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INTRODUCTION
Multidentate ligands which have several donor atoms in their structure form more
stable chelates, have found wide applicability in complexometric titrations. The
polyamino carboxylic acids have been found to be useful as titrants. These chelating
agents satisfy the type of properties required as successful titrant ie. (a) Formation of
a stable and soluble complex (b) A stoichiometric complex with the metal ions in
single step (c) Should be selective in nature.
1
1) The reaction reaches equilibrium rapidly following each addition of titrant.
2) Interfering situations do not arise (such as stepwise formation of various
complexes resulting in the presence of more than one complex in solution
in significant concentration during the titration process).
3) A complexometric indicator capable of locating equivalence point with fair
accuracy is available.
Ethylenediaminetetraacetic acid has four carboxyl groups and two amine groups that
can act as electron pair donors, or Lewis bases. The ability of EDTA to potentially
donate its six lone pairs of electrons for the formation of coordinate covalent bonds
to metal cations makes EDTA a hexadentate ligand. However, in practice EDTA is
usually only partially ionized, and thus forms fewer than six coordinate covalent
bonds with metal cations. Disodium EDTA, commonly used in the standardization of
aqueous solutions of transition metal cations, only forms four coordinate covalent
bonds to metal cations at pH values less than or equal to 12 as in this range of pH
values, the amine groups remain protonated and thus unable to donate electrons to
the formation of coordinate covalent bonds.
EDTA forms an octahedral complex with most M2+ cations in aqueous solution. The
main reason that EDTA is used so extensively in the standardization of metal cation
solutions is that the formation constant for most metal cation EDTA complexes is
very high, meaning that the equilibrium for the reaction,
M2+ + H4Y MH2Y + 2H+ lies far to the right. Carrying out the reaction in a basic
buffer solution removes H+ as it is formed, which also drives the reaction to the right.
For most purposes it can be considered that the formation of the metal cation-EDTA
complex goes to completion, and this is chiefly why EDTA is used in titrations /
standardizations of this type.
To carry out metal cation titrations using EDTA it is almost always necessary to use
a complexometric indicator, usually an organic dye such as Fast Sulphon Black,
2
Eriochrome Black T, Eriochrome Red B or Murexide, to determine when the end
point has been reached.
These dyes bind to the metal cations in solution to form colored complexes.
However, since EDTA binds to metal cations much more strongly than does the dye
used as an indicator, the EDTA will displace the dye from the metal cations as it is
added to the solution of analyte.
A color change in the solution being titrated indicates that all of the dye has been
displaced from the metal cations in solution, and that the endpoint has been
reached.
EDTA forms stable, soluble 1:1 complex with metal ions of different oxidation state.
The metal ions which can be determined by direct or back titration with EDTA are
Mg2+, Ca2+, Sr2+, Ba2+, Sc, Y, Ti, Zr, Hf, V, Nb, Cr, Mo, W, Mn2+, Fe2+, Co2+, Ni2+,
Cu2+, Zn2+, Cd2+, Hg2+, Al3+, Ga, In, Tl, Sn, Pb, Sb, Bi, Th, U, Pu and lanthanides (2).
Direct complexometric titration has been used for simultaneous determination of Th4+
and lanthenons using semimethylthymol blue [SMTB] as indicator with EDTA. Th4+ is
titrated at pH 2 and subsequently pH was adjusted to 5.5 - 6.0 by adding hexamine
and acetylacetone – acetone solution and lanthanides were then titrated (3). Alkaline
EDTA with degrees of neutralization Xo in the range 0.950 – 0.990 has been used
successively as a titrant for the determination Mg2+ (Range 5 x 10-3 – 100 x 10-3
moldm-3) and other divalent cations. Sharp end points can be obtained
potentiometrically with a glass electrode and detected visually with phenolphthalein
as indicator instead of Eriochrome Black – T (4).
The precise and accurate results have been achieved in consecutive back titrations
of Ga3+, In3+ and Tl3+ with solutions of EDTA and standard Th (NO3)4 of the same
concentration, using semithymol blue (SMTB) as a metallochromic indicator with
visual end point indication (6).
Trichromatic colorimetry has been applied for the evaluation of the color changes of
the metallochromic indicators uiz. Hematoxylin, Gallocyanine, Gallamine blue,
3
Solochrome prune as, Celestine blue, EBT, Xylenol orange and catechol violet in
complexometric titration of Zr (IV) with EDTA to measure the quality of color changed
at the equivalence point (7).
Complexometric study is widely used in the medical industry because of the micro
liter-size sample involved. The method is efficient in research related to the biological
cell because.
A number of compounds which act as suitable titrant for metal ions have been
synthesized with the objective of specifying the titrating reagent.
HEDPHA has been proposed by Pribil and Vesely (12) as a highly selective titrant for
thorium. The titration method is based on the formation of mixed ligand complexes.
In the presence of CDTA a soluble binuclear ternary complex is formed. The titration
is carried out in a slightly acidic medium (pH 5.0 to 5.5) in the presence of a slight
excess of CDTA or EDTA which will mask other metal ions but not the color reaction
of Th-CDTA with Xylenol orange; the amount of HEDPHA consumed corresponds to
one half of thorium present.
4
Nitrilotriacetic acid is also called ammoniatriacetic acid. It is similar to EDTA in its
reaction with metal ions. There are only four ligand groups in the molecule and
therefore the chelate effect is less as compared to EDTA. The complexes are less
stable than the corresponding EDTA complexes but are sufficiently stable to be of
interest in the analytical chemistry for determination of a number of metal ions (14).
The copper complexes with Nitrilotriacetic acid have been thoroughly investigated
(15). A number of procedures for the titrimetric determination of copper with NTA
have been reported (16).
The Cu (II) has been determined using chromozurol indicator in the buffer of
hexamethylene tetra amine in pH range 5.5 – 6.0. The indicator changes color from
blue to green (17). Ammonia buffer of pH = 10 has been used when muroxide
indicator is employed (18) and color change from yellow-green to violet is obtained.
Cu (II) is determined in the concentration range of 10-50 mg at pH 9 with mean error
0.1% Chromozural indicator has been used in buffer of haxamethylene tetramine
(17) (PH 5-6) to determine Cu (II) in presence of Mn(II), Fe(III), Al(III) and alkaline
earth metals.
DTPA has two CH2CH2 bridges linking three nitrogen atoms and is octadentate. The
diethylenetriaminepentaacetic acid (DTPA) forms complexes with copper and many
other metal ions. The complexes of DTPA are more stable than the corresponding
EDTA complexes, and are used for chelometric titrations (14, 19, 20, and 21).
Copper is titrated in an acetate or ammonical solution of pH 5-9.2 at 600c (21, 22). A
copper – PAN indicator changes color from red to yellow at the end point. Indium-III
DTPA complex is a widely used compound in diagnostic nuclear medicine (23).
This compound designated as DCTA is similar to EDTA in its complexing action, but
the metal DCTA complexes are more stable than the corresponding EDTA
complexes (26, 27).
5
10-3M solution of DCTA is used as titrant to give an accuracy of 0.5%. Cd (II), Mn
(II), Ni (II) and Zn (II) show interference in the determination.
Cu (II) has been determined with DCTA using pyrocatechol violet indicator in
presence of pyridine. Pyridine is added to Cu (II) solution containing 30 mg/100 ml till
pH becomes 6-7 indicated by the formation of Blue color of Cu-Pyridine complex.
Pyrocatechol indicator is added to this blue solution and titrated with DCTA to a color
change of Yellow to Green (28). In acidic medium Mo (VI) forms a stable complex on
boiling with excess DCTA and hydroxylamine hydrochloride. Molybdenum can then
be determined by back titration of the excess of DCTA either with zinchloride at pH
5-5.5 or with thorium nitrate at pH 3-4.5 where Xylenol orange is used as indicator.
The general theoretical expressions for complexometric titration curves have been
described by Tanaka and Nakagawa (29). The effect of pH, complexing agent and
the presence of second metal ion are taken into account. The sharpness of the end
point and the accuracy of the titrations by direct techniques are discussed
theoretically. Pribil and Coworkers have reported the titrations of mixtures of metal
ions. The titration of Galium and Indium in a mixture is based on their different
complex formation with TTHA. Galium and Indium forms 1:1 complexes with EDTA
but with TTHA, Galium forms 2:1 and Indium a 1:1 complex (30).
The progress of a complexometric titration can be monitored with the help of a visual
indicator which are termed metallochromic indicator.
The end point can be computed with monitoring the change of –logM or pM which is
equivalent of pH and plotting a graph between pM and volume of titrant added. An
‘S’ shaped curve is obtained as shown in fig. and inflection point gives the end point.
PM
Volume of titrant
Fig.
End points of metal-Polyaminocarboxylic acid and polyamine titrations can be
detected by potentiometry. Since, there is no change in oxidation state during the
6
titration, a redox couple and a suitable indicator electrode must be introduced into
the system.
Metallochromic Indicators
Metallochromic indicators are organic dyes which form chelates with the metal ions
which are normally colored. Indicator metal ion complex has a different color from
the free indicator. Metallochromic indicators respond to the change in the pM value
of metal ion as well as pH of the solution. The pH maintenance of the solution
becomes very important.
OH
OH
-
O 3S N=N
NO2
The acids and their conjugate bases have different colors. Thus EBT behaves as an
acid / base indicator as well as metal ion indicator. The metal complexes of
Eriochrome Black T are generally red, similar to H2In-.Thus, for metal ion detection, it
is necessary to adjust the pH to 7 or above so that the blue form of the species, HIn2-
, predominates in the absence of a metal ion. The indicator forms complex with the
excess metal ion until the equivalence point is reached and there after the solution is
red when EDTA is in slight excess, the solution turns blue as a result of the following
reaction.
7
The indicator forms stable 1:1 complexes, which are wine red in color with metal ions
such as Mg2+, Ca2+, Zn2+ and Ni2+. Many EDTA titrations are performed in buffer of
pH 8 to 10, the range in which the predominant form of EBT is the blue HIn2- form.
This reaction will proceed if the metal – indicator complex M-In is less stable than the
metal EDTA complex M-EDTA. The former dissociates to a limited extent, and during
the titration the free metal ions are progressively complexed by the EDTA until
ultimately the metal is displaced from the complex M-In to leave the free indicator
(In). The stability of the metal-indicator complex may be expressed in terms of the
formation constant (or indicator constant) Kin.
The indicator color change is affected by the hydrogen ion concentration of the
solution. Thus solochrome black, which may be written as H2In-, exhibits the
following acid-base behavior:
pH pH
- 2-
H2In HIn In3-
Red 5.3 – 7.3 Blue 10.5 – 12.5 Yellow – Orange
In the pH range 7-11, in which the dye itself exhibits a blue color, many metal ions
form red complex. These colors are extremely sensitive, as is shown, for example,
by the fact that 10-6 – 10-7 molar solutions of magnesium ion give a distinct red color
with the indicator. From the practical viewpoint, it is more convenient to define the
apparent indicator constant K’In, which varies with pH as:
log K’In gives the value of pM when half the total indicator is present as the metal ion
complex. Some values for log K’In for CaIn- and MgIn- respectively (where H2In- is the
8
anion of solochrome black) are : 0.8 and 2.4 at pH = 7; 1.9 and 3.4 at pH = 8; 2.8
and 4.4 at pH = 9; 3.8 and 5.4 at pH = 10; 4.7 and 6.3 at pH = 11; 5.3 and 6.8 at pH
= 12. For a small titration error K’In should be large (>104), the ratio of the apparent
stability constant of the metal – EDTA complex K’MY to that of the metal – indicator
complex K’In should be large (>104), and the ratio of the indicator concentration to the
metal ion concentration should be small (<10-2).
The visual metallochromic indicators discussed above form by far the most important
group of indicators for EDTA titration.
Eriochrome Black T is of this type of indicator. The reaction of this indicator with
magnesium at various pH may be known from the following graph (31).
10
8 -
H2 I
Red HI2-
6 Blue
pMg
4
MgI-
2 p
pt
Red
H)
2
(O
Mg
0
I I I I I I
4 6 8 10 12 14
pH
The figure illustrates the color change of the indicator considered as an acid base
indicator and as a metal indicator. It is obvious that the indicator is not sufficiently
sensitive at low pH value. While at high pH Mg (OH) 2 precipitates. The best color
change occurs in the pH range 10 to 11.
9
The indicator Arsenezo is useful for the rare earths and Thorium (34). Methylthymol
Blue is prepared from the acid-base indicator thymolblue and is used for metal ions
of group (III) and also group (II) at pH values below 7.2 (34). Calcein which is
prepared from the acid base indicator fluorescein retains the fluorescent properties
of fluorescein and hence end points in EDTA titrations using this indicator are
detected by a change in fluorescence (16).
The end point is obtained by plotting the absorbance of the titration solution against
ml of titrant added. The resulting graph shows intersection of two straight lines which
gives the end point. The shape of the photometric titration curve will depend on the
condition of the chemical reaction.
CURVE A:
In a titration where the colorless reactant result in the formation of a colored reaction
product and absorbance is measured at the max of the product.
CURVE B:
The titration where one of the reactant is colored and product of the reaction is
colorless and absorbance is measured at the max of colored reagent.
CURVE C:
The titration where, one reagent and product is colored and course of reaction is
followed at max of either reactant or product.
10
O.D O.D
O.D O.D
volume of reagent added volume of reagent added volume of reagent added volume of reagent added
Curve A Curve B (a) (b)
Curve C
Let M, L and ML be the extinction coefficients of the metal, ligand and the
complex respectively, the change in absorbance before the equivalence point
depends upon the difference
CM
[M]eq =
C ML
Photometric titrations have been successfully employed in the titration of metal ion
using different ligand. An advantage of photometric titration is simultaneous
determination of two metal ions in presence of each other.
11
Determination of Bi3+ and Cu2+ has been reported by photometric titration. (35) The
selected wave length for measurement, 745 nm is maximum absorption for Cu-
EDTA complex where Bi-EDTA complex does not absorb at this wave length.
Salicylic acid and Fe3+ forms a deep colored complex with a maximum absorption at
525 m. This complex has been used as the basis for the photometric titration of
Fe3+ (31).
Photometric titration of Erbium has been reported with PAR at pH 8.0 – 8.8 and at
540 nm (39).N, N’ – Ethylenediaminedipropionic acid has been used for the
photometric titration of copper at 261 nm (16). The relative error is 1-2%. Calcium,
lead, magnesium, mercury (II) and zinc do not interfere.
12
Absorption laws:
Thus, Io = Ia + It + Ir
Bouguer – Lambert – Beer law relates the absorption of light to the concentration of
absorbing species and the thickness of the absorber layer.
Mathematically it is expressed as
A = log Ii / It = .C.X
Where is a constant called the molar absorptivity (or molar absorption coefficient),
C is the concentration of the absorbing species (moles.ltr -1), X is the thickness of the
absorbing layer, Ii and It are the intensities of incident and transmitted light.
1
A = log T
If a solution contains more than one non-interacting absorbing species, the total
absorbance is equal to the sum of absorbances of individual components. If the
optical path length (X) is constant, this law of additivity is expressed as
For an ideal system obeying beer’s law, a plot of A vs C for a fixed value of ‘X’ gives
a straight line, passing though the origin and having slope equal to as per the
equations given above.
The straight line relationship between concentration and absorbance at some times
shows deviation. The deviation from Beer’s law may be positive or negative
depending on the curvature of graph line weather it is on left hand or right hand side.
13
(A) Chemical factor
The interaction of solution components within the solution may cause certain
changes in absorbing species. pH condition of the solution, dissociation of the
absorbing species, and association of absorbing species are important factors which
govern the deviation from the Beer’s law.
(B)Physical factor
The physical factors which are responsible for deviation are mainly dependent on
optical factors. The scattering of light by particles in the solution, the change of
temperature of solution, related thermochromy and the entry of stray radiation in the
detector compartment.
= A
C.X
Where A is the absorbance, C is the concentration in moles per liter and ‘X’ the
absorber thickness in Cm. The molar absorptivity () is expressed in LMol-1 Cm-1. For
sensitive Spectrophotometric method () is greater than 1 X 104 LMol-1 Cm-1. This
value cannot exceed ~ 1.5 x 105, according to quantum theory. The sensitivities of
Spectrophotometric methods for elements with similar atomic weights can be
interpreted in terms of molar absorptivity.
Specific absorptive (a) = ______________
Atomic wt x 1000
The value ‘a’ (in ml g-1 Cm-1) corresponds to the absorbance of a g ml-1 (1 ppm)
solution of the determinant in a cuvette with an optical path length of 1 Cm.
14
10
S=
a
2
It is expressed in g Cm . The sensitivity of Spectrophotometric measurements also
depends on the monochromaticity of radiations; molar absorptivity diminishes as the
band – width increases.
Instrumentation
Spectrophotometers offer the considerable advantage that the wavelength used can
be varied continuously and thus making it possible to obtain the entire absorption
spectrum. The component of the instruments, more or less remains the same with
minor changes,
The entire instrument for absorption measurements in ultraviolet, visible radiation are
made up of the following components.
1. Source
The source provides continuous radiation that is made up of all wave lengths within
the spectral region to be used and it must provide stable output.
2. Monochromators
The monochromator is that part of spectrophotometer which when operated with a
suitable radiant energy source can provide a narrow band of radiant energy of
desired wavelength range. The advantage of this is that the Beer’s law is more likely
to be obeyed and greater selectivity is ensured and sensitivity is also increased. A
diffraction grating or a quartz prism is used as dispersive device to separate a
continuous spectrum into its constituent wavelengths.
3. Sample containers
15
The cells or cuvettes that hold samples are fabricated from a material that is
transparent to radiation in the spectral region of interest. The best cells have
windows that are exactly perpendicular to the light path. The most common cell path
for work in the ultraviolet and visible region is 1 Cm and optical windows are made of
quartz.
4. Radiation detectors
The detector converts the electromagnetic energy to an electrical signal.
Photoelectric detectors are used to convert radiant energy to photocurrents which
can be measured.
The power supply unit, electronic amplifier and readout meter or recorders are
additional essential components of the photometric system.
Quantitative Applications
Spectrophotometry is a very important quantitative method of analysis of traces of
organic and inorganic substances. The methods for the trace quantities of most of
the metal ions have been reported in the literature. Organic reagents which form
coloured metal chelates are used extensively.
(1) Oxine
Metals such as AI (III), Ca (II), Cr (II), Fe (III), Ga, In, Mg, rare earths, Sc, U (VI), V
(V) and Zr have been determined spectrophotometrically with oxine after chloroform
extraction (40).
16
(3) Glyoxal bis – (2 – hydroxyanil)
It is one of the useful reagent for the determination of calcium.It has also been
proposed as a reagent for the determination of cadmium and uranium (43).
(9) Chromazurol S
The reaction of antimony and chromazurol S was developed in PH 5-6 buffer
solution. The determination of trace amounts of antimony in waste water was studied
by -Correction spectrophotometry. The results showed that Beer’s law is obeyed
over the concentration range 0 – 1.0 mgl-1 of antimony. The detection limit is 0.009
mgl-1 which is low enough to determine in environmental waters (50).
(10) - amylthioglyconate
17
A simple, rapid and direct Spectrophotometric method using n-amylthioglyconate has
been developed for the simultaneous Spectrophotometric determination of Nickel
and Palladium. The molar absorptivities are calculated to be 0.45 x 104 mole-1 Cm-1
and 0.73 x 104 mole-1 Cm-1 for Nickel and palladium respectively. The method has
been applied to synthetic mixtures and various alloys. Various parameters have
been studied (51).
18
It is a new reagent for the rapid and selective estimation of pt (III). The yellow
complex is extractable in oxygenated solvents. Possible analytical applications have
been reported (56).
(17) 8- hydroxyquinoline
A Simple and rapid Spectrophotometric method of determination of vanadium have
been developed by the Reduction of the metal ion with Zn / Hg in the presence of 8-
hydroxyquinoline under the acidic conditions employing acetylacetonechlotoform as
extractant. The method has a std. deviation of 0.0065 and sandells sensitivity 8.6956
x 10-2 gV/Cm2(57).
19
References:
2. Gopala Rao, Vistas in Analytical Chemistry’, S. Chand & chand & Co. (P) Ltd; (1971).
4. M. V. Rossi, F.A. Eduardo and E. V. Maria; The Analyst, 119, 1633 (1994).
7. K. M. M. Krishna Prasad, P. V. Lakshmi and C. K. Sastri; The Analyst, 119 2817 (1994).
applications pure appl. Chem., 77(8) : 1445 – 1495 doi 10.1351 (2005).
11. J. H. Grimes, A. J. huggard and S. P. Willford; J. inorg. Null, Chem; 1225, (1963)
13. Andergg, “Critical Survey of stability constants of NTA complexes.’ Pure Appl. Chem.
14. F. Bermejo Martines and A Prieto Bouga; Inform, Quim, anal (Madrid), 15 103-12(1961);
C.A. 57, 5284 (1962)
15. B. Kirson and R. Bornstein; Bull Soc. Chim., France, 288, 1960; C.A. 54, 16250 (1960)
16. Frank J. Welcher and Erwin Boschmann; ‘Organic Reagents for copper’ 1st Edn., Robert
17. P. Whber; Z. Anal, Chem., 149, 419-32 (1956); C.A. 50, 8369 (1956).
18. P. Wlehber & W. Johannsen; Z. Anal. Chem., 153, 324-7 (1956); C.A. 51, 7935 (1957).
19. N. Tanaka and M. Kimura; Bull. Chem. Soc; Jap. 40, 2100, (1967).
20. E. J. Durham and D. P. Ryskiewich; J. Am. Chem. Soc. 80, 4812-17 (1958), C. A. 53,
2749 (1959).
21. E. Wanninen, Acta, Acad, Aboensis, Math et. Phys., 21, 110 (1960).
20
22. E. Wannien, Soumen Kemistilchti, 28B, 146-52 (1955).
23. Helmut R. Marcke, Andreas Riesen and Walter Ritter. Dept. of nuclear medicine, Uni.
24. F.Bermejo Martinez, M. Paz Castro and R. Ray Mendoga; Inform,. Quim. Aunal. (madrid)
14, 34-7 (1960), C.A. 55, 16266 (1961).
25. F.Bermejo Martinez, M.Paz Castro and R. Ray Mendoga; Inform Quim. And (Madrid) 14,
61-3 80 (1960) C.A. 55, 19285 (1961).
26. N. Tanaka and M. Kimura; Bull. Chem. Soc; Jap. 40, 2100, (1967).
27. S. Takei and T. Kato; Technol, Repts, Tokoku Univ. 67-73 (1959), C.A. 54, (1960).
st n
31. Gurudeep Chatwal and M. S. Yadav; ‘Coordination Chemistry’; 1 Ed . Himalaya
Publishing house, Delhi. (1992).
32. Harris, Daniel C. Quantitative chemical Analysis, W. H. Freeman and company, ISBN,
0716770415. (2007).
th n
33. R. A. Day, A. L. Underwood; ‘Quantitative Analysis’ 5 Ed ., Prentice-Hall of India Pvt.
Ltd. (1988).
34. Pietrzyk and Frank; ‘Analytical Chemistry’ Iind Edn., Academic Press, New York, (1979)
35. G. W. Ewing; ‘Instrumental Methods of Chemical Analysis’, Fifth Ed., (191) McGraw – Hill
Book Company.
st n
39. H. A. Flaschlka, a. J. Barnarch Jr. Chelates in Analytical Chemistry; Vol-4, 1 Ed ., Marcel
Dekker, INC. New York; (1972).
41. L. N. Lapin and N. V. Reis, Zh. Anal. Khim; 13, 426 (1958).
42. V. K. Akimv, A. I. Busev and L. Ya. Kilot; Zh. Anal. Khim., 28, 1014, (1973).
44. J. H. Saylor and J. W. Ledbetter; Anal. Chim. Acta; 30, 427 (1964).
49. Nan Zhon and Chun Xieng He; The Analyst, 119, 2105 (1994).
51. A. K. malik, Atmasyot and ALJ Rao; Ind. J. Chem. 32A, 180 (1993).
55. H. S. Sanke & L. R. Kakkar; Ahmed and J. B. Raj; Ind. J. Chem., 29A, 95 (1990).
22
1.2 The Metals
1.2.1 CHROMIUM
Symbol: - Cr; At Wt: - 52.01 At No: - 24;
Electronic configuration: [Ar] 3d5 4s2
OCCURRENCE:
Chromium does not occur free in nature. It occurs combined with oxygen, as chrome
ore which is chromium (III) Oxide, Cr2O3. The most important ore of chromium is
chromites or chrome iron, FeCrO4 or FeO Cr2O3. It also occurs as crocoisite which is
lead chromate. PbCrO4. Chromium forms nearly 0.037 percent of the earth crust.
Vanquelin discovered the metal chromium in 1797. Its name is derived from the
Greek word ‘Chroma’ meaning colour, as most of its salts are either green or violet.
Physical Properties:
Chromium is a bluish white lustrous metal. Its M.P. is 18750C. It takes a good polish
which lasts long because of the formation of an invisible, self protective oxide
coating. Pure metal is a soft and malleable but, as usually obtained, chromium is
among the hardest of the common metals. This is due to the presence of a small
amount of carbon as impurity. It is resistant to corrosive agents. The compounds of
chromium are all coloured. The density of the metal is 7.1 where as boiling point is
22000C. It is soluble in acid (except nitric Acid) and strong alkalies and is insoluble in
water.
The oxidation state of +1 arises from the transference of the solitary S-electron to
other atoms, but this state is not common and exists only when chromium is present
in certain complex compound for e.g. [(Cr (diphenyl)3]+clo4-.
23
The stable oxidation states of chromium are +2, +3 and +6. This arises from the
transference or sharing of one or more d-electrons. The compounds such as (CrO,
Cr(OH) 2, CrCl2, CrSO4 and (CH3COO)2 Cr exhibits +2 oxidation state of chromium.
CrCl3 Cr2 (SO4)3, Cr2O3 and Cr(OH)3 are the compounds in which chromium is in +3
oxidation state, where as +6 oxidation state is shown in the compound as CrO3,
K2CrO4, K2Cr2O7, NaCrO4, and Na2Cr2O7.
Chromium (II) compounds are very good reducing agents as they are readily
oxidized by air to highly stable chromium (III) compounds. Cr (II) ion is blue in colour.
Hence all the chromium (II) compounds have beautiful colours. Chlorine compounds
containing Cr (III) ion, e.g. chromic chloride, CrCl3 are the most important
compounds of chromium. They form a number of coordination complexes.
The +3 oxidation state is highly stable in acid solutions but it gets oxidized readily to
+6 oxidation state in alkali solutions.
Thus, while chromium compounds in +2 oxidation state are reducing agents, those in
+6 oxidation state are strong oxidizing agents.
The +3 and +6 oxidation states of chromium are important. These have extensive
solution chemistry.
Chromium is widely used in various industries and alloys. Chromium salts are used
in electroplating industry. Chromium (III) is used as a green pigment in glass,
porcelain and oil paint. Chromate compounds are often used for corrosion control.
The normal level of Cr (VI) in drinking water is 3 to 40 ppm, the permissible level
being 50 ppm as certified by the WHO. Chromium enters water bodies through
discharges of waters. It has been determined in various steels, alloys and in polluted
water bodied. There are many sensitive techniques for chromium determination,
such as ICP- MS, ICP – AES, HPLC, neutron activation analysis (1), X- ray
absorption spectroscopy (2), complexometric (3), flow-injection (4), sequential
injection (5, 6), flourogenic method (7) and spectrophotometry (8, 9). A survey of
literature reveals that Cr (III) reacts with many organic reagents at high temperature
24
due to the inert nature of [Cr (H2O) 6]3+ complex. The time required varied from 20
minutes to 2 hours depending on the nature of reagents (10-12). The need to
monitor chromium in the environment has led to the application of increasingly
complex analytical techniques (13, 14)
(ii) Steel
Chromium has been determined in various steels as chromium (III) by reacting it with
Arsenazo-DBSzx which forms 1:2 complexes at acidic pH 2.5 to 3.5 after keeping in
boiling water bath for twenty minutes (16). The complex shows λmax at 620 nm, and
the molar absorbance 5.5. x 104. Beer’s law is obeyed for concentration range of 1 –
18 µg Cr/25 ml.
Chromium (VI) (1-100µg) has been determined by this method at 365 nm (molar
absorbance 1.38 x 103 L-1Mole-1) after its extraction as pentamethylenebis (triphyenyl
phosphonium) dichromate into 1, 2 dichloroethane. The method has been applied for
the determination of chromium in steels. (17)
A preconcentration method with the collection of metal complex on chitin for the
Spectrophotometric determination of chromium (VI) in water has been reported by
Hishi and co-workers (19). The chromium (VI) was collected as its 1, 5-
diphenylcarbazide (DPC) complex on a column of chitin in the presence of dodecyl
sulfate as counter ion. The Cr-DPC complex retained on the chitin was eluted with a
methanol-1 M acetic acid mixture (7:3, v/v) and the absorbance of the eluent was
measured at 541 nm. Beer’s law was obeyed over the concentration range of 0.05 –
0.6 µg of chromium (VI) in 1 mL of the eluent. The apparent molar absorptivity was
3.5 x 104 dm3 moL-1cm-1. The tolerance limits for Fe (III) was low, i.e. ten times that
of chromium (VI), but some metal ions and common inorganic anions do not interfere
25
in concentration range of 100 – 10000 times that of chromium (VI). Xiaoyuan and
colleagues reported two sensitive flow-injection methods for the determination of
trace amount of Cr (VI), based on the microwave-accelerated reactions of Cr2O72-
with dibromocarboxyarsenao (DBM-AsA, in system 1) and dibromo-0-
carborylchlorophonazo DBOK-CPA at 556 nm. The sampling frequencies for both
systems were 40h-1. The calibration graphs are linear in the range between 1.62 and
27.0 µgmL-1, and 0.40 and 10.80 µg mL-1 for systems 1 and 2, respectively. The
respective detection limits were 0.087 and 0.10 µg mL-1. The methods developed
were used for determining chromium in a steel sample and electroplating solutions
with satisfactory results.
Chromium has been determined in plating mist by colourimetric analysis (20). The
sample is reacted with 1, 5 diphenylcarbazide to give Cr (VI) chromogen. The
accuracy of the method is 10% and the recoveries of Cr (III), Cr (VI) and the total
chromium are 98, 85 and 90% respectively.
(iv) Alloys
Chromium has been determined in the alodine film coated on alluminium alloy by
spectrophotometry (22). The total amount of chromium as Cr (VI) has been
determined by diphenyl carbazide. The measurement is easy with excellent
reproducibility.
A new method of adsorption of Cr (VI) ions on two Lewatit – anion exchange resins
has been reported. Their quantitative determination was carried out by using UV-
Visible spectrophotometer (23). The adsorption of Cr(VI) from aqueous solutions with
macro porous resins which contain quaternary amine groups (Lewatit MP 64 and
Lewatit MP 500) was studied at varying Cr(VI) concentration, adsorbent dose, pH,
contact time and temperature.
26
Variamine blue as a reagent for the spectrophotometric determination Chromium (VI)
has been reported by Fabiyi. It reacts with potassium iodide in acid medium to
liberate iodine that oxidizes variamine blue to produce violet colored substance
having an absorption maximum at 615 nm whose molar absorptivity was 8.12 x 104 L
mol-1 cm-1.Beer’s law was valid over the concentration range 0.0003-15.0 µg mL-
1
(24). Spectrophotometric determination of trace chromium (VI) by micro emulsion
medium was studied by chemist Wie and others (25). The method was based on the
catalytic effect of chromium (VI) on the oxidation of nuclear fast red in the presence
of Tween – 80 micro emulsion and HAx-NaAc buffer solution (pH = 5.2).
27
and Sandell’s sensitivity of the system were 3.77 x 104 L mol-1cm-1 and 2.76 x 10-2
µgcm-2 respectively.
28
spectrophotometrically at 362 nm after its extraction as dihydrogen dichromate into
propylene carbonate. Tropolone has been used for the spectrophotometric
determination of chromium (39). Chromium formed a golden yellow complex with
Tropolone on heating on a water bath; the colored moiety was extracted in CHCl3.
The complex exhibited maximum absorbance at 400 nm. Spectrophotometric
determination of chromium (III) with phenathrenequinone monoxime into molten
naphthalene has also been reported (40). The method obeyed Beer’s law at 410 nm
in the concentration range 6.5 – 65.0 g of chromium in 10 mL of
dimethylformanide. The molar absorptivity and Sandell’s sensitivity were 5.24 x 103
mol L-1cm-1 and 0.0099 µg cm-2, respectively.
Chromium was determined in oriented and unoriented single ruby crystals by Dodd
and co-workers by spectrophotometric method (45). It makes use of the absorption
coefficient for the blue and green bands and for the red lines at 3000K. The
coefficients were based on concentration data obtained by 3 independent methods.
29
(vi) Industrial waste water:
Chromium (III) has been determined in industrial waste water by its reaction with
xylenol orange (47). Chromium has been determined as Cr (VI) in sample solutions
at pH 1-2 or by reacting with oxalic acid (at 1000C, 2 min). Chromium has been
determined in Cr-Sulphate solution, Cr- sulphate - Al - sulphate - mixture; glucose
reduced tanning solution, waste water, rare earth containing solutions with
satisfactory results (48).
Metabromocarboxy azo-m has been used for the determination of Cr (III). The
absorption maximum is at 680 nm and the molar absorptivity is 1.2 x 105L Cm-1 mole-
1
. Bear’s law is obeyed in the range 1-25µg/25 ml. Chromium has been determined
in water samples with satisfactory results (49).
Chan and Co-workers have extracted chromium (III) as the chelate with
acetylacetone into methyl isobutyl ketones and aspirated the extract to the flame for
absorbance measurements. The detection limit is 0.015 ppm chromium with the
acetylene -air flame, and the sensitivity was enhanced to twice that obtained with an
aquous solution. The method has been applied to chromium in sea water (53).
30
Methods for the determination of chromium have been classified and their
applications in the determinations of chromium in alloys and ores are reviewed (55).
32
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Geb. Lebensmittelunters.
16. Liyoufen; yang, Fenglin; Xiangtan Daxue Zirane kexue Xuebao. (1), 86-91,(1986).
17. Burns D. Throbum; Chimpalee, D. Hagan, PF Anal. Chim. Acta, 198. 293-6 (Eng) (1987)
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20. J. G. Edward, S. J. Haswell, C. J. Jackson; Heavy Met. Enurion. Int. Conf. 5 , 2, 460-2 (Eng.),
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21. H. A. Flaschlka, a. J. Barnarch Jr. Chelates in Analytical Chemistry; Vol-4, 1st Edn, Marcel
Dekker, INC. New York; (1972)
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33
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61. C.F.Wang.,C.J.Chin. S.K. Luo & L.C.Men. Anal. Chim. Acta 389,257,(1999).
35
1.2.2 MANGANESE
Symbol: - Mn; At Wt: - 55 At No: - 25;
Electronic configuration: [Ar] 3d5 4s2
Occurrence
Manganese makes up about 1000 ppm of the Earth's crust. Soil contains 7–
9000 ppm of manganese with an average of 440 ppm. Seawater has only 10
ppm manganese and the atmosphere contains 0.01 µg/m3. Manganese occurs
principally as pyrolusite (MnO2), braunite, (Mn2+Mn3+6)(SiO12), psilomelane
(Ba,H2O)2 Mn5O10, and to a lesser extent as rhodochrosite (MnCO3).
The most important manganese ore is pyrolusite (MnO2). Other economically
important manganese ores usually show a close spatial relation to the iron
ores. Land-based resources are large but irregularly distributed. About 80% of the
known world manganese resources are found in South Africa. Other important
manganese deposits are in Ukraine, Australia, India, China, Gabon and Brazil. In
1978, 500 billion tons of manganese nodules were estimated to exist on the ocean
floor. Attempts to find economically viable methods of harvesting manganese
nodules were abandoned in the 1970s.
In South Africa most identified deposits are located near Hotazel in the Northern
Cape Province with an estimated 15 billion tons in 2011. In 2011 South Africa was
the world's largest producer of manganese producing 3.4 million tons.
Physical properties
Manganese is a silvery-gray metal that resembles iron. It is hard and very brittle,
difficult to fuse, but easy to oxidize. Manganese metal and its common ions
are paramagnetic. Manganese tarnishes slowly in air and "rusts" like iron, in water
containing dissolved oxygen.
The most common oxidation states of manganese are +2, +3, +4, +6 and +7, though
oxidation states from −3 to +7 are observed. Mn2+ often competes with Mg2+ in
biological systems. Manganese compounds where manganese is in oxidation state
+7, which are restricted to the unstable oxide Mn2O7 and compounds of the intensely
purple permanganate anion MnO4− are powerful oxidizing agents. Compounds with
oxidation states +5 (blue) and +6 (green) are strong oxidizing agents and are
vulnerable to disproportionation.
The most stable oxidation state for manganese is +2, which has a pale pink color,
and many manganese (II) compounds are known, such as manganese (II)
sulfate (MnSO4) and manganese (II) chloride (MnCl2). This oxidation state is also
36
seen in the mineral rhodochrosite (manganese (II) carbonate). The +2 oxidation of
Mn results from removal of the two 4s electrons, leaving a "high spin" ion in which all
five of the 3d orbital’s contain a single electron. Absorption of visible light by this ion
is accomplished only by a spin-forbidden transition in which one of the d electrons
must pair with another, to give the atom a change in spin of two units. The
unlikeliness of such a transition is seen in the uniformly pale and almost colorless
nature of Mn (II) compounds relative to other oxidation states of manganese.
The +3 oxidation state is known in compounds like manganese(III) acetate, but these
are quite powerful oxidizing agents and also prone to disproportionation in solution to
manganese(II) and manganese(IV). Solid compounds of manganese (III) are
characterized by their preference for distorted octahedral coordination due to
the Jahn-Teller effect and its strong purple-red color. The oxidation state +5 can be
obtained if manganese dioxide is dissolved in molten sodium nitrite. Manganese (VI)
salts can also be produced by dissolving Mn compounds, such as manganese
dioxide, in molten alkali while exposed to air. Permanganate (+7 oxidation state)
compounds are purple, and can give glass a violet color. Potassium permanganate,
sodium permanganate and barium permanganate are all potent oxidizers. Potassium
permanganate, also called Condi’s crystals, is a commonly used
laboratory reagent because of its oxidizing properties. Solutions of potassium
permanganate were among the first stains and fixatives to be used in the preparation
of biological cells and tissues for electron microscopy
Manganese has no satisfactory substitute in its major applications, which are related
to metallurgical alloy use in minor applications. Zinc and sometimes vanadium are
viable substitutes. Manganese is essential for iron and steel production because of
its sulfur-fixing, deoxidizing, and alloying properties. Steelmaking including its iron
making component, has accounted for most manganese demand. Among a variety
of other uses, manganese is a key component of low-cost stainless
steel formulations.
Small amounts of manganese improve the workability of steel at high temperatures,
because it forms a high-melting sulfide and therefore prevents the formation of a
liquid iron sulfide at the grain boundaries. If the manganese content reaches 4%, the
embrittlement of the steel becomes a dominant feature. The embrittlement
decreases at higher manganese concentrations and reaches an acceptable level at
8%. Steel containing 8 to 15% of manganese can have a high tensile strength of up
to 863 MPa. Steel with 12% manganese was used for British steel helmets. This
steel composition was discovered in 1882 by Robert Hadfield and is still known
as Hadfield steel.
The second large application for manganese is as an alloying agent for aluminium.
Aluminium with a manganese content of roughly 1.5% has an increased resistance
against corrosion due to the formation of grains absorbing impurities which would
37
lead to galvanic corrosion. The corrosion-resistant aluminium alloys 3004 and 3104
with a manganese content of 0.8 to 1.5% are the alloys used for most of
the beverage cans. The second large application for manganese is as an alloying
agent for aluminium. Aluminium with a manganese content of roughly 1.5% has an
increased resistance against corrosion due to the formation of grains absorbing
impurities which would lead to galvanic corrosion. The corrosion-resistant aluminium
alloys 3004 and 3104 with a manganese content of 0.8 to 1.5% are the alloys used
for most of the beverage cans
38
concentration of dissolved manganese in natural waters ranges from 10 to 10,000 µg
dm3 where as tap water contains greater than 1 mg dm3. Aromatic amines, azo dyes,
oxime, porphyrins and other reagents have been used for the colorimetric
determination of manganese. Manganese can be determined by spectrophotometry
with previous oxidation of Mn (II) using 3, 3’, 5, 5’ – tetra methyl Benzedrine as a
chromogenic reagent (19).Spectrophotometric determination of Mn in water samples
by bismuthate oxidation method is possible. This method is employed for Mn
determination in ground water of Shillong City (20).
39
References:
1. Deb K K & Mishra R K, J Indian Chem soc, 55(3), 289 (1978).
10. Burns D T, Harriott M & Barakal S A, Fresenius J Anal Chem, 343(6), 488 (1992).
13. Indian Journal of Chemical Technology, Vol-8, May-2001, P.P. 200-203 (2001).
14. F. Salinas, M. Jimenez-Arrabal & M. C. Nahedero Analytical Letters, Vol-16, Issue 17-18,
P.P. 1449-1455,(1983).
17. Dejene Ayele & B.S. Chandravanshi Analytical Letters, Volume -23, Issue-9, Pages 1729-
1741,(1990).
18. Tatiana. D. Saint Pierre, Roledao R. U. De Queiroz, Ivan G. De Souza and Jose A.
Gomes Neto J. Braz. Chem. Soc. Vol-9, No. 2, (1998).
21. F. Rehman, Samya Mairaj, International Journal of Chem Tech Research, Vol. 5, No. 4,
P.P. 1609 – 1614,(2000).
23. Patel N.B.K. Desai K.K., Asian Journal of Chemistry, 16(2), 1076-80 (2004).
24. Dave J.A., Shah S.S., Asian Journal of Chemistry, 20, 4141, (2008).
40
25. Shukla J. R, Shah S.S., International Journal of Chemistry Tech Research, 1(4), 868-
872,(2009).
28. P Saifulla khan; P Raveendra Reddy; International journal of chemical and analytical
science, 2011 2(10), 1215-1218, (2011).
41
1.2.3 IRON-Fe
Symbol: - Fe; At Wt: - 56. At No: - 26;
Electronic configuration: [Ar].3d6 4s 2
Occurrence
Iron is a chemical element with symbol Fe (from Latin: ferrum) and atomic
number 26. It is a metal in the first transition series. It is by mass the most common
element on Earth, forming much of Earth's outer and inner core. It is the fourth most
common element in the Earth's crust. Its abundance in rocky planets like earth is due
to its plenty of production by fusion in high-mass stars.
Metallic or native iron is rarely found on the surface of the earth because it tends to
oxidize, but its oxides are known and represent the primary ores. While it makes up
about 5% of the Earth's crust, both the earth's inner and outer core are believed to
consist largely of an iron-nickel alloy constituting 35% of the mass of the earth as a
whole. The main sources are the hematite (Fe2O3), magnetite (Fe3O4), limonite (FeO
(OH) nH2O), ilmenite (FeTiO3), siderite (FeCO3), and pyrites (FeS2). Most of the iron
in the crust is found combined with oxygen as iron oxide minerals such
as hematite (Fe2O3) and magnetite (Fe3O4). Large deposits of iron are found
in banded iron formations. These geological formations are a type of rock consisting
of repeated thin layers of iron oxides alternating with bands of iron-
poor shale and chert. The banded iron formations were laid down in the time
between 3,700 million years ago and 1,800 million years ago.
Physical properties
The mechanical properties of iron and its alloys can be evaluated using a variety of
tests, including the Brinell test, Rockwell test and the Vickers hardness test. The
data on iron is so consistent that it is often used to calibrate measurements or to
compare tests. However, the mechanical properties of iron are significantly affected
by the sample's purity. Pure research-purpose single crystals of iron are actually
softer than aluminum, and the purest industrially produced iron (99.99%) has a
hardness of 20–30 Brinell. An increase in the carbon content of the iron will initially
cause a significant corresponding increase in the iron's hardness and tensile
strength. Maximum hardness of 65 RC is achieved with 0.6% carbon content,
although this produces a metal with a low tensile strength.
Because of its significance for planetary cores, the physical properties of iron at high
pressures and temperatures have also been studied extensively. The form of iron
that is stable under standard conditions can be subjected to pressures up to ca.
15 GPA before transforming into a high-pressure form.
42
ELECTRONIC CONFIGURATION AND OXIDATION STATES
Like other group 8 elements, iron exists in a wide range of oxidation states, −2 to +6,
although +2 and +3 are the most common. Elemental iron occurs in meteoroids and
other low oxygen environments, but is reactive to oxygen and water. Fresh iron
surfaces appear lustrous silvery-gray, but oxidize in normal air to give hydrated iron
oxides, commonly known as rust. Unlike many other metals which
form passivating oxide layers, iron oxides occupy more volume than the metal and
thus flake off, exposing fresh surfaces for corrosion.
43
References
1. I. H. Hashmi, i. Arain and M. Hanif Menon J. Chem. Soc. Pak. Vol.3, No. 4, (1981).
14. Yamakato D., Hirqoka S. and Hikawa M. Bunseki Kagaku 30: 626 (1981).
15. Patil V. R. Kharatand R. B. Deshmukh B. K. J. Inorg, Nucl. Chem 43: 3397 (1981).
16. Novova D. and Stoyanov K. Anal. Chim. Acta. 138. 321 (1982).
19. Lal K and Malhotra S. R., J. Ind. Chem. Soc. 60: 308 (1983).
21. Malik A. K. and Rao A. L., ind. J. Chem., 329A : 829 (1983).
25. Sarkar P. Karia P.K. and Muzumdar S. K., Ind. J. Chem. Soc., 26:987 (1987).
27. Rao D. M. Reddy K. H. Reddy D. V. And Shrikrishnadevarya Ind. J. Chem. Sec A (1989).
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28. Rama S. Lokhande, Sushama M. Lele and Poonam P. Shevde Oriental journal of
Chemistry, Vol-27, No (3); PP-1249-1252. (2011).
29. Singh RB, Garg BS, and Singh RP, Talanta, 26(2): 525-526. (1979).
30. Karthikeyan J. Naik PP., Shetty AN, Environ Monit, Assess, 176(1-4): 419-26. (2011).
31. Amer SM, El-sahatry YS, Metwally FH, Younes KM, Spectrophotometric study of
complexes with copper (II) and Iron (II), I agric food Chem., 53(14) : 5492-5498.(2005).
32. Lingayat, SK, Development of New Spectrophotometric method for the Determination of
Some Metal ions from Transition Metals, Ph.D. Thesis, University of Mumbai (2006).
33. Bhaskare CK, Kawatkar SG, Extractive photometric simultaneous determination of Iron
(II) and copper (II) with Syn-Phenyl- -pyridyl ketoxime and analysis of ferrites, Talanta,
22(2): 189-193, (1975).
35. Lokhande RS, Makhijani Mamta and Barhate VD, Indian J. Chem, 15(1): 535-537, (2003).
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113-117, (1998).
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45
1.2.4 Nickel-Ni
Symbol: - Ni; At Wt: - 58.7 At No: - 28
Electronic configuration: [Ar] 3d8 4s 2
Occurrence
Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-
white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals
and is hard and ductile.It is found in the minerals pentlandite (NiS), Pyrrhoite [(Fe,
Ni) S], and garnierite (Ni, Mg) 6(OH) 6Si4O11.H2O). Nickel is also present in certain iron
meteorites. Nickel is reactive enough with oxygen. Native nickel is always found in
combination with iron.
Physical properties
Nickel is a silvery-white metal with a slight golden tinge that takes a high polish. It
has magnetic property at or near room temperature like the others being
iron, cobalt and gadolinium. Its Curie temperature is 355 °C (671 °F), meaning that
bulk nickel is non-magnetic above this temperature. The unit cell of nickel is a face
centered cube with the lattice parameter of 0.352 nm, giving an atomic radius of
0.124 nm. This crystal structure is stable to pressures of at least 70 GPA. Nickel
belongs to the transition metals and is hard and ductile.
The nickel atom has two electron configurations, [Ar] 3d8 4s2 and [Ar] 3d9 4s1, which
are very close in energy – the symbol [Ar] refers to the argon-like core structure.
There is some disagreement as to which should be considered the lowest energy
configuration. Chemistry textbooks quote the electron configuration of nickel as [Ar]
4s2 3d8, or equivalently as [Ar] 3d8 4s2. This configuration agrees with the Madelung
energy ordering rule, which predicts that 4s is filled before 3d. It is supported by the
experimental fact that the lowest energy state of the nickel atom is a 3d8 4s 2 energy
level, specifically the 3d8(3F) 4s 2 3F, J = 4 level.
However, each of these configurations in fact gives rise to a set of states of different
energies. The two sets of energies overlap, and the average energy of states having
configuration [Ar] 3d9 4s 1 is in fact lower than the average energy of states having
configuration [Ar] 3d8 4s 2. For this reason, the research literature on atomic
calculations quotes the ground state configuration of nickel as [Ar] 3d9 4s 1.
A Simple and rapid spectrophotometric method for the determination of Ni has been
described by R. S. Lokhande and co-workers. In this method Ni forms a red colored
complex with –methylisonit rosoacetophenonehydrazone (1).Nickel is reported to
46
react with 4-benzyl-1 piperazine glyoxime (BPGH) and forms yellow complex which
is extracted into carbon tetrachloride. This method is applied for determining Ni in
steel and other practical samples (2).
47
References
1. R. S. Lokhande and A. S. Jaywant, Asian journal of Chemistry Vol. 11, No. 2 , 684-
686(1999).
2. Macit, M; Bati, H; Bati, B; Turkish Journal of Chemistry issue: 1, Vol: 24, pages: 81-8,
(2000).
3. H. C. Gandhi and K. K. Desai, Asian Journal of Chemistry Vol. 15, No. 1, 549 –
551(2003).
4. Bhat N. G., Sreekumar NV & Nambiar CHR Indian Journal of Chemical Society Vol. 80,
No. 10, pp. 939 – 940,(2003).
7. K. Hussain Reddy, N.B.L. Prasad T. Sreenivasulu Reddy, Talanta, Volume – 59, Issue –
3, Page – 425 – 433(2003).
10. Dipak J. Garole and A. D. Sawant Journal of Scientific & Industrial Research Vol – 64, pp-
581- 584(2005).
48
1.3 THE LIGANDS - PYRIDIINE DICARBOXYLIC ACIDS:
Pyridine dicarboxylic acids are known Ligands. The first pyridine carboxylic acid was
obtained in the course of the studies of the odoriferous constituents of Musk from the
Perfume gland of the musk deer.
Schinz, Ruzica, Geyer and Prelogn isolated an optically active base, C6H25N, D
+174 , max 267 nm which was named muscopyridine. The prolong oxidation of
0
There are five isomers of pyridine carboxylic acids. The oxidation of quinoline and
substituted quinoline with different regents in presence of catalyst yield different
pyridine carboxylic acids.
Properties:
Pyridine dicarboxylic acids are good complexing agents. Pyridine 2,3-, 2,4-, 2,5-, 2,6-
, 3,4-, 3,5- dicarboxylic acids exhibit various co-ordination modes. Pyridine 2, 6-
49
dicarboxylic acid can act as partly or fully deprotonated and shows diverse
coordination modes. 2, 6 pyridinedicarboxylic acid is found to be suitable ligand as it
is well known versatile N, O chelator in coordination chemistry due to its diverse
coordination modes (1-5). It is also reported that this ligand is used to develop more
effective anti HIV agents (6-8). Pyridine dicarboxylic acids are found in the metabolic
pathways of animals and they are used for the transport and scavenging of metal
ions by the body. Pyridine 2, 6 dicarboxylic acid is reported to be present in bacillus
spores, which is responsible for high thermal and UV stability of Bacillus spores (9).
Pyridine dicarboxylic acid has important biological function in the metabolism such
as enzyme inhibitor (10), plant preservative (11), and food sanitizer (12). These
properties have attracted the interest of scientist not only in the field of coordination
chemistry but also in inorganic and bioorganic chemistry. Europium aquoion form
chelate complexes with pyridine 2, 6 – dicarboxylic acid (8). The structure of the
complex is given as.
-
3
O O
O
O C C O-
-
N C O
3+
Eu
N
O N O- C
-
O C C O
O
O
The 1:2 complexes of copper (II) and Zinc (II) with pyridine 2, 6 – dicarboxylic acid
has been reported (13). These complexes have distorted octahedral geometries.
OH O
C O O C
N Cu N H 2O
C O O C
OH O
(1)
OH O
C O O C
N Zn N
C O O C
O
OH
(2)
The complexes of Cobalt (II), nickel (II), rhodium (II) and rhodium (III) has been
synthesized and their spectral and magnetic properties been studied (14). Nickel is
reported forming 1:2 complex i.e. Ni (dpCH) 2 3H2O. Cobalt forms 1:1 complex i.e.
50
Co (dpc) 3H2O which is six coordinate and contain co-ordinate water. Anhydrous
polymeric [Co-(dpc)] n has also been reported (14). Rhodium (II) and rhodium (III)
forms Rh (dpc).3H2O and Na [Rh (dpc) 2].2H2O respectively. Another study reports
the dimeric complexes of Ni and Co with pyridine 2, 6 di-carboxylic acid. The
structure of these complexes has been determined by single crystal x-ray
crystallography (15). These dimeric complexes have been reported to have hexa
coordinated environment with two different type of donor atoms i.e. nitrogen and
oxygen (15). Manganese (II) has been reported to form a binuclear complex i.e.
hexaaquabis (Pyridine – 2, 6 – dicarboxylato) dimanganese (II) complex (16). Each
Mn (II) ion is coordinated by three oxygen atoms and one Nitrogen atom from the
pyridine 2, 6 dicarboxylate ligand and by three water oxygen atoms. Each
manganese possesses distorted pentagonal bipyramidal coordination.
The complex formation studies of large number of cations are reported. Mixed ligand
complexes of Nickel (II) and Cadmium (II) with Pyridine 2, 6 dicarboxylic acid have
been studied potentiometrically (18). Lanthanum, Dysprosium and Gadolinium (La,
Dy, and Gd) reacts with 2, 6 pyridine dicarboxylic acid in aqueous alkaline solution to
give Ln (pdc) (HPdc) m.H2O. The thermal dehydration of these lanthanum
compounds have been studied (19). The study of complex formation of Dysprosium
(III) and pyridine 2, 6 dicarboxylic acid has been reported (20). Electron Spin
Resonance studies of complexes of silver (I) and copper (II) with pyridine 2, 6
dicarboxylic acid have been reported (21). The complex of copper with pyridine 2, 3-
dicarboxylic acid i.e. [Cu (2, 3- pydcH) 2] has been reported (22). It is a chain
polymer. Two ligand occupy the equatorial plane of each tetragonally elongated Cu+2
coordination sphere, chelating through the pyridine nitrogen and one oxygen of the
deprotonated 2- carboxylic acid group, the axial positions are occupied by long
bonds to a 3-carboxylic acid oxygen of adjacent Cu (2, 3 PydcH)2 repeat unit. The
coordination polymer of Mn with pyridine 2, 3 dicarboxylate has been synthesized
and crystal structure has been proposed based on the experimental data (23).
According to this report Mn+2 ion is coordinated in a distorted octahedral environment
by the O atoms of two water molecules, one N and one O atoms of the chelating
pyridine 2, 3- dicarboxylate (PDC) dianion, and two axial bridging carboxylate O
atoms from two adjacent PDC ligands(23).
The complexes of the type M (H-Quin) 2. 2H2O (M = Mn, Co, Ni and Zn) where H2 –
Qin =Quinolinic acid i.e. Pyridine 2, 3dicarboxylic acid have been prepared and
characterized (24). All these reported complexes have octahedral distorted structure.
The nickel atom in Ni (H-Quin) 2.2H2O is octahedrally coordinated by two nitrogen
atoms and two oxygen atoms belonging to the two H-Quin- anions and two trans-
51
aqua molecules (24). The structure of Ni (II) with Quinolinic acid can be represented
as,
H
H
N
N
O
Ni
O=
C
C O C=0
O= H
H C=
O- O
HO O
O
H
The crystal structure of Ni (II) with pyridine 2, 5 dicarboxylic acid has been reported
(25). This compound i.e. [Ni (C7H3No4) (H2O) 4].H2O is synthesized by reaction of Ni
(II) with pyridine-2, 5-dicarboxylic acid and piperazine in water. The compound
contains a six coordinate Ni (II) ion which has a distorted octahedral structure.
Following is the reported structure.
O
H 2O
C O
N
H 2O
O
Ni
H 2O OH2
OH2
The complex Mn (H-Quin) 2.2H2O has been formulated as [Mn (H2O) 6] [Mn (H-Quin)
- 2+
3] 2. The octahedral [Mn (H-Quin)3] and, [Mn(H2O)6] units lie on different three fold
axis.(24) Lanthanide (III) quinolinate complexes have been prepared and reported
and evidence is presented which indicates that these complexes may be six-
coordinated(26). A calcium (II) complex with pyridine 2, 3- dicarboxylate (Quinolinic
acid) has been synthesized and crystal structure has been reported (27).The
complexes of uranium (IV) with quinolinic acid has been synthesized and reported
(28).Two types of complexes of cadmium with quinolinic acid has been synthesized
and reported (29). They are [Cd ( 2,3 pydcH)3][Cd(H2O)6] and [Cd (2, 3 pydc)
(H2O)3]n. The chromium (III) – quinolinato complexes [Cr(quinH)3]+3
[Cr(QuinH)2(H2O)2]+ and [Cr(quinH)(H2O)4]2+ have been obtained and characterized
in solution(30).
The structure of some Cu (I), Ag (II) and Cu (II) compounds with quinolinic acid have
been established based on X-ray crystallographic studies (31-33). In each case, quin
is bonded as a monoanion through pyridine nitrogen and carboxyl ate oxygen atoms
forming the 5-membered chelate ring. The same coordination mode is postulated for
other quin-complexes with Cr (III), Cd (II), Fe (II) (34, 37) though no structural studies
52
were conducted. The spectrophotometric evaluation of iron (II) quinolinic acid
complex (1:2) metal ligand system has been reported (38). Quinolinic acid i.e.
pyridine 2, 3 dicarboxylic acid forms a 1:2 complex with Fe (II) at 5.9 pH which
absorbs at 420 nm. The complex of cobalt with quinolinic acid has been synthesized
and structure has been reported (39).The following structure of hydrated cobalt (II)
complex of quinolinic acid has been reported (39).
H H
O O
N O H
O C C
O
Co
OH C C=O
O O N
O
H H
The crystal structure of copper with pyridine 2, 3 dicarboxylic acid has been
investigated (40). Following structure has been reported.
The complex formed by Mn (II) and pyridine 2, 5 dicarboxylic acid has been
synthesized and characterized by elemental analysis, IR, electronic spectra, thermo
gravimetric analysis and x-ray diffraction techniques (41). The Mn (II) ion is
coordinated by two water molecules and two chelated Pyridine 2, 5 dicarboxylic
ligands. Water molecules coordinate with Mn (II) ion in cis mode.
H H
H O
O H
O N H
Mn
N O
C
O
C O C C
O
H O O O
53
Conductometric and Potentiometric methods of quantitative determination of
Aluminum (III), Indium (III), and Lanthanum (III) with pyridine 2, 6 dicarboxylic acids
have been reported (42). Uranium (VI) and Vanadium (III) forms complexes with
pyridine 2, 6 dicarboxylic acid which has been used for quantitative determination by
conductometric and Potentiometric methods (43). Nickel (II) has been determined
spectrophotometrically with pyridine 2, 6 dicarboxylic acid. Ni (II) forms 1:2 colored
complexes which are stable and independent of pH and its max is at 1025 m (44).
Iron (II) has been determined spectrophotometrically with pyridine 2, 6 dicarboxylic
acid. Fe (II) forms 1:2 complexes at pH 5.2 and maximum absorption is at 510 nm
(45). Cr (III) forms 1: 2 complexes with pyridine 2, 6 dicarboxylate in aq. Solution.
The stability constants of the metals as Ba2+, Ca2+, Cd2+, Ce3+, Co2+, Cu2+, Dy3+, Er3+,
Eu3+, Fe2+, Fe3+, Gd3+, Ho3+, La3+, Lu3+, Hg2+, Mg2+, Mn2+, Nd3+, Ni 2+, Pb2+, Pr2+, Pr3+,
Sm3+, Sr2+, Tb3+, Tm3+, Y3+, Yb3+ and Zn2+ with pyridine 2, 6 dicarboxylic acid have
been reported.
A further literature survey showed that the solution studies of Ni (II), Mn (II) and Cr
(III) with pyridine 2, 3 dicarboxylic acid has not been reported. The solution studies of
Fe (II) and Ni (II) with pyridine 2, 5 dicarboxylic acid has also not been reported.
Similarly solution studies of Mn (II) and Cr (III) with pyridine 2, 6 dicarboxylic acids
has not been reported.
Therefore a study of complexation of these metals with pyridine dicarboxylic acids
and their application for quantitative determination has been carried out. The
complexes are synthesized and an FTIR study has also been carried out.
54
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