Nitrate photolysis in seawater by sunlight     

Oliver C Zafiriou  Mary B True 《Marine Chemistry》1979,8(1):33-42

The photolysis of nitrate in seawater by sunlight has been re-examined using abiotic seawater and naturally occurring concentrations. Photochemical formation of nitrite from nitrate was observed. First-order nitrate photolysis rate coefficients calculated from nitrite appearance (corrected for concomitant nitrite photolysis) ranged from 0 to 2.3 yr^?1, median 0.7 yr^?1. The coefficients did not correlate well with water chemistry, but decreased with increasing light dose. A first-order rate coefficient of 0.4 yr^?1 was calculated for the primary photochemical process $\text{NO}{}_3{}^{\mathrm{?}}\text{+}\text{h}\text{υ =}\text{NO}{}_2{}^{\mathrm{?}}\text{+ O(}{}^3\text{P)}$ under sea surface equatorial insolation and cloudiness conditions. However, no significant nitrate concentration decreases could be detected, suggesting an upper limit for the net first-order nitrate loss rate coefficient of 0.3 yr^?1. The data thus imply some conversion in the reverse sense: NO₂^? + hυ →→ NO₃^?.If our median rate estimate applies to surface oceanic conditions, nitrate photolysis proceeds at roughly 0.02–0.5% of the rate of N incorporation during primary production. It is thus not a significant NO₃-N sink. Since such reactive species as oxygen atoms, nitrogen dioxide, and hydroxyl radicals are produced, the reaction may have significant consequences in seawater. However, nitrite photolysis is almost certainly a more significant process.The results show internal inconsistencies and our rates are markedly different from those calculated using data from other studies. Nitrate photolysis rates are theoretically concentration- and light dose-dependent. Whether these dependencies explain the apparent discrepancies is unclear, as methodological effects may also be involved. The system requires further study.  相似文献   

Solubility of hydrous ferric oxide and iron speciation in seawater     

Robert H. Byrne  Dana R. Kester 《Marine Chemistry》1976,4(3):255-274

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 ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. 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 ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. 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   

A potentiometric study of ferric ion complexes in synthetic media and seawater     

Robert H. Byrne  Dana R. Kester 《Marine Chemistry》1976,4(3):275-287

An investigation of ferric ion complexing has been conducted in synthetic media and seawater at 25°C. Formation constants were potentiometrically determined for the species FeCl²⁺, FeCl₂⁺, FeOH²⁺, and Fe(OH)₂⁺ at an ionic strength of 0.68 m. Formation constants for the ferric chloride complexes were determined as _Clβ₁ = 2.76 and _Clβ₂ = 0.44. In a study of the reaction Fe³⁺ + nH₂O ? Fe(OH)_n^(3?n)+ + nH⁺ in NaClO₄, NaNO₃ and NaCl the formation constants ${}^1\text{β}{}_1\text{and}{}^1\text{β}{}_2$ were shown to be relatively independent of medium when the effects of nitrate and chloride complexing were taken into account. The average values obtained for these constants are ${}^1\text{β}{}_1\text{= 1.93 · 10}{}^{\mathrm{?3}}\text{and}{}^1\text{β}{}_2\text{= 8.6 · 10}{}^{\mathrm{?8}}$. Reasonable agreement with these values was obtained when these constants were determined in seawater by accounting for the effects of chloride, fluoride and sulfate complexing.  相似文献   

Copper(II) interaction with carbonate species based on malachite solubility in perchlorate medium at the ionic strength of seawater     

James L Symes  Dana R Kester 《Marine Chemistry》1985,16(3):189-211

Equilibrium constants for copper(II)-carbonate and -bicarbonate species have been determined at 25°C from consideration of malachite, Cu₂(OH)₂CO_3(s), solubility in UV-photo-oxidized perchlorate solutions of 0.72 m ionic strength. The ratios of total dissolved copper, T(Cu), to free copper(II) ion, [Cu ²⁺], in 30 malachite saturated experimental solutions of 1–10 × 10^?3eq kg^?1 H₂O initial total alkalinity (TA_i in the pH range 5.0–9.3 were fitted to a copper(II)-ion speciation model. The experimental data indicate the existence of CuCO₃⁺, CuHCO₃⁺ and Cu(OH)CO₃^? in addition to the hydrolys and Cu(OH)CO₃^? in addition to the hydrolysis products in the range of conditions defined by this study. The stoichiometric equilibrium constants, applicable to seawater at 0.72 m ionic strength, 25°C and 1 atm are A speciation model employing the equilibrium constants determined in this study and copper(II) hydrolysis constants from previous work suggests that the inorganic speciation in seawater (pH = 8.2, TA = 2.3 meq kg ^?1, 25°C) is dominated by the CuCO₃⁰ complex (82%) and that only 2.9% of the total inorganic copper exists as the free copper(II) ion. Hydrolysis products, CuOH⁺ and Cu(OH)₂⁰, account for 6.5% while CuHCO₃⁺ and Cu(OH)CO₃^? species comprise 1.0 and 6.3% of the total inorganic copper, respectively.  相似文献   

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3− and SiO2(OH)22−. A precision study at 25°C in a simplified seawater medium     

Staffan Sjöberg  Agneta Nordin  Nils Ingri 《Marine Chemistry》1981,10(6):521-532

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)₂^2? 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)₂^2? + 2H⁺) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with $\text{-}\text{log[H}{}^{\mathrm{+}}\text{] ? 10.7}$ their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.  相似文献   

The solubility of aragonite in seawater at 25.0°C and 32.62‰ salinity     

David C. Plath  Ricardo M. Pytkowicz 《Marine Chemistry》1980,10(1):3-7

The apparent solubility product of aragonite in 32‰ seawater at 25.0°C is reported as K′_sp = (0.869±0.049) × 10^?6(mol²kgseawater^?2) thus confirming the value of R.A. Berner, 1976 (Am. J. Sci., 276: 713–730). The apparent solubility product ratio for aragonite and calcite is reported as $\text{K′}{}_{\mathrm{aragonite}}\text{K′}{}_{\mathrm{calcite}}\text{= 2.05}$ The deviation of this value from the thermodynamic ratio is atttributed to the formation of a stable low Mg-calcite coating on pure calcite in seawater measurements of solubility.  相似文献   

Theory of interaction intensities,buffer capacities,and pH stability in aqueous systems,with application to the pH of seawater and a heterogeneous model ocean system     

Francois Morel  Russell E. McDuff  James J. Morgan 《Marine Chemistry》1976,4(1):1-28

The choice of convenient basic constituents for evaluating pH stability of aqueous systems is discussed, and two useful interaction parameters are defined and related to the buffer capacity: the interaction capacity, $\text{δ′}{}_{\mathrm{X,Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{TOT}\text{Y}$, and the interaction intensity, $\text{δ}{}_{\mathrm{X,\; Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{pTOT}\text{Y}$; for pH and TOTH, δ′_{H, H} = ?β_H^?1, where β_H is the pH buffer capacity. A method is presented for the computation of exact values of all interaction capacities and intensities through inversion of the Jacobian matrix of the system of non-linear equations describing the aqueous system. The major species of an aqueous system (H₂O, H⁺, solid phases, gases, and the most abundant solute species) are shown to constitute a useful set of basic constituents for evaluation of approximate pH buffer capacities according to a simple rule: the major-minor species rule for zeroth order pH-TOTH interaction. The concepts of buffering and pH-statting are examined and contrasted; it is demonstrated that the buffer capacity of an aqueous system cannot be infinite: it is limited by the concentration of solutes in solution. The effect upon pH of variations in constituents other than H⁺ is described in terms of first order interactions via complex formation and solid formation; approximate formulas for calculation are derived. Higher order interactions are derived from combinations of first order ones. The pH stability of the ocean system is examined in terms of an aqueous phase model including ion-association reactions and a heterogeneous model incorporating CO₂ in the gas phase, quartz, kaolinite, calcite, chlorite, and illite, in addition to the aqueous phase. There is an approximately three-fold enhancement of buffer capacity in the aqueous model as a consequence of ion-association. Only a few interaction pathways are of quantitative significance in establishing the buffer capacity. Results for the heterogeneous ocean model lend quantitative support to Sillén's notion of pH stability: the buffer capacity is about four hundred times greater than that of the aqueous phase model.  相似文献   

The solubility of calcite — probably containing magnesium — in seawater     

David C. Plath  Kenneth S. Johnson  Ricardo M. Pytkowicz 《Marine Chemistry》1980,10(1):9-29

The apparent solubility product of calcite was measured by saturometry as a function of temperature and salinity. Simplified equations for the carbonic-acid dissociation constants of Mehrbach et al., 1973 (Limnol. Oceanogr., 18: 897–907) have been derived from their experimental data and used to calculate apparent solubility product, K′_sp, K′_sp at 25°C and 35‰ salinity, was found to be K′_sp = 4.70 × 10^?7(mol²kgseawater^?2) An equation was fitted to the experimental data, resulting in pK′_sp = 6.5795 ? 3.7159 × 10⁵(TS) + 0.91056(T/S) ? 22.110(1.0/S)The mean activity coefficients, $\text{γ±}\text{CaCO}{}_3$, were calculated at various temperatures and salinities, using the thermodynamic solubility product of Jacobson and Langmuir, 1974 (Geochim. Cosmochim. Acta, 38: 301–318) and the apparent solubility products quoted in their paper. The change in K′_sp at each salinity, as a function of temperature, was used to calculate the apparent enthalpy of dissociation for calcite, ΔH′, and the extrapolated value of ΔH⁰ was in good agreement with that of Jacobson and Langmuir. Finally, this work was used to calculate saturation profiles for oceanic stations and as a basis for comment of the accuracy of in-situ saturometry, as well as the applicability of in-situ K′_sp pressure corrections.  相似文献   

The effect of nitrite on the spectrophotometric determination of iodate in seawater     

P Chapman  P.S Liss 《Marine Chemistry》1977,5(3):243-249

A widely used method for determining iodate in seawater involves reaction of the IO₃^? with excess I^?, under acid conditions, to form I₂ which is measured colorimetrically. It is known that when the acidification is by mineral acid, nitrite can interfere with the method by oxidising I^? to I₂ in an analogous way to IO₃^?. Some workers have used sulphamic acid for acidification since it is reported to destroy nitrite in solution.We have investigated the extent of nitrite interference in the colorimetric determination of iodate using both mineral acid and sulphamic acid for acidifying the reaction mixture. In seawater the extent of the interference is equivalent to 0.212 μM 1^?1 IO₃^? per μM 1^?1 NO₂^? with sulphuric acid, and 0.128 μM 1^?1 IO₃^? per μM 1^?1 NO₂^? with sulphamic acid. This means that for a seawater containing 0.31 μM 1^?1 (39 μg 1^?1) IO₃^?, the presence of 0.5 μM 1^?1 NO₂^? will lead to an error of 25% in the iodate determined colorimetrically in methods using sulphuric acid, and 15% in methods in which sulphamic acid is used.  相似文献   

Prediction of the partial molal volumes of electrolytes in seawater     

J.V. Leyendekkers 《Marine Chemistry》1974,2(2):89-110

A general equation is derived for predicting the partial molal volume (pmv) of an electrolyte in seawater, using binary solution data, and seawater density data. The composition of seawater need not be “average” - prediction can be made for any composition. Simpler equations are derived for “average” seawater. The ranges cover $\text{S = 0–50‰}$, t = 0–30°C and p = 1–1,000 bar, subject to the availability of binary solution data. Estimates of the pmv's of a number of electrolytes are made and compared with experimental values and the summed ionic values.  相似文献   

Diffusion coefficients of major ions in seawater     

A. Poisson  A. Papaud 《Marine Chemistry》1983,13(4):265-280

Self-diffusion coefficients of five major ions have been determined by a radioactive tracer method (capillary tube method) in seawater of salinity 34.86 at 25°C. Data are presented for Na⁺, Ca²⁺, Cl⁻, SO₄², and HCO₃⁻, which constitute about 95% by weight of sea salt. The influence of temperature and salinity on these coefficients has been studied for Na⁺ and Cl⁻ which are the major components of sea salt: self-diffusion coefficients of these two ions have been measured in seawater, at different temperatures for a salinity of 34.86 and at different salinities for a temperature of 25°C. Diffusion coefficients of the same ions have been determined at 25°C by using another radioactive tracer method (quasi-steady cell method). In this experiment, seawater ions were allowed to diffuse from natural seawater into dilute seawater. Data have been obtained at 25°C for Na⁺, Ca ²⁺, Cl⁻, SO₄²⁻ and HCO₃⁻, corresponding to different salinity gradients.  相似文献   

The density and expansibility of artificial seawater solutions from 0 to 40°C and 0 to 21‰ chlorinity     

Frank J. Millero  Fred K. Lepple 《Marine Chemistry》1973,1(2):89-104

The density of artificial seawater has been measured with a magnetic float densitometer at 1 atm. from 0 to 40°C (in 5° intervals) and from 0 to 21‰ chlorinity. The densities at each temperature have been fitted to a modified Root (1933) equation, $\text{d = d}{}^0\text{+}\text{A}{}_{\mathrm{V}}\text{′ Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{V}}\text{′ Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and an equation based on the Debye-Hückel limiting law, $\text{d = d}{}^0\text{+}\text{A}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{+ C}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}{}^2$ where A_V′, B_V′, A_V, B_V and C_V are temperature-dependent constants (related to the ion-water and ion-ion interactions of the major components), d⁰ is the density of pure water and Cl_V is the volume chlorinity — $\text{Cl}{}_{\mathrm{V}}\text{= Cl (‰) × density}$. The densities fit these equations to ±9 p.p.m. from 0 to 25°C and ±18 p.p.m. from 30 to 40°C. The densities for artificial seawater are in good agreement with our measurements of Copenhagen seawater and the results for natural seawater obtained from Knudsen's tables.The expansibilities of the artificial seawater mixtures have been calculated from the temperature dependence of the densities. The resulting expansibilities at each temperature were fitted to the equations $\text{α = α}{}^0\text{+}\text{A}{}_{\mathrm{E}}\text{′ Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{E}}\text{′ Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{α = α}{}^0\text{+}\text{A}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{+ C}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}{}^2$ where A_E′, B_E′, A_E, B_E and C_E are constants (related to the effect of temperature on the ion-water and ion-ion interactions of the major components) and α⁰ is the expansibility of pure water. The expansibilities fit these equations to ±1 p.p.m. and at 35‰ S agree within ±1 p.p.m. with the expansibilities obtained for natural seawater from Knudsen's tables.Theoretical density and expansibility constants have been determined from the apparent equivalent volumes and expansibilities of the major components of seawater by using the additivity principle. The average deviations of the calculated densities and expansibilities are, respectively, ±20 and ±3 p.p.m. over the entire temperature range.  相似文献   

Silicate correction in the colorimetric determination of phosphate in seawater     

Shinichiro Noriki 《Journal of Oceanography》1983,39(6):324-326

An improved Strickland and Parsons' method, in which silicate correction is made, is described for the colorimetric determination of phosphate in seawater. Silicate correction is made by subtracting the value of 0.025 (C/100)², whereC is silicate concentration (µg atoms 1^?1), from the observed phosphate concentration. The relative standard deviations are 2 % at the 1 µg atom PO ₄ ^3? ?Pl^?1 level and less than 1 % at the 3 µg atoms PO ₄ ^3? ?Pl^?1 level in seawater.  相似文献   

MgSO4 ION association in seawater     

F.H Fisher  J.M Gieskes  C.C Hsu 《Marine Chemistry》1982,11(3):279-283

Examination of the consequences of the stoichiometric association constant $\text{K}{}^1{}_{\mathrm{<mtext>a</mtext>}}\text{= 41.7}$ for MgSO₄ in seawater as advocated by Johnson and Pytkowicz (1979) leads to a thermodynamic association constant K_a = 212.6, a value 32% greater than K_A = 160 derived from conductance data. Use of K_a = 160 leads to a $\text{K}{}^1{}_{\mathrm{<mtext>a</mtext>}}$ in essential agreement with the value of 10.2 reported by Kester and Pytkowicz (1969).  相似文献   

Arsenic,barium, germanium,tin, dimethylsulfide and nutrient biogeochemistry in Charlotte Harbor,Florida, a phosphorus-enriched estuary     

P.N. Froelich  L.W. Kaul  J.T. Byrd  M.O. Andreae  K.K. Roe 《Estuarine, Coastal and Shelf Science》1985,20(3):239-264

Concentrations of dissolved nutrients (NO₃, PO₄, Si), germanium species, arsenic species, tin, barium, dimethylsulfide and related parameters were measured along the salinity gradient in Charlotte Harbor. Phosphate enrichment from the phosphate industry on the Peace River promotes a productive diatom bloom near the river mouth where NO₃ and Si are completely consumed. Inorganic germanium is completely depleted in this bloom by uptake into biogenic opal. The $\text{Ge}\text{Si}$ ratio taken up by diatoms is about 0·7 × 10^?6, the same as that provided by the river flux, confirming that siliceous organisms incorporate germanium as an accidental trace replacement for silica. Monomethylgermanium and dimethylgermanium concentrations are undetectable in the Peace River, and increase linearly with increasing salinity to the seawater end of the bay, suggesting that these organogermanium species behave conservatively in estuaries, and are neither produced nor consumed during estuarine biogenic opal formation or dissolution. Inorganic arsenic displays slight removal in the bloom. Monomethylarsenic is produced both in the bloom and in mid-estuary, while dimethylarsenic is conservative in the bloom but produced in mid-estuary. The total production of methylarsenicals within the bay approximately balances the removal of inorganic arsenic, suggesting that most biological arsenic uptake in the estuary is biomethylated and released to the water column. Dimethylsulfide increases with increasing salinity in the estuary and shows evidence of removal, probably both by degassing and by microbial consumption. An input of DMS is observed in the central estuary. The behavior of total dissolvable tin shows no biological activity in the bloom or in mid-estuary, but does display a low-salinity input signal that parallels dissolved organic material, perhaps suggesting an association between tin and DOM. Barium displays dramatic input behavior at mid-salinities, probably due to slow release from clays deposited in the harbor after catastrophic phosphate slime spills into the Peace River.  相似文献   

Sulphate complexation in seawater: A relation between the stability constants of sodium sulphate and magnesium sulphate in seawater from a determination of the stability constant of hydrogen sulphate and a calculation of the single ion activity coefficient of sulphate     

Bengt Elgquist  Margareta Wedborg 《Marine Chemistry》1974,2(1):1-15

The conditional stability constant of HSO₄^? has been determined at 25°C, 1 atm and a formal ionic strength of 0.7 M in solutions containing sodium, magnesium, chloride and sulphate. This was done spectrophotometrically (UV), using diphenylamine as indicator. The value obtained was 17.0 ± 0.1 (molar scale). Single ion activity coefficients for Na₂SO₄, K₂SO₄ and MgSO₄ have been calculated according to the Bates et al. (1970) model, assuming that the sulphate ion is not hydrated. It was found that the single ion activity coefficient of sulphate changes very little between Na₂SO₄, K₂SO₄ and MgSO₄ when the formal ionic strength is kept constant.These results have been used to obtain relations between the stability constants of NaSO₄^? and MgSO₄ valid for seawater.  相似文献   

Variations in the boundary-drag coefficient in the tidal entrance to Chesapeake Bay,Virginia     

John C. Ludwick 《Marine Geology》1975,19(1):19-28

Use of the quadratic shear-stress law for estimating boundary drag requires specific knowledge of the magnitude of a drag coefficient, C_D, and sectional mean velocity, $\text{u}\text{?}$. In previous attempts to adapt the relationship for use in studies of marine-sediment transport, the flow measurement has been standardized at a level 100 cm above the bed. The particularized value of the drag coefficient has been designated as C₁₀₀.In the entrance area to Chesapeake Bay, Virginia, C₁₀₀ has been found to range through unacceptably wide limits. Two-thirds of the values obtained are between 3.5 · 10^?3 and 5.4 · 10^?2. Mean C₁₀₀ for the area is 1.3 · 10^?2 as compared to 3 · 10^?3 for tidal channels within Puget Sound, Washington.Present data suggest that, given a moveable bed, a size hierarchy of mobile bed forms, time-varying flow, and a lack of equilibrium between flow and bed, C₁₀₀ changes continuously with boundary shear stress.Accurate evaluation of boundary shear stress in tidal entrances with high flow rates and mobile beds presently requires measurement of velocity profiles.  相似文献   

Stability of ion pairs from gypsum solubility degree of ion pair formation between the major constituents of seawater     

Bengt Elgquist  Margareta Wedborg 《Marine Chemistry》1975,3(3):215-225

The stability constants of the ion pairs NaSO₄^?, KSO₄^?, MgSO₄^?, CaSO₄, MgCl⁺ and CaCl⁺ were determined at 25°C and 0.7 M formal ionic strength, by measuring the solubility of gypsum (CaSO₄ · 2H₂O) in different media. The media used contained one or two of the following electrolytes: NaCl, KCl, MgCl₂, NaClO₄, Mg(ClO₄)₂, Na₂SO₄. Values for the stability constants are 1.22, 1.84, 12.3, 30.6, 0.48 and 1.20 M^?1, respectively, and the solubility product for gypsum is 2.87 · 10^?4M². The distribution of the main constituents of seawater was calculated using these results and the values of the carbonate and bicarbonate constants given by Dyrssen and Hansson (1972–1973). The solubility of gypsum in seawater as calculated and determined experimentally was 21.43 mM and 21.10 mM, respectively.  相似文献   

Equilibrium and structural studies of silicon(iv) and aluminium(iii) in aqueous solution. V. Acidity constants of silicic acid and the ionic product of water in the medium range 0.05–2.0 M Na(CI) at 25°C     

Staffan Sjöberg  Yvonne Hägglund  Agneta Nordin  Nils Ingri 《Marine Chemistry》1983,13(1):35-44

The apparent ionization constants for silicic acid, k₁ and k₂, and the ionic product of water, k_w, have been determined in 0.05, 0.1, 0.2, 0.4 and 2.0 M Na(CI) media at 25°C. The medium dependence of these constants was found to fit equations of the form where K₁ is the ionization constant in pure water, α_i and b_i are parameters of which b_i has been adjusted to present data. The following results were obtained (α_i, b_i): pK₁ = 9.84, (1.022, ?0.11); pK₂ = 13.43, (2.044, ?0.20); and pK_w = 14.01 (1.022, ?0.22). k_i values are collected in Tables I and II. Attempts have been made to explain the medium dependence of k₁ and k₂ with weak sodium silicate complexing according to the equilibria giving k₁₁ = 0.37M^?1 and k₂₁= 3.0M^?1. However, these weak interactions cannot be interpreted unambiguously from potentiometric data at different 1-levels. Probably the medium dependence could equally well be expressed by variations in the activity coefficients.The measurements were performed as potentiometric titrations using a hydrogen electrode. The average number of OH^- reacted per Si(OH)₄, Z, has been varied within the limits 0 ? Z ? 1.1 and B₁, the total concentration of Si(OH)₄, between 0.001 M and 0.008 M. k₁ was evaluated from experimental data with B ? 0.003 M, and k₂ with B ? 0.008 M and Z ? 0.95.  相似文献   

The refractive index of seawater — comparison of experimental values and estimates from binary solution data     

J.V. Leyendekkers  R.J. Hunter 《Marine Chemistry》1978,6(1):71-76

The Tait-Gibson parameter, $\text{B}{}^1$, and the refractive index of seawater are estimated from binary solution data. The predicted and experimental values agree closely. The maximum deviations, at $\text{S = 40‰}$, are 1.7 bars for $\text{B}{}^1$ and 0.0001 for the refractive index. The results show that binary solution data, analysed on the basis of the Tammann-Tait-Gibson model for aqueous solutions, can be used to predict the properties of seawater of composition different to that of standard seawater.  相似文献