Indian Journal of Chemical Technology

 

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VOLUME 14

NUMBER 1

JANUARY 2007

CODEN:ICHTEU

 

ISSN:0971-457X

 

CONTENTS

 

Papers

 

 

Corrosion studies of organicdithiol/monothiol derived self assembled monolayer on copper substrate towards corrosion protection in 0.5 M NaCl

 

5

        IPC Code: C23F11/00, C23F13/08

 

        S S Pathak, V Yegnaraman, J Mathiyrasu, M Maji & A S Khanna

 

 

Study of Schiff’s bases as surface modifiers for corrosion protection of copper in sulphuric acid

16

        IPC Code: C07C251/00, C23F11/00

 

        Ganesha Achary, H P Sachin, Y Arthoba Naik & T V Venkatesha

 

 

A comparative study of inorganic versus organic corrosion inhibitors for mitigation of steel in chloride contaminated alkaline solution

 

22

        IPC Code: C23F11/06, C23F11/00

 

        M Vishnudevan & K Thangavel

 

 

Corrosion behaviour of copper in mandapam seawater

29

        IPC Code: C23F11/00, C23F15/00

 

        S Palraj & G Venkatachari

 

 

Synthesis and characterization of 1-azido, 2,3-dihydroxy 2-azidomethylpropane (ADMP):
A new energetic organic azide

 

34

        IPC Code: C07C247/00

 

        N S Karanjule, M B Talawar, R Sivabalan, G M Gore, D D Dhavale & S N Asthana

 

 

Study of local boiling phenomenon on different metallic surfaces in non-circular flow passages under laminar flow conditions

 

39

        IPC Code: G01F1/684

 

        P V  Ravi Kumar  & M  Venkateswara  Rao

 

 

Vapour phase pinacol rearrangement over modified sulphated zirconia

47

        IPC Code: B01J32/00, B01J31/33

 

        N Nagaraju & S Z Mohamed Shamshuddin

 

 

Kinetics of hydrogenation of palm stearin fatty acid over Ru/Al2O3 catalyst in presence of small quantity of water

 

52

        IPC Code: C07C51/00, C11C3/12

 

        Manoj A Tike & Vijaykumar V Mahajani

 

 

Palladium(II) catalysis on N-bromosuccinimide oxidation of ethylenediaminetetraacetic acid:
A kinetic study

 

64

        IPC Code: B01J23/44, C07B33/00

 

        Rashmi Tripathi & Santosh K Upadhyay

 

Photocatalytic degradation of tatrazine dye using TiO2 catalyst: Salt effect and kinetic studies

71

        IPC Code: B01J21/00, C09B27/00, D06P

 

        A Valentine Rupa, D Manikandan, D Divakar, S Revathi, M Esther Leena Preethi,
K Shanthi  & T Sivakumar

 

 

Studies on thermal degradation of cellulose benzylphosphonate and its metal complexes

79

        IPC Code: C22B4/00, D21B1/00

 

        J B Dahiya, Sushila Rana & Deepa Malhotra

 

 

Nucleate boiling of saturated liquids from a copper coated tube surface

85

        IPC Code: C09K5/00, B05D1/00

 

        L Prasad, V K Agarwal & S C Gupta

 

 

Validation of theoretical model for ion exchange chromatographic separation of boron isotopes

92

        IPC Code: B01J39/06, B01J39/00

 

        D Sujish, B K Sharma & C Anand Babu

 

 

Quantitative complexometric determination of Palladium(II) in its synthetic alloys, complexes and catalysts using 2-mercaptopropionic acid as a selective masking agent

 

96

        IPC Code: C22B11/00, C01G55/00

 

        J Karthikeyan, P Parameshwara, A Nityananda Shetty &  Prakash Shetty

 

 

Notes

 

 

Study on thermodynamic properties of solvent extraction for 2-chloro-4,6-dinitro-resorcinol

100

        IPC Code: B01D11/00

 

        Shi Ruixin & Huang Yudong

 

 

Synthesis of parabens using montmorillonite K10 clay as catalyst: A green protocol

104

        IPC Code: B01J21/00, B01J21/16

 

        Mridul Kumar Hazarika, Raghab Parajuli & Prodeep Phukan

 

 

Auther Index

 

107

Keyword Index

 

108

Guidelines to Authors

109

 

 

 

 

 

 

 

 

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 5-15

 

Corrosion studies of organicdithiol/monothiol derived self assembled monolayer on copper substrate towards corrosion protection in 0.5 M NaCl

S S Pathak, V Yegnaraman, J Mathiyrasu, M Maji & A S Khanna*

 

The corrosion resistance of 1-decanthiol (DT), 1,9-nonanedithiol (NDT) and 1,4-benzendimethanethiol (BDMT) self assembled monolayer (SAM) covered copper were investigated using several electrochemical methods including polarization studies and electrochemical impedance spectroscopy (EIS) in aqueous 0.5 M NaCl solution. The SAM covered surface was characterized by Fourier transform infrared reflectance spectroscopy (FTIR), atomic force microscopy (AFM) and cyclic voltammetry. The inhibition efficiency (IE) of the SAM/copper was investigated by varying; concentration of thiol in solution used for self assembly, assembly period for the formation of SAM and effect of solvents (DMF, toluene, ethanol and acetonitrile) for preparing the thiol solution. The inhibition efficiency of the different thiol compounds under similar experimental conditions for copper corrosion was found to be in the following order: NDT > DT > BMDT. The concentration of thiol and self assembly period affect the quality significantly. At the higher concentration, the self assembled monolayer was formed immediately after the solution was introduced to a substrate. There was only a marginal effect of using different solvent for dissolving the thiols on the inhibition efficiency (IE). FTIR and AFM confirm the self assembling of thiols on copper surface.

Keywords: Self assembled monolayer (SAM), Corrosion resistance, Dithiol, Copper

IPC Code: C23F11/00, C23F13/08

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 16-21

 

Study of Schiff’s bases as surface modifiers for corrosion protection of

copper in sulphuric acid

 

Ganesha Achary, H P Sachin, Y Arthoba Naik* & T V Venkatesha

 

Surface modification of copper by newly synthesised Schiff’s bases, N- [(1E)-2-furylmethylene]-N-phenylamine (FA), 3-{[(1E)-2-furylmethylene] amino} phenol (FAP), 4-{[(1E)-2-furylmethylene] amino} benzoic acid (FAB) and 2-{(E)-[(3-hydroxyphenyl) imino] methyl} phenol (SAP), in 0.5 M sulphuric acid solution was investigated. The corrosion behavior of surface treated copper specimens was tested by galvanostatic polarization technique. The effect of concentration of Schiff’s bases in the treatment bath, treatment time and temperature of the corrosive medium on the corrosion protection efficiency of Schiff’s bases was investigated. Among the compounds studied, the protective film formed by FAB showed maximum protection efficiency. The inhibitive action of Schiff’s bases was due to their adsorption and consequent growth of the protective film on the metal surface. The inhibitive effectiveness depended strongly on the molecular structure of the Schiff’s base. The interaction of the compounds with the metal surface was confirmed by FTIR technique. The SEM studies showed the modification of copper surface due to the adsorption of Schiff’s bases.

Keywords: Schiff base, Surface modifier, Copper corrosion, Sulphuric acid

IPC Code: C07C251/00, C23F11/00

 

 

 

 

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 22-28

 

A comparative study of inorganic versus organic corrosion inhibitors for mitigation of steel in chloride contaminated alkaline solution

M Vishnudevan & K Thangavel*

 

Inorganic inhibitor like calcium nitrite is identified as an effective corrosion inhibiting admixture for rebar corrosion problem in concrete structures. But leaching of calcium nitrite results under dosage leading to pitting corrosion of rebars in presence of chloride. Hence the objective of the present investigation is to develop an alternative corrosion inhibiting system. Disodium phthalate is identified as an alternative system. The efficiency of the system was evaluated by conducting solubility limit test, gravimetric test, potentiodynamic polarization, anodic passivation and electrochemical impedance studies. From the above tests conducted it was proven beyond doubt that the organic inhibitor studied may be considered as an effective corrosion inhibitor than the inorganic type.

Keywords: Anodic passivation, Pitting, Corrosion inhibitor, Rebar

IPC Code: C23F11/06, C23F11/00

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 29-33

 

Corrosion behaviour of copper in mandapam seawater

S Palraj* & G Venkatachari

 

The corrosion characteristics of copper were investigated in the palk bay waters of the Mandapam coast, India over a period of a year. This work comprises both field exposure as well as laboratory studies. The experimental method included determination of corrosion rate by weight loss measurement and analysis of the corrosion products by x-ray diffraction. The XRD analysis of the products on copper threw more light on the nature of the oxide film formed and their impact on the overall corrosion rate/bio fouling of the material. The effect of biofilm on corrosion behaviour of copper was investigated by Tafel polarization and impedance techniques. The annual (oct’96-sep’97) corrosion rate of copper was 0.045 mmpy with no fouling.

Keywords: Biofouling, Corrosion, Impedance, Polarization, Copper, Seawater

IPC Code: C23F11/00, C23F15/00

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 34-38

 

Synthesis and characterization of 1-azido, 2,3-dihydroxy 2-azidomethylpropane (ADMP): A new energetic organic azide

 

N S Karanjule, M B Talawar, R Sivabalan *, G M Gore, D D Dhavale & S N Asthana

 

This paper reports the synthesis of title compound (ADMP) for its possible use as an energetic azido plasticizer. The synthesis was carried out by protecting readily available sugar D-mannitol (1) by treating it with acetone in presence of fused FeCl3 at room temperature, leading to the formation of 1,2-5,6 di-O-isopropylidene-D-mannitol (2), which on further oxidation with sodium meta periodate in acetone gave 2,3- O-isopropylidene 1-propanal (3). The subsequent treatment with formaldehyde in presence of base (Aldol-Cannizarro condensation) yielded 2,3-O-isopropylidene 2-hydroxymethyl-1- propanol (4). Tosyl protection (5) of the resulting compound followed by introduction of azide substituents gave 2,3-O-isopropylidene-2- azidomethyl-1-propane (6) and finally deprotection of acetonoide functionality using 10% H2SO4 gave title compound (ADMP, 7). All the intermediates and the final product have been characterized by IR and NMR spectra. The differential scanning calorimetry (DSC) study on ADMP indicated that it undergoes exothermic decomposition in the temperature in the range of 191-260°C with heat release of the order of 1390 J/g. The theoretical performance parameters suggest its superior energetic in comparison to that of non-energetic plasticizers such as dioctyl phthalate, diamyl phthalate and dibutyl phthalate.

Keywords: ADMP, Aldol-Cannizarro condensation, Theoretical performance, Energetic azido plasticizer

IPC Code: C07C247/00

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 39-46

 

Study of local boiling phenomenon on different metallic surfaces in non-circular flow passages under laminar flow conditions

 

P V Ravi Kumar & M Venkateswara Rao*

 

The thermal diffusivities of the metals are found to be an influencing parameter in explaining the different threshold temperatures required for the local boiling phenomenon to occur on different metallic surfaces and the Fourier number is used in the correlation to account for the thermal diffusivities. The effect of the degree of sub-cooling on local boiling is also quantified by modifying the Jakob number by replacing the term giving the difference between the temperature of the boiling liquid film and saturation temperature of the liquid, with the ratio of excess temperature to the degree of sub-cooling with an index of 0.2. The proposed final correlation comprising of local boiling coefficient, non-boiling coefficient, Fourier number and modified Jakob number is Klb = 0.11(Knb) (Fo)0.25(Jamod)2.5.

Keywords: Local boiling coefficient, Non-boiling coefficient, Surface temperature, Laminar flow

IPC Code: G01F1/684

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 47-51

 

Vapour phase pinacol rearrangement over modified sulphated zirconia

 

N Nagaraju* & S Z Mohamed Shamshuddin

 

The catalysts, sulphated zirconia and Fe(III) and Mn(II) ions containing sulphated zirconia were prepared by wet impregnation method. These catalysts were characterized for BET surface area, total surface acidity, elemental analysis and powder XRD. The catalytic activity of these catalysts was evaluated in vapour phase pinacol-pinacolone rearrangement of 2,3-dimethyl-2,3-butanediol (pinacol). 2,3-dimethyl-2-butanone (pinacolone) and 2,3-dimethyl-1,4-butadiene were the two main products obtained. The effect of Fe(III), Mn(II) and their mixture on the physico-chemical characteristics and catalytic activity of sulphated zirconia was studied. The effect of nature of solvent on the extent of conversion of pinacol and selectivity towards the products (ketone or diene) was also studied. The activity of sulphated zirconia and its modified forms was compared with the activity of pure ZrO2, Fe2O3 and MnO in the above mentioned reaction to evaluate the nature of effect of support and metal ions.

Keywords: Sulphated zirconia, Fe(III) and Mn(II) modified sulphated zirconia, Pinacol rearrangement, Solvent effect

IPC Code: B01J32/00, B01J31/33

 

 

 

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 52-63

 

Kinetics of hydrogenation of palm stearin fatty acid over Ru/Al2O3 catalyst in presence of small quantity of water

 

Manoj A Tike & Vijaykumar V Mahajani*

 

The liquid phase hydrogenation of palm stearin fatty acid was studied in the presence of 2% (w/w) water, using n-dodecane as solvent. The catalyst, 5% Ru/Al2O3 was found to be more effective than that of Ni catalyst. The presence of water enhanced hydrogenation rate for ruthenium-supported catalyst. The kinetics for palm stearin fatty acid hydrogenation over 5% Ru/Al2O3 catalyst was investigated in a slurry reactor in the range of temperature (393-423 K) and H2 pressure (0.68-2.72 MPa). The rate of hydrogenation was described in terms of reduction in iodine value (IV) using power law model. The Langmuir–Hinshelwood type kinetic expressions for a single site mechanism with molecular adsorption of H2 was proposed, and this model provided the best fit of the experimental data. The catalyst could be reused thrice without any loss in activity.

Keywords: Hydrogenation, Palm stearin fatty acid, Catalyst, Kinetics

IPC Code: C07C51/00, C11C3/12

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 64-70

 

Palladium(II) catalysis on N-bromosuccinimide oxidation of ethylenediaminetetraacetic acid: A kinetic study

Rashmi Tripathi & Santosh K Upadhyay*

 

The kinetics of palladium(II) catalysed oxidation of ethylenediaminetetraacetic acid (EDTA) by N-bromosuccinimide (NBS) in acidic (HClO4) as well as in alkaline medium have been investigated. The rate of reaction is always proportional to the concentration of NBS and catalyst. The order of reaction with respect to substrate was also found to decrease from unity to zero in acidic as well as in alkaline medium. The effect of succinimide on the rate of oxidation was negative in each case. In acidic medium, a negligible effect of H+ on the rate of oxidation has been observed while in alkaline medium a retarding effect of OH- on the rate has been observed. The proposed mechanism involves the formation of {EDTA-PdII} complex which has been verified spectrophotometrically.

Keywords: Palladium, Catalysis, Oxidation of ethylenediaminetetraacetic acid, Kinetics of N-bromosuccinimide

IPC Code: B01J23/44, C07B33/00

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 71-78

 

Photocatalytic degradation of tatrazine dye using TiO2 catalyst:
Salt effect and kinetic studies

 

A Valentine Rupa, D Manikandan, D Divakar, S Revathi, M Esther Leena Preethi, K Shanthi  &

 T Sivakumar*

The effluents from the textile industry are the major water pollutants for several decades. Photocatalytic degradation of dyes is one of the important methods for removing the pollution of water. In the present study, the degradation of a pollutant namely tatrazine (azo dye) using TiO2 as photocatalyst has been discussed. The experiments carried out by using UV or visible lamps with different wattages and in presence of sunlight have been compared. Comparison of photocatalytic activity has also been made with different grades of TiO2. Catalyst weight has been optimized for the complete degradation of tatrazine. In addition, the effects of pH and addition of different salts on the photocatalytic activity of TiO2 have been carried out. Kinetics for the degradation of tatrazine has also been discussed.

Keywords: Photocatalysis, Tatrazine, Titanium dioxide, Salt effect

IPC Code: B01J21/00, C09B27/00, D06P

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 79-84

 

Studies on thermal degradation of cellulose benzylphosphonate and
its metal complexes

J B Dahiya*, Sushila Rana & Deepa Malhotra

 

Cellulose benzylphosphonate (CBP) and its metal complexes with transition metals such as chromium, iron, copper and zinc have been synthesized as flame-retardant formulations on cellulose and when heated, these compounds give rise to high char yields. Enthalpy changes and char yields suggest that such derivatisation may give rise to novel flame retardant treatments for cellulosic materials. The thermal degradation of cellulose, CBP and metal complexes of CBP has been studied by using TG and DSC from ambient temperature to 600°C in static air. The FTIR spectra of chars of modified cellulose indicate that dehydration takes place and compounds containing C=O, C=C, P–O–P and P=O groups are formed.

Keywords: Thermal degradation, Cellulose, Char, Enthalpy, FTIR, Flame retardant

IPC Code: C22B4/00, D21B1/00

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 85-91

 

Nucleate boiling of saturated liquids from a copper coated tube surface

L Prasad, V K Agarwal* & S C Gupta

 

This paper presents an experimental investigation on nucleate pool boiling of saturated liquids, viz. water, methanol and isopropanol on a 26 mm thick copper coated mild steel heating tube at atmospheric and subatmospheric pressures. Enhancement of heat transfer coefficient due to coating is found for all boiling liquids. Thermal performance of a coated tube is evaluated in terms of heat flux and pressure and thereby a criterion for enhancement of heat transfer coefficient for the boiling of saturated liquids on a copper coated tube is established.

Keywords: Nucleate Boiling, Coated surface, Saturated liquids

IPC Code:  C09K5/00, B05D1/00

 

 

 

 

 

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 92-95

 

Validation of theoretical model for ion exchange chromatographic

separation of boron isotopes

 

D Sujish, B K Sharma* & C Anand Babu

 

Ion exchange chromatography and distillation route have been used for separation of boron isotopes. Of these, ion exchange chromatography is more economical and industrially viable technique. Mathematical model for isotope separation using ion exchange chromatography is reported in literature and was used to predict the enrichment profile for boron. Experiments were conducted using six columns of 50 mm diameter and boron enrichment profile measured. The prediction of the model was found to be reasonably matching with the experimental measurements.

Keywords: Modeling, Boron enrichment, Ion exchange chromatography, HETP

IPC Code: B01J39/06, B01J39/00

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 96-99

 

Quantitative complexometric determination of palladium(II) in its
synthetic alloys, complexes and catalysts using 2-mercaptopropionic
acid as a selective masking agent

J Karthikeyan, P Parameshwara, A Nityananda Shetty* & Prakash Shetty

 

A simple, rapid and accurate complexometric method for the determination of palladium(II) is proposed, based on the selective masking property of 2-mercaptopropionic acid towards palladium(II). In the presence of diverse metal ions, palladium(II) is complexed with excess of EDTA and the surplus EDTA is backtitrated with standard zinc sulphate solution at pH 5-5.5 (acetic acid-sodium acetate buffer) using xylenol orange as indicator. An excess of a 0.5% aqueous solution of 2-MPA is then added to displace EDTA from Pd(II)-EDTA complex. The released EDTA is titrated with the same standard zinc sulphate solution as before. Reproducible and accurate results are obtained in the concentration range 0.5-17.80 mg of palladium with relative error of ± 0.50% and coefficient of variation not exceeding ± 0.33%. The effects of diverse ions are studied. The method is used for the determination of palladium in its complexes, catalysts and synthetic alloy mixtures.

Keywords: EDTA, 2-Mercaptopropionic acid, Masking agent, Palladium determination

IPC Code: C22B11/00, C01G55/00

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 100-103

 

Study on thermodynamic properties of solvent extraction for

2-chloro-4, 6-dinitro-resorcinol

 

Shi Ruixin & Huang Yudong*

 

Thermodynamic properties of solvent extraction of 2-chloro-4,6-dinitro-resorcinol from aqueous phase were investigated. With ethyl acetate as the extractant and an organic solvent, such as benzene, toluene, cyclohexane and n-heptane as the diluent, the composition of the extracted species was determined by the method of slope analysis and the results show that the composition relates to the diluent. It is also found that the distribution coefficient of 2-chloro-4,6-dinitro-resorcinol in the organic phase increases with the increase of the dielectric constant of the diluent. It is confirmed that the extraction of 2-chloro-4,6-dinitro-resorcinol is an exothermic process and the apparent thermal effect, , is -10.088 kJmol-1.

          Keywords: Solvent extraction, Thermodynamic properties, 2-Chloro-4,6-dinitro-resorcinol

          IPC Code: B01D11/00

 

 

Indian Journal of Chemical Technology

Vol. 14, January 2007, pp. 104-106

 

Synthesis of parabens using montmorillonite K10 clay as catalyst:

A green protocol

 

Mridul Kumar Hazarika, Raghab Parajuli & Prodeep Phukan*

 

Synthesis of three parabens is achieved using montmorillonite K10 clay as heterogeneous catalyst. Methyl, ethyl, and propyl parabens were synthesized by esterification of 4-hydroxy benzoic acid with the corresponding alcohol. The catalyst can easily be separated from the reaction mixture and reused successfully without affecting the catalytic activity.

          Keywords: Paraben, Montmorillonite K10, Clay, Alcohol, p-Hydroxy benzoic acid, Esterification

          IPC Code: B01J21/00, B01J21/16