Isoperibol Reaction-Solution Calorimetry

2008 ◽  
Author(s):  
José A. Martinho Simões ◽  
Manuel Minas da Piedade
Keyword(s):  
Accurate Method ◽  
Solution Calorimetry ◽  
Combustion Calorimetry ◽  
Separate Experiment ◽  
Time Curve ◽  
Reaction Solution ◽  
Static Bomb ◽  
The One ◽  
Temperature Time

The determination of enthalpies of reaction in solution, using isoperibol reaction-solution calorimetry, is often the easiest and most accurate method of determining enthalpies of formation of compounds that cannot be studied by combustion calorimetry. The technique was pioneered by Thomsen who, between 1882 and 1886, performed thermochemical measurements involving the solution of various substances in liquids (e.g., diluted acids). Many types of isoperibol reaction-solution calorimeters have been developed since then. The designs vary according to the nature of the reactions of interest. One of the most widely used consists of a vessel, such as the one shown in figure 8.1, immersed in a thermostatic water bath. The sample is sealed inside a thin-walled glass ampule A, fixed to an ampule breaking system B in the calorimeter head C. The calorimeter head also supports the temperature sensor D, the stirrer E, and an electrical resistance F, used for calibration of the apparatus. The Dewar vessel G, containing the solution to be reacted with the sample, is adjusted to C. The assembled calorimetric vessel is transferred to the thermostatic bath, and from then on, the experimental procedure closely follows that already described in section 7.1 for isoperibol static-bomb combustion calorimetry. The reaction is initiated at the end of the fore period by pushing down the plunger H and breaking the ampule against a pin situated at the bottom of the ampule breaking system B. As a result of the calorimetric experiment, a temperature-time curve such as the one in figure 7.2 is obtained. Note that figure 7.2 is typical of an exothermic process. In the case of an endothermic process, a decrease of the temperature of the calorimetric system is observed during the reaction period. The experiments are usually carried out at atmospheric pressure and the initial goal is the determination of the enthalpy change associated with the calorimetric process under isothermal conditions, ΔHICP, usually at the reference temperature of 298.15 K. This involves the determination of the corresponding adiabatic temperature change, ΔTad, from the temperature-time curve just mentioned, by using one of the methods discussed in section 7.1; the determination of the energy equivalent of the calorimeter in a separate experiment.

Application of methods for analysing combinations of wheelset sizes and switch elements to determine the size of gutters of check-rail assemblies

2021 ◽  
pp. 3-9
Author(s):  
B. E. Glyuzberg ◽  
◽  
A. A. Loktev ◽  
V. V. Korolev ◽  
V. S. Kuskov ◽  
...  
Keyword(s):  
Cross Sections ◽  
Accurate Method ◽  
The Other ◽  
Conditional Probabilities ◽  
Rail Wear ◽  
Method Of Determination ◽  
Train Operation ◽  
Motion Paths ◽  
The One

The paper considers methods for analysis of size combinations of wheelsets and elements of switches that are used at determination of dimensions of gutters for check-rail assemblies. The method of limit combinations, from the one side, doesn’t guarantee a reliable train operation on crossing assemblies in real operation, but, from the other side, it makes unreasonably strict demands to the design of the assembly. In order to eliminate the contradictions the paper proposes to use a method of probable compositions that allows not only solving an issue of limited safe dimensions of gauge and gutters, but also determining repeatability of impacts on check-rails in the most loaded cross sections and repeatability of motion paths of wheels on crossing. However, while using this method the authors have revealed a number of contradictions between calculated results and real operation. They show that it is possible to avoid the contradictions by the use of conditional probabilities method that allows calculating probabilities of phenomena for specific size combinations of gauge and gutters. As a result, the authors have concluded that it is the most accurate method of determination of permissible dimensions for gauge and gutters on switches. With the use of the method the authors have determined the maximal values of check-rail wear for straight track made of SP special profiles in conditions of nonexceedance of «impact effect» in bent part of the check-rail for switches with various angles.

Combustion Calorimetry

2008 ◽  
Author(s):  
José A. Martinho Simões ◽  
Manuel Minas da Piedade
Keyword(s):  
Pressure Vessel ◽  
Inorganic Compounds ◽  
Combustion Calorimetry ◽  
Late Nineteenth Century ◽  
Macro Scale ◽  
New Apparatus ◽  
Internal Volume ◽  
Calorimetric Studies ◽  
Static Bomb ◽  
The One

Calorimetric studies of combustion reactions in oxygen and fluorine atmospheres have been a major source of enthalpy of formation data, particularly for organic and inorganic compounds. As referred to in the previous chapter, in bomb combustion calorimetry the reaction proceeds inside a pressure vessel—the bomb—at constant volume, and in this case the derived quantity is ΔcUo. In flame calorimetry the reaction occurs in a combustion chamber, which is in communication with the atmosphere, and the measurements lead to ΔcHo. The methods of combustion calorimetry will be described in the following paragraphs. “Conventional” combustion calorimeters operate on a “macro” scale, that is, they require samples of 0.5–1.0 g per experiment. Unfortunately, many interesting compounds are available only in much smaller amounts. In the case of oxygen combustion calorimetry, however, several combustion microcaloriemeters that only demand 2–50 mg samples have been developed in recent years. The achievements and trends in this area through 1999 have been reviewed, and interested readers are directed to these publications. Since then, a few new apparatus have been reported. Nevertheless, it should be pointed out that the general principles and techniques used to study compounds at the micro scale are not greatly different from those used in macro combustion calorimetry. Static-bomb combustion calorimetry is particularly suited to obtaining enthalpies of combustion and formation of solid and liquid compounds containing only the elements C, H, O, and N. The origins of the method can be traced back to the work of Berthelot in the late nineteenth century. Most static-bomb calorimeters used are of the isoperibol type, such as the one in figure 7.1. Here, the bomb A is a pressure vessel of ∽300 cm3 internal volume. Combustion bombs are usually made of stainless steel and frequently have an internal platinum lining to prevent corrosion. In a typical high-precision experiment, the platinum ignition wire B connects the two electrodes C, which are affixed to the bomb head. A cotton thread fuse D (other materials such as polyethene are also used), of known energy of combustion, is weighed to a precision of±10−5−10−6 g and tied to the platinum wire.

Effect of Fire Model Parameter Variability on Determination of Fire Resistance of Concrete Structural Members

2020 ◽  
Vol 309 ◽  
pp. 208-215
Author(s):  
Martin Benýšek ◽  
Radek Štefan ◽  
Jaroslav Procházka
Keyword(s):  
Fire Resistance ◽  
Concrete Slab ◽  
Maximum Temperature ◽  
Model Parameters ◽  
Time Curve ◽  
Fire Model ◽  
Model Parameter ◽  
Parameter Ranges ◽  
Temperature Time

The paper is focused on the fire model parameter variability and its effect on the determination of fire resistance of concrete structural members.For the modelling of fire, the parametric temperature-time curve given in EN 1991-1-2 is used.First part of the paper is aimed on the fire model parameter variability in general.First, fire model parameter ranges are described and their combinations are created using two common sampling methods -- Monte Carlo and Latin Hypercubes.Then, the combinations are analysed, unreasonable combinations are identified, and viable combinations are illustrated.Moreover, the characteristics of the temperature-time curves obtained using the parameter combinations are discussed. Namely, we focus on the temperature evolution, duration of fire, andthe maximum temperature reached.In the second part of the paper, an illustrative example is presented.The example is focused on the analysis of the fire resistance of a concrete slab panel. The panel is placed in a fire compartment with given fire model parameter ranges. In the example, the variability of the fire model parameters is captured using the Latin Hypercubes sampling method.The thermal analysis of the slab panel as well as the subsequent mechanical analysis are both conducted by using numerical methods described in our previous work. The calculations are performed in MATLAB environment.Finally, the obtained results are presented and discussed.It is shown that the Latin Hypercube sampling can be used as an effective tool for the investigation of the effect of fire model parameter variability on the fire resistance.

Determination of temperature-time curve of two mild moxibustion methods: Reinforcing and reducing

2013 ◽  
Vol 11 (2) ◽  
pp. 67-71
Author(s):  
Xian Song ◽  
Jian-zi Wei ◽  
Hui-juan Mao ◽  
Ling Zhao ◽  
Xue-yong Shen
Keyword(s):  
Time Curve ◽  
Mild Moxibustion ◽  
Temperature Time

scholarly journals The Use of Complete Temperature?Time Curves for Determination of Thermal Conductivity with Particular Reference to Rocks

1959 ◽  
Vol 12 (3) ◽  
pp. 203 ◽  
Author(s):  
JC Jaeger
Keyword(s):  
Thermal Conductivity ◽  
Time Curve ◽  
Transient Methods ◽  
Temperature Time

Most of the transient methods at present in use for the determination of thermal conductivity involve the study of the asymptote of a temperature-time curve. This implies that they require relatively long times of experiment and make no use of the information contained in measurements of temperature at smaller times.

Two-Stage Procedure for the Quantitative Determination of Autoprothrombin III Concentration and Some Applications

1967 ◽  
Vol 18 (01/02) ◽  
pp. 198-210 ◽  
Author(s):  
Ronald S Reno ◽  
Walter H Seegers
Keyword(s):  
Prothrombin Time ◽  
Factor Vii ◽  
Two Stage ◽  
Pronounced Increase ◽  
One Stage ◽  
Assay Procedure ◽  
Bovine Plasma ◽  
The One ◽  
Autoprothrombin C

SummaryA two-stage assay procedure was developed for the determination of the autoprothrombin C titre which can be developed from prothrombin or autoprothrombin III containing solutions. The proenzyme is activated by Russell’s viper venom and the autoprothrombin C activity that appears is measured by its ability to shorten the partial thromboplastin time of bovine plasma.Using the assay, the autoprothrombin C titre was determined in the plasma of several species, as well as the percentage of it remaining in the serum from blood clotted in glass test tubes. Much autoprothrombin III remains in human serum. With sufficient thromboplastin it was completely utilized. Plasma from selected patients with coagulation disorders was assayed and only Stuart plasma was abnormal. In so-called factor VII, IX, and P.T.A. deficiency the autoprothrombin C titre and thrombin titre that could be developed was normal. In one case (prethrombin irregularity) practically no thrombin titre developed but the amount of autoprothrombin C which generated was in the normal range.Dogs were treated with Dicumarol and the autoprothrombin C titre that could be developed from their plasmas decreased until only traces could be detected. This coincided with a lowering of the thrombin titre that could be developed and a prolongation of the one-stage prothrombin time. While the Dicumarol was acting, the dogs were given an infusion of purified bovine prothrombin and the levels of autoprothrombin C, thrombin and one-stage prothrombin time were followed for several hours. The tests became normal immediately after the infusion and then went back to preinfusion levels over a period of 24 hrs.In other dogs the effect of Dicumarol was reversed by giving vitamin K1 intravenously. The effect of the vitamin was noticed as early as 20 min after administration.In response to vitamin K the most pronounced increase was with that portion of the prothrombin molecule which yields thrombin. The proportion of that protein with respect to the precursor of autoprothrombin C increased during the first hour and then started to go down and after 3 hrs was equal to the proportion normally found in plasma.

SIMPLIFIED DEXAMETHASONE SUPPRESSION TEST

1969 ◽  
Vol 61 (2) ◽  
pp. 219-231 ◽  
Author(s):  
V. H. Asfeldt
Keyword(s):  
Cushing’S Syndrome ◽  
Normal Subjects ◽  
Cushing's Syndrome ◽  
Dexamethasone Suppression Test ◽  
Clinical Value ◽  
Suppression Test ◽  
The One ◽  
Steroid Excretion ◽  
Dexamethasone Suppression

ABSTRACT This is an investigation of the practical clinical value of the one mg dexamethasone suppression test of Nugent et al. (1963). The results, evaluated from the decrease in fluorimetrically determined plasma corticosteroids in normal subjects, as well as in cases of exogenous obesity, hirsutism and in Cushing's syndrome, confirm the findings reported in previous studies. Plasma corticosteroid reduction after one mg of dexamethasone in cases of stable diabetes was not significantly different from that observed in control subjects, but in one third of the insulin-treated diabetics only a partial response was observed, indicating a slight hypercorticism in these patients. An insufficient decrease in plasma corticosteroids was observed in certain other conditions (anorexia nervosa, pituitary adenoma, patients receiving contraceptive or anticonvulsive treatment) with no hypercorticism. The physiological significance of these findings is discussed. It is concluded that the test, together with a determination of the basal urinary 17-ketogenic steroid excretion, is suitable as the first diagnostic test in patients in whom Cushing's syndrome is suspected. In cases of insufficient suppression of plasma corticosteroids, further studies, including the suppression test of Liddle (1960), must be carried out.

Alcohol Determination by HPLC with Postcolumn Derivatization Based on the Thiosulfate-catalyzed Reaction of Alcohols and Cerium(IV) and Fluorescence Detection of Cerium(III)

2020 ◽  
Vol 16 ◽  
Author(s):  
Ikko Mikami ◽  
Eri Shibayama ◽  
Kengo Takagi
Keyword(s):  
Detection Limit ◽  
Fluorescence Detection ◽  
Reaction Rate ◽  
Detection Method ◽  
Fluorescence Detector ◽  
Reaction Solution ◽  
Optimum Detection ◽  
Postcolumn Derivatization ◽  
Sensitive Method

Background: Determination of a reducing substance based on the reaction between Ce(IV) and a reducing substance and fluorescence detection of Ce(III) generated has been reported as a selective and sensitive method. However, this method could not be applied to the determination of alcohol due to the low reaction rate of alcohol and Ce(IV). Objective: We found that thiosulfate catalytically enhanced reaction of alcohols (such as, methanol, ethanol, and propanol) and Ce(IV). Utilizing this effect, we developed a new method for the determination of alcohols. Results: In the presence of thiosulfate, an increase in fluorescence intensity was detected by injecting alcohol at concentrations of several millimolar, whereas it was not observed even at the concentration of 10% v/v (2 M for ethanol) in the absence of thiosulfate. The optimum detection conditions were determined to be 4.0 mM Ce(IV) sulfate and 0.50 mM thiosulfate, and the detection limit (S/N = 3) of ethanol under these conditions was 1 mM. In the calibration curves, changes in the slope were observed when the alcohol concentrations were approximately 10–25 mM. Using a thiosulfate solution containing ethanol as the reaction solution, a calibration curve without any change in slope was obtained, although the concentration of ethanol at the detection limit increased. The alcohols in the liquor and fuel were successfully analyzed using the proposed detection method as a postcolumn reaction. Conclusion: This new alcohol detection method using a versatile fluorescence detector can be applied to the postcolumn reaction of HPLC omitting need of time-consuming pretreatment processes.

Development of an HPLC-UV Method for Quantification of Stattic

2019 ◽  
Vol 15 (6) ◽  
pp. 568-573
Author(s):  
Soheil Sedaghat ◽  
Ommoleila Molavi ◽  
Akram Faridi ◽  
Ali Shayanfar ◽  
Mohammad Reza Rashidi
Keyword(s):  
High Performance ◽  
Accurate Method ◽  
Plasma Samples ◽  
Promising Target ◽  
Relative Standard ◽  
Dimerization Inhibitor ◽  
Oncogenic Protein ◽  
First Time ◽  
Transcription 3

Background: Signal transducer and activator of transcription 3 (STAT3), an oncogenic protein found constitutively active in many types of human malignancies, is considered to be a promising target for cancer therapy. Objective: In this study for the first time, a simple and accurate method has been developed for the determination of a STAT3 dimerization inhibitor called stattic in aqueous and plasma samples. Methods: A reverse-phase high-performance liquid chromatography (RP-HPLC) composed of C18 column as stationary phase, and the mixture of acetonitrile (60%) and water (40%) as mobile phase with a UV detection at 215 nm were applied for quantification of stattic. The developed method was validated by Food and Drug Administration (FDA) guideline. Results: The method provided a linear range between 1-40 and 2.5-40 µg mL-1 for aqueous and plasma samples, respectively, with a correlation coefficient of 0.999. The accuracy (as recovery) of the developed method was found to be between 95-105% for aqueous medium and 85-115% for plasma samples. The precision (as relative standard deviation) for aqueous and plasma samples was less than 6% and 15%, respectively. The sensitivity of the developed method based on FDA guideline was 1 µg mL-1 for aqueous and 2.5 µg mL-1 for plasma samples. Conclusion: These results show that the established method is a fast and accurate quantification for stattic in aqueous and plasma samples.

A Validated 2D-LC-UV Method for Simultaneous Determination of Imatinib and N-demethylimatinib in Plasma and Its Clinical Application for Therapeutic Drug Monitoring with GIST Patients

2020 ◽  
Vol 17 ◽  
Author(s):  
Houli Li ◽  
Di Zhang ◽  
Xiaoliang Cheng ◽  
Qiaowei Zheng ◽  
Kai Cheng ◽  
...  
Keyword(s):  
Therapeutic Drug Monitoring ◽  
One Dimension ◽  
Therapeutic Drug ◽  
Plasma Samples ◽  
Column Temperature ◽  
Injection Volume ◽  
Target Analytes ◽  
The One ◽  
Middle Column

Background: The trough concentration (Cmin) of Imatinib (IM) is closely related to the treatment outcomes and adverse reactions of patients with gastrointestinal stromal tumors (GIST). However, the drug plasma level has great interand intra-individual variability, and therapeutic drug monitoring (TDM) is highly recommended. Objective: To develop a novel, simple, and economical two-dimensional liquid chromatography method with ultraviolet detector (2D-LC-UV) for simultaneous determination of IM and its major active metabolite, N-demethyl imatinib (NDIM) in human plasma, and then apply the method for TDM of the drug. Method: Sample was processed by simple protein precipitation. Two target analytes were separated on the one-dimension column, captured on the middle column, and then transferred to the two-dimension column for further analysis. The detection was performed at 264 nm. The column temperature was maintained at 40˚C and the injection volume was 500 μL. Totally 32 plasma samples were obtained from patients with GIST who were receiving IM. Method: Sample was processed by simple protein precipitation. Two target analytes were separated on the one-dimension column, captured on the middle column, and then transferred to the two-dimension column for further analysis. The detection was performed at 264 nm. The column temperature was maintained at 40˚C and the injection volume was 500 μL. Totally 32 plasma samples were obtained from patients with GIST who were receiving IM. Conclusion: The novel 2D-LC-UV method is simple, stable, highly automated and independent of specialized technicians, which greatly increases the real-time capability of routine TDM for IM in hospital.

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