Method and means for vaporizing liquids by means of heating a sample capillary tube for detection or analysis

• US 4,960,992 A
• Filed: 03/20/1989
• Issued: 10/02/1990
• Est. Priority Date: 08/30/1983
• Status: Expired due to Fees

• Current Assignee: Research Corporation Technologies
• Original Assignee: Research Corporation Technologies
• Inventors: Blakely, Calvin R., Fergusson, Gordon J., Vestal, Marvin L.
• Primary Examiner(s): Berman, Jack I.
• Application Number:
  US07/326,150
• Time in Patent Office: 561 Days
• Field of Search: 250/281, 250/282, 250/288, 250/423 R, 422/70, 436/161, 73/61.1 C, 73/863.12, 73/863.21, 73/864.81
• US Class Current: 250/288
• CPC Class Codes: G01N 2030/3038 temperature control of column exit, e.g. of restrictors
• CPC Class Codes: G01N 2030/3053 using resistive heating
• CPC Class Codes: G01N 30/32 of pressure or speed G01N30/36 takes precedence
• CPC Class Codes: G01N 30/7253 by thermal means, e.g. thermospray
• CPC Class Codes: H01J 49/0445 with means for introducing as a spray, a jet or an aerosol electrospray ion sources H01J49/165
• CPC Class Codes: H01J 49/0486 with means for monitoring the sample temperature
• CPC Class Codes: H01J 49/049 with means for applying heat to desorb the sample; Evaporation

Abstract

This disclosure is concerned with method and apparatus for vaporizing liquid solutions in order to detect, quantitate, and/or determine physical or chemical properties of samples present in liquid solution. Mixtures may be separated by an on-line liquid chromatographic column and the methods used for detection, quantitation, identification, and/or determination of chemical and physical properties include mass spectrometry, photoionization, flame ionization, electron capture, optical photometry, including UV, visible, and IR regions of the spectrum, light scattering, light emission, atomic absorption, and any other technique suitable for detecting or analyzing molecules or particles in a gaseous or vacuum environment. The method and apparatus involves controlled partial vaporization of the solution. Methods are disclosed for controlling the degree of partial vaporization and the temperature at which this vaporization occurs, and for maintaining this degree of vaporization essentially constant even though the solvent flow rate and/or composition may vary in either a controlled or an uncontrolled fashion. This

GOVERNMENT SUPPORT

The invention described herein was made in the course of work under a grant or award from the Department of Health and Human Services (formerly Health Education and Welfare).

CROSS REFERENCE TO RELATED APPLICATIONS

Claims

1. A thermospray device for vaporizing a liquid sample into an ion vapor containing large molecules of interest for analysis, said device comprising:

(a) a metal capillary tube for receiving said sample, said tube defining a nozzle portion at one end thereof,

(b) heating means for heating said capillary tube to vaporize a predetermined fraction of the sample passing therethrough,

(c) a control means for controlling the temperature of the sample within the capillary and to maintain from 1% to 35% of the sample in liquid form as it is ejected from the nozzle as a particle beam of minute particles entrained in an intense vapor jet, said control means including a means for measuring the temperature of the liquid sample in the capillary tube, said means for measuring including a temperature sensor mounted in thermal contact with the capillary tube within a first third of a predetermined length heated by said heating means, and

(d) a means for separating the large molecules from said vapor jet as said molecules are selected for further analysis.

2. The thermospray device as claimed in claim 1 wherein said device comprises an ionization means.

3. The thermospray device as claimed in claim 1 further includes a detecting means for detecting said molecules of interest, said detection means is selected from one of the following:

(1) photo ionization detection means

(2) flame ionization detection means

(3) electron capture detection means

(4) optical photometry detection means

(5) atomic absorption detection means, or

(6) optical admission detection means

4. The thermospray device as claimed in claim 3 wherein said separating means comprises at least one separation chamber in which said vapor jet passes through a gas stream which is flowing perpendicular to said vapor jet in said at least one separation chamber(s), said gas stream being sufficient to sweep away most of the solvent vapor without significantly deflecting said sample molecules.

5. The thermospray device as claimed in claim 4 wherein said separating means comprises a first and second separation chamber having a first baffle with a first aperture which separates said first and second separation chambers, and a second baffle with a second aperture which separates said second separation chamber and said detection means.

6. The thermospray device as claimed in claim 4 wherein said gas stream is clean air.

7. The thermospray device as claimed in claim 4 wherein said gas stream is at atmospheric or higher pressure.

8. The thermospray device as claimed in claim 1 wherein said device further includes a detecting means which comprises a detection chamber in which said molecules from said separating means are deflected by a flow gas to a heated metal surface where final sample vaporization occurs.

9. The thermospray device as claimed in claim 1 wherein said device further includes a detecting means which comprises a detection chamber in which said molecules from said separating means are deflected by a flow gas which is heated to provide final sample vaporization.

10. The thermospray device as claimed in claims 8 or 9 wherein said flow gas is helium.

11. The thermospray device as claimed in claim 1 wherein said separating means comprises a first and second separation chamber in which said vapor jet passes through a gas stream which is flowing perpendicular to said vapor jet in said first and second separation chambers, said gas stream is sufficient to sweep away most of the solvent vapor without significantly deflecting said sample molecules, said separating means includes means for directing said sample molecules through a heated capillary nozzle where further rapid vaporization occurs resulting in a supersonic seeded beam of nonvolatile molecules.

12. The thermospray device as claimed in claim 11 wherein said separating means further comprises a first baffle with a first aperture which separates said first and second separation chambers, and a second baffle with a second aperture which separates said second separation chamber and a vacuum chamber.

13. The thermospray device as claimed in claim 12 wherein said vacuum chamber is a supersonic beam system comprising a skimmer and collimator in which the chambers in between said skimmer and said collimator are separately pumped by a first and second vacuum pump.

14. The thermospray device as claimed in claim 11 wherein said gas stream is at atmospheric or higher pressure.

15. A method of vaporizing a liquid sample containing large molecules of interest for analysis, said method comprising the steps of:

(a) receiving said sample in a metal capillary tube, said tube defining a nozzle portion at one end thereof,

(b) heating said capillary tube to vaporize a predetermined fraction of the sample passing therethrough,

(c) controlling the temperature of the sample within the nozzle and maintaining from 1% to 35% of the sample in liquid form as it is ejected from the nozzle as a particle beam of minute particles entrained in an intense vapor jet, said controlling step includes measuring the temperature of the liquid in the capillary tube, and

(d) separating the large molecules from said vapor jet as said molecules are selected for further analysis.

16. The method of vaporizing a liquid sample according to claim 15 further including a detecting step for detecting said molecules of interest, said detection step is selected from one of the following:

(1) photo ionization detection

(2) flame ionization detection

(3) electron capture detection

(4) optical photometry detection

(5) atomic absorption detection, or

(6) optical admission detection

17. The method of vaporizing a liquid sample according to claim 15 wherein said separating step comprises passing said vapor jet through a first gas stream flowing perpendicular to said vapor jet and subsequently passing said vapor jet through a aperture and through a second gas stream flowing perpendicular to said vapor jet, said first and second gas stream is sufficient to sweep away most of the solvent vapor without significantly deflecting said sample molecules.

18. The method of vaporizing a liquid sample according to claim 15 wherein said detecting and analyzing step comprises deflecting said molecules by a flow gas to a heated metal surface where final sample vaporization occurs, said molecules are then photoionized by an ultra violet lamp and collected for analysis.

19. The method of vaporizing a liquid sample according to claim 15 wherein said detecting and analyzing step comprises deflecting said molecules by a heated flow gas causing final sample vaporization, said molecules are then photoionized by an ultra violet lamp and collected for analysis.

20. The method of vaporizing a liquid sample according to claim 15 wherein said separating step comprises passing said vapor jet through a first and second gas stream flowing perpendicular to said vapor jet and sweeping away most of the solvent vapor without significantly deflecting said sample molecules and subsequently passing the molecules through a heated c capillary nozzle where further rapid vaporization occurs resulting in a supersonic seeded beam of nonvolatile molecules.

21. The method of vaporizing a liquid sample according to claim 20 wherein said separating step further comprises passing said supersonic beam through a vacuum chamber for adiabatic cooling.