US3631724A - Process of liquid chromatography for dosed introduction of small amounts of liquid into a flow of carrier liquid - Google Patents

Process of liquid chromatography for dosed introduction of small amounts of liquid into a flow of carrier liquid Download PDF

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Publication number
US3631724A
US3631724A US3904A US3631724DA US3631724A US 3631724 A US3631724 A US 3631724A US 3904 A US3904 A US 3904A US 3631724D A US3631724D A US 3631724DA US 3631724 A US3631724 A US 3631724A
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US
United States
Prior art keywords
tubule
liquid
channel
opening
carrier liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US3904A
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English (en)
Inventor
Helmut Oster
Ernst Ecker
Frank Wichmann
Frank Oppermann
Erich Joss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Siemens Corp
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Siemens Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19691902620 external-priority patent/DE1902620C/de
Application filed by Siemens Corp filed Critical Siemens Corp
Application granted granted Critical
Publication of US3631724A publication Critical patent/US3631724A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/24—Automatic injection systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G01N30/18—Injection using a septum or microsyringe
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G01N30/22—Injection in high pressure liquid systems

Definitions

  • the tubule is shifted into a second position so that the opening is then situated in the range of the flow of the carrier liquid.
  • the liquid contained in the tubule is injected through the opening into the flow of the carrier liquid. The process prevents a pressure surge from being propagated in the flow of the carrier liquid.
  • the purpose of the invention is to eliminate the above difficulties. Further, it provides for a process of liquid chromatography for dosed introduction of small quantities of liquid by means of an injection device into the flow of a carrier liquid so as to avoid a pressure surge propagated in the flow of the carrier liquid.
  • the process of the invention is further characterized in that at least one lateral opening is provided in a tubule or a cannula of an injection member, with the member being movable transversely relative to the flow of the carrier liquid so as to be positioned outside of the flow of the carrier liquid at which time the lateral opening is brought into contact with the liquid to be dosed.
  • the liquid is introduced into the interior of the injector containing the tubule, and then the tubule is reciprocated back toward its initial position so that the lateral opening may be placed into the range of the flow of the carrier liquid. Finally, the liquid contained in the injector is then injected through the lateral opening into the flow of the carrier liquid, and, after the predetermined amount of liquid is introduced into the stream, the tubule may once again be returned into a position to be refilled.
  • a further process of liquid chromatography for dosed introduction of small amounts of liquid by means of traversing an injection device into a flow of carrier liquid so as to avoid a pressure surge being propagated in the current of liquid with the ultimate cleaning of a tubule associated with the injection device is characterized in that in addition to the first lateral opening there may be at least one further terminal or end side opening in the dosage device.
  • At least one lateral opening of the tubule which is movable transversely in relation to the flow of the carrier liquid is situated outside of the flow of liquid in a first of several pomible positions of the tubule, and at least one opening thereof is brought in contact with the liquid to be dosed.
  • an injector containing the tubule is filled with the liquid in this first position.
  • the end side opening and the lateral openings with the exception of one opening or in the case where there is no end side opening the lateral openings with the exception of one opening are closed.
  • the tubule is then shifted into a second position in such a manner that the open lateral opening is placed in the range of the flow of the carrier liquid, whereupon the liquid contained in the injector is then injected through the lateral opening into the flow of carrier liquid.
  • the remaining openings are released after the introduction of the liquid and after the analysis and the tubule bore is rinsed with the carrier liquid penetrating from the flow of carrier liquid through a lateral opening and the tubule is then returned into its first position.
  • Another object of the invention is to provide apparatus for the realization of the process disclosed herein.
  • Such apparatus includes a separation column head provided with intersecting bores, one bore being arranged for travel of the carrier liquid and the other arranged to receive the cannula which, when projected beyond one side of the head per se, is adapted to be filled through appropriate perforations therein any may then be retracted into the head to deposit a predetermined dosage into the carrier liquid.
  • FIG. I is a view of the apparatus partially in cross section and partially in elevation.
  • FIG. 2 is a cross-sectional view of a further embodiment of the dosage device.
  • the column head is identified as l and is shown as having a bore K extending therethrough, one end of the head being provided with feed pipe Z and the other end with a separation column T.
  • the head 1 is provided with diametrically opposed bores F1 and F2 which are arranged to receive the hollow needle KA for reciprocation therein.
  • the tubule KA is of smaller diameter than the passageway K so that flow therethrough is not impeded.
  • the tubule KA is arranged to project beyond each side of the column head 1 and the bores 81 and S2, through which it passes, are provided with perforated Teflon packing members 2 and 2', each of which is sealed against leakage by means of gland members 3 and 3. It is advantageous to position the tubule KA in channels F1 and F2 with a snug fit to substantially prevent the carrier liquid flowing in passageway K from contacting (and thus chemically attacking) the packing members 2, 2'.
  • a piston rod ST is surrounded by the cannula KA and is adapted to be sealed against leakage with the rod being reciprocable, either manually or automatically, by the piston KO. Note double arrow at piston KO. In one end position the terminal or end of the piston rod ST is scarcely protruding beyond the end wall of the tubule opening 6, whereas the other end position is determined by the required volume that should be rendered free in tubule bore KB for the liquid FL to be dosed.
  • the stroke of piston rod ST is piston KO.
  • Piston rod ST is not absolutely necessary for sucking the liquid FL into the interior of the tubule KA or for injecting the liquid from the openings arranged in tubule KA that are to be described later in more detail. It is sutficient if the tubule KA is formed as a part of an injector SP (as customary in medicine), wherein only the piston KO must be displaced for filling of the liquid FL or emptying from tubule KA and parts of injector SP surrounding piston KO.
  • a lateral opening 5 is arranged in the tubule wall, the opening being situated in the external space denoted A in the position illustrated.
  • the tubule KA proper is likewise reciprocable by hand or automatically in the direction indicated by the double arrows.
  • the tubule is situated in a first position by means of a nut M which abuts the gland member 3'.
  • the second position (not shown) is determined by nut M abutting against side bar L which is attached to the column head I by means of a rod G.
  • the stroke of this translatory movement is to be dimensioned so that lateral opening 5 is situated outside gland member 3 in one end position of travel and inside head bore K of column head 1 in another end position of travel.
  • the length of tubule KA is to be selected so that when the tubule is in its second end position, the opening 6 provided at the end thereof is situated outside or at. least still inside Teflon packing 2.
  • piston rod ST must have a sufficient length so that, as shown in the drawing, its tip projects from opening 6 or can be led at least up to the opening 6.
  • the end opening 6 is absolutely necessary for an accurate operation of the device of the invention. It can be replaced by a lateral opening arranged at the terminal end, e.g., in the manner of opening 5, or be completely omitted. However, if the opening at the end is eliminated, a cleaning of the tubule interior with the carrier liquid TF flowing through head bore K, as it will be carried out in a step still to be described, is more difficult. In such a case, tubule KA must be cleaned in a position wherein lateral opening 5 is no longer situated in the range of the carrier liquid.
  • a revolving drum R rotatable about a shaft C and displaceable along shaft C in parallel with the axis of the tubule, is situated in front of opening 6 of tubule KA at a distance determined by the distance from the end opening 6 and the lateral opening 5.
  • Revolving drum R contains a plurality of containers BH for the liquid FL to be dosed and a stopper plug SF provided with a protective sack means in bore 7.
  • Revolving drum R is rotatable about shaft C so that either container Bl-l or stopper SF may be situated at the level of the tubule tip.
  • container BH or stopper SF may also be manually placed over or on the tip of tubule KA without any need for the revolving drum R.
  • the container BH may include a housing 8, as shown in FIG. 2, the housing being filled by a liquid FL which is to be dosed.
  • Housing 8 is provided with an inlet feed line 9 and a discharge outlet line 10.
  • a part of tubule KA sealed in relation to the atmosphere and housing 8 by a further Teflon seal 12 and gland-packing member 13, is situated inside housing 8 for the purpose of drawing out liquid FL.
  • a lateral opening 14 is thus situated in the range of liquid FL (the lateral opening may be replaced by an end opening 6 as shown in FIG. 1 or by further lateral openings).
  • liquid FL may be drawn by suction through opening 14, while all other openings that may be arranged on tubule KA and not situated inside housing 8 must be sealed.
  • tubule KA When the interior of the tubule or injector member is filled with liquid FL, tubule KA may be withdrawn from housing 8, whereafter opening 14 must be sealed with a stopper SF and the perforation in the gland member 13 must be tightly closed.
  • container BH is removed from the tip of tubule KA (i.e., the revolving head R is displaced along shaft C away from the tip of tubule KA and turned about shaft C until stopper SF reaches alignment with the tip and is then again displaced toward the tip) and the stopper SP is placed on the tip. (If end opening 6 is completely omitted, stopped SF need not be placed on the tip.)
  • This procedure is followed by reciprocating tubule KA back toward the column head 1 until nut M abuts against side bar L and the lateral opening 5 is situated inside bore K, the revolving drum R also participating in this stroke so that opening of tubule KA remains covered.
  • tubule bore KB may also be cleaned immediately before a new analysis.
  • piston rod ST is stopped adjacent to the lateral opening 5, whereafter the stopper SF is removed, prior to the movement of the opening 5 into alignment with bore K.
  • Carrier liquid TF which is subjected to internal pressure, then penetrated through opening 5 into internal bore KB in tubule KA and displaces the residues of liquid F L.
  • piston rod ST may either be shifted so that lateral opening 5 is blocked, or tubule KA may then be brought into its second position of abutment so that lateral opening 5 is covered by the Teflon packing 2 (or other corresponding packing member). A further injection may then be carried out.
  • a liquid chromatography injection device for introducing into a first, or carrier liquid metered quantities of a second liquid, the improvement comprising a. a separation column head,
  • a hollow tubule contained in said second channel and traversing said first channel; said hollow tubule being movable in said second channel into and between first and second positions; said hollow tubule extending fully across said first channel in said first and second positions and in any other position therebetween, means for moving said tubule into and between said first and second positions,
  • dosage-dispensing means containing said second liquid and positioned externally of the location of intersection between said first and second channels, said dosagedispensing means communicating with said tubule at least in the first position thereof,
  • a lateral opening provided in said tubule; said opening communicating with said first channel in the second position of said tubule.
  • a device wherein the means defined in (H) include an elongated rod disposed within said tubule and a reciprocable piston connected with said rod to cause movement of the latter.
  • said dosagedispensing means includes A. a housing having an inlet and an outlet; said second liquid traverses said housing by flowing through said inlet and said outlet and B. sealing means provided in said housing; said tubule is surrounded by the last-named sealing means and extends into said housing at least in the first position of said tubule.
  • tubule is disposed in said second channel in a snug fit at least between said first channel and the respective packing members on either side of said first channel.
  • a device wherein the dosagedispensing means is rotatable about its axis relative to the column head and in a plane perpendicular to the first channel 6.
  • the axis of rotation of the dispensing means is in a plane parallel to the tubule.
  • a device wherein the rotatable dispensing means is provided with a plurality of dosage devices and at least one stopper means.
  • tubule is connected to an injection body movable therewith as a unit; said piston is positioned in said injection body.
  • a device wherein the tubule is provided with abutment means arranged to cooperate with the separation column head.
  • a device according to claim 1, wherein the separation column head supports stop means offstanding therefrom and arranged to cooperate with abutment means carried by said tubule.
  • a method of injecting metered quantities of liquid by means of a hollow tubule into a carrier liquid flowing through a channel comprising the steps of A. positioning said tubule to pass entirely through said channel in an intersecting relationship therewith,

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Fluid Mechanics (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
US3904A 1969-01-20 1970-01-19 Process of liquid chromatography for dosed introduction of small amounts of liquid into a flow of carrier liquid Expired - Lifetime US3631724A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691902620 DE1902620C (de) 1969-01-20 Vorrichtung fur die Flüssig keitschromatographie zum dosierten Einbringen kleiner Probefiussigkeits mengen in einen Tragerflussigkeits strom

Publications (1)

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US3631724A true US3631724A (en) 1972-01-04

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US3904A Expired - Lifetime US3631724A (en) 1969-01-20 1970-01-19 Process of liquid chromatography for dosed introduction of small amounts of liquid into a flow of carrier liquid

Country Status (6)

Country Link
US (1) US3631724A (enrdf_load_stackoverflow)
BE (1) BE744679A (enrdf_load_stackoverflow)
FR (1) FR2028732A1 (enrdf_load_stackoverflow)
GB (1) GB1281962A (enrdf_load_stackoverflow)
LU (1) LU60197A1 (enrdf_load_stackoverflow)
NL (1) NL7000303A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3754443A (en) * 1972-02-04 1973-08-28 R Harris Automatic fluid injector
FR2336673A1 (fr) * 1975-12-22 1977-07-22 Sandoz Sa Nouvelle tete d'introduction d'echantillons pour colonnes de chromatographie en phase liquide sous haute pression
US4057997A (en) * 1976-03-31 1977-11-15 Phillips Petroleum Company Sample preparation
DE2807249A1 (de) * 1977-02-25 1978-10-12 Waters Associates Inc Vorrichtung zum einspritzen einer fluessigkeitsprobe
US4237733A (en) * 1978-04-26 1980-12-09 Bodenseewerke Perkin-Elmer & Co. GmbH Sampling device for measuring instruments
US4289029A (en) * 1979-11-02 1981-09-15 Uop Inc. High temperature injection and vaporization system for gas chromatography
US6146895A (en) * 1990-03-02 2000-11-14 Tekmar Company Method of static headspace analyzer
US20040183869A1 (en) * 2002-12-06 2004-09-23 Birgit Muller-Chorus Device for parallel metering of liquids

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4094196A (en) * 1977-02-25 1978-06-13 Waters Associates, Inc. Sample injection with automatic cleaning of sampling conduit
DE10260700A1 (de) * 2002-12-24 2004-07-08 Chankvetadze, Bezhan, Prof. Dr. Vorrichtung zur Trennung von Substanzgemischen mittels Flüssigchromatographie

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137174A (en) * 1962-11-09 1964-06-16 Le Roy R Hawk Fluid metering device
US3306502A (en) * 1965-04-28 1967-02-28 Prec Sampling Corp Apparatus for injection of fluids
US3508442A (en) * 1968-09-18 1970-04-28 Hewlett Packard Co Automatic liquid sampler for chromatography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137174A (en) * 1962-11-09 1964-06-16 Le Roy R Hawk Fluid metering device
US3306502A (en) * 1965-04-28 1967-02-28 Prec Sampling Corp Apparatus for injection of fluids
US3508442A (en) * 1968-09-18 1970-04-28 Hewlett Packard Co Automatic liquid sampler for chromatography

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3754443A (en) * 1972-02-04 1973-08-28 R Harris Automatic fluid injector
FR2336673A1 (fr) * 1975-12-22 1977-07-22 Sandoz Sa Nouvelle tete d'introduction d'echantillons pour colonnes de chromatographie en phase liquide sous haute pression
US4057997A (en) * 1976-03-31 1977-11-15 Phillips Petroleum Company Sample preparation
DE2807249A1 (de) * 1977-02-25 1978-10-12 Waters Associates Inc Vorrichtung zum einspritzen einer fluessigkeitsprobe
US4237733A (en) * 1978-04-26 1980-12-09 Bodenseewerke Perkin-Elmer & Co. GmbH Sampling device for measuring instruments
US4289029A (en) * 1979-11-02 1981-09-15 Uop Inc. High temperature injection and vaporization system for gas chromatography
US6146895A (en) * 1990-03-02 2000-11-14 Tekmar Company Method of static headspace analyzer
US6168759B1 (en) 1990-03-02 2001-01-02 Tekmar Company Analyzer transport device
US6180060B1 (en) 1990-03-02 2001-01-30 Tekmar Corporation Analyzer transport device
US20040183869A1 (en) * 2002-12-06 2004-09-23 Birgit Muller-Chorus Device for parallel metering of liquids
US7036917B2 (en) * 2002-12-06 2006-05-02 Steag Microparts Gmbh Device for parallel metering of liquids

Also Published As

Publication number Publication date
FR2028732A1 (enrdf_load_stackoverflow) 1970-10-16
NL7000303A (enrdf_load_stackoverflow) 1970-07-22
DE1902620B2 (de) 1972-09-07
BE744679A (fr) 1970-07-20
LU60197A1 (enrdf_load_stackoverflow) 1970-03-19
DE1902620A1 (de) 1970-10-08
GB1281962A (en) 1972-07-19

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