CN109580413B - Infrared spectroscopic analysis method of binary mixture and application thereof - Google Patents
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000012844 infrared spectroscopy analysis Methods 0.000 title claims description 4
- 239000000126 substance Substances 0.000 claims abstract description 140
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000001228 spectrum Methods 0.000 claims abstract description 81
- 239000011159 matrix material Substances 0.000 claims abstract description 47
- 238000012545 processing Methods 0.000 claims abstract description 28
- ADNPLDHMAVUMIW-CUZNLEPHSA-N substance P Chemical compound C([C@@H](C(=O)NCC(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCSC)C(N)=O)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](N)CCCN=C(N)N)C1=CC=CC=C1 ADNPLDHMAVUMIW-CUZNLEPHSA-N 0.000 claims description 34
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000002835 absorbance Methods 0.000 claims description 7
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- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 abstract description 18
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- 239000007789 gas Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000009897 systematic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000000003 thermogravimetry coupled to Fourier transform infrared spectroscopy Methods 0.000 description 2
- -1 and likewise Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
Abstract
The invention discloses an infrared spectrum analysis method of a binary mixture and application thereof, wherein the method comprises the steps of firstly obtaining a one-dimensional infrared spectrum and an original data matrix of the binary mixture (a substance m and a substance n) by adopting a thermogravimetry-infrared technology, then processing the two-dimensional infrared spectrum to obtain a two-dimensional asynchronous spectrum, and then cutting off the system peak lacking part in the two-dimensional asynchronous spectrum to respectively obtain the one-dimensional infrared spectrum of the substance m and the one-dimensional infrared spectrum of the substance n. The method can be used for infrared resolution of water-containing substances, and can remove the influence of moisture on the infrared spectrum of the substances, particularly for infrared resolution of water-containing organic substances. The method can perform infrared analysis without completely separating the mixture, and can obtain the one-dimensional infrared spectrum of the pure substance by only one test generally without repeated tests. When the method is applied to a water-containing substance, the influence of moisture on the infrared spectrum of the substance can be removed without drying before detection.
Description
Technical Field
The invention relates to infrared spectroscopy, in particular to an infrared analysis method of a binary mixture and application thereof, and particularly relates to an infrared analysis method of a binary mixture system by adopting thermogravimetry-infrared and application thereof.
Background
In the field of analytical chemistry, infrared detection has been widely used, however, analysis of mixtures has been one of the important challenges. Typically, the mixture is separated and the different components of the mixture are identified by spectroscopic analysis. However, incomplete separation is common in the analysis of complex mixtures, and finding suitable separation conditions is often tedious and tedious. Therefore, in many cases, spectra of a mixture are obtained rather than spectra of pure substances, which makes chemical identification very difficult.
One common treatment method is to improve the separation capacity and optimize the separation conditions, but in the separation process of a multi-component mixture, the search for suitable separation conditions is not only time-consuming and labor-consuming, but also generally has certain requirements on the equipment used, and the universality is limited.
Another common processing method is to reduce the corresponding outflow curve and infrared information of each substance in the chromatographic process by using a metrology method through mathematical post-processing of the chromatographic-infrared combined data, so as to provide support for qualitative and quantitative determination of each component in the mixture. Such methods include Multivariate Curve Resolution (MCR), Self-modeling curve resolution (SMCR), Alternating trilinear decomposition (Alternating trilinear decomposition method), and other technical means. These methods have good analysis results for specific systems, but in general, analysis of mixture data remains a current research difficulty.
In the prior art, thermogravimetric-infrared coupled techniques have also been widely used to analyze the thermal decomposition or evaporation of various components in a sample. In practice, however, the release characteristics of the different gas components overlap significantly, which makes it difficult to identify the various components from the infrared spectrum of the sample.
Therefore, a mixed system infrared analysis method is needed to obtain infrared spectra with single components.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies, and have obtained a one-dimensional infrared spectrum and an original data matrix of a binary mixture (a substance m and a substance n) by using a thermogravimetric-infrared technique, and then have processed the two-dimensional asynchronous spectrum to find that the intensity of a part of peaks appearing in the one-dimensional infrared spectrum is zero in the two-dimensional asynchronous spectrum, that is, a system missing peak exists in the two-dimensional asynchronous spectrum, and have found that the system missing peak is truncated in the two-dimensional asynchronous spectrum to obtain a spectrum of one of pure components, and then the system missing peak is truncated in the other system missing positions to obtain a spectrum of the other pure component, thereby achieving infrared analysis of a binary system, and thus completing the present invention.
The invention provides an infrared analysis method of a binary mixture, which is embodied in the following aspects:
(1) a method for infrared spectroscopic analysis of a binary mixture, wherein the method comprises the steps of:
step 3, performing data truncation at the system peak lacking position of the two-dimensional asynchronous spectrum to obtain one-dimensional data, and performing data processing to obtain a one-dimensional infrared spectrum of each substance in the binary mixture;
wherein the system peak-lacking is: in the one-dimensional infrared spectrum of the binary mixture, absorption peaks exist at the wavelength x and the wavelength y, but no cross peak appears at the point (x, y) in the two-dimensional asynchronous spectrum, and the point (x, y) in the two-dimensional asynchronous spectrum is the system defect peak.
(2) The method according to the above (1), wherein the binary mixture is set to include a substance m and a substance n, wherein, in the one-dimensional infrared spectrum of the substance m and the substance n which are independent from each other,
substance m contains at least one independent peak not possessed by substance n;
substance n contains at least one independent peak that substance m does not have.
(3) The method according to the above (1) or (2), wherein, in step 1, the raw data matrix is represented by formula (1):
wherein, in formula (1), the element A (t)i,λj) Corresponding to heating time tiWavelength lambda in the lower recorded one-dimensional spectrumjAbsorbance of (d) in (d).
(4) The method according to one of the above (1) to (3), wherein the element A (t) in the original data matrixi,λj) As shown in formula (2):
A(ti,λj)＝Cm(ti)fm(λj)+Cn(ti)fn(λj) Formula (2);
wherein, in the formula (2), m and n represent a substance m and a substance n, C in a binary mixture, respectivelym(ti) AndCn(ti) Respectively, m and n are heated at tiConcentration at time fm(λj) And fn(λj) Respectively representing the infrared spectrum functions of the substance m and the substance n.
(5) The method according to one of the above (1) to (4), wherein in step 2, the data correlation process is represented by formula (3):
Ψ(x,y)＝A(x)TNA (y) formula (3);
wherein, in formula (3):
ψ (x, y) represents the intensity at a point (x, y) in the two-dimensional asynchronous spectrum, and when ψ (x, y) is 0, it represents that the intensity at this point is zero, that is, no cross peak occurs at (x, y) in the two-dimensional asynchronous spectrum;
n denotes a Hilbert-Noda transform matrix, T denotes a transpose of the matrix, and the Hilbert-Noda transform matrix is expressed by equation (3-1):
wherein, in the formula (3-1), NjkRepresenting the elements of the jth row and kth column in the transform matrix N.
(6) The method according to one of the above (1) to (5), wherein in step 2, the system off-peak is at least two, respectively set to a point ψ (x)m,ym) Point phi (x)n,yn) In the process, wherein,
xmand ymAre peak positions of independent peaks in a one-dimensional infrared spectrum of a substance m, wherein xm＝ymOr xm≠ym；
xnAnd ynAre all the peak positions of independent peaks in the one-dimensional infrared spectrum of a substance n, wherein xn＝ynOr xn≠yn。
(7) The method according to one of the above (1) to (6), wherein the step 3 includes the substeps of:
step 3-1, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrummOr x ═ xmCutting to obtain a group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the substance n;
step 3-2, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrumnOr x ═ xnAnd cutting to obtain another group of one-dimensional data, and processing to obtain the one-dimensional infrared spectrum of the substance m.
According to a further aspect of the present invention there is provided a use according to the first aspect of the present invention for infrared resolution of water-containing substances, to remove the effect of moisture on the infrared spectrum of the substance, and in particular for infrared resolution of water-containing organic substances.
(8) Use of the method according to one of (1) to (7) above for infrared resolution of water-containing substances, for removing the influence of moisture on the infrared spectrum of the substances, in particular for infrared resolution of water-containing organic substances.
(9) According to the use of (8) above, the substance to be detected is set to be an aqueous substance p comprising a pure substance p and water, wherein the pure substance p contains at least one independent peak which the pure substance p does not have in the one-dimensional infrared spectrum in which the pure substance p and the water are independent from each other, and the water contains at least one independent peak which the pure substance p does not have.
(10) The use according to the above (8) or (9), wherein the infrared resolution of the aqueous substance is performed as follows:
step a, detecting a water-containing substance p by using a thermogravimetry-infrared combined instrument to obtain a one-dimensional infrared spectrum and an original data matrix;
b, carrying out data correlation processing on the original data matrix obtained in the step a to obtain a two-dimensional asynchronous spectrum of the water-containing substance p, and analyzing by combining with a one-dimensional infrared spectrum of the water-containing substance p to confirm system peak lack in the two-dimensional asynchronous spectrum;
c, performing data truncation at the system peak lacking part of the two-dimensional asynchronous spectrum to obtain one-dimensional data, and performing data processing to obtain respective one-dimensional infrared spectrums of the pure substance p and the water;
preferably, step c comprises the sub-steps of:
step c-1, namely y is taken along the system peak lack position of the two-dimensional asynchronous spectrumpOr x ═ xpCutting to obtain a set of one-dimensional dataProcessing to obtain a one-dimensional infrared spectrum of the water;
step c-2, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrumWater (W)Or x ═ xWater (W)Cutting to obtain another group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the pure substance p;
wherein x ispAnd ypAll are peak positions of independent peaks in a pure substance p one-dimensional infrared spectrum, wherein, xp＝ypOr xp≠yp；xWater (W)And yWater (W)Are all the peak positions of independent peaks in the water one-dimensional infrared spectrum, wherein, xWater (W)＝yWater (W)Or xWater (W)≠yWater (W)。
Drawings
Fig. 1(a) shows a two-dimensional asynchronous spectrum diagram of a binary mixture, curves above and to the right of the two-dimensional asynchronous spectrum being a one-dimensional infrared spectrum diagram of the binary mixture, and fig. 1 (B) shows a one-dimensional infrared spectrum diagram of each of a substance m and a substance n in the binary mixture;
FIG. 2(A) shows the two-dimensional asynchronous spectrum obtained in example 1, and FIG. 2(B) shows CO2/One-dimensional IR spectrum of the CO mixture, Curve 1 shows the CO separated according to the process of the invention2Curve 3 shows the one-dimensional infrared spectrum of CO separated according to the method of the invention;
in fig. 3(a) shows the two-dimensional asynchronous spectrum obtained in example 2, in fig. 3(B) curve 1 shows the standard one-dimensional infrared spectrum of water obtained by detecting water alone, curve 2 shows the one-dimensional infrared spectrum of water separated according to the method of the present invention, curve 3 shows the one-dimensional infrared spectrum of aqueous isopropanol (water/isopropanol mixture), curve 4 shows the one-dimensional infrared spectrum of isopropanol separated according to the method of the present invention, and curve 5 shows the standard one-dimensional infrared spectrum of isopropanol obtained by detecting isopropanol alone;
wherein, in fig. 2 and 3: x (-1) means multiply by-1, making all data points non-negative.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention provides an infrared spectrum analysis method of a binary mixture, wherein the binary mixture is set to comprise a substance m and a substance n, and then the substance m has at least one independent peak relative to the substance n in a one-dimensional infrared spectrum, and the substance n has at least one independent peak relative to the substance m in a one-dimensional infrared spectrum, wherein the method comprises the following steps:
According to a preferred embodiment of the present invention, in step 1, the original data matrix is represented by formula (1):
wherein the matrix shown in formula (1) is a dynamic infrared matrix, specifically, each element A (t)i,λj) Corresponding to heating time tiWavelength lambda in the lower recorded one-dimensional spectrumjAbsorbance of (d) in (d).
In a further preferred embodiment, the element a (t) in the original data matrixi,λj) As shown in formula (2):
A(ti,λj)＝Cm(ti)fm(λj)+Cn(ti)fn(λj) Formula (2).
Wherein, in the formula (2), m and n represent a substance m and a substance n, C in a binary mixture, respectivelym(ti) And Cn(ti) Respectively, m and n are heated at tiThe concentration at the moment, C can be seenm(ti) And Cn(ti) Respectively representing the concentration of the substance m and of the substance n with respect to the time tiAs a function of (c). f. ofm(λj) And fn(λj) Respectively generation by generationTable substance m and substance n. And a is the absorbance, so each element in a is the sum of the contributions of substance m and substance n.
And 2, carrying out data correlation processing on the original data matrix obtained in the step 1 to obtain a two-dimensional asynchronous spectrum of the binary mixture, and analyzing by combining a one-dimensional infrared spectrum of the binary mixture to confirm the system peak lack in the two-dimensional asynchronous spectrum.
According to a preferred embodiment of the present invention, in step 2, the data-dependent processing is represented by formula (3):
Ψ(x,y)＝A(x)TNA (y) formula (3).
Specifically, the raw data matrix obtained in step 1 is processed according to equation (3), preferably in MATLAB software, to obtain a two-dimensional asynchronous spectrum of the binary mixture. In equation (3), ψ (x, y) represents the intensity at a point (x, y) in the two-dimensional asynchronous spectrum, and when ψ (x, y) is 0, it represents that the intensity at the point is zero, that is, no cross peak appears at (x, y) in the two-dimensional asynchronous spectrum; in equation (3), N denotes a Hilbert-Noda transform matrix, and T denotes a transpose of the matrix. Specifically, the Hilbert-Noda transformation matrix is shown as formula (3-1):
wherein N isjkRepresenting the elements of the jth row and kth column in the transform matrix N.
According to a preferred embodiment of the present invention, the system peak-off is: in the one-dimensional infrared spectrum of the binary mixture, absorption peaks exist at the wavelength x and the wavelength y, but no cross peak appears at the point (x, y) in the two-dimensional asynchronous spectrum, and the point (x, y) in the two-dimensional asynchronous spectrum is a system defect peak.
Specifically, as shown in fig. 1(a), a two-dimensional asynchronous spectrum of a binary mixture of a substance m and a substance n is shown, and a one-dimensional infrared spectrum of the binary mixture is shown above and to the right. In the one-dimensional infrared spectrum of the mixture, the wavelength is 588cm-1And a wavelength of 730cm-1The attachments all have absorption peaks, however, in a two-dimensional asynchronous spectrumNo cross-over peak occurs near the midpoint (588,730). Similar phenomena occur in all the regions marked by boxes, and in the present invention, we define the box in fig. 1(a) as a system defect.
And when the infrared spectrum of the substance m contains lmA peak (called independent peak) which is not coincident with the infrared spectrum of the substance n, i appears on the two-dimensional asynchronous spectrum of the mixed systemm×lmA system of missing peaks which formm×lmA square matrix of (a). Specifically, as shown in fig. 1 (B), substance m has 3 independent peaks on the one-dimensional infrared spectrum that substance n does not have, and 3 × 3 system missing peaks appear on the two-dimensional asynchronous spectrum in fig. 1(a), and these system missing peaks form a 3 × 3 square matrix, specifically, as shown in fig. 1, the abscissa and ordinate of the system missing peaks are any two-by-two combination of wavelengths at 3 independent peaks; substance n has 2 independent peaks on the one-dimensional infrared spectrum that substance m does not have, and 2 × 2 system missing peaks appear on the two-dimensional asynchronous spectrum in fig. 1(a), and these system missing peaks form a 2 × 2 square matrix, specifically, as shown in fig. 1(a), the abscissa and ordinate of the system missing peaks are arbitrary two-by-two combinations of wavelengths at 2 independent peaks.
The analysis reason is as follows: in combination with formulas (1) to (3), in a two-dimensional asynchronous spectrum of a binary mixture:
where A is the absorbance, which is the sum of the absorbance of substance m and the absorbance of substance n. In formula (4), x and y represent that substance m has absorption peaks in the one-dimensional infrared spectrum at wavelength x and wavelength y that substance n does not have, i.e., substance m has independent peaks at wavelength x and wavelength y. Specifically, when a substance m has an absorption peak at only one wavelength that substance n does not have, x ═ y; if the substance m is inmHas an absorption peak at one wavelength which is not contained in the substance n, and (x, y) is lmAny two of the wavelengths are combined.
When substance m has an independent peak with respect to substance n, in formula (4), fn(x)＝0，fnWhen (y) is 0, formula (4) becomes formula (5):
wherein, in formula (5), fm(x) And fm(y) is a constant and the Hilbert-Noda transform matrix has the following properties:
may be any given nth order vector and, therefore, in equation (5),
thus, Ψ (x, y) ≡ 0.
It is stated that when substance m has an independent peak in the one-dimensional infrared spectrum relative to substance n, there is a system missing peak in the two-dimensional asynchronous spectrum at the wavelength of the independent peak. And when the one-dimensional infrared spectrum of the substance m contains lmWhen a peak (called independent peak) which is not coincident with the one-dimensional infrared spectrum of the substance n appears, l appears in the two-dimensional asynchronous spectrum of the mixed systemm×lmAnd (4) lacking peaks in the system. The same applies to the substance n, i.e. when the infrared spectrum of the substance n has lnA peak that does not coincide with the infrared spectrum of the substance m (called an independent peak), l will appear on the two-dimensional asynchronous spectrumn×lnA systematic defect, which can form an×lnA square matrix of the form.
According to a preferred embodiment of the present invention, in step 2, the number of system peaks is at least two, and the system peaks are respectively set to the point ψ (x)m,ym) And point psi (x)n,yn) Wherein:
xmand ymAre all the peak positions of independent peaks in the one-dimensional infrared spectrum of a substance m, wherein, xm＝ymOr xm≠ym；
xnAnd ynAre all the peak positions of independent peaks in the n-dimensional infrared spectrum of the substance, wherein, xn＝ynOr xn≠yn。
In the present invention, when the substance m has an independent peak with respect to the substance n, xm＝ym(ii) a Two-dimensional asynchronous spectrum midpoint ψ (x) when substance m has multiple independent peaks relative to substance nm,ym) Any combination of peak positions (or wavelengths) of a plurality of independent peaks is possible, that is, in this case, xmAnd ymMay or may not be equal. The same applies to substance n.
And 3, performing data truncation at the system peak lacking position of the two-dimensional asynchronous spectrum to obtain one-dimensional data, and performing data processing to obtain a one-dimensional infrared spectrum of each substance in the binary mixture.
Wherein the two-dimensional asynchronous spectrum further has the following properties: let xmAnd ymAll are the peak positions of independent peaks in the one-dimensional infrared spectrum of the substance m, and the one-dimensional infrared spectrum of the substance n can pass through the two-dimensional asynchronous spectrum, wherein y is equal to ymOr x ═ xmDerived from truncated data, i.e. Ψ (x, y)m) Or Ψ (x)mAnd y) is the one-dimensional infrared spectrum data of the substance n. Similarly, let xnAnd ynAll are the peak positions of the independent peaks of the substance n, the infrared spectrum of the substance m can pass through the two-dimensional asynchronous spectrum, and y is equal to ynOr x ═ xnDerived from truncated data, i.e. Ψ (x, y)n) Or Ψ (x)nAnd y) is one-dimensional infrared spectrum data of the substance m.
The analysis reason is as follows: in a two-dimensional asynchronous spectrum y ═ ymOr x ═ xmWhere the intercepted data is Ψ (x, y)m) Or Ψ (x)mY) are respectively shown in formula (6-1) and formula (6-2):
wherein, in the formulae (6-1) and (6-2), ymAnd xmAre all the peak positions of the independent peaks of the substance mn is not absorbing at this wavelength, so fn(ym)＝0，fn(xm) Formula (6-1) and formula (6-2) may be converted to formula (7-1) and formula (7-2), respectively, when ═ 0:
among them, as can be seen from the basic properties of the Hilbert-Noda matrix, in the formulae (7-1) and (7-2),
then, the formulae (7-1) and (7-2) can be converted into the formulae (8-1) and (8-2), respectively:
wherein, in the formula (8-1) and the formula (8-2),
is a constant with respect to x,
for y to be constant, then, it is known that: f. ofn(x)∝Ψ(x,ym) And fn(y)∝Ψ(xmY), say that the spectrum of substance n can be represented by y-y in a two-dimensional asynchronous spectrummOr x ═ xmAnd (4) processing the truncated data to obtain the final product.
According to a preferred embodiment of the invention, step 3 comprises the following sub-steps:
step 3-1, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrummOr x ═ xmCutting to obtain a group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the substance n;
step 3-2 in two-dimensional asynchronous spectrumY is the edge of the system at the peak lacking positionnOr x ═ xnAnd cutting to obtain another group of one-dimensional data, and processing to obtain the one-dimensional infrared spectrum of the substance m.
Wherein x ismAnd ymAre the peak positions, x, of the independent peaks in the one-dimensional infrared spectrum of the substance mmAnd ymMay or may not be equal; x is the number ofnAnd ynPeak positions, x, which are all independent peaks of substance nnAnd ynMay or may not be equal.
The binary mixture, the object of analysis of the method of the invention, needs to satisfy the following conditions: substance m has at least one independent peak in a one-dimensional infrared spectrum relative to substance n, and substance n has at least one independent peak in a one-dimensional infrared spectrum relative to substance m. In this case, even if the one-dimensional infrared spectra of the substance m and the substance n overlap each other at other peak positions, the one-dimensional infrared spectra of the substance m and the substance n, respectively, can be obtained.
According to a further aspect of the invention there is provided the use of a method according to the first aspect of the invention for the infrared resolution of aqueous material to remove the effect of moisture on the infrared spectrum of the material, particularly for the infrared resolution of aqueous organic material.
In the infrared spectrum, even a trace amount of water exists in a substance, the identification of a spectrum peak is greatly disturbed, and particularly, the infrared spectrum peak of water is wide, so that the characteristic peak of the substance is easily covered to influence an analysis result. Therefore, in the prior art, the test sample needs to be dried to remove water before infrared detection is performed, but this makes the operation complicated, and in many cases, the water in the substance cannot be completely removed even if drying is performed.
The invention adopts the method of the first aspect to carry out the infrared resolution of the water-containing substance, wherein the substance to be detected is set to be the water-containing substance p which comprises a pure substance p and water, and the water-containing substance p needs to satisfy the following conditions: pure substance p has at least one independent peak in the one-dimensional infrared spectrum relative to water, which has at least one independent peak in the one-dimensional infrared spectrum relative to pure substance p.
According to a preferred embodiment of the invention, the infrared resolution of the aqueous substance is performed as follows:
step a, detecting a water-containing substance p by using a thermogravimetry-infrared combined instrument to obtain a one-dimensional infrared spectrum and an original data matrix;
b, carrying out data correlation processing on the original data matrix obtained in the step a to obtain a two-dimensional asynchronous spectrum of the water-containing substance p, and analyzing by combining with a one-dimensional infrared spectrum of the water-containing substance p to confirm system peak lack in the two-dimensional asynchronous spectrum;
and c, performing data truncation at the system peak lacking position of the two-dimensional asynchronous spectrum to obtain one-dimensional data, and performing data processing to obtain respective one-dimensional infrared spectrums of the pure substance p and the water.
According to a preferred embodiment of the present invention, in step b, the number of system peaks is at least two, and the system peaks are respectively set to the point ψ (x)p,yp) And point psi (x)Water (W),yWater (W))。
Wherein x ispAnd ypAll are peak positions of independent peaks in a pure substance p one-dimensional infrared spectrum, wherein, xp＝ypOr xp≠yp；xWater (W)And yWater (W)Are all the peak positions of independent peaks in the water one-dimensional infrared spectrum, wherein, xWater (W)＝yWater (W)Or xWater (W)≠yWater (W)。
According to a preferred embodiment of the invention, step c comprises the following sub-steps:
step c-1, namely y is taken along the system peak lack position of the two-dimensional asynchronous spectrumpOr x ═ xpCutting to obtain a group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the water;
step c-2, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrumWater (W)Or x ═ xWater (W)Cutting to obtain another group of one-dimensional data, and processing to obtain the one-dimensional infrared spectrum of the pure substance p.
Because the water is 2200-3300 cm-1No absorption peak exists nearby, and most of organic matters almost have the absorption peak of C-H bonds in the range; and the water is 3700-4000 cm-1Has absorption peak nearby and is organicThere is no absorption peak in this range, which results in a separate peak for most organics relative to water, and likewise, water relative to most organics. It is stated that the method according to the invention can be applied to a large part of organic systems.
The invention has the following beneficial effects:
(1) the method of the invention can carry out infrared analysis without completely separating the mixture;
(2) the method does not need repeated tests, and generally only carries out one-time test to obtain the one-dimensional infrared spectrum of the pure object;
(3) the method is simple, and can analyze the infrared spectrum which is seriously overlapped;
(4) the method can be used for infrared resolution of the water-containing substance and removing the influence of water on an infrared spectrogram.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the present example, isopropanol is AR grade, and N is used2As the purge gas, the flow rate was set to 70mL/min,
2example 1 Infrared analysis of a binary Mixed System of CO and CO
Performing thermogravimetric-infrared detection on calcium oxalate, wherein the calcium oxalate is subjected to thermal decomposition, and CO are generated in 400-900s2Is discharged simultaneously
Specifically, 20g of calcium oxalate was loaded on a TGA-FTIR spectrometer. The sample was heated from 30 ℃ to 900 ℃ at a heating rate of 50 ℃/min and then held at 900 ℃ for 5 minutes. Nitrogen purge gas was used throughout the experiment. FTIR spectra of the emitted gas samples were recorded every 6 seconds and spectra of the vapors were collected, yielding a raw data matrix.
Then carrying out data correlation processing in MATLAB software according to the formula (3) to obtain CO and CO2The one-dimensional infrared spectrum and the two-dimensional asynchronous spectrum of the mixture are respectively shown as the figure 2(B)Middle curve 2 and fig. 2 (a).
As can be seen in fig. 2(a), there are a large number of systematic missing peaks (SACPs) in the resulting two-dimensional asynchronous spectrum. In this example, we collected 5 systematic missing peaks, identified in fig. 2(a) and labeled with rectangles, (2366,650), (2366,2360), (212,2360), (212,650), and (2150), respectively.
The system can be divided into two groups: the system imperfections at (2366,650), (2366,2360), (212,2360), and (212,650) form a 2 × 2 matrix; the system at (2150) lacks peaks to form a 1 x 1 matrix.
Making y 2150cm on two-dimensional asynchronous spectrum-1The obtained slice was horizontally sliced, and the obtained slice was shown as curve 1 in FIG. 2(B), i.e., CO was obtained2(ii) infrared spectroscopy; at y 2360cm-1Another horizontal slice is prepared and shown as curve 3 in FIG. 2(B), i.e., an infrared spectrum of CO is obtained.
Example 2 Infrared resolution of aqueous systems
Thermogravimetric-infrared detection was performed on water and isopropanol systems, where the boiling points of water and isopropanol were 100 ℃ and 88 ℃, respectively, and the release curves of the two substances overlapped due to a slight difference in boiling points.
Specifically, pure water and pure isopropanol and H2Mixtures of O/isopropanol (31.2mg, v: v ═ 1:1) were loaded separately onto a TGA-FTIR spectrometer. Each sample was heated from 30 ℃ to 150 ℃ at a heating rate of 30 ℃/min, and then the samples were held at 150 ℃ for 5 minutes. Nitrogen purge gas was used throughout the experiment. FTIR spectra of the emitted gas samples were recorded every 6 seconds and spectra of the vapors were collected, yielding a raw data matrix.
Then, data correlation processing is carried out in MATLAB software according to the formula (3), and a one-dimensional infrared spectrum two-dimensional asynchronous spectrum of the mixture is obtained, and is respectively shown as a curve 3 in a graph 3(B) and a curve (A) in a graph 3.
Where in FIG. 3 curve 1 is the IR spectrum for pure water, curve 5 is the IR spectrum for pure isopropanol and curve 3 is the IR spectrum for a water/isopropanol mixture, it can be seen that in curve 3, water and isopropanol are presentThe absorption peaks of (A) overlap, especially water in 3300-4000 cm-1The near broad peak makes isopropanol 3660cm-1The absorption peak of the appendage is masked.
As can be seen in fig. 3(a), there are a large number of systematic missing peaks (SACPs) in the resulting two-dimensional asynchronous spectrum. In this example, we collected 8 systematic missing peaks, identified in fig. 3(a) and labeled with rectangles, (3903,1717), (3903), (1717,3903), (1717), (2978,951), (2978), (951,2978), and (951), respectively.
The system can be divided into two groups: the system imperfections at (3903,1717), (3903), (1717,3903), and (1717) form a 2 × 2 matrix; the system imperfections at (2978,951), (2978), (951,2978), and (951) form another 2 x 2 matrix.
Making y 951cm on two-dimensional asynchronous spectrum-1The obtained slice was horizontally sliced, and the obtained slice was shown as curve 2 of FIG. 3(B), i.e., the infrared spectrum of the water in the mixture was obtained; at y 3903cm-1Another horizontal slice is prepared and shown as curve 4 in FIG. 3(B), which is an infrared spectrum of isopropanol in the mixture.
Therein, for comparison, the infrared spectra of pure water and pure isopropanol exist as curve 1 and curve 5, respectively. The IR spectrum of the water/isopropanol mixture is also shown as curve 3 in FIG. 3 (B). The shape of curve 2 is the same as the shape of curve 1. The shape of curve 4 is the same as that of curve 5.
The phase angles were also calculated to demonstrate the similarity between curve 1/curve 2 and curve 4/curve 5, with the phase angle of curve 1/curve 2 being 0.04 ° and the phase angle of curve 4/curve 5 being 0.07 °. That is, curve 2 is essentially the infrared spectrum of water and curve 4 is the infrared spectrum of isopropanol.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. A method for infrared spectroscopic analysis of a binary mixture, said method comprising the steps of:
step 1, detecting the binary mixture by using a thermogravimetry-infrared combined instrument to obtain a one-dimensional infrared spectrum and an original data matrix of the binary mixture;
step 2, carrying out data correlation processing on the original data matrix obtained in the step 1 to obtain a two-dimensional asynchronous spectrum of the binary mixture, and analyzing by combining with a one-dimensional infrared spectrum of the binary mixture to confirm system peak lack in the two-dimensional asynchronous spectrum;
step 3, performing data truncation at the system peak lacking position of the two-dimensional asynchronous spectrum to obtain one-dimensional data, and performing data processing to obtain a one-dimensional infrared spectrum of each substance in the binary mixture;
wherein the system peak-lacking is: absorption peaks exist at the positions of the wavelength x and the wavelength y in the one-dimensional infrared spectrum of the binary mixture, but no cross peak appears at the positions of the points (x, y) in the two-dimensional asynchronous spectrum, and the points (x, y) in the two-dimensional asynchronous spectrum are system defect peaks;
setting the binary mixture to comprise a substance m and a substance n, and in the one-dimensional infrared spectrum of the substance m and the substance n respectively,
substance m contains at least one independent peak not possessed by substance n;
substance n contains at least one independent peak that substance m does not have.
2. The method of claim 1, wherein in step 1, the raw data matrix is represented by equation (1):
wherein, in formula (1), the element A (t)i,λj) Corresponding to heating time tiWavelength lambda in the lower recorded one-dimensional spectrumjAbsorbance of (d) in (d).
3. The method of claim 2, wherein the element a (t) in the raw data matrixi,λj) As shown in formula (2):
A(ti,λj)＝Cm(ti)fm(λj)+Cn(ti)fn(λj) Formula (2);
wherein, in the formula (2), m and n represent a substance m and a substance n, C in a binary mixture, respectivelym(ti) And Cn(ti) Respectively, m and n are heated at tiConcentration at time fm(λj) And fn(λj) Respectively representing the infrared spectrum functions of the substance m and the substance n.
4. The method of claim 1, wherein in step 2, the data correlation process is represented by equation (3):
Ψ(x,y)＝A(x)TNA (y) formula (3);
wherein, in formula (3):
ψ (x, y) represents the intensity at a point (x, y) in the two-dimensional asynchronous spectrum, and when ψ (x, y) is 0, it represents that the intensity at this point is zero, that is, no cross peak occurs at (x, y) in the two-dimensional asynchronous spectrum;
n denotes a Hilbert-Noda transform matrix, T denotes a transpose of the matrix, and the Hilbert-Noda transform matrix is expressed by equation (3-1):
wherein, in the formula (3-1), NjkRepresenting the elements of the jth row and kth column in the transform matrix N.
5. The method of claim 1, wherein in step 2, the system is starved toAt least two are set as the point psi (x)m,ym) Point phi (x)n,yn) In the process, wherein,
xmand ymAre peak positions of independent peaks in a one-dimensional infrared spectrum of a substance m, wherein xm＝ymOr xm≠ym；
xnAnd ynAre all the peak positions of independent peaks in the one-dimensional infrared spectrum of a substance n, wherein xn＝ynOr xn≠yn。
6. The method according to claim 1, characterized in that step 3 comprises the following sub-steps:
step 3-1, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrummOr x ═ xmCutting to obtain a group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the substance n;
step 3-2, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrumnOr x ═ xnAnd cutting to obtain another group of one-dimensional data, and processing to obtain the one-dimensional infrared spectrum of the substance m.
7. Use of the method according to one of claims 1 to 6 for infrared resolution of aqueous substances, to remove the influence of moisture on the infrared spectrum of the substance.
8. Use according to claim 7, characterized in that the method is used for infrared resolution of aqueous organic substances.
9. The use according to claim 7, wherein the substance to be detected is an aqueous substance p comprising a pure substance p and water, wherein the pure substance p has at least one distinct peak which the water does not have and the water has at least one distinct peak which the pure substance p does not have in the one-dimensional infrared spectra of the pure substance p and the water, which are independent of each other.
10. Use according to claim 7, wherein the infrared resolution of the aqueous substance is carried out by:
step a, detecting a water-containing substance p by using a thermogravimetry-infrared combined instrument to obtain a one-dimensional infrared spectrum and an original data matrix;
b, carrying out data correlation processing on the original data matrix obtained in the step a to obtain a two-dimensional asynchronous spectrum of the water-containing substance p, and analyzing by combining with a one-dimensional infrared spectrum of the water-containing substance p to confirm system peak lack in the two-dimensional asynchronous spectrum;
and c, performing data truncation at the system peak lacking position of the two-dimensional asynchronous spectrum to obtain one-dimensional data, and performing data processing to obtain respective one-dimensional infrared spectrums of the pure substance p and the water.
11. Use according to claim 10, characterized in that step c comprises the following sub-steps:
step c-1, namely y is taken along the system peak lack position of the two-dimensional asynchronous spectrumpOr x ═ xpCutting to obtain a group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the water;
step c-2, along y ═ y at the system peak lack position of the two-dimensional asynchronous spectrumWater (W)Or x ═ xWater (W)Cutting to obtain another group of one-dimensional data, and processing to obtain a one-dimensional infrared spectrum of the pure substance p;
wherein x ispAnd ypAll are peak positions of independent peaks in a pure substance p one-dimensional infrared spectrum, wherein, xp＝ypOr xp≠yp；xWater (W)And yWater (W)Are all the peak positions of independent peaks in the water one-dimensional infrared spectrum, wherein, xWater (W)＝yWater (W)Or xWater (W)≠yWater (W)。
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