Arakawa, S.

Hosoda, K.

Itano, A.

Okayama University Scientific Achievement Repository

Investigation on the Bi1mann's Quinhydrone Electrode. III. (Further studies on the electrode and ag町 bridge.)By A. Itano， S.Arakawa and K. Hosoda. [Feb. 20th， 1927] Introd uction : In our previous publications， the description of the quinhydrone methodt) and the table for calculations of the electromotive force into the PH values2) were published. In this paper， the results of the following investigations are reported: J. To test the e伍ciencyof the method in determination of PH and titra-tion of di任erentsolution by using various arrangements. 2. On the uses of agar bridge and its study under different working conditions and treatment. Experimental. Experimentよ Determinationof PH of the following six differ百 1tsolu-tions were carried out with di白b明lIchain， and compa，red with the H2-electrode as noted ir the table : Solution A. CLARK'S buffer solution.8) " B. Soil solution.め" C. Soil Filtrate.5) " D. N utrient broth.め" E. Medium for the cellulose fermenter.7) " F. ASHBY'S solution.8) 1) ITANU， A.alJd K. Hc洛0.¥，J. Agr. Chem. Soc. of Japan，.IT， 2， IJ， 1926. 2) Jbid 1 lJ， 3. 2J， 1926. 3) CLA且K，M.， Tbe determ~nati円nof Hydr噌聞いns，1923. 106. 4) p問pa問dby JSCHEREKOV'S metbod: F. N. Parker， Sflil Science XIJ， 214， 1926; described in detail later. 5) se p. 340 for tbe p陪parati円，n.6) • The standard brotb (F陀d，Soil B.1cteriol唱y，89. 1916). 7) Vilj噌 netc.， J. Agr. Science XVJ， part 1， 3， 1926. 8) ASHBV， S. F.， ibid n. 35. 1907・338 A. ITANO， S.ARAKAWA & K. HOSODA: These soIutions were chosen since they are used frequently in our Iabo-ratory， and may be of interest to those who are engaged in the similar work. The determinations were carried out by the H 2• electrode and the quin-hydrone electrode against the calomel and quinhydrone standard electrode. The results are given in the following table : Table 1. Deぬrmina.tionof PH in di偽 rentSolutions. PH determined by Solutins Q-C+ Q-Qs* Hz.electrode・A I ~_ 3・96 4.∞ B. I 6.71 I 7・01 I 7.04 C. I 6.29 I 6.45 I 6.43 D. 7・55 I p2 I 7.19 E. 6.96 6.70 I 6.71 F. I 7勾 I 7.64 7・70Table 1. indicates that the quinhydrone electrode gives slightly Iower PH except in B and C. However the quinhydrone electrode may be used sati-factorily in aI these solutions for general pu中ose.Experi初ent11. Titration of the Solutions used in Experiment 1. The titration was carried out in those solutions which were used in Ex-periment 1 to ascertain the efficiency of the electrode as well as the buffer property of these solutions. Solution A. Buffer Solution. 5occ. of the buffer solution was taken and titrated with N/lO NaOH. The results are given in Table 1. and Graph 1. Table 1. Titra.tion of位ldBuffer Solution. NぷNaOHI Q-Ci Q-Qs i 'lt PH 'lt O. 0.1355 3・96 0.1106 3. 0.1162 4.30 0.1296 前. 0.10[4 4・54 0.1450 9. 0089; 4・78 0.1564 [2. 0.0757 5.0J 01'0、15. 0.0585 5.33 0.[871 18. 0.0330 5・76 0.2119 21. -0.1 [74 8.43 0・3637• Hydr(ヰ~eDg錨 electrnde~ainst the calnn首Ielectrnde. (See Figure IT.) + Quinhydro出:lgaIDstlbe calnmel standard electrnde. (See Figure IIr.) * " "" quinhydmne" " """ 12・cI'H 4.∞ 4・334・594.81 5.04 5・335.78 8.45 i &i F，円ran arrangeπent ()f apparatus， se Figu陀 V. The arrangement shηwn in Figu陀 IVis used when the titration is caried哨 tby H~.el配trnde.IDvestigation I)D the Biilmann's Quinhydrone EJectrode. II. 339 PH 9.0 8.0 7.0 6.0 5・04.0 Graph 1. m色rationof也eBufter Solution. ←一-e Q.一一C.0四--0 Q.一Qs.21. 18. JS・1:2. 9. 6. 3. o. cc. Table I. and Graph 1. indicate that the buffer solution has the strong buffer action as expected. After each addition of the alkaIi， an equilibrium was estabIished veηr quickJy and the electrode responded accurately. So far as the chains are concerned， they gave very c10se results. Solution B. Soil Solution. As it was indicated previously， this 'solution w剖 preparedaccording to IscHEREKOV's method: 5∞grams of the air dried soil from our experimental plot (rice-field) was packed in a glass tube of which diameter is about one and one half inch. The soil was saturated with the distilled water for about twelve hours. The water holding臼 pacityof the soil was found to be 20%. After the saturation， the water was displaced by means of the absolute alcohol. About 80 cc. of the solution was obtained by this pr∞ess in ten hours， and 50 cc. of it was taken in our experiment. The solution thus prepared was found to be PH 7.01. First enough N/w NaOH was added to bring the PH to 8.55 and then N/1∞H Cl was added oneとc.at a time. The results are given in Table 11. and Graph I. 340 CC. N/I∞HCl O. 1. 2. 3. 4・5. 6. 7・8. 9. PH 8.5 7・56.5 S5 4・53・5ム lT.ANO，S. ARAKAWA & K. HOSODA: π -0・1258一0.11230ー・句49-0.0578 0ー.0228O.∞50 0.0350 0.0770 0.1173 0.1422 Table II. Ti色ra.tionof也eSoil Solution. Q-C Q-Qs PH 7τ 8.55 0.37∞ 8.33 0・35808.01 0.3370 7・37 0.3014 6.75 0.2670 6.26 0.2<j!∞ 5・73 0.2073 S.∞ 0.1676 4.29 0.1266 3.85 0.1010 Graph I. Titra.tion of也eSoil Solu色ion.ふー → Q;-一C0---0 Q一Qs.O. 1・ 2・ 3・ 4・ 5・ 6. 7. S. 9・∞.1~.C. PH 8.54 8.33 7・967・346.74 6.25 5.68 4・974・263・79Table II. and Graph I. indicate that the electrode in both of these chains gave veη， close readings， and veη， litle buffer action exist in the soIution. Solution C. Soil FiItrate. SO gm. of the air dried soil， the same ~oiI which was used for preparation of tne soil soll1tion， was mixed with 2 SO cc. of the distiIled water and Iet the • Investigation on the Biilmann's Quinhydro田 Electrooe. 111. 341 mixture stand over night， and filtered through the filter paper.τbe filtrate thus prepared was found to be PH 6.45・ Previousto the titration， the PH was made to 8勾 byaddingN/20 NaOH， and was titrated with N/I∞HCl by adding one CC. at a time. The results are shown in Table IV. and Graph II. c. N/I∞HCl . Tab!e IV. Titration of色.heSoil Suspension. Q-C 140C. Q-Qs π PH π PH -0.1110 8.29 0・3S'iO 8.26 -0.0803 7・75 0.3Z78 7-78 O.∞87 6.19 0.2340 6.15 0.1180 4・29 0.1250 4・230.1521! 3.68 0.0905 3.63 0.1681 3.40 0.0757 3・370.1778 3.Z3 0.0667 3.20 Graph II. 四tra色ionofぬeSoil. PH 8.0 1. 。.2 • •..• ??????7.0 ←-eQ.一C~---o Q一Qs.6.0 50 4.0 3・0。， 6. c. 3. 1. 2. 4・ 5・342 A. ITANO， S.ARAKAWA & K. HOSODA: 1t is interesting to note that a marked bu能raction was observed from PH 4・3and lower. This may be due to the presence of coIloidal matter・inthe filtrate， thus prepared， more than in the solution which was used in the preced-ing experiment. Solution D. N utrient Broth. The standard nutrient broth was used. The PH value of the broth was 7.22， and the reaction was adjusted to PH 8.39 with NjlO NaOH previous to the titration with Njso HCl of which results are given in Table V. and Graph 1V. Table V. Titration of色heNutrient Broth. 14・C.c. Q-C Q-Qs N/50 HCl Tτ PH マτ PH O. -0.1160 8.39 0.3600 8.37 2. -0.0808 7・77 0.3250 .7・7O4. ー0.0514 7.25 0.2971 7.26 6. -0.03∞ 6.87 0.2750 6.88 8. 0ー.0122 6.56 0.2565 6.55 10. 0.01l5 6.14 0.2330 6.13 12. 0.0385 5.67 0・2065 5.66 14. 0.0630 5・24 0.1815 5.23 16. 0.0828 4ト89 0.1618 4.b8 18. O.句90 4・白 0.1451 4.59 20. 0.II35 4・32 0.1308 4.34 22. 0.1265 4.13 0.1170 4.10 24. 0.1378 3・92 0.1065 3・91PH Graph 1V. ~O ， Titration of也eNutrient Broぬ.8.0 • " ι_'Q;一一C.7.0 6.0 5.0 4.0 O. 2・ 4. 6. 8. 10. 12. 14・ 16. 18. 20. 22. cc. Jnvestigation on the B脳i“lmann山l'、sQ恥u叫山lI取t訂E向 d命ron円予)eElec山tr円nde' 1町I口r. 343 Table V. and Graph IV. indicate the presence of bu能raction as it is natura11y expected from the nature of the solution Solution E. Medium for the Cellulose Fermenter. The pH of this solution was 6.70， and N/IO HCl was added to bring it to PH 3.08 and was titrated with N/20 NaOH. The results are shown in Table VI. and Graph V. N/:'NaOH I O. 2. 4・6. 8. [0. 12. [4. 16. 18. 20. 22. pH 8.0 7.0 6.0 5.0 4.0 3.0 Table VI. Ti色rationof Medium for也.eCellulose Fermen旬r.Q-C Q-Qs ヲτ PH π 0.1884 3・08 0.05∞ 0.[704 3・37 0.0736 0.1416 3.87 0.1024 0.1∞5 4.62 0.[43[ 0，0440 5・57 0.2000 O.∞l!2 6.:n 0.2384 ー0.0065 6.47 0.25叩-ーO.O:UO 6.7[ 0.2650 -0.0348 b.96 0.2786 一0.0490 7.22 0.2927 -0.0663 7・5[ 0.309[ -0.0980 8.07 0.3425 Graph V. Titration of Medium for位砲 CelluloseFermenter. ι__. Q;-ー C.0---0 Q;--Qs. 14'・C.PH 308 3・323.84 4.55 5.54 6.2[ 6.43 6.匂6.93 7.17 7-47 8.04 22. 20. 18. 16. 14・ 12. 10. 8. 6. 4・ 2. 0・凪344 A. ITANO， S.ARAKAWA & K. HOSODA: τbe marked buffer action is noted， which is due to the presence of such salts as phosphates and calcium. There is a slight di佐renceamong the results obtained by two chains but it is so smaII that practically no significance. So!ulion F. Ashby soIution. The determination of pH in Ashby solution was carried out by various chain to see if the presence of CaCOa in excess has any influence on the results. Table VII. De色erminationof PH in ABhby Solution. H.-C 7・857・76Q-C 7.64 7.65 H.-Qs 7.89 7.84 Q-Qs 7.70 7均As the above resuIts indicate， the various chain， inboth cases， with or without CaCOR makes litle difer百lce.五ψerimtnt111. Investigation on the Use of Agar Bridge. This experiment was carried out in two parts， asdescribed below: Paげよ Totest the e侃ciencyof the agar bridge in connection with the determination of hydrogeQ ion concentration of the soil in suspension and the filtrate: the agar bridge was prepared according to MICHAELlS1) in two shape， as illustrated in Fig. 1. A and B. The bridge B was used by placing the solid potぉsiumchloride in a arm-cup (c). The soil sample was prepared by tak-ing I∞gm. of the rice-field soiI and 2∞cc. of distilled water， shaken for half an hour. A portion of the suspension was filtered and the remainder was used without. The determination was carried out as follows : Materials. Fi1trate: H.ー CQ-C Suspensinn : H.-C Q -C Table VIII. Investiga低onon也euse of .Aga.r Bridge. Agar Bridge With剖 t A 6.12 6.24 6.19 6.21 6.14 6.%7 6.0J 6.00 1) MI叩 AELlS，L. Praktikum der Physikali民henChemie， 192Z， 161・B 6.04 6.16 5・715.66 lnvestigation on the Biilmann's Quinhydrone Electrode. lII. 345 As the table indicates， with the filtrate both chains with or without any one of the bridge gave veη， close results. How，ever with the suspension， a chain (QーC)gave higher concentration especiaIIy with the bridge B. The diffusion of solid KCI in the bridge seenis to cause the difference. PIERRE1) stated that the use of a new bridge， inthe soiI work， gives the higher hydrogen ion concentration which is due to a sIight diffusion of KCI from the ends of the agar bridge. To eIiminate this error， he recommends the soaking of the newly prepared agar bridge for one hour in conductivity water before the use， and to keep it in contact with the soiI suspension only while the successive readings are taken. The results obtained in our experiment with the bridge B confirms his statement. Part II. To test the effect of agar bridge on the determination of hy-drogen ion concentration under various conditions. The bridge is inserted as shown in Fig. VI. in the chain A. and B. as foIIows: Chωin A. Hg-HgCI I N/IO KCll Sat. KCI ， Cha切 B.1 Quinhydrone Pt (b凶削 HClo.OlN I Sat. KCI I KCI 0.09 N Unknown soIution 1.，. Bridge l+Qui向 drone戸(blank)I Unknown soIution 1-. Bridge I '"'+~Q~i向The buffer soIution (Clark)， PH 5.84 was used for the determination with di任erentchain as noted in the table : Table IX. Deぬrmina.tionof Hydrogen lon Conoentra.tion wi白血.eBridge. Method H..eletrode Chain A. " " ， withnut bridge Chain B. " "， with円utbridge PH determined 5.84 5.84 5・935・145・93Table IX. indicates that with or without insertion of the bridge makes very Iitle difference， ifthe diffusion is eIiminated. N ext the bridge was subjected to the di任erenttreatments as foI1ows : 1. The bridge was kept in the quinhydrone mixture for 30 minutes. 2. ibid for 2 hours. 3. ibid for 4 hours. 1) PIER.RE， W. lL，S円ilscience， 20， '9Z 5， 287・346 A. ITANO， S.ARAKAWA & K. HOSODA: 4. The bridge was soaked in the disti1Ied water for 2 hours. 5. ibid in the saturated KCI for 2 hours. Table X. The Aga.r Bridge a.nd VariOU8 Treatment. Chaios Treatments PH Determioed A. 1. 5.84 2 5.89 " 3・ 5.88 " 4・ 5.91 5・ 5.88 B. 1. 5.86 " 2. 5・92" 3・ 5.')0 l，t 4・ 5・96" 5. 5.92 Table X. indicates that various treatments of the bridge do not effect the results appreciably， and an old bridge can be used repeatedly with due pre-cautions such as thorough immersion of the bridge in disti1Ied water and kept in the saturated KCI solution. Summary and conclusion: 1. The quinhydrone electrode can be used satisfactorily for determination of the hydrogen ion concentration and also for the titration of al the solutions used in this investigation. 2. The electrode giv回 closeresults， ¥Vith any chain as iIlustrated in this paper. 3. Various treatments given to the bridge， have practically no effect except a fresh bridge， and bridge B. with an addition of solid KCl. 4. The old agar bridge can be used rep伺 tedlywith due precautions. 5. The soil filtrate h笛 astronger buffer action than the soil solution. 6. A complex medium such as the cellulose medium used in our investi-gation has a strong buffer action， and the electrode does not suffer the pre-sence of various salts. 7. The presence of a alkali salt viz. CaCO， dose not effect the results of determination hy the quiohydrone electrode. Jnvestigation 0目theBiilmann's Quinhydrone Electrode. III. 347 Fig. 1. 門 J-3Fig. ln. Fig. V. Fig. n. マ宮守、Sat. f¥CL H2 electrode Fig. IV. Hz electrode Fig. VI. H2 or Q.eltctr-ocU C.orQs. 

Investigation on the Biilmann's Quinhydrone Electrode. III. (Further studies on the electrode and agar bridge.)

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