Critical solution point and chain dimension of branched-polystyrene solutions

Summary Critical solution point and chain dimension were measured for branched polystyrene(BPS) in solution as a function of molecular weight(M) and compared with those for linear polystyrene(LPS). The critical concentration _c of BPS was quite different from that of LPS at a fixed M, but the same at a fixed overlap-concentration ^*, i.e., plots of _c vs. ^* fall on a single straight line for both BPS and LPS (gf_c ^*). Reduced critical temperature _c defined by gt_c=(–T_c)/ [T_c: critical temperature, : the -temperature] was related to _c as _{c c} ² for BPS, whereas _{c c} for LPS.     

Porous mullite ceramics through diphasic gels of large boehmite and small silica particles

Mullite formation process has been studied in stoichiometric mullite (3Al₂O₃·2SiO₂) diphasic gel containing large boehmite (1 m) and small silica (10 nm) particles. It has been found that initial mullitization did not take place inside the silica phase (cristobalite), but took place in the defect -alumina phase. -alumina was stabilized by silica when the temperature was below 1350°C. At temperatures above 1350°C, mullite crystallized directly. It was suggested that silica diffused into the pores (<1.8 nm) of -alumina and prevented the collapse of -alumina pore structure. On the other hand, when silica was not present, the pore structure of -alumina collapsed and -alumina crystallized at 1100°C. Porous mullite ceramics were obtained by using special diphasic gels containing large boehmite and small silica particles.     

Liquid-phase mass transfer enhancement by gas evolution at inclined plates

The limiting current technique has been employed to determine mass transfer coefficients at vertical and inclined plates with stirring by coplanar electrochemical oxygen evolution. Orientation of the plate has been varied from –45 (down-facing inclined position) to +45 (up-facing inclined position) at ten intervals. At a constant oxygen evolution rate, maximum mass transfer enhancement was achieved at down-facing inclined orientations where (the angle from vertical) is small. The inclination angle at which mass transfer attained its highest value depended on the oxygen evolution rate and is given by _max =a + 10.96 logI _g whereI _g (mA) is the electrochemical current for the oxygen evolution.For the range of the inclination angle, 0 _max, the relationship between the mass transfer coefficient and can be represented byK =K _o +aK _o(sin )^0.3 whereK _o is the mass transfer coefficient at the vertical plate.     

Adsorption and corrosion inhibition properties of thymol

On the basis of electrocapillary and differential capacitance measurements it was established that thymol from acid solutions was adsorbed on a mercury electrode. The shape of the thymol adsorption isotherm, the positive value of the attraction constanta and the position of the minimum of the Inc/ vs dependence (wherec is thymol concentration and is electrode coverage) indicated the applicability of the Frumkin equation.The characteristics of thymol as a corrosion inhibitor were studied by observing the dissolution of aluminium and zinc in hydrochloric acid with and without thymol addition. The values of the reaction numbers (RN) plotted against thymol concentration were compared with the adsorption curves. The analysis of the results, i.e. the comparison of theRN(c) and(c) curves for the liquid and solid metal electrodes and the difference between theRN(c) curves for aluminium and zinc, indicated a different adsorption mechanism and also a different corrosion inhibition efficiency by thymol for aluminium and zinc.     

Adsorbed Atoms and Molecules Destined for a Reaction

The idea of an activation complex is popular for explaining reaction rates, but the characteristics of reactions and catalysis may not be explained in this way. A predestined state for each reaction composed of surface atoms and adsorbed species is responsible for these features. Two single Sn atoms trapped in adjacent half-unit cells of an Si(111) 7 × 7 surface is an example of a predestined state. An isolated Sn atom in a half-unit cell does not migrate to other half-unit cells at room temperature, but when two single Sn atoms are in adjacent half-unit cells they undergo rapid combination to form an Sn₂ dimer. In addition, these two single Sn atoms replace the center Si adatoms and an Si₄ cluster is formed. The spatial distribution of molecules desorbing from surfaces may reflect the predestined states for the desorption processes. The spatial distribution in the temperature-programmed desorption (TPD) of NO on Pd(110) and Pd(211) surfaces and that in the temperature-programmed reaction (TPR) of NO + H₂ were studied. N₂ desorbing from Pd(110) by the recombination of N atoms obeys cos⁶ – cos⁷ but the N₂ produced by a catalytic reaction of NO with H₂ obeys cos. In contrast, the N₂ desorbing with NO at 490 K in the TPD of Pd(110) shows a sharp off-normal distribution expressed by cos⁴⁶( – 38). The adsorption of NO on Pd(211) predominantly occurs on the (111) terrace but the spatial distribution suggests that the predestined states for the reaction and desorption are formed on both the (111) terrace and (100) step surfaces.     

Activation of Ni/A12O3 catalysts through modification of the Al2O3 support

The effect of alumina pretreatment on the performance of alumina supported nickel catalysts was demonstrated in gas phase hydrogenation of toluene to methylcyclohexane. The state of the alumina was changed from pure to pure phase through various heat treatments in air. The catalysts were prepared from vapor phase by saturating the accessible binding sites on the pretreated alumina with the nickel precursor. The highest number of active sites for hydrogenation was observed for catalysts prepared on alumina having an incomplete phase transition and a / alumina phase ratio between 0.5 and 10. Results from temperature programmed desorption (TPD) studies revealed that a maximum in weakly chemisorbed hydrogen as well as in total amount of desorbed hydrogen was found for the same catalysts. By hydrogen chemisorption studies the total hydrogen uptake was found to correlate with the observed hydrogenation maximum. It is suggested that both the chemical and physical properties of the alumina influence the activity. An optimal metal-support interaction and structural defects on the alumina due to the phase transition can explain the observed maximum in the number of active sites and in hydrogen uptake.     

Lean NOx catalysis over alumina‐supported catalysts

aluminasupported catalysts show promise as lean NO_x catalysts. The role of alumina in influencing the structural and chemical properties of the active phase supported on it is discussed using some effective aluminabased lean NO_x catalysts. These include Ag/Al₂O₃, CoO_x/Al₂O₃ and SnO₂/Al₂O₃. Alumina plays an important role in stabilizing Ag in the oxidic phase and cobalt in the 2+ oxidation state. For SnO₂/Al₂O₃, alumina increases the SnO₂ surface area. On both Ag/Al₂O₃ and SnO₂/Al₂O₃, alumina also participates actively in the NO_x reduction reaction. An active organic intermediate is formed on Ag or Sn oxide which reacts with NO_x subsequently on alumina to form N₂.     

Preparation of nanosize Pt clusters using ion exchange of Pt(NH3) 4 2+ inside mesoporous channel of MCM-41

Mesoporous molecular sieve MCM-41 with a Si/Al ratio of 35 was obtained by hydrothermal synthesis using a gel mixture with a molar composition of 6 SiO₂0.1 Al₂O₃1 hexadecyltrimethylammonium chloride 0.25 dodecyltrimethylammonium bromide 0.25 tetrapropylammonium bromide0.15 (NH₄)₂O1.5 Na₂O300 H₂O. The MCM-41 sample was calcined in O₂ flow at 813 K and subsequently ion exchanged with Ca²⁺. A small Pt cluster has been supported on the MCM-41 sample following a procedure using ion exchange of Pt(NH₃) ₄ ²⁺ . The Pt(NH₃) ₄ ²⁺ ion supported on MCM-41 has been activated in O₂ flow at 593 K and subsequently reduced with Fh flow at 573 K, in the same way used for the preparation of a Pt cluster entrapped inside the supercage of zeolite NaY. The resulting Pt cluster supported on the MCM-41 shows hydrogen chemisorption oftotal two H atoms per Pt at 296 K (based on the total amount of Pt) and high catalytic activity for hydrogenolysis of ethane. The chemical shift in¹²⁹Xe NMR spectroscopy of adsorbed xenon indicates that the Pt cluster is located inside the mesoporous molecular sieve.     

The impedance of the alkaline zinc-manganese dioxide cell. II. An interpretation of the data

The impedance of small alkaline zinc-manganese dioxide cells has been interpreted in terms of a controlling charge-transfer and diffusion process at the zinc electrode throughout the early stages of discharge. After about 20% of the available charge has been removed, it becomes necessary to include the manganese dioxide electrode circuit components. This network has the circuit elements for charge transfer and a proceeding chemical reaction. The Warburg component for the manganese dioxide electrode need not be considered since the effective area considerably exceeds that of the zinc. The relative areas are confirmed by the magnitudes of the circuit element components. The decomposition of the impedance data has been successfully accomplished as far as 80% discharge; after this point cells show considerable differences from cell to cell, especially in the low-frequency range, which makes a confident interpretation difficult. It is considered that this is due to the loss of the physical definition of the system.Nomenclature C _m,C _z double-layer capacitances of MnO₂ and Zn electrodes, respectively - C _X,R _X parallel branch accounting for current density varying with fractional electrode coverage - R resistance of electrolyte - V open-circuit voltage of cell - Z, Z, Z impedance of cell,resistive component ofZ and reactive component ofZ, respectively - _m, _z transfer resistance of MnO₂ and Zn electrodes, respectively - , _R, _C in Warburg equation:Z _W = ^–1/2(1–i) orZ _W = _R^–1/2– i_Cco^–1/2     

Note of the estimation of the Θ temperature and Ψ parameter from the critical temperature data

Summary Critical values of the polymer volume fraction _2,c and the interaction parameter _c have been computed for the case that the equation for the chemical potential of solvent contains terms _{c 2} ³ and _{c 2} ⁴ in addition to ₂ ² . For 0 _c 1/3, the limits for infinite chain length are _2,c = 0 and _c = 0.5. Quite different results are obtained for _c > 1/3, _2,c being finite and _c lower than 1/2. Conclusions for the estimation of the temperature and the entropy-of-dilution parameter are discussed.     

Mechanism of copper-nickel alloy electrodeposition

The codeposition kinetics of copper and nickel alloys in complexing citrate ammonia electrolytes has been investigated by means of polarization and electrochemical impedance techniques. It is confirmed that the two-step discharge of the complexed cupric species Cu(II)Cit is diffusion-controlled during the alloy deposition, resulting in an increase in the nickel content of the alloy with electrode polarization. Impedance spectra are also consistent with a two-step discharge of Ni(II) cations involving an intermediate adsorbate, Ni(I)_ads, originating from the reversible first step. A reaction model is developed for the parallel discharge of Cu(II)Cit and Ni(II) in which the reactions for nickel deposition are catalysed by active sites permanently renewed at the surface of the growing alloy. The surface density of these sites, slowly nucleated from Ni(I)_ads and included in the deposit, varies with the electrode polarization, thus generating a low-frequency feature specific of Cu–Ni codeposition. This reaction model reproduces to a reasonable extent the potential dependence of the partial current densities for nickel and copper discharge, the current dependence of the alloy nickel content and also most of the experimental relaxation processes observed on impedance spectra.Nomenclature b ₁,b ₂,b ₃,b ₃ b ₄,b ₅,b ₇ Tafel coefficients (V^–1) - C concentration of Cu(II)Cit at distancex (mol cm^–3) - [Cu(II)] bulk concentration of Cu(II)Cit (mol cm^–3) - C ₀ concentration of Cu(II)Cit atx=0 (mol cm^–3) - C* concentration of Cu(I)Cit atx=0 (mol cm^–3) - C ₀, C* variations inC ₀,C* due to E - (Cu), (Ni) molecular weights (g) - C _dl double layer capacitance (F cm^–2) - D diffusion coefficient of Cu(II)Cit (cm² s^–1) - E electrode potential (V) - f frequency (s^–1) - F Faraday (constant 96 487 A s mol^–1) - g interaction factor between adsorbates - i,i _Cu,i _Ni current densities (A cm^–2) - Im(Z) imaginary part ofZ - j (–1)^1/2 - k mass transfer coefficients (cm s^–1) - K ₁,K ₃ rate constants (cm s^–1) - K ₂ rate constants (s^–1) - K ₃,K ₄,K ₅,K ₆,K ₇ rate constants (cm^–2 s^–1) - [Ni(II)] bulk concentration of NiSO₄ (mol cm^–3) - R _t charge transfer resistance ( cm²) - Re(Z) real part ofZ - t time (s) - x distance from the electrode (cm) - Z _F faradaic impedance ( cm²) - Z electrode impedance - maximal surface concentration of Ni(I)_ads intermediates (mol cm^–1) - nickel content in the deposited alloy (wt %) - thickness of Nernst diffusion layer (cm) - ₁ electrode coverage by adsorbed Ni(I)_ads intermediate - ₂ electrode coverage by active sites - ₁, ₂ variations in ₁, ₂ die to E - * =K ₂ ^–1 (s) - _d diffusion time constant (s) - ₁ time constant relative to ₁ (s) - ₂ time constant relative to ₂ (s) - angular frequency (rad s^–1) - electrode rotation speed (rev min^–1)     

Oxidation of carbon monoxide and deuterium on a Pd(100) film

For Pd/MgO(100) pre-exposed to oxygen, the catalytic oxidation of CO and D₂, respectively, has been studied in the temperature range 100–300°C. At temperatures 200°C, the CO₂ desorption rate is independent of oxygen coverage, _O, and the reactive sticking coefficient for CO is close to unity. The D₂O desorption rate is strongly dependent on _O. D₂ adsorption is blocked by adsorbed oxygen and the maximum D₂O desorption rate is reached when almost all oxygen has been consumed (<0.03). The formation of an oxygen c(2×2) structure, coexisting with the initial p(2×2) phase, is reflected in the oxidation rates.     

Differentiation between conformational transitions of polymers and the transition observed near the theta conditions

Summary The differentiation between the conformational transitions of polymers and the transition observed near the conditions has been investigated. The conformational transitions are related with side-group effects and vanish under the influence of an appropriate amount of a polar solvent. In the contrary, the transition observed in the vicinity of the temperature is related with chain-backbone effects. The addition of a polar solvent shifts this transition to a different temperature in accordance with the resulted change of the temperature of the system.     

Relationship between preferential adsorption coefficient and intrinsic viscosity in ternary systems

Summary The relation proposed between the preferential adsorption coefficient, , and the intrinsic viscosity, ¦¦ ¦¦=¦¦+AK has been applied in this paper to previously published data. This equation is found to be valid in theta condi tions and far away from them. The obtained results are compared to the ones calculated with the Dondos-Benoit equation.     

Analysis of irreversible oxidation wave of adsorbed CO at Pt(1 1 1), Pt(1 0 0) and Pt(1 1 0) electrodes

The oxidation wave of CO preadsorbed at 50 mV on Pt(1 1 1), (1 0 0) and (1 1 0) electrodes in phosphate buffer solution of pH 3 was observed as a function of the sweep rate. The sweep rate dependence of the peak current and peak potential, as well as the form of the wave, were examined on the basis of the Gilman mechanism that the electron transfer from a complex consisting of CO and oxygen containing species is the rate-determining step. An electron transfer step from CO itself was excluded. The peak current and peak potential analyses and the wave simulation gave the same value for f, the change in the interaction energy during the formation of the activated complex from the reactants. f was sweep-rate and surface-structure dependent. The nature of f was discussed.Nomenclature symmetry factor - reversible work required to bring an adsorbed species from its standard state - µ electrochemical potential - electrode potential referred to the reversible hydrogen electrode - _p peak potential - _1/2 width at half height of the oxidation wave - (a) adsorbed state - f() mutual interaction energy of the activated complex inRT units - f(R) mutual interaction energy of the reactants in RT units - f f() –f(R) - i oxidation current density, mA cm^–2 - i _p peak current, mA CM^–2 - k rate constant - Q ₀ electric charge, mCcm^–2 - v sweep rate, m Vs^–1 This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribuion to electrochemistry.     

Kinetics and Mechanism of Copolymerization of α-terpineol with Methylmethacrylate in Presence of Azobisisobutyronitrile as an Initiator

The radical copolymerization of -terpineol with methyl-methacrylate in xylene at 80±0.1C for 50 minutes in the presence of azobisisobutyronitrile (AIBN) follows ideal kinetics and results in the formation of a functional and random copolymer. The activation energy is 33 KJ/mole. The IR spectrum and NMR spectra of the copolymer(s) shows the bands at 1750 and 3400 cm^–1 for ester group of methylmethacrylate and alcoholic group of -terpineol and peaks at 3 to 4 for methoxy group and at 6.5 to 7.5 due to alcoholic group of methylmethacrylate and -terpineol repectively. The values of reactivity ratios, calculated by Kelen–Tüdos method, are r ₁ (MMA) = 0.18 and r ₂ (-terpineol) = 0.046. The Alfrey-Price; Q–e parameters for -terpineol has been calculated as 0.149 and 2.486. The mechanism of copolymerization has been elucidated and it is concluded that the double bond present in the monocyclic ring of -terpineol is an active site for copolymerization and the alcoholic group of -terpineol remain to give functional copolymer.     

Chemical modification of copoly(methylsilylene/1,4-phenylene) by Pt-catalyzed hydrosilation reactions with functionally substituted alkenes

Copoly(methyl-3-biphenoxypropylsilylene 1,4-phenylene), copoly(methyl-3-cyanopropylsilylene 1,4-phenylene), copoly(methyl-3-ethoxypropylsilylene 1,4-phenylene), copoly(methyl-3-phenoxypropylsilylene 1,4-phenylene), and copoly(methyl-4,7,10,13-tetraoxatetradecanylsilylene 1,4-phenylene) have been prepared by platinum-catalyzed hydrosilation graft reactions between poly (methylsilylene 1,4-phenylene) and appropriate functionally substituted alkenes. These polymers have been characterized by¹H,¹³C, and²⁹Si NMR as well as by FT-IR and UV-vis spectroscopy. The molecular weight distribution of these polymers has been determined by gel permeation chromatography (GPC), and their glass transition temperatures (T _e) by DSC.     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Studies concerning charged nickel hydroxide electrodes IV. Reversible potentials in LiOH,NaOH, RbOH and CsOH

The variation of reversible potential E_r with log a_moh and has been studied for several nickel hydroxide/oxyhydroxide couples in various alkali hydroxides. Both activated and deactivated -phase couples show only a small dependence ofE _r with log_moh (or where known) in LiOH, NaOH, RbOH and CsOH electrolytes. The change in MOH content on oxidation/reduction is found to be about 0.1 mol MOH per two-electron transfer and is the same as found previously in KOH. These results confirm that the bulk oxidized -phase lattice is devoid of alkali cation although a small quantity may be adsorbed by the surface. On the other hand both activated and deactivated /-phase couples show a marked dependence of 0.45 mol MOH per two-electron transfer in LiOH, NaOH and RbOH (at concentrations > 0.5 m), also in good agreement with earlier data for KOH. On the basis of these results a general stoichiometry can be inferred for the -phase, namely M_0.32NiO₂ · 0.7H₂O where M=Li⁺, Na⁺, K⁺ or Rb⁺. Measurements imply that the Cs⁺ ion or the Rb⁺ ion at low concentration (<0.5 m) do not enter the interlayer structure of the -phase. This behaviour is thought to be related to the low Rb-O and Cs-O bond strengths afforded by the -phase structure.