Kinetics of CO2 with primary and secondary amines in aqueous solutions - I. Zwitterion deprotonation kinetics for DEA and DIPA in aqueous blends of alkanolamines

The deprotonation kinetics of the DEA—CO2 and the DIPA—CO2 zwitterions have been studied in aqueous blends of amines at 298 K. Amine mixtures investigated were: DEA—TEA, DEA—MDEA, DEA—DMMEA, DEA—DEMEA, DIPA—TEA. DIPA—MDEA, DIPA—DMMEA, DIPA—DEMEA. For each blend the zwitterion deprotonation constant of the additional base present in solution (i.e. the tertiary amine) was determined. The observed deprotonation rate constants for the DEA-zwitterion and for the DIPA-zwitterion could be summarized in two Brønsted-type relationships. These relationships can be used to estimate the overall reaction rate of CO2 with DEA or DIPA in aqueous blends of amines. The present work on the zwitterion deprotonation kinetics of the reaction of CO2 with DEA and DIPA in aqueous amine blends provides additional verification for the validity of the zwitterion mechanism proposed by Caplow(1968) for the description of the reaction between CO2 and primary and secondary alkanolamines

Kinetics of CO2 with primary and secondary amines in aqueous solutions - II. Influence of temperature on zwitterion formation and deprotonation rates

The kinetics of the reaction of CO2 with various alkanolamines (MEA, DGA, DIPA, DEA, MMEA) in aqueous solutions has been studied as a function of temperature. Also kinetic data at 303 K were obtained for the reaction between CO2 and the cyclic amine morpholine in aqueous solutions. All observed phenomena can be explained very satisfactorily with the zwitterion mechanism proposed by Caplow. With respect to the temperature influence on the overall reaction rate for primary and secondary amines, two classes can be distinguished: when the zwitterion formation is rate determining a significant temperature influence is observed whereas only a slight temperature dependence is observed when the zwitterion deprotonation is rate determining. All kinetic experiments were interpreted with the aid of a numerically solved absorption model which describes gas absorption accompanied by reversible chemical reactions. For last reversible reactions like those in the present study, only in this way reliable reaction-rate data can be deduced from absorption experiments. The Brønsted relationship between the zwitterion-formation rate constant and the acid dissociation constant of the alkanolamine, as proposed by Versteeg and van Swaaij (1988a), seems to be valid over a wide range of temperatures and for a great variety of alkanolamines. This relationship is not valid for cyclic amines like MOR

Physical absorption of CO2 and propene into toluene/water emulsions

The physical absorption of CO2 and propene into toluene/water emulsions is studied in a stirred cell and laminar film absorber. Experimentally observed masstransfer rates are compared to an absorption model, based on Higbie's penetration theory describing physical gas absorption into an emulsion. For all absorption experiments in a stirred cell absorber (toluene fractions and stirring rates), experimentally observed mass-transfer rates are considerably higher than the rates predicted by the absorption model. Moreover, the absorption rate decreases with increasing stirring rate, whereas no influence of the stirring rate is predicted by the absorption model. In contradiction to the absorption experiments in a stirred cell absorber, the observed mass-transfer rates in the laminar film absorber agree with the model simulations. Probable existence of a very thin toluene layer is observed on top of the emulsion for the stirred cell experiments, likely due to minor phase separation. Since in the laminar film absorber gas-liquid interface and the gravity force are parallel, this phenomenon does not probably occur significantly for absorption experiments in this absorber. The observed mass-transfer phenomena can be explained, at least qualitatively, from the occurrence of a thin toluene layer

Kinetics of Carbon Dioxide with tertiary Amines in aqueous solution

The reaction of CO2 with TEA, DMMEA, and DEMEA has been studied at 293, 303, 318 and 333 K. All the kinetic experiments were carried out in a stirred cell reactor operated with a flat, smooth and horizontal gas-liquid interface. A numerical method, which describes mass transfer accompanied by reversible chemical reactions, has been applied to infer rate constants from the experimental data. It is argued that the contribution of the CO2 reaction with OH- to the observed reaction rate may have been overstimated in most literature on tertiary amine kinetics as serious depletion of OH- toward the gas-liquid interface usually occurs. \ud For all the amines studied, the reaction order in amine was found to be about one for each temperature investigated. This is in good agreement with the base catalysis mechanism proposed by Donaldson and Nguyen (1980). All kinetic data could be summarized reasonably well in one Brønsted relationship

The effects of prolonged abstinence on the processing of smoking cues: an ERP study among smokers, ex-smokers and never-smokers

Abstract Processing bias is an important feature of substance abuse. The issue whether processing bias is a more or less permanent feature of nicotine addiction remains to be resolved. The present study addresses the role of smoking status on smoking-related processing bias. We employed Event-Related Brain Potentials (ERPs) as measure of processing bias to investigate this issue. Further, self-report measures of nicotine craving and pleasantness ratings of smoking stimuli were obtained. Three groups, smokers, ex-smokers and never-smokers, were compared on their electrophysiological brain response to smoking-related and neutral pictures. The present study shows that both the P300 and SPW amplitudes in response to smoking-related pictures are significantly more enhanced for smokers than for ex-smokers and never-smokers at frontal and central sites, whereas the magnitude of the P300 and SPW amplitudes in response to neutral pictures does not differ between the three groups. Accordingly, it can be concluded that smokers show more bias for smoking-related pictures than ex-smokers and smokers. Because there is no significant difference between the P300 and SPW amplitudes of ex-smokers and never-smokers, it can also be concluded that ex-smokers display the same (low) level of processing bias as never-smokers. In addition, nicotine-craving ratings and pleasantness ratings of smoking stimuli were higher in smokers compared to ex-smokers. It can be concluded that the smoking-related craving, pleasantness rating, and processing bias decreases after a period of prolonged abstinence

Intentional modulation of the late positive potential in response to smoking cues by cognitive strategies in smokers

Attentional bias is considered an important concept in addiction since it has been found to correlate with subjective craving and is strongly associated with relapse after periods of abstinence. Hence, investigating in ways to regulate attention for drug cues would be of major clinical relevance. The present study examined deliberate, cognitive modulation of motivated attention for smoking cues in smokers. The effects of three different reappraisal strategies on an electrophysiological measure of attentive processing were investigated. Early and late LPP components in response to passively viewed neutral and smoking pictures were compared with LPPs in response to smoking pictures that were reappraised with three different reappraisal strategies. Results show that when smokers actively imagine how pleasant it would be to smoke (pleasant condition), their early LPP in response to smoking cues increases, but when smokers actively focus on an alternative stimulus (distraction condition) or think of a rational, uninvolved interpretation of the situation (rational condition), smoking-related late LPP amplitude decreases to the processing level of neutral stimuli. Present results are the first to indicate that smoking cue-elicited LPP amplitudes can be modulated by cognitive strategies, suggesting that attentive processing of smoking cues can be intentionally regulated by smokers with various levels of dependence. Although cognitive strategies can lead to enhanced processing of smoking cues, it is not completely clear whether cognitive strategies are also successful in reducing smoking-related motivated attention. Although findings do point in this direction, present study is best considered preliminary and a starting point for other research on this topic. A focus on the distraction strategy is proposed, as there are indications that this strategy is more successful than the rational strategy in decreasing LPP amplitude

Kinetic study of COS with tertiary alkanolamine solutions. 2. Modeling and experiments in a stirred cell reactor

Absorption experiments of COS into aqueous solutions of MDEA and DEMEA at 303 K have been carried out in a stirred cell reactor. An absorption model, based on Higbie’s penetration theory, has been developed and applied to interpret the absorption experiments, using the kinetic data obtained in part 1 of the present work. Experimental and calculated absorption rates agreed reasonably well at relatively low amine concentrations but deviated increasingly with increasing amine concentration. These deviations must very probably be attributed to an underestimation, by the COS-N20 analogy, of the COS solubility in rather concentrated amine solutions. The absorption model has been applied to investigate the discrepancies between the present work and kinetic data for MDEA reported in the open literature. It has been shown that these discrepancies were possibly due to small amounts of rapidly reacting contaminants

Psychometric properties of the brief Questionnaire on Smoking Urges (QSU-Brief) in a Dutch smoker population

Abstract We investigated the reliability, validity, and factor structure of the 10-item Questionnaire on Smoking Urges (QSU-Brief) in a Dutch smokers sample (N = 208). The questionnaire displayed good internal consistency (Cronbach’s alphas > 0.83), and scores were strongly correlated with three other rating scales for measuring craving, urge, and desire for cigarettes, and moderately linked to questionnaires that tap related constructs, such as cigarette dependence. As in previous research, a two factor structure was revealed. The first factor was best described by ‘the relief from nicotine withdrawal or negative affect with an urgent and overwhelming desire to smoke’, and appeared to be associated with negative affect, but not with positive affect. The second factor reflected ‘the desire and intention to smoke’, and was neither associated with positive nor negative affect. The factor structure, however, slightly deviates from the original, English version of the QSU-Brief, which might be explained by language differences. Overall, the Dutch translation of the QSU-Brief offers a reliable, valid, and multidimensional assessment of cigarette craving and appears suitable for use in a general population of young, Dutch adults

Changes in the electroencephalographic spectrum in response to smoking cues in smokers and ex-smokers

Aims: To investigate the changes in the electroencephalographic (EEG) spectrum in smokers during exposure to a neutral and a smoking-related cue to determine whether these EEG changes are still present in ex-smokers after prolonged abstinence and to examine the relationship between the power in each spectral bandwidth and subjective craving. Methods: EEG frequencies in response to a smoking-related and a neutral cue were examined in 23 smokers and 21 ex-smokers, who quit smoking for 1.4 years on average. Additionally, self-report measures of cigarette craving and nicotine dependence were obtained. The spectral power of each bandwidth was computed, log-transformed, and analyzed using a within-subject design. Differences between EEG activity under neutral and smoking conditions were correlated with differences between pre- and postexperimental subjective craving. Results: Increases in reward craving (desire and intention to smoke) were associated with reduced theta activity, whereas increases in withdrawal craving (reduction of negative affect and withdrawal symptoms) were correlated with increases in both delta and higher alpha power. Furthermore, in smokers, but not in ex-smokers, a significant beta power increase was observed between the neutral condition and the smoking condition. Conclusion: Since the beta band is associated with arousal, attention, and alertness, it is suggested that the beta increase in response to the smoking cue might reflect an enhanced allocation of resources to smoking-related stimuli, i.e. a processing bias, which is an important feature of substance abuse. Since ex-smokers do not respond to the smoking cue with beta activity enhancement, we preliminarily conclude that smoking cues do not arouse ex-smokers or capture their attention as much as they do in smokers