SE190819C1

SE190819C1 -

Info

Publication number: SE190819C1
Authority: SE
Publication date: 1964-01-01

Description

Uppfinnare: M H Pelavin Prioritet begdrd tram den 3 juli 1961 (USA) Uppfinningen hanfor sig till analys- och registreringsapparater och narmare bestamt till kontrollsystemet i en apparat for kvantitativ matning och registrering av resultat erhallna vid analys av de spektra, som utsandas av en i en brannare inford substans, allt i andamal att kvantitativt bestamma ett element i substansen. Inventor: MH Pelavin Priority requested tram on July 3, 1961 (USA) The invention relates to analysis and recording apparatus and more particularly to the control system of an apparatus for quantitative feeding and recording of results obtained by analyzing the spectra emitted by one in one. burner inford substance, all in andamal to quantitatively determine an element in the substance.

Den registrerande spektralfotometern enligt uppfinningen kan anvandas for kvantitativ analys av olika vatskor med avseende pa en eller flera substanser dari, exempelvis, men utan begransning dartill, analys av blodserum med avseende pa natrium och/eller kaHum. Vid sadan analys sattes litiumklorid eller en annan, ldmplig substans till provet av blodserum, for att man skall erhalla ett prov innehallande en standard eller referens. Nan provet, som innehaller litiumktorid, infores i brannarens laga, erhalles kvantitativ bestamning av exempelvis natrium genom overforing av spektralljuset, som svarar mot spektrallinjen fOr natrium, till en ljuskanslig anordning eller ljusdetektor for astadkommande av en elektrisk strain, vans styrka ãr proportionell till mangden av namnda spektralljus och samtidigt overfOres spektralljuset, som motsvarar spektrallinjen for litium till en annan ljuskanslig anordning, sa att man en-hailer en en annan stromstyrka, som fir proportionell till mangden av sistnamnda spektralljus. En registreringsapparat, som regleras av en differensmatbrygga (null-type balance current ratio system) av noll-typ, registrerar fiirhallandet mellan strommarna som ett matt for den i blodserumet ingaende natriummangden. The recording spectral photometer according to the invention can be used for quantitative analysis of different fluids with respect to one or more substances therein, for example, but without limitation thereof, analysis of blood serum with respect to sodium and / or potassium. In such an assay, lithium chloride or another, exemplary substance was added to the blood serum sample to obtain a sample containing a standard or reference. When the sample, which contains lithium chloride, is introduced into the burner layer, quantitative determination of, for example, sodium is obtained by transferring the spectral light corresponding to the spectral line of sodium to a light-sensing device or light detector for producing an electric strain, the strength of which is proportional to the manganese. said spectral light and at the same time the spectral light, which corresponds to the spectral line of lithium, is transferred to another light-sensing device, so that a different current is obtained which is proportional to the amount of the latter spectral light. A recording apparatus, controlled by a zero-type balance current system (zero-type balance current ratio system), records the ratio between the streams as a mat for the amount of sodium entering the blood serum.

I en apparat av ovan angivet slag uppsta ibland falska maxima och minima i registreringen av spektralanalysen av provet pa grund av lagans »butler», som interfererar med registreringarnas riktiga avlasning. Enligt hu vudandamalet med uppfinningen ar apparatens matbrygga forsedd med medel, som eliminerar effekten av namnda »butler», sa att den erhallna registreringen har fa am nagra ails falska maxima och minima. In an apparatus of the kind indicated above, false maxima and minima sometimes occur in the recording of the spectral analysis of the sample due to the law 'butler', which interferes with the correct reading of the recordings. According to the main object of the invention, the food bridge of the apparatus is provided with means which eliminate the effect of the said "butler", so that the obtained registration has few false maximums and minimums.

Uppfinningens andamal, kannetecken och fordelar torde klart framga av foljande beskrivning av den for narvarande foredragna utforingsformen under hfinvisning till bifogade ritning. I fig. 1 visas ett kopplingssehema och en sehematisk vy av en spektralanalys- och registreringsfotometer, varmed sattet och apparaten enligt uppfinningen askadliggores. 1 fig. 2 visas spektralanalyskurvor, som anvfindas vid forklaring av apparaten enligt fig. 1. The spirit, features and advantages of the invention will become apparent from the following description of the presently preferred embodiment, taken in conjunction with the accompanying drawings. Fig. 1 shows a switching diagram and a semantic view of a spectral analysis and recording photometer, with which the set and the apparatus according to the invention are exposed. Fig. 2 shows spectral analysis curves used in explaining the apparatus of Fig. 1.

Den registrerade spektralfotometern 10 omfattar en spektralbrannare 12 och en registreringsapparat 14, som styres av differensmatbryggan 16. Spektralljus motsvarande spektrallinj en fOr det element, som skall analyseras, 8verfores till den ljuskansliga anordningen eller detektorn 18 och spektralljus svarande mot spektrallinj en for den i provet inforda, interna standarden, overfores till den ljuskansliga anordningen eller detektorn 20. Ett filter 22 dr anordnat i ljusets bana fran lagan F till detektorn 18 och endast ljus, som svarar mot det for analys avsedda elementets spektrallinje passerar genom detta filter. Mellan. detektorn 20 och lagan ar ett filter 24 anordnat och genom detta passerar endast ljus, som svarar mot standardelementets spektrallinje. De ljuskansliga anordningarna utgoras lampligen av fotokonduktiva celler av kadmiumsulfid, vilka aro valkanda anordningar och som i&e behova beskrivas narmare. Pd var och en av de fotosensitiva anordningarna är en reglerad, konstant spanning fran shornkallan 26 patryckt och den darav i var och en av de ljuskansliga anordningarnas krets orsakade striimmen ar proportionell till det 2— — spektralljus, som instralas i resp. anordning. The recorded spectral photometer 10 comprises a spectral burner 12 and a recording apparatus 14 controlled by the differential feed bridge 16. Spectral light corresponding to spectral line one for the element to be analyzed is transferred to the light sensor device or detector 18 and spectral light corresponding to the spectral line in the sample , the internal standard, is transmitted to the light-sensing device or detector 20. A filter 22 is arranged in the path of light from the layer F to the detector 18 and only light corresponding to the spectral line of the element to be analyzed passes through this filter. Between. the detector 20 and the layer are a filter 24 arranged and through this only light passes, which corresponds to the spectral line of the standard element. The light-sensing devices are suitably constituted by photoconductive cells of cadmium sulphide, which are optional devices and which need to be described in more detail. On each of the photosensitive devices a regulated, constant voltage from the horn source 26 is printed and the current caused by it in the circuit of each of the light sensing devices is proportional to the 2 - - spectral light, which is irradiated in resp. device.

I kretsen med den ljuskansliga anordningen 18 ingar ett motstand 28 och en kapacitans 30 och i den. ljuskansliga anordningens 20 krets ingar ett motstand 32 och en variabel kapacitans 31. Enligt uppfinningen är kapacitansen 31, sasom narmare skall forklaras har nedan, installd pa ett varde, som eliminerar effekten av falska maxima och minima I strOmmarna i de ljuskansliga kretsarna, vilka upptrada till foljd av brannarens drift och resultera i falska maxima och minima i diagrammet 36, som av pennan 40 i registreringsapparaten 14 skrives pa papperet 38. Motstanden 28 och 32 anya..ndas for att minska kondensatorernas 30 och 34 storlek till praktiska matt. I den ljuskansliga anordningens 18 krets finnes ett belastningsmotstand 42 med en glidkontakt 44. Potentiometern 46 är forbunden med den ljuslansliga anordningens 20 krets via ledningarna 48 och 50. In the circuit with the chancel device 18 a resistor 28 and a capacitance 30 enter and into it. According to the invention, the capacitance 31, which will be explained in more detail below, is set at a value which eliminates the effect of false maxima and minima in the currents in the light-sensing circuits which occur at followed by the operation of the burner and result in false maxima and minima in the diagram 36, which is written by the pen 40 in the recording apparatus 14 on the paper 38. The resistors 28 and 32 are used to reduce the size of the capacitors 30 and 34 to practical mat. In the circuit of the chandelier device 18 there is a load resistor 42 with a sliding contact 44. The potentiometer 46 is connected to the circuit of the chandelier device 20 via the lines 48 and 50.

Atgarder aro vidtagna f Sr neutralisation av motstandsforandringarna i de ljuskansliga anordningarna 18 och 20 pa grund av variationer i omgivningens temperatur. Narmare bestamt avtar motstandet hos de ljuskansliga anordningarna med Skning av ljuset, for vilket anordningarna utsattas, men motstandet okas med stigande temperatur. Den omgivande temperaturens effekt pa anordningens motstand upphaves med hjalp av termistorer 52 och 51 i serie med anordningarna 18 resp. 20, temperaturutjamnande fOrhallande dartill. Termistorerna 52 och 54 aro, om sã erfordras, utrustade med utjamnande motstand 56 resp. 58 i shunt med namnda termistorer for att harrnoniera med eller reducera skillnaderna i temperaturmotstandskarakteristiken hos termistorn och dess motsvarande ljusltansliga anordning. Measures have been taken to neutralize the changes in resistance in the light sensor devices 18 and 20 due to variations in the ambient temperature. More specifically, the resistance of the chancel devices decreases with the exposure of the light to which the devices are exposed, but the resistance increases with increasing temperature. The effect of the ambient temperature on the resistance of the device is obtained by means of thermistors 52 and 51 in series with the devices 18 and 18, respectively. 20, temperature equalizing relationship thereto. The thermistors 52 and 54 are, if required, equipped with equalizing resistors 56 and 56, respectively. 58 in shunt with said thermistors to harmonize with or reduce the differences in the temperature resistance characteristic of the thermistor and its corresponding light emitting device.

Registreringsanordningen 14 Sr av den valkanda, sjalvbalanserande glidtradstypen, sasom ovan angivits. Den rorliga kontakten 60 pa potentiometern. 46 Sr forskjutbar i overensstammelse med pennan 40$ registreringsanordningen och bada aro forbundna med muttern 62, som fares utefter gangorna pa den roterande staven 64, som drives av en tvafasmotor 66. Givetvis fasthalles muttern 62 gentemot rotation och staven 64 fasthalles gentemot forskjutning i sin langdriktning, sa att nar den vrides av motorn 66 flyttas mutter. 62 utefter staven for balanserande manovrering av kontakten 60 och darmed samtidigt skeende forflyttning av pennan 40, varigenom kurvan 36 ritas pa papperet 38. The recording device 14 Sr of the selective, self-balancing slide line type, as indicated above. The movable connector 60 on the potentiometer. 46 is displaceable in accordance with the pen 40 $ recording device and both are connected to the nut 62, which is driven along the passages of the rotating rod 64, which is driven by a two-phase motor 66. Of course, the nut 62 is held against rotation and the rod 64 is held against displacement in its longitudinal direction. , so that when it is turned by the motor 66, the nut is moved. 62 along the rod for balancing maneuvering of the contact 60 and thereby simultaneous movement of the pen 40, whereby the curve 36 is drawn on the paper 38.

Sasom Sr valkant far fackmannen pa. omradet varierar strommen genom anordningen pa grund av den ljuskansliga anordningens 18 gensvar pa spektralljuset och det uppstar en strom genom motstandet 42, som ger upphov till ett spanningsfall Over namnda mot-stand, och en del av denna spanning till- Hires via kontakten 44 och ledningen 68 till en omformare 70. Pa samma satt varierar strommen genom anordningen p0. grund av den ljuskansliga anordningens 20 gensvar pS spektralljuset och det uppstar en strom genom motstandet 32 och glidtradspotentiometern 46 i registreringsanordningen och det bar beaktas, att namnda glidtrad Sr forbunden med kretsen for den. ljuskansliga anordningen for den interna standarden. Kontakten 60 ph glidtradspotentiometern. 46 Sr forbunden med omformaren 70 via ledningen 72, sa att spanningsskillnaden mellan kontakten 60 och kontakten 44 patryckes omformaren. Denna forandrar likstromsspanningen till en vaxelstromsspanning och vaxelstromsspanningen p0. omformarens utgangssida patryckes transformatorn 74, forstarkes av forstarkaren 76 och patryckes lindningen 78 pa tvafasmotorn 66. Den andra lindningen tvafasmotorn matas med vaxelstrom fran en stromkalla 82. Motor. 66 arbetar i beroende av spanningsdifferensen mellan kontakterna 60 och 44 och driver kontakten 60 pa potentiometern for balans av systemet, vid vilken punkt det icke patryckes flagon spanning pa. omformaren 70. Pennans 40 rorelse under balanseringsoperationen medfor en registrering pa papperet, vilken utgor forhallandet mellan de ljuskansliga anordningarnas gensvar och utgor ett matt fill'. elementmangden i den analyserade substansen. Sasom Sr valkant far fackmannen pa. the current varies through the device due to the response of the light sensor device 18 to the spectral light and a current arises through the resistor 42, which gives rise to a voltage drop across said resistor, and a part of this voltage is supplied via the contact 44 and the wire. 68 to a converter 70. In the same way, the current through the device p0 varies. due to the response of the light sensor device 20 to the spectral light and a current is generated through the resistor 32 and the glide path potentiometer 46 in the recording device and it should be considered that said glide line Sr is connected to the circuit for it. the chancel device for the internal standard. Contact 60 ph glide wire potentiometer. 46 Is connected to the converter 70 via the line 72, so that the voltage difference between the contact 60 and the contact 44 is pressed into the converter. This converts the DC voltage to an AC voltage and the AC voltage p0. the output side of the converter is depressed by the transformer 74, amplified by the amplifier 76 and the winding 78 is pressed on the two-phase motor 66. The second winding the two-phase motor is supplied with alternating current from a cold source 82. Motor. 66 operates depending on the voltage difference between the contacts 60 and 44 and drives the contact 60 on the potentiometer for balancing the system, at which point no flagon voltage is pressed. the movement of the pen 70. The movement of the pen 40 during the balancing operation entails a registration on the paper, which constitutes the ratio between the response of the light-sensing devices and constitutes a dull fill '. the amount of elements in the analyzed substance.

Den »buller»-eliminerande effekten av kapacitansen 34 kan bast forklaras under hanvisaing till fig. 2, i vilken visas en starkt forstorad del av en kurva 84 erhallen vid spektralanalys av ett prov med avseende pa enbart litium, och en kurva 86 i samma skala som kurvan 84, erhallen vid spektralanalys av ett prov exempelvis med avseende pa en-hart natrium. Dessa kurvor kunna erhallas genom att apparaten laires »single-endech i motsats till »double-ended». Med det sistnamnda uttrycket avses att bade litium- och natriumhalten i provet samtidigt bestammes och jamforas med varandra. The "noise" eliminating effect of capacitance 34 can best be explained with reference to Fig. 2, which shows a greatly enlarged part of a curve 84 obtained by spectral analysis of a sample with respect to lithium alone, and a curve 86 of the same scale. as curve 84, obtained by spectral analysis of a sample, for example with respect to one sodium. These curves can be obtained by letting the device "single-endech" as opposed to "double-ended". The latter term means that both the lithium and sodium contents of the sample are simultaneously determined and compared with each other.

Den ljuskansliga anordningen, som paverkas av litiumhalten i provet Sr shuntkopplad och beledsagande, icke-ljuskansliga elektriska anordningar aro insatta i stallet for att astadkomma en strom for referenssidan, som omfattar glidtraden 40 for reglering av registreringsanordningens verkan, nar anordningen Wires »single-endeth, sO. att det bildas en kurva 86, som representerar natriumhalten i provet utan nagon inverkan frail litiumhalten. FOr att erhalla kurvan 84 for litiumhalten anvandes vid >> single-ended» manovrering av registreringsanordningen, en icke-ljuskanslig, elektrisk anordning for att astadkonnma en strain for referenssidan och provsidan av kretsen gores kanslig for litiums spektralljus. I hada fallen visar registreringsanordningen forhallandet mellan spektral- —3 ljusen frail provet och en fixerad spanning som fir ersatt i referenssidan av kretsen. Engl. »single-ended» och »double-ended» drift av en spektralfotometer aro valkanda och i oeh for sig joke utgora nh.gon del av uppfinning- en, fir det OverflOdigt att ingh. pa flagon ytterligare beskrivning. The light-sensing device, which is affected by the lithium content of the sample. sO. that a curve 86 is formed, which represents the sodium content of the sample without any effect on the lithium content. In order to obtain the curve 84 for the lithium content, in "single-ended" operation of the recording device, a non-light-sensitive electrical device is used to provide a strain for the reference side and the sample side of the circuit is made sensitive for the spectral light of the lithium. In all cases, the recording device shows the relationship between the spectral lights from the sample and a fixed voltage which is replaced in the reference side of the circuit. Engl. "Single-ended" and "double-ended" operation of a spectral photometer aro valkanda and in oeh for itself joke constitute nh.gon part of the invention, fir it Superfluous to ingh. on flag further description.

En granskning av kurvorna 84 och 86 ger vid handen, att »bullret» som orsakar maxi- ma 88 och minima 90 ph kurvorna, vilka re- presentera en vaxelstromsvariation i det genomsnittliga likstromsvardet ph den strain, som flyter genom kretsen for den ljuskansliga anordningen 18 resp. 20. Effekten av des- sa vaxelstromsmaximum-maximumvariationer kunna reduceras eller helt elimineras genom injustering av kapacitansens 34 varde, sh att forhallandet mellan vaxelstromsmaximamaximavardet och det genomsnittliga likstromsvardet hos de strommar, som ga genom resp. kretsar i de ljuskansliga anordningarna aro samma och likuande variationer darigenom elimineras i de resulterande kurvorna, som astadkommas av registreringsanordningen under analysen, nar apparaten kores »double-ended». Narmare bestamt har, sasom antydes i fig. 2, kapacitansen 34 instfillts pa ett varde, varigenom forhallandet mellan vaxelstromsmaxima-maximavardet 6, for litiumkurvan 84, till det genomsnittliga likstromsvardet 63 är 9,52 %. For natriumkurvan 86 ãr forhallandet mellan vaxelstromsmaximum-maximumvardet 5 till det genomsnittliga likstromsvardet 52,5 aven g,52 %, sd att forhallandena mellan vaxelstromsmaximum-maximumvardet och det genomsnittliga liks Lromsvardet for hada kurvorna aro samma och effekten av »bullret» frfin brannaren elimineras under normal »double-ended» analys med apparaten och registreringen av analysen joke omfattar falska maxima och minima. An examination of curves 84 and 86 suggests that the "noise" causing the maximum 88 and minimum 90 ph curves, which represent an alternating current variation in the average DC value ph the strain flowing through the circuit of the light sensor device 18 resp. 20. The effect of these alternating current maximum variations can be reduced or completely eliminated by adjusting the value of the capacitance 34, sh that the ratio between the alternating current maximum value and the average direct current value of the currents passing through resp. circuits in the chancel devices are the same and similar variations are thereby eliminated in the resulting curves produced by the recording device during the analysis when the device is run "double-ended". More specifically, as indicated in Fig. 2, the capacitance 34 is set to a value, whereby the ratio between the alternating current maximum value 6, for the lithium curve 84, to the average direct current value 63 is 9.52%. For the sodium curve 86, the ratio between the alternating current maximum value 5 to the average direct current value is 52.5, also 52%, so that the ratios between the alternating current maximum value and the average equilibrium value for the curves are the same and the effect of the "noise" is below the burner. normal "double-ended" analysis with the device and the registration of the analysis joke includes false maxima and minima.

Ehuru apparaten beskrivits med en variabel kapacitans 34, Or det givet, att flagon av kapacitanserna 30 eller 34 kan eras justerbar och den andra kapacitansen kan ha ett fixerat varde. En av kapacitanserna 30 eller 34 kan varieras sa, att forhallandet mellan vaxelstromsmaximum-maximumvarde och det genomsnittliga likstromsvardet for varje kurva är samma. Det är ocksh klart, att bada kapacitanserna 30 och 34 kunna vara fixerade och att ett av dem kan forses med en utjfimningskapacitans fOr uppniende av det riktiga kapacitansvardet for att erhalla samma forhallanden for hada kurvorna. Although the apparatus is described with a variable capacitance 34, it is given that the flake of the capacitances 30 or 34 may be adjustable and the other capacitance may have a fixed value. One of the capacitances 30 or 34 can be varied so that the ratio between the maximum current maximum value and the average direct current value for each curve is the same. It is also clear that both capacitances 30 and 34 can be fixed and that one of them can be provided with an equalizing capacitance to achieve the correct capacitance value in order to obtain the same ratios for the curves.

Claims

Patent claim:

A recording flame spectrophotometer apparatus for spectral analysis of a liquid, which contains in part a substance to be determined. an internal standard, which apparatus comprises a spectral layer burner (12), a recording device (14) and a differential feed bridge containing a light-sensing device (18) for receiving the spectral light corresponding to said substance and generating a first current, and another light-sensing device (20) for receiving the spectral light corresponding to the internal standard and generating a second strain, the recording device 5. being arranged to be influenced by the differential feed bridge corresponding to the ratio between the bent currents, characterized in that the voltage circuit One of the light sensor devices (20) comprises an installable capacitance means (34) for eliminating the effect of false maxima and minima in the two currents, which would cause false maxima and minima in the diagram produced by the recording device.

Apparatus according to claim 1, characterized in that the capacitance means (34) is such that the ratio of the difference between the maximum and minimum alternating current values to the average direct current value in the first current is the same as the corresponding ratio for the second current.

Apparatus according to claim 1 or 2, characterized in that each of the photovoltaic devices (18, 20) is connected to thermistors (52, 54) for neutralizing the effect on the photovoltaic devices exerted by variations in the environment. temperature. Request Publications: U.S. Patent Nos. 2,843,007, 3,031,915.