Archives of Petroleum and Environmental Biotechnology

Volume 2017; Issue 01
7 Aug 2017

Coordination Commpounds ofHexaaqua Bisbezol-1,2,4,5-TetracarbonateDiiron (II) withaLayerd-Porous Structure, To Reduce Viscosity Crude Oil

Research Article

NurullayevValiHanaqa*1, UsubaliyevBeybalaTaji2,TaghiyevDilqamBabir3, AliyevaFB4,Munshiyeva MK5,Safarova PS6

1*Technical Sciences State Oil Company of the Azerbaijan Republic (SOKAR) Quality ControlDepartment28,Khodzhalaave,Republic of Azerbaijan
2Geotechnological Problems of Oil, Gas and Chemistry, Scientific Research Institute, Azerbaijan State Oil Academy, Republic of Azerbaijan
3,4,5,6Institute of Catalysis and Inorganic Chemistry, M.FNaghiyevNational Academy of Sciences of Azerbaijan, Republic of Azerbaijan

*Corresponding author:Nurullayev ValiHanaqa, Technical Sciences State Oil Company of the Azerbaijan Republic (SOKAR) Engineer of Quality ControlDepartment28,Khodzhalaave,Baku,Az1025, Republic of  Azerbaijan.Tel: +9945210979; Fax+ 6616542693;E-Mail: veliehet1973@mail.ru

Received Date: 26January, 2017; Accepted Date: 20 February, 2017; Published Date:27February,2017

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Abstract

Introduction

References

Figures

Tables

Suggested Citation

Abstract

 

The complex compounds of Diiron (II) bisbenzoll,2,4,5 Tetra carbonate were  synthesized for the first time with porous structure. This article presents the results of X-ray diffraction, elemental and IR analyzes of spectroscopic derivatographic complex compound of 1,2,4,5-bis benzene tetra carbonate of Diiron (II). By means of the indicated physical-chemical analyzes the individual coordination form of carboxyl groups, chemical formula and unit cell parameters of the complex compound have been identified. Also, the process of thermal degradation of the studied complex has been studied. It was revealed that the compound after losing six molecules of water is resistant until the temperature 300°С.In all likelihood coordinately related the water molecules form intermolecular hydrogen bonds both with oxygen of the carboxyl groups, and among themselvesin all likelihood coordinately related the water molecules form intermolecular hydrogen bonds both with oxygen of the carboxyl groups, and among themselves. Here molecules of coordination water in the different layers play an active role in this interaction. Thus, a two-dimensional structure of a complex compound by means of the hydrogen bonds is transformed into 3D structure.

 

Keywords:A Layered Porous Structure; Complex Compound;Chemical Formula; Pyromellitic Acid;Thermal Decomposition; IR Spectrum

Introduction

 

Considerable interest to phthalates and terephthalates of various metals emerging recently is determined with their layered structure and the possibility of wide application. The layered structure of phthalates and terephthalates allows their use as molecular sieves and adsorbents, and particularly copper terephthalate is used for absorption of N2, Ar, Xe [1]. Tetraphtalate of zinc, calcium, and tin is used respectively as an activator of vulcanization in the rubber production, as a lubricant to prevent adhesion of rubber to technological fibers [2] as the capacitive dielectric [3] and terephthalate of ruthenium exhibits semiconductor properties [4,5]. Also, we have synthesized a number of non-bonded compounds on the basis of the complexes of terephthalates of copper, cadmium (II) obtained in a slightly acid medium with formic acid, [6],

 

Phthalates and terephthalates of cadmium, nickel (II) with acetic acid and phthalates and terephthalates of cadmium, cobalt, nickel and zinc (II) obtained in a basic medium (pH> 8.5) with acetic acid due to its layered structures [7-10].The complex compounds of copper (II) has been synthesized with benzene of 1,2,4,5-tetracarboxylic acid (pyromellitic acid) and crystal-crystalline structure [11] have been decrypted (Figure 1). As can be seen from the structure, it also has a polymer- laminate structure with pores of a certain size which are available for self-assembly. That is, a number of non-bonded compounds with various organic molecules of various sizes and geometries can be obtained on its bases. For this purpose, on the basis of pyromellitic acid we obtained a number of complex compounds of various metals [12,13]. This work presents the results of the synthesis, physical-chemical and structural studies of the chemical complex of hexaquabisbenzene1,2,4,5-tetracarbonate of Diiron (II). Preliminary studies have shown that they improve the rheological properties of heavy oil.

 

  1. Experimental Section

 

The elemental composition of the obtained compound was determined by gas chromatography on an analyzer CHN30E Carlo ERBA. The metal content was calculated from the weight loss curve on quantity of oxide obtained after heating on derivatographic up to 8000С. X-ray diffraction analysis was performed on the device CommanderSampleID (Coupled Two Theta/Theta) WL 1.54060.   IR spectra were recorded on a device SPECORD-MBO in the area of 400-4000 sm-1.Derivatograms ware recorded on a derivategraph NETZSCH STA 449F3STA449F3A-0836-M (Range 21/10.0(К/min)/800).

 

  • Synthesis of the compound

 

The starting materials were C6H2(COO)4, (pyromellitic acid), FeCl2, NaHCO3 of qualification XCH (GOST 3759-75). Complex compound was obtained by reacting pyromellitic acid sodium salt with iron chloride (II) in a weakly acidic medium. During the reaction, polycrystalline powder of the complex falls abundantly. Polycrystalline powder is heated up to boiling and kept boiling for 15 minutes. Then it was filtered while it was hot and washed for several times with distilled water. First it was dried on a filter paper at a room temperature and then in a drying oven at 500С. The chemical formula of the complex connections was established on the basis of X-ray diffraction, elemental, TGA and IR spectroscopic analysis.

 

  • Discussion of Results

 

X-ray analysis: (Figure 2) shows the X-ray of the complex compound.

 

As seen from the radiographs, this compound is highly crystalline and has a high symmetry, as the peaks are located in all corners.The parameters of the elementary cell of the complex compound have been determined with indexing

Diffraction patterns of: a = 10,1,b= 18,24,c=11,76Å.Comparison of the unit cell parameters of the current complex compound with the parameters of the known complexes

 

a = 9,679(5),b= 18,17(2),c=12,18(1)Å[11],

a = 10,68,b = 19,11,c = 11,28 Å,    [12],

a = 9,78,b = 19,7,c = 11,76 Å,    [13],

a = 10,10,b = 18,24,c = 11,76 Å,   [current complex],

 

It showed that they are isomorphic, but not isostructural.The resulting complex compound is studied with IR spectroscopy methods and differential thermal elemental analysis.

 

Elemental analysis: Elemental analysis results are presented in (Table 1) According to the results of the elemental analysis of the obtained compound, the following chemical formula can be written – Fe2(C6H2(COO)4) (H2O) 6.

 

  • Thermal decomposition

 

Thermogravigramma of the complex compound of the iron (II) is shown in (Figure 3).Decomposition of the complex compound of hex aquabisbenzene 1,2,4,5 tetra carbonate of Diiron (II) begins at 1100С in the temperature range of 110 – 2050С and is accompanied by a shallow, but a clear endothermic with the peak at 1500С and corresponds to the removal of six molecules of water.As it is seen from the thermo grams of the complex compound (Figure 3), all six water molecules leave the crystal lattice at one stage and are focal points, since their removal temperature is too high.Experimental mass loss value is 24% (calculated 22,98%).

 

Removal of the water molecules with one precise endothermic effect and a sufficiently high temperature (110 – 2050С) shows that they are coordinated and quite strongly linked to the central atom. Its zinc analogue has 4 moles of water which are removed step by step (2mol, 1.5mol and 0,5mol) [13].  Intermediate anhydrous complex is stable up to 3000С which is extremely rare for the complex compounds. At 3000С gradually at 300 – 5300С temperature range decomposition of anhydrous complex and parching of an organic residue with a single precise endothermic effect with a maximum 4400С takes place. Here the weight loss is experimentally 53% (calculated 53,19%). Since on TG curve after the full decomposition of the complex compound, a slight increase in weight and a good agreement between the experimental and theoretical values is observed, the oxidation of ion (Fe2+) is due to atmospheric oxygen. As the final product FeO is left. Below, a diagram of a solid phase transformation of the complex compound is given:

 

 

Basic thermo graphic data of the complex compound are shown in (Table 2) Thus, the results of thermogravimetric studies showed that the investigated complex has a chemical formula of Fe2(C6H2(COO)4)(H2O)6which is consistent with the formula obtained by elemental analysis.

 

  • IR spectroscopic study

 

IR spectroscopic study also shows the frequencies at 3600-3200 sm-1, in particular at 3416 sm-1 which refers to the asymmetric and symmetric vibrations of OH for the water coordination[14](Figure 4). The absorption bands at 1667, 1586 (νa) and 1458, 1376 sm-1s) refer to the carboxyl groups of pyromellitic acid anion [15]. Significance of difference of the values Δ(νa– νs) is respectively 209 and 210 cm-1and it is in good agreement with the values of monodentate complexes and show that all four carboxyl groups bound to the central atom as in the complex [11].Thus, the central atom is five coordinated. The coordination of the iron (II) includes two oxygen atoms of two carboxylic groups of two different anions and three oxygen atoms of three water molecules.

 

The coordination polyhedron is a pyramid.   Estimated schematic structure of the complex compound along the axis [11] is shown in (Figure 5). In all likelihood coordinately related the water molecules form intermolecular hydrogen bonds both with oxygen of the carboxyl groups, and among themselves.

 

  1. Conclusions

 

In the crystal, the layers are interconnected with one another also by the hydrogen bonds, since the unit cell parameter (a) which is perpendicular to the layers; slightly (0,42Å) differs from the parameter (s) of the known complex [11]. Here molecules of coordination water in the different layers play an active role in this interaction. As the unit cell parameter (a) slightly (0,07Å) differs from the parameter (c) of the known complex, we assume that the layers are slightly displaced relative to each other.

 

Acknowledgements

 

Thus, a two-dimensional structure of a complex compound by means of the hydrogen bonds is transformed into 3D structure. This work was supported by the Science Development Fund under the President of Azerbaijan Republic – Grant № EİF / GAM-3-2014-6 (21) -24/09/4.Farbod M., Batvandi M.R., Fabrication and Size Control of Ag Nanoparticles, Iranaian Journal of Physics Research, 12: 77-83 (2012).

References

 

  1. Moci W, Inoue F, Yoshida K ((1977)Synthesis of New Adsorbent Copper (II) Terephthalates.ChemLett 12:1219-1220.
  2. Grossman RT, McKaneFWIr (1988)Einsatz von Terephthalaten in Kautschukmischungen . Gumi, Fasern Kunst7:
  3. Grossman RT, Tanno DMUS (1992) 235.
  4. Grossman RT, Tanno DMUS (1992)162: 557.
  5. Grossman RT, Tanno DMUS (1991) 888.
  6. Usubaliyev BT, Ganbarov DM, TomuyevaA Sh(2012) Chemistry and Chemical technology 2: 104-110.
  7. Ganbarov DM, TomuyevaA Sh, Usubaliyev BT (2009) Chemistry and Chemical technology3: 3-11.
  8. Usubaliyev BT, TomuyevaA Sh, Munshiyeva MK (2013)Journal of general chemistry7: 1181.
  9. Usubaliyev BT, Ganbarov DM, Tomuyeva ASh (2013)Newsletter of Azerb Engineer Academy 2:100-114.
  10. Usubaliyev BT, Shabanov AL, TomuyevaA Sh(2014)Preparation of non-valence compounds of zinc(II) with 1,2- and 1,4-benzenedicarboxylic acids via self-assembly.Journal of general chemistry7:1183.
  11. Usubaliyev BT, Shnulin AN, MamedovKh S (1982) Coordination chemistry11:1532.
  12. Usubaliyev BT, MunshiyevaMK,Nurullayev VH, AlievaF, Safarova PS, et al. (2016) Synthesis, physical – and structure-chemical research of coordinating compounds of diaquo-1,2,4,5-benzoltetracarbonat dicopper (II), Bull. Env Pharmacol Life Sci5:12-17.
  13. Usubaliyev BT, Nurullayev VH, Aliyeva FB(2016)Synthesis and structure-chemical research of coordination compounds of tetraaqua bisbenzol-1,2,4,5-tetracarboksilat dizinc (II), Bull Env Pharmacol Life Sci5:10-16.
  14. Bellami (1971) “New data on IR spectra of complex molecules”. Mir Moscov.
  15. Nakamoto K(1991) “IR spectra and KR spectra of non-organic and coordinating compounds” MirMoscov.
Figures

 

Figure 1:The crystal line structure of the complex compound – [Cu2(C6H2(COO)4(H2O)8](H2O)2

 

 

Figure 2: XRD of complex compound of iron (II).

 

Figure 3:Thermogram of complex compound of iron (II).

Figure 4:  IR spectra of complex compound of iron (II).

Figure 5:Alleged schematic structure of the complex.

Tables

 

Found, % Formula Calculated, %
H C Fe   Fe C H
3,028 25,582 23,780 Fe2C10H14O14 23,769 25,561 3,003

 

Table 1: The results of elemental analysis of synthesized complex

 

Compounds Тendo,0С Тecdo,0С Тekzo,0С, Тekzo,0С Weight loss
Found% Calculated%
Fe2(C6H2(COO)4)·6H2O

-6H2O

Anion acid

FeO

 

110-205

 

 

150

 

 

300-530

 

 

440

 

23,0

51,5

25,5

 

22,98

49,79

27,23

 

Table 2: Basic thermographic parameters of the complex compound.

Suggested Citation

 

Citation:ValiHanaqa N,BeybalaTaji U, Dilqam Babir T, Aliyeva FB, Munshiyeva MK, et al.(2017)Coordination Commpounds ofHexaaqua Bisbezol-1,2,4,5-TetracarbonateDiiron (II) with a Layerd-Porous Structure, To Reduce Viscosity Crude Oil.Arch Petro Environ Biotechnol 2017: APEB-107.

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