Abstract
The critical examination of the spectrophotometric method for determining microgram quantities of phosphate by the n-butyl acetate extraction as molybdophosphoric acid and subsequent development of the molybdenum blue has been made. In this procedure from 2 to 8 ${\mu}g$. of phosphate-phosphorus can be determined under optimum conditions. The final concentration of ammonium molybdate and the final acidity of perchloric acid for the formation of heteropoly acid are suitable to be ranges of 0.5 to 1.1% and 0. 5 to 1. 1 N respectively, and subsequently extracted with 10 ml. of n-butyl acetate. The extract is developed to molybdenum blue with 5.0 ml. of 1. 3% stannous chloride in 1N hydrochloric acid. The color is stable for at least one hour in the use of perchloric acid for the condensation. In order to determination of submicrogram amounts of phosphate, the sensitivity of the molybdenum blue method is hardly sufficient, a sensitive and stable molybdenum(V)-thiocyanate complex method has been investigated. By the procedure less than 1.2 ${\mu}g$. of phosphate-phosphorus can be determined with an accuracy of less than 5% the relative error. The molybdenum(Ⅵ) extracted by the above procedure is reduced to molybdenum(V) in the extract directly with a solution of 4 to 10% of stannous chloride, 0.5 to 1.5 mM of copper, and 0.1 to 0.9 N of perchloric acid as final concentration in 4.3 to 6.3 N of hydrochloric acid or 9.0 to 13.0 N of sulfuric acid by heating for one minute in boiling water, after cooling, the molybdenum(V)-thiocyanate complex color is developed by adding 6.0 M ammonium thiocyanate solution making the final concentration to be in a range of 0.4 to 0.9 M. This procedure the very sensitive, reliable, and stable can be applied to determining submicrogram amounts of phosphate in natural waters with a precision of 1.6 ${\times}\;10^{-2}$ the standard deviation as absorbance.
첫째로 微量燐酸鹽의 定量法으로서 燐몰르브덴酸의 醋酸부틸抽出一鹽化第一주석還元法에 依한 몰리브덴靑法을 더욱 檢討하여 2~8 ${\mu}g$의 燐을 몰리브덴酸 암모늄 및 過鹽素酸濃度 0.5∼1.1%, 0.5~1.1N에서 縮合시켜 溶媒 10ml로 抽出하여 이것을 1.3%鹽化第一주석의 1N鹽酸溶液 5.0ml로 還元시키면 吸光度로서 標準假差 2 ${\times}\;10^{-3}$의 精密度로써 安定한 皇色을 얻을 수 있다. 試料量을 많이 取하면 0.1p.p.m. 以下의 燐酸鹽-燐도 相對誤差 5% 以內에서 容易하게 定量할 수 있다. 다음에 極微量의 燐酸鹽 定量法으로서 몰리부덴(V)-티오시안酸錯鹽發色法을 利用하여 0.3∼1.2${\mu}g$의 燐을 위의 方法에 따라 抽出하여 燐몰리브덴酸 內의 몰리브덴을 溶媒內에서 바로 4.3∼6.3 N 鹽酸 또는 9.0 ∼ 13.0 N 硫酸에서 銅 및 過鹽素酸濃度 0.5~1.5 mM, 0.1∼0.9 N 共存下에서 鹽化第一주석濃度 4∼10% 되도록 하여 1分間加熱還元시켜 6.0M 티오시안酸암모늄을 加해 0.4∼0.9M 되도록 하면 直時 銳敏하고 大端히 安定한 皇色을 얻을 수 있어 1cm셀로써도 天然水中의 燐酸鹽 같은 極微量도 容易하게 定量할 수 있다. 本法의 精密度는 吸光度로서 標準偏差가 1.6 ${\times}\;10^{-2}$며 試料量을 많이 取하면 0.02p.p.m. 以下 0001p.p.m. 까지의 燐酸鹽-燐도 5%以內의 相對誤差로써 選擇的으로 定量할 수 있다.