A kinetic and thermochemical database for organic sulfur and oxygen compounds.

نویسندگان

  • Caleb A Class
  • Jorge Aguilera-Iparraguirre
  • William H Green
چکیده

Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and oxygen. This includes 11 H2O addition, 8 H2S addition, 11 hydrogen abstraction, 7 beta scission, and 3 elementary tautomerization reactions, which are potentially relevant in the combustion and desulfurization of sulfur compounds found in various fuel sources. Geometry optimizations and frequencies were calculated for reactants and transition states using B3LYP/CBSB7, and potential energies were calculated using CBS-QB3 and CCSD(T)-F12a/VTZ-F12. Rate coefficients were calculated using conventional transition state theory, with corrections for internal rotations and tunneling. Additionally, thermochemical parameters were calculated for each of the compounds involved in these reactions. With few exceptions, rate parameters calculated using the two potential energy methods agreed reasonably, with calculated activation energies differing by less than 5 kJ mol(-1). The computed rate coefficients and thermochemical parameters are expected to be useful for kinetic modeling.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Computational Model of Reaction Mechanism of Alkyl Peroxy Radicals with Organic Compounds in the Presence and Absence of Oxygen

On the basis of experimental data a kinetic model for the heterogeneous interaction between alkylperoxyradicals and organic compounds in Langmuir- Hinshelwood approach at room temperature has been offered.The effect of oxygen on the kinetics of process in the presence, [O2]o = 1 x 1011 – 1.6 x 1012 molecules.cm-2, and absence of oxygen has been analyzed. Over time the chain degenerate branching...

متن کامل

An EPR Study of Heterogeneous Reaction of CH3O2 Radicals with Organic Compounds: Effect of Organic Compound and Surface Nature

The reaction of CH3O2 radicals with acetaldehyde on the solid surface of NH4NO3 has been studied in a flow capillary reactor at low pressure and room temperature. The experiments were performed using EPR spectrometer combined with the kinetic method of radicals freezing. Peroxy radicals revealed an oscillation complex behavior during the process regarding to the phenomenon of radicals multiplic...

متن کامل

Degradation Efficiency and Kinetic Study of Phenol by Catalytic Ozonation Process in the Presence of Calcined Scallop Shell

Abstract Introduction: Phenol is amongst the dangerous environmental pollutants, which due to its presence in the industrial effluents, should be removed. Objective: The aim of this study was to evaluate the efficiency of catalytic ozonation by calcined scallop shell as a catalyst in the removal of phenol Materials and Methods: Scallop shells were collected from the coast of Caspian Sea in G...

متن کامل

ThermInfo: Collecting and Presenting Thermochemical Properties

Due to the large amount of chemical data available, it is essential to organize them and given the numerous problems derived from applying spreadsheets, it motivated us to construct an improved tool geared to contain large amounts of data. This paper presents ThermInfo, a public web tool that integrates a database based upon a relational data specification for describing structural and thermoch...

متن کامل

Identification of Functional Groups

Purpose: The purpose of this experiment is to observe chemical reactions characteristic of common organic functional groups. The observations will be used to identify a set of unknown compounds Introduction: Most organic and biochemical compounds are composed of carbon, hydrogen, and a few other elements (such as oxygen, nitrogen, and sulfur). These compounds participate in a wide variety of re...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:
  • Physical chemistry chemical physics : PCCP

دوره 17 20  شماره 

صفحات  -

تاریخ انتشار 2015