• Title/Summary/Keyword: entropy method

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Kinetics of the Reaction of Benzyl Chlorides with Pyridine in Methanol Solvent under High Pressure (고압하의 메탄올 용매내에서 염화벤질류와 피리딘과의 반응에 대한 반응속도론적 연구)

  • Oh Cheun Kwon;Young Cheul Kim;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.413-418
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    • 1987
  • Rates of the reaction for p-nitro benzyl chloride, benzyl chloride and p-methyl benzyl chloride with pyridine in methanol solvent have been measured by an electric conductivity method at 40$^{\circ}$C and 50$^{\circ}$C under various pressures (1∼2000bar). Pseudo first-order rate constants and second-order rate constants were determined. Rates of these reactions were increased in the order p-NO$_2$ < p-H < p-CH$_3$ and increased with temperature, pressure and concentration of pyridine. From those rate constants, the activation parameters were evaluated. The activation volume and the activation compressibility coefficient are both negative values, but the activation enthalpy is positive and the activation entropy is large negative value. From the evaluation of the ground state and transition state which was resulted from substituents and pressure, it was found that this reaction proceeds through S$_N$2 reaction, and S$_N$2 fashion is slightly disappeared as pressure increases.

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A VLSI Design of High Performance H.264 CAVLC Decoder Using Pipeline Stage Optimization (파이프라인 최적화를 통한 고성능 H.264 CAVLC 복호기의 VLSI 설계)

  • Lee, Byung-Yup;Ryoo, Kwang-Ki
    • Journal of the Institute of Electronics Engineers of Korea SD
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    • v.46 no.12
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    • pp.50-57
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    • 2009
  • This paper proposes a VLSI architecture of CAVLC hardware decoder which is a tool eliminating statistical redundancy in H.264/AVC video compression. The previous CAVLC hardware decoder used four stages to decode five code symbols. The previous CAVLC hardware architectures decreased decoding performance because there was an unnecessary idle cycle in between state transitions. Likewise, the computation of valid bit length includes an unnecessary idle cycle. This paper proposes hardware architecture to eliminate the idle cycle efficiently. Two methods are applied to the architecture. One is a method which eliminates an unnecessary things of buffers storing decoded codes and then makes efficient pipeline architecture. The other one is a shifter control to simplify operations and controls in the process of calculating valid bit length. The experimental result shows that the proposed architecture needs only 89 cycle in average for one macroblock decoding. This architecture improves the performance by about 29% than previous designs. The synthesis result shows that the design achieves the maximum operating frequency at 140Mhz and the hardware cost is about 11.5K under a 0.18um CMOS process. Comparing with the previous design, it can achieve low-power operation because this design is implemented with high throughputs and low gate count.

Adsorption Equilibrium, Kinetics and Thermodynamic Parameters Studies of Bismarck Brown R Dye Adsorption on Granular Activated Carbon (입상 활성탄에 대한 비스마르크 브라운 R 염료의 흡착평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.24 no.3
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    • pp.327-332
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    • 2013
  • Batch experiments were carried out for adsorption equilibrium, kinetics and thermodynamic parameters of the brilliant brown R onto granular activated carbon. The operating variables studied were the initial dye concentration, contact time and temperature. Experimental equilibrium adsorption data were fitted to Langmuir and Freundlich adsorption isotherm by linear regression method. The equilibrium process was well described by Freundlich isotherm model and from the determined separation factor (1/n), granular activated carbon could be employed as an effective treatment for the removal of bismarck brown R. From kinetic experiments, the adsorption processes were found to confirm the pseudo second order model with a good correlation and the adsorption rate constant ($k_2$) increased with increasing adsorption temperature. Thermodynamic parameters like the activation energy, change of Gibbs free energy, enthalpy, and entropy were also calculated to predict the nature of adsorption in the temperature range of 298~318 K. The activation energy was determined as 8.73 kJ/mol for 100 mg/L. It was found that the adsorption of bismarck brown R on the granular activated carbon was physical process. The negative Gibbs free energy change (${\Delta}G$ = -2.59~-4.92 kJ/mol) and the positive enthalpy change (${\Delta}H$ = +26.34 kJ/mol) are indicative of the spontaneous and endothermic nature of the adsorption process.

Design and Implementation of an In-Memory File System Cache with Selective Compression (대용량 파일시스템을 위한 선택적 압축을 지원하는 인-메모리 캐시의 설계와 구현)

  • Choe, Hyeongwon;Seo, Euiseong
    • Journal of KIISE
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    • v.44 no.7
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    • pp.658-667
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    • 2017
  • The demand for large-scale storage systems has continued to grow due to the emergence of multimedia, social-network, and big-data services. In order to improve the response time and reduce the load of such large-scale storage systems, DRAM-based in-memory cache systems are becoming popular. However, the high cost of DRAM severely restricts their capacity. While the method of compressing cache entries has been proposed to deal with the capacity limitation issue, compression and decompression, which are technically difficult to parallelize, induce significant processing overhead and in turn retard the response time. A selective compression scheme is proposed in this paper for in-memory file system caches that rapidly estimates the compression ratio of incoming cache entries with their Shannon entropies and compresses cache entries with low compression ratio. In addition, a description is provided of the design and implementation of an in-kernel in-memory file system cache with the proposed selective compression scheme. The evaluation showed that the proposed scheme reduced the execution time of benchmarks by approximately 18% in comparison to the conventional non-compressing in-memory cache scheme. It also provided a cache hit ratio similar to the all-compressing counterpart and reduced 7.5% of the execution time by reducing the compression overhead. In addition, it was shown that the selective compression scheme can reduce the CPU time used for compression by 28% compared to the case of the all-compressing scheme.

A Study on the Micellization of Sodium Dodecyl Sulfate in 𝜔-Phenylakylammonium Salt Solution (𝜔-Phenylalkylammonium Salt의 수용액에서 Sodium Dodecyl Sulfate의 미셀에 관한 연구)

  • Ryu, Yeanho;Oh, Jung Hee
    • Applied Chemistry for Engineering
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    • v.8 no.6
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    • pp.1041-1047
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    • 1997
  • The influence of $\omega$-phenylalkylammonium salt on the critical micelle concentration (CMC) of SDS has been examined using the electric conductivity method. CMC of SDS exhibited the tendency to decrease with the length of alkyl group of additives. The effect of temperature on CMC of SDS in additive solutions has been observed in the range of $18^{\circ}C-50^{\circ}C$. The free energy(${\Delta}G_m^{\circ}$) for the micellization of SDS is negative and the entropy(${\Delta}S_m^{\circ}$) is a large positive value. The enthalpy(ΔHm0is positive in low temperature($18^{\circ}C$) and negative in high temperature($>25^{\circ}C$). In the prensence of organic additives, the micellization of SDS was considered as a spontaneous process and to involve a phase transition. The values of ΔGm0has shown the tendency to increase but the values of ${\Delta}S_m^{\circ}$ and ${\Delta}H_m^{\circ}$ to decrease with the length of alklyl group of additive salts. The changes in ${\Delta}\kappa$(difference of specific conductivity) with increasing mole ratio of additives in the mixed solutions indicated the formation of mixed micelles between SDS and additives. The effect of the length of alkyl chain on the micellization of SDS demonstrated the penetration of organic additives into the palisade layer of the SDS micelle.

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Equilibrium, Kinetic and Thermodynamic Parameter Studies on Adsorption of Allura Red from Aqueous Solution by Granular Activated Carbon (입상활성탄에 의한 수용액으로부터 오로라 레드의 흡착에 대한 평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.25 no.4
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    • pp.430-436
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    • 2014
  • Allura Red (AR) is a water-soluble harmful tar-based food colorant (FD & C Red 40). Batch adsorption studies were performed for the removal of AR using bituminous coal based granular activated carbon as adsorbent by varying the operation parameters such as adsorbent dosage, initial concentration, contact time and temperature. Experimental equilibrium adsorption data were analyzed by Langmuir, Freundlich and Temkin isotherms. The equilibrium process was described well by Freundlich isotherm. From determined separation factor ($R_L$), adsorption of AR by granular activated carbon could be employed as effective treatment method. Temkin parameter, B was determined to 1.62~3.288 J/mol indicating a physical adsorption process. By estimation of adsorption rate experimental data, the value of intraparticle diffusion rate constant ($k_m$) increased with the increasing adsorption temperature. The adsorption process were found to confirm to the pseudo second order model with good correlation. Thermodynamic parameters like change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption in the temperature range of 298~318 K. The negative Gibbs free energy change (${\Delta}G$ = -2.16~-6.55 kJ/mol) and the positive enthalpy change (${\Delta}H$ = + 23.29 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption process, respectively.

The Electromotive Force and Thermodynamic Properties of the Cell at High Pressure (고압하에서의 전지의 기전력과 열역학적 성질)

  • Jee Jong-Gi;Jung Jong-Jae;Hwang Jung-Ui
    • Journal of the Korean Chemical Society
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    • v.18 no.5
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    • pp.320-328
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    • 1974
  • It is unable to derive the standard emf ($E^{\circ}$) of the cell at high pressure from the conventional method. However, when the concept of the complete equilibrium constant($K{\circ})$) is available to the conventional Nernst equation, it is possible to get the standard emf of the cell at high pressure(complete Nernst equation). Moreover, the other thermodynamic properties, such as the net change of solvation number(k), the compressibility of solvent(${\beta}$), ionization constant(K), the standard free energy change(${\Delta}G^{\circ}$), the standard enthalpy change(${\Delta}H^{\circ}$) and the standard entropy change (${\Delta}S^{\circ}$) of the cell reaction at equilibrium state have been also obtained. In this experiment, the emf of the cell; 12.5 % Cd(Hg)│$CdSO_4(3.105{\times}10^{-3}M),\;Hg_2SO_4│Hg$ have bee measured at temperature from 20 to $35^{\circ}C$ and at pressures from 1 to 2500 atms. The emf of the cell increased with increasing pressure at constant temperature, and did with increasing temperature at constant pressure. The net change of solvation number(k) of the cell reaction was 41.96 at $25^{\circ}C$, and kept constant value with pressure, while, K and ${\Delta}S^{\circ}$ increased with pressure, but whereas ${\Delta}G^{\circ}$ and ${\Delta}H^{\circ}$ decreased. Since the standard emf of the cell at high pressure can be calculated from the complete Nernst equation, the theory of chemical equilibrium could be developed with at high pressure as well as at the atmosphere.

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Kinetics for the Transformation of Outer Charge Transfer Complex to Inner Complex (Outer Charge Transfer Complex가 Inner Complex로의 변환에 따른 속도론적 연구)

  • Kwon Oh-Yun;Paek U-Hyon;Kim Eung-Ryul
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.343-349
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    • 1991
  • Formation of charge transfer complex between iodine and substituted aniline [aniline, N,N-dimethylaniline(N,N-DMA), 2,6-dimethylaniline(2,6-DMA), 2,4,6-trimethylaniline(2,4,6-TMA)] in CHCl$_3$, CH$_2$Cl$_2$ : CHCl$_3$ (1 : 1), and CH$_2$Cl$_2$ have been studied kinetically by using conductivity method. In the transformation of initially formed outer charge transfer complex to inner complex, the effects of substituted aniline as electron donor and polar medium on the reaction were investigated. The rate of transformation depend on the dielectric contribution of medium and pK$_a$ value of substituted aniline. The order of rate increasing is 2,4,6-TMA, 2,6-DMA, aniline, and N,N-DMA. The activation enthalpy ${\Delta}H^{\neq}$ for 2.5 M-substituted aniline in CHCl$_3$ at 25$^{\circ}C$ is respectively N,N-DMA, 3.47 kcal/mol; aniline, 4.25 kcal/mol; 2,6-DMA, 7.79 kcal/mol and 2,4,6-TMA, 7.96 kcal/mol; and activation entropy ${\Delta}S^{\neq}$ is large and negative value of -41 ~ -55 cal/mol${\cdot}$K.

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Integrated Authentication and Key Management Method among Heterogeneous Wireless Mobile Networks (이기종 무선 이동망간 통합 인증 및 키관리 기법)

  • Park Hyung-Soo;Lee Hyung-Woo;Lee Dong-Hoon
    • Journal of the Institute of Electronics Engineers of Korea TC
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    • v.43 no.7 s.349
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    • pp.50-59
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    • 2006
  • The new communication paradigm is rapidly shifted from wireless mobile networks to an All-IP(Internet Protocol) network, led by service industry leaders and communication manufacturers. In this paradigm, providing authentication and session keys of a subscriber becomes one of the critical tasks because of IP open accessibility among heterogeneous networks. In this paper, we introduce authentication process procedure of heterogeneous wireless mobile networks and develop so-called IMAS(Integrated Mobile Authentication Server) which can securely inter-work among all mobile networks and support the legacy networks with backward compatibility. Especially, in designing IMAS, mobile authentication inter-working mechanism, key management technique, and other issues to be overcome are presented. We analyze and evaluate the performance of authentication algorithm which creates session key. A simulation environment of IMAS is established, and a performance(TPS; Transaction Per Second) result is analyzed and evaluated. It turned out that IMAS works among heterogeneous wireless mobile networks without compensating efficiency and functionalities of the legacy networks and decrease the entropy of data redundancy and data inconsistency among networks because of the integrity of the distributed Data Base(DB).

Oxygen Ring Formation Reaction of Mono-Oxo-Bridged Binuclear Molybdenum(V) Complex (II). Reaction of $[Mo_2O_3(Phen)_2(NCS)_4]$ with Solvent Water in Water + Co-Solvent Mixtures (한개의 산소다리를 가진 몰리브덴(V) 착물의 산소고리화 반응 (II). 2성분 혼합용매에서 용매물과 $[Mo_2O_3(Phen)_2(NCS)_4]$의 반응)

  • Sang-Oh Oh;Huee-Young Seok
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.203-210
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    • 1988
  • Mono-oxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_3(Phen)_2(NCS)_4]$ produces di-oxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_4(Phen)_2(NCS)_2]$ in water + co-solvent, where the co-solvent are acetone, acetonitrile and N,N-dimethylformamide. The rate of conversion of $[Mo_2O_3(Phen)_2(NCS)_4]\;into\;[Mo_2O_4(Phen)_2(NCS)_2]$ has been measured by spectrophotometric method. Temperature was $10^{\circ}C$ to $40^{\circ}C$ and pressure was varied up to 1500 bar. The rate constants are increased with increasing water mole fraction and decreased with increasing concentration of hydrogen ion. The order of oxygen ring formation reaction rate in various cosolvent is as follows, ACT > AN > DMF which is agreed with solvent dielectric constants. The observed negative activation entropy ($[\Delta}S^{\neq}$), activation volume($[\Delta}V^{\neq}$) and activation compressibility coefficient(${\Delta}{\beta}^{\neq}$) values show that the solvent water molecule is strongly attracted to the complex at transition state. From these results, the oxygen ring formation reaction of $[Mo_2O_3(Phen)_2(NCS)_4]$ is believed association mechanism.

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