US3820660A - Fluid analytical instrument - Google Patents

Fluid analytical instrument Download PDF

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Publication number
US3820660A
US3820660A US00329142A US32914273A US3820660A US 3820660 A US3820660 A US 3820660A US 00329142 A US00329142 A US 00329142A US 32914273 A US32914273 A US 32914273A US 3820660 A US3820660 A US 3820660A
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US
United States
Prior art keywords
tubing
tube
fluid
chromatographic
length
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
US00329142A
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English (en)
Inventor
I Halasz
P Walkling
H Gerlach
K Gutlich
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Individual
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Individual
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Filing date
Publication date
Priority to DE19681675313 priority Critical patent/DE1675313C3/de
Priority claimed from DE19681675313 external-priority patent/DE1675313C3/de
Priority to NL6902180A priority patent/NL6902180A/xx
Priority to FR6903628A priority patent/FR2001967A1/fr
Priority to GB8101/69A priority patent/GB1220552A/en
Application filed by Individual filed Critical Individual
Priority to US00329142A priority patent/US3820660A/en
Application granted granted Critical
Publication of US3820660A publication Critical patent/US3820660A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/12—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting
    • F16L11/121—Hoses, i.e. flexible pipes made of rubber or flexible plastics with arrangements for particular purposes, e.g. specially profiled, with protecting layer, heated, electrically conducting specially profiled cross sections
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/56—Labware specially adapted for transferring fluids
    • B01L3/561—Tubes; Conduits
    • 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
    • G01N30/60—Construction of the column
    • G01N30/6052—Construction of the column body
    • G01N30/6086—Construction of the column body form designed to optimise dispersion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/08—Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor using a stream of discrete samples flowing along a tube system, e.g. flow injection analysis
    • 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
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/38—Flow patterns

Definitions

  • the shape reduces overlapping of compositions.
  • a tube of elliptical cross section is improved when major and minor axes of e1- lipse alternate along length of tube as by twisting the tube or providing offset pinches to a round tube. Additional efficiency is obtained when the tube with thealtemating positions of axes is wound into a helix of the order of 10 mm diameter.
  • a fluid analyzing instrument including a tube conduit having a cross section of non-circular shape and the tube being acutely contorted.
  • the problem outlined above is of special significance in chromatography, both gas and liquid, where a partitioningcolumn has a carrier medium flowing therethrough,into which medium a small slug of mixture is injected for separation into its components.
  • the inner walls ofthe open tube are coated with a thin film acting as a stationary phase which reversibly interacts with the molecules ofthe mixture-under study e.g. by absorption and desorption.
  • the several components of the mixture have different transit times through the interior of the column and hence are eluted from the column at different points of timefBecause the times of elution differ for the components, the latter can be determined by detectors based on heat conductivity or by differential refractometers. An important requirement for satisfactory measurement of the several components is that the different constituents ofthe mixture not overlap as they emerge or are eluted.
  • the ideal condition would be, that the length of the injected slug remained constant throughout the entire movement in the instrument, so that the individual components would emerge as slugs equally spaced one after the other. This has been found not to be the case however, but instead the slug undergoes a lengthening deformation which can lead to overlapping of the individual emerging slugs of the components to be determined in the mixture.
  • the lengthening increases with the flow-through speed dictated by the operating speed, which in turn is dictated by the duration of time in which an analysis must be made.
  • the lengthening deformation is traceable to. mixing actions which occur at the separation between the slugs and the carrier medium upon its movement inside of round tubular conduits in apparatus having a column formed as an open tube.
  • the invention shows a way to hold the above de scribed mixing action to an especially small amount in the longitudinal direction of the tube. It has been found if the clean cross section of the tube is not circular and the flow of the medium in the tube in the general direction of the tube is additionally altered or contorted or turned, the non-circular cross section and turning of the carrier flow each makes for greater efficiency and the two may be combined for still better results.
  • An effective and easily produced form of the invention is a tube having a substantially elliptical inner cross section that is additionally wound about an axis representing the direction of general flow through the tube. Results are better if the major axis of the ellipse lies in an approximate plane of a turn.
  • the tube is preferably formed from conventional capillary tube for columns having an inner diameter of about 1 mm by partially flattening such a tube to give an elliptical cross section having major and-minor axes in the ratio 3:1.
  • the 1 mm tube is wound into a helix having a diameter of about 10 mm.
  • the contorted flow may be obtained by twisting an elliptical tube formed in the manner mentioned above to give a full twist every 25 mm, and then winding the twisted tube into a helix of 10 mm diameter.
  • Equally as satisfactory as the twisted tube is a form in'which successive sections of a round tube are partially flattened to elliptical cross sections and wherein alternate sections are at right angles to each other about the main longitudinal axis of the tube. If the sectional lengths are not more than 50 times the length of the major axis of the cross section the desired action is obtained. The resulting tube can be additionally woun'd helically to give even greater efficiency.
  • FIG. 1 shows schematically a chromatographic apparatus including a source 1 of mobile phase or carrier medium, such as helium, providing a continuous stream of carrier gas.
  • the source may be a storage tank provided with a regulating valve.
  • the carrier medium is supplied small amounts of the sample to be analysed-by a syringe 3 through a serum cap, so that a small injected slug of the sample starts off inside the transfer medium stream at zone 2.
  • This slug migrates through the partitioning column 4 which is in the form of an open capillary tube whose inner walls are coated, the coating acting and reacting with components to be determoned in the sample. Owing to the different characteristic properties of the components to be separated, they undergo a differential separatory delay during passage through the column so as to leave the column serially, one component after another.
  • a detector 5 for example a measuring instrument based on heat conductivity, receives the separated fractions and indicates the amounts by registration on a recording chart 6.
  • the composition may be determined by area-integration under the peaks of the chart curve in conventional manner after, for example, the column has been timecalibrated for operation of the system under fixed conditions. For good measurements it is essential that the peaks not overlap. They should be steep sided. This means that the slugs formed from the different components should not become so elongated inside the column that they may mix with each other. Since the column is of capillary dimensions and must be very long, the column is coiled helically to conserve space.
  • FIG. 2 shows a column in one form of the invention.
  • a capillary cylindrical tube of about I mm inside diameter has been squeezed to produce one of elliptical cross section.
  • the major and minor axes of the cross sections are about in the ratio 3:1 and are denoted a and b.
  • the squeezing of the tube, if of metal, may be carried out between rollers, but it may be carried out in the same manner at softening temperatures if glass or plastic tubing is used.
  • the tube is moreover coiled to form a relatively tightly wound helix of about 8 to 30 mm in diameter preferably about 10 mm, which is in the general course of the tube.
  • the novel feature is then not as to the general loose coiling which is as shown in FIG.
  • FIG. 2 The construction in FIG. 2 is thus a tight winding according to FIG. 2 incorporated in the further loose coiling shown in FIG. 1.
  • the conduit is first formed according to FIG. 2 and then the coiled tube is loosely wound according to FIG. I in order to reduce space requirements.
  • FIG. 3 A modification of the invention is shown in FIG. 3.
  • the same tube of elliptical cross section is used, but the tube is twisted so as to provide a full turn for each say, to 50 mm of length, preferably about mm, along its l ongitudinal axis.
  • This twisting can be done by holding one end of a straight tube fast and turning the other about the tube axis.
  • the lie of the different sectional portions is shown in FIG. 3a.
  • Such a tube exhibits, in this very form, an increased effect in inhibition of overlapping. It can thus be coiled to conserve space as shown in FIG. I and used as a chromatographic column. An especially good effect is obtained if the twisted tube is first tightly wound as a helix similar to that in FIG. 2, and then the helical coil loosely looped in order to conserve space as shown in FIG. 1.
  • FIG. 4 shows another modification of the invention.
  • a straight cylinder (1 mm diameter).
  • straight denotes a coiling into loops with the loop diameter of at least 50 mm in diameter to save space.
  • Looping of the diameter was found to be essentially of the same effect as actually straight tubing.
  • the total length of tubing used in a column was from I 20 to 30 meters for liquids and 45 meters for gas.
  • FIGS. 5 and 6 the widening h of the slugs in cm is plotted against flow rate of the carrier medium in cm/sec. for the various forms of tubes A to F.
  • FIG. 5 shows the results in the case of liquid chromatography.
  • the values of h are less than those for the cylindrical tubing, whether tightly helically wound or not, at any given flow rate. It may be noted that the different forms vary in their effect.
  • the curve F for the elliptical, twisted, and then helically wound tube This form of the tube gives a very low value for h and the action is nearly independent of flow rate.
  • the action is independent from the action of the partitioning column.
  • the slug lengthening is accordingly reduced when alternate action of the molecules does 1 not take place with the coating of the partitioning column.
  • Chromatographic apparatus for examining fluids comprising a source of carrier fluid, means connected to said source adapted to define a stream for the carrier fluid, means for introducinga sample into a stream of the carrier fluid, a chromatographic column defining a path for the fluid stream following the point of introduction of the sample, a detector connected to said chromatographic column for measuring a characteristic parameter of the fluid stream emerging from said chromatographic column, said chromatographic column being formed of tubing which has been geometrically deformed along a substantial portion of its length so that the tubinghas a major and a minor diameter, said major and minor diameters being alternatively rotated along the deformed portion to produce a movement of the fluid transverse to the direction of flow, said major and minor diameters being of constant lengths throughout the length of said tubing whereby the volume of fluid flow is unchanged throughout the length of said tubing.
  • Chromatographic apparatus according to claim 1 wherein said tubing is formed by successively pinching the tubing at spaced invervals along the length thereof with alternate pinchings disposed at 90 to each other.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Clinical Laboratory Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
US00329142A 1968-02-15 1973-02-02 Fluid analytical instrument Expired - Lifetime US3820660A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE19681675313 DE1675313C3 (de) 1968-02-15 1968-02-15 Rohr zur Führung sich in ihrer Zusammensetzung ändernder Medien für analytische Geräte
NL6902180A NL6902180A (de) 1968-02-15 1969-02-12
FR6903628A FR2001967A1 (de) 1968-02-15 1969-02-14
GB8101/69A GB1220552A (en) 1968-02-15 1969-02-14 Instruments for analysing or separating fluids
US00329142A US3820660A (en) 1968-02-15 1973-02-02 Fluid analytical instrument

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEH0065321 1968-02-15
DE19681675313 DE1675313C3 (de) 1968-02-15 1968-02-15 Rohr zur Führung sich in ihrer Zusammensetzung ändernder Medien für analytische Geräte
US79835869A 1969-02-11 1969-02-11
US00329142A US3820660A (en) 1968-02-15 1973-02-02 Fluid analytical instrument

Publications (1)

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US3820660A true US3820660A (en) 1974-06-28

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US00329142A Expired - Lifetime US3820660A (en) 1968-02-15 1973-02-02 Fluid analytical instrument

Country Status (4)

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US (1) US3820660A (de)
FR (1) FR2001967A1 (de)
GB (1) GB1220552A (de)
NL (1) NL6902180A (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416234A2 (de) * 1989-09-05 1991-03-13 Hewlett-Packard Company Elektroforesegerät
US5032283A (en) * 1983-03-03 1991-07-16 The Perkin Elmer Corporation Low dispersion fluid conduit useful in chromatography systems
US5273655A (en) * 1989-10-10 1993-12-28 The Regents Of The University Of California Organic contaminant separator
US5308493A (en) * 1989-10-10 1994-05-03 The Regents Of The University Of California Organic contaminant separator
US5391296A (en) * 1994-01-05 1995-02-21 Rotundo; David A. Pool skimmer deflecting device
EP0990133A1 (de) * 1996-02-08 2000-04-05 Lab Connections, Inc. Düsenanordnung zum sammeln von flüssigkeitskomponenten zur analyse
US20090139934A1 (en) * 2007-12-03 2009-06-04 Schlumberger Technology Corporation Differential acceleration chromatography
EP2098284A2 (de) * 2008-03-05 2009-09-09 Dionex Softron GmbH Kapillarartige Verbindung für die Flüssigkeitschromatographie, insbesondere für die Hochleistungsflüssigkeitschromatographie mit verminderter Dispersion und verbesserten thermischen Eigenschaften
WO2011061769A1 (en) * 2009-11-18 2011-05-26 Avantech Group S.R.L. Supporting devices for capillary and nano hplc columns
CN102214491A (zh) * 2010-04-07 2011-10-12 通用电气-日立核能美国有限责任公司 用于最大化钼-99洗提效率的塔几何结构
CN107149794A (zh) * 2017-06-30 2017-09-12 西华大学 一种高效分离生物大分子的方法及所用碟片式螺旋管柱
WO2018150842A1 (ja) * 2017-02-15 2018-08-23 株式会社島津製作所 分析装置用の配管デバイス及びその配管デバイスを用いた分析装置

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5032283A (en) * 1983-03-03 1991-07-16 The Perkin Elmer Corporation Low dispersion fluid conduit useful in chromatography systems
EP0416234A2 (de) * 1989-09-05 1991-03-13 Hewlett-Packard Company Elektroforesegerät
EP0416234A3 (en) * 1989-09-05 1991-07-03 Hewlett-Packard Company Electrophoresis apparatus
US5273655A (en) * 1989-10-10 1993-12-28 The Regents Of The University Of California Organic contaminant separator
US5308493A (en) * 1989-10-10 1994-05-03 The Regents Of The University Of California Organic contaminant separator
US5389251A (en) * 1989-10-10 1995-02-14 The Regents Of The University Of California Organic contaminant separator
US5403477A (en) * 1989-10-10 1995-04-04 The Regents Of The University Of California Organic containment separator
US5391296A (en) * 1994-01-05 1995-02-21 Rotundo; David A. Pool skimmer deflecting device
EP0990133A1 (de) * 1996-02-08 2000-04-05 Lab Connections, Inc. Düsenanordnung zum sammeln von flüssigkeitskomponenten zur analyse
EP0990133A4 (de) * 1996-02-08 2000-04-05 Lab Connections Inc Düsenanordnung zum sammeln von flüssigkeitskomponenten zur analyse
US8778059B2 (en) 2007-12-03 2014-07-15 Schlumberger Technology Corporation Differential acceleration chromatography
WO2009073270A1 (en) * 2007-12-03 2009-06-11 Services Petroliers Schlumberger Differential acceleration chromatography
US20090139934A1 (en) * 2007-12-03 2009-06-04 Schlumberger Technology Corporation Differential acceleration chromatography
US8512457B2 (en) 2007-12-03 2013-08-20 Schlumberger Technology Corporation Differential acceleration chromatography
EP2098284A3 (de) * 2008-03-05 2009-11-11 Dionex Softron GmbH Kapillarartige Verbindung für die Flüssigkeitschromatographie, insbesondere für die Hochleistungsflüssigkeitschromatographie mit verminderter Dispersion und verbesserten thermischen Eigenschaften
US20090266752A1 (en) * 2008-03-05 2009-10-29 Hermann Hochgraeber Capillary-like connector for liquid chromatography, in particular, high-performance liquid chromatography with reduced dispersion and improved thermal characteristics
EP2098284A2 (de) * 2008-03-05 2009-09-09 Dionex Softron GmbH Kapillarartige Verbindung für die Flüssigkeitschromatographie, insbesondere für die Hochleistungsflüssigkeitschromatographie mit verminderter Dispersion und verbesserten thermischen Eigenschaften
WO2011061769A1 (en) * 2009-11-18 2011-05-26 Avantech Group S.R.L. Supporting devices for capillary and nano hplc columns
CN102214491A (zh) * 2010-04-07 2011-10-12 通用电气-日立核能美国有限责任公司 用于最大化钼-99洗提效率的塔几何结构
US9240253B2 (en) * 2010-04-07 2016-01-19 Ge-Hitachi Nuclear Energy Americas Llc Column geometry to maximize elution efficiencies for molybdenum-99
WO2018150842A1 (ja) * 2017-02-15 2018-08-23 株式会社島津製作所 分析装置用の配管デバイス及びその配管デバイスを用いた分析装置
JPWO2018150842A1 (ja) * 2017-02-15 2019-11-07 株式会社島津製作所 分析装置用の配管デバイス及びその配管デバイスを用いた分析装置
CN107149794A (zh) * 2017-06-30 2017-09-12 西华大学 一种高效分离生物大分子的方法及所用碟片式螺旋管柱
CN107149794B (zh) * 2017-06-30 2019-11-08 西华大学 一种高效分离生物大分子的方法及所用碟片式螺旋管柱

Also Published As

Publication number Publication date
DE1675313A1 (de) 1972-03-16
GB1220552A (en) 1971-01-27
DE1675313B2 (de) 1975-05-28
NL6902180A (de) 1969-08-19
FR2001967A1 (de) 1969-10-03

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