• 제목/요약/키워드: Corresponding rate

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The Effect of Solvent on the $\alpha$-Effect(3): Nucleophilic Substitution Reactions of Aryl Acetates in $MeCN-H_2O$ Mixtures of Varying Compositions

  • Um Ik-Hwan;Hahn Gee-Jung;Lee Gwang-Ju;Kwon Dong-Song
    • Bulletin of the Korean Chemical Society
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    • 제13권6호
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    • pp.642-647
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    • 1992
  • Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

pH and Micellar Effects on the Quenching of Tris(2,2'-bipyridine)Ruthenium(Ⅱ) Luminescence by 1-Alkyl-4,4'-bipyridinium : Evidence of Deep Enbedment of the Quencher Cations in Sodium Dodecyl Sulfate Micelle

  • 박준우;김유나
    • Bulletin of the Korean Chemical Society
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    • 제18권2호
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    • pp.185-189
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    • 1997
  • The effect of pH and sodium dodecyl sulfate (SDS) micelle on the quenching of Ru(bpy)32+ luminescence by N-alkyl-4,4'-bipyridinium ions (RBPY+: R=methyl, octyl, dodecyl, benzyl) were investigated. In the absence of SDS, the quenching rate at pH 2 is similar to that of the corresponding methylalkyl viologens and much greater than that in pH 8 solution due to greater reducibility of the protonated form of RBPY+ (HRBPY2+). The quenching rate at pH 2 is strongly enhanced by the presence of SDS, while that at basic pH is greatly retarded. These observations are explained by deep embedment of RBPY+ into the hydrophobic hydrocarbon region of the micelle, whereas Ru(bpy)32+ and HRBPY2+ locate in the Stern layer of the micelle.

Ni-Al계 금속간화합물 코팅에 미치는 고주파유도 가열 조건의 영향 (Effects of Induction Heating Conditions on Ni-Al Based Intermetallic Compound Coating)

  • 이한영;김태준;조용재
    • 대한금속재료학회지
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    • 제48권2호
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    • pp.141-147
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    • 2010
  • An Ni-Al intermetallic coating has been produced by induction heating on mild steel. The effect of the induction heating conditions on the microstructure of the coating has been investigated. The reaction synthesis of the intermetallic compounds was promoted while increasing the heating rate and the holding time at reaction temperature. Especially, an NiAl phase corresponding to the initial composition of mixed powder was predominantly formed. However, the synthesis at low reaction temperatures occurred by solid state diffusion during the holding time and an Fe-Al reaction layer was formed at the interface with the substrate, regardless of the heating rate. The combustion synthesis of the intermetallic compound occurred at a temperature higher than 1023 K and resulted in an almost single phase NiAl structure.

Partial Spectrum Detection and Super-Gaussian Window Function for Ultrahigh-resolution Spectral-domain Optical Coherence Tomography with a Linear-k Spectrometer

  • Hyun-Ji, Lee;Sang-Won, Lee
    • Current Optics and Photonics
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    • 제7권1호
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    • pp.73-82
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    • 2023
  • In this study, we demonstrate ultrahigh-resolution spectral-domain optical coherence tomography with a 200-kHz line rate using a superluminescent diode with a -3-dB bandwidth of 100 nm at 849 nm. To increase the line rate, a subset of the total number of camera pixels is used. In addition, a partial-spectrum detection method is used to obtain OCT images within an imaging depth of 2.1 mm while maintaining ultrahigh axial resolution. The partially detected spectrum has a flat-topped intensity profile, and side lobes occur after fast Fourier transformation. Consequently, we propose and apply the super-Gaussian window function as a new window function, to reduce the side lobes and obtain a result that is close to that of the axial-resolution condition with no window function applied. Upon application of the super-Gaussian window function, the result is close to the ultrahigh axial resolution of 4.2 ㎛ in air, corresponding to 3.1 ㎛ in tissue (n = 1.35).

Modifying linearly non-separable support vector machine binary classifier to account for the centroid mean vector

  • Mubarak Al-Shukeili;Ronald Wesonga
    • Communications for Statistical Applications and Methods
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    • 제30권3호
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    • pp.245-258
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    • 2023
  • This study proposes a modification to the objective function of the support vector machine for the linearly non-separable case of a binary classifier yi ∈ {-1, 1}. The modification takes into account the position of each data item xi from its corresponding class centroid. The resulting optimization function involves the centroid mean vector, and the spread of data besides the support vectors, which should be minimized by the choice of hyper-plane β. Theoretical assumptions have been tested to derive an optimal separable hyperplane that yields the minimal misclassification rate. The proposed method has been evaluated using simulation studies and real-life COVID-19 patient outcome hospitalization data. Results show that the proposed method performs better than the classical linear SVM classifier as the sample size increases and is preferred in the presence of correlations among predictors as well as among extreme values.

매실함유 음료섭취가 장시간 운동시 심박수, 호흡가스 변인 및 혈중 젖산농도 변화에 미치는 영향 (Effects of Sports Drink Including the Extract from Prunus mume on the Changes of Respiratory Variables, Heart Rate, and Blood Lactate Concentration in Submaximal Exercise)

  • 김기진;배지현
    • 동아시아식생활학회지
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    • 제9권2호
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    • pp.177-187
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    • 1999
  • 본 연구에서는 1시간동안의 최대하운동시 매실함유 음료, 생수 및 기온이온음료 등의 섭취에 따른 호흡가스변인, 심박수 및 혈중 젖산농도의 변화를 비교하여 매실을 주된 성분으로 한 기능성 음료의 효능을 검증하고자 하였다. 1시간 동안의 최대하운동중 산소섭취량 및 환기량의 변화는 음료유형간 유의한 차이는 없었으며, 시기간에는 유의한(P<0.0001) 차이를 나타냈다. 그러나, Placebo군이 다른 음료유형에 비해서 통계적 유의성은 없으나 다소 높은 환기량을 나타냈으며, 음료 E군이 다소 낮은 환기량을 나타냈다. 또한 산소섭취량에 대한 환기량의 비율은 음료 E군이 현저히 낮은 수준을 나타냈다. 최대하운동중과 회복기의 심박수 및 혈중 젖산농도의 변화도 음료유형간 유의한 차이는 없었으며, 시기간에는 유의한(P<0.0001) 차이를 나타냈는데 운동중에 증가한 후 회복기에 감소하는 동일한 변화양상을 나타냈다 그러나, Placebo군이 다른 음료유형에 비해서 통계적 유의성은 없으나 다소 높은 심박수 변화양상을 나타냈으며, 매실음료군이 다소 낮은 심박수를 나타냈다. 그러나, Placebo군은 운동중 모든 시기에서 젖산역치수준의 2.25$\pm$0.32mM을 상회하는 혈중 젖산농도를 나타낸데 반해서, Control군과 매실함유음료군은 젖산역치수준의 혈중젖산농도보다 낮게 나타나는 시기가 많았다. 특히 매실함유량이 높은 D군과 E군은 운동중 40분부터 1.44-2.00mM 범위의 현저히 낮은 혈중 젖산농도를 나타냈다. 이상의 결과에서 1시간동안의 최대하운동시 산소섭취량, 심박수 및 혈중 젖산농도의 변화에서 매실함유 음료섭취가 유의한 영향을 미치지는 않았으나, 최대하운동시 매실함유 음료섭취가 환기효율의 증가, 심박수 및 혈중 젖산농도 감소 등과 같은 긍정적인 영향을 미칠 가능성이 제기되었다.

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인가전위 하에서 HT-60강 용접부의 SCC특성 평가 (Evaluation on the Characteristics of Stress Corrosion Cracking for the Weldment of HT-60 Steel under Applied Potentials)

  • 나의균
    • 대한기계학회논문집A
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    • 제26권5호
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    • pp.896-903
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    • 2002
  • The susceptibility of SCC for the weldment and PWHT specimens of HT-60 steel was evaluated using a slow strain rate method under applied potential by means of the potentiostat in synthetic seawater. In case of the parent, anodic polarization voltage was inappropriate in elongating the time to failure(TTF). -0.8V corresponding to cathodic protection range is most effective in improving the SCC resistance against corrosive environment. In case of the weldment, the values of reduction of area(ROA) and TTF at -0.68V corresponding to cathodic polarization value were 45.2% and 715,809sec which were the largest and longest life among other applied potentials. Those were vise versa at -1.1V. In case of the PWHT specimens, TTF and ROA at -0.68V was longest and largest like the weldment. Besides, PWHT is effective in prolonging the time to failure of the welded off-shore structure due to softening of effect. Regardless of the weldment and PWHT specimen, as corrosion rate gets higher, TTF becomes shorter and deformation behaviour for the weldment and PWHT specimen at -1.1V was shown to be irregular. Finally, it was found that specimens showed brittle fracture at -1.1V, but more ductile fracture accompanying the micro-cracks at applied potential of -0.68V.

PHYSIOLOGICAL RESPONSES, FEED INTAKE, URINE VOLUME AND SERUM OSMOLALITY OF AARDI GOATS DEPRIVED OF WATER DURING SPRING AND SUMMER

  • El-Nouty, F.D.;Al-Haidary, A.A.;Basmaeil, S.M.
    • Asian-Australasian Journal of Animal Sciences
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    • 제3권4호
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    • pp.331-336
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    • 1990
  • In order to evaluate the adaptability of Aardi goats to arid environment, 5 Aardi bucks were deprived of water for four days during spring and summer seasons. The rise in average maximum ambient temperature from $24.8^{\circ}C$ in spring to $35.8^{\circ}C$ in summer caused a significant rise in rectal temperature ($0.3^{\circ}C$), respiratory rate (62%), serum osmolaity (8%) and serum sodium concentration (17%). While, it resulted in a significant decline in dry matter intake (50%), urine volume (74%) and fecal water excretion (60%) compared with their values in spring, but had no significant effect on the volume of drinking water. At the end of the 4-days deprivation period during spring, respiratory rate, dry matter intake and urine volume were reduced by 18, 77 and 91% relative to their average in control goats. The corresponding reduction in summer were 58, 100 and 100%. Serum osmolaity was risen by 15% in spring deprived goats and 29% in summer deprived goats. Rectal temperature rose by a mean value of $1.3^{\circ}C$ only in goats deprived of water in summer. Percent of moisture in the feces declined from 64 in control goats, to 24% in water deprived goats during spring season. The corresponding values in summer were 25 and 6%. These responses of Aardi goats deprived of water in summer indicate that they possess a water economy mechanism enable them to tolerate infrequent drinking in hot-arid environment.

The Effect of Different Inflows on the Unsteady Hydrodynamic Characteristics of a Mixed Flow Pump

  • Yun, Long;Dezhong, Wang;Junlian, Yin;Youlin, Cai;Chao, Feng
    • International Journal of Fluid Machinery and Systems
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    • 제10권2호
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    • pp.138-145
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    • 2017
  • The problem of non-uniform inflow exists in many practical engineering applications, such as the elbow suction pipe of waterjet pump and, the channel head of steam generator which is directly connect with reactor coolant pump. Generally, pumps are identical designs and are selected based on performance under uniform inflow with the straight pipe, but actually non-uniform suction flow is induced by upstream equipment. In this paper, CFD approach was employed to analyze unsteady hydrodynamic characteristics of reactor coolant pumps with different inflows. The Reynolds-averaged Naiver-Stokes equations with the $k-{\varepsilon}$ turbulence model were solved by the computational fluid dynamics software CFX to conduct the steady and unsteady numerical simulation. The numerical results of the straight pipe and channel head were validated with experimental data for the heads at different flow coefficients. In the nominal flow rate, the head of the pump with the channel head decreases by 1.19% when compared to the straight pipe. The complicated structure of channel head induces the inlet flow non-uniform. The non-uniformity of the inflow induces the difference of vorticity distribution at the outlet of the pump. The variation law of blade to blade velocity at different flow rate and the difference of blade to blade velocity with different inflow are researched. The effects of non-uniform inflow on radial forces are absolutely different from the uniform inflow. For the radial forces at the frequency $f_R$, the corresponding amplitude of channel head are higher than the straight pipe at $1.0{\Phi}_d$ and $1.2{\Phi}_d$ flow rates, and the corresponding amplitude of channel head are lower than the straight pipe at $0.8{\Phi}_d$ flow rates.

Kinetic Study on Aminolysis of 4-Pyridyl X-Substituted Benzoates: Effect of Substituent X on Reactivity and Reaction Mechanism

  • Lee, Jong-Pal;Bae, Ae-Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제32권6호
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    • pp.1907-1911
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    • 2011
  • A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.