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AIAA 2015-1156

AIAA SciTech
5-9 January 2015, Kissimmee, Florida
53rd AIAA Aerospace Sciences Meeting

Methane Absorbance Measurements at


Pressure/Temperature Conditions Associated With
Hypersonic Flight

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Daanish Maqbool1 and Christopher Cadou2


University of Maryland, College Park, MD, 20742

A facility constructed for simulating high pressure and temperature fuel flows in
endothermic cooling channels for hypersonic air-breathing engine components has been
used to investigate methane absorption at elevated temperature and pressure. Absorption by
two rovibrational lines around 1654 was measured at pressures ranging from 1 to 15 atm
and at 300 and 700K. The results show that measured integrated absorbance differs
substantially from HITRAN predictions and can lead to errors of more than 40% in
predicted concentration. This is probably because HITRAN relies almost entirely on
spectroscopic data acquired at atmospheric temperature and pressure but more detailed
investigations are required to confirm these findings and to better quantify the discrepancy.

Nomenclature
C
D
E

H
I
k
L
P
Pe
Re

Sc
T
u

=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=

concentration
diffusion coefficient
error
molar absorptivity
height of channel
Intensity
absorption coefficient
length scale
pressure
Peclet number
Reynolds number
density
Schmidt number
temperature/transmittance
velocity
viscosity
optical frequency/wavenumber
length

I. Introduction

ne thermal protection strategy being considered for hypersonic engines is active cooling of internal engine
components by endothermically decomposing fuel in millimeter-scale passages machined into the
components1. An important additional benefit of this approach is that the decomposition products typically have
lower ignition delay and reaction times making it easier to complete combustion in the high speed engine
environment2. However, the thermodynamics of the gas-phase cracking process favors soot-producing pathways that
would quickly clog the small cooling passages2,3 and cause a catastrophic loss of cooling performance. An
interdisciplinary team of researchers from the University of Virginia, North Carolina State University, and the
1

Research Assistant, Department of Aerospace Engineering, Univ. of Maryland, College Park, MD 20742
Associate Professor, Department of Aerospace Engineering, Univ. of Maryland, College Park, MD 20742,
Associate Fellow of AIAA
1
American Institute of Aeronautics and Astronautics

Copyright 2015 by Daanish Maqbool and Christopher Cadou. Published by the American Institute of Aeronautics and Astronautics, Inc., with permission.

II. Experiment Design


A. Determination of representative hypersonic conditions
Calculations were performed to identify fuel injector conditions that are representative of flight between Mach 3 and
7 at altitudes between 30,000 and 100,000 feet. Atmospheric conditions as a function of altitude are determined
using the International Standard Atmosphere (ISA). Static pressure and temperature of the air entering the
combustor are plotted in Fig. 1 (log scale) for incoming Mach numbers of 0.3 and Mach 1.5. The dashed lines show
the boundary beyond which dodecane (i.e. the fuel surrogate of interest here) is supercritical. The green box shows
the region accessible in the experimental facility.

Mach 7 at
30,000 ft

10

Supercritical

Mcombustor

10

= 0.3

Experiment Test Conditions


Pressure (atm)

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University of Maryland is pursuing a solution to this problem where mixed metal acid catalysts are used to promote
non-soot producing endothermic decomposition pathways. Part of this effort involves making non-intrusive
measurements of fuel and decomposition product concentration profiles along the length of cooling micro-channels
at temperatures and pressures that are representative of injection conditions in hypersonic engines (up to 50 atm and
1100 K). Chemical kinetic analyses indicate that knowledge of the concentrations of stable species like CH4, C2H2,
C2H4, and C2H6, and radical species like CH3 and C3H3 will be especially important for understanding the
decomposition process. However, making non-intrusive measurements of these species is challenging not only
because of the small size of the cooling passages but because of the lack of spectroscopic data at the appropriate
temperatures and pressures.
This paper describes the development of a facility for investigating the endothermic decomposition of liquid
hydrocarbon fuel surrogates like dodecane (C12H26) in micro-channels and its first use to acquire some of the basic
absorption data needed to make non-intrusive measurements of species concentrations in microchannels at
conditions that are representative of the hypersonic environment. The focus of the latter effort is on measuring
absorption line strength of the R(3) line in the 23 manifold of methane (~1654 nm) at high temperature and
pressure. This line was selected not only for its relevance to the endothermic decomposition problem but also for its
usefulness in the development of non-intrusive equivalence ratio sensors for gas turbine combustors that are accurate
at realistic combustor temperatures and pressures.

Mach 7 at
100,000 ft
Super-critical

10

Mach 3 at
30,000 ft
Mcombustor

10

-1

10

= 1.5
Mach 3 at
100,000 ft
3

10
Temperature (K)

Fig. 1: Representative hypersonic combustor inlet conditions.


2
American Institute of Aeronautics and Astronautics

B. Determination of flow rates


Fig. 2 is a schematic illustration of the lower half of the flow in the simulated cooling channel. A fuel surrogate
in this case dodecane heavily diluted with N2 to avoid coking upstream enters from the left. The wall supported
catalyst initiates decomposition to lighter species (H2, CH4, etc.) that diffuse off the surface back into the flow. The
channel has a 4 mm x 4 mm square cross-section and is 152 mm (6 inches) long. These dimensions were selected to
be consistent with what one might find in a practical endothermic cooling application and to be consistent with
similar experiments being carried out at other laboratories. The objective is to make non-intrusive measurements of
chemical composition at different axial locations in order to observe the streamwise evolution of the decomposition
process. However, it is important that the experiments span the full range of conditions that could be encountered in
the real flow.
Interrogation
Beam
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C-L

Tfuel
Dodecane

H2, CH4, C2H4, C6H6,


etc. diffusing upward

C12H26 diffusing
downward

Species Boundary
Layer

Catalytic Surface

Wall

Twall

Fig. 2: Diffusive transport in the microchannel.


The Peclet number is a convenient parameter for describing mass transport in this flow. It is defined as follows

Pem = Re Sc =

uL uH

=
D D

(Eq. 1)

where H is the cross-sectional dimension of the passage, u is the convective velocity, and D is the diffusion
coefficient of the particular species of interest. When the Peclet number is large, the time required for a molecule to
diffuse from the core flow to the wall is much larger than the time required for the molecule to be convected
downstream and the decomposition rate is said to be transport limited. Conversely, when the Peclet number is small,
the time required to diffuse to the wall is much smaller than the time to be convected downstream and the
decomposition rate is determined by the activity of the catalyst and is said to be rate limited. Since the channel
dimensions (H) and the diffusion coefficient (D) are fixed parameters of the experiment, exploring the full range of
operating conditions from transport limited to rate limited is achieved by varying the flow velocity (u).
It should be noted that determining the diffusion coefficient upon which these calculations are based is not
necessarily trivial for the supercritical conditions expected in the experiment. One could use numerical tools that
rely on molecular dynamics4 (such as CANTERA5) or empirical correlations (such as the Wilke-Change6, StokesEinstein7, or He-Yu7) to calculate the diffusion coefficients of the various species into N2. Unfortunately, however,
these methods give results that vary by over two orders of magnitude. This is mainly because the correlations have
been developed for specific industrial processes that are not relevant here and because CANTERA uses gas
dynamics models which are strictly valid only in the gaseous phase. In order to avoid getting bogged down in a
different problem, the approach taken here is to compute all diffusion coefficients using CANTERA in order to
ensure some measure of consistency. The results of these calculations for the diffusion of several important species
into N2 are tabulated in Table 1. These diffusion coefficients are averaged (4.85e-6 m2/sec) for the purpose of
determining the general range of u.

3
American Institute of Aeronautics and Astronautics

Table 1: CANTERA results for diffusion into N2.

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Solute (diffusion into N2) D (m2/sec.) CANTERA


Hydrogen (H2)

1.39e-5

Methane (CH4)

4.22e-6

Ethylene (C2H4)

3.20e-6

Benzene (C6H6)

1.82e-6

Dodecane (nC12H26)

1.11e-6

The range of Peclet numbers of interest here is 0.1 to 100 and is chosen to span the range from rate-limited to
transport-limited performance. Under these conditions, the corresponding flow velocities (using Eq. 1) will range
between 0.000121 and 0.121 m/s. Assuming a 90% dilution (by volume) with N2, and given the state of the N2-fuel
mix (from CANTERA), the required mass flow rate of the fuel is between 4.33e-8 kg/sec (43.4 ug/sec) to 4.33e-5
kg/sec (43.3 mg/sec). Given the available fuel metering pump (an Eldex Laboratories Model 1LMP metering pump
that can meter between 0.002 and 2.5 mL/min. at up to 6000 psi), Peclet numbers as low as 1 should be attainable.
C. Overall Design
Fig. 3 is a sketch of the experiment layout. The test section is a rectangular channel with two sides (top and
bottom) serving as the catalyst surface, and the other two sides formed by Zinc-Selenide windows for optical access
in the IR-region. It is housed in a pressure vessel equipped with optical ports and a 3-zone tube furnace (Fig. 4). The
vessel can be pressurized up to 50 atm with Nitrogen in order to ensure that the fuel inside cannot oxidize in case the
test section leaks or breaks. The internal dimensions of the pressure vessel are 0.254 m (10 inches) in diameter and
0.6096 m (24 inches) in length.
Nitrogen from the high pressure environment enters the test section via a 1.82 m (6 foot) long tube coiled inside
the furnace as shown in Fig. 5. This ensures that the Nitrogen enters the test section at the furnace temperature. A
thermocouple monitors the temperature of the N2-fuel mix before it enters the test section. The flow rate of the
Nitrogen is controlled by a choked flow orifice downstream of the test section and the fuel flow rate is set
independently by the metering pump.
The flow is probed optically at various downstream locations through the 6 inch long ZnSe windows using a
Thermo-Nicolet Nexus 870 FT-IR spectrometer with a Thorlabs BF20LSMA optic fiber. Unreacted fuel leaving the
test section is condensed out in an external shell-and-tube heat exchanger before the gas stream is exhausted to the
atmosphere.

4
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Pressure
Controller
Independently
Set Temperature

Independently
Set System
Pressure

N2

Pressure
Chamber
High
Pressure
N2

Tube Furnace (up to 1100 K)


N2

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Test Section

Do not want to
release vaporized
fuel at 800 C and
50 atm into air

Fuel
Shell and Tube
heat exchanger
condenses
reaction products
for safe ejection

Water

Measure P, T
N2
Choked
Orifice Flow
Meter

Pump
Independently
Set Fuel Flow
Rate

Condensed
Fuel

Fig. 3: Experiment Layout.

Fig. 4: Pressure vessel with tube furnace inside.


5
American Institute of Aeronautics and Astronautics

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Fig. 5: Test section with heating coil for N2.

III. Spectroscopic Measurements


A. Absorption Spectroscopy
Absorption spectroscopy is a well-established technique for making non-intrusive measurements of species
concentration. The Beer-Lambert law8,9 describes the relationship between optical absorption and absorbing-species
concentration:

dI ( )
= k ( )Cdx
I 0 ( )

(Eq. 2)

In this expression, I0 is the initial light intensity, dI is the measured change in transmitted intensity, is the optical
frequency (typically in cm-1), C is the concentration in moles/m3, dx is the differential path length, and k is a
coefficient that accounts for the variation of absorption with wavelength. Note that k may also depend on
temperature and pressure. Integrating over the optical path length L and converting natural logarithms to base 10
gives:

log 10

dI ( )
= A( ) = ( )CL
I 0 ( )

where A is the absorbance and is the molar absorptivity,

(Eq. 3)

The wavelength-integrated absorbance (

A = ( )CLd = CL ) is the sum of the absorbance over a particular absorption feature or the entire
absorbing rovibrational band. In cases where the molar absorptivity is not known directly, concentration can be
inferred from a calibration:

Csample =

Asample Lcalibration
Ccalibration.
Acalibration Lsample

(Eq. 4)

B. Selection of Absorption Lines


This experiment will use absorption spectroscopy to infer concentrations of species of interest at different axial
locations in a test section. As explained in the previous section, at a given temperature and pressure, and for a given
geometry (i.e. path length), absorbance (or transmittance) is just a function of the concentration. A higher
absorbance implies a higher concentration and vice versa. Absorption lines to probe must be selected for each
species of interest. These lines should be as strong as possible (to facilitate detection) and should be free of
interference from absorption by other species in the experiment. Table 2 shows the main species involved in
dodecane cracking. Spectroscopic data for four of these species are available in HITRAN12 and their respective
linestrengths are plotted in Fig. 6. The figure shows that interference-free lines for CH4 can be sought in the region
6
American Institute of Aeronautics and Astronautics

2700-2900 cm-1, for C2H2 in the region 6400-6700 cm-1, for C2H4 in the region 900-1100 cm-1, and for C2H6 in the
narrow region 800-820 cm-1.

-20

CH4

10

1000

2000

3000

4000

5000

6000

7000

8000

Linestrength (cm-1/mol cm-2)

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-20

9000

10000

C2H2

10

1000

2000

3000

4000

5000

6000

7000

8000

-20

9000

10000

C2H4

10

1000

2000

3000

4000

5000

6000

7000

8000

-20

9000

10000

C2H6

10

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

Wavenumber (cm-1)

Fig. 6: Linestrengths for species of interest (from HITRAN12/SpectralCalc29). Minimum intensity (Icut) is 1e-23
cm-1/(mol-cm-2).

C. Motivation for Methane and Spectroscopic Challenges


The chemical species of interest in dodecane cracking are listed in Table 2 along with references to spectroscopic
data for these molecules taken from the HITRAN 2012 database13. The table shows that most of the data available
for these species has been acquired at temperatures and pressures that are much lower than those of interest in this
work. Other databases (GEISA, JPL Mol. Spec., etc.) are, to the authors knowledge, also intended for lowtemperature studies. This could pose a problem for the use of non-intrusive measurement techniques if the
spectroscopic parameters of these molecules (line positions, line strengths, pressure broadening coefficients, etc.) are
substantially different at the elevated pressures and temperatures of interest here. So, the first step of this research
endeavor is to establish the degree to which the spectral parameters of the various molecules of interest vary with
temperature and pressure.
Table 2: Species of interest in dodecane cracking.
Species
Spectral Data
T (K)
P(atm)
Reference
CH4
<= 296
<=1
11-13
C2H2
< 299
<= 25
13, 14
C2H4
<= 300
<= 1
15, 16
C2H6
< 299
<=1
17, 18
CH3
Not available in HITRAN13
C3H3
Not available in HITRAN13
It was decided to begin with methane since it is a common, well-studied molecule that has many absorption
bands in the mid-infrared that may be probed using our FT-IR spectrometer. Since the field appears to be wide
open, we will focus initially on the R(3) line in the 23 manifold of methane (~1654 nm) because it is relatively free
from interferences with air 19,20, is well separated (according to HITRAN calculations) from other methane lines at
7
American Institute of Aeronautics and Astronautics

high pressures and temperatures, and is accessible through the inexpensive borosilicate glass windows of the
pressure vessel.
Table 3: Previous spectroscopic investigations of methane.

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Author

Frankenberg
Gharavi et. al.
Darnton and Margolis
Nagali et. al
Margolis
Margolis
Li et. al
Lackner
Niederer

Year

2008
2005
1973
1996
1988
1990
2011
2003
2011

Wavelenngth
Max
Min
(nm)
(nm)
1670.84 1616.81
1650.98 1653.99
1662.33 1659.41
1645.57 1645.53
1818.18 1618.12
1818.18 1618.12
1653.73 1653.73
1687.42 1683.90
11111.11 833.33

Temperature
Max
Min
(K)
(K)
296.15
295.65
908
296
300
100
295
292
296.2
295.6
220
180
578
297
296
296
80
80

Pressure
Max
Min
(atm)
(atm)
0.123
0.888
0.021
0.003
1.711
0.658
0.017
0.004
0.059
0.002
0.026
1.000
1.000
0.010
1.283
0.007

Ref

21
22
23
24
25
26
20
27
28

D. Experiment Setup
Fig. 7 shows the experiment setup for making the measurements described in the previous section. White light
from a Thermo-Nicolet Nexus 870 FT-IR is channeled into a Thorlabs BF20LSMA optic fiber using a customassembled fiber coupler using Thorlabs cage-and-tube kit components. The light exits the fiber into a Thorlabs
RC04SMA-P01 reflective collimator. The 0.66 mm (0.26 in.) diameter collimated beam passes through the pressure
vessel and furnace (which host the gas mixture to be probed) via two 0.0127 m (0.5 inch) thick Borosilicate
windows. An MCT/A* detector on the other side of the vessel receives the beam and interfaces with the
spectrometer. The resolution of the spectrometer is 0.5 cm-1 and the spectra represent the average of 600 scans.
It was determined that 600 scans were adequate to resolve the main features of interest by computing the change
in mean transmittance with the number of scans which should be set high enough that the mean transmittance is


independent of the number of scans. The mean transmittance () is defined as  =
 
, where T is the
 

transmittance ( =   ) at a given wavenumber (), and 1 and 2 are the lower and upper limits of the wavenumber
range of interest. For the test case at 700 K and 15 atm,  averaging 100 scans gives  =93.0929, 350 scans gives
 = 92.9397, and 600 scans gives  =92.9326. While  is not an indication of the level of random noise in the
signal (because the random noise component should integrate to zero), the convergence in values indicates that 600
scans is at least sufficient to resolve physical features. Of course, higher numbers of scans are still desirable to
reduce noise, especially given the challenge of obtaining good Signal-to-Noise Ratio (SNR) in this apparatus, but
600 scans appears to represent a good compromise between accuracy and measurement time.

8
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MCTA*
Detector

Test Vessel

Collimator

Spectroscope

Fiber
Coupler

Optic
Fiber

Borosilicate
Windows

Fig. 7: Top View of Spectroscopic Measurement Setup.

IV. Results
The upper sections of each plot in Fig 8 show percent transmittance of 6% mixtures of methane (CH4) in
nitrogen (N2) around 1654 nm at temperatures of 300 K and 700 K and at several pressures between 1 and 15 atm.
The lower section of each plot shows error computed by taking the difference between the measured transmittance
and that predicted using SpectralCalc29 and the HITRAN database12. Fig. 9 shows corresponding absorbance at each
condition. The residual is the difference between the measured and predicted values normalized by the maximum
measured absorbance of each peak. Thus, the absorbance used for normalization in the left half of the plots
corresponds to the peak at ~6057 cm-1 and the value used for normalization in the right half of the plot corresponds
to the peak ~6057 cm-1.
The results illustrate the competing effects of pressure and temperature. Generally speaking, raising the
temperature decreases absorbance, because it lowers the density and thus the total number of light-molecule
interactions. Conversely, raising the pressure increases the density resulting in more interactions and higher
absorbance. Pressure broadening is also apparent in all cases but is not strong enough to render individual peaks
indistinguishable for these lines under these conditions.
It is also apparent from Figs. 8 and 9 that there are differences between the measured and HITRAN-predicted
spectra that seem to increase with temperature. The importance of these differences for making non-intrusive
measurements of concentration is determined by computing the error in predicted concentration. The error is
defined as:
 
 = 100   
(Eq. 5)


where CH and CM are the concentrations computed using Eqn. 4 and the Hitran (H) and measured (M) absorbance
spectra. Since all measurements and HITRAN simulations have been performed at one path length and one
concentration, Eq. 5 reduces to:
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American Institute of Aeronautics and Astronautics

 = 100  




1

(Eq. 6)

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Fig. 10 shows percent error in predicted concentration as a function of pressure at two temperatures: 300K and
700K. To obtain respective  values, the absorbance was integrated between 6046 cm-1 and 6048 cm-1 for the peak
at ~6047 cm-1, and between 6056 cm-1 and 6058 cm-1 for the peak at ~6057 cm-1. While error is relatively modest at
300K (a few percent which probably of the order of the uncertainty in the measurement although this has not been
calculated yet) and remains so at pressures up to about 5 atm, it grows substantially beyond this point and errors in
predicted concentration of 30-40% are observed when using either line. The results are even worse at 700K where
the error at 5 atm is already ~30-40%. However, the high temperature results in particular expose an important
problem with the experiment which is generally low absorbance (and thus SNR) throughout. The problem was so
severe at 700K and 1 atm that the absorption features of interest disappeared and hence no comparisons between
HITRAN and experiment were possible.

V. Conclusions and Future Work


A facility has been constructed for simulating the high pressure and temperature fuel flows encountered in
miniature channels used for cooling hypersonic air-breathing engine components via endothermic fuel
decomposition. Before the facility may be used to measure chemical composition as a function of downstream
distance in the optically accessible cooling channels, it is necessary to establish the efficacy of the non-intrusive
absorption-based technique used to measure chemical composition. To this end, the absorption by two rovibrational
transitions of methane around 1654nm has been explored at two temperatures (300K and 700K) over pressures
ranging from 1 to 15 atm. These lines were selected for their additional usefulness in the development of nonintrusive equivalence ratio sensors for gas turbines19,20. The results show that measured integrated absorbance differs
substantially from that predicted by HITRAN and can lead to substantial errors of more than 40% in predicted
concentration. This is probably because HITRAN relies almost entirely on spectroscopic data acquired at
atmospheric temperature and pressure but a more detailed investigation is required to confirm these findings and to
better quantify the discrepancy. In particular, uncertainty levels associated with each data point in Fig. 10 need to be
determined, the range of conditions needs to be expanded (experiments 50 atm and 1100K are planned), experiments
at concentrations other than 6% need to be performed, and the SNR of the measurement system needs to be
improved. Once these steps have been taken, we will move on to C2H2, C2H4, C2H6, and other molecules relevant to
dodecane cracking.

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300 K

700 K
120

% Transmission

% Transmission

1 atm

120
100
80
60
40
20

Error

Error
6045

6050

6055
-1

% Transmission

80
60
40
20

0
6045

6050

6055
-1

80
60
40
20

0
6045

6050

6055
-1

6060

0
-10
6040

6045

6050

6055
-1

6060

6045

6050

6055
-1

6060

6045

6050

6055
-1

6060

6045

6050

6055
-1
)

6060

100
80
60
40
20

0
-10
6040

100
80
60
40
20

100
80
60
40

Error

20

6045

6050
-1

Wavenumber (cm

6055
-1
)

0
-10
6040

120

% Transmission

120

% Transmission

HITRAN (SPECTRA)

0
10

Error

Error

0
10

Error

Experiment

20

120

% Transmission

% Transmission

6060

100

0
15
10
5
0
-5
6040

40

0
10

0
10

-10
6040

60

120

100

120

10 atm

6060

Error

% Transmission
Error

5 atm

120

15 atm

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-10
6040

80

0
10

0
10

-10
6040

100

6060

100
80
60
40
20
0
0
-5
-10
-15
6040

-1

Wavenumber (cm

Fig. 8: Spectroscopic Measurements of Methane (Transmittance).


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700 K

0.2
0.1
0

6045

6050

6055
-1

6060

0.3
0.2
0.1
0
20
0
-20
6040

6045

6050

6055
-1

6060

Absorbance

0.4
0.3
0.2
0.1
0
20
10
0
-10
6040

6045

6050

6055
-1

6060

Absorbance

0.4
0.3
0.2
0.1
0
40
20
0
6040

Residual (%)

Absorbance

0.4

6045

6050
-1

Wavenumber (cm

6055
-1
)

6060

0.2
0.1
0
100
0

-100
6040

Residual (%)

40
20
0
-20
-40
6040

HITRAN (SPECTRA)

0.3

Residual (%)

0.3

Experiment

0.4

Absorbance

0.4

Residual (%)

Absorbance
Absorbance

Residual (%)

Absorbance

Residual (%)

Absorbance

Residual (%)

5 atm
10 atm
15 atm

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Residual (%)

1 atm

300 K

6045

6050

6055
-1

6060

6045

6050

6055
-1

6060

6045

6050

6055
-1

6060

6045

6050

6055
-1
)

6060

0.4
0.3
0.2
0.1
0
50
0
-50
6040

0.4
0.3
0.2
0.1
0
20
0
-20
-40
6040

0.4
0.3
0.2
0.1
0
0
-20
-40
6040

-1

Wavenumber (cm

Fig. 9: Spectroscopic Measurements of Methane (Absorbance).


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American Institute of Aeronautics and Astronautics

50
700 K

7
APercentError

40

30
Line 1 (~6047 cm -1)

20

300 K

-1

Line 2 (~6057 cm )

Downloaded by UNIVERSITY OF MARYLAND on August 8, 2015 | http://arc.aiaa.org | DOI: 10.2514/6.2015-1156

10

10

15

Pressure (atm)
Fig. 10: Percent error in predicted values of .

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