Comparator apparatus and process

• US 4,327,323 A
• Filed: 12/03/1979
• Issued: 04/27/1982
• Est. Priority Date: 12/03/1979
• Status: Expired due to Term

• Current Assignee: Siemens AG
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Walker, Starnes E.
• Primary Examiner(s): Krawczewicz, Stanley T.
• Application Number:
  US06/099,272
• Time in Patent Office: 876 Days
• Field of Search: 324/61 R, 324/140 R, 73/61.1 C, 73/23.1, 361/281, 361/278, 361/285, 361/292, 361/295, 361/299, 361/300
• US Class Current: 324/663
• CPC Class Codes: G01N 27/221 by investigating the dielectric properties using microwaves G01N22/00; measuring loss factors or dielectric constants per se G01R27/26
• CPC Class Codes: G01R 23/15 Indicating that frequency of pulses is either above or below a predetermined value or within or outside a predetermined range of values, by making use of non-linear or digital elements (indicating that pulse width is above or below a certain limit)
• CPC Class Codes: G01R 27/2635 Sample holders, electrodes or excitation arrangements, e.g. sensors or measuring cells

Abstract

Comparator apparatus and method produce a signal representative of the relationship between two signals. In a further aspect, the comparator apparatus and method are used to provide a calibration and status monitor for a chromatographic analyzer.

Claims

1. Apparatus comprising:

column means for chromatographically separating sample constituents to produce an eluate stream;

means for passing a first carrier fluid stream to the column means;

means for injecting sample constituents into the first carrier fluid stream being passed to the column means;

dielectric constant detector means including sample cell means having a first capacitance representative of a fluid passing therethrough and reference cell means having a second capacitance representative of a fluid passing therethrough;

means for passing the eluate stream through the sample cell means;

means for passing a second carrier fluid stream to the reference cell means;

first oscillator means comprising said sample cell means for producing a first frequency representative of the first capacitance;

second oscillator means comprising said reference cell means for producing a second frequency representative of the second capacitance;

means for combining the first frequency and the second frequency to produce an analysis frequency; and

comparator means for determining a threshold frequency and for producing a sensible signal representative of a difference between the threshold frequency and the analysis frequency.

2. Apparatus as in claim 1 further comprising:

means for converting the analysis frequency signal to a DC voltage, the DC voltage being representative of the concentration of the component of the sample passing through the sample cell.

3. Apparatus as in claim 2 wherein the dielectric constant detector means further comprises:

means for adjusting the capacitance of the sample cell and the capacitance of the reference cell so that the capacitance of the sample cell is substantially equal to the capacitance of the reference cell when only carrier fluid is flowing both through the reference cell and through the sample cell.

4. Apparatus as in claim 3 further comprising:

means for passing carrier fluid stream containing separated sample constituents from the column means to the sample cell means of the dielectric constant detector means; and

means for passing a carrier fluid stream to the reference cell means of the dielectric detector means.

5. Apparatus as in claim 4 wherein the dielectric constant detector means further comprises:

a reference cell means having first and second plates which form a first capacitor;

a sample cell means having first and second plates which form a second capacitor; and

means for substantially matching the capacitance of the first capacitor with the capacitance of the second capacitor when the same fluid is flowing through both the reference cell and the sample cell.

6. Apparatus as in claim 5 wherein the means for substantially matching the capacitance of the first capacitor with the capacitance of the second capacitor comprises means for varying the volume of fluid which can be present between the first and second plates of at least one of the first capacitor and the second capacitor.

7. Apparatus as in claim 6 wherein the means for substantially matching the capacitance of the first capacitor with the capacitance of the second capacitor comprises:

means for varying the volume of fluid which can be present between the first and the second plates of the first capacitor; and

means for varying the volume of fluid which can be present between the first and the second plates of the second capacitor.

8. Apparatus as in claim 7 wherein the dielectric constant detector further comprises:

an outer plate having an opening extending through at least a portion of the outer plate, the opening forming at least first, second, and third cylindrical openings;

a first inner plate concentric with the portion of the outer plate which encloses a portion of the first cylindrical opening and a portion of the second cylindrical opening, the first inner plate and the portion of the outer plate with which the inner plate is concentric thereby forming a sample cell;

a second inner plate concentric with the portion of the outer plate which encloses a portion of the second cylindrical opening and a portion of the third cylindrical opening, the second inner plate and the portion of the outer plate with which the second inner plate is concentric thereby forming a reference cell;

means for providing a fluid to the sample cell;

means for providing a fluid to the reference cell;

a first end cap located at the first end of the outer plate and operably coupled to the outer plate in such a manner that the first end cap may be moved into or out of the opening;

a second end cap located at the second end of the outer plate and operably coupled to the outer plate in such a manner that the second end cap may be moved into or out of the opening;

movement of the first end cap and the second end cap effecting movement of the first and second inner plates so as to provide means for substantially matching the capacitance of the sample cell and the capacitance of the reference cell when the same fluid is provided to both the reference cell and the sample cell.

9. Apparatus as in claim 8 wherein the dielectric constant detector further comprises:

an outer plate having a prism having a substantially square transverse cross section, the opening extending completely through the central portion of the prism and having a longitudinal axis which is substantially perpendicular to the substantially square transverse cross section.

10. Apparatus as in claim 9 having a dielectric constant detector wherein the diameter of the first cylindrical opening is substantially equal to the diameter of the third cylindrical opening and the diameter of the second cylindrical opening is less than the diameter of the first cylindrical opening.

11. Apparatus as in claim 10 wherein the dielectric constant detector further comprises:

a first electrically insulating spacer operably located between the first inner plate and the second inner plate;

a second electrically insulating spacer operably located between the first inner plate and the first end cap; and

a third electrically insulating spacer operably located between the second inner plate and the second end cap.

12. Apparatus as in claim 11 wherein the dielectric constant detector further comprises:

first and second O-rings operably located so as to support the first inner plate and to seal the sample cell to prevent fluid leakage from the sample cell; and

third and fourth O-rings operably located so as to support the second inner plate and seal the reference cell to prevent fluid leakage from the reference cell.

13. Apparatus as in claim 12 wherein the dielectric constant detector has an outer plate which is elecrically grounded.

14. Apparatus as in claim 13 wherein the dielectric constant detector has an inner plate electrically connected to a first oscillator circuit and the second inner plate is electrically connected to the second oscillator means.

15. Apparatus as in claim 14 wherein the first end cap is threaded onto the first end of the outer plate and the second cap is threaded onto the second end of the outer plate.

16. Apparatus comprising:

column means for chromatographically separating sample constituents to produce an eluate stream;

means for passing a first carrier fluid stream to the column means;

means for injecting sample constituents into the first carrier fluid stream being passed to the column means;

dielectric constant detector means including sample cell means having a first capacitance representative of a fluid passing therethrough and reference cell means having a second capacitance representative of a fluid passing therethrough;

means for passing the eluate stream through the sample cell means;

means for passing a second carrier fluid stream to the reference cell means;

first oscillator means comprising said sample cell means for producing a first frequency representative of the first capacitance;

second oscillator means comprising said reference cell means for producing a second frequency representative of the second capacitance;

means for combining the first frequency and the second frequency to produce an analysis frequency; and

comparator means for determining a threshold frequency and for producing a sensible signal representative of a difference between the threshold frequency and the analysis frequency

said comparator means comprising;

pulse generating means having an analysis frequency input, a timing circuit input, and a pulse output, and operable for producing a pulse at the pulse output responsive to an edge of an input pulse at the analysis frequency input, the pulse having a duration determined by a pulse width signal appearing at the timing circuit input;

first means for electrically connecting the analysis frequency to the analysis frequency input of the pulse generating means;

timing circuit means for determining a threshold frequency and for producing a pulse width signal output responsive to an input pulse at the analysis frequency input;

second means for electrically connecting the timing circuit means output to the timing circuit input of the pulse generating means; and

sensible signal means connected to the pulse output of the pulse generating means for producing a sensible signal representative of the difference between the threshold frequency and the analysis frequency.

17. Apparatus as in claim 16 wherein the sensible signal means further comprises:

bias means electrically connected to the pulse output of the pulse generating means for producing a first bias signal responsive to a condition that the analysis frequency is greater than the threshold frequency; and

sensible signal drive means connected to the bias means for producing a sensible signal responsive to the first bias signal.

18. Apparatus as in claim 17 wherein the sensible signal means comprises:

a voltage source;

wherein the pulse generating means comprises a monostable multivibrator having a timing circuit input, an analysis frequency input, and a pulse output;

wherein the timing circuit comprises a selectable RC network electrically connected to the timing circuit input of the multivibrator, the selectable RC network comprising a switch having a fixed terminal electrically connected to the timing circuit input and a plurality of selectable terminals, a capacitor having a first lead connected to the fixed terminal of the switch and a second lead electrically connected to ground, a plurality of resistors each having a respective first lead electrically connected to a selectable respective one of the plurality of selectable terminals of the switch and having a respective second lead electrically connected to a voltage source;

wherein the first means further comprises an input network electrically connected to the analysis frequency input of the pulse generating means, the input network comprising a first input network resistor having a first lead electrically connected to the voltage source and a second lead electrically connected to the analysis frequency input of the pulse generating means, a second input network resistor having a first lead electrically connected to the analysis frequency input and a second lead electrically connected to ground and an input network capacitor coupling the analysis frequency to the analysis frequency input of the pulse generating means;

wherein the bias means comprises an RC bias network electrically connected to the pulse output of the pulse generating means, the RC bias network comprising a diode having a cathode electrically connected to the pulse output and an anode, a bias capacitor having a first lead electrically connected to the anode of the diode and a second lead electrically connected to ground, a first bias resistor having a first lead electrically connected to the voltage source and a second lead electrically connected to the anode, a second bias resistor having a first lead electrically connected to the anode of the diode and a second lead, a third bias resistor having a first lead electrically connected to the ground and a second lead, the second lead of the second bias resistor being electrically connected to the second lead of the third bias resistor; and

wherein the sensible signal drive means comprises an NPN resistor having an emitter electrically connected to ground, a base electrically connected to the second lead of the second bias resistor and to the second lead of the third bias resistor and a collector, a light emitting diode having a cathode electrically connected to the collector of the NPN transistor and an anode, and a load resistor having a first lead electrically connected to the anode of the light emitting diode and a second lead electrically connected to the voltage source.

19. Method comprising:

passing a first stream through a chromatographic column to produce an eluate stream;

passing the eluate stream through a first dielectric constant detector cell to produce a first capacitance representative of the eluate stream;

passing a second stream through a second dielectric constant detector cell to produce a second capacitance representative of the thus passed through second stream;

generating a first signal representative of the first capacitance;

generating a second signal representative of the second capacitance;

generating an analysis frequency representative of the difference between the first signal and the second signal; and

generating a sensible signal representative of the difference between a threshold frequency and the analysis frequency.

20. Method as in claim 19 wherein generating the sensible signal further comprises:

determining a threshold frequency by selecting an RC network, the RC time constant of the RC circuit being representative of the threshold frequency;

generating a pulse at pulse intervals determined by the period of the analysis frequency;

charging a capacitor in the selected RC network responsive to a thus generated pulse, the time constant of the RC network determining the duration of the pulse;

producing a first sensible signal responsive to a condition that the analysis frequency is well below the threshold frequency;

producing a second sensible signal responsive to a condition that the analysis frequency is approaching, but less than, the threshhold frequency; and

producing a third sensible signal responsive to a condition that the analysis frequency is equal to or greater than the threshold frequency.

21. A method in accordance with claim 19 wherein generating said sensible signal comprises producing a first sensible signal condition in response to said analysis frequency being substantially lower than said threshold frequency and producing a second sensible signal condition in response to said analysis frequency being at least substantially equal to said threshold frequency.

22. A method in accordance with claim 19 additionally comprising:

selecting said threshold frequency representative of substantially equal capacitance of said first dielectric constant detector cell and said second dielectric constant detector cell,

passing a reference fluid through both said first dielectric constant detector cell and said second dielectric constant detector cell, and

adjusting the relative capacitance of said first dielectric constant detector cell and said second dielectric constant detector cell to produce a preselected sensible signal condition when said analysis frequency is substantially lower than said reference frequency.

23. A method in accordance with claim 19 additionally comprising:

selecting said threshold frequency representative of a preselected maximum capacitance difference between said first dielectric constant detector cell and said second dielectric constant detector cell and

producing a preselected sensible signal condition in response to said analysis frequency being at least substantially equal to said reference frequency.