5Q~-&/y ---------__F

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, ,

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..

..,/ Water Content; of Sout Systems.. ,, .. 1,.Hydrocarbon ,_ .,..

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1

,~. Jo I. UKACS 0. B. ROBINSON U. OF ALBERTA I%IMONTON,.ALTA. , ,; 4/ / t, ,1 ,,

.1 ,..
.,

et ~ al, 6 can be used to predict water solubilit ys with confidence at most temperatures and. pressures A hnowtedge of the equilibrium water copteat of i of interest+ Hqwever, existing theoretical. relationhydrocarbon systems tinder pressu(e .fs irhportant ,shi~s do not permit a calculrttlori of the deviation to the natural gas industrp The information auailfrom these curves when polar substances like able on the volubility of water -in hydrocmbon, hydrogen sulfide are present .?:,:the system, Thus hydrogetr ,sulfide,.. and carbon diozide s~stenrs ~~ , one mu%t reso~ to an experuit~:!tal, approach .,to ~reviewed in thi; paper. and the inflrle$ce of the. , obtain the necessary information. The fact that - mwe important var~abtes. such as tehvperature, laboratory experimental methods frequently involve ,Jwessure and rnrilecrflar structure on volubility in the use of mercury which reasts with hydrogen .liquid,s ar@.gases is discuss~d. sulfide in the presence of watert and that hydrogen A sbitable. cbromatographic technique has been sulfide interferes with many chemical reactions developek for a%itemiriing low concentra~ions of specific for water has contributed to rhe difficqlt y water. Tai!in& of the water peaks %asbeen etimof studying water solbbility in systems ,contahting r?rated by addin~ water to the ,,cartier gas :trea@ @ydiogen ~sulfide. In this investigation the, water The.l method: is :applicbb~e for both gas or Jiquid - content of ..a limited member .of methane-hydrogen samples and is effective in the presence of hydrogen sulfide mixtures was detetmineii using a special > . . - sulfide. t~chnique with ~as chromatography. in The t?xpe;imenta~ study of water volubility ,, metbaue-hydrogen.. sulfide systems izt a t temperature RiVIEW OF PUBL&ED DATA oj 160F has shown that the presence of hydrogen Exprmim&taiIy determined water volubility data sul{icfe causek only a modest increase in ~water have been reported for methane, 14 ethane, -15 cbntent at pressures up to 1~400 .psi~ Theoretical proptie, 9 n-butane, 16 l-butene, 11 ,hydroken considerations and data on pure hydrogen sulfide sulfide 18 and carbon dioxide, 1? These stvdies and carbon dioxide suggest that the effect of both leport the effect of, pressure; tempeiat&e and these ct@ounds wi~l be greater at higher pressures molecular atructt#e on water solubiIity in single and .in. the.liquid phase. , ... . , component gases and liqdds, - ,, ., ~ Fig, 1 compares experimentally determined water , INTROtiUCTION -; solubilitiee in several hydroc,stbons, carbon dioxide .. Before ,transporting br processing aacural gase k and ,hydrogen ~~ sulfide-. at l@F as taken from this and gas condensate s,, it is usuqlly nedgssary to ; . . .! &y ;hem. using suitable dehydration ,equiprnenc. The design and operation of this equi~ment requires a knowledge of the amotuit of water present in the fluid at the reservoir.. and operating conditions; This is influenced by temperature, pressure and . . composition, p,artidtiy - when certain non- .,; hydrocarbon components are. presert~. Field expe,. rience indicates that hydrogen sulfide and carbon ilioxide,, for example, alter the usual water solubiIity relationships appreciably. EIowever, ~n extensive s@irch of tHe Iiterat,pte does not reveal any tpkmti,. tative data on buch:s ystems. !:::-;L=:-;~-\~Foti5wXFi-:nktw~Egase-sj= gen~iaiized:-~rnfiirical= ~. correlations such as the ~one proposed by Katz, d . ..
MOLE FRACTION OF WATER

ABS~~AC~

1 ---

...=

..=-.

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.,

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FIG.

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. ...

. . . . . . .. .

SOLUBILITY OF WATER IN FURE COM1 PONEN13 AT lW. .. . . . . . . .: .. . .. . . ,7 ..,.

., hydrogen sulfide and water-carbon dioxide mixtures> Tle dotted line represents Water consuggest that the presence of these substances in centrations calculated from the vapor pressure of hydrocarbon systems would increase the equilibrium pure water and ideal soIubiIit y reIationships, None .. water content of the syatem~~ especially at higher ~ of the components can be considered to behave ... pressures and pr@cularly in the, hydrocarbon-rich ideally and think+%% significa~t. difference between liqui~_~@e. the soltibilitv , in saturated and unsaturated hvdro= . . carbons , and between hydrocarbons and non:A DEV~LOPMENT OF ANALYTICAL .! hydrocarbons, TEC*IQUE Experimental work o; wa;er volubility: in binary hydrocarbon sjwtems is Iirnited to that of l$cKetta , In addition to the many difficulties wh~ch are ,apd Katz 13on the methane n-butane water ,system, They f$und that at a given pressure and ~~ inlier$nt in che detg~minstion of trace quantities of water in any mifiure, the presence of hydrogen ,$here both the hydrocarbon-rich. temperature, sulfide renders the problem even more difficult, , liquid and vapor exist in equilibrium, dte ~,ater The, formation of mercury sdfide in the presence content of thti. vapor phase is always higher than, 1 of water,and hydrofietr sulfide tweclud~s che use of ., ,.the. water content of the hydrocarbon-rich liquid ,.. mercuiy. as -a ~onf~ning fIuid ht equilibrium cells. , when calculated on a mole fraction basis. The The use of: solid adscrbants is limited to low-. water content of th~- hydrocarbon-rich liquid phask, boiling=poikt. hydrocarbons, Hydrogen sulfide unlike the single component hydrocarbon liquids, interferes in die anaiysis for water by the Karlincreased with increasing pressure. at a constant Fischer method. It was the purpose of this study temperat~e. The water vapor content of more comCOfind a method that would be rapid and accurate, ., plex natbal gas systems h~s b$e,tt investi ated by that would reqtiire only a small sample, and that Dodson and Standing 4 and others, 3#G~ lo, ~~ These. wo@d quantitatively determine water. iit small . studias indicatqd that although the water solconcentrations even in the presence d hydrogen @ility curves fch the. hydrocarbon mixtures deviate sulfide or heavier hydrocarbons. With tljs h mind from ideal behavior, they can be cep~esented by one gas .,chromatography was investigated as a possible average cufke. ovkr a wide. range ~f pressure without .:method. introduq ing serious error. Chromatography has been wideiy used for che Several authors ~)s~g: 11, 14?15, have -attempted analysis of trace compounds. In the direct deterco. describe the equilibrium water content of hydromination of traces of wares however, the chromatoc,srbon systems by . thermodynamic or qn@iricaI ,, graphic technique has been complicated b,y the equations. The success of these efforts :hqs been formaiion of br~ad asymmedic water peaks which very limited and no relationship is available that -{.>~ould be- used for naturally occurring systems at made the method, inaccurate for quantitative w~rk. In 195S, Knight7 found that if water w?re added the pressure and temperatures of interest. , . I > to the carrier gas stream the tailing of water peaks could be reduced; however, no literature has been EFFECT OF Hl@ROGEN SUL~ID~ Ah found on the application of this. method for trace CARBON DIOXIDE water anal yil~. In W52i Knight and We,iss8 agal yzed hydroge~ sulfide and The volubility of water-in for traces &f water by, reacting water and calcium in carbon dioxide differs considerably from the carbide and then anal yzing for the resulting acety: solubilit y of water .in hydrocarbon s ystem-.as.~ho.wn lene by chromatography: -A similar procedure b.aqed in Fig. 1, This can probabiy be ex#ained by the on the production of hy~gen from water has also different molecular structures of these substances. been reported. Both of these methods are advtirsely .,, .. Hydrogen sulfide, for example, poisesseq higher affected by the presence of. hydrogen sulfide in the polarity. than hydrocarbons becaus: of the asym-. ,~ampk. .Carlstrom, Spencer and Jghnson2 used, a metric arrangement of its at9ms. Since water is a ( trapping arrangement to concentrate the water untif ... strongly polar materi@ itself ~. it will. have higher the waier sample was big enough to give a symmetric. , soiubilit yin materials with higher polarity. Carbon peak, but this method fras obvious disadvantages dioxide on the-other hand has zero dipole moment for Iabortory samples. , ~ and. one might expect thqt w,ater, wouid be. less Since the determination of water by chromatosoluble .in carbon dioxide than. in hydrogen sulfide: graphy. has.been hind:red in. the past by.asymmetric The., low water solubi~ity in carbon dioxide at Iow. wate~ peaks, che cause and possibie soiution of prei$sure is most Iikely -dtie COthe fact that. water water ~ailing, were studied. A gas chromatography* and carbon dioxide form carbonic acid in the waterwas ,-used for the. anal~ical work with. helium as rich liquid phase which lowers the vapor pressuie carrier gas, Several columns were prepared and of water in the v@or phase.- At high$r--preswres, ,, used: in- die ;chromatograph to give the required. wher~ the, distanc$s_ between thk -. individual MOL . ..-. resolution betwqgn methane-? hy~ogen sulf id~ and 'ecule"44are=+~eduESd;-'th&'-r@rn%kab1exiri6reas&-Ain--:=-- ,mtytiFlibr~~Z-8@~arid~~eflon-T-~6 were~kviih.tatkd--=---water scdubility in, both the hydrogen sulfide and as the solid support in the column. They .vere carbon dioxide may be due to some stronger packed in ~M in,,0 D glass spirai tubes made CO . mokuiar fcrces such as hydrogen bonding. ~. - . .,, .:epo~ced -, in water*Beckrn7~ Madel.(3C. 2 ,. , .... . . . . The .. . .. sol~ili~y ,,.r$lations .- .,..- ..., . . . . . . .. . ... . .,, >x. .. ... . . .. ,. .,,,
literature.
. .. . . . . ..: _. J._... -. - ._- ______ .. ______ .. . .. ... . - __.* __... ---.7 ----. ..-. . -...... .. .. +_. _. . .._ --- ~ _ ~ . . .. ... . . . . . . . .. . . . . . . .. . .90 CIttTY OP PETli OLEUM ENfENB@RS 10 URN.4L --... .- .. 294 .- . . . .< -... . .. ---... ..... . _ .-,.. -.+~a- . m---..-.-.;. .)-.< ... >.-.. ..... ~ .: .,. _# -,... . .. --,, . .. . . ... ,.,. ---- .. .. ~.. >. .. ..... ... . . .. . s.. . .. . ~. . . .. .. ... ., .>=...., . . .... _.. . ... ... .. . . . .. .... . . -.. .. .. .

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,,. size. In the, case of. large water. samples, however, a fit in the constant temperature compartment of the the amount of water retarded is relatively small chromatography, me types of columns used for the as compared to the bulk of the sample; and con- studies included Ansul Ether on preliminary sequently the water peak is not significantly Fluoropak 80, Carbowax 1500 on , Fluoropak 80, distorted. In the case of a small water sample, Diisooctyl phthalate on Fluoropak 80, and Carbowax such as water in methane, the amount of water ~ 400 on Teflon T-6, The column len~th was varied retarded on the column represents a relatively between ,,4 and 10 ft and the concentration of the larger portio~ of the sampli+, and hence the whole ~~ Ipsrtitionir$ Iiquid on.the solid support{ was varied peak is distorted. It was aIso noticed that when > from 1 to 20 ,,per cent by weight. The operating one water peak, was, put on the tail of another temperature of the colurim and the helium flow rate water. peak there was a remarkable improvement were SISO varied over a wide range, Most of these in peak height and shapci. cihrnns gave good sepstation for water and ,. ~ The two phenomena described above indicate> symmetric water peaks for liquid water samples of that every time a water sample is introduced iqto ~ 0.0002 cc or larger, Small water samples were thk column a constant amount of wa&r will be c prepared for injection with- the chromatographic retained on the column for a Ionger time ~han the colunin by saturating. methane with whter at room rest of thd sample, dtie to die interaction ,between temperature and atmospheric pressure. All columns the water and the column materials. This suggested water peaks with,= jrnolersble gave asymmetric ; that, if a constant saturation of water was maintained tailing, on the column in sufficient quantity to eliminate ~xamining the .whter peaks for diffqrent sample this interaction, the tailing could be reduced, sizes, - it was found that the tailing was of the , Following this reasoning, a constant quantity of same magnitude for all ssnqple sizes, as shown on Fig. 2. The first chromatogram on Fig, 2 was ,, water was introduced continuously, into the helium carrier stream. In this way an equilibrium was obtained for a 0,001 cc liquid water sample and reached between the water & the ~olumn And the the. second for a 1 cc gas s%ple of appr~~imately carrier gas stream and ii :emained constant, provided 3 per cent water and 97 per cent rnethan~. The the operating. conditions did not change., Tesrs, attenuator waschanked to a more sensitive posi?ion simiI iar to that shown on Fig; 2 were repeated. after the majority of the 0.001 bc water sample With this procedure the tailing of water was almoat passed through the detector to show the tailing, completely eliminated. -A. typical. chrornhtogram for T~e tailing ,cif the large water sample. is evidently a 3,8 cc meth,ane-,water vapor aarnple i+ shown on the sqme nature and magtiitude as tke tailing of the- Fig. 3: The water content of the methane s,ample small water s~mpIe introduced witki the meth~e, Fig, 2 i~/licates that the sbme quantity of warer was approximately 3 per cent. As shown on Fig. is retarded on the column regardless of the sample
.

COLUMN - 6 FT. 5 % BY W1. ANSUL ETHER E 181 ,CIN FLUOROPAK 60 REGULATOR PRE5SURE -25 CARRIER GAS - H&: R WITH

,,

FLOW RATE - 45 .$C /MIN. COLUMN TEMP. -70 CURRENT. - 390. mA CHART SPEED -1.0 lN./MlN SAMPLE -3.8 CC METHANE AND WATER SENiTfilTY - 4S NOTED + C .

-.. .

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,. ,, :.... . . FIG.. 2 .-... TY.PICAL .CHROMATOGRAM.. OR. WATER.

CHROtiT~RAM OF ~THAN~ FIG,. 3 - TYPICAL& ---- AND WATER-WITHWAT~ l@J CARB~R. ~= .-..

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3, the constant water saturation on the column eliminated the tailing ,qf the water in the sample and made it possible to obtain symmetric water peaks. . ,.Several different tests were then conduct~d to evaiuate the effect of hydrogen sulfide on the chromatographic column, and it was coocluded that hydrogen sulfide did not interfere, The effect of other factors on the resolution of the sample components aid the optimum operating conditions were evalticed experirnentaiiy and the optimum water content of the helirim stream was det&mined. It was found that the amount of, wsyer in the carrier gaa stream significantly affect~d the size of water ,signals, For example{.: increasing the amoant of water in -the helium str~am over, a certain level dettreased the water peak. Base line, fluctuations were also increased by inci+sing the amount of water in the helium stream. After studying the effe:ct of the, different variables on the column performance, a column. 4 ft iong packed with 5 per cent Carbowax 400 on Teflon T-6 ,wiis chosen for the experimental tiwrk. The water content of the helium- stream was 0.23 mol peq cent with Q ~ flow rate of 50 cc/ritin, The column temperature was held at 97,5C, and a sample size of 3.8 cc , . . was used. .< The chrornatograph was calibrated for water by saturating methane, helium and mixiutea of methane and hydrogen sulfide with water at atmospheric preakuie ,and it a series of fixed temperatures in a controlled temperature bath, B was very important. to carefully control-the process of s&urating these gases with water. The range of water concentrations covered was from: O to about 43,000 ppm, and over this entire range the relationship between peak heighr and concentration was linear. A complete and de~ailed discussion of the calibr~ipn t.eciiniques and the operating procedures has.,&4n given by Lukacs.t2
5

a minimum of 4 hours, After equilibrium had been established the agitation was, discontinued and the gas phase was sampled by slowly releasing the gas through the expansion valve. During the ssmplihg period, mercury or water was injected irsto the cell to maintain the constant., pres sure. Th~ sample from the expansion valve travelled td the chromatography tlirough 1/8 in, O D stainiess steel tubipg, The expansion valve and the stainless steel tubing were heated t~ 300 to 400F to reduce water condensation on the walis. The sample was continuously purged through the chromatography and., the water cotttent. determined at about six niinu{e int&vals over a period of time, With tifis technique,~the effect of the lead line and ~onnections on the water contene of the sample while traveling from the cell to the chrofiatograph could readily be ascertained. As many as 10 td 20 samples were analyzed for one conclusive point at each set of equilibrium conditioris. EXPERIMENTAL RESULTS ~

EXPERIMENT&

TECHNI@JE

The experimental apparatus consisted, of an <, . a equilibrium cell where the gas was saturated with ., 16 .: -water, an auxili~y ceil which was used for a water. .2715 > .8 reservois,. a high pressure pump and tlie chro ~-:to. 17 \\ . Am graph with its accessories. .The equilibri~m cell 1,000 ..,;: ,,9 .___:h ( was assembled from a 316 stainless-steel doublewindowed liquid-level gauge, The cell was enclosed a \ in a cylindrical lucite jacket in which a suitable m. ~ \ .. oil-was circulated co maintain the req~iired constant * temperature, The jacketed cell could be continG - SAGEANDLACfY04) ..= . . . ~ ME~HANE ., . 0 METHANE - THIS wORK uously rocked about its central axis ~o attqin + tWOROGEN SULPHIDE -SELLEK (l@) -q equilibriti, A METHANE - HYOROGEN SULPPIDE %% -1 ~ l SYSTEM - THIS WORK The e~ilib:ium cell was ch~ged with djstilled ; PERCENT .. %%%o&Rc%:P;~{ !i% A.POUR PHASH ., xl the gas, to be studied was brou~hr to . water- and . --- IDEAL GAS. \ . -. . .. by purn~ing either. ;. , the .d~:S&S_d.~p~rI:SUr,e. -:= -+ ... [2LeLL_:_L_.:o.~5. -..: .....-. :.. :.,;:J -=.-:-100 ~oo;5_:L:._2:lL..L:io:; tR3ii& water ntto the ceIl;~Fliii%iiid?l$z .system, mercury was .used as the confining fluid, i , iOLk tiRACTiON OF WATER ,,+but for the methane-hydro8en. aulfide:water s yatem, EQUILIBWUM WATER cONCENTRATION . , : FIG. 4.water itself was used. The contents of th~ cell IN METHANE-HYDROGEN SULFIDE IkUXTURES AT , .. -. . . were. stgitated by--rocking:the celK continuously for, . .. . . .. .. - .. . --- -:. --- 160F... J .. . . .... .. .. . . . . .. ..... .. ..:_ ___. _. ___ ..4.. .-.. . .. . . ,. : --.: -. .. .. . .

,,

-. I A ,. k ~~ (l {.:
i-,, b

i In order to verify the sampling tethniqu~, the method of operation of the chromatography and thk ~ attaining equilibrium, a series of tests were condticted to check tie water content of pure methane at pressurea up to 1,495 psia and at a temperature of 160F. The r~suits of rhese measurements are shown on Fig, 4, And. it will be seen that excellent agreement was, obtained with the previously pubIishsid work of Olds, Sage and Lacey, 14 For th6 studies on the methane-hydrogen sulfide system, water was used as the confining fluid. Since the amount of methane and hydrogen sulfide dissolved in the water depended on the pressure,

,.

,.

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. .

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., ....

,--=-=. -: .-. ..-:.,:._ -_ ..

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- . .. -_._...

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EQUILIBRIUM WATER CONTENT OF tY?l$t4EYYDRo,GEN suLFIDE VAPOR AT 160 F

AV. Peak H2S i I&ht Crmten+ water

Pressure $~;:
of

No*of

#&~~;n
% - 2.6; t 197 -4.5; +8 - 0+?6;+ 1 - 2,3; + 3 -2; +.2 ,- 1,6; + 0.8

.psla 1395 1010 611 :: 358 13?2 995 116 199 379 ) ~l? 140 ,,240

V~pOr Content Samples And yzed iwm . 7 16 i ~~ 10 6160 17, 9300 -6 19 8 .; 15000 21 ,4: 5200 27.5 6 .29 ..: : 6900 ,

caution be exercised when reducing the pressure on die sample and transferring it to the chromatographic column, All points in the connection izystem should b kept at a constant, temperature in the order of 5 00 to 500F to reduce the ad&oiption of water on the steel. , ACKNOWLEDGEMENT , . . . The fi&ncial support offered by the Impe$ial Oil Co. of Canada and the J3echcei Corp. in support of this work is gratefully acknowledged. ., .> <, REFERENCES .:.:<,.. ~~ .;
L Black,
f%ys,

 

~,? co k ep th~ composition of the vapor phase constant ~e{, ,a range of pressures for &ach charge of the cell. Z e. data for systems containing up. co 29 per; cent \ ydrwn sulfide in die vapor phase ate sho$m in Table 1 and g? Fi& 4. It wili be observed that while. the presen.cd of hydrogen suifide increa~ed the volubility of the water in the vapor pha~e, the- effect is perhaps nor as pronounced as ~ne might have expected from theoretical considerations.
it waq not possible

C,,

Jo~$=i G. G. 4ind Taylor,

(194S~VoL

16,,537.

H, S.; J. Cbem. .{

F. and Johnaon, J. F.: Anal. ,Cbem, (1960) Vol. 32, No. 9, 1956. 3. Deaton, W. M. and Frost, E. M., Jr.: Pry. AGA (1941) 143. 4. Dodaon, C. R. and Standing, M, B.: DrilL mad Rod.: Prac. API (1944) 173, :7 5. Hibbard, R. R. and Schalla, R. L.: NatL Ad~iaory Comm, for Aeronautic, Washington, RM E.S2D24

2. Csrlstrom, A. A., Spencer, ~

DISCUSSION

(19S2).

6. Katz, D. L., el al: Handbook of Natural Gas Engineer-

,.

.-..

-.

,. .,-

The chromatographic technique deve~oped here ~ 7. Knight, H. S.: And. Ctwrn. (i9.5S) ..voi. 30;. ?030. has proven to be a satisfactory method for ,deter8. K&k, EL S. and Weiss, F. T,: Anal. Cbeia. (1962} mining low concentration of wgter iit hydrocarbons vol. 34, No. 7, 749. ,:. in the preserice of hycirogen sidfide, Thelimited data R. ~.d Katz, D. L.:, ln~ Et@ Ch~. 9. K&ayaahi, obtained have shown thar hydrogen sulfide ~auses (1953) vol. 45, 440. - .! only a moderate .irrcrease in water solubilic~ in the 10. Laulhere, ~. M. and Briscoe, C. F.: Gas (1939) Vol. ;15, 21. ! gas phase at pressures up to fi!500 psia. ..-,. ... 11. Leland, ~, W,, M6Ketta, J. J., Jr. and K6$e, K. A.: Modifications are being made in the e~erimental Ind Eng. Che~. (f$?S5) VOL 47!, 126% equipment to facilitate sthdiep ori Che e@.ubiiity in the liquid phases as well as in the ,@as. An effort 1; Lukacs, J.: ~Sc.~?h@SiS,-. U. of Alberta-.( 19G2). 13. McKetta, ;J. J., Jr;;and Katz, D. L,: ind. Eng. ,~heh: is being made to fiqd a confining fluid that will be .. (1948) yO1. 40. 8!$8. . inert to WJd will =pt dissolve. hydtogen ?ulfid~ or 14. Olda,R. H,, Sage, B. H. and:L@yjW.. N.: rnq. Erzg. hydrocarbons in the presq?ce of water at the presCbem. (1942) Vol. 34, 1223;, ., sues and temPeFa&e of- iqtetest in working with . ., 15. Reamer, ~. EL, Olda, R, H,, Sag~;, B, H, and Lacey, soy condensate fluids. ,; W. N.: lnd. Eng, Cbem. (1943) Voli,.35, 790.: ~ ; .Only a Iimited.number of.chr~natogr.aph!s @~n5 16. Reamer, ,H,H. ~ Sage, B; H. &d Lficeyj -W.-~:: l~ti and column materials have been evaluated in this Eng. Cbem, (1952) Vol. 44, 609. work tid it is possible that other even b&ter com17. Rusael,. G. F., Thompson, R;,, vance, ~. P. and binations rntght be fourid. The.optimum water content Huntington, R. L.: Trans., AIMK(1954) VOL 16, 150. of the carrier gas will depend on the nature of die .18. Selleck, F. T., Carmichael, t,.. T, land ~ge, B. H.: column atid should always be the minimum which rn# Eng. Chem$ (1952) Vol. 44, 2219. will effSctiveIy reduce tailing. The use of the cbe-%~OCC 19. Weiba, R. and Geddy, V. L.: ~,.Ara.. \\, , (1941) vol. 63, 475. technique described here requires that utmost . +*+
.,

ing, McCjraw-Hill Book Co., Inc., N. Y: (1959), ;

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