 (1985)

44-49.

[40] M. G. Vargas, M. Milla, I. Antequera, J. A. Perez-Bustamanre,

Simultaneous spectrophotometric determination of binary mixture of

nickel, cobalt and vanadium with 3-(picolydene)benzenesulphonic acid

2-hydroxybenzoylhydrazone, Anal. Chim. Acta 171 (1985) 313-323.

[41] T. Odashima, H. Ishii, Synthesis and properties of hydrazones

from 3-and/or 5-nitro-2-pyridylhydrazine and heterocyclic aldehydes,

characterization of their complexes and extraction-spectrophotometric

determination of traces of nickel with 2-pyridinecarbaldehyde 3,5-

dinitro-2-pyridylhydrazone, Anal. Chim. Act. 277 (1993) 79-88.

[42] L. K. Gupta, U. Bansal, S. Chandra, Spectroscopic and physicochemical

studies on nickel(II) complexes of isatin-3,2’-quinolyl-hydrazones and

their adducts, Spectrochim. Acta Part A 66 (2007) 972–975.

[43] S. H. Guzar, J. Qin-Han, Simple, selective and sensitive

spectrophotometric method for determination of trace amounts of

nickel(II), copper(II), cobalt(II), and iron(III) with a novel reagent

2-pyridine carboxaldehyde isonicotinyl hydrazone, Chem. Res. Chin.

Uni. 42 (2) (2008) 143-147.



132

[44] G. A. Zachariadis, D. G. Themelis, D. J. Kosseoglou, J. A. Stratis,

Flame AAS and UV-VIS determination of cobalt, nickel and palladium

using the synergetic effect of 2-benzoylpyridine-2-pyridylhydrazone and

thiocyanate ions, Talanta 47 (1998) 161–167.

[45] M. Gallego, M. G. Vargas, F. Pino, M. Valcarcel, Analytical

applications of picolinealdehyde salicyloylhydrazone:

Spectrophotometric determination of nickel and zinc, Microchem. J. 23

(1978) 353-359.

[46] A. Safavi, H. Abdollahi, M. R. H. Nezhad, R. Kamali, Cloud point

extraction, preconcentration and simultaneous spectrophotometric

determination of nickel and cobalt in water samples, Spectrochim. Acta

Part A 60 (2004) 2897–2901.

[47] S. L. C. Ferreira, A. C. S. Costa, D. S. De Jesus, Derivative

spectrophotometric determination of nickel using Br-PADAP, Talanta

43 (1996) 1649-1656.

[48] A. Afkhami, M. Bahram, Successive ratio-derivative spectra as a new

spectrophotometric method for the analysis of ternary mixtures,

Spectrochim. Acta Part A 61 (2005) 869–877.

[49] A. C. S. Costa, S. L. C. Ferreira, M. G. M. Andrade , I. P. Lobo,

Simultaneous spectrophotometric determination of nickel and iron in

copper-base alloy with bromo-PADAP, Talanta, 40 (8) (1993)

1267-1271.

[50] M. A. Chamjangali, G. Bagherian, G. Azizi, Simultaneous

determination of cobalt, nickel and palladium in micellar media using

partial least square regression and direct orthogonal signal correction,


[51] M. Ghaedi, Selective and sensitized spectrophotometric determination of

trace amounts of Ni(II) ion using α-benzyl dioxime in surfactant media,


[52] L. T. Skeggs Jr., An automatic method for calorimetric analysis, Am. J.

Clin. Pathol. 28 (1957) 311.



133

[53] J. Ruzicka, E. H. Hansen, Flow injection analysis: 1. New concepto of

fast continuous-flow analysis, Anal. Chim. Acta 78 (1975) 145.

[54] J. A. Vieira, I. M. Raimundo Jr. J. J. R. Rohwedder, B. F. Reis, A

versitile set up for implementing different flow analysis approaches

spectrophotometric determination of nickel in steel alloys, Microchem.

J. 82 (2006) 56-60.

[55] P. B. Martelli, B. F. Reis, E. A. M. Kronka, H. F. Bergamin, M. Korn,

E. A. G. Zagtto, J. L. F. C. Lima, A. N. Araujo, Multicommutation in

flow analysis. Part 2. Binary sampling for spectrophotometric

determination of nickel, iron and chromium in steel alloys, Anal. Chim.

Acta 308 (1995) 397-405.

[56] S. Vicente, N. Maniasso, Z. F. Queiroz, E. A. G. Zagatto,

Spectrophotometric flow-injection determination of nickel in biological

materials, Talanta 57 (2002) 475–480.

[57] N. Chimpalee, D. Chimpalee, P. Keawpasert, D. T. Burns, Flow

injection extraction spectrophotometric determination of nickel

using bis(acetylacetone)ethylenediimine, Anal. Chim. Acta 408 (2000)

123-127.

[58] D. Vendramini, V. Grassi, E. A. G. Zagatto, Spectrophotometric flow-

injection determination of copper and nickel in plant digests exploiting

differential kinetic analysis and multi-site detection, Anal. Chim. Acta

570 (2006) 124–128.

[59] D. B. Gazda, J. S. Fritz, M. D. Porter, Determination of nickel(II) as the

nickel dimethylglyoxime complex using colorimetric solid phase

extraction, Anal. Chim. Acta 508 (204) 53-59.

[60] Y. Liu, X. Chang, S. Wang, Y. Guo, B. Din, S. Meng, Solid-phase

spectrophotometric determination of nickel in water and vegetable

samples at sub-µg l−1

level with o-carboxylphenyldiazoamino

azobenzene loaded XAD-4, Talanta 64 (2004) 160–166.



134

[61] S. L. C. Ferreira, D. S. De Jesus, R. J. Cassella, A. C. S. Costa, M. De

Carvalho, R. E. Santelli, An on-line solid phase extraction system using

polyurethane foam for the spectrophotometric determination of nickel in

silicates and alloys, Anal. Chim. Acta 378 (1-3) (1999) 287-292.

[62] A. M. G. Rodriguez, A. G. De Torres, J. M. C. Pavon, C. B. Ojeda,

Simultaneous determination of iron, cobalt, nickel and copper by

UV-visible spectrophotometry with multivariate calibration, Talanta 47

(1998) 463–470.

[63] A. Izquierdo, J. L. Beltran, Spectrophotometric study of the complex

formation of 3-(l-naphthyl)-2-mercaptopropenoic acid with nickel(II),

palladium(II) and hydrogen ions, Talanta 36 (3) (1989) 419-423.

[64] P. Pakalns, Y. J. Farrar, The effect of surfactants on the extraction-

atomic absorption spectrophotometric determination of copper, iron,

manganese, lead, nickel, zinc, cadmium and cobalt, Water Res. 11

(1975) 145-151.

[65] B. D. Ozturk, H. Filik, E. Tutem, R. Apak, Simultaneous derivative

spectrophotometric determination of cobalt(II) and nickel(II) by

dithizone without extraction, Talanta 53 (2000) 263–269.

[66] A. R. Fakhari, A. R. Khorrami, H. Naeimi, Synthesis and analytical

application of a novel tetradentate N2O2 Schiff base as a chromogenic

reagent for determination of nickel in some natural food samples,

Talanta 66 (2005) 813–817.

[67] W. Naixing, L. Weian, Simultaneous third-derivative

spectrophotometric determination of copper and nickel in iron alloys and

aluminium alloy, Talanta 40 (6) (1993) 891-899.

[68] M. A. Taher, A. M. Dehzoei, B. K. Puri, S. Puri, Derivative UV-visible

spectrophotometric determination of nickel in alloys and biological

samples after preconcentration with the ion pair of 2-nitroso-1-naphthol-

4-sulfonic acid and tetradecyldimethylbenzylammonium chloride onto

microcrystalline naphthalene or by a column method, Anal. Chim. Acta

367 (1998) 55-61.



135

[69] A. H. M. Siddalingaiah, A. F. Dodamani, S. G. Naik,

Spectrophotometric study on the adduct formation of nickel(II)-di(2,4-

dimethylphenyl)carbazonate with heterocyclic nitrogen bases,


[70] J. Ghasemi, N. Shahabadi, H. R. Seraji, Spectrophotometric

simultaneous determination of cobalt, copper and nickel using nitroso-

R-salt in alloys by partial least squares, Anal. Chim. Acta 510 (2004)

121–126.

[71] B. Rezaei, A. A. Ensafi, F. Shandizi, Simultaneous determination of

cobalt and nickel by spectrophotometric method and artificial neural

network, Microchem. J. 70 (2001) 35-40.

[72] Q. Wei, B. Du, Rapid and selective method for the spectrophotometric

determination of nickel naphthenate in gasoline in a microemulsion,

Talanta 45 (1998) 957–961.

[73] J. Ghasemi, S. Ahmadi, K. Torkestani, Simultaneous determination of

copper, nickel, cobalt and zinc using zincon as a metallochromic

indicator with partial least squares, Anal. Chim. Acta 487 (2-8) (2003)

181-188.

[74] T. R. Galán, A. A. Ramírez, M. R. Ceba, Spectrophotometric

determination of nickel by extraction of the complex nickel-purpurin,

Microchem. J. 27 (2) (1982) 210-216.

[75] F. I. Nwafiue, E. N. Okafo, Studies on the extraction and

spectrophotometric determination of Ni(II), Fe(II), Fe(III) and V(IV)

with bis(4-hydroxypent-2-ylidene)diaminoethane, Talanta 39 (3) (1992)

273-280.

[76] A. L. J. Rao, C. Shekhar, Extraction spectrophotometric determination

of cobalt and nickel using ethylthioxanthate, Microchem. J. 30 (3)

(1984) 283-288.



136

[77] S. K. Sahoo, S. E. Muthu, M. Baral, B. K. Kanungo, Potentiometric and

spectrophotometric study of a new dipodal ligand N,N’-bis{2-[(2-

hydroxybenzylidine)amino]ethyl}malonamide with Co(II), Ni(II),

Cu(II) and Zn(II), Spectrochim. Acta Part A 63 (2006) 574–586.

[78] T. Sakai, N. Ohno, Extraction-spectrophotometric determination of

nickel in steels and aluminium metal with 3-(2-pyridyl)-5,6-diphenyl-

1,2,4-triazine and ethyl tetrabromophenolphthalein, Anal. Chim. Acta,

221 (1989) 109-115.

[79] M. Blanco, J. Coello, F. Gonzalez, H. Iturriaga, S. Maspoch,

Simultaneous determination of metal ions spectrophotometric

determination of binary, ternary and quaternary mixtures of aluminium,

iron, copper, titanium and nickel by extraction with 8-hydroxyquinoline,

Anal. Chim. Acta 226 (1989) 271-279.

[80] A. I. Vogel, A Text Book of Quantitative Inorganic Analysis, 3rd

Ed.

Longmans, London, 1975.

[81] R. Mathes, 2-Pyrimidinethiols, J. Am. Chem. Soc. 75 (1953) 1747-1748.

[82] H. A. Flaschka, A. J. Barnard Jr., Chelates in Analytical Chemistry, A

collection of monographs, Vol. 4, Marcel Dekkar, Inc., New York 1972.

[83] Z. Marczenko, Spectrophotometric Determination of Elements, Ellis

Horwood limited, Chichester, 1976.

[84] A. Z. Ringbom, Uber die Genauigkeit der colorimetrischen

Anlysenment, Z. Anal. Chem. 115 (1939) 332.

[85] G. S. Kamble, S. S. Kolekar, S. H. Han, M. A. Anuse, Synergistic

liquid-liquid extractive spectrophotometric determination of gold(III)

using 1-(2’,4’-dinitro aminophenyl)-4,4,6-trimethyl-1,4-dihydro-

pyrimidine-2-thiol, Talanta 81 (2010) 1088-1095.

[86] G. S. Kamble, S. S. Kolekar, M. A. Anuse, Synergistic extraction and

spectrophotometric determination of copper(II) using 1-(2’,4’-dinitro-

aminophenyl)-4,4,6-trimethyl-1,4-dihydropyrimidine-2-thiol:analysis of

alloys, pharmaceuticals and biological samples, Spectrochem. Acta A 78

(2011) 1455-1466.



137

[87] E. B. Sandell, Colorimetric Determination of Traces Metals, 3rd

Ed.,

Interscience Publ. New York, 1965.

[88] M. A. Anuse, M. B. Chavan, Studies on extraction separation of

platinum metals and gold(III) with pyrimidinethiol: spectrophotometric

determination of palladium(II), osmium(VIII) and ruthenium(III), Chem.

Anal. (Warsaw) 29 (1984) 409-420.

4.1 INTRODUCTION - Shodhganga : a reservoir of Indian...

Documents

Transcript of 4.1 INTRODUCTION - Shodhganga : a reservoir of Indian...