Studies of metal–organic interactions in model systems pertaining to natural waters

1976 ◽  
Vol 54 (16) ◽  
pp. 2600-2611 ◽  
Author(s):  
Robert D. Guy ◽  
C. L. Chakrabarti
Keyword(s):  
Humic Acid ◽  
Organic Acids ◽  
Stability Constants ◽  
Tannic Acid ◽  
Natural Waters ◽  
Model Systems ◽  
Organic Complexes ◽  
Metal Organic ◽  
Acid Release ◽  
The Stability

The interactions of Cu(II), Pb(II), Cd(II), and Zn(II) with humic and tannic acids were studied to evaluate the possibility of metal speciation using a combination of dialysis/atomic absorption spectroscopy, and the pH characteristics of the metal–organic species. The stability constants of metal–organic complexes were found to decrease in the order Pb(II) > Cu(II) > Cd(II) > Zn(II) and EDTA > humic acid > tannic acid. Scatchard plots for the metal–humic acid systems indicated two types of binding sites with a difference in stability constants of about 10. Ultrafiltration of metal–humic acid solutions indicated that the metal ions were concentrated in the large molecular size fractions (> 3.1 nm). Separation by dialysis was used to investigate the release of metal from model sediment components by the organic acids (the metal–organic complexes were non-dialyzable). For release of copper from bentonite, it was found that the amount of copper released depended on both the concentration of ligand and the stability constant of metal complex, with the ratio of metal release to complexing sites decreasing in the order EDTA > humic acid > tannic acid. Release of metal from the solids decreased in the order: bentonite > MnO2 > humic acid. Release of metal from the hydrous oxides via a redox decomposition of the oxide by natural organics was investigated using pyrogallol, gallic, and tannic acids. At natural water pH levels (6–8), 20 μg/ml solutions of the organic acids released 20 μmol manganese per 100 ml solutions whereas at pH 2, 60 μmol manganese were released. The pH behaviour of the organic acids has been explained in terms of formation of oxalic acid at pH &([a-z]+); 5, which then reduces the hydrous oxide.

scholarly journals Investigation of the Interaction of Gadolinium with Several Organic Ligands and Humic Acid by Ligand Competition Using 4-(2-Pyridylazo)-Resorcinol (PAR)

Environments ◽  
2020 ◽  
Vol 7 (9) ◽  
pp. 69
Author(s):  
Spencer Steinberg ◽  
Vernon Hodge ◽  
Luis Becerra-Hernandez
Keyword(s):  
Humic Acid ◽  
Organic Acids ◽  
Stability Constants ◽  
Reasonable Agreement ◽  
Organic Ligands ◽  
Competitive Displacement ◽  
Colored Complex ◽  
Method Of Continuous Variation ◽  
The Stability ◽  
Displacement Approach

Gd3+ forms a strongly colored complex with 4-(2-pyridylazo)-resorcinol (PAR) in aqueous solutions. We characterized the Gd3+-PAR complex in order to use it as a probe of Gd3+ speciation in the presence of environmentally relevant ligands. The formation of the Gd3+-PAR complex was investigated from pH 5 to 8 in the presence of excess PAR. The absorbance of the Gd3+-PAR complex dramatically increased from pH 5 to 8 and application of the method of continuous variation indicates that the complex was primarily 1:2 Gd(PAR)2 at pH 8. Stability constants for Gd3+ with other ligands can be quantified by competitive displacement of the PAR ligand. To establish the viability of this approach, we measured the stability constants between Gd3+ and several organic acids and carbonate. Our measurements show reasonable agreement with the literature values. We used the competitive displacement approach to establish that humic acids can competitively displace PAR from the Gd(PAR)2 complex.

Studies on the Coordination Reaction of VO2+ and Tannic Acid in the Tannin Extract Desulfurization

2012 ◽  
Vol 239-240 ◽  
pp. 1573-1576
Author(s):  
Zhu Qing Gao ◽  
Xiao Dong Cai ◽  
Kai Cheng Ling
Keyword(s):  
Stability Constants ◽  
Tannic Acid ◽  
Ph Value ◽  
Protonation Constants ◽  
Conditional Stability ◽  
Tannin Extract ◽  
Acid Effect ◽  
Different Temperatures ◽  
The Stability ◽  
Apparent Stability

At different temperatures, the protonation constants of tannic acid and the complex apparent stability constants between tannic acid and VO2+ were determined by using pH potentimetric method. The results showed that the protonation constants and the complex apparent stability constants slightly decreased with the raising temperature. In accordance with the pH value in the tannin extract technology, the conditional stability constants of the complex were calculated on the basis of the acid effect of tannic acid and the hydrolysis effect of VO2+. It was found that pH greatly affected the stability constants of the complex , so pH must be strictly controlled in the tannin extract technology.

scholarly journals Estimation of Buffer Capacity of Model Systems and Natural Waters by Experimental and Calculation Methods

2020 ◽  
Vol 6 (12) ◽  
pp. 68-72
Author(s):  
O. Kochergina ◽  
S. Onina
Keyword(s):  
Natural Waters ◽  
Buffer Capacity ◽  
Carbonic Acid ◽  
Water Bodies ◽  
Model Systems ◽  
Negative Consequences ◽  
Small Lakes ◽  
Acid Base ◽  
Acid Base Equilibrium ◽  
The Stability

The aim of this work is to teach students to determine the stability of small lakes in relation to acidification processes by calculating the buffer capacity of water. A decrease in the pH of natural waters is caused by the influx of acid-forming oxides of sulfur and nitrogen into the atmosphere and water bodies. An increase in the acidity of water bodies has extremely negative consequences, contributes to the leaching of heavy metals, changes the ionic composition of water, and reduces the ability of natural water bodies to heal themselves. Low salinity waters of small lakes in the northern regions are especially vulnerable to acidification processes. The indicators of acid-neutralizing ability, the content of hydrocarbons, the value of the buffer capacity of natural waters are used as criteria for the stability of natural waters. To calculate the buffer capacity, the following indicators of the chemical composition of waters were used in this work: hydrogen index (pH), the content of organic (Corg) and mineral (Cmin) forms of carbon. Concentrations of conjugated forms of components of natural acid-base systems are calculated based on the concept of acid-base equilibrium in solutions of carbonic acid and humic acids.

scholarly journals Copper(II) and lead(II) complexation by humic acid and humic-like ligands

2011 ◽  
Vol 76 (9) ◽  
pp. 1325-1336 ◽  
Author(s):  
Ivana Kostic ◽  
Tatjana Andjelkovic ◽  
Ruzica Nikolic ◽  
Aleksandar Bojic ◽  
Milovan Purenovic ◽  
...  
Keyword(s):  
Salicylic Acid ◽  
Humic Acid ◽  
Stability Constants ◽  
Comparative Investigation ◽  
Binding Ability ◽  
Exchange Method ◽  
Mononuclear Complexes ◽  
Ion Exchange Method ◽  
The Stability

The stability of metal-humate complexes is an important factor determining and predicting speciation, mobility and bioavailability of heavy metals in the environment. A comparative investigation of the complexation of Cu(II) and Pb(II) with humic acid and humic-like ligands, such as benzoic and salicylic acid, was performed. The analysis was realized at pH 4.0, a temperature of 25?C and at an ionic strength of 0.01 (NaCl) using the Schubert ion-exchange method and its modified form. The stability constants were calculated from the experimental data by the Schubert method for complexes with benzoic and humic acid. A modified Schubert method was used for the determination of the stability constants of the complexes with salicylic acid. It was found that Cu(II) and Pb(II) form mononuclear complexes with benzoic and humic acid while with salicylic acid both metals form polynuclear complexes. The results indicate that Pb(II) has a higher binding ability than Cu(II) to all the investigated ligands. The Cu(II)-salicylate and Pb(II)-salicylate complexes showed noticeable higher stability constants compared with their complexes with humic acid, while the stabilities of the complexes with benzoic acid differed less. Salicylic and benzoic acids as humic-like ligands can be used for setting the range of stability constants of humic complexes with Cu(II) and Pb(II).

scholarly journals Comparative study of binding strengths of heavy metals with humic acid

2013 ◽  
Vol 67 (5) ◽  
pp. 773-779 ◽  
Author(s):  
Ivana Kostic ◽  
Tatjana Andjelkovic ◽  
Ruzica Nikolic ◽  
Tatjana Cvetkovic ◽  
Dusica Pavlovic ◽  
...  
Keyword(s):  
Heavy Metals ◽  
Heavy Metal ◽  
Humic Acid ◽  
Metal Ions ◽  
Stability Constants ◽  
Metal Ion ◽  
Heavy Metal Ions ◽  
Exchange Method ◽  
Divalent Metal Ion ◽  
The Stability

The complexation of humic acid with certain heavy metal ions (Co(II), Ni(II), Cu(II), Zn(II) and Pb(II)) was investigated. The stability constants of humate complexes were determined by method which is based on distribution of metal ions between solution and resin in the presence and the absence of ligand, known as Schubert?s ion exchange method. Experiments were performed at 25 ?C, at pH 4.0 and ionic strength of 0.01 mol dm-3. It was found that the 1:1 complexes were formed between metal ions and humic acid. Obtained results of the stability constants, log ?mn, of complexes formed between the metal ions and humic acid follow the order Co(II) < Ni(II) < Cu(II) > Zn(II) which is the same like in the Irving-Williams series for the binding strength of divalent metal ion complexes. Stability constant of complex between Pb(II) ions and humic acid is greater than stability constants of other investigated metal-humate complexes. The investigation of interaction between heavy metal ions and humics is important for the prediction of the distribution and control of the migration of heavy metals in natural environment.

scholarly journals Studies on Metal Gluconic Acid Complexes

2006 ◽  
Vol 932 ◽  
Author(s):  
Peter Warwick ◽  
Nick Evans ◽  
Sarah Vines
Keyword(s):  
Radioactive Waste ◽  
Stability Constants ◽  
Gluconic Acid ◽  
Detrimental Effect ◽  
Solubility Product ◽  
Salt Formation ◽  
High Ph ◽  
Organic Complexes ◽  
The Stability ◽  
Intermediate Level Radioactive Waste

ABSTRACTThe presence of organic complexants, such as gluconic acid, in an intermediate-level radioactive-waste (ILW) repository may have a detrimental effect on the sorption of radionuclides, by forming organic complexes in solution. In order to assess this, stability constants are required for the complexes formed with radionuclides at high pH. This study reports the stability constants for the reactions of some divalent metals with gluconic acid (Gl). The metals studied were Cd, Co, Fe(II), and U(VI) at pH 13.3; and Co and U(VI) at pH 7. The constants were measured by the Schubert (ion-exchange) or solubility product methods. Stoichiometries of the complexes were also determined. At pH 7 each complex was of the form M1Gl1, with log β values suggestive of salt formation. At high pH, log β values were between 13 and 20. The constants have enabled speciation calculations to be performed showing the effect of gluconic acid on the metal's solubility, with data for Ni included. Solubility is predicted to increase in the presence of Gl from pH 9 to 13.5, suggesting that it may have an impact on radionuclide behaviour. The largest solubility increases are for Cd and Co, the smallest, U(VI).

The Application of a Simple Chemical Model of Natural Waters to Metal Fixation in Particulate Matter

1975 ◽  
Vol 53 (5) ◽  
pp. 661-669 ◽  
Author(s):  
Robert D. Guy ◽  
C. L. Chakrabarti ◽  
Laurier L. Schramm
Keyword(s):  
Humic Acid ◽  
Natural Waters ◽  
Anodic Stripping Voltammetry ◽  
Copper Ion ◽  
Freundlich Isotherm ◽  
Stripping Voltammetry ◽  
Differential Pulse ◽  
Chemical Model ◽  
Organic Complexes ◽  
Simple Chemical

A simple chemical model was used to investigate the mechanisms controlling the distribution of metals between soluble and particulate fractions in natural waters. The model particulates used were potassium bentonite, hydrous MnO2, and solid humic acid. The soluble species in natural waters were modelled by soluble humic acid, tannic acid, and bicarbonate. The sorption curves for Cu(II), Cd(II), and Zn(II) onto humic acid and MnO2 obeyed Langmuir adsorption isotherms whereas the sorption of the above ions onto bentonite followed a Freundlich isotherm. Chemical analysis of the total model using atomic absorption spectroscopy and differential pulse anodic stripping voltammetry indicated that copper distribution depends on the pH of the suspension: above pH 6.0, 50 % of the copper is sorbed onto the particulates whereas the copper in solution is in a complexed form; between pH 6 and 3.8 the soluble copper is distributed between organic complexes and "free" copper ion; between pH 4.2 to 2.5 copper is being desorbed from the particulates; and below pH 2.5 all the copper is present in solution as "free" copper ion.

Changes in the Humic Acid–Metal Complexation Characteristics Depending on Humification Degree / Humīnskābju – Metālu Kompleksveidošanās Rakstura Izmaiņas Atkarībā No Humifikācijas Pakāpes

2012 ◽  
Vol 51 (3) ◽  
pp. 228-237
Author(s):  
D. Dudare ◽  
M. Klavins
Keyword(s):  
Humic Acid ◽  
Stability Constants ◽  
Humic Acids ◽  
Complex Stability ◽  
Peat Layer ◽  
Raised Bog ◽  
Complexing Capacity ◽  
Humification Degree ◽  
Complexation Process ◽  
Complex Stability Constants

The aim of this study is to determine the Cu(II) complexing capacity and stability constants of Cu(II) complexes of humic acids isolated from two well-characterized raised bog peat profiles in respect to the basic properties and humification characteristics of the studied peats and their humic acids. The complex stability constants significantly change within the studied bog profiles and are well correlated with the age and decomposition degree of the peat layer from which the humic acids have been isolated. Among factors that influence this complexation process, molecular mass and ability to form micellar structures (supramolecules) of humic substances are of key importance.

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