International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec.

2013
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

SYNTHESIS, COMPOSITIONAL AND STRUCTURAL STUDIES OF SOME

TRANSITION METALLOXALATES

Dr.Sangale Mohan Dattu

Head and Associate professor,Dept. of Chemistry,A.A.College, Manchar, Pune-410503.

INTRODUCTION:

In the experiments of Synthetic Inorganic Chemistry, the metal coordination compound

selected should be such that its preparation and analysis should be easy. The metallo-oxalates
seem to be ideal in this respect.

Our literature Survey indicates that the study of ammonium salts of metallo oxalates is
limited as compared to the potassium salts the thermal investigation of sodium and ammonium
metallodicarboxilates of metals like Mn(II),Fe(II), Fe(III), Co(II),Ni(II), Cu(II),Zn(II) and Cd(II)
with ligand oxalate has been reported1. Also study of metallo oxalates of Ni(II), Cu(II),Zn(II) has
been reported2.

Using information given in earlier reports, the study of synthesis, analysis and thermo
gravimetry of ammonium salts of metallo-oxalates of Ni(II), Mn(II), Co(II) is carried out. The
compositions have been ascertained from the analysis of metals (by titrimetry), ammonium (by
potentiometry), oxalate (by permagnometry) as well as metal and water(by TGA), from this
study we gain experience about the preparation of complex, standard titrimetric estimation of all
constituents and use of thermogravimetric analysis.

Present investigation:

1) Synthesis of Ammonium divalent metallo-oxalate by using metals- Manganese,

Cobalt and Nickel.
2) Analysis of oxalate by redox titration using titrant Potassium per magnate.

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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
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3) Estimation of metal ions by complexometry using titrant as EDTA and Eriochrome

Black-T indicator for nickel and Manganese and Xylenol Orange for Cobalt(II).
4) Estimation of Ammonium by potentiometry using titrant Sodium Hydroxide.
5) Study of magnetic properties of divalent metallooxalate.
6) Thermogravimetry.

EQUATIONS:

Synthesis of ammonium salts of metallo-oxalates.

MCl2 +2(NH4)2C2O42(NH4)2M(C2O4)2]2H2O + 2NH4Cl

Analysis of Metallo oxalates

Estimation of oxalate

Standardization of KMnO4

Na2C2O4 + H2SO4 Na2SO4 + H2C2O4

5H2C2O4 + 2KMnO4 +3H2SO4 K2SO4 +2MnSO4 +10CO2 +8H2O

Ammonium salt of metallo oxalate----(dil H2SO4) H2C2O4

5H2C2O4 +2KM NO4 +3H2SO4 K2SO4 +2MnSO4 +10CO2 +8H2O

Estimation of metal ion

Disintegration of metal complex

Metal complex

Standardization of EDTA

M2+ + In Min (where M=Zn2+)

Min + Na2C10H14N2O8 [M(C10H14N2O8)]2+ + 2H+ 2Na+ + In-

Back titration of excess (unused) EDTA with standard Zn2+ ion solution
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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

Mn+ + EDTA M(EDTA) Complex

EDTA +Zn2+Zn(EDTA) Complex

Blank titration

Zn2+ + In-(blue) ZnIn (wine red)

Zn2+ + EDTA Zn(EDTA) Complex

Estimation of NH4+

Standardization of NaOH

4NH4+ + 6HCHO (CH2)N4 +6H2O + 4H+ (reaction with HCHO)

H+ +OH- H2O (titration with NaOH)

Decomposition of metallo-oxalates

(NH4)2[M(C2O4)]2H2O (NH4)2[M(C2O4)] +2H2O

(NH4[M(C2O4)] MO +2NH3 +4CO2 +H2O

EXPREMENTAL:

Synthesis of Ammonium salts of metalo-oxalates.

Analysis of metal-oxalates.

Estimation of metal ions.

Estimation of Ammonium

Thermogravimetry

Synthesis of M(II) complexes:

Estimation of oxalate from Mn(II) complex

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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
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Result table:

Sr.no. Complex formula ml of aliquot Titration %of oxalate % of oxalate

taken reading (ml) observed expected
1 10ml 4.9 57.79 58.10
2 10ml 4.6 54.25 57.39
3 10ml 4.7 55.43 57.30

Estimation of Ni2+

Sr.no. Complex formula ml of aliquot Titration %of metal % of metal

taken reading (ml) obsrved expected

1 10ml 3.7 19.10 19.45

2 10ml 3.0 17.61 19.01
3 10ml 3.1 18.15 19.21

Estimation of Ammonium from ammonium salts of metallo oxalates:

Sr.no. Complex Amount of Titration %of NH4+ % of NH4+

formula compound taken reading (ml) observed expected

1 0.90 3.9 10.0 11.80

2 0.10l 3.6 9.21 11.70

3 0.94l 3.9 9.55 11.70

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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954

THERMOGRAVIMETRY OF AMMONIUM METALLO-OXALATES

Sr.no. Complex ml of aliquot Titration %of oxalate % of oxalate

taken reading (ml) observed expected

1 Mn 125-200 10 Loss of lattice Brownish

280-335 86.2 water black
Decomposition
2 Ni 90-150 8.83 Loss of lattice Gray color
185-325 94.8 water
Decomposition
3 Co 120-195 8.61 Loss of lattice Black residue
230-295 86.1 water CoO
decomposition

Magnetic Susceptibility:

Diamagnetic substances are repelled quickly by the magnetic field while paramagnetic
compounds are attracted by the magnetic field.

Diamagnetism is property of all forms of matter it is because of presence of closed shells of

electrons. If the substance has no unpaired electrons then the substance will tend to move away
from the strong part of the magnetic field and it is said to be diamagnetic.

Magnetic susceptibility of a diamagnetic compound is negative and is independent of field

strength and of the temperature.

Any atom or ion or molecule that has one or more unpaired electrons is paramagnetic.
Ferromagnetism arises when individual paramagnetic atom or ion are close together and the
interaction of magnetic field is constructive.

Curies Law: for most paramagnetic substances magnetic susceptibility varies inversely with
absolute temperature.

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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
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Magnetic susceptibility is the measure of force exerted by magnetic field on unit specimen.
Magnetic moment may be calculated by applying correction to measure susceptibility per mole.

M=[n(n+2)]1/2

M should be in Bohr Magnetos.

Applications of magnetic susceptibility measurements:

a. Number of unpaired electrons can be found out.

b. Physical heat of adsorption for O2 species can be obtained.

Sr.no. Complex eff observed (BM) eff expected (BM)

1 Mn 4.57 5.47
2 Ni 0 0
3 Co 2.98 3.46

Result and discussion:

The result of analysis of oxalate, metal ion and ammonium are in good agreement with the
composition 2(NH4)2M(C2O4)]2H2O (where M=Mn /Ni /Co). these compositions are similar to
those of reported metal oxalates of the metal ion under persent study. There is slight variation in
percentage of residue in three complexes than the reported residue because the rate of
decomposition of every complex at a given temperature is different.

The analysis indicate that for Mn, Ni, Co complexes water molecules are not associated with the
metal. Because the temperature at which the complex loses water was lower than 1000C, which
suggests that, the water is not co-ordinated water but lattice water.

From the magnetic susceptibility we get eff less than expected because of the square planar
geometry of the crystal field splitting parameter B larger. In the case of Co(II) it forms a dimer

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International Journal of Advanced Scientific and Technical Research Issue 3 volume 6, Nov.-Dec. 2013
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with another Co atom of complex which results in the anti Ferro magnetic coupling interactions
eff decreases from 3.7 to 2.93.

Acknowledgements:

We express our gratitude to UGC (WRO) Pune and BCUD University of pune, who have
financially supported through research projects for their kind help.

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3.Booth, H. S., Inorganic Synthesis,VOL-I (Mc_Graw Hill,New York),37(1939)

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