Iraqi National Journal Of Chemistry

Two new simple, sensitive and economical spectrophotometric methods have been developed for the determination of 1-naphthol in pure form. These methods are based on the reaction of 1-naphthol as n-electron donor with chloranil in method A and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in method B as π-acceptors to give highly coloured complex species in aqueous solution which are absorb maximally at 349nm and 423 nm respectively. Beer's law is obeyed in the concentration ranges 1-36 µg ml-1 and 0.4-5.0 µg ml-1 with high apparent molar absorptivities of 2.59×103and 94.9×103 for methods A and B respectively.

In this study the adsorption of Fe+3 , Cr+3 , Cd+2 ions on Red Kaolin from an aqueous solution was studied . The effect of various operation variable mainly adsorbate concentration, adsorbent dosage, temperature , PH and contact time of ions were evaluated . The optimum contact time to attain equilibrium at 90min of Cr+3 ion , 60min of Fe+3 ion , and 120min of Cd+2 ion , and the maximum of adsorbent dosage was 0.1gm of Cr+3 , Cd+2 and Fe+3 and the best PH values in the range (2-14) , the result showed in PH optimum at pH = 6 of Cr+3 , pH = 2 of Fe+3 and pH =3 of Cd+2. The effect of temperature and thermodynamic parameters wear also studied , the adsorption amount was increased with increased the temperature and the reaction was endothermic . The adsorption isotherms data was analyzed using the Freundlich and Langmuir .

The surface area of a local silicate rock was investigated using different methods after being thermally treated at 200, 400,600 and 800 C° to detect the optimum temperature of treatment. The study has disclosed that the optimum temperature of treatment was 600C° for its maximum surface areas as compared to others. The surface area of the thermally treated samples was determined by many methods including retention by ethylene glycol mono ethyl ether (EGME), adsorption from solution using PNP and MB as solutes as well as the adsorption from vapor phase using acetone vapor. These samples, however, exhibited good surface areas as compared to the untreated silicate .Also, the adsorption isotherm of PNP and MB of all samples were determined and found to be fit to Langmuir type of isotherm which refers to clear micro porous tendency

This study concerns with the doping of Ninivite silica gel by selenato and oxalate chromium complex in ratio of 1:1 for the two complexes and studying their physical and structural properties. Results of x-ray powder diffraction, x-ray fluorescence, thermal analysis, infrared spectra and technical instrumental analysis evaluated the scientific and economic utilization of those samples as adsorbents to separate Qaiyarah heavy crude oil Petrolene into four simple components according to their polarities. Infrared spectroscopy has been applied to study the chemical the chemical composition of the separated fractions.

In this study, the adsorption of certain water-soluble cationic and anionic two dyes, (Fast Green and Crystal violet) from aqueous solutions on modified Clay ( Polymer of kaoline- poly vinyl Alcohol) as an adsorbent.A series of experiments were undertaken in a batch adsorption technique to access the effect of the process variables i.e. initial dye concentration, contact time, initial pH, adsorbent dose, temperature and agitation rate. The adsorption capacity of basic dyes was higher (3.1,7.12 mg.g-1) with the Lower value of the temperature (293 K), adsorbent dosage (0.1, 0.05 gm) higher values at pH7 and agitation rate (100 rpm) for (F.G) and (C.V) respectively. The equilibrium in the solution was observed within (30 min) which indicated by UV-Visible absorption spectroscopy technique.The equilibrium data for adsorption were fitted to the Freundilch and Langmuir isotherm, . The thermodynamic parameters ∆G, ∆H, and ∆S have been calculated which the values of percent adsorbed(%) and Distribution ratio(KD )for two dyes by modified Clay were calculated

A new Cr(III) complex of mixed ligands of picolinic acid (Hpic) and L-cysteine has been synthesized from acid catalyzed hydrolysis of the blue colored solution of sodium salt of bis L-cysteinato(N,O,S) chromateIII complex with solution of Hpic restrictive acidic media of pH=3-4 with gentle heating. The red-brown color product complex of sodium bis L- cysteinato(N,O) monohydroxy picolinato(N)chromateIII have been characterized by element analysis ,electronic and i.r spectroscopy comparison to the properties of some well known related Cr(III) complexes leads to the conclusion that Hpic binds to Cr(III) center via its nitrogen donor atom. The kinetics and mechanism of the formation of this complex, from the acid catalyzed cleavage of Cr—S bond and subsequent Hpic substitution, have been studied spectrophotometrically in a limited pH 3-4.5 range, which was adjusted by HClO4 (μ =0.2M).The rate of the production shows two reaction paths ;one for mono protic thiol,[ Cr(III) (L-cysH)(L-cysN,O,S) (H2O)] and other for diprotic both thiol, [Cr (L-CysH)2 (H2O)2]+2,with Hpic ligand substitution on Cr(III) through N atom.The speices of monoprotic reacts faster with an acid dependent than the diprotic species reaction .The pseudo first order rate constant equation is of the form; k = k1Ka2 [H+]-1 + k2 (where k1 represents the rate constant for first step, k2 for second step reactions and Ka2 is acid dissociation constant for diprotic species) was obtained with ΔH# and ΔS# for both paths are 67.195 kJ mol-1,- 25.41JK-1mol-1 and 68.96 kJ mol-1,-93.64 JK-1 mol-1 respectively.

The synthesis of phenolxy herbicides- Zn/Al-layered double hydroxides nanohybrids by reacting 2, 4-di chloro- (24D) and 2, 4, 5-trichlorophenoxy acetic acid (TCPA) nanocomposites were accomplished using direct method of ion exchange. The release of nanohybrids into various aqueous salutions; carbonate and phosphate was found to be controlled by parabolic diffusion at the beginning of the process. On the other hand, the whole process is governed by pseudo-second order rate expression. The percentage saturated released was found to be anionic-dependent, in the order of carbonate > phosphate for the release media and 24D >TCPA for the anionic guest. This study suggests that the release of the phenoxyherbicides agrochemicals from the nanohybrid compounds can be tuned by choosing the right combination exchangeable anions both in the incoming and the out coming anions.

The MINDO/3-FORCES method was applied for the calculation of the vibration frequencies and normal coordinates of the neutral aromatic perylene molecule and its radical cation and anion. The resulting frequency values were quite near the experimental values when available. Comparison of the results showed that for the C-H and C-C stretching vibrations the sym. mode shows higher frequency values than the asym. As for the CH and CC deformation the asym. vibrations where of higher frequency values than the sym. Comparing the frequencies of the three species with each other it was found that; CH str. (C20H12)˙ + > CH str. (C20H12) >  CH str. (C20H12)˙ ¯ and,sym CC str. > sym CC str.˙ ¯ > sym CC str. ˙ + asym CC str.˙ + > asym CC str. > asym CC str. ˙ ¯ These relations are discussed in terms of the change of the  electron densities at the C atoms of the C-H bonds and the changes in the C-C bond orders of the related bonds.

A new heterocyclic azo ligand 2-[(6-Methoxy-2-benzothiazolyl) azo] hydroquinone (6-MBTAHQ= H2L) was prepared by the reaction between 6-methoxy-2-benzothiazodiazonium chloride with hydroquinone in alkaline alcoholic solution. Six new chelate complexes of Co (III), Ni (II), Cu (II), Zn (II), Cd (II) and Hg (II) have been prepared and characterized by elemental analysis, magnetic susceptibility, molar conductivity, infrared spectra and electronic spectra. The stability constants of complexes follows the sequence; Cu (II) > Zn (II) > Hg (II) > Co (III) > Ni (II) > Cd ((II). The isolated solid complexes have proposed the general formula [M(LH)2].XH2O, where X=1, M= Cu(II), Zn(II), Hg(II) and X=0 for M=Ni(II) Cd(II). When M= Co (III) the formula is [M (LH)2]Cl. H2O. The different measurements revealed that the metal ion in these complexes has hexa-coordination number with octahedral structure..The analytical data show that the metal to ligand ratio (M : L) in all complexes is (1 : 2) .

A bidentate ligand (L), {[(3-hydroxy-1-methylbutyl)-2-en-1-yliedene]amino} hexanoic acid, derived from acetylacetone and 6-aminocaproic acid and its cobalt(II), nickel(II) and copper(II) complexes have been synthesized and characterized by metal analysis, molar conductances, magnetic moments, IR and electronic spectral measurements. The stoichiometric reaction between the metal(II) ion and the synthesized ligand in molar ratio of M:L (1:2) forms the metal complexes of type [M(L)2(H2O)2] (where M = Co(II), Ni(II) or Cu(II)), and of M:L (1:1) of type [M(L)(H2O)2] Cl (where M = Ni(II) or Cu(II) and Co:L (1:1) of type [Co(L) (H2O)4] Cl. Infrared spectra of all the complexes agree that the complexes with the coordination to the central metal ion through the nitrogen of azomethine group and the negative oxygen atom of the carboxylate group. The magnetic moment data suggested for the complexes with metal : ligand ratio as 1:2 and of Co:L (1:1) to have an octahedral geometry around the central metal ion and a square planar configuration for nickel and copper complexes with the metal : ligand ratio as 1:1. The electronic spectral data also agree with their proposed structures.

New coordination polymers of the transition metal ions Cu(II), Mn(II)m Cr(III) with six polyurea ligands were prepared. The polyurea ligands were synthesized by the condensation of urea with the corresponding diamine. These ligands were:- Poly (N,N`-1,4-phenylene diamine) urea(PPU)- Poly (N,N`-1,3-phenylene diamine) urea(PMU)- Poly (N,N`-1,2-phenylene diamine) urea(POU)- Poly (N,N`-2,4-Toluidene diamine) urea(PTU)- Poly (N.N`-Benzidene) urea(PBU)- Poly (N,N`-ethylene diamine) urea(PEU)The prepared compounds were characterized by elemental analysis, UV, IR and H1NMR spectroscopy and magnetic susceptibility measurements. Moreover, thermal stability were investigated by thermogravimetric analysis (TGA). For polyureas it was found that increasing aromaticity inhances thermal stability as follows:PBU > PPU > PMU ≈ PTU > POU > PEUOn the other hand, the higher thermal stability was observed for Mn(II) followed by Cr(III) then Cu(II) complexes. The structure of the complexes was suggested on the basis of the physicochemical measurements obtained. The ligand acts as mono or bidentate with copper and manganese complexes with tetracoordination while the chromium complexes are hexadentate.

The preparation and characterization of new cobalt(II) and nickel(II) complexes with mixed ligands including isatinazine-IAH2 and semicarbazone ligands (including benzoin- semicarbazone-B'SCH2 or isatinsemicarbazone-ISCH2 or isatinbis(semicarbazone)-ISCH3) have been carried out in both neutral (or slightly acidic) and basic medium. The resulted complexes have been characterized using metal analysis by atomic absorption spectroscopy and by precipitation methods, relative molecular weight determina- tion, molar conductance measurements, molar refraction, magnetic susceptibilities, infrared and electronic spectra. The resulted complexes have general formula [M(IAH2)(LH2,3)](NO3)2 or [M(IAH2)(LH2,3)NO3]NO3 in neutral (or slightly acidic) medium whereas neutral or negative ionic complexes of the general formula [M(IAH2-y΄)(LH2,3-y˝)] or Naw[Co(IAH2-y')(LH2,3-y") have been resulted in basic medium, (where M= Co(II) or Ni(II); w=1 or 2; y´=1 or 2; y˝=1 or 2; LH2,3= the ligands B'SCH2 or ISCH2 or ISCH3) in which the ligands acted as neutral or anionic (-1 or -2) in neutral (or slightly acidic) or basic medium, respectively. Accordingly, hexacoordinated mononuclear complexes have been proposed for the resulted complexes had octahedral geometry.

The study is started with the synthesis of benzoin, 4-methoxybenzoin and 4-nitrobenzoin by well known method. Their structures are confirmed by physical methods such as m.p., UV and IR spectra. The study deals with the tautomerism reactions of type enediol keto form by simple halogen titration method. The results show that the keto forms in compounds stated are predominant in benzoin and 4-methoxybenzoin shows a similar result at only 298K, and reverse results at other higher temperatures. Finally, the calculated thermodynamic parameters were estimated, namely Gْ, Hْ and Sْ support, the tautomerism reactions stated.

Several new substituted-4-alkyl/aryl semicarbazides (2a-d) were synthesized. Subsequent ring closure of substituted (2a-d) yield 2-amino alkyl/aryl-5-substituted-1,3,4-oxadiazoles (3a-d) and substituted-1,2,4-triazoles (4a-d) under acidic and basic media respectively. Methylation of compounds (4a-d) gave substituted methoxy-1,2,4-triazoles (5a-d). The reaction of benzilic acid hydrazide (I) with formic acid gave 1-formyl-2-( , -diphenyl- -hydroxyacetyl) hydrazine (6). Refluxing of the later with phosphorus pentoxide and phosphorus pentasulfide gave oxa/thiadiazole (7 and 8) respectively. The structures of all products were elucidated by physical and Spectroscopic methods.

In this research new tri(1,3,4-oxadiazole) derivatives [5-10] were prepared starting from 4-{bis[3-(5-mercapto-1,3,4-oxadiazol-2-yl)-4- methoxyphenyl]methylene}-2-(5-mercapto-1,3,4-oxadiazol-2-yl)cyclohexa-2,5-dienone [4]. The triester derivative [2] obtained from treatment of 5,5'-[(3-carboxy- 4-oxocyclohexa-2,5-dienylidene)methylene]bis(2-hydroxybenzoic acid) [1] with dimethyl sulphate in presence of anhydrous sodium carbonate in dry acetone which was then converted into the trihydrazide derivative [3] by reaction with hydrazine monohydrate in absolute ethanol. Treatment of trihydrazide derivative [3] with carbon disulfide in presence of potassium hydroxide in absolute ethanol resulted in the formation of tri(1,3,4-oxadiazole) derivative [4] which was then converted into the trithioalkyl derivatives [5], [6] and [7] by reaction with benzyl chloride, n-butyl bromide and n-propyl bromide in basic medium, respectively. Treatment of trithioalkyl derivatives [5], [6] and [7] with potassium permanganate in acidic medium resulted in the formation of trisulfone derivatives [8], [9] and [10], respectively. These new synthesized compounds [2-10] probably have some biological activity.All new compounds were characterized by melting points and were uncorrected, (C.H.N.) Elementary Analysis and FT-IR spectra.

This research included detection of five trace elements Co , Ni , Mo , V , and Ge in the serum of 60 patients ( 35 males with mean age 41±17:07.6SE years and25 female with mean age 31 ±2.31268SE SE years ) with lymphoma and 70 healthy( 40 male with mean age 34.6±1.91724SE years and 42 females with mean age 42±3.8223SE years ) cancer enrolled in Margin Hospital countryside Babylon governorate /Iraq by using atomic absorption spectrophotometry flam-less .Analysis t-test dose not reflect the true levels of these elements because of wide range of ages and different interferences .These reasons turned the data from atomic absorption spectrophotometry to grapher 5 program ,and the resulted diagrams were divided the level of these elements into new 4 age groups raising 10 years for each, and solution the mean of each 10 years( 25 , 35 , 45 , and55 year age ) using 2nd order equation to give a new results represented the real serum levels of trace elements, which are lower than healthy for males and females , in agreements with published levels of these elements in addition gave significant results compared with control of age groups by take the mean of these 4 age groups .The new levels of trace elements( μg/l for males and females respectively) are 0.0120582 , 0.0154365 of patients 0.0205877 , 0.152809 of control of Co , and 0.0136302 , 0.011899 of patient 0.0175932, 0.0113087of controls of Ni , and 0.0092995 , 0.0092762 of patients 0.0110997 , 0.145282 of controls of Mo , and 0.0128912 , 0.0072407 of patients 0.033547 , 0.0229725 of controls of V , and the last serum level of Ge trace element is 0.0346395 , 0.0346395 of patients 0.036890 , 0.0612455 of controls .while these results are lower than published , but it’s reflected the related with malnutrition\'s of people in Babylon / Iraq .