bluuebunny/crossref_metadata_2025 huggingface dataset:
Inference and Hierarchical Modeling in the Social Sciences
Authors: Draper David
Published: March 2008

Hierarchical models (HMs; Lindley & Smith, 1972) offer considerable promise to increase the level of realism in social science modeling, but the scope of what can be validly concluded with them is limited, and recent technical advances in allied fields may not yet have been put to best use in implementing them. In this article, I (a) examine 3 levels of inferential strength supported by typical social science data-gathering methods, and call for a greater degree of explicitness, when HMs and other models are applied, in identifying which level is appropriate; (b) reconsider the use of HMs in school effectiveness studies and meta-analysis from the perspective of causal inference; and (c) recommend the increased use of Gibbs sampling and other Markov-chain Monte Carlo (MCMC) methods in the application of HMs in the social sciences, so that comparisons between MCMC and better-established fitting methods—including full or restricted maximum likelihood estimation based on the EM algorithm, Fisher scoring, and iterative generalized least squares—may be more fully informed by empirical practice.
Questioning Multilevel Models
Authors: de Leeuw Jan , Kreft Ita G. G.
Published: March 2008

In this article, practical problems with multilevel techniques are discussed. These problems, brought to our attention by the National Center for Education Statistics (NCES), have to do with terminology, computer programs employing different algorithms, and interpretations of the coefficients in one or two steps. We discuss the usefulness of the hierarchical linear model (HM) in the most common situation in education—that of a large number of relatively small groups. We also point to situations where the more complicated HMs can be replaced with simpler models, with statistical properties that are easier to study. We conclude that more studies need to be done to establish the claimed superiority of restricted versus unrestricted maximum likelihood, to study the effects of shrinkage on the estimators, and to explore the merits of simpler methods such as weighted least squares. Finally, distinctions must be made between choice of model, choice of technique, choice of algorithm, and choice of computer program. While HMs are an elegant conceptualization, they are not always necessary. Traditional techniques perform as well, or better, if there are large groups and small intraclass correlations, and if the researcher is interested only in the fixed-level regression coefficients.
A Generalization of the Marginal Homogeneity Model for Square Contingency Tables With Ordered Categories
Authors: Tomizawa Sadao
Published: March 2008

This article introduces an extended marginal homogeneity model for the analysis of square contingency tables with the same ordinal row and column classifications. The model indicates that the odds that an observation will fall in row category k or below and in column category k + 1 or above, instead of in column category k or below and in row category k + 1 or above, increase (decrease) exponentially as the cut point k increases. An example is given.
Evaluating Statistics Texts Used in Education
Authors: Harwell Michael R. , Herrick Mary Lee , Curtis Deborah , Mundfrom Daniel , Gold Karen
Published: March 2008

Evaluating texts is an important activity associated with teaching statistics. Surprisingly, the statistical education literature offers little guidance on how these evaluations should be conducted. This lack of guidance may be at least partly responsible for the fact that published evaluations of statistics texts almost invariably employ evaluation criteria that lack any theory-based rationale. This failing is typically compounded by a lack of empirical evidence supporting the usefulness of the criteria. This article describes the construction and piloting of instruments for evaluating statistics texts that are grounded in the statistical education and text evaluation literatures. The study is an initial step in a line of research which we hope will result in the establishment and maintenance of a database of evaluations of statistical texts. Evaluative information of this kind should assist instructors wrestling with text selection decisions and individuals charged with performing evaluations, such as journal reviewers, and should ultimately benefit the direct consumers of these texts—the students.
A Meta-Analysis of Gender Differences in Applied Statistics Achievement
Authors: Schram Christine M.
Published: March 2008

This meta-analysis of gender differences examines statistics achievement in postsecondary-level psychology, education, and business courses. Thirteen articles examining 18 samples were obtained and coded for the analysis. The average effect size was –0.08 standard deviation units favoring females; however, the results were heterogeneous. Although no model accounted for all between-studies variation, gender differences could best be predicted from the percentage of undergraduate students in the sample, the department offering the course, and the use of course grade or points for the outcome measure. Undergraduate males showed an advantage over undergraduate females. Univariate tests showed that males also significantly outscored females when the outcome was a series of exams. Conversely, females significantly surpassed males when the outcome was total course performance. Lastly, females outscored males in courses offered by business departments.
Teacher’s Corner: Negative Information and The Three-Parameter Logistic Model
Authors: Bradlow Eric T.
Published: March 2008

The 3-parameter logistic model is commonly used to describe the relationship among an unobserved latent trait (ability), unobserved item properties, and an observed binary outcome. We show that for certain values of the item properties and latent ability, the observed information about ability contained in the binary response is negative. This result has implications for maximization procedures, such as Newton-Raphson; approximate sampling methods, such as the Metropolis-Hastings algorithm; and Bayesian adaptive testing. All of these typically utilize the observed information. This result is contrasted with the fact that observed negative information does not occur in the limiting case with no guessing (2-parameter logistic model). The probability of negative information is expressed by a simple formula. This research extends the work of Samejima (1973) and Yen, Burket, and Sykes (1991).
Reconciling Experts’ Differences in Setting Cut Scores for Pass-Fail Decisions
Authors: Longford Nicholas T.
Published: March 2008

Standard setting is a routine procedure in educational testing. Each examinee in the administration of a test is assigned a score, and the responses of a sample of the examinees are reviewed by a panel of experts. Each expert rates every selected examinee as pass or fail. Based on these ratings a cut score is to be established. A random effects logistic regression method is applied to set the cut score and to estimate the associated standard error. Two examples illustrate that taking account of between-rater differences is essential.
An Alternative Method for Scoring Adaptive Tests
Authors: Stocking Martha L.
Published: March 2008

Modern applications of computerized adaptive testing are typically grounded in item response theory (IRT; Lord, 1980 ). While the IRT foundations of adaptive testing provide a number of approaches to adaptive test scoring that may seem natural and efficient to psychometricians, these approaches may be more demanding for test takers, test score users, and interested regulatory institutions to comprehend. An alternative method, based on more familiar equated number-correct scores and identical to that used to score and equate many conventional tests, is explored and compared with one that relies more directly on IRT. It is concluded that scoring adaptive tests using the familiar number-correct score, accompanied by the necessary equating to adjust for the intentional differences in adaptive test difficulty, is a statistically viable, although slightly less efficient, method of adaptive test scoring. To enhance the prospects for enlightened public debate about adaptive testing, it may be preferable to use this more familiar approach. Public attention would then likely be focused on issues more central to adaptive testing, namely, the adaptive nature of the test.
The Runs Test for Autocorrelated Errors: Unacceptable Properties
Authors: Huitema Bradley E. , McKean Joseph W. , Zhao Jinsheng
Published: March 2008

The runs test is frequently recommended as a method of testing for nonindependent errors in time-series regression models. A Monte Carlo investigation was carried out to evaluate the empirical properties of this test using (a) several intervention and nonintervention regression models, (b) sample sizes ranging from 12 to 100, (c) three levels of α, (d) directional and nondirectional tests, and (e) 19 levels of autocorrelation among the errors. The results indicate that the runs test yields markedly asymmetrical error rates in the two tails and that neither directional nor nondirectional tests are satisfactory with respect to Type I error, even when the ratio of degrees of freedom to sample size is as high as .98. It is recommended that the test generally not be employed in evaluating the independence of the errors in time-series regression models.
Estimating the Importance of Differential Item Functioning
Authors: Rudas Tamás , Zwick Rebecca
Published: March 2008

Several methods have been proposed to detect differential item functioning (DIF), an item response pattern in which members of different demographic groups have different conditional probabilities of answering a test item correctly, given the same level of ability. In this article, the mixture index of fit, proposed by Rudas, Clogg, and Lindsay (1994) , is used to estimate the fraction of the population for which DIF occurs, and this approach is compared to the Mantel-Haenszel ( Mantel & Haenszel, 1959 ) test of DIF developed by Holland (1985 ; see Holland & Thayer, 1988) . The proposed estimation procedure, which is noniterative, can provide information about which portions of the item response data appear to be contributing to DIF.
An Evaluation of Rosenthal and Rubin’s Binomial Effect Size Display
Authors: Thompson Kenneth N. , Schumacker Randall E.
Published: March 2008

The binomial effect size display (BESD) has been proposed by Rosenthal and Rubin (1979 , 1982 ; Rosenthal, 1990 ; Rosenthal & Rosnow, 1991) as a format for presenting effect sizes associated with certain experimental and nonexperimental research. An evaluation of the BESD suggests that its application is limited to presenting the results of 2 × 2 tables where φ is employed as the index of effect size. Findings indicate that the BESD provides little added information beyond an examination of the raw percentages in the 2 × 2 table and dramatically distorts effect sizes when binomial success rates vary from .50.
Teacher’s Corner: Moving Between Hierarchical Modeling Notations
Authors: Ferron John
Published: March 2008

Students studying hierarchical models are often confronted with multiple notational representations. The purpose of this note is to illustrate the relationship between HLM notation and mixed model notation. This is accomplished by explicitly mapping the parameters across notations for a concrete example involving the hierarchical modeling of change.
Using Omitted Variable Bias to Assess Uncertainty in the Estimation of an AIDS Education Treatment Effect
Authors: Marcus Sue M.
Published: March 2008

In a comparison of a treatment group and a control group, a difference in results can correspond to the effect of the treatment; however, the difference might also be, at least in part, a reflection of pretreatment differences between the two populations. Covariance adjustment can reduce bias in the estimate of the treatment effect ( Cochran & Rubin, 1973 ); however, baseline group differences with respect to unobserved covariates which cannot be controlled can lead to hidden bias. This article presents a simple method which uses omitted variable bias to assess the uncertainty of the hidden bias by describing what scenarios regarding the unobserved covariate can lead to a given level of hidden bias. A comparison of a culturally sensitive AIDS video education program and a standard AIDS video education program is used as an illustration.
Model Selection Information Criteria for Non-Nested Latent Class Models
Authors: Lin Ting Hsiang , Dayton C. Mitchell
Published: March 2008

Latent class models have been developed for assessment of hierarchic relations in scaling and behavioral analysis. This article investigated the use of three model selection information criteria—Akaike AIC, Schwarz SIC, and Bozdogan CAIC—for non-nested models. In general, SIC and CAIC were superior to AIC for relatively simple models, whereas AIC was superior for more complex models, although accuracy was often quite low for such models. In addition, some effects were detected for error rates in the models.
A Decision Theory Model for Course Placement
Authors: van der Linden Wim J.
Published: March 2008

The problem of how to place students in a sequence of hierarchically related courses is addressed from a decision theory point of view. Based on a minimal set of assumptions, it is shown that optimal mastery rules for the courses are always monotone and a nonincreasing function of the scores on the placement test. On the other hand, placement rules are not generally monotone but have a form depending on the specific shape of the probability distributions and utility functions in force. The results are further explored for a class of linear utility functions.
A Power Comparison of the Welch-James and Improved General Approximation Tests in the Split-Plot Design
Authors: Algina James , Keselman H.J.
Published: March 2008

Power for the improved general approximation (IGA) and Welch-James (WJ) tests of the within-subjects (trials) main effect and the within-subjects × between-subjects (groups × trial) interaction was estimated for a design with one between- and one within-subjects factor. The distribution of the data had two levels: multivariate normal and multivariate lognormal Power estimates for conditions in which there were between-groups differences in dispersion matrices showed that, for both effects, there were conditions in which the IGA test was more powerful and conditions in which the WJ test was more powerful. The power advantage for the IGA test tended to be fairly small, whereas the power advantage for the WJ test was quite large in many conditions. Furthermore, the number of conditions favoring the WJ test was much larger than the number of conditions favoring the IGA test. Power for IGA, WJ, ε̃-adjusted, and MANOVA tests was compared for conditions in which dispersion matrices were equal across groups. Results indicate that little if any power was sacrificed by using WJ or IGA tests in place of MANOVA or ε̃-adjusted tests.
Using SAS PROC MIXED to Fit Multilevel Models, Hierarchical Models, and Individual Growth Models
Authors: Singer Judith D.
Published: March 2008

SAS PROC MIXED is a flexible program suitable for fitting multilevel models, hierarchical linear models, and individual growth models. Its position as an integrated program within the SAS statistical package makes it an ideal choice for empirical researchers and applied statisticians seeking to do data reduction, management, and analysis within a single statistical package. Because the program was developed from the perspective of a “mixed” statistical model with both random and fixed effects, its syntax and programming logic may appear unfamiliar to users in education and the social and behavioral sciences who tend to express these models as multilevel or hierarchical models. The purpose of this paper is to help users familiar with fitting multilevel models using other statistical packages (e.g., HLM, MLwiN, MIXREG) add SAS PROC MIXED to their array of analytic options. The paper is written as a step-by-step tutorial that shows how to fit the two most common multilevel models: (a) school effects models, designed for data on individuals nested within naturally occurring hierarchies (e.g., students within classes); and (b) individual growth models, designed for exploring longitudinal data (on individuals) over time. The conclusion discusses how these ideas can be extended straighforwardly to the case of three level models. An appendix presents general strategies for working with multilevel data in SAS and for creating data sets at several levels.
Application of a Method of Estimating DIF for Polytomous Test Items
Authors: Camilli Gregory , Congdon Peter
Published: March 2008

In this paper, a method for studying DIF is demonstrated that can used with either dichotomous or polytomous items. The method is shown to be valid for data that follow a partial credit IRT model. It is also shown that logistic regression gives results equivalent to those of the proposed method. In a simulation study, positively biased type 1 error rates of the method are shown to be in accord with results from previous studies; however, the size of the bias in the log odds is moderate. Finally, it is demonstrated how these statistics can be used to study DIF variability with the method of Longford, Holland, & Thayer (1993) .
Computer‐Aided Design of Solid Catalysts
Authors: Holena Martin , Baerns Manfred
Published: March 2008

The sections in this article are

Introduction

Theoretical Methods

Rational Methods for the Design of Catalytic Experiments

The Statistical Design of Experiments

Optimization Methods for Empirical Objective Functions

Evolutionary Methods

Feature 1

Feature 2

Feature 3

Feature 4

Other Stochastic Methods

Deterministic Methods

Group 1 Methods

Group 2 Methods

Group 3 Methods

Concluding Remarks

Data Analysis and Data Mining

Statistical Methods: An Overview

Artificial Neural Networks

Concluding Remarks

Conclusions
Heteropoly Compounds
Authors: Lee Kwan‐Young , Misono Makoto
Published: March 2008

The sections in this article are

Structure and Catalytic Properties

Heteropolyacids: Acid Forms in the Solid State and in Solution

K
eggin‐Type
HPAs

W
ells–
D
awson‐Type
HPAs

Salts of Heteropolyacids: Cation‐Exchanged Forms

Acid Catalysis of Salts of Heteropolyacids

Oxidation Catalysis of Salts of Heteropolyacids

Bifunctional Catalysts

Shape Selectivities of Acidic Salts of Heteropolyacids

Preparation

Mixed‐Coordinated Heteropoly Compounds

Supported Heteropoly Compounds

Oxide Supports

Mesoporous Supports

Carbon Supports

HPA
Salt Supports

Polymer Supports

Clay Supports

HPA
Encaged in Supercages

Heteropolyanions Intercalated in Layered Double Hydroxides

Lacunary and Metal‐Substituted Heteropoly Compounds

Lacunary Silicotungstate

Transition Metal‐Substituted Polyanions (
TMSP
)

Heteropolyanion‐Supported Metals

Microstructured
POM
toward a Shape‐Selective Catalyst
Carbons
Authors: Schlögl Robert
Published: March 2008

The sections in this article are

Introduction

The Complexity of Carbon

Electronic Structure of Carbon Allotropes

Basic Structures

Diamond

Graphite

Carbynes

Nanostructured Carbons

Carbolites and Fullerenes

Disordered Graphites

Nanocrystalline Carbon: Carbon Black

Formation of Carbon: General Pathways

Formation of Solid Carbon: Mechanistic Aspects

Catalytic Formation of Carbon from Molecules

Carbon on Noble Metal Catalysts

Carbon Formation in Zeolites

Graphitization of Carbons

Reaction of Oxygen with Carbon

Surface Chemistry of Carbon

Chemical Quantification of Oxygen Groups

Non‐Oxygen Heteroelements on Carbon Surfaces

Chemical Analysis of Surface Oxygen Groups

Reactivity in Fluid Phase

Spectroscopy of Functional Groups:XPS

Vibrational Spectroscopy of Functional Groups

Advanced Thermal Desorption

Synopsis: Carbon and Catalysis
Ion Exchange and Impregnation
Authors: Marceau Eric , Carrier Xavier , Che Michel , Clause Oliver , Marcilly Christian
Published: March 2008

The sections in this article are

Deposition of Active Component Precursors

Ion Exchange: Physicochemical Aspects

Impregnation: Physical Aspects

Support and Precursor during the Preparation Steps: Chemical Aspects

Applications

Conclusions
Metal Clusters in Zeolites
Authors: Sachtler Wolfgang M. H. , Zhang Z. Conrad
Published: March 2008

The sections in this article are

Introduction

Nano Clusters of Metal
versus
Macroscopic Metals

Preparation of Mono‐ or Bimetal Clusters in Zeolite Cavities

Ion Exchange

Calcination

Reduction

Interaction of Metal Clusters and Zeolite Protons

B
rønsted Acids in Zeolites

Metal Clusters as
Lewis
Bases

Chemical Anchoring

Heterogeneous Catalysis by Single Metal Atom Sites

Electron Deficiency

Is Bifunctionality due to “Shuttling” between Sites or to “Collapsed Sites”?

Metal Oxidation by Protons, Selective “Leaching”

Effects of Zeolite Geometry on Catalysis

Transport and Transition State Restrictions

Collimation of Molecules in Pores

Types of Pore Diffusion in Zeolites; Effects on Apparent Activation Energy

Beneficial Damage of Zeolite Matrix by Growing Metal Particles

Conclusions

Acknowledgments
Supported Catalysts from Chemical Vapor Deposition and Related Techniques
Authors: Tada Mizuki , Iwasawa Yasuhiro
Published: March 2008

The sections in this article are

Chemical Vapor Deposition (CVD) Technique

CVDPrecursors and Equipment

CVDCatalysts

Gold (Au)

Cobalt (Co)

Chromium (Cr)

Copper (Cu)

Iron (Fe)

Gallium (Ga)

Molybdenum (Mo)

AMoCarbonyls

BMoCl5

CAllylmolybdenum

DMoO3Vapor

Niobium (Nb)

Nickel (Ni)

Osmium (Os)

Palladium (Pd) Films and Particles

Pd/Zeolites

Platinum (Pt)

Rhenium (Re)

Rhodium (Rh)

Ruthenium (Ru)

SiO2

Tin (Sn)

Titanium (Ti)

Vanadium (V)

Tungsten (W)

Zirconium (Zr)

Bimetals

Mixed Metal Oxides and Sulfides

CVD‐Related Techniques

Concluding Remarks
Supported Liquid Catalysts
Authors: Riisager Anders , Fehrmann Rasmus , Wasserscheid Peter
Published: March 2008

The sections in this article are

Introduction

Historical Development

The Sulfuric Acid Catalyst

Solid Phosphoric Acid (
SPA
) Catalyst

Supported Ionic Liquid‐Phase (
SILP
) Catalysts

Conclusions
Non‐Zeolitic Standard Catalysts
Authors: Bond Geoffrey C.
Published: March 2008

The sections in this article are

Introduction

EUROCAT
Metal Catalysts

EUROPT
‐1

EUROPT
‐2

EUROPT
‐3 and
EUROPT
‐4

EURONI
‐1

Other
EUROCAT
Catalysts

Vanadia‐Titania
EUROCAT
Oxides

EUROTS
‐1 Zeolite

Gold Reference Catalysts

Other Programs

Summary and Conclusions
Gamma Spectroscopy
Authors: Niemantsverdriet Hans , Butz Tilman
Published: March 2008

The sections in this article are

Introduction

Mössbauer Spectroscopy

Time‐Differential Perturbed Angular Correlations (TDPAC)

Conclusions and Outlook
Solid‐StateNMRSpectroscopy
Authors: Hunger Michael , Wang Wei
Published: March 2008

The sections in this article are

Introduction

Interactions of Nuclear Spins in Solids

Experimental Techniques of Solid‐StateNMRSpectroscopy

Preparation of Catalyst Samples for Solid‐StateNMRSpectroscopy

NMRInvestigations of Catalyst Frameworks

NMRInvestigations of Heterogeneously Catalyzed Reactions

Conclusions
Vibrational Spectroscopy
Authors: Mestl Gerhard , Knözinger Helmut
Published: March 2008

The sections in this article are

Introduction

Basic Principles of Vibrational Spectroscopies

Vibrational Spectra of Bulk Oxides

Vibrational Spectra of Supported Catalysts

Vibrational Spectra of Surface and Structural Hydroxy Groups
Morphological Characteristics
Authors: Schmidt Friedrich
Published: March 2008

The sections in this article are

Introduction

Morphological Characteristics of Catalyst Beds

Size and Shape of Catalyst Powder Particles and their Morphological Parameters

Morphology of Bulk and Eggshell Catalysts

Morphology of Bulk Honeycombs and Other Bulk Monoliths

Morphology of Catalysts on the Micrometer Scale

Morphology of Catalysts on the Nanometer and Sub‐Nanometer Scale
Surface Chemical Composition
Authors: Taglauer Edmund
Published: March 2008

The sections in this article are

Introduction

Electron Spectroscopies (AES,XPS)

Basic Aspects

Auger Electron Spectroscopy (AES)

X‐Ray Photoemission Spectroscopy (XPS)

Ion Scattering Spectroscopies

General Aspects

Collision Kinematics

Low‐Energy Ions

Rutherford Scattering

Secondary Particles

Secondary Ion Mass Spectrometry

Secondary Neutrals

Photon Stimulation
X
‐Ray Photoelectron and Auger Electron Spectroscopy
Authors: Moretti Giuliano
Published: March 2008

The sections in this article are

Introduction

X
‐Ray and
UV
Photoelectron Spectroscopy

A
uger Electron Spectroscopy

Surface Sensitivity

Reference Level

Chemical Shifts in
XPS
and
AES

W
agner Plots

Thermochemical Approach

Illustrative Examples of Application of
XPS
and
AES
‐
XAES
to Heterogeneous Catalysis
UV–Vis–NIRandEPRSpectroscopies
Authors: Sojka Zbigniew , Bozon‐Verduraz François , Che Michel
Published: March 2008

The sections in this article are

Introduction

UV–Vis–NIRSpectroscopy

EPRSpectroscopy

Comparison betweenUV–Vis–NIR(DRS) andEPRSpectroscopies

Conclusions
Photoluminescence Spectroscopy and Its Application to the Characterization of Active Sites and Reaction Dynamics in Catalysis
Authors: Matsuoka Masaya , Kamegawa Takashi , Anpo Masakazu
Published: March 2008

The sections in this article are

Introduction

Characterization of Catalysts by Photoluminescence and Time‐Resolved Photoluminescence Spectroscopy

Investigations of the Dynamics of Photocatalysis by Time‐Resolved Photoluminescence Spectroscopy

Conclusions
Temperature‐Programmed Reduction and Oxidation1A list of symbols used in the text is provided at the end of the chapter.
Authors: Knözinger Helmut
Published: March 2008

The sections in this article are

Introduction

TheTPRExperiment

Kinetics and Mechanism of Reduction

Mathematical Treatment ofTPRProfiles and Influence of Experimental Parameters

Examples

Conclusion
Concepts and Analysis of Surface Acidity and Basicity
Authors: Karge Hellmut G.
Published: March 2008

The sections in this article are

Introduction

Concepts of Acidity and Basicity of Zeolite and Oxide Catalysts

Analysis of Acidity and Basicity

Conclusion
Carbonaceous Deposits
Authors: Albers Peter W. , Weitkamp Jens
Published: March 2008

The sections in this article are

Introduction

Formation and Chemical Nature of Carbonaceous Deposits

Educt Molecules and Alkaline Elements

Coke Distribution, Porosity and Pore Blocking

Graphiticity

Hydrogen Content and Hydrogen Analysis

Hydrogasification

Conclusions
Theoretical Modelling of Catalytic Reactions
Authors: Stoltze Per , Nørskov Jens K.
Published: March 2008

The sections in this article are

Introduction

The Hierarchy of Models

The Full Reaction Dynamics

The Kinetic
M
onte
C
arlo Approach

L
angmuir–
H
inshelwood Description

Power‐Law Kinetics

Microkinetic Modeling

Equilibrium

Statistical Thermodynamics

Sticking

Temperature‐Programmed Desorption

Catalytic Reaction at Steady State

Catalytic Reaction at Quasi‐Equilibrium

Parameters

Test

Applications

Ab Initio
Kinetics

Applications
Hydrocarbon Reaction Mechanisms
Authors: Santilli Don S. , Gates Bruce C.
Published: March 2008

The sections in this article are

Introduction

Acid–Base Catalysis

Carbocations and Their Reactions

Nature and Formation of Carbocations

Carbenium Ions

Carbonium Ions

Reactions of Carbenium Ions

Intramolecular Reactions

A
Hydride and Alkyl Shifts

B
β‐Elimination

C
β‐Scission

D
Cyclization

Intermolecular Reactions

A
Reactions with Alkanes: Hydride Transfer

B
Disproportionation

C
Reactions with Alkenes: Dimerization

D
Reactions with Aromatics

Catalytic Reactions Involving Carbocation Intermediates

Alkene Oligomerization and Polymerization

Isomerization

Cracking

Alkylation

Transalkylation of Aromatics

Aromatization of Alkanes and Alkenes

Coke Formation

Steric Influence of the Catalyst

Metal Surface Catalysis

Skeletal Isomerization of Hydrocarbons

Hydrogenation of Alkenes

Hydrogenolysis and Homologation of Alkenes

Acknowledgments
Computer Simulation of Sorption and Transport in Zeolites
Authors: Papadopoulos George K. , Theodorou Doros N.
Published: March 2008

The sections in this article are

Introduction

Reconstruction of Zeolitic Media

Atomistic Reconstruction

Mesoscopic Reconstruction

A
Stochastic

B
Particle‐Based

Zeolite Force Field

Sorption Equilibria

Sorbate Dynamics

Methodology

Survey of Dynamics Simulation Studies

A
Intracrystalline Dynamics

B
Intercrystalline Dynamics

Conclusions
Determination of Diffusion Coefficients in Porous Media
Authors: Kärger Jörg
Published: March 2008

The sections in this article are

Definitions

Measurement of Transport Diffusion

Steady‐State Measurements

Time Lag Measurements

Sorption Rate Measurements

Frequency Response Measurements

Chromatographic and Flow Methods

Microscopic Measurement

Measurement of Self‐Diffusion

Elementary Steps of Diffusion

Quasi‐elastic Neutron Scattering

Pulsed Field GradientNMR

Tracer Techniques

Diffusion in Multicomponent Systems

Correlation Between the Different Diffusivities

A Look into the Future
Deactivation and Regeneration
Authors: Moulijn Jacob A. , van Diepen Annelies E. , Kapteijn Freek
Published: March 2008

The sections in this article are

Introduction

Causes of Deactivation

Poisoning

Formation of Deposits

Thermal Degradation

Mechanical Deactivation

Corrosion/Leaching

Stability Too Low: What To Do?

Measures on the Scale of the Catalyst Particle

Tailored Reactor and Process Design

Relation Between Time‐Scale of Deactivation and Choice of Reactor

Chemical Reaction Engineering Solutions Allowing for Regeneration

Good Engineering Practice

Feed Purification

Optimizing Reaction Conditions

Optimal Conditions as a Function of Time‐on‐Stream

Regeneration or Replacement of the Catalyst

Poisoning

Deposits

Sintering

Leaching

Conclusion
Recycling of Spent Catalysts Containing Precious Metals
Authors: Hagelüken Christian
Published: March 2008

The sections in this article are

Introduction

Impact of Catalysis on Precious Metals Demand and Price Development

Recycling Technologies

Responsible Care and Trans‐Border Shipments

Shipment of Spent Catalysts—What Has to Be Considered?

A
Classification as Green or Amber Listed Waste

B
Green List Procedure

C
Amber List Procedure

Commercial Execution of a Refining Job

Catalyst Lifecycles and Future Recycling Potential

Closed Cycles—the Typical Case for Industrial Catalysts

Open Cycles—Recycling from Automotive Catalysts and Other Consumer Durables

Future Recycling Potential
Chemical Sensors Based on Catalytic Reactions
Authors: Barsan Nicolae , Schierbaum Klaus D. , Weimar Udo
Published: March 2008

The sections in this article are

Introduction

Definitions and Classifications

Typical Examples

Calorimetric Sensors

Electronic Conductance Sensors

Sensing Process and Signal Transduction

Modeling the Sensor Response

Role of Contacts

Materials

Tin Oxide (SnO2)

Tungsten Oxide (WO3)

Chromium Titanium Oxide (Cr2−xTixO3)

Gallium Oxide (Ga2O3)

Solid‐State Electrochemical Sensors

Conclusions
Heterogeneous Catalysis in Non‐Conventional Solvents
Authors: Gläser Roger
Published: March 2008

The sections in this article are

Introduction and Scope

Non‐Conventional Solvents

Supercritical Fluids (SCFs)

Properties ofSCFs

Opportunities forSCFsin Heterogeneous Catalysis

Ionic Liquids (ILs)

Properties ofILs

Opportunities forILsin Heterogeneous Catalysis

Gas‐Expanded Liquids (GXLs)

Properties ofGXLs

Opportunities forGXLsin Heterogeneous Catalysis

Other Non‐Conventional Solvents

Heterogeneously Catalyzed Conversions in Non‐Conventional Solvents

Conversions in Supercritical Fluids

Hydrogenations and Dehydrogenations

Fischer–Tropsch Synthesis

Hydroformylation

Oxidations

Alkylations

Isomerizations

Miscellaneous

Conversions in Ionic Liquids

Hydrogenations and Oxidations

CCBond Formation

Conversions in Gas‐Expanded Liquids

Outlook
Sonocatalysis
Authors: Suslick Kenneth S. , Skrabalak Sara E.
Published: March 2008

The sections in this article are

Introduction and the Origins of Sonochemistry

Effects of Ultrasound on Heterogeneous Catalysts

Metal Powders

Modification of Bulk Metals

Amorphous and Nanostructured Metal Catalysts

Metal Oxides as Catalysts

Metal Carbides and Sulfides

Catalyst Supports: Sonogels and Zeolites

Supported Catalysts

Polymerization Catalysts

Conclusion
Microstructured Reactors1A list of abbreviations/acronyms used in the text is provided at the end of the chapter.
Authors: Kiwi‐Minsker Lioubov , Renken Albert
Published: March 2008

The sections in this article are

Introduction

Microstructured Reactors for Gas‐Phase Catalytic Reactions

Packed‐Bed Reactors

Catalytic Wall Microstructured Reactors

Main Characteristics of Microstructured Reactors

Pressure Drop

Residence Time Distribution (RTD)

Mass Transfer Performance

Internal Mass Transfer

External Mass Transfer

Heat Transfer Performance

Design Criteria for Microstructured Multichannel Reactors

Heterogeneous Catalytic Reactions Limited by Chemical Transformation

Heterogeneous Catalytic Reactions Limited by Mass Transfer

Conclusions and Outlook

Symbols and Abbreviations
Catalysis in Environmental Protection
Authors: Keim Wilhelm
Published: March 2008

The sections in this article are

Introduction

How Novel is Environmental Catalysis?

Environmental Catalysis: Potential and Opportunities

Catalysis for Environmentally Benign Products and Processes

Products and Environmental Concern

Processes and Environmental Compatibility

Catalysis for Environmental Protection: Future Prospects
Flue Gases from Stationary Sources
Authors: Gabrielsson Pär , Pedersen Henrik Guldberg
Published: March 2008

The sections in this article are

Emissions from Stationary Sources

Drivers for Flue Gas Cleaning Technology

The
USA

E
urope

A
sia

C
hina

J
apan

NO

x

Removal Technologies

Nitrous Oxide (N
2
O)

Selective Catalytic Reduction (
SCR
)

SCR
Technology

SCR
Catalysts

Different Catalyst Types

Choice of Carrier

Optimization of Activity

The Effect of Increasing V
2
O
5
Loading

Activation Energy as a Function of Vanadium Content

The Effect of Co‐Oxides

SCR
Reaction Mechanism for Vanadium Catalysts: the Eley–Rideal Route

Global Kinetics

The Importance of
B
rønsted Acidity

The Influence of Reoxidation or
NO
2

The Influence of Gas Composition on Reaction Rate

The Influence of Water

The Influence of
O
2

Modeling

Definition of Different Model Types

Estimation of Interphase Mass Transfer

Intraporous Mass Transfer

Kinetic Expressions

The Feasibility of Different Models

Deactivation

Chemical Poisoning

Surface Fouling, Pore and Channel Clogging

Sintering

Catalyst Management and Regeneration

SCR
Catalyst Testing

Laboratory‐ and Bench‐Scale Testing

Pilot‐Scale Testing

Slip‐Stream Reactors

Full‐Scale Catalyst Testing

Gas Sampling and Analysis

Other Emissions

Sulfur Removal

The Wet Sulfuric Acid (
WSA
) Process and Combined
WSA
and
De
NO

x

(
SNOX
)

Hydrogen Sulfide

Carbon Monoxide

Carbon Dioxide

Hydrocarbons

Dioxins

Hg
Oxidation and Capture

Hg
Oxidation Thermodynamics

Hg
Removal from Coal‐Fired Power Plants

A
Conventional Flue Gas Cleaning Processes

B
Sorbent Injection, Coal Additives, and Coal Blending

Hg
Oxidation Mechanism and Catalysis

Alternative Processes

Multipollutant Processes

The
DESONOX
Process

Other Combined Processes

Catalytic Filters

New Technologies

Plasma‐Assisted Processes

Photocatalytic Processes
Solid Catalysts for the Oxidation of Volatile Organic Compounds
Authors: Spivey James J.
Published: March 2008

The sections in this article are

Introduction

Significance of the Problem

Applications of Catalytic Oxidation for
VOC
Control

Catalytic Oxidation

Scope of this Chapter

Reactors and Process Configurations for Catalytic Oxidation Systems

Reactors

Process Configurations

General Considerations

Specific Problems in Chlorinated
VOC
(
CVOC
) Oxidation

Catalyst Deactivation in
CVOC
Oxidation

Byproducts

Higher Temperatures

Mixture Effects

Deactivation

Noble Metal Catalysts

Pt
catalysts

Effect of Synthesis Conditions

Support Effects

Pt
‐Based Catalysts: Catalyst Deactivation

Pd
Catalysts

Effect of Reduction

Effect of Promoters

Pd
Catalysts:
CVOC
Oxidation

Metal Oxide Catalysts

Vanadium‐Based Catalysts

V
‐Based Catalysts:
CVOC
Oxidation

Ceria‐Based Catalysts

Manganese‐Based Catalysts

Mn
‐Based Catalysts:
CVOC
Oxidation

Effect of Water Vapor

Byproducts

Effect of Support Acidity

Chlorine Retention

Zeolite‐Supported
Mn
versus
Mn
Perovskites

Chromia‐Based Catalysts

Cr
‐Based Catalysts:
CVOC
Oxidation

Effect of Support

Deactivation

Copper‐Based Catalysts

Cu
‐Based Catalysts:
CVOC
Oxidation

Cobalt‐Based Catalysts

Co
‐Based Catalysts:
CVOC
Oxidation

Nickel‐Based Catalysts

Tungsten‐Based Catalysts

Uranium‐Based Catalysts

U
‐Based Catalysts:
CVOC
Oxidation

Kinetics

L
angmuir–
H
inshelwood (
L
–
H
) Models

M
ars–van
K
revelen (
M
–
v
K
) Model
Heterogeneous Catalysis in the Troposphere
Authors: Parmon Valentin M.
Published: March 2008

The sections in this article are

Introduction

The Atmosphere as a Global Catalytic and Photocatalytic Reactor

Thermal Heterogeneous Catalytic Processes over Ice Particles, and Liquid and Solid Aerosols

Hydrolytic Reactions

Redox Reactions

Acid‐Catalyzed Reactions of Organic Compounds over Aerosols

Heterogeneous Photocatalytic Reactions in the Troposphere

Role of Heterogeneous Photocatalytic Processes in the Global Chemistry of the Atmosphere

Experimental Data on Photocatalytic Reactions of Atmospheric Components

Photocatalytic Reactions of the Main Atmospheric Components over Semiconductor Oxides

Photocatalytic Reactions of Trace Components of the Atmosphere over Semiconductor Oxides

Photocatalysis over Compounds with Wide Band Gaps

Photocatalysis by Dissolved Transition Metal Ions

Photogenerated Catalysis

Destructive Photoadsorption by Alkaline Earth Oxides

Role of Thermal Absorption and Adsorption in Tropospheric Catalysis and Photocatalysis

Conclusions
Hydrogen Sulfide to Sulfur (Claus Process)
Authors: Jüngst Eckhard , Nehb Wolfgang
Published: March 2008

The sections in this article are

Occurrence of Hydrogen Sulfide

Hydrogen Sulfide Removal from Gases

History of the Claus Process

Chemistry of the Claus Process

Typical Claus Plant

Claus Catalysts

Desirable Properties of Claus Catalysts

Deactivation of Claus Catalysts

Classification of Claus Catalysts

Surface Reactions on a Claus Catalyst

Adsorption of Sulfur Dioxide

Adsorption of Hydrogen Sulfide

Adsorption of Sulfur Dioxide and Hydrogen Sulfide (Claus Reaction)

Typical Design of a Claus Reactor

Sulfur Recovery Increase

Claus and Oxygen Fit Together

Superclaus and Euroclaus Process

Tail Gas Treating Units
Müller–Rochow Synthesis: The Direct Process to Methylchlorosilanes
Authors: Kalchauer Wilfried , Pachaly Bernd
Published: March 2008

The sections in this article are

Introduction

Formation of Methylchlorosilanes

Reaction Mechanism

Copper Catalyst

Promoters and Inhibitors

Reactants and Raw Materials

Influence of Temperature and Pressure

Applications in the Silicones Industry

Industrial Process

Parameters and Process Control

Course of Production Runs

Byproduct Utilization and Waste Treatment

Outlook
Catalytic Decomposition of Energetic Compounds: Gas Generators and Propulsion1A list of abbreviations/acronyms used in the text is provided at the end of the chpater
Authors: Batonneau Yann , Kappenstein Charles J. , Keim Wilhelm
Published: March 2008

The sections in this article are

Introduction

Energetic Compounds

Propellants

Gas generators

Explosive Materials

Ignition systems

Scope of the Chapter, and Literature Data

Units

Some Propulsion Elements

A Short Introduction to Propulsion Theory

Comparison of Propulsion Types and Propellants

Propulsion System Types

Propellants

Advantages of Catalytic Propulsion

A Brief History of Rocketry and Catalytic Propulsion

The Current Supremacy of Hydrazine

Introduction

Catalysts

Heterogeneous Catalysis: General Studies

Mechanistic Considerations

ALiterature Overview

BThermodynamic Data

CIsotope‐Related Studies

DSingle‐Crystal Studies

ECatalytic Cycle Proposals

Iridium‐Based Industrial Catalysts

AShell 405 Catalyst (USA)

BKaliChemieKC12GACatalyst (Germany)

CCnesro Catalyst (France)

DGIPKhCatalysts (formerUSSR)

New Hydrazine Decomposition Catalysts

Homogeneous Catalysis and Coordination Chemistry of Hydrazine

Applications of Hydrazine Catalytic Decomposition

Gas Generators

Use in Fuel Cells

Corrosion Protection

Drawbacks of Hydrazine

“Green” Propellants as Hydrazine Replacements

Introduction

Energetic Aqueous Ionic Liquids

Thermal Decomposition

Catalytic Decomposition ofHAN,ADN, andHNF

AHydroxyl Ammonium Nitrate (HAN)

BHydrazinium NitroFormate (HNF)

CAmmonium DiNitramide (ADN)

Development of Tools for Catalyst Evaluation

The Comeback of Hydrogen Peroxide

Introduction

Thermal and Catalytic Decomposition

Catalysts for Monopropellant Engines

Kinetic Rate of Decomposition

Hybrid Engine

Hypergolic Bipropellant Engine

Effect of Stabilizers on Catalytic Decomposition

Nitrous Oxide (N2O) for Monopropellant Engines or Hybrid Engines

Introduction

Catalysts

Use of N2O as a Monopropellant

Use of N2O for Hybrid Engine

Future Prospective Applications of Catalytic Propulsion

New Energetic Liquids

Catalysts for Air‐Breathing Supersonic or Hypersonic Jets

Catalysts for Pulse Detonating Engine

Ignition of Gaseous Hydrogen–Oxygen Mixtures

Gas Generator to Power Micropumps through Small Turbines

Conclusion: A Biological System using H2O2Decomposition for Tactical Defense

Acknowledgement
Steam Reforming1A list of abbreviations/acronyms used in the text is provided at the end of the chapter.
Authors: Rostrup‐Nielsen Jens Richard
Published: March 2008

The sections in this article are

Introduction

Reactions

Thermodynamics

Applications

Industrial Developments

The Reforming Process

The Tubular Reformer

Convective Reformers

Reforming Rates and New Reformer Concepts

Catalysts

Catalyst Activity

Non‐Metal Catalysts

Kinetics

Industrial Catalysts

Major Catalyst Problems

Sintering

Sulfur Poisoning

Carbon Formation

Catalyst Promotion

The Active Site

Step Sites

Carbon Formation

Blockage of Step Sites

Geometric and Electronic Effects
Water Gas Shift and
COS
Removal
Authors: Hinrichsen Kai‐Olaf , Kochloefl Karl , Muhler Martin
Published: March 2008

The sections in this article are

Introduction

Thermodynamics

High‐Temperature Shift (
HTS
)

Fe

Cr
Catalysts

Kinetics and Mechanism

Industrial Realization

Co

Cr
Catalysts

Chromium‐Free Catalysts

Low‐Temperature Shift (
LTS
)

Copper Catalysts

Kinetics and Mechanism

Industrial Realization

“Sour Gas” Shift

Molybdenum Catalysts

Kinetics and Mechanism

Industrial Realization

COS
Removal

Thermodynamics

Catalysts

Kinetics and Mechanism

Industrial Realization

WGS
over Supported Noble Metals

Platinum Catalysts

Gold Catalysts
Gas‐to‐Liquids
Authors: Remans Tom J. , Jenzer Gregor , Hoek Arend
Published: March 2008

The sections in this article are

Introduction toGTL

Basic Steps inGTL

Synthesis Gas Production and Purification

Purification of Natural Gas

Sulfur Removal

Hydrocarbon Removal

Trace Components Removal

Present Syngas Generation Technologies

Non‐catalytic Partial Oxidation (POX)

Autothermal Reforming (ATR)

Developments

Purification of Syngas

Fischer–Tropsch Reaction

Reactor Types

Catalysts

Active Metals

Carriers

Promoters

Reaction Mechanisms and Kinetics

Catalyst Poisons

Sulfur Compounds

Others

Mild Hydrocracking

Process Description

Catalysts

Composition

Other Requirements

Reaction Mechanism

Reactor

Products

LPG

Naphtha

Kerosene

Base Oils

Gas Oil

Challenges inGTL,CTLandBTL
Oxidative Coupling of Methane
Authors: Kondratenko Evgenii V. , Baerns Manfred
Published: March 2008

The sections in this article are

Introduction

Fundamentals of the
OCM
Reaction

Catalytic Materials and Their Performance

Mechanistic Aspects

Oxygen Species in the
OCM
Reaction

Structural Defects and Related Physicochemical Properties

New Approaches in Catalyst Design

Reaction and Process Engineering

Chemical Kinetics

Modeling, Simulation and Performance of Catalytic Reactors

Distributed Oxygen Supply to a Catalytic Fixed‐Bed Reactor

Counter‐Current Moving‐Bed Reactor

Fluidized‐Bed Reactors

Membrane Reactors

Process Concepts

Conclusion
Catalysis in Direct Coal Liquefaction
Authors: Haenel Matthias W.
Published: March 2008

The sections in this article are

Introduction

Coal Structure

Organic Structure

Inorganic Structure

Physical Structure

Fundamental Transformations in Direct Coal Liquefaction

Coal Properties

Primary Liquefaction Products

Solvent

Catalysis in Direct Coal Liquefaction

Dissolution Catalysts in the First Liquefaction Stage

Supported Catalysts

Dissolved Catalysts

Perspectives for Direct Coal Liquefaction
Fuel Processors
Authors: Peters Ralf
Published: March 2008

The sections in this article are

Introduction

Energy Carriers for Fuel Cells

Thermodynamic Calculations

Reforming Processes for Hydrogen Production

Thermodynamic Equilibrium Calculations

Carbon Formation and Deposition

Fuel Pre‐Processing

Removal of Harmful Species from Methanol and Water

Desulfurization

Evaporation of Liquid Fuels

Methanol Steam Reforming

Catalysts for Methanol Steam Reforming

Reaction Path of Methanol Steam Reforming onCu/ZnOCatalysts

Active Sites ofCu/ZnOCatalysts

Pd/ZnOCatalysts

Kinetics of Methanol Steam Reforming

Reformer Design Based on Laboratory‐Scale Experiments

Example of Methanol Steam Reformer Development

Autothermal Reforming of Gasoline and Diesel

Internal Steam Reforming of Methane forSOFCSystems

Gas Treatment forPEFCSystems

Water‐Gas Shift Reaction

COFine Cleaning

AH2Separation Membranes

BPreferentialCOOxidation

CSelectiveCOMethanation

Catalytic Combustion of Fuel Cell Tail Gases

Component and System Design

Heat Exchanger Networks

Innovative Reactor Concepts

Dynamic System Modeling

Outlook

Acknowledgments
Aromatization of Light Alkanes
Authors: O'Connor Cyril T.
Published: March 2008

The sections in this article are

Introduction

Thermodynamics of Alkane Aromatization

Catalysts

Ga/HZSM‐5

Pt/KL

Other Catalysts for Alkane Aromatization

Aromatization of Alkanes in the RangeC3C8

Aromatization of Propane

Aromatization of Ethane

Aromatization of Butane

Aromatization of Hexane

Aromatization of Pentanes, Heptanes and Octanes

Commercial Applications of Aromatization of Light Alkanes

Conclusion
Ring Opening of Aromatics
Authors: Weitkamp Jens
Published: March 2008

The sections in this article are

Introduction

Fundamentals of Hydrodecyclization of Cycloalkanes

Hydrogenolysis on Metals

Hydrocracking on Bifunctional Catalysts

Cracking and Activation of Hydrogen on Monofunctional Acidic Catalysts

Ring Opening of Aromatics in Diesel and Jet Fuels

Bifunctional Catalysts

Metal Catalysts

Acid Catalysts

Ring Opening of Aromatics in Gasoline Without Degradation of the Carbon Number

Ring Opening of Aromatics in Pyrolysis Gasoline Followed by Hydrocracking into a Synthetic Steam‐Cracker Feed

Hydrodecyclization and Hydrocracking of Cycloalkanes on Acid Zeolites

Direct Ring Opening of Aromatics on Bifunctional Zeolites

Conclusions

Acknowledgments
Alkylation of Aromatics
Authors: Clark Michael C. , Smith C. Morris , Stern David L. , Beck Jeffrey S.
Published: March 2008

The sections in this article are

Introduction

Alkylation of Benzenes, Phenols and Anilines

Acid‐Catalyzed Synthesis of Alkylbenzenes

General Aspects

A
Mechanistic Considerations

B
Kinetic Considerations

C
Substrate Selectivity

D
Positional Selectivity

E
Depolyalkylation

F
Monoalkylation and Polyalkylation

Commercial Processes

A
Ethylbenzene

B
Isopropylbenzene

C
Ethyltoluene

D
Isopropyltoluene

E
Diisopropylbenzene

F
Higher Alkylbenzenes

Base‐Catalyzed Synthesis of Alkylbenzenes

General Aspects

Synthesis of Styrene from Toluene with Methanol

Isobutylbenzene

tert
‐Amylbenzene

Butenylation of Alkylaromatics

Alkylphenols

Methylphenols

Higher Alkylphenols

Alkylanilines

Alkylation of Binuclear Aromatics

Alkylation of Naphthalene

Alkylation of Biphenyl

Conclusions