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A Detailed Study of Transition Metal Complexes of A Schiff Base With Its Physicochemical Properties by Using An Electrochemical Method

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A Detailed Study of Transition Metal Complexes of A Schiff Base With Its Physicochemical Properties by Using An Electrochemical Method

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 86

Research Article
A detailed study of Transition Metal Complexes of a Schiff base with its Physico-
chemical properties by using an electrochemical method
*
Abhishek Ghara, Dr. Abhik Si, Mritunjoy Majumder, Anindya Bagchi , Anusree Raha, Prosenjit
Mukherjee, Monit Pal, Ranajoy Kr. Saha, Souvik Basu
Netaji Subhas Chandra Bose Institute of Pharmacy, West Bengal, India

Received: 7 June 2017 Revised: 2 July 2017 Accepted: 9 July 2017


Abstract
Background: Activities of metal ions in biology have stimulated the development of metal based therapeutics. It has
been found that biologically active compounds became more effective and bacteriostatic upon chelation with metal
ions. Objective: The present work deals with the synthesis of metal (Cu and Zn) complexes derived from a novel Schiff
base drug synthesized from urea and salicylaldehyde and its physico-chemical analysis was carried out to find out
ligand- metal ratio of this complex in solution. Material and methods: For the determination of complexing nature of
these complexes “Monovariation method (Mole ratio method/ Yoe-Jones Method)” have been used to ascertain the
ligand-metal ratio in the complex. The stability constant of the formed complexes was calculated by molar conductance
measurement using Modified Job's method (Method of Continuous Variations). The analysis was carried out by using
conductometry. To confirm metal-ligand ratio, conductometric titrations was been carried out at room temperature
using analytical grade metal salts. Results and conclusion: Titrations were carried out with “systronics conductivity-
meter” using dip type conductivity cell having cell constant 1 at room temperature. Data after the analysis showed the
formation of 1:1 [M:L] ratio in the case of Cu ion and 1:3 [M:L] in the case Zn ion. The coordination behavior of the
metal ions towards to the investigated Schiff base takes place through –C=N and –OH groups.
Keywords: Yoe-Jones Method, Conductometry, Modified Job's method, Chelation, Metal ions.

Introduction as copper, zinc etc. They are all hard, with high melting and
Long before the chemist S. M. Jorgensen (1837-1914) started boiling points. They conduct heat and electricity well, form
his extensive studies on the synthesis of complex compounds in alloys with one another and with other metallic elements.
Many of them are highly electropositive to dissolve in
which metal halides and other salts could give compounds with
neutral molecules it was known that many of these compounds mineral acids, although a few are noble i.e. have low
could easily be formed in aqueous solutions. The recognition of electrode potentials and hence are unaffected by simple
acids. Many of them exhibit variable valency, and their ions
the true nature of complexes originated with Alfred Werner
(1866-1914), followed by the ideas of G. N. Lewis and N. V. and compounds are coloured (Cotton and Wilkinson, 1980).
Sidgwick, who proposed that the chemical bond requires the The intense colour of metal chelates is due to charge transfer
transitions. This is simply the movement of electrons from
sharing of an electron pair. This led to the concept that a neutral
molecule with an electron donor, Lewis base can donate these the metal ion to the ligand or vice versa. Such transitions
electrons to a metal ion or an electron acceptor Lewis acid. include promotion of electrons from levels in the ligand or
from a σ bonding orbital to the unoccupied orbital of the
The d-block elements are elements which have partly filled d-
metal ion or promotion of σ-bonded electrons to unoccupied
shell in many of their commonly occurring oxidation states such
orbital of the ligand (Christian, 1970).
The Schiff base ligands and their metal complexes have
*Address for Corresponding Author:
Anindya Bagchi specific importance in the field of coordination chemistry.
Assistant Professor As the present work deals with the complexes of Schiff base
Netaji Subhas Chandra Bose Institute of Pharmacy, West Bengal, India ligands, it is mandatory to include a brief general discussion
Email id: [email protected]. on the chemistry of Schiff bases and their metal complexes.
Mobile No: +91-9330954315 Hugo Schiff, a German chemist, isolated (Schiff, 1864) the

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 87

first condensed product of amines with carbonyl compounds, concentration of the metal is kept constant and the
which was referred as Schiff base as the compounds containing concentration of the ligand is varied under similar
an Azomethine group (-CH=N-). condition. A plot is prepared by conductance as a function
of the ratio of moles of ligand against the moles of the metal.
This plot expected to give straight line from the origin to the
point where equivalent amounts of the constituents are
present; the curve will then become horizontal if only one
Where “R” may be an aliphatic or aromatic group. Schiff's bases complex of high stability is formed. The corresponding
of aliphatic aldehydes are relatively unstable and are readily point at the molar ratio axis to each intersecting point gives
polymerizable (Campbell et al., 1944; Hine and Yeh, 1967; directly the ligand to metal ion ratio in each complex.
Savich et al., 1956). While those of aromatic aldehyde having an Modified Job's method (Method of Continuous
effective conjugation system are relatively more stable (Tazoki Variations)
and Miyano, 1959; Robertson, 1960; Brewster, 1924; Munir et
The modification of the Job's (Job, 1928) continuous
al., 1985). Schiff bases are generally bi or tri- dentate ligands
variation method performed by Vesburge and Cooper
capable of forming very stable complexes with many transition
(Vesburge and Cooper, 1941) was applied to find the
metals. In Medicinal chemistry Schiff's base has versatile
stoichiometric and formation constant of the complex. The
medicinal use (Brand and Berg, 1943; Dane et al.,1962; Sheehan
case of co-ordination may be described by:
and Grenda, 1962).
mM + nL = MmLn
Previously a considerable interest has been focused on the
complexing property of bi, tri and tetradentate Schiff base A series of solutions are prepared in which the sum of total
ligands having oxygen-nitrogen, oxygen-sulphur, nitrogen- concentration of M and L is kept constant but their
sulphur and oxygen-nitrogen-sulphur as potential donor sites proportions are continuously varied. The conductance of
(Etting, 1840). The Schiff bases are considered as useful the series is plotted against the mole fraction of the ligand.
chelating agents when a suitable functional groups like –OH, - The ratio of the stoichiometric coefficients is determined
SH, or -NO2 etc. are present sufficiently close to the azomethine from the mole fraction at the point of intersection formed by
group so as to form five or six membered chelating ring upon extrapolation of the two sides of the triangle.
reaction with the metal ion. Most of the cases for the stability of Conductometric titration (Bagchi et al., 2016)
the complexes have centred on the ligand properties and not on The electrical current through a chemical cell is carried out
those of the metal ion (Irving and Willams, 1953). by the ionic species in the solution conductometrically. The
Such a Schiff base and its complexes has been synthesized and ease with which current is conducted through a solution
used in the present work which is made from urea and (under the influence of potential difference applied across
salicylaldehyde: two electrodes) is mainly depends upon the concentrations
and kind of ions in the solution. If two suitable electrodes
are present in a solution and potential difference is applied
across those electrodes then current will flow through the
solution. During progress of a conductometric titration
changes in the conductivity of the solution usually occur
and at the end point involving neutralization or
precipitation reaction the conductivity of the solution will
be minimum. The equivalence point may be located
graphically by plotting the change in conductance as a
function of the volume of titrant added. The present account
details deals with the synthesis of metal complexes (Cu &
Figure 1: Structure of ligand (Schiff base)
Zn) derived from a Schiff base drug synthesized from urea
Material and methods and salicylaldehyde and their physico-chemical analysis
Monovariation method (Mole ratio method/Yoe-Jones was carried out to find out ligand- metal ratio of these
method) complexes in solution by using conductometric method.
This method was introduced by Yoe and Jones (Yoe and Jones, Calibration of conductivity meter
1944). Number of solutions were prepared in which the total A Systronics model 306 CONDUCTIVITY METER with

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 88

Figure 2: Estimated structure of Bis-(2-hydroxy-N-benzyl) Urate

Conductivity Cell and a simple weight machine from EAGLE same amount of ethanolic solution of the metal salts (0.01
and a BOROSILICATATE GLASS was used. Conductance mol); Cu-acetate (1.99 g), Zn- acetate (2.19 g). If the
reading was noted which having the unit called Siemens. chelates did not isolate, few drops of ammonium hydroxide
were added to adjust the pH = 8. The reaction mixture was
Synthesis of Schiff Base compound
refluxed with stirring for 3 h and then filtered, collected.
Urea (SRL, India 1gm, 0.02 M) was dissolved in 1ml of double The chelates were dried in desiccators over anhydrous
distilled water and cooled to 0º C in ice bath. Salicylaldehyde CaCl2 under vacuum. (Yield: Cu-acetate: 75%, Zn-acetate:
(Merck, India, 1.2 gm, 0.01M) was taken separately in 1ml 76%).
alcohol and cooled to 0º C. After that Salicylaldehyde was added
Conductometric titrations for detection of Metal-
to urea solution in 100 ml conical flask slowly with stirring at
Ligand ratio (Monovariant method) (Sengupta, 1966)
room temperature. The solution was again stirred for half an hour
at room temperature (20º C) in a magnetic stirrer with the Solution of drug (Schiff's Base) having strength 0.01M was
addition of 4 drops of NaOH (10%), and then allowed to stand for prepared with water in 100ml. Similarly, 0.01 M of metal
half an hour. Soon after that 2ml water-alcohol (1:1) was added to salts (Cupric acetate & Zinc acetate) was prepared and
the reaction mixture and was place in ice bath for one hour. suitably diluted as and when required. Ligand solution was
Yellow precipitate obtained after addition of sufficient amount of taken in a beaker and this was titrated conductometrically
against 0.01M metal salt solution taken in a burette.
10% NaOH and was filtered, washed in cold alcohol and re-
Conductance was recorded after every addition of 0.5ml of
crystallized in alcohol. The compound (yield 68%) was dried
metal salt solution with constant stirring at constant
over vacuum. The structure of the compound has been
temperature. Volume corrections were applied as:
determined by UV, IR MASS and NMR spectrophotometric
studies which has been previously established (Bagchi et al., Conductance= {(V+v)/V}*(Observed Conductance)
2015).The proposed chemical name of this compound is Bis-(2- Where, V=initial volume of ligand solution, v=volume of
hydroxy-N-benzyl) Urate. metal solution added.
Preparation of chelates The correction presupposes that the conductivity is a linear
function of dilution. Results were plotted in the form of a
The chelates under investigation were prepared by mixing 30 ml
graph between corrected conductance and volume of metal
ethanolic solution of the Schiff base (2.68 g; 0.01 mol) with the
salts.

Figure 3: Proposed Structures of Schiff's Base Chelate.

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 89

Modified Job's Method of continuous variation (Carradona Table 1. For Cupric Acetate salt with Schiff base (ligand)
and Lippard, 1988) for determining composition and stability
S. Volume of metal Observed Corrected
constant of complex salt added (ml) Conductance Conductance
No.
(µS) (µS)
Equimolar solutions of ligand and metal solutions were prepared
1 0 81 81
and three series C1, C2, C3 of solutions were made. In set C1
2 1 82 90.2
metal salt solution was filled with volume 0.0ml to 12.0ml and
3 2 81.9 98.28
total volume was made to 12.0ml in each. Similarly, in C2 ligand
4 3 81.6 106.08
solution was filled and set C3 was prepared by mixing metal salt
5 4 81.2 113.68
solution from 0.0ml to 12.0ml and ligand solution from 12.0ml to
6 5 80.8 121.2
0.0ml. Conductance was recorded for each solution. Δ
7 6 80 128
Conductance was calculated as “C1+C2-C3” (Huhey,
1973).Graphs was plotted between corrected conductance and 8 7 79.4 134.98

mole metal-ligand ratio. The composition and stability constants 9 8 79 142.2

were determined from the equivalence point in the graph 10 9 78.6 149.34

(Longmann, 1959). 11 10 78 156

12 11 79.1 166.11
In the present work the study was carried out using Schiff base
13 12 79.1 174.02
made of urea and salicylaldehyde as ligand and Cu (II) and Zn
(II) as metal salts. 14 13 80.9 186.07
15 14 82.1 197.04
Turner Anderson Method for determination of stability
16 15 83.7 209.25
constant
17 16 85.3 221.78
Turner and Anderson (Anderson, 1980) have modified Job's 88.6 239.22
18 17
method and have successfully used for determination of stability
19 18 90 252
constant. By plotting a continuous variation curve for a given
20 19 91 263.9
range of compositions and then repeating the procedure for more
21 20 93 279
dilute solutions. If the initial concentrations of the metallic ions
and ligands are 'a' and 'b' respectively, then

Where, K = Stability Constant


X = Concentration of the complex
It is assumed that Beer's Law is obeyed, i.e. the optical
density of the solution is proportional to the concentration of the
complex in the given range. If, therefore, any two solutions on
the two curves have the same optical density, as shown in the Figure 4. Conductometric titration of Cu ion and ligand by
graph a1, a2 and b1, b2 represent the concentrations of the metal using observed conductance
and the ligand respectively on the two curves, then:

Where, the subscripts 1 and 2 refer to the reagent concentrations.


Thus “K” be calculated by solving the equation.
Results and discussion
Conductometric titration for detection of Metal-Ligand
ratio (Monovariant method)
Concentration of metal= 0.01M, Concentration of ligand=
Figure 5. Conductometric titration of Cu ion and ligand by
0.01M
using corrected conductance

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 90

Figure 4 and 5. Conductometric method to determine metal :


ligand ratio (Metal: Cupric acetate salt)
Determination of metal-ligand ratio (Cu: Schiff base)
V1S1= V2S2
Where, V1 = Initial volume of ligand
V2 = Volume of metal added
S1 = Strength of ligand
S2 = Strength of complex

Figure 6. Conductometric titration of Zn ion and ligand by


using observed conductance

So that the metal ligand ratio is 0.01: 0.01 = 1: 1.

Concentration of metal= 0.01M, Concentration of ligand=


0.01M.

Table 2: For Zinc Acetate salt with Schiff base (ligand)

Serial Volume of metal Observed Corrected


No. salt added (ml) Conductance (µS) Conductance (µS)

1 0 81 81
2 1 82.4 90.64 Figure 7. Conductometric titration of Zn ion and ligand by
using corrected conductance
3 2 82.2 98.64
4 3 81.1 105.43 Determination of metal-ligand ratio (Zn: Schiff base)
5 4 84 117.6 V1 S1= V2 S2
6 5 84 126
Where, V1 = Initial volume of ligand
7 6 87 139.2
8 7 89.7 152.49 V2 = Volume of metal added
9 8 90 162 S1 = Strength of ligand
10 9 92 174.8
S2 = Strength of complex
11 10 94 188
12 11 96 201.6
13 12 98 215.6
14 13 100 230
15 14 102 244.8
16 15 105 262.5
17 16 107 278.2
18 17 109 294.3 So that the metal ligand ratio is 0.01: 0.03 = 1:3.
19 18 111 310.8
Modified Job's Method of continuous variation for
20 19 113 327.7
determining composition and stability constant of
21 20 117 351 complex

Figure 6 and 7 Conductometric method to determine metal: Concentration of metal= 0.01M, Concentration of
ligand ratio (Metal: Zinc acetate salt) ligand= 0.01M

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 91

Table 3: Conductance of Schiff base (ligand) and Cupric acetate Concentration of metal= 0.01M, Concentration of
ligand= 0.01M
Serial Ratio M:S S:L M:L ΔConductance Corrected
No. (C1) (C2) (C3) (C1+C2-C3) Conductance
(µS) (µS)

1 00:12 2.39 80.5 80.7 2.19 2.19


2 01:11 4.84 80.8 81.4 4.24 4.664
3 02:10 11.8 80 81.2 10.6 12.72
4 03:09 14.9 78.4 81.7 11.6 15.08
5 04:08 21.1 77.6 83 15.7 21.98
6 05:07 26 77.2 84.5 18.7 28.05
7 06:06 31.5 76.2 86.2 21.5 34.4
8 07:05 30.3 74.5 87.1 17.7 30.09 Figure 9. Conductometric estimation of composition of
complex of Schiff base (ligand) and Zn salt by using
9 08:04 34.8 74 89.5 17.7 31.86
observed conductance
10 09:03 36 71.5 90 17.1 29.25
Turner Anderson Method for determination of stability
11 10:02 40.8 71.1 91 16.9 30.98
constant
12 11:01 41.5 69.7 92 16.6 31.81
Concentration of metal= 0.01M, Concentration of
13 12:00 44 69.2 94 16 32
ligand= 0.01M
Table 5: Conductance of Schiff base (ligand) and cupric
acetate

Serial Ratio M:S S:L M:L ΔConductance Corrected


No. (C1) (C2) (C3) (C1+C2-C3) Conductance
(µS) (µS)

1 00:12 2.39 80.5 80.7 2.19 2.19


2 01:11 4.84 80.8 81.4 4.24 4.664
3 02:10 11.8 80 81.2 10.6 12.72
4 03:09 14.9 78.4 81.7 11.6 15.08
Figure 8. Conductometric estimation of composition of complex
5 04:08 21.1 77.6 83 15.7 21.98
of Schiff base (ligand) and Cu salt by using observed
6 05:07 26 77.2 84.5 18.7 28.05
conductance
7 06:06 31.5 76.2 86.2 21.5 34.4
Table 4: Conductance of Schiff base (ligand) and Zinc acetate 07:05 30.3 74.5 87.1 17.7 30.09
8
9 08:04 34.8 74 89.5 17.7 31.86
Serial Ratio M:S S:L M:L ΔConductance Corrected
No. (C1) (C2) (C3) (C1+C2-C3) Conductance (µS) 10 09:03 36 71.5 90 17.1 29.25
(µS) 11 10:02 40.8 71.1 91 16.9 30.98

1 00:12 2.71 80.5 80.7 2.51 2.51 12 11:01 41.5 69.7 92 16.6 31.81
2 01:11 6.58 80.8 81.3 6.08 6.688 13 12:00 44 69.2 94 16 32
3 02:10 13.2 80 81.9 11.3 13.56
4 03:09 18 78.4 81.9 14.5 18.85
Concentration of metal= 0.005M, Concentration of
5 04:08 24.8 77.6 89.4 13 18.2
05:07 29.7 77.2 93 13 19.5
ligand= 0.005M
6
7 06:06 32.7 76.2 96 12.9 20.64
8 07:05 37.5 74.5 101 11 18.7
9 08:04 41.5 74 103 10.5 18.9
10 09:03 45.7 72.6 107 10.3 19.57
11 10:02 51.5 71.1 110 10.2 20.4
12 11:01 56.4 69.7 113 10.1 21.21
13 12:00 59.3 69.2 116 10 22

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 92

Table 6: Conductance of Schiff base (ligand) and Cupric acetate From equation (ii),
Value of x comes out to be x = 0.00115
Serial Ratio M:S S:L M:L ΔConductance Corrected Thus from equation (i)
No. (C1) (C2) (C3) (C1+C2-C3) Conductance K = 14.6828*103
(µS) (µS) logK = 4.1668
Thus free energy change,
1 00:12 3.6 48.6 28.9 23.3 23.3
ΔG= -2.303 RT log K
2 01:11 5.7 48.5 28.9 25.3 27.83
ΔG= -2.303 * 8.314 * 273 * 4.1668
3 02:10 8.22 47.7 29 26.92 32.304 ΔG= -21780.5709 Kcal/mol
4 03:09 10.3 46.7 29.1 27.9 36.27 Concentration of metal= 0.01M, Concentration of
5 04:08 13 45.7 29.2 29.5 41.3 ligand= 0.01M
6 05:07 15.4 45.2 29.3 31.3 46.95 Table 7: Conductance of Schiff base (ligand) and Zinc
acetate
7 06:06 18.2 44.3 27.8 34.7 55.52
Serial Ratio M:S S:L M:L ΔConductance Corrected
8 07:05 19.9 43.5 29.2 34.2 58.14
No. (C1) (C2) (C3) Conductance
(C1+C2-C3)
9 08:04 22.6 42.7 31.2 34.1 61.38 (µS)
(µS)
10 09:03 24.3 42 32.3 34 64.6 1 00:12 2.71 80.5 80.7 2.51 2.51

11 10:02 26.7 41.2 34 33.9 67.8 2 01:11 6.58 80.8 81.3 6.08 6.688

12 11:01 29.5 40.6 36.4 33.7 70.77 3 02:10 13.2 80 81.9 11.3 13.56

12:00 31.5 40 38 33.5 73.7 4 03:09 18 78.4 81.9 14.5 18.85


13
5 04:08 24.8 77.6 89.4 13 18.2
6 05:07 29.7 77.2 93 13 19.5
7 06:06 32.7 76.2 96 12.9 20.64
8 07:05 37.5 74.5 101 11 18.7
9 08:04 41.5 74 103 10.5 18.9
10 09:03 45.7 72.6 107 10.3 19.57
11 10:02 51.5 71.1 110 10.2 20.4
12 11:01 56.4 69.7 113 10.1 21.21
13 12:00 59.3 69.2 116 10 22

Figure 10. Stability complex of Cu ion by using corrected Concentration of metal= 0.005M, Concentration of
conductance of 0.01M & 0.005M ligand= 0.005M
Stability constant calculation of Cu ion Table 8: Conductance of Schiff base (ligand) and Zinc
acetate
………..(i) Serial Ratio M:S S:L M:L ΔConductance Corrected
No. (C1) (C2) (C3) (C1+C2-C3) Conductance
Where, K= Stability constant (µS)
(µS)
x = Concentration of complex 1 00:12 1.93 48.6 27.5 23.03 23.03
a = Initial concentration of metal 2 01:11 5.23 48.5 30 23.73 26.103
3 02:10 8.3 47.7 30.8 25.2 30.24
b = Initial concentration of ligand
4 03:09 10.8 46.7 31.7 25.8 33.54
If, therefore, any two solutions on the two curves have the same
5 04:08 13.2 45.7 33.2 25.7 35.98
optical density, as shown in the graph a1, a2 and b1, b2 represent the
6 05:07 15.5 45.2 35.1 25.6 38.4
concentrations of the metal and the ligand respectively on the
7 06:06 17.1 44.3 36 25.4 40.64
two curves, then:
8 07:05 20.4 43.5 38.6 25.3 43.01
9 08:04 22.2 42.7 39.8 25.1 45.18

………..(ii) 10 09:03 24.3 42 41.3 25 47.5

From Figure 7, 11 10:02 26.6 41.2 42.9 24.9 49.8

a1= (0.01*6)/12 = 0.005, b1 = (0.01*6)/12 = 0.005 12 11:01 28.4 40.6 44.3 24.7 51.87

a2 = (0.005*7)/12 = 0.00291, b2 = (0.005*5)/12 = 0.00208 13 12:00 30 40 45.5 24.5 53.9

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Asian Journal of Pharmacy and Pharmacology 2017; 3(3): 86-94 93

stability constant of the complex and the free energy


change. The value of free energy change is negative
showing the feasibility of complex formation. After
determining the metal-ligand ratio, the stability constant
and free energy changes, the complex was synthesized. Also
it can be concluded that 0.01M is carrying the standard
conc. for optimal complex formation.
Acknowledgement
The authors are thankful to the respected Principal Sir, Dr.
Arnab Samanta, Netaji Subhas Chandra Bose Institute of
Figure 11. Stability complex of Zn ion by using corrected Pharmacy, West Bengal for providing necessary facilities
conductance of 0.01M & 0.005M for the completion of research work.
Stability constant calculation of Zn ion References
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………..(i) Medicine, 1980.ACS Symposium series, American
Where, K= Stability constant Chemical Society, Washington DC.

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2016. Development and validation of a comparative
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study of standardization process between titrimetric
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If, therefore, any two solutions on the two curves have the same Journal of Recent Advances in Pharmaceutical
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curves, then: characterization of a novel schiff base. Universal
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Value of x comes out to be x = 0.00264 Photoreduction of benzophenone by amines, alcohols,
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