Measurement of apex angle of the prism using total internal reflection

Total internal reflection technique is examined critically for the measurement of apex angle of the prism. Recognition of the critical boundary completely specifies the apex angle ‘A’ of the prism by keeping constant the ratio of refractive index of sample fluid (n₁=1.4) to that of glass (n₂=1.7). Recording of observations in the laboratory is dependent upon whether the apex angle ‘A’ of prism is greater than or less than or equal to critical angle ‘r_c’. The minimum value of error function ‘χ’ in the proximity of Abbe angle explain the choice of Abbe type instruments and shown invariant by relating positive ‘₊’ and the negative angle of emergence ‘₋’. Using ray-tracing technique, an expression for the length of the critical boundary ‘l’ is derived and is shown as a measure of the apex angle ‘A’ of the prism.

The choice of the realistic grazing condition leads us to two turning points for which error function ‘χ’ is minimal and yields appropriate option of the measurement of apex angle ‘A’ of the prism. It is further shown that the small error ‘ζ’ crept in the apex angle ‘A’ of the prism can lead to a significant error in the design of Pulfrich type instruments.

Experimental measurements are in-line with the predictions made.     

Thiosalicylic acid-immobilized Amberlite XAD-2: metal sorption behaviour and applications in estimation of metal ions by flame atomic absorption spectrometry

Thiosalicylic acid (TSA)-modified Amberlite XAD-2 (AXAD-2) was synthesized by coupling TSA with the support matrix AXAD-2 through an azo spacer. The resulting chelating resin was characterized by elemental analyses, thermogravimetric analysis (TGA) and infrared spectra. The newly designed resin quantitatively sorbs CdII, CoII, CuII, FeIII, NiII and ZnII at pH 3.5-7.0 when the flow rate is maintained between 2 and 4 ml min-1. The HCl or HNO3 (2 mol l-1) instantaneously elutes all the metal ions. The sorption capacity is 197.5, 106.9, 214.0, 66.2, 309.9 and 47.4 mumol g-1 of the resin for cadmium, cobalt, copper, iron, nickel and zinc, respectively, whereas their preconcentration factor is between 180-400. The breakthrough volume of HCl or HNO3 for elution of these metal ions was found to be 4-8 ml. The limit of detection (LOD) for CdII, CoII, CuII, FeIII, NiII and ZnII was 0.48, 0.20, 4.05, 0.98, 1.28 and 3.94 micrograms l-1, respectively, and the limit of quantification (LOQ) was found to be 0.51, 0.29, 4.49, 1.43, 1.58 and 4.46 micrograms l-1, respectively. The loading half time, t1/2, for the cations was found to be less than 2.0 min, except for nickel for which the value was 13.1 min. The determination of each of these six cations is possible in the presence of other five, if their concentration is up to 4 times. All six metals were determined in river water (RSD approximately 0.7-7.7%) and tap water samples (RSD approximately 0.3-5.7%). The estimation of Co was made in the samples of multivitamin tablets (RSD < 2.3%). The results agree with those quoted by manufacturers.     

Poly(vinyl acetate) as a template for the radical polymerization of acrylonitrile

The template polymerization of acrylonitrile (AN) along with atactic-poly(vinyl acetate) of M _v (47,090), at 60°C for 120 min in dimethyl formamide (DMF) has been studied dilatometrically to study the effects of template, monomer, and initiator (benzoyl peroxide) concentration upon kinetics. Viscometric measurements showed that complexation between at-PVAc and PAN was maximum when template/polymer ratio was 1:1 and time required for complete complexation was 15 min. The overall energy of activation was 57.76 and 77.01 kJ/mol in the presence and absence of, PVAc, respectively. The overall system follows mechanism I, i.e., the monomer molecules get adsorbed on the surface of the template macromolecules and then propagation proceeds.     

Über die Eigenschaften hydratisierten Chromoxydes. Teil V

Ohne ZusammenfassungÜbersetzt von Dr. K. Jäckel, Marburg/L.Wir danken Herrn Prof. N. R. Dhar D.Sc. (London und Paris), F.R.I.C., F.N.I., I.E.S. (Eetd) Direktor Shila Dhar Institut für Bodenkunde und Vorstand der Chemischen Abteilung, Universität Allahabad, für sein lebhaftes Interesse und seine Ratschläge für die Arbeit.     

Thermodynamics of the conversion of aqueous glucose to fructose

The thermodynamics of the conversion of aqueous glucose to fructose has been investigated using both heat conduction microcalorimetry and high pressure liquid chromatography (HPLC). The reaction was carried out in both aqueous Tris/HCl buffer and in aqueous phosphate buffer in the pH range 7–8 using the enzyme glucose isomerase and the cofactors CoCl₂ and MgSO₄. The temperature range over which this reaction was investigated was 298.15–358.15 K. We have found that the enthalpy of reaction is independent of pH over the range investigated. A combined analysis of both the HPLC and microcalorimetric data leads to the following results at 298 15 K:ΔG° = 349 ± 53 J mol^-1, ΔH° = 2.78 ± 0.20 kJ mol^-1, and ΔC _p ^° = 76 ± 30 J mol^-1 K^-1. The stated uncertainties are based upon an analysis of both the random and systematic errors inherent in the measurements. Comparisons are made with literature data. The percent conversion of glucose to fructose has been calculated for the temperature range 300–373.15 K.     

Aqueous solubilities and octanol-water partition coefficients of binary liquid mixtures of organic compounds at 25°C

From thermodynamics and certain assumptions it is shown that, under the usual experimental conditions, the octanol-water partition coefficient (K_o/w) of a given organic liquid should be the same whether the substance is partitioned neat or as part of a mixture. Measurements of several mixtures of n-propylbenzene (log K_o/w=3.71±0.04)+ethylbenzene (log K_o/w=3.16±0.01) clearly confirm this. It is also shown that the aqueous solubility (S_w) of a neat organic liquid can be related to its aqueous solubility (S _w ), when it is present at volume fraction in an organic liquid mixture, by S _w =S_w, where is its activity coefficient in the organic mixture. The measured S _w values for n-propylbenzene + ethylbenzene (1), n-hexane + nitrobenzene (>1) and di-isopropyl ether + chloroform (<1) are found to be in good agreement with the predicted values (average differences of, respectively, <2%, 8% and 6%). In general, the bounds on S _w are expected to be 0w w.     

An equilibrium and calorimetric investigation of the hydrolysis of L-tryptophan to (indole + pyruvate + ammonia)

Apparent equilibrium constants and calorimetric enthalpies of reaction have been measured for the reaction L-tryptophan(aq) + H₂O(l) = indole(aq) + pyruvate(aq) + ammonia(aq) which is catalyzed by L-tryptophanase. High-pressure liquid-chromatography and microcalorimetery were used to perform these measurements. The equilibrium measurements were performed as a function of pH, temperature, and ionic strength. The results have been interpreted with a chemical equilibrium model to obtain thermodynamic quantities for the reference reaction: L-tryptophan(aq) + H₂O(l) = indole(aq) + pyruvate^–(aq) + NH ₄ ⁺ (aq). At T=25°C and I_m=O the results for this reaction are: K^o=(1.05±0.13)×10^–4, G°=(22.71±0.33) kJ-mol^–1, H°=(62.0±2.3) kJ-mol^–1, and S°=(132±8) J-K^–1-mol^–1. These results have been used together with thermodynamic results from the literature to calculate standard Gibbs energies of formation, standard enthalpies of formation, standard molar entropies, standard molar heat capacities, and standard transformed formation properties for the substances participating in this reaction.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

New paper chromatographic separation of microquantities of opium alkaloids

Summary A paper Chromatographic technique on salt-buffered papers for separating the alkaloids of opium has been devised. The method has been used for determining the origin of opium samples by studying the pattern of theR _f values of the alkaloids present and the effect on it produced by the presence of various adulterants.

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Zusammenfassung Die chromatographische Trennung der Opiumalkaloide auf gepuffertem Papier wurde beschrieben. Das Verfahren wurde zur Herkunftsbestimmung von Opiumproben auf Grund desR _f -Musters der anwesenden Alkaloide benützt. Der Einfluß verschiedener Fälschungszusätze wurde untersucht.

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Résumé Mise au point d'une technique de Chromatographie sur papier pour la séparation des alcaloïdes de l'opium, oú les papiers sont imprégnés des sels tampons. Utilisation de la méthode pour déterminer l'origine des échantillons d'opium en étudiant les valeurs duR _f des alcaloïdes présents et l'effet produits sur celles-ci par la présence d'adultérants divers.

     

Polymerization initiated by ylide: Polymerization of ethyl methacrylate with the use of 4-picolinium p-chloro phenacylide as initiator

The ylide 4-picolinium, p-chloro phenacylide-initiated thermal polymerization of ethyl methacrylate (EMA) was studied. 4-Picolinium p-chloro phenacylide induces the thermal polymerization of ethyl methacrylate at 65°C. The rate of polymerization (R_p) rose as the initiator concentration increased from 2 × 10^?3 to 4 × 10^?3 M and the initiating exponent was computed as 1.9. The R_p decreased as the concentration of ylide increased from 6 × 10^?2 to 1M. The greater initiator concentration also affected the molecular weight inversely. The polymerization was carried out at different temperatures and the overall activation energy was computed as 4.08 Kcal/mol. Polymerization was inhibited in the presence of hydroquinone as a radical scavenger. Kinetic studies and other data show that the overall polymerization takes place in a radical mechanism. The various kinetic parameters, such as the rate and average degree of polymerization, molecular weight, and energy of activation of the present system, were evaluated.     

Charge and Stability of Colloids

Summary Effect of non-electrolytes like methyl alcohol, ethyl, n-propyl, n-butyl, n-hexyl alcohols, glucose, sucrose, urea, starch and iso-electric gelatin on negatively charged selenium oxide sol has been studied by Spekker absorptiometer in presence of barium chloride as coagulating electrolyte. It has been observed that the substances studied generally stabilise the sol except ethylalcohol in all concentrations, methyl and n-propyl alcohols in high concentrations which have been found to sensitise it. It has been found that dielectric constant does not seem to explain completely the phenomenon of sensitisation and protection.

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Zusammenfassung Mit Hilfe eines Spekker-Absorptionsmeters wurde der Einflu? von Nichtelektrolyten für Bariumchlorid als koagulierender Elektrolyt auf negativ geladenes Selenoxyd-Sol untersucht. Die angewendeten Nichtelektrolyte waren Methyl-, ?thyl-, n-Propyl-, n-Butyl- und n-Hexyl-Alkohol, Glukose, Sucrose, Harnstoff, St?rke und Gelatine (isoelektrisch). Es wurde festgestellt, da? in allen F?llen das Sol im allgemeinen stabilisiert wird au?er durch ?thyl-Alkohol bei allen Konzentrationen, Methyl- und Propyl-Alkohol bei hohen Konzentrationen. In diesen F?llen wurde das Sol sensibilisiert. Au?erdem wurde festgestellt, da? die Dielektrizit?tskonstante offensichtlich nicht vollst?ndig die Ph?nomene der Sensibilisierung und des Schutzes erkl?rt.