Determination of Free Acid in Presence of Hydrolyzable Ions

Booman, G. L.; Elliott, Mark; Kimball, R.B.; Cartan, F.O.; Rein, J.E.

doi:10.1021/ac60134a035

Cited by 41 publications

(14 citation statements)

References 7 publications

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“…The free acidity of the sample was also determined at the predetermined end-point pH value of 3.0 as well as by the standard method of using potassium oxalate as the complexing agent. 16 …”

Section: Determination Of Free Aciditymentioning

confidence: 99%

Sequential Determination of Free Acidity and Plutonium Concentration in the Dissolver Solution of Fast-Breeder Reactor Spent Fuels in a Single Aliquot

Dhamodharan

Pius

2016

ANAL. SCI.

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A simple potentiometric method for determining the free acidity without complexation in the presence of hydrolysable metal ions and sequentially determining the plutonium concentration by a direct spectrophotometric method using a single aliquot was developed. Interference from the major fission products, which are susceptible to hydrolysis at lower acidities, had been investigated in the free acidity measurement. This method is applicable for determining the free acidity over a wide range of nitric acid concentrations as well as the plutonium concentration in the irradiated fuel solution prior to solvent extraction. Since no complexing agent is introduced during the measurement of the free acidity, the purification step is eliminated during the plutonium estimation, and the resultant analytical waste is free from corrosive chemicals and any complexing agent. Hence, uranium and plutonium can be easily recovered from analytical waste by the conventional solvent extraction method. The error involved in determining the free acidity and plutonium is within ±1% and thus this method is superior to the complexation method for routine analysis of plant samples and is also amenable for remote analysis.

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“…The free acidity of the sample was also determined at the predetermined end-point pH value of 3.0 as well as by the standard method of using potassium oxalate as the complexing agent. 16 …”

Section: Determination Of Free Aciditymentioning

confidence: 99%

Sequential Determination of Free Acidity and Plutonium Concentration in the Dissolver Solution of Fast-Breeder Reactor Spent Fuels in a Single Aliquot

Dhamodharan

Pius

2016

ANAL. SCI.

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“…With conventional methods the loss of titrant due to this hydrolysation is indistinguishable from the titrant necessary for the neutralisation of the sulphuric acid, and the titrations are erroneously high. The problem is magnified as the ratio of hydrolysable cation to free acid increases, particularly to ratios higher than Although various methods have been reported to determine the concentration of sulphuric acid in the presence of hydrolysable cations, no universal methods exist for this determination [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The methods are usually specific to a defined matrix and can be classified into five main groups according to the strategy employed:…”

Section: Samevattingmentioning

confidence: 99%

“…Of the seven procedures on file at Mintek based on previous research [4][5][6][7][8][9][10][11][12][13][14][15][16], two are based on the formation of complexes with the hydrolysable cations (the potassium oxalate method and the fluoride method). The lithium chloride method is based on the enhancement of the activity of hydrogen ions.…”

Section: Overcoming Interferencementioning

confidence: 99%

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Overcoming interference from hydrolysable cations during the determination of sulphuric acid by titration

Pillay

Barnes

Staden

2001

Analytica Chimica Acta

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interference, but all suffer from certain limitations -especially at high cation to free acid ratios. A simple and practical method is suggested to overcome the effect at high cation concentrations. It is based on the addition of neutral salt to enhance the activity of the protons, which coincides with a shift in the inflection of the titration curve. This results in a shift of the titration end point to a lower pH, and a better separation of the free acid and cation curve. This effect, combined with performing the titration in a methanolic environment, decreases the hydrolysation of the cations and improves the inflection of the titration curve to such an extent that more than a ten-fold excess of iron (III) concentration (the most serious interference) could safely be tolerated during the free acid titration. SamevattingGedurende To Dr Elaine lones-Watson, the opportunities you afforded me gave me the confidence to take on this project. Thank you for your guidance, and encouragement.To my parents, you have enabled me to have an education, which you yourselves never had. Thanks to you I have achieved this academic milestone. I will be eternally grateful.Thanks to MINTEK for the financial support and the time allowed for completion of this project. During the acid-base titration, the hydrolysable cations form basic salts or hydroxides, which consume part of the titrant [2,3]. With conventional methods the loss of titrant due to this hydrolysation is indistinguishable from the titrant necessary for the neutralisation of the sulphuric acid, and the titrations are erroneously high. The problem is magnified as the ratio of hydrolysable cation to free acid increases, particularly to ratios higher than Although various methods have been reported to determine the concentration of sulphuric acid in the presence of hydrolysable cations, no universal methods exist for this determination [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. The methods are usually specific to a defined matrix and can be classified into five main groups according to the strategy employed:• addition of a complexometric reagent [4][5][6][7][8][9][10] • removal or reducing of concentration, of the interfering cation in the aqueous phase to be analysed [4] • electronic or mathematical resolution of the inflections on the titration curve [7] • use of mathematical derivative techniques [7] • Gran Plots [9,10,17,18] The reported methods are able to tolerate an iron(III) to free acid ratio of 2: 1. The samples usually analysed at MINTEK have a higher iron(III) to free acid ratio. To compound the problem, the samples also contain high concentrations of copper(II), iron(II), manganese(II), cobalt(II), and nickel(II).It has been reported [13][14][15][16] that changing the medium in which one performs the titration can alter the activity of the proton and cations. Lithium chloride has been suggested as a neutral salt that would enhance the activity of the proton thereby reducing the interference from the hydrolysable cations.The aim of this inves...

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“…The acidity of a salting solution was determined by an oxalate complexing-pH titrimetric method 9 and this salting solution then was used to investigate the effect of acid on the determination of uranium. This salting solution was prepared as 2.8M Al(NO:i),H, 0.025M tetrapropylammonium hydroxide, 2M NH 4 OH.…”

Section: Effect Of Acidity Onmentioning

confidence: 99%

Analytical methods for fissionable materials in the nuclear fuel cycle. Covering June 1974--June 1975

Waterbury¹

1975

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REFERENCES i4It* I.I.J S,,,n "",-,1,, nl"TT, ? ANALYTICAL METHODS FOR FISSIONABLE MATERIALS IN THE NUCLEAR FUEL CYCLECompiled by Glenn R. Waterbury ABSTRACT Progress continued on method development for the dissolution of difficult-to-dissolve materials, the automated analysis of plutonium and uranium, the preparation of plutonium materials for the Safeguard Analytical Laboratory Evaluation (SALE) Program, and the analysis of HTGR fuel and SALE uranium materials. The previously developed Teflon-container, metal-shell apparatus was applied to the dissolution of various nuclear materials. Gas-solid reactions, mainly using chlorine at elevated temperatures, are promising for separating uranium from refractory compounds. An automated spectrophotometer designed for determining plutonium and uranium has been tested successfully by the New Brunswick Laboratory. Procedures were developed for this instrument to analyze uranium-plutonium mixtures and the effects of diverse ions upon the analysis of plutonium and uranium were further established. A versatile apparatus was assembled to develop electrotitrimetric methods that will serve as *he basis for precise automated determinations of plutonium. Progress with the first of these methods is reported. Plutonium materials prepared for the SALE Program were plutonium oxide, uranium-plutonium mixed oxide, and plutonium metal. Improvements were made in the methods used for determining uranium in HTGR fuel materials and SALE uranium materials. Plutonium metal samples were 'prepared, characterized, and distributed, and half-life measurements were in progress as part of an inter-ERDAlaboratory program to measure accuracy the half-lives of longlived plutonium isotopes.

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Determination of Free Acid in Presence of Hydrolyzable Ions

Cited by 41 publications

References 7 publications

Sequential Determination of Free Acidity and Plutonium Concentration in the Dissolver Solution of Fast-Breeder Reactor Spent Fuels in a Single Aliquot

Sequential Determination of Free Acidity and Plutonium Concentration in the Dissolver Solution of Fast-Breeder Reactor Spent Fuels in a Single Aliquot

Overcoming interference from hydrolysable cations during the determination of sulphuric acid by titration

Analytical methods for fissionable materials in the nuclear fuel cycle. Covering June 1974--June 1975

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