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1.
2.
The mass‐transfer area of nine structured packings was measured in a 0.427 m ID column via absorption of CO2 from air into 0.1 kmol/m3 NaOH. The mass‐transfer area was most strongly related to the specific area (125–500 m2/m3), and liquid load (2.5–75 m3/m2·h). Surface tension (30–72 mN/m) had a weaker but significant effect. Gas velocity (0.6–2.3 m/s), liquid viscosity (1–15 mPa·s), and flow channel configuration had essentially no impact on the mass‐transfer area. Surface texture (embossing) increased the effective area by 10% at most. The ratio of mass‐transfer area to specific area (ae/ap) was correlated within the limits of ±13% for the entire experimental database ${{a_{\rm{e}} } \over {a_{\rm{p}} }}= 1.34 \left[ {\left( {{{\rho _{\rm{L}} } \over \sigma }} \right)g^{1/3} \left( {{Q \over {L_{\rm{p}} }}} \right)^{4/3}} \right]^{\,0.116}$ . © 2010 American Institute of Chemical Engineers AIChE J, 2010  相似文献   

3.
The literature on the reaction of cytochrome c with the radiolytically generated radicals \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm e}_{{\rm eq}}^ -,^. {\rm OH,}^{\rm .} {\rm H,CO}_2^ -,{\rm O}_{\rm 2}^ -,{\rm Br}_{\rm 2}^ - $\end{document} and various organic radicals is reviewed. It would appear that negatively charged radicals, aided by the electric field of cytochrome c, react at the exposed haem edge. Uncharged organic radicals also react at this site. \documentclass{article}\pagestyle{empty}\begin{document}$ ^. {\rm H} $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ ^. {\rm OH} $\end{document} are likely to reduce the prosthetic group indirectly by a tunnelling mechanism.  相似文献   

4.
The heterogeneous bulk polymerization of acrylonitrile initiated by AIBN has been studied by means of an improved dilatometric technique and a new method of analysis, where the initial reaction rate (vw)0 results from the intercept of a straight line in a \documentclass{article}\pagestyle{empty}\begin{document}$ \frac {\ln \left( 1 \hbox{---} {\rm U} \right)} {{\rm e}^{{- 0,5} {\rm k}_{\rm s}{\rm t} \hbox{---} 1}}$\end{document} versus t plot. It has been found that the initial reaction rate is proportional to the square root of the initial catalyst concentration S0. The ratio of the rate coefficients of propagation and termination\documentclass{article}\pagestyle{empty}\begin{document}$\frac { {\rm k}_{\rm a} } { {\rm k}_{ {\rm w}^{2} } } $\end{document} could be calculated from the slope of a straight line passing through the origin in a plot of (vw)0 versus \documentclass{article}\pagestyle{empty}\begin{document}$\sqrt { {\rm S}_{0} }$\end{document} and yielded a value of 280 mol 1?1.  相似文献   

5.
$\begin{array}{l}{\hbox{R}^1\hbox{R}^2\hbox{CHOH}} \\ {\hbox{RCH}_2\hbox{OH} }\end{array} \dynrightarrow{Oxone}{\hbox{CH}_3\hbox{CN/H}_2\hbox{O}, 70^{\circ}\hbox{C}} \begin{array}{l}{\hbox{R}^1\hbox{R}^2\hbox{CO}} \\ {\hbox{RCOOH}} \end{array} A simple and environmentally friendly procedure for the oxidation of alcohols is presented utilizing Oxone? (2KHSO5 · KHSO4 · K2 SO4) as oxidant and polymer-supported 2-iodobenzamide as catalyst in CH3CN/H2O mixed solvents.  相似文献   

6.
A kinetic study of the hydrolysis of 39.8 wt.-% acetyl cellulose acetate has been made as a function of pH and temperature over the pH range of 2.2–10 and temperature range of 23–95°C. The hydrolysis reaction was carried out on highly porous membranes under quasihomogeneous conditions and the data have been treated as a pseudo-first-order reaction in acetyl concentration. The reaction can be represented by the equation \documentclass{article}\pagestyle{empty}\begin{document}$k_1 {\rm = }\;k_{\rm H ^ +} \left[ {{\rm H^+}} \right]{\rm +}k_{\rm OH^-}\left[ {{\rm OH}^ - } \right] + k_{\rm H_2O} $\end{document}, and where \documentclass{article}\pagestyle{empty}\begin{document}$k_{\rm H} ^ + {\rm = 5}{\rm .24}\;{\rm x 10}^{\rm 5} {\rm exp }\left\{ {{\rm ‐ 16}{\rm .4 x 10}^{\rm 3} /RT} \right\},{\rm }k_{{\rm OH}} ^ ‐ {\rm = 1}{\rm .55}\;{\rm x 10}^{\rm 4} {\rm exp }\left\{ {{\rm ‐ 8}{\rm .1 x 10}^{\rm 3} /RT} \right\}$\end{document}, and \documentclass{article}\pagestyle{empty}\begin{document}$k_{\rm H_2O} {= 4.25\;\times 10}^{- 2} {\rm exp }\left\{ {{- 11.5 \times 10^3 /RT}} \right\}$\end{document} (where the quantities in brackets are activities of the ions shown).  相似文献   

7.
Experimental results on the rate of lateral flame spread and time for piloted ignition under an externally imposed radiant flux were analyzed with a simple theroretical model. The data were developed from a radiant panel apparatus that considers a wall mounted sample with a flux distribution \documentclass{article}\pagestyle{empty}\begin{document}$ (\dot q_{\rm e} ^{\prime \prime } ) $\end{document} of 5 W cm?2 at the ignited end to 0.2 W cm?2 at the other end. It is shown that after an appropriate preheating time (flux exposure time before sample is ignited) the rate of flame spread (Vf) results can be correlated by \documentclass{article}\pagestyle{empty}\begin{document}$ V_{\rm f} - {\textstyle{1 \over 2}} = C\left( {\dot q''_{{\rm o,ig}} - \dot q_{\rm e} ^{\prime \prime } } \right) $\end{document} where C is a material ‘constant’ and \documentclass{article}\pagestyle{empty}\begin{document}$ \dot q''{\rm }_{{\rm o,ig}} $\end{document} is minimum flux for piloted ignition—also a material (and configuration) constant. An extension of this model demonstrates that Vf can also be expressed in terms of an ‘ignition temperature’ and the surface temperature of the material. Both correlations are derivable from a single flame spread experiment. Results are presented for a number of typical wood and plastic materials.  相似文献   

8.
The influence of CO2 and H2O on the activity of 4% Sr-La2O3 mimics that observed with pure La2O3, and a reversible inhibition of the rate is observed. CO2 causes a greater effect, with decreases in rate of about 65% with O2 present and 90% in its absence, while with H2O in the feed, the rate decreased around 35-40% with O2 present or absent. The influence of these two reaction products on kinetic behavior can be described by assuming competitive adsorption on the surface, incorporating adsorbed CO2 and H2O in the site balance, and using rate expressions previously proposed for this reaction over Sr-promoted La2O3. In the absence of O2, the rate expression is $$r_{N_2 } = \frac{{k'P_{{\text{NO}}} P_{{\text{CH}}_{\text{4}} } }}{{{\text{(1 + }}K_{{\text{NO}}} P_{{\text{NO}}} {\text{ + }}K_{{\text{CH}}_{\text{4}} } P_{{\text{CH}}_{\text{4}} } {\text{ + }}K_{{\text{CO}}_{\text{2}} } P_{{\text{CO}}_{\text{2}} } {\text{ + }}K_{{\text{H}}_{\text{2}} {\text{O}}} P_{{\text{H}}_{\text{2}} {\text{O}}} {\text{)}}^{\text{2}} }},$$ which yields a good fit to the experimental data and gives optimized equilibrium adsorption constants that demonstrate thermodynamic consistency. With O2 in the feed, nondifferential changes in reactant concentrations through the reactor bed were accounted for by assuming integral reactor behavior and simultaneously considering both CH4 combustion and CH4 reduction of NO, which provided the following rate law for total CH4 disappearance: $$(r_{{\text{CH}}_{\text{4}} } )_{\text{T}} = \frac{{k'_{{\text{com}}} P_{{\text{CH}}_{\text{4}} } P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} + k'_{{\text{NO}}} P_{{\text{NO}}} P_{{\text{CH}}_{\text{4}} } P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} }}{{{\text{(1 + }}K_{{\text{NO}}} P_{{\text{NO}}} {\text{ + }}K_{{\text{CH}}_{\text{4}} } P_{{\text{CH}}_{\text{4}} } {\text{ + }}K_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} {\text{ + }}K_{{\text{CO}}_{\text{2}} } P_{{\text{CO}}_{\text{2}} } {\text{ + }}K_{{\text{H}}_{\text{2}} {\text{O}}} P_{{\text{H}}_{\text{2}} {\text{O}}} {\text{)}}^{\text{2}} }}.$$ The second term of this expression represents N2 formation, and it again fit the experimental data well. The fitting constants in the denominator, which correspond to equilibrium adsorption constants, were not only thermodynamically consistent but also provided entropies and enthalpies of adsorption that were similar to values obtained with other La2O3-based catalysts. Apparent activation energies typically ranged from 23 to 28 kcal/mol with O2 absent and 31-36 kcal/mol with O2 in the feed. With CO2 in the feed, but no O2, the activation energy for the formation of a methyl group via interaction of CH4 with adsorbed NO was determined to be 35 kcal/mol.  相似文献   

9.
Acetoacetaldehyde Dimethylacetal as a Starting Material for Syntheses The use of acetoacetaldehyde dimethylacetal (1) leads to the introduction of the group \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm =}\mathop {\rm C}\limits^{\mathop |\limits^{{\rm CH}_{\rm 2}}} ---{\rm CH}_{\rm 2} ---{\rm CH(OCH}_{\rm 3} {\rm)}_{\rm 2} $\end{document} by reaction at the carbonyl carbon atom, and of the group CH3–CO–CH2–CH?or CH3–CO–CH?CH– by reaction at the acetalic carbon atom. For synthetic purposes it is important that methanol can be splitten off from 1, and the acetoacetaldehyde enol ether methoxybutenone (2) is generated. With catalytic amounts of acids or bases an equilibrium mixture with 70% 1 and 30% 2 is formed; 2 shows the higher reactivity of a vinylogous acetic ester. 1 as well as 2 can be attacked at each of the four carbon atoms; ring closure reactions were observed with the carbon atom 2 or 4 alone, or with two carbon atoms (6 possibilities, prevalent 2 + 4), and occasionally by participation of two molecules of 1 or 2.  相似文献   

10.
A method for measuring the unperturbed radius of gyration and the degree of long-chain branching in Gaussian-distribution polymers is proposed. Polyvinyl chloride (PVC) and polyvinyl acetate (PVAc) were selected to illustrate the method. It was observed that PVC samples prepared by homogeneous and heterogeneous polymerizations exhibit the same degree of long-chain branching. This conclusion is supported by viscometric data. The polydispersity ratios (Mw/Mn) indicate that both types of polymerizations would yield a very small amount of total branching (long chain and short chain.) The calculated unperturbed radius of gyration of linear PVC samples was found to be 0.185 \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {\frac{{{\rm \dot A}^{\rm 2} {\rm mole}}}{{{\rm gm}}}} \right) $\end{document}, and that of PVAc was determined to be 0.107 \documentclass{article}\pagestyle{empty}\begin{document}$ \left( {\frac{{{\rm \dot A}^{\rm 2} {\rm mole}}}{{{\rm gm}}}} \right) $\end{document}. The value obtained for PVC is shown to be in agreement with the value determined from the viscometric method as described in our previous work.  相似文献   

11.
Kinetic Studies on the Autoxidation of Olefins The oxidabilities \documentclass{article}\pagestyle{empty}\begin{document}$ {{{\rm k}_{\rm p} } \mathord{\left/ {\vphantom {{{\rm k}_{\rm p} } {\sqrt {2{\rm k}_{\rm t} } }}} \right.\kern-\nulldelimiterspace} {\sqrt {2{\rm k}_{\rm t} } }} $\end{document} at 50°C were determined for 37 olefins, using chlorobenzene as the solvent and azodiisobutyronitril as the initiator. In the group of acyclic aliphatic olefins the oxidability rises with increasing number of alkyl groups bound to the double bond. This is also true for cyclic olefins, but in this case the ring size has also a great influence on the oxidability. So the oxidability decreases from five-ring to eight-ring cycloolefins. Particularly high oxidabilities are found in the case of olefins in which a phenyl group is attached directly to the C C-double bond.  相似文献   

12.
Experimental data are reported on the volumetric behavior of four mixtures of ethane and hydrogen sulphide containing 77.55, 63.52, 39.95, and 21.42% ethane in the temperature range from 50° to 125°C at pressures to about 5,000 psia. Compressibilities were fitted to the Benedict-Webb-Rubin equation of state for each mixture with an average deviation of 0.47%, although the variation of the coefficients with composition was not in accord with Benedict's mixing rules. Simultaneous evaluation of all coefficients other than γ using an equation of the form \documentclass{article}\pagestyle{empty}\begin{document}${\rm k}_{\rm m} = \sum\limits_{{\rm i} = 1}^{\rm N} {\sum\limits_{{\rm j} = 1}^{\rm N} {{\rm x}_{\rm i} \,\,{\rm x}_{\rm j} \,\,{\rm k}_{{\rm ij}} } } $\end{document} and the data from 639 experimental points gave an average deviation of 0.645% and a maximum of 5.61%.  相似文献   

13.
The influence of electrolytes, which are dissolved in the aqueous absorbent and do not react with nitrogen oxides, on the absorption kinetics of both these components was investigated experimentally. In addition to demineralized water, various salt solutions of different concentrations as well as sodium hydroxide solution were used as absorbents. The term H \documentclass{article}\pagestyle{empty}\begin{document}$ H\sqrt {k_1 D} $\end{document} for N2O4 and N2O3, which is important for the design of industrial absorbers, was determined as a function of composition and concentration of the absorbents. In the case of N2O4, the chosen measuring and evaluation methods permitted a separate determination of the rate constant k of the pseudo first order reaction and of the solubility H. The diffusion coefficient D of the gas in the absorbent can be obtained only by calculation. Experimental results showed that \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document} decreases with increasing ionic strength I, however, without a clear indication of any ion-specific effects. This decrease does not appear to be caused simply by a reduction in solubility (salting out effect), or in diffusion coefficient, but at least, to the same extent, through a decrease of the rate constant k with increasing electrolyte content in the absorbent. The measurements permitted the determination of the gas-based salting out parameter for N2O4. The investigations on the absorption of N2O3 in water and in an Na2SO4 solution showed no experimentally detectable influence of dissolved salts on \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document}. The numerical value of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document} is six times that of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document}.  相似文献   

14.
The orientation (tilt angle φ) of thermotropic liquid crystals (LC) on the interface to a polymer-coated surface is not only determined by the numerical value ${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$ of the substrate surface tension. However, the ratio between the dispersive and the polar part of ${\rm \gamma }_{\rm S} {\rm }\left( {{\rm\gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$ also influences the LC orientation on the substrate surface. A polyimide and an amide-modified styrene/maleic anhydride copolymer were used as polymers.  相似文献   

15.
A new gel permeation chromatography (GPC) method is proposed for determining the unperturbed end-to-end distance, \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} $\end{document}, of polymers of known molecular weights, Mn and Mw. This method requires the value of \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} _{{\rm ps}} $\end{document} of polystyrene which was determined through viscometry to be 0.735 \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{{\rm {\AA}}^2-{\rm mole}}}{{gm}}} \right)^{0.5} $\end{document} Polyvinyl chloride (PVC) was chosen to illustrate the method and \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2}}{M}} \right)^{0.5} _{pvc} $\end{document} was found to be 0.99 from GPC data which is in agreement with the result obtained from viscometry, \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2}}{M}} \right)^{0.5} _{pvc} $\end{document} = 1.01. All \documentclass{article}\pagestyle{empty}\begin{document}$ \left({\frac{{r_0 ^2 }}{M}} \right)^{0.5} $\end{document} values were determined at 30°C. The advantage to this method lies in its speed and economy of materials.  相似文献   

16.
The kinetics of the electrochemical oxidation of sulfide ions in salt water were studied using rotating graphite disc electrodes, polarization techniques, Electrochemical Impedance Spectroscopy (EIS), X-ray Photoelectron Spectroscopy (XPS) and Electron Dispersion Spectroscopy (EDS). Elemental sulfur was shown to be the final product under various temperatures, potentials and times of electrolysis, in amounts that increased with increase in the above variables. The rate of the process is controlled by electron transfer across the interface, while diffusion in the electrolyte has only a modest effect. The apparent reaction orders with respect to the sulfide concentration and pH are 0.60 and 0, respectively. The proposed overall reaction is: while the rate determining step is: The charge transfer coefficient is αa = 0.23 and the standard rate constant at the equilibrium potential is cm s−1. The degree of coverage of the electrode with sulfur and the polarization resistance of the interface increase, while the current decreases, with the time of electrolysis as more sulfur is deposited on the electrode surface.  相似文献   

17.
In order to investigate the partial electronic conduction in the high oxide ion conductor of the system Bi2O3-Y2O3 under low oxygen pressure, e.m.f. and polarization methods were employed. Although the electrolyte was decomposed when the \(P_{{\text{O}}_{\text{2}} }\) was lower than the equilibrium \(P_{{\text{O}}_{\text{2}} }\) of Bi, Bi2O3 mixture at each temperature, the ionic transport number was found to be close to unity above that \(P_{{\text{O}}_{\text{2}} }\) . The hole conductivity (σ p) and the electron conductivity (σ p) could be expressed as follows, $$\begin{gathered} \sigma _p \Omega cm = 5 \cdot 0 \times 10^2 \left( {P_{O_2 } atm^{ - 1} } \right)^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \exp \left[ { - 106 kJ\left( {RT mol} \right)^{ - 1} } \right] \hfill \\ \sigma _p \Omega cm = 3 \cdot 4 \times 10^5 \left( {P_{O_2 } atm^{ - 1} } \right)^{ - {1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \exp \left[ { - 213 kJ\left( {RT mol} \right)^{ - 1} } \right] \hfill \\ \end{gathered} $$ These values were much lower than the oxide ion conductivity under ordinary oxygen pressure.  相似文献   

18.
Summary Phenylacetylene could be polymerized by (mesitylene)W(CO)3 in CCl4 to give a polymer with 12,000 in ca. 80% yield. UV irradiation was unnecessary unlike the W(CO)6–CCl4-h catalyst. The present polymerization did not proceed in toluene. The (mesitylene)W(CO)3 catalyst afforded high molecular weight polymers from phenylacetylenes bearing bulky substituents (e.g., Me3Si and CF3) at the ortho position. The Mo counterpart, (mesitylene)Mo(CO)3, catalyzed the polymerization of 1-chloro-2-phenylacetylene and 1-chloro-1-octyne to provide high molecular weight polymers . Catalytic amounts of Lewis acids accelerated the polymerization of phenylacetylene by (mesitylene)W(CO)3, but decreased the polymer molecular weight; this polymerization proceeded not only in CCl4 but also in toluene.  相似文献   

19.
Diluted solutions of linear polystyrene (PS) in toluene and dioxane were studied by the light-scattering method. The solutes were mixtures of high-M?w and low M?w PS. The dissolved PS mixtures were regarded as polymer solutions containing microgels, the high-M?w PS being looked upon as the microgel counterpart. The calculation method as proposed by Strazielle1 and Burchard2 was used to evaluate the microgel percentage and particle size, whereby the method could be verified against mixtures with well-known weight composition and \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {\left( {r_g ^2 } \right)} ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $\end{document}. The \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {\left( {r_g ^2 } \right)} ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $\end{document} values evaluated for the mixtures from the experimental data were compared with those estimated from the molecular weights of the components, their weight concentrations, and their \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {\left( {r_g ^2 } \right)} ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $\end{document} values. The method1,2 was found to be useful for evaluating the microgel content in a sample, but not for \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {\left( {r_g ^2 } \right)} ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $\end{document} values as calculated by Guinier's procedure nor those calculated by Zimm's procedure; the former were low and the latter were even incongruous. A comparative analysis of the theoretical function P?1(θ)-versus-sin2 (θ/2) and experimental (Kc/R(θ))c=0-versus-sin2 (θ/2) curves allowed to discuss the effect of the course of these curves at samll angles from 0° to 30° on M?w and \documentclass{article}\pagestyle{empty}\begin{document}$ \overline {\left( {r_g ^2 } \right)} ^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} $\end{document} as determined for the high and low molecular weight polystyrene mixtures in toluene as solvent.  相似文献   

20.
The generation of chlorine dioxide from the reaction between hypochlorous acid and chlorite with or without an initial chloride addition has been studied under slightly acidic conditions. Chloride (Cl-), one of the products from the reaction, not only changes the reaction stoichiometry, but also alters the rate law. It was found that the formation of chlorine dioxide from the HOCI-ClO2- system consists of two distinct parts, one is promoted by chloride, the other is independent of chloride. The overall kinetics of the chlorine dioxide generation from the reaction is: This model can very well predict the reaction under the following conditions: $ 273 - 303{\rm K},\left[ {ClO_2^ - } \right] = 0.001 - 0.00267\;{\rm mol}/{\rm L},\left[ {ClO_2^ - } \right]/\left[ {HOCl} \right] = 2,\;{\rm and}\;{\rm pH}\;3.86 - 4.91 $  相似文献   

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