Compression studies on aqueous polystyrene latices

An apparatus, that allows simultaneous measurements to be made of excess osmotic pressure and optical diffraction of polymer colloid dispersions, has been constructed. Results are reported for monodisperse polystyrene latices at several salt concentrations. An interesting feature of the results is a clear indication of a co-existence region occurring with particles of 182 nm diameter in sodium chloride concentrations of 10^–4 mol dm^–3     

Nonionic latices in aqueous media

Nonionic latices in aqueous media prepared using methoxy polyethylene glycol methacrylate as a comonomer/stabiliser and ascorbic acid/hydrogen peroxide as the initiator have been examined for stability in the presence of the 21 electrolyte, barium chloride. These latices were found to be stable up to the concentrations of barium chloride examined, 0.75 mol dm^–3. Charge stabilised latices, on the other hand, were coagulated in 2.1×10^–2 mol dm^–3 barium chloride. The high stability of the nonionic latices was attributed to the grafting, during polymerisation, of methoxy polyethylene glycol chains to the surface of the core particle of polystyrene. The nonionic latices on concentration to high volume fraction gave highly ordered packing of the particles even in the presence of 0.1 mol dm^–3 sodium chloride.     

Preparation of titania colloids by thermal hydrolysis of urea and densification behavior of the collid-derived monolithic titania gels

Hydrous titania colloids with different sizes and shapes were prepared from urea-containing TiCl₄ solutions by controlled thermal hydrolysis of urea. Very small colloidal particles (Sw=280–290 m²/g) with anatase structure were precipitated from aqueous HCl solutions of [TiCl₄] <1.0 mol/dm³ and [urea] >16.6 mol/dm³. Sols containing such colloids could be converted to translucent monolithic gels. A decrease in urea concentration ([urea]=8.3 mol/dm³) caused the production of aggregated rutile-type particles with a large aspect ratio, from which only titania powder was obtained. Heating of a monolithic gel above 500°C resulted in the accelerated densification of the gel. A highly densified titania with 96% of theoretical density was produced from the monolithic gel after heating at 700°C for 6 h.     

Kinetics and mechanism of exchange reaction of [Y(APTA)] (APTA=o-aminophenol-N,N, O-triacetic acid) with copper(II)

Summary The kinetics of the exchange reaction between [Y(APTA)] and Cu^II have been investigated over a range of [H⁺] from 2.5×10^–5 to 7.5×10^–4 mol dm^–3 at 30°C and ionic strength 0.2 mol dm^–3 KNO₃. The results show that the exchange reaction proceeds via both self-and proton-catalyzed dissociation of [Y(APTA)] and also by the direct attack of Cu^II on [Y(APTA)]. The corresponding rate constants k_d, k _h and k_Cu have been evaluated as 6.3s^–1, 8.4×10⁴ mol^–1 dm³ s^–1 and 416mol^–3 dm³ s^–1 respectively. The possible intermediates are discussed in terms of the structure of APTA. The complex-formation rate constants of Y^III with APTA^3- and HAPTA^2- were also obtained.     

Extraction and stripping study of strontium ions across D2EHPA-TBP-kerosene oil based supported liquid membranes

A Sr ion transport study across D2EHPA-TBP kerosene oil based liquid membranes supported on microporous polypropylene film has been performed. The parameters studied were the effect of di(2-ethylhexyl)phosphoric acid (D2EHPA) and TBP concentration variation in the membrane liquid, HNO₃ concentration variation in the stripping phase and citric acid concentration variation in the feed solution. The optimum conditions of transport are 0.3 mol/dm³ D2EHPA, 0.1 mol/dm³ TBP, 0.01 mol/dm³ citric acid in feed and 2 mol/dm³ HNO₃ in the stripping phase. The mechanism of transport observed is counter-ion coupled transport. The coupling ions are protons. The maximum flux for Sr ion transport observed is 5.33·10^–5 mol·m^–2·s^–1 and maximum permeability under optimum conditions observed is 8.08·10^–11 m^–2·s^–1.     

Formation of uniform silver particles from bis (1,2-ethanediamine)silver(I) complex

Uniform spherical silver particles were produced by decomposing the bis(1,2-ethanediamine)silver(I) complex, by aging a solution of 1.0×10^–3 mole dm^–3 in silver (I) nitrate, 1.0 mole dm^–3 in 1,2-ethanediamine, and 2.5×10^–1 mole dm^–3 in nitric acid (basic solution) at 100°C for 42 min. The average modal diameter was estimated to be 0.52 m with a relative standard deviation of 0.10. A moderately oxygenrich layer, 40 Å thick, on the surface of the particles was detected by means of photoelectron surface microanalysis (XPS). The silver particles grew through a polynuclear-layer mechanism, as judged from the concentration change in soluble silver(I) species in the supernatant solution. The particles' point of zero charge (PZC) was estimated at pH 6.5 by potentiometric titration.     

The aggregation in dodecyltrimethylammonium hydroxide aqueous solutions

The aggregation of dodecyltrimethylammonium hydroxide (DTAOH) aqueous solutions has been studied by several methods. It is stepwise and four critical points were found. AtC _T=(2.51±0.10)×10^–4 mol · dm^–3 the surface excess becomes zero, atC _T=(1.300±0.041)×10^–3 mol · dm^–3 small aggregates from, which grow with concentration. AtC _T=(1.108±0.010)×10^–2 mol · dm^–3 true micelles form (CMC) and at (3.02±0.28)×10^–2 mol · dm^–3 the structure of micelles probably changes affecting their properties. The DTAOH micelles are highly ionized (=0.8) at the CMC, and decreases to reach very small values when the total concentration increases.     

On the characteristics and mechanism of the radiation-induced chain reaction between sulfur dioxide and molecular oxygen in acid solutions

Characteristics of the -induced chain reaction between sulfur dioxide and molecular oxygen in perchloric and sulfuric acid media in the presence of Ce(III) ions have been studied. The concentration effects of dissolved oxygen (0.2·10^–3–9.4·10^–3 mol/dm³, sulfur dioxide (0.3·10^–1–2.0·10^–1 mol/dm³ and Ce(III) (0.2·10^–3–4.8·10^–3 mol/dm³) and dose rate (0.26·10¹⁹–1.0·10¹⁹ eV/dm³·s) on the radiation — chemical yield of oxygen consumption G(–O₂) and accumulation of sulfate G(HSO ₄ ^– ), have been investigated. The reaction proceeds with G(–O₂) reaching 10²–10³ molecule/100eV in a catalytic regime. The reaction rate in perchloric acid medium is 3–4 times lower than that in the sulfuric acid medium and depends on the SO₂, O₂ and Ce(III) concentrations, the reaction order varying from 1.0 to 0 and/or in the reverse direction. The mechanism of the process involves chain propagation with 3 stages and 3 intermediates: SO₃H, HSO₅ and Ce(IV). The catalytic effect is caused by the interaction of HSO₄ with Ce(IV) ions followed by their reduction when interacting with SO₂, yielding SO₃H radicals. Chain termination may be due to one or two of the three intermediates or due to all three particles, the kinetics depending on this. Kinetic equations describing the experimental data have been obtained.     

Adsorptive stripping voltammetric determination of 1-(4′-bromophenyl)-3,3-dimethyltriazene

The optimum conditions were established for the determination of the genotoxic substance 1-(4-bromophenyl)-3,3-dimethyltriazene by differential-pulse voltammetry at a hanging mercury drop electrode in the concentration range 1 × 10^–4 to 1 × 10^–7 mol dm^–3. The sensitivity of the determination can be improved through adsorptive accumulation of the investigated substance on the surface of the hanging mercury drop electrode: differential pulse adsorptive stripping voltammetry can be used in the concentration range 1 × 10^–7 to 2 × 10^–10 mol dm^–3. The relative standard deviation (for ten determinations at 2 × 10^–10 mol dm^–3) was 7.5%.     

Anion-exchange behaviour of a number of metal ions on DEAE-cellulose in hydrobromic and hydriodic acid media

Summary The adsorption behaviour of 48 metal ions on DEAE-cellulose layers has been investigated in aqueous hydrobromic and hydriodic acid media. R_F values are given as a function of the hydrobromic and hydriodic acid concentration over the ranges 0.01–6 mol dm^–3 and 0.01–3 mol dm^–3, respectively, and are compared with those obtained with Avicel SF. R_F spectra are comparatively simple in both media, reflecting the strong affinity of the bromide and iodide ions to the DEAE-cellulose phase. Pd, Pt, Re, Au and Hg are distributed chromatographically in either system, while most other metal ions exhibit rather extreme R_F values of near unity or zero. Therefore, the selectivity of the systems is particularly high for Pd, Pt, Re, Au and Hg, providing the possibility of their excellent selective separations.     

Short-time mobility of spherical particles in concentrated aqueous dispersions determined by diffusing wave spectroscopy

Summary The diffusion of optically dense, charge stabilized, polystyrene latex spheres of 500 nm radius in water at 25°C was determined by diffusing wave spectroscopy in the backscattering mode. The diffusion coefficient of the latex spheres had a value of 4.8×10^–13 m² s^–1 at infinite dilution and monotonically decreased as the number density of latex spheres increased. The diffusion coefficient dropped by a factor of 3 at 38 volume % latex and a factor of 20 at 59 volume % latex. Comparison was made to diffusion of sterically stabilized poly(methyl methacrylate) latex in refractive index matched mixed organic fluids as determined by dynamic light scattering. The concentration dependence determined by diffusing wave spectroscopy matched closely to the short-time diffusion determined by dynamic scattering and not to the long-time diffusion. Although the difference in repulsive potential between the charge and the sterically stabilized lattices must be large, it has a surprisingly small effect on the translational diffusion of the latex over distances small compared to the intersphere distance.     

Preparation,Characterization and Standard enthalpy of formation of Sr2CeO4.

Sr₂CeO₄ has been prepared by sol-combustion and co-precipitate routes and the resulting products have been characterized by XRD analysis. The molar enthalpies of solution of Sr₂CeO₄(s), Sr(NO₃)₂(s) and Ce(NO₃)₃·6H₂O(s) in 0.150 dm^–3 of (4.41 mol dm–3 H₂O₂+4.23 mol dm^–3 of HNO₃) solvent as well as the molar enthalpies of solution of Sr₂CeO₄(s), SrCl₂(s) and CeCl₃(s) in 0.150 dm³ of (1.47 mol dm^–3 H₂O₂+3.05 mol dm^–3 of HClO₄) solvent have been measured using an isoperibol type calorimeter. From these results and other auxiliary data, the standard molar enthalpy of formation of Sr₂CeO₄ has been derived to be –2277.3±3.1 kJ mol^–1 at 298.15 K. This is the first reported thermodynamic data on this compound.     

Preparation and properties of yttrium,lanthanum, and lanthanidem-nitrobenzoates

The conditions of the formation of rare earth elementm-nitrobenzoates were studied and their quantitative composition and solubilities in water and benzene at 298 K were determined (their solubilities are in the orders of 10^–3 mol dm^–3 and 10^–4 mol dm^–3, respectively). From the values of solubilities in water the solubility products were established (they are in the orders of 10^–10 mol⁴ dm^–12).The IR and X-ray spectra for the prepared complexes and the dehydrated rare earthm-nitrobenzoates were recorded. All obtained complexes were found to be crystalline compounds. The conditions of thermal decomposition for complexes were also studied. It was found that on heating above 573 K the complexes decompose explosively and undergo a melting process at the same time. Therefore the thermal decomposition was carried out in the temperature range 273–573 K. The obtained results show that during dehydration process no transformation of the nitro group to nitrito occurs.

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Darstellung und Eigenschaften von Y, La und Lanthaniden-meta-Nitrobenzoaten

Zusammenfassung Die Bedingungen zur Darstellung von Y-, La- und Lanthanidenmeta-Nitrobenzoaten wurden untersucht. Ihre quantitative Zusammensetzung und ihre Wasserlöslichkeit bei 298K wurden bestimmt (die Löslichkeit ist in der Größenordnung 10^–3 mol dm^–3). Die Infrarot- und Röntgenspektren der erhaltenen Komplexe sowie derm-Nitrobenzoate der seltenen Erden nach der Dehydratisierung wurden gemessen und dabei festgestellt, daß es sich stets um kristalline Verbindungen handelt. Das thermische Verhalten der erhaltenen Komplexe wurde festgestellt: Sie zerfallen über 573 K explosiv und schmelzen zugleich. Der thermische Zerfall der erhaltenenm-Nitrobenzoate der seltenen Erden wurde im Temperaturbereich von 273–573 K untersucht. Es wurde festgestellt, daß die Y-, La- und Lanthaniden-m-Nitrobenzoate bei Temperaturzunahme oder im Dehydratisierungsprozeß keiner Umgruppierung in entsprechende Nitritoverbindungen unterliegen.

     

Adsorption of Cl? ions on electrodeposited rhodium black layer (rhodized electrode) at low concentrations

The adsorption of Cl^– ions on rhodium black layer (rhodized electrodes) was studied by radiotracer technique at low Cl^– ion concentrations (c10^–5 mol dm^–3) in 1 mol dm^–3 H₂SO₄ supporting electrolyte. The specific adsorption of Cl^– ions was treated in terms of partition between solution phase and electrodeposited Rh black layer. The potential dependence of the partition coefficient is determined.     

Aqueous polymerization of methacrylamide initiated by potassiumpersulfate-L-cystein hydrochloride redox system

The aqueous polymerization of methacrylamide initiated by potassiumpersulfate-L-cystein hydrochloride redox system has been studied at 35±0.01 C under nitrogen atmosphere. The initial rate of polymerization has been found to be directly proportional to the monomer and activator concentration, in the range of 1.0 × 10^–1 to 4.0 × 10^–1 mol dm^–3 and 1.25 × 10^–3 to 5.0 × 10^–3 mol dm^–3 respectively. The order with respect to initiator has been found to be 0.5, indicating thereby that the termination takes place by bimolecular process. The overall energy of activation has been found to be 53±1 KJ/mol.     

Pulse radiolysis of Triton X-100 aqueous solution

Pulse radiolysis of deaerated aqueous solutions of 4·10^–5–2.4·10^–3 mol dm^–3 Triton X-100 gives rise to a transient species originating from the reactions of OH radicals and H atoms. The rate constants of these reactions were found to be 8.8·10⁹ mol^–1·dm³·s^–1 and 1.25·10⁹ mol^–1·dm³·s^–1, respectively, for Triton X-100 concentrations below CMC. The corresponding transient species were found to decay according to second order kinetics. The mechanism of the reactions involved including concentration effects is discussed.     

Precipitation separation of strontium and calcium from acidic solutions using crown ether and tungstosilicic acid

Strontium forms a compound of composition (SrL)₂A·nH₂O with low solubility (5.0·10^–6 mol Sr·dm^–3) in the presence of 18-crown-6 (L) and tungstosilicic acid (H₄A) in acid media, as has been found by radiometric precipitation titration. Formation of the compound with limited solubility was used for separation of strontium and calcium from 1 mol·dm^–3 HCl. It is possible to separate strontium in the range from trace to 6 mmol·dm^–3 in the presence of calcium with its concentration up to 0.2 mol ·dm^–3 and the recovery determined was 95% of Sr and 5% Ca or 90% of Sr and 4% Ca, respectively. The ratio of Sr/Ca depends on the stability constants ratio of metal-L (⊃_SR/⊃_ca) in the case of gradual addition of L. Potassium up to the concentration of 0.05 mol·dm^–3 does not influence recovery of strontium.     

Stoichiometry and kinetics of the oxidation of hydroxylammonium ion by 12-tungstocobaltate(III) anion in aqueous solution

Summary The stoichiometry and kinetics of the oxidation of hydroxylammonium ion by the 12-tungstocobaltate(III) anion has been studied in hydrochloric acid medium. The ratio of mols of oxidant consumed per mol of hydroxylammonium ion is 11 and the evolution of nitrogen is confirmed. In the 0.1–1.0 mol dm^–3 [H⁺] region, the oxidation is acid-independent and obeys the empirical rate law: –d[oxidant]/dt=k[oxidant] [reductant] where k=(3.51±0.18)×10^–4 mol^–1dm³s^–1 at 22.4±0.1C and I=2.0 mol dm^–3 (NaCl). Possible reaction steps and mechanism are suggested.     

90Sr and137Cs in atmospheric precipitations during 1980–1985 in the Bucharest area

Samples of precipitations were collected quarterly and analyzed for⁹⁰Sr and¹³⁷Cs. The values obtained ranged from 0.001 to 0.004 Bq dm^–3, with a maximum of 0.010 Bq dm^–3 for⁹⁰Sr;¹³⁷Cs values ranged from 0.001 to 0.005 Bq dm^–3, with a maximum of 0.070 Bq dm^–3. The highest values were observed during the 2nd and 3rd quarters of 1981.     

Kinetics and mechanism of the base hydrolysis of thecis-chlorobis(ethylenediamme)(benzimidazole)cobalt(III) cation

Summary The hydrolysis ofcis-[CoCl(en)₂(bzmH)]²⁺ (en=ethylenediamine, bzmH=benzimidazole) has been studied over the pH range 8.31–11.58 at I=0.1 mol dm^–3 and 25°. Potentiometric titration of aqueous solutions of the [Co(en)₂(bzmH)OH₂]³⁺ complex obtained by silver(I) catalysed aquation of the chloro-complex give pK₁=5.81 and pK₂ = 8.84 for Equilibria (1) and (2) at 25° and I=0.1 mol dm^–3. Spectrophotometric titration of the hydroxy complex also gives a value of pK₂=8.88 for the ionisation of the coordinated benzimidazole. The kinetic data can be interpreted in terms of base hydrolysis ofcis-[CoCl(en)₂(bzmH)]²⁺ (k_OH=220 dm³ mol^–1s^–1) andcis-[CoCl(en)₂(bzm)]⁺ (k_OH=14.9 dm³ mol^–1s^–1). Comparisons with the corresponding imidazole and pyridine complexes are made.