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Tracer Study Using $H_2O^{18}$ on the Oxidation of Vanadium (III) by Molecular Oxygen (산소에 의한 바나듐 (III) 이온의 산화반응에 대한 $O^{18}$ 동위원소 연구)

  • Kim, Myeong Ja;Choe, Dong Sik
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.259-266
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    • 1974
  • Isotopic experiments using $H_2O^{18}$ on the oxidation of V(III) in acid perchlorate by molecular oxygen were performed in the range pH 1.0 to 3.0. At pH < 2, where a rate equation of the form TEX>$ -\frac{d[V(III)]}{dt}=k_1\frac{[O_2][V(III)]}{[H^+]}$ is adequate, the tracer study clearly indicated that all the product vanadyl ion's ($VO^{2+}$) oxygen originated from the molecular oxygen. At pH > ~2, where a different rate expression of the form $-\frac{d[V(III)]}{dt}=K_2\frac{[O_2][V(III)]^2}{[Ht]^2}$is required, the isotopic experiment showed that half the vanadyl oxygen originated from the molecular oxygen. Considering the results of the isotopic study, a mechanism for the V(Ⅲ)-O2 reaction at pH < ~2, may be suggested as follows: The tracer results at pH > ~2 imply that the rate determining step may be $$ V_2(OH)_2^{4+} + O_2 \rightarrow 2VO^{2+} + H_2O_2$$ followed by $$V_2(OH)_2^{4+} + H_2O_2 \rightarrow 2VO^{2+} + 2H_2O$$ after establishing the equilibria V^{3+} + H_2O \leftrightarrow VOH^{2+} + H^+, and 2VOH^{2+}\leftrightarrow V_2(OH)_2^{4+}$$

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Temperature Dependence of the Vibration-Vibration Energy Transfer for HF(v = n) + $H_2$(v = 0) and DF(v = n) + $D_2$(v = 0)

  • Lee, Chang-Soon;Kim, Yoo-Hang
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.11-17
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    • 1992
  • Vibration-to-vibration energy transfer probabilities for $HF(v=n)+H_2(v=0){\to}HF(v=n-1)+H_2(v=1)$ and $DF(v=n)+D_2(v=0){\to}DF(v=n-1)+D_2(v=1)$ including both the vibration-to-vibration and translation (V-V, T) and vibration-to-vibration and rotation (V-V, R) energy transfer paths have been calculated semiclassically using a simplified collision model and Morse-type intermolecular interaction potential. The calculated results are in reasonably good agreement with those obtained by experimental studies. They also show that the transition processes for $HF(v=1-3)+H_2(v=0){\to}HF(v=0-2)+H_2(v=1)$ and $DF(v=1,\;4)+D_2(v=0){\to}DF(v=0,\;3)+D_2(v=1)$ are strongly dependent on the V-V, T path at low temperature but occur predominantly via the V-V, R path with rising temperature. The vibration-to-vibration energy transfer for $HF(v=4)+H_2(v=0){\to}HF(v=3)+H_2(v=1)$ and $DF(v=2-3)+D_2(v=0){\to}DF(v=1-2)+D_2(v=1)$ occur predominantly via V-V, R path and V-V, T path through whole temperatures, respectively.

Synthesis of Silicon Carbide Whiskers (I) : Reaction Mechanism and Rate-Controlling Reaction (탄화규소 휘스커의 합성(I) : 반응기구의 율속반응)

  • 최헌진;이준근
    • Journal of the Korean Ceramic Society
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    • v.35 no.12
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    • pp.1336-1336
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    • 1998
  • A twt -step carbothermal reduction scheme has been employed for the synthesis of SiC whiskers in an Ar or a H2 atmosphere via vapor-solid two-stage and vapor-liquid-solid growth mechanism respectively. It has been shown that the whisker growth proceed through the following reaction mechanism in an Ar at-mosphere : SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) the third reaction appears to be the rate-controlling reaction since the overall reaction rates are dominated by the carbon which is participated in this reaction. The whisker growth proceeded through the following reaction mechaism in a H2 atmosphere : SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) The first reaction appears to be the rate-controlling reaction since the overall reaction rates are enhanced byincreasing the SiO vapor generation rate.

Study on Metal Cupferrate Complex (Part IV). Determination of Vanadium(IV) and Vanadium(V) Cupferrate Compositions (Metal Cupferrate Complex에 關한 硏究(第4報) Spectrophotometry에 의한 바나듐(IV) 및 바나듐(V)-Cupferrate 의 化學組成의 決定)

  • Kim, Si-Joong
    • Journal of the Korean Chemical Society
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    • v.8 no.4
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    • pp.147-152
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    • 1964
  • Vanadium (IV) and vanadium (V) cupferrate compositions in benzene phase were determined by molar ratio method and continuous variation method spectrophotometrically at 450$m{\mu}$ or 445$m{\mu}$ of wavelength. Compositions of vanadium (IV) cupferrates, V(IV)/Cupf, varied from 1/2 to 1/4 with the acidity of solution from which the complexes were precipitated. The complexes precipitated were vanadium(IV) cupferrate($VCupf_4$) in solution with lower pH than 1.0, and vanadyl(IV) cupferrate ($VOCupf_2$) in solution with 1.8-4.3 of pH. It was considered, however, that the complexes in solution with 1.3-1.7 of pH might be hydrogen vanadyl(IV) cupferrate ($HVOCupf_3$) or nearly equimolar mixture of $VCupf_4\;and\;VOCupf_2$ complexes. Vanadium (V) cupferrate composition did not vary with the acidity of solution from which the complexes were precipitated. In solution with lower pH than 1.8, the complex precipitated was hydrogen vanadyl (V) cupferrate, $HVO_2Cupf_2$.

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Rates and Mechanism of the Reactions of Aquaoxomolybdenum(V) Dimer with Vanadium(V) (아쿠아옥소몰리브텐(V) 이합체 착물과 바나듐(V)과의 반응에 대한 속도와 메카니즘)

  • Chang-Su Kim;Moon-Pyoung Yi
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.532-537
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    • 1986
  • The kinetics of the reaction of $[Mo_2O_4(H_2O)_6]^{2+}$ with $VO_2^+$ have been studied at $25^{\circ}C$ by spectrophotometric method. Stoichiometry of the oxidation of$ [Mo_2O_4(H_2O)_6]^{2+}$ is followed as $Mo_2^V + 2V^V {\rightleftharpoons} 2Mo^{VI} + 2V^{IV}$. Observed rate constants are dependent on $ [H^+]\;and\;[VO_2^+]$. Mechanism for the redox of $[Mo_2O_4(H_2O)_6]^{2+}\;and\;VO_2^+$ is proposed and discussed.

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Synthesis and Structures of $(NH_4)_{10}[Ni(H_2O)_5]_4[V_2P_2BO_{12}]_6{\cdot}nH_2O$ and $(NH_4)_{3.5}(C_3H_{12}N_2)_{3.5}[Ni(H_2O)_6]_{1.25}{[Ni(H_2O)_5]_2[V_2P_2BO_{12}]_6{\cdot}nH_2O$

  • Yun, Ho-Seop;Do, Jung-Hwan
    • Korean Journal of Crystallography
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    • v.15 no.1
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    • pp.35-39
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    • 2004
  • Two new nickel vanadium borophosphate cluster compounds, $(NH_4)_{10}[Ni(H_2O)_5]_4[V_2P_2BO_{12}]_6{\cdot}nH_2O$ (1) and $(NH_4)_{3.5}(C_3H_{12}N_2)_{3.5}[Ni(H_2O)_6]_{1.25}{[Ni(H_2O)_5]_2[V_2P_2BO_{12}]_6{\cdot}nH_2O$ (2) have been synthesized and structurally characterized. Inter-diffusion methods were employed to prepare the compounds. The cluster anion $[(NH_4)\;{\supset}\;V_2P_2BO_{12}]_6$ is used as a building unit in the synthesis of new compounds containing $Ni(H_2O){^{2+}_5}$ in the presence of pyrazine and 1,3-diaminopropane. Compounds contain isolated cluster anions with general composition ${[Ni(H_2O)_5]_n[(NH_4)\;{\supset}\;V_2P_2BO_{12}]_6}^{-(17-2n)}$ (n = 2, 4). Crystal data: $(NH_4)_{10}[Ni(H_2O)_5]_4[V_2P_2BO_{12}]_6{\cdot}nH_2O$, monoclinic, space group C2/m (no. 12), a = 27.538(2) ${\AA}$, b = 20.366(2) ${\AA}$, c = 11.9614(9) ${\AA}$, ${\beta}$ = 112.131(1)$^{\circ}$, Z = 8; $(NH_4)_{3.5}(C_3H_{12}N_2)_b[Ni(H_2O)_6]_{3.5}{[Ni(H_2O)_5]_2[V_2P_2BO_{12}]_6{\cdot}nH_2O$, triclinic, space group P-1 (no. 2), a = 17.7668(9) ${\AA}$, b = 17.881(1) ${\AA}$, c = 20.668(1) ${\AA}$, ${\alpha}$ = 86.729(1)$^{\circ}$, ${\beta}$ \ 65.77(1)$^{\circ}$, ${\gamma}$ = 80.388(1)$^{\circ}$, Z = 2.

Epr Spectra of $\alpha$-1,2,3-$[H_{n}PV(IV)V_{2}W_{9}O_{40}]^{(7-n)-}$(n = 1, 2 or 3). The Effects of Protonation on the Electron Transfer Rate

  • Lee, Chul-Wee;So, Hyun-Soo;Lee, Kyu-Ryong
    • Bulletin of the Korean Chemical Society
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    • v.7 no.2
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    • pp.108-110
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    • 1986
  • The solution epr spectra of ${\alpha}-1,2,3-[H_nPV(IV)V_2W_9O_{40}]^{(7-n)-}$were measured at various pH and three protonated species have been identified. The spectrum of $H_3PV(IV)Ⅴ_2$ consisting of 8 lines indicates that the V-OH-V bridge prevents effectively the electron transfer between the vanadium atoms. The spectrum of $H_2PV(IV)V_2$ consisting of 15 lines can be interpreted by assuming that the electron is hopping fast between the two vanadium atoms in the V-O-V sequence. The multi-line spectrum of $HPV(IV)V_2$ is interpreted as a poorly resolved 43-line spectrum which originates from the electron hopping among the three vanadium atoms with the forward and backward transition probabilities of 4:1 in the OH-V-O-V sequence.

Synthesis and Characterization of Molybdeum(V) Complexes (몰리브덴(V) 착물의 합성 및 특성에 관한 연구)

  • Kim, Il-Chool
    • Journal of the Korean Applied Science and Technology
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    • v.18 no.4
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    • pp.254-260
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    • 2001
  • The Mo(V) $di-{\mu}-oxo$ type [$Mo_{2}O_{4}(H_{2}O)_{2}L_{2}$] $SO_{4}$ complexes(L: 2,2'-dipyridyl,4,4'-ethylenedianlline) have been prepared by the reaction of $[Mo_{2}O_{4}(H_{2}O)_{6}]SO_{4}$ with a series of chelate ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate types. In $Mo_{2}O_{4}(H_{2}O)_{2}L_{2}$, two $H_{2}O$ coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, $^{1}H$ nuclear magnetic resonance spectra, and thermal analysis(TG-DTA). In the potential range -0.00V to -1.00V at a scan rate of $50mVs^{-1}$, a cathodic peak at -0.81V ${\sim}$ -0.87V (vs SCE) and an anodic peak at -0.61V ${\sim}$ -0.63V (vs SCE) have been observed in aquous solution. We infer these redox are irreversible reaction.

Synthesis and Characterization of a Di-$\mu$-oxo-bridged Molybdeum(V) Complexes (두 개 산소가교형 몰리브덴(V) 착물의 합성과 그 성질에 관한 연구)

  • Doh, Gil Myung;Kim, Ill Chool;Choi, Bo Yong
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.198-203
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    • 1995
  • The Mo(V) $di-\mu-oxo$ type $(Mo_2O_4(H_2O)_2L)$ complexes $(L:\;C_3H_7CH(SCH_2COOH)_2,\;C_6H_5CH(SCH_2COOH)_2,\;CH_3OC_6H_4CH(SCH_2COOH)_2,\;C_5H_{10}C(SCH_2COOH)_2,\;C_3H_7C(CH_3)(SCH_2COOH)_2,\;C_3H_7CH(SCH_2CH_2COOH)_2,\;C_6H_5CH(SCH_2CH_2COOH)_2)$ have been prepared by the reaction of $[Mo_2O_4(H_2O)_6]^{2+}$ with a series of dithiodicarboxy ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate type between two molybdenum. In $Mo_2O_4(H_2O)_2L$, two $H_2O$ coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, electronic spectra, and nuclear magnetic resonance spectra. In the potential range -0.00 V to -1.00 V at a scan rate of 20 $mVs^{-1}$, a cathodic peak at -0.50∼-0.58 V (vs. SCE) and an anodic peak at -0.40∼-0.43 V (vs. SCE) have been observed in aquous solution. The ratio of the cathodic to anodic current ($I_{pc}/I_{pa}$) is almost 1, we infer that redox is reversible reaction.

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Fabrications and Characterization of High Temperature, High Voltage Ni/6H-SiC and Ni/4H-SiC Schottky Barrier Diodes (고온, 고전압 Ni/4H-SiC 및 Ni/6H-SiC Schottky 다이오드의 제작 및 전기적 특성 연구)

  • Lee, Ho-Seung;Lee, Sang-Wuk;Shin, Dong-Hyuk;Park, Hyun-Chang;Jung, Woong
    • Journal of the Korean Institute of Telematics and Electronics D
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    • v.35D no.11
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    • pp.70-77
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    • 1998
  • Ni/SiC Schottky diodes have been fabricated using epitaxial 4H-SiC and 6H-SiC wafers. The epitaxial n-type layers were grown on $n^{+}$ substrates, with a doping density of 4.0$\times$10$^{16}$ c $m^{-3}$ and a thickness of 10${\mu}{\textrm}{m}$. Oxide-termination has been adopted in order to obtain high breakdown voltage and low leakage current. The fabricated Ni/4H-SiC and Ni/6H-SiC Schottky barrier diodes show excellent rectifying characteristics up to the measured temperature range of 55$0^{\circ}C$. In case of oxide-terminated Schottky barrier diodes, breakdown voltage of 973V(Ni/4H-SiC) and 920V(Ni/6H-SiC), and a very low leakage current of less than 1nA at -800V has been observed at room temperature. On non-terminated Schottky barrier diodes, breakdown voltages were 430V(Ni/4H-SiC) and 160v(Ni/6H-SiC). At room temperature, SBH(Schottky Barrier Height), ideality factor and specific on-resistance were 1.55eV, 1.3, 3.6$\times$10$^{-2}$ $\Omega$.$\textrm{cm}^2$ for Ni/4H-SiC Schottky barrier diodes, and 1.24eV, 1.2, 2.6$\times$10$^{-2}$$\Omega$.$\textrm{cm}^2$/ for Ni/SH-SiC Schottky barrier diodes, respectively. These results show that both Ni/4H-SiC and Ni/6H-SiC Schottky barrier diodes are very promising for high-temperature and high power applications.s..

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