• Title/Summary/Keyword: Law of Chemistry

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Kinetics and Mechanism of Triethylamine Catalysed Michael Addition of Benzenethiol to 1-(2-Nitrovinyl)benzene in Acetonitrile

  • Sarathi, P.A.;Gnanasekaran, C.;Shunmugasundaram, A.
    • Bulletin of the Korean Chemical Society
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    • v.29 no.4
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    • pp.790-794
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    • 2008
  • Nucleophilic addition reaction of benzenethiols (PhSH) to 1-(2-nitrovinyl) benzenes ($\beta$ NS) in the presence of triethylamine (TEA) has been studied in acetonitrile at 25 ${^{\circ}C}$. The rate is first order with respect to [PhSH], [TEA] and [$\beta$ NS]. The reaction is found to proceed with the formation of ion-pair between benzenethiol and TEA. A suitable mechanism with the formation of an adduct between ion-pair and substrate in a slow step followed by its rearrangement to 1,2-addition product in a fast step has been proposed and corresponding rate law derived. From the rate law, the rate constants for the interaction between ion-pair and $\beta$NS have been evaluated. Interestingly, in both para-substituted substrates and benzenethiols the rate increases with the electron-withdrawing power of the substituents. The positive sign of $\rho_x$ in benzenethiols has been explained. The magnitude of cross-interaction constant, $\rho_{xy}$ is small (0.08). The magnitude of the Hammett $\rho_x$ values is higher than that of the Bronsted, $\beta_x$ values for benzenethiols. The kinetic isotope effect, $k_H/k_D$, is found to be greater than unity. A suitable transition state with simultaneous formation of $C_\beta$ -H and $B_\alpha$ -S bonds involving the ion-pair and $\beta$NS in a single concerted step has been proposed to account for these observations.

The Concentration of Magnolia Aroma Model Solution Using Pervaporation and Preparation of PVDF/PDMS Composite Membranes (투과증발법을 이용한 Magnolia Aroma 모델액의 농축 및 PVDF/PDMS 복합막의 제조)

  • Lee, Yong-Taek;Park, Joong-Won;Shin, Dong-Ho
    • Membrane Journal
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    • v.17 no.1
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    • pp.14-22
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    • 2007
  • This is the research about the concentration of trace Magnolia flavor components in water by pervaporation. We have investigated the change of selectivity depending on support membrane structure and active layer thickness using prepared PVDF/PDMS composite membrane. Through the pure water flux test for PVDF support membrane, we could indirectly confirm that as the coagulation temperature decreases and the polymer concentration increases, the surface porosity and pore diameter decreases. Appling these results to transport mechanism, we could explain the effect of support membrane structure for the composite membrane. The selectivity increases as the thickness of PDMS active layer increases. We could know that there is a limitation to describe the transport on the active layer by Fick's law through these results.

Analysis of Connection Errors by Students' Field Independence-Dependence in Learning Chemistry Concepts with Multiple External Representations (다중 표상을 활용한 화학 개념 학습에서 학생들의 장독립성-장의존성에 따른 연계 오류 분석)

  • Kang, Hun-Sik;Lee, Jong-Hyun;Noh, Tae-Hee
    • Journal of The Korean Association For Science Education
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    • v.28 no.5
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    • pp.471-481
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    • 2008
  • This study investigated connecting errors by students' field independence-dependence in learning chemistry concepts with multiple external representations in current science textbooks. Seventh graders (N=196) at a middle school were assigned to the BL and CL groups, which were respectively taught "Boyle's Law" and "Charles's Law." A field independence-dependence test was administered. After learning the target concept with text and picture emphasizing the particulate nature of matter, a connecting test was also administered. Five types of connecting errors were identified: Insufficient connection, misconnection, rash connection, impossible connection, and failing to connect. 'Failing to connect,' 'Misconnection,' and 'Rash connection' were found to be the frequent types of connecting errors regardless of the target concepts. The frequencies and percentages of the types of connecting errors were not significantly different between the field independent and field dependent students. Educational implications of these findings are discussed.

The Effects of the Prescribed Instructional Strategy for Reducing Students' Connecting Errors in Learning Chemistry Concepts with Multiple External Representations (다중 표상을 활용한 화학 개념 학습에서 학생들의 연계 오류 감소를 위한 처방적인 교수 전략의 효과)

  • Kang, Hun-Sik;Kim, You-Jung;Noh, Tae-Hee
    • Journal of The Korean Association For Science Education
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    • v.28 no.6
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    • pp.675-684
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    • 2008
  • This study investigated the effects of the prescribed instructional strategy for reducing students' connecting errors in learning chemistry concepts with multiple external representations by students' field independence-dependence. Seventh graders (N=126) at a coed middle school were assigned to control and treatment groups. The students learned "Boyle's Law" and "Charles's Law" for two class periods. Results revealed that the students in the treatment group scored significantly higher than those in the control group in a conception test. The scores of the treatment group were significantly higher than those of the control group in a motivational learning test, especially in 'attention' of the test. However, there was no significant interaction between the instruction and students' field independence-dependence in the two tests. Most students in the treatment group perceived the instruction positively in cognitive and motivational aspects.

Determination of Buprenorphine in Raw Material and Pharmaceutical Products Using Ion-pair Formation

  • Amanlou, Massoud;Khosravian, Peghah;Souri, Effat;Dadrass, Orkideh Ghorban;Dinarvand, Rasoul;Alimorad, Mohammad Massoud;Akbari, Hamid
    • Bulletin of the Korean Chemical Society
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    • v.28 no.2
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    • pp.183-187
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    • 2007
  • A simple and sensitive extractive spectrophotometric method has been described for the determination of buprenorphine either in raw material or in pharmaceutical formulations. The developed method is based on the formation of a colored ion-pair complex (1 : 1 drug/dye) of buprenorphine and bromocresol green (BCG) in buffer pH 3 and extracting in chloroform. The extracted complex shows absorbance maxima at 415 nm. Beer's law is obeyed in the concentration range of 1.32-100.81 μ g mL-1. The proposed method has been applied successfully for the determination of drug in commercial sublingual tablets and injectable dosage form. No significant interference was observed from the excipients commonly used as pharmaceutical aids with the assay procedure.

Solvent Extraction, Preconcentration and Determination of Thorium with Monoaza 18-Crown-6 Derivative

  • Dolak, I.;Karakaplan, M.;Ziyadanogullar, B.;Ziyadanogullari, R.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1564-1568
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    • 2011
  • A solvent extraction separation, preconcentration and determination of thorium with a new crown, 2-ethyl-N-benzyl-4,7,10,13,16-pentaoxa-1-azacyclooctadecane (MACE), is described in the study. The amount of thorium in the aqueous phase and organic phase was determined by Inductively Coupled Plasma-Optical Emission Spectroscopy and Ultraviolet-Visible, respectively. Thorium loaded organic phase was quantitatively stripped in a stage by using 1.0 M $HNO_3$. Thorium was effectively extracted with MACE in the pH range of 6-7 to produce a 3:2 complex ratio in the chloroform. A highly sensitive and rapid spectrophotometric method was described for determination of trace amounts of thorium with MACE. The effective molar absorption coefficient at 281 nm is $1.98{\times}10^3\;mol^{-1}cm^{-1}$, and the system complies with Beer's law in the range from 0.464 to 2.32 ${\mu}gm\;L^{-1}$ of thorium. Thorium was also determined in standard and environmental samples.

Utility of solid phase extraction for colorimetric determination of lead in waters, vegetables, biological and soil samples

  • Al-Mallah, Zakia;Amin, Alaa S.
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.461-468
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    • 2018
  • A highly sensitive, selective and rapid method for the determination of lead based on the reaction of lead (II) with 5-(4'-chlorophenylazo)-6-hydroxypyrimidine-2,4-dione (CPAHPD) and the solid phase extraction of the Pb(II)-CPAHPD complex with Amberlite XAD-2000 was developed, in the presence of pH 5.6 buffer solution and Triton X-114 medium. CPAHPD reacts with lead to form a violet complex with a molar ratio of 2:1 (CPAHPD to lead). This complex was enriched by the solid phase extraction with Amberlite XAD-2000. An enrichment factor of 500 was obtained by elution of the complex from the resin with a minimal amount of isopentyl alcohol(0.2 mL). In isopentyl alcohol medium,the molar absorptivity of the complex is $1.13{\times}10^6L\;mol^{-1}cm^{-1}$ at 647 nm. Beer's law is obeyed in the range of $5.0-160ng\;mL^{-1}$ in the measured solution. The relative standard deviation for 10 replicate samples of $50ng\;mL^{-1}$ level is 1.26%. The detection and quantification limits reaches 1.5 and $4.7ng\;mL^{-1}$ in the original samples. The presented procedure was successfully applied for determination of lead content in real samples such as vegetables, waters, biological and soil samples with satisfactory results.

Impurity profiling and chemometric analysis of methamphetamine seizures in Korea

  • Shin, Dong Won;Ko, Beom Jun;Cheong, Jae Chul;Lee, Wonho;Kim, Suhkmann;Kim, Jin Young
    • Analytical Science and Technology
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    • v.33 no.2
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    • pp.98-107
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    • 2020
  • Methamphetamine (MA) is currently the most abused illicit drug in Korea. MA is produced by chemical synthesis, and the final target drug that is produced contains small amounts of the precursor chemicals, intermediates, and by-products. To identify and quantify these trace compounds in MA seizures, a practical and feasible approach for conducting chromatographic fingerprinting with a suite of traditional chemometric methods and recently introduced machine learning approaches was examined. This was achieved using gas chromatography (GC) coupled with a flame ionization detector (FID) and mass spectrometry (MS). Following appropriate examination of all the peaks in 71 samples, 166 impurities were selected as the characteristic components. Unsupervised (principal component analysis (PCA), hierarchical cluster analysis (HCA), and K-means clustering) and supervised (partial least squares-discriminant analysis (PLS-DA), orthogonal partial least squares-discriminant analysis (OPLS-DA), support vector machines (SVM), and deep neural network (DNN) with Keras) chemometric techniques were employed for classifying the 71 MA seizures. The results of the PCA, HCA, K-means clustering, PLS-DA, OPLS-DA, SVM, and DNN methods for quality evaluation were in good agreement. However, the tested MA seizures possessed distinct features, such as chirality, cutting agents, and boiling points. The study indicated that the established qualitative and semi-quantitative methods will be practical and useful analytical tools for characterizing trace compounds in illicit MA seizures. Moreover, they will provide a statistical basis for identifying the synthesis route, sources of supply, trafficking routes, and connections between seizures, which will support drug law enforcement agencies in their effort to eliminate organized MA crime.

The Absorbance and Fluorescence of Chlorophyll-b in Organic Solvents (II) (유기용매 중에서 Chlorophyll-b의 흡광 및 형광 (제2보))

  • Choong-Hwa Lee;Myong-Suk Kim;Koo-Chun Chung;Myon-Yong Park
    • Journal of the Korean Chemical Society
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    • v.26 no.4
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    • pp.224-228
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    • 1982
  • The wavelength of chlorophyll-b on the absorbance and fluorescence emission were shifted to the longer depending on the increasing of solvent polarities but fluorescence excitation spectra were not. The presence of chl-b oligomers and monomers were identified by the specra of fluorescence emission. Fluorescence excitation, absorbance and the measurement of its intensities vs. the concentration of n-prOH added to chl-b solution. The calibration curve of chl-b solution were not obeyed to Beer's law in the range of concentrated soln. because of the presence as the oligomers.

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Transient State Theory of Significant Liquid Structure Applied to A Binary Mixture of Benzene and Carbon Tetrachloride (이성분 액체 혼합물 ($C_6H_6-CCl_4$)의 통계열역학적 연구)

  • Choi, Dong-Sik;Ahn, Woon-Sun;Kim, Kak-Choong;Chang, Sei-Hun
    • Journal of the Korean Chemical Society
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    • v.11 no.4
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    • pp.143-149
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    • 1967
  • The Transient State Theory of Significant Liquid Structure is applied to a binary liquid solution of benzene and carbon tetrachloride, which gives slightly positive deviation from Raoults law. The partition function for the solution is derived according to the proposed theory. The various thermodynamic properties such as total and partial vapor pressures, molar volumes, entropies of mixing, and compressibilities are calculated at three different temperatures, 298.15^{\circ}K$, 313.15^{\circ}K$ and 343.1515^{\circ}K$. The calculated values agree satisfactorily with experimental data.

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