10th AIAA/ASME Joint Thermophysics and Heat Transfer Conference AIAA 2010-4520

28 June - 1 July 2010, Chicago, Illinois

AIAA 2010-4520 1

Nonequilibrium Chemistry and Radiation for Neptune Entry

Chul Park
Korea Advanced Institute of Science and Technology, Daejeon, Korea
A theoretical model to describe the thermochemical during the entry flights into outer planets. In Ref. [2], the
nonequilibrium and radiation phenomena in the shock model was applied to predict the radiative heat flux in an
layer over a spacecraft entering the planet Neptune is de- entry flight into the planet Neptune. Both [1] and [2] pre-
rived by assembling the existing information. This model dict a relatively slow equilibration. The nonequilibrium
is applied to predict the flow in a constant-area channel region was found to emit strong radiation: the radiative
behind a normal shock wave in a mixture representing heat flux produced in a nonequilibrium flow is typically
the atmosphere of the planet. Calculation is made for the three times that from an equilibrium flow.
aerobraking flights in Neptune considered in the past. It Refs. [1] and [2] and the present work are all moti-
is shown that presence of methane shortens the time for vated by the desire to carry out aerobraking maneuver
equilibration, produces a nonequilibrium radiation over- in Neptune. The maneuver is for the purpose of placing
shoot, and more than doubles the radiative heat flux. Ra- a spacecraft into an elliptic orbit around Neptune that
diative heat flux values are calculated over a range of den- passes the orbit of the satellite Triton. Because Triton
sities and velocities expected in an aerobraking flight in rotates in a retrograde direction, the entry flight must be
Neptune. also in a retrograde direction. Such a mission was pro-
posed by several previous investigators (see, e.g., [3] and
Nomenclature [4]). Neptune and Triton are interesting because they are
A : Reaction rate constant, Eq. (1), cm3 /s. the closest to the Kuiper Belt which may hold clues about
e : Energy feed back factor. formation of the solar system and the origin of life.
E : Energy level, eV. Refs. [1] and 2 ignore the presence of CH4 in Neptune.
k : Boltzmann constant, 1.3806×10−16 erg/K. CH4 will quickly decompose into C and H. C has a rela-
kf : Forward reaction rate coefficient, cm3 /s. tively low ionization potential, and therefore is likely to
n : Pre-exponential power in rate coefficient, dim- ionize first. This fast ionization may change the radiative
: ensionless, Eq. (1). heat flux falling onto the entry vehicle. The purpose of
N : Number density, cm−3 . the present work to explore such effects of CH4 .
p : Pressure, Pascal or Torr. Chemistry Model
qr : Radiative heat flux, kW/cm2 .
T : Heavy particle translational temperature, K. Reaction Kinetics of H2 -He Mixture
Ta : Effective temperature of reaction, K. Neptune’s atmosphere [5] is believed to consist of, by
Td : Reaction temperature, Eq. (1), K. mol, about 80 to 82% H2 , 17 to 18% He, and 1 to 2%
Tv : Vibrational-electron-electronic temperature, K. hydrocarbon, mostly CH4 . The present work assumes it
Us : Shock velocity, m/s or km/s. to be 81% H2 , 17.5% He, and 1.5 % CH4 . In [1], the
x : Distance from shock wave, cm. reaction kinetics of H2 -He mixtures was developed. The
µ : Equivalent mass, gram. main features of the H2 -He mixture are: 1) the collisions
ρ : Density, kg/m3 . of H and He on H produce electronic transition in H with
σc : Cross section for excitation of C by collision of a cross section of 10−17 cm2 ; 2) absorption of radiation
: H, cm2 . by the Lyman-α line affects the rate of ionization of H; 3)
collisions of electrons, H, and He produces eight rate co-
Subscripts efficients governing ionization of H; and 4) this model can
1 : Freestream. numerically reproduce the experimental data obtained in
shock tubes. This model is made a part of the present
Introduction model for H2 -He-CH4 mixtures. The chemical reaction
scheme in this gas mixture is summarized in Table 1.
In Ref. [1], a thermochemical model is developed to de- Therein, the quantities A, n, and Td are the three pa-
scribe the thermochemical relaxation and radiation phe- rameters in the expression for the forward reaction rate
nomena occurring in an H2 -He mixture. The work was coefficient
for the purpose of describing the phenomena occurring
kf = ATan exp(−Td /Ta ) cm3 /s. (1)
Visiting Professor, Department of Aerospace Engi-
∗ The quantity e is the energy feedback factor, i.e., the
neering; Fellow, AIAA; cpark216@kaist.ac.kr. amount of the energy fed back to vibrational-electron-

Copyright © 2010 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.
2 AIAA 2010-4520

electronic mode during a reaction, expressed as a frac- actions involving H will be much faster than thermal de-
tion of the reaction energy. Explanation of each reaction composition.
parameters is given below Vibrational and rotational relaxation in an H2 -He mix-
ture is investigated thoroughly in [10] and [11] and is sum-
Dissociation of CH4 marized in [1]. A two-temperature model can be used to
describe even though rotational mode is not in equilibrium
For decomposition of CH4 , only exchange reactions [6- with the translational mode. Vabration and rotation of
9] are considered. The flow undere consideration is dom- the carbon-bearing molecules is neglected.
inated by H. In such an environment, the exchange re-
Table 1. Reaction mechanisms and rate coefficients. A is in the units of cm3 /s.
No. Reaction A n Td e Remarks
R1 H2 + H2 → H + H + H2 -4.48 eV 2.967−7 -0.5165 52,530 0.73 Kim et al(2009)
R2 H2 + H → H + H + H - 4.48 eV 3.18−4 -1.0735 55,105 0.65 Kim et al (2009)
R3 H2 + He → H + H + He - 4.48 eV 9.272−4 -1.4773 55,105 0.63 Kim et al (2009)
R4 CH3 + H2 → CH4 + H - 0.00 eV 3−20 3 4,045 0 Sutherland et al(2001)
R5 CH3 + H → CH2 + H2 - 0.22 eV 1−10 0 7,600 0 Baulch et al(1994)
R6 CH2 + H → CH + H2 + 0.12 eV 1−11 0 900 0 NIST(2003)
R7 C + H2 → CH + H - 0.99 eV 6.6−10 0 11,700 0 Dean et al(1991)
R8 C + H → CH+ + e - 7.15 eV 1.26−21 2 90,300 0 Present work
R9 C+ + H2 → CH+ + H - 0.37 eV 6.86−10 -0.115 5086 0 Present work
R10 C+ + H → C + H+ - 2.34 eV 4.31−31 3.26 13,018 0 Present work
R11 H + M → H+ + e + M - 13.6 eV ∗ ∗ ∗ 0.8 Park (2010)
R12 C + e → C+ + e + e - 11.26 eV 1.63−8 0.330 98810 0.8 Dunn (1971)
∗ Not expressible as a simple function, see Park (2010).

Electron-Impact Ionization of C C(1 S) + H(1s) → CH+ (X) + e − 4.47 eV. (4c)

The electron-impact ionization rate of C is derived from
the work of Dunn [12]. The process of interest is (4a).
The reverse processes of (4a) to (4c) have been studied
C + H → CH+ + e experimentally by Mul et al [14] and Amity and Zajfman
The C- and H-atoms can form CH+ through the asso- [15]. Theoretical study was made by Takagi et al [16]. In
ciative ionization process Fig. 1, the measured total cross sections for dissociative
recombination of CH+ are shown and are compared with
C + H → CH+ + e − 7.15 eV. (2) the theories. To a rough measure, the cross section varies
inversely with electron energy.
No research work was done on this reaction. However, Amity and Zajfman [15] separately measured the
there are several research papers on its reverse process, branching ratios among the three processes, (4a) to (4c).
dissociative recombination, Their results show that the reverse process of (4a) oc-
curs when electron energy is greater than 0.9 eV, and
CH+ + e → C + H + 7.15 eV. (3) that its cross section is 1/4 of the measured total. Us-
ing this result, a cross section model is constructed in the
This associative ionization/dissociative recombination pro- present work. According to this model, the cross section
3
cess can occur because there is a repulsive C( P) + H(1s) is 0.323× 10−17 cm2 at 0.9 eV, and varies as inverse of elec-

state, named (1 Π)4σ [13], that meets the ground state tron energy. This model is shown in Fig. 1 by a dotted
X1 Σ+ of CH+ . In reality, there are three branches in line. By integrating over the Maxwellian velocity distri-
reaction (2): bution of electron energies, one obtains the reverse rate
coefficient for process (4a) shown in Fig. 2 by a solid line.
C( P) + H(1s) → CH (X) + e − 7.15 eV (4a)
3 + By invoking the principle of detailed balance, one can
deduce the rate coefficient for the associative ionization
C(1 D) + H(1s) → CH+ (X) + e − 5.89 eV (4b) process. The coefficient so deduced is fitted in the present
 AIAA 2010-4520 3

work by has been studied by several researchers both theoretically

and experimentally. There is general agreement among
kf = 1.26 × 10
21 T 2 exp(−90, 300/T ) cm3 /s.−
(5) their results. One small difficulty was spreading of the
energy in the beam of C+ produced in the laboratory.
In Fig. 2, the dissociative recombination rate coefficient Ervin [17] collated all those results, and theoretically ac-
implied by Eq. (5) is compared with the values deduced counted for the energy spreading. The rate coefficient
from Fig. 1. obtained by integrating the resulting cross sections over
the Maxwellian velocity distribution is shown in Fig. 3.
It is fitted in the present work by
= 6.9 × 10 10 T 0 115 exp(−5086/T ) cm3 /s.
-14
10
kf − − .
(7)

3
2
Cross section, cm

-15
10
2

Rate coefficient, cm /s
3
-16
10 +
CH + e -> C + H cross section -10
10
experiment, total, Mul et al (1981) 9
experiment, total, Amity & Zajfman (1996) 8
theory, total, Takagi et al (1981) + +
present fit 7 C +H2-->CH +H
Derived from Ervin (1984)
6 -10 -0.115
-17 6.9x10 T exp(-5086/T)
10
2 3 4 5 6 78 2 3 4 5 6 78 5
0.01 0.1 1
4
Electron energy, eV
Figure 1. Cross sections for dissociative
recombination CH+ + e → C + H.
2
3
0.0 0.5 1.0 1.5 2.0 2.5
10000/T

Figure 3. The rate coefficient for CH+ + H →

10
-8 C+ + H2 .
Deduced from associative ionization

C+ + H → C + H+
9
Rate coefficient, cm /s

8 -17 1.4
rate coef = 3.3x10 T exp(-82990/T)
3

Considerable amount of work has been done on the

6

cross section for the charge exchange reaction

5

3 From cross section data C+ + H → C + H+ − 2.34 eV. (8)

2
+ 3 Stancil et al [18] summarized these works. By integrat-
CH + e -> C( P) + H(1s)
ing their cross section values over the Maxwellian velocity
distribution, one obtains the rate coefficient shown in Fig.
-9 4. As indicated in Fig. 4, the calculated reaction rate co-
10
0.4 0.6 0.8 1.0 1.2 1.4 1.6x10
4
efficient is fitted in the present work by
= 4.31 × 10 31 T 3 26 exp(−13018/T ) cm3 /s.
Electron temperature, K
Figure 2. Rate coefficient for dissociative kf − .
(9)
recombination CH+ + e → C(3 P) + H(1s).
Electronic Excitation of C by Collisions of H
CH+ + H → C+ + H2 In Fig. 5, the interaction potentials[19] of CH are
The cross section for the reaction shown. As seen, levels cross at several places. Predis-
sociation is known to occur at such level-crossing points
CH+ + H → C+ + H2 − 0.37eV (6) (see, e.g., [20] and [21]). This implies that the collisions
4 AIAA 2010-4520

of C and H will lead to electronic transitions in C. This is significantly ionized (ionization level of 1% or more),
process will transfer the translational energy of the heavy and so the energy exchange between the heavy particle
particles to the vibrational-electron-electronic mode. translational mode and the vibrational-electron-electronic
mode occurs mostly by the elastic collisions between the
heavy particles and electrons. However, for slower entries
-15
10

where ionization level is lower, this process may be im-

portant. For this reason, this process is retained in the
present work. By designating the cross section for this
-16
10
+ +

transition by σ , the rate coefficient can be written as

C + H -> C + H
Stancil et al (1998)
Rate coefficient, cm /s

c
-31 3.26
3

4.3 x 10 T exp(-13018/T)

8kT exp(−∆E/kT ) cm3 /s

-17
10
kf =σ c
πµ
(11)

where µ is the equivalent mass for the C+H collision and

-18
10

∆E is the energy of the transition. The cross section σ c

is tentatively assumed to be 10 17 cm2 , the value found

−

for the excitation of H by the collisions of H and He [1].

-19
10

This is with the hope that future works will determine it

concretely.
By involving the detailed balance relationship, one ob-
-20
10
0.0 0.5 1.0 1.5 2.0 2.5
10,000/T tains the corresponding reverse (downward) transition
Figure 4. The rate coefficient for C+ + H → rate, k . By multiplying the net transition rate
r

C + H+ . Net transition rate = k N1 N

f H − k N2 N
r H

(where N1 and N2 are the number densities of the 3 P

and 1 D states of C and N is the number density of H),
H

by the reaction energy, one obtains the rate of energy

transfer from the heavy particle translational mode to the
vibrational-electron-electronic mode as
Energy transfer rate = 2.025 × 10 13 σρ N N
− c

C H

× 8kT exp(− ∆E )[1 − T exp(− ∆E + ∆E )] (12)

v

πµ kT T kT kT v

J/(kg − s).
Here, the number densities N and N are in cm 3 , and
C H
−

Figure 5. Interaction potentials of CH.
Of particular interest is the excitation of the first ex-
cited state of C:
C(3 P) + H(1s) → C(1 D) + H(1s) − 1.26 eV
because this will be the most prevalent process in excita-
tion of C. As will be shown later, the energy transfer by
this process has only a small effect in the environments ex-
pected in Neptune aerobraking. This is because the flow
density ρ is in kg/m3 .
Calculation Procedure
Calculation procedure is the same as in [1]. The flow
condition immediately behind a normal shock wave is de-
termined from the Rankine-Hugoniot relations assuming
a frozen flow across the shock. The post-shock flow is cal-
culated by integrating in distance. Viscous phenomena
are neglected. Within each integrating steps, the quasi-
steady state distribution of the electronic states of H is
(10) calculated accounting for the collisions by electrons, H,
and He, and thereby ionization rate coefficient. From the
flow solution so obtained, radiative transfer calculation is
performed. The radiative transfer calculation yields the
radiation escape factor for the Lyman-α line, the radiative
gain or loss of the vibrational-electron-electronic energy,
 AIAA 2010-4520 5

and the spectrally- and directionally-resolved intensity of

the radiation leaving the shock wave into the upstream
direction. Then the radiative transfer equation is solved
for the flow upstream of the shock wave to determine the
precursor behavior. The precursor calculation yields the
condition of the flow entering the shock wave. This flow-
radiation iteration is repeated up to 25 times to obtain a
converged solution.
Twelve chemical species, C, H, He, CH, H2 , CH2 , CH3 ,
CH4 , C+ , H+ , CH+ , and electron are considered in the
chemical set. Equilibrium states, necessary in calculat-
ing the reverse reaction rates from the forward rates,
are calculated through the Gibbs free energy minimizing
technique using the JANAF coefficients. However, the
coefficients for H and H+ are modified so that the cal-
culated equilibrium states would be nearly the same as
those calculated from partition functions in the tempera-
ture ranges of interest [22].
The wavelength range from 600 to 8000 A is repre-
sented by 39160 selected points. In calculating the lines of Figure 6. Comparison of calculated conditions
H, the Stark line shape is convoluted with the Doppler line between a 84.17%H2 -14.43%He-1.5%CH4 mixture
shape. The radiation mechanisms considered are: Lines and a 84.17%H2 -15.93%He mixture; p1 = 1 Torr,
of H, bound-free continua of H, free-free continuum of H, Us = 30 km/s. (a) Electron density.
B-X and C-X band systems of H2 , lines of C, bound-free 4
continua of C, and, for low entry speeds, A-X, B-X, and 2.0x10

C-X band systems of CH. Heavy particle

Calculation was made on personal computers. Up to translational
10 hours were expended to obtain a converged solution.
Most of this time was spent on computing radiation. 1.5
84%H2-16%He

Results
Temperatures, K

Livingston-Poon Experiment Case 1.0

84%H2-14.5%He-1.5%CH4
Vibrational-electron-electronic
In [1], the experimental data obtained by Livingston
and Poon [23] for a 84.17%H2 -15.93%He mixture flow
were analyzed in detail. In the present work, calculation is
Calculated temperatures
p1=1 Torr, Us=30 km/s
performed for a hypothetical flow in which the 15.93%He 0.5
84%H2-14.5%He-1.5%CH4
partial pressure is replaced by 14.43%He + 1.5%CH4 . In 84%H2-16%He
Figures 6(a) to (e), results are shown. Equilibrium

Fig. 6(a) shows that equilibration is considerably faster

with the addition of 1.5% CH4 . Electron density is lower 0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
with CH4 , understandably because dissociation of CH4
cools the mixture. Between the σ = 10 17 and zero cm2 ,
− Distance from shock wave, cm
c

only a negligibly small difference is seen. The nonequilib-
rium electron density value is appreciably larger than the
equilibrium value. This phenomenon was observed exper-
imentally by Livingston and Poon [23], and was discussed
thoroughly in [1].
In Fig. 6(b), two temperatures are shown. Temper-
atures equilibrate faster with CH4 here. Interestingly,
the plateau temperature for the flow with CH4 is slightly
higher than the equilibrium Rankine-Hugoniot value. The
cause for this behavior is difficult to ascertain at this time
because of the complexity of the problem.
Figure 6. (b) Temperatures.
In Fig. 6(c), species mol fractions are shown. One
notices here that C and C+ are the dominant carbon-
bearing species: CH4 is almost totally decomposed and is
ionized. Concentration of H2 is small but not negligible.
In Fig. 6(d), radiative heat fluxes in two directions are
shown and are compared with those for the flow without
CH4 . As seen, radiative heat flux is more than twice with
CH4 . The downstream-directed flux undergoes a peak at
about x = 0.25 cm. This represents a radiation overshoot.
This phenomenon is well known for air. Apparently, a
6 AIAA 2010-4520

similar phenomenon occurs for the mixture of H2 , He,

and CH4 .
C lines
4
0 10 H2(B-X,C-X)
10

Spectral intensity, W/(cm2-µm-sr)

H
-1
10 3
10 CH (A-X,
B-X,C-X)
Species mol fractions

+ +
H C
-2
10
2
Calculated species mol fractions 10
p1=1 Torr, Us=30 km/s
-3 84%H2-14.5%He-1.5%CH4
10 84%H2-16%He
Calculated spectrum at x=1.2 cm, p1=1 Torr, Us=30 km/s
C
+
10
1 84%H2-14,5%He-1.5%CH4, σc=10-17 cm2(2.41 kW/cm2)
2
-4 CH4 84%H2-16%He (1.02 kW/cm )
10
CH3 6 7 8 9 2 3 4 5 6 7 8
CH CH2 H2 1000
Wavelength, A

10
-5

0.0 0.2 0.4 0.6 0.8 1.0 1.2

Figure 6. (e) Spectral intensity.
Distance from shock wave, cm In Fig. 7, equilibration distance is compared between
Figure 6. (c) Species mol fractions. the present calculation and the experimental data of Liv-
ingston and Poon. As mentioned, the experimental data
is for a flow without CH4 , while the present model is for
4000
a flow with CH4 .
4

Calculated radiative heat fluxes Ionization equilibration distance, p1=1 Torr

3
p1=1 Torr, Us=30 km/s Experiment, Livingston & Poon (1976)
84%H2-16%He
3000 84%H2-14.5%He-1.5%CH4, σc=10-17 cm2
2

2 Present model, 84%H2-14.5%He-1.5%CH4

Radiative heat flux, W/cm

84%H2-16%He
Equilibration distance, cm

1
9
2000 8
Downstream-directed 7
6
5

4
1000 Upstream-directed 3

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
0.1
Distance from shock wave, cm
26 28 30 32 34 36 38 40
Figure 6. (d) Radiative heat fluxes. Shock speed, km/s

Figure 7. Comparison of ionization equilibration

In Fig. 6(e), spectral intensity is compared between distance between the experimental data without
the flows with and without CH4 . As seen, radiation in CH4 and calculation with CH4 .
the flow with CH4 is different from that without in that it
has stronger vacuum-ultra violet continuum and carbon As seen, the calculated values are considerably smaller
line radiation. CH radiation is too weak to be recognized than the experimental data. In [1], a good agreement was
for this case. The wavelength-integrated radiative heat seen between the measurement and the calculation. The
flux is more than twice with CH4 . difference seen in Fig. 6(e) is, therefore, due solely to the
 AIAA 2010-4520 7

presence of CH4 . This result underscores what was seen point in Hollis et al’s flight trajectory. As seen, C con-
already in Fig. 6(a): CH4 accelerates equilibration. tributes nearly 2/3 of the total radiation. This differs
from the findings by Hollis et al [3]: they found that the
Neptune Aerobraking contribution of C was small. Suspicion exists that, in
In Fig. 8, the radiative heat flux values are calcu- their
enough
calculation, the line calculations did not extend far
into the wings.
lated for the Neptune aerobraking vehicle considered by
Jits et al [4]. The calculated values are compared with 5
those in [1] where CH4 is not accounted for. The heat
flux values are for the stagnation point. The stagnation
Calculated radiative heatflux
2.8 cm behind shock in 1-D flow
streamline is assumed to be that of a constant-area one- 4
Hollis et al (2004) trajectory
2

dimensional flow of 1 cm length. The length of 1 cm Present model (164 kJ/cm )

Equilibrium (104 kJ/cm )
2

is thought to be the approximate thickness of the shock

2
Radiative heat flux, kW/cm
2
Hollis et al (2004) (46 kJ/cm )
layer over the aerobraking vehicle considered by Jits et
al. As seen, CH4 more than doubles the radiative heat 3

fluxes. Compared with the equilibrium case, the calcu-

lated nonequilibrium values are nearly twice. The heat
load value of 93.5 kJ/cm2 is approximately 1/4 of that of 2
Galileo Probe vehicle, which was about 350 kJ/cm2 [22].
4
1
Calculated radiative heat flux,1 cm behind shock in 1-D flow
Jits et al (2005) trajectory
81%H2-14.5%He-1.5%CH4, σc=10-17 cm2 (93.5 kJ/cm2)
2
81%H2-19%He (40.7 kJ/cm ) 0
3 2
Equil. 81%H2-14.5%He-1.5%CH4 (47.4 kJ/cm ) 150 160 170 180 190 200 210 220
2
Radiative heat flux, kW/cm

Flight time, sec

Figure 9. Calculated radiative heat fluxes for
aerobraking flight in Neptune considered
2
by Hollis et al (2004).
Table 2. Calculated radiative heat fluxes for aero-
braking flight in Neptune considered by Hollis et
1 al (2004).
Time ρ Us q (Hollis) q (Park) q (equil)
sec kg/m3 m/s kW/cm2 kW/cm2 kW/cm2
r r r

150 1.35 5 31480 0.566 1.914 0.458

0
−

5 30570
150 160 170 180 190 200 210
170 9.42 1.33 3.63 2.60 −
Flight time, sec
180 1.47 4 29270 1.28 3.80 2.65
Figure 8. Calculated radiative heat fluxes for
−

190 1.61 4 27660 0.634 2.85 1.75

aerobraking flight in Neptune considered
−

210 5.88 5 25730 0.075 0.520 0.391

by Jits et al (2005).
−

In Fig. 9 and in Table 2, the calculated radiative heat Heat load kJ/cm2 47.4 164 104
fluxes are shown for the large vehicle in the flight tra-
jectory considered by Hollis et al [3]. For this case, the It is to be noted here also that the radiative heat flux
length of the constant-area channel is taken to be 2.8 cm, values presened by Hollis et al are at the wall. The
the shock layer thickness for the vehicle [3]. The present presently calculated fluxes approximately represent the
heat load value of 164 kJ/cm2 is about 3.5 times Hollis et heat fluxes at the boundary layer edge. Because most of
al’s value of 46 kJ/cm2 . Compared with the equilibrium the presently calculated radiation power is in the vacuum-
value of 104 kW/cm2 , the nonequilibrium value is about ultra violet wavelength range, much of it will be absorbed
1.5 times. The heat load of 164 kJ/cm2 is about half of in the boundary layer. This absorption phenomenon heats
the Galileo’s 350 kJ/cm2 . the boundary layer and thereby increases convective heat
In Table 3, the contributions of the three radiating flux [24]. Hollis et al report high convective heat fluxes.
species, H, H2 , and C, are shown for the 180 sec time A portion of this convective heat flux values may be due
8 AIAA 2010-4520

to radiation. If this is true, perhaps there is not much dif- a range of conditions anticipated in Neptune aerobraking
ference in the calcualted values between the present work flight.
and the work of Hollis et al.
Table 3. Contribution of radiation mechanisms for References
the 180 sec time point in aerobraking trajectory 1. Park, C., “Nonequilibrium Ionization and Radiation
considered by Hollis et al (2004). in Hydrogen-Helium Mixtures,” AIAA Paper 2010-814;
submitted to Journal of Thermophysics and Heat Trans-
Radiater qr fer.
kW/cm2 2. Park, C., “Stagnation-Point Radiative Heat Fluxes
in Neptune aerobraking,” paper presented at 7th Interna-
H + H2 + C 3.80 tional Planetary Probe Workshop, Barcelona, June 14-18,
H+C 3.56 2010.
H 1.31 3. Hollis, B. R., Wright, M. J., Olejniczak, J.,
Takashima, N., Sutton, K., and Prabhu, D., “Preliminary
Parametric Calculation Convective-Radiative Heating Environments for a Nep-
tune Aerocapture Mission,” AIAA Paper 2004-5177, 2004.
In Table 4, the results of parametric calculation are 4. Jits, R., Wright, M., and Chen, Y-K., “Closed-Loop
given. Here again, the radiative heat fluxes are those for Trajectory Simulation for Thermal Protection System De-
a constant-area channel flow. The flux values are at x sign for Neptune Aerocapture,” Journal of Spacecraft and
= 1 cm, representative of the cases considered by Jits et Rockets, Vol. 42, No. 6, November-December 2005, pp.
al, and x = 3 cm, representing Hollis et al’s cases. The 1025-1034.
Table indicates that the radiative heat flux values do not 5. Gautier, D., Conrath, B. J., Owen, T., de Pater,
behave monotonically. This is a result of the nonequi- I., and Atreya, S. K., “The Troposphere of Neptune,” in
librium radiation overshoot phenomenon observed in Fig. Neptune and Triton, edited by D. P. Cruikshank, The
6(d). University of Arizona Press, Tucson, Arizona, 1995, pp.
Table 4. Radiative heat flux at the end of a 547-610.
constant-area channel of x = 1 and 3 cm. 6. Sutherland, J. W., Su, M. C., and Michael, J. V.,
“Rate Constants for H + CH4 , CH3 + H2 , and CH4 Dis-
Frstrm ρ, kg/m3 1.0 5 3.16 5 1.0 4
− − −
3.16 4
− sociation at High Temperature,” International Journal of
Chemical Kinetics, Vol. 33, No. 11, 2001, pp. 669-684.
x = 1 cm 7. Dean, A. J., Davidson, D. F., and Hanson, R. K.,
Us, km/s 32 0.722 2.64 3.23 8.247 “A Shock Tube Study of Reactions of C Atoms with H2
30 0.580 2.42 2.50 5.04 and O2 Using Eximer Photolysis of C3 O2 and C Atom
28 0.381 1.60 1.39 2.97 Atomic Resonance Absorption Spectroscopy,” The Jour-
26 0.186 0.818 0.671 1.61 nal of Physical Chemistry, Vol. 95, No. 1, 1991, pp.
24 .0353 0.137 0.150 0.321 183-181.
x = 3 cm 8. http://kinetics.nist.gov/CKMech/Links.jsp, NIST
Us, km/s 32 2.38 1.99 5.46 9.62 Chemical Kinetics Database, Ver. 7.0, 2003.
30 2.20 1.55 3.59 6.56 9. Baulch, D. L., Cobos, C. J., Cox, R. A., Prank,
28 1.60 0.946 1.85 5.69 P., Hayman, G., Just, Th., Kerr, J. A., Murrels, T.,
26 0.789 0.476 0.881 2.46 Pilling, M. J., Troe, J., Walker, R. W., and Warnatz,
24 0.131 0.130 0.198 0.585 J., “Evaluated Kinetic Data for Combustion Modelling,
Supplement I,” Journal of Physical Chemistry Reference
Conclusions Data, Vol. 26, No. 6, 1994, pp. 847-1033.
10. Kim, J. G., Kwon, O. J., and Park, C., “Master
Addition of 1.5% of CH4 into a H2 -He mixture sig- Equation Study and Nonequilibrium Chemical Reactions
nificantly shortens ionization equilibration distance and for H + H2 and He + H2 ,” Journal of Thermophysics and
more than doubles radiative heat flux values. Radiative Heat Transfer, Vol. 23, No. 3, July-September 2009, pp.
heat flux exhibits an overshoot phenomenon, and is typ- 443-453.
ically 1.5 times the equilibrium value. Two-thirds of the 11. Kim, J. G., Kwon, O. J., and Park, C., “State-
radiation is from carbon atoms. For the Neptune aero- to-State Rate Coefficients and Master Equation Study for
braking flights considered by Jits et al and by Hollis et H2 + H2 ,” AIAA Paper 2009-1023, January 2009; to be
al, the radiative heat load is calculated to be 94 and 164 published in Journal of Thermophysics and Heat Trans-
kJ/cm2 . The radiative heat flux value are calculated over fer.
 AIAA 2010-4520 9

12. Dunn, M. G., “Measurement of C+ + e + e and

CO+ + e Recombination in Carbon Monoxide Flows,”
AIAA Journal, Vol. 9, No. 11, Vol. 9, No. 11, November
1971, pp. 2184-2191.
13. Giusti-Suzor, A., and Lefebvre-Brion, H., “The
Dissociative Recombination of CH+ Ions,” The Astro-
physical Journal, Vol. 214, June 1977, pp. L101-L103.
14. Mul, P. M., and Mitchell, J. B. A., D’Angelo,
V. S., Defrance, P., McGowan, J. W., and Forelich, H.
R., “Merged Electron-Ion Experiments IV. Dissociative
Recombination for the Methane Group CH+ ,....,CH+5 ,”
Journal of Physics B: Atomic, Molecular, and Optical
Physics, Vol. 14 (1981), pp. 1353-1361.
15. Amity, Z., and Zajfman, D., “Dissociative Recom-
bination of CH+ : Cross Section and Final States,” Phys-
ical Review A, Vol. 54, No. 5, November 1996, pp. 4032-
4050.
16. Takagi, H, Kosugi, N., and Le Dourneuf, M.,
“Dissociative Recombination of CH+ ,” Journal of Physics
B: Atomic, Molecular, and Optical Physics, Vol. 24,
(1991), pp. 711-732.
17. Ervin, K. M., and Armentrout, P. B., “Threshold
Behavior of Endothermic Reactions: C+ (2 P) + H2 →
CH+ + H,” Journal of Chemical Physics, Vol. 80, No.
6, March 1984, pp. 2978-2980.
18. Stancil, P. C., Havener, C. C., Krstic, P. S.,
Schultz, D. R., Kimura, M., Gu, J.-P., Hirsch, G.,
Buenker, R. J., and Zygelman, B., “Charge Transfer in
Collisions of C+ with H and H+ with C,” The Astrophys-
ical Journal, , Vol. 502, August 1998, pp. 1006-1009.
19. Jakenism A., and Mavridis, A., “An Accurate De-
scription of the Ground and Excited States of CH,” Jour-
nal of Chemical Physics, Vol. 111, No. 21, December
1999, pp. 9536-9548.
20. Metropulos, A., and Mavridis, A., “Predissociation
Lifetimes of the E2 Π and F2 Π States of CH,” Chemical
Physics Letters, Vol. 331, 2000, pp. 89-94.
21. Luque, J., Jeffries, J. B., Smith, G. P., and
Crosley, D. R., “Predissociation of CH B2 Σ+ v =0,1
Levels Studied by Cavity Ring-Down Absorption Spec-
troscopy,” Chemical Physics Letters, Vol. 346, 2001, ii
209-216.
22. Chul Park, ”Stagnation Region Heating Environ-
ment of Galileo Probe,” Journal of Thermophysics and
Heat Transfer,Vol. 23, No. 3, July-August 2009, pp. 417-
424.
23. Livingston, F. R., and Poon, T. Y., “Relaxation
Distance and Equilibrium Electron Density Measure-
ments in Hydrogen-Helium Plasmas,” AIAA Journal, Vol.
14, No. 9, 1976, pp. 1335-1337.
24. Park, C., “Radiative to Convective Heat Flux
Conversion by Boundary Layer Absorption,” AIAA Pa-
per 2009-1583, January 2009.