Indian Journal of Chemical Technology
VOLUME 8 / NUMBER 6 / NOVEMBER 2001CONTENTS
PapersInvestigation of the non-pair formation of palladium (II) with N-n-octylaniline by solvent extraction from weak organic acid media / 445
SS Kolekar & M A Anuse
Thin-layer chromatography of heavy metal-diethyl dithiocarbamate complexes / 452
B R Rao, H S Rathore, S Mital & Y N Singh
Retention behaviour and mechanism of adsorption of some chloropyridine isomers in normal phase liquid chromatography on silica, cyano-silica and amino-silica columns / 458
AS R Krishnamurthy & R Narsimha
Corrosion inhibition of mild steel in sulphuric acid by n-octylamine and
iodoacetic acid / 463
S Shabanna Begum,R Subramanian, V Lakshminarayanan & S M Mayanna
Isopropylation of naphthalene over large pore zeolites / 469
Ishwarya Mathew,Smita Sabne, S Mayadevi, S A Pardhy & S Sivasanker
Rheological behaviour of fatty acid methyl esters / 473
A Srivastava & R Prasad
Modifications of ZSM-5 zeolite catalyst for dimethyl ether conversion to olefins / 482
Framcoise Duprat & Victor Cruz Morales
Hexavalent chromium removal using iron bearing industrial sludges / 487
I B Singh & D R Singh
Degradation of basic yellow auramine O-A textile dye by semiconductor photocatalysis / 496
A Pandurangan, P Kamala, S Uma, M Palanichamy & V Murugesan
Design of commercial batch fractionating columns for separation of - & - pinenes from turpentine oil by the simple method developed / 500
J KSama& P Bandopadhyay
Phase transfer catalysed polymerisation of butyl methacrylate using potassium peroxydisulphate as initiator-A kinetic study / 510
M J Umapathy& D Mohan
Notes
Synthesis and characterization of new polycrown ether (schiff base) / 515
Pradip Kumar Dutta
Educator
The history of iodine from discovery to commodity / 518
JaimeWisniak
Index / 527
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 445-451
Investigation of the ion-pair formation of palladium(II) with N-n-octylaniline by solvent extraction from weak organic acid media
S S Kolekar & M A Anuse*
Analytical Chemistry Laboratory, Department of Chemistry, Shivaji University, Kolhapur 416 004 India
Received 18 January 2001; revised 30 May 2001; accepted 12 June 2001
The use of N-n-octylaniline in xylene for extraction of palladium(II) from salicylate media is studied. The extraction system is studied as a function of equilibration time, diluent, pH, metal and extractant concentrations. Experimental data have been analyzed graphically to determine the stoichiometry of extracted species. It was found that palladium(II) was extracted into the organic phase by ion-pair formation of the [RR’NH2+ Pd(C7H5O3)3-]org. The method is free from interferences due to commonly associated elements and permits the separation of palladium(II) from other metal ions associated with it. The results are employed in the determination of the metal ions in several synthetic mixtures, alloys and catalyst samples.
Indian Journal of Chemical Technology
Vol. 7, November 2001pp.452-457
Thin-layer chromatography of heavy metal-diethyl dithiocarbamate complexes
B R Raoa, H S Rathoreb*, S Mitalb & Y N Singhb
a Indian Institute of Chemical Technology, Hyderabad 500 007, India
bDepartment of Applied Chemistry, Zakir Hussain College of Engineering and Technology, Aligarh Muslim University, Aligarh 202 002, India
Received 17 November 2000; revised 11 June 2001; accepted 9 July 2001
Thin-layer chromatographic behaviour of some heavy metal-diethyldithiocarbamate complexes has been studied using calcium carbonate, calcium citrate, calcium oxalate, calcium phosphate dibasic, calcium sulphate dehydrated, cellulose and silica gel G as stationary phase and acetonitrile, acetone, benzene, butanol, chloroform, 1,4-dioxan, distilled water, ethyl acetate, EDTA-ammonia buffer (1:1), methanol and propanol as mobile phase. Cd(II) and Pb(II) from Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Hg(I) and Hg(II) have been practically separated on cellulose impregnated with sodium diethyldithiocarbamate in ethyl acetate.
Indian Journal of Chemical Technology
Vol. 7, November 2001 pp.458-462
Retention behavior and mechanism of adsorption of some chloropyridine isomers in normal phase liquid chromatography on silica, cyano-silica and amino-silica columns
A S R Krishnamurthy* & R Narsimha
Analytical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Received 12 July 2000, revised 18 June 2001; accepted 10 July 2001
The retention behaviour of some chloropyridine isomers on silica, cyano-silica and amino-silica columns in normal phase liquid chromatography has been studied. Retention times on first two columns follow similar pattern while is different on amino-silica column. An equation for inter comparison of columns for selectivity purpose is developed and verified. Log k’ versus log XB plots follow Snyder and Soczewinski model of adsorption. A mixed interaction of involving hydrogen bonding and dipolar interactions are responsible for the retention of solutes on silica and cyano-silica columns and weak hydrogen bonding interaction lead to separation on amino-silica column. Cyano-silica column is preferred for their separation considering the retention times. However, best selectivity is seen for monoisomers and 2,6-DCP on either silica or cyano-silica column and 3,5-DCP and 2,3,5-TCP on amino-silica column.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp.463-468
Corrosion inhibition of mild steel in sulphuric acid by n-octylamine and iodoacetic acid
S Shabanna Beguma, R Subramanianb, V Lakshminarayananb & S M Mayannaa*
aDepartment of Post-Graduate Studies in Chemistry, Central College, Bangalore University, Bangalore 560 001, India
bRaman Research Institute, C V Raman Avenue, Sadashivanagar, Bangalore 560 080, India
Received 30 October 2000; revised 10 May 2001; accepted 28 May 2001
The influence of iodoacetic acid (IAA) on the corrosion inhibition of mild steel in 0.5 M sulphuric acid (H2SO4) containing octylamine (OA) has been studied using weightloss, polarization and a.c. impedence techniques. Corrosion data obtained by different methods are consistent. IAA and OA individually retard the corrosion of mild steel in sulphuric acid. The addition of IAA enhances the inhibitor efficiency of OA considerably. Adsorption of inhibitors follows quasi-substitution process at the interfaces. OA cations are adsorbed by coulombic interaction on the metal surface, which is pre-occupied by IAA molecules as dipoles. Adsorption model is suggested to account the synergistic action of IAA on the corrosion inhibition of mild steel in sulphuric acid solution by OA.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 469-472
Isopropylation of naphthalene over large pore zeolites
Ishwarya Mathewa, Smita Sabneb, S Mayadevib*, S A Pardhyb & S Sivasankerb
a Department of Applied Chemistry, Cochin University of Science and Technology, Cochin 682 022, India
b National Chemical Laboratory, Pune 411 008, India
Received 22 November 2000; revised 31 May 2001; accepted 8 June 2001
Isopropylation of naphthalene with isopropanol (IPA) proceeds at 2000Cover the large pore zeolites HY, H, H-Mordenite and REY in the presence of N2. Over H, conversion is more in N2 than when cyclohexane is used as solvent or in absence of N2. Conversions and selectivities to diisopropyl naphthalenes fall in the sequence H > REY > HM > HY, but 2,6: 2,7 ratio is greatest with HM. With H, conversion is maximum at 2000C, and increasing the IPA : naphthalene ratio leads to deactivation of the catalyst.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 473-481
Rheological behaviour of fatty acid methyl esters
A Srivastava & R Prasad†
Department of Chemical Engineering, H B Technological Institute, Kanpur 208 002, India
Received 28 November 2000; revised 18 June 2001; accepted 9 July 2001
Rheology of fatty acid methyl esters of soyabean, used-soyabean, mustard and used-mustard oils has been examined experimentally in the temperature range of 3 to 15C. Such a low temperature is encountered in the use of these fatty esters as diesel fuels. These fatty esters were prepared in the laboratory by the transesterification of oils with methanol in the presence of sodium hydroxide as a catalyst. Brookfield Synchro-Lectric Viscometer has been used to observe the dependence of shear rate, time, temperature on the apparent viscosity of these fatty esters. Kerosine works satisfactorily as the bath fluid in the Ultra Cryostat for the desired temperature range. The fatty acid methyl esters of soyabean, used-soyabean, mustard and used-mustard oils are found to behave as Newtonian fluids above a temperature of about 5C. Below this temperature, they are expected to behave as pseudoplastic fluids. These methyl esters also exhibit a thixotropic behaviour. The decrease in the apparent viscosity of these methyl esters with increase in temperature is approximately exponential.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 482-486
Modifications of ZSM-5 zeolite catalyst for dimethyl ether conversion to olefins
Françoise Duprat* & Victor Cruz Morales
ENSSPICAM, Av. Esc. Normandie-Niemen, F-13397 Marseille Cedex 20, France
Received 9 October 2000; revised 17 July 2001; accepted 28 July 2001
The influence of modifications of the ZSM-5 catalyst on the conversion of dimethyl ether to olefins is studied at low hydrocarbon conversion in order to explore the possibility of selective formation of C4=-C6=. Three modifications designed in order to reduce catalyst acidity without increasing steric hindrance are compared, namely, dealumination, partial neutralization with ammonia and ion-exchange with lithium. The unmodified H-ZSM-5 produces 60% of ethene and propene, 30% of olefins C4=-C6= and 10% of heavy olefins plus aromatics. In the same conversion range, the three modified catalysts promote the formation of C4=-C6= and even more the formation of C7=-C8=, and they lower the formation of light olefins and aromatics. There is only a slight difference between modified catalysts : lithium exchanged ZSM-5 leads to higher ratio of C4=-C6= to heavy by-products. An enhanced diffusivity in modified catalysts probably plays a role in the increase in the average molecular weight of olefins produced.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 487-495
Hexavalent chromium removal using iron bearing industrial sludges
I B Singh* & D R Singh
Regional Research Laboratory, Council of Scientific & Industrial Research, Bhopal 462026,India
Received 29 September 2000; revised 26 April 2001; accepted 21 May 2001
The use of iron bearing metallic and mineral materials for the treatment of highly toxic Cr(VI) containing industrial wastewater have received increased attention for the past decade. In conventional treatment, a large amount of chromium hydroxide generates as secondary solid waste which poses a serious problem of disposal. In the presence of iron bearing materials, Cr(VI) reduces to Cr(III) and Fe(II) oxidises to Fe(III) generating mixed complexes from which separation probability of individual element reduces. Based on this chemical principle it is expected that such industrial solid wastes containing iron as a major constituent have potential to reduce highly toxic Cr(VI) to less toxic Cr(III). In view of this, present investigation was aimed to utilise iron bearing industrial wastes like sludges of steel tube making industry and aluminium industry for removal of Cr(VI). Studies include identification of suitable pH for the Cr(VI) reduction, optimisation of dosage and contact time and determination of reaction kinetics. No Cr(VI) was detected from the reacted wastes and total chromium was measured as Cr(III).Toxicity characteristics leaching procedure(TCLP) has been employed to estimate the leachability of chromium, iron etc from the reacted wastes. TCLP results indicate a negligible amount of chromium as Cr(III) and iron leachability from the reacted wastes.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 496-499
Degradation of basic yellow auramine O-A textile dye by semiconductor photocatalysis
A Pandurangan, P Kamala, S Uma, M Palanichamy & V Murugesan*
Department of Chemistry, Anna University, Chennai 600 025, India
Received 24 March 2000; revised 19 July 2001; accepted 28 July 2001
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 500-509
Design of commercial batch fractionating columns for separation of
- & -pinenes from turpentine oil by the simple method developed
J K Sama*a & P Bandopadhyayb
aChemical Engineering and Design Division, Regional Research Laboratory, Canal Road, Jammu-Tawi 180016, India
bFuel and Mineral Engineering Department, Indian School of Mines, Dhanbad 826 004, Bihar, India
Received 25 May 2000; revised 3 August 2001; accepted 20 August 2001
A commercial batch fractionating column, for separating - & -pinenes from a multicomponent mixture, such as tupentine oil was designed, installed and commissioned. The practical results obtained speak well of the accuracy of the simple graphical method developed for designing such columns and calculations for isolating different components.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 510-514
Phase transfer catalysed polymerisation of butyl methacrylate using potassium peroxydisulphate as initiatorA kinetic study
M J Umapathy & D Mohan
Department of Chemical Engineering, AC College of Technology, Anna University, Chennai 600 025, India
Received 3 February 2000; revised 23 May 2001; accepted 28 June 2001
The kinetics of phase transfer catalysed free radical polymerisation of butyl methacrylate using potassium peroxydisulphate as water soluble initiator and propiophenonebenzyldimethylammonium chloride (PPBDAC) as phase transfer catalyst were studied. The polymerisation reactions were carried out in cyclohexanone-water biphase media at 60C in an inert atmosphere under unstirred condition. The effect of various experimental conditions such as different concentrations of monomer, initiator, phase transfer catalyst (PTC) and different ionic strength, temperature and the volume fraction of aqueous phase is studied. The order with respect to monomer, initiator and the phase transfer catalyst is found to be 1, 0.5 and 0.5 respectively. The rate of polymerisation (Rp) is independent of ionic strength and pH. However, an increase in the polarity of solvent and volume fraction of aqueous phase slightly increases the Rp value. Based on the results obtained, a mechanism has been proposed for the polymerisation reaction.
Indian Journal of Chemical Technology
Vol. 8, November 2001. pp. 515-517
Synthesis and characterization of new polycrown ether (schiff base)
Pradip Kumar Dutta*
Department of Applied Chemistry, Shri G. S. Institute of Technology & Science, Indore452 003, India
Received 27 December 2000; revised 25 May 2001; accepted
12 June 2001
A semirigid 32-membered ring dialdehyde crown ether, bis (5-aldoxy-1, 3-phenylene)-32-crown-10 (3), has beensynthesized in one step using 3,5-dihydroxy benzaldehyde (1) and tetra (ethylene glycol) dichloride (2) in the presence of sodium hydride in DMF. A direct polycondensation reaction of bis (5-aldoxy-1,3-phenylene)-32-crown-10(3) and diamines (5) in DMF formed a high molecular weight poly crown ether (schiff base). The polymers are characterized by viscometry, elemental analysis, IR and NMR spectroscopies. The polymers are soluble in common organic solvents. The thermal characteristics of the polymers have been studied by TGA and DTA.
Indian Journal of Chemical Technology
Vol. 8, November 2001, pp. 518-526
The History of Iodine From Discovery to Commodity
Jaime Wisniak*
Department of Chemical Engineering, Ben-Gurion University of the Negev, Beer-Sheva, Israel 84105
The discovery of iodine by accident and the turning of this event into its industrial manufacturing constitutes a fascinating chapter in the development of chemical technology. We see in it how political and economical events brought drastic changes in the raw materials used and the production technologies. From a strictly European activity it turned into an important economic commodity for Chile and Japan.