ME348 - Intro to Spectroscopy & Laser

Diagnostics
Fall 2020

Project presentation

Mohamad Abou Daher*

Muhammad Hummayun Yousaf*
Vigneshwaran Sankar*
*Ph.D Student, CCRC, Mechanical Engineering Program, KAUST.
Introduction:
• Major public health
concern
• Major risk factor for
many diseases
• relating to heart
• respiratory problems
• lung cancer
• Pollutants: includes
CO2, NOx, Sulphur, CO,
VOCs and so on
• No safe level exposure
Fig 1. Potential sources of Benzene and other
pollutants from the indoors (WWW)
Literature Review:

• Arnold et al [8] performed a case study on the exposure & human health risk
assessment with benzene & reported the biggest knowledge gap as factor that
limits the advancement.

• Krol et al [11] reported that passive sampling can be an added advantage in

scanning the benzene concentration and its evolution, both temporally and
spatially.

• Abinaya et al [12] analysed the benzene's air quality standards across the 193 UN
member countries and claims that in most of the countries the standards that
being used were not protective of public health.
Rotational and vibrational parameters:
• The ground state vibrational energy for ν = 674 /cm as:
G(0) = 341.5 /cm
• Rotational constants as:

Calculated (/cm) Literature [4] (/cm)

A 0.0942 0.0946
B 0.1885 0.1896
C 0.1910 constants from
0.1896
• Centrifugal distortion [18, 19]:
Range of
Detection
•• Strongest
  peak
• Low spectral
interference
• Use a laser beam
targeting the range of
672-682
 Sensor Theory
• 
• Limited to isobaric, isothermal and
diluted solutions in air.
• Line-shape assumed to be conserved
• For data simulation:

• Add random noise to the incident and

transmitted rays within ±10% of their
intensities. Fig 2. Frequency-dependent absorption coefficient for all
components in the studied range
 Sensor theory
•  Specifications: L = 100 cm, P = 1atm, T =
• Detection Limit corresponding for absorbance of :

Species Benzene Toluene o-xylene m- p-xylene Ethyl Water Carbon Ethene

xylene benzene dioxide
0.07414
0.07414 12.36
12.36 1559.47
1559.47 20.2
20.2 1659.06
1659.06 13.04
13.04 529.1
529.1 0.55
0.55 0.57
0.57
Example Case
Study
 Spectral Analysis

• 

• MLR to determine molar fractions

Species Benzene Toluene o-xylene m-xylene p-xylene Ethyl Water Carbon Ethene
benzene dioxide
3500
3500 4000
4000 2000
2000 4500
4500 1800
1800 2750
2750 3800
3800 860
860 900
900
3500 4000.0 1999.95 4499.99 1800.03 2749.99 3799.98 860 900
3500 4000.0 1999.95 4499.99 1800.03 2749.99 3799.98 860 900
 Sensor Performance
Species detection Water
6000
Benzene 45000
5000 Linear (Benzene)
Toluene 37500
o-Xylene
4000 m_Xylene 30000

X predicted
X predicted

3000 22500

15000
2000
7500
1000
0
0 5000 10000 15000 20000 25000 30000 35000 40000 45000
0 X simulated
0 1000 2000 3000 4000 5000 6000
X simulated
 Method Benzene Comments
detection
limit [ppm]

IR at 674 11.5 ppm Higher detection limit and haven’t consider other
absorbing pollutants in air.
IR at 3090 200 ppb Higher detection limit than ours. (Doesn’t account for
interference with isoprene).
IR at 3040 2 ppb − Lower detection limit but used cavity enhanced
Other sensors absorption
− Much higher L and that’s sheds light on the potential of
improving our detector.
− Can detect other aromatics at lower detection limits,
but there is the tradeoff of interference.
Tiger Select 1 ppb − The lowest we’ve found
Tiger Select
portable 1 ppb −− The lowestdetection
Maximum we’ve found
limit of 20000 ppb
portable
detector −− Maximum detection
Can report benzene aslimit ofas
well 20000
total ppb
aromatic content
detector −− Can report benzene as
Commercially available. well as total aromatic content
− Commercially available.
 Boltmann Distribution of Rovibrational
Energy
Total Energy (Rovibroic)

Rotaional Energy

Vibrational Energy

Boltzmann Disstribution

Partition Functions

 
 
𝜈  4=6 7 4 𝑐 𝑚 −1 𝜈  13 =1486 𝑐 𝑚 − 1

𝜈  12 =3063 𝑐 𝑚 −1 𝜈  14 =1038 𝑐 𝑚 − 1
𝜈  4=674 𝑐 𝑚 − 1 𝜈  13 =1486 𝑐 𝑚 − 1

𝜈  12 =3063 𝑐 𝑚 −1 𝜈  14 =1038 𝑐 𝑚 − 1
 Peak distribution Peak distribution
T= 298 K T= 1000 K
Vibration Mode J=32; K=+32 ,-32 J=60; K=+60 ,-60

0.001000 0.000962
0.000005 0.000326
0.000278 0.001074
0.000810 0.001473
Linestrength Calculations:
• 
• ; ;
• was obtained from at 295 K and 674 cm-1
ML model for monitoring Acetylene Aromatization

• Important catalytic reaction in astrochemistry

• Mechanistic study requires monitoring benzene and acetylene
concentrations.
• Generate data for X=0-5000 ppm
• Normalize the dataset
• 80% of data is fed to the Regression Learner app where 25% of
these data are to be used for cross validation
• Use Regression Trees coupled with PCA
ML model performance
Benzene Acetylene
Thank You!
REFERENCES:

[1] W. Chen, F. Cazier, F. Tittel, and D. Boucher, \Measurements of benzene concentration by

dierence-frequency laser absorption spectroscopy," Applied optics, vol. 39, no. 33, pp.
6238{6242, 2000.
[2] Pnnl spectroscopic database.
[3] T. Shimanouchi et al., Tables of molecular vibrational frequencies. US Government Printing
Oce, 1973.
[4] G. Herzberg, Molecular spectra and molecular structure. D. van Nostrand, 1945.
[5] W. H. Organization et al., \Who guidelines for indoor air quality: selected pollutants," 2010.
[6] M. Mhanna, G. Zhang, N. Kunnummal, and A. Farooq, \Cavity-enhanced measurements of
benzene for environmental monitoring," IEEE Sensors Journal, 2020.
[7] C. P. Weisel, \Benzene exposure: an overview of monitoring methods and their ndings,"
Chemico-biological interactions, vol. 184, no. 1-2, pp. 58{66, 2010.
[8] S. M. Arnold, J. Angerer, P. J. Boogaard, M. F. Hughes, R. B. O'Lone, S. H. Robison, and A.
Robert Schnatter, \The use of biomonitoring data in exposure and human health risk assessment:
benzene case study," Critical reviews in toxicology, vol. 43, no. 2, pp. 119{153, 2013.
[9] N. E. Hester and R. A. Meyer, \A sensitive technique for measurement of benzene and
alkylbenzenes in air," Environmental Science & Technology, vol. 13, no. 1, pp. 107{109, 1979.
[10] O. Raaschou-Nielsen, O. Hertel, E. Vignati, R. Berkowicz, S. S. Jensen, V. B. Larsen, C.
Lohse, and J. H. OLSEN, \An air pollution model for use in epidemiological studies: evaluation
with measured levels of nitrogen dioxide and benzene," Journal of Exposure Science &
Environmental Epidemiology, vol. 10, no. 1, pp. 4{14, 2000.
[11] S. Krol, B. Zabiega la, and J. Namiesnik, \Measurement of benzene concentration in urban
air using passive sampling," Analytical and bioanalytical chemistry, vol. 403, no. 4, pp.
1067{1082, 2012.
[12] A. Sekar, G. K. Varghese, and M. R. Varma, \Analysis of benzene air quality standards,
monitoring methods and concentrations in indoor and outdoor environment," Heliyon, vol. 5, no.
11, p. e02918, 2019.
[13] M. Karlowatz, M. Kraft, and B. Mizaiko, \Simultaneous quantitative determination of
benzene, toluene, and xylenes in water using mid-infrared evanescent
eld spectroscopy," Analytical Chemistry, vol. 76, no. 9, pp. 2643{2648, 2004.
[14] M. Mhanna, G. Zhang, N. Kunnummal, and A. Farooq, \Cavity-enhanced measurements of
benzene for environmental monitoring," IEEE Sensors Journal, 2020.
[15] R. Sur, Y. Ding, R. Jackson, and R. Hanson, \Tunable laser-based detection of benzene using
spectrally narrow absorption features," Applied Physics B, vol. 125, no. 11, p. 195, 2019.
[16] https://spectraplot.com/absorption.
[17] N. C. Handy and A. Willetts, \Anharmonic constants for benzene," Spectrochimica Acta Part
A: Molecular and Biomolecular Spectroscopy, vol. 53, no. 8, pp. 1169{1177, 1997}.
[18] R. K. Hanson, R. M. Spearrin, and C. S. Goldenstein, Spectroscopy and optical diagnostics
for gases. Springer, 2016.
[19] W. Jarzba, V. V. Matylitsky, A. Weichert, and C. Riehn, \Rotational coherence spectroscopy
of benzene by femtosecond degenerate four-wave mixing," Physical Chemistry Chemical
Physics, vol. 4, no. 3, pp. 451{454, 2002.
[20] M. Oldani and A. Bauder, \Pure rotational spectrum of benzene-d1," Chemical physics
letters, vol. 108, no. 1, pp. 7{10, 1984.
[21] C. H. Kruger and W. Vincenti, \Introduction to physical gas dynamics," John Wlley & Sons,
1965.
[22]https://www.ionscience.com/products/tiger-select-portable-benzene-gas-detector/#technical
specication. (pnnl spectroscopic database).
[23] Q. Li, B. Liu, P. Sarre, and A. S. Cheung, \Laboratory astrochemistry: catalytic reactions of
organic molecules over olivine-type silicates and sic," Proceedings of the International
Astronomical Union, vol. 13, no. S332, pp. 320{325, 2017.