Nano ZSM-5 type ferrisilicates as novel catalysts for ethylbenzene dehydrogenation in the presence of N2O

Nanosized ZSM-5 type ferrisilicates were successfully prepared using hydrothermal process. Several parameters including gel initiative compositions (Na⁺ or K⁺ alkali system), SiO₂/Fe₂O₃ molar ratios and hydrothermal temperature were systematically investigated. The samples were characterized by XRD, TEM, SEM-EDS, BET surface area and ICP techniques. It was found that surface areas and the total pore volume increase with increasing in the SiO₂/Fe₂O₃ molar ratio at Na-FZ ferrisilicates. The catalytic performance of the synthesized catalysts was evaluated in ethylbenzene dehydrogenation to styrene in the presence of N₂O or steam at temperatures ranging from 400 °C to 660 °C under atmospheric pressure. The effects of gel initiative compositions, SiO₂/Fe₂O₃ molar ratio as well as the hydrothermal synthesis temperature on the catalytic performance of these catalysts have been addressed. It was shown that styrene yield significantly influenced by altering in the SiO₂/Fe₂O₃ ratio but was not greatly influenced by changes in hydrothermal synthesis temperatures. The comparison between performance of potassium and sodium containing catalysts was shown that the one with potassium has higher yield and selectivity toward styrene production at an optimum temperature of 610 °C.     

In‐situ Raman spectroscopy study of Ru/TiO2 catalyst in the selective methanation of CO

Raman spectroscopic technique has been used to characterize a Ru/TiO₂ catalyst and to follow in situ their structural changes during the CO selective methanation reaction (S‐MET). For a better comprehension of the catalytic mechanism, the in‐situ Raman study of the catalysts activation (reduction) process, the isolated CO and CO₂ methanation reactions and the effect of the composition of the reactive stream (H₂O and CO₂ presence) have been carried out. Raman spectroscopy evidences that the catalyst is composed by islands of TiO₂–RuO₂ solid solutions, constituting Ru–TiO₂ interphases in the form of Ru_xTi_{1 − x}O₂ rutile type solid solutions. The activation procedure with H₂ at 300 °C promotes the reduction of the RuO₂–TiO₂ islands generating Ru^o–Ti³⁺ centers. The spectroscopic changes are in agreement with the strong increase in chemical reactivity as increasing the carbonaceous intermediates observed. The selective methanation of CO proceeds after their adsorption on these Ru^o–Ti³⁺ active centers and subsequent C―O dissociation throughout the formation of CH_x/C_nH_x/C_nH_xO/CH_x―CO species. These intermediates are transformed into CH₄ by a combination of hydrogenation reactions. The formation of carbonaceous species during the methanation of CO and CO₂ suggests that the CO presence is required to promote the CO₂ methanation. Similar carbonaceous species are detected when the selective CO methanation is carried out with water in the stream. However, the activation of the catalysts occurs at much lower temperatures, and the carbon oxidation is favored by the oxidative effect of water. Copyright © 2015 John Wiley & Sons, Ltd.     

Co/Mg/Al hydrotalcite-type precursor, promoted with La and Ce, studied by XPS and applied to methane steam reforming reactions

Catalysts’ precursor of Co/Mg/Al promoted with Ce and La were tested in the steam reforming of methane (SRM). The addition of promoters was made by anion-exchange. The oxides characterization was made by X-ray Photoelectron Spectroscopy (XPS) analysis that confirmed Co²⁺ species in free form on surface and interacted with Mg and Al in the form of solid solution. In the SRM with high fed molar ratio of H₂O:CH₄ = 4:1, the catalysts showed a great affinity with water and immediately deactivated by oxidation of the active sites. In the stoichiometric ratio of H₂O:CH₄ = 2:1 the catalysts were active and presented low carbon deposition during the time reaction tested. Also a test with low fed molar ratio H₂O:CH₄ = 0.5:1 was carried out to evaluate the stability of the catalysts by CH₄ decomposition and all the catalysts were stable during 6 h of reaction. Promoted catalysts presented lower carbon deposition.     

Green approaches via nanocatalysis with nanoporous materials: Functionalization of mesoporous materials for single site catalysis

Among the various green keys, catalysis, especially using heterogeneous catalysts, has been powerfully applied to achieve greener chemical processes. Here are presented nanoporous materials which have mesoporosity with the functional groups on the inner pore walls. The materials were synthesized via a rather greener process, such as microwave synthesis, and over these nanocatalysts some of the green chemical reactions were carried out with high activities and selectivities. Cobalt species has been successfully functionalized and stabilized as a Co(III) complex onto SBA-15 support and proven to be an active catalyst in alkylaromatic oxidation with molecular oxygen, styrene epoxidation with tert-butyl hydroperoxide (TBHP), and allylic oxidation of cycloolefins with H₂O₂. Short-channeled amino-functionalized SBA-15 catalyst with hexagonal plate morphology was synthesized directly by using microwave synthesis from the co-condensation of aminopropyl triethoxysilane (APTES) and sodium metasilicate under a strong acidic condition. The catalyst showed high catalytic activity in liquid-phase Knoevenagel condensation reactions, due to easy diffusion and mass transfer of substrates into the short mesopore channel. The HO₃S–SBA-15 was prepared by grafting of mercaptopropyl trimethoxysilane onto the calcined mesoporous silica surface and subsequently oxidized with H₂O₂. The resulting catalyst was applied as a Bronsted solid-acid catalyst for the esterification of oleic acid with methanol.     

Characterization and catalytic performance of Zr-Mo-oxide catalysts for selective oxidation of methane to formaldehyde

The selective oxidation of methane to formaldehyde has been investigated over a series of Zr-Mo-oxide catalysts. Comparative characterization of these catalysts has been carried out by BET specific surface area (BET), X-ray diffraction (XRD), laser Raman spectroscopy (LRS), temperature programmed reduction of hydrogen (H₂-TPR), and X-ray photoelectron spectroscopy (XPS). The Zr-Mo-oxide catalyst with 12 wt% Mo is found to be highly selective and yields formaldehyde by selective oxidation of methane. The interaction between Mo and Zr induces changes of physicochemical properties such as structure, crystal size, reducible properties, charge of ion and molybdenum oxide species etc., which in turn determines the catalytic performance. These effects are a function of Mo content. Zr(MoO₄)₂in these catalysts might be responsible for selective oxidation of methane to formaldehyde.     

Sonocatalytic and sonophotocatalytic degradation of rhodamine 6G containing wastewaters

The present work deals with degradation of aqueous solution of Rhodamine 6G (Rh 6G) using sonocatalytic and sonophotocatalytic treatment schemes based on the use of cupric oxide (CuO) and titanium dioxide (TiO₂) as the solid catalysts. Experiments have been carried out at the operating capacity of 2 L and constant initial pH of 12.5. The effect of catalyst loading on the sonochemical degradation has been investigated by varying the loading over the range of 1.5–4.5 g/L. It has been observed that the maximum degradation of 52.2% was obtained at an optimum concentration of CuO as 1.5 g/L whereas for TiO₂ maximum degradation was observed as 51.2% at a loading of 4 g/L over similar treatment period. Studies with presence of radical scavengers such as methanol (CH₃OH) and n-butanol (C₄H₉OH) indicated lower extents of degradation confirming the dominance of radical mechanism. The combined approach of ultrasound, solid catalyst and scavengers has also been investigated at optimum loadings to simulate real conditions. The optimal solid loading was used for studies involving oxidation using UV irradiations where 26.4% and 28.9% of degradation was achieved at optimal loading of CuO and TiO_2, respectively. Studies using combination of UV and US irradiations have also been carried out using the optimal concentration of the catalysts. It has been observed that maximum degradation of 63.3% is achieved using combined US and UV with TiO₂ (4 g/L) as the photocatalyst. Overall it can be said that the combined processes give higher extent of degradation as compared to the individual processes based on US or UV irradiations.     

Sensitivity of styrene oxidation reaction to the catalyst structure of silver nanoparticles

This study shows how different morphologies of silver nanoparticles affect the selective oxidation of styrene in the gas phase using oxygen as oxidant. Silver nanoparticles (nanowires and nanopolyhedra), prepared using the polyol process, were supported on α-Al₂O₃. For comparison, a conventional catalyst obtained by wet impregnation was also prepared. Phenylacetaldehyde (Phe) and styrene oxide (SO) were the main products for nanoparticles catalysts. The promotion effect on the catalytic activity of potassium and cesium on the silver nanowires catalysts was also studied. At 573 K, the styrene conversion and selectivity to styrene oxide with the silver nanowires catalyst were 57.6 and 42.5%, respectively. Silver nanopolyhedra catalyst showed 57.5% conversion and 30.8% selectivity to styrene oxide. The promotion by cesium played an important role in improving the epoxidation of styrene. The samples were structurally characterized using X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR) were applied to characterize the oxygen species detected (O_β, O_γ) on the silver surface.     

Preparation of periodic mesoporous silica-included divacant Keggin units for the catalytic oxidation of styrene to synthesize styrene oxide

Periodic mesoporous composite catalysts, [(n-C₄H₉)₄N]₄[γ-SiW₁₀O₃₄(H₂O)₂]/SBA-15 (TBA-1*/SBA-15, where TBA-1* = [(n-C₄H₉)₄N]₄[γ-SiW₁₀O₃₄(H₂O)₂]), with TBA-1* loadings of 4.3-14.8% were prepared by simultaneous hydrolysis and co-condensation of the tetraethoxysilane (TEOS) in the presence of divacant Keggin-type polyoxometalate and triblock copolymer surfactant (P123) followed by hydrothermal treatment process. Structure integrity of the Keggin unit in as-prepared composites was studied by Fourier transform infrared spectroscopy (FT-IR), Raman scattering spectra, and ²⁹Si magic-angle spinning (MAS) NMR. Periodic mesoporous structure of the composites was evaluated by low-angle X-ray powder diffraction (LXRD) patterns, nitrogen porosimetry, and transmission electron microscope (TEM) measurements. As-prepared TBA-1*/SBA-15 was used as an heterogeneous oxidation catalyst for the styrene epoxidation reaction to synthesize styrene oxide in the presence of dilute H₂O₂ (30%), and influences of solvent, molar ratio of styrene to H₂O_2, TBA-1* loading on the styrene conversion, styrene oxide yield and selectivity were considered.     

Oxidation behavior and mechanism of powder metallurgy Rene95 nickel based superalloy between 800 and 1000 °C

The oxidation behaviors of powder metallurgy (PM) Rene95 Ni-based superalloy in the temperature range of 800-1000 °C are investigated in air by virtue of isothermal oxidation testing, X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The results show that the oxidation kinetics follows a square power law as the time extends at each temperature. The oxidation layers are detected to be composed of Cr₂O₃, TiO₂ and a small amount of NiCr₂O₄. The cross-sectional morphologies indicate that the oxidation layer consists of three parts: Cr-rich oxide layer, Cr and Ti duplex oxide layer, and oxidation affected zone. Theoretical analyses of oxidation kinetics and thicknesses of oxidation layers confirm that the activation energy of oxidation of PM Rene95 superalloy is 165.32 kJ mol⁻¹ and the oxidation process is controlled by diffusions of oxygen, Cr, and Ti. Accordingly, a diffusion-controlled mechanism is suggested to understand the oxidation behaviors of PM Rene95 superalloy at elevated temperatures.     

Heterogeneous reaction mechanism of elemental mercury oxidation by oxygen species over MnO2 catalyst

MnO₂-based catalysts have attracted great attention in the field of elemental mercury (Hg⁰) catalytic oxidation because of their superior catalytic performance and wide temperature window. Quantum chemistry calculations based on density functional theory (DFT) combined with periodic slab models were carried out to investigate the heterogeneous mechanism of Hg⁰ oxidation by oxygen species (gas-phase O₂, chemisorbed oxygen, and lattice oxygen) on MnO₂ surface. The results indicate that Hg⁰ and HgO are chemically adsorbed on MnO₂ surface with the adsorption energies of ?69.50 and ?226.48?kJ/mol, respectively. The adsorption of O₂ on MnO₂ surface belongs to chemisorption. O₂ can decompose on MnO₂ surface with an energy barrier of 97.46?kJ/mol to produce two atomic adsorbed oxygen. The perpendicular adsorbed O₂ and dissociative adsorbed O₂ are more favorable for Hg⁰ catalytic oxidation than lattice oxygen, and perpendicular adsorbed O₂ is the most active oxygen for Hg⁰ oxidation. The reaction pathway of Hg⁰ oxidation by perpendicular adsorbed O₂ includes three reaction steps: Hg⁰?→?Hg(ads)?→?HgO(ads)?→?HgO. The third step (HgO(ads)?→?HgO) is endothermic by 168.17?kJ/mol with an energy barrier of 179.48?kJ/mol, and it is the rate-limiting step of the whole Hg⁰ oxidation reaction.     

Highly selective epoxidation of styrene over mesoporous Au-Ti-SBA-15 via photocatalysis process: Synthesis, characterization, and catalytic application

Highly ordered Au-Ti-SBA-15 mesoporous molecular sieves were successfully synthesized by one-pot hydrothermal synthesis in acid medium, and were characterized by XRD, UV-vis, SEM, element-mapping, HRTEM, N₂ adsorption, XPS, ²⁹Si MAS NMR, NH₃-TPD and FT-IR. The as-prepared Au-Ti-SBA-15 samples were possessed of highly ordered mesostructures with larger pore diameter, pore volume and uniform mesopore size distribution. In the oxidation of styrene with H₂O₂ as the oxidant over Au-Ti-SBA-15 catalyst under photo-irradiation, reaction parameters, such as molar ratio of H₂O₂ to styrene, reaction time, solvent, the amount of catalyst, catalyst species, and the amount of 3% NaOH, were conditioned at length. As a result, highly selective epoxidation of styrene over catalyst was carried out perfectly for 10 min with high TOF of 4.75 × 10³ min⁻¹.     

Fabrication of nanosized Pt on rutile TiO2 using a standing wave sonochemical reactor (SWSR) – observation of an enhanced catalytic oxidation of CO

Fine particles of rutile TiO₂ supporting nanosized particles of Pt were prepared by a simultaneous in situ sonochemical reduction and deposition method using a standing wave sonochemical reactor (SWSR). The mean diameter of sonochemically obtained Pt particles are of 2 nm. Following this sonochemical technique, rutile TiO₂ was also deposited with different weight percentages of Pt. Catalytic function of the prepared composite catalysts were tested by the oxidation of CO to CO₂. From the catalytic activity results, it has been found out that the catalysts prepared by the sonochemical method exhibited higher catalytic activity for CO oxidation, probably attributed to the higher Pt particle distribution achieved under sonication. Transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and diffuse reflectance spectroscopy (DRS) were employed to characterize the resulting material.     

Electrochemical promotion of electronically isolated and dispersed Pt catalysts

In this paper we discuss the first attempts to induce the effect of Electrochemical Promotion or Non-Faradaic Electrochemical Modification of Catalytic Activity (NEMCA) on highly dispersed catalyst-electrodes systems which can compete in terms of dispersion and surface area with industrial catalysts. Three systems are discussed:

1. Electrochemical promotion of C₂H₄ oxidation on electronically isolated Pt catalysts on Y₂O₃-stabilized-Zirconia (YSZ) where NEMCA is induced via potential application between two terminal Au electrodes also supported on the solid electrolyte (bipolar design).
2. Electrochemical promotion of C₂H₄ oxidation on a finely dispersed Pt catalyst deposited on a Au electrode which is supported on YSZ.
3. Induction of NEMCA during CH₃OH oxidation on Pt without external voltage application by utilizing the potential difference developed between the catalyst and a catalytically inert counter electrode.

In all cases significant non faradaic behavior has been obtained. The underlying catalytic/ electro-catalytic phenomena are discussed together with some of the engineering challenges for potential practical applications.     

焙烧温度对SiO2负载的Co3O4纳米粒子表面氧缺陷浓度和CO氧化催化性能的影响

以传统的浸渍法,在不同焙烧温度下制备了用于CO氧化反应的Co₃O₄/SiO₂催化剂．通过激光拉曼光谱(Raman)、X射线光电子能谱(XPS)、X射线衍射(XRD)、程序升温还原(TPR)和X射线吸收精细结构谱(XAFS)表征了该系列催化剂的结构．在所有的催化剂中,XRD和Raman光谱都只检测到了Co₃O₄晶相的存在．与Co₃O₄体相相比,XPS结果表明在200 oC焙烧的(Co₃O₄(200)/SiO₂)催化剂中Co₃O₄表面上存在着过量的Co²⁺．与XPS的结果一致,TPR结果表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄表面上存在氧缺陷, 并且XAFS结果也表明Co₃O₄(200)/SiO₂催化剂中Co₃O₄具有更多的Co²⁺．提高焙烧温度使得过量的Co²⁺进一步氧化为Co³⁺,同时降低了表面氧缺陷浓度,从而得到计量比的Co₃O₄4/SiO₂催化剂．在所有的负载催化剂中Co₃O₄(200)/SiO₂催化剂表现出了最好的CO氧化催化性能,表明过量Co²⁺和表面氧缺陷的存在能够促进Co₃O₄催化CO氧化反应的活性.     

Role of Cl ions in photooxidation of propylene on TiO2 surface

The effect of Cl⁻ ions on photooxidation of propylene on TiO₂ semiconductor was investigated. Cl⁻/TiO₂ catalysts were prepared by annealing Degussa P25 TiO₂ in the gas flow of N₂ and Cl₂ under 100-400 °C. The photocatalytic oxidation of propylene was carried out in a continuous flow system, with the chromatograph to analyze the products on line. The experimental results showed that the activity of Cl⁻/TiO₂ catalysts increased as heat-treated temperature decreased. The activity of the sample heat-treated at 100 °C was about two times higher than that of pure TiO₂. Moreover, as to TiO₂, the main product of the propylene photocatalytic oxidation was CO₂, but with Cl⁻/TiO₂ catalysts, not only CO₂ but also trace CO was determined. The adsorbed species on TiO₂ surface before and after reaction were analyzed by X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermal analyses (TG-DTA) coupled to a mass spectrometer (MS). XPS analysis showed that there was Cl⁻ absorbed on the Cl⁻/TiO₂ surface, and the absorption amount of Cl⁻ decreased after the photooxidation reaction of propylene. TG-DTA-MS analysis confirmed chlorine absorbed on the surface of TiO₂ in the form of Cl⁻ ion. These results illuminated that absorbed Cl⁻ on the surface of TiO₂ formed a weak physical absorption on TiO₂ at low temperature, and subsequently participated in the photooxidation of propylene, finally removed from TiO₂ surface.     

Application of a cw quantum cascade laser CO2 analyser to catalytic oxidation reaction monitoring

Catalytic oxidation reaction monitoring has been performed for the first time with a trace gas carbon dioxide analyser based on a continuous wave (cw), thermoelectrically cooled (TEC), distributed feedback (DFB) quantum cascade laser (QCL) operating at around 2307 cm^?1. The reaction kinetics for carbon monoxide oxidation over a platinum catalyst supported on yttria-stabilised zirconia were followed by the QCL CO₂ analyser and showed that it is a powerful new tool for measuring low reaction rates associated with low surface area model catalysts operating at atmospheric pressures. A detection limit was determined of 40 ppb (1 standard deviation) for a 0.1 s average and a residual absorption standard deviation of 1.9×10^?4.     

Ru(III), Os(VIII), Pd(II) and Pt(IV) catalysed oxidation of glycyl–glycine by sodium N‐chloro‐p‐toluenesulfonamide: comparative mechanistic aspects and kinetic modelling

The Ru(III)/Os(VIII)/Pd(II)/Pt(IV)‐catalysed kinetics of oxidation of glycyl–glycine (Gly‐Gly) by sodium N‐chloro‐p‐ toluenesulfonamide (chloramine‐T; CAT) in NaOH medium has been investigated at 308 K. The stoichiometry and oxidation products in each case were found to be the same but their kinetic patterns observed are different. Under comparable experimental conditions, the oxidation‐kinetics and mechanistic behaviour of Gly‐Gly with CAT in NaOH medium is different for each catalyst and obeys the underlying rate laws:

• Rate = k [CAT]_t [Gly‐Gly]⁰ [Ru(III)][OH^?]^x
• Rate = k [CAT]_t[Gly‐Gly]^x [Os(VIII)]^y[OH^?]^z
• Rate = k [CAT]_t[Gly‐Gly]^x [Pd(II)][OH^?]^y
• Rate = k [CAT]_t[Gly‐Gly]⁰ [Pt(IV)]^x[OH^?]^y

Here, and x, y, z < 1 in all the cases. The anion of CAT, CH₃C₆H₄SO₂NCl^?, has been postulated as the common reactive oxidising species in all the cases. Under comparable experimental conditions, the relative ability of these catalysts towards oxidation of Gly‐Gly by CAT are in the order: Os(VIII) > Ru(III) > Pt(IV) > Pd(II). This trend may be attributed to the different d‐electronic configuration of the catalysts. Further, the rates of oxidation of all the four catalysed reactions have been compared with uncatalysed reactions, under identical experimental conditions. It was found that the catalysed reaction rates are 7‐ to 24‐fold faster. Based on the observed experimental results, detailed mechanistic interpretation and the related kinetic modelling have been worked out for each catalyst. Copyright © 2008 John Wiley & Sons, Ltd.     

Role of holes states on metal to insulator transition and collapse of magnetic ordering in LaFe1−xNixO3 (x = 0.0–0.5)

Polycrystalline LaFe_1?xNi_xO₃ (x = 0.0, 0.1, 0.3 and 0.5) have been prepared by the standard solid state reactions method. The phase formation has been confirmed by the powerful synchrotron X-ray diffraction experiment. In order to investigate the effects of Ni doping on the oxidation state, spin state and the magnetic ordering of the iron cations, ⁵⁷Fe Mössbauer Spectroscopy has been carried out at room temperature. Iron is present as Fe³⁺ in high spin state in LaFeO₃. Ni doping has no effect on the spin state of the Fe³⁺ cations. However, a progressive increase in the concentration of Fe⁴⁺ cations has been inferred. Relatively stronger covalent character of the Fe⁴⁺–O^?2 bond causes a progressive collapse in the magnetic ordering and delocalization of the hole states.     

Effect of the Calcination Atmosphere on the Structural Properties of the Reduced Fe/SiO2 System

Iron supported systems are frequently used as catalysts in the Fischer–Tropsch synthesis being the Fe⁰ the active phase for the reaction. We have studied the influence of the calcination atmosphere (air or nitrogen) on the iron oxide reducibility and the metallic iron particle size obtained in Fe/SiO₂ system. We have impregnated a silicagel with Fe(NO₃)₃·9H₂O aqueous solution and the solid obtained was calcinated in air or N₂ stream. These precursors, with 5% (wt/wt) of Fe, were characterized by Mössbauer Spectroscopy at 298 and 15 K. Amorphous Fe₂O₃ species with 3 nm diameter in the former, and α-Fe₂O₃ crystals of 48 nm diameter were detected in the last one. Both precursors were reduced in H₂ stream. Two catalysts were obtained and characterized by Mössbauer spectroscopy in controlled atmosphere at 298 and 15 K, CO chemisorption and volumetric oxidation. α-Fe⁰, Fe₃O₄ and Fe²⁺ were identified in the catalyst calcined in air. Instead, only α-Fe⁰ was detected in the catalyst calcined in N₂. The iron metallic crystal sizes were estimated as ≈2 nm for the former and ≈29 nm for the last one. The different oxide crystal sizes, obtained from the diverse calcination atmospheres, have led to different structural properties of the reduced solids. It has been possible to reduce totally the existing iron in an Fe/SiO₂ system with iron loading lower than 10% (wt/wt).     

Effect of Composition on Chain Dimensions of Styrene-Methylmethacrylate Random Copolymers under Theta Condition

Rotational-isomeric-state (RIS)-Metropolis Monte Carlo simulations are performed on poly(styrene-ran-methylmethacrylate) random copolymers to study the intrinsic unperturbed (θ-condition) dimensions. Mean-squared end-to-end distance (?r²?_o ), mean-squared radius of gyration (?s²?_o ), and characteristic ratio (C_n) have been calculated for these copolymers constituted by different overall chemical compositions (styrene fractions 0.29, 0.56, and 0.70). Calculations were carried out with chains of 500 repeating units. With an increase in the styrene content there is an increase in ?r ²? _o, `, and C_n, in agreement with experimental observations. An increase in the fraction of trans conformational states in the backbone torsion angles is found to be responsible for the exhibited chain expansion behavior. The dimensions calculated by the Monte Carlo simulations agree well with experimental values reported in the literature.