mechanism of the complex formation was studied. the...
TRANSCRIPT
Nitrilotriacetic acid behaves as an excellent polydentate ligand like other
amino - poly carboxylic acids. It forms stable complexes with a large
number of metal ions at low pH values (1, 2, 3, 4, 5), acting as tridentate
(6) or Tetradentate (7) ligand depending upto the nature of the metal
ions. The metal complex formation even at considerably high pH values
(8).
The absorption spectrum of the Co (II) nitrilotriacetic acid complex
was studied by Nielsch and Beltz (9). Cheng and Warmuth (10) gave a
method for the determination of cobalt in nickel alloys and steel using
NTA. Study of the asorption spectra of chromium (III) nitrilotriacetic acid
was done by Dan Boef and poeder (II). The complex Cu (II)
nitrilotriacetic acid was studied by Man Mohan et.al (12) and the log 1 =
12.96 was found. Nard (13) determined electrometrically the rate
constants of the conversion of Cu (II) ethyl glyclinate N1 diacetate to Cu
(II) - NTA. Nielsch and Boltz (14) reported the Cu (II) - nitrilotriacetic
acid complex (in slightly acidic medium) has maximum absorbance in the
range of 690-710 nm and in alkaline medium in the range of 640-648
nm. Thermodynamic study of the reaction between various bivalent
cations and NTA as a ligand have been done by Hull and Coworkers (15).
At OºC, and U = 0.1 the heat of formation of the 1:1 complexes of Mn
(II), Co (II), Ni (II), Cu (II), Ca (II) and Sn (II) with NTA were measured
calorimetrically. They also found the existence of 1:2 complex of Cu (II)
NTA.
Qian Gao (16) studied bismuth (III) – NTA complex with help of
polarography. The polarographic behaviour of Bi (III) complex with NTA
including the stability constant, thermodynamic function and the
mechanism of the complex formation was studied. The stability constants
of the B1 complex was determined by suing the equation for shift of half
wave potential of kinetic wave. Kornevet. al (17) have done
spectrophotmetric study of the complexing of Co (II) with NTA. Instability
of CoX– and CoX2
4– are 8.85 x 10-11 at 3 pH 7 - and 4.74 10–15 at pH 7
respectively. Where NTA= H3X.
Elenkova and Tsoneva (18) studied the reaction between As
(III) and nitrilotriacetic acid (NTA) was investigated
polarographically and potentiometricall. As (III), in presence of
NTA gave a diffusion controlled current proportional to the
complex concentration in the pH and variable NTA concentration
were calculated from the change of the limiting currents. The
same conditional constants were determined by potentiometric
measurements to the potential of the redox system As (V) - As
(III) NTA at varied pH.
The complex [As (OH)2 Hx–] in formed under the experimental
conditions, whose overall formation constant is log - 15.33 ± 0.15 at ionic
strength = 0.1M and 25.0 ± 0.2ºC.
Redevich (19) reported the composition of complex compounds of
Cu2+, Ni2+, Zn2+ or Co2+ and Nitrilotriacetic acid (1) in the sepration of Y
and samarium by displacement complexing chromatography on the
exchange resin KV-2 in Cu–, Ni– or Co– cycle respectively depends on the
nature of the returningion. Pitre & Chitale (20) have done a polarographic
study of the complexes of neodymium (III) with glycine. Iminiodiacetic
acid and NTA. The studies were done at 32 ± 0.1ºC and pH 2.75 ± 0.02.
The stability constants increased in the order of glycine Iminodiacetic Acid
nitrilotriacetic Acid.
Sepctrophotometic study of complexes of Zinc (II) and cadmium
(II) with nitrilotriacetic and ethylene diamine tetracetic acids were done
by Kornev et. al (21). The method used was competing reaction method
using Co+2 as indicator ion, Formation constant of complexes was
calculated.
Tannanaeva et. al (22) have studied complex formation of
Europium (III) in aquous solution (pH 5-9) containing sodium salts of
EDTA (H4A) and nitrilotriacetate (H3B) by a high resolution
spectrophotometer. 1:1:1 complex EuAB4- forms in the solution and the
log of its stability constant was 21.66.
Simple and mixed complexes of iron (III) involving NTA
(nitrilotriacetic acid) as primary ligand and a series of oxygen bonding
organic anion as secondary ligands was studied by Ramamoorthy and
manning (23). Equilibrium constants are also reported for the
corresponding simple Mln complexes.
Mananin et. al (24) applied the lrving- Rossotti technique to the
study of formation constant of the reaction (MA) - + L2– --- (MAL)2– where
HL2 = catechol, pyragallol and 2, 3 dihydroxynaphthalene, M = Cu²+, Ni²+
& Cd²+ A = Anion of NTA). A similar equatin with L3- represents co-
ordination of protocatechnic acid. The value of formation constant of
KMAL was found to be less that Kf value i.e. the formation constant value
for KML (Binary complex). This behaviour can be explained by the
difference in electrostatic repulsion experienced by L2–.
Rubin and Martell (25) presented a calculation based upon metal
ligand equilibrium, known environmental concentrations of NTA following
extensive detergent usage, and the presence of competitive metal
binding ligands and trace elements demonstrates that NTA will be present
almost completely as Ca and Mg chelates. As analogous estimation of the
completely of NTA over long periods of time caused reproducible are
without measurable effect.
Isotope exchange reactions between the chlorides of Cerium (3+),
Cobalt (3+), mercury (2+) and Zn (2+) and their complexes with
nitrilotriactic acid were studied by Nicholas et. al (26). The experiments
were performed at different temperature and acidity ranges always
keeping the reacting in solution.
Barbara and Cowarkers (27) studied the nitrilotriacetate complexes
of ion (III) . Cobalt (II), Zinc (II), and Cadmium (11) arising in ion
exchange separation of lanthanides with the use of separation of
lanthanides with the use of separators. (NH4)3 FeL2). NH2O (H3L = NTA)
[Cu (HL)] 2H2O,. H (Cu4L3] H2, M2 [Ml2]. NH2O (M = Co1, Zn1 and H4
[ZnL2]. 4th were isolated from the eluted solution of rare earth elements
in an ion exchange persons involving the non-lanthanide elements as
separators. The complexes were characterized by elements in an ion
exchange. The complexes were characterized by elemental analysis, X-
ray differactometry and electronic spectral methods.
Spectrophtometric studies of various metal nitrilotriacetic acid
complex have been made by different workers. Yoshimura and Tanmura
(28) studied the Cr (VI) - NTA complex in dimethyl furunamide as the
solvent and have there by worked out a photometric determination of the
metal. Longman and coworkers (29) studied five published methods that
describe measures for the removal of interferences. However in non of
these methods interfering metals were displaced completely from their
NTA complexes. This method was quite similar in nature in the reduction
in the colour of the zinc- zircon complex by NTA. Tabatbai et. al (30)
determined the amount of NTA in soils applying the same technique and
also by eliminating metal interferences by ion exchange separation and
using a chelating resin. NTA present in trace in tape water was
determined on the basis of quenching of the fluorescence of the gallium -
8 quinolinal complex (31).
MIXED LIGAND COMPLEXES WITH NTA
Mixed ligand complexes are those in which the donor atoms belong
to different ligand molecules. Mixed ligand complexes are frequently
formed in solution but in comparison to simple complex, these have been
only scantily studied. Knowledge of the stability constants of the
appropriate mixed complex is essential for an understanding of problems
particularly related to analytical and biological chemistry. In the recent
year the work on mixed ligands system (32) receiving considerable
attention, which can be evinced by large number of publication.
Miggal et. al (33) studied mixed complexes of cadmium with
thiourea and halide ions in water alcohol solution. They also calculated
the stability constants at 250C and detected the components of the
complexes. At a give co-ordination no. The Thiourea- bromide complexes
of cadmium are more stable than those of iodide, Which are more stable
than thiourea - cadmium complexes, whose stability in turn is slightly
greater than that of cadmium aqueous complexes. The formation of
mixed complexes does not follow statistical distribution. Studnickova et.al
(34) determined stability of mixed complexes of zinc by the extraction
method. Ternary chelates Zn A2B and Zn AB2 formed during extraction of
a zinc salt with acetylactone (HA) and 2,2' bipyridyl or 1, 10
phenonthroline (B) were studied. They showed that ZnA2B chelate has
the character of an adduct with a higher stability and extra stability than
ZnA2. They also detected the stability constant of the ternary chelates by
graphical analysis of the dependence of the zinc distribution ratio on the
equilibrium concentration of B in the aqueous phase with constant
concentration of A. Kodama and Ebine (35) carried out a
spectrophotometric study of Zn- NTA Eriochrome black T system. Jackob
; and Margerum (36) evaluated the formation constants for the system Ni
(II) - NTA - oxalic acid. Ternary system of type M - NTA - L m = Cu, Ni L
= ligands viz. Thiourea, phenyl thourea, were studied by Chidambaram
and Bhattacharya (37) and Day et. al (38), Ramamoorthy et. al (39, 40)
have examined the complexes of Fe (III) and Cu (II) with NTA as a
primary ligand and as series of oxygen bonding organic anions as
secondary ligands.
Rahmani et. al., (41) prepared compounds viz. TIL5x ( where L=
(phenyl thiourea, X = Cl, Br) and TIL5 Qx. (Where Q = 2, 2' - dipyridine,
1, 10- phenanthroline) TIL' x ( L'= Diphenyl thiourea) TIL' QX1 TIL2 11
and TIL2 Q. These compounds were characterized by IR spectra and
electrical conductance. The thiourea are N- bonded; TIL X1T1 L5I and TIL'
× are 1 : 1 electrolytes whereas in the mixed ligand complexes the halo
group is co - ordinate, giving complexes with co-ordination number of T1
of 4 of 8. Some studied on mixed ligand complexes of cobalit (III), Nickel
(II) and Zinc (II) with hydozine and oxalic acid conducted by Mishra et. al
(42). Co (N2H4)2 Xn H20 (X = SO4, oxalte) NiN2H4) SO4, 2H20 were
prepared and characterized by elemental, analytical, thermal, IR studies
and magnetic measurements. They further showed the Cobalt and Nickel
complexes were octahedral.
Mixed ligand complexes of Cadmium with thiourea and
thiocyanatate ions in aqueous alcohol solutions were studied by
Tsiplyalova and Coworkers (43). A paleographic study is 0 – 93% MeOH
(ETOH) at 250 and ionic strength 0.5 was made by them. Mixed
complexes stabilities increase in the order MeOH E+OH. They also
determined stability constants for mixed complexes and co-operation
constants and compared to statistical stability constants for mixed
complexes.
Sirkar (44) have made electrophoretic studies of Cobalt (II), Zinc
(II), beryllium (II), Uranyl (II) Chromium (III) and thorium (IV) oxalate
nitrilotriacetate complexes in solution. A new method involving the use of
paper electrophoresis (PE), was described for the study of equilibrium in
mixed ligand complex systems in solution. This technique was based
upon the movement of a spot of a metal ion under a potential field, with
the complexants added in the background electrolyte (0.1 M NaCIO4) at
pH 10.0. The concentration of one of ligand was kept constant while that
of second ligands concentration as varied. A graph of log (L) against
mobility was used to obtain information on the formation of the mixed
ligand complex and to calculate the stability constant.
Singh et. al (45) studied the system Cu (II), Zn (II), and Co (II)
glutarate - nitrilotriacetate by paper electrophoresis. Yadava et. al (46)
have done electrophoretic studies of mixed ligand complexes in solution ;
Copper (II), Nickel (II), Uranyl (II) and Thorium (IV) Tartarate
Nitrilotriacetate. Singh et. al (47) have done electrophoretic study of
Nickel (II). Uranyl (IV) and thorium (IV) glutarate nitrilotriacetate
systems.
Sirkar (48) have studied electrophoretically Copper (II) < Nickel
(I), Cobalt (II) and Uranium dioxide (II) citrate-nitrilotriacetate
complexes in solution.
Ionophoretic technique has been applied in the study of mixed
complexes (M - Nitrilotriacetate - Valinate) system by Singh et.al (49).
Gupta et. al (50) have studied the M - Nitrilotriacetate - Prolinate system
by applying ionophoretic study. Number of mixed ligand complexes
invading NTA as primary ligand and amino acids as secondary ligand was
studied by Singh et. al recently. (51, 52, 53, 54, 56, 57, 58, 59, 60).
Tiwari et al. studied mixed complexes of sulphur containing amino acid
and NTA with number of metal ions and determined stability constants(61
- 77).
The present chapter deals with the electrophoretic investigation of
dissociation constant of NTA, binary complexes of M - NTA and ternary
complexes of type M - L -NTA.
EXPERIMENTAL
• Metal ions
5.0 × 10-4M solution of Cu (II), Ni (II), Co (II) and Zn (II)
perchlorates were obtained by suitable dilution of the stock solutions.
• Medium
The medium was of strength 0.1 M. The strength of NTA was kept
at 5 × 10-3 for, binary complexes. For dissociation constant 1 × 10-2 M
NTA has used while studying the mixed complexes concentration of NTA
was used; ranging from a strength of 1 × 10-7 M-5 – 1 × 10-3 M.
PROCEDURE
• Dissociation Constant of NTA
A 10 ml solution was made containing 4 × 10-3 NTA and 0.1
perchloric acid. This was taken in the electrophoretic tube, which was in a
water thermostat (35ºC), 50 volt potential difference was imposed on the
two platinum foil electrodes emerged in cup ends of the tube. After
allowing the electrolysis for 30 minutes the contents of negative
compartment was also washed with water, which was added into the
conical flask. Then 5 ml of Fe (III) solution of appropriate concentration
was added to it. The pH of the solution was adjusted by addition of 2.0 ml
of 50% acetic acid and requisite volume of sodium acetate solution. A
pinch of KI was then added and reaction mixture was allowed to rest for 5
minutes. The liberated iodine in the solution was titrate against 1×10-2M
hypo solution by using starch indicator. These observations were taken at
different pH value of the NTA solution of electrophoretic tube. On
electrolysis the negatively charged anions of the NTA migrate from the
negative compartment towards the positive compartment resulting in the
decrease in anion concentration in the negative compartment. Hence the
decrease in the concentration of the anion in the compartment will give a
measure of speed of the negatively charged anion. The iodometric
titration described above helps in determination of the concentration of
the anion in the negative compartment Ferric ion forms a very stable
complex with anion of NTA which is incapable of liberation iodine from the
potassium iodide. Hence the difference intitre values of the ferric ion in
absence and in presence of NTA anion give the concentration of anion.
Binary complexes of M - NTA - The experimental conditions are the
same as in metal - amino acid system.
Ternary complexes of NTA
For the study of mixed complexes, of metal ions with Serine,
Homo Serine, Proline and Hydroxy Proline as primary ligand and NTA
as secondary ligand, the usual experimental procedure adopted for simple
complexation studies was modified. An appropriate reaction mixture
containing metal ion and Serine, Homo Serine, Proline and Hydroxy
Proline and 0.1 M perchloric acid is adjusted to pH 8 by adding caustic
soda. This is important because stable complexes of 1:1 composition with
all the four ligands begin to form much ahead of this pH and remain
intact even beyond this pH.
To the solution the secondary ligand concentration i.e. of NTA was
increased progressively and the electrophoretic observations were made
at every addition of the secondary ligand. Care was taken always for
maintaining the pH of the solution at pH 8.5. All the observation has been
recorded under the following condition. 10 ml of the solution as
electrolyzed in the tube under the potential difference of 50 Volts, for 30
minutes. The contents of the negative compartment was analysed for
metal ions. These observations were repeated at several concentrations
of NTA.
Experimental observations are described in various sections and
attempts have made to interpret them.
Table - 4.1.1
H+ - NTA SYSTEM
[NTA] = 4 × 10–3
pH Titrant Value pH Titrant Value
0.95 1.95 3.81 0.95
1.16 1.95 4.08 0.95
1.27 1.95 4.51 0.95
1.18 1.80 4.85 0.95
1.69 1.75 5.06 0.95
1.80 1.35 5.31 0.95
2.02 1.30 5.76 0.95
2.21 1.30 6.35 0.95
2.32 1.25 6.81 0.95
2.43 1.25 7.11 0.95
2.54 1.05 7.70 0.95
2.76 0.90 8.34 0.95
3.01 0.95 8.96 0.95
3.21 0.95 9.05 0.95
3.18 0.95 9.43 0.95
3.62 0.95 9.43 0.95
3.62 0.95 9.90 0.95
10.31 0.50
Table - 4.2.1
Cu (II) - NTA SYSTEM
[Cu (II)] = 5 × 10–5 M B.E. = 0.350
[NTA] = 1 × 10–3 M A.E. = 0.270
pH Absorbance DA
1.43 0.270 0.080
1.56 0.275 0.075
1.54 0.280 0.070
1.65 0.290 0.060
1.66 0.295 0.055
1.77 0.300 0.050
1.78 0.310 0.040
1.89 0.315 0.035
1.10 0.325 0.025
1.92 0.330 0.020
1.93 0.335 0.015
2.06 0.345 0.005
2.07 0.355 -0.005
2.18 0.360 -0.010
2.19 0.365 -0.015
2.30 0.370 -0.020
2.37 0.370 -0.020
2.46 0.370 -0.020
2.57 0.370 -0.020
3.63 0.370 -0.020
3.96 0.370 -0.020
4.25 0.375 -0.025
4.53 0.370 -0.020
4.83 0.370 -0.020
5.21 0.370 -0.020
5.62 0.370 -0.020
6.03 0.365 -0.015
6.54 0.370 -0.020
7.05 0.370 -0.020
8.58 0.370 -0.020
9.09 0.370 -0.020
9.56 0.370 -0.020
10.10 0.370 -0.020
11.40 0.370 -0.020
12.50 0.370 -0.020
Table - 4.2.2
Ni (II) - NTA SYSTEM
[Ni (II)] = 5 × 10–5 M B.E. = 0.320
[NTA] = 1 × 10–3 M A.E. = 0.260
pH Absorbance DA
1.55 0.260 0.060
1.62 0.260 0.060
1.63 0.265 0.055
1.75 0.270 0.050
1.74 0.280 0.040
1.86 0.285 0.035
1.87 0.295 0.025
1.90 0.300 0.020
1.96 0.305 0.015
2.01 0.315 0.005
2.02 0.320 0.000
2.11 0.325 0.005
2.12 0.335 0.015
2.23 0.340 -0..020
2.23 0.340 -0.020
2.36 0.340 -0.020
2.57 0.340 -0.020
3.02 0.340 -0.020
3.33 0.340 -0.020
3.65 0.340 -0.020
4.06 0.340 -0.020
6.01 0.340 -0..020
6.32 0.345 -0.025
6.83 0.340 -0.020
7.34 0.335 -0.015
7.75 0.340 -0.020
8.16 0.340 -0.020
8.67 0.340 -0.020
9.08 0.340 -0.020
9.59 0.340 -0.020
10.54 0.340 -0.020
11.06 0.340 -0.020
11.58 0.340 -0.020
12.09 0.340 -0.020
12.50 0.340 -0.020
Table - 4.2.3
Co (II) - NTA SYSTEM [Co (II)] = 5 × 10–5 M B.E. = 0.390
[NTA] = 1 × 10–3 M A.E. = 0.315
pH Absorbance DA
1.50 0.315 0.075
1.52 0.315 0.075
1.82 0.315 0.075
2.53 0.330 0.060
2.54 0.335 0.055
2.66 0.340 0.050
2.68 0.345 0.045
2.71 0.350 0.040
2.72 0.355 0.035
2.84 0.360 0.030
2.85 0.365 0.025
2.96 0.370 0.020
2.92 0.380 0.010
3.18 0.400 -0.010
3.20 0.405 -0.015
3.24 0.410 -0.020
3.52 0.410 -0.020
3.81 0.410 -0.020
4.03 0.410 -0.020
4.22 0.410 -0.020
4.46 0.410 -0.025
4.61 0.410 -0.020
4.81 0.410 -0.020
5.01 0.410 -0.015
5.34 0.410 -0.020
5.63 0.410 -0.020
5.98 0.415 -0.025
6.38 0.410 -0.020
6.61 0.410 -0.020
7.01 0.410 -0.020
7.54 0.410 -0.020
8.03 0,410 -0.015
8.57 0.410 -0.020
9.01 0.410 -0.020
11.57 0.410 -0.020
12.08 0.410 -0.020
Table - 4.2.4
Zn (II) - NTA SYSTEM [Zn (II)] = 5 × 10–5 M B.E. = 0.500
[NTA] = 1 × 10–3 M A.E. = 0.400
pH Absorbance DA
1.53 0.400 0.100
1.62 0.400 0.100
1.75 0.400 0.100
1.86 0.400 0.100
1.87 0.400 0.095
1.98 0.400 0.090
1.92 0.410 0.080
2.03 0.420 0.075
2.01 00425 0.070
2.24 0.430 0.060
2.25 0.440 0.055
2.26 0.445 0.045
2.27 0.455 Q.035
2.34 0.470 0.030
2.38 0.480 0.020
2.49 0.485 0.015
2.40 0.495 0.005
2.51 0.500 0.000
2.73 0.520 -0.020
2.81 0.520 -0.020
3.02 0.520 -0.020
3.26 0.520 -0.020
3.43 0.520 -0.020
3.78 0.520 -0.020
4.31 0.520 -0.020
4.62 0.520 -0.020
4.91 0.520 -0.020
5.34 0.525 -0.025
7.51 0.520 -0.020
8.08 0.520 -0.020
8.57 0.520 -0.020
9.06 0.520 -0.020
9.55 0.520 -0.020
10.03 0.520 -0.020
10.52 0.520 -0.020
12.56 0.520 -0.020
Table - 4.3.1
Cu (II) - SERINE-NTA SYSTEM
[Cu (II)] = 5 × 10–5 M B.E. = 0.350
[Serine] = 1 × 10–3 M A.E. = 0.350
-Log [NTA] Absorbance
DA
7.01 0.000 0.000
6.82 0.000 0.000
6.63 0.000 0.000
6.44 0.000 0.000
6.25 0.000 0.000
6.06 0.000 0.000
5.87 0.000 0.000
5.68 0.000 0.000
5.49 0.000 0.000
5.21 0.000 0.000
5.12 0.000 0.000
5.00 0.355 -0.005
4.90 0.360 -0.010
4.75 0.365 -0.0 15
1.00 0.370 -0.020
4.50 0.375 -0.025
4.33 0.380 -0.030
4.14 0.385 -0.035
4.01 0.385 -0.035
3.80 0.385 -0.035
3.62 0.385 -0.035
3.40 0.390 -0.040
3.22 0.385 -0.035
3.00 0.385 -0.035
2.82 0.385 -0.035
2.60 0.385 -0.035
2.43 0.380 -0.035
2.20 0.385 -0.035
2.03 0.385 -0.035
1.80 0.385 -0.035
1.63 0.385 -0.035
1.40 0.385 -0.035
1.23 0.385 -0.035
1.00 0.385 -0.035
Table - 4.3.2
Ni (II) - SERINE -NTA-SYSTEM
[Ni (II)] = 5 × 10–5 M B.E. = 0.320 [Serine] = 1 × 10–3 M A.E. = 0.320
-Log [NTA] Absorbance DA
7.01 0.320 0.000
6.82 0.320 0.000
6.63 0.320 0.000
6.44 0.320 0.000
6.25 0.320 0.000
6.06 0.320 0.000
5.87 0.320 0.000
5.68 0.320 0.000
5.49 0.320 0.000
5.21 0.320 0.000
5.02 0.320 0.000
4.83 0.320 0.000
4.74 0.325 -0.005
4.65 0.330 -0.010
4.46 0.335 -0.015
4.37 0.340 -0.020
4.28 0.345 -0.025
4.09 0.350 -0.030
3.91 0.350 -0.030
3.72 0.350 -0.030
3.63 0.350 -0.030
3.44 0.350 -0.030
3.25 0.355 -0.035
2.96 0.350 -0.030
2.67 0.350 -0.030
2.38 0.350 -0.030
2.09 0.345 -0.030
1.81 0.350 -0.025
1.62 0.350 -0.030
1.43 0.350 -0.030
1.24 0.350 -0.030
1.01 0.350 -0.030
Table - 4.3.3
Co (II) - SERINE -NTA-SYSTEM
[Co (II)] = 5 × 10–5 M B.E. = 0.390 [Serine] = 1 × 10–3 M
A.E. = 0.390
-Log [NTA] Absorbance DA
7.01 0.390 0.000
6.82 0.390 0.000
6.63 0.390 0.000
6.44 0.390 0.000
6.25 0.390 0.000
6.06 0.390 0.000
5.87 0.390 0.000
5.68 0.390 0.000
5.49 0.390 0.000
5.20 0.390 0.000
5.01 0.390 0.000
4.82 0.390 0.000
4.63 0.390 0.000
4.44 0.390 0.000
4.25 0.395 -0.005
4.16 0.400 -0.010
5.97 0.405 -0.015
3.88 0.410 -0.020
3.79 0.415 -0.025
3.50 0.420 -0.030
3.31 0.420 -0.030
3.22 0.420 -0.030
3.03 0.420 -0.030
2.84 0.420 -0.030
2.65 0.420 -0.030
2.46 0.420 -0.035
2.27 0.420 -0.030
2.08 0.420 -0.030
1.09 0.415 -0.025
1.60 0.420 -0.030
1.41 0.420 -0.030
1.22 0.420 -0.030
1.03 0.420 -0.030
Table - 4.3.4
Zn (II) - SERINE -NTA-SYSTEM
[Zn (II)] = 5 × 10–5 M B.E. = 0.500 [Serine] = 1 × 10–3 M A.E. = 0.500
-Log [NTA] Absorbance DA
7.01 0.500 0.000
6.82 0.500 0.000
6.63 0.500 0.000
6.44 0.500 0.000
6.25 0.500 0.000
6.06 0.500 0.000
5.87 0.500 0.000
5.68 0.500 0.000
5.49 0.500 0.000
5.20 0.500 0.000
5.02 0.500 0.000
4.84 0.500 0.000
4.66 0.500 0.000
4.48 0.500 0.000
4.22 0.505 -0.005
4.14 0.510 -0.010
4.06 0.515 -0.015
3.88 0.529 -0.020
3.70 0.525 -0.025
3.62 0.530 -0.030
3.44 0.530 -0.030
3.26 0.530 -0.030
3.08 0.530 -0.030
2.81 0.535 -0.035
2.63 0.530 -0.030
2.50 0.530 -0.030
2.35 0.530 -0.030
2.20 0.530 -0.030
1.80 0.525 -0.025
1.80 0.530 -0.030
1.60 0.530 -0.030
1.40 0.530 -0.030
1.20 0.530 -0.030
1.00 0.530 -0.030
Table - 4.4.1
Cu (II) - HOMO SERINE -NTA-SYSTEM
[Cu (II)] = 5 × 10–5 M B.E. = 0.350 [Homo Serine] = 1 × 10–3 M A.E. = 0.350
-Log [NTA] Absorbance DA
7.00 0.350 0.000
6.80 0.350 0.000
6.60 0.350 0.000
6.40 0.350 0.000
6.20 0.350 0.000
6.00 0.350 6.000
5.80 0.350 0.000
560 0.350 0.000
5.40 0.350 0.000
5.20 0.350 0.000
5.00 0.350 0.000
4.90 0.355 -0.005
4.75 0.360 -0.010
4.65 0.365 -0.015
4.50 0.370 -0.020
4.35 0.375 -0.025
4.20 0.380 -0.030
4.05 0.385 -0.035
3.90 0.390 -0.040
3.80 0.390 -0.040
3.60 0.390 -0.040
3.40 0.390 -0.040
3.20 0.390 -0.035
3.00 0.390 -0.040
2.80 0.390 -0.040
2.60 0.390 -0.040
2.40 0.390 -0.045
2.20 0.390 -0.040
2.00 0.390 -0.040
1.80 0.390 -0.040
1.60 0.390 -0.040
1.40 0.390 -0.040
1.20 0.390 -0.040
1.00 0.390 -0.040
Table - 4.4.2
Ni (II) - HOMO SERINE -NTA-SYSTEM
[Ni (II)] = 5 × 10–5 M B.E. = 0.320 [Homo Serine] = 1 × 10–3 M A.E. = 0.320
-Log [NTA] Absorbance DA
7.00 0.320 0.000
6.80 0.320 0.000
6.60 0.320 0.000
6.40 0.320 0.000
6.20 0.320 0.000
6.00 0.320 0.000
5.80 0.320 0.000
5.60 0.320 0.000
5.40 0.320 0.000
5.20 0.320 0.000
5.00 0.320 0.000
4.80 0.320 0.000
4.05 0.320 0.000
3.95 0.325 -0.005
3.80 0.330 -0.010
3.70 0.335 -0.015
3.55 0.340 -0.020
3.45 0.345 -0.025
3.30 0.350 -0.030
3.20 0.355 -0.035
3.00 0.355 -0.035
2.50 0.355 -0.035
2.50 0.355 -0.035
2.50 0.355 -0.035
2.40 0.360 -0.040
2.30 0.355 -0.035
2.15 0.355 -0.035
2.00 0.355 -0.035
1.80 0.350 -0.030
1.60 0.355 -0.035
1.40 0.355 -0.035
1.20 0.355 -0.035
1.00 0.355 -0.035
Table - 4.4.3
Co (II) - HOMO SERINE-NTA-SYSTEM
[Co (II)] = 5 × 10–5 M B.E. = 0.390 [Homo Serine] = 1 × 10–3 M
A.E. = 0.390
-Log [NTA] Absorbance DA
7.00 0.390 0.000
6.80 0.390 0.000
6.60 0.390 0.000
6.40 0.390 0.000
6.20 0.390 0.000
6.00 0.390 0.000
5.80 0.390 0.000
5.60 0.390 0.000
5.40 0.390 0.000
5.20 0.390 0.000
5.00 0.390 0.000
4.80 0.390 0.000
4.60 0.390 0.000
4.40 0.390 0.000
4.25 0.395 -0.005
4.10 0.400 -0.010
5.95 0.405 -0.015
3.80 0.410 -0.020
3.70 0.415 -0.025
3.55 0.420 -0.030
3.35 0.420 -0.035
3.20 0.420 -0.035
3.00 0.420 -0.035
2.80 0.420 -0.035
2.60 0.420 -0.030
2.40 0.425 -0.035
2.20 0.420 -0.035
2.00 0.420 -0.035
1.0O 0.430 -0.040
1.60 0.425 -0.035
1.40 0.425 -0.035
1.20 0.425 -0.035
1.00 0.425 -0.035
Table - 4.4.4
Zn (II) - HOMO SERINE-NTA-SYSTEM
[Zn (II)] = 5 × 10–5 M B.E. = 0.500 [Homo Serine] = 1 × 10–3 M
A.E. = 0.500
-Log [NTA] Absorbance DA
7.00 0.500 0.000
6.80 0.500 0.000
6.60 0.500 0.000
6.40 0.500 0.000
6.20 0.500 0.000
6.00 0.500 0.000
5.80 0.500 0.000
5.60 0.500 0.000
5.40 0.500 0.000
5.20 0.500 0.000
5.00 0.500 0.000
4.80 0.500 0.000
4.60 0.500 0.000
4.45 0.500 0.000
4.30 0.505 -0.005
4.20 0.510 -0.010
4.05 0.515 -0.015
3.90 0.520 -0.020
3.75 0.525 -0.025
3.65 0.530 -0.030
3.50 0.530 -0.030
3.30 0.530 -0.030
3.10 0.530 -0.030
2.95 0.535 -0.035
2.80 0.530 -0.030
2.60 0.530 -0.030
2.40 0.530 -0.030
2.20 0.535 -0.025
2.00 0.535 -0.030
1.80 0.535 -0.035
1.60 0.535 -0.035
1.40 0.535 -0.035
1.20 0.535 -0.035
1.00 0.535 -0.035
Table - 4.5.1
Cu (II) - PROLINE-NTA-SYSTEM
[Cu (II)] = 5 × 10–5 M B.E. = 0.350 [Proline] = 1 × 10–3 M A.E. = 0.350
-Log [NTA] Absorbance DA
7.00 0.350 0.000
6.80 0.350 0.000
6.60 0.350 0.000
6.40 0.350 0.000
6.20 0.350 0.000
6.00 0.350 0.000
5.80 0.350 0.000
5.60 0.350 0.000
5.40 0.350 0.000
5.20 0.350 0.000
4.00 0.350 0.000
4.90 0.350 0.000
4.75 0.355 -0.005
4.G5 0.360 -0.010
1.50 0.365 -0.015
4.35 0.370 -0.020
4.25 0.375 -0.025
4.15 0.380 -0.030
4.05 O.385 -0.035
3.90 0.385 -0.035
3.70 0.385 -0.035
3.50 0.385 -0.035
3.30 0.390 -0.040
3.10 0.385 -0.035
3.00 0.385 -0.035
2.65 0.385 -0.035
2.75 0.385 -0.035
2.60 0.385 -0.035
2.45 0.385 -0.035
2.35 0.385 -0,035
2.20 0.385 -0,035
1.80 0.385 -0.035
1.40 0.385 -0.035
1.00 0.385 -0.035
Table - 4.5.2
Ni (II) - PROLINE-NTA-SYSTEM
[Ni (II)] = 5 × 10–5 M B.E. = 0.320
[Proline] = 1 × 10–3 M A.E. = 0.320
-Log [NTA] Absorbance DA
7.00 0.320 0.000
6.80 0.320 0.000
6.60 0.320 0.000
6.40 0.320 0.000
6.20 0.320 0.000
6.00 0.320 0.000
5.80 0.320 0.000
5.60 0.320 0.000
5.40 0.320 0.000
5.20 0.320 0.000
5.00 0.320 0.000
4.90 0.325 -0.000
4.75 0.330 -0.005
4.65 0.335 -0.010
4.50 0.340 -0.015
4.35 0.345 -0.020
4.20 0.345 -0.025
4.00 0.345 -0.025
3.80 0.345 -0.025
3.50 0.345 -0.025
3.20 0.345 -0.025
2.90 0.350 -0.030
2.60 0.345 -0.025
2.40 0.345 -0.025
2.20 0.345 -0.025
2.00 0.350 -0.030
1.80 0.345 -0.025
1.60 0.345 -0.025
1.40 0.345 -0.025
1.20 0.345 -0.025
1.00 0.345 -0.025
Table - 4.5.3
Co (II) - PROLINE-NTA-SYSTEM
[Co (II)] = 5 × 10–5 M B.E. = 0.390
[Proline] = 1 × 10–3 M A.E. = 0.390
-Log [NTA] Absorbance DA
7.00 0.300 0.000
6.80 0.300 0.000
6.60 0.390 0.000
6.40 0.390 0.000
6.20 0.390 0.000
6.00 0.390 0.000
5.80 0.390 0.000
5.60 0.390 0.000
5.40 0.390 0.000
5.20 0.390 0.000
5.00 0.390 0.000
4.80 0.390 0.000
4.70 0.390 0.000
4.50 0.300 0.000
4.30 0.390 0.000
4.15 0.395 -0.005
4.00 0.400 -0.010
3.90 0.405 -0.015
3.75 0.410 -0.020
3.60 0.415 -0.025
3.50 0.420 -0.030
3.35 0.420 -0.030
3.20 0.420 -0.030
3.00 0.415 -0.025
2.80 0.420 -0.030
2.60 0.420 -0.030
2.30 0.425 -0.035
1.90 0.420 -0.030
1.60 0.420 -0.030
1.40 0.420 -0.030
1.20 0.420 -0.030
1.00 0.420 -0.030
Table - 4.5.4
Zn (II) - PROLINE-NTA-SYSTEM
[Zn (II)] = 5 × 10–5 M B.E. = 0.500 [Proline] = 1 × 10–3 M A.E. = 0.500
-Log [NTA] Absorbance DA
7.00 0.500 0.000
6.80 0.500 0.000
6.60 0.500 0.000
6.40 0.500 0.000
6.20 0.500 0.000
6.00 0.500 0.000
5.80 0.500 0.000
5.60 0.500 0.000
5.40 0.500 0.000
5.20 0.500 0.000
5.00 0.500 0.000
4.80 0.500 0.000
4.60 0.500 0.000
4.45 0.510 -0.005
4.35 0.515 -0.010
4.20 0.520 -0.015
4.15 0.525 -0.020
4.00 0.525 -0.025
3.85 0.525 -0.025
3.70 0.525 -0.025
3.50 0.525 -0.025
3.30 0.525 -0.025
3.15 0.525 -0.025
3.00 0.530 -0.030
2.85 0.525 -0.025
2.70 0.525 -0.025
2.55 0.525 -0.025
2.40 0.530 -0.030
2.20 0.525 -0.025
2.00 0.525 -0.025
1.80 0.525 -0.025
1.60 0.525 -0.025
1.40 0.525 -0.025
1.20 0.525 -0.025
1.00 0.525 -0.025
Table - 4.6.1
Cu (II) - HYDROXY PROLINE-NTA-SYSTEM
Cu (II)] = 5 × 10–5 M B.E. = 0.350 [Hydroxy Proline] = 1 × 10–3 M A.E. = 0.350
-Log [NTA] Absorbance DA
7.00 0.350 0.000
6.80 0.350 0.000
6.60 0.350 0.000
6.40 0.350 0.000
6.20 0.350 0.000
6.00 0.350 6.000
5.80 0.350 0.000
560 0.350 0.000
5.40 0.350 0.000
5.20 0.350 0.000
5.00 0.350 0.000
4.90 0.355 -0.005
4.75 0.360 -0.010
4.65 0.365 -0.015
4.50 0.370 -0.020
4.35 0.375 -0.025
4.20 0.380 -0.030
4.05 0.385 -0.035
3.90 0.390 -0.040
3.80 0.390 -0.040
3.60 0.390 -0.040
3.40 0.390 -0.040
3.20 0.390 -0.035
3.00 0.390 -0.040
2.80 0.390 -0.040
2.60 0.390 -0.040
2.40 0.390 -0.045
2.20 0.390 -0.040
2.00 0.390 -0.040
1.80 0.390 -0.040
1.60 0.390 -0.040
1.40 0.390 -0.040
1.20 0.390 -0.040
1.00 0.390 -0.040
Table - 4.6.2
Ni (II) - HYDROXY PROLINE-NTA-SYSTEM
[Ni (II)] = 5 × 10–5 M B.E. = 0.320 [Hydroxy Proline] = 1 × 10–3 M
A.E. = 0.320
-Log [NTA] Absorbance DA
7.00 0.320 0.000
6.80 0.320 0.000
6.60 0.320 0.000
6.40 0.320 0.000
6.20 0.320 0.000
6.00 0.320 0.000
5.80 0.320 0.000
5.60 0.320 0.000
5.40 0.320 0.000
5.20 0.320 0.000
5.00 0.320 0.000
4.85 0.320 0.000
4.75 0.325 -0.005
4.60 0.330 -0.010
4.50 0.335 -0.015
4.35 0.340 -0.020
4.25 0.345 -0.025
4.10 0.350 -0.030
4.00 0.355 -0.035
3.85 0.360 -0.040
3.70 0.360 -0.040
3.50 0.360 -0.040
3.10 0.355 -0.035
2.70 0.360 -0.040
2.40 0.360 -0.040
2.20 0.360 - 0.040
2.00 0.360 -0.040
1.80 0.360 -0.040
1.60 0.360 -0.040
1.40 0.360 -0.040
1.20 0.360 -0.040
1.00 0.360 - 0.040
Table - 4.6.3
Co (II) - HYDROXY PROLINE-NTA-SYSTEM
[Co (II)] = 5 × 10–5 M B.E. = 0.390 [Hydroxy Proline] = 1 × 10–3 M A.E. = 0.390
-Log [NTA] Absorbance DA
7.00 0.390 0.000
6.80 0.390 0.000
6.60 0.390 0.000
6.40 0.390 0.000
6.20 0.390 0.000
6.00 0.390 0.000
5.80 0.390 0.000
5.60 0.390 0.000
5.40 0.390 0.000
5.20 0.390 0.000
5.00 0.390 0.000
4.80 0.390 0.000
4.60 0.390 0.000
4.50 0.395 -0.005
4.35 0.400 -0.010
4.20 0.405 -0.015
4.10 0.410 -0.020
3.95 0.415 -0.015
3.80 0.420 -0.020
3.70 0.425 -0.035
3.55 0.425 -0.035
3.40 0.425 -0.035
3.20 0.425 -0.035
3.00 0.425 -0.030
2.80 0.425 -0.035
2.60 0.425 -0.035
2.40 0.425 -0.035
2.20 0.430 -0.040
2.00 0.425 -0.035
1.80 0.425 -0.035
1.60 0.425 -0.035
1.40 0.425 -0.035
1.20 0.425 -0.035
1.00 0.425 -0.035
Table - 4.6.4
Zn (II) - HYDROXY PROLINE-NTA-SYSTEM
[Zn (II)] = 5 × 10–5 M B.E. = 0.500
[Hydroxy Proline] = 1 × 10–3 M A.E. = 0.500
-Log [NTA] Absorbance DA
7.00 0.500 0.000
6.80 0.500 0.000
6.60 0.500 0.000
6.40 0.500 0.000
6.20 0.500 0.000
6.00 0.500 0.000
5.80 0.500 0.000
5.60 0.500 0.000
5.40 0.500 0.000
5.20 0.500 0.000
5.00 0.500 0.000
4.80 0.500 0.000
4.60 0.500 0.000
4.45 0.500 0.000
4.30 0.505 -0.005
4.20 0.510 -0.010
4.05 0.515 -0.015
3.90 0.520 -0.020
3.75 0.525 -0.025
3.65 0.530 -0.030
3.50 0.530 -0.030
3.30 0.530 -0.030
3.10 0.530 -0.030
2.95 0.535 -0.035
2.80 0.530 -0.030
2.60 0.530 -0.030
2.40 0.530 -0.030
2.20 0.525 -0.025
2.00 0.530 -0.030
1.80 0.530 -0.030
1.60 0.530 -0.030
1.40 0.530 -0.030
1.20 0.530 -0.030
1.00 0.530 -0.030
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