Fujinaga, Taitiro

Kuwamoto, Tooru

Murai, Shigeo

Sugiura, Kenji

Yamada, Kiyotsugu

English

Kyoto University Research Information Repository

RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:New Gas Chromatograph withCarrier Containing Ligand Vapour :The Instrumentation and theFundamental CharacteristicsFujinaga, Taitiro; Kuwamoto, Tooru; Murai, Shigeo;Yamada, Kiyotsugu; Sugiura, KenjiFujinaga, Taitiro ...[et al]. New Gas Chromatograph with Carrier Containing Ligand Vapour : The Instrumentation and theFundamental Characteristics. Memoirs of the Faculty of Science, Kyoto University. Series of physics, astrophysics,geophysics and chemistry 1974, 34(3): 321-3261974-10http://hdl.handle.net/2433/257549Piv(emoirs of the Faculty of Science, Kyoto University, Series of Physics, Astrophysics,       Geophysics and Chemistry, Vol. XXXIV, No. 3, Article 10, 1974.NEWTheGAS CHROMATOGRAPH WITH CARRIER  CONTAINING LIGAND VAPOURInstrumentation and the Fundamental CharacteristicsBYTaitjro FUJINAGA, Tooru KUWAMOTO, Shigeo MURAI",       Kiyotsugu YAMADA** and Kenji SUGIURADepartment of Chemistry, Faculty of Science, Kyoto University, Kyoto               (reeceived 2Yarcli J9, 1974)                           ABSTRACT   By using the carrier gas containing ligand vapour, it was found that the metal chelatesare quantitatively eluted. Accordingly, the ligand vapour generator was devised forthe gas chromatography of metal chelate cempounds and its instrurnentation and thefundamental characteristics xvere clarified.l. Introduction    In the previous papersi)2)3}, it was reported that the metal chelates can be elutedquaRtitatively by using a carrier gas containing ligand vapour in gas chromatography.Since there have been some dlscussions about this problem, we will clarlfy the details of theappratus used for the experlments and its fundamental characteristics in this paper.    The ligand vapour generator which is used te add a defiBite amount of Iigand vapourto the heiium carrier by passing through the vessel containing ligand solution was manu-factured. The carrier gas containing ligand vapour which is prepared by this generatorwas used for the gas chromatography of metal chelates instead of the original carrier gas.The ligand vapour in carrier gas was continuously supplied into the column and distributedto the gas and liquid phase at a uniform ratio.2. Experimental2-l. Gas Chromatograph    A Yanaco Model G-1800 equlpped with a GCG-252 recorder (Yanagimoto Co., Ltd.,)was used.2-2. Gas Chromatographic Column    Columns were prepared from 3 mm i.d. Å~ leO cm long stainless steel tubing and thecolumn support was 60-80 mesh Gas Chrom-CLH-AW-DCMS. For the stationary liquid  * present address; R & D Division, Sumitomo Electric Ind. Co., Ltd., Osaka ** present address; Shimadzu Seisakusho Ltd., Kyoto322 T. FUJINAGA, T. KUWAMOTO, S. MURAI, K. YAMADA and K. SUGIURAphase, 50/o Silicone DC-550 oil was used, and 50/o Apiezon L and O.50/, Polyethylene glycol(PEG) #20000 were used for comparative investigations.2-3. Gas Chromatographic Conditions   For the most experiments, the column oven was maintained at a temperature of !600C.The injection port and tlte detector block was maintained at a temperature of 2200C. Thefilament current of the theymal conductivity cell was 80mA and the scale of therecorder was set at 2mV/20 cm. The water bath temperature was maintained at20Å}O.050C.   Under these conditions, it was found that the areas of H-TFA(trifiuoro acetylacetone)sample were proportional to the amounts of H-TFA as shown in Fig. 2-b, and thiscalibration curve was used for the following experlments.Vl ,,i HV2 P2gl FF:    s,,ylUe-ii•l   iIIL[tii]v]      i ,l'FAThemnostat:P39s,7 s 9E Eyhaustiv•; p,;rvTR."Fig. 1. 0utline ofVl.•-V;1 Needile VaivePlr"pq Presstire Galigel.w4 Feur-way wap5 Air lnjection PortS $a:np!e lniectian l)ort7 Cc co2umng VFtl Vapor T:ntlS PIow Meterapparatus.He•l tt-TrA adidStien    'Ut centaSnSngH-TFA vapet                  beedsFig. 2. I.igand vapuor generation cell.32 Nni1o aFig. 2-bO: enrrie: : heii-"A; eattkt : hetiun centmtnlng     H+trn vapa"r e.s l.o 1,sAmaupt  ot tl-TrA sample ( gei)Relation between peak area andamounts of H-TFA sample.Column; 50/. Silicone DC-550,Flow rate; 33 m}lmin.INSTRUMENTATION OF NEW GAS CHROMATOGRAPHY3233. Apparatus    The ligand vapour generator was constructed •with two parts; a ligand vapourgeneration cell and a thermostat(water bath). An outline of the fiow circuit from the vapourgenerator to the gas chromatograph is shown in Fig. 1. The generator was connected tothe original fiow circuit before the sample injection port and the portion of the gas linefrom the generator to the injection port was wrapped with asbestos. As shown in Fig. 2,the carrier gas was passed through the ligand vapour generation cell containing ligandreagent in the water bath maintained at a constant temperature. The ligand vapourgeneration cell which is made with giass was constructed with three units ; a chelate reagentreservoir, the mixing unit aRd the prevention of backward current. The reservoir wasfiIIed with approximately 5 m} ligand reagent and about 2 g of 50-80 mesh glass beads.The flow rate of the carrier was regulated with needle valves ViNV4 and pressure gaugesPitvP4 which were installed in the line just before the generator. In addition, the stainlesssteel four way stopcock lt--J4 was used for changing the fiow path of the carrler gas.4. Results and Discussion4-1. Relation between the Water Bath Temerature aRd the Amounts of     Generated K-TFA Vapeur    The amount of generated H-TFA(trifluoroacetylacetone) vapour was regulated bychanging the temperature of the water bath. Then, the amount of generated H-TFAwas calculated from the area which is surrounded by the difference of the heights of thebase lines of helium carrier and H-TFA additive carrier per unit time.    As shown in Fig. 3, the amounts of generated H-TFA was in proportioR to the tem-perature of the water bath over the range of iOON250C and the amount of H-TFAfiuctuation in carrier gas was 50/e for a 10C change of water bath temperature.4-2. Relation between the Amounts of H-TFA Vapour Generated and the Flow     Rate of tke Carrier Gas    The amounts of H-TFA vapour generated depends on the flow rate of the carrier gas,1lls'il1     O XO IO 20 30          Tenperatu:e eE H-TEA vapor gene:ator C ec }Fig. 3. Relation between thermostat temperature and amounts of      generated H-TFA vapour.      Column; 50/o Silicone DC-550, F}ow rate; 33 ml/min.324 T. FUJINAGA, T. KUWAMOTO, S. MURAI, K. YAMADA and K. SUGIURAbecause the generator was constructed by utlllzing the stream of the helium carrier. Asa result, the amount of H-TFA in the carrier gas increases proportionally when the flowrate is above 20 mlfmin., but not vihen it is below 20 mllmin.. The results are shown inFlg. 4. From these results, it was estimated that the decrease in the amounts of H-TFAwere caused by the dilution effect which is due to the fiow circuit. It was found thatthe amount of H-TFA in the carrier gas was regulated toÅ}O.2 ptglml by the fiow rateof the carrier.4-3. Amounts of H-TFA in the liquid phase   The amount of H-TFA in the liquid phase was obtained by ttslng the method ofmeasurements for the surface area4)5). After the base line on the helium carerier settled,Gs321li.,Fig. 4.o                  FiokT rate C ta!lmin.}  Relation between flow rate and amounts of generated H-TFA vapour.  Column; 50/, Si}icone DC-550, H-TFA bath; 20:i:O.050C.Fig. 5.GsgIlx2:iD O 10 20 ]O         TEMPERAk'URE OS H-TFA VAPOR GENERATOR { OC )Relation between temperature of K-TFA vapour generator andsaturated amounts of H-TFA in liq. phase at the equillibrium.Column; 50/o Silicone DC-550, Column Temp.; 1600C,Flow rate; 43 ml/min.esINSTRUMENTATION OF NEW GAS CHROMATOGRAPKY3257ssii,g 4Efi..;sooomoO ; Tb"tl bat}1 3eeca ; TFA bat!1 23- ec   i               le ?e              :'ir,e length of addSng Il-TFA vapov {Fig. 6. Relation between time of H-TFA vapour      of H-TFA in liq, phase.      Column; 50/. Silicone DC-550; Column      rate; 43 mlfmin.  ]erin,)addition and amountsTemp.; 1600C, F}owH-TFA vapour was added to the carrier gas. Wlten the amount of H-TFA was equi-librated in the column, the addition of H-TFA to the carrier gas was stopped. The amountof H-TFA in the liquid phase can be obtalned graphically as the area which is recordedfrom the tlme of the end of the H-TFA addition to the time required for the return to thebase }ine. But, the correction of the amount of H-TFA has to be done for the gas phase,because the area is obtalned as the total of the amounts of H-TFA in the liquid and gasphases. The results are shown in Fig. 5.   Moreover, the time required for the amounts of H-TFA to be equilibrated in theliquid phase was demonstrated by setting the water bath at the temperature of 200C and250C, respectively. As a result, lt was found that the amount of H-TFA in the liquidphase was equilibrated after 30 minutes as shown in Fig. 6. Therefore, a definite amountof H-TFA had to be added for above 30 minutes into the carrier gas in order to keep theamount of H-TFA ln the liquid phase.4-4. Relation between the Amounts ef H-TFA in the Liquid Phase and the    Amounts of H-TFA in the Gas Phase   From the results mentioned above, it was clear that the relatien between the amountof H-TFA in the liquid and gas phases gives straight line when the flow rate of the carriergas is fixed. Accordingly, it was found that any amount of H-TFA in the liquld phasecalt be contrelled by changing the temperature of the water bath and the fiow rate of thecarrler gas.4-5. Gas-Liquid Partition of H-TFA Vapour on the Varieus Stationary Phases   It has been shown empirically that stationary liquids such as non-polarized Apiezon Land weaker poiarized Silicone DC-550 are suitable for the elution of metal chelates. Butthe elution characteristlcs of meta} chelates very remarkably accord!ng to the kind ofstationary iiguid. In view of the above facts, it appeared of lnterest to investigate the effectsof stationary phases on H-TFA vapour. Accordingly, the gas-liquid partition coerdcient326 T. FUJINAGA, T. KUWAMOTO, S. .MURAI, I<. YAiMADA and I<. SUGIURA"i'loeo1 :.: o o sx'6-oBAO; DC sseM; APIEZe: 1.A; nrc. n?.ooeosoDoe1soeo                 !ee lso ?.oo                        COI,v"vl -rEltl. { oe )Fig. 7. Relation between column temperature and the partition coethcient of H-TFA.of H-TFA was obtained at various temperature by using three stationary liquids, that isApiezon L, Sllicone DC-500 and PEG #20000. From Fig. 7, it can be seen that the valuesefthe partition coeficients, k, of H-TFA on Apiezon L and Silicone DC-500 did notvary significantiy under the column temperature of 1300C but decreased gradually attemperatures above 1300C. In the case of PEG #20000, the values of fe, were constaRtunder 2000C but increased rapidly at temperatures above 2eOOC. IB other words, it seemedreasonale to assurne that the gas-iiquid partition properties of the H-TFA in stationaryIiquids expresses the degree of solubiiity of H-TFA vapour in the staÅíinoary liquid at highertemperature.5. Conclusien   The ligand vapour generator was devised for the gas chromatography of metal chelatecompounds. In this apparatus, the amounts of H-TFA in the carrier gas were preciselyregulated to w!thin Å}O.2 pag per 1mi of carrier gas by the flew rate of the carrier gasand the temperature of the water baÅíh.   The behavior of ]E[-TFA vapour in statlonary !iquids was fundamentaliy investigatedand clarified. In addition, it was found that the concentration of N-TFA in PEG #20eOOhaving stronger polarity are very high compared with those in stationary liquids such asSilicone DC-500 and Apiezon L having weaker polarity.                             REFERENCES •2) T. Fujinaga, T. I<uwamoto and S. Murai; Talanta, 18, 429 (1971)2) T. Fujinaga, T. Xuwamote and S. Murai; International Congress on Anal. Chem,, Kyoto, Japan,  Abstract p.103 (1972).3) T. Fujinaga, T. Kuwamote and S. iMurai; Anal. Chim. Acta in press (1974).4) S. J. Gregg, R. Stock; "Gas chromatography 1958" ed. D. H. Desty, p. 90 Butterworth, London (1958).5) R. Stock; Anal. Chern., 33, 966 (1961).

New Gas Chromatograph with Carrier Containing Ligand Vapour : The Instrumentation and the Fundamental Characteristics

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New Gas Chromatograph with Carrier Containing Ligand Vapour : The Instrumentation and the Fundamental Characteristics

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