Indian Journal of Chemical Technology

Volume 9            Number 3            May 2002

 

CODEN:ICHTEU 9(3) 179-278                                                               ISSN: 0971-457X

 

CONTENTS

 

Research Articles

 

 

New rodent repellent and UV resistant nylon tapes for aircraft arrester net

185

K Ganesan, Santosh Kumar, D K Dubey, Shri Prakash,   Jagat Singh,

J K Tyagi   & M P Kaushik

 

 

 

 

Utilisation of Jatropha seed oil in the stabilisation of poly (vinly chloride) against thermal degradation

 

188

F E Okieimen  

 

 

 

Role of Zn2+ in the inhibition of corrosion of mild steel by 1-hydroxyethane-1,1-diphosphoric acid

 

197

Susai Rajendran, R   Maria Joany, B V Apparao & N Palaniswamy

 

 

 

Basic dye adsorption on a low cost carbonaceous sorbent – kinetic and equilibrium studies

 

201

B Stephen Inbaraj   & N Sulochana

 

 

 

Kinetic studies on the photocatalytic decolourisation of water-soluble crown dyes using Fe° and Zn° catalysts

 

209

Y K Agrawal, B R   Pandya & S K Menon

 

 

 

Thermodynamic dissociation constants of glycine and dl-alanine in water-ethanol mixtures

 

212

M Ashfaqur Rahman, A R   Chowdhury & M R Zaman

 

 

 

Galactose oxidase immobilised on Ocimum sanctum seeds for the enzymatic preparations of L-glucose, L-galactose and L-xylose

 

218

K K Yadav, S K   Vernwal, Z Afaq & K D S Yadav

 

 

 

Study on the formation of dinitramide using mixed acid nitrating agents

223

G Santhosh, S   Venkatachalam, M Kanakavel & K N Ninan

 

 

 

Scale-up and optimization studies on lignin biodegradation of rice straw using Phanerochaete chrysosporium

 

227

Sk Masud Hossain,   Manas Das & S H Ibrahim

 

 

 

Pressure mediated reduction of nitro to amino functionality with FeSO4/NH3/H2O/EtOH system

 

235

Hari Sankar Kakati   & Dibakar Chandra Deka

 

 

 

Retention behaviour of metal ions on calcium sulphate layers: Separation of mercury

 

239

Aditya K Misra   & Sonu Pachauree

 

 

 

 

Contd.

Sorption aided process for the removal and recovery of Zinc(II) using salicylaldoxime immobilised silica gel

 

245

Mitali Sarkar   & Pradip Kumar Datta

 

 

 

The phosphine oxides Cyanex-921, Cyanex-923 and Cyanex-925 as extractants for Pb(II) from aqueous media

 

251

J N Iyer, S D Pawar   & P M Dhadke

 

 

 

Ion-exchange kinetics on styrene supported zirconium(IV) tungstophosphate: An organic-inorganic type cation exchanger

 

256

A A Khan, R Niwas   & M M Alam

 

 

 

Notes

 

 

An efficient route for the synthesis of chloroaceticanhydride and benzyl mercaptan

261

R L Jagadish, T R   Vijayakumar & K M Lokanatha Rai

 

 

 

Educator

 

 

The history of bromine from discovery to commodity

263

Jaime Wisniak

 

 

 

Chem-Tech Scan

272

 

 

Announcement

276

 

 

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 185-187

 

 

New rodent repellent and UV resistant nylon tapes for aircraft arrester net

 

K Ganesana, Santosh Kumara, D K Dubeya, Shri Prakasha, Jagat Singhb, J K Tyagib & M P KaushikaT

Received 2 August 2001; revised received 11 February 2002; accepted 6 March 2002

A new rodent repellent and UV resistant nylon tape for the fabrication of fighter aircraft arrester net has been developed. Oleoresin, a sensory irritant from natural sources has been used along with black carbon and butyl recinoleate. These tapes have been found to be effective against rodents under laboratory conditions

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 188-196

 

 

Utilisation of Jatropha seed oil in the stabilisation of poly (vinyl chloride)

against thermal degradation

 

F E Okieimen

Received 5 March 2001; revised received 4 January 2002; accepted 14 February 2002

Jatropha seed meal was extracted with n-hexane and the oil obtained was found to have iodine value 157.37, acid value 5.61 and free fatty acid 2.70. The fatty acid profile of the oil showed that oleic acid (31.35%), palmitic acid (20.9%) stearic acid (15.68%) and caprylic acid (10.45%) were the major fatty acid components. The seed oil was epoxidised at 29°C using peracetic acid produced in situ by reacting hydrogen peroxide (30% v/v) with various amounts of glacial acetic acid. Barium, cadmium, lead and zinc soaps of the oils were prepared by metathesis in alcohol solution. Thermal degradation studies on poly (vinyl chloride) in the presence of Jatropha seed oil, the epoxidised oil and the metal soaps of the oils were carried out at various temperatures (170, 180 and 190°C) under oxidative and non-oxidative conditions. Changes in intrinsic viscosity and levels of unsaturation in the degraded polymer samples together with kinetic data (rate measurements at 1% conversion) were used to evaluate the relative stabilising effect of the additives on the thermal degradation of poly (vinyl chloride). It was found that although the values of the rate of dehydrochlorination were of about the same order of magnitude (10-2% min-1), the rates were relatively lower, and the time at which degradation reached 1% conversion considerably higher than the corresponding values obtained in the absence of the additives. The data from solution viscosity measurements and from estimates of the level of unsaturation in the degraded polymer samples indicate that metal soaps of the oil exert stabilising effect on the oxidative and monoxidative thermal degradation of poly (vinyl chloride).

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 197-200

 

 

Role of Zn2+ in the inhibition of corrosion of mild steel by

1-hydroxyethane-1, 1-diphosphonic acid

 

Susai Rajendrana*, R Maria Joanyb, B V Apparaoc & N Palaniswamyd

Received 22 May 2001; revised received 7 February 2002; accepted 19 March 2002

 

50 ppm sodium salt of 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) offered only 11% inhibition efficiency (IE) to corrosion of mild steel immersed in neutral aqueous environment containing 60 ppm chloride. When 50 ppm Zn2+ is added to 50 ppm HEDP, the IE increased to 98%. The influence of Zn2+ on the corrosion -inhibition by HEDP is discussed based on the results obtained from UV-visible, FTIR and luminescence spectra. Presence of Zn2+ facilitates the transport of HEDP from the bulk of the solution to the metal surface; both the anodic reaction and cathodic reaction are controlled effectively.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 201-208

 

Basic dye adsorption on a low cost carbonaceous sorbent – Kinetic and equilibrium studies

 

B Stephen Inbaraj & N Sulochana*

Received 5 March 2001; revised received 17 March 2002; accepted 20 March 2002

A carbonaceous sorbent prepared from an indigenous agricultural waste, jack fruit peel, by acid treatment was tested for its efficiency in removing basic dyes. Malachite green, a common basic dyestuff of triphenyl methane series used for dyeing silk and wool directly and cotton mordanted with tannin to deep green, was chosen for investigation. The process parameters studied include agitation time, initial dye concentration, carbon dose, pH and temperature. The adsorption followed first order reaction equation and the rate is mainly controlled by intraparticle diffusion. Freundlich, Langmuir and Redlich-Peterson isotherm models were applied to the equilibrium data. The adsorption capacity (Qo) obtained from the Langmuir isotherm plot was 166.37 mg g-1 at an initial pH of 6.0 and at 32 ± 0.5°C. The influence of pH on dye removal was not significant and the adsorption capacity increased with increase in temperature. A portion of the dye was recovered from the spent carbon using 50% acetic acid (v/v).

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 209-211

 

 

Kinetic studies on the photocatalytic decolourisation of water-soluble crown dyes using Feo and Zno catalysts

 

Y K Agrawal*, B R Pandya & S K Menon

Received 5 March 2001; revised received 27 January 2002; accepted 14 February 2002

Photodecolourisation of crown dyes with Feo and Zno as catalysts is discussed. Effects of pH and concentration of catalyst on the decolourisation and kinetics for degradation etc have been studied.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 212-217

 

 

Thermodynamic dissociation constants of glycine and dl-alanine in
water - ethanol mixtures

 

M Ashfaqur Rahman*, A R Chowdhury & M R Zaman**

Received 12 June 2001; revised received 10 January 2002; accepted 7 February 2002

The thermodynamic dissociation constants of glycine and dl-alanine in 0, 20, 40, 60 and 80% (w/w) water - ethanol mixtures at 30°C and at a constant ionic strength, Is = 0.1 M KNO3 have been measured pH-metrically using Irving and Rossotti technique. pK1 and pK2 values in aqueous medium have been found to agree well with previously reported ones. It is observed that the pK1 values of these acids increase regularly with the increase of ethanol contents in the mixtures while pK2 values show distinct minima ca. at 40% (w/w) ethanol content. The variation in pK values with the solvent composition is discussed in terms of the free energy transfer from water to ethanol-water mixtures. It is concluded that the specific solute-solvent interactions play a vital role in changing the pK values in ethanol-water mixtures.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 218-222

 

 

Galactose oxidase immobilised on Ocimum sanctum seeds for the enzymatic preparations of L-glucose, L-galactose and L-xylose

 

K K Yadav, S K Vernwal, Z Afaq & K D S Yadav*

Received 4 July 2001; revised received 28 February 2002; accepted 20 March 2002

Galactose oxidase has been immobilised on a solid support developed by modification and activation of surface of Ocimum sanctum seeds. The conversions of xylitol to L-xylose; galactitol to L-galactose and D-sorbitol to L-glucose using the above immobilised enzyme preparation have been shown. Galactose oxidase co-immobilised with catalase increases the conversion yields. Conversion of D-sorbitol to L-glucose using the immobilised galactose oxidase in a mini flow bed reactor has been demonstrated.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 223-226

 

 

Study on the formation of dinitramide using mixed acid nitrating agents

 

G Santhosh, S Venkatachalam*, M Kanakavel & K N Ninan

Received 9 August 2001; revised received 27 February 2002; accepted 21 March 2002

Nitration of ammonium sulphamate was carried out using a mixture of sulphuric acid and nitric acid at -30 to –40°C. The mole ratio of sulphuric acid to nitric acid was varied from 0 to 4 and the extent of formation of ammonium dinitramide (ADN) was measured. The initial yield of ADN increases with increase of sulphuric acid content in the acid mixture and starts decreasing as the reaction time is increased. The variation of product yield with change in reaction time and total acid concentration was studied.

 

 

Indian Journal of Chemical Technology

Vol. 9, May 2001. pp. 227-234

 

 

Scale-up and optimization studies on lignin biodegradation of rice straw using Phanerochaete chrysosporium

Sk Masud Hossaina*, Manas Dasb & S H Ibrahimc

Received 19 February 2001; revised received  28 January 2002; accepted 10 March 2002

 An effective batch aerobic study on lignin biodegradation with Phanerochaete chrysosporium is performed and process parameters are optimized. The optimum time is 14 days for lignin biodegradation of rice straw. At the optimum time, 2 percent glucose (carbon source) and 0.20 percent L-asparagine (nitrogen source) calculated on raw material, can degrade maximum lignin. The percent of lignin degradation at optimum GNC dose is 47.38 with lowest kappa number (k) value 23.58 with optimum inoculum concentration 20 percent (v/v) and optimum age of inoculum 7 days with pH 4.5. The minimum COD and BOD values for optimum GNC Dose treated effluents after 14 days digestion are 1,050 mg/L and 625 mg/L respectively. The optimum GNC Dose treated effluents having colour (OD at 465 nm) is 0.20 which is minimum.

 

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 235-238

 

 

Pressure mediated reduction of nitro to amino functionality with

FeSO4/NH3/H2O/EtOH system

Hari Sankar Kakati & Dibakar Chandra Deka*

Received 8 August 2001; revised received 11 February 2002; accepted 20 March 2002

Pressure mediated reduction of nitro to amino group by FeSO4/NH3/H2O/EtOH system has been carried out. Moderate nitrogen pressure (1.1 MPa at reaction temperature) at 100o C for 4 h has almost doubled the yield to 70.7% from 39.7% when no pressure is applied. Functional groups like chloro and olefinic double bond remain intact but esters are incompatible.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 239-244

 

 

Retention behaviour of metal ions on calcium sulphate layers: Separation of mercury

Aditya K Misra* & Sonu Pachauree

Received 16 December 2000; revised received 27 March 2002; accepted 1 April 2002

Calcium sulphate static phase thin layer chromatography (TLC) has been performed in eight pure and mixed solvent systems containing acetonitrile and dioxane. Separations of Pb2+ from Hg2+, Bi3+ and UO22+; UO22+ from VO2+; Ni2+ from Cr3+; Ag+ from Bi3+; Ce4+ from Ce3+; Hg2+ from Cd2+; Zn2+ from Hg2+ have been achieved successfully. Rapid quantitative separation of mercury (2-20 mg) from binary, ternary and multicomponent mixtures containing several metal ions has also been successfully achieved.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 245-250

 

 

Sorption aided process for the removal and recovery of Zinc (II) using salicylaldoxime immobilised silica gel

Mitali Sarkar* & Pradip Kumar Datta

Received 27 April 2001; revised received 3 January 2002; accepted 6 March 2002

Salicylaldoxime immobilised silica gel was used as an effective solid phase surface, for the preconcentration, removal or recovery of zinc ion from aqueous phase. The efficiency was tested by the equilibrium sorption study both in batch and column operations. The efficiency increases with the shaking period, agitation speed, adsorbent dose, temperature and flow rate but is independent on the volume of the solution. Maximum adsorption was found to occur at pH 5.5. Alkali metal, alkaline earth metal and ammonium salts do not influence the adsorption process. Heavy metal ions viz. Cu(II), Ni(II), Co(II) and Fe(III) get adsorbed by the said process but at much different pH values. Complexing ligands like EDTA and cyanide markedly decrease the adsorption of Zn(II) by the said procedure. The adsorption data fits well the Langmuir adsorption isotherm model. The negative free energy change indicates that the process is favourable as well as spontaneous. The merit of the process lies with its high preconcentration factor.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 251-255

 

 

The phosphine oxides Cyanex-921, Cyanex-923 and Cyanex-925 as
extractants for Pb(II) from aqueous media

 

J N Iyer, S D Pawar & P M Dhadke*

Received 19 June 2001; revised received 27 January 2002; accepted 1 March 2002

The behaviour of neutral phosphine oxides Cyanex-921, Cyanex-923 and Cyanex-925 in the extraction of Pb(II) from nitrate media is described. The extraction of Pb(II) was found to be quantitative in the pH range 8.0-9.0 with these extractants. From the metal loaded organic phases for these extractants, Pb(II) was stripped back with 0.5 M H2SO4. The effects of pH, temperature, equilibrium time, diluents, diverse ions and stripping ability using various acids on the extraction of Pb(II) have been studied. The methods are also extended for the analysis of real samples.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 256-260

 

 

Ion-exchange kinetics on styrene supported zirconium(IV) tungstophosphate:
An organic-inorganic type cation exchanger

A A Khan*, R Niwas & M M Alam

Received 25 November 2000; revised received 15 January 2002; accepted 19 March 2002

Kinetics of exchange reaction of Mg2+, Ca2+, Sr2+, Ba2+, Cu2+, Mn2+, Ni2+ and Zn2+ on styrene supported zirconium (IV) tungstophosphate cation exchanger has been studied at 25, 33, 50 and 65oC. The rate of exchange is found to be particle diffusion controlled at a metal ion concentration ³ 0.02 M in aqueous medium. Various kinetic parameters such as self-diffusion coefficient, D0 , energy of activation, Ea, and entropy of activation, DS*, have been calculated.

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 261-262

 

Note

 

An efficient route for the synthesis of chloroaceticanhydride and benzyl mercaptan

 

R L Jagadish*a, T R Vijayakumar & K M Lokanatha Raib

Received 20 September 2001; revised received 21 February 2002; accepted 21 March 2002

An efficient and cost saving procedure for the synthesis of chloroacetic anhydride and benzyl mercaptan is discussed here.

 

 

Indian Journal of Chemical Technology

Vol. 9, May 2002, pp. 263-271

 

 

The history of bromine from discovery to commodity

 

Jaime Wisniak*

The discovery of bromine represents one of the first experimental evidences that elements could be grouped in families of similar properties. Transformation of the new element and its derivatives into a commercial reality had to wait until automobiles begun to be mass-produced. The pattern end use of bromine has reflected the changes in social appreciation of environmental protection and safety. From a strong initial use as gasoline additive and agricultural chemical, the end uses are changing drastically into flame-retardants and sanitary uses. From a strictly initial European industrial activity it has turned into an important chemical activity for the United States, Jordan, and Israel.