Co-reporter:Kodai Kitada, Yusuke Suda, and Norimichi Takenaka
The Journal of Physical Chemistry A July 27, 2017 Volume 121(Issue 29) pp:5383-5383
Publication Date(Web):June 29, 2017
DOI:10.1021/acs.jpca.7b03246
Some reactions (e.g., oxidation of nitrite, denitrification of ammonium) are accelerated in freeze-concentrated solution (FCS) compared to those in aqueous solution. Ice is highly intolerant to impurities, and the ice excludes those that would accelerate reactions. Here we show the acceleration of the N-nitrosation reaction of dimethylamine (DMA) with nitrite to produce N-nitrosodimethylamine (NDMA) in FCS. NDMA is a carcinogenic compound, and this reaction is potentially accelerated in frozen fish/meat. The eaction rate of the N-nitrosation reaction becomes fastest at specific pH. This means that it is a third-order reaction. Theoretical pH values of the peak in the third-order reaction are higher than the experimental one. Freeze-concentration of acidic solution causes pH decrement; however, the freeze-concentration alone could not explain the difference of pH values. The theoretical value was obtained under the assumption that no solute took part in ice. However, solutes are incorporated in ice with a small distribution coefficient of solutes into ice. This small incorporation enhanced the decrement of pH values. Using the distribution coefficient of chloride and sodium ion and assuming those of nitrite and DMA to explain the enhancement, we succeeded in estimating the distribution coefficients of nitrite: 2 × 10–3 and DMA: 3 × 10–2.
Co-reporter:Phan Quang Thang, Yasuaki Maeda, Nguyen Quang Trung, Norimichi Takenaka
Fuel 2014 Volume 117(Part B) pp:1170-1171
Publication Date(Web):30 January 2014
DOI:10.1016/j.fuel.2013.06.054
Co-reporter:Norimichi Takenaka, Itaru Takahashi, Hiroshi Suekane, Koji Yamamoto, Yasuhiro Sadanaga, and Hiroshi Bandow
The Journal of Physical Chemistry A 2011 Volume 115(Issue 50) pp:14446-14451
Publication Date(Web):November 14, 2011
DOI:10.1021/jp2093466
A reaction of ammonium nitrite in ice was investigated. Upon freezing, some nitrite is oxidized by dissolved oxygen and some nitrite reacts with ammonium to produce nitrogen and water in a denitrification reaction. The former reaction was accelerated only during freezing, and the latter one was accelerated even after the whole sample was frozen. The denitrification reaction proceeded at very low concentration in ice, which were conditions under which the reaction would not proceed in solution. The nitrogen production increased linearly with increasing initial concentration of ammonium nitrite. The concentration factor in the unfrozen solution in ice was estimated to be 50.6 when the initial concentration was 0.5 mmol dm–3, as obtained from comparison of reaction rates in solution and in ice. A new method for determination of the activation energy is proposed that gives a value of 53 to 61 kJ mol–1 for denitrification. The reaction order of the denitrification process is also determined using our method, and it is concluded to follow third-order kinetics.
Co-reporter:Norimichi Takenaka, Kayoko Takayama, Naofumi Ojiro, Wataru Shimazaki, Kingo Ohira, Hiroyuki Soda, Takahiko Suzue, Yasuhiro Sadanaga, Hiroshi Bandow and Yasuaki Maeda
The Journal of Physical Chemistry A 2009 Volume 113(Issue 44) pp:12233-12242
Publication Date(Web):October 9, 2009
DOI:10.1021/jp9054395
The fate of salts in drying aqueous solution was investigated. In the drying of acidic solutions, weak acid ions and chloride ions combine with protons and evaporate, depending on the proton concentration. In the drying of alkaline solutions, weak acid ions evaporate or remain as salts depending on the ratio of the concentrations of excess nonvolatile cations (the difference between concentrations of nonvolatile cation and nonvolatile anion) to volatile anions defined as ΔCA. Under neutral and alkaline conditions, the fate of nitrite depends not only on ΔCA but also on the drying speed. Nitrite is converted to N2, which is formed by reacting nitrite with ammonium (denitrification), NO and NO2, HONO and salts. In urban areas, nitrite and ammonium can appear in high concentrations in dew. HONO in the atmosphere affects the ozone concentration, but dew formation decreases the concentration of HONO. If chemical denitrification occurs, nitrogen species will decrease in the environment, and as a result, the ozone concentration could decrease. Ozone levels show an ozone depression when dew formed, and a Box model simulation showed an ozone depression by decreasing HONO levels.