• Analytical Science and Technology
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• v.12 no.3
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• pp.177-183
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• 1999

The determination method of free acid in spent U-Al nuclear fuel solutions by Gran plot titration was described. Effect of U(VI) and Al(III) on the alkalimetric titration of nitric acid was investigated in oxalate complexing media as well as in noncomplexing media. Positive biases were observed in both titration media when the end-point was estimated by the Gran plot method. It was found that the cause of the bias was U(VI) in the oxalate complexing media, but Al(III) in the noncomplexing media. The relative error was less than 1% in the titration of 0.1 M $HNO_3$ at a U(VI) : Al(III) : $H^+$ mole ratio of up to 2:12:1 as long as the pH of the oxalate titration media was sustained to be below 5.0 at the beginning of titration. The method was successfully applied to the determination of nitric acid in a solution of HANARO reactor fuel with U:Al mole ratio of 1:6.

• Bulletin of the Korean Chemical Society
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• v.20 no.1
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• pp.59-64
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• 1999

Based on the study of hydrolysis behaviour of U(Ⅵ) ion and major fission product metal ions such as Cs(Ⅰ), Ce(Ⅲ), Nd(Ⅲ), Mo(Ⅵ), Ru(Ⅱ), and ZR(Ⅳ) in the titration media, the performance of noncomplexing-alkalimetric titration method for the determination of free acid in the presence of these metal ions was investigated and its results were compared to those from the completing methods. The free acidities could be determined as low as 0.05 meq in uranium solutions in which the molar ratio of U(Ⅵ)/H+ was less than 5, when the end-point of titration was estimated by Gran plot. The biases in the determinations were less than 1% and about +3% respectively for 0.4 meq and 0.05 meq of free acid at the U(Vl)/H+ molar ratio of up to 5. Applicability of this method to the determination of free acid in spent fuel solutions was confirmed by the analysis of nitric acid content in simulated spent fuel solutions and in a real spent fuel solution.

• Journal of Soil and Groundwater Environment
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• v.24 no.1
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• pp.10-16
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• 2019

Alkalinity is an essential parameter for understanding geochemical processes and calculating partial pressure of $CO_2$, dissolved inorganic carbon, and mineral saturation indices. The Gran Titration Method (GTM) is one of the most accurate methods for measuring the alkalinity in water samples. However, this method has not been widely employed in measuring groundwater alkalinity in Korea, probably due to inadequate and insufficient understanding of the method. In this regard, this article was prepared to introduce GTM and related know-hows learned from the authors' experiences in measuring alkalinity. This paper also introduces a MS Excel-based alkalinity calculator as a handy tool for GTM.

• Economic and Environmental Geology
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• v.51 no.6
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• pp.509-520
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• 2018

Alkalinity is one of the basic variables, which determine geochemical characteristics of natural waters and participate in processes changing concentrations of various contaminants either directly or indirectly. However, not a few laboratories and researchers of Korea still use alkalinity-measurement methods not appropriate for groundwaters, and which becomes one of the major reasons for the poor ion balance errors of the geochemical analysis. This study was performed to review alkalinity-measurement methods, to discuss their advantages and disadvantages, and, thus, to help researchers and analytical specialists in analyzing alkalinity of groundwaters. The pH-titration-curve-inflection-point (PTC-IP) methods, which finds the alkalinity end point from the inflection point of the pH titration curve are revealed to be most accurate. Gran titration technique among them are likely to be most appropriate for accurate estimation of titrant volume to the end point. In contrast, other titration methods such as pH indicator method and pre-selected pH method, which are still commonly being used, are likely to cause erroneous results especially for groundwaters of low ionic strength and alkalinity.

• Journal of the Korean Chemical Society
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• v.51 no.1
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• pp.21-30
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• 2007

A multiwavelength spectrophotometric titration method was applied to study protolytic constants of four water-soluble vitamins, folic acid(vitamin B9 or B0), thiamine(vitamin B1), riboflavin(vitamin B2) and pyridoxal (vitamin B6) in binary ethanol-water mixtures at 25oC and an ionic strength of 0.1M NaNO3. The protolytic equilibrium constants, spectral profiles, concentration diagrams and also the number of components has been calculated from the curve fitting of the pH-absorbance data with appropriate mass balance equations by an established factor analysis model. DATAN program was used for determination of acidity constant and SPECFIT program was used for calculation of standard deviations and partial correlation coefficients. A glass electrode calibration procedure based on the four parameter equation pH=α+SpcH+JH+[H+]+ JOH-Kw/[H+] based on the Gran,s plots was used to obtain pH-readings in the concentration scale (pcH). The effect of the solvent on the protolytic constants was discussed.

• Journal of Soil and Groundwater Environment
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• v.29 no.1
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• pp.1-9
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• 2024

As part of monitoring technology aimed at verifying the stability of CO₂ geologic storage and mitigating concerns about leakage, a method for measuring the pH and alkalinity of high-pressure fluid samples was established to obtain practical technology. pH measurement for high-pressure samples utilized a high-pressure pH electrode, and alkalinity was measured using the Gran titration method for samples collected with a piston cylinder sampler (PCS). Experimental samples, referencing CO₂-rich water and CO₂ geologic storage studies, were prepared in the laboratory. The PCS controls the piston, preventing CO₂ degassing and maintaining fluid pressure, allowing mixing with KOH to fix dissolved CO₂. Results showed a 6.1% average error in high-pressure pH measurement. PCS use for sample collection maintained pressure, preventing CO₂ degassing. However, PCS-collected sample alkalinity measurements had larger errors than non-PCS measurements, limiting PCS practicality in monitoring field settings. Nevertheless, PCS could find utility in preprocessing for carbon isotope analysis and other applications. This research not only contributes to the field of CCS monitoring but also suggests potential applications in studies related to natural analogs of CCS, CO₂-rock interaction experiments, core flooding experiments, and beyond.

• Journal of the Korean Society for Marine Environment & Energy
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• v.18 no.1
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• pp.1-8
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• 2015

To evaluate accuracy and precision of determination of total alkalinity ($Alk_T$) and carbon dioxide ($TCO_2$) derived from present study, experiment was applied with $CO_2$ CRM (Batch 132, Scripps Institution of Oceanography; $Alk_T=2229.24{\pm}0.39{\mu}mol/kg$, $TCO_2=2032.65{\pm}0.45{\mu}mol/kg$). As the result, average concentration of $Alk_T$ and $TCO_2$ was $2354.09{\mu}mol/kg$ (~5.6% difference with $CO_2$ CRM) and $2089.60{\mu}mol/kg$ (~2.3% difference with $CO_2$ CRM), respectively. For previous method (Gran Titration) by addition $NaHCO_3$ to deionized water($Alk_T$ $2023.33{\mu}mol/kg$), average concentration was $2193.39{\mu}mol/kg$ (sd=57.15, n=7). Whereas, average concentration was $2017.02{\mu}mol/kg$ (sd=10.98, n=7) for the present study. Recovery yield experiments of total alkalinity in deionized water and seawater were implemented by addition of $NaHCO_3$. The recovery yield of deionized water in the range 0 to $4952.39{\mu}mol/kg$ was 100.8% ($R^2$=0.999), and seawater in the range 0 to $2041.32{\mu}mol/kg$ was 102.3% ($R^2$=0.999). Comparison of $pCO_2$ sensor (PSI $CO_2-Pro^{TM}$) with present method showed very meaningful correlation coefficient ($R^2$=0.977) in the range of 427 to $705{\mu}atm$ and 9.16 to $15.24{\mu}mol/kg$ throught elapsed time for two weeks. Field experiment of diurnal variation of total carbon dioxide was accomplished at Sachon harbor in the coastal waters of East Sea of Korea. Concentration of $Alk_T$ and $TCO_2$ was increased during night, and decreased during daylight hours. The results showed mirror type between $TCO_2$ and dissolved oxygen, which was attributable to photosynthesis and respiration of phytoplankton. Also, open ocean field study was performed to obtain vertical profile of $Alk_T$ and $TCO_2$ in C-C zone (Clarion-Clipperton Fracture Zone), Northeastern Pacific. Average concentrations of $Alk_T$ in the surface mixed layer (0~60 m) and deeper layer below 200 m were $2422.38{\mu}mol/kg$ (sd=78.73, n=20) and $2465.87{\mu}mol/kg$ (sd=57.68, n=103), respectively. And average concentrations of $TCO_2$ were $2134.47{\mu}mol/kg$ (sd=65.4, n=20) and $2431.87{\mu}mol/kg$ (sd=65.02, n=103) in the same depth ranges such as $Alk_T$. Vertical distributions of $Alk_T$ and $TCO_2$ concentrations tended to increase with depth, and analyzed concentrations showed slightly higher than those of previous studies in this area.