共查询到20条相似文献,搜索用时 93 毫秒
1.
The hydrolysis of silicic acid, Si(OH)4, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH− was generated coulometrically. The total concentration of Si(OH)4, B, and log[H+] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H+] 11.7, respectively. Within these ranges the formation of SiO(OH)3− and SiO2(OH)22− with formation constants log β−11(Si(OH)4 SiO(OH)3− + H+) = −9.472 ±0.002 and log β−21(Si(OH)4 SiO2(OH)22− + 2H+) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H+] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID. 相似文献
2.
The hydrolysis of silicic acid, Si(OH)4, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH? was generated coulometrically. The total concentration of Si(OH)4, B, and log[H+] were varied within the limits 0.00075 ? B ? 0.008 M and 2.5 ? -log[H+] ? 11.7, respectively. Within these ranges the formation of SiO(OH)3? and SiO2(OH)22? with formation constants log β?11(Si(OH)4 ? SiO(OH)3? + H+) = ?9.472 ±0.002 and log β?21(Si(OH)4 ? SiO2(OH)22? + 2H+) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID. 相似文献
3.
Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH2+ species were found to be insignificant relative to Fe(OH)2+ at p[H+] = ?log [H+] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of . Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)30 species. The formation constant for this species can be calculated as . The Fe(OH)4? species is present at concentrations which are negligible compared to Fe(OH)2+ and Fe(OH)30 in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H+] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)2+ and Fe(OH)30 species. 相似文献
4.
Interconversion rates of the mononuclear ferric iron species Fe(OH)30 and Fe(OH)2+ are derived and their implications for the behavior of these species in seawater are examined. The previously reported formation constant for Fe(OH)30 and its claimed extreme adsorptive reactivity in seawater are shown to be mutually inconsistent. Although Fe(OH)30 is probably a stoichiometrically minor dissolved iron species, its rapid formation from Fe(OH)2+ could substantially enhance the rates of heterogeneous reaction rates of the [Fe(OH)2+ + Fe(OH)30] pool if the latter species is very reactive. 相似文献
5.
The solubility of aluminum hydroxide in seawater of 35‰ salinity at pH = 7.4−8.2 and 25°C was determined experimentally for
three samples synthesized in different ways. The solubilities of two phases subjected to ageing and precipitated (a) from
a boiling solution of aluminum sulfate and (b) immediately from seawater at room temperature were a little different and showed
the minimum within pH = 8.05−8.10. The solubility of aluminum hydroxide precipitated from a solution of sulfate aluminum at
room temperature and not subjected to ageing was about twofold at pH∼7.9. The analysis of the pH dependence of the concentration
of dissolved aluminum allows one to suppose that an Al(OH)2+ hydroxo complex is the primary form of the aluminum occurrence in seawater at pH < 8.05, whereas the Al(OH)4− anion is prevailing at pH > 8.10. Electrically neutral Al(OH)30 hydroxocomplexes may be prevailing within the narrow range of pH = 8.05−8.10 and, in general, are of secondary importance. 相似文献
6.
《Deep Sea Research Part I: Oceanographic Research Papers》2006,53(4):684-688
The precision of spectrophotometric measurements of indicator absorbance ratios is sufficient to allow evaluation of small isotopically induced differences in the dissociation constant of boric acid (KB). The quotient of 11KB and 10KB, obtained using isotopically ⩾99% pure borate/boric acid buffers, provides an equilibrium constant for the reaction 10B(OH)3+11B(OH)4−⇔11B(OH)3+10B(OH)4− which heretofore had not been experimentally determined. Previous theoretical and semi-empirical evaluations of this equilibrium, which is important for assessments of the paleo-pH of seawater and the paleo-pCO2 of the atmosphere, have yielded constants, 11–10KB=10KB/11KB, that have ranged between 1.0194 and approximately 1.033. The experimentally determined value 11–10KB=1.0285±0.0016 (mean±95% confidence interval) obtained at 25 °C and 0.63 molal (mol kg−1 H2O) ionic strength is in much better agreement with recent theoretical assessments of 11–10KB that have ranged between 1.026 and 1.033, than the much-cited original estimate (1.0194) of Kakihana et al. (1977) [Fundamental studies on the ion-exchange separation of boron isotopes. Bulletin of Chemical Society of Japan 50, 158–163]. Since the activity quotient for the fractionation reaction is almost equal to unity, it is expected that the 11–10KB value obtained in this study will be applicable over a wide range of solution compositions and ionic strengths. 相似文献
7.
It is shown that the values of pK1C and pK2C for carbonic acid, pKB for boric acid and the ionic product of water, pKw, in sea water may be explained on the basis of their determination in 0.7 Mw sodium chloride and the formation of the following ion-pairs: NaSO4?, MgSO4, CaSO4, MgCO3, CaCO3, MgHCO3+, CaHCO3+, MgOH+, HSO4?, MgB(OH)4+ and CaB(OH)4+. On the whole the calculated stability constants are lower than those given by Garrels and Thompson (1962). 相似文献
8.
9.
This study aims to quantify the effects of different pretreatment methods on the stable carbon isotope values of fatty acids in marine microalgae(Isochrysis zhanjiangenisis).To identify the effects of sample preparation on theδ~(13)C value and the fatty acid composition,we examined eight types of pretreatment methods including:(a) drying the sample followed by direct methyl esterification using HCl-CH_3OH;(b) drying the sample followed by direct methyl esterification using H_2SO_4-CH_3OH;(c) drying the sample by ultrasonic extraction and methylesterification using HCl-CH_3OH;(d) drying the sample by ultrasonic extraction and methyl-esterification using H_2SO_4-CH_3OH;(e) fresh sample followed by direct methyl-esterification using HCl-CH_3OH;(f) fresh sample followed by direct methyl-esterification using H_2SO_4-CH_3OH;(g) fresh sample with ultrasonic extraction followed by methyl-esterification using HCl-CH_3OH,and(h) fresh sample with ultrasonic extraction followed by methylesterification using H_2SO_4-CH_3 OH.The results show that the δ~(13)C values from Groups a–e,g and h fluctuated within 0.3‰,and the δ~(13)C values of Group f were approximately 0.7‰ lower than the other seven groups.Therefore,the different sample pretreatment methods used towards the extraction of fatty acids from marine microalgae may result in different results regarding the stable carbon isotope ratios,and if necessary a correction should be applied. 相似文献
10.
《Marine Chemistry》2001,73(2):113-124
Dissolved boron in seawater occurs mainly in the form of boric acid (B(OH)3) and borate (B(OH)4−). While the equilibrium properties of the dissociation of boric acid have been studied in detail, very little work has focused on the kinetics of the boric acid–borate equilibrium in seawater. Here, we present a theoretical study of the relaxation of the seawater borate–carbonate system towards equilibrium using the experimental data of Mallo et al. [Nouv. J. Chim. 8 (1984) 373] and Waton et al. [J. Phys. Chem. 88 (1984) 3301]. The reaction rate constants are two to four orders of magnitude smaller than typical rate constants of diffusion-controlled reactions of other acid–base equilibria. This is presumably due to the substantial structural change that is involved in the conversion from planar B(OH)3 to tetrahedral B(OH)4. The time required to establish the boric acid–borate equilibrium in seawater is calculated to be ∼95μs at temperature T=25°C and salinity S=35. Considering stable boron isotopes 11B and 10B, the isotopic equilibration time is ∼125 μs. As a result, kinetic isotope effects during coprecipitation of boron in calcium carbonate are unlikely and therefore do not affect the use of stable boron isotopes as a paleo-pH recorder. 相似文献
11.
Mathieu Mongin David M. Nelson Philippe Pondaven Mark A. Brzezinski Paul Trguer 《Deep Sea Research Part I: Oceanographic Research Papers》2003,50(12):1445-1480
We report the first application of a biogeochemical model in which the major elemental composition of the phytoplankton is flexible, and responds to changing light and nutrient conditions. The model includes two phytoplankton groups: diatoms and non-siliceous picoplankton. Both fix C in accordance with photosynthesis-irradiance relationships used in other models and take up NO3− and NH4+ (and Si(OH)4 for diatoms) following Michaelis-Menten kinetics. The model allows for light dependence of photosynthesis and NO3− uptake, and for the observed near-total light independence of NH4+ uptake and Si(OH)4 uptake. It tracks the resulting C/N ratios of both phytoplankton groups and Si/N ratio of diatoms, and permits uptake of C, N and Si to proceed independently of one another when those ratios are close to those of nutrient-replete phytoplankton. When the C/N or Si/N ratio of either phytoplankton group indicates that its growth is limited by N, Si or light, uptake of non-limiting elements is controlled by the content of the limiting element in accordance with the cell-quota formulation of Droop (J. Mar. Biol. Ass. U.K 54 (1974) 825).We applied this model to the Bermuda Atlantic Time-series Study (BATS) site in the western Sargasso Sea. The model was tuned to produce vertical profiles and time courses of [NO3−], [NH4+] and [Si(OH)4] that are consistent with the data, by adjusting the kinetic parameters for N and Si uptake and the rate of nitrification. The model then reproduces the observed time courses of chlorophyll-a, particulate organic carbon and nitrogen, biogenic silica, primary productivity, biogenic silica production and POC export with no further tuning. Simulated C/N and Si/N ratios of the phytoplankton indicate that N is the main growth-limiting nutrient throughout the thermally stratified period and that [Si(OH)4], although always limiting to the rate of Si uptake by diatoms, seldom limits their growth rate. The model requires significant nitrification in the upper 200 m to yield realistic time courses and vertical profiles of [NH4+] and [NO3−], suggesting that NO3− is not supplied to the upper water column entirely by physical processes. A nitrification-corrected f-ratio (fNC), calculated for the upper 200 m as: (NO3− uptake—nitrification)/(NO3− uptake+NH4+ uptake) has annual values ranging from only 0.05–0.09, implying that 90–95% of the N taken up annually by phytoplankton is supplied by biological regeneration (including nitrification) in the upper 200 m. Reported discrepancies between estimates of organic C export based on seasonal chemical changes and POC export measured at the BATS site can be almost completely resolved if there is significant regeneration of NO3− via organic-matter decomposition in the upper 200 m. 相似文献
12.
The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔHapp of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression
−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]2