Laser Raman Spectrometer for Process Control

Arieh M. Karger; Richard P. English; Ray J. D. Smith

doi:10.1364/AO.12.002083

Applied Optics
Vol. 12,
Issue 9,
pp. 2083-2087
(1973)
•https://doi.org/10.1364/AO.12.002083

Laser Raman Spectrometer for Process Control

Arieh M. Karger, Richard P. English, and Ray J. D. Smith

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Arieh M. Karger, Richard P. English, and Ray J. D. Smith, "Laser Raman Spectrometer for Process Control," Appl. Opt. 12, 2083-2087 (1973)

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Abstract

An interference filter laser Raman spectrometer has been assembled and tested. Sensitivity and linearity of response have been demonstrated for a number of gases, volatile liquids, and mixtures thereof. It has been demonstrated that the bread-board device will function with less than 1 W of laser power, with a consequent tradeoff in sensitivity. It is felt that this device has demonstrated the principles required for implementation of the design and construction of a prototype process control instrument.

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Constituent	Wavelength λ_R	Bandwidth		Transmittance	Cross section¹σ (cm²/Sr)

		1/2	0.01%
H₂	6545 Å	30 Å	300 Å	55%	13.74 × 10⁻³¹
H₂O	6335	30	300	53	11.45
HCO₂H	6064	7	60	13
CH₃OH	6028	7	62	42
N₂	5846	30	300	50	4.58
HCHO	5652	11	90	47
O₂	5593	11	90	49	5.49
CO₂	5541	11	90	32	5.59

Species	Sensitivity	MDP (1 W)
H₂O	20.4 × 10⁻¹²A/Torr	2.1 Torr
H₂	19.2 × 10⁻¹²	6.2
N₂	7.66 × 10⁻¹²	5.5
CH₃OH	5.45 × 10⁻¹²	5.7
HCO₂H	4.9 × 10⁻¹²	0.8
O₂	4.8 × 10⁻¹²	3.2
CO₂	3.12 × 10⁻¹²	4.2

Species	S_max (amperes)	N_max (amperes)	(S/N)_max	S_min (amperes)	N_min (amperes)	(S/N)_min
H₂O	3.6 × 10⁻¹⁰	4.4 × 10⁻⁹	0.82	1.6 × 10⁻¹⁰	4.4 × 10⁻⁹	0.36
H₂	1.52 × 10⁻⁸	1.44 × 10⁻⁹	10.5	2.15 × 10⁻⁹	0.96 × 10⁻⁹	2.24
N₂	5.88 × 10⁻⁹	5.2 × 10⁻¹⁰	11.3	8 × 10⁻¹⁰	2.8 × 10⁻¹¹	2.85
CH₃OH	3.32 × 10⁻¹⁰	0.44 × 10⁻¹⁰	7.5	5.7 × 10⁻¹¹	3.24 × 10⁻¹¹	1.76
HCO₂H	1.28 × 10⁻¹⁰	2.64 × 10⁻¹¹	4.85	1.9 × 10⁻¹¹	2.4 × 10⁻¹¹	0.79
O₂	3.67 × 10⁻⁹	4 × 10⁻¹⁰	9.2	4.8 × 10⁻¹⁰	1.56 × 10⁻¹⁰	3.08
CO₂	2.42 × 10⁻⁹	3.48 × 10⁻¹⁰	6.95	3.19 × 10⁻¹⁰	1.56 × 10⁻¹⁰	2.04

Power	S_max (amperes)	N_max (amperes)	(S/N)_max	S_min (amperes)	N_min (amperes)	(S/N)_min
1 W	2.16 × 10⁻⁹	3 × 10⁻¹⁰	7.2	7.56 × 10⁻¹⁰	1.8 × 10⁻¹⁰	4.2
0.5	1.13 × 10⁻⁹	2.28 × 10⁻¹⁰	4.9	3.06 × 10⁻¹⁰	1.32 × 10⁻¹⁰	2.3
0.2	4.44 × 10⁻¹⁰	4.4 × 10⁻¹¹	10	1.20 × 10⁻¹⁰	2.8 × 10⁻¹¹	4.3
0.06	1.26 × 10⁻¹⁰	2.4 × 10⁻¹¹	10	1.20 × 10⁻¹⁰	2.8 × 10⁻¹¹	4.3

Laser power:	1 W (unless otherwise indicated)
Photomultiplier tube voltage:	−2250 V
Photomultiplier temperature:	−20°C
Scattering cell temperature:	+55°C
Photomultiplier tube dark current:	~2 × 10⁻¹¹ A
Pressure measurements:
$\begin{array}{l} H_{2}, N_{2}, {CO}_{2}, O_{2} & \pm 2 Torr & (1000 Torr full scale) \\ {CH}_{3} OH & \pm 0.2 Torr & (100 Torr full scale) \\ H_{2} O, {HCO}_{2} H & \pm 0.06 Torr & (30 Torr full scale) \end{array}} \sim 1 %$
Signal recording accuracy:	±0.5%
Electrometer accuracy:	±0.5%
Observed laser stability:	±1%
Overall error (rms):	${({0.5}^{2} + {0.5}^{2} + 1 + 1 + 1)}^{\frac{1}{2}} = \sqrt 3.5 = 1.87 %$

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Applied Optics