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Australian Centre for Research on Separation Science (ACROSS) and School of. 4. Natural Sciences ... sources such as lasers,2-3 particularly due to hi...
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Letter

A chemometric approach to the calibration of LEDbased optical gas sensors using HITRAN data Parvez Mahbub, John Leis, and Mirek Macka Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b01295 • Publication Date (Web): 30 Apr 2018 Downloaded from http://pubs.acs.org on May 1, 2018

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Analytical Chemistry

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A chemometric approach to the calibration of LED-based optical gas sensors using HITRAN data Parvez Mahbub1,2,*, John Leis3, Mirek Macka1,4

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*corresponding author: [email protected]

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Australian Centre for Research on Separation Science (ACROSS) and School of Natural Sciences, University of Tasmania, Private Bag 75, Hobart 7001, Australia Institute of Sustainability and Innovation, Victoria University, Footscray Park Campus, Melbourne, Victoria 3011, Australia School of Mechanical and Electrical Engineering, University of Southern Queensland, Australia Department of Chemistry and Biochemistry, Mendel University in Brno, Zemedelska 1, CZ 613 00 Brno, Czech Republic

Abstract

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Modelling the propagation of light from LED sources is problematic since the emission

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covers a broad range of wavelengths and thus cannot be considered as monochromatic.

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Furthermore, the lack of directivity of such sources is also problematic. Both attributes are

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characteristic of LEDs. Here we propose a HITRAN (high-resolution transmission molecular

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absorption database) based chemometric approach that incorporates not-perfect-

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monochromaticity and spatial directivity of near-infrared (NIR) LED for absorbance

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calculations in 1% to 6% methane (CH4) in air, considering CH4 as a model absorbing gas.

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We employed the absorbance thus calculated using HITRAN to validate the experimentally

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measured absorbance of CH4. The maximum error between the measured and calculated

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absorbance values were within 1%. The approach can be generalised as a chemometric

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calibration technique for measuring gases and gas mixtures that absorb emissions from

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polychromatic or not-perfect-monochromatic sources, provided the gas concentration, optical

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pathlength, as well as blank and attenuated emission spectra of the light source are

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incorporated into proposed chemometric approach.

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Keywords: HITRAN, chemometrics, calibration of gas sensor, not-perfect-

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monochromaticity, spatial directivity, optical pathlength, emission spectra of LED 1 ACS Paragon Plus Environment

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Remote monitoring of hazardous gases using optical sensors based on the theories of

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absorption spectroscopy has become a routine task in modern-day industrial environments

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such as mining, landfills as well as in laboratories, office spaces, medical care facilities, and

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livestock enclosures. The absorbance-based gas detection is mainly undertaken in the infrared

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(IR) region due to the selective absorption of IR radiation by a wide range of gas molecules.

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In this context, the absorption parameters of gas molecules (absorption cross-section and line

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intensity) at specified pressures and temperatures are tabulated using spectroscopic databases

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such as HITRAN* and employed for establishing HITRAN-based (theoretical) calculations of

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absorbance of gas molecules at different concentrations and pathlengths using the

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fundamental principle of absorption of light (known as the Bouguer-Beer-Lambert law). For

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in-situ gas sensing by optical sensors, this is very straightforward for monochromatic light

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sources such as lasers,2-3 particularly due to high degree of coherency, monochromaticity and

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directivity of laser sources. Mizaikoff and co-workers employed quantum cascade lasers with

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hollow waveguides for in-situ and laboratory measurement of different gases such as

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benzene, toluene, xylene, methane, propane, butane, carbon dioxide, cyclopropane and

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isobutylene.4-6 Although lasers are predominantly used for gas sensing in IR spectral region,

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Light Emitting Diodes (LEDs), whose emission spectra is not strictly monochromatic, are

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increasingly becoming a preferred choice as light sources, since LEDs facilitate portability,

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low-cost and less energy consumption.7 The not-perfect-monochromaticity (polychromatic

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emission spreading across a narrow wavelength range) and spatial directivity (the angle of

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spread of radiation in 3D space) associated with the LEDs employed in optical sensors is

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characterised by the bandwidth (full width at half of maximum emission intensity) and

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divergent optical paths, respectively. Hence, absorbance calculations without incorporating

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the not-perfect-monochromaticity and spatial directivity using spectral databases such as *

HITRAN is a molecular absorption database which compiles the spectroscopic parameters of different gases and gas mixtures and utilises computer codes to predict and simulate the transmission and emission of light in the atmosphere.1 2 ACS Paragon Plus Environment

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Analytical Chemistry

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HITRAN would incorporate a systematic bias. Mayrwöger et al.8 reported HITRAN-based

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absorbance calculation for gases where absorbance of CO2 was simulated using ray tracing

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software (ZEMAX®) that required complex post-processing of ray tracing data. Such

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simulations become complicated since the thermal IR emitters using heated filaments do not

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feature a narrowly-formed radiation pattern in the study reported. In this context, LEDs offer

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a better choice since the IR emission can be modulated in the kHz range, which substantially

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reduces surface heating of the emitter. To date, there have been numerous illustrations of the

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use of mid infrared (MIR) and near infrared (NIR) LEDs for sensing of various gases such as

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CH4 and CO2.9-13 However, to the best of authors’ knowledge, no scientific investigations

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involving LED-based optical gas sensors to date has demonstrated accurate calculation of

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absorbance of gases from the fundamental principles of light absorption by gaseous

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molecules, taking the not-perfect-monochromaticity and spatial directivity of LEDs into

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consideration simultaneously. In most LED based gas sensing studies, a single-point

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calibration and validation was reported,11-12 which did not provide any concrete evidence on

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the accuracy of the sensor calibration over certain concentrations ranges. Therefore, while

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LED emitters present the possibility of low-cost and rugged sources for IR gas detection, the

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principles for accurate absorbance-based gas detection are not yet fully established. In this

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short communication, we present as a proof of principle, a chemometric approach to

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calculating of methane (CH4) absorbances using HITRAN data, taking not-perfect-

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monochromatic emission and spatial directivity of the LED into consideration for the first

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time, using a rapidly pulsed NIR LED-based CH4 sensor within a closed optical path.14 We

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also demonstrate that our approach to calculation of the absorbance of gases for a wide

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concentration range using the HITRAN database lays the foundation for simple and accurate

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chemometric approach of calculating absorbance of gases or gas mixtures using LEDs.

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Not-perfect-monochromaticity of NIR LEDs

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As LEDs’ emission spectra exhibit polychromaticity across a narrow wavelength range, the

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emission maxima cannot be regarded as a single parameter for the purposes of calculation of

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the absorbance of a species at different concentrations using the Bouguer-Beer-Lambert law.

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In this study, we integrated the area under the attenuated emission spectra of the employed

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LED (Lms16LED-R, Alfa Photonics, Latvia) in the range of 1% to 6% CH4 in air and

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calculated the absorbance as the negative logarithm of the ratio of area under the attenuated

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emission spectra compared to the blank emission spectra of the LED source. We derived the

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LED attenuated emission spectra in 1% to 6% CH4 as a product of LED emission spectra in

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blank and transmittance (i.e., 10

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HITRAN generated absorption cross-section, gas concentration and optical pathlength as

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illustrated in eqn.1. The absorbance values at a particular wavelength, for a specific HITRAN

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absorption cross-section and gas concentration, were integrated as a function of optical

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pathlength (which varies according to the directivity of the LED and discussed in the next

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section). The total absorbance was then calculated according to eqn.2. The detailed procedure

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of calculating the LED attenuated emission spectra in 1% to 6% CH4 is described in the

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electronic supplementary information (ESI).

-absorbance

), where the absorbance was calculated from

   

    =  

    × 10( ! "#$%&'()%* +&%$$ $,+()%* ×-"$ +%*+,*(&"()%* ×%'()+". '"(/.,*-(/) (1)

96 &," 7*8,& (/, 9:; "((,*7"(,8 ,

(2)

(A-F) in the ESI.

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Analytical Chemistry

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Insert Figure 1

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In Fig. 1, we observe that the emission spectra of the NIR LED (Lms16LED-R, Alfa

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Photonics, Latvia) is spread across the 1.4 to 1.8 µm range. In this wavelength range, we

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acquired HITRAN generated absorptivity spectra of CH4 (known as absorption cross-section)

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at 1 atm pressure and 25° C temperature. The calculated absorbance (which is a function of

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absorption-cross section, gas concentration and optical pathlength) can vary significantly at a

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particular wavelength, depending on the variation of the optical pathlength travelled by light

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from emitter to detector. In the next section, we demonstrate the effects of spatial directivity

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of the IR LED on the optical pathlength in an 80 cm long electropolished aluminium tube

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used in an experimental CH4 sensor.14

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Spatial Directivity of IR LEDs

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The spatial directivity plot of LEDs is an established method developed by the Commission

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Internationale de l’Éclairage (CIE) to indicate the angular spread of the emitted light.15 Figure

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S2 in the ESI illustrates the spatial directivity of NIR LED employed in this study, where the

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IR rays are emitted at angles from 0° to 70°.16 We calculated the optical pathlengths travelled

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by the rays emitted at 1° intervals between 0° and 70° using trigonometric rules (for details,

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see Fig. S3 and associated calculations in the ESI). For calculating optical pathlength, we

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initially employed the viewing angle of the LED as a guide for considering each possible path

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travelled by the rays emitted from the LED. The viewing angle is defined as the angle where

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the measured light intensity is 50% of its maximum value.17 The 35° viewing angle of the

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NIR LED in this study covers ~90% (according to Fig. S2 in ESI) of the emission. However,

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considering the rays emitted at angles between 0° and 35° can only serve as a first estimate of

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the HITRAN based absorbance calculation of CH4 as it resulted unsatisfactory agreement

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between the experimentally measured and the calculated absorbance values (Fig. 2A). We

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then included more light paths (~95%) into the HITRAN based absorbance calculations by

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considering rays emitted at angles between 0° and 60°. Nonetheless, the error in measured

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absorbance was ±40% when compared to the calculated absorbances (Fig. 2B). Further, we

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included more light paths (~99%) into the HITRAN based absorbance calculations by

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considering rays emitted at angles between 0° and 70°, which reduced the error to ±1%

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between the experimental and calculated absorbance values over the range of 1% to 6% CH4

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as demonstrated in Fig.2C. Hence, a careful observation of the emitted rays in the spatial

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directivity plot of LED is a crucial step in the chemometric approach using the HITRAN

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database for accurate calculation of absorbance values.

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Insert Figure 2

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The simplified approach of including the maximum amount of light emitted from the LED

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based on the spatial directivity plots as explained above yields an agreement with the

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experimentally established calibration as shown in Fig. 2C. This approach is relatively

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straightforward and does not require use of any specialised software (such as ZEMAX or

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similar) as employed by Mayrwöger et al.8 for ray tracing.

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Proof-of-Principle

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In this study, the NIR LED emits according to vendor’s specification between 1400 nm to

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1800 nm with maximum emission at 1660 nm (Fig. S1A in ESI). The bandwidth of this NIR

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LED at half of its maximum emission is approximately 130 nm (from 1580 nm to 1710 nm)

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which is significantly larger than other UV to near infrared LEDs used in other studies (e.g.,

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see Table S1 in the supplementary information of Noori et al.20). We have used CH4 as a

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model gas and in Fig.1, we observe that some considerable portion of the HITRAN generated

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CH4 absorption cross-section peaks fell within the bandwidth of the LED employed. As the

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HITRAN generated spectra of absorption cross-section change for different gases, the not-

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perfect-monochromaticity of the LED plays a significant role in the absorption and hence,

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needs to be considered in modelling approach for LED emission spectra calculation. In this 6 ACS Paragon Plus Environment

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Analytical Chemistry

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study, we have demonstrated that the not-perfect-monochromaticity of LED sources can be

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better modelled for the gas detection application by employing the chemometric approach of

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calculating the emission spectra of the LED using eqn. 1. Additionally, the absorbance values

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at a specific wavelength varied as a function of optical pathlength, and we have demonstrated

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that the spatial directivity of IR LEDs can be incorporated via the proposed chemometric

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approach.

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Although we achieved excellent agreement between the calculated absorbance and the

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experimentally measured absorbance values for 1% to 6% CH4 by considering rays emitted

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between 0° and 70° that captured ~99% of the emission from LED, still there could be some

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insignificant amount of light from outside the limits of this angular spread of emission which

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may not be captured or detected. In this regard, we note the work of Moreno and co-

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workers,18, 19 who demonstrated three basic electromagnetic radiation zones: near-field, mid-

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field and far-field regarding the modelling of propagation of light from LEDs. Please check

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ESI for detailed discussions on the effects of such extraneous electromagnetic regions on the

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propagation of light from the LED.

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Conclusions

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Although LEDs are relatively low-cost, low-power light sources and facilitate portability of

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optical gas sensors, the not-perfect-monochromaticity and spatial directivity of LED emitters

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are yet to be considered simultaneously in absorption-based gas measurements. Through

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incorporating the attenuation of the LED emission spectra across a narrow absorption band

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and the directivity of the LED into HITRAN based absorbance calculations, this study

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establishes a framework for experimental calibration curves used for IR LED-based optical

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sensors. The significance of this approach is that it is applicable to a wide range of gas

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sensors employing polychromatic or not-perfect-monochromatic LEDs as light sources and to

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gases or gas mixtures that absorb in UV, visible or infrared wavelengths. This study has

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established that the considerations of not-perfect-monochromaticity and spatial directivity of

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LEDs are desirable to develop chemometric approach to enhancing accuracy in such sensors.

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Acknowledgements

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This research did not receive any specific grant from funding agencies in the public,

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commercial, or not-for-profit sectors. MM acknowledges his ARC Future Fellowship

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(FT120100559) to support his contributions to this study.

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Figure Captions

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Figure 1 NIR LED attenuated emission spectra (1400-1800 nm) in 6% 12CH4 (natural abundance 98.82%) calculated from the HITRAN generated absorption cross sections of CH4 within the 1400-1800 nm wavelength range, gas concentrations and optical pathlength (see ESI for HITRAN simulation details).

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Figure 2 Absorbance values of pure CH4 experimentally measured by rapid pulsing of NIR LED compared to the HITRAN calculated absorbance values of different CH4 concentrations (% CH4 converted to Molecule.cm-3) considering rays emitted between (A) 0° to 35°, (B) 0° to 60° and (C) 0° to 70° from the NIR LED. The HITRAN data show unsatisfactory agreement (A), within ±40% of the experimentally measured CH4 absorbance data (B) and within ±1% of the experimentally measured CH4 absorbance data (C). The error bars represent general experimental error of ±1%.

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Figures

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Figure 1

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0.012

A

0.012

Experimental

0.010

HITRAN

0.008

Linear (Experimental)

0.006

Linear (HITRAN)

y = 0.157x - 0.0003 R² = 0.9983

0.004 y = 0.0108x + 5E-07 R² = 1

0.002 0.000

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B

Experimental

Absorbance, a.u.

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Absorbance, a.u.

0.010

y = 0.157x - 0.0003 R² = 0.9983

HITRAN

0.008

Linear (Experimental)

0.006

Linear (HITRAN)

0.004 y = 0.0656x + 2E-05 R² = 1

0.002 0.000

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1%

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3%

4%

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6%

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Methane, %

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Absorbance, a.u.

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0.010

HITRAN

0.008

Linear (Experimental)

y = 0.157x - 0.0003 R² = 0.9983

Linear (HITRAN)

0.006

y = 0.1484x + 9E-05 R² = 0.9999

0.004 0.002

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Figure 2

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Methane, % 10

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