Itano, Arao

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Investigation on Antimony Electrode for Determination of Hydrogen Ion Cencentration. I. Standardization of an antimony electrode in the buffer solutions and calculation of PH.

Okayama University Scientific Achievement Repository

Investigation on Antimony Electrode for Determination of Hydrogen Ion Cencentration. 1. Standardization of an antimony electrode in 出ebuffer solutions and calculation of PH. By Arao ltano. Ph. D. [August 1 1929] ln the electrometric metheds for determination of the concentration of hy-drogen ions， the hydrogen electrode has been used extensivly and regarded as the standard. Recently the quinhydrone') and hydro-quinhydrone1) electrodes are used to a large extent on account of their simplicity. However aJl these electrodes are inadequate in some instances when some poisonous substances are pre目ntin the担 mples. For example， the hydro~en electrode is known to be poisoned by hydrogen sulfide1駒 ，sodium sulfite刷)， arsenicの，制d関 V町alother substancesd). On the other hand， the other two electrodes are inadequate in presence of fr白 sulfurdioxide') and they are not satisfactory in solutions which contain oxidizing and reducing agents. For these reasons， the use of antimony electrode is recommended especial1y where these causes of error for the other electrodes may be present. The use of antimony electrode in measuring the hydrogen ion concen甘酢tion was investigated in 1923 by UHL and KEsTRANEKベand1(OLTHoFF and HARTONd) in 1925. ln 1928， FRANKE and WILLAMANS) have made a study of the antimony electrode and its application to the determination of hydrogen ion concentration of paper-mill liquor; SNYDER8) applied the method to the deter-mination of the PH values of soils and reported some promising preliminatγ results in comparison with the hydrogen electrode in some soils r却 gingin PH values from about 3.6 to 9.2. 1) BIILMANN， E.， J.Cbem. S侃.(Loodon) 125， 1954， 1921. 2) DAWSON， Sugar. 28， 211， 310， 369， 2926. J) FRANKB， K. W. and J. J. Wlu.AMAN， J. Ind. Chem. 20， 8.句28.4) BREWSTER姐 dRAINES， Intero. Sugar J. 25， sS.192J. 5) CLAI.K， M.， The Determination of Hydrogen 1005， 1923， 265-270. 6) UHL， A.aod KESTllANEK， W.， Monatsh. Chem. 44. 29-34， 1923. 7) KOLTHOFF， 1.M. and B. D. HARTONG， Rec. Trav. Cbim. l'ays.Bao.， 44， llJ， 1925. S) S附 DER，E. F.， Soil ScieDce， 26， 107， 1928. 274 A.ITANO: τrus paper reports on some comparative results obtained by hydrogen and antimony electrodes in the buffer solutions， and later it is intended to test with various types of soils under various conditions. Theoretical. It was found by UHL and K.EsTRAEKt)， and KOLTHOFF) that a metaIic + antimony used as a test electrode， gives a definite potential and SbO is produced， as follows + + Sbρ8 + 2H~2SbO + Hρ. The potential di陥rencebetween the antimony electrode and the solution + is governed by the concentration of SbO which is in turn depend upon the con-centration of hydrogen ions. On the other hand， the solubi1ty ofSbllOs in N/IO HCl and N/lO NaOH is so small that it does not influence the concentration of hydrogen ions in the solution. The equation for caJculation of PH measured against N/IO Calomel elect-rode at 140 C. are given by KOLTHOFF and HAR'τONGぺasfo1o¥'s ( 1 ) E =0.0415 + 0.0485 PH， at 180 C. (from PH 1-5) ( II) E = 0.0句 +0.0536 PH; at 140 C. (above PH 9) On the other hand， FRANKE and WILLAMA:ro..4) offers the equation below: ( II ) E = 0.050 + 0.054 PH， at 250 C. The results given in this publication are based on the叩 ation(III)， cor-rected for N/lo calome1 e1ectrode at 180 C.， which is shown below ; (IV) For， PH= E-0.104 0.054 日 ClI N/IO KCl卜at叫認elm1) UHL :lnd KESTR.ANEK， Loc. cit. 2) KOLTHOFF， Loc. cit. 3) KOLTHOFF組 dHAlITONG， UlC. cit. 4) FB.ANKE and WIIJ...Uf制， Loc. cit. Inv回tigation円nAntimony Electrode for Determination of H' con仰 tration. 1・ 275Experimental. A stick of metallic antimony of about 7 mm. in diameter and about 40 mm. long which was smoothed with a file祖 dwith emery， and solde~ed to a copper lead was used. As the control， the HILDEBRAND'S hydrogen electrode was used as usuaI. The readings for the antimony electrode were taken at the end of one minute while the content of the vessel being shaken by a girl assistant as uni-formly as possible， having a part of the electrode immersed in the solution constantly. A series of KOLTHOFF'S and CLARK'S bu悔rsolutions were used as indicat-ed in Table 1. s ω 圃2Mu， The results are given in Table 1 and Fig. 1. Table 1. Compa.ra.tive Study of Ht-a.nd Antimony Electrode. 1よミ竺::¥ 神I 神1. 神1II. 神IV. 帯V.Ht一ClO 3.80 4.86 6，82 7.86 8.47 Sb-C1。 3.67 4.81 6.92 7079 8.17 Ht一C10 3.97 5.24 6.06 7.74 8.50 Sb-C10 4.∞ 5.20 6.II 7.85 8.26 N. B. The results were corrected for 13・C.，by using the temperatu問 factorprepared by the author and published tc司gelherwith the table for calculali円目 ofPH.The experimental data are plotted against the theoretical line， and shown in Figure 1. (Fig. 1. s. P. 276.) As Table 1. indicates， the antimony electrode gives ve庁 closereadings to those obtained by the hydrogen electrode， and the experimental data obtained by both of these electrodes are in close agreement with the theoretical line as shown in Fig. 1. However somewhat a larger difference is obtained in the a1kaline solutions where the PH values become larger than 8， and this matter wi1l be investigated further in the next paper. ?? 、 ? 、????? ? 、 ? 、? ? ?? 、 ?? ? ? ???? ?•.•• ?????? ? ? ?????? ? 、 ?? ? ? ?? 、? ???????A.ITANo: 。????? ??『 ????????? ????????? ?《?「??? ? ? ? ???? ? 、 ?? ?? 、 ? ? 、 ??雪，. 、• 、.除。，. ‘ 喝両。。•. 、~ ~ : i5; ¥ 輔“ . s E a ー? ? ??、????? ??????s . ‘ 276 ? ??? ?? ?? ? ? ? ? ? ? ?-h・? ??【Summary and Conclusion. The comparative study of the hydrogen and antimony electrodes in the CLARK'S and KOLTHOFF'S bu能rsolutions was carried out， and the results may be summarized as follows : ， which is based on FRANKE and E -O.I04 0.054 Formula IV， PH = I. Jn川叫E伊a瓜ti()n円川叩3流)00叩nA加ntirnon町yEl凶匂叫tr叫叫ef4伽。肘rDe禄以胤t除加e町rminWILLAMAN'S equation， E = 0.050 + 0.054 PH， at250 C.， can be used satisfac-torily for the chain and conditions noted previously. 2. The antimony e1ectrode used in this investigation gave c10se readings to these obtained by the hydrogen electrode in bo血 theCLARK'S and KOL-THOFF'S buffer solutions. 3. Somewhat larger variation among the results were noted in the alkaline solutions which wi1 be investigated further in future together with some other factors such as manner and duration of shaking， and condition of the e1ectrode. 4. In general， an equi1brium was obtained at the end of one minute， shaken by hand. The adequecy of the antimony electrode for determination of the hydrogen_ ion concentration of soils together with田meexperimental factors， wi1 be in-vestigated further and reported in future. 

Investigation on Antimony Electrode for Determination of Hydrogen Ion Cencentration. I. Standardization of an antimony electrode in the buffer solutions and calculation of PH.

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