Thermal decomposition of 2,3,5-triphenyl tetrazolium halochromate complexes

Thermal decomposition studies of 2,3,5-triphenyl tetrazolium halochromates have been carried out upto 1000°C at a linear heating rate of 10 deg·min^?1. The complexes undergo two stage decomposition. First one corresponds to the redox decomposition of the complex along with the loss of a phenyl halide molecule and 3/2 mol of oxygen. While, the second step corresponds to the oxidation of the formazan type structure formed in the first step. The first step decomposition follows diffusion controlled reaction mechanism in a sphere governed by the equationg(α)=[1?(1?α)^1/3]². Activation energy and pre-exponential factors have been determined by Coats-Redfern model and Dixit-Ray model. Activation energy decreases as the electronegativity of the halide ion decreases.     

Thermal behaviour of benzenesulfenamides and of their chromium carbonyl complexes

Benzenesulfenamides with the formula R-S-N-(R)₂ (R=C₆H₅ andR=NC₄H₈O, C₇H₇ and C₆H₁₁) and their chromium carbonyl complexes were studied by means of TG and mass spectrometric methods. The thermal behaviour of the compounds the stabilities of free sulfenamides are lower than those observed for the corresponding chromium carbonyl complexes. Combined thermogravimetry — mass spectrometry results suggest that the fragmentation mechanism of the carbonyl complexes involves cleavage of the Cr-S and Cr-CO bonds while that of sulfenamide depends mainly on the dissociation rates of the NR₂ groups.This work was partially supported by the Departamento técnico de Investigation of the Universidad de Chile, Grant Q3280/9324.     

Thermal analysis study of some transition metal complexes by TG and DSC methods

The thermodynamic and thermal properties of [Cu(L)₂·Cl₂], [Ni(L)₂]·Cl₂, [Co(L)₂·Cl₂]; L=1,2-bis(o-aminophenoxy)ethane (BAFE), complexes have been investigated. The thermal decomposition of the complexes took place in two distinct steps in endothermic reaction up to 700°C. The activation energy E, the entropy change S ^#, enthalpy H change and Gibbs free energy change G ^# were calculated from the results of thermogravimetry analysis (TG) and heat capacity from the results of differential scanning calorimetry (DSC). It was found that the thermal stabilities and activation energies of the complexes follow the order Ni(II)>Cu(II)>Co(II) and E _Co<E _Ni<E _Cu, respectively.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal behaviour of hydrated copper(II) complexes

Dehydration steps of aquacopper(II) complexes with homogeneous and heterogeneous coordination sphere are investigated from the view point of structural changes taking place under their heating to the decomposition temperature and during the dehydration. The role of loosening of intra-and intermolecular hydrogen bonds in the decomposition reaction for the structure changes of the remainder, the structural presumptions of the reactants for lower hydrates formation are discussed. Activation parameters of dehydration were found to be the lower, the smaller are the structure differences between the reactants and products. They do not reflect the bond length central atomvolatile ligand, much more the overall structure differences between the starting and resulting compounds. From all data on crystal and molecular structures of dehydrated compounds is the reaction pathway best indicated by anisotropic temperature parameters of donor atoms corrected for the thermal movement of the central atom: the higher these values in the bond direction are, the lower the values of activation energies of dehydration are.     

Thermal stabilities,electronic properties and structures of metformin-metal complexes

The atomic superposition and electron delocalization molecular orbital (ASED-MO) theory was used to calculate structures and relative stabilities of metformin-metal complexes. The relative stabilities and decomposition pathways were discussed in terms of bond order, binding energy and the nature of charge on the central metal atom. The electronic transitions and their energy gaps were also studied. The optimization of the structures shows that the most stable state is distorted from planarity for Co^II and Ni^II complexes.     

Thermal analysis study of 5,10,15,20-tetrakis (methoxyphenyl) porphyrins and their nickel complexes

The thermal stability in air of 5,10,15,20-tetrakis (4-methoxyphenyl) porphyrin (4-TMPP), 5,10,15,20-tetrakis (3-methoxyphenyl) porphyrin (3-TMPP), and their nickel metallo-complexes (4-TMPP-Ni and 3-TMPP-Ni) has been investigated by thermogravimetry (TG). 4-TMPP and 4-TMPP-Ni exhibit higher thermal stability compared to 3-TMPP and 3-TMPP-Ni. Nickel complexes exhibit a little higher thermal stability than the corresponding porphyrins. The thermal behavior including melting temperature and enthalpy of fusion was determined by differential scanning calorimetry (DSC) and infrared spectra (IR). The activation energies of thermal decompositions of 4-TMPP-Ni and 3-TMPP-Ni were obtained by integral model-free method; the mechanism functions and pre-exponential factors were determined by master plots method. The kinetic models follow the same mechanism function, Avramie-Erofeev equations with integral forms g() = [−ln (l − )]^0.278 and g() = [−ln (l − )]^0.260, respectively.     

Thermal investigations on arylmercury(II) complexes of kojic acid and maltol

Arylmercury(II) derivatives of kojic acid and maltol of the typep-XC₆H₄HgL¹ (I) andp-XC₆H₄HgL² (II) [HL ¹=kojic acid,HL ²=maltol;X=M, MO, NO₂] have been synthesised. IR spectral studies indicate that both the ligands act as bidentate groups, bonding to the mercury(II) ion through phenolic and carbonyl oxygens. From TG curves, the order and activation energy of the thermal decomposition reaction have been elucidated. The variation of the activation energy has been correlated with the nature of the substituents on the phenyl ring. The heat of reaction has been elucidated from differential scanning calorimetric studies. The fragmentation pattern has been analysed on the basis of mass spectra.The authors are grateful to the Council of Scientific and Industrial Research, New Delhi, for the award of a senior research fellowship to J. K.     

Thermal analysis of thione compounds

The thermal behavior of thiourea (Tu), N-methylthiourea (MeTu), N, N-dimethylthiourea (Me₂Tu) and N, N, N, N-tetramethylthiourea (Me₄Tu) was investigated by means of conventional thermal analysis in O₂ and N₂ and IR spectroscopy of the residues on heating in air at various temperatures.At ordinary pressure, the compounds are thermally stable up to the melting points. After melting, they show high vapor pressure, combustion in O₂ atmosphere and isomerization to ammonium thiocyanate, with the exception of Me₄Tu.Financially supported by the Italian MURST.     

Thermal properties of cyanatocopper(II) complexes with pyridine,bipyridine and phenanthroline

The thermal properties of cyanatocopper complexes with pyridine, bipyridine and phenanthroline are described in this paper. It was found that the thermal stabilities of the complexes were found to increase in the order pybipy2(NCS)₂ (L=pyridine and its methyl derivates) which are composed of the liberation of ligandsL and redox reactions of thiocyanate ligands with the central Cu(II) atom [1, 2]. The decomposition temperature of thiocyanate ligands depends on the properties of the ligandsL present in the coordination sphere. An analogous course of thermal decomposition was also observed for [Cu(bipy)₂(NCX)](NCX) (X=S or Se) [3]. For the phenanthroline complexes [Cu(phen)₂(NCX)₂] (X=S or Se) the thermal stability was found to increase significantly (by about 140C) and the decomposition stoichiometry was also changed [3].The present paper contains the results of thermoanalytical studies on bipyridine and phenanthroline cyanatocopper complexes, and a comparison of the thermal properties of pyridine cyanato and isothiocyanatocopper complexes.     

Thermal decompositions of some divalent transition metal complexes of triethanolamine

The thermal behaviours of the Ti(II), Mn(II), Fe(II), Ni(II), Cu(II) and Zn(II) complexes of triethanolamine were studied by means of thermogravimetry, differential thermogravimetry, differential thermal analysis infrared spectrophotometry and elemental analysis. The sequence of thermal stability of the metal complexes, determined by using the initial decomposition temperature, was found to be Ti(II)?Mn(II)>Fe(II)>Ni(II)>Zn(II)>Cu(II). Some of the kinetic parameters, such as the activation energy and order of reaction for the initial decomposition reaction, were calculated and the relationship between the thermal stability and the chemical structure of the complexes is discussed.     

Thermal analysis of calix[4]resorcinarene complexes with secondary and tertiary amines

Tetra-n-undecylcalix[4]resorcinarene forms solid adducts with secondary and tertiary amines. Thermal decomposition of these complexes was investigated by means of thermogravimetry (TG) and differential scanning calorimetry (DSC). It was found that deamination of complexes occurs as multi-step process. The stoichiometry of complexes was evaluated on the basis of TG studies and total heats of deamination were calculated from DSC measurements.Presented at the CCTA9 31.08-05.09 2003, Zakopane PolandThis work was supported by Grant No. 3T09A 02419 from The Polish Committee for Scientific Research. The authors thank to prof. W. Zielenkiewicz for helpful discussion during realisation of this project and prof. T. Borowiak for X-ray structure of the tetra-n-undecylcalix[4]resorcinarene. tetra-n-undecylcalix[4]resorcinarene.     

Thermal behaviour of complexes of antipyrine derivatives II

Parent and mixed ligand complexes of cobalt(II) and copper(II) ions with N,N-bis-(4-antipyrylmethyl)piperazine or N,N-tetra(4-antipyryl-methyl)-1,2-diaminoethane or/and imidazole as ligand and ClO ₄ ^– or SCN^– as counterion were synthesised and their thermal behaviour was investigated.This work was performed in the framework of cooperation between the Hungarian Academy of Sciences and Romanian Academy and was supported financially, in part, by the Hungarian Scientific Research Foundation (OTKA T 029554).     

Thermal behavior of some new isatin complexes

The complexes of the type SnCl₄(HL)·EtOH and SnCl₂L₂ (HL ¹ : the Schiff base resulted in 1:1 condensation of isatin and aniline; HL ² : the Schiff base resulted in 1:1 condensation of isatin and p-toluidine) have been synthesized and characterized. The thermal analysis of the new ligands and complexes has evidenced the thermal intervals of stability and also the thermal effects that accompany them. The Schiff bases thermal transformations consist in phase transitions, C_arom–N bond cleavage and thermolysis processes. The different nature of the complexes generates their different thermal behaviour. The complexes lead in three steps to SnO₂ and in all cases the Schiff bases degradation generates a pyrrolidone-coordinated derivative. As for the SnCl₄(HL)·EtOH complexes, the SnCl₄ formed during the last step is involved in two competitive processes, one consists in their volatilisation while the other one leads to SnO₂. As result the SnO₂ residue is smaller than the theoretically expected.     

Thermal investigations of cefadroxil complexes with transition metals

The cefadroxil (Cef) complexes with transition divalent metals of the formula MCef·nH₂O (where n=2 for M=Cu²⁺, Ni²⁺, Zn²⁺ and n=3 for Co²⁺) and CdCef_1.5·4H₂O were prepared and characterized by elemental and infrared spectra. The thermal analysis of the investigated complexes in air atmosphere was carried out by means of simultaneous TG-DSC technique. During heating in air they lose bound water molecules and then decompose to oxides: Co₃O₄, NiO, CuO, ZnO and CdO. The CdCef_1.5·4H₂O complex forms probably an intermediate product Cd₂OSO₄. The combined TG-FTIR technique was employed to study of decomposition pathway of the investigated complexes. The first mass loss step is the water loss of the complexes. Next, decomposition of cefadroxil ligand occurs with evolution of CO₂ and NH₃. At slightly higher temperature COS is observed according to decomposition of cephem ring. Additionally, as decomposition gaseous products: HCN, HNCO (HOCN), H₂CNH, CO, SO₂, hydrocarbons and carbonyl compounds were observed. The formation of metal sulfates is postulated as solid intermediate product of decomposition in the argon atmosphere. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal analysis of dithiomalonamide complexes

Dithiomalonamide [H₂A, CH₂(CSNH₂)₂] and 2,2-dimethyldithiomalonamide [H₂B, C(CH₃)₂(CSNH₂)₂] can act as bidentate ligands and form stable, cationic 1∶2 complexes with general formula M₂(H₂L)₂X₂ [M=Ni²⁺, Pd²⁺, Pt²⁺;X=C1, Br, I; H₂L=H₂A, H₂B] in strong acidic medium. An elaborate thermal study is presented, based on results from elemental analyses and vibrational studies (IR and Raman spectroscopy). The H₂A complexes start to decompose by releasing two HX molecules whereafter a stable intermediate M(HA)₂ is formed. The H₂B complexes degrade in a different way; the metal-sulphur bond is broken and the ligand is expelled as a whole. Influences of the metal ion and of the halogenide counterions are investigated.     

Thermal decomposition of nicotinate complexes of cobalt and nickel in dynamic nitrogen atmosphere

Thermal decomposition of cobalt and nickel nicotinate was studied by TG, DTG and DSC. The mechanism of decomposition has been established from TG and DSC data. The kinetic parameters namelyE, A together with ΔH were calculated from DSC curves using mechanistic and non-mechanistic integral equations.

---

Zusammenfassung Mittels TG, DTG und DSC wurde die thermische Zersetzung von Cobaltund Nickelnikotinat untersucht. Der Zersetzungsmechanismus wurde anhand der TG-und DSC-Daten entwickelt. Die kinetischen ParameterE, A wurden zusammen mit ΔH anhand der DSC-Kurven mit Hilfe von mechanistischen und nichtmechanistischen Integrationsgleichungen berechnet.

     

Thermal behavior of some new triazole derivative complexes

A series of new complexes with mixed ligands of the type [ML(C₃H₃O₂)₂]·nH₂O (((1) M=Mn, n=1; (2) M=Co(II), n=2; (3) M=Ni(II), n=4; (4) M=Cu(II), n=1.5; (5) M=Zn(II), n=0; L=3-amino-1,2,4-triazole and (C₃H₃O₂)=acrylate anion) were synthesized and characterised by chemical analysis and IR data. In all complexes the 3-amino-1,2,4-triazole acts as bridge while the acrylate acts as bidentate ligand except for complex (5) where it is found as unidentate. The thermal behaviour steps were investigated in nitrogen flow. The thermal transformations are complex processes according to TG and DTG curves including dehydration, acrylate ion and 3-amino-1,2,4-triazole degradation respectively. The final products of decomposition are the most stable metal oxides, except for complex (4) that leads to metallic copper.     

Thermal decomposition of nickel(II) complexes under quasi-equilibrium conditions

The stoichiometry of thermal decomposition and the relationship between the thermal parameters (quasi-equilibrium decomposition temperaturesT _D and decomposition entalpies H _D) of NiL₄(NCS)₂ complexes (L=imidazole derivatives) were studied. It was found that changes in the experimental conditions strongly influence the decomposition stoichiometry. TheT _D and H _D can be ordered in the following sequence (according toL): imidazole<2-Me imidazole<2-Et imidazole相似文献   

Thermal behavior of some new complexes bearing ligands with polymerisable groups

This paper reports the investigation of the thermal stability of a series of new complexes with mixed ligands of the type M(dipy)(C₃H₃O₂)₂(H₂O)_y ((1) M: Mn, y=1; (2) M: Ni, y=2; (3) M: Cu, y=1; (4) M: Zn, y=2; dipy: 2,2’-dipyridine and C₃H₃O₂ is acrylate anion). The thermal behaviour steps were investigated. The thermal transformations are complex processes according to TG and DTG curves including dehydration, oxidative condensation of acrylate and thermolysis processes. The final products of decomposition are the most stable metal oxides.