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  • 2000-2004
  • 1995-1999  (143)
  • 1990-1994
  • 1996  (143)
  • Genetics
  • Nuclear reactions
  • Physical Chemistry
  • 1
    Electronic Resource
    Electronic Resource
    Detection of oncogene mutation from neoplastic colonic cells exfoliated in feces (1996)
    Springer
    Diseases of the colon & rectum 39 (1996), S. 1238-1244 
    Details
    ISSN: 1530-0358
    Keywords: Colorectal neoplasms ; Genetics ; K-ras ; Gene mutations ; Early diagnosis ; Polymerase chain reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Purpose: Best chances of a cure from colorectal cancer are obtained before metastatic spread. Lack of specific tests allowing early diagnosis of the tumor accounts for investigation of gene alterations involved in carcinogenesis by a noninvasive method. In the present study, K-ras codons 12 and 13 mutations were studied in neoplastic cells shed from the bowel into the stool and those contained in the tumor and normal mucosa. Moreover, healthy patients and a few others with precancerous conditions were examined. METHODS: Stool, tumor, and mucosa samples were taken from 25 patients with colorectal adenocarcinoma. Stool and mucosa samples were obtained from 11 healthy patients, and stool, pathologic bowel tissue, and normal mucosa samples were obtained from 3 patients with adenoma (1) or ulcerative colitis (2). Polymerase chain reaction amplification and restriction enzyme analysis were performed. RESULTS: K-ras codon 12 mutations were detected in both tumor and stool samples of 10 cancer patients, and no gene alterations were observed in 14 patients. In one patient with a tumor, a mutation was shown in only the tumor tissue. The agreement rate in tumor and stool analysis was 96 percent. A normal pattern of K-ras codons 12 and 13 was observed in the bowel mucosa. All stool and mucosa samples from healthy patients were not altered in K-ras.Agreement was registered between samples taken from patients with preneoplastic lesions. CONCLUSIONS: These preliminary findings show a high rate of accuracy in the investigation of K-ras alterations in the colorectal cells shed into the feces, suggesting that such an approach could be used to study other gene alterations and, prospectively, to identify early colorectal cancers.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02055116
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  • 2
    Electronic Resource
    Electronic Resource
    Evaluation of the BCL-2 gene locus as a susceptibility locus linked to the clinical expression of systemic lupus erythematosus (SLE) (1996)
    Springer
    Rheumatology international 16 (1996), S. 121-124 
    Details
    ISSN: 1437-160X
    Keywords: SLE ; Apoptosis ; bcl-2 gene ; Susceptibility ; Linkage ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Systemic lupus erythematosus (SLE) is an autoimmune disease characterised by the production of a large number of autoantibodies. It has been postulated that this may be the result of prolonged longevity of auto-reactive B cells due to defective regulation of programmed cell death (apoptosis). The proto-oncogenebcl-2 is involved in the control of apoptosis in immunocompetent cells, and its over-expression is noted in T and B cells from SLE patients. This study examined the genetic linkage between thebcl-2 gene locus and SLE susceptibility using the affected sib-pair method in SLE families. Seventeen caucasian multiplex families were evaluated. A polymorphic microsatellite marker closely linked to thebcl-2 gene on 18g21.3 was used to determine thebcl-2 genotype. We demonstrated that haplotype sharing among the affected sibling pairs was not statistically different from random (P〉0.5). This suggests that thebcl-2 gene locus does not confer a genetic susceptibility to SLE expression.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01409984
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  • 3
    Electronic Resource
    Electronic Resource
    Do animal models have a place in the genetic analysis of quantitative human behavioural traits? (1996)
    Springer
    Journal of molecular medicine 74 (1996), S. 515-521 
    Details
    ISSN: 1432-1440
    Keywords: Emotionality ; Behaviour ; Genetics ; Animal models ; QTL analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract It seems that the genetic basis of common psychiatric diseases such as schizophrenia and manic-depressive psychosis is amenable to the genetic mapping strategies that have been successful in other complex disorders such as diabetes. The next challenge is the genetic dissection of quantitative behavioural traits such as mood, personality and intelligence. Quantitative traits pose new problems for gene cloning experiments. We argue that one way forward is by using animal models. One of the features of quantitative traits is that the DNA sequence variants which are responsible for them are unlikely to be immediately recognizable. In contrast to many qualitative traits where a discrete phenotypic difference is often the consequence of an inactivating mutation, the allelic variation responsible for quantitative traits probably has a more subtle basis. This distinction means that strategies to clone the genetic basis of quantitative behavioural traits will have to rely on functional assays of alleles thought to be important in determining the phenotype. We suggest that an efficient strategy for detecting sequences that give rise to quantitative behavioural traits can be devised in the mouse. The importance and utility of the mouse for quantitative trait analysis make it worthwhile to investigate mouse models of human behaviour; these advantages outweigh the difficulties that arise in attempts to validate the animal models. As an example we review the evidence that validates rodent emotionality as an animal model for susceptibility to human anxiety. We show that there is good evidence that rodent emotionality is a central nervous system state with a genetic basis, and that there are neuropharmacological and neuroanatomical parallels with human anxiety. Furthermore, our own work has shown that the genetic basis of the trait is relatively simple, and that the task of characterizing it at a molecular level is feasible. We expect that future experiments will show us how genetic variation gives rise to quantitative behavioural traits.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00204977
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  • 4
    Electronic Resource
    Electronic Resource
    Do animal models have a place in the genetic analysis of quantitative human behavioural traits? (1996)
    Springer
    Journal of molecular medicine 74 (1996), S. 515-521 
    Details
    ISSN: 1432-1440
    Keywords: Key words Emotionality ; Behaviour ; Genetics ; Animal models ; QTL analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract  It seems that the genetic basis of common psychiatric diseases such as schizophrenia and manic-depressive psychosis is amenable to the genetic mapping strategies that have been successful in other complex disorders such as diabetes. The next challenge is the genetic dissection of quantitative behavioural traits such as mood, personality and intelligence. Quantitative traits pose new problems for gene cloning experiments. We argue that one way forward is by using animal models. One of the features of quantitative traits is that the DNA sequence variants which are responsible for them are unlikely to be immediately recognizable. In contrast to many qualitative traits where a discrete phenotypic difference is often the consequence of an inactivating mutation, the allelic variation responsible for quantitative traits probably has a more subtle basis. This distinction means that strategies to clone the genetic basis of quantitative behavioural traits will have to rely on functional assays of alleles thought to be important in determining the phenotype. We suggest that an efficient strategy for detecting sequences that give rise to quantitative behavioural traits can be devised in the mouse. The importance and utility of the mouse for quantitative trait analysis make it worthwhile to investigate mouse models of human behaviour; these advantages outweigh the difficulties that arise in attempts to validate the animal models. As an example we review the evidence that validates rodent emotionality as an animal model for susceptibility to human anxiety. We show that there is good evidence that rodent emotionality is a central nervous system state with a genetic basis, and that there are neuropharmacological and neuroanatomical parallels with human anxiety. Furthermore, our own work has shown that the genetic basis of the trait is relatively simple, and that the task of characterizing it at a molecular level is feasible. We expect that future experiments will show us how genetic variation gives rise to quantitative behavioural traits.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001090050054
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  • 5
    Electronic Resource
    Electronic Resource
    Die Genetik der Migräne (1996)
    Springer
    Der Nervenarzt 67 (1996), S. 837-845 
    Details
    ISSN: 1433-0407
    Keywords: Schlüsselwörter Migräne ; Genetik ; Familiäre Hemiplegische Migräne ; Linkageanalyse ; Zwillingsstudien ; Assoziationsstudien ; Key words Migraine ; Familial Hemiplegic Migraine ; Genetics ; Linkage analysis ; Twin studies ; Association studies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Summary Several historical reports focusing on the heredity of migraine, as well as recent studies on its epidemiology and molecular biology, have revealed evidence for a decisive role of genetic factors in the aetiopathogenesis of familial migraine. Indeed, family studies, segregation analyses and twin studies have shown that genetic factors play an important role in disposition towards migraine but could not explain the entire aetiopathogenesis. The influence of extragenetic factors, however, remains mostly unknown. Recent linkage analyses have provided evidence for genetic heterogeneity. A locus for Familial Hemiplegic Migraine (FHM), the only known type of migraine that follows autosomal-dominant transmission, has been linked to chromosome 19p13 but genetic heterogeneity has also been shown, i. e. different types of migraine could be excluded from this locus. Further investigations should concentrate on identifying the FHM gene on chromosome 19p13, on linkage analyses with markers for different susceptibility genes, and on genomic analyses of highly informative pedigrees. This would lead to further clues to the pathogenesis underlying migraine and, thus, to therapeutic developments.
    Notes: Zusammenfassung Nachdem bereits in historischen Beschreibungen eine genetische Verursachung der Migräne vermutet worden war, haben epidemiologische und molekularbiologische Forschungen in den letzten Jahren differenzierte Ergebnisse über genetische Faktoren in der Ätiopathogenese der familiären Migräne geliefert. Aufgrund von Familien- und Segregationsanalysen und von Zwillingsstudien wird dargestellt, daß genetische Faktoren mit größter Wahrscheinlichkeit eine Rolle in der Pathogenese der typischen Migräne spielen. Inwieweit extragenetische Faktoren auf die Ätiopathogenese der Migräne Einfluß nehmen, ist weitgehend offen. Linkageanalysen haben in jüngster Zeit gezeigt, daß möglicherweise mehrere verschiedene Gene für diese Erkrankung verantwortlich sind. Für die Familiäre Hemiplegische Migräne (FHM), der einzigen Migräneform, für die ein autosomal-dominanter Erbgang nachgewiesen ist, konnte ein Genlocus auf Chromosom 19p13 gefunden werden, gleichzeitig wurde aber auch genetische Heterogenität nachgewiesen. Verschiedene andere Formen der Migräne zeigten keine Linkage zu diesem Locus. Weitere Forschungen sollten neben der Identifizierung des FHM-Gens auch Linkageanalysen für Kandidatengene und Genomanalysen an großen informativen Familien zum Ziel haben. Letztlich werden die Ergebnisse genaueren Einblick in die Pathophysiologie der Migräne liefern und damit therapeutisch relevant sein.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001150050061
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  • 6
    Electronic Resource
    Electronic Resource
    The genetics of proximal femur geometry, distribution of bone mass and bone mineral density (1996)
    Springer
    Osteoporosis international 6 (1996), S. 178-182 
    Details
    ISSN: 1433-2965
    Keywords: Bone density ; Femor geometry ; Genetics ; Twins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract To estimate genetic effects on femoral neck geometry and the distribution of bone mineral within the proximal femur a cross-sectional twin analysis was carried out at a university hospital that compared correlations in these traits in pairs of mono- and dizygo-tic female twins. Monozygotic (MZ, n=51 pairs, age 49.1±9.3 years) and dizygotic (DZ, n=26 pairs, age 45.7±11.3 years) twins were randomly selected from a larger sample of twins previously studied. Measurements of bone mineral density (BMD), femoral neck angles and length, cross-sectional area and moment of interia, the center of mass of the narrowest cross-section of the femoral neck, and BMDs of regions within the femoral neck were made. A summary index of the resistance of the femoral neck to forces experienced in a fall with impact on the greater trochanter (Fall Index, FI) was calculated. MZ pair intraclass correlations (rMZ) were significantly (p〈0.05) different from zero for all bone mass and femoral geometry variables (0.35〈rMZ〈0.82). DZ pair correlations (rDZ) were lower thanrMZ for all variables (0.04〈rDZ〈0.52) except femoral neck length (rDZ=0.38, rMZ=0.36). After adjustment for BMD of the femoral neck,rMZ was significantly greater thanrDZ, yielding high heritability estimates for regional BMDs (0.72〈H 2〈0.78), the center of mass of the femoral neck (H 2=0.70, −0.04 to 1.43 95% CI) and the resistance of the femoral neck to forces experienced in a fall (FI,H 2=0.94, 0.06 to 1.85 95% CI), but not for femoral neck length. Adjustments for age did not alter these findings. It is concluded that there are significant familial influences on the distribution of femoral bone mass and on the calculated structural strength of the proximal femur, but not on femoral neck length. If the assumptions of the twin model are correct, this is evidence for genetic factors influencing these traits.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01623944
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  • 7
    Electronic Resource
    Electronic Resource
    Differential genetic etiology of reading disability as a function of mathematics performance (1996)
    Springer
    Reading and writing 8 (1996), S. 295-306 
    Details
    ISSN: 1573-0905
    Keywords: Differential diagnosis ; Etiology ; Genetics ; Mathematics performance ; Reading disability ; Twins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Education
    Notes: Abstract In order to assess the etiology of reading disability as a function of mathematics performance, data from 168 monozygotic (MZ) and 127 same-sex dizygotic (DZ) twin pairs in which at least one member of each pair was reading-disabled were subjected to quantitative genetic analyses. MZ and DZ concordance rates for reading disability were computed for different levels of mathematics performance, and reading performance data were fitted to an extension of the basic multiple regression model for the analysis of selected twin data. Results of these analyses suggest that genetic factors may be especially salient as a cause of reading disability in children with borderline deficits in mathematics performance: thus, mathematics performance may be a valid dimension for diagnosing subtypes of reading disability.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00395110
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  • 8
    Electronic Resource
    Electronic Resource
    Early-onset dementias: clinical, neuropathological and genetic characteristics (1996)
    Springer
    Acta neuropathologica 91 (1996), S. 451-465 
    Details
    ISSN: 1432-0533
    Keywords: Key words Alzheimer’s disease ; Clinicopathological ; correlations ; Early-onset dementia ; Genetics ; Pick’s ; disease
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004010050452
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  • 9
    Electronic Resource
    Electronic Resource
    Maternally inherited diabetes and deafness: a new diabetes subtype (1996)
    Springer
    Diabetologia 39 (1996), S. 375-382 
    Details
    ISSN: 1432-0428
    Keywords: Genetics ; maternally inherited diabetes and deafness ; NIDDM ; IDDM ; mitochondria ; MELAS syndrome
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Diabetes mellitus is a common disease with many forms of clinical expression. In addition, the development of diabetic complications is not only dependent on glycaemic control but also on individual factors which may be related to genetic heterogeneity. At present, multiple genetic factors are being recognized as contributing to the development of diabetes or possibly modulating its clinical expression. The purpose of this review is to give an overview of our current knowledge on a subtype of diabetes which is apparently caused by a single mutation in the mitochondrial DNA.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00400668
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  • 10
    Electronic Resource
    Electronic Resource
    Geographic variation in seed dormancy among populations of Echinochloa crus-galli (1996)
    Springer
    Oecologia 108 (1996), S. 419-423 
    Details
    ISSN: 1432-1939
    Keywords: Barnyard grass ; Seed dormancy ; Geographic variation ; Genetics ; Ecophysiology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In 1991–1993, we investigated the incidence of seed dormancy in 25 local populations of barnyard grass, Echinochloa crus-galli (L.) P.Beauv., in the western Czech Republic. The percentage of germination after 4 months afterripening of dry seeds at 25°C varied between 0.0 and 83.6%. Although there were significant annual differences in the percentage of germination at some localities, typical proportions of dormant seeds persisted over 3 years at field sites where the seed bank was not disturbed. One-way ANOVA (using data from 14 cultivated or abandoned fields) revealed that 73.0% of variance in seed dormancy incidence could be attributed to the effect of locality (P〈0.001). Incidence of dormancy was not correlated with mother plant stature (dry above-ground biomass, number of tillers, maximal stem height) nor seed mass. There was a significant correlation (r 2=0.403, P〈0.005) between dormancy incidence at natural localities in 1991 and in F1 offspring sown at experimental grounds at Praha-Ruzyně in 1992. The results indicate that heredity is important in maintaining local variation in seed dormancy, probably favoured by the self-pollinating reproduction of barnyard grass.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00333716
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  • 11
    Electronic Resource
    Electronic Resource
    The clinical and genetic correlates of MRI findings in myotonic dystrophy (1996)
    Springer
    Neuroradiology 38 (1996), S. 629-635 
    Details
    ISSN: 1432-1920
    Keywords: Key words Myotonic dystrophy ; Magnetic resonance imaging ; Brain ; Muscles ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Amplification of an unstable CTG trinucleotide repeat sequence in a protein kinase gene on chromosome 19 has recently been recognised as the molecular basis of myotonic dystrophy (DM), a multisystem disorder with a wide spectrum of muscular and extramuscular manifestations. The CTG expansion of 40 patients was assessed by direct genotype analysis of the white blood cell DNA and correlated with MRI of the brain and muscles, and with functional clinical data. Cerebral pathology on MRI consisted of diffuse atrophy (68 %), subcortical white matter lesions (65 %), wide Virchow-Robin spaces (38 %) and thickening of the skull (35 %). Cerebral atrophy and extent of white matter disease correlated significantly with mental retardation, duration of disease and CTG fragment amplification. MRI of the muscular system showed fatty degeneration of different degrees in neighbouring muscles causing a mosaic pattern of the thigh in 38 % and the calf in 44 %. Muscular changes on MRI were strongly correlated with muscular impairment but less strongly with CTG expansion. Changes on MRI reflect the stage of development of tissue pathology in DM, modified by defect of the DM gene. Pathology on MRI is strongly correlated with functional deficits.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s002340050322
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  • 12
    Electronic Resource
    Electronic Resource
    Familial Mediterranean fever in Arab children: the high prevalence and gene frequency (1996)
    Springer
    European journal of pediatrics 155 (1996), S. 540-544 
    Details
    ISSN: 1432-1076
    Keywords: Key words Amyloidosis ; Arab ; children ; Familial Mediterranean ; fever ; Genetics ; Recurrent ; abdominal pain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Over a period of 3 years, 192 children with familial Mediterranean fever were prospectively studied. Of these, 106 (55%) were girls and 86 (45%) were boys. The prevalence was 1 : 2600 children with a gene frequency of 1 : 50. The age at onset ranged between 4 months and 16 years. Of these patients 24% started their illness below the age of 2 years and 88% were symptomatic before the age of 10 years; 82% had recurrent abdominal pain, 43% had pleurisy, 37% had arthritis, 15% had cutaneous manifestations, 12% had splenomegaly and 4% had hepatomegaly. The presenting symptoms were abdominal pain in 51%, unilateral chest pain in 23% and arthritis in 26%. The family history was positive in 62%. Of 12 affected families 19 members had/have renal failure and amyloidosis was confirmed in 7 patients. Conclusion Our data show a high prevalence of familial Mediterranean fever and a high gene frequency in Arab children similar to that reported in Jews and Armenians.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01957901
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  • 13
    Electronic Resource
    Electronic Resource
    Familial Mediterranean fever in Arab children: The high prevalence and gene frequency (1996)
    Springer
    European journal of pediatrics 155 (1996), S. 540-544 
    Details
    ISSN: 1432-1076
    Keywords: Amyloidosis ; Arab children ; Familial Mediterranean fever ; Genetics ; Recurrent abdominal pain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Over a period of 3 years, 192 children with familial Mediterranean fever were prospectively studied. Of these, 106 (55%) were girls and 86 (45%) were boys. The prevalence was 1∶2600 children with a gene frequency of 1∶50. The age at onset ranged between 4 months and 16 years. Of these patients 24% started their illness below the age of 2 years and 88% were symptomatic before the age of 10 years: 82% had recurrent abdominal pain, 43% had pleurisy, 37% had arthritis, 15% had cutaneous manifestations, 12% had splenomegaly and 4% had hepatomegaly. The presenting symptoms were abdominal pain in 51%, unilateral chest pain in 23% and arthritis in 26%. The family history was positive in 62%. Of 12 affected families 19 members had/have renal failure and amyloidosis was confirmed in 7 patients.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01957901
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  • 14
    Electronic Resource
    Electronic Resource
    Inbred mouse strains vary in oral self-selection of nicotine (1996)
    Springer
    Psychopharmacology 124 (1996), S. 332-339 
    Details
    ISSN: 1432-2072
    Keywords: Nicotine ; Genetics ; Self-administration ; Reinforcement ; Seizures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Inbred mouse strains differ in sensitivity to a first dose of nicotine and in the development of tolerance to nicotine. The experiments reported here used six inbred mouse strains (A, BUB, C3H, C57BL/6, DBA/2, ST/b) that differ in sensitivity to an acute challenge dose of nicotine to determine whether differences in oral self-selection of nicotine exist. Animals were presented with solutions containing nicotine or vehicle (water or 0.2% saccharin) and their daily intake of the two fluids was measured for 4 days starting with a 10 µg/ml nicotine solution. This was followed by sequential 4-day testing with 20, 35, 50, 65, 80, 100, 125, 160, and 200 µg/ml nicotine solutions. The strains differed dramatically in their self-selection of nicotine and in maximal daily dose (mg/kg); the rank order of the strains was C57BL/6〉DBA〉BUB〉A≥C3H≥ST/b for both the tap water and 0.2% saccharin choice experiments. Correlations between nicotine consumption and sensitivity to nicotine, as measured by a battery of behavioral and physiological responses, were also calculated. Strain differences in nicotine intake were highly correlated with senstivity to nicotine-induced seizures. As senstivity to nicotine-in-duced seizures increases, oral self-selection of nicotine decreases. This finding may suggest that this toxic action of nicotine serves to limit intake.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02247438
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  • 15
    Electronic Resource
    Electronic Resource
    Eye tracking dysfunction in families with multiple cases of schizophrenia (1996)
    Springer
    European archives of psychiatry and clinical neuroscience 246 (1996), S. 175-181 
    Details
    ISSN: 1433-8491
    Keywords: Schizophrenia ; Genetics ; Liability ; Vulnerability ; Eye-tracking dysfunction ; Eye movements ; Smooth-pursuit eye movements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract There is increasing evidence that the genetic predisposition for schizophrenia in families affects more individuals than those fulfilling the criteria for schizophrenia. This finding is supposed to be one of the major problems in molecular genetic schizophrenia research, especially when linkage studies are employed. Eye-tracking dysfunction (ETD), which is conceived as a possible phenotypic marker for genetic liability to schizophrenia, may offer considerable advantages. However, there is only little information from families with multiple occurrence of schizophrenia. It is still unclear whether in these families ETD aggregates with diagnoses from the schizophrenia spectrum. This first report from an ongoing study presents the results of 48 individuals from 6 multiplex families. Smooth-pursuit eye movements were recorded by infrared reflectometry and assessed by quantitative measurement techniques. Along with the high degree of psychiatric morbidity in these families, in 56.3% of the individuals ETD was assessed. Reduced mean pursuit gain was present in 39.6%. The distribution of eye-tracking dysfunction resembles the distribution of schizophrenia-related psychiatry morbidity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02188950
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  • 16
    Electronic Resource
    Electronic Resource
    Pathophysiology of non-insulin-dependent diabetes and the search for candidate genes: dangerous liaisons? (1996)
    Springer
    Acta diabetologica 33 (1996), S. 257-262 
    Details
    ISSN: 1432-5233
    Keywords: Key words NIDDM ; Candidate genes ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00571560
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  • 17
    Electronic Resource
    Electronic Resource
    Pathophysiology of non-insulin-dependent diabetes and the search for candidate genes: dangerous liaisons? (1996)
    Springer
    Acta diabetologica 33 (1996), S. 257-262 
    Details
    ISSN: 1432-5233
    Keywords: NIDDM ; Candidate genes ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00571560
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  • 18
    Electronic Resource
    Electronic Resource
    The genetics of adult-plant blackleg (Leptosphaeria maculans) resistance from Brassica juncea in B. napus (1996)
    Springer
    Theoretical and applied genetics 92 (1996), S. 382-387 
    Details
    ISSN: 1432-2242
    Keywords: Genetics ; Blacking resistance ; Brassica napus ; Brassica juncea ; Leptosphaeria maculans
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The genetic control of adult-plant blackleg (Leptosphaeria maculans) resistance in a Brassica napus line (579NO48-109-DG-1589), designated “R13” possessing Brassica juncea-like resistance (JR), was elucidated by the analysis of segregation ratios in F2 and F3 populations from a cross between “R13” and the highly blackleg-susceptible B. napus cultivar “Tower”. The F2 segregration ratios were bimodal, demonstrating that blackleg resistance in “R13” was controlled by major genes. Analysis of the segregation ratios for 13 F3 families indicated that blackleg resistance in these families was controlled by three nuclear genes, which exhibited a complex interaction. Randomly sampled plants of F3 progeny all had the normal diploid somatic chromosome number for B. napus. The similarities between the action of the three genes found in this study with those controlling blackleg resistance in B. juncea is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00223683
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  • 19
    Electronic Resource
    Electronic Resource
    Comparative mapping in F2∶3 and F6∶7 generations of quantitative trait loci for grain yield and yield components in maize (1996)
    Springer
    Theoretical and applied genetics 92 (1996), S. 817-826 
    Details
    ISSN: 1432-2242
    Keywords: Zea mays ; RFLPs ; Plant breeding ; Genetics ; Recombination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This study was conducted to compare maize quantitative trait loci (QTL) detection for grain yield and yield components in F2∶3 and F6∶7 recombinant inbred (RI) lines from the same population. One hundred and eighty-six F6∶7 RIs from a Mo17×H99 population were grown in a replicated field experiment and analyzed at 101 loci detected by restriction fragment length polymorphisms (RFLPs). Single-factor analysis of variance was conducted for each locus-trait combination to identify QTL. For grain yield, 6 QTL were detected accounting for 22% of the phenotypic variation. A total of 63 QTL were identified for the seven grain yield components with alleles from both parents contributing to increased trait values. Several genetic regions were associated with more than one trait, indicating possible linked and/or pleiotropic effects. In a comparison with 150 F2∶3 lines from the same population, the same genetic regions and parental effects were detected across generations despite being evaluated under diverse environmental conditions. Some of the QTL detected in the F2∶3 seem to be dissected into multiple, linked QTL in the F6∶7 generation, indicating better genetic resolution for QTL detection with RIs. Also, genetic effects at QTL are smaller in the F6∶7 generation for all traits.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00221893
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  • 20
    Electronic Resource
    Electronic Resource
    The genetics of blackleg [Leptosphaeria maculans (Desm.) Ces, et De Not.] resistance in rapeseed (Brassica napus L.) (1996)
    Springer
    Theoretical and applied genetics 93 (1996), S. 932-940 
    Details
    ISSN: 1432-2242
    Keywords: Genetics ; Adult-plant ; Blackleg resistance ; Brassica napus ; Leptosphaeria maculans ; Australian cultivar
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The genetic control of adult-plant blackleg [Leptosphaeria maculans (Desm.) Ces. et De Not.] resistance in rapeseed (Brassica napus L.) was studied in the F2 and first-backcross populations of the cross “Maluka” (blackleg-resistant) x “Niklas” (highly susceptible). A L. maculans isolate possessing high levels of host specificity (MB2) was used in all inoculations. Resistance/susceptibility was evaluated using three separate measures of crown-canker size, i.e. the percentage of crown girdled (%G), external lesion length (E) and internal lesion area (%II). Disease severity scores for the F2 and first-backcross populations based on E and %II gave discontinuous distributions, indicating major-gene control for these measures of resistance; but those for %G were continuous, indicating quantitative genetic control for this measure. Chi-square tests performed on the (poorly-defined) resistance classes, based on E, in the F2 and first-backcross populations indicated the likelihood for resistance being governed by a single, incompletely dominant major gene. Although the distributions of the F2 and first-backcross populations, based on%II, were clearly discontinuous, the observed segregation ratios for resistance and susceptibility did not fit any of the numerous Mendelian ratios which were considered. Differences in inheritance of resistance according to the assessment method and blackleg isolate used, were discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00224096
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  • 21
    Electronic Resource
    Electronic Resource
    Genetics of virulence in Leptosphaeria maculans (Desm.) Ces. et De Not., the cause of blackleg in rapeseed (Brassica napus L.) (1996)
    Springer
    Theoretical and applied genetics 93 (1996), S. 301-306 
    Details
    ISSN: 1432-2242
    Keywords: Leptosphaeria maculans ; Brassica napus ; Blackleg ; Genetics ; Virulence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The genetic basis of virulence of 24 isolates of L. maculans collected from various sites throughout south-eastern and south-western Australia were studied using five clone-lines of B. napus. The experimental design allowed the estimation of the environmental and genetic components of variance using a standard analysis of variance. Virulence of these isolates (as measured by the percentage of stem girdling, %G) on the clonelines NCII and Tap was found to be most likely controlled by a small number of genes; the broad-sense heritabilities were 79.7% and 67.5% for virulence on NCII and Tap, respectively. The significance of these results in relation to the potential of L. maculans in adapting to new resistant B. napus cultivars is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00223169
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  • 22
    Electronic Resource
    Electronic Resource
    Diallel analysis for aluminium tolerance in tropical soybeans [Glycine max (L.) Merrill] (1996)
    Springer
    Theoretical and applied genetics 92 (1996), S. 267-272 
    Details
    ISSN: 1432-2242
    Keywords: Cerrado ; Savannah ; Acid soils ; Hydroponics ; Nutrient ; Variety ; Genetics ; Inheritance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The soybean is a major crop in the agricultural systems of the Brazilian Cerrados (Savannahs), whose soils are acidic, devoid of nutrients and need to be amended before they are cultivated. However, below the ploughed layer there is a scarcity of nutrients and toxic aluminium (Al). These limit root growth, subsequently causing nutritional imbalance and drought stress. Our aim in the investigation described here was to identify genetic differences in the aluminium tolerance of soybeans by a 9 × 9 diallel cross among contrasting varieties grown in high-Al areas and in hydroponics. Combining ability analysis indicated predominantly additive gene effects, and the additive-dominance model explained most of the genetic differences in this germ plasm for mineral element absorption and root growth under aluminium stress. The relationship between the two factors suggest that conjugation hydroponics and field evaluations in breeding programmes would further improve soybeans with respect to yield stability under tropical cultivation conditions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00223384
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  • 23
    Electronic Resource
    Electronic Resource
    Comparative mapping in F2:3 and F6:7 generations of quantitative trait loci for grain yield and yield components in maize (1996)
    Springer
    Theoretical and applied genetics 92 (1996), S. 817-826 
    Details
    ISSN: 1432-2242
    Keywords: Key words  Zea mays ; RFLPs ; Plant breeding ; Genetics ; Recombination ; Abbreviations  RFLPs Restriction fragment length polymorphisms ; QTL quantitative trait loci ; RIs recombinant inbreds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract   This study was conducted to compare maize quantitative trait loci (QTL) detection for grain yield and yield components in F2:3 and F6:7 recombinant inbred (RI) lines from the same population. One hundred and eighty-six F6:7 RIs from a Mo17×H99 population were grown in a replicated field experiment and analyzed at 101 loci detected by restriction fragment length polymorphisms (RFLPs). Single-factor analysis of variance was conducted for each locus-trait combination to identify QTL. For grain yield, 6 QTL were detected accounting for 22% of the phenotypic variation. A total of 63 QTL were identified for the seven grain yield components with alleles from both parents contributing to increased trait values. Several genetic regions were associated with more than one trait, indicating possible linked and/or pleiotropic effects. In a comparison with 150 F2:3 lines from the same population, the same genetic regions and parental effects were detected across generations despite being evaluated under diverse environmental conditions. Some of the QTL detected in the F2:3 seem to be dissected into multiple, linked QTL in the F6:7 generation, indicating better genetic resolution for QTL detection with RIs. Also, genetic effects at QTL are smaller in the F6:7 generation for all traits.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s001220050198
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  • 24
    Electronic Resource
    Electronic Resource
    Variability and genetics of tolerance for aluminum toxicity in rice (Oryza sativa L.) (1996)
    Springer
    Theoretical and applied genetics 93 (1996), S. 738-744 
    Details
    ISSN: 1432-2242
    Keywords: Aluminum toxicity ; Diallel analysis ; Genetics ; Rice ; Variability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A study was undertaken to investigate the variability among lowland rice cultivars and the mode of gene action of aluminum (Al) toxicity tolerance in rice. Pregerminated seeds were grown in a nutrient solution containing 30 ppm Al and in normal nutrient solution, and relative root length (RRL) was determined at the 14-day-old stage to characterize genotypes for tolerance. Sixty-two traditional rice cultivars grown on lowland acid sulfate soil areas of Asia and West Africa were tested. Tolerant varieties ‘Azucena’, ‘IRAT104’, and ‘Moroberekan’, moderately sensitive ‘IR29’ and ‘IR43’, and sensitive ‘IR45’ and ‘IR1552’ were used to investigate the genetics of tolerance by diallel analysis. Of the 62 cultivars tested, only 3 were found to be sensitive to A l toxicity. Among the tolerant cultivars identified, 11 (‘Siyam Kuning’, ‘Gudabang Putih’, ‘Siyam’, ‘Lemo’, ‘Khao Daeng’, ‘Siyamhalus’, ‘Bjm-12’, ‘Ketan’, ‘Seribu Gantang’, ‘Bayer Raden Rati’, and ‘Padi Kanji’) were found to possess higher levels of tolerance than the improved tolerant upland cultivar ‘IRAT104’. Diallel analysis revealed that high RRL is governed by both additive and dominance effects with a preponderance of additive effects. The trait exhibited partial dominance, and one group of genes was detected. Heritability was high, and environmenal effects were low. Findings suggest that when breeding for A1 toxicity tolerance, selection can be made in early generations. The pedigree method of breeding would be suitable. Combining ability analysis revealed the importance of both general combining ability (GCA) and specific combining ability (SCA) in the genetics of A1 toxicity tolerance in rice. GCA was more prevalent than SCA. Tolerant parens ‘Azucena’, ‘IRAT104’, and ‘Moroberekan’ were the best general combiners. The presence of reciprocal effects among crosses suggested the proper choice of parents in hybridization programs. Results indicated that ‘Azucena’, ‘IRAT 104’, and ‘Moroberekan’ should be used as the female in crosses for A1 toxicity tolerance.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00224070
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  • 25
    Electronic Resource
    Electronic Resource
    Inheritance of resistance to potato viruses Y and A in progeny obtained from potato cultivars containing gene Ry:evidence for a new gene for extreme resistance to PVA (1996)
    Springer
    Theoretical and applied genetics 93 (1996), S. 710-716 
    Details
    ISSN: 1432-2242
    Keywords: Extreme virus resistance ; Potyviruses ; Genetics ; Genes Ry and Ra ; New gene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Extreme resistance in cultivated potato (Solanum tuberosum) to potato viruses Y and A (PVY and PVA) conditioned by the presence of Ry genes introduced from Solanum stoloniferum was described by Cockerham (1970). Cockerham detailed a number of genes which controlled a variety of reactions, including extreme resistance to both viruses (i.e. little or no visible reaction of plants and no viral replication following graft and manual inoculation) controlled by gene Ry sto. In the present study, cvs ‘Pirola’ and ‘Barbara’, which contain a Ry gene, were found to have extreme resistance to PVY isolates from the ordinary (PVY°), veinal necrosis (PVYN) and potato tuber necrotic ringspot (PVYNTN) subgroups, and PVA. The inheritance of this phenotype was examined in seedling progenies obtained by crossing ‘Barbara’ and ‘Pirola’ with susceptible cultivars. Segregation data for resistance to PVY and PVA in a progeny involving cv ‘Pirola’ best fitted a genetical model of one gene controlling extreme resistance to both PVY and PVA, although the possibility that there are two genes, each controlling resistance to one virus but closely linked, cannot be excluded. Segregation data from progenies involving cv ‘Barbara’ best fitted a genetical model in which there are two independent genes, one controlling extreme resistance to PVA and PVY and a second gene controlling extreme resistance to PVA but not to PVY. This previously unrecognised gene conferring extreme resistance to PVA only, should be given the notation Ra in keeping with nomenclature used for other resistance genes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00224066
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  • 26
    Electronic Resource
    Electronic Resource
    Differential risk for developmental reading disorders in the offspring of compensated versus noncompensated parents (1996)
    Springer
    Reading and writing 8 (1996), S. 407-417 
    Details
    ISSN: 1573-0905
    Keywords: Compensation ; Dyslexia ; Environment ; Familial aggregation ; Genetics ; Risk
    Source: Springer Online Journal Archives 1860-2000
    Topics: Education
    Notes: Abstract When one or both parents have a history of developmental reading disorder (RD) in childhood, the risk to their offspring for developing reading problems is substantially increased. However, risk research has usually assumed a stability of reading problems across the lifespan (i.e., if a parent was affected in childhood, he or she remains affected in adulthood). Yet, some individuals with RD in childhood compensate for the disorder as they grow older. Both an environmental and genetic hypothesis would predict that the risk for RD in offspring will vary as a function of parental compensation. This study examined whether risk to offspring was dependent on the parents' successful or unsuccessful compensation for their childhood reading problems. Two large family data sets were analyzed (N=907). Diagnoses with either an age discrepant or IQ discrepant criteria essentially showed that having at least one still affected parent (i.e., RD both as a child and as an adult) put the offspring at a higher risk for RD than having at least one compensated parent (i.e., RD as a child but not as an adult). The lowest risk to an offspring occurred when both parents were never affected (i.e., not RD as a child or as an adult). The implications of these findings are discussed with regard to counseling and early diagnosis of reading problems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00404002
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  • 27
    Electronic Resource
    Electronic Resource
    Understanding Candida albicans at the Molecular Level (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Yeast 12 (1996), S. 1677-1702 
    Details
    ISSN: 0749-503X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: No Abstract
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 28
    Electronic Resource
    Electronic Resource
    Yeast Protein Serine/Threonine Phosphatases: Multiple Roles and Diverse Regulation (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Yeast 12 (1996), S. 1647-1675 
    Details
    ISSN: 0749-503X
    Keywords: yeast ; phosphorylation ; protein phosphatase ; PP1 ; PP2A ; PP2B ; calcineurin ; Sit4 ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: Since the isolation of the first yeast protein phosphatase genes in 1989, much progress has been made in understanding this important group of proteins. Yeast contain genes encoding all the major types of protein phosphatase found in higher eukaryotes and the ability to use powerful genetic approaches will complement the wealth of biochemical information available from other systems. This review will summarize recent progress in understanding the structure, function and regulation of the PPP family of protein serine-threonine phosphatases, concentrating on the budding yeast Saccharomyces cerevisiae.
    Additional Material: 2 Ill.
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  • 29
    Electronic Resource
    Electronic Resource
    Cyclins and the Wiring of the Yeast Cell Cycle (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Yeast 12 (1996), S. 1635-1646 
    Details
    ISSN: 0749-503X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: No Abstract
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 30
    Electronic Resource
    Electronic Resource
    Pyruvate Metabolism in Saccharomyces cerevisiae (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Yeast 12 (1996), S. 1607-1633 
    Details
    ISSN: 0749-503X
    Keywords: Yeast ; glycolysis ; TCA cycle ; sugar metabolism ; metabolic engineering ; pyruvate decarboxylase ; pyruvate carboxylase ; pyruvate dehydrogenase complex ; alcoholic fermentation ; Crabtree effect ; Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: In yeasts, pyruvate is located at a major junction of assimilatory and dissimilatory reactions as well as at the branch-point between respiratory dissimilation of sugars and alcoholic fermentation. This review deals with the enzymology, physiological function and regulation of three key reactions occurring at the pyruvate branch-point in the yeast Saccharomyces cerevisiae: (i) the direct oxidative decarboxylation of pyruvate to acetyl-CoA, catalysed by the pyruvate dehydrogenase complex, (ii) decarboxylation of pyruvate to acetaldehyde, catalysed by pyruvate decarboxylase, and (iii) the anaplerotic carboxylation of pyruvate to oxaloacetate, catalysed by pyruvate carboxylase. Special attention is devoted to physiological studies on S. cerevisiae strains in which structural genes encoding these key enzymes have been inactivated by gene disruption.
    Additional Material: 7 Ill.
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  • 31
    Electronic Resource
    Electronic Resource
    1996: A vintage year for yeast and Yeast (1996)
    New York, NY [u.a.] : Wiley-Blackwell
    Yeast 12 (1996), S. 1603-1606 
    Details
    ISSN: 0749-503X
    Keywords: Life and Medical Sciences ; Genetics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology
    Notes: No Abstract
    Additional Material: 1 Tab.
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  • 32
    Electronic Resource
    Electronic Resource
    Rate constants for the reactions of O(3P) with selected monoterpenes (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 1-8 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas-phase reactions of O(3P) atom with a series of monoterpenes have been determined at ambient temperature (ca. 302-309 K) and atmospheric pressure using a relative rate technique. Using the literature rate constants for O(3P) + isobutene, cis and trans-2-butene, 3-methyl-1-butene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene as the standards, the O(3P) rate constants derived for the terpenes (in units of 10-11 cm3 molecule-1s -1) are 2.8 ± 0.4 for α-pinene, 2.8 ± 0.5 for β-pinene, 3.1 ± 0.5 for Δ 3-carene, 3.5 ± 0.5 for 2-carene, 2.6 ± 0.5 for camphene, 7.6 ± 1.2 for d-limonene, 9.0 ± 1.6 for γ-terpinene, and 10.7 ± 1.6 for terpinolene. The relative rate constants in this work agreed with literature values to within ± 10% for the standard alkenes, and to within ± ca. 35% for the terpenes. © 1996 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.1
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  • 33
    Electronic Resource
    Electronic Resource
    Dynamics of ternary complex formation in the reaction of diaquoanthranilato-N, N-diacetatonickelate(II) with 2,2′-bipyridine and 1,10-phenanthroline (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 275-282 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dynamics of ternary complex formation in the reaction of diaquoanthranilato-N, N-diacetatonickelate(II) with 2,2′-bipyridine and 1,10-phenanthroline. $\rm Ni(ada)(H_2O)_2^{-}$ $+$ $L\rightleftharpoons Ni(ada)(L)^{-}$ $+$ $2 H_20;$ $- {{d[Ni(ada)^{-}]}\over{dt}}$ $=$ $k_f[Ni(ada)^{-}][L]+k_d\ [Ni(ada)(L)];$ $\ ada^{3-}=$anthranilate-N, N-diacetate; and L=bipy or phen.The kinetics of formation of ternary complexes by diaquoanthranilato-N, N-diacetatonickelate(II). [Ni(ada)(H2O)]- with 2,2′-bipyridine (bipy) and 1,10-phenanthroline (phen) have been studied under pseudo-first-order conditions containing excess bipy or phen by stopped-flow spectrophotometry in the pH range 7.1-7.8 at 25°C and λ = 0.1 mol dm-3. In each case, the reaction is first-order with respect to both Ni(ada)- and the entering ligand (ie., bipy, phen). The reactions are reversible. The forward rate constants are: $k^{\rm Ni(ada)}_{\rm Ni(ada)(bipy)}=0.87\times10^3{\rm dm}^3 {\rm mol}^{-1}{\rm s}^{-1}$,. $k^{\rm Ni(ada)}_{\rm Ni(ada)(phen)}=1.87\times10^3{\rm dm}^3 {\rm mol}^{-1}{\rm s}^{-1}$; and the reverse rate constants are: $k^{\rm Ni(ada)(bipy)}_{\rm Ni(ada)}=1.0{\rm s}^{-1}$ and $k^{\rm Ni(ada)(phen)}_{\rm Ni(ada)}=2.0{\rm s}^{-1}$. The corresponding stability constants of ternary complex formation are: $\log K^{\rm Ni(ada)}_{\rm Ni(ada)(bipy)}=2.94$ and $\Delta\log K_M =-4.13; \log K^{\rm Ni(ada)}_{\rm Ni(ada)(phen)}=2.97$, $\Delta\log K_M =-5.03$. The observed rate constants and huge drops in stability constants in ternary complex formation agree well with the mechanism in which dissociation of an acetate arm of the coordinated ada3- prior to chelation by the aromatic ligand occurs. The observations have been compared with the kinetics of ternary complex formation in the reaction Ni(ada)- - glycine in which the kinetics involves a singly bonded intermediate, N(ada)((SINGLE BOND)O(SINGLE BOND)N)2- in rapid equilibrium with the reactants followed by a sluggish ring closure step. The reaction with the aromatic ligands conforms to a steady-state mechanism, while for glycine it gets shifted to an equilibrium mechanism. The cause of this difference in mechanistic pathways has been explained. © 1996 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.5
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  • 34
    Electronic Resource
    Electronic Resource
    Masthead (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550281001
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  • 35
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the oxidation of L-α-amino-n-butyric acid by permanganate in acid medium (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 799-805 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetic study of the oxidation of L-α-amino-n-butyric acid by permanganate ions has been carried out in buffered acid medium at pH = 1-3, using a spectrophotometric technique. An auto-catalytic effect has been observed in all cases due to Mn2+ ions formed as a product of the reaction. A first-order reaction with respect to the amino acid and the permanganate ions in both processes, catalyzed and uncatalyzed was obtained. The influence of several factors (pH, temperature, ionic strength, and reactants concentration) on the rate constants has also been investigated. In this article we propose a reaction mechanism in accordance with the experimental results obtained. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.2
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  • 36
    Electronic Resource
    Electronic Resource
    Kinetics of esterification of acetic acid with propyl alcohol by heterogeneous catalysis (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 649-656 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic data on the esterification of acetic acid with propyl alcohol catalyzed by the ion exchange resin DOWEX MONOSPHERE 650 C have been obtained using a stirred batch reactor. It was checked if there is an influence of pore diffusion and film resistance on the reaction rate when varying reaction temperature, initial molar ratios, and amount of resin. The possible mechanisms of reaction were mathematically treated using the theories of Langmuir-Hinshelwood and Rideal-Eley. Taking the nonideal behavior of the system acetic acid, propyl alcohol, propyl acetate, and water into account, all calculations were realized with activities using the UNIQUAC-equation. By using the experimental results in a process of model discrimination the best kinetic parameter set was found out by the aid of the commercial software package SIMUSOLV. The resulting data of rate constants and the experimental determined equilibrium constants served as a basis for the calculation of the thermodynamic parameters of esterification, as reaction enthalpy, reaction entropy, and activation enthalpies. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.2
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  • 37
    Electronic Resource
    Electronic Resource
    Kinetics of vanadium (V) catalyzed oxidation of gallic acid by potassium bromate in acid medium (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 673-679 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of gallic acid with potassium bromate in the presence of vanadium(V) catalyst in aqueous acid medium has been studied under varying conditions. The active species of catalyst and oxidant in the reaction were understood to be HBrO3 and VO2+. The autocatalysis exhibited by one of the products, i.e. Br-, was attributed to complex formation between bromide and vanadium(V). A composite scheme and rate law were possible, some reaction constants involved in the mechanism have been evaluated. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.5
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  • 38
    Electronic Resource
    Electronic Resource
    Kinetic and mechanistic studies on the complexation and anation of dioxotetracyanomolybdate (IV) with 2,2′-bipyridyl in aqueous solution (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 705-711 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dioxotetracyanomolybdate(IV) has been found to form a 1 : 2 complex with 2,2′-bipyridyl. The kinetics of the reaction has been studied over the pH range 5.3-8.7 by visible spectrophotometry under pseudo conditions. The effect of the 2,2′-bipyridyl and dioxotetracyanomolybdate(IV), temperature, ionic strength, and pH on the reaction rate was determined. The reaction follows first-order kinetics with respect to dioxotetracyanomolybdate(IV) ion and fractional-order kinetics with respect to 2,2′-bipyridyl. Values for the outer-sphere complex formation constant (Kos2) and rate constants (k2) were also calculated from the kinetic data. It was found that rate of the reaction increases with the decreasing pH. The following rate equation based on the outersphere complexation equilibrium preceding the associative interchange has been derived.\documentclass{article}\pagestyle{empty}\begin{document}$$\rm {{1}\over{{\it k}_{obs}}}={{1+K_{a2}[H^+]}\over{B_1[2,2\prime-bipyridyl]}}+B_2$$ ${\rm where}$ $\rm B_1={\it k}_1K_{os1}+{\it k}_2K_{os2}[H^+]K_{a2}$ ${\rm and}$ $\rm B_2={{K_{os1}+K_{a2}K_{os2}[H^+]}\over {{\it k}_1K_{os1}+{\it k}_2K_{os2}[H^+]K_{a2}}}.$\end{document}On the basis of the observed results probable mechanism has been proposed. © 1996 John Wiley & Sons, Inc.
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    Pyrolysis of aminonitriles, cyanohydrazones, and cyanoacetamides. Part II. Elimination reactions of arylacetylhydrazone, arylcyanoacetylhydrazone, and substituted cyanoacetamides (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 749-754 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of pyrolytic reactions of arylacetylhydrazone and arylcyanoacetylhydrazone (1-4) of the general formula GCH2CONHN=CHAr (G = H,CN) have been measured. The increase in the acidity of the hydrogen atom involved in the six-centered elimination process suggested for these reactions causes a significant increase in rates and thus appears to be the limiting factor in these pyrolytic reactions. The implication of this conclusion for the pyrolytic reactions of substituted cyanoacetamides (5-8), NCCH2CONHAr are considered. The mechanism of pyrolytic reactions of compounds (5-8) appears to proceed through a 4-membered cyclic transition state. © 1996 John Wiley & Sons, Inc.
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    Electronic Resource
    Impact of SO2 and NO on CO oxidation under post-flame conditions (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 773-790 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental and theoretical study on the effect of SO2 on moist CO oxidation with and without NO present has been carried out. The experiments were performed in an isothermal quartz flow reactor at atmospheric pressure in the temperature range 800-1300 K. Inlet concentrations of SO2 ranged from 0 to 1800 ppmv, while the NO ranged between 0, 100, or 1500 ppm.SO2 inhibits CO oxidation under the conditions investigated, shifting the fast oxidation regime 20-40 K towards higher temperatures at 1500 ppm SO2. The inhibition is most pronounced at high O atom levels. The experimental data supported by model analysis suggest that SO2 primarily reacts with O atoms forming SO3, which is subsequently consumed mainly by reaction with O and HO2. Addition of NO significantly diminishes the effect of SO2. Since NO is usually present in combustion flue gases, the impact of SO2 on CO burnout in most practical systems is projected to be small.The H/S/O thermochemistry and reaction subset has been revised based on recent experimental and theoretical results, and a chemical kinetic model has been established. The model provides a reasonable overall description of the effect of SO2 and NO on moist CO oxidation, while the SO3/SO2 ratio is well predicted over the range of conditions investigated. In order to enhance model performance further, rate constants for a number of SO2 and SO3 reactions need to be determined with higher accuracy. © 1996 John Wiley & Sons, Inc.
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    Kinetics and mechanism of the Cl + CO reaction in air (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 763-771 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-path FTIR spectroscopy was used to study the kinetics and mechanism of the reaction of Cl atoms with CO in air. The relative rate constants at 298 K and 760 torr for the forward direction of the reaction of Cl with 13CO and the reaction of Cl13CO with O2 were k1 = (3.4 ± 0.8) × 10-14 cm3 molecule-1 s-1 and k2 = (4.3 ± 3.2) × 10-13 cm3 molecule-1 s-1, respectively (all uncertainty limits are 2σ). The rate constant for the net loss of 13CO due to reaction with Cl in 1 atm of air at 298 K was kCl+COobs = (3.0 ± 0.6) × 10-14 cm3 molecule-1 s-1. The only observed carbon-containing product of the Cl + 12CO reaction was 12CO2, with a yield of 109 ± 18%. Our results are in good agreement with extrapolations from previous studies. The reaction mechanism and the implications for laboratory studies and tropospheric chemistry are discussed. © 1996 John Wiley & Sons, Inc.
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    Electronic Resource
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    Vilsmeier-Haack formylation of coumarin derivatives. A solvent dependent kinetic study (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 865-872 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of the reaction of coumarin derivatives with Vilsmeier-Haack (VH) reagent (1:1 DMF-POCl3) in various solvent media revealed second-order kinetics with a first-order in [Substrate] and first-order in [VH reagent]. The reaction rates altered nonlinearly with an increase in the dielectric constant of the medium and the data did not fit completely well with either Amis or Kirkwood's theories of ion (SINGLEBOND) dipole and dipole (SINGLEBOND) dipole type reactions. On the basis of kinetic and spectroscopic results, participation of VH-adduct and coumarin molecule in the rate limiting step, has been proposed. Kinetic and activation parameters have been evaluated and discussed in terms of isokinetic relationship and as a function of solvent compositions. Linearity of Leffler's and Exner's plots indicate a similar type of mechanism to be operative in different dielectric media at all temperatures. © 1996 John Wiley & Sons, Inc.
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    Electronic Resource
    Template mechanism and kinetics for the complexation of ninhydrin with copper (II) complexes of asparagine and serine (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 893-897 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ninhydrin has been found to form a 1:1 complex with Cu(II) complexes of asparagine and serine. The kinetics of the complexation reaction has been studied spectrophotometrically in acetate buffer. The effect of the [ninhydrin], pH, and temperature on the reaction rate of the reaction was studied. The reaction follows fractional-order kinetics with respect to ninhydrin and first-order with respect to asparagine-Cu(II) and serine-Cu(II), respectively. The reaction proceeds through the coordination of ninhydrin with the same Cu(II) of asparagine and serine complexes. The results are best accounted by the “Template mechanism” for the inner sphere complexation. The values for the inner sphere complex formation constant were also calculated from the kinetic data. The role of Cu(II) in this reaction is to inhibit the breaking of C(SINGLEBOND)C (evolution of CO2) as well as stabilize the C(DOUBLEBOND)N of Schiff base. On the basis of observed results, probable mechanism has been proposed. © 1996 John Wiley & Sons, Inc.
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    Electronic Resource
    The dependence of quinine fluorescence quenching on ionic strength (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 919-923 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Stern-Volmer constant for the quenching of quinine fluorescence by chloride ions has been found to be markedly dependent on acid concentration. Steady-state and time-resolved fluorescence measurements under different acid and salt concentrations have further shown that the decrease in quenching arises from the influence of increasing ionic strength on the diffusion-controlled rate constant for the bimolecular quenching process. Two possible mechanisms for this dependence are discussed: a decrease in the intrinsic rate constant for the reaction due to the kinetic salt effect, and a decrease in the effective encounter distance due to screening of the charges on the reactants. © 1996 John Wiley & Sons, Inc.
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    Electronic Resource
    Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. II. Reactions of •CF3 +CF3CH2CH2• and CF3CH2CH2• + CF3CH2CH2• (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 61-68 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation/combination rate constant ratios, kd /kc, have been measured for the collision between CF3CH2CH2 and CF3 radicals to be 0.022 ± 0.002 and for CF3CH2CH2 and CF3CH2CH2 radicals to be 0.100 ± 0.002. Comparison to previous work from this laboratory for the reaction of CF3CH2CHCl with CF3 radicals shows that substitution of Cl for H increases the kd /kc by about 50%; however, for the auto disproportionation-combination of CF3CH2CH2 radicals the chlorine substituent decreases the observed rate constant ratio by a factor of two. The chlorine substituent effect on the observed kd /kc ratios is compared to predictions from molecular orbital calculations. © 1996 John Wiley & Sons, Inc.
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    Shock tube study of OH reactions with linear hydrocarbons near 1100 K (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 79-87 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of the hydroxyl radical with several linear hydrocarbon species occurring in combustion chemistry have been considered at temperatures near 1100 K and 1 atmosphere in shock tube experiments. The OH density was monitored using 310 nm UV absorption of the A2Σ+ (SINGLEBOND) X 2Π transition. Rate coefficients for the reaction of OH with ethane (8.37 × 10-12 cm3 molecule-1 s- 1; 970 K), hexane (2.18 × 10-11; 962 K), heptane (3.34 × 10-11, 1186 K), octane (4.42 × 10-11; 1078 K), nonane (4.55 × 10-11; 1097 K), and decane (5.64 × 10-11; 1109 K) have been determined. These values are compared with previous experimental results and transition state theory calculations. © 1996 John Wiley & Sons, Inc.
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    Substituent effects on the disproportionation-combination rate constant ratios for gas-phase halocarbon radicals. Part III: Reactions of CF3 + CF3CH2 CHCF3 and CF3 CH2CHCF3 + CF3CH2 CHCF3 (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 109-114 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation/combination rate constant ratios, kd/kc, for the reactive collision between CF3CH2CHX + CF3 radicals and between CF3CH2CHX + CF3CH2CHX radicals have been measured for X = CF3. The kd/kc = 0.066 ± 0.013 when H is transferred to the CF3 radical and 0.125 ± 0.025 for H transfer to the CF3CH2CHCF3 radical. Comparison of these results with previous work shows that X = CF3 increases the kc/kc' s relative to X = Cl or H. The effect of the CF3 substituent on the disproportionation rate is discussed. © 1996 John Wiley & Sons, Inc.
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    The mechanism of ethylene pyrolysis at small conversions (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 181-193 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic modelling is used in conjunction with measurements of product yields to develop a mechanism for the pyrolysis of ethylene at 896K and ethylene pressures ranging from approximately 3 to 78 kPa. An induction period was observed for all products except H2, and was followed by a steady rate, which was of second-order for all products except 1,3-C4H6, the most abundant product. The mechanism quantitatively accounts for the yields of H2, CH4, C2H6, C3H6, 1-C4H8 and 1,3-C4H6. The reaction is initiated by disproportionation of C2H4 and the product 1,3-C4H6 results from decomposition of the C4H7 radical, formed by addition of C2H3 to C2H4. The other organic products that were measured are formed as a result of reactions involving the C2H5 radical. The hydrogen is produced by abstraction from C2H4 by atomic hydrogen and its rate is controlled by the reaction C2H5 → C2H4 + H which is nearly equilibrated. The main termination reaction is recombination of C2H5. The auto-acceleration which is evident particularly in the yields of H2, CH4, C2 H6, and C3H6 is accounted for by the decomposition of 1-C4H8. © 1996 John Wiley & Sons Inc.
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    Electronic Resource
    Masthead (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550280301
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    Acceleration effect of electroless nickel deposition by thiourea (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 259-264 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It was found that the presence of thiourea can increase the electroless nickel (EN) deposition rate and hydrogen evolution simultaneously. Influences of thiourea on the electrochemical behaviors of EN solution and activation energy of EN reaction were studied. The composition of the deposit was also determined by means of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). The results show that thiourea accelerates the nickel deposition due to interference in the anodic process of EN plating. © 1996 John Wiley & Sons, Inc.
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    Reaction kinetics of lactic acid with methanol catalyzed by acid resins (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 37-41 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The esterification of aqueous lactic acid solution with methanol and its reverse reaction catalyzed by acidic cation exchange resins in the H+ form were carried out in a batch system. The inhibiting effects of water and methanol on the resins were evaluated. The experimental data were correlated by a kinetic model that the inhibition by methanol and water was included. The reaction rate constants and the adsorption coefficients were determined from the experiments. The activity of acidic resin was compared with that of sulfuric acid as catalyst. © 1996 John Wiley & Sons, Inc.
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    The use of free energy relationships to rationalize kinetic data in complex solvent mixtures (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 57-60 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron transfer reaction [(NH3)4COIII(μ-pzCO2)FeII(CN)5]- → [(NH3)4COII(μ-pzCO2)FeIII(CN)5]- has been studied in water-cosolvent mixtures at ionic strength of I = 0.5 mol dm-3 (NaClO4). A multiparameter regression coefficients have been compared to those obtained for the same reaction to a different ionic strength (I = 2.8 10-3 mol dm-3). The magnitude of these coefficients changes with the ionic strength. An explanation is given for this behavior. © 1996 John Wiley & Sons, Inc.
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    Erratum (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 69-70 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    A unified approach to kinetic processing of nonisothermal data (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 95-101 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Basic problems of kinetic processing of nonisothermal data ascertained from thermal analysis measurements can be solved by isoconversional methods. Analysis of the dependence of the activation energy on conversion often permits the identification of the kinetic scheme for the process. This dependence may also be used to solve applied kinetic problems related to predicting the behavior of a substance outside the range of experimental temperatures. Methods for using this dependence for evaluating both the preexponential factor and the reaction model, as well as for detecting isokinetic relationships, have been discussed. Because all of these operations have a common origin in computing the dependence of the activation energy on conversion, isoconversional methods may be considered as a basis of a unified approach to kinetic processing of nonisothermal data. © 1996 John Wiley & Sons, Inc.
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    Kinetics of the complexation of Al3+ with aminoacids, IDA and NTA (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 125-136 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the complexation of Al3+ with aminoacids, IDA and NTA are investigated by the stopped flow method with conductivity detection in the range of pH 〈 4. Reaction amplitudes and pseudo-first-order rate constants are evaluated yielding equilibrium and rate constants. It is shown that Al3+ forms only complexes with the negatively charged species and that the kinetics of all investigated ligands can be explained with the same reaction scheme. For aspartic acid, IDA and NTA a stepwise complexation is observed where monodentate complexes are formed by a fast reaction (2s -1 〈 k 〈 20s1) which is base catalyzed. The rate determining step is the solvent exchange at Al3+ according to the Eigen-Wilkins mechanism. However, the ligand influences this exchange rate and a linear free energy relation is found between log k and pKa, which also describes the kinetics of other ligands. This fast reaction is followed by the much slower formation of chelates (for NTA:k = 0.27 s -1) which is controlled by the deprotonation of the nitrogen atom. The overall association constant of the Al-NTA complex is determined as log (Kass/dm3mol-1) = 13.0 ± 0.3. © 1996 John Wiley & Sons, Inc.
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    A kinetic study of electron transfer from L-Ascorbic acid to sodium perborate and potassium peroxy disulphate in aqueous acid and micellar media (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 153-164 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of oxidation of L-ascorbic acid (H2A) by sodium perborate (SPB) and peroxy disulphate (PDS) have been investigated in aqueous acid and micellar media. Reaction kinetics indicated first-order dependence on both |oxidant| and |H2A|. Increase in ionic strength (μ) increased reaction rate only in H2SO4 media. Rate of SPB oxidation of H2A has been accelerated by acidity in HNO3 and HCl media while a decreasing trend is observed in HClO4 and H2SO4 media. The results are interpreted by various theories of acidity functions. Reaction rate is enhanced by the addition of added |H2O2| indicating a H2O2 coordinated boron species to be active in the present system. In the absence of micelle, increase in |acid| altered the PDS(SINGLEBOND)H2A reaction rate marginally (a very small positive effect with HClO4 and negative effect with H2SO4). Most plausible mechanisms have been proposed on the basis of experimental results. Activation parameters evaluated for specific kinetic constants are in accord with outer sphere electron transfer mechanism. In SPB(SINGLEBOND)H2A system, addition of anionic micelle (Sodium lauryl sulfate) increased the rate, stabilizing the cationic species in the transition state in all the acid media. Although rate of PDS oxidation of H2A was catalyzed by TX and inhibited by SDS at critical micellar concentration (CMC) increase in |acid| (both HClO4 and H2SO4) beyond 9.6 × 10-4 M decreased the rate of oxidation. This trend was explained due to the repulsive interaction of coanion, HA-, and negatively charged micellar species. © 1996 John Wiley & Sons, Inc.
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    An exploratory investigation of the use of alkali metals in nitrous oxide control (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 217-234 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using chemical kinetic modeling, we have investigated the feasibility of using sodium hydroxide (a representative alkali-metal compound) to control nitrous oxide emissions from combustion sources. The key reaction is \documentclass{article}\pagestyle{empty}\begin{document}$${\rm N}_a {\rm + N}_{2} {\rm O } \leftrightarrow {\rm NaO + N}_{2}$$\end{document} where the sodium atom is produced by the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm NaOH + H } \leftrightarrow {\rm Na + H}_{2} {\rm O}$$\end{document} when small amounts of fuel are added to lean combustion products. Because sodium hydroxide is regenerated by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm NaO + H}_{2} {\rm O } \leftrightarrow {\rm NaOH + OH} $$\end{document} one sodium atom is potentially capable of destroying several N2O molecules. The mechanism is discussed in detail. Moreover, we have studied the possibility of using NaOH in conjunction with RAPRENOX (cyanuric acid injection) to control NO x emissions without producing N2O as a by-product. The results are discussed at length. © 1996 John Wiley & Sons, Inc.
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    A shock tube study of reactions of CN with HCN, OH, and H2 using CN and OH laser absorption (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 245-258 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantitative, narrow-line laser absorption measurements of CN time-histories at 388.444 nm were acquired in high-temperature pyrolysis and laser photolysis shock tube experiments. The data were analyzed using a detailed kinetics mechanism to determine the rate coefficients of the reactions $$\rm CN + OH\ \longrightarrow Products \eqno{(1)}$$ $$\rm CN + HCN \longrightarrow C_2N_2+H \eqno{(2)}$$ $$\rm CN + H_2\ \longrightarrow HCN+H \eqno{(3)}$$for temperatures between 940 and 1860 K. Two independent experimental approaches were utilized: laser photolysis (at 193 nm) of dilute C2N2/HCN/argon and C2N2/H2/argon mixtures in reflected shock wave experiments, and shock heating of HNO3/HCN/argon mixtures in incident and reflected shock wave experiments. Laser absorption measurements of OH at 306.687 nm were also taken in the HNO3/HCN/argon experiments The results are in good agreement with rate coefficient determinations from previous studies at different temperatures. The expression $$k_2=1.51\times 10^{7}\times T^{1.71}\exp(-770/T){\rm cm}^3\ {\rm mol}^{-1}\ s^{-1}\ \ \ (f=0.85, F=1.15),$$derived by Yang et al (1992) from their k2 measurements in combination with those of Szekely et al (1983), is recommended for the broad temperature range 300-3000 K. The uncertainty factors f and F give the limiting values of the rate coefficient kmin = f kbest fit, kmax = Fkbest fit. The recommended expression for the rate coefficient of reaction (3) $$k_3=2.95\times 10^{5}\times T^{2.45}\exp(-1126/T){\rm cm}^3\ {\rm mol}^{-1}\ s^{-1}\ \ \ (f=0.83, F=1.22),$$also valid for temperatures 300-3000 K, is taken from the transition state theory analysis of the CN + H2 reaction by Wagner and Bair (1986). The rate coefficient for reaction (1) was measured to be 4.0 × 1013cm3mol-1 s-1(f = 0.61, F = 1.40) for the temperature range 1250-1860 K. © 1996 John Wiley & Sons, Inc.
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    Rate constants for reactions of OH radicals with a series of asymmetrical ethers and tert-Butyl alcohol (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 291-297 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reactions of OH radicals with butyl ethyl ether (k1), methyl tert-butyl ether (k2), ethyl tert-butyl ether (k3) tert-amyl methyl ether (k4) and tert-butyl alcohol (k5) have been measured over the temperature range 230-372 K using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique. The temperature dependence of k1 - k5 when expressed in Arrhenius form gave: k1 = (6.59 ± 0.66) × 10 -12 exp|(362 ± 60)/T|, k2 = (5.03 ± 0.27) × 10-12 exp|&minus(133 ± 30)/T|, k3 = (4.40 ± 0.24) × 10-12 exp|(210 ± 37)/T|,k4 = (4.7 ± 0.7) × 10-12 exp|(82 ± 85)/T|, and k5 = (2.66 ± 0.48) × 10-12 exp| -(270 ± 130)/T|. However, the Arrhenius plots for k1-k5, were slightly curved and are best fitted by the three parameter fits which are given in the article. The room temperature values of k1, k2, k3, k4, and k5 are (2.08 ± 0.23) × 10-11, (3.13 ± 0.36) × 10-12, (8.80 ± 0.50) × 10-12, (6.28 ± 0.45) × 10-12, and (1.08 ± 0.10) × 10-12, respectively, in cm3 molecule-1 s-1. © 1996 John Wiley & Sons, Inc.
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    Oxidation of toluene in NOχ free air: Product distribution and mechanism (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 315-332 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Product distributions resulting from the oxidation of toluene in air initiated by chlorine atoms, by toluene photolysis, and by hydroxyl radicals were studied at atmospheric pressure in the absence of nitrogen oxides. In the first case only benzaldehyde and benzylalcohol with a ratio of 7.8 ± 1.7 were observed, from which a branching ratio α = 0.76 ± 0.05 was derived for the radical propagating pathway of the self-reaction of benzylperoxy radicals. In the second and third case the apparent branching ratio decreased to α = 0.56 ± 0.07 and 0.37 ± 0.08, respectively, indicating the occurrence of additional reactions between benzylperoxy and other peroxy radicals. The major ring retaining products resulting from the reaction of OH with toluene were o-cresol, p-cresol. and methyl-p-benzo-quinone (57.9 ± 12.5% reacted carbon, corrected for secondary losses), in addition to 7.7 ± 1.6% benzaldehyde and benzylalcohol arising from methyl hydrogen abstraction. Formaldehyde, acetaldehyde, glyoxal, methylglyoxal, carbon monoxide, and carbon dioxide were observed as ring cleavage products (25.0 ± 7.2%). Except for CO2, which appears to be an important ring cleavage product only under NOχ-free conditions, the distribution of ring cleavage products was similar to that found by Gery et al (1985) in the presence of NOχ. Comparison of experimental data and results from computer simulations show that self-reactions of the hydroxy-methyl-cyclo-hexadienylperoxy radicals are negligible compared to internal rearrangement reactions leading to ring stabilization or ring cleavage. The mechanism of CO2 production appears to require the formation of a Criegee intermediate. © 1996 John Wiley & Sons, Inc.
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    Masthead (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550280801
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    Kinetics and mechanism of hydrogen peroxide oxidation of chromone-3-carboxaldehydes in aqueous acid and micellar media (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 637-648 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidation of chromone-3-carboxaldehyde (CCA) and substituted analogues by H2O2 has been carried out in aqueous acid (HCl and H2SO4) and micellar media. Reaction kinetics indicated order in [CCA] as well as [H2O2] to be unity while it is a fraction (1 〉 n 〉 O) in [acid]. Reaction rates were found to be faster in the solvents of low-dielectric constant (D). Added salt (KCl or (NH4)2SO4) increased the rate of oxidation marginally. On the basis of observed linearity of Amis plot and marginal positive salt effect, protonated CCA (enol form of CCA, a cation) and H2O2 (neutral molecule) were considered as reactive species in the rate limiting step. Reaction rates were found to be enhanced significantly in anionic and nonionic micellar (sodium dodecylsulfate (SDS) and Triton X-100 (Tx), respectively) media. However, cationic micelles [cetyl trimethyl ammonium bromide (CTAB)] indicated marginal retardation effect. Effect of anionic and cationic micelles has been interpreted in terms of electrostatic interactions, while that of nonionic micelles in terms of hydrophobic interactions. Structure-reactivity correlations have been interpreted by Hammett's equation. Negative “ρ” (reaction constant) values indicated cationic transition state. © 1996 John Wiley & Sons, Inc.
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    Theoretical study of reactions of N2O with NO and OH radicals (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 693-703 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of N2O with NO and OH radicals have been studied using ab initio molecular orbital theory. The energetics and molecular parameters, calculated by the modified Gaussian-2 method (G2M), have been used to compute the reaction rate constants on the basis of the TST and RRKM theories. The reaction N2O + NO → N2 + NO2 (1) was found to proceed by direct oxygen abstraction and to have a barrier of 47 kcal/mol. The theoretical rate constant, k1 = 8.74 × 10-19 × T2.23 exp (-23,292/T) cm3 molecule-1 s-1, is in close agreement with earlier estimates. The reaction of N2O with OH at low temperatures and atmospheric pressure is slow and dominated by association, resulting in the HONNO intermediate. The calculated rate constant for 300 K ≤ T ≤ 500 K is lower by a few orders than the upper limits previously reported in the literature. At temperatures higher than 1000 K, the N2O + OH reaction is dominated by the N2 + O2H channel, while the HNO + NO channel is slower by 2-3 orders of magnitude. The calculated rate constants at the temperature range of 1000-5000 K for N2O + OH → N2 + O2H (2A) and N2O + OH → HNO + NO (2B) are fitted by the following expressions: $$k_{2A}=2.15\times 10^{-26}\times T^{4.72}\exp(-18,400/T),$$ $$k_{2B}=1.96\times 10^{-28}\times T^{4.33}\exp(-12,623/T),$$ in units of cm3 molecule -1s-1. Both N2O + NO and N2O + OH reactions are confirmed to enhance, albeit inefficiently, the N2O decomposition by reducing its activation energy. © 1996 John Wiley & Sons, Inc.
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    Pyrolysis of aminonitriles, cyanohydrazones, and cyanoacetamides. Part I. Elimination reaction of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles and substituted benzaldehyde cyanoacetylhydrazones (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 741-748 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of the Schiff bases of 1-arylmethyleneamino-1,2-dihydro-4,6-dimethyl-2-oxopyridine-3-carbonitriles (1-5) has been studied. These compounds eliminate via a six-membered transition state to produce substituted benzonitriles and 2-hydroxy-4,6-dimethylpyridine-3-carbonitrile. These eliminations are unimolecular first-order reactions. The kinetic data gave a good correlation with σ0 values of the substituents on the aryl group with ρ = 0.83 at 520 K. Utilization of the pyrolytic reaction in synthesis of various benzonitriles is considered, and mechanistic information has been obtained by comparing the kinetic data and product analysis of the Schiff bases with their open-chain substituted benzaldehyde cyanoacetylhydrazones (6-9) analogues. © 1996 John Wiley & Sons, Inc.
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    Pulsed laser powered homogenous pyrolysis for reaction kinetics studies: Probe laser measurement of reaction time and temperature (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 817-828 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pulsed laser powered homogeneous pyrolysis (LPHP) is a technique which can be used to measure rate parameters for purely homogeneous unimolecular decomposition reactions at high temperatures (600-1500 K). The reaction temperature in pulsed LPHP may be obtained from the speed of sound in the reacting gas, which may be measured by observing the thermal lens effect of the gas on a probe laser beam. The reaction time may be obtained directly from the thermal lens measurements. In this work experiments were performed using ethyl acetate (EtAc) and isopropyl chloride (2-ClPr), two reactants whose unimolecular decomposition rate parameters are well established. This allowed us to assess the accuracy and precision attainable with this technique. Pulsed LPHP proved capable of providing rate parameters in good agreement with those in the literature. The results for which the measured activation energies were closest to the literature values gave the temperature dependence of the rate constants as log(kEtAc) = (12.0 ± 0.9) - 47.7 ± 4.4(kcal/mol)/2.303RT and log(k2-ClPr) = (13.3 ± 1.0) - 50.8 ± 4.8(kcal/mol)/2.303RT. These may be compared with the literature recommendations, log(kEtAc) = 12.6 - 48.0(kcal/mol)/2.303RT and log(k2-ClPr) = 13.6 - 51.1(kcal/mol)/2.303RT. In all cases the measured rate parameters agreed with the recommended values to within the error limits of the measured values. Potential sources of error in the temperature measurement and the kinetic parameters are explored. The expected accuracy of the experiments is assessed, and possible improvements in the experiment are suggested. © 1996 John Wiley & Sons, Inc.
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    Homogeneous reaction of carbon disulfide and o-phenylene diamine catalyzed by tertiary amines (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 885-892 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of 2-mercaptobenzimidazole (MBI) was carried out by reacting o-phenylene diamine and carbon disulfide catalyzed by tertiary amine (R3N) in a homogeneous solution. Dichloromethane, chlorobenzene, chloroform, toluene, and benzene were employed as the organic solvent. The advantage of using such organic solvents is that MBI precipitates from the organic solution. Only mechanical separation processes, such as filtration and centrifugation, can be used to obtain the MBI product of high purity. Based on the reaction mechanism, a kinetic model, which included two steps of reactions in the organic phase, was proposed, i.e.: (i) a chemical equilibrium of the reaction of CS2 and R3N to produce an active intermediate (R3N(SINGLEBOND)CS2) was built up within a short period of time and (ii) this active intermediate further reacted with o-phenylene diamine to produce the desired MBI product. A combination of the zeroth order and pseudo-first-order rates law was used to describe the kinetic data. However, the reaction follows pseudo-first-order rate law at higher temperature, and the reaction follows zeroth-order rate law at lower temperature. The effects of the operating conditions on the conversion of o-phenylene diamine were also investigated. © 1996 John Wiley & Sons, Inc.
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    Rate constants for the gas-phase reaction of ozone with 1, 1-disubstituted alkenes (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 911-918 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of ozone with eight alkenes including six 1,1-disubstituted alkenes has been investigated at ambient T (285-298 K) and p = 1 atm. of air. The reaction rate constants are, in units of 10-18 cm3 molecule-1 s-1, 9.50 ± 1.23 for 3-methyl-1-butane, 13.1. ± 1.8 for 2-methyl-1-pentene, 11.3 ± 3.2 for 2-methyl-1,3-butadiene (isoprene), 7.75 ± 1.08 for 2,3,3-trimethyl-1-butene, 3.02 ± 0.52 for 3-methyl-2-isopropyl-1-butene, 3.98 ± 0.43 for 3,4-diethyl-2-hexene, 1.39 ± 17 for 2,4,4-trimethyl-2-pentene, and 〉370 for (cis + trans)-3,4-dimethyl-3-hexene. For isoprene, results from this study and earlier literature data are consistent with: k (cm3 molecule-1 s-1) = 5.59 (+ 3.51, &minus 2.16) × 10-15 e(-3606±279/RT), n = 28, and R = 0.930. The reactivity of the other alkenes, six of which have not been studied before, is discussed in terms of alkyl substituent inductive and steric effects. For alkenes (except 1,1-disubstituted alkenes) that bear H, CH3, and C2H5 substituents, reactivity towards ozone is related to the alkene ionization potential: In k〈(10-18 cm3 molecule-1 s-1) = (32.89 ± 1.84) - (3.09 ± 0.20) IP (eV), n = 12, and R = 0.979. This relationship overpredicts the reactivity of C≥3 1-alkenes, of 1,1-disubstituted alkenes, and of alkenes with bulky substituents, for which reactivity towards ozone is lower due to substituent steric effects. The atmospheric persistence of the alkenes studied is briefly discussed. © 1996 John Wiley & Sons, Inc.
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    Product formation from the reaction of the NO3 radical with isoprene and rate constants for the reactions of methacrolein and methyl vinyl ketone with the NO3 radical (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 925-934 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate method, rate constants for the gas-phase reactions of the NO3 radical with methacrolein and methyl vinyl ketone were determined to be (4.4 ± 1.7) × 10-15 cm3 molecule-1 s-1 and 〈6 × 10-16 cm3 molecule-1 s-1, respectively, at 296 ± 2 K. The molar formation yields of methacrolein and methyl vinyl ketone from the gas-phase reaction of the NO3 radical with isoprene at 296 ± 2 K and atmospheric pressure of air were measured to be 0.035 ± 0.014 each. The tropospheric implications of these kinetic and product data are discussed, and it is concluded that the nighttime NO3 radical reactions with methacrolein and methyl vinyl ketone are not important. However, during nighttime the formation of methacrolein and methyl vinyl ketone from the reaction of isoprene with the NO3 radical may dominate over their formation from the O3 reaction with isoprene. Atmospheric pressure ionization tandem mass spectrometry (API-MS/MS) was used to investigate the products of the reactions of the NO3 radical with isoprene and isoprene-d8, and C5-nitrooxycarbonyl(s) (e.g., O2NOCH2C(CH3) (DOUBLEBOND) CHCHO), C5-hydroxynitrate(s) (e.g., O2NOCH2C(CH3)(DOUBLEBOND) CHCH2OH), C5-nitrooxyhydroperoxide(s) (e.g., O2NOCH2C(CH3)(DOUBLEBOND) CHCH2OOH), and C5-hydroxycarbonyl(s) (e.g., HOCH2CH(DOUBLEBOND) C(CH3)CHO) and their deuterated analogs were observed from these reactions. © 1996 John Wiley & Sons, Inc.
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    Oxidation of tris(1, 10-phenanthroline)iron(II) ion by iodate and periodate ions in neutral medium (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 103-108 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of iodate and periodate with Fe(phen)32+ have been studied in neutral medium iodate ion is unreactive with ferroin in aqueous solution. The reaction is autocatalytic in the case of IO4-. The autocatalysis disappears in an excess of IO3-. The rate constants of both processes were determined and a reaction mechanism has been proposed. © 1996 John Wiley & Sons, Inc.
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    Kinetics of the reaction CH + N2 rarr; [M]⇒[M] products in the range 10-620 torr and 298-1059 K (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 115-123 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of CH(X2 Π) radicals with molecular nitrogen was studied in the temperature range 298-1059 K at total pressures between 10 and 620 torr. CH radicals were generated by excimer laser photolysis of CHCIBr2 at 248 nm and were detected by laser-induced fluorescence. The investigated reaction shows a strong temperature and pressure dependence. At pressures of 20, 100, and 620 torr the Arrhenius plots exhibit a strong decrease of the rate constant with increasing temperature. The rate constant is well described by, with E0 in kJ/mol. The pressure dependence was studied at temperatures of 298, 410, 561, and 750 K. The rate constants for each temperature were fitted by the Troe formalism. From the calculated values of k0 and kinfinity, the Arrhenius expressions, were obtained with E0 (k0) and EA (kinfinity) in units of kJ/mol. Within the range of 298-750 K the temperature dependence of the broadening factor is well described by Fc = 0.029 + (173.3/T). © 1996 John Wiley & Sons, Inc.
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    Shock tube and modeling study of 1,3-butadiene pyrolysis (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 137-151 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Butadiene (1,3-C4H6) was heated behind reflected shock waves over the temperature range of 1200-1700 K and the total density range of 1.3 × 10-5 -2.9 × 10-5 mol/cm3. Reaction products were analyzed by gas-chromatography. The concentration change of 1,3-butadiene was followed by UV kinetic absorption spectroscopy at 230 nm and by quadrupole mass spectrometry. The major products were C2H2, C2H4, C4H4, and CH4. The yield of CH4 for a 0.5% 1,3-C4H6 in Ar mixture was more than 10% of the initial 1.3-C4H6 concentration above 1500 K. In order to interpret the formation of CH4 successfully, it was necessary to include the isomerization of 1,3-C4H6 to 1,2-butadiene (1,2-C4H6) and to include subsequent decomposition of the 1,2-C4H6 to C3H3 and CH3. The present data and other shock tube data reported over a wide pressure range were qualitatively modeled with a 89 reaction mechanism, which included the isomerizations of 1,3-C4H6 to 1,2-C4H6 and 2-butyne (2-C4H6). © 1996 John Wiley & Sons, Inc.
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    Kinetics and mechanism of the thermal decomposition reaction of dihydro-3,6-diphenyl-5-benzyl-1,2,4,5-trioxazine (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 21-25 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition reactions of dihydro-3,6-diphenyl-5-benzyl-1,2,4,5-trioxazine (DHT) in the initial concentrations and temperature ranges of 0.004-0.013 M and 353-393 K, respectively, have been investigated in benzene, toluene, and methanol solutions. In these solvents the reaction follows a first-order kinetic law up to ca. 50% DHT conversions. However, at the higher temperatures and higher initial concentrations, an induced decomposition reaction of the DHT molecule is observed, which is suppresed by the addition of a free radical scavenger. The pseudo-first-order rate constant values for the reactions of the trioxazine in acetic acid solution (0.004 M) in the temperature range of 313-323 K, lead to activation parameters significantly different from those of the unimolecular thermolysis in other media. This supports a marked effect of the solvent on that reaction. The kinetics and the nature of the products observed in the DHT thermolysis favors a general stepwise mechanism of decomposition which resembles the type of reaction already postulated for other cyclic peroxides in solution. © 1996 John Wiley & Sons, Inc.
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    The nitrosation of N-alkylureas: Evidence for a proton transfer mechanism (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 307-313 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the nitrosation of methyl, ethyl, propyl, butyl, and allyl urea were studied by conventional and stopped-flow spectrophotometry in the presence or absence of acetate or mono-, di-, or trichloroacetate anions. In the presence of a large excess of urea, the observed rate equation was $$v={{\rm [urea][nitrite][H^{+}]^2}\over{\rm K_a + [H^{+}]}} \left(\vartheta+\xi{{\rm K_R[carboxylic\ acid]}\over{\rm K_R+[H^{+}]}}\right)$$where Ka is the acidity constant of nitrous acid and KR that of the carboxylic acid. The ureas exhibited the reactivity order methylurea ≫ (ethylurea ≅ propylurea ≅ butylurea) ≫ allylurea. Experiments in D2O afforded values of kH2O/kD2O in general agreement with the values 4.1-5.5 predicted by a semiclassical transition state theory of kinetic isotope effects [i.e., kH2O/kD2O = exp(0.130hv⊼/kT)], where v⊼ is the frequency of R3N—H stretching (2700-2250 cm-1) in the protonated urea. This result, the observed catalysis by carboxylate ions and the value of the Bronsted parameter β(0.45) show the rate-controlling step of these reactions to be the transfer of a proton from the protonated N-alkyl-N-nitrosourea to the solvent or to the organic anion, if present. The observed order of substrate reactivities is explicable in terms of the capacity of the protonated N-alkyl-N-nitrosourea for forming a hydrogen bond with the water molecule to which the proton will be transferred, and the degree to which the formation of such bonds is hindered by the hydrophobic alkyl chain of the nitrosourea. © 1996 John Wiley & Sons, Inc.
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    Gas-phase thermolysis of t-butylsulfenamides: N, N-dimethyl t-butylsulfenamide, 2,6-dimethylpiperidinyl t-butylsulfenamide, and N-t-butyl t-butylsulfenamide (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 353-359 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amide derivatives of t-butylsulfenic acid mentioned in the title have been thermolyzed in a stirred-flow reactor at temperatures of 273-390°C and pressures of 7-15 torr, using toluene as carrier gas, at residence times of 0.4-2 s. Isobutene formed in 95-99% yields, through order one reactions, following the Arrhenius equations: N, N-dimethyl t-butylsulfenamide: $$k(s^{-1})=10^{14.45\pm 0.46}\exp(-175\pm 5 {\rm kJ/mol}\,{\bf RT})$$ 2,6-dimethylpiperidyl t-butylsulfenamide: $$k(s^{-1})=10^{14.38\pm 0.26}\exp(-161\pm 3 {\rm kJ/mol}\,{\bf RT})$$ N-t-butyl t-butylsulfenamide: $$k(s^{-1})=10^{14.75\pm 0.37}\exp(-184\pm 7 {\rm kJ/mol}\,{\bf RT})$$These thermolyses are considered to take place through unimolecular, four-center cyclic transition-state reaction mechanisms, giving rise to isobutene plus the corresponding S-unsubstituted thiohydroxylamines. The latter decompose outside the reactor at temperatures above -78°C forming free sulfur and dimethylamine, 2,6-dimethylpiperidine, and t-butylamine, respectively. © 1996 John Wiley & Sons, Inc.
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  • 75
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    Kinetic study of the reaction of BrO radicals with dimethylsulfide (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 383-389 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the reaction of BrO with dimethylsulfide (DMS) have been studied by the mass spectrometric discharge-flow method in the temperature range (233-320) K and at a total pressure around 1 torr. The temperature dependence of the reaction rate constant k1 = (1.5 ± 0.4) × 10-14 exp [(845 ± 175)/T] cm3 molecule-1s-1 has been determined under pseudo-first-order conditions in excess of DMS over BrO radicals. Mass spectrometric calibration of the reaction product dimethylsulfoxide (DMSO) allowed for a determination of the branching ratio of (0.94 ± 0.11) for the DMSO forming channel. These data indicate that the reaction is likely to proceed through a channel involving a long-lived intermediate: BrO + CH3SCH3 →[CH3S(OBr)CH3]* → CH3S(O)CH3 + Br. The atmospheric application of the data is briefly discussed. © 1996 John Wiley & Sons, Inc.
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  • 76
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    Pd(II) inhibition during hexacyanoferrate(III) oxidation of sugars: A kinetic study (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 413-419 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inhibition effect of PdCl2 on the rate of oxidation of sugars by alkaline hexacyanoferrate(III) has been observed. The order of reactions in hexacyanoferrate(III) and OH- is zero and unity, respectively, while that in sugars decreases from unity at higher sugar concentration. The kinetic data and spectrophotometric evidence support the formation of {PdII - (sugar)} and {PdII - sugar)2} complexes and their resistance to react with Fe(CN)63- © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 77
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    Atmospheric chemistry of CH2BR2: Rate coefficients for its reaction with Cl atoms and OH and the chemistry of the CHBr2O radical (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 433-442 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for the reaction of OH radicals and Cl atoms with dibromomethane OH + CH2Br2 → CHBr2 + H2O (1) and Cl + CH2 Br2 → CHBr2 + HCL (3) and for the reaction of Cl atoms with methyl bromide, Cl + CH3Br → HCl + CH2Br (4), have been obtained using relative rate techniques. At 298 K, the value of k1 was determined to be (1.2 ± 0.31) × 10-13 cm3 molec-1 s-1. The rate coefficients k3 and k4 were determined at a series of temperatures ranging from 228 K to 296 K and combined with the measurements of Gierczak et al., yielding the following Arrhenius expressions for k3 and k4; k3 = (6.35 ± 0.6) × 10-12 exp(-807 ± 50/T) cm3 molec-1 s-1 and k4 = (1.49 ± 0.2) × 10-11 exp(-1056 ± 50/T) cm3 molec-1 s-1.In addition, the Cl atom initiated oxidation mechanism of CH2Br2 in air has been studied at 298 K. The products observed were HC(O)Br and small amounts of CO. The dominant atmospheric fate of the alkoxy radical, CHBr2O is elimination of a Br atom, which occurs at a rate estimated to be greater than 4 × 106 s-1 in 700 torr of O2 at 298 K. © 1996 John Wiley & Sons, Inc.
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  • 78
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    Rates of reaction between the nitrate radical and some unsaturated alcohols (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 467-474 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for nitrate radical gas-phase reactions with prop-2-en-l-ol (allyl alcohol), but-1-en-3-ol, and 2-methylbut-3-en-2-ol have been determined. Both absolute (fast flow discharge with diode laser detection of NO3) and relative (batch reactor and FTIR spectroscopy) rate techniques were used to measure the rate coefficients. The rate coefficients at 294 K are: (1.3 ± 0.2) × 10-14, (1.2 ± 0.3) × 10 -14, and (2.1 ± 0.3) × 10-14 cm3 molecule-1 s-1 for prop-2-en-1-ol, but-1-en-3-ol, and 2-methylbut-3-en-2-ol, respectively. The activation energy for reaction of NO3 with prop-2-en-1-ol was determined to 2.8 ± 2.5 kJ mol-1 in the temperature range between 273 and 363 K. The atmospheric importance of unsaturated alcohols and structure-reactivity considerations are also discussed. © 1996 John Wiley & Sons, Inc.
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  • 79
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    Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NOx (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 497-530 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed photochemical mechanism for the atmospheric reactions of isoprene and its major oxidation products in the presence of NOx, which incorporates the most recent laboratory results and our current understanding of the system, is described. It is evaluated by comparing its predictions against results of NOx-air irradiations of isoprene and its two major products, methacrolein, and methyl vinyl ketone (MVK), in five different types of environmental chambers at two different laboratories. In most cases it simulated experimental results within the uncertainty of the data and the chamber and run characterization model. However, the photodecomposition quantum yields of methacrolein and MVK and the organic nitrate yield from the OH + isoprene reaction had to be adjusted to obtain satisfactory simulations of the data. The major discrepancy observed was that the model tended to underpredict PAN by ca. 40% in the isoprene experiments, despite the fact that the model predicted PAN from methacrolein and MVK reasonably well. The uncertainties and additional data needed to completely characterize the isoprene atmospheric photooxidation system are discussed. © 1996 John Wiley & Sons, Inc.
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    Thermodynamics of organic compounds in the gas state, Vols. I and II, by M. Frenkel, G. J. Kabo, K. N. Marsh, G. N. Roganov, and R. C. Wilhoit. ISBN 1-883400-05-8, 1994, $500, 1812 pp., hardbound. Thermodynamics Research Center, The Texas A&M System, College Station, Texas, 77843 (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 553-554 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No. Abstract
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550280702
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  • 81
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    Kinetics of the reactions of CH3O with Cl and CIO (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 589-598 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions CH3O + Cl → H2CO + HCl (1) and CH3O + ClO → H2CO + HOCl (2) have been studied using the discharge-flow techniques. CH3O was monitored by laser-induced fluorescence, whereas mass spectrometry was used for the detection or titration of other species. The rate constants obtained at 298 K are: k1 = (1.9 ± 0.4) × 10-11 cm3 molecule-1 s-1 and k2 = (2.3 ± 0.3) × 10-11 cm3 molecule-1 s-1. These data are useful to interpret the results of the studies of the reactions of CH3O2 with Cl and ClO which, at least partly, produce CH3O radicals. © 1996 John Wiley & Sons, Inc.
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  • 82
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    Gas-phase reaction of ozone with trans-2-hexenal, trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 373-382 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of ozone with the unsaturated oxygenates trans-2-hexenal, trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one, which are components of biogenic emissions and/or close structural homologues thereof, has been investigated at atmospheric pressure and ambient temperature (286-291 K) and humidity (RH = 55 ± 10%). Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 1.28 ± 0.28 for trans-2-hexenal, 21.8 ± 2.8 for trans-2-hexenyl acetate, and 394 ± 40 for 6-methyl-5-hepten-2-one. Carbonyl product formation yields, measured with sufficient cyclohexane added to scavenge the hydroxyl radical, are 0.53 ± 0.06 for n-butanal and 0.56 ± 0.04 for glyoxal from trans-2-hexenal, 0.47 ± 0.02 for n-butanal and 0.58 ± 0.14 for 1-oxoethyl acetate from trans-2-hexenyl acetate, 0.55 ± 0.07 for formaldehyde and 0.44 ± 0.03 for 2-oxobutanal from ethylvinyl ketone, and 0.28 ± 0.02 for acetone from 6-methyl-5-hepten-2-one. Reaction mechanisms are outlined and the atmospheric persistence of the compounds studied is briefly discussed. © 1996 John Wiley & Sons, Inc.
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  • 83
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    Masthead (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550280501
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  • 84
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    Kinetic studies on general base-catalyzed cleavage of phthalimide (PTH) in 2-hydroxyethylamine and 2-methoxyethylamine buffers (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 421-431 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic studies on the nucleophilic cleavage of phthalimide (PTH) in buffers of 2-hydroxyethylamine and 2-methoxyethylamine reveal nonlinear plots of kn vs. [Buf]T (at constant pH) where kn and [Buf]T represent apparent second-order rate constant and total amine buffer concentration, respectively. The nonlinear variation of kn against [Buf]T is attributed to the occurrence of a stepwise mechanism in the aminolysis of PTH. Intermolecular general base catalysis is detected in the reactions of both amines with nonionized PTH (SH) only within the pH range of the present study. © 1996 John Wiley & Sons, Inc.
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  • 85
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    Gas-phase pyrolysis mechanism and kinetics of 3-t-butoxyquadricyclane (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 481-487 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase pyrolysis of 3-t-butoxyquadricyclane [1] was investigated over the temperature range 511-542 K at one atm in helium. The initial pyrolysis step is the isomerization of 3-t-butoxyquadricyclane to 7-t-butoxynorbornadiene (Ea = 38.49 ± 0.85 kcal/mole, log A = 15.44 ± 0.35). 7-t-butoxynorbornadiene exhibits a single unimolecular reaction pathway which produces a mixture of t-butoxycycloheptatrienes (Ea = 38.44 ± 0.63 kcal/mole, log A = 15.05 ± 0.26). This two-step mechanism affords fewer reactions than unsubstituted quadricyclane in the gas phase and could be useful for its reduced sooting potential. © 1996 John Wiley & Sons, Inc.
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  • 86
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    Electronic Resource
    Masthead (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550280701
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  • 87
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    Studies on the oxidation of α-amino acids by N-Bromo oxidants: Kinetics of the reaction of bromide ion with N-Bromoacetamide (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 545-551 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of oxidation of amino acids (AA) by N-Bromoacetamide (NBA) was studied in aqueous buffered medium at 35°C. The rate of disappearance of [NBA] is catalyzed by the Br- produced from the reduction of NBA. Analysis of the autocatalyzed reaction gives the kinetic data for the oxidation of bromide ion by NBA. The results suggest that the protonated NBA reacts with Br- to form Br2 which rapidly oxidizes amino acids. The rate constant for the reaction between protonated NBA and Br- at 35°C is estimated. © 1996 John Wiley & Sons, Inc.
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  • 88
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    Rate coefficients for the gas-phase reactions of bromine radicals with a series of alkenes, dienes, and aromatic hydrocarbons at 298 ± 2 K (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 565-577 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the relative kinetic method rate coefficients have been determined for the gas-phase reaction of bromine (Br) radicals with a series of alkenes, chloroalkenes, dienes, and aromatic hydrocarbons in 1000 mbar of synthetic air at 298 ± 2 K. Both the UV photolysis of CH2Br2 (λ = 254 nm) and the visible photolysis of Br2 (320 ≤ λ ≤ 480) were used to generate Br radicals. For the alkenes and dienes the following rate coefficients were obtained (in units of 10-12 cm3 molecule-1 s-1): trans-2-butene 9.26 ± 1.85; 2-methyl-1-butene 15.20 ± 3.00; 2-methyl-2-butene 19.10 ± 3.80; 2,3-dimethyl-2-butene 28.20 ± 5.60; α-pinene 22.20 ± 4.40. β-pinene 28.60 ± 5.70; 1,3-butadiene 57.50 ± 11.50; isoprene 74.20 ± 14.80; and 2,3-dimethyl-1,3-butadiene 81.7 ± 16.30. For the chloroalkenes and aromatic hydrocarbons the following rate coefficients were obtained (in units of 10-13 cm3 molecule-1 s-1): chloroethene 7.37 ± 1.92; 1,1-dichloroethene 3.66 ± 0.73; trichloroethene 0.90 ± 0.18; tetrachloroethene ≤ 0.1; benzene ≤ 0.10; toluene ≤ 0.10; p-xylene ≤ 0.10; and furan ≤ 0.10. With the exception of trans-2-butene, this study represents the first determination of the rate coefficients for all of the compounds. © 1996 John Wiley & Sons, Inc.
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  • 89
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    Kinetics of the reaction of OH radicals with a series of esters under simulated conditions at 295 K (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 609-614 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants of the isopropyl acetate, n-propyl acetate, isopropenyl acetate, n-propenyl acetate, n-butyl acetate, and ethyl butyrate reactions with OH radicals were determined in purified air under atmospheric conditions, at 750 torr and (295 ± 2) K. A relative rate experimental method was used; n-heptane, n-octane, and n-nonane were the reference compounds, with, respectively, rate constants for the reaction with OH of 7.12 × 10-12, 8.42 × 10-12, and 9.70 × 10-12 molecule-1 cm3s-1. The following rate constants were obtained in units of 10-12 molecule-1 cm3s-1; isopropyl acetate, (3.12 ± 0.29); n-propyl acetate, (1.97 ± 0.24); isopropenyl acetate, (62.53 ± 1.24); n-propenyl acetate, (24.57 ± 0.24); n-butyl acetate, (3.29 ± 0.35); and ethyl butyrate, (4.37 ± 0.42). Tertiary butyl acetate has a low reactivity with OH radicals (〈1 × 10-12 molecule-1 cm3s-1). © 1996 John Wiley & Sons, Inc.
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  • 90
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    Ruthenium (III)-Schiff base complex catalyzed oxidation of secondary alcohols by N-methylmorpholine-N-oxide or thallium (III) acetate (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 657-664 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Ru(III) Schiff base complex [Ru(L)Cl2]Cl; L = bis(picolinaldehyde) o-phenylenediimine, catalyzes the oxidation of secondary alcohols by N-methylmorpholine-N-oxide(NMO) or thallium(III) acetate as oxidant. Kinetic studies showed the formation of Ru(V) species as the active intermediate. © 1996 John Wiley & Sons, Inc.
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  • 91
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    Kinetics and mechanism of the oxidation of some thioacids by benzyltrimethylammonium dichloroiodate (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 681-685 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of thioglycolic, thiolactic, and thiomalic acids by benzyltrimethylammonium dichloroiodate (BTMAIC) to the corresponding disulfide dimer, is first-order with respect to each the thioacid and BTMAIC. The rates of oxidation were determined at different temperatures and the activation parameters were evaluated. The reaction failed to induce polymerization of acrylonitrile. The reaction rate increases with the increase in the concentration of zinc chloride. Addition of benzyltrimethylammonium chloride enhances the reaction rate. Suitable mechanism has been proposed. © 1996 John Wiley & Sons, Inc.
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  • 92
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    Kinetics and mechanism for oxime formation from 2-quinolinecarboxaldehyde (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 687-691 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxime formation from 2-quinolinecarboxaldehyde occurs with rate-limiting carbinolamine dehydration under both acidic and neutral conditions. Carbinolamine dehydration occurs via a transition state bearing a single positive charge, similar to the corresponding reaction for 2-pyridinecarboxaldehyde and unlike the same reaction for 2-, 3-, and 4-formyl-1-methylpyridinium ions and for the conjugate acids of 3- and 4-pyridinecarboxaldehydes. © 1996 John Wiley & Sons, Inc.
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  • 93
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    Kinetics of oxidation of certain pyrimidines by Ce(IV) (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 713-720 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of certain biologically important pyrimidine bases (Uracil, Thymine, and 6-Methyluracil) by Ce(IV) in aqueous H2SO4 has been investigated. A first-order dependence of rate each on [Ce(IV)], [pyrimidine], and an inverse first-order dependence on [H2SO4] has been observed. Rate and activation parameters for the oxidation of these pyrimidines have been computed. A suitable rate law and a mechanism consistent with the kinetic observations and product analysis have been proposed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.1
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  • 94
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    Electronic Resource
    Temperature-dependent kinetics studies of the reactions of C2H5O2 and n-C3H7O2 radicals with NO (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 731-740 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficients for the gas-phase reactions of C2H5O2 and n-C3H7O2 radicals with NO have been measured over the temperature range of (201-403) K using chemical ionization mass spectrometric detection of the peroxy radical. The alkyl peroxy radicals were generated by reacting alkyl radicals with O2, where the alkyl radicals were produced through the pyrolysis of a larger alkyl nitrite. In some cases C2H5 radicals were generated through the dissociation of iodoethane in a low-power radio frequency discharge. The discharge source was also tested for the i-C3H7O2 + NO reaction, yielding k298 K = (9.1 ± 1.5) × 10-12 cm3 molecule-1 s-1, in excellent agreement with our previous determination. The temperature dependent rate coefficients were found to be k(T) = (2.6 ± 0.4) × 10-12 exp{(380 ± 70)/T} cm3 molecule-1 s-1 and k(T) = (2.9 ± 0.5) × 10-12 exp{(350 ± 60)/T} cm3 molecule-1 s-1 for the reactions of C2H5O2 and n-C3H7O2 radicals with NO, respectively. The rate coefficients at 298 K derived from these Arrhenius expressions are k = (9.3 ± 1.6) × 10-12 cm3 molecule-1 s-1 for C2H5O2 radicals and k = (9.4 ± 1.6) × 10-12 cm3 molecule-1 s-1 for n-C3H7O2 radicals. © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.3
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  • 95
    Electronic Resource
    Electronic Resource
    Kinetics and modeling of the thermal reaction of propene at 800 K. Part I. Pure propene (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 829-847 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Around 800 K and at low extent of reaction, the thermal reaction of propene (initial pressures 30-200 torr) gives a very large number of products: H2, CH4, C2H4, C2H6, allene, C3H8, 1,3-C4H6, butenes, methylcyclopentenes, diallyl, hexenes, etc. It is shown that most of these molecules are produced in a free-radical chain mechanism. But some of them originate from a molecular or a biradical path. Allene is thus produced in a concerted four-center dehydrogenation of propene and 4-methylpent-1-ene arises from a bimolecular ene reaction. The Arrhenius parameters of these reactions have been measured and are discussed. A modeling of the concentration-time profile of the products has been performed and rate constants of many steps were evaluated and compared with literature data. © 1996 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.5
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  • 96
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reaction of OH with amines: tert-Butyl amine, 2,2,2-Trifluoroethyl amine, and 1,4-Diazabicyclo[2.2.2] octane (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 807-815 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds were selected to test the current predictions of OH reaction rate constants. The reactions are studied employing flash photolysis/resonance fluorescence in 130 mbar He at room temperature and up to 420 K. Experimental difficulties were encountered due to the polar and hygroscopic properties of the compounds. The rate constants obtained at 298 K, 12, 0.9, and 22·10-12cm3/s for tert-Butyl amine (TBA), 2,2,2-Trifluoroethyl amine (TFEA), and 1,4-Diazabicyclo[2.2.2]octane (DABCO®), respectively, are much lower (up to a factor 〉 20) than calculated with the incremental system devised by Atkinson, indicating that electronic and steric effects should not be neglected. Activation energies are slightly negative for TBA and DABCO and some +450 K for TFEA. The reactivity of TFEA was also determined (as 1.2·10-12cm3/s) relative to a set of hydrocarbons employing continuous photolysis of H2O2 in a glass chamber. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.3
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  • 97
    Electronic Resource
    Electronic Resource
    Kinetics and modeling of the thermal reaction of propene at 800 K. Part II. Propene in the presence of hydrogen (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 849-863 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that, at low extent of reaction, molecular hydrogen (30-260 torr) improves the selectivity of the thermal reaction of propene (30-200 torr), around 800 K, by increasing the rates of production of methane, ethene, and propane whereas it has no effect on those of allene and 4-methylpent-1-ene, and reduces those of buta-1,3-diene and 2- or 3-methylcyclopentenes. A kinetic scheme and a modeling of the reaction are proposed to account for the experimental results. The molecular mechanism of production of allene and of 4-methylpent-1-ene are confirmed. Many rate constants of elementary steps are evaluated and shown to broadly agree with literature data. © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.6
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  • 98
    Electronic Resource
    Electronic Resource
    Oxidation of some primary amines by bromamine-B in alkaline medium: A kinetic and mechanistic study (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 873-878 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of the aliphatic primary amines, n-propylamine, n-butylamine, and isoamylamine, by sodium N-bromobenzenesulfonamide or bromamine-B (BAB) in sodium hydroxide medium has been studied at 35° C. The reaction rate shows a first-order dependence each on [BAB] and [amine], and fractional order on [OH-]. Additions of halide ions and the reduction product of BAB (benzenesulfonamide), and variation of ionic strength and dielectric constant of the medium do not have any significant effect on the reaction rate. Activation parameters have been evaluated. A Taft linear free-energy relationship is observed for the reaction with ρ* = -3.0 and δ = - 2.0 indicating that electron-donating groups enhance the rate. An isokinetic relationship is observed with β = 393 K indicating that enthalpy factors control the rate. The existence of the relationship has been supported by the Exner criterion. Mechanisms consistent with the observed kinetic data have been proposed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.2
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  • 99
    Electronic Resource
    Electronic Resource
    Temperature dependence of the reaction of NO with CFCl2CH2O2 and CH3CFClO2 radicals (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 9-19 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of NO with the peroxy radical CFCl2CH2O2, and with CH3CFClO2 was investigated at 8(SINGLEBOND)20 torr and 263(SINGLEBOND)321 K by UV flash photolysis of CFCl2CH3/O2/NO gas mixtures. The kinetics were determined from observations of the growth rate of the CFCl2CH2O radical and the decay rate of NO by time-resolved mass spectrometry. The temperature dependence of the bimolecular rate coefficients, with their statistical uncertainties, can be expressed as (2.9 ± 0.7) e(435±96)/T × 10-12 cm3 molecule -1s-1, or (1.3 ± 0.2) (T/300)&minus(1.5±0.2) × 10-11 cm3 molecule-1 s-1 for NO + CFCl2CH2O2, and (3.3 ± 0.6)e(516±73)/T × 10-12 cm3 molecule-1 s-1, or (2.0 ± 0.3) (T/300)&minus(1.8±0.3) × 10-11 cm3 molecule-1 s-1 for NO + CH3CFClO2. No pressure dependence of the rate coefficients could be detected over the 8(SINGLEBOND)20 torr range investigated. © 1996 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.2
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  • 100
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    Electronic Resource
    The pyrolysis of CCl4 and C2Cl6 in the gas phase. Mechanistic modeling by thermodynamic and kinetic parameter estimation (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 27-36 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed radical reaction mechanism is proposed to describe the thermal reactions of CCl4 and C2Cl6 in the gas phase quantitatively.A consistent set of activation energies and preexponential factors for all elementary reactions, in combination with enthalpies of formation and entropies for all species involved, is computer optimized to fit experimental pressure-rise curves and concentration profiles.For this purpose new experimental results on the pyrolysis of CCl4 are used, together with published kinetic data on the pyrolysis of C2Cl6 (in the absence and in the presence of Cl2). © 1996 John Wiley & Sons, Inc.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.4
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