DE1648946C - Method and apparatus for Be agree the small amounts of organic components contained in total in aqueous liquids - Google Patents

Description

end:. '■ ird
'■, ^ he; .1 :: r jn

a ti. · ". \ nspru>: i

die Reduk ;: insst'.üi. a », aijf S-.
sorn; erte Nickeis ··! "! - ¹ !! ', \ erwend
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7. \ 'he!'. '. Iirei-. nac ¹ ; Expectations.

The invention relates to a procedure for; ,, Remaining of the small amounts of organic constituents contained in total in aqueous liquids It also relates to a device which enables this method to be carried out.

Processes which determine the total organic constituents contained in aqueous liquids are important economic as well as social wedge. In the chemical industry it is necessary to determine 0: 1 the organic content of the water that is used during the course of chemical processes or is returned to the cycle in order to establish the carbon levels for the process. · ■ by calculation. In the industrial eye, it is desirable to control the proportion of organic components contained in the water if the water is used in steam generators. A considerable application of these methods also in the control ντ: industrial and other wastewater, the for'.geici ·; - '

Previously known method / um üev. Ganic! ' ^1st Shares in aqueous solution time-consuming: usually work: ·; ■ dation of organic Üesiand; ei: -jd Mult · '. Example you; omai. Z :: r! Kohienuio.wd. Which is usually absorbed in other Aikahlosiing, what v'erl'ahren / ur karhonatbestmiinung a

The task is. a process ziüv wii ,, ng liquids enthalpy " standiciie »-or / uschkigen. pci dem sc a very small liquid wedge]> robe e:

: ^τ w ir ..-, mc au:

we are able to identify

draws because :: · the K: iwi: y.-jio '_;,; i: 'a temperature in here; .. :: MM) up to 35'. '· f.'.teiialte'iwe> i.

ίί. Expiration re τι after, one of the statements 1 to ':. thereby draw iiekenr. d; eat that emerging from the reduction sisifc ·. · Ck ^ s by Hinrichün-ge · '· /' at the absorption of d's griWUer; "Iiis of the existing water vapor is gclüb.n \ i>! It is integrated in the flame ionization door; wirc !.

^u . Vorriciiüing /. To direct the process according to all claims! up ^ .. gekennzeicliiiei by a "')>,> since io:! · soft with a filled di in aqueous F'iis> iekeitsp ^r ohcn uniöslicher · Feststoffoxydationsmittel f / i 1: i> i rinnc itung (...' l is associated with an injection opening 1 /); fii; the Flüssigkettsproben a Finlaiij / '; a lne ^r ttragergas and a Auslal.'!.> ka - is seen, \ i (l · '> \ the..!. over cm F.ini: il.pipe (/ i for V. asseistoff with a reduction unit (λ 1 \ eibLinden is;, in which a carbon diowci in the presence of water slofi / 11 methane-leading catalyst is located. and those with a 'llanimenionisation detector (Wi in connection with stone.

Ui device naci: claim ^l ). marked / cichne 'durth an ilüfsiniektionsoffninig (//' in Aiislaßk.i: - 1! (I)

! '' ■ ι · .. ': \: ιι) ί · ικκ'ι Xi'spruci', Ü). dad'i: -! i ■ jckenn / eichiici, da: * em leii ti; ¹ - Aiisiaükan.'l ·. ι / ι on d ·. ·; ' Rope '.-' the 'iii! . ^ i'i'ci · ι ümisiim ihiiil: (/ '' imeine, ί 1; ^{'^:} vi' ·: ν · Γ \ .Ιιιιιιι: ^':!:, · ■ scm...!. ■■: i r.iMier. N Si: k!

de: or outer.-:

ersuuuni; '.O '.lücr · -nd: r icii kiassiS '.' N

her Beü Ha ^: ii bri! s he

F.rge

:> his task will be a lindunescemai.i üadmcii u'tlos', that a liquid sample with a solid;, sn of the liquid uniquely oxidized in contact is brought, whereby the organic constituents of the liquid; '. u carbon dioxide is oxidized become, which then reduce to Met nan; is done by Hydrogen / ugemischl and the mixture with a suitable catalyst and c \ '. Ss that Quantitative methane formed in a flame ionization detector is measured.

The solid oxidant that is used in the etlinüum'.sgem Method preferably used, i.-t copper oxide. that at a temperature in the range of 850 to 900'C is held. The conditions under which the liquid sample passes through the hot copper oxide is oxidized, may suitably be those based on the combustion or detection oes carbon in organic compounds have prevailed. The oxidation occurs in the presence a stream of an inert carrier gas, preferably nitrogen, performed, whereby the during The carbon dioxide formed by the oxidation quatitati ·· '/ is transferred to the reducing catalyst.

The reducing catalyst can be any catalyst that is suitable. the reduction of carbon dioxide in the presence of hydrogen to methane for a year!). I-in preferred katalysato: hestehi from one. ', Ui dem fcuer- ¹ CMCIi Siein h / .v .. den; SchamoUesirüi adsorbed ^ icki'isc'iichl. the AU! eir.c:! eniper.vur above '.'. '.' · L. we / .ugsweisc au! one! er.iper.iiur in the range ι, ιΐι MM to 350 Γ.:ii is. ! <: '. dv Kcliiktion Ic, KohiendioKvus to bring about. HnJ eir. .: eeignetei v \ assersioffanleil dem; ilis der ι) x \ dalionsslufe out-

I f

; ret.-iKlen gas stream added before this came into contact

■ ivι the catalyst comes.

The flame ionization detector, through which the methane formed at the end of the reduction step, is eaten, can be a commercially available de- •:; k'.or, as it is, for example, generally in the ^; v! tischen patent specification S3H 189 is described. whereby

■ lic associated electrical equipment known per se Use to record the signal generated by the methane in the detector in visual form Can be found. However, a detection is preferred

T. like him in the publication by Cropper i.ikl K a m i η s k y is described in Analytical neimstn. Vol. 35 (1963). on pages 735 to 743 ^ write is !.

The jus of the reduction stage emerging from inert gas. Hydrogen and methane and besieiu nde gas stream may be conducted directly to the gewünschtenfalis \ ..menionisationsdetektor. Preferable: ν "UiIm one, however, the exiting gas flow through a suitable device for absorbing" much larger part of the water that is present .-. , - · .. nspi seilen des Deiekicr ·; au: that in the gas-iron; enth; -. Ii; iii. · Metiian disadvantageia is influenced by the presence -ers-inissigt'i water vapor ^. That is why one absorbs in a safe way

': i

V- .is-erdamp! in a Siin.aselkoionne. by un nu; i ι!. · -. au ^ b'iriimeiKJe step on the gas loudly.

Dan-":! du-, ν'.in Flammeniorisationsüetekfor / eici'iie'e Signa! directly as an indication of the Kohicrstoffj 1, everything i! I-r exposed to the test. Pwöen mi ^ r-T '! Vt! -: i "L worth it, it is necessary to check the dc.ekioreiniii.niung using well-known Meiha'i- ■ .i-Uimina to calibrate. The procedure to the Durer: - 3 .- 'uiir.ing this calibration will be explained in more detail below -rhncbc ..

The ν orrichiung for performing the advisory Veriahrens is indicated by a O \ ydations? Mrichuing. soft with one in aqueous Liquid "-probe π insoluble" -cs'.atoffoxydaiion «- center! gel '-. ilh is. the ν, ίί of an injection port for die LüiSigkeitsprohen, an inlet for an inert carrier gas and an outlet channel is given away, the trische Heizwmuung is surrounded, which is able. to heat the catalyst inside the tube to a temperature in the range from 3 (K) to 350 ° C. The flame ionization detector is designed in this way. as described in the aforementioned publication by Cropper and K a m i η s k y is described. the The outlet duct of the reduction unit is at a point near its connection with the flame ionization detector mi: an inlet for da-ο burner gas, which supplies the designer flame, provided. The burner gas used consists of a mixture of 1: 1 volume percent of hydrogen and nitrogen.

It has already been pointed out that Ii it wnr: - is worth seeing. Detector and associated recording interior devices -h ". ..ας to calibrate with angry methane volumes.

L <m through this process · ¹ ' ¹ .. a t! Mis opening should be arranged, the 7v.t-: hep. your Aiisia:

as the oxidation unit and the water ^ to; '· -

: o Insert the inlet in a slope as close as possible to the exit point; is. The auxiliary opening ji ·: '"-l · - siehi - ¹ JS. A"kur'cn. at the outlet channel ai: - de "Oxydaiionseinheii attached side pipe. da · - oürei", a flexible membrane, through the methane sample :; c ¹ -

; s can be carried out: ":, ^ ersclilosse;) is'.

v \ he admonished above, vsüiiicht nia.i uewöMiiic'.i · :. . üi au «der Redukiionssiiji'e iiusstrnmenoeii G ;;>. hailerio water vapor! For this ί ·.; Ί di · .- Vo'Tichli'ng therefore eit! suitable Mitiel / im: i-.:U-len this water vapor. that in the Λιι ^ ίϋ'.Ν-kana! inserted from the accumulation unit. ^; ': - Drying in enrichment: g can expediently'. a>i>a; Sihkageikolonns exist, whereby a few.e: · e '-:> part of this column preferably made of silica! -λί- · .- self-indicator. see the 'type'.

The method and device according to the Irrlindun ^ -ι · ν.1 particularly suitable for fixing organic constituents in aqueous. Liquid wedges i: n Uiirani; - .: - scale: for liquids that contain an equivaien · νν · ι ο 500 to 5000 ppm Kohienstofi ', it is mu ~' icii. ^{to work with 1} , a sample of only two 2u.l (which contains the equivalent of 1 to 10 μπ of carbon). ^:: ': "Ben higher Koiiiensioffgehai' as MKK) pn;; are ahaekochtem with water before \ ersiu-h

diluted with a Reduk- 45 via a Fin.aU tube for hydrogen. The 7xr required for this read. iiegi

tion unit is connected, in which the carbon on this basis at about 2 minutes, the Zc; 1.

Dioxide in the presence of hydrogen to methane starting from the moment the probe is introduced

reducing catalyst is located, and which with one in the combustion tube until the occurrence of the spit '?

Flame ionization detector is in communication. ouch a flame ionization detector recorder. in

The oxidation unit may be drawn _t .us a vertical 5'· consideration. The reproducibility wedge of this SYiika or Kiesclerder pipe exist, the one with Κυρ-fer (ll) -O \ id for the determination by combustion
de.s carbon in organic compounds

KohiensK

Beneficial part quality is filled or packed, whereby a method is based on
salary estimated.

Uas method according to the invention gives a measure ^; .> for the total carbon content of the sample, d. I :. dii

electric oven is provided. of the temperature 55 amount of the organic constituent i any the copper oxide coating to a temperature in the carbon dioxide that may be present. Is it optional increases from 850 to 90 ole. The upper end of the apparently that the amount of free '.- n carbon dioxide Kicselerderrohrs is by a suitable flexible is considerably. so this can be separated by reduction Membrane closed, which is used as an inlet opening for methane and measurement by a Flainmendie Fluid test serves. The upper end of the raw 60 ionization detector in the Wires described above also carries a connecting pipe that can be fixed with direction; for this purpose a

Sample the aqueous liquid into the device through the same! lilfsöffniing like those through which the iVIetanprnben are introduced for calibration purposes, brought in. In order to ensure adequate evaporation of the introduced sample so that the herein contained carbon dioxide .-. vd to the deduction unit

a source of an inert gas, preferably nitrogen.

The Reduktionsein! .I "t consists of a vertical pipe heat-resistant glass, which is consisting from stored on refractory bricks nickel, packed with a specially prepared catalyst (wei-1 iTi ¹ see below) and by a ek'k-Trust, uassiro 1 v. is required, becomes part of the

Outlet duct from the combustion unit to tier Be the aid to the opening of the year. those of the unit is arranged remotely, preferably with an auxiliary / unit equipped by a filling (ilask balls is added and by an electric IIci / Tspiilc liicrum is arranged, which is in the I.agc. the ulaskugel to a temperature of about 150 ° C bring to.

The process according to the invention is generally applicable to aqueous organic compounds containing Liquids in which, in addition to carbon, any or all of the elements hydrogen, Oxygen, nitrogen and chlorine are present; an excess of volatile substances can be present in the liquids inorganic compounds such as ammonia or hydrochloric acid or non-volatile inorganic compounds Components are present.

The method according to the invention can be applied to the determination of non-volatile substances at much lower concentrations existing components (in the range corresponding from 0.1 to 1.5 ppm) in demineralized Use water that is used in chemical engineering and as feed water for high pressure steam boilers should be used. For this purpose, the samples can first be evaporated, for example around the lOOfachc, to be concentrated, and the amount of more concentrated, necessary for the test Sample can be reduced to 10 μ! to be increased Fs is also It is desirable to have the recording device connected to the flame ionization detector in one to operate a slightly higher degree of sensitivity than is the case with samples with a relatively high content of organic components; in addition, certain minor modifications are made to the device desirable in order to account for the proportionally greater water content of the samples provided for the test compensate. These modifications are discussed in more detail below. The procedure owns a reproducibility of about 0.1 ppm carbon. ~ ** · «

F. an exemplary embodiment of the invention will now be explained in more detail with reference to the drawings, in which

F i g. 1 schematically shows the cmc device that is used for this purpose is used, aqueous liquids ηυΐ organic Examine constituents with an equivalent of more than 500 ppm carbon;

Fig. 2 is a schematic representation of the modifications, the at the in F i g. 1 shown device were made and desirable are, if aqueous liquids are examined, the organic components at much lower Concentrations included.

in Fig. 1 is denoted by Λ a silica combustion tube, which has a length of about 30 cm and an internal diameter of 7 mm and which is filled with a column B of copper (II) oxide of microanalytical reagent quality iVcm long. which is held in place by a silica wool pot. The tube A is inserted into a 230-Voit electric furnace C with a bore 20 cm long and 10 mm in diameter, so that the copper oxide filling B is kept completely inside the furnace. The upper end of the combustion tube A is provided with a Sihkon rubber plug D , which serves as an inlet opening, and a side arm E. which is connected to a nitrogen supply. If the flow rate of nitrogen is measured by a capillary flow measuring device, not shown. The lower linden of the combustion pipe A is connected to an outlet pipe [· ' of about (> mm outside diameter, which in turn leads to an auxiliary device (; which consists of a length of a heat-resistant glass tube of about K mm outside diameter and with a chrome -Nickel resistance wire 102 cm long and 7.6 μ in diameter is wrapped around its resistance

ίο is about 14 ohms and that in a spiral of about Wrapped 9.9 cm in length and connected to a 12 volt power source connected. In the lower end of the tube of the auxiliary device G 'is a side tube / led that to a source of a 1: 1 volumetric !!

Mixture of hydrogen and nitrogen is connected. The part of the pipe of the auxiliary heater G, which is surrounded by the electrical winding is filled with glass spheres 2 mm in diameter, the held in place by stoppers made of silica wool

be ao. An outlet pipe J leads the auxiliary heating device G and the hydrogen inlet / outlet gases to a tube-shaped reduction unit K, which consists of a heat-resistant glass tube 13 cm long and 6 mm bore, around which an electrical heating device similar to the one on the auxiliary heater G is used, but has a resistance of 26 ohms and is connected to a variable, 25-volt supply. There? Tube K is packed with a nickel-fireclay catalyst prepared in situ essentially by the method described in the paper by Porter and Volman (published in Analytical Chemistry, Vol. 34 [1962], p. 748) ). The upper end of the reduction tube A 'is through a dryer tube /. length of 13 cm and a 6 mm hole, which is filled with self-indicating silica gel. which are held in place with stoppers made of silica wool, which in turn is connected to another dryer column M , which consists of a 46 cm long U-tube with a bore of 5 mm, which is filled with silica gel with a mesh size of 0 , 42 to 0.29 mm packed. At the exit from this column Λ / there is a T-piece Λ 'arranged, the side leg P of which is connected to a source of a 1: 1 volumetric !! Hydrogen and .jckstofflösung is connected, which serves as a burner gas for a flame ionization detector R. The detector R is provided with an air inlet 5 and outlet ducts T which are provided with suitable amplifying and recording devices; the recording has a recording speed of T h cm. (30 "/ hr.). The various units au ¹ constituting the device, of a silicone rubber tube can be connected via Hulser.
The device is used as follows:

(a) Structure

The device is constructed so that by the

Bo inlet f is introduced with nitrogen at a rate of 10 ml, the hydrogen stick sloff mixture through the side tube / as a reducing gas at 20 ml / min and the same mixture through the side tube P as burner gas at 30 ml is fed to me. Air is introduced through inlet S to be 400 ml ^; min fed; Combustion tube A, auxiliary heating / before direction G and reduction tube K each have temperatures of 850 to 900, 1 SO and 3 (K) bi herebc

3 ^{s ii!} 'I ^"1;.! · Uli''■ iiillKlikcl - li'uci iiiiut'ü on Ham iesailiik>ihlens'lu (fgchall the Originalprohe from the

nienionis Um aisd \ -jr 11 · ί \. 11.- c ■ ι ■. h ι, '. ■ [sin.! . ·> -Inge <l! Ekhung hcrei line! ■ (i cs; i ml k ι> 1τ lt.-n -. T ι>fj'ui_-ha 11. siel '!, d.il' i-ine ': nl,' t mim about. 'Λ ji Diülei des villas

Rashes ·,! Ruh Ιη, ο-, ο-, Μ from el,, 20 ,! Mdhan,. ^ ,,,,,,, _v ,, """." ⁽⁾ - " ^{S Λ} . '. · ■ ₍

ι ι '"ih du ί Hf iiilf Mim? // iiiiiei \ ei ■' ■ ciidmm cmc: .Ί / I

H.ii'iiiiiiM-Sprii /! · Echo 'λιιΊ

therein I denote the net peak.

^{1 &quot; 1} ^ ^{η! Π} ί 'lumen of the Ongiudlpiobi :, the / to volume I ₄ devi-

Using a 25-; il-Hamiltoii-Sprit / c was thinned, and / 'is the factor Neltospilz.enfläche'

sets of 5. U), 15 and 20 j / I become pure Mc- i < >; ig carbon, derived from the methaivieh-

thans naeheinaiuler into the device at the auxiliary diagram.

opening // introduced. The resulting peaks are carbon dioxide freely present in the sample

den about 4? Seconds after each injection on- is determined by adding 2 μI of the diluted sample

drawn. The height of the tip is measured at the injection port // inji / .icrt and as above with

(Shown as the product of the height of the tip and the height of the 15 Uezu ^ on the total carbon test position.

Peak at half height), the diagram will then The total free carbon dioxide present will be

recorded, consisting of peak / surface area over con - calculated from the following equation:

lengewiehl in ag. where a μΙ methane is equivalent to free. CO, (calculated: ds carbon), is assumed to be 0.5 μρ carbon. The resultant application should be a line that goes straight through the 20 _{ticwichlsprozcnl} , volume ^O '° ⁵ " ■' ² C ₂ coordinated zero point. / ■■ I ₁

(C) Monitoring of oxidation and induction _{|)) crm js | fl djc NcUospil / cnfläc for dic} diluted,

^step at the opening // injected sample.

Using einci ΙΟ-μΙ-Hanullon-Sprilze 25 the entire existing in the original Piobc

different parts of 2.0 μΐ of a particularly organic constituent then result as

Ready-to-use aqueous glycerine solution after C, C ₂ .
each other into the device through the injection

jlTnung /> injected, with one between each ine) regeneration of the filling of the combustion

Allow jcktion about 3 minutes to pass; the needle 30 ro Ii rs .I and drying tube /.

the syringe is inserted so that it is about 0.63 cm

in the copper oxide filling H of the combustion crude oil is necessary, the filling / i of the combustion

res.l einrim't. Leder I'eiU ilycerin solution is intended to regenerate a crude res .1 as soon as m;:. n is established. ^ d \!

Peak of about two-thirds of the full scale range - test results on glycerine lead to results,

sclilai-es lead The aqueous used glycerin- 35 which is more than 5 "" under the iüehimcau for methane

solution is made by carefully weighing lying areas. This is achieved. by going into the

1 g Gluenn. that to a total volume of 100 ml nungsrohr f from the rest of the device Inst and air

is prepared with boiled Was'vi: 1 μΙ of this at a rate of 50 to 100 ml

solution is equivalent to λ 'times the weight of | By the one held at H 50 to 900 C for an hour

in grams of the glycerine used, 40 mhait flow loads. After this treatment v.inj

in μι; Carbon, finely charged, is then introduced through the pipe with a stream of nitrogen

Inject through the opening / 'of 2 μΙ of the ab- long cleaned before putting it back to the device

boiled water L ": fii!; it. that is connected to the preparation of the.

(ilycerin solution was used. The making of the silica gel drying tube /. is made from the above

M -.- '. Iianspitzcn nemesseii and the surface of each direction are separated as soon as the indicator changes color

Tip fm the water drained from each empty and put in an oven at 130 C for regeneration

messiMiL 'recorded; the mean net area d-τ of the contents heated.

Spikes are then determined and the carbon content is essentially the same as that described above

in ug of the 2;> 'file of the glycerine solution used, the device can be used to determine quantities (0.1 br

calculated. The corresponding point on the above 50] 5 ppm) non-volatile organic matter ii

Solid demineralized water will be used for the Hich diagram described under (h), certainly

placed: the point _{harbors within 5 "0 of} the Fichunia. changes as small as they are schematised ii

It can be assumed that () xyd: .tions- and Re- (i g. 2 are shown, but are desirable Ii

work satisfactorily in production levels. F i g. 2 represents A the lower I nde of the combustion

55 pipe. This in its entirety in V ig 1 ge / eiu

(The experiment. in the aqueous I lussigke.tsprohen _{is ,. djesc <> JM mlUds cmcr} silicone KaulschiikhüKc mi

Samples of aqueous liquids are used for the test in a T-piece C with a bore of 4 to 5 mm

adjusted by adding boiled water, so connected, the lower limb of which by cinei

that there are solutions in which 2 μ! I.m - \ us is sealed between the silicone rubber bung Γ

Contains 5 and 10 μg of carbon. ^{5o outlet} pipe F ' from the T-piece is about 46 cm (IS ") long?

The total carbon content of the sample is then d. h is much longer than the corresponding one in I i g.

fcstuelc'Jt. by attaching the illustrated pipe F to the opening Γ) 2.0 μϊ

thinned dissolving of the sample in the same way as for the glycerine way! be to make the device compact ζ

hold the solution as described under (c). The other I'ndc of the pipe / - "is mn the

become: a! eerversueh is also at 2 μΙ de ·. O5 lateral leg tube of the auxiliary device U wi

Boiled water ·, carried out since it was connected to the her- beforehand. line more in I 1 a. 2 flour dai

stcilunu the l'robcnln.sting served The net top- put! - change of the device can then b ·.

area fi'i! the l'roheniosun !. ' vvirii uaiiii fc-igclegi. the place:!, d.iü;! ie S.iuk.vjeikohTuu · M ι ·. \ der! fsnue.!>.

ctwii 137 em is extended (and can, if desired, also fallen). Is also necessary that l-disability ('es Hammcninnisaiionsdctcktors "i / Ii win. by adjusting the attenuation of the amplifier will; a five-fold increase has been found to be satisfactory, so d. iu; of carbon lead to SO "n of the full scale stroke. This procedure to carry out the discoveries of mineralized water is also similar to that previously described, with the main modifications consist in (a) the preparation of a starting concentrate by evaporation of a sample

of the mineralized water to about ■ ·. of the primordial

\\ nJ

i original volume, (b) using the test sample (concentrate) of 10 μΙ instead of the sample of 2 μΙ, whereby the larger sample is slowly injected (over about 5 seconds) into the combustion tube A , lim the disturbance of the flow of the carrier gas Reason for the evaporation of the existing water to reduce the hoof to a minimum. The extended outlet pipe F ' acts as a delay pipe and ensures that the methane peak is not recorded until the disturbance has subsided. The water that condenses under these circumstances when it exits the combustion tube A is allowed to collect in the lower leg of the T-piece U and is removed from time to time by inserting the needle of a lipodermic syringe upwards through the silicone rubber plug V.

A modified calibration is used in which the common methane quantities are one tenth of that given in the above description; instead of using a single glycerol before checking whether the device is operating satisfactorily, a series of solutions with concentrates 1, 2, 3, 4 and / ₀ respectively of the Konzentralionen Miiik-r Lin described / used ellösung 5 °. ll); jl solutions are injected into each I all. In practice si. h stand out ¹ . that the light line for these cereal solutions, if they are plotted on the surface of the surface over the carbon content, does not coincide with the median line, but parallel to the latter with an overlap on the carbon fiber between U and 0.2 | xg lies. This overlap represents a

ίο represents an "empty" device and, provided that the two lines are parallel and the intersection is not greater than 0.2 | xg, the device can be assumed to work satisfactorily if the size of the overlap exceeds 0.2 | xg , the filling B of the combustion tube Λ should be regenerated. In all cases, if one works according to this modified procedure, one should use the glycine line and not the median line as the reference variable for determining the carbon content of the

Use ao test samples.

Due to the considerable influence on the accuracy of the results of any organic pollution the needle of the syringe, which is used to inject the sample concentrate or the glycine solution

a5 is used, which can occur when the needle is inserted through the silicone rubber cap of the injection opening D , a modified injection technique is used in which the Hamilton syringe is first filled with about 12 μΙ of the sample or solution and after the introduction of the needle up to about 0.63 (Vi ") into the copper oxide filling B of the combustion tube A , the plunger is lowered until 10 μ1 remain. The syringe is then left in its position until the methane peak caused by the initial injection is recorded; the remaining 10 μl solution then become injected slowly as described above.

1 sheet of drawings

Claims (1)

Claims: Ϊ. Method for determining the total small amounts of organic constituents contained in aqueous liquid bottoms; Liquid carbon dioxide can be oxidized, which is then reduced by methane being reduced by mixing hydrogen and the mixture with a suitable catalyst and so that the methane formed is ciiamuatr * ιτ> a "! H.irnnvontorns.iuor ^ cieiektOT y. : ". esseii YwPJ 1. Verü.iiron after -spring!. known thereby p c gken draws that the coal furnace.;!: in that of the i-i i-ie- s; uv, π; υ π
rich; iir> .interworner:
5: ιι.Κ / \ er: ahie ^: i; iüc; i - \: "-> ni · .. '■ ^: LiηJ 2. thereby gekeniveicnne :. that ais lcsles Ox ⁱ ii.i: ionsir;, ile! Kunie-owi.1 \ -r \>ende; will. J.is j;: i ei nor Tempera:;,; nvi her · ;; ·, · ;. ■ -..-; -. S5 ·. · bi »9DO C siehai : · .. '! ·.:: A! Is Jaci:; i \