• 제목/요약/키워드: stability constants

검색결과 324건 처리시간 0.02초

Evaluation of thermal stability of quasi-isotropic composite/polymeric cylindrical structures under extreme climatic conditions

  • Gadalla, Mohamed;El Kadi, Hany
    • Structural Engineering and Mechanics
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    • 제32권3호
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    • pp.429-445
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    • 2009
  • Thermal stability of quasi-isotropic composite and polymeric structures is considered one of the most important criteria in predicting life span of building structures. The outdoor applications of these structures have raised some legitimate concerns about their durability including moisture resistance and thermal stability. Exposure of such quasi-isotropic composite/polymeric structures to various and severe climatic conditions such as heat flux and frigid climate would change the material behavior and thermal viability and may lead to the degradation of material properties and building durability. This paper presents an analytical model for the generalized problem. This model accommodates the non-linearity and the non-homogeneity of the internal heat generated within the structure and the changes, modification to the material constants, and the structural size. The paper also investigates the effect of the incorporation of the temperature and/or material constant sensitive internal heat generation with four encountered climatic conditions on thermal stability of infinite cylindrical quasi-isotropic composite/polymeric structures. This can eventually result in the failure of such structures. Detailed critical analyses for four case studies which consider the population of the internal heat generation, cylindrical size, material constants, and four different climatic conditions are carried out. For each case of the proposed boundary conditions, the critical thermal stability parameter is determined. The results of this paper indicate that the thermal stability parameter is critically dependent on the cylinder size, material constants/selection, the convective heat transfer coefficient, subjected heat flux and other constants accrued from the structure environment.

치환기를 가진 질소-산소(N2O2)계 네 자리 리간드의 합성과 중금속(II)이온 착화합물의 안정도상수 결정 (Syntheses of Tetradentate Nitrogen-Oxygen(N2O2)) Ligands with Substituents and the Determination of Stability Constants of Their Heavy(II) Metal Complexes)

  • 김선덕;설종민
    • 한국환경과학회지
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    • 제21권4호
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    • pp.421-435
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    • 2012
  • Novel $N_2O_2$ tetradentate ligands, H-3BPD and H-2BPD were synthesized. Hydrochloric acid salts of Br-3BPD, Cl-3BPD, Br-2BPD and Cl-2BPD having Br and Cl substituents at the $para$ position of the phenol hydroxyl group, were synthesized. The ligands were characterized by C. H. N atomic analysis, $^1H$ NMR, $^{13}C$ NMR, UV-visible, and mass spectra. The proton dissociation constants ($logK_n{^H}$) of the phenol hydroxyl group and secondary amine of the synthesized $N_2O_2$ ligands were shown by four step wise values. The orders of the calculated overall proton dissociation constants ($log{\beta}_p$) were Br-3BPD < Cl-3BPD < H-3BPD in case of 3BPD and Br-2BPD < Cl-2BPD < H-2BPD in case of 2BPD respectively. The order agreed well with that of $para$ Hammett substituent constants(${\delta}_p$). The stability constants($logK_{ML}$) of the complexes between the synthesized ligands and transition metal(II) ions agreed with the order of $log{\beta}_p$ of the ligands. The order of the $logK_{ML}$ value of the each transition metal (II) ion was Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II), which agreed well with that of Iriving-Williams series.

Stability Constants of First-row Transition Metal and Trivalent Lanthanide Metal Ion Complexes with Macrocyclic Tetraazatetraacetic and Tetraazatetramethylacetic Acids

  • 홍춘표;김동원;최기영;김창태;최용규
    • Bulletin of the Korean Chemical Society
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    • 제20권3호
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    • pp.297-300
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    • 1999
  • The protonation constants of the macrocyclic ligands, 1,4-dioxa-7,10,13,16-tetraaza-cyclooctadecane-N,N',N",N"'-tetra(acetic acid) [N-ac4[18]aneN402] and 1,4-dioxa-7,10,13,16-tetraazacyclooctadecane-1,4-dioxa-7,10,13,16-N,N',N",N"'-tetra(methylacetic acid) [N-meac4[18]aneN4O2] have been determined by using potentiometric method. The protonation constants of the N-ac4[18]aneN4O2 were 9.31 for logK1H, 8.94 for logK2H, 7.82 for logK3H, 4.48 for logK4H and 2.94 for logK5H. And the protonation constants of the N-meac4[18]aneN4O2 were 9.34 for logK1H, 9.13 for logK2H, 8.05 for logK3H, 5.86 for logK4H, and 3.55 for logK5H. The stability constants of complexes on the divalent transition ions (Co2+, Ni2+, Cu2+, and Zn2+) and tiivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with ligands N-ac4[18]-aneN4O2 and N-meac4[18]aneN4O2 have been obtained from the potentiometric data with the aid of the BEST program. The three higher values of the protonation constants for synthesized macrocyclic ligands correspond to the protonation of nitrogen atoms, and the fourth and fifth values correspond to the protonation of the carboxylate groups for the N-ac4[18]aneN4O2 and N-meac4[18]aneN4O2. The meatal ion affinities of the two tetra-azamacrocyclic ligands with four pendant acetate donor groups or methylacetate donor groups are compared. The effects of the metal ions on the stabilities are discussed, and the trends in stability constants resulting from changing the macrocyclic ring with pendant donor groups and acidity of the metal ions.

Determination of Stability Constants of the Inclusion Complexes of ${\beta}$-Blockers in Heptakis (2,3-Dimethyl-6-Sulfato)- ${\beta}$-Cyclodextrin

  • Phuong, Nuyen Thi;Lee, Kyung-Ah;Kim, Kyung-Ho;Choi, Jung-Kap;Kim, Jong-Moon;Kang , Jong-Seong
    • Archives of Pharmacal Research
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    • 제27권12호
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    • pp.1290-1294
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    • 2004
  • The ${\beta}$-blockers possess at least one chiral center and the S(-)-enantiomer shows higher affinity for binding to the ${\beta}$-adrenergic receptors than antipode. The stability constants of acebutolol, celiprolol, propranolol and terbutaline in the inclusion complexes with single-isomer heptakis (2,3-dimethyl-6-sulfato)- ${\beta}$-cyclodextrin (HDMS-${\beta}$-CD) were determined by capillary electrophoresis. The approximation and linear double reciprocal methods were adapted with comparable results. Among the ${\beta}$-blockers studied, propranolol had the lowest stability constant but the highest enantioselectivity, indicating that the magnitudes of the stability constants carried little information about enantioseparation. The magnitudes of enantioselectivities between the enantiomer pair were in the order of propranolol > celiprolol > terbutaline > acebutolol.

Synthesis, Protonation Constants and Stability Constants for $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, and $Zn^{2+}$ Ions of 1,15-bis(2-pyridyl)-2,5,8,11,14-pentaazapentadecane

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Jung, Woo-Sik;Chung, Koo-Chun
    • 분석과학
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    • 제9권4호
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    • pp.411-415
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    • 1996
  • The new potentially heptadentate $N_7$ ligand 1, 15-bis(2-pyridyl)-2, 5, 8, 11, 14-pentaazapentadecane(pytetren) has been synthesized and characterized by EA, IR, NMR, and mass spectrometry. Its proton association constants (log $K{_H}^n$) and stability constants(log $K_{ML}$) for $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, and $Zn^{2+}$ ions were determined at 298.1K and ionic strength=0.100M($KNO_3$) by potentiometry: log $K{_H}^1=9.36$, log $K{_H}^2=9.12$, log $K{_H}^3=8.09$, log $K{_H}^4=6.62$, log $K{_H}^5=4.02$, log $K{_H}^6=2.54$: log $K_{ML}(CO^{2+})=22.67$, log $K_{ML}(Ni^{2+})=26.25$. log $K_{ML}(Cu^{2+})=28.46$, log $K_{ML}(Zn^{2+})=19.90$.

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A New Substituent Constant $σ^{c+}4_s$;a Fit for π-Participation in Modified Hammett-Brown Equation

  • 조정호;신정휴
    • Bulletin of the Korean Chemical Society
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    • 제17권4호
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    • pp.347-348
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    • 1996
  • A set of substituent constants, σc+, has been widely used comparing the stability of carbocation in super acid condition. Plotting of 13C chemical shifts of cationic carbon (Δδc+) against σc+ constants yields an excellent correlation with a good correlation coefficient (r=0.999) for a cyclopentyl cation system. But these σc+ constants show poor linearity in norbornenyl cations that well known to show homoallylic stabilization in a cationic condition. We calculated the new substituent constant, σc+π, and found that the new substituent constants give an excellent correlation in π- and πσ-participating cation systems.

새로운 산소-질소(N2O2)계 네 자리 리간드의 합성과 전이금속 착물 안정도상수에 대한 치환기 효과 (Synthesis of new N2O2 tetradentate ligands and the substituent effect on the stability constants of the transition metal complexes)

  • 김선덕;진경록
    • 분석과학
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    • 제19권2호
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    • pp.131-141
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    • 2006
  • 새로운 산소-질소($N_2O_2$)계 네 자리 리간드 N,N'-bis(2-hydroxybenzyl)-ethylenediamine($H-BHE{\cdot}2HBr$)의 브롬산염을 합성하였다. 또한 $H-BHE{\cdot}2HBr$의 페놀기 5-위치에 치환기로 브롬, 염소, 메틸기 및 메톡시기를 가진 $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$$CH_3O-BHE{\cdot}2HBr$을 합성하였다. 그리고 페놀기 대신에 naphthalen-2-ol을 가진 $Nap-BHE{\cdot}2HBr$도 합성하였다. 합성된 리간드들의 양성자 해리는 수용액에서 전위차 적정한 결과 4 단계로 일어났으며, 계산된 각 리간드의 총괄 양성자 해리상수(${\log}{\beta}_p$) 값은 Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE의 순서로 Hammett 상수(${\sigma}_P$) 값의 순서와 비교적 같은 경향을 나타내었다. 전이금속(II) 이온들의 착물의 안정도상수(${\log}K_{ML}$) 값의 크기는 Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II)의 순서이었다. 또한 각 리간드들의 전이금속(II) 이온들의 착물 안정도상수(${\log}K_{ML}$) 값들의 크기 순서도 리간드의 총괄 양성자 해리상수(${\log}{\beta}_p$) 값과 서로 잘 일치하였다.

Pb-Acetato Complexes의 이온强度 및 溫度 變化에 따른 安定度常數에 關한 考察 (The Stability Constants of Lead Acetato Complexes as Function of Temperature and Ionic Strength)

  • 황정의;전영주
    • 대한화학회지
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    • 제11권2호
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    • pp.63-69
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    • 1967
  • NaAc와 HAc로 된 緩衝溶液에서 납의 mono di, tri, Acetato Complexes의 安定度常數를 이온强度 2.00, 1.00, 0.75, 그리고 溫度 $150^{\circ}C$, $20^{\circ}C$, $25^{\circ}C$, $35^{\circ}C$에서 Leden의 電位測定法으로 測定하고, $15^{\circ}C$에서는 Hume과 DeFord의 Polarographie Method로서도, 아울러 測定比較하였다. 安定度常數(Kijk)와 이온强度(${\mu}j$), 그리고 溫度(Tk) 사이에 다음과 같은 關係가 있음을 알았다. log Kijk = (Ai/${\mu}j^3$+ Bi) / Tk + Ci/${\mu}j^3$ + Di

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Chemometric 방법에 의한 메탄올/물 계에서 전이 금속 이온과 소염제 Piroxicam의 산성도 및 착체 형성에 관한 분광광도법 연구 (Spectrophotometric Study of Acidity and Complex Formation of Anti-Inflammatory Drug Piroxicam with Some Transition Metal Ions in Different Methanol/Water Mixtures by Chemometric Methods)

  • Ghasemi, Jahan B.;Jalalvand, Alireza
    • 대한화학회지
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    • 제53권6호
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    • pp.693-703
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    • 2009
  • 소염제 piroxicam (PX, 4-hydroxy-2-methyl-N-2-pridyl-2H-1, 2-benzothiazine-3-carboxadiamide-1,1-dioxide)의 착물형성을 전이금속이온, Co(II), Ni(II), Cu(II), Zn(II)과 함께 메탄올(MeOH)/물 이성분 혼합물에서 25$^{\circ}C$, 일정한 pH=5.0와 I=0.1 M에서 분광광도법으로 연구하였다. 컴퓨터 프로그램 SQUAD를 스팩트라 데이터로부터 원하는 정보를 얻는데 사용하였다. Fitting 과정의 output은 안정도 상수, 평가한 안정도 상수의 표준편차, 농도분포 다아그램, 모든 종의 스팩트럼 프로파일이다. Co(II), Ni(II), Cu(II), Zn(II)의 PX 착체의 안정도 순서는 Cu(II) > Co(II) > Ni(II) ${\approx}$ Zn(II) 순서이다. 이것은 이들 금속이 온들이 기하학적 경향이 다른 이유일 것이다. PX의 산성도 상수는 다른 pH 값에서 흡수 스펙트럼으로 부터 위의 조건에서 역시 결정하였다. 컴퓨터 프로그램 DATAN을 PX의 산성도 상수의 결정하는 데 사용하였다. 산성도 상수의 validity는 잘 알려진 컴퓨터 프로그램 SPECFIT/32을 사용하였다. 안정 및 산성도 상수의 용매성질, 음이온과 같은 다른 인자의 효과에 관하여 자세하게 논의하였다.

새로운 질소-산소계 여러 자리 리간드의 합성 및 전이금속(Ⅱ)이온 착물의 안정도상수 (Syntheses of New Nitrogen-Oxygen Multidentate Ligands and Their Stability Constants of Transition Metal(Ⅱ) Ions)

  • 김선덕;장기호;김준광
    • 대한화학회지
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    • 제42권5호
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    • pp.539-548
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    • 1998
  • 여러자리 산소-질소계 리간드들은 시프염기 리간드인 Bis(salicylidene)-ethylendiamine(BSED), Bis(salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylenetriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) 및 Bis(salicylidene)-tetraethylenepentaamine(BSTP)의 이민기를 수소환원장치에서 백금촉매를 이용하여 네자리 리간드인 N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED)과 N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), 다섯자리 N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), 여섯자리 N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT), 일곱자리 N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine(BHTP) 리간드들을 합성하였다. 리간드들의 양성자 해리상수와 전이금속(Ⅱ)과 착물의 안정도상수는 전위차 적정법으로 측정하였다. 리간드별 전이금속(Ⅱ)이온에 대한 착물 안정도상수값$(logK_{ML})$의 크기는 BHED아연(Ⅱ)의 순서로 이 결과는 Irving-Williams 서열과 잘 일치하여 증가하였다.

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