CN105486675B - Quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition - Google Patents
Quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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Abstract
The present invention provides a kind of quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition, includes the following steps：First, it calculates12CO2Raman quantizing factor F12CO2；2nd, it calculates13CO2Raman quantizing factor F13CO2；3rd, according to formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/F12CO2) calculate CO2In gas12CO2With13CO2Molar ratio C[12CO2]/C[13CO2].The present invention is to different proportion12CO2/N2Mixed gas and13CO2/N2Mixed gas carries out micro laser Raman spectroscopy test analysis, the micro-Raman spectroscopy of use have the characteristics that in high precision, it is in situ, lossless and quick, being capable of quantitative analysis CO using micro-Raman spectroscopy2The composition of carbon isotope, is with a wide range of applications.
Description
Technical field
The invention belongs to field of spectral analysis technology, and in particular to a kind of quantitative analysis CO2Gas carbon isotope composition
LR laser raman detection method.
Background technology
Raman spectrum is an important modern molecular spectral technique, be widely used to physics, chemistry, material, oil,
The fields such as biology, environment, geology, celestial body.Laser micro-raman spectrometry (LRM) is to focus on incident laser by microscope
On sample, not under by ambient substance disturbed condition, it is accurate obtain in the same old way the related chemical composition of product microcell, crystal structure,
The information such as interaction of molecules and molecularly oriented.Laser Raman spectroscopy is increasingly becoming a weight in geoscience basic research
Want analysis means.
Fluid inclusion is that mineral are captured during crystalline growth and are stored in mineral crystal defect primitively
Mass flow body, by the ingredient and property of studying mineral fluid inclusions, it will be appreciated that Diagenesis And Mineralization physicochemical condition, fluid composition,
Substance source and geologic process etc..CO2It is a kind of important volatile component, CO in fluid inclusion2Stable isotope
Have12CO2With13CO2.CO in fluid inclusion2Gaseous carbon Isotope Compositions originate from Research on Crustal and outer mantle Minerals
And fluid Evolution etc. has an important geological Significance, and for the research mineralization in mineral deposit, Gas Accumulation He Chengzang,
Matter fluid Evolution and tectonodynamics etc. provide important information.
At present when carrying out analysis test to inclusion enclave isotope, conventional method is with thermal explosion method, polishing, crush method etc.
Open inclusion enclave, the CO then released by spectrometer analysis inclusion enclave2Carbon isotope.But what is obtained in this way is
CO of the mineral under the not same period time, different origins source2Carbon isotope mixing resultant, it is impossible to obtain representing in mineral certain it is specific into
The Individual fluid inclusion CO of rock ore-forming stages2The composition of carbon isotope.But micro-Raman spectroscopy is with high-precision
The features such as spending, be in situ, lossless and quick.Therefore, micro-Raman spectroscopy quantitative analysis Individual fluid inclusion CO is utilized2
The composition of carbon isotope has good application prospect.
Invention content
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, to provide a kind of quantitative analysis
CO2The LR laser raman detection method of gas carbon isotope composition.The micro-Raman spectroscopy that this method uses has high-precision
The features such as spending, is in situ, lossless and quick, therefore, this method can utilize the single stream of micro-Raman spectroscopy quantitative analysis
Body inclusion enclave CO2The composition of carbon isotope has good application prospect.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of quantitative analysis CO2Gas carbon isotope
The LR laser raman detection method of composition, which is characterized in that this method includes the following steps：
Step 1: it calculates12CO2Raman quantizing factor F12CO2, specific method is：
Step 101 is incited somebody to action using gas proportion mixing device12CO2And N2By different volumes than be uniformly mixed, obtain it is a series of not
With proportioning12CO2/N2Mixed gas；
Step 102, using Laser-Raman microspectroscopy to proportionings various in step 10112CO2/N2Mixed gas point
Not carry out micro laser Raman spectroscopy detection, obtain N2Characteristic peak ν[N2]And12CO2The double characteristic peak ν of Fermi resonance- [12CO2]With
ν+ [12CO2], ν under various conditions of mixture ratios is then calculated respectively- [12CO2]The peak area A at place- [12CO2]、ν+ [12CO2]The peak area at place
A+ [12CO2]And ν[N2]The peak area A at place1 [N2]；The ν- [12CO2]、ν+ [12CO2]And ν[N2]Unit be cm-1；
Step 103, the A according to step 102- [12CO2]And A+ [12CO2]It calculates under various conditions of mixture ratios12CO2Feature
The peak area A at peak[12CO2], the A[12CO2]=A- [12CO2]+A+ [12CO2], then according to the A[12CO2]Calculate various proportioning items
Under part12CO2With N2Characteristic peak peak area compare K1, the K1=[A[12CO2]/Σ12CO2)/A1 [N2]；The Σ12CO2For12CO2's
With respect to raman scattering cross section normalization factor；
Step 104, with K described in step 1031As ordinate, with12CO2And N2Molar ratio C[12CO2]/C[N2]As
Abscissa throwing figure simultaneously carries out linear fit, calculates the slope of fitting a straight line, obtains F12CO2；
Step 2: it calculates13CO2Raman quantizing factor F13CO2, specific method is：
Step 201 is incited somebody to action using gas proportion mixing device13CO2And N2By different volumes than be uniformly mixed, obtain it is a series of not
With proportioning13CO2/N2Mixed gas；
Step 202, using Laser-Raman microspectroscopy to proportionings various in step 20113CO2/N2Mixed gas point
Not carry out micro laser Raman spectroscopy detection, obtain N2Characteristic peak ν[N2]And13CO2The double characteristic peak ν of Fermi resonance- [13CO2]With
ν+ [13CO2], ν under various conditions of mixture ratios is then calculated respectively- [13CO2]The peak area A at place- [13CO2]、ν+ [13CO2]The peak area at place
A+ [13CO2]And ν[N2]The peak area A at place2 [N2]；The ν- [13CO2]And ν+ [13CO2]Unit is cm-1；
Step 203, the A according to step 202- [13CO2]And A+ [13CO2]It calculates under various conditions of mixture ratios13CO2Feature
The peak area A at peak[13CO2], the A[13CO2]=A- [13CO2]+A+ [13CO2], then according to the A[13CO2]Calculate various proportioning items
Under part13CO2With N2Characteristic peak peak area compare K2, the K2=[A[13CO2]/Σ13CO2)/A2 [N2]；The Σ13CO2For13CO2's
With respect to raman scattering cross section normalization factor；
Step 204, with K described in step 2032As ordinate, with13CO2And N2Molar ratio C[13CO2]/C[N2]As
Abscissa throwing figure simultaneously carries out linear fit, calculates the slope of fitting a straight line, obtains F13CO2；
Step 3: using Laser-Raman microspectroscopy to by12CO2With13CO2The CO mixed2Gas carries out micro-
LR laser raman detects, and obtains CO2In gas12CO2The peak area A of characteristic peak12CO2And13CO2The peak area A of characteristic peak13CO2, so
Afterwards according to formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/F12CO2) calculate CO2In gas12CO2With13CO2's
Molar ratio C[12CO2]/C[13CO2]。
Above-mentioned quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition, which is characterized in that step
ν described in 102- [12CO2]=1287cm-1, the ν+ [12CO2]=1390cm-1, the ν[N2]=2332cm-1。
Above-mentioned quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition, which is characterized in that step
Σ described in 10312CO2=1.49.
Above-mentioned quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition, which is characterized in that step
ν described in 202- [13CO2]=1267cm-1, the ν+ [13CO2]=1372cm-1。
Above-mentioned quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition, which is characterized in that step
Σ described in 20313CO2=1.437.
Compared with the prior art, the present invention has the following advantages：
The present invention is by preparing different proportion12CO2/N2With13CO2/N2Blend sample simultaneously carries out micro laser Raman spectroscopy survey
Examination analysis, the raman characteristic peak peak area ratio of gas with its molar fraction than direct proportionality, recognized by the slope of fitting a straight line
To be Raman quantizing factor.CO2Gas carbon isotope molar fraction ratio can be according to Raman peaks peak area ratio and Raman quantizing factor
The product of ratio is obtained.The present invention has high-precision, in situ, lossless and quick etc. special due to the micro-Raman spectroscopy of use
Point, therefore, being capable of quantitative analysis Individual fluid inclusion CO using micro-Raman spectroscopy2The composition of carbon isotope, tool
Have wide practical use.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Description of the drawings
Fig. 1 is the present invention12CO2With N2Characteristic peak peak area compare K1With molar ratio C[12CO2]/C[N2]Fitting a straight line figure.
Fig. 2 is the present invention13CO2With N2Characteristic peak peak area compare K2With molar ratio C[13CO2]/C[N2]Fitting a straight line figure.
Specific embodiment
The present invention is by the method for laser micro-raman spectrometry analysis and linear fit to CO2The group of carbon isotope in gas
Into progress quantitative analysis.Quantitative analysis CO of the present invention2The LR laser raman detection method of gas carbon isotope composition includes following step
Suddenly：
Step 1: it calculates12CO2Raman quantizing factor F12CO2, specific method is：
Step 101 is incited somebody to action using gas proportion mixing device12CO2And N2By different volumes than be uniformly mixed, obtain it is a series of not
With proportioning12CO2/N2Mixed gas；
Step 102, using Laser-Raman microspectroscopy respectively to proportionings various in step 10112CO2/N2Gaseous mixture
Body carries out micro laser Raman spectroscopy detection, obtains N2Characteristic peak ν[N2]And12CO2The double characteristic peak ν of Fermi resonance- [12CO2]With
ν+ [12CO2], ν under various conditions of mixture ratios is then calculated respectively- [12CO2]The peak area A at place- [12CO2]、ν+ [12CO2]The peak area at place
A+ [12CO2]And ν[N2]The peak area A at place1 [N2]；The ν- [12CO2]、ν+ [12CO2]And ν[N2]Unit be cm-1；
Step 103, the A according to step 102- [12CO2]And A+ [12CO2]It calculates under various conditions of mixture ratios12CO2Feature
The peak area A at peak[12CO2], the A[12CO2]=A- [12CO2]+A+ [12CO2], then according to the A[12CO2]Calculate various proportioning items
Under part12CO2With N2Characteristic peak peak area compare K1, the K1=[A[12CO2]/Σ12CO2)/A1 [N2]；The Σ12CO2For12CO2's
With respect to raman scattering cross section normalization factor；
Step 104, with K described in step 1031As ordinate, with12CO2And N2Molar ratio C[12CO2]/C[N2]As
Abscissa throwing figure simultaneously carries out linear fit, calculates the slope of fitting a straight line, obtains F12CO2；
Step 2: it calculates13CO2Raman quantizing factor F13CO2, specific method is：
Step 201 is incited somebody to action using gas proportion mixing device13CO2And N2By different volumes than be uniformly mixed, obtain it is a series of not
With proportioning13CO2/N2Mixed gas；
Step 202, using Laser-Raman microspectroscopy respectively to proportionings various in step 20113CO2/N2Gaseous mixture
Body carries out micro laser Raman spectroscopy detection, obtains N2Characteristic peak ν[N2]And13CO2The double characteristic peak ν of Fermi resonance- [13CO2]With
ν+ [13CO2], ν under various conditions of mixture ratios is then calculated respectively- [13CO2]The peak area A at place- [13CO2]、ν+ [13CO2]The peak area at place
A+ [13CO2]And ν[N2]The peak area A at place2 [N2]；The ν- [13CO2]And ν+ [13CO2]Unit is cm-1；
Step 203, the A according to step 202- [13CO2]And A+ [13CO2]It calculates under various conditions of mixture ratios13CO2Feature
The peak area A at peak[13CO2], the A[13CO2]=A-[13CO2]+A+ [13CO2], then according to the A[13CO2]Calculate various proportioning items
Under part13CO2With N2Characteristic peak peak area compare K2, the K2=[A[13CO2]/Σ13CO2)/A2 [N2]；The Σ13CO2For13CO2's
With respect to raman scattering cross section normalization factor；
Step 204, with K described in step 2032As ordinate, with13CO2And N2Molar ratio C[13CO2]/C[N2]As
Abscissa throwing figure simultaneously carries out linear fit, calculates the slope of fitting a straight line, obtains F13CO2；
Step 3: using Laser-Raman microspectroscopy to by12CO2With13CO2The CO mixed2Gas carries out micro-
LR laser raman detects, and obtains CO2In gas12CO2The peak area A of characteristic peak12CO2And13CO2The peak area A of characteristic peak13CO2, so
Afterwards according to formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/F12CO2) calculate CO2In gas12CO2With13CO2's
Molar ratio C[12CO2]/C[13CO2]。
In specific implementation process, carrying out12CO2/N2When mixed gas micro laser Raman spectroscopy detects：To different ratio12CO2/N2Mixed gas carries out Laser Roman spectroscopic analysis of composition, can be found on spectrogram：In CO2Raman spectrum in occur two
Strong characteristic spectral line, this is CO2Fermi resonance doublet, frequency is respectively in 1287cm-1And 1390cm-1(i.e. ν- [12CO2]With
ν+ [12CO2]).It is 2332cm in frequency-1Place has the intensity at a peak very strong, this is N2Characteristic peak (i.e. ν[N2])。
It is right in specific implementation process12CO2/N2When mixed gas carries out the analysis of laser micro-raman spectrometry characteristic peak：Raman
Bands of a spectrum go out peak position, shape and intensity be only dependent upon molecule in itself in vibration processes molecular polarizability change.Therefore, often
A kind of substance with Raman active has its specific Raman spectral characteristics, can be recognized according to the Raman spectrum of substance
Go out substance classes, here it is the basic principles of Raman spectra qualitative analysis.ΣjIt is opposite raman scattering cross section normalization factor,
N is provided in the world2ΣjIt is 1 to be worth, and is obtained under the conditions of this Laboratory Instruments by test of many times12CO2ΣjBe worth is 1.49.
The ratio of the corresponding opposite raman scattering cross section normalization factor Σ of the raman characteristic peak peak area of molecule is A/ Σ, this
Ratio is directly proportional to the relative molar concentration of molecule, i.e.,： (Aa/Σa)/(Ab/Σb)=(Ca/Cb)·(Fa/Fb), wherein A, C, F
Respectively raman characteristic peak peak area, molar fraction, Raman quantizing factor.Table 1 lists12CO2/N2Mixed gas is matched in difference
Raman spectrum data than under the conditions of.By 1287cm-1(ν- [12CO2]), 1390cm-1(ν+ [12CO2]) and 2332cm-1 (ν[N2]) at
Characteristic peak peak area is denoted as A respectively- [12CO2], A+ [12CO2]And A1 [N2]。
Table 112CO2/N2The Raman spectrum data of mixed gas
In specific implementation process, Raman quantizing factor F is obtained by fitting a straight line12CO2When：12CO2Raman spectrum occur
Fermi vibration it is bimodal, when with12CO2With N2Characteristic peak peak area compares K1As ordinate, with molar ratio C[13CO2]/C[N2]As horizontal stroke
When coordinate carries out throwing figure (as shown in Figure 1), the linear equation of zero crossing has been obtained：Y=1.16349x, and coefficient R2For
0.99919.Slope, that is, F of fitting a straight line12CO2, value 1.16349.
In specific implementation process, carrying out13CO2/N2When mixed gas micro laser Raman spectroscopy detects, to different ratio13CO2/N2Mixed gas carries out Laser Roman spectroscopic analysis of composition, can be found on spectrogram：In CO2Raman spectrum in occur two
Strong characteristic spectral line, this is CO2Fermi resonance doublet, frequency is respectively in 1267cm-1And 1372cm-1(i.e. ν- [13CO2]With
ν+ [13CO2]).It is 2332cm in frequency-1Place has the intensity at a peak very strong, this is N2Characteristic peak (i.e. ν[N2])。
It is right in specific implementation process13CO2/N2When mixed gas carries out the analysis of laser micro-raman spectrometry characteristic peak：Raman
Bands of a spectrum go out peak position, shape and intensity be only dependent upon molecule in itself in vibration processes molecular polarizability change.Therefore, often
A kind of substance with Raman active has its specific Raman spectral characteristics, can be recognized according to the Raman spectrum of substance
Go out substance classes, here it is the basic principles of Raman spectra qualitative analysis.ΣjIt is opposite raman scattering cross section normalization factor,
N is provided in the world2ΣjIt is 1 to be worth, and is obtained by calculating analysis13CO2ΣjBe worth is 1.437.The raman characteristic peak peak face of molecule
The ratio of the corresponding opposite raman scattering cross section normalization factor Σ of product is the Relative mole of A/ Σ, this ratio and molecule
Concentration is directly proportional, i.e.,： (Aa/Σa)/(Ab/Σb)=(Ca/Cb)·(Fa/Fb), wherein A, C, F are respectively raman characteristic peak peak face
Product, molar fraction, Raman quantizing factor.Table 2 lists13CO2/N2Mixed gas molar ratio is respectively 0,0.166,0.8,1 and
1.5 Raman spectrum data.By 1267cm-1(ν- [13CO2]), 1372cm-1(ν+ [13CO2]) and 2332cm-1(ν[N2]) at feature
Peak peak area is denoted as A respectively- [13CO2], A+ [13CO2]And A2 [N2]。
Table 213CO2/N2The Raman spectrum data of mixed gas
In specific implementation process, Raman quantizing factor F is obtained by fitting a straight line13CO2When,13CO2Raman spectrum occur
Fermi vibration it is bimodal, when with13CO2The sum of Fermi resonance doublet peak area and N2Peak area ratio K2As ordinate, mole
Compare C[13CO2]/C[N2]When carrying out throwing figure (as shown in Figure 2) as abscissa, the linear equation of zero crossing has been obtained：Y=
1.61086x and coefficient R2=0.99975.Linear equation slope, that is, F of fitting13CO2, value 1.61086.
In specific implementation process, according to formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/F12CO2) calculate
Go out in mixed gas12CO2With13CO2Molar ratio C[12CO2]/C[13CO2]When：Specifically, it is known that Raman quantizing factor F13CO2
And F12CO2Respectively equal to 1.61086 and 1.16349, their ratio F13CO2/F12CO2It is 1.3845, is a constant.Therefore, if
It can be measured with micro-Raman spectroscopy13CO2With12CO2Raman characteristic peak peak area value, then molar ratio C12CO2/C13CO2It can
According to A12CO2/A13CO2And F13CO2/F12CO2Product obtain.
Below with result of study of the present invention to CO2The composition progress quantitative analysis progress example of carbon isotope is said in gas
It is bright.
Embodiment 1
It is prepared in laboratory12CO2/13CO2Mixed type CO2Artificial inclusion enclave, it is known that CO2In artificial inclusion enclave12CO2With13CO2Molar ratio C[12CO2]/C[13CO2]=1, then according to formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/
F12CO2), it estimates in artificial inclusion enclave12CO2With13CO2Molar ratio, and compare relative error.It is 1 in molar ratio12CO2/13CO2In the Raman spectrogram of artificial inclusion enclave, it can significantly see and peak position in 1267cm-1(ν- [13CO2]), 1372cm-1(ν+ [13CO2]),1287cm-1(ν- [12CO2]) and 1390cm-1(ν+ [12CO2]) at peak, they are12CO2With13CO2Raman signatures
Peak, the peak area of characteristic peak is A- [13CO2]、A+ [13CO2]、 A- [12CO2]、A+ [12CO2], the sum of peak area A- [12CO2]+A+ [12CO2]With
A- [13CO2]+A+ [13CO2]It is denoted as A respectively12CO2、A13CO2.It is listed in table 3 in artificial inclusion enclave12CO2With13CO2Fermi's doublet
Peak area value and the molar ratio estimated with formula.By calculating, the molar ratio of artificial inclusion enclave is 1.03542, they
Relative error is 3.54%.This, which is indicated that, works as F13CO2And F12CO2When respectively 1.61086 and 1.16349, if swashed using micro-
Light Raman spectroscopy is measured13CO2With12CO2Raman characteristic peak peak area value, so that it may according to A12CO2/A13CO2And F13CO2/F12CO2
Product estimate CO2Molar ratio C[12CO2]/C[13CO2], therefore quantitative analysis CO can be set up2Gas carbon isotope laser
Raman test method.
3 embodiment of table, 1 inclusion enclave sample detection data
Embodiment 2
It is prepared in laboratory12CO2/13CO2Mixed type CO2Artificial inclusion enclave, it is known that12CO2With13CO2Molar ratio C[12CO2]/C[13CO2]=2, then according to formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/F12CO2), estimation is artificial
In inclusion enclave12CO2With13CO2Molar ratio, and compare relative error.It is 2 in molar ratio12CO2/13CO2Artificial inclusion enclave
It can significantly see in Raman spectrogram and peak position in 1267cm-1(ν- [13CO2]),1372cm-1(ν+ [13CO2]), 1287cm-1(ν- [12CO2]) and 1390cm-1(ν+ [12CO2]) at peak, they are12CO2With13CO2Raman characteristic peak, remember the peak face of characteristic peak
Product is A- [13CO2]、A+ [13CO2]、A- [12CO2]、A+ [12CO2], the sum of peak area A- [12CO2]+A+ [12CO2]With A- [13CO2]+A+ [13CO2]Respectively
It is denoted as A12CO2、 A13CO2.It is listed in table 4 in artificial inclusion enclave12C and13Fermi's doublet peak area value of C and estimated with formula
The molar ratio of calculating.By calculating, the molar ratio of artificial inclusion enclave is respectively 1.93855, and their relative error is-
1.53%.This, which is indicated that, works as F13CO2And F12CO2When respectively 1.61086 and 1.16349, if using laser micro-raman spectrometry
Method is measured13CO2With12CO2Raman characteristic peak peak area value, so that it may according to A12CO2/A13CO2And F13CO2/F12CO2Product estimation
Go out CO2Molar ratio C[12CO2]/C[13CO2], therefore quantitative analysis CO can be set up2Gas carbon isotope LR laser raman test side
Method.
4 embodiment of table, 2 inclusion enclave sample detection data
In conclusion the present invention is the different proportion to preparation12CO2/N2With13CO2/N2Mixed gas sample carries out micro-
LR laser raman tests and analyzes, the raman characteristic peak peak area ratio of gas and its molar ratio direct proportionality, fit equation it is oblique
Rate is considered as Raman quantizing factor.CO2Gas carbon isotope molar ratio can according to Raman peaks peak area ratio and Raman quantization because
The product of sub- ratio is obtained.The present invention has high-precision, in situ, lossless and quick etc. due to the micro-Raman spectroscopy of use
Feature, therefore, being capable of quantitative analysis Individual fluid inclusion CO using micro-Raman spectroscopy2The composition of carbon isotope,
With good application prospect.
The above is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art substantially makees above example, still fall within technical solution of the present invention
Protection domain in.
Claims (5)
1. a kind of quantitative analysis CO2The LR laser raman detection method of gas carbon isotope composition, which is characterized in that this method includes
Following steps：
Step 1: it calculates12CO2Raman quantizing factor F12CO2, specific method is：
Step 101 is incited somebody to action using gas proportion mixing device12CO2And N2By different volumes than being uniformly mixed, obtain a series of differences and match
Ratio12CO2/N2Mixed gas；
Step 102, using Laser-Raman microspectroscopy to proportionings various in step 10112CO2/N2Mixed gas carries out respectively
Micro laser Raman spectroscopy detects, and obtains N2Characteristic peak ν[N2]And12CO2The double characteristic peak ν of Fermi resonance- [12CO2]With
ν+ [12CO2], ν under various conditions of mixture ratios is then calculated respectively- [12CO2]The peak area A at place- [12CO2]、ν+ [12CO2]The peak area at place
A+ [12CO2]And ν[N2]The peak area A at place1 [N2]；The ν- [12CO2]、ν+ [12CO2]And ν[N2]Unit be cm-1；
Step 103, the A according to step 102- [12CO2]And A+ [12CO2]It calculates under various conditions of mixture ratios12CO2The peak of characteristic peak
Area A[12CO2], the A[12CO2]=A- [12CO2]+A+ [12CO2], then according to the A[12CO2]It calculates under various conditions of mixture ratios12CO2With N2Characteristic peak peak area compare K1, the K1=[A[12CO2]/Σ12CO2)/A1 [N2]；The Σ12CO2For12CO2It is opposite
Raman scattering cross section normalization factor；
Step 104, with K described in step 1031As ordinate, with12CO2And N2Molar ratio C[12CO2]/C[N2]As abscissa
Throwing figure simultaneously carries out linear fit, calculates the slope of fitting a straight line, obtains F12CO2；
Step 2: it calculates13CO2Raman quantizing factor F13CO2, specific method is：
Step 201 is incited somebody to action using gas proportion mixing device13CO2And N2By different volumes than being uniformly mixed, obtain a series of differences and match
Ratio13CO2/N2Mixed gas；
Step 202, using Laser-Raman microspectroscopy to proportionings various in step 20113CO2/N2Mixed gas carries out respectively
Micro laser Raman spectroscopy detects, and obtains N2Characteristic peak ν[N2]And13CO2The double characteristic peak ν of Fermi resonance- [13CO2]With
ν+ [13CO2], ν under various conditions of mixture ratios is then calculated respectively- [13CO2]The peak area A at place- [13CO2]、ν+ [13CO2]The peak area at place
A+ [13CO2]And ν[N2]The peak area A at place2 [N2]；The ν- [13CO2]And ν+ [13CO2]Unit is cm-1；
Step 203, the A according to step 202- [13CO2]And A+ [13CO2]It calculates under various conditions of mixture ratios13CO2The peak of characteristic peak
Area A[13CO2], the A[13CO2]=A- [13CO2]+A+ [13CO2], then according to the A[13CO2]It calculates under various conditions of mixture ratios13CO2With N2Characteristic peak peak area compare K2, the K2=[A[13CO2]/Σ13CO2)/A2 [N2]；The Σ13CO2For13CO2It is opposite
Raman scattering cross section normalization factor；
Step 204, with K described in step 2032As ordinate, with13CO2And N2Molar ratio C[13CO2]/C[N2]As abscissa
Throwing figure simultaneously carries out linear fit, calculates the slope of fitting a straight line, obtains F13CO2；
Step 3: using Laser-Raman microspectroscopy to by12CO2With13CO2The CO mixed2Gas carries out micro laser drawing
Graceful detection, obtains CO2In gas12CO2The peak area A of characteristic peak12CO2And13CO2The peak area A of characteristic peak13CO2, then basis
Formula C[12CO2]/C[13CO2]=(A12CO2/A13CO2)×(F13CO2/F12CO2) calculate CO2In gas12CO2With13CO2Molar ratio C[12CO2]/C[13CO2]。
2. quantitative analysis CO according to claim 12The LR laser raman detection method of gas carbon isotope composition, feature
It is, ν described in step 102- [12CO2]=1287cm-1, the ν+ [12CO2]=1390cm-1, the ν[N2]=2332cm-1。
3. quantitative analysis CO according to claim 12The LR laser raman detection method of gas carbon isotope composition, feature
It is, Σ described in step 10312CO2=1.49.
4. quantitative analysis CO according to claim 12The LR laser raman detection method of gas carbon isotope composition, feature
It is, ν described in step 202- [13CO2]=1267cm-1, the ν+ [13CO2]=1372cm-1。
5. quantitative analysis CO according to claim 12The LR laser raman detection method of gas carbon isotope composition, feature
It is, Σ described in step 20313CO2=1.437.
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