Method and apparatus for nox analysis

• US 3,970,430 A
• Filed: 10/17/1974
• Issued: 07/20/1976
• Est. Priority Date: 10/17/1974
• Status: Expired due to Term

• Current Assignee: EMA Corp. (Ametek Incorporated)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Seago, James L., Williamson, James A. Jr., Reader, John R. Jr.
• Primary Examiner(s): Reese, Robert M.
• Application Number:
  US05/515,709
• Time in Patent Office: 642 Days
• Field of Search: 23/232 R, 23/232 C, 23/232 E, 23/254 R, 23/254 E, 23/255 R, 23/255 E, 356/201, 356/205, 356/206, 250/373, 250/343
• US Class Current: 436/116
• CPC Class Codes: G01N 21/272 for following a reaction, e.g. for determining photometrically a reaction rate (photometric cinetic analysis)
• CPC Class Codes: G01N 33/0013 by a chemical reaction G01N33/0024 takes precedence
• CPC Class Codes: G01N 33/0067 by measuring the rate of variation of the concentration
• CPC Class Codes: Y10T 436/177692 Oxides of nitrogen

Abstract

Apparatus and method for NO_x analysis in which a sample gas is introduced into a sample cell and mixed with oxygen to induce conversion of NO to NO₂. After a given time, prior to complete conversion of NO to NO₂, the absorbance and the time rate of change of absorbance is measured. The time rate of change of absorbance is indicative of the initial NO concentration in the sample gas; and the sum of the absorbance and the time rate of change of absorbance is indicative of the initial NO_x concentration in the gas. A better indication of the initial NO_x concentration can be obtained from the sum of the absorbance and the square root of the time rate of change of absorbance.

Claims

1. An apparatus for determining the amount of NO_x in a sample gas, comprising:

a. a gas-tight sample cell having windows transparent to radiation of a wavelength in the range of about 410 to about 600 nm.;

b. means for introducing a known volume of sample gas into said cell;

c. radiation source means for passing radiation of a wavelength in the range of about 410 to about 600 nm. through said cell;

d. means for detecting the intensity of the radiation emerging from said cell;

e. means for introducing at least about 2 atmospheres of an oxygen-containing gas into said cell to form a gas mixture with the sample gas;

f. means for maintaining the gas mixture at a substantially constant temperature;

g. means for maintaining the gas mixture at a substantially constant pressure;

h. means for measuring, at a given time, the time rate of change of the absorbance of radiation by the gas mixture in said cell and generating a signal proportional to the measured absorbance;

i. means for measuring, at the same time, the time rate of change of the absorbance of radiation by the gas mixture in said cell and for generating a signal proportional to the measured time rate of change of absorbance, the sum of the measured absorbance and the measured rate of change of absorbance being indicative of the initial NO_x content of the sample gas; and

j. means for summing the two generated signals.

2. The apparatus of claim 1 further comprising means to multiply the time rate of change of absorbance by a scale factor between 1.1 and 1.3 and displaying the result.

3. An apparatus for determining the amount of NO_x in a sample gas, comprising:

a. a gas-tight sample cell having windows transparent to radiation of a wavelength in the range of about 410 to about 500 nm.;

b. means for introducing a known volume of sample gas into said cell;

c. radiation source means for passing radiation of a wavelength in the range of about 410 to about 600 nm. through said cell;

d. means for detecting the intensity of the radiation emerging from said cell;

e. means for introducing at least about 2 atmospheres of an oxygen-containing gas into said cell to form a gas mixture with the sample gas;

f. means for maintaining the gas mixture at a substantially constant temperature;

g. means for maintaining the gas mixture at a substantially constant pressure;

h. means for measuring, at a given time, the absorbance of radiation by the gas mixture in said cell and for generating an electrical signal proportional to the measured absorbance; and

i. means for measuring, at the same time, the time rate of change of the absorbance of radiation by the gas mixture in said cell and for generating an electrical signal proportional to a power, between about 0.4 and about 0.6, of the measured time rate of change of absorbance;

the sum of the measured absorbance and the power of the measured rate of chanage of absorbance being indicative of the initial NO_x content of the sample gas.

4. The apparatus of claim 3 wherein said means for introducing an oxygen-containing gas into said cell comprises means for introducing at least about 4 atmospheres of substantially pure oxygen into said cell.

5. The apparatus of claim 4 wherein:

a. said means for measuring the absorbance of radiation by the gas mixture in said cell is a means to generate an electrical signal proportional to the measured absorbance; and

b. said means for measuring the time rate of change of absorbance of radiation by the gas mixture in said cell is a means to generate an electrical signal proportional to the measured time rate of change of absorbance.

6. The apparatus of claim 4 wherein

said means for measuring the time rate of change of absorbance of radiation by the gas mixture in said cell and for generating an electrical signal proportional to a power of the measured time rate of change of absorbance is a means to generate an electrical signal proportional to the square root of the measured time rate of change of absorbance, the sum of the absorbance and the square root of the time rate of change of absorbance being indicative of the initial NO_x content of the sample gas.

7. The apparatus of claim 6 further comprising:

a. means to sum the electrical signal proportional to the measured absorbance and the electrical signal proportional to the square root of the measured time rate of change of absorbance; and

b. means to display the output of said means to sum.

8. The apparatus of claim 7 wherein said radiation source means comprises:

a. means for passing detecting radiation through said cell, said detecting radiation being of a wavelength strongly absorbed by NO₂ ; and

b. means for passing reference radiation through said cell, said reference radiation being of a wavelength weakly absorbed by NO₂, and wherein said means for detecting the intensity of the radiation emerging from said cell comprises means for separately detecting the intensity of the detecting radiation and the reference radiation.

9. A method for measuring the concentration of NO_x in a sample gas comprising the following steps:

a. introducing a known volume of the sample gas into a gas-tight sample cell;

b. introducing at least about 2 atmospheres of an oxygen-containing gas into the cell to form a gas mixture with the sample gas;

c. controlling the temperature and pressure of the gas mixture;

d. passing detecting radiation of a wavelength between about 410 to about 600 nm. through the gas mixture in the cell, said detecting radiation being of a wavelength strongly absorbed by NO₂ ; and

e. measuring, at the same given time, the absorbance and the time rate of change of absorbance of the detecting radiation passing through the cell by the gas mixture in the cell, the sum of the measured absorbance and the measured time rate of change of absorbance being indicative of the initial NO_x content of the sample gas.

10. The method of claim 9 wherein, prior to the step of introducing sample gas into the cell, air is introduced into the cell and radiation of the same wavelength as said detecting radiation is passed through the air in the cell;

and wherein the step of measuring the absorbance of the gas mixture is accomplished by generating an electrical signal proportional to the difference between the intensity of the detecting radiation passing through the cell when it is filled with air and the intensity of the detecting radiation passing through the cell when it is filled with sample gas.

11. The method of claim 10 wherein, in addition to detecting radiation, reference radiation is passed through the gas mixture in the cell, said reference radiation being of a wavelength weakly absorbed by NO₂.

12. The method of claim 11 wherein the step of measuring the absorbance and the time rate of change of absorbance of the detecting radiation passing through the gas mixture in the cell includes the step of generating an electrical signal proportional to the measured absorbance and an electrical signal proportional to the square root of the measured time rate of change of absorbance.

13. The method of claim 12 further comprising the step of summing the measured absorbance and the square root of the measured time rate of change of absorbance by generating an electrical signal proportional to the sum of measured absorbance and the square root of the measured time rate of change of absorbance.

14. The method of claim 13 further comprising the step of displaying the sum of the measured absorbance and the square root of the measured time rate of change of absorbance.

15. The method of claim 14 wherein the step of introducing an oxygen-containing gas into the cell is accomplished by introducing at least about 4 atmospheres of substantially pure oxygen into the cell.